2016 j2 h2 Chem Prelim-Updated-Pw

JC2 Prelim Paper
2016
H2 Chemistry
1 ANGLO CHINESE JUNIOR COLLEGE
2 ANDERSON JUNIOR COLLEGE
3 CATHOLIC JUNIOR COLLEGE
4 DUNMAN HIGH SCHOOL
5 HWA CHONG INSTITUTION
6 INNOVA JUNIOR COLLEGE
7 JURONG JUNIOR COLLEGE
8 MILLENNIA INSTITUTE
9 MERIDIAN JUNIOR COLLEGE
10 NATIONAL JUNIOR COLLEGE
11 NANYANG JUNIOR COLLEGE
12 PIONEER JUNIOR COLLEGE
13 RAFFLES INSTITUTION
14 RIVER VALLEY HIGH SCHOOL
15 ST. ANDREWS JUNIOR COLLEGE
16 SERANGOON JUNIOR COLLEGE
17 TAMPINES JUNIOR COLLEGE
18 TEMASEK
19 VICTORIA JUNIOR COLLEGE
20 YISHUN JUNIOR COLLEGE
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ANGLO-CHINESE JUNIOR COLLEGE

DEPARTMENT OF CHEMISTRY
Preliminary Examination
CHEMISTRY 9647/01
Higher 2
Paper 1 Multiple Choice

29 August 2016
1 hour
Additional Materials: Multiple Choice Answer Sheet
Data Booklet
READ THESE INSTRUCTIONS FIRST
Write in soft pencil.

Do not use staples, paper clips, glue or correction fluids.
Write your name, index number and tutorial class on the Answer Sheet in the spaces provided unless this
has been done for you.
There are forty questions on this paper. Answer all questions. For each question there are four possible
answers A, B, C and D.
Choose the one you consider correct and record your choice in soft pencil on the separate Answer Sheet.
Read the instructions on the Answer Sheet very carefully.
Each correct answer will score one mark. A mark will not be deducted for a wrong answer.
Any rough working should be done in this booklet.
The use of an approved scientific calculator is expected, where appropriate.
9647/01/Prelim/16
ACJC 2016
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This
is document consists of 17 printed pages and
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ANGLO CHINESE JUNIOR
ANGLO-CHINESE NIO COLLEGE
Department of Chemistry
a 1 blank page.
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ACJC 2016 9647/01/Prelim/2016 [Turn over

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Section A
For each question there are four possible answers, A, B, C, and D. Choose the one you consider
to be correct.
1 3.00 g of an impure sample of calcium carbonate was heated strongly until there was no
change in mass. 200 cm3 of carbon dioxide, measured at room conditions, was obtained.
What is the percentage purity of calcium carbonate?
A 27.8 % B 29.8 % C 30.4 % D 35.8 %
2 Use of the Data Booklet is relevant to this question.
Which underlined element in the following species has the +6 oxidation number?
A ReOCl4
B H2P2O72
C TiCl4
D SbCl52
Deuterium, 21D, is an isotope of hydrogen.
Which of the following species has more electrons than protons, and more neutrons than
protons?
A D3O+ B ND4+
C OD D AlD4
4 In which of the following pairs does the first compound have a higher melting point than the
second compound?
first compound second compound
A Mg3N2 Al2O3
B NH2OH H2O
C CH3OCH3 (CH3)2NH
D
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5 Which of the following bonds is not present in the following molecule?
escitalopram
A a bond formed by sp3sp2 overlap between two C atoms

B a bond formed by spsp overlap between C and N atoms
C a bond formed by sp2sp2 overlap between two C atoms
D a bond formed by sp3sp2 overlap between C and N atoms
6 Which of the following sets of compounds and ions is arranged in increasing bond angles?
A NO2+ < CO32 < SO42

B IF4 < N2O4 < N3
C ICl2 < H2S < NO2
D SCl2 < C2H2 < CH2Cl2
7 0.50 g of a volatile liquid was placed in a syringe with a frictionless piston. The syringe was
slowly warmed up till 91.0 oC at atmospheric pressure. The volume occupied in the syringe
was 200.0 cm3 when all the liquid was vaporised.
Assuming the vapour behaves as an ideal gas, what is the relative molecular mass of the
liquid?
A 18.7 B 74.9 C 93.5 D 149.8
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8 The enthalpy change when solid calcium chloride dissolves in water is 120 kJ mol1.
250 g of water is placed in an insulated cup containing 11.1 g of calcium chloride.
If the solution has the same specific heat capacity as liquid water, what is the rise in
temperature of the solution?
11.1120 11.1 120103

A K B K
2504.18 111 250 4.18
250 4.18 11.1120
C 3 K D K
11.1 12010 111 2504.18
The standard half-cells of four metals Mg, P, Q and R and their respective cations in
solution were connected in pairs and the potential difference recorded.
The results obtained are as shown.
positive electrode negative electrode e.m.f. /V
P Mg +1.60
Q Mg +2.22
Q R +2.55
Which of the following is the decreasing order of reducing power for the four metals?
A R > Mg > P > Q

B R > Mg > Q > P
C Q > P > Mg > R
D P > Q > Mg > R
10 Which of the following statements is always true for a chemical reaction that has reached
chemical equilibrium?
A The yield of the product(s) is greater than 50%.

B The rate of the forward reaction is greater than the backward reaction.
C The amounts of reactants and products do not change.
D Both forward and backward reactions have stopped.
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11 The graph shows the change in pH when 0.10 mol dm3 acid is gradually added to V cm3 of
0.10 mol dm3 alkali.
Which of the following combinations could have given these results?
V alkali acid
A 10 Sr(OH)2 CH3CO2H
B 20 Ba(OH)2 HCl
C 10 Ca(OH)2 H2SO4
D 20 NaOH HO2CCO2H
12 Nitrogen oxide reacts with hydrogen gas as shown in the equation below.
2NO(g) + 2H2(g) N2(g) + 2H2O(g)
The reaction was determined to be second order with respect to NO and first order with
respect to H2. In an experiment, 2.0 mol dm3 of excess NO was used to react with H2, the
concentration of H2 decreased to 6.25% of its original value in 24 minutes.
How many minutes will it take for the concentration of H2 to decrease to 6.25% of its original
value if the experiment was repeated using an excess of 4.0 mol dm3 of NO?
A 1.5 B 4.5 C 6.0 D 9.0
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13 Figure 1 shows the melting points of eight consecutive elements whereas Figure 2 shows
the third ionisation energies of another set of eight consecutive elements, inclusive of
element Z in Figure 1.
Which of the options in Figure 2 correspond to element Z in Figure 1?
third IE / kJ mol1
melting point / OC
B
A
Z C
elements elements
Figure 1 Figure 2
14 An equimolar amount of MgCl2, PCl5 and KCl were separately added to three beakers,
each containing 50 cm3 of water.
Which option correctly shows the resultant solutions arranged in increasing pH?
A MgCl2, PCl5, KCl

B PCl5, MgCl2, KCl
C KCl, MgCl2, PCl5
D PCl5, KCl, MgCl2
15 Which of the following properties would not be expected for Group II elements or their
compounds?
A Barium sulfate has a higher temperature of decomposition than magnesium sulfate.

B Barium oxide in water produces a solution which reacts with dilute hydrochloric acid to
give a solution with a pH of approximately 7.
C Beryllium forms compounds with the least covalent character.
D Upon heating the nitrates of Group II elements, the volume of nitrogen dioxide
evolved is four times as great as the volume of oxygen.
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16 Interhalogen compounds contain atoms of two or more different halogens. The interhalogen
ICl was reacted with excess aqueous sodium hydroxide for a period of time.
What is the relative proportion of each ion present in the solution after this reaction?
Cl I IO IO3
A 1 1 0 0
B 1 0 1 0
C 1 2 3 1
D 3 2 0 1
17 Which statement about hydrogen halides is incorrect?
A The acidity of hydrogen halides increases down the group.

B The reducing power of hydrogen halides increases down the group.
C The halogens, with the exception of fluorine, react with hydrogen to form hydrogen
halides which have permanent dipole permanent dipole interactions.
D The thermal stability of hydrogen halides increases down the group due to a larger
electron cloud that is more polarisable.
Which of the following is not true about the first row transition metals and their compounds?
A Fe(CN)63 does not oxidise I.

B Fe2(CO3)3 can be prepared by reacting FeCl3(aq) with Na2CO3(aq).
C On addition of H2O2(aq) to hot acidified K2Cr2O7(aq), a green solution is formed.
D On addition of Co(NO3)3 to water, a gas that relights a glowing splint is produced.
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19 Aklavinone is a tetracycline antibiotic.
aklavinone
Which combination of the number of chiral centres and of the number of sp2 and sp3
hybridised carbon atoms does it possess?
number of chiral centres number of sp2 hybridised number of sp3 hybridised

carbon carbon
A 3 14 8
B 3 15 7
C 5 14 8
D 5 15 7
20 Methylcyclopentane reacts with bromine in the presence of UV light.
Which statement is true about this reaction?
A A possible rate determining step for this reaction is
B There are three possible monosubstituted products.

C Methylcyclopentane will react slower with chlorine than bromine in the presence of UV
light.
D A by-product formed in this reaction is hydrogen.
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21 Which is the main product formed when one mole of 2methylbuta1,3diene is allowed to
react with one mole of HBr at room temperature for a prolonged period of time?
A B
C D
22 Which of the following could be the reagents and conditions for the three steps used in the
synthesis shown below.
step 1 step 2 step 3
concentrated HNO3 and

A CH3Cl and AlCl3 KMnO4 and H2SO4, heat
concentrated H2SO4, heat

B CH3(CH2)2Cl and AlCl3 K2Cr2O7 and H2SO4, heat

C CH3Cl and AlCl3 K2Cr2O7 and H2SO4, heat

D CH3(CH2)2Cl and AlCl3 KMnO4 and H2SO4, heat
23 A student investigated four different fuels. Each fuel was used separately to raise the
temperature of 1 dm3 of water from 20 oC to 100 oC. Each fuel undergoes complete
combustion. All other conditions were kept the same in each experiment.
Which fuel will produce the smallest amount of carbon dioxide in these experiments?
standard enthalpy change

fuel
of combustion/ kJ mol1
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n n
A ethane 1560
B ethanol 1367
C methanol
th 715
15
D propane 2220

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24 The main reason that phenol is a better Brnsted acid than cyclohexanol is
A that it is a better proton donor.

B the cyclohexyl group is an electron donating group by induction, which destabilises
the anion formed during the dissociation.
C phenol is able to stabilise the anion formed during the dissociation by resonance,
where the electrons are delocalised in the phenyl ring.
D the phenyl group is an electron withdrawing group by induction, which stabilises the
anion formed during the dissociation.
25 Propanone reacts with methylamine to form an imine as shown in the equation.
Similarly, propanone also reacts with hydroxylamine, NH2OH, to form an oxime.
Which of the following best describes the type of reaction that has occurred and the
structural formula of the oxime?
type of reaction structural formula of the oxime
A nucleophilic addition
B nucleophilic addition
C condensation
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n yli e
condensation

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26 Compound A is an example of a prostaglandin, which belongs to a group of physiologically

active lipid compounds having diverse hormone-like effects in animals.
compound A compound B
Which reagent will convert compound A to compound B efficiently?
A NaBH4 B LiAlH4/dry ether

C H2/Pt D Sn/concentrated HCl
27 Lactic acid, CH3CH(OH)CO2H, is found in sour milk.
Which of the following equations represent a possible reaction with lactic acid?
A CH3CH(OH)CO2H + CH3OH o CH3CH(OCH3)CO2H + H2O

B CH3CH(OH)CO2H + CH3CO2H o CH3CH(OCOCH3)CO2H
C CH3CH(OH)CO2H + PCl5 o CH3CH(Cl)CO2H + POCl3 + HCl
D CH3CH(OH)CO2H + 4I2 + 7NaOH o (CO2Na+)2 + CHI3 + 5NaI + 6H2O
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The tetrapeptide
ide
de above is a fragment of SNAP-25,
SNAP
SNA -25, a substrate
subst of Botulinum toxin (Botox).
How many molesoles of NaOH will react with

wit 1 mole of the tetrapeptide when it is heated under
reflux with aqueous
ueous sodium hydroxide
hydroxid until
until no further reaction occurs?
occurs?
A 3 B 5 C 6 D 7

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29 The demand for natural shampoos and detergents has led to the development of more
biodegradable detergents such as sorbitan monolaurate, which is made from plants.
sorbitan monolaurate
Which of the following statements about sorbitan monolaurate is correct?
A It is optically inactive.
B It can react with concentrated sulfuric acid on heating.
C There will be an orange precipitate formed upon adding 2,4dinitrophenylhydrazine to
the compound.
D There will be no colour change on heating the compound with acidified potassium
dichromate(VI) solution.
30 Hydrocortisone is a steroid hormone produced by the adrenal gland and is released in

response to stress. It is commonly used as an active ingredient in anti-inflammatory
creams.
hydrocortisone
Which of the following statements about hydrocortisone is correct?
A When treated with an excess of hot concentrated acidified KMnO 4, it forms a

compound containing seven carbonyl groups.
B When warmed with aqueous alkaline iodine, a yellow precipitate is observed.
C When treated with cold dilute KMnO4, it forms a compound containing two additional
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hydroxyy groups.
g
D When treated with NaBH4 in the presence of methanol, it for
forms a compound
containing
ng seven hydroxy groups.

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Section B
For each of the questions in this section, one or more of the three numbered statements 1 to 3
may be correct.
Decide whether each of the statements is or is not correct (you may find it helpful to put a tick
against the statements that you consider to be correct).
The responses A to D should be selected on the basis of
A B C D
1, 2 and 3 1 and 2 2 and 3 1 only

are only are only are is
correct correct correct correct
No other combination of statements is used as a correct response.
31 Epsom salt is a sedative for the nervous system. Its active ingredient is magnesium sulfate
which is soluble in water. The corresponding barium sulfate is insoluble in water.
What factors account for the difference in solubility between magnesium sulfate and barium
sulfate?
1 Magnesium sulfate has a higher solubility product than barium sulfate.

2 Magnesium ions have a higher enthalpy of hydration than barium ions.
3 Magnesium sulfate has a larger magnitude of lattice energy than barium sulfate.
32 The diagram shows a set-up used to find the transition temperature at which white tin and
grey tin are in equilibrium. This was found to be 15 C. Above 15 C, grey tin from
electrode I dissolves and is deposited on electrode II as white tin.
V
grey tin white tin
electrode I
electrode II
thermostat tank
(NH4)2SnCl6 (aq)
Which of the following

ollowing statements about the
e set-up
set-up are
re true?
ru
1 At 15 C,
C,, no current flows.
2 Below 15
5 C, electrons flow through the external circuit from I to II.
II
3 The conversion of white tin to grey tin is an endothermic process.

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A B C D
1, 2 and 3 1 and 2 2 and 3 1 only

33 The pKa values of some ammonium ions at 298 K are given below.
ammonium ion pKa
CH3NH3+ 10.66
(CH3)3NH+ 9.81
Based on the data given, which of the following statements are correct?
1 The pH of 0.1 mol dm3 of (CH3)3NH+Cl is 5.4.

2 (CH3)3N is more basic than CH3NH2 due to the presence of more electron donating
alkyl groups.
3 1 mol of (CH3)3N requires more HCl for complete neutralisation than 1 mol of CH3NH2.
34 Curve Z represents the distribution of energies of the gaseous molecules for an uncatalysed
reaction.
Curve W
Curve Z
P Q
Which of the following statements are false?
1 Curve W will be the distribution curve obtained when the reaction is catalysed and Q
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nts the most probable energy of the molecules.
represents molecule
2 Curve W will be the e distribution curve obtained at a higher temperature
te and S
nts the most probable energy of the molecules.
represents
3 Curve Z will be the distribution curve obtained
taine when the reaction is uncatalysed
u and P
represents the most probable energy off the molecules.

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A B C D
1, 2 and 3 1 and 2 2 and 3 1 only

35 Sulfur burns in chlorine gas to form disulfur dichloride, S2Cl2. In excess chlorine gas, the
following equilibrium is established.
S2Cl2 + Cl2 2SCl2
Which statements regarding S2Cl2 and its equilibrium with SCl2 are correct?
1 S2Cl2 dissolves in water to give a solution with pH greater than 7.

2 S2Cl2 is a liquid at room temperature.
3 The sulfur atoms have a bent geometry in both S2Cl2 and SCl2.
Which of the following statements are true for green aqueous solution of V2(SO4)3?
1 Zn metal can reduce V3+(aq) to V2+(aq).

2 The solution appears green as the d-orbitals are split by the presence of the sulfate
ions.
3 V3+(aq) can serve as a homogeneous catalyst in the reaction between iodide ions and
peroxodisulfate ions.
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A B C D
1, 2 and 3 1 and 2 2 and 3 1 only

37 Unripe fruits often contain polycarboxylic acids. These are acids with more than one
carboxylic acid group in their molecule. One such acid is citric acid shown below.
Another polycarboxylic acid present in unripe fruit is a colourless crystalline solid, W, which
has molecular formula of C4H6O5.
A sample of W of mass 1.97 g was dissolved in water and the resulting solution titrated with
1.00 mol dm3 NaOH. 29.4 cm3 of 1.00 mol dm3 NaOH was required for complete
neutralisation.
What could W be?
38 Which of the following statements are always true of the isoelectronic point, pI, of an amino
acid?
1
2
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It is the pH where the zwitterionic form of the amino acid is most dominant.
do
dom
It is the pH where the amino acid does not migrate when placed in an
It is the average of the first two pKa values.
a electric field.

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A B C D
1, 2 and 3 1 and 2 2 and 3 1 only

39 The rod cells in the retina at the back of the eye contain an alcohol called retinol which is
responsible for their sensitivity to light. Retinol is oxidised by an enzyme-catalysed reaction
to retinal with the following structure:
retinal
Which of the following statements about retinal are correct?

1 It can react with NH2NH2.
2 The molecular formula of retinal is C20H28O.
3 Oxidative cleavage of retinal gives two different organic products.
40 Benzocaine and menthol are local anaesthetics used in sunburn ointments and skin lotions.
Their structures are shown below:
benzocaine menthol
Which of the following reagents and conditions can be used to distinguish between the two
compounds?
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1 aqueouss b
bromine, dark
2 iodine in
n aqueous sodium hydroxide, heat
3 acidified
d aqueous potassium manganate(
mangana VII),
VII
manganate(VII),), heat

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BLANK PAGE
Answers:
1 2 3 4 5 6 7 8 9 10
A A D B D B B B A C
11 12 13 14 15 16 17 18 19 20
A C A B C D D B B A
21 22 23 24 25 26 27 28 29 30
A D A C D B D D B C
31 32 33 34 35 36 37 38 39 40
C D D B C D C B A B
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Index No. Name Form Tutorial Subject
Class Class Tutor

CHEMISTRY 9647/02
Higher 2
Paper 2 Structured Questions 16 August 2016
2 hours
Candidates answer on the Question Paper
Additional Materials: Data Booklet
Write your name, index number, form class, tutorial class and subject tutors name on all the work you
hand in.
Write in dark blue or black pen.
You may use a soft pencil for any diagrams, graphs or rough working.
Do not use staples, paper clips, glue or correction fluid.
Answer all questions.

A Data Booklet is provided.
The number of marks is given in brackets [ ] at the end of each question or part question.
At the end of the examination, fasten all your work securely together.
For Examiner's Use

Question no. Marks
1
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This document consists of 15 printed

inte pages and 1 blank page
page.
9647/02/Prelim/16 ANGLO-CHINESE JUNIOR COLLEGE

ACJC 2016 Department of Chemistry [Turn over
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2
1 Planning (P)
The solubility of a metal hydroxide, M(OH)2 at a particular temperature is defined as the

mass of metal hydroxide that dissolve in 100 g of water.
A saturated solution of the metal hydroxide is one in which no more solid can dissolve at
this fixed temperature. At 25oC, the solubility of metal hydroxide is approximately less than
2g /100g of water.
You are to plan an experiment using the method of gravimetric analysis to achieve these
objectives:
1. determine the solubility product, Ksp of the metal hydroxide accurately;
2. determine how the solubility of the metal hydroxide in sodium hydroxide is affected
by the concentration of hydroxide ions.
(a) (i) Write an equation with state symbols to show the dissolution of the metal
hydroxide in water.
. [1]
(ii) Suggest and explain how the solubility of the metal hydroxide varies with the
concentration of hydroxide ions.
...
. [1]
(b) You are provided with:

x pure solid metal hydroxide
x 2.0 mol dm-3 of sodium hydroxide
x the apparatus and chemicals normally found in a school or college laboratory.
Your plan should include details of:

x the preparation of a saturated metal hydroxide solution
x the preparation of a suitable range of diluted sodium hydroxide solutions
x an outline of how the results could be used to calculate the solubility of metal
hydroxide and its Ksp and show how the solubility of metal hydroxide in sodium
hydroxide varies with the concentration of hydroxide ions
x the risks involved and safety precautions taken
...
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(c) Suggest another experimental method to determine how the solubility of metal
hydroxide changes with the presence of sodium hydroxide. Suggest the results to be
collected.
...
...
...[2]
[Total: 12]
2 A, B and C are three organic molecules which share the same molecular formula,
C8H9NO2.
You are to make use of the data about the reactions of A, B and C given in the table
below to deduce their identities.
reaction reagent used A B C

1 KMnO4(aq), purple colour purple MnO4 purple MnO4
H2SO4(aq) remains decolourised decolourised
heat
2 excess Br2 (aq) white solid no visible white solid
formed with Mr reaction formed with Mr
= 308.8 = 308.8
3 NaOH (aq) at dissolves to give dissolves to does not
room a colourless give a dissolve at all
temperature solution colourless
solution
4 Na2CO3 (aq) no visible effervescence no visible
reaction seen reaction
5 HCl (aq) at does not dissolves to dissolves to
room dissolve at all give a give a
temperature colourless colourless
solution solution
(a) (i) Deduce the molecular formula of the white solid formed from A in reaction 2.
[1]
(ii) What type of reaction takes place in reaction 2 for A?
[1]
(iii) Hence list the possible functional groups present in A based on reaction 2
alone.
(b) (i)
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List
[2]
st the functional groups that are being tested for in reaction 3.
[2]
3
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(ii) Identify the gas that is being produced in reaction 4 for B and how you would
confirm its identity.
[2]
(iii) Which of the functional groups you have named in b(i) is confirmed by
reaction 4?
[1]
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(c) You now have enough information to determine the identities of A, B and C. Below
are three possible structures of A, B and C (not in order).
Draw the structural formula of the three compounds in the boxes below.
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e y [3]
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(d) Hydroxydanaidal is an insect pheromone synthesised by male tiger moths from

heliotrine in plants. It is an isomer of the three organic molecules above and is made
up of two five-membered rings.
In order for a ring to be aromatic, it has to fulfil the following criteria:
x The ring must have 4n+2 electrons in the delocalised porbital cloud
(where n is a positive integer).
x The ring must be planar.
x Every atom in the ring must be able to participate in delocalising the
electrons.
(i) Given that the N atom is sp2 hybridised, what is the number of p electrons in
the right ring of hydroxydanaidal?
[1]
(ii) Hence state if the right ring is aromatic.
[1]
(iii) Suggest reagents and conditions for a reaction that that will distinguish
hydroxydanaidal from the three isomers A, B and C.
[1]
[Total: 15]
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3 Group VII elements can form oxoanions of XOn which are strong oxidising agents. One
such example is bromate(V) anion, BrO3 which can oxidise iodide to form iodine, and
itself reduced to bromide.
(a) Write a balanced ionic equation for the reaction between bromate(V) and iodide.
... [1]
(b) A student wished to analyse the amount of iodine and the bromide ions produced
from the above reaction and hence he carried out the following procedures.
1) Add 25.0 cm3 of 0.150 mol dm-3 potassium bromate(V) solution to excess
potassium iodide (3 grams) and 5 cm 3 of 1 mol dm-3 H2SO4 in a 250 cm3 conical
flask.
2) Add sufficient chloroform, CHCl3, to the above solution immediately and transfer
the mixture to a separating funnel.
3) Separate the organic and aqueous layers and add barium nitrate solution to the
aqueous layer in a beaker.
4) Filter the above mixture and add silver nitrate to the filtrate in the conical flask.
5) To the resultant mixture in the conical flask in step 4, add sufficient concentrated
ammonia and filter once again.
(i) What is the purpose of adding chloroform in step 2?
...
[1]
(ii) What is the reason for adding barium nitrate in step 3?
...
[1]
(iii) A mixture of two precipitates will be formed when silver nitrate is added into
step 4. Suggest the identities of the precipitates.
[1]
(iv) Describe clearly what the student will observe in step 5 after he added in
concentrated ammonia and performed a filtration. Explain the chemistry
behind his method.
...
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...

...
[3]
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(c) Explain why fluorine does not form oxoanions such as FO3.
[1]
[Total: 8]
4 Compound X and compound Y are oxides formed from period 3 elements.
When water is added to both oxides, only X dissolves but not Y. However, Y will dissolve
when it is added to the aqueous solution of X and NaOH (aq) separately.
It is known that aqueous solution of X can react with solid potassium hydroxide in a ratio
of 1:3.
Identify compound X and Y, and explain the above reactions with the aid of balanced
equations.
...
...
...
...
...
...
...
...
[Total: 7]
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5 Chymotrypsin is a digestive enzyme found in the small intestines that can hydrolyse
peptide bonds within proteins. It is also used as a form of treatment for sports injuries to
reduce pain and inflammation. The three main amino acids involved in the catalytic activity
are histidine, aspartic acid and serine.
(a) The graph shows the results of an investigation of the initial rate of hydrolysis of
peptide D by the enzyme chymotrypsin. In the experiments, the initial concentration
of peptide D was varied but that of chymotrypsin was kept constant.
Rate
[Peptide D]
Explain the difference in the rate of hydrolysis at high and low concentrations of
peptide D.
...
...
......
... [2]
(b) The first step of the mechanism of the action of chymotrypsin is shown:
(i) In an aqueous external environment, suggest and explain whether the three
amino acids are orientated inward or outward of the compact structure.
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...

... [2]
ACJC 2016 9647/02/Prelim/2016

29
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11
(ii) State the roles of histidine in the mechanism shown above.
... [1]
(iii) Explain with reference to the mechanism, how a low pH might affect the
enzymatic activity of chymotrypsin.
...
... [2]
(iv) Draw the structural formula of a tripeptide with the sequence ser-his-asp,
showing the form which it would exist at pH 4.5 given the pKa of the R-group
in his = 6.04 and pKa of the R-group in asp = 3.90.
[2]
[Total: 9]
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ACJC 2016 9647/02/Prelim/2016
30
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12
6 Three unknown cations J2+, K2+ and L3+ are analysed according to the flowchart below.
J, K and L can be any one of the following: Al, Mn, Fe, Co, Ni, Pb, Zn, Sc.
(a) Identify the three cations and the three unknowns A, B and C. [6]
cations
J2+:
K2+:
L3+:
unknowns
A:
B:
C:
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31 trendyline
13
(b) Vanadium(II) chloride, VCl2 is prepared by the thermal decomposition of

vanadium(III) chloride, VCl3.
(i) Write the electronic configuration of a vanadium atom.
[1]
(ii) Hence explain why the third ionisation energy of vanadium is higher than the
second ionisation energy.
...
...
... [1]
(iii) Predict, with reason, which of the chlorides of vanadium, VCl2 or VCl3 will
have a higher melting point.
...
...
... [1]
[Total: 9]
7 Nitryl fluoride, NO2F is a colourless gas which acts as a strong oxidising agent and
fluorinating agent.
(a) Draw a dot-and-cross diagram of NO2F.
[1]
(b) It is known that NO2F can be produced from nitrogen dioxide and fluorine according
to the equation below.
2NO2(g) + F2(g) 2NO2F(g)
The rate equation for the reaction was also found to be Rate = k[NO2][F2].
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(i) Propose
ropose
op a two-step mechanism
m consistent
consi
c stent
nt with the above equation,
equ indicating
thee rate determining step
step.

...
... [2]

32 trendyline
14
(ii) Given that the reaction is exothermic, sketch a labelled energy profile
diagram for the complete reaction path including the formation of the
intermediate species.
[3]
(c) When NO2 and excess F2 were mixed together, [NO2F] varies with time, as shown in
the table below. The initial [NO2] used is 0.400 mol dm3.
>12)@
t / min [NO2F] / mol dm3 / mol dm3 min1 [NO2] / mol dm3
W
0.25 0.150 0.60 0.250

0.50 0.245
0.75 0.300
1.00 0.340
1.25 0.360
1.50 0.375 0.06 0.025
(i) Explain why it is necessary to use excess fluorine in this experiment to

confirm the order with respect to nitrogen dioxide.
...
... [1]
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33 trendyline
15
(ii) The rate at a particular time can be approximated using:

>12 )@
rate = W
Complete the table above by calculating >12)@ (to 2 decimal places) and
W
the [NO2] left (to 3 decimal places) at the respective timings. [2]
(iii) Hence, plot a graph of >12)@ against [NO2] to confirm and explain that the
W
reaction is first order with respect to NO2.
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[3]

[Total: 12]

34 trendyline
16
BLANK PAGE
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e
35 trendyline
1 2 3 4 5 6 7 8 9 10
A A D B D B B B A C
11 12 13 14 15 16 17 18 19 20
A C A B C D D B B A
21 22 23 24 25 26 27 28 29 30
A D A C D B D D B C
31 32 33 34 35 36 37 38 39 40
C D D B C D C B A B
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36 trendyline
Index No. Name Form Tutorial Subject
Class Class Tutor

CHEMISTRY 9647/02
Higher 2
2 hours
Write your name, index number, form class, tutorial class and subject tutors name on all the work you
hand in.

For Examiner's Use

Question no. Marks
1
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li TOTAL
This document consistss of 12 printed pages.

pages
9647/02/Prelim/16 ANGLO-CHINESE JUNIOR COLLEGE
ACJC 2016 Department of Chemistry [Turn over
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2
1 Planning (P)
The solubility of a metal hydroxide, M(OH)2 at a particular temperature is defined as the

mass of metal hydroxide that dissolve in 100 g of water.
A saturated solution of the metal hydroxide is one in which no more solid can dissolve at
this fixed temperature. At 25oC, the solubility of metal hydroxide is approximately less than
2g /100g of water.
You are to plan an experiment using the method of gravimetric analysis to achieve these
objectives:
1. determine the solubility product, Ksp of the metal hydroxide accurately;
2. determine how the solubility of the metal hydroxide in sodium hydroxide is affected
by the concentration of hydroxide ions.
(a) (i) Write an equation with state symbols to show the dissolution of metal
hydroxide in water. [1]
M(OH)2(s) + aq M2+(aq) + 2OH(aq) [1]
(ii) Suggest and explain how the solubility of the metal hydroxide varies with the
concentration of hydroxide ions. [1]
The solubility of metal hydroxide decreases when the concentration of sodium

hydroxide increases as there is common ion effect or explanation of eqm
shifting to the left when concentration of hydroxide increases (LCP).
Examiners Comments:
Students wrote full arrow instead of half arrows. Metal hydroxide is a sparingly
soluble salt hence the solid exists in equilibrium with its aqueous ions.
(b) You are provided with:

pure solid metal hydroxide
2.0 mol dm-3 of sodium hydroxide
the apparatus and chemicals normally found in a school or college laboratory.

the preparation of a saturated metal hydroxide solution
the preparation of a suitable range of diluted sodium hydroxide solutions
an outline of how the results could be used to calculate the solubility of metal
hydroxide and its Ksp and show how the solubility of metal hydroxide in sodium
hydroxide varies with the concentration of hydroxide ions
the risks involved and safety precautions taken [8]
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Method 1::
1. U sing a 50 cm3 burette/ 100 cm3 measuring cylinder/ 50 cm3 pipette, place
Using
100 cm3 of distilled water into a pre-weighted 250 cm3 dry and clean conical
aker (M1 g) placed in a thermostated
flask/beaker most water bath contro
controlled at a fixed
temperature. Weigh again with the distilled water inside to obtain the total mass of
the distilled water and beaker, M2 g.
ACJC2016 9647/JC2 Prelim Exam/2016

38
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3
2. Add about 2-4g (> solubility and depending on volume of solution used) mass of
solid metal hydroxide to the solution and stir with a glass rod. Stir the mixture
continuously until no more solid dissolves to ensure a saturated solution is obtained.
Let the mass of metal hydroxide be M3 g.
3. Allow reaction mixture to stand/ leave for a long time to reach equilibrium.
4. Pre-weigh the dry filter paper, M4 g. Filter the mixture with the use of a filter paper
and filter funnel into a beaker. Discard the filtrate. Weigh the mass of the filter paper
and solid, M5 g.
5. Wash the residue with some cold water and dry the filter paper with residue in an
oven/IR lamp. Temperature should be pre-set to 60oC (lower than the decomposition
temperature and to prevent the filter paper from burning). Let the filter paper cool
down in a dessicator. Weigh the filter paper and its contents.
6. Repeat the process of heating, cooling and weighing till constant mass of the filter
paper and its contents is obtained.
Mass of dissolved solute = M3 (M5 M4) = X g

(mass of solid M(OH)2 added - mass of residue)
Mass of solvent = M2 M1 = Y g
Solubility of metal hydroxide in 100g of water = X/ Y x 100 (g/100g of water)
OR
Method 2:
1. Measure about 100 cm3 (any volume) of water using a measuring cylinder and
place it in a dry and clean beaker placed in a themostated water bath.
2. Add about 2g (> solubility and depending on volume of solution used) mass of
solid metal hydroxide to the solution and stir with a glass rod. Stir the mixture
continuously until no more solid dissolves to ensure a saturated solution is
obtained.
3. Allow reaction mixture to stand/ leave for a long time to reach equilibrium.
4. Using an electronic weighing balance, measure and record the mass of an

empty, dry crucible/beaker. This is recorded as M1 g.
5. Using a dry filter funnel and filter paper, filter the suspension and collect the
saturated filtrate in the crucible. Measure the mass of the filtrate and crucible.
The mass obtained is M2 g.
g).
g a Bunsen burner, heat the solution until all the liquid is evap
6. Using
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tant
eva
evaporated off and
ant mass is obtained, cool it and re-weigh the beaker with its contents (M3
constant
Mass of dissolved solute = (M3 M1) = Xg

Mass of solvent = (M2 M1) = Yg
Solubility of metal hydroxide in 100g of water = 100 x X/Y
39
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4
6. Repeat the experiment with another mass of metal hydroxide to get reliable
results.
7. Conversion of solubility in g/ 100 g of water to mol dm-3 assume density of water =

1g cm-3
Calculate the Ksp of metal hydroxide as Ksp = [M2+][OH-]2.
Results:
M(OH)2(s) M2+(aq) + 2OH (aq)
Equilibrium concentration x 2x
(mol dm-3)
In a saturated solution,
Ksp = [x][2x]2 = 4x3
Preparation of standard solutions of sodium hydroxide
Volume of Initial concentration Final concentration

Volume of NaOH
3
water / cm3 of NaOH of NaOH
/ cm
(mol dm-3) (mol dm-3)
50 50 2 1
50 50 1 0.5
7. Prepare at least three standard solutions of sodium hydroxide of different

concentration (2 mol dm-3, 1 mol dm-3 and 0.5 mol dm-3).
8. Use of a burette to transfer 50 cm3 of the 2 mol dm-3 sodium hydroxide solution
into a 100 cm3 volumetric flask. Measuring cylinder is not accepted.
9. Top up to the mark with distilled water. Stopper, invert and shake to obtain a
homogeneous solution of 1 mol dm-3 sodium hydroxide.
10. Repeat steps 1-3 using 50 cm3 of the 1 mol dm-3 sodium hydroxide to obtain a
stock solution of 0.5 mol dm-3 sodium hydroxide.
OR vary the volume of water and sodium hydroxide used (keeping total volume
constant), use the same concentration of sodium hydroxide to obtain diluted
solutions
To investigate how the solubility of metal hydroxide varies with the

concentration of sodium hydroxide:
11. Repeat steps 1- 6 using the other three standard solutions of sodium hydroxide
of concentration (2 mol dm-3, 1 mol dm-3 and 0.5 mol dm-3).
12. Calculate the solubility of metal hydroxide for the three concentrations of sodium
hydroxide and tabulate how the solubility of metal hydroxide change with
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concentration
entration
ntration of sodium hydroxide.
Solubility
bility of metal hydroxide in sodium hydroxide = g / 100g of so
solvent
13. Observe
rve the trend that when concentrations of sodium h
erve hydroxide used
eases,
ases, the solubility of metal hydroxide increase
decreases, increases.
Risk and safety precaution:

Metal hydroxide and sodium hydroxide is corrosive and toxic in nature. Minimise
contact by using gloves and goggles.
40
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5
OR
Use oven/heat resistant gloves or tongs to handle the hot beaker/crucible.
OR Cool hot crucible before handling OR wear gloves when heating.
Examiners Comments:
1. Students need to pay more attention to details such as choosing appropriate
apparatus and suitable capacity for the apparatus.
2. Only some students were able to show more attention to details of how the
experimental data should be collected. For example, the mass of the solid
metal hydroxide should be known accurately to 2 or 3 decimal places.
Another example: to weigh the residue of the filtration, the mass of the dry
filter paper must be measured so that its mass can be deducted from the
combined mass of the dried residue and filter paper.
3. When determining how the solubility of metal hydroxide in sodium hydroxide
varies with the concentration of hydroxide ions, a known mass of solid metal
hydroxide must be dissolved into a fixed volume of known concentration of
NaOH (aq). This is not the same as adding NaOH (aq) to a saturated solution
of metal hydroxide.
4. If students suggest drawing a graph of mass of residue collected against
concentration of NaOH (aq), it is also necessary to state the expected shape
and gradient of the graph obtained. (Refer to N2012/III/1planning)
5. Very few students were able to apply their knowledge that the group II metal
hydroxide M(OH)2 undergoes thermal decomposition. In acknowledgement of
the likely decomposition reaction, the filtered M(OH)2 should not be dried at
high temperature i.e. over a Bunsen flame. Instead, drying should be carried
out under an infrared lamp or in a desiccator to prevent thermal
decomposition.
6. Students need to prepare at least 2-3 solutions of sodium hydroxide of
different concentrations to give a range of diluted solutions.
7. Students also need to recognise the fact that solubility is dependent on
temperature and to prepare a saturated solution in a thermostat controlled
water bath.
8.
(c) Suggest another experimental method to determine how the solubility of metal
hydroxide changes with the presence of sodium hydroxide. Suggest the results to be
collected. [2]
Titrimetric method. Prepare a saturated solution of metal hydroxide in sodium

hydroxide of known concentration and titrate the solution with standard HCl solution.
Results to be collected are: Initial burette reading/ final burette reading / titre volume
Examiners Comments:
Some students wrote that initial volume and final volume collected which is wrong.
[Total: 12]
C8H9NO2.
You are to make

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2 A, B and C are three organic molecules which share the same mol
ake use of the data about the reactions

below to deduce their identities.
eac
molecular formula,
of A, B and C given
giv in the table
reaction reagent used A B C

41
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6
1 KMnO4(aq), purple colour purple MnO4 purple MnO4

H2SO4(aq) remains decolourised decolourised
heat
2 excess Br2 (aq) white solid no visible white solid
formed with Mr reaction formed with Mr
= 308.8 = 308.8
3 NaOH (aq) at dissolves to give
dissolves to does not
room a colourless give a dissolve at all
temperature solution colourless
solution
4 Na2CO3 (aq) no visible effervescence no visible
reaction seen reaction
5 HCl (aq) at room does not dissolves to dissolves to
temperature dissolve at all give a give a
colourless colourless
solution solution
(a) (i) Deduce the molecular formula of the white solid formed from A in reaction 2.
[1]
C8H7NO2Br2
(ii) What type of reaction takes place in reaction 2 for A? [1]
Electrophilic substitution
(iii) Hence, list the possible functional groups present in A based on reaction 2
alone. [2]
Phenol, phenylamine
Examiners Comments:
(b) (i) List the functional groups that are being tested for in reaction 3. [2]
phenol and carboxylic acid

.
(ii) Identify the gas that is being produced in reaction 4 for B and how you would
confirm its identity. [2]
CO2.
Pass the gas through a solution of Ca(OH)2. It should form a white precipitate.
(iii) Which of the functional groups you have named in b(i) is confirmed by
reaction 4? [1]
Carboxylic acid
Examiners
rs Comments:
ers

42
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7
(c) You now have enough information to determine the identities of A, B and C. Below
are three possible structures of A, B and C (not in order).
Draw the structural formula of the three compounds in the boxes below. [3]
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tre
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43
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8
Examiners Comments:
1. Chemical structures must be drawn using a PEN in examinations.
(d) Hydroxydanaidal is an insect pheromone synthesised by male tiger moths from

heliotrine in plants. It is an isomer of the three organic molecules above and is made
up of two five-membered rings.
In order for a ring to be aromatic, it has to fulfil the following criteria:
The ring must have 4n+2 electrons in the delocalised porbital cloud
(where n is a positive integer)
The ring must be planar
Every atom in the ring must be able to participate in delocalising the
electrons.
(i) Given that the N atom is sp2 hybridised, what is the number of p electrons in
the right ring of hydroxydanaidal? [1]
(ii) Hence, state if the right ring is aromatic. [1]
Yes.
(iii) Suggest reagents and conditions for a reaction that that will distinguish
hydroxydanaidal from the three isomers A, B and C. [1]
Add Tollens reagent and warm/heat.

Add 2,4-DNPH or Bradys Reagent.
If student stated in (ii) that it is not aromatic then accept:
Add Fehlings solution and warm/heat as ecf
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Examiners
er s Comments:
[Total: 15]
3 Group VII elements can form oxoanions of XOn which are strong oxidising agents. One
such example is bromate(V) anion, BrO3 which can oxidise iodide to form iodine, and
44
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9
itself reduced to bromide.
(a) Write a balanced ionic equation for the reaction between bromate(V) and iodide. [1]
BrO3 + 6I + 6H+ Br + 3I2 + 3H2O [1]
Examiners Comments:
1. Students should use the information provided in the question (identity of products)
to construct the balanced redox reaction and not propose their own products.
(b) A student wished to analyse the amount of iodine and the bromide ions produced
from the above reaction and hence he carried out the following procedures.
1) Add 25.0 cm3 of 0.150 mol dm-3 potassium bromate(V) solution to excess
potassium iodide (3 grams) and 5 cm 3 of 1 mol dm-3 H2SO4 in a 250 cm3 conical
flask.
2) Add sufficient chloroform, CHCl3, to the above solution immediately and transfer
the mixture to a separating funnel.
3) Separate the organic and aqueous layers and add barium nitrate solution to the
aqueous layer in a beaker.
4) Filter the above mixture and add silver nitrate to the filtrate in the conical flask.
5) To the resultant mixture in the conical flask in step 4, add sufficient concentrated
ammonia and filter once again.
(i) What is the purpose of adding chloroform in step 2? [1]
It is to extract iodine into the organic layer as iodine is more soluble in CHCl3
due to the formation of effective interaction (induced dipole - induced dipole).
Examiners comments:
1. Students need to be clear in their reasoning that the removal of iodine will
allow for easy identification of the precipitates formed later since I2 forms an
equilibrium with I that results in a brown solution (I3).
(ii) What is the reason for adding barium nitrate in step 3?
[1]
It is to remove sulfate as barium sulfate so that it will not interfere with the
reaction when silver nitrate is added.
Examiners comments:
1. To state that BaNO3 is needed for reaction with H2SO4 is vague as it
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equires
quires the examiner to infer the product of the reaction. Also,
requires Als H2SO4 is an
acid
cid so such an answer brings up a possibility of a misconc
misconception whereby
BaNO
aNO
N 3 reacts with an acid.
(iii) A mixture of two precipitates will be formed when silver nitrat

nitra
nitrate is added into
ep 4
step 4. Suggest the identities of the
e precipitates.
p
precipitates [1]
AgBr and AgI

45
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10
(iv) Describe clearly what the student will observe in step 5 after he added in
concentrated ammonia and performed a filtration. Explain the chemistry
behind his method. [3]
Cream ppt of AgBr dissolves to give a colourless filtrate and yellow ppt of AgI
is obtained as the residue.
Ag+(aq) + 2NH3(aq) [Ag(NH3)2]+(aq) ----- (1)
When concentrated NH3 is added, the soluble complex of [Ag(NH3)2]+ is

formed, lowering the concentration of Ag+.
Hence the eqm (2) position shifts to the RHS, causing AgBr to dissolve.
AgBr (s) Ag+(aq) + Br-(aq) ----- (2)

OR
The ionic product [Ag+][Br] become smaller than Ksp.
However the Ksp values of AgI(s) is extremely low such that its ionic product
[Ag+][I] still exceed its Ksp [1], hence AgI remains insoluble even when
concentrated NH3 is added.
Examiners Comments:
1. This question has two parts: one on observations and the other on the theory
behind.
2. Students need to be clear in describing the observations (colour of solutions or

precipitates, effervescence of gas and the corresponding test to confirm its identity,
dissolution of solids etc)
3. Account for the observations based on the knowledge of factors affecting

solubility and the difference in Ksp values of the silver halides.
4. Some students do not know the reaction of Ag+ with NH3.
(c) Explain why fluorine does not form oxoanions such as FO3. [1]
1. F does not have 3d orbitals that are energetically accessible for electrons to
occupy / for expansion of octet to occur.
2. Fluorine is too / highly electronegative to have a positive oxidation number OR

cannot form dative bonds (if student include answer 1)
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ne
e is a small atom such that 3 oxygen atoms around it would result in too
3. Fluorine
much electronic
ectronic repulsion / steric hindrance.
hindrance
[Total: 8]
Examinersrs Comments:
ers
1. The fluorine
uorine here is an atom though it should
sho be noted the entire sp
species is a
polyatomic ion. Hence ideas of charge density / polarising power of F that
destabilise the ion are not correct.
46
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11
2. Students should pay attention to the usage of terms such as atomic or ionic
radius of F and what such terms imply of their description of F.
4 Compound X and compound Y are oxides formed from period 3 elements.
When water is added to both oxides, only X dissolves but not Y. However, Y will dissolve
when it is added to the aqueous solution of X and NaOH (aq) separately.
It is known that aqueous solution of X can react with solid potassium hydroxide in a ratio
of 1:3.
Identify compound X and Y, and explain the above reactions with the aid of balanced
equations.
Compound X: P4O10 / phosphorus (V) oxide / phosphorus pentoxide

Compound Y: Al2O3 / aluminium oxide
Only X is soluble in water but not Y:

P4O10 (s) + 6H2O (l) 4H3PO4 (aq)
ECF from identity of compound X for P2O5
Al2O3 has high lattice energy / strong ionic bonds and hence is not able to dissolve in
water.
Y will dissolve when added to the aqueous solution of X and NaOH (aq) separately:
Al2O3 is amphoteric and will react with both acids and alkalis.
Al2O3 (s) + 2H3PO4 (aq) 2AlPO4 (aq) + 3H2O (l)
OR
Al2O3 + 6H+ Al3+ + 3H2O
Al2O3 (s) + 2NaOH (aq) + 3H2O (l) 2NaAl(OH)4 (aq)

OR
Al2O3 (s) + 2OH (aq) + 3H2O (l) 2Al(OH)4
Reactions of solutions of X with potassium hydroxide:

H3PO4 (aq) + 3KOH (s) K3PO4(aq) + 3H2O(l)
OR
3H+ (aq) + 3KOH (s) 3K+ (aq) + 3H2O(l)
Examiners Comments:
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rmula
mula should not be used as an identity of su
1. Empirical formula substances.
[Total: 7]

47
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12
5 Chymotrypsin is a digestive enzyme found in the small intestines that can hydrolyse
peptide bonds within proteins. It is also used as a form of treatment for sports injuries to
reduce pain and inflammation. The three main amino acids involved in the catalytic activity
are histidine, aspartic acid and serine.
(a) The graph shows the results of an investigation of the initial rate of hydrolysis of
peptide D by the enzyme chymotrypsin. In the experiments, the initial concentration
of peptide D was varied but that of chymotrypsin was kept constant.
Rate
[Peptide D]
Explain the difference in the rate of hydrolysis at high and low concentrations of
peptide D. [2]
At low concentration of peptide D, substrates do not saturate or occupy all the

available active sites. Rate of reaction will be directly proportional to [substrate] or
first order reaction with respect to substrate.
At high concentration of peptide D, substrates saturate or occupy all the available

active sites. Rate of reaction will be independent of [substrate] Or zero order
reaction with respect to substrate.
(b) The first step of the mechanism of the action of chymotrypsin is shown:
(i) In an aqueous external environment, suggest and explain whether the three
amino acids are orientated inward or outward of the compact structure.
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[2]]
Three
hree
ree amino acids are orientated outward of the compact st structure as they
contain
ntain the polar hydroxyl and amine group which are able to form hydrogen
ontain
bonds/
nds/ ion-dipole with water molecules/ catalytic activity as there
onds/ the is binding to
th
substrate
ubstrate .
Examiners comments:
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13
Some students did not recognise that hydrophobic groups tend to face inward
and hydrophilic groups tend to face outward.
(ii) State the roles of histidine in the mechanism shown above.

[1]
It is both an acid (proton donor) and a base (proton acceptor). Or protonate

and deprotonate.
Examiners comments
1. Do not confuse between acid-base and redox reactions! The particle
that they give out are different!
Donor of H+ ion Bronsted-Lowry acid
Acceptor of H+ ion Bronsted-Lowry base
Loss of H atom Reducing agent
Gain of H atom Oxidising agent
(iii) Explain with reference to the mechanism, how a low pH might affect the
enzymatic activity of chymotrypsin. [2]
At low pH, excess H+ will react with the basic amine group of histidine OR it
will react with the COO- group of asp OR ionic bonds are disrupted, hence
this will lead to changes in enzyme shape and cause denaturation/ lose
enzymatic activity/ mechanism will not work.
(iv) Draw the structural formula of a tripeptide with the sequence ser-his-asp,
showing the form which it would exist at pH 4.5 given the pKa of the R-group
of his = 6.04 and pKa of the R-group of asp = 3.90. [2]
Examiners Comments:
1. The side chain of ser cannot be deprotonated, since alcohols are weaker
acids that water. (The effect of this relative acid strength is that alcohols will
not deprotonate in an aqueous medium.)
2. All protein / peptide sequences, in this case ser-his-asp, are shown with the
N-terminal is on the left and the C-terminal is on the right.
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3. The
he alpha-carboxy group for asp is also deprotonated
depro as it is more acidic
han the R group for asp as the COO- group is closer to the el
than e
electron
+
withdrawing
ithdrawing NH3 group.
4. The
he nitrogen atom on the left (Nx) is
s less basic compared to Ny as the lone
pair of electrons on Nx is unavailable
ble for protonation due to the overlap of p
orbitals on Nx atom with the p orbital of the neighbouring C atom. The lone
pair of electrons on Ny is found in a different plane hence it is available for
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14
protonation.
[Total: 9]
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50
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12
6 Three unknown cations J2+, K2+ and L3+ are analysed according to the flowchart below.
J, K and L can be any one of the following: Al, Mn, Fe, Co, Ni, Pb, Zn, Sc.
(a) Identify the three cations and the three unknowns A, B and C. [6]
Cations
J2+ : Pb2+ or [Pb(H2O)6]2+
K2+ : Zn2+ or [Zn(H2O)6]2+
L3+ : Fe3+ or [Fe(H2O)6]3+
Unknowns
A : [Fe(SCN)(H2O)5]2+
B : PbSO4
C : Zn(OH)2
trendyline
Identity
y of J and K can be switched.
ers
rs Comments:
Examiners
(b) Vanadium m (II) chloride, VCl2 is prepared by the thermal decomposition

decompositi of vanadium
(III) chloride, VCl3.
ACJC2016 9647/JC2 Prelim Exam/2016 [Turn over

51 trendyline
12
(i) Write the electronic configuration of the vanadium atom. [1]
V: 1s2 2s2 2p6 3s2 3p6 3d3 4s2
Examiners comments
1. Always write the full electronic configuration. It is not the candidates
(aka students) prerogative to use the shortform [Ar].
(ii) Hence, explain why the third ionisation energy of vanadium is higher than the
second ionisation. [1]
The second electron removed is from the 4s orbital whereas the third electron
is removed from the 3d orbital. The third electron removed is from an inner
principal quantum shell, which experiences greater nuclear attraction and
hence, requires more energy to remove.
(iii) Predict, with reason, which of the chlorides of vanadium, VCl2 or VCl3 will
have a higher melting point. [1]
Lattice energy q+ q-
r+ + r-
VCl3 will have a higher melting point. As V3+ has a smaller ionic radius and a
higher charge, VCl3 will have a more exothermic lattice energy requiring more
energy to melt. [1]
Examiners Comments:
1. Thermal decomposition is not the same as melting as the former involves a

chemical change in the substance while the latter involves a physical process with
no change in the chemical identity of the substance.
[Total: 9]
7 Nitryl fluoride, NO2F is a colourless gas which acts as a strong oxidising agent and
fluorinating agent.
(a) Draw a dot-and-cross diagram of NO2F. [1]
F
N
O O
Examiners comments
1. Students are reminded that the least electronegative atom should be the
central atom.
trendyline
2. Students should check their own answers to ensure that they did not attempt
to
o assign an expanded octet to the N atom, a Period 2 element.
elemen
(b) It is known
wn that NO2F can be produced from nitrogen dioxide and flu
fluorine according
quation below.
to the equation
2NO2 (g) + F2 (g) 2NO2F (g)

52 trendyline
12
The rate equation for the reaction was also found to be Rate = k[NO2][F2].
(i) Propose a two-step mechanism consistent with the above equation, indicating
the rate determining step. [2]
NO2 (g) + F2 (g) NO2F (g) + F (g) (slow; rate determining step)
NO2 (g) + F (g) NO2F (g)
Examiners comments
1. Students are reminded that the power of concentrations in the rate
equation must correspond to the stoichiometry of the slow step and
2. that the sum of the elementary steps should match the overall
balanced equation.
3. Charge conservation must also be observed in each step. i.e make
sure that charges are balanced in each step.
(ii) Given that the reaction is exothermic, sketch a labelled energy profile
diagram for the complete reaction path including the formation of the
intermediate species. [3]
Energy
Ea (Step 2)
Ea (Step 1)
NO2F +
F + NO2
2NO2 + F2
H = -ve
2NO2F (g)
Progress of reaction
Examiners Comments:
1. Number of elementary steps in the mechanism must match the number of
peaks in the energy profile diagram.
2. The first Ea should be higher to show that the first step is the slow step. Ea is
the difference between the energy of the reactants and transition state or
intermediate and transition state.
trendyline
3. The energygy level of the intermediate is never lower than that of the reactants
or products!

53 trendyline
12
(c) When NO2 and excess F2 were mixed together, [NO2F] varies with time, as shown in
the table below. The initial [NO2] used is 0.400 mol dm3.
t / min [NO2F] / mol dm3 [NO 2F] / mol dm3 min1 [NO2] / mol dm3
t
0.25 0.150 0.60 0.250
0.50 0.245 0.38 0.155
0.75 0.300 0.22 0.100
1.00 0.340 0.16 0.060
1.25 0.360 0.08 0.040
1.50 0.375 0.06 0.025
Examiners comments
1. [NO2] is calculated by Initial [NO2F] Instantaneous [NO2F]. (Refer to mole
ratio of NO2 and NO2F in the overall equation.)
2. [NO 2F] is calculated using ([NO2F]t [NO2F]t-1) (timet timet-1)
t
e.g. At = 0.75 min, [NO 2F] = 0.300 0.245 0.75 0.50 = 0.22
t
(i) Explain why it is necessary to use excess fluorine in this experiment to

confirm the order with respect to nitrogen dioxide. [1]
This is to keep the concentration of fluorine relatively constant during the

experiment so that the rate depends only on the concentration of NO2. /
pseudo first order wrt NO2.
(ii) [NO 2F]

The rate at a particular time can be approximated using rate = t .
Complete the table above by calculating [NO 2F] (to 2 decimal places) and
t
the [NO2] left (to 3 decimal places) at the respective timings. [2]
(iii) Hence, plot a graph of [NO 2F] against [NO2] to confirm and explain that the
t
reaction is first order with respect to NO2. [3]
trendyline
54 trendyline
12
trendyline
55 trendyline
12
[NO 2F] / mol dm-3 min-1
t
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00 [NO2] / mol dm-3

0.000 0.050 0.100 0.150 0.200 0.250 0.300
As a straight line graph passing through the origin is obtained, OR

the rate is directly proportional to the concentration of NO2, hence the
reaction is first order with respect to NO2.
Examiners Comments:
1. The graph of rate of reaction against time MUST pass through the origin. It
indicates that the reaction does not occur when concentration is zero.
2. Rate of reaction and [NO2] have a directly proportional relationship; not
proportional.
3. The relationship of rate and [NO2] must be described as a general trend (i.e.
directly proportional) and should not only be described using the comparison
of two data points.
[Total: 12]
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56 trendyline
2016 ACJC H2 Chem Prelim Paper 3
2
1 Besides reducing carbon dioxide emission, CO2 levels in the atmosphere can be lowered
through a process known as carbon capture and sequestration (CCS). One form of
naturally occurring CCS is the conversion of CO2 into plant biomass during
photosynthesis.
Scientists have also devised chemical methods of CCS. The processes for isolating
carbon dioxide and for storing it has been the focus of some research.
(a) Amine gas treating has been studied as a reaction for the first part of the CCS
process. This method uses aqueous solutions of various alkylamines to capture
carbon dioxide from the waste gases of industrial productions.
(i) Monoethanolamine (MEA) and dimethylethanolamine (DMEA) are two

alkylamines that are commonly used in amine gas treating.
base pKb
HOCH2CH2N(CH3)2 (DMEA) 3.73
HOCH2CH2NH2 (MEA) 4.52
C6H5NH2 9.13
Explain the difference in pKb values in the table. [3]
(ii) The aqueous solution containing 32% MEA by weight can neutralise up to
0.5 mol CO2 per mole of the amine. Assume that density of the solution is
1 kg dm3.
Calculate the pH of 32% MEA solution. [3]

3
(b) (i) Another alkylamine, dimethylpiperazine (DMP), has the molecular formula
C6H14N2.
1 mole of DMP can be formed from 2 moles of N-methyl-2-chloroethylamine

under suitable conditions.
1. State the conditions needed for this reaction.
2. Write the balance equation for the conversion of N-methyl-2-

chloroethylamine into DMP, showing the structural formulae of N-
methyl-2-chloroethylamine and DMP.
[2]
(ii) Under room conditions, N-methyl-2-chloroethylamine reacts with
1. ClCH2CO2H and
2. CH3COCl
Name the type of reaction that occur and suggest the structure of the
compound formed in each reaction.
[3]

4
(c) CO2 that is captured from amine gas treating needs to be sequestered so that it does
not return into the atmosphere.
Carbon sequestration has been attempted using mineral carbonation. In this

method, liquid CO2 is buried under a volcanic rock known as basalt. Over a period of
time, CO2 reacts with metal oxides in the rock to form MgCO3 and CaCO3. This
method allows a large amount of CO2 in the atmosphere to be trapped as solid thus
reducing its effect as a greenhouse gas.
(i) In volcanic areas, underground temperatures rises with increasing depth. Two
types of carbonates found in these areas are rhodochrosite MnCO3 and calcite
CaCO3.
By quoting suitable data from the Data Booklet, explain whether MnCO3 or
CaCO3 decomposes more readily in the presence of geothermal heat. [3]
(ii) Magnesite, MgCO3, forms an equilibrium with CO2 when it is trapped

underground in high temperature.
Reaction 1 MgCO3(s) MgO(s) + CO2(g) Hr = +117 kJ mol1
Suggest how mineral carbonation can be maintained despite high temperature

and justify your answer. [2]
(iii) Fosterite, Mg2SiO4, is a component of basalt that reacts with CO2 in the
following reaction.
Reaction 2 Mg2SiO4(s) + 2CO2(g) 2MgCO3(s) + SiO2(s) Hr < 0

5
enthalpy change of combustion of Mg(s) = 607 kJ mol1

enthalpy change of formation of Mg2SiO4(s) = 59.5 kJ mol1
enthalpy change of formation of SiO2(s) = 911 kJ mol1
Using the information above and relevant data from the Data Booklet, draw an
energy level diagram and hence calculate the enthalpy change of reaction 2.
[4]
[Total: 20]

2 (a) The primary fermentation of grape juice produces wine and carbon dioxide.
Sometimes, a secondary fermentation takes place a few months after the primary
fermentation is finished and the wine has been bottled. This secondary fermentation
converts 2-hydroxybutanedioic acid (malic acid) in the wine into 2-hydroxypropanoic
acid (lactic acid). There are two benefits: the carbon dioxide produced can be used
to make the wine sparkling; the conversion of the malic acid into lactic acid
decreases the acidity of the wine.
HOOCCH2CH(OH)COOH CH3CH(OH)COOH + CO2
A typical concentration of malic acid in wine is 0.05 mol dm3.
(i) Calculate the volume of carbon dioxide produced at room temperature and
pressure conditions when 1.0 dm3 of wine undergoes secondary fermentation.
[1]
(ii) A typical wine bottle has a capacity of 1.5 dm3. Using the ideal gas equation,
calculate the pressure the carbon dioxide produced would exert inside the air
gap of the bottle containing 1.3 dm3 of wine at room temperature.
[1]
(iii) In fact, the pressure inside the bottle is much less under these conditions.
Explain why this differs from the pressure you calculated in (a)(ii).
[1]
ACJC2016 9647/03/Prelim/2016 [Turn over

(b) Another way by which the acidity in wine can be decreased is by acid-catalysed
ester formation:
ethanol + acid ester + water
Wine consists of ethanol and water. A 1.0 dm3 of wine typically contains 10% of
ethanol by mass and a 0.10 mol dm3 concentration organic acid, assuming density
of wine is 1 g cm3.
(i) Calculate the value for the equilibrium constant Kc for the ester formation,
given that 17.4% of acid is converted to ester. [3]
(ii) Maturation is the process where the wine evolves to a state of readiness for
bottling or drinking. Before the wine is ready to be kept in a dark and cool
environment at an ambient temperature below 20 oC in barrels for storage,
they will equilibrate to form ester. Suggest two reasons why wine needs
several months to mature before this reaction takes place significantly.
[2]
(c) Describe a laboratory test to distinguish between 2-hydroxybutanedioic acid (malic

acid) and 2-hydroxypropanoic acid (lactic acid). State the reagents and conditions
you would use and any observations that you would make for each compound. Write
equation for any reaction that occurs.
[3]
[1]

(d) Typically, esters can be hydrolysed in dilute acid or alkali.
The mechanism of both hydrolysis methods are shown as follow:
alkaline hydrolysis
acidic hydrolysis
In alkaline hydrolysis, the hydroxide anion attacks the electron deficient carboxyl
carbon.
In acid hydrolysis, the acid protonates the carboxyl oxygen to render the carboxyl
carbon more electrophilic towards nucleophilic attack by water.
(i) What is the role of
1. OH in step 1 of alkaline hydrolysis

2. H+ in acidic hydrolysis respectively? [2]

(ii) What is the role of water in acid hydrolysis? [1]
(iii) Outline the two advantages of alkaline hydrolysis. [2]
(e) Claisen condensation is a carboncarbon bond forming reaction that can occur
between two esters in the presence of a strong base, resulting in a keto ester. In
the mixture of methyl ethanoate and ethyl methanoate, the following Claisen
condensation products are formed.
and
(Deuterium, 21D, is an isotope of hydrogen.)
Predict the structures of keto esters formed when ethyl ethanoate is mixed with
methyl propanoate under suitable reaction conditions.
ethyl ethanoate methyl propanoate [4]

[Total:20]

3 (a) The characteristic properties of transition metals include coloured ions, complex
formation, variable oxidation states and catalytic activity.
Transition metals are used extensively as heterogeneous catalysts in industrial

processes. An example is the use of iron as a catalyst in the Haber process to
manufacture ammonia.
(i) Explain what is meant by the term heterogeneous? [1]
(ii) State, in the correct order, three essential steps for the mechanism of
heterogeneous catalysis. [2]
(iii) The strength of the adsorption of reactants and products onto the surface of a
transition metal helps to determine its efficiency as a heterogeneous catalyst.
Suggest a reason why transition metals which adsorb weakly are usually not
good heterogeneous catalysts.
[1]
(iv) A catalyst containing molybdenum(VI) was analysed for its molybdenum

content by reducing a sample to the molybdenum(III) state.
When titrated with acidified potassium manganate(VII), the molybdenum(III)

was oxidised back to molybdenum(VI).
A 0.330 g sample of the catalyst, after reduction, required 27.50 cm3 of

0.0200 mol dm3 potassium manganate(VII) to convert the molybdenum(III)
into molybdenum(VI).
Calculate the percentage by mass of molybdenum in the catalyst. [2]

(b) (i) The chemistry of the transition metal, tungsten, has certain similarities to that
of sulfur. Both elements reach their maximum +6 oxidation states when
combined with the electronegative element, oxygen.
Most tungsten occurs naturally in the tungsten anion, WO42-, analogous to the
sulfate ion, SO42-. A common mineral is Scheelite which is calcium tungstate,
CaWO4.
Draw the structure showing the bonding in the WO42 ion and give the OWO
bond angle. [2]
(ii) Tungsten(VI) oxide, WO3, is used in electrochromic windows which change

colour when an electrical voltage is applied.
In electrochromic windows, a voltage is applied between a transparent layer of

tungsten(VI) oxide and a source of ions such as a lithium salt, and the
following reaction takes place during which some of the lithium ions are
incorporated into the structure of the oxide:
WO3 + xLi+ + xe LixWO3
The product, LixWO3, is known as a tungsten bronze and its colour depends on
the value of x. The value of x can vary from 0 to 1; a typical value giving blue-
black colour is when x = 0.3.
Calculate the average oxidation state of the tungsten when x = 0.3. [1]

(iii) A complex of tungsten, W(CO)6, has zero oxidation state for tungsten. It reacts
with CH3Li as shown by the following equation:
CH3Li + W(CO)6 Li[W(CO)5(COCH3)]
The reaction is nucleophilic addition where CH3 is a nucleophile.
Illustrate the shape of [W(CO)5(COCH3)] by drawing the displayed formula of

the anionic complex.
[1]
(c) CoF63 and Co(NH3)63+ are two octahedral complexes which are blue and yellow in
colour respectively.
The colours of the two complexes are different due to different ligands which cause
splitting of the five 3d orbitals by different amount.
The following diagram shows how the five d-orbitals are split in an octahedral
environment.

(i) Draw two diagrams like the one above to show the electronic configurations of
cobalt ions in CoF63 and Co(NH3)63+ respectively. [2]
Examiners comments
Students who got this wrong often miscalculated the number of d electrons.

(ii) Hence, explain which of the two complexes will have a larger energy gap, E.
[1]
(iii) Explain why electrons usually prefer to occupy orbitals singly, rather than in
pairs.
[1]
(d) Salbutamol is an anti-asthma drug which is prepared from aspirin, which in turn is
prepared from salicylic acid.
Salbutamol
The following reaction scheme shows the synthesis of Salbutamol from salicylic acid.

(i) Draw the structures of aspirin, product Z and reagent Y. [3]
(ii) A carbonyl compound with a hydrogen atom on its carbon rapidly equilibrates
with its corresponding enol form as shown.

This rapid inter-conversion between the keto and enol form is a special kind of
isomerism known as tautomerism.
In the presence of strong bases, the hydrogen atom on its carbon is
abstracted to form a resonance-stabilised enolate anion as shown below:
Resonance structures differ only in the position of their electrons.
The mechanism for the reaction from product W to form product X using Br2
and NaOH involves the intermediate, enolate anion. The two steps are:
The first step involves an acid-base reaction between the hydroxide ion
and the methyl group to give the enolate anion.
Using its resonance structure with the C=C bond, the enolate anion
undergoes electrophilic attack by Br2 to give product X.
Based on the information given, describe the mechanism for the reaction to
form product X from product W. In your answer, show any relevant charges,
lone pairs of electrons and arrows to show movement of electrons.
[3]

[Total: 20]

4 This question concerns ascorbic acid (vitamin C, C6H8O6) and its chemistry. The structure
of ascorbic acid is provided below.
ascorbic acid
(a) Ascorbic acid can be used in the synthesis of other compounds, with the use of
Si(CH3)3Cl as a protecting group for the alcohol groups.
(i) In water, Si(CH3)3Cl hydrolyses at a much faster rate than C(CH3)3Cl.
Explain the difference in the ease of hydrolysis. [2]
(ii) State and describe the mechanism for the hydrolysis of C(CH3)3Cl in water.
You should include in your answer:
Dipoles of relevant covalent bonds
Curly arrows
Label for the slow step [3]

(b) Dehydroascorbic acid (DHA), C6H6O6, with its structure shown below, is the oxidised
product of ascorbic acid.
(i) State the oxidation number of:

the carbon labelled C1 in ascorbic acid.
the carbon labelled C2 in DHA. [2]
(ii) Write a balanced half equation, showing their structural formulae, for the
reduction of DHA to ascorbic acid. [1]
(iii) The electrode potential of ascorbic acid at pH 2 is +0.281 V. Explain how the
electrode potential value changes as the pH increases.
[2]
(c) Electrolysis of an aqueous solution of Fe(ascorbate)2 buffered at pH 2 was carried

out, with 22.4 cm3 of hydrogen gas obtained at room temperature and pressure,
Ascorbate is the conjugate base of ascorbic acid.
(i) Using information from the Data Booklet, determine the minimum voltage
required to run this electrolysis. [2]
(ii) Calculate the mass of the product obtained at the anode. [2]
(d) To 50 cm3 of an aqueous solution of ascorbic acid, 200 cm3 of ethanol was added.
Some FeCl3 was dissolved in this solution and the solid, Fe(ascorbate)2X with an
Mr of 422.8, was filtered off. The equation is as follows:
(i) Suggest the role of ethanol in the preparation of the precipitate. [1]

(ii) Determine the identity of the ion [1]
(iii) The formation of Fe(ascorbate)2X from Fe(H2O)63+ involves a ligand

substitution between H2O and the ascorbate ion as shown above.
Explain the sign of the entropy change for the formation of Fe(ascorbate)2X.
Hence given that the formation is exothermic, deduce the sign of the standard
Gibbs free energy change. [4]
[Total: 20]
5 The use of the Data Booklet is relevant to this question.
(a) 2methylbuta1,3diene, also known as isoprene, is produced by many plants and

serves as a building block for monoterpenes when two isoprene units combine without
any rearrangement of the carbon skeleton. Monoterpenes all have molecular formula
of C10H16.
isoprene
Compounds A and B are geometric isomers of a monoterpene commonly used in

perfumes for their sweet herbal scent. Compounds A and B react with cold dilute
alkaline potassium manganate(VII) to produce stereoisomers of C10H22O6.
Compounds A and B react with hot concentrated acidified potassium manganate(VII)

to produce compounds C, C3H4O3, D, C3H4O4, E, C3H6O and a gas F. Both C and E
give a yellow precipitate with aqueous alkaline iodine. A 1.04 g sample of D reacted
with excess sodium metal to produce 240 cm3 of gas.
Use the information to suggest, with explanation, identities of A to F. [9]

(b) Fehlings solution is often used as a distinguishing test in the qualitatively analyses of
organic compounds. It is prepared by mixing two separate solutions, known as
Fehlings A and Fehlings B. Fehlings A is aqueous copper(II) sulfate while Fehlings
B is an aqueous solution of potassium sodium tartrate made in sodium hydroxide.
Tartaric acid, H4T, can exist as a tetraanion, T4, in a strongly alkaline medium. In
Fehlings B, it exists as the H2T2 anion.

The standard electrode potentials, E , of several species are shown in the table
below.

Electrode reaction E /V
1 Cu2O + H2O + 2e 2Cu + 2OH 0.36
2 2Cu2+ + H2O + 2e Cu2O + 2H+ +0.20
3 [Cu(HT)2]4 + 2H2O + 2e Cu + 2H2T2 + 2OH +0.25
4 HCO2H + 2H+ + 2e HCHO + H2O 0.03
5 CO2 + 4H+ + 4e HCHO + H2O 0.07
6 CO2 + 2H+ + 2e HCO2H 0.11
Adding Fehlings solution to methanal causes a reaction to take place.
(i) By selecting appropriate electrode reactions from the Data Booklet or the table
above, construct a balanced equation for this reaction. [1]

(ii) Use your answer in part (i) to calculate the Ecell for this reaction. [1]
(iii) Describe the observations for this reaction. [1]
(c) Electrode potential values are often quoted with reference to the standard hydrogen
electrode (SHE). It is however, seldom used because it is difficult to regulate the
pressure of hydrogen gas at 1 atm.
One of the more commonly used reference electrodes in electrochemistry is the

silver/silver chloride electrode (SSCE). It is made of a silver wire that is coated with a
thin layer of silver(I) chloride, immersed in a potassium chloride solution saturated
with silver(I) chloride.
Ag
AgCl
KCl and
saturated AgCl
ACJC2016 solution
9647/03/Prelim/2016 [Turn over
porous contact
schematic of a silver/silver chloride electrode
One of the advantages of using the SSCE is that it can be directly immersed into the
other half-cell, thereby negating the use of a salt bridge.
(i) Suggest the purpose of having the porous contact. [1]
The solution in the SSCE is colourless in spite of the presence of a dblock element.
(ii) Explain how the colour in transition metal compounds arise. [2]
(iii) Write the full electronic configuration of Ag+ and hence explain why it is not
coloured. [2]

(d) Adding a reagent that selectively brings one of the ions out of a solution as a
precipitate while leaving the other ion in the solution is a technique known as selective
precipitation.
Data about the solubilities in water and solubility products of silver(I) hydroxide and
copper(II) hydroxide at 298 K are given below. Only the numerical values of the
solubility products are given.
hydroxide solubility/mol dm3 solubility product
AgOH 1.23 104 1.52 108
Cu(OH)2 1.77 107 2.20 1020
As a general standard, two ions are selectively separated when a maximum 0.01% of
the precipitated compound still remains as the aqueous ions.
Determine if selective precipitation can be performed on a solution containing

0.200 mol dm3 Ag+ and 0.200 mol dm3 Cu2+ with the addition of solid potassium
hydroxide. [3]

2
1 Besides reducing carbon dioxide emission, CO2 levels in the atmosphere can be lowered
through a process known as carbon capture and sequestration (CCS). One form of
naturally occurring CCS is the conversion of CO2 into plant biomass during
photosynthesis.
Scientists have also devised chemical methods of CCS. The processes for isolating
carbon dioxide and for storing it has been the focus of some research.
(a) Amine gas treating has been studied as a reaction for the first part of the CCS
process. This method uses aqueous solutions of various alkylamines to capture
carbon dioxide from the waste gases of industrial productions.
(i) Monoethanolamine (MEA) and dimethylethanolamine (DMEA) are two

alkylamines that are commonly used in amine gas treating.
base pKb
HOCH2CH2N(CH3)2 (DMEA) 3.73
HOCH2CH2NH2 (MEA) 4.52
C6H5NH2 9.13
Explain the difference in pKb values in the table. [3]
Basic strength:
C6H5NH2 < HOCH2CH2NH2 (MEA) < HOCH2CH2N(CH3)2 (DMEA)
C6H5NH2 is the weakest base as the lone pair of electron on the N atom is
delocalised into the phenyl group. This makes the lone pair less available
to accept H+.
DMEA is a stronger base than MEA because it has two additional electron
donating methyl groups which increases the electron density on the N
atom and improves is ability to accept proton.
Examiners comments
Common wrong usage of term would be that the alkyl electron donating groups
increases the negative charge on N atom, instead of electron density.
(ii) The aqueous solution containing 32% MEA by weight can neutralise up to
0.5 mol CO2 per mole of the amine. Assume that density of the solution is
1 kg dm3.
Calculate the pH of 32% MEA solution. [3]
n(MEA) in 1 dm3 of 32% solution

= 320 [16.0 + 14.0 + 2(12.0) + 7(1.0)]
= 5.246 mol
Concentration MEA solution = 5.246 mol dm-3
trendyline
tren
Kb = 10-4.52 = 3.162 10-5 mol dm-3
ett [OH-] be y mol d

Let dm-33
[ ][[ ]
Kb =
[ ]
3.162 10-55 =
.

57 trendyline
3
y = 0.01288 mol dm-3
pOH = 1.89
pH = 12.1 (correct to 1 d.p.)
Examiners comments
Many students could not interpret what 32% by weight of the solution meant.
(b) (i) Another alkylamine, dimethylpiperazine (DMP), has the molecular formula
C6H14N2.
1 mole of DMP can be formed from 2 moles of N-methyl-2-chloroethylamine

under suitable conditions.
1. State the conditions needed for this reaction.
2. Write the balance equation for the conversion of N-methyl-2-

chloroethylamine into DMP, showing the structural formulae of N-
methyl-2-chloroethylamine and DMP.
[2]
1. Ethanol, heat under pressure / in a sealed tube
2.
(ii) Under room conditions, N-methyl-2-chloroethylamine reacts with
1. ClCH2CO2H and
2. CH3COCl
Name the type of reaction that occur and suggest the structure of the
compound formed in each reaction.
[3]
1. Acid-base reaction
2. Condensation reaction / Nucleophilic substitution
trendyline
yl i
Examiners
xaminers comments
Students are not able to draw correct structure of the nomenclature given.

58 trendyline
4
Many also failed to see that reaction 1 was a simple acid-base reaction and
proceeded to form an amide with the secondary amine and carboxylic acid.
(c) CO2 that is captured from amine gas treating needs to be sequestered so that it does
not return into the atmosphere.
Carbon sequestration has been attempted using mineral carbonation. In this

method, liquid CO2 is buried under a volcanic rock known as basalt. Over a period of
time, CO2 reacts with metal oxides in the rock to form MgCO3 and CaCO3. This
method allows a large amount of CO2 in the atmosphere to be trapped as solid thus
reducing its effect as a greenhouse gas.
(i) In volcanic areas, underground temperatures rises with increasing depth. Two
types of carbonates found in these areas are rhodochrosite MnCO3 and calcite
CaCO3.
By quoting suitable data from the Data Booklet, explain whether MnCO3 or
CaCO3 decomposes more readily in the presence of geothermal heat. [3]
Ion Radii / nm
Ca2+ 0.099
Mn2+ 0.080 (Quote both values with units)
MnCO3 is expected to decompose more readily than CaCO3.
This is because Mn2+ has smaller ionic radius than Ca2+. This causes the
charge density and polarising power of Mn2+ to be greater than that of
Ca2+ thus polarising the C-O bond / distorting the electron cloud in the C
O bond of the anion in MnCO3 to a greater extent.
* Polarising effect is on the covalent bond in the anion; it is not sufficient to

comment on polarising effect on the anion. (Refer to examiners report for
question N2015/III/5cii)
Examiners comments
Some students had mistakenly discussed the question based on Mg2+ instead.
Students who did not include units to the quoted values were not awarded
marks as quantities without units are meaningless.
(ii) Magnesite, MgCO3, forms an equilibrium with CO2 when it is trapped

underground in high temperature.
Reaction 1 MgCO3(s) MgO(s) + CO2(g) Hr = +117 kJ mol1
Suggest how mineral carbonation can be maintained despite high temperature

and justify your answer. [2]
High partial pressure of CO2 must be maintained so that the backward

reaction is favoured to lower the number of moles of gaseous particles.
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Examiners
xaminers
am comments
(iii) Fosterite,
osterite,
sterite, Mg2SiO4, is a component of basalt that reacts w
with CO2 in the
llowing
owing reaction.
following
Reaction 2 Mg2SiO4(s) + 2CO2(g) 2MgCO3(s) + SiO2(s) Hr < 0

59 trendyline
5
enthalpy change of combustion of Mg(s) = 607 kJ mol1

enthalpy change of formation of Mg2SiO4(s) = 59.5 kJ mol1
enthalpy change of formation of SiO2(s) = 911 kJ mol1
Using the information above and relevant data from the Data Booklet, draw an
energy level diagram and hence calculate the enthalpy change of reaction 2.
[4]
Enthalpy / kJ mol1
2Mg(s) + 2O2(g) + Si(s) + 2CO2(g)

0
59.5 Mg2SiO4(s) + 2CO2(g)
2(607)
2MgO(s) + O2(g) + Si(s) + 2CO2(g) Hr
-911
2MgO(s) + SiO2(s) + 2CO2(g)

2(+117) 2MgCO3(s) + SiO2(s)
Hr = 2(117) + 2(607) + 59.5 911

Hr = 2299.5
Hr = 2300 kJ mol-1 (correct to 3 s.f.)
Check that each step has the correct chemical formulae and state
symbols, multiple for the enthalpy values or symbols and direction of
arrows.
Examiners comments
This question was poorly done. Many students were not able to balance the
correct processes required.
[Total: 20]
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60 trendyline
2 (a) The primary fermentation of grape juice produces wine and carbon dioxide.
Sometimes, a secondary fermentation takes place a few months after the primary
fermentation is finished and the wine has been bottled. This secondary fermentation
converts 2-hydroxybutanedioic acid (malic acid) in the wine into 2-hydroxypropanoic
acid (lactic acid). There are two benefits: the carbon dioxide produced can be used
to make the wine sparkling; the conversion of the malic acid into lactic acid
decreases the acidity of the wine.
HOOCCH2CH(OH)COOH CH3CH(OH)COOH + CO2
A typical concentration of malic acid in wine is 0.05 mol dm3.
(i) Calculate the volume of carbon dioxide produced at room temperature and
pressure conditions when 1.0 dm3 of wine undergoes secondary fermentation.
[1]
Amount of CO2 = amount of malic acid = 0.05 x 1.0 = 0.05 mol
Volume of carbon dioxide produced = 0.05 x 24 = 1.20 dm3 (correct to 3

s.f.)
Examiners comments
Simple question which was well answered. Some students had mistakenly
used 22.4 dm3 as the molar volume of a gas at r.t.p. when that is the value at
s.t.p.
(ii) A typical wine bottle has a capacity of 1.5 dm3. Using the ideal gas equation,
calculate the pressure the carbon dioxide produced would exert inside the air
gap of the bottle containing 1.3 dm3 of wine at room temperature.
[1]
PV = nRT
P = (0.065)(8.31)(298)/(0.2x10-3) = 8.05 x 105 Pa (correct to 3 s.f.)
Examiners comments
Most students could not appreciate that the total volume of the bottle (1.5 dm3),
subtracting the volume of the wine (1.3 dm3), would have given a gas volume
of 0.20 dm3.
(iii) In fact, the pressure inside the bottle is much less under these conditions.
Explain why this differs from the pressure you calculated in (a)(ii).
[1]
This is due to the fact that CO2 is not an ideal gas and as such, it will not
obey the ideal gas equation. CO2 is a relatively massive non-polar
molecule, thus its molecular volume is not considered to be negligible as
compared to the total volume of the gas at such a high pressure.
OR
ttrendyline
d li
Intermolecular
termolecular
rmolecular interactions between CO2 molecules
m are n
not negligible at
such
uch a high pressure too. Thus, C
CO2 deviate more from ide
id
ideality.
OR
R
Carbon
arbon dioxide can dissolve in
n aqueous
a solution. Thus less CO2 will
occupy in the empty space.
61 trendyline
Examiners comments
(b) Another way by which the acidity in wine can be decreased is by acid-catalysed
ester formation:
Wine consists of ethanol and water. A 1.0 dm3 of wine typically contains 10% of
ethanol by mass and a 0.10 mol dm3 concentration organic acid, assuming density
of wine is 1 g cm3.
(i) Calculate the value for the equilibrium constant Kc for the ester formation,
given that 17.4% of acid is converted to ester. [3]

I/mol 100/46 0.1 0
C -0.0174 -0.0174 +0.0174
E/mol 2.1565 0.0826 0.0174
Kc = 0.0977
Examiners comments
(ii) Maturation is the process where the wine evolves to a state of readiness for
bottling or drinking. Before the wine is ready to be kept in a dark and cool
environment at an ambient temperature below 20 oC in barrels for storage,
they will equilibrate to form ester. Suggest two reasons why wine needs
several months to mature before this reaction takes place significantly.
[2]
The reaction is slow due to low temperature.
Concentration of acid is low thus leading to slow rate of reaction.
Examiners comments
(c) Describe a laboratory test to distinguish between 2-hydroxybutanedioic acid (malic

acid) and 2-hydroxypropanoic acid (lactic acid). State the reagents and conditions
you would use and any observations that you would make for each compound. Write
equation for any reaction that occurs.
[3]
Reagents & Conditions: aqueous I2, NaOH (aq), warm to 60 oC
Observations: 2-hydroxypropanoic acid will give yellow ppt. while 2-
hydroxybutanedoic acid will not.
Equation:
ttrendyline
r dyy nee [1]

62 trendyline
Examiners comments
Some students had forgotten to remove the proton from the carboxylic acid group by
reacting with an extra mole of OH.
(d) Typically, esters can be hydrolysed in dilute acid or alkali.
The mechanism of both hydrolysis methods are shown as follow:
alkaline hydrolysis
acidic hydrolysis
In alkaline hydrolysis, the hydroxide anion attacks the electron deficient carboxyl
carbon.
In acid hydrolysis, the acid protonates the carboxyl oxygen to render the carboxyl
carbon more electrophilic towards nucleophilic attack by water.
(i) What is the role of
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1
1. OH in step 1 of alkaline
e hydrolysis
+
2. H in acidic hydrolysis respectively? [2]
H- is acting as a nucleophile.
OH
+
H is acting as a catalyst.
catalys
Examiners comments
63 trendyline
(ii) What is the role of water in acid hydrolysis? [1]
Water is acting as a nucleophile.
Examiners comments
(iii) Outline the two advantages of alkaline hydrolysis. [2]
The reaction is irreversible or complete which means that there will be

high yield.
The products are easier to separate as one of the products is ionic

(aqueous layer) and will be found in a different phase from the organic
reactants.
Examiners comments
(e) Claisen condensation is a carboncarbon bond forming reaction that can occur
between two esters in the presence of a strong base, resulting in a keto ester. In
the mixture of methyl ethanoate and ethyl methanoate, the following Claisen
condensation products are formed.
and
(Deuterium, 21D, is an isotope of hydrogen.)
Predict the structures of keto esters formed when ethyl ethanoate is mixed with
methyl propanoate under suitable reaction conditions.
trendyline
y ethyl
hyl ethanoate methyl propanoa
propanoate [4]

64 trendyline
Examiners comments
Many students who attempted this question only gave two out of four possible
structures. They did not realise that one particular ester could also react with
another molecule of the same ester.
[Total:20]
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65 trendyline
3 (a) The characteristic properties of transition metals include coloured ions, complex
formation, variable oxidation states and catalytic activity.
Transition metals are used extensively as heterogeneous catalysts in industrial

processes. An example is the use of iron as a catalyst in the Haber process to
manufacture ammonia.
(i) Explain what is meant by the term heterogeneous? [1]
Reactants and catalyst are in different phase.
Examiners comments
(ii) State, in the correct order, three essential steps for the mechanism of
heterogeneous catalysis. [2]
1) Surface adsorption/adsorption of reactant molecules on surface of

catalyst
2) Reaction between reactant molecules Allow :bonds in reactants
weakened
3) Products desorbed from the surface
Examiners comments
(iii) The strength of the adsorption of reactants and products onto the surface of a
transition metal helps to determine its efficiency as a heterogeneous catalyst.
Suggest a reason why transition metals which adsorb weakly are usually not
good heterogeneous catalysts. [1]
Reactants not brought together or

No increase in reactant concentration on catalyst surface or
Reactants not held long enough for a reaction to occur or
Reactant bonds not weakened
Examiners comments
(iv) A catalyst containing molybdenum(VI) was analysed for its molybdenum

content by reducing a sample to the molybdenum(III) state.
When titrated with acidified potassium manganate(VII), the molybdenum(III)

was oxidised back to molybdenum(VI).
A 0.330 g sample of the catalyst, after reduction, required 27.50 cm3 of

0.0200 mol dm3 potassium manganate(VII) to convert the molybdenum(III)
into molybdenum(VI).
trendyline
y
alculate
lculate the percentage by mass of molybdenum
Calculate molybden in the cataly
catalyst. [2]
1 mole of molybdenum(IIIII) compound

ompound loses 3 moles of ele
electrons on
oxidation
xidation manganate(VII
idation while 1 mole of manganate II) accept 5 moles o
of electrons in
cidic medium (recognise mole ratio)
acidic ratio
Amount of MnO4- in 27.50 cm3 = 27.5 x 103 x 0.02 = 5.50 x 104 mol
66 trendyline
Amount of Mo = 5/3 x 5.50 x 104 = 9.17 x 10-4 mol
Mass of Mo = 95.9 x 9.17 x 104 = 8.80 x 10-2 g
% Mo = (8.80 x 10-2/0.330) x 100 = 26.7 % (correct to 3 s.f.)
Examiners comments
1) Students do not know how to work out the mole ratio between
molybdenum(III) and manganate(VII)
(b) (i) The chemistry of the transition metal, tungsten, has certain similarities to that
of sulfur. Both elements reach their maximum +6 oxidation states when
combined with the electronegative element, oxygen.
Most tungsten occurs naturally in the tungsten anion, WO42-, analogous to the
sulfate ion, SO42-. A common mineral is Scheelite which is calcium tungstate,
CaWO4.
Draw the structure showing the bonding in the WO42 ion and give the OWO
bond angle. [2]
2
O O
W O or W O
O O O O
Bond angle:109.5o
(Do not accept range of values as tungstate is symmetrical.)
Examiners comments
1) Many students gave the dot-cross diagram instead of the structural
formula
2) Charge of ion is not shown.
3) Structural formula requires students to show the bonds between atoms,
hence type of covalent bonds is necessary.
(ii) Tungsten(VI) oxide, WO3, is used in electrochromic windows which change

colour when an electrical voltage is applied.
In electrochromic windows, a voltage is applied between a transparent layer of

tungsten(VI) oxide and a source of ions such as a lithium salt, and the
following reaction takes place during which some of the lithium ions are
incorporated into the structure of the oxide:
WO3 + xLi+ + xe LixWO3
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The
he product, LixWO3, is known as a tungsten bronze and its co
black
ck colour is when x = 0.3.
ack
Calculate
ccolour depends on
e value of x. The value of x can vary from 0 to 1; a typical vvalue giving blue-
the
ate of the tungsten when x = 0.3.

alculate the average oxidation state [1]

67 trendyline
Let oxidation state of the tungsten be m
0.3 + m + (-2)3 = 0
m = +5.7
Examiners comments
1) Students need to show the working as they were told to calculate.
(iii) A complex of tungsten, W(CO)6, has zero oxidation state for tungsten. It reacts
with CH3Li as shown by the following equation:
CH3Li + W(CO)6 Li[W(CO)5(COCH3)]
The reaction is nucleophilic addition where CH3 is a nucleophile.
Illustrate the shape of [W(CO)5(COCH3)] by drawing the displayed formula of

the anionic complex.
[1]
Note: all covalent bonds must be shown as it is a displayed formula.

Octahedral shape illustrated with wedge and dash bonds.
Examiners comments
1) Many students did not know that carbon-oxygen bond is a triple bond
(carbon must form 4 bonds)
2) Students cannot relate what they learn in organic chemistry to this
inorganic complex even though question state that it is nucleophilic
addition.
3) Many students bond CH3 to oxygen instead of a C-C bond.
4) Students did not display all the bonds in structure. Students showed
lack of understanding of the term displayed formula
5) Students should use wedge and dash so as to illustrate shape in 3-
dimension.
(c) CoF63 and Co(NH3)63+ are two octahedral complexes which are blue and yellow in
colour respectively.
The colours of the two complexes are different due to different ligands which cause
splitting of the five 3d orbitals by different amount.
trendyline
lowing
wing diagram shows how the five d
The following orb
orbitals are split in an octahedral
d-orbitals
me
ment.
environment.

68 trendyline
of cobalt ion
mplex
In the high spin state, the electrons occupy all the d-orbitals singly, before starting
to pair up in the lower energy d-orbitals.
In the low spin state, the lower energy d-orbitals are filled first, by pairing up if
necessary before the higher energy d-orbitals are used.
CoF63 is a high spin complex while Co(NH3)63+ is a low spin complex.
(i) Draw two diagrams like the one above to show the electronic configurations of
cobalt ions in CoF63 and Co(NH3)63+ respectively. [2]
trendyline
Examiners
xaminers comments
Students who got this wrong often miscalculated the number of d electrons.

69 trendyline
(ii) Hence, explain which of the two complexes will have a larger energy gap, E.
[1]
Co(NH3)63+ since E is large so pairing of electrons at lower level is

preferred rather than promotion of electrons to a higher level.
Examiners comments
1) Students are expected to use c(i) to answer this question and hence
cannot answer question based on colour.
(iii) Explain why electrons usually prefer to occupy orbitals singly, rather than in
pairs. [1]
There will be electrostatic repulsion between electrons if they are paired

up.
Examiners comments
1) This is very well answered.
(d) Salbutamol is an anti-asthma drug which is prepared from aspirin, which in turn is
prepared from salicylic acid.
Salbutamol
The following reaction scheme shows the synthesis of Salbutamol from salicylic acid.
trendyline
70 trendyline
(i) Draw the structures of aspirin, product Z and reagent Y. [3]
aspirin product Z reagent Y
Examiners comments
1) Many students missed out giving structure of aspirin.
t d li
trendyline
(ii) A carbonyl
arbonyl compound with a hydrogen atom on its carbon rapidly equilibrates
with
th its corresponding enol form as shown.

71 trendyline
This rapid inter-conversion between the keto and enol form is a special kind of
isomerism known as tautomerism.
In the presence of strong bases, the hydrogen atom on its carbon is
abstracted to form a resonance-stabilised enolate anion as shown below:
Resonance structures differ only in the position of their electrons.
The mechanism for the reaction from product W to form product X using Br2
and NaOH involves the intermediate, enolate anion. The two steps are:
The first step involves an acid-base reaction between the hydroxide ion
and the methyl group to give the enolate anion.
Using its resonance structure with the C=C bond, the enolate anion
undergoes electrophilic attack by Br2 to give product X.
Based on the information given, describe the mechanism for the reaction to
form product X from product W. In your answer, show any relevant charges,
lone pairs of electrons and arrows to show movement of electrons.
[3]
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72 trendyline
O O
H H
R C R C + H2O
H OH H
H
O
O
H Br
R C + Br Br R C + Br
H
H
H
Note: Need to show the key to rep R or draw out the structure in full
+ and - on Br2
Examiners comments
1) Students need to understand the use of arrows to show the transfer of
a pair of electrons either from a bond or lone pair to form another bond
pair or lone pair.
2) Many students did not do this question d(ii)
3) Students need to explain any symbol used, for example R.
[Total: 20]

73 trendyline
4 This question concerns ascorbic acid (vitamin C, C6H8O6) and its chemistry. The structure
of ascorbic acid is provided below.
ascorbic acid
(a) Ascorbic acid can be used in the synthesis of other compounds, with the use of
Si(CH3)3Cl as a protecting group for the alcohol groups.
(i) In water, Si(CH3)3Cl hydrolyses at a much faster rate than C(CH3)3Cl.
Explain the difference in the ease of hydrolysis. [2]
Si has empty 3d orbitals that can accept a lone pair of electrons from
water while there are no empty orbitals available to accept lone pair for
C, requiring the formation of a carbocation prior to nucleophilic attack by
water.
Examiners comments
1) Some students failed to realise that compound is covalent in nature and
cannot mention the charge density of Si4+.
2) Many students discussed the difference in the bond strength of SiCl

and CCl but did not appreciate the fact that the mechanism of
hydrolysis was different and therefore the bonds broken in the slow
step would differ. Also, the bond strength of Si Cl is greater than that
of CCl.
(ii) State and describe the mechanism for the hydrolysis of C(CH3)3Cl in water.
You should include in your answer:
Dipoles of relevant covalent bonds
Curly arrows
Label for the slow step [3]
SN1 / unimolecular nucleophilic substitution
+ -
trre
rend
endyliine
ne
74 trendyline
Examiners comments
1) Students failed to read question properly and omitted stating the type of
mechanism.
2)
(b) Dehydroascorbic acid (DHA), C6H6O6, with its structure shown below, is the oxidised
product of ascorbic acid.
(i) State the oxidation number of:

the carbon labelled C1 in ascorbic acid.
the carbon labelled C2 in DHA. [2]
Ascorbic acid: +1
DHA: +2
Examiners comments
(ii) Write a balanced half equation, showing their structural formulae, for the
reduction of DHA to ascorbic acid. [1]
Examiners comments
1) Some students wrote the electrons on the right hand side of the
equation which represents the process of oxidation!
(iii) The electrode potential of ascorbic acid at pH 2 is +0.281 V. Explain how the
electrode potential value changes as the pH increases. [2]
With an increase in pH, there is a decrease in the concentration of H+.

Thus the position of equilibrium for the reaction in (ii) shifts to the left,
favouring the tendency for oxidation of ascorbic acid. Hence the
electrode potential becomes less positive / more negative with a rise in
pH.
(c)
ttrendyline
dyli
Examiners
xaminers comments
1) Many students confused electrode potentials and how h their values
change with changes in equilibrium with the behaviour of ascorbic acid
ns which
under differing pH conditions w co
are two different concepts.
Electrolysis of an aqueous solution of Fe(ascorbate)2 buffered at pH 2 was carried

75 trendyline
out, with 22.4 cm3 of hydrogen gas obtained at room temperature and pressure,
Ascorbate is the conjugate base of ascorbic acid.
(i) Using information from the Data Booklet, determine the minimum voltage
required to run this electrolysis. [2]
Cathode
Fe2+ + 2e Fe 0.44V
2H+ + 2e H2 +0.00V
Anode
DHA + 2H+ + 2e ascorbic acid +0.281V
O2 + 4H+ + 4e 2H2O +1.23V
Ecell = 0.00 (+0.281) = 0.281V
A minimum of 0.281V is required to run the electrolysis.
Examiners comments
1) Many students could not identify the correct electrode potential
occurring at the cathode.
(ii) Calculate the mass of the product obtained at the anode. [2]
The oxidation of ascorbic acid is easier at the anode than water.

Identifies DHA as the product at the anode in words or working
22.4
Amount of H2 = = 9.333 x 104 mol
24000
2e H2
DHA 2e
Mass of DHA = 9.333 x 104 x 174 = 0.162 g (correct to 3 s.f.)
Examiners comments
(d) To 50 cm3 of an aqueous solution of ascorbic acid, 200 cm3 of ethanol was added.
Some FeCl3 was dissolved in this solution and the solid, Fe(ascorbate)2X with an
Mr of 422.8, was filtered off. The equation is as follows:
(i)
trendyline
Suggest
uggest
ggest the role of ethanol in the preparation of the precipitate
It serves to reduce the solubility

encourages precipitation.
ubil
precipitate.
of the compound in solution /

[1]

76 trendyline
Examiners comments
(ii) Determine the identity of the ion X. [1]
422.8 55.8 2(175) = 17
Hydroxide / OH
Examiners comments
1) Some answers mentioned Cl. However, this ion is not shown in the
equation. Students should make use of information provided in the question.
(iii) The formation of Fe(ascorbate)2X from Fe(H2O)63+ involves a ligand
substitution between H2O and the ascorbate ion as shown above.
Explain the sign of the entropy change for the formation of Fe(ascorbate)2X.
Hence given that the formation is exothermic, deduce the sign of the standard
Gibbs free energy change. [4]
Being bidentate, each ascorbate ion replaces 2 water molecules

coordinated to Fe3+ and increases the number of species/particles. There
is an increase in the entropy during the formation of Fe(ascorbate)2X.
Hence S > 0.
As G = H - TS and H < 0,
G will have a negative sign.
Examiners comments
[Total: 20]
(a) 2methylbuta1,3diene, also known as isoprene, is produced by many plants and

serves as a building block for monoterpenes when two isoprene units combine without
any rearrangement of the carbon skeleton. Monoterpenes all have molecular formula
of C10H16.
isoprene
Compounds A and B are geometric isomers of a monoterpene commonly used in

perfumes for their sweet herbal scent. Compounds A and B react with cold dilute
alkaline potassium manganate(VII) to produce stereoisomers of C10H22O6.
trendyline
Compounds
unds A and B react with hot concentrated ac acidified potassium manganate(VII)
uce compound
to produce compounds C, C3H4O3, D D,, C3H4O4, E,
E, C3H6O and a gasga F. Both C and E
give a yellow precipitate with aqueous alkaline iodine. A 1.04 g sasample of D reacted
ess sodium metal to produce 240 cm3 of gas.
cess
with excess gas
Use the information to suggest, with explanation,

lana identities of A to F. [9]

77 trendyline
Statements Explanations/Inferences/Deductions
1. A and B react A and B underwent mild oxidation.
with cold dil.
KMnO4/OH to An increase of 6 OH groups suggests 3 alkenes.
produce C10H22O6.
2. A and B react A and B underwent vigorous oxidation.

with hot conc.
KMnO4/H+ to F is CO2.
produce C, C3H4O3, a terminal alkene is present on A and B.
D, C3H4O4, E, C3H6O
and a gas F.
3a. C and E give C and E contain CH3CO group.

yellow ppt. with (Do not accept CH3CH(OH) since these are products
I2(aq)OH. of vigorous oxidation.)
C is 2oxopropanoic acid.
E is propanone.
3b. 1.04 g of D (D) = 1.04 104 = 0.0100 mol

produces 240 cm3 of Gas is H2, (H2) = 240 24000 = 0.0100 mol
gas with Na.
Since 1 D 1 H2 D has 2 acidic protons.
i.e. 2 carboxylic acid groups.
D is propane1,3dioic acid.
4. Alternative to Since C, D and E are oxidised products of alkene

deducing C, D and cleavage, they either possess ketone and/or
E. carboxylic acid functional groups.
Based on molecular formula of C, the 3 O atoms can

be attributed to (1) 3 ketones OR (2) 1 carboxylic acid
and 1 ketone. Since there are only 3 C atoms, option
(1) is invalid.
C is a ketoacid 2oxopropanoic acid.
Based on molecular formula of D, the 4 O atoms can

be attributed to (1) 2 carboxylic acid groups OR (2) 1
carboxylic acid group and 2 ketones OR (3) 4
ketones. Since there are only 3 C atoms, options (2)
and (3) are invalid.
D has to be a 3 C dicarboxylic acid.

propane1,3dioic acid.
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y
Based on molecular formula
formu of E, the 1 O atom can
only be a ketone functional group.
E is propanone.
C D E

78 trendyline
Deducing A and B
With the structures of C to F, we get the fragments below.
W from C, X from D, Y from E and Z from F.
Fragments Y and Z have to be on the ends of the molecule as they were

cleaved from one end of an alkene. W has two different ends so they have
been labelled W1 and W2 for ease of connection; X is symmetrical so it
doesnt matter which way it connects.
This leaves us with 4 combinations of:

(1) Y W1 W2 X Z (2) Z W1 W2 X Y
(3) Y X W1 W2 Z (4) Z X W1 W2 Y
N.B. that all options can undergo geometric isomerism as well.
However, options (1) and (4) are invalid as they are not made from the
combination of two isoprene units.
Therefore, acceptable structure for A and B would be the cis/trans isomers of

either (2) OR (3).
(2) Z W1 W2 X Y
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79 trendyline
OR
(3) Y X W1 W2 Z
&
Examiners comments
1) Many students wrote the structural formulae of A to F in pencil. They
should take note that only answers in ink will be marked unless it is
graph plotting or the drawing of diagrams.
2) Many students failed to use data given to do simple mole calculations
and hence made the deduction based on mole ratio of reactants.
3) Some students proposed the wrong structures for A and B because they
had forgotten to include the given fact that they were made up of two
isoprene units, without rearrangement to the carbon framework.
(b) Fehlings solution is often used as a distinguishing test in the qualitatively analyses of
organic compounds. It is prepared by mixing two separate solutions, known as
Fehlings A and Fehlings B. Fehlings A is aqueous copper(II) sulfate while Fehlings
B is an aqueous solution of potassium sodium tartrate made in sodium hydroxide.
Tartaric acid, H4T, can exist as a tetraanion, T4, in a strongly alkaline medium. In
Fehlings B, it exists as the H2T2 anion.

The standard electrode potentials, E , of several species are shown in the table
below.

Electrode reaction E /V
1 Cu2O + H2O + 2e 2Cu + 2OH 0.36
2 2Cu2+ + H2O + 2e Cu2O + 2H+ +0.20
3 [Cu(HT)2]4 + 2H2O + 2e Cu + 2H2T2 + 2OH +0.25
4 HCO2H + 2H+ + 2e HCHO + H2O 0.03
5 CO2 + 4H+ + 4e HCHO + H2O 0.07
6 CO2 + 2H+ + 2e HCO2H 0.11
Adding Fehlings solution to methanal causes a reaction to take place.
(i) By selecting appropriate electrode reactions from the Data Booklet or the table
above, construct a balanced equation for this reaction. [1]
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alance equations 3 and 5 in acidic OR alkaline
Balance alkali medium.
[Cu(HT)2] + HCHO + H2O 2Cu + 4H2T2 + CO2
2[Cu(HT) 4

ORR
Cu(H 2]4 + HCHO + 2OH 2Cu
[Cu(HT)
2[Cu(HT) Cu + 4H2T22
+ CO32
Balance equations 3 and 4 in acidic

ic or alkaline medium.
medium
4 2
[Cu(HT)2] + HCHO + H2O Cu + 2H2T + HCO2H
80 trendyline
OR
[Cu(HT)2]4 + HCHO + OH Cu + 2H2T2 + HCO2
Examiners comments
A large number of students had chosen equation 2 as the reduction half
equation. This is not correct because the question had already provided
sufficient evidence for the incorporation of the hydrogen tartrate anion as a
ligand to Cu2+. In addition, it has been covered before that methanal will
produce a different observation for the Fehlings test by producing a copper
mirror instead of the Cu2O precipitate.

(ii) Use your answer in part (i) to calculate the Ecell for this reaction. [1]

Ecell = Ecat Ean
= +0.25 (0.07)
= +0.32 V
OR

Ecell = Ecat Ean
= +0.25 (0.03)
= +0.28 V
Examiners comments

Most students were able to demonstrate their ability to calculate the Ecell for this
reaction.
(iii) Describe the observations for this reaction. [1]
Blue coloured solution decolourised with the formation of a reddishbrown/ pink

coloured mirror/solid/precipitate.
Examiners comments
Many students were able to identify the colour of the precipitate formed but
failed to describe the colour change in the solution.

Effervescence to produce
CO2 was not accepted. Even though the Ecell could be balanced in acidic
medium as the equations were quoted in acidic medium, the experiment was
performed in an alkaline medium during to the pH of Fehlings solution.
(c) Electrode potential values are often quoted with reference to the standard hydrogen
electrode (SHE). It is however, seldom used because it is difficult to regulate the
pressure of hydrogen gas at 1 atm.
One of the more commonly used reference electrodes in electrochemistry is the

silver/silver chloride electrode (SSCE). It is made of a silver wire that is coated with a
thin layer of silver(I) chloride, immersed in a potassium chloride solution saturated
with silver(I) chloride.
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ndy
ndy Ag
Ag
AgCl
KCl and
saturated AgCl
ACJC2016 solution
9647/03/Prelim/2016 [Turn over
81 trendyline
porous contact
schematic of a silver/silver chloride electrode
One of the advantages of using the SSCE is that it can be directly immersed into the
other half-cell, thereby negating the use of a salt bridge.
(i) Suggest the purpose of having the porous contact. [1]
The porous contact allows for the exchange of ions/ close the
circuit/maintain electrical neutrality/acts as salt bridge/maintain osmotic
potential between the two halfcells.
Examiners comments:
Generally well done. Most students were able to show understanding that the
porous contact served as the salt bridge to maintain electrical neutrality in the
absence of an actual salt bridge.
The solution in the SSCE is colourless in spite of the presence of a dblock element.
(ii) Explain how the colour in transition metal compounds arise. [2]
When ligands approach transition metal atom/ion, the degenerate orbitals in

the d-subshell split into two nondegenerate energy levels. When an
electron from the lower energy level absorbs energy from visible/white light
and gets promoted to the higher energy level, colour seen is complementary
to the wavelength of light absorbed.
Examiners comments
Generally well done. Some students did not demonstrate awareness that the
approaching ligands cause the original degenerate d orbitals to split into two
different levels. The most common misconception was the absorbance of
visible light that caused the orbitals to split into two different levels
(iii) Write the full electronic configuration of Ag+ and hence explain why it is not
coloured. [2]
Ag+: 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10
As Ag+ has a full d subshell/lacks vacant d orbitals, an electron is unable to

promote from the lower energy level to the higher energy level OR no energy
corresponding to a wavelength in the visible light spectrum is absorbed and all
are transmitted, making Ag+ colourless.
Examiners comments
The electronic configuration was generally well answered. Some students did
not read the question carefully and used the noble gas configuration of [Kr] to
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runcate
uncate the configuration. These answers were
truncate w accepte as the question
not accepted
ad already specified for the full configuration.
had configuration
ome students described Ag+ as not having a partially filled

Some fille d-subshell. This
an imply that the d-subshell iss either
can e t
totally empty or totally filled. Such
answers did not score the full mark.

82 trendyline
(d) Adding a reagent that selectively brings one of the ions out of a solution as a
precipitate while leaving the other ion in the solution is a technique known as selective
precipitation.
Data about the solubilities in water and solubility products of silver(I) hydroxide and
copper(II) hydroxide at 298 K are given below. Only the numerical values of the
solubility products are given.
hydroxide solubility/mol dm3 solubility product
AgOH 1.23 104 1.52 108
Cu(OH)2 1.77 107 2.20 1020
As a general standard, two ions are selectively separated when a maximum 0.01% of
the precipitated compound still remains as the aqueous ions.
Determine if selective precipitation can be performed on a solution containing

0.200 mol dm3 Ag+ and 0.200 mol dm3 Cu2+ with the addition of solid potassium
hydroxide. [3]
Since solubility of Cu(OH)2 is lower than AgOH, it will be precipitated first.
To maximally precipitate Cu(OH)2, AgOH has to be saturated.
8
1.52 10
[OH] when AgOH is sat. = = 7.60 108 mol dm3
0.200
20
2+ 2.20 10
[Cu ] when AgOH is sat. = 2 = 3.81 106 mol dm3
7.60 10-8
6
2+ 3.81 10
%[Cu ] remaining = 100% = 0.001905% 0.00191% < 0.01%
0.200
Therefore Cu2+ can be selectively precipitated from Ag+.
Examiners comments
The question was poorly attempted. Most candidates scored 1 mark at best for the
calculation of [OH] when [Ag+]=0.200 mol dm3, even though they had not fully
appreciated why that value of [Ag+] was used.
The question had asked for students to "Determine" if selective precipitation can be
performed. Determine often implies that the quantity concerned cannot be measured
directly but is obtained via calculation, substituting measured or known values of other
quantities into a standard formula. As such, students have to utilise the value of 0.01%
to determine the percentage of [Cu2+] remaining, just before AgOH starts precipitate.
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ANDERSON JUNIOR COLLEGE
2016 JC2 PRELIMINARY EXAMINATIONS
CHEMISTRY 9647/01
Higher 2 22 September 2016
Paper 1 Multiple Choice 1 hour

Data Booklet

There are forty questions on this paper. Answer all questions. For each question there are four
possible answers A, B, C and D.
Choose the one you consider correct and record your choice in soft pencil on the Multiple
Choice Answer Sheet.
Multiple Choice Answer Sheet
Write your name, PDG and NRIC / FIN number, including the reference letter.
Shade the NRIC / FIN number.
Exam Title: JC2 Prelim
Exam Details: H2 Chemistry / Paper 1
Date: 22/09/2016
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y This document consists of 18 printed pages.
AJC JC2 Prelim 2016 9647/01/H2 [Turn over

84 trendyline
2
Section A
For each question there are four possible answers, A, B, C and D. Choose the one you consider to
be correct.
1 Antimony (Sb) can be produced in a twostage process from its ore stibnite, Sb 2 S 3 .
The ore is first roasted in oxygen, producing Sb 4 O 6 and SO 2 .
The Sb 4 O 6 is then reduced by carbon, producing Sb and CO 2 .
What volume of CO 2 , measured at room temperature and pressure, is produced from

20 moles of Sb 2 S 3 ?
A 360 dm3 B 670 dm3 C 720 dm3 D 1440 dm3
2 Alpha particles, 4He2+, are commonly emitted by large radioactive nuclei.
The path of a mixture of 16O2+ ions, alpha particles and two unknown ions, F and G, upon
entering an electric field is shown below.
Source
16
alpha F O2+ G
particles
Which of the following represent F and G?
F G
1
A H+ 9
Be2+
27
B 12
C2+ Al3+
9
C Be2+ 14
N3+
12
D C+ 1
H+
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3
3 In a research on the atomic nucleus, scientists have been comparing the stability of isotopes
with the same neutron : proton ratio.
Which isotope has the same neutron : proton ratio as 10B?

32 32 40 40
A P B S C Ar D K
4 Two glass vessels X and Y are connected by a closed valve.
X Y
X contains helium at 20 C at a pressure of 1 x 105 Pa. Y has been evacuated, and has three
times the volume of X. In an experiment, the valve is opened and the temperature of the
whole apparatus is raised to 100 C.
What is the final pressure in the system?
A 3.18 x 104 Pa
B 4.24 x 104 Pa
C 1.25 x 105 Pa
D 5.09 x 105 Pa
5 The interhalogen compound BrF 3 is a volatile liquid which autoionises.
2BrF 3 BrF 2 + + BrF 4
The electrical conductivity of BrF 3 decreases with increasing temperature.
Which statement is correct?
A The autoionisation process is endothermic and the shape of the cation is linear.
B The autoionisation process is endothermic and the shape of the cation is nonlinear.
C The autoionisation process is exothermic and the shape of the cation is linear.
D The autoionisation process is exothermic and the shape of the cation is nonlinear.
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4
6 In an experiment, it was found that complete combustion of 10.0 g of an alcohol, J, raised the
temperature of 100 g of water in a container from 25 oC to 75 oC.
Given that the process is only 65% efficient and the specific heat capacity of water is
4.18 J g1 K1, what is the total heat energy released per gram of J burnt?
A 2.09 kJ g1 B 3.22 kJ g1 C 13.5 kJ g1 D 20.8 kJ g1
7 Limestone is a sedimentary rock largely made up of different crystal forms of calcium

carbonate. At high temperatures, calcium carbonate decomposes to form calcium oxide and
carbon dioxide.
CaCO 3 (s) CaO(s) + CO 2 (g)
What are the correct signs of H and S for this decomposition?
H S
A
B +
C +
D + +
8 The circuit shown in the diagram was set up.
Which electrode reactions will occur on closing the switch?
anode reaction cathode reaction

A neither nickel nor copper is dissolved hydrogen is evolved
B copper is dissolved preferentially copper is deposited
C nickel is dissolved preferentially hydrogen is evolved
D nickel and copper are both dissolved copper is deposited
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5
9 The reaction of hydrogen peroxide with iodide ions in acidic solution can be monitored by an
initial rate method.
H 2 O 2 (aq) + 2H+(aq) + 2I(aq) 2H 2 O(l) + I2 (aq)
The following results were obtained for a series of experiments with different volumes of each
reagent used.
experiment volume of volume of volume of volume of time

number H 2 O 2 (aq) / cm3 H+(aq) / cm3 I(aq) / cm3 water / cm3 taken / s
1 40 40 20 0 33
2 20 40 20 20 66
3 40 20 30 10 22
4 20 40 30 10 44
What could be the mechanism of this reaction?
A H 2 O 2 + H+ H 2 O + OH+ (fast)
OH+ + 2I + H+ H 2 O + I2 (slow)
B H 2 O 2 + I H 2 O + IO (slow)
+
H + IO
HIO (fast)
HIO + H + I+
I2 + H 2 O (fast)
C 2H+ + 2I 2HI (fast)

2HI + H 2 O 2 I 2 + 2H 2 O (slow)
D H 2 O 2 + I + H+ H 2 O + HIO (fast)
HIO + I I 2 + OH (slow)
OH + H+ H2O (fast)
10 The same amount of electricity is passed through two electrolytic cells connected in series for
30 minutes. Cell 1 and Cell 2 contain aqueous solutions of Mn(NO 3 ) 2 and Au(NO 3 ) 3
respectively.
Given that 1.3 g of manganese is deposited on the cathode for Cell 1, what is the current used
for electrolysis and the mass of the gold deposited on the cathode for Cell 2?
current mass of gold

A 1.3 A 3.1 g
B 1.3 A 4.7 g
C 2.5 A 3.1 g
D 2.5 A 4.7 g

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6
11 Cobalt forms many coloured complexes with ligands such as H 2 O and SCN.
A 100 cm3 solution of Co2+(aq) turns from pink to bright blue when 10 cm3 of KSCN(aq) is
added to the solution.
[Co(H 2 O) 6 ]2+(aq) + 4SCN(aq) [Co(SCN) 4 ]2(aq) + 6H 2 O(l)

pale pink bright blue
At equilibrium, [Co(H 2 O) 6 ]2+ and [Co(SCN) 4 ]2 are found to be present in a mole ratio of 1:10.
Given that lg K c for the equilibrium is 3.00, which of the statements is incorrect?
A The units of K c is mol4 dm12.

B At equilibrium, [SCN ] = 3.16 x 101 mol dm3.
C [Co(SCN) 4 ]2 is more stable than [Co(H 2 O) 6 ]2+.
D Dilution of the reaction mixture decreases the proportion of [Co(H 2 O) 6 ]2+ at equilibrium.
12 In which reaction is the underlined substance acting as a base?
A HNO 3 + H 2 SO 4 H 2 NO 3 + + HSO 4
B HSiO 3 + HCN CN + H 2 O + SiO 2
C HNO 2 + HCO 3 H 2 O + CO 2 + NO 2
D C 6 H 5 O + CH 2 ClCO 2 H C 6 H 5 OH + CH 2 ClCO 2
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7
13 The change of colour for an indicator occurs over a limited range of pH that falls between
1.00 of the pK a value of the indicator.
Which is the most suitable indicator that can be used to determine the end point of the
corresponding titration?
alizarin yellow
A
(pK a = 11.0)
bromothymol blue
B
(pK a = 7.1)
methyl yellow
C
(pK a = 3.3)
thymol blue
D
(pK a = 1.6)
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8
14 The bar chart shows the melting points of a series of consecutive elements arranged in order
of increasing atomic number. The elements sodium to chlorine form part of this series.
Which bar represents sodium?
melting C
point / K
atomic number
15 Which oxide does not react with dilute sodium hydroxide to produce a salt?
A Al 2 O 3 B P 4 O 10 C SO 2 D SiO 2
16 The three minerals below are obtained from mines around the world. Each one behaves as a
mixture of two carbonate compounds. They can be used as fire retardants because they
decompose in the heat, producing CO 2 . This gas smothers the fire.
Barytocite BaCa(CO 3 ) 2
Dolomite CaMg(CO 3 ) 2
Huntite Mg 3 Ca(CO 3 ) 4
What is the order of effectiveness as fire retardant, from best to worst?
best worst
A dolomite barytocite huntite
B dolomite huntite barytocite
C huntite barytocite dolomite
D huntite dolomite barytocite
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9
17 Iodine is far less soluble in water than it is in aqueous potassium iodide, where it forms the
complex ion I 3 . For this reason, reactions involving aqueous iodine are often carried out in
potassium iodide solution.
Which equation describes the quantitative determination of iodine in the presence of excess
potassium iodide?
A I 2 + 2SO 4 2 2I + S 2 O 8 2
B 2I + 2S 2 O 3 2 I 2 + S 4 O 6 2
C I 3 + 2SO 4 2 3I + S 2 O 8 2
D I 3 + 2S 2 O 3 2 3I + S 4 O 6 2
18 Astatine, At, is below iodine in Group VII of the Periodic Table.
Which statement is most likely to be correct?
A AgAt(s) reacts with excess dilute aqueous ammonia to form a solution of a soluble
complex.
B At 2 and KCl(aq) react to form KAt(aq) and Cl 2 .
C KAt(aq) and dilute sulfuric acid react to form white fumes of HAt(g).
D NaAt(s) and concentrated sulfuric acid react to form At 2 .
19 In 1869 Ladenburg suggested a structure for benzene, C 6 H 6 , in which one hydrogen atom is
attached to each carbon atom.
Ladenburg structure
A compound C 6 H 4 Cl 2 could be formed with the same carbon skeleton as the Ladenburg
structure.
How many structural isomers would this compound have?
A 3 B 4 C 5 D 6
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10
20 Highenergy irradiation in the stratosphere produces radicals from chlorofluoroalkanes,

commonly known as CFCs.
Which radical could result from this irradiation of CHFClCF 2 Cl?

A CHFClCFCl

B CHClCF 2 Cl

C CHFCF 2 Cl

D CFClCF 2 Cl
21 Compound L has the following structure.
OH OH
What is the total number of geometrical isomers that can be formed from the product of the
reaction of compound L with excess concentrated sulfuric acid at 170 oC?
A 8 B 7 C 4 D 3
22 1,1dichloropropane reacts with excess hot aqueous sodium hydroxide in a series of steps to
give propanal.
NaOH(aq)
CH3CH2CHCl2 CH3CH2CHO
Which term describes the second step of this reaction?
A addition
B elimination
C oxidation
D substitution
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11
23 4chloroaniline is a pale yellow solid which is an important building block used for the
production of pesticides, drugs and dyestuffs.
Cl NH2
4chloroaniline
Which of the following shows a suitable starting compound and sequence of steps to produce
a good yield of 4chloroaniline?
starting compound step 1 step 2
conc. HNO 3 , Sn, conc. HCl

A Cl
conc. H 2 SO 4 followed by NaOH(aq)
B Cl dil. HNO 3 LiAlH 4
Sn, conc. HCl

C NO2 Cl 2 , AlCl 3
followed by NaOH(aq)
D NO2 LiAlH 4 Cl 2 in CCl 4
24 Why does hydrogen cyanide add to propanone but not to propene?
A Propanone is more susceptible to H+ attack than propene.

B Propanone is more susceptible to CN attack than propene.
C The C=C bond in propene is stronger than the C=O bond in propanone.
D The two methyl groups in propanone exert a stronger electron donating effect than the
single methyl group in propene.
25 Equal amounts of compounds P, Q, R and S are separately shaken with 100 cm3 of water.
The pH of each resultant solution is then measured.
CH 3 CH 2 CO 2 H CH 3 CH 2 COCl ClCH 2 CH 2 CO 2 H BrCH 2 CH 2 CO 2 H

P Q R S
Which of the following shows the correct order of decreasing pH of the solutions formed?
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A P, R, S, Q
B P, S, R, Q
C Q, P, S, R
D Q, S, R, P

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12
26 Saccharin is an artificial sweetening agent which can be synthesised from methylbenzene in

the laboratory.
O
CH3 CH3 CH3 CO2H C NH
SO2Cl SO2NH2 SO2NH2 SO2
saccharin
What type of reaction is not shown in this reaction scheme?
A electrophilic substitution
B elimination
C nucleophilic substitution
D oxidation
27 Which pair of organic compounds cannot be distinguished by a chemical test?
O O
C C
A O and NH
B and
CH2OH CH2OH
C
and
HO CO2H HO CO2H
D
and
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13
28 Cortisol is a steroid hormone which is released in response to stress and low blood glucose.
Its structure is shown in the diagram below.
OH
O
HO OH
Cortisol is reduced with hydrogen in the presence of a platinum catalyst, and then oxidised by
heating with acidified KMnO 4 . The product formed is further reacted with excess sodium to
give an organic ion.
What is the charge on the organic ion produced?
A 1 B 2 C 3 D 5
29 Consider the four species below.
I II
NH3 Cl NH3
III IV
CH2NH3 NH2CH3
Which of the following shows the given species arranged in order of decreasing pK a values?
A III, IV, I, II
B III, IV, II, I
C IV, III, I, II
D IV, II, III, I
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14
30 The amino acids glutamine and glutamic acid can react with each other to form amide
linkages.
NH2 O O O
O OH HO OH
NH2 NH2
glutamine glutamic acid
What is the maximum number of different compounds, each containing one amide linkage,
that can be formed from one molecule of glutamine and one molecule of glutamic acid?
A 2
B 3
C 4
D 5
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15
Section B
For each of the questions in this section, one or more of the three numbered statements 1 to 3 may
be correct.
against the statements that you consider to be correct.)
A B C D
1, 2 and 3 1 and 2 2 and 3 1 only
are correct only are correct only are correct is correct
31 Which of the following ions has more electrons than protons and more protons than neutrons?
[ H = 11H ; D = 21H ; C = 126 C ; O = 168 O ]
1 OH
2 HCO 3
3 DCO 3
32 An energy level diagram is shown below for the case of dissolving lithium chloride in water.
Li+(g) + Cl(g)
energy
H1 H2
LiCl(s)
Li+(aq) + Cl(aq)
Which of the following about the enthalpy change of solution of lithium chloride is correct?
1 It is equal to H 1 + H 2 .
2
3
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It implies that dissolving lithium
ected
thium chloride
cted to be less exothermic
It is expected
loride is accompanied by an
a increas
exothermic than that of silver chloride
increase
chloride.
ncrea in temperature.

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16
A B C D
1, 2 and 3 1 and 2 2 and 3 1 only
33 Why does raising the pressure of a fixed mass of gaseous reactants at a constant
temperature cause an increase in the rate of reaction?
1 More collisions occur per second when the pressure is increased.

2 More molecules have energy greater than the activation energy at the higher pressure.
3 Raising the pressure lowers the activation energy.
Which ions contain one or more unpaired electrons?
1 Cu2+
2 Mn3+
3 V3+
35 When a hot glass rod is placed in a gas jar of hydrogen iodide, there is an immediate reaction
as the hydrogen iodide decomposes.
Which statements about this reaction are correct?
1 Brown hydrogen iodide decolourises.

2 The hot rod provides the activation energy.
3 Purple fumes are observed.
36 Which of the following statements are correct about compound M?
z O
H2C C CH C H
y
x
CN
compou M
compound
1 d angles in compound
The bond compou M increase
increa in the order
orde x < y < zz..
2 There is only one sp hybridised carbon atom
om in compound M.
3 Compound M is planar.
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17
37 A reaction pathway diagram is shown.
energy
reaction progress
Which reactions would have this profile?
1 (CH 3 ) 3 CBr + NaOH (CH 3 ) 3 COH + NaBr

2 CH 3 CH 2 Br + NaOH CH 3 CH 2 OH + NaBr
3 (CH 3 ) 3 CCH 2 CH 2 Cl + 2NH 3 (CH 3 ) 3 CCH 2 CH 2 NH 2 + NH 4 Cl
38 Which of the following reactions will produce a racemic mixture?
1 CH 3 CH 2 C(CH 3 ) 2 Cl heated under reflux with aqueous KOH.

2 CH 3 CHO with HCN and a small amount of KOH.
3 CH 3 CH=CHCH 3 with HBr dissolved in CCl 4 .
39 Compound N can react with alkaline aqueous iodine to form a yellow precipitate. When
compound N reacts with hot acidified KMnO 4 , two products are obtained. Both products can
also form a yellow precipitate with alkaline aqueous iodine.
What could be the identity of compound N?
1
OH
O
2
OH O
O
O
3
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O

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18
A B C D
1, 2 and 3 1 and 2 2 and 3 1 only
40 Haemoglobin is a type of protein found in red blood cells. It transports oxygen from the lungs
to body tissues. A haemoglobin molecule is a tetramer made up of four globular protein
subunits. Each subunit is composed of a protein chain tightly associated with a nonprotein
haem group.
The diagram below shows the structure of a haem group.
CH2
CH3
CH2
H3C
N N
II
Fe
N N
H3C CH3
HO OH
OH O
Which of the following is correct about haemoglobin?
1 Haemoglobin has higher affinity for carbon monoxide than oxygen.

2 Each haemoglobin molecule can carry four oxygen molecules.
3 The polypeptide chains in haemoglobin are held together by hydrogen bonding only.
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H2 Chemistry 9647 2016 JC2 Prelim P1 Worked Solutions
1 2Sb 2 S 3 + 9O 2 Sb 4 O 6 + 6SO 2 C
Sb 4 O 6 + 3C 4Sb + 3CO 2
2Sb 2 S 3 3CO 2
20Sb 2 S 3 30CO 2
Volume of CO 2 produced at r.t.p. = 30 x 24 = 720 dm3
2 ionic charge B
Angle of deflection, (i.e. z/m ratio)
mass
Arranging the species in order of decreasing angle of deflection, :
27
species 1
H+ 4
He2+ 9
Be2+ 14
N3+ 12
C2+ 16
O2+ Al3+ C+
12
z/m 1.00 0.500 0.222 0.214 0.167 0.125 0.111 0.0833

identity F F F G G
3 no. of neutrons no. of protons ratio B

10
B 5 5 1:1
32
P 17 15
32
S 16 16 1:1
40
Ar 22 18
4 p1V1 p 2 V2 A
Using
T1 T2
p VT
p2 1 1 2
V2 T1
1 x 10 5 x V1 x 373

(3V1 V1 ) x 293
1 x 10 5 x 1 x 373

4 x 293
3.18 x 10 4 Pa
5 2BrF 3 BrF 2 + + BrF 4 D
Since the electrical conductivity of BrF 3 decreases (i.e. the position of equilibrium shifts
left) when temperature increases, the reverse endothermic process is favoured to
absorb the extra heat. Hence, the forward autoionisation process is exothermic.
F Br F
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Since there are atom, BrF 2 + has a
re 2 bond pairs and 2 lone pairs around the central Br atom
bent (nonlinear)
ear)) shape.
ear
2016AndersonJC/CHEM 1
102 trendyline
6 100 B
Total heat released = ( 100 4.18 50) = 32.2 kJ
65
1
Total heat released per gram = (32.154) = 3.22 kJ g1
10
7 Since n gas = +1 mol; S > 0. D

Since G < 0 only at high temperatures, H > 0.
(Since reaction involves breaking of CO bond during thermal decomposition, H > 0.)
8 At the positive electrode (anode): C
species Eo
Cl 2 /Cl +1.36
Cu2+/Cu +0.34
Ni2+/Ni 0.25
Since Eo(Ni2+/Ni) is the least positive, Ni will be oxidised to Ni2+.
At the negative electrode (cathode):
species Eo
H+/H 2 0.00
H+ will be reduced to H 2 .
9 Comparing expt. 1 and 2, B

When volume of H 2 O 2 is halved, time taken is doubled (i.e. rate is halved).
first order w.r.t. H 2 O 2
Comparing expt. 2 and 4,

When volume of I increased 1.5 times, time taken decreased 1.5 times (i.e. rate
increased 1.5 times).
first order w.r.t. I
Comparing expt. 3 and 4,

When volume of H 2 O 2 is halved and volume of H+ is doubled, time taken is doubled (i.e.
rate is halved).
Since reaction is first order w.r.t. H 2 O 2 , increasing [H+] has no effect on the time taken.
zero order w.r.t. H+
Rate equation: rate = k [H 2 O 2 ] [I]

one molecule of H 2 O 2 and one I ion are involved in the slow step (r.d.s) of the
mechanism
10 Mn2+ + 2e Mn C
n(Mn) = 1.3 / 54.9 = 0.0237 mol

n(e) = 2 x 0.0237 = 0.0474 mol
Using Q = n e F
trendyline
Q = 0.0474 x 96500 = 4574.1
Using Q = It, I = Q/t

I = 4574.1/ (30
4574.1 C
0 x 60) = 2.5
25A
103 trendyline
Au3+ + 3e Au
n(Au) = n(e) / 3 = 0.0474 / 3 = 0.0158 mol

mass of Au = 0.0158 x 197 = 3.1 g
11 [Co(H 2 O) 6 ]2+(aq) + 4SCN(aq) [Co(SCN) 4 ]2 (aq) + 6H 2 O(l) D
KC
[Co(SCN) ] ] 4
2
[Co(H O) ] ][SCN ]
2 6
2 4
mol dm-3
Units of K c
mol dm- 3 (mol dm- 3 )4
Units of K c = mol4 dm12 Hence, statement A is correct.
10
10 3
1 [SCN ] 4
[SCN] = 3.16 x 101 mol dm3 Hence, statement B is correct.
Since K c is more than 1, the position of equilibrium lies to the right. This indicates that
[Co(SCN) 4 ]2 is a more stable complex ion than [Co(H 2 O) 6 ]2+. Hence, statement C is
correct.
Dilution of the reaction mixture decreases the concentration of ions in the solution.
Hence, the position of equilibrium shifts to the left to increase the concentration of
ions. This increases the proportion of [Co(H 2 O) 6 ]2+. Hence, statement D is incorrect.
12 HNO 2 + HCO 3 H 2 O + CO 2 + NO 2 C
HCO 3 acts as a Bronsted base which accepts a proton from HNO 2 , a Bronsted acid.
The H 2 CO 3 formed is unstable and decomposes to H 2 O and CO 2 .
13 The working pH range of an indicator is between pK a 1.00 and pK a + 1.00. B
A suitable indicator will be one where the working pH range of the indicator lies within
the range of rapid pH change at the endpoint of the titration.
Hence, only the indicator in B fulfils the condition.
14 B
Si
Mg
e Na
ne
104 trendyline
15 reacts with D
oxide nature of oxide remarks
dil. NaOH
Al 2 O 3 amphoteric yes
P 4 O 10 acidic yes
SO 2 acidic yes
only reacts with hot and concentrated
SiO 2 acidic no
strong alkalis to form silicates
16 Each mineral behaves as a mixture of two carbonate compounds. D
mineral formula behaves as a mixture of

barytocite BaCa(CO 3 ) 2 1 mol BaCO 3 and 1 mol CaCO 3
dolomite CaMg(CO 3 ) 2 1 mol CaCO 3 and 1 mol MgCO 3
huntite Mg 3 Ca(CO 3 ) 4 3 mol MgCO 3 and 1 mol CaCO 3
The effectiveness of each of the three minerals as fire retardant is dependent on its
ease of thermal decomposition to produce CO 2 , which smothers the fire.
The ease of thermal decomposition of the minerals is dependent on the charge density
and hence the polarising power of the respective Group II metal ions (Ba2+, Ca2+ and
Mg2+).
The order of effectiveness as fire retardant, from best to worst, corresponds to the order
of decreasing polarising power of the Group II metal ions: Mg2+, Ca2+, Ba2+.
Huntite is a more effective fire retardant than dolomite as huntite contains more MgCO 3
and hence it produces more CO 2 upon complete thermal decomposition.
17 I 2 undergoes a redox reaction with S 2 O 3 2, forming I and S 4 O 6 2. (Recall from Group D

VII)
In the presence of excess KI, I 2 forms the complex ion I 3 . Hence, the overall equation
is as shown:
I 3 + 2S 2 O 3 2 3I + S 4 O 6 2
18 Since At is below I in Group VII, D

Similar to AgI, AgAt is likely to be insoluble in excess dilute aqueous NH 3
At 2 is a weaker oxidising agent than Cl 2 and hence, At 2 is unable to oxidise Cl to
form At and Cl 2
KAt and concentrated sulfuric acid react to form At 2 (HAt formed initially is oxidised
by the sulfuric acid)
19 The compound C 6 H 4 Cl 2 has the following three structural isomers: A
CCl CCl
CCl CCl
trendyline
endyy
e
CCl
Cl
ClC
Cl
105 trendyline
20 bond bond energy / kJ mol1 C
CF > 410
CH 410
CCl 340
Irradiation of CHFClCF 2 Cl results in homolytic fission of the weakest CCl bond,

forming the CHFCF 2 Cl radical.
21 OH OH D
excess conc. H2SO4
170 oC
The three geometrical isomers of the product are as follows:
trans trans trans cis cis cis
Note: The following two structures are equivalent.
trans cis cis trans
22 H B
NaOH(aq) - H2O
CH3CH2CHCl2 CH3CH2 C OH CH3CH2 C H
nucleophilic elimination
substitution OH O
23 conc HNO3 A
conc H2SO4
Cl O2N Cl
1. Sn, conc HCl

2. aq NaOH
trendyline
nd
dy
H2N Cl
Note that NO
O 2 is 3directing and NO2 cannot be reduced using
us LiAlH 4 .
106 trendyline
24 The CN nucleophile attacks the electron deficient carbon in propanone in the B
nucleophilic addition mechanism.
25 Q hydrolyses in water to produce a strongly acidic solution of CH 3 CO 2 H and HCl. B

Hence, the resulting solution formed has the lowest pH.
P, R and S are weak acids which ionise partially in water.

The presence of electronegative atoms (Cl and Br) on R and S exerts an electron
withdrawing effect on ClCH 2 CH 2 COO and BrCH 2 CH 2 COO respectively, which
disperses the negative charge and stabilises the anion. Hence, the dissociation of
CH 3 CH 2 COOH to give H+ ions is least favourable. The resulting solution from P has the
highest pH.
Since Cl is more electronegative than Br, it exerts a stronger electronwithdrawing

effect on ClCH 2 CH 2 COO and hence ClCH 2 CH 2 COOH is more acidic than
BrCH 2 CH 2 CO 2 H. Hence, the resulting solution from R has a lower pH than S.
26 CH3 CH3 CH3 CO2H B

SO2Cl SO2NH2 SO2NH2
oxidation
electrophilic
substitution
nucleophilic
substitution /
condensation
O
C NH
SO2
saccharin
27 A: aqueous KMnO 4 , dilute H 2 SO 4 , heat D

For the compound on the left, purple solution decolourises.
(hydrolysis of ester + oxidation of primary alcohol)
For the compound on the right, purple solution remains.
B: aqueous KMnO 4 , dilute H 2 SO 4 , heat
For the compound on the left, purple solution remains.
For the compound on the right, purple solution decolourises.
(sidechain oxidation on benzene ring)
C: aqueous Br 2 / neutral FeCl 3
For the compound on the left, orange solution remains / no violet colouration
observed.
For the compound on the right, orange solution decolourises / violet
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ation
tio observed.
colouration
107 trendyline
28 O B
COO- Na+
O O- Na+
29 The four species given are conjugate acids of their corresponding amines. A
A low pK a value for its conjugate acid will indicate a high pK b value for the amine.
A decreasing pK a value for the conjugate acids of the amines also indicates an
increasing pK b value for the amines.
Hence, the species can be arranged in the order of decreasing basicity of the
corresponding amine.
amine of I amine of II
NH2 Cl NH2
amine of III amine of IV
CH2NH2 NHCH3
Amine of III is the most basic as the electrondonating alkyl group (C 6 H 5 CH 2 )

increases the availability of lone pair on N.
Amines I, II and IV are less basic than that of III since the lone pair on N can be
delocalised into the electron cloud of the benzene ring, decreasing the availability of
the lone pair.
Amine of IV is more basic than that of I and II as it is a secondary amine. The presence
of the electrondonating alkyl group (CH 3 ) increases the availability of the lone pair as
compared to amines of I and II.
Amine of II is less basic than that of I as the presence of electronwithdrawing Cl

decreasing the availability of the lone pair on N to a greater extent.
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108 trendyline
30 Possible combinations: B
Glutamine
NH 2 CO 2 H
Glutamic acid
NH 2 3 different compounds can

be formed
CO 2 H (1)
CO 2 H (2)
31 no. of protons no. of electrons no. of neutrons B

OH 9 10 8
HCO 3 31 32 30
DCO 3 31 32 31
32 Li+(g) + Cl(g) B
energy
H1 H2
LiCl(s) Hsol
Only options 1 and 2 are correct: Li+(aq) + Cl(aq)
1. By Hess law, H sol (LiCl) = H 1 + H 2 .
2. From the energy level diagram, LiCl(s) Li+(aq) + Cl(aq) is an exothermic
process. Hence, the process is accompanied by an increase in temperature.
3. Silver chloride is sparingly soluble while lithium chloride is soluble. Hence,
H sol (LiCl) is expected to be MORE exothermic than H sol (AgCl).
33 1. When pressure is increased, the gaseous reactant particles become closer together. D
Hence, the frequency of effective collisions increases.
2. More molecules have energy greater than the E a at a higher temperature.
3. Raising the pressure has no effect on the E a . The E a is lowered only in the
presence of a catalyst.
34 electronic config. no. of unpaired electrons A

1. Cu2+ [Ar] 3d9 1
2. Mn3+ [Ar] 3d4 4
3. V3+ [Ar] 3d2 2
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35 2HI H 2 + I2 C
1. Gaseous hydrogen iodide appears as a white fumes NOT brown

brow
od
2. The hot rodd provides the activation energy to break the H
HI bond
HI
3. The I 2 formed
med appears as purple fumes (violet
ole black I 2 solids are also observed)
109 trendyline
36 D
37 The reaction pathway diagram illustrates a twostep reaction mechanism. D
1. Tertiary RX undergoes a twostep S N 1 mechanism

2. Primary RX undergoes a single step S N 2 mechanism
3. Same as option 2
38 The nucleophile (OH, CN, Br) can attack the carbocation / planar molecule from C
either side with equal probability in the S N 1 / nucleophilic addition / electrophilic addition
mechanism.
A racemic mixture will not be formed in (1) since the product is not even chiral.
39 Compound 1 will undergo oxidative cleavage and compound 2 will undergo hydrolysis B
when reacted with hot acidified KMnO 4 .
H O
will form a yellow ppt with
Compounds with the structure CH3 C or CH3 C
alkaline aqueous iodine.
OH
40 Option 1: Fe2+ in haemoglobin forms a stronger dative covalent bond with carbon B
monoxide than oxygen.
Option 2: Each haemoglobin molecule contains 4 haem groups. One molecule of
oxygen binds to the Fe2+ on each haem group.
Option 3: The polypeptide chains in haemoglobin are held together by R group
interactions.
trendyline
110 trendyline
NAME:______________________________ PDG:_____ /15 Register No: _____
CHEMISTRY 9647/02
Paper 2 Structured Questions 2 hours
Candidates answer on the Question Paper.

Write your name, PDG and register number on all the work you hand in.
You may use a pencil for any diagrams or graphs.

For Examiners Use
3
Paper 2
4
Total / 72
5
tren
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tr ndyline
dyline 6
This document consists of 20 printed pages.

111 trendyline
2
1 Planning (P)
Group II nitrates decompose on heating to form metal oxide, nitrogen(IV) oxide and oxygen.
Group II nitrates and their oxides are solids that can be easily weighed to determine the amount
present. Nitrogen(IV) oxide is an acidic gas and can be absorbed by a known amount of excess
strong alkali such as sodium hydroxide.
2NaOH + 2NO 2 NaNO 2 + NaNO 3 + H 2 O
The amount of strong alkali remaining can then be determined by titrating against a standard
solution of strong acid.
The oxygen produced from the decomposition can be trapped by a simple gas collection setup to
measure the volume collected.
You are to plan an experiment to confirm that the molar quantities of magnesium oxide,
nitrogen(IV) oxide and oxygen produced agree with the equation for the thermal decomposition of
magnesium nitrate.
(a) Write an equation for the thermal decomposition of magnesium nitrate. You should include
state symbols in your equation.
.. [1]
(b) Suggest the capacity of the apparatus to be used to collect the oxygen gas.
Hence calculate the mass of magnesium nitrate to be heated to produce a stated volume of
oxygen gas appropriate for the apparatus.
You should assume that one mole of any gas occupies 24.0 dm3 under room conditions.
capacity of apparatus:
mass of magnesium nitrate to be heated: . [2]
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112 trendyline
3
(c) Use your answer to (b) to calculate the minimum volume of 1.00 mol dm3 aqueous sodium
hydroxide needed to absorb the nitrogen(IV) oxide produced from the thermal decomposition
of magnesium nitrate.
volume of sodium hydroxide needed: ........ [1]
(d) You may assume that you are provided with:
solid magnesium nitrate

1.00 mol dm3 sodium hydroxide
0.20 mol dm3 hydrochloric acid
the apparatus and chemicals normally found in a school or college laboratory
Your plan should include:
a diagram of the assembled apparatus capable of absorbing the nitrogen(IV) oxide

and collecting the oxygen separately and in sequence;
an outline of how the results would be obtained, including the essential details of the
titration procedure;
measures to ensure reliability of results;
brief, but specific, details of how the results will be used to
determine the amounts in moles of reactant and all products at the end of
complete thermal decomposition
confirm that the decomposition had occurred according to the molar ratios in the
equation.
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4
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.............
.............

.............

.............
.............
.............
114 trendyline
5
.............
.............
.............
.............
.............
.............
.............
.............
.............
.............
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.............
.............
.............
.............
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.............
.............
.............
.............
.............
.............
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.............

.. [8]
[Total: 12]

115 trendyline
6
2 (a) Ethoxyethane, CH 3 CH 2 OCH 2 CH 3 , may be regarded as a water molecule in which each of the
hydrogen atoms has been replaced by an ethyl group.
At room temperature, boron trifluoride is a gas and ethoxyethane is a liquid. When boron
trifluoride is mixed in a 1 : 1 molar ratio with ethoxyethane, a liquid with a boiling point of 127 oC
is formed.
(i) Suggest what type of bond is formed between boron trifluoride and ethoxyethane,
explaining your answer.
...
...
[2]
(ii) Draw a diagram to illustrate the shape of and bonding in the product.
(You may represent the CH 2 CH 3 group with R)
[1]
Often in the preparation of an organic compound the product is obtained as an aqueous solution.
The chemist needs to separate the organic compound from water by using solvent extraction
method. Organic compounds are more soluble in organic solvents than in water.
Ethoxyethane is a good solvent for many organic compounds. It is immiscible with water and has a
low boiling point (35 oC). When an aqueous solution containing an organic compound is shaken with
ethoxyethane in a separating funnel, the compound distributes itself between the two layers, in
accordance with its partition coefficient between ethoxyethane and water, until equilibrium is
reached.
The partition coefficient, K partition , of an organic compound, J, between ethoxyethane and water is
given by the following expression.
trendyline
d li
concentration of J in
i ethoxyetha
ethane
n (organic layer
layer)
K partition
p
concentrat
oncentration of J in water (aqueous
aqueous layer)
ration of J can be expressed in g cm3

where the concentration
tration
.
The partition coefficient

i i t iis a constant
t t att a constant
t t temperature.
t t

116 trendyline
7
(b) When 20 cm3 of ethoxyethane were shaken with 75 cm3 of an aqueous solution containing
5.00 g of J, it was found that 2.14 g of J were extracted into the ethoxyethane.
(i) Calculate the partition coefficient, K partition , of J between ethoxyethane and water.
[1]
(ii) In another experiment
10 cm3 of ethoxyethane were shaken with 75 cm3 of an aqueous solution containing

5.00 g of J and the layers were separated.
The aqueous layer was shaken with a second 10 cm3 portion of ethoxyethane and the
layers were separated.
The two organic layers were combined.
Use the value of K partition you calculated in (b)(i) to calculate the total mass of J extracted
by this procedure.
[2]
(iii) Hence comment whether it is more efficient to use one 20 cm3 portion of ethoxyethane or
two successive portions of 10 cm3 ethoxyethane for extraction.
..... [1]
trendyline
(c) alcium
lcium chloride was then added to the combin
Anhydrous calcium laye obtained in (b)(ii).
combined organic layers
eason for the addition of anhydrous calcium chloride

Suggest the reason chloride.
.........................
......
........................................................... [1]
[Total: 8]

117 trendyline
8
3 Nitrogen and phosphorus are both Group V elements. Nitrogen exists in its elemental form as
simple molecules, N 2 , while phosphorus occurs in one of the many forms, including white
phosphorus and red phosphorus. Some data about these two forms of phosphorus are shown in
Table 1.1.
Table 1.1
white phosphorus red phosphorus

appearance at room
creamy white solid red solid
temperature
melting point / oC 44 590
solubility in methylbenzene soluble insoluble
(a) Suggest the type of structure and bonding in red phosphorus. Explain your reasoning.
............
............
............
[2]
(b) The 2s and 2p orbitals of nitrogen atoms can hybridise in the same way as the 2s and 2p
orbitals of carbon atoms.
Suggest the type of hybridisation in N 2 and draw the arrangement of the hybrid orbital(s)
around each nitrogen atom.
type of hybridisation
[2]
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118 trendyline
9
(c) The corresponding form of phosphorus, P 2 , is not stable under standard conditions. Instead,
white phosphorus consists of molecules with a tetrahedral structure as shown.
P P
P
white phosphorus
(i) Unlike N 2 , P 2 is not stable under standard conditions. Suggest a reason for this.
...
.. [1]
(ii) Using the data in Table 1.2, construct an appropriate energy cycle and use it to
determine the enthalpy change for the conversion of white phosphorus to the gaseous
diatomic molecule, P 2 .
P 4 (s) 2P 2 (g)
Table 1.2
PP bond energy 200 kJ mol1
PP bond energy 485 kJ mol1
enthalpy change of vaporisation of P 4 (s) +12 kJ mol1
trendyline [3]

119 trendyline
10
(iii) The formation of P 2 (g) from white phosphorus is not spontaneous under standard
conditions.
Suggest how the conditions would need to be changed to make it spontaneous. Explain
your reasoning.
...
...
...
.. [2]
(d) Although nitrogen gas makes up about 79% of the atmosphere, it does not easily form
compounds.
(i) Explain why the conditions in a car engine lead to the production of oxides of nitrogen.
...
.. [1]
(ii) Give an equation for a reaction involved in the removal of nitrogen monoxide, NO, from
a cars exhaust gases, in the catalytic converter.
.. [1]
[Total: 12]
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120 trendyline
11
4 (a) (i) What is meant by the term ligand in the context of transition element chemistry?
...
.... [1]
(ii) Although the five dorbitals are at the same energy in an isolated atom, when a
transition element ion is in an octahedral complex the orbitals are split into two groups,
as shown in the following diagram.
energy gap E
dorbitals of an isolated dorbitals of the transition element

transition element ion ion in an octahedral complex
Use this diagram as an aid in explaining the following.
Transition element complexes are often coloured.
...
...
...
...
...
...
The colour of a complex of a given transition element often changes when the
ligands around it are changed.
...
...
. [5]
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121 trendyline
12
(b) Heating a solution containing potassium ethanedioate, iron(II) ethanedioate and hydrogen
peroxide produces the light green complex K 3 Fe(C 2 O 4 ) 3 , which contains the ion
[Fe(C 2 O 4 ) 3 ]3.
The structure of the ethanedioate ion is as follows.
-
O O-
C C
O O
(i) Determine the oxidation number of carbon in this ion.
.... [1]
(ii) Determine the oxidation number of iron in [Fe(C 2 O 4 ) 3 ]3.
.... [1]
(iii) The iron atom in the [Fe(C 2 O 4 ) 3 ]3 ion is surrounded octahedrally by six oxygen atoms.
Draw a threedimensional diagram to show the shape of this ion.
[2]
(c) Kidney stones are usually made up of an inorganic salt of calcium with ethanedioate. Thus,
people who are prone to kidney stones have to limit or avoid eating foods with high
ethanedioate content such as spinach, peanuts and sweet potatoes.
(i) Write the expression for the solubility product of calcium ethanedioate.
.... [1]
(ii) The value of K sp for calcium ethanedioate is 2.3 x 109. Calculate [C 2 O 4 2] in a

saturated solution of calcium ethanedioate.
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122 trendyline
13
[1]
(iii) A solution W is saturated with both calcium ethanedioate and calcium chloride.
The concentration of ethanedioate ions in solution W is less than that calculated in

(c)(ii). Explain why this is so.
..........
........ [1]
(d) By quoting relevant data from the Data Booklet, explain the following observations:
compound pH of a 1.0 mol dm3 solution in water

NaCl 7.0
MgCl 2 6.5
AlCl 3 3.0
.. [2]
[Total: 15]
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123 trendyline
14
5 (a) Kekul proposed the following structure for benzene.
The enthalpy change of hydrogenation of cyclohexene, as shown, is 121 kJ mol1.
+ H2
Based on this value for cyclohexene it is possible to calculate the enthalpy change of
hydrogenation of benzene, based on Kekuls structure, to be 363 kJ mol1.
Explain the difference between this calculated value and the actual value for the enthalpy
change of hydrogenation of benzene of 209 kJ mol1.
.....
........ [1]
(b) Benzene undergoes electrophilic substitution reactions.
Nitrobenzene, C 6 H 5 NO 2 , can be formed from benzene. Give the reagents and conditions
necessary for this process and identify the electrophile.
reagents ..
conditions ..............
electrophile ... [2]
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124 trendyline
15
(c) Fig. 5.1 shows a reaction scheme starting from nitrobenzene.
1. Sn / conc. HCl 1. limited CH3CH2Br

C6H5NO2 C6H5NH2 X
2. excess NaOH 2. CH3COCl
Br2, FeBr3 Br2, CCl4

strong heat room temperature
BrC 6H4NO2 BrC 6H4NH2
Fig. 5.1
(i) Explain why the bromination of phenylamine, C 6 H 5 NH 2 , is possible with the milder
conditions shown in Fig. 5.1.
...
...
...
...... [2]
(ii) Write an equation for the reaction between nitrobenzene and the reducing mixture,
Sn / conc. HCl. Use [H] to represent the formula of the reducing agent in your equation.
[1]
(iii) Draw the structural formula of X.
[1]
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125 trendyline
16
(d) When heated with chlorine, the hydrocarbon 2,2dimethylbutane produces compounds L, M
and N.
CH3 CH3 CH3 CH3

CH3CH2 C CH3 CH2CH2 C CH3 + CH3CH C CH3 + CH3CH2 C CH2
CH3 Cl CH3 Cl CH3 CH3 Cl
2,2-dimethylbutane L M N
It is observed that the rate of substitution of a hydrogen atom in 2,2dimethylbutane by a

chlorine atom is dependent on the type of hydrogen substituted primary, secondary or
tertiary.
The table below shows the relative rate of substitution by chlorine.
Reaction Type of hydrogen substituted Relative rate

RCH 3 RCH 2 Cl primary 1
R 2 CH 2 R 2 CHCl secondary 7
R 3 CH R 3 CCl tertiary 21
Using the information from the table and by considering the number of hydrogen atoms of
each type (primary, secondary or tertiary) within 2,2dimethylbutane, predict the ratio of the
three products L, M and N.
Explain how you arrived at your answer.
ratio of L to M to N: ..
explanation:
...........
.. [2]
[Total: 9]
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17
6 (a) The interhalogen compound ICl reacts with alkenes in an addition reaction. ICl reacts faster
with alkenes than the pure halogens.
(i) Describe the mechanism of the reaction between ICl and propene.
[3]
(ii) Suggest why ICl reacts with alkenes faster than the pure halogens, Cl 2 , Br 2 and I 2 .
.....
... [1]
Cyclohexa1,4diene behaves as a typical alkene.
cyclohexa1,4diene
(b) State the total numbers of bonds and bonds in a molecule of cyclohexa1,4diene.
number of bonds
number of bonds [1]
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127 trendyline
18
(c) Cyclohexa1,4diene can be made by heating buta1,3diene with ethyne in the DielsAlder
reaction. The diagram below shows the movement of electron pairs, represented by curly
arrows, needed to generate the cyclohexa1,4diene in a single step.
heat
buta1,3diene ethyne cyclohexa1,4diene
(i) In a similar type of reaction, cyclohexene can be formed from buta1,3diene and
another alkene, Y.
+ Y
heat
buta1,3diene cyclohexene
Suggest the name of the alkene, Y, that would react with buta1,3diene to form
cyclohexene in this type of reaction.
... [1]
(ii) In another similar reaction, penta1,3diene reacts with propene to form two products
that are structural isomers.
Deduce the structures of these two isomers.
[2]
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128 trendyline
19
(d) Chlorogenic acid occurs naturally in coffee and an edible species of bamboo.
OH
O O OH
OH
HO2C
OH
OH
chlorogenic acid
(i) Draw the structural formula of the compound formed when chlorogenic acid is treated
with an excess of sodium metal.
[1]
On heating with dilute acid, chlorogenic acid produces two compounds, B and C.
OH
O OH
dil. H+ (aq)
chlorogenic acid + C
heat
HO OH
OH
Br2(aq)
B in excess
conc. H2SO4
heat
E
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d D

129 trendyline
20
(ii) State the type of reaction undergone by chlorogenic acid when B and C are formed.
Draw the displayed formula of compound C.
type of reaction
compound C
[2]
When compound B is heated with concentrated H 2 SO 4 , compound D, C 7 H 6 O 3 , is formed.
CO 2 is evolved when compound D is treated with Na 2 CO 3 (aq). Compound D decolourises

Br 2 (aq) giving a white precipitate, but does not react with cold, alkaline KMnO 4 .
When compound C is treated with an excess of Br 2 (aq), compound E is produced.
(iii) Identify the functional group that would have been shown to be present in D if the test
with cold, alkaline KMnO 4 had been positive.
. [1]
(iv) Name the functional groups in compound D that react with the following.
Na 2 CO 3 (aq) .. Br 2 (aq) .. [2]
(v) Suggest structures for compounds D and E.
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trendy
yline
D E
[2]
[Total: 16]

130 trendyline
H2 Chemistry 9647 2016 JC2 Prelim P2 Suggested Solutions
1 (a) 2Mg(NO 3 ) 2 (s) 2MgO(s) + 4NO 2 (g) + O 2 (g) [1]
OR
Mg(NO 3 ) 2 (s) MgO(s) + 2NO 2 (g) + O 2 (g)
(b) Correctly stated volume, with units, of apparatus to be used for gas collection.
E.g. 100 ml or 100 cm3 gas syringe [1]
AND
Correctly calculated mass of magnesium nitrate to produce a stated volume of O 2 gas

that would be appropriate for the stated volume of apparatus.
E.g. for 60 cm3 of O 2 ,

n(O 2 ) = 60/24000 = 2.50 x 103 mol
n[Mg(NO 3 ) 2 ] = 2 x n(O 2 ) = 5.00 x 103 mol
mass of Mg(NO 3 ) 2 = 5.00 x 103 x [24.3 + 2(14.0) + 6(16.0)] = 0.742 g [1]
(c) 2Mg(NO 3 ) 2 (s) 2MgO(s) + 4NO 2 (g) + O 2 (g)

2NaOH + 2NO 2 NaNO 2 + NaNO 3 + H 2 O
n(NO 2 ) = 2 x n[Mg(NO 3 ) 2 ] = 2 x 5.00 x 103 = 0.0100 mol

n(NaOH) = n(NO 2 ) = 0.0100 mol
min. volume of 1.00 mol dm3 NaOH needed = 0.0100 / 1.00 x 1000 = 10.00 cm3 [1]
(d) A diagram of the assembled apparatus capable of absorbing the nitrogen(IV) oxide and [2]
collecting the oxygen separately and in sequence
Directly heated vessel (boiling tube) labelled magnesium nitrate with tube at exit
Gas stream led into a liquid labelled (1.00 mol dm3) NaOH which will absorb the
nitrogen(IV) oxide / NO 2
Collects a gas in a syringe or over a liquid, provided it is properly connected
All parts of the apparatus are connected and airtight AND nitrogen(IV) oxide
absorption precedes oxygen collection
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An outline of how the results would be obtained and measures to ensure reliability of
results
[4]
1. Record the mass of the empty boiling tube.
2. Weigh accurately about 0.75 g of magnesium nitrate into a boiling tube.
3. Using a burette, add 20.00 cm3 of 1.00 mol dm3 sodium hydroxide into the
chamber collecting nitrogen(IV) oxide / NO 2 .
4. Set up the apparatus according to the diagram above.
5. After ensuring that all the connections are properly sealed, start heating the
magnesium nitrate in the boiling tube. Heat strongly for about 5 minutes, moving
the boiling tube to ensure even heating of the solid. Continue heating until no
further bubbling is seen in the sodium hydroxide solution and the syringe shows no
further change in volume of oxygen gas collected.
6. Remove the delivery tube from the alkali before taking the boiling tube off the
flame. (To prevent back flow of liquid into the boiling tube due to cooling of air)
7. Allow all the apparatus and chemicals to cool to room temperature before taking
measurements.
8. Weigh the boiling tube and residue. Subtract the mass of the empty boiling tube to
determine the mass of magnesium oxide produced.
9. Transfer all the sodium hydroxide solution into a 100 cm3 volumetric flask. Top up
to the mark with distilled water. Stopper the flask and shake well to obtain a
homogeneous solution.
10. Pipette 25.0 cm3 of the solution into a 250 cm3 conical flask for titration.
11. Add a few drops of methyl orange indicator. Titrate with the 0.20 mol dm3
hydrochloric acid from the 50.00 cm3 burette until the solution turns from yellow to
orange.
12. Repeat the titration until consistent results within 0.10 cm3 are obtained.
13. Record the volume of oxygen gas collected in the syringe.
Brief, but specific, details of how results will be used to determine the amounts in moles
of reactant and all products at the end of complete thermal decomposition AND confirm
that the decomposition had occurred according to the molar ratios in the equation
n(MgO) = mass of MgO / M r of MgO = x mol
n(NO 2 ) = n(NaOH that reacted with NO 2 )

= (20/1000 x 1) [(vol. of HCl/1000 x 0.20) x 100/25.0] = y mol [1]
n(O 2 ) = volume of O 2 /24000 = z mol
Compare each of the values x, y and z with n[Mg(NO 3 ) 2 ] XVHG 5.00 x 103 mol) to
check if the decomposition has occurred according to the molar ratios in the equation. [1]
[Total: 12]
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2 (a) (i) B atom in BF 3 molecule is electrondeficient as it has only 6 electrons around it. [2]
Hence, the B atom can accept another 2 electrons from the lone pair of O atom in
ethoxyethane molecule. By forming a dative bond with the O atom of
CH 3 CH 2 OCH 2 CH 3 , the B atom achieves the octet configuration.
(ii) O [1]
F CH2CH3
B
CH2CH3
F
F
(b) (i) concentration of J in ethoxyethane (organic layer)

K partition
concentration of J in water (aqueous layer)
2.14 / 20
2.81 [1]
(5 2.14) / 75
(ii) 1st extraction [2]
2.81 = (x / 10) / [(5 x) / 75]

2.81 (5 x) = 7.5 x
x = 1.36 g
2nd extraction
Mass of J remaining in aqueous layer after 1st extraction = 5.00 1.36 = 3.64 g
2.81 = (y / 10) / [(3.64 y) / 75]

2.81 (3.64 y) = 7.5 y
y = 0.992 g
total mass of J extracted = 1.36 + 0.992 = 2.35 g
(iii) It is more efficient to use two successive portions of 10 cm3 ethoxyethane than [1]
one 20 cm3 portion of ethoxyethane since total mass of J extracted is greater
using two successive portions.
(c) Anhydrous calcium chloride (drying agent) was added to remove water present in the [1]
organic layer.
[Total: 8]
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3 (a) Giant covalent structure with strong covalent bonds between P atoms. [1]
Relatively high melting point OR insolubility in organic solvent (methylbenzene) [1]

suggests strong bonding throughout the structure.
(b) type of hybridisation: sp [1]
[1]
(c) (i) Phosphorusphosphorus triple bonds are much weaker than nitrogennitrogen [1]
triple bonds as phosphorus atoms are too big to come close enough together to
form strong bonds.
OR
Orbitals of P are larger and more diffused hence overlap of orbitals is less
effective.
(ii) H [2]
P 4 (s) 2P 2 (g)
+12 2(485)
P 4 (g) 4P(g)
6(+200)
H = +12 + 6(+200) + 2(485)

= +242 kJ mol1 [1]
(iii) Increase temperature [1]
G = H TS
Since H > 0, S > 0 (as there is an increase in no. of moles of gas),
for G to be negative (i.e. spontaneous), magnitude of TS must be greater than
that of H. Hence, T must be large. [1]
(d) (i) High temperature (needed for reaction between N 2 and O 2 ) [1]
(ii) 2NO + 2CO N 2 + 2CO 2 [1]

OR 2NO + C N 2 + CO 2
[Total: 12]
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4 (a) (i) A ligand is a neutral molecule or an anion which possesses at least one lone pair [1]
of electrons which can be used to form dative bonds with the central atom or ion.
(ii) Transition element complexes are often coloured:
In the presence of ligands, the d orbitals of transition metal ion are split into two
levels.
The energy gap E between the nondegenerate orbitals is small and corresponds [1]
to that in the visible light region.
Energy is absorbed from the visible region when an electron is promoted from [1]
a lower level d orbital to a vacant higher level d orbital (dd transition).
The colour of the transition metal complex is the complement of the colour [1]
absorbed.
The colour of a complex of a given transition element often changes when the
ligands around it are changed:
The size / magnitude of the energy gap E depends on the ligand. [1]
(Since E = hc / ),
When the ligand changes, E changes, (absorbed) also changes (hence colour of [1]
the complex changes).
(b) (i) Let O.N. of C in C 2 O 4 2 be x
2(x) + 4(2) = 2
x = +3 [1]
(ii) Let O.N. of Fe in [Fe(C 2 O 4 ) 3 ]3 be y
y + 3(2) = 3
y = +3 [1]
(iii) 3- [2]
O
O
O
O O O
Fe III
O
O O
O
O
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dy
O
(c) (i) K sp = [Ca ][ 2 O 4 22]

Ca2++][C [1]
(ii) [C 2 O 4 2] = (2.3 x 109)1/2 = 4.80 x 105 mol dm3 [1]
135 trendyline
(iii) CaC 2 O 4 (s) Ca2+(aq) + C 2 O 4 2(aq)
Increase in [Ca2+] due to the presence of the common ion Ca2+ (from CaCl 2 ) in
solution W shifts the position of the above equilibrium to the left. Hence, [C 2 O 4 2] [1]
in solution W is less than that calculated in (c)(i).
(d) cation ionic radius / nm

Na+ 0.095
Mg2+ 0.065
Al3+ 0.050 [1]
The charge density of the cation increases from Na+ to Mg2+ to Al3+. Thus, the polarising
power of the cation increases in the same order.
As a result, NaCl does not hydrolyse in water (pH = 7); MgCl 2 hydrolyses only to
a small extent (pH = 6.5) and AlCl 3 hydrolyses to a larger extent (pH = 3.0). [1]
[Total: 15]
5 (a) The actual value for the enthalpy of hydrogenation of benzene is less exothermic [1]
as more energy is needed to break the bonds in benzene due to delocalisation of the
electrons.
OR
Benzene is resonancestabilised and hence has a lower energy level.
(b) reagents: conc. HNO 3 + conc. H 2 SO 4 [1]

conditions: 55 60 C
electrophile: NO 2 + [1]
(c) (i) In phenylamine, the lone pair on the N atom is delocalised into the benzene ring, [1]
making the ring more electronrich.
Hence, the ring is more susceptible to (electrophilic) attack and hence does not [1]
require the strong electrophile Br+ generated by the reaction between Br 2 and
FeBr 3 .
(ii) C 6 H 5 NO 2 + 6[H] C 6 H 5 NH 2 + 2H 2 O [1]
(iii) O [1]
CH3 C N CH2CH3
136 trendyline
(d) 3 : 14 : 9 [1]
Relative rate suggests 1 : 7 : 1, but there are 3 primary to 2 secondary to 9 primary [1]
hydrogen atoms in L, M and N respectively. Hence, this ratio becomes 3 : 14 : 9.
[Total: 9]
6 (a) (i) H H H H H [3]

H slow fast
C C CH3 H C C CH3 H C C CH3
H
I I Cl
I Cl-
Cl
(ii) ICl is polar while pure halogens are not. [1]
(b) number of bonds: 14 [1]

number of bonds: 2
(c) (i) ethene [1]
(ii) [2]
(d) (i) [1]

O-Na+
O O O-Na+
O O-Na+
+Na-O
O-Na+
O-Na+
(ii) (acid) hydrolysis [1]
O
OH
HO
[1]
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OH
e OR C=C
(iii) alkene C [1]
137 trendyline
(iv) Na 2 CO 3 (aq): carboxylic acid [1]
Br 2 (aq): phenol [1]
(v) OH
OH [1]
D:
OR
HO2C HO2C
Br Br
HO2C OH
E:
Br [1]
Br OH
Br
[Total: 16]
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CHEMISTRY 9647/03
Paper 3 Free Response 2 hours
Candidates answer on separate paper.

Additional Materials: Writing Paper
Data Booklet
Graph Paper
Write your name, PDG and register number on all the work you hand in.
Write in dark blue or black pen on both sides of the paper.
You may use a pencil for any diagrams or graphs.
Answer any four questions.

Start each question on a fresh sheet of paper.

You are reminded of the need for good English and clear presentation in your answers.
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his document consists of 12 printed
This rinted pages
pages.

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2
1 (a) Transition elements show typical properties that distinguish them from sblock elements
such as calcium. The following table gives data about some physical properties of the
elements calcium, iron and copper.
property calcium iron copper

relative atomic mass 40.1 55.8 63.5
atomic radius (metallic) / nm 0.197 0.126 0.128
ionic radius (2+) / nm 0.099 0.076 0.069
o
melting point / C 839 1535 1085
3
density / g cm 1.54 7.86 8.92
6 1
electrical conductivity / x 10 S cm 0.298 0.100 0.596
(i) Explain why the atomic radii of iron and copper are similar to each other. [2]
(ii) The melting point of iron is significantly higher than that of calcium. Explain this in
terms of the type and strength of bonding in each metal.
[3]
(iii) Using relevant data from the table, explain why the densities of iron and copper are
significantly greater than that of calcium. (No calculations are required.)
[2]
(b) Cu(I) ions are unstable and readily undergo disproportionation in aqueous solution.
Write an ionic equation showing the disproportionation of Cu+(aq) ions, and choose relevant
Eo values from the Data Booklet to calculate E cell o for the reaction.
[2]
(c) Cu(I) is stable in insoluble salts and in some complexes. Complexes of Cu(I) are colourless
whereas complexes of Cu(II) are coloured. Use these facts to explain the following
observations, writing equations for all reactions.
(i) The addition of KI(aq) to CuSO 4 (aq) produces a white precipitate, CuI, and a brown
solution. The brown solution turns colourless when aqueous sodium thiosulfate,
Na 2 S 2 O 3 , is added, and the white precipitate remains.
[2]
(ii) On boiling with copper foil, the colour of a solution of CuCl 2 in concentrated
hydrochloric acid changes from blue to colourless. The colourless solution contains a
linear complex ion of copper and chlorine.
After filtering off the excess copper metal and diluting the solution with water, a white
precipitate is formed, which contains 35.9 % of chlorine by mass.
[3]
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3
(d) Some copper compounds have found a use as reagents for unusual organic reactions. An
example is the use of a mixture of copper(II) ethanoate and lead(IV) ethanoate for the
conversion of carboxylic acids into alkenes containing one less carbon atom. This reaction is
known as oxidative decarboxylation.
R R
Cu(OCOCH3)2 , Pb(OCOCH3)4 R R
R C C H C C
R H
H CO2H
secondary tertiary
carboxylic acid alkene
When a secondary carboxylic acid G, C 9 H 16 O 2 , was treated in this way, alkene H, C 8 H 14 ,

was formed. On treatment with hot acidified concentrated KMnO 4 , H produced a single
compound J, C 8 H 14 O 3 .
Compound J evolved CO 2 with Na 2 CO 3 (aq), gave an orange precipitate with

2,4dinitrophenylhydrazine reagent, and gave a yellow precipitate with alkaline aqueous
iodine.
When the yellow precipitate had been filtered off, acidification of the aqueous solution
produced 3,3dimethylpentan1,5dioic acid, K.
HO 2 CCH 2 C(CH 3 ) 2 CH 2 CO 2 H
K
Use the information above to deduce the structures for compounds G, H and J, explaining
all the reactions involved.
[6]
[Total: 20]

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4
2 (a) One frequently used method for preparing methyl esters is by reaction of carboxylic acids
with diazomethane, CH 2 N 2 .
RCO 2 H + CH 2 N 2 RCO 2 CH 3 + N 2
The reaction of a carboxylic acid with diazomethane occurs via a twostep mechanism.
Protonation of diazomethane by the carboxylic acid to yield methyldiazonium ion,

CH 3 N 2 +, and carboxylate ion in the first step.
Reaction of the carboxylate ion with CH 3 N 2 + to form N 2 in the second step.
(i) A and B are two possible resonance structures of diazomethane, CH 2 N 2 .
H H
C N N C N N
H H
A B
Suggest which resonance structure of diazomethane, A or B, is likely to be involved in

the first step of the mechanism.
[1]
(ii) Using your answer from (a)(i), suggest the mechanism for the reaction between
RCO 2 H and diazomethane. Show any relevant lone pairs, dipoles and charges, and
indicate the movement of electron pairs with curly arrows.
[3]
(b) (i) Write an equation for the complete combustion of methyl ethanoate, CH 3 CO 2 CH 3 .
[1]
(ii) Define the term standard enthalpy change of formation. [2]
(iii) Use the standard enthalpy changes of combustion, H c o in Table 2.1 to calculate the
standard enthalpy change of formation of methyl ethanoate.
Table 2.1
H c o / kJ mol1
carbon 393.5
hydrogen 285.8
methyl ethanoate 1592.1
[3]
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5
(c) Describe one simple chemical test to distinguish between HCO 2 CH 2 CH 3 and CH 3 CO 2 CH 3 .
State clearly how each compound behaves in the test.
[3]
(d) Consecutive elements W, X, Y and Z are in the third period of the Periodic Table. Element Y
has the highest first ionisation energy and the lowest melting point of these four elements.
(i) Describe what you would see when elements W and Z are separately burned in air or
oxygen.
[2]
(ii) The oxides of elements X and Y can be obtained when the elements are burned in
excess oxygen. The oxides of X and Y have melting points of 1720 oC and 580 oC
respectively.
Briefly relate these melting points to the structure of and bonding in each of these
oxides.
[2]
(iii) Describe the reactions, if any, of the oxides of elements X and Y with water.
Include the approximate pH value of any resulting solutions, and write equations for
any reactions that occur.
[3]
[Total: 20]
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6
3 (a) Nickelmetal hydride (NiMH) batteries are the most common rechargeable batteries used
for devices that require large amounts of energy such as digital cameras and MP3 players.
Most NiMH batteries use an alloy containing mainly lanthanum and nickel.
In one such battery, one of the electrodes is LaNi 5 H 6 and the other is NiO(OH). The
electrolyte is aqueous KOH. During discharge, an electrochemical reaction takes place to
produce LaNi 5 (s) and Ni(OH) 2 (s) and releases electrical energy.
(i) Construct the two halfequations for the reactions that take place at each electrode
during discharge. Indicate the polarity of the electrodes in your answer.
[2]
(ii) During recharge, an electrical potential is applied across the electrodes to reverse the
electrochemical reaction.
Using your answer in (a)(i), write the overall equation for the reaction that occurs
during recharge.
[1]
(iii) Overcharging the NiMH battery may result in the electrolyte being discharged at the
electrodes. A safety vent is thus incorporated in the battery to release the excess
pressure.
With reference to the Data Booklet, suggest a relevant halfequation for the formation
of one product at the electrode of the NiMH battery.
[1]
(b) Zinccerium battery is another type of rechargeable battery using a twoelectrolyte system.
The overall equation for the discharging process is given below.
Zn + 2Ce4+ Zn2+ + 2Ce3+
(i) Given that the typical cell voltage for the cell is 2.2 V, calculate the standard electrode
potential of the cerium halfcell, using relevant data from the Data Booklet.
[1]
(ii) Using relevant data from the Data Booklet, deduce if the Ce4+/Ce3+ halfcell can be
replaced with Br 2 /Br halfcell.
[1]
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7
(c) Amines can be made from a variety of compounds.
Suggest, in no more than three steps, how each of the following transformations can be
achieved.
For each transformation, draw the structures of the intermediate compounds and indicate
reagents and conditions for each of the steps.
(i) CH3 CH2CH2NH2
[3]
(ii) O NH2
[3]
(d) The buffer of 2amino2methylpropan1ol (AMP) has been shown to be well suited for
the determination of the activity of enzymes like alkaline phosphatase and lactate
dehydrogenase. It hydrolyses in water with a pK b value of 4.3.
HOCH 2 C(CH 3 ) 2 NH 2 + H 2 O HOCH 2 C(CH 3 ) 2 NH 3 + + OH
(i) A 100 cm3 solution containing 0.500 mol dm3 of HOCH 2 C(CH 3 ) 2 NH 2 is mixed with
a 100 cm3 solution containing 0.800 mol dm3 HOCH 2 C(CH 3 ) 2 NH 3 +.
Calculate the pH of the buffer solution formed.

[2]
[HOCH2CCH3 2 NH2 ]
(ii) State the ratio of when the pH of the buffer solution is 9.7.
[HOCH2CCH3 2 NH3 ]

Hence calculate the mass of solid NaOH to be added to the buffer solution in (d)(i) to
achieve this ratio.
[2]
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8
(e) Proteins are longchain molecules made by linking together amino acids.
Myoglobin is one such protein that stores and releases oxygen in vertebrate muscle cells.
The table below shows some of the amino acids in a molecule of myoglobin.
aspartic
amino acid serine alanine lysine
acid
abbreviation asp ser ala lys
formula of side
CH 2 CO 2 H CH 2 OH CH 3
chain (CH 2 ) 4 NH 2
(i) Given that asplysala is a particular section of the protein chain of myoglobin, draw
the displayed formula for this section at pH 7.
[1]
(ii) Describe two types of sidechain interaction that would occur between the amino
acids residues of myoglobin. Illustrate your answer with suitable pairs of amino acids
from the table above.
[2]
(iii) Casein is the predominant protein found in milk. The conversion of milk to cheese is a
denaturation process involving the addition of the Lactobacillus bacterium which
produces lactic acid.
Explain this phenomenon by considering the types of sidechain interaction that are
affected during the denaturation of casein.
[1]
[Total: 20]
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9
4 (a) 1,3dibromopropane is the starting material for a fourstep reaction sequence which produces
2,4dihydroxypentane1,5dioic acid. The four reactions are shown.
O O
reaction 1 reaction 2 reaction 3 reaction 4
Br Br E F G HO OH
H+/H2O
OH OH
1,3-dibromopropane 2,4-dihydroxypentane-1,5-dioic acid
Compound F has the molecular formula C 3 H 4 O 2 . On treatment with Tollens reagent, it gives a
silver mirror.
(i) Draw the structures of E and F. [2]
(ii) When preparing compound F from E it is important that the product is distilled off rather than
continually refluxed.
State which unwanted product is avoided by distilling off compound F.

[1]
(iii) In an experiment, 9.0 g of 1,3dibromopropane was converted into compound F with an

overall yield of 67 %. Calculate the mass of F that was obtained.
[2]
(iv) Compound G is converted into the final product by reaction with dilute acid. Suggest the
structure of G.
[1]
(b) The oxides of Group I and II metals have many uses. Beryllium oxide, BeO, is used in many high
performance semiconductor parts for applications such as radio equipment, while sodium oxide,
Na 2 O, is a significant component of glasses and windows.
(i) Using the given data and other relevant data from the Data Booklet, construct an energy level
diagram and use it to calculate the lattice energy of beryllium oxide. Label each energy level
in your diagram and draw arrows representing the energy terms involved. Use symbols or
numbers to represent these energy terms.
enthalpy change of formation of beryllium oxide 609 kJ mol1

enthalpy change of atomisation of beryllium +324 kJ mol1
first electron affinity of oxygen 141 kJ mol1
second electron affinity of oxygen +798 kJ mol1
[3]
(ii) The theoretical lattice energy of beryllium oxide is 4293 kJ mol1. Suggest a reason why this
value is different from your answer in (b)(i).
[1]
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(iii) Explain how
ow you would expect the numerical magnitude
magn of the lattice
latt energy of beryllium
oxide to compare with that of sodium oxide.
[2]

147 trendyline
10
(iv) Explain the reaction(s) that occur(s) when chlorine gas is bubbled into a flask containing
water, at room temperature, to which sodium oxide has been added. Write equation(s) where
appropriate.
[2]
(c) Soluble chromates(VI) in the soil are toxic at low concentrations for plants.
In water treatment to remove the chromate(VI) ions, CrO 4 2(aq), from a sample of soil water,
aqueous acidified iron(II) sulfate is first added to the water sample to convert the chromate(VI) ions
to chromium(III) ions, Cr3+(aq). This is followed by adding aqueous sodium carbonate to the
resultant solution to produce effervescence and an insoluble compound.
(i) Construct an equation for the reaction between aqueous acidified iron(II) sulfate and
chromate(VI) ions.
[1]
(ii) Identify the insoluble compound formed upon adding aqueous sodium carbonate.
With the aid of an appropriate ionic equation, explain its formation. [2]
(d) Chromium(III) ions coordinate with both monodentate and polydentate ligands.
Consider the following complex formation reactions with thiocyanate, SCN, and ethylenediamine,
H 2 NCH 2 CH 2 NH 2 , ligands:
I [Cr(H 2 O) 6 ]3+(aq) + 6SCN(aq) [Cr(SCN) 6 ]3(aq) + 6H 2 O(l)
II [Cr(H 2 O) 6 ]3+(aq) + 3(en)(aq) [Cr(en) 3 ]3+(aq) + 6H 2 O(l)
where (en) is ethylenediamine
(i) Explain what is meant by entropy. [1]
(ii) Explain how \RXZRXOGH[SHFWWKHHQWURS\FKDQJHS r o, for reaction II to compare with that

for reaction I.
[2]
[Total: 20]
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11
5 Nitrogen forms numerous oxides, two of which are dinitrogen monoxide, N 2 O, and dinitrogen tetroxide,
N2O4.
(a) Dinitrogen monoxide, N 2 O, is a nontoxic gas that is used commercially as the propellant in cans of
whipped cream.
Given that N 2 O is a linear molecule, draw a dotandcross diagram showing the electrons (outer
shells only) in N 2 O.
You should distinguish carefully between electrons originating from each of the nitrogen atoms.
[1]
(b) At 1200 K and in the presence of a gold wire, N 2 O decomposes as follows.
2N 2 O(g) 2N 2 (g) + O 2 (g)
The kinetics of this reaction can be followed by measuring the total pressure, P, as it changes with
time, t. In one such experiment, the total pressure changes as follows.
total pressure, P / kPa 25.0 27.5 30.0 32.5 34.0 35.0

time, t / s 0 1030 2360 4230 5870 7420
partial pressure, p, of N 2 O / kPa 25.0
(i) What is the total pressure when the reaction is complete? [1]
(ii) Show that the partial pressure of N 2 O at any time, t, is equal to (75.0 2P) kPa. [2]
(iii) Hence calculate the partial pressures of N 2 O after 1030 s, 2360 s, 4230 s, 5870 s and
7420 s.
[1]
(iv) Using your answers from (b)(iii) and the data above, plot these data on suitable axes and use
your graph to determine the order of reaction with respect to N 2 O.
You should show all your working and draw clearly any construction lines on your graph.
[3]
(v) The rate of reaction is expressed in kPa s1. Write the rate equation for the reaction, and
calculate a value for the rate constant. Include units in your answer.
[3]
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12
At a temperature of 27 oC, gaseous N 2 O 4 and NO 2 are in dynamic equilibrium according to the following
equation.
N 2 O 4 (g) 2NO 2 (g)
pale yellow deep redbrown
(c) When 4.60 g of N 2 O 4 is placed in an evacuated 1.48 dm3 flask at 27 oC, the equilibrium pressure is
1.00 atm (101 kPa).
(i) Calculate the number of moles of N 2 O 4 at the start. [1]
(ii) Calculate the number of moles of gas at equilibrium, assuming the gases behave ideally. [1]
(iii) Hence calculate the percentage of the N 2 O 4 that has been dissociated. [2]
(iv) Write an expression for the equilibrium constant, K p , for the reaction and show it has a value
of 0.17 atm at 27 oC.
[3]
(d) When the equilibrium mixture from (c) at 27 oC is suddenly compressed in a gas syringe, the
mixture immediately darkens and then slowly becomes paler. Suggest why the mixture behaves in
this way.
[2]
[Total: 20]
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H2 Chemistry 9647 2016 JC2 Prelim P3 Suggested Solutions
1 (a) (i) Nuclear charge / proton number increases from Fe to Cu.
However, additional electrons are being added to the inner 3d subshell. As such, [1]
there is an increase in shielding effect caused by the increasing number of
d electrons from Fe to Cu.
Hence, effective nuclear charge remains fairly constant from Fe to Cu. [1]
(ii) Fe uses both the 3d and 4s electrons while Ca only uses the 4s electrons for [1]
metallic bonding.
The ionic radius of Fe is also smaller than that of Ca, resulting in higher charge [1]
density.
This results in stronger metallic bonding between Fe ions and the valence [1]
electrons.
(iii) density = mass / volume

[1]
Fe and Cu have greater atomic mass
and smaller atomic radius. [1]
(b) 2Cu+(aq) Cu(s) + Cu2+(aq) [1]
State symbols not required
Eo(Cu+/Cu) = +0.52 V
Eo(Cu2+/Cu+) = +0.15 V
E cell o = +0.52 (+0.15) = +0.37 V [1]
(c) (i) I and Cu2+ undergo a redox reaction to produce the white precipitate copper(I)
iodide, CuI, and brown solution I2 .
[1]
2+
2I (aq) + Cu (aq) CuI(s) + I2 (aq)
S 2 O 3 2 then reduces I 2 to I (colourless solution), itself oxidises to S 4 O 6 2 (redox

reaction).
[1]
2 2
2S 2 O 3 (aq) + I 2 (aq) 2I (aq) + S 4 O 6 (aq)
(ii) Cu and Cu2+ undergo a redox reaction (or comproportionation) to form a colourless
Cu(I) complex, [CuCl 2 ].
trendyline
dyy
[1]
Cu(s)) + Cu2+(aq) + 4Cl
4Cl(aq) uCl 2 ](aq)
2[CuCl
2
2[ Cu
152 trendyline
Element Cu Cl
% by mass 64.1 35.9
Ar 63.5 35.5
No. of moles 64.1/63.5 35.9/35.5
= 1.009 = 1.011 [1]
Simplest whole no. ratio 1 1
The white precipitate is CuCl.
[CuCl 2 ](aq) CuCl(s) + Cl(aq) [1]
(d) Information Type of reaction Deduction(s) [6]

On treatment with hot Oxidative H contains a C=C / alkene.
acidified concentrated cleavage
KMnO 4 , H produced a Since a single compound is formed
single compound J, (without loss of C), H is a cycloalkene.
C 8 H 14 O 3 .
J evolved CO 2 with Acidbase J contains RCO 2 H / carboxylic acid.
Na 2 CO 3 (aq),
gave an orange precipitate Condensation J contains a ketone.
with 2,4DNPH, (J cannot contain an aldehyde since J
is produced from strong oxidation of H
with KMnO 4 )
and gave a yellow Oxidation / J has a CH 3 CO structure

precipitate with alkaline triiodomethane (J cannot have a CH 3 CH(OH)
aqueous iodine. reaction structure since J is produced from
strong oxidation of H with KMnO 4 )
O CH3
CH3 C CH2 C CH2 CO2H
CH3
CO2H
G H J
Do not accept for structure of G as G is a secondary carboxylic acid

CO2H
trendyline
[Total: 20]
153 trendyline
2 (a) (i) B [1]
(ii) O O O [3]
R C CH2 N N R C CH3 N N R C + N2
O H O O CH3
(b) (i) CH 3 CO 2 CH 3 + 7/2O 2 3CO 2 + 3H 2 O [1]
Accept equation multiplied through by 2
(ii) The amount of heat absorbed or evolved when one mole of substance is formed [2]
from its constituent elements in their standard states at 298 K and 1 atm.
(iii) H f o
3C(s) + 3H 2 (g) + O 2 (g) CH 3 CO 2 CH 3 (l)
H f o = H c o(reactants) H c o(products)
= [3(393.5) + 3(285.8) + 0] [1592.1)] = 446 kJ mol1 [3]
(c) Heat each compound separately with NaOH(aq), and then add I2 (aq) to the resulting [1]
solution.
A yellow precipitate (CHI3 ) is observed for HCO 2 CH 2 CH 3 . [1]

No (yellow) precipitate is observed for CH 3 CO 2 CH 3 . [1]
(d) (i) W (aluminium) burns in O 2 with an intense white flame to give a white solid of Al 2 O 3 . [1]
Z (sulfur) burns in O 2 on gentle heating with a pale blue flame to give a colourless [1]
gas of SO 2 .
(ii) The oxide of X (SiO 2 ) has a giant molecular structure. Large amount of energy is [1]
required to break the strong covalent bonds between Si and O atoms.
The oxide of Y (P 4 O 10 or P 4 O 6 ) has a simple molecular structure. Less energy is [1]

required to break the weak van der Waals forces of attraction between the
molecules.
(iii) The oxide of X (SiO 2 ) is insoluble in water. Hence, the pH of the resulting solution is [1]
7.
The oxide of Y (P 4 O 10 or P 4 O 6 ) reacts readily in water to produce a strongly acidic [1]

solution of pH 2.
P 4 O 10 + 6H 2 O 4H 3 PO 4 OR P 4 O 6 + 6H 2 O 4H 3 PO 3 [1]
[Total: 20]
trendyline
154 trendyline
3 (a) (i) At LaNiH 6 electrode: LaNi 5 H 6 + 6OH LaNi 5 + 6H 2 O + 6e [2]

At NiO(OH) electrode: NiO(OH) + H 2 O + e Ni(OH) 2 + OH

++
(ii) LaNi 5 + 6Ni(OH) 2 LaNi 5 H 6 + 6NiO(OH) [1]
(iii) 4OH O 2 + 2H 2 O + 4e [1]
OR
2H 2 O + 2e H 2 + 2OH
(b) (i) Eo(Zn2+/Zn) = 0.76 V
2.2 = Eo(Ce4+/Ce3+) (0.76)

Eo(Ce4+/Ce3+) = +1.44 V [1]
(ii) Eo(Br 2 /Br) = +1.07 V
Eo cell = +1.07 (0.76)

= +1.83 V > 0 (feasible)
Since it is feasible for the battery to discharge electricity, the Ce4+/Ce3+ halfcell [1]
can be replaced with Br 2 /Br halfcell.
(c) (i) CH3 CH2Cl CH2CN CH2CH2NH2 [3]

(limited) Cl2(g) NaCN in ethanol LiAlH4
uv light heat under reflux in dry ether
(ii) O OH Cl NH2 [3]

LiAlH4 excess conc. NH3
in dry ether SOCl2 heat in sealed tube
(d) (i) Since equal volume of HOCH 2 C(CH 3 ) 2 NH 2 and HOCH 2 C(CH 3 ) 2 NH 3 + are mixed,
concentration of both species are halved.
[HOCH2CCH3 2 NH3 ][OH- ]

Kb
[HOCH2CCH3 2 NH2 ]
(0.400)[OH ] [1]
10 -4.3
0.250
[OH] = 3.13 x 105 mol dm3
pOH
H=
ttrendyline
log(3.13 x 1055) = 4.5
log(3.13
pH = 9.5 [1]
155 trendyline
(ii) Since pK b (AMP) = 4.3, pK a (conjugate acid of AMP) = 9.7.
When pH of the buffer = 9.7, the buffer solution is at its maximum buffering
capacity.
[HOCH2CCH3 2 NH2 ] [1]

Hence = 1.
[HOCH2CCH3 2 NH3 ]

initial n(HOCH 2 C(CH 3 ) 2 NH 3 +) = 100/1000 x 0.800 = 0.0800 mol

initial n(HOCH 2 C(CH 3 ) 2 NH 2 ) = 100/1000 x 0.500 = 0.0500 mol
Let x be n(OH) added
HOCH 2 C(CH 3 ) 2 NH 3 + + OH HOCH 2 C(CH 3 ) 2 NH 2 + H 2 O

initial (mol) 0.0800 x 0.0500
change x x +x
final (mol) 0.0800 x 0 0.0500 + x
[HOCH2CCH3 2 NH2 ]
Since = 1,
[HOCH2CCH3 2 NH3 ]

0.0800 x = 0.0500 + x
x = 0.015 mol
mass of NaOH added = 0.015 x (23.0 + 16.0 + 1.0) = 0.600 g [1]
(e) (i) H O H O H O [1]
N C C N C C N C C
H H C H H H C H C
H H
C H C H H
O O
H C H
H C H
N
H
H H
(ii) Ionic bonding between charged R groups containing the CO 2 groups, NH 3 + [1]
groups.
Example: Between lysine (containing NH 3 +) and aspartic acid (containing
trendyline
tren dyli
y
C 2 )
CO
Hydrogen bonding between

etwee polar R groupsroup containing the carboxyl groups [1]
(
CO 2 H), amino groups (NH
(CO (NH 2 ) or hydroxyl (
(OH)
(OH) groups.
Example: Between aspartic acid and serine or between lysine and serine.
156 trendyline
(iii) Lactic acid dissociates to give H+ which may protonate the carboxylate group (in [1]
glutamic acid) or the amine group (in lysine), disrupting ionic bonds between the
charged R groups.
OR
disrupting the hydrogen bonding between the polar R groups (e.g. lysine and
serine, leading to denaturation.
[Total: 20]
trendyline
157 trendyline
4 (a) (i) O O [2]
HO OH H H
E F
(ii) O O O O [1]
HO OH OR H OH
Accept propanedioic acid Accept 3oxopropanoic acid
(iii) n(1,3dibromopropane) = 9.0 / 201.8 = 0.0446 mol [1]

mass of F = 0.67 x 0.0446 x 72.0 = 2.15 g [1]
(iv) OH OH [1]
NC CN
(b) (i) Energy [2]

Be2+(g) + O2(g)
(+900) + (+1760) + (141) + 798 (+3317)
Be(g) + O(g)
lattice energy of BeO(s)
(+324) + (496) (+572)
Be(s) + O2(g)

BeO(s)
trendyline
Lattice
ce
e energy of BeO(s)
= (3317
BeO(s
3317 + 572 + 609)
98 kJ mol11
= 4498
498 [1]
158 trendyline
(ii) Theoretical calculation assumes pure ionic character.
But Be2+ ion is small and highly charged, hence it has high polarising power
BeO exhibits covalent character [1]
Attraction is stronger, so observed value is more exothermic.
(iii) q q-
Given LE
r r-
ionic charge of Be2+ > ionic charge of Na+

ionic radius of Be2+ < ionic radius of Na+ [1]
Stronger attraction between oppositely charged ions in BeO

LE (BeO) > of LE (Na 2 O) in magnitude [1]
(iv) Na 2 O(s) + H 2 O(l) 2NaOH(aq)

Sodium oxide dissolves in water to produce sodium hydroxide [1]
Cl 2 (g) + 2NaOH(aq) NaCl(aq) + NaClO(aq) + H 2 O(l)

Chlorine undergoes disproportionation reaction when reacted with NaOH. [1]
(c) (i) CrO 4 2 + 8H+ + 3e Cr3+ + 4H 2 O

Fe2+ Fe3+ + e
CrO 4 2 + 3Fe2+ + 8H+ Cr3+ + 3Fe3+ + 4H 2 O [1]
(ii) chromium(III) hydroxide OR Cr(OH) 3 (H 2 O) 3 OR Cr(OH) 3
2[Cr(H 2 O) 6 ]3+ + 3CO 3 2 2[Cr(OH) 3 (H 2 O) 3 ] + 3CO 2 + 3H 2 O [1]
Cr3+(aq) undergoes hydrolysis with water liberating H+(aq)

[1]
Undergoes acidbase reaction with Na 2 CO 3 (aq)
(d) (i) a state function that measures the degree of disorder / randomness in a system [1]
OR
gives a measure of the extent to which particles and energy are distributed
within the system OR
the greater the disorder / randomness, the larger is the entropy.
(ii) In reaction I, there is no change in number of particles in aqueous solution, [1]

whereas in reaction II, there is an increase of 3 particles.
Increase in number of ways of arrangement and energy distribution of the

particles
S r o is more positive [1]
[Total: 20]
trendyline
159 trendyline
5 (a) [1]
N N O
(b) (i) total pressure, P, when reaction is complete = 3/2 x 25 = 37.5 kPa [1]
(ii) 2N 2 O(g) 2N 2 (g) + O 2 (g)

initial / kPa 25 0 0
change / kPa x +x +1/2x
final at any time, t / kPa 25 x x 1/2x
25 x + x + 1/2x = P
25 + 1/2x = P
x = 2P 50 [1]
Hence, partial pressure of N 2 O at any time, t, is
25 x = 25 (2P 50)
= 25 2P + 50
= 75.0 2P (shown) [1]
(iii) P / kPa 27.5 30.0 32.5 34.0 35.0

t/s 1030 2360 4230 5870 7420
p of N 2 O / kPa 20 15 10 7 5 [1]
trendyline
160 trendyline
(iv) [2]
[1]
Since t 1/2 is constant at 3200 s, the order of reaction w.r.t. N 2 O is 1.
(v) rate k pN2 O [1]
ln 2
t1/2
k
ln 2
k
t1/2
trendyline
ren
ln 2 [1]
2.17 x 10
1 - 4 s-1 [1]
3200
161 trendyline
(c) (i) n(N 2 O 4 ) = 4.60 / 92.0 = 0.0500 mol [1]
(ii) pV = nRT
n = pV / RT
101 x 103 x 1.48 x 10 -3
= = 0.0600 mol [1]
8.31 x 300
(iii) N 2 O 4 (g) 2NO 2 (g)

initial / mol 0.05 0
change / mol x/2 +x
eqm / mol 0.05 x/2 x
0.05 x/2 + x = 0.06

x = 0.02 [1]
n(N 2 O 4 ) dissociated = x/2 = 0.02/2 = 0.01

% of N 2 O 4 dissociated = 0.01 / 0.05 x 100 = 20.0 % [1]
(iv) pNO2
2 [1]
Kp
pN2O4
p(NO 2 ) = 0.02/0.06 x 1.00

= 1/3 atm [1]
p(N 2 O 4 ) = 0.04/0.06 x 1.00

= 2/3 atm
( 1 )2
Kp 3 = 1/6 0.17 (shown)
2 [1]
3
(d) N 2 O 4 (g) 2NO 2 (g)

pale yellow deep redbrown
When the equilibrium mixture is suddenly compressed in a gas syringe, [N 2 O 4 ] and [NO 2 ] [1]
increase due to the reduced volume.
Compression of the gas also results in an increase in pressure. The position of the
above equilibrium shifts left to decrease pressure by producing fewer gas molecules. The [1]
mixture becomes paler as [N 2 O 4 ] increases.
[Total: 20]
trendyline
162 trendyline

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CATHOLIC JUNIOR COLLEGE
JC2PRELIMINARY EXAMINATIONS
Higher 2
CANDIDATE
NAME
CLASS 2T
CHEMISTRY 9647/02
Paper 2 Structured Questions Monday 22 August 2016
2 hours
Write your name and class on all the work you hand in.
You may use an HB pencil for any diagrams or graphs.
Do not use staples, paper clips, or correction fluid.

The use of an approved scientific For Examiners Use
calculator is expected, where appropriate.
A Data Booklet is provided. Paper 1 40
Q1 12
At the end of the examination, fasten all
your work securely together. Q2 15
The number of marks is given in brackets
[ ] at the end of each question or part Paper 2
Q3 15
question.
Q4 15
Q5 15 72
Q1 20
Q2 20
Paper 3 Q3 20
Q4 20
Q5 20 80
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yli
Total
ta 192
9647/02/CJC JC2 Preliminary Examination 2016

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2
1 Planning (P) For

Examiners
Use
One method of studying the kinetics of a chemical reaction, to find the order of reaction
with respect to a particular reactant, is to measure the initial rates, by using the clock
experiment.
To determine the initial rate, we can measure the time taken for a prominent visual change
to occur in the course of a reaction.
When aqueous sodium thiosulfate, Na 2 S 2 O 3 , is added to a solution containing dilute

hydrochloric acid, HCl, a fine, pale yellow precipitate of solid sulfur will be formed after a
while. This is the prominent visual change that can be clearly identified.
The overall equation for the reaction is represented as follows:
S 2 O 3 2-(aq) + 2H+(aq) S(s) + SO 2 (g) + H 2 O(l)
The initial rate of this reaction is determined by measuring the time taken for sufficient
precipitate of sulfur to be formed to just obscure a cross marked on a piece of white
paper below a reaction container.
A student carried out a series of preliminary experiments, using approximate volumes of

the two reactants and each reaction mixture was made up to the same total volume with
deionised water. The student found that the time taken for the pale yellow precipitate to
appear doubled when the volume of hydrochloric acid added was halved.
(a) (i) State the relationship between the initial rate of reaction and the time taken for
thepale yellow precipitate to appear.
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...................................................................................................................... [1]
(ii) Explain why it is necessary to top up the reaction mixture with deionised water
to the same total volume.
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3
(b) Hence, based on the results of the students preliminary experiments, predict the For
Examiners
order of the reaction with respect to H+ ions. Use
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(c) You are to design an experiment to study the kinetics of the reaction between S 2 O 3 2-
ions and H+ ions.
The following data in tabulated form is shown below.
experiment volume of volume of volume of time taken for

1.00 mol dm-3 1.00 mol dm-3 deionised water the marked
Na 2 S 2 O 3 / cm3 HCl / cm3 / cm3 cross to be
obscured / s
1 10 20 20 t1
2 20 t2
3 10 t3
(i) Fill in the blanks in the table above, appropriate volumes of the reactants and
deionised water to be used in experiments 2 and 3 such that the order of
reaction with respect to S 2 O 3 2- and H+ ions can be determined and verified. [1]
(ii) Outline in a series of numbered steps, how experiment 1 could be carried out.
the apparatus used to measure the various volumes,
the order that the various solutions are mixed,
how the time to determine the rate of reaction is measured, and
other experimental details to ensure the consistency of the
experiment.
Based on the table in (c)(i), explain how the results of any two of the three
experiments can be used to determine the order of reaction with respect to
S 2 O 3 2- ions.
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9647/02/CJC JC2 Preliminary Examination 2016 [Turn over

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4
For
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Use
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(d) Identify one potential safety hazard in this experiment and state how you would
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ise
minimisese this risk.
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..... [1]
[Total: 12]
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5
For
2 Silver halides (silver chloride, silver bromide and silver iodide) are useful in qualitative Examiners
Use
analysis as they are insoluble in water. In qualitative analysis, silver nitrate is added to a
test solution to identify the presence of halide ions by forming a precipitate.
(a) (i) When aqueous silver nitrate was added to a test solution which was known to
contain a halide ion, a cream precipitate was formed.
Identify the precipitate and deduce the identity of the halide ion present in the
solution.
..........................................................................................................................
...................................................................................................................... [1]
(ii) To confirm the identity of the halide, aqueousammonia was added dropwise,
and the precipitate remained unchanged at first, but as more ammonia was
added, the precipitate dissolved.
With the aid of an equation, brieflyexplain why the precipitate dissolved.
..........................................................................................................................
..........................................................................................................................
...................................................................................................................... [2]
(iii) Draw the structure of the silver-containing product in solution after the
precipitate dissolved, displaying any lone pair of electrons where appropriate.
[1]
In photography, after an image is developed, sodium thiosulfate, Na 2 S 2 O 3 , is used

to dissolve any remaining silver halide away, to fix the image and ensure that it
does not change upon further exposure to light.
(iv) An equal volume of sodium thiosulfate was added to the solution

from (ii). State the type of reaction that occurred when sodium thiosulfate was
added.
...................................................................................................................... [1]
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(v) Suggest silver-containing
uggest the identity of the silve
silver ning product which has
containing h a coordination
number of 2.
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6
(b) The table below shows data about silver and two other metals, iron and copper. For
Examiners
Use
silver iron copper

10 1 6 2
electronic configuration [Kr] 4d 5s [Ar] 3d 4s [Ar] 3d104s1
conductivity at room 6.3 x 107 1.0 x 107 ?
temperature/ S m1
(i) Explain, in terms of structure and bonding, why the three metals have high
electrical conductivity.
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...................................................................................................................... [2]
(ii) Silver and copper are known to be excellent metallic conductors at room
temperature. Noting the electronic configuration, suggest the value of the
conductivity of copper at room temperature.
......................................... S m-1[1]
(iii) Iron is used as a catalyst in the synthesis of ammonia in the Haber process.
State the type of catalysis and explain clearly how it carries out its function.
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For
(c) When a jar is filled with gaseous hydrogen iodide,HI, and a red-hot glass rod Examiners
Use
inserted into the jar, violet fumes are observed.
(i) State the identity of the violet fumes.
...................................................................................................................... [1]
(ii) When the same procedure is carried out with HBr instead of HI, no fumes are
observed, but on strong heating, reddish-brown vapour is obtained.
With reference to values in theData Booklet, explain the difference in the

behaviour of HBr and HI.
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[Total: 15]
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For
3 Methanol is one of the alternative fuels proposed to replace fossil fuels. It has the Examiners
advantage of more efficient production and ease of storage as compared to other Use
alternatives.
Methanol can be formed from carbon monoxide and hydrogen as shown below.
CO(g) + 2H 2 (g) CH 3 OH(g)
The reaction was investigated by mixing 3.2 mol of CO and 3.2 mol of H 2 in a 10.0
dm3sealed vessel, and equilibrium was established at 120 C under a pressure of
1.60 x 106 Pa.
(a) (i) Assuming ideal gas behaviour, determine the total amount of gas in moles,at
equilibrium.
[2]
(ii) Hence, calculate the amounts of CO, H 2 and CH 3 OH in moles, present at

equilibrium.
[3]
(iii) Write an expression for the equilibrium constant, K c for the above reaction,
and use your answers in (a)(ii) to calculate its value under the stated
conditions.
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9
(b) Standard Gibbs free energy change,Gois related to K c by the following equation. For
Examiners
Use
o
G = RTln K c
where Gois in joules per mole, T is the temperature at which equilibrium is

established and R is the molar gas constant.
(i) Use this equation and your answer in (a) to calculate Gofor the formation of
methanol from carbon monoxide and hydrogen at 120 C.
[1]
(ii) With reference to theData Booklet, calculate the enthalpy change offormation
of methanol from carbon monoxide and hydrogen.Use
-1
1072 kJ mol for the bond energy of CO bond.
[2]
(iii) Hence, state briefly why higher temperature is not used industrially for the
formation of methanol from carbon monoxide and hydrogen.
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(iv) Use your answers in (b)(i) and (ii) to calculate the standard entropy change for
the reaction at 298K.
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10
For
(v) Explain the significance of the sign of the calculated entropy change and Examiners
comment if this is expected. Use
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[Total:15]
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For
4 (a) Acetanilide was the first aniline derivative found to possess analgesic and antipyretic Examiners
Use
properties.It was introduced into medical practice under the name of the drug,
Antifebrin.
Suggest the reagents and conditions that can be used to distinguish acetanilide from
compound X. State clearly the expected observations for each compound.
H O
N
N
O H
Acetanilide Compound X
Reagents and conditions ..
....
Observations .
....
....[2]
(b) It was later discovered that acetanilide was toxic and thus paracetamol, a derivative
of acetanilide, was produced.
H
N
O
HO
Paracetamol
(i) State the shape about N atom in paracetamol and hence identify the type
ofhybridisation involved.
Shape about N atom ..
Hybridisation of N .. [2]
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12
For
(ii) A reaction scheme was proposed for the synthesis of paracetamol from phenol. Examiners
Fill in the boxes provided with the reagents, conditions and intermediates for Use
the synthesis.
OH OH
Step 1 Step 2
Intermediate
NH2
Step 3
OH
N
H
O
Paracetamol
Reagents and conditions:
Step 1 ..
Step 2 ..
Step 3 ..
Structure of intermediate:
[4]
(iii) In the synthesis of paracetamol from phenol, two possible side-products,

compound Y and Z, are formed. Given that only compound Y is a position
isomer of paracetamol, suggest the identities of compound Y and Z.
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trendy ine Compound Y Compound
Compo Z
[2]
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13
For
(iv) Predict, with explanation, how the boiling point of paracetamol might compare Examiners
to that of compound Y. Use
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(c) In a typicalpain relief tablet, there are500 mg of paracetamol.
(i) An adult can consume up to a maximum dosage of 4000 mg of paracetamol

within 24 hours. The average adult weight is 62 kg. Calculate the number of
tablets a childwho weighs 45 kg, can consume within 24 hours. (Maximum
dosage is dependent on weight of an individual.)
[2]
(ii) It was recommended to consume the tablets at 6 hours intervals. Using your
answer in (c)(i), calculate the recommended number of tablets the child should
take at each interval without exceeding dosage.
[1]
[Total: 15]

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For
5 The compound p-cresol is used in the production of antioxidants. It is also used in the Examiners
Use
fragrance and dye industries.
CH3
OH
-creso
p l
(a) Draw the displayed formula of a functional group isomer of p-cresol, and describe a
laboratory test that will distinguish these two compounds. You should state the
reagents used and the observations expected.
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............................................................................................................................... [3]
(b) p-Cresol can be prepared industrially by a 2-step process as shown below.
CH3 CH3 CH3
+ +
concentrated I II
SO3
H2SO4
SO3H OH
- -
p toluenesulf onic acid p cresol
Reaction I involves sulfonation of methyl benzene to give p-toluenesulfonic acid.

The proposed mechanism of reactionI involves electrophilic substitution.
(i)
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The first step of the proposed mechanism of reaction I involves
reaction +
i
in
eaction in the generation of an electrophile, HSO 3 . Writ
how how the electrophile HSO 3 iss formed.
show +
acid-base
Write an equation to
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15
(ii) Complete the proposed mechanism to produce p-toluenesulfonic acid as For

Examiners
shown above. In the mechanism, show clearly the curly arrows to indicate the Use
movement of electrons and all charges.
[3]
(c) p-Cresolis used in the production of antioxidants such as butylated hydroxytoluene,

BHT, which is mainly used as an antioxidant in the food industry. The reaction
involves a dialkylation of p-cresol with 2-methylpropene in the presence of an
acidcatalystgiven below.
CH3 CH3
+
H
+
OH OH
-creso -
p l 2 methylpropene BHT
(i) Draw a labelled diagram to show how the orbitals overlap to form the C=C
bond in 2-methylpropene and state the type of hybridisation involved.
[1]
Type of hybridisation: ...................................................................................[1]
(ii) Explain why 2-methylpropene cannot exhibit geometric isomerism.
...
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16
For
(iii) In order for BHT to act as an antioxidant, it forms a very stable radical on the Examiners
Use
oxygen atom as shown below. Suggest an explanation why this stable BHT
radical is unable to react further with other molecules.
CH3
O
BHT radical
...
...................................................................................................................... [1]
(iv) Compound R, C 14 H 20 O 2 , is a metabolite derived from the biotransformation of

BHT. It is structurally related to BHT, C 15 H 24 O, and is also a cyclic compound.
State the type of reaction and deduction for the following observations.
I 1 mole of Compound R will react with 2 moles of 2, 4-DNPH.
Type of reaction:.......................................................................................
Deduction: ...........................................................................................[1]
II Compound R will not react with Tollens reagent.
Deduction: ........................................................................................... [1]
III 1 mole of compound R willdecolourise 2 moles of aqueous Br 2 but no

HBr is formed.
Type of reaction:.......................................................................................
Deduction: ...........................................................................................[1]
IV Deduce the structure of compound R.
trendyline [Total: 15]

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Higher 2
CHEMISTRY 9647/03
Paper 3 Free Response Friday 26 August 2016
2 hours
Additional Materials: Answer Paper

Data Booklet

ttrendyline
d liThis
his documents consists of 10 printed
9647/03/CJC JC2 Preliminary

rinted pages.
pages
nary Examination 2016 [Turn over
245 trendyline
2
(a) When potassium manganate(VII), KMnO 4 , is heated with concentrated sodium hydroxide,
NaOH, bubbles of oxygen are seen and a green solution of MnO 4 2- is obtained. The
addition of barium chloride, BaCl 2 , to this solution precipitated out a solid X with
composition by mass of 53.5% barium, 21.5% manganese and 25.0% oxygen.
(i) Calculate the empirical formula of X. [1]
(ii) When the green solution above is acidified, a brown precipitate in a purple solution
is formed.
Suggest the identities of the species formed upon acidification and hence state the
type of reaction that has occured. [3]
(b) A solution of acidified potassium manganate(VII), KMnO 4 , can be standardised through

titration against sodium ethanedioate, Na 2 C 2 O 4 . The ethanedioate ion is oxidised to
carbon dioxide in this reaction.
(i) State the oxidation numbers of C in the ethanedioate ion and in carbon dioxide. [1]
(ii) Write the half-equation for the oxidation of the ethanedioate ion. [1]
(iii) Hence, write the overall balanced equation for the reaction between acidified
manganate(VII) and ethanedioate ions. [1]
(iv) In one such standardisation procedure, 25.0 cm3 of 0.0150 mol dm3 Na 2 C 2 O 4
solution required 28.85 cm3 of acidified KMnO 4 to reach the end-point.
Determine the concentration of KMnO 4 in the solution. You may assume that
2MnO 4 & 2 O 4 2. [3]
(c) Myrcene, A and ocimene, B,are isomers with the molecular formula C 10 H 16 . When
subjected to hydrogen with platinum catalyst, both isomers give 2,6-dimethyloctane,
C 10 H 22 .
2,6-dimethyloctane
When treated with hot concentrated acidified KMnO 4 , A gives CO 2 and compound C,
C 7 H 10 O 4 ; B gives CO 2 and compounds D, C 5 H 8 O 3 , and E, C 3 H 4 O 3 .
Compounds C, D andE give one mole of CHI3 with alkaline aqueous iodine. On addition
trendyline
Na
of aqueous NaHCO 3 , compounds C, D andE
and
ndE produce
ce effervescence.
eff
Suggest structures
ctures for A-E,
uctures A-E, and explain the observations described abov
above. [10]
[Total: 20]

246 Examination 2016 trendyline
3
2 The table below lists the standard enthalpy change of formation of four compounds.
Compound H f o/kJ mol1

H 2 O(l) 286
HCl(g) 92.0
SiO 2 (s) 910
SiCl 4 (l) 640
(a) What is meant by the term, standard enthalpy change of formation of a compound? [1]
(b) SiCl 4 (l) undergoes hydrolysis to give SiO 2 (s).
(i) Write the balanced equation with state symbols for the hydrolysis reaction. [1]
(ii) Using the above data, calculate the standard enthalpy change for the hydrolysis
reaction. State one assumption made in your calculation. [1]
(iii) Does the hydrolysis have a positive, negative or zero entropy change? Explain your
answer. [1]
(iv) Hence, by the use of the Gibbs free energy, Go, explain why the hydrolysis of
SiCl 4 (l) is always a spontaneous process. [1]
(c) Consider reaction1and reaction 2 shown below.
anhydrous AlCl3
dimethylated benzenes
reacti on 1: + CH Cl
3 CH3 + an other ro ucts
d p d
Heat
anhydrous AlCl3
reacti on 2: + CH COCl
3 COCH3
Heat
(i) Both reaction 1 and reaction 2proceed via a similar mechanism. Name the type of
reaction undergone. [1]
(ii) Suggest why reaction 1 gives a mixture of organic products while reaction 2 gives
only one mono-substituted product. [2]
(d) The organic product in reaction 2, phenylethanone, COCH3, reacts with HCN to
produce the corresponding cyanohydrin under certain experimental conditions.
(i) State the experimental conditions. [1]
(ii)
trendyline
Describe
ibe the mechanism of reaction, of phenylethanone with HCN, showing clearly
the curly
ly arrows to indicate the movement of electrons and all charges.
rly char [3]

247 Examination 2016 [Turn
trendylineover
4
(iii) Hence, suggest the reagents and conditions used in the following conversion,
stating clearly the intermediate products in the process of synthesis. [2]
CONH2
COCH3 C CH3
Cl
(e) The rate of reaction between phenylethanone and iodine in acid medium to give
2-iodo-1-phenylethanone, COCH2I , is found to be independent of [ I 2 ], but
directly proportional to [H+] and directly proportional to [phenylethanone].
(i) Write the rate equation for this reaction and state the overall order and the
units of the rate constant. [2]
(ii) The reaction between phenylethanone and bromine proceeds by a similar

mechanism. How would you expect the rate of this reaction to compare with
that of the above reaction? Explain your answer. [1]
(iii) When a basic medium is used instead for the reaction between
phenylethanone and iodine, a different mechanism of reaction is followed and
different organic products are produced.
(I) State the type of reaction undergone. [1]
(II) Give the structures of all the organic products formed in this reaction. [2]
[Total: 20]
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5
3 Fireworks are a traditional part of many celebrations. Their colours can come from heating
ofGroup II metals and their salts. These salts often contain anions such as chlorates,
perchlorates, and nitrates which are oxidising agents.
(a) One of the Group II metals,M, when heated with oxygen under pressure, forms a metal
peroxide which can be used as anoxidising agent in fireworks to produce a vivid green
colour. The equation for the reaction is shown below:
2MO(s) + O 2 (g) 2MO 2 (s)
When equilibrium is attained, the mixture of oxides was found to have a mass of 1.60g,
where MO 2 has a percentage mass of 18.7%. When the mixture was treated with dilute
sulfuric acid, a white solid was precipitated and a solution of hydrogen peroxide was
produced.
An excess of acidified potassium iodide was added to the hydrogen peroxide solution.
The reaction between hydrogen peroxide and acidified potassium iodide is as follows.
H 2 O 2 + 2I+ 2H+ I 2 + 2H 2 O
The iodine liberated needed 11.80 cm3 of 0.300 moldm3 sodium thiosulfate, Na 2 S 2 O 3 , for
complete reaction.
I 2 + 2S 2 O 3 2 6 4 O 6 2 + 2I
(i) Write a balanced equation to represent the reaction between MO 2 and sulfuric
acid. [1]
(ii) By determining the amount of MO 2 that has reacted,calculate the relative atomic
mass of M and suggest its identity. [5]
(b) Strontium nitrate, Sr(NO 3 ) 2 is an oxidising agent and is commonly used as a red colouring
agent in fireworks.
(i) Write a balancedequation for the reaction that occurs when Sr(NO 3 ) 2
undergoesthermal decomposition. [1]
(ii) Predictwhether the decomposition temperature of Sr(NO 3 ) 2 will be higher or lower

than the decomposition temperature of Mg(NO 3 ) 2 . Explain your answer. [3]
(c) Anotheroxidising agent used in fireworks is potassium chlorate(V), KClO 3 .When KClO 3
undergoes thermal decomposition, two products are obtained, one of which is KCl.
(i) Write a balanced equation to show how KClO 3 is produced from Cl 2 gas and hot,
aqueous potassium hydroxide. [1]
(ii)
trendyline
Write a balanced equation for
suggest
st why KC
or the thermal decomposition of KClO 3 and hence
ClO 3 is an important ingredient
ingredien used in fireworks. [2]

trendylineover
6
(d) Fireworks which produce bright sparks, flashes and coloured flames also involve the
elements phosphorus, sulfur and chlorine.
The table below gives the melting points of these elements.
element phosphorus sulfur chlorine

melting point /K 317 392 172
In terms of structure and bonding, explain why sulfur has the highest melting point among
the three elements. [2]
(e) Sodium salicylate and sodium benzoate are used as whistle mixes in fireworks. Both are
white crystalline powder.
OH O O
+ +
O Na O Na
sodium salicylate sodium benzoate
(i) Suggest methods by which sodium salicylate and sodium benzoate can be
distinguished from each other by a simple chemical test. State the reagents and
conditions used and the expected observations for each compound. [2]
(ii) The pK a values of the two acidic groups in salicylic acid are pK a1 = 2.98 and
pK a2 =13.6.
OH O
OH
salicylic acid
Draw the displayed formula of the mono-anion produced after the dissociation of the
carboxylic acid group and use your formula to explain why the dissociation of the
phenol group is unlikely to occur. [3]
[Total: 20]
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7
4 Strecker synthesis is a method used for the synthesis of amino acids. It is often studied due to
the simplicity of the process.
(a) Alanine, an amino acid, can be formed using this method as shown below.
+
O NH2 Cl NH2
C
NH4Cl H3C C KCN
H3C C NaOH, heat
H3C Products
step 1 step 2 CN step 3
H H H
(i) Construct a balanced equation for step 1 and suggest the type of reaction that has
occurred. [2]
(ii) Give the structural formulae for allthe products formed in step 3. [2]
(b) Insulin is a hormonal protein which was first discovered in 1921. In 1959, it became the
first protein to have its primary structure determined. These led to the award of two Nobel
Prizes, in Physiology/Medicine and Chemistry respectively.
The basic unit of insulin consists of two polypeptides, A-chain and B-chain. A-chain has
21amino acid residues, and some of these are listed in the following table(You may use
the abbreviations for your answers).
formula of R group side chain number of amino acid

amino acid abbreviation
at pH 7.4 (physiological pH) residues in A-chain
cysteine cys CH 2 SH 4

glutamic acid glu CH 2 CH 2 CO2 2
glutamine gln CH 2 CH 2 CONH 2 2
glycine gly H 1
isoleucine ile CH(CH 3 )CH 2 CH 3 2
threonine thr CH(OH)CH 3 1
valine val CH(CH 3 )CH 3 1
In order to determine the sequence of the A-chain, partial hydrolysis was carried out with
two separate methods to obtain several polypeptide fragments. One method of hydrolysis
involves the use of 6 mol dm-3 HCl or NaOH, while the othermethod causes hydrolysis at
specific peptide bonds.
(i) State what may be used in the method for the hydrolysis at specific peptide bonds.[1]
(ii) subjecte for further hyd

One of the polypeptides was isolated and subjected hydrolysis giving the
following
ng smaller tri-peptide
tri--peptide fragments.
tri
cys-cys-thr,
cys
cys-
-cys ile-val-glu,
cy -thr, ile val--glu, glu-gln-cys,
ile-val glu n-cys, gly-ile-val
glu-gln gly
g -ile
e-val
val
Using the same abbreviations, write out the amino acid sequenceof the smallest
polypeptide that couldproduce the above fragments. [2]

trendylineover
8
(iii) Describe the tertiary structure of insulin A-chain, include the type of bondings or
interactions with reference to all the relevant amino acid residues listed in the above
table. [4]
(iv) In further confirmation of structures of insulin, chemicals can be used to affect the
structures. Suggest one type of bond or interaction from your answer in (b)(iii) that
can be broken by chemicals and state the chemicals that can be used. [2]
(v) Zinc has an important role in the the production, storage and use of insulin. Zinc
cation can bind to insulin through interactions with the amino acids. Suggest the
type of interaction and state an amino acid that may be involved. [1]
(c) Zinc compounds are often used in paints for various purposes. The properties of some of
these compounds are given below.
compound solubility product,K sp use in paints

17
Zn(OH) 2 3.00 x 10 White pigment
23
ZnS 3.21 x 10 Luminous pigment
ZnCO 3 1.46 x 1010 Fire Retardant
(i) Write an expression for K sp for Zn(OH) 2 and determine its solubility. Hence,
calculate the pH of a saturated solution of Zn(OH) 2 . [4]
(ii) In preparation of a water-based luminous paint mixture, all 3 of the above

compounds have to be precipitated. Given that concentration of Zn2+ is
2.00x 107 mol dm3, calculate the minimum amount of S2 that must be present in
250 cm3of this mixture. [2]
[Total: 20]
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9
Aredoxflow batteryis a type of rechargeablebatterywhere rechargeability is provided by two

chemical components dissolved in liquids contained within the system. The two half-cells are
separated by a ion-exchange membrane instead of a salt bridge. A typical redox flow battery
uses vanadium ions and inert electrodes.
(a) Vanadium flow battery stores energy using vanadium redox couples. During the discharge
cycle, V2+ loses an electron to the external circuit to form V3+ in the negative half-cell and
acidified VO 2 + accepts an electron from the external circuit to form VO2+ in the positive
half-cell.
Proton
Exchange
Membrane
Inert electrode Inert electrode
V3+/V2+ VO2+/VO2+
- +
(i) Write out the two half-equations for the electrode processes that occur at the two
half-cells. [2]
(ii) Calculate the e.m.f. of the cell. [1]
(iii) Suggest whyvanadium ionscan beused in this redoxflow battery. [1]
trendyline
(iv) Suggest
st the role of a proton exchange membrane.
est [1]

trendylineover
10
(b) Calcium hydride is used in the synthesis of proton exchange membrane used in the
vanadium flow battery. Data about calcium and vanadium are given below.
Calcium Vanadium
Electronic configuration [Ar]4s2 [Ar]3d34s2
Relative atomic mass 40.1 50.9
Atomic radius/ nm 0.197 0.122
-3
Density/ gcm 1.54 6.07
(i) Using relevant data from the table, suggest why the density of vanadium is
significantly greater than that of calcium. [2]
(ii) Explain why vanadium compounds are usually coloured whereas calcium
compounds are usually colourless. [4]
(c) Compounds of calcium contain the Ca2+ ion. The corresponding ion of vanadium is V2+.
(i) Write an equation to show the third ionization energy for calcium. [1]
(ii) Hence explain why Ca3+ compounds do not exist whilst V3+ compounds do. [2]
(d) The following properties and reactionsare exhibited byCompound X, C 7 H 9 ON.
Compound X is insoluble in dilute NaOH, but dissolves in dilute HCl(aq).
On reaction with acidified potassium dichromate(VI)under certain condition,

compound X forms compound Y, C 7 H 7 ON.
On reaction with ethanoyl chloride, CH 3 COCl, X forms compound Z, C 11 H 13 NO 3 .
Deduce the structures of compounds X, Y and Z. Explain the chemistry of the

reactionsdescribed. Write an equation for the formation of compound Z. [6]
[Total: 20]
trendyline
Higher 2
CHEMISTRY 9647/03
Paper 3 Free Response Friday 26 August 2016
2 hours

Data Booklet

ANSWER SCHEME&
EXAMINERS
COMMENTS
ttrendyline
This
his
d li
is documents consists of 17printed
printed pages and 1 blank

lank page
pages.
nary Examination 2016 [Turn over
255 trendyline
2
(a) When potassium manganate(VII), KMnO 4 , is heated with concentrated sodium hydroxide,
NaOH, bubbles of oxygen are seen and a green solution of MnO 4 2- is obtained. The
addition of barium chloride, BaCl 2 , to this solution precipitated out a solid X with
composition by mass of 53.5% barium, 21.5% manganese and 25.0% oxygen.
(i) Calculate the empirical formula of X. [1]
Element Ba Mn O
% mass 53.5 21.5 25.0
Ar 137 54.9 16.0
No. of 0.391 0.392 1.56
moles
Mole ratio 1 1 4
Empirical formula of X is BaMnO 4
(ii) When the green solution above is acidified, a brown precipitate in a purple solution
is formed.
Suggest the identities of the species formed upon acidification and hence state the
type of reaction that has occured. [3]
Brown precipitate is MnO 2

Purple solution is MnO 4
Disproportionation
(b) A solution of acidified potassium manganate(VII), KMnO 4 , can be standardised through

titration against sodium ethanedioate, Na 2 C 2 O 4 . The ethanedioate ion is oxidised to
carbon dioxide in this reaction.
(i) State the oxidation numbers of C in the ethanedioate ion and in carbon dioxide. [1]
O.N. of C in C 2 O 4 2 = +3
O.N. of C in CO 2 = +4
(ii) Write the half-equation for the oxidation of the ethanedioate ion. [1]
C 2 O 4 2 2CO 2 + 2e
(iii) Hence, write the overall balanced equation for the reaction between acidified
manganate(VII) and ethanedioate ions. [1]
2MnO 4 + 16H+ + 5C 2 O 4 2 2Mn2+ + 10CO 2 + 8H 2 O
trendyline
3
(iv) In one such standardisation procedure, 25.0 cm3 of 0.0150 mol dm3 Na 2 C 2 O 4
solution required 28.85 cm3 of acidified KMnO 4 to reach the end-point.
Determine the concentration of KMnO 4 in the solution. You may assume that
2MnO 4 & 2 O 4 2. [3]
25.0
No. of moles of C 2 O 4 2 = 0.0150
1000
= 0.000375 mol
Since 2MnO 4 & 2 O 4 2,
2
No. of moles of MnO 4 = 0.000375
5
= 0.000150 mol
0.000150
Concentration of KMnO 4 = 1000
28.85
= 0.00520 mol dm3
(c) Myrcene, A and ocimene, B,are isomers with the molecular formula C 10 H 16 . When
subjected to hydrogen with platinum catalyst, both isomers give 2,6-dimethyloctane,
C 10 H 22 .
2,6-dimethyloctane
When treated with hot concentrated acidified KMnO 4 , A gives CO 2 and compound C,
C 7 H 10 O 4 ; B gives CO 2 and compounds D, C 5 H 8 O 3 , and E, C 3 H 4 O 3 .
Compounds C, D andE give one mole of CHI3 with alkaline aqueous iodine. On addition
of aqueous NaHCO 3 , compounds C, D andE produce effervescence.
Suggest structures for A-E, and explain the observations described above. [10]
trendyline
trendylineover
4
C10H22
H2/Pt
hydrogenation / reduction
=> 3 moles H added
2
=> 3 x C=C / alkene in A, B
A B
C10H16 C10H16
KMnO4/H , heat
+
oxidative cleavage
=> 3 C atoms lost as CO in A
C has 4 oxygen atoms => 3 terminal C=C in A
2
=> 1 x CH CO-
3
=> 1 x -CO H or
2 => 2 C atoms lost as CO in B
=> 1 x ketone without 2
adjacent -CH3 => 2 terminal C=C in B
C D E
+ + +
C7H10O4 CO2 C5H8O3 C3H4O3 CO2
KMnO4/H , heat
+
oxidative cleavage
=> C, D and E have ketone and/or carboxylic acid groups
Iodof orm/Triiodomethane test

=> C, D and E have CH CO- groups
3
NaHCO3(aq)
- -
Acid carbonate/acid base/neutralisation reaction
=> C, D and E produce CO
2
=> they have carboxylic acid groups
CO2
HO
O O CO2
Hence, A: CO2 O
HO
O CO2
CO2
Hence, B: O E O
ttrendyline
ine
ne
ne
O
D
HO
HO
[Total: 20]

5
2 The table below lists the standard enthalpy change of formation of four compounds.
Compound H f o/kJ mol1

H 2 O(l) 286
HCl(g) 92.0
SiO 2 (s) 910
SiCl 4 (l) 640
(a) What is meant by the term, standard enthalpy change of formation of a compound? [1]
The enthalpy change when 1 mol of a compound is formed from its elements(in its
most stable form), under standard conditions (25oC, 1 atm pressure).
(b) SiCl 4 (l) undergoes hydrolysis to give SiO 2 (s).

(i) Write the balanced equation with state symbols for the hydrolysis reaction. [1]
SiCl 4 (l) + 2H 2 O(l6L2 2 (s) + 4HCl(g)
(ii) Using the above data, calculate the standard enthalpy change for the hydrolysis
reaction. State one assumption made in your calculation. [1]
H r o H f o(products) H f o(reactants)
= [ 910 + 4(-92.0)] [ 640 + 2( 286)]
= 66.0 kJ mol-1
Assumption:
- SiCl 4 (l) is in excess. The hydrolysis gives HCl(g) instead of HCl(aq).
- Hess Law is followed/obeyed.
(iii) Does the hydrolysis have a positive, negative or zero entropy change? Explain your
answer. [1]
Positive entropy change. 4 moles of gas (HCl) are produced. There is an
increase in disorder of the system as there are more ways of arranging the
partciples in the system.
(iv) Hence, by the use of the Gibbs free energy, Go, explain why the hydrolysis of
SiCl 4 (l) is always a spontaneous process. [1]
o o o
G = H - TS
Since Ho is negative and So is positive, Go is always negative. So the
process is spontaneous.
(c) Consider reaction 1 and reaction 2 shown below.
anhydrous AlCl3
dimethylated benzenes
reacti on 1: + CH Cl
3 CH3 + an other ro ucts
d p d
Heat
reacti on 2:
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re dyliine
re ne + CH
CH3COC
COCll
nhyd
anhydrous
drous
s AlCl
Heat
AllCl3
COCH3
CO

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6
(i) Both reaction 1 and reaction 2proceed via a similar mechanism. Name the type of
reaction undergone. [1]
Electrophilic substitution.
(ii) Suggest why reaction 1 gives a mixture of organic products while reaction 2 gives
only one mono-substituted product. [2]
Reaction 1
The CH 3 is an electron donating or activating group. It activates the benzene
ring and so makes the delocalised electrons more susceptible/available to
electrophilic attack/electrophiles. This favours further substitution to give
multi-substituted products.
Reaction 2
The C=O is an electron withdrawing or deactivating group. It deactivates the
benzene ring and so makes the delocalised electrons less
susceptible/available to electrophilic attack/electrophiles. Further substitution
is less favourable.
(d) The organic product in reaction 2, phenylethanone, COCH3, reacts with HCN to
produce the corresponding cyanohydrin under certain experimental conditions.
(i) State the experimental conditions. [1]
Trace amount of NaOH/NaCN and 10 20oC
(ii) Describe the mechanism of reaction, of phenylethanone with HCN, showing clearly
the curly arrows to indicate the movement of electrons and all charges. [3]
Nucleophilic Addition Mechanism.
HCN H+ + :CN-

O O
+ slow
CH3 H CH2CH3
CN
CN
(intermediate)
O CH3
fast
+ H CN C OH + CN
-
CH3 +
CN CN
(iii) Hence, suggest the reagents and conditions used in the following conversion,
ttrendyline
tr nd
dyyli
stating
g clearly
y the intermediate p
products in the p
process of synthesis.
y [2]
CONH2
COCH
OCH3 C C 3
CH
Cl

7
HCN/
CN COOH
Trace NaOH H2SO4 (aq)
COCH3 - o C CH3 C CH3
10 20 C H t under reflux
ea
OH OH
PCl5
CONH2 COCl
NH3,
C CH3 room temperature C CH3
Cl Cl
(e) The rate of reaction between phenylethanone and iodine in acid medium to give
2-iodo-1-phenylethanone, COCH2I , is found to be independent of [ I 2 ], but
directly proportional to [H+] and directly proportional to [phenylethanone].
(i) Write the rate equation for this reaction and state the overall order and the
units of the rate constant. [2]
+
Rate = k [ COCH3 ][H ]
Overall order = 2, units: mol-1 dm3 s-1
(ii) The reaction between phenylethanone and bromine proceeds by a similar

mechanism. How would you expect the rate of this reaction to compare with
that of the above reaction? Explain your answer. [1]
The reaction rate is unchanged as it is also independent of [Br 2 ] like I 2 .
(iii) When a basic medium is used instead for the reaction between
phenylethanone and iodine, a different mechanism of reaction is followed and
different organic products are produced.
(I) State the type of reaction undergone. [1]
Triidomethane/iodoform reaction.
(II) Give the structures of all the organic products formed in this reaction. [2]
CO2
CHI 3
[Total: 20]
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8
3 Fireworks are a traditional part of many celebrations. Their colours can come from heating
ofGroup II metals and their salts. These salts often contain anions such as chlorates,
perchlorates, and nitrates which are oxidising agents.
(a) One of the Group II metals,M, when heated with oxygen under pressure, forms a metal
peroxide which can be used as anoxidising agent in fireworks to produce a vivid green
colour. The equation for the reaction is shown below:
2MO(s) + O 2 (g) 2MO 2 (s)
When equilibrium is attained, the mixture of oxides was found to have a mass of 1.60g,
where MO 2 has a percentage mass of 18.7%. When the mixture was treated with dilute
sulfuric acid, a white solid was precipitated and a solution of hydrogen peroxide was
produced.
An excess of acidified potassium iodide was added to the hydrogen peroxide solution.
The reaction between hydrogen peroxide and acidified potassium iodide is as follows.
H 2 O 2 + 2I+ 2H+ I 2 + 2H 2 O
The iodine liberated needed 11.80 cm3 of 0.300 moldm3 sodium thiosulfate, Na 2 S 2 O 3 ,for
complete reaction.
I 2 + 2S 2 O 3 2 6 4 O 6 2 + 2I
(i) Write a balanced equation to represent the reaction between MO 2 and sulfuric acid.[1]
MO 2 + H 2 SO 4 062 4 + H 2 O 2
(ii) By determining the amount of MO 2 that has reacted,calculate the relative atomic
mass of M and suggest its identity. [5]
H 2 O 2 + 2I + 2H+ I 2 + 2H 2 O
I 2 + 2S 2 O 3 2 6 4 O 6 2 + 2 I
MO 2 + 2 O 2 I 2 6 2 O 3 2
MO 2 6 2 O 3 2
Amount of S 2 O 3 2= 11.8 x 103 x 0.3
= 3.54 x 103mol
Amount of MO 2 = 0.5 x 3.54 x 103
= 1.77 x 103 mol
Let the relative atomic mass of M be x g
Mass of MO 2 = (x+ 2 x 16.0) x 1.77 x 103
18.7
1.60 =(x+216.0)1.7710-3
100
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=137
Identityty of M: Barium
Bariu

9
(b) Strontium nitrate, Sr(NO 3 ) 2 is an oxidising agent and is commonly used as a red colouring
agent in fireworks.
(i) Write a balancedequation for the reaction that occurs when Sr(NO 3 ) 2
undergoesthermal decomposition. [1]
2SrO(s) + 4NO 2 (g) + O 2 (g)
2Sr(NO 3 ) 2 (s)
(ii) Predictwhether the decomposition temperature of Sr(NO 3 ) 2 will be higher or lower

than the decomposition temperature of Mg(NO 3 ) 2 . Explain your answer. [3]
Higher.
cationic radius Sr2+ is larger than that of Mg2+ and charge density or polarising
power of Sr2+ is smaller.
electron cloud of NO 3 anion is less distorted 12 ERQG ZHDNHQHG WR D

smaller extent, does not break as easily.
Thus Sr(NO 3 ) 2 is thermally more stable than MgNO 3 , and decomposition

temperature is higher.
(c) Anotheroxidising agent used in fireworks is potassium chlorate(V), KClO 3 .When KClO 3
undergoes thermal decomposition, two products are obtained, one of which is KCl.
(i) Write a balanced equation to show how KClO 3 is produced from Cl 2 gas and hot,
aqueous potassium hydroxide. [1]
3Cl 2 (g) + 6KOH(aq) 5KCl(aq) + KClO 3 (aq) + 3H 2 O(l)
(ii) Write a balanced equation for the thermal decomposition of KClO 3 and hence
suggest why KClO 3 is an important ingredient used in fireworks. [2]
2KClO 3 (s) 2KCl(s) + 3O 2 (g)

O 2 gas is produced when heat is applied to potassium chlorate. O 2 gas
supports subsequent combustion of fireworks/explosives, therefore it is an
important ingredient.
(d) Fireworks which produce bright sparks, flashes and coloured flames also involve the
elements phosphorus, sulfur and chlorine.
The table below gives the melting points of these elements.
element phosphorus sulfur chlorine

melting point / K 317 392 172
In terms of structure and bonding, explain why sulfur has the highest melting point among
the three elements. [2]
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ndyy e
ents exist as simple covalent molecules
All 3 elements olecules with van
n de
d
der Waals forces
between the
e molecules.
S 8 has the
he
e largest number of electrons
electrons,, compared to t P4 a and Cl 2 ; it has
the strongest forces, hence
est van der Waals forces ce iit needs the largest amo
amount of energy to
overcome these attractions during melting.

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10
(e) Sodium salicylate and sodium benzoate are used as whistle mixes in fireworks. Both are
white crystalline powder.
OH O O
+ +
O Na O Na
sodium salicylate sodium benzoate
(i) Suggest methods by which sodium salicylate and sodium benzoate can be
distinguished from each other by a simple chemical test. State the reagents and
conditions used and the expected observations for each compound. [2]
Method 1
To 2 separate test tubes containing sodium salicylate and sodium benzoate,
add neutral FeCl 3 (aq). A violet colouration will be observed in the test tube
containing sodium salicylate. No violet colouration is seen in the test tube
containing sodium benzoate.
OR
Method 2
To 2 separate test tubes containing sodium salicylate and sodium benzoate,
add aqueous Br 2 and shake. White precipitate formed in test tube
containing sodium salicylate and orange bromine water decolourises.
Orange aqueous bromine water remains orange in test tube containing
sodium benzoate.
(ii) The pK a values of the two acidic groups in salicylic acid are pK a1 = 2.98 and
pK a2 =13.6.
OH O
OH
salicylic acid
Draw the displayed formula of the mono-anion produced after the dissociation of the
carboxylic acid group and use your formula to explain why the dissociation of the
phenol group is unlikely to occur. [3]

H Intramolecular hydrogen bonding
- O O
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ttr
ren
e O
[Total: 20]

11
4 Strecker synthesis is a method used for the synthesis of amino acids. It is often studied due to
the simplicity of the process.
(a) Alanine, an amino acid, can be formed using this method as shown below.
+
O NH2 Cl NH2
C
NH4Cl H3C C KCN
H3C C NaOH, heat
H3C Products
step 1 step 2 CN step 3
H H
H
(i) Construct a balanced equation for step 1 and suggest the type of reaction that has
occurred. [2]
+
O NH2 Cl
H3C C + NH4Cl H3C C + H2O
H H
Condensation/Addition-Elimination
(ii) Give the structural formulae for allthe products formed in step 3. [2]
NH2 O N
+ H H
CH3 CH C O Na H
(b) Insulin is a hormonal protein which was first discovered in 1921. In 1959, it became the
first protein to have its primary structure determined. These led to the award of two Nobel
Prizes, in Physiology/Medicine and Chemistry respectively.
The basic unit of insulin consists of two polypeptides, A-chain and B-chain. A-chain has
21amino acid residues, and some of these are listed in the following table(You may use
the abbreviations for your answers).
formula of R group side chain number of amino acid

amino acid abbreviation
at pH 7.4 (physiological pH) residues in A-chain
cysteine cys CH 2 SH 4
glutamic acid glu CH 2 CH 2 CO
2 2
glutamine gln CH 2 CH 2 CONH 2 2
glycine gly H 1
isoleucine ile CH(CH 3 )CH 2 CH 3 2
threonine thr CH(OH)CH 3 1
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tren
ndylin
ne
valine val CH(CH
C 3 )CH
CH 3 1
In order to determine
deter
et mine the sequence of the A-chain,
A-cchain, partial hydrolysis was
wa carried out with
two separatee methods to obtain several polypeptide fragments.
fragmen
fragm e tss. One me
method of hydrolysis
involves the use of 6 mol dm-3 HCl or NaOH
NaOH,H while the othermethod cau causes hydrolysis at
specific peptide bonds.

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12
(i) State what may be used in the method for the hydrolysis at specific peptide bonds.[1]
Enzyme
(ii) One of the polypeptides was isolated and subjected for further hydrolysis giving the
following smaller tri-peptide fragments.
cys-cys-thr, ile-val-glu, glu-gln-cys, gly-ile-val
Using the same abbreviations, write out the amino acid sequenceof the smallest
polypeptide that couldproduce the above fragments. [2]
gly-ile-val-glu-gln-cys-cys-thr
(iii) Describe the tertiary structure of insulin A-chain, include the type of bondings or
interactions with reference to all the relevant amino acid residues listed in the above
table. [4]
The tertiary structure of insulin A-chainis the overall 3-dimensional shape of
the protein resulting from folding or coiling of the chains due to various R-
group interactionswithin a polypeptide chain. These may be hydrogen
bonding between R-groups of gln and thrresidues, covalent disulfide linkages
between sulfur of cys residues and van der Waals between R-groups of gly,ile
and val residues.
(iv) In further confirmation of structures of insulin, chemicals can be used to affect the
structures. Suggest one type of bond or interaction from your answer in (b)(iii) that
can be broken by chemicals and state the chemicals that can be used. [2]
Disulfide linkage can be broken by heavy metal ions, such as Ag+ or Hg2+,
hence either AgNO 3 or Hg(NO 3 ) 2 can be used.
(v) Zinc has an important role in the the production, storage and use of insulin. Zinc
cation can bind to insulin through interactions with the amino acids. Suggest the
type of interaction and state an amino acid that may be involved. [1]
Ionic interactions with glutamic acid (glu);OR ion-dipole attractions with
threonine (thr) or glutamine (gln); OR Covalent dative bonds with glutamic
acid (glu), threonine (thr) or glutamin (gln).
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13
(c) Zinc compounds are often used in paints for various purposes. The properties of some of
these compounds are given below.
compound solubility product, K sp use in paints

Zn(OH) 2 3.00 x 1017 White pigment
ZnS 3.21 x 1023 Luminous pigment
10
ZnCO 3 1.46 x 10 Fire Retardant
(i) Write an expression for K sp for Zn(OH) 2 and determine its solubility. Hence,hence
calculate the pH of a saturated solution of Zn(OH) 2 . [4]
2+ -
Zn(OH) 2 (s) Zn (aq) + 2OH (aq)
K sp = [Zn2+][OH-]2
Let solubility of Zn(OH) 2 be xmol dm-3

K sp = (x)(2x)2
3.00 x 10-17 =4x3
3 -17
3.00 10
x= = 1.96 x 10-6 mol dm-3
4
[OH-] = 2x = 2(1.96 x 10-6) = 3.92 x 10-6mol dm-3
pOH = lg (3.92 x 10-6) = 5.41

pH = 14 5.41 = 8.59
(ii) In preparation of a water-based luminous paint mixture, all 3 of the above

compounds have to be precipitated. Given that concentration of Zn2+ is
2.00x 107 mol dm3, calculate the minimum amount of S2 that must be present in
250 cm3of this mixture. [2]
For precipitation, [Zn2+][S2-]>K sp

[S2-] > 3.21 x 10-23 / 2.00 x 10-7
[S2-] > 1.605 x 10-16
Minimum amount of S2- = 1.605 x 10-16 x 250/1000

= 4.0125 x 10-17 mol = 4.02 x 10-17 mol
[Total: 20]
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14
A redox flow battery is a type of rechargeable battery where rechargeability is provided by two
chemical components dissolved in liquids contained within the system. The two half-cells are
separated by a ion-exchange membrane instead of a salt bridge. A typical redox flow battery
uses vanadium ions and inert electrodes.
(a) Vanadium flow battery stores energy using vanadium redox couples. During the discharge
cycle, V2+ loses an electron to the external circuit to form V3+ in the negative half-cell and
acidified VO 2 + accepts an electron from the external circuit to form VO2+ in the positive
half-cell.
Proton
Exchange
Membrane
Inert electrode Inert electrode
V3+/V2+ VO2+/VO2+
- +
(i) Write out the two half-equations for the electrode processes that occur at the two
half-cells. [2]
2+ 3+ -
Negative half-cell: V V + e
Positive half-cell: VO 2 + + 2H+ + e- VO2+ + H 2 O
(ii) Calculate the e.m.f. of the cell. [1]

Eo cell =Eo red Eo oxi =(+1.00) ( 0.26) = +1.26V
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(iii) est
Suggestst whyvanadium ionscan beused se in this redoxflow
redo flow battery.
redox [1]
y to exist in different oxidation states
Ability states
(iv) est
st the role of a proton
Suggest ro exchange membrane. [1]
To maintain
aintain electrical neutrality

15
(b) Calcium hydride is used in the synthesis of proton exchange membrane used in the
vanadium flow battery. Data about calcium and vanadium are given below.
Calcium Vanadium
Electronic configuration [Ar]4s2 [Ar]3d34s2
Relative atomic mass 40.1 50.9
Atomic radius/ nm 0.197 0.122
-3
Density/ g cm 1.54 6.07
(i) Using relevant data from the table, suggest why the density of vanadium is
significantly greater than that of calcium. [2]
Both vanadium and calcium have a metallic structure. The relative atomic
mass of vanadium is higher than that of calcium.The atomic volume
4
(V= r3) of vanadium is lower than that of calcium due to its smaller atomic
3
radius.
With the greater Ar of vanadium and its smaller atomic volume, the density of
vanadium is significantly higher since density = mass/volume.
(ii) Explain why vanadium compounds are usually coloured whereas calcium
compounds are usually colourless. [4]
Vanadium compounds are usually coloured because they have incompletely

filled d- orbitals.In the presence of ligands, the 3d orbitals become non-
degenerate and split into two groups with slightly different energy (d-d*
splitting). When a d-electron from the lower energy group is promoted to the
higher energy group (d-d* electronic transition), radiation in the visible region
of the electromagnetic spectrum is absorbed. Thecomplementary colour not
absorbed will be seen.
Calcium compounds are usually colourless because they have no d-electrons

and so, d-d* electronic transition cannot take place.
(c) Compounds of calcium contain the Ca2+ ion. The corresponding ion of vanadium is V2+.
(i) Write an equation to show the third ionization energy for calcium. [1]
Ca2+(g) Ca3+(g) + e-
(ii) Hence explain why Ca3+ compounds do not exist whilst V3+ compounds do. [2]
Formation of Ca3+ involves removing an electron from the inner principal
ttrendyline
yli
quantum
um shell(3p
shell(3p subshell) which
ch is more e strongly
str attracted by the nucleus
and this
his requires a lla
large electron. Hence Ca3+
rge amount of energy to remove the elec
compounds
ounds do not exist.
exis
3+
Formation
tion of V involves
ation involv remov
removal
al of electrons from the 3d orb
or
orbital which has a
arable energy with that of 4s orbital.
comparable orbital Therefore,
Therefore it isi less strongly
attracted by the nucleus and this requires much less energy to remove the
electron. Hence V3+ compounds can be formed.

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16
(d) The following properties and reactionsare exhibited byCompound X, C 7 H 9 ON.
Compound X is insoluble in dilute NaOH, but dissolves in dilute HCl(aq).
On reaction with acidified potassium dichromate(VI)under certain condition,

compound X forms compound Y, C 7 H 7 ON.
On reaction with ethanoyl chloride, CH 3 COCl, X forms compound Z, C 11 H 13 NO 3 .
Deduce the structures of compounds X, Y and Z. Explain the chemistry of the

reactionsdescribed. Write an equation for the formation of compound Z. [6]
Structures of X, Y and Z are:
O
CH2OH CH2 O C CH3
NH2 NH2 NHCOCH3

X Y Z
Compound Xdissolves in HCl(aq) shows that it contains a basic group.
Compound Xdoes not dissolve in NaOH(aq), Hence, it does not contain a phenol group.
Compound Xundergo oxidation with acidified potassium dichromate (VI) and therefore, it is
a (primary/secondary) alcohol.
Compound Xundergo condensation/ acylation/ addition-eliminationwith ethanoyl chloride to give

compoundZ.
O
C CH3
CH2OH
CH2 O
+ 2 CH3COCl + 2 HCl
NH2
NHCOCH3
[Total: 20]

1
Name: Index Number: Class:
DUNMAN HIGH SCHOOL

Preliminary Examinations 2016
Year 6
H2 CHEMISTRY 9647/01
Paper 1 Multiple Choice 27 September2016
1 hour
Additional Materials: Optical Mark Sheet
Data Booklet
INSTRUCTIONS TO CANDIDATES
1 Write your name and class on this question paper.
2 There are forty questions on this paper. Answer all questions. For each question there are
four possible answers A, B, C and D.
Choose the one you consider correct and record your choice in soft pencil on the separate
Optical Mark Sheet.
3 Each correct answer will score one mark. A mark will not be deducted for wrong answer.
4 Any rough working should be done in this booklet.
5 You may use a calculator.
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This question paper consists of18 printed pages and 0blank page.
DHS 2016 [Turn over
271 trendyline
2
Section A
For each question, there are four possible answers,A, B, C, and D. Choose the one you consider
to be correct.
1 Ferrous sulfate (FeSO 4 ) tablets are commonly prescribed by doctors as 350 mg tablets and
serve as a dietary supplement for pregnant women. However, it was found that these tablets
may cause poisoning in young children if accidentally consumed. The lethal dosage for a
12.0 kg child is 590 mg of Fe2+.
What is the minimum number of tablets that would constitute a lethal dose to a 12.0 kg child?
A 1
B 2
C 4
D 5
2 25.0 cm3 of a solution of 0.0518 moldm3hydroxylammonium chloride, NH 3 OH+Cl was

added to a solution containing an excess of acidified Fe3+ ions and the mixture boiled. The
Fe2+ ions in the resultant solution was titrated with 25.90 cm3 of 0.02 moldm3 potassium
manganate (VII) solution.
Given the mole ratio MnO 4 )H2+, which of the following nitrogencontaining species is
formed in the reaction?
A NH 4 +
B N2O
C NO 2
D NO 3
3 Two elements, Y and Z, have the following properties.
Property 1: Y and Z form ionic compounds Na 3 Y and Na 3 Z respectively.

Property 2: Element Z forms ZCl 5 molecule whereas Y is unable to form YCl 5 .
Which pair of electronic configurations of Y and Z is correct?
Y Z
A [He] 2s2 2p2 [Ne] 3s2 3p3
B [He] 2s2 2p3 [Ne] 3s2 3p3
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C [He] 2s2 2p2 [He] 2s2 2p3
D [Ne] 3s2 3p2 [Ne] 3s2 3p3
DHS 2016 9647/01 [Turn over

272 trendyline
3
4 For one mole of an ideal gas, which plot produces a straight line graph passing through the
origin?
Yaxis Xaxis
A PV P at constant T (K)
B P V at constant T (K)
C P T (C) at constant V
D P 1/V at constant T (K)
5 Use of Data Booklet is relevant to this question.

Which substance is considered to have the largest covalent character?
A AlF 3 B Al 2 O 3 C Be 3 N 2 D BeO
6 Which substance does not contain an atom that has an unpaired electron?
A ClO 2 B NO C NO 2 D N2O
7 Ammonia is made via the Haber Process. The reactants are nitrogen and hydrogen.
N 2 (g) + 3H 2 (g) 2NH 3 JH = 92 kJ mol1
What will increase the rate of the forward reaction?
A Adding argon to the mixture but keeping the total volume constant.
B Decreasing the temperature.
C Increasing the total pressure by reducing the total volume at constant temperature.
D Removing nitrogen from the mixture but keeping the total volume of the mixture the
same.
8 How much water must be added to a 10 cm3solution of 0.05 moldm3 sulfuric acid in order to
increase its pH to 2.0?
A 10 cm3
B 50 cm3
C 90 cm3
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D 100 cm3

273 trendyline
4
9 Given that the K sp for magnesium hydroxide, Mg(OH) 2 , is 1.80 x 1011 mol3dm9 at 298 K,
calculate the pH of a saturated solution of Mg(OH) 2 .
A 3.48
B 3.78
C 10.2
D 10.5
10 The reaction of nitrogen monoxide and hydrogen gas
2NO(g) + 2H 2 (g) N 2 (g) + 2H 2 O(g)
is hypothesised to involve the following steps:
I NO + NO N 2 O 2 (fast)
II N 2 O 2 +H 2 H 2 O + N 2 O (slow)
III N 2 O +H 2 N 2 +H 2 O (fast)
Which of the following is true about the reaction?
A H 2 acts as a catalyst in this reaction.

B The overall order of the reaction is 2.
C There are 2 intermediates present in the reaction mechanism.
D Increasing the concentration of NO will increase the rate constant.
11 The radius and charge of each of the six ions are shown in the table.
ion J+ L+ M2+ X Y Z2
radius / nm 0.14 0.18 0.15 0.14 0.18 0.15
Which of the following pair shows the first compound having a smaller magnitude of lattice
energy than the second?
A JX, MZ
B JX, LX
C JY, LX
D MZ, LY

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5
12 The common rubber band has very interesting thermodynamic properties due to its
randomly coiled long polymeric molecular structure. When the rubber band is stretched, a
slight warming effect is felt.
:KDW DUH WKH FRUUHFW VLJQV RI 6 + DQG * LI WKH VWUHWFKHG UXEEHU EDQG LV UHOHDVed
quickly?
S H G
A + +
B + +
C +
D +
13 The nickelcadmium cell is a rechargeable battery which contains an alkaline electrolyte

such as aqueous KOH.
During the discharging process, Cd is oxidised to solid Cd(OH) 2 whileNiO(OH) is reduced to

solid Ni(OH) 2 .
Which statement is true about this rechargeable battery?
A Water is produced in the discharging process.

B The mass of cadmium remains unchanged.
C The alkaline electrolyte can be replaced by an acid.
D The concentration of the alkaline electrolyte remains unchanged in the discharging
process.
14 Which statement regarding the oxides across Period 3 is true?
A The covalent character decreasesfrom Na to S.
B The oxides of the elements changes from basic to neutral then to acidicfrom Na to S.
C The oxides formed are increasing soluble in water from Na to S.
D The standard entropy change of formation of the oxides becomes morenegativefrom

Na to Al.
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6
15 The following information is about a Period 3 element L.
The oxide of L is a solid at room temperature.

The oxide of L, when added to water, gives a non-acidic solution.
The aqueous chloride of L gives a white precipitate with aqueous sodium hydroxide.
In which Group of the Periodic Table could L be found?
A Vonly
B I and III only
C II and III only
D II, III and IVonly
16 Which property shows an increasing trend down Group II from Mg to Ba?
A Polarising power of metal cation

B Second ionisation energy
C Reducing strength
D Melting point
17 Which statement regarding the halogens or their hydrides is correct?
A HCl has a higher melting point than HF due to its larger electron cloud.
B Iodine, when dissolved in hexane, gives a colour that is similar to its vapour.
C The halogens become less volatile from fluorine to iodine due to the weaker covalent
bonds.
D HF is less thermally stable than HI because of the larger electronegativity difference
between the H and F atoms.
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18 Photolysis of a solution of Fe(CO) 5 in ethanoic acid produces Fe 2 (CO) 9 according to the

following equation.
O
CO C
OC CO
OC O
C
2 Fe CO
OC Fe Fe CO + CO
OC CO
CO OC C
O
What is the oxidation state of Fe in Fe(CO) 5 and the coordination number of Fe in

Fe 2 (CO) 9 ?
oxidation state of Fe coordination number of Fe

in Fe(CO) 5 in Fe 2 (CO) 9
A +5 9
B +5 6
C 0 9
D 0 6
19 The structure of 11-ketotestosterone, a sex hormone in fish, is shown below.
OH
O
Which statement about 11-ketotestosterone is correct?
A Its molecular formula is C 19 H 26 O 3 .

B It has a total of 27 stereoisomers.
C It has six sp2-hybridised carbon atoms.
D It has a tertiary alcohol functional group.
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20 The following compounds have the same molecular formula.
Cl Cl Cl H
Cl Cl
H CH3 Cl CH3
X Y Z
Which of the following best describes the isomeric relationships between the compounds?
X and Y Y and Z
A chain optical
B positional functional group
C cistrans positional
D positional chain
21 Which of the following is a non-greenhouse gas that could be released from the catalytic
converter of a car exhaust?
A CO 2
B H2O
C CH 4
D N2
22 Which compound is not possibly formed when cyclopentane is reacted with excess bromine
gas in the presence of ultraviolet light?
Br
A Br B
Br
C D
Br Br
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23 Carbonyl groups in aldehydes and ketones, C=O, undergo nucleophilic addition while alkene
groups, C=C, undergo electrophilic addition.
Which statement explains the above reactions?
A Oxygen is more reactive than carbon.

B The different lengths of the double bonds.
C The different strengths of the double bonds.
D The electronegativity difference between the carbon and oxygen atoms in the carbonyl
group.
24 The citrus flavour of lemons is due to the compound limonene, present in both the peel and
the juice.
limonene
Limonene is separately treated with

cold, dilute acidified KMnO 4 ,
hot, concentrated acidified KMnO 4 .
What is the change in the number of chiral carbon atoms in the molecule during each
reaction?
cold, dilute acidified KMnO 4 hot, concentrated acidified KMnO 4

A +3 0
B +3 1
C +4 0
D +4 1
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25 The diagram shows the structure of a derivative of propofol.
When reacted with a dilute solution of Cl 2 , a chlorine atom may substitute a hydrogen atom
on the benzene ring but not for a hydrogen atom on the alkyl branches.
Given that any number of the benzene hydrogen atoms may be substituted, how many
possible products of the reaction are there?
A 3
B 4
C 5
D 6
26 In the body, cellular respiration produces energy from the oxidation of glucose.
The diagram shows the structure of glucose.
OH
H O OH
H
OH H
HO H
H OH
A new artificial sweetener has been produced by replacing all of the hydroxyl groups
attached directly to the ring carbon atoms in glucose with chlorine atoms.
What is the empirical formula of this chlorinated glucose?
A CH 2 Cl
B C 3 H 4 Cl 2 O
C C 6 H 7 Cl 5 O
D C 6 H 8 Cl 4 O 2
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27 Tetrangomycinis one of the first member of the class of antibiotics under the angucycline
group. What is the maximum number of optical isomers that can be obtained when
1 mole of tetrangomycinfully reacts with NaBH 4 ?
O CH3
O
OH
OH O
T et rangomy ci n
A 2
B 8
C 16
D 32
28 The small hive beetle, which invades colonies of the honeybee, identifies these colonies by
detecting the bees own alarm signal, the pheromone 3-methylbutyl ethanoate.
How may this ester be made in the laboratory?
A CH 3 COCl + (CH 3 ) 2 CHCH 2 CH 2 OH ester + HCl

B CH 3 COCl + CH 3 CH 2 CH(CH 3 )CH 2 OH ester + HCl
conc. H2SO4
C (CH3)2CHCH2CO2H + CH3CH2OH ester + H2O
heat
conc. H2SO4
D (CH3)2CHCH2CH2CO2H + CH3CH2OH ester + H2O
heat
29 Why are amides, RCONH 2 , less basic than amines, RNH 2 ?
A Amides form a zwitterion in which the nitrogen atom carries a positive charge.
B Amides have a resonance structure involving the movement of a pair of electrons from
the nitrogen atom to the oxygen atom.
C
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ns on the nitrogen atom of amides move
Electrons
haracter
aracter so that it is more difficult to break.
bond character
mide
ve on the C-N
de carbonyl group withdraws electrons from the -NH

The amide
en atoms acidic.
hydrogen acidic
break
C-
C-N bond giving
NH 2 g
giv it some double
group to make the

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30 3-aminoisobutyric acid was shown to prevent diet induced diabetes in mouse. It has the
structure shown below.
H2N OH
Which statement about 3-aminoisobutyric acid is not true?
A It migrates to the cathode at pH 10.

B It exists predominately as a zwitterion at pH 7.
C It reacts with ethanoyl chloride to form an amide.
D It exists as a crystalline solid at room temperature.
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Section B
For each question, one or more of the three numbered statements 1 to 3 may be correct.
against the statements which you consider to be correct).

A B C D
1, 2 and 3 1 and 2 only 2 and 3 only 1 only
are correct are correct are correct is correct
31 Which statement about ethanoic acid can be deduced from the sketch below?
Ka of ethanoic
acid
T / C
1 The ionic dissociation of ethanoic acid is an endothermic process.

2 The pH of the ethanoic acid decreases with increasing temperature.
3 At T = 40 C, pH of ethanoic acid = 14 pOH
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A B C D
32 The following graph represents how the solubility of a sparingly soluble salt lead(II) chloride,
PbCl 2 , changes upon addition of solid potassium chloride.
solubility of PbCl2
Z
mass of KCl added
1 The K sp value decreases along XY and then increases along YZ.

2 The change in solubility along XY is caused by common ion effect.
3 The change in solubility along YZ is caused by the formation of a complex between

Pb2+ and Cl ions.
33 In a chemical reaction, P reacts with Q to form R. The rate equation is found to be

rate = k [P] [Q].
The energy profile diagram for the reaction is as shown.
energy
progress of reaction
Which is the likely overall equation of the above reaction?
1
2
3
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R
2P + QR
R
P + 2QR
R
P + QR

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A B C D
The half-cells for four metals: Mg, X, Y and Z were in turn connected in pairs and the
potential difference was recorded at room temperature.
salt bridge
metal metal
1 moldm3 of the metal 1 moldm3 of the metal

cation solution cation solution
The results obtained are as shown in the table below.
positive electrode negative electrode

o
E /V
X Mg +2.10
Y Mg +2.72
Mg Z +0.33
Which of the following statements is true?
1 Yis likely to be copper metal.

2 X is stronger than Y in terms of reducing power.
3 Ease of oxidation of metals: Z<X<Y.
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16

A B C D
35 Solid P dissolves in aqueous chlorine to give a solution Q which gives precipitate R on adding
excess aqueous sodium thiosulfate followed by aqueous lead(II) nitrate.
Which combination could agree with the procedure above?
Identity of P Colour of Q Colour of R

1 NaI brown mixture of white and bright yellow
2 NaBr orange white only
3 NaCl colourless white only
36 Consider the two reactions of Cu2+(aq) below.
[Cu(H 2 O) 6 ]2+ + EDTA4 [Cu(EDTA)]2 + 6H 2 O (equilibrium 1)
[Cu(H 2 O) 6 ]2+ + 4NH 3 [Cu(NH 3 ) 4 (H 2 O) 2 ]2+ + 4H 2 O (equilibrium 2)
What can you deduce from the equilibria above?
1 The entropy change of equilibrium 1 is more positive than that of equilibrium 2.

2 [Cu(NH 3 ) 4 (H 2 O) 2 ]2+ in equilibrium 2 has two possible isomers:
2+ 2+
H2O NH 3
H3N NH 3 H2O NH 3
Cu Cu
H3N NH 3 H2O NH 3
H2O NH 3
3 EDTA4 is a stronger ligand than NH 3.
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A B C D
37 Compounds L and M are precursors to the synthesis of some analgesic drugs.
O CH3
OH
OH OH
CHO
O
H3C
L M
Which statement is true?
1 Only L reacts with KBr in concentrated H 2 SO 4 to give a bromine-based compound

under heat.
2 Both L and M react with HCN to form a product with at least one chiral carbon atom.
3 L is expected to be more acidic than M.
38 Which of the following will yield an organic compound containing deuterium? (D = 2H)
O DCl (D2O)
1 C NH2
heat
O O
dil D2SO4
2 C O C CH3
D2O
O
LiAlD4
3 C OH
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18

A B C D
39 Which reagent can be used to distinguish catechol from benzene 1,2 dicarboxylic acid?
OH
OH
catechol
1 Sodium bicarbonate solution

2 Neutral iron(III) chloride solution
3 Aqueous bromine solution
40 Aspartame is an artificial sweetener used as a sugar substitute in some foods and

beverages. The structure is shown below:
O OCH3
N
H
OH NH2 O
Which deduction about the reactions of aspartame can be made from this structure?
1 It undergoes hydrolysis to form two -amino acids.

2 It reacts with 2,4-dinitrophenylhydrazine to give an orange precipitate.
3 The solution remains orange when heated with acidified potassium dichromate(VI).
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2016 DHS H2 CHEMISTRY YEAR 6PRELIMS
Paper 1 MCQ Answers
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
D B B D C D C C D C A A D D C C B D A B
21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40
D C D A C B C A B A B C B B A B A A A D
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2
DUNMAN HIGH SCHOOL

Preliminary Examination 2016
Year 6
Paper 2 Structured 16 September 2016
2 hours
1 Write your name, index number and class on this cover page.
2 Answer allquestions.
3 Write your answers in the spaces provided on the question paper.
4 A Data Booklet is provided.
5 The number of marks is given in brackets [ ] at the end of each question or part question.
6 You may use a calculator.
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tre
end
e
en
n
nd
ddylin
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y lin
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ne
Question
1 2 3 4 5 Total %
No.
Marks
12 15
5 15 15
1 15
1 [[72]
This question paper consists of16 printed pages and 2blank pages.
DHS 2016 [Turn over
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2
Answer all questions in the spaces provided.
1 Planning (P)
The reaction between peroxodisulfate ions, S 2 O 8 2, and ethanedioate ions, C 2 O 4 2, is

slow and can be catalysed by Cu2+ ions.
S 2 O 8 2+ C 2 O 4 2 2SO 4 2 + 2CO 2
To determine the rate law of this reaction, it is necessary to selectively vary the
concentrations of S 2 O 8 2 and C 2 O 4 2 ions and determine how the rate of reaction
responds to these changes. The concentrations of the reactants are varied in such a
way that one is in excess compared to the other in each experiment.
A suitable end point (the point at which the final time reading is made) for the
experiments will be when the reaction produced the same volume of CO 2 gas. With
the measured reaction time, relative rate of the reaction can be determined.
You are required to write a plan to determine the rate law of the reaction between
S 2 O 8 2 and C 2 O 4 2 ions.
(a) Suggest an explanation why this reaction is slow when performed in the absence
of a catalyst.
[1]
(b) You may assume that you are provided with
1.00 moldm3peroxodisulfate ions

1.00 moldm3ethanedioate ions
10 cm3 aqueous copper (II) ions
the equipment and materials normally found in a school laboratory.
It can be assumed that a reactant is in excess if its volume is at least five times
the volume of the other reactant used.
Your plan should include the following:
quantities of reactants and condition you would use in four differentreaction

mixtures
the measurements you would take
an outline of how one of the reaction mixtures is prepared
brief, but specific details of how the results would then be used to determine
the rate law of reaction
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[8]
(c) Temperature can also affect the rate of reaction and the activation energy, E a , of
this reaction can be found by repeating the experiments at several different
temperatures.
Using equation (1) and by means of a suitable graph, the activation energy of
the reaction can be determined.
Ea 1
ln (relative rate) = ( ) + ln (constant) (1)
R T
Briefly describe, with specific experimental details, of how the activation energy,
E a , of the reaction could be determined.
[3]
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[Total: 12]

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5
2 (a) A leadacid car battery is a reversible cell that consists of a lead anode and a
grid of lead coated with lead (IV) oxide as the cathode. The electrolyte is a 30%
solution of sulfuric acid. When the cell supplies electric current to power the car,
the process is known as discharging. The reversible process is thus known as
charging.
The overall reaction that takes place in the leadacid car battery is as follows:
discharging
Pb(s) + PbO2(s) + 2H2SO4(aq) 2PbSO4(s) + 2H2O(l)
charging
(i) Write the halfequations, with state symbols, for the reactions that take
place at the anode and the cathode during the discharging process.
Hence, state the polarity at the two electrodes.
Halfequations Polarity
Anode
Cathode
[3]
(ii) When the lead and lead(IV) oxide have been converted to lead(II) sulfate,
the cell can no longer give a current and the battery becomes flat. As the
car moves, the generator then charges the battery. When the leadacid
battery is fully charged, the sulfuric acid has a relative density of about
1.275.
Predict and explain what happens to the relative density of the sulfuric acid
during the discharging process.
[2]
(iii) Overcharging the leadacid battery with high voltages causes hydrogen
and one other gas to form. In addition, the electrolyte level is observed to
have dropped.
Explain briefly what happens during overcharging and hence, suggest the
identity of the other gas that is formed.
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(iv) A simple rechargeable cell similar to that of leadacid car battery may be
constructed by dipping two lead electrodes into aqueous lead(II) nitrate
and passing a current for a few minutes. During the charging process,
lead(IV) oxide is deposited on one of the electrodes. By reference to the
Data Booklet, calculate the value of E when the cell discharges.
[2]
(v) The voltage of a typical leadacid battery is 2.0V. Explain the difference in
the voltage and the E calculated in (a)(iv), based on the concentration of
ions.
[2]
(b) (i) Pb2+ ions are often used in qualitative analysis to identify halide ions as
they form insoluble precipitates. However, it is not an ideal test to
distinguish between Cl and Br ions as both ions form white precipitate
with Pb2+ ions.
Suggest another simple chemical test involving precipitation that could be

used to distinguish between Cl and Br ions, stating clearly the steps and
reagents involved and the expected observations.
[2]
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(ii) With reference to your answer in (b)(i), explain the chemistry involved and
writing equations where appropriate.
[2]
[Total: 15]
3 Cobalt and vanadium are transition elements with more than one oxidation state and
many of its compounds are coloured.
(a) When a few drops of aqueous ammonia is added to a testtube containing

Co3+(aq), a brown precipitate, X is observed. The chemical formula of X does
not contain water molecules. The precipitate then dissolves in excess aqueous
ammonia to give a cationY which has a coordination number of 6.
(i) Complete the electronic configuration of cobalt (III) ions.
Co3+: 1s22s22p6
[1]
(ii) Suggest the identities of X and Y.
X:
Y:
[2]

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8
(iii) With the use of appropriate ionic equations, explain the formation of X and
Y.
[3]
(b) When concentrated hydrochloric acid is added to Co2+(aq), the colour changes
from pink to blue. When water is added to the blue solution, it returns to the pink
colour.
The chemistry of Co2+(aq) with concentrated hydrochloric acid closely resembles

that of Cu2+(aq).
Write a balanced ionic equation to account for the observations. In your answer,
state the change in coordination number of cobalt ion in this reaction (if any).
[2]
(c) Vanadium is also another commercially important transition element.
(i) Explain why V2+ is coloured.
[2]

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9
(ii) V 2 O 5 is used as a catalyst to speed up the conversion of SO 2 into SO 3 in

the contact process for making sulfuric acid.
2SO 2 (g) + O 2 (g) 2SO 3 J+ 197 kJ mol1
For the reaction above, explain clearly how the catalyst works.
[2]
(iii) When a 2:1 ratio of sulfur dioxide and oxygen is passed over V 2 O 5 , the
catalyst in a fixed volume steel vessel at 430 C, the percentage
conversion of SO 2 to SO 3 is 95%.
Given that K p is 7200 atm1 at 430 C, calculate the initial total pressure, in
atm, in the steel vessel.
[2]
(iv) Comment on the effect on the rate of conversion if another unreactive but
toxic gas was accidentally added to V 2 O 5 .
[1]
[Total: 15]
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4 One of the factors that establishes the quality of a water supply is its degree of
hardness. Water hardness is usually reported as parts per million (ppm) of calcium
carbonate in the water sample.
mass of CaCO3
ppm CaCO 3 = x 106
mass of water
Water Supply Classification

calcium carbonate (ppm) Hardness Level
043 soft
43150 slightly hard
150300 moderately hard
300450 hard
>450 very hard
Water hardness can be determined by titrating Ca2+ ions with

ethylenediaminetetraacetic acid (represented by H 4 Y).
HOOC CH2 CH2 COOH

N CH2CH2 N
HOOC CH2 CH2 COOH
H4Y
The titration is often carried out in a buffered basic medium, where H 4 Y exists mainly
as HY3 (buffered solution).
Ca2+(aq) + HY3DT&D<2(aq) + H+(aq) where Y = C 10 H 12 N 2 O 8
(a) A 50 g sample of hard water was titrated against the buffered solution of
concentration 0.0149 moldm3. The volume of the buffered solution required was
25.55 cm3.
(i) Calculate the mass of CaCO 3 present in the water sample.
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11
(ii) Hence calculate the ppm of CaCO 3 in the water sample and determine its
hardness level.
[2]
There are two types of water hardness, temporary and permanent. The difference is
due to the presence of different dissolved calcium compounds in the water.
Temporary hardness is caused by the presence of dissolved calcium

hydrogencarbonate, Ca(HCO 3 ) 2 . This type of hardness is called temporary hardness
because the calcium ions can be removed from the water causing it to precipitate as
CaCO 3 .
Ca2+(aq) + 2HCO3 (aq) CaCO3(s) + H2O(l) + CO2(aq) + SRVLWLYH
(b) Using the given equilibrium, suggest and explain one way how the removal of
Ca2+ from the water sample can be enhanced.
[2]
A common detergent contains sodium dodecylbenzenesulfonate, C 18 H 29 SO 3 Na. In

hard water, it is ineffective as a detergent because it reacts with calcium ions to give a
precipitate.
(C 18 H 29 SO 3 ) 2 Ca(s) Ca2+ (aq) + 2C 18 H 29 SO 3 (aq)K sp = 1.2 x 1017 mol3dm9
A typical sample of hard water has a concentration of calcium ions of

2.5 x 104moldm3.
(c) (i) Calculate the maximum concentration of C 18 H 29 SO 3 in a solution of hard

water.
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The manufacturers claim that the detergent contains 17.4% by mass of

C 18 H 29 SO 3 Na [M r = 348]. In hard water, 1.0 g of the detergent should be used
per dm3 of hard water.
(ii) Calculate the number of moles of C 18 H 29 SO 3 Na added to 1 dm3 of hard

water.
[1]
(iii) Using your answer in (c)(i) and (c)(ii), show that 99% of C 18 H 29 SO 3 Na in
the detergent added will precipitate out of the hard water.
[2]
(d) In order for the detergent to be used in hard water, sodium tripolyphosphate,
Na 5 P 3 O 10 , is added as a water softening agent.
The sodium tripolyphosphate softens water by complexing with calcium ions.
Equilibrium 1: Ca2+ (aq) + P 3 O 10 5 (aq) CaP 3 O 10 3 (aq)

K c = 7.7 x 108mol1 dm3
(i) Explain qualitatively why the addition of Na 5 P 3 O 10 will allow the detergent
to be used in the hard water.
[2]

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(ii) What is the oxidation state of phosphorus in sodium tripolyphosphate?
[1]
(iii) Suggest a likely structure for the tripolyphosphate anion.
[1]
(iv) Magnesium ions can also cause water hardness. It forms a complex with
tripolyphosphate ions as well.
State the effect, if any, of adding magnesium ions on the equilibrium

position and value of K c of Equilibrium 1 at constant temperature. Explain
your answer.
[2]
[Total: 15]
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5 The male silk moth secretes juvenile hormone, C 16 H 26 O 4 , which contains an

unknown number of epoxide rings. Epoxide rings are readily hydrolysed by cold
aqueous acid.
OH OH
1 O 3 1 3
R R H+ R R
C C C C
2 4 2 4
R R R R
The reactions that juvenile hormone and the resulting derivatives undergo are shown
in the table below.
Reactant Reagent Result

hydrogen in the presence
S, C 16 H 28 O 4 , formed.
of a palladium catalyst
Juvenile hormone T, C 16 H 30 O 6 , containing four
cold dilute hydrochloric
alcoholic groups and three
acid
chiral centres is formed.
warmed with aqueous
Methanol and U, C 15 H 28 O 6
T sodium hydroxide and then
are formed.
acidified
V, C 15 H 24 O 6 , which has two

U Mild oxidation
alcoholic groups, is formed.
hot concentrated acidified Two moles of carbon dioxide

V KMnO 4 and one mole of W,
C 13 H 22 O 5 are formed.
2,4
dinitrophenylhydrazine orange precipitate formed.
W reagent
alkaline aqueous iodine yellow precipitate formed.
In addition, it is known that juvenile hormone has a continuous 12carbon long

backbone. There are three methyl substituents on the skeletal backbone of juvenile
hormone and that each methyl substituent is five carbon atoms apart from the next
methyl substituent.
(a) Give the products that will be formed when methylethyl ether, CH 3 OCH 2 CH 3
undergoes hydrolysis with aqueous acid.
[1]
(b) State and explain the number of epoxide ring(s) in juvenile hormone.
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15
(c) State the type of reaction that T has undergone and the functional group that it
contains other than the four alcoholic groups.
[1]
(d) Classify the two alcoholic groups in V into either primary, secondary and tertiary
alcohols. State the number of each alcohol and explain how you arrive at your
conclusion.
[2]
(e) V produced an intermediate upon reacting with hot concentrated acidified

KMnO 4 which eventually produced carbon dioxide. Draw the displayed formula
of this intermediate.
[1]
(f) State the type of reaction between W and 2,4 dinitrophenylhydrazine reagent.
State the deduction about W from the result of W reacting with aqueous alkaline
iodine.
[2]

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(g) Suggest the structures for compounds S to W and for juvenile hormone.
Compound Structure
Juvenile
hormone
[6]
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1 (a)
Repulsion between two negatively charged ions causes the activation energy to
be high.
[1]
(b)
Preparation of reaction mixture
1. Using a 50.0 cm3 measuring cylinder, add 25.0 cm3 of peroxodisulfate ions
into a 250 cm3 conical flask.
2. Using a 10.0 cm3 measuring cylinder, add 2.0 cm3 of aqueous copper (II)
ions into the same conical flask.
3. Using a 50.0 cm3 measuring cylinder, add 45.5 cm3 of deionised water into
the conical flask.
4. Using a 10.0 cm3 measuring cylinder, measure out 2.5 cm3 of ethanedioate
ions.
5. Transfer the ethanedioate ions into the conical flask and insert a rubber bung
into the conical flask. The rubber bung has a delivery tube connected to
rubber tubing with the other end of the tubing inserted into an inverted
burette filled with water.
6. Start the stopwatch immediately and gently swirl the conical flask
continuously.
7. Monitor the water level in the burette and stop the stopwatch when
40.00 cm3 of CO 2 is produced. Record the time taken.
8. Repeat step 1 to 7 using the following volumes of reactants, copper (II) ions
and deionised water shown in experiment 2 to 4, at the same temperature.
Experiment Volume of Volume of Volume of Volume of

S 2 O 8 2 / cm3 C 2 O 4 2 / cm3 Cu2+ / cm3 water / cm3
1 25.0 2.5 2.0 45.5
2 25.0 5.0 2.0 43.0
3 2.5 25.0 2.0 45.5
4 5.0 25.0 2.0 43.0
Treatment of results
1. Relative rates (= 1/t) of expt 1 to 4 are calculated. Since total volume of

mixture is constant in expt 1 to 4, concentration of reactant is proportional to
its volume used.
2. Compare the relative rates of expt 1 to 2 and 3 to 4, to find the order of
reaction with respect to (w.r.t) C 2 O 4 2 and S 2 O 8 2 respectively. If volume of
C 2 O 4 2 doubles and rate remains the same, it is zero order w.r.t C 2 O 4 2. If
volume of C 2 O 4 2 doubles, and rate remains doubles, it is first order w.r.t
C 2 O 4 2. If volume of C 2 O 4 2 doubles and rate quadruples, it is second order
w.r.t C 2 O 4 2. The same applies for S 2 O 8 2.
3. The rate law of reaction can then be found, rate = k[S 2 O 8 2]n[ C 2 O 4 2]m,
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where
here n and m are the orders of reaction r t S 2 O 8 2 and
w.r.t to
C 2 O 4 2respectively.
[8]

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2
(c)
1. Repeat one of the experiments (e.g. expt 2) at two (at least) different
temperatures, other than that for experiment 1 to 4 above. This can be done
by immersing conical flasks in water bath maintained at different constant
temperatures e.g. 40 C and 60 C.
2. Using the results in experiment 2 and that of the two further experiments,
relative rate, followed by ln (relative rate) for each expt is calculated.
1
3. A graph of ln (relative rate) against is plotted. The gradient of the best fit
T
E
line is then determined, where gradient = a . E a is given by gradient x
R
R.
[3]
[Total: 12]
2 (a) (i) Halfequations Polarity

2
Anode Pb(s) + SO 4 (aq) PbSO 4 (s) + 2e
PbO 2 (s) + 4H+(aq) + SO 4 2(aq) + 2e

Cathode +
PbSO 4 (s) + 2H 2 O(l)
[3]
(ii)
The relative density of the sulfuric acid will decrease.
During discharging, as sulfuric acid is used up to produce PbSO 4 , the

concentration of sulfuric acid will decrease, resulting in a decrease in
density.
[2]
(iii)
Overcharging will result in electrolysis of water.

Identity of other gas: Oxygen
[2]
(iv)
E = 1.47 (0.13) = +1.60 V
[2]
t d li
trendyline
(v)
Lead acid battery has a higher voltage as PbSO 4 form

Leadacid formed is insoluble,
which resulted in a lower concentration of Pb2++ in
n the electrolyte,
e thus
driving the forward reaction.
[2]

309 trendyline
3
(b) (i)
To 1 cm3 of halide ions, add AgNO 3 (aq) dropwise. Then add aqueous NH 3
in excess.
Cl ions form white ppt with AgNO 3 which is soluble in excess NH 3 (aq).
Br ions form cream ppt with AgNO 3 which is insoluble in excess NH 3 (aq)
[2]
(ii)
Ag+ (aq) + X (aq) AgX (s), where X is Cl and Br

Both halide ions form insoluble ppt with Ag+.
Ag+ (aq) + 2NH 3 (aq) [Ag(NH 3 ) 2 ]+ (aq)

Ag+ ions form soluble diammine complex which decreases the [Ag+],
resulting in a corresponding decrease in ionic product (i.e. I.P = [Ag+][X])
for both halide ions.
As K sp value of AgCl is much larger than that of AgBr, the ionic product of
AgCl will fall below its Ksp but not for AgBr.
[2]
[Total: 15]
3 (a) (i)
Co3+: 1s22s22p63s23p63d6
[1]
(ii) Suggest the identities of X and Y.
X: Co(OH) 3
Y: [Co(NH 3 ) 6 ]3+
[2]
(iii)
[Co(H 2 O) 6 ]3+ + 3OH Co(OH) 3 + 6H 2 O (1)
When aqueous ammonia is added in excess, a ligand exchange reaction

occurs. The stronger NH 3 ligands replace weaker H 2 O ligands in the
[Co(H 2 O) 6 ]3+ ions to form [Co(NH 3 ) 6 ]3+ complex.
[Co(H 2 O) 6 ]3+(aq) + 6NH 3 (aq) [Co(NH 3 ) 6 ]3+(aq) + 6H 2 O(l) (2)
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3+
This decreases the concentration of [Co(H [C 2 O) 6 ] in solution.
s By Le
Chateliers Principle, equilibrium (1) shifts left to increase ththe concentration
of [Co(H 2 O) 6 ]3+
3
(aq). Hence the brown precipitate of Co(OH
Co(OH) 3 dissolves [1].
[3]

310 trendyline
4
(b)
[Co(H 2 O) 6 ]2+ + 4Cl [CoCl 4 ]2 + 6H 2 O
There is a change of coordination number from 6 to 4.

[2]
(c) (i)
The partiallyfilled d orbitals of V2+ are split into two groups of different
energy levels by H 2 O ligands. When white light shines on the complex, a d
electron undergoes dd transition and is promoted to a higher energy d
orbital. During the transition, the d electron absorbs light from the yellow
region of the visible spectrum. The colour observed is the colour of
transmitted light, which is a mixture of remaining wavelengths that have
not been absorbed.
[2]
(ii)
The reactant molecules are physically adsorbed onto the catalyst surface.
This allows for formation of weak bonds between reactants and the
surface catalyst, thus weakening the intramolecular bonds in the reactants
and helps to catalyse the reaction. After reaction, the reactant molecules
desorb from the catalyst surface.
[2]
(iii)
2SO 2 (g) + O 2 (g) 2SO 3 (g)

Initial pressure
0.6667x 0.3333x 0
/atm
Change in
0.6333x 0.3167x +0.6333x
pressure /atm
Equilibrium
0.0334x 0.0166x 0.6333x
pressure /atm
Let the initial total pressure be x atm.
K p = (0.6333x)2 / (0.0166x)(0.0334x)2 = 7200

x = (0.6333)2 / 7200(0.0166)(0.0334)2
= 3.01 atm
[2]
(iv)
Rate of conversion will slow down/decrease due to poisoning of the
catalyst.
[1]
[Total: 15]
4 (a) (i)
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No. off moles
N H 3 required = 0.0149 x
l of HY
25 5
25.55
1000
= 0.00038070 mol

311 trendyline
5
No. of moles of Ca2+ present = 0.00038070 mol

No. of moles of CaCO 3 = 0.00038070 mol
Mass of CaCO 3 = 0.00038070 x [40.1 + 12 + 3(16)]
= 0.0381g (3 sf)
[1]
(ii)
0.038107
ppm CaCO 3 = x 106 = 762 (3 sf)
50
The water is very hard.
[2]
(b)
Ca2+ can be removed by heating the water sample.
By Le Chateliers Principle, the position of equilibrium will shift right to remove

the heat supplied causing a decrease in the concentration of Ca2+ ions.
OR
Ca2+ can be removed by heating the water sample.
Heating the water sample removes CO 2 (g) hence decreasing the concentration
of CO 2 (aq).
By Le Chateliers Principle, the position of equilibrium will shift right to increase

the concentration of CO 2 (aq) causing a decrease in the concentration of Ca2+
ions.
[2]
(c) (i)
[C 18 H 29 SO 3 @ [17 / 2.5 x 104)

= 2.1908 x 107 moldm3
= 2.19 x 107 moldm3
[1]
(ii)
Mass of C 18 H 29 SO 3 Na added to 1.0 dm3 = 0.174 g
0.174
No of moles of C 18 H 29 SO 3 Na added to 1.0 dm3 = = 5.00 x 104 mol
348
[1]
ttrendyline
d li
(iii)
Maximum moles of C 18 H 29 SO 3 dissolved dm3 = 2.19
solved in 1.0 d 2.1908 x 107 mol
2.1
No of moles of C 18 H 29 SO 3 precipitated out = 5.00 x 1044 2.1908 x 107

=4 9978 x 1044 mol
4.9978

312 trendyline
6
4.9978 x 104
Percentage of C 18 H 29 SO 3 precipitated = x 100%
5.00 x 104
= 99% (shown)
[2]
(d) (i)
Ca2+(aq) + P 3 O 10 5(aq) CaP 3 O 10 3(aq) (1)
Ca2+ (aq) + 2C 18 H 29 SO 3 (aq) (C 18 H 29 SO 3 ) 2 Ca (s) (2)
P 3 O 10 5 form complexes with Ca2+ causing a decrease in the concentration

of Ca2+.
By Le Chaterliers Principle, the equilibrium position of (2) shifts left to

increase the concentration of Ca2+. Hence reducing the amount of
(C 18 H 29 SO 3 ) 2 Ca formed.
Hence, preventing the formation of precipitate when detergent is added

into hard water.
[2]
(ii)
+5
[1]
(iii)
[1]
(iv)
Concentration of P 3 O 10 5 decreases as it complexes with the added Mg2+
to form MgP 3 O 10 3.
By Le Chateliers Principle, the equilibrium position of (1) will shift left to

increase the concentration of P 3 O 10 5.
There is no change to the value of K c as temperature is kept constant.

[2]
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[Total: 15]
5 (a)
CH 3 OH an
and CH 3 CH 2 OH.
O
[1]

313 trendyline
7
(b)
Two epoxide rings.
Two alcoholic groups are produced for every epoxide ring that will be
hydrolysed. Since there are four alcoholic groups formed after juvenile
hormone undergoes hydrolysis, this implies that there are two epoxide rings in
juvenile hormone.
[2]
(c) State the type of reaction that T has undergone and the functional group that it
contains other than the four alcoholic groups.
T undergoes basic hydrolysis to give methanol and U. T is likely to contain an
ester.
[1]
(d)
Two tertiary alcohol groups.
T has four alcohol groups which were retained in U even after basic hydrolysis.
Since V has only two alcohol groups left after mild oxidation, this implies that the
two alcohol group must be tertiary in order to resist oxidation.
[2]
(e)
O O
C C
H O O H
[1]
(f)
OH
O
H3C C CH3
C
CH3
Condensation. W contains eitherH3C or H
[2]
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314 trendyline
8
(g)
O
Juvenile hormone
O O
O
S
O O O
O
T
HO OH O
OH OH
O
U
HO OH OH
OH OH
O
V
HO OH OH
O O
W
HO OH O
O O
[6]
[Total: 15]
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315 trendyline
DUNMAN HIGH SCHOOL

Preliminary Examination 2016
Year 6
Paper 3 Free Response 20 September 2016
2 hours

Writing Papers
Graph Paper
Write your name, index number and class on this question paper and on the Cover Sheet provided.
Do not use staples, paper clips, highlighters, glue or correction fluid.

Start each question on a fresh sheet of paper.
At the end of the examination:
Fasten all work securely together with the Cover Sheet on top.
Hand in the question paper separately.
The total marks for this paper is 80 marks.
trendyline
This question paper consists of15 printed pages and 1blank page.
DHS 2016 [Turn over
316 trendyline
2
1 Blue #1 (Na 2 C 37 H 34 N 2 S 3 O 9 ) is a synthetic food colouring often found in ice cream.
Na O S SO 3 Na
3
+
N N
H 5C 2 C 2H 5
SO 3
(a) One of the main compounds used to produce Blue #1 is benzenesulfonic acid, which is
produced by heating benzene under reflux with concentrated sulfuric acid for several
hours.
SO 3H
+ +
H2SO4 H2O
(i) The first step of the mechanism involves the protonation of one molecule of sulfuric
acid by another and the loss of a molecule of water.
Name the type of reaction and describe the mechanism. In your answer, show
relevant lone pairs and charges, and use curly arrows to indicate the movement of
electrons.
[4]
(ii) Benzenesulfonic acid is a useful starting material as it can be easily converted to

phenol by heating with NaOH(aq) at 300C followed by acidification. It also has
similar chemical reactivity as nitrobenzene.
SO 3H
ONa O H
NaOH (aq)
HCl (aq)
3000C
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317 trendyline
3
Compound A can be synthesised from either benzenesulfonic acid or

ethylbenzene in not more than 4 steps.
The first step of the synthesis using either benzenesulfonic acid or ethyl benzene is
as shown below in Scheme 1 and 2 respectively:
Scheme 1:
SO H SO 3
H
3
CH2CH3
CH3CH2Cl / AlCl3
Scheme 2:
CH2CH3
CH2CH3
SO 3 H
conc. H2SO4
heat
Identify the correct scheme that will give compound A and copy the synthetic
scheme in your answer.
Using information in (a)(ii), suggest the next three steps to synthesise compound
A. Show all intermediates, reagents and conditions clearly in your synthetic route.
[4]
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318 trendyline
4
(b) Blue #1 can be oxidised by household bleach to form colourless products, as

represented by the equation below.
Na 2 C 37 H 34 N 2 S 3 O 9 + bleach products
blue colourless colourless
To study the kinetics of the reaction, a student used an UV spectrophotometer to study

the absorbance of Blue #1 over time during the bleaching process.
In experiment 1, the student mixes 3.0 cm3 of 0.1 moldm3 Blue #1, 1.0 cm3 of water and
0.5 cm3 of 3.5 moldm3 bleach together. The resultsof experiment 1 are as shown below.
Time (s) 15 30 45 60 75 90 105 120 135

Absorbance 0.495 0.424 0.371 0.328 0.285 0.251 0.218 0.191 0.170
(i) Explain why bleach is used in large excess as compared to that of Blue #1.
[1]
(ii) Given that absorbance measured varies linearly with the concentration of
Blue #1, use a suitable graphical method to determine the order of reaction
with respect to the blue food colouring, Blue #1.
[3]
(iii) The student subsequently conducted a few more experiments using other
volumes of Blue #1 and bleach. The table below shows the results obtained.
Experiment Volume of Volume of Volume of
Rate
Blue #1 distilled water bleach
constant
/ cm3 / cm3 / cm3
1 3.0 1.0 0.5
2 4.0 0.0 0.5 0.00882
3 3.0 0.5 1.0 0.01698
Using results from (b)(ii), determine the rate constant for experiment 1. Hence,
deduce the overall order of reaction, showing your reasoning clearly.
[3]
(c) (i) Household bleach is also often known as chlorine water. The active chemical
responsible for the bleaching action in household bleach is the anion, OCl,
which is easily formed by the disproportionation of chlorine in water.
Write a balanced equation between chlorine and water, and hence, suggest
the identity of the other compound formed.
[1]
(ii) Chlorine reacts with Period 3 elements, Mg and Si, to give chlorides. The two
chlorides differ in their reaction with water. Describe their differences, and
explain them in terms of the different structures and types of chemical
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bonding. Write an equation for the reaction,
reaction if any.
[4]
[Total: 20]

319 trendyline
5
2 Vanillin and vanillyl alcohol (derived from vanillin) are both used as flavouring, usually in
sweet foods such as chocolate. Vanillyl alcohol is commonly synthesised via the reduction of
vanillin using sodium borohydride, as shown below.
O H OH
4 + NaBH4 (aq) + 4H2O (l) 4 + H3BO3 (aq) + NaOH (aq)

O O
OH OH
vanillin vanillyl alcohol
(a) (i) Draw a dotandcross diagram to show the bonding in sodium borohydride.
[1]
(ii) Suggest why sodium borohydride is used in this reduction instead of lithium aluminium
hydride.
[1]
(iii) Given that the melting points of vanillin and vanillyl alcohol are 355 K and
388 K respectively, predict and explain the sign of the entropy change of reaction at
360 K.
[1]
(iv) A higher temperature leads to a faster rate of reaction. However, thermodynamic factors
must also be taken into consideration when considering appropriate conditions for a
reaction.
Explainhow higher temperatures will affect thethermodynamic outcome.

[2]
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320 trendyline
6
(b) The procedure for the reduction of vanillin to vanillyl alcohol is as follows:
1. Place 2 g of vanillin in a 25 cm3 round bottom flask followed by 4 cm3 ethanol. Add
a magnetic stirrer, clamp the flask above a stir plate and commence stirring at room
temperature to dissolve vanillin.
2. After the vanillin dissolves, add an ice bath under the flask to cool the solution.
3. In a separate reaction vial, dissolve 0.5 g of NaBH 4 in 3.8 cm3 of

1 moldm3NaOH solution.
4. Using a glass pipette, slowly add the NaBH 4 solution dropwise to the vanillin
solution over a period of 10 minutes.
5. Only after the addition is complete, remove the ice bath. This is because NaBH 4
decomposes at high temperatures.
6. Stir the resulting mixture for 10 minutes at room temperature.
7. Add 6 moldm3HCldropwiseuntil the evolution of hydrogen gas stops.
8. Stir to allow the product to precipitate from solution.
(i) State a reason why sodium borohydride must be added dropwise to the reaction mixture
(in Step 4).
[1]
(ii) In Step 7, hydrochloric acid was added to react with excess sodium borohydride present
in the reaction mixture. Write an equation for this reaction, given that boric acid (H 3 BO 3 )
is one of the products formed.
[1]
(iii) State one way you could modify the procedure to increase the isolated yield.
[1]
(iv) A preliminary way to determine whether the reaction has gone to completion is to draw
out aliquots of the reaction mixture and test for the presence of vanillin in it.
Describe a simple chemical test to test for the presence of vanillin. Give the expected
observations and write a balanced equation for the reaction with vanillin.
[2]
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321 trendyline
7
(c) Compound W, an isomer of V, can also be used as a starting reagent to synthesise vanillic
acid and other organic compounds shown in the reaction scheme below.
W Step 1 Step 2 Br2(aq) Y

X (Mr = 339.8)
(C10H12O2) HBr(g)
O
hot OH
acidified
KMnO4
O OH O O
Step 3 Step 4
Z
O O
OH HO
vanillic acid
(i) Draw the structures of compounds W, X and Y, and state the reagents and conditions
for Steps 2 and 4.
[4]
(ii) Vanillic acid (4hydroxy3methoxybenzoic acid) has an isomer,

2hydroxy3methoxybenzoic acid.
State which of the two isomers has a higher boiling point. Explain your answer.
[2]
(d) Organometallic compounds, usually a metal attached to an R group, can be used to convert
carbonyl compounds to alcohols.
A common type of organometallic compound are Grignard reagents. They have the formula
RMgX, where X is a halogen and R is an alkyl or aryl group.
O OMgX OH
dry ether H+
+ R'-MgX
R H R H R H
R' R'
carbonyl compound intermediate alcohol
trendyline
Draw the structure
ructure
ucture of the intermediate formed when vanillin reacts w
with ethylmagnesium
bromide.
[1]

322 trendyline
8
(e) The chemistry of lithium and its compounds differs significantly from the rest of the Group I
metals. In fact, lithium shows many similarities to magnesium exemplifying the socalled
diagonal relationship because of their positions in the periodic table.
In an experiment, a sample of solid magnesium amide, Mg(NH 2 ) 2 and lithium amide, LiNH 2
are heated separately.
Magnesium amide decomposes when heated to give magnesium nitride, Mg 3 N 2 and

ammonia gas.
(i) Write a balanced chemical equation for the decomposition of lithium amide.
[1]
(ii) With reference to Data Booklet, predict the decomposition temperature of LiNH 2 when
compared to Mg(NH 2 ) 2 , given that the ionic radius of Li+ is 0.060 nm. Explain your
answer.
[2]
[Total: 20]
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323 trendyline
9
3 (a) Methanal undergoes reaction with water to yield 1,1diol. The reaction is reversible and
the 1,1diol can eliminate water to regenerate methanal.
O OH
C + H2O C
H H H OH
H
(i) State the type of reaction for the above reaction.

[1]
(ii) The reaction is slow but the rate is increased by the addition of a small amount of
NaOH as catalyst. Suggest why NaOH is needed to initiate the reaction in the
mechanism.
[1]
The oxygen in water is primarily 99.8% 16O but water enriched with the heavy
isotope, 18O, is also available. When methanal is dissolved in 18Oenriched water, the
isotopic label becomes incorporated into the 1,1diol which regenerates methanal.
(iii) Using your answer to (a)(ii), suggest how 18O is incorporated into the 1,1diol.
*OH
C
H OH
H where *O = 18O
18
O-enriched 1,1-diol
[1]
(iv) The addition of water to aldehydes proceeds more rapidly than it does to ketones.
Suggest a reason why.
[1]
(b) Methanal also reacts with HCN to form 2hydroxyacetonitrile, HCH(OH)CN.

The 2hydroxyacetonitrile formed can be further converted to 2hydroxyethanoic acid,
as shown below.
HCH(OH)CN HCH(OH)COOH
(i) Explain whether 2hydroxyethanoic acid has a larger or smaller K a than ethanoic
acid.
[2]
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Phenol an
and 22hydroxyethanoic
hydroxyethanoic acid are weak Br
B n
nsted acids with pK a values of 9.80
and 3.86
6 respectively.
re of 20.0 cm3 of phenol and 2

ure
A mixture 2hydroxyethanoic
hydroxyethanoic acid was
wa titrated against a
3
solution
n of 1 moldm of sodium hydroxide.
xide Only 1 to 2 drops of p
phenolphthalein and
bromothymol blue indicators are used in this titration.

324 trendyline
10
It was found that the first colour change occurs at 17.20 cm3 and the second colour
change occurs at 26.80 cm3 of sodium hydroxide used.
A sketch (not drawn to scale) of the pH titration curve is shown below.
pH
volume of NaOH
8.60 added / cm3
(ii) Both phenolphthalein and bromothymol blue are weak acids. State the effect on
the volume of sodium hydroxide used for titration, if both indicators are added in
larger amount.
[1]
(iii) State the value of point X.

[1]
(iv) Write an equation to illustrate how the species found in point Y can maintain the
pH of a solution when a small amount of H+(aq) is added.
[1]
(v) Calculate the concentration of phenol and 2hydroxyethanoic acid in the original
mixture.
[2]
(c) The Strecker synthesis is a route to preparing amino acids. Methanal can be used to
synthesise glycine, 2aminoethanoic acid, in this way.
O NH NH2 H2N O
NH3 KCN, H2O H3O+
H
H2O H H
H H H H CN H OH
imine
The amino acid shown below is glutamic acid.
trendyline
dyy H2N
H
C
CH
COO
COOH
H2CH2COOH

325 trendyline
11
(i) Identify the aldehydecontaining compound and the imine intermediate which are
needed to synthesise glutamic acid via the Strecker synthesis.
[2]
(ii) Suggest, with a reason, if there is any difference in the optical activity of a sample
of glutamic acid synthesised by Streckers method and that of natural occurring
glutamic acid.
[1]
(d) Glycine and glutamic acid are among the many amino acids which constitute the long
amino acid sequence of protein kinase.Protein kinaseis an enzyme whichplays a major
role in protein regulation. It modifies other proteins by chemically adding phosphate
groups to them. This process is called phosphorylation.
(i) In phosphorylation, a phosphate group (PO 4 3) from adenosine triphosphate

(ATP) is transferred to and replaces a free hydroxyl group of amino acid. Shown
below are the structures of three amino acids and phosphate group.
serine (ser) glycine (gly) glutamic acid (glu)

H H H
H2N C COOH H2N C COOH H2N C COOH
CH2OH H CH2CH2COOH
P
O O
O
phosphate group (PO 4 3):
Draw the structure of the tripeptide, serglyglu, after phosphorylation.

[2]
(ii) The secondary structure of protein kinase consists of segments of -helix.

Describe the bonding which holds the -helix in place.
[2]
(iii) The protein kinase is destroyed during the process of denaturation. Explain how
this can occur by heating.
[2]
[Total: 20]
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326 trendyline
12
4 In 1849, the German chemist Adolf Kolbe reported his investigations into the electrolysis of
aqueous solutions of some carboxylate anions, using inert platinum electrodes. The Kolbe

electrolysis of trifluoroacetate (CF 3 CO 2 ), for example, is known to produce trifluoromethyl
radical (CF 3 , M r = 69) and a gas at the anode.
(a) Suggest the identity of the gas and hence construct a half-equation for the reaction at
the anode.
[2]
When the Kolbe electrolysis of trifluoroacetate was carried out in the presence of alkenes
such as CH 2 =CHCO 2 CH 3 , the radical intermediate X was formed which further dimerised to
yield product Y shown below.
CO 2CH3

CF3COO
F 3C F 3C
CO 2CH3 CO 2CH3 CF 3
electrolysis
X
CO 2CH3
Y
(b) State the oxidation number of the carbonyl carbon atom in CH 2 =CHCO 2 CH 3 .
[1]
(c) Suggest a two-step mechanism for the reaction above to form Y, starting from the
reaction between trifluoromethyl radical (CF 3 ) and the alkene. Use curly arrowsto
indicate the movement of single electrons and indicate any unpaired electrons by a dot
().
[3]
The Kolbe electrolysis in (c) was performed by continuous introduction of a water/CH 3 CN

solution containing trifluoroacetate and the alkene into an electrochemical microreactor at
constant current and room temperature.
The electrochemical microreactor has a flow channel sandwiched between two platinum
electrodes as shown in the figure below.
(d) (i) Given that the flow channel has a volume of 23 L and reaction mixture was
injected at a rate of 20 L min1, calculate the time (in seconds) in which the
current was passed through the solution.
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= 103 cm3)
(1 L
[1]
(ii) The
hee purified product
produc Y ((M
M r = 310) was obtained as a colourless
colou solid weighing
401
01 g. Using your answers from
0.401 fro (
(a) d (d)(i),
and (d ca
calculate the current
n ampere) that would have been applied
(in ap to the microreactor
microreactor.
[2]

327 trendyline
13
(e) (i) How many stereoisomers does Y have?

[1]
(ii) Draw the isomer of Y that is not optically active, showing clearly the
stereochemistry of the molecule using wedged and dashed bonds .
[1]
(f) When the Kolbe electrolysis of trifluoroacetatewas carried out in the presence of another
alkene, CH 2 =CHCONH 2 ( M r = 71), a non-dimer product ( M r = 209) was formed instead.
Suggest the structure of the product obtained.
[1]
(g) The trifluoromethyl (CF 3 ) group is regarded as an important structural feature in many
pharmaceutically relevant molecules because it is known to enhance chemical
inertness. Suggest an explanation for its property.
[1]
(h) (i) Deduce the structure of the radical intermediate formed when Kolbe electrolysis of
difluoroacetate, CHF 2 CO 2 , was carried out in the presence of the alkene,
CH 2 =C(CH 3 )CO 2 CH 3 .
[1]
(ii) The yield of the dimer product for this electrolysis was much poorer than that for
trifluoroacetate and CH 2 =CHCO 2 CH 3 . Use your answer in (h)(i) to suggest a
reason for the difference in yield.
[2]
Some carboxylate anions, L, are also known to form 1:1 complexes with divalent metal ions,
M2+, according to the following equilibrium.
M2+ + L ML+
(i) The table below gives the values of log K for some 1:1 metal-carboxylate complexes.
metal ion acetate (CH 3 COO) chloroacetate (CH 2 ClCOO)

Cd2+ 1.30 0.99
Cu2+ 1.76 1.07
Ni2+ 0.72 0.23
Using relevant data from the table, deduce
I the relative stabilities of the metal complexes formed with the acetate ligand.
[1]
II the relative magnitude of the log Kvalues of 1:1 Cu2+-CH 3 COO and
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Cu HCOO complexes and suggest
u2+-HCOO uggest a reason for your answer.
answe
[3]
[Total: 20]

328 trendyline
14
5 This question is about Period 3 elements and the uses of its compounds.
(a) A sample of magnesium oxideis suspected to be contaminated with a substantial

amount of aluminium oxide.Describe a simple gravimetric method to prove that the
contamination has taken place. Include equation(s)for the chemical reaction(s) involved,
if any.
[3]
(b) Another Period 3 oxide, sulfur trioxide dissolves in water to form sulfuric acid, H 2 SO 4
which can be converted into peroxodisulfuric acid, H 2 S 2 O 8 via the two-step process
below, with chlorosulfonic acid, HSO 3 Cl, as an intermediate:
H 2 SO 4 + HCl HSO 3 Cl + H 2 O
H 2 O 2 + 2HSO 3 Cl H 2 S 2 O 8 + 2HCl
(i) The structure of HSO 3 Clis given below.
O
S
HO O
Cl
The boiling point of H 2 SO 4 is 290 C whereas that of HSO 3 Cl is 152 C. By

making reference to the structures of the two compounds, explain the difference in
the boiling points.
[2]
(ii) Draw the structure of a H 2 S 2 O 8 molecule, showing the spatial arrangement and
estimated bond angle around any one sulfur atom.The H 2 S 2 O 8 molecule contains
a OO bond.
[2]
(c) Chlorine forms an oxide, Cl 2 O 7 , with the structure O 3 ClOClO 3 and a boiling point of
82C. Its standard enthalpy change of formation is 546 kJ mol1.
(i) Write the equation which corresponds to the standard enthalpy change of
formation of Cl 2 O 7 .
[1]
(ii) Given that the bond energy of ClO bond is 269 kJ mol1 and using relevant data
from the Data Booklet, estimate the average bond energy of the Cl=O bond.
[2]
(iii) The bond energy calculated in (c)(ii) could have been more accurate if the value
of an additional enthalpy change is known. State what process this enthalpy
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g corresponds
change p to.
[1]
(iv) iven
ven that the
Given th value of the enthalpy change in (c)(iii)
(c (iii)
(c) + 5 kkJmol1, construct an
i) iss +45
nergy
ergy level diagram to calculate the enthalpy change of formation
energy ffo of gaseous
Cll 2 O 7 .
[3]

329 trendyline
15
(d) Aluminium oxide is used extensively in organic synthesis as a dehydrating agent.
An organic compound A, C 12 H 18 O, contains a benzene ring with 2 substituents on the

1 and 4 positions on the ring. A is optically active. When it is treated with Al 2 O 3 ,
compound B is formed. Bcan be converted into another optically active compound C by
reacting with dry gaseous HCl. When C is heated under reflux with acidified KMnO 4 ,
compound D, C 11 H 14 O 2 , is produced. Treatment of D with PCl 5 produces compound E.
When E is heated with gaseous NH 3 , a neutral compound F is formed.
Identify the six compounds A F.

[6]
[Total: 20]
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16
BLANK PAGE
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e
331 trendyline
2016 Y6 H2 Chemistry Preliminary Examination Paper 3
(Answer Scheme)
1 (a) (i) Electrophilic substitution
(ii) Choose scheme 2

CH2CH3 CH2CH3
CH2CH3
+
SO 3 H O Na
conc. H2SO4 NaOH (aq)
heat 3000C
Cl2, uv
CH2CH2Cl
+
O Na
heat
(b) (i) To ensure that [bleach] remains almost constant throughout the reaction so
that the rate can be measured with respect to Blue #1 in a pseudo-order
reaction.
DHS 2016 9647/03

332 trendyline
(ii)
From graph hand-plotted,

when absorbance decreases from 0.40 to 0.20, t 78s
when absorbance decreases from 0.50 to 0.25, t 76s
Since almost constant t 77s is observed, the order of reaction wrt to [Blue#1] is 1.
OR
Reaction is first order with respect to[Blue#1].
(iii) Using t = ln 2, find value of k for experiment 1.

= 277 = 0.00900 s-1
Compare experiment 1 and 3, when the volume of bleach doubles, rate

constant almost doubles (i.e. 0.014980.00900 = 1.67 2).
The reaction is first order with respect to [bleach].
Hence, overall order of reaction is 2.
(c) (i) Cl 2 + H 2 2+&l + HOCl
(ii) MgCl 2 is an ionic compound which ionises in water to form hydrated Mg2+ and
Cl ions.
As Mg2+ has a high charge and small ionic radius / has a high charge density,
it hydrolyses slightly in water to form a weakly acidic solution of pH 6.5
[Mg(H 2 O) 6 ]2+ + H 2 O [Mg(H 2 O) 5 OH]+ + H 3 O+
SiCl 4 is a covalent compound which hydrolyses in water to form an acidic
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s
solution of pH 2.
SiC 4 + H 2 26L2+
SiCl 26L2+ 4 + 4HCl
4HCl
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333 trendyline
2(a) (i)
H -
+ x
Na H x
B x
H
H
(ii) Sodium borohydride is a milder reducing agent and hence is less reactive
and will not react as violently with water present.
OR
Lithium aluminium hydride is a very strong reducing agent and hence is

highly reactive and will react violently with water present.
(iii)
At 360 K, vanillin is a liquid while vanillyl alcohol is a solid. There is a
decrease in the degree of disorderliness, hence the entropy change of
reaction at 360 K is negative.
(iv) Ho and So will change as temperature increases.

Go may become more/less negative as temperature increases.

(b) (i) The reaction is exothermic / large amounts of heat will be produced. If it was
added all at once and this may cause NaBH 4 to decompose.
(ii) NaBH4 + 3H2O + HCl 1D&l + H3BO3 + 4H2
(iii) Use excess NaBH 4 as it may decompose at high temperatures.

Allow reactants to stir for a longer period.
(iv) To the aliquot drawn out, add a small amount of 2,4DNPH.
An orange precipitate will be seen if vanillin is present.
H O H2N H N NH NO 2
C NH C
NO 2
+ + H2O
OCH3 OCH3 NO 2
OH NO 2 OH
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334 trendyline
(c) (i) W X Y
Br HO Br
Br OH
or
Br O Br O
O O OH OH
OH OH
Step 2: alcoholic KOH, heat under reflux

Step 4: phenol, room temperature
(ii) Vanillic acid has a higher boiling point.

Due to proximity of OH and COOH groups, 2hydroxy3
methoxybenzoic acid is capable of forming intramolecular hydrogen
bonding, thus reduces the extent of intermolecular hydrogen bonding
formed.
More energy is needed to overcome the more extensive
intermolecular hydrogen bonds in vanillic acid.
(d)
BrMgO
O
OH
(e) (i) 3LiNH 2 Li 3 N + 2NH 3
(ii)
1 2
Charge density: Li+ ( ) << Mg2+ ( )
0.06 0.065
Polarising power: Li+<< Mg2+ OR
Distortion of electron cloud of NH 2 by both cations: Li+<< Mg2+
Therefore LiNH 2 will have a higher decomposition temperature than
Mg(NH 2 ) 2 .
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3 (a) (i) Nucleophilic addition
(ii) NaOH provides the OH ions which is a stronger nucleophile for the nucleophilic
attack on the carbonyl carbon.
(iii)
OH + H2O* H2O + *OH
The OH will deprotonate the 18Oenriched water to form the *OH. *OH then
attacks the methanal via nucleophilic addition reaction.
(iv) The carbonyl carbon in aldehyde is less sterically hindered than that in ketones,
hence more easily attacked by the nucleophile.
OR
The carbonyl carbon in aldehyde is more electron deficient (+) than that of
ketones as ketones have an additional electron donating alkyl group.
(b) (i) 2hydroxyethanoic acid has a largerK a as it is a stronger acid.
HCH(OH)COOH HCH(OH)COO + H+ - (1)
CH 3 COOH CH 3 COO + H+ - (2)
The electronwithdrawing OH group disperses the negative charge on the

conjugate base of 2hydroxyethanoic acid / 2hydroxyethanoate ion hence
stabilising the conjugate base/ 2hydroxyethanoate ion. The equilibrium
position of reaction (1) lies more to the right, producing more H+ ions, resulting
in 2hydroxyethanoic acid being a stronger acid.
OR
Intramolecular hydrogen bond can be formed in the 2hydroxyethanoate ion

between the carboxylate ion and the H of the alcohol group hence stabilising
the conjugate base/ 2hydroxyethanoate ion. The equilibrium position of
reaction (1) lies more to the right, producing more H+ ions resulting in 2
hydroxyethanoic acid being a stronger acid.
(ii) If both indicators are used in larger amount, a larger volume of sodium
hydroxide will be used to reach the endpoint to deprotonate the indicators
which are also weak acids.
(iii) X = 3.86
X corresponds to the pH of the buffer at maximum buffering capacity.

At maximum buffer capacity, pH = pK a
(iv)
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nd
dylin
ne
ne O
+ H+
H
OH
O
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(v) First endpoint corresponds to the neutralisation of 2hydroxyethanoic acid.
17.20 20
Concentration of 2hydroxyethanoic acid = ( x1)
1000 1000
= 0.860 mol dm3
Second endpoint corresponds to the neutralisation of phenol.
Volume of NaOH used for reaction with phenol = 26.80 17.20 = 9.60 cm3
9.60 20
Concentration of phenol = ( x1)
1000 1000
= 0.480 mol dm3
(c) (i) O NH
C C
H CH 2CH 2COOH H CH 2CH 2COOH
(ii) Streckers synthesis produces a racemic mixture and hence, do not display any
optical activity while naturally occurring glutamic acid is present as one of the
enantiomers and will rotate plane polarised light.
(d) (i) H O O H O O
H2N C C N CH2 C N C C O P O
CH2 H H CH2 O
O CH2
O P O C O
O O
O P O
(ii) The alpha helix is held in place due to hydrogen bonding.

Hydrogen bonding occurs between the peptide C=O group of the nth amino
acid and the peptide NH group of the (n+4)th amino acid which is in the
adjacent turn.
(iii) Heat increases thermal vibrations of the protein molecule, disrupting van der
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Waals interactions formed between uncharged R Rgroups in the
tertiary/quaternary structure.
The hydrogen bonds between polar R groups in tertiary structure are also
broken.
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4 (a) CO 2
CF 3 CO 2 CF 3 + CO 2 + e
(b) +3
(c)
F 3C
CO 2CH3 CO 2CH3
F 3C
X
CO 2CH3
CO 2CH3
F 3C F 3C
CF 3
CF 3
CO 2CH3
CO 2CH3
Y
(d) (i) time = 23/20 60 = 69 s
(ii) n(Y) = 0.401/310 = 0.0012935 mol

Since 2e 2CF 3 2X Y,
n(e) = 0.0025870 mol
Q = (0.0025870)(96500) = 249.65 C
I = 249.65/69 = 3.62 A
(e) (i) 3
(ii) CO 2CH 3 CO 2CH 3

H H
CH 2CF 3 CH 2CF 3
(f) CF 3
F 3C
CONH2
(g) The CF bonds in the CF 3 group are relatively strong and hence inert to chemical
reactions.
(h) (i) CH3

CHF 2
CO 2CH3
(ii) The presence of the methyl group at the C atom with the unpaired electron
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makes it more sterically hindered. It is more
mo difficult for two
tw bulkier radicals to
collide effectively to form the dimer.
(i) I CuL+> Cd
CuL L+> NiL
CdL NiL+
II log K (Cu2+-CH 3 COO) > log K (Cu2+-HCOO)
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From the table, the stability of the complexes is in the same order as the
availability of the lone pair of electrons on the negatively charged oxygen of
the carboxylate anions for dative bonding with the metal ion. Since the lone
pair of electrons on the negatively charged oxygen of CH 3 COO is more
available than that of HCOO for dative bonding with Cu2+, the
Cu2+-CH 3 COO complex is expected to be more stable than the Cu2+-HCOO
complex.
5 (a) 1. Weigh the original sample first.

2. Add aqueous sodium hydroxide in excess.
3. Only aluminum oxide will dissolve to form a soluble complex:
Al 2 O 3 + 2NaOH + 3H 2 O 2NaAl(OH) 4
4. The mixture is then filtered.
5. Dry the residue and reweigh the sample again.
6. If there is contamination, then there should be a difference in mass.
(b) (i) The molecular formulae suggest that the structure of chlorosulfonic acid is
derived from that of sulfuric acid, with O atom being replaced by Cl atom.
Hence the extent of hydrogen bonding is lesser between chlorosulfonic acid
molecules and hence requires less energy to overcome, giving it a lower
boiling point.
(ii) O
HO 109.5o
O O S
S O O
HO
O
(c) (i) Cl 2 (g) + 7/2 O 2 (g) Cl 2 O 7 (l)
(ii) Bond energy of ClCl = 244 kJ mol1

Bond energy of O=O = 496 kJ mol1
546 = 244 + 7/2(496) [2269 + 6(Cl=O)]
Bond energy of Cl=O = +331 kJ mol1
(iii) Vaporisation of Cl 2 O 7 (l)
(iv) Energy
Cl2(g) + 7/2 O2(g)

0
HfCl2O7(g)
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r ndylil
546 Cll2O7(g)
C
+45
45
Cll2O7(l)
C (l
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By Hess Law,
H fCl2O7(g) = +45 + (546)
= 501 kJ mol1
(d)
CH3 CH3 CH3 CH3 CH3
H3C C CH3 H3C C CH3 H3C C CH3 H3C C CH3 H3C C CH3
H C CH3 C H C CH3 C C
H CH2 HO O Cl O
OH Cl
A B C D E
CH3
H3C C CH3
C
H2N O
F
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HWA CHONG INSTITUTION
C2 Preliminary Examinations
Higher 2
CANDIDATE
CT GROUP 15S
NAME
CENTRE INDEX
NUMBER NUMBER
CHEMISTRY 9647/01
Paper 1 Multiple Choice 21 September 2016
1 hour
Additional Materials: Optical Mark Sheet (OMS)
Data Booklet

Complete the information on the optical mark sheet (OMS) as shown below.
There are forty questions on this paper. Answer all questions. For each question, there are four
Choose the one you consider correct and record your choice in soft pencil on the OMS.
trendyline
Each correct answer
err will score one mark. A mark will not be deducted
ded for a wron
wrong answer.
The use of an approved
oved scientific calculator is expected, where appropriate.
roved

341 trendyline
2
SECTION A
For each question, there are four possible answers A, B, C and D. Choose the one you consider
to be correct.
1 Methyl mercaptan, CH3SH, is one of the substances responsible for bad breath and is
often used to impart a smell to natural gas in a pipeline. When a sample of 10 cm3 of
CH 3 SH is exploded with 60 cm3 of oxygen, the final volume of gas after burning is
passed into an excess of aqueous alkali. The chemical equation for the combustion
process is shown below.
CH3SH + 3O 2 CO 2 + SO 2 + 2H 2 O
What percentage of the final volume of gas after burning dissolves in the alkali? All
gaseous volumes are measured at room temperature and pressure.
A 40.0% B 28.5% C 20.0% D 14.3%
2 Figure 1 shows the first six ionisation energies of an element Q while Figure 2 shows the
second ionisation energies of eight consecutive elements, including Q, in the Periodic
Table.
Figure 1 Figure
se 2
co
io ndi
ni oni
sa sat
tio ion
n en
en erg
er y/ B
gy kJ A
/ mo
kJ l1 C
m
ol
1
D
1 2 3 4 5 6
proton number
number of electrons removed
Which of the elements A, B, C or D could be the element Q?
3 Which statement is not always true when an ionic solid dissolves in water?
A Energy is absorbed to separate the ions in the solid.
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B Energy
gy is
s absorbed
abso bed to break
b ea tthe
e hydrogen bonding
yd oge bo between
d g bet ee water
ate molecules.
C Energy
gy is released when the ions are hydrated
hydrated.
D Energy
gyy is released when the ionic solid dissolves completely.
Hwa Chong Institution 2016 9647 / 01 / C2 Prelim 2016

342 trendyline
3
4 Which of the following explains the non-ideal behavior of the gases present in the
reaction chamber in the Haber process?
A the presence of a catalyst
B the high temperature of 450 C
C the high pressure of 150 atm
D the strong bonds between the atoms in the nitrogen molecules
5 Which enthalpy change would best indicate the relative strengths of the intermolecular
forces in liquid hydrogen halides?
A bond dissociation energy
B enthalpy change of formation
C enthalpy change of solution
D enthalpy change of vaporisation
6 CH 3 COCH 3 and I 2 react in the presence of an acid catalyst. The rate of reaction is
independent of [I 2 ] but directly proportional to [H+] and to [CH 3 COCH 3 ].
Which graph is correct?
A [I 2 ] B rate
0 time 0 [H+][CH 3 COCH 3 ]
C [CH 3 COCH 3 ] D [H+][CH 3 COCH 3 ]
0 rate 0 time
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4
7 When the system X 2 (g) + 3Y 2 (g) 2XY 3 (g) is at equilibrium at 500 K and 1 atm, the
value of the equilibrium constant, K p , is 100. What is the value of K p at a pressure of
2 atm at the same temperature?
A 25 B 100 C 200 D 400
8 The numerical values of the solubility product of BaSO 4 , BaCO 3 and Ba(IO 3 ) 2 at 25 C
are given in the table below.
Compound Solubility product

BaSO 4 1.1 1010
BaCO 3 2.6 109
Ba(IO 3 ) 2 4.0 109
An aqueous solution of BaCl 2 was added slowly, until in excess, to a solution

containing 0.5 mol dm3 Na 2 SO 4 , 1.0 mol dm3 Na 2 CO 3 and 1.5 mol dm3 NaIO 3 at 25
C.
What is the correct order of precipitation of the three barium salts?
First to precipitate Last to precipitate
A BaSO 4 BaCO 3 Ba(IO 3 ) 2
B Ba(IO 3 ) 2 BaCO 3 BaSO 4
C BaSO 4 Ba(IO 3 ) 2 BaCO 3
D BaCO 3 Ba(IO 3 ) 2 BaSO 4
9 What is the pH of the final solution formed when Vdm3of dilute hydrochloric acid of
pH 1.0 is mixed with Vdm3of dilute sulfuric acid of pH 1.0, followed by the addition of
2V dm3 of water?
A 1.1 B 1.3 C 2.0 D 4.0
10 Stomach juices have a pH of 1.0.
Aspirin is a monobasic acid represented by HA (K a = 104 mol dm3) which dissociates

into H+ and A ions.
What are the relative concentrations of H+, A and HA when aspirin from a tablet enters
the stomach?
A [H+] > [HA] > [A] B [H+] > [A] > [HA]
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C A]
[HA] > [H+] = [A D A] > [HA]
H+] = [A
[H

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5
11 In the construction of heart pacemakers, a tiny magnesium electrode is used which
creates an electrochemical cell with the inhaled oxygen. The relevant half-equations are
as follows.
Mg2+ + 2e- Mg Eo = -2.38 V

O 2 + 2H+ + 2e- H 2 O Eo = +1.23 V
Under standard conditions, the cell e.m.f. would be 3.61 V. However, in the body, a
potential of 3.25 V is more usual.
Which of the following is an explanation for this lower e.m.f. in the body?
A the pH of about 7.4 of the body fluid surrounding the electrodes
B the low concentration of Mg2+ ions surrounding the electrodes
C the small size of the magnesium electrode
D the large amount of oxygen inhaled
12 Ethanol fuel cells are more practical than hydrogen fuel cells since ethanol is easier to
store and transport than hydrogen. Ethanol is converted to carbon dioxide when the fuel
cell is operated.
wire connecting a pair of
graphite electrodes
ethanol air
H2SO4 (aq)
Which statement is correct about ethanol fuel cells?
A Ethanol fuel cells can work indefinitely as long as there is a supply of ethanol
and air.
B For every 1 mol of ethanol oxidised, 6 mol of electrons are produced.
C H+ ions react with air to produce water at the anode.
D The acid needs to be replenished as hydrogen ions are being used up.
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6
13 How many structural isomers of C 3 H 4 Br 2 contain C=C and how many do not contain
C=C?
structural isomers with C=C structural isomers without C=C

A 4 0
B 4 2
C 5 0
D 5 2
14 2-methylbuta-1,3-diene, CH 2 =C(CH 3 )CH=CH 2 , is used as a monomer in the

manufacture of synthetic rubbers. Which compound would not produce this monomer on
treatment with excess concentrated sulfuric acid at 170C?
A OH B
HO
OH
OH
C OH D
OH
HO
HO
15 Sorbitol is a naturally-occurring compound with a sweet taste. It is often used as a

substitute for sucrose by the food industry.
OH OH OH OH OH OH
H C C C C C C H
H H H H H H
sorbitol
How many chiral centres are present in sorbitol?
A 3 B 4 C 5 D 6
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7
16 Deuterium, D, is a heavy isotope of hydrogen. Deuteriobenzene is reacted with chlorine
and AlCl 3 under controlled condition so that only monochlorination takes place.
Assuming that the carbon-deuterium bond is broken as easily as a carbon-hydrogen

bond, which proportion of the chlorinated products will be 2-chlorodeuteriobenzene?
D D
Cl
-
deuteriobenzene 2 chlorodeuteriobenzene
A 16% B 20% C 33% D 40%
17 What is the correct set of reagents and conditions for the conversion of methylbenzene to
2-nitromethylbenzene?
A dilute nitric acid, 100 C
B concentrated HNO 3 , 30 C
C concentrated HNO 3 and concentrated H 2 SO 4 , 30 C
D concentrated HNO 3 and concentrated H 2 SO 4 , 100 C
18 Which reaction gives the best yield of products? [(alc) indicates an alcoholic solution.]
A Cl
uv light
(alc) + Cl2 (aq) + HCl
B Br NH2
heat in
(alc) + NH3 (alc) + HBr
sealed tube
C Br
heat
(alc) + CH3CH2ONa (alc) + NaBr + CH3CH2OH
D CO2H COCl
r.t.p
(l) + PCl5 (aq) + POCl3 + HCl
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19 Chlorofluorocarbons (CFCs) have been widely used in aerosol sprays, refrigerators and
347 trendyline
8
in making foamed plastics, but are now known to destroy ozone in the upper atmosphere.
Which compound will not destroy ozone, and therefore can be used as a replacement for
CFCs?
A CHBr 3
B CCl 3 CBr 3
C CHClFCClF 2
D CH 3 CH 2 CH 2 CH 3
20 Compound X has the following properties.
It changes the colour of acidified sodium dichromate(VI) from orange to green.

It gives yellow precipitate with alkaline aqueous iodine.
Which compound could be X?
A O OH B O
CH3 C C CH2I CH3 C OCH2CH2OH
CH3
C O O D I
H C C CH2I CH3 C CH2OH
OH
21 -naphthol is a crystalline solid that is widely used in the production of dyes.
OH
-
naphthol
Which of the following is likely to be a property of -naphthol?
A Its pK a is lower than that of phenol.
B It gives white fumes with SOCl 2 .
C It reacts with carboxylic acid to form ester.
D It undergoes nucleophilic substitution in the reaction below.
tre
trendyline
en
n ne
ndyl
OH
+ ++N
N2 SO3 + OH + H2O
N
N SO3
OH
22 Cinnamaldehyde, gallic acid and vanillin are naturally occurring organic compounds

348 trendyline
9
found in plants.
OH OH
O
OCH3
HO OH
CO2H O
cinnamaldehyde gallic acid vanillin
The CH 3 O group is inert and can be disregarded in this question.
Which set of reagents can be used to distinguish these three compounds?
A Aqueous bromine and aqueous sodium hydrogencarbonate
B Aqueous bromine and Tollens reagent
C Fehlings solution and neutral iron(III) chloride
D Fehlings solution and hot acidified potassium manganate(VII)
23 Two esters can react via Claisen condensation in the presence of a strong base. The two
steps of this reaction are shown below.
OR' OR'
R B R + BH+
Step 1:
O = O
(B base)
R
OR' OR' R'O
R + R R + R'O
Step 2:
O O O O
product of
Claisen condensation
Which compound will be formed when CH 3 CH 2 OCOCH 3 undergoes Claisen

condensation?
A O H O B O O
CH3 C C O C CH3 CH3 C CH2 C O CH2CH3
CH3
C O H O D O O
CH3O C C C CH2CH3 CH3 C CH2 CH2 C OCH3
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CH3

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10
24 Ergometrine is a drug used in obstetrics to treat heavy bleeding after childbirth.
OH
O NH
N
H ergometrine
Which statement about ergometrine is correct?
A pK b of the labelled three nitrogen atoms in increasing order is N < N < N .
B It reacts with both dilute NaOH and dilute HCl at room temperature.
C It forms orange precipitate with 2,4-dinitrophenylhydrazine.
D One mole of ergometrine reacts with 3 moles of CH 3 COCl.
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11
25 The graph represents the change in mass that occurs when 1.0 g of powdered calcium
carbonate, CaCO 3 , is heated at a temperature, T.
Mass / g
1.0
0.5
Time / min
0
Which graph would be obtained by heating 1.0 g of powdered magnesium carbonate,
MgCO 3 , at the same temperature,T?
A Mass / g B Mass / g
1.0 1.0
0.5 0.5
Time / min Time / min

0 0
C Mass / g D Mass / g
1.0 1.0
0.5 0.5
Time / min Time / min

0 0
26 What chlorine-containing products are formed when chlorine is bubbled into hot aqueous
sodium hydroxide?
A NaClO only
B NaClO 3 only
C NaCl and NaClO
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D NaCl an
and NaClO
NaClO 3

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12
27 Which statement concerning the Period 3 elements, sodium to chlorine, is correct?
A Chlorine has the largest anion.
B Aluminium has the highest melting point.
C Chlorine exhibits the most number of different oxidation states.
D Phosphorus reacts most vigorously with water.
28 Element X is one of the first five elements in Period 3 of the Periodic Table. The following
four statements were made about the properties of element X or its compounds.
Three statements are correct descriptions and one is false.
Which statement does not fit with the other three?
A The oxide of X dissolves in excess dilute NaOH(aq).
B X exhibits only one possible oxidation number in its chloride, which is not a
solid at room temperature.
C The oxide of X has a very high melting point.
D The chloride of X reacts with water to give an acidic solution with pH 1.
29 Which property of the first row transition elements doesnot remain relatively constant?
A atomic radius B melting point
C first ionisation energy D ionic radius of the +2 ions
30 Aqueous platinum(IV) chloride reacts with ammonia to form compounds in which the
coordination number of platinum is 6. When dissolved in water,1 mol of such compound
gave 3 mol of ions.
What is the formula of this compound?
A Pt(NH 3 ) 2 Cl 4 B Pt(NH 3 ) 3 Cl 4
C Pt(NH 3 ) 4 Cl 4 D Pt(NH 3 ) 6 Cl 4
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13
SECTION B
For each of the questions in this section, one or more of the three numbered statements 1 to 3
may be correct.
A B C D
1, 2 and 3 are 1 and 2 only 2 and 3 only 1 only is
correct are correct are correct correct
31 Which statements about one mole of a metal are always correct?
1 It contains the same number of atoms as one mole of hydrogen atoms.
2 It contains the same number of atoms as that in 12 grams of 12C.
3 It is liberated by one mole of electrons.
32 Beryllium is the first member of Group II and forms covalent compounds which are said to
be electron deficient. In many ways, beryllium resembles aluminium.
Which of the following are possible?
1 F F
Be Be
F F
2
F F
Be Be
F F n
3 2
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tr
re
F F
Be
F F

353 trendyline
14
A B C D
33 When 25.0 cm3 of a 0.100 mol dm3 strong monobasic acid was titrated against
0.200 mol dm3 of a weak base X, 12.50 cm3 of the base was required to completely
neutralise the acid.
Which statement is correct for this experiment?
1 Bromocresol green (pK In = 4.7) is a suitable indicator for this titration.
2 1 mole of X reacts with 1 mole of the monobasic acid.
3 A solution of maximum buffering capacity was formed when 6.25 cm3 of the
base was added.
Electrolysis of a solution of Mn+(aq) led to the deposition of M atoms at the cathode.

5.00 103 mol of M is deposited when 965 C of electricity are passed through the
solution.
What could Mn+be?
1 Sn2+
2 Cr2+
3 Ag+

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15
35 Humulene can be extracted from carnation flowers.
CH3
CH3
CH3
CH3
humulene
Which products are obtained from the reaction of humulene with hot acidified
concentrated KMnO 4 ?
1 CH 3 COCH 2 CH 2 CO 2 H
2 CH 3 COCH 2 CO 2 H
3 HO 2 CCH 2 C(CH 3 ) 2 CO 2 H
36 Consider the following reaction scheme.
Cl O Step I
O OH
M
Step IV
Cl
Cl
Which of the following statements about this reaction scheme are correct?
1 Step I requires a catalyst.
2 Compound M is a planar molecule.
3 Step IV is a substitution reaction.
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355 trendyline
16
A B C D
37 PGE 2 is a prostaglandin that has pharmacological activity.
O
CO2H
CH3
HO OH
PGE2
What is the correct number of hydrogen atoms incorporated per molecule of PGE 2 when
PGE 2 is reacted with each of the following reducing agents?
Number of hydrogen atoms

Reducing agent
incorporated per molecule of PGE 2
1 H 2 / Ni 6
2 LiAlH 4 in dry ether 4
3 NaBH 4 in ethanol 4
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356 trendyline
17
38 The cyclic peptide gramicidin S can act as an antibiotic.
NH2
O O
H H
N N
N N
H H
N O O
O
OO O N
H H
N N
N N
H H
O O
H2N
gramicidin S
Which statements about gramicidin S are correct?
1 It is made up of 5 different amino acids.
2 1 mole of gramicidin S reacts with 10 moles of hot dilute HCl.
3 Its three-dimensional structure can be stabilised by ionic interaction.
39 Which of the following are trends across Period 3 of the Periodic Table?
1 The electronegativity of the elements increases.
2 The oxides of the elements change from ionic to covalent.
3 The electrical conductivity of the elements decreases.
40 Prussian blue, Fe 4 [Fe(CN) 6 ] 3 , is a dark blue pigment often used in painting and dyeing.
It can be synthesised in the laboratory by mixing iron(III) chloride, FeCl 3 , with potassium
ferrocyanide, K 4 [Fe(CN) 6 ].
Based on the information given above, which conclusions can be made about Prussian
blue?
1 The percentage by mass of iron in Prussian blue is 45.5%.
2 A redox reaction has taken place in the formation of Prussian blue.
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Prussian
dy
sian blue absorbs blue light strongly.
strongl
The End

357 trendyline
2016 C2 H2 CHEMISTRY PRELIMINARY EXAM
SUGGESTED SOLUTIONS
Paper 1
1 2 3 4 5 6 7 8 9 10
A D D C D C B C B A
11 12 13 14 15 16 17 18 19 20
A A D B B C C C D C
21 22 23 24 25 26 27 28 29 30
A D B A C D C A B C
31 32 33 34 35 36 37 38 39 40
B C B D A D B D B D
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2016 HCI C2 H2 Chemistry Preliminary Exam / Paper 1
358 trendyline
Higher 2
CANDIDATE
CT GROUP 15S
NAME
CENTRE INDEX
NUMBER NUMBER
CHEMISTRY 9647/02
2 hours
1) Write your name, CT group, centre number and index number clearly in the spaces at
the top of this page.
2) Answer all questions in the spaces provided in this Question Paper.
INFORMATION FOR CANDIDATES

You may use a calculator.
For Examiners Use
1 / 12
2 / 17
3 / 14
4 / 13
5 /16
Deductions
Calculator Model:
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tren ne Total / 72
This document consists

359 of 18 printed pages. trendyline
2
1 Planning (P) For

Examiner's
use
An electrochemical cell is a device that produces an electric current as a result of redox
reactions. Any spontaneous redox reaction can be harnessed to produce electrical energy
under the right conditions. Electrons are generated at one electrode and driven towards the
other by electromotive force, also known as the cell potential, measured in volts.
The Gibbs Free Energy equation is given as G = H- TS. G may be obtained from the
cell potential of an electrochemical cell by the relationship:
G = -nFE
where n = number of moles of electrons transferred in the reaction

F = Faradays constant
E = cell potential
By constructing an electrochemical cell, the cell potential can be measured over a range of
temperatures. The entropy change of a reaction can then be determined by plotting a suitable
linear graph using the data obtained.
(a) (i) Write an ionic equation for the reaction between Cu and Fe3+. You should include
state symbols in your equation.
[1]
(ii) Predict the sign of Sfor the above reaction. Explain your answer.
[1]
(b) Using the information given above, you are required to write a plan for determining the
entropy change for the redox reaction between Cu and Fe3+. You will measure the cell
potential over a 30C range of temperature.
You are also required to explain how the data you obtain from this experiment may be
used to determine the entropy change of the reaction.
You may assume that the values of H and S are constant over this measured
temperature change.
You may also assume that you are provided with:
0.20 mol dm-3 aqueous FeCl 3

0.10 mol dm-3 aqueous CuSO 4
0.50 mol dm-3 aqueous H 2 SO 4
solid hydrated iron(II) sulfate, FeSO 4 .7H 2 O
common electrodes
the apparatus
pparatus normally found in a school or colleg
college laboratory.
Hwa Chong Institution 2016 9647 / 02 360

/ C2 Prelim 2016 trendyline
3
Your plan should include: For

Examiner's
use
a fully-labelled diagram of the set-up of the electrochemical cell you would use to
monitor how cell potential varies with temperature;
details for the preparation of 100 cm3 of 0.20 mol dm3 aqueous acidified FeSO 4 ;
details of the appropriate quantities and concentrations of solutions used;
the temperatures at which the experiments would be carried out;
an outline of how the results would be obtained;
a sketch of the graph you would expect to obtain;
how the data obtained from the graph would be used to determine the entropy
change for the reaction.

1

2

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7

8

9

10


4
For
Examiner's
use
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5
For
Examiner's
use
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...[10]

[Total: 12]

6
2 (a) The transition metals form many complexes. Two examples of complexes formed by Fe3+ For
Examiner's
are [Fe(H 2 O) 5 (SCN)]2+ and [Fe(CN) 6 ]3. use
These complexes contain the ligands, H 2 O, SCN, and CN, in which the "donor atom"
for dative bonding are O, S and C respectively.
(i) Explain why the atomic radius of oxygen (0.066 nm) is smaller than that of carbon
(0.077 nm).
[2]
(ii) Explain why the atomic radius of sulfur (0.104 nm) is larger than those of oxygen
and carbon.
[1]
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7
(b) When water ligands in an aqua complex are replaced by other ligands, the equilibrium For
Examiners
constant for the reaction is called the stability constant, K stab , of the new complex. use
For example,
[Fe(H 2 O) 6 ]3+(aq) + 6CN(aq) [Fe(CN) 6 ]3(aq) + 6H 2 O(l)
[Fe(CN) 6 3]
K stab =
[Fe(H 2 O) 6 3+][CN]6
The K stab value is an indication of the stability of a complex ion with reference to the aqua
complex. The table below lists the K stab values of some iron complexes.
complex K stab
[Fe(H 2 O) 5 (SCN)]2+ 1 102
[Fe(CN) 6 ]3 1 1031
[Fe(CN) 6 ]4 1 1024
[Fe(edta)] 1 1025
[Fe(edta)]2 2 1014
edta = (O 2 CCH 2 ) 2 NCH 2 CH 2 N(CH 2 CO 2 ) 2
(i) State the colour of the solution obtained when aqueous potassium thiocyanate,
KSCN, is added to aqueous Fe3+.
[1]
(ii) Suggest why the colour you stated in (b)(i) is not obtained when aqueous KSCN
is added to aqueous [Fe(CN) 6 ]3.
[1]
(iii) Predict whether edta would make the reduction potential for the Fe(III)/Fe(II)
system higher or lower than +0.77 V. Explain your answer.
[Fe(H 2 O) 6 ]3+ + e [Fe(H 2 O) 6 ]2+ E = +0.77 V
[1]
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(c) A series of tests was conducted as follow: For
Examiners

8
I When concentrated hydrochloric acid wasadded to dissolve black copper(II) use
oxide, a yellow solution wasobtained.
II Dilution of this yellow solution with water changed its colour to green and then
blue.
III When aqueous ammonia was then added, a pale blue precipitate formed which
dissolved in excess aqueous ammonia to give a dark blue solution.
(i) Identify the copper-containing species formed in each test.
Test Identity of copper-containing species

I
Yellow solution:
....
II
Blue solution:
III
Pale blue precipitate:
...
Dark blue solution:

...
[2]
(ii) Write equations to illustratethe ligand exchange reactions in forming
the blue solution inTest II:
the dark blue solution in Test III:
...... [2]
(d) Aluminium is extracted from molten aluminium oxide, Al 2 O 3 , by electrolysis.
(i) With reference to E data from the Data Booklet, explain why an aqueous
solution of Al3+ (from a soluble aluminium salt) would be unsuitable as the
electrolyte.
[1]
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9
In the industry, Al 2 O 3 is dissolved in molten cryolite, Na 3 AlF 6 to lower the melting point of For
Examiners
Al 2 O 3 . The molten mixture is then electrolysed using graphite electrodes. use
(ii) The electrode reactions are very complicated. In one simplified study, some
scientists say that, in molten cryolite, Al 2 O 3 ionises into Al3+ ions and AlO 2 ions.
At the cathode, Al3+ is converted to Al metal: Al3+ + 3e Al

At the anode, AlO 2 is converted to Al 2 O 3 and oxygen gas.
Write an equation for the anode reaction.
... [1]
(iii) A typical cell operates at 104 A. Calculate the time, in hours, needed to produce
1 tonne of aluminium. (1 tonne = 1000 kg)
[2]
(e) A saturated solution of XeF 2 (M r = 169) in water at 0 C contains 25.0 g dm3 of XeF 2 .
The solution is a strong oxidising agent, quantitatively oxidising another solution
containing 0.150 mol dm3 of a Cr(III) salt. XeF 2 is reduced to Xe in the reaction.
In an experiment, 15.20 cm3 of the XeF 2 solution is required to completely react with
10.0 cm3 of the Cr(III) solution.
Determine the oxidation state of Cr after the reaction.
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[Total: 17]
10
3 The hydrogenation of but-2-ene is shown in the equation below For

Examiner's
use
CH 3 CHCHCH 3 (g) + H 2 (g) CH 3 CH 2 CH 2 CH 3 (l)
(a) Describe the changes in bond angle and the type of hybridisation involved at the site of
the hydrogenation reaction.
.....
.....
.....
.....[2]
(b) Under certain conditions,but-2-ene gives alcohol A, C 4 H 10 O, which exists as a liquid at

room temperature.
(i) State the reagents and conditions required in this reaction. Draw the displayed
formula of alcohol A formed in this reaction.
.
A:
[2]
(ii) Explain, in terms of structure and bonding, the difference in the physical state of
but-2-ene and alcohol A at room temperature. Draw a diagram to illustrate your
answer for alcohol A.
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Diagram:
agram

11
[3]
(iii) Ester C is used in synthetic fruit flavours. Alcohol A reacts with compound B at For
Examiners
room temperatureto give a good yield of ester C with relative molecular mass use
of 116.
Draw the structures of compounds B and C.
B: C:
[2]
(c) (i) In a separate reaction, butane is treated with a small quantity of bromine in the
presence of ultraviolet light to give 1-bromobutane and 2-bromobutane. It is
found experimentally that the hydrogen atom is substituted by bromine at
different rates, as shown in the table below.
Type of H atom Relative rate of substitution

Primary hydrogen 1
Secondary hydrogen 4.5
Using this information, and considering the number and types of hydrogen within
butane, determine the mole ratio of the two monobrominated products.
..
..
..
..[2]
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12
(ii) Name and outline the mechanism for the formation of 2-bromobutane in this For
Examiner's
reaction. use
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[3]
[Total: 14]

13
4 (a) Using relevant data from the Data Booklet, describe and explain how the thermal stability For
Examiner's
of the hydrogen halides varies down Group VII. use
.....
.....
.....
.....
.....[2]
(b) In the laboratory, three bottles each containing one of the following reagents were mixed
up:
NaI(aq), KBr(aq) and KCl(aq).
Describe chemical test(s), which does not involve silver nitrate, that could distinguish and
identify the contents of each bottle.
.....
.....
.....
.....
.....
.....
.....[3]
(c) HF behaves as a medium-strength acid and dissociates only partially in aqueous

solutions as shown below. K 1 and K 2 representthe numerical values of the respective
equilibrium constants.
HF + H 2 O H 3 O+ + F K 1 = 1.1 103
HF + F HF 2 K 2 = 2.6 101
(i) Write the overall equation for the reaction of liquid HF with H 2 O to form HF 2 and
calculate the numerical value of the equilibrium constant for this reaction.
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[2]
(ii) The dissociation equilibrium of a solute in a solvent can be significantly shifted by For

14
the addition of a suitable substance into the solution. Suggest an inorganic Examiner's
use
reagent which can be added to increase the dissociation of HF in water. Explain
your choice.
[2]
(d) Similar to water, pure liquid hydrogen fluoride also undergoes auto-ionisation according
to the following equilibrium:
3HF H 2 F+ + HF 2
The ionic product of HF is 8.0 1012 mol2 dm.
(i) Draw the structures of both the cationic and anionic species in liquid HF. Label
the types of bonding within the anionic species.
[2]
(ii) Calculate the fraction of H 2 F+ in liquid HF (density= 1.002 g cm3), supposing that
only these three species are present in the system.
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[Total: 13]
5 The following reaction scheme is proposed for the synthesis of the amino acid proline. For

15
Examiner's
use
multiple O
O
O HCl steps
Cl N
Cl H2N H
H2N step I
Cl
Cl
enzyme
amidase
N N N N
H H H H
step III step II
CO2H CONH2 CN Cl
proline ro
p linamide
(a) (i) Draw structures of two possible intermediates formed in step I. Hence, explain
why the yield of the product in step I is low.
....
....
....[2]
(ii) With the aid of a sketch of the Boltzmann distribution, explain how an increase in
temperature affects the rate of reaction in step II.
....
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..
....
....
..
....[3]
(iii) It was found that only 50% of prolinamide synthesised by the method above could For
Examiners
16
be converted to proline by enzyme amidase in step III. Suggest an explanation for use
this observation.
....
....
....[1]
(b) The enzyme amidase used in step III contains amino acids listed in the following table.
name abbreviation structural formula
aspartic acid asp HO 2 CCH 2 CH(NH 2 )CO 2 H

asparagine asn H 2 NCOCH 2 CH(NH 2 )CO 2 H
cysteine cys HSCH 2 CH(NH 2 )CO 2 H
glycine gly CH 2 (NH 2 )CO 2 H
isoleucine ile CH 3 CH 2 CH(CH 3 )CH(NH 2 )CO 2 H
lysine lys H 2 N(CH 2 ) 4 CH(NH 2 )CO 2 H
phenylalanine phe C 6 H 5 CH 2 CH(NH 2 )CO 2 H
serine ser HOCH 2 CH(NH 2 )CO 2 H
(i) There are three pK a values associated with aspartic acid: 2.1, 3.7 and 9.8. In the
boxes below, draw the structures of the major species present in solutions of
aspartic acid at pH 3 and pH 8.
pH 3 pH 8
[2]
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(ii) Complete the following table by indicating the type of interaction between each
Examiners
pair of amino acid residues that stabilises the tertiary structure of enzyme use
17
amidase at pH 7.
amino acid residue 1 amino acid residue 2 type of interaction
aspartic acid lysine
isoleucine phenylalanine
serine asparagine
[2]
(iii) Explain how mercury ion, Hg2+(aq), affects the activity of the enzyme amidase
through denaturation.
.......
....
....[2]
(c) A section of the polypeptide chain in enzyme amidase was partially hydrolysed and the
following peptide fragments are produced.
lys-gly, asp-lys-ser, cys-asn-phe, gly-cys-asn, ser-phe-lys
State the smallest possible sequence of amino acids in this section of the polypeptide
chain using the 3-letter abbreviations.
.....[1]
(d) A scientist extracted a new compound Dfrom

f microorganisms. He proposed the following For
Examiners
structure for D. use

18
O
S OH
O N
H2N N
O
H
(i) D was postulated to be synthesised from amino acids.
-amino acids that could be used in the synthesis.

Identify from the list in (b), two
....[1]
(ii) Assuming that the SC bond is inert, draw the organic products if D was heated in
aqueous H 2 SO 4 .
[2]
[Total: 16]
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Paper 2
1 (a) (i) Cu(s) + 2Fe3+(aq) Cu2+(aq) + 2Fe2+(aq) [1]
(ii) Positive. More aqueous ions produced and thus more ways that
energy can be distributed in the system through the motion of ions.
[1]
1 (b)
M1 [1/2] voltmeter and salt bridge
[1/2] a single water bath or hot plate (not separate)
M2 Correct Fe3+/Fe2+ half cell:

[1/2] electrode + [1/2] solutions (with correct concentration)
M3 Correct Cu2+/Cu half cell:

[1/2] electrode + [1/2] solution (with correct concentration)
M4 [1/2] 5.56 g of solid
[1/2] details for weighing electronic balance, weighing bottle/

beaker, reweigh or tare and rinse out all solid
M5 Preparation of acidified FeSO 4 solution:

[1/2] adding acid before topping up to 100 cm3 mark
trend
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d
dy
[1/2] 100 cm3 volumetric flask
[1 f
M6 Preparation of FeSO 4 solution:

lution:
Transfer solid to beaker
Dissolve solid in beaker
ke
Transfer solution to volumetric flask
7
377 trendyline
Transfer washings to volumetric flask
Top up volumetric flask
Shake
[1/2] any 3 5 points

[1] all 6 points
M7 [1/2] measure volumes of solutions used for both half-cells

(minimum volume of electrolyte in each half-cell: 20 cm3)
[1/2] use appropriate apparatus e.g. measuring cylinder for

measurement of solutions for both half-cells
M8 [1/2] measure temperature using thermometer or set temperature

of thermostatically controlled water bath
[1/2] range of temperature used at least 30 C should have at

least 5 readings with at least 5 C intervals (lowest temperature
should not be below 20 C)
M9 Sketch of graph:
[1/2] Correct choice of axes E vs T (ignore units)
[1/2] Linear graph with positive gradient
$OORZDSORWRI*YV T. In this case, a linear graph with negative

gradient would be obtained. Candidate needs to explain clearly
KRZ*FDQEHREWDLQHG
M10 [1] explain how entropy change could be obtained from the graph
HJ*UDGLHQW S/ nF (for E vs T graph)
Gradient = 6IRU*YV7JUDSK
Sample procedure
1. Using an electronic weighing balance, weigh accurately 5.56g of
FeSO 4 .7H 2 O in a weighing bottle.
2. Transfer this solid into a 100 cm3 beaker. Reweigh the weighing
bottle to account for any residual solid. Record the mass of the solid
used.
3. Dissolve the solid usingg about 20 cm3of 0.50 moldm3H 2 SO 4 (aq).
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4. Transfer this solution into a 100 cm3 volumetric flas
beaker
eaker thoroughly and transfer all washin
he
e mark with deionised water/
the water/H
solution. Label
homogeneous solution
washing
washings
H 2 SO
el this
flask.
flask Rinse the
s into the flask. Top up to
O 4 (aq) and shake well to obtain a
th solution as FA1 FA1.

378 trendyline
5. Transfer 15 cm3 of FA1 and 15 cm3 of 0.20 mol dm-3 FeCl 3 into a
100 cm3 beaker using separate burettes.
6. Transfer 30 cm3 of 0.10 mol dm-3 CuSO 4 into a 100 cm3 beaker
using a burette.
7. Set up the apparatus as shown in the diagram above.
8. Ensure that the water bath is maintained at 25oC by measuring the
temperature with a thermometer.
9. Record the cell potential using a voltmeter.
10. Record the cell potential at different temperatures: 30oC, 35oC,
40oC, 45oC, 50oC, 55oC.
Plot a graph of E against T.

E
S = gradient of the graph x F x n
2 (a) (i) m each:

O atom has more protons (or higher nuclear charge than C atom)
shielding effect is similar (or almost the same)
O has higher effective nuclear charge
its outer electrons are pulled (or attracted) more closely to the
nucleus
(ii) 1m: S atom has 1 more occupied quantum shell than O and C.
2 (b) (i) 1m: blood red
(ii) m each:
[Fe(CN) 6 ]3 has (much) higher K stab than [Fe(H 2 O) 5 (SCN)]2+
SCN (and H 2 O) unable to replace CN as the ligands attached to
Fe3+ i.e. no ligand exchange
(iii) 1m:
So
OR
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m:
e(edta has (much) highe
e(edta)]
[Fe(edta)] han [Fe(edta)]2.
higher K stab than
o [Fe(edta)] is less likely to be reduced to [Fe(edta)
[Fe(edta)]2.
edt )] + e [Fe(edta)]22 lies more to
R reduction equilibrium [Fe(edta)]
[Fe(edta
the left.
8
379 trendyline
OR edta ligand stabilises +3 oxidation state of Fe relative to +2 state.
reduction potential for Fe(III)/Fe(II) with edta as ligands or for
[Fe(edta)]/[Fe(edta)]2 would be lower than +0.77 V.
2 (c) (i) m each:

yellow solution: [CuCl 4 ]2
blue solution: [Cu(H 2 O) 6 ]2+
pale blue ppt: Cu(OH) 2 or [Cu(OH) 2 (H 2 O) 4 ]
dark blue solution: [Cu(NH 3 ) 4 (H 2 O) 2 ]2+
(ii) 1m each:
Test II [CuCl 4 ]2 + 6H 2 O [Cu(H 2 O) 6 ]2+ + 4Cl
Test III [Cu(H 2 O) 6 ]2+ + 4NH 3 [Cu(NH 3 ) 4 (H 2 O) 2 ]2+ + 4H 2 O
Accept
2 (d) (i) m each:

Eo(H 2 O/H 2 ) = 0.83 V and Eo(Al3+/Al) = 1.66 V
or Eo(H+/H 2 ) = 0 V and Eo(Al3+/Al) = 1.66 V
Eo(H 2 O/H 2 ) is higher or less negative, so H 2 O would be
preferentially reduced to H 2 , Al3+ would not be reduced to give Al.
orEo(H+/H 2 ) is higher or less negative, so H+ would be
preferentially reduced to H 2 , Al3+ would not be reduced to give Al.
(ii) 1m: 2AlO 2 Al 2 O 3 + O 2 + 2e

or 4AlO 2 2Al 2 O 3 + O 2 + 4e
(iii) 1m: calculates no. of moles of electrons

1m: calculates time in hours
1000103
Amount of Al deposited = = 3.704 104mol
27
Amount of electrons passed = 3 3.704104 = 1.111 105mol
Q = It = 1.111105 96500 = 1.072 1010 C

1.0721010
t= 4 = 1.072 106 s = 298 h (or 297.8 h)
10
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2 (e) 1m: concludes
ncludes
c +6
1m: calculates
culates 0.00225 mol XeF 2 and 0.00150 mol Cr(III)
1m: explains
lains how to conclude +6, e.g. 1 mol Cr(III) loses 3 mol electrons
plains
Sample
e working:

380 trendyline
15.2 25
Amount of XeF 2 = = 0.002249 mol
1000 169
XeF 2 reduced to Xe, oxidation state of Xe changes from +2 to 0
Amount of electrons transferred = 2 0.002249 = 0.004497 mol
10
Amount of Cr(III) = 0.150 = 0.00150 mol
1000
0.004497
= 3 mol of electrons lost from 1 mol of Cr(III)
0.00150
oxidation state of Cr increases by 3 units
oxidation state of Cr is +6 after reaction
3 (a) The carbon atom of the reactant (but-2-ene) in the CC bond is

sp2hybridised [1/2] and the bond angle around the carbon atom is 120o
[1/2].
The carbon atom of the product (butane) in the CC bond is sp3hybridised

[1/2], and the bond angle around the carbon atom is 109.5o. (accept 109o)
[1/2]
(b) (i) Steam, 300C, 70 atm (or 60 atm), (conc) H 3 PO 4 [1]

ORconc H 2 SO 4 followed by warming with water.
H H H H
H C C C C H
H H H
O
A: H [1]
(ii) Both but-2-ene and alcohol are simple covalent compounds /simple,
discrete molecules /have simple molecular structure. [1/2]
For but-2-ene, there are weak dispersion forces between its

molecules. For alcohol A (butan-2-ol) with polar OH bond, there are
strong intermolecular hydrogen bonding between its molecules. [1/2]
More energy is required to overcome the stronger intermolecular
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ydrogen
drogen bonding in alcohol
hydrogen alcoho A thanan the weak di disp
dispersion forces in
ut-2-
ut -2-ene
ene which is therefore in gaseous state. [1/2]
but-2-ene
ORR
thee energy provided by room temperature is insuffic
insufficie to overcome
insufficient
thee strong hydrogen bonds between
tw alcohol A molecules,
molecu
9
381 trendyline
Hence alcohol A exists as a liquid at room temperature and but-2-
ene exists as gas. [1/2]
Diagram [1]
o showing correct hydrogen
bond (must be oxygen atom
and the H atom from the OH
group)
o labelling hydrogen bond
o showing lone pair of electrons
on oxygen
o labelling+ and - for the OH
group forming H bond.
Each mistake minus 1/2 mark
(iii) O O
B: Cl [1] C: O [1]
3 (c) (i) Ratio of 1-bromobutane : 2-bromobutane = 1 : 3 [1]
In 1-bromobutane: there are 6 possible primary (1o) H atoms for

substitution and in 2-bromobutane: there are only 4 secondary (2o) H
atoms for substitution [1/2]
Relative rate of substitution suggests that
the mole ratio of 1-bromobutane : 2-bromobutane
= 1 x 6 : 4.5 x 4 = 6 : 18 [1/2] for working
(ii) Type of mechanism: Free radical substitution [1]
uv light
Initiation: BrBr 2 Br [1/2]
Propagation: [1]

CH 3 CH 2 CH 2 CH 3 + Br CH 3 CH 2 CHCH 3 + HBr

CH 3 CH 2 CHCH 3 + Br 2 CH 3 CH 2 CH(Br)CH 3 + Br
t endy
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y
Termination [[1/2]]
Br + Br Br 2

Br + CH 3 CH 2 CHCH 3 CH 3 CH 2 CH(Br)
CH(Br)CH 3

382 trendyline

CH 3 CH 2 CHCH 3 + CH 3 CH 2 CHCH 3
CH 3 CH 2 CH(CH 3 )CH(CH 3 )CH 2 CH 3
4 (a) The thermal stability of the hydrogen halidesdecreases down the group
[1/2] as the bond energy of HX decreases accordingly from +562 (HF)
to +431 (HCl) to +366 (HBr) to +299 kJ mol (HI) [1/2].
Down the group, less energy is required to break the bond [1/2] as the
bond strength decreases [1/2].
(b) Step 1: To 1 cm3 of each reagent in separate test tubes, add a few drops
of aqueous lead(II) nitrate and shake. [1/2]
If yellow ppt (of PbI 2 ) is obtained, the test tube contains NaI. If white ppt is
obtained, the test tube contains KBr or KCl. [1]
Step 2: To 1 cm3 of each reagent that gave white ppt in step 1, add a few
drops of acidified sodium chlorate(I) OR Cl 2 (aq) and shake. [1/2]
If the solution turned yellow-orange, the test tube contains KBr. If the
solution remained colourless, the test tube contains KCl. [1]
OR
Step 1: To 1 cm3 of each reagent in separate test tubes, add a few drops
of acidified sodium chlorate(I) OR Cl 2 (aq), followed by 1 cm3 of
hexane.Shake well and leave to stand. [1]
If both layers remained colourless, the test tube contains KCl.
If the aqueous layer turned yellow-orange, while the organic layer turned
reddish-brown, the test tube contains KBr.
If the aqueous layer turned brown, while the organic layer turned violet,
the test tube contains KI. [3obs correct:2m; 2 obs correct:1m]
4 (c) (i) 2HF + H 2 O H 3 O+ + HF 2 [1]

K K1 K 2 (1.1 10 3 )(2.6 10 1 ) 2.86 10 4 [1]
(ii) NaOH, Na 2 CO 3 , etc. Base reacts with acid, lowers [H 3 O+] and shifts
position of equilibrium forward. [2]
(d) (i) hydrogen bonding

H F H F H F
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tr
re dy i
re
R
OR

H F H F H F
hydrogen bonding
en
[1] x 2
10
383 trendyline
(ii) [H F+] = [HF ] = (8.0 10 12 ) 2.83 10 6 mol dm3
2 2 [1]
1.002 10
3
[HF] = 50.1mol dm3
1.0 19.0
The auto-dissociation causes a negligible change in [HF], hence the

[H2F ] 2.83 106
requested fraction is 5.65 108
[HF] 50.1 [1]
5 (a) (i) O
Cl
H2N
First intermediate: [1/2]
O
Cl
Second intermediate: H2N [1/2]
Product formed is from the first intermediate which is less stable than
second intermediate. [1/2]
This is because the positive charge is intensified by electron

withdrawing chlorine through inductive effect. [1/2]
(ii) Boltzmann distribution diagram: [1]
No. of Proportion of molecules with KE Ea at T1

T1
molecules
/proportion T2
of + Proportion of molecules with KE Ea at T2
molecules /
percentage T2 > T1
of
molecules
0 energy
Ea
At higher temperatures, the proportion of molecules with kinetic

energy greater than or equal to activation energy increases [1].
Thus, frequency of effective collision increases [0.5], reaction rate

increases [0.5]
(iii) The prolinamide is synthesised as a racemic mixture containing
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qual
ual proportions of two enantiomers. [1
equal [1/2]
ence
nce only 50% of the synthesisedprolinamide can fit into / would
Hence
ossess
ssess the correct 3D shape to bind to the ac
possess active site of the
nzyme. [1/2]
enzyme.

384 trendyline
5 (b) (i) O O
+
H3N CHC O H3N CHC O
CH2 CH2
C O C O
pH 3: OH [1] pH 8: O [1]
(ii)
aspartic acid lysine Ionic interaction
isoleucine phenylalanine dispersion forces / van der
Waals interaction
serine asparigine Hydrogen bond
3 correct = [2], 2 correct = [1], 1 correct = [1/2]
(iii) Mercury ion disrupts the disulfide bridge by binding tightly with SH
of cysteine residue
OR
Mercury ion disrupts the ionic interaction by forming ionic
interactionwith CO 2 side chain of aspartic acid. [1]
The tertiary structure / shape of the enzyme is altered, and hence its
function is lost. [1]
5 (c) Asp-lys-ser-phe-lys-gly-cys-asn-phe [1]
(d) (i) Glycine [1/2], cysteine [1/2]
(d) (ii) O O
S OH
H3N OH
NH2
H3N OH
O [1] each
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11
385 trendyline
Higher 2
CANDIDATE
CT GROUP 15S
NAME
CENTRE INDEX
NUMBER NUMBER
CHEMISTRY 9647/03
Paper 3Free Response 19September 2016
2 hours
Data Booklet
Answer any fourquestions.
Begin each question on a newpiece of paper.

Write down the question numbers for the questions attempted on the cover page
provided.
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2
1 (a) Suggest and explain how the boiling points of 1-chlorobutane and 1-bromobutane
differ from each other. [2]
(b) (i) Define the term standard enthalpy change of combustion. [1]
(ii) Use of the Data Booklet is relevant to this question.
In an experiment to determine the enthalpy change of combustion of

bromobutane, a quantity of the fuel was burnt underneath a copper can
containing 200 g of water. It was found that the temperature rose by 45.0 C after
2.35 g of bromobutane had been burnt. The heat transfer was known to be only
80% efficient.
Calculate the enthalpy change of combustion of the bromobutane. Ignore the heat
capacity of the copper can. [2]
(c) An experiment was set up to study the reaction between 2-bromo-3-methylbutane and
sodium hydroxide. The reagents used were FA1,containing 0.0100 mol dm3 of
2-bromo-3-methylbutane and FA2, containing 0.0100 mol dm3 NaOH. In each
experiment, the reagents were dissolved in a suitable solvent to ensure good mixing.
The results are recorded in the table below.
Expt Volume of FA1 Volume of FA2 Volume of solvent Rate / mol dm3 s1
/ cm3 / cm3 / cm3
1 10.0 30.0 60.0 7.40 x 10-7
2 5.0 20.0 25.0 9.86 x 10-7
3 10.0 5.0 35.0 4.93 x 10-7
(i) Use the data in the table to deduce the order of reaction with respect to
2-bromo-3-methylbutane and sodium hydroxide. Hence, write a rate equation for
this reaction. [3]
(ii) With reference to your answer to (c)(i), describe the mechanism for the reaction
between 2-bromo-3-methylbutane and sodium hydroxide. [3]
(iii) Calculate the rate constant for the reaction, stating the units. [2]
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a Chong Institution 2016 9647 / 03 / C2 Prelim 2016
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3
(d) In a separate experiment, a student performed the following qualitative analysis tests
on three different bromoalkanes: 1-bromobutane, 2-bromobutane and 2-bromo-2-
methylpropane. Different solvents were used for Test 1 and Test 2 and it was
observed that the choice of solvents did have an effect on the type of reaction
mechanisms undergone by the bromoalkanes.
Test 1:
When silver nitrate was added to the bromoalkanes using ethanol as the solvent,
silver bromide was precipitatedfor all three bromoalkanes at different rates.
AgNO 3 + RBr + C 2 H 5 OH ROC 2 H 5 + HNO 3 + AgBr
Test 2:
When sodium iodide in propanone solvent was added to the bromoalkanes,

sodium bromide was precipitated for 1-bromobutane and 2-bromobutane at different
rates, but not 2-bromo-2-methylpropane.
NaI + RBr RI + NaBr
The observations for each test were recorded in the following table.
Time taken for precipitate to appear

Test 1 Test 2
1-bromobutane 5 min Almost immediately
2-bromobutane 3 min 5 min
2-bromo-2-methylpropane Almost immediately No precipitate
(i) Different nucleophilic substitution mechanisms have been proposed for the
reactions in the two tests.
Considering the information provided, suggest the predominant mechanism

undergone in each test. [1]
(ii) Considering the structure of the bromoalkane, explain why the test results support
your answer in (d)(i). [2]
(iii) Considering the interactions involved with the solvent, explain why the suggested
mechanism for Test 1 occurs predominantly. [1]
(e) 2-methylbenzonitrile can be used as a starting reagent to form compound A. Propose

a synthesis route for the formation of compound A in no more than 3 steps, showing
clearly the reagents, conditions and structures of the intermediates formed.
CH3
NH
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d li
N
CN
C
2-methylbenzonitrile
benzonitrile Compound A
[3]
[Total: 20]
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4
2 Ethanoic acid behaves as a weak acid in water, with K a = 1.8 x 105 mol dm3.
In contrast, ethanoate ion behaves as a weak base in water, withK b = 5.6 x 1010 mol dm3.
(a) (i) Write the expressions for K a and K b of ethanoic acid and ethanoate ion
respectively, and use these expressions to show that the product K a K b has a
constant value at a fixed temperature. [2]
(ii) Compare the relative strength of ethanoate ion and water as bases, and explain
with the aid of an equation, whether a solution of sodium ethanoate is acidic,
alkaline, or neutral. [2]
(iii) Calculate the pH of a solution which contains 0.50 mol dm3 ethanoic acid and
0.50 mol dm3 sodium ethanoate. [1]
(b) The Strecker synthesis is a route to prepare amino acids. Glycine

(2-aminoethanoic acid) can be prepared from methanal as shown in the reaction
scheme below.
elimination NH2
O of H2O NH
NH3 HCN
C A C H C C N
reaction I reaction II reaction III
H H H H H
reaction IV
NH2
O
H C C
OH
H
glycine
(i) Suggest a structure for compound A. [1]
(ii) The product of reaction II is an imine, which has a C=N bond. Methanal
undergoes reaction with another compound B to form an orange solid C which
also has a
C=N bond. Name compound B and draw the structure of the orange solid C. [2]
(iii) What type of reaction is occurring duringreaction III? [1]
(iv) State the reagents and conditions for reaction IV. [1]
(v) Compound D is an isomer of glycine. Upon warming D with dilute sodium

hydroxide, a gas which turns litmus blue is evolved. Draw the structure of D. [1]
(vi) A carbonyl compound E can be used as the starting material to prepare another
amino acid, alanine (2-aminopropanoic acid) using the Strecker synthesis. Draw
the structure of E. [1]
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te
State
i (b)(vi)
(vii) The synthesis of alanine in (b)(vi produces a mixture of two optical isomers.
e which one of the reactions, I to IV
yourr choice briefly.
V, gives rise to this mix
IV, mixture, and explain
[2]
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5
(c) In organic chemistry, the number of bonds that a given carbon atom has with
electronegative atoms like O or N is called the functional group level of that carbon
atom. Some examples are shown below, but there are many other possibilities.
Functional group level

1 2 3
R R
O N O O
C
C C C C
R
OH
R R H R R R OH R OCR3
(R = alkyl or aryl group or H atom)
(i) State the functional group level of the carbon atom in methane and in carbon
dioxide. [1]
Keeping track of the functional group level can be used to understand a large number
of organic reactions.
During oxidation reactions, the functional group level increases as CH bonds are
converted into new CO bonds.
During reduction reactions, the functional group level decreases as CO bonds are
converted into new CH bonds.
During hydrolysis reactions, the functional group level of every carbon remains the
same.
In each of the reactions in (c)(ii) and (c)(iii), no carbon-carbon bonds are broken or
formed.
(ii) Ethyl butanoate undergoes the following reaction to form two products. State the
functional group level of the circled carbon atom at the start and end of the
reaction, and hence deduce whether the reaction is an oxidation, a reduction, or a
hydrolysis reaction.
O
C2H5OH
OH
OC2H5
ethyl butanoate [2]
(iii) Gyromitrin, a toxin found in fungi, undergoes hydrolysis to give three different
products, F, G, and H. Suggest structures for these products using their relative
molecular masses (shown in brackets) and the functional group levels of the
carbon atoms.
O
N F G H
N H
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r
(58) (46) (46)
(114)
114
gyromitrin [3]
[Total: 20]
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6
In 2016, 4 new elements were added to the Periodic Table. Part of the Periodic Table
showing information about the 4 new elements is shown below.
Key
relative atomic mass
Nh Mc Ts Og atomic symbol
nihonium moscovium tennessine oganesson name
113 115 117 118 proton number
Mc, Ts, and Og were synthesised by accelerating calcium ions into atoms of heavier
elements. Once in every few billion collisions, the nuclei of the 2 particles would fuse and
give rise to the new element. For example, Ts was synthesised using berkelium ( 97 Bk).
(a) (i) State the heavy element used in the synthesis of Mc. [1]
(ii) Based on the relative position of Ts in the Periodic Table, predict the physical
state of Ts at room temperature. Give a brief explanation for your answer. [2]
(iii) Scientists have predicted the existence of superheavy elements above proton
number 120 that are stable under standard conditions. One such element, if
successfully synthesised in large quantities, would give rapid effervescence of a
colourless gas in water, and its oxide would be basic in nature. The sulfate
compound of the element would be insoluble in water.
State, with reasons, the group of the Periodic Table that this element is likely to
belong. [2]
(b) Scientists are already working on the next element of proton number 119 using
berkelium and titanium.
(i) Explain, using relevant electronic configurations, why titanium is considered a

transition element but not zinc. [2]
(ii) Tetrahydrofuran(THF), M r = 72.1, is a simple covalent molecule that behaves as

a monodentate ligand. Titanium forms a complex with zero net charge with THF
and chloride ligands. A 1.00 g sample of the complex was completely hydrolysed
in water and filtered. The residue contained 2.99 103 mol of TiO 2 . The filtrate
yields 1.72 g of silver chloride after treating with aqueous silver nitrate. Determine
the coordination number of the central titanium of the complex. [3]
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7
Calcium and titanium are both metals but differ in their chemical and physical properties.
(c) (i) Compounds of calcium contain the Ca2+ ion. The corresponding ion of titanium is
Ti3+. Use relevant data from the Data Booklet to explain why Ca3+ compounds do
not exist and Ti3+ compounds do. [3]
(ii) Draw labelled diagrams to show the shapes of the orbitals in the outermost
occupied quantum shell of a Ca2+ ion. [2]
(iii) Explain why the melting point of titanium is higher than that of calcium. [2]
(iv) Describe the observations when calcium is burned in air, and excess water is
added to the resulting oxide. Write equations where appropriate and suggest the
pH value of the aqueous solution formed.
[3]
[Total: 20]
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8
4 Transition metal catalysed reactions have emerged in recent years as powerful tools for
preparing organic compounds from previously unavailable routes. Ruthenium-based
catalysts have been at the heart of these advances.
(a) The ruthenium(II) based catalyst RuH 2 (PPh 3 ) 4 , where PPh 3 = P(C 6 H 5 ) 3 , is able to
catalyse the formation of an amide under suitable conditions, as shown in the scheme
below.
O
RuH2(PPh3)4
NH2 OH
N
H
(i) Draw the structure of the product for the reaction below.
RuH2(PPh3)4
OH
H2N C4H7NO [1]
(ii) RuH 2 (PPh 3 ) 4 also catalyses the formation of the amide shown in the reaction
scheme below. Draw the structures of compounds A and B.
CH3
RuH2(PPh3)4 O
A+B
N
H
[2]
(iii) Propose a synthetic route for the formation of compounds A and B, using only
methylbenzene as the starting compound in each case. [3]
(b) The catalyst RuH 2 (PPh 3 ) 4 exhibits geometric isomerism. In the cis configuration, the
H-Ru-H angle is 90, while in the trans configuration, the H-Ru-H angle is 180.
Draw labelled diagrams showing the structures of the two isomers. [2]
(c) In addition to RuH 2 (PPh 3 ) 4 , other ruthenium complexes like the one shown below,
also proved to be effective in organic synthesis.
H
N N
Ru
P P
Ph Ph Ph Ph
State the oxidation number of ruthenium in the complex above. [1]
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9
(d) The complex ion tris(bipyridine)ruthenium(II) is a catalyst which has received much
attention because of its ability to exhibit optical isomerism. Two of its isomers are
shown below.
2+ 2+
N N
N N N N
Ru Ru
N N N N
N N
(i) Explain why the complex above exhibits optical isomerism. [1]
(ii) Tris(bipyridine)ruthenium(II) cation contains three bipyridine rings, which can be

represented by the symbol, bipy. The formation of tris(bipyridine)ruthenium(II)
from aqueous ruthenium(II) ions is shown in the equation below. The enthalpy
change for this reaction is approximately zero.
[Ru(H 2 O) 6 ]2+(aq) + 3bipy(aq) [Ru(bipy) 3 ]2+(aq) + 6H 2 O(l)
Deduce the sign of the entropy change,S, and hence the sign of the free energy
change, G, in this reaction. [3]
Iron is directly above ruthenium in the transition metal block of the Periodic Table.
(e) Ligands are able to modify the difference in energy between the non-degenerate
d-orbitals in an octahedral crystal field.
The following table lists the different colours of visible light and their corresponding
wavelengths. The energy of light is inversely proportional to its wavelength.
Colour violet blue green yellow red

Wavelength / nm 400 450 500 600 650
The equation below represents the hydrolysis of Fe(III) ions in water. The pale yellow
colour of Fe(III) solutions observed commonly is actually due to the presence of the
complex ion [Fe(H 2 O) 5 (OH)]2+, while unhydrolysed [Fe(H 2 O) 6 ]3+ is pale purple in color.
[Fe(H 2 O) 6 ]3+(aq) + H 2 O(l) [Fe(H 2 O) 5 (OH)]2+(aq) + H 3 O+(aq)

pale purple yellow
(i) With reference to the colours of the two complexes above, explain which complex
ion has a larger energy gap between their d-orbitals. [2]
(ii) Electrons in both [Fe(H 2 O) 6 ]3+ and [Fe(H 2 O) 5 (OH)]2+ exhibit a high spin state,
where electrons occupy the d-orbitals singly before starting to pair up in the lower
energy d-orbitals.
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Draww a suitable diagram to show the electron distribution in th
Fe3++ ion in a high sp
rbital
bital has been promoted to a higher energy d-
d-orbital
certain
in wavelength.
ain wavelength
spin excited
d-orbital
the 3d subshell of a
dstate, where an electron from a lower energy
excitedstate,
bital by ab
d-orbital absorbing light of a
[1]
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10
(f) K 2 FeO 4 is a strong oxidising reagent which is dark red in colour.
FeO 4 2(aq) + 8H+(aq) + 3e Fe3+(aq) + 4H 2 O(l)E = +2.20 V
Using relevant data from the Data Booklet, describe and explain the observations
when the following solutions are mixed together in I and in II respectively.Calculate
the E cell andwrite a balanced equation for any reaction occured.
I K 2 FeO 4 and H 2 O 2
II KMnO 4 and Fe(NO 3 ) 3 [4]
[Total: 20]
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11
5 (a) Ag 2 CO 3 is a sparingly soluble salt. A 100 cm3 saturated solution of Ag 2 CO 3 in water

was found to contain 2.57 10mol dm3 of Ag+ ions.
(i) Calculate the K sp of Ag 2 CO 3 and state its units. [2]
(ii) Hence, calculate the solubility of Ag 2 CO 3 when 2.50 g of Na 2 CO 3 solid was

added to the solution above. [2]
(b) The table below shows the pK a values of benzoic acid and its derivatives.
Acid benzoic acid 2-hydroxybenzoic acid 4-hydroxybenzoic acid

OH
Structure CO2H HO CO2H

CO2H
pK a 4.20 2.98 4.58
Rank the three compounds in order of increasing acid strength and account for the
trend. [3]
(c) Compounds P and Q can be synthesised from 4-hydroxybenzoic acid.
Cl OH
O O
OH OH
HO Cl
P Q
Suggest the reagents and conditions for a reaction that could be used to distinguish
between P and Q. You need to state how each of P and Q react.
[2]
(d) Heating compound A, C 13 H 14 O 3 , under reflux with dilute H 2 SO 4 produces compound

B, C 8 H 8 O, and compound C, C 5 H 8 O 3 .
B reacts with aqueous bromine to give compound D, C 8 H 7 O 2 Br 3 . On heating B with

acidified KMnO 4 , 4-hydroxybenzoic acid and carbon dioxide gas are formed.
When C is heated with acidified KMnO 4 , compound E is the only organic product
formed. Both C and E gave yellow precipitate when warmed with alkaline aqueous
iodine. Treatment of E with aqueous Na 2 CO 3 liberates carbon dioxide gas.
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(i) p
When vaporised pp , 0.219 g of E occupied
in a suitable apparatus, p a volume of 70
cm3 at 150 C
C and a pressure of 125 kPa.
Calculate
ulate the relative molecular mass of E and hence suggest
culate sugg a molecular
mula
ula
formula for E,
E, given that it contains 3 carbon atoms.
[2]
(ii) Suggest structures for A to E, explain your reasoning. [9]
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12
[Total: 20]
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Paper 3
1 (a) 1-bromobutane has a higher boiling than 1-chlorobutane. Both

1-bromobutane and 1-chlorobutane are simple molecular. Since
1-bromobutane has a larger electron cloud size[1], there is stronger
dispersion forces between its molecules as compared to
1-chlorobutane. Hence, more energy[1] is needed to break the stronger
dispersion forces for 1-bromobutane.
(b) (i) Standard enthalpy change of combustion is the heat

evolvedwhenone mole of the substance is completely burnt in
excess oxygen at 298 K and 1 atm. [1]
(ii) Heat absorbed by water q= (200)(4.18)(45.0) = 37620 J

= 37.6 kJ [1]
Enthalpy change of combustion = [100/80 37.62] / (2.35/136.9)

= 2.74 103 kJ mol1[1]
(c) (i) Comparing Expt 1 and 2,

(Total volume in Expt 2 is half that of Expt 1.)
Concentration of 2-bromo-3-methylbutane is constant, when
concentration of NaOHincreases 4/3 times, rate increases 4/3 times.
Hence, the reaction is 1st order with respect to NaOH[1]
Comparing Expt 2 & 3,

(Total volume in Expt 2 and 3 are the same)
When concentration of 2-bromo-3-methylbutane increases 2 times
and concentration of NaOHdecreases 4 times, the rate decreases 2
times. Since the reaction is first order with respect to NaOH, the
reaction is thus 1st order with respect to 2-bromo-3-methylbutane[1]
[Calculation method also accepted]
Rate = k [2-bromo-3-methylpentane][NaOH] [1] ecf
(ii) S N 2 Nucleophilic substitution [1]
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398 trendyline
CH(CH3)2 CH(CH3)2 CH(CH3)2
HO C Br HO C Br HO C Br
+
H H
H CH3 CH3
CH3
2m for mechanism
(iii) Rate = k [2-bromo-3-methylbutane][NaOH]
To obtain the numerical value for k, substitute the rate and the
respective concentrations into the rate equation.
10 30
(0.0100) (0.0100)
7.40 10-7 = k 1000
10.0+30.0+60.0 1000
10.0+30.0+60.0

1000 1000
k = 0.247 [1] Calculation
To derive the units,

mol dm3 s1 = k (mol dm3)2
k = mol1 dm3 s1[1] Units
(d) (i) Test 1: S N 1 mechanism

Test 2: S N 2 mechanism [1]
(ii) In Test 1, the rate of reaction is the fastestfor thetertiary

bromoalkane. The carbocation formed from the tertiary bromoalkane
is stabilised by three electron-donating alkyl groups, hence it
undergoes S N 1 rapidly. [1]
In Test 2, the rate of reaction is the fastestfor theprimary

bromoalkane asthere is least steric hindrance when the nucleophile
attacks the electron deficient carbon atom of the primary
bromoalkane, hence it undergoes S N 2 rapidly. [1]
(iii) The carbocation formation is favoured as ethanol can form ion-dipole
t
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interactions with the carbocation intermediate therebyy stabilising it
].
[1].
1
399 trendyline
(e)
CH3 CH2Cl
LiAlH4 in
Cl2(g), UV dry NH
ether
[1] [1]
CN CN
[1]
For the second step, accept H 2 , Ni, high temp and high pressure. Also
accept if split up last step to show reduction followed by nucleophilic
substitution with heat for last step.
2 (a) (i) [CH 3 CO 2 ][H+]

Ka =
[CH 3 CO 2 H]
[CH 3 CO 2 H][OH]
Kb =
[CH 3 CO 2 ]
[1]
[3 2 ][ + ] [3 2 [] ]
K a K b = x
[3 2 ] [3 2 ]
= [H+] [OH]
= K w (ionic product of water), which is a constant. [1]
(ii) CH 3 CO 2 H is a weak acid so its conjugate base CH 3 CO 2 is a

stronger base than water.
So CH 3 CO 2 undergoes hydrolysis forming OH ions, forming an
alkaline solution.[1]
CH 3 CO 2 (aq) + H 2 O (l) CH 3 CO 2 H (aq) + OH (aq) [1]
(iii) As [CH 3 CO 2 H] = [CH 3 CO 2 ], this is a maximum capacity buffer;

so pH = pK a
ORJ[5 )
= 4.74 [1]
(b) (i) A[1]
OH
NH2
C
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H H
(ii) B = 2,4
2,4-dinitrophenylhydrazine
2,4--dinitrophenylhydrazine
nitrophenylhydrazine [1]

400 trendyline
C [1]
NO2
H H
C N N NO2
H
(iii) addition [1]
(iv) Dilute H 2 SO 4 / HNO 3 / HCl, heat [1]
(v) D [1]
OH
O
H C C
NH2
H
(vi) E [1]
O
C
CH3 H
(vii) Reaction III[1]

The imine is trigonal planar about the imine carbon atom. The
nucleophile can thus attack this + carbon atom in equal probability
from the top as well as the bottom[1], resulting in forming equal
proportions of the two optical isomers / racemic mixture.
(c) (i) Functional group level of C in CH 4 = 0; in CO 2 = 4

[1]
(ii) Functional group level of circled C at the start = 3; at the end= 1

[1]
As the functional group level decreases, the reaction is reduction. [1]
(iii) H
O
N H
H N
O HO H
CH3
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F G/H
1m
m each
2
401 trendyline
3 (a) (i) [1] Americium (Am)
(ii) Ts lies below astatine in Group VII, following the trend of increasing
melting point down the group[1], it should be a solid [1] like iodine or
astatine.
(iii) [1] Group II.
[0.5]: Effervescence of hydrogen gas with water => Group I or II

metal
or
Basic oxide hydrolyses to give metal hydroxide in water => Group I or
II metal
[0.5]: Sulfate insoluble => Group II metal as Group I sulfates all
soluble. Or Group II sulfate solubility decreases down the group.
(b) (i) Titanium is able to form ions with incomplete d-subshell, Ti2+:
1s22s22p63s23p63d2 or Ti3+: 1s22s22p63s23p63d1[1]
but
zinc forms only the Zn2+ ion which has 1s22s22p63s23p63d10
configurationwith a fully filled d-subshell [1].
(ii) No. of moles of titanium = no. of moles of TiO 2 = 2.99 103 mol
No. of moles of chloride = 1.72 / 143.5 = 0.0120 mol
Ratio of chloride ions to titanium = 0.0120 / 2.99 103 = 4.01 = 4 [1]
1st mark can be awarded if student is able to provide an answer that
clearly recognises from TiO 2 that the complex is formed from a Ti(IV)
center [0.5] and since complex is electrically neutral, there must be 4
chloride ions [0.5]
Mass of titanium and chloride in 1 g sample = 2.99 103 189.9 =

0.568 g
Mass of coordinated THF molecules in 1 g sample = 0.432 g
0.432 / (72.1 n) = 2.99 103
No. of THF molecules coordinated = 0.432 / (2.99 103 72.1) =
2.00 = 2 [1](working forno. of THF ligands must be shown)
Coordination number = 6 [1](this answer must be based on an actual

no. of chloride and THF ligands stated earlier)
Allow ecf from errors in number or chloride and THF ligands

calculated, rounded up to whole numbers.
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tren
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ylin
y
(c) (i) he 3rd ionization energy of Ca (+4940
The (+4940 mo 1) is much
4940 kJ mol m higher than
nd
d 1
1 rd
d
the
e 2 ((+1150
1150 kJ mol )as the 3 electronlectron in Ca is removed
re from an
inner
ner
er quantum sh shell
shell[1]
[1] which
whic requires a lot of eneenergy. Thus, Ca3+
compounds
mpounds do not exist.

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For Ti, the 2nd and 3rd ionisation energies (+1310, +2720 kJ mol1) do
not differ greatly as 4s and 3d electrons are close in energy[1]. Thus,
Ti3+ can be formed.
[1]: some comparison/discussion of ionisation energies for Ca and Ti

pertaining to the high 3rd ionisation energy for Ca compared to Ti.
(ii)
z
y
x
3px
3s 3px 3py
3py 3pz
3s 3pz
[2]
(iii) In calcium, only the 4s electrons are donated to the sea of

delocalised electrons, while in titanium, both the 4s and 3d electrons
are involved (idea of more electrons contributed towards metallic
bonding). OR Titanium cations have higher charge/ smaller ionic
radius / greater charge density than calcium cations. [1]
This leads to titanium having stronger metallic bond strength and

more energy is needed to overcome the metallic bonds[1] and hence
a higher melting point.
(iv) Burns slowly with brick-red flame , leaving a white residue [1]
2Ca(s) + O 2 (g) 2CaO(s)
CaO(s) + H 2 O(l) Ca(OH) 2 (aq) [1]
Ca(OH) 2 dissolves / gives a colorless solution in water to give an
alkaline solution of pH = 12[1] (Accept any value above 7)
4 (a) (i) O
HN
[1]
(ii) CH2OH
[1] [1]
NH2
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3
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.
(iii) 1 Sn, conc HCl, heat
conc HNO3 .
2 NaOH (aq)
conc H2SO4
30C [1]
. NO2
[0 5] NH2
CO2H LiAiH4 CH2OH

KMnO4 (aq) dry ether
H2SO4 (aq)
. [1]
heat [0 5]
accept Cl 2 (g), UV or heat, followed NaOH (aq), heat to get

phenylmethanol.
(b) H H
PPh3 H PPh3 PPh3
Ru Ru
PPh3 PPh3 PPh3 PPh3
PPh3 H
cis trans [1] x 2
(c) +1 [1]
(d) (i) The complex is chiral as the two optical isomers are non-
superimposable mirror images of each other. [1]
(ii) S is positive[0.5] as the number of product particles is greater than

the number of reactant particlestherefore the number of ways to
distribute energy in the system increases.[1]
G H 7S.
$VH DQGG = 7S[1]7KXVG is negative [0.5]
(e) (i) The wavelength of light (complementary of yellow) absorbed by

[Fe(H 2 O) 5 (OH)]2+ is of a lower wavelength than that for
[Fe(H 2 O) 6 ]3+[1]. Therefore, the energy gap between the d-orbitals
must be larger in [Fe(H 2 O) 5 (OH)]2+[1].
(ii) Energy
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[1]
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(f) (I)
O 2 + 2H+ + 2e H 2 O 2 +0.68 V
E cell = +2.20 (0.68)
= +1.52 V > 0 reaction is feasible
2
2FeO 4 + 10H + 3H 2 O 2 2Fe3+ + 8H 2 O + 3O 2
+
Observations: Red solution turns pale yellow, as FeO 4 2is reduced to

Fe3+.Effervescence of O 2 OR effervescence of a colourless and odourless
gas that rekindles a glowing splint. [3]
(II)
MnO 4 + 8H+ + 5e Mn2+ + 4H 2 O +1.52 V
E cell = +1.52 (2.20) <0 reaction is not feasible
Solution remains purple [1]
5 (a) (i) K sp = [Ag+]2[CO 3 2]

= (2.57104)2(2.57104/2) = 8.49 1012 mol3 dm9
[1m for numerical answer; 1m for units]
(ii) K sp = [Ag+]2[CO 3 2]
8.49 1012 = [Ag+]2 (2.50 (23 2 + 12 + 16 3) (100/1000))
[Ag+] = 6.00 106 mol dm-3[1]
Solubility of Ag 2 CO 3 = 6.00 106 = 3.00 106 mol dm-3[1]
(b) 4-hydroxybenzoic acid, benzoic acid, 2-hydroxybenzoic acid [1]
4-hydroxybenzoic acid is a weaker acid than benzoic acid because the

OH group attached to the benzene ring is electron-donating (lone pair of
electrons on O atom is delocalised into the benzene ring), hence
intensifying the negative charge on the carboxylate anion and reducing its
stability.[1]
2-hydroxybenzoic acid is a stronger acid than benzoic acid because its

conjugate base can be stabilised by intramolecular hydrogen bonding/ion-
dipole interactions. [1]
(c) Add AgNO 3 (aq) at room temperature [1]
Q : White ppt of AgCl formed immediately
P: No white ppt formed[1]
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OR
Add K 2 Cr 2 O 7 , dilute H 2 SO
O 4 , heat [1]
[1]
nge K 2 Cr 2 O 7 turns
Q : Orange urns green
P: Orange
nge K 2 Cr 2 O 7 remains orange e [1]
[1
4
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OR
Add water [1]

Q: Dense white fumes evolved
P: No white fumes evolved[1]
(d) (i) PV = nRT

Mr = (mass R T) / PV
(0.219 8.31 423) / (125 x 103 70 10-6) = 88.0[1]
C 3 H 4 O 3 [1]
(ii) A, C 13 H 14 O 3 , and B, C 8 H 8 O have high C:H ratioBenzene ring

present in A and B
A undergoes acidic hydrolysis with dilute H 2 SO 4 to form B and CA

contains an ester group
B undergoes electrophilic substitution and electrophilic addition with

aqueous bromine to form D, C 8 H 7 O 2 Br 3 B contains phenol and
alkene respectively.
B undergoes oxidative cleavage with acidified KMnO 4 to form 4-

hydroxybenzoic acid and CO 2 in a 1:1 mole ratio B contains a
terminal alkene
C undergoes oxidative cleavage with acidified KMnO 4 to form E,

C 3 H 4 O 3 , and carbon dioxide gas in a 1:2 mole ratio Ccontains
alkene and possibly forms ethanedioic acid (further oxidised to form 2
CO 2 ) upon oxidation
C and E undergo oxidation / forms CHI 3 yellow ppt / gave positive

iodoform test with warm aqueous alkaline iodine
C contains CO(CH3) or CH(CH 3 )(OH) group or E contains
CO(CH3) group
E undergoes acid-base reaction with Na 2 CO 3

E contains a carboxylic acid group
O
OH
O
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r dy
dyliine
OH
HO
O
A: B: C: OH

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OH
Br Br
HO
Br
D: HO E: O
4m max for explanations

1m for each structure
[9m]
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5
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INNOVA JUNIOR COLLEGE
JC 2 PRELIMINARY EXAMINATION
in preparation for General Certificate of Education Advanced Level
Higher 2
CANDIDATE
NAME
CLASS INDEX NUMBER
CHEMISTRY 9647/01
Paper 1 Multiple Choice 30 August 2016
1 hour
Answer Sheet.
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InnovaJunior College [Turn over

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2
Section A
to be correct.
1 Carbon disulfide, CS 2 , is a volatile liquid used in the production of cellophane which is used
for food packaging.
On combustion, CS 2 is oxidised as follows:
CS 2 (g) + 3O 2 (g) CO 2 (g) + 2SO 2 (g)
A 20 cm3 sample of carbon disulfide vapour is ignited with 100 cm3 of oxygen. The final
volume of gas after burning is treated with an excess of aqueous alkali.
Which percentage of this final volume dissolves in alkali? (All volumes are measured at
room temperature and pressure.)
A 20%
B 40%
C 60%
D 80%
2 Consider the following half-equations
C 2 O 4 2 2CO 2 + 2e
Fe2+ Fe3+ + e
MnO 4 + 8H+ + 5e

Mn2+ + 4H 2 O
What volume of 0.01 mol dm3 potassium manganate(VII) is needed to completely oxidise
25.0 cm3 of an acidified solution of 0.01 mol dm3 FeC 2 O 4 ?
A 5 cm3
B 7.5 cm3
C 10 cm3
D 15 cm3
3 Which electronic configuration represents an element that forms a simple ion with a
chargeof 3?
A 1s22s22p63s23p1
B 1s22s22p63s23p3
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C 1s22s22p
p63s23p63d14s2
D 1s22s22p
p63s
s23p63d34s2
IJC 2016 Prelim/9647/01 [Turn over

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3
4 Carbon dioxide is a gas at room temperature while silicon dioxide is a solidbecause
A carbon dioxide contains double covalent bonds while silicon dioxide contains single
covalent bonds.
B instantaneous dipole induced dipole attractions are weaker than permanent dipole
permanent dipole attractions.
C carbon-oxygen bonds are less polar than silicon-oxygen bonds.
D van der Waals forces are much weaker than covalent bonds.
5 Under which conditions will the behaviour of a gas be most ideal?

pressure temperature
A high high
B high low
C low high
D low low
6 The enthalpy changes involving some oxides of nitrogen are given below:
N 2 (g) + O 2 J12J H = +180 kJ mol1
1
2NO 2 (g)+ O 2 J1 2 O 5 (g) H = 55 kJ mol1
2
5
N 2 (g) + O 2 J1 2 O 5 (g) H = +11 kJ mol1
2
What is the enthalpy change, in kJ mol1, of the following reaction?
2NO(g) + O 2 J12 2 (g)
A 114 B +114 C 136 D +136
7 A typical protein forms hundreds of hydrogen bonds and thousands of van der Waals forces
in folding from primary to tertiary structures.
Which of the following thermodynamic state functions of the protein best represents the
folding process?
G / kJ mol1 H / kJ mol1 S / J K1 mol1
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e y e
B + +
C +
D + +

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4
8 When 1 mole of carbon dioxide gas solidifies as dry ice, 25.2 kJ of heat energy is
evolved.The sublimation temperature of carbon dioxide is 78.5 C.
What is the entropy change when 132 g of carbon dioxide gas solidifies at this
temperature?
A +130 J K1
B 130 J K1
C +389J K1
D 389 J K1
9 A student set up the hydrogen electrode shown in the diagram below.
What would have to be changed to make this a standard hydrogen electrode?
A the acid solution used

B the temperature of the gas and of the acid solution
C the pressure of the gas
D the metal comprising the electrode
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5
Using inert electrodes, a current was passed through two beakers containing aqueous
silver sulfate and aqueous copper(II) nitrate, connected in series under standard
conditions.
A
At 25oC, 1 atm
1.00 mol dm- 0.50 mol dm-

3 3
Cu(NO3)2(aq) Ag2SO4(aq)
What is the ratio of the mass of silver to copper deposited after the current was passed for
t minutes?
A 0.59 B 0.85
C 1.70 D 3.40
11 A nitrogen-hydrogen mixture, initially in the mole ratio of 1:3, reached equilibrium with
ammonia when 50% of the nitrogen had reacted. The total equilibrium pressure was p.
N 2 (g) + 3H 2 (g) 2NH 3 (g)
What was the partial pressure of ammonia in the equilibrium mixture?
A p B p C p D 2p
3 4 6 7
12 Solid calcium hypochlorite pellets, Ca(ClO) 2 (s), are added to swimming pools to form
HClO(aq), which kills disease-causing bacteria and algae.

Ca(ClO) 2 (s) Ca2+(aq) + 2ClO (aq)

ClO (aq) + H 2 O(l) HClO(aq) + OH (aq)
What is the effect on the solubility of calcium hypochlorite and bacterial growth when pH
decreases?
solubility of calcium hypochlorite effect on bacterial growth
C
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trend
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li
decreases
ecrease
decreases
creases
decreases
increases
more favourable
more favourab
ess favourable
less
more favourable

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6
D increases less favourable

13
The dissociation constant, K w , for the ionisation of water, H 2 O H+ + OH , at different
temperatures is given below.
temperature / C Kw
0 1.15 x 10-15
25 1.00 x 10-14
50 5.50 x 10-14
What can be deduced from this information?
A Only at 25 C are [H+]and [OH-] equal.

B The equilibrium lies furthest to the right at 0C.
C The forward reaction is exothermic.
D The pH of water decreases as temperature increases.
14 A sparingly soluble salt, Mg 3 (PO 4 ) 2 dissociates in aqueous solution as follows:

Mg 3 (PO 4 ) 2 3 Mg2+ + 2 PO 4 3-
Given that the solubility product, K sp of Mg 3 (PO 4 ) 2 is Q, what is the value of [Mg2+] in a
saturated solution?
9 1 1 1 9 1
A ( )5 B ( )3 C ( )5 D ( )3
4 27 108 64
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7
15. The reaction of hydrogen peroxide with iodide ions in an acidic solution is first order with
respect to hydrogen peroxide as well as iodide ions, and zero order with respect to
hydrogen ions.
H 2 O 2 (aq) + 2H+(aq) + 2I(aq) 2H 2 O(l) + I 2 (aq)
Two experiments were carried out. Which pair of diagrams represents the variation of
[H 2 O 2 ] and [H+] with time?
Experiment 1: In the presence of Experiment 2: In the presence of

excess I excess I and H 2 O 2
[H2O2] [H+]
0 time 0 time
[H2O2]
[H+]
0 time
0 time
[H2O2]
[H+]
0 time
0 time
[H2O2] [H+]
0 time 0 time
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8
16 Aluminium is an element in the third period, Na to Ar, of the Periodic Table.
What is true for aluminium?
A Aluminium has the highest melting point of the elements in this period.
B Aluminium is the only element in this period whose chloride reacts with water to form
an acidic solution.
C Aluminium is the only element in this period which can exist, at room temperature
and pressure, as solid and conduct electricity.
D Aluminium is the only element in this period whose oxide reacts with both acids and
bases.
17 Which of the following statements regarding Group II elements or their compounds is

correct?
A Magnesium chloride has a higher melting point than barium chloride.

B Magnesium is a stronger reducing agent than strontium.
C Calcium hydroxide is more thermally stable than barium hydroxide.
D Strontium reacts more readily with oxygen than radium.
18 Which of the following statements about astatine, the element below iodine in Group VII
of the periodic table, is incorrect?
A Silver astatide is insoluble in aqueous ammonia.

B Hydrogen astatide is less stable to heat than hydrogen iodide.
C Sodium astatide and hot concentrated sulfuric acid react to form astatine.
D Astatine and aqueous potassium chloride react to form aqueous potassium astatide
and chlorine.
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9
19 When copper(II) chloride is dissolved in water it gives a blue solution. When this solution is
treated with an excess of concentrated hydrochloric acid it turns yellow.
What are the formulae of the copper species in the blue and yellow solution?
blue yellow
A CuCl 2 [CuCl 4 ]2-
B CuCl 2 (H 2 O) 4 [CuCl 6 ]4-
C Cu(OH) 2 CuCl 2 (H 2 O) 4
D [Cu(H 2 O) 6 ]2+ [CuCl 4 ]2-
20 Four carbon-carbon bonds are labelled in the diagram.

w
x y z
CH CH C CH
Which bonds are made up of an sp2sp2 overlap?
A w and y only
B w, x and y only
C w, x, y and z
D x and y only
21 When heated with chlorine, the hydrocarbon 3,3-dimethylpentane undergoes free radical
substitution. In the propagation step, the free radical X is formed by the loss of one
hydrogen atom.
CH3
CH3CH2 C CH2CH3 Cl X HCl
CH3
How many different forms of Xare theoretically possible?

A 2 B 3 C 4 D 5
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10
22 Bromoethene, CH 2 =CHBr, is unreactive to nucleophiles whereas 3-bromopropene,

CH 2 =CHCH 2 Br is very reactive by comparison.
What explains the lack of reactivity of CH 2 =CHBr?
A Substituted alkenes undergo only electrophilic addition.

B The C=C double bond and the Br atom are both electron withdrawing which
stabilises CH 2 =CHBr.
C The electrons on the Br atom delocalise into the bond.
D The presence of the bond prevents free rotation of the C-Br bond this decreasing
the reactivity.
23 Phosgene, COCl 2 ,is a colourless gas that gained infamy as a chemical weapon during
World War I. It is formed when trichloromethane, CHCl 3 , is left exposed to the atmosphere.
Below is a reaction scheme that involves trichloromethane and phosgene:
CHCl 3 COCl 2 COCl(OH) CO 2 + HCl
Which of the following type of reaction is not being observed in the reaction scheme?
A oxidation
B elimination
C electrophilic addition
D nucleophilic substitution
24 A chlorine-containing organic compound, X, undergoes an elimination reaction when treated

with hot ethanolic potassium hydroxide solution.
What is X?
A CH 2 Cl 2
B C 2 Cl 6
C (CH 3 ) 2 CHCH 2 Cl
D (CH 3 ) 3 CCH 2 Cl
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11
25 Dopamine is an important organic chemical that helps control the brains reward and pleasure
centres. It also helps regulate movement and emotional responses.
NH2
HO CH2CH
CO2H
HO
dopamine
Which of the following statements about dopamine isincorrect?
A It is able to rotate plane-polarized light.

B It is soluble in water due to zwitterion formation.
C It migrates to the negative electrode of an electrolytic cell at pH 14.
D The acidity of dopamine will increase when aqueous bromine is added.
26 Two bottles containing the following reagents had their labels removed.
CH2CH2OH CH2COOH
Cl Cl Cl CH3
Which one of the following reagents can be used to distinguish between them?
A sodium metal
B sodium hydroxide
C hot acidified potassium manganate(VII)
D hot acidified potassium dichromate
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12
27 Marijuana (cannabis) is the most widely used illegal drug in many developed countries.
Medical studies have shown that the active ingredient in marijuana, tetrahydrocannabinol,
might provide medical benefits to some patients.
OH
O
tetrahydrocannabinol
In the following reactions, the O remains unaltered.
Which reaction will tetrahydrocannabinol undergo?
A It reacts with aqueous bromine to incorporate up to 2 atoms of bromine in each

molecule.
B It reacts with hot acidified potassium dichromate(VI) to form a green solution.
C It reacts with dilute nitric acid to form a substitution product.
D It reacts with ethanoic acid to form a sweet-smellingproduct.
28 A student carried out an experiment to study the ease of hydrolysis of a series of chlorinated
compounds, and recorded the observations based on the addition of acidified silver nitrate
solution.
Which of the following gives the expected results?
time taken for precipitate to appear
shortest longest
A C 6 H 5 Cl CH 2 ClCONH 2 CH 3 COCl COCl 2
B CH 2 ClCONH 2 C 6 H 5 Cl COCl 2 CH 3 COCl
C CH 3 COCl COCl 2 C 6 H 5 Cl CH 2 ClCONH 2
D COCl 2 CH 3 COCl CH 2 ClCONH 2 C 6 H 5 Cl
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13
29 In the following two-step synthesis, Y a solid which is insoluble in water, is one of the
components in the final reaction mixture.
COOH
PCl5, warm NH3

CH2OH X Y
then heat
What is Y?
A CO C CONH2
NH
CH2 CH2OH
+
B COO D CO2 NH4
+
CH2NH3 CH2NH2
30 Benzylamine has the formula C 6 H 5 CH 2 NH 2 and is a common precursor in organic

synthesis.
Which of the following statements about benzylamine is correct?
A It decolourises aqueous Br 2 .
B It can be produced by reduction of C 6 H 5 CH 2 CN.
C It reacts with CH 3 COOH to form C 6 H 5 CH 2 NHCOCH 3 .
D It reacts with excess CH 3 CH 2 Cl to form the compound, C 13 H 22 NCl.
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14
Section B
be correct.
A B C D
1, 2 and 3 1 and 2 2 and 3 1 only

are only are onlyare is
31 Gaseous particle Y has a proton(atomic) number n and a charge of +1.
Gaseous particle Z has a proton(atomic) number of n+1 and is isoelectronic with Y.
Which statement correctly describes Y and Z?
1 Y has a larger radius than Z.

2 Y requires more energy than Z when a further electron is removed from each particle.
3 Y releases more energy than Z when an electron is added to each particles.
32 Which of the following molecules will form a hydrogen bond with another of its own
molecules?
1 CH 3 NH 2
2 CH 3 CHO
3 CH 3 CH 2 F
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15
33 The graph below shows the results of an investigation of the initial rate of hydrolysis of
maltose by the enzyme amylase. In the experiments, the initial concentration of maltose
was varied but that of amylase was kept constant.
Initial rate of
reaction
[maltose]
Which conclusions can be deduced from these results?
1 When [maltose] is low, the rate is first order with respect to[maltose].
2 When [maltose] is high, the rate is independent of[maltose].
3 When [maltose] is high, the rate is independent of[amylase].
34
With reference to the Data Booklet and the data below, deduce which of the following
statements are correct.
Half-equation E/V
VO 2 +(aq) + 2H+(aq) + e- VO2+(aq) + H 2 O(l) +1.00
VO2+(aq) + 2H+(aq) + e- V3+(aq) + H 2 O(l) +0.34
V3+(aq) + e- V2+(aq) + H 2 O(l) -0.26

Xx
1 An excess of zinc is capable of reducing VO 2 +(aq) to V2+(aq) in acidic conditions.
2 Fe3+(aq) is capable of oxidising V2+(aq) to VO 2 + (aq) in acidic conditions.
3 Zn2+(aq) ions will oxidise V2+(aq) ions to V3+(aq) ions.
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16
35 The working range and colourchange of chlorophenol red is given below.
colour change
indicator working pH range
Acid Alkali
chlorophenol red 4.8 6.4 Yellow Red
Two drops of this indicator are added to each of the three aqueous solutions listed below.
Which solution has its colour correctly stated?
solution colour
1 aluminium oxide added to water Red
2 0.1 mol dm-3 of CH 3 COOH (K a = 1.8 x 10-5 mol dm-3) Yellow
solution of sodium ethanoate and ethanoic acid in

3 Orange
1:2 proportion [pK a of ethanoic acid = 4.7]
Which statements about the trends in properties of the hydrogen halides are correct?
1 Volatility decreases in the order: HF > HCl> HBr > HI.

2 Thermal stability increases in the order: HI< HBr < HCl< HF.
3 Ease of oxidation increases in the order: HF < HCl< HBr < HI.
37 Nickel is purified by a method called the Mond process. The equation of the first step of the
purification is shown below.
Ni(s) + 4CO(g) Ni(CO) 4 (l)
Which of the following statements are correct?
1 CO is a monodentate ligand.
2 Ni in Ni(CO) 4 has a co-ordination number of 4.
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3 The oxidation
dation
a number of Ni in Ni(CO) 4 is zero.

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17
38 Compound X is a synthetic precursor of meloscine, an alkaloid isolated from the New

Caledonian plant Melodinus Scandens Forst.
compoundX
Which of the following statements about its reactions are correct?
1 1 mol of X reacts with 2 mol of HBr(g) when heated.

2 1 mol of X reacts with 4 mol of Br 2 (aq) at room temperature.
3 1 mol of X reacts with 2 mol of CH 3 COCl at room temperature.
39 Which of the following reactions give products that does not rotate the plane of polarised
light?
1 1bromobutane refluxed with aqueous KOH

2 butanone reacted with HCN, trace amount of NaOH
3 bXWHQHUHDFWHGZLWKEURPLQHGLVVROYHGLQRUJDQLFVROYHQW
40 Which of the following could result in the loss of the tertiary structure of a protein?
1 addition of weak acid

2 addition of alcohol
3 addition of AgNO 3 solution
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ne
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JC 2 PRELIMINARY EXAMINATION 2
Higher 2
CANDIDATE
NAME
CLASS INDEX NUMBER
CHEMISTRY 9647/01
Paper 1 Multiple Choice 30 August 2016
1 hour
Answer Sheet.
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This
y
Thi document
d t consists
i t off 16 printed
i t d pages and
d 0 blank
bl k page.
InnovaJunior College [Turn over

425 trendyline
2
Section A
to be correct.
1 Carbon disulfide, CS 2 , is a volatile liquid used in the production of cellophane which is used
for food packaging.
On combustion, CS 2 is oxidised as follows.
CS 2 (g) + 3O 2 (g) CO 2 (g) + 2SO 2 (g)
A 20 cm3 sample of carbon disulfide vapour is ignited with 100 cm3 of oxygen. The final
volume of gas after burning is treated with an excess of aqueous alkali.
Which percentage of this final volume dissolves in alkali? (All volumes are measured at
room temperature of pressure.)
A 20%
B 40%
C 60%
D 80%
Answer: C
1 mole of CS 2 reacts with 60cm3 of O 2 , remaining volume of O 2 = 40 cm3
produces 1 mole of CO 2
20 cm3 of CS2 produces 20 cm3 of CO 2 and 40 cm3 of SO 2
Total volume of gases at the end of reaction = 40 + 20 + 40 = 100 cm3
Both CO 2 and SO 2 are acidic gases which will react with NaOH
Hence % of final volume dissolved in alkali 60/100 x 100% = 60%
2 Consider the following half-equations
C 2 O 4 2 2CO 2 + 2e
Fe2+ Fe3+ + e
MnO 4 + 8H+ + 5e

Mn2+ + 4H 2 O
What volume of 0.01 mol dm3 potassium manganate(VII) is needed to completely oxidise
25.0 cm3 of an acidified solution of 0.01 mol dm3 FeC 2 O 4 ?
A 5 cm3
B 7.5 cm3
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C 10 cm3
D 15 cm3
Answer: D
qns:
Combining eqns:
FeC 2 O 4 Fe3++ 2CO 2 + 3ex5
IJC 2016Prelim 2/9647/01[Turn over

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3
MnO 4 + 8H+ + 5e Mn2+ + 4H 2 O x3
Overall equation: 3MnO 4 + 5FeC 2 O 4 10CO 2 + 5Fe3+ + 3Mn2+ + 12H 2 O
Amount of FeC 2 O 4 = 25/100 x 0.01 = 0.00025 mol

Mole ratio of FeC 2 O 4 : MnO 4 = 5 : 3
Amount of MnO 4 = 3/5 x 0.00025 = 0.00015 mol
Volume of MnO 4 = 0.00015 / 0.01 = 0.015 dm3 = 15 cm3
3 Which electronic configuration represents an element that forms a simple ion with a charge
of 3?
A 1s22s22p63s23p1
B 1s22s22p63s23p3
C 1s22s22p63s23p63d14s2
D 1s22s22p63s23p63d34s2
Answer:B
A : Group III element : + 3 ion
B: Group V : 3 ion
C and D are transition elements forms positively charged ions
4 Carbon dioxide is a gas at room temperature while silicon dioxide is a solidbecause
A carbon dioxide contains double covalent bonds while silicon dioxide contains single
covalent bonds.
B instantaneous dipole induced dipole attractions are weaker than permanent dipole
permanent dipole attractions.
C carbon-oxygen bonds are less polar than silicon-oxygen bonds.
D van der Waals forces are much weaker than covalent bonds.
Answer D
Carbon dioxide is a simple molecules with weak can der waals forces of attraction
between molecules while silicon dioxide is a giant covalent structure with strong covalent
bonds. Thus, less amt of energy is required to overcome the weaker VDW forces of
attraction between CO 2 molecules, resulting in lower boiling point.
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4
5 Under which conditions will the behaviour of a gas be most ideal?
pressure temperature
A high high
B high low
C Low high
D Low low
Answer: C
Gas behave most ideally at high temperatures and low pressures.
At high temperatures, particles have sufficient energy to overcome the intermolecular forces of
attraction.
At low pressures, particles are very far apart. The volume of the particles is negligible to the
volume of container which they moves in; intermolecular forces of attraction is negligible.
6 The enthalpy changes involving some oxides of nitrogen are given below:
N 2 (g) + O 2 J12J H = +180 kJ mol1
1
2NO 2 (g)+ O 2 J1 2 O 5 (g) H = 55 kJ mol1
2
5
N 2 (g) + O 2 J1 2 O 5 (g) H = +11 kJ mol1
2
What is the enthalpy change, in kJ mol1, of the following reaction?
2NO(g) + O 2 J12 2 (g)
A 114 B +114 C 136 D +136
Answer: A
5HYHUVH(TXDWLRQ12J1 2 (g) + O 2 JH = 180 kJ mol1
1
Reverse Equation 2: N 2 O 5 J12 2 (g)+ O 2 JH = +55 kJ mol1
2
5
Equation 3 remains: N 2 (g) + O 2 J1 2 O 5 (g) H = +11 kJ mol1
2
Sum up these 3 equations:2NO(g) + O 2 J12 2 JH = 180+55+11

= 114 kJ mol1

428 trendyline
5
7 A typical protein forms hundreds of hydrogen bonds and thousands of van der Waals forces
in folding from primary to tertiary structures.
Which of the following thermodynamic state functions of the protein best represents the
folding process?
G / kJ mol1 H / kJ mol1 S / J K1 mol1
B + +
C +
D + +
Answer: A
When hydrogen bonds and van der Waals forces are formed, heat will be released. Thus H
is negative.
When the protein is folded from primary to tertiary structures, the system becomes less
disordered. Thus S is negative.
The process of protein folding is spontaneous. Thus, G is negative.
8 When 1 mole of carbon dioxide gas solidifies as dry ice, 25.2 kJ of heat energy is
evolved.The sublimation temperature of carbon dioxide is 78.5 C.
What is the entropy change when 132 g of carbon dioxide gas solidifies at this
temperature?
A +130 J K1
B 130 J K1
C +389 J K1
D 389 J K1
Answer: D
This is a phase change reaction.G = 0
G = H TS

S =

25200 0
S =
78.5+273
ttrendyline
25200
0
S =
194.5
6 J K-1
S = 129.56
132
Swhen 132 g of carbon dioxide gas solidifies = 129.56
129 56 x = 389 J K-1
44

429 trendyline
6
9 A student set up the hydrogen electrode shown in the diagram below.
What would have to be changed to make this a standard hydrogen electrode?
A the acid solution used

B the temperature of the gas and of the acid solution
C the pressure of the gas
D the metal comprising the electrode
Answer:A
In 1.0 mol dm3 sulfuric acid, [H+] = 2.0 mol dm3. To make the electrode a standard
hydrogen electrode, either change the acid to a 1.0 mol dm3 monoprotic acid (option A),
or halve the concentration of sulfuric acid used.
Using inert electrodes, a current was passed through two beakers containing aqueous
silver sulfate and aqueous copper(II) nitrate, connected in series under standard
conditions.
At 25oC, 1 atm
1.00 mol dm- 0.50 mol dm-

3 3
Cu(NO3)2(aq) Ag2SO4(aq)
t minutes?
A
trendyline
What is the ratio
atio of the mass of silver to copper deposited after the curren
0.59
59 B 0.85
0 85
current was passed for

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7
C 1.70 D 3.40
Answer: D
It = n e F
It
transferred =
F
Cu2+ + 2e Cu
It
Cu =
2F
Ag+ + e Ag
It
Ag =
F
It
mass of Ag formed Ar x no. of moles of Ag formed 108 x F
= = It =3.40
mass of Cu formed Ar x no. of moles of Cu formed 63.5 x
2F
11 A nitrogen-hydrogen mixture, initially in the mole ratio of 1:3, reached equilibrium with
ammonia when 50% of the nitrogen had reacted. The total equilibrium pressure was p.
N 2 (g) + 3H 2 (g) 2NH 3 (g)
What was the partial pressure of ammonia in the equilibrium mixture?
A p B p C p D 2p
3 4 6 7
Ans A
N 2 (g) + 3H 2 (g) 2NH 3 (g)

Initial amt x 3x
Change x/2 3x/2 x
Eqm amt x/2 3x-3x/2 x
Total final pressure = sum of eqm partial pressure = x/2 + (3x-3x/2) + x = p

3x = p x = p/3
12 Solid calcium hypochlorite pellets, Ca(ClO) 2 (s), are added to swimming pools to form
HClO(aq), which kills disease-causing bacteria and algae.

Ca(ClO) 2 (s) Ca2+(aq) + 2ClO (aq)

ClO (aq) + H 2 O(l) HClO(aq) + OH (aq)
What is the effect on the solubility of calcium hypochlorite and bacterial growth when pH
decreases?
B
ttrendyline
trend
dyline
bility
li
ility of calcium hypochlorite
Solubility
crease
decreases
decreases
Effect on bacterial growth
ore favourable
more
less favourable

431 trendyline
8
C increases more favourable
D increases less favourable

Answer: D
When pH decreases, [H+] increases and [OH] decreases, equilibrium position of second
equation shift to the right and [HClO] increases. Bacterial growth will be less favourable.
When [ClO] decreases, equilibrium position of first equation shift to the right
and solubility of calcium hypochlorite increases.
13
The dissociation constant, K w , for the ionisation of water, H 2 O H+ + OH , at different
temperatures is given below.
temperature / C Kw
0 1.15 x 10-15
25 1.00 x 10-14
50 5.50 x 10-14
What can be deduced from this information?
A Only at 25 C are [H+]and [OH-] equal.

B The equilibrium lies furthest to the right at 0C.
C The forward reaction is exothermic.
D The pH of water decreases as temperature increases.
Answer: D
Option A is wrong as [H+]and [OH-] are equal at all temperature for pure water.
Option B is wrong as the equilibrium lies furthest to the right at 50C (as shown by K w
value).
Option C is wrong as the forward reaction is endothermic. When temperature increases,
K w increases. This shows that equilibrium lies to the right.
Option D is correct as the forward reaction is endothermic. When temperature increases,
K w increases. This shows that equilibrium lies to the right.[H+] increases and this leads to
decrease in pH.
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9
14 A sparingly soluble salt, Mg 3 (PO 4 ) 2 dissociates in aqueous solution as follows:

Mg 3 (PO 4 ) 2 3 Mg2+ + 2 PO 4 3-
Given that the solubility product, K sp of Mg 3 (PO 4 ) 2 is Q, what is the value of [Mg2+] in a
saturated solution?
9 1 1 1 9 1
A ( )5 B ( )3 C ( )5 D ( )3
4 27 108 64
Answer: A
Mg 3 (PO 4 ) 2 3 Mg2+ + 2 PO 4 3-
Change x + 3x + 2x
Equilibrium 3x 2x
K sp = [Mg2+]3 [PO 4 3-]2
Q = (3x)3 (2x)2
Q = (27x3) (4x
1

x=( ) 5
108
1

[Mg2+] = 3 x ( )5
108
1
243 5
=( )
108
1
9 5
=( )
4
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10
15. The reaction of hydrogen peroxide with iodide ions in an acidic solution is first order with
respect to hydrogen peroxide as well as iodide ions, and zero order with respect to
hydrogen ions.
H 2 O 2 (aq) + 2H+(aq) + 2I(aq) 2H 2 O(l) + I 2 (aq)
Two experiments were carried out. Which pair of diagrams represents the variation of
[H 2 O 2 ] and [H+] with time?
Experiment 1: In the presence of Experiment 2: In the presence of

excess I excess I and H 2 O 2
[H2O2] [H+]
0 time 0 time
[H2O2]
[H+]
0 time
0 time
[H2O2]
[H+]
0 time
0 time
[H2O2] [H+]
trendyline
tre
e yline
n
D
0 time
tim 0 time
Ans B

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11
Given in question: Rate = k[H 2 O 2 ][I],

For expt 1: [I-] is first order
The graph of [H 2 O 2 ] against time is a downward sloping curve with decreasing gradient.
Rate = k[H 2 O 2 ] where k = k[I]
For expt 2:
[H+] is zero order. The graph of [H+] against time is a decreasing straight line with a constant
gradient.
Rate = k where k = k[I][H 2 O 2 ]
16 Aluminium is an element in the third period, Na to Ar, of the Periodic Table.
What is true for aluminium?
A Aluminium has the highest melting point of the elements in this period.
B Aluminium is the only element in this period whose chloride reacts with water to form
an acidic solution
C Aluminium is the only element in this period which can exist, at room temperature
and pressure, as solid and conduct electricity.
D Aluminium is the only element in this period whose oxide reacts with both acids and
bases.
Answer: D
Period 3 trends
Aluminium is the only amphoteric oxide in third period.
17 Which of the following statements regarding Group II elements or their compounds

is correct?
A Magnesium chloride has a higher melting point than barium chloride.

B Magnesium is a stronger reducing agent than strontium.
C Calcium hydroxide is more thermally stable than barium hydroxide.
D Strontium reacts more readily with oxygen than radium.
Answer:
MgCl 2 has a larger magnitude of lattice energy than BaCl 2 since ionic radius of Mg2+ is
smaller than that of Ba2+ ion.
Mg is a weaker reducing agent or undergoes oxidation less readily than Sr since
trendyline
Eo(Mg2+/Mg) is less negative than Eo(Sr2+/Sr).
/Sr)
Ca(OH) 2 is less
ess Ba(O 2 as Ca2+
ss thermally stable than Ba(OH) 2
has a higher charge
cha density than
Ba2+ (due to the
he smaller ionic radius of Ca2+. Ca2+ polarises
larises tthe electron ccloud of OH- ions
O bond in the hydroxide ions to a greater extent, thus less energy is
and weakens the O-H

435 trendyline
12
required for the decomposition of Ca(OH) 2.
The reactivity of Group II metals increases down the group due to increasing reducing
power of the metals down the Group. Since Sr is above Ra in Group II, Sr is expected to
react less readily with oxygen than Ra.
18 Which of the following statements about astatine, the element below iodine in Group VII
of the periodic table, is incorrect?
A Silver astatide is insoluble in aqueous ammonia.

B Hydrogen astatide is less stable to heat than hydrogen iodide.
C Sodium astatide and hot concentrated sulfuric acid react to form astatine.
D Astatine and aqueous potassium chloride react to form aqueous potassium astatide
and chlorine.
Answer:
AgI is insoluble in both dilute and concentrated NH 3 and since Ksp of AgX decreases
down the group, AgAt is expected to be less soluble in both dilute and concentrated NH 3
than AgI.
H-At bond is weaker than H-I bond since At atom is bigger and more diffuse leading to
less effective orbital overlap in H-At bond.
Since reducing power of the halides increases down the group and NaI reacts with conc
H 2 SO 4 to give I 2 , NaAt is similarly expected to react with conc H 2 SO 4 to give I 2.
At 2 cannot undergo displacement reaction with KCl since At 2 is a weaker oxidising agent
(or less likely to undergo reduction) than Cl 2 as oxidising power of halogen decreases
down the group.
19 When copper(II) chloride is dissolved in water it gives a blue solution. When this solution is
treated with an excess of concentrated hydrochloric acid it turns yellow.
What are the formulae of the copper species in the blue and yellow solution?
blue yellow
A CuCl 2 [CuCl 4 ]2-
B CuCl 2 (H 2 O) 4 [CuCl 6 ]4-
C Cu(OH) 2 CuCl 2 (H 2 O) 4
trendyline
tre
endyyline
D (H 2 O)) 6 ]2+
[Cu(H [[CuCll 4 ]2-
[CuC
Answer: D
hloride
oride dissolves in water, it dissociates into C
When copper(II) chloride Cu2+ and
d Cl- iions. The Cu2+ ions
2+
exist in the hydrated
d form,
form [Cu(H 2 O) 6 ] , which is blue
ue in colour.
colour

436 trendyline
13
When excess conc HCl is added, ligand exchange occurs, where the Cl- ligand displace the H 2O
ligands to form [CuCl 4 ]2-, according to the following equation.
[Cu(H 2 O) 6 ]2+ + 4Cl- [CuCl 4 ]2- + 6 H2O
20 Four carbon-carbon bonds are labelled in the diagram.

w
x y z
CH CH C CH
Which bonds are made up of an sp2sp2 overlap?
A w and y only
B w, x and y only
C w, x, y and z
D x and y only
Answer: B
$OOWKHFDUERQVDUHVSH[FHSWWKHERQGIRU]ZKHUHWKHFDUERQLQ&&LVVSK\EULGL]HG
21 When heated with chlorine, the hydrocarbon 3,3-dimethylpentane undergoes free radical
substitution. In the propagation step, the free radical X is formed by the loss of one
hydrogen atom.
CH3
CH3CH2 C CH2CH3 Cl X HCl
CH3
How many different forms of Xare theoretically possible?

A 2 B 3 C 4 D 5
Answer: B
There are 3 types of Hydrogen atoms that can be lost.
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i
437 trendyline
14
22 Bromoethene, CH 2 =CHBr, is unreactive to nucleophiles whereas 3-bromopropene,

CH 2 =CHCH 2 Br is very reactive by comparison.
What explains the lack of reactivity of CH 2 =CHBr?
A Substituted alkenes undergo only electrophilic addition.

B The C=C double bond and the Br atom are both electron withdrawing which
stabilises CH 2 =CHBr.
C The electrons on the Br atom delocalise into the bond.
D The presence of the bond prevents free rotation of the C-Br bond this decreasing
the reactivity.
Answer: C
For halogen-containing organic compounds, reactivity to nucleophiles (such as OH-)
depends on the bond strength of C-X bonds. The unreactivity of bromoethene with
nucleophile possibly suggest stronger C-Br bonds, as a result of the p orbital of Br
overlapping with bonds, hence having partial double-bond character.
23 Phosgene, COCl 2 ,is a colourless gas that gained infamy as a chemical weapon during
World War I. It is formed when trichloromethane, CHCl 3 , is left exposed to the atmosphere.
Below is a reaction scheme that involves trichloromethane and phosgene:
Which of the following type of reaction is not being observed in the reaction scheme?
A Oxidation
B Elimination
C Electrophilic addition
D Nucleophilic substitution
Ans:C

Oxidation nucleophilic substitution elimination
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438 trendyline
15
24 A chlorine-containing organic compound, X, undergoes an elimination reaction when treated

with hot ethanolic potassium hydroxide solution.
What is X?
A CH 2 Cl 2
B C 2 Cl 6
C (CH 3 ) 2 CHCH 2 Cl
D (CH 3 ) 3 CCH 2 Cl
Answer: C
To undergo elimination, there must be a hydrogen atom on the carbon atom adjacent to the
carbon atom bearing the halogen atom. Only option C fulfils this criterion.
25 Dopamine is an important organic chemical that helps control the brains reward and pleasure
centres. It also helps regulate movement and emotional responses.
NH2
HO CH2CH
CO2H
HO
Dopamine
Which of the following statements about dopamine isincorrect?
A It is able to rotate plane-polarized light.

B It is soluble in water due to zwitterion formation.
C It migrates to the negative electrode of an electrolytic cell at pH 14.
D The acidity of dopamine will increase when aqueous bromine is added.
trendyline
439 trendyline
16
Ans: C
Option A: Dopamine indeed contains a chiral carbon and exhibits optical activity
Option B: Dopamine is able to exist as a zwitterion RCH(NH3+)(COO-) which is able to form

ion-dipole interactions with water.
Option C: At pH 14, the COOH group is deprotonated. The predominant form is the anionic
form, which should migrate to the positive electrode instead of the negative electrode.
Option D: When aqueous bromine is added, electrophilic substitution occurs with the
introduction of Br into the benzene ring. Br is electron withdrawing and is able to disperse the
negative charge on the oxygen atoms in the anion, thus increasing the acidity of the
compound.
26 Two bottles containing the following reagents had their labels removed.
CH2CH2OH CH2COOH
Cl Cl Cl CH3
Which one of the following reagents can be used to distinguish between them?
A sodium metal C hot acidified potassium

manganate(VII)
B sodium hydroxide D hot acidified potassium dichromate
Ans: D
Option A: Both compounds react with Na. Effervescence will be seen for both compounds.
Gas evolved will extinguish lighted splint with a pop sound.
CH2COOH CH2CH2OH
Cl CH3
Option B: can react with NaOH but not Cl Cl .
However, the reaction is not easily visible.
CH2CH2OH CH2COOH
trendyline
re
e li
Cll
C CH3
CH
oth C
Option C: Both Cll Cll and reacts with hot acidified
KMnO 4 via side
de
e chain oxidation. Hence purple KMnO 4 will decolourise for both compounds
and effervescence
cence will be seen for both. Gas evolved will form white ppt with
w Ca(OH) 2 .

440 trendyline
17
CH2CH2OH
Option D: Cl Cl reacts with hot acidified K 2 Cr 2 O 7 via oxidation of primary

CH2COOH
Cl CH3
alcohol (orange solution turns green). does not undergo side chain
oxidation as K 2 Cr 2 O 7 is a weaker oxidizing agent than KMnO 4 .
27 Marijuana (cannabis) is the most widely used illegal drug in many developed countries.
Medical studies have shown that the active ingredient in marijuana, tetrahydrocannabinol,
might provide medical benefits to some patients.
OH
O
tetrahydrocannabinol
In the following reactions, the O remains unaltered.
Which reaction will tetrahydrocannabinol undergo?

A It reacts with aqueous bromine to incorporate up to 2 atoms of bromine in each
molecule.
B It reacts with hot acidified potassium dichromate(VI) to form a green solution.
C It reacts with dilute nitric acid to form a substitution product.
D It reacts with ethanoic acid to form a sweet-smelling product.
Ans: C
Option A is incorrect because both alkene group and phenol group will react with
aqueous Br 2 to incorporate 3 Br atoms, forming the following products:
OH Br
Br OH
OH OH
Br Br
OR
O O
Br Br
trendyline
(more major) (less major)
Option B iss incorrect. K 2 Cr 2 O 7 is not strong enough to oxidise

oxidis side-chain of
benzene andd alkene. Phenol is not oxidised as wewell.
Option C is correct. Dilute

t Dil t nitric
it i acidid reacts
t with
ith phenol
h l functional
f t group via
electrophilic substitution to form the following product:

441 trendyline
18
OH OH
NO2 Or
O O
NO2
Option D is incorrect. Phenol functional group does not react readily with ethanoic
acid (even in the presence of conc. H 2 SO 4 as catalyst). Hence, no ester will be
formed. (To form the ester, the phenol should be treated with aq. NaOH to generate
a stronger phenoxide ion before added into ethanoyl chloride)
28 A student carried out an experiment to study the ease of hydrolysis of a series of chlorinated
compounds, and recorded the observations based on the addition of acidified silver nitrate
solution.
Which of the following gives the expected results?
time taken for precipitate to appear
shortest longest
A C 6 H 5 Cl CH 2 ClCONH 2 CH 3 COCl COCl 2
CH 3 COCl
B CH2ClCONH2 C6H5Cl COCl2
C
CH 3 COCl CH 2 ClCONH 2
COCl2 C6H5Cl
D
COCl 2
CH3COCl CH2ClCONH2 C6H5Cl
Ans: D
COCl 2 and CH 3 COCl more reactive as the highly electronegative O and Cl atoms that are
bonded to acyl carbon make it more electron deficient (or more + charged), thus attract
nucleophiles more readily. COCl 2 hydrolyses more rapidly than CH 3 COCl as the former has
its acyl carbon more electron deficient due to its additional Cl atom.
In addition, the acyl carbon atoms are sp2 hybridised, so they have trigonal planar
arrangement with respect to C, resulting in less steric hindrance for the approach of
nucleophiles compared to the sp3 C atom (that is bonded to Cl in CH 2 ClCONH 2 ).
CH 2 ClCONH 2 is the next most reactive as the C atom bonded to only one highly
electronegative Cl atom is less electron deficient (or less + charged) compared to COCl 2
and CH 3 COCl.
C 6 H 5 Cl is a halogenoarene (or aryl halide) where its Cl atom is bonded directly to benzene
ring. The p orbital of Cl overlaps with the electron cloud of benzene ring resulting its lone
trendyline
pair being delocalized
calized into benzene and double bond character
ocalized char in its C-Cl
C-Cl bond. Since its C-
Cl is most difficult
cult to break, nucleophilic substitution (or hydrolysis) cannot o
occur.
29 In the following
ng two-step synthesis, Y a solid which is insoluble in water,
id w wa is one of the
components in the final reaction mixture.

442 trendyline
19
COOH
PCl5, warm NH3

CH2OH X Y
then heat
What is Y?
A CO C CONH2
NH
CH2 CH2OH
+
B COO D CO2 NH4
+
CH2NH3 CH2NH2
Ans: A
COOH COCl COCl
PCl5, warm NH3
CH2OH CH2Cl CH2NH2
then heat
X
heat
CO
NH
CH2
Y
COCl
CH2NH2
The reaction of X with NH 3 produces a mixture of products. is one of the
products which contains an amine group and an acyl chloride group. The amine group is
nucleophilic and undergo intramolecular reaction with the electron-deficient C of the acyl
chloride to form a cylic product.
Since reaction with PCl 5 converts COOH to COCl and CH 2 OH to CH 2 Cl (as shown in
trendyline
X), the product should not contain COO- or CH 2 OH g
group.
p Hence,, by elimination of
options, B, C and D are incorrect.
30 Benzylamine has the formula C 6 H 5 CH 2 NH

N 2 and is a common precursor
pre in organic
synthesis.

443 trendyline
20
Which of the following statements about benzylamine is correct?
A It decolourises aqueous Br 2 .
B It can be produced by reduction of C 6 H 5 CH 2 CN.
C It reacts with CH 3 COOH to form C 6 H 5 CH 2 NHCOCH 3 .
D It reacts with excess CH 3 CH 2 Cl to form the compound, C 13 H 22 NCl.
(A) CH 2 NH 2 group is not strongly activating, hence benzylamine, C 6 H 5 CH 2 NH 2 , cannot

undergo easy electrophilic substitution with aqueous Br 2 . This is not to be confused
with phenylamine, C 6 H 5 NH 2 .
(B) When C 6 H 5 CH 2 CN undergoes reduction, C 6 H 5 CH 2 CH 2 NH 2 is produced, not
C 6 H 5 CH 2 NH 2 .
(C) C 6 H 5 CH 2 NH 2 undergoes acid base reaction, not condensation reaction, with
CH 3 COOH to give C 6 H 5 CH 2 NH 3 +CH 3 COO. An amide is formed from condensation
between a primary or secondary amine and acyl halide.
(D) A quaternary ammonium salt (shown below) is formed from successive nucleophilic
substitutions (polyalkylation).
CH2CH3
+
CH2N CH2CH3 Cl-
CH2CH3
Section B
be correct.
A B C D
1, 2 and 3 1 and 2 2 and 3 1 only

are only are onlyare is
31 Gaseous particle Y has a proton(atomic) number n and a charge of +1.
Gaseous particle Z has a proton(atomic) number of n+1 and is isoelectronic with Y.
Which statement correctly describes Y and Z?
1 Y has a larger radius than Z.

2
3
Ans: D trendyline
Y requires
res more energy than Z when
ses
es more energy than
Y releases
hen a further electron is removed ffrom
fr each particle.
th Z when an electron is added to each particles.
Statement 1 (correct) Y (less protons) and isoelectronic

and has a larger radius.
oele
p
pa
with Z has a low

lower nuclear charge

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21
Statement 2: (wrong) Z has a higher nuclear charge and hold electrons more
strongly(stronger attraction) and hence requires more energy.
32 Which of the following molecules will form a hydrogen bond with another of its own
molecules?
1 CH 3 NH 2
2 CH 3 CHO
3 CH 3 CH 2 F
Answer: D
Option 1: There is H-bonding between CH 3 NH 2 .
Option 2: No H-bonding as O is not directly bonded to H atom.
Option 3: No H-bonding as F is not directly bonded to H atom.
33 The graph below shows the results of an investigation of the initial rate of hydrolysis of
maltose by the enzyme amylase. In the experiments, the initial concentration of maltose
was varied but that of amylase was kept constant.
Initial rate of
reaction
[maltose]
1 When [maltose] is low, the rate is first order with respect to[maltose].
2 When [maltose] is high, the rate is independent of[maltose].
3 When [maltose] is high, the rate is independent of[amylase].
Answer: B
Answer: B
Option 1:
At low substrate concentration[maltose], not all of the active sites are occupied.
- rate [maltose] reaction is first order with respect to the maltose.
Option 2:
At high [maltose], all the active sites are occupied, i.e. the active sites of the enzyme [amylase]
trendyline
become saturated with
w maltose.
- Any increase in [maltose] will not have any effect on the reaction rate.
- The reaction is
s zero
ero order with respect to the maltose
maltose.
Option 3: If substrate
trate is not the limiting factor, increasing
reas enzyme amylase
concentration will increase theh rate off reaction,
i as there
h will be more active
ill b i sites
i of enzyme.

445 trendyline
22
34
With reference to the Data Booklet and the data below, deduce which of the following
statements are correct.
Half-equation E/V
VO2+(aq) + 2H+(aq) + e- V3+(aq) + H 2 O(l) +0.34
V3+(aq) + e- V2+(aq) + H 2 O(l) -0.26

Xx
1 An excess of zinc is capable of reducing VO 2 +(aq) to V2+(aq) in acidic conditions.
2 Fe3+(aq) is capable of oxidising V2+(aq) to VO 2 + (aq) in acidic conditions.
3 Zn2+(aq) ions will oxidise V2+(aq) ions to V3+(aq) ions.
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446 trendyline
23
Answer: D
Answer: D
Half-equation E/V
Zn2+ + 2e Zn 0.76
Option 1:
Excess Zn is the reducing agent which can reduce VO 2 +(aq) to VO2+(aq)
Ecell = +1.00 (0.76) =1.76V > 0
Excess Zn can further reduce VO2+(aq) to V3+(aq) :
Ecell = +0.34 (0.76) = 1.10V >0
Excess Zn can further reduce V3+(aq) + e- V2+(aq) :
Ecell: 0.26 (0.76) = 0.50V > 0
Quick thinking for MCQ:

Since Ecell = Ered Eoxi > 0 for reaction to proceed (Zn is oxidised),
Ered (0.76) > 0
Ered > 0.76 for reaction to proceed
Option 2: wrong
Quick thinking for MCQ:
Since Ecell = Ered Eoxi > 0 for reaction to proceed
(Fe3+ is reduced to Fe2+),
+0.77 Eoxi > 0
Eoxi < + 0.77 for reaction to proceed
Fe3+ can oxidise V2+ to VO2+ but not VO 2 +
Fe3+ + e Fe2+ +0.77

Ecell = +0.77 1.00 = 0.23v < 0
Another factor: Fe3+ is not in excess, successive oxidation of vandadium compounds
may not occur.
35 The working range and colourchange of Chlorophenol red is given below.
Colour change
Indicator Working pH range
Acid Alkali
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tren
ndyline
e
Chlorophenol
hlorophenol
o red 4.8 6.4
6 Yellow
Y Red
R
Two drops of this

his indicat
indicator
or are added to each of the three aqueous solutio
solutions listed below.
Which solution has its colour correctly stated?

447 trendyline
24
Solution Colour
1 Aluminium oxide added to water Red
2 0.1 mol dm-3 of CH 3 COOH (K a = 1.8 x 10-5 mol dm-3) Yellow
Solution of sodium ethanoate and ethanoic acid in

3 Orange
1:2 proportion [pK a of ethanoic acid = 4.7]
Answer: B
Option 1 is correct.
Aluminium oxide does not dissolve in water and it gives a pH7 solution. According
to the working pH range of this indicator, the color is red.
[H+] = K a [acid]
= 1.8X10-5 [0.1]
= 1.342 10-3 mol dm-3
pH = - log 10 (1.342 10-3) = 2.87
According to the working pH range of this indicator, the color shown for a solution
of pH 2.87 is yellow.
Option 3 is incorrect.
[]
pH = pK a + log =4.7 + log 0.5 = 4.7 0.3 = 4.4
[]
According to the working pH range of this indicator, the color shown for a solution
of pH 4.4 is yellow and not orange.
Which statements about the trends in properties of the hydrogen halides are correct?
1 Volatility decreases in the order: HF > HCl> HBr > HI.
2 Thermal stability increases in the order: HI< HBr < HCl < HF.
3 Ease of oxidation increases in the order: HF < HCl< HBr < HI.
Ans: C
Option 1:Volatility is inversely proportional to the boiling point. The higher the boiling point,
the less volatile the substance. HF has stronger intermolecular hydrogen bonding that
requires more energy to break while the strength of instantaneous dipole-induced dipole
interaction increases from HCl to HBr to HI due to increasing polarizability of electron cloud
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of the molecules. Thus the correct trend of volatilityy is HF < HI < HBr < HCl.
Option 2:Thermal strength of H-X. The

ermal stability of hydrogen halides depend on the bond stre
stronger the H-X
H--X bond, the more thermally stable the hydrogen halides. Do
Down the group, the
valence orbital overlap between the
al is more diffused, as there is less effective orbital ove
valence orbitals
als of hydrogen and halogen OR down
dow the group, as the atom
atomic size of halogen
increases, the H-X bond length increases. As such, the H-X bond strength is weaker, and

448 trendyline
25
less thermally stable. Therefore, the trend of increasing thermal stability (HI< HBr < HCl <
HF) is correct.
Option 3:The ease of oxidation or reducing power of the halides increases down the group
due to the less positive Eo(X 2 /X-) down the group. Hence, the trend is correct.
37 Nickel is purified by a method called the Mond process. The equation of the first step of the
purification is shown below.
Ni(s) + 4CO(g) Ni(CO) 4 (l)
1 CO is a monodentate ligand.
2 Ni in Ni(CO) 4 has a co-ordination number of 4.
3 The oxidation number of Ni in Ni(CO) 4 is zero.
Ans: A
CO is a monodentate ligand as it forms one dative bond (using the lone pair of electron on
the carbon atom) per formula unit.
Ni in Ni(CO) 4 has 4 dative or coordinate bonds formed with 4 CO ligands, thus its
coordination number is 4.
Since the charges of the complex compound, Ni(CO) 4 and CO ligands are zero, the charge
of Ni is zero too.
38 Compound X is a synthetic precursor of meloscine, an alkaloid isolated from the New

Caledonian plant Melodinus Scandens Forst.
compoundX
Which of the following statements about its reactions are correct?
1 1 mol of X reacts with 2 mol of HBr(g) when heated.

2 1 mol of X reacts with 4 mol of Br 2 (aq) at room temperature.
3 1 mol of X reacts with 2 mol of CH 3 COCl at room temperature.
Ans: C
Option 1: Incorrect. 1 mol of X reacts with 3 mol of HBr.
Each C=C will undergo electrophilic addition with HBr. 1 alcohol will undergo nucleophilic
substitution with HBr, heat.
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Option 2: Correct
rect
Each C=C will undergo electrophilic additionadditio with h Br 2 (aq).
aq). Phenyla
Phenylamine
Phenylam will undergo
electrophilic substitution with 2 mol of Br 2 to form the di
d
di-substituted
-substituted
substituted produc
product.
rect
Option 3: Correctect
1 alcohol willl undergo condensation reaction with
wit CH 3 COCl to form an ester.
e Phenylamine
will undergo condensation reaction with 1 mol of CH 3 COCl to form amide.

449 trendyline
26
39 Which of the following reactions give products that does notrotate the plane of polarised
light?
1 1bromobutane refluxed with aqueous KOH

2 Butanone reacted with HCN, trace amount of NaOH
3 %XWHQHUHDFWHGZLWKEURPLQHGLVVROYHGLQRUJDQLFVROYHQW
Ans: A
Option 1: 1-bromobutane is a 1 halogenoalkane hence it will react with aq KOH via S N 2
mechanism. Since the product does not contain a chiral carbon, it is unable to rotate plane
of polarised light.
Option 2: Butanone reacts with HCN via nucleophilic addition. As the nucleophiles can
attack the carbonyl carbon (trigonal planar in shape) either from the top or the bottom of the
plane with equal chance, it results in a racemic mixture Hence, even though the products
are chiral, they are unable to rotate plane of polarised light.
Option 3: But-1-ene reacts with bromine via electrophilic addition. As the electrophile can
attack the C atom of the carbocation intermediate is trigonal planar in shape, either from the
top or the bottom of the plane with equal chance, it results in a racemic mixture Hence, even
though the products are chiral, they are unable to rotate plane of polarised light.
40 Which of the following could result in the loss of the tertiary structure of a protein?
1 Addition of weak acid

2 Addition of alcohol
3 Addition of AgNO 3 solution
Ans: A
Note: The tertiary structure of proteins refers to the 3D arrangement of the protein due to the
folding of a polypeptide chain. Folding is due to R group (side chain) interactions.
Option 1: Addition of weak acid pH can change the ionic charges on amino acid residues
(i.e. groups containing acidic COOH or basic NH 2 groups) and hence disrupt the ionic
interactions.
In acidic conditions), protonation occurs, i.e. COO is converted to COOH.
Option 2: Alcohol can disrupt the original hydrogen bonds between polar R groups thereby
disrupting their normal folding.
Option 3: Metal ions (Ag+) are positively charged cations. They compete with positively
charged groups (e.g. NH 3 +) for attraction to negatively charged groups (e.g. -COO), hence
disrupting the original ionic interactions.
1 C 6 A 11 A 16 D 21 B 26 D 31 D 36 C
2 D 7 A 12 D 17 A 22 C 27 C 32 D 37 A
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tre
re
endy
e nd
dy
ylin
liin
in
nee
3 B 8 D 13 D 18 D 23
2 C 28 D 33 B 38 C
4 D 9 A 14 A 19 D 24 C 29 A 34 D 39 A
5 C 10 D 15
1 B 20
2 B 25
2 C 30 D 35 B 40 A
A = 10
B=6
C=9

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27
D = 15
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451 trendyline
Higher 2
CANDIDATE
NAME
CLASS INDEX NUMBER
CHEMISTRY 9647/02
2 hours
Write your index number, name and civics group.

You may use pencil for any diagrams, graphs or rough working.
Answer all questions in the space provided.

A Data Booklet is provided. For Examiners Use
Section A
You are advised to show all working in calculations.
You are reminded of the need for good English and
clear presentation in your answers.
1 12
You are reminded of the need for good handwriting. 2
Your final answers should be in 3 significant figures. 17
You may use a calculator. 3

10
The number of marks is given in brackets [ ] at the end of each 4
question or part question. 18
5
At the end of the examination, fasten all your work 15
securely together. Significant
figures
Handwriting
Total
72
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nted pages and 1 blank page.
page
Innova Junior College [Turn over
452 trendyline
For
2 Examiners
Use
Answer ALL questions on the spaces provided.
1 Planning
Using the information below, you are to write a plan for determining number of molecules
of water of crystalisation, n, in barium chloride crystals, BaCl 2 .nH 2 O where n = 1,2 or 3.
The basis of this investigation is a technique known as precipitation titration with the use of
silver nitrate solution, AgNO 3 (aq).
AgCl, Ag 2 CrO 4 and BaCrO 4 are sparing soluble salts and relevant information about these
salts are given in the table below.
compound colour numerical value of K sp at 25 O C

AgCl white 2.0 1010
Ag 2 CrO 4 red 2.0 1012
BaCrO 4 yellow 1.0 1010
Some barium chloride crystals, BaCl 2 .nH 2 O, is dissolved to make up 250.0 cm3 of
standard solution. Approximately 10 cm3 of 0.2 mol dm3 of reagent X solution is added to
a portion of this standard solution to precipitate the barium ions before a few drops of
K 2 CrO 4 indicator solution is added. A titration is then carried out on this portion of solution
against silver nitrate solution, AgNO 3 (aq). Ag 2 CrO 4 would just precipitate only when almost
all of the Cl ions have been precipitated as AgCl. The titration is repeated until a more
reliable average value, V cm3, can be determined.
(a) (i) Identify reagent X.
... [1]
(ii) A student suggested that BaCrO 4 is more soluble than Ag 2 CrO 4 as BaCrO 4
has larger numerical value of K sp than Ag 2 CrO 4 .
Suggest whether this students claim is valid.
........
........
........
........
... [1]
(iii) Suggest why reagent X is added before a few drops of K 2 CrO 4 indicator
solution is added.
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........
........

... [1]
453 trendyline
For
3 Examiners
Use
0.10 mol dm3 silver nitrate
0.2 mol dm3 of reagent X solution
10 g of barium chloride crystals, BaCl 2 .nH 2 O
Potassium chromate solution, K 2 CrO 4 (aq)
The equipment and materials normally found in a school or college

laboratory.
Your plan should include the following
brief, but specific details of the apparatus you would use, bearing in mind the
levels of precision they offer
details, including quantities, for preparation of 250.0 cm3 of BaCl 2 solution

from barium chloride crystals, BaCl 2 .nH 2 O
essential details of the titration procedure
an outline of how the results obtained, including V cm3 , would be used to

determine n, in barium chloride crystals (BaCl 2 .nH 2 O)
....................
....................
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.........

.........

.........

.........

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For
4 Examiners
Use
.........
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....................
.........
.........
.........
.........
.........
.........
.........
.........
.........
.........
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.........
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.........

.........

.........

........ [8]
455 trendyline
For
5 Examiners
Use
(c) Explain why this titration cannot be conducted under acidic or alkaline medium.
.........
.........
.........
........ [1]
[Total: 12]
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456 trendyline
For
6 Examiners
Use
2 This question is about the oxides of nitrogen and its reactions. Oxides of nitrogen
constitute air pollutants originating from emission of car exhaust that cause acid rain
and photochemical smog.
The two gases of NO and N 2 O 4 slowly react to form the blue compound, N 2 O 3
according to the following equation.
2NO(g) + N 2 O 4 (g) 2N 2 O 3 (g)
(a) (i) Draw the dot and cross diagrams of the two molecules, NO and N 2 O 3 .
The N 2 O 3 molecule containVD11ERQG.
[2]
(ii) From your answer in (a)(i), suggest why the forward reaction is likely to
occur.
...
...
..... [1]
(b) In an experiment, a mixture containing NO and N 2 O 4 was introduced into a

1.48 dm3 evacuated vessel was allowed to reach equilibrium at 280 K. The
equilibrium pressure is 98.9 kPa.
Calculate the total number of moles of gases at equilibrium, assuming the gases
behave ideally.
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457 trendyline
For
7 Examiners
Use
(c) Two colourless gases NO and N 2 O 4 slowly react to form the blue compound,
N 2 O 3 according to the following equation.
2NO(g) + N 2 O 4 (g) 2N 2 O 3 (g)
Equimolar mixtures of NO and N 2 O 4 are mixed at varying pressure P but at two

different temperatures of 300 K and 330 K, and the variation in colour intensity
was monitored over a period of time.
The graphs below show the variation of the colour intensity with pressure at
temperatures of 300 K and 330 K.
colour
colour 300 K
intensit
y
intensity
330 K
0 pressure/ atm
(i) What is the significance of the colour intensity in this reaction?
...
..... [1]
(ii) Explain why colour intensity of the reaction mixture increases with increasing
pressure.
...
...
..... [1]
(iii) Using information from the graphs, state and explain whether the formation
of N 2 O 3 from NO and N 2 O 4 is an exothermic reaction.
...
...
...
...
...
...
...
...
...

..... [2]
458 trendyline
For
8 Examiners
Use
(d) Nitrogen monoxide reacts with chlorine to form nitrosyl chloride, according to the
equation:
2NO(g) + Cl 2 (g) 2NOCl(g).
In an experiment, the amount of Cl 2 (g) was kept in large excess while the initial
partial pressure of NO(g) was varied at constant temperature of 500K.
The table below shows the experimental results obtained.
time / s P NO / atm (Rate / P NO ) (Rate / (P NO )2)

/ s1 / (atm s1)
0 0.917 1.033 104 1.126 104
1000 0.827 9.312 105 1.126 104
2000 0.753 8.486 105 1.127 104
3000 0.691 7.788 105 1.127 104
4000 0.638 7.190 105 1.127 104
(i) Suggest why the amount of Cl 2 (g) was kept in large excess.
...
..... [1]
(ii) Using the data from the table above, deduce the order of reaction with
respect to NO(g).
...
..... [1]
(iii) In another experiment, the initial partial pressure of NO(g) was 4.2 atm and it
was reacted with Cl 2 (g) at a constant temperature of 500 K. The partial
pressure of Cl 2 (g) was recorded at time intervals of 30 s. The data obtained
are tabulated below.
time / s partial pressure time / s partial pressure

of Cl 2 (g) / atm of Cl 2 (g) / atm
0 0.78 300 0.49
30 0.76 330 0.46
60 0.72 360 0.44
90 0.70 390 0.42
120 0.66 420 0.39
150 0.63 450 0.38
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re
endyylin
ne
180 0.59 480
48 0.36
0
2
210 0.57 510
51 0.34
0
2
240 0.54 540
54 0.33
0
270 0.52
0 52 570 0.32
0

459 trendyline
For
9 Examiners
Use
Using the data but without the plotting of any graph, deduce the order of
reaction with respect to Cl 2 (g).
...
...
..... [1]
(iv) Write the rate equation for this reaction.

Hence, calculate the rate constant, including its units
[3]
(v) One possible mechanism of the reaction is given below.
Step I NO(g) + Cl 2 (g) NOCl 2 (g) fast
Step II NOCl 2 (g) + NO(g) 2NOCl(g) slow
Explain whether it is consistent with the observed kinetics data in (d)(iv).
...
...
...
...
..... [2]
[Total: 17]
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460 trendyline
For
10 Examiners
Use
3 Organic compounds can undergo combustion. Chemical companies produce containers

filled with butane for use by campers.
The enthalpy change of combustion of butane is 3000 kJ mol 1.
(a) (i) Define the term standard enthalpy of combustion of butane.
...
..... [1]
(ii) Calculate the mass of water at 25 C that could be brought to the boiling point
by the combustion of 1.2 dm3 of butane gas. Assume 75 % of the heat from
the butane is absorbed by the water.
[2]
(b) Explain in terms of structure and bonding, why butanone has a higher boiling point
than pentane.
...
...
...
...
...
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.....

[2]

461 trendyline
For
11 Examiners
Use
(c) Organic compounds are also widely used for pharmaceutical purposes such as
ephedrine which is an anti-asthmatic and stimulant. Ephedrine can be converted
into ethylephedrine via a S N 2 reaction.
OH OH
N N
H
Ephedrine Ethylephedrine
(i) Suggest the reagent that can be used to perform this conversion.
....[1]
(ii) Explain why an S N 2 mechanism is favoured for this reaction.
.....
.[1]
(d) Complete hydrolysis of proteins produces individual units of amino acids, but partial
hydrolysis can break the protein down into dipeptide or tripeptide fragments.
Partial hydrolysis of a tetrapeptide (containing four amino acid residues) produces
the following three dipeptides, as well as the individual amino acids.
NH 2 CH 2 CONHCH(CH 3 )CO 2 H
NH 2 CH 2 CONHCH 2 CO 2 H
NH 2 CH(CH 3 )CONHCH(CH 3 )CO 2 H
(i)
Define the primary structure of a protein.
...
..... [1]
(ii) Deduce the order in which the amino acids are bonded together in the
tetrapeptide.
...
..... [1]
(iii) Suggest suitable reagents and conditions to hydrolyse the tetrapeptide into its
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ividual
vid
individual amino acids.
...
...
...
...
..... [1]
[Total: 10]
462 trendyline
For
12 Examiners
Use
4 (a) A 0.031 mol dm-3 solution of a base, MOH, has a pH of 12.5. (M is a metal.)
25 cm3 of the solution of MOH was titrated with 0.025 mol dm-3 propanoic acid,
CH 3 CH 2 COOH, at 25 C. The pH of the solution was followed using a pH meter
and the following titration curve was obtained.
pK a of propanoic acid = 1.29 x 10-5 mol dm-3
pH
volume of propanoic acid

V added/cm3
(i) Calculate the concentration of hydroxide ions present in the sample of MOH
and use it to explain whether it is a strong or weak base.
...
...
......[1]
(ii) Calculate the value of V.
[1]
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463 trendyline
For
13 Examiners
Use
(iii) Explain, with the aid of an equation, why the pH when V cm3 of propanoic
acid was added, is greater than 7.
...
...
...
..... [2]
(b) The colour of blackberries is due to a compound known as cyanidin. Cyanidin is a

weak organic acid which may be represented by CyH. In aqueous solution, CyH
dissociates slightly:
CyH (aq) Cy (aq) + H+ (aq)

red purple
The colours of CyH and Cy are indicated in the above equation.

Acid dissociation constant, K a , of CyH is 5.0 x 105 mol dm3 at 25 C.
A glass of blackberry juice has a pH of 3.00 at 25 C. Calculate the ratio of the red
to purple form in the juice, and hence predict its colour.
[3]
(c) When chlorine is bubbled through cold sodium hydroxide solution and acidified
silver nitrate solution, only half of the chlorine that has dissolved is precipitated as
silver chloride. When the sodium hydroxide is hot, up to fivesixth of the chlorine
can be precipitated. Explain the observations, giving balanced equations where
appropriate.
............
........
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........

........

........

464 trendyline
For
14 Examiners
Use
...... [3]
(d) The table below gives data about some physical properties of the elements
calcium, nickel and copper.
calcium nickel copper

atomic radius / nm 0.197 0.124 0.128
electronic
[Ar]4s2 [Ar]3d84s2 [Ar]3d104s1
configuration
(i) What do you understand by the term transition element?
......
......
..... [1]
(ii) Although the nickel and copper atoms have more electrons than the calcium
atom, the atomic radii of nickel and copper are smaller than that of calcium.
Suggest an explanation for this.
...
...
...
...
...
...
...
...[3]
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465 trendyline
For
15 Examiners
Use
(e) The following are some reactions involving copper(II) nitrate.
hydrated excess water KHCO (aq)

3
copper(II) Cu(NO3)2 (aq) blue ppt + CO
2
nitrate solid
excess NH (aq)
3
D
dark blue solution
excess KCN(aq)
E
violet solution
(i) Explain why carbon dioxide is evolved when KHCO 3 (aq) is added to
aqueous copper(II) nitrate. Include any relevant equations with state
symbols in your answer.
...
...
...
...
...
...[2]
(ii) Suggest a formula for the complex ion present in D.
.... [1]
(iii) The metal ion in complex E is known to have a coordination number of four.
Suggest a formula for complex ion E.
... [1]
[Total: 18]
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466 trendyline
For
16 Examiners
Use
5 Benzene reacts with propanoyl chloride and 1-phenylpropan-1-one is formed in the
reaction.
(a) State the reagents and conditions needed to convert 1-phenylpropan-1-one into
compound Q. Show the structure of the intermediate in the box provided.
O OH
Step 1 Step 2
C CH2CH3 C COOH
CH2CH3
- - -
1 phenylpropan 1 one compound Q
Reagents and conditions
Step 1 .
Step 2 .
[3]
(b) Describe the mechanism in Step 1 in part (a). In your answer, you should show all
charges and lone pairs and show the movement of electrons by curly arrows.
[3]
(c) The 2,4-D weed killer, C 8 H 6 Cl 2 O 2, is widely used on cereal crops, pastures and
orchards. Compound R is an isomer of the weed killer under development to improve
its properties. It is an aromatic compound which contains three functional groups.
The following tests are carried out in the order given. In each case, state all
deductions about the compound R you can make at that stage. When identifying the
functional groups, your answers should be unambiguous.
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(i) Compound R is
When Compoun with
s treated with Na, C 8 H 5 C
Cll 2 O 2 Na is forme
formed.
form
deduction(s)..........................................................................................................
eduction(s)...............................................................................
duction(s)...............................................................................
..........................................................................................................................[1]
................................................................................................
...

467 trendyline
For
17 Examiners
Use
(ii) When Fehlings solution is added to Compound R, red brick precipitate is

obtained.
deduction(s)..........................................................................................................
..........................................................................................................................[1]
(iii) When 1 mole of Compound R is boiled with ethanolic silver nitrate, 287 g of
white precipitate is formed.
deduction(s)..........................................................................................................
.............................................................................................................................
.............................................................................................................................
..........................................................................................................................[2]
(iv) When Compound R is treated with concentrated nitric acid, C 8 H 3 Cl 2 N 3 O 8 is

formed.
1. What type of reaction takes place?
..................................................................................................................
2. Name the functional group present in Compound R that is confirmed by
this reaction.
..................................................................................................................
[2]
(v) You now have enough information to determine the structural formula of R.
1. Draw the fully displayed structure of R.
2. Explain clearly why you have placed each of the aromatic substituent
groups in their particular positions.
.............................................................................................................................
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e
............................................................................................................................
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..........................................................................................
.......................................................................................
.............................................................................................................................
..........................................................................................
........................................................................................
[3]
[Total: 15]

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For
18 Examiners
Use
BLANK PAGE
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469 trendyline
Higher 2
CANDIDATE
NAME
CLASS INDEX NUMBER
CHEMISTRY 9647/02
2 hours
Write your index number, name and civics group.

You may use pencil for any diagrams, graphs or rough working.

A Data Booklet is provided. For Examiners Use
Section A
clear presentation in your answers.
1 12
You are reminded of the need for good handwriting. 2
Your final answers should be in 3 significant figures. 17
You may use a calculator. 3

10
The number of marks is given in brackets [ ] at the end of each 4
question or part question. 18
5
At the end of the examination, fasten all your work 15
securely together. Significant
figures
Handwriting
Total
72
trendyline
nted pages and 1 blank page.
page
470 trendyline
For
2 Examiners
Use
1 Planning
Using the information below, you are to write a plan for determining number of molecules
of water of crystalisation, n, in barium chloride crystals, BaCl 2 .nH 2 O where n = 1,2 or 3.
The basis of this investigation is a technique known as precipitation titration with the use of
silver nitrate solution, AgNO 3 (aq).
AgCl, Ag 2 CrO 4 and BaCrO 4 are sparing soluble salts and relevant information about these
salts are given in the table below.
compound colour Numerical value of K sp at 25 O C

AgCl white 2.0 1010
Ag 2 CrO 4 red 2.0 1012
BaCrO 4 yellow 1.0 1010
Some barium chloride crystals, BaCl 2 .nH 2 O, is dissolved to make up 250.0 cm3 of
standard solution. Approximately 10 cm3 of 0.2 mol dm3 of reagent X solution is added to
a portion of this standard solution to precipitate the barium ions before a few drops of
K 2 CrO 4 indicator solution is added. A titration is then carried out on this portion of solution
against silver nitrate solution, AgNO 3 (aq). Ag 2 CrO 4 would just precipitate only when almost
all of the Cl ions have been precipitated as AgCl. The titration is repeated until a more
reliable average value, V cm3, can be determined.
(a) (i) Identify reagent X. [1]
Na 2 SO 4 (aq) or K 2 SO 4 (aq) [1]
(ii) A student suggested that BaCrO 4 is more soluble than Ag 2 CrO 4 as BaCrO 4
has larger numerical value of K sp than Ag 2 CrO 4 .
Suggest whether this students claim is valid. [1]
This claim is not true as both Ag 2 CrO 4 and BaCrO 4 are of different unit
formula or have different number of ions per formula unit. [1]
Alternatively, students can prove from calculations of solubility of the

two salts.
Solubility of BaCrO 4 = = 1.00 105 mol dm3
Solubility of Ag 2 CrO 4 = = 7.94 105 mol dm3
From the calculations above, Ag 2 CrO 4 has a higher solubility than
ttrendyline
tr
r d li
Ba
BaCrO 4 despite Ag 2 CrO 4 having
aving a smalle
smaller numerical value of K sp than
BaCrO 4 . [1
[1]]
(iii) Suggest why reagent

reage X iss adde
added before
befor a few drops of K 2 CrO 4 indicator
olution is added.
solution [1]
This is to prevent the precipitation of BaCrO 4 that uses up the CrO 4 2-

ions.
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For
3 Examiners
Use
0.10 mol dm3 silver nitrate
0.2 mol dm3 of reagent X solution
10 g of barium chloride crystals, BaCl 2 .nH 2 O
Potassium chromate solution, K 2 CrO 4 (aq)
The equipment and materials normally found in a school or college

laboratory.
Your plan should include the following
brief, but specific details of the apparatus you would use, bearing in mind the
levels of precision they offer
details, including quantities, for preparation of 250.0 cm3 of BaCl 2 solution

from barium chloride crystals, BaCl 2 .nH 2 O
essential details of the titration procedure
an outline of how the results obtained, including V cm3 , would be used to

determine n, in barium chloride crystals (BaCl 2 .nH 2 O)
Assuming titre volume of AgNO 3 (aq) used is 25.00 cm3 and the volume of BaCl 2
solution pipetted is 25.0 cm3,
Ag+(aq) + Cl(aq) AgCl(s)
BaCl 2 (aq) Ba2+(aq) + 2Cl(aq)
Amt of Ag+(aq) = = 0.00250 mol = Amt of Cl(aq) in 25 cm3
Amt of Cl(aq) in 250 cm3 = 0.00250 = 0.0250 mol
Amt of BaCl 2 (aq) in 250 cm3 = 0.0250 mol 2 = 0.0125 mol
Conc of BaCl 2 (aq) = 0.0125 mol = 0.0500 mol dm3

Assuming n = 1,
Min mass of BaCl 2 .nH 2 O in 250 cm3 = 0.0125 226.0 = 2.825 g
OR
Assuming n = 3,
Max mass of BaCl 2 .nH 2 O in 250 cm3 = 0.0125 262.0 = 3.725 g
Thus the suitable mass of BaCl 2 .nH 2 O to be weighed ranges 2.825 g to 3.725 g.
ttrendyline
d
Preparation
at o of
o standard
sta da d solution
so ut o of
o BaCl
aCl 2
1. Weighgh 2.825g 3.275g g of BaC BaCll 2 ..nH

H 2 O crystals in
nH n a clean and dry weighing
bottlee using a weighing balanc
le balance.
2. Transfer
nsfer BaCll 2 .nH
sfer the BaC H 2 O crystals to a 10 cm3 beaker.
100 cm beak
3. Weighgh the emptied weighing bottle and nd tthe residual BaC
BaCll 2 .nH 2 O crystals to
determine the mass of BaCl 2 .nH 2 O crystals dissolved, m grams, by finding the
difference the weighings in (i) and (iii).
4. Add 100 cm3 of de-ionised water to the BaCl 2 .nH 2 O crystals in the 100 cm3
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Use
beaker.
5. Use a glass stirrer to stir the solution in the 100 cm3 beaker to ensure a
homogeneous solution is obtained.
6. Transfer the homogeneous solution carefully to a 250 cm3volumetric flask.
7. Using 50 cm3 of de-ionised water, rinse the beaker, the weighing bottle and the
stirrer and transfer the washings carefully to the solution in the 250 cm3volumetric
flask.
8. Top up to the mark with de-ionised water, stopper the bottle and shake this
solution to obtain a homogeneous solution. Label this solution obtained as FA 2.
Titration Procedures
1. Fill up the burette with AgNO 3 (aq), noting the initial volume reading.
2. Pipette 25.0 cm3 of FA 2 to a 250 cm3 conical flask.
3. Using a 10cm3 measuring cylinder, add 10 cm3 of 0.2 mol dm3 of Na 2 SO 4
solution to the solution in the conical flask. Shake the mixture and let it equilibrate
for about 15 minutes.
4. Add 5 drops of K 2 CrO 4 (aq) indicator solution to the mixture in the conical flask.
5. Carry out the titration until permanent pink colour is obtained. (Colour change is
from white ppt to pink due of 1 drop of AgNO 3 (aq) in excess to cause
precipitation of red Ag 2 CrO 4 )
6. Repeat titration until at least 2 consistent titre readings are obtained (titre volume
differ not more than 0.10 cm3). Use the average of these 2 consistent titres to
obtain volume, V cm3 for subsequent calculations.
Calculation Procedure
Amt of Cl ions in titration (25 cm3) = = 0.000100V mol

3
Amt of Cl ions in 250 cm = 0.000100V x 10 = 0.00100V mol
Amt of BaCl 2 = 0.00100V 2 = 0.000500V mol
Mass of BaCl 2 = 0.000500V 208.0 = 0.104 V g
Mass of water of crystalisation = (m V ) g
Amt of water of crystalisation = ((m V ) 18) mol
No of molecules of water of crystalisation, n

= Amt of water of crystalisation Amt of BaCl 2
= ((m V ) 18) 0.0000500V
Marking points
1. use of appropriate apparatus with correct capacities i.e. weighing bottle

for measuring mass of BaCl 2. nH 2 O crystals, 250 cm3 volumetric flask to
prepare BaCl 2 solution, 10 cm3 measuring cylinder for measuring vol of
reagent X solution, pipette+burette+ 250 cm3 conical flask
2. Appropriate volumes of solutions pipetted being 20.00 25.00 cm3
based on appropriate choice of titre volume of 20.00 25.00 cm3 and max
of 5 drops of indicator to be used.
3. appropriate mass of BaCl 2. nH 2 O crystals used = 2.825g 3.275g
4. Quantitative transfer of BaCl 2 solution to volumetric flask or mass
difference of weighing bottle+ crystals and mass of emptied weighing
trendyli
trendyline
dylil e
bottle to determine mass of B BaCl
BaCl 2. nH 2 O crystals
cr
5. Repeat titration until two consistent readings (+ 0.10 cm3) are obtained.
6. Correct
Correc colour change (white to pink or red) red at end point
7. Derivation of mass of water of crystallisation
8. Derivation n being mole ratio of water
wa of crystallisation to BaCl 2
[8]
(c) Explain why this titration cannot be conducted under acidic or alkaline medium. [1]
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Use
Under acidic medium, CrO 4 ions will undergo condensation or acid-base

reaction to form Cr 2 O 7 ions, thus the indicator ions of CrO 4 will be absent and
the end-point of the titration cannot be detected. [1]
OR
Under alkaline medium, Ag+ ions will be precipitated as Ag 2 O resulting in a much

higher than accurate titre reading. [1]
[Total: 12]
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Use
2 This question is about the oxides of nitrogen and its reactions. Oxides of nitrogen
constitute air pollutants originating from emission of car exhaust that cause acid rain
and photochemical smog.
The two gases of NO and N 2 O 4 slowly react to form the blue compound, N 2 O 3
according to the following equation.
2NO(g) + N 2 O 4 (g) 2N 2 O 3 (g)
(a) (i) Draw the dot and cross diagrams of the two molecules, NO and N 2 O 3 .
The N 2 O 3 molecule containVD11ERQG.
[2]
xx
x
O xO x
x x x
x x x
N N N
x x O
xx x x
x
x O
xx
x
N2O3 NO
(ii) From your answer in (a)(i), suggest why the forward reaction is likely to
occur.
[1]
The NO molecule contains an unpaired electron/lone electron>@ or The

NO molecule is a free radical.
Thus, it is highly reactive/unstable>@, and reacts to form N 2 O 3 molecule
(that has all atoms attaining noble gas configuration).
(b) In an experiment, a mixture containing NO and N 2 O 4 was introduced into a 1.48

dm3 evacuated vessel was allowed to reach equilibrium at 280 K. The equilibrium
pressure is 98.9 kPa.
Calculate the total number of moles of gases at equilibrium, assuming the gases
behave ideally.
[2]
39 Q57Q = 0.0629 mol [1]

[1] for working (correct unit conversion)
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(c) Two colourless gases NO and N 2 O 4 slowly react to form the blue compound,
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For
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Use
N 2 O 3 according to the following equation.
2NO(g) + N 2 O 4 (g) 2N 2 O 3 (g)
Equimolar mixtures of NO and N 2 O 4 are mixed at varying pressure P but at two

different temperatures of 300 K and 330 K, and the variation in colour intensity
was monitored over a period of time.
The graphs below show the variation of the colour intensity with pressure at
temperatures of 300 K and 330 K.
colour 300 K
intensity
330 K
0 Pressure/ atm
(i) What is the significance of the colour intensity in this reaction? [1]
The colour intensity changes with changes in partial pressure/ concentration/

amount of N 2 O 3 produced. [1]
Accept any answers of similar meaning.
(ii) Explain why colour intensity of the reaction mixture increases with increasing
pressure. [1]
When the pressure is increased, the equilibrium position shifts right>@,

to decreasing the number of moles of gaseous molecules>@ present.
Or
An increase in pressure favours the forward reaction, causing more N 2 O 3

to be formed. Hence, the colour intensity increases.
(iii) Using information from the graphs, state and explain whether the formation
of N 2 O 3 from NO and N 2 O 4 is an exothermic reaction.
[2]
At the higher temperature of 330 K, the colour intensity is lower. This

implies less N 2 O 3 is produced [] and hence indicates that the backward
ttrendyline
d li
reaction
action is favoured at higher temperatures.
temperatures []
Byy Le Chateliers principle, when

en temperature of a system is increased,
the
he e system favours endothermic reaction in order to remove the
excess
xcess heat []
[
]
Since
i the
h bbackward
k d reaction
i iis ffavoured/
d/ lless products
d are formed,
the forward reaction is exothermic. []
IJC 2016 Prelim/9647/02

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Use
Or
At the lower temperature of 300 K, the colour intensity is higher. This

implies more N 2 O 3 is produced [] and hence indicates that the forward
reaction is favoured at lower temperatures. []
By Le Chateliers principle, when temperature of a system is decreased,

the system favours exothermic reaction in order to produce heat [].
Since the forward reaction is favoured/ more products are formed,

the forward reaction is exothermic. []
(d) Nitrogen monoxide reacts with chlorine to form nitrosyl chloride, according to the
equation:
2NO(g) + Cl 2 (g) 2NOCl(g).
In an experiment, the amount of Cl 2 (g) was kept in large excess while the initial
partial pressure of NO(g) was varied at constant temperature of 500K.
The table below shows the experimental results obtained.
time / s P NO / atm (Rate / P NO ) (Rate / (P NO )2)

/ s1 / (atm s1)
0 0.917 1.033 104 1.126 104
1000 0.827 9.312 105 1.126 104
2000 0.753 8.486 105 1.127 104
3000 0.691 7.788 105 1.127 104
4000 0.638 7.190 105 1.127 104
(i) Suggest why the amount of Cl 2 (g) was kept in large excess.
[1]
Since the amount of Cl 2 (g) was kept in large excess, the partial pressure
of Cl 2 (g) remains relatively constant [1] so that any change in rate is due
to the changes in the partial pressure of NO(g) only.
(ii) Using the data from the table above, deduce the order of reaction with
respect to NO(g).
[1]
trendyline
tren d li e
Sincec Rate / (P NO )2 is constantt throughout the
ince t reaction [] (and thus rate
off reaction is directly proportional to (P NO )2),, the
he reaction is s
second order
with
ith
th respect to NO
NO.. [
[]
]
(iii) In another experiment, the initial partial pressure of NO(g) wa

was 4.2 atm and it
was
as reacted with Cl 2 (g) at a constant
nst temp
temperature
erature of 500 K. The partial
pressure of Cl 2 (g) was recorded at time intervals of 30 s. The data obtained
are tabulated below.
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Time / s Partial pressure Time / s Partial pressure

of Cl 2 (g) / atm of Cl 2 (g) / atm
0 0.78 300 0.49
30 0.76 330 0.46
60 0.72 360 0.44
90 0.70 390 0.42
120 0.66 420 0.39
150 0.63 450 0.38
180 0.59 480 0.36
210 0.57 510 0.34
240 0.54 540 0.33
270 0.52 570 0.32
Using the data but without the plotting of any graph, deduce the order of
reaction with respect to Cl 2 (g). [1]
1st t 1/2
= time taken for P Cl2 to decrease from 0.78 atm to 0.39 atm
= 420 s
2nd t 1/2
= time taken for P Cl2 to decrease from 0.72 atm to 0.36 atm (or 0.66 0.33)
= 480 60
= 420 s
Since t 1/2 is constant at 420s [], the reaction first order with respect to Cl 2 .
Hence order of reaction with respect to Cl 2 = 1 []
(iv) Write the rate equation for this reaction.

Hence, calculate the rate constant, including its units [3]
Rate = k (P NO )2(P Cl2 ) [1] , allow ecf based on answers in (ii) and (iii)
Rate = k (P Cl2 ) where k = k (P NO )2
t 1/2 = 420 s = =
k = 9.36 105 [1] atm2 s1 [1]
(v) One possible mechanism of the reaction is given below.
Step I NO(g) + Cl 2 (g) NOCl 2 (g) fast
trendyline
Step
ep II
tep g)
NOCl 2 (g) + NO(g) 2NOC
2NOCl(g)
NOCll(g) slow
Explain
plain whether it is consistent with the observed kinetics data
xplain d in (d)(iv).
[2]]
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Use
If Step II is the rds: rate = k (P NOCl2 )(P Cl2 )
Since rate equation should not contain NOCl 2 intermediate, from step 1:
PNOCl2
Kp
PNOPCl2
Hence, PNOCl2 K pPNOPCl2
Substitute into the rate equation:
rate = k (P NOCl2 )(P Cl2 ) = k K p (P NO )(P Cl2 )(P NO ) = k (P NO )2(P Cl2 ) [1]
Step II is the rate-determining step since its rate equation is consistent

with the experimentally determined rate law, rate = k (P NO )2(P Cl2 ). [1]
[Total: 17]
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IJC 2016 Prelim/9647/02
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Use
3 Organic compounds can undergo combustion. Chemical companies produce containers

filled with butane for use by campers.
The enthalpy change of combustion of butane is 3000 kJ mol 1.
(a) (i) Define the term standard enthalpy of combustion of butane.[1]

It is enthalpy change when 1 mole of butane is burnt in excess oxygen under
standard conditions of 298K and 1 atm. [1]
(ii) Calculate the mass of water at 25 C that could be brought to the boiling point
by the combustion of 1.2 dm3 of butane gas. Assume 75% of the heat from the
butane is absorbed by the water. [2]
Heat = mcT
Moles of butane = (1.2) / 24 = 0.05 moles
Heat released = 3000 x 0.05 = 150 kJ
Heat absorbed = 0.75 x 150 = 112.5 kJ [1]
112.5 x 103 = m x 4.18 x (100 25)
m = 358 g [1]
(b) (i) Explain in terms of structure and bonding, why butanone has a higher boiling
point than pentane. [2]
Both butanone and pentane have simple molecular structures>@ with similar
Mr
Butanone has a higher boilng point as it requires more energy>@
to overcome its stronger p.d-pd interactions between its molecules
>@FRPSDUHGWRid-id interactions between butane molecules. >@
>@ 2m (accept answers along this line SBE, comparing strength)
(c) Organic compounds are also widely used for pharmaceutical purposes such as
ephedrine which is an anti-asthmatic and stimulant. Ephedrine can be converted into
ethylephedrine via a S N 2 reaction.
OH OH
N N
H
Ephedrine Ethylephedrine
(i) Suggest the reagent that can be used to perform this conversion.[1]
CH 3 CH 2 I [1]
(ii) Explain why an S N 2 mechanism is favoured for this reaction. [1]

There is only 1 bulky alkyl group bonded to the carbon of the CH 3 CH 2 I
that could possibly block the backside approach of the nucleophile. Thus
trendyline
d
there
ere is less steric hindrancece in thee halogenoalkane
ha and
a hence S N 2
mechanism favoured [1]
echanism is favoured.
(d) Completee hydrolysis of proteins produces individual units of amino acids, but partial
ete
hydrolysis
sis can break the protein down into
to dipeptide
d fragments.
or tripeptide frag
Partial hydrolysis of a tetrapeptide (containing four amino acid residues) produces
the following three dipeptides, as well as the individual amino acids.
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Use
NH 2 CH 2 CONHCH(CH 3 )CO 2 H
NH 2 CH 2 CONHCH 2 CO 2 H
NH 2 CH(CH 3 )CONHCH(CH 3 )CO 2 H
(i)
Define the primary structure of a protein [1]
Primary structure is the sequence of amino acids in a polypeptide chain[1]
(ii) Deduce the order in which the amino acids are bonded together in the
tetrapeptide. [1]
NH 2 CH 2 CONHCH 2 CONHCH(CH 3 )CONHCH(CH 3 )CO 2 H [1]
(iii) Suggest suitable reagents and conditions to hydrolyse the tetrapeptide into its
individual amino acids. [1]
Reagents : dilute H 2 SO 4 / HCl >@
Condition: prolonged heating (many hours) >@
[Total: 10]
4 (a) A 0.031 mol dm-3 solution of a base, MOH, has a pH of 12.5. (M is a metal.)
25 cm3 of the solution of MOH was titrated with 0.025 mol dm-3 propanoic acid,
CH 3 CH 2 COOH, at 25 C. The pH of the solution was followed using a pH meter and
the following titration curve was obtained.
Ka of propanoic acid = 1.29 x 10-5 mol dm-3
(i) Calculate the concentration of hydroxide ions present in the sample of MOH
and use it to explain whether it is a strong or weak base. [1]
pH = 12.5
pOH = 14 12.5 = 1.5
[OH-] = 10-1.5 = 0.0316 mol dm-3 []
(ii) trendyline
OH has dissociated completely, thus it is a strong base [].
MOH
alculate the value o

Calculate of V
V..
CO -M+ + H 2 O
H 3 CH 2 COOH + MOH CH 3 CH 2 COO
CH
[].
[1]
Amt of MOH = 0.031 x 25/1000

= 7.75 x 10-4 mol
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Use
Amt of CH 3 CH 2 COOH required = 7.75 x 10-4 mol []
Volume of CH 3 CH 2 COOH required = (7.75 x 10-4) / 0.025

= 0.031 dm3
= 31.0 cm3
V = 31.0 []
(iii) Explain, with the aid of an equation, why the pH when V cm3 of propanoic acid
was added, is greater than 7. [2]
When V cm3 of acid is added, the acid and base react completely to produce
a basic salt, which undergoes hydrolysis in water to produce hydroxide
ions / an alkaline solution. [1]
CH 3 CH 2 COO- (aq) + H 2 O (l) CH 3 CH 2 COOH (aq) + OH- (aq) [1]
(b) The colour of blackberries is due to a compound known as cyanidin. Cyanidin is a

weak organic acid which may be represented by CyH. In aqueous solution, CyH
dissociates slightly:
CyH (aq) Cy (aq) + H+ (aq)

red purple
The colours of CyH and Cy are indicated in the above equation.

Acid dissociation constant, K a , of CyH is 5.0 x 10-5 mol dm-3 at 25 C.
A glass of blackberry juice has a pH of 3.00 at 25 C. Calculate the ratio of the red to
purple form in the juice, and hence predict its colour. [3]
When a mix of CyH and Cy- is present, system is an acidic buffer.
pH = pK a + log 10
salt
acid
3.00 = - log 10 (5.0 x 10-5) + log 10

Cy - [1]
CyH
Cy - = 0.05
CyH
CyH = 20 : 1 [1]
Cy -
Colour of juice: red [1]
(c) When chlorine is bubbled through cold sodium hydroxide solution and acidified silver
trendyline
nitrate solution,
olution, only half of the chlorine that has d prec
dissolved is precipitated as silver
e. When the sodium hydroxide is hot, up to fivesixth
chloride. five
fivesixth
sixth of the chlorine can be
precipitated.
ted. Explain the observations, giving balanced equations wh
ated. where appropriate.
[3]
OH 2OH ((aq)) + Cl 2 ((aq)) Cl ((aq)) + ClO ((aq)) + H 2 O (l)

cold NaOH: [1]
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Use
hot NaOH: 6 OH (aq) + 3 Cl 2 (aq) 5 Cl (aq) + ClO 3 (aq) + 3 H 2 O (l) [1]
The free chloride ions will be precipitated out as silver chloride with silver nitrate.
When chlorine reacts with cold NaOH, mole ratio of Cl: ClO = 1 : 1 []
When chlorine reacts with hot NaOH, Cl : ClO 3 = 5 : 1 []
(d) The table below gives data about some physical properties of the elements calcium,
nickel and copper.
calcium nickel copper

atomic radius / nm 0.197 0.124 0.128
electronic [Ar]4s2 [Ar]3d84s2 [Ar]3d104s1
configuration
(i) What do you understand by the term transition element? [1]

A transition element is a d-block element that forms at least one stable ion
with a partially filled d-subshell. [1]
(ii) Although the nickel and copper atoms have more electrons than the calcium
atom, the atomic radii of nickel and copper are smaller than that of calcium.
Suggest an explanation for this. [3]
Nuclear charge of Ni and Cu are larger. [] However, shielding effect of 3d
electrons of Ni and Cu is poorer [1] than that of 3s and 3p electrons of Ca
because 3d orbitals are more diffused. Hence, Ni and Cu have larger
effective nuclear charge. [1] Valence electrons of Ni and Cu are attracted
more strongly to nucleus [], so have smaller atomic radii.
OR
Ni and Cu has higher nuclear charge than Ca. []

For Ni and Cu, electrons are added to the inner 3d subshell. These
inner 3d electrons shield the outer 4s electrons more effectively. []
For Ni and Cu, the effect of increasing nuclear charge is reduced by the
increasing shielding effect. / the increase of nuclear charge outweighs
the increase of shielding effect [1]
Thus effective nuclear charge of Ni and Cu is slightly higher than
Ca []
Valence electrons of Ni and Cu are attracted more strongly to
nucleus [], so have smaller atomic radii
trendyline
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Use
(e) The following are some reactions involving copper(II) nitrate.
hydrated excess water KHCO (aq)
3
copper(II) Cu(NO3)2 (aq) blue ppt + CO
2
nitrate solid
excess NH (aq)
3
D
dark blue solution
excess KCN(aq)
E
violet solution
(i) Explain why carbon dioxide is evolved when KHCO 3 (aq) is added to aqueous
copper(II) nitrate. Include any relevant equations with state symbols in your
answer. [2]
A solution of Cu2+ is acidic [] in nature due to the high charge density [] of
the cation and is able to polarise the electron cloud of water molecule.
[Cu(H 2 O) 6 ]2+(aq) + H 2 O(l) [Cu (H 2 O) 5 (OH)]+(aq) + H 3 O+(aq)

(good to have but not necessary)
2H+ + CO 3 2- CO 2 + H 2 O [1]
(ii) Suggest a formula for the complex ion present in D. [1]

[Cu(H 2 O) 2 (NH 3 ) 4 ]2+ OR [Cu(NH 3 ) 4 ]2+
(iii) The metal ion in complex E is known to have a coordination number of four.
Suggest a formula for complex ion E. [1]
[Cu(CN) 4 ]2-
[Total: 19]
5 Benzene reacts with propanoyl chloride and 1-phenylpropan-1-one is formed in the

reaction.
(a) State the reagents and conditions needed to convert 1-phenylpropan-1-one into
compound Q. Show the structure of the intermediate in the box provided.
O OH
Step 1 Step 2
C CH2CH3 C COOH
CH2CH3
- - -
1 phenylpropan 1 one compound Q
Reagents
nts
Step 1
Step 2
trendyline
s and condition
conditions
.
[3]
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O OH OH
Step 1 Step 2
C CH2CH3 C CN C COOH
CH2CH3 CH2CH3
[1]
Step 1 HCN, trace amt of NaOH/NaCN, 10-20oC (can they use cold?) [1]
Step 2 Dilute or (aq) HCl/H 2 SO 4 , heat [1]
(b) Describe the mechanism in step 1 in part(a). In your answer, you should show all
charges and lone pairs and show the movement of electrons by curly arrows.
[3]
Mechanism: Nucleophilic Addition[1]
Step 1:
HCN H+ CN-
1D&11D+ + CN-
Step 2: Nu attack on butanone to form intermediate
Step 3: Protonation
Step 4: Regeneration of catalyst
Correct mechanism (include all important aspect)

-correct arrows
-partial charges
-correct intermediate [2]
(c) The 2,4-D weed killer, C 8 H 6 Cl 2 O 2, is widely used on cereal crops, pastures and
orchards. Compound R is an isomer of the weed killer under development to improve
its properties. It is an aromatic compound which contains three functional groups.
The following tests are carried out in the order given. In each case, state all
deductions about the compound R you can make at that stage. When identifying the
functional groups, your answers should be unambiguous.
(i) When Compound R is treated with Na, C 8 H 5 Cl 2 O 2 Na is formed.
deduction(s)..........................................................................................................
..........................................................................................................................[1]
Acid metal reaction.[@
Possible functional groups present: alcohol or phenol or carboxylic acid>@
>@ [1]
Must give both functional possible functional gps based on 2 O atoms.
(ii)
trendyline
When Fehlings solution is added to Compound R,
obtained.
btained.
tained
R, red br
brick precipitate is
deduction(s)..........................................................................................................
eduction(s)...............................................................................
duction(s).............................................................................
..........................................................................................................................[1]
Mild oxidation occurs. [@
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Aliphatic aldehyde is present >@
2>@ - [1] [aldehyde alone is not accepted]
(iii) When 1 mole of Compound R is boiled with ethanolic silver nitrate, 287 g of
deduction(s)..........................................................................................................
.............................................................................................................................
.............................................................................................................................
..........................................................................................................................[2]
2 moles of AgCl is formed with 1 mole of compound R. This suggests the

presence of 2 aliphatic chloro substituted atoms undergone nucleophilic
substitution.
Alphatic halogeno compound is present or chlorine atoms are on the aliphatic
side chain and not bonded to the ring.
[1]: identify aliphatic halogeno compound

[1] : identify two Cl aliphatic atoms
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IJC 2016 Prelim/9647/02
486
[Turn over
trendyline
For
18 Examiners
Use
(iv) When Compound R is treated with concentrated nitric acid, C 8 H 3 Cl 2 N 3 O 8 is

formed.
1. What type of reaction takes place?
.........................................................
Electrophilic substitution[1]
2. Name the functional group present in Compound R that is confirmed by

this reaction.
........................................................
[2]
Phenol- [1]
aromatic compound not accepted as catalyst will be required
(v) You now have enough information to determine the structural formula of R.
1. Draw the fully displayed structure of R.

+
2
&O 2
& & +
&O side chain must be at position 3
2. Explain clearly why you have placed each of the aromatic substituent
groups in their particular positions.
[3]
As phenol is 2- and 4- directing, and trisubstitution took place, as seen by
3NO 2 substituent groups added in the electrophilic substitution reaction. Thus,
the side chain is not on the 2-, 4- or 6- position but on position 3.
[1m for explanation along the lines]
+
2
12
21
&O 2
& & +
12 &O
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&+&O12
[1m] tri-substitution
m] tri-
tri-substitution takes position 2,4,6
m] side chain on 3rd position
[1m] ositio
[Total:15]
IJC 2016 Prelim/9647/02

487
[Turn over
trendyline
JC 2PRELIMINARY EXAMINATION
Higher 2
CHEMISTRY 9647/03
Paper 3 Free Response 26 August 2016
2 hours
Additional Materials: Writing Papers

Data Booklet
Cover Page

Begin each question on a fresh sheet of paper.

You are reminded of the need for good handwriting.
Your final answers should be in 3 significant figures.
The number of marks is given in the brackets [ ] at the end of each question or part question.
trendyline
y This document consists of 12printed pages
pages.

488 trendyline
2
1 Data concerning the elements of group II of the Periodic Table, at 298K, are given in the
table. Further data may be found in the Data Booklet. M refers to elements of group II.
st nd 2+
1 and 2 IE of M + atom of M + hydration of M E /V
-1 -1 -1
/ kJ mol / kJ mol / kJ mol
Ca 1740 178 1650 2.87
Sr 1608 164 1480 2.89
(a) The electrode reduction potential E of Group II elements gives an indication of the
ease with which the following reaction occurs:
M(s) M2+(aq) + 2e Reaction 1
The enthalpy change of reaction 1 can be related to the following factors:

first and second ionisation energy of the element
enthalpy change of atomisation and
enthalpy change of hydration of its gaseous ion.
(i) Construct an energy cycle relating the factors above, and use the values given
above to calculate the enthalpy change of Reaction 1 for calcium. [3]
(ii) By quoting appropriate data from Data Booklet, explain the difference in
enthalpy change of hydration of calcium and strontium ions. [2]
(b) Calcium oxide is the key ingredient for the process of making cement.
When calcium is burned in oxygen, calcium oxide is produced.

When 1.50g calcium is burned in air, a mixture of ionic solids calcium oxide and red
brown solid is formed.
The red brown solid has the following composition by mass: Ca, 81.1%; N,18.9%.
Adding water to the red brown solid produces calcium hydroxide and 19.2 cm3 of
ammonia gas at room temperature and pressure.
(i) Calculate the formula of the red brown solid. [1]
(ii) Write an equation for the reaction between red brown solid with water. [1]
(iii) Write equations for the reactions of calcium with air and use them to calculate
the mass of CaO formed when 1.5g of calcium is burnt in air. [3]
(c) Calcium oxide is normally made by heating calcium carbonate to a temperature above
825oC. A gas which turns lime water chalky is produced in the process.
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(i) Writete an equation for the decomposition of CaCO 3 .
[1]]
(ii) xplain
plain why barium carbonate decomposes at a higher temperature than
Explain
alcium
cium carbonate.
calcium [2]
IJC 2016Prelim/9647/03[Turn over 489 trendyline

3
(d) Methylcyclohexene reacts with hydrogen bromide to form alkyl bromides.
+%U &+%U
PHWK\OF\FORKH[HQH
(i) The above reaction could produce two isomers with molecular formula C 7 H 13 Br.
However, when the reaction is carried out, mainly one product is formed. Give
the structural formula of the major product, explaining your answer. [2]
(ii) Describe the mechanism of the reaction between hydrogen bromide and
methylcyclohexene, C 6 H 9 CH 3 , showing curly arrows, charges, dipoles and any
relevant lone pairs. [3]
(iii) Unsymmetrical dihalides reacts with alkene in a similar way as hydrogen halides.
Predict the structure of the product when IBr reacts with methylcyclohexene, and
explain your answer by considering the polarity within the molecule IBr.[2]
[Total: 20]
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4
2 Alcohols and carboxylic acids have many scientific, medical and industrial uses worldwide.
(a) Methanol is made from the following gaseous reaction.
CO(g) + 2H 2 (g) CH 3 OH(g)
A 1:2 mixture of CO and H 2 was pumped into a sealed reactor at 6 atm and then
heated to 227 oC and maintained at this temperature for some time. When equilibrium
was reached, the partial pressure of CH 3 OH was found to be 1.6 atm.
(i) Write an expression for K p for the reaction.Hence, determine the value of
K p stating its units.
[3]
(ii) Suggest the effect on the position of equilibrium and value of K p when methanol
is removed from the reaction vessel. Explain your answer. [2]
(b) Grignard reagent, RMgX, is an important reagent in organic synthesis. Grignard

reagents are prepared by the addition of activated magnesium on an alkyl halide or
aryl halide in non-polar solvents such as ether in anhydrous conditions.
- +
R CH2 X + Mg R CH2 MgX X = Cl or Br
An example of a Grignard reagent reacting with a ketone to form an alcohol via a two
stage process is given below:
R' R
Stage 1 : R CH2 MgCl + C O R CH2 C O MgCl
R'' R''
R' R'
H2O
Stage 2 : R CH2 C O MgCl R CH2 C OH + Mg(OH)Cl
R'' R''
R' and R'' could be alkyl / aryl group / H atoms
(i) Suggest the type of reaction occurred between the Grignard reagent and the
carbonyl compound in Stage 1 and 2. [2]
(ii) Suggest the structural formula of the final organic product formed when
CH2MgBr
t
trendyline
is reacted
ed with propanone,
propanone
propan , CH 3 COCH 3 , in a similar two-
tep
ep process.
step [1]
(iii) educe the structures of a suitable Grignard reagent, RMgBr,

Deduce RMg
RMgB and a suitable
arbonyl compound, RRCO, tto synthesize the following
carbonyl fo alcohol,
(CH 3 ) 2 CHCH 2 CH(OH)CH 2 CH 2 CH 3 .
[2]

5
(iv) The Grignard reagent CH 3 CH 2 CH 2 MgBr can be readily converted into a

carboxylic acid by using carbon dioxide.
Suggest the structural formula of the organic product formed. [1]
(v) The product formed by using Grignard reagent in (b) (iii)does not rotate the
plane polarised light. Explain your reasoning. [2]
(c) Describe and explain the relative acidities of phenol, benzoic acid and
phenylmethanol. [3]
(d) Lactic acid, glycolic acid and salicylic acid are three organic acids commonly used in
chemical peel.
CH3CHCO2H CH2CO2H OH
OH OH
COOH
lactic acid glycolic acid salicylic acid
Suggest a simple chemical test that can be used to distinguish each of the following
pairs.State what you would observe for each chemical test.
1. lactic acid from glycolic acid, and

2. glycolic acid from salicylic acid.
[4]
[Total: 20]
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6
3 Aluminium, is the third most abundant element (after oxygen and silicon) found in the
Earths crust. Aluminium reacts readily with carbon to form aluminium carbide, Al 4 C 3 .
(a) Aluminium carbide can react with protic reagents such as hydrochloric acid to produce
methane gas and aluminium(III) chloride.
(i) Write a balanced equation for the reaction between aluminium carbide and
hydrochloric acid. [1]
(ii) Using the equation in (a)(i), calculate the maximum volume of methane gas that
can be produced when 12.0 g of aluminium carbide reacts with 250 cm3 of2.0
mol dm-3 hydrochloric acid at standard temperature and pressure.
[3]
(b) Aluminium chloride is used as a catalyst in electrophilic substitution reactions. The

chlorination of benzene is represented by the following overall equation.
Cl
AlCl3
+ Cl + HCl
2
The reaction occurs in several steps.
The first step is the reaction between Cl 2 and AlCl 3 .
Cl 2 + AlCl 3 Cl + AlCl 4
The benzene ring is then attacked by the Clcation in the second step.
AlCl 3 reacts in a similar way with halogenoalkanes and acyl chlorides, producing a
carbocation that can then attack a benzene ring.
Using the reactions described above as parts of a synthesis route, a student

suggested the following route to form phenyl 4-phenylbutanoate, from benzene.
I
Cl Cl OH
with AlCl3
step 1 step 2
A
step 3
O OH
O Route B O
-
phenyl 4 phenylbutanoate 2 steps
(i)
(ii) trendyline
xplain why step 1 has to be carried out in an anhydrous condition.
Explain
raw
aw the carbocation formed in step 1.
Draw
cond [1]
[1]

7
(iii) A student suggested that A could have the following structure:
By quoting appropriate data in the Data Booklet, explain why the structure
suggested by the student is less likely to be formed. [2]
(iv) Give appropriate reagents and conditions necessary for steps 2 and 3. [2]
(v) Suggest the reagents and conditions for each of the two steps in route B. [2]
(vi) Predict the structure of the product of each of the following reactions. Both
compoundsEandFreact with 2,4-dinitrophenylhydrazine.[2]
AlCl3 E
Cl C9H8O
O
C
O
AlCl3 F
Cl C9H8O
(vii) Describe and explain the relative ease of hydrolysis of the two
chloro-compounds C and D. [2]
(c) By considering the structure and bonding, explain why
(i) the boiling point of aluminium fluoride is higher than that of aluminium chloride.
[2]
COOH COOH
OH
(ii) salicylic acid, is less soluble in water than benzoic acid, .
[2]

8
4 The Strecker synthesisis a term used for a series of chemical reactions that synthesize an
amino acid from an aldehyde or ketone. This reaction requires acid and HCN is supplied
from cyanide salts.
NH2
Stage 1 Stage 2 NH2
O
KCN H+ O
R R
R H NH4Cl N
OH
One example of the Strecker synthesis is a multikilogram scale synthesis of amino acids.
(a) Name the type of reaction occurring in Stage 2 and state the reagent and conditions
used in this reaction. [2]
(b) InStage 1, ammonia formed from the reaction between KCN and NH 4 Cl reacts with
the aldehyde.
Suggest an equation for the formation of ammonia from the reaction between KCN
and NH 4 Cl and describe the role of KCN in stage 1. [2]
(c) Explain why isobutyramide is less basic than 3-aminobutan-2-one.
NH2 O NH2
- - -
isobutyramide 3 aminobutan 2 one
[2]
(d) Predict the outcomes of the following reactions starting from isobutyramide, drawing
the structures of the intermediate Jand the productsKand L.
O
LiAlH4 excess CH3Cl
J K
C7H18NCl
NH2
isobutyramide
NaOH(aq),
reflux
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L + gas
[3]

9
(e) Compound P, C 9 H 12 O 2 , shows optical activity and does not react with aqueous
potassium carbonate. However, it is soluble in aqueous potassium hydroxide.
When P reacts with hot acidified potassium dichromate(VI), the solution turns from
orange to green. P also decolourises aqueous bromine to form a white precipitate,Q,
C 9 H 10 O 2 Br 2 .
Upon heating with concentrated sulfuric acid, P gives only compound R, C 9 H 10 O,

which displays geometric isomerism. R gives compound S and ethanoic acid on
reacting with hot acidified potassium manganate(VII) solution.
Suggest the structuresof P, Q, Rand S, explaining the reactions involved. [7]
(f) The structure of squaric acid is shown below.
O OH
O OH
(i) State the functional groups in squaric acid.[2]
(ii) Squaric acid is a stable molecule although it has high angle strain associated
with a four-membered ring. Itis a strong diprotic acid with a pK a values 1.5 and
3.4 respectively. Explain the high acidity of squaric acid. [2]
[Total: 20]
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10
5 Iron is, by mass, the most common element on Earth, forming much of Earth's outer and
inner core. Iron and its compounds have been used as catalysts in many reactions. For
example, aqueous iron(II) chloride can be used to catalyse the reaction between I and
S 2 O 8 2, to form I2 and SO 4 2ions.
(a) (i) Write an equation to represent the third ionisation energy of Fe. [1]
(ii) Write the electronic configuration for Fe2+. Hence, suggest why the third
ionisation energy of 26 Fe is lower than that of 25 Mn. [2]
(iii) State the type of catalysis for the reaction between I and S 2 O 8 2 that is
catalysed by aqueous iron(II) chloride. [1]
(iv) The reaction between I and S 2 O 8 2 can also be catalysed by aqueous cobalt(II)
chloride. Using relevant E values from the Data Booklet, explain why cobalt(II)
chloride can be a catalyst for this reaction. [2]
(b) A green solution of aqueous iron(II) chloride is reacted with acidified potassium
manganate(VII). The resultant solution D is treated with aqueous sodium carbonate to
form a reddish brown precipitate E, together with a colourless gas which forms white
precipitate in aqueous calcium hydroxide. When aqueous NH 4 SCN is added to D, a
blood red solution is formed.
(i) Explain why aqueous iron(II) chloride is coloured. [2]
(ii) Identify precipitate E. [1]
(iii) Suggest the type of reaction that has occurred for the formation of the blood red
solution. [1]
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11
(c) Iron is also used in making iron-air battery which is a low-cost and environmental
friendly rechargeable energy source. An iron-air battery comprises of iron electrode,
porous carbon-containing air electrode. The electrolyte used is aqueous potassium
hydroxide.
external circuit
e e
Fe3O4 OH O2
O2
Fe O2
OH
O2
KOH(aq) O2
iron electrode air electrode
separator
At the iron electrode, iron is oxidised to magnetite, Fe 3 O 4 , during discharging,

according to the following reaction:
3Fe + 8OH Fe 3 O 4 + 4H 2 O + 8e
At the air electrode, oxygen is reduced to form hydroxide ions.
(i) Write the half-equation for the reaction that occurred at the air electrode during
discharging. [1]
(ii) During discharging, the cell acts as a power source and the overall reaction
occurred is as follows:
3Fe + 2O 2 Fe 3 O 4
Suggest, with explanation, for the sign of the G for this reaction. [1]
(iii) The battery is capable of producing an e.m.f. of 1.28V. By using suitable data
from the Data Booklet suggest a value for the Eof the Fe 3 O 4 |Fe electrode
reaction.[1]
During charging, at the iron electrode, magnetite and water undergo the following
reaction:
Fe 3 O 4 + 4H 2 O + 8e 3Fe + 8OH
At the same electrode, a competing side-reaction occurs where water reacts to form
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y
hydrogenn gas according to the following reaction:
en
2H
2 2 O + 2e H 2 + 2OH

12
After a 1-hour charging, the volume of H 2 gas evolved, measured at r.t.p., is 0.652
dm3.
(iv) Calculate the amount of electrons that was required to produce H 2 gas. [1]
(v) A current of 9.5 A is supplied to the battery during the 1-hour charging.
Use this information and your answer in (c)(iv) to calculate the amount of iron
produced during the charging. [2]
(d) The separator used in the iron-air battery is an organic polymeric membrane, made
from compound X.
Compound X has a molecular formula C 3 H 3 N. On heating with dilute sulfuric acid, X

forms compound Y, C 3 H 4 O 2 . Both X and Ydecolourise aqueous bromine, however,
only Y reacts with sodium carbonate to form gas which forms white precipitate in
Ca(OH) 2 (aq).
Suggest structures for compounds X and Y, giving reasons for your answers. [4]
[Total: 20]
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TEACHERS COPY
JC 2PRELIMINARY EXAMINATION
Higher 2
CHEMISTRY 9647/03
Paper 3 Free Response 26 August 2016
2 hours
Additional Materials: Writing Papers

Data Booklet
Cover Page


You are reminded of the need for good handwriting.
Your final answers should be in 3 significant figures.
The number of marks is given in the brackets [ ] at the end of each question or part question.
trendyline
y This document consists of 18printed pages.

500 trendyline
2
1 Data concerning the elements of group II of the Periodic Table, at 298K, are given in the
table. Further data may be found in the Data Booklet. M refers to elements of group II.
st nd 2+
1 and 2 IE of M + atom of M + hydration of M E /V
-1 -1 -1
/ kJ mol / kJ mol / kJ mol
Ca 1740 178 1650 2.87
Sr 1608 164 1480 2.89
(a) The electrode reduction potential E of Group II elements gives an indication of the
ease with which the following reaction occurs:
M(s) M2+(aq) + 2e reaction 1
The enthalpy change of reaction 1 can be related to the following factors:

first and second ionisation energy of the element
enthalpy change of atomisation and
enthalpy change of hydration of its gaseous ion.
(i) Construct an energy cycle relating the factors above, and use the values given
above to calculate the enthalpy change of reaction 1 for calcium. [3]
Reaction 1
2+
Ca(s) Ca (aq) + 2e
Enthalpy change of atomisation
Ca(g) 2+
Hhydration(Ca )
st
1 ionisation energy
+
-
Ca (g) + e
nd
2 ionisation energy
2+ -
Ca (g) + 2e
Cycle: all correct compounds with state symbols [2]
(deduct 1m for omission of state symbols,
Enthalpy change of reaction 1 = 178 + 1740 + (-1650) = +268 kJ mol-1 [1]
(ii) By quoting appropriate data from Data Booklet, explain the difference in
enthalpy change of hydration of calcium and strontium ions. [2]
Ca2+(0.099nm) has smaller ionic radius than Sr2+(0.113nm) -[1]
trendyline
ndyline
li
Since
nce they have the same charge, arge density of Ca2+ is larger,
charg the charge
2+
Thus Ca forms strongertronger ion
ion-dipole
dipole interactions with water molecules
m [1]
+
+ hydration
ra of Ca2+ is
s more exothermic than that of Sr2+.
PRELIMINARY EXAM INNOVA9647/03/2016 501

[Turn over trendyline
3
(c) Calcium oxide is the key ingredient for the process of making cement.
When calcium is burned in oxygen, calcium oxide is produced.

When 1.50g calcium is burned in air, a mixture of ionic solids calcium oxide and red
brown solid is formed.
The red brown solid has the following composition by mass: Ca, 81.1%; N,18.9%.
Adding water to the red brown solid produces calcium hydroxide and 19.2 cm3 of
ammonia gas at room temperature and pressure.
(i) Calculate the formula of the red brown solid. [1]
Ca N
Mass in 100g 81.1 18.9
Amt in 100g 2.0224 1.35
Simplest ratio 1.50 1
ratio 3 2
Empirical formula of solid: Ca 3 N 2
(ii) Write an equation for the reaction between red brown solid with water. [1]
Ca 3 N 2 + 6H 2 O 2NH 3 + 3Ca(OH) 2
(iii) Write equations for the reactions of calcium with air and use them to calculate
the mass of CaO formed when 1.5g of calcium is burnt in air. [3]
Ca + O 2 CaO
3Ca + N 2 Ca 3 N 2
2equations correct : [1]
No. of moles of ammonia produced = 19.2/24000 = 0.0008

No. of moles of Ca 3 N 2 produced = 0.0008/2 = 0.0004
No. of moles of calcium used to react with nitrogen= 0.0004 x 3 = 0.0012
mass of CaO formed = (1.5/40.1 0.0012)(40.1+16) = 2.03g
(d) Calcium oxide is normally made by heating calcium carbonate to a temperature above
825oC. A gas which turns lime water chalky is produced in the process.
(i) Write an equation for the decomposition of CaCO 3 .

[1]
CaCO 3 (s) CaO(s) + CO 2 (g)
(ii) Explain why barium carbonate decomposes at a higher temperature than

calcium carbonate. [2]
Ba2+ has larger cation size than Ca2+,thus has lower charge density. [1]
The polarising power of Ba2+ is lower, thus less able to polarize electron
cloud of carbonate anion, weakening covalent bonds (CO) in the anion to a
smaller extent [1]
More energy is needed to break down the anion and hence decomposition
ttrendyline
d
temperature for BaCO 3 is higher
higher.
g .

4
(e) Methylcyclohexene reacts with hydrogen bromide to form alkyl bromides.
+%U &+%U
PHWK\OF\FORKH[HQH
(i) The above reaction could produce two isomers with molecular formula C 7 H 13 Br.
However, when the reaction is carried out, mainly one product is formed. Give
the structural formula of the major product, explaining your answer.
[2]
+
%U
[1]
Presence of an additional (more) electron donating alkyl group directly

+
bonded to the positively charged carbon in disperse the positive

+
charge to a greater extent thus is more stable, leading to the

formation of the major product. [1]
(ii) Describe the mechanism of the reaction between hydrogen bromide and
methylcyclohexene, C 6 H 9 CH 3 .
[3]
Electrophilic addition [1]

CH3 CH3
slow H
+ H Br + Br

CH3
CH3
Br
H H
+ Br f ast
2 marks for mechanism

(penalise 1 mark for 1-2 errors, penalise 2 marks for 3 errors or more)
slow step and balanced equation
arrows and lone pair
trendyline
polarity
correct intermediate
Unsymmetrical
metrical dihalides reacts with alkene in a similar way as hydro
hydrogen halides.
(iii) Predict the structure

di t th t t off th
the product
d t when IB reacts
h IBr t with
ith methylcyclohexene,
th and
explain your answer by considering the polarity within the molecule IBr.[2]

5
Understanding that iodine is less EN than bromine:

Iodine is less electronegative (or electron-deficient or electrophile) than bromine
[]
Thus, iodine will be added across the C=C first. []

(or Brwill attack the carbocation formed)
Thus, product is
I
Br
product [1]
[Total: 20]
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6
2 Alcohols and carboxylic acids have many scientific, medical and industrial uses worldwide.
(a) Methanol is made from the following gaseous reaction.

CO(g) + 2H 2 (g) CH 3 OH(g)
A 1:2 mixture of CO and H 2 was pumped into a sealed reactor at 6 atm and then
heated to 227 oC and maintained at this temperature for some time. When equilibrium
was reached, the partial pressure of CH 3 OH was found to be 1.6 atm.
(i) Write an expression for K p for the reaction.Hence, determine the value of
K p stating its units.
[3]
PCH3OH
Kp = [1]
PCOPH2 2
CO(g) + 2H 2 (g) CH 3 OH(g)
Initial / atm 2 4 0
Change / atm 1.6 3.2 +1.6
Equilibrium / atm 0.4 0.8 1.6
Correct equilibrium pressure for each reactant and product [1]
1.6
Kp= = 6.25 atm2[1] (correct units and values)
0.4 0.82
(ii) Suggest the effect on the position of equilibrium and value of K p when methanol
is removed from the reaction vessel. Explain your answer. [2]
When methanol is removed from the equilibrium, the partial pressure of
methanol decreases>@. By Le Chateliers Principle, the equilibrium position
would shift to the right to increase the partial pressure of methanol>@.
The value of K p would remain the same[1]as there is no change in

temperature. (K p is temperature dependent)
(b) Grignard reagent, RMgX, is an important reagent in organic synthesis. Grignard

reagents are prepared by the addition of activated magnesium on an alkyl halide or
aryl halide in non-polar solvents such as ether in anhydrous conditions.
- +
R CH2 X + Mg R CH2 MgX X = Cl or Br
An example of a Grignard reagent reacting with a ketone to form an alcohol via a two
stage process is given below:
trendyline
7
R' R
Stage 1 : R CH2 MgCl + C O R CH2 C O MgCl
R'' R''
R' R'
H2O
Stage 2 : R CH2 C O MgCl R CH2 C OH + Mg(OH)Cl
R'' R''
R' and R'' could be alkyl / aryl group / H atoms
(i) Suggest the type of reaction occurringin Stages1 and 2.

[2]
Stage 1: Nucleophilic Addition[1]
Stage 2: Hydrolysis [1]
(ii) Suggest the structural formula of the final organic product formed when
CH2MgBr
is reacted with propanone, CH 3 COCH 3 , in a similar two-

step process. [1]
H OH
C C CH3
H CH3
[1]
(iii) Deduce the structures of a suitable Grignard reagent, RMgBr, and a suitable
carbonyl compound, RRCO, to synthesize the following alcohol.
(CH 3 ) 2 CHCH 2 CH(OH)CH 2 CH 2 CH 3 [2]
(CH 3 ) 2 CHCH 2 CHO [1] and CH 3 CH 2 CH 2 MgBr[1]
OR
CH 3 CH 2 CH 2 CHO[1] and(CH 3 ) 2 CHCH 2 MgBr [1]
(iv) The Grignard reagent CH 3 CH 2 CH 2 MgBr can be readily converted into a

carboxylic acid by using carbon dioxide.
Suggest the structural formula for the organic product formed. [1]
CH 3 CH 2 CH 2 COOH[1]
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yyline
(v) p
The product formed byy using g Grignard
g g
reagent ( ) ((iii)does
in (b) ) not rotate the
ane polarised light. Explain your reasoning.
plane [2]
As the Grignard reagents can n attack the sp2 hybridised carbonyl carbon (trigonal
planar shape)>@
shap >@
shape) @ either from the top or the bottom of the plane p with equal
chance>@,
e>@, it results in a racemic mixture
mixture>@
ure>@ of products being formed.
for The optical
activity of the two isomers cancel out each other>@and the resulting mixture does
not the rotate plane polarised light.

8
(c) Describe and explain the relative acidities of phenol, benzoic acid and
phenylmethanol.
[3]
Acid strength: benzoic acid > phenol >phenylmethanol[1]
In benzoate ion, C 6 H 5 COO , the negative charge on oxygen is delocalised over

the two highly electronegative oxygen atoms.>@The C 6 H 5 COO anion is most
stable among the 3 anions and hence benzoic acid is the most acidic.
In the phenoxide ion of phenol, C 6 H 5 O-, the p-orbital of O overlaps with the -
electron cloud of the benzene ring so that the negative charge on O delocalises
into the benzene ring. >@This stabilization is not as great as that in the
C 6 H 5 COOion in which the negative charge is delocalized over 2 highly
electronegative O atoms. The phenoxide ion is less stable than benzoate ion and
hence phenol is less acidic than benzoic acid.
In the phenylmethoxide, C 6 H 5 CH 2 O-, the electron-donating alkyl/benzyl group

intensifies the negative charge on O atom.>@The C 6 H 5 CH 2 O- ion is, therefore, the
least stable and phenylmethanol is least acidic.
>@ comparing the stability of the 3 anions
Marking along the line of giving credit for the EDG/EWG/delocalisation +
stability of anions
(d) Lactic acid, glycolic acid and salicylic acid are three organic acids commonly used in
chemical peel.
CH3CHCO2H CH2CO2H OH
OH OH
COOH
lactic acid glycolic acid salicylic acid
Suggest a simple chemical test that can be used to distinguish each of the following
pairs.State what you would observe for each chemical test.
1) lactic acid from glycolic acid, and

2) glycolic acid from salicylic acid.
[4]
1) reagents and conditions: I 2 , NaOH (aq), warm[1]
ttrendyline
nd
dyylliin
dy
Yellow
llow
lo ppt of CHI 3 formed for lactic acid but not glycolic ac
acid[1]
OR
agents
gents and conditions:
reagents conditio KMn 4 (aq), H 2 SO
KMnO O 4 (aq), heat
heat[1]
[1]
1]
rple
ple KMnO 4 decolourises for
Purple fo lactic
actic acid and an glycolic acid.
a For glycolic
acid,
id effervescence of colourless s gas
g which formed white ppt with calcium
hydroxide was observed but not for lactic acid.[1]

9
2) reagents and conditions: neutral FeCl 3 (aq)[1]

Violet complex formed for salicylic acid but not for glycolic acid.[1]
OR
reagents and conditions: Br 2 (aq)[1]
Observation with: Reddish brown Br 2 (aq) decolourised for salicylic acid but
not for glycolic acid.[1]
*NaOH cannot be used to distinguish these 2 compounds as there is no

observable change in both compounds although phenol reacts with NaOH.
[Total: 20]
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10
3 Aluminium, is the third most abundant element (after oxygen and silicon) found in the
Earths crust. Aluminium reacts readily with carbon to form aluminium carbide, Al 4 C 3 .
(a) Aluminium carbide can react with protic reagents such as hydrochloric acid to produce
methane gas and aluminium(III) chloride.
(i) Write a balanced equation for the reaction between aluminium carbide and
Al 4 C 3 (s) + 12HCl (aq) 4AlCl 3 (aq) + 3CH 4 (g) [1] ss not required
(ii) Using the equation in (a)(i), calculate the maximum volume of methane gas that
can be produced when 12.0 g of aluminium carbide reacts with 250 cm3 of
2.0 mol dm-3 hydrochloric acid at standard temperature and pressure.[3]
12.0
Amt of Al 4 C 3 = 0.08333 mol
4(27.0) 3(12.0)
Amt of HCl = 0.250 x 2.0 = 0.5 mol [1]

If Al 4 C 3 is limiting, amt of HCl required = 12 x 0.08333= 1.000 mol
So Al 4 C 3 is in excess. HCl is limiting reagent [1]
0.5
Amt of CH 4 produced = 3 0.125 mol
12
Volume of CH 4 obtained = 0.125 x 22.4= 2.80 dm3 [1]
(b) Aluminium chloride is used as a catalyst in electrophilic substitution reactions. The

Cl
AlCl3
+ Cl + HCl
2
Cl 2 + AlCl 3 Cl + AlCl 4
The benzene ring is then attacked by the Cl cation in the second step.
AlCl 3 reacts in a similar way with halogenoalkanes and acyl chlorides, producing a
carbocation that can then attack a benzene ring.
Using the reactions described above as parts of a synthesis route, a student

suggested the following route to form phenyl 4-phenylbutanoate, from benzene.
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11
I
Cl Cl OH
with AlCl3
step 1 step 2
A
step 3
O OH
O Route B O
-
phenyl 4 phenylbutanoate 2 steps
(i) Explain why step 1 has to be carried out in an anhydrous condition. [1]
AlCl 3 undergoes hydrolysis when reacted with water. [1]
(Accept hydration)
(ii) Draw the carbocation formed in step 1. [1]
Cl
(iii) A student suggested that Acould have the following structure:
By quoting appropriate data in the Data Booklet, explain why the structure
suggested by the student is less likely to be formed. [2]
E(CI) = + 240 kJ mol1E(CCl) = + 340 kJ mol1 [1] for quoting data

Since E(C-I) is smaller than E(CCl) and thus CI bond is weaker than the C
Cl bond, [1] it is easier to break CI bond. Hence, F should contain the Cl atom,
rather than I atom.
(iv)
Give appropriate reagents and conditions necessary for steps 2 and 3. [2]
Step 2: KOH(aq) or NaOH(aq), heat [1]
Step 3: K 2 Cr 2 O 7 , dilute H 2 SO 4 , heat [1]
(v)
t d li
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Suggest
g the reagents
g and conditions for each of the two steps in route B. [2]
Route
oute B step 1:
1 PCl 5 (s)
((s),
), room
m temp OR PCl
PC 3 , room ttemp
tempOR
OR SOCl
S 2 , room temp
Route
oute B step 2:
2: NaOH(aq), phenol or phenoxide ion

12
(vi)
Predict the structure of the product of each of the following reactions.
Both compounds E andFreact with 2,4-dinitrophenylhydrazine. [2]
AlCl3 E
Cl C9H8O
O
C
O
AlCl3 F
Cl C9H8O
E O
F
[1] for each structure
(vii) Describe and explain the relative ease of hydrolysis of the two chloro-
compoundsC and D. [2]
Compound D undergoes hydrolysis more readily than compound C. [1]
The C atom of the acyl groupin compound D is attached to two

electronegative atoms, Cl and O. Hence this carbon atom is more electron
deficient>@and thus more susceptible to nucleophilic attack >@FRPSDUHGWR
the carbon atom of C-Cl in compound C.
(c) By considering the structure and bonding, explain why

(i) the boiling point of aluminium fluoride is higher than that of aluminium chloride.
[2]
AlCl 3 hassimple molecular structure while AlF 3 has giant ionic structure.>@
More energy>@ is required to overcome the stronger electrostatic forces of

attraction between oppositely charged ions in AlF 3 >@than the weak van der
waals forces of attraction between AlCl 3 molecules>@. This results in the
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en
en
higher
g boiling
g point
p in AlF 3 .
COOH
COOH COOH
H
OH
O
salicylic acid, , is less soluble in water than benzoic acid,

.
[2]
Both compounds are simple covalent molecules and can form hydrogen
13
bonding with water molecules.
However, intramolecular hydrogen bonding present in salicylic acid due to

the close proximity of the carboxyl group and hydroxyl group. [1]
Thus, the intermolecular hydrogen bonding between salicylic acid and

water is less extensive than the hydrogen bonding between benzoic acid and
water. [1]
This results in the lower solubility of salicylic acid in water.
[Total: 20]
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14
4 The Strecker synthesis is a term used for a series of chemical reactions that synthesize an
amino acid from an aldehyde or ketone. This reaction requires acid and HCN is supplied
from cyanide salts.
NH2
Stage 1 Stage 2 NH2
O
KCN H+ O
R R
R H NH4Cl N
OH
One example of the Strecker synthesis is a multikilogram scale synthesis of amino acids.
(a) Name the type of reaction occurring in Stage 2 and state the reagent and
conditions used in this reaction.[2]
Acidic hydrolysis[1]
Reagents and conditions: dilute sulfuric acid , heat [1]
(b) InStage 1, ammonia formed from the reaction between KCN and NH 4 Cl reacts
with the aldehyde.
Suggest an equation for the formation of ammonia from the reaction between
KCN and NH 4 Cl and describe the role of KCN in stage 1. [2]
NH 4 Cl + KCN NH 3 + HCN + KCl [1]

Accept if above reaction is irreversible.
KCN supplies CN- which acts as a proton acceptor or base.[1]OR CN- acts a
nucleophile [1]
(c) Explain why isobutyramide is less basic than 3-aminobutan-2-one.
NH2 O NH2
- - -
isobutyramide 3 aminobutan 2 one
[2]
.
Isobutyramide is an amide and is neutral as lone pair of electrons on N atom

is delocalised into the pi electron cloud[1] of the adjacent C=O group making
the lone pair on N atom unable to accept a proton[] In 3-aminobutan-2-
one, the lone pair on N atom is available to accept a proton[].
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15
(d) Predict the outcomes of the following reactions starting from isobutyramide, drawing
the structures of the intermediate J and the products Kand L.
O
LiAlH4 excess CH3Cl
J K
C7H18NCl
NH2
isobutyramide
NaOH(aq),
reflux
L + gas
[3]
Ans:
+ -
Cl
NH2 N
- +
O Na
1m each
(e) Compound P, C 9 H 12 O 2 , shows optical activity and does not react with aqueous
potassium carbonate. However, it is soluble in aqueous potassium hydroxide.
When P reacts with hot acidified potassium dichromate(VI), the solution turns from
orange to green. P also decolourises aqueous bromine to form a white precipitate, Q,
C 9 H 10 O 2 Br 2 .
Upon heating with concentrated sulfuric acid, P gives only compound R, C 9 H 10 O,
trendyline
isplays geometric isomerism. R gives
which displays s compound
com S and ethanoic acid on
g with hot acidified potassium manganate(VII) solution.
reacting solutio
Suggestt the structuresof
structureso PP,, Q
Q,, R and
a S S,, explaining the reactions involved.
invo
[7]

16
OH
OH OH
C CH2CH3
C H
H3CH2C H
P: OH OR
OH
Br Br OH OH
Br C CH2CH3
C
H3CH2C H
Q: OH OR Br
OH
OH
H
C CHCH3
C
H CHCH3
R: OR
OH
OH
ttrendyline
r dyyl
COOH
COOH
CO
C
S: HO O OR
1m for each structure

17
P shows optical activity P has chiral carbon>@
P does not react with aqueous No -COOH

potassium carbonate.
However, it is soluble in aqueous Undergoes acid-base reaction.

potassium hydroxide. Contains phenol >@
P reacts with hot acidified potassium P undergoes oxidation. >@

dichromate(VI), the solution turns from
orange to green Contains primary or secondary
alcohol >@
P also decolourises aqueous bromine to Pundergoes electrophilic

form a white precipitate, Q, substitution>@
C 9 H 10 O 2 Br 2 .
PcontainphenolJURXS>@
Br atoms added to 2 or 4 positions on

ring
Upon heating with concentrated sulfuric P undergoes elimination of H 2 O>@

acid, P gives only compound R,
C 9 H 10 O, which displays geometric R is an alkeneFRQWDLQV& &>@
isomerism.
R gives compound S and ethanoic acid R undergoes oxidative cleavage>@
on reacting with hot acidified potassium
manganate(VII) solution.
9 [] 3m
6-8 [] 2m
3-5 [] 1m
0-2 [] 0m
(f) The structure of squaric acid is shown below.
O OH
O OH
(i) State the functional groups in squaric acid.[2]
Ketone, alkene and alcohol

2m for all 3 functional groups ; 1m for 2 functional groups
trendyline
y
(ii) quaric
uaric acid is a stable molecule although it has high angle strain associated
Squaric
ith a four
with four--membered ring. It is a strong diprotic acid with a p
four-membered pK a values 1.5 and
3.44 respectively. Explain the high acidity
acidity of squaric acid. [2]
The
he e high acidity of the squaric acid is due to the formation of a very stable
anion[1]due
nion[1]due to negative charges rges being delocalised across the sp2
hybridised carbon[1].
[Total: 20]
18
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19
5 Iron is, by mass, the most common element on Earth, forming much of Earth's outer and
inner core. Iron and its compounds have been used as catalysts in many reactions. For
example, aqueous iron(II) chloride can be used to catalyse the reaction between between I
and S 2 O 8 2, to form I 2 and SO 4 2ions.
(a) (i) Write an equation to represent the third ionisation energy of Fe. [1]
Fe2+(g) Fe3+(g) + e [1, state symbols must be included]
(ii) Write the electronic configuration for Fe2+. Hence, suggest why the third
ionisation energy of 26 Fe is lower than that of 25 Mn.
[2]
Fe2+: 1s2 2s2 2p6 3s2 3p6 3d6 [1]
The lower 3rd IE of Fe is due to inter-electronic repulsion>@by the paired
electrons in the d orbital>@.
(iii) State the type of catalysis for the reaction between I and S 2 O 8 2 that is
catalysed by aqueous iron(II) chloride. [1]
Homogenous catalysis[1]
(iv) The reaction between I and S 2 O 8 2 can also be catalysed by aqueous cobalt(II)
chloride. Using relevant E values from the Data Booklet, explain why cobalt(II)
chloride can be a catalyst for this reaction. [2]
S 2 O 8 2 + 2Co2+ 2Co3+ + SO 4 2
Ecell = +2.01 (+1.82)

= +0.19 V (reaction is energetically feasible) [1]
2 I + 2Co3+ 2Co2+ + I 2
Ecell = +1.82 (+0.54)
= +1.28 V (reaction is energetically feasible)[1]
(b) A green solution of aqueous iron(II) chloride is reacted with acidified potassium
manganate(VII). The resultant solution D is treated with aqueous sodium carbonate to
form a reddish brown precipitate E, together with a colourless gas which forms white
precipitate in aqueous calcium hydroxide. When aqueous NH 4 SCN is added to D, a
blood red solution is formed.
(i) Explain why aqueous iron(II) chloride is coloured. [2]

FeCl 2 (aq) is coloured due to:
presence of incompletely filled 3d orbitalsin the Fe2+ ions.
In the presence of ligands, 3d orbitals split into two groups with small
energy gap >@
Some of the light energy is used to promote an electron from a 3d
orbital of lower energy into the partially filled 3d orbital of higher
energy.[1]
Colour seen is the complement of the colour absorbed in thevisible
t
regionof the spectrum
rregionof
(ii) entify precipitate E

Identify E.. [1]]
on(III) hydroxide [1]]
iron(III)
ron(III)
(iii) Suggest the type of reaction that has occurred for the formation of the blood red
solution. [1]

20
Ligand exchange[1]

21
(c) Iron is also used in making iron-air battery which is a low-cost and environmental
friendly rechargeable energy source. An iron-air battery comprises of iron electrode,
porous carbon-containing air electrode. The electrolyte used is aqueous potassium
hydroxide.
external circuit
e e
Fe3O4 OH O2
O2
Fe O2
OH
O2
KOH(aq) O2
iron electrode air electrode
separator
At the iron electrode, iron is oxidised to magnetite, Fe 3 O 4 , during discharging,

according to the following reaction:
3Fe + 8OH Fe 3 O 4 + 4H 2 O + 8e
At the air electrode, oxygen is reduced to form hydroxide ions.
(i) Write the half-equation for the reaction that occurred at the air electrode during
discharging. [1]
O 2 + 2H 2 O + 4e 4OH[1]
(ii) During discharging, the cell acts as a power source and the overall reaction
occurred is as follows:
3Fe + 2O 2 Fe 3 O 4
6XJJHVWZLWKH[SODQDWLRQIRUWKHVLJQRIWKH* for this reaction. [1]

Negative>@. The reaction that occurred during discharging should be a
spontaneous reaction>@.
(iii) The battery is capable of producing an e.m.f. of 1.28V. By using suitable data
from the Data Booklet suggest a value for the Eof the Fe 3 O 4 |Fe electrode
reaction.[1]
Ecell = Ered Eox
+1.28 = +0.40 E(Fe 3 O 4 |Fe)
E(Fe 3 O 4 |Fe) = 0.88 V[1]
During charging, at the iron electrode, magnetite and water undergo the following
trendyline
yli
reaction:
n:
Fe 3 O 4 + 4H 2 O + 8e Fe + 8OH
3Fe
At the same electrode, a competing side

side-reaction
e-re
reaction occurs where water
wa reacts to form
hydrogen gas according
di to the
h following
f ll i reaction:
i
2H 2 O + 2e H 2 + 2OH
22
After a 1-hour charging, the volume of H 2 gas evolved, measured at r.t.p., is 0.652
dm3.
(iv) Calculate the amount of electrons that was required to produce H 2 gas.
[1]
Amount of H 2 evolved = 0.652/24 = 2.717 x 10-2 mol
Amount of electrons required = 5.434 x 10-2 mol[1]
(v) A current of 9.5 A is supplied to the battery during the 1-hour charging.
Use this information and your answer in (c)(iv) to calculate the amount of iron
produced during the charging. [2]
It = n e F
Ne = (9.5)(3600)/96500 = 0.3544 mol[1]
Amount of electrons reacted with Fe 3 O 4 = 0.3544 - 5.434 x 10-2 = 0.3001 mol
Amount of Fe produced = 0.3001 x 3/8 = 0.113 mol[1]
Ignore if student went on to calculate mass of Fe.

(d) The separator used in the iron-air battery is an organic polymeric membrane, made
from compound X.
Compound X has a molecular formula C 3 H 3 N. On heating with dilute sulfuric acid, X

forms compound Y, C 3 H 4 O 2 . Both X and Y decolourise aqueous bromine, however,
only Y reacts with sodium carbonate to form gas which forms white precipitate in
Ca(OH) 2 (aq).
Suggest structures for compounds X and Y, giving reasons for your answers. [4]
Evidence Deduction
Both X and Y decolourise Both X and Y undergoes electrophilic [1]
aqueous bromine addition.
X and Y contains alkene group.
Y reacts with sodium carbonate to Y undergoes acid-carbonate reaction [1]
form gas which forms white with sodium carbonate.
precipitate in Ca(OH) 2 (aq).
Y contains carboxylic acid group.
On heating with dilute sulfuric X undergoes acidic hydrolysis to form [1]
acid, X forms compound Y, Y.
C3H4O2. X contains nitrile group
[max 2m]
X: CH 2 =CHCN[1]Y: CH 2 =CHCOOH[1]
[Total: 20]
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JURONG JUNIOR COLLEGE
2016 JC 2 PRELIMINARY EXAMINATION
Higher 2
CANDIDATE
NAME
EXAM INDEX
CLASS 16S
NUMBER
CHEMISTRY 9647/01
1 hour

Data Booklet

Write your name, class and exam index number on the Answer Sheet in the spaces provided unless this has
been done for you.
There are forty questions on this paper. Answer all questions. For each question there are four possible
answers A, B, C or D.
Choose the one you consider correct and record your choice in soft pencil on the separate Answer Sheet.
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ocument
cu
This document consists of 15 printed pages and 1 blank page.
[Turn over
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2
Section A
to be correct.
Which particle would, on losing an electron, have a configuration that corresponds to the
ground state of an element in Group V?
A Cl+ B Si C N D C+
2 In the following, the species in each pair contain the same number of electrons and the same
number of neutrons.
Identify the pair of species that does not fit the above description.
A HF F
B H2O OH
C NH 3 NH 4 +
D CH 4 CH 3 +
3 Four substances have the physical properties shown.
Which substance could be aluminium chloride?
electrical electrical
electrical
melting point conductivity conductivity
conductivity
/ oC of molten of aqueous
of solid
substance solution
A 98 poor poor poor
B 190 poor poor good
C 660 good good insoluble
D 800 poor good good
4 In which of the following pairs does the second compound have a higher boiling point than
the first?
A NaF NaI
B CaO Na 2 O
C CH 3 OH CH 3 OK
D CH 3 CH 2 OH CH 3 CH 2 SH
Jurong Junior College
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EXAMINATION
AMINAT /201
016
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3
5 The interhalogen compound BrF 3 is a volatile liquid which autoionises.
2BrF 3 BrF 2 + + BrF 4 H
The electrical conductivity of BrF 3 decreases with increasing temperature.
Which combination correctly represents the sign of H and the shape around bromine
in BrF 4 ?
H BrF 4
A + tetrahedral
B tetrahedral
C square planar
D + square planar
6 A quantity of ethanol was burned underneath a copper can containing 400 g of water at 30
o
C. The temperature of the water rose to 85 oC after the complete combustion of 5 g of
ethanol (M r = 46).
The efficiency of heat transfer to the water will not be 100% after taking into considerations
the heat capacity of the copper can.
Given that the specific heat capacity of water is 4.2 J g1 K1 and the enthalpy change of
combustion of ethanol is 1367 kJ mol1, what is the efficiency of heat transfer to the water?
A 7.4% B 62% C 63% D 96%
7 Clouds and rain form when air saturated with water vapour cools.
H 2 O(g) H 2 O(l)
What are the correct signs of H and S for this reaction?
H S
A
B + +
C +
D +
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016 [Turn over
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8 Hydrazine, N 2 H 4 , is used as a rocket fuel because it reacts with oxygen as shown, producing
environmentally friendly gases.
N 2 H 4 (l) + O 2 J1 2 (g) + 2H 2 O(g) H N-PRO1
Despite its use as a rocket fuel, hydrazine does not burn readily in oxygen.
Which statement explains why hydrazine does not burn readily?
A The activation energy is too high.

B Hydrazine is a liquid.
C The NN bond is very strong.
D G of the reaction is negative.
During electrolysis under suitable conditions, 1.18 g of chromium is deposited on the cathode
when 4370 C of electricity is passed into a chromium-containing electrolyte.
Which of the following could have been the electrolyte?
A CrCl 2
B CrCl 3
C K 2 CrO 3
D K 2 Cr 2 O 7
10 A sample of hydrogen iodide gas is maintained at a constant temperature of 600 K.

A dynamic equilibrium is established with hydrogen, iodine and hydrogen iodide all present.
Which statement describes this situation?
A The amount of hydrogen iodide present is constantly changing at equilibrium.

B Half of the original amount of hydrogen iodide is present at equilibrium.
C At equilibrium, hydrogen iodide is being formed at the same rate as it decomposes.
D The amount of hydrogen iodide present at equilibrium is affected by the pressure.
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11 Metal sulfides are generally insoluble and some relevant K sp values are given in the table.
Salt Colour K sp / mol2dm6

CuS black 6.3 1036
ZnS white 1.6 1024
When aqueous copper sulfate is added to white solid of ZnS, black precipitate of CuS
is observed according to the following reaction.
ZnS(s) + Cu2+(aq) CuS(s) + Zn2+(aq)
What is the equilibrium constant for the reaction above?
A 1.0 1059
B 3.9 1012
C 5.0 105
D 2.5 1011
12 A solution was made by mixing 0.040 mol of lactic acid and 0.030 mol of sodium hydroxide.
Water was added until the volume of the solution was 2 dm3.
What is the pH of the solution?

[Lactic acid is a monobasic acid with K a = 8.4 104 mol dm3 ]
A 2.6 B 2.7 C 3.0 D 3.6
13 A piece of magnesium ribbon was added to 25 cm3 of dilute hydrochloric acid. The
magnesium was completely dissolved and the total volume of hydrogen gas evolved was
measured.
In a second experiment an identical piece of magnesium ribbon was used. This was added to
another 50 cm3 of the same dilute hydrochloric acid. The total volume of hydrogen evolved
was measured.
How will the initial rate of reaction and total volume of hydrogen evolved in the second
experiment compare to that of the first experiment?
initial rate of total volume of

reaction hydrogen evolved
A increase increase
B increase no change
C no change increase
D no change no change
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14 In acid solution BrO 3 ions will slowly oxidise Br ions to Br 2 .

BrO 3 + 5Br + 6H+ 3Br 2 + 3H 2 O
The variation for the initial rate of reaction with the concentrations of the reactants was
investigated in two experiments.
experiment initial [BrO 3 ] initial [Br ] initial [H+] initial rate

/mol dm3 /mol dm3 /mol dm3 /mol dm3 min1
1 0.10 0.15 0.08 3.5
2 0.20 0.30 y 3.5
The rate equation for this reaction is
Rate = k [BrO 3 ] [Br ] [H+] m
where k is the rate constant with units of mol3 dm9 min1.
What is the value of y in experiment 2?
A 0.02 B 0.04 C 0.16 D 0.32
15 Covalent chlorides like SiCl 4 and PCl 3 undergo hydrolysis to give an acidic solution. Formatted: Not Highlight
Formatted: Not Highlight
Which of the following chlorides is not expected to undergo hydrolysis?
A CCl 4 B GeCl 4 C AsCl 3 D SbCl 3 Formatted: Not Highlight

16 Which of the following is not a result of the high charge density of Al3+?
A AlCl 3 has a tendency to form Al 2 Cl 6 . Formatted: Not Highlight

B A solution of AlCl 3 has a lower pH than MgCl 2 .
C Al 2 O 3 is an amphoteric oxide. Formatted: Not Highlight
D Al(OH) 3 has a lower decomposition temperature than Ca(OH) 2 . Formatted: Not Highlight
17 Lime mortar is made from quicklime, water and sand. Over a period of time, lime mortar
changes into a much harder form. Both fresh and old lime mortar react with aqueous
hydrochloric acid but only the old lime mortar effervesces during the reaction.
Which equation describes the change from fresh to old lime mortar?
A CaO + CO 2 CaCO 3
B CaO + H 2 O Ca(OH) 2 Formatted: Not Highlight
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C Ca(OH) 2 CaO + H 2 O
D Ca(OH) 2 + CO
O 2 CaCO 3 + H 2 O
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AMINAT /201
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18 A sodium halide evolved thick white fumes when reacted with phosphoric acid. The white
fumes was then passed through AgNO 3 (aq) which gives a precipitate insoluble in
concentrated NH 3 .
What is the role of phosphoric acid in the reaction and the identity of the sodium halide?
Role of phosphoric acid Identity of sodium halide

A Acid Sodium bromide
B Acid Sodium iodide Formatted: Not Highlight
C Oxidising agent Sodium bromide

D Oxidising agent Sodium iodide
191 Which of the following is not a result of the small energy gap between 3d and 4s orbitals? Formatted: Not Highlight
A Transition metals have higher electrical conductivity than aluminium.

B Transition metals can exhibit variable oxidation states.
C Transition metals have higher melting point than calcium.
D Transition metals ions are usually coloured. Formatted: Not Highlight
20 Which compound cannot be readily prepared from 4-nitromethylbenzene?
A CH3 B CCl3 C COOH D CH3 Formatted: Not Highlight
Br
NH2 NO2 NO2 NO2
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21 Benzaldehye is the simplest aromatic aldehyde and one of the most industrially useful.
CHO
Benzaldehyde
Which of the following is true about the electrophilic reaction of benzaldehye?
A AlCl 3 (aq) can be used as a catalyst in its reaction with Cl 2 .

B It reacts with concentrated HNO 3 in the presence of concentrated H 2 SO 4 at 30 oC.
C A halogen carrier, FeCl 3 , can be used as a catalyst in its reaction with Br 2 . Formatted: Not Highlight
D It is more reactive towards Br 2 than alkene as it has delocalised electrons and is more
electron-rich.
22 Which of the following compounds, in its reaction with NaCN, is the least likely to form a
carbocation as an intermediate?
A C(CH 3 ) 3 Br
B CH 3 CHBrCH 2 CH 3
C CH 3 CH 2 CH 2 CH 2 Br Formatted: Not Highlight
D
CH2Br
23 1-bromopropane is converted to 2-bromopropane by a two-step process involving the
intermediate T.
step 1 step 2
CH 3 CH 2 CH 2 Br T CH 3 CHBrCH 3
What could be the reagent for step 1 and for step 2 to get the highest yield of
2-bromopropane?
step 1 step 2
A Concentrated H 2 SO 4 , heat SOBr 2 , heat
B NaOH(aq), heat HBr(aq)
C NaOH in ethanol, heat HBr(g) Formatted: Not Highlight
D NaCN in ethanol, heat PBr 3 , heat
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24 A solid compound Z dissolved readily in water to give a weakly alkaline solution.
On evaporation of the water, Z was recovered unchanged.
What could Z be?
A CH 3 NH 3 +Cl B CCl 3 CO 2 Na+ C C 6 H 5 O Na+ D H 2 NCH 2 CO 2 H Formatted: Not Highlight

I think I made a typo, was thinking of friedal crafts and testing them on the directing effect
of CH 3 and NO 2 .
252 N-Methyl-D-aspartic acid is a neuroprotective agent which is used in the treatment of
strokes, trauma and epilepsy. Its structure is shown below.
CO2H
CH2
CH3NHCHCO2H
Which of the following statements is correct?
A r solutionIt exists as an anion at pH 7.exists as an anion at pH 7. Formatted: Not Highlight

Formatted: Strikethrough, Not
B It reacts with phenol to form an ester. Highlight
C It cannot form intramolecular hydrogen bonding. Formatted: Not Highlight
D One mole of N-Methyl-D-aspartic acid reacts with Na metal to give two moles of H 2
gas.
26 Which of the following reagents is able to convert compound Q to compound R?
CH3CHBrCH(OH)COOH CH3CHBrCH(Br)COOH
Compound Q Compound R
A PBr 3 B HBr C SOBr 2 D NaBr Formatted: Not Highlight

Qn 7 was the original qn 2, I changed the option (a) so that it will not overlap with the pka
question. But I feel that the 2 assessment objectives are rather different. The original option
of it exists as an anion at pH 7 is to let them recognise the low pka values of the COOH and
high pKa value of NH 3 + (this was asked in N2014 P3). While the pka values require them to
assign pKa value to get the correct species at a certain pH.
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This question students have to think of S N 1 mechanism, so they would narrow it down to
option C and D. as there is only one answer, they have to compare the stability of the
carbocation and eliminate D
27 Which reagent will convert compound G to compound E efficiently?
O CN HO CN Formatted: Centered
Cl Cl
O O O O
Compound G Compound E
A H 2 /Ni B H 2 O/H+ C LiAlH 4 D NaBH 4 Formatted: Not Highlight

3 Amides and esters both undergo hydrolysis, however esters are more reactive towards
hydrolysis compared to amides. Formatted: Not Highlight
When comparing CH 3 COOCH 3 and CH 3 CONHCH 3 , which factor best contributes to this
difference in ease of hydrolysis?
A A lone pair of electrons on the nitrogen in NHCH 3 , is more readily delocalised into the
>C=O group than is the corresponding pair on the oxygen, OCH 3
B The nitrogen atom in CH 3 CONHCH 3 is less electronegative than the OCH 3 group in
CH 3 CO 2 CH 3.
C There is greater positive charge on the carbon atom in the >C=O group in
CH 3 CONHCH 3 .
D CH 3 COOCH 3 has a lower energy content than CH 3 CONHCH 3 .
28 A student added aqueous silver nitrate into test tubes containing compounds W, X, Y and Z.
The following observations were obtained.
Compound Observation
W precipitate formed immediately
X precipitate formed after 5 minutes
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Y precipitate formed after 10 minutes
Z no precipitate
cipitat formed

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What could be the identities of compounds W, X, Y and Z?
W X Y Z
A CH 3 COCl CH 3 CH 2 Cl CH 3 CH 2 Br C 6 H 5 Br
B CH 3 COCl CH 3 CH 2 Br CH 3 CH 2 Cl C 6 H 5 Br Formatted: Not Highlight
C CH 3 CH 2 Br CH 3 COCl C 6 H 5 Br CH 3 CH 2 Cl
D CH 3 CH 2 Br C 6 H 5 Br CH 3 COCl CH 3 CH 2 Cl Formatted: Not Highlight
29 Chlorogenic acid occurs naturally in both coffee and an edible species of bamboo.
O
HO Formatted: Not Highlight
OH Formatted: Not Highlight
O Formatted: Not Highlight

HO O
OH
OH
Chlorogenic acid OH
Which statement about chlorogenic acid is not correct? Formatted: Font: Bold
A It reacts with 4 mol of NaOH when heated with NaOH(aq). Formatted: Not Highlight
B It gives CO 2 (g) when heated with acidified potassium manganiate (VII). Formatted: Not Highlight
C It reacts with Br 2 (aq) to incorporate up to 5 atoms of bromine in each molecule.
D It reacts with a heated acidified solution of potassium dichromate (VI) to give a product
with 112 sp2 carbons.
Formatted: Font: (Default) Times
5 Non covalent chlorides like SiCl 4 and PCl 3 undergo hydrolysis to give an acidic solution. New Roman, Not Highlight
Which of the following chlorides is not expected to undergo hydrolysis? Formatted: Not Highlight
A CCl 4 B GeCl 4 C AsCl 3 D SbCl 3
6 Which compound cannot be prepared directly from 4-nitromethylbenzene?
A CH3 B CH3 O C COOH D CH3
C
New Roman, Not Highlight
Cl
Br Formatted: Not Highlight
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NH2 NO2 NO2
NO2

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7 Which reagent will convert compound G to compound E efficiently.

O CN HO CN
Cl Cl
O O O O
Compound G Compound E
+
A H 2 /Ni B H 2 O/H C NaBH 4 D LiAlH 4
8 A sodium halide was reacted with phosphoric acid which evolves thick white fumes. The
white fumes was then passed through AgNO 3 (aq) which gives a precipitate insoluble in
concentrated NH 3 .
What is the role of phosphoric acid in the reaction and the identity of the sodium halide?
Role of phosphoric acid Identity of sodium halide
A Acid Sodium bromide
B Acid Sodium iodide
C Oxidising agent Sodium bromide
D Oxidising agent Sodium iodide
9 When heated with bromine, the hydrocarbon 3-methylpropane undergoes free radical
substitution. In a propagation step, the free radical X is formed by the loss of one hydrogen
atom.
CH3
CH3CH2CHCH2CH3 + Cl X + HCl
Which X formed is the most stable?

A B
CH3 CH3
CH2CH2CHCH2CH3 CH3CHCHCH2CH3
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C D
CH3 CH2
CH3CH2CCH2CH3 CH3CH2CHCH2CH3
10 Histidine, an essential amino acid, is present in many proteins and enzymes and plays a vital
role in the structure and oxygen-binding function of haemoglobin.
Similar to Q2
O
Remove Q2
N
OH
NH2
HN
histidine
Histidine has pKa values of 1.8, 6.0 and 9.2.
What is the structure of the major species in a solution of histidine at pH 7?
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A B

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COOH COO
+ +
H3N H3N
+ +
HN HN
NH NH
C D
COO COO
+
H3N H2N
N N
NH NH
11 1-bromopropane is converted to 2-bromopropane by a two-step process involving the

intermediate T.
step 1 step 2
CH 3 CH 2 CH 2 Br T CH 3 CHBrCH 3
What could be the reagent for step 1 and for step 2 to get the highest yield of 2-
bromopropane?
step 1 step 2
A Concentrated H 2 SO 4 , heat SOBr 2 , heat
B NaOH(aq), heat HBr(aq)
C NaOH in ethanol, heat HBr(g)
D NaCN in ethanol, heat PBr 3 , heat
302 The structure of 1-acetylpiperidine is shown below.
N C CH3
-
1 acetylpiperidine
Which pair of compounds would produce 1-acetylpiperidine when reacted together?
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A
N H + CH3COOH
B Formatted: Not Highlight

N H + CH3COCl Formatted: Not Highlight
C
N COOH + CH3OH
D
N COCl + CH3OH
13 A student added aqueous lead(II) nitrate into test tubes containing compounds W, X, Y and
Z. The and obtained the following observations were obtained.
Compound Observation
W White precipitate formed immediately
X White precipitate formed after 5 minutes
Y White precipitate formed after 10 minutes
Z No precipitate formed
What could be the identity of Compounds compounds W, X, Y and Z?

W X Y Z
A CH 3 COCl CH 3 CH 2 Cl CH 3 CH 2 Br C 6 H 5 Br
B CH 3 COCl CH 3 CH 2 Br CH 3 CH 2 Cl C 6 H 5 Br
C CH 3 CH 2 Br CH 3 COCl C 6 H 5 Br CH 3 CH 2 Cl
D CH 3 CH 2 Br C 6 H 5 Br CH 3 COCl CH 3 CH 2 Cl
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Section B
be correct.
A B C D
1, 2 and 3 1 and 2 2 and 3 1 only
31 Consider the reaction below:
2H+(aq) + 2NO 2 (aq) H 2 O(l) + NO(g) + NO 2 (g)
Which statements correctly describe the process?
1 The bond angle in NO 2 ion is larger than that in H 2 O.

2 This is a disproportionation reaction.
3 H+(aq) is oxidised by NO 2 (aq).
32 The boiling points of six consecutive elements, lettered T to Y, are given in the table below.
(Note: these letters are not the atomic symbols of the elements concerned.)
Element T U V W X Y
Atomic Number z z+1 z+2 z+3 z+4 z+5
Boiling Point / K 73 93 83 23 1163 1373
Which of the following statements are true?
1 Only X and Y have giant structures.

2 The atomic radius of W is smaller than that of X.
3 First ionisation energy of T is higher than that of U.
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33 The value of pV is plotted against p for 2 gases, A and B, where p is the pressure
and V is the volume of the gas.
pV
Which of the following could be the identities of the gases?
gas A gas B
1 0.5 mol of CH 4 at 25 C 0.5 mol of CH 4 at 50 C
2 0.5 mol of NH 3 at 25 C 1.0 mol of CH 4 at 25 C
3 0.5 mol of NH 3 at 25 C 0.5 mol of NH 3 at 323 C
34 The diagram shows apparatus that can be used to measure the E of a half-cell.
hydrogen Ga
H2SO4(aq)
gallium chloride
solution
platinum foil coated with
finely divided platinum
Which factors are essential for an accurate measurement of E for the following electrode
system?
Ga3+ + 3e Ga
1 The H 2 SO 4 (aq) should be at a concentration of 0.5 mol dm3.

2 The Ga3+(aq) and Cl (aq) should each be at a concentration of 1.0 mol dm3.
3 The hydrogen should be dry.
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A B C D
1, 2 and 3 1 and 2 2 and 3 1 only
35 Aqueous CuCl 2 undergoes the following reactions:
Step 1 Step 2 Cu(NH3)4(H2O)22+ Formatted: Font: Not Bold

CuCl2(aq) Cu(OH)2
Formatted: Font: Not Bold
Pale blue solution dilute ammonia pale blue pptexcess dilute deep blue solution
ammonia Formatted: Centered
Formatted: Font: Not Bold
Conc HCl Formatted: Font: Not Bold
A
CuCl4 CuCl2(a)
Yellow-green solutuion
1 CuCl 4 2 is a more stable complex than Cu(NH 3 ) 4 (H 2 O) 2 2+. Formatted: Not Highlight
2 2+ Formatted: Font: (Default) Times

2 CuCl 4 , Cu(NH 3 ) 4 (H 2 O) 2 and CuCl 2 (aq) have different colours due to the different New Roman, Not Highlight
ligands present. Ammonia acts as base to give a source of OH in step 1.
3 Ligand exchange takes place in step 2 as NH 3 is a stronger ligand than H 2 O. Formatted: Not Highlight
32 The halogens are oxidising agents which oxidises sodium thiosulfate, Na 2 S 2 O 3. Which of the Formatted: Not Highlight
following statements is true regarding the halogenthiosulfate reaction? Formatted: Not Highlight
1 The oxidising power of the halogens decreases down the group Formatted: Not Highlight
2 When Iodine is the oxidising agent, the average oxidation state of S changes from +2 to
+2.5 after the reaction. Formatted: Not Highlight
3 When bromine is the oxidising agent, one of the products gives a white precipitate with
Ba(NO 3 ) 2.
Potential question to replace question on which is true about alpha amino acid.
New Roman, Not Highlight
3631 Consider the following reaction scheme. Formatted: Subscript
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OH O OCH3 OCH3
CH3Br NH2NH2
Na
CHO CHO CHO HC N NH2
Which of the following type of reactions is involved in the reaction scheme.?
1 Acid base reaction

2 Condensation Formatted: Not Highlight
3 Nucleophilic substitution Formatted: Not Highlight
32 Chlorogenic acid occurs naturally in coffee and an edible species of bamboo.

O
HO
OH
O
HO O
O
H OH
Chlorogenic acid OH
Which reaction will ajulmeic acid undergo?
1 It reacts with 4 mol of NaOH(aq) when heated with NaOH(aq).
2 It reacts with Br 2 (aq) to incorporate up to 5 atoms of bromine in each molecule.
3 It will turn a heated acidified solution of potassium dichromate (VI) from orange to
green.
3743 Chlorofluorocarbons (CFCs) have been widely used in aerosol sprays, refrigerators and in
making foamed plastics, but are now known to destroy ozone in the upper atmosphere.

What will not destroy ozone, and therefore can be used as a replacement for CFCs?
1 CH 2 FCH 2 F
2 CH 3 CH 2 CH 3 Formatted: Not Highlight
3 CHBr 3 Formatted: Not Highlight
34 Which of the following is true about an -amino acid?
t e
1 It is amphoteric.. Formatted: Not Highlight
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20 Formatted ...
Formatted ...
2 It is soluble in water.
Formatted ...
3 It always exists as a zwitterion at pH 7.
Formatted ...
Formatted ...
Formatted ...
3855 Which aspect of the protein structure will be affected by strong acids at room temperature? Formatted ...
Formatted ...
1 Tertiary structure Formatted ...

Formatted ...
2 Secondary Structure
Formatted ...
3 Primary Structure Formatted ...
Formatted ...
OR Formatted ...
394 Which compounds will react to produce CH 3 CCH 2 HCH 2 CH 2 OH in good yield? Formatted ...
Formatted ...
Formatted ...
1 CH 3 CCH 2 HCH 2 OCOCH 2 CH 3 + NaOH(aq) with heat
Formatted ...
2 CH 3 CH=CH 2 + concentrated H 2 SO 4 followed by steam CH 3 COOH + D 2 , Ni with heat Formatted ...
3 CH 3 CH 2 COOH + H 2 , Ni with heat CH 3 CH=CH 2 + D 2 O with H+ Formatted ...
Formatted ...
Formatted ...
Formatted ...
40 Most of the chemistry of magnesium relates to its ionic compounds. However, magnesium
6 does form an important group of covalent compounds known as Grignard reagents. Formatted ...
Formatted ...
A typical example of the use of a Grignard reagent is the two-step reaction of C 2 H 5 MgBr Formatted ...
RMgBr with carbonyl compounds like propanone to form RC(CH 3 ) 2 (OH), CH 3 COCH 3 , to form Formatted ...
2-methylbutan-2-ol.
Formatted ...
Formatted ...
You may take R to represent an alkyl group.
Formatted ...
Formatted ...
OMgBr OH
Formatted ...
Step 1 Step 2
RMgBr + CH3COCH3 H3C C CH3 H3C C CH3 + Mg(OH)Br Formatted ...
H2O Formatted ...
R R Formatted ...
Formatted ...
Which of the following compounds could be the product of a Grignard reagent reacting with Formatted ...
an aldehyde?
Formatted ...
Formatted ...
1 CH 3 CH(OH)CH 3 Formatted ...
2 CH 3 CH(CH 3 )CH(OH)CH 3 Formatted ...
3 CH 3 CH 2 C(OH)(CH 3 )CH 2 CH 3 Formatted ...
Formatted ...
This is a pattern recognition question
Formatted ...
Formatted ...
Formatted ...
Formatted ...
Formatted ...
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Formatted ...
Formatted ...
Formatted ...
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BLANK PAGE

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Answer Key to 2016Jurong Junior College H2 Chemistry Prelim Exam Paper 1
1 A 11 D 21 C 31 B
2 D 12 D 22 C 32 A
3 B 13 D 23 C 33 C
4 C 14 B 24 C 34 D
5 C 15 A 25 A 35 C
6 B 16 A 26 B 36 C
7 A 17 D 27 D 37 B
8 A 18 B 28 B 38 D
9 A 19 D 29 D 39 D
10 C 20 D 30 B 40 B
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2016 H2 Chemistry Prelim Exam Paper 2 Suggested Mark Schemes
1 (a) CH 3 COCH 3 + I 2 CH 3 COCH 2 I + HI [1]
(b)
1. Using a 50.00 cm3burette, run **50.00 cm3 of the 5.0
moldm3propanone solution into a *250 cm3 [1]prepn of 1.0 mol
-
volumetric/standard flask. Make up to the graduated dm
3
propanonesoution
mark with deionised water. Stopper and shake the flask to
obtain a homogeneous solution.
*any appropriate capacity e.g. 100 cm3, 150 cm3

**calculated volume based on chosen capacity of standard
flask
2. Using a 50 cm3 measuring cylinder/burette, add 50.0 cm3

[1]prepn of
of the diluted propanone solution prepared in step 1 into a solution Y
200 cm3 beaker.
Using another 50 cm3 measuring cylinder/burette, add
50.0 cm3 of1.0 mol dm dilute sulfuric acid into the
same beaker. Stir well and label the solution Y.
[1]prepare X and Y
3. Using a 10 cm3 measuring cylinder/pipette/burette, add in separate boiling
10.0 cm3of solution Y into a boiling tube (labelled Y). tubes
Using another 10 cm3 measuring cylinder/pipette/burette,
add 10.0 cm3 of solution X to a second boiling tube
(labelled X). [1]place X and Y in
water bath set at a
particular temp.
4. Place both boiling tubes X and Y in the water bath
maintained at 15 C which is prepared by mixing tap water
and ice water. [1]Mixing and
Place a 0.2 oC interval thermometer inside tubeX record both t
and leave both tubes inside the water bath for some & temp. of mixture
timeto allow both solutions in the boiling tubes to equilibrate.
5. Then quickly add solution Y from boiling tube Y to boiling [1]state 4 other
tube X, starting the stopwatch simultaneously. Stir well temps
o
with the thermometer. Record the time taken for the < 50 C
reaction mixture to completely decolourise and and state how the
the temperature of the reaction mixture. temp.of both warm
& cool water-
bathscan be
6. Repeat the experiment (steps 3-5) at 4 other different achieved
temperatures, *20 oC, 25 oC, 30 oC and 35oC.
For temperature above room temp., prepare the water
bath by mixing tap water and hot water.
For temperature below room temp., prepare the water
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d
bath by mixing tap water and ice
ic water
water..
Use a thermometer to monitor the temperature of the wate
water-
water
bath.
*One of the chosen temp. should be below 25 oC.

e be
562 trendyline
2
(c) As propanone is flammable, do not use direct/naked flame

from Bunsen burner for heating. Use hot water to prepare the [1]
water bath.
1 (d) (i) 1

k [1]
t
(ii) 1 E 1
ln = ln A a
t R T
1 1
By plotting ln against graph, astraight line graph
t T
( [1]
with gradient of D is obtained.
5
(e) Since therate is independent of [I 2 ], [1]

when [I 2 ] is halved, t is halved. [1]
[Total: 12]
2 (a) (i) K sp = [Ag+]2 [CrO 4 2][1]units:mol3 dm9[1]
(ii) 1.1 x 1012 = 4x 3

x = 6.50 x 105mol dm-3 [1]
Solubility of Ag 2 CrO 4 in g dm3 = 6.50 x 105 332 = 0.0216 [1]
(iii) [Ag+]2 [CrO 4 2] [Ba2+][CrO 4 2]

2
8.0 10 5 2.0 10 4 8.0 10 5 2.0 10 4
= =
2 2 2 2
= 1.60 x 1013<K sp (Ag 2 CrO 4 )[1] =4.00 x 109>K sp (BaCrO 4 )[1]
yellow ppt. of BaCrO 4 is observed. [1]
(b) Precipitation of BaCrO 4 [1]reduces [CrO 4 2] and causes

the equilibrium position to shiftto the right. [1]
Therefore, [H+] increases and hence pHof the solution decreases. [1]
(c) E cell = 0.41 (0.76) = +0.35 V > 0
ttrendyline
trend
r d
Equation: Z + 2Cr3+ 2Cr2++ Zn2+
n: Zn [1]
Hence Zn reduces green Cr3+(aq) to blue Cr2+(aq)
(aq).. [1]
E cell = 0.00 (0.41) = +

00 (0.41) +0.
+0.41
41
1V>0 [1]
2+ + 3+
Equation: n: 2Cr + 2H 2Cr + H 2 [1]
Hence, on standing, the H+ present in the solution oxidises blue
Cr2+(aq) back to green Cr3+(aq) and H 2 gas is produced.
Jurong Junior College 9647/02/J2 PRELIMINARY EXAMINATION/2016
563 trendyline
3
[Total: 14]
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Jurong Junior College 9647/02/J2 PRELIMINARY EXAMINATION/2016 [Turn over
564 trendyline
4
3 (a) Due to smaller size of Li+, Li+ has higher charge density.
Li+ polarises the large O 2 2 anion to a large extent, hence it forms [1]
Li 2 O instead of Li 2 O 2 .
(b) (i) X:P 4 O 6 Y:SiO 2 Z:MgO [1]
(ii) SiO 2 has giant molecular structure. Due to the strong covalent
bond between Si and O atoms throughout the whole giant
[1]
structure, it does not hydrolyse in water.
(iii) P 4 O 6 + 6H 2 O 4H 3 PO 3 [1]
MgO+ H 2 O Mg(OH) 2 Accept [1]
(iv) SiO 2 + 2OHSiO 3 2+ H 2 O [1]

P 4 O 6 + 8OH4HPO 3 2 + 2H 2 O [1]
(c) (i) H sol (Ca(OH) 2 ) = (2506) + (1579) + 2(460)

=+7 kJ mol1 [1]
(ii)
Hr
Ca(s) + 2H 2 O(l) Ca(OH) 2 (aq) + H 2 (g)
2(286) (+7) [1]
987)
(
Ca(s) + 2H 2 (g) + O 2 (g) Ca(OH) 2 (s) + H 2 (g)
By Hess Law,
H r = 2(286) + (987) + (+7) = -408 kJ mol1 [1]
(e.c.f. from ans(c)(i))
[Total: 10]

565 trendyline
5
4 (a)
[NO] / moldm3
0.14
0.12
0.1
0.08
0.06
0.04
0.03
0.02
(t1/2)1 = 5 (t1/2)2 = 5
0
0 2 4 6 8 10 12 14 16
5
(i) t = 5 min
(t ) 1 = 5 min, (t ) 2 = 5 min [1]
Sincehalf-lives are constant, the reaction isfirst orderwith [1]

respect to NO.
(ii) Let rate = k [NO][F 2 ]a

1
Since rate ,
t [1]

D

D

a = 1

Hence, order of reaction with respect to F 2 is1. [1]
(iii) rate = k[NO][F 2 ] [1]
(iv) Step 1: NO + F 2 ONF + F slow step [1]

Step 2: F + NO ONF [1]
(b) (i)

O O
N O O
C

[1]
[1]
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yi

(ii) Thepermanent
hepermanent
he ermanent dipole-permanent
dipole-permanent dipole attraction between
dipole-
NO
O 2 molecules is stronger than
han the van der Waa
Waals forces [1]
between
etween CO 2 molecules.
[Total: 10]

566 trendyline
6
5 (a) (i) Tertiary alcohol [1]
(ii) H H
H H H H
H H C H H H C H
H C CCC H H C CCC H
H H Br H H H O H
H
[1] [1]
A B
(iii) Initiating: H
uv
Br Br 2Br( 1 )
Propagating step:
(2)

CH 3 CH 2 CH(CH 3 ) 2 + Br CH 3 CH 2 C(CH 3 ) 2 + HBr( 3 )

CH 3 CH 2 C(CH 3 ) 2 + Br 2 CH 3 CH 2 C(CH 3 ) 2 + Br( 4 )
Br
Termination ste:
Br+ BrBr 2

CH 3 CH 2 C(CH 3 ) 2 + Br CH 3 CH 2 C(CH 3 ) 2
( 5 ) Br
( 6 )

CH 3 CH 2 C(CH 3 ) 2 + CH 3 CH 2 C(CH 3 ) 2 CH 3 CH 2 C(CH 3 ) 2
CH 3 CH 2 C(CH 3 ) 2
6 (
) [3]
45 () [2]
23 () [1]
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7
5 (b) (i) alkaline aqueous iodine

[1]
CH 3 C=O and CH 3 CH(OH) groups
Ketones and aldehydes [1]
(ii) O CH 2 =CHCH 2 CH=C CH=CH 2

CH 3 C
CH 3
COOH
or
CH 2 =CHCH 2 CH=C C=CH 2
E [1] H CH 3
[1]
D
(c) (i)
Step 1:
-
Br CH 3 CH 2
+
CH 3 CH 2 C CH 2 CH 2 CH 3 C + 2 CH 2 CH 3 + :Br
CH [1]
CH 3 CH 3
Step 2:
CH 3 CH 2 H CH 3 CH 2 CH 2 CH 3

+C CCH 2 CH 3 +
OCH 2 CH 3 C C + CH 3 CH 2 OH [1]
CH 3 H CH 3 H
(ii)
CH 2 =C CH 2 CH 2 CH 3 CH 3 CH=C CH 2 CH 2 CH 3
CH 2 CH 3 CH 3
[1] [1]
(iii) OCH 2 CH 3
CH 3 CH 2 C CH 2 CH 2 CH 3
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y
CH 3
[1
[1]
F
Type off reaction:

ti Nucleophilic
ucleophilic substitution [1
[1]

568 trendyline
8
5 (c) (iv) CH 2 NH 2
H 3 C C CH=CHBr
CH 3
H [1]
The p orbital of Br atom overlaps with the p orbital of carbon

atom of C=C double bond, forming partial double bond [1]
character in the CBr bond, thereby strengthening the CBr
bond.
[Total: 18]
6 (a) (i) POCl 3 and the acyl chloride group inchloroacetyl chloride can [1]
undergo hydrolysisif water is present.
(ii) Excess CH 3 NH 2 in ethanol, heat in sealed tube [1]
(iii) Reduction [1]
(b) Twoelectrondonating alkyl groups bonded to N atom in

epinephrine, as compared to only one alkyl group bonded to N atom in [1]
cordabrine, make the lone pair on N in epinephrine more available for
protonation.
So epinephrine is expected to be the stronger base. [1]
(c) O HO O
OH CH3OH
+
NH3 H3N
+
HO O
[1] for each correct hydrolysed product
[Total: 8]
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569 trendyline
JURONG JUNIOR COLLEGE
2016 JC 2PRELIMINARY EXAMINATION
Higher 2
CANDIDATE
NAME
CLASS 16S
CHEMISTRY 9647/03
Paper 3Free Response 14 September 2016
2 hours

Data Booklet
Write your name, class and exam index number on all the work you hand in.
You may use anHB pencil for any diagrams or graphs.

trendyline
This document consists of 9 printed pages and 1blank page.
570 [Turn over

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2
1 Methane, the main component of natural gas, is converted into a combustible mixture of
gases by reaction with steam in the presence of a heated nickel catalyst.
CO(g) + 3H 2 (g)
reaction 1: CH 4 (g) + H 2 O(g)
(a) (i) The total bond energy in the carbon monoxide molecule is 1046 kJ mol1.
Suggest why this value is higher than either of the bond energies between
carbon and oxygen found in the Data Booklet. [1]
(ii) Using the given bond energy value for the carbon monoxide molecule and
other relevant data from the Data Booklet, calculate the enthalpy change of
reaction for reaction 1. [2]
(b) The standard Gibbs free energy change of a reaction can be calculated based on
its standard enthalpy as well as its standard entropy change.
(i) The G for the forward reaction in reaction 1 is +142 kJ mol1.

Using the given value for G and your answer in (a)(ii), calculateS for the
forward reaction in reaction 1 at 25 C. [2]
(ii) Calculate the temperature at which the reaction just becomes feasible. [1]
(c) When a 2:1 mole ratio of methane and steam at aninitialtotal pressure of 5atm is
passed over the catalyst at 450 C, the partial pressure of hydrogen at equilibrium
is found to be 1.8 atm.
(i) Calculate the partial pressures of methane, steam and carbon monoxide at
equilibrium. [1]
(ii) Write an expression for the equilibrium constant, K p , and calculate its value,
giving its units. [2]
(iii) Calculate the percentage yield of hydrogen gas at equilibrium under the
above given conditions. [1]
(iv) Suggest what conditions of temperature and pressure would increase the
yield of hydrogen gas. Explain your answer in each case. [3]
(d) The hydrogen gas from reaction 1 can be harnessed and used as a fuel in fuel
cells. Oxygen from air is pumped into the fuel cell at the cathode. An alkali such
as warm aqueous potassium hydroxide can be used as an electrolyte.
(i) Write the halfequations of the reactions which would take place at the
anode and the cathode of such a fuel cell. [2]
(ii) Using relevant E values from the Data Booklet, calculate the standard cell
potential of the above fuel cell. [1]
(iii) One refinement of the fuel cell design is to replace the alkaline electrolyte
solution with a film of solid OH ion-conducting polymer.
riefly
iefly explain why this would be an improvement.
Briefly improvem [1]
Jurong Junior College 9647/03/J2 PREIMINARY EXAMINATION/2016

571 trendyline
3
1 (e) The carbon monoxide attained from reaction 1is also useful for the production of
aromatic aldehydes from various aromatic compounds, including derivatives of
benzene.
One such example is the GattermannKoch reaction, in which carbon monoxide,

hydrochloric acid, and aluminium chloride are used to react with benzene to
produce benzaldehyde.
CO + HCl + AlCl3
O
Gattermann-Koch reaction
Using the Gattermann-Koch reaction as the first step of the synthesis, show how
compound Gcan be formed from methylbenzene in a three-step synthesis.
You should suggest the reagents and conditions to be used for the second and
third steps and identify the intermediates involved.
CH3 CH3
HO C COOH
CompoundG [3]
[Total: 20]
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Jurong Junior College 9647/03/J2 PREIMINARY EXAMINATION/2016 [Turn over
572 trendyline
4
2 (a) By passing dry chlorine over aluminium metal, aluminium chloride, AlCl 3 ,
a yellow-white solid that sublimes at low temperatures, can be prepared.
(i) Other than the formation of the yellow-white solid, describe another
observation that you can make between the reaction of aluminium and
chlorine. [1]
(ii) Describe and explain what you would see when a sample of solid AlCl 3 is
added to a solution of litmus in water.
Include relevantequation(s) in your answer. [3]
(iii) When NaOH(aq) is added dropwise to the resulting solution formed in

(a)(ii), a white precipitate forms, which is soluble on adding excess
NaOH(aq).
With the aid of suitable equations with state symbols, explain these
observations. [3]
(b) AlCl 3 is used to catalyse electrophilic substitution reactions such as the

chlorination of benzene.
Chlorination of benzene takes place in several steps.
Cl 2 + AlCl 3 Cl+ + AlCl 4
The benzene ring is then attacked by the Cl+ cation in the second step.
Alkylation of benzene can also be catalysed by AlCl 3 in a similar way.

When benzene and propene react together in the presence of AlCl 3 and HCl,
cumene is formed in a high yield.
CH3
AlCl3
+ CH3CH=CH2 C CH3
HCl
propene H
cumene
(i) By considering the structure of cumene, write a balanced equation showing

the formation of the carbocation obtained from the reaction of CH 3 CH=CH 2 ,
AlCl 3 and HCl. [1]
(ii) Hence, using the above information provided, describe the mechanism for
the reaction between the carbocation and benzene to give
cumene. In your answer, show relevant charges and use curly arrows to
show the movements of electron pairs. [2]
(iii) In the above reaction between benzene and propene, propylbenzene is

obtained in small quantities. Suggest a reason for this.
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nd
dy
y CH2CH
C 2CH3
propylbenzene
ropy [1]

573 trendyline
5
2 (b) (iv) When cumene is treated with a small quantity of bromine in the presence of
ultraviolet light, only two monobrominated compounds can be formed.
Suggest the structure of an isomer of cumene that will also give only two
monobrominated products under the same reaction conditions.
Assume no bromination takes place on the benzene ring. [1]
(v) Describe a simple chemical test to distinguish the isomer drawn in (b)(iv)
from cumene. [2]
(c) Phosphorus and sulfur are in the same Period as aluminium. In addition to
forming halides like aluminium, both phosphorus and sulfur form oxyhalides that
are commonly used as chlorinating agents in organic syntheses. These include
POCl 3 and SOCl 2 .
(i) Draw the shape for the SOCl 2 molecule. [1]
(ii) POCl 3 boils at 106 C while SOCl 2 boils at 75 C.

Account for the difference in boiling points between the two oxyhalides. [2]
(d) Phosphoric(V) acid, H 3 PO 4 , is one of the most well-known triprotic acids.

Apart from phosphoric(V) acid, there exists other phosphorus-containing acids
that dissociate to give more than three protons per molecule. One such acid is W,
which can be formed when H 3 PO 4 reacts with POCl 3 . HCl gasis also produced
during the reaction.
W has the following composition by mass: P, 34.8%; O: 62.9%; H, 2.3%.
(i) Calculate the empirical formula of W. [1]
(ii) Given that the empirical formula of W is the same as its molecular formula
and that the constituent atoms in W show their usual valencies, suggest the
structure of molecule W. [1]
(iii) Write an equation for the reaction between H 3 PO 4 and POCl 3 . [1]
[Total: 20]
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6
3 Thermogravimetry is an analytical method used to determine the composition of solids

which decompose on heating. The change in mass which is measured during the
heating process provides information about the composition of the mixture analysed.
A mixture of calcium oxalate, CaC 2 O 4 , and magnesium oxalate, MgC 2 O 4 , was heated
up to 900 C. During this process, the mass of the mixture was measured continuously.
It is known that the following two decomposition reactions take place at around 400 C.
MgC 2 O 4 (s) MgO(s) + CO(g) + CO 2 (g)
CaC 2 O 4 (s) CaCO 3 (s) + CO(g)
At 700 C, a third decomposition with the evolution of an acidic gas is observed.
(a) (i) Write an equation to illustrate the third decomposition reaction. [1]
(ii) At 500 C, the mass of the mixture obtained was 3.06 g.

At 900 C, the mass of the mixture obtained was 2.03 g.
moles of MgC2O4
Calculate the ratio prior to heating.
moles of CaC2O 4 [3]
(b) Other than bonding with Group II metal ions, the oxalate ion, C 2 O 4 2, is known to
act as a bidentate ligand to transition metal ions to form complex ions.
An example is the light green Fe(C 2 O 4 ) 3 3 complex ion.
The structure of the oxalate ion is as follows.
O O
O O
(i) What do you understand by the term, ligand? [1]
(ii) State the oxidation number of iron in Fe(C 2 O 4 ) 3 3. [1]
(iii) Draw the structure of the Fe(C 2 O 4 ) 3 3complex ion, showing the geometry
around Fe. [2]
(iv) Briefly explain how the light green colour of Fe(C 2 O 4 ) 3 3 arises. [3]
(v) Explain why iron forms complex ions while calcium does not. [1]
(c) Compound K has the molecular formula, C 4 H 7 NO 2 . When compound K was

warmed with aqueous sodium hydroxide, a colourless pungent gas was evolved.
Acidification of the resulting solution gives compound L, C 4 H 6 O 3 .
L gives an orange precipitate with 2,4-dinitrophenylhydrazine but has no reaction
with Fehlingssolution. Effervescence was observed when L was treated with
aqueous sodium hydrogencarbonate. When lithium aluminium hydride was added
to L, compound M, C 4 H 10 O 2 , was produced.
M can also be obtained from the reaction of coldacidified potassium
ate(VII) with compound N, C 4 H 8 .
manganate(
na
Deducee the structures of compounds K,
K, L,, M and
nd N and explain the reactions
ed
ed.
described.
[8]
[Total: 20]

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7
4 This question concerns chemical reactions of halogens, halides and the organic
derivatives of halogens.
(a) Chlorine-containing bleaches are usually made by reacting chlorine gas with cold
aqueous sodium hydroxide.
State the type of reaction and the products formed in this reaction.
Write an equation to illustrate what happens when chlorine gas reacts with hot
aqueous sodium hydroxide instead. [3]
(b) Three unmarked jars contain HCl, HBr and HI respectively.

Describe how plunging a red hot glass rod into each of the jars in turn can help to
identify the gaseous hydrogen halide present.
Explain your answer in terms of relevant bond energies. Where relevant, include
equation(s) to support your answer. [3]
(c) Both halogenoalkanes and hydrogen halides undergo hydrolysis under

specific reagents and conditions.
(i) Suggest reasons why reaction I must be heated for some time for it to
occur, whereas reaction II takes place almost instantaneously at room
temperature.
ICH 3 CHBrCH 2 CH 3 (l) + NaOH(aq) CH 3 CH(OH)CH 2 CH 3 (aq) + NaBr(aq)
IIHBr(aq) + NaOH(aq) H 2 O(l) + NaBr(aq) [2]
(ii) How would the rate of the reaction between CH 3 CHClCH 2 CH 3 and NaOH
compare to that of reaction I? Explain your answer with the aid of the
Data Booklet. [2]
(iii) In reaction I,an inversion of the stereochemical configuration of the organic

product was observed.
Describe the mechanism for reaction I.Show relevant lone pairs and
dipoles, and use curly arrows to indicate the movement of electron pairs. [2]
(iv) Write the rate equation for reaction I.

With the help of your rate equation, estimate the effect on the rate of
reaction I of diluting the solution with an equal volume of solvent. Explain
your answer. [3]
(v) Rates of reactions can also be dependent on the temperature used.

Describe, and explain in molecular terms, how the rate of a reaction is
affected by a change in temperature. You should include a reference to the
Boltzmann distribution in your answer. [3]
(d) With the use of NaOH(aq) and another reagent, describe how you could
distinguish 1-bromopropane from 2-bromopropane. [2]
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[Total: 20]

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8
5 Ovalbumin, OVA, is the predominant protein in egg white, making up approximately

54% of the total protein content. It is also a key reference protein used in protein
research, vaccination experiments and immunology.
Some of the predominant and significant amino acids found in OVA are listed in the
table below.
name abbreviation structural formula

H2N CH COOH
cysteine cys
CH2SH
H2N CH COOH
aspartic acid asp
CH2COOH
H2N CH COOH
leucine leu
CH2CH(CH3)2
H2N CH COOH
lysine lys
CH2CH2CH2CH2NH2
HN CH COOH
proline pro H2C CH2

CH2
H2N CH COOH
serine ser
CH2OH
H2N CH COOH
valine val
CH(CH3)2
(a) Research has shown that the C-terminal sequence of OVA is cys-val-ser-pro,
with proline being the last amino acid residue of the polypeptide chain.
Draw the structure of this C-terminal portion at pH 1. [2]
(b) When heat is applied, OVA undergoes denaturation. The structure of

OVA, when denatured by heat, exists mostly in the form of-pleated sheets.
(i) Define what a -pleated sheet is. Sketch a diagram to show how a
polypeptide chain is held in the shape of a -pleated sheet. [3]
(ii) Explain what is meant by the term denaturation.

Using suitable pairs of amino acids from the table above, draw labelled
diagrams to illustrate two different types of side-chain interactions that will
be affected by the heat-induced denaturation. [4]
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(iii) Aggregation
ggregation
gr of the -pleated sheets form formed during the heat-induced
denaturation
enaturation of OVA results in the formation of a white insoluble
insolubl solid.
From
om the given table, suggest
sugges three amino acidswhose side chains are on
the
e outside of the -pleated
pleated sheets such that the denatured OVA
OV is insoluble
O
in water
water. [1]

577 trendyline
9
5 (c) OVA can be administered to treat suspected poisoning by heavy metal ions via
ingestion.
In this treatment, consumption of a small amount of OVA causes the heavy metal
ions in the gastrointestinal tract to be trapped by the protein, thus preventing the
ions from being absorbed by the body.
Suggest possible chemical interactionsbetween OVA and heavy metal ions in this
treatment. [2]
(d) Aspartic acid, which can be found in OVA, is a non-essential amino acid that can
be synthesised by the human body. It plays a vital role in the construction of
biochemicals in the citric acid cycle and assists the liver in removing excess
ammonia and other toxins from the bloodstream.
2 1
H2N CH COOH
CH2COOH
3
It is found that the length of the C 1 -C 2 bond is shorter than the C 2 -C 3 bond.
Suggest a reason for this difference. [1]
(e) There are three pK a values associated with aspartic acid: 2.1, 3.9 and 9.8.
Starting with the cationic form, aspartic acid undergoes the first two stages of acid
dissociation as shown below:
- +
- +
H3N CH COOH H H3N CH COO H H3N CH COO
. .
pK a1 = 2 1 pK a2 = 3 9
CH2COOH CH2COOH CH2COO
(i) Explain why the-COOH dissociates in preference to the

side-chain COOH in the first stage of dissociation. [2]
(ii) Ignoring the effect of pK a2 and pK a3 on the pH, calculate the pH of a

0.050 mol dm3 solution of aspartic acid. [1]
A solution of aspartic acid can resist pH changes when a small amount of acid or
base is added.
(iii) Draw the structures of the species responsible for this characteristic of the
solution at pH 9.8. [2]
(iv) With the aid of equations, show how this solution of aspartic acid can
maintain its pH at 9.8. [2]
[Total: 20]
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10
BLANK PAGE
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579 trendyline
1
Suggested Answers
2016 H2 Chemistry Preliminary Examination Paper 3
1 (a) (i) The two bond energies of bonds between C and O in the Data Booklet are
E(C=O): +740 kJ mol1 and E(CO): +360 kJ mol1, which are double and
single bonds respectively. The bond between C and O in carbon
monoxide is however a triple bond which is stronger than both the
double and single carbon-oxygen bonds.[1m]
(ii) Energy due to bond formation

= E(CO) 3E(HH) = 1046 3(436) = 2354 kJ mol1
Energy due to bond breaking
= 4E(CH) + 2E(OH) = 4(410) + 2(460) = +2560 kJ mol1
Enthalpy change of reaction
= BE(bonds broken) BE (bonds formed)
=2354 + 2560[1m]
= +206 kJ mol1[1m]
(b) (i) G = H TS; Since H = +206 kJ mol1, and G = +142 kJ mol1.

Hence at 298K, +142 = +206 (298)S[1m]
S = +0.215kJ mol1 K1 [1m]
(ii) When the reaction just becomes feasible, G= 0.

Assuming H and S do not change over a large temperature change,
H = TS , hence T = 958 K[1m] for correct ans + 3sf + units
(c) (i) CH 4 (g) + H 2 O (g) CO (g) + 3H 2 (g)

Initial pressure/ atm 10/3 5/3 00
Change in pressure/ atm 1.8/3=0.61.8/3=0.6 +1.8/3= 0.6+1.8
Eqm pressure/ atm3.330.6 = 2.731.670.6 = 1.070.6+1.8
[1m]
(ii)

3
PCO . PH2
Kp = [1m]
PCH4 .PH2O
K p = [0.6(1.8)3]/[2.73(1.07)]
= 1.20 atm2[1m]
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580 trendyline
2
1 (c) (iii) Percentage yield of H 2 = (1.8/5) x 100 = 36% [1m]
(iv) The yield will be higher at a higher temperature.()

This is because higher temperature favours the endothermic reaction
asthe reaction that absorbs heat is favoured at higher temperature
and position of equilibrium shifts right. [1m]
The yield will be increased at a lower pressure. ()

This is because since the forward reaction produces more gaseous
molecules than the backward reaction, a lower pressure favours
the forward reaction that produces more gaseous molecules to
counteract the decrease in pressure so that position of equilibrium shifts
right, thus increasing the yield. [1m]
2(): [1m]
(d) (i) When an alkaline electrolyte (e.g. warm KOH) is used, the reactions are
as follows:
At the anode: H 2 (g) + 2OH(aq) 2H 2 O(l) + 2e [1m]ss not reqd
At the cathode: O 2 (g) + 2H 2 O(l) + 4e 4OH(aq) [1m]ss not reqd
(ii) E cell = (+0.40) ( 0.83) = +1.23V [1m]
(iii) Eradicate/Prevent/Avoid/Remove the possibility of alkali leakage from

the fuel cell. [1m]
(e)
CH3 CH3 CH3 CH3

HCN,
trace amount of
CO + HCl + AlCl3 NaCN / NaOH H2SO4(aq) or HCl (aq)
Gattermann-Koch heat under reflux

reaction
C H C OH
[1m] H C OH
H O
CN COOH
[1m] [1m]
2 (a) (i) Pale greenish-yellowcolour of Cl 2 gas fades

OR
Aluminium glows/ burns.[1m]
(ii) AlCl 3 dissolves in water to give[Al(H 2 O) 6 ]3+, which hydrolyses (to a large
extent) in water to give H+ ions / to give a weaklyacidic solution. [1m]
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ndy
dylin
nce, the solution turns red
enc
Hence, /pinkish
in -red
d.[1m]
[1m
red/pinkish-red.[1m]
AlCl
Cl 3 (s) + 6H 2 O( l)
O(l)
O(l [A H 2 O) 6 ]3+
[Al(H
Al(H 3
((aq) 3Cl(aq)
aq) + 3Cl (aq)
[1m]
l(H 2 O) 6 ]3+ (aq) [Al
[Al(H [Al(H )]2+(aq) + H+(aq)
A (H 2 O) 5 (OH)]

581 trendyline
3
2 (a) (iii) On addition of a small quantity of NaOH(aq),[Al(H 2 O) 6 ]3+/ Al3+(aq) forms the
white Al(OH) 3 precipitate.
On addition ofexcess NaOH(aq), Al(OH) 3 /white precipitate forms a
soluble, colourless complex Al(OH) 4 . [1m]
OR
As Al(OH) 3 is an amphoteric hydroxide, so it can further react with
NaOH(aq).
[Al(H 2 O) 6 ]3+(aq) + 3OH(aq)

Al(OH) 3 (s) + 6H 2 O(l)[1m]ss are reqd
[Note: Accept Al3+(aq) + 3OH(aq) Al(OH) 3 (s)]
Al(OH) 3 (s) + OH(aq) [Al(OH) 4 ](aq)[1m]ss are reqd
H
(b) (i)
CH 3 CH=CH 2 + AlCl 3 + HCl CH3C CH2 + AlCl4 [1m]
+
H
(ii) H H
CH3
+ CH3C CH2 C
+
H
+ H
CH3
H
CH3 CH3
C + AlCl4 CH3
C
+ H
CH3
+ AlCl3 + HCl
[2m]
+ +
(iii) CH 3 CH 2 CH 2 carbocation is less stable than CH 3 CHCH 3
[1m]
asit has one less electron-donating alkyl group.
+
Hence, the positive charge on CH 3 CH 2 CH 2 is less dispersed and this
carbocation is formed in a smaller quantity.
(iv)
CH3
CH3
tr
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[1m]
C 3
CH

582 trendyline
4
5 (c) (v) Test: Add acidified KMnO 4 to each compound separately and heat. Pass
any gas evolved through limewater. [1m]
Observations: Both cumene and the isomer in (iv) will decolourise purple
KMnO 4 but only the cumene will give CO 2 gas which gives a white ppt with
limewater. [1m]
(i)

S
[1m]
Cl O
Cl
(ii) POCl 3 has more electrons per molecule than SOCl 2 . [1m]
As a result, more energy is required to overcome the stronger van der
Waals forces / induced dipole-induced dipole attractions between POCl 3
molecules than the weaker van der Waals forces / induced dipole-
induced dipole attractions (and permanent dipole-permanent dipole
attractions) between SOCl 2 molecules.[1m]
(d) (i) P O H
% by mass 34.8 62.9 2.3
Amount/mol 1.12 3.93 2.3
Ratio 1 3.5 2
2 7 4
The empirical formula of W is P 2 O 7 H 4 . [1m]
(ii) O O
P P
O OH
OH [1m]
OH
OH
(iii) 5H 3 PO 4 + POCl 3 3P 2 O 7 H 4 + 3HCl[1m]
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583 trendyline
5
3 (a) (i) CaCO 3 CaO + CO 2 [1m]
(ii) At 500 C, the solids present are MgO and CaCO 3 .

At 900 C, the solids present are MgO and CaO.
So, mass of CO 2 = 3.06 2.03 = 1.03 g
Since CaC 2 O 4 CaCO 3 CO 2 ,
1.03
Amount of CaC 2 O 4 = = 0.0234 mol[1m]
44.0
Mass of MgO = 3.06 mass of CaCO 3

= 3.06 (0.0234 100.1)
[1m]
= 0.718 g (or 0.717)
ORMass of MgO = 2.03 (0.0234 56.1) = 0.717 g
0.718
Hence, amount of MgC 2 O 4 = amount of MgO = =0.0178 mol
40.3
0.0178
So, the ratio is = 0.761(or 0.760) [1m]
0.0234
(b) (i) A ligand is an anion or molecule which has at least one lone pair of
electrons to form dative / co-ordinate bonds with metal ion or atom.[1m]
(ii) +3 [1m]
(iii) O 3
O
O

O
O O
Fe

O O O

O O
[2m]
O
(iv) The colour of the complex arises due to electron transition between the d
orbitals.The presence ofligands causes the 3d orbitals in Fe3+to split into
two different energy levels with relatively small energy difference.
Radiation from thevisible lightregion of the electromagnetic spectrum is
absorbedwhen an electron transits from a d-orbital of lower energy to
anunfilled / partially-filled d-orbital of higher energy.
The colour seen is the complement of the colour absorbed. [3m]
(v)
ttrendyline
trend
Fehas
rendyline
ren
ehas energetically accessible vacantorbitals that can accept
off electrons from ligandsto
onds,
nds, unlike calcium
bonds,
ligand
ligandsto
calciu . [1m]
calcium.
a
ac
o form dative covalent bond
lone pair
bonds / coordinate

584 trendyline
6
3 (c) K undergoesalkaline hydrolysis with NaOH(aq) on warming to give anion of L

and NH 3 gas.
K is a primary amide.
L is carboxylic acid.
L undergoes condensation reaction with 2,4-DNPH to give positive test.
L is a carbonyl compound/ is either a ketone or an aldehyde
L has no reaction with Fehlings solution
L is not an aldehyde/L is a ketone
L undergoes acid-hydrogencarbonate reaction with NaHCO 3 (aq)
L is carboxylic acid.
L undergoes reduction reaction with LiAlH 4 .
M is a primary alcoholandsecondary alcohol.
N undergoes mild oxidation to give M.
M is a diol.
N is an alkene.
Explanation: [4m]
O O O O H H
CH3CH2C C NH2 CH3CH2C C OH CH3CH2C C H CH3CH2CH=CH2
K L N
OH OH
M
[1m] each
4 (a) Type of reaction: Disproportionation [1m]
Products formed: Cl(aq), ClO(aq) [or NaCl (aq), NaClO(aq)] [1m]
3Cl 2 (g) + 6OH(aq) 5Cl(aq) + ClO 3 (aq) + 3H 2 O(l) [1m]
[OR3Cl 2 (g) + 6NaOH(aq) 5NaCl (aq) + NaClO 3 (aq) + 3H 2 O(l)]
(ss not reqd)
(b) Bond energy and bond strengthof HX decreases down the Group. [1m]
Hence, down the Group, HX becomes less thermally stable.
Thermal decomposition of HX involves the reaction (for X = I and Br)
[1m]
2HX(g) H 2 (g) + X 2
With HI, copious violet fumes of I 2 are seen.

With HBr, somered-brown / orange fumes of Br 2 are seen. [1m]
With HCl, no fumes observed (or no observation).

585 trendyline
7
4 (c) (i) Energy must be supplied to break the covalent bond between C & Br,
hence reactionI has high E a [1m] and must be heated.
In aqueous state, HBr andNaOHaredissociated into ionsORexist as ions)
as they are strong acid and strong base. Net reaction is the formation of bonds
between H+ and OH ions to give water. Since neutralisation
involves attraction ofoppositelycharged ionsH+ and OHwhichrequires low E a ,
rate of reaction II is faster. [1m]
(ii) Rate of reaction will be slower [1m].

The carbon-halogen bond is broken in the rate-determining step and
since CCl bond (340 kJ mol1) is stronger than CBr bond (280 kJ
mol1), more energy will be required to break the CCl bond and hence the
rate will be slower [1m].
(iii) Since the stereochemical configuration of the product is reversed, the reaction
follows the S N 2mechanism.
CH3 CH3 H CH3

H H
:OH
C Br HO C Br HO C + Br

CH2CH3 CH2CH3 CH2CH3
[2m]
(iv) Rate = k[CH 3 CHBrCH 2 CH 3 ][NaOH][1m]
Rate of reactiondecreases by 4 times[1m] as concentration of each

reactant is halved [1m].
OR
Diluting the solution with equal volume of solvent will lower the
concentrations of both reagents by half [1m] and hence, the rate will be
decreased by four times [1m].
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586 trendyline
8
4 (c) (v) As the temperature is increased, more reactant particles / molecules

have(kinetic)energies greater than or equal to the activation energy[1m]
Hence thefrequency of effectivecollision between reactant particles/
moleculesincreases and reaction rate increases.[1m]
This is evident from the Boltzmann distribution curve of kinetic energies as
shown below:
Number of particles /Fraction of particles
No. of particles with energy Ea at T1

T1 No. of particles with energy Ea at T2
T2 > T1
T2 Ea: Activation energy
[1m]
0 Ea Energy
Effect of temperature on Boltzmann distribution of molecular energies
(d) Add NaOH(aq) (or alkaline), I 2 (aq), then heat.

bromopropanebut no precipitate formed for
Yellow precipitate formed for 2
1bromopropane. [1m]
5 (a) H H O H O H O H
N C C N C C N C C N C COOH
CH2SH H CH(CH3)2 H CH2OH

[2m]
(b) (i) A pleated sheet consists of adjacent polypeptide strands stabilised

by hydrogen bonds between the backbone C=O group of one strand and the
backbone NH group of the adjacent strand.[1m]
adjacent
C
strand

O
hydrogen
H
bonds

N C a strand of
trendyline
re
e
polypeptide
chain
O

H

N adjacent
strand
[2m]

587 trendyline
9
5 (b) (ii) Denaturation involves the disruption of R-group interactions

/ side-chain interactions of a protein, [1m]
leading to possible destruction of the secondary, tertiary and quaternary
structures of the protein.
OR
which in turnalters the conformation/shape of the protein and causes the
protein to lose its ability to perform its specific function. [1m]
Category Diagram illustrating R group interaction (Any one of the suggested pairs)
hydrogen
bond
[1m]
van der
Waals
forces
[1m]
(b) (iii) Leucine, valine, proline, cysteine [1m]

(Any 3 of the 4 stated amino acid residues)
5 (c) Heavy metal ionshave a high affinity for sulfur and will bind tightly(to SH group
/ sulfur) group(of cysteineresidue / in OVA). [1m]
Heavy metal ionsform ionic interactions with COO. [1m]
These interactions between OVA and heavy metal ions may lead to precipitation
and prevent the metal ions from being absorbed by the body.
(d) The C 1 -C 2 bond is a sp2-sp3 overlap, whereas the C 2 -C 3 bond is a sp3-sp3

overlap.
OR
The C 1 -C 2 bond is formed by the overlap of the sp2 hybrid orbital of C 1 and
the sp3 hybrid orbital of C 2 . In contrast, the C 2 -C 3 is formed by the overlap of
the sp3 hybrid orbital of C 2 and the sp3 hybrid orbital of C 3 . [1m]
The sp2 orbital of C 1 contains greater s-character
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n
ne
whereelectrons
lectrons nucleus, the bonding e
ectrons can penetrate closer to the nucleus electrons are
more strongly attracted to the nucleus of the C 1 atom atom.. He
Hence
H the bond
formed by the sp2-sp3 overlap is shorter.

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10
5 (e) (i) The pK a YDOXHRIWKH-COOH is lower, hence the -COOH is a stronger

acid than side-chain COOH [1m]
because theelectron-withdrawing N / NH 2 / NH 3 + LV FORVHU WR WKH -
COOH group.
The negative charge RI -COO anion is more dispersed DQG WKH - [1m]
COOanion is more stable/stabilised to a larger extent.
(ii)
[H+] = K a1 0.050 = 10 2.1 0.050 = 0.0199 moldm3
Hence, pH = lg(0.0199) = 1.70 [1m]
(iii) The two species present in the buffer solution at pH 9.8:
[2m]
(iv)
[1m]
[1m]
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Class Adm No
Candidate Name:
2016 Preliminary Examination II

Pre-University 3
Paper 1 Multiple Choice 21st Sept 2016
1 hour
Additional materials: Multiple Choice Answer Sheet
Data Booklet
Do not turn over this question paper until you are told to do so
Write your name, class and admission number in the spaces provided at the top of this page
and on the Multiple Choice Answer Sheet provided.
There are forty questions on this paper. Answer ALL questions. For each question there are
Choose the one you consider correct and record your choice in soft pencil on the Multiple
Choice Answer Sheet provided.
Read the instructions on the Multiple Choice Answer Sheet very carefully.
Any rough working should be done in this question paper.
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yline
li
The use of an approved
proved scientific calculator is expected, where
pproved whe appropriate.
FOR EXAMINERS
EXAMINER USE
TOTAL
OTAL (4
((40
40 marks)
This question paper consists of 23 printed pages and 1 blank page.

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2
Section A
For each question there are four possible answers, A, B, C, and D. Choose the one you consider to
be correct.
1 Gaseous hydrochloric acid was bubbled through a solution of sodium carbonate until the
solution turned blue litmus paper red.
How will the total number of ions present in solution in the reaction mixture vary?
A B
number number
of ions of ions
0 0
amount of amount of
acid added acid added
C D
number number
of ions of ions
0 0
amount of amount of
acid added acid added
2 In winter, ice forms only on the surface of lakes and rivers, allowing aquatic life to survive
below the surface.
Which of the following statements about ice does not explain this phenomenon?
A Ice has an open structure.

B The water molecules in ice are in an orderly tetrahedral arrangement.
C Water molecules can form intermolecular hydrogen bonding in ice.
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D ec
ecules
Water molecules have a much lower energy
ergy in ice than in water.
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3
3 An ion SF 3 n is T-shaped as shown below.
n
F
F S
F
What is the value of n?
A 2 B 1 C +1 D +2
4 What is the new pressure of a sample of gas, initially at 1 atm, when it is heated from 25 C to
75 C at constant volume?
A 0.3 atm B 0.9 atm C 1.2 atm D 3.0 atm
5 Diboron tetrachloride, B 2 Cl 4 , is a colourless liquid at room temperature. The combination of

gaseous atoms of boron and chlorine to form B 2 Cl 4 (g) is represented by the equation below.
2B(g) + 4ClJ% 2 Cl 4 (g+ 2127 kJ mol-1
The bond energy of a BB bond is +303 kJ mol-1.
What is the bond dissociation energy of a BCl bond?
A 608 kJ mol-1 B 456 kJ mol-1 C +456 kJ mol-1 D +608 kJ mol-1
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4
A student carried out an experiment to determine the heat capacity of a copper can using the
setup below.
copper can water
spirit burner
methanol (Mr = 32.0)
The following data was recorded by the student:
Initial temperature of water / C 25 C

Final temperature of water / C 42 C
Mass of spirit burner before burning / g 220.00 g
Mass of spirit burner after burning / g 219.50 g
3
Volume of water / cm 150 cm3
Given that the enthalpy change of combustion of methanol is 715 kJ mol-1, determine the
heat capacity of the copper can.
A 30.2 J K-1 B 43.8 J K-1 C 626 J K-1 D 655 J K-1
7 The following reaction is thermodynamically feasible only at a high temperature.
CaCO 3 V&D2V&2 2 (g)
What are the VLJQVRIH DQGS for the reaction?
H S
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A
B +
C +
D + +
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5
8 The mechanism involved in the formation of compound Z is as follows:
Step I: W + X Y (fast)
Step II: W + Y Z (slow)
What is the rate equation for this reaction?
A Rate = k[W][X]
B Rate = k[W][Y]
C Rate = k[W][Y]2
D Rate = k[W]2[X]
9 Alkenes in an acidic medium can isomerise in the presence of Al 2 O 3 catalyst.
Ealkene Zalkene
The energy profile diagram of the reaction is shown below.
A (E1 E2) corresponds to the enthalpy change of the forward reaction.
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B Leaving pure Ealkene to isomerise for a long
g duration yields
y mainlyy Zalkene.
C The isomerisation more Zalkene
erisation produces mor Zalkene at high temperatures and
an produces more
Ealkene att low temperatures.
temperatures
D There are 2 intermediates in the isomerisation process.
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6
10 At 313 K, iodine monochloride exists in equilibrium with iodine and chlorine.
I 2 (g) + Cl 2 (g) 2ICl(g)
When a mixture of iodine and chlorine in the mole ratio of 1:1 is heated at 313 K and
a constant pressure of 1 atm, the mole fraction of iodine monochloride present at equilibrium
is 0.23.
What is the equilibrium constant, K p ?
A 0.299 B 0.357 C 0.597 D 1.55
11 The concentration of Sr2+ ions in a 0.5 dm3 solution is 2.0 x 10-2 mol dm-3. Na 2 CO 3 solid was
added to the solution in excess until the concentration of CO 3 2- ions remained at
2.5 x 10-6 mol dm-3.
Given that the K sp of SrCO 3 is 1.6 x 10-9, what mass of SrCO 3 was precipitated?
A 0.0472 g
B 0.0944 g
C 1.43 g
D 2.86 g
12 Halogens T 2 , U 2 and V 2 were added to separate aqueous solutions containing T, U and V

ions and observations recorded in the table below.
T(aq) U(aq) V(aq)

T2 no reaction U 2 formed V 2 formed
U2 no reaction no reaction no reaction
V2 no reaction U 2 formed no reaction
In which sequence is reducing power of the halides arranged in increasing order?
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A T < V < U
B U < T < V
C U < V < T
D V < U < T
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13 It is known that lithium and magnesium have similar chemical properties.
Which property of the following lithium compounds is likely to be wrong?
A Li 2 CO 3 undergoes thermal decomposition to produce carbon dioxide as the only gas.

B LiNO 3 produces oxygen as the only gas upon heating.
C Li 2 O dissolves in water to form a solution of pH greater than 7.
D LiSO 4 is soluble in water.
14 The following Group II elements form sulfates with the following crystalline forms:
MgSO 4 .7H 2 O CaSO 4 .2H 2 O SrSO 4 BaSO 4
Which of the following explains the observed trend in number of moles of water of
crystallisation?
A Atomic radius of the elements increases down the group.

B Ionic character of sulfates increases down the group.
C Ionisation energy of the elements decreases down the group.
D Radius of the cations increases down the group.
15 What are the products formed when chlorine gas is bubbled into cold aqueous sodium
hydroxide?
A NaCl and NaClO

B NaCl and NaClO 3
C NaClO only
D NaClO 3 only
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8
16 The graphs below show the variation of two properties of the halogen hydrides.
Graph I Graph II
HF HCl HBr HI HF HCl HBr HI
Which properties are illustrated in Graphs I and II?
Graph I Graph II
A Boiling point Thermal stability
B pH of solution Thermal stability
C Thermal stability Melting point
D Thermal stability pH of solution
17 When halogenomethanes are warmed in aqueous NaOH followed by acidified AgNO 3 , the
rate of formation of precipitate is observed to be in the order:
CH 3 F < CH 3 Cl < CH 3 Br < CH 3 I
Which of the following best explains this observation?
A Anionic radius increases from F to I.

B Bond energy decreases from CF to CI.
C Bond polarity decreases from CF to CI.
D Charge density decreases from F to I.
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18 The Co2+ ion forms a blue complex with Cl ions. Various samples containing different
amounts of Co2+ and Cl were prepared, and their colour intensities measured using a
colorimeter. The following graph was obtained.
Which statement about the complex ion formed is correct?
A The complex ion absorbs blue light.

B The co-ordination number of the Co2+ ion is 4.
C The geometry of the complex ion is octahedral about Co2+.
D The overall charge of the complex ion is 2+.
19 A compound with the molecular formula C 5 H 10 reacts with hot acidified KMnO 4 to form
products that give a white precipitate with limewater and a yellow precipitate with aqueous
alkaline iodine.
What is the identity of the compound?
A CH 3 CH 2 CH 2 CH=CH 2
B CH 3 CH 2 CH=CHCH 3
C CH 3 CH(CH 3 )CH=CH 2
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D CH 3 CH 2 C(CH
(CH
C 3 )=CH 2
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10
20 The deep purple colour of elderberries originates from cyanidin 3-sambubioside.
OH
OH
Cl
HO O
OH OH
OH O OH
O
HO O
OH OH
OH
cyanidin 3-sambubioside
How many optical isomers does cyanidin 3-sambubioside have?
A 26 B 28 C 29 D 211
21 Which species could be an intermediate in an S N 1 substitution?
+ CH3
A CH2 B +
H
OH CH3

C Br C CH3 D HO C Br
-
O CH3 CH3
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11
22 When heated with bromine, hydrocarbon Q undergoes free radical substitution. In the
propagation step, free radical R is formed.
Q + Br R + HBr
If there are exactly three possible structures of R, which of the following is a possible
structure of Q?
A B
C D
23 What is the major organic product formed when excess aqueous bromine is added to the
following compound?
OH
OH OH
Br Br
A B
OH Br
Br Br Br
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e yylliine
H
OH H
OH
O
Br Br Br Br
C D
Br OH
Br OH Br Br
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12
24 Which graph shows the amounts of gases evolved when 1 mol of compound M is subjected to
reagents I and II separately?
HO CHO
HO COOH
M
I: Na 2 CO 3 (s) in excess
II: Na(s) in excess
A B
C D
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13
25 The mechanism of esterification with acyl derivatives in base is as follows, where ROH is the
alcohol and X is the leaving group.
acyl leaving
derivative group
The rate of esterification is known to increase with better leaving group ability, which is related
to basicity. The less basic the leaving group, the better its ability to leave.
Which of the following is the reactivity of acyl derivatives arranged in increasing order?
Acyl derivative
O O O O
A < <
R Cl R O R NH2
O O O O
B < <
R Cl R NH2 R O
O O O O
C < <
R NH2 R Cl R O
O O O O
D < <
R NH2 R O R Cl
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14
26 Compounds K, L and M have the following structures.
H H
O O
N
O O O
O
K L M
Which pair of statements about the properties of K, L and M are correct?
gives a red precipitate with gives a yellow precipitate with hot

Fehlings solution alkaline aqueous iodine
A K, L and M L only
B L and M only L and M only
C L only L only
D L only K and L only
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15
27 Serotonin is a neurotransmitter found in the central nervous system of humans.
H
N
HO
NH2
serotonin
Which of the following could be used to synthesise serotonin?
H
N
KCN
+
in ethanol H (aq)
A intermediate serotonin
HO
reflux heat
Br
H
N
LiAlH4
in dry ether NH3
B
HO OH intermediate serotonin
reflux
O
H
N
LiAlH4 ethanolic
Br
i dry ether
n NaOH
C HO intermediate serotonin
CN reflux
H
N
HBr(g) NH3
D
HO intermediate serotonin
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e
reflux
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16
28 +XFNHOV UXOH GLFWDWHV WKDW ZKHQ WKHUH DUH GHORFDOLVHG -electrons, the compound has
additional stability and is considered to be aromatic. Benzene is one such aromatic
compound.
Pyrrole and pyridine are two nitrogen containing aromatic compounds with 6 delocalised
-electrons.
N H N
pyrrole pyridine
How many electrons do the nitrogen atoms in pyrrole and pyridine contribute to their
GHORFDOLVHG-electron cloud respectively?
pyrrole pyridine
A 1 1
B 1 2
C 2 1
D 2 2
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17
29 A mixture of two amino acids, leucine and aspartic acid, were run on a gel electrophoresis
plate. The following results were obtained:
mixture of amino acids

Before
Cathode Anode (+)
After
&DWKRGH Anode (+)
pK a
Amino acid Side chain
COOH NH 3 + Side chain
Leucine CH 2 CH(CH 3 ) 2 2.3 9.7
Aspartic acid CH 2 COOH 2.0 9.9 3.9
What pH was the gel likely to be buffered at?
A 1.5 B 3.9 C 9.8 D 10.5
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18
30 The Mitsunobu reaction is a procedure that allows for the conversion of primary and
secondary alcohols into esters with the addition of a carboxylic acid and a DEAD catalyst. The
reaction is highly useful as the stereochemistry at the chiral carbon is completely inverted.
O
OH O
+
DEAD O R3
R1 R2 R3 OH PPh3
R1 R2
Which pair of alcohol and carboxylic acid could give compound E?
O
O
O
O
Compound E
alcohol carboxylic acid
OH
O
A CH 3 CH 2 OH O
O
OH
O
B CH 3 CH 2 OH O
O
O
COOH
C
O
OH
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re dy
dy
O
COOH
COO
OOHH
D
O
H
OH
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19
Section B
be correct.

A B C D
1, 2 and 3 1 and 2 2 and 3 1 only
31 Which properties of beryllium chloride are related to its electron-deficient Be atom?
1 its tendency to polymerise

2 its covalent character
3 its acidity in aqueous solution
32 The following diagram illustrates the energy changes of a set of reactions.
H = 581 kJ mol1
X2(standard state) X(aq)
H = +351 kJ mol1
X(g) X(g)
H = 342 kJ mol1
Which of the following can be deduced from the diagram?
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1 m -1.
ectron affinity of X is 581 kJ mol
ec
The first electron
2 lpy
py change from X
The enthalpy J X(aq)
XJX q) is exothermic
exothermic.
3 lpy
py change for the reaction X
The enthalpy X 2 VWDQGDUGVWDWH
VWDQGDUGVWDWHX(g)
DQGDUGVWDWH X(g) +112 kJ mol1.
g) is +1
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20

A B C D
1, 2 and 3 1 and 2 2 and 3 1 only
A voltaic cell is set up using a Zn2+(aq)/Zn(s) half-cell and a Cu2+(aq)/Cu(s) half-cell. What are
the features of the above set up?
1 Electrons flow in the external circuit from zinc to copper.

2 Reduction takes place at the copper terminal and the copper electrode increases in
mass over time.
3 The zinc electrode is the negative electrode.
34 Three elements H, I and J belong to the same period of the Periodic Table.
The oxide of H reacts with both strong acids and bases. The oxide of I gives a solution of
pH > 7 in water and the oxide of J gives a solution pH < 7 in water.
Which statements about elements H, I and J are always correct?
1 Element H has the highest electrical conductivity.

2 The ionic radius decreases in the order I, H, J.
3 The electronegativity of the elements decreases in the order I, H, J.
35 Samples of strontium and barium are burnt in air.
Which of the following flame colours are observed?
1
2
3
n
pale green
orange-red
lilac
d
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21
36 Which of the following titanium compounds are likely to exist?
1 Ti 2 O 5
2 TiBr 4
3 K 2 Ti 2 O 3
37 Capsaicin is the chemical found in chillies that gives rise to the sensation of spiciness.
O
CH3
N
H
CH3
HO
OCH3
Capsaicin
Which of the following statements about capsaicin are correct?
1 Capsaicin decolourises cold alkaline potassium manganate(VII).

2 Capsaicin gives a positive FeCl 3 test.
3 Capsaicin gives an orange precipitate with 2,4-dinitrophenylhydrazine.
38 Bromobenzene is unreactive to nucleophiles while 3-bromopropene is very reactive in

comparison.
What could be reasons for the lack of reactivity of bromobenzene with nucleophiles?
1 The electrons repel incoming attacking nucleophiles.

2 The CBr bond in bromobenzene is stronger than the CBr bond in 3-bromopropene.
3 The CBr bond is unable to rotate freely.
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22

A B C D
1, 2 and 3 1 and 2 2 and 3 1 only
39 The Claisen Condensation is a reaction that occurs between two esters, or between one ester
and another carbonyl compound.
O O O
2
O O
O O O O
+
H O H
Which of the following are examples of the Claisen Condensation reaction?
O O O
O
+
1 O H O
H O
O O O O
O +
2
O O
O
O
3
O
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23
40 Hair contains chains of the protein keratin, which comprises amino acids forming interactions
with other keratin chains. Hair can be treated in many ways to achieve a desired hair style.
Which of the following treatments will produce the desired styles?
1 Heating hair with steam can help to elongate it.

2 The curling of hair requires both reducing and oxidising agents.
3 Usage of ammonia causes hair to soften and uncurl.
END OF PAPER
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[Turn over
2016 PU3 H2 CHEM PRELIM 2 EXAM
ANSWER SHEET (H2)
Question Question
Key Key
Number Number
1 B 21 A
2 D 22 B
3 B 23 D
4 C 24 A
5 C 25 D
6 A 26 D
7 D 27 C
8 D 28 C
9 B 29 D
10 B 30 D
11 C 31 D
12 A 32 C
13 B 33 A
14 D 34 D
15 A 35 D
16 A 36 C
17 B 37 B
18 B 38 B
19 D 39 A
20 C 40 A
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Class Adm No
Candidate Name:

Pre-University 3
Paper 2 Structured 15th Sept 2016
2 hours
Additional materials: Data Booklet

Write your name, class and admission number on all the work you hand in.
Answer all the questions.

Question 1 2 3 4 5 6 Total
Marks
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tre
en
en
ndy
dyyli
ylin
liine
ine
12
2
e 12
1 7 16 11 14 72
This question paper consists of 21 printed pages and 1 blank page.

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2
1 Planning For
examiners
A student found a bottle of solid transition metal complex, X, in the laboratory. The
use
label on the bottle showed that the molecular formula of X is Cr(H 2 O) 6 Br 3 and that
the cation of complex X is octahedral in shape. The label also showed that X is
soluble in water.
(a) State the oxidation state of Cr in complex X and hence the full electronic
configuration of the Cr ion in X.
.......[2]
The student researched online and found out that X could have any of the four
structural formulae below:
[Cr(H 2 O) 6 ]Br 3
[CrBr(H 2 O) 5 ]Br 2 H 2 O
[CrBr 2 (H 2 O) 4 ]Br 2H 2 O
[CrBr 3 (H 2 O) 3 ] 3H 2 O
The student wanted to determine the structural formula of X using precipitation and
gravimetric analysis. Gravimetric analysis involves the measurement of mass of the
precipitate collected after a suspension is filtered.
In order to perform the experiment, a 100 cm3 standard solution of 0.100 mol dm-3 of
Cr(H 2 O) 6 Br 3 needs to be prepared.
(b) Write a plan to prepare the standard solution. In your plan, provide details of
calculation of mass of solid X used. You may assume you are provided with:
solid X
distilled water
apparatus normally found in a school laboratory.
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.......
.......
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3
For
examiners
use
.......
.......
.......
.......
[3]
With the standard solution of X prepared, the student wanted to carry out an
experiment to determine the structural formula of X.
(c) You are to design an experiment to help the student determine the structural
formula of X using the method of precipitation of silver bromide followed by
gravimetric analysis.
You may assume that you are provided with:
standard solution prepared in (b)
aqueous silver nitrate of concentration 2.0 mol dm-3
the quantity of the reagents used
the procedure for the precipitation and gravimetric analysis
an outline of how the experimental data would be used to determine the
structural formula of X.
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.......
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4
....... For
examiners
use
.......
.......
.......
.......
.......
.......
.......
[5]
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5
(d) In an experiment using a different sample of Cr(H 2 O) 6 Br 3 , it was found that the For
examiners
mole ratio of Cr(H 2 O) 6 Br 3 to AgBr formed is 1: 1. Given that the shape of the
use
cation of this sample is also octahedral and that it can exhibit geometric
isomerism, draw the structures of the two isomers of the cation.
[2]
[Total: 12]
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6
2 (a) This question is about the chemistry of crown ethers. For

examiners
use
Crown ethers are cyclic chemical compounds that consist of a ring containing
several ether groups. The most common crown ethers are oligomers of ethylene
oxide, the repeating unit being ethyleneoxy, i.e. -CH 2 CH 2 O-. The term crown
refers to the resemblance between the structure of a crown ether bound to a
cation, and a crown sitting on a persons head.
The first number in a crown ethers name refers to the number of atoms in the
ring, and the second number refers to the number of oxygen atoms in the crown
ether.
Crown ethers strongly bind to certain cations, forming complexes. The oxygen
atoms are well situated to coordinate with a cation located at the interior of the
ring, whereas the exterior of the ring is hydrophobic.
Structures of common crown ethers are shown below.
12-crown-4 15-crown-5 Q
(i) Name the crown ether Q.
...[1]
(ii) Predict and explain whether crown ethers are soluble in water.
...
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...[2]

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7
Crown ethers are size-selective, as they form the most stable complexes with For
examiners
metal ions that fit best into the ring. The metal cation sits in the centre of the ring
use
and interacts with lone pairs from all of the oxygen atoms.
Q forms stable complexes with K+ metal ion.
(iii) Illustrate how K+ metal ion binds to Q with an aid of a diagram. State the
type of bonding between the crown ether and the metal ion.
[2]
(iv) Suggest the identity of a Group I cation which would be most suitable to bind
with 15-crown-5.
...[1]
(v) When propyl bromine is treated with KF in benzene, no reaction takes place.
But when the crown ether Q is added to the reaction mixture, the desired
propyl fluoride is produced.
Br KF
no reaction
benzene
Br KF F
benzene
O
O O
O O
O
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8
Explain why this is so. For

examiners
use
..........................................................................................................................
......................................................................................................................[2]
(b) Crown ethers are generally synthesised involving the Williamson ether syntheses
between excess dichloride derivatives of the appropriate ethylene glycols and the
appropriate bishydroxy benzenes. The synthesis scheme for the synthesis of
difunctionalised 32-crown-10 derivative is shown below.
Cl O O O Cl O O O O Cl
NaH O
+
Step F CH3O
OH O O O O Cl
O
CH3O OH
OH
CsF
O
OH
OCH3
O O O O O
O O O O O
O O
Step G
HO OH
CH3O OCH3
O O O O O
O O O O O
Step H
O O O O O
Br Br
O O O O O
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32-crown-10 derivative
(i) uggest
ggest the roles of NaH and CsF in the reaction scheme.
Suggest
...[1]
(ii) State the type of reaction occurring in steps F and G.
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9
...[1]
(iii) State the reagents and conditions required for step H. For
examiners
..
use
[2]
[Total: 12]
3 In the Periodic Table, there is said to be a diagonal relationship between elements of

the second and third periods of the Periodic Table exemplified by lithium and
magnesium.
An element R is related to aluminium by such a relationship and R also has the highest
first ionisation energy of its group.
(a) (i) Identify R and explain the similarity in polarising powers of the cations of R
and Al3+.
..........................................................................................................................
......................................................................................................................[2]
(ii) Predict and explain the pH of the solution formed when the chloride of R
dissolves in water.
..........................................................................................................................
......................................................................................................................[2]
(b) Another class of chlorides, acid chlorides, can react with alcohols to form esters
which are sweet-smelling. Esters have been used as flavourings in food and
perfumes. For example, ethyl propanoate is an ester with pineapple-like smell.
The kinetics of the hydrolysis of ethyl propanoate in alkaline medium at T K was

studied.
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eparate
parate experiments were carried out wi
Two separate with varying con
concentrations of
aqueouss sodium hydroxide solution. For each experiment, the co
concentration of
ropanoate
opanoate was determined
ethyl propanoate deter
dete mined
ined at regular time intervals.
interva
The graph
aph below shows the results of Experiment
xpe 2 mol dm-3.
1 with [NaOH] = 2.0 For
examiners
use
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10
[CH3CH2COOCH2CH3] / mol dm-3
Experiment 1
Time / min
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11
The results of Experiment 2 with [NaOH] = 1.0 mol dm-3 are shown below. For
examiners
use
Time Experiment 2 with [NaOH] = 1.0 mol dm3
/ min [CH 3 CH 2 COOCH 2 CH 3 ] / mol dm3
0 0.0200
25 0.0152
50 0.0115
75 0.0088
100 0.0067
125 0.0051
(i) Plot the results of Experiment 2 on the same graph above. Label your graph
clearly. [1]
(ii) Use the two graphs to determine the order of reaction with respect to
[CH 3 CH 2 CO 2 CH 2 CH 3 ] and [NaOH], showing your working clearly.
[2]
[Total: 7]
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12
4 2-propanol is a colourless, flammable liquid with a strong odour. It is widely used as a For
examiners
solvent in many industrial applications.
use
(a) 2-propanol can be used as a fuel in the fuel cell. At the anode of the cell,
2-propanol is oxidised to carbon dioxide. The electrons pass around the external
circuit to the cathode. The protons formed from the oxidation move through the
conducting polymer electrolyte to the cathode, where they react with oxygen to
produce water.
(i) Construct ion-electron equations for the reactions at the anode and cathode
respectively.
Anode:.........
Cathode:..[2]
(ii) Hence construct the equation for the overall reaction.
.....[1]
(iii) The cell is capable of producing an e.m.f. of 1.56 V. By using suitable data
from the Data Booklet, suggest a value for the Eo of the CO 2 /CH 3 CH(OH)CH 3
electrode reaction.
[2]
(iv) Suggest a possible advantage of using the 2-propanol fuel cell compared to a
hydrogen fuel cell.
........
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.....[1]
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13
(b) 2-propanol reacts with hot excess concentrated sulfuric acid to form propene. The For
examiners
reaction follows a 3-step mechanism as described below:
use
Step 1 The oxygen atom on 2-propanol is protonated by H 2 SO 4 forming
intermediate A and HSO 4 - in an exothermic reaction.
H
+
O H
CH3 C CH3
H
Intermediate A
Step 2 The C-O bond in intermediate A breaks, forming a carbocation B
and water. This step is endothermic and is the rate determining
step.
Step 3 The carbocation is then deprotonated in an exothermic reaction,
forming propene. H 2 SO 4 is regenerated.
(i) State the type of reaction undergone when 2-propanol reacts with hot excess
concentrated sulfuric acid.
.....[1]
(ii) Use the information given in the table above to draw out the full mechanism
for the reaction between 2-propanol and concentrated sulfuric acid, indicating
the movement of electrons using curly arrows and showing clearly the lone
pair of electrons involved in the mechanism. You are advised to use structural
formulae for all species, so that it is clear which bonds are broken and which
are formed.
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14
(iii) Using the information given in the table in (b), sketch a fully labelled energy For
examiners
profile diagram of the reaction between 2-propanol and concentrated sulfuric
use
acid.
[2]
(c) 2-propanol reacts with methanoic acid in the presence of concentrated sulfuric acid,
producing an ester, isopropyl formate, and water. The equilibrium below is set up
during the reaction:
O OH O
+ + H 2O
OH O
isopropyl formate
If 0.500 mol of methanoic acid and 0.300 mol of 2-propanol were mixed with a small
amount of concentrated sulfuric acid and allowed to reach equilibrium, the
equilibrium mass of isopropyl formate was found to be 16.64 g.
(i) Write an expression for the equilibrium constant, K c , for the reaction.
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[1]
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15
(ii) Calculate a value for K c . For

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use
[2]
(iii) A molecular sieve is a crystalline substance with pores of molecular

dimensions which permits the passage of very small molecules such as water.
The use of molecular sieves in the reaction above increases the yield of
isopropyl formate. Suggest a reason for the increase in yield.
......
.....[1]
[Total: 16]
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16
5 Hydrastine is a nitrogen containing drug used in the treatment of memory-related For

examiners
disorders such as Alzheimers disease and schizophrenia and has the structure shown
use
below.
N
O CH3
O
O
OCH 3
Hydrastine
A chemist planned a synthetic route to synthesise Hydrastine from

1,2-dimethylbenzene through the intermediates, compounds W and X, as shown below.
O
N
CH3 CH 2 OH O
a few steps step A many steps
CH3
O
O
CH3 O
O
OH
O
Compound W Compound X O
OCH 3
Hydrastine
(a) Hydrastine can be hydrolysed in either

I acidic or
II basic conditions.
Draw the structures of the products obtained for each case. Assume that the ether
group (C-O-C) is inert. [2]
I II
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y
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17
(b) Devise a reaction scheme to help him synthesise compound X via compound W For
examiners
from 1,2-dimethylbenzene. Show clearly the reagents and conditions required for
use
each step.
[4]
(c) State the oxidation numbers of the carbon atoms, labelled with an *, in
1,2-dimethylbenzene and compound X.
*
*
CH 3 O
CH3 O
Oxidation number of C* in 1,2-dimethylbenzene:...
Oxidation number of C* in compound X: ........[2]
(iv) Compare the relative acidity of the alcohol and the carboxylic acid groups
present in compound W.
.........
.....
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.....[3]

[Total: 11]
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18
6 (a) Boiling raw eggs in hot spring water at pH = 9.2 produces black eggs (kuro tamago) For
examiners
through a chemical reaction with geothermal heat and volcanic gas as iron
use
properties ahere to the porous shells. The black colour of iron sulfide is a result of a
reaction with hydrogen sulfide, and it produces boiled eggs with black shells.
Iron sulfide is precipitated according to the following reaction.
reaction 1: Fe2+(aq) + S2(aq) FeS(s)
Hydrogen sulfide gas from volcanic systems is released into the hot spring water
and behaves as a dibasic (diprotic) weak acid.
H 2 S(g) + aq 2H+(aq) + S2(aq)
In a saturated solution of hydrogen sulfide,
[H+]2[S2-] = 1.0 x 10-23 mol3 dm-9
(i) Calculate the maximum concentration of sulfide ions present in hot spring
water.
[2]
(ii) Hence, calculate the minimum concentration of Fe2+ that must be present in
hot spring water in order for precipitation to occur.
(K sp of FeS = 4.9 1018 mol2 dm6)
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19
(iii) Use the following data, together with relevant data from the Data Booklet, to For
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calculate for reaction 1 with the aid of an energy cycle.
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standard enthalpy change of formation of FeS(s) 102 kJ mol1

standard enthalpy change of atomisation of Fe(s) +415 kJ mol1
standard enthalpy change of atomisation of S(s) +279 kJ mol1
sum of first two electron affinities of S(g) +337 kJ mol1
enthalpy change of hydration of Fe2+(g) 1981 kJ mol1
enthalpy change of hydration of S2(g) 1372 kJ mol1
[4]
(b) When a precipitate is formed, , in J mol1, is given by the following expression.
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li
(i) Use
se
e the data given in (a)(ii) to calculate , in kJ mol-1, for F
FeS.
[1]
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20
(ii) Use your answer in (a)(iii) and (b)(i) to calculate , in J mol-1 K-1, for the For
examiners
formation of the precipitate FeS(s) at 298 K.
use
[1]
(c) Geraniol (C 10 H 18 O) appears as a clear to pale-yellow oil that is insoluble in water

but soluble in most common organic solvents. It has a rose-like scent and is
commonly used in perfumes.
OH
Geraniol
Geraniol reacts with HBr(g) to form the two possible products:
I: Br Br OH
OH
II: Br Br
(i) State which of the products would be the major product. Explain your answer.
...
......
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.[3]

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21
(ii) Draw a diagram to illustrate the bonding in C=C bond in geraniol in terms of For
examiners
orbital overlap.
use
[2]
[Total: 14]
END OF PAPER
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Class Adm No
Candidate Name:

Pre-University 3
Paper 3 Free Response 19th Sept 2016
2 hours
Additional materials: Cover Page
Answer Paper
Data Booklet

Write your name, class and admission number on all the work you hand in.

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This question paper consists of 15
635printed pages and 1 blank page. trendyline
2
1 (a) At room temperature, the electrode potential E for the system

[MnO 4 -(aq) + 8H+(aq)], [Mn2+(aq) + 4H 2 O(l)] / Pt
is given by the equation
-
0.059 [MnO4 (aq)] [H+ (aq)] 8
E = E + log
5 [Mn2+ (aq)]

where E = +1.51 V. E values at various pH are given below when
[MnO 4 -(aq)] = 0.01 mol dm-3 and [Mn2+(aq)] = 0.0001 mol dm-3.
pH E/V
0 +1.52
3 +1.24
7 +0.83
(i) Define what the symbol Erefers to. [1]
(ii) Calculate the electrode potential of the cell at pH 1, when the

manganate(VII) ion concentration is 0.01 mol dm-3 and the manganese(II)
ion concentration is 0.001 mol dm-3. [2]
(iii) Predict at which pH value (0, 3 or 7) the solution is the most oxidising. [1]
The electrolytic conductivity ,, of a solution in a cell is given by the following

formula:
(c) (l)

a
where c is the conductance of the cell and a is the cross-sectional area of the
electrodes, separated by a distance l.
(iv) l
Often the term is replaced by a cell constant K. Calculate the cell
a
constant of a particular cell if it was found that the conductance of the cell
containing Mn2+(aq) of concentration 0.100 mol dm-3 LV-1 and the
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HOHFWURO\WLFFRQGXFWLYLW\ZDV-1 cm-1. State the units of K.
HOHFWURO\WLFFRQGXFWLYLW\ZDV [2]
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3
(b) A diaphragm cell consisting brine solution, concentrated NaCl, is used in the
commercial electrolytic production of chlorine and sodium hydroxide.
product
(i) Write the ion-electron equations for the reactions occurring at the cathode
and at the anode. [2]
(ii) The chlorine gas is collected separately at the anode to prevent a side
reaction that will occur with one of the products formed. Write a balanced
equation for this side reaction that occurs at room conditions. State the
oxidation numbers of chlorine in all the products formed. [2]
(iii) In an electrolytic experiment using this diaphragm cell, 1.0 mol of gas is
produced at the cathode. Calculate the mass of chlorine gas that is
produced in the same experiment. [1]
(c) Chlorine contains electrons which occupy the n = 2 principal quantum shell.
Draw all the possible shapes of orbitals at the energy level, n = 2. [2]
(d) Explain why aqueous manganese(II) ions are coloured. [3]
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4
(e) Cocaine, C 17 H 21 NO 4 , was first used as a local anaesthetic. It is also a powerful

stimulant and its structure is shown below.
O CH3
O
O
O
N
CH3
Cocaine
Student X was asked to suggest a suitable synthetic route to prepare cocaine

from methylbenzene and compound A.
OH
O
HO
N
CH3
Compound A
Student X suggested the following steps:
Step 1 Methylbenzene is oxidised with hot, acidified KMnO 4 (aq) to give

benzoic acid.
Step 2 Benzoic acid is converted into benzoyl chloride by reacting the
resultant solution from step 1 with thionyl chloride.
Step 3 Benzoyl chloride is reacted with compound A at room temperature.
Step 4 The resultant compound from step 3 is reacted with methanol in the
presence of concentrated sulfuric acid.
(i) Give two reasons why the method suggested would not work. [2]
(ii)
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Draw the aromatic organic product formed when cocaine
hydrolysis.
acidic hydrolysis
cocain undergoes
[1]
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5
Cocaine is smuggled and inhaled as its protonated hydrochloride salt, known as

cocaine hydrochloride. Smoking cocaine is more stimulating than inhaling the
salt as it is absorbed quickly by the capillaries in the lung tissues. The salt is
hence converted back to cocaine before smoking. This is also done as the salt
will decompose before it vapourises.
(iii) Suggest a suitable reagent to convert cocaine hydrochloride back into

cocaine. [1]
[Total: 20]
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2 Researchers at the Max Planck Institute of Chemistry conducted a study to determine

whether the chemicals emitted by human beings via their breath and their skin vary in
response to audiovisual stimulus. In one of the experiments carried out during the
screening of The Hunger Games 2 in a cinema, the researchers detected that there
were spikes of emission of a diene, isoprene, twice; when the heroines dress caught
fire and when the final battle began. Isoprene is associated with muscle contraction,
hence the spikes in emission could be due to unconscious muscle twitching as the
audience empathised with the heroine.
The structure of isoprene is shown below. In its pure form, it exists as a colourless
volatile liquid.
Isoprene
(a) Isoprene reacts with gaseous HBr at room temperature.
(i) Draw the structure of the major product of the reaction and hence state the
IUPAC name of the major product. [2]
(ii) Name and illustrate with a diagram the type of stereoisomerism exhibited by
the major product of the reaction. [2]
(b) Polyisoprene, a polymer of isoprene, is the primary chemical constituent of natural

rubber.
CH3 CH3
CH2 C CH2 C
n CH H < 0
CH
CH2 CH2
n
Isoprene Polyisoprene
(i) Predict, with a reason, the sign of the entropy change of the polymerisation
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process of isoprene. [1]
(ii) With reference to your answer in (b)(i)

(b)(
(b)(i),, state and explain if the
polymerisation is more spontaneous
ane spontane
or less spontaneous at higher
temperatures. [2]
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7
(iii) Natural rubber is insoluble in water. With reference to the structure of

polyisoprene, explain why. [2]
(c) In a Diels-Alder reaction, 2 moles of isoprene react to form 1 mole of limonene.

Limonene is a colourless liquid which possesses a strong smell of oranges. The
mechanism of the reaction proceeds as follow.
limonene
The enthalpy changes of vaporisation of isoprene and limonene are

+26.4 kJ mol-1 and +39.4 kJ mol-1 respectively.
Using the data given and relevant data from the Data Booklet, construct an energy
cycle to calculate the enthalpy change for the reaction below.
2
(l) (l)
Limonene
You may use C 5 H 8 and C 10 H 16 in your energy cycle to represent isoprene and
limonene respectively. [3]
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8
(d) Compound P is an isomer of limonene. When P is oxidised by hot acidified

potassium manganate(VII), Q, C 3 H 4 O 3 , and R, C 7 H 12 O 3 , are formed.
Both Q and R give orange precipitate with 2,4-dinitrophenylhydrazine and give

effervescence when reacted with solid calcium carbonate. Only Q gives a yellow
precipitate with warm alkaline iodine.
When Q reacts with NaBH 4 in methanol, S is formed. 1 mole of S gives 1 mole of

H 2 (g) upon reaction with excess sodium metal.
R reacts with phosphorus pentachloride, giving white fumes and T, C 7 H 11 ClO 2 .

When T reacts with ethereal LiAlH 4 , U, as shown below is formed.
O
O
compound U
Deduce the structures for compounds P T, explaining the chemistry involved. [8]
[Total: 20]
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9
3 Compound U reacts with aqueous hydroxide ions when heated under reflux.
Cl
Cl
Compound U
The product of the reaction between U and hot aqueous hydroxide ions does not have
optical activity.
(a) (i) Describe the full mechanism of the reaction. [3]
(ii) Explain why the product of the reaction does not exhibit optical activity. [2]
(b) When 0.100 mol dm-3 of hydroxide ions react with 0.00100 mol dm-3 of compound
U at 90 C, the half-life of compound U is 25 s.
(i) Define the term half-life. [1]
(ii) Using your answer in (a)(i), state the rate equation of the reaction. [1]
(iii) Calculate the rate constant at 90 &VWDWLQJLWVXQLWV [1]
(iv) If the reaction is repeated using 0.100 mol dm-3 of hydroxide ions and
0.00200 mol dm-3 of U at the same temperature, state the half-life of U in
the new experiment. [1]
(v) With the aid of a clearly labelled Boltzmann distribution curve, explain why
the rate of the reaction decreases when the temperature of the reaction
decreases. [2]
(c) 0.450 g of U was reacted completely with excess hot aqueous sodium hydroxide.
The reaction mixture was cooled and acidified with excess HNO 3 (aq). Calculate
the mass of silver chloride formed when an excess of AgNO 3 (aq) was added.
[2]
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(d) Compound V can be formed from compound U in 3 steps.

O
N
Cl H
compound V
Propose a 3-step synthesis of V from U, indicating clearly all reagents and

conditions used. Draw the structures of all intermediates. [5]
(e) Compound W is an isomer of U.

Cl
Cl
compound W
When W is boiled with aqueous sodium hydroxide, it immediately loses water to

form an organic compound X which gives a yellow precipitate with a medicinal
smell when reacted with warm iodine in KOH(aq).
Suggest the structure of X and write a balanced chemical equation for the reaction
of X with warm iodine in KOH(aq). [2]
[Total: 20]
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11
4 (a) Boron is a metalloid chemical element in Group III. However due to its smaller
size compared to other Group III elements, its charge over mass ratio is closer to
that of silicon. Hence it resembles silicon in many reactions.
(i) Predict the pH of the solution when BCl 3 is added into water. Hence write
an equation for the reaction. [2]
(ii) Explain why CCl 4 does not undergo the same reaction as BCl 3 when it is
added to water. [1]
(iii) The oxide of boron reacts with NaOH the same way SiO 2 reacts with
NaOH. One of the products of the reaction is Na 3 BO 3 . Propose a chemical
equation for the reaction between the oxide of boron and NaOH.
[1]
(b) The following equilibrium exists when BCl 3 (g) is mixed with NH 3 (g).
BCl 3 (g) + NH 3 (g) Cl 3 BNH 3 (s)
(i) Draw a dot-and-cross diagram of the Cl 3 BNH 3 molecule showing clearly its
co-ordinate (dative covalent) bonds. [1]
(ii) Suggest the shape and the bond angle of the BCl 3 molecule. [1]
(iii) Predict the effect of decreasing the temperature on the above equilibrium.
Explain your answer. [3]
(iv) At a total initial pressure of 3 atm, a 1 : 2 mixture of BCl 3 and NH 3 was

DOORZHG WR UHDFK HTXLOLEULXP DW & ,W ZDV IRXQG WKDW WKH HTXLOLEULXP
partial pressure of BCl 3 was 0.68 atm.
Determine the value of the equilibrium constant, K p , for this reaction at
&VWDWLQJLWVXQLWV [2]
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12
(c) Keratin is a fibrous protein that acts as the key structural component of hair. The
amino acid content of keratin in hair of human varies slightly with ethnicity.
The hair sample of an Asian was analysed. Eight of the amino acids in a keratin
molecule present in the hair are listed below.
Amino acid Formula of side chain Number of amino acid residues

(R in RCH(NH 2 )COOH) per molecule of keratin
cysteine -CH 2 SH 1200
glutamic acid -CH 2 CH 2 COOH 1026
serine -CH 2 OH 990
threonine -CH(OH)CH 3 572
leucine -CH 2 CH(CH 3 ) 2 520
aspartic acid -CH 2 COOH 478
glycine -H 464
valine -CH(CH 3 ) 2 456
(i) Use any three of the above amino acids to construct the displayed formula
of a possible section of the protein chain of keratin. [2]
(ii) Describe how a polypeptide chain of keratin is held in the shape of an

-helix. [2]
(iii) The cysteine residues in the keratin molecule can form disulfide bridges.
Illustrate this process by means of a balanced equation.
Assuming all the disulfide bridges are intramolecular, what is the maximum
number of bridges which could be formed within each keratin molecule? [2]
(iv) Apart from the disulfide bridges mentioned in (c)(iii), describe, by means of
diagrams, two other types of side-chain interaction, using suitable pairs of
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amino
mino acids from the table above. [2]
(v) Glutamic acid has three pK

pK a values: 2.1, 4.1 and 9.5.
9.5
Suggest the structure of the major
jor sspecies present in soluti
solutions of glutamic
acid at pH 7. [1]
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13
[Total: 20]
5 Fluorine is a highly toxic pale yellow diatomic gas under standard conditions. As the
most electronegative element, it is highly reactive.
Hydrogen fluoride is also a highly toxic gas which forms corrosive hydrofluoric acid
upon contact with water.
(a) State and explain which gas, fluorine or hydrogen fluoride, displays greater
deviation from ideal gas behaviour. [2]
(b) Fluorine reacts with hydrogen to form hydrogen fluoride.

Write an equation with state symbols for the reaction and describe how you would
expect the reaction of hydrogen with fluorine to differ from that of hydrogen with
chlorine. [2]
(c) Hydrofluoric acid is a weak acid. It forms a buffer solution with salts containing its
conjugate base.
Calculate the mass of solid sodium fluoride required to be added into a 250 cm3
solution of 0.00420 mol dm-3 of HF to form a buffer solution of pH 5.6.
[K a of HF = 7.20 10-4 mol dm-3]
[2]
(d) Hydrofluoric acid is a poison with greater hazards than strong acids even though it
is a weak acid. It can react with calcium in the blood leading to hypocalcemia and
potentially causing death through cardiac arrhythmia. This is due to the formation
of sparingly soluble calcium fluoride in the body.
(i) The solubility of calcium fluoride in water is 2.707 10-4 mol dm-3. Calculate
the solubility of calcium fluoride in a solution of 0.00200 mol dm-3 of aqueous
NaF. [2]
(ii) Explain briefly how the presence of NaF affects the solubility of calcium
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fluoride.
luoride.
uoride. [1]
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14
(e) HCl is a reagent often used in organic reactions.
(i) For each of the following types of reaction, write a balanced equation for a
reaction involving HCl as a reagent or as a catalyst. You may use any
organic compound as the starting material for each reaction.
I Hydrolysis
II Neutralisation
III Addition [3]
(ii) A student proposed the following reaction for the conversion of

2-methylphenol to 4-chloro-2-methylphenol using aqueous hydrochloric acid
as the reagent.
CH3 CH3
HCl(aq)
OH rtp Cl OH
2 methylphenol 4 chloro 2 methylphenol
Explain why the reaction he proposed is not likely to work, and suggest how
the student can improve the conversion. [3]
(iii) Suggest a simple chemical test to distinguish between 2-methylphenol and

phenylmethanol. State clearly the reagent and conditions used as well as the
observations expected. [2]
OH
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y methanol
p enyl
ph
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15
(iv) Compound Z can be formed from 2-methylphenol in two steps.

O
O
O
O
compound Z
Propose a two-step synthesis of Z from 2-methylphenol, stating the reagents

and conditions for each step and showing the structure of the intermediate.
Your synthesis should involve 2-methylphenol as the only organic
reactant. [3]
[Total: 20]
END OF PAPER
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1 Planning For
examiners
A student found a bottle of solid transition metal complex, X, in the laboratory. The
use
label on the bottle showed that the molecular formula of X is Cr(H 2 O) 6 Br 3 and that
the cation of complex X is octahedral in shape. The label also showed that X is
soluble in water.
(a) State the oxidation state of Cr in complex X and hence the full electronic
configuration of the Cr ion in X. [2]
+3
1s2 2s2 2p6 3s2 3p6 3d3
The student researched online and found out that X could have any of the four
structural formulae below:
[Cr(H 2 O) 6 ]Br 3
[CrBr(H 2 O) 5 ]Br 2 H 2 O
[CrBr 2 (H 2 O) 4 ]Br 2H 2 O
[CrBr 3 (H 2 O) 3 ] 3H 2 O
The student wanted to determine the structural formula of X using precipitation and
gravimetric analysis. Gravimetric analysis involves the measurement of mass of the
precipitate collected after a suspension is filtered.
In order to perform the experiment, a 100 cm3 standard solution of 0.100 mol dm-3 of
Cr(H 2 O) 6 Br 3 needs to be prepared.
(b) Write a plan to prepare the standard solution. In your plan, provide details of
calculation of mass of solid X used. You may assume you are provided with:
solid X
distilled water
apparatus normally found in a school laboratory. [3]
Mass of X needed = (100/1000) 0.100 399.7 = 3.997g
Using a mass balance, weigh accurately 3.997g of solid X in a weighing
bottle.
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250 3 beaker,
Transfer the solid into a 250cm eaker, rinsing the weighing
we
weig bottle with
distilled water and pouring the washing into the beaker. D
Dissolve the solid
with distilled water.
wate
Transfer
T f the
th solution
l ti iinto 100cm3 volumetric
t a 10
100 l t i flask,
fl k making sure all
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3
washing goes into the volumetric flask.

Add distilled water into the volumetric flask and top up to the mark.
Stopper the volumetric flask and shake well to form a homogeneous
solution.
With the standard solution of X prepared, the student wanted to carry out an
experiment to determine the structural formula of X.
(c) You are to design an experiment to help the student determine the structural
formula of X using the method of precipitation of silver bromide followed by
gravimetric analysis.
standard solution prepared in (b)
aqueous silver nitrate of concentration 2.0 mol dm-3
the quantity of the reagents used
the procedure for the precipitation and gravimetric analysis
an outline of how the experimental data would be used to determine the
structural formula of X. [5]
Using a pipette, transfer 10.0 cm3 of the standard solution of X into a
beaker.
Add aqueous silver nitrate until in excess and stir with a glass rod. Stop
adding when the cream precipitate formed does not increase in mass (or at
least 3 times the amount of X in 10 cm3).
Using a filter funnel, filter the mixture to obtain the residue.
Transfer the residue to a pre-weighed dry evaporating dish and heat the
residue to dryness by placing the evaporating dish on top of a Bunsen
burner with tripod.
Cool and reweigh the evaporating dish to obtain mass of the residue.
Repeat the heating, cooling and weighing until a constant mass is
obtained.
Amount of X used = (10/1000) 0.100 = 0.00100 mol
Amount of residue formed = mass of residue / 187.9 = y
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Mol ratio of X to AgBr Structural
ctura formula
1:0 [CrBr
CrBr 3 (H
H 2 O) 3 ] 3
3H 2 O
1:1 [CrBr 2 (H
H 2 O) 4 ]Brr 2H 2 O
1:2 [CrBr(H
[ 2 O) 5 ]Br 2 H 2 O
1:3 [Cr(H 2 O) 6 ]Br 3
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4
(d) In an experiment using a different sample of Cr(H 2 O) 6 Br 3 , it was found that the
mole ratio of Cr(H 2 O) 6 Br 3 to AgBr formed is 1: 1. Given that the shape of the
cation of this sample is also octahedral and that it can exhibit geometric
isomerism, draw the structures of the two isomers of the cation.
[2]
[Total: 12]
2 (a) This question is about the chemistry of crown ethers.
Crown ethers are cyclic chemical compounds that consist of a ring containing several ether
groups. The most common crown ethers are oligomers of ethylene oxide, the repeating unit
being ethyleneoxy, i.e. CH 2 CH 2 O-. The term crown refers to the resemblance between
the structure of a crown ether bound to a cation, and a crown sitting on a persons head.
The first number in a crown ethers name refers to the number of atoms in the ring, and the
second number refers to the number of oxygen atoms in the crown ether.
Crown ethers strongly bind to certain cations, forming complexes. The oxygen atoms are
well situated to coordinate with a cation located at the interior of the ring, whereas the
exterior of the ring is hydrophobic.
Structures of common crown ethers are shown below.
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5
12-crown-4 15-crown-5 Q
(i) Name the crown ether Q. [1]
18-crown-6
(ii) Predict and explain whether crown ethers are soluble in water. [2]
Crown ethers are generally insoluble in water because the energy released in
hydrogen bonds formed between crown ethers and water are not exothermic enough
to overcome the temporary dipole-induced dipole interactions between crown ether
molecules and hydrogen bonds between water molecules.
Crown ethers are size-selective, as they form the most stable complexes with metal ions
that fit best into the ring. The metal cation sits in the centre of the ring and interacts with lone
pairs from all of the oxygen atoms.
Q forms stable complexes with K+ metal ion.

(iii) Illustrate how K+ metal ion binds to Q with an aid of a diagram. State the type of
bonding between the crown ether and the metal ion. [2]
Coordinate / Dative bonding

(iv) Suggest the identity of a Group I cation which would be most suitable to bind with
15-crown-5. [1]
Na+
Remarks: Based on question context, as qns say the most stable complex are with
trendyline
trend
d li
gg crown ether bind to K+, a slightly smaller
the one that fits best into ring. Since a bigger
crown ether will bind to Na+.
(v) When
hen propyl bromine is treated with KF in benzene, no re
reaction takes place. But
when the crown ether Q is added to the reaction mixture, the desired propyl fluoride is
[Turn over
653 trendyline
6
produced.
Br KF
no reaction
benzene
Br KF F
benzene
O
O O
O O
O
Explain why this is so. [2]

KF is insoluble in benzene, so F- is unavailable to attack the propyl bromine.
When 18-crown-6 is added, the crown ether surrounds the K+ ion, allowing the F- ion
to be formed for nucleophilic substitution, so the reaction can proceed
Remarks: recognise that you need to ans according to the context. From earlier part,
K+ will react with crown ether, thus producing F-.
(b) Crown ethers are generally synthesised involving the Willaimsen ether syntheses between
excess dichloride derivatives of the appropriate ethylene glycols and the appropriate
bishydroxy benzenes. The synthesis scheme for the synthesis of difunctionalised
32-crown-10 derivative is shown below.
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7
Cl O O O Cl O O O O Cl
NaH O
+
Step F CH3O
OH O O O O Cl
O
CH3O OH
OH
CsF
O
OH
OCH3
O O O O O
O O O O O
O O
Step G
HO OH
CH3O OCH3
O O O O O
O O O O O
Step H
O O O O O
Br Br
O O O O O
(i) Suggest the roles of NaH and CsF in the reaction scheme. [1]
They act as bases, abstracting a proton from phenol.
(ii) State the type of reaction occurring in steps F and G [2]
Step F: Nucleophilic Substitution (S N 2)
Step G : Reduction
(remarks: Calculate the change in OS of the carbon centre)
(iii) State the reagents and conditions required for Step H. [2]
PBr 3 / SOBr 2 , rtp
[Total: 12]
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8
3 In the Periodic Table, there is said to be a diagonal relationship between elements of the
second and third periods of the Periodic Table exemplified by lithium and magnesium.
An element R is related to aluminium by such a relationship and R also has the highest first
ionisation energy of its group.
(a) (i) Identify R and explain the similarity in polarising powers of the cations of R and
Al3+. [2]
R is beryllium.
Polarising power Is directly proportional to charge density (charge/size).
Although Al3+ is of a higher charge than Be2+, Al3+ is also larger in size. The two
ions have similar charge densities and hence, similar polarising powers.
(ii) Predict and explain the pH of the solution formed when the chloride of R
dissolves in water. [2]
pH = 3 ( accept any value from 1 to 4 )
Due to the high charge density of Be2+, it undergoes hydrolysis whereby it
weakens and breaks the O-H bond in H 2 O, readily donating a proton. Hence the
solution becomes acidic.
(b) Another class of chlorides, acid chlorides, can react with alcohols to form esters which
are sweet-smelling. Esters have been used as flavourings in food and perfumes. For
example, ethyl propanoate is an ester with pineapple-like smell.
The kinetics of the hydrolysis of ethyl propanoate in alkaline medium at T K was

studied.
Two separate experiments were carried out with varying concentrations of aqueous
sodium hydroxide solution. For each experiment, the concentration of ethyl
propanoate was determined at regular time intervals as the reaction proceeded.
The graph below shows the results of Experiment 1 with [NaOH] = 2.0 mol dm-3. The
results of Experiment 2 with [NaOH] = 1.0 mol dm-3 are shown below.
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9
[CH3CH2COOCH2CH3] / mol dm-3
Experiment 1
Time / min
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[Turn over
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10
Time Experiment 2 with [NaOH] = 1.0 mol dm3

/ min [CH 3 CH 2 COOCH 2 CH 3 ] / mol dm3
0 0.0200
25 0.0152
50 0.0115
75 0.0088
100 0.0067
125 0.0051
(i) Plot the results of Experiment 2 on the same graph above. Label your graph
clearly. [1]
(ii) Use the two graphs to determine the order of reaction with respect to
CH 3 CH 2 CO 2 CH 2 CH 3 and NaOH, showing your working clearly.
[2]
To find the order of reaction with respect to the ester.

Consider the graph for experiment 1.
1st t 1/2 = 31.0 min (with construction lines shown on the graph)
2nd t 1/2 = 32.0 min (with construction lines shown on the graph)
Since t 1/2 is almost constant, order of reaction with respect to ethyl propanoate =
1
Alternative answer
Can also use the graph for experiment 2 to find two t 1/2 values.
1st t 1/2 = 63.0 min (with construction lines shown on the graph)
2nd t 1/2 = 63.0 min (with construction lines shown on the graph)
Since t 1/2 is constant, order of reaction with respect to ethyl propanoate = 1
To find the order of reaction with respect to NaOH.

For experiment 1, initial rate = 0.010/24.0 = 4.17 x 104 mol dm3 min1
For experiment 2, initial rate = 0.010/48.0 = 2.08 x 104 mol dm3 min1
When [NaOH] is doubled, initial rate is also doubled (4.17x10-4/2.08x10-4 = 2).
Hence order of reaction with respect to NaOH = 1
Alternative answer
Consider the graph for experiment 2.
t 1/2 = 63.0 min
t 1/2 for experiment 2 = (2)(t 1/2 for experiment 1)
reaction rate is halved when [NaOH] is halved.
Hence order of reaction with respect to NaOH = 1
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[Total: 7]
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11
4 2-propanol is a colourless, flammable liquid with a strong odour. It is widely used as a

solvent in many industrial applications.
(a) 2-propanol can be used as a fuel in the fuel cell. At the anode of the cell,
2-propanol is oxidised to carbon dioxide. The electrons pass around the external
circuit to the cathode. The protons formed from the oxidation move through the
conducting polymer electrolyte to the cathode, where they react with oxygen to
produce water.
(i) Construct ion-electron equations for the reactions at the anode and cathode
respectively. [2]
+
Anode: CH 3 CH(OH)CH 3 + 5H 2 O &2 2 + 18H + 18e
Cathode: O 2 + 4H+ + 4e + 2 O
(ii) Hence construct the equation for the overall reaction. [1]
2CH 3 CH(OH)CH 3 + 9O 2 &2 2 + 8H 2 O
(iii) The cell is capable of producing an e.m.f. of 1.56 V. By using suitable data
from the Data Booklet, suggest a value for the Eo of the
CO 2 /CH 3 CH(OH)CH 3 electrode reaction.
[2]
1.56 = +1.23 Eo anode
Eo anode = -0.33V
(iv) Suggest a possible advantage of using the 2-propanol fuel cell compared to
a hydrogen fuel cell. [1]
2-propanol is a liquid but hydrogen is a gas at rtp. 2-propanol is easier to
store and transport.
(b) 2-propanol reacts with hot excess concentrated sulfuric acid to form propene. The
reaction follows a 3-step mechanism as described below:
Step 1 The oxygen atom on 2-propanol is protonated by H 2 SO 4 forming
intermediate A and HSO 4 - in an exothermic reaction.
H
+
O H
CH3 C CH3
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tr
rrendyline
endyline
H
Intermediate A
Step 2 he C-O
The C-O bond in intermediate A breaks, forming a ca
C- carbocation B
and water
water. This step is endothermic
nd and is the rate determining
step.
[Turn over
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12
Step 3 The carbocation is then deprotonated in an exothermic reaction,

forming propene. H 2 SO 4 is regenerated.
(i) State the type of reaction undergone when 2-propanol reacts with hot
excess concentrated sulfuric acid. [1]
Elimination
(ii) Use the information given in the table above to draw out the full mechanism
for the reaction between 2-propanol and concentrated sulfuric acid,
indicating the movement of electrons using curly arrows and showing
clearly the lone pair of electrons involved in the mechanism. You are
advised to use structural formulae for all species, so that it is clear which
bonds are broken and which are formed. [3]
H
H O O +
O
O H
CH3 C CH3 + H O S OH +
-
O S OH
CH3 C CH3
H O O
H
H
+
O H +
CH3 C CH3 + O
CH3 C CH3 H H
H
H
H O O
+ - = +
CH3 C C H + O S OH CH3CH CH2 HO S OH
O O
H H
(iii) Using the information given in the table above, sketch a fully labelled
energy profile diagram of the reaction between 2-propanol and
concentrated sulfuric acid. [2]
t
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13
(c) 2-propanol reacts with methanoic acid in the presence of concentrated sulfuric
acid, producing an ester, isopropyl formate, and water. The equilibrium below is
set up during the reaction:
O OH O
+ + H 2O
OH O
isopropyl formate
If 0.500 mol of methanoic acid and 0.300 mol of 2-propanol were mixed with a
small amount of concentrated sulfuric acid and allowed to reach equilibrium, the
equilibrium mass of isopropyl formate was found to be 16.64 g.
(i) Write the expression for KC.
[1]
[isopropyl formate][H O]
2
KC = [methanoic acid][2-propanol]
(ii) Calculate a value for KC.

[2]
Amount of isopropyl formate = 16.64 / 88 = 0.189 mol
acid + alcohol ester + water
Initial amount / mol 0.500 0.300 0 0
Change / mol -0.189 -0.189 +0.189 +0.189
Eqm amount / mol 0.311 0.111 0.189 0.189
. .

KC =
. . = 1.03

(iii) A molecular sieve is a crystalline substance with pores of molecular

dimensions which permits the passage of very small molecules such as
water. The use of molecular sieves in the reaction above increases the yield
of isopropyl formate. Suggest a reason for the increase in yield. [1]
The molecular sieve removes water, causing concentration of water to
decrease. By LCP, equilibrium will then shift to the right to replenish water,
hence increasing the yield.
[Total: 16]
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14
5 (a) Hydrastine is a nitrogen containing drug used in the treatment of memory-related

disorders such as Alzheimers disease and schizophrenia and has the structure
shown below.
N
O CH3
O
O
OCH 3
Hydrastine
A chemist planned a synthetic route to synthesise Hydrastine from
1,2-dimethylbenzene through the intermediates, compounds W and X, as shown
below.
N
CH3 CH 2 OH O
a few steps step A many steps
CH3
O
O
CH3 O
O
OH
O
Compound W Compound X O
OCH 3
Hydrastine
(i) Hydrastine can be hydrolysed in either

I acidic or
II basic conditions.
Draw the structures of the products obtained for each case. Assume that the
trendyline
ther
he group (C-O-C)
ether (C-O-C) is inert. [2]
662 trendyline
15
O O
+ H
N N
O CH3 O CH3
OH OH
-
O OH O O
OCH 3 O OCH 3 O
Acidic conditions basic conditions

Remarks: In this case, since no specific acid or base is given, you may leave ans as
charged species. In cases where qns give a specific acid/base and asked for organic

compound formed, pls give compound in your answers (ie. COONa instead of COO for
example)
(ii) Devise a reaction scheme to help him synthesise compound X via compound W
from 1,2-dimethylbenzene. Show clearly the reagents and conditions required for
each step.
[4]
O
CH3 KMnO4,H2SO4, CH 2 OH
OH limited LiAlH4
heat O
O
CH3 dryether
OH
OH
Conc. H2SO 4, heat
(iii) State the oxidation numbers of the carbon atoms, labelled with an *, in
1,2-dimethylbenzene and compound X.
*
*
CH3
O
CH3 O
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[2]
In 1,2
1,2-dimethylbenzene,
dimethylbenzene, C = -3
-3
In compound X , C = -1
(iv) Compare
ompare
mpare the relative acidity of the alcohol and the carb
carbo
carboxylic acid groups
resent in compound W
present W.
The R-CH 2 OH is less acidic as compared to R-COOH; The electron donating R
group intensifies the negative charge on the oxygen of the conjugate base
[Turn over
663 trendyline
16
(alkoxide ion), making it less stable; The R-COOH is more acidic because the
negative charge can be delocalised across two electronegative oxygen which
are both electron withdrawing, thus dispersing the charge and stabilising the
conjugate base, making it more acidic.
[Total: 11]
6 (a) Boiling raw eggs in hot spring water at pH = 9.2 produces black eggs (kuro tamago)
through a chemical reaction with geothermal heat and volcanic gas as iron properties
ahere to the porous shells. The black colour of iron sulfide is a result of a reaction with
hydrogen sulfide, and it produces boiled eggs with black shells.
Iron sulfide is precipitated according to the following reaction.
reaction 1: Fe2+(aq) + S2(aq) FeS(s)
Hydrogen sulfide gas from volcanic systems is released into the hot spring water and
behaves as a dibasic (diprotic) weak acid.
H 2 S(g) + aq 2H+(aq) + S2(aq)
In a saturated solution of hydrogen sulfide,
[H+]2[S2-] = 1.0 x 10-23 mol3 dm-9
(i) Calculate the maximum concentration of sulfide ions present in hot spring water.
[2]
+ 9.2
[H ] = 10
= 6.31 1010 mol dm3
[S2] = = 2.51 105 mol dm3
(ii) Hence, calculate the minimum concentration of Fe2+ present in hot spring water
in order for precipitation to occur.
(K
trendyline
K sp
[1]]
of
K sp = [Fe2+][S2]
FeS = 4.9 1 18
10 18
mol2 dm6)
664 trendyline
17
[Fe2+] = = 1.95 1013 mol dm3
(iii) Use the following data, together with relevant data from the Data Booklet, to
calculate for reaction 1 with the aid of an energy cycle.
standard enthalpy change of formation of FeS(s) 102 kJ mol1

standard enthalpy change of atomisation of Fe(s) +415 kJ mol1
standard enthalpy change of atomisation of S(s) +279 kJ mol1
sum of first two electron affinities of S(g) +337 kJ mol1
enthalpy change of hydration of Fe2+(g) 1981 kJ mol1
enthalpy change of hydration of S2(g) 1372 kJ mol1
[4]
102 = 415 + 279 + 337 + 762 + 1560 1981 1372 +

= 102 kJ mol1
Remarks: Do reflect the magnitude for each enthalpy change by the size of the
gap between each energy level (the ans here failed to do so) when constructing
your level diagram.
trendyline
dylin
n
(b) When a precipitate is formed, , in J mol1, is giv
given by the follow
following expression.
(i) Use the data given in (a)(ii) to calculate , in kJ mol-1, for FeS. [1]
[Turn over
665 trendyline
18
= 2.303 8.31 298 lg(4.9 1018)

= 98.7 kJ mol1
(ii) Use your answer in (a)(iii) and (b)(i) to calculate , in J mol-1 K-1, for the
formation of the precipitate FeS(s) at 298 K. [1]
98.7 = 102 298

= = 11.1 J mol1 K1
(c) Geraniol (C 10 H 18 O) appears as a clear to pale-yellow oil that is insoluble in water but
soluble in most common organic solvents. It has a rose-like scent and is commonly
used in perfumes.
OH
Geraniol
Geraniol reacts with HBr(g) to form the two possible products:
I: Br Br OH
OH
II: Br Br
(i) State which of the products would be the major product. Explain your answer. [3]
I would be the major product. This is due to the fact that the tertiary carbocation
intermediate formed after the addition of H is more stable than that of II, which
forms a secondary carbocation, due to more electron donating alkyl groups
attached to the carbocation which stabilises the cation more by dispersing the
positive charge.
(ii) Draw a diagram to illustrate the bonding in any of the C=C bond in geraniol in
terms of orbital overlap. [2]
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19
[Total: 14]
[Turn over
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2
1 (a) At room temperature, the electrode potential E for the system

[MnO 4 -(aq) + 8H+(aq)], [Mn2+(aq) + 4H 2 O(l)] / Pt
is given by the equation
-
0.059 [MnO4 (aq)] [H+ (aq)] 8
E = E + log
5 [Mn2+ (aq)]
where E = +1.51 V. E values at various pH are given below when

[MnO 4 -(aq)] = 0.01 mol dm-3 and [Mn2+(aq)] = 0.0001 mol dm-3
pH E/V
0 +1.52
3 +1.24
7 +0.83
(i) Define what the symbol E refers to. [1]

It refers to the standard electrode potential under standard conditions of
298K, 1 atm and 1 mol dm-3 electrolyte used.
(ii) Calculate the electrode potential of the cell at pH 1, when the
manganate(VII) ion concentration is 0.01 mol dm-3 and the manganese(II)
ion concentration is 0.001 mol dm-3. [2]
pH = 1
[H+] = 10-1 = 0.100 mol dm-3
0.059 (0.01) [0.1] 8
E = +1.51 + log = + 1.43 V
5 [0.001]
(iii) Predict at which pH value, from the table above, the solution is the most
oxidising. [1]
At pH=0
The electrolytic conductivity of a solution in a cell is given by the following

formula:
(c) (l)

a
trendyline
where c is the conductance of the
e cell and a is
s the cross-sectional
cross-secti area of the
odes,
des, separated by a distance l.
electrodes, l.
(iv) l
Often the term is replaced by a cell constant K. Calculate the cell constant
a
of a particular cell if it was found that the conductance of the cell containing
668 trendyline
3
Mn2+(aq) of concentration 0.100 mol dm-3 LV -1 and the electrolytic
FRQGXFWLYLW\ZDV-1 cm-1. State the units of K. [2]
0.011 = K (0.022)
K = 0.500 cm-1
(b) A diaphragm cell consisting brine solution, concentrated NaCl, is used in the
commercial electrolytic production of chlorine and sodium hydroxide.
product
(i) Write the ion-electron equations for the reactions occurring at the cathode
and at the anode. [2]
Anode: 2Cl- Cl 2 + 2e-
Cathode: 2H 2 O + 2e- H 2 + OH-
(ii) The chlorine gas is collected separately at the anode to prevent a side
reaction that will occur with one of the products formed. Write a balanced
equation for this side reaction that occurs at room conditions. State the
oxidation numbers of chlorine in all the products formed. [2]
Cl 2 + 2OH- Cl- + ClO- + H 2 O
Oxidation no. of Cl in Cl- = -1 Oxidation no of Cl in ClO- = +1
(iii) In an electrolytic experiment using this diaphragm cell, 1.0 mol of gas is
produced at the cathode. Calculate the mass of chlorine gas that is produced
in the same experiment. [1]
trendyline
1 mol
m of H 2 SURGXFHGPRORI&O
R 2 produced
duce
Mass of Cl 2 produced = 1 x 71.0 = 71.0 g
669 trendyline
[Turn over
4
(c) Chlorine contains electrons which occupy the n=2 principal quantum shell. Draw all
the possible shapes of orbitals at the energy level, n=2. [2]
(d) Explain why aqueous manganese(II) ions are coloured. [3]

2+
Mn has partially-filled d-orbitals. When the ligands approach the central metal ion, splitting
of the d-orbitals occurs.
7KHenergy gap, E, between the non-degenerate orbitals corresponds to the wavelength
of light in the visible region of the electromagnetic spectrum.
:KHQDQHOHFWURQIURPDlower energy d orbital is promoted to a higher energy d orbital (d-
d electron transition), radiation corresponding to E is absorbed. The complementary colour
will be seen as the colour of the complex.
(e) Cocaine, C 17 H 21 NO 4 , was first used as a local anaesthetic. It is also a powerful

stimulant and its structure is shown below.
O O
O CH3
O
N
CH3
Cocaine
Student X was asked to suggest a suitable synthetic route to prepare cocaine from
methylbenzene and compound A.
O OH
HO
N
CH3
trendyline
l
nt X suggested the following steps:
Student s:
Compoun A
Compound
670 trendyline
5
Step 1 Methylbenzene is oxidised with hot, acidified KMnO 4 to give benzoic

acid.
Step 2 Benzoic acid is converted into benzoyl chloride by reacting the
resultant solution from step 1 with thionyl chloride.
Step 4 The resultant compound from step 3 is reacted with methanol in the
presence of concentrated sulfuric acid.
(i) Give two reasons why the method suggested would not work. [2]
1. In step 2, thionyl chloride will hydrolyse in the presence of aqueous
solution
2. The final product will be the protonated form of cocaine since it is
prepared in an acidic medium.
3. Heat is required for step 4.
(ii) Draw the aromatic organic product formed when cocaine undergoes acidic
hydrolysis. [1]
O
OH
Cocaine is smuggled and inhaled as its protonated hydrochloride salt, known as

cocaine hydrochloride. Smoking cocaine is more stimulating than inhaling the salt
as it is absorbed quickly by the capillaries in the lung tissues. The salt is hence
converted back to cocaine before smoking. This is also done as the salt will
decompose before it vapourises.
(iii) Suggest a suitable reagent to convert cocaine hydrochloride back into

cocaine. [1]
Dilute NaOH
[Total: 20]
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[Turn over
6
2 Researchers at the Max Planck Institute of Chemistry conducted a study to determine

whether the chemicals emitted by human beings via their breath and their skin vary in
response to audiovisual stimulus. In one of the experiments carried out during the
screening of The Hunger Games 2 in a cinema, the researchers detected that there
were spikes of emission of a diene, isoprene, twice; when the heroines dress catches
fire and when the final battle begins. Isoprene is associated with muscle contraction,
hence the spikes in emission could be due to unconscious muscle twitching as the
audience empathises with the heroine.
The structure of isoprene is shown below. In its pure form, it exists as a colourless
volatile liquid.
Isoprene
(a) Isoprene reacts with gaseous HBr at room temperature.

(i) Draw the structure of the major product of the reaction and hence state the
IUPAC name of the major product. [2]
Br
Br
2,3-dibromo-2-methylbutane
(ii) Name and illustrate with a diagram the type of stereoisomerism exhibited by
the major product of the reaction. [2]
Optical isomerism
CH3 CH3
CH3 Br CH3 Br
C C
C C
H Br Br
H
CH3 CH3
(b) Polyisoprene, a polymer of isoprene, is the primary chemical constituent of natural

rubber.
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672 trendyline
7
CH3 CH3
CH2 C CH2 C
n CH H < 0
CH
CH2 CH2
n
Isoprene Polyisoprene
(i) Predict, with a reason, the sign of the entropy change of the polymerisation
process of isoprene. [1]
Negative, because the system becomes less disorderly as the number of
molecules decrease, hence having less way to arrange
(ii) With reference to your answer in (b)(i), state and explain if the
polymerisation is more spontaneous or less spontaneous at higher
temperatures. [2]
G = H - TS
H and S are both negative. At high temperature, magnitude of TS is
larger than magnitude of H hence G is more positive.
Less spontaneous
(iii) Natural rubber is insoluble in water. With reference to the structure of
polyisoprene, explain why. [2]
Energy evolved from the formation of temporary dipoled-induced dipole
between polyisoprene and water is not sufficient to overcome the hydrogen
bonds between water molecules.
(c) In a Diels-Alder reaction, 2 moles of isoprene react to form 1 mole of limonene.
Limonene is a colourless liquid which possesses a strong smell of oranges. The
mechanism of the reaction proceeds as follow.
limonene
The enthalpy changes of vaporisation of isoprene and limonene are

+26.4 kJ mol-1 and +39.4 kJ mol-1 respectively.
cycle totrendyline
Using the data given and relevant data from the Data Booklet,
Booklet, cons
o calculate the enthalpy change for the reaction below.
construct an energy
673 trendyline
[Turn over
8
2
(l) (l)
Limonene
You may use C 5 H 8 and C 10 H 16 in your energy cycle to represent isoprene and
limonene respectively. [3]
;
Using bond energy,
H 1 = 2 BE(C=C) 4 BE(C-C) = 2(610) 4(350) = -180 kJ mol-1
By Hess Law,
H = 2(+26.4) +(-180) (+39.4) = --167 kJ mol-1
(d) Compound P is an isomer of limonene. When P is oxidised by hot acidified
potassium manganate(VII), Q, C 3 H 4 O 3 , and R, C 7 H 12 O 3 , are formed.
Both Q and R give orange precipitate with 2,4-dinitrophenylhydrazine and give

effervescence when reacted with solid calcium carbonate. Only Q gives a yellow
precipitate with warm alkaline iodine.
When Q reacts with NaBH 4 in methanol, S is formed. 1 mole of S gives 1 mole of

H 2 (g) upon reaction with excess sodium metal.
R reacts with phosphorus pentachloride, giving white fumes and T, C 7 H 11 ClO 2 .

When T reacts with ethereal LiAlH 4 , U, as shown below is formed.
O
O
trendyline
ompound U
co
com
Deduce
e the structures for compounds P T
T,, explaining the chemist
chemistry involved. [8]
674 trendyline
9
Information Deduction
Both Q and R give orange precipitate Q and R are ketones.
with 2,4-dinitrophenylhydrazine and Q and R has carboxylic acid group.
give effervescence when reacted with
solid calcium carbonate.
Only Q gives a yellow precipitate with Q has the structure CH 3 CO-
warm alkaline iodine.
When Q reacts with NaBH 4 in Reduction of ketone.
methanol, S is formed. S is secondary alcohol.
1 mole of S gives 1 mole of H 2 (g) Acid-metal reaction
upon reaction with excess sodium S has two OH groups
metal.
R reacts with phosphorus Substitution reaction
pentachloride, giving white fumes and T has acyl chloride
T, C 7 H 11 ClO 2 .
When T reacts with ethereal LiAlH 4 , Reduction of ketone to secondary
U is formed. alcohol
Followed by nucleophilic substitution
to form ester.
O OH
OH OH
O O
P Q S
O O
HO Cl
O O
R T
trendyline
Alternative
dy
ative answer for P:
Remarks:
P:
ks: Recognise that q is 8marks for 5 structures, and they asked for
chemistry
ry involved in each reaction, so the type of reaction for ea
very important, need to be stated clearly!
y!
each conversion is
[Total: 20]
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[Turn over
10
3 Compound U reacts with aqueous hydroxide ions when heated under reflux.
Cl
Cl
Compound U
The product of the reaction between U and hot aqueous hydroxide ions does not have
optical activity.
(a) (i) Describe the full mechanism of the reaction. [3]
Nucleophilic substitution (S N 1)

Cl
slow Cl + Cl
Cl + +
OH
-
Cl +
+ OH Cl
Remarks: clue of S N 1 from qns stem that the ion does not have optical
activity.
(ii) Explain why the product of the reaction does not exhibit optical activity. [2]
The intermediate formed in the first step is trigonal planar at the C with the
positive charge. The nucleophile can attack the carbon from the top or the
bottom of the plane, forming a racemic mixture where rotation of plane-
polarised light by one enantiomer is cancelled out by the other enantiomer.
(b) When 0.100 mol dm-3 of hydroxide ions react with 0.00100 mol dm-3 of compound
U DW&WKHKDOI-life of compound U is 25 s.
(i) Define the term half-life. [1]
Half-life is the time taken for the concentration of a reactant to reduce to half
its original value.
(ii) Using your answer in (a)(i), state the rate equation of the reaction. [1]
Cl
Rate = k[ Cl ]
(iii) Calculate the rate FRQVWDQWDW&VWDWLQJLWVXQLWV>@
trendyline
tre
ln 2 ln 2
k= = =0.0277
alf life 25
half
s-1
(iv) d -33 of hydr

Iff the reaction is repeated using 0.100 mol dm hydroxide ions and
dm-3 of U at the
002 moll d
0.002 e same temperature, state the half-life
h
half of U in the
new experiment. [1]
25 s
676 trendyline
11
(v) With the aid of a clearly labelled Boltzmann distribution curve, explain why
the rate of the reaction decreases when the temperature of the reaction
decreases. [2]
T 1 <T 2
At lower temperature, kinetic energy of molecules decreases, less
molecules have energy greater than or equal to activation energy.
Frequency of effective collision decreases, thus rate of reaction decreases.
(c) 0.450 g of U was reacted completely with excess hot aqueous sodium hydroxide.
The reaction mixture was cooled and acidified with excess HNO 3 . Calculate the
mass of silver chloride formed when an excess of AgNO 3 (aq) was added.
[2]
Amount of U = 0.450 / 175 = 0.002571 mol
Amount of AgCl = 0.002571 mol
Mass of AgCl = 0.002571 (108+35.5) = 0.369 g
(d) Compound V can be formed from compound U in 3 steps.
O
N
Cl H
compound V
Propose a 3-step synthesis of V from U, indicating clearly all reagents and

conditions used. Draw the structures of all intermediates. [5]
Cl CN
ethanolic KCN
Cl Cl
heat under reflux
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n
LiAllH4 in
LiAlH4
dry eth
heerr
CH2NH2
C6H5COC
COCll
CO
compound V Cl
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[Turn over
12
(e) Compound W is an isomer of U.

Cl
Cl
compound W
When W is boiled with aqueous sodium hydroxide, it immediately loses water to

form an organic compound X which gives a yellow precipitate with a medicinal
smell when reacted with warm iodine in KOH(aq).
Suggest the structure of X and write a balanced chemical equation for the reaction
of X with warm iodine in KOH(aq). [2]
O
-
O
+ 3I + 4OH + CHI + 3I + 3H O
2 3 2
O O
[Total: 20]
4 (a) Boron is a metalloid chemical element in Group III. However due to its smaller
size compared to other Group III elements, its charge over mass ratio is closer to
that of silicon. Hence it resembles silicon in many reactions.
(i) Predict the pH of the solution when BCl 3 is added into water. Hence write
an equation for the reaction. [2]
pH 2 (accept between 1 to 2)
BCl 3 + 3H 2 O B(OH) 3 + 3HCl
Also accept:
2BCl 3 + 3H 2 O B 2 O 3 + 6HCl
(ii) Explain why CCl 4 does not undergo the same reaction as BCl 3 when it is
added to water. [1]
B in BCl 3 has energetically accessible empty orbital to accept lone pair from
O of H 2 O but C in CCl 4 do not.
(iii) The oxide of boron reacts with NaOH the same way SiO 2 reacts with
NaOH. One of the products of the reaction is Na 3 BO 3 . Prop
Propose a chemical
equation for the reaction between the oxide of boron
equati boro and NaOH.
1]
[1]
B 2 O 3 + 6NaOH 2Na 3 BO 3 + 3
3H 2 O
(b) The following equilibrium exists when BCl 3 (g) is mixed with NH 3 (g).
678 trendyline
13
BCl 3 (g) + NH 3 (g) Cl 3 BNH 3 (s)

(i) Draw a dot-and-cross diagram of the Cl 3 BNH 3 molecule including its
co-ordinate (dative covalent) bonds. [1]
(ii) Suggest the shape and the bond angle of the BCl 3 molecule. [1]
WULJRQDOSODQDU
(iii) Predict the effect of decreasing the temperature on the above equilibrium.
Explain your answer. [3]
Reaction is exothermic since it involves formation of dative bonds
By LCP, position of equilibrium will shift to the right
This is to increase the temperature of the system by favouring the
exothermic reaction.
(iv) At a total initial pressure of 3 atm, a 1 : 2 mixture of BCl 3 and NH 3 was
DOORZHG WR UHDFK HTXLOLEULXP DW & ,W ZDV IRXQG WKDW WKH HTXLOLEULXP
partial pressure of BCl 3 was 0.68 atm.
Determine the value of the equilibrium constant, K p , for this reaction at
&VWDWLQJLWVXQLWV [2]
BCl 3 (g) + NH 3 (g) Cl 3 BNH 3 (s)
Initial partial pressure 1 2 0
Change / atm -0.32 -0.32 +0.32
Eqm partial pressure 0.68 1.68 0.32
1
Kp = =0.875 atm-2
(.)(.)
(c) Keratin is a fibrous protein that acts as the key structural component of hair. The
amino acid content of keratin in hair of human varies slightly with ethnicity.
The hair sample of an Asian was analysed. Eight of the amino acids in a keratin
molecule present in the hair are listed below.
trendyline
tre
endyyline
mino
n acid
Amino Formula of side
e chain Number
Num of amino acid
ac residues
(R in RCH(NH 2 )COOH) per molecule of keratin
cysteine
ysteine
steine -CH
CH 2 SH 1200
glutamic
amic acid -CH 2 CH 2 COOH
H 1026
serine -CH 2 OH 990
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[Turn over
14
threonine -CH(OH)CH 3 572

leucine -CH 2 CH(CH 3 ) 2 520
aspartic acid -CH 2 COOH 478
glycine -H 464
valine -CH(CH 3 ) 2 456
(i) Use any three of the above amino acids to construct the displayed formula
of a possible section of the protein chain of keratin. [2]
H H O H H H O
N C C N C C N C C
H H O H C H
H C H O
S H
H
or any other combination
(ii) Describe how a polypeptide chain of keratin is held in the shape of an

-helix. [2]
The a-helix is held in place via hydrogen bonds formed between O of -C=O
of a peptide and H of NH of another peptide.
(iii) The cysteine residues in the keratin molecule can form disulfide bridges.
Illustrate this process by means of a balanced equation.
Assuming all the disulfide bridges are intramolecular, what is the maximum
number of bridges which could be formed within each keratin molecule? [2]
2 -CH 2 SH -CH 2 S-SCH 2 - + 2H
600
(iv) Apart from the disulfide bridges mentioned in (c)(iii), describe, by means of
diagrams, two other types of side-chain interaction, using suitable pairs of
amino acids from the table above. [2]
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15
(v) Glutamic acid has three pK a values: 2.1, 4.1 and 9.5.
Suggest the structure of the major species present in solutions of glutamic
acid at pH 7. [1]
NH3
- -
O O
C C
O O
[Total: 20]
5 Fluorine is a highly toxic pale yellow diatomic gas under standard conditions. As the
most electronegative element, it is highly reactive.
Hydrogen fluoride is also a highly toxic gas which forms corrosive hydrofluoric acid
upon contact with water.
(a) State and explain which gas, fluorine or hydrogen fluoride, displays greater
deviation from ideal gas behaviour. [2]
Hydrogen fluoride is held by hydrogen bonds and fluorine is held by td-id.
Hydrogen fluoride has stronger intermolecular forces of attraction hence has
greater deviation from ideal gas behaviour.
(b) Fluorine reacts with hydrogen to form hydrogen fluoride.
Write an equation with state symbols for the reaction and describe how you would
expect the reaction of hydrogen with fluorine to differ from that of hydrogen with
trendyline
e.
chlorine. [2]
H 2 (g) + F 2 (g)
(g 2HF(g)
2HF(g
ne
e reacts explosively and more vigorously with hydrogen
Fluorine hydroge compared to
e with hydrogen.
chlorine hydrogen
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[Turn over
16
(c) Hydrofluoric acid is a weak acid. It forms a buffer solution with salts containing its
conjugate base.
Calculate the mass of solid sodium fluoride required to be added into a 250 cm3
solution of 0.00420 mol dm-3 of HF to form a buffer solution of pH 5.6.
[K a of HF = 7.20 10-4 mol dm-3]
[2]
pH = pK a + lg ([salt]/[acid])
5.6 = -lg(7.20 10-4) + lg ([NaF]/0.0042)
[NaF] = 1.204 mol dm-3
mass of NaF = 1.204 (250/1000) (23.0 + 19.0) = 12.6 g
(d) Hydrofluoric acid is a poison with greater hazards than strong acids even though it
is a weak acid. It can react with calcium in the blood leading to hypocalcemia and
potentially causing death through cardiac arrhythmia. This is due to the formation
of sparingly soluble calcium fluoride in the body.
(i) The solubility of calcium fluoride in water is 2.707 10-4 mol dm-3. Calculate
the solubility of calcium fluoride in a solution of 0.00200 mol dm-3 of aqueous
NaF. [2]
2+ -
CaF 2 (s) Ca (aq) + 2F (aq)
K sp = [Ca2+][F-]2 = (2.707 10-4)(2 2.707 10-4)2 = 7.93 10-11 mol3 dm-9
7.93 10-11 = y (2y + 0.002)2 \2
y = 1.98 10-5 mol dm-3
(ii) Explain briefly how the presence of NaF affects the solubility of calcium
fluoride. [1]
CaF 2 (s) Ca2+(aq) + 2F-(aq)
The presence of NaF increases [F-], hence by LCP, shifting the equilibrium to
the left to partially offset the increase in F. Hence, solubility decreases.
Remarks: Pls rmb to write your eqm equation before explanation, otherwise,
0 mark.
(e) HCl is a reagent often used in organic reactions.

(i) For each of the following types of reaction, write a balanced equation for a
trendyline
reaction
eaction involving
involvi HCl
HCl ass a reagent or as a catalyst. You
Yo may use any
organic
rganic compound
compoun as the starting material for each
e reaction.
[3]
3]]
I Hydrolysis
any correct equation showing hydrolysis of ester, amide or nitrile
682 trendyline
17
II Neutralisation
any correct equation showing acid-base reaction of amine or
carboxylate salt
III Addition
any correct equation showing addition equation of alkene forming
alcohol (must balance equation with water)
(ii) A student proposed the following reaction for the conversion of

2-methylphenol to 4-chloro-2-methylphenol using aqueous hydrochloric acid
as the reagent.
CH3 CH3
HCl(aq)
OH rtp Cl OH
2 methylphenol 4 chloro 2 methylphenol
Explain why the reaction he proposed is not likely to work.

Hence suggest the correct reagent and conditions for the conversion. [3]
The reaction involves electrophilic substitution of benzene. Hence a
electrophile Cl+ is required for the reaction
However in HCl, since Cl is more electronegative, Cl+ is not likely to be
formed.
Cl 2 in CCl 4 at room temperature
(iii) Suggest a simple chemical test to distinguish between 2-methylphenol and

phenylmethanol. State clearly the reagent and conditions used as well as the
observations expected. [2]
OH
phenylmethanol
K 2 Cr 2 O 7 in dilute H 2 SO 4 , heat
trendyline
orange
range solution turns green for phenylmethanol
phenylmethan
range solution remains
orange rem
remains 2-methylphenol
ns orange for 2-
2-methylphenol
OR
R
Br 2 (aq) ;
orange solution decolourises for 2-methylphenol, forming white ppt
683 trendyline
[Turn over
18
orange solution remains orange for phenylmethanol, no ppt formed

OR
neutral FeCl 3 ;
violet colouration formed for 2-methylphenol
no violet colouration for phenylmethanol
(iv) Compound Z can be formed from 2-methylphenol in two steps.

O
O
O
O
compound Z
Propose a two-step synthesis of Z from 2-methylphenol, stating the reagents

and conditions for each step and showing the structure of the intermediate.
Your synthesis should involve 2-methylphenol as the only organic
reactant. [3]
CH3 COOH
KMnO4 dil H2SO4
heat
OH OH
PCl5
O
O
O
O
[Total: 20]
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684 trendyline
Calculator Model / No.
Name: ____________________ Class: 15S_________ Reg Number:

______
MERIDIAN JUNIOR COLLEGE

JC2 Preliminary Examination
Higher 2
____________________________________________________________________
Chemistry 9647/01
Paper 1 Multiple-Choice Questions 23 September 2016
1 hour
OMR Answer Sheet
Write your name, class and register number in the spaces provided at the top of this page.
There are forty questions in this section. Answer all questions. For each question, there are
four possible answers labelled A, B, C and D. Choose the one you consider correct and
record your choice in soft pencil on the OMR answer sheet.
Read very carefully the instructions on the OMR answer sheet.
You are advised to fill in the OMR Answer Sheet as you go along; no additional time will be
given for the transfer of answers once the examination has ended.
Use of OMR Answer Sheet
Ensure you have written your name, class register number and class on the OMR
Answer Sheet.
Use a 2B pencil to shade your answers on the OMR sheet; erase any mistakes cleanly.
Multiple shaded answers to a question will not be accepted.
For shading of class register number on the OMR sheet, please follow the given
examples:
trendyline
y
If your register
g number is 1, then shade
de 01 in the
e inde
index number column.
egister number is 21, then shade 2
If your register 21 in
n the index number column.
co
This document consists of 23 printed pages
MJC Prelim 2016

685 trendyline
Answer all questions in this section.
For each question there are four possible answers, A, B, C, and D. Choose the one
you consider to be correct.
Sodium percarbonate, (Na 2 CO 3 ) x y(H 2 O 2 ), is an oxidising agent in some home and

laundry cleaning products.
20.0 cm3 of 0.0500 moldm3 sodium percarbonate releases 48.0 cm3 of carbon
dioxide at room conditions on acidification.
An identical sample, on titration with 0.0500 moldm3 K 2 Cr 2 O 7 , requires

20.0 cm3 before the first green colour appears. K 2 Cr 2 O 7 reacts with H 2 O 2 in the
mole ratio of 1 : 3.
y
What is the ratio ?
x
1 2 3
A B C D
3 3 1
2 Magnesium nitrate(V), Mg(NO 3 ) 2 decomposes on heating to form magnesium

oxide, nitrogen dioxide and oxygen, while sodium nitrate(V), NaNO 3 decomposes to
formNaNO 2 and oxygen only.
Mg(NO 3 ) 2
MgO + 2NO 2 + O 2
NaNO 3
NaNO 2 + O 2
A mixture of magnesium nitrate(V) and sodium nitrate(V) was heated until no more
gases were evolved. The water soluble part of the residue was used to prepare
1.00 dm3 of solution. 10.00 cm3 of this solutionwas reacted with 30.00 cm3 of
0.0200 moldm3 of acidified potassium manganate(VII) solution.
2MnO 4 + 6H+ + 5NO 2

2Mn2+ + 5NO 3 + 3H 2 O
The excess potassium manganate(VII) solution required 10.00 cm3 of

0.0500 moldm3ethanedioic acid solution for complete reaction
2MnO 4 + 5(COO) 2 2 + 16H+

2Mn2+ + 10CO 2 + 8H 2 O
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What is the
he mass of sodium nitrate(V) in the mixture?
Given M r of NaNO 3 = 85.0
A 85
5g
0.85 B 1 36
1. 6g
1.36 C 4.25
25 g
4.25 D 8
8.50 g
3 h D
Use of the t B
Data kl t iis relevant
Booklet l t to
t this
thi question.
ti
Dinitrogen tetraoxide, N 2 O 4 , has a melting point of 11 C and a boiling point of 21

MJC Prelim 2016 2 [Turn Over
686 trendyline
C.
A sample of 18.4 g of N 2 O 4 (s) is placed in a 24 dm3 vessel under an atmosphere of

helium gas chilled to 20 C at a pressure of 1.0 atm. When the vessel is warmed
to 25 C and the contents are allowed to reach equilibrium, 40 % of the N 2 O 4 (g)
has dissociated into NO 2 (g).
What is the total pressure of the gases in the vessel at 25 C?
A 0.28 atm B 1.28 atm C 1.38 atm D 1.46 atm
The ion X4+ contains 46 electrons and 69 neutrons.
Which of the following statements about X4+ or X2+ is correct?
A X4+ is deflected to approximately twice the extent as Rb+ when subjected to

an electric field.
B X4+has the same electronic configuration as Sr2+.
C X2+ undergoes hydration in water to a greater extent than X4+.
D X2+ can be oxidised by Fe3+.
Which particle contains a single unpaired electron?
A a molecule of N 2 O
B one of the particles formed after the heterolytic fission of a HBr molecule
C the vanadium ion in VO 2
D the chromium ion in Cr 2 O 3
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687 trendyline
In which of the following pairs of compounds would the first compound have a lower
melting point than the second compound?
A CH 3 CH(NH 2 )COOH and CH 3 CH(OH)COOH

B CH 3 CH 2 CH 2 CH 3 and CH 3 CH(CH 3 )CH 3
C GaF 3 , GaCl 3
D Na 2 S, MgF 2
7 Compound X has the following properties.

It is very hard.
It is a lubricant.
It can conduct electricity in the solid state.
What is the most likely structure of compound X?
A simple molecular
B giant molecular
C giant metallic
D giant ionic
8 The MaxwellBoltzmann distribution curve shown below is for a chemical reaction in

living systems.
fraction of molecules
with a given energy
fraction of molecules with

energy > Ea at a particular
temperature
kinetic
0 Ea energy
(activation energy)
Which statement is not true?
A The total area under the curve is 1.
trendyline
B The activation energy will decrease with a decrease in temperature.
C When
hen temperature is increased, the peak of the curve becomes
become lower.
D The
e shaded area of the curve will decrease when enzymes are denatured.
9 ne
e reacts with iodine in the presence of an acid:
Propanone
CH 3 COCH 3 + I 2
H+
CH 3 COCH 2 I + HI
688 trendyline
The mechanism involves the following steps.
+

H
CH 3 COCH 3 CH 3 C(OH)CH 2 slow
CH 3 C(OH)CH 2 + I 2
CH 3 CI(OH)CH 2 I fast
CH 3 CI(OH)CH 2 I
CH 3 COCH 2 I + HI fast
Which graph would be obtained?
A [I2]
[reactant] / mol dm -3 B [I2]
0
time
time/s rate
C +
D [CH3COCH3][H ]
+
[CH3COCH3][H ]
time rate
10 The following data was obtained from the studies of the reaction between O 2 and
NO in a vessel at constant temperature.
Experiment 1 2 3
Initial total pressure of O 2 and NO/ atm 1.00 1.30 1.80
Initial partial pressure of O 2 / atm 0.60 0.90 1.20
Initial rate of reaction/ atm s1 1.08 1.62 4.86
Which of the following statements is correct regarding the above system?
A The order of reaction with respect to O 2 is zero.

B The rate constant k has units of atm1s1.
C The rate equation is rate = k [NO][O 2 ]2.
D The overall order of the reaction is three.
11 Aluminium m chloride exists in two different forms in the
th vapour state. When some
Al 2 Cl 6 was
as added into a reaction vessel, the following equilibrium is slowly
s set up.
Al 2 C
Cll 6 (g) 2AlCl
2Al
2AlCl 3 J
JH
H = +ve
At different times during the experiment, changes were made to the conditions in
the reaction vessel. At each time, there was only one change made to the
689 trendyline
conditions in the reaction vessel.
The change in the concentrations in the mixture with time is shown in the graph
below.
Concentration
Al2Cl6
AlCl3
t1t2t3 time
Which conclusion can be drawn from the graph?
A At t 1 , the pressure of the system was increased by increasing the volume.

B At t 2 , a catalyst was added to the system.
C The temperature of the mixture at t 2 was higher than that at t 1 min.
D The equilibrium constant, K p ,remains the same at t 1 and t 3 .
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690 trendyline
12 Citrate buffers are commonly used to control pH in household cleaners and
pharmaceuticals.
H3C6H5O7 + H2O H 2 C 6 H 5 O 7 + H 3 O+ pK a1 = 3.1
H2C6H5O7 + H2O HC 6 H 5 O 7 2 + H 3 O+ pK a2 = 4.8
HC 6 H 5 O 7 2 + H 2 O C 6 H 5 O 7 3 + H 3 O+ pK a3 = 6.4
A citrate buffer with pH 5.1 was prepared by dissolving solid NaH 2 C 6 H 5 O 7 and
Na 2 HC 6 H 5 O 7 . The total sodium concentration of the prepared buffer was 1.0
moldm3.
What are the concentrations of NaH 2 C 6 H 5 O 7 and Na 2 HC 6 H 5 O 7 in this buffer?
[NaH 2 C 6 H 5 O 7 ] / moldm3 [Na 2 HC 6 H 5 O 7 ] / moldm3

A 0.10 0.20
B 0.20 0.40
C 0.20 0.10
D 0.40 0.30
Excess aqueous (COOH) 2 was added to an acidified solution of

potassium dichromate(VI) in a conical flask. Effervescence was observed until all
(COOH) 2 had completely reacted. The resulting solution was then left to stand in
air for a long time.
Given : 2CO 2 + 2H+ + 2e (COOH) 2 E= 0.44V
What is the colour of the final solution?
A Blue B Green
C Yellow D Orange
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691 trendyline
14 When heated, magnesium carbonate decomposes to form carbon dioxide and
magnesium oxide.
$JUDSKLFDOSORWRI*YHUVXV7GHVFULELQJWKHFKDQJHRIWKHGibbs free energy of

the decomposition of magnesium carbonate with respect to temperature, is shown
below.
*N-PRO-1
200
180
160
140
120
100
80
60
40
20
0
0 100 200 300 400 500 600 700 800 900 100011001200
T/K
Using the information from the graph, what is the value of 6ofor the
decomposition reaction?
A + 6.22 x 103J mol1 K1 B + 6.04 x 102 J mol1 K1

C + 1.61 x 102 J mol1 K1 D + 1.80 x 106 J mol1 K1
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692 trendyline
An electrochemical cell is set up as shown:
T = 298K
Ni salt bridge Pt
Ni2+ Fe2+ Fe3+
[Ni2+] = 0.1moldm3 [Fe3+] = [Fe2+] = 0.1moldm3
Which statement about the e.m.f. of the above cell is correct?
A The e.m.f of the cell is +1.02 V.

B Addition of water to the Fe3+ / Fe2+ halfcell increases the e.m.f of the cell.
C Increasing the mass of the nickel electrode decreases the e.m.f of the cell.
D Addition of excess aqueous ammonia to the Ni2+/ Ni halfcell increases the
e.m.f of the cell.
16 In which row of the table are all statements comparing calcium and barium as well
as their hydroxides correct?
Solubility of
Melting point Flame Test
hydroxide
Calcium Barium Calcium Barium Ca(OH) 2 Ba(OH) 2
A higher lower green red lower higher
B higher lower red green lower higher
C higher lower white green higher lower
D lower higher red green higher lower
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693 trendyline
17 Element Z is in Period 3 of the Periodic Table. The following four statements were
made about the properties of element Z or its compounds.
Three statements are correct descriptions and one is false.
Which statement does not fit with the other three?
A Element Z burns in oxygen with a bright white flame.

B Element Z is a solid at room temperature which does not conduct electricity.
C The oxide ofelement Z reacts with water to form a solution that turns red on
addition of Universal Indicator.
D Adding NaOH (aq) to the solution resulting from the reaction of the chloride
of Z with water produces a white precipitate which is soluble in an excess of
NaOH (aq).
Paramagnetism is the property of being attracted to a magnetic field. Many

transition compounds that contain unpaired electrons tend to be paramagnetic
while those that do not contain unpaired electrons tend to be diamagnetic. Some
compounds are more paramagnetic than others as they contain more
unpaired electrons.
A blue solution of VO2+ undergoes the following reactions.
MnO4/ H+
VO2+ VO2+
excess Sn2+ excess Sn
solutionY
Which of the following statements is incorrect?
A Solution Y contains [V(H 2 O) 6 ]3+.
B Both Sn2+ and Sn act as reducing agents.
C The reacting ratio of VO2+ and MnO 4 is 5 : 1.
D VO2+ is diamagnetic while VO 2 +is paramagnetic.
19
trendyline
udents, W
Three students,
operties
W,, Y and Z Z,, were asked to draw bar charts to represent
perties of the halogens
some properties
Their diagrams
re
halogens and their compounds differ in magnitude.
shown.
grams are shown
magnit
how
Student Y
MJC Prelim 2016 10 For H2 (g) + X2 (g)

2HX (g)Over
[Turn
694 trendyline
o
H
Student W
Ka of HX
Cl Br I
Student Z
For reaction of X2 and cold NaOH (aq)
Oxidation number of
X in XOn formed
0
Cl Br I
Which of the students diagrams are correct?
A both W and Z B both W and Y

C both Y and Z D none of the diagrams
20 How many isomers (both structural and stereoisomers) are there for a compound
with the formula C 4 H 10 O that can react with Na (s)?
A 3 B 4 C 5 D 6
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695 trendyline
21 Isopropylcyclohexane reacts with bromine gas to form different
monosubstituted products. Three of the products are shown below.
Br
Br
Limited Br2 (g) Br

uv
A B C
Given that the rate of abstraction of primary, secondary and tertiary

hydrogen is 2: 3: 6 respectively, what is the expected ratio of the mono
substituted products A: B : C formed?
A 6:2:3 B 1:1:1
C 1:2:2 D 1:6:4
22 Which of the following reactions will not incorporate deuterium (D) into any
2
of the organic products formed? (D= 1H, an isotope of hydrogen)
O
A NaOH, D2O
reflux
O
O
B D2SO4, D2O
reflux
O
O
NaOD, D2O
C reflux
O
O
D2SO4, D2O
D reflux
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r
O
23 t t iis commonly
Phenyl acetate l used
d iin th
h llaboratory
the b t as a precursor for organic

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synthesis.
O CH3
O
phenyl acetate
Which pair of compounds would produce phenyl acetate in high yield when reacted
together?
OH O
A
HO CH3
O-Na+ O
B
HO CH3
O Cl
C CH3OH
O
OH O
D
Cl CH3
Use of the following reaction scheme is relevant for Q24 and Q25.
NO2 NH2 N N Cl CN CH2NH2

HNO2, HCl CuCN
I II III IV
24
Which of the following statements is correct about the reaction scheme?
A The reagent for stage I is LiAlH 4 .

B Stage II is neutralisation reaction.
C Stage III is nucleophilic substitution reaction.
D The reagent for stage IV is hot aqueous NaOH.
25
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Stage IIis
with other
yes
useful dyes.
alt, which can undergo coupling
s theformation of the diazonium salt, cou
compounds
err organic compounds, such as phenol, to form azo compo
compou
reactions
which are

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N N Cl OH
+ N=N OH + HCl
azo compound
diazonium salt
What is the structure of the azo compound formed when P and Q react together in
the presence of HNO 2 and HCl?
CH3
HO3S NH2 N
CH3
P Q
A HO3S N=N OH
CH3
B HO3S N=N N
CH3
CH3 CH3 CH3

C N N N
CH3
CH3 CH3
D HO3S N N
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26 Williamson ether synthesis is a very useful reaction in the formation of ethers via
the S N 2 mechanism shown below.
- -
RO R' X RO R' X
Which of the following compounds will be formed as a major product when

compound Y undergoes Williamson ether synthesis followed by acidification?
Br
OH OH
compound Y
O
O
A B
O
OH
O HO
C D O
OH
27 When a conjugated diene undergoes electrophilic addition with Br 2 , it forms two

products through the 1,2addition and the 1,4addition, which is shown in the
mechanism below.
- Br
Br Br Br
diene
Br Br
Br
Br
Br Br
, -a -
1 2 ddition 1,4 addition
Which of the following statements is not correct?
A The overall rate law is second order.
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ne
e
B The carbocation intermediates are resonance stabilised.
C The 1,2addition
1,2addition product formed when HCl
e 1,2 HCl is used is Cl .
Cll
C
D The
e 1,4addition
1,4
1,4 dition product formed when IICl
addition Cl is used is I.

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28 Which of the following shows the given species arranged in order of decreasing K b
values?
CH2O OCH3 NO2
O O
CH 3 CH(I)COO
I II III IV
A I, III, IV, II B I, IV, III, II

C II, III, IV, I D II, IV, III, I
29 The rod cells at the back of the eye contain a primary alcohol called retinol
which is responsible for their sensitivity to light. Retinol is oxidised by an
enzymecatalysed reaction that keeps the double bonds intact, to retinal, an
aldehyde.
OH
retinol
Which of the following is correct?
A The number of stereoisomers in retinol is 32.

B There are six bonds formed by 2sp22sp3 overlap in a molecule of
retinol.
C In laboratory preparations, retinal can be formed from heating retinol
under reflux with hot potassium dichromate(VI).
D One mole of retinol reacts with 4 moles of hydrogen gas in the
presence of palladium catalyst.
30
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b l
The table below i
gives i f i pertaining
some information i i to three
h i acids.
amino id

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isoelectric
amino acid structure
point
O
lysine H 2N CH C OH 9.6
(lys)
(CH2 )4 NH 2
O
serine H 2N CH C OH 5.7
(ser)
CH2 OH
O
aspartic acid
H2 N CH C OH 2.9
(asp)
CH 2COOH
A mixture of these three amino acids can be separated by electrophoresis.
Which of the following diagrams shows the result of the separation of the
amino acids mixture at pH 7.0?
anode cathode anode cathode

A B
ser asp lys asp ser lys
anode cathode anode cathode

C D
lys ser asp lys asp ser
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For questions 31 to 40, one or more of the three numbered statements 1 to 3 may be
correct. Decide whether each of the statements is or is not correct (you may find it
helpful to put a tick against the statements which you consider to be correct.)

A B C D
1, 2 and 3 are 1 and 2 only 2 and 3 only
1 only is correct
correct are correct are correct
31 In a closed reaction vessel of 10 dm3 maintained at a temperature of 150 C,

gaseous hydrazine decomposes into nitrogen and hydrogen. The system reaches
equilibrium with a total pressure of 1 atm.
N 2 H 4 (g) N 2 (g) + 2H 2 (g)
The average M r of the equilibrium gas mixture in the 10 dm3 vessel is found to be
20.
1 In liquid form, both reactants and products flowing from a burette remain
undeflected when subjected to close vicinity to a charged rod.
2 The mass of the gaseous mixture inside the reaction vessel is 5.75 g.
3 The following graphs depicts the correct behaviour of the three gases under
standard conditions.
N2H4
S9
Q57
N2
H2
1.0 ideal gas
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The responsess A to
A
y
o D should be selected on the basis of
B C D

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1 only is correct
32 Metal thiocyanates have very different industrial uses. For example, calcium
thiocyanate,Ca(NCS) 2 , is used as a stiffening agent of fabrics.
The following data is provided:

H latt o (Ca(NCS) 2 ) = 2118 kJ mol1
o
H hyd (NCS ) = 310 kJ mol1
H hyd o (Ca2+) = 1577 kJ mol1
1 The magnitude of Ho soln of Ca(NCS) 2 is 79 kJ mol1.
2 Magnitude ofHo latt of Ba(NCS) 2 is smaller than that of Ca(NCS) 2 .
3 Go soln of Ca(NCS) 2 is negative at all temperatures.
33 The graph below shows the variation in the standard enthalpy change of
YDSRULVDWLRQ H(vaporisation), for eight consecutive elements in the Periodic
Table, all with atomic number, Z 20.
1
H (vaporisation) / kJ mol
Q
P
S V
R T
U
atomic number, Z
1 The chloride of element Q is acidic in aqueous solution.
2 The oxide of element R has a higher melting point than that of
element S.
3
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tre
end
The responsess A to
A
dylin
dy
Electrical
ne
B C
W..
ectrical conductivity decreases from element P to W

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1 only is correct
34 A lithiumion battery consists of: a cathode made from cobalt oxide, CoO 2 ; an
anode made from graphite with lithium atoms inserted between the layers.
During discharge, Li atoms at the anode give up electrons to become Li+ ions. The
electrons travel round the external circuit, and are picked up by the cathode. A Li+
ion from the electrolyte also moves to the cathode. This is illustrated in the following
diagram in which CCCCC is a simplified representation of a layer of carbon
atoms in graphite.
external circuit
e
e
Co O Co O C C C C C
O O
Li+
Co O Co O Li
C C C C C
O O
electrolyte
cathode anode
Co O Co O C C C C C
O O Li+
Li+
Co O Co O C C C C C
O O
electrolyte
cathode
1 The mass of lithium metal that is deposited when a current of 3 A is passed

through the battery during the charging process in 1 h 20 min is 1.03 g.
2 The oxidation number of cobalt oxide cathode after discharge is +3.
3 The bonding between the lithium atoms and the layers of carbon atoms is
ionic in nature.
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A B C D
1 only is correct
35 A chemist allowed a halogen, X 2 , to react completely with S 2 O 3 2 (aq). This

resultant acidic solution was treated with an excess of aqueous barium nitrate to
produce a white precipitate which is insoluble in dilute nitric acid.
Another halogen, Y2, gave a different sulfurcontaining product with

S 2 O 3 2 (aq).
Which of the following statements are correct with regards to the chemistry
described?
1 A possible identity for X 2 is Br 2 .
2 A possible identity for Y 2 is I 2 .
3 Y 2 is a stronger oxidising agent than X 2 .
36 Which statements concerning the first row transition metal ions are incorrect?
1 Addition of K 2 CO 3 (aq) to CrCl 3 (aq) produces a green precipitate of

Cr 2 (CO 3 ) 3 .
2 Addition of KI (aq) to Fe 2 (SO 4 ) 3 (aq) produces a brown precipitate of FeI 3 .
3 Addition of NaOH (aq) to K 2 CrO 4 (aq) produces an orange solution of

K 2 Cr 2 O 7 (aq).
37 A catalytic converter is part of the exhaust system of modern cars.
Which reactions occur in a catalytic converter?
y
1 2C x H y + (4x + y) NO
2x CO 2 + y H 2 O + (2x + ) N 2
2
2 2CO + 2NO
2CO 2 + N 2
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tre
end
dylin
dy ne
3 O 2 + NO
CO CO + NO 2
The responsess A to
A B C D

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1 only is correct
38 A non-cyclic organic compound has the molecular formula C 5 H 9 O 2 N.
Which pair of functional groups could be present in this molecule?
1 one ketone group and one amide group
2 one ester group and one nitrile group
3 one carboxylic acid group and one nitrile group
39 Doxorubicin is an anti-cancer drug used to treat a wide range of cancers

includingblood cancers, likeleukaemiaandlymphoma.
[The ether group, R-O-R is inert].

OH
O OH
O
OH
O O OH O NH2
O
OH
doxorubicin
Which of the following statements about doxorubicin are true?
1 Addition of sodium boron hydride causes six atoms of hydrogen to be

incorporated into the molecule.
2 On reacting with ethanoyl chloride, six moles of ethanoyl chloride is used up
trendyline
per mole of doxorubicin.
3 On
n reacting with thionyl
hionyl chloride, five moles of thionyl ch
chloride
chl is used
up per mole of doxorubicin.
doxorubicin

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A B C D
1 only is correct
40 A reaction pathway diagram is shown.
Which organic reactions could have such a profile?

H H
H H
C C + H SO H C C H
2 4
1
H H
H OSO3H
Br
2 + HBr
+ Br2
O O O
O O
C2H5 C2H5 base
+ H C2H5 C2H5
O O
O O
H H
3
HO
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PAPER

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2016 MJC H2 Chemistry Prelim Paper 1 (9647/01)
Suggested Answers
Qn Ans Qn Ans Qn Ans Qn Ans

1 C 11 D 21 C 31 C
2 D 12 B 22 C 32 A
3 D 13 B 23 D 33 B
4 D 14 C 24 C 34 A
5 C 15 D 25 B 35 B
6 D 16 B 26 B 36 A
7 B 17 D 27 C 37 B
8 B 18 D 28 C 38 D
9 B 19 A 29 B 39 B
10 D 20 C 30 B 40 A
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Calculator Model / No.
Name: ____________________ Class: 15S_________ Reg Number:

______
MERIDIAN JUNIOR COLLEGE

JC2 Preliminary Examination
Higher 2
__________________________________________________________________________
Chemistry 9647/02
Paper 2 Structured Questions 19September 2016
2 hours
INSTRUCTIONS TO CANDIDATES Examiners Use

Write your name, class and register number in the
spaces provided at the top of this page. Paper 1 MCQ / 40
Write your calculator brand and model/number in the Q1 / 12

box provided above.
Q2 / 17
Answer all questions in the spaces provided on the
question paper. Q3 / 15
All working must be shown clearly.
Paper 2 Q4 /9
INFORMATION FOR CANDIDATES Q5 /7
The number of marks is given in brackets [ ] at the Q6 / 12

end of each question or part question.
Total /72
clear presentation in your answers. Paper 3 / 80
Total / 192
Percentage
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e
Grade
This document consists of 28printed pages
MJC Prelim 2016

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1 Planning (P)
Lead iodide, PbI2 , is a sparingly soluble salt.
PbI2 (s) Pb2+ (aq) + 2I (aq)
One method of determining the relative solubility and an approximate value of

the solubility product of the salt, K sp , would be through direct observation. Two
standard solutions (one of a soluble lead(II) salt, and the other of a soluble
iodide salt) in different proportions are mixed and allowed to stand and reach
an equilibrium. In some mixtures, the ionic product of the particular solution
exceeds the K sp value and precipitation of PbI2 crystals will occur. In other
mixtures, the final concentrations of lead and iodide ions will be such that
precipitation does not occur.
The experimental ionic product can be determined for each solution. In the
experiment, the value of K sp lies between the ionic product values for solutions
with precipitate and those values for solutions without precipitate. The value for
K sp can be given as:
Maximum ionic product Minimum ionic product

<Ksp<
that does not gives ppt that givesppt
The value for K sp can be estimated by determining the mean between the
above two ionic products. In order for a more precise determination of K sp , the
concentration of the solution mixtures should be prepared in a manner that
would result in a relatively small range of ionic products.
In the experiment, two standard solutions of lead(II) nitrate and potassium
iodide are prepared and then diluted appropriately using relevant volumes of
the solutions and water. To avoid localised supersaturation that brings about
erroneous precipitation, water has to be mixed in first.
In order to predetermine the concentrations required, a student prepared two
solutions, A and B.
Solution A contains 2.50 cm3 of 0.0100 mol dm3 lead(II) nitrate, Pb(NO 3 ) 2
with 5.50 cm3 of deionised water added.
Solution B contains 2.00 cm3 of 0.0100 mol dm3 potassium iodide, KI.
Mixing these above solutions (at 25C) produced the yellow precipitate of PbI2 .
These solutions provide an ionic product which just exceeds the K sp of PbI2 .
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(a) Calculate the ionic product of PbI2 in this given mixture to determine a
rough estimate of the K sp value of PbI 2 .
[1]
(b) Consider the description of the precipitation experiment given in this

question.
Write a plan for such a series of four experiments to determine a value for
the K sp of PbI2 . In your plan, you should use the same total volume as
described when solutions A and B are mixed.
Your plan should ensure that

at least two of your experiments do not produce a precipitate
the estimated range for the value of K sp is relatively small. (< 10%
deviation from the estimated ionic product in (a)).
You should use the quantities specified in (a) in one of your experiments.
You may assume that you are provided with

solid lead nitrate, Pb(NO 3 ) 2
0.0400 mol dm3 aqueous potassium iodide, KI,
deionised water,
the equipment and materials normally found in a school or college
laboratory.
Your plan should include the following.

details, including quantities, for the preparation of a 100 cm3 stock
solution of 0.0100 mol dm3 of Pb(NO 3 ) 2
details, including quantities for the preparation of a 100 cm3 stock
solution of 0.0100 mol dm3 of KI
suitable format summarising appropriate quantities of solutions to
be used in each experiment (for four experiments),
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the corresponding concentrations and calculated ionic
centrations an ion products
outline of all essential experimental procedures
brief, but specific details on how the K sp value can be estimated
from the experiment.
[8]

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(c) Explain how the solubility of PbI2 would change if PbI2 is dissolved in a
solution of hydroiodic acid, HI.
[1]
(d) Lead(II) salts are toxic and prolonged exposure affects the mental
development in children. Pb2+ ions can be removed from contaminated
water through precipitation by adding a soluble salt solution containing the
appropriate anion.
The solubility products of some sparingly soluble lead(II) salts, at 25 C
are given in the table below.
Salt K sp
PbCO 3 7.4 1014 mol2 dm6
Pb(IO 3 ) 2 3.7 1013 mol3 dm9
Pb 3 (PO 4 ) 2 7.9 1043 mol5 dm15
Calculate the solubility of the above lead(II) salts in mol dm-3at 25C.
Hence, state the most effective anion in removing Pb2+ from the
contaminated water sample.
[2]

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2 Amines are a class of compounds that are widely used in both the
pharmaceutical and agricultural industry. An aminecontaining drug, Tamiflu is
an effective drug against the H1N1 strain of influenza A virus. Another amine,
ethylamine, CH 3 CH 2 NH 2 , is widely used in the production of herbicides.
(a) In order to determine the standard enthalpy change of neutralisation,
60.0 cm3 of 0.370 mol dm3 aqueous ethylaminewas placed in a
polystyrene cup. Dilute HCl was added and after each addition, the
mixture was stirred and the temperature noted.
The highest temperature reached was recorded and plotted on the graph
below.
Graph of temperature of mixture against volume of HCl added

30
X
X
Temperatue of mixture / C
X
29 X
X
X
28 X
X
27
26
0 10 20 30 40 50
Volume of HCladded / cm3
(i) Calculate the initial pH of aqueous ethylaminein the polystyrene cup.

Base dissociation constant of ethylamine is 5.6 104 mol dm3.
[1]
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(ii) Calculate the concentration of dilute HCl used in the experiment.
[1]
(iii) Calculate the enthalpy change of neutralisation for the reaction

between HCl and ethylamine.
(You may assume the density of the solutions is 1.00 g cm3 and
their specific heat capacity is 4.18 J g1 K1.)
[2]
(iv) With reference to your answer in (a)(iii), explain why the temperature
of the mixture was reported to be higher when the above experiment
was repeated using an aliquot of aqueous potassium hydroxide of
the same concentration as that of the ethylamine sample.
[1]
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(b) In another experiment, a sample of 0.640 mol dm3 aqueous ethylamine
was added to 10.0 cm3 dilute HNO 3 in a conical flask. The equivalence
point can be detected by a distinct colour change brought about by the
use of a suitable indicator.
The graph below shows the change in pH of the reaction mixture against
the volume of ethylamine added.
pH
Volume of ethylamine added / cm3
(i) Suggest a suitable indicator for this acidbase titration and state the
colour change observed at the equivalence point.
[1]
Indicator:
Colour
change:
(ii) Circle clearly on the graph, the region within which the mixture is
acting as a buffer.
[1]
(iii) Write an equation to suggest how the solution in (b) (ii) acts a buffer
upon the addition of a small amount of aqueous sodium hydroxide.
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[1]

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(c) An agricultural chemistsynthesised ethylamine from ethanal in an
industrial laboratory via a twostep procedure as shown in the scheme
below.
I II
CH 3 CHO CH 3 CH=NOH CH 3 CH 2 NH 2
NH 2 OH, H+
(i) Suggest the type of reactions for both steps and the reagents and
conditions for step II.
[2]
Step Type of reaction Reagents and conditions
II
(ii) Suggest a chemical test that the chemist can perform to confirm
that theprocedure is complete.
[1]
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(d) Use the following data and relevant data from the Data Booklet to
construct an energy cycle to calculate the enthalpy change of formation of
CH 3 CH 2 NH 2 (l).
Enthalpy change of vapourisation of CH 3 CH 2 NH 2 (l) = +29 kJ mol1
Enthalpy change of atomisation of C(s) = +715 kJ mol1
[3]
(e) The structure of Tamiflu is shown below.
O
O
O O
NH
NH2
(i) Name the two nitrogencontaining functional groups present in
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Tamiflu.
[1]

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(ii) Compound Q is a derivative of Tamiflu while compound R is an
aromatic compound with similar functional groups as Tamiflu.
O
O
O
O O O
O O
NH
NH
N
H CH3 NH2
compound Q compound R
Describe and explain the relative basicities of the following

compounds:
Compound Q and Tamiflu

[1]
Compound R and Tamiflu

[1]

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3 Halogens have a wide range of uses, such as in water purification and as
antiseptics. Halogens form compounds, such as halides and oxoanions which
are used in photography and as oxidising agents respectively.
(a) When potassium iodide reacts with concentrated sulfuric acid, violet
vapour is observedand a pungent gas is detected.
(i) Write achemical equationfor the reaction to account for the formation
of the violet vapour.
[1]
(ii) When potassium bromide reacts with concentrated sulfuric acid,

different observations are made.
By quoting suitable values from the Data Booklet, explain the

difference in the observations.
[2]
(iii) In order to prepare HBr as the only brominecontaining product from

KBr, concentrated H 3 PO 4 should be used instead of concentrated
H 2 SO 4 .
Suggest a plausible reason for this. Write a balanced equation for

this reaction.
[2]
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(b) Precipitates are formed whenaqueous silver nitrate is added to separate
tubes containing aqueous potassium chloride, aqueous potassium
bromide and aqueous potassium iodide.
(i) Describe the effect of adding concentrated NH 3 to each of the

resulting mixtures.
[1]
Tube containing KCl
Tube containing KBr
Tube containing KI
(ii) Provide a qualitative explanation to substantiate your answer for

observations in the tube containing KI.
[2]
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(c) 5.0104mol of a bromate salt containing theBrO 4 nanion was added to
20.0 cm3 of acidified KI present in excess to yield iodine and bromide
ions.
The remaining solution was made up to 250 cm3 with distilled water.
A 25.0 cm3 aliquot of the resultant solution required 40.0 cm3 of
0.010 mol dm3 sodium thiosulfate, Na 2 S 2 O 3 , for complete reaction.
Calculate the value of n.

[2]

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(d) When heated in chlorine, magnesium forms magnesium chloride.
Magnesium can also be heated in air to give magnesium oxide. Similarly,
aluminium and zinc can be vapourised and reacted with air to form the
respective oxides.
(i) Describe the reactions, if any, of magnesium chloride and

magnesium oxide with water, suggesting the pH of the resulting
solutions and writing equations where appropriate.
[3]
(ii) Zinc oxide has acidbase properties that are similar to aluminium
oxide. Write equations for two reactions which demonstrate these
properties of zinc oxide.
[2]

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4 The Williamson reaction is widely used in the laboratory and industrial
synthesis of ethers. It is the simplest and most popular method of preparing
ethers.
In a typical Williamson reaction, an alkoxide ion is prepared in situ and is

reacted with a halogenoalkane according to the general equation shown below.
RONa+ + RX
ROR + NaX
where R,R are alkyl groups and X is Br or Cl.
The following experimental procedure details the synthesis of

(3methylbutoxy)benzene using the Williamson reaction.
+
OH O Na O
Na (CH3)2CHCH2CH2Br
Stage 1 Stage 2
(3-methylbutoxy)benzene
PROCEDURE:
Preparation of (3-methylbutoxy)benzene
1 2.90 g of sodium metal is added to a dry round-bottom flask equipped with a

dropping funnel and a condenser. This apparatus set-up is shown below.
The set-up is protected from atmospheric moisture with the use of a calcium
chloride guard tube.
CaCl2 guard tube
dropping funnel
thermometer
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ndy
n
nd
dyylin
d condenser
round bottom flask ccontaining

reaction mixture

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2 Prepare an ethanolic solution containing 11.8 g of phenol. Add dropwise to the
reaction mixture using the dropping funnel. If the reaction becomes too vigorous,
cool the flask with a cold towel until the reaction is again under control.
3 Transfer 20.0 cm3 of 1-bromo-3-methylbutane to the dropping funnel and add it

to the flask slowly over 3 4minutes.
4 Boil the reaction mixture gently over a water bath for 30 minutes.
5 Evaporate as much of the ethanol solvent as possible.
Purification of (3-methylbutoxy)benzene
6 Add about 20 cm3 of water to the residue in the flask and separate the organic
layer using a separating funnel.
7 Wash the organic layer with sodium hydroxide.
8 Then, wash the organic layer with dilute sulfuric acid and water again.
9 Add anhydrous magnesium sulfateto the organic layer.

10 Distill the organic layer to purify (3-methylbutoxy)benzene at a suitable
temperature.
molar physical boiling

density / solubility in
substance formula mass / state at point /
g cm3 water
g mol1 r.t.p. C
ethanol C 2 H 5 OH 46 liquid 0.789 soluble 78
phenol C 6 H 5 OH 94 solid 1.07 insoluble 182
1bromo3methylbutane C 5 H 11 Br 151 liquid 1.21 insoluble 120
(3methylbutoxy)benzene C 11 H 16 O 164 liquid 0.91 insoluble 216
sodium bromide NaBr 103 solid 3.21 soluble
water H2O 18 liquid 1.00 100
Table 4: Physical Properties of the reagents and the organic product
(a) (i) Suggest why it is necessary to protect the apparatus setup from
moisture using the calcium chloride guard tube instep 1.
[1]
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(ii) Determine the theoretical yield (in g) of(3methylbutoxy)benzene for
this reaction. You may assume that the reaction between sodium
and phenol to form phenoxide in stage 1 is complete.
[2]
+
OH O Na O
Na (CH3)2CHCH2CH2Br
Stage 1 Stage 2
(3-methylbutoxy)benzene
(iii) On the diagram of the separating funnel below, label the two layers
that will be observed after step 6.
[1]
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e
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(b) Other than the crude product, the organic layer (Step 6) also contains
several impurities. These impurities comprises of unreacted reactants,
byproducts or products from undesired reactions.
In the purification of the crude product (Steps 6 9), the impurities are
removed from the crude product with each subsequent addition of
chemicals.
(i) Suggest the impurity removed by each of the chemicals below.
[1]
1 sodium hydroxide
2 anhydrous magnesium sulfate
(ii) With reference to the data provided in Table 4, account for the
observed boiling points of ethanol and the product,
(3methylbutoxy)benzene.
In your answer, you should state the predominant type of
interactions present in the two compounds.
[2]
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(iii) The final stage in the purification process is the distillation of the
crude product (Step 10).
Suggest why distillation is a suitable technique to obtain a pure
sample of (3methylbutoxy)benzene. Propose a suitable range of
temperature for the distillation setup.
[2]
[Total: 9]
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5 On 21st April 2016, famed American pop artiste, Prince Rogers Nelson died of
an accidental overdose of the drug, fentanyl.
Fentanyl, an opioid analgesic was first synthesised in 1960. It was primarily
used for pain relief in clinical practice. Its efficacy is about 100 times that of
morphine.
HO
N N
N
O HO
Fentanyl Morphine
Fentanyl can be synthesised from 2bromoethylbenzene following the reaction

scheme below.
HN O
Reactant A
Br N N
Step 1 N O
Step 2
Step 3 NaBH4
Cl
N N Intermediate B
pyridine
O Step
ep 4
Fentanyl

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(a) Name and outline the mechanism for the reaction in step 1. Show relevant
lone pairs and dipoles, and use curly arrows to indicate the movement of
electron pairs.
[2]
(b) Suggest the displayed formula of reactant A in Step 2.

[1]
(c) Propose the structure of intermediate B.

[1]

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(d) Propanyl chloride is used in step 4 in the synthesis of fentanyl.
Explain why the use of propanoic acid as a replacement in step 4 is not
suitable.
[1]
(e) Suggest achemical test that can be used to distinguish between fentanyl
and morphine.
[2]
[Total: 7]

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6 Copper forms compounds with variable oxidation states and these compounds
are used in numerous industries such as in wastewater treatment and as
mineral supplements.
(a) The following scheme illustrates the reactions between different

compounds of copper.
pink solid
Cu2SO4 H2O,
white solid filter
Rochelle salt blue solution
CuSO4
D
excess CH3CH2NH2 (aq)
deep blue solution

C
(i) State the full electronic configuration of copper in the white solid.
[1]
(ii) With reference to relevant E data from the Data Booklet, describe
and explain the type of reaction undergone when the white solid
dissolves in water.
[2]
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733 trendyline
(iii) Identify the species in solution C that is responsible for the deep blue
colour and account for its formation from CuSO 4 . Include a relevant
equation in your answer.
[2]
(iv) Solution D is formed when Rochelle salt (an aqueous solution of

potassium sodium tartrate KNaC 4 H 4 O 6 ) is mixed with a solution of
CuSO 4 in basic medium.
Use the following data to determine the chemical formula of the

copper tartrate anion complex.
The composition by mass of the elements is
Cu: 17.76 % C: 26.85% H: 1.68% O: 53.71%
The chemical formula takes the form of [ML 2 ]n.

[2]
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734 trendyline
(b) Copper(II) ions are commonly used as homogeneous catalysts in the
removal of harmful cyanide ions, CN from wastewater by hydrogen
peroxide to form the less harmful cyanate CNO ions as illustrated in the
following reaction.
CN (aq) + H 2 O 2 (aq)
CNO (aq) + H 2 O (l)
By considering relevant Evalues from the Data Booklet, explain how

copper(II) ions act as homogeneous catalyst in this reaction, writing
balanced equations where appropriate.
[3]
Given: CNO + H 2 O + 2e CN + 2OH E= 0.97 V
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735 trendyline
(c) When aqueous glycine solution is added to a heated ethanolic solution of
copper(II) ethanoate, light blue needles of a planar, neutral
copperglycinate complex is obtained upon cooling.
H2N
O
-

O
glycinate ion
(i) Draw the threedimensional structure of the copperglycinate

complex ion.
[1]
(ii) State the type of isomerism exhibited by the copperglycinate

complex ion.
[1]
[Total: 12]
END OF PAPER
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736 trendyline
2016 MJC Prelim P2 Suggested Answers
1 Planning (P)
(a) Ionic product = (2.50 10-3) (2.00 10-3)2= 1.00 10-8 mol3dm9.Show working
to consider total volume is different.
(b) Preparation of 0.01 moldm3Pb(NO 3 ) 2 standard solution (100 cm3)

1) Weigh a clean, dry empty weighing bottle using a mass balance.
2) Weigh out approximately 0.331 g of solid Pb(NO 3 ) 2 .
3) Transfer the solid into a clean 100 cm3 beaker and reweigh the
weighing bottle with the residue to determine the exact mass of
Pb(NO 3 ) 2 used.
4) Dissolve the solid carefully with some deionised water and transfer it
into a 100 cm3 volumetric flask.
5) Top up the flask to the mark with deionsed water, stopper and mix
well to obtain a homogeneous solution.
Dilution of KIstandard solution (100 cm3)
1) Pipette 25.0 cm3 of given 0.0400 moldm3 PbI2 solution into a

100 cm3 volumetric flask.
2) Top of top the mark with deionised water, stopper and mix well.
Possible quantities and concentrations of solutions to be used(4 expt sets)
Vol. of Vol of Vol of

[Pb2+] (mixture) [I ] (mixture) Ionic product of
Expt Pb2+ I H2O
/ moldm3 / moldm3 PbI2
/ cm3 / cm3 / cm3
5 2.50 2.00 5.50 0.00250 0.00200 y 1 : 1.00 108
6 1.00 3.00 6.00 0.00100 0.00300 y 2 : 9.00 109
7 2.00 2.00 6.00 0.00200 0.00200 8.00 109
8 1.50 2.00 6.50 0.00150 0.00200 6.00 109
9 1.00 1.00 8.00 0.00100 0.00100 1.00 109
Experimental procedure
1) Fill three 50.00 cm3 burettes with the prepared 0.0100 moldm3Pb(NO 3 ) 2
stock solution, 0.0100 moldm3 KI stock solution and deionised water
respectively.
trendyline
2) Run out o 1.00 cm3 of deionised 5.00 cm3 of KI into a 100 cm3
d water and 5
conical
ical
cal flask / beaker.
3) Run out 4.00 cm3 off Pb(NO 3 ) 2 into the conical flask / beake
beaker and swirl the
flaskk well / stir with a glass rod
rod.
4) Allow w the flask / beaker to stand undisturbed
un 30 min to attain
for at least 3
equilibrium.
MJC Prelim 2016 1 chemistry unit @ mjc

737 trendyline
5) Note if any precipitate of yellow PbI 2 is present on standing.
6) Repeat the experiment using the various volumes shown in table
(Total volume = 10.00 cm3 / constant).
7) Estimated K sp = y1+y 2 where y 1 : minimum ionic product with precipitation
2
and y 2 :maximum ionic product without precipitation.
(c) Solubility would decrease.

PbI2 (s) Pb2+ (aq) + 2I (aq) (1)

HI (aq) H+ (aq) + 2I (aq) (2)
Due to presence ofcommon ion (I ), equilibrium position of (1) shifts left.
(d)
Salt Solubility
s2 = 7.4 1014
PbCO 3 Solubility = s = 2.72 10-7mol dm-3
4s3 = 3.7 1013

Pb(IO 3 ) 2 Solubility = s = 4.52 10-5mol dm-3
108s5 = 7.9 1043

Pb 3 (PO 4 ) 2
Solubility = s = 1.49 10-9mol dm-3
Most effective: PO 4 3-
4
2(ai) [OH] = 0.370 5.610 = 0.01439 moldm3
pOH= lg 0.01439 = 1.84 hence pH = 12.2
(ii) No. of mole of ethylamine = 0.370 60 = 0.0222

1000
[HCl] = 0.0222 = 1.11 moldm3

20
1000
(iii) Heat absorbed by solution =80 4.18 3.5 = 1170 J

60
trendyline
ylline
e
No. of moles
ol of H 2 O produced = 0.370
37 = 0.0222
0
1000
0
1170
170
Enthalpyy change of neutralisation
neutralisatio = = 52.7 kJ mol11
=
=
0.0222
(iv) Some energy

nergy evolved from the neutralisation
utra process is u
used to further
dissociate the weak base completely

738 trendyline
(bii)
pH
3
Volume of ethylamine added / cm
(bi) Methyl orange.Red to orange.
(iii)CH 3 CH 2 NH 3 + + OH
CH 3 CH 2 NH 2 + H 2 O
(ci)
Step Type of reaction Reagents and conditions
I condensation
II reduction LiAlH 4 in dry ether
(ii) Add 2,4-DNPH to sample and heat.Synthesis is complete when no orange ppt is
observed. Accept other possible tests.
(d)
CH 3 CH 2 NH 2 (l) CH 3 CH 2 NH 2 (g)
H f [CH 3 CH 2 NH 2 (l)]
7 1
2C(s) +2 H 2 (g) + 2
N 2 (g)
5(410)+350+305+2(390)
7 1
2(715)+2(436)+2(994)
2C(g) + 7H(g) + 2N(g)
H f [CH
H f [CH trendyline
nd
dy
H 3 CH 2 NH
H 2 ((l)]
H 3 CH 2 NH
l)] + 29+3485 = 3453
H 2 ((l)]=
l)]
)]= 0 kJ mol11
= 61.0
6 .0
61
(ei) amide, amine

739 trendyline
(ii) Compound Q ismore basic than Tamiflu.Theelectron-donating R group
increases the electron density of the lone pair on N atom hence more
available to accept a proton.Compound Risless basic. The lone pair of
electron on N atom is delocalised into the benzene ring hence less available
to accept a proton.
3(ai) 8HI + H 2 SO 4
4I2 + H 2 S + 4H 2 O
(ii) E = +0.54 Vand E = +1.07 V. As E Br2/Br- is more positive than E I2/I ,Br is a
weaker reducing agent than I.
(iii)Conc. H 3 PO 4 is a weaker oxidising agent .than conc. H 2 SO 4

KBr(s) + H 3 PO 4 (l) HBr (g) + KH 2 PO 4 (s)
(bi) KCl: pptdissolves

KBr: ppt dissolves
KI: ppt does not dissolve
(ii) NH 3 ligand combines with Ag+(aq) to form diamminesilver(I) complex or

[Ag(NH 3 ) 2 ]+.Ionic product (of [Ag+][I]easily)exceed the low K sp value
hencethus AgIdoes not dissolve.
1
(c) Number of mole of iodine in 25.0cm3 aliquot = (0.0400 0.010)
2
Number of mole of iodine in 250 cm3 = 2.00 103
nI 2 2 103
4
nBrO 4n 5 104
Oxidation: 2I I 2 + 2e
Mole ratio: BrO 4 nI 2 H
Oxidation number of Br in BrO 4 n= +7
+7 + 4(2) = n(1)
n=1
trendyline
2+
(di)MgCl 2 (s) + 6H 2 O (l) 2Cll (aq)
[Mg(H 2 O)) 6 ] (aq) + 2
2C
[Mg(H 2 O)) 6 ]2+(aq) (OH +(aq) + H+(aq) pH
[Mg(H 2 O) 5 (OH)] H = 6.5
MgO (s) + H 2 O ((l)

l)) Mg(OH) 2 (aq
(aq)) S+
+
(ii)ZnO + 2HCll
ZnCl 2 + H 2 O
ZnO + 2NaOH + H 2 O
Na 2 Zn(OH) 4
740 trendyline
4(ai) Prevent the moisturefrom reacting with the sodium metal.
(ii)No. of moles of phenol = (11.8 / 94) = 0.1255( same as phenoxide)
No. of moles of 1-bromo-3-methylbutane = (20.0 x 1.21) / 151
Mass of (3-methylbutoxy)benzene = 0.1255 x 164 = 20.6 g
(iii)
Organic layer
Aqueous layer
(bi) 1 (unreacted) phenol; 2water
(ii) (3-methylbutoxy)benzene has a higher boiling point.The extensive van der

Waals forces of attraction between3-methylbutoxy)benzene molecules is
stronger than the hydrogen bonding in ethanol.
(iii) Boiling point of the (3-methylbutoxy)benzene is significantly higher than the

other impuritiesTemperature range is from 214 oC - 218 oC.
trendyline
741 trendyline
5(a)S N 2
-
+ Br
+ - + - O N C
C Br O N C Br H
O N H
H H
H
H H H H
[1/2]
[1/2]
[1/2]
O N C + HBr
H
H
(b)
H
(c)
N N
(d)Carboxylic acid will undergo acid-base reaction with the amine groups instead.
(e) Add aqueousneutral iron (III) chloride. For morphine, a violet complex observed but
not for fentanyl. Accept other tests.
trendyline
742 trendyline
6(ai) 1s2 2s2 2p6 3s2 3p6 3d10
(ii)E cell = 0.52 0.15 = + 0.37 > 0. Hence, Cu+disproportionatesinto pink solid Cu
and blue solution of Cu2+.
(iii)The stronger CH 3 CH 2 NH 2 ligands replace H 2 O ligandsto form a deep blue

complex[Cu(CH 3 CH 2 NH 2 ) 4 (H 2 O) 2 ]2+.
[Cu(H 2 O) 6 ]2+ + 4 CH 3 CH 2 NH 2 [Cu(CH 3 CH 2 NH 2 ) 4 (H 2 O) 2 ]2+ + 4H 2 O
(iv)
Cu C H O
% by mass 17.76 26.85 1.68 53.71
No. of moles 17.76 26.85 1.68 53.71
63.5 12.0 1.0 16.0
Simplest ratio 1 8 6 12
Chemical formula of anion is [Cu(C 4 H 3 O 6 ) 2 ]4
(b) E cell = 0.15 (0.97) = + 1.12V > 0 hence reaction is feasible.
2Cu2+ + CN +2OH
2Cu+ + CNO+ H 2 O
E cell = 1.77 0.15 = + 1.62V > 0 hence reaction is feasible.
H 2 O 2 + 2H+ + 2Cu+
2H 2 O + 2Cu2+
(ci)
O O- O- O O O- H2N
+
Cu2 Cu2
+
OR
NH2 H2N NH2 O- O
(ii) Cis-transisomerism
trendyline
743 trendyline
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2016 MJC Prelim Paper 3 Suggested Answers
1(a)
CH2I
CH3Cl, AlCl3 anhydrous PI3, heat

electrophilic substitution OR
.
NaI in conc H2SO4, heat
nucleophilic substitution
CH3
CH2OH
KMnO4, H2SO4 (aq) COOH .. .

heat LiAlH4 in dry ether, r t p
oxidation reduction
(b)
+ slow
Step 1: H C Br +
C
+ Br
~

H H H
Carbocation intermediate

f ast
Step 2: C
+ I H C I
H H H
(i) Add AgNO 3 (aq). Observation: No yellow precipitate observed.
(ii) The C 6 H 5 CH 2 + carbocation is resonance stabilised
(ci)
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KBr is
is precipitated out as a solid.
solid Position
Position of equilibrium shi
shifts
shif to the right.

762 trendyline
(ii)

O

O O

+ -

K ion dipole interactions
O O

O
(iii) Enthalpy change of solution for KI in propanoneis more exothermic.
(di) As a base.
(ii) BE (CI) = 240 kJ mol1 ; BE ( CBr) = 280 kJ mol1
The CBr bond is stronger than CI bond hence rate is slower.
(iii) Step III: alkaline KMnO 4 (aq), heat
Step IV: alkaline aqI2 , heat
StepV: hydrogen iodide
(iv)
H 2N
NH NO2 N
NH NO 2
+ + H 2O
O
NO2
NO 2
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2(ai) Zn + 2 OH
ZnO + H 2 O + 2e
O 2 + 2H 2 O + 4e
4 OH
2 Zn + O 2
2 ZnO
(ii) +1.59 = 0.40 E o (ZnO / Zn)

E o (ZnO / Zn) = 1.19 V
(iii) Prevent entry of O 2 so to minimise the batterys discharging process to prolong the
shelf-life of the battery.
(iv) Partial pressure of O 2 hence the equilibrium position shifts left. Eo (O2/OH) will be
less positive hence E cell < 1.59 V.
I t I 60 60
(v) No. of moles of O 2 = =
n F 4 96500
Current output of battery = 0.188 A
(bi) ZnCO 3 (s)

CO 2 (g) + ZnO (s)
(ii) Zn2+ 0.074 nm;Ba2+: 0.135 nm.Charge density: Zn2+> Ba2+.Zn2+ distorts the anion
charge cloud to a greater extent, weakening and breaking the CO bond in
CO 3 2.Hence, decomposition temperature of ZnCO 3 is lower than BaCO 3 .
(iii)
Zn2+(g) + C(s) + 3/2 O 2 (g) + 2e
o
H f (CO 3 2(g))
2nd IE Zn2+(g) + CO 3 2 (g)___
Zn+(g) + C(s) + 3/2 O2 (g) + e H latt

st
1 IE
Zn(g) + C(s) + 3/2 O 2 (g)
o
H at (Zn)
0 Zn (s) + C(s) + 3/2 O 2 (g)
o
H f
ZnCO 3 (s)
By Hess Law,H
aw,
w,H
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H latt ZnCO 3 ) = 3266 kJ mol
l (ZnCO
1

764 trendyline
(c) Zn is a heterogeneous catalyst because of the availability of 3d&4s electrons for
temporary bond formation with reactants.Reactant molecules are adsorbed onto
the Zn catalyst surface.This adsorption increases the surface concentration of
the reactants and weakens the covalent bonds lowering the activation energy
such that molecules are brought close for reaction to take place easily. Products
formed diffuse away from the surface of the catalyst.
(d)
Anode:zinc
object to be Graphite
coated with cathode
ZnO
dilute H2SO4
Anode :2H 2 O (l) O 2 (g) + 4H+ (aq) + 4e
Overall :2 Zn(s) + O 2 (g) 2 ZnO (s)
PV 1.01 105 103.7 10 6

3(ai) No of moles of NO 2 gas produced = =
RT 8.31 353
1
M r of atorvastatin = = 560
-3
1.785 10
(ii) NO 2 is a real gas with significant intermolecular forces of attraction.
(bi) No of tablets required in year = 2 x 365.

730
No of bottles needed = = 8.11 9
90
(ii) The weak van der Waals forces between the atorvastatin molecules is compatible
with that between CCl 4 molecules. The atorvastatin calcium cannot form ion
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dipole interaction
eraction
ra with the CCl
CCl 4 molecules,
cules, hence iti will not dissolve.
dissol

765 trendyline
(i)
O
O O
R slow R
N O R H N O
H H
R O-
O O
R R
N O N O
H+
H H
R O- R OH
O H O
(ii)
(di) NaBH 4 in ethanol
(ii) Nucleophilic substitution
O O O
H2N OH
(iii)
O
NC
(iv) O
(ei) The carboxylic acid group has higher K a .The carboxylate anion is resonance
stabilised.The alcohol has lower K a. The electron donating alkyl group increases
the intensity of the negative charge on the oxygen atom of the alkoxide anion
hence destabilising it.
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766 trendyline
(ii)
O O O
O H
N OH
HO
R
R NH3
F
4(ai) + rxn =2(1079) + 4(460) + 1(350) + 2(610) + 6(410) [ 5(350) + 2(740) + 2(360) +
2(460) + 8(410) = 122 kJ mol1
(ii) The difference is due to + fusion plusvaporisation of adipic acid.Accept other answers.
(iii) For adipoyl dichloride, the carbonyl C atom is bonded to electronegative atoms
hence the electron deficient carbonyl C atom is very susceptible to hydrolysis.
For compound A, the lone electron pair of the chlorine atom is delocalised with the
adjacent C=C double bond hence rendering partial double bond character.
..
..O
.. .. 2
-
..S O..
xx
.
O
. ..
.. .
x
..
x
xx
..
O
..
(bi)
(ii)
-
O O 2
O - O
- S O O or S O O
O O S O O S
O O
O O
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The shape
ape with respect to S is tetrahedral.
The shape
tetrahedral
ape with respect to O is bent

767 trendyline
(iii) Let y dm3.=vol of base added.
No. of mole of HA = 0.2y
Final no. of mole of H 2 A = 5 x 103 0.2y
0.2/(0.5+)
4.6 = 4.4 + lg(5 x 103 0.2)/(0.5+)
y = 0.0153 dm3
(ci) B undergoes acidic hydrolysis B is an ester.

C does not undergo condensation with 2,4dinitrophenylhydrazine.
C does not containaldehyde or ketone
C undergoes elimination with hot Al 2 O 3 .E to G contains alkene
E and F are cis-trans isomersandG contains chiral carbonandis a structural isomer
ofE&F.
D undergoes oxidation with Fehlings D contains aliphatic aldehyde.
Disethanedioic acid and it undergoes further oxidation to form carbon dioxide.
H OH
HO C
C CH3
CH3 H
Structure of C is
H H
H OH C C
CH3 OH
C C C C HO C H
CH3 CH3 H H
CH3
CH3
E F G
E and F (can interchange)
C OH
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d
H C
Structure
tructure
ructure of D is O

768 trendyline
O H OH
C O C
H C C CH3
O CH3 H
Structure of B is
(i)
O O
C OH C O- + Cu2O
+ 2 Cu2+ + 6OH- -
H C O C + 4H2O
O O
5(a) Quaternary structure is the combination of two or more polypeptide chains interacting
to form a more complex structure.The subunits in the structureinteract via van der
Waals forces, ionic bonds and hydrogen bonds.
(bi) [O 2 ] =
0.13 1.01 10 5
= = 5.30 x 103moldm3.Accept answer in mol m-3

8.31 298
1
K c = 0.33 = 62.3
5.30 10 3
(ii) G= (8.31) (298) ln (62.3)= 10.2 kJ mol1
(iii) S is negative since there is a decrease is disorder as there is a decrease in

number of moles of gas.H is negative .When temperature is high, IH I < I
TSI,hence G is positive hence oxygenation of squid is not supported leading to
death.
(iv) Cu(II) has partially-filled d orbitals. The d orbitals are split into two groups by
ligands. The d electron is promoted to the higher d orbital.During the transition, the
d electron absorbs red/orange/yellow wavelength light from the visible region of the
electromagnetic spectrum and the remaining wavelengths (blue) not absorbed will
appear as the colour observed.
(c) gly ile val glu gln cys cys ala ser val cys ser leu
(d) van der Waals

aals
als attraction between val
v andleu;
andleu
and leu;; h
hydrogen
ydrogen bond betw
between gln and ser;
disulfide bond
ond
nd between side chains of cys.
c

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(e)
H O H O H O
-
H2N C C N C C N C C O
HC H HC H H2C
H2C CH3H3C CH3 CH2
CH3 C -
O O
ile val glu
(fi) The plot is a straight line graph.[NaOH] is kept constant hence the rate is
independent of [NaOH]
(ii) k = = 8.21 x 1010Allow range of 8.0 8.4 x 1010
(iii) 8.21 x 1010 = k [1.5]

k = 5.47 x 1010
(g) pH 2.4pH 7.0
O O
-
HO -
O -
O O
+ +
O NH3 O NH3
and
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1
H
NATIONAL JUNIOR COLLEGE
SH2 PRELIMINARY EXAMINATION
Higher 2
CANDIDATE
NAME
SUBJECT REGISTRATION
CLASS NUMBER
CHEMISTRY 9647/01
Paper 1 Multiple Choice
Friday16Sept 2016
1 hour
Data Booklet
Write your name, subject class and registration number on the Answer Sheet in the spaces
provided unless this has been done for you.
There are 40 questions on this paper. Answer all questions. For each question there are four
Answer Sheet.
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This paper consists
s of
o 20 printed
ted pages
p
pages..
NJC/H2 Chem/01/2016 [Turn over

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2
Instructions on how to fill in the Optical Answer Sheet
Example:
Shade the index number in a 5 digit format on the optical answer sheet:2nd digit and the last
4 digits of the Registration Number.
Student Example of Registration No. Shade
Tan Ah Teck 1505648 55648
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3
Section A
For each question there are four possible answers A, B, C, and D. Choose the one you consider to
be correct.
1 3 g of hydrogen reacted with 160 g of bromine gas to give hydrogen bromide, HBr.
How many molecules are present at the end of the reaction?
A 6.02 1023 C 12.0 1023
B 9.03 1023 D 15.1 1023
2 In an experiment, 50 cm3 of a 0.1 mol dm3 solution of a metallic salt reacts exactly with
25 cm3 of 0.1 mol dm3 aqueous sodium sulfite.
The half-equation for the oxidation of sulfite ion is shown below:
SO 3 2(aq) + H 2 O(l) SO 4 2(aq) + 2H+(aq) + 2e
If the original oxidation number of the metal ion is +3, what is the new oxidation number of the
metal ion?
A 0 B 1 C 2 D 4
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4
3 The graph below shows the variation in the third ionisation energies for the consecutive
elements M to U in the Periodic Table, all with proton number below 20.
The symbols M to U do not represent the actual elements.
8000
6000
3rdIE / kJ mol1
4000
2000
0
M N O P Q R S T U
Elements
Elements
What can be deduced from the above graph?

A M has a noble gas configuration.
B M reacts with R to form compound MR 2 .
C The atomic radius of T is smaller than that of S.
D The decrease in 3rd I.E from O to P is due to inter-electronic repulsion.
4 Which set of compounds includes a giant ionic structure, a giant covalent structure and a
simple covalent structure?
A C 60 , C 2 H 5 CO 2 NH 4 , SiO 2 C CO 2 , Na 2 O, SO 2
B Al 2 O 3 , PbO, SiO 2 D AlCl 3 , P 4 O 6 , KHF 2
5 Which pair of species has the same bond angle?
A IF 3 , NF 3
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B NO 2 ,SO
O2
C XeF 4 , CF
F4
D O 3 2
NO 3 , CO

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5
6 Which statement best explains why iodine is a solid while water is a liquid at room
temperature?
A Iodine has a much larger molar mass than water.

B Iodine has stronger and more extensive covalent bonds between its atoms in its
molecular structure.
C The van der Waals forces of attraction between iodine molecules are stronger than the
intermolecular hydrogen bonding in water.
D The intermolecular hydrogen bonding in water is stronger than the intermolecular van der
Waals forces of attraction in iodine.
7 How does the volume of a 1.0 dm3 sample of gas change when it is heated from 20 C to40
C at constant pressure?
A It increases to about 1.1 dm3.

B It increases to about 2.0 dm3.
C It decreases to about 0.9 dm3.
D It decreases to about 0.5 dm3.
8 The data below refer to gas phase reactions at constant pressure.
CH 3 CH 3 CH 3 CH 2 + H H= +412 kJ mol1
CH 3 CH 2 CH 2 =CH 2 + H H= +168 kJ mol1
What is the enthalpy change for the following reaction?
2CH 3 CH 2 CH 3 CH 3 + CH 2 =CH 2
A +244 kJ mol1
B 122 kJ mol1
C 244 kJ mol1
D 580 kJ mol1
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6

The energy level diagram shown belowinvolves magnesium and water.
Mg2+(g) + 2H+(aq) + 2OH(aq) + 2e

Energy
/ kJ 116
B
Mg2+(g) + 2H2O(l) + 2e-
1926
Mg2+(aq) + 2H+(aq) + 2OH(aq)+ 2e
Mg(g) + 2H2O(l)
+146
Mg(s) + 2H2O(l) 796
C
Mg2+(aq) + 2OH(aq) + H2(g)
Which statement is incorrect?
A Step A represents the first and second ionisation energies of magnesium.
B Step B represents 2 H f (H 2 O).
C The enthalpy change for step C is 274 kJ mol1.
D The enthalpy change of hydration of magnesium ion is 1926 kJ mol1.
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7
10 Measured amounts of hydrogen and iodine are allowed to reach an equilibrium at 300 C in
a container of known volume.
H 2 (g)+ I2 (g) 2HI(g)
From which experimental method can the equilibrium constant, K c , be determined?
A measuring the total pressure in the container
B slow cooling to 25 oC, breaking open the container under aqueous potassium iodide,
and titrating the iodine present with aqueous sodium thiosulfate
C rapid cooling to 25 oC, breaking open the container under aqueous potassium iodide,
and titrating the iodine present with aqueous sodium thiosulfate
D withdrawal of a measured sample of the equilibrium mixture, followed by complete

decomposition of the hydrogen iodide present, and then titrating the total amount of
iodine with aqueous sodium thiosulfate
11 For the reaction:

2E(g) 3F(g)
the numerical values of the equilibrium constant, K p , are 1.50 107 at 500 K and 1.60 106
at600 K.
Which statement about the equilibrium is true?
A Decreasing the pressure increases the proportion of E in the equilibrium mixture.
B Adding a catalyst increases the proportion of F in the equilibrium mixture.
C The forward reaction is endothermic.
D The reaction is feasible at all temperatures.
12 The rate of removal of paracetamol, a pain-killing drug, from the body is a first order reaction
with a rate constant, k = 0.26 h1.
How long will it take to remove 75% of the paracetamol that a patient consumes?
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A 0.20 h B 0.26 h C 2.7 h D 5.3 h
5.

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8
13 Using a colorimeter, the following reaction is studied by finding the time taken for acoloured
reactant, A, to decolourise. The reaction is catalysed by Y.
A+B
Y
C + D
The following results are obtained:
Vol of solution added / cm3

Experiment Time taken / s
A B Y H2O
1 10 20 10 10 20
2 10 10 10 20 40
3 10 20 5 15 40
4 5 20 10 15 10
What is the rate equation for the reaction?
A rate = k[A][B] C rate = k[B][Y]
B rate = k[A][Y] D rate = k[A][B][Y]

Which reagent can be used to convert Na 4 Fe(CN) 6 to Na 3 Fe(CN) 6 ?
A Cl(aq) B Cu2+(aq) C Fe3+(aq) D Mn2+(aq)
15 Water dissociates into ions to establish following equilibrium:

H 2 O(l) H+(aq) + OH(aq)
Which is true about the dissociation of water?
A Dissociation of water is an exothermic process.
B When temperature increases, pH becomes lower than pOH.
C Water is only neutral at room temperature.
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D ure
re water, the values of its dissociation constant
For pure const (K product (K w ) and [H+]
(K a ), ionic pr
increase
ase in the order:
order K a <
<KK w < [H+].

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9
16 Bromocresol green indicator has a pH range of 3.8 5.5. It is yellow at pH < 3.8 and blue at
pH > 5.5.
Which statement about bromocresol green is incorrect?
A The indicator is suitable for a strong acidweak base titration.
B The indicator is yellow in 0.10 mol dm3 of an acid with K a = 105 mol dm3.
C The indicator is green in a solution containing equimolar concentrations of

CH 3 CO 2 H and CH 3 CO 2 K. (pK b of CH 3 CO 2 K = 9.24)
D When an acid in the conical flask is titrated against a base, the indicator changes
from yellow to blue at the end-point.
17 Four compounds of some Period 3 elements are listed below.
Na 2 O SiCl 4 SO 2 NaCl
Water is added separately to each compound. Pairs of the resulting solutions are mixed
together.
Which pair of solutions would give a solution of pH 7?
A NaCl and Na 2 O C NaCl and SO 2
B Na 2 O and SiCl 4 D SiCl 4 and SO 2
18 In the preparation of silicon, silicon dioxide is heated with magnesium.
SiO 2 + 2Mg 2MgO + Si
The product mixture contains only MgO and Si only.
To separate the silicon from the product mixture, a student proposed the following methods.
1 Shake the mixture with aqueous hydrochloric acid and filter.

2 Heat the mixture gently and collect the evaporated silicon.
Which methods would work?
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A 1 only
y C 1 and 2
B 2 onlyy D neither
neither 1 or 2

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10
19 The high UHDFWLYLW\RIIOXRULQHLVODUJHO\GXHWRWKHORZHQHUJ\RIWKH)F bond.
Which statement best DFFRXQWVIRUWKHZHDN))ERQG"
A The FF bond is weak because of the repulsion between the non-bonding electrons.
B The FF bond is weak because of the short bond length.
C The FF bond is weak because of the small nuclear charge of fluorine atom.
D The FF bond is weak because of the small size of fluorine atom.
20 7KHPROHFXOHLVRSURS\OFKROHVWDQHZKLFKKDVEHHQLVRODWHGIURPDFODVVRIVSRQJHFDQ
serve as a biomarker and has determined the first revolutionary appearances from some
species.
LVRSURS\OFKROHVWDQH
Carbon atoms in a hydrocarbon molecule are classified as primary, secondary, tertiary or

quaternary, depending on whether they are directly bonded to one, two, three or four other
carbon atoms.
How many tertiary and chiral carbon atoms are presentin a molecule of
LVRSUopylcholestane?
number of number of
tertiary carbon atoms chiral carbon atoms
A 9 4
B 9 8
tren
ndylin
n
C 11 4
D 11
1 8

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11
21 A reaction pathway diagram is shown below.
Which reactions could have this profile?
I (CH 3 ) 3 CBr + NaOH (CH 3 ) 3 COH + NaBr
II CH 3 CH 2 Br + NaOH CH 3 CH 2 OH + NaBr
III C 6 H 5 CH 2 Cl + NH 3 C 6 H 5 CH 2 NH 2 + HCl
IV (CH 3 ) 3 CCH 2 CH 2 Cl + NH 3 (CH 3 ) 3 CCH 2 CH 2 NH 2 + HCl
A Iand IIonly
B I and III only
C II and IV only
D II, III and IV only
22 The alkanes used to be known as the paraffin hydrocarbons paraffin meaning lack of
affinity (i.e. unreactive).
Which statement is best explains the lack of affinity in alkanes?
A The atoms are arranged tetrahedrally around each carbon atom.
B The alkanes have van der Waals forces of interaction.
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C DUHQRVLJQLILFDQWGLSROHPRPHQWVLQ& +DQ
+DQG& &ERQGV
7KHUHDUHQRVLJQLILFDQWGLSROHPRPHQWVLQ&+DQG&&ERQGV
D LVIUHHURWDWLRQDERXW&&VLQJOHERQGV
LVIUHHURWDWLRQDERXW&&VLQJOHERQGV
7KHUHLVIUHHURWDWLRQDERXW&&VLQJOHERQGV

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12
23 A new industrial preparation of ethyl ethanoate has been developed using cheap sources of
ethanol.
Which type of reaction is involved at some stage of this reaction sequence?
A nucleophilic addition
B condensation
C disproportionation
D reduction
24 Which compound is least likely to be prepareddirectly from methylbenzene?

COOH
CH3
Br
CH2Br
CH3
NO2
D
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13
25 Compound Y can be prepared from compound X in the following reaction sequence.
(CH2)4CH3
(CH2)4CH3
CH3
CH3
Step 1 O
OH C
C CH3
CH3 H2C
H2C
Compound X
Step 2
(CH2)4CH3
CH3
O(CH2)2CO2H
C
H2C CH3
Compound Y
Which reagents can be used to prepare compound Y?
Step I Step II
A Na CH 2 (OH)(CH 2 ) 2 CO 2 H
B NaOH CH 2 ClCH 2 CO 2 H
C NaOH CH 2 ClCH 2 CH 2 CO 2 H
D Na 2 CO 3 CH 2 (OH)CH 2 CO 2 H

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14
26 Compound Zis optically active and exists as zwitterions.
Which could be the structure ofZ?
A OH C CH(OH)CH3
CO2H
NO2
CH3
NH2
B H CH2CH3 D CH(NH2)CH3
H N C CO2H
CH2CH3
CO2H
27 Which isthe most feasiblesynthetic route?
A H H H H
aqueous NaOH acidified KMnO4
H C C H H C C H O C C O
heat heat
Br Br OH OH OH OH
B CH3 CH3 CO2H
Br Br
aqueous Br2 acidified KMnO4
FeBr3 heat
C OH OH OCOCH3
Br Br Br Br
aqueous Br2 CH3CO2H
conc. H2SO4, heat
Br Br
D O CH2I HO CH2I
CO2
NaBH4 I2
t nd e
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aqueous NaOH,
NaOH heat

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15
28 Compound Y gives a positive result when treated with [Ag(NH 3 ) 2 ]+and PCl 5 but a negative
result when treated with alkaline Cu(II) tartrate.
What could Y be?
A C
O O
OH
OH
B D
O O
OH
O O
29 What is the order of increasing pK a of the organic compounds?
A CCl 3 CH 2 OH, CHCl 2 CH 2 OH, CH 3 CO 2 H
B CH 3 CHClCO 2 H, CH 3 CH 2 CO 2 H, C 6 H 5 OH
C C 6 H 5 OH, CH 3 CHClCO 2 H, CH 3 CHFCO 2 H
D CH 2 ClCH 2 CO 2 H, CH 3 CHClCO 2 H, CH 3 CH 2 CO 2 H
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16
30 The first stage in the synthesis of compound P, a drug used in reducing fever, is the reaction
between compound O and phenylhydrazine.
CH3COCH2CO2CH2CH3 + NHNH2 P
O phenylhydrazine
What is P?
A
CH3COCH2CONH
B CH3
N C
CH2CO2CH2CH3
C CH3
N N C
CH2CO2CH2CH3
H
D CH2CH3
N N C
CH2COCH3
H
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17
Section B
be correct. Decide whether each of the statements is or is not correct (you may find it helpful to put
a tick against the statements that you consider to be correct.)
A B C D
1,2, and 3 are 1 and 2 only are 2 and 3 only are

1 only is correct
correct correct correct
31 For which pair does the first species contain more unpaired electrons than the second
species?
1 N, C+
2 Mn2+, Co2+
3 Mn4+, Co
32 Which reactions represent standard enthalpy changes?
1 NH 3 (g) + HCl(g) NH 4 Cl(s)

2 6C(s) + 6H(g) C6H6(l)
3
CH3OH(l) + O2(g) CO2(g) + 2H2O(g)
33 At 298 K, the numerical values for the dissociation constant of the aliphatic carboxylicacids,
RCO 2 H and R 1 CO 2 H in aqueous solution are 2.1 108 and 2.2 104 respectively.
Which statements can be inferred from the given information?
1 The pH of 1 mol dm3RCO 2 H is greater than 1 mol dm3R 1 CO 2 H.
2 The K b of RCO 2 is greater than that of R 1 CO 2 .
3 The acid strength of RCO 2 H is greater than that of R 1 CO 2 H.
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18
A B C D

1 only is correct
34 Which statements correctly describe the role of ammonia in the reactions below?
reaction role of ammonia
1 CuO + 6NH 3 [Cu(NH 3 ) 4 ]2+ + 2NH 2 + H 2 O Brnsted acid
2 2Na + 2NH 3 2NaNH 2 + H 2 oxidising agent
3 CH 3 Cl + NH 3 CH 3 NH 2 + HCl Brnsted base
35 Barium sulfate is opaque to X-rays and barium ions are toxic to humans. In hospitals, before
an X-ray examination is carried out, patients with digestive tract problems are sometimes
given a barium meal, consisting of a suspension of barium sulfate in water.
[Given: K sp of BaSO 4 = 1.3 1010 mol2 dm6; K sp of BaCO 3 = 5.5 1010 mol2 dm6]
Which statements regarding the barium meal are true?
1 Barium sulfate is used because it is insoluble in water and hence is not poisonous
when ingested by mouth.
2 Barium carbonate can be used since it is also insoluble in water.
3 Barium hydroxide can also be used since it is thermally stable in the human body.

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36 Deuterium, D, is the 21H isotope of hydrogen. DBr has the same chemical properties as HBr.
Which compounds could be made by the reaction of DBr with another compound in a single
reaction?
1 Br
D
2 CHBr 2 CHDBr
3 CH 3 CHBr(OD)
37 Which compounds form a single organic product when each is heated separately with
acidified potassium manganate(VII) solution?
1
CH3 CH3
CH3
3 CH 3 CH 2 CH 2 CH=CH 2
38 Ethyl propanoate, CH 3 CH 2 OCOCH 2 CH 3 undergoes acidic hydrolysis in the presence of

H 2 18O.
Which products are formed?
1 CH 3 CH 2 18OH
2 CH 3 CH 2 CO18OH
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3 CH
H 3 CH 2 OH

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20
A B C D

1 only is correct
39 The structure of benzene, C 6 H 6 , is a regular hexagon in which the electrons are described
as delocalised.
Which statements support this structure?
1 Benzene does not undergo addition reactions.
2 The length of the C-C bonds in benzene are intermediate between CC bond in an
alkane and C=C bond in an alkene.
3 The hydrogenation of benzene is less exothermic than that predicted forcyclohexa-

1,3,5-triene.
40 Aigialomycin D, a fungal metabolite, has the structure shown below.
OH O
HO
OH
OH
Aigialomycin D
Which observations arecorrect?
1 It reacts with hot, acidified K 2 Cr 2 O 7 to give a diketone.
2 One mole of AigialomycinD reacts with Na metal to produce 2 moles ofhydrogen.
3 It reacts with cold, dilute acidified KMnO 4 to give a product that has 7 chiral
centres in each molecule.
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H
NATIONAL JUNIOR COLLEGE
Higher 2
CANDIDATE
NAME
CLASS NUMBER
CHEMISTRY 9647/02
Paper 2 Planning Question
Wednesday 24Aug2016
For Examiners Use

Write your subject class, registration number and name on all

1 /12
the work you hand in.
You may use a soft pencil for any diagrams, graphs or rough
working.
Do not use paper clips, highlighters, glue or correction
fluid/tape.
Answers all questions.

The number of marks is given in brackets [ ] at the end of each

question or part question.
Total /12
trendylineThis document consists o

of 6printed
6printed pages
pages..
NJC PRELIM PLANNING QUESTION9647/02/16

803 trendyline
2 For
Examiners
Use
Answer the question.
1 Planning (P)
The solubility of silver chloride at a particular temperature, is defined as the mass of silver
chloride that can dissolve in and just saturate 100 g of a solvent at that temperature.
In a saturated solution in contact with undissolved solid, the following

equilibrium is established:
AgCl(s) + aq Ag+(aq) + Cl(aq) Ksp value = 1.8 1010
(a) A student was tasked to investigate the concentration of chloride ions in a sample of
sea water from the East Coast Park. Keeping in mind the low solubility of silver
chloride, she carried out her investigation through a method known as precipitation
titration, which is useful for reactions that yield ionic compounds of limited solubility.
In her investigation, solutions of chlorides were titrated with aqueous silver ions in the
presence of chromate ions. The end point of the titration occurred when almost all the
chloride ions have been precipitated and is signalled by the appearance of brick-red
silver chromate precipitate, Ag 2 CrO 4 .
The reactions are as follows:
2Ag+(aq) + CrO 4 2(aq) Ag 2 CrO 4 (s)
From the stoichiometry and amount of reactants used, the amount of chloride ions in
the sample of sea water can be determined.
Using the information given above, you are to plan an experiment to determine the
concentration of chloride ions in the sample of sea water.

a sample of 250 cm3 of sea water of approximate chloride concentration of
2.0 103 mol dm3
1.00 mol dm3 potassium chromate(VI) solution, K 2 CrO 4
0.1 mol dm3 silver nitrate solution
deionised water
the apparatus normally found in a school or college laboratory.

preliminary calculation to decide if the silver nitrate solution provided is suitable
for use in the titration
preparation of a standard silver nitrate solution from the 0.1 mol dm3 silver
nitrate solution provided, if necessary
trendyline
appropriate
ppropriate quantities of solutio
solutions
all essential experimental details
an outline of how the results would be used to determine th the concentration of
hloride ions in the sample of sea water
chloride wat
NJC/H2 Chem/02/2016[Turn over

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[6]

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5 For
Examiners
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(b) The student obtained a titre volume of 20.60 cm3from her experiment.
Determine the concentration of chloride ions remaining in the solution at the end point.
You may assume the following:
25.0 cm3 of sea water was used in the titration

1 cm3 of 1.00 mol dm3 potassium chromate(VI) solution, K 2 CrO 4 was used as
the indicator
K sp value of Ag 2 CrO 4 is 1.1 1012
[2]
(c) Subsequently, the student investigates the solubility of silver chloride in aqueous
hydrochloric acid.
By considering the ions present in a solution of silver chloride in aqueous hydrochloric

acid, predict and explain how the solubility of silver chloride will be affected by the
concentration of the acid.
Prediction:...................
Explanation:.........
....
....
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.

[2]
807 trendyline
6 For
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(d) Identify the following variables in the investigation of solubility of silver chloride in
hydrochloric acid.
Independent variable: .....
Dependent
variable: ....
[1]
(e) Calculate the solubility of silver chloride in a 2 mol dm3 hydrochloric acid solution.
[1]
[Total: 12]

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Suggested Answers for 2016 SH2 Chemistry Paper 2
(P) (a) Preliminary Calculation
3
For titration, 25cm of sea water is used,
3 3
Amt of Cl in 25.0 cm = 25/1000 x 2.0 x 10
5
= 5.0 x 10 mol
+
= Amt of Ag
3
Assuming titre volume to be 25.00 cm ,
5
Required [AgNO 3 ] = (5.0 x 10 )/25 x 1000
3 3
= 2.0 x 10 mol dm
3
Hence, the 0.1 mol dm silver nitrate solution provided is unsuitable for use in the titration (i.e. too
concentrated)
3 3 3
Need to dilute the given 0.1 mol dm silver nitrate solution to 2.0 x 10 mol dm
Need to dilute it 50 times.
3 3
Preparation of a standard silver nitrate solution of 2.0 x 10 mol dm
3
1. Using a burette, transfer 5.00 cm of the given silver nitrate solution into a 250
3
cm volumetric flask. Top up to the mark using deionised water.
2. Cap the flask, invert it and shake to obtain a homogeneous solution.
Precipitation Titration
3
1. Fill a burette with the newly-prepared 2.0 x 10 mol dm silver nitrate solution.
3 3
2. Pipette 25.0 cm of sea water into a 250 cm conical flask.
3
3. Add 1 cm of potassium chromate(VI) solution into the conical flask.
4. Titrate until brick-red precipitate first appears.
3
5. Repeat titration till results within 0.10cm are obtained.
Sample calculation of concentration of chloride ions in sea water

3 3
Let concentration of standard silver nitrate solution be Mmol dm , titre volume be y cm , volume
3
of sea water used for titration be 25.0 cm
+
Amt of Ag = y/1000 x M
= yM/1000 mol

= Amt of Cl

[Cl ] = yM/1000 25/1000
3
= yM/25 mol dm
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3
(b) The student obtained a titre volume of 20.60 cm from her experiment.
p
Determine point.
ne the concentration of chloride ions remaining in the solution at the end po
You mayy assume the following:

3
25.0 cm of sea water was used in the titration
titrat
824 trendyline
3
1 cm of 1.00 mol dm potassium chromate(VI) solution, K 2 CrO 4 was used as the indicator
12
K sp value of Ag 2 CrO 4 is 1.1 10
+ 10
Ag (aq) + Cl (aq) AgCl(s) K sp value = 1.8 x 10
+ 2 12
2Ag (aq) + CrO 4 (aq) Ag 2 CrO 4 (s) K sp value =1.1 x 10
2
Amt of CrO 4 = 1/1000 x 1.00
3
= 1.0 x 10 mol
2 3
At endpoint, [CrO 4 ] = (1.0 x 10 )/ [(25.0+1+20.60)/1000]
3
= 0.02146 mol dm
IP of Ag 2 CrO 4 = K sp
+ 2 2 12
[Ag ] [CrO 4 ] = 1.1 x 10
+ 2 12
[Ag ] [0.02146] = 1.1 x 10
+ 6 3
[Ag ] = 7.16 x 10 mol dm
IP of AgCl = K sp
+ 10
[Ag ] [Cl ] = 1.8 x 10
6 10
[7.16 x 10 ] [Cl ] = 1.8 x 10
5 3
[Cl ] = 2.51 x 10 mol dm
(c) Subsequently, the student investigates the solubility of silver chloride in aqueous hydrochloric acid.
By considering the ions present in a solution of silver chloride in aqueous hydrochloric acid, predict and
explain how the solubility of silver chloride will be affected by the concentration of the acid.
Prediction: Solubility of AgCl decreases when concentration of HCl increases.

+
Explanation: Ag (aq) + Cl (aq) AgCl(s)

In the presence of HCl, there is common ion effect. [Cl ] increases, position of equilibrium shifts
right, solubility decreases.
(d) Identify the following variables in the investigation of solubility of silver chloride in hydrochloric acid.

Independent variable: concentration of HCl / amount of HCl / concentration of Cl
Dependent variable: mass of AgCl that dissolved / solubility of AgCl / amount of AgCl that
dissolved
3
(e) Calculate the solubility of silver chloride in a 2 mol dm hydrochloric acid solution.
+ 10
[Ag ] [Cl ] = 1.8 x 10
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e
10
[x] [x+2.0]
0]] = 1.8 x 10
Assume
e x <<< 2.0,
10
10
[x] [2.0] = 1.8 x 10
825 trendyline
11 3
x = 9.00 x 10 mol dm
[1]
[Total:12]
1 One means of measuring toxicity is using LD, which stands for "Lethal Dose". LD 50 is the amount of a material which
causes the death of 50% of a group of test animals. LD 50 value is expressed as the weight of a chemical
administered per kg body mass of a test animal.
Another means of measuring toxicity is using LC, which stands for "Lethal Concentration". The concentrations of the
chemical in air that kills 50% of the test animals during the observation period is the LC 50 value.
The table below shows the values for the LD 50 and LC 50 along with the toxicity ratings.
Toxicity Commonly used 1

LD 50 : Oral (mg kg ) LC 50 : Inhalation (ppm)
Rating term
1 Extremely Toxic 1 or less 10 or less
2 Highly Toxic 1 50 10 100
3 Moderately Toxic 50 500 100 1000
4 Slightly Toxic 500 5000 1000 10,000
Practically Non-
5 5000 15,000 10,000 100,000
toxic
6 Relatively Harmless 15,000 or more 100,000 >
4
(a) 9.90 10 mol of a toxic compound, C 4 H 5 NO, was found to cause death in 50% of test animals weighing 1
kg.
Calculate the LD 50 of the compound and state its toxicity rating. [2]
4
Mass of compound = 9.90 x 10 x (48 + 5 + 14 + 16)
= 0.08217 g
0.19206 10 3
Hence, LD 50 = = 82.17 mg/kg
1
82.2 mg/kg [1]
The compound is moderately toxic/3 [1]
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826 trendyline
(b) Phosphine is a gas that is widely used in the semi-conductor industry as a dopant and as a precursor for the
deposition of compound semiconductors.
1
For safety of operations, the permissible limits of phosphine must not exceed of its LC 50 value.
10
When expressing a small quantity of gas, parts per million (ppm) can be used to indicate it. Ppm is usually
used for volume of gases and is expressed in the equation below:
volume of gas
Concentration in ppm = 106
volume of air
3
(i) Given that the LC 50 for phosphine is 55 mg m at room temperature, convert the LC 50 to ppm and
determine its toxicity rating. [3]
55 10 3 3
Volume of PH 3 = x 24 dm
34.0
3 3
= 1.6176 x 10 x 24 dm
3
= 0.03882 dm [1]
0.03882 103 6
LC 50 = 1
x 10
= 38.82
38.8 ppm [1]
The toxicity rating is highly toxic/2 [1]
(ii) A semiconductor factory releases 36 g of phosphine in a day.
Using your value in (i), determine the minimum volume of the factory that will allow the volume of
phosphine to be within permissible limits at room temperature.
[2]
Allowed amount of PH 3 in ppm = 38.82 10
= 3.882 ppm [1]
Given amount of of PH 3 produced a day is 36g

6
3.882 =
3
x 10
36
24 6
3.882 =
34

x 10
6 3
Minimum volume of factory = 6.546 x 10 dm [1]
[Total:7]
2 (a)
water. The
trendyline
Liquefaction
n of air is done industrially by surrounding pre-cooled
on
This behaviour
viour is not exhibited by ideal gases.
pre cooled high-pressure
high ressure air in a coil surrounded by cold
pressure.
e air cools down by a large amount when it expands into a region of low pre
827 trendyline
(i) State two assumptions of the kinetic theory of gases.
A gas is composed of tiny particles that have negligible volumes compared to the volume
in which they move or the volume of the gas container.
There are no attractive or repulsive forces between the gas particles.[2]
(ii) Suggest why air cools when it expands.
For expansion of air, energy is needed to overcome the intermolecular forces of

attraction between the air molecules, which is absorbed from the surroundings.
[1]
(iii) Conversely, gases can be liquefied at room temperature by compressing them under high pressure.
Explain why a gas liquefy when compressed.
When compressed, the gas particles are close enough for the intermolecular forces of
attraction to be significant and liquification occurs. [1]
(b) Critical temperature is the maximum temperature at which a gas can be converted into a liquid by an increase
in pressure. When the temperature is above the critical temperature, the vapour cannot be liquefied no matter
how much pressure is applied.
(i) Draw the dot - and - cross diagram for the N 2 O, where N is the central atom.
N NO N NO[1]
(iii) Arrange the gases N 2 O, F 2 and H 2 O, in increasing order of their critical temperatures and explain
your answer.
__F 2 ___ < __N 2 O_ < __H 2 O__
The hydrogen bonds between water molecules is the strongest, followed by the weaker
permanent dipole-dipole interactions between N 2 O molecules and the temporary dipole-
induced dipole between the F 2 molecules being the weakest.
Hence, H 2 O can remain as a liquid even at high temperature due to strongest

intermolecular forces and hence it has the highest critical temperature or the stronger the
intermolecular forces, a higher temperature is needed to convert the liquid to gas and hence
the higher the temperature.
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[3]
[Total:8]
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3 Hydrogen is a better source of fuel compared to fossil fuels as it is clean and renewable. The conventional method
of obtaining pure hydrogen is to electrolyse water. However, many industries still prefer fossil fuel or coal as the
main source of energy. One reason is the high cost of electrolysis.
(a) State another reason why the use of hydrogen as a fuel is not popular.
Hydrogen exists as a gas and it is difficult/high cost to store or transport.

Or
Hydrogen is dangerous as it is explosive.[1]
(b) The diagram below shows an alternative method of producing hydrogen from organic material where
ethanoic acid is converted by bacteria to carbon dioxide.
voltmeter
+
H
CH3COOH +
X Y
H
+
H
+ H
CH3COO
+
H
CH3COOH
Ion exchange membrane

(i) Complete the table below.
Electrode Type of reaction Polarity
X Oxidation Negative
Y Reduction Positive
[1]
(ii)
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Construct an equation for
f the reaction at each electrod
electrode.
829 trendyline
+
Electrode X: CH 3 COOH + 2H 2 O 2CO 2 + 8H + 8e
+
Electrode Y: 2H + 2e H 2 [2]
[Total: 4]
4 Chromium is a transition element which exhibits more than one oxidation state in its compounds, many of which are
coloured.
The flow chart below shows the reaction of a purple chromium(III) compound, X, which has a crystalline structure.
Purple crystal of X
water
Dark green solution
Portion 1 Portion 2
NaOH(aq) Zn(s) Acidified KMnO4(aq)

dropwise
Grey-green ppt Blue Orange solution

solution
Excess
NaOH(aq) NaOH(aq)
Dark green
Yellow solution
(a) (i) Write the electronic configuration of the chromium ion in A.

2 2 6 2 6 3
1s 2s 2p 3s 3p 3d [1]
(ii) Suggest an explanation for A being coloured.
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3+ 3+
When ligand approach Cr , the 3d orbitals of C
Cr splits
p into 2 different
diff energy levels (d-d
splitting).
When an electron in the lower energy d orbital is excited to the hhigher energy d orbital, a
photon with wavelength in the visible region is absorbed (d-d
(d-d
d transition).
tra
trans
830 trendyline
The colour of A observed is the complementary colour.
[3]
(b) (i) Explain why B dissolves in excess NaOH(aq) to form C. You should use the ideas behind the Le
Chaterliers principle and solubility product, K sp , in your answer.
3
B is Cr(OH) 3 and C is [Cr(OH) 6 ] .
3
Cr(OH) 3 + 3OH [Cr(OH) 6 ]
3
When excess OH is added, equilibrium shifts to the right to form [Cr(OH) 6 ] . This
3+
decreases the concentration of Cr and hence causing the ionic product of Cr(OH) 3 to
fall below its K sp . Therefore, Cr(OH) 3 dissolves.
Or
3+
Cr(OH) 3 Cr (aq) + 3OH (aq) Equilibrium 1
3+ 3
Cr + 6OH [Cr(OH) 6 ] -- Equilibrium 2
3
When excess OH is added, position of equilibrium 2 shifts right to form [Cr(OH) 6 ] . The
3+
concentration of Cr decreases and the ionic product of Cr(OH) 3 falls below its K sp .
(ii) Identify the chromium-containing species in D.

2+ 2+
[Cr(H 2 O) 6 ] or Cr (aq)
[1]
(iv) State the type of reaction and write an equation for the conversion of E to F.
Acid base reaction or Neutralisation reaction
2 2
Cr 2 O 7 + 2OH 2CrO 4 + H2O [2]
(c)
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Consider
der the two chromium complexes, [CrCl(NH
[CrCl
[CrCl(NH
(N 3 ) 5 ]SO 4 and [CrF(N
[CrF(NH 3 ) 5 ]C
]Cll 2 .
831 trendyline
(i) Describe a chemical test, which does not involve silver nitrate, that could distinguish between
aqueous solutions of [CrCl(NH 3 ) 5 ]SO 4 and [CrF(NH 3 ) 5 ]Cl 2 .
Add Ba(NO 3 ) 2 (aq) or BaCl 2 (aq) or Ba(OH) 2 (aq) or Ca(NO 3 ) 2 (aq). [CrCl(NH 3 ) 5 ]SO 4 will
form a white precipitate and [CrF(NH 3 ) 5 ]Cl 2 will not form any white precipitate or the
solution will remain colourless. [2]
2+ 2+
(ii) Explain why the ionic radius of Cr is much smaller than that of Ca .
2+ 2+
Cr has higher nuclear charge (more protons) than Ca and the electrons in the d
orbitals are poorly shielding. Therefore, the nuclear attraction on valence electron is
2+ 2+
higher in Cr and electrons are attracted closer to the nucleus in Cr . [1]
[Total: 12]
5 Piperidines are cyclic amines while pyridines are heterocyclic organic compounds structurally related to benzene.
N N
H
piperidine pyridine
(a) The structure of 2,3,5trimethylpiperidine is shown below.
N
H
It can be synthesised by reacting ammonia with a dibromo compound G.
NH 3 + C 8 H 16 Br 2 2,3,5trimethylpiperidine + 2HBr
G
(i) Suggest the structure of compound G.
trendyline
B
ren
Br
n Br
832 trendyline
(ii) When compound G is reacted with NaOH in ethanol, a mixture of isomeric alkenes with molecular
formula C 8 H 14 is formed.
Suggest the structures of all the isomers.
You may use skeletal representations in your answers.
2,4-dimethylhexa-1,5-diene geometirc isomers of 2,4-dimethylhexa-1,4-diene
(iii) Compound G can be converted to compound H by first converting it to a diol, followed by two more
steps as shown.
I II
G
HO HO O O
compound H
Complete the table below.
Step Reagents and Conditions Type of reaction
aqueous alkaline iodine / I 2 , NaOH(aq) / I 2 (aq), Oxidation

I
NaOH(aq); warm (not heat)
concentrated sulfuric acid (trace amount); heat Condensation

II
under reflxu
(b) The table below shows the pK b values of three monoprotic bases, ammonia, 2-ethylpiperidine and 2,3-
dimethypyridine.
NH
NH 3 N
ammonia 2-ethylpiperidine 2,3-dimethypyridine
pK b 4.74 3.55 7.43
(i) Give an equation which represents the reaction of 2-ethylpiperidine with water.
trend
tr d NH
+ H2O
NH2+
+ OH
833 trendyline
(ii) Explain why 2-ethylpiperidine has a lower pK b value than ammonia.
o
2-ethylpiperidine: 2 aliphatic amine with 2 electron-donating alkylgroups, lone ep of
+
N is readily available to be donated to H
Ammonia does not have any electron-donating alkyl group.
3
A 10.0 cm sample of J, a solution containing 2-ethylpiperidine and 2,3-dimethypyridine, was titrated
against 0.50 mol dm HCl(aq) in the presence of two indicators, bromothymol blue and methyl orange.
3
3
It was found that 12.20 cm of HCl(aq) were needed to change the colour of the first indicator and a
3
further 7.80 cm were needed to change the colour of the second indicator.
(iii) Use the data to calculate the concentration of each of the two bases in J.
In titrating a mixture of bases, the stronger or strongest base will be neutralised first.
2-ethylpiperidine in J = HCl to reach 1st eq pt
12.20
= x 0.50 = 6.10 103 mol
1000
12.20
x 0.50
[2-ethylpiperidine] in J = 1000 = 0.610mol dm3
10.0
1000
nd
2,3-dimethypyridine in J = HCl to reach 2 eq pt
7.80
= x 0.50 = 3.90 103 mol
1000
7.80
x 0.50
[2,3-dimethypyridine] in J = 1000 = 0.390mol dm3
10.0
1000
(iv) Calculate the initial pH of J.
3.88
K b (2-ethylpiperidine) is = 10 ( 7600) x K b (2,3-dimethylpyridine), 2-ethylpiperidine is
a much stronger base)
initial pH of solution J = pH of 2-ethylpiperidine in solution
[OH] = ([base] x K b ) = (0.610 x 103.55)
= 1.31 102 mol dm3
trendyline
pOH = 1.88, pH = 12.1
(v) Hence, sketch the shape of the pH curve during this titration, showing the
t pH values and volumes
of HCl(aq)
HC at significant points
points.
834 trendyline
- initial pH = 12.1
st 3
- pH at 1 max buffer capacity = 10.45 (= 14 3.55), 6.10 cm HCl(aq)
nd 3
- pH at 2 max buffer capacity = 6.57 (= 14 7.43), 16.10cm HCl(aq)
st 3
- 1 eq pt 12.20 cm HCl(aq)
nd 3
- 2 eq pt 20.00 cm HCl(aq)
- correct shape (2-steps)
pH
12.1
10.45
>7
6.57
<7
6.10 12.20 16.10 20.00

3
volume of HCl(aq) / cm
6
trendyline
The reaction scheme
cheme below shows the synthesis of compound
[The CH 3 O group
oup can be considered to b
compoun E starting
be inert.]
nert ]
arting from an alkene and a phenol derivative.
835 trendyline
OCH3
CH3CH=CH2
HO CH2CH3
OCH3
II
I
Compound A Compound B
NH(CH3)2
O CH3
OH CH3
N
HO COCl CH3
Compound D
OCH3
Compound C
O CH3
O H H
CH3
HO C O C C N
CH3
CH3 H
OCH3
Compound E
(a) (i) State reagents and conditions for steps Iand II.
Step I: KMnO 4 , dil H 2 SO 4 , heat

Step II: Cl 2 (aq) or Br 2 (aq)
(ii) Suggest the identities of compounds A and B.
A Compound B
O CH3 CH3 H
H C C H
HO CO2H
OH Cl
OCH3
(iii) Describe a mechanism for the reaction taking place in step II. In your answers, include all
necessary curly arrows, lone pairs and relevant dipoles.
trendyline
Electrophilic Addition
mechanism:
Detailed mechanism
H H
C C CH3 H
H
CH3 H C C H Cl
Cl Cl
Cl
CH3 H 836 CH3 H trendyline
H C C H H C C H
H
slow
+
Penalty:
any missing arrow/ wrong direction of arrow/arrow pointing to wrong atoms (for 1st
and 2nd step)
missing partial charge
2+LQVWHDGRI+2DWWDFNLQQGVWHS
missing slow step in 1st step
missing lone pair on nucleophile
(iv) State the type of stereoisomerism exhibited by D. Draw appropriate structures to illustrate your
answer.
Optical Isomerism
OH OH
N C H H C N
CH3 CH3
(v) Draw the organic product formed when compound A reacts with compound D.
trendyline
837 trendyline
OCH3
HO CO2 CH3CH(OH)CH2NH(CH3)2
OCH3
OCH3
O
HO
O
OCH3 N
- .
(b) Compound F is an isomer of E.
OCH3
O H H CH3
HO C O C C N
CH3 H CH3
OCH3 compound F
Describe a simple chemical test to distinguish between compounds E and F.
Add aqueous bromine:
E: yellow brown / orange bromine decolourises
F: yellow brown / orange colour remains
Or
Add liquid bromine:
E: reddish brown bromine decolourises
F: reddish brown colour remains
trendyline
838 trendyline
1
NATIONALJUNIOR COLLEGE
H
Higher 2
CANDIDATE
NAME
CLASS NUMBER
CHEMISTRY 9647/03
Paper 3 Free response
Monday 29 Aug 2016
2 hour
The use of an approved scientific calculated is expected, where appropriate.
At the end of the examination, fasten all your work securely behind the cover page.
The number of marks is given in brackets [ ] at the end of each question or part
question.
trendyline
NJC/H2Chem/03/2016 [Turn over
839 trendyline
2
This paper consists of 11 printed pages.
1 (a) Alums are salts formed when a monovalent cation with a large radius (e.g. K+
or NH 4 +) and a trivalent cation with a small radius (e.g. Al3+, Fe3+ or Cr3+)
combine with sulfate ions.
An ammonium iron alum has the formula (NH 4 ) a Fe(SO 4 ) b .12H 2 O.
To determine the chemical formula of the alum, two separate samples of

0.500 g of the alum were each dissolved in 100 cm3 of water.
An excess of NaOH(aq) was added to the first alum solution and the mixture
was boiled. The ammonia gas evolved exactly neutralised 5.2 cm3 of 0.200 mol
dm3 HCl(aq).
An excess of zinc was added to the second alum solution, which reduced Fe3+
to Fe2+, and the resulting solution was filtered. The filtrate collected required
10.4 cm3 of 0.0200 mol dm3acidified KMnO 4 (aq) for complete reaction.
(i) Calculate the amount of NH 4 + ions present in 0.500g of the alum. [1]
(ii) Write an equation for the reaction between the filtrate and acidified
KMnO 4.
Hence, calculate the amount of Fe3+ ions present in 0.500 g of the alum.
[2]
(iii) Using your answers in (i) and (ii), determine the values of a and b. [2]
(b) The Pauson-Khan reaction is a gas phase reaction between an alkyne, an

alkene and carbon monoxide to form a cyclic carbonyl compound, as shown
below.
O
Y
O Y
+ + catalyst
C
Y'
Y'
where Y and Y can be Cl or H.
nd
Cl and
trendyline
rganic
ganic compound A was produced from the Pauson-Khan
An organic
pound
ound has the following composition by mass; 51.5 % C, 13.7%
compound
d 4.3%
4 3% H.
H M r of A is 116.5.
116 5
Pauson-
Pauson-Khan reaction. The
13 O, 30.5%
840 trendyline
3
Upon heating with ethanolic AgNO 3 , Agave a white precipitate.
(i) Determine the molecular formula ofA and draw its structural formula.
[3]
(ii) By quoting relevant data from the Data Booklet and given that the bond
HQHUJ\ RI &2 LV N- PRO1, prove that the enthalpy change of
reaction in the Pauson-Khan reaction to form A LVN-PRO1.[2]
(iii) Predict the sign of the entropy change for the formation of Ain the above
reaction. Hence, deduce if the reaction is feasible at a high or low
temperature.
[2]
(iv) With the aid of a Boltzmann diagram, predict and explain the effect on
the rate of the Pauson-Khan reaction without a catalyst.
[3]
(c) Another possible product of the Pauson-Khan reaction is shown below:

O
CO2H
(i) Draw the product formed when B reacts with each of the following.
I. cold KMnO 4 (aq) in KOH(aq)

II. H 2 , Pt
III. LiAlH 4
[3]
(ii) Compound C is an isomer of B, and has the structure shown below:

O
CO2H
trendyline
C yl
841 trendyline
4
Deduce which compound, B or C, is more acidic.

[2]
[Total: 20]
trendyline
842 trendyline
5
2 Bovine serum albumin(BSA)is a serum albumin protein which is a main constituent of

cow milk. It is often used as a protein concentration standard in laboratory
experiments. The BSA molecule is a single chain of 607 amino acids, 66% of which
are incorporated into -pleated sheets. It is a globular protein and takes up a roughly
spherical shape in water.
Six of the most common amino acids in the BSA molecule are listed below.
Amino acid Formula of side chain

(R in RCH(NH 2 )CO 2 H)
Isoleucine -CH(CH 3 )CH 2 CH 3
Methionine -CH 2 CH 2 SCH 3
Tyrosine -CH 2 C 6 H 4 OH
Asparagine -CH 2 CONH 2
Lysine -CH 2 (CH 2 ) 3 NH 2
Asparate -CH 2 CO 2 H
Table 1
(a) (i) There are three pK a values associated with lysine: 2.17, 9.04, 12.48.
Make use of these pK a values to suggest the major species present in

aqueous solutions of lysine with the following pH values:
pH 1
pH 3
pH 10
pH 14
[4]
(ii) Suggest two positive tests (stating reagents, conditions and

observations) that could be used to confirm the identity of two amino
acids: asparagine and tyrosine.
[2]
(b) (i) Describe the conditions needed to hydrolyse a protein non-

enzymatically.
[1]
(ii) Briefly describe what is meant by the primary structure of proteins.
[1]
(iii) Describe how a polypeptide chain is held in the shape of a -pleated
trendyline
sheet.
[1]
(iv) With the aid of a diagram and using suitable amino acids from Table 1,
describe how hydrogen bondingding maintains the tertiary structure of
843 trendyline
6
proteins.
[2]
(v) The following recipe illustrates how a lemon sponge cake can be made.
Steps:
1. Cream butter and sugar until light and fluffy.

2. Beat in eggs.
3. Sift over the flour, add lemon juice and rind.
4. Bake for 10 minutes at 180C.
Suggest how any of the two steps described above can cause
denaturation, making specific reference to suitable pairs of amino acids
present in BSA.
[4]
(c) When a beam of 31T + particles is passed through an electric field, the angle of
P
deflection is found to be +5.00o. You may assume that all the 31T + particles
P
travel at the same speed through an electric field of constant strength.

(i) Calculate the angles of deflection if 31T + is replaced with the following,
P
leaving your answers to 2 decimal places:
32
S2
56
Fe3+
[2]
The mass of particle D is 25 times that of 31T +.When a beam of D is passed

P
through the same electric field asthat used for 31T +, the angle of deflection is
P
found to be +0.60o.
(ii) Determine the overall charge on a particle of D.

[1]
(iii) A particle of D contains 27 protons. Deduce the number of electrons in
this particle and hence write its electronic configuration.
[1]
(iv) A nuclear reaction is a reaction in which there is a change inthe atomic

nucleus.
An experimental nuclear reactor uses 13C and tritium, 31T , as fuel. A
trendyline
nuclear reaction between these two atoms are described below (n is a
neutron).
13
C + 3T X + n + 4He
H
844 trendyline
7
Suggest the identity of X with the aid of the Data Booklet.
[1]
[Total: 20]
3 (a) The kinetics of the hydrolysis of methyl ethanoate may be investigated by

determining the concentration of ethanoic acid produced.
CH 3 CO 2 CH 3 + H 2 O CH 3 CO 2 H + CH 3 OH
In a 1 dm3vessel, 0.350 mol of CH 3 CO 2 CH 3 was heated with dilute

hydrochloric acid which acted as a catalyst. The following results were
obtained.
Time / s [CH 3 CO 2 H] / mol dm3

0 0
340 0.105
680 0.185
1080 0.243
1440 0.278
(i) What is meant by the term order of reaction?

[1]
(ii) By drawing a suitable graph using the data given above, determine the
order of reaction with respect to methyl ethanoate.
[3]
(iii) Given that the hydrolysis reaction is first order with respect to
hydrochloric acid, write the rate equation for this reaction.
[1]
(b) Esters can also undergo reduction in the presence of a strong reducing agent
such as lithium aluminium hydride, LiAlH 4 . The reaction produces two alcohols.
RCO 2 R RCH 2 OH + ROH
Using this information, and that provided below, draw out the full mechanism
trendyline
for the
he
e formation of ethanol from methyl ethanoate.
ethanoate
ere is an initial nucleophilic attack by hydride ion, H, on the ester to

There
here
enerate
nerate a negatively charged ion.
generate io
ion.
The
he C=O bond reforms and the OR OR group is eliminated from
O f the ester,
845 trendyline
8
forming an aldehyde.
A second hydride ion attacks the aldehyde to generate an alkoxide ion.
The alkoxide ion is then protonated to form the alcohol.
[3]
(c) Besides esters, nitriles can also undergo reduction to give aldehydes in the
presence of another strong reducing agent, diisobutyl aluminium hydride
(DIBAL).
RCN RCHO
(i) By considering the change in oxidation states of the reacting carbon,

suggest why the conversion of a nitrile to an aldehyde is a reduction
reaction.
[1]
CH2Br 4 steps
CH2CH(OH)CO2H
Compound E
(ii) Compound E can be synthesised using DIBAL as a reducing agent in

one of the steps above.
Suggest the reagents and conditions required for each step of synthesis
and identify all the intermediate compounds.
[5]
(d) A Wittig reagent can convert an aldehyde to an enone, a ketone with an

adjacent double bond.
O O
Ph3P R' CHO R'
R R
Wittig reagent enone
(wKHUH3KUHSUHVHQWV& 6 H 5 )
Wittig reagent F was reacted with an aldehyde G to give an enone H. H was

then reacted with hot acidified potassium manganate(VII) to give two different
trendyline
compounds,
ounds, J and K.
pounds,
H cann also be synthesised
synthesised by the following route.
synthesis
846 trendyline
9
OH
ethanolic NaOH hot acidified K2Cr2O7
heat
L H
enone
Cl
(i) Suggest the identities of compounds H, J, Kand L. [4]
(ii) Suggest the identities of compounds F and G. [2]

[Total: 20]
4 (a) The question below is related to some compounds of Group II elements.

(i) Write an equation, with state symbols, for the thermal decomposition of
strontium nitrate.
[1]
(ii) Use the Data Booklet to explain how the thermal stability of zinc nitrate
might compare to strontium nitrate. [3]
(iii) The chemical properties of beryllium and its compounds show similarity
to those of aluminium. Beryllium form complexes of coordination number
4.
I. Aluminium chloride, AlCl 3 , dimerises to form Al 2 Cl 6 .

Draw the displayed formula of Al 2 Cl 6 , showing clearly the bond
angle about Al.
[1]
II. Explain why AlCl 3 dimerises. [1]
III. Explain, using a relevant equation, why a solution of beryllium

chloride is acidic. [2]
IV. Beryllium oxide, similar to aluminium oxide, is amphoteric.

Suggest the nature of bonding in beryllium oxide.
[1]
V. Write equations for the reaction of beryllium oxide with HCl(aq)

and NaOH(aq). [2]
(b) Capsaicin is a slightly acidic compound responsible for the burning sensation of
chilli peppers. Its molecular structure can be deduced by the following reaction
scheme.
trendyline
[Assumem that OCH 3 group is inert.]
ume inertt.]
847 trendyline
10
boil with H+ NH2

C18H27NO 3 + C10H18O 2
Capsaicin N
HO
OCH 3
M
(i) When N is heated with concentrated acidified potassium

manganate(VII), P, C 6 H 10 O 4 , and Q, C 4 H 8 O, are formed.
P is formed from the reaction of Br(CH 2 ) 4 Br with hot ethanolic KCN

followed by hydrolysis. Q can be reduced to an alcohol, R, which is
optically active.
Deduce the structures of N, P, Q, R and capsaicin.

[5]
(ii) Draw the organic compound formed when M reacts with CH 3 CH 2 COCl.
[1]
(c) Peroxodisulfate(VI) ion, S 2 O 8 2-, is capable of oxidising tartaric acid,

(CH(OH)CO 2 H) 2 , to carbon dioxide and methanoic acid.
The Eo cell of the reaction is +0.99 V.
(CH(OH)CO 2 H) 2 + 3S 2 O 8 + 2H 2 O 2CO 2 + 2HCO 2 H + 6H+ + 6SO 4
The reaction is very slow, even when temperature is increased.

However, the reaction rate can be increased by adding a suitable catalyst.
The half equation for the reduction of carbon dioxide to tartaric acid is
2CO 2 + 2HCO 2 H + 6H+ + 6e(CH(OH)CO 2 H) 2 + 2H 2 O
Using the Data Booklet, show how cobalt(III) ion can act as a homogenous
catalyst.
[3]
[Total: 20]
trendyline
848 trendyline
11
5 (a) Chlorine is manufactured from brine (concentrated NaCl) by electrolysis using

inert electrodes at room temperature. The anode and cathode compartments
are separated by a diaphragm which is a permeable membrane.
BrineCl2(g)Gas S
Compound T
Diaphragm
trendyline
n
(i) Suggest
gg the identities of g
gas S and compound
p T. [1]
(ii) Using relevant Eodata ta from th

the Data Booklet, suggest
ggest a reason
re why the
electrolysis of dilute NaC (aq) produces mainly oxygen at
NaCl(aq) a the anode,
whereas the electrolysis of brinee produces
pr mainly chlorine gas.
g
849 trendyline
12
[2]
(iii) Suggest the products that might be formed if the diaphragm is removed
and the solution is stirred. Write an equation for any reaction that occurs.
[1]
(b) Orchids can be made into jewellery that gleams with either a reddish tint of
copper or shiny gold. In copper-plating, orchids are coated with a thin layer of
graphite paste before placing them in a bath of aqueous copper(II) sulfate and
electroplating.
(i) Suggest a reason why orchids are first coated with graphite. [1]
(ii) To ensure high standards of electroplated orchids, the copper coating

must be at least 0.5 mm thick. Given that the total surface area of a
typical orchid is 10 cm2 and the operating current is 20 A, calculate the
time required to electroplate an orchid.
[Density of copper = 8.96 g cm3]
[3]
trendyline
850 trendyline
13
(c) The use of Data Booklet is relevant to this question.
When iron is heated with bromine, FeBr 3 is produced. However, when heated
with iodine, FeI 2 is produced instead.
(i) Write the two equations for the formation of FeBr 3 .

[2]
(ii) Hence explain why when iron is heated with iodine, FeI 2 is produced but
notFeI3 . [2]
(iii) An unknown elementUis diatomic and is below iodine in Group VII of the
Periodic Table. The hydride of U, HU, and hydride of iodine, HI, differ in
their physical properties and reactivities.
(I) Suggest and explain how the polarities of H-U and H-I bonds
differ.
(II) Suggest and explain how the boiling points of HU and HI

differ.
(III) Suggest and explain how the acidities of HU and HI differ

when dissolved in water.
[4]
(d) Methane and steam react to give hydrogen and carbon monoxide as follows.
CH 4 (g) + H 2 O(g) 3 H 2 (g) + CO(g)
A mixture of 3.0 mol of CO and 8.0 mol of H 2 is heated in a closed container of

2 dm3 and allowed to reach dynamic equilibrium at 300 K. The amount of
hydrogen at equilibrium was found to be 6.5 mol.
(i) Determine the amounts of methane and steam at equilibrium.

[2]
(ii) Write the expression for the equilibrium constant, K c , for the above
equilibrium and calculate the K c at 300 K.
[2]
[Total: 20]
851 trendyline
Suggested answers for 2016 SH2 Chemistry Paper 3
+ +
1 (a) Alums are salts formed when a monovalent cation with a large radius (e.g. K or NH 4 ) and a trivalent cation with a
3+ 3+ 3+
small radius (e.g. Al , Fe or Cr ) combine with sulfate ions.
An ammonium iron alum has the formula (NH 4 ) a Fe(SO 4 ) b .12H 2 O.
To determine the chemical formula of the alum, two separate samples of 0.5 g of the alum were each dissolved in 100
3
cm of water.
An excess of NaOH(aq) was added to the first alum solution and the mixture was boiled. The ammonia gas evolved
3 3
exactly neutralised 5.2 cm of0.200 mol dm HCl(aq).
3+ 2+
An excess of zinc was added to the second alum solution, which reduced Fe to Fe , and the resulting solution was
3 3
filtered. The filtrate collected required10.4 cm of 0.0200 mol dm acidified KMnO 4 (aq) for complete reaction.
+
(i) Calculate the amount of NH 4 ions present in 0.5 g of the alum. [1]
HCl + NH 3 NH 4 Cl
+ 5.2 3
Amount of NH 4 = x 0.200 = 1.04 x 10 mol [1]
1000
(ii) Write an equation for the reaction between the filtrate and acidified KMnO 4.
3+
Hence, calculate the amount of Fe ions present in 0.5 g of the alum. [2]
2+ 3+
[O] Fe Fe +e
+ 2+
[R] MnO 4 + 8H +5e Mn + 4H 2 O
2+ + 2+ 3+
Overall: 5Fe + MnO 4 + 8H Mn + 4H 2 O + 5Fe []
10.4 4
Amount of MnO 4 = x 0.0200 = 2.08 x 10 mol []
1000
3+ 4 3
Amount of Fe = 2.08 x 10 x5 = 1.04 x 10 mol [1]
(iii) Using your answers in (i) and (ii), determine the values of a and b. [2]
3+
There is 1Fe per formula unit of (NH 4 ) a Fe(SO 4 ) b .12H 2 O
3+ 1.04 10 3 1
= =
4+ 1.04 10 3 1
Hence, a =1 [1]
Comparing the charges of the ions:
b) =0
b =2 [1]
or
0.5
M r of compound = = 480.77
1.04 10 3
Given than a= 1, 14.0 + 1.0 x 4 + 55.8 + (32.1 + 16.0 x 4) b + 12 x (16.0 + 2.0) = 480.77
b
(b) The Pauson-Khan reaction is a gas phase reaction between an alkyne, an alkene and carbon monoxide to form a
cyclic carbonyl compound, as shown below.
Y O
O Y
+ + catalyst
C
Y'
Y'
trendyline
where Y and Y ca
can be Cl or H.
An organic compound
mpound A was produced from the Pauson
Pauson-Khan has the following composition
an reaction.The compound h
by mass; 51.5 % C, 13.7% O, 30.5% Cl and nd 4.3% H. M r of
o A is 116.5
116.5.
th ethanolic AgNO 3 , A gave
Upon heating with ve a white precipita
precipitate.
852 trendyline
(i) Determine the molecular formula of A and draw its structural formula. [3]
C O Cl H
% by mass 51.5 13.7 30.3 4.3
Relative amount / mol 4.29 0.856 0.853 4.3
Simplest ratio 5 1 1 5
[1] for table
Empirical formula of A: C 5 H 5 OCl
Let molecular formula of Abe (C 5 H 5 OCl) n
n(12.0 x 5 + 1.0 x 5 + 16.0 + 35.5) = 116.5
n =1
O
Molecular formula of A= C 5 H 5 OCl [1] Cl [1]
1
(ii) By quoting relevant data from the Data Booklet DQGJLYHQWKDWWKHERQGHQHUJ\RI&2LVN-PRO , prove
1
that the enthalpy change of reaction in the Pauson-Khan reaction to form A LVN-PRO . [2]
Bonds broken:1 &21 &&1 C=C

Bonds IRUPHG&&& && 2 [1]
+ = BE (bonds broken) BE(bonds formed)
1
= 1079 + 840 + 610 [ N-PRO [1]
(iii) Predict the sign of the entropy change for the formation of A in the above reaction. Hence, deduce if the
reaction is feasible at a high or low temperature. [2]
There is a decrease in the number of gaseous particles, hence there is a decrease in the degree
of disorderliness; entropy decreases or S is negative. [1]
Both + DQG 6 DUH of negative values; temperature must be low enough for 76
+VXFKWKDW*. [1]
(iv) With the aid of a Boltzmann diagram, predict and explain the effect on the rate of the Pauson-Khan reaction
without a catalyst. [3]
Marking
trendyline
g points
- y-axis:
xis:
- start
roportio number of particles;
is proportion/
rt from zero (origin)
- peak
(orig
particles x-axis:
ak of the graph lies on the left half

- graph plateaus off towards the end
axis energy
x-axis: energ / kinetic energy
853 trendyline
- labelling of particles with energies above E a and E a
Total marks for graph:[1]; each point missing:[-]
Without a catalyst, the activation energy will be higher, thus there are fewer particles [] with
energy greater than or equal to the activation energy, resulting in lower frequency ofeffective
collisions[] and rate of the reactiondecreases.[]
(c) Another possible product of the Pauson-Khan reaction is shown below:

O
CO2H
B
(i) Draw the product formed when B reacts with each of the following.
I. cold KMnO 4 (aq) in KOH(aq)
II. H 2 , Pt
III. LiAlH 4
[3]
O
OH OH
CO2- K+
HO CO2H CH2OH
I. HO II. III.
[1]each
(ii) Compound C is an isomer of B, and has the structure shown below:

O
CO2H
C
Deduce which compound, B or C, is more acidic.[2]
C is a stronger acid than B. [1]

The delocalisation of lone pair of electrons from Oin CO 2 to the overlapped p orbitals in C=O
and C=C helps to disperse the negative charge on the conjugate base (carboxylate anion) of C,
O- , to a greater extent than that of B,making the anion of Cmore stable. [1]
[Total: 20]
2 Bovine serum albumi, BSAis a serum albumin protein which is a main constituent of cow milk. It is often used as a protein
concentration standard in lab experiments. The BSA molecule is a single chain of 607 amino acids, 66% of which are
incorporated into a -pleated sheet. It is a globular protein and takes up a roughly spherical shape in water.
Six of the most common amino acids in the BSA molecule are listed below.
trendyline
trendy
e dyyline
e
Amino acid Formula
Fo of side cha
chain
(R in RCH(NH 2 )CO 2 H H)
Isoleucine -CH(CH
CH(CH 3 )CHCH 2 CHH3
Methionine -CH
-CH
C 2 CH 2 SCH 3
Tyrosine -CH
-CH 2 C 6 H 4 OH
Asparagine -CH 2 CONH 2
Lysine
L i -CH
CH 2 CH 2 CH 2 CH 2 NH 2
Asparate -CH 2 COOH
3
854 trendyline
Table 1: Types of amino acid
(a) (i) There are three pK a values associated with lysine: 2.17, 9.04, 12.48.
Make use of these pK a values to suggest the major species present in solutions of lysine with the following pH values:
pH 1
pH 3
pH 10
pH 14
[4]
H H H
H
H 3N + C COOH H 3N + C COO- H2N C COO-
-
H2N C COO
(CH2)4 (CH2)4
(CH2)4
+ (CH2)4
+
NH3 NH3 NH2
+
NH3
pH 1 pH 3 pH10 pH14
(ii) Suggest two positive tests (stating reagents and observations) that would enable the amino acids asparagine and
tyrosine to confirm their identities. [2]
[1 each]
Test 1: Add NaOH(aq), warm
Observations: Tyrosine: no evolution of alkaline gas which turns red litmus paper blue;
Asparagine: alkaline gas evolves, turns red litmus paper blue.
Test 2a:Add neutral FeCl 3 (aq)
Observations: Tyrosine: purple complex forms; Asparagine: no purple complex forms.
Test 2b: Add Br 2 (aq)
Observations: Tyrosine: yellow / orange solution decolourised; Asparagine: yellow / orange solution
remains.
(b) (i) Describe the conditions needed to hydrolyse a protein non-enzymatically. [1]
HCl(aq)/H 2 SO 4 (aq); prolonged heating

or
NaOH(aq)/KOH(aq); prolonged heating
(ii) Briefly describe what is meant by the primary structure of proteins. [1]
Primary protein structure is a unique sequence of amino acids joined by peptide bonds in a polypeptide
chain.
(iii) Describe how a polypeptide chain is held in the shape of a -pleated sheet. [1]
The polypeptide backbone (polypeptide chain) is folded into -pleatedsheet.It is maintained through
hydrogen bonding found at regular intervals between N-H group of one peptide and C=Ogroup of
another peptide of the polypeptide backbone.
(iv) Using suitable amino acids in Table 1, describe hydrogen bonding interaction in the tertiary structure of proteins with
the aid of a diagram. [2]
855 trendyline
Tyrosine/Lysine/Asparate/Asparagine [1] [1]
(v) The following recipe illustrates how a lemon sponge cake can be made.
1. Cream butter and sugar until light and fluffy.
2. Beat in eggs.
3. Sift over the flour, add lemon juice and rind.
4. Bake for 10 minutes at 180C
Suggest how the above changes can cause denaturation, making specific reference to suitable pairs of amino acids
present in BSA. [2]
Beat in eggs:Mechanical agitation can break the weak interactions (van der Waals and Hydrogen
bonding) that hold the configuration of the protein together. (Isoleucine, Methionine, Tyrosine,
Asparagine) [2]
Add lemon juice:Destruction of ionic bonds occurs extensively at extreme pH conditions.

+
Adding acids: H + COO COOH
+
H from acids reacts ZLWK&22 on R groups of amino acid residues to formCOOH.Ionic bonds present
are broken. (Lysine and Asparate) [2]
Bake for 10 minutes at 180C: Energy supplied is sufficient to overcome the intermolecular
interactions/ionic bonds which hold the configuration of the protein together.(any pairs of amino acids)
[2]
+ o
(c) When a beam of 31T particles is passed through an electric field, the angle of deflection is found to be +5.00 . You may
+
P
assume that all the 31T particles travel at the same speed through an electric field of constant strength.
P
+
Calculate the angles of deflection if 31T is replaced with the following, leavingyour answers to 2 decimal places.
P
32 2-
(i) S [1]

Angle of deflection

2
1 5 = 0.94 [1]
Angle of deflection for 32S2= 32
3
56 3+
Fe [1]

Angle of deflection

3
Angle of deflection = + 561 5 = +0.80 [1]
3
+
The mass of particle Q is 25 times that of 31T .When a beam of Q is passed through the same electric field as in (a), the angle
P
o
of deflection is found to be +0.60 .
(ii) Determinethe overall charge on a particle of Q. [1]
trendyline
re
Q is positively charged

Angle of deflection
ction

+0.60 = 75
1 5
3
x 1]
= +3 [1]
856 trendyline
(iii) A particle ofQ contains 27 protons. Deduce the number of electrons in thisparticle and hence write its electronic
configuration. [1]
No of proton = 27
No of electron = 27-3 = 24
2 2 6 2 6 6
Electronic configuration: 1s 2s 2p 3s 3p 3d
(iv) A nuclear reaction is a reaction in which is a change to an atomic nucleus.

An experimental nuclear reactor use 13 C and Tritium, 31T, as fuel. A nuclear reaction between these two atoms are
described below (n is a neutron).
13
C + 31T ;Q 4He
Suggest the identities of X with the use of the Data Booklet. [1]
11
X: 5B or boron or B
3 (a) The kinetics of the hydrolysis of methyl ethanoate may be investigated by determining the concentration of ethanoic acid
produced.
CH 3 CO 2 CH 3 + H 2 O CH 3 CO 2 H + CH 3 OH
3
In a 1 dm mixture, 0.350 mol of CH 3 CO 2 CH 3 was heated with dilute hydrochloric acid which acts as the catalyst. The
following results were obtained.
3 3
Time / s [CH 3 CO 2 H] / mol dm [CH 3 CO 2 CH 3 ] / mol dm
0 0 0.350
340 0.105 0.245
680 0.185 0.165
1080 0.243 0.107
1440 0.278 0.072
(i) What is meant by the term order of reaction? [1]

m n
Rate = k [A] [B] where
m =order of reaction with respect to A
n =order of reaction with respect to B
m+n =overall order of reaction
or
The order of reaction is the power to which the concentration of a reactant is raised in an
experimentally determined rate equation.
(ii) By drawing a suitable graph using the data given above, determine the order of reaction with respect to methyl
ethanoate. [3]
Since CH 3 CO 2 CH 3 CH 3 CO 2 H, 0.350 mol of CH 3 CO 2 H must be formed with 100% yield as 0.350 mol
of CH 3 CO 2 CH 3 was used.
st
50% yield, [CH 3 CO 2 H] formed = 0.175 mol (1 half-life)
nd
75% yield, [CH 3 CO 2 H] formed = 0.263 mol (2 half-life)
trendyline
6
857 trendyline
Correctly plotted of all points [1]
Correctly labelled axes and 2 half-lives
Correctly identified 2 half-lives:
t (1) = t (2) [1]
order of reaction wrt methyl ethanoate is 1. [1]
(stating order is 1 wo correct reasoning will not score this mark)
(iii) Given that the hydrolysis reaction is first order with respect to hydrochloric acid, write down the rate equation for
this reaction. [1]
+
Rate = k[CH 3 CO 2 CH 3 ][H ]
0.400 [CH3CO2CH3] / mol dm3

0.375
0.350
0.325
0.300
0.275
0.250
0.225
0.200
0.175
0.150
0.125
0.100
0.075
0.050
0.025 t (1) = 630 s t (2) = 630 s
0.000
0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300
00
0 14
1400
00
0
trendyline
(b) Esters can also undergo
dergo reduction in the presence of a strong reducing agent such as lithium
ndergo lithiu aluminium hydride, LiAlH 4 .
The reaction produces
uces two alcohols
alcohols.
RCO
CO 2 R RCH
RC 2 OH + ROH
Using this information,
tion,
on, and that provided below, suggest a mechanism for the formation of et ethanol from methyl ethanoate.

There is an initialal nucleophilic attack by hydride ion, H , on the ester to generate a negat
tial negatively charged ion.
The C=O bond ndd reforms
f andd th OR group is eliminated from the ester, forming an ald
the OR aldehyde.
A second hydrideride ion attacks the aldehyde to generate e an alkoxide ion
ion.
The alkoxide ion is then protonated to form the alcohol.
858 trendyline
O O
+
O O
H
H
Mark Scheme:
O O
Penalise 1 m if wrong starting cpd given.
O
Penalise 0.5m for every following
H
mistakes:
O O Each missing/wrong arrows (up
to 2 m)
+ H Missing any partial charge on
H ester and aldehyde
H Missing lone pairs on hydride
O
OH
H+
H
H
[3]
(c) Besides esters, nitriles can also undergo reduction to give aldehyde in the presence of another strong reducing agent,
dissobutyl aluminium hydride (DIBAL).
RCN RCHO
(i) By considering the change in oxidation states of the reacting carbon, suggest why the conversion of a nitrile to an
aldehyde is a reduction reaction. [1]
The oxidation state of carbon changes from +3 in nitrile to +1 in aldehyde.
CH2Br 4 steps
CH2CH(OH)CO2H
Compound X
(ii) Compound X can be synthesised using DIBAL as a reducing agent in one of the steps above.
Suggest the reagents and conditions required for each step of synthesis and identify all the intermediate
compounds.
[5]
CH2Br CH2CN CH2CHO CH2CH(OH)CN CH2CH(OH)Co2H
ethanolic NaCN DIBAL HCN dil H2SO4
heat trace amount of NaCN heat
[1]: each intermediate product(total 3m)

[]: each reagent and condition (total 2m)
(d) A Wittig reagent can convert an aldehyde to an enone, a ketone with an adjacent double bond.
O O
Ph3P R' CHO R'
R R
wittig reagent enone
:KHUH3KUHSUHVHQWV&
VHQWV& 6 H 5 )
859 trendyline
Wittig reagent F was reacted with an aldehyde G to give an enone H. H was then reacted with hot acidified potassium
manganate (VII) to give two different compounds, J and K.
H can also be synthesised by the following route.
OH
ethanolic NaOH hot acidified K2Cr2O7
heat
L H
enone
Cl
(i) Suggest the identities of compounds H, J, K and L. [4]

H: J/K:
O OH
K/J: L:
O OH
HO
O
[1] each
(iii) Suggest the identities of compounds F and G. [2]
1 each
F: Ph 3 PCH 2 COCH(CH 3 ) 2 G: CH 3 CH 2 CHO [1] each
4 (a) The question below is related to some Group II compounds.

(i) Write an equation, with state symbols, for the thermal decomposition of strontium nitrate. [1]
Sr(NO 3 ) 2 V6U2V12 2 (g) + O 2 (g) [1]

Or
2Sr(NO 3 ) 2 V6U2V12 2 (g) +O 2 (g) [1]
(ii) Use the Data Booklet to explain how the thermal stability of zinc nitrate might compare to strontium nitrate.
[3]
From Data Booklet,
2+ 2+
ionic radius of Zn = 0.074 nm ; ionic radius of Sr = 0.113 nm []
2+ charge
Zn has a higer ratio / charge-density and hence a higher polarizing power. []
size
2+
Hence Zn will polarise/distort the electron cloud of NO 3 to a greater extent; NO bond is
weakened more []
Easier/requires less energy to overcome the N-O bond in zinc nitrate. []
Thus, Zn(NO 3 ) 2 is thermally less stable than Sr(NO 3 ) 2 . [1].
(iii) The chemical properties of beryllium and its compounds show similarity to that of aluminium. Beryllium
complexes have coordinate number 4.
I. Aluminium chloride, AlCl 3 , dimerises to form Al 2 Cl 6 . Draw the displayed formula of Al 2 Cl 6 , showing
clearly the bond angle about Al. [1]
trendyline
d
109.5
860 trendyline
II. Explain why AlCl 3 dimerises. [1]
Al is electron deficient/has one vacant p orbital/has not achieved octet and hence can
accept a lone pair from Cl.
III. Explain, using relevant equations, why a solution of beryllium chloride is acidic. [2]
2+ + +
[Be(H 2 O) 4 ] + H 2 O [Be(H 2 O) 3 OH] + H 3 O [1]
2+ charge
Be has high charge density (or ratio) and is able to polarise O-H bond of water,
size
+
weakening and breaking the OH bond to give H . [1]
IV. Beryllium oxide, similar to aluminium oxide, is amphoteric.

Suggest the nature of bonding in beryllium oxide. [1]
Beryllium oxide is ionic with covalent character. [1]
V. Write equations for the reaction of beryllium oxide with HCl(aq) and with NaOH(aq). [2]
BeO + 2HCl BeCl 2 + H 2 O [1]

2
BeO + 2OH + H 2 O [Be(OH) 4 ] [1]
or BeO + 2NaOH + H 2 O Na 2 [Be(OH) 4 ]
(b) The compound responsible for the hot taste of chilli peppers is capsaicin. Its molecular structure can be
deduced by the following reaction scheme. Capsaicin is slightly acidic.
boil with H+ NH2
C18H27NO 3 + C10H18O 2
Capsaicin N
HO
OCH 3
M
(i) When N is heated with concentrated acidified potassium manganate(VII), P, C 6 H 10 O 4 and Q, C 4 H 8 O, are
formed.
P is formed from the reaction of Br(CH 2 ) 4 Br with hot ethanolic KCN followed by hydrolysis. Q can be reduced
to an alcohol, R, which is optically active.
Deduce the structures of N, P, Q, R and capsaicin. [5]
P: HOOCCH 2 CH 2 CH 2 CH 2 CO 2 H Q: CH 3 COCH 2 CH 3 R: CH 3 CH(OH)CH 2 CH 3

CH3
HO
O CH3
N:
Capcaisin:
CH3
NH
HO O
CH3
OCH 3
trendyline
[1] each
10
861 trendyline
(ii) Assuming that OCH 3 is inert, draw the organic compound formed when M reacts with CH 3 CH 2 COCl.
O
O N
H
O
OCH3
[1]

(iii) Peroxodisulfate(VI) ion, S 2 O 8 , is capable of oxidising tartaric acid, (CH(OH)CO 2 H) 2 , to carbon dioxide and
o
methanoic acid. The E cell of the reaction is +0.99 V.
+
(CH(OH)CO 2 H) 2 + 3S 2 O 8 + 2H 2 O 2CO 2 + 2HCO 2 H + 6H + 6SO 4
The reaction is very slow, even when temperature is increased.
However, the reaction rate can be increased by adding a suitable catalyst.
The half equation for the reduction of carbon dioxide to tartaric acid is
+
2CO 2 + 2HCO 2 H + 6H + 6e (CH(OH)CO 2 H) 2 + 2H 2 O
Using the Data Booklet, show how cobalt(III) ion can act as a homogenous catalyst.
2 2 0
S 2 O 8 + 2e 2SO 4 E red = +2.01V
o o 2 o
Since E cell =E red (S 2 O 8 / SO 4 ) + E ox ((CH(OH)CO 2 H) 2 /HCO 2 H, CO 2 )
o
+0.99 =+ 2.01 + E ox ((CH(OH)CO 2 H) 2 /HCO 2 H, CO 2 )
o
E ox ((CH(OH)CO 2 H) 2 /HCO 2 H, CO 2 9
0
HenceE red (HCO 2 H, CO2 / (CH(OH)CO 2 H) 2 ) =+ 1.02 V [1]
3+
With Co catalyst,
Step 1
3+ 2+ o
Co +e Co E red = +1.82 V
+ o
(CH(OH)CO 2 H) 2 + 2H 2 O 2CO 2 + 2HCO 2 H + 6H + 6e E ox 9
3+ + 2+
(CH(OH)CO 2 H) 2 + 2H 2 O + 6Co 2CO 2 + 2HCO 2 H + 6H + 6Co
o
E cell = + 0.80 V > 0, reaction is feasible. [1]
Step 2
2+ 3+ o
Co Co +e E ox 9
2 2 o
S 2 O 8 + 2e 2 SO 4 E red = +2.01 V
2+ 2 3+ 2
2Co + S 2 O 8 2Co + 2 SO 4
o
E cell = + 0.19 V > 0, reaction is feasible. [1]
3+ 2+ 2+
Co oxidises tartaric acid to give CO 2 and HCOOH and itself is reduced to Co . Co then
2 2 3+ 3+
reduces S 2 O 8 to SO 4 and Co is regenerated. Hence Co acts as a homogeneous catalyst.
11
862 trendyline
5 (a) Chlorine is manufactured from brine, concentrated NaCl, by electrolysis using inert electrodes at room
temperature.The anode and cathode compartments are separated by a diaphragm which is a permeable membrane.
Brine Cl2(g) Gas S
Diaphragm
(i) Suggest the identities of gas S and compound T. [1]
S: Hydrogen / H 2 []T: NaOH []

o
(ii) Using relevant E data from the Data Booklet, suggest the reason why the electrolysis of dilute NaCl(aq)
produces mainly oxygen at the anode, whereas the electrolysis of brine produces mainly chlorine gas.[2]
+ o
2 H2O O 2 + 4 H + 4 e---(1) E ox = 1.23 V
o
2 Cl Cl 2 + 2 e---(2) E ox = 1.36 V []
of Cl, hence water is

When dilute NaCl is used, E ox H 2 O is more positive/less negative than E ox
preferentially oxidised to O 2 . []
When brine is used, concentration of Cl is high, eqm (2) shifts right and
E ox (Cl) is more positive/less negative than E ox of H 2 O [] (due the small initial difference
o
between theE ox values ) hence Clis preferentially oxidised to Cl 2 . []

o
(iii) Suggest what the products might be if the diaphragm is removed and the solution is stirred, by writing an
equation for any reaction that occurs. [1]
Cl 2 (g) + 2 NaOH (aq) NaCl (aq) + NaClO (aq) + H 2 O (l) OR

Cl 2 (g) + 2 OH DT&l (aq) + ClO (aq) + H 2 O (l)
No need for state symbols. [1] or [0]
(b) Orchids can be made into jewellery that gleams with either a reddish tint of copper or shiny gold. In copper-plating,
orchids are coated with a thin layer of graphite paste before placing them in a bath of aqueous copper(II) sulfate and
electroplating.
(i) Suggest a reason why orchids are first coated with graphite. [1]
To conduct electricity
(ii) To ensure high standards, the copper coating must be at least 0.5 mm thick. Given that the total surface area
2
of a typical orchid is 10 cm and the operating current is 20 A, calculate the time required to plate an orchid.
3
trendyline
[Density of copper = 8.96 g cm ] [3]
12
863 trendyline
0.5 3
Volume of Cu layer = 10 = 0.5 cm
10
Mass of Cu layer = 8.96 0.5 = 4.48 g
4.48
Amt of Cu in the layer = = 0.07055 mol [1]
63.5
Amt of electrons required = 2(0.07055) = 0.14110 mol [1]
Amt of charge required = 0.14110 96500 = 13616 C
13616
Time required to plate an orchid = = 680.81 = 681 s [1]
20
(c) The use of Data Booklet is relevant to this question.
When iron is heated with bromine, FeBr 3 is produced. However, when heated with iodine, FeI 2 is produced instead.
(i) Write the two equations for the formation of FeBr 3 . [2]
Fe + Br 2 )H%U 2 [1 or 0]
FeBr 2 + Br 2 )H%U 3 [1 or 0]
(ii) Hence explain why when iron is heated with iodine, FeI 2 is produced but not FeI 3 . [2]

I 2 + 2e I E = +0.54 V---(1)
2+
Fe Fe + 2e E ox = +0.44 V---(2)
2+ 3+
Fe Fe +e E ox = -0.77 V---(3)
(1) + (2): Fe + I 2 )H, 2

E cell = +0.54 + 0.44 = +0.98 V > 0,reaction is feasible [1]
(1) + (3): FeI 2 + I 2 )H, 3

E cell = +0.54 -0.77 = -0.23 V < 0, reaction is not feasible
2+ 3+
Iodine can only oxidise iron to Fe , not Fe . [1]
(iii) An unknown element, U, which exists as diatomic molecules, is said to be positioned below iodine in Group
VII. The hydride of U, HU, and of iodine, HI, differ in their physical properties and reactivities.
(I) Suggest and explain how the polarities of H-U and H-I bonds differ. [1]
H-U bond is less polar [] as U is less electronegative [].
(II) Suggest and explain how the boiling points of HU and HI differ. [2]
HU molecules have a larger electron cloud [] than HI molecules, hence a greater ease of
distortion of electron cloud [; temporary dipole-LQGXFHG GLSROH LQWHUDFWLRQV WGLG DUH PRUH
readily induced.
More energy is required to RYHUFRPHWKHVWURQJHUWGLGLQWHUDFWLRQVEHWZHHQ+8PROHFXOHV>@
(III) Suggest and explain how the acidities of HU and HI differ when each is dissolved in water.
[1]
HU is a stronger acid []
HU bond is weaker than HI bond [].
OR
y
+
HU bond
nd is longer than HI
H I bond, hence
e is easier to break
br H U bonds to give H . []
H-U
(d) eam react to give hydrogen and carbon monoxide as follows.
Methane and steam
CH 4 (g)
g) + H 2 O(g)
(g) 3 H 2 (g)
g) + CO(g)
3
A mixture of 3.0
0 moll
m of CO and 8.0 molll of H 2 is heated in a closed container of 2 dm d and allowed to reach
dynamic equilibrium
um at 300 K. The amount of hydrogen at equilibrium was found to be 6.5 m
ium mol.
(i) e the amounts of methane and steam at equilibrium.
Determine equ [2]
13
864 trendyline
CH 4 (g) + H 2 O(g) 3H 2 (g) + CO(g)
Initialamt/ moll 0 0 8.0 3.0
1.5
Eqm amt/moll 0.5 0.5 6.5 3.0 =2.5
3
0.500 mol each for methane and steam
(ii) Write the expression for the equilibrium constant, K c , for the above equilibrium and calculate K c at 300 K. [2]
[ H 2 ]3 [CO]
kc
[CH 4 ][H 2 O]
3
6.5 2.5

2.0 2.0

2
0.5

2.0
687 mol 2 dm 6
Expression [1] answer with units [1]
trendyline
14
865 trendyline
H
NANYANG JUNIOR COLLEGE
Higher 2
CHEMISTRY 9647/01
Paper 1 Multiple Choice 27September 2016
1 hour
Data Booklet

Write your name, class and tutors name on the Answer Sheet in the spaces provided unless
this has been done for you.
There are forty questions on this paper. Answer all questions. For each question there are
Choose the one you consider correct and record you choice in soft pencil on the separate
Answer Sheet.

[Turn over
2
Section A
For each question there are four possible answers, A, B, C and D. Choose the one
1 In an experiment, lanthanum, 57La, was reacted with hydrogen to produce the

non-stoichiometric ionic compound LaH 2.9 . Assuming that the compound
contains H, La2+ and La3+, what is the percentage of La3+ present in LaH 2.9 ?
A 10%
B 20%
C 80%
D 90%
2 The two most common isotopes of titanium are 56

22Tiand
58
22Ti.
Which statement about the isotopes of titanium is correct?
A Both isotopes have more electrons than neutrons.

B One of the isotopes has more protons than the other.
C The electronic configuration of Ti2+ ion for both isotopes is the same.
56 58
D In the same electric field strength, 22Tiwill be deflected more than 22Ti.
3 Which compound does not have a co-ordinate bond?
A CO B CS 2 C NO 3 D NH 4 +
4 In which of the following pairs do the species have the same bond angle?
A H 2 O 2 and N 2 F 2 B PH 3 and SF 3 +
C POCl 3 and SO 3 2 D HCHO and BrF 3
H2 Chemistry 9647/01 NYJC J2/16 PX

3
5 Two glass vessels M and N are connected by a closed valve.
M contains helium at 20 qC at a pressure of 1 105 Pa. N has been evacuated,

and has three times the volume of M. In an experiment, the valve is opened and
the temperature of the whole apparatus is raised to 100qC.
A 3.18 104 Pa
B 4.24 104 Pa
C 1.25 105 Pa
D 5.09 105 Pa
6 Which value would be required to estimate the lattice energy for the hypothetical
ionic compound MgH?
A the electronic affinity of hydrogen

B the first ionisation energy of hydrogen
C the magnesiumhydrogen bond energy
D the standard enthalpy change of formation of MgH 2
H2 Chemistry 9647/01 NYJC J2/16 PX [Turn over

4
7 A student performed an experiment to investigate a hypothetical reaction.

2A + BoC
The graph of [A] against time(t) for the experiment is shown below.
[A]
0.0500
0.0250
0.0125
t / min
0 20 40
Given that the initial [B] is 2.0 mol dm3 and units for the rate constant is
mol1 dm3 min1, which of the following statementsis true?
A The reaction is elementary.

B The half-life of the reaction remains constant when a catalyst is added.
C The gradient of tangent at t = 0 min increases by four times when the initial
[B] doubles.
D The half-life of the reaction remains constant when [A] doubles but halved
when [B] doubles.
8 Glaubers salt, Na 2 SO 4 10H 2 O, was used by J. R. Glauber in the 17th century as

a medicinal agent. At 25 oC, the numerical value of the equilibrium constant, K p
for the loss of water of hydration from Glaubers salt is 4.08 10.
Na 2 SO 4 10H 2 O(s) Na 2 SO 4 (s) + 10H 2 O(g)
Which of the following statements can be correctly deduced about this
equilibrium reaction?
A The reaction reaches dynamic equilibrium when the forward and reverse rate
constants are equal.
B The numerical value of the vapour pressure of water at 25 oC in a closed
container holding a sample of Na 2 SO 4 10H 2 O(s) is 3.64 10.
C The ratio of the hydrated form to anhydrous form of the Glaubers salt
remains the same when nitrogen gas is added while keeping the total
pressure of the system constant.
D The numerical value of K p will increase when temperature is increased.

5
9 Highly toxic disulfur decafluoride decomposes by a free-radical process.

S 2 F 10 (g) SF 4 (g) + SF 6 (g)
In a study of the decomposition, S 2 F 10 was placed in a 2.0 dm3 flask and heated
to 100 oC. The equilibrium [S 2 F 10 ] was found to be 0.5 mol dm. More S 2 F 10
was then added and the new equilibrium [S 2 F 10 ] was 2.5 mol dm.
What is the amount of S 2 F 10 reacted in terms of the equilibrium constant, K c of
the decomposition reaction when more S 2 F 10 was added?
A (0.5K c )0.5 K c )0.5

B (2.5K c )0.5 K c )0.5
C (2K c )0.5 K c )0.5
D (10K c )0.5 K c )0.5
10 Phosphorus acid, H 3 PO 3 , has two acid dissociation values:

K a1 = 1.0 102 mol dm3 K a2 = 2.5 107 mol dm3
Which of the following statements is correct about H 3 PO 3 ?
I: H 3 PO 3 is a dibasic acid as one of the H atom is bonded to P atom.
II: The K b values of H 2 PO 3 and HPO 3 2are 4.0 1012 and 1.0
1012respectively.
III: K a2 is smaller than K a1 because it gets increasingly difficult to remove a H+
from a negatively charged ion.
A I only
B I&III
C II&III
D All statements are correct

6
11 The diagram below shows the change of pH produced when 20.0 cm3 of
trimethylamine was titrated with 0.01 mol dm3 of HCl(aq) at 25 oC.
pH
11
Volume of acid/ cm3

25.00N
A The K b value of trimethylamine is 8.00 105.

B When 35.00 cm3 of acid is added, pH of the solution is 2.7.
C Phenolphthalein is not a suitable indicator for the above titration.
D When concentration of HCl is doubled, the end point volume of the titration
would be halved while the pH at equivalence point would remain the same.
12 The e.m.f of three different experiments was measured under standard

conditions and the results are shown below:
Experiment 1: W(s) + X2+(aq) o W2+(aq) + X(s) E cell > 0
+ 2+
Experiment 2: X(s) + 2Y (aq) o X (aq) + 2Y(s) E cell < 0
Experiment 3: Z(s) + W2+(aq) oZ2+(aq) + W(s) E cell > 0
A Z2+ is the strongest oxidising agent.

B If concentration of Y+(aq) is lowered in experiment 2, the E cell would be more
positive.
C The reaction of Z(s) + W2+(aq) oZ2+(aq) + W(s) is spontaneous.
D The reducing power decreases in the order Z>W>Y>X.
13 In a lead-acid battery reaction, the charging process is achieved by passing an

electric current through the cell. The overall reaction equation for the charging
process is given below.
2PbSO 4 + 2H 2 O o Pb + PbO 2 + 2H 2 SO 4
7
After charging, PbSO 4 on one plate is converted to PbO 2 . The other plate is
converted to Pb. When the two plates are connected, a current will flow, enabling
the discharging process to take place.
Which species is oxidised when the battery is discharged?
A Pb
B H2O
C PbO 2
D SO 4 2
14 The diagram represents an unsuccessful attempt to prepare and collect sulfur

dioxide.
dilute
hydrochloric acid
X Y
sodium
aqueous concentrated
sulfite,
heat NaOH sulfuric acid
Na2SO3
Which modification would make the experiment successful?
A omitting flask X entirely

B omitting flask Y entirely
C using dilute sulfuric acid instead of dilute hydrochloric acid
D collecting by upward delivery

8
15 Which of the following statements for strontium or its compounds is incorrect?
A Strontium sulfate is sparingly soluble in water.

B Strontium hydroxide is dehydrated to the oxide on strong heating.
C Strontium reacts with cold water to form strontium oxide and hydrogen.
D Strontium carbonate decomposes at a higher temperature than calcium
carbonate.
16 Letters written on paper using aqueous ammonium thiocyanate are invisible until
turned blood red by brushing the paper with aqueous iron(III) chloride. If the
ammonium thiocyanate is first made alkaline, the letters are orange and less
clear.
A The colour changes are due to ligand exchange reactions only.

B Aqueous iron(III) chloride can exist as [Fe(OH)(H 2 O) 5 ] 2+ in solution.
C With aqueous ammonium thiocyanate, [Fe(SCN)(H 2 O) 5 ]3+ complex is formed.
D With alkaline ammonium thiocyanate, the letters are less clear because a
less stable complex is formed.
17 For the sequence hydrogen chloride, hydrogen bromide and hydrogen iodide,
there is a decrease in
I volatility
II pK a value
III thermal stability
IV reducing power
A I&IV
B II&III
C I, II&III
D All of the above
18 A mixture of 1 mol of chlorine and 1 mol of bromine was reacted completely with
iron(II) solution. The resulting mixture was subsequently treated with excess
AgNO 3 (aq). After standing for 5 minutes,excess dilute NH 3 (aq) was added to the
mixture and filtered to obtain filtrate F and residue G.
A If excess HNO 3 (aq) is added to filtrate F, a white precipitate of mass 143.5 g

will be obtained.
B Mass of residue G is 376 g.
C Filtrate F contains [Ag(NH 3 ) 2 ]+,Cl and Fe3+ ions.
D Residue G is made up of more than one precipitate.
9
19 Cracking is a thermal decomposition process by which large hydrocarbon

molecules are broken down by passing them over a heated catalyst at high
pressure. The products are smaller alkanes and alkenes.
The cracking of a single hydrocarbon molecule, C n H 2n+2 , produces two
hydrocarbon molecules only. Each hydrocarbon product contains the same
number of carbon atoms in one molecule. Each hydrocarbon product has non-
cyclic structural isomers.
What is the value of n?
A4 B6 C8 D9
20 Carvone is found in spearmint.
Carvone
How many V and S bonds are present in this molecule?
V S
A 11 6
B 13 6
C 25 3
D 25 6
21 Many different compounds have been used in aerosol sprays, refrigerators and in
making foamed plastics.
Which compound will cause the most ozone depletion?
A CCl 3 F
B CH 2 FCHClF
C CH 3 CH 2 CH 2 CH 3
D N2O

10
22 The reactivity of methoxybenzene, C 6 H 5 OCH 3 is similar to that of phenol.
How many moles of aqueous nitric acid are required to react with one mole of
bis(4-methoxyphenyl)amine?
NH
H3CO OCH3
bis(4-methoxyphenyl)amine
A 2
B 3
C 4
D 5
23 Which of the following will not yield a final organic product containing deuterium?
(D = 2H)
compound reagents and conditions
NH2
A H3C DCl, D 2 O, heat under reflux
O
B CH 3 CH 2 CH 2 COCl D 2 O, room conditions
C CH 3 CH 2 CHO DCN, trace NaCN, 15 oC
OH
H3C CH 3 OD, conc D 2 SO 4 , heat under
D
reflux
O

11
24 Compound X is used to synthesize DEET, a common active ingredient in

mosquito repellent. A brick-red precipitate is observed when it reacts with
Fehlings reagent. 1 mol of Xundergoes the following reactions.
K2Cr2O7/H+ KMnO4/H+
V X Y
' '
Y reacts with HNO 3 under suitable conditions to produce only 1 possible organic
product. V reacts with Na 2 CO 3 to produce only 1 mol of CO 2 (g).
What could X be?

A B
CH2OH COOH
CHO CH2CHO
C D
CH2OH CH=CHCOOH
CH2CHO COCH3

12
25 Which of the following statements about compound W is correct?
Cl
HO2C
O
O HN
O
O
compound W
A An aqueous solution of W is approximately neutral as there is 1 carboxylic

acid group and 1 amine group present in the structure.
B The product formed when W is reduced by LiAlH 4 will react with Na to
produce 2 moles of H 2 (g).
C The reduction of W by LiAlH 4 will cause the oxidation state of any carbon
LQYROYHGLQWKHUHGXFWLRQWRGHFUHDVHIURPWR
D W will require 3 moles of NaOH(aq) for complete reaction if the reaction is to
take place with heating.

13
26 The Hofmann elimination is a process where an amine undergoes treatment with

excess methyl iodide to form a tertiary amine intermediate followed by treatment
with silver oxide, water and heat to form an alkene.
CH3 H
CH3
CH3 excess CH3I CH3 Ag2O, H2O H3C
H H3C
+ -
heat
+
NH2 N (CH3)3 II
(CH3)3N
What is the structure of the alkene formed when a cyclic amine, piperidine,
undergoes the Hofmann elimination?
NH
Piperidine
A CH 2 =CHCH 2 CH 2 CH 2 N(CH 3 ) 2
B CH 2 =CHCH 2 CH 2 CH 3
C N CH3
27 Which of the following compounds can be used, in a 1-step conversion, to

produce the following cyclic structure?
O O
O N
H
A HO 2 CCH 2 NH 2 and HO 2 CCH 2 OH
B HO 2 CCH 2 CONHCH 2 OH
C ClOCCH 2 COCl and H 2 NCH 2 OH
D ClOCCH 2 OH and H 2 NCH 2 CO 2 H

14
28 One gram of each of the following compounds was heated with NaOH(aq), and
then dilute HNO 3 (aq) and AgNO 3 (aq) were added.
Which compound will produce the largest mass of AgCl(s) in 30 seconds?
A B C D
O CH2Cl O
Cl
Cl Cl
Cl
Cl Cl
O CH2Cl
O
C 3 H 2 O 2 Cl 2 C 6 H 10 Cl 2 C 6 H 4 Cl 2 C 4 H 4 O 2 Cl 2
M r = 141 M r = 153 M r = 147 M r = 155
29 Consider the following four compounds.

1 ethanamide, CH 3 CONH 2
NH2
2 phenylamine,
3 piperidine, NH
H H
C C
4 pyridine, N H C N H
C C
H H
What is the relative order of decreasing basicity of these compounds?
A 3 2 1 4
B 3 2 4 1
C 3 4 2 1
D 3 4 1 2

15
30 Upon complete hydrolysis, 1 mol of polypeptide X gives the following amino acids.
amino acid structure Mr mass of amino acid / g
asparagine O 132 16.8
C NH2
H2C
NH2
C
H
COOH
proline NH 115 7.3
COOH
serine OH 105 13.3
H2C
NH2
C
H
COOH
What is the M r of X?
A 352
B 499
C 517
D 589

16
Section B
For each of the questions in this section one or more of the three numbered
statements 1 to 3 may be correct.
Decide whether each of the statements is or is not correct (you may find it helpful to
put a tick against the statements which you consider to be correct).
A B C D
1, 2 and 3 1 and 2 2 and 3 1 only
31 The hexagonal form of boron nitride, h-BN, is analogous to graphite where it has
a planar hexagonal layered structure of alternating boron and nitrogen atoms.
Which properties are shown by h-BN?
1 Its N atoms are sp2 hybridised.

2 It can be used as a dry lubricant.
3 It is soluble in organic solvents but not soluble in water.
32 Which of the following has the same value as the standard enthalpy change of
formation of carbon monoxide?
1 'H
(CO 2 ) 'H
(CO)
2 'H
(CO) 'H
(graphite)
3 'H
(CO 2 )

17
A B C D
1, 2 and 3 1 and 2 2 and 3 1 only
33 A student investigated the reaction between iodide and peroxodisulfate.
2I(aq) + S 2 O 8 2(aq) oI 2 (aq) + 2SO 4 2(aq)
He first performed the experiment by adding Fe3+(aq) as catalyst. He then

performed a second experiment under the same condition but did a change at t 1 .
The graphs of [I 2 ] against time for both experiments are shown below.
[I2]
First experiment
Second experiment
time / min
t1
1 acidified VO 2 Cl(aq) can also be used as a catalyst.

2 Sodium cyanide could have been added at t 1 .
3 The Boltzmann distribution graph for the first experiment is as follow
Number of
Particles
Kinetic Energy
Ea (catalysed)

18
A B C D
1, 2 and 3 1 and 2 2 and 3 1 only
34 Phosphorus is an element in the third period, Na to Ar, of the Periodic Table.

What is true for phosphorus and none of the other elements in this period?
1 Phosphorus is the only element in this period with exactly four atoms in its
molecules.
2 Phosphorus is the only element in this period which forms two acidic oxides.
3 Phosphorus is the only element in this period whose chlorides react with
water to form acidic solutions.
35 Which of the statements of the Group II elements (magnesium to barium) or their

compounds is correct?
1 Reactivity of Group II elements with oxygen increases down the group.

2 The volume of acidic gas evolved from the decomposition of 1 mol of Group
II nitrate is four times that of the neutral gas evolved.
3 Solubility of the Group II sulfates decreases down the group.

19
A B C D
1, 2 and 3 1 and 2 2 and 3 1 only

Which of the following species would convert manganese(II) sulfate to
manganese(IV) oxide in acidic solution?
1 Pb(NO 3 ) 4
2 Na 2 S 2 O 8
3 CoCl 2
37 Which of these alwaysapplies to a nucleophile?
1 It has a lone pair of electrons.

2 It is negatively charged.
3 It attacks a double bond.
38 Long-chain alkanes are converted on an industrial scale into alkylsulfates for use
as detergents, e.g. sodium lauryl sulfate.
H H H O
H C C C O S ONa
H H H O
10
sodium lauryl sulfate
What deductions about the properties of this substance can be made from this
structure?
1 Part of the structure is polar and is hydrophilic.

2 The alkyl chain is soluble in oil droplets.
3 All the CCC bond angles are 109o.

20
A B C D
1, 2 and 3 1 and 2 2 and 3 1 only
39 There is a range of reactions of the aldehyde group which have the pattern
OH
H3C H3C
C O + HX C
H X
H
of which the formation of a cyanohydrin (where X = CN) is one.
Which compounds could be obtained by such an addition to an aldehyde group,

followed by a dehydration?
1 CN
2 H
O
O OCH3
NH CH
N CH3
3
40 Which of the following reactions produce a carbocation as an intermediate

product and an organic molecule containing a chiral centre that is optically
inactive as the final product?
1 C 6 H 10 + HBro C 6 H 11 Br
2 CH 3 CH=CH 2 + Br 2 + NaNO 3 o CH 3 CH(ONO 2 )CH 2 Br + NaBr
3 CH 3 C(CH=CH 2 )(CH 2 CH 3 )Br + NaOH o CH 3 C(CH=CH 2 )(CH 2 CH 3 )OH +
NaBr

21

H
Higher 2
CANDIDATE
NAME
INDEX
CLASS 1 5 NO.
TUTOR
CHEMISTRY 9647/02
2 hours


For Examiners Use
1 P /12
2 / 15
3 / 6
4 / 13
5 / 6
6 / 20 /60

For
2 Examiner's
Use
1 Planning (P)
Bakers yeast is a useful enzyme which can be used to catalyse the decomposition of hydrogen
peroxide.
H2O 2 o H2O + O 2
You are provided with
Set-up apparatus:
x 1 x retort stand with clamp
x 1 x 100 cm3 conical flask
x 1 x L-shape glass tube connector fitted with a rubber bung
x 1 x rubber tubing connection
x 1 x gas syringe (possible capacities of 10, 20 or 100 cm3)
Reagents and apparatus

x 100 cm3 of yeast suspension
x 100 cm3 of 3% (by weight) hydrogen peroxide
x Distilled water
x Stopwatch
x All other common laboratory equipment
When 8.0 cm3 of the yeast suspension, 4.0 cm3 of H 2 O 2 and 18.0 cm3 of distilled water is mixed,
10 cm3 of oxygen gas was produced in 90 s.
Use the above information and the reagents provided to design an experiment to
x prove first order reaction with respect to yeast by a graphical method

x prove first order reaction with respect to hydrogen peroxide by a graphical method
In your experiment, you should perform 4 other experimental runs (including the above run) to
measure the volume of oxygen gas produced at regular intervals. The volume of yeast suspension
used should be varied in all the runs while keeping volume of H 2 O 2 constant at 4.0 cm3 .
In your experiment, illustrate / describe the following:
x A labelled set-up for your experiment using the set-up apparatus provided
x Table of volumes that you will be using in your experiment
x Calculations to determine the maximum volume of oxygen gas produced in each
experimental run. In your calculations, assume that the density of H 2 O 2 is 1.00 g cm3 and
conditions are at r.t.p.
x Procedure for measuring the volume of oxygen gas produced at regular intervals and use
the results to find the initial rate for each run graphically
x Graphical analysis involving initial rates to deduce order with respect to yeast
x Graphical analysis involving half-lives to deduce order with respect to H 2 O 2 based on one
selected run

For
3 Examiner's
Use
Experimental setup:
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For
4 Examiner's
Use
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[Total: 12]

For
5 Examiner's
Use
BLANK PAGE

For
6 Examiner's
Use
2 A solder is an alloy of metals which is used to join other metal pieces together. A specialist
solder that can be used to join together pieces of aluminium is made from a mixture by
mass of 65% zinc, 20% aluminium and 15% copper.
An H[SHULPHQWDO SURFHGXUH FDQ FRQUP WKH FRPSRVLWLRQ RI D SRZGHUHG VDPSOH RI WKLV
solder, by adding reagents and then extracting from the mixture each of the following in
sequence;
(i) copper metal,
(ii) aluminium as aluminium hydroxide,
(iii) zinc as zinc hydroxide.

DVDPSOHRIWKLVVROGHUZLWKDSSUR[LPDWHPDVVJ
PROGP3 sulfuric acid,
PROGP3 ammonia.
No other reagents should be used. Standard laboratory equipment is available.
(a) &RPSOHWHWKHRZFKDUWEHORZWR show the order in which the reagents would be added to
the solder to allow you to extract and separate the components as copper metal, aluminium
hydroxide and zinc hydroxide in Step 1, Step 2 and Step 3 respectively.
Step 1 Step 2 Step 3

reagent(s) added reagent(s) added reagent(s) added
substance(s) present substance(s) present substance(s) present

in solution in solution in solution
substance(s) removed substance(s) removed substance(s) removed

by filtration (if any) by filtration (if any) by filtration (if any)
[3]

For
7 Examiner's
Use
(b) (i) For some of the steps in the procedure you would need to be careful to add an
appropriate quantity of a reagent.
For each step of your procedure, explain why particular quantities of reagent should
be chosen.
Step 1 ................................................................................................................
..........................................................................................................................
..........................................................................................................................
Step 2 ................................................................................................................
..........................................................................................................................
..........................................................................................................................
Step 3 ................................................................................................................
..........................................................................................................................
...................................................................................................................... [4]
(ii) Write the ionic equations for the reactions taking place in Step 2.
..........................................................................................................................
...................................................................................................................... [2]
(iii) State the observations for the reactions taking place in Step 1 and Step 3.
Step 1 ................................................................................................................
Step 3 ............................................................................................................ [2]
(c) $OXPLQLXPK\GUR[LGHDQG]LQFK\GUR[LGHWKDWKDYHEHHQH[WUDFWHGDUHGLIFXOWWRGU\VRLWLV
better to convert them to their oxides.
Describe how this could be done and how you would ensure that each hydroxide has been
completely converted into its oxide.
....................................................................................................................................
....................................................................................................................................
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....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
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................................................................................................................................ [2]
For
8 Examiner's
Use
(d) If the mass of aluminium oxide obtained was 1.50 g, calculate the mass of aluminium that
was present in the solder. [1]
(e) (YHQ LI WKH H[SHULPHQWDO GLIFXOWLHV RI H[WUDFWLQJ DOO RI WKH FRSSHU IURP WKH PL[WXUH ZHUH
RYHUFRPHLWZRXOGEHGLIFXOWWRREWDLQDQDFFXUDWHPDVVRIFRSSHUIURPWKLVH[SHULPHQW
Suggest why this is so.
....................................................................................................................................
....................................................................................................................................
................................................................................................................................ [1]
[Total: 15]

For
9 Examiner's
Use
3 The relationship pV=nRT can be derived from the laws of mechanics by assuming ideal
behaviour for gases.
(a) The graph below represents the relationship between pV and p for a real gas at three
different temperatures, T 1 , T 2 and T 3 .
pV T1 T2
T3
p
(i) Draw one line on the graph to show what the relationship should be for the same
amount of an ideal gas. [1]
(ii) With reference to the graph, state and explain which temperature, T 1 , T 2 or T 3 is the
lowest temperature.
.........................................................................................................................
.........................................................................................................................
.........................................................................................................................
.........................................................................................................................
..................................................................................................................... [2]
(b) A flask with a volume of 100 cm3 was first weighed with air filling the flask, and then with
another gas Y, filling the flask. The results, measured at 26 oC and 1.00 x 105 Pa are shown.
Mass of flask containing air = 47.930 g

Mass of flask containing Y = 47.989 g
Density of air = 0.00118 g cm3
Calculate the relative molecular mass, M r , of Y. [3]
[Total: 6]

For
10 Examiner's
Use
4 PbCl 2 is a sparingly soluble salt.
PbCl 2 (s) Pb2+(aq) + 2Cl(aq) 'H > 0
A student investigated the solubility product and solubility of PbCl 2 under different
conditions. He first added 0.0100 g of solid PbCl 2 into 120 cm3 of an unknown
concentration of HCl(aq) at 25 oC and subsequently made four changes at t 1 , t 2 , t 3 and t 4 .
The graphs below show the mass of PbCl 2 dissolved and solubility product of PbCl 2
against
time.
Mass of PbCl2
dissolved
0 t1 t2 t3 t4
time
Ksp
1.70 105
0 t1 t2 t3 t4
time

For
11 Examiner's
Use
(a) Given that 0.00465 g of PbCl 2 remained undissolved after addition of 0.0100 g of PbCl 2
into HCl, deduce the unknown concentration of the HCl. [3]
(b) Determine the mass of PbCl 2 that can dissolve in 500 cm3 of water at 25 oC. [2]

For
12 Examiner's
Use
(c) Some possible changes listed below were made by the student at t 1 , t 2 and t 3 .
1. Cool reaction mixture to 10 oC in water bath
2. Heat reaction mixture to 50 oC in water bath
3. Addition of AgNO 3 (aq)
4. Addition of PbCl 2 (s)
5. Addition of water
With reference to both graphs, suggest and explain the changes made at t 1 , t 2 and t 3 .
change made at t 1 ..........................................................................................................
explanation ...................................................................................................................
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change made at t 2 .........................................................................................................
explanation ...................................................................................................................
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change made at t 3 ..........................................................................................................
explanation ...................................................................................................................
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................................................................................................................................[6]
(d) The student added concentrated HCl at t 4 . On both the graphs on Page 10, draw how the
two graphs would look like after t 4 . [2]
[Total: 13]

For
13 Examiner's
Use
6 Compound A (C 12 H 16 O 2 ) exhibits optical isomerism. It does not react with hot acidified
K 2 Cr 2 O 7 . 1 mole of A reacts with 1 mole of PCl 5 to form B. A reacts with cold dilute KMnO 4
to form C (C 12 H 18 O 4 ). Upon heating with acidified KMnO 4 , A gives D (C 9 H 10 O 4 ) and E. D
produces effervescence when aqueous Na 2 CO 3 is added. 1 mole of D reacts with 3 moles
of aqueous bromine. E gives F, a yellow precipitate with warm alkaline aqueous iodine.
Draw the structures of A, B, C, D, E and F.
A B
C D
E F
[Total: 6]

For
14 Examiner's
Use
5 The Ritter reaction is an organic reaction used to convert a nitrile and a tertiary alcohol, in a
second order reaction, to form an amide using strong aqueous acid as the catalyst.
O R2
R2 + R3
H (aq) C C
R1 CN R3 C OH
R1 N R4
R4
H
, ,
R1 R2 R3 and R4 are alkyl groups
The proposed mechanism is as follows:
R2 R2
R3 C OH H C R3 H2O
+
step 1
R4 R4
H H
R2 R2 O R2
H2O
R1 CN C R3 step 2 R1 C N C R3 step 3 R1 C N C R3
R4 R4 R4
step 4
H
O R2 O R2
R1 C N C R3 H+ step 5 R1 C N C R3
H R4 H R4
(a) Predict the structures of P, Q and T for each of the following Ritter reactions. [3]
+ O
H (aq)
+
N
H
P Q
R
(C 8 H 7 N) (C 6 H 12 O)

For
15 Examiner's
Use
+
HO CN H (aq)
(C 8 H 15 NO)
(b) Describe a simple chemical test to distinguish compound R and S, stating clearly the
observations.
Test .............................................................................................................................
Observation .................................................................................................................
....................................................................................................................................
................................................................................................................................ [2]
(c) Suggest the types of reaction occurring in steps 3 and 4.
Step 3 ...........................................................................................................................
Step 4 ....................................................................................................................... [2]
(d) Complete the mechanism of step 3 and 4 below with arrows, showing the lone pairs and
dipole charges. [3]
H O H H H
R2 O R2 O R2
R1 C N C R3 step 3 R1 C N C R3 step 4 R1 C N C R3
R4 R4 H R4
(e) Suggest which step of the proposed mechanism on Page 14 is the slowest step. Explain
your reasoning.
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....................................................................................................................................
................................................................................................................................[1]

For
16 Examiner's
Use
(f) Primary alcohols such as ethanol are not suitable reagents for the Ritter reaction.
(i) Draw a diagram to show the orbitals of the carbon in the carbocation in step 1 and
state the type of hybridisation involved. [1]
(ii) Suggest why tertiary alcohols are used in the Ritter reaction but not primary
alcohols.
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..................................................................................................................... [2]
(iii) Suggest why phenylmethanol is a suitable reagent for the Ritter reaction even
though it is a primary alcohol.
OH
phenylmethanol
.........................................................................................................................
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.........................................................................................................................
..................................................................................................................... [1]

For
17 Examiner's
Use
(g) This equation for the Ritter reaction is repeated from page 14.
O R2
R2 + R3
H (aq) C C
R1 CN R3 C OH
R1 N R4
R4
H
, ,
(i) Using suitable data from the Data Booklet, calculate the enthalpy change of reaction.
[2]
(ii) Suggest and explain if the Ritter reaction is spontaneous at high or low temperature.
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..................................................................................................................... [3]
[Total: 20]
H2 Chemistry 9647/02 NYJC J2/16 PX [End[Turn over

of Paper]
H
Higher 2
CHEMISTRY 9647/03
2 hours
Candidates answer Section A on the Question Paper

Data Booklet

[Turn over
2
1(a) Copper(I) sulfate, Cu 2 SO 4 , can be made from copper(I) oxide under non-aqueous
conditions. On adding this salt to water, it immediately undergoes a disproportionation
reaction.
(i) Suggest, with a reason, the colour of copper(I) sulfate. [2]
(ii) Using suitable data from the Data Booklet, explain why the disproportionation
reaction occurs, and write an equation for it. [3]
(b) Palladium(II) salts can form square planar complexes. Successive addition of ammonia and
hydrogen chloride to an aqueous palladium(II) salt produces, under different conditions,
three compounds with empirical formula PdN 2 H 6 Cl 2 . Two of these, A and B, are non-ionic,
with M r = 211. A has a dipole moment, whereas B has none. The third compound, C, is
ionic, having M r = 422, and contains palladium in both its cation and anion.
For each A, B and C, deduce a structure that fits the above data, explaining your reasons
fully. [6]
(c) Benzene ring is often represented as a structure that has a ring within the hexagon.
Alternatively, chemists have also represented the structure of benzene in the following
forms, known as resonance structures.
Benzene (two resonance forms)
The resonance relationship is indicated by the double headed arrow between them. The
only difference between resonance forms is the placement of the pi electrons and
non-bonding electrons.
Most aromatic compounds undergo electrophilic substitution. However aryl halides undergo
a limited number of substitution reactions with strong nucleophiles.
An example of a reaction is as follows:
Nu
A X A Nu + X
where A is an electron withdrawing group and X is a halogen
The mechanism of this reaction has two steps:

x addition of the nucleophile
x elimination of the halogen leaving group
H2 Chemistry 9647/03 NYJC J2/16 PX [Turn Over

3
Step 1 involves the addition of the nucleophile (Nu). The Nu attacks the carbon atom
bonded to a halogen, causing the pi bond to break. A resonance stabilised carbanion with a
QHZ&1XERQGLVIRUPHG7KHDURPDWLFULQJLVGHVWUR\HGLQWKLVVWHS
Nu
X X
Nu

A A
Step 2 involves the loss of the halogen X, reforming the aromatic ring.
Nu
X Nu
X

A A
Two other resonance structures of the intermediate in Step 1 are shown below:
Nu Nu
X X
I II
Z
A A
(i) Copy the above diagram and draw the resonance structure, Z. In your answer,
show any relevant charges, lone pairs of electrons and movement of electrons in
forming Z. [2]
The reaction below shows the synthesis of compound, D.
N(CH3)2 N(CH3)2
O 2N
O 2N
potassium metal +
+ HCl
Cl HO O
D
(ii) Suggest the role of potassium metal in the reaction. [1]
(iii) Use the information given above to draw out the full mechanism for the reaction that
forms D, labelling the slow and fast steps. In your answer, showing any relevant
charges, lone pair of electrons and movement of electrons. [3]
(d) Describe and explain the relative ease of hydrolysis of the following three
chloro-compounds. [3]
Cl COCl CH2Cl
[Total: 20]

4
2 Sulfuric acid, H 2 SO 4 , can behave as an acid, an oxidising agent or as a dehydrating agent
in various reactions.
(a) Draw a diagram to illustrate the shape of pure sulfuric acid and indicate the bond angle
about the sulfur atom. [2]
(b) The Contact Process is used for the manufacture of sulfuric acid. One of the reactions that
takes place is the following reversible reaction:
2SO 2 (g) + O 2 (g) 2SO 3 (g) 'H = 197 kJ mol1
Sulfur dioxide and oxygen in a 2:1 molar ratio at a total initial pressure of 3 atm is passed
over a catalyst in a fixed volume vessel at 400 oC. When equilibrium is established, the
percentage of sulfur trioxide in the mixture of gases is found to be 30%.
(i) Write an expression for the equilibrium constant, K p , of the reaction. [1]
(ii) Calculate the value of K p at 400 oC, stating its units. [3]
(iii) How would the percentage conversion of SO 2 into SO 3 be affected when the
pressure is raised? Explain. [2]
(c) Dilute sulfuric acid takes part in typical acid-base reactions and it can be used to distinguish
the following solids: MgO, BaO and SiO 2 .
State the observations, if any, to indicate the differences in their reaction when water is
added to each solid followed by dilute sulfuric acid. [4]
(d) Sulfur dioxide is a major pollutant from sulfuric acid plants. The SO 2 emitted into the
atmosphere is oxidised in the air, which then reacts with water to form sulfuric acid, hence
causing acid rain:
2SO 2 (g) + O 2 (g) + 2H 2 O(l) o 2H 2 SO 4 (l) 'H 1
Using the data below and data from (b), construct an energy cycle to calculate
(i) the enthalpy change of formation of SO 2 (g), and hence
(ii) the enthalpy change of reaction, 'H 1 for the above reaction.
Enthalpy change of formation of H 2 O(l) = 286 kJ mol1

Enthalpy change of formation of H 2 SO 4 (l) = 811 kJ mol1
Enthalpy change of formation of SO 3 (g) = 493 kJ mol1
[4]

5
(e) Alcohols react with concentrated sulfuric acid at high temperatures to form alkenes. A
common side reaction that can happen is the formation of ethers, which is also catalysed
by concentrated sulfuric acid.
R R R
conc H2SO4
2R C OH R C O C R + H2O
heat
R R R
R R R
conc H2SO4
heat
R R R
The mechanism occurs via 3 steps:
Step 1:
An acid base reaction in which H+ from H 2 SO 4 protonates the oxygen atom in alcohol. This
step is very fast and reversible.
Step 2:
A second alcohol molecule functions as the nucleophile and attacks the product from
step 1. The CO bond is cleaved and a water molecule leaves the molecule. This creates
R
+
O
an oxonium ion R' H intermediate.
Step 3:
Another acid base reaction in which the proton in the oxonium ion is removed by a suitable
base (in this case a water molecule) to give the ether product. This step is very fast and
reversible.
(i) Draw the ether formed when cyclopentanol undergoes the above reaction.
OH
cyclopentanol
[1]
(ii) Draw out the full mechanism for the reaction between two cyclopentanol molecules
to form an ether. In your answer, show any relevant charges, lone pairs of electrons
and movement of electrons. [3]
[Total: 20]

6

7
3 Garlic contains many amino acids, minerals and enzymes. Garlic also contains at least 33
sulfur compounds like alliin, allicin and ajoene. The sulfur compounds are responsible for
both garlics pungent odour and many of its medical effects.
(a) When raw garlic is chopped or crushed, the enzyme allinase converts alliin into allicin,
which is responsible for the odour of fresh garlic.
O NH2 O
S allinase S
COOH S
alliin allicin
Allicin can also be biosynthesised by using serine and glutathione.
NH2 COOH O
HO NH
COOH H2N NH COOH
O
SH
serine glutathione
(i) Explain why raw chopped garlic has a stronger odour than when it is cooked. [1]
(ii) When one molecule of serine reacts with one molecule of glutathione, it is possible
to form two esters with different structural formulae.
Draw the structural formula of each of these esters. [2]
(iii) Draw the structural formulae of the products when glutathione is hydrolysed. [3]
Alliin has pK a values of 1.84 and 8.45.
(iv) Make use of these pK a values to suggest the major species present in solutions of
alliin with the following pH values. [3]
x pH 1
x pH 7
x pH 11
(v) Calculate the pH of 0.10 mol dm3 solution of alliin. [1]
(vi) With reference to the pK a values, identify the major species formed when 10 cm3 of
0.10 mol dm3 NaOH is added to 10 cm3 of 0.10 mol dm3 protonated alliin. Hence,
deduce whether the solution is acidic, neutral or alkaline. [2]
(vii) Sketch the pH-volume added curve you would expect to obtain when 30 cm3 of
0.10 mol dm3 NaOH is added to 10 cm3 of 0.10 mol dm3 protonated alliin.
Briefly describe how you have calculated the various key points on the curve. [4]

8
(b) Diallyl disulfide is one of the principal components of the distilled oil of garlic. It is a
yellowish liquid which is insoluble in water and has a strong garlic odour. It is produced
during the decomposition of allicin.
S S
S S
allicin diallyl disulfide

Diallyl disulfide can be produced industrially from sodium disulfide and allyl chloride at
temperatures of 40 60 C in an inert atmosphere.
40 60 oC
Cl S
Na2S2 + 2 S + 2NaCl
inert gas
allyl chloride
(i) Give the IUPAC name of allyl chloride. [1]
(ii) Explain, in thermodynamic terms, suggest why diallyl disulfide is insoluble in water.
[2]
(iii) State the type of reaction when diallyl disulfide is converted back to allicin. [1]
[Total: 20]

9
4 Alkynes are organic molecules which contain carbon-carbon triple bonds and are part of the
homologous series with formula of C n H Q i.e.
R1 C C R2
where R 1 and R 2 = H or alkyl or aryl groups
Alkynes exhibit similar chemical properties to alkenes.

e.g. addition reactions with electrophiles i.e. X 2 or HX to form alkenes
R1 R2
HX
R1 C C R2 C C
H X
e.g. oxidation by hot concentrated KMnO 4 to form mixture of carboxylic acids
KMnO 4
R1 C C R2 R1COOH + R2COOH
However, unlike alkenes, terminal alkynes are able to react with strong bases like sodium
amide.
+
RC CH + NaNH2 RC C Na + NH3
(a) Ethyne, C 2 H 2 , is heated with excess sodium bromide and concentrated sulfuric acid to
produce a dihalide, C 2 H 4 Br 2 . The overall reaction may be considered to take place in two
stages, the first between inorganic reagents only and the second involving the organic
reagent.
(i) Write an equation for the first stage. [1]
(ii) Suggest a structure for the dihalide formed. [1]
(iii) When the concentrated sulfuric acid is added to the reaction mixture, cooling is
necessary to prevent the formation of inorganic by-products.
Write an equation to explain the formation of these inorganic by-products. [1]
(b) Compound A, is an enyne chloride (i.e. compounds that contains chloro, alkyne and alkene
functional groups).
Cl
Compound A
One mole of compound A reacts with two moles of Br 2 to produce a mixture of

4 stereoisomers. Draw structures of the stereoisomers formed. [3]

10
(c) Compound B, which is an isomer of Compound A and also an enyne chloride, is treated
with sodium amide, NaNH 2 followed by heating under reflux to form compound C, C 8 H 10 .
Compound C reacts with hot concentrated KMnO 4 to produce butane-1,4-dioic acid only.
(i) Explain the reaction with NaNH 2 . [1]
(ii) Hence, explain the formation of compound C. [1]
(iii) Suggest skeletal structures for compounds B and C. [2]
When a current of 1.0 A was passed through aqueous potassium maleate (KO 2 CCH=CHCO 2 K) for
15 minutes, it was found that 110 cm3 H 2 , measured at r.t.p, was collected at the cathode. The
following reaction took place.
2H 2 O + 2e o H 2 + 2OH
(d) State the relationship between the Faraday constant, F and the Avogadros constant, L. [1]
(e) Using the data above and the Data Booklet, calculate a value for Avogadros constant. [3]
(f) Ethyne and CO 2 gas were produced at the anode. In order to determine the stoichiometry
of the anode reaction, the volume of the gases collected at the anode was measured. The
anode gas was first passed through aqueous NaOH before being collected in a gas
syringe. The following data was collected:
x mass of bottle containing NaOH before experiment = 10.501 g

x mass of bottle containing NaOH after experiment = 10.904 g
x initial reading on syringe = 10.0 cm3
x final reading on syringe = 120.0 cm3
(i) State the oxidation state of carbon in ethyne. [1]
(ii) With the help of an equation, explain the purpose of passing the anode gas through
NaOH. [1]
(iii) Calculate the volume of CO 2 produced, assuming r.t.p conditions. [1]
(iv) Hence, suggest an ionic equation for the reaction that occurred at the anode. [1]
(g) When aqueous potassium maleate was acidified, maleic acid, HO 2 CCH=CHCO 2 H
(pK a1 = 1.90 and pK a2 = 6.07) was liberated. Fumaric acid (pK a1 = 3.03 and pK a2 = 4.44) is
a stereoisomer of maleic acid.
With a suitable illustration, suggest a reason why maleic acid has a lower pK a1 but higher
pK a2 than fumaric acid.
[2]
[Total: 20]

11
5(a) Dopamine is an organic compound of the catecholamine and phenethylamine families that
plays several important roles in the brain and body. Its name is derived from its chemical
structure: it is an amine synthesised by removing a carboxyl group from a molecule of
its precursor compound, L-DOPA.
Below is a synthetic route involving L-DOPA and dopamine:
O
HO HO NH2
OH
+ CO 2
NH2
HO HO
L-DOPA Dopamine
Reaction I Reaction III

Compound H
O
Product J
HO
Cl
HO N
NH2
HO
HO
Reaction II
anhydrous AlCl 3
Isomers F and G
C9H9O 3N
(i) State the reagents and conditions and any observations in Reaction I. [1]
(ii) Aluminium chloride is used as a catalyst in electrophilic substitution reactions. The

Cl
+ Cl 2 + HCl

x The first step is the reaction between Cl 2 and AlCl 3 .
Cl 2 + AICl 3 Cl+ + AICI 4
+
x The benzene is then attacked by the Cl cation in the second step.
The first step is the reaction between Cl 2 and AICI 3 .

+
The benzene ring is then attacked by the CI cation in the second step.
AICl 3 reacts in a similar way with acyl chlorides, producing a carbocation
that can then attack a benzene ring.
Predict the structures of isomers F and G in Reaction II. [2]

12
(iii) In Reaction III, dopamine was reacted with alkyl halide H to give the final product J.
Draw the displayed formula of H. [2]

13
(b) Dopamine is a bidentate ligand. When different volumes of 0.0030 mol dm3 of aqueous
Cr(III) and 0.0020 mol dm3 of alkaline dopamine solution were mixed, a complex R is
formed. Analysis of R shows that its formula is [Cr(C 8 H 9 NO 2 ) x (H 2 O) y ]z, where x, y and z
are integers.
To determine the stoichiometry of the complex ion formed, the colour intensities of these
different mixtures were measured using a colorimeter. The following absorption spectrum
was obtained.
Relative Absorbance
Volume of Cr3+ / cm3
10 9 8 7 6 5 4 3 2 1
Volume of alkaline dopamine / cm3
(i) Use the graph and the information given to determine the formula of complex R.
Show your workings clearly. [3]
(ii) The crystal field describes the breaking of orbital degeneracy in transition metal
complexes due to the presence of ligands. When the d-orbitals split into high energy
and low energy orbitals, the difference in enerJ\RIWKHWZROHYHOVLVGHQRWHGDV o .
7KH UHODWLRQVKLS EHWZHHQ o and colours of complexes can be described in the
equation below:
hc
'o =
O
where h is Plancks constant, c is the speed of light and O is the wavelength of light
absorbed
colour absorbed O / nm
violet 410
indigo 430
blue 480
blue-green 500
green 530
yellow 580
orange 610
red 680
*LYHQWKDW o for complex R is 4.125 x 1022 kJ and using relevant data from the Data
Booklet, calculate the wavelength of light. Deduce the colour of complex R. [2]
14
(c) Iodine is not very soluble in water, it is freely soluble in KI(aq), according to the following
equilibrium:
I(aq) + I 2 (s) I 3 (aq)
(i) Draw a fully labelled experimental set-up for a voltaic cell made up of a
Cr 2 O 7 2/ Cr3+ half-cell and a I 2 /I half-cell under standard conditions. Indicate clearly
the anode and cathode and show the flow of electrons. [3]
(ii) By using appropriate values from the Data Booklet, predict what, if anything, will
happen when a small amount of acidified vanadium(II) chloride is added to a
solution of I 2 (aq). the I 2 /I half-cell.
[3]
(d) Explain the following statements.
(i) BrF 3 is a covalent compound which exhibits electrical conductivity in liquid state
at room temperature. With the aid of an equation, suggest an explanation for its
electrical conductivity. [2]
(ii) SiCl 4 reacts violently in water but CCl 4 has no reaction with water. [1]
(iii) Compounds NeF 2 and NeF 4 do not exist but XeF 2 and XeF 4 exist.
[1]
[Total: 20]
[End of Paper]
NYJC 2016 Prelim H2 Chemistry Paper 1 Answers
1 D 6 A 11 D 16 B 21 A 26 A 31 B 36 B
2 C 7 D 12 C 17 C 22 B 27 D 32 B 37 D
3 B 8 B 13 A 18 D 23 D 28 A 33 B 38 A
4 B 9 D 14 A 19 C 24 C 29 C 34 D 39 C
5 A 10 B 15 C 20 C 25 B 30 C 35 A 40 C
trendyline
H
Higher 2
CANDIDATE
NAME Teachers Mark Scheme
INDEX
CLASS 1 5 NO.
TUTOR
CHEMISTRY 9647/02
2 hours


For Examiners Use
1 P /12
2 / 15
3 / 6
4 / 13
5 / 6
6 / 20 /60
trendyline
y

For
2 Examiner's
Use
1 Planning (P)
Bakers yeast is a useful enzyme which can be used to catalyse the decomposition of hydrogen
peroxide.
H2O 2 o H2O + O 2
Set-up apparatus:
x 1 x retort stand with clamp
x 1 x 100 cm3 conical flask
x 1 x L-shape glass tube connector fitted with a rubber bung
x 1 x rubber tubing connection
x 1 x gas syringe (possible capacities of 10, 20 or 100 cm3)
Reagents and apparatus

x 100 cm3 of yeast suspension
x 100 cm3 of 3% (by weight) hydrogen peroxide
x Distilled water
x Stopwatch
x All other common laboratory equipment
When 8.0 cm3 of the yeast suspension, 4.0 cm3 of H 2 O 2 and 18.0 cm3 of distilled water is mixed,
10 cm3 of oxygen gas was produced in 90 s.
Use the above information and the reagents provided to design an experiment to
x prove first order reaction with respect to yeast by a graphical method

x prove first order reaction with respect to hydrogen peroxide by a graphical method
In your experiment, you should perform 4 other experimental runs to measure the volume of
oxygen gas produced at regular intervals. The volume of yeast suspension used should be varied
in all the runs while keeping volume of H 2 O 2 constant at 4.0 cm3 .
In your experiment, illustrate / describe the following:
x A labelled set-up for your experiment using the set-up apparatus provided
x Table of volumes that you will be using in your experiment
x Calculations to determine the maximum volume of oxygen gas produced in each
experimental run. In your calculations, assume that the density of H 2 O 2 is 1.00 g cm3 and
conditions are at r.t.p.
x Procedure for measuring the volume of oxygen gas produced at regular intervals and use
the results to find the initial rate for each run graphically
x Graphical analysis involving initial rates to deduce order with respect to yeast
x Graphical analysis involving half-lives to deduce order with respect to H 2 O 2 based on one
selected run
trendyline
For
3 Examiner's
Use
Experimental setup:
1 mark 3 apparatus drawn and labelled correctly

1 mark all apparatus drawn, labelled and connected correctly
Table of volumes
Run Vol of yeast /cm3 Vol of H 2 O 2 /cm3 Vol of water /cm3 Total volume /cm3
1 4.0 4.00 22.0 30.0
2 6.0 4.00 20.0 30.0
3 8.0 4.00 18.0 30.0
4 10.0 4.00 16.0 30.0
5 12.0 4.00 14.0 30.0
1 mark volume of yeast is between 2 20 cm3, volume of H 2 O 2 is constant

1 mark volume of water added accordingly to keep total volume constant
Calculations to determine the maximum volume of oxygen gas produced in each

experimental run
Mass of 4.00 cm3 of H 2 O 2 = 1.00 x 4.00 = 4.00 g
Moles of H 2 O 2 = (4.00 x 0.03) / 34.0 = 0.00353 mol [1]
Moles of O 2 gas = (0.00353) = 0.00176 mol
Volume of O 2 gas = 0.00176 x 24000 = 42.4 cm3 [1]
Hence minimum size of syringe to be used is the 100 cm3 size if the reaction is allowed to
go to completion
trendyline
For
4 Examiner's
Use
Procedure for measuring the volume of oxygen gas produced at fixed intervals
1. Record the initial reading on the syringe
2. Using a burette, measure 2.0 cm3 of the yeast suspension and add into the conical flask
3. Using a measuring cylinder, measure 24.0 cm3 of the distilled water and add into the
conical flask.
4. Using a burette, measure 4.00 cm3 of the H 2 O 2 into a small beaker.
5. Pour the H 2 O 2 into the conical flask, stopper the conical flask with the conical flask and
start the stop watch immediately. Swirl the conical flask a few times
6. Record the reading on the syringe every 10 seconds (or other regular time intervals, until 5
readings are collected i.e. 10 cm3 is produced.
7. Repeat steps 1 9 for the next 4 experimental runs, changing the volumes according to the
table given. For run 5 (or any other run), make sure to use the 100 cm3 syringe and allow
the reaction to go to completion.
1 mark 3/7 steps correctly written with appropriate apparatus used

1 mark all steps correctly written with appropriate apparatus used
Graphical analysis using the initial rates to deduce order with respect to yeast
For the five set of readings, plot the volume of O 2 produced against time. The tangent at
time = 0 is the initial rate (see graph below)
Vol of O2 Tangent = initial rate
Time
1 mark
Using the initial rates obtained, plot a graph of initial rates against volume of yeast used. If
order is 1, a straight line through the origin should be obtained.
rate
Volume
trendyline
of yeast
1 mark

For
5 Examiner's
Use
BLANK PAGE
Graphical analysis using a half-life method to deduce order with respect to H 2 O 2

using the selected run
Using the graph for run 5, find 2 consecutive half-lives. If order is one, the half-lives should
be constant i.e. t 1 = t 2 . [1]
Vol of
O2
42
(42)
(42)
Time
t1 t2
1 mark correct graph. X accepted instead of 42 but the graph must plateau.
[Total: 12]

For
6 Examiner's
Use
2 A solder is an alloy of metals which is used to join other metal pieces together. A specialist
solder that can be used to join together pieces of aluminium is made from a mixture by
mass of 65% zinc, 20% aluminium and 15% copper.
An experimHQWDO SURFHGXUH FDQ FRQUP WKH FRPSRVLWLRQ RI D SRZGHUHG VDPSOH RI WKLV
solder, by adding reagents and then extracting from the mixture each of the following in
sequence;
(i) copper metal,
(ii) aluminium as aluminium hydroxide,
(iii) zinc as zinc hydroxide.

DVDPSOHRIWKLVVROGHUZLWKDSSUR[LPDWHPDVVJ
PROGP3 sulfuric acid,
PROGP3 ammonia.
No other reagents should be used. Standard laboratory equipment is available.
(a) &RPSOHWHWKHRZFKDUWEHORZWRVKRZWKe order in which the reagents would be added to

the solder to allow you to extract and separate the components as copper metal, aluminium
hydroxide and zinc hydroxide in Step 1, Step 2 and Step 3 respectively.

reagent(s) added reagent(s) added reagent(s) added
H 2 SO 4 NH 3 H 2 SO 4
substance(s) present substance(s) present substance(s) present

in solution in solution in solution
ZnSO 4 Zn(NH 3 ) 4 2+ (NH 4 ) 2 SO 4 blank ok
Al 2 (SO 4 ) 3 (NH 4 ) 2 SO 4 blank ok
substance(s) removed substance(s) removed substance(s) removed

by filtration (if any) by filtration (if any) by filtration (if any)
Cu Al(OH) 3 Zn(OH) 2
[3]
6 points 3 mks.
trendyline
For
7 Examiner's
Use
(b) (i) For some of the steps in the procedure you would need to be careful to add an
appropriate quantity of a reagent.
For each step of your procedure, explain why particular quantities of reagent should
be chosen.
Step 1 excess H 2 SO 4 to completely dissolve Zn and Al [1] ..................................
..........................................................................................................................
..........................................................................................................................
Step 2 excess NH 3 to ppt Al(OH) 3 and Zn(OH) 2 and subsequently form Zn(NH 3 ) 4 2+
/dissolve Zn(OH) 2 [1] ...........................................................................................
..........................................................................................................................
Step 3 sufficient/enough H 2 SO 4 [1] neutralise/react with NH 3 [1] so that Zn(OH) 2

is .......................................................................................................................
re-ppt but not excess as that Zn(OH) 2 reacts/dissolves ..........................................
...................................................................................................................... [4]
(ii) Write the ionic equations for the reactions taking place in Step 2.
Al3+ + 3OH- Al(OH) 3 [1]...........................................................................................
[Zn(H 2 O) 6 ]2+ + 4NH 3 Zn(NH 3 ) 4 2+ [1] ................................................................... [2]
(iii) State the observations for the reactions taking place in Step 1 and Step 3.
Step 1 Pink solid in colourless solution. Effervescence produced. Gas evolved

extinguished lighted splint with a pop sound. ......................................................
Step 3 White ppt re-ppt/re-forms............................................................................ [2]
(c) $OXPLQLXPK\GUR[LGHDQG]LQFK\GUR[LGHWKDWKDYHEHHQH[WUDFWHGDUHGLIFXOWWRGU\VRLWLV
better to convert them to their oxides.
Describe how this could be done and how you would ensure that each hydroxide has been
completely converted into its oxide.
x Weigh the hydroxides and heat [1]

x Cool and re-weigh
x Repeat heating and cooling until constant mass is achieved [1]
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
trendyline
.....................................................
....................................................
....................................................................................................................................
................................................................................................................................ [2]

For
8 Examiner's
Use
(d) If the mass of aluminium oxide obtained was 1.50 g, calculate the mass of aluminium that
was present in the solder. [1]
2Al Al 2 O 3
n(Al 2 O 3 ) = 1.50/102.0 = 0.0147 mol
n(Al) = 2(0.0147) = 0.0294 mol
m(Al) = 0.0294 x 27.0 = 0.794 g [1]
(e) (YHQ LI WKH H[SHULPHQWDO GLIFXOWLHV RI H[WUDFWLQJ DOO RI WKH FRSSHU IURP WKH PL[WXUH ZHUH
RYHUFRPHLWZRXOGEHGLIFXOWWRREWDLQDQDFFXUDWHPDVVRIFRSSHUIURPWKLVH[SHULPHQW
Suggest why this is so.
Mass/amount/percentage of copper is small ..........................................................................
....................................................................................................................................
................................................................................................................................ [1]
[Total: 15]
trendyline
For
9 Examiner's
Use
3 The relationship pV=nRT can be derived from the laws of mechanics by assuming ideal
behaviour for gases.
(a) The graph below represents the relationship between pV and p for a real gas at three
pV T1 T2
T3
[1]
p
(i) Draw one line on the graph to show what the relationship should be for the same
amount of an ideal gas. [1]
(ii) With reference to the graph, state and explain which temperature, T 1 , T 2 or T 3 is the
lowest temperature.
T 1 (because it shows greatest deviation) [1]...............................................................
With decrease in temperature, KE of particles is reduced, and intermolecular ...........
forces of attraction become more significant, and the gas behaves less ideally [1] ....
.........................................................................................................................
..................................................................................................................... [2]
(b) A flask with a volume of 100 cm3 was first weighed with air filling the flask, and then with
another gas Y, filling the flask. The results, measured at 26 oC and 1.00 x 105 Pa are shown.

Calculate the relative molecular mass, M r , of Y. [3]
Mass of air = 100 x 0.00118 = 0.118 g

Mass of flask = 47.930 0.118 = 47.812 g
Mass of Y = 47.989 47.812 = 0.177 g [1]
m
pV nRT RT
Mr
m 0.177 u 8.31u 299
Mr RT [1]correct working
pV 1u 105 u 100 u 10 6
trendyline
44.0 [1]correct answer
[Total: 6]

For
10 Examiner's
Use
4 PbCl 2 is a sparingly soluble salt.
PbCl 2 (s) Pb2+(aq) + 2Cl(aq) 'H > 0
A student investigated the solubility product and solubility of PbCl 2 under different
conditions. He first added 0.0100 g of solid PbCl 2 into 120 cm3 of an unknown
concentration of HCl(aq) at 25 oC and subsequently made four changes at t 1 , t 2 , t 3 and t 4 .
The graphs below show the mass of PbCl 2 dissolved and solubility product of PbCl 2
against
time.
Mass of PbCl2
dissolved [1]
0 t1 t2 t3 t4
time
Ksp
[1]
1.70 105
0 t1 t2 t3 t4
time
trendyline
For
11 Examiner's
Use
(a) Given that 0.00465 g of PbCl 2 remained undissolved after addition of 0.0100 g of PbCl 2
into HCl, deduce the unknown concentration of the HCl. [3]
Mass of PbCl 2 dissolved = 0.0100 0.00465 = 0.00535 g [1]
Solubility of PbCl 2 in HCl(aq), x = = 1.604 104 mol dm3 [1]
Let x be the unknown concentration of HCl(aq),

PbCl 2 (s) Pb2+(aq) + 2Cl(aq)
3
4
1.604 10 mol dm 2(1.604 104) mol dm3
HCl(aq) o H+(aq) + Cl(aq)

x mol dm3 x mol dm3 x mol dm3
At saturation, ionic product = K sp

K sp = [Pb2+][Cl]2
1.70 10 = (1.604 104)(2 1.604 104 + x)2
5
x = 0.3252
= 0.325 mol dm3 [1]
Alternative:
Assuming 2(1.604 104) is small,
Ksp = [Pb2+][Cl]2
1.70 105 = (1.604 104)(x)2
x = 0.3256
= 0.326 mol dm3
(b) Determine the mass of PbCl 2 that can dissolve in 500 cm3 of water at 25 oC. [2]
Let m be the mass of PbCl 2 dissolve in 500 cm3 of water.
PbCl 2 (s) Pb2+(aq) + 2Cl(aq)
Solubility of PbCl 2 in water = [1]
K sp remain unchanged at 25 oC.

K spp = [Pb2+][Cl]2
4( )3 = 1.70 105 mol2 dm6
m = 2.252 g = 2.25 g [1]
trendyline
For
12 Examiner's
Use
(c) Some possible changes listed below were made by the student at t 1 , t 2 and t 3 .
1. Cool reaction mixture to 10 oC in water bath
2. Heat reaction mixture to 50 oC in water bath
3. Addition of AgNO 3 (aq)
4. Addition of PbCl 2 (s)
5. Addition of water
With reference to both graphs, suggest and explain the changes made at t 1 , t 2 and t 3 .
Addition of water or Addition of AgNO (aq) [1] 3
change made at t 1 ..........................................................................................................
explanation ...................................................................................................................
total volume increase when water is added to reaction mixture, hence [Pb2+] and [Cl]
....................................................................................................................................
The
decrease. According to Le Chateliers Principle, position of equilibrium shifts right to increase
the [Pb2+] and [Cl]. Thus, more PbCl2 dissolve. Ksp remain constant as Ksp is temperature
....................................................................................................................................
dependent [1]
or Addition of AgNO3(aq), presence of Ag+ caused precipitation of AgCl(s), hence [Cl]
....................................................................................................................................
decrease. According to Le Chateliers Principle, position of equilibrium shifts right to increase

[Cl ]. Thus, more PbCl2 dissolve and Ksp remain constant as Ksp is temperature dependent.
....................................................................................................................................
change made at t 2 Addition of PbCl 2 (s) [1] .............................................................................
explanation The solution is already saturated. Hence, as more PbCl 2 (s) is added, the mass
of PbCl 2 dissolve will not increase. K sp remain constant as K sp is temperature dependent. [1]
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
change made at t 3 Heat reaction mixture to 50 oC in water bath [1] ..............................
explanation According to Le Chateliers Principle, as temperature increase, the position of...
equilibrium shifts right to favour the forward endothermic reaction, to absorb heat. ...............
Hence, [Pb2+] and [Cl] increase. The mass of CaSO 4 dissolved and K sp increase. [1]...........
................................................................................................................................[6]
(d) The student added concentrated HCl at t 4 . On both the graphs on Page 10, draw how the
two graphs would look like after t 4 . [2]
PbCl 2 + 2Cl- PbCl 4 2
Formation of complex, PbCl 4 2, increases the solubility of PbCl 2 . Hence, mass of PbCl 2
dissolve increase. K sp remain constant as K sp is temperature dependent.
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[Total: 13]

For
13 Examiner's
Use
5 Compound A (C 12 H 16 O 2 ) exhibits optical isomerism. It does not react with hot acidified
K 2 Cr 2 O 7 . 1 mole of A reacts with 1 mole of PCl 5 to form B. A reacts with cold dilute KMnO 4
to form C (C 12 H 18 O 4 ). Upon heating with acidified KMnO 4 , A gives D (C 9 H 10 O 4 ) and E. D
produces effervescence when aqueous Na 2 CO 3 is added. 1 mole of D reacts with 3 moles
of aqueous bromine. E gives F, a yellow precipitate with warm alkaline aqueous iodine.
Draw the structures of A, B, C, D, E and F.
CH3 H CH3 CH3 H CH3
HO C C C CH3 Cl C C C CH3
OH [1] OH [1]
A B
CH3 H CH3 CH3 OH
HO C C C CH3 HO C C O
OH OH
OH [1] OH [1]
C D
CH3
CHI 3 [1]
O C CH3 [1]
E F
[Total: 6]

For
14 Examiner's
Use
6 The Ritter reaction is an organic reaction used to convert a nitrile and a tertiary alcohol, in a
second order reaction, to form an amide using strong aqueous acid as the catalyst.
O R2
R2 + R3
H (aq) C C
R1 CN R3 C OH
R1 N R4
R4
H
, ,
The proposed mechanism is as follows:
R2 R2
R3 C OH H C R3 H2O
+
step 1
R4 R4
H H
R2 R2 O R2
H2O
R1 CN C R3 step 2 R1 C N C R3 step 3 R1 C N C R3
R4 R4 R4
step 4
H
O R2 O R2
R1 C N C R3 H+ step 5 R1 C N C R3
H R4 H R4
(a) Predict the structures of P, Q and T for each of the following Ritter reactions. [3]
CN
[1] OH [1]
+ O
H (aq)
+
N
H
Q R
P
(C 6 H 12 O)
(C 8 H 7 N)
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For
15 Examiner's
Use
O
H
+
HO CN H (aq) N
S [1]
(C 8 H 15 NO)
(b) Describe a simple chemical test to distinguish compound R and S, stating clearly the
observations.
(1) Na, room temp or (2) PCl5/SOCl2, room temp or (3) KMnO4, H2SO4(aq), heat [1]
Test .............................................................................................................................
(1) Compound S: effervescence of H2 gas evolved which extinguishes lighted
Observation .................................................................................................................
splint with a pop sound. Compound R: no effervescence of H2 observed.
(2) Compound S: white fumes of HCl evolved Compound R: no white fumes.
....................................................................................................................................
(3) Compound R: Purple KMnO4 decolourise, white ppt of Benzoic acid formed.
................................................................................................................................
Compound S: purple KMnO4 remained. [1] [2]
(c) Suggest the types of reaction occurring in steps 3 and 4.

Nucleophilic Addition [1]
Step 3 ...........................................................................................................................
Acid-base [1]
Step 4 ....................................................................................................................... [2]
(d) Complete the mechanism of step 3 and 4 below with arrows, showing the lone pairs and
dipole charges. [3]
H O H H H
R2 O R2 O
R2
R4 R4 H R4
H
G G
H O H H H
R2 O R2 O R2
G G
R4 R4 H R4
x correct arrows for step 3
x correct arrows for step
p4
x show G and G in n both step

stepstrendyline
x lone pairs on H 2 O and N atom of imine
PDUNV PDUNV PDUN PDUNV

For
16 Examiner's
Use
(e) Suggest which step of the proposed mechanism on Page 14 is the slowest step. Explain
your reasoning.
Step 1 is the slowest step as Ritter reaction is a second order reaction (as stated in the
question), involving one molecule of tertiary alcohol and a H+ ion. [1]
................................................................................................................................ [1]
(f) Primary alcohols such as ethanol are not suitable reagents for the Ritter reaction.
(i) Draw a diagram to show the orbitals of the carbon in the carbocation in step 1 and
state the type of hybridisation involved. [1]
sp2 [1]
(ii) Suggest why tertiary alcohols are used in the Ritter reaction but not primary
alcohols.
H R3
C C
R H R2 R4
primary carbocation tertiary carbocation
Tertiary alcohol forms a tertiary carbocation in step 1, which is more stable than a
primary carbocation from a primary alcohol. [1]
The three electron donating alkyl groups donate electrons to the carbocation to
disperse the positive charge (decrease the positive charge intensity) and stablise
the tertiary carbocation. [1]
..................................................................................................................... [2]
(iii) Suggest why phenylmethanol is a suitable reagent for the Ritter reaction even
though it is a primary alcohol.
OH Note:
The primary carbocation formed from
phenylmethanol in step 1 has an
unhybridised p-orbital which forms an
phenylmethanol
RYHUODSZLWKWKH-orbital of the carbons
trendyline
nd
n dyyline
d
in benzene.
H
C
H

For
17 Examiner's
Use
The positive charge on the carbocation delocalised into the benzene ring, therefore
stabilising the primary carbocation. [1]
or
Electron from the benzene ring delocalised to the carbocation, stabilising the
positive charge.
..................................................................................................................... [1]
(g) This equation for the Ritter reaction is repeated from page 14.
O R2
R2 + R3
H (aq) C C
R1 CN R3 C OH
R1 N R4
R4
H
R1, R2, R3 and R4 are alkyl groups
(i) Using suitable data from the Data Booklet, calculate the enthalpy change of reaction.
[2]
From the Data Booklet,
%(&1 %(&1

%(&2 BE (C=O) = 740
%(2+ %(1+
'H r %(ERQGVEURNHQ%(ERQGVIRUPHG

= 890 + 360 + 460 (2305 + 740 + 390) [1] for correct substitution of values
N-PRO1 [1] for final answer and allow ecf
(ii) Suggest and explain if the Ritter reaction is spontaneous at high or low temperature.
'G = '+7'S
x Low temperature
x 'S is negative
x as there is a decrease in entropy, whereby two reactant molecules
undergo Ritter reaction to form one product molecule.
x T'S is positive, 'G is negative only at low temperature
1 = 0 mark 2 = 1 mark 3 = 2 marks 4 = 3 marks
.........................................................................................................................
..................................................................................................................... [3]
[Total: 20]
trendyline
H2 Chemistry 9647/02 NYJC J2/16 PX [End[Turn over
of Paper]
H
Higher 2
Teachers Mark Scheme

CHEMISTRY 9647/03
2 hours
Candidates answer Section A on the Question Paper

Data Booklet

Section B
Answer all questions on separate answer paper. For Examiners Use
Section A
Total
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[[Turn over
2
1(a) Copper(I) sulfate, Cu 2 SO 4 , can be made from copper(I) oxide under non-aqueous
conditions. On adding this salt to water, it immediately undergoes a disproportionation
reaction.
(i) Suggest, with a reason, the colour of copper(I) sulfate. [2]
Colourless. [1] Cu+ has an electronic configuration of [Ar] 3d10 or fully filled d
orbitals, hence d-d transition cannot take place. [1]
(ii) Using suitable data from the Data Booklet, explain why the disproportionation
reaction occurs, and write an equation for it. [3]
E (Cu2+/Cu+) = +0.15 V
E (Cu+/Cu) = +0.52 V
[1] for quoting E values
E cell = E (Cu+/Cu) E (Cu2+/Cu+) = +0.52 (+0.15) = + 0.37 V > 0

Since E cell > 0, reaction is feasible. [1]
2Cu+ Cu2+ + Cu [1]
(b) Palladium(II) salts can form square planar complexes. Successive addition of ammonia and
hydrogen chloride to an aqueous palladium(II) salt produces, under different conditions,
three compounds with empirical formula PdN 2 H 6 Cl 2 . Two of these, A and B, are non-ionic,
with M r = 211. A has a dipole moment, whereas B has none. The third compound, C, is
ionic, having M r = 422, and contains palladium in both its cation and anion.
For each A, B and C, deduce a structure that fits the above data, explaining your reasons
fully. [6]
M r (PdN 2 H 6 Cl 2 ) = 106 + 2(14.0) + 6 +2(35.5) = 211

A and B have the molecular formula PdN 2 H 6 Cl 2. ()
C has the molecular formula (PdN 2 H 6 Cl 2 ) 2 Pd 2 N 4 H 12 Cl 4 . ()
Since palladium (II) salts form square planar complexes, it has a coordination number of
4.()
Structures of A and B:
Cl NH3 H3N Cl
Pd Pd
A: B:
Cl NH3
[1] Cl NH3 [1]
Since A has a dipole moment and B has no dipole moment, A is a polar molecule and B is
a non-polar molecule. ()
4() [2], 3(),2() [1]
C: [Pd(NH 3 ) 3 Cl]+ ; [Pd(NH 3 )Cl 3 ] OR

[Pd(NH 3 ) 4 ]2+; [PdCl 4 ]2
[1] each for correct cation and anionM r (PdN 2 H 6 Cl 2 ) = 106 + 2(14.0) + 6 +2(35.5) = 211
A and B have the molecular formula PdN 2 H 6 Cl 2. [1]

C has the molecular formula (PdN 2 H 6 Cl 2 ) 2 Pd 2 N 4 H 12 Cl 4 . [1]
trendyline
H2 Chemistry
y 9647/03 NYJC J2/16 PX
P [[Turn
T Over
3
Structures of A and B:
Cl NH3 H3N Cl
Pd Pd
A: B:
Cl NH3 [1] Cl NH3 [1]
C: [Pd(NH 3 ) 3 Cl]+ ; [Pd(NH 3 )Cl 3 ] OR

[Pd(NH 3 ) 4 ]2+; [PdCl 4 ]2
[1] each for correct cation and anion
(c) Benzene ring is often represented as a structure that has a ring within the hexagon.
Alternatively, chemists have also represented the structure of benzene in the following
forms, known as resonance structures.
Benzene (two resonance forms)
The resonance relationship is indicated by the double headed arrow between them. The
only difference between resonance forms is the placement of the pi electrons and
non-bonding electrons.
Most aromatic compounds undergo electrophilic substitution. However aryl halides undergo
a limited number of substitution reactions with strong nucleophiles.
An example of a reaction is as follows:
Nu
A X A Nu + X
where A is an electron withdrawing group and X is a halogen
The mechanism of this reaction has two steps:

x addition of the nucleophile
x elimination of the halogen leaving group
trendyline
4
Step 1 involves the addition of the nucleophile (Nu). The Nu attacks the carbon atom
bonded to a halogen, causing the pi bond to break. A resonance stabilised carbanion with a
QHZ&1XERQGLVIRUPHG7KHDURPDWLFULQJLVGHVWUR\HGLQWKLVVWHS
Nu
X X
Nu

A A
Step 2 involves the loss of the halogen X, reforming the aromatic ring.
Nu
X Nu
X

A A
Two other resonance structures of the intermediate in Step 1 are shown below:
Nu Nu
X X
I II
Z
A A
(i) Copy the above diagram and draw the resonance structure, Z. In your answer,
show any relevant charges, lone pairs of electrons and movement of electrons in
forming Z. [2]
Nu Nu Nu
X X

X
I II

A A A
[1] for correct structure of Z

[1] for correct arrow pushing
The reaction below shows the synthesis of compound, D.
N(CH3)2 N(CH3)2
O 2N
O 2N
potassium metal +
+ HCl
Cl HO O
D
(ii) Suggest the role of potassium metal in the reaction. [1]
It is used to generate a stronger nucleophile, C 6 H 5 CH(O)CH 2 CH 2 N(CH 3 ) 2. [1]

trendyline
5
(iii) Use the information given above to draw out the full mechanism for the reaction that
forms D, labelling the slow and fast steps. In your answer, showing any relevant
charges, lone pair of electrons and movement of electrons. [3]
N(CH3)2 N(CH3)2
+ + 1/2 H2
K + HO K O
N(CH3)2
N(CH3)2
O 2N
O 2N
slow Cl
+
O
Cl
O
N(CH3)2 N(CH3)2
O 2N O 2N
fast
Cl
+ Cl
O O
[1] for step 1 (accept OH as the nucleophile)

[1] for step 2
[1] for labelling slow and fast steps correctly
(d) Describe and explain the relative ease of hydrolysis of the following three
chloro-compounds. [3]
Cl COCl CH2Cl
The relative ease of hydrolysis of the three chloro-compounds in increasing order is as

follows:
Cl CH 2Cl COCl
< <
[1]
trendyline
6
Chlorobenzene is resistant to hydrolysis. The p orbital of chlorine overlaps with S electron
cloud of benzene ring hence strengthening the C-Cl bond and hence the bond does not
break easily. [1]
COCl
Hydrolysis of is the fastest. The acyl/C=O carbon atom is attached to 2 highly

CH 2 Cl
electronegative atoms, O and Cl while that in is only attached to one

electronegative atom (Cl).
COCl
Hence acyl/C=O carbon atom in is more electron deficient (i.e. carries a larger
SDUWLDOSRVLWLYHFKDUJHWKDQWKHFDUERQDWRPLQ& 6 H 5 CH 2 Cl.
Therefore is most susceptible to nucleophilic attacks. [1]

[Total: 20]
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7
2 Sulfuric acid, H 2 SO 4 , can behave as an acid, an oxidising agent or as a dehydrating agent
in various reactions.
(a) Draw a diagram to illustrate the shape of pure sulfuric acid and indicate the bond angle
about the sulfur atom. [2]
tetrahedral shape + Diagram [1]
S
O OH
OH
bond angle about S = 109.5O [1]
(b) The Contact Process is used for the manufacture of sulfuric acid. One of the reactions that
takes place is the following reversible reaction:
2SO 2 (g) + O 2 (g) 2SO 3 (g) 'H = 197 kJ mol1
Sulfur dioxide and oxygen in a 2:1 molar ratio at a total initial pressure of 3 atm is passed
over a catalyst in a fixed volume vessel at 400 oC. When equilibrium is established, the
percentage of sulfur trioxide in the mixture of gases is found to be 30%.
(i) Write an expression for the equilibrium constant, K p , of the reaction. [1]
P
2
SO3
KP = [1]
P P
2
SO2 O2
(ii) Calculate the value of K p at 400 oC, stating its units. [3]
2SO 2 (g) + O 2 (g) 2SO 3 (g)

Initial Partial Press /atm 2 1 0
Change in Press /atm -2x -x +2x
Final Partial Press /atm 2 - 2x 1-x 2x
Total Pressure, P T = 2 - 2x + (1 x) + 2x = 3- x [1]

2x
SO 3 = 3 - x = 0.30
? x = 0.391 [1]
0.782
2
KP = 0.679 atm 1 correct answer and units [1]

1.218 (0.609)
2
(iii) How would the percentage conversion of SO 2 into SO 3 be affected when the
pressure is raised? Explain. [2]
conversion to SO 3 will increase.

With increased pressure, by Le Chateliers Principle, position of equilibrium will shift
to the right so as to favour the side which produces the less number of moles of gas.
trendyline
8
(c) Dilute sulfuric acid takes part in typical acid-base reactions and it can be used to distinguish
the following solids: MgO, BaO and SiO 2 .
State the observations, if any, to indicate the differences in their reaction when water is
added to each solid followed by dilute sulfuric acid. [4]
Solid MgO is insoluble in water / sparingly soluble in water.

It is a basic oxide and dissolves in H 2 SO 4 (aq) to form a colorless solution.
Solid BaO dissolves in water to form colorless solution , upon adding H 2 SO 4 (aq) a white
ppt BaSO 4 is formed
SiO 2 does not dissolve in water or acid.
[2] for observations with water
[2] for observations with dil H 2 SO 4
(d) Sulfur dioxide is a major pollutant from sulfuric acid plants. The SO 2 emitted into the
atmosphere is oxidised in the air, which then reacts with water to form sulfuric acid, hence
causing acid rain:
2SO 2 (g) + O 2 (g) + 2H 2 O(l) o 2H 2 SO 4 (l) 'H 1
Using the data below and data from (b), construct an energy cycle to calculate
(i) the enthalpy change of formation of SO 2 (g), and hence

2 x 98.5
2SO2 (g) + O2 (g) o 2SO3 (g)
2 x -493
2S (s) + 3 O2 (g)
2 x 'Hf (SO2) = 2 x 493 (2 x 98.5)

= 789 kJmol-1
[1] for ans, [1] for working
(ii) the enthalpy change of reaction, 'H 1 for the above reaction.
Enthalpy change of formation of H 2 O(l) = 286 kJ mol1

Enthalpy change of formation of H 2 SO 4 (l) = 811 kJ mol1
Enthalpy change of formation of SO 3 (g) = 493 kJ mol1
[4]
'H rxn
2SO2 (g) + O2 (g) + 2H2O (l) o 2H2SO4 (g)
789 - 2 x -286 2 x -811
2S (s) + 4O2 (g) + 2H2 (g)
? 'Hrxn = (2 x 811) (789) (2 x 286)

= 261 kJmol-1
[1] for ans, [1] for working
9
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10
(e) Alcohols react with concentrated sulfuric acid at high temperatures to form alkenes. A
common side reaction that can happen is the formation of ethers, which is also catalysed
by concentrated sulfuric acid.
R R R
conc H2SO4
heat
R R R
R R R
conc H2SO4
heat
R R R
The mechanism occurs via 3 steps:
Step 1:
An acid base reaction in which H+ from H 2 SO 4 protonates the oxygen atom in alcohol. This
step is very fast and reversible.
Step 2:
A second alcohol molecule functions as the nucleophile and attacks the product from
step 1. The CO bond is cleaved and a water molecule leaves the molecule. This creates
R
+
O
an oxonium ion R' H intermediate.
Step 3:
Another acid base reaction in which the proton in the oxonium ion is removed by a suitable
base (in this case a water molecule) to give the ether product. This step is very fast and
reversible.
(i) Draw the ether formed when cyclopentanol undergoes the above reaction.
OH
cyclopentanol
[1]
O
[1]
(ii) Draw out the full mechanism for the reaction between two cyclopentanol molecules
to form an ether. In your answer, show any relevant charges, lone pairs of electrons
and movement of electrons. [3]
trendyline
11
+
:OH OH2
fast
Step 1:
+
H
H H
+ H
O +
:OH slow O
Step 2: + H2O
G
H fast
+
Step 3: O O + H3O+
H2O:
1 mk for each step (with arrows, lone pairs) total 3 mks
[Total: 20]
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12
3 Garlic contains many amino acids, minerals and enzymes. Garlic also contains at least 33
sulfur compounds like alliin, allicin and ajoene. The sulfur compounds are responsible for
both garlics pungent odour and many of its medical effects.
(a) When raw garlic is chopped or crushed, the enzyme allinase converts alliin into allicin,
which is responsible for the odour of fresh garlic.
O NH2 O
S allinase S
COOH S
alliin allicin
Allicin can also be biosynthesised by using serine and glutathione.
NH2 COOH O
HO NH
COOH H2N NH COOH
O
SH
serine glutathione
(i) Explain why raw chopped garlic has a stronger odour than when it is cooked. [1]
Enzyme allinase is denatured by heat. [1]
(ii) When one molecule of serine reacts with one molecule of glutathione, it is possible
to form two esters with different structural formulae.
Draw the structural formula of each of these esters. [2]
NH2
O
COOH
O C O
NH
H2N NH COOH
O
SH [1]
COOH O NH2
NH O
H2N NH C COOH
O O
SH [1]
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13
(iii) Draw the structural formulae of the products when glutathione is hydrolysed. [3]
COOH O
OH H2N
H2N OH H2N COOH
O
SH
[1] x 3
Alliin has pK a values of 1.84 and 8.45.
(iv) Make use of these pK a values to suggest the major species present in solutions of
alliin with the following pH values. [3]
x pH 1
x pH 7
x pH 11
pH 1
+
O NH3
S
COOH [1]
pH 7
+
O NH3
S -
COO [1]
pH 11
O NH2
S -
COO [1]
(v) Calculate the pH of 0.10 mol dm3 solution of alliin. [1]
[H+] = 10 1.84 u 0.10 = 0.03801 mol dm3

pH = lg 0.01188 = 1.42 [1]
(vi) With reference to the pK a values, identify the major species formed when 10 cm3 of
0.10 mol dm3 NaOH is added to 10 cm3 of 0.10 mol dm3 protonated alliin. Hence,
deduce whether the solution is acidic, neutral or alkaline. [2]
pKa = 8.45
+
O NH3 Ka = 108.45 = 3.54 109
S -
COO pKb = 14 1.84 = 12.16
Kb = 1012.16 = 6.918 1013
[1]
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14
Since K a (NH 3 +) > K b (COO), the solution will be acidic. [1]
(vii) Sketch the pH-volume added curve you would expect to obtain when 30 cm3 of
0.10 mol dm3 NaOH is added to 10 cm3 of 0.10 mol dm3 protonated alliin.
Briefly describe how you have calculated the various key points on the curve. [4]
At 5 cm3, 1st maximum buffering capacity point

pH = pK 1 = 1.84
At 10 cm3, 1st equivalence point, solution contains RCH(NH 3 )+COO which is an

acidic salt with K a = K 2 = 108.45
RCH(NH 3 )+COO + H 2 O RCH(NH 3 )+COOH + H 3 O+ K 2 = 108.45
10
u 0.10
+
[RCH(NH 3 ) COO ] = 1000 =0.05 mol dm3
20
1000
pH = lg 0.05 u 10 8.45 = 4.875 | 4.88
pK a1 pK a 2 1.84 + 8.45
OR pH= = 5.145 = 5.15
2 2
At 15 cm3, 2nd maximum buffering capacity point

pH = pK 2 = 8.45
At 20 cm3, 2nd equivalence point, solution contains RCH(NH 2 )COO which is a basic
salt with K b = 10(14 K2) = 10(14 8.45) = 105.55
10
u 0.10
[RCH(NH 2 )COO ] = 1000 = 0.03333 mol dm3
30
1000
pOH = lg 0.03333 u 10 5.55 = 3.513
pH = 14 3.513 = 10.48 | 10.5
At 30 cm3, solution contains 10 cm3 excess NaOH
[OH] = concentration of the 10 cm3 of excess NaOH in a total solution
10
u 0.10
= 1000 = 0.025 mol dm3
40
1000
pH = 14 pOH = 14 (lg 0.025) = 12.4
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15
pH
12.4
Equivalence point 2
10.5
Equivalence point 1
8.45
4.88 or 5.15
1.84
1.42
0
5 10 15 20 25 30 VNaOH/cm3
Key points to look out for
x Label the x and y-axis clearly
x Curve start at pH = 1.42 with a sharp increase before flattening off due to formation
of buffer
x Two neutralisation points at 10 cm3 and 20 cm3, labelling of pH values at equivalence
points is not needed
x Two buffer regions centred at pH values 1.84 and 8.45 (clearly labelled) respectively
x When V NaOH = 30 cm3, pH = 12.4, showed calculations on how this pH value is
obtained
Total of 4 marks
Deduct 1 mark for each missing bullet point
(b) Diallyl disulfide is one of the principal components of the distilled oil of garlic. It is a
yellowish liquid which is insoluble in water and has a strong garlic odour. It is produced
during the decomposition of allicin.
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O
S S
S S
allicin diallyl disulfide

Diallyl disulfide can be produced industrially from sodium disulfide and allyl chloride at
temperatures of 40 60 C in an inert atmosphere.
40 60 oC
Cl S
Na2S2 + 2 S + 2NaCl
inert gas
allyl chloride
(i) Give the IUPAC name of allyl chloride. [1]
3-chloroprop-1-ene [1]
(ii) Explain, in thermodynamic terms, suggest why diallyl disulfide is insoluble in water.
[2]
Diallyl disulfide is a non-polar molecule. The energy evolved in the formation of
dispersion forces between diallyl disulfide and water molecules is insufficient [1] to
overcome the energy required to break the dispersion forces between diallyl
disulfide molecules and hydrogen bonding between water molecules. [1]
(iii) State the type of reaction when diallyl disulfide is converted back to allicin. [1]
Oxidation [1]
[Total: 20]
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4 Alkynes are organic molecules which contain carbon-carbon triple bonds and are part of the
homologous series with formula of C n H Q i.e.
R1 C C R2
where R 1 and R 2 = H or alkyl or aryl groups
Alkynes exhibit similar chemical properties to alkenes.

e.g. addition reactions with electrophiles i.e. X 2 or HX to form alkenes
R1 R2
HX
R1 C C R2 C C
H X
e.g. oxidation by hot concentrated KMnO 4 to form mixture of carboxylic acids
KMnO 4
R1 C C R2 R1COOH + R2COOH
However, unlike alkenes, terminal alkynes are able to react with strong bases like sodium
amide.
+
RC CH + NaNH2 RC C Na + NH3
(a) Ethyne, C 2 H 2 , is heated with excess sodium bromide and concentrated sulfuric acid to
produce a dihalide, C 2 H 4 Br 2 . The overall reaction may be considered to take place in two
stages, the first between inorganic reagents only and the second involving the organic
reagent.
(i) Write an equation for the first stage. [1]
NaBr + H 2 SO 4 oNaHSO 4 + HBr [1]
(ii) Suggest a structure for the dihalide formed. [1]
CH 3 CHBr 2 [1] follow markovnikov rule
(iii) When the concentrated sulfuric acid is added to the reaction mixture, cooling is
necessary to prevent the formation of inorganic by-products.
Write an equation to explain the formation of these inorganic by-products. [1]
2HBr + H 2 SO 4 oBr 2 + SO 2 + 2H 2 O [1]
(b) Compound A, is an enyne chloride (i.e. compounds that contains chloro, alkyne and alkene
functional groups).
Cl
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Compound A
One mole of compound A reacts with two moles of Br 2 to produce a mixture of

4 stereoisomers. Draw structures of the stereoisomers formed. [3]
CH2Cl CH2Cl
CH3 CH3
H3C CH3
Br Br
cis Br
CH3 CH3
Br
Br Br Br Br
CH2Cl CH2Cl
CH3 CH3
Br Br
Br Br
trans Br Br
CH3 CH3
H3C Br Br CH3
(c) Compound B, which is an isomer of Compound A and also an enyne chloride, is treated
with sodium amide, NaNH 2 followed by heating under reflux to form compound C, C 8 H 10 .
Compound C reacts with hot concentrated KMnO 4 to produce butane-1,4-dioic acid only.
(i) Explain the reaction with NaNH 2 . [1]
To deprotonate the terminal alkyne group

Or acid-base reaction with terminal alkyne. [1]
(ii) Hence, explain the formation of compound C. [1]
The deprotonated alkyne acts as a nucleophile which undergoes

intramolecular nucleophilic substitution to form Compound C [1]
(iii) Suggest skeletal structures for compounds B and C. [2]
Cl
B:
C:
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When a current of 1.0 A was passed through aqueous potassium maleate (KO 2 CCH=CHCO 2 K) for
15 minutes, it was found that 110 cm3 H 2 , measured at r.t.p, was collected at the cathode. The
following reaction took place.
2H 2 O + 2e o H 2 + 2OH
(d) State the relationship between the Faraday constant, F and the Avogadros constant, L. [1]
F = Le where e = charge on 1 electron [1]
(e) Using the data above and the Data Booklet, calculate a value for Avogadros constant. [3]
Q = 1.0 15 60 = 900 C [1]

n(H 2 ) = 110 / 24000 = 0.00458 mol
n(e) = 2 n(H 2 ) = 0.00917 mol [1]
F = Q / n(e) = 98182 = 98200 C
L = 98182 / 1.60 1019 = 6.14 1023 [1]
(f) Ethyne and CO 2 gas were produced at the anode. In order to determine the stoichiometry
of the anode reaction, the volume of the gases collected at the anode was measured. The
anode gas was first passed through aqueous NaOH before being collected in a gas
syringe. The following data was collected:
x mass of bottle containing NaOH before experiment = 10.501 g

x mass of bottle containing NaOH after experiment = 10.904 g
x initial reading on syringe = 10.0 cm3
x final reading on syringe = 120.0 cm3
(i) State the oxidation state of carbon in ethyne. [1]
1 [1]
(ii) With the help of an equation, explain the purpose of passing the anode gas through
NaOH. [1]
2NaOH + CO 2 oNa 2 CO 3 + H 2 O
Purpose of NaOH is to absorb CO 2 [1]
(iii) Calculate the volume of CO 2 produced, assuming r.t.p conditions. [1]
Change in mass of NaOH = mass of CO 2 produced = 0.403 g

n(CO 2 ) = 0.403 / 44.0 = 0.009159 mol
V(CO 2 ) = 24000 n(CO 2 ) = 220 cm3 [1]
(iv) Hence, suggest an ionic equation for the reaction that occurred at the anode. [1]
Volume of ethyne gas = 110 cm3

O 2 CCH=CHCO 2 o C 2 H 2 + 2CO 2 + 2e
(g) When aqueous potassium maleate was acidified, maleic acid, HO 2 CCH=CHCO 2 H
(pK a1 = 1.90 and pK a2 = 6.07) was liberated. Fumaric acid (pK a1 = 3.03 and pK a2 = 4.44) is
a stereoisomer of maleic acid.
With a suitable illustration, suggest a reason why maleic acid has a lower pK a1 but higher
pK a2 than fumaric acid.
[2]
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hydrogen bonding
G G
G OH O-
O O
[1]
Maleic acid is the cis-isomer while fumaric acid is the trans isomer. Hence the negative
carboxylate ion is stabilised by intramolecular hydrogen bonding. Hence maleic acid is stronger
acid than fumaric acid. [1]
[Total: 20]
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5(a) Dopamine is an organic compound of the catecholamine and phenethylamine families that
plays several important roles in the brain and body. Its name is derived from its chemical
structure: it is an amine synthesised by removing a carboxyl group from a molecule of
its precursor compound, L-DOPA.
Below is a synthetic route involving L-DOPA and dopamine:
O
HO HO NH2
OH
+ CO 2
NH2
HO HO
L-DOPA Dopamine
Reaction I Reaction III

Compound H
O Product J
HO
Cl
HO N
NH2
HO
HO
Reaction II
anhydrous AlCl 3
Isomers F and G
C9H9O 3N
(i) State the reagents and conditions and any observations in Reaction I. [1]
Reagents & conditions: PCl 5 or SOCl 2

Observation: White fumes of HCl
1 mark for both
(ii) Aluminium chloride is used as a catalyst in electrophilic substitution reactions. The

Cl
+ Cl 2 + HCl

x The first step is the reaction between Cl 2 and AlCl 3 .
x The benzene is then attacked by the Cl+ cation in the second step.
The first step is the reaction between Cl 2 and AICI 3 .

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+
The benzene ring is then attacked by the CI cation in the second step.
AICl 3 reacts in a similar way with acyl chlorides, producing a carbocation
that can then attack a benzene ring.
Predict the structures of isomers F and G in Reaction II. [2]

OH
HO HO
NH2 NH2
HO
O O 1 mark each
(iii) In Reaction III, dopamine was reacted with alkyl halide H to give the final product J.
Draw the displayed formula of H. [2]
H H
H H H
Br C C Br
C C C
H H
H H H [12] correct RX & displayed formula
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(b) Dopamine is a bidentate ligand. When different volumes of 0.0030 mol dm3 of aqueous
Cr(III) and 0.0020 mol dm3 of alkaline dopamine solution were mixed, a complex R is
formed. Analysis of R shows that its formula is [Cr(C 8 H 9 NO 2 ) x (H 2 O) y ]z, where x, y and z
are integers.
To determine the stoichiometry of the complex ion formed, the colour intensities of these
different mixtures were measured using a colorimeter. The following absorption spectrum
was obtained.
Relative Absorbance
| | | | | | | | | | | | | | | | | | | |
Volume of Cr3+ / cm3
| | | | | | | | | | | | | | | | | | | | |
10 9 8 7 6 5 4 3 2 1
Volume of alkaline dopamine / cm3
(i) Use the graph and the information given to determine the formula of complex R.
Show your workings clearly. [3]
n(Cr3+) : n(dopamine)
2.5 7.5
= 0.0030 x : 0.0020 x
1000 1000
= 7.50 x 106 : 1.50 x 105
= 1:2 [1]
?x=2
(ii) The crystal field describes the breaking of orbital degeneracy in transition metal
complexes due to the presence of ligands. When the d-orbitals split into high energy
and low energy orbitals, the difference in energ\RIWKHWZROHYHOVLVGHQRWHGDV o .
7KH UHODWLRQVKLS EHWZHHQ o and colours of complexes can be described in the
equation below:
hc
'o =
O
where h is Plancks constant, c is the speed of light and O is the wavelength of light
absorbed
colour absorbed O / nm
violet 410
indigo 430
blue 480
blue-green 500
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green 530
yellow 580
orange 610
red 680
*LYHQWKDW o for complex R is 4.125 x 1022 kJ and using relevant data from the Data
Booklet, calculate the wavelength of light. Deduce the colour of complex R. [2]
hc
'o =
O
6.63 x 10-34 (3 x 108 )
[1]
4.125 x 10-22 x 1000
= 4.82 x 10-7m or 482 nm
Since colour absorbed is blue (482 nm blue), the colour of complex R should be the
orange (complementary colour). [1]
(c) Iodine is not very soluble in water, it is freely soluble in KI(aq), according to the following
equilibrium:
I(aq) + I 2 (s) I 3 (aq)
(i) Draw a fully labelled experimental set-up for a voltaic cell made up of a
Cr 2 O 7 2/ Cr3+ half-cell and a I 2 /I half-cell under standard conditions. Indicate clearly
the anode and cathode and show the flow of electrons. [3]
Platinised Pt anode Platinised Pt cathode

() (+)
1 mol dm3 of
Cr2O72 & Cr3+
1 mol dm3 of H+
1 mol dm3 of I&
1 mol dm3 of I3
All 5 points 3 marks, 3-4 points 2 marks, 2 points 1 mark

x Cr 2 O 7 2/Cr3+ half cell (with acidified medium)
x I 3 /I half cell (with Pt electrode)
x Complete circuit (salt bridge), standard condition (1 mol dm3)
x Direction of electron flow
x Clear indication of anode, cathode
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(ii) By using appropriate values from the Data Booklet, predict what, if anything, will
happen when a small amount of acidified vanadium(II) chloride is added to a
solution of the I 2 (aq). /I half-cell.
[3]
I 2 + 2e- 2I (+0.54)

V3+ + 2e- V2+
VO2+ + 2H+ + e- V3+ + H 2 O
VO 2 + + 2H+ + e- VO2+ + H 2 O (+1.00)
I 2 (aq) + V2+(aq) o 2I(aq) + V3+(aq)

E cell = (+0.54) (0.26) = +0.80 V > 0 ?reaction is feasible. x
I 2 (aq) + 2V3+(aq) + 2H 2 O(l) o 2I(aq) + 2VO2+(aq) + 4H+(aq)

E cell = (+0.54) (+0.34) = +0.20 V > 0 ?reaction is feasible. x
I 2 (aq) + 2VO2+(aq) + 2H 2 O(l) o 2I(aq) + 2VO 2 +(aq) + 4H+(aq)

E cell = (+0.54) (+1.00) = 0.46 V < 0 ?reaction is not feasible. x
V2+ will be oxidised to V3+ and finally VO2+ while I 2 will be reduced to I. x
All 4 points 3 marks, 2-3 points 2 marks, 1 point 1 mark

A must to show calculation of E cell for all 3 equations.
(d) Explain the following statements.
(i) BrF 3 is a covalent compound which exhibits electrical conductivity in liquid state
at room temperature. With the aid of an equation, suggest an explanation for its
electrical conductivity. [2]
BrF 3 autoionisesI ionises in the liquid state to give BrF 2 + and BrF 4 ions
which are mobile, thus accounting for its electrical conductivity. [1]
2BrF 3 o BrF 2 + + BrF 4 [1]
(ii) SiCl 4 reacts violently in water but CCl 4 has no reaction with water. [1]
Water molecules could not form co-ordinate bonds with the central carbon
atom of CCl 4 because carbon is in period 2 and cannot accommodate lone pair
of electrons from H 2 O. [1]
(iii) Compounds NeF 2 and NeF 4 do not exist but XeF 2 and XeF 4 exist.
[1]
Xenon has larger radii; therefore the electron attraction to the nucleus is
weaker in comparison to the smaller noble gases. OR
Energy levels of the 5p orbital, 6s and 4f orbitals are very close and hence
energetically accessible. Only a small amount of energy is needed to excite the
paired electrons from the 5p orbitals to the 6s and 4f electrons where they can then
form covalent bonds with other atoms. [1]
[Total: 20]
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[End of Paper]
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PIONEER JUNIOR COLLEGE
JC2 PRELIMINARY EXAMINATION

HIGHER 2
CANDIDATE
NAME
CT INDEX
1 5 S
GROUP NUMBER
CHEMISTRY 9647/01
1 hour
Data Booklet

Write your name, Centre number and index number on the Answer Sheet in the spaces provided
unless this has been done for you.
Answer Sheet.
This document consists of 20 printed pages [Turn over

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Section A
For each question, there are four possible answers labelled A, B, C and D. Choose the
one you consider to be correct.
1 Which of the following quantities is equal to the Avogadro constant?
A the number of atoms in 24 dm3 of nitrogen gas at r.t.p. condition

B the number of molecules in 1 dm3 of oxygen at 273 K and 1 atm
C the number of electrons removed to form Ne+ ions from 6.02 x 10-23 mol of Ne
atoms
D the number of ions in 83.5 g of [Co(NH 3 ) 5 Cl]Cl 2
2 Which of the following species has no unpaired electrons?
A Fe B Ge2+ C Si D Ti3+
3 Why is the molecule of BCl 3 planar, whereas the molecule of PH 3 is pyramidal?
A The repulsion between chlorine atoms is greater than that between hydrogen
atoms.
B The covalent radius of chlorine is greater than that of hydrogen.
C The boron atom is BCl 3 has six electrons in its valence shell, whereas the
phosphorus atom in PH 3 has eight.
D The boron atom has no d-orbitals available for bonding.
4 In which pair do the isomers have identical boiling points?
A CH3 CH3
and
H C C H
Cl CH2Cl ClCH2 Cl
B H3C H H3C CH3

C C and C C
H CH3 H H
C CH 3 CH 2 CH 2 CH 2 OH and (CH 3 ) 2 CHCH 2 OH
D CH 3 (CH
CH
H 2 ) 4 CH 3 and (CH
C 3 ) 2 CHCH(CH
CH(C 3 ) 2
PJC 2016 9647/01/JC2/H2/MYE/2016 [Turn Over

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3
5 P
Which of the following shows a graph of against T for an ideal gas?

(P = pressure; = density; T = temperature in C).
A P B P

T T
C D
P P

T T
6 One mol of neon gas at temperature T 1 was added to another one mol of neon and
the temperature was increased to T 2 .
Which of the following diagrams correctly represents the Boltzmann distribution of
molecular speeds before and after the changes were made?
A B T2
T2 T1
proportion of
proportion of
molecules
molecules
T1
molecular speed molecular speed
C D
T2 T1
proportion of
of
molecules
molecules
T1 T2
proportion
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tr
trend
tren in
ine
mole
propo
pro
molecular speed molecular speed

sp
@PJC 2016 9647/01/JC2/H2/Preliminary Exam/2016 [Turn over

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4
Dinitrogen oxide burns in ethyne to produce water vapour, carbon dioxide and
nitrogen gas as the only products.
5N 2 O(g) + C 2 H 2 (g) H 2 O(g) + 2CO 2 (g) + 5N 2 (g)
Given that the N=N and N=O bond energies in dinitrogen oxide are +418 kJ mol1
and +686 kJ mol1 respectively, what is the enthalpy change of the reaction?
A +1670 kJ mol1
B +1710 kJ mol1
C 1670 kJ mol1
D 1710 kJ mol1
8 Quarter-life, t 1/4 , of a radioactive isotope is defined as the time taken for the sample
to decay to its original amount.
Potassium-argon dating is used to determine the age of a rock. 40K is a radioactive

isotope of potassium and it decays to 40Ar with a constant t 1/4 of 2.50 x 109 years. A
sample of moon rock was found to contain 6.25% of the original amount of 40K.
How old is the rock?
A 2.50 x 109 years B 5.00 x 109 years

C 7.50 x 109 years D 1.00 x 1010 years
9 During electrolysis, 0.785 g of chromium is deposited on the cathode when 8690 C

of electricity is passed into a chromium-containing electrolyte.
Which of the following could have been the electrolyte?
A CrCl 2 B CrCl 3 C K 2 CrO 3 D K 2 Cr 2 O 7
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The graph below shows the variation in electromotive force (emf) of the following
electrochemical cell with lg [A+(aq)] at 298 K.
Cu(s) | Cu2+(aq, 1 mol dm3) || A+(aq) | A(s)
emf / V
0.46
lg [A+(aq)] 0
7.80
A Cu(s) is the negative electrode.

B The direction of electron flow in the external circuit will be reversed when the
concentration of A+(aq) is 1.00 x 10-7 mol dm-3 .
C The standard electrode potential of the A+(aq) | A(s) half-cell is +0.80 V.
D The emf of the given cell under standard conditions will be +0.46 V.
11 Gas D dissociates on heating to set up the equilibrium below:
D(g) E(g) + F(g)
A quantity of D was heated at a constant pressure, p, at a certain temperature. The

1
equilibrium partial pressure of D was found to be p.
7
What is the equilibrium constant, K p , at this temperature?
A 6p B 9p C 36p D 6p
7 7 7
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12 Paracetamol (pK a = 9.5) is a widely used over-the-counter pain reliever and fever
reducer. Its solubility in water is 12.78 mg cm-3 at 25 oC. (M r of Paracetamol =
151.0)
O O
-
NH OH NH O + H+
paracetamol
What is its pH in water at 25 oC?
A 1.07
B 5.29
C 6.79
D 8.71
13 The pH change when 0.0500 mol dm-3 HCl is added dropwise to 5.00 cm3 of
0.100 mol dm-3 CH 3 NH 2 (aq) is shown in the graph below.
At which point on the graph is pH= 14 - pK b , where K b is the base dissociation

constant of the weak base?
A

B

C
D

Volume of 0.0500 mol dm-3 HCl added / cm3
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14 Which of the following statements explains the observations that magnesium

hydroxide dissolves in ammonium chloride, but not in aqueous sodium chloride?
A The ammonium ion changes the solubility product of Mg(OH) 2 .

B NH 4 + ion is first formed, and then acts through a common ion effect.
C NH 4 Cl dissociates less fully than NaCl.
D The NH 4 + ion acts as an acid.
15 A saturated solution of Ca(OH) 2 is found to have a pH of 12.3 at 25 C.
A The K sp of Ca(OH) 2 is 4 10-6 mol3 dm-9.

B The solubility of Ca(OH) 2 would increase when temperature is raised to 35 C.
C The solubility of Ca(OH) 2 will decrease when solid Na 2 O is added.
D The pH of the solution would increase when Ca(NO 3 ) 2 is added
Natural water in reservoirs often contains very finely divided solid particles of
between 1 and 100 nm in diameter which have negative charges on their surface.
One stage in the water purification process consists of adding salt solutions
containing high charge-density cations which will neutralise the negative charges
and cause the solid particles to join together and be precipitated out.
Which compound, in aqueous solution, would be the most effective in precipitating

the finely divided solid particles?
A AlCl 3
B MgCl 2
C SiCl 4
D PCl 3
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17
white ppt,
NaOH(aq)
insoluble in excess
O2 water colourless
M white solid
solution
H2SO4(aq) white ppt
Based on the information above, what could element M be?
A aluminium
B calcium
C potassium
D silicon
18 HCl is stable to heat, but HI decomposes into its elements when heated.
What is the reason for this difference?
A HI is a stronger reducing agent than HCl.

B Cl Cl bond is stronger than II bond.
C HCl bond is stronger than HI bond.
D HI is more volatile than HCl.
Which of the following solutions would result in a colour change when left to stand in
the atmosphere?
A an acidified solution of cobalt(II) nitrate

B a solution of potassium hexacyanoferrate(III)
C an acidified solution of tin(II) chloride
D an acidified solution of vanadium(II) sulfate

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20 Adding concentrated HCl(aq) to CuSO 4 (aq) causes the colour of the solution to
change from blue to green.
Which of the following row correctly shows the number of d-electrons and the
energy gap between the d-orbitals, before and after the reaction?
number of d-electrons energy gap between the d-orbitals

A changes changes
B changes remains the same
C remains the same changes
D remains the same remains the same
21 In the reaction of methane with chlorine in the presence of light, the following energy
level diagram (for single reaction step) is obtained.
energy
reactants
reaction pathway
To which of the following steps does this diagram apply?
A CH3 + CH3 C2H6
B CH4 + Cl CH3Cl + H
C CH3 + Cl2 CH3Cl + Cl
D Cl2 Cl + Cl
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22 The cholesterol-lowering agents called statins, such as pravastatin, are among the
most widely prescribed drugs in the world.
HO O
OH OH O
C
OH
Pravastatin
CH3
How many chiral centres are present in the product when pravastatin was treated
with H 2 , Ni catalyst at 200 0C?
A 6 B 7 C 8 D 9
23 CH=CHCH3
CN
CH2CH3
compound P
Which of the following statements about compound P is incorrect?
A There is only one sp hybridised carbon atom in a molecule of P.

B A molecule of P contains four bonds.
C After P reacts with HCl(g), all but one carbon atom in the product formed are
sp3 hybridised.
D After P reacts with LiAlH 4 , all the carbon atoms in the product formed are sp3
hybridised.
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24 Industrially, ethyl ethanoate may be prepared from cheap, low-grade ethanol as
follows:
Cu catalyst Cu catalyst
CH3CH2OH CH3CHO CH3CH(OH)OCH2CH3
- H2 + CH3CH2OH
Cu catalyst
-H2
CH3CO2CH2CH3
Which process is included in the above reaction sequence?
A disproportionation
B electrophilic addition
C nucleophilic addition
D reduction
25 Which process will not give a good yield of CH 3 CO(CH 2 ) 3 CO 2 H?
A
Cl KOH in ethanol hot KMnO4 (aq), H3O+
heat
B KOH(aq) hot KMnO4 (aq), H3O+

H2NCO(CH2)3CHClCH3
heat
C NaOH in ethanol hot KMnO4 (aq), H3O+

CH3CH(OH)(CH2)3CH2Cl
heat
D
hot KMnO4 (aq), H3O+
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26 Which of the following reactions would not produce 1,3-dicarboxylic acid?
A CHO
+ Fehling's solution followed by acidification
CHO
B H
C=CH2CH3
+ hot acidified potassium manganate(VII)
CO 2CH3
C CN
+ aq H2SO4, heat
CO 2CH3
D CH(OH)CH3
+ warm, alkaline aqueous iodine followed by acidification
COCH3
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27 When heated strongly, phthalic acid undergoes condensation reaction to form
phthalic anhydride.
O O
C C
OH
O + H2O
OH
C C
O O
phthalic acid phthalic anhydride
On reaction with water, the anhydride gives phthalic acid. What would be formed
when phthalic anhydride reacts with ethanol instead of water?
A O B O
C C
OH OCH2CH3
OCH2CH3 OCH2CH3
C O D O
C C
OCH2CH3 OCH2CH3
OCH2CH3
OH
C
C
O
O
28 Experiments are carried out on three compounds Q, R, and S.

CH3(CH2)16CO2 CH2
CH3(CH2)16CO2 CH
BrCH2CH2CH2Br
CH3(CH2)16CO2 CH2 CN
Q X R
Y SZ
A sample of 0.01 mol of each compound is heated under reflux with 50 cm3 of
1 mol dm-3 aqueous NaOH (in excess) until hydrolysis is completed and any
ammonia gas produced was expelled from the solution. The excess NaOH was
then titrated in each case and was found to require 20 cm3, 30 cm3 and 40 cm3 of
1 mol dm-3 HCl for neutralisation.
Which sequence of compounds matches these results?
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20 c 3
0 cm 30 cm3 0 cm3
40
A Q R S
B Q S R
C R S Q
D S R Q

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29 Why are amides, RCONH 2 , less basic than amines, RNH 2 ?
A Amides form zwitterion in which the nitrogen atom carries a positive charge.
B Amides have a resonance structure involving the movement of a pair of
electrons from the nitrogen atom to the oxygen atom.
C Electrons on the nitrogen atom move on the C-N bond giving it some double
bond character so that it is more difficult to break.
D The amide carbonyl group withdraws electrons from the NH 2 group to make
the hydrogen atoms more acidic.
30 Silk fibroin is a type of fibrous protein made up almost entirely of pleated sheets.
The main amino acids found in silk fibroin are alanine, glycine, serine and cysteine.
The structures of these amino acids are given below.
H2N CH COOH H2N CH COOH H2N CH COOH H2N CH COOH

H CH3 CH2OH CH2SH
glycine alanine serine cysteine
Which of the following statements about the type of interactions present in silk
fibroin is incorrect?
A The pleated sheets are held together by hydrogen bonding.

B There are van der Waals forces between glycine and alanine in the protein.
C There are disulfide linkages present in silk fibroin.
D Serine forms ionic bonds with another serine amino acid in the protein.
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15
Section B
For each of the questions in this section, one or more of the three numbered statements
1 to 3 may be correct.
Decide whether each of the statements is or is not correct (you may find it helpful to put a
tick against the statements that you consider to be correct).
A B C D
1, 2 and 3 are 1 and 2 only are 2 and 3 only are 1 only is correct
31 A 0.0200 mol sample of an oxochloride of T, TOCl y required 10.00 cm3 of

0.400 mol dm-3 acidified potassium manganate(VII) for oxidation to TO 3 - ions.
1 5 mol TOCl y react with 1 mol MnO 4 -.

2 The change in oxidation state of T in the reaction is +1.
3 The value of y in TOCl y is 2.
32 The ion U5+ has 38 electrons and 46 neutrons.
1 In an electric field, the ion U5+ will be deflected to the same extent as the
yttrium ion, 89Y5+.
2 The electronic configuration of U5+ is [Kr] 4d2.
3 The third ionisation energy of element U is significantly higher than its second
ionisation energy.
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976 trendyline
16
A B C D
33 The graph shows the results of an investigation of the initial rate of hydrolysis of
casein by the enzyme trypsin. In the experiments, the initial concentration of casein
was varied but that of trypsin was kept constant.
initial
reaction
rate
0 [casein]
1 When [casein] is low, the rate is first order with respect to [casein].
2 When [casein] is high, the rate is dependent of [trypsin].
3 When [casein] is high, the rate is dependent of [casein].
34 Button cells are tiny cells used to power small electronic devices such as wrist
watches and calculators. One such cell consists of lithium electrode and a paste of
manganese(IV) oxide electrode dipped in an organic electrolyte. The e.m.f.
produced by the cell is 3.00 V. In discharging the cell, LiMnO 2 will be formed.
Which of the following statements about the Li-MnO 2 cell are correct?
1 Electrons flow from the lithium electrode to the manganese(IV) oxide electrode.
2 The equation for the reaction at the cathode is MnO 2 + e MnO 2 -.
3 Water is added to manganese(IV) oxide to form the paste.
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977 trendyline
17
A B C D
35 Which of the following graphs correctly represents the variation in the specified
property of the elements in Period 3?
1 0.25
0.2
atomic radii/nm
0.15
0.1
0.05
0
11 12 13 14 15 16 17 18
atomic number
2 0.25
0.2
ionic radii/nm
0.15
0.1
0.05
0
11 12 13 14 15 16 17
atomic number
3
0.25
conductivity
0.2
atomic radii/nm
0.15
electrical
0.1
ttrendyline
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ren
rendy
dyl
dy
yliline
l nee
0.05
0
11 12 13 14 15 16 17 18
umb
atomic number

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18
A B C D
36 For the reaction,
(CH 3 ) 3 CX + CH 3 CH 2 O- &+ 3 ) 3 COCH 2 CH 3 + X- (where X = Cl, Br or I)
which of the following statements are likely to be correct?
1 The reaction involves an electrophilic attack by CH 3 CH 2 O-.

2 The rate determining step involves the formation of a carbocation.
3 The reaction will take place more rapidly when X is I than when X is Cl.
37 The reaction of phenylhydrazine is similar to that of 2,4-dinitrophenylhydrazine.
CHO + NHNH2 products
phenylhydrazine
Which changes in bonding occur in the reactants and products during the reaction
above?
Bond broken Bond formed

1 CH CC
2 NH OH
3 . C=O C=N
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979 trendyline
19
A B C D
38 Dopamine is a neurotransmitter found in many animals, including vertebrates and

invertebrates.
CO2H
HO CH2CH
NH2
HO
Dopamine
1 1 mole of dopamine reacts with 3 moles of acyl chloride

2 1 mole of dopamine reacts with 1.5 moles of Br 2 (aq).
3 1 mole of dopamine reacts with 3 moles of Na 2 CO 3.
39 Compound V, with molecular formula C 6 H 12 , was reacted with acidified potassium

manganate(VII) and the resultant mixture obtained was colourless. The mixture was
thereafter distilled to form distillate W and residual solution X.
Distillate W is able to form a yellow precipitate with alkaline aqueous iodine.

Residual solution X reacts with sodium carbonate to form a colourless gas.
1 Compound V will decolourise aqueous bromine.

2 Distillate W can form an orange precipitate with 2,4-dinitrophenylhydrazine.
3 Residual solution X can form white fumes with PCl 5 .
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20
A B C D
40 Benzoylglycine (hippuric acid) was first isolated from stallions urine.
CONHCH2CO 2H
Benzoylglycine
Which properties does this compound possess?
1 It can be hydrolysed to produce an amino acid.

2 It can be made by reacting benzoyl chloride with aminoethanoic acid.
3 It can be neutralised by reaction with cold aqueous sodium hydroxide.
End of Paper
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981 trendyline
H2 Chemistry Preliminary Examination Paper 1 Worked solution
1 D Option A is wrong: the number of atoms in 24 dm3 of nitrogen gas at r.t.p. condition
24 dm3 N 2 1 mol N 2 2 mol N 2 x L
Option B is wrong: the number of molecules in 1 dm3 of oxygen at 273 K and 1 atm
1 dm3 O 2 1/22.4 mol O 2 1/22.4 x L
Option C is wrong: the number of electrons removed to form Ne+ ions from 6.02 x 10-23 mol
of Ne atoms
No of electrons removed = (6.02 x 1023) x (6.02 x 10-23) = 6.022 electrons
Option D is correct: the number of ions in 83.5 g of [Co(NH 3 ) 5 Cl]Cl 2

Amount = 83.5/250.4 = 1/3 mol
1 mol [Co(NH 3 ) 5 Cl]Cl 2 3 mol ions
1/3 mol [Co(NH 3 ) 5 Cl]Cl 2 1 mol ions = L
2 B Fe : [Ar] 3d6 4s2 (one unpaired d-orbital)
Option A is wrong: 26
2
Option B is correct: 32 Ge : [Ar] 3d10 4s2 (no unpaired, all paired)
Option C is wrong: 14 Si : [Ne] 3s2 3p2 (two unpaired p-orbitals)
Option D is wrong: Ti3 : [Ar] 3d1 (one unpaired d-orbital)

22
3 C By VSEPR theory, BCl 3 has 3 bond pairs, and no lone pairs. This give rise to trigonal planar
structure.
PH 3 has 3 bond pairs and 1 lone pair, therefore it is trigonal pyramidal structure.
4 A The molecules in option A are a pair of enantiomers. Enantiomers are known to have
identical chemical and physical properties, with the exception of its ability to rotate plane
polarised light. Therefore the enantiomers will have identical boiling point.
5 B RT
Option A is wrong : P =
Mr
P
kT = k (toC + 273) (similar to y = mx + c)

Plot wrong as y-intercept is zero. Note temp axis is in C and y-intercept = 273k.
P
Option B is correct: kT = k (t + 273) (similar to y = mx + c)

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Option C is
s wrong:
w Not a linear plot of y = mx + c
Option D is
s wrong: Not a linear plot of y = mx + c
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6 C One mol of neon gas at temperature T 1 was added to another one mol of neon and the
temperature was increased to T 2 .
As such, the area under the curve should increase since there is an increase in the number
of moles of gases.
When temperature increases to T 2, the curve should tend to the right as the molecular speed
should increase at a higher temperature.
Option C is correct
7 C H = (5(BE(N=N) + BE(N=O)+2BE(C-H) + BE(CC)) (2BE(O-H) + 4BE(C=O) +
5(NN))
= (5(418 + 686)+2(410) + (840)) (2(460) + 4(740) + 5(994))
= - 1670 kJ mol-1
8 B
No. of quarter life Amount of 40K left
0 100%
1 25%
2 6.25%
Since two quarter life have passed, the time required would be 2.5 x 109 x 2 = 5.0 x 109
years
9 D 0.785 g Cr 0.0151 mol Cr
8690 C 0.09005 mol e
0.0151 mol Cr 0.09005 mol e
1 mol Cr 5.96 mol e 6 mol e
Crn+QH&U
n=6
Option A is wrong : OS of Cr = +2
Option B is wrong : OS of Cr = +3
Option C is wrong : OS of Cr = +4
Option D is correct: : OS of Cr = +6
10 B Cu(s) | Cu2+(aq, 1 mol dm3) || A+(aq) | A(s)

Option A is wrong as statement is correct : The Cu2+/Cu half-cell is the anode and Cu is the
negative electrode
Option B is correct as statement is incorrect : [A+(aq)] = 1.00 x 107 and log [A+(aq)] = -7.
From the graph, emf> 0 and the direction of electron flow will not be reversed.
Option C is wrong as statement is correct : E cell = E red + E ox +0.46 = E red + (-0.34) E red
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y
= + 0.8
0.80V
Option D iss wrong as statement is correct : At st
std [A+(aq)] = 1.00 mol dm-3
d conditions, [A
+
[A (aq)] = 0 emf = +0.46 V (from graph)
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11 B D(g) E(g) + F(g)
Initial pressure/atm p 0 0
Eqm pressure/atm1p3p3p 7 7 7
Note : Total pressure = p (constant)
3
( atm)2
Kp = 7 = 9p/7atm
1
( atm)
7
12 B Method 1: Calculation confirmation method
pK a = 9.5
K a = 10-9.5
[paracetamol] = [(12.78 x 10-3)/151] / (1 x 10-3) = 0.084 mol dm-3
[anion][H ]
Ka
[paracetamol]
[anion][H ]
109.5
[0.0846]
[ H ] 5.17 x106
pH lg[ H ] 5.29
Method 2: Elimination method smart guess

Paracetamol behaves as weak acid, which undergoes partial dissociation
hence pH must be near to 7
Most probable pH is 5.29
13 A pH = 14- pK b
pK b = 14- pH
pK b = pOH
i.e. max buffer capacity
Option A is correct
14 D NH 4 + is the conjugate acid of a weak base, NH 3 .
NH 4 + dissociates partially in water to produce H 3 O+ as follows:

NH 4 + + H 2 O NH 3 + H 3 O+
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yll
y
Mg(OH) 2 (s)) tthen undergoes an acid base reaction (neutralisation) with the H 3 O+ ions
acidbase
produced.
g(OH) 2 (s) + 2H 3 O+(aq)
Mg(OH) aq Mg2+(aq)
q) + 4H 2 O
O(l)
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15 D A saturated solution of Ca(OH) 2 is found to have a pH of 12.3 at 25 C.
Ca(OH) 2 Ca2+ + 2OH-.. eqm (1)
Option A is correct:K sp of Ca(OH) 2 = [Ca2+][OH-]2 = (1/2 x 10-1.7) (10-1.7)2 = 4 10-6 mol3 dm-9.
Option B is correct: The solubility of Ca(OH) 2 would increase when temperature is raised to
35 C.
Option C is correct: When solid Na 2 O is added, NaOH is formed, hence [OH-] increases. As
such, POE of eqm (1) above will shift to the left, hence [OH-] decrease. The solubility of
Ca(OH) 2 will decrease.
Option D is incorrect: When Ca(NO 3 ) 2 is added, [Ca2+] increases. As such, POE of eqm
(1) above will shift to the left, hence [OH-] decrease. The pH of the solution would decrease.
16 A Important information in question : high charge-density cations

Only AlCl 3 and MgCl 2 will dissolve in water to give cations, Al3+ and Mg2+
Hence, most effective high charge-density cation is Al3+
17 B All of the elements burns in presence of oxygen to give respective oxides. All the metal
oxides formed will be soluble in water but SiO 2 is insoluble in water.
Al 2 O 3 is amphoteric oxide which reacts with NaOH, ie soluble in excess NaOH through
formation of the following complex
Al 2 O 3 (s) + 2NaOH(aq) + 3H 2 O(l1D>$l(OH) 4 ](aq)
Both K 2 O and CaO are basic oxide which do not react with NaOH, thus remains as white
ppt.
However, only CaO will react with H 2 SO 4 to give a sparingly soluble white ppt.
CaO(s) + H 2 SO 4 DT&D62 4 (s) + H 2 O(l)
18 C Thermal decomposition of hydrogen halides, HX, involves the breaking of the covalent
H-X bond.
General trend of Group VII halides: Going down Group VII, the valence np orbital of the
halogen atom is larger and more diffused. Thus, the overlap of orbitals between the 1s
orbital of H and the np orbital of halogen atom becomes less effective. Consequently, the
H-X bond is longer and weaker as indicated by the bond energies. Less energy is
required to break the H-X bond going down the group, i.e. thermal stability decreases.
Conclusion : HClbond is stronger than HI bond.
19 D Option A :E cell = -0.59V, reaction is not feasible.
Option B: hexacyanoferrate(III) cannot be further oxidised.
Option C: Sn is not a transition element, therefore while it can be oxidised from Sn2+ to Sn4+,
there is no color change.
Option D is
3+
to V which
correct:
s correct
h is violet.
y
corre : E cell = 0.97V, therefore reaction is feasible. V2+ is g
green, and it changes
985 trendyline
20 C [Cu(H 2 O) 6 ] 2+ + 6 Cl- [CuCl 4 ]2-+ 6H 2 O
Blue yellow
The oxidation state of Cu is +2 in both complexes; therefore the number of d electrons will
be the same.
Different ligand splits the field differently and thus accounting for the different colors. The
energy gap is going to be different.
Thus option C is the only correct answer.

21 D The graph shows that the reactants are of lower energy than the products. Hence, the best
possible answer will be option D as the reactant which is Cl 2 will be of lower energy than the
product which are the highly reactive radicals.
22 D When treated with H 2 , Ni cat at 200oC, the product will be
As shown in the diagram, there are 9 chiral carbons in the product.

23 D Option A:The CN in compound P has sp hybridised carbon atom. (Correct)
Option B7KHSLERQGVLQWKHWZRGRXEOHERQGVSLERQGVLQ&1. (Correct)
Option C: Reaction with HCl(g) will lead to all the alkenes in the compounds to undergo
electrophilic addition and the carbon will become a sp3 hybridised except for -&1(Correct)
Option D: LiAlH 4 will not be able to reduce the C=C, hence not all the carbons in the
product formed will not be sp3 hybridised. (Incorrect)
24 C Cu catalyst Cu catalyst
CH3CH2OH CH3CHO CH3CH(OH)OCH2CH3
- H2 + CH3CH2OH
Cu catalyst
-H2
CH3CO2CH2CH3
First step: oxidation
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Second step: p: nucleophilic addition
Third step: oxidation
986 trendyline
25 C
26 A The rest of the options will produce 1,3-dicarboxylic acid.
27 C Using the example of phthalic anhydride producing phthalic acid with water, ethanol should
follow the same reaction as water. The general formula of the reaction is shown in the
equation below.
C 6 H 4 (CO) 2 O (anhydride) + ROH C 6 H 4 (COOH)COOR [R CH 3 CH 2 -]

28 B Q 1 mol of Q requires 3 mol of NaOH for the hydrolysis process.
Amount of NaOH left after hydrolysis = (50/100 x 1) 0.03 = 0.02 mol
1 mol NaOH requires 1 mol of HCl for neutralisation
Vol of HCl required to neutralise the remaining NaOH = 0.02 / 1 = 0.02dm3= 20cm3
R 1 mol of R requires 1 mol of NaOH for the hydrolysis process.

Amount of NaOH left after hydrolysis = (50/100 x 1) 0.01= 0.04 mol
1 mol NaOH requires 1 mol of HCl for neutralisation
Vol of HCl required to neutralise the remaining NaOH = 0.04 / 1 = 0.04dm3 = 40cm3
S 1 mol of S requires 2 mol of NaOH for substitution of 2 Br.
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Amount
unt of NaOH left after hydrolysis = (50/100 x 1) 0.02 = 0.03 mol
ount
1 mol
ol NaOH requires 1 mol of HCl for neutralisation
quired to neutralise the remaining NaOH = 0.03 / 1 = 0.03dm3= 30cm3
Vol off HCl required
987 trendyline
29 B Option A: Amino acids form zwitterions not amides.
Option B: Basicity depends on the availability of lone pairs of electron on nitrogen for
coordination with proton. The lone pair of electrons on the N atom can be delocalised with
the electrons of the C=O double bond. This creates the resonance structure. This makes
the amides less basic than amines.
Option C: Need to concentrate on the availability of lone pairs of electrons on nitrogen, not
on how it is more difficult to break the C-N bond.
Option D: The powerful electron-withdrawing effect of the carbonyl group C=O reduces
the electron density on the N atom, making it less effective as a proton acceptor. Not make
the hydrogen atoms more acidic.
30 D Option A: True
Option B: Both glycine and alanine have non polar R groups, hence would have van der
Waals forces between them.
Option C: Cystein is a sulfur containing amino acid which is capable of forming disulfide
linkages between the cysteine molecules.
Option D: Serine forms hydrogen bonds with another serine amino acid in the protein as the
side group is an alcohol group.
31 A Option 1 is correct : 0.0200 mol T 0.00400 mol MnO 4 -
5 mol T 1 mol MnO 4 -
Option 2 is correct : 5 mol T 1 mol MnO 4 - 5 mol e

1 mol T 1 mol e
1 mol T lost1 mol e
Change in OS of T =+1
Option 3 is correct : TOCl y TO 3 -

+4 +5
y
OCl y = +4
OC
OS of T inTOCl
In TOCl y , +4 + ((-2)
2) + (y (-1))
( )) = 0
y=2
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89 5
32 A U
Option 1 is correct: The ion U5+ has the symbol 43 and thus the same charge by mass
ratio as yttrium ion,89Y5+. Both deflected to same extent.
Option 2 is correct:U is the technetium, T c . Electronic configuration of T c is[Kr] 4d5 5s2 and
that of U5+is[Kr] 4d2.
Option 3 is correct :U2+ (g) U3+ (g) + e (3rd IE)

[Kr] 4d5[Kr] 4d4
The energy required to remove the a mol of e from U2+ (g) will be significantly higher than
2nd IE as it involves the removal of electron from an inner quantum shell.
33 B Trypsin is an enzyme that catalyses the reaction. When the [substrate] (casein) is low,
increasing the concentration of casein will increase the rate of reaction as there are plenty of
active sites available on the catalyst, therefore its first order with respect to casein.
However, as the concentration of casein rise, the active sites in the enzyme will be
saturated, and therefore, increasing the concentration of casein will have no effect on the
rate of reaction, thus its a zero order reaction.
34 B Option 1 is correct:In discharging the cell, Li+ MnO 2 - will be formed. Li is oxidised to Li+ and
electrons released will flow to the MnO 2 electrode.
Option 2 is correct: At the MnO 2 electrode (cathode), MnO 2 gains electron and is reduced to
MnO 2 -.
Option 3 is wrong: Water cannot be used as it will react with Li, a Group I metal.
35 A Graph 1 is correct: (Explanation can be found in Pg 4 Periodicity notes)
The atomic radii of the elements decrease across period 3 gradually. Across a period,
there is an increase in the effective nuclear charge, due to increasing number of
protons in the nucleus and approximately constant shielding effect.
The radius of Ar is, in fact, the van der Waals radius between two atoms. Hence, largest
radius.
Graph 2 is correct: explanation will use actual element and its ion to minimise confusion (Pg
4 Periodicity notes)
The cationic radius decreases from atomic number 11 to 14 (which is actually Na+ to
Si4+) (Electronic configuration: 1s2 2s2 2p6).
- Nuclear charge increases from Na+ to Si4+ due to an increase in protons.
- Shielding effect remains approximately constant as these cations are isoelectronic.
- Due to the increase in nuclear charge, the valence electrons in these ions are held
more tightly to the nucleus, accounting for a smaller cationic radius.
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n radius decreases from Si4- to Cl- (Electronic
The anionic
onic configuration 1s2 2s2 2p6 3s2
ectronic configuration:
configurat
6
3p )
arly for the anions (Si4-, P3-, S2- and Cl
- Similarly
ila Cl-) are isoelectronic (constant shielding).
The decrease in anionic radii is also due to the increase in nucle
nuclea
nuclear charge.
Radii of anions > Radii of cations because se of
o an extra shell of electr
electrons in the anions.
989 trendyline
Graph 3 is correct: Explanation can be found in Pg 5 Periodicity notes
Na, Mg and Al are metals.
Conductivity increases from Na to Al due to an increase in the number of valence
electrons donated to the delocalised electron cloud by the metal atoms.
Si is a metalloid (having both properties of metals and non-metals). It has low
conductivity. It is a semi-conductor.
P, S and Cl are non-metals. The electrons are localised in covalent pairs and are unable
to move to conduct electricity. They have very low conductivities. They are non-
conductors (insulators).
Na Mg Al Si P4 S8 Cl 2
Metals Metalloid Non-Metals
36 C Option 1: The reaction involves nucleophilic attack not electrophilic attack.

Option 2: The RX compound is a tertiary RX hence it will be undergoing SN 1 mechanism
which involves the formation of a carbocation in the slow step.
Option 3: The reaction involves the cleaving of C-X bond so if the X is I, the reaction will take
place rapidly as the C-I bond is weaker than C-Cl bond.
37 C During the reaction, C=O bond from benzaldehyde and 2 N-H bonds from phenylhydrazine
will be broken. The products will have C=N bond and O-H (from water) being formed.
38 D Option 1: One mole of dopamine has 1 NH 2 group and 2 OH groups. Hence, one mole of
dopamine will react with 3 moles of RCOCl. ( the NH 2 group will form amide with RCOCl
and the OH group will form ester with RCOCl).
Option 2: Dopamine will undergo electrophilic substitution with 3 moles ofBr 2 (aq) wrt to the
two phenol groups.
Option 3: One mole of dopamine will react with one mole of Na 2 CO 3 as only the COOH
group in the compound will react.
39 A Distillate W forms a yellow ppt with alkaline aq iodine W has C=O group.
X reacts with Na 2 CO 3 X has COOH group.
Option 1: Given the formula of V, V should have unsaturated bonds in it so it should be able
to decolourise aq bromine.
Option 2: W is a carbonyl compound so it should be able to form orange ppt with 2,4-DNPH.
Option 3: X has COOH group so it should be able to react with PCl 5 .
40 A Option 1: It can be hydrolysed to form Benzoic acid and aminoethanoic acid.
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Option 2: Benzoyle oy cchloride
o de a and
d a aminoethanoic
oet a o c acid
ac d can
ca undergo
u nucleophilic
/condensation
condensatio to form benzoylglycine and HCl
substitution/condensation HC as the
t e products.
product
p odu
Option 3: Cold
old NaOH(aq) can react with
wi COOH
COOH group through acid
acid-base
bas reaction.
acid-bas
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HIGHER 2
CANDIDATE
NAME
CT INDEX
1 5 S
GROUP NUMBER
CHEMISTRY 9647/02
2 hours
Write your class, index number and name on all work you hand in.
You may use a soft pencil for any diagrams, graphs or rough workings.
FOR EXAMINERS USE

Paper 2
1 /12
2 /12
3 /14
4 /8
5 /9
6 /17
Penalty sf units
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Total
/72
PJC 2016 9647/02/JC2/H2/Preliminary Exam/2016 [Turn Over

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2
1 Planning (P)
The formation of a cobalt(II) complex ion, from Co2+ and an unknown ligand(L-), is
accompanied by the appearance of a blue colouration.
Co2+ + 4L- >&R/ 4 ]2-
A machine, known as a spectrometer, is able to measure the amount of light that is

absorbed when a specific wavelength of visible light is shone through a few cm3 of the
solution. The amount of light absorbed is then expressed as an absorbance value, and
the absorbance value is proportional to the concentration of the cobalt(II) complex ion.
This technique can be used to confirm the formula of the cobalt(II) complex ion. A
series of solutions containing varying volume ratios of L- to Co2+, both of the same
concentration, while keeping the total volume of the Co2+ and L- constant, is prepared.
A spectrometer is used to measure the absorbance of the solutions. A graph of
absorbance value against volume of L- is then plotted.
Using the graph of absorbance value against volume of L-, the ratio of L- to Co2+ equal
to that in the cobalt(II) complex ion can be then determined from the maximum point.
This is known as the Jobs Method.
(a) The spectrometer is set to use the wavelength of the light that is absorbed most
strongly by the complex ion.
Colour Wavelengths (nm)

Red 620-750
Orange 590-620
Yellow 570-590
Green 495-590
Cyan 475-495
Blue 450-475
Violet 380-450
Suggest a wavelength in the visible spectrum from which a suitable wavelength of

light might be chosen. Explain your answer.
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.
.

[2]

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3
(b) Using the information given above, you are required to write a plan to confirm the
formula of the cobalt(II) complex ion as [CoL 4 ]2-.

solid cobalt(II) nitrate, Co(NO 3 ) 2 .6H 2 O;
solution of L-, of concentration 0.100 mol dm-3;
access to a spectrometer and instructions for its use;
graph paper;

the preparation of 250 cm3 of 0.100 mol dm-3 aqueous cobalt(II) nitrate;
the preparation of five 50 cm3 complex ion solutions containing varying volume
ratios of L- to Co2+;
how the absorbance values would be obtained;
a sketch of the graph of absorbance value against volume of L- that you would
expect to obtain;
how the calculation can be performed to determine the formula of [CoL 4 ]2-.
....
....
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....
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....
....
....
....
....
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...
..
....
...
....
...

....
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4
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....
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....
....
....
....
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...
...
[10]
[Total: 12]

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5
2 The mission of the Hydrogen and Fuel Cells Programme by the U.S. Department of
Energy (DoE) is to reduce petroleum use, greenhouse gas emissions, and air pollution
and to contribute to a more diverse and efficient energy infrastructure by enabling the
widespread commercialisation of hydrogen and fuel cell technologies.
One such technology involves creating an energy system concept that stores hydrogen
in the form of metal hydrides. Magnesium hydride (MgH 2 ) is one of the compounds
currently being researched on its viability on hydrogen storage. One way to release
hydrogen from metal hydrides is to react them with water, where a hydroxide is formed
as a side product.
The other way to obtain hydrogen is through the thermal decomposition of the metal
hydride MH 2 . When hydrogen is needed, these metal hydrides can be heated to
release molecular hydrogen.
MH 2 M + H2
This adsorption and desorption of hydrogen in metals serves like a hydrogen bank.
The rate of desorption of hydrogen is proportional on the strength of ionic bonds formed
between the metal and hydride ions.
Apart from MgH 2 , other Group II hydrides are also being studied and researched on the
same purpose. The table below shows some properties of the Group II hydrides.
MgH 2 CaH 2 SrH 2 BaH 2

Percentage of H / % by mass of H 7.7 4.8 2.2 1.4
Density / g cm-3 1.74 1.54 2.64 3.62
Melting point / & 650 842 777 727
H f / kJ mol-1 -114 -144 -119 -118
(a) (i) Write an equation for the reaction between solid MgH 2 and water.
..
[1]
(ii) Draw the dot-and-cross diagram for MgH 2 .
trendyline [1]

995 trendyline
6
(b) (i) Explain, with reasoning, the trend on the rate of desorption of hydrogen for
the Group II metal hydrides from CaH 2 to BaH 2.
..
..
..
..
[2]
(ii) Which metal hydride, CaH 2 or BaH 2, would you expect to decompose more
readily? Explain your answer by using relevant data from the above table.
..
..
..
..
[2]
(iii) Using relevant information from the Data Booklet and the information given
below, construct a Born-Haber cycle to calculate the lattice energy for
CaH 2 .
(The first electron affinity for hydrogen is -72.8 kJ mol-1 and the enthalpy
change of atomisation of calcium is +178 kJ mol-1)
trendyline
..

[3]

996 trendyline
7
(c) A car company is planning to develop cars that run on hydrogen fuel produced by
MgH 2 .
The following information is for a typical petrol-fuelled car.
Weight of vehicle / kg 1088

Fuel tank / L 42
Fuel consumption / km L-1 17
Energy consumption of petrol / kJ kg-1 46.4
Density of petrol / g cm-3 0.8 g
(i) Calculate the energy produced by a petrol-fuelled car running at full tank.
[1]
(ii) It was found that 1 kg of hydrogen produce 3 times more energy than petrol
with the same mass.
Assuming 100% efficiency, calculate the amount of magnesium metal

needed to store the hydrogen as the hydride to provide the same amount of
energy in the hydrogen-fuelled car. (1 L = 1000 cm3)
MgH 2 Mg + H 2
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[Total: 12]

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8
3 (a) In the presence of excess oxygen, a liquid alcohol, compound A, C x H y O,
undergoes complete combustion to produce 3.19 dm3 of hot gases at a
temperature of 250 C at a pressure of 1 atm,
Upon cooling to room temperature, the volume contracted to 836 cm3. The gases
were then passed through aqueous sodium hydroxide and the final volume
remaining was 100 cm3.
(i) Fill in the following blanks for the equation for the complete combustion of
A.
C x H yO + O2 CO 2 + H2O
[1]
(ii) Using the ideal gas equation, find the amount of CO 2 and amount of H 2 O
that was produced respectively from the complete combustion of compound
A.
[3]
(iii) Using your answer to (a)(i) and (a)(ii), calculate the value of x and y and
hence, write down the empirical formula for A.
[1]
(ii) The actual number of moles of gases obtained from the combustion is
found to be higher than that calculated when using the ideal gas equation.
Account for the difference between the two results.
trendyline
.

.

[1]

998 trendyline
9
(b) Methane can be obtained when carbon monoxide is heated to 900 C with
hydrogen gas as shown in the following equation.
CO(g) + 3H 2 (g) CH 4 (g) + H 2 O(g)
(ii) Write an expression for the K c of the reaction, stating its units.
[1]
(iii) 1 mol of carbon monoxide was heated with 4 mol of hydrogen gas in a
10 dm3 vessel. At equilibrium, the vessel contained 0.387 mol of methane.
Calculate the K c for the reaction of carbon monoxide.
[2]
(iv) Suggest, with an explanation, how the position of equilibrium might alter
when 1 mol of helium was added into the vessel.
[1]
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999 trendyline
10
(c) Anhydrous aluminium sulfate is commonly used in organic reactions to remove
water. It decomposes at 600 C to produce an insoluble white solid and misty
fumes. The white solid dissolves in both aqueous sodium hydroxide and aqueous
hydrochloric acid while the misty fumes turn moist blue litmus red.
(i) Suggest the identities of the white solid and the misty fumes. Hence, write a
balanced equation for the decomposition of aluminium sulfate.
.
[2]
(ii) Write equations for the reactions of the white solid with aqueous sodium
hydroxide and hydrochloric acid.
.
[2]
[Total: 14]
4 Batteries for hearing aids comprise of zinc and carbon electrodes. These electrodes in
an electrolyte, maintained at a pH of 11, forms a galvanic cell in which zinc is oxidised
and oxygen from the air is reduced.
External circuit
Carbon
Rod
Electrolyte gel
Zinc Electrode
(a) Write a balanced equation for the overall chemical reaction and calculate the
E cell of this cell.
trendyline [2]

1000 trendyline
11
(b) Indicate, on the diagram on page 10, the polarity of both electrodes and the
direction of electron flow in the external circuit.
[2]
(c) Explain how the e.m.f. of the cell would change if the pH of the electrolyte
decreases.

[2]
(d) If a current of 4 x 10-5 A was drawn from the cell, calculate how long a zinc
electrode weighing 2 g will last before it needs to be replaced. Give your answer
correct to the nearest day.
[2]
[Total: 8]
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1001 trendyline
12
5 Insulin is a hormone made by the pancreas that allows your body to use glucose from
carbohydrates in the food that you eat for energy. Insulin helps keeps your blood sugar
level from getting too high or too low.
The insulin molecule consists of 51 amino acid residues, in two polypeptide chains.
H2N
Section X
H2N
CO2H
CO2H
Some information on the amino acids of insulin is given below.
amino acid Abbreviated Formula of side chain pI

name (R in RCH(NH 2 )CO 2 H)
arginine arg -(CH 2 ) 3 NHC(NH 2 )=NH 10.76
cysteine cys -CH 2 SH 5.07
glutamic acid glu -CH 2 CH 2 COOH 3.22
glycine gly -H 5.97
(a) Draw the structural formula of section X in insulin.
trendyline [1]

1002 trendyline
13
(b) The diagram shows the results of electrophoresis on a mixture of the amino acids
obtained from hydrolysis of section X at pH 6.0.
Draw the structure of the species responsible for the spots labelled R, S and T.
R S T
[3]
(c) The polypeptide chains of insulin coil to form short sections of -helix which
stabilises the secondary structure.
Describe with the aid of a sketch, how a polypeptide chain is held in the shape of
DQ-helix.
trendyline
[3]

1003 trendyline
14
(d) The three-dimensional structure of insulin is further stabilised by disulfide
linkages. Write an equation for the formation of such linkage and state the type of
reaction involved.
..................................................................................................................................
..................................................................................................................................
[2]
[Total: 9]
6 Lactones are cyclic esters. They are formed by intramolecular esterification of the
corresponding hydroxycarboxylic acids.
(a) (i) The reaction scheme below shows how lactone E is synthesised from
compound D.
Complete the reaction scheme by giving the structural formulae of the

intermediate organic products in the spaces provided and stating the
reagents and conditions for steps I, III, IV, V and VI.
O O
I II Br
Al2O3, 400oC
III
V IV
NC
VI
trr
ttrendyline
O

1004 trendyline
15
Step Reagents and conditions
III
IV
VI
[8]
(ii) Suggest a simple chemical test to distinguish compound D from E.
..
..
..
..
[2]
(iii) Name and outline the mechanism when compound D is treated with HCN in
the presence of aqueous NaOH at 10 oC.
trendyline [3]

1005 trendyline
16
(b) Lactones with three- or four-membered rings are very reactive compared to five-
or six-membered rings, making their isolation difficult.
Suggest why lactones with three- or four-membered rings are very reactive.
.
[1]
(c) Iodolactonisation reaction was first reported by M. J. Bougalt in 1904 and has
since become one of the most effective ways to synthesise lactones.
An example of the iodolactonisation is the reaction of 4-pentenoic acid as shown

below.
O I2, NaHCO3
I
OH O
O
Two simplified steps in the iodolactonisation mechanism are given below.
Step 1
O O
+ HCO3- + H2O + CO2
OH -
O
Step 2
O slow Intermediate fast I
+ I2 + I-
- F O
O O
(i) Suggest the role of HCO 3 - in step 1 of the mechanism.
..
[1]
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1006 trendyline
17
(ii) The type of reaction in Step 2 of the mechanism is electrophilic addition.
Draw the structure of intermediate F.
[1]
(iii) Suggest the structural formulae of the final organic product formed when
CH 2 =CHCH(CH 3 )CH 2 CH 2 COOH undergoes iodolactonisation in a similar
process as above.
[1]
[Total: 17]
End of Paper
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1007 trendyline

HIGHER 2
CANDIDATE
NAME
CT INDEX
1 5
GROUP NUMBER
CHEMISTRY 9647/02
2 hours
Write your class, index number and name on all work you hand in.
FOR EXAMINERS USE

Paper 2
1 / 12 5 / 9
2 / 12 6 / 17
3 / 14 Penalty sf units
4 / 8 Total / 72
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y
This document consists of 19 printed pages and 1 BLANK page.
1008 trendyline
2
1 Planning (P)
The formation of a cobalt(II) complex ion, from Co2+ and an unknown ligand (L-), is
accompanied by the appearance of a blue colouration.
Co2+ + 4L- >&R/ 4 ]2-
A machine, known as a spectrometer, is able to measure the amount of light that is

absorbed when a specific wavelength of visible light is shone through a few cm3 of the
solution. The amount of light absorbed is then expressed as an absorbance value, and
the absorbance value is proportional to the concentration of the cobalt(II) complex ion.
This technique can be used to confirm the formula of the cobalt(II) complex ion. A
series of solutions containing varying volume ratios of L- to Co2+, both of the same
concentration, while keeping the total volume of the Co2+ and L- constant, is prepared.
A spectrometer is used to measure the absorbances of the solutions. A graph of
absorbance against volume of L- is then plotted.
Using the graph of absorbance against volume of L-, the ratio of L- to Co2+ equal to that
in the cobalt(II) complex ion can be then determined from the maximum point. This is
known as the Jobs Method.
(a) The spectrometer is set to use the wavelength of the light that is absorbed most
strongly by the complex ion.
Colour Wavelengths (nm)

Red 620-750
Orange 590-620
Yellow 570-590
Green 495-590
Cyan 475-495
Blue 450-475
Violet 380-450
Suggest a wavelength in the visible spectrum from which a suitable wavelength of

light might be chosen. Explain your answer.
[2]
Any value from 591 to 619 nm.
The observed colour of the cobalt complex ion is blue thus the colour
complementary to blue, orange, will be absorbed.
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1009 trendyline
3
(b) Using the information given above, you are required to write a plan to confirm the
formula of the cobalt(II) complex ion as [CoL 4 ]2-.

solid cobalt(II) nitrate, Co(NO 3 ) 2 .6H 2 O;
solution of L-, of concentration 0.100 mol dm-3;
access to a spectrometer and instructions for its use;
graph paper;
the preparation of 250 cm3 of 0.100 mol dm-3 aqueous cobalt(II) nitrate;
the preparation of five 50 cm3 complex ion solutions containing varying volume
ratios of L- to Co2+;
how the absorbance values would be obtained;
a sketch of the graph of absorbance against volume of L- that you would
expect to obtain;
how the calculation can be performed to determine the formula of [CoL 4 ]2-.
[10]
2+
Preparation of aqueous Co
M r of cobalt nitrate = 290.9
Amount of cobalt nitrate in 250 cm3 = (0.1 / 1000) x 250 = 0.0250 mol
Mass of cobalt nitrate required = 0.0250 x 290.9 = 7.27 g
Using a clean and dry weighing boat / bottle, weigh accurately 7.27 g of
solid cobalt nitrate with an electronic balance.
Transfer the solid into a 100 cm3 beaker.
Rinse the weighing boat with deionised water and transfer the washings
into the beaker.
Dissolve the solid with deionised water.
Transfer the solution into a 250 cm3 graduated flask with the aid of a filter
funnel and a glass rod.
Rinse the beaker with deionised water and transfer the washings into the
graduated flask.
Top the graduated flask to the mark with deionised water.
Cap the graduated flask and shake well to ensure the solution is well mixed.
Preparation of 4 solutions
Flask Vol of L- / cm3 Vol of Co2+ / cm3
1 25.00 25.00
2 35.00 15.00
3 40.00 10.00
4 42.00 8.00
5 (max 6:1 ratio) 45.00 5.00

trendyline
5 solutions
otal volume = 50 cm3
Total
Att least 2 volume smaller cm3 of L-
smaller or greater than 40 c
No volume of L- or Co2+ shouldld be 0 cm3.

1010 trendyline
4
Procedure
Fill a burette with the prepared Co2+ solution and another with the
L- solution.
Transfer 25 cm3 of Co2+ solution into a 100 cm3 conical flask, followed
by 25 cm3 of L- solution.
Swirl the solution to ensure it is homogeneous
Repeat steps 1 to 3 for with the stated volumes of solutions for Flask
2 to 4.
Set up the spectrometer to absorb yellow light.
Measure and record the absorbance of each of the 4 solutions.
Plot a graph of absorbance against volume of L- solution.
Calculations
Maximum of point = 40 cm3 of L-
Amount of L- = (40 / 1000) x 0.1 = 0.00400 mol
Amount of Co2+ = (10 / 1000) x 0.1 = 0.00100 mol
Ratio of L- to Co2+ = 4:1
Graph
[10]
[Total: 12]

1011 trendyline
5
2 The mission of the Hydrogen and Fuel Cells Programme by the U.S. Department of
Energy (DoE) is to reduce petroleum use, greenhouse gas emissions, and air pollution
and to contribute to a more diverse and efficient energy infrastructure by enabling the
widespread commercialisation of hydrogen and fuel cell technologies.
One such technology involves creating an energy system concept that stores hydrogen
in the form of metal hydrides. Magnesium hydride (MgH 2 ) is one of the compounds
currently being researched on its viability on hydrogen storage. One way to release
hydrogen from metal hydrides is to react them with water, where a hydroxide is formed
as a side product.
The other way to obtain hydrogen is through the thermal decomposition of the metal
hydride MH 2 . When hydrogen is needed, these metal hydrides can be heated to
release molecular hydrogen.
MH 2 M + H2
This adsorption and desorption of hydrogen in metals serves like a hydrogen bank.
The rate of desorption of hydrogen is proportional on the strength of ionic bonds formed
between the metal and hydride ions.
Apart from MgH 2 , other Group II hydrides are also being studied and researched on the
same purpose. The table below shows some properties of the Group II hydrides.
MgH 2 CaH 2 SrH 2 BaH 2

Percentage of H / % by mass of H 7.7 4.8 2.2 1.4
Density / g cm-3 1.74 1.54 2.64 3.62
Melting point / & 650 842 777 727
H f / kJ mol-1 -114 -144 -119 -118
(a) (i) Write an equation for the reaction between solid MgH 2 and water.
MgH 2 (s) + 2H 2 O(l) Mg(OH) 2 (s) + 2H 2 (g)
[1]
(ii) Draw the dot-and-cross diagram for MgH 2 .

xx 2+ -
x
x Mg xx 2 Hx
xx
[1]
(b) (i) Explain, with reasoning, the trend on the rate of desorption of hydrogen for
the Group II metal hydrides from CaH 2 to BaH 2.
q q
Strength of ionic bond
r r
trendyline
nd
dyyl
d
Radius
ylin
ne
ne a2+ < Srr2+ < Ba2+
adius of cation, r + : Ca
Strength
trength
rength of ionic bond : BaH
Rate
aH 2 < Sr
SrH 2 < CaH 2
ate of desorption of hydrogen from CaH 2 < SrH 2 < Ba
BaH 2 (fastest)
[2]

1012 trendyline
6
(ii) Which metal hydride, CaH 2 or BaH 2, would you expect to decompose more
readily? Explain your answer by using relevant data from the above table.
H f becomes less exothermic from CaH 2 to BaH 2
-H f becomes less endothermic from CaH 2 to BaH 2
Hence,
Ease of decomposition: CaH 2 < BaH 2
[2]
(iii) Using relevant information from the Data Booklet and the information given
below, construct a Born-Haber cycle to calculate the lattice energy for
CaH 2 .
(The first electron affinity for hydrogen is -72.8 kJ mol-1 and the enthalpy
change of atomisation of calcium is +178 kJ mol-1)
enthalpy
kJ mol-1
Ca2+(g) + 2e + 2H(g)
2 x 1st EA H Ca2+(g) + 2H-(g)
1st + 2nd IE Ca
Ca(g) + 2H(g) LE CaH2

BE (H-H) or
Ca(g) + H2(g) 2 x Hatom H
Ca(s) + H2(g) Hatom Ca

0
Hf (CaH2)
CaH2 (s)
H f o (CaH 2 ) = H at o (Ca)+ 2H at o (H)+ 1st IE(Ca)+2nd IE(Ca)+

2 x 1st EA(H) + H latt o (CaH 2 )
trendyline
tre
e d
en
-144 = 178 + 436 + 590 2(-72.8) + H latt o (CaH 2 )
2(-72.8)
90 + 1150 + 2
LE= 2.35 x 103 kJ mo

E= -2.35 mol-11
[3]

1013 trendyline
7
(c) A car company is planning to develop cars that run on hydrogen fuel produced by
MgH 2 .
The following information is for a typical petrol-fuelled car.
Weight of vehicle / kg 1088

Fuel tank / L 42
Fuel consumption / km L-1 17
Energy consumption of petrol / kJ kg-1 46.4
Density of petrol / g cm-3 0.8 g
(i) Calculate the energy produced by a petrol-fuelled car which is running at

full tank.
Mass of fuel at full tank = 42 x 1000 x 0.8 = 33600 g
Energy produced by the petrol at full tank = 33600/1000 x 46.4

= 1559.04 kJ
[1]
(ii) It was found that 1 kg of hydrogen produce 3 times more energy than petrol
with the same mass.
Assuming 100% efficiency, calculate the amount of magnesium metal

needed to store the hydrogen as the hydride to provide the same amount of
energy in the hydrogen-fuelled car. (1 L = 1000 cm3)
MgH 2 Mg + H 2
1 kg petrol produces 46.4 kJ of energy

1 kg H 2 produces (46.4 x 3) = 138.9 kJ of energy
Hence to produce 1559.04 kJ of energy,

mass of hydrogen required = 1559.04/138.9 =11.15 kg
or
Mass of H2 = 33600 / 3 = 11.2 kg
Mg + H 2 MgH 2
Number of mole of H 2 needed = 11.15 x 1000/2 = 5575 or 5600
0J+ 2
Number of mole of Mg needed = 5575
Mass of Mg metal needed = 5575 x 0.0243

= 135 kg or 136 kg
trendyline [2]
[Total: 12]

1014 trendyline
8
3 (a) In the presence of excess oxygen, a liquid alcohol, compound A, C x H y O,
undergoes complete combustion to produce 3.19 dm3 of hot gases at a
temperature of 250 C at a pressure of 1 atm,
Upon cooling to room temperature, the volume contracted to 836 cm3. The gases
were then passed through aqueous sodium hydroxide and the final volume
remaining was 100 cm3.
(i) Fill in the following blanks for the equation for the complete combustion of
A.
C x H yO + (x + y - 1)O 2 xCO 2 + (y/2)H 2 O

[1]
(ii) Using the ideal gas equation, find the amount of CO 2 and amount of H 2 O
that was produced respectively from the complete combustion of compound
A.
Amount of gases in hot gases = (101000 x 3.19 x 10-3) / (8.31 x 523)

= 0.0741 mol
Volume of CO 2 = 836 100 = 736 cm3

Amount of CO 2 = (101000 x 736 x 10-6) / (8.31 x 298) = 0.0300 mol
Volume of O 2 = 100 cm3

Amount of O 2 = (101000 x 100 x 10-6) / (8.31 x 298) = 0.00408 mol
Amount of H 2 O = 0.0741 0.0300 0.00408 = 0.0401 mol
[3]
(iii) Using your answer to (a)(i) and (a)(ii), solve for x and y in C x H y O and
hence determine the empirical formula of A.
Amount of C = 0.0300 mol
Amount of H = 0.0401 x 2 = 0.0802 mol
Empirical ratio (C:H) = 0.0300 : 0.0802

x = 3; y = 8
Empirical formula = C 3 H 8 O
[1]
(ii) The actual number of moles of gases obtained from the combustion is
found to be higher than that calculated when using the ideal gas equation.
trendyline
trendy
Account
ccount for the difference between the two results.
Significant
ignificant
gnificant intermolecul
intermolecular forces exists between the
th gas molecules,
hence
ence
nce thee gases deviates from ideality.
[1]

1015 trendyline
9
(b) Methane can be obtained when carbon monoxide is heated to 900 C with
hydrogen gas as shown in the following equation.
CO(g) + 3H 2 (g) CH 4 (g) + H 2 O(g)
(ii) Write an expression for the K c of the reaction, stating its units.
[CH4 ][H2 O]
Kc = 3
mol-2 dm6
[CO][H2 ]
[1]
(iii) 1 mol of carbon monoxide was heated with 4 mol of hydrogen gas in a
10 dm3 vessel. At equilibrium, the vessel contained 0.387 mol of methane.
Calculate the K c for the reaction of carbon monoxide.

CO 3H 2 CH 4 H2O
Initial mol 1 4 0 0
mol -0.387 -1.161 +0.387 +0.387
Eq mol 0.613 2.839 0.387 0.387
[ ] mol dm-3 0.0613 0.284 0.0387 0.0387
(0.0387 )(0.0387 )
Kc = = 1.07 mol-2 dm6
(0.0613 )(0.284 ) 3
[2]
(iv) Suggest, with an explanation, how the position of equilibrium might alter
when 1 mol of helium was added into the vessel.
When an inert gas is added, the total pressure increase but the partial
pressure of the reactants and products do not change. There
would not be any change to the position of equilibrium.
OR
When an inert gas is added, since the volume of the vessel remains
the same, the concentration of the reactants and products do not
change. There would not be any change to the position of equilibrium.
[1]
(c) Anhydrous aluminium sulfate is commonly used in organic reactions to remove

water. It decomposes at 600 C to produce only an insoluble white solid and misty
fumes. The white solid dissolves in both aqueous sodium hydroxide and aqueous
hydrochloric acid while the misty fumes turn moist blue litmus red.
(i) Suggest the identities of the white solid and the misty fumes. Hence, write a
balanced equation for the decomposition of aluminium sulfate.
White solid: Al 2 O 3 Misty fumes: SO 3
Al 2 (SO 4 ) 3 Al 2 O 3 + 3SO 3
[2]
trendyline
(ii) with aqueous sodium
Write equations for the reactions of the white solid w
hydroxide
ydroxide and hydrochloric acid.
All 2 O 3 + 6HCl
6HCl $lCl
$lCl 3 + 3H 2 O [1]
$
All 2 O 3 + 2NaOH + 3H 2 21D>$
21D>$l(OH)
1D>$l $l(OH)
H 4 ] [1]
1]
[2]
[Total: 14]

1016 trendyline
10
4 Batteries for hearing aids comprise of zinc and carbon electrodes. These electrodes in
an electrolyte, maintained at a pH of 11, forms a galvanic cell in which zinc is oxidised
and oxygen from the air is reduced.
External circuit +ve
Carbon
Rod
Electrolyte gel
-ve Zinc Electrode
(a) Write a balanced equation for the overall chemical reaction and calculate the
E cell of this cell.
2 Zn + O 2 + 2H 2 O 2 Zn2+ + 4OH- [or 2 Zn(OH) 2 (s)]
E o cell = +0.40 + (+0.76) = + 1.16 V

[2]
(b) Indicate, on the diagram above, the polarity of both electrodes and the direction of
electron flow in the external circuit.
[2]
(c) Explain how the e.m.f. of the cell would change if the pH of the electrolyte
decreases.
When pH decreases, [OH-] falls and so, position of equilibrium of the
reduction half-cell shifts to the right. Hence, E reduction becomes more
positive, making e.m.f. more positive.
[2]
(d) If a current of 4 x 10-5 A was drawn from the cell, calculate how long a zinc
electrode weighing 2 g will last before it needs to be replaced. Give your answer
correct to the nearest day.
2
Amount of Zn = = 0.03058 mol
65.4
Zn Zn2+ + 2 e
trendyline
tre yl
Amountt of electrons = 2 0.0305858 = 0.06116 mol
m
Q = 0.06116 96500 = 5902 C
Q 59
5902
t= = 5
1.476 108 s = 1708
= 1.47 708 days
day
I 4 10
1
[2]
[Total: 8]

1017 trendyline
11
5 Insulin is a hormone made by the pancreas that allows your body to use glucose from
carbohydrates in the food that you eat for energy. Insulin helps keeps your blood sugar
level from getting too high or too low.
The insulin molecule consists of 51 amino acid residues, in two polypeptide chains.
H2N
Section X
H2N
CO2H
CO2H
Some information on the amino acids of insulin is given below.
amino acid Abbreviated Formula of side chain pI

name (R in RCH(NH 2 )CO 2 H)
arginine arg -(CH 2 ) 3 NHC(NH 2 )=NH 10.76
cysteine cys -CH 2 SH 5.07
glutamic acid glu -CH 2 CH 2 COOH 3.22
glycine gly -H 5.97
(a) Draw the structural formula of section X in insulin.

Formula must start with N terminus, showing R groups, ending with C
terminus:
H H O H H O H H O
N C C N C C N C C
H H C H H C H
trendyline
dy
H C H H C H
H C H COO
COOH
N
HN
HN C H
NH2
[1]

1018 trendyline
12
(b) The diagram shows the results of electrophoresis on a mixture of the amino acids
obtained from hydrolysis of section X at pH 6.0.
Draw the structure of the species responsible for the spots labelled R, S and T.
R S T
+ - + - + -
H3N CH CO2 H3N CH CO 2 H3N CH CO 2
+
(CH 2)3NHC(NH 3) =NH
CH2 H
CH2
-
Accept protonation on
CO2 any basic amine group
of side chain. (more
than 1 protonation also
k allowed)
[3]
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1019 trendyline
13
(c) The polypeptide chains of insulin coil to form short sections of -helix which
stabilises the secondary structure.
Describe with the aid of a sketch, how a polypeptide chain is held in the shape of
DQ-helix.
[3]
(d) The three-dimensional structure of insulin is further stabilised by disulfide

linkages.
Write an equation for the formation of such linkage and state the type of reaction
involved.
Type of reaction: oxidation
-CH 2 S-H + H-SCH 2 - -CH 2 -S-S-CH 2 - + 2[H] (or H 2 )

OR
-CH 2 S-H + H-SCH 2 - + [O] (or O 2 ) -CH 2 S-SCH 2 - + H 2 O
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[Total: 9]

1020 trendyline
14
6 Lactones are cyclic esters. They are formed by intramolecular esterification of the
corresponding hydroxycarboxylic acids.
(a) (i) The reaction scheme below shows how lactone E is synthesised from
compound D.
O
D
Complete the reaction scheme by giving the structural formulae of the
intermediate organic products in the spaces provided and stating the
reagents and conditions for steps I, III, IV, V and VI.
O O O
I II Br
Br
Al2O3, 400oC
HO
D
III
O
OH O
V IV
NC
HOOC HOOC
VI
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E

1021 trendyline
15
Step Reagents and conditions

I Br 2 (aq)
III NaCN/KCN in ethanol, heat
IV H 2 SO 4 (aq), heat
V NaBH 4 in methanol
VI concentrated H 2 SO 4 , heat
[8]
(ii) Suggest a simple chemical test to distinguish compound D from E.

Reagents and conditions: 2,4-dinitrophenylhydrazine
Observations:
For compound D, orange ppt is formed.
For compound E, no orange ppt is formed (or no observable change)
Or
Reagents and conditions: K 2 Cr 2 O 7 , H 2 SO 4 (aq), heat
Observations:
For compound D, orange solution remains (or no observable change)
For compound E, orange solution turned green.
[2]
(iii) Name and outline the mechanism when compound D is treated with HCN in
the presence of aqueous NaOH at 10 oC.
Name of mechanism: Nucleophilic Addition
1D2+DT+&1DT+ 2 O(l) + Na+(aq) + CN-(aq)
O -
O
C CN
CN- C
slow
- OH
O H-CN CN
fast C
CN
C
+ CN-
ttrendyline
tr
re
e in
in
[3]

1022 trendyline
16
(b) Lactones with three- or four-membered rings are very reactive compared to five-
or six-membered rings, making their isolation difficult.
Suggest why lactones with three- or four-membered rings are very reactive.
Three- or four-membered rings have significant ring/angle strain.

[1]
(c) Iodolactonisation reaction was first reported by M. J. Bougalt in 1904 and has
since become one of the most effective ways to synthesise lactones.
An example of the iodolactonisation is the reaction of 4-pentenoic acid as shown

below.
O I2, NaHCO3
I
OH O
O
Two simplified steps in the iodolactonisation mechanism are given below.
Step 1
O O
+ HCO3- + H2O + CO2
OH -
O
Step 2
O slow Intermediate fast I
+ I2 + I-
- F O
O O
-
(i) Suggest the role of HCO 3 in step 1 of the mechanism.
It acts as a base to abstract H+ from the carboxylic acid.

[1]
(ii) The type of reaction in Step 2 of the mechanism is electrophilic addition.
Draw the structure of intermediate F.

+
I C O
H
-
O
[1]
(iii) Suggest the structural formulae of the final organic product formed when
CH 2 =CHCH(CH 3 )CH 2 CH 2 COOH undergoes iodolactonisation in a similar
process as above.
CH3
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ttr
re O O
End of Paper
[1]
[Total: 17]

1023 trendyline

HIGHER 2
CANDIDATE
NAME
CT INDEX
1 5 S
GROUP NUMBER
CHEMISTRY 9647/03
2 hours

Graph Paper
Data Booklet
Cover Page
Write your class, index number and name on all work that you hand in.

trendyline
y
This document consists of 12 printed pages and 1 BLANK Page.
1024 trendyline
2
Begin each question on a fresh piece of writing paper.
1 (a) Linalyl acetate is a naturally occurring phytochemical found in many flowers. It is

one of the principal components of the essential oils of bergamot and lavender. It
has the following structure.
Linalyl acetate can be synthesised by the reaction of carboxylate anion with an

alkyl halide as shown below:
CH 3 CO 2 -Na+ + RC(CH 3 )(CH=CH 2 )I 1DI + RC(CH 3 )(CH=CH 2 )OCOCH 3
where R =
The kinetics of this reaction was determined by measuring the concentration of the
remaining RC(CH 3 )(CH=CH 2 )I with time.
The initial concentrations of RC(CH 3 )(CH=CH 2 )I and CH 3 CO 2 -Na+ were
0.0050 mol dm3 and 0.100 mol dm3 respectively. The following data was obtained.
Time/ min [RC(CH 3 )(CH=CH 2 )I] / mol dm-3

0 0.0050
15 0.0040
30 0.0032
45 0.0026
60 0.0021
75 0.0017
(i) Plot a suitable graph to show that the order of reaction with respect to
RC(CH 3 )(CH=CH 2 )I is one.
[3]
(ii) A new set of experiment was carried out and the initial concentrations of
RC(CH 3 )(CH=CH 2 )I and CH 3 CO 2 -Na+ was increased to 0.0100 mol dm-3,
trendyline
0.200 mol dm-3 respectively
and 0. respectively.
ly. When a similar
s graph was
wa plotted, it was
found
d that the gradient at each point doubled.
doubled
Deduce th order of reaction with respect to CH 3 CO 2 -Na+, and explain your

uce the
answer.
wer. [2]
PJC 2016 9647/03/JC2 Preliminary Exam/2016 [Turn Over

1025 trendyline
3
(iii) Construct a rate equation for the reaction between CH 3 CO 2 -Na+ and
RC(CH 3 )(CH=CH 2 )I, stating the units for the rate constant.
[1]
(iv) Using your answer in (a)(iii), suggest the mechanism for the reaction
between CH 3 CO 2 -Na+ and RC(CH 3 )(CH=CH 2 )I that leads to the formation of
the ester, RC(CH 3 )(CH=CH 2 )OCOCH 3 .
[3]
(b) An example of a homogeneous catalyst is Fe2+(aq), which is used in the oxidation

of sodium ethanedioate, Na 2 C 2 O 4 , with acidified potassium manganate(VII),
KMnO 4 . Ethanedioate is oxidised to carbon dioxide.
(i) What do you understand by the term homogeneous catalyst? [1]
(ii) Write an overall equation for the reaction of sodium ethanedioate with
acidified potassium manganate(VII). [1]
(iii) The Eo cell of the reaction between sodium ethanedioate with acidified
potassium manganate(VII) is +2.01 V. However, the reaction is found to
proceed at a very slow rate.
Explain why the reaction between sodium ethanedioate and acidified

potassium manganate(VII) is slow. [1]
(iv) By considering suitable Eo values from the Data Booklet and the data given
below, explain how Fe2+ functions as a catalyst for the reaction between
sodium ethanedioate with acidified potassium manganate(VII), writing
equations where appropriate.
2CO 2 (g) + 2e- C 2 O 4 2-(aq) E = - 0.49V

[3]
(v) In the absence of a Fe2+ catalyst, the rate of reaction between potassium
manganate(VII), and sodium ethanedioate is shown in the graph below.
Rate
0 time
trendyline
d li
Explain
ain the shape of the graph. [2]
(c) The rate off a chemical temperatures.

chemical reaction is usually increased at elevated tem
Explain, with the aid of a Boltzmann Distribution

D graph, why an increase in
temperature increases the rate of reaction. [3]

1026 trendyline
4
[Total: 20]
2 (a) Ammonia and para-phenylenediamine, H 2 NC 6 H 4 NH 2 , are Bronsted-Lowry bases

that are used widely in permanent hair dyes. Para-phenylenediamine has the
structure shown below:
H2N NH2
para-phenylenediamine
Para-phenylenediamine, H 2 NC 6 H 4 NH 2 , can ionise in stages.
+ H+ +H+
+ + +
H2N NH2 H2N NH3 H3N NH3
pKb1 pKb2
The two pK b values associated with para-phenylenediamine are shown in the table
below.
Base formula pK b1 pK b2
ammonia NH 3 4.7 -
para-phenylenediamine H 2 NC 6 H 4 NH 2 7.7 11.0
(i) Explain what is meant by the term Bronsted-Lowry base. [1]
(ii) Suggest a reason why the pK b1 value of para-phenylenediamine is higher

than the pK b1 of ammonia. [1]
(iii) Suggest a reason why the pK b1 value of para-phenylenediamine is lower than

pK b2 . [1]
(iv) Explain what is meant by a buffer solution. [1]
(v) Assuming that a solution at pH 6.5 contains only [H 2 NC 6 H 4 NH 2 ] and

[ H 2 NC6 H 4 NH 3 ]
[H 2 NC 6 H 4 NH 3 +], calculate the ratio of in the solution.
[ H 2 NC6 H 4 NH 2 ]
(ignore the effect of pK b2 of para-phenylenediamine on the pH) [2]
(vi) Calculate the pH of solution containing equimolar amount of H 2 NC 6 H 4 NH 3 +
trendyline
and +H 3 NC 6 H 4 NH 3 + [2]

1027 trendyline
5
(b) Ammonia is commonly used in qualitative analysis of halides in aqueous solutions,

such as detecting the presence of chloride and bromide ions in natural water
sources such as rivers, lakes and streams.
(i) 5 cm3 of 0.0100 mol dm-3 of silver nitrate is added to a 30 cm3 sample of river
water containing chloride ions.
What is the minimum concentration, in mol dm-3 , of chloride ions present in

the river water when the first trace of precipitate appears?
Given solubility product of the silver chloride is 2.0 x 10-10 mol2 dm-6.
[2]
(ii) To a test tube containing another river sample containing bromide ions,
describe what you would see when aqueous silver nitrate is added to the
sample, followed by excess aqueous ammonia to the resulting mixture. [1]
(iii) Explain, with aid of appropriate equation(s), the observations in (b)(ii).
You should use the concepts of Le Chateliers Principle and solubility

product, K sp , to explain your answer. [4]
(c) (i) When iodine reacts with sodium hydroxide, iodide and iodate(V) are formed.
Write a balanced ionic equation, with state symbols, for the formation of IO 3 -
when iodine reacts with sodium hydroxide. Name the type of reaction taking
place. [2]
(ii) When Group II iodates(V), M(IO 3 ) 2 , are heated at high temperature, it form
the metal oxide, iodine vapour and a colourless gas that relights glowing
splinter.
It was observed that Group II iodates(V) down the group have to be heated
more strongly before the iodine vapour appears. Explain why thermal stability
increases down the group for Group II iodate(V). [3]
[Total: 20]
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1028 trendyline
6
3 (a) Liquid methyl t-butyl ether, MTBE, is a fuel additive that is used as an oxygenate to
raise the octane number in fuel. This will help the fuel to burn completely and
reduce air pollution.
O
MTBE
(i) What is meant by the term standard enthalpy change of formation of MTBE?
[1]
(ii) Use the following data and relevant data from Data Booklet to construct an
appropriate energy cycle, find the standard enthalpy change of formation of
MTBE.
Standard enthalpy change of atomisation of C(s) +715 kJ mol1

Standard enthalpy change of atomisation of MTBE(l) +6822 kJ mol1
[4]
(iii) Given that the standard enthalpy change of vaporisation of MTBE is

+30.4 kJ mol-1 and using relevant data from the Data Booklet and (a)(ii),
calculate the bond energy of C-O in MTBE. [2]
(iv) Suggest a reason for the difference in the C-O bond energy in (a)(iii) from
the value given in the Data Booklet. [1]
(b) MTBE can be produced from methanol and but-1-ene by the following equation.
The reaction has a standard entropy change of reaction of -281 J mol1 K1.
CH 3 OH(l) + C 4 H 8 (l) C 5 H 12 O(l) H

MTBE
The table below lists the H f (standard enthalpy change of formation) values for
some compounds.
compound H f / kJ mol-1
CH 3 OH(l) -239
C 4 H 8 (l) -0.4
(i)
(ii)
trendyline
Calculate
culate the
above
ve
HH f for the reaction in (b)
e and your answer to (a)(ii).
Determine
(a i)).
(a)(i
ermine the feasibility of the pro

but-1-ene at 298 K.
(b using the value
values from the table
production of MTBE from

fro methanol and
[2]
[1]

1029 trendyline
7
(c) Methyl shift can occur in organic chemistry reactions in reactions involving
carbocation intermediates.
An example of a methyl shift in a reaction between an alcohol and HI is shown

below. In this reaction compound D is produced as the major product.
OH H I +
OH2
+
Step 1
-
+ I
+ H2O + I-
carbocation A
methyl shift
+
I + H2O I- + H2O
compound D carbocation B
(i) What is the role of HI in step 1? [1]
(ii) Suggest a reason why there is a methyl shift to produce carbocation B from
carbocation A. [1]
(iii)
The structure of compound E is OH .
Predict the major final product formed when compound E reacts with HBr
based on the methyl shift reaction given in (c). [1]
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1030 trendyline
8
(iv) Compound D undergoes the following reactions.
step 1 CH3COCl
I NH2 NHCOCH3
D F
step 2
step 3
NH2
Suggest suitable reagents for steps 1, 2 and 3. [3]
(v) Suggest one simple chemical test which would enable you to distinguish
O
H2N
between compound F and .
You should state the reagents and conditions for the test and describe the
observations.
[3]
[Total: 20]
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1031 trendyline
9
BLANK PAGE
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1032 trendyline
10
4 (a) Compound G, C 10 H 15 NO 3 , is a natural stimulant made in the adrenal gland of the

kidney and is carried in the bloodstream and affects the autonomous nervous
system, which controls functions such as heart rate and dilation of the pupils.
G is soluble in dilute sodium hydroxide and dilute hydrochloric acid but does not
react with sodium carbonate.
G undergoes reaction with hot acidified potassium dichromate(VI) to form J. J

gives an orange precipitate with 2,4-dinitrophenylhydrazine but does not give a
silver mirror with Tollens reagent. Upon heating with concentrated H 2 SO 4, G forms
K, C 10 H 13 NO 2 . K does not react with PCl 5 . On heating with acidified potassium
manganate(VII), K forms three compounds, L, C 7 H 6 O 4 , M, C 2 H 4 O 2 , and an
ammonium salt, CH 3 NH 3 +.
Deduce the structures for each compound, G to M, and give an account of the
chemistry involved. [10]
(b) Like alcohols and halogenoalkanes, amines can be converted into alkenes by an
elimination reaction known as Hofmann elimination.
For example, 1-methyl-pentylamine is converted into hex1ene as shown.
Hofmann Elimination
+ side products
NH2
reaction
An interesting feature of the Hofmann elimination is that it gives a less substituted

alkene compared to other elimination reactions.
(i) Draw the likely structure of the starting amine if the following alkene N is the
main product formed when the amine undergoes a Hofmann elimination
reaction.
N
[1]
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1033 trendyline
11
(ii) Suggest, in no more than 3 steps, a suitable synthetic pathway to convert N

into the following compounds.
For each step, state clearly the reagents and conditions, indicating the
structural formula of all intermediate compounds formed.
(I) OH
HO
[2]
(II)
O
[3]
(c) Amines can be formed by reductive amination of an aldehyde or ketone with

ammonia or amine in the presence of reducing agent.
A reductive amination to produce an amine P takes place in the pathway shown.
CH2Cl CH2Cl OH CH2Cl

CH2COCH3 NH3 CH2 C NH2 CH2 C NH
CH3 Step II CH3
Step I
Step III
CH2Cl
CH2 CH NH2
CH3
P (C10H14NCl)
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(i) g
Suggest yp of reaction that occurs in steps
the type p I and II. [2]
(ii) Suggest
gest the reagents and conditions for step III.
III
II. [1]
(iii) On heating,
eatin P forms Q,
Q, C 10 H 13 N. Suggest a structure for Q.
Q.
[1]
[Total: 20]

1034 trendyline
12
5 (a) An electrochemical cell involving tartaric acid, (CH(OH)CO 2 H) 2 , has the following
cell diagram notation.
Pt(s)|(CH(OH)CO 2 H) 2 (aq) |CO 2 (g) |H+(aq) || Co3+(aq), Co2+(aq)|Pt(s)
(i) Given that the e.m.f of the cell is +0.80 V and using relevant data from the
Data Booklet, determine the standard electrode potential of the
CO 2 (g)|(CH(OH)CO 2 H) 2 (aq) half-cell. [2]
(ii) Draw a labelled diagram of the above electrochemical cell. [3]
(b) Fehlings solution is made by adding equal volumes of a blue solution A containing
aqueous copper(II) sulfate and a colourless solution B containing potassium
sodium tartrate and sodium hydroxide. In a strong base, an alpha-hydroxy group in
the tartrate ion, (CH(OH)CO 2 ) 2 , deprotonates as shown in the diagram below.
O O
-
- OH - O
O O
- O
- + H+
O OH
OH
O O
Deprotonated tartrate ion
The deprotonated tartrate ion acts as a bidentate ligand and binds to the Cu2+(aq)
using both oxygen atoms from the alpha-hydroxy groups. A square planar
bistartratocuprate(II) complex, [Cu(tart) 2 ]4, forms, and a deep blue solution is seen.
[tart = deprotonated tartrate ion]
(i) Draw the shape of [Cu(tart) 2 ]4 complex, indicating clearly the type of bonds
formed between the Cu2+ and the ligands. [2]
(ii) The open straight chain form of Dglucose, a reducing sugar, is shown.
OH OH O
HO
H
OH OH
Dglucose
State
e what would be observed when Dglucose
D glucose
u solution is warmed with a
few drops of Fehlings solution. Hence, or otherwise, write
w the balanced
equation
tion for the reaction described above.
ation above. [2]
(iii) Explain
ain
in why there is a need to form the [C (t t 2 ]44 comple
t [Cu(tart) complex in the Fehlings
solution
ti ttest.
t [1]

1035 trendyline
13
(iv) Explain why the Fehlings solution is deep blue while potassium sodium
tartrate solution is colourless. [4]
(v) Stronger field ligands are known to give rise to a larger energy gap between
the two sets of d-orbitals in a transition metal complex.
Violet Blue Green Yellow Orange Red

400 nm 430 nm 480 nm 560 nm 590 nm 630 nm 750 nm
. Energy of light decreases
To test for proteins, Biuret reagent which also contains the [Cu(tart) 2 ]4
complex is used. In the presence of peptides, it undergoes ligand exchange
to form [Cu(peptide) 2 ]2+. The deep blue solution turns violet.
Using the above electromagnetic spectrum of visible light, state the relative
field strength of peptides and deprotonated tartrate ions. Explain your
answer. [3]
(c) Adolf Kolbe first published a method describing the preparation of an alkane from
the electrolysis of an aqueous solution of sodium salt of a monoprotic acid, using
inert electrodes.
In the Kolbe electrolysis of sodium propanoate, butane was formed at the anode in
the following reaction.
2CH 3 CH 2 CO 2 CH 3 CH 2 CH 2 CH 3 + 2CO 2 + 2e-
(i) Write the half equation for the reaction at the cathode during the electrolysis
of sodium propanoate. Hence write an equation for the overall reaction. [2]
(ii) A student tried to synthesise another hydrocarbon using an aqueous solution

of a sodium salt of a diprotic acid, succinic acid, (CH 2 CO 2 H) 2 . The succinate
ion, (CH 2 CO 2 ) 2 ,undergoes a similar reaction as propanoate ion at the
anode.
(CH 2 CO 2 ) 2 R + 2CO 2 + 2e-
Suggest an identity of the hydrocarbon R. [1]

[Total : 20]
End of Paper
trendyline
1036 trendyline

HIGHER 2
CANDIDATE ANSWER SCHEME

NAME
CT INDEX
1 5
GROUP NUMBER
CHEMISTRY 9647/03
2 hours

Data Booklet
Cover Page
Write your class, index number and name on all work that you hand in.

trendyline
y This document consists of 22 printed pages.
1037 trendyline
2
Begin each question on a fresh piece of writing paper.
1 (a) Linalyl acetate is a naturally occurring phytochemical found in many flowers. It is

one of the principal components of the essential oils of bergamot and lavender. It
has the following structure.
Linalyl acetate can be synthesised by the reaction of carboxylate anion with an

alkyl halide as shown below:
CH 3 COO-Na+ + RC(CH 3 )(CH=CH 2 )I 1DI + RC(CH 3 )(CH=CH 2 )OCOCH 3
where R =
The kinetics of this reaction was determined by measuring the concentration of the
remaining RC(CH 3 )(CH=CH 2 )I with time. The initial concentrations of
RC(CH 3 )(CH=CH 2 )I and CH 3 COO-Na+ were 0.0050 mol dm3 and 0.100 mol dm3
respectively . The following data was obtained.
Time/ min [RC(CH 3 )(CH=CH 2 )I] / mol dm-3

0 0.0050
15 0.0040
30 0.0032
45 0.0026
60 0.0021
75 0.0017
(i) Plot a suitable graph to show that the order of reaction with respect to
RC(CH 3 )(CH=CH 2 )I is one. [3]
constant t (at about 48.25 minutes) first order
trendyline
PJC 2016 9647/03/JC2 Preliminary Exam/2016
1038 trendyline
3
(ii) A new set of experiment was carried out and the initial concentrations of
RC(CH 3 )(CH=CH 2 )I and CH 3 CO 2 -Na+ was increased to 0.0100 mol dm-3,
and 0.200 mol dm-3 respectively. When a similar graph was plotted, it was
found that the gradient at each point doubled.
Deduce the order of reaction with respect to CH 3 CO 2 -Na+, and explain your
answer. [2]
- +
The reaction was zero order with respect to CH 3 COO Na .
Gradient of a concentration-time graph gives the rate of reaction.
The reaction is first order with respect to RC(CH 3 )(CH=CH 2 )I, and doubling
the concentration will double the rate. This implies that changing the
concentration of CH 3 CO 2 -Na+ has no effect on the rate of reaction.
(iii) Construct a rate equation for the reaction between CH 3 COO-Na+ and
RC(CH 3 )(CH=CH 2 )I, stating the units for the rate constant. [1]
Rate = k[RC(CH 3 )(CH=CH 2 )I]
Units of k = min-1
(iv) Using your answer in (iii), suggest the mechanism for the reaction between
CH 3 CO 2 -Na+ and RC(CH 3 )(CH=CH 2 )I that leads to the formation of the
ester, RC(CH 3 )(CH=CH 2 )OCOCH 3 .
[3]
Nucleophilic substitution (S N 1)
R
CH3
slow +
C I C R + I
CH3 CH2=CH2
CH2=CH2
CH3
CH2=CH2
+ R
C R CH3
-
CH3COO : fast
CH2=CH2 C
OOCCH3
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1039 trendyline
4
(b) An example of a homogeneous catalyst is Fe2+(aq), which is used in the oxidation
of sodium ethanedioate, Na 2 C 2 O 4 , with acidified potassium manganate(VII),
KMnO 4 . Ethanedioate is oxidised to carbon dioxide.
(i) What do you understand by the term homogeneous catalyst. [1]
A homogeneous catalyst is a catalyst that exists in the same phase as the

reactants.
(ii) Write an overall equation for the reaction of sodium ethanedioate with
acidified potassium manganate(VII). [1]
2MnO 4 - + 16H+ + 5C 2 O 4 2- --> 2Mn2+ + 8H 2 O + 10CO 2
(iii) The Eo cell of the reaction between sodium ethanedioate with acidified
potassium manganate(VII) is +2.01 V. However, the reaction is slow.
Explain why the reaction is slow. [1]
High activation energy due to the repulsion between two negatively charged
ions MnO 4 - and C 2 O 4 2- to react, the rate of reaction is very slow.
(iv) By considering suitable Eo values from the Data Booklet and the data given
below, explain how Fe2+ functions as a catalyst for the reaction between
sodium ethanedioate with acidified potassium manganate(VII), writing
equations where appropriate.
2CO 2 (g) + 2e- C 2 O 4 2-(aq) E = - 0.49V

[3]
Fe2+ can speed up the rate of reaction as it is able to attract the oppositely
charged ions in the following equations:
MnO 4 - + 8H+ + 5Fe2+ ------> 5Fe3+ + 4H 2 O + Mn2+ E = +0.75V
C 2 O 4 2- + 2Fe3+ --------> 2CO 2 + 2Fe2+ E = +1.26V
Since the E is positive for both reactions, they are energetically feasible.
trendyline
1040 trendyline
5
(iv) In the absence of a Fe2+ catalyst, the rate of reaction between potassium
manganate(VII), and sodium ethanedioate is shown in the graph below.
Rate
0 time
Explain the shape of the graph. [2]
The rate of reaction is slow at the beginning of the reaction.
As the reaction proceeds, [Mn2+] increases, which catalyses the reaction.

The rate of reaction increases.
The rate of reaction will eventually decrease as [reactants] decreases to very

low levels despite the increasing concentration of the Mn2+ catalyst.
(c) The rate of a chemical reaction is usually increased at elevated temperatures.
Explain, with the aid of a Boltzmann Distribution graph, why an increase in

temperature increases the rate of reaction. [3]
[Total: 20]
At a higher temperature, the average kinetic energy of the particles is higher.

The particles move faster and collide with each other more frequently.
In addition, the number of particles with energy E a increases exponentially,

resulting in a greater number of effective collisions per unit time. This gives
rise to a large increase in the rate of reaction.
trendyline
1041 trendyline
6
2 (a) Ammonia and para-phenylenediamine, H 2 NC 6 H 4 NH 2 , are Bronsted-Lowry bases
that are used widely in permanent hair dyes. Para-phenylenediamine has the
structure shown below:
H2N NH2
para-phenylenediamine
Para-phenylenediamine, H 2 NC 6 H 4 NH 2 , can ionise in stages.
+ H+ +H+
+ + +
H2N NH2 H2N NH3 H3N NH3
pKb1 pKb2
The two pK b values associated with para-phenylenediamine are shown in the table
below.
Base formula pK b1 pK b2
ammonia NH 3 4.7 -
para-phenylenediamine H 2 NC 6 H 4 NH 2 7.7 11.0
(i) Using ammonia, NH 3 , explain what is meant by the term Bronsted-Lowry

base.
[1]
Ammonia, NH 3 , has a lone pair of electrons which acts as a base to accept a
proton.
(ii) Suggest a reason why the pK b1 value of para-phenylenediamine is higher

than the pK b1 of ammonia. [1]
The lone pair of electrons on N of H 2 NC 6 H 4 NH 2 can be delocalized into the

bezene ring, making it less available to accept a proton, compared to NH 3 .
Hence pK b1 value of para-phenylenediamine is larger than the pK b1 of
ammonia.
(iii) Suggest a reason why the pK b1 value of para-phenylenediamine is lower

than pK b2 . [1]
More energy is required to accept another H+ by H 2 NC 6 H 4 NH 3 +, from H 2 O to
form H 3 NC 6 H 4 NH 3 2+, which is electrostatically unfavourable. Hence pK b1
trendyline
y
value
e of
o para-phenylenediamine e is lower than pK
pK b2.
OR
H 3 + can b
The lone pair of electrons on NH 2 of H 2 NC 6 H 4 NH be delocalized into
the bezene ring to a greater extent
extent,
tent, making it less available
avail to accept a
proton. Hence pK b1 value of para-phenylenediamine is lower than the pK b2 .

1042 trendyline
7
(iv) Explain what is meant by a buffer solution. [1]
A buffer solution is one which is able to resist a change in pH (i.e. maintain
an almost constant pH) upon the addition of a small amount of acid or alkali,
or on dilution.
(v) Assuming that a solution at pH 6.5 contains only [H 2 NC 6 H 4 NH 2 ] and
+
[ H 2 NC6 H 4 NH 3 ]
[H 2 NC 6 H 4 NH 3 ], calculate the ratio of in the solution.
[ H 2 NC6 H 4 NH 2 ]
[2]
pH + pOH = 14
pOH = 14 - 6.5 = 7.5
[ H 2 NC6 H 4 NH 3 ]
pOH pK1 lg
[ H 2 NC6 H 4 NH 2 ]
[ H 2 NC6 H 4 NH 3 ]
7.5 7.7 lg
[ H 2 NC6 H 4 NH 2 ]
[ H 2 NC6 H 4 NH 3 ]
0.63
[ H 2 NC6 H 4 NH 2 ]
(vi) Calculate the pH of solution containing equimolar amount of H 2 NC 6 H 4 NH 3 +

and +H 3 NC 6 H 4 NH 3 +.
[2]
when equimolar amount of H 2 NC 6 H 4 NH 3 + and H 3 NC 6 H 4 NH 3 2+ is formed,

[H 2 NC 6 H 4 NH 3 +] = [+H 3 NC 6 H 4 NH 3 +]
This is the maximum buffer capacity at second stage of neutralization.

Hence
[ H 3 NC6 H 4 NH 32 ]
pOH pK 2 lg
[ H 2 NC6 H 4 NH 3 ]
pOH = pK 2
pOH = 11
pH = 3

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8
(b) Ammonia is commonly used in qualitative analysis of halides in aqueous solutions,
such as detecting the presence of chloride and bromide ions in natural water
sources such as rivers, lakes and streams.
(i) 5 cm3 of 0.0100 mol dm-3 of silver nitrate is added to a 30 cm3 sample of river
water containing chloride ions.
What is the minimum concentration, in mol dm-3 , of chloride ions present in

the river water when the first trace of precipitate appears?
Given solubility product of the silver chloride is 2.0 x 10-10 mol2 dm-6.
[2]
+
Ag (aq) + X DT$J;s)
The ppt is AgX.

[Ag+] at point of mixing = no. of moles of Ag+ before mixing total vol
= (0.0100 x 5/1000) 35/1000
= 1.428 10-3 mol dm-3
[Cl-] at point of mixing = no. of moles of X-before mixing total vol.

= ([Cl-] initial x 30/1000) 35/1000 mol dm-3
For precipitation to take place,

Ionic product (AgCl) Ksp(AgCl)
( [Ag+][Cl -] ) at point of mixing 2.0 x 10-10
30
[Cl ]initial
(1.428 103 ) ( 1000 )
35 2.0 x 10-10
1000
-
[Cl ] initial 1.63 x 10-7
Hence, minimum concentration is 1.63 x 10-7 mol dm-3
(ii) To a test tube containing another river sample containing bromide ions,
describe what you would see when aqueous silver nitrate is added to the
sample, followed by excess aqueous ammonia to the resulting mixture
[1]
Br-: cream ppt of AgBr observed; insoluble in excess NH 3 (aq)
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1044 trendyline
9
(iii) Explain, with aid of appropriate equation(s), the observations in (b)(ii).
You should use the concepts of Le Chateliers Principle and solubility

product, K sp , to explain your answer.
[4]
Ag+(aq) + Br-(aq) AgBr(s) ....(1)

Precipitate of AgBr is observed when I.P> K sp
Ag+(aq) + 2NH 3 (aq) [Ag(NH 3 ) 2 ]+(aq) .(2)

When excess NH 3 is added (high [NH 3 ]) to AgBr(s), the position of
equilibrium (2) shifts to the right in order to reduce the effect of excess
NH 3 (aq). OR complex [Ag(NH 3 ) 2 ]+ is formed
[Ag+] decreases hence equilibrium (1) shifts to the left.

but the ionic product of AgBr is still larger than K sp (AgBr),
AgBr remains insoluble.
OR
AgBr(s) + 2NH 3 (aq) [Ag(NH 3 ) 2 ]+(aq) + Br -(aq)
(c) (i) When iodine reacts with sodium hydroxide, iodide and iodate(V) are formed.
Write a balanced ionic equation, with state symbols, for the formation of IO 3 -
when iodine reacts with sodium hydroxide. Name the type of reaction taking
place. [2]
3I 2 (s) + 6OH-(aq) 5I-(aq) + IO 3 -(aq) + 3H 2 O(l)
Disproportionation
(ii) When Group II iodates(V), M(IO 3 ) 2 , are heated at high temperature, it form
the metal oxide, iodine vapour and a colourless gas that relights glowing
splinter.
It was observed that Group II iodates(V) down the group have to be heated
more strongly before the iodine vapour appears. Explain why thermal stability
increases down the group for Group II iodate(V). [3]
[Total: 20]
Cationic size of M2+ increases down Group II

resulting in decreasing charge density and/or hence decreasing
polarising power.
Thus the electron cloud of the IO 3 - is less distorted and thus less
weakening effect on the I-O bond in IO 3 -.
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More energy required to bring about decomposition of M(IO 3 ) 2 ,
re
resulting
esulting in higher temperature required for the purple iodine
io vapour to
be
e observed.
Thermal o M(IO 3 ) 2 increases down the group.
hermal stability of

1045 trendyline
10
3 (a) Methyl t-butyl ether, MTBE, is a fuel additive that is used an oxygenate to raise the
octane number in fuel. This will help the fuel to burn more completely and reduce
air pollution.
O
Methyl t-butyl ether, MTBE
(i) What is meant by the term standard enthalpy change of formation of

MTBE?
[1]
Standard enthalpy change of formation of MTBE is the heat change when
1 mole of a MTBE is formed from its constituent elements in their standard
states under standard conditions of 298 K and 1 atmospheric pressure.
(ii) Use the following data and relevant data from Data Booklet to construct an
appropriate energy cycle, find the standard enthalpy change of formation of
MTBE.
Standard enthalpy change of atomisation of C(s) +715 kJ mol1

Standard enthalpy change of atomisation of MTBE(l) +6822 kJ mol1
[4]
+I 07%(
5C(s) + 6H2(g) + 1/2 O2(g) C5H12O(l)
5 Hat(C ) %( 2 2
6BE(H2)
Hat(C5H12O)
5C(g) + 12H(g) + O(g)
By Hess Law,
H f (MTBE) = 5H at (C) + 6BE(H 2 ) + BE (O 2 ) H at (C 5 H 12 O)
H f (MTBE) = 5(715) + 6BE(H-H) + BE(O=O) - 6822
H f (MTBE) = 3575 + (6 x 436) + (496) - 6822
H f (MTBE) = -383 kJ mol-1
(iii) Given that the standard enthalpy change of vaporisation of MTBE is

+30.4 kJ mol-1 and using relevant data from the Data Booklet and (a)(ii),
calculate the bond energy of C-O in MTBE.
Bond energy of C 5 H 12 O involves breaking a total of:
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2(C-O), 3(C-C)
O), 3(C
O C) and 12(C-H)
12(C H) bonds.nd

H at (C 5 H 12 2 + vap (C 5 H 12 O) + 2BE(C-O)
2BE(C
2BE( -O) + 3BE(C-C)
3BE(C
3BE(C--C) + 12BE(C-H)
68222 = 30.4 + 2BE(C-O)
2BE(C
BE(C-O) O) + 3BE(C-C)
3BE(C--C) + 12BE(C-H)
3BE(C 12BE(C
12BE(C--H)
6791.6
1.6
6 = 2BE(C
2BE(C-O)
O) + (3 x 350) + (12 x 41 410)
6791.6
16 = 2BE(C-O) + 5970
BE(C-O) = +411 kJ mol-1

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11
(iv) Suggest a reason for the difference in the C-O bond energy in (a)(iii) from
the value given in the Data Booklet. [1]
The bond energy values from the Data Booklet are average values. The
actual bond dissociation energy values depend on the specific chemical and
electronic environment that a bond is in.
(b) MTBE can be produced from methanol and but-1-ene by the following equation.
The reaction has a standard entropy change of reaction of -281 J mol1 K1.
CH 3 OH(l) + C 4 H 8 (l) C 5 H 12 O(l) H

MTBE
The table below lists the H f (standard enthalpy change of formation) values for
some compounds.
compound H f / kJ mol-1
CH 3 OH(l) -239
C 4 H 8 (l) -0.4
(i) Calculate the Ho for the reaction in (b) using the values from the table
above and your answer to (a)(ii).
[1]
H= P+ f (products) Q+ f (reactants)
= -383 (-239 0.4)
= -143.6 kJ mol1
= -144 kJ mol1
(ii) Determine the feasibility of the production of MTBE from methanol and
but-1-ene at 298 K. [2]
* = + T6
= -143.6 298(-281 x 103)
= -59.9 kJ mol1 < 0, reaction is energetically feasible at 298 K.
(ECF)
Final answer and statement on energetically feasible.
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12
(c) Methyl shift can occur in organic chemistry reactions in reactions involving
carbocation intermediates.
An example of a methyl shift in a reaction between an alcohol and HI is shown

below. In this reaction compound D is produced as the major product.
OH H I +
OH2
+
Step 1
-
+ I
+ H2O + I-
carbocation A
methyl shift
+
I + H2O I- + H2O
compound D carbocation B
(i) What is the role of HI in step 1?
acid
(ii) Suggest a reason for the methyl shift to produce carbocation B from
carbocation A. [1]
B is a secondary carbocation which is more stable than the A which is a

primary carbocation. Hence, a more stable carbocation B is formed as an
intermediate during the reaction.
(iii)
The structure of compound E is OH .
Predict the major final product formed when compound E reacts with HBr
based on the methyl shift reaction in (c). [1]
Br
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1048 trendyline
13
(iv) Compound D undergoes the following reactions.
step 1 CH3COCl
I NH2 NHCOCH3
D F
step 2
step 3
NH2
Suggest suitable reagents for steps 1, 2 and 3. [3]
step 1: excess NH 3 in ethanol and heat it in sealed tube.

step 2: NaCN in ethanol, heat
step 3: LiAlH 4 in dry ether / H 2 , Ni cat, 2000C.
(v) Suggest one simple chemical test which would enable you to distinguish
O
H2N
between compound F and .
You should state the reagents and conditions for the test and describe the
observations.
[Total: 20]
Reagents and conditions: NaOH(aq), heat
O
H2N
Observation: the gas liberated which is NH 3 turns moist red

litmus paper blue.
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trendyl
For F, m
moist
oist red litmus paper remains red

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14
4 (a) Compound G, C 10 H 15 NO 3 , is a natural stimulant made in the adrenal gland of the
kidney and is carried in the bloodstream and affects the autonomous nervous
system, which controls functions such as heart rate, dilation of the pupils.
react with sodium carbonate.
G undergoes reaction with hot acidified potassium dichromate(VI) to form J. J

gives an orange precipitate with 2,4-dinitrophenylhydrazine but does not give a
silver mirror with Tollens reagent. Upon heating with concentrated H 2 SO 4, G forms
K, C 10 H 13 NO 2 . K does not react with PCl 5 . On heating with acidified potassium
manganate(VII), K forms three compounds, L, C 7 H 6 O 4 , M, C 2 H 4 O 2 , and an
ammonium salt, CH 3 NH 3 +.
Deduce the structures for each compound, G to M, and give an account of the
chemistry involved.
[10]
react with sodium carbonate. G contains basic/amine groups and phenol
G undergoes oxidation with acidified potassium dichromate(VI) to form J, which

undergoes condensation with 2, 4 - DNPH.
=> J is a ketone
=> G contains secondary alcohol
G undergoes elimination with concentrated H 2 SO 4 , heat to form K, C 10 H 14 NO 2

=> G is confirmed to be a secondary alcohol.
=> K is an alkene
K does not react with PCl 5

=> K is a has 2 phenol groups
K undergoes oxidation and acidic hydrolysis with acidified potassium manganate

to form L, M and CH 3 NH 3 +.
OH
CH 3 HO
C
O
O OH C
MI LH OH
OH
OH OH
HO
HO HO
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ttr
re dyyli e
CH 3
CH 3 CH 3
H
C CH 3
C CH 3
C CH
H3 C N
C N
C N H
H
O H
OH H
KG H H G JF
E
*The position of the substituent is not important in this question.
[1 for each of the compound]
1050 trendyline
15
(b) Like alcohols and halogenoalkanes, amines can be converted into alkenes by an
elimination reaction known as Hofmann elimination.
For example, 1-methyl-pentylamine is converted into hex1ene as shown.
Hofmann Elimination
+ side products
NH2
reaction
An interesting feature of the Hofmann elimination is that it gives a less substituted

alkene compared to other elimination reactions.
(i) Draw the likely structure of the starting amine if the following alkene N is the
main product formed when the amine undergoes a Hofmann elimination
reaction.
[1]
NH2
(ii) Suggest, in no more than 3 steps, a suitable synthetic pathway to convert N

into the following compounds.
For each step, state clearly the reagents and conditions, indicating the
structural formula of all intermediate compounds formed.
[5]
(I) OH
HO
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1051 trendyline
16
COOH
COOH
KMnO4, dil H2SO4
heat
LiAlH4 in dry ether,

r.t.p
CH2OH
= CH2OH
HO OH
(II)
OH O
Br2 (aq) KMnO4(aq),

Br Br
H2SO4(aq),
heat
NaOH in
ethanol
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1052 trendyline
17
(c) Amines can be formed by reductive amination of an aldehyde or ketone with
ammonia or amine in the presence of reducing agent.
A reductive amination to produce an amine P takes place in the pathway shown.
CH2Cl CH2Cl OH CH2Cl

CH2COCH3 NH3 CH2 C NH2 CH2 C NH
CH3 Step II CH3
Step I
Step III
CH2Cl
CH2 CH NH2
CH3
P (C10H14NCl)
(i) Suggest the type of reaction that occurs at steps I and II.
[2]
Step I Nucleophilic addition
Step II - Elimination
(ii) Suggest the reagents and conditions for step III.

[1]
H 2 in nickel catalyst, 200oC, LiAlH 4
(iii) On heating, P forms Q, C 10 H 13 N. Suggest a structure for Q.

[1]
H
N
[Total: 20]
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1053 trendyline
18
5 (a) An electrochemical cell involving tartaric acid, (CH(OH)CO 2 H) 2 , has the following
cell diagram notation.
Pt(s)|(CH(OH)CO 2 H) 2 (aq) |CO 2 (g) |H+(aq) || Co3+(aq), Co2+(aq)|Pt(s)
(i) Given that the e.m.f of the cell is +0.80 V and using relevant data from the
Data Booklet, determine the standard electrode potential of the
CO 2 (g)|(CH(OH)CO 2 H) 2 (aq) half-cell.
At the cathode, E red (Co3+(aq), Co2+(aq)) = +1.82 V
Since e.m.f. of cell = +0.80 V, and E cell = E red + E oxid

E oxid = E cell E red
= +0.80 (+1.82) = -1.02 V
At the anode, E red = +1.02 V
(ii) Draw a labelled diagram of the electrochemical cell.
electron flow
V <
platinum electrode CO2 gas at

salt bridge
25oC, 1 atm
1 mol dm3 Co3+(aq) 1 mol dm3 H+(aq)
1 mol dm3 Co2+(aq)) 1 mol dm3
(CH(OH)CO2H)2(aq)
platinum electrode
(b) Fehlings solution is made by adding equal volumes of a blue solution A containing
aqueous copper(II) sulfate and a colourless solution B containing potassium
sodium tartrate and sodium hydroxide. In a strong base, an alpha-hydroxy group in
the tartrate ion, (CH(OH)CO 2 ) 2 , deprotonates as shown in the diagram below.
O O
-
- OH - O
O O
- O
- + H+
O OH
OH
O O
Deprotonated tartrate ion
using both
trendyline
tonated tartrate ion acts as a bidentate ligand and binds to the Cu2+(aq)
The deprotonated
h oxygen atoms from tthe alpha
bistartratocuprate(II)
seen.
cuprate(
uprat III) compl
complex
alpha-
alpha-hydroxy
complex,, [Cu(tart)
[tart = deprotonated tartrate ion]

4
4
-hydroxy
ydroxy groups.
Cu(tart 2 ] , forms
groups A square planar
forms, and
a a deep blue solution is

1054 trendyline
19
(i) Draw the shape of [Cu(tart) 2 ]4 complex, indicating clearly the type of bonds
formed between the Cu2+ and the ligands.
(may want to include coordination number)

[2]
O O
-
OH O
-
.. -
O O
2+
Cu
- -
O O
-
O HO
..
O O
(ii) The open straight chain form of Dglucose, a reducing sugar, is shown.
OH OH O
HO
H
OH OH
Dglucose
State what would be observed when Dglucose solution is warmed with a

few drops of Fehlings solution.
Write the balanced equation for the reaction described above.

[2]
Observation: Brick-red/reddishbrown precipitate of Cu 2 O observed
Equation:
OH OH O OH OH O
HO
H
+ 2Cu 2+
+ 5OH -
Cu2O + HO O
- + 3H2O
OH OH OH OH
(iii) Explain why there is a need to form the [Cu(tart) 2 ]4 complex in the Fehlings
solution test.
[1]
The deprotonated tartrate ions, by complexing with Cu2+ prevents the

precipitation of Cu2+ as solid Cu(OH) 2 from the reaction of CuSO 4 and
t dyli
trendyline
NaOH.
The Cu22++ in the complex can then be reduced to Cu+ in the fform of copper(I)
oxide,
e, Cu 2 O.
2Cu2+ + H 2 O + 2
2e- Cu 2 O + 2
2H+

1055 trendyline
20
(iv) Explain why the Fehlings solution is deep blue while potassium sodium
tartrate solution is colourless.
[4]
In the presence of ligands, the partially filled 3d-orbitals of Cu2+ split into 2
sets of different energy levels.
The small difference in energy between the two sets of orbitals corresponds
to the energy of visible light in the electromagnetic spectrum
On absorbing energy from the visible light, an electron from a lower d-orbital
gets promoted to a vacant / half-filled orbital of higher energy.
The colour observed is complementary to that absorbed.
For a compound of Group I, the metal ion does not have electrons in the 3d-
orbitals and hence the d-d electron transitions would not occur. Hence, the
solution of this compound is colourless.
(v) Stronger field ligands are known to give rise to a larger energy gap between
the two sets of d-orbitals in a transition metal complex.
Violet Blue Green Yellow Orange Red

400 nm 430 nm 480 nm 560 nm 590 nm 630 nm 750 nm
. Energy of light decreases
To test for proteins, Biuret reagent which also contains the [Cu(tart) 2 ]4
complex is used. In the presence of peptides, it undergoes ligand exchange
to form [Cu(peptide) 2 ]2+. The deep blue solution turns violet.
Using the above electromagnetic spectrum of visible light, state the relative
ligand field strength of peptides and deprotonated tartrate ions. Explain your
answer.
[3]
Peptides are stronger field ligands than the deprotonated tartrate ions.
[Cu(tart) 2 ]4 appears blue because it absorbs orange light. [Cu(peptide) 2 ]2+

appears violet because it absorbs yellow light.
Yellow light has higher energy than orange light, the energy gap between
the d orbitals of [Cu(peptide) 2 ]2+ is larger than that of [Cu(tart) 2 ]4.
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1056 trendyline
21
(c) Adolf Kolbe first published a method describing the preparation of an alkane from
the electrolysis of an aqueous solution of sodium salt of a monoprotic acid, using
inert electrodes.
In the Kolbe electrolysis of sodium propanoate, butane was formed at the anode in
the following reaction.
2CH 3 CH 2 CO 2 CH 3 CH 2 CH 2 CH 3 + 2CO 2 + 2e-
(i) Write the half equation for the reaction at the cathode during the electrolysis
of sodium propanoate. Hence write an equation for the overall reaction.
[2]

2H 2 O + 2e H 2 + 2OH
Overall reaction:
2CH 3 CH 2 CO 2 + 2H 2 O CH 3 CH 2 CH 2 CH 3 + 2CO 2 + H 2 + 2OH
(ii) A student tried to synthesise another hydrocarbon using an aqueous

solution of a sodium salt of a diprotic acid, succinic acid, (CH 2 CO 2 H) 2 . The
succinate ion, (CH 2 CO 2 ) 2 ,undergoes a similar reaction as propanoate ion
at the anode.
(CH 2 CO 2 ) 2 R + 2CO 2 + 2e-
Suggest an identity of the hydrocarbon R.

[1]
CH 2 =CH 2 OR C 2 H 4 [1]
[Total : 20]
End of Paper
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1057 trendyline
1
RAFFLES INSTITUTION
2016 YEAR 6 PRELIMINARY EXAMINATION
Higher 2
CHEMISTRY 9647/01
1 hour
Data Booklet
Do not open this question booklet until you are told to do so.

Write your name, class and index number in the spaces provided on the Answer Sheet.
There are forty questions in this paper. Answer all questions.
For each question there are four possible answers A, B, C and D.

Answer Sheet.
Any rough working should be done in the question booklet.
trendyline This
rinted pages.
pages
Raffles Institution 2016 9647/01/S/16 [Turn Over
1058 trendyline
2
Section A
For each question, there are four possible answers, A, B, C, and D. Choose the one you
consider to be correct.
1 Which of the following statements best explains why helium has the highest first
ionisation energy among all the elements in the Periodic Table?
A It is unreactive.
B It is the least electronegative element.
C It has only one completely filled principal quantum shell.
D Its valence electron is poorly shielded and is very close to the nucleus.
2 When a beam of protons travelling at the same speed passes through an electric field
of constant strength, the protons, 1H+, are deflected through an angle of +12o.
Under identical conditions, which particle would be deflected through an angle of +8o?
2
A H+ B 3
He2+ C 6
Li2+ D 12
C3+
Which particle has three unpaired electrons?
A V3+ B F2+ C Ni D S
4 FeSO4 reacts with K2Cr2O7 in acid solution according to the following equation.
14H+ + 6Fe2+ + Cr2O72 o 2Cr3+ + 6Fe3+ + 7H2O
A 20.0 cm3 sample of FeSO4 solution required 13.10 cm3 of 0.100 mol dm3 acidified
K2Cr2O7 for complete reaction.
What was the concentration of the FeSO4 solution?
A 0.0655 B 0.153 C 0.393 D 0.916
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1059 trendyline
3
5 1,3,5-triazine is an aromatic compound and its structure resembles that of benzene.
1,3,5-triazine
Which statement about 1,3,5-triazine is correct?
A Its empirical formula is CN.

B A molecule of 1,3,5-triazine has six V bonds.
C The CNS bond is formed by 2sp22sp2 overlap.
D All the carbon-nitrogen bonds have equal bond lengths.
6 Which of the following shows the correct shape and bond angle of the molecule given?
molecule shape bond angle

A OF2 bent 117o
B BH3 trigonal pyramidal 120o
C XeF4 tetrahedral 109.5o
D SF6 octahedral 90o
7 At 25 oC and 101 kPa, a 1.00 g sample of dry air contains 78.09% nitrogen,
20.95% oxygen, 0.93% argon and 0.03% carbon dioxide by volume.
What is the average relative molecular mass of the air sample?
A 14.67 B 24.52 C 28.95 D 30.26
8 Which of the following statements about an ideal gas is correct?
A The total volume of the individual molecules is significant when compared to the
volume of the container which the gas occupies.
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B An ideal g
gas can liquefy
q y at low temperature
p and high
g pressure.
p
C The gas
as molecules are in constant, random motion.
motion
D The gas
as molecules have no mass.
mas
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4
9 Sodium carbonate reacts with ethanoic acid according to the equation below.
'Hr
Na2CO3(s) + 2CH3COOH(aq) o 2CH3COONa(aq) + H2O(l) + CO2(g)
In an experiment to determine the enthalpy change of reaction, 'Hr, 7.5 g of solid

sodium carbonate (Mr = 106) was added to 50 cm3 of excess aqueous ethanoic acid.
The temperature of the resultant solution was monitored at various time intervals and
the following graph was obtained.
time of mixing of reactants
Given that the specific heat capacity of the solution is 4.18 J cm3 K1, what is the
enthalpy change of reaction, 'Hr?
A +27.5 kJ mol1
B +29.5 kJ mol1
C +31.6 kJ mol1
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D +34.0 kJ mol1
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5
10 The DNA double helix consists of two DNA strands held together by hydrogen bonding.
When heated, the DNA double helix separates into two random-coil single strands.
When cooled, the random coils reform the double helix.
DNA double helix 2 random coils
Which of the following graphs corresponds to the forward process?
A B
'G / kJ mol1 'G / kJ mol1
0 T/K
0 T/K
C D
'G / kJ mol1 'G / kJ mol1
0 T/K 0 T/K
1,10-phenanthroline (phen) is an organic compound that is used as a ligand in

coordination chemistry. It forms complexes with metal ions such as Fe3+ and Fe2+.
The redox equilibrium between [Fe(phen)3]3+ and [Fe(phen)3]2+ is shown below.
[Fe(phen)3]3+ + e [Fe(phen)3]2+ E{ = V
Aqueous chlorine oxidises [Fe(phen)3]2+ to [Fe(phen)3]3+, but both aqueous bromine
trendyline
and iodine do not.
What could ?
of?
d be the value of
A 0.88 B 1.18
1 18 C +0.88
0 88 D +1.18
1062 trendyline
6
An electrochemical cell is set up as shown:
T = 298 K
Pt salt bridge Cu
[Cr2O72] = [Cr3+] = [H+] = 0.1 mol dm

m3 [Cu2+] = 0.1 mol dm3
Which statement about the e.m.f. of the above cell is correct?
A The e.m.f. of the cell is +0.99 V.

B Addition of water to the Cr2O72/Cr3+ half-cell decreases the e.m.f. of the cell.
C Addition of H+(aq) to the Cu2+/Cu half-cell decreases the e.m.f. of the cell.
D Addition of excess NH3(aq) to the Cu2+/Cu half-cell decreases the e.m.f. of the cell.
13 The two-step mechanism for the reaction

2X(g) + Y(g) o X2Y(g)
is shown below.
Step 1: X(g) + Y(g) o XY(g) (slow)

Step 2: XY(g) + X(g) o X2Y(g) (fast)
Which of the following is the rate equation for the reaction?
A rate = k[X]2
B rate = k[X][Y]
C rate = k[XY][X]
D rate = k[X]2[Y]
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7
14 Ethanoic acid dissociates in aqueous solution as follows, where is the degree of

dissociation.
CH3CO2H(aq) CH3CO2(aq) + H+(aq)

1
2C
A The Ka, in terms of and initial concentration C, is .
1
B pH decreases with decreasing concentration of ethanoic acid.
C Ka increases with increasing concentration of ethanoic acid.
D does not change with the concentration of ethanoic acid.
15 The solubility product, Ksp, of magnesium hydroxide at 25 C is X.
The solubility of magnesium hydroxide at 25 C is S.
Which of the following statements is correct at 25 C?
A The pH of a saturated solution of magnesium hydroxide is 14 + lg(2X)1/3.
B The solubility of magnesium hydroxide in a solution of magnesium chloride is

larger than S.
C When solid sodium hydroxide is dissolved in a saturated solution of magnesium
hydroxide, Ksp of magnesium hydroxide becomes smaller than X.
D The Ksp of barium hydroxide is smaller than X.
16 Which property of the Period 3 elements, from Na to Cl, increases consistently across
the period?
A enthalpy change of atomisation

B number of unpaired electrons
C electronegativity
D atomic radius
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8

W, X, Y and Z are four consecutive elements in the third period of the Periodic Table.
The formula of the hydride formed by each element is given in the table below.
element W X Y Z
formula of hydride WH2 XH3 YH4 ZH3
Which of the following shows the correct trends when the second ionisation energies of
the elements are plotted against the highest oxidation numbers that the elements
exhibit in their oxides?
A B
C D
18 An azide ion, N3, is called a pseudohalide because it has some properties which are
similar to those of chloride ions.
Which of the following statements is not likely to be correct?
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A CH3CH
H2N3 reacts with hot, ethanolic KCN to give CH3CH2CN.
B N3 ions
s react with a Cu2+ ion
ns n to give a complex, [Cu(N3)4]22.
C HN3 may
ay be prepared by warming NaN
Na 3 with
wit concentrated H2SO4.
D AgN3 is soluble in water.
water
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9
19 Which chlorine-containing products are obtained when chlorine is bubbled into hot
concentrated NaOH?
A NaClO3 only
B NaClO only
C NaCl and NaClO3
D NaCl and NaClO
20 A Lewis acid is an electron-pair acceptor, while a Lewis base is an electron-pair donor.
1 C6H6 + Br+ o [C6H6Br]+

2 CH3CH2NH3+ + NH3 o CH3CH2NH2 + NH4+
3 CH3CH2+ + Br o CH3CH2Br
Which equations represent a Lewis acid-base reaction?
A 3 only
B 1 and 2
C 2 and 3
D 1, 2 and 3
21 What is the total number of isomers possible for C3H4?
A 1 B 3 C 5 D 7
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22 The following reaction was found to be exothermic.
(CH3)3CBr + NaOH o (CH3)3COH + NaBr
The rate equation of the reaction is: rate = k[(CH3)3CBr].
Which reaction profile fits the given information?
A B
Energy Energy
(CH3)3CBr product
products

+ OH
(CH3)3CBr
products + OH

Progress of reaction Progress of reaction
C D
Energy Energy
(CH3)3CBr (CH3)3CBr

+ OH + OH
products products
Progress of reaction Progress of reaction
23 One gram of each of the following compounds was heated with NaOH(aq), and then
dilute HNO3(aq) and AgNO3(aq) were added.
CH3CH2Cl CH2=CHBr CH3COBr C6H5I
A The reaction with C6H5I gave a pale yellow precipitate.
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B The reaction
eaction
ac with CH3COBr gave a precipitate that dissolved completely
comp in NH3(aq).
C The reaction
eaction with CH2=CHBr
CHBr gave 1.76 g of precipitate.
D The reaction
eaction
action with CH3CH2Cl gave the largest mass of precipitate.
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11
24 Sorbitol is a sugar alcohol with a sweet taste, and is used as a sugar substitute.
The structures of sorbitol and glucose are given below.
sorbitol glucose
A sample containing a mixture of sorbitol and glucose reacts completely with 0.2 mol of
hydrogen gas in the presence of nickel catalyst.
Another identical sample reacts with excess sodium metal to form 1.4 mol of hydrogen
gas at room temperature and pressure.
What is the sorbitol : glucose ratio in the sample?
A 3:2
B 3:1
C 6:1
D 7:1
25 Aspirin has the following structure.
If 2-hydroxybenzoic acid is used as the starting material for making aspirin, which set of
reagents and conditions will give the best yield?
A ethanoyl chloride at room temperature

B phosphorus pentachloride at room temperature
C heat with ethanol and a small amount of concentrated sulfuric acid
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D heat with
th ethanoic acid and a small amount of conc
concentrated sulfuri
sulfuric acid
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12
26 Alkylbenzenes can be synthesised from benzene by introducing an acyl group via

electrophilic substitution, followed by the reduction of the carbonyl group with zinc
amalgam and hydrochloric acid.
For example, ethylbenzene can be synthesised by the following route:
CH3COCl, AlCl3 Zn(Hg), HCl, heat
Which compound cannot be synthesised by the same method?
A B
C D
27 Cortisone is a hormone released by the adrenal gland in response to stress.
cortisone
When cortisone is reacted with excess lithium aluminium hydride, how many chiral
centres will be present in the product molecule?
A 7 B 8 C 9 D 10
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28 Consider the following four compounds, which are structural isomers of one another.
1 CH2ClCHClCOOH
2 CHCl2CH2COOH
3 CHCl2COCH2OH
4 ClCH2OCOCH2Cl
Which sequence arranges the compounds in order of decreasing Ka?
A 1 2 3 4
B 2 1 3 4
C 4 3 1 2
D 4 3 2 1
29 The Hunsdiecker reaction is a reaction in which halogenoalkanes can be produced

from silver carboxylate salts, with the use of halogens. A proposed mechanism of the
reaction is shown below.
Which statement is not correct?
A Step 1 is favoured by the formation of a precipitate.

B Step 2 involves heterolytic fission.
C CO2 is also a product in step 3.
D Alkane RR is a possible side-product of the reaction.
30 In the tertiary structure of a water-soluble globular protein, it was found that the types of
amino acid residues present on the outer surface of the protein were different from
those present on the inside.
Which of the following amino acid residues is most likely found on the outer surface of
such proteins?
A B
C
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rre
e liine
n D
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14
Section B
For each of the following questions, one or more of the three numbered statements 1 to 3
may be correct.
A B C D
1, 2 and 3 1 and 2 2 and 3 1 only
31 In which pairs does compound 1 have a higher melting point than compound 2?
compound 1 compound 2
1 CH3CO2NH4 CH3CH2NH2
2 SiCl4 SiO2
3 Ni(CO)4 NiSO4
32 The Maxwell-Boltzmann distribution for gas M at a given temperature is shown below.
n = number of molecules
with a given energy
nb
nc
na
0 A B C molecular energy
Which statements are correct for the number of molecules with molecular energies
A, B and C?
1
2
3
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nc decreases
creases
reases when more gas M is added at the same temperature.
na increases
reases
eases when temperature is lowered.
Addition
on of catalyst at the same temperature
temperature
ratu has no effect on na, nb and nc.
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15

A B C D
1, 2 and 3 1 and 2 2 and 3 1 only
33 The stoichiometry of a catalysed reaction is shown by the equation below.
P(g) + Q(g) R(g) + S(l)
Two experiments were carried out in which the rate of production of R was measured.
The results are shown in the diagram below.
Which changes in the conditions might explain the results shown?
1 A lower pressure was used in experiment 2.

2 A different catalyst was used in experiment 2.
3 Product S was continuously removed from the reaction vessel in experiment 2.
Two catalysed reactions and their respective catalysts are shown below.
Reaction Equation Catalyst

I S2O82 + 2I o 2SO42 + I2 Fe3+
II 2MnO4 + 5C2O42 + 16H+ o 2Mn2+ + 10CO2 + 8H2O Mn2+
Which statements about the reactions and the catalysts are correct?
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1 Mn2+ iss an auto-catalyst in reaction II.
a auto-catalyst
2 Fe2+ could
ould replace Fe3++ as a homogeneous catalyst in reaction I.
3 Mn2+ could
ould replace Fe3++ as a homogeneous catalyst in reaction I.
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16

A B C D
1, 2 and 3 1 and 2 2 and 3 1 only

Element 117 is one of the most recently discovered elements in the Periodic Table.
In June 2016, the International Union of Pure and Applied Chemistry announced that
the discoverers have proposed the name, Tennessine (117Ts), for this element.
Which properties are Tennessine most likely to have?
1 Ts is a dark coloured solid at room temperature and pressure.

2 The covalent radius of Ts is greater than 0.140 nm.
3 The 6d and 7s orbitals of a Ts atom are completely filled with electrons.
36 Which of the following reactions will form a coloured product?
heat
1 Ca(NO3 )2 (s) o
heat
2 NaI(s) H2SO4 (l) o
3 2,4-DNPH
37 In which reactions is the product shown a possible product?
2 excess Br2(aq)
dark, rtp
3
endyl
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17

A B C D
1, 2 and 3 1 and 2 2 and 3 1 only
38 The reaction of methyl alcohols with alkaline aqueous iodine can be described by the
following scheme:
Which of the following types of reactions are present?
1 oxidation
2 acid-base reaction
3 nucleophilic addition
39 Lithium acetylide, HCC Li+, is a useful nucleophilic reagent in organic synthesis.

Lithium acetylide is reacted with compound X, followed by the addition of water.
X
Which of the following could be the products of the above reaction?
3 trendyline
tr
r
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18
A B C D
1, 2 and 3 1 and 2 2 and 3 1 only
40 Fibroin, a protein present in Spidermans web, consists of layers of anti-parallel beta-

pleated sheets. Its primary structure consists of the amino acid sequence shown below:
Man-made Kevlar can be stretched without snapping easily. Spiderman is impressed

by the tensile strength of the man-made Kevlar and intends to upgrade his spider silk
so that it will not snap midway through his swings.
The primary structure of Kevlar is shown below:
Which statements are correct?
1 Both fibroin and Kevlar have high tensile strength due to their ability to form
intermolecular hydrogen bonding between adjacent strands.
2 Kevlars additional strength is derived from instantaneous dipole induced dipole

interactions between the aromatic rings of adjacent strands.
3 Kevlar is less water-absorbent than fibroin due to the non-polar aromatic rings,
and thus could be used on rainy days.

APE
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1
RAFFLES INSTITUTION
Higher 2
CANDIDATE
NAME
CLASS INDEX NUMBER
CHEMISTRY 9647/02
Paper 2 Structured Questions 14 September 2016
2 hours
Write your name, class and index number in the spaces provided at the top of this page.
Write in dark blue or black pen in the spaces provided.

A Data Booklet is provided. Do not write anything in it.
For Examiners Use
1 / 12
2 / 13
3 / 13
4 / 18
5 / 16
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tren
ndy
dylin
line
Paper 1 Paper
aper 2 Paper 3 Planning
nn Pen
Penalty Total
Tota Grade
/ 40 / 60
6 / 80 / 12
1 / 100

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2
1 Planning (P) For

examiners
use
Copper plating is a method employed to coat an objects surface with a thin layer of
copper. The object to be plated is lowered into an electrolyte containing Cu2+ ions, which
are reduced on the surface of the object to form a thin layer of copper when an electric
current is passed through the set-up.
This set-up can also be used to determine the Faraday constant (F), which is the charge
carried by 1 mol of electrons, as described below.
A pre-weighed metal object and a pure copper rod are placed in a copper(II) sulfate
solution, and then connected to an electrical source. After a sufficient duration, the mass
of copper plated onto the metal object is determined by taking the difference between the
objects mass before and after plating.
The mass of copper plated is dependent on the amount of electrical charge flowing
through the circuit. The value of the Faraday constant may be determined graphically by
repeating the experiment several times using different amounts of electrical charge, and
plotting the collected data on a graph.
(a) The amount of electrical charge flowing through the circuit is dependent on time
and electrical current.
Show that the relationship between the mass of copper plated onto the metal object
and the time taken for the copper plating is given by:
63.5 I where
m t m = mass of copper plated in grams (g),
2F I = current of circuit in amperes (A),
t = time in seconds (s)
[2]
(b) The value of the Faraday constant (F) is widely accepted by chemists to be
96500 C mol1.
Using this value and given an electrical power source that supplies a constant
current of 0.500 A, calculate the maximum time (to the nearest second) for which
copper plating can be carried out so that the mass of copper plated onto the metal
object will not exceed 1.00 g.
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aximum time = ......
max ............ [1]

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3
(c) By considering your answers to (a) and (b), write a plan for determining the value of For
the Faraday constant in a laboratory. examiners
use
x 0.0500 mol dm3 copper(II) sulfate solution,

x 5 pieces of pure copper, each weighing approximately 1.5 g,
x 5 pieces of metal objects to be plated, each weighing exactly 2.00 g,
x an electrical power source that supplies a constant current of 0.500 A,
x distilled water,
x filter paper,
x the equipment and materials normally found in a school or college laboratory.
Your plan should include the following:
x a clearly labelled diagram of the set-up,

x details of how you would vary a variable of this experiment to collect 5 sets of
data that will be used to calculate the Faraday constant,
x a sketch of the graph you would expect to obtain using the data collected and
how the graph can be used to calculate the Faraday constant,
x the measures you would take to ensure the accuracy of the experiment.
Diagram for experimental set-up:
..
..
..
..
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..
..
..
..
..
..
..

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4
For
examiners
.. use
..
..
..
..
..
..
..
..
..
..
..
..
..
..
..
..
..
..
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[Total: 12]

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5
2 (a) Vitamin C refers to a group of compounds which includes ascorbic acid and its For
salts. examiners
use
ascorbic acid compound A
Compound A is the mirror image of ascorbic acid.
(i) Besides compound A, ascorbic acid has two other stereoisomers. Draw the
structures of these two isomers.
[2]
(ii) Pure ascorbic acid rotates plane-polarised light clockwise by 20 (or +20).
Compound A was mixed with ascorbic acid, in an unknown proportion, in a
beaker.
Plane-polarised light was shone through the beaker and it was found that
the light had rotated 10 anti-clockwise (or 10).
Calculate the percentage of ascorbic acid and compound A in the mixture.
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% ascorbic acid = .;; % compound A = . [2]

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6
(iii) Ascorbic acid is used as a food additive due to its solubility in water. Explain For
why ascorbic acid is soluble in water. examiners
use
..
..
..
..
[1]
(b) Ascorbic acid has antioxidant properties and it exists mainly as the ascorbate ion at
the physiological pH of 7.4.
An ascorbate ion reacts with a hydroxyl free radical in a 1:1 ratio to give product B
and a radical anion C as shown below:
(i) Explain what is meant by a free radical.
..
..
[1]
(ii) Suggest the identity of B.
..
[1]
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7
(c) Asparagine and serine are important D-amino acids in the synthesis of proteins. For
examiners
use
asparagine serine
Suggest, with reagents and conditions, a simple chemical test to distinguish

between the two D-amino acids.
...
...
Observations:
...
...
...
...
[2]

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8
(d) Nitrogen mustard gas is commonly used in chemotherapy for cancer. For
examiners
It was suggested that the synthesis of nitrogen mustard can be carried out via the use
following pathway:
ICl in CCl4
compound D
step 1
step 2
ethene
where X = Cl or I
nitrogen mustard
(i) Suggest the structure for compound D.
[1]
(ii) State and explain whether X (in nitrogen mustard) is more likely to be Cl
or I.
..
..
..
[1]
(iii) Suggest the reagents and conditions for step 2.
..
..
[2]
[Total: 13]
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9
3 Use of the Data Booklet is relevant to this question. For

examiners
(a) Haemocyanin is the primary oxygen transport molecule found in the blood stream use
of lobsters.
Unlike haemoglobin which contains iron, haemocyanin contains copper that binds
reversibly to oxygen molecules. Oxygenation of haemocyanin results in an
oxidation reaction, and a colour change as shown below:
Cu(I) Cu(II)
deoxygenated oxygenated
colourless blue
(i) Write the full electronic configuration of a Cu2+ ion.
[1]
(ii) By considering your answer to (a)(i), explain why oxygenated haemocyanin

is coloured.
..
..
..
..
..
..
..
..
..
..
[3]
(iii) Account for the absence of colour in deoxygenated haemocyanin.
..
..
..
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..

..

[1]

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10
(b) Bis(tartrate) complex of Cu2+, which is present in Fehlings solution, is used to test For
for aldehydes. examiners
use
(i) The reduction half-equation of bis(tartrate) complex of Cu2+ is given as:

2Cu2+(complex) + 2OH + 2e o Cu2O + H2O
Construct the half-equation for the oxidation of aldehyde (RCHO) under
alkaline conditions, and hence, construct the overall equation.
Oxidation half-equation:
..
Overall equation:
..
[2]
(ii) The bis(tartrate) complex of Cu2+ has the following structure:
It is synthesised by reacting aqueous Cu2+ ions with tartrate ions, C4H4O62,

in an alkaline medium as shown below:
2C4H4O62 + Cu2+ + 2OHo 2H2O
Draw the structure of the tartrate ion, C4H4O62.
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11
(c) Silver is a common metal used for jewellery. However, due to the increased For
amounts of hydrogen sulfide being released into the atmosphere by the examiners
use
combustion of fossil fuels, tarnishing of silver occurs relatively quickly, resulting in
the formation of black silver sulfide.
Tarnished silver has a layer of silver sulfide, Ag 2S, on its surface. It may be
restored easily by dipping it into warm water containing a piece of aluminium foil
and a pinch of sodium chloride.
warm water
containing NaCl
tarnished silver
jewellery aluminium foil
(i) The piece of aluminium acts as the anode which reduces the silver sulfide;
itself being oxidised to aluminium sulfide. Write the balanced equation for
this reaction.
..
[1]
(ii) A student calculated E{cell for this reaction using E{(Ag+/Ag) and E{(Al3+/Al).
However, the actual Ecell of this reaction is different from what he has
calculated. Besides not being performed under standard conditions,
suggest another reason to account for the difference.
..
..
..
..
[1]
(iii) Suggest a purpose for the addition of sodium chloride in this reaction.
..
..
..
..
[1]

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12
(iv) While carrying out this procedure, a faint aroma of rotten egg smell is given For
off. This is due to the further reaction of aluminium sulfide with water, examiners
use
producing aluminium hydroxide and hydrogen sulfide gas.
Al2S3 + 6H2O 2Al(OH)3 + 3H2S
17.1 cm3 of hydrogen sulfide gas was released at the end of the experiment,
which was conducted at room temperature and pressure.
Using the information given and your answer to (c)(i), calculate the
percentage of silver that was tarnished if the original jewellery contained
2.00 g of pure silver.
[2]
[Total: 13]
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13
4 Phenols and compounds containing the phenol functional group have many uses. For
examiners
(a) One use of phenol is in studying the kinetics of the reaction between bromide and use
bromate(V) ions in acid solution.
The initial rate of this reaction can be studied by the clock method using phenol
and methyl orange. The equations for the reactions are as follows:
5Br + BrO3 + 6H+ 3Br2 + 3H2O reaction I
+ 3Br2 + 3HBr reaction II
Br2 + methyl orange (acid form) o bleached methyl orange + 2Br reaction III
pink colourless
Aqueous Br is added to acidified BrO3 solution containing a small and constant
amount of phenol solution and methyl orange indicator. The Br2 produced by
reaction I will immediately react in reaction II until all the phenol has been used up.
At that point, free Br2 will be present in the solution and bleach the methyl orange
reagent in reaction III. This causes the reaction mixture to turn from pink to
colourless.
To study the kinetics of reaction I, KBr(aq), KBrO3(aq) and H2SO4(aq), each with
an initial concentration of 0.100 mol dm3, are reacted with 0.00010 mol dm3 of
phenol solution.
(i) Explain briefly why bromination of phenol occurs readily.
..
..
..
..
[1]
(ii) It is noticed that the reaction mixture turns a little cloudy as the reaction
progresses. Give a reason for the observation of cloudiness in the reaction
mixture.
..
trendyline
..

..

..

[1]

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14
For
To find the order of reaction with respect to H+, five experiments are conducted. examiners
use
In all the experiments, 10 cm3 of KBr(aq), 10 cm3 of KBrO3(aq), 5 cm3 of phenol
solution and 2 drops of methyl orange indicator are used, with water added to keep
the total volume constant. The volume of H2SO4(aq) used and the time taken for the
mixture to turn from pink to colourless for the 5 experiments are shown in the table
below:
Time taken for

Experiment Volume of 1
colour to change
H2SO4(aq), V V2 / cm6 / s1
No. from pink to t
/ cm3
colourless, t / s
1 24.00 576 10.0 0.100
2 20.00 400 14.4 0.069
3 16.00 256 22.5 0.044
4 12.00 144 40.0 0.025
5 8.00 64 90.0 0.011
(iii) State the relationship between

x initial rate and t
x concentration of H+ and V.
..
..
..
..
[1]
(iv) To determine the order of reaction with respect to H+, use the data in the
table above to plot a straight line graph on the grid provided on page 15.
Label the axes clearly.
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15
For
examiners
use
[3]
(v) With reference to the graph, state the order of reaction with respect to H+.
Briefly explain your answer.
..
..
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..

..

[2]

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16
(b) Bisphenol A, commonly known as BPA, has the structure shown below: For
examiners
use
It is one of the two reactants used to make polycarbonate plastic which is a

lightweight, high-performance polymer used in making containers, sports safety
equipment and medical devices.
When reacted with compound E, BPA undergoes condensation to form

polycarbonate plastic. The structure of the polycarbonate, showing two repeat units,
is shown below:
(i) Compound E contains carbon, oxygen and halogen only. It reacts with
aqueous silver nitrate to give a white precipitate. Draw the displayed formula
of compound E.
[1]
Bakelite, a polymer made from the condensation reaction of phenol and

methanal, has the structure shown below:
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ndyl e
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17
(ii) With reference to their structures, explain why Bakelite is more rigid than For
polycarbonate plastic. examiners
use
..
..
..
..
..
..
[1]
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18
(c) Umbelliferone is a yellowish-white crystalline solid occurring naturally in carrots and For
is used as a sunscreen agent. It has the structure shown below: examiners
use
The following reaction scheme shows how umbelliferone may be synthesised from
compound F, which has a molecular formula of C8H8O3.
In the boxes provided, fill in the missing
x reagents and conditions,
x structures of compounds F and G.
compound F H2SO4(aq),
C8H8O3 heat under reflux
compound G
tre
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re dy in
umbelliferone
ne
i [5]

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19
(d) Thymol is a white crystalline solid with a pleasant odour and provides the distinctive For
strong flavour of the herb thyme. It has the structure shown below: examiners
use
thymol
(i) Carvacrol is a positional isomer of thymol.
When warmed with acidified aqueous potassium manganate(VII), both

thymol and carvacrol gave the same organic product.
Draw the structure of carvacrol.
[1]
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20
(ii) Compound H has the structure shown below: For

examiners
use
compound H
To separate H from a mixture of H and thymol, the following method is used.

Using a separatory funnel, an ether solution of H and thymol is shaken with
an aqueous solution J, and the aqueous layer is separated from the organic
layer.
1. Add 2. Vigorous 3. Remove

aqueous shaking aqueous
solution J layer
ether solution of H aqueous solution J

and thymol
aqueous layer
If the organic layer contains only compound H after separation, suggest a

suitable reagent which can be used as aqueous solution J. Give a reason
for your answer.
..
..
..
..
..
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..

[2]
[Total: 18]

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21
5 The table below gives data about some physical properties of some Group I and II For
examiners
elements. use
property potassium calcium strontium barium radium
relative atomic mass 39.1 40.1 87.6 137
atomic radius (metallic) / nm 0.227 0.197 0.215 0.217 0.220
ionic radius (2+) / nm 0.099 0.113 0.135 0.140
3
density / g cm 0.890 1.55 2.60 3.50 5.50
1st ionisation energy / kJ mol1 418 590 548 502 509
2nd ionisation energy / kJ mol1 3070 1150 1060 966 979
solubility of sulfate in water
11.1 0.210 0.0130 0.000240
(at 20 C) / g per 100 cm3
(a) Explain why the atomic radius of barium is larger than that of strontium.
...
...
...
...
...
...
[2]
(b) Calcium and barium were separately added to cold water. Describe what you would
observe and write equations for the reactions that occur.
...
...
...
...
...
...
...
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...

...

[3]

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22
(c) When added to water, potassium floats on the water surface. Explain whether For
calcium floats or sinks when it is first added to water. examiners
use
...
...
...
...
[1]
(d) Determination of the relative atomic mass of an element depends on information

like the relative isotopic masses of the isotopes and the relative abundance of each
of the isotopes. Suggest why no value is quoted for the relative atomic mass of
radium in the table.
...
...
...
...
[1]
(e) Write the expression for the solubility product, Ksp, of SrSO4.
Using data given in the table on page 21, calculate the solubility product of SrSO4
and state its units.
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23
(f) The ionic radius of the sulfate ion is much larger than the ionic radii of Group II For
examiners
metal ions. This results in the magnitude of the lattice energy of Group II sulfates to use
decrease only very slightly down the group.
(i) State and explain the trend of the enthalpy change of hydration of Group II
sulfates down the group.
..
..
..
..
..
..
[1]
(ii) The relationship between lattice energy, the enthalpy change of hydration
and the enthalpy change of solution is given as follows:
'Hsol = 'Hhyd LE
Deduce the variation of the 'Hsol of Group II sulfates down the group and
hence explain the trend of the solubility of Group II sulfates shown in the
table on page 21.
..
..
..
..
..
..
..
..
..
..
trendyline
..

..

[2]

1098 trendyline
24
(g) Barium forms barium peroxide, BaO2, on heating in oxygen. For

examiners
The reaction involves the following energy change: use
O2(g) + 2e o O22(g) 'H1
By using the following data and those given in the table on page 21, construct a
Born-Haber cycle for barium peroxide in the grid below and calculate 'H1.
enthalpy change of formation of barium peroxide 630 kJ mol1
lattice energy of barium peroxide 3443 kJ mol1
enthalpy change of atomisation of barium +176 kJ mol1
Energy

ER
[3]
[Total: 16]

1099 trendyline
1
RAFFLES INSTITUTION
Higher 2
CHEMISTRY 9647/03
2 hours

Data Booklet
Do not open this question booklet until you are told to do so.
Write your name, class and index number on all the work you hand in.

A Data Booklet is provided. Do not write anything in it.
trendyline This
rinted pages.
pages

1100 trendyline
2

1 (a) Gallium trichloride, GaCl3, can be formed by direct combination of the elements.
It has a melting point of 78 qC.
Suggest the type of chemical bonding present in GaCl3 and explain why gallium
has a high tendency to form chlorides of this nature. [2]
(b) Gallium hydride, with empirical formula GaH3, can be prepared from GaCl3.
A 0.55 g sample of gaseous gallium hydride occupies a volume of 68 cm 3 at a
temperature of 243 K and a pressure of 1.12 x 105 Pa.
Determine the Mr of gallium hydride and hence its molecular formula. [3]
(c) GaH3 reacts with (CH3)3N at 178 K to give compound A, which has the following
composition by mass:
H, 11.0%; C, 37.8%; N, 14.7%; Ga, 36.5%.
A molecule of compound A has only one Ga atom.
(i) Determine the molecular formula of A. [1]
(ii) Draw a structure to show clearly

x the shape of A around the gallium atom and
x the types of bonds around the gallium atom. [2]
(d) Lithium aluminium hydride, LiAlH4, and lithium gallium hydride, LiGaH4, are both
donors of hydride, H. Thus, they are capable of reducing a large number of organic
molecules.
Suggest a possible reason why LiAlH4 is a stronger reducing agent than LiGaH4. [1]
(e) LiAlH4 can be used to reduce amides to amines as shown below:
1 LiAlH4 1
in dry ether
2 2
DEET is the active ingredient in many insect repellents. The following reaction
scheme involves the preparation and reaction of DEET.
ttrendyline
tr
r y e step 1
B
step
tep 2
DEET
T
LiA
step 3
AlH4 in dry ether

1101 trendyline
3
(i) Suggest the structures of compound B and DEET. [2]
(ii) Suggest the organic reactant used in step 2. [1]
(f) Venturamide A is a cyclic peptide with anti-malarial activity. It has the following
structure.
Suggest reagents and conditions for the basic hydrolysis of Venturamide A and
draw the structures of the organic products.
Assume that the 2 rings, and , are inert in the reaction. [3]
(g) The identity of the side-chain and pKa values associated with aspartic acid, asp,
and alanine, ala, are as follows :
amino acid aspartic acid, asp alanine, ala

R CH2COOH CH3
amino acid aspartic acid, asp alanine, ala

pKa1 2.10 2.35
pKa2 3.86 9.87
pKa3 9.82
(i) Draw the structures of the major species present in a solution of the asp-ala
dipeptide at each of the following pH values at room temperature.
pH = 1
pH = 3.86
pH = 12 [3]
(ii) Draw the zwitterionic form of asp-ala and write an equation to show how it
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can remove small amounts of H+. [2]
[Total: 20]

1102 trendyline
4
2 (a) Hydrazine, N2H4, is used as a rocket fuel.

It combusts in oxygen according to the equation:
N2H4(l) + O2(g) o N2(g) + 2H2O(l)
Using the following data, calculate the enthalpy change of combustion of hydrazine.
compound 'Hf / kJ mol1

N2H4(l) +51
H2O(l) 286
[2]
(b) The standard electrode potential for the O2/H2O half-cell was measured.
O2(g) + 4H+(aq) + 4e 2H2O(l) E{ = +1.23 V
Draw a labelled diagram to show how the standard electrode potential of the
O2/H2O half-cell was measured. Include in your diagram the direction of electron
flow. [3]
(c) (i) Hydrazine is increasingly used in fuel cells, and these direct hydrazine fuel
cells are a more practical and viable source of energy as compared to
hydrogen fuel cells.
wire connecting a pair of

graphite electrodes
N2H4(l) air (contains O2 gas)
N2 H2O
anode NaOH
H cathode
Write balanced half-equations, with state symbols, for the reactions taking
place at the anode and the cathode when the fuel cell, using aqueous sodium
hydroxide as electrolyte, is in operation. [2]
(ii) Given that E{cell for the reaction that takes place in the fuel cell is +1.56 V,
use values from the Data Booklet to calculate the standard electrode potential
for the N2/N2H4 half-cell. [1]
(iii) Suggest an advantage of using hydrazine as a fuel over hydrogen gas in a

fuel cell. [1]
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1103 trendyline
5
(d) 2-chloronitrobenzene undergoes nucleophilic aromatic substitution when heated

with aqueous NaOH at 100 oC.
Cll
C
+ NaOH + NaC
NaCll reaction I
2-chloronitrobenzene
(i) Suggest what is unusual about reaction I. [1]
The mechanism for reaction I involves a negatively charged anion intermediate.

Three resonance structures of the anion intermediate are shown below:
OH OH
.. OH
CCl
l CCl
l CCl
l
.. ..
1 2 3
(ii) Explain why structure 3 is the most stable resonance structure. [1]
Compounds Q and R can undergo nucleophilic aromatic substitution that is similar

to reaction I in (d).
C
Cll F
compound Q compound R
(e) Despite the stronger CF bond in R as compared to the CCl bond in Q,

R is more reactive than Q. Suggest why this is so. [2]
(f) The structure of 2,4-dinitrophenylhydrazine is given below.
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yll
1 2
Suggest,
st, with reasons, how the basicity of the N atoms labelled N-1 and N-2 on
nitrophenylhydrazine
trophenylhydrazine compare with each other. [1]

1104 trendyline
6
(g) Nitronium tetrafluoroborate, NO2+BF4, is a nitronium salt which can be used as a

nitrating agent for aromatic compounds.
C6H6 + NO2+BF4 o C6H5NO2 + HF + BF3
p-anisidine may be prepared using the following route.

(Assume that the OCH3 group is unreactive.)
step 1 step 2
NO2BF4
p-anisidine
(i) Name the type of reaction and describe the mechanism for the reaction in
step 1. Show relevant lone pairs and charges, and use curly arrows to
indicate the movement of electrons. [3]
(ii) Suggest reagents and conditions for step 2. [1]
Fats and oils are sometimes oxidised to form aldehydes and ketones that cause a
rancid smell in food. p-anisidine is widely used for detecting the presence of such
aldehydes and ketones.
The reaction between an aldehyde and p-anisidine is similar to the reaction

between an aldehyde and 2,4-dinitrophenylhydrazine.
(iii) Name the type of reaction which RCHO, an aldehyde found in palm oil,
undergoes with p-anisidine. [1]
(iv) Draw the displayed formula of the product formed by the reaction between
RCHO and p-anisidine. [1]
[Total: 20]
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1105 trendyline
7
3 (a) Isoprenol is a terpenoid that can be used to prepare other useful compounds.
Br2(aq)
isoprenol compound E
Name and draw a mechanism for the conversion of isoprenol to compound E. Show
relevant lone pairs and charges, and use curly arrows to indicate the movement of
electrons. [4]
(b) Limonene is a compound used in perfumery because of its strong orange scent.
F
(C10H20O4)
limonene
compound G
Compound F can be prepared from either limonene or compound G. One mole of F

reacts with excess PCl5 to produce 4 moles of gas.
(i) Suggest a structure for compound F. [1]
(ii) Suggest reagents and conditions for the preparation of compound F from
x limonene
x compound G [2]
(c) Compound W, C10H16, is a structural isomer of limonene. It is used in perfumery for

its sweet herbal scent.
W exhibits geometric isomerism. When W is reacted with hydrogen in the presence

of platinum catalyst, (CH3)2CH(CH2)3CH(CH3)CH2CH3 is formed.
When W is treated with hot acidified KMnO4(aq), it produces three organic

compounds X, Y and Z , each having the same number of carbon atoms.
Both compounds X and Z react with 2,4-dinitrophenylhydrazine to give an orange

precipitate.
Both compounds Y and Z react with excess magnesium to give an explosive gas.
Suggest
ound
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st structures for compounds X,
un W
compound W..
X, Y and
d Z,
Z, and draw the geometric
geom isomers of
[5]

1106 trendyline
8
(d) Platinum(IV) chloride reacts with ammonia to form a platinum(IV) salt with the
formula, Pt(NH3)xCly. The cation in the salt is an octahedral complex.
When 0.100 mol of Pt(NH3)xCly is dissolved in excess aqueous AgNO3, 28.7 g of

Determine the formula of the cation present in Pt(NH3)xCly. [2]
(e) [Pt(NH3)2Cl2] is a square planar complex which displays geometric isomerism.
Cisplatin, the cis-isomer of [Pt(NH3)2Cl2], kills cancer cells by altering the

configuration of their DNA. The trans-isomer, transplatin, does not exhibit such anti-
cancer activity.
(i) Draw the structures for both cisplatin and transplatin. [1]
(ii) When cisplatin enters cancer cells, one of the chloride ligands in the complex
is first replaced by a water molecule.
Write a balanced equation for this reaction. [1]
(f) Carboplatin also exhibits anti-cancer activity, but it does not result in the severe
side-effects which cisplatin causes.
Carboplatin has a square planar structure around Pt and it can be made by

replacing the two chloride ligands in cisplatin with a bidentate
cyclobutanedicarboxylate ion.
cyclobutanedicarboxylate ion
(i) Explain what is meant by a bidentate ligand. [1]
(ii) Draw the structure of carboplatin. [1]
(g) Another method of killing cancer cells involves injecting concentrated ethanol
directly into the tumour.
Explain,
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n, in terms of bonding,
cancerr cells.
bonding, how ethanol may cause the denaturation
denatura
denaturat of proteins in
[2]
[Total: 20]

1107 trendyline
9
4 (a) Phosphorus pentachloride, PCl5, is a solid which melts at 162 C.
Describe how a pure solid sample of PCl5 can be made from its elements. [2]
(b) Phosphazenes are a group of P(V)/N(III) compounds with cyclic structures.
PCl5 reacts with NH4Cl to give phosphazene S, N3P3Cl6, and steamy white fumes
are evolved.
Write an equation for this reaction and suggest a structure for phosphazene S. [2]
(c) Some halogens also react readily with methane.
CH4(g) + X2(g) o CH3X(g) + HX(g)
(i) Use bond energy data from the Data Booklet to calculate the 'H{ of this
reaction where X is iodine, I. [2]
(ii) Hence, suggest why it is not possible to make iodomethane, CH3I, by this
reaction. [1]
(d) Halogenoalkanes can undergo homolytic fission in the upper atmosphere.
(i) Explain the term homolytic fission. [1]
(ii) Suggest the most likely organic radical that would be formed by the homolytic
fission of bromochloromethane, CH2BrCl. Explain your answer. [1]
(e) Methylene, :CH2, is a neutral carbon electrophile containing two unpaired

electrons.
Methylene has a few possible structures. In one of them, the centre carbon atom is
sp3 hybridised, with each unpaired electron occupying a hybrid orbital. The HCH
bond angle is 136.
Explain why
(i) methylene can act as an electrophile, [1]
(ii) the HCH bond angle is larger than a regular tetrahedral angle of 109.5. [1]
(f) Two moles of methylene combine to form one mole of ethene.
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A saturated hydrocarbon
y T,, C4H8, can be formed byy combining four moles of
methylene.
lene
lene.
Draw the
he structure of T.
T. [1]

1108 trendyline
10
(g) Methylene undergoes further homolytic fission to form a CH fragment with three
unpaired electrons. In 1978, a symmetrical and saturated molecule, tetrahedrane
(CH)4, was made by a German chemist, by combining 4 CH fragments.
Draw the structure of tetrahedrane. [1]
(h) Ketenes are very reactive organic compounds. A ketene J can be prepared by
reacting methylene with carbon monoxide. J can also be prepared from ethanoyl
chloride by an elimination reaction in which HCl is lost.
(i) Use the information to deduce the structure of J, and hence, draw its
displayed formula. [1]
(ii) Identify the type of hybridisation of each carbon atom in J. [2]
(i) Diketene K is formed by dimerisation of ketene J.
diketene K
Ethyl acetoacetate is used in perfume to achieve a sweet smell similar to that of

green apples.
1 mole of diketene K reacts with 1 mole of ethanol to form 1 mole of ethyl

acetoacetate as the only product.
Heating 1 mole of ethyl acetoacetate with alkaline aqueous iodine produces 1 mole
of propanedioate ions and 2 moles of yellow precipitate.
(i) Determine the molecular formula of ethyl acetoacetate. [1]
(ii) Explain why one mole of ethyl acetoacetate forms two moles of yellow
precipitate after heating with alkaline iodine solution, and hence suggest the
structure of ethyl acetoacetate. [2]
(iii) Ethylamine reacts with diketene K in the same way as ethanol.
Deduce the structure of the product formed when diketene K reacts with
ethylamine. [1]
[Total: 20]
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1109 trendyline
11
5 An oxocarbon is a chemical compound consisting of only carbon and oxygen, with the
most common being carbon monoxide (CO) and carbon dioxide (CO2).
(a) Carbon monoxide is one of the most widespread and dangerous industrial hazards.
The formation of carboxyhaemoglobin, Hb(CO)4, takes place much more readily
than the formation of oxyhaemoglobin, Hb(O2)4.
Hb(aq) + 4O2(aq) Hb(O2)4(aq)
Hb(aq) + 4CO(aq) Hb(CO)4(aq)
(i) Draw a dot-and-cross diagram for CO. [1]
(ii) With reference to haemoglobin, describe and explain what is meant by the
quaternary structure of proteins. You should state the type of bonding or
interaction involved. [2]
(iii) A treatment method for carbon monoxide poisoning is to provide the patient
with pure oxygen gas over a period of time.
With reference to the equations given above, explain why this is a suitable
treatment method. [2]
(b) The water-gas shift reaction is used to produce hydrogen gas industrially by
reacting carbon monoxide with water vapour.
CO(g) + H2O(g) CO2(g) + H2(g)
(i) Write an expression for the equilibrium constant, Kp. [1]
An evacuated tank was initially filled with 0.0197 atm of CO and 0.0394 atm of H2O
at 600 K. It was sealed and left to stand. At equilibrium, the partial pressure of CO 2
was found to be 0.0191 atm.
(ii) Calculate the value of Kp at 600 K. [2]
The table below shows how the value of Kp varies with temperature.
T/K 300 900 1500

value of Kp 1.170 x 105 1.978 0.2195
(iii) Suggest whether the forward reaction of the water-gas shift reaction is an
exothermic or an endothermic reaction. Explain your answer. [1]
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1110 trendyline
12
The Gibbs free energy, 'G{ (in J mol1), and the equilibrium constant, Kp, of a
reaction are related by the following equation:
'G{ = RT ln Kp,
where R is the molar gas constant and T is the temperature in kelvins.
(iv) Using the given values of Kp, calculate the values of 'G{ at 300 K and 900 K.
Hence, determine the value of 'S{ for the water-gas shift reaction.
(Assume that both 'H{ and 'S{ are independent of temperature.) [3]
(v) Comment on the magnitude of the calculated value of 'S{. [1]
(c) Two organic acids which dissociate to form oxocarbon anions are shown below.
Name Deltic acid Squaric acid
Structure
pKa1 2.6 1.5

pKa2 6.0 3.4
(i) Sketch a clearly labelled titration curve to show how pH changes when a
10 cm3 solution of 0.100 mol dm3 deltic acid is titrated against 30 cm3 of
0.100 mol dm3 aqueous sodium hydroxide. [3]
(ii) Suggest a reason why squaric acid has a lower pKa1 value than deltic acid. [1]
(d) An aromatic compound X, C12H6O12, produces carbon dioxide when reacted with
aqueous sodium carbonate.
Heating X with concentrated sulfuric acid for several hours produces a neutral
oxocarbon Y, C12O9.
When Y is heated strongly with ammonia, a compound Z, C12H3O6N3, is formed.
When Z is heated strongly with dilute sulfuric acid, compound X is formed.
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Suggest
st structures for
f compounds
p X,
X, Y and Z. [3]
[Total: 20]
END OF PAPER
APE

1111 trendyline
Raffles Institution
2016 Year 6 Preliminary Examination
Suggested Answers to H2 Chemistry Paper 1
1 2 3 4 5 6 7 8 9 10
D B B C D D C C B D
11 12 13 14 15 16 17 18 19 20
D B B A A C C D C D
21 22 23 24 25 26 27 28 29 30
B D D A A B C A B A
31 32 33 34 35 36 37 38 39 40
D C B A A B D A B A
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1112 trendyline
Raffles Institution
Question 1
(a) Cu2+ + 2e o Cu
m 2m
To plate m g ( mol) of copper requires mol of electrons,
63.5 63.5
2m
i.e. to plate m g of copper requires F C of electrical charge.
63.5
2m
Since Q = It, it follows that F It .
63.5
63.5 I
m t (shown)
2F
63.5 u 0.500
(b) 1.00 t t 6079 s
2 u 96500
maximum t is 6079 s (or 6080, correct to 3 sf)
(c) Set-up diagram

+
electrical
power
source
pure copper
rod
object to be
0.0500 mol dm3 plated
CuSO4
pure copper rod + object to be plated + electrolyte

electrical power source connected in correct direction
(Object to be plated does not need to be fully submerged for the determination of
Faraday)
Procedure
1. Connect the metal object to be plated to the circuit as shown in the set-up above. (Metal
object should be the cathode, with the negative end of the battery connected to it.)
2. Turn on power source and start stopwatch at the same time. After some time, copper
should be deposited on the metal object.
3. Power source can be turned off after 1200 s.
4. Remove copper-plated object from solution and wash it with distilled water to remove
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traces of CuSO4.
5. Allow object
ct to dry on a piece of filter paper.
pape
6. Record the e mass of the plated object, and obtain the difference in ma mass by subtracting
2.00 g from
m this value.
7. Repeat stepsps 1 to 6 with durations of 2400 s, 3600 s, 4800 s, 6000 s.
eps
ph of mass of copper deposited against
8. Plot a graph gain time and obtain a line o
of best-fit.
63.5 u 0.500
9. Gradient of line = and Faraday can be calculated from this equation.
2uF
2016 Raffles Institution 1
1113 trendyline
Graph
Mass of
1.2
copper
deposited
1
(m) / g
0.8
0.6
0.4
0.2
0
00 5000
1000 10000
2000 15000
3000 20000
4000 25000
5000 30000 Time/s
6000 35000
Best-fit line passing through origin
Question 2
(a)(i)
(a)(ii) Let y be the % of ascorbic acid in the mixture.

(+20)(y/100) + (100y)(20/100) = 10
y = 25
Hence, the mixture contained 25% of ascorbic acid and 75% of compound A.
(a)(iii) Ascorbic acid contains 4 hydroxyl groups which can form intermolecular hydrogen bonding
with water, hence making it soluble.
(b)(i) atom / group of atoms with unpaired electron(s)
(b)(ii) H2O
(c) Reagents and conditions: aqueous sodium hydroxide, heat strongly

Observations: A gas that turned damp red litmus paper blue was evolved for asparagine
trendyline
endyyline
yl
but not for serine.
ine.
ne
OR Reagents and conditions: K2CrC 2O7(aq), H2SO4(aq),
aq), heat
heat
Observations: For serine, solution
solutio changed from orange to o green.
green. N No
o ccolour change was
observed for asparagine.
sparagine.
OR Reagents and conditions: KMnO4(aq), H2SO4(aq), q), heat
Observations: For
F serine,
i solution
l ti changed
h d ffrom purple
l ((or violet)
i l t) tto colourless.
l No colour
change was observed for asparagine.
1114 trendyline
(d)(i) structure of compound D:
Cl I
(d)(ii) X is likely to be Cl as the CI bond is weaker / easier to break / has lower bond energy.
(d)(iii) Reagents: alcoholic ammonia or (limited) ammonia dissolved in ethanol

Condition: heat in sealed tube
Question 3
(a)(i) 1s2 2s2 2p6 3s2 3p6 3d9
In oxygenated haemocyanins, the presence of ligands causes the splitting of the five
originally degenerate 3d orbitals in Cu2+ into two sets of slightly different energy levels.
As these orbitals are partially filled, the electrons from the lower energy d-orbitals can
absorb energy corresponding to the visible light spectrum and get promoted to higher
energy d-orbitals (i.e. d-d transition).
The colour observed is the complement of the colour absorbed.
(a)(ii) Deoxygenated haemocyanin contains Cu+, which has a fully filled 3d subshell. Hence, an
electron from a lower energy d-orbital cannot be promoted to a higher energy d-orbital.
As no light in the visible light spectrum is absorbed (or all wavelengths in the visible light
spectrum are transmitted), deoxygenated haemocyanin is colourless.
(b)(i) [O]: RCHO + 3OH o RCOO + 2H2O + 2e

[R]: 2Cu2+(complex) + 2OH + 2e o Cu2O + H2O
Overall: 2Cu2+(complex) + 5OH + RCHO o Cu2O + 3H2O + RCOO
(b)(ii) tartrate ion
(c)(i) 2Al + 3Ag2S o 6Ag + Al2S3
(c)(ii) The redox reaction involves the reduction of Ag2S(s) to Ag and the oxidation of Al to Al2S3(s)
rather than the reduction of Ag+(aq) to Ag and the oxidation of Al to Al3+(aq).
(c)(iii) NaCl acts as the salt bridge in this redox reaction / facilitates electron transfer.
(c)(iv) 2Al + 3Ag2S o 6Ag + Al2S3

Al2S3 + 6H2O o 2Al(OH)3 + 3H2S
Amount of H2S given off = (17.1 / 24000) = 7.125 x 104 mol
3Ag2S Al2S3 3H2S 6Ag
Amount of tarnished silver = 7.125 x 104 x 2 = 1.425 x 103 mol
[(1.425 x 103 x 108)) / 2.00]] x 100% = 7.70%
trendyline
trendyl
n
% of tarnished silver = [(
Question 4
(a)(i) The lone pairr of electrons on O of OHOH delocalises into the benzene ring,
ring causing the ring
rin
to be more electron-rich and hence susceptible to electrophilic su substitution. Hence,
bromination off phenol occurs rapidly.
rapidly

1115 trendyline
(a)(ii) 2,4,6-tribromophenol formed in reaction II is insoluble and appeared as a white precipitate,
thus causing the reaction mixture to appear a little cloudy.
1
(a)(iii) initial rate v and [H+] v VH+
t
(a)(iv) 1/t / s1
0.120
0.100
0.080
0.060
0.040
0.020
0.000 VH+2/ cm6

0 100 200 300 400 500 600 700
(a)(v) Order of reaction with respect to H+ is 2.

1
As rate v and [H+] v VH+, the straight line obtained, which passes through the origin, shows
t
1
that v (VH+)2 rate v [H+]2 reaction is second order with respect to H+.
t
(b)(i) displayed structure of compound E:
Cl Cl
(b)(ii) Multiple cross-links / covalent bonds between the polymer strands in Bakelite cause the
structure to be more rigid.
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1116 trendyline
(c)
10 20 oC
compound F H2SO4(aq),
C8H8O3 heat under reflux
compound G
excess concentrated H2SO4,

170 oC
PCl3, PCl5 or SOCl2
(d)(i)
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rre
(d)(ii) Solution J is aqueous
queou NaOH (or KOH)
KOH).
Thymol reactss with NaOH(aq) to form an ionic salt,
alt, which is insoluble in the o
soluble in the aqueous layer due to the formation of ion-dipole interactions.
organic layer but is

1117 trendyline
Question 5
(a) Since Ba has a greater number of filled principal quantum shells, its valence electrons are
located in a shell with a larger principal quantum number.
The valence electrons are further away from the nucleus, resulting in a larger radius.
(b) Small pieces of calcium react steadily with cold water producing bubbles of hydrogen and a
white precipitate of calcium hydroxide.
Ca(s) + 2H2O(l) o Ca(OH)2(s) + H2(g)
Small pieces of barium react vigorously with cold water producing bubbles of hydrogen and
a solution of barium hydroxide.
Ba(s) + 2H2O(l) o Ba(OH)2(aq) + H2(g)
(c) The density of calcium (1.55 g cm3) is greater than the density of water (1.00 g cm3), so
calcium sinks in water.
(d) Radium is radioactive, so some or all of the isotopes are unstable. Hence, the relative
abundance of some or all of the isotopes is difficult to determine.
(e) Ksp of SrSO4 = [Sr2+][SO42]

Solubility of sulfate in water in mol dm3
= (0.0130 / 183.7) x 1000 / 100
= 7.077 x 104 mol dm3
Ksp = (7.077 x 104)2 = 5.01 x 107 mol2 dm6
(f)(i) Cationic radii of Group II ions increase down the group, resulting in decreasing charge
density. Hence, the magnitude of hydration energy decreases significantly down the group.
(f)(ii) The magnitude of LE decreases only very slightly down the group, whereas the magnitude of
hydration energy decreases significantly down the group.
Hence, Hsol is less exothermic down the group,

and solubility of Group II sulfates decreases down the group.
(g)
Energy
Ba2+ (g) + O22 (g)
'H1
Ba2+ (g) + O2 (g) + 2e
1st IE + 2nd IE of Ba
LE of BaO2
Ba(g) + O2 (g)
'Ha [Ba (s)]
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dy i
Ba(s) + O2 (g)
0
'H
Hf [BaO
Ba 2 (s)]
B 2(s)
BaO (
By Hess Law,
'H1 = 1468 176 630 + 3443 = +1169 kJ mol1
1118 trendyline
Raffles Institution
1 (a) covalent bonding

Ga3+ has a high charge density and so it distorts the electron cloud of Cl to such an extent that
electron sharing becomes predominant.
(b) 0.55
(1.12 x 105)(68 x 106) = x 8.31 x 243
M
M = 146 g mol1
Mr = 146
molecular formula is Ga2H6
(c) (i) H C N Ga
% 11.0 37.8 14.7 36.5
% / Ar 11.0 3.15 1.05 0.524
ratio 21 6 2 1
molecular formula of A is GaN2C6H21
(ii) CH3
CH3
N CH3
H
H Ga
H
CH3 N CH
3
CH3
trigonal bipyramidal shape with N(CH3)3 groups in axial positions;
two NoGa dative bonds and three GaH covalent bonds
(d) AlH bond is more polar than the GaH bond, and hence, it is easier to break the AlH bond to
release the hydride.
OR Al is less electronegative/more electropositive than Ga, and so, there is a larger Gon H of
AlH. Hence, it is easier for the GH to gain an electron pair from AlH bond to form H.
(Note: Electronegativity values for H: 2.20, Al: 1.61, Ga: 1.81)
(e) (i)
O Cll
C O N
(ii)
B:
H N
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r dy DEET :

1119 trendyline
1 (f) NaOH(aq), heat under reflux/prolonged heating/prolonged boiling
COO-Na+
Na+-OOC NH2
H2N S N
N
O
N S
NH2 COO Na - +
(g) (i) O
H3N
N COOH
H
COOH
pH = 1
O O
H 3N H3N
N COO- N COO-
H H
COOH COO-
pH = 3.86
O
H2N
N COO-
H
COO-
pH =12
(ii) O
H3N
N COO-
H
COOH
O O
H 3N H 3N
N COO- + N COOH
+H
H H
COOH COOH
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1120 trendyline
2 (a) 'Hc = 2(286) (+51)
= 623 kJ mol1
(b)
e e T = 298 K
V
H2(g) salt bridge O2(g)

(1 atm) (1 atm)
Pt Pt
H+(aq) H+(aq)
[H+(aq)] = 1 mol dm3 [H+(aq)] = 1 mol dm3
(c) (i) Cathode: O2(g) + 2H2O(l) + 4e o 4OH(aq)

Anode: N2H4(l) + 4OH(aq) o N2(g) + 4H2O(l) + 4e
(ii) E{cell = +0.40 (y) = +1.56 V

y = 1.16 V
E{(N2/N2H4) = 1.16 V
(iii) As the fuel is liquid at room temperature, it can be handled and stored more easily than
hydrogen. OR Hydrazine has an e.m.f. of 1.56 V, which is higher than the 1.23 V for a
hydrogen fuel cell. OR Hydrogen yields explosive mixtures with air or oxygen, so it must be
handled with great care.
(d) (i) Due to partial double bond character of the C-Cl bond, it is very strong and nucleophilic
substitution does not usually take place. OR The benzene ring is electron-rich and does
not usually attract nucleophiles.
!
(ii) The electron-withdrawing NO2 group is bonded directly (OR closest to) to the carbon
with the negative charge, and thus, is able to disperse the negative charge most
effectively.
!
(e) F is more electronegative than Cl
and disperses the negative charge on the anion intermediate to a larger extent
(f)
1
2
tre
ren
N-1 is less basic than N-2. The lone pair of electrons on N-1 is delocalised into the
benzene ring, and is hence less available for donation to a proton.
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2 (g) (i) Electrophilic substitution
slow
BF4 + fast
BF3 HF
(ii) Sn, concentrated HCl, followed by NaOH(aq)
(iii) condensation OR nucleophilic addition elimination
(iv)
OR
3 (a) Electrophilic addition
slow
G
G+
..
fast
..
..
..
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tr
re
re
ennd
dyli
yliiin
ne fast
ast
H3O

1122 trendyline
3 (b) (i)
ROH + PCl5 o RCl + POCl3 + HCl
1 mole of F has 4 moles of OH

groups, so 4 moles of HCl(g) will
be produced.
Compound F is
(ii) limonene to F: cold KMnO4(aq), NaOH(aq)

G to F: LiAlH4, dry ether
(c) O
HO OH
OH
O
O O
O
X Y Z
W
(E isomer) (Z isomer)
(d) Amount of AgCl precipitate formed = 28.7 / (108 + 35.5) = 0.200 mol
Amount of Cl in 0.100 mol of complex = 0.200 mol
Mole ratio of complex to chloride is 0.100 : 0.200 = 1 : 2
Since there are 2 Cl per cation, and the charge on the cation is 4+, the charge on the complex
cation is 2+.
As the coordination number is 6, there must be 6 2 = 4 NH3 per cation
The cation is [Pt(NH3)4Cl2]2+.
(e) (i)
Cl Cl
Cl Cl
cisplatin transplatin
(ii) [Pt(NH3)2Cl2] + H2O o [Pt(NH3)2Cl(H2O)]+ + Cl
(f) (i) A bidentate ligand is one which can form 2 co-ordinate bonds simultaneously with the
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central me
metal ion (or atom) / donatess 2 lone pairs of
o electrons to tthe central metal ion (or
atom).

1123 trendyline
3 (f) (ii)
(g) Ethanol can disrupt the tertiary and quaternary structures of proteins as its OH group can
form hydrogen bonds with hydrophilic R groups such as C=O, CO2H, OH, NH2, NHR
groups.
The ethyl group of ethanol can disrupt tertiary and quaternary structures by forming van der
Waals forces of attraction with the non-polar hydrophobic R groups such as alkyl groups.
Hence, the protein rearranges itself and is denatured.
4 (a) P reacts with excess chlorine gas. Collect solid and recrystallise.
(b) 3PCl5 + 3NH4Cl o N3P3Cl6 +12HCl

Cl Cl
Cl Cl
Cl Cl
(c) (i) energy change for bonds broken = BE[CH] + BE[II] = 410 + 151 = 561 kJ mol1
energy change for bonds formed = {BE[CI] + BE[HI]} = (240 + 299) = 539 kJ mol1
'H = 561 539 = +22 kJ mol1
(ii) The overall reaction is endothermic. 'S | 0 as number of (moles of) gaseous molecules
before and after the reaction is the same. 'G = 'H T'S > 0 such that the reaction is not
energetically feasible OR no strong bonds / only weak bonds are formed OR high Ea
(d) (i) breaking of a bond to form (two) radicals / species with unpaired electrons
(ii) CH2Cl AND the C-Br bond is the weakest / needs the least energy to break
(e) (i) electron-deficient / able to accept (lone pair of) electrons

(ii) Electron-electron repulsion increases in the order:
unpaired-unpaired < unpaired bond pair < bond pair bond pair
(f)
cyclobutane
(g)
trr
1124 trendyline
4 (h) (i)
(ii) sp (for carbonyl C) and sp2 (for C bonded to 2 H)
(i) (i) C6H10O3

(ii)
due to CH3COR and CH3CH2OH (after hydrolysis)
(iii) CH3COCH2CONHCH2CH3 (amide formation)
5 (a) (i)
x
C O x
xx
x
x
(ii) The quaternary structure of haemoglobin consists of four polypeptide chains, where two
D-subunits and two E-subunits are held together through R group interactions, namely
ionic attractions, van der Waals interactions, hydrogen bonds and disulfide linkages.
Each subunit is covalently bonded to a haem residue, which contains a central Fe2+
ion that forms dative bonds with 4 N atoms in a porphyrin ring and an N atom of a histidine.
(iii) Providing O2 forms Hb(O2)4(aq), which shifts the position of equilibrium of

Hb(aq) + 4O2(aq) Hb(O2)4(aq) to the right, removing Hb(aq) from the bloodstream.
By Le Chateliers Principle, the position of equilibrium of Hb(aq) + 4CO(aq)

Hb(CO)4(aq) will shift left to counteract the loss of Hb(aq), thus reducing the amount of
Hb(CO)4(aq) in the body.
(b) (i) pCO2 pH2

Kp
pCO pH2O
(ii)
CO (g) + H2O (g) CO2 (g) + H2 (g)
Initial pressure
0.0197 0.0394 0 0
/ atm
Change in
pressure / atm
0.0191 0.0191 +0.0191 +0.0191
Eqm pressure
0.0006 0.0203 0.0191 0.0191
/ atm
(0.0191)(0.0191)
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y e
Kp 30.0
.0006)(0.0203
.0006)(0.0203)
(0.0006)(0.0203)
(iii) The valuelue

ue of Kp decreases as temperature increase
increases, so increa
increasing the temperature
favours s the endothermic reverse reaction
reaction.
actio . Thus, the forward re
reaction of the water-gas
shift reaction
ti is
i an exothermic
th i reaction.
ti

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5 (b) (iv) 'G{ (300) RT ln Kp (300)
(8.31)(300) ln (117000)
29090 J mol1 (4 sf)
'G{ (900) RT ln Kp (900)

(8.31)(900) ln (1.978)
5101 J mol1 (4 sf)
'G{ (300) 'H{ (300)'S{ 29090 J mol1 ----- (1)

'G{ (900) 'H{ (900)'S{ 5101 J mol1 ----- (2)
(1) (2): 'S{ 40.0 J K1 mol1 (3 sf)
(v) The magnitude is small as there is no change in the number of (moles of) gaseous
molecules when reactants changed to products. Hence, there is little change in the number
of ways that energy can be distributed over the molecules.
(c) (i)
6.0
2.6
Sketch should include the following:

x labelled axes, with volume of NaOH up to 30.0 cm3, and correct shape of graph
x the 2 pKa values with the 2 corresponding volumes of NaOH
x volumes of NaOH required to reach the 2 equivalence points
(c) (ii) There are more electron withdrawing C=O groups in squaric acid than in deltic acid. As
such, the conjugate acid anion of squaric acid is more stable than that of deltic acid.
Hence, squaric acid is more acidic and has a lower pKa1 value than deltic acid.
(d)
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1126 trendyline
RIVER VALLEY HIGH SCHOOL
YEAR 6 PRELIMINARYEXAMINATIONII
CANDIDATE
NAME
CLASS 6
CENTRE INDEX
NUMBER S NUMBER
1 hour

Data Booklet

Write your name, class, centre number and index number on the Answer Sheet in
the spaces provided.
There are forty questions on this paper. Answer all questions. For each question
there are four possible answers A, B, C and D.
Choose the one you consider correct and record your choice in soft pencil on the
separate Answer Sheet.
Each correct answer will score one mark. A mark will not be deducted for a wrong
answer.
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Any rough working
king should be done in this booklet.
b

ted pages and 3 blank page
pages.
1127 trendyline
2
Section A
For each question there are four possible answers, A, B, C and D. Choose the one
1 For complete combustion of 20.0 g of heptane, what is the minimum volume of

oxygen gas required at s.t.p.?
A 0.2 dm3
B 2.2 dm3
C 49.3 dm3
D 52.8 dm3
2 Element X exists as 3 different isotopes and has a relative atomic mass of 66.6.
Which of the following compositions of isotopes is correct?
A 25% 65X, 50% 66X and 25% 67X
B 30% 65X, 60% 66X and 10% 67X
C 50% 65X, 20% 66X and 30% 67X
D 10% 65X, 20% 66X and 70% 67X
3 Which of the following does not contain a singly occupied orbital?
A N2+ B S C Br+ D Sc3+
4 Dinitrogen tetroxide, N 2 O 4 , has a simple covalent structure.

Which of the following correctly describes the bonding within the dinitrogen tetroxide
molecule?
bond bond dative bond
A 3 2 2
t dyli
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B 5 0 4
C 5 2 2
D 5 4 0
River Valley High School 9647/01/PRELIM II/16 [Turn over

1128 trendyline
3
5 The Valence Shell Electron Pair Repulsion (VSEPR) theory is used to predict the
shapes of molecules.
Which shape is correctly predicted by VSEPR?
number of bonded
number of lone pairs
electron pairs around shape
around central atom
central atom
A 2 4 non-linear
B 3 2 T-shaped
C 4 1 square planar
D 3 2 see-saw
6 Equal masses of gaseous N 2 , NH 3 and N 2 O are injected into an evacuated

container to produce a total pressure of 3 atm.
How do the partial pressures of N 2 , NH 3 and N 2 O compare?
A p N2 = p NH3 = p N2O B p N2 <p NH3 <p N2O
C p NH3 <p N2 <p N2O D p N2O <p N2 <p NH3

The enthalpy changes for three reactions are given below:
Na(s) Na(g) H = +107 kJ mol1
H+(aq) + OH(aq) H 2 O(l) H = 58 kJ mol1
2Na+(g) + 2H+(aq) + 2e 2Na+(aq) + H 2 (g) H = 1700 kJ mol1
What is the enthalpy change for the following reaction?

Na(s) + H 2 O(l) Na+(aq) + OH(aq) + H 2 (g)
A 191 kJ mol1
B 307 kJ mol1
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C 685 k mol1
5 kJ
D 1 kJ mol11
1041
41

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4
8 The dissolution of ammonium nitrate is a chemical reaction commonly used in cold

packs that serve to relief pain in sports injury. A thin plastic membrane separates
powdered ammonium nitrate and water. When the cold pack is squeezed, the
membrane breaks and the ammonium nitrate dissolves in water.
NH 4 NO 3 (s) NH 4 NO 3 (aq)
What are the signs of H, S, G for the overall process?
H S G
A +
B +
C + +
D + + +
9 Hydrogen reacts with iodine according to the equation:
H 2 (g) + I 2 (g) 2HI(g)
P atm of hydrogen is allowed to react with Q atm of iodine at constant temperature.

At equilibrium, it is found that
A the partial pressure of hydrogen is greater than P.
B the total pressure of the system is (P + Q) atm.
C the total pressure of the system is greater than (P + Q) atm.
D the total pressure of the system is less than (P + Q) atm.
10 When 10 cm3 of 0.02 mol dm3 aqueous Ba(OH) 2 is added to separate solutions of
10 cm3 of 0.1 mol dm3 MgCl 2 and 10 cm3 of 0.1 mol dm3 CaCl 2 , what would be
observed?
(K sp of Mg(OH) 2 = 3.2 1011 mol3 dm9; K sp of Ca(OH) 2 = 1.35 105 mol3 dm9)
A Only Ca(OH) 2 would be precipitated.
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B Only Mg(OH)
M 2 would be precipitated.
ta
C Both Mg(OH) 2 and Ca(OH

Ca(OH) 2 would
ould be precipitate
precipitated.
D Neither
her Mg(OH)
M (OH) 2 nor Ca(OH)
C (OH) 2 would be precipitated
precipitated.

1130 trendyline
5
11 The auto-ionisation of water is represented by the following equation:
H 2 O(l) H+(aq) + OH(aq) H = +57 kJ mol1
Given that the value of the equilibrium constant, K w , is 1.0 1014 mol2 dm6 at
298 K, which of the following statements is true?
A Water is not a neutral liquid at a temperature lower than 298 K.
B When water is heated, the concentration of OH increases.
C The pH of water at temperatures higher than 298 K is greater than 7.
D The association of water molecules by hydrogen bonding increases as

temperature rises.
12 Consider the following reaction:

3X + Y X 3 Y
The mechanism involves the following steps:
2X X 2 (fast)
X2 + Y X2Y (slow)
X2Y + X X3Y (fast)
Based on the information, what is the rate equation for this reaction?
A Rate = k[X]2 B Rate = k[X 2 ][Y]
C Rate = k[X]2[Y] D Rate = [X]3[Y]
13 The decomposition of compound A is a first order reaction which proceeds

according to the equation:
A(s) 2B(s) + C(g)
A sample of A gave 80 cm3 of C on complete decomposition and it took

40 min for 40 cm3 of C to be evolved.
For another identical sample of A, how long would it take for 70 cm3 of C to be
evolved?
C
40 min
80 min
n
trendyline B
D
70 min
120 min

1131 trendyline
6
14 The Daniell Cell comprises two half-cells a copper electrode dipped in copper(II)
sulfate solution and a zinc electrode dipped in zinc sulfate solution linked by a salt
bridge.
Which of the following will increase the cell e.m.f. of the Daniell Cell?
A Adding solid copper(II) sulfate to the copper half-cell.
B Increasing the mass of copper electrode.
C Increasing the concentration of the zinc sulfate solution.
D Allow the system to reach equilibrium before measuring cell e.m.f.
15 Two separate electrolyses were performed as follows, under the same conditions of
temperature and pressure.
1. When aqueous hydrochloric acid was electrolysed for five minutes, 100 cm3
of hydrogen were collected from the cathode.
2. When aqueous sulfuric acid was electrolysed for five minutes, 200 cm3 of
oxygen were collected from the anode.
If the current used in electrolysis 1 was I, what was the current used in electrolysis
2?
A 4I B 2I C I D 0.5I
16 Which of the following is a trend across Period 3 of the Periodic Table?
A The radii of ions decrease.
B The first ionisation energy decreases.
C The melting points of elements decrease.
D The compounds of elements become increasingly covalent.
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1132 trendyline
7
17 Which of the following equations represents the reaction when calcium nitrate is
heated strongly?
A Ca(NO 3 ) 2 CaO + N 2 O 5
B Ca(NO 3 ) 2 Ca(NO 2 ) 2 + O 2
C 2Ca(NO 3 ) 2 2CaO + 4NO 2 + O 2
D 3Ca(NO 3 ) 2 Ca 3 N 2 + 4NO 2 + 5O 2

Which of the following solutions of halide will not change the colour of acidified
potassium dichromate(VI) ?
A chloride B bromide C iodide D astatide
19 Which statement correctly defines a transition element?
A Transition elements exhibit more than one oxidation state in their compounds.
B Transition elements or their compounds are widely used as catalysts.
C Transition elements form many coloured compounds.
D Transition elementshave partially filled d orbitals.
20 Which of the following compounds cannot be obtained from propene in a single

reaction?
A CO 2 B CH 3 CH 2 CH 3
C CH 3 CH 2 CH 2 CN D CH 2 (OH)CH(OH)CH 3
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1133 trendyline
8
21 How many alkenes (including stereoisomers) can be formed when the following
alcohol is heated with concentrated sulfuric acid?
OH
A 0 B 2 C 3 D 4
22 Saccharin, an artificial sweetening agent, can be synthesised from methylbenzene

using the following reaction scheme:
CH3 CH3 O O CH3 O O
S S
ClSO3H Cl NH3 NH2
Step 1 Step 2
Step 3
O
NH
O
S
Saccharin
What type of reactions do steps 1 and 2 illustrate?
Step 1 Step 2
A Electrophilic substitution Condensation
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trendy
dyline
li
B Electrophilic
ect op c subst
substitution
tut o Nucleophilic
uc eop Addition
C Nucleophilic substitution Conde

Condensation
D Nucleophilic substitution Nucleophi

Nucleophilic
ucleoph Addition

1134 trendyline
9
23 Fluothane, CF 3 CHBrCl, is a volatile liquid widely used as an anaesthetic.

Which of the following statements about fluothane is not correct?
A Fluothane may cause the depletion of the ozone layer.
B Weak van der Waals forces hold molecules of fluothane together.
C Fluothane undergoes elimination when treated with hot ethanolic NaOH.
D When a sample of fluothane is heated with aqueous silver nitrate, a mixture of

white and cream precipitate is formed.
24 Eugenol is a common component of perfumes and essential oils. It is also used as

an antiseptic.
H3C O
HO CH2CH=CH2
eugenol
(You may treat the OCH 3 group attached to the benzene ring as inert.)
Which of the following statements about eugenol is correct?
A It reacts with 2,4-DNPH to give an orange precipitate.
B It gives white fumes when reacted with thionyl chloride.
C It decolourises hot acidified potassium manganate(VII).
D It reacts with 2 moles of Br 2 in a suitable solvent to form a product with 4

bromine atoms incorporated.
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1135 trendyline
10
25 Cyclohex-3-en-1-one has the following structure:
cyclohex-3-en-1-one
Which of the following compounds is formed when cyclohex-3-en-1-one is reacted
with NaBH 4 dissolved in an organic solvent?
A B
OH OH
C D
O O
26 Compound J gives the following observations with Tollens Reagent and

Na 2 CO 3 (aq).
Reagent Observation
Tollens Reagent Silver mirror observed
Na 2 CO 3 (aq) No effervescence observed
From the above observations, what could be a possible structure for J?
A (COOH) 2
B CH 3 COCHO
C CH 3 COCOOH
D CH 3 COCOCH 3
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1136 trendyline
11
27 In the study of organic reaction mechanisms, radioactive oxygen-18, 18O, is often

used to tag organic molecules. The radioactivity of the products can then be
detected to deduce which products contain 18O.
When 18O-tagged propan-1-ol is heated with ethanoic acid in the presence of a
small amount of concentrated sulfuric acid, which of the following set of products will
be obtained?
A CH 3 CH 2 CH 2 18OCOCH 3 and H 2 O
B CH 3 CH 2 CH 2 OCOCH 3 and H 2 18O
C CH 3 CH 2 CH 2 18OCOCH 3 and H 2 18O
D CH 3 CH 2 CH 2 OCOCH 3 and H 2 O
28 Which of the following correctly shows the compounds arranged in decreasing pK a

values?
A CH 2 FCOOH > CH 2 ClCOOH > CH 2 BrCOOH
B CH 3 COOH > C 6 H 5 COOH > C 6 H 5 OH
C CCl 3 COOH > CHCl 2 COOH > CH 2 ClCOOH
D C 2 H 5 OH > C 6 H 5 OH > C 6 H 5 COOH
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1137 trendyline
12
29 Valinomycin is a peptide-like molecule that disrupts plasma membrane formation in

bacteria.
valinomycin
Which of the following will not be produced when valinomycin is heated with dilute
H 2 SO 4 (aq) for a period of time?
A O B O
+
OH NH3
HO HO
C O D O
+
NH3 OH
HO HO
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1138 trendyline
13
30 Denaturation of proteins occurs due to the destruction of the tertiary structure where
various R group interactions are disrupted by external factors.
Which of the following correctly shows the R group interactions that will be affected
by the corresponding external factor?
R group interactions External factor
A disulfide bridges extreme pH changes
B ionic interactions addition of alcohol
C van der Waals forces addition of heavy metal ions
D hydrogen bonding extreme pH changes
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1139 trendyline
14
Section B
For each of the questions in this section, one or more of the three numbered
put a tick against the statements that you consider to be correct).
A B C D
1, 2 and 3 are 1 and 2 only are 2 and 3 only are 1 only is

31 Which statements about aluminium are correct?
1 It forms amphoteric oxides.
2 It forms an ionic compound with oxygen.
3 It forms an ionic compound with chlorine.
32 Between ethanol molecules, there exists
1 hydrogen bonds.
2 instantaneous dipole-induced dipole interactions.
3 covalent bonds.
33 For a first order reaction, which of the following graphs will be a straight line passing
through the origin?
1 Initial rate vs concentration of reactant
2 Initial rate vs time taken for complete reaction
3 Concentration of reactant vs time taken for complete reaction

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15
A B C D

34 Which statements correctly describe an electrolytic cell?
1 It is driven by an external battery.
2 The polarities of the cathode and anode are negative and positive respectively.
3 It is used to extract unreactive metals from the ores.
35 Which of the following statementsare true for astatine, the element below iodine in
Group VII of the Periodic Table?
1 Silver astatide is insoluble in concentrated aqueous ammonia.
2 Astatine oxidises potassium chloride to chlorine.
3 Hydrogen astatide is more stable to heat than hydrogen iodide.
36 When placed in a strong magnetic field, paramagnetic objects are attracted to the
field. Paramagnetism arises when an element has unpaired electrons.
Which of the following chemical species would you expect to exhibit
paramagnetism?
1 Cr
2 Mn
3 Cu+
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1141 trendyline
16
A B C D

37 Deuterium, D, is the 2H isotope of hydrogen.
Which of the following reactions could give an organic compound having a

deuterium atom incorporated?
O
DCN
1
NaCN in D2O
H
NaOD in D2O
2 CN heat
DBr
3 OH
heat
38 In which of the following reactions will the inorganic reagent act as the nucleophile?
Br
HBr
1
NaCN
2
Br CN
O O
NH3
3
Cl NH2
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1142 trendyline
17
A B C D

39 Compound X is a flavouring agent in food.

CHO
HO O
O
X
Which of the following reagents will cause a colour change when the reagent is
added to a sample of compound X?
1 aqueous bromine
2 neutral iron(III) chloride solution
3 hot acidified potassium dichromate(VI)
40 Which of the following descriptions about haemoglobin are correct?
1 Both O 2 and CO can bind to haemoglobin.
2 The quaternary structure of haemoglobin consists of two -helices and two

-pleated sheets.
3 A maximum of six oxygen molecules may be bound to each haemoglobin

molecule.
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- End off Paper -

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18
BLANK PAGE
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19
BLANK PAGE
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20
BLANK PAGE
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1

CANDIDATE
ANSWER KEY
NAME
CLASS 6
CENTRE INDEX
NUMBER S 3 0 4 4 NUMBER
0 0
1 hour
1. C 11. B 21. D 31. B
2. D 12. C 22. A 32. B
3. D 13. D 23. C 33. D
4. C 14. A 24. C 34. B
5. B 15. A 25. B 35. D
6. D 16. D 26. B 36. B
7. A 17. C 27. A 37. D
8. C 18. A 28. D 38. C
9. B 19. D 29. C 39. A
10. C 20. C 30. D 40. D
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River Valley High School
2016 Preliminary Examinations II(Answer Key)
1147 trendyline
CANDIDATE
NAME
CLASS 6
CENTRE INDEX
NUMBER S NUMBER
Paper 2Structured Questions 13 September 2016
2 hours
Write your name, class, centre number and index number on all the work you hand in.
Write in dark blue or black pen on both sides of paper.

A Data Booklet is provided. Do NOT write anything on it.
The number of marks is given in brackets [] at the end of each question or part question.
For Examiners Use

Paper 2
Question Total
1 2 3 4 5 6
Number (Paper 2)
Marks
12 13 8 9 16 14 72
trre
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reen
ndylin
in
ne
Paper 1 Paper 3
Pa Total
40 80 192
This
his document consists of 18
18 printed pages and 2 blank pages.
page
pag

2016 Preliminary ExaminationII
1148 trendyline
2
1 Planning (P)
Salicylic acid is known for its ability to ease aches and pains as well as reduce
fevers. Its analgesic and anti-inflammatory properties makes it one of the most
important medications needed in a basic health system, placing it on the World
Health Organisation Model List of Essential Medicines.
It can be synthesised via the alkaline hydrolysis of methyl salicylate, followed
by acidification.
COOCH3 COOH
OH OH
methyl salicylate salicylic acid

(M r = 152) (M r = 138)
Methyl salicylate is a liquid with a density of 1.174 g cm3.

Aqueous sodium hydroxide used for the hydrolysis has a concentration of
6.0 mol dm3.
Like most organic reactions, the yield of this reaction is less than 100%. Using
the procedure described below, a typical yield of pure salicylic acid is 60%.
Methyl salicylate is mixed with aqueous sodium hydroxide in a molar ratio of

1:2. The reaction is heated under reflux conditions for around 30 minutes to
form a di-sodium salicylate salt.
When the reaction mixture has cooled down, concentrated hydrochloric acid is
added until in excess to cause the crude salicylic acid to precipitate. This
process is highly exothermic.
The crude salicylic acid is then purified by recrystallisation from water.
(a) Using the information given above:
(i) write a balanced equation for the formation of the di-sodium

salicylate salt;
[1]
River Valley High School 9647/02/PRELIM II/16

1149 trendyline
3
(ii) calculate the volumes of methyl salicylate and aqueous sodium
hydroxide you would use to prepare 10 g of pure salicylic acid,
showing your working.
[2]
(b) Write a plan for the preparation of 10 g of pure salicylic acid.

In your plan, you should:
draw a diagram of the assembled apparatus you would use when
heating the reaction mixture;
give a full description of the procedures, including the capacities
of the apparatus involved, you would use to prepare and purify
the salicylic acid;
explain how you would minimise a potential safety hazard.

1150 trendyline
4
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1151 trendyline
5

[9]
[Total: 12]

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6
2 Sodium azide is a chemical found in car safety airbags. When the car
undergoes a head-on collision, a series of chemical reactions occur in the gas
generator chamber. The first reaction produces nitrogen gas to fill the airbag.
The equation for the reaction is shown below:
3
NaN 3 (s) Na(s) + N 2 (g) H< 0
2
(a) The volume of a fully inflated airbag is 60 dm3.

Calculate the mass of NaN 3 needed to fill such an airbag to an internal
pressure of 150 kPa at 300 C.
[2]
(b) (i) Given that S r = S(products) S(reactants) and the following

information, calculate S for the above reaction.
Molar entropy of NaN 3 (s) 70.5 J mol1 K1
Molar entropy of Na(s) 51.3 J mol1 K1
Molar entropy of N 2 (g) 191.6 J mol1 K1
[1]
(ii) Explain why the reaction is feasible at all temperatures.
trendyline

[1]

1153 trendyline
7
(iii) Suggest why the reaction in fact occurs only at temperatures
above 300 C.

[1]
(c) Sodium metal formed in the above reaction is very reactive and is made
to react with potassium nitrate present in the airbag, forming sodium
oxide as one of the products.
(i) Explain what is meant by the lattice energy of sodium oxide.

[1]
(ii) Using the information given below and relevant information from
the Data Booklet, construct an energy level diagram to calculate
the lattice energy of sodium oxide.
Enthalpy change of formation of sodium oxide = 416 kJ mol1
Enthalpy change of atomisation of sodium = +107 kJ mol1
Sum of 1st and 2nd electron affinity of oxygen = +702 kJ mol1
trendyline [3]

1154 trendyline
8
(iii) Given that the 1st electron affinity of oxygen is 142 kJ mol1,
calculate the 2nd electron affinity of oxygen and explain the
significance of its sign.

[2]
(d) A working airbag should become fully inflated within 0.04 s of the initial
collision. At this point, it is actually unsafe for the drivers body to hit the
inflated airbag due to the high internal pressure (150 kPa). The airbag is
hence designed to deflate immediately such that by the time the drivers
body hit the airbag, usually 2 s after the initial collision, the internal
pressure of the airbag would have dropped to 101 kPa, providing a
softer cushioning for the driver.
An airbag at a safety test has a depressurisation rate of 23 kPa s1.
Explain if this airbag is safe for use, showing relevant calculations.
...
[2]
[Total: 13]
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1155 trendyline
9
BLANK PAGE
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1156 trendyline
10
3 (a) What do you understand by the term standard electrode potential?

[2]
(b) The following cell was set up between a copper electrode and an
unknown metal electrode M2+(aq)/M(s). The standard cell potential was
found to be 0.76V, and the copper foil was connected to the positive
end of the voltmeter.
Direction of electron flow
salt bridge
1 mol dm3 M2+ 1 mol dm3

CuSO4
Unknown metal Copper foil
wire, M
(i) Use the Data Booklet to calculate the standard electrode potential
of the M2+(aq)/M(s) system.

[1]
trendyline
(ii)) Draw an arrow in the box
b above
ve to show the direction
direc of electron
voltmeter.
flow through the voltmeter [1]

1157 trendyline
11
(iii) Predict the outcomes of the following situations. Describe what
you will see and write ionic equations, with state symbols, for any
reactions that occur.
I A rod of metal M is dipped into a solution of 1 mol dm3 CuSO 4 .
[2]
II Dilute sulfuric acid is added into a beaker containing a powdered

sample of metal M.

[2]
[Total: 8]

1158 trendyline
12
4 The four most abundant salts in sea-water are as follows.
Salt kg per m3
Sodium chloride 27.5
Magnesium chloride 6.75
Magnesium sulfate 5.625
Calcium sulfate 1.80
Magnesium oxide is obtained from sea-water by the following steps.

Step 1:
controlled Step 2:
sea water addition of filtrate addition of Mg(OH)2

CO3 OH Step 3: heat
MgO
The relevant numerical values of the solubility products are given below.
Salt K sp
Sodium carbonate -
Calcium carbonate 5.0 109
Magnesium carbonate 1.0 105
Magnesium hydroxide 1.5 1011
Calcium hydroxide 7.9 106
(a) Explain why the addition of carbonate ions in Step 1 is necessary and
has to be controlled.
trendyline

[2]

1159 trendyline
13
(b) Suggest why the Ksp value of sodium carbonate is not provided.

[1]
(c) Using the reaction scheme above, Barny used 1 dm3 of sea water to
extract magnesium oxide.
(i) Calculate the concentration of Mg2+ in sea water.
[2]
(ii) Barny chose a pH of 9.5 to carry out the extraction of Mg(OH) 2 .

Calculate the maximum mass of magnesium oxide that can be
obtained at pH 9.5.
You may assume that negligible volumes of CO 3 2 and OHwere
used.
[3]
(iii) Suggest how Barny can modify his experiment to improve on the
yield of MgO?
trendyline

[1]
[Total: 9]

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14
5 (a) In the periodic table, elements can exhibit either single or variable
oxidation states. One example of an element which can exhibit variable
oxidation state is manganese, Mn, while aluminium, Al is an example of
an element which cannot exhibit variable oxidation state.
(i) Draw a dot and cross diagram for aluminium chloride, AlCl 3 .
[1]
(ii) In the vapour state, the M r of aluminium chloride was found to be

267. However, when aluminium chloride is in the solid state, its
M r was found to be 133.5.
With the aid of suitable diagram, explain this behaviour exhibited
by aluminium chloride and the type of bonding involved.
trendyline

[3]

1161 trendyline
15
(b) Manganese is often found in minerals in combination with iron and is a
metal with important industrial metal alloy uses, particularly in stainless
steels. Manganese is found in various black minerals known
as pyrolusite. Pyrolusite consists mainly of manganese(IV) oxide.
Manganese(IV) oxideis the most common starting material for the
production of compounds of manganese in other oxidation states.
Manganese(IV) oxide undergoes a 2-step reaction to produce Y and Z.
Hot water
Oxidation in alkaline
/ alkaline medium
medium Brown black solid Y in a
MnO 2 MnO 4 2
I II purple solution
containingZ
(i) Define the term transition element.

[1]
(ii) Write the electronic configuration of Mn.
[1]
(iii) Explain why manganese can exhibit variable oxidation state.
[1]
(iv) The brown black solid Y contains 63.8% by mass of manganese

and 36.2% by mass oxygen.
Determine the empirical formula of Y.
trendyline [1]

1162 trendyline
16
(v) Suggest the identity of Z and state the type of reaction that
occurs at step II.
Hence, construct a balanced equation for the reaction.
[3]
(vi) With reference to your answer in (v), suggesthow bubbling

carbon dioxide gas into the hot solution of MnO 4 2 increases the
yield of Y and Z.

[2]
(c) Manganese(II) carbonate, MnCO 3 , undergoes thermal decomposition in

a similar wayto a Group II carbonate.
MnCO 3 decomposesat 200 C while CaCO 3 decomposes at 840 C.
(i) Write an equation, with state symbols, for the thermal

decomposition of MnCO 3 .
[1]
(ii) Explain why MnCO 3 decompose at a lower temperature than

CaCO 3 .

[2]

1163 trendyline
17
BLANK PAGE
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18
6 (a) 4-Amino-N-phenylbenzamide, the structure of which is drawn below, is

used in the treatment of epilepsy.
O H
H2N C N
4-amino-N-phenylbenzamide
(i) 4-Amino-N-phenylbenzamide is hydrolysed by warm aqueous

sodium hydroxide. Draw the displayed formulae of the two
hydrolysis products below.
AB [2]
(ii) Which of the two hydrolysis product A&B is a liquid?
. [1]
(iii) When the other product is carefully neutralised with an aqueous

mineral acid to pH 7, C is obtained.
Draw the structure of C.
[1]
(iv) Upon evaporation of all the solvent from the solution of C, a white
solid is obtained.
trendyline
Suggest a physical property of the solid.
. [1]


1165 trendyline
19
(b) State the reagents and conditions required for the conversion of
benzene into phenylamine in two steps. In your answer, identify the
structure of the intermediate.

[3]
(c) The following structure shows part of a protein molecule.

H H O H H O H H O
N C C N C C N C C
CH2 CH2 (CH2)4
OH CO2H NH2
(i) Using suitable diagrams, describe two interactions that the

protein fragment above can exhibit in its tertiary structure
trendyline [3]

1166 trendyline
20
(ii) In solution, amino acids exist as zwitterions. Choose one of the

amino acids that can be hydrolysed from the protein molecule
above to illustrate what is meant by this term.
[1]
(iii) Amino acids act as buffers in solution. By means of equations,

show how your chosen amino acid can act as a buffer when:
(I) dilute hydrochloric acid is added to its solution;
[1]
(II) dilute sodium hydroxide is added to its solution.
[1]
[Total: 14]

Pape

1167 trendyline
CANDIDATE
NAME
CLASS 6
CENTRE INDEX
NUMBER S NUMBER
Paper 2Structured Questions 13 September 2016
2 hours

A Data Booklet is provided. Do NOT write anything on it.
The number of marks is given in brackets [] at the end of each question or part question.
For Examiners Use

Paper 2
Question Total
1 2 3 4 5 6
Number (Paper 2)
Marks
12 13 8 9 16 14 72
trre
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reen
ndylin
in
ine
ne
Paper 1 Paper 3
Pape Total
tal
40 80 192

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2
1 (a) (i)
[1]
(ii) 10
Amount of salicylic acid in 10 g = = 0.0725 mol
138
0.0725
Theoretical amount of salicylic acid = 100 = 0.121 mol
60
Amount of methyl salicylate required = 0.121 mol
Mass of methyl salicylate required = 0.121 152 = 18.4 g
18.4
Volume of methyl salicylate required = = 15.7 cm3
1.174
Amount of sodium hydroxide required = 0.121 2 = 0.242 mol
0.242
Volume of sodium hydroxide required = 1000
6 .0
[2]
= 40.3 cm3
(b)
Water out
(Liebig)
condenser
Water in
(100 cm3) round bottom

flask containing reaction
mixture
Heating mantle
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y
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3
1. Using a 25 cm3 measuring cylinder, measure 16 cm3 (accept up

to 20 cm3) of methyl salicylate and place it in a 100 cm3 round
bottom flask.
2. Using a 50 cm3 measuring cylinder, measure 41 cm3 (accept up
to 50 cm3) of aqueous sodium hydroxide and place it into the
100 cm3 round bottom flask. Add some boiling chips to the
mixture.
3. Set up the reflux set-up shown in the above diagram and heat
the mixture for 30 minutes.
4. Allow the reaction mixture to cool down to room temperature
and remove the boiling chips.
5. Place the round bottom flask in an ice bath.
6. Add concentrated hydrochloric acid to the reaction mixture
slowly, with stirring.
7. Test the acidity of the mixture with a blue litmus paper.
8. Filter the mixture and wash the residue (crude salicylic acid)
with a small amount of cold water.
9. Transfer the crude salicylic acid to a clean 100 cm3 conical
flask. Add a small volume of water and heat the mixture until all
the crude product dissolves.
10. Filter the hot solution, using a fluted filter paper, into a pre-
warmed clean and dry conical flask. Allow the solution to cool
down slowly for crystals to form.
11. When the solution is cooled to room temperature, submerge the
conical flask into an ice bathto allow more crystals to form.
12. Filter the mixture to obtain the pure salicylic acid crystals
and pat dry the crystals using filter paper.
[9]
[Total: 12]
2 (a) pV = nRT
(150 103)(60 103) = n(8.31)(300 + 273)
Amount of nitrogen gas = 1.89 mol
1.89
Amount of sodium azide = = 1.26 mol
3/2
Mass of sodium azide = 1.26 65.0 = 81.9 g [2]
(b) (i) 3
S = (51.3 + 191.6) 70.5 = +268.2 J mol1 K1
2 [1]
trendyline
yline
y
(ii)
i) H
H iss negative, S is positive, TS
TS
S iss negative.
negative.
Since
G
G = H
H T S
S,
TS, G
G is always negative regardless of
temperature
temperature. [1]

1170 trendyline
4
(iii) The activation energy of the reaction is very high. [1]
(c) (i) Lattice energy of sodium oxide is the enthalpy change

when one mole of solid sodium oxide is formed from
its constituent gaseous ions Na+ and O2. [1]
(ii)
Energy / kJ mol1
2Na+(g) + O2(g)
+702
2Na+(g) + 2e + O(g)
2(+494)
2Na(g) + O(g) LE (Na2O)
2(+107) +
(+496)
2Na(s) + O2(g)
0
416
Na2O(s)
LE (Na 2 O) = 416 2(+107) (+496) 2(+494) (+702)

= 2568 kJ mol1
[3]
(iii) 2nd electron affinity = +702 (142) = +844 kJ mol1

The positive sign of 2nd EA means that energy is required
to overcome the repulsion between the anion and the electron
to be added since both are negatively charged. [2]
(d) (150 101)

Safe depressurisation rate = = 25 kPa s1
2 0.04
Since the airbag being tested depressurises more slowly than the safe
depressurisation rate, it is not safe for use. [2]
[Total: 13]
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1171 trendyline
5
3 (a) What do you understand by the term standard electrode potential?

Standard electrode potential, E , of an electrode is the relative
potential of this electrode under standard conditionscompared with the
standard hydrogen electrode whose electrode potential is assigned as
0 V. The standard hydrogen electrode consists of H 2 (g) at 1 atm
bubbling over platinum electrode coated with finely divided platinum
which is dipped into 1 mol dm3 H+(aq) at 298 K. [2]
(b) The following cell was set up between a copper electrode and an
unknown metal electrode M2+(aq)/M(s). The standard cell potential was
found to be 0.76V, and the copper foil was connected to the positive
end of the voltmeter.
Direction of electron flow
salt bridge
1 mol dm M
3 2+
1 mol dm
3
CuSO4
Unknown metal
Copper foil
wire, M
(i) Use the Data Booklet to calculate the standard electrode

potential of the M2+(aq)/M(s) system.
Since copper is the positive electrode of the galvanic cell, it is

the cathode.
Standard electrode potential of the M2+(aq)/M(s)
= 0.34 0.76= 0.42V [1]
(ii) Draw an arrow in the box above to show the direction of electron
flow through the voltmeter.
[1]
trrendyline
(iii)
i)) Predict the outcomes of the following
followi situations. Describe what
you will see and write ionic equations,
equations, with state symbols, for
any reactions that occu
occur.

1172 trendyline
6
I A rod of metal M is dipped into a solution of 1 mol dm3 CuSO 4 .
Metal M dissolves in (blue) solution and pink solid of Cu is

formed. (Blue solution lightens in colour.)
M(s) + Cu2+(aq) Cu(s) + M2+(aq) [2]
II Dilute sulfuric acid is added into a beaker containing a

powdered sample of metal M.
Efferversence is observed; colourless odourless gas evolved

that extinguishes a lighted splint with a pop sound. Metal M
dissolves in (colourless) solution.
2H+(aq) + M(s) M2+(aq) + H 2 (g) [2]
[Total: 8]
4 The four most abundant salts in sea-water are as follows.
Salt kg per m3
Sodium chloride 27.5
Magnesium chloride 6.75
Magnesium sulfate 5.625
Calcium sulfate 1.80
Magnesium oxide is obtained from sea-water by the following steps.
Step 1: Step 2:
sea water filtrate addition of Mg(OH)2
controlled

addition of OH Step 3:

CO3 heat
MgO
The relevant numerical values of the solubility products are given below.
trendyline
y
1173 trendyline
7
Salt K sp
Sodium carbonate -
Calcium carbonate 5.0 109
Magnesium carbonate 1.0 105
Magnesium hydroxide 1.5 1011
Calcium hydroxide 7.9 106
(a) Explain why the addition of carbonate ions in Step 1 is necessary and
has to be controlled.
Both calcium carbonate and magnesium carbonate are sparingly

soluble salts. Carbonate ions are added to precipitate out calcium
carbonate first.
In Step 1, the addition of carbonate must be controlled such
that little/no magnesium carbonate is precipitated/magnesium ions
remain in the filtrate. [2]
(b) Suggest why the Ksp value of sodium carbonate is not provided.
Sodium carbonate is not a sparingly soluble salt/it is very solublein

water. [1]
(c) Using the reaction scheme above, Barny used 1 dm3 of sea water to
extract magnesium oxide.
(i) Calculate the concentration of Mg2+in sea water.
In 1 dm3 of sea water,

6.7510 3
Amount of MgCl 2 = (24.3 + 35.5 2)
10 3
= 7.08 102 mol
5.62510 3
Amount of MgSO 4 = (24.3 + 32.1 + 16.0 4)
10 3
= 4.67 102 mol
[Mg2+] = 0.118 mol dm3
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y [2]

1174 trendyline
8
(ii) Barny chose a pH of 9.5 to carry out the extraction of Mg(OH) 2 .

Calculate the maximum mass of magnesium oxide that can be
obtained at pH 9.5.
You may assume that negligible volumes of CO 3 and OH
were used.
At pH 9.5, [OH] =104.5 mol dm3

K sp = [Mg2+][OH]2
Max [Mg2+] after addition of OH(aq) = 1.5 1011 (104.5)2
= 0.0150mol dm3
Amount of Mg2+ precipitated = 0.118 0.0150 = 0.103 mol
Maximum mass of MgO = 0.103 (24.3 + 16.0) = 4.13 g
(or 4.15 g) [3]
(iii) Suggest how Barny can modify his experiment to improve on the
yield of MgO?
He can use a higher pH to lower the concentration of Mg2+(aq)

to increase his yield/He can lower the temperature to lower the
K sp / He can add NaOH(aq) directly to sea water in a controlled
manner. [1]
[Total: 9]
5 (a) In the periodic table, elements can exhibit either single or variable oxidation
states. One example of an element which can exhibit variable oxidation
state is manganese, Mn, while aluminium, Al is an example of an element
which cannot exhibit variable oxidation state.
(i) Draw a dot and cross diagram for aluminium chloride, AlCl 3 .

Cl

Al Cl
Cl

[1]
(ii) In the vapour state, the M r of aluminium chloride was found to be

267. However, when aluminium chloride is in the solid state, its M r
was found to be 133.5.
ttrendyline
y behaviour exhibited by
With the aid of suitable diagram, explain this behav
involved.
aluminium chloride and the type of bonding involved

1175 trendyline
9
Aluminium chloride molecules can form dimers (between

themselves) where one aluminium chloride molecule forms dative
covalent bonds with another Aluminium chloride molecule. Hence,
the observed M r of the dimer is 267 at vapour state.
Dative bond is formed. The lone pair on the Cl atom of AlCl 3 is

donated to the empty orbital of the electron-deficient Al in AlCl 3 to
form a dative (covalent) bond so that Al can attain a stable octet
configuration. [3]
(b) Manganese is often found in minerals in combination with iron. Manganese

is a metal with important industrial metal alloy uses, particularly in stainless
steels. Manganese is found in various black minerals known
as pyrolusite.Pyrolusite consists mainly of manganese(IV) oxide.
Manganese(IV) oxide is the most common starting material for the
production of compounds of manganese in other oxidation states.
Manganese(IV) oxide undergoes a 2-step reaction to produce Y and Z.
Hot water
Oxidation in alkaline
/ alkaline medium
medium Brown black solid Y in a
MnO 2 MnO 4 2 purple solution
I II
containingZ
(i) Define the termtransition element.
A transition element is a d-block element which forms at least one

stable simple ion in which there is a partially-filled d subshell. [1]
(ii) Write the electronic configuration of Mn.
Mn : 1s2 2s2 2p6 3s2 3p6 3d5 4s2 [1]
(iii) Explain why manganese can exhibit variable oxidation state.
3d and 4s electrons are of similar energies, hence a variable

number of 3d and 4s electrons can be involved in bonding (ionic or
covalent).
t
trendyline
y [1]

1176 trendyline
10
(iv) The brown black solid Y contains 63.8% by mass of manganese and
36.2% by mass oxygen.
Determine the empirical formula of Y.
element Mn O
mass ratio 63.8 36.2
63.8 36.2
mole ratio = 1.16 = 2.26
54.9 16.0
1.16 2.26
simplest ratio = 1.00 = 1.94
1.16 1.16
1 2
Empirical formula: MnO 2 .

[1]
(v) Suggest the identity of Z and state the type of reaction that occurs at
step II.
Hence, construct a balanced equation for the reaction.
Zis MnO 4
Step IIis a disproportionation/redoxreaction.
3MnO42+ 2H2O 2MnO4+ MnO2 + 4OH [3]
(vi) With reference to your answer in (v), suggest how bubbling carbon
dioxide gas into the hot solution of MnO 4 2increases the yield of Y
and Z.
CO 2 is acidic in nature. It can remove the OH.

Equilibrium position of 3MnO42+ 2H2O 2MnO4+ MnO2 +
4OHshifts to the right to replenish the OH, hence it helps in the
disproportionation. [2]
(c) Manganese(II) carbonate, MnCO 3 , undergoes thermal decomposition in a

similar way to a Group II carbonate.
MnCO 3 decomposes at 200 C while CaCO 3 decomposes at 840 C.
(i) Write an equation, with state symbols, for the thermal decomposition
of MnCO 3 .
MnCO 3 (s) MnO(s) + CO 2 (g)
ttrendyline
e dy
d li e
[1]
(ii) Explain why MnCO 3 decompose at a lower te

temperature than
CaCO 3 .

1177 trendyline
11
The ionic radius of Mn2+ is smaller, hence Mn2+ has a higher charge
density than Ca2+.
As a result, the ability of Mn2+ to polarise the large CO 3 2anion is
greater and the CO bonds are weakened to a larger extent. Hence
MnCO 3 decomposes at a lower temperature than CaCO 3. [2]
[Total: 16]
6 (a) 4-Amino-N-phenylbenzamide, the structure of which is drawn below, is

used in the treatment of epilepsy.
O H
H2N C N
4-amino-N-phenylbenzamide
(i) 4-Amino-N-phenylbenzamide is hydrolysed by warm aqueous [2]

sodium hydroxide. Draw the displayed formulae of the two
hydrolysis products below.
H O H
N C
H
-
O Na
+ N
AB
(ii) Which of the two hydrolysis product A&B is a liquid? [1]
(iii) When the other product is carefully neutralised with an aqueous [1]
mineral acid to pH 7, C is obtained.
Draw the structure of C.
ttrendyline
re
en
nd
nddyy
H
+
H N C
-
H O

1178 trendyline
12
(iv) Upon evaporation of all the solvent from the solution of C, a white [1]
solid is obtained.
Suggest a physical property of the solid.
High melting and boiling point / conduct electricity in molten or

aqueous state
(b) State the reagents and conditions required for the conversion of benzene [3]
into phenylamine in two steps. In your answer, identify the structure of the
intermediate.
Step 1: concentrated H 2 SO 4 , concentrated HNO 3 , 55C

Step 2: Sn, Concentrated HCl, heat, followed by NaOH(aq)
Intermediate: nitrobenzene
(c) The following structure shows part of a protein molecule.

H H O H H O H H O
N C C N C C N C C
CH2 CH2 (CH2)4
OH CO2H NH2
(i) Using suitable diagrams, describe two interactions that the protein [3]
fragment above can exhibit in its tertiary structure
Hydrogen bonding between serine and aspartic acid/serine and

lysine (reject aspartic acid and lysine)
Ionic interactions between aspartic acid and lysine
+
CH2COO H3N (CH2)4
(asp) (lys)
ionic interactions
E.g. of hydrogen bonding

(CH2)4 N H O CH2
H
H

(Lys) (Ser)
ttrendyline
hydrogen bonding

1179 trendyline
13
(ii) In solution, amino acids exist as zwitterions. Choose one of the [1]
amino acids that can be hydrolysed from the protein molecule above
to illustrate what is meant by this term.
H H H
- + - -
+
+
H3N C CO2 H3N C CO2 H3N C CO2
CH2 CH2 (CH2)4
OH CO2H NH2
OR OR [1]
(iii) Amino acids act as buffers in solution. By means of equations, show [2]
how your chosen amino acid can act as a buffer when
(I) dilute hydrochloric acid
(II) dilute sodium hydroxide
is added to its solution.
H H
+ - +
H3N C CO2 H3N C CO2H
CH2 CH2
I OH + H+ OH
H H
+ - -
H3N C CO2 H2N C CO2
CH2 CH2
II OH + OH OH + H2O
[Total: 14]
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1180 trendyline
RIVER VALLEYHIGH SCHOOL
YEAR 6 PRELIMINARY EXAMINATION II
CANDIDATE
NAME
CLASS 6
CENTRE INDEX
NUMBER S NUMBER
2 hours

Cover Page
Data Booklet

A Data Booklet is provided. Do not write anything on it.
At the end of the examination, fasten all your work securely together, with the cover page on
top.
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This
his document consists of
o 10 printed pages
page and 2 blank
ank pages.
page

1181 trendyline
2
1 Many compounds of chlorine are manufactured from brine, NaCl(aq). The

electrolysis of brine produces Cl 2 (g)and NaOH(aq). In some industrial
electrolytic cells, these two substances are allowed to react further. The
products formed in this second reaction dependp on the operating conditions
used.
(a) Write balanced equations for the reaction between Cl 2 (g) and
(i) cold aqueous NaOH; [1]
(ii) hot aqueous NaOH. [1]
(b) Chlorine dioxide, ClO 2 , is used in the treatment of water. It is formed from
ClO 3 ions in an acidic solution.
ClO 3 + 2H+ + e ClO 2 + H 2 O
(i) Draw the dot-and-cross diagrams of ClO 2 and H 2 O 2 .

You may assume that there is no dative bond in either compound. [2]
(ii) Construct the overall equation for the reaction of ClO 3 ions with
H 2 O 2 in acidic solution. [1]
(iii) What is the role of H 2 O 2 in the reaction? [1]
(c) Chlorine can also be used to disinfect water. When chlorine is added to
water, it produceshypochlorous acid, HOCl. Hypochlorous acid is a weak
acid that dissociates into hypochlorite ions, OCl, according to the
following equation.
HOCl(aq) H+(aq) + OCl(aq)
Free chlorine refers to the total chlorine content in HOCl and OCl. The
dissociation curve below illustrates the ratio of hypochlorous acid to
hypochlorite at different pH values.
H
O
O
C
Cl
l
t
[Source: www.hach.com]
1182 trendyline
3
(i) Determine the pK a of hypochlorous acid. [1]
(ii) Hence, calculate the pH of a 0.0025 moldm3hypochlorous acid

solution. [2]
To determine whether the free chlorine in a sample of tap water meets the
regulatory limit (4mg Clper litre), OCl is quantitatively reduced to Cl by I
ions, which is in turn oxidised to I 2 . The I 2 is titrated with standard sodium
thiosulfate. The following reaction takes place during the titration.
I 2 + 2S 2 O 3 I + S 4 O 6
(iii) Construct a balanced equation between OCl(aq) and acidified

KI(aq). [1]
(iv) When 2 dm3 of tap water was tested, 6.0 cm3 of 0.00455mol dm3
sodium thiosulfate was required to discharge the colour of iodine.
Calculate the concentration of OCl in the sample of water. [2]
(v) Suggest why the calculated concentration of OClhas the same

value as the concentration of free chlorine. [2]
(vi) Determine if the sample of tap water is safe for consumption. [2]
(d) Chlorine is also used in organic chemistry to produce the Lewis acid
catalyst, FeCl 3 ,for the reaction between methylbenzene and chlorine.
(i) Describe the mechanism of the above reaction. [3]
(ii) FeCl 3 reacts in a similar way with acyl chlorides. Predict the
structure of the product of the following reaction.
O
Cl
FeCl 3
C9H8O
[1]
[Total: 20]
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1183 trendyline
4
2 (a) Nitrous oxide or dinitrogen oxide, N 2 O, is commonly known as "laughing

gas" due to the euphoric effects of inhaling it.It is used in surgery and
dentistry for its anesthetic and analgesic effects. To produce N 2 O,
ammonium nitrate is decomposed at 170 C. Water is a by-product of this
reaction.
(i) Write an equation for the production of dinitrogen oxide from

ammonium nitrate. [1]
(ii) In the manufacturing of N 2 O gas, 1kg of N 2 O gas is produced for

every 2.1kg of ammonium nitrate used. Determine the percentage
yield of dinitrogen oxide. [2]
(b) At 1200K, in the presence of gold wire, dinitrogen oxide decomposes as

shown:
2N 2 O(g) 2N 2 (g) + O 2 (g).
To follow the rate of reaction, the change in concentration of a sample of
N 2 O is measure against time. The results are shown below:
Time, t / s Concentration of N 2 O / 103moldm3
0 2.50
1000 2.01
2000 1.62
3000 1.31
4000 1.05
5000 0.85
6000 0.68
7000 0.55
(i) What do you understand by the term half-life of N 2 O? [1]
(ii) Plot the above data on a graph paper.

Use the following scale:
2 cm to represent 1000 s on the x-axis; and
trendyline
2 cm to represent
nt to represen 25 103m
0.25
represent 0. moldm3 on the
y-axis.
y-axis. [2]
(iii) From your graph, deduce the order of the reaction

reactio with respect
toN 2 O. [2]

1184 trendyline
5
(iv) Calculate the rate constant for the reaction and state its units. [2]
(v) The gold wire acts as a heterogeneous catalyst in this reaction.
Explain the terms in italics and outline the mode of action of the
catalyst. [3]
(c) Alkenes react withcarbenes R 2 C: to yieldcyclopropanes.

One way to generate a substituted carbene is by reacting chloroform,
CHCl 3 , with a strong base.
The mechanism to generate a carbeneis described below.
1. Potassium hydroxide, KOH, removes the proton from CHCl 3 , leaving
behind the electron pair. An anionic intermediate is formed.
2. Cl is lost and a neutral dichlorocarbene is formed.
(i) Based on the description above, draw a mechanism to show the

generation of dichlorocarbene.
Show relevant lone pairs and use curly arrows to indicate the
movement of electron pairs. [3]
An example of a reaction between an alkene and a carbene is as shown:

Cl Cl
CH3CH2 H
C C
+ CHCl + KOH H H
3 + KCl + H O
2
C C C
H CH3 CH3CH2 CH3
(ii) Suggest the structure of the productformed when cyclohexene

reacts with chloroform in the presence of KOH. [1]
(iii) Suggest the role of carbene in its reaction with an alkene. Explain
your answer. [2]
(iv) Suggest the type of reaction when carbene reacts with an alkene. [1]
[Total: 20]
3
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Copper is a rare element, constituting only 6.8 103 percent of the Earths
1185 trendyline
6
crust by mass. However, it has a wide range of uses such as in alloys,

plumbing and in electrical cables. The common oxidation states of copper are
+2 and +1.
(a) Copper can be obtained by roasting a copper ore, CuFeS 2 , to give Cu 2 S,

which is further oxidised to form metallic copper. This impure copper can
be purified by electrolysis.
(i) Draw a diagram to illustrate the electrolytic cell used in the

purification of copper, using CuSO 4 (aq) as the electrolyte. [2]
(ii) If a current of 0.8 A was passed through the cell, calculate the time
required for 0.25 g of pure copper to be collected. [2]
(b) Anhydrous copper(II) sulfate, CuSO 4 (s), is a white powder. It dissolves in

water to form a pale blue solution.
(i) State the species responsible for the pale blue colour of the
solution. [1]
(ii) Explain why the solution is pale blue in colour. [3]
(iii) Describe the colour changes observed when the following solutions
are added to the pale blue solution, giving the formulae of all
relevant species.
I.Dilute NH 3 (aq), until in excess;
II.KI(aq). [4]
(c) When Na 2 CO 3 is added to a solution of CuSO 4 and the resultant mixture

is filtered, a green solid, cupric carbonate, is obtained. The formula of this
solid is Cu 2 (OH) a (CO 3 ) b .
0.10 mol of Cu 2 (OH) a (CO 3 ) b required 0.40 mol of hydrochloric acid for
complete reaction. The products of this reaction include copper(II)
chloride, carbon dioxide and water.
(i) Given that 2.4 dm3 of CO 2 was formed at room temperature and
pressure, determine the values of a and b. [2]
(ii) Hence, write an equationfor the reaction of cupric carbonate with

(d)
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Cu 2 O, a brick red solid, is a compound where copper is in the oxidation
1186 trendyline
7
state of +1. It can be formed by reacting an alkaline solution of complexed

Cu2+ with a particular organic functional group.
(i) State the functional group that will produce Cu 2 O with the alkaline
solution of complexed Cu2+. [1]
(ii) Name the type of reaction undergone by the functional group in (i). [1]
(e) Organocopper compounds are useful reagents in organic synthesis. One

such class of compounds is the Gilman reagents, with the general formula
R 2 CuLi, where R represents an alkyl group.
Gilman reagents are effective nucleophiles used in conjugate addition
reactions. Conjugate addition involves theaddition of a nucleophile across
a C=C bond instead of across aC=O bond. This is illustrated in the
example below:
.
O 1 R2CuLi, ether O
.
2 HCl
+ RCu + LiCl
R
The Gilman reagent can be seen as providing the R nucleophile while a

mineral acid (e.g. HCl) provides the proton that is added to one of the
carbon atoms in the C=C bond.
The following synthesis involves a Gilman reagent for one of the steps:
OH O
.
1 (CH3CH2)2CuLi, ether
. NaBH4
2 HCl
A B
I II III
Suggest the reagent and conditions for Step I and the structures of
compounds A and B. [3]
[Total: 20]
4 (a) Copper(I)
per(II) chloride is used as a precursor of a fungicide and
per( an a catalyst for
a variety
riety of organic reactions.
reactions It is sparingly
sp water.
soluble in water

1187 trendyline
8
(i) Define the standard enthalpy change of hydration of an ion. [1]
(ii) Using the data given in the following table, draw an appropriate
energy cycle and calculate the standard enthalpy change of
solution for copper(I) chloride.
H hyd (Cu+) 593 kJ mol1
H hyd (Cl) 378 kJ mol1
Lattice Energy of CuCl 979 kJ mol1 [3]
(b) (i) Explain what is meant by the term entropy of a chemical system. [1]
Describe and explain how the entropy of the following systems will change
during the stated process. Assume the pressure of each system remains
at 1 atm throughout.
(ii) 1 mol of Cl 2 (g) at 298 K is heated to 500 K. [1]
(iii) 1 mol of Cl 2 (g) at 298 K is reacted with copper according to the

following equation.
Cu(s) + Cl 2 J&X&l 2 (s) [1]
(c) Copper(II) ions are pollutants found in water. One method of purification is
via precipitation of Cu(OH) 2 and CuS.
K sp (298K)
CuS 6.3 1036
Cu(OH) 2 2.0 1019
Using the above data, calculate:
(i) the minimum concentration of Cu2+ for a precipitate of CuS to form

in 10 ppm S2 solution;
(1 ppm = 1 mg dm3) [2]
(ii) the maximum pH of a solution containing 0.100 moldm3 Cu2+ ions. [3]
trendyline
(d) Manyy organic compounds also contain chlo
chlorine. An exam
example would be
1,2-dichlorocyclohexane,
dichlorocyclohexane,, which exhibits both geometrica
dichlorocyclohexane geometrical and optical
isomerism.
merism.
erism
(i) Explain why 1,2-dichlorocyclohexane

cyc can exhibit
exhib geometrical
isomerism. [1]

1188 trendyline
9
(ii) The effect of plane polarised light on 1,2-dichlorocyclohexane was

investigated. Three different types of 1,2-dichlorocyclohexane was
identified:
Molecule X rotated plane polarised light to the left
Molecule Y rotated plane polarised light to the right
Molecule Zhad no effect on plane polarised light
Suggest an explanation for these observations. [3]
(e) Compounds C and D both have the molecular formula C 7 H 7 Cl. In an

experiment, both compounds are separately heated under reflux for some
time with aqueous sodium hydroxide. The resulting solutions are cooled
and acidified with dilute nitric acid. When aqueous silver nitrate is added
subsequently, a white precipitate is formed with C while no precipitate is
formed with D.
Suggest the structures of C and D. Explain your reasoning for each
compound. [4]
[Total: 20]
5 (a) The electrical conductivities of some Period 3 elements are shown below.
ttrendyline
ren
ndyline
ndy li e
Element
Electrical
conductivity
at 298 K /
Na
a
2.1
Mg
2.3
3
All
A
3
3.5
P
Non-
Non
S
Non-conductors
-cond
Cl

1189 trendyline
10
107 S m1
(i) With reference to the data above, describe and explain the
difference in electrical conductivities of the elements above. [3]
(ii) Silicon carbide (SiC), also known as carborundum and moissanite,

is used in abrasive and cutting tools.
Suggest the structure and bonding of SiC. [2]
(b) Chlorides of Period 3 elements dissolve in water to give solutions of

varying pH.
Explain the following pH values and write the chemical equations for any
reactions that occur:
(i) AlCl 3 dissolves readily in water to form an acidic solution (pH = 3). [3]
(ii) SiCl 4 (l) dissolves in water to form a strongly acidic solution (pH =
[2]
2).
(c) Caffeic acid is an organic compound found in all plants as it is a key

intermediate in the biosynthesis of lignin, one of the principal components
of plant biomass.
Caffeic acid has the molecular formula C 9 H 8 O 4 . Caffeic acid reacts with
Br 2 (l) to give C 9 H 8 O 4 Br 2 . When treated with hot KMnO 4 and H 2 SO 4 ,
caffeic acid reacts to give F, C 7 H 6 O 4 , and a colourless gas that produces
a white solid with Ca(OH) 2 (aq). F reacts with PCl 5 to give G, C 7 H 5 O 3 Cl,
with the production of steamy white fumes. G reacts with water to form an
acidic solution. When added to neutral FeCl 3 (aq), G also forms a violet
colouration. G reacts with Br 2 (aq) to give H, C 7 H 3 O 4 Br 3 .
Use the information above to deduce the structuresof caffeic acid and
compounds F to H, explaining all the reactions involved. [10]
[Total: 20]
End of Paper
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PAG

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11
BLANK PAGE

1191 trendyline
RIVER VALLEYHIGH SCHOOL
YEAR 6 PRELIMINARY EXAMINATION II
CANDIDATE
NAME
CLASS 6
CENTRE INDEX
NUMBER S NUMBER
2 hours

Cover Page
Data Booklet

A Data Booklet is provided. Do not write anything on it.
At the end of the examination, fasten all your work securely together, with the cover page on
top.
trendyline
1192 trendyline
2
1 Many compounds of chlorine are manufactured from brine, NaCl(aq). The

electrolysis of brine produces Cl 2 (g)and NaOH(aq). In some industrial
electrolytic cells, these two substances are allowed to react further. The
products formed in this second reaction depends on the operating conditions
used.
(a) Write balanced equations for the reaction between Cl 2 (g) and
(i) cold aqueous NaOH; [1]
Cl 2 + 2NaOH NaCl + NaClO + H 2 O
(ii) hot aqueous NaOH. [1]
3Cl 2 + 6NaOH 5NaCl + NaClO 3 + 3H 2 O
(b) Chlorine dioxide, ClO 2 , is used in the treatment of water. It is formed from
ClO 3 ions in an acidic solution.
ClO 3 + 2H+ + e ClO 2 + H 2 O
(i) Draw the dot-and-cross diagrams of ClO 2 and H 2 O 2 .

You may assume that there is no dative bond in either compound. [2]
. .. .
xx . . x xx x
x x .
xO x Cl xO x
. xx xx .
H xO
xx
xxO x H
xx
(ii) Construct the overall equation for the reaction of ClO 3 ions with
H 2 O 2 in acidic solution. [1]
2ClO 3 + 2H+ + H 2 O 2 2ClO 2 + 2H 2 O + O 2
(iii) What is the role of H 2 O 2 in the reaction? [1]
Reducing agent
t
1193 trendyline
3
(c) Chlorine can also be used to disinfect water. When chlorine is added to
water, it produces hypochlorous acid, HOCl. Hypochlorous acid is a weak
acid that dissociates into hypochlorite ions, OCl, according to the
following equation.
HOCl(aq) H+(aq) + OCl(aq)
Free chlorine refers to the total chlorine content in HOCl and OCl. The
dissociation curve below illustrates the ratio of hypochlorous acid to
hypochlorite at different pH values.
H O
O C
Cl l
[Source: www.hach.com]
(i) Determine the pK a of hypochlorous acid [1]
pH = pK a when [HA] = [A]. From the graph, pH = 7.5 when [OCl]=

[HOCl]. Therefore, pK a is 7.4 7.6.
(ii) Hence, calculate the pH of a 0.0025 mol dm3 hypochlorous acid

solution. [2]
pK a = 7.5, K a = 107.5 = 3.16 108 mol dm3

[H+] = (3.16 108 0.0025)1/2 = 8.89 106 mol dm3
S+ OJ8.89 106) = 5.05
To determine whether the free chlorine in a sample of tap water meets the
regulatory limit (4 mg Clper litre), OCl is quantitatively reduced to Cl by
I ions, which is in turn oxidised to I2 . The I2 is titrated with standard
sodium thiosulfate. The following reaction takes place during the titration.
ttrendyline
rendyline
I 2 + 2S 2 O 3 II + S 4 O 6
(iii) Constru
Construct
onstruct
ct a balanced equation between OCl(aq) and acidified
betwee OCl
KI(aq)
( [1]
2H+(aq) + 2I(aq) + OCl DT&l (aq) + I 2 (aq) + H 2 O(l)

1194 trendyline
4
(iv) When 2 dm3 of tap water was tested, 6.0 cm3 of 0.00455 mol dm3
sodium thiosulfate was required to discharge the colour of iodine.
Calculate the concentration of OCl in the sample of water. [2]
Amount of S 2 O 3 = 2.73 105 mol

Amount of iodine produced = 1.37 105 mol
Amount of OCl present = 1.37 105mol
Concentration = 6.83 104 mol dm6
(v) Suggest why the calculated concentration of OClhas the same

value as the concentration of free chlorine. [2]
In the equilibrium, HOCl(aq) H+(aq) + OCl(aq), as OCl is

reduced by I, [OCl] decreases and the equilibrium position shifts
right to favour the formation of more OCl until all the HOCl
completely dissociates.
(vi) Determine if the sample of tap water is safe for consumption. [2]
Mass concentration of free chlorine = 6.83 106 35.5 = 0.242

mg per litre.
The tap water is safe for consumption.
(d) Chlorine is also used in organic chemistry to produce the Lewis acid
catalyst, FeCl 3 ,for the reaction between methylbenzene and chlorine.
(i) Describe the mechanism of the above reaction. [3]
FeCl 3 + Cl 2 FeCl 4 + Cl+

Cl
H Cl

FeCl 4 + HCl + FeCl
+ +
Cl slow f ast 3
ttrendyline
rendyline
(ii) FeCl 3 reacts in a similarlar way with acyl chlorides.
chloride Predict the
structure of the product of the following reaction. [1]

1195 trendyline
5
Cl
FeCl 3
C9H8O
[Total: 20]
trendyline
1196 trendyline
6
2 (a) Nitrous oxide or dinitrogen oxide, N 2 O, is commonly known as "laughing

gas" due to the euphoric effects of inhaling it.It is used in surgery and
dentistry for its anesthetic and analgesic effects. To produce N 2 O,
ammonium nitrate is decomposed at 170 C. Water is a by-product of this
reaction.
(i) Write an equation for the production of dinitrogen oxide from

ammonium nitrate. [1]
NH 4 NO 3 V H 2 O (g) + N 2 O (g)
(ii) In the manufacturing of N 2 O gas, 1kg of N 2 O gas is produced for

every 2.1kg of ammonium nitrate used. Determine the percentage
yield of dinitrogen oxide. [2]
2.1 1000
Amount of NH 4 NO 3 used = = 26.3 mol
14 2 4 16 3
Theoretical amt of N 2 O produced = 26.3 mol
Theoretical mass of N 2 O produced = 26.3 (14 2+16) = 1157g
1000
% yield = 100% = 86.4%
1157
(b) At 1200K, in the presence of gold wire, dinitrogen oxide decomposes as

shown:
2N 2 O(g) 2N 2 (g) + O 2 (g).
To follow the rate of reaction, the change in concentration of a sample of
N 2 O is measure against time. The results are shown below:
Time, t / s Concentration of N 2 O / 103 mol

dm3
0 2.50
1000 2.01
2000 1.62
3000 1.31
4000 1.05
ttrendyline
rendyline
5000 0.85
6000 0.68
.6
7000 0.55
0 55

1197 trendyline
7
(i) What do you understand by the term half-life of N 2 O? [1]
Half-life is time taken for the concentration of N 2 O to be halved.
(ii) Plot the above data on a graph paper.

Use the following scale:
2 cm to represent 1000 s on the x-axis; and
2 cm to represent to represent 0.25 103 mol dm3 on the
y-axis. [2]
3
Concentration of N2O / 103 mol
2.5
2
1.5
dm3
1
0.5
0
0 2000 4000 6000 8000
Time/s
(iii) From your graph, deduce the order of the reaction with respect to
N 2 O. [2]
When concentration decreases from 2.5 103 to 1.25 103, time

taken is 3300 s.
When concentration decreases from 1.25 103 to 0.7 103, time
taken is 3100 s. (to be shown on the graph)
Since half-life is approximately constant, the order of reaction with
respect to N 2 O is 1.
Show on graph that half time constant
(iv) Calculate the rate constant for the reaction and state its units. [2]
ln 2
Rate constant = = 2.17 x 104 s1
ttrendyline
t1 / 2
Correct
orrect answer
answe
Correct unit
units
(v) The gold wire acts as a heterogeneous catalyst in this reaction. [3]
1198 trendyline
8
Explain the terms in italics and outline the mode of action of the
catalyst.
A catalyst is a substance that provides an alternative pathway with

lower activation energy, remaining chemically unchanged at the
end of reaction. A heterogeneous catalyst is one that is in a
different phases as the reactants.
Adsorption
The gold wire provides active sites whereby N 2 O molecules may
be adsorbed.
The adsorption weakens NO bonds so that the N 2 O molecules
are more reactive.
Reaction
The N 2 O molecules on the gold surface are in close proximitand
the correct orientationso that they can readily react together.
Desorption
The products, N 2 and O 2 , formed diffuse away from the surface of

the catalystand the active sites become available again.
(c) Alkenes react with carbenes R 2 C: to yield cyclopropanes.

One way to generate a substituted carbene is by reacting chloroform,
CHCl 3 , with a strong base.
The mechanism to generate a carbene is described below.
1. Potassium hydroxide, KOH, removes the proton from CHCl 3 , leaving
behind the electron pair. An anionic intermediate is formed.
2. Cl is lost and a neutral dichlorocarbene is formed.
(i) Based on the description above, draw a mechanism to show the

generation of dichlorocarbene.
Show relevant lone pairs and use curly arrows to indicate the
movement of electron pairs. [3]
trendyline
1199 trendyline
9
HO
H
Cl C Cl KOH
Cl C Cl + H2O
Cl Cl
Cl
C + Cl
Cl
An example of a reaction between an alkene and a carbene is as shown:

Cl Cl
CH3CH2 H
C C
+ CHCl + KOH H H
+ KCl + H O
3
2
C C C
H CH3 CH3CH2 CH3
(ii) Suggest the structure of the productformed when cyclohexene

reacts with chloroform in the presence of KOH. [1]
Cl
Cl
(iii) Suggest the role of carbene in its reaction with an alkene. Explain
your answer. [2]
Carbene acts as an electrophile.

Carbon in carbene is electron deficient as it is bonded to two
ttrendyline
y
electronegative
g chlorine atoms/it has onlyy 6 valence electrons,
hence it acts as an electrophile.
electroph
(iv) Suggest the type of reaction when carbene reacts with an alkene. [1]

1200 trendyline
10
Addition
[Total: 20]
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1201 trendyline
11
3 Copper is a rare element, constituting only 6.8 103 percent of the Earths
crust by mass. However, it has a wide range of uses such as in alloys,
plumbing and in electrical cables. The common oxidation states of copper are
+2 and +1.
(a) Copper can be obtained by roasting a copper ore, CuFeS 2 , to give Cu 2 S,

which is further oxidised to form metallic copper. This impure copper can
be purified by electrolysis.
(i) Draw a diagram to illustrate the electrolytic cell used in the

purification of copper, using CuSO 4 (aq) as the electrolyte. [2]
battery connected
correctly
pure Cu
(cathode)
impure Cu
(anode)
dilute CuSO4
(ii) If a current of 0.8 A was passed through the cell, calculate the time
required for 0.25 g of pure copper to be collected. [2]
Amt of Cu = 0.25 / 63.5 = 3.94 103 mol

Cu2+(aq) + 2e &XV
Amt of e required = 2(3.94 103) = 7.88 103 mol
Quantity of charge required = nF = 7.88 103 96500 = 760 C
Time required = Q / I = 760 / 0.8 = 950 s (or 15.8 min)
(b) Anhydrous copper(II) sulfate, CuSO 4 (s), is a white powder. It dissolves in

water to form a pale blue solution.
(i) State the species responsible for the pale blue colour of the
solution. [1]
ttrendyline
rendyline
dyli
[Cu(H 2 O) 6 ]2+
(ii) Explain
xplain why the solution is pale blue in colour.
colour [3]
Cu2+
C 2
has a partially filled 3d subshell (electronic configuration
1s 2s 2p63s23p63d9). In the presence of H 2 O ligands in
2 2

1202 trendyline
12
[Cu(H 2 O) 6 ]2+, the 3d orbitals of Cu2+are split into 2 sets of orbitals

with different energies/become non-degenerate.The difference in
energies (E) between these 2 sets of non-degenerate 3d orbitals
is small and radiation from the visible region of the electromagnetic
spectrum is absorbedwhen an electron is promoted from a lower
energy d-orbital to another unfilled/partially-filled d orbital of higher
energy. The (blue)colour observed corresponds to the complement
of the (orange) lightabsorbed.
(iii) Describe the colour changes observed when the following solutions
are added to the pale blue solution, giving the formulae of all
relevant species.
I.Dilute NH 3 (aq), until in excess;
II.KI(aq). [4]
I. A (pale) blue precipitate of Cu(OH) 2 is formed, which is soluble

in excess NH 3 (aq) to form a dark blue
2+
solutionof [Cu(NH 3 ) 4 (H 2 O) 2 ] .
II. An off-white/cream precipitateof CuI(Accept: Cu 2 I 2 ) is
formed in a brown solutionof I 2 .
(c) When Na 2 CO 3 is added to a solution of CuSO 4 and the resultant mixture

is filtered, a green solid, cupric carbonate, is obtained. The formula of this
solid is Cu 2 (OH) a (CO 3 ) b .
0.10 mol of Cu 2 (OH) a (CO 3 ) b required 0.40 mol of hydrochloric acid for
complete reaction. The products of this reaction include copper(II)
chloride, carbon dioxide and water.
(i) Given that 2.4 dm3 of CO 2 was formed at room temperature and
pressure, determine the values of a and b. [2]
Cu 2 (OH) a (CO 3 ) b + (a+2b)H+ &X2+ + bCO 2 + (a+b)H 2 O

Amt of CO 2 formed = 2.4 / 24 = 0.10 mol
1 0.10
b = 1
b 0.10
ttrendyline
y
1 0.10
a+ 2b = 4 a
a = 2
a 2b 0.440
(ii) Hence, write an equationfor

Hence or the
t reaction of cupric ccarbonate with [1]

1203 trendyline
13
hydrochloric acid.
Cu 2 (OH) 2 CO 3 + 4HCl &XCl 2 + CO 2 + 3H 2 O
(d) Cu 2 O, a brick red solid, is a compound where copper is in the oxidation

state of +1. It can be formed by reacting an alkaline solution of complexed
Cu2+ with a particular organic functional group.
(i) State the functional group that will produce Cu 2 O with the alkaline
solution of complexed Cu2+. [1]
Aliphatic/Non-aromatic aldehyde
(ii) Name the type of reaction undergone by the functional group in (i). [1]
Oxidation
(e) Organocopper compounds are useful reagents in organic synthesis. One

such class of compounds is the Gilman reagents, with the general formula
R 2 CuLi, where R represents an alkyl group.
Gilman reagents are effective nucleophiles used in conjugate addition
reactions. Conjugate addition involves theaddition of a nucleophile across
a C=C bond instead of across aC=O bond. This is illustrated in the
example below:
.
O 1 R2CuLi, ether O
.
2 HCl
+ RCu + LiCl
R
The Gilman reagent can be seen as providing the R nucleophile while a

mineral acid (e.g. HCl) provides the proton that is added to one of the
carbon atoms in the C=C bond.
The following synthesis involves a Gilman reagent for one of the steps:
OH O
.
1 (CH3CH2)2CuLi, ether
. NaBH4
2 HCl
A B
I II III
trendyline
y
gest the reagent and conditions for Step I and the structures of
Suggest
compounds
pound A and B
pounds B..
Reagents and conditions for Step I:

[3]

1204 trendyline
14
acidified K 2 Cr 2 O 7 (aq), heat (under reflux)

Structures:
O OH
A B
[Total: 20]
trendyline
1205 trendyline
15
4 (a) Copper(I) chloride is used as a precursor of a fungicide and a catalyst for

a variety of organic reactions. It is sparingly soluble in water.
(i) Define the standard enthalpy change of hydration of an ion. [1]
The standard enthalpy change of hydration of an ion is the enthalpy

change when one mole of gaseous ions is hydrated under
standard conditions.
(ii) Using the data given in the following table, draw an appropriate
energy cycle and calculate the standard enthalpy change of
solution for copper(I) chloride.
H hyd (Cu+) 593 kJ mol1
H hyd (Cl) 378 kJ mol1
Lattice Energy of CuCl 979 kJ mol1 [3]
H soln (CuCl(s)) = H hyd (Cu+) + H hyd (Cl) LE(CuCl)

= (593) + (378) (979) = +8 kJ mol1
Hsoln(CuCl(s))
CuCl(s) Cu+(aq) + Cl(aq)
Hhyd(Cu+)
LE(CuCl) Hhyd(Cl)
Cu+(g) + Cl(g)
(b) (i) Explain what is meant by the term entropy of a chemical system. [1]
Entropy is a measure of the disorder in a system. (The more

disordered a system, the greater the number of ways for particles
and energy to be dispersed, therefore the larger its entropy.)
Describe and explain how the entropy of the following systems will change
during the stated process. Assume the pressure of each system remains
at 1 atm throughout.
(ii) 1 mol of Cl 2 (g) at 298 K is heated to 500 K. [1]
S> 0. There is an increase in disorder as the

Entropy increases/
ttrendyline
rendyline
rendy
d liine
particles have more kinetic energy
energ on average
averag and there
are more ways to distribute
distribu the larger number of quanta of
energy.
nergy.
(iii) 1 moll off Cl 2 (g) at 298 K is reacted with copper according

a
ac to the
ffollowing
ll i equation. ti [1]

1206 trendyline
16
Cu(s) + Cl 2 J&X&l 2 (s)
Entropy decreases/S< 0. There is an decrease in disorder as

the number of gaseous molecules decreases from 1 to 0.
(c) Copper(II) ions are pollutants found in water. One method of purification is
via precipitation of Cu(OH) 2 and CuS.
K sp (298 K)
CuS 6.3 1036
Cu(OH) 2 2.0 1019
Using the above data, calculate:
(i) the minimum concentration of Cu2+ for a precipitate of CuS to form

in 10 ppm S2 solution;
(1 ppm = 1 mg dm3) [2]
[S2] = (0.01 / 32.1) = 3.12 104 mol dm3

[Cu2+] = (6.3 1036) / (3.12 104) = 2.02 1032 mol dm3
(ii) the maximum pH of a solution containing 0.100 moldm3 Cu2+ ions. [3]
K sp (Cu(OH) 2 ) = [Cu2+][OH]2
2.0 1019 = (0.1)(x)2
[OH] = 1.41 109 mol dm3
pOH = lg(1.41 109) = 8.85

pH= 14 pOH = 14 8.85 = 5.15
(d) Many organic compounds also contain chlorine. An example would be

1,2-dichlorocyclohexane, which exhibits both geometrical and optical
isomerism.
(i) Explain why 1,2-dichlorocyclohexane can exhibit geometrical

isomerism. [1]
There is restricted rotation about the carbon-carbon bond in the

ring structure, resulting in cis- and trans-1,2-
dichlorocyclohexane[1].
ttrendylin
rendyylin
ne
e
Cll
C Cll
C Cl
Cl OR Cl Cl

1207 trendyline
17
cis isomer trans isomer
(ii) The effect of plane polarised light on 1,2-dichlorocyclohexane was

investigated. Three different types of 1,2-dichlorocyclohexane was
identified:
Molecule X rotated plane polarised light to the left
Molecule Y rotated plane polarised light to the right
Molecule Zhad no effect on plane polarised light
Suggest an explanation for these observations. [3]
Molecule Explanation
Cl
Molecules possess two
X chiral carbons and no plane
of symmetry. Hence, they
are mirror images of each
Cl
other that are non-
Cl superimposable (i.e.
enantiomers of each other)
Y Structure of X and Y can be
interchanged.
Cl
Cl
Although the molecule has

Cl OR two chiral carbons, there is a
Z plane of symmetry present.
Cl Hence, the mirror images are
superimposable.
Cl
Cl Cl
ttrendyline
X
nd
dy nne
e Cll
C
Y
Cll
C

1208 trendyline
18
(e) Compounds C and D both have the molecular formula C 7 H 7 Cl. In an

experiment, both compounds are separately heated under reflux for some
time with aqueous sodium hydroxide. The resulting solutions are cooled
and acidified with dilute nitric acid. When aqueous silver nitrate is added
subsequently, a white precipitate is formed with C while no precipitate is
formed with D.
Suggest the structures of C and D. Explain your reasoning for each
compound. [4]
C CH2Cl
C undergoes nucleophilic substitution when heated with

NaOH. Free chloride ion then combines with Ag+ to form white
precipitate of AgCl.
D Cl
Cl Cl
OR OR
CCl bond in D has partial double bond character due to

the delocalisation of a lone pair of electrons of chlorine into
the benzene ring. Hence, D does not undergo nucleophilic
substitution with NaOH.
[Total: 20]
5 (a) The electrical conductivities of some Period 3 elements are shown below.
Element Na Mg Al P S Cl
ttrendyline
ndy
d li
Electrical
conductivit
conductivity
at 298 K /
107 S m1
2.1 2.3 3
3.5 Non-
Non
Non-conductors
-cond

1209 trendyline
19
(i) With reference to the data above, describe and explain the
difference in electrical conductivities of the elements above. [3]
Na, Mg &Al
They are metals/have giant metallic structure.
Presence of delocalised valence electrons which act as mobile
charge carriers thus making them good conductors.
Electrical conductivity increases from Na (2.1 107 S m1) to Mg
(2.3 107 S m1) to Al (3.5 107 S m1)as the number of valence
electrons increases.
P 4 , S 8 &Cl 2
They are non-metals / have simple covalent structure.
Absence of mobile charge carriers thus they are non-conductors.
(ii) Silicon carbide (SiC), also known as carborundum and moissanite,

is used in abrasive and cutting tools.
Suggest the structure and bonding of SiC. [2]
Giant covalent structurewithstrong electrostatic forces of attraction

between the Si and C nuclei and the shared pair of electrons.
(b) Chlorides of Period 3 elements dissolve in water to give solutions of

varying pH.
Explain the following pH values and write the chemical equations for any
reactions that occur:
(i) AlCl 3 dissolves readily in water to form an acidic solution (pH = 3). [3]
Both hydration of ions and substantial hydrolysis of Al3+(aq) occurs.

Due to its high charge density, Al3+ is highly polarising
and weakens the OH bonds in the water molecules of the
complex, causing the OH bonds to break and hence release the
hydrogen ions.
AlCl 3 (s) + 6H 2 2O>$l(H 2 O) 6 ]3+(aq) + 3Cl(aq)
[Al(H 2 O) 6 ]3+(aq) + H 2 O(l) [Al(H 2 O) 5 (OH)]2+(aq) + H 3 O+(aq)
(ii)
ttrendyline
rendyline
d li
SiCl 4 (l) dissolves in water to form a strongly acidic solution (pH =
SiC
2))
SiCl 4 undergoes hydrolysis in water. This is becau

because Si atom in
SiCl 4 has energetically accessible vacant 3d orbital for dative
[2]
bonding with water molecules.

1210 trendyline
20
SiCl 4 (l) + 2H 2 O(l) SiO 2 (s) + 4HCl(aq)
(c) Caffeic acid is an organic compound found in all plants as it is a key

intermediate in the biosynthesis of lignin, one of the principal components
of plant biomass.
Caffeic acid has the molecular formula C 9 H 8 O 4 . Caffeic acid reacts with
Br 2 (l) to give C 9 H 8 O 4 Br 2 . When treated with hot KMnO 4 and H 2 SO 4 ,
caffeic acid reacts to give F, C 7 H 6 O 4 , and a colourless gas that produces
a white solid with Ca(OH) 2 (aq). F reacts with PCl 5 to give G, C 7 H 5 O 3 Cl,
with the production of steamy white fumes. G reacts with water to form an
acidic solution. When added to neutral FeCl 3 (aq), G also forms a violet
colouration. G reacts with Br 2 (aq) to give H, C 7 H 3 O 4 Br 3 .
Use the information above to deduce the structuresof caffeic acid and
compounds F to H, explaining all the reactions involved. [10]
Caffeic acid &+UDWLR1:1which suggests presence of benzene ring.

Caffeic acid has a C=C double bond/has an alkene group as it
undergoes electrophilic addition with Br 2 .
Caffeic acid undergoes oxidation/oxidative cleavagewith hot KMnO 4 to
give carbon dioxide gas. Loss of 2 carbons as CO 2 suggests formation
of ethanedioic acid/HO 2 CCO 2 Hafter oxidative cleavage.
F contains a carboxylic functional group as it undergoes
(nucleophilic) substitution with PCl 5 to give G, an acid chloride that
hydrolyses in water, and fumes of HCl.
G contains phenol functional group as it forms a complex with FeCl 3 (aq).
G undergoes electrophilic substitutionwith Br 2 (aq). Substitution of 3 Br
atoms suggests 3 positions on benzene ring that are available for
substitution.
Caffeic acid O
HO
OH
HO
F O
tre
endyline
end
nd yl
HO
H
OH
HO

1211 trendyline
21
G O
HO
Cl
HO
H Br O
HO
OH
HO Br
Br
[Total: 20]
End of Paper
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(1'2)3$3(5
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1
Name: Class:
ST ANDREWS JUNIOR COLLEGE
JC 2 Preliminary Exam
Chemistry 9647/02
Higher 2 31August2016
Paper 2 2 hours
Candidates answer in the spaces provided on the question paper.

For Examiners Use:
Question Marks
1
2
3
4
5
t endy
tre
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6
7
Total (72 marks)
ks)
s)
This document consists of27printed pages including this page.
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BLANK PAGE
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1 A student found a bottle of solid benzoic acid in the school laboratory. She was tasked to
determine the standard enthalpy change of neutralisation of benzoic acid. The standard
enthalpy change of neutralisation is when one mole of water is formed between an acid and
a base.
H+ (aq) + OH (aq) H 2 O (l)
You may assume you are provided with the following:

FA 1, aqueous sodium hydroxide, NaOH
Solid benzoic acid
Polystyrene (styrofoam) cups
Apparatus normally found in a school laboratory
Before carrying out the experiment, an aqueous solution of 2.00 mol dm-3 benzoic acid
(FA 2) is first prepared. Subsequently, in separate experiments, different volumes of FA 2
and FA 1 are mixed while keeping the total volume of the reaction mixture constant. In each
H[SHULPHQWWKHWHPSHUDWXUHULVH7LVWREHGHWHUPLQHG$JUDSKRI7DJDLQst volume of
FA 1 used is then plotted.
Data from the graph can then be used to determine:

the 7 max ,
the concentration of FA 1,
the enthalpy change of neutralisation between FA 1 and FA 2.
It is given that 4.18 J is required to raise the temperature of 1 cm3 of any solution by
1 oC.
(a) Write an equation to represent the standard enthalpy change of neutralisation

between sodium hydroxide and benzoic acid.
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[1]
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1 (b) (i) Write a detailed plan to prepare 2.00 mol dm-3 solution of FA 2.
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(ii) It is predicted that the maximum temperature change for the neutralisation
would occur when the volume of FA 1 mixed is between 25 cm3 and 30 cm3.The
total volume of any mixture should be kept constant at 50 cm3.
Write a detailed plan on how you could determine the temperature changes for
the series of reactions between FA 1 and FA 2.
all essential experimental details,
appropriate volumes of solutions to be used,
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a tabulation of the experimental data to be collec
collected (including volumes
used)
sed),,
used),
ow these measurements can be used to obtain the temperature change,
how
T
T.
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1 (b) (ii)
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1 (b) (iii) The following plots were plotted on a grid after another similar experiment was
conducted. Draw suitable graphs through the plotted points.
[1]
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1 (c) By using the graph in (b)(iii), calculate

the concentration of FA 1, given that the total volume of the mixture is 50 cm3.
the enthalpy change of neutralisation for the reaction between FA 1 and FA 2.
[2]
[Total: 12]
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2 (a) Chromium carbonyl, alsoknown as chromium hexacarbonyl, is a chemical compound with

the formula Cr(CO) 6 . Cr(CO) 6 is zerocovalent, meaning that Cr has an oxidation state of
0. Draw the structure of the complex and state the shape and bond angle around the Cr
atom in the complex.
[2]
(b) Chromium hexacarbonyl undergoes the following ligand replacement reaction.
Cr(CO) 6 + PR 3 Cr(CO) 5 PR 3 + CO
Two separate experiments were carried out to study the rate of this reaction.
In the first experiment, the ligand PR 3 was in a large excess and [Cr(CO) 6 ] was
measured against time. The results are shown on the graph below.
y
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2 (b) In the second experiment, Cr(CO) 6 was in a large excess, and [PR 3 ] was measured
against time. The following results were obtained.
time / s [PR 3 ] / moldm3
0 0.0100
120 0.0076
200 0.0060
360 0.0028
(i) On the graph, plot the data given in the table.

[1]
(ii) Use the graphs to determine the order of reaction with respect to Cr(CO) 6 and
PR 3 .In each case explain how you arrived at your answer.
Cr(CO) 6
PR 3
[2]
(iii) Write the rate equation for the reaction, and calculate a value for the rate constant,
stating the units of the rate constant.
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2 (b) (iv) Two possible mechanisms for this reaction are given below. State themechanism
which is consistent with the rate equation you have written in (b)(iii) and explain
your answer.
Mechanism A Cr(CO) 6 Cr(CO) 5 + CO slow

Cr(CO) 5 + PR 3 Cr(CO) 5 PR 3 fast
Mechanism B Cr(CO) 6 + PR 3 [OC- - -Cr(CO) 4 - - -PR 3 ] Cr(CO) 5 PR 3 +

CO
(transition state)
[2]
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3 This question refers to compounds of calcium and barium.
(a) Oil paints contain traces of red Ca2+ and green Ba2+ions which give them their
characteristic red and green colours respectively.Oil painting is typically done on canvas.
During the manufacturing process of canvas, hydrogen orthoperiodateions, HIO 6 4, is left
on the canvas.
Orthoperiodate salts are formed when orthoperiodate ions, IO 6 5-,reacts with the Ca2+ and
Ba2+ions in the paint, causing the decolourisation of the red and green colour of the paint.
The equations below show the formation of IO 6 5- and its salts.
HIO 6 4 (aq) H+ (aq) + IO 6 5 (aq) K a = 4.04 x 10-6mol dm-3
5 M2+ (aq) + 2 IO 6 5 (aq) M 5 (IO 6 ) 2 (s) where M2+isCa2+ or Ba2+
Relevant K sp values are given in the table below :
Salt K sp
Ca 5 (IO 6 ) 2 4.0 x 10-9
Ba 5 (IO 6 ) 2 1.6 x 10-15
The painting was stored in a display cabinet at a low pH environment.Over the weekend,
the electrical supply of the display cabinet was disrupted which resulted in an increase of
the environments pH. It was found that the green portions of the painting were
decolourised due to the formation of solid barium orthoperiodate, Ba 5 (IO 6 ) 2 .
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3 (a) Explain qualitatively why the green colouredareas of the painting were decolourised but
not the red coloured areas when the pH increased.
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3 (b) G, H and S are related by the following equation.

G = H - TS
The Ellingham diagram below shows how G changes between0K and 1800Kfor the
following reaction.
CaO (s) + H 2 O (l) Ca(OH) 2 (s)
For the range of temperatures in the graph above, it can be assumed that the enthalpy
change and the entropy change of the reaction remain approximately constant.
(i) Predict the sign of S for the reaction, showing your reasoning.
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[2]
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3 (b) (ii) Using the graph, calculate S.
[1]
(iii) Using the graph, determine H.
.
[1]
(iv) Determine the temperature above which the reaction become non-spontaneous.
.
[1]
[Total: 8]
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4 The table below gives data about some physical properties of the elements calcium, copper
and chromium.
Physical Property Calcium Copper Chromium
Relative atomic mass 40.1 63.5 52.0
Atomic radius / nm 0.197 0.128 0.117
Density/ gcm-3 1.54 8.92 7.20
First ionisation energy/ kJ mol-1 590 745 653
(a) (i) Explain why the first ionisation energy of copper and chromium are both higher
than that of calcium.
[2]
(ii) Use relevant data from the table to explain qualitatively why the densities of copper
and chromium are significantly greater than that of calcium.
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4 (b) Chromium (III) nitrate is more acidic than chromium (II) nitrate. Explain with the aid of a
relevant equation.
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[2]
(c) When a particular copper ore was reduced, an alloy was produced which was composed
mainly of copper, but with gold and chromium impurities. It contained no other metal. In
order to purify it, the alloy was made the anode of an electrolytic cell, with a pure copper
cathode and aqueous copper (II) sulfate as the electrolyte.
Explain, with reference to E values, what happens to the gold and chromium impurities
during this purification process. The electrode reaction for the standard Au3+/Au half cell
is Au3+ (aq) + 3e Au (s) E= +1.50 V
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4 (d) A current of 1.8 A was passed through the cell described in (c) for17 minutes, and the
electrodes removed, washed, dried and weighed. It was found that some mass was lost
from the anode.
After filtering it off and drying it, the deposit below the anode weighed 0.085g. On adding
an excess of hydroxide ions to the electrolyte, a grey-green precipitate was formed. Its
mass was 0.304g. (You may assume that negligible amount of copper ions remained in
the electrolyte.)
(i) Calculate the expected increase in mass of the cathode.
[2]
(ii) Identify the grey-green precipitate.
grey-green precipitate: .
[1]
(iii) It was found that the mass of copper removed from the alloy was 0.466g. Calculate
the masses of gold and chromium removed from the alloy. Hence calculate the total
mass lost by the anode.

[3]
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5 (a) A student conducted an experiment to identify the trend in thermal stability of hydrogen
halides. The reaction occurred according to the following equation:
2HX(g) H 2 (g) + X 2 (g)
The approximate K c values for the above equilibrium at 500oC is shown in the table
below.
Kc
Temperature /oC
HCl HBr HI
500 1013 109 105
(i) Using the Data Booklet, explain the trend in thermal stability of hydrogen halides
down the group.
[2]
(ii) Hence, deduce if thetrend in (a)(i) agrees with the K c data given above.
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5 (b) A student conducted another experiment to distinguish between samples of sodium

chlorideand phosphoruspentachloride. It was found that red onion water can be used as
an indicator. The table below shows the colour of the indicator at various pH.
pH Colour
Less than 7 Red

7 Violet
(i) To each unknown sample of chlorides, he added a few drops of red onion water.
He recorded the colour of the indicator. Predict the identities of the chlorides.
Colour of red onion water Identity of chloride
Red
Violet
[1]
(ii) With the aid of an equation, describe the action of water on

phosphoruspentachloride.
[2]
[Total: 6]
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6 Paracetamol is an effective analgesic discovered by Joseph von Mering in 1893. Its structure
is as shown.
HO NH
(a) Explain why all the carbon-carbon bonds in benzene are of the same length.
.......
...
[1]
(b) (i) Paracetamol may be synthesised from phenol as shown.
Step 1 Step 2 Step 3 HO NH

HO A B
State the reagents and conditions for steps 1 to 3. Draw the structure of the
intermediate product B.
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Step 1:
....
Step 2:
....
Step 3:
Structure of B
....
[4]
6 (b) (ii) Based on Step 3 of the given reaction scheme, draw the structure of a possible
side-product.
[1]
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(iii) Phenylephrine is a decongestant which may be taken with paracetamol when a

person is suffering from cold. The structure of phenylephrine is as shown.
OH
H
HO N
State and explain how the basicity of phenylephrinemight compare with that of
paracetamol.
[2]
6 (b) (iv) Suggest a simple chemical test to distinguish between paracetamol and
compound A.
CONH2
HO
Compound A
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[2]
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6 (c) (i) Hoechst and Celanese discovered a simpler synthetic route for paracetamol as
shown.
O O
OH OH OH OH
O CF3COOH,
SOCl 2,
HF catalyst NH2OH Amberlyst 15
Step 1 Step 2 N Step 3 HN O

O
OH
State the types of reaction for steps 1 and 2.
Step 1:
....
Step 2:
....
[2]
(ii) Step 3is known as the Beckmann arrangement, where an oxime is converted into
an amide.
N OH R
R O
HN
R R
Oxime Amide
N
Draw the structure of the product formed when OH undergoes the
Beckmann arrangement.
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[Total: 13]
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7 Coffee beans contain chlorogenic acid, which is an antioxidant and an important biosynthetic
intermediate. The structure of chlorogenic acid is as shown.
OH
OH
O O
OH
O
OH
HO HO
(a) State the number of moles of hot NaOH (aq) that will react with 1 mole of chlorogenic
acid.
.....
[1]
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7 (b) On heating with dilute acid, chlorogenic acid produces two compounds, X and Y.
HO O OH
OH
O
OH
OH
HO HO
OH
Compound X Compound Y
When compound Y reacts with hot excess concentrated sulfuric acid, a product with a
molecular formula of C 7 H 6 O 3 is formed. A student claims that the product formed has the
following structural formula but the teacher disagrees.
OH
HO
Draw the correct structure of the product and explain what is wrong with the students
answer.
Structure of product
.....

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7 (c) HO O
OH
OH
Compound Z
(i) Compound Z reacts with Br 2 (l) at room temperature and in the dark. Describe the
mechanism showing curly arrows, charges, dipoles and any relevant lone pairs.
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7 (c) (ii) The product of(c)(i) exists as a mixture of 4 stereoisomers. State the type of
isomerism exhibited by the product and draw all the stereoisomers.
...
[3]
[Total: 9]

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1308 trendyline
1
Name: Class:
JC2 Preliminary Examinations

Chemistry 9647/03
Paper 3 2 hours
Additional Materials: Writing paper, Data Booklet
Write your name and civics group on all the work you hand in.

This document consists of 14printed pages including this page.
trendyline [Turn over
1309 trendyline
2
1 Propenoic acid, also commonly known as acrylic acid, is used in the formation of many
polymers.
(a) Acrylic acid can be synthesised from 2-chloroethanol in the laboratory by the following
route.
NaCN
in ethanol A
HO
Cl CN CO2H
acrylic acid
(i) Suggest the structure for intermediate A. [1]

(ii) Suggest reagents and conditions for step 2 and for step 3. [2]
(iii) What type of reaction is occurring in step 2? [1]
(b) Acrylic acid is manufactured industrially from the reaction of propene and oxygen gas.
(i) Write a balanced equation for this reaction. [1]
(ii) Propenal was isolated as an intermediate product in the reaction.
Draw the structure of propenal. [1]
(c) Polyacrylate is used in environmentally-friendly detergents to remove calcium ions and

magnesium ions in water.
In the manufacture of polyacrylate, acrylic acid was first converted into acrylic chloride,
followed by reaction with an alcohol to form a monomer. Polyacrylate is formed when the
monomer undergoes polymerisation.
SOCl 2
pyridine CH3OH
CO2H COCl CO2CH3
acrylic chloride
polymerisation
H CO2CH3
C C
H H n
o acr a
p ly yl t e
trendyline
(i) e a balanced equation for the conversion of acrylic
Write ac acid into a
acrylic chloride. [1]
(ii) gest
est the type of reaction occurring in the fo
Suggest formation of the monomer
formation m from
c chloride.
acrylic [1]
(iii) gest how polyacrylate can remove
Suggest ove magnesium ions from water through
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3
complex formation. [1]
1 (d) In the kinetic studies of polymerisation, transition element-containing catalysts were used.
A copper(I)-containing catalyst is shown below.
nBu
N N
Cu
N N
nBu
Cu(I)-nBuPCA catalyst
(i) What is the co-ordination number of copper in the Cu(I)-nBuPCA catalyst? [1]
(ii) What is the electronic configuration of copper in Cu(I)-nBuPCA? [1]
(iii) Suggest whether copper in Cu(I)-nBuPCA catalyst can be classified as a
transition element. [1]
(e) Cu(I) undergoes disproportionation to form Cu and Cu(II).

(i) Use relevant data from the Data Booklet to predict the spontaneity of this
disproportionation reaction. [2]
(ii) Describe and explain what you would see when aqueous ammonia is added
slowly to an aqueous solution of copper(II) chloride, until the aqueous ammonia
is in excess. Write equations for any reactions that occur. [4]
(iii) Suggest an explanation for the difference in colour between [Cu(H 2 O) 6 ]2+ and
[CuCl 4 ]2. [2]
[Total: 20]
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4
[Turn Over
2 In a Mixed Claisen Condensation Reaction, an ester and a NHWRQHUHDFWWRIRUPD-diketone.
.
O 1 CH3CH2ONa, ethanol O O
O . +
2 H
+ + CH CH OH
3 2
OCH2CH3
-
diketone
(a) (i) 'UDZ WKH -diketone formed when 2,2-dimethylcyclohexanone reacts with
ethylethanoate in the Mixed Claisen Condensation Reaction.
O
O
CH3CH2O
2,2-dimethylcyclohexanone ethylethanoate
[1]
(ii) In not more than 3 steps, propose the synthesis of 2,2-dimethylcyclohexanone

from the following starting material.
Cl
[5]
(b) Due to the presence of two ketone IXQFWLRQDO JURXSV -diketones are a highly
valuable substrate in several organic chemistry syntheses.
One of the many examples is selective reduction, in which only one of the ketone
reduced.
O O O OH
selective reduction
- - -
4 hydroxypentan 2 one
Draw the mechanism for the reaction between 4-hydroxypentan-2-one and HCN.
[3]
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5
2 (c) -diketones exist in equilibrium with a tautomeric form, known as an enol.

This is known as keto-enol tautomerisation. The keto-enol tautomerisation of
pentan-2,4-dione is shown below.
O O O OH
H<0
-
keto enol tautomerisation
keto enol
(i) Write an expression for K c for the keto-enol tautomerisation of pentan-2,4-dione. [1]
(ii) In the case of pentan-2,4-dione, 76% of the mixture exists as an enol at room
temperature and pressure. Calculate a value for K c . [1]
(iii) Sketch a graph showing how the rates of the forward and reverse reactions
change from the time pure keto is added to the time the reaction reaches
equilibrium. Label your two lines clearly. [2]
(d) The keto-enol tautomerisation is catalysed by the presence of an inorganic base, such as
NaOH.
O O
O O
+ OH +H O
2
keto
O OH
+ OH
enol
(i) State how the presence of NaOH would affect the K c , as calculated in (c)(ii). [1]
trendyline
(ii) he
e same diagram in (c)(iii), show
On the how how the ra forwa and reverse
rates of the forward
ions change for the base catalysed keto-
reactions keto-enol tautomerisation.
keto-enol tautomerisation
Labell your lines clearly. [1]
(iii) ce, explain the effect of NaOH on the reaction.
Hence, [2]
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6
[Turn Over
2 (e) The enol form is more stable than the keto form due to two reasons
Reason I: Intramolecular hydrogen bonding
Reason II: Position of p orbitals
O OH
1 3
2
enol
(i) Draw an appropriate diagram to show how reason I contributes to the stability [1]
of the enol form.
(ii) State the hybridisation of the carbon atoms at positions 1, 2 and 3.
Hence, explain how reason II contributes to the stability of the enol form. [2]
[Total: 20]
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7
3 (a) Antiseptics and disinfectants are used to kill bacteria. The difference between
antiseptics and disinfectants is that antiseptics are used on living skin and
disinfectants are used on surfaces of objects.
Calcium hypochlorite, Ca(OCl) 2 , is often used to sanitise public swimming pools. It is
produced by treating calcium hydroxide with chlorine gas.
2Ca(OH) 2 + 2Cl 2 Ca(OCl) 2 + CaCl 2 + 2H 2 O
(i) Write an equation for the decomposition of calcium hydroxide. [1]
(ii) Deduce whether calcium hypochlorite would decompose at a higher or
lower temperature than calcium hydroxide. Explain your reasoning. [2]
(iii) In order to test the percentage purity of the calcium hypochlorite granules,
1 g of the calcium hypochlorite granules above was dissolved in water
and the solution was then reacted with excess iodide in an acidic medium.
OCl + 2H+ + 2I Cl + H 2 O+ I2
The resulting solution was then titrated with 0.500 mol dm3 sodium
thiosulfate. 22.5 cm3 of thiosulfate was required to reach the end-point.
Calculate the percentage purity of the granules. [2]
(iv) Commercially, calcium hypochlorite is available as granules. Using your
answer in (a)(iii),calculate the volume of chlorine gas (measured at room
temperature and pressure) required to manufacture 1 kg of calcium [2]
hypochlorite granules.
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8
[Turn Over
3 (b) Chloroxylenol is commonly used in antibacterial soaps due to its disinfecting
and sanitising properties. It is also responsible for the distinctive odour of
Dettol.
An isomer of chloroxylenol is compound X.
Cl
OH
CH2CH2Cl
OH
chloroxylenol compound X
When hot ethanolic silver nitrate was added to chloroxylenol and compound X
separately, the observations were different. State what you would observe for
each compound and explain the difference in observations. [3]
(c) Compounds A and B are structural isomers of chloroxylenol. Both A and Bgive
a violet colouration with neutral FeCl 3 .
A rotates plane-polarised light, but B does not.When B is treated with hot
alcoholic sodium hydroxide, a compound of molecular formula C 8 H 8 O is
formed.
When A is treated carefully with hot aqueous sodium hydroxide, compound C,
C 8 H 10 O 2 , is formed.
C reacts with hot concentrated potassium dichromate(VI) to form compound D.
C reacts with hot concentrated potassium manganate(VII) to form compound
Eand carbon dioxide gas.
D gives an orange precipitate with 2,4-dinitrophenylhydrazine, but E does not.
Suggest structures for A to E, and explain the observations described above. [10]
[Total: 20]
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9
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10
4 The table below summarises the different types of acids found in various types of beverages.
Beverage Acid Formula pK a1 pK a2 pK a3

Beer Carbonic H 2 CO 3 6.37 10.3
Fruit Juices Malic HO 2 CCH 2 CH(OH)CO 2 H 3.46 5.10
Soda Phosphoric H 3 PO 4 2.12 7.21 12.3
(a) (i) Explain why the pK a1 of malic acid is so much lower than the pK a1 of
carbonic acid. [2]
(ii) Explain why the pK a3 of phosphoric acid is so much higher than the pK a2 of
malic acid. [1]
(b) (i) 50.0 cm3 of 0.5 mol dm3 aqueous H 3 PO 3 was mixed with 30cm3 of excess
aqueous NaOH. It was found that the temperature of the solution rose by
8.4C after mixing. Calculate the enthalpy change of reaction per mole of
H 3 PO 3 (aq).
Given: Specific heat capacity of water = 4.18 J g1 K1;

Density of water = 1.0 g cm3. [2]
(ii) Hence, given that the enthalpy change of neutralisation of HCl (aq) by
1D2+DTLV kJ mol1, suggest the basicity of H 3 PO 3 .
[1]
(c) A medical student wanted to investigate the buffer solution in fluids for
intravenous injection. He needed to prepare a buffer of pH 7.2. Of the pK a values
given in the table above, suggest a conjugate acidbase pair which is most
suitable as the buffer solution. [1]
trendyline [Turn Over
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11
4 (d) A student titrated 20 cm3 of the buffer sample in (c) containing an acid and its salt, with
0.1 mol dm3 NaOH(aq) and obtained the titration curve below. The maximum buffer
capacity is obtained when 20 cm3 of NaOH is added.
The equivalence point of the titration is obtained when 60 cm3 of aqueous sodium
hydroxide is added.
[You may use HA and A to represent the species identified in (c) to answer part (d)].
pH
7.2
Vol of NaOH / cm3

20 60
(i) Explain why the pH rises only slightly at the start of the titration when a
small amount of sodium hydroxide is added. [1]
(ii) Determine the total amount of acid in the buffer. Hence, show that the ratio
of concentrations of the [HA] and [A] at the start of the titration is 3:1. [2]
(iii) Calculate the K a of the acid at the start of the titration. [1]
(e) An electrochemical cell is composed of two halfcells, namely the AgBrAg and
Ag+Ag half-cells at 298K.
AgBr(s) + e Ag(s) + Br (aq) E = +0.088 V
(i) Using the data booklet and the half-equation of AgBrAg above, write the
overall equation for the cell reaction and calculate the E cell . [2]
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12
4 (e) (ii) The Nernst equation is used to calculate the voltage, E cell , generated
under nonstandard conditions.
RT 1
E cell = E cell nF
ln ( )
Ksp
where n is the number of moles of electrons transferred per mole of

equation, R is the molar gas constant, F is the Faraday constant and K sp is
the solubility product of AgBr.
When E cell = 0, the system has achieved equilibrium.
Decide on a suitable value of n and hence, use your answer in(e)(i) and
the Nernst equation to calculate the solubility product of AgBr at 298 K,
[3]
stating its units.
(iii) Predict how the voltage of the cell, E cell , will change when NH 3 (aq) is
added to the Ag+Ag cell. [2]
(iv) Given that silver arsenate, Ag 3 AsO 4 has a K sp of 1.40x1022, show by
calculation, if AgBr or Ag 3 AsO 4 is the more soluble salt. [2]
[Total: 20]
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13
5 About 10% of the mass of a chicken egg is made up of proteins. The main protein in egg whites
is ovalbumin.
Three of the amino acids obtained from the complete hydrolysis of ovalbumin and their
isoelectric points are given in the table below.
Amino acid Formula of side chain Isoelectric point
Aspartic acid (asp) CH 2 CO 2 H 2.77
Lysine (lys) (CH 2 ) 4 NH 2 9.74
Tyrosine (tyr) 5.66
CH2 OH
(a) State how ovalbumin could be hydrolysed in the laboratory to form the amino acids in [1]
the table above.
(b) (i) Define the term isoelectric point. [1]

(ii) Electrophoresis is an electrolytic method used to separate amino acids based
on their isoelectric points. A simplified diagram of an electrophoresis set-up is
shown below. Depending on the pH of the buffer solution used, the amino
acids will move differently. The positions of the amino acids are ascertained by
spraying the solution with ninhydrin solution. The colourless amino acid spots
will turn blue.
cathode
Mixture of amino anode
acids
Buffer solution
Using data from the table above, explain how electrophoresis can be used to
separate and identify the constituent amino acids in a mixture of aspartic acid,
trendyline
lysine
e and tyrosine in a buffer solution of pH 8. You should
ne shoul include the
structural
ctural formulae of the three amino acids at pH 8 in your answ
answer. [3]
1321 trendyline
14
5 (c) With reference to protein structure, explain why egg white coagulates when cooked. [2]
(d) Besides reacting with amino acids, ninhydrin is also commonly used in fingerprint
analysis in criminal investigations. Another method to analyse fingerprints is called
cyanoacrylate (Super Glue) fuming. One common cyanoacrylate used for this
purpose is ethyl cyanoacrylate. The structures of ninhydrin and cyanoacrylate are
given below.
O
O
OH
OH O
CN
O
ninhydrin ethyl cyanoacrylate
Suggest a chemical test that could be used to distinguish ninhydrin and ethyl
cyanoacrylate from each other. You should state what you would observe for each
compound in the test. [2]
(e) Besides being rich in protein, eggs are also consumed widely as it contains vitamins
and minerals needed on a daily basis. An example of a key nutrient that can be
obtained from eating eggs is phosphorus, which is as important as calcium in building
strong bones in our body.
(i) Describe the reaction of phosphorus(III) oxide, P 4 O 6 , with water. Include the pH
value of the resulting solution, and write an equation for the reaction that occurs. [2]
(ii) Write an equation to illustrate the acid-base nature of phosphorus(V) oxide,
P 4 O 10 . [1]
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15
5 (f) Eggs are also rich in iodine which is a key component of hormones in the thyroid
gland. Iodine deficiency results when we do not consume enough iodine in our diet.
In order to combat iodine deficiency, table salt is mixed with various salts of iodine in
the production of iodised salts.
Potassium iodate, KIO 3 , is often used in iodised salts. With the aid of an equation,
describe how potassium iodate can be prepared using iodine as a starting material. [2]
(g) Describe what you would see if concentrated sulfuric acid is added to separate
samples of solids KBr and KI. Suggest an explanation for the differences in reaction,
and write equations for the reactions that occurred. [4]
(h) Iodine has many isotopes. Only two of its isotopes are used in medicine, such as
radiotherapy and imaging. In order to identify the mass of these two isotopes, they
were first ionised to form singly-charged ions of +1 charge and passed through an
electric field of constant strength. Their angles of deflection, along with a reference
sample of helium nucleus, 42He, were recorded in the table below.
Angle of deflection
Isotope X 1.07
Isotope Y 1.14
Heliumnucleus, 42He 70.1
Calculate the mass of each isotope, giving your answer to the nearest whole number.
[2]
[Total: 20]
~ END OF PAPER ~
trendyline
1323 trendyline
1
Name: Class:
JC2 Preliminary Examinations

Chemistry 9647/03
Paper 3 2 hours
Additional Materials: Writing paper, Data Booklet
Write your name and civics group on all the work you hand in.

This document consists of 14printed pages including this page.
trendyline [Turn over
1324 trendyline
2
1 Propenoic acid, also commonly known as acrylic acid, is used in the formation of many
polymers.
(a) Acrylic acid can be synthesised from 2-chloroethanol in the laboratory by the following
route.
NaCN
in ethanol A
HO
Cl CN CO2H
acrylic acid
(i) Suggest the structure for intermediate A. [1]

HO
CN
(ii) Suggest reagents and conditions for step 2 and for step 3. [2]
Step 2: excess conc. H 2 SO 4 , 170OC
Step 3: H 2 SO 4 (aq), heat
(iii) What type of reaction is occurring in step 2? [1]
Elimination
(b) Acrylic acid is manufactured industrially from the reaction of propene and oxygen gas.
(i) Write a balanced equation for this reaction. [1]
CH 3 CH=CH 2 + 3/2O 2 CH 2 =CHCO 2 H + H 2 O
(ii) Propenal was isolated as an intermediate product in the reaction. Draw the
structure of propenal. [1]
O
(c) Polyacrylate is used in environmentally-friendly detergents to remove calcium ions and

magnesium ions in water.
In the manufacture of polyacrylate, acrylic acid was first converted into acrylic chloride,
followed by reaction with an alcohol to form a monomer. Polyacrylate is formed when the
monomer undergoes polymerisation.
trendyline
1325 trendyline
3
SOCl 2
pyridine CH3OH
CO2H COCl CO2CH3
acrylic chloride
polymerisation
H CO2CH3
C C
H H n
p oly acr ylate
(i) Write a balanced equation for the conversion of acrylic acid into acrylic chloride. [1]
+ SOCl 2 + SO2 + HCl
CO2H COCl
(ii) Suggest the type of reaction occurring in the formation of the monomer from
acrylic chloride. [1]
Nucleophilic substitution/Condensation
(iii) Suggest how polyacrylate can remove magnesium ions from water through
complex formation. [1]
The lone pair of electrons on O of the ester functional group / ligandcan
form dative bond/coordinate bonds with empty orbitals of the cation.
(d) In the kinetic studies of polymerisation, transition element-containing catalysts were used.
A copper(I)-containing catalyst is shown below.
nBu
N N
Cu
N N
nBu
Cu(I)-nBuPCA catalyst
(i) What is the co-ordination number of copper in the Cu(I)-nBuPCA catalyst? [1]
4
trendyline
(ii) C I)-nBuPCA?
Whatt is the electronic configuration of copper in Cu( [1]
1s22s
s22p
2 63s23p63d10
(iii) est whether copper in Cu(I))-nBuPCA
gest
Suggest -nBuPCA
uPCA catalyst can be classified
c as a
[1]
1326 trendyline
4
transition element.
No. Cu+ is not a transition element as it does not have incompletely filled
3d orbitals / does not have partially filled 3d orbitals / has completely filled
3d orbitals.
(e) Cu(I) undergoes disproportionation to form Cu and Cu(II).

(i) Use relevant data from the Data Booklet to predict the spontaneity of this
disproportionation reaction. [2]
Cu+ + e Cu E = +0.52V
Cu2+ + e Cu+ E = +0.15V
E cell = (+0.52) (+0.15) = +0.37V

E cell>0, spontaneous
(ii) Describe and explain what you would see when aqueous ammonia is added
slowly to an aqueous solution of copper(II) chloride, until the aqueous ammonia
is in excess. Write equations for any reactions that occur. [4]
When NH 3 is added slowly, blue ppt is formed.
NH 3 + H 2 O NH 4 + + OH
[Cu(H 2 O) 6 ]2+ + 2OH Cu(OH) 2 + 6H 2 O --- Eqm 1
Blue solution blue ppt
When NH 3 is added in excess, ligand exchange occurs.

[Cu(H 2 O) 6 ]2+ + 4NH 3 [Cu(NH 3 ) 4 (H 2 O) 2 ]2+ + 4H 2 O
deep blue solution
The formation of [Cu(NH 3 ) 4 (H 2 O) 2 ]2+ decreases the concentration of

[Cu(H 2 O) 6 ]2+ and shifts the position of Eqm 1 to left. Hence, the blue ppt
dissolves to form a deep blue solution.
(iii) Suggest an explanation for the difference in colour between [Cu(H 2 O) 6 ]2+ and
[CuCl 4 ]2. [2]
The different ligands, H 2 O and Cl, result in a different energy gap.
Different amount of energy/wavelength of light is absorbed to promote the
trendyline
trendy
tron
ron from the lower energy group to the hi
electron higher energy gro
group.
Lightt refl
ref ected/not absorbed is different.
reflected/not different.
[Total: 20]
1327 trendyline
5
2 In a Mixed Claisen &RQGHQVDWLRQ5HDFWLRQDQHVWHUDQGDNHWRQHUHDFWWRIRUPD-diketone.

.
O 1 CH3CH2ONa, ethanol O O
O . +
2 H
+ + CH CH OH
3 2
OCH2CH3
-
diketone
(a) (i) 'UDZ WKH -diketone formed when 2,2-dimethylcyclohexanone reacts with
ethylethanoate in the Mixed Claisen Condensation Reaction.
O
O
CH3CH2O
2,2-dimethylcyclohexanone ethylethanoate
[1]
O O
(ii) In not more than 3 steps, propose the synthesis of 2,2-dimethylcyclohexanone

from the following starting material.
Cl
[5]
OH O
Cl
. KMnO4/
ethanolic NaOH 1 conc H2SO4 at 0OC
heat . o n water K2Cr2O7
2 b ili g H2SO4 (aq)
heat
[1] [1] [1] [1] [1]
(b) 'XH WR WKH SUHVHQFH RI WZR NHWRQH IXQFWLRQDO JURXSV -diketones are a highly
valuable substrate in several organic chemistry syntheses.
trendyline
y examples
One of the many p is selective reduction, in which onlyy one of the ketone
reduced.
1328 trendyline
6
O O O OH
selective reduction
- - -
4 hydroxypentan 2 one [3]
Draw the mechanism for the reaction between 4-hydroxypentan-2-one and HCN.
Nucleophilic addition
HCN H+ + CN
NaCN Na+ + CN
OR
NaOH + HCN NaCN + H 2 O
O O OH
=
R

O OH
O H
CN
CN
slow + CN

R
CN CN
R R
(c) -diketones exist in equilibrium with a tautomeric form, known as an enol.

This is known as keto-enol tautomerisation. The keto-enol tautomerisation of
pentan-2,4-dione is shown below.
O O O OH
H<0
-
keto enol tautomerisation
keto enol
(i) Write an expression for K c for the keto-enol tautomerisation of pentan-2,4-dione. [1]
Kc = [enol]/[keto]
trendyline
(ii) e case
In the c pentan-2,4-dione, 76% of the mixt
of pentan-2,4-dione, mixture exists as an enol at room
erature and pressure. Calculate a value for K c .
temperature [1]
Kc = 0.76/0.24
1329 trendyline
7
= 3.17 (3sf)
(iii) Sketch a graph showing how the rates of the forward and reverse reactions
change from the time pure keto is added to the time the reaction reaches
equilibrium. Label your two lines clearly. [2]
rate
forward
reverse
time
teqm
(d) The keto-enol tautomerisation is catalysed by the presence of an inorganic base, such as
NaOH.
trendyline
1330 trendyline
8
O O
O O
+ OH +H O
2
keto
O OH
+ OH
enol
(i) State how the presence of NaOH would affect the K c , as calculated in (c)(ii). [1]
No effect.
(ii) On the same diagram in (c)(iii), show how the rates of the forward and reverse
reactions change for the base catalysed keto-enol tautomerisation.
Label your lines clearly. [1]
rate
forward,
catalysed
forward
reverse
reverse,
catalysed
teqm teqm time

(catalysed)
trendyline
1331 trendyline
9
(iii) Hence, explain the effect of NaOH on the reaction. [2]

The catalyst NaOH provides an alternative pathway of lower activation
energy, which increases the number of particles having energy more than
or equals to the activation energy. Hence, the frequency of effective
collision increasesandboth the rate of the forward and reverse reaction
increases / equilibrium reached faster.
(e) The enol form is more stable than the keto form due to two reasons
Reason I: Intramolecular hydrogen bonding
Reason II: Position of p orbitals
O OH
1 3
2
enol
(i) Draw an appropriate diagram to show how reason I contributes to the stability [1]
of the enol form.

H
hydrogen bond

O O
(ii) State the hybridisation of the carbon atoms at positions 1, 2 and 3.

Hence, explain how reason II contributes to the stability of the enol form. [2]
sp2
The carbons 1, 2 and 3 have an unhybridised p orbital each. The adjacent
p orbitals allow the GHORFDOLVDWLRQRIHOHFWURQV.
[Total: 20]
trendyline
1332 trendyline
10
3 (a) Antiseptics and disinfectants are used to kill bacteria. The difference between
antiseptics and disinfectants is that antiseptics are used on living skin and
disinfectants are used on surfaces of objects.
Calcium hypochlorite, Ca(OCl) 2 , is often used to sanitise public swimming pools. It is
produced by treating calcium hydroxide with chlorine gas.
2Ca(OH) 2 + 2Cl 2 Ca(OCl) 2 + CaCl 2 + 2H 2 O
(i) Write an equation for the decomposition of calcium hydroxide. [1]
Ca(OH) 2 CaO + H 2 O
(ii) Deduce whether calcium hypochlorite would decompose at a higher or
lower temperature than calcium hydroxide. Explain your reasoning. [2]
Hypochlorite ion has a larger electron cloud, hence it is more easily
polarised. The O-Cl bond is weakened to a greater extent thus less
energy is required to decompose calcium hypochlorite and it decomposes
at a lower temperature.
(iii) In order to test the percentage purity of the calcium hypochlorite granules,
1 g of the calcium hypochlorite granules above was dissolved in water
and the solution was then reacted with excess iodide in an acidic medium.
OCl + 2H+ + 2I Cl + H 2 O+ I2
The resulting solution was then titrated with 0.500 mol dm3 sodium
thiosulfate. 22.5 cm3 of thiosulfate was required to reach the end-point.
Calculate the percentage purity of the granules. [2]
I 2 + 2S 2 O 3 2I + S 4 O 6
Amount of thiosulfate = 0.0225 x 0.5
= 0.01125 mol
Amount of I2 = 0.01125 / 2 = 0.005625 mol
OCl + 2H+ + 2I Cl + H 2 O+ I2
Amount of hypochlorite = 0.005625 mol
Amount of calcium hypochorite, Ca(OCl) 2 = 0.005625 / 2
= 0.0028125 mol
Mass of calcium hypochlorite = 0.0028125 x (40.1 + 32 + 71)
= 0.40246 g
Percentage purity = (0.40246 / 1) x 100% = 40.2 %
trendyline
(iv) Commercially,
ommercially, calcium hypochlorite
e is available as granules. Using
Us your
1333 trendyline
11
answer in (a)(iii),calculate the volume of chlorine gas (measured at room

temperature and pressure) required to manufacture 1 kg of calcium [2]
hypochlorite granules.
Amount of calcium hypochlorite = 1000 / (40.1 + 32 + 71) = 6.988 mol
Theoretical amount of calcium hypochlorite to manufacture
= (100/40.2) x 6.988
= 17.38 mol
Amount of chlorine gas required = 17.38 x 2 = 34.76 mol
Volume of chlorine gas required = 34.76 x 24 = 834 dm3
(b) Chloroxylenol is commonly used in antibacterial soaps due to its disinfecting

and sanitising properties. It is also responsible for the distinctive odour of
Dettol.
An isomer of chloroxylenol is compound X.
Cl
OH
CH2CH2Cl
OH
chloroxylenol compound X
When hot ethanolic silver nitrate was added to chloroxylenol and compound X
separately, the observations were different. State what you would observe for
each compound and explain the difference in observations. [3]
No ppt for chloroxylenol,whiteppt for compound X
Lone pair of electrons on chlorine is delocalised into benzene ring, giving rise
to partial double bond character to C-Cl in chloroxylenol, thus more energy is
required to break C-Cl bond / C-Cl bond is stronger / harder to break, hence it
trendyline
yli e
is not broken. Hence,, no ppt
pp seen.
C-Cl bond
nd in compound X is broken to form ree Cl / white ppt ofAgC
orm free offAgClis
ofAg
formed.
1334 trendyline
12
(c) Compounds A and B are structural isomers of chloroxylenol. Both A and Bgive
a violet colouration with neutral FeCl 3 .
A rotates plane-polarised light, but B does not.When B is treated with hot
alcoholic sodium hydroxide, a compound of molecular formula C 8 H 8 O is
formed.
When A is treated carefully with hot aqueous sodium hydroxide, compound C,
C 8 H 10 O 2 , is formed.
C reacts with hot concentrated potassium dichromate(VI) to form compound D.
C reacts with hot concentrated potassium manganate(VII) to form compound
Eand carbon dioxide gas.
D gives an orange precipitate with 2,4-dinitrophenylhydrazine, but E does not.
Suggest structures for A to E, and explain the observations described above. [10]
[Total: 20]
A and B gives violet colouration with neutral phenol present

FeCl 3 .
A rotates plane polarised light, but B does not. A has a chiral centre
Or indicate * on the chiral carbon of A correctly
OH Cl
C
*
CH3
H
When A is treated with hot aq NaOH, C, Nucleophilic substitutionof halogenoalkane /

C 8 H 10 O 2 , is formed. chloroalkaneto form alcohol.
-Cl in A is replaced by -OH in C.
OH OH
CH3
C
H
C reacts with hot conc

trendyline
dy
yll
onc K 2 Cr 2 O 7 to form D. Oxid
C
Oxidation of 2 alcohol to form D, a ketone.
1335 trendyline
13
OH O
C reacts with hot conc KMnO 4 to form Eand Oxidationof benzylic H to form E, with a benzoic
carbon dioxide gas. OH
CO2H
E
acidfunctional group
D gives an orange ppt with 2,4-DNPH, but E Condensation
does not. D is aketone
B forms C 8 H 8 O when treated with hot alcoholic Elimination of HCl.
NaOH B is a 1Ohalogenoalkane
OH
CH2CH2Cl
trendyline
1336 trendyline
14
4 The table below summarises the different types of acids found in various types of beverages.
Beverage Acid Formula pK a1 pK a2 pK a3

Beer Carbonic H 2 CO 3 6.37 10.3
Fruit Juices Malic HO 2 CCH 2 CH(OH)CO 2 H 3.46 5.10
Soda Phosphoric H 3 PO 4 2.12 7.21 12.3
(a) (i) Explain why the pK a1 of malic acid is so much lower than the pK a1 of
carbonic acid. [2]
HO 2 CCH 2 CH(OH)CO 2 has an electron-withdrawing group (-OH or CO 2 H)
which disperses the negative charge on the COOincreasing the stability
of anion compared to HCO 3 -, hence malic acid is more acidic.
OR
Malic acid has a more stable anion, HO 2 CCH 2 CH(OH)CO 2 , which is

stabilised by intramolecular hydrogen bonding and this helps to disperse
the negative charge. HCO 3 cannot be stabilised this way, hence malic
acid is more acidic.
(ii) Explain why the pK a3 of phosphoric acid is so much higher than the pK a2 of
malic acid. [1]
It is harder to lose a H+ from a doubly charged(or more negatively-
charged) ion, HPO 4 2 than from singly charged anion,

HO 2 CCH 2 CH(OH)CO 2 .
(b) (i) 50.0 cm3 of 0.5 mol dm3 aqueous H 3 PO 3 was mixed with 30cm3 of excess
aqueous NaOH. It was found that the temperature of the solution rose by
8.4C after mixing. Calculate the enthalpy change of reaction per mole of
H 3 PO 3 (aq).
Given: Specific heat capacity of water = 4.18 J g1 K1;
trendyline
m3.
Density of water = 1.0 g cm [2]
2
No. of moles of H 3 PO 3 used
ed = 2.5 10 mol
Q = mc
mcT = 80 4.18 8.4 = 2808.96J
mcT
1337 trendyline
15
Enthalpy change RIUHDFWLRQ N-PRO1

(ii) Hence, given that the enthalpy change of neutralisation of HCl (aq) by
1D2+DTLV kJ mol1, suggest the basicity of H 3 PO 3 .
[1]
2 or dibasic
(c) A medical student wanted to investigate the buffer solution in fluids for
intravenous injection. He needed to prepare a buffer of pH 7.2. Of the pK a values
given in the table above, suggest a conjugate acidbase pair which is most
suitable as the buffer solution. [1]
2
H 2 PO 4 , HPO 4
(d) A student titrated 20 cm3of the buffer sample in (c) containing an acid and its salt, with
0.1 mol dm3 NaOH(aq) and obtained the titration curve below. The maximum buffer
capacity is obtained when 20 cm3 of NaOH is added.
The equivalence point of the titration is obtained when 60 cm3 of aqueous sodium
hydroxide is added.
[You may use HA and A to represent the species identified in (c) to answer part (d)].
pH
7.2
Vol of NaOH / cm3

20 60
(i) Explain why the pH rises only slightly at the start of the titration when a small
amount of sodium hydroxide is added. [1]
trendyline
tren li
mall amount of NaOH is added, th
When a small e large
the e res
reservoir of HA will remove it,
ng
g fairly
maintaining irly constant pH.
pH.
(ii) Determine
rmine
mine the total amount of acid in the buffer. Hence, show
sshow that
tha the ratio
oncentrations of the [HA] and [A
of concentrations A] at the start of the titration is 3:1. [2]
1338 trendyline
16
Total no. of moles of HA in buffer = no. of moles of NaOH required to reach

equivalence point = 0.1 x 60/1000 = 6 x 103 moles
Let original amount of A-in bufferbe y mol.

When 20cm3 of NaOH is added, MBC occurs.
Amount of Aat MBC = (2 x 103 +y) mol
Note: HA + OHA+ H 2 O
At MBC, [HA] = [A]

Hence, amount of HA = amount of A (since volume is the same).
Since a further 40cm3 of NaOH is required to neutralise all HA at MBC,
amount of HA at MBC = 4 x 103 mol = amount of A at MBC.
=>(2 x 103 +y) = 4 x 103
y = 4 x 103 2 x 103 = 2 x 103
No. of moles of HA:A = 6 x 103 : 2 x 103 = 3:1
(iii) Calculate the K a of the acid at the start of the titration. [1]
pH = pK a + lg [salt]/[acid]
7.2 = lgK a + lg (1/3)
K a = 2.10 x 108 mol dm3
(e) An electrochemical cell is composed of two halfcells, namely the AgBrAg and
Ag+Ag halfcells at 298K.
AgBr(s) + e Ag(s) + Br (aq) E = +0.088 V
(i) Using the data booklet and the half-equation of AgBrAg above, write the
overall equation for the cell reaction and calculate the E cell . [2]
AgBr + e Ag+ + Br
Ag+ + e Ag
Overall equation: Ag+ +Br AgBr
trendyline
en
E cell = 0.80
80
0 0.088
088 = +0.712
0.712 V
(ii) The Nernst equation is used to calculate the voltage

voltage, E cellll , genera
generated under
1339 trendyline
17
nonstandard conditions.
RT 1
E cell = E cell nF
ln ( )
Ksp
where n is the number of moles of electrons transferred per mole of

equation, R is the molar gas constant, F is the Faraday constant and K sp is
the solubility product of AgBr.
When E cell = 0, the system has achieved equilibrium.
Decide on a suitable value of n and hence, use your answer in(e)(i) and the
Nernst equation to calculate the solubility product of AgBr at 298 K, stating
[3]
its units.
n = 1;
At equilibrium, E cell = 0 V
0 = E cell (RT/nF) ln(1/K sp )
Therefore, 0 = +0.712 (8.31)(298)/(1)(96500) ln (1/K sp )
K sp = 8.92 x 1013 mol2 dm6
(iii) Predict how the voltage of the cell, E cell , will change when NH 3 (aq) is
added to the Ag+Ag cell. [2]
[Ag+] will decreasedue to [Ag(NH 3 ) 2 ]+ formed:
Ag+ + 2NH 3 [Ag(NH 3 ) 2 ]+ + Br
OR
Aqueous NH 3 will react with Ag+ to form a soluble complex, [Ag(NH 3 ) 2 ]+.
Ag+ + e Ag
Position of equilibrium will shift left,resulting in less positive E cathode .
Since E cell =E cathode E anode , Voltage/ E cell will be less positive and E cell
will be less positive.
(iv) Given that silver arsenate, Ag 3 AsO 4 has a K sp of 1.40x1022, show by

calculation, if AgBr or Ag 3 AsO 4 is the more soluble salt. [2]
Let x be solubility of AgBr.
trendyline
tre
e
K sp = x2
9.4 x 107 mol dm-3
x = 9.44
1340 trendyline
18
Let y be solubility of Ag 3 AsO 4

K sp = y(3y)3 = 27y4
y= 1.51 x 106mol dm-3
Since Ag 3 AsO 4 has a higher solubility, Ag 3 AsO 4 is more soluble.
[Total: 20]
5 About 10% of the mass of a chicken egg is made up of proteins. The main protein in egg
whites is ovalbumin.
Three of the amino acids obtained from the complete hydrolysis of ovalbumin and their
isoelectric points are given in the table below.
Amino acid Formula of side chain Isoelectric point
Aspartic acid (asp) CH 2 CO 2 H 2.77
Lysine (lys) (CH 2 ) 4 NH 2 9.74
Tyrosine (tyr) 5.66
CH2 OH
(a) State how ovalbumin could be hydrolysed in the laboratory to form the amino acids [1]
in the table above.
Aqueous acid / alkali (must specify),
heat for several hours / prolonged heating
Or
Conc HCl (6 mol dm3), heat for 24 hours
(b) (i) Define the term isoelectric point. [1]

Isoelectric point is defined as the pH at which the amino acid carries no net
electrical charge.
(ii) Electrophoresis is an electrolytic method used to separate amino acids based
on their isoelectric points. A simplified diagram of an electrophoresis set-up is
shown below. Depending on the pH of the buffer solution used, the amino
acids will move differently. The positions of the amino acids are ascertained by
trendyline
spraying
g the solution with ninhydrin solution. The colourless amino
ng amin acid spots
will turn
rn
n blue
blue.
cathode
1341 trendyline
19
Mixture of amino anode

acids
Buffer solution
Using data from the table above, explain how electrophoresis can be used to
separate and identify the constituent amino acids in a mixture of aspartic acid,
lysine and tyrosine in a buffer solution of pH 8. You should include the
structural formulae of the three amino acids at pH 8 in your answer. [3]
At pH 8:
COO
H2N
COO
COOH
H2N
H3N (CH2)4NH3
COO
O
aspartic acid lysine tyrosine
Lysine has an overall positive charge, hence it will move towards the
cathode.
Aspartic acid and tyrosine both have an overall negative charge, hence both
will move towards the anode.
Since tyrosine has a larger mass (or heavier), it will move slower than
aspartic acid, hence it is closer to the middle. (Or vice versa)
(c) With reference to protein structure, explain why egg white coagulates when cooked. [2]
Heatwill disrupt hydrogen bonds and van der Waals forces, causing the secondary
and tertiary(and quaternary) structures to be destroyed / denatured. Hence, the
trendyline
egg white coagulates.
(d) Besides reacting

acting
cting with
h amino acids, ninhydrin is also commonly used in fingerprint
f
1342 trendyline
20
analysis in criminal investigations. Another method to analyse fingerprints is called

cyanoacrylate (Super Glue) fuming. One common cyanoacrylate used for this
purpose is ethyl cyanoacrylate. The structures of ninhydrin and cyanoacrylate are
given below.
O
O
OH
OH O
CN
O
ninhydrin ethyl cyanoacrylate
Suggest a chemical test that could be used to distinguish ninhydrin and ethyl
cyanoacrylate from each other. You should state what you would observe for each
compound in the test. [2]
Add 2,4-DNPH to each compound separately. Orange ppt formed for ninhydrin but
no ppt formed for ethyl cyanoacrylate.
OR
Add cold KMnO 4 and H 2 SO 4 (aq) to each compound separately. Purple solution
decolourised for ethyl cyanoacrylate but remains purple for ninhydrin.
OR
Add cold KMnO 4 and NaOH (aq) to each compound separately. Purple solution
decolourised for ethyl cyanoacrylate and brown ppt formed. But solution remains
purple for ninhydrin.
OR
Add Br 2 (aq) to each compound separately. Orange solution decolourised for ethyl
cyanoacrylate but remains orange for ninhydrin.
(e) Besides being rich in protein, eggs are also consumed widely as it contains vitamins
and minerals needed on a daily basis. An example of a key nutrient that can be
obtained from eating eggs is phosphorus, which is as important as calcium in
building strong bones in our body.
trendyline
(i) ibe the reaction of phosphorus(
Describe phosphorus III
II ) oxide,
xide, P 4 O 6 , with water.
water Include the
wate
ue of the resulting solution, and write an equation for the reaction that [2]
lue
pH value
s.
occurs.
1343 trendyline
21
P 4 O 6 reacts vigorously (or readily or violently) with water.

pH = 3
P 4 O 6 + 6H 2 O 4H 3 PO 3
(ii) Write an equation to illustrate the acid-base nature of phosphorus(V) oxide,
P 4 O 10 . [1]
P 4 O 10 + 12NaOH 4Na 3 PO 4 + 6H 2 O
(f) Eggs are also rich in iodine which is a key component of hormones in the thyroid
gland. Iodine deficiency results when we do not consume enough iodine in our diet.
In order to combat iodine deficiency, table salt is mixed with various salts of iodine in
the production of iodised salts.
Potassium iodate, KIO 3 , is often used in iodised salts. With the aid of an equation,
describe how potassium iodate can be prepared using iodine as a starting material. [2]
Add iodine to KOH
3I 2 + 6KOH KIO 3 + 5KI + 3H 2 O
(g) Describe what you would see if concentrated sulfuric acid is added to separate
samples of solids KBr and KI. Suggest an explanation for the differences in
reaction, and write equations for the reactions that occurred. [4]
KX + H 2 SO 4 HX + KHSO 4
2HX + H 2 SO 4 SO 2 + X 2 + 2H 2 O
X = Br and I
White fumes are seen.
Reddish-brown fumes are seen for KBrwhile violet vapouris observed for KI.
8HI + H 2 SO 4 H 2 S + 4I 2 + 4H 2 O
Iodide ion is more easily oxidisedthan bromide ion OR iodide ion is a better reducing
agentthan bromide ion, hence further reaction will take place for KI.
trendyline
(h) Iodine has many isotopes. Only two of its isotopes are used in medicine
medicine, such as
pyy and imaging. In order to identify the mass of these two isot
radiotherapy isotopes, they
1344 trendyline
22
were first ionised to form singly-charged ions of +1 charge and passed through an
electric field of constant strength. Their angles of deflection, along with a reference
sample of helium nucleus, 42He, were recorded in the table below.
Angle of deflection
Isotope X 1.07
Isotope Y 1.14
Heliumnucleus, 42He 70.1
Calculate the mass of each isotope, giving your answer to the nearest whole
number. [2]
2
= 70.1
4
1
= 1.07
2
( ) 70.1
4
1 =
( ) 1.07

x = 131
1
= 1.14
2
( ) 70.1
4
1 =
( ) 1.14

y = 123
[Total: 20]
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1345 trendyline
1
SERANGOON JUNIOR COLLEGE

General Certificate of Education Advanced Level
Higher 2
Candidate Name
Class
CHEMISTRY 9647/01
JC2 PreliminaryExamination 23 September2016
Paper 1 Multiple Choice 1 hour
Optical Mark Sheet (OMS)
On the separate multiple choice OMS given, write your name, subject title and class in the
spaces provided.
Shade correctly your FIN/NRIC number.
There are 40 questions in this paper. Answer all questions.

For each question there are four possible answers A, B, C and D.
Choose the one you consider correct and record your choice using a soft pencil on the
separate OMS.
Each correct answer will score one mark.
A mark will not be deducted for a wrong answer.
You are advised to fill in the OMS as you go along; no additional time will be given for the
transfer of answers once the examination has ended.
Any rough working should be done in this question paper.
trendyline
This document consists of18printed
of18
of1 printed pages.
Turn Over]
1346 trendyline
2
Answer all questions

1 The relative abundances of the isotopes of a sample of titanium are shown in the table
below.
Relative Isotopic Mass 46 47 48 49 50
Relative Abundance 11.2 10.1 100.0 7.3 7.0
What is the relative atomic mass of titanium in this sample?
A 48.00
B 47.92
C 47.90
D 47.89
2 To identify an oxide of nitrogen, 0.10 mol of the oxide is mixed with an excess of
hydrogen and passed over a catalyst at a suitable temperature.
H 2 (g)
N x O yxNH 3 + yH 2 O
The water produced weighs 7.20 g. The ammonia produced is neutralised by 200 cm3
of 1.0 mol dm-3 HCl.
What is the formula of the oxide of nitrogen?
A N2O
B NO
C NO 2
D N2O4
3 50 cm3 of a 0.10 mol dm-3 solution of a metallic salt was found to react exactly with
25.0 cm3 of 0.10 mol dm-3 aqueous sodium sulfite. In this reaction, the sulfite ion is
oxidised as follows.
2- 2- +
SO 3 (aq) + H 2 O(l)SO 4 (aq) + 2H (aq) + 2e
What is the new oxidation number of the metal in the salt if its original oxidation number
was +3?
A +1
B +2
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C +4
D +5
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3
4 Of the following, which is the strongest oxidising agent?
A O2+
B O2
C O2
D O 2 2
5 Paramagnetism refers to the magnetic state of an atom with one or more unpaired
electrons. The greater the number of unpaired electrons in an atom, the greater the
paramagnetism.
Which atom has the greatest paramagnetism?
A Oxygen
B Chlorine
C Scandium
D Arsenic
6 Which of the following is true of both real and ideal gases?
A Molecules can be liquefied.

B Molecules occupy a finite volume.
C Molecules are in constant random motion.
D Molecules behave identically at high pressure and low temperature.
7 The Valence Shell Electron Pair Repulsion Theory (VSEPR) is used to predict the
shapes of molecules.
Which shape is correctly predicted by VSEPR?
number of regions number of lone pairs shape

of electron density
A 3 1 Tetrahedral
B 3 1 Trigonal pyramidal
C 5 1 See-saw
D 5 1 Square pyramidal
8 trendyline
nitude
tude of the lattice energy of calcium oxide and calcium carbonate is
The magnitude
ol1 and 2814 kJmol1 respectively.
3414 kJmol respectivelyy The
T enthalpy change of decomposition
d
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1348 trendyline
4
of calcium carbonate is +176 kJmol1.
Using the information provided, calculate the enthalpy change of the following
reaction.
CO 3 2(g) O2(g) + CO 2 (g)
A - 424 kJ mol1
B +424 kJmol1
C - 776 kJmol1
D +776 kJmol1
9 Primary, secondary and tertiary amine have similarly shaped molecules.
What is the predominant intermolecular force of attraction in methylamine,

dimethylamine and trimethylamine?
methylamine dimethylamine trimethylamine

A hydrogen bonds hydrogen bonds hydrogen bonds
B hydrogen bonds permanent dipole Instantaneous dipole
permanent dipole induced dipole
C permanent dipole permanent dipole permanent dipole
permanent dipole permanent dipole permanent dipole
D hydrogen bonds hydrogen bonds permanent dipole
permanent dipole
10 The integrated form of first-order rate law is as shown.
ln A = kt + lnA o
where A is the activity at time t,

A o is the initial activity,
k is the rate constant,
t is the time taken.
What is the half-life for a first order reaction if 68% of a substance is reacted within
66s?
A 33 s
B 40 s
C 49 s
D 119 s
11 h equilibrium is K c = K p ?
For which
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1349 trendyline
5
A C(s) + H 2 O(l) CO(g) + H 2 (g)
B H 2 (g) + I 2 (g) 2HI(g)
C N 2 (g) + 3H 2 (g) 2NH 3 (g)
D 2NO 2 (g) N 2 O 4 (g)
12 The ionic product of water, K w , at two different temperatures is shown below,
K w / mol2 dm6 Temperature / K

1.00 x 1014 298
1.44 x 1014 303
A Self-ionisation of water is an exothermic process.

B At 303 K, [H+] = 0.72 x 1014 mol dm3
C [H ][OH ]
Kw =
[H2O]
D At 303 K, pH < 7
13 Calculate the pH of the resulting solution when 10 cm3 of potassium hydroxide with
7 3
concentration at 7.5 x 10 mol dm is mixed with an equal volume of
8
hydrogen bromide with concentration at 8.5 x 10 mol dm .
A 4.18
B 6.36
C 7.64
D 9.82
14 Aqueous hydrochloric acid was electrolysed for ten minutes, 200 cm3 of gasA was
collected at the anode.
The same current was then applied to concentrated sodium chloride solution in
another experiment and 400 cm3 of a gasB is collected at the cathode.
Which of these statements is correct?
A GasB is pale yellow.

B The time taken for the second electrolysis is also ten minutes.
trendyline
C ne gas was collected initiallyy in the first electrolysis system.
Chlorine
D Mercuryry
y electrodes can be used for the second electrolysis system if gas B is to
lected.
ected
be collected.
15 he
e following properties could be predicted for strontium or itits compounds?
Which of the
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1350 trendyline
6
A It does not burn in air.

B It forms a soluble sulfate.
C It reacts with cold water, liberating hydrogen.
D It forms a water-soluble carbonate which does not decompose on heating.
16 Equal volumes of chlorine gas were bubbled into hot and cold sodium hydroxide
separately until reactions were complete.
Which of the following statements is incorrect about the above reactions?
A Disproportionation reactions will occur.
B Greenish-yellow chlorine gas decolourises in both reactions.
C When aqueous silver nitrate is added to the resulting solutions, white precipitate
is formed.
D Sodium chlorate(VII) and sodium chlorate(I) are formed in the reactions

respectively.
17 Aqueous chlorine is added to aqueous sodium bromide and the mixture is shaken
with an equal volume of trichloromethane.
Which observation will be made?
A The solution in the test-tube turns colourless.

B The solution in the test-tube turns orange.
C A colourless layer forms on top of a purple layer.
D A colourless layer forms on top of an orange layer.
18 A reaction scheme starting from aqueous copper(II) sulfate solution is shown below.
Both G and H are copper-containing species.
excess
NH3(aq) NH3(aq) Na4edta(aq) 2-
CuSO4(aq) G H [Cu(edta)] (aq)
I II III
A Reaction III is a redox reaction.

B NH 3 acts as a ligand in reactionI.
trendyline
C H is a deep blue solution containing [Cu(NH 3 ) 4 (H
H 2 O) 2 ]SO 4 .
D The entropy
ntropy of the system reactionIIIoccurs.
syste decreases when reaction
reactionIII
II occurs.
ccurs
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1351 trendyline
7
19 Stigmasterol is an unsaturated plant sterol occurring in the plant fats of soybean.
How many stereoisomers does stigmasterol have?
A 29
B 210
C 211
D 212
20. Four carbon-carbon bonds are labelled in the diagram.
x
CH
y
z
Which bonds are made up of a sp2-sp2 overlap?
A x only
B x and y only
C w, x and y only
D w, y and z only
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1352 trendyline
8
21. When heated with chlorine, the hydrocarbon 2,2,3,4-tetramethylpentane undergoes

free radical substitution. In a propagation step, the free radical J is formed by the
loss of one hydrogen atom.
CH3
H3C CH3
+ Cl J + HCl
H3C
CH3 CH3
How many different forms of J are theoretically possible?
A 3
B 4
C 5
D 6
22 Saccharin was an artificial sweetener used in some soft drinks. It was manufactured
from methylbenzene by a series of reactions.
CH3 CH3 CH3
ClSO3H SO2Cl NH3 SO2NH2
I II
Which of the following shows the correct reaction type for steps I and II?
I II
A Electrophilic substitution Electrophilic addition
B Electrophilic substitution Nucleophilic substitution
C Nucleophilic substitution Nucleophilic substitution
D Nucleophilic substitution Electrophilic substitution
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9
23 Which of the following cannot be used to distinguish between the following compounds?
O O HO CHO
A Hot acidified K 2 Cr 2 O 7
B Neutral iron(III) chloride
C Diammine silver complex
D Phenylhydrazine
24 The reaction scheme below shows the synthesis of compound S.
Cl Br
CH3 NaOH(aq) K2Cr2O7/H2SO4(aq)

S
heat heat
Which of the following can be S?
A Cl O C OH O
O
CH3 CH3 C
C
OH
OH
C
B OH O D O Cl O
CH3 C C
HO OH
OH
C
trendyline
Turn Over]
1354 trendyline
10
25 The following synthetic route consists of three steps.
CH3 COOH
NO 2
Br
Which sequence of steps would give the highest yield?
A KMnO 4 , H 2 SO 4 , heat conc HNO 3 , conc H 2 SO 4 , Br 2 , Fe, r.t.p

heat
B conc HNO 3 , conc H 2 SO 4 , Br 2 , Fe, r.t.p KMnO 4 , H 2 SO 4 , heat

heat
C Br 2 , AlBr 3 , r.t.p conc HNO 3 , dilute H 2 SO 4 , KMnO 4 , H 2 SO 4 , heat

heat
D Br 2 , Fe, r.t.p KMnO 4 , H 2 SO 4 , heat conc HNO 3 , conc H 2 SO 4 ,

heat
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11
26 Ten grams of each of the following was heated with NaOH(aq) for a prolong period of
time. Subsequently, dilute HNO 3 (aq) and AgNO 3 (aq) were added.
Which compound will produce the greatest mass of silver halide precipitate?
A Br C Br
(M r = 134.9) Br(M r = 235.8)
B CH 3 COCl D Cl
(M r = 78.5)
Cl
(M r = 153.0)
27 After the reduction using tin and concentrated acid of nitrobenzene to phenylamine, an
excess of sodium hydroxide is added.
What is the purpose of the sodium hydroxide?
A to dry the product
B to liberate the phenylamine
C to neutralise the excess acid
D to lower the boiling point for subsequent distillation
28 Which of the following shows the correct order of basicity?
High pK b Low pK b
A
CH2 NH2 CH2 NH2 NH2 CONH2
B
CONH2 CH2 NH2 NH2 CH2 NH2
C
CONH2 NH2 CH2 NH2 CH2 NH2
D
t end
trendyline
dyyl ne
NH2ne ONH2
CO
CONH H2 NH2
CH CH
C H2 NH2
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1356 trendyline
12
29 Aspartame is a dipeptide derivatives used as an artificial sweetener. Its general

usefulness is restricted because it loses its sweetness after hydrolysis.
H2NCHCONHCHCO2CH3
CH2 CH2
- +
CO2 Na
Which product would be formed after prolong acid hydrolysis.
A + +
H3NCHCO2H H3NCHCO2CH3
CH2
- + CH2
CO2 Na
and
B +
H3NCHCO2H H2NCHCO2CH3
CH2
CH2
COOH and
C + +
H3NCHCO2H H3NCHCO2H
CH2
CH2
COOH
and andCH 3 OH
D +
H3NCHCO2H CH2CO2H
CH2
CH2
COOH and andCH 3 OH
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1357 trendyline
13
30 Electrophoresis is a technique of separating and identifying amino acids. A solution of

amino acids is absorbed into paper that is moistened with a buffer solution and
stretched between two electrodes. Positively charged species move towards the
cathode, negatively charged species towards the anode.
With a buffer at pH 5, which amino acid will move most readily towards the cathode?
A O C NH2 O
HO OH O OH
NH2 NH2
B O O D O
HO OH OH
NH2 NH2
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14
For questions 31 40, one or more of the numbered statements 1 to 3 may be correct.
Decide whether each of the statements is or is not correct. The responses A to D should be
selected on the basis of
A B C D
No other combination of statements is to be used as correct response.
31 The graph below shows the first twelve ionisation energies for element T.
ionisation
energy
number of electrons removed
1 It is in Group Iof the Periodic Table.
2 It forms an oxide which dissolves readily with acid.
3 It is in the third period (Na to Ar) of the Periodic Table.
32 The following chemical reactions are listed below.
Combustion of ethandioic acid

Evaporation of water
Atomisation of magnesium
Photolysis of chlorine
1
2
3 trendyline
S is positive for all reactions
reactions.
G is negative for all reactions.
H is positive
ositive for all reactions
reactions.
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1359 trendyline
15
33 A reaction in which a product acts as a catalyst is said to be autocatalytic.
2MnO 4 -(aq) + 5C 2 O 4 2-(aq) + 16H+(aq) 2Mn2+(aq) + 10CO 2 (g) + 8H 2 O(l)
In the oxidation of ethanedioate ions by manganate(VII) ions, the reaction is

accelerated by the Mn2+ ions produced during the reaction.
Graph of [MnO4-] against time
[MnO4-]/mol dm-3
(1) (1) Initially the reaction is slow.
(2) But the reaction rate increases as

(2) Mn2+ ions catalyse the reacton.
(3) The reaction rate falls the concentrations

of reactants decrease.
(3)
0 time/s
Which of the following statements can be deduced from the graph above?
1 Initial rate of reaction is the fastest at (1).
2 Reaction rate increases at (2) as Mn2+ is generated.
3 Reaction rate decreases at (3) as the concentration of the reactants

decrease.
34 The graph below shows how the percentage of reactant U(g) that remained in an
equilbrium mixture varies with 1/T at pressures of 1.5atm and 2 atm.
2 atm
%U (g) at 1.5 atm

equilibrium
trendyline
Which of the
e following statement can be deduced from this information?
he
1 The forward endothermic.

orward reaction is endothermic
2 The equation for

for the above reaction could beU(g)
beU
beU(g) V(g)) + W
g) V(g) W(g).
(g).
(g)
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1360 trendyline
16
3 The equilibrium constant, K p , increases as pressure increases in the system.
A B C D
35 A student was investigating the possibility of an electrochemical cell using Cu2+/Cu+

and Fe3+/Fe2+ half-cells.
Pt electrode Pt electrode
Salt Bridge
1 mol dm3 Cu+ (aq)

1 mol dm3 Fe2+ (aq)
3 2+
1 ld C ( ) 3 3+
1 ld F ( )
Which statements are true of the above set up?
1 Eocell = +0.62 V.
2 Copper and iron electrodes cannot be used instead.
3 When excess sodium hydroxide is added to the Fe2+/Fe3+ half-cell, the polarity of
the electrodes are reversed.
36 Barium sulfate is less soluble than magnesium sulfate.
Which of these factors are needed to be considered in order to explain this

observation?
1 H hyd of barium ion and magnesium ion.

2 H f of barium sulfate and magnesium sulfate.
3 Atomic radii of barium and magnesium.
37 Which observation about bromine or its compounds is correct?
1 When aqueous lead(II) nitrate is added to aqueous sodium bromide, a cream

precipitate is observed.
trendyline
2 When sodium bromide is treated with concentrated sulfuric acid, a gas that turns
moist blue litmus paper red is evolved
evolved.
3 Silver bromide is soluble in both dilute

ute and concentrated ammonia solution.
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1361 trendyline
17
A B C D
38 The catalytic converter is part of the exhaust system of modern cars.

Which reactions occur in the catalytic converter?
1 2CO + O 2 &2 2
2 12&21 2 + 2CO 2
CxHy + (2x+ y ) 12xCO 2 + y H 2 O+ (x+ ) N 2

y
3
2 2 4
39 Halogenoalkanes react with aqueous alkali. One mechanism of this reaction has the
reaction pathway diagram shown below.
Energy
X

Y
R-Hal +OH
R-OH + Hal
Reaction Pathway
Which statements are true? ( indicates a partial bond)
1 The reaction is a type of nucleophilic substitution.
2 X is C Hal
-
trre
e
3 Y is HO C H
Hal
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1362 trendyline
18
40 Which of the following phenomena involves denaturation of proteins?

1 Heating of egg white.
2 Production of bean-curd from soy milk.
3 Dissolving Penicillin in a test tube of hot acid.
Penicillin
END OF PAPER 1
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1
CHEMISTRY 9647/01
Paper 1 Multiple Choice 19th September 2016

1 hour
Additional materials: Multiple Choice Answer Sheet
Data Booklet

Write yourname
andCivics Group
Write and shade

your CG number
followed by
last 3 digits of NRIC
Answer Sheet.
trendyline
This document consistss of 18 printed
nted p
pages.
2016 TJC H2 Chemistry Preliminary Examination [Turn Over

1444 trendyline
2
Section A
Part 1
For each question there are four possible answers, A, B, C and D. Choose the one you
1 During the bacterial leaching of low grade copper ores, acidified water is sprayed onto the ore
chalcopyrite, CuFeS 2 . Bacteria then convert the insoluble ore into a solution according to the
equation shown below:
4CuFeS 2 + 17O 2 + 4H+ 4Cu2+ + 4Fe3+ + 8SO 4 2- + 2H 2 O
No change occurs in the oxidation state of copper.
What changes in oxidation state occur for the iron and the sulfur in this reaction?
Change in oxidation state

Fe S
A +1 +8
B +1 -8
C -1 +6
D -1 -6
2 When cobalt metal is reacted with a solution containing cobalt(III) ions, only cobalt(II) ions are
formed. How many moles of Co and Co3+(aq) would result in a mixture containing both
cobalt(II) and cobalt(III) ions in the mole ratio of 3:1 after the reaction had taken place?
Moles of Co Moles of Co3+

A 1 2
B 1 3
C 1 5
D 2 3
3 Sodium hydrogen carbonate, NaHCO 3 , can be prepared from sodium sulfate by a three-step
process.
Na 2 SO 4 (s) + 4C(s) Na 2 S(s) + 4CO(g)
Na 2 S(s) + CaCO 3 (s) CaS(s) + Na 2 CO 3 (s)
Na 2 CO 3 (s) + H 2 O(l) + CO 2 (g) 2NaHCO 3 (s)
trendyline
sodium hydrogen carbonate (M r = 84.
What is the mass of sodiu 84.0),
84 0), to the ne
n
nearest kg, that could be
formed from 100 kg of the sodium sulfate (M r = 142
142.1),
142.1), assuming a 90% yyield in each step?
A 43 B 86 C 106 D 118 kg

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3
4 The following are flight paths of charged particles when accelerated in an electric field.
+
RS
ST

TU
Which of the following correctly identifies S, T and U?

S T U
15
A O+ 14
C+ 14
N+
15 14
B O C+ 28
Si+
14 16
C 1 O2+ 28
Si2+
14 14
D 1 C+ 28
Si4+
5 Lecithinis used as an emulsifying and stabilising agent in the food, pharmaceutical and
cosmetic industries.
R
O
O
O
O O P O
O O CH3
+
R N
H3C CH3
lecithin
=
where R long hydrophobic carbon chains
Which of the following statements about lecithin is correct?
A It can form van der Waals forces with other non-polar molecules.
B It has a low boiling point.
C It cannot rotate plane of polarised light.
D It can form hydrogen bonds between its own molecules.
6 Mixtures of argon and another gas are commonly used during welding. One such gaseous
mixture has a density of 1.82 g dm3 at s.t.p.
trendyline
e the other gas in this mixture? [Density of argon
What could be ar = 1.78 g dm3 at s.t.p.]
A neon B oxygen
xyge
oxygen
C fluorine D carbon
bon dioxide
carbon diox

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4
7 Which line in the table gives the signs of H, S and G for the melting of ice at room
temperature and pressure?
H S G
A +
B +
C + + +
D + +
8 Which reaction represents standard enthalpy change at 298 K?
A P 4 (l) 4P(g)
B H 2 (g) + Br 2 (g) 2HBr(g)
C HF(aq) + NaOH(aq) NaF(aq) + H 2 O(l)
D CH 4 (g) + 2O 2 (g) CO 2 (g) + 2H 2 O(g)
9 In the construction of heart pacemakers, it is possible to use a tiny magnesium electrode

which creates an electrical cell with the inhaled oxygen. The relevant half-cells are as
follows:
Mg2+ + 2e- Mg E= -2.38V
O 2 + 2H+ + 2e-H 2 O E= +1.23V
V
Under standard conditions, the cell e.m.f. would be +3.61V, but in the body a potential of
+3.25V is more usual.
What is the best explanation for this lower e.m.f.?
A the low concentration of Mg2+ ions surrounding the magnesium electrode

B the pH of between 7 and 8 of the body fluid surrounding the electrodes
C the high resistance of the body fluids surrounding the electrodes
D the small size of the magnesium electrode
10 Consider the following equilibrium system:

2AlCl 3 (g) Al 2 Cl 6 (g)
Which of the following statements will cause the position of the above equilibrium to shift to
the left?
trendyline
A decreasing
g the volume of the vessel
ng
B increasing
g the temperature
C pumping inert
nert gas into the vessel at constant volume
D pumping AlCl 3 gas into the vessel

1447 trendyline
5
11 Which of the following statements is true about the following energy profile for a catalysed
reaction?
Energy F
E3
E1
E2
Extent of reaction
A F is the intermediate formed.

B The enthalpy change of the reaction is E 2 E 3 .
C The reaction is catalysed by a heterogenous catalyst.
D The second step of the reaction is the rate determining step.
12 Ethyl ethanoate undergoes a slow acid-catalysed hydrolysis in water where the concentration
of acid in the solution remains constant.
H+
CH 3 CO 2 CH 2 CH 3 + H 2 O CH 3 CO 2 H + CH 3 CH 2 OH
The rate equation is found to be

rate = k[CH 3 CO 2 CH 2 CH 3 ][H+]
In an experiment, when 1.0 mol dm-3HCl was reacted with 0.10 mol dm-3 ethyl ethanoate, the
half-life was found to be 42 min.
In a second experiment, 2.0 mol dm-3HCl was reacted with 0.20 mol dm-3 ethyl ethanoate.
What is the half-life of the second experiment?
A 10.5 min B 21 min C 42 min D 63 min
13 Ethanol has a pK a of 15.5 at room temperature. Sodium ethoxide can be produced by

reacting ethanol with sodium metal, and Solution P is 0.1mol dm-3 sodium ethoxide.
trendyline
A s a weak acid.
Ethanol is
B Ethoxide is a strong base
base.
C The pH off Solution P is
s 13.
D The type of reaction between ethanol and sod
sodium is acid -base
acid-base

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6
14 Which of the following graphs shows the correct trend in the physical property of the
period 3 elements?
A B
C D
15 Which of the following elements has an oxide with a giant structure and a chloride which is
readily hydrolysed?
A sodium B carbon
C silicon D phosphorus
16 Two experiments are carried out with anhydrous potassium chloride and observations 1
and 2 are made at the end of each experiment.
Experiment 1: Concentrated sulfuric acid is added to potassium chloride and the fumes
produced are bubbled into aqueous potassium bromide solution observation 1.
Experiment 2: Potassium chloride is dissolved in concentrated aqueous ammonia and the
resulting solution is then added to aqueous silver nitrate observation 2.
What are the observations1 and2?
observation1 observation2
A colourless solution colourless solution
B colourless solution white precipitate
preci
C brown solution
own soluti colourless
olourless solution
s
D own solution
brown soluti white precipitate
prec
preci

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7
17 Which property of the Group II elements (magnesium to barium) and their compounds
increases with increasing proton number?
A the magnitude of the enthalpy change of hydration of the metal ion
B the solubility of the sulfate
C the stability of the carbonate to heat
D the tendency to form complex ions
18 Letters written on paper using aqueous ammonium thiocyanate are invisible until turned
blood red by brushing the paper with aqueous iron(III) chloride. If the ammonium
thiocyanate is first made alkaline, the letters turned orange brown and are less clear.
Which of the following substances, when formed on the paper in these reactions, best
explains these observations?
with aqueous ammonium thiocyanate with alkaline aqueous

ammonium thiocyanate
A [Fe(H 2 O) 6 ]3+ Fe(OH) 3
B [Fe(H 2 O) 5 (SCN)]2+ [Fe(H 2 O) 6 ]3+
C [Fe(H 2 O) 5 (SCN)]2+ Fe(OH) 3
D [Fe(H 2 O) 5 (SCN)]2+ [Fe(OH) 4 ]-
19 An energy profile diagram for a single reaction step is shown below.
To which of the following steps in the reaction of ethane with bromine in the presence of
light does this diagram apply?
A CH 3 CH 2 + CH 3 CH 2 CH 3 CH 2 CH 2 CH 3
B CH 3 CH 2 + Br 2 CH 3 CH 2 Br + Br
C CH 3 CH 2 + Br CH 3 CH 2 Br
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D Br 2 Br
B
Br+
+ Br

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20 The oxo reaction is an important industrial process in which an alkene combines directly
with carbon monoxide and hydrogen under suitable conditions. The reaction with ethene is
shown below.
catalyst
CH 2 =CH 2 + CO + H 2 CH 3 CH 2 CHO
hightemperature
and pressure
Which of the following structural formulae correctly represents the product of the oxo
reaction starting with but-2-ene?
A CH 3 CH 2 CH(CH 3 )CHO
B CH 3 CH 2 CH 2 CH 2 CHO
C CH 3 CH 2 COCH 2 CH 3
D (CH 3 ) 2 CHCH 2 CHO
21 Compounds X and Y are isomers with the molecular formula C 3 H 6 O 2 .

O O
C O CH
CH3 3
CH3CH2 C OH
Compound XCompound Y
Which reagent can be used to distinguish between X and Y?
A sodium metal
B 2,4-dinitrophenylhydrazine
C aqueous alkaline iodine
D aqueous sodium hydroxide
22 The compound hex-3-en-1-ol has a strong leafy smell of newly cut grass and is used in
perfumery.
CH 3 CH 2 CH=CHCH 2 CH 2 OH
hex-3-en-1-ol
What are the organic products when hex-3-en-1-ol is treated with hot acidic K 2 Cr 2 O 7 ,
followed by hydrogen gas in the presence of platinum?
A CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 OH
B CH 3 CH 2 CO 2 H and HO 2 CCH 2 CO 2 H
trendyline
C CH 3 CH
H 2 CH
C 2 OH and HOCH 2 CH 2 CH 2 OH
D CH 3 CH
H 2 CH 2 CH 2 CH
C 2 CO 2 H

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9
23 Which of the follow reaction produces an organic species that contains deuterium atom?
NaOD(aq)
A CH3CH2Br
heat
MnO4-, NaOD(aq)
B CH3CH2OH
heat
conc D2SO4
C CH3CH2OH
heat
conc D2SO4
D CH3CO2H + CH3OH
heat
24 Compound Z, C 4 H 6 O 2 , undergoes the following reactions.

It gives a red precipitate with Fehlings solution.
It gives white fumes with PCl 5 .
Upon reaction with hydrogen gas and nickel catalyst, an optically active product
is obtained.
What is compound Z?
O O OH
O
H C CH CH C H
A 2 2 B
H OH O OH
O
C C C H H C C H
C CH2 D C
H H CH 2
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25 Psilocin is the pharmacologically active agent in the body after ingestion of some species
of psychedelic mushrooms.
H
OH
CH2 CH2 N
CH3
N
H
psilocin
Which bond formed by the following orbitals overlap is not present in psilocin?
A sp3 sp3 overlap between two C atoms

B sp2 sp2 overlap between two C atoms
C sp3 sp2 overlap between C and N atoms respectively
D sp3 sp3 overlap between C and N atoms respectively
26 How many stereoisomers are possible for the following compound?
A 23 B 27
C 28 D 210
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27 What is the structure of the compound formed when compound W was heated with
aqueous sodium hydroxide, followed by acidification?
Br Br
NC CONHCH 3
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12
28 Which one of the following shows the given molecules arranged in order of decreasing pK b
values?
A Cl
, Cl ,
B Cl
Cl , ,
C Cl
, Cl ,
D Cl
, , Cl
29 A polypeptide is subjected to hydrolysis.

The following was found:
The enzyme trypsin hydrolyses a peptide bond at the carboxylic end of arginine (arg) to
give 2 tripeptides and gly
The enzyme chemotrypsin hydrolyses a peptide bond at the carboxylic end of
tyrosine (tyr) to give 2 dipeptides and a tripeptide
The chemical cyanogen bromide cleaves the peptide bond at the carboxylic end of
methionine (met) to give a tetrapeptide and a tripeptide
What is the primary structure of the polypeptide?

A protyr-arg-met-tyr-arg-gly
B glyarg-tyr-met-arg-tyr-pro
C protyr-arg-tyr-met-arg-gly
D glyarg-met-tyr-arg-tyr-pro
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30 Carnosine LVDGLSHSWLGHIRUPHGIURP-alanine and histidine, and has been documented in

recent research as having the ability to prevent many of the detrimental effects of aging.
carnosine
The isoelectric point of carnosine is 6.83. Which of the following is the predominant species
present in an aqueous solution at physiological pH 7.4?
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Part 2
For each of the questions in this section, one or more of the three numbered statements 1 to
3may be correct.
Decide whether each of the statements is or is not correct. (You may find it helpful to put a tick
against the statements which you consider to be correct.)
A B C D
1,2 and 3 are 1 and 2 only 2 and 3 only 1 only is
31 Boron nitride, BN, exists in two possible forms, hexagonal boron nitride and cubic boron
nitride. The structure of hexagonal boron nitride and cubic boron nitride are similar to
graphite and diamond respectively.
nitrogen atom
boron atom
hexagonal boron nitride cubic boron nitride
1 There is dative bonding in cubic boron nitride.

2 The layers in hexagonal boron nitride are held together by van der Waals forces.
3 The boron-nitrogen bond in cubic boron nitride is shorter than that in hexagonal
boron nitride.
32 The standard enthalpy changes of combustion of carbon are as follows:

C(graphite) = 393.1 kJ mol-1
C(diamond) = 395.0 kJ mol-1
Which of the following deductions can be made from the data above?
trendyline
1 e is less stable than diamond.
Graphite
2 e has a lower energy content than diamond
Graphite diamon
diamond..
3 nversion
version of diamond to graphite is exothermic.
The conversion exothermic

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A B C D
33 The circuit shown in the diagram was set up.

switch
brass electrode (an alloy 0.05 mol dm-3sulfuric acid platinum electrode
of copper and zinc
A steady current of 1.00 A was passes through the electrolyte for 10 minutes at room
conditions.
Which statements regarding the electrolysis are correct?
1 Zinc dissolves preferentially at the anode.

2 Effervescence is observed at the cathode.
3 pH of the solution increases.
34 Consider the following equilibrium system:

Fe 3 O 4 (s) + CO(g) CO 2 (g) + 3FeO(s) + YH
1 Increasing the temperature causes the position of equilibrium to shift to the right.
2 The equilibrium constant, K C , for this reaction has no units.
3 Adding FeOcauses the position of equilibrium to shift to the left.
35 Which of the following shows a general decrease for Period 3 chlorides from MgCl 2 to PCl 5 ?
trendyline
1 pH of the resulting solution when dissolve in water
2 m oxidation states of the elements in the chlorides
maximum chloride
3 electrical conductivity in solid state

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16

A B C D
36 The following data refer to copper as a typical transition element and to calcium as an s-
block element.
For which property are the data under the correct element?
property copper calcium
1 density/g cm-3 8.92 1.54
2 melting point/C 1085 842
3 electrical conductivity/ relative units 9.6 85
37 Consider the following equilibria shown together with the magnitude of their respective
equilibrium constants:
[Ni(H 2 O) 6 ]2+ + 6NH 3 [Ni(NH 3 ) 6 ]2+ + 6H 2 O
K stab = [[Ni(NH 3 ) 6 ]2+] = 2.0 x 108
[[Ni(H 2 O) 6 ]2+][NH 3 ]6
[Ni(H 2 O) 6 ]2+ + 3en [Ni(en) 3 ]2+ + 6H 2 O

K stab = [[Ni(en) 3 ]2+] = 4.0 x 1018
[[Ni(H 2 O) 6 ]2+][en]3
whereen represents ethylenediamine, a bidentate ligand.
1 Ammonia is a stronger ligand than water.

2 Ethylenediamine is a stronger ligand than ammonia.
3 The equilibrium constant, K stab , for the following reaction is equal to K stab / K stab :
[Ni(NH 3 ) 6 ]2+ + 3en [Ni(en) 3 ]2+ + 6NH 3
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17

A B C D
38 Epoxy resins are polymers which are used in adhesives. One monomer used in their
manufacture has the following structure:
CH 2
CH CH 2
C l
This monomer is manufactured from propene in three stages:
CH CH
Cl2 (g) CH CH C
Stage I : CH2 3 CH2 2 l
Cl2 (aq) CH CH C
CH CH C CH2 2 l
Stage II : CH2 2 l
Cl OH
CH CH C OH- (aq) CH CH CH C
CH2 2 l 2 2 l
Stage III :
Cl OH
O
Which statements are correct for the above synthesis?
1 Stage I involves free radical substitution.

2 Stage II involves electrophilic addition.
3 Stage III involves nucleophilic addition.
39 Ovalbumin is the predominant protein in egg white.

A perfect poached egg, with firm white surrounding a velvety yolk, can be made by the
addition of vinegar into boiling water, before tipping the egg in and leaving it to cook for 1-2
minutes.
The addition of vinegar allows the egg white to coagulate faster around the yolk, instead of
dispersing in the water. Which of the following explains this observation?
1 H+ in vinegar denatures ovalbumin by protonating the R groups of amino acid
residues.
trendyline
2 H+ in vinegar
negar
egar denatures ovalbumin by protonating the N atom of the p
peptide linkages.
3 H+ in vinegar
negar denatures ovalbumin by breaking it down to its constitu
constituent amino acids.

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18

A B C D
40 Which of the following reagents can be used to distinguish between the two compounds
shown below?
1 aqueous bromine
2 acidified KMnO 4 , reflux
3 CH 3 Br with heating, followed by the addition of AgNO 3
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1
PRELIMINARY EXAMINATIONS
s HIGHER 2
CANDIDATE
NAME
CIVICS
GROUP /
CENTER INDEX
S
NUMBER NUMBER
CHEMISTRY 9647/02
Paper 2 Structured Questions 29th August 2016
2 hours

Write your Civics Group, centre number, index number and name on all the work you
hand in.
Answer all questions. For Examiners Use

The use of an approved scientific calculator is expected, 1 / 12
where appropriate.
A Data Booklet is provided. 2 / 15
3 / 12
At the end of the examination, fasten all your work securely
together. 4 /9
The number of marks is given in brackets [ ] at the end of 5 /24
each question or part question.
Paper 1 / 40
Paper 3 / 80
Total
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This
Answer all
A ll the
2 printed pages.
th questions
ti
2016 TJC H2 Chemistry Preliminary Exam [Turn over

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2
1 Planning (P)
Potentiometric titration is a technique similar to direct titration of a redox reaction and can
be used to determine the concentration of a reducing ion such as Fe2+ without the use of an
indicator. It involves measurement of E cell at intervals as anoxidising titrantis added. The
titration is carried out on one side of a cell whose other half is a reference electrode which
can be a standard hydrogen electrode or a calomel electrode.
Consider the titration of Fe2+ with standard Ce4+, the course of which is monitored
potentiometrically as shown in Figure 1 below. The reference electrode used is the calomel
electrode shown in Figure 2.
Figure 1: Set-up for potentiometric

Figure 2: A calomel titration
electrode
Titration reaction: Fe2+ + Ce4+ Fe3+ +
To follow the course of the reaction, a pair of electrodes is inserted into the reaction mixture.
At the calomel reference electrode,
Reference half reaction is:Hg 2 Cl 2 (s) + 2e 2Hg(l) + 2Cl- E = + 0.24 V
At the suitable electrode, there are two reactions that will come to equilibrium:
Fe3+ + e Fe2+ E = + 0.77 V

Ce4+ + e Ce3+ E = + 1.70 V
As the Ce4+ titrant is added, Fe2+ is oxidised to Fe3+and the cell potential is controlled by the
ratio of reduced and oxidised iron according to the Nerst equation which causes the
potential to rise as more iron becomes oxidised.
[Fe2 ]
E(Fe3+/Fe2+) 0.24.(1)
trendyline
y
E cell = - 0.05916log
[Fee3 ]
valence point is reached, the Fe2+ will have been totally co

When the equivalence consumed, and the
en be controlled by the concentration ratio of Ce33+/ C
potential will then Ce4+. Thus beyond the
C 4+/Ce3+ cell with excess Ce4+.
end-point the potential rises rapidly to that of a Ce

1468 trendyline
3
[Ce3 ]
E cell = E(Ce4+/Ce3+) - 0.05916 log 0.24..(2)
[Ce 4 ]
A graph of E cell against volume of titrant added can be drawn and the resulting titration curve
looks much like the familiar acid-base titration curve. The end point is found not by
measuring a particular cell voltage, but by finding what volume of titrant gives the steepest
part of the curve.
Solution FA 1 was prepared by dissolving 0.960 g of iron tablets in 100 cm3 of 1 mol dm-3
HClO 4 acid. By titration method using KMnO 4 , the percentage of iron(II) ions in the iron
tablets used to make FA 1 was found to be 12.5%. A student wishes to verify the
percentage of iron(II) ions present in FA 1 by potentiometric titration using standard 0.100
mol dm-3 Ce4+ solution.
(a) Suggest a suitable electrode for the potentiometric titration between Fe2+ and Ce4+
solution.
Suitable indicator electrode:
[1]
(b) Perform a pre-calculation to estimate the end-point volume for the potentiometric
titration of 100 cm3 of FA 1 with 0.100 mol dm-3Ce4+ solution.
[1]
trendyline
trendylin
dyline
(c) Using allll the
t above information including
uding the estimated
estim end-point
end-point volume, you are
required to writea plan to verify e percentage of Fe2+ present inFA
verifythe inFA1by potentiometric
titration.
You may assume that you are provided with the following:
followin

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4
100 cm3 of FA 1 solution prepared by dissolving 0.960 g of iron tablets in 1 mol dm-3
HClO 4 acid.
1.25 mol dm-3 Ce4+ solution
a calomel reference electrode
a suitable electrode
a voltmeter
the apparatus normally found in a school laboratory.
Your plan should include details of
the preparation of 0.100 mol dm-3 Ce4+solution

how the electrochemical cell set-up in Figure 1 is assembled
how you would recognize that the end-point has been reached
a table for the recording of readings needed for the plotting of titration curve,
showing suitable volumes of titrant added
the calculation to verifythe percentage of Fe2+ in FA 1 in terms of theend-point
volume, V o cm3 of Ce4+
trendyline
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5
[6]
trendyline
tre
(d) Use the Nerst equation (1)) and (2) to calculate theE ce
cell values when
(i) e3+] = [Fe2+]

[Fe

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6
E cell :
(ii) [Ce3+] = [Ce4+]
E cell :
[1]
(e) If the end-point volume is V o cm3 of Ce4+, sketch the graph you would expect to obtain.
Show clearly in your sketch, the titration volumes in terms of V o when you will be
obtaining the E cell values calculated in (d)(i) and (d)(ii).
[3]
[Total:12]
trendyline
Gases A and B react as shown in the equation given.
given

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7
GasesA, B and D were injected into a vessel at 25oC and allowed to reach dynamic
equilibrium. The graph below (not drawn to scale) shows how the concentration of the four
gases varies with time.
concentration / moldm-3
3.0
A and B
0.25
0.1 C
0
t0 t1 t2 t3 t4 time
(a) (i) Explain what is meant by dynamic equilibrium.
[1]
(ii) Write an expression for K c for this equilibrium, stating the units.
[1]
(iii)
trendyline
Calculate
alculate the value for K c at time,
time t 1 .

1473 trendyline
8
[2]
(b) (i) State Le Chateliers principle.
[1]
At time, t 2 , the volume of the system was reduced which lead to an increase in
concentration of the gases. This causes the position of the equilibrium to shift.
(ii) Suggest and explain what happens to the system between time t 3 to t 4 .
[2]
(iii) Sketch on the same axes how the concentration of the four gases will change when
more gas C was introduced at time, t 4 .
trendyline
[2]
(iv) State
tate explain the effect of the presence of a catalyst on the equilibrium
ate and explain
position
sition and the value of the equilibrium constant.
osition constant

1474 trendyline
9
[2]
(c) The standard Gibbs free energy change of reaction, Go in J mol-1, is related to the
equilibrium constant by the following equation.
Go = RT ln (0.02478K c )
(i) Using your answer in (a)(iii), calculate Goin kJ mol-1.
[1]
(ii) Explain the significance of the sign of your answer in (c)(i).
[1]
(iii) Using your answer in (c)(i) and any other information on page 7, calculate So.
[2]
3 (a) trendyline
1- chloropropane
opropane can be synthesized by the following reaction at roo
[Total: 15]
room temperature.

1475 trendyline
10
uv light
CH 3 CH 2 CH 3 (g) + Cl 2 (g) CH 3 CH 2 CH 2 Cl(g) + HCl(g) -------- Reaction I
With reference to the Data BookletFDOFXODWHH r of Reaction I.
[1]
(b) An alternate method of synthesis of 1-chloropropane is as follows:

CH 3 CH 2 CH 2 OH(l) + PCl 5 (s) CH 3 CH 2 CH 2 Cl(l) + POCl 3 (l) + HCl(g) ----Reaction II
(i) Suggest one reason why Reaction II is a better method to produce 1-

chloropropane than Reaction I.
[1]
(ii) Suggest whether the standard change in entropy of Reaction II is likely to be

positive or negative, explaining your reasoning.
trendyline
[2]

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11
(c) 1-chloropropane is an important reactant in the synthesis of propylbenzene:

C 6 H 6 (l) + CH 3 CH 2 CH 2 Cl (l) C 6 H 5 CH 2 CH 2 CH 3 (l) + HCl(g) ----- Reaction III
(i) Define standard enthalpy change of formation.
[1]
(ii) Using the data listed below,

H f o/kJ mol-1
CH 3 CH 2 CH 2 Cl(l)161.3
HCl(l) 167.2
C 6 H 6 ( l) +49.0
C 6 H 5 CH 2 CH 2 CH 3 (l)38.4
enthalpy change of vapourisation of HCl is +74.9 kJ mol-1
FRQVWUXFWDQHQHUJ\F\FOHWRFDOFXODWHH r of Reaction III.
trendyline [2]

1477 trendyline
12
(d) Propylbenzene is a fuel additive and solvent.It undergoes the following chemical
reactions.
ICl,
AlCl3
PCl5
(i) State the reagents and conditions for the following steps:
Step 1 :
Step 2 :
[2]
(ii) Draw the structural formula of the organic compounds X, Y and Z.
X: Y:
trendyline
trendyline
1478 trendyline
13
Z:
[3]
[Total:12]
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14
4 When propanone vapour is passed over a heated filament, it breaks down into methane and
a reactive substance called ketene.
O
||
1
CH 3 C CH 3 CH 4 + CH 2 = 2C = O
ketene
(a) (i) Draw the hybrid orbitals around each of the 2 carbon atoms, 1C and 2C in ketene
molecule. State the type of hybridisation for each carbon atom.
Carbon atom 1C Carbon atom 2C
Hybridisation: .... Hybridisation: .
[2]
(ii) Draw the displayed formula for the ketene molecule and on it show suggested
values of the bond angles around 1C and 2C atoms.
[1]
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1480 trendyline
15
Ketene is a highly reactive compound. It readily undergoes the reactions shown below.
CH 2 = C = O + HCl CH 3 C = O
|
Cl
CH 2 = C = O + H 2 O CH 3 C = O
|
OH
(b) Name and describe the mechanism for the reaction between ketene and water,
showing all charges and using curly arrows to show the movement of electron pairs.
[3]
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1481 trendyline
16
(c) Ketene reacts with ethanol to form a sweet smelling compoundP, C 4 H 8 O 2 , which
reacts with LiAlH 4 to give Q.Identify P and Q. Name the type of reaction for the
transformation of P to Q.
P Q
Type of reaction from P to Q:

[3]
[Total: 9]
trendyline
1482 trendyline
17
5 Ethanedioic acid, H 2 C 2 O 4 , reacts with sodium hydroxide to form sodium ethanedioate,

Na 2 C 2 O 4 . One of the main applications of ethanedioate ions is in rust-removal, as
ethanedioate ions form water-soluble derivatives with iron(III) ions.
(a) An electrochemical cell is set up using Cu2+/Cu and CO 2 /C 2 O 4 2- half-cells. The

electrode in CO 2 /C 2 O 4 2- half-cell is the negative electrode and the cell potential is
+0.77V.
(i) Using relevant data from the Data Booklet, determine the electrode potential of
the CO 2 /C 2 O 4 2- half-cell.
[2]
(ii) A small quantity of solid potassium iodide is added to the Cu2+/Cu half-cell. Write
an equation and state the observations for the reaction that will occur in this half-
cell. Hence, predict and explain the effect on the e.m.f. of the electrochemical
cell.
[3]
trendyline
1483 trendyline
18
(b) The K a values for the step-wise dissociation of ethanedioic acid are given below.
HO 2 C-CO 2 H HO 2 C-CO 2 - + H+ K a1 = 5.6 x 10-2 mol dm-3

HO 2 C-CO 2 --O 2 C-CO 2 - + H+ K a2 = 5.4 x 10-5 mol dm-3
Calculate the pH of 0.10 mol dm-3 of sodium ethanedioate salt, Na 2 C 2 O 4 .
[2]
(c) Hydrated salt of magnesium ethanedioate has the formula MgC 2 O 4 .nH 2 O. When
6.18 g of hydrated magnesium ethanedioate is heated strongly, a white solid W
and three gases X, Y and Z are generated. Gases X, Y and Z are passed through
anhydrous calcium chloride, followed by aqueous sodium hydroxide. The flasks
containing anhydrous calcium chloride and aqueous sodium hydroxide had an
increase in mass of 1.50 g and 1.83 g respectively. The residual gas Z occupied 1
dm3 at room temperature and pressure. Gas Z is poisonous and can be heated
with oxygen to give gas Y.
(i) Suggest the identities of W, X, Y and Z.
W:
X:
Y:
Z:
trendyline
[2]

1484 trendyline
19
(ii) Hence, determine the value of n, showing your working clearly.
[3]
(iii) Ethanedioate ions form insoluble precipitates with many metal ions, one of
which is calcium ethanedioate, a primary constituent of kidney stones.
Calcium ethanedioate decomposes in the same manner as magnesium

ethanedioate. Using relevant data from the Data Booklet, deduce whether
calcium ethanedioate would decompose at a higher or lower temperature
than magnesium ethanedioate. Explain your reasoning.
trendyline [3]

1485 trendyline
20
(d) A tetradentate ligand, ethylenediamine-N,N-diacetate (EDDA) ion, can be

synthesised from ethanedioic acid through a series of steps. Ethanedioic acid is
first converted to ethane-1,2-diamine through a 3-step synthesis. Steps 4 to 7
represent the mechanism of Skrecker synthesis, which can be used to synthesise
amino acids.
E: F:
step 1 step 2
HO 2 CCO 2 H
ethanedioic acid
step 3
H 2 NCH 2 CH 2 NH 2
ethane-1,2-diamine
step 4
OH H H OH
H C N CH2CH2 N C H
H H
G: step 5
step 6 H C N CH2CH2 N C H
HCN
H H
step 7
OH-(aq), heat
CO2- H H CO2-
trendyline
e
H C N CH2CH2 N C H
H H
EDDA

1486 trendyline
21
(i) Propose the 3-step synthesis for the formation of ethane-1,2-diamine from
ethanedioic acid, naming the reagents and conditions used in each step.
Draw the structures of the intermediate compoundsE and F in the spaces
provided in the synthetic route.
Step 1:
Step 2:
Step 3:
[5]
(ii) Carbonyl compound and amine react in the following way.
O OH H
C
C + R"NH2 R N R"
R R'
R'
Step 4 of the synthetic route in (d) involves the reaction of ethane-1,2-

diamine with 2 moles of a carbonyl compound. Identify the carbonyl
compound.
[1]
(iii) Draw the structure of compound G in the space provided. [1]
(iv) State the types of reaction in step 5 and step 7.
Step 5:
ep 7:
Step
[2]
[Total: 24]

1487 trendyline
1
PRELIMINARY EXAMINATIONS
s HIGHER 2
CANDIDATE
NAME
CIVICS
GROUP /
CENTER INDEX
S
NUMBER NUMBER
CHEMISTRY 9647/02
Paper 2 Structured Questions 29th August 2016
2 hours

Write your Civics Group, centre number, index number and name on all the work you
hand in.
Answer all questions. For Examiners Use

The use of an approved scientific calculator is expected, 1 / 12
where appropriate.
A Data Booklet is provided. 2 / 15
3 / 12
At the end of the examination, fasten all your work securely
together. 4 /9
The number of marks is given in brackets [ ] at the end of 5 /24
each question or part question.
Paper 1 / 40
Paper 3 / 80
Total
trendyline rinted pages.


1488 trendyline
2
Answer all the questions
1 Planning (P)
Potentiometric titration is a technique similar to direct titration of a redox reaction and can
be used to determine the concentration of a reducing ion such as Fe2+ without the use of an
indicator. It involves measurement of E cell at intervals as anoxidising titrantis added. The
titration is carried out on one side of a cell whose other half is a reference electrode which
can be a standard hydrogen electrode or a calomel electrode.
Consider the titration of Fe2+ with standard Ce4+, the course of which is monitored
potentiometrically as shown in Figure 1 below. The reference electrode used is the calomel
electrode shown in Figure 2.
Figure 1: Set-up for potentiometric

Figure 2: A calomel titration
electrode
Titration reaction: Fe2+ + Ce4+ Fe3+ +
To follow the course of the reaction, a pair of electrodes is inserted into the reaction mixture.
At the calomel reference electrode,
Reference half reaction is:Hg 2 Cl 2 (s) + 2e 2Hg(l) + 2Cl- E = + 0.24 V
At the suitable electrode, there are two reactions that will come to equilibrium:
Fe3+ + e Fe2+ E = + 0.77 V

Ce4+ + e Ce3+ E = + 1.70 V
As the Ce4+ titrant is added, Fe2+ is oxidised to Fe3+and the cell potential is controlled by the
ratio of reduced and oxidised iron according to the Nerst equation which causes the
t dyli
trendyline
potential to rise
e as more iron becomes oxidised.
oxidise
[Fe2 ]
E cell = E(Fee3+/Fe
Fe2+) - 0.0591
0.05916log
log 0.24.(1)
[Fe3 ]
e2+ will have been totally consumed, and the

When the equivalence point is reached, the Fe

1489 trendyline
3
potential will then be controlled by the concentration ratio of Ce3+/ Ce4+. Thus beyond the
end-point the potential rises rapidly to that of a Ce4+/Ce3+ cell with excess Ce4+.
[Ce3 ]
E cell = E(Ce4+/Ce3+) - 0.05916 log 0.24..(2)
[Ce 4 ]
A graph of E cell against volume of titrant added can be drawn and the resulting titration curve
looks much like the familiar acid-base titration curve. The end point is found not by
measuring a particular cell voltage, but by finding what volume of titrant gives the steepest
part of the curve.
Solution FA 1 was prepared by dissolving 0.960 g of iron tablets in 100 cm3 of 1 mol dm-3
HClO 4 acid. By titration method using KMnO 4 , the percentage of iron(II) ions in the iron
tablets used to make FA 1 was found to be 12.5%. A student wishes to verify the
percentage of iron(II) ions present in FA 1 by potentiometric titration using standard 0.100
mol dm-3 Ce4+ solution.
(a) Suggest a suitable electrode for the potentiometric titration between Fe2+ and Ce4+
solution.
Suitable indicator electrode: Pt [1]
(b) Perform a pre-calculation to estimate the end-point volume for the potentiometric titration
of 100 cm3 of FA 1 with 0.100 mol dm-3Ce4+ solution.
No of moles of Fe2+ in 100 cm3 of FA 1 = (0.125 x 0.960) 55.8 = 0.00215 mol
Vol of Ce4+required to reach the end-point = (0.00215 0.100) dm3 = 21.50 cm3[1]
(c) Using all the above information including the estimated end-point volume, you are
required to writea plan to verifythe percentage of Fe2+ present inFA1by potentiometric
titration.
100 cm3 of FA 1 solution prepared by dissolving 0.960 g of iron tablets in 1 mol dm-3
HClO 4 acid.
1.25 mol dm-3 Ce4+ solution
a calomel reference electrode
a suitable electrode
a voltmeter
the apparatus normally found in a school laboratory.
t dy
trendyl
trendyline
Your plan
n sshould include details off
eparation of 0.100 mol dm-3 Ce

the preparation e44+solution
how thee electrochemical
ectrochemical cell set-up in Figure 1 is assembled
how you would ld recognize
i that
th t the end-point
d point ha
has b
been reached
a table for the recording of readings needed for the plotting of titration curve,

1490 trendyline
4
showing suitable volumes of titrant added

the calculation to verifythe percentage of Fe2+ in FA 1 in terms of theend-point
volume, V o cm3 of Ce4+
Preparation of the standard 0.100 mol dm-3 Ce4+solution

1. Using a burette, transfer 20.00 cm3of 1.25 mol dm-3 Ce4+ solution directly into
a 250 cm3 standard flask.
2. Make up to the mark with distilled water. Stopper and shake well to obtain a
homogeneous solution.
1mcorrect volume for dilution using burette/pipette for measurement.
1m- using a standard & logical procedure in the preparation
Procedure to record cell potential in the potentiometric titration
1. Transfer the given 100.0 cm3 of FA 1 solution into a 500 ml beaker.
2. Fill a burette with the prepared 0.100 mol dm-3Ce4+ solution.
3. Assemble the apparatus as shown in Figure 1.
4. Titrate FA 1 solution with Ce4+solution . Read and record the cell voltage
registered on the voltmeter as each aliquot of Ce4+solution is introduced
from the burette.Carry out a more careful titration by adding titrant in small
increments as the volume gets close to the equivalence point.
5. The end-point volume is reached when the E cell value switches from cell
potential based on Fe3+/Fe2+ to one based on Ce4+/Ce3+.
Table of readings
Volume of Ce4+ solution added / cm3 E cell / V

5.00
10.00
15.00
17.00
19.00
21.00
23.00
25.00
30.00
35.00
40.00
45.00
1m Procedure on the assembly of set-up as in figure 1 and titrating carefully

by adding titrant in small increments nearing the end-point
1m -how to recognize that the end-point had been passed
1m table of readingswith volume exceeding 21.50 cm3 of Ce4+solution
Calculationof % of Fe2+ in FA 1 in terms of end-point volume, V o cm3of Ce4+soluton
No of moles of Ce4+ used = 0.100V o 1000 mol = 10-4 V o
trendyline
y
ol of Fe2++ present
= no of moles re in 100 cm3 of FA 1
Mass of Fe22+ present in 0.960 g of iron tablets = 1
10-44 V o x 55.8 = 5.58 x 10-3V o g
Hence % of Fe2+ in FA 1 = (5.58 x 10-3 V o 0.960) x 100 = 0.581V o % [6]
(d) Use the Nerst equation (1) and (2) to calculate

l theE cell values when

1491 trendyline
5
(i) [Fe3+] = [Fe2+] and

(ii) [Ce3+] = [Ce4+].
(i) E cell = +0.53 V (ii) E cell = +1.46V [1]
(e) If the end-point volume is V o cm3 of Ce4+, sketch the graph you would expect to obtain.
Show clearly in your sketch, the titration volumes in terms of V o when you will be
obtaining the E cell values calculated in (d)(i) and (d)(ii).
Shape of titration with axes clearly labelled.

E cell at X = +0.53 V at V o when [Fe2+] = [Fe3+]
E cell at Y = +1.46V at 2V o when [Ce3+] = [Ce4+][3]
[Total:12]
trendyline
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6
2 Gases A and B react as shown in the equation given.
GasesA, B and D were injected into a vessel at 25oC and allowed to reach dynamic
equilibrium. The graph below (not drawn to scale) shows how the concentration of the four
gases varies with time.
concentration / moldm-3
3.0
A and B
0.25
0.1 C
t0 t1 t2 t3 t4 time
(a) (i) Explain what is meant by dynamic equilibrium.
When a reversible reaction reaches a state of dynamic equilibrium, reaction

continues to occur but the rates of the forward and backward
reactions areequal such that there is no net change in the concentrations of the
reactants and products.
[1]
(ii) Write an expression for K c for this equilibrium, stating the units.
K c = [C][D]2/[A][B] mol dm-3
[1]
trendyline
1493 trendyline
7
(iii) Calculate the value for K c at time, t 1 .
Initial conc. / mol dm-3 0.25 0.25 0 3.0
Change in conc. / mol dm-3 0.1 0.1 + 0.1 + 0.2
Equil. conc. / mol dm-3 0.15 0.15 0.13.2
K c = 0.1 x 3.22 / 0.15 x 0.15 = 45.5mol dm-3
[2]
(b) (i) State Le Chateliers principle.
If a system at dynamic equilibrium is subjected to a change which disturbs the

equilibrium, the system will respond in such a way so as to counteract the effect of
the change so as to re-establish the equilibrium.
[1]
At time, t 2 , the volume of the system was reduced which lead to an increase in
concentration of the gases. This causes the position of the equilibrium to shift.
(ii) Suggest and explain what happens to the system between time t 3 to t 4 .
Position of equilibrium shifts to the left as concentration of A and B increases

gradually and concentration of C and D decreases gradually.
Since the backwardreaction is exothermic, hence the temperature of the system

must have beendecreasedat time, t 3 .
[2]
(iii) Sketch on the same axes how the concentration of the four gases will change when
more gas C was introduced at time, t 4 .
Sharp increase in [C] followed by decrease in [C], decrease in [D] and increase
in [A]&[B]
Decrease in [D] is twice the increase in [A], [B] and [C]. Equilibrium [C] should
not be lower than the initial [C] at t 4 .
[2]
(iv)
trendyline
osition
y
tate and explain the effect of the presence of a catalyst on the
State
sition and the value of the equilibrium constant.
position
equ
constant
A catalyst have no effect on the equilibrium

th equilibrium
position and the vvalue of K c.

1494 trendyline
8
The presence of catalystincreases the rate of the forward and backward reaction
to the same extent. (K C = k f / k b K c constant.)
[2]
(c) The standard Gibbs free energy change of reaction, Go in J mol-1, is related to the
equilibrium constant by the following equation.
Go = RT ln (0.02478K c )
(i) Using your answer in (a)(iii), calculate Goin kJ mol-1.
8.31 x 298 x ln (0.02478 x 45.5)

Go = = 0.297kJ mol-1
1000
[1]
(ii) Explain the significance of the sign of your answer in (c)(i).
Since Go< 0, the reaction is spontaneous at room temperature.
[1]
(iii) Using your answer in (c)(i) and any other information on page 7, calculate So.
Go = Ho TSo
So = [90 (0.297)] / 298 = +303 J mol-1K-1
Note: sign must be shown
[2]
[Total: 15]
3 (a) 1- chloropropane can be synthesized by the following reaction at room temperature.
uv light
CH 3 CH 2 CH 3 (g) + Cl 2 (g) CH 3 CH 2 CH 2 Cl(g) + HCl(g) -------- Reaction I
With reference to the Data BookletFDOFXODWHH r of Reaction I.
Bonds broken: 1 C-H bond, 1 Cl-Cl bond

Bonds formed: 1 C-Cl bond, 1 H-Cl bond
trendyline

+
+r
+ = +(410+244) (340+431)
43
J mol-11
= 117 kJ
[1]

1495 trendyline
9
(b) An alternate method of synthesis of 1-chloropropane is as follows:

CH 3 CH 2 CH 2 OH(l) + PCl 5 (s) CH 3 CH 2 CH 2 Cl(l) + POCl 3 (l) + HCl(g) ----Reaction
II
(i) Suggest one reason why Reaction II is a better method to produce

1-chloropropane than Reaction I.
Reaction I can undergo further free-radical substitution to give a mixture of

halogenoalkanes thus the yield is much lower compared to Reaction II.
[1]
(ii) Suggest whether the standard change in entropy of Reaction II is likely to be
positive or negative, explaining your reasoning.
So is likely to be positive.

This is because in the reaction, gaseous molecules are formed& highly
disordered.There are more ways to arrange the molecules and distribute
the energy.
[2]
(c) 1-chloropropane is an important reactant in the synthesis of propylbenzene:
C 6 H 6 (l) + CH 3 CH 2 CH 2 Cl (l) C 6 H 5 CH 2 CH 2 CH 3 (l) + HCl(g) ----- Reaction III
(i) Define standard enthalpy change of formation.
The standard enthalpy change of formation of a substance, H f o, is the

enthalpy change when one mole of the substance is formed from its constituent
elementsin their standard states at 298 K and 1 atm.
[1]
(ii) Using the data listed below,

H f o/kJ mol-1
CH 3 CH 2 CH 2 Cl(l)161.3
HCl(l) 167.2
C 6 H 6 ( l) +49.0
C 6 H 5 CH 2 CH 2 CH 3 (l)38.4
enthalpy change of vapourisation of HCl is +74.9 kJ mol-1
FRQVWUXFWDQHQHUJ\F\FOHWRFDOFXODWHH r of Reaction III.
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1496 trendyline
10
C6H6(l) + CH3CH2CH2Cl (l) C6H5CH2CH2CH3(l) + HCl(g)

Hor
+49.0 + (-161.3)
- 38.4 + (- 167.2) + 74.9
9C(s) + 13/2H2(g) + Cl2(g) C6H5CH2CH2CH3(l) + HCl(l)
FRUUHFWHQHUJ\F\FOHstate symbols and coefficients)

By Hess Law, +49.0 + (-161.3) + Ho r = -38.4 + (- 167.2) + 74.9
Ho r = - 18.4 kJ mol-1
[2]
(d) Propylbenzene is a fuel additive and solvent.It undergoes the following chemical
reactions.
ICl,
AlCl3
PCl5
(i) State the reagents and conditions for the following steps:
Step 1 : Concentrated H 2 SO 4 , concentrated HNO 3 , UHIOX[0C
Step 2 : Heat under reflux with Sn, concentrated HCl, followed by

NaOH (aq)
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[2]
(ii) Draw
raw
aw the structural formula of the organic
organi compounds X, Y and Z.

1497 trendyline
11
X: or Y:
Z:
[3]
[Total:12]
4 When propanone vapour is passed over a heated filament, it breaks down into methane and
a reactive substance called ketene.
O
||
1
CH 3 C CH 3 CH 4 + CH 2 = 2C = O
ketene
(a) (i) Draw the hybrid orbitals around each of the 2 carbon atoms, 1C and 2C in ketene
molecule. State the type of hybridization for each carbon atom.
Carbon atom 1C Carbon atom 2C
Hybridisation: sp2 Hybridisation: sp
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[2]

1498 trendyline
12
(ii) Draw the displayed formula for the ketene molecule and on it show suggested
values of the bond angles around 1C and 2C atoms.
[1]
Ketene is a highly reactive compound. It readily undergoes the reactions shown below.
CH 2 = C = O + HCl CH 3 C = O
|
Cl
CH 2 = C = O + H 2 O CH 3 C = O
|
OH
(b) Name and describe the mechanism for the reaction between ketene and water,
showing all charges and using curly arrows to show the movement of electron pairs.
Name of mechanism: Electrophilic Addition
Step 1:
Step 2:
[3]
(c) Ketene reacts with ethanol to form a sweet smelling compoundP, C 4 H 8 O 2 , which
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t LiAlH 4 to give Q.Identify
reacts with y P and Q. Na
Name the type o
of reaction for the
transformation
mation of P to Q
Q..

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13
P Q
Type of reaction from P to Q: Reduction

[3]
[Total: 9]
5 Ethanedioic acid, H 2 C 2 O 4 , reacts with sodium hydroxide to form sodium ethanedioate,

Na 2 C 2 O 4 . One of the main application of ethanedioate ions is in rust-removal, as
ethanedioate forms water-soluble derivatives with iron(III) ions.
(a) An electrochemical cell is set up using Cu2+/Cu and CO 2 /C 2 O 4 2- half-cells. The
electrode in CO 2 /C 2 O 4 2- half-cell is the negative electrode and the cell potential is
+0.77V.
(i) Using relevant data from the Data Booklet, determine the electrode potential of
the CO 2 /C 2 O 4 2- half-cell.
E Cu2+/Cu = +0.34V = E red
E cell = E red - E ox
+0.77 = +0.34 - E CO2/C2O42-
E CO2/C2O42- = -0.43V
[2]
2+
(ii) A small quantity of solid potassium iodide is added to the Cu /Cu half-cell. Write
an equation and state the observations for the reaction that will occur in this half-
cell. Hence, predict and explain the effect on the e.m.f. of the electrochemical
cell.
2Cu2+(aq) + 4I-DT&XI(s) + I 2 (aq)
White ppt in brown solution/ brown ppt observed in the Cu2+/Cu half-cell.
Since CuI is formed, the [Cu2+(aq)] will decrease. E Cu2+/Cu (E red ) will become
more negative and the e.m.f. of the electrochemical cell will be less positive/
decrease.
[3]
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e
(b) The K a va
values for the step
step-wise
-wise dissociation
ciation of ethanedioic
ethan acid are given
g below.
O 2 C-
HO C-CO
CO 2 H CO 2 - + H+
HO 2 C-CO 1 -2 mol dm
K a1 = 5.6 x 10 d -3

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14
HO 2 C-CO 2 --O 2 C-CO 2 - + H+ K a2 = 5.4 x 10-5 mol dm-3
Calculate the pH of 0.10 mol dm-3 of sodium ethanedioate salt, Na 2 C 2 O 4 .

-
O 2 C-CO 2 - + H 2 O HO 2 C-CO 2 - + OH-
[OH-@ . b F [-14/(5.4x10-5) = 4.30 x 10-6 mol
pH = 14 lg(4.30 x 10-6) = 8.63
[2]
(c) Hydrated salt of magnesium ethanedioate has the formula MgC 2 O 4 .nH 2 O. When 6.18
g of hydrated magnesium ethanedioate is heated strongly, a white solid W and three
gases X, Y and Z are generated. Gases X, Y and Z are passed through anhydrous
calcium chloride, followed by aqueous sodium hydroxide. The flasks containing
anhydrous calcium chloride and aqueous sodium hydroxide had an increase in mass
of 1.50 g and 1.83 g respectively. The residual gas Z occupied 1 dm3 at room
temperature and pressure. Gas Z is poisonous and can be heated with oxygen to give
gas Y.
(i) Suggest the identities of W, X, Y and Z.

W: MgO, X: H 2 O
Y: CO 2 , Z: CO
Any 2 correct = 1 mark
[2]
(ii) Hence, determine the value of n, showing your working clearly.
No. of moles of CO = 1/24 = 0.0417 mol
Mass of CO = 0.0417 x (12.0 + 16.0) = 1.17 g
Mass of MgO = 6.18 - 1.50 - 1.83 - 1.17 = 1.68 g
No. of moles of MgO = 1.68/ (24.3 + 16.0) = 0.0417 mol
No. of moles of H 2 O = 1.50/ 18.0 = 0.0833 mol
n = 0.0833/ 0.0417 = 2
[3]
(iii) Ethanedioate ions form insoluble precipitates with many metal ions, one of which
is calcium ethanedioate, a primary constituent of kidney stones.
Calcium ethanedioate decomposes in the same manner as magnesium

ethanedioate. Using relevant data from the Data Booklet, deduce whether
calcium ethanedioate would decompose at a higher or lower temperature than
magnesium ethanedioate. Explain your reasoning.
Ionic radius of Ca2+ = 0.099 nm, Mg2+ = 0.065 nm
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tren y
Ca2+ is larger than Mg2+, hence
ence possesses
possesse smaller charge charg density / lower
power.. Electron cloud of C 2 O 4 2-- is distorted to a smaller extent and
polarising power
the C-O
C O bond is weaken to a smaller extent.
extent
Calcium ethanedioate has

Calc as a higher decomposition
composition tempera
temperature.
[3]

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15
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16
(d) A tetradentate ligand, ethylenediamine-N,N-diacetate (EDDA) ion, can be synthesised

from ethanedioic acid through a series of steps. Ethanedioic acid is first converted to
ethane-1,2-diamine through a 3-step synthesis. Steps 4 to 7 represent the mechanism
of Skrecker synthesis, which can be used to synthesise amino acids.
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(i) Propose
ropose the 3-step synthesis forr the
t formation of ethane-1,2-diamine
ethane- from

1503 trendyline
17
ethanedioic acid, naming the reagents and conditions used in each step. Draw
the structures of the intermediate compoundsE and F in the spaces provided in
the synthetic route.
Step 1: Anhydrous LiAlH 4 , dry ether as solvent, room temperature
Step 2: PCl 5 (s), cold
Step 3: Excess conc NH 3 in ethanol, heat in sealed tube
Alternative Answer:
Step 1: PCl 5 (s), cold
E: (COCl) 2
Step 2: NH 3 (g), room temperature
F: (CONH 2 ) 2
Step 3: Anhydrous LiAlH 4 , dry ether as solvent, room temperature

[5]
(ii) Carbonyl compound and amine react in the following way.
O OH H
C
C + R"NH2 R N R"
R R'
R'
Step 4 of the synthetic route in (d) involves the reaction of ethane-1,2-diamine

with 2 moles of a carbonyl compound. Identify the carbonyl compound.
CH 2 O
[1]
(iii) Draw the structure of compound G in the space provided. [1]
(iv) State the types of reaction in step 5 and step 7.
ep 5:
Step Elimination
Step
ep 7:
7 Alkaline
li h hydrolysis
d l i
[2]

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18
[Total: 24]
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1
CHEMISTRY 9647/03
Paper 3 Free Response 13th September 2016
2 hours
Additional materials: Answer paper

Graph Paper
Data Booklet

Write your name, Civics Group, Centre number and Index number in the spaces provided on the
cover page and on all the work you hand in.
You may use a HB pencil for any diagrams, graphs or rough working.

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pages
2016TJC H2 Chemistry Preliminary Exam [Turn Over
1506 trendyline
2
Answer any four questions
1 Ethanedioic acid is a substance found in many plant foods. Cabbage is among the plant foods
with high ethanedioic acid content. However, its anion, C 2 O 4 2- can bind to iron to form iron(II)
ethanedioate, which renders much of the iron in cabbage unusable by the body.
(a) 50.0 cm3 sample of iron(II) ethanediaote, FeC 2 O 4 was extracted from 300 g of cabbage,
diluted in water and the solution made up to 250 cm3. A 25.0 cm3 portion of this solution
was acidified and required 26.90 cm3 of 0.0100 mol dm-3 potassium manganate(VII) for
oxidation of iron(II) to iron(III) and ethanedioate ions to carbon dioxide.
(i) State the change in oxidation number for manganese and carbon in the reaction.
[1]
(ii) Write down all the relevant ion-electron halfequations and hence the overall redox
equation for the reaction between potassium manganate(VII) and iron(II)
ethanedioate. [2]
(iii) Calculate the concentration, in mol dm-3, of iron(II) ethanedioate in the original
sample.[2]
(iv) Calculate the number of moles of iron in each gram of cabbage. [1]
(b) Ethanedioic acid dissociates in water according to the following equation.
HOOC-COOH + H 2 O HOOC-COO- + H 3 O+
The table below compares the K a values of three organic acids.
Formula Ka
Ethanoic acid CH 3 COOH 1.74 x 10-5
Ethanedioic acid HO 2 CCO 2 H 6.46 x 10-2
Oxoethanoic acid (CHO)COOH 4.79 x 10-4
With reference to the K a values, comment on the order of acidity of the three organic
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acids. [2]
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3
(c) Compound A,with molecular formula C 5 H 8 O, decolourises aqueous bromine and reacts
with PCl 5 giving off white fumes. Upon refluxing A with acidified potassium
manganate(VII), a symmetrical product B, C 5 H 6 O 5 , is formed. B does not give a red
precipitate with Fehlings solution but an orange precipitate is observed with 2,4-
dinitrophenylhydrazine. 1 mole of B also reacts with 1 mole of Na 2 CO 3 with
effervescence observed. B reacts with NaBH 4 to form C. Deduce the structures of
compounds A, B and C, explaining the chemistry of the reactions involved.
[8]
(d) (i) Describe what you see when separate samples of sodium and sulfur are burned in
excess air. Write equations for the reactions that occur. [2]
(ii) The products resulting from the reactions in (d)(i) both react with water. Write
equations for these two reactions and describe the effect of the resulting solutions
on Universal Indicator solution. [2]
[Total: 20]
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y
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4
2 Thallium is a Group III element discovered in 1861, and its toxicity was quickly noted.
Thallium isotopes and compounds have useful applications, sometimes despite their toxic
nature.
(a) Thallium forms compounds similar to aluminium, and thallium(III) chloride and
thallium(III) fluoride have very different structures and bonding.
(i) Draw and state the shape of thallium(III) chloride, TlCl 3 .

[1]
(ii) In gaseous phase, thallium(III) chloride is able to form a compound with a M r of

621. Draw a dot-and-cross diagram of this compound, and state the Cl-Tl-Cl bond
angle.
[2]
(iii) Explain, in terms of structure and bonding, why thallium(III) fluoride has a high
melting point of 550 oC.[2]
(iv) Thallium is also able to form thallium(I) chloride, which is crystalline in nature.
In the crystal lattice of sodium and potassium chlorides, the co-ordination number
of each ion is 6. In the crystal lattice of thallium(I) chloride, TlCl, the co-ordination
number has a different value.
Suggest an explanation for the co-ordination number in the TlCl lattice being
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different from those in NaCland KCl.[1]
[ ]
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5
(b) Thallium(III) chloride, TlCl 3 , reacts with hot water to produce thallium(III) oxide
precipitate and hydrochloric acid.
(i) Write a balanced equation for the above reaction.[1]
(ii) In an experiment, a 15 g impure sample of thallium(III) chloride (M r = 310.5) was

mixed with hot water, and filtered. Water was then added to the filtrate to make a
standard solution in a 250 cm3 volumetric flask. A 25.0 cm3 aliquot was titrated
against 0.5 mol dm-3 aqueous sodium hydroxide, requiring a titre of 22.00 cm3.
Determine the percentage purity of the sample.
You may assume that the impurities are insoluble in water and are inert.
[2]
(c) Thallium(I) sulfate(M r = 504.1) was often employed as a rodenticide and is highly
poisonous. The lethal dosage is 16 ppm of the rats mass. Assuming a typical rat has a
mass of 230 g, determine the number of moles of thallium(I)sulfate needed to kill a rat.
[2]
(d) Thallium(III) ethanoate, Tl(CH 3 CO 2 ) 3 , is able to react with an alkene through addition.
When cyclohexene reacts with thallium(III) ethanoate, a compound with the molecular
formula C 10 H 16 O 4 is formed. Suggest the structural formula of this compound, and state
the number of stereoisomers that this compound has.[2]
201
(e) Tl is an isotope of thallium that is often used in medical diagnostics due to its
radioactive decay by electron capture with emission of gamma rays. The electronic
configuration of the Tl atom is [Xe]4f145d106s26p1.
Electron capture is a process in which a proton-rich nucleus of an atom absorbs one
electron from the first or second quantum shell to change one proton into a neutron.
201
(i) Suggest the species formed, including the nucleon number, when Tl undergoes
electron capture.[1]
(ii) The species formed immediately after electron capture is known to be in excited
state, before returning to ground state by emitting gamma rays.
Name the orbital where the excited electron is most likely located in, and explain
why high energy gamma rays are emitted when the species return to ground
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state.
ate.
te
[2]]
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6
(iii) A patient is typically injected with 0.02 g of thallium for heart diagnosis. The
following graph shows the radioactive decay (through electron capture) of a 0.02
g sample of 201Tl dissolved in 1 dm3 of inert solvent.
[201Tl] / g dm-3
0.02
0.01
0
100 200 300 Time / h
Using the graph, deduce the order of reaction for the radioactive decay of 201Tl.[2]
(iv) Hence, write the rate equation for this reaction and determine the rate constant,
stating its units.[2]
[Total: 20 m]
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7
3 The halogens and organic halides are useful laboratory reagents and have many applications.
(a) State and explain the difference in the reactions of chlorine and iodine with sodium
thiosulfate respectively. Write balanced equations for the reactions. [3]
(b) Deduce which gas, fluorine or chlorine, would behave more ideally at low pressure.
Explain your answer.
[1]
Organic halides are a group of compounds comprising alkyl halides, ethenylhalides and aryl
halides.
Alkyl halides are used as solvents for relatively non-polar compounds.They are also used as the
starting materials for the synthesis of many compounds.
(c) Alcohols react with hydrogen halides to produce alkyl halides.
(i) Suggest the type of reaction that occur. [1]
(ii) 2-iodopropane is formed from propan-2-ol in the presence of sodium iodide

andconcentrated phosphoric acid.
Explain, with the aid of an equation, why concentrated sulfuric acid is not used.[2]
(d) 2-chloro-2-methylpropane undergoes alkaline hydrolysis to form 2-methylpropan-2-ol.
(i) Name and describe the mechanism of the hydrolysis of 2-chloro-2-methylpropane.

[3]
(ii) With the aid of the Data Booklet, explain what will happen to the rate of reaction if 2-
bromo-2-methylpropane was used instead. [2]
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8
(e) Ethenylchloride is an important industrial chemical mainly used to produce the

polymer,PVC.
Ethynereacts with anhydrous hydrogen chloride gas over a mercuric chloride catalyst to
give ethenyl chloride.
ethyne ethenyl chloride
(i) With the aid of the Data Booklet, determine the enthalpy change of the reaction.
[2]
(ii) Explain why ethenyl chloride does not undergo alkaline hydrolysis readily. [1]
(f) 1-iodopropane can be converted to butylamine via a two-stage synthesis.Butylamineis

then used as an ingredient in the manufacture of pesticide.
(i) Suggest reagents and conditions for the two stages. Draw the structure of the
intermediate compound. [3]
(ii) Suggest a chemical test to distinguish between 1-iodopropane and

1-chloropropane. [2]
[Total: 20]
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1513 trendyline
9
4 Co-Cr alloys are most commonly used to make artificial joints including knee and hip joints
due to high wear-resistance and biocompatibility. However in 2010, faulty Co-Cr alloy hip
joints manufactured by DePuy was removed from market due to leakage of toxic chromium
and cobalt into the body muscles and blood stream.
(a) State the electronic configurations of
(i) an atom of chromium,

[1]
(ii) the Co3+ion. [1]
(b) Why are transition metal complexes coloured? [3]
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1514 trendyline
10
(c) The colour of the complexes can be measured by a spectrometer. The amount of light
absorbed is expressed as an absorbance value. The higher the absorbance, the more
of a particular wavelength of light is being absorbed.
The spectrum below shows the major absorption peaks for [CrL 6 ]3+(aq) and[CrJ 6 ]3+(aq).
Relative
absorbance
[CrJ6]3+(aq)
[CrL6]3+(aq)
300 400 500 600 700 800

Higher energy Lower energy
Wavelength/nm
colour Wavelength/nm
Violet 400-430
Blue 430-490
Green 490-570
Yellow 570-590
Orange 590-620
(i)
trendyline
rend
dyline
li e red
What are the coloursof [CrL 6 ]3+

3
(aq)
aq) and
620-750
620--750
620 5
[CrJ 6 ]3+
a [CrJ 3
(aq)? [2]
1515 trendyline
11
(ii) What deduction can be made from the spectra about the size of the d-orbital
splitting in the two complexes? [2]
Cobalt forms many complexes with ligands such as H 2 O, NH 3 and . The most
common oxidation states of cobalt are +2 and +3.
Cations containing cobalt in these two oxidation states have significantly different colours
even when the ligands are the same.
(d) When H 2 O 2 is mixed with pink Co2+(aq) solution, no significant colour change is
observed.
When Co2+(aq) is mixed with excess NH 3 (aq) a slight colour change occurs and cationQ
is formed.
When cationQ is mixed with H 2 O 2 , a reddish brown solution is observed.
E data for the cobalt complex ions and hydrogen peroxide are given below.
[CoL 6 ]3+ + e- [CoL 6 ]2+E = +1.82V for L = H 2 Oand E = +0.11V for L = NH 3
H 2 O 2 + 2e- 2OH- E = +0.87V
Suggest an explanation for the above observations, giving equations where appropriate
and identify the cationQ.[5]
(e) Explain why the neutral complex formed between a Co2+ ion and two
ions is soluble in cyclohexane.
[1]
The direct oxidation of methanoic acid in a fuel cell, DFAFC, shown below represents
potentially the most efficient method of obtaining useful energy from a renewable fuel.
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12
(f) The electrons pass around the external circuit to the cathode.
The protons produced migrate across the proton exchange membrane, PEM, to the
cathode, where they react with oxygen from air, producing water.
Write the equations for the anode and cathode reactions.Hence construct the equation
for the overall reaction. [2]
(g) One method for the construction of DFAFC, involves electroplating a layer of platinum
onto the surface of the proton exchange membrane, PEM. The electrolyte for this
process is a solution containing Pt(NH 3 ) 4 2+ and Cl- ions. The PEM is the cathode in this
electrolytic cell.
(i) Suggest the half-equation for the cathode reaction that deposits platinum on the
PEM. [1]
(ii) In one such preparation, a PEM with a surface area of 25 cm2 was immersed in
an electrolyte bath and a current of 0.0875 A was passed for 95 minutes.
Calculate the mass of platinum deposited onto the surface of PEM. [2]
[Total: 20]
5 (a) Myoglobin and haemoglobin are globular proteins that serve to bind and deliver oxygen.
The former serves as an intracellular storage site for oxygen in the muscle tissues, while
the latter transports oxygen in the bloodstream.
Each myoglobin molecule contains one haem group.
In deoxygenated myoglobin, a water ligand is weakly bound to the Fe2+ of the haem group
as shown:
haem group
y
1517 trendyline
13
(i) Briefly describe how myoglobin maintains its three-dimensional shape.

[2]
(ii) In the presence of the haem group, the polypeptide chain coalesces into a
myoglobin molecule.
With the aid of the equation,
* + 76
and by considering the chemical interactions involved, explain why this is a
spontaneous process at low temperatures.
[2]
(iii) Deoxygenated myoglobin is responsible for the dull purplish red muscle colour,
observed in the depth of the muscle. When meat is freshly cut, colour change occurs
in two stages:
Stage 1: Bright red colour when muscle surface is exposed to air.
Stage 2: With time, the bright red colour slowly changes to an unattractive, dull
brown colour associated with stale and spoiled meat.
With reference to the structure of the haem group and the reaction that occurs in
each stage, explain the colour changes involved.
[2]
(b) One of the isolated compounds that is primarily responsible for the umami (savory) flavor
is glutamate, which is a salt formed from glutamic acid that is commonly found in meat.
glutamate
t dyli
trendyline
It is thought
ought that glutamate stimulate a specific receptor site located
the tongue,
locate in the taste buds on
gue, which is essentially a protein molecule. A simplified d
site is shown
hown below:
diagram of the receptor
1518 trendyline
14
OH +
H3N
H2 N
(i) State two different types of interactions that can be formed between glutamate and
the receptor protein. Illustrate your answer with labelled diagram(s).
[2]
(ii) To enhance the flavor of food, many retailers in the food industry use monosodium
glutamate (MSG) as a food additive, which can be easily synthesized in the
laboratory.
Given that laboratory synthesis gives a racemic mixture, explain why 50% of the
glutamate synthesized in the laboratory is unable to bind precisely with the correct
orientation to the receptor protein. [1]
The structure of glutamic acid is shown below:
t d li
trendyline
glutamic
ic acid
10 cm3 of the fully protonated glutamic acid is titrated with 20 cm3 o

of 1.00 moldm3 sodium
hydroxide solution. Its titration curve is show
shown below:
1519 trendyline
15
pH
Vol of NaOH / cm3
(iii) Show that the concentration of glutamic acid is 1.0 moldm3 at A.

[1]
(iv) Hence, calculate the pH of the solution at A.

[1]
(v) Identify the specie(s) present at B.

With the help of an equation, explain how the solution at B can resist a change in pH
when a small amount of base is added. [2]
(vi) In a separate experiment, the solution at B was reacted with 10.0 cm3 of
0.05 moldm3 sodium hydroxide.
Calculate the pH of the mixture after the reaction.
You may find it useful to represent the fully protonated glutamic acid as HA.
[2]
(c) Compound P, C 9 H 11 NO 2 , rotates the plane ofpolarised light and reacts with the following
reagents:
aqueous bromine to give compound Q, C 9 H 9 NO 2 Br 2
sodium carbonate to give a salt
PCl 5 to give a 5-membered cyclic compound R
Deduce
t dyli
trendyline
e the structural formulae of compounds P, Q and
nd R.[5]
R.[5
[Total: 20]
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16
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1
CHEMISTRY 9647/03
Paper 3 Free Response 13th September 2016
2 hours
Additional materials: Answer paper

Graph Paper
Data Booklet

Write your name, Civics Group, Centre number and Index number in the spaces provided on the
cover page and on all the work you hand in.
You may use a HB pencil for any diagrams, graphs or rough working.

trendyline
pages
1522 trendyline
2
Answer any four questions
1 Ethanedioic acid is a substance found in many plant foods. Cabbage is among the plant foods
with high ethanedioic acid content. However, its anion, C 2 O 4 2- can bind to iron to form iron (II)
ethanedioate, which renders much of the iron in cabbage unusable by the body.
(a) 50.0 cm3 sample of iron(II) ethanediaote, FeC 2 O 4 was extracted from 300 g of cabbage,
diluted in water and the solution made up to 250 cm3. A 25.0 cm3 portion of this solution
was acidified and required 26.90 cm3 of 0.0100 mol dm-3 potassium manganate(VII) for
oxidation of iron(II) to iron(III) and ethanedioate ions to carbon dioxide.
(i) State the change in oxidation number for manganese and carbon in the reaction.
[1]
Mn: From +7 to +2 [Or decrease by 5]

C: From +3 to +4 [Or increase by 1]
(ii) Write down all the relevant ion-electron halfequations and hence the overall redox
equation for the reaction between potassium manganate(VII) and iron(II)
ethanedioate. [2]
MnO 4 - + 8H+ + 5e- Mn2+ + 4H 2 O

C 2 O 4 2- 2CO 2 + 2e-
Fe2+ Fe3+ + e-
3MnO 4 - + 24H+ + 5C 2 O 4 2- + 5Fe2+ 3Mn2+ + 5Fe3+ + 12H 2 O + 10CO 2
(iii) Calculate the concentration, in mol dm-3, of iron(II) ethanedioate in the original
sample [2]
5
Number of moles of FeC 2 O 4 in 25.0 cm3 = x 2.69 x 10-4
3
= 4.48 x 10-4mol
Number of moles of FeC 2 O 4 in 250 cm3= 4.48 x 10-4 x 250/25.0

= 4.48 x 10-3 mol
4.48 x 10 -3
Concentration of FeC 2 O 4 in the original sample =
50 x 10 -3
= 0.0896 mol dm-3
(iv) Calculate the number of moles of iron in each gram of cabbage. [1]
4.48 x 10 -3
No. of moles of iron per gram of spinach =
300
= 1.49 x 10-5mol/g
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3
(b) Ethanedioic acid dissociates in water according to the following equation.
HOOC-COOH + H 2 O HOOC-COO- + H 3 O+
The table below compares the K a values of three organic acids.
Formula Ka
Ethanoic acid CH 3 COOH 1.74 x 10-5
Ethanedioic acid HO 2 CCO 2 H 6.46 x 10-2
Oxoethanoic acid (CHO)COOH 4.79 x 10-4
With reference to the K a values, comment on the order of acidity of the three organic
acids. [2]
The bigger the K a , the stronger the acid. Acid strength is dependent on the
stability of the anion formed when the acid ionises. The more stable the anion,
the stronger is the acid.
Strength of acid: Ethanedioic acid >Oxoethanoic acid >Ethanoic acid
Oxoethanoic acid is a stronger acid than ethanoic acid as -CHO group is

electron withdrawing. The negative charge on the anion is dispersed, thereby
stabilizing the ion compared to ethanoate ion.
Ethanedioic acid is the strongest acid as stabilisation of the monoanion

byintramolecular hydrogen bonding with the unionised COOH groupresults in
the highest K a value compared with the other two acids.
(c) Compound A,with molecular formula C 5 H 8 O, decolourises aqueous bromine and reacts
with PCl 5 giving off white fumes. Upon refluxing A with acidified potassium
manganate(VII), a symmetrical product B, C 5 H 6 O 5 , is formed. B does not give a red
precipitate with Fehlings solution but an orange precipitate is observed with 2,4-
dinitrophenylhydrazine. 1 mole of B also reacts with 1 mole of Na 2 CO 3 with
effervescence observed. B reacts with NaBH 4 to form C. Deduce the structures of
compounds A, B and C, explaining the chemistry of the reactions involved.
[8]
A decolourises aqueous bromine C=C present

A reacts with PCl 5 giving off white fumes of HCl -OH present
A undergoes oxidation with KMnO 4 where the OH group is oxidised and C=C
in a ring undergoes total bond cleavage to form B
OR A undergoes oxidation with KMnO 4 to give a symmetrical product B with
no loss in C atoms C=C is in a ring and A is a cyclic compound
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y n
B does
oes not give a red precipitate with Fehlin
Fehlings solution bbut form an orange
precipitate -dinitrophenylhydrazine B is a ket
cipitate with 2,4
2,4- ketone and A is a 2o
keto
alcohol
ohol
h
1 mole O 3 B has 2 COOH
ole of B also reacts with 1 mole of Na 2 CO CO groups.
eacts with NaBH 4 to form C onl
B reacts only
o nly the carbonyl group iin B is reduced but
the carboxylic
b li acid
id groups remaini unaffected.
ff d
1524 trendyline
4
OH
A:
O O
HO C CH2 C CH2 COOH
B:
C:
( 9 marking points: Maximum 8)
(d) (i) Describe what you see when separate samples of sodium and sulfur are burned in
excess air. Write equations for the reactions that occur. [2]
Sodium burns readily with a brilliant yellow flame in air or oxygen to form
white sodium oxide, Na2 O.
4Na(s) + O 2(g) 2Na 2 O(s)
Sulfur burns slowly with a blue flame on heating in air or oxygen to form
colourless sulfur dioxide, SO 2. (Note: SO 3 is not formed)
S(s) + O 2 (g) SO 2 (g) or S 8 + 8O 2 8SO 2
Both equations correct

Both observations correct
(ii) The products resulting from the reactions in (d)(i) both react with water. Write
equations for these two reactions and describe the effect of the resulting solutions
on Universal Indicator solution. [2]
Na 2O(s) + H 2 O(l) 2NaOH(aq)
Universal Indicator turns violet.
SO 2 (g) + H 2O(l) H 2 SO 3(aq)
Universal Indicator turns red.
[Total: 20]
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1525 trendyline
5
2 Thallium is a Group III element discovered in 1861, and its toxicity was quickly noted.
Thallium isotopes and compounds have useful applications, sometimes despite their toxic
nature.
(a) Thallium forms compounds similar to aluminium, and thallium(III) chloride and
thallium(III) fluoride have very different structures and bonding.
(i) Draw and state the shape of thallium(III) chloride, TlCl 3 .

[1]
Cl
Tl
Cl Cl
Trigonal planar
(ii) In gaseous phase, thallium(III) chloride is able to form a compound with a M r of

621. Draw a dot-and-cross diagram of this compound, and state the Cl-Tl-Cl bond
angle.
[2]
Based on the M r , the compound is Tl 2 Cl 6 .

Cl Cl Cl
x x x
Tl
x x
Tlx
Cl

Cl
Cl
109.5o
(iii) Explain, in terms of structure and bonding, why thallium(III) fluoride has a high
melting point of 550 oC.[2]
Thallium(III) fluoride exists as a giant ionic lattice structure and

a large amount of energy is needed to break strong ionic bonds between
oppositely charged ions.
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1526 trendyline
6
(iv) Thallium is also able to form thallium(I) chloride, which is crystalline in nature.
In the crystal lattice of sodium and potassium chlorides, the co-ordination number
of each ion is 6. In the crystal lattice of thallium(I) chloride, TlCl, the co-ordination
number has a different value.
Suggest an explanation for the co-ordination number in the TlCl lattice being
different from those in NaCl and KCl..[1]
The size of the Tl+cations is larger than the Group Ications such as Na+ and
K+. More chloride ions can be packed around the larger Tl+cations.
(b) Thallium(III) chloride, TlCl 3 , reacts with hot water to produce thallium(III) oxide
precipitate and hydrochloric acid.
(i) Write a balanced equation for the above reaction.[1]
2TlCl 3 + 3H 2 O Tl 2 O 3 + 6HCl
(ii) In an experiment, a 15 g impure sample of thallium(III) chloride (M r = 310.5) was

mixed with hot water, and filtered. Water was then added to the filtrate to make a
standard solution in a 250 cm3 volumetric flask. A 25.0 cm3 aliquot was titrated
against 0.5 mol dm-3 aqueous sodium hydroxide, requiring a titre of 22.00 cm3.
Determine the percentage purity of the sample.
You may assume that the impurities are insoluble in water and are inert.
[2]
2TlCl
TllCl 3 +&l
o of moles of NaO
No NaOH = 0.022 x 0.5 = 0.0110 mo
mol
o of moles of HC
No HCll produced
oduced from the sample = 0.0110 x 10
1 = 0.110 mol
o of moles of TlCl 3 in sample = 0.110
No 01110 / 3 = 0
0.0367
0367 mol
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7
Mass of TlCl 3 in sample = 310.5 x 0.0367 = 11.4 g

Percentage purity of TlCl 3 in sample = 11.4 / 15 x 100% = 76.0%
(c) Thallium(I) sulfate(M r = 504.1) was often employed as a rodenticide and is highly
poisonous. The lethal dosage is 16 ppm of the rats mass. Assuming a typical rat has a
mass of 230 g, determine the number of moles of thallium(I)sulfate needed to kill a rat.
[2]
Mass of thallium(I) sulfate needed for lethal dosage = 230 x 16 / 106 = 0.00368 g
No of moles of thallium(I) sulfate needed = 0.00368 / 504.1= 7.30 x 10-6mol
(d) Thallium(III) ethanoate, Tl(CH 3 CO 2 ) 3 , is able to react with an alkene through addition.
When cyclohexene reacts with thallium(III) ethanoate, a compound with the molecular
formula C 10 H 16 O 4 is formed. Suggest the structural formula of this compound, and state
the number of stereoisomers that this compound has.[2]
CH3COO OCOCH3
This compound has a cis- and a trans-isomer, and the trans-isomer is optically
active with two enantiomers. Therefore this compound will have 3 stereoisomers.
201
(e) Tl is an isotope of thallium that is often used in medical diagnostics due to its
radioactive decay by electron capture with emission of gamma rays. The electronic
configuration of the Tl atom is [Xe]4f145d106s26p1.
Electron capture is a process in which a proton-rich nucleus of an atom absorbs one
electron from the first or second quantum shell to change one proton into a neutron.
201
(i) Suggest the species formed, including the nucleon number, when Tl undergoes
electron capture.[1]
201Hg
(ii) The species formed immediately after electron capture is known to be in excited
state, before returning to ground state by emitting gamma rays.
Name the orbital where the excited electron is most likely located in, and explain
why high energy gamma rays are emitted when the species return to ground
state.
[2]
6p. (can accept any orbital of higher energy than 6p)

When the electron capture occurs, an inner shell (1 or 2) is now short of an
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tren d li
dyline
p electron is at a high
electron. The 6p g energy
gy level,, and needs to release a
large
rge
ge amount of energy
energ to replace the absorbed electron in shell 1 or 2 as
e atom returns to ground state.
the
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8
(iii) A patient is typically injected with 0.02 g of thallium for heart diagnosis. The
following graph shows the radioactive decay (through electron capture) of a 0.02
g sample of 201Tl dissolved in 1 dm3 of inert solvent.
[201Tl] / g dm-3
0.02
0.01
0
100 200 300 Time / h
Using the graph, deduce the order of reaction for the radioactive decay of 201Tl.[2]
From the graph, (t ) 1 = (t ) 2 = 75 h. Since t is constant,

order of reaction is 1.
(iv) Hence, write the rate equation for this reaction and determine the rate constant,
stating its units.[2]
rate = k[201Tl]
k = ln2 / t = ln2 / 75 h = 0.00924 h-1
[Total: 20 m]
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9
3 The halogens and organic halides are useful laboratory reagents and have many applications.
(a) State and explain the difference in the reactions of chlorine and iodine with sodium
thiosulfate respectively. Write balanced equations for the reactions. [3]
Cl 2 + e 2Cl- E = +1.36 V
I2 + e 2I- E = +0.54 V
Oxidising power of the halogens decreases down the group as can be seen from
the less positive E value, hence iodine can only oxidise thiosulfate to tetrathionate.
4Cl 2 + S 2 O 3 2- + 5H 2 O 8Cl- + 2SO 4 2- + 10H+
I 2 + 2S 2 O 3 2- S 4 O 6 2- + 2I -
(b) Deduce which gas, fluorine or chlorine, would behave more ideally at low pressure.
Explain your answer.
[1]
Fluorine gas will behave more ideally. The electron cloud size of chlorine is larger
than fluorine, hence the van der Waals forces of attraction is stronger.
Organic halides are a group of compounds comprising alkyl halides, ethenylhalides and aryl
halides.
Alkyl halides are used as solvents for relatively non-polar compounds. They are also used as
the starting materials for the synthesis of many compounds.
(c) Alcohols react with hydrogen halides to produce alkyl halides.
(i) Suggest the type of reaction that occur. [1]
Nucleophilic substitution
(ii) 2-iodopropane is formed from propan-2-ol in the presence of sodium iodide
andconcentrated phosphoric acid.
Explain, with the aid of an equation, why concentrated sulfuric acid is not used. [2]
The hydrogen iodide produced will be readily oxidised by concentrated

sulfuric acid to iodine hence will not be availble to react with the alcohol.
8HI + H 2 SO 4 4I 2 + H 2 S + 4H 2 O
(d)
2-chloro-2-methylpropane undergoes alkaline hydrolysis to form 2-methylpropan-2-ol.
(i) Name and describe the mechanism of the hydrolysis of 2-chloro-2-methylpropane.

[3]
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d
Nucleophilic
p substitution S N 1

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10
(ii) With the aid of the Data Booklet, explain what will happen to the rate of reaction if 2-
bromo-2-methylpropane was used instead. [2]
BE(C-Cl) = 340 kJ mol-1

BE(C-Br) = 280 kJ mol-1
Since bond energy of C-Cl is higher than that of C-Br, the bond strength of
C-Cl is greater than that of C-Br. Hence the reactivity of the alkyl halides
decreases in the order RBr>RCl.The rate of reaction will increase
(e) Ethenylchloride is an important industrial chemical mainly used to produce the

polymer,PVC.
Ethynereacts with anhydrous hydrogen chloride gas over a mercuric chloride catalyst to
give ethenyl chloride.
ethyne ethenyl chloride
(i) With the aid of the Data Booklet, determine the enthalpy change of the reaction.
[2]
H r = enthalpy change for bond break + enthalpy change for bond form

= BE(H-Cl%(&& [BE(C-Cl) + BE(C-H) + BE(C=C)]
= 431 + 840 (340 + 410 + 610) = -89 kJ mol-1
(ii) Explain why ethenyl chloride does not undergo alkaline hydrolysis readily. [1]
The lone pair of electrons on chlorine delocalised across the double bond
resulting in partial double bond character in CCl bond, hence a stronger CCl
bond which is harder to break.
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OR
The carbon-carbon double
The nucleophile is unlikely to attack the carbon d bond as it is
electron
lectron rich.
(f) 1-iodopropane
ropane can be converted to butylamine
buttylamine
yla via a two-stage synthesis.Butylamine is
two stage sy
1531 trendyline
11
then used as an ingredient in the manufacture of pesticide.
(i) Suggest reagents and conditions for the two stages. Draw the structure of the
intermediate compound. [3]

(ii) Suggest a chemical test to distinguish between 1-iodopropane and 1-chloropropane.

[2]
Procedure:
Step: (1) Boil RX with NaOH(aq).
(2) Acidify with dilute HNO 3 .
(3) Add AgNO 3 (aq).
OR
Boil with silver(I) ethanoate in alcohol.
White precipitate (AgCl) observed for 1-chloropropane.

Yellow precipitate (AgI) observed for 1-iodopropane.
[Total: 20]
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y
Co-Cr alloys are most commonly used to make artificial joints including knee and hip joints
due to high wear-resistance and biocompatibility.
bilit However in 2010, faulty Co-Cr alloy hip
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12
joints manufactured by DePuy was removed from market due to leakage of toxic chromium
and cobalt into the body muscles and blood stream.
(a) State the electronic configurations of
(i) an atom of chromium,

[1]
1s22s22p63s23p63d54s1
(ii) the Co3+ion. [1]
1s22s22p63s23p63d6
(b) Why are transition metal complexes coloured? [3]
Transition metal complexes are often coloureddue to the presence of partially

filled d-orbitals in the metal ion.
In complexes, the presence of ligands causes a splitting of the energy of d
orbitals into 2 groups ZLWKDQHQHUJ\JDS(EHWZHHQWKHP
When a d-electron from lower energy group is promoted to the higher energy
group (d-d transition), radiation in the visible region of the electromagnetic
VSHFWUXPFRUUHVSRQGLQJWR(LVDEVRUEHG
Light energy that is not absorbed will be seen as the colour of the complex.
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1533 trendyline
13
(c) The colour of the complexes can be measured by a spectrometer. The amount of light
absorbed is expressed as an absorbance value. The higher the absorbance, the more
of a particular wavelength of light is being absorbed.
The spectrum below shows the major absorption peaks for [CrL 6 ]3+(aq) and[CrJ 6 ]3+(aq).
Relative
absorbance
[CrJ6]3+(aq)
[CrL6]3+(aq)
300 400 500 600 700 800

Higher energy Lower energy
Wavelength/nm
The wavelengths associated with each colour of light are given below.
colour Wavelength/nm
Violet 400-430
Blue 430-490
Green 490-570
Yellow 570-590
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rend
dyline
yli e Orange
red
590-620
590--620
590 2
620-750
620
0-750
5
1534 trendyline
14
(i) What are the coloursof [CrL 6 ]3+(aq) and [CrJ 6 ]3+(aq)? [2]
[CrL 6 ]3+(aq) : yellow/orange

[CrJ 6 ]3+(aq) : green/blue
(ii) What deduction can be made from the spectra about the size of the d-orbital
splitting in the two complexes? [2]
The d-orbital splitting for [CrL 6 ]3+(aq) is larger than [CrJ 6 ]3+(aq)
because electrons in lower d-subshell absorbs energy in shorter
wavelength and higher energy to excite to higher d-VXEVKHOO(LV
larger.
Cobalt forms many complexes with ligands such as H 2 O, NH 3 and . The most
common oxidation states of cobalt are +2 and +3.
Cations containing cobalt in these two oxidation states have significantly different colours
even when the ligands are the same.
(d) When H 2 O 2 is mixed with pink Co2+(aq) solution, no significant colour change is
observed.
When Co2+(aq) is mixed with excess NH 3 (aq) a slight colour change occurs and cationQ
is formed.
When cationQ is mixed with H 2 O 2 , a reddish brown solution is observed.
E data for the cobalt complex ions and hydrogen peroxide are given below.
[CoL 6 ]3+ + e- [CoL 6 ]2+E = +1.82V for L = H 2 Oand E = +0.11V for L = NH 3
H 2 O 2 + 2e- 2OH-E = +0.87V
Suggest an explanation for the above observations, giving equations where appropriate
and identify the cationQ.[5]
E Co3+/Co2+ =+1.82V
E H2O2/OH- =+0.87V
E H2O2/H2O is less positive than E Co3+/Co2+ , H 2 O 2 is unable to oxidiseCo(aq)2+ to
Co(aq)3+ and there is no ligand exchange reaction taking place. Hence, no
colour change.
When excess NH 3 is added, a ligand exchange reaction occurs. NH 3 replaces
H 2 O, ligands, resulting in a slight colour change.
[Co(H 2 O) 6 ]2+ + 6NH 3 [Co(NH 3 ) 6 ]2++ 6H 2 O
[explanation & equation: 1m]
Cation Q is [Co(NH 3 ) 6 ]2+.
E[ Co(NH3)6] 3+ /[Co(NH3)6] 2+ =+0.11 V
e dyy
E H2O2/OH-
H- =+0.87V
OH
E cell = +0.87
+0.87-(+0.11)
(+0.11) = +0.76 V > 0
When H 2 O 2 is added to Q,
Q
H 2 O 2 oxidises Co2+ in
n [Co(NH 3 ) 6 ]2+
2
tto
oCCo3+ in [Co(NH
[Co( 3 ) 6 ]3+, res
re
resulting in a reddish
brownwn solution observed
observed.
1535 trendyline
15
H 2 O 2 + 2[Co(NH 3 ) 6 ]2+ 2OH- + 2[Co(NH 3 ) 6 ]3+

(e) Explain why the neutral complex formed between a Co2+ ion and two
ions is soluble in cyclohexane. [1]
It is a simple covalent molecule. The weak van der Waals forces of

attraction formed between Co-complex and cyclohexane
molecules liberate sufficient energy to overcome van der Waalsforces of
attraction between Co-complex molecules and those between cyclohexane
molecules.
For your information:
The direct oxidation of methanoic acid in a fuel cell, DFAFC, shown below represents
potentially the most efficient method of obtaining useful energy from a renewable fuel.
(f) The electrons pass around the external circuit to the cathode.
The protons produced migrate across the proton exchange membrane, PEM, to the
cathode, where they react with oxygen from air, producing water.
Write the equations for the anode and cathode reactions.Hence construct the equation
for the overall reaction. [2]
HCO 2 H CO 2 + 2H+ + 2e- [Anode]

O 2 + 4H+ + 4e- 2H 2 O [cathode]
2HCO 2 H + O 2 2CO 2 + 2H 2 O [overall reaction]
(g) One method for the construction of DFAFC, involves electroplating a layer of platinum
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onto thee surface of the proton exchange membrane,membr PEM. The electrolyte for this
Cl- ions. The PEM iis the cathode in this
processs is a solution containing Pt(NH 3 ) 4 2+ and Cl
electrolytic
ytic cell.
(i) Suggest the ha

half -equation
equation for the cathode reaction that depo
half-equation deposits platinum on the
PEM. [1]
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16
Pt(NH 3 ) 4 2+ + 2e- Pt + 4NH 3
(ii) In one such preparation, a PEM with a surface area of 25 cm2 was immersed in
an electrolyte bath and a current of 0.0875 A was passed for 95 minutes.
Calculate the mass of platinum deposited onto the surface of PEM. [2]
Q = It = 0.0875 x 95 x 60 = 498.75 C
No of mol of electrons = 498.75/96500 = 5.17 x 10-3mol
No of mol of Pt deposited = 5.17 x 10-3/2 = 2.58 x 10-3mol
mass of Pt deposited = 2.58 x 10-3 x 195 = 0.504 g
[working : 1m & answer:1m]

[Total: 20]
5 (a) Myoglobin and haemoglobin are globular proteins that serve to bind and deliver oxygen.
The former serves as an intracellular storage site for oxygen in the muscle tissues, while
the latter transports oxygen in the bloodstream.
Each myoglobin molecule contains one haem group.
In deoxygenated myoglobin, a water ligand is weakly bound to the Fe2+ of the haem group
as shown:
haem group
Myoglobin Haem group in

deoxygenated myoglobin
(i) Briefly describe how myoglobin maintains its three-dimensional shape.

[2]
trendyli
trendyline
ndyline
dyli
It is maintained by the interactions
nteractions between
be the R-groups of the amino
acids,
cids, such as hydrogen bonds between polar group groups (OH, NH 2 ), ionic
bondsbetween
ondsbetween oppositely charged group CO 2 & +N
groups (CO -
NH 3 ), van der Waals
forcesof
rcesof attractio
attraction between non
non-polar
olar side chains (e.g: alkyl group)
and disulfide linkagesbetween SH groups.
1537 trendyline
17
(ii) In the presence of the haem group, the polypeptide chain coalesces into a
myoglobin molecule.
With the aid of the equation,
* + 76
and by considering the chemical interactions involved, explain why this is a
spontaneous process at low temperatures.
[2]
The bending and folding of the primary structure into a tertiary structure
is exothermic(negative H) due to the formation of various interactions
between the R-groups of the constituent amino acids.
The process is accompanied by a decrease in entropy (negative S) as the
formation of a more ordered myoglobin molecule decreases the degree of
disorder because there are now fewer ways in which the molecule and energy
can be distributed.
Hence G is negative at low temperatures.
(iii) Deoxygenated myoglobin is responsible for the dull purplish red muscle colour,
observed in the depth of the muscle. When meat is freshly cut, colour change occurs
in two stages:
Stage 1: Bright red colour when muscle surface is exposed to air.
Stage 2: With time, the bright red colour slowly changes to an unattractive, dull
brown colour associated with stale and spoiled meat.
With reference to the structure of the haem group and the reaction that occurs in
each stage, explain the colour changes involved.
[2]
The colour of meat depends on the ligand attached to the 6th coordinate site in
the haem group, and the oxidation stage of the iron centre.
:KHQ WKH PHDW LV H[SRVHG WR R[\JHQ IURP WKH DLU OLJDQG H[FKDQJH
(oxygenation) occurs to form oxymyoglobin. O 2 replaces H 2 O ligand and is
dative bonded to the haem group, which gives the bright red colour observed.
:KHQ PHDW KDV EHHQ VWRUHG IRU WRR ORQJ WKH )H2+ in the haem group
undergoes oxidation to form Fe3+, which gives rise to the dull brown colour.
(b) One of the isolated compounds that is primarily responsible for the umami (savory) flavor
is glutamate, which is a salt formed from glutamic acid that is commonly found in meat.
trendyline
dyline
y glutamate
utam
1538 trendyline
18
It is thought that glutamate stimulate a specific receptor site located in the taste buds on
the tongue, which is essentially a protein molecule. A simplified diagram of the receptor
site is shown below:
OH +
H3N
H2 N
(i) State two different types of interactions that can be formed between glutamate and
the receptor protein. Illustrate your answer with labelled diagram(s).
[2]
Any two illustrated
(ii) To enhance the flavor of food, many retailers in the food industry use monosodium
glutamate (MSG) as a food additive, which can be easily synthesized in the
laboratory.
Given that laboratory synthesis gives a racemic mixture, explain why 50% of the
glutamate synthesized in the laboratory is unable to bind precisely with the correct
ttrendyline
e dy e
orientation
ientation to the receptor protei
protein. [1]
Only
Only one mirror image form of glutamate
glutamat synthesized provides the desired
biological
ological effect as it has the correct orientation to bind to the protein
receptors. The other form is inactive.
ctiv
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19
The structure of glutamic acid is shown below:
glutamic acid
10 cm3 of the fully protonated glutamic acid is titrated with 20 cm3 of 1.00 moldm3 sodium
hydroxide solution. Its titration curve is shown below:
pH
Vol of NaOH / cm3
(iii) Show that the concentration of glutamic acid is 1.0 moldm3 at A.

[1]
n(NaOH) used to reach 1st endpoint = 0.010 mol

n(glutamic acid) = 0.010 mol
[glutamic acid] = 0.010/0.0100= 1.0 moldm3
(iv) Hence, calculate the pH of the solution at A.

[1]
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pH
dy
H+] = = . . = 0.0804 mol dm3
[H
pH at A = log
og 110 (0.0804) = 1.
1.10
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20
(v) Identify the specie(s) present at B.

With the help of an equation, explain how the solution at B can resist a change in pH
when a small amount of base is added. [2]

and
When a small amount of alkali is added,
+ OH+ H 2O
Negligible change in pH as OH ions are removed.
(vi) In a separate experiment, the solution at B was reacted with 10.0 cm3 of
0.05 moldm3 sodium hydroxide.
Calculate the pH of the mixture after the reaction.
You may find it useful to represent the fully protonated glutamic acid as HA.
[2]
HA + OH- A- + H 2O
At point B, nHA = n A- = 0.010 / 2= 0.005 mol
Number of moles NaOH added = 0.05 x 10/1000 = 5.00 x 10-4mol
Number of moles HA at equilibrium = 0.005 5.00 x 10-4mol = 0.0045 mol

Number of moles A at equilibrium = 0.005 + 5.00 x 10-4mol = 0.0055 mol
pH = pKa + lg [salt]/[acid]
= 2.19 + lg {(0.0055/0.025) / (0.0045/0.025)} = 2.28
(c) Compound P, C 9 H 11 NO 2 , rotates plane polarised light and reacts with the following
reagents:
aqueous bromine to give compound Q, C 9 H 9 NO 2 Br 2
sodium carbonate to give a salt
PCl 5 to give a 5-membered cyclic compound R
Deduce the structural formulae of compounds P, Q and R.[5]
P rotates plane polarised light P contains a chiral carbon; has no plane of
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symmetry
try and a non-superimposable
ble mirror imag
image.
P reacts
cts with aq Br 2 to
o give compound Q, C 9 H 9 NO 2 Br 2
P isphenylamine
henylamine or pheno
phenol
one of the 2, 4, 6 positions relative
ve to first substituent on benzene is occupied
1541 trendyline
21
with another substituent

P reacts with sodium carbonate to give a salt
P contains a COOH group.
(Hence, P cant be phenol as molecular formula only contains 2 O atoms)
OH in COOH reacts with PCl 5 to give COCl . Formation of 5-membered ring
NH 2 group in P attacks the electron deficient carbonyl C in the COClgroup.
NH 2 group &the other substituent on benzene ring are ortho to each other.
[4 marking points, max 2 marks]
P: R:
Q:
[1m for each structure]

[Total: 20]
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Tampines Junior College
2016 Preliminary Examination
H2 Chemistry Paper 1
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1543 trendyline
2
Section A
For each question, there are four possible answers, A, B, C and D. Choose the one you
How many atoms are present in 1 cm3 of ethane gas under room conditions?
(8 x 24000) (8 x 6.02 x1023 )

A 23 B
(6.02 x 10 ) (22400)
(8 x 6.02 x1023 )
C D 6.02 x 1023 x 30
(24000)
2 Sodium percarbonate, x(Na2CO3).y(H2O2) is a chemical that is used in cleaning

powders. When dissolved in water, it releases hydrogen peroxide and sodium carbonate,
both useful cleaning agents.
A sample of 10.0 cm3 of 0.100 mol dm-3 sodium percarbonate requires 20.0 cm3 of
0.100 mol dm-3 of acidified KI before the end point of titration is reached.
Another identical sample releases 48.0 cm3 of carbon dioxide at room conditions on
reaction with excess acid.
What is the value of x and y respectively?
A 2 and 1 B 3 and 2
C 2 and 3 D 3 and 1
3 Which of the following molecules is non polar?
A AsBr3
B C2Cl4
C CH3CBr3
D H2S
4 Which of the following pairs does the first molecule have a larger bond angle than the
second molecule?
A PCl3, PBr3
B H2S, H2O
C NH3, BF3
D SnCl2, OC
OCl
Cl2
TPJC 9647/1/JC2/Prelim/16
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3
5 Which statement is not true about the structure of silicon dioxide, SiO2?
A The bond angle about Si is 109.5o.

B The bond angle about O is 180o.
C SiO2 has a giant molecular structure.
D SiO2 is insoluble in water.
Which one of the following species has the same number of neutrons and protons, and
more electrons than protons?
37
A Cl B 48
Ti4+ C 79
Br+ D 32
S2-
7 Which statement regarding isotopes is incorrect?
A They have the same atomic number.

B They have the same neutron number.
C They have different mass number.
D They have different physical properties.
The standard enthalpy change of formation of C3H8(g) is 104 kJ mol1.
3C(s) + 4H2(g) 3C(g) + 8H(g)
C3H8(g)
What is the standard enthalpy change of atomisation of carbon, C(s)?
A 711 kJ mol-1 B +711 kJ mol-1

C 129 kJ mol-1 D +129 kJ mol-1
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9 Hydrogen gas and fluorine gas react to form hydrogen fluoride as shown in the equation
below:
H2(g) + F2(g) 2HF(l) Ho = 542 kJ mol1
The standard entropy change of this reaction is 160 J K1 mol1.
A At room temperature, the reaction is not spontaneous.

B An addition of catalyst will increase the yield of the product.
C There is an increase in the degree of disorder.
D The products are more stable than the reactants.
10 For the reaction 3A(aq) + 2B(aq) C(aq) at room temperature, the rate equation is
Rate = k [H+][B]
A The reaction involves more than one step.

B H+ is a catalyst in the above reaction.
C When the concentration of A is doubled at 10 oC, the rate of reaction decreases as
compared to room temperature.
D When the concentration of H+ and B is doubled, the amount of C formed is increased
four-fold.
11 The value of Kp of the reaction D2(g) + 2E2(g) 2DE2(g) is 3. Under the same reaction
conditions, what is the value of Kp for the reaction DE2(g) D2(g) + E2(g)?

A
B 3 C 1.5 D 3
12 What is the pH of the solution when 60 cm3 of 0.15 mol dm3 of CH3COOH and 80 cm3 of
0.10 mol dm3 CH3COONa+ are mixed at 25 oC?
(Ka of CH3COOH = 1.78 x 10-5 mol dm-3)
A 4.70 B 4.75 C 9.20 D 9.25
13 A 1.50 A current passed through a solution of osmium chloride, resulting in the reduction
of the metal ion. After 20 minutes, 0.888 g of osmium has been deposited. What is the
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oxidation state of osmium in osmium chloride?
A +1 B +2
+2 C +3
+3 D +4
+4
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5
14 Phosphorus trichloride and chlorine react according to the following equation:
PCl3(g) + Cl2(g) PCl5(g) 'Ho = +202 kJ mol1
A mixture of PCl3 and Cl2 was placed in a syringe and equilibrium was achieved. The
following graph was obtained. What could have happened at time t?
[PCl3]
t
A A catalyst was added to the mixture.
B The plunger was compressed by 5 cm3.
C The syringe was dropped in ice cold water.
D Cl2 was removed from the mixture.
15 On strong heating, SrSO4 decomposes into SrO and SO3. The compound Sr(NO3)2
decomposes at a much higher temperature than SrSO4. Which statement best explains
the lower thermal stability of SrSO4?
A SrSO4 has a more exothermic lattice energy than Sr(NO3)2.

B NO2 is a smaller molecule than SO3.
C SO42 is more easily polarised than NO3.
D The charge on SO42 is greater than that on NO3.
16 Which property of the elements in the Period 3 (sodium to sulfur) decreases numerically
across the Period?
A pH of its oxides in water

B Ionic radius
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C Melting po
points of its oxides
D 1st ionisation
ation
tion energy
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6
17 Radium is the last element in Group II in the Periodic Table.
Which statement is not true for radium?
A Its oxide dissolves in water to form a basic solution.

B It is the most reactive element in the group.
C The melting point of its chloride is lower to that of FrCl.
D It reacts with water to form hydrogen gas.
18 The hexaaquairon(III) complex hydrolyses as shown.
[Fe(H2O)6]3+ [Fe(H2O)5OH]2+ + H+
A There is a colour change from yellow to green.

B The hydrolysis is favoured by low pH values.
C The electronic configuration of Fe3+ changed from [Ar]3d5 to [Ar]3d6.
D [Fe(H2O)6]2+ is less acidic in solution as compared to [Fe(H2O)6]3+.
19 Vanadium(III) chloride reacts with carbon monoxide, CO, to form a compound in which
the coordination number of the vanadium complex is 6. A formula unit of one such
compound contains a cation and only one chloride ion.
A V(CO)5Cl B V(CO)5Cl2
C V(CO)4Cl3 D V(CO)3Cl3
20 In which reaction is the inorganic reagent acting as an electrophile?
Cl
A + Cl2 + HCl
Cl OH
B + KOH + KCl
+ Br2 Br
+ HBr
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end
C
O
O
OH
D + HCN
N CN
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7
21 Dopamine is a compound present in the body that functions as a neurotransmitter and a

precursor for other substances including adrenaline. It is also synthesized as a drug for
treatment of some neurodegenerative disease such as Parkinsons disease.
NH2
OH
O
HO
OH
Dopamine
Which statement about dopamine is not true?
A It is optically active.
B It can form a zwitterion in aqueous solution.
C It forms an orange precipitate with 2,4DNPH.
D One mole of dopamine forms an anion with 3 charge when reacted with 3 moles of
NaOH.
22 Codeine is an opioid pain medication. It is used to treat mild to severe pain in patients.
H3CO
O H
N
H
HO
Codeine
(The COC and OCH3 groups do not undergo any reaction.)
Four students made claims about the reactions of codeine.
F 1 mol of codeine reacts with 2 mol of H2(g).
G 1 mol of codeine reacts with 1 mol of PCl5(s).
H 1 mol of codeine reacts with 2 mol of CH3CO2H(l) under suitable conditions.
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I 1 mol of codeine reacts with 1 mol of dry HCl(g).
Which pair of students claims is correct?
A F and G B G and
nd H
C H and I D F and I
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8
23 Which reaction scheme is unable to produce the intended final product?
COOH COCl COOCH2CH3

D
PCl5 CH3CH2OH
24 An organic compound has the following properties:

x It decolourises hot, acidified KMnO4(aq).
x It gives a yellow precipitate with aqueous alkaline iodine.
x It forms a silver mirror with Tollens solution.
Which compound could give these results?
A CH3COOCH2CH2COCH3
B CH3CH(OH)CH2CH2CHO
C HCOCH2CH2CH2CHO
D CH3CH2C(CH3)(OH)(CH2)2COCH3
25
1,2ethanediamine, can be synthesised from ethanol through a
series of reactions.
Which set of reagents, used in sequential order, would be the most suitable for this
synthesis?
A PCl5, Cl2 in UV, aqueous NH3
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B Excess concentrated
o HNO3, LiAlH4
C CH3NH2, aqueous NH3
D Concentrated
trated
rated H2SO4, liquid Br2, ethanolic NH3
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9
26 Vitamin D exists in 2 forms, D2 and D3. The structure of vitamin D2 is shown below.
HO
Vitamin D2
How many stereoisomers does vitamin D2 have?
A 32 B 64 C 128 D 256
27 Which statement on protein is correct?
A Denaturation breaks down all the structures of the protein.
B Some examples of Rgroup interactions are ionic bonds, covalent bonds and
hydrogen bonds.
C Hydrogen bond in the secondary structure is formed between the O of the C=O
group and the H on the carbon.
D Heavy metal ions affect the hydrogen bonds in the proteins which will then lead to
denaturation.
28 Which reagent and conditions can be used to distinguish between the two compounds
below?
OH
H2N
OH
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OH
OH OH
A Aqueouss NaOH
NaO
B Acidified
d aqueous KMnO
KMn 4, heat
C Aqueous bromine
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10
D Acidified aqueous K2Cr2O7, heat

29 Treatment of compound J with hot alcoholic KOH produces a mixture of compounds.
Which of the following compounds could be produced in this reaction?
Br
OH
Br
Compound J
Br
OH
B
A
C D
30 Which one of the following shows the given ions arranged in order of increasing basicity?
A CH3O-, CH3COO-, CH2(Cl)COO-

B CH3CH(Cl)CH2COO-, CH3CH2COO-, C6H5O-
C CH3CH(Cl)CH2COO-, CH3CH(Cl)COO-, CH3CH(F)COO-
COO- COO- COO-
, , Br
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11
Section B
For each question in this part, one or more of the three numbered statements 1 to 3 may be
correct.
tick against the statement that you consider to be correct).
A B C D
No other combination of statements can be used as a correct response.
31 Which of the following diagrams correctly describes the behaviour of a fixed mass of an ideal
gas?
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12
A B C D
32 The graph shows the first fifteen ionisation energies for element L.
What can be deduced about the element L from the graph?
1 It is in Period 3 of the Periodic Table.
2 It is in Group IV of the Periodic Table.
3 The oxide of L can react with hot concentrated NaOH.
33 The rate equation for the reaction between compounds M and N to give one product is
shown below.
Rate = k [M]2 [N]p
The expression for the unit of rate constant, k, is given as molq dmr s-1.
Which sets of values of p, q and r fit the information?
p q r
1 0 -1 +3
2 1 -2 +6
3 2 -3 +12
Based on its position in the Periodic Table, which properties will element Te (atomic
number 52) have?
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1 Its oxide
e can react with water readily to form a strongly
stron acidic solution.
solutio
2 It will form
orm an oxide with formula T
Tee2O3.
3 It will form
orm
rm a chloride with formula T
TeCl
eCl5.
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13
A B C D
35 In a fuel cell in which hydrazine (H2NNH2) comes into contact with fresh air on the
surface of a catalyst, the reactions taking place at the two electrodes are as follows.
Anode: H2NNH2 + 4OH 4H2O + N2 + 4e
Cathode: O2 + 2H2O + 4e 4OH
1 Nitrogen is oxidised at the anode.
2 Oxygen is reduced at the cathode.
3 The electrode potential of the cell becomes less positive as the concentration of
hydrazine increases.
36 Which of the following molecules are optically inactive?
3
Cl
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A B C D
37 Myrcene can be extracted from sweet basil.
Mycrene
Which of the following options show the correct major product formed based on the
given reaction conditions?
Reaction Conditions Product
Cold, alkaline
1
KMnO4(aq)
2 Dry HBr(g)
tren
ndyline
n y in
Br2(aq)
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15
A B C D
38 Which compounds give only one organic product when reacted with hot, acidified
KMnO4(aq)? Ignore optical isomers.
39 Dexamethasone could be administered to women at the risk of pre-term birth to reduce

the chances of complications in babies such as respiratory distress syndrome,
intraventricular haemorrhage and pre-natal death.
Dexamethasone
Which reagents will react with dexamethasone?
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1 Fehlings
s solution
2 2, 4DNPH
NPH
P
3 Red phosphorus
osphorus and bromine
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16
A B C D
40 Which of the following compounds would react with NaBH4?
--End of Paper--
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Tampines Junior College 2016 Preliminary Examination
H2 Chemistry Paper 1 Worked Solution
1 2 3 4 5 6 7 8 9 10
C A B D B D B B D D
11 12 13 14 15 16 17 18 19 20
A A D B C A C D C A
21 22 23 24 25 26 27 28 29 30
C B C B D C B D A B
31 32 33 34 35 36 37 38 39 40
A C B D B D A D C B
Section A
How many atoms are present in 1 cm3 of ethane gas under room conditions?
(8 x 24000) (8 x 6.02 x1023 )

A B
(6.02 x 1023 ) (22400)
(8 x 6.02 x1023 )
C D 6.02 x 1023 x 30
(24000)
Ans: C

1 cm3 of ethane is equals to mol of ethane molecule. There are 8 atoms per

ethane molecule, so the total amount of atoms is . The number of atoms

would then be x 6.02 x1023
2 Sodium percarbonate, x(Na2CO3).y(H2O2) is a chemical that is used in cleaning
powders. When dissolved in water, it releases hydrogen peroxide and sodium
carbonate, both useful cleaning agents.
A sample of 10.0 cm3 of 0.100 mol dm-3 sodium percarbonate requires 20.0 cm3 of
0.100 mol dm-3 of acidified KI before the end point of titration is reached.
Another identical sample releases 48.0 cm3 of carbon dioxide at room conditions on
reaction with excess acid.
What is the value of x and y respectively?
A 2 and 1 B 3 and 2
3 and 1
C 2 and 3 D
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Ans: A
Amount of sodium percarbonate = 10/1000 x 0.10 = 0.001 mol
m
As 1 mole of sodium percarbonate will produce y mole of H2O2 and x mole of
Na2CO3
Amount of H2O2 = 0.001y
001y mol
mo
Amount of Na2CO3 = 0.001x
0 001x mol
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3
H2O2 + 2H+ + 2I- I2 + 2H2O

Amount of KI reacted = 20/1000 x 0.100 = 0.002 mol
Since KI: H2O2 is 2:1,
Amount of H2O2 = 0.001 mol, thus y = 1
Na2CO3 + 2H+ H2O + CO2 + 2Na+

Amount of carbon dioxide released = 48.0/24000 = 0.002 mol
Since Na2CO3: CO2 is 1:1
Amount of Na2CO3 = 0.002 mol, thus x =2
3 Which of the following molecules is non polar?
A AsBr3
B C2Cl4
C CH3CBr3
D H2S
Ans: B
AsBr3 is trigonal pyramidal in shape, there is a net dipole so it is polar. C2Cl4 is
trigonal planar in shape about each C. There is no net dipole as the dipole
moments cancels out each other. The shape about each C in CH3CBr3 is
tetrahedral but since the atoms connected to atoms with different
electronegativity, it is polar. H2S is bent in shape and thus there is a net dipole
moment.
4 Which of the following pairs does the first molecule have a larger bond angle than the
second molecule?
A PCl3, PBr3
B H2S, H2O
C NH3, BF3
D SnCl2, OCl2
Ans: D
PCl3, PBr3 both are trigonal pyramidal. As Cl is more electronegative than Br,
thus the bond pairs of electrons are further away from the central atom. There is
lesser repulsion between the bond pairs of electrons and thus bond angle is
smaller in PCl3.
H2S, H2O both are bent. As S is less electronegative than O, thus the bond pairs
of electrons are further away from the central atom. There is lesser repulsion
between the bond pairs of electrons and thus bond angle is smaller in H2S.
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NH3, BF3 NH
H3 is trigonal pyramidal and B
BF
F3 is
s trigonal planar. The
Th bond angles
are 107o and
nd 120o respectively.
SnCl2, OCl2 both are bent. SnC

SnCl
Cl2 has one lone pair of electrons wh
while OCl2has 2.
pulsion between the lone pair lon
Greater repulsion lone pair and lone pair b
bond pair of
electrons; therefore the bond angle in OCl2 will be smaller.
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4
5 Which statement is not true about the structure of silicon dioxide, SiO2?
A The bond angle about Si is 109.5o.

B The bond angle about O is 180o.
C SiO2 has a giant molecular structure.
D SiO2 is insoluble in water.
Ans: B
The structure of SiO2 is as such
Black dot Si; Red dot - O
Si has 4 O atoms tetrahedrally attached to it and thus the bond angle is 109.5o. The
structure is similar to that of diamond (giant molecular) and is insoluble in water.
We can see that the bond angle about O is not 180o as it is bent due to the 2 lone
pair of electrons on O.
Which one of the following species has the same number of neutrons and protons, and
more electrons than protons?
37
A Cl B 48
Ti4+ C 79
Br+ D 32
S2-
Ans: D
neutrons protons electrons
37
Cl 20 17 18
48 4+
Ti 26 22 18
79
Br+ 44 35 34
32 2-
S 16 16 18
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5
7 Which statement regarding isotopes is incorrect?
A They have the same atomic number.

B They have the same neutron number.
C They have different mass number.
D They have different physical properties.
Ans: B
Isotopes are atoms with the same number of protons but that have a different
number of neutrons. Thus they cannot have the same neutron number.
The standard enthalpy change of formation of C3H8(g) is 104 kJ mol1.
3C(s) + 4H2(g) 3C(g) + 8H(g)
C3H8(g)
What is the standard enthalpy change of atomisation of carbon, C(s)?
A 711 kJ mol-1 B +711 kJ mol-1

C 129 kJ mol-1 D +129 kJ mol-1
Ans: B 3x + 4(436)
3C(s) + 4H2(g) 3C(g) + 8H(g)
-104 2(350) + 8(410)
C3H8(g)
Besides 104 kJ mol-1, the other values are obtained from the Data Booklet. Using
Hess law and solving for x, we get option B.
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9 Hydrogen gas and fluorine gas react to form hydrogen fluoride as shown in the equation
below:
H2(g) + F2(g) 2HF(l) Ho = 542 kJ mol1
The standard entropy change of this reaction is 160 J K1 mol1.
A At room temperature, the reaction is not spontaneous.

B An addition of catalyst will increase the yield of the product.
C There is an increase in the degree of disorder.
D The products are more stable than the reactants.
Ans: D
G = H TS. The value of G at room temperature = 542 (298)(160/1000)
= 494 kJ mol-1, since G < 0, it is spontaneous at room temperature. Adding a
catalyst only speeds up the rate of the reaction but does not increase the reaction
yield. The reaction has a decrease in the degree of disorder as 'S is negative (or
there is a decrease in gaseous molecules from 2 to 0). Only option D is correct as
the reaction is exothermic, the products contains less energy (more stable) than
the reactants.
10 For the reaction 3A(aq) + 2B(aq) C(aq) at room temperature, the rate equation is
Rate = k [H+][B]
A The reaction involves more than one step.

B H+ is a catalyst in the above reaction.
C When the concentration of A is doubled at 10 oC, the rate of reaction decreases as
compared to room temperature.
D When the concentration of H+ and B is doubled, the amount of C formed is increased
four-fold.
Ans: D
The rate equation does not involve all the reactants, this can only mean that the
reaction is a multi-step reaction. A catalyst doesnt take part in the reaction and
should not be present in either the reactants or products. Option C is correct
because a decrease in temperature and doubling of the concentration of A (not
part of rate equation hence does not affect rate), the rate of reaction will decrease.
Option D is wrong because when both the species involved in the rate equation is
doubled, the rate increases 4-fold, not the amount of C formed.
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7
11 The value of Kp of the reaction D2(g) + 2E2(g) 2DE2(g) is 3. Under the same reaction
conditions, what is the value of Kp for the reaction DE2(g) D2(g) + E2(g)?

A
B 3 C 1.5 D 3
Ans: A

D2(g) + 2E2(g) 2DE2(g), Kp = = 3, = . Taking the inverse

on both sides, = Kp = (Kp is the Kp of the 2nd equation)

12 What is the pH of the solution when 60 cm3 of 0.15 mol dm3 of CH3COOH and 80 cm3 of
0.10 mol dm3 CH3COONa+ are mixed at 25 oC?
(Ka of CH3COOH = 1.78 x 10-5 mol dm-3)
A 4.70 B 4.75 C 9.20 D 9.25
Ans: A
The above system is a buffer. We need to use pH = pKa + lg [salt]/[acid]. The new
total volume is 140 cm3 (60 + 80). Hence the new concentrations of the acid and
salt are 60/140 x 0.15 = 0.0643 mol dm-3 and 80/140 x 0.10 = 0.0571 mol dm-3
respectively. Hence pH = -lg (1.78 x 10-5) + lg (0.0571 / 0.0643) = 4.70
13 A 1.50 A current passed through a solution of osmium chloride, resulting in the reduction
of the metal ion. After 20 minutes, 0.888 g of osmium has been deposited. What is the
oxidation state of osmium in osmium chloride?
A +1 B +2 C +3 D +4
Ans: D
Q = It = 1.50 x 20 x 60 = 1800 C
Q = nF, n = 1800/96500 = 0.0187 mol
Amount of Os = 0.888/190 = 0.00467 mol
One mol of Os received 0.0187/0.00467 = 4 mol of electrons. Thus the oxidation

state of Os in osmium chloride is +4.
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8
14 Phosphorus trichloride and chlorine react according to the following equation:
PCl3(g) + Cl2(g) PCl5(g) 'Ho = +202 kJ mol1
A mixture of PCl3 and Cl2 was placed in a syringe and equilibrium was achieved. The
following graph was obtained. What could have happened at time t?
[PCl3]
t
A A catalyst was added to the mixture.
B The plunger was compressed by 5 cm3.
C The syringe was dropped in ice cold water.
D Cl2 was removed from the mixture.
Ans: B
At time t, the concentration of PCl3 increased rapidly, only option B is correct as
when the plunger was compressed, the volume decreased rapidly and hence the
concentration would increase rapidly. Option A is wrong as a catalyst does not
affect equilibrium position and hence change the concentrations of the reactants.
Options C would cause the equilibrium to shift to the right and thus decrease the
concentration of PCl3. For option D, although the equilibrium would shift to the
left, the increase would be gradual, not rapidly.
15 On strong heating, SrSO4 decomposes into SrO and SO3. The compound Sr(NO3)2
decomposes at a much higher temperature than SrSO4. Which statement best explains
the lower thermal stability of SrSO4?
A SrSO4 has a more exothermic lattice energy than Sr(NO3)2.

B NO2 is a smaller molecule than SO3.
C SO42 is more easily polarised than NO3.
D The charge on SO42 is greater than that on NO3.
Ans: C
nion is larger and more easily polarised, the electron cl
When the anion cloud is easier to
distort and
d thus the compound is easier to decompose
decompos as the co covalent bonds in
the anion are weakened to a greater extent.
extent
ent.
t The ease of decompo
decomposition explains
why the thermal stability of SrSO4 is low.
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9
16 Which property of the elements in the Period 3 (sodium to sulfur) decreases numerically
across the Period?
A pH of its oxides in water

B Ionic radius
C Melting points of its oxides
D 1st ionisation energy
Ans: A
The oxides changes from basic to acidic as we move across the period. Thus the
pH decreases across the period.
17 Radium is the last element in Group II in the Periodic Table.
Which statement is not true for radium?
A Its oxide dissolves in water to form a basic solution.

B It is the most reactive element in the group.
C The melting point of its chloride is lower to that of FrCl.
D It reacts with water to form hydrogen gas.
Ans: C
Melting point of ionic solids depends on their lattice energies. For RaCl and FrCl,
Ra ions has a higher charge (2+) and smaller size than Fr ions (1+), thus RaCl
would have a higher melting point.
18 The hexaaquairon(III) complex hydrolyses as shown.
[Fe(H2O)6]3+ [Fe(H2O)5OH]2+ + H+
A There is a colour change from yellow to green.

B The hydrolysis is favoured by low pH values.
C The electronic configuration of Fe3+ changed from [Ar]3d5 to [Ar]3d6.
D [Fe(H2O)6]2+ is less acidic in solution as compared to [Fe(H2O)6]3+.
Ans: D
Fe3+ will polarise the O-H bond in water (or undergo cation hydrolysis) more than
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Fe2+ due too the higher charge. Thus H+ will bee generate
generated in a sm
smaller extent for
Fe2+ in water
er and hence
hence less acidic.
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10
19 Vanadium(III) chloride reacts with carbon monoxide, CO, to form a compound in which
the coordination number of the vanadium complex is 6. A formula unit of one such
compound contains a cation and only one chloride ion.
A V(CO)5Cl B V(CO)5Cl2
C V(CO)4Cl3 D V(CO)3Cl3
Ans: C
Since the compound only contains one chloride ion as the counter ion, the
Vanadium complex must have a 1+ charge. Taking into account that V is in a +3
oxidation state, the only correct option that allows for the complex to have 1+
charge and have 6 coordinate/dative bonds is C. (the complex is [V(CO)4Cl2]+)
20 In which reaction is the inorganic reagent acting as an electrophile?
Cl
A + Cl2 + HCl
Cl OH
B + KOH + KCl
+ Br2 Br
+ HBr
C
O
OH
D + HCN CN
Ans: A
The chlorine molecule in option A will be acting as the electrophile (benzene
undergoes electrophilic substitution). Other options, the inorganic reagents are
acting as the nucleophile (B and D) or radical (C).
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21 Dopamine is a compound present in the body that functions as a neurotransmitter and a

precursor for other substances including adrenaline. It is also synthesized as a drug for
treatment of some neurodegenerative disease such as Parkinsons disease.
NH2
OH
O
HO
OH
Dopamine
Which statement about dopamine is not true?
A It is optically active.
B It can form a zwitterion in aqueous solution.
C It forms an orange precipitate with 2,4DNPH.
D One mole of dopamine forms an anion with 3 charge when reacted with 3 moles of
NaOH.
Ans: C
Option C is not correct as there is no carbonyl group (aldehyde or ketone) in
dopamine. Thus there is no reaction with 2,4 DNPH to form an orange
precipitate.
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22 Codeine is an opioid pain medication. It is used to treat mild to severe pain in patients.
H3CO
O H
N
H
HO
Codeine
(The COC and OCH3 groups do not undergo any reaction.)
Four students made claims about the reactions of codeine.
F 1 mol of codeine reacts with 2 mol of H2(g).
G 1 mol of codeine reacts with 1 mol of PCl5(s).
H 1 mol of codeine reacts with 2 mol of CH3CO2H(l) under suitable conditions.
I 1 mol of codeine reacts with 1 mol of dry HCl(g).
Which pair of students claims is correct?
A F and G B G and H
C H and I D F and I
Ans: B
Student F is incorrect as only the C=C would undergo electrophilic addition with
H2(g). Student G is correct as PCl5 undergoes nucleophilic substitution with R-OH.
Student H is correct as there are 2 functional groups that react with CH3COOH (-
OH (condensation) and NR3(acid-base neutralisation)). Student I is incorrect as
there is more than one functional group that reacts with the dry HCl(g)
( nucleophilic substitution with R-OH and electrophilic addition on C=C)
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13
23 Which reaction scheme is unable to produce the intended final product?
COOH COCl COOCH2CH3

D
PCl5 CH3CH2OH
Ans: C
The first step is wrong as the dehydration step requires excess concentrated
sulfuric acid at 170oC rather than ethanolic KOH. So reaction C cannot take place
at all.
24 An organic compound has the following properties:

x It decolourises hot, acidified KMnO4(aq).
x It gives a yellow precipitate with aqueous alkaline iodine.
x It forms a silver mirror with Tollens solution.
Which compound could give these results?
A CH3COOCH2CH2COCH3
B CH3CH(OH)CH2CH2CHO
C HCOCH2CH2CH2CHO
D CH3CH2C(CH3)(OH)(CH2)2COCH3
Ans: B
x It decolourises hot, acidified KMnO4(aq) contains groups that can be oxidised
e.g. primary/secondary alcohols, aldehydes
x It gives a yellow precipitate with aqueous alkaline iodine contains the
C(CH3)(OH)H group (cannot be ketone as the first test indicates that it can be
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oxidised)
x It forms a silver mirror with Tollens solution aldehydes present.
Only B fulfils
fils
ls all the above criteria.
criteri
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14
25
1,2ethanediamine, can be synthesised from ethanol through a
series of reactions.
synthesis?
A PCl5, Cl2 in UV, aqueous NH3

B Excess concentrated HNO3, LiAlH4
C CH3NH2, aqueous NH3
D Concentrated H2SO4, liquid Br2, ethanolic NH3
Ans: D
Br NH2
OH Br H2N
26 Vitamin D exists in 2 forms, D2 and D3. The structure of vitamin D2 is shown below.
HO
Vitamin D2
How many stereoisomers does vitamin D2 have?
A 32 B 64 C 128 D 256
Ans: C
The chiral carbons are marked with an asterisk. There is a total of 6 chiral
carbons. And there is also one C=C bond (circled in the diagram below) that can
exhibit cis-trans isomerism. Thus the total number of stereoisomers is 26+1 = 128.
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15
27 Which statement on protein is correct?
A Denaturation breaks down all the structures of the protein.
B Some examples of Rgroup interactions are ionic bonds, covalent bonds and
hydrogen bonds.
C Hydrogen bond in the secondary structure is formed between the O of the C=O
group and the H on the carbon.
D Heavy metal ions affect the hydrogen bonds in the proteins which will then lead to
denaturation.
Ans: B
The R-group interactions are hydrogen bonding, ionic bonding, Van der Waals
interactions and disulfide linkages. The covalent bonds mentioned is the disulfide
linkages.
28 Which reagent and conditions can be used to distinguish between the two compounds
below?
OH
H2N
OH OH
OH OH
A Aqueous NaOH
B Acidified aqueous KMnO4, heat
C Aqueous bromine
D Acidified aqueous K2Cr2O7, heat
Ans: D
K2Cr2O7 is a weaker oxidising agent and is capable of oxidising the 2o alcohol in
the molecule on the right where a colour change from orange to green would be
observed.
KMnO4 cannot be used as the both compounds will react to give benzoic acid.
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16
29 Treatment of compound J with hot alcoholic KOH produces a mixture of compounds.

Which of the following compounds could be produced in this reaction?
Br
OH
Br
Compound J
Br
OH
B
A
C D
Ans: A
J undergoes dehydrohalogenation (elimination) with hot alcoholic KOH. (remove
HBr). Only option A can be formed. For B, C and D, the OH should still be on the
molecule.
30 Which one of the following shows the given ions arranged in order of increasing
basicity?
A CH3O-, CH3COO-, CH2(Cl)COO-

B CH3CH(Cl)CH2COO-, CH3CH2COO-, C6H5O-
C CH3CH(Cl)CH2COO-, CH3CH(Cl)COO-, CH3CH(F)COO-
COO- COO- COO-
, , Br
Ans: B
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aker an acid, the stronger the conjugate base. So in optio
The weaker
with electron
ctron group, carboxylic acid, phenol)
tron withdrawing group, phenol
option B, the acid
that the salts were derived from becomes progressive weaker. (carboxylic
(c acid
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17
Section B
For each question in this part, one or more of the three numbered statements 1 to 3 may be
correct.
tick against the statement that you consider to be correct).
A B C D
31 Which of the following diagrams correctly describes the behaviour of a fixed mass of an ideal
gas?
Ans: A
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All 3 options
ns are correct. Using pV
we plot a graph
pV = nRT as
we plot p against 1/T, y = 1/x type curve

curve.
as the equation. For 1
raph of p against V, y = 1/x type curve.
curve For 2
e. For
F 3 3, p
pV
1,, we have p = nRT/V, so if
2, we have rreciprocal graph when
V = nRT which is a constant for any
values of V, thus we get y = c type line, where c is a constant.
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18
32 The graph shows the first fifteen ionisation energies for element L.
What can be deduced about the element L from the graph?
1 It is in Period 3 of the Periodic Table.
2 It is in Group IV of the Periodic Table.
3 The oxide of L can react with hot concentrated NaOH.
Ans: C
There is a big jump in the ionisation energy between the 4th and 5th electron. This
means that there were 4 valence electrons in the outermost shell (Group IV).
Being in Group IV, the oxides will be acidic and thus react with a base.
33 The rate equation for the reaction between compounds M and N to give one product is
shown below.
Rate = k [M]2 [N]p
The expression for the unit of rate constant, k, is given as molq dmr s-1.
Which sets of values of p, q and r fit the information?
p q r
1 0 -1 +3
2 1 -2 +6
3 2 -3 +12
Ans: B
Rate = k [M]2 [N]p

k = rate/ [M]2 [N]p
the units of k can be worked out as shown.
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Simplifying
g the equation and comparing with the given units of k, we get
q = p 1 and
nd r = 3 + 3p. Looking at the options, only 1 and 2 gi
give the correct
values of each of the unknowns.
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19
Based on its position in the Periodic Table, which properties will element Te (atomic
number 52) have?
1 Its oxide can react with water readily to form a strongly acidic solution.
2 It will form an oxide with formula Te2O3.
3 It will form a chloride with formula TeCl5.
Ans: D
Te is in group VI, same as O and S. As such, we would expect the properties to
have some similarities to them. Statement 1 only is correct as with S, Te would
react with water to form an acidic oxide in solution. Similar to S, Te would form
oxides with formula of TeO2 or TeO3. Its chloride formula is TeCl4 or TeCl6.
35 In a fuel cell in which hydrazine (H2NNH2) comes into contact with fresh air on the
surface of a catalyst, the reactions taking place at the two electrodes are as follows.
Anode: H2NNH2 + 4OH 4H2O + N2 + 4e
Cathode: O2 + 2H2O + 4e 4OH
1 Nitrogen is oxidised at the anode.
2 Oxygen is reduced at the cathode.
3 The electrode potential of the cell becomes less positive as the concentration of
hydrazine increases.
Ans: B
Both statements 1 and 2 are correct. The oxidation number of N changes from -2
to 0 at the anode (oxidation). The oxidation number of O changes from 0 to -2 at
the cathode (reduction). Statement 3 is wrong because the potential should
increase (become more positive) when the concentration of hydrazine increases.
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20
36 Which of the following molecules are optically inactive?
3
Cl
Ans: D
A compound with chiral carbons isx optically inactive if the molecule is
symmetrical. For the 1st compound, there is such a mirror plane, which cancels
out the optical activity of each of the individual chiral C.
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21
37 Myrcene can be extracted from sweet basil.
Mycrene
Which of the following options show the correct major product formed based on the
given reaction conditions?
Reaction Conditions Product
Cold, alkaline
1
KMnO4(aq)
2 Dry HBr(g)
3 Br2(aq)
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Ans: A
The firstt reaction is a mild oxidation reaction; an alkene
a function group
functional
becomes s a diol. The second reaction is an electrophilic addition reaction,
n of H and Br across the alkene double bond (major produ
addition product shown),
and the 3rdd reaction is another electrophilic addition reaction of OH
O and Br
across the C=C (major product shown))
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22
38 Which compounds give only one organic product when reacted with hot, acidified
KMnO4(aq)? Ignore optical isomers.
Ans: D
After undergoing oxidation with hot, acidified KMnO4(aq), the products formed
O
OH
OH
for is O . For , O and

O OH
. For compound 2, the compound formed is HO O , which

decomposes to form carbon dioxide and water. Hence only compound 1 gives 1
organic compound after reaction.
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23
39 Dexamethasone could be administered to women at the risk of pre-term birth to reduce

the chances of complications in babies such as respiratory distress syndrome,
intraventricular haemorrhage and pre-natal death.
Dexamethasone
Which reagents will react with dexamethasone?

1 Fehlings solution
2 2, 4DNPH
3 Red phosphorus and bromine
Ans: C
Fehlings solution reacts with aldehyde functional groups only, which is not
present in dexamethasone. 2,4DNPH reacts with carbonyl functional groups
while red phosphorus and bromine (forms PBr3) reacts with alcohol functional
groups via nucleophilic substitution reaction to form RBr.
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24
40 Which of the following compounds would react with NaBH4?
Ans: B
NaBH4 reduces aldehydes and ketones only. Functional groups in the 3rd compound
(carboxylic acid and alkene) do not undergo reduction with NaBH4. (They can only be
reduced by LiAlH4 and H2/Pd respectively)
--End of Paper--
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2

1 Planning (P)
The solubility of a salt is determined by the amount of salt that can dissolve in a given volume
of water at a specific temperature. If the solubility is less than 104 mol dm3 of water, the salt
is said to be sparingly soluble.
(a) Barium carbonate is a sparingly soluble salt. Write the Ksp expression for barium
carbonate, stating its units.
.[1]
(b) Solubility can also be defined as the mass of a substance that can dissolve in
100 cm3 of water at a specific temperature. In this experiment, you are tasked to write a
detailed plan for an experiment on how you could determine the solubility of barium
carbonate, in grams per 100 cm3 of water at 25 oC.
You are provided with the following:

x Solid barium carbonate
x Deionised water
x Evaporating dish
x Oven
x Filter Paper
x Water bath
x And other apparatus normally found in a school laboratory
No other chemicals may be used in your plan.
Your plan should contain the following:

x determining the minimum mass of barium carbonate to be used
x appropriate procedure to measure a suitable mass of barium carbonate
x appropriate procedure and apparatus used for the dissolution process
x determining the mass of barium carbonate dissolved
x appropriate table to record measured data
x simple calculations on how the solubility can be determined
........
........
........
........
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........

........
........

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3
........
........
........
........
........
........
........
........
........
........
........
........
........
........
........
........
........
........
........
........
........
........
........
........
........
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........

........
........

TPJC 9647/2/JC2/Prelim/16 [Turn Over

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4
........
........
........
........
........
........
........
........
........
........
........
........
........
........
........
........
.[9]
(c) Describe one major source of error for the experiment and suggest an improvement
which could significantly increase the accuracy of the experiment.
........
........
........
........
........
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....[2]

[Total: 12]
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5
2 Ammonia, NH3, is a colourless gas with a sharp and distinct odour. Made by both humans
and nature, ammonia serves as a starting material for the production of many commercially
important nitrogen compounds.
(a) (i) Ammonia can be produced by heating ammonium chloride with calcium hydroxide.
The reaction also produces a white solid. Write a balanced equation for this
reaction.
...[1]
(ii) One such synthesis in (a)(i) produced 200 dm3 of ammonia at 400 oC and
50 kPa. Calculate the mass of ammonium chloride that was used in the reaction.
[2]
(iii) Under high temperature, ammonia behaves as if there are no intermolecular

forces of attraction between molecules. Explain why this is so.
...[1]
(b) The Haber process uses atmospheric nitrogen and hydrogen to produce ammonia gas
in the presence of an iron catalyst. The equilibrium to represent the Haber process is as
follows:
'H < 0
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3H2(g) + N2(g) 2NH3(g)
(i) State
ate
e the
e reaction conditions used for the Haber process.

...[1]

1585 trendyline
6
(ii) Explain for your chosen temperature in (b)(i).
...[2]
(iii) The iron catalyst used in the Haber process behaves as a heterogeneous catalyst.
Explain what is meant by the term heterogeneous catalyst.
[1]
(iv) Explain which feature of iron allows it to act as an appropriate catalyst for the
Haber process.
...[1]
(c) When an equimolar mixture of gaseous ammonia and gaseous hydrogen bromide at an
initial total pressure of 4 atm were injected into a chamber that was maintained at
450 oC, white crystals of ammonium bromide were formed as shown in the following
equilibrium:
NH3(g) + HBr(g) NH4Br(s) 'H > 0
It was found that the value of the equilibrium constant for the forward reaction,
Kp, at 450 oC was 10.0.
(i) Write down an expression for Kp.
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1586 trendyline
7
(ii) Calculate the value of the equilibrium constant for the reverse reaction,
Kp, at 450 oC, stating its units.
[1]
(iii) Calculate the pressure exerted by hydrogen bromide at equilibrium.
[3]
(iv) State and explain how the partial pressure of the gases and the value of Kp would
change if the temperature of the chamber was 600 oC.
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.. [2]
[Total: 16]

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8
3 (a) Draw a dot and cross diagram to show the bonding in a phosphate(V) ion, PO43.
[1]
(b) State the expected bond angle in a phosphate(V) ion.
...[1]
(c) (i) The following information involving potassium phosphate, K3PO4 is shown below.
Enthalpy change of hydration for K+(g) 320 kJ mol1

Enthalpy change of hydration for PO43(g) 290 kJ mol1
Enthalpy change of solution for K3PO4(s) +23.0 kJ mol1
Write an equation to represent the enthalpy change of solution for potassium

phosphate.
.[1]
(ii) Using the enthalpy values given in (c)(i), draw an appropriate energy level
diagram and hence, determine the lattice energy of potassium phosphate.
[3]
(iii) State and explain if the numerical value of the lattice energy of calcium phosphate
is higher or lower than the lattice energy of potassium phosphate.
.
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.

.[1]
[Total: 7]
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9
4 (a) The properties of Period 3 elements show a periodic trend. These elements occur in
nature and have at least one stable isotope.
(i) Sketch a graph to show the trend of atomic size across Period 3 from sodium to
chlorine. Explain the trend observed.
[3]
(ii) State and explain the difference between the first ionisation energies of sulfur and
phosphorus.
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[2]

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10
(b) Chlorate(V) ions, ClO3, are powerful oxidisers which are commonly used in
pyrotechnics and fertilizers.
In an experiment, it was found that 31.0 cm3 of ClO3 reacts exactly with 25.8 cm3 of
0.030 mol dm3 of lead(II) ions to form chlorine gas and lead(IV) ions.
Write an overall equation for the reaction and hence, calculate the concentration of
ClO3 required.
[3]
(c) Chlorate(V) ions can also be formed by reacting chlorine gas with NaOH(aq). State the
reaction conditions required and write an equation for the transformation.
..
..
..[2]
[Total: 10]
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11
5 FeCl2(aq) underwent a series of reactions as shown below.
(a) Write down the electronic configuration for the Fe2+ ion.
..[1]
(b) State the colour observed for FeCl2(aq).
..[1]
(c) State the identities of A D.
A:
B:
C:
D: [4]
(d) The Kstab of C is less than the Kstab of D. Account briefly for the difference in Kstab values.
.....
.....
......[1]
[Total: 7]
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12
6 A reaction scheme involving aromatic molecules is shown below.
(a) State the reagents and conditions for steps 1-4 of the reaction scheme above.
Step 1:
Step 2:
Step 3:
Step 4: .......[4]
(b) Draw the structure of the other possible isomer that can be obtained from step 1.
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13
(c) When compound F is placed in water, an acidic solution of pH 2 is formed. Write an

equation to account for the observation.
[1]
(d) Draw the structure of the organic products formed when compound G reacts with
hot NaOH(aq).
[2]
(e) Suggest a simple chemical test which would allow you to distinguish between
compound G and compound H.
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...[2]
[Total: 10]

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14
7 The structure of silk, a natural protein fibre, have been the subject of much research in recent
years. The structure of silk fibre is composed of protein chains, which mainly consists of
glycine, alanine and serine amino acids.
Amino Acid Structure

Glycine (gly) NH2CH2COOH
Alanine (ala) NH2CH(CH3)COOH
Serine (ser) NH2CH(CH2OH)COOH
(a) (i) Draw the structural formula of the tripeptide ala-gly-ser.
[1]
(ii) Suggest how many other tripeptides can be formed by the three amino acids in
(a)(i) (each amino acid can only be used once).
.[1]
(iii) With the aid of a diagram, suggest how the tertiary structure can be stabilised with
a polypeptide chain consisting only of these three amino acids.
[2]
(iv) Hence explain if a change in pH would denature the tertiary structure described in
(a)(iii).
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[1]

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15
(b) (i) Amino acids can act as a buffer in water. Define the term buffer.
[1]
(ii) Write equations to represent how a solution of serine can behave as a buffer when
a small amount of acid and base is separately added.
[2]
(c) Serine can also react with chloroethane under suitable conditions in a 1:1 mole ratio.
Draw the structure of the organic compound produced and state the type of reaction
involved.
[2]
[Total: 10]
---End of Paper---

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1
For
Tampines Junior College 2016 Preliminary Examination Examiners
H2 Chemistry Paper 2 Solution Use
1 Planning (P)
The solubility of a salt is determined by the amount of salt that can dissolve in a given
volume of water at a specific temperature. If the solubility is less than 104 mol dm3 of
water, the salt is said to be sparingly soluble.
(a) Barium carbonate is a sparingly soluble salt. Write the Ksp expression for barium
carbonate, stating its units.
[1]
2+ 2 2 6
Ksp = [Ba ] [CO3 ] mol dm
(b) Solubility can also be defined as the mass of a substance that can dissolve in
100 cm3 of water at a specific temperature. In this experiment, you are tasked to write
a detailed plan for an experiment on how you could determine the solubility of barium
carbonate, in grams per 100 cm3 of water at 25 oC.
You are provided with the following:

x Solid barium carbonate
x Deionised water
x Evaporating dish
x Oven
x Filter Paper
x Water bath
x And other apparatus normally found in a school laboratory
No other chemicals may be used in your plan.
Your plan should contain the following:

x determining the minimum mass of barium carbonate to be used
x appropriate procedure to measure a suitable mass of barium carbonate
x appropriate procedure and apparatus used for the dissolution process
x determining the mass of barium carbonate dissolved
x appropriate table to record measured data
x simple calculations on how the solubility can be determined
[9]
3 -4 -3
1. Solubility of sparingly soluble salt in 100 cm = 10 x 10 = 10 mol per
100cm3
Minimum mass of BaCO3 to be used = 10-3 x 197 = 0.197 g
2. Using an electronic balance, weigh about 1.00 1.50 g of BaCO3 into the
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ne
weighing bottle.
3. Use a 50 cm3 burette to measure 100 .00 cm3 of deionised water and
100.00
transfer
ansfer the water into a clean, dry beaker.
ransfer
4. Place into a water bath maintained at 25 oC [1 for step 3&4]
lace the beaker in
5. Add the barium carbonate into the water and stir the solu
solution with the
glass rod until the solid does not dissolve anymore.
2016 JC2 H2 Chem/ SA2 Exam/ Paper 2 [Turn Over

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6. Weigh the mass of a piece of filter paper. Filter the mixture using the
filter paper.
7. Transfer the filter paper + residue onto an evaporating dish and place the
dish into an oven to dry.
8. (After 10 minutes, take the evaporating dish out of the oven and let it
cool down in a desiccator.)
9. Using an electronic balance, weigh the residue with the filter paper.
10. Repeat steps 7-9 until a constant mass is obtained.
11. Repeat steps 1 10 with another similar sample.
Table
Experiment 1 Experiment 2
Mass of empty weighing m1 m'1
bottle
Mass of weighing bottle + m2 m'2
barium carbonate
Mass of barium carbonate m3 = m2 m 1 m'3 = m'2
before dissolution m'1
Mass of filter paper m4 m'4

Mass of filter paper + m5 m'5
excess barium carbonate
residue
Mass of excess barium m6 = m5 m 4 m'6 = m'5
carbonate residue m'4
Mass of barium carbonate m7 = m3 m 6 m'7 = m'3 -

dissolved m'6
Calculations:
Solubility of barium carbonate = (m7 + m7) / 2 = M g per 100 cm3
(c) Describe one major source of error for the experiment and suggest an improvement
which could significantly increase the accuracy of the experiment.
[2]
Heat loss to surrounding can lead to the water baths temperature being
inconsistent.
We can improve this by using an electric water bath which can help us to
maintain a consistent temperature.
or
Ensure consistency when stirring to allow maximum amount of barium
carbonate before filtering.
We can improve by using a magnetic stirrer.
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or
ature of the reaction should remain at 25 oC durin
Temperature during
durin the filtration
process.
s.
We can conduct the experiment in a laboratory with a thermosta
thermostat.
[Total: 12]
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3
For
2 Ammonia, NH3, is a colourless gas with a sharp and distinct odour. Made by both humans Examiners
and nature, ammonia serves as a starting material for the production of many commercially Use
important nitrogen compounds.
(a) (i) Ammonia can be produced by heating ammonium chloride with calcium
hydroxide. The reaction also produces a white solid. Write a balanced equation
for this reaction.
[1]
2NH4Cl + Ca(OH)2 2NH3 + CaCl2 + 2H2O
(ii) One such synthesis in (a)(i) produced 200 dm3 of ammonia at 400 oC and
50 kPa. Calculate the mass of ammonium chloride that was used in the
reaction.
[2]
In order to solve for the amount of ammonia gas,
PV = nRT
(50 x 103) x (200 x 10 3) = n x 8.31 x (400+273)
n = 1.788 mol
Since 2NH4Cl : 2NH3 (allow ecf)

Amount of NH4Cl = 1.788 mol
Mass of NH4Cl = 1.788 x (14 + 4 + 35.5)
= 95.7 g
(iii) Under high temperature, ammonia behaves as if there are no intermolecular

forces of attraction between molecules. Explain why this is so.
[1]
At a higher temperature, particles have greater (kinetic) energy. Thus with
sufficient kinetic energy, particles can overcome the existing
intermolecular attractions (or hydrogen bonding).
(b) The Haber process uses atmospheric nitrogen and hydrogen to produce ammonia
gas in the presence of an iron catalyst. The equilibrium to represent the Haber
process is as follows:
3H2(g) + N2(g) 2NH3(g) 'H < 0
(i) State the reaction conditions used for the Haber process.
[1]
o
Conditions: 200 atm, 450 500 C, (finely divided iron)
(ii) Explain for your chosen temperature in (b)(i).
[2]
According to Le Chateliers Principle, the use of a low temperature will
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trend
dyli
favour
vour
our the exothermic reaction,
reaction, hence equil
equilibrium will shift to the right (or
forward
rward reaction is favoured),
favoured), and result in a high yield of N
NH3.
nce, a moderate temperature of 450oC is chosen so tthat the rate of
Hence,
production
oductio
ducti n of NH3 will
w notno be too slow.
slow

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(iii) The iron catalyst used in the Haber process behaves as a heterogeneous
catalyst. Explain what is meant by the term heterogeneous catalyst.
[1]
Catalyst and reactants are in different states/phases.

(iv) Explain which feature of iron allows it to act as an appropriate catalyst for the
Haber process.
[1]
In Fe, there are available 3d and 4s electrons and empty d orbitals which
allows for the ready adsorption (through the formation of bonds) of
reactant molecules onto the catalyst surface.
(c) When an equimolar mixture of gaseous ammonia and gaseous hydrogen bromide at
an initial total pressure of 4 atm were injected into a chamber that was maintained at
450 oC, white crystals of ammonium bromide were formed as shown in the following
equilibrium:
NH3(g) + HBr(g) NH4Br(s) 'H > 0
It was found that the value of the equilibrium constant for the forward reaction, Kp, at
450 oC was 10.0.
(i) Write down an expression for Kp.
[1]
Kp = 1
(PNH3)(PHBr)
(ii) Calculate the value of the equilibrium constant for the reverse reaction, Kp, at
450 oC, stating its units.
[1]
Kp = 1 / 10.0 = 0.100 atm2
(iii) Calculate the pressure exerted by hydrogen bromide at equilibrium.

[3]
Let x be the partial pressure of NH3 reacted.
NH3 HBr
Initial partial pressure /atm 2 2
Change partial pressure /atm x x
Equilibrium partial pressure /atm 2x 2x
Kp = 1
(PNH3)(PHBr)
10.0 = 1 / (2 x)2
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0.1 = (2 x
Solving
Solving for x,x,
x = 1.68 atm or 2.32

32 atm
a (rejected as x cannot
cann be > 2)
Equilibrium pressure of HBr = 2 1.68 = 0.32 atm
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5
For
(iv) State and explain how the partial pressure of the gases and the value of Kp Examiners
would change if the temperature of the chamber was 600 oC. Use
[2]
When temperature increases, according to Le Chateliers Principle, the
system would respond by decreasing the temperature system, favouring
the endothermic reaction.
Hence favours the forward reaction, equilibrium shifts right, partial

pressure of the gases decreases and the value of Kp increases.
[Total: 16]
3 (a) Draw a dot and cross diagram to show the bonding in a phosphate(V) ion, PO43.
[1]
(b) State the expected bond angle in a phosphate(V) ion.

[1]
Angle: 109.5o
(c) (i) The following information involving potassium phosphate, K3PO4 is shown
below.
Enthalpy change of hydration for K+(g) 320 kJ mol1

Enthalpy change of hydration for PO43(g) 290 kJ mol1
Enthalpy change of solution for K3PO4(s) +23.0 kJ mol1
Write an equation to represent the enthalpy change of solution for potassium

phosphate.
[1]
K3PO4(s) 3K+(aq) + PO43-(aq)
(ii) Using the enthalpy values given in (c)(i), draw an appropriate energy level
diagram and hence, determine the lattice energy of potassium phosphate.
[3]

1600 trendyline
Lattice Energy = (3 x 320) + ( 290) 23 = 1273 kJ mol1
1270 kJ mol1 (3.s.f)
(iii) State and explain if the numerical value of the lattice energy of calcium
phosphate is higher or lower than the lattice energy of potassium phosphate.
The numerical value of lattice energy of calcium phosphate would be
higher. Since the phosphate anion is the same for both compound,
calcium ions has a higher charge of 2+ and smaller radius as compared to
that of potassium ions 1+ charge and larger radius.
[Total: 7]
4 (a) The properties of Period 3 elements show a periodic trend. These elements occur in
nature and have at least one stable isotope.
(i) Sketch a graph to show the trend of atomic size across Period 3 from sodium to
chlorine. Explain the trend observed.
[3]
trendyline
(Period 3 Elements/ Proton Number)
Labelling
b lli off atomic
t i radius
di on y axis,
i and d th
the respective
ti elements on the
x axis. (Atomic radius values are not required). Graph shows a decreasing
1601 trendyline
7
For
trend. Examiners
Use
Across the Period, nuclear charge increases as the number of protons
increase and shielding effect remains similar as electrons are being added
to the same quantum shell.
Hence, valence electrons are more strongly attracted to the nucleus.

Atomic radius decreases across the period.
(ii) State and explain the difference between the first ionisation energies of sulfur
and phosphorus.
[2]
Inter-electronic repulsion occurs between the paired electrons in the 3p
orbital in sulfur.
Therefore, less energy is required to remove a (paired) 3p electron from

sulfur than (an unpaired electron) from phosphorous, hence sulfur has a
lower 1st ionisation energy than phosphorus.
(b) Chlorate(V) ions, ClO3, are powerful oxidisers which are commonly used in
pyrotechnics and fertilizers.
In an experiment, it was found that 31.0 cm3 of ClO3 reacts exactly with 25.8 cm3 of
0.030 mol dm3 of lead(II) ions to form chlorine gas and lead(IV) ions respectively.
Write an overall equation for the reaction and hence, calculate the concentration of
ClO3 required.
[3]
2+ 4+
Oxidation: Pb Pb + 2e
Reduction: 2ClO3 + 12H+ + 10e Cl2 + 6H2O [1 for reduction half equation]
Overall Equation: 2ClO3 + 12H+ + 5Pb2+ o Cl2 + 6H2O + 5Pb4+
Amount of lead (II) ions = 25.8/1000 x 0.030 = 7.74 x 104 mol
2ClO3 5Pb2+
Amount of ClO3 = (2/5) x 7.74 x 104 = 3.096 x 104 mol
Concentration of ClO3 = 3.096 x 104 / 31 x 103 = 9.99 x 103 mol dm3

(3 s.f. with units)
(c) Chlorate(V) ions can also be formed by reacting chlorine gas with NaOH(aq). State
the reaction conditions required and write an equation for the transformation.
trendyline
[2]
Reactionn conditions: Hot
Hot: 3Cl2((aq)) + 6NaOH(aq)

6N OH( o 5NaCl(aq) + NaClO3(aq)) + 3H2O
O(l)
[Total:10]

1602 trendyline
5 FeCl2(aq) underwent a series of reactions as shown below.
(a) Write down the electronic configuration for the Fe2+ ion.
[1]
2 2 6 2 6 6
1s 2s 2p 3s 3p 3d
(b) State the colour observed for FeCl2(aq).
[1]
FeCl2(aq) is a green solution.
(c) State the identities of A D.
[4]
A: Fe(OH)2
B: Fe(OH)3
C: [Fe(CN)6]3
D: [Fe(edta)]
(d) The Kstab of C is less than the Kstab of D. Account briefly for the difference in Kstab
values.
[1]
4-
D has one polydentate/hexadentate ligand(or edta ) is generally more stable(or
stronger) than C which consist of 6 monodentate ligands (or CN-).
[Total: 7]
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1603 trendyline
9
For
6 A reaction scheme involving aromatic molecules is shown below. Examiners
Use
(a) State the reagents and conditions for steps 1-4 of the reaction scheme above.
[4]
Step 1: Add dilute HNO3, rtp
Step 2: Add acidified KMnO4(aq), heat
Step 3: Add PCl3 or PCl5 or SOCl2, rtp
Step 4: Add phenol, rtp
(b) Draw the structure of the other possible isomer that can be obtained from step 1.
[1]
(c) When compound F is placed in water, an acidic solution of pH 2 is formed. Write an

equation to account for the observation.
[1]
tre
trendyline
rendylin
in
ne
ne
1604 trendyline
(d) Draw the structure of the organic products formed when compound G reacts with
hot NaOH(aq).
[2]
(e) Suggest a simple chemical test which would allow you to distinguish between
compound G and compound H.
[2]
Neutral FeCl3. A purple solution would be observed for Compound G but no

purple solution would be observed for Compound H.
or Br2(aq). The reddish brown solution of Br2(aq) will decolourize in Compound

G but will not decolourize in Compound H.
or Na(s) effervescence will be observed in Compound G but there will not be

effervescence in Compound H.
[Total: 10]
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1605 trendyline
11
For
7 The structure of silk, a natural protein fibre, have been the subject of much research in Examiners
recent years. The structure of silk fibre is composed of protein chains, which mainly Use
consists of glycine, alanine and serine amino acids.
Amino Acid Structure

Glycine (gly) NH2CH2COOH
Alanine (ala) NH2CH(CH3)COOH
Serine (ser) NH2CH(CH2OH)COOH
(a) (i) Draw the structural formula of the tripeptide ala-gly-ser.

[1]
(ii) Suggest how many other tripeptides can be formed by the three amino acids in
(a)(i) (each amino acid can only be used once).
[1]
5
(iii) With the aid of a diagram, suggest how the tertiary structure can be stabilised
with a polypeptide chain consisting only of these three amino acids.
[2]
or van der Waals between appropriate Rgroups

or hydrogen bonding between 2 ser Rgroups
(iv) Hence explain if a change in pH would denature the tertiary structure described
in (a)(iii).
[1]
ttren
endyline
i
No it would not as a change in pH would only disrupt io ionic interactions
between
tween the R
Rgroups.
Rgroups
groups..
or
No as there are no ionic
ionic interactions between the R
R
Rgroups.
groups

1606 trendyline
(b) (i) Amino acids can act as a buffer in water. Define the term buffer.
[1]
A buffer solution is a solution that is able to resist drastic change in pH
when a small amount of acid or base is added.
(ii) Write equations to represent how a solution of serine can behave as a buffer
when a small amount of acid and base is separately added.
[2]
+ + +
NH3 CH(CH2OH)COO + H NH3 CH(CH2OH)COOH
NH3+CH(CH2OH)COO + OH NH2CH(CH2OH)COO- + H2O
(c) Serine can also react with chloroethane under suitable condition in a 1:1 mole ratio.
Draw the structure of the organic compound produced and state the type of reaction
involved.
[2]
SN2 Nucleophilic Substitution
[Total: 10]
---End of Paper---
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1607 trendyline
1 (a) (i) Write an equation to show how phenylamine acts as a weak base in
water. [1]
(ii) The base dissociation constant, Kb, for phenylamine is

3.98 x 1010 mol dm3 at 25 oC. Calculate the pH of a buffer solution
made up of phenylamine and its salt in a 3:1 ratio. [2]
(b) Sunset Yellow is used as an aqueous food colourant in sweets, orange

squash and jams. It is synthesised from 4-aminobenzenesulfonic acid.
4-aminobenzenesulfonic acid
(i) Explain why 4-aminobenzenesulfonic acid is less basic than

phenylamine. [2]
(ii) The structure of Sunset Yellow is shown below.
Sunset Yellow
The sodium sulfonate groups (SO3Na+) have little effect on the

colour of Sunset Yellow. Hence, suggest a reason why the sodium
sulfonate groups are needed in the molecule. [1]
(c) Tetralin can undergo mono-bromination by reacting with bromine in the

presence of anhydrous FeBr3.
(i) trendyline
trendylin
d Tetralin
Suggest a reason why the FeBr3 used

Sugge sed is anhydrous.
anhydro [1]
1608 trendyline
2
(ii) Name and describe the mechanism for this reaction, including curly
arrows showing the movement of electrons, and all charges. [3]
(iii) Explain why the bromination of phenylamine does not require the
use of anhydrous FeBr3. [1]
(d) Another possible catalyst for the bromination reaction is the use of
transition elements.
(i) Define what is meant by the term transition element. [1]
(ii) A white precipitate is formed initially when aqueous ammonia is

gradually added to aqueous copper(I) nitrate.
Write an equation for this reaction. [1]
(iii) However, the white precipitate in (d)(ii) dissolves when an excess of

aqueous ammonia is added, resulting in a colourless solution.
Explain why the final solution is colourless. [1]
(iv) When excess aqueous ammonia is added to a solution containing

copper(II) nitrate, a deep blue solution was formed.
Explain for the deep blue colouration and state the colour of light
absorbed by the solution. [4]
(v) Suggest the series of colour change and formula of the complex
formed when excess concentrated HCl is gradually added to a
solution of copper(II) nitrate. [2]
[Total: 20]
trendyline
1609 trendyline
3
2 (a) (i) Name and describe the mechanism of the hydrolysis reaction of
CH3CH2Cl using NaOH(aq). In your answer, show any relevant curly
arrows charges, dipoles or lone pairs of electrons you consider to be
important in this mechanism. [3]
(ii) Write the rate equation for the above reaction. [1]
(iii) State, if any, how the rate constant is affected with an increase in the
concentration of CH3CH2Cl. [1]
(iv) CH3CH2Cl can be prepared by reacting ethanol with SOCl2. Write an

equation for this reaction and suggest an advantage of using SOCl2
as a reagent for halogenation. [2]
(b) (i) Hydrolysis of halogenoalkanes releases halide ions that can be

precipitated as silver halides upon addition of AgNO3(aq). The
halogenoalkanes can be distinguished by the different colours of the
silver halides.
When NH3(aq) is added in excess, the white precipitate of AgCl(s)

dissolves to give a colourless solution. Explain the dissolution of
AgCl(s) precipitate in excess NH3(aq) with the aid of relevant
equations. [3]
(ii) Halide ions can also be distinguished by the addition of acidified

K2Cr2O7(aq).
Use relevant Eo values in the Data Booklet to predict the reaction, if

any, when acidified K2Cr2O7(aq) is added to Cl(aq) and I(aq)
separately. In each case, calculate Ecell and write a balanced
(c) Silver chloride is sparingly soluble in water at room temperature.
Predict the signs of 'Hppt and 'Sppt for the precipitation reaction. Give a
reason for each of your prediction. [3]
trendyline
1610 trendyline
4
(d) (i) When a precipitate is formed, 'Gppt, in J mol-1, is given by the

'Gppt = 2.303RTlogKsp
The Ksp of silver fluoride, AgF(s), is 1.01 mol2 dm6 at room

temperature.
Use the above 'Gppt expression to determine whether AgF(s) is

soluble in water at room temperature. [2]
(ii) Hence, predict and explain how the solubility of AgF in water would
change when a solution of NaF is added. [2]
[Total: 20]
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1611 trendyline
5
3 Cosmetic chemistry has been responsible for inventing a range of different

cosmetic products. Over the years, it is estimated that the cosmetic industry
makes 42.8 billion dollars per annum, and a large part of the industry depends
on the research and development behind the chemistry of cosmetics.
Benzaldehyde imparts a bitter almond flavour and aroma. It is commonly used

to produce almond-flavoured food and certain cosmetic products. Benzaldehyde
can be synthesised from cinnamaldehyde obtained from the oil of cinnamon.
(a) (i) Devise a three-step synthesis, starting from cinnamaldehyde, for the
manufacture of benzaldehyde. Give the reagents and conditions
required and the structure of the intermediates involved.
[5]
(ii) Suggest one simple chemical test which would enable you to
distinguish between cinnamaldehyde and benzaldehyde. State the
observations for each compound. [2]
(iii) Benzaldehyde is considered to be soluble in water. By considering

relevant interactions, explain the solubility of benzaldehyde in water. [2]
(b) Ethanol, a common solvent used in cosmetic products due to its volatility,
can undergo oxidation to form ethanoic acid as shown in the half-equation
below:
CH3COOH + 4H+ + 4e CH3CH2OH + H2O E = 0.06 V
The cell notation of an electrochemical cell involving ethanol is given below
Pt(s) | CH3CH2OH(aq), CH3COOH(aq) || MnO4(aq), Mn2+(aq) | Pt(s)
(i) Draw a fully labelled diagram of the electrochemical cell, indicating
trendyline
the flow..
h direction of electron flow [3]
(ii) With reference to the

t Data Booklet
Booklet,, write
write
e an overall equation for the
reaction
eaction which take
takes place in the cell.
cell [2]
1612 trendyline
6
(iii) Hence, calculate the Ecell for the reaction. [1]
(iv) Describe and explain the effect on Ecell when the concentration of
hydrogen ions is increased in the Mn2+(aq), MnO4(aq) | Pt(s) half
cell. [2]
(c) In the cosmetic jewellery industry, electroplating is the application of a

metal coating to a conducting surface (e.g. pendant) by an electrochemical
process.
One common electrolytic cell for the plating of silver consists of a silver
electrode connected to the anode and the article to be plated connected to
the cathode. The electrolyte used is silver(I) sulfate solution.
(i) Calculate the time taken, in hours, for 2.00 g of silver to be plated
when a current of 0.250 A flows through the electrolyte. [2]
(ii) Suggest and explain whether the electroplating process would be

accelerated if an electrolyte with a higher concentration is used. [1]
[Total: 20]
1613 trendyline
7
4 Shikimic acid, C7H10O5, is a monobasic carboxylic acid used in the production of

Tamiflu, an antiviral medical that is used to treat children with Influenza A and
Influenza B. Shikimic acid can be extracted from the seeds of the sweetgum
fruit.
(a) When the extract of 0.300 g of sweetgum fruit seeds was titrated with
1.00 g dm3 aqueous sodium hydroxide, 16.45 cm3 of aqueous sodium
hydroxide was required to neutralise the Shikimic acid present.
Calculate the percentage by mass of Shikimic acid extracted from the

sweetgum fruit seeds.
You may assume that Shikimic acid is the only compound in the
sweetgum fruit seeds that reacts with sodium hydroxide. [3]
(b) Shikimic acid can undergo condensation with ethanol using concentrated
sulfuric acid as a catalyst to form an ester and water. The enthalpy
change for the forward reaction is 20.0 kJ mol1 and the activation
energy is +50.0 kJ mol1.
(i) Draw a fully labelled reaction pathway diagram for this reaction. [2]
(ii) Determine the activation energy of the reverse reaction. [1]
(iii) On the diagram you have drawn in (b)(i), draw the reaction
pathway diagram for the condensation reaction carried out in the
absence of sulfuric acid. Label the graph for the uncatalysed
reaction as (b)(iii). [1]
(iv) Describe, with the aid of a labelled Boltzmann distribution diagram,

the effect of adding concentrated sulfuric acid on the rate of the
condensation reaction. [4]
trendyline
1614 trendyline
8
(c) The following information were obtained from tests that were conducted
to deduce the structure of Shikimic acid.
x Shikimic acid is a hexacyclic monobasic carboxylic acid with the

molecular formula, C7H10O5.
x Shikimic acid does not produce an orange precipitate with Bradys
reagent.
x On treatment of Shikimic acid with H2(g) and nickel catalyst at
150 oC, compound A was formed.
x 1 mole of Shikimic acid reacts exactly with 4 moles of PCl5 to give
compound B.
x Shikimic acid decolourises hot acidified potassium manganate(VII)
solution to give a single compound C. The structure of compound C is
shown in the diagram below.
Compound C
(i) Deduce the structures of Shikimic acid, and compounds A and B. [7]
(ii) State the number of possible stereoisomers of Shikimic acid. [1]
(iii) Draw the structure of the organic product formed when compound
C reacts with NaBH4. [1]
[Total: 20]
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1615 trendyline
9
5 (a) Describe the action of water on separate samples of magnesium and

barium, writing equations including state symbols for any reaction that
occurs. [4]
(b) (i) Calcium hydroxide is sparingly soluble in water and has a solubility
product with a numerical value of 5.50 x 106.
Write an expression for the solubility product, Ksp, of calcium

hydroxide and calculate the solubility of calcium hydroxide in water. [2]
(ii) A student tried to precipitate Ca(OH)2 by mixing 0.20 mol dm3 of

Ca2+(aq) with an equal volume of 0.20 mol dm3 NH3(aq).
Show through calculation why precipitation of Ca(OH)2 will not occur.

(Kb of NH3 = 1.80 x 105 mol dm3) [2]
(iii) Hence, deduce the minimum concentration of Ca2+(aq) that the

student must use that will result in precipitation of Ca(OH)2. [2]
(c) Draw the structural formula of the organic products formed when
compound D reacts with the following reagents.
Compound D
x Alkaline KMnO4(aq), heat

x NaOH(aq)
x Dry HCl(g) [3]
(d) (i) Compound D contains two functional groups that exhibit acidic
properties. Identify the two functional groups. [1]
(ii) Based on the two functional groups identified in (d)(i), state and
explain which of these two groups has a smaller pKa value. [4]
(iii)
trendyline
d li
dy
Suggest a common reagent that
strength of the functional
illustrate
llustra the
he reactio
reaction.
th t can
n be used to illustrate tthe acid
functiona group stated in
n (d)(
(d)(ii).. Write
te an equa
equation to
[2]
[Total: 20]
1616 trendyline
H2 Chemistry Paper 3 Solutions
1 (a) (i) Write an equation to show how phenylamine acts as a weak base in
water. [1]
C6H5NH2(aq) + H2O(l) C6H5NH3+(aq) + OH(aq)
(ii) The dissociation constant, Kb, for phenylamine is

10 3 o
3.98 x 10 mol dm at 25 C. Calculate the pH of a buffer solution
made up of phenylamine and its salt in a 3:1 ratio. [2]
pOH = pKb + lg [salt]/[base]
pOH = -lg(3.98 x 10-10) + lg (1/3)
= 9.400 + (-0.477)
= 8.923
pH = 14 8.923 = 5.08
(b) Sunset Yellow is used as an aqueous food colourant in sweets, orange

squash and jams. It is synthesised from 4-aminobenzenesulfonic acid.
4-aminobenzenesulfonic acid
(i) Explain why 4-aminobenzenesulfonic acid is less basic than

phenylamine. [2]
SO3H is an electron-withdrawing group, hence it increases the
delocalisation of the lone pair of electrons on N atom into the
benzene ring.
The lone pair of electrons on N atom in 4-aminobenzenesulfonic

acid is thus less available to accept a proton, making it a
weaker base than phenylamine.
(ii) The structure of Sunset Yellow is shown below.
t dyli
trendyline
colour of Sunset
Sunset Yellow
The sodium sulfonate groups (SO3Na a+) have little effect on the
nset Yellow. Suggest a reason
re why the sodium susulfonate [1]
1617 trendyline
2
groups are needed in the molecule.

The sodium sulfonate groups increases the solubility of Sunset
Yellow in water through ion-dipole interactions.
(c) Tetralin can undergo bromination by reacting with bromine in the presence
of anhydrous FeBr3.
Tetralin
(i) Suggest a reason why the FeBr3 used is anhydrous. [1]
To prevent FeBr3 from undergoing hydrolysis/reaction with
water making it unable to act as a Lewis acid.
(ii) Name and describe the mechanism for this reaction, including curly
arrows showing the movement of electrons, and all charges. [3]
Mechanism is electrophilic substitution
FeBr3 + Br2 [FeBr4] + Br+ (single arrow accepted)
(2, 3, 4 & 5 position is accepted)
(iii) Explain why the bromination of phenylamine does not require the
use of anhydrous FeBr3. [1]
S
The lone pair of electrons on the N atom delocalises into the (S
t dyli
trendyline
tren
system/electron
sy
system /electron cloud of the)
he benzenene ring,
ri
ring, hence incr
increasing
the electron density ofo the benzene ring (or more electro
electron rich
or more activated),
activated making phenylamine more reactive to towards
electrophilic substitution.
substitution
1618 trendyline
3
(d) (i) Another possible catalyst for the bromination reaction is the use of
transition elements.
Define what is meant by the term transition elements. [1]

A transition element is a d-block element which forms at least
one stable ion with a partially filled d subshell.
(ii) A white precipitate is formed initially when aqueous ammonia is
gradually added to aqueous copper(I) nitrate.
Write an equation for this reaction. [1]

[Cu(H2O)6]+(aq) + OH(aq) CuOH(s) + 6H2O(l)
white precipitate
Or
Cu+(aq) + OH(aq) CuOH(s)
white precipitate
(iii) However, the white precipitate in (d)(ii) dissolves when an excess of
aqueous ammonia is added, resulting in a colourless solution.
Explain why the final solution is colourless. [1]

Cu+ has a completely filled d subshell / does not have a vacant
d-orbital such that do od electronic transition cannot occur.
(iv) When excess aqueous ammonia is added to solution containing
copper(II) nitrate, a deep blue colour arises.
Explain for the deep blue colouration and state the colour of light
absorbed by the solution. [4]
In transition element complexes, the central Cu2+ ion has
partially filled d orbital.
In the presence of ligands, the d orbitals split into two groups of

different energy levels, with an energy gap (E) between them.
Electrons in a lower energy d-orbital can jump/promote to a

higher energy level by absorbing light energy. This process is
known as dood electronic transition.
The energy absorbed corresponds to the energy gap between

the lower and higher energy d-orbitals. The colour observed is
trendyline
y
the complementary
p y of the colours absorbed.
Blue colour is observed as orange colour is absorbed

absorbed.
(v) Suggest
S
Sugg est the series of colour change and formula of the complex
c [2]
1619 trendyline
4
formed when excess concentrated HCl is gradually added to a

solution of copper(II) nitrate.
It turns from blue to green (yellow-green) to yellow.
Complex formed: [CuCl4]2-
[20 marks]
trendyline
1620 trendyline
5
2 (a) (i) Name and describe the mechanism of the hydrolysis reaction of
CH3CH2Cl using NaOH(aq). In your answer show any relevant curly
arrows charges, dipoles or lone pairs of electrons you consider to be
important in this mechanism. [3]
Mechanism is nucleophilic substitution, SN2
(ii) Write the rate equation for the above reaction. [1]
Rate = k [CH3CH2Cl] [OH]
(iii) State how the rate constant is affected with an increase in the
concentration of CH3CH2Cl.
No effect (rate constant is only affected by temperature and
catalyst)
[1]
(iv) CH3CH2Cl can be prepared by reacting ethanol with SOCl2. Write an
equation for this reaction and suggest an advantage of using SOCl2
as a reagent for halogenation. [2]
CH3CH2OH + SOCl2 CH3CH2Cl + SO2 + HCl
This method has the advantage of forming only gaseous side-

products which are easily removed from the system.
(b) (i) Hydrolysis of halogenoalkanes releases halide ions that can be

precipitated as silver halide upon addition of AgNO3(aq). The
halogenoalkanes can be distinguished by the different colours of the
silver halides.
When NH3(aq) is added in excess, the white precipitate of AgCl

dissolves to give a colourless solution. Describe the dissolution of
AgCl precipitate in excess NH3(aq) with the aid of relevant
equations. [3]
AgCl(s) Ag+(aq) + Cl(aq) (1)
trendyline
y
Ag+ (aq) + 2NH3 (aq) [Ag(NH
NH3)2]+ (aq) (2)
According to Le Chateliers Principle, addition

a dition of excess
NH3(aq)/ [NH3] increases shifts equilibrium (2)
2) to the right which
+
causes [Ag (aq)] to decrease.
1621 trendyline
6
This results in the position of equilibrium (1) to be shifted to the

right, hence AgCl dissolves.
Or
This causes the ionic product of AgCl < Ksp of AgCl, hence AgCl
dissolves.
(ii) Halide ions can also be distinguished by the addition of acidified

K2Cr2O7(aq).
Using relevant Eo values in the Data Booklet to predict the reaction, if

any, when acidified K2Cr2O7(aq) is added to Cl(aq) and I(aq)
separately. In each case, calculate Ecell and write a balanced
Cr2O72 + 6Cl + 14H+ 2Cr3+ + 3Cl2 + 7H2O (for reference)
Ecell = +1.33 (+1.36) = 0.03 V < 0 (reaction is not feasible)
Cr2O72 + 6I + 14H+ 2Cr3+ + 3I2 + 7H2O

Ecell = +1.33 (+0.54) = +0.79 V > 0 (reaction is feasible)
(c) Silver chloride is sparingly soluble in water at room temperature.
Predict the signs of 'Hppt and 'Sppt for the precipitation reaction. Give a
reason for each of your prediction. [3]
Both 'Hppt and 'Sppt would be negative.
'Sppt is negative as the system becomes less disordered/less varied

ways of arranging particles due to a phase/physical state change
from (aq) to (s).
'Hppt is negative because more heat is released during the formation

of strong ionic bonds between Ag+ ions and Cl ions in AgCl(s) but
less heat is absorbed to overcome the weaker ion-dipole interactions
between Ag+ ions and Cl ions with water molecules.
(d) (i) When a precipitate is formed, 'Gppt, in J mol-1, is given by the
trendyline
trendyline
fo
'Gppt= 2.303RTlogK
Ksp
The Ksp of silver fluoride,

fluoride AgF, is 1.01 m 2 dm
1 01 mol m6 a
at room [2]
1622 trendyline
7
temperature.
Use the above expression of 'Gppt to determine whether AgF is

soluble in water at room temperature.
'Gppt = 2.303 x8.31 x298 x log(1.01)
= +24.6 J mol1 (sign + units + 3 s.f.)
A positive value of 'Gppt indicates that the precipitation

process is not spontaneous/not feasible/will not occur. Hence,
AgF is soluble in water at room temperature.
(ii) Hence, predict and explain how the solubility of AgF would change
when a solution of NaF is added. [2]
The presence of F ions from the dissolved NaF increases [F] /
due to common ion effect.
By Le Chateliers principle, this causes the position of

equilibrium of AgF(s) Ag+(aq) + F(aq) to shift to the left,
resulting in a lower solubility of AgF in NaF solution than in
water.
[20 marks]
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3 Cosmetic chemistry has been responsible for inventing a range of different

cosmetic products. Over the years, it is estimated that the cosmetic industry
makes $42.8 billion dollars per annum, and a large part of the industry depends
on the research and development behind the chemistry of cosmetics.
Benzaldehyde imparts a bitter almond flavour and aroma. It is commonly used

to produce almond-flavoured food and certain cosmetic products. Benzaldehyde
can be synthesised from cinnamaldehyde obtained from the oil of cinnamon.
(a) (i) Devise a three-step synthesis, starting from cinnamaldehyde, for the
manufacture of benzaldehyde. Give the reagents and conditions
required and the structure of the intermediates involved.
[5]
Step 1) Acidified KMnO4(aq), heat/reflux
Step 2) LiAlH4 in dry ether
Step 3) Acidified K2Cr2O7 (aq), heat with immediate distillation
Intermediate 1:
Intermediate 2:
(ii) Suggest one simple chemical test which would enable you to
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yyline
distinguish
d st gu s between
bet ee cinnamaldehyde
c a a de yde anda d benzaldehyde.
be a de yde Sta
State any
observations you would make with each compound
compound.. [2]
To each of the two compounds, add Fehlings solution.
Cinnamaldehyde
i ld h d will give a reddish
ddish brown precipitate
precipitate.
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Benzaldehyde will not give a reddish brown precipitate.
To each of the two compounds, add Br2(aq) / Br2(l) in CCl4.
Cinnamaldehyde will decolourize reddish brown Br2 solution.

Benzaldehyde will not decolourize reddish brown Br2 solution.
(iii)Benzaldehyde is considered to be soluble in water. By considering

relevant interactions, explain the solubility of benzaldehyde in water. [2]
Benzaldehyde is soluble in water because the energy released
by the formation of hydrogen bonds between molecules of
benzaldehyde and water [1] is sufficient to overcome the
permanent dipole-permanent dipole interactions between
benzaldehyde molecules and the hydrogen bonds between
water molecules.
(b) Ethanol, a common solvent used in cosmetic products due to its volatility,
can undergo oxidation to form ethanoic acid as shown in the half equation
below:
CH3COOH + 4H+ + 4e CH3CH2OH + H2O E = 0.06 V
The cell notation of an electrochemical cell involving ethanol is given below
Pt(s) | CH3CH2OH(aq), CH3COOH(aq) || MnO4-(aq), Mn2+(aq) | Pt(s)
(i) Draw a fully labelled diagram of the electrochemical cell, indicating

the flow of electrons. [3]
e-
Temperature 298 K
Pressure 1 atm
Salt bridge
Pt(s) electrode
Pt(s) electrode
CH3CH2OH (aq) MnO4- (aq)

1 mol dm-3 1 mol dm-3
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dyli
CH3COOH (aq)
C Mn2+ (aq)
(a
1 mol dm-3 dm-3
1 mol d
(ii) With reference to the Data Booklet,

ook , write an overall balanced
Booklet ba [2]
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10
equation for the reaction which takes place in the cell.

From the Data Booklet,
MnO4- + 8H+ + 5e- Mn2+ + 4H2O E = + 1.52 V
Oxidation: CH3CH2OH + H2O CH3COOH + 4H+ + 4e (x5)

Reduction: MnO4- + 8H+ + 5e- Mn2+ + 4H2O (x4)
Overall equation:
5CH3CH2OH + 4MnO4- + 12H+ 5CH3COOH + 4Mn2+ + 11H2O
(iii) Hence, calculate the Ecell for the reaction. [1]
Ecell = Ered - Eoxi
= + 1.52 ( 0.06)
= + 1.58 V
(iv) Describe and explain the effect on the cell potential when the
concentration of hydrogen ions is increased in the
2+ -
Mn (aq), MnO4 (aq) | Pt half cell. [2]
MnO4- + 8H+ + 5e- Mn2+ + 4H2O
When [H+] increase, system attempts to decrease [H+]. By Le

Chateliers Principle, the position of equilibrium shifts right
favouring reduction process. E MnO4-/Mn2+ will be more positive
(than +1.52 V).
Ecell will be more positive [1] (than +1.58 V)

(c) In the cosmetic jewellery industry, electroplating is the application of a
metal coating to a conducting surface (e.g. pendant) by an electrochemical
process.
One of the common electrolytic cell consists of a silver electrode

connected to the anode and the article to be plated connected to the
cathode. The electrolyte used is silver(I) sulfate solution.
(i) Calculate the time taken, in hours, for 2 g of silver to be plated when
a current of 0.250 A flows through the electrolyte. [2]
Ag+(aq) + e- Ag(s)
Amount of silver to be plated = 2/108

= 1.852 x 10-2 mol
t
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e- Ag
Amount of electrons, n = 1.85 0--22 mol
1.852 x 10 mo
Quantity of charge, Q = nF
0--22 x 96500
= 1.852 x 10
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= 1787 C
Time, t = 1787/0.250
= 7148 s
= 7148/3600
= 1.99 hr
(ii) Suggest and explain if the electroplating process would be

accelerated if an electrolyte with a higher concentration is used. [1]
No as the electroplating process is dependent on the time and
current of the electrolytic cell.
Or
Concentration of the electrolyte does not affect the amount of
electrons discharged in the solution.
[Total: 20]
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4 Shikimic acid, C7H10O5, is a monobasic carboxylic acid used in the production of

Tamiflu, an antiviral medical that is used to treat children with influenza A and
influenza B symptoms. Shikimic acid can be extracted from the seeds of the
sweetgum fruit.
(a) When the extract of 0.300 g of sweetgum fruit seeds was titrated with
1.00 g dm-3 aqueous sodium hydroxide, the titration required 16.45 cm3 of
aqueous sodium hydroxide to neutralise the shikimic acid present.
Calculate the percentage by mass of shikimic acid extracted from the

sweetgum fruit seeds.
You may assume that shikimic acid is the only active ingredient in the
sweetgum fruit seeds that reacts with sodium hydroxide. [3]
RCOOH + NaOH RCOO-Na+ + H2O
Mr of Shikimic acid = 174, Mr of NaOH = 40
Concentration of sodium hydroxide= 1.00 / 40 = 0.0250 mol dm-3
Amount of NaOH used in titration = 0.0250 x 16.45/1000 = 4.11 x 10-

4
mol
Since RCOOH NaOH
Amount of RCOOH used in titration = 4.11 x 10-4 mol
Mass of RCOOH used in titration = 4.11 x 10-4 x 174 = 0.0716 g

% mass of shikimic acid = 0.0716 / 0.30 x 100% = 23.9%
(b) Shikimic acid can undergo condensation with ethanol using concentrated
sulfuric acid as a catalyst to form an ester and water. The enthalpy
change for the forward reaction is 20.0 kJ mol-1 and the activation
energy is +50.0 kJ mol-1.
(i) Draw a fully labelled reaction pathway diagram for this catalysed
reaction. [2]
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13
bi) Catalysed reaction
+50.0
(ii) Determine the activation energy of the reverse catalysed reaction. [1]
Activation energy = 50.0 + 20.0 = +70.0 kJ mol-1
(iii) On the same diagram in (b)(i), draw the reaction pathway diagram
for the condensation reaction in the absence of sulfuric acid. Label
the graph as for this uncatalysed reaction as (b)(iii) clearly. [1]
(iv) Describe, with the aid of a labelled Boltzmann distribution diagram,

the effect of concentrated sulfuric acid on the condensation
reaction. [4]
Fraction of
molecules
Number of molecules with
energy t Ea (uncatalysed)
Number of molecules with
energy t Ea (catalysed)
0
energy E
Ea Ea
A catalyst provides an alternative pathway of lower activation
energy.
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dyline
y
As a result, there is a greater number of molecules having
energy greater than or equal to activation energy
an increase in the number/frequency
energy. This leads
numberr equenc of effective col
and therefore increases the rate
ate of reaction
reaction..
co
le to
collisions
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14
(c) The following information were obtained from tests that were conducted
to deduce the structure of shikimic acid.
x Shikimic acid is a hexacyclic monobasic carboxylic acid with the

molecular formula, C7H10O5.
x Shikimic acid does not produce an orange precipitate with Bradys
reagent.
x On treatment of shikimic acid with H2(g) and platinum catalyst,
compound A was formed.
x 1 mole of shikimic acid reacts exactly with 4 moles of PCl5 to give
compound B.
x Shikimic acid decolourises hot acidified potassium manganate(VII)
solution to give a single compound C. The structure of compound C is
shown in the diagram below.
Compound C
(i) Deduce the structures of shikimic acid and compounds A and B. [7]
Shikimic acid A B
Or
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Shikimic
kimic acid A B
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15
Evidence Deduction
Shikimic acid does not Shikimic acid does not
produce an orange contain an aldehyde or a
precipitate with Bradys ketone (carbonyl) functional
reagent. group.
On treatment of shikimic Shikimic acid contains

acid with H2(g) and platinum alkene which undergoes
catalyst, compound A was (catalytic) addition or
formed. reduction to form alkane in
A.
1 mole of shikimic acid Shikimic acid contains 4

reacts exactly with 4 moles alcohol or carboxylic acid
of PCl5 to give compound B. which undergoes
nucleophilic substitution to
give chloroalkane or acyl
chloride in B.
Since shikimic acid is

monobasic, it contains 1
carboxylic acid and 3
alcohol functional groups
Shikimic acid decolourises Shikimic acid contains 2o
hot acidified potassium alcohol and alkene which
manganate(VII) solution to undergoes oxidation to give
give a single compound C. ketone and carboxylic acid
respectively.
(ii) State the number of possible stereoisomers of shikimic acid. [1]
Number of isomers = 23 = 8
(iii) Draw the structure of the organic product when compound C reacts
with NaBH4. [1]
t d li
[Total 20]
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5 (a) Describe the action of water on separate samples of magnesium and

barium, writing equations including state symbols for any reaction that
occurs. [4]
Mg has no reaction with cold water. It only reacts with steam.
Mg(s) + H2O(g) MgO(s) + H2(g)
Ba reacts violently/vigorously with cold water.
Ba(s) + 2H2O(l) Ba(OH)2(aq) + H2(g)
(b) (i) Calcium hydroxide is sparingly soluble in water and has a solubility
product with a numerical value of 5.50 x 106.
Write an expression for the solubility product, Ksp, of calcium

hydroxide and calculate the solubility of calcium hydroxide in water. [2]
Let the solubility of Ca(OH)2 be y mol dm3.
Ca(OH)2(s) Ca2+(aq) + 2OH(aq)
y y 2y
Ksp = [Ca2+] [OH]2
5.50 x 106 = (y) x (2y)2

= 4y3
y = 1.11 x 102 mol dm3
(ii) A student tried to precipitate Ca(OH)2 by mixing 0.20 mol dm3

Ca2+(aq) with equal volume of 0.20 mol dm3 NH3(aq).
Show through calculation why precipitation of Ca(OH)2 will not occur.

(Kb of NH3 = 1.80 x 105 mol dm3) [2]
NH3(aq) + H2O(l) NH4+(aq) + OH(aq)
Since dissociation of NH3(aq) is negligible,

and [OH] = [NH4+]
[NH4+] [OH]
Kb = [NH3]
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[OH]2
1.80 x 105 = (0.20)
[OH] = 1.90
1.9 x 103 mol
ol dm3
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17
Ionic product of Ca(OH)2 = [Ca2+] [OH]2
2
=(
)( )

= 9.00 x 108 mol3 dm9 < Ksp Ca(OH)2, no precipitation

[1]
(iii) Hence, deduce the minimum concentration of Ca2+(aq) that the
student must use that will result in precipitation. [2]
2+ 2
[Ca ] [OH ] = Ksp Ca(OH)2
[Ca2+] (1.90 x 103)2 = 5.50 x 106
[Ca2+] = 1.52 mol dm3
Minimum [Ca2+] needed for precipitation to occur

= 2 x 1.52 = 3.04 mol dm3
(c) Draw the structural formula of the organic products formed when
compound D reacts with the following reagents.
Compound D
x Alkaline KMnO4(aq), heat [1]
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d li
x NaOH(aq) [1]
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18
x Dry HCl(g) [1]
(d) (i) Compound D contains two acidic functional groups that exhibit acidic
properties. Identify the two functional groups. [1]
Phenol and carboxylic acid
(ii) Based on the two functional groups identified in (d)(i), state and
explain which of these two groups has a smaller pKa value. [4]
The carboxylic acid group has a lower pKa.
The negative charge on the carboxylate ion is dispersed

through delocalisation of electrons within the RCOO S
system.
The negative charge of the phenoxide ion is dispersed through

delocalisation of electrons within the benzene S system/ p
orbital of O overlaps with the S system of benzene ring
However, the dispersal of negative charge is more effective in

the carboxylate ion than the phenoxide ion. This results in the
carboxylate ion to be more stable and hence, a greater extent of
dissociation by the carboxylic acid functional group and thus a
stronger acid, lower pKa.
t dyli
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(iii) Suggest a common reagent that
Su th can be e used
use to illustrate the acid
strength of the functional group stated in (d)(
(d)(ii).. Write an equ
equation to
illustrate
llustra the reaction.
reactio [2]
Reagent and condition: Na2CO3
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[20 marks]
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VICTORIAJUNIOR COLLEGE
JC 2 PRELIMINARY EXAMINATIONS
Higher 2
CHEMISTRY 9647/01
Paper 1Multiple Choice 22 September 2016
1 hour

Data Booklet

Write your NRIC/FIN number, name and CT group on the Answer Sheet.
There are fortyquestions. Answer all questions. For each question there are four possible
answers A, B, C and D.
Choose the one you consider correct and record your choices in soft pencil on the separate
Answer Sheet.
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This document consists of 16 printed pagesand 0 blank page.
VJC 2016 9647/01/PRELIM/16

1636 [Turn over trendyline
2
Section A
For each question there are four possible answers, A, B, C, and D. Choose the one you
The most common ionmolecule reaction in gas clouds of the Universe is as shown.
H 2 (g) + H 2 +(g) H(g) + H 3 +(g)
What could be the composition of an H 3 + ion?
protons neutrons electrons

A 2 1 1
B 2 1 2
C 3 0 1
D 3 0 2
2 Two glass vessels M and N are connected by a closed valve.
M N
M contains helium at 20 oC at a pressure of 1 x 105 Pa. N has been evacuated, and has
three times the volume of M. In an experiment, the valve is opened and the temperature
of the whole apparatus is raised to 100 oC.
A 3.18 104 Pa
B 4.24 104 Pa
C 1.25 105 Pa
D 5.09 105 Pa
3 The shell of a chickens egg makes up 5% of the mass of an average egg. An average
egg has a mass of 50 g.
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Assume the
e egg shell is pure calcium carb
he carbonate.
How many neutralise 50 cm3 of 2.0

y complete chickens egg shells would be needed to neutrali
mol dm3 ethanoic
thanoic acid?
A 1 B 2 C 3 D 4
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3
4 Aluminium carbide, Al 4 C 3 , reacts readily with aqueous sodium hydroxide. The two
products of the reaction are NaAlO 2 and a hydrocarbon. Water molecules are also
involved as reactants.
What is the formula of the hydrocarbon?
A CH 4 B C2H6 C C3H8 D C 6 H 12
5 Which statement about the ammonium ion, NH 4 +, is correct?
A All bond angles are 107o.

B Ammonium ions are formed when ammonia behaves as an acid.
C Ammonium ions are unreactive when heated with NaOH(aq).
D The bonds are all of the same length.
6 2methylpropan1ol and butan1ol are structural isomers. 2methylpropan1ol has

a lower boiling point.
Which statement explains why the boiling point of 2methylpropan1ol is lower than
that of butan1ol?
A 2methylpropan1ol cannot form hydrogen bonds.

B 2methylpropan1ol has weaker covalent bonds than butan1ol.
C 2methylpropan1ol has weaker dispersion forces than butan1ol.
D 2methylpropan1ol molecules have more surface area than butan1ol
molecules.
7 The Gibbs free energy change, G eq , is related to the equilibrium constant, K eq , by the
following equation.
G eq = 2.303 RT lg K eq
where R is the gas constant and T is the temperature in Kelvin.
Which statement about the following equilibrium is correct?
CO 2 (g) CO 2 (aq)
A Increasing the pressure at constant temperature makes G eq more negative.

B Adding a catalyst makes G eq more negative.
C The dissolution of CO 2 in water is spontaneous for all values of K eq .
D At constant temperature, a shift in position of equilibrium to the right results in the
same value of G eq .
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VJC 2016 9647/01/PRELIM/16
4
8 Metaldehyde, (CH 3 CHO) 4 , is used as a solid fuel for camping stoves. The equation for
the complete combustion of metaldehyde is shown.
(CH 3 CHO) 4 (s) + 10O 2 (g) 8CO 2 (g) + 8H 2 O(l)
H{ c = standard enthalpy change of combustion.
Which expression will give a correct value for the enthalpy change of formation of
metaldehyde?
A H{ c metaldehyde (8H{ c carbon + 8H{ c hydrogen)

B H{ c metaldehyde (8H{ c carbon + 16H{ c hydrogen)
C (8H{ c carbon + 8H{ c hydrogen) H{ c metaldehyde
D (8H{ c carbon + 16H{ c hydrogen) H{ c metaldehyde
In research laboratories, the standard calomel reference electrode and the AgCl/Ag
reference electrodes are often used in place of the standard hydrogen electrode (SHE).
Their standard reduction potentials with respect to the SHE are shown below.
Calomel electrode: Hg 2 Cl 2 + e Hg + Cl Eo = +0.27 V

AgCl/Ag electrode: AgCl + e Ag + Cl Eo = +0.22 V
A halfcell containing Au+/Au has a reduction potential of +1.56 V with respect to a

calomel electrode.
A The reduction potential of the Au+/Au halfcell with respect to the SHE is +1.83 V.
B The reduction potential of the Au+/Au halfcell with respect to the AgCl/Ag
electrode is +1.78 V.
C Ag has a higher tendency to be oxidised than H 2 .
D Hg 2 Cl 2 has a lower tendency to be reduced than AgCl.
10 What is the volume of 0.100 mol dm3 NaOH that should be added to 20 cm3 of
0.100 mol dm3 CH 3 CO 2 H (K a = 1.8 x 105 mol dm3) to form a buffer of pH 5.5?
A 15.0 cm3 B 16.0 cm3 C 17.0 cm3 D 18.0 cm3
11 H 2 (g) and I 2 (g) react according to the following equilibrium.
H 2 (g) + I 2 (g) 2HI(g)
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When 0.10 m of H 2 (g) and 0.10 mol of I2 (g) are heated in a seale
0 mol sealed vessel at 600 K,
0.06 mol of HI was present at equilibrium
equilibrium.
e K c value for the reaction at 600 K?

What is the
A 0.184 B 0.360 C 0.735 D 1.36
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5
12 After the Fukushima nuclear disaster in 2011, a radioactive isotope of iodine, 131I, was
detected at water purification plants in Japan. Radioactive decay is a first order reaction,
and the halflife of radioactive 131I is 8 days.
What is the mass of 131I left after 40 days if the initial mass of 131I was 15 g?
15 15 15 15
A g B 5g C g D g
2 5 2 28 28
13 Which of the following shows the properties of a Group II element? [ = ohm]
melting electrical
point / oC density / g cm 3
conductivity / 1 m1
A 98 0.97 2.4 107
B 113 2.07 7.7 107
C 649 1.74 2.2 107
D 1744 11.3 6.0 107
14 X, Y and Z are elements in the third period of the Periodic Table. The oxide of X is
amphoteric, the oxide of Y is basic and the oxide of Z is acidic.
What is the order of increasing ionic radius for these three elements?
A X, Y, Z B X, Z, Y C Y, X, Z D Y, Z, X
15 Sulfur is an element in the third period, Na to Ar, of the Periodic Table.
Which is the correct statement for sulfur?
A Sulfur is the only element in this period which forms two acidic oxides.
B Sulfur has the highest first ionisation energy of the elements in this period.
C Sulfur is the only element in this period which can form compounds with variable
oxidation states.
D Sulfur is the only element in this period which can exist, at room temperature and
pressure, as a simple molecule containing eight atoms.
16 Which anions containing chlorine are formed when chlorine is passed into hot aqueous
potassium hydroxide?
A Cl and ClO
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B Cl and
nd ClO 3
d ClO
C Cl and ClO 4
nd ClO
Cl
D ClO and ClO
C 3
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6
17 Four different complexes can be obtained by reacting aqueous cobalt(III) chloride with
ammonia under various conditions. Different proportions of chloride are precipitated
when each complex is treated with aqueous silver nitrate.
empirical number of moles of AgCl

formula colour of solid precipitated per mole of complex
I CoCl 3 (NH 3 ) 6 orange 3

II CoCl 3 (NH 3 ) 5 violet 2
III CoCl 3 (NH 3 ) 4 violet 1
IV CoCl 3 (NH 3 ) 4 green 1
Which of the following statements is correct regarding the four different complexes?
A Only complexes III and IV have the coordination number of 6.

B The cations in all four complexes have the same charge.
C Ligands of complex I consists of both chloride and ammonia.
D Complexes III and IV are stereoisomers.
18 In 1869 Ladenburg suggested a structure for benzene, C 6 H 6 , in which one hydrogen

atom is attached to each carbon atom.
Ladenburg structure
A compound C 6 H 4 Br 2 could be formed with the same carbon skeleton as the

Ladenburg structure.
How many structural isomers would this compound have?
A 2 B 3 C 5 D 6
19 Samples of the gases CH 3 CH 2 Cl and Cl 2 are mixed together and irradiated with light.
Which of the following is not likely to be formed in the reaction?
A CH 3 CHCl 2
B CHCl 2 CH 2 Cl
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C CH 3 CH
H 2 CH 2 CH 3
D CH 2 C
ClCH(Cl)CH(Cl)CH
lCH(C
CH(Cll)CH(C
)CH(Cll)CH 3
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20 Compound U gives a positive test with Tollens reagent and can be oxidised with
acidified K 2 Cr 2 O 7 to form 3methylbutanoic acid.
Compound U can be reduced by NaBH 4 to form compound V which reacts with

ethanoyl chloride to form compound W.
What is the structure of compound W?
A CH 3 CH(CH 3 )CH 2 CH 2 CO 2 CH 3
B CH 3 CH 2 CH 2 CH(OCOCH 3 )CH 3
C CH 3 CH(CH 3 )CH 2 CH 2 OCOCH 3
D CH 3 CH 2 CH(CH 3 )CH 2 OCOCH 3
21 The Wittig reaction offers a highly versatile method to synthesise a wide variety of
alkenes. The mechanism for the reaction is summarised as follows.
Ph3P O PPh3
+ X PHPh3 1) NaH O PPh3
+
X CH R I HC R C C R
O II C C R
2) R'
R' R' C R'
,
(Ph denotes a phenyl group C6H5 )
Which of the following correctly represents the type of reaction occurring in stages I and
II?
stage I stage II
A nucleophilic substitution elimination
B nucleophilic substitution condensation
C nucleophilic addition elimination
D nucleophilic addition condensation
22 Which of the following can be used to distinguish between the two compounds?
H O
C HO O O
O O C
A H 2 and Pd
B Br 2 (aq)
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C g reagent
warm Fehlings g
D hot acidified K 2 Cr 2 O 7
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8
23 The presence of a halogen in an organic compound may be detected by warming the

organic compound with aqueous silver nitrate.
Which compound would be the quickest to produce a precipitate?
A B C D
F F Cl Cl
F Cl Cl Br
I F Cl F
24 Warfarin (M r = 308) is an oral anticoagulant that is used to prevent heart attacks,

strokes and blood clots. The structural formula of warfarin is given below.
O O
O
OH
Which of the following statements about warfarin is correct?
A It has a total of 4 stereoisomers.

B It reacts with CH 3 COCl to form white fumes.
C 1 mol of warfarin reacts with 1 mol of alcoholic potassium cyanide in the presence
of heat.
D 1 mol of warfarin reacts with 1 mol of hydrogen gas in the presence of nickel
catalyst and heat.
25 The reaction conditions for four different transformations are given below.
Which transformation has a set of reagents or conditions that is not correct?

+
CH3CH2O Na (alc)
A CH3CHBrCH3 CH3CH=CH2
reflux
OH Na(s) O Br
B Br
Br heat
O O O O
CH3NH2
C C CH3 C C CH3
C N N
HO OH
H H
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re
e
H2
D CH3CN
CN H3C
CH
C H2NH2
CH
Ptt
P
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26 Compound R is formed from compound Q as shown below.
PCl5
compound Q N
O
compound R
Which structure could be Q?
CO2H
A
N
H
CO2H
B
N
H
CO2H
C
N
H
CO2H
D
N
H
27 The reaction of compound E (M r = 152) with hot acidified potassium manganate(VII)

yields three products, F, G and H.
F can be converted to G with the use of alkaline aqueous iodine followed by

acidification with aqueous sulfuric acid.
Which of the following shows the structure of compound E?
A O
B O
C OH
te
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OH
D
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10
28 Compound J is a pharmaceutical drug.

OH
CH3CONH
H2N CO2CH2CH3
J
What is the species formed when compound J is heated with HCl(aq)?
OH
CH3CONH
A
H3N CO2CH2CH3
OH
H3N
B
H3N CO2H
OH
H3N
C
H3N CO2CH2CH3
OH
CH3CONH
D
H3N CO2H
29 Which synthetic route will lead to the successful synthesis of the following product?
CO2H
CH2CH2CH3
CHO LiAlH4 CH2OH K2Cr2O7 CO2H
A in dry ether H2SO4(aq)

CH2CH=CH2 CH2CH2CH3 heat CH2CH2CH3
CHO CH2OH CO2H
LiAlH4 KMnO4
B in dry ether H2SO4(aq)
CHO CH2OH CO2H
H2 KMnO4
C
D
H2C
CH CH
t dy i e
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H=CH
H2
HO
CHO
C
Ptt
P
H2
Pt
H2C
CH
C H2C
CH H3
CH
CH2O
CH H
OH
H2SO4(aq)
at
hea
K2Cr2O7
H2SO4(aq)
CH2CH2CH3
CO2H

VJC 2016 9647/01/PRELIM/16
1645 trendyline
11
30 Soy sauce is produced by the fermentation of soy beans by the mould Aspergillus
oryzae. The distinctive salty taste of the sauce is due to salts of glutamic acid formed
during fermentation.
NH2
HO2C CO2H
glutamic acid
The pHvolume curve obtained when 30 cm3 of NaOH is added to 10 cm3 of the
protonated form of glutamic acid of the same concentration is given below.
pH
9.5
4.1
2.1
0 10 20 30 VNaOH added / cm3
Which of the following is the major species present at point S?
A B
+ +
NH3 NH3
-
HO2C CO2H HO2C CO2
C D
+
NH3 NH2
- - - -
O2C CO2 O2C CO2
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VJC 2016 9647/01/PRELIM/16
12
Section B
For each of the questions in this section, one or more of the three numbered statements 1 to
3 may be correct.
A B C D
1, 2 and 3 1 and 2 2 and 3 1 only
31 Hydrogen reacts with gaseous bromine to form hydrogen bromide
H 2 (g)+ Br 2 (g) 2HBr(g)
and with gaseous iodine to form hydrogen iodide.
H 2 (g)+ I 2 (g) 2HI(g)
For the first reaction, the rate equation is
k1 [H2 ][Br2 ]1.5

rate =
[Br2 ]+k2 [HBr]
For the second reaction, the rate equation is
rate = k[H 2 ][I2 ]
What can be deduced from this information only?
1 For the hydrogen / bromine reaction, the formation of HBr slows down the rate of
the forward reaction.
2 Only the hydrogen / iodine reaction could be a single step reaction.
3 The mechanism of the hydrogen / bromine reaction involves free radicals.
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VJC 2016 9647/01/PRELIM/16
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13
Given the enthalpy changes of the following reactions.
Mg(s) + Cl 2 (g) MgCl 2 (s) H = 642 kJ mol1

Mg(s) Mg2+(g) H = +2334 kJ mol1
Cl 2 (g) + 2e 2Cl(g) H = 454 kJ mol1
1 The enthalpy change of formation of MgCl 2 (s) is 642 kJ mol1.

2 The enthalpy change of atomisation of Mg(s) is +148 kJ mol1.
3 The electron affinity of Cl(g) is 698 kJ mol1.
The Direct Borohydride Fuel Cell (DBFC) is a type of alkaline fuel cell that uses NaBH 4
as the fuel and O 2 as the oxidant. A DBFC was set up under standard conditions
according to the diagram below.
The electrode potential of the NaBH 4 /NaBO 2 halfcell is given below.
NaBO 2 + 6H 2 O + 8e NaBH 4 + 8OH Eo = 1.24 V
Which of the following statements regarding the DBFC are correct?
1 The voltmeter will register a reading of +1.64 V.

2 Electrode X is the anode and electrode Y is the cathode in the DBFC.
3 The BO 2 ion produced at electrode X has a bond angle of 180o.
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VJC 2016 9647/01/PRELIM/16
14
A B C D
1, 2 and 3 1 and 2 2 and 3 1 only
34 The K sp values of three metal hydroxides are given in the table below.
metal hydroxide K sp
Ca(OH) 2 4.7 x 10 mol3 dm9
6
Sn(OH) 2 5.4 x 1027 mol3 dm9

Cr(OH) 3 6.7 x 1031 mol4 dm12
1 The concentration of OH in a saturated solution of Ca(OH) 2 is 0.021 mol dm3.

2 Ca(OH) 2 (s) will be precipitated if equal volumes of 0.02 mol dm3 NaOH(aq) and
0.02 mol dm3 Ca(NO 3 ) 2 (aq) are mixed together.
3 Cr(OH) 3 has the lowest solubility amongst the three metal hydroxides.
35 Which of the following properties generally increase down Group II?
1 thermal stability of the iodate(V) salt, M(IO 3 ) 2

2 magnitude of the lattice energy of the oxide, MO
3 charge density of the M2+ ion
36 Which of the following statements regarding the metal complex below are correct?
Cl CH3
O
O N
M CH3
N Cl
H2
N
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1 The oxidation number of M in the complex is +3.
2 The coordination
oordination number of M in the
he complex is 6.
6
3 The complex
omplex contains a tetradentate ligand.
ligan
VJC 2016 9647/01/PRELIM/16

1649 trendyline
15
37 Compound L has a chiral centre and forms a zwitterion.
Which could be the structure of L?
HO
CH3
1 H2N C CO2H
H
H NH2
2 HO C C H
H CO2H
H H NH2
3 C C C H
H H CO2H
38 In which of the following pairs are the members, I and II,

stereoisomers of each other, and
the overall dipole moment of I is larger than that of II?
I II
O2N Br O2N H
1 C C C C
H H H Br
CH3 H CH3 Br
2 C C C C
Br Cl H Cl
Br Br
Br C Br C
C H C H
3
C Br C Cl
H H
Cl Br
39 Which of the following statements regarding compound T are correct?
CH3
HN CH3 OH
C N CONHCH2CH2CO2H
H H
compound T
1 CompoundTreacts
poundT
pound Treacts with excess aqueous bromine to give a product
p with five
mine
ne atoms.
bromine
2 ol of compound T reacts with 3 mol of ethanoyl chloride.
1 mol
3 ol of compound T reacts with 3 mol
1 mol ol of
o cold dilute hydrochloric acid.
VJC 2016 9647/01/PRELIM/16

16
A B C D
1, 2 and 3 1 and 2 2 and 3 1 only
40 The diagram shows a molecule of a compound used as a flame retardant.
Br
Br
Br
Br Br
Br
Which statements about this structure are correct?
1 Each brominated C atom is chiral.

2 The molecular formula is C 12 H 20 Br 6 .
3 The CCC bond angles are all 120o.
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VJC 2016 9647/01/PRELIM/16
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17
Level of difficulty Percentage No of questions

Easy 22.5 9
Moderate 55 22
Difficult 22.5 9
MCQ Questions for H2

Qn Topic Remarks Answer
1 Atomic Structure (p, n, e) E D
2 Gases (calculation) M A
3 Atoms, Molecules, Stoichiometry (calculation) M B
4 Atoms, Molecules, Stoichiometry (equation) M A
5 Bonding (, bond length) & IE I (acidbase properties) M D
6 Bonding (IMF) M C
7 Entropy T D
8 Enthalpy (H f , H c ) M C
9 Eo (electric cells) T B
10 IE I (buffer calculation) M C
11 Chemical Eqm (K c calculation) E C
12 Kinetics I (t 1/2 calculation) E B
13 Group II (physical properties) E C
14 Periodic Table (ionic radius) M A
15 Periodic Table (properties of S) M D
16 Group VII (Cl 2 + hot OH reaction) E B
17 Transition Metals (ligand / coordination no.) T D
18 Organic (structural isomerism) M A
19 Organic (FRS mechanism) M C
20 Organic (RCHO, ROH reactions) M C
21 Organic (types of mechanism) M A
22 Organic (distinguishing test: RCHO, ester, phenol) M D
23 Organic (RX: AgNO 3 reaction) E A
24 Organic (C=C, ester, RCO, ROH reactions) M B
25 Organic (RX, C=C, RCO 2 H reactions) T C
26 Organic (RX, RCO 2 H, amine reactions) T B
27 Organic (C=C, ROH, RCO reactions) T A
28 Organic (hydrolysis reaction: amide, amine, ester) M B
29 Organic (phenol, C=C, amine reactions) M D
30 Organic (amino acid titration curve) E C
31 Kinetics II (mechanism, rate equation) M B
32 H calculation M B
33 Eo (fuel cell) + Bonding (bond ) T A
34 IE II (K sp calculation) T D
35 Group II (physical/chemical properties) E D
36 Transition Metals (reaction) M A
37 Organic (amino acid) E A
38 Organic (stereoisomers, dipole moment) M D
39 Organic (phenol, RCO 2 H, amine, amide reactions) T B
40 Organic (chiral C, MF, ) M D
Qn
No trendyline
trendylin
y ne Modified/New MCQ Questions for H1
Topic Remarks Answer
VJC 2016 9647/01/PRELIM/16

Victoria Junior College Option A: Both 2methylpropan1ol and butan
2016JC2 H2 Chemistry Prelim Paper 1 1ol can form intermolecular hydrogen bonds due
Suggested Answers to the presence of OH in the molecules.
Option B: Both molecules have strong covalent
No. Ans No. Ans No. Ans No. Ans bonds between their atoms.
1 D 11 C 21 A 31 B Options C and D: 2methylpropan1ol has
weaker dispersion forces than butan1ol as 2
2 A 12 B 22 D 32 B
methylpropan1olis more spherical and has less
3 B 13 C 23 A 33 A (not more) surface area for electron interaction
4 A 14 A 24 B 34 D than butan1ol.
5 D 15 D 25 C 35 D
7 D
6 C 16 B 26 B 36 A
Options A, B and D: K eq is unaffected by
7 D 17 D 27 A 37 A increasing the pressure, adding a catalyst or a
8 C 18 B 28 B 38 D shift in position of equilibrium. K eq is only affected
9 A 19 C 29 D 39 B by a change in temperature. Hence G eq has the
10 C 20 C 30 C 40 D same value at constant temperature.
Option C: When K eq < 1, lg K eq will be negative
1 D and G eq will be positive according to the
+
In H 3 , equationG eq =2.303 RT lg K eq , i.e. the
p = 3, n = 0, e = 3 1 = 2 (one less e than p) dissolution of CO 2 in water is nonspontaneous
when K eq < 1.
2 D
No. of moles of helium remains the same at the 8 C
P1 V1 P2 V2 (CH 3 CHO) 4 (s) + 10 O 2 (g) 8CO 2 (g) + 8H 2 O(l)
two temperatures. Using = ,
T1 T2 H{ c metaldehyde
1 105 V1 P2 (V1 + 3V1) = (8H{ f CO 2 + 8H{ f H 2 O) H{ f metaldehyde
=
20 + 273 100 + 273
4
Hence H{ f metaldehyde
P 2 = 3.18 10 Pa = (8H{ f CO 2 + 8H{ f H 2 O) H{ c metaldehyde
= (8H{ c carbon + 8H{ c hydrogen) H{ c metaldehyde
3 B
Mass of CaCO 3 in one chickens egg shell 9 A
5
= 50 = 2.5 g
100
No. of moles of CaCO 3 in one chickens egg shell
= 2.5 100.1= 0.025 mol
No. of moles of ethanoic acid, CH 3 CO 2 H used
3
= 2.0 50 10 = 0.10 mol
2+
2CH 3 CO 2 H + CaCO 3 Ca (CH 3 CO 2 ) 2 + H 2 O + CO 2
No. of moles of CaCO 3 needed
= 0.10 2= 0.050 mol
No. of complete chickens egg shells needed
= 0.050 0.025= 2
o +
Option A: E (Au /Au) wrt the SHE = +1.56 +
4 A (+0.27) = +1.83 V(refer to diagram above)
Equation: o +
Option B: E (Au /Au) wrt the AgCl/Ag electrode =
Al 4 C 3 + 4NaOH + 4H 2 O 4NaAlO 2 + 3CH 4 +1.56 + (0.27 0.22) = +1.61 V (refer to diagram
Hydrocarbon is CH 4 . above)
Option C: The reduction potential of AgCl/Aghalf
5 D +
cell (+0.22 V) is more positive than that of H /H 2
+
H +
NH4 is tetrahedral. The bond halfcell (0.00V). Hence Ag has a lower tendency
o
angles are 109 and the bonds to be oxidised than H 2 .
N are all of the same length. Option D: The reduction potential of
H H +
NH4 ions are formed when NH3 Hg 2 Cl 2 /Hghalfcell (+0.27V) is more positive than
H behaves as a base, i.e. a proton that of AgCl/Ag halfcell (+0.22V). Hence Hg 2 Cl 2
acceptor. has a higher tendency to be reduced than AgCl.
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+
On heating, NH 4 + OH NH 3 + H 2 O
10 C
1
3
6 C Let volume of 0.100 mol dm NaOH added be V
3
CH3 c .
cm
+
CH3 C CH2OH CH3CH
CH H2CH2C
CH H2OH
CH H NaOH
OH + CH 3 COO 2 H CH 3 CO 2 Na + H 2 O
No. of moles of NaOH added
add (limiting reagent)
4
H = 0.100 V 1000 = V 10 mol
- - - - -
2 methylpropan 1 ol butan 1 ol = no. of moles of CH 3 CO 2

1
1653 trendyline
No. of moles of CH 3 CO 2 H left
4
= (0.100 20 1000) (V 10 ) 16 B
4
= (20 V) 10 mol In hot KOH(aq),Cl 2 undergoes disproportionation
+
H [CH3 CO2 ]
- reaction as shown below.
Ka =
3Cl 2 + 6OH 5Cl + ClO 3 + 3H 2 O
[CH3 CO2 H]
5 (105.5 )(V 104 )
1.8 x 10 = 4
17 D
20V 10
3 Formula of complex
V = 17.0 cm I [Co(NH 3 ) 6 ]Cl 3
II [Co(NH 3 ) 5 Cl]Cl 2
11 C III [Co(NH 3 ) 4 Cl 2 ]Cl
H 2 (g) + I 2 (g) 2HI(g) IV [Co(NH 3 ) 4 Cl 2 ]Cl
Initial / mol 0.10 0.10 0 Option A: All complexes, I to IV, have
Change / mol 0.03 0.03 +0.06 coordination number of 6.
Eqm / mol 0.07 0.07 0.06 Option B: Charge of the cation depends on how

many Cl ligand it has. Only cations in complexes
[HI]2 (0.06)2
Kc = = = 0.735 III and IV have the same charge of +1. Cation in
[I2 ][H2 ] (0.07)2
complex I has a charge of +3 and cation in
complex II has a charge of +2.
12 B
Option C: Complex I only consists of ammonia

ligands since all 3 moles of Cl are precipitated by
AgNO 3 per mole of the complex.
Option D: ComplexesIII and IV have the same
structural formula but the ligands have different
40 days is equivalent to 5 halflives; hence the
131 15 arrangement in space as they have different
mass of I left would be 5 g. colours.
2
13 C 18 B
Option A shows the properties of a Group I 3 structural isomers are shown below.
CBr CBr CH
element.
CH CH CH CBr CH CBr
Option B shows the properties of a nonmetal
with low electrical conductivity.
CH CH CH
Option C shows the properties of a Group
CH CBr CH CH CH CBr
IIelement with relatively high melting point and
has high electrical conductivity. Melting point is
higher for Group IIelements than Group I 19 C
Option A: CH 3 CHCl 2 can be formed from one of
elements due to stronger metallic bonds.
the propagation steps:
Option Dshows the properties of a transition metal
o
with very high melting point> 1000 C and very CH CHCl + Cl2
3 CH CHCl2 + Cl
3
high density. Option B: CHCl 2 CH 2 Cl can be formed from
CH 3 CHCl 2 in the propagation step:
14 A
CH CHCl2 + Cl
3 CH CHCl + HCl
From the acidbase nature of the oxides,it can be 2 2
deduced that X is in Group III,Yis in Group I or CH2CHCl2 + Cl2 CH2ClCHCl2 + Cl

GroupII, and Z is a nonmetal. Since ionic radius
of metal ion decreases across the period due to Option C: CH3CH2 is not produced from
increasing nuclear charge, ion ofX is smaller than CH 3 CH 2 Cl as the CCl bond is not broken.Hence
ion ofY. Nonmetal ion of the same period has a CH 3 CH 2 CH 2 CH 3 is not likely to be formed.
larger ionic radius than a metal ion as it gains Option D: CH 2 ClCH(Cl)CH(Cl)CH 3 can be formed
electrons to form an additional shell of electrons. from a termination step:
Hence, ion ofZ has the largest ionic radius. CH2ClCH(Cl) + CH(Cl)CH 3
CH2ClCH(Cl)CH(Cl)CH3
15 D
Option A: Phosphorus also forms two
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acidicoxides, P 4 O 6 and P 4 O 10 . 20 C
Option B: Ar has
st
s tthe highest 1 ionisation sitive test with Tollens reagent U contains
Positive
energy.Option C: Phosphorus and chlorine can CHO group.Since U is oxidised by acidified
alsoform compounds ds with variable oxidation
oxidatio K 2 Cr 2 O 7 to
o CH 3 CH(CH 3 )CH 2 CO 2 H, U is

states, e.g. PCl 3 andd PCl
PCl 5 , Cll and ClO
CO . C 3 CH(CH 3 )CH
CH H 2 CHO.
CHO.Ucan
CH Uc be reduced by
Option D:Only sulfur ulfur exists
i t as S 8 simple NaBHBH 4 tto form
fformV,
V, CHH 3 CH(
CH(CH 3 )CH 2 CH 2 OH, which
CH
molecules. reacts with CH 3 COCl to form an esterW,
CH 3 CH(CH 3 )CH 2 CH 2 OCOCH 3 .
2
1654 trendyline
24 B
Option A: Warfarin has 2 stereoisomers as it has
21 A only one chiral centre. It has no geometric
Nucleophilic substitution of X by :PPh 3 in stage I. isomers as the C=C bond is found in the ring
structure.
X PPh3
Ph3P X C R OptionB: The OH group reacts with CH 3 COCl to
IHC R form an ester and white fumes of HCl.
R'
R' OptionC: Warfarin does not react with KCN(alc) in
Elimination by removal of atom or groups of atoms the presence of heat as there is no alkyl halide
from adjacent carbon atoms in stage IIto form a (i.e. RX) present. The ketone functional group
multiple bond. present in Warfarin can react with HCN, NaCN
catalyst at room temperature, not KCN(alc).
O PPh3
O PPh3 + OptionD: 1 mol of warfarin reacts with 2 mol of H 2
C C R gas in the presence of nickel catalyst and heat as
II C C R
R' R'
both the ketone and the alkene functional groups
are reduced.
[In condensation reaction, two molecules react
and become covalently bonded with the 25 C
concurrent loss of a small molecule, e.g. H 2 O, Option A:CH 3 CHBrCH 3 undergoes elimination
HCl.] +
reaction with CH 3 CH 2 O Na (alc), reflux to form
CH 3 CH=CH 2 .
22 D OptionB:
Option A: The benzaldehyde is reduced by H 2 , Pd.
However, there is no visible observation to -
OH Na O Na
+
distinguish between the two compounds. Br B-r +
Option B: Phenol cannot react with Br 2 (aq) in this
Br Br
question as it has substituents at the 2,4and 6
positions w.r.t. the phenol functional group.
Option C: The benzaldehyde cannot react with O
Fehlings reagent. It can only react with Tollens Br
reagent.
Option D: Orange acidified K 2 Cr 2 O 7 turns green OptionC:Amine does not react with carboxylic
for the following molecule. acid to form amide. N.B.Amine reacts with acyl
O O O O chloride to form amide.
C C OptionD:CN is reduced by H 2 , Pt toCH 2 NH 2 .
H O H OH
acid
hydrolysis OH 26 B
CO2H COCl
oxidation
O O PCl 5
C N
HO OH N
N
C O H H O
OH compound Q compound R
Orange acidified K 2 Cr 2 O 7 remainsorange for the
following molecule as there is no oxidation taking
27 A
place.
OptionA:
O O OH
HO O O HO OH + +
C O O O O
OH OH
acid O H F
C G
hydrolysis CH3 OH - O O+ -
OH + 3I2 + 5OH CHI3 + 3I + 4H2O
- -
O O O O
F
23 A +
H (aq)
Size of atom: F<Cl<Br<I
O O
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y e
Strength of bond: CF> CCl> CBr > CI
The larger the size e of the halogen atom, the OH OH
O
longer and weakerr the C CX
C X bond (where X= G
F,Cl,Br,I) which is more
ore easily broken. Hence C
C OptionB:
Optio
OptionB:
OH
Ibond is most easily ly broken and the I ions
sily ons +O +
O O
+ O O
formed will react with Ag (aq) to form a yellow O OH OH
OH
precipitate of AgI.
None of the products react with alkaline aqueous
iodine to form any of the other product.
3
1655 trendyline
OptionC: case for the hydrogen / bromine reaction. Hence,
OH O O the slow rate determining step involves 1
O
+
OH O OH molecule of H 2 and 1 molecule ofI 2 , which could
OH
O be a single step reaction for the hydrogen / iodine
Only two products are formed. reaction.
OptionD:
HO OH
OH O O
OH + O + Option3: Incorrect
O O
O O There is no evidence from the rate equation that
OH OH the mechanism of the hydrogen / bromine
reactioninvolves free radicals.
OH O
- -
O + 3I + 6OH O + CHI + 3I + 5H O 32 B (1 and 2 only are correct)
O 2 3 2
O O O Option1: Correct
-
OH CH3
-
O O From Mg(s) + Cl 2 (g) MgCl 2 (s), the enthalpy
1
+
change of formation of MgCl 2 is 642 kJ mol , i.e.
H (aq) the energy change when 1 mol of MgCl 2 is
formed from its constituent elements in their
OH
O
standard states, Mg(s) and Cl 2 (g).
O O Option2: Correct
2+
From Mg(s) Mg (g),
OH OH st nd
+2334 = H atom (Mg) + 1 I.E. + 2 I.E.
H atom (Mg) = +2334 736 1450 = +148 kJ
28 B mol
1
Both the amide and ester functional groups will Option3: Incorrect
undergo acid hydrolysis. Amine will undergo acid
From Cl 2 (g) + 2e 2Cl (g),
base reaction with HCl(aq). st
454 = B.E.(ClCl) +2(1 E.A.)
st 1
1 E.A. = (454 244) 2 = 349 kJ mol
29 D
Options A and B: LiAlH 4 in dry ether is unable to 33 A (1, 2 and 3 are correct)
reduce alkene. Option1: Correct
OptionC: KMnO 4 with H 2 SO 4 (aq), heat will cause
NaBO 2 + 6H 2 O + 8e NaBH 4 + 8OH

E
o
9
both CH 2 OH and CH 2 CH 2 CH 3 side chains on
O 2 + 2H 2 O + 4e 4OH

E = +0.40 V
o
the benzene ring to be oxidised to CO 2 H as both o

E cell = 0.40 9
side chains have a benzylic hydrogen. Option 2: Correct
OptionD: Both aldehyde and alkene functional NaBH 4 is oxidised to NaBO 2 at the anode X while
groups will be reduced by H 2 , Pt. Only the primary
O 2 is reduced to OH at the cathode Y.
alcohol will be oxidised by K 2 Cr 2 O 7 with Option3: Correct
H 2 SO 4 (aq), heat to form CO 2 H. 180o
O B O
30 C The BO 2 anion has 2 bond pairs
Point S corresponds to the second equivalence and 0 lone pair around the central B atom, giving
+ o
it a linear shape with a bond angle of 180 .
NH3
34 D (1 only is correct)
HO2C CO2H Option1: Correct
point for the titration of with 2+
NaOH. Ca(OH) 2 (s) Ca (aq) + 2OH (aq)
3
Relative acid strength: CO 2 H > alkyl Let the solubility of Ca(OH) 2 be y mol dm .
2+ 2 6
CO 2 H >NH 3 .
+ [Ca ][OH ] = 4.7 x 10
2 6
Thus the species present at point S is (y)(2y) = 4.7 x 10
3
+ y = 0.0106 mol dm
3
NH3 [OH ] = 2y = 0.021 mol dm
Option2: Incorrect
O2C CO2 When equal volumes of solutions are mixed
.
together, dilution occurs and their concentrations
2+
31 B (1 and 2 only are correct) are halved. Hence, new [Ca ] = 0.01 mol
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3 3
Option1: Correct dm and nd new [OH ] = 0.01 mol dm .
2+ 2 2
Since [HBr] is in the denominator of the rate Ionic
onic product = [Ca
[ ][OH ] = (0.01)(0.01)
6
6 6
6 3 9
equation, an increase se in its concentration will
ase w = 1.0 1 < 4.7 x 10 mo
.0 10 mol dm
lower the value of rate.
ate.
e. Since ionic product < <KK sp (Ca(OH) 2 ), precipitation
Option2:Correct occur.
will not occu
For the hydrogen / iodine reaction
reaction, the given rate Option3: Incorrect
equation follows the molecularity of the given Sn(OH) 2 has the lowest solubility amongst the
three metal hydroxides.
equation(H 2 (g)+ I 2 (g) 2HI(g)) but this is not the
4
1656 trendyline
metal Solubility / mol the C=C bond in molecule I, the overall dipole
K sp
hydroxide dm moment is larger than that in molecule II.
6
4.7 10 Option 2: Incorrect
Ca(OH) 2 3 9 0.0106
mol dm Molecules I and IIare structural isomers of each
27
5.4 10 other and are not stereoisomers.
Sn(OH) 2 3 9 1.11 x 10
mol dm Option 3: Incorrect
31
6.7 10 Molecules I and IIare enantiomers, hence they
Cr(OH) 3 4 12 1.26 x 10
mol dm are stereoisomers.The overall dipole moment of
35 D (1 only is correct) the two molecules are identical.
Option1: Correct
Down the group, cationic radius increases and 39 B (1 and 2 only are correct)
2+
charge density of M decreases. Polarising Option 1: Correct
2+
power of M decreases and the electron cloud of CH3
iodate(V) ion is less distorted. Thermal stability of HN OH excess
CH3
M(IO 3 ) 2 increases. Br2(aq)
Option2: Incorrect C N CONHCH2CH2CO2H
q+ q- H H
Since L.E. , magnitude of L.E. decreases CH3
r+ + r-
down the group with increasing cationic radius, r + . HN Br Br OH
CH3
Option3: Incorrect
2+ Br C N CONHCH2CH2CO2H
Charge density of M ion decreases down the
group as ionic radius increases while the charge Br H H Br
remains the same. Option 2:Correct
CH3
36 A (1, 2 and 3 are correct) HN OH
Option1: Correct CH3 + 3CH COCl
3

Overall charge of complex is neutral with two Cl C N CONHCH2CH2CO2H

ligands and one RCO 2 ligand.Hence the H H
oxidation number of M is +3. CH3
Option2: Correct O
C N CH3
OCOCH3
Coordination number is the number of dative
bonds around M which is equal to 6 in the CH3 C N CONHCH2CH2CO2H
complex. H C
Option3: Correct + 3HCl
O CH3
Besides the two Cl ligands, the other four dative
bonds are from the same tetradentate ligand. Option 3: Incorrect
Only 2 mol of cold HCl would react with 1 mol of T.
CH3
37 A (1, 2 and 3 are correct)
Option1: Correct HN OH
CH3
HO
CH3 C N CONHCH2CH2CO2H + 2HCl
* H H
H3N C CO2
Cl CH
3
H H
N OH
Option2: Correct H CH3 Cl
H NH3 C N CONHCH2CH2CO2H
* HH H
HO C C H
H CO2 40 D (1 only is correct)
Option 1:Correct Br
Option3: Correct
H H NH3
Option 2:Incorrect Br

The molecular formula
*
C C C H is C 12 H 18 Br 6 . Br

Option 3:Incorrect
H H CO2 The CCC bond
trendyline
angles
gles a
o
are all 109.5 as Br Br
38 D (1 only is correct)
t) every C at atomis
om sp
3
Br
Option 1: Correct hybridised.
hybridi
hybr i sed.
Molecule I is the cis molecu IIIis th
s isomer and molecule the
trans isomer, hence they are stereoisomers.
stereoisomers Both
NO 2 and Br are electronwithdrawing
lectronwithdrawing in nature.
Since these two groups are on the same side of
5
1657 trendyline
VICTORIA JUNIOR COLLEGE
JC 2 PRELIMINARY EXAMINATIONS
Higher 2
CANDIDATE
NAME ...
CT GROUP ..
CHEMISTRY 9647/02
Paper 2Structured 13 September 2016
Candidates answer on the Question Paper. 2 hours
Write your name and CT group on all the work you hand in.

For Examiners Use
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ne Total
This document consists of 16printed pages and 0 blank page.
1658 trendyline
VJC 2016 9647/02/PRELIM/16[Turn over
2
Answer all the questions in the space provided.
1 Planning (P)
When potassium manganate(VII) reacts with sodium ethanedioate, a redox reaction occurs as
shown below:
2MnO 4 + 5C 2 O 4 2 + 16H+ 2Mn2+ + 10CO 2 + 8H 2 O reaction 1
A product that is generated during the course of the reaction and helps to speed up the
reaction rate is known as an autocatalyst. The autocatalyst for the above reaction is Mn2+.
The kinetics of this reaction can be investigated by determining the concentration of MnO 4
over the course of the reaction. Fixed aliquots (portions) of the reaction mixture are withdrawn
at regular time intervals and added to an excess of potassium iodide.
The MnO 4 in the aliquots reacts with excess iodide as shown below.
2MnO 4 + 10I + 16H+ 2Mn2+ + 5I2 + 8H 2 O reaction 2
The amount of iodine formed can then be determined by titration with the sodium thiosulfate
solution as shown below.
I 2 + 2S 2 O 3 2 2I + S 4 O 6 2 reaction 3
The volume of sodium thiosulfate used is proportional to the concentration of MnO 4 .
(a) In this experiment, both sodium ethanedioate and sulfuric acid are used in large excess.
Explain the purpose of using a large excess of sodium ethanedioate and sulfuric acid.

[1]
(b) Using the information given above, you are required to write a plan for the determination
of the concentration of MnO 4 at regular timing intervals.
0.0500 moldm3 potassium manganate(VII), KMnO 4
0.500 moldm3 sodium ethanedioate, Na 2 C 2 O 4
1.00 moldm3 sulfuric acid, H 2 SO 4
0.200 moldm3 potassium iodide, KI
solid Na 2 S 2 O 3
starch indicator
stopwatch
apparatus and chemicals normally found in a school or college laboratory.

justification for
o the volume of each reactants to be used in reaction 1 so as to allow a
trendyline
minimum
nimum
m of 6 aliquots of the e reaction mix withdrawn and the
mixture to be with
ncentration of MnO 4 in each aliquot to be determined;
concentration determined
o the intended concentration of the sodium thiosulfate, Na 2 S 2 O 3 , to be used;
brief, but specific, details of the apparatus you would use, bearing
bear in mind the
levels of precision they offer;
an outline
tli off h
how th lt would
the results ld b bt
b i d
be obtained;
a sketch of the graph you would expect to obtain.

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VJC 2016 9647/02/PRELIM/16
3
trendyline
1660 trendyline
4

trendyline [10]
(c) The order of reaction with respect to MnO 4 can be determined by initial rate method.
Use your graph in (b), suggest how the initial rate can be determined.
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VJC 2016 9647/02/PRELIM/16
5
....[1]
[Total: 12]
2 (a) Proline (pro) is one of the naturally occurring amino acids. It can be synthesised
from 4hydroxybutanal in 4 steps.
step I step II OH step III step IV O

HO CHO E HO C H F
OH
CO2H
4 hydroxybutanal NH
proline
(i) Suggest the structures of Eand F.
E F
[2]
(ii) Suggest the reagents and conditions required for the following steps.
stepI: .
stepIII: ..
stepIV: ...[3]
(b) The two pK a values associated with proline are2.0 and 10.5.
Make use of these pK a values to suggest the major species present in the solution
of proline with the following pH values.
pH 1 pH 7 pH 1 pH pH
12 7 pH 12
(c)
tren
trendyline
ndylin
ndylin
ne
ne
The structures ofamino acids, valine (val) and cys are shown below.
[3]
1662 trendyline
6
O O
OH HS OH
NH2 NH2
valine cysteine
(i) Draw the structure of valprocys peptide.
[2]
(ii) State the possible R group interactions that valprocys may have with
another valprocys peptide.
[2]
[Total: 12]
3 (a) A student used the following setup in an attempt to produce chlorine gas using
potassium chloride solution.
graphite graphite
salt bridge graphite electrode B electrode A
Zn electrode
1.00 mol dm3 1.00 mol dm3 200 cm3 of 1.0 mol dm3
Zn2+ (aq) Co2+ (aq), Co3+ (aq) KCl (aq)
half-cell 1 half-cell 2
(i) Using relevant data from the Data Booklet, predict the type of redox reaction
that occurs at each halfcell.State the polarity at the graphite electrodes A
and B.
Halfcell 1:
Halfcell 2:
trendyline
Graphite electrode A:
A:
:
Graphite electrode B: [2]
(ii) 20 cm3of hydrogen gas was collected on one of the electrodes after 10
minutes at room temperature and pressure. Assuming 20% of the hydrogen
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VJC 2016 9647/02/PRELIM/16
7
gas was lost during collection, calculate the current produced by the battery
setup.
[2]
(iii) With reference to relevant data from the Data Booklet, explain the absence
of chlorine being discharged on the other electrode.
.. [1]
(b) 20 cm3 of a gas mixture containing gaseous ethanol, carbon monoxide and excess
oxygen was burned completely. There was a contraction of 1 cm3. When the
product mixture was passed through sodium hydroxide, there was a further
contraction of 6 cm3. All gas volumes are measured at 400 K and 1 atm.
Determine the molar composition of the ethanol and carbon monoxide in this gas
mixture.
trendyline [3]
[Total: 8]
4 Magnesium and beryllium are Group II elements but beryllium behaves differently from
that of magnesium. There is said to be 1664
a diagonal relationship between beryllium and
trendyline
8
aluminium as they show similar chemical behaviour due to their similarities in
electronegativity and charge density.
(a) (i) When a few drops of water are added to solid beryllium chloride, steamy
white fumes are evolved and a white solid remains, which is insoluble in
water.
Write a balanced equation for this reaction.
.. [1]
(ii) When a large amount of water is added to solid beryllium chloride, a clear,
weakly acidic solution is obtained. Explain.
.. [1]
(iii) At 750 oC, the relative molecular mass of gaseous beryllium chloride
corresponds to the formula BeCl 2 . At 550 oC, gaseous beryllium chloride
exists as a mixture of BeCl 2 and Y (relative molecular mass of Y is 160).
Determine the molar composition of gaseous beryllium chloride at 550 oC
which has a relative molecular mass of 100. Draw a diagram to illustrate the
nature of the bonding in Y and indicate the value of the bond angle about Be.
[2]
(iv) When aluminium chloride, AlCl 3 , is mixed with ammonia, compound Z is

formed and the reaction is exothermic. The diagram below shows the
relationship between the heat evolved per mole of the mixture and the mole
fraction of AlCl 3 .
Heat evolved /
J mol1
0 0.5 1.0
1
Mole fraction of AlCl
AlC
A Cl3
Draw a diagram to show the bonding in a molecule of compound Z.

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VJC 2016 9647/02/PRELIM/16
9
[1]
(v) Sketch a labelled diagram similar to (a)(iv) that you would expect to obtain
when AlCl 3 is replaced by BeCl 2 .
Heat evolved/
J mol1
0
1.0
Mole fraction of BeCl2 [1]
(vi) Write a balanced equation of a chlorination reaction in Organic Chemistry

that uses anhydrous BeCl 2 as a catalyst.
[1]
(b) Magnalium is an alloy of aluminium and magnesium which is used in boat-building.

The diagram below shows some reactions of magnalium.
sample of HCl(aq) colourless excessNaOH(aq) white

magnalium solution ppt
filter
HCl(aq)
added
white dropwise colourless white
solid, filtrate, residue,
D C B
Identify B,C and D.
trendyline
B: ..
.
.. C:
C: .. D: .. [3]
(c) Grignard reagents, RMgX, can be prepared by the reaction of magnesium with
halogenoalkane, RX, using dry ether as the solvent.
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10
The mechanism of the reaction involves two steps.
Step 1: It involves the transfer of one electron from Mg to the halogen X followed
by the homolytic fission of the carbonhalogen bond. This forms MgX,
which is a radical.
R X + Mg R + Mg X
Step 2: MgX radical couples with the alkyl radical formed in step 1.
R + Mg X RMgX
(i) Draw curve arrows to show the movement of electrons in step 1 of the
mechanism given above.
[1]
(ii) Suggest which step in the mechanism is the ratedetermining step. Explain
your answer.
.. [1]
Grignard reagents can be used to prepare alcohols from carbonyl compounds as

shown by the reaction of CH 3 CH 2 MgBr with ethanal below:
O step I OMgBr step II OH

CH3CH2MgBr + CH3 C CH3 C H CH3 C H + Mg(OH)Br
H CH2CH3 CH2CH3
(iii) What type of reaction takes place in steps IandII?

stepI: ..
stepII: ....[2]
(iv)
trendyline
The variation of the rate constantant k with temperature for the reaction of
CH 3 CH 2 MgBr with ethanal is given below:
k E 1 1
ln 2 a ( )
k1 R T2 T1
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VJC 2016 9647/02/PRELIM/16
11
whereE a denotes the activation energy in J mol1, R is the gas constant, and
T is the temperature in Kelvin.
Given that at 25 oC, the rate constant and activation energy of the reaction is
9.16 x 103mol1dm3 s1 and 102 kJ mol1 respectively.
Explain, with calculations, the effect of temperature change on the rate of the
reaction when the temperature is raised by 5 oC.
.. [2]
(v) Draw the structural formula of the Grignard reagent that will react with
butan2one to form 3methylpentan3ol in a similar twostep reaction.
[1]
(vi) Suggest why CH 3 CO(CH 2 ) 3 CH 2 Br and magnesium cannot be used to

prepare the Grignard reagent CH 3 CO(CH 2 ) 3 CH 2 MgBr.
...[1]
(vii) Ethanal is oxidised to ethanoic acid by acidified potassium dichromate.

Using data from the Data Booklet and the data below, calculate Eo cell of the
reaction.
Eo(CH 3 CO 2 H|CH 3 CHO) = +0.92 V
Hence, explain why the reaction takes place only in the presence of heat.
.. [2]
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[Total: 20]
5 (a) The relationship pV = nRT can be derived

de from the laws of mechanics by
assuming ideal behaviour for gases.
The graph represents the relationship between pV and p for a real gas at three
1668 trendyline
12
pV
(i) Draw one line on the graph to show what the relationship should be for the
same amount of an ideal gas and state which of T 1 , T 2 or T 3 is the lowest
temperature.
Lowest Temperature: .. [1]
(ii) State and explain the effect of pressure on the extent to which a gas
deviates from ideal behaviour.
.. [1]
(b) A flask with a volume of 100 cm3 was first weighed with air filling the flask.The
same flask was then weighed withonly gas, Y, filling the flask. The results,
measured at 26oC and 1.00 105 Pa, are shown.

Calculate the relative molecular mass, M r , of Y.
trendyline
[2]
(c) In recent
ent years there has been worldwide interest in the possible
cent possib extraction of
shale gas (a form of natural gas) as an important energy source.
One of the problems associated with using shale gas is its variable composition.
Table 1 shows the percentage composition of shale gas from four different
sources J, K, L and M.
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VJC 2016 9647/02/PRELIM/16
13
Table 1
source CH 4 C2Hx C3Hy CO 2 N2
J 80.3 8.1 2.3 1.4 7.9
K 82.1 14.0 3.5 0.1 0.3
L 88.0 0.8 0.7 10.4 0.1
M 77.5 4.0 0.9 3.3 14.3
In the formula above, x and y are variables.
(i) Draw the structures of three possible compounds with the formula C 3 H y .
[1]
(ii) Which source of shale gas, J, K, L or M, will provide the most energy when
burned? Explain your answer.
.. [1]
(iii) Suggest one method by which carbon dioxide can be removed from shale
gas.
.. [1]
Table 2 shows a comparison of the relative amounts of pollutants produced when

shale gas, fuel oil and coal are burned to produce the same energy.
Table 2
air pollutant shale gas fuel oil coal
CO 2 117 164 208
CO 0.040 0.033 0.208
NO 2 0.092 0.548 0.457
SO 2 0.001 1.12 2.59
particulates 0.007 0.84 2.74
(iv) Suggest why shale gas produces the smallest amount of CO 2 .
.. [1]
(v)
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Explain which of the three fuels, shale gas, fuel oil or coal,
contributor
ontributor to acid rain.
rain

coa is the largest
.. [1]
1670 trendyline
14
(d) Use the following data and data from the Data Booklet to construct a labelled
energy level diagram to determine the lattice energy of Fe 2 O 3 .
enthalpy change of 4Fe(s) + 3O 2 (g) 2Fe 2 O 3 (s) 1644 kJ mol1

enthalpy change of atomisation of Fe(s) +414 kJ mol1
electron affinity of the oxygen atom 141 kJ mol1
electron affinity of the O ion +844 kJ mol1
Energy
[4]
[Total: 13]
6 (a)
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Coffee
e beans contain chlorogenic acid.
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VJC 2016 9647/02/PRELIM/16
15
OH
O O OH
O OH
HO OH
HO
chlorogenic acid
(i) How many moles of H 2 (g) will be evolved when 1 mol of chlorogenic acid
reacts with an excess of sodium metal?
.. [1]
On heating with dilute aqueous acid, chlorogenic acid produces two compounds D
and E.
OH
+ OH OH
chlorogenic H (aq) O
+
acid heat HO
HO OH O OH
OH
D E
conc. H2SO4 excess
heat Br2(aq)
F G
C7H6O3
When compound D is heated with concentrated H 2 SO 4 , compound F, C 7 H 6 O 3 , is

formed.
Compound F does not decolourise cold dilute acidified KMnO 4 but reacts with
Br 2 (aq).
When compound E is treated with an excess of Br 2 (aq), compound G is produced.
(ii) If the test with cold dilute acidified KMnO 4 had been positive, which
functional group would this have shown to be present in F?
.. [1]
(iii) Suggest the structures for compounds F and G, and draw them in the
relevant boxes below.
trendyline
y C7H6O3
F G
[2]
(b) Allyl alcohol, CH 2 =CHCH 2 OH, is a colourless liquid which is soluble in water.
Crotyl alcohol, CH 3 CH=CHCH 2 OH,1672
is a colourless liquid. trendyline
16
(i) Describe how you would distinguish between allyl alcohol and crotyl alcohol.
The compounds may be distinguished by a preliminary chemical reaction
followed by a subsequent testing of the reaction products. Include clearly the
reagents, conditions and observations for each compound.

.. [2]
(ii) Allyl alcohol may be converted into propanal by using a ruthenium(IV)

catalyst in water.
ruthenium(IV)
CH 2 =CHCH 2 OH CH 3 CH 2 CHO
State the type of reaction and explain your answer.
[1]
[Total: 7]
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VJC 2016 9647/02/PRELIM/16
2016 H2 Chemistry Prelim Exam Paper 2 Suggested Answers
1 Planning (P)
When potassium manganate(VII) reacts with sodium ethanedioate, a redox reaction occurs as
shown below:
2MnO 4 + 5C 2 O 4 2 + 16H+ 2Mn2+ + 10CO 2 + 8H 2 O reaction 1
A product that is generated during the course of the reaction and helps to speed up the
reaction rate is known as an autocatalyst. The autocatalyst for the above reaction is Mn2+.
The kinetics of this reaction can be investigated by determining the concentration of MnO 4
over the course of the reaction. Fixed aliquots (portions) of the reaction mixture are withdrawn
at regular time intervals and added to an excess of potassium iodide.
TheMnO 4 in the aliquots reacts with excess iodide as shown below.
2MnO 4 + 10I + 16H+ 2Mn2+ + 5I2 + 8H 2 O reaction 2
The amount of iodine formed can then be determined by titration with the sodium thiosulfate
solution as shown below.
I 2 + 2S 2 O 3 2 2I + S 4 O 6 2 reaction 3
The volume of sodium thiosulfate used is proportional to the concentration of MnO 4 .
(a) In this experiment, both sodium ethanedioate and sulfuric acid are used in large excess.
Explain the purpose of using a large excess of sodium ethanedioate and sulfuric acid.
This is to ensure that the concentration of sodium ethanedioate and sulfuric

acid remains almost constant throughout the reaction / concentration do not
affect rate. Hence, the order of reaction with respect to MnO 4 can be determined.
(b) Using the information given above, you are required to write a plan for the determination
of the concentration of MnO 4 at regular timing intervals.
0.0500 moldm3 potassium manganate(VII), KMnO 4
0.500 moldm3 sodium ethanedioate, Na 2 C 2 O 4
1.00 moldm3 sulfuric acid, H 2 SO 4
0.200 moldm3 potassium iodide, KI
solid Na 2 S 2 O 3
starch indicator
stopwatch
apparatus and chemicals normally found in a school or college laboratory.

justification for
o the volume of each reactants to be used in reaction 1 so as to allow a
minimum of 6 aliquots of the reaction mixture to be withdrawn and the
trendyline
concentration
ncentration
e of MnO 4 in each aliquot
liquot to be determined;
determined
det ;
o the intended concentration of the sodium thiosulfate, Na N 2 S 2 O 3 , to be used;
brief, but specific, details of the apparatus you would use, bearing
bear in mind the
levels of precision they offer;
an outline
tline
ine of how the results would be obtained;
obtained
a sketchch of the graph you would expectt to obtain
obtain.
[10]
1674 trendyline
2
Justification
Assuming 10 cm3 aliquot is withdrawn for each titration, minimum volume
required for reaction 1 is 60 cm3.
Volume of MnO 4 used = 25.0 cm3
Volume of Na 2 C 2 O 4 used = 50.0 cm3
Volume of H 2 SO 4 used = 25.0 cm3
Total volume used for reaction 1 = 100 cm3
for all the volumes used.
Calculation for concentration of Na 2 S 2 O 3 to be used

25.0
Amount of MnO 4 present in reaction 1 =0.0500 x
1000
= 1.25 x 103mol
10.0
Amount of MnO 4 present in 10 cm3 aliquot =1.25 x 103 x
100
4
=1.25 x 10 mol
5
Amount of I 2 produced in reaction 2 =1.25 x 104 x
2
=3.13 x 104mol
Amount of S 2 O 3 2 required in reaction 3 =3.125 x 104 x 2

=6.25 x 104mol
Assuming a titre volume of 25.00 cm3 (acceptable range 1030 cm3)

25.00
[S 2 O 3 2] used for titration =6.25 x 104
1000
=0.0250 moldm3
To prepare a standard solution of 100 cm3 Na 2 S 2 O 3

100
Mass of Na 2 S 2 O 3 used =0.0250 x x (158.2)
1000
=0.396 g
Preparation of Na 2 S 2 O 3 standard solution

1. Weigh accurately about 0.315 g of Na 2 S 2 O 3 into a beaker.
2. Add distilled water to the beaker to dissolve Na 2 S 2 O 3 and transfer the
solution quantitatively into a 100 ml standard flask.
3. Add distilled H 2 O to the mark and shake the flask to give a homogenous
solution.
Preparation of reaction mixture

1. Using a 100 cm3measuring cylinder, add 50.0 cm3 of Na 2 C 2 O 4 and 25 cm3
H 2 SO 4 into a conical flask.
2. Add 25 cm3 MnO 4 to a 50 cm3measuring cylinder.
3. Pour MnO 4 to the reaction mixture in the conical flask and start the
stopwatch immediately.
ttrendyline
end
ndyyline
l
Ensure thorough g mixing g by
y swirling
g the flask.
(marking
king point for starting stopwatch is awarded only if MnO Mn 4 is added as
st rre
the last agent.)
reagent.)
4. out 1 min, pipette 10.0 cm3 of the reaction mixture into a conical
At about
bout
ontaining 10 cm3 of KI solution
flask containing solution.. Label conical flask 1.
solut
5. Repeatat step 4 five more times at aboutout two minute intervals, ttransferring the
aliquots into 5 separate conical flasks. Label conical flask 2 to 6.
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VJC 2016 9647/02/PRELIM/16
3
Titration with sodium thiosulfate

1. Fill a 50 cm3 burette with Na 2 S 2 O 3 .
2. Titrate the iodine in conical flask 1 against Na 2 S 2 O 3 .
3. When the colour of the solution turns pale yellow, add about 1 cm3
of starchindicator. The solution will turn blueblack.
4. Continue the titration and the endpoint is reached when the blue
black colour just disappears.
3. Repeat step 2 to 4 for conical flask 2 to 6.
Shape of graph expected
Volume of S2O32- /
cm3
time / min
[12, max 10]
(c) The order of reaction with respect to MnO 4 can be determined by initial rate method.
Use your graph, suggest how the initial rate can be determined.
As shown in the graph in (b), draw the tangent and then determine the gradient
which gives the initial rate of reaction.
[1]
[Total: 12]
2 (a) Proline (pro) is one of the naturally occurring amino acids. It can be synthesised
from 4hydroxybutanal in 4 steps.
step I step II OH step III step IV O
HO CHO E HO C H F
OH
CO2H
4 hydroxybutanal NH
proline
(i) Suggest the structures of Eand F.
E F
OH Cl
HO C H Cl C H
CN CO2H
[2]
(ii) Suggest the reagents and conditions required for the following
followin steps.
I: HCN
Step I: CN with KCN catalyst, room temperature
Step III: concHCl,
concHCl ZnCl 2 , heat
heat,
Step IV: NH 3 (alc) heat in a sealed tube
[3]
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4
(b) The two pK a values associated with proline are2.0 and 10.5.
Make use of these pK a values to suggest the major species present in the solution
of proline with the following pH values.
pH 1 pH 7 pH 12
O O O
- -
OH O O
+ +
NH2 NH2 NH
[3]
(c) The structures ofamino acids, valine (val) and cys are shown below.
O O
OH HS OH
NH2 NH2
valine cysteine
(i) Draw the structure of valprocys peptide.
SH
O
N OH
H2N N
H
O O
[2]
(ii) State the possible R group interactions that valprocys may have with
another valprocys peptide.
Disulfide bond formed between the CH 2 SH in the cys groups.

van der waals forces formed between the nonpolar CH(CH 3 ) 2 groups
in the valine or the nonpolar CH 2 CH 2 CH 2 in the proline.
[2]
[Total: 12]
3 (a) A student used the following setup in an attempt to produce chlorine gas using
potassium chloride solution.
graphite graphite
salt bridge graphite electrode B electrode A
Zn electrode
ttrendyline
dy ne
1.00 mol dm3
Zn2++ ((aq)
half-cell
-cell 1
1.00 mol dm3
Co2++ (aq), Co3++ ((aq)
ha -cell 2
half-cell
1 mol dm3
200 cm3 of 1.0
KCl (aq)
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VJC 2016 9647/02/PRELIM/16
5
(i) Using relevant data from the Data Booklet, predict the type of redox reaction
that occurs at each halfcell. State the polarity at the graphite electrodes A
and B.
Halfcell 1: oxidation
Halfcell 2: reduction
Graphite electrode A: negative (reduction occurs)
Graphite electrode B: positive (oxidation occurs)
[2]
(ii) 20 cm3of hydrogen gas was collected on one of the electrodes after 10
minutes at room temperature and pressure. Assuming 20% of the hydrogen
gas was lost during collection, calculate the current produced by the battery
setup.
Graphite electrode A: 2H 2 O + 2e H 2 + 2OH
Amount of hydrogen gas collected = 20 / 24000 = 8.33 x 104mol

Actual amount of hydrogen produced= (8.33 x 104) x= 1.04 x 103mol
Number of moles of electrons transferred = 2 x (1.04 x 103)
= 2.08 x 103mol
Q = It
2.08 x 103 x (96500) = I x (10 x 60)
Current, I = 0.335 A
[2]
(iii) With reference to relevant data from the Data Booklet, explain the absence
of chlorine being discharged on the other electrode.
O 2 + 4H+ + 4e 2H 2 O Eo = +1.23 V
Cl 2 + 2e 2Cl Eo = +1.36 V
At the anode, Eo(O 2 |H 2 O) is less positive than Eo(Cl 2 |Cl), so H 2 O will
undergo oxidation preferentially to give O 2 .
[1]
(b) 20 cm3 of a gas mixture containing gaseous ethanol, carbon monoxide and excess
oxygen was burned completely. There was a contraction of 1 cm3. When the
product mixture was passed through sodium hydroxide, there was a further
contraction of 6 cm3. All gas volumes are measured at 400 K and 1 atm.
Determine the molar composition of the ethanol and carbon monoxide in this gas
mixture.
Let the volume of C 2 H 5 OH and CO measured at 1 atm be x cm3and y cm3,
respectively.
C 2 H 5 OH + 3O 2 2CO 2 + 3H 2 O
c/cm3 x 3x +2x +3x
Total change in volume = 2x + 3x x 3x = x
2CO + O 2 2CO 2
c/cm3 y 1/2y +y
Total change in volume = y y y = y
Hence x y = 1
trendyline
The further
rther contraction is due to the removal of CO 2 by NaOH,
urther
Hence,e, 2x + y = 6
x = 1, y =4
Molarr composition of ethanol = 1/20 x 100% = 5%

Molarr composition of CO = 4/20 x 100%
0% = 20%
[3]
[Total: 8]
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6
4 Magnesium and beryllium are Group II elements but beryllium behaves differently from
that of magnesium. There is said to be a diagonal relationship between beryllium and
aluminium as they show similar chemical behaviour due to their similarities in
electronegativity and charge density.
(a) (i) When a few drops of water are added to solid beryllium chloride, steamy
white fumes are evolved and a white solid remains, which is insoluble in
water.
Write a balanced equation for this reaction.
BeCl 2 (s) + H 2 O(l) BeO(s) + 2HCl(g)
OR BeCl 2 (s) + 2H 2 O(l) Be(OH) 2 (s) + 2HCl(g)
[1]
(ii) When a large amount of water is added to solid beryllium chloride, a clear,
weakly acidic solution is obtained. Explain.
Due to the high charge density of Be2+, BeCl 2 undergoes hydration
and hydrolysis/ Be2+ (aq) pulls electrons away from one of the
surrounding water molecules, hence weakening the OH bond which
results in the release of a proton and give rise to an acidic solution.
[1]
(iii) At 750 oC, the relative molecular mass of gaseous beryllium chloride
corresponds to the formula BeCl 2 . At 550 oC, gaseous beryllium chloride
exists as a mixture of BeCl 2 and Y (relative molecular mass of Y is 160).
Determine the molar composition of gaseous beryllium chloride at 550 oC

which has a relative molecular mass of 100. Draw a diagram to illustrate the
nature of the bonding in Y and indicate the value of the bond angle about Be.
100 = 80x + 160(1x)
x = 0.75 and 1x = 0.25
Composition is 75% BeCl 2 and 25% Y
Cl
Cl Be Be Cl
Cl
Trigonal planar with respect to Be, hence bond angle is 120o
[2]
(iv) When aluminium chloride, AlCl 3 , is mixed with ammonia, compound Z is

formed and the reaction is exothermic. The diagram below shows the
relationship between the heat evolved per mole of the mixture and the mole
fraction of AlCl 3 .
Heat evolved /
J mol1
0 0.5 1.0
Mole fraction of AlCl3
tre
re
Draw a diagram to show the bonding in a mo
molecule of compound
compo Z.
Diagram of Compound Z :
Cl
Cl H
Cll A
C All N H
Cll
C H
[1]
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VJC 2016 9647/02/PRELIM/16
7
(v) Sketch a labelled diagram similar to (a)(iv) that you would expect to obtain
when AlCl 3 is replaced by BeCl 2 .
Heat evolved/
J mol1
0 0.33 1.0
Mole fraction of BeCl2
[1]
(vi) Write a balanced equation of a chlorination reaction in Organic Chemistry

that uses anhydrous BeCl 2 as a catalyst.
anhydrous BeCl2 Cl
+ Cl
2 room temp + HCl
[1]
(b) Magnalium is an alloy of aluminium and magnesium which is used in boat-building.

The diagram below shows some reactions of magnalium.
sample of HCl(aq) colourless excess NaOH(aq) white

magnalium solution ppt
filter
HCl(aq)
added
white dropwise colourless white
solid, filtrate, residue,
D C B
Identify B,C and D.
B : Mg(OH) 2
C : Al(OH) 4
D :Al(OH) 3
[3]
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8
(c) Grignard reagents, RMgX, can be prepared by the reaction of magnesium with
halogenoalkane, RX, using dry ether as the solvent.
The mechanism of the reaction involves two steps.
Step 1: It involves the transfer of one electron from Mg to the halogen X followed
by the homolytic fission of the carbonhalogen bond. This forms MgX,
which is a radical.
R X + Mg R + Mg X
Step 2: MgX radical couples with the alkyl radical formed in step 1.
R + Mg X RMgX
(i) Draw curve arrows to show the movement of electrons in step 1 of the
mechanism given above.
R X Mg R + Mg X
[1]
(ii) Suggest which step in the mechanism is the ratedetermining step. Explain
your answer.
Step 1 is the ratedetermining step
Step 1 has higher activation energy as it involves breaking of covalent
bond.
[1]
Grignard reagents can be used to prepare alcohols from carbonyl compounds as

shown by the reaction of CH 3 CH 2 MgBr with ethanal below:
O step I OMgBr step II OH

CH3CH2MgBr + CH3 C CH3 C H CH3 C H + Mg(OH)Br
H CH2CH3 CH2CH3
(iii) What type of reaction takes place in steps IandII?

stepI : Nucleophilic addition
stepII : Hydrolysis or Acidbase reaction
[2]
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VJC 2016 9647/02/PRELIM/16
9
(iv) The variation of the rate constant k with temperature for the reaction of
CH 3 CH 2 MgBr with ethanal is given below:
k2 Ea 1 1
ln ( )
k1 R T2 T1
whereE a denotes the activation energy in J mol1, R is the gas constant, and
T is the temperature in Kelvin.
Given that at 25 0C, the rate constant and activation energy of the reaction is
9.16 x 103mol1dm3 s1 and 102 kJ mol1 respectively.
Explain, with calculations, the effect of temperature change on the rate of the
reaction when the temperature is raised by 5 oC.
k2 102000 1 1
ln 3
= ( )
9.16 10 8.31 303 298
k 2 = 1.81 x 102mol1 dm3 s1

A rise in temperature results in a larger rate constant. Since the
concentrations of the reactants are kept constant, a larger rate
constant indicates a faster reaction. (or rate constant doubles, hence
rate doubles)
[2]
(v) Draw the structural formula of the Grignard reagent that will react with
butan2one to form 3methylpentan3ol in a similar twostep reaction.
CH 3 CH 2 MgBr
[1]
(vi) Suggest why CH 3 CO(CH 2 ) 3 CH 2 Br and magnesium cannot be used to

prepare the Grignard reagent CH 3 CO(CH 2 ) 3 CH 2 MgBr.
CH 3 CO(CH 2 ) 3 CH 2 MgBr cannot be prepared as it will react further with
the ketone group in the same molecule.
[1]
(vii) Ethanal is oxidised to ethanoic acid by acidified potassium dichromate.

Using data from the Data Booklet and the data below, calculate Eo cell of the
reaction.
Eo(CH 3 CO 2 H|CH 3 CHO) = +0.92 V
Hence, explain why the reaction takes place only in the presence of heat.
Eo cell = 1.33 0.92
= 0.41 V
Eo cell > 0, hence reaction is thermodynamically feasible.
Heat is needed to overcome the high activation energy needed
tobreak strong covalent bonds.
(or reaction is kinetically not feasible in the absence of heat as it
trendyline
d li
involves
nv breaking of strong
g covalent bonds)
bonds
bon )
[2]
[Total: 20]
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10
5 (a) The relationship pV = nRT can be derived from the laws of mechanics by
assuming ideal behaviour for gases.
The graph represents the relationship between pV and p for a real gas at three
pV
(i) Draw one line on the graph to show what the relationship should be for the
same amount of an ideal gas and state which of T 1 , T 2 or T 3 is the lowest
temperature.
T 1 is the lowest temperature.
[1]
(ii) State and explain the effect of pressure on the extent to which a gas
deviates from ideal behaviour.
A gas deviates from ideal behaviour at high pressure as the molecular
volume is significant / no longer negligible OR the intermolecular
forces of attraction are significant.
[1]
(b) A flask with a volume of 100 cm3 was first weighed with air filling the flask.The
same flask was then weighed withonly gas, Y, filling the flask. The results,
measured at 26oC and 1.00 105 Pa, are shown.

Calculate the relative molecular mass, M r , of Y.
Mass of air = 0.00118 100 = 0.118 g

Mass of flask = 47.930 0.118 = 47.812 g
Mass of Y = 47.989 47.812 = 0.177 g
0.177
1.00 105 100 106 = 8.31 (26 + 273)
Mr
M r of Y = 44.0
[2]
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VJC 2016 9647/02/PRELIM/16
11
(c) In recent years there has been worldwide interest in the possible extraction of
shale gas (a form of natural gas) as an important energy source.
One of the problems associated with using shale gas is its variable composition.
Table 1 shows the percentage composition of shale gas from four different
sources J, K, L and M.
Table 1
source CH 4 C2Hx C3Hy CO 2 N2

J 80.3 8.1 2.3 1.4 7.9
K 82.1 14.0 3.5 0.1 0.3
L 88.0 0.8 0.7 10.4 0.1
M 77.5 4.0 0.9 3.3 14.3
In the formula above, x and y are variables.
(i) Draw the structures of three possible compounds with the formula C 3 H y .
CHand CH 2 CCH 2 [Any 3 of 4.]

CH 3 CH 2 CH 3 , CH 3 CH=CH 2 , CH 3 C
[1]
(ii) Which source of shale gas, J, K, L or M, will provide the most energy when
burned? Explain your answer.
Source K
Souce K has the highest percentage composition of hydrocarbons
which will provide the most energy when burned.
[1]
(iii) Suggest one method by which carbon dioxide can be removed from shale
gas.
Carbon dioxide can be removed from shale gas by passing it through

aqueous sodium hydroxide.
[1]
Table 2 shows a comparison of the relative amounts of pollutants produced when

shale gas, fuel oil and coal are burned to produce the same amount of energy.
Table 2
air pollutant shale gas fuel oil coal

CO 2 117 164 208
CO 0.040 0.033 0.208
NO 2 0.092 0.548 0.457
SO 2 0.001 1.12 2.59
particulates 0.007 0.84 2.74
(iv) Suggest why shale gas produces the smallest amount of CO 2 .

Shale gas contains small hydrocarbon moleculeswith low C:H
ttrendyline
ratiounlike
ratio
at unlike fuel oil and coal
al which contain
cont more carb
carbon atoms, and
thus produces the smallest amount of CO 2 .
[1]
(v) Explain
xplain which of the three fuels, shale gas, fuel oil or coal,
ccoa is the largest
t ib t to
contributor t acid
id rain.
i
coal
Coal produced the largest relative amounts of CO 2 , NO 2 and SO 2 when
burned to produce the same amount of energy.
1684 [1]
trendyline
12
(d) Use the following data and data from the Data Booklet to construct a labelled
energy level diagram to determine the lattice energy of Fe 2 O 3 .
enthalpy change of 4Fe(s) + 3O 2 (g) 2Fe 2 O 3 (s) 1644 kJ mol1

enthalpy change of atomisation of Fe(s) +414 kJ mol1
electron affinity of the oxygen atom 141 kJ mol1
electron affinity of the O ion +844 kJ mol1
Energy
2Fe3+(g) + 3O2(g)
3(844) = 2532
2Fe3+(g) + 3O(g) + 6e
3/2(496) = 744 3(141) = 423

2Fe3+(g) + 3O(g) + 3e
2Fe3+(g) + 3/2 O 2 (g) + 6e
2(762 + 1560 + 2960)

= 10564
LE
2Fe(g) + 3/2 O 2 (g)
2(414) = 828
2Fe(s) + 3/2 O 2 (g)

0
1644/2 = 822
Fe 2 O 3 (s)
By Hess law,
822 = 828 + 10564 + 744 423 + 2532 + LE (ecf)
LE = 15067 1.51 x 104 kJ mol1
[5, max 4]
[4]
[Total: 13]
6 (a) Coffee beans contain chlorogenic acid.
OH
O O OH
O OH
trendyline
d
HO OH
HO
HO
chlorogenic
hlorogenic acid
ac
(i) How many moles of H 2 (g) will be e

evolved when 1 mol of cchlorogenic acid
reacts with an excess of sodium metal?
3 mol
[1]
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VJC 2016 9647/02/PRELIM/16
13
On heating with dilute aqueous acid, chlorogenic acid produces two compounds D
and E.
OH
+ OH OH
chlorogenic H (aq) O
+
acid heat HO
HO OH O OH
OH
D E
.
conc H2SO4 excess
heat Br2(aq)
F G
C7H6O3
When compound D is heated with concentrated H 2 SO 4 , compound F, C 7 H 6 O 3 , is

formed.
Compound F does not decolourise cold dilute acidified KMnO 4 but reacts with
Br 2 (aq).
When compound E is treated with an excess of Br 2 (aq), compound G is produced.
(ii) If the test with cold dilute acidified KMnO 4 had been positive, which
functional group would this have shown to be present in F?
C=C bond OR alkene functional group

[1]
(iii) Suggest the structures for compounds F and G, and draw them in the
relevant boxes below.
OH OH OH Br
O OH
HO2C
Br
Br OH
OR Br
HO2C OH
C7H6O3
F G
[2]
(b) Allyl alcohol, CH 2 =CHCH 2 OH, is a colourless liquid which is soluble in water.
Crotyl alcohol, CH 3 CH=CHCH 2 OH, is a colourless liquid which is used as a

solvent.
(i) Describe how you would distinguish between allyl alcohol and crotyl alcohol.
trendyline
p
The compounds mayy be distinguished
g byy a preliminary
p y chemical reaction
followed by a subsequent testing of the reaction products. In
Include clearly the
reagents, conditions and observations for each compound.
Step I: KMnO 4 , NaOH(aq),

Na
NaOH(aq), cold
col
Step II: I 2 , NaOH(aq), warm
Crotyl alcohol gives yellow ppt.
Allyl alcohol does not give yellow ppt.
[2]
1686 trendyline
14
(ii) Allyl alcohol may be converted into propanal by using a ruthenium(IV)

catalyst in water.
ruthenium(IV)
CH 2 =CHCH 2 OH CH 3 CH 2 CHO
State the type of reaction and explain your answer.
It is a disproportionation reaction where the C=C bond is reduced and

the primary alcohol is oxidised.
[1]
[Total: 7]
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VJC 2016 9647/02/PRELIM/16

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Section A
consider to be correct and shade your choice on the answer sheet provided.
1 For indoor air quality safety standards, the maximum safe tolerance level of carbon
monoxide gas is 6 104 m3 of carbon monoxide in 1 m3 of air. Given that a typical room
measures4 m by 4 m by 3 m, calculate the number of molecules of carbon monoxide
present in the room at this tolerance level at room temperature and pressure?
A 1.13 1024
B 7.22 1023
C 1.51 1022
D 7.22 1020
2 Soluble mercury compounds such as mercury(II) nitrate are highly toxic. One removal
method involves the treatment of wastewater contaminated with mercury(II) nitrate with
sodium sulfide to produce solid mercury(II) sulfide and sodium nitrate solutions.
Calculate the mass of mercury(II) sulfide formed when 0.020 dm3 of 0.100 mol dm3
sodium sulfide reacts with 0.050 dm3 of 0.010 mol dm3 mercury(II) nitrate?
A 0.117 g B 0.133 g C 0.280 g D 0.466 g
3 Gaseous particle X hasa proton number n, and a charge of +1.

Gaseous particle Y has a proton number (n+1), and is isoelectronic with X.
Which statement about X and Y is correct?
A When placed in an electric field, the angle of deflection for X is the same as that of
Y.
B X requires more energy than Y when a further electron is removed from each
particle.
C X releases more energy than Y when an electron is added to particle.
D X has a larger radius than Y.
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9647 / YJC / 2016 / JC2 Preliminary Examination / Paper 1
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3
4 Covalent bonds are formed by orbital overlap. The shape of unsaturated hydrocarbon
molecules can be explained in terms of hybridisation of orbitals.
Which bond is not present in the molecule shown below?
H C C H
C C
H
C H
H
H
A bond formed by 2sp3 2sp2 overlap.
B bond formed by 2sp3-2sp overlap.
C bond formed by 1s-2sp overlap.
D bond formed by 2p-2p overlap.
5 Which statement about graphite is not correct?
A The carbon-carbon bonds in graphite are shorter than those in diamond.
B It can act as a good lubricant due to the weak forces of attraction between the layers
of atoms.
C Carbon to carbon distances between the planes of hexagonal rings are smaller than
those within the planes.
D It acts as a good conductor of electricity in the direction parallel to the planes

containing hexagonal rings of carbon.
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4
6
Gas T
Gas U
Gas T Gas U
A H 2 (g) at 298 K CO 2 (g) at 298 K
B CH 4 (g) at 298 K NH 3 (g) at 298 K
C O 2 (g) at 500 K O 2 (g) at 298 K
D N 2 (g) at 298 K N 2 (g) at 500 K
7 The polymerisation of propene to form polypropene occurs readily at room temperatures.
What will be the signs of G, H and S for the polymerisation reaction at

roomtemperature?
G H S
A +
B + +
C +
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d li
D
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5
8 The rate of the redox reaction between hydrochloric acid and Mg
Mg + 2HCl MgCl 2 + H 2
can be followed by measuring the time taken for the same volume of hydrogen to be
produced from a range of hydrochloric acid concentrations.
To find the order with respect to hydrochloric acid, which would be the most suitable graph
to plot using the data?
A [HCl] against time
1
B [HCl] against
time
C Volume H 2 against time
1
D Volume H 2 against
time
9 The numerical value of the solubility product of nickel(II) carbonate is 6.6 109 while that
of silver carbonate is 2.1 1011 at 25 C.
A Addition of silver nitrate increases the solubility of silver carbonate.
B The solubility of silver carbonate is higher than the solubility of nickel(II) carbonate.
C Addition of nitric acid to a solution containing nickel(II) carbonate increases the

solubility product of nickel(II) carbonate.
D Nickel(II) carbonate precipitates first when sodium carbonate is added to a solution

containing equal concentrations of nickel(II) and silver ions.
10 What is the pH of 10 cm3 of 0.05 moldm3 sodium benzoate?
[K a of benzoic acid = 6 105moldm3]
A 6.46
B 7.46
C 8.46
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D 9.46
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6
11 A sample of 20.0 cm3 of 0.20 moldm3 iron(II) sulfate is titrated against 0.05 moldm3
potassium manganate(VII) in the presence of excess fluoride ions. It is found that
20.0 cm3 of the manganate(VII) solution is required to reach the end-point.
What is the oxidation number of manganese at end-point?
A +3
B +4
C +5
D +6
12 Anodisation is a process to increase corrosion resistance and surface hardness in

aluminium objects.
A possible set up for the process is shown as below:
Which of the following statements about the anodisation of aluminium is true?
A Aluminium dissolves at the anode.
B Hydrogen gas is liberated at the anode.
C Water is oxidised at the anode to form oxygen gas.
D Replacing the electrolyte with NaOH(aq) will cause the reaction to cease.
13 Which of the following elements forms an oxide with a giant structure and a chloride which
is readily hydrolysed?
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A on
Silicon
B um
m
Barium
C um
m
Sodium
D Phosphorus
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7
14 An element in Period 3 has the following properties:
- Its first ionisation energy is larger than both the elements before and after it across the
period.
- It conducts electricity.
- It reacts slowly with cold water but react readily with steam to give a gas.
Which statement about this element is not correct?
A It has a high melting and boiling point.
B It forms an oxide that produces a solution that is acidic when added to water.
C It forms a chloride that produces a solution that isslightly acidic when added to water.
D Its oxidation state in compounds usually follows the group number it belongs to in the
Periodic Table.
15 The following report appeared in a newspaper article.
Drums of bromine broke open after a vehicle crash on the motorway. Traffic was diverted
aspurple gaseous bromine drifted over the road (it is denser than air), causing irritation to
drivers eyes. Firemen sprayed water over the scene of the accident, dissolving the
bromineand washing it away.
What is wrong with the report?
A Bromine does not dissolve in water.
B Bromine does not vapourise readily.
C Bromine is less dense than air.
D Bromine is not purple.
16 When crystalline potassium chromate(VI) was dissolved in water, a yellow solution Q was
formed. Addition of dilute sulfuric acid to Q gave an orange solution R. When hydrogen
sulfide was bubbled through solution R, there was a color change in the solution and yellow
sulfur was produced.
Which process did not occur in the above experiment?
A Ligand exchange
B Redox reaction
17
C
D trendyline
ipitation
Precipitation
-base
base
Acid-base
Chlorine compounds show oxidation states ranging from 1 to +7.
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8
What are the reagents and conditions necessary for the oxidation of chlorine gas into
acompound containing chlorine in the +5 oxidation state?
A Cold dilute NaOH
B Hot concentrated NaOH
C Concentrated H 2 SO 4 at room temperature
D AgNO 3 (aq) followed by NH 3 (aq) at room temperature
A Transition elements form many coloured compounds.
B Transition elements or their compounds are widely used as catalysts.
C Transition elements form one or more stable ions with partially filled d-orbitals.
D Transition elements exhibit more than one oxidation state in their compounds.
19 How many stereoisomers does a molecule of Nandrolone has?

O
O C
O
Nandrolone
A 8 B 16 C 32 D 64
20
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The structure of compound Z is as seen below:
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9
OH
Compound Z
It is completely reacted with hot concentrated H 2 SO 4 to form compound Y. What is the total
number of isomers of Y?
A 2 B 3 C 4 D 5
21 2methylpropanoic acid can be synthesised from 1chloropropane through a series of

reactions.
synthesis?
A PCl 5 , acidified KMnO 4
B ethanolic KCN, dilute HCl
C aqueous KOH, HCl, ethanolic KCN, dilute HCl
D ethanolic KOH, HBr, ethanolic KCN, dilute H 2 SO 4
22 Which statement about ethanal and propanone is not correct?
A Both give a positive tri-iodomethane test.
B Both react with 2,4-dinitrophenylhydrazine reagent.
C Both may be prepared by the oxidation of an alcohol.
D Both react with hot acidified sodium dichromate(VI).
23
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When sodium optically
dium iodide in propanone iss added to an optical ly active sample of
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10
2-bromobutane, a sodium bromide precipitate is formed after 13 minutes upon heating.
NaI + CH 3 CHBrCH 2 CH 3 CH 3 CHICH 2 CH 3 + NaBr(s)
The experiment was repeated several times and the rate equation was found to be
Rate = k[CH 3 CHBrCH 2 CH 3 ][NaI]
A The mechanism involves a reactive intermediate.
B The organic product sample obtained rotates the plane of polarised light.
C A similar experiment, using 1-bromobutane, will produce a precipitate in less than 13

minutes.
D A similar experiment, using 2-chlorobutane, will take more than 13 minutes to

produce a precipitate.
24 Which reagent can be used to distinguish between compounds R and S under suitable
conditions?
CH3 O
HO C C
H O CH2 Br
HO C C
CH3 H
CHO
R S
A Acidified potassium dichromate (VI)
B Alkaline copper(II) solution
C Sodium metal
D Phosphorus pentachloride
25 The two-stage reaction sequence given shows a possible mechanism for the reaction
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11
between phenoxide ion and ethanoyl chloride.
CH3 CH3 CH3
PhO C O PhO C O PhO C O
Cl Cl Cl
where Ph = phenyl
How should the overall reaction be classified?
A Electrophilic addition
B Nucleophilic addition
C Electrophilic substitution
26 Cyanohydrins can be made from carbonyl compounds by generating CN ions from HCN in
the presence of a weak base.
1 1
R R OH
--
CN
C O + HCN C
R2 R2 CN
In a similar reaction, CH 2 COOCH 3 ions are generated from CH 3 COOCH 3 by strong bases.
Which compound can be made from an aldehyde and CH 3 COOCH 3 ?
A CH 3 CH(OH)COOCH 3
B CH 3 COOCH 2 CH(OH) CH 3
C CH 3 CH 2 CH(OH)CH 2 COOCH 3
D (CH 3 ) 2 C(OH)CH 2 COOCH 3
27
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Two common drugs administered when a patient experiences headache or fever are
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12
paracetamol and aspirin.
COOH
O O
HO NH O
paracetamol aspirin
A solution of the two drugs was hydrolysed using hot aqueous sodium hydroxide.
Which organic product would be produced?
A B
COO -
O
-O N
H O
O
C D
O
-O NH2
28 Acetaminophen is a drug used in headache remedies. It has the following structure:
Acetaminophen
Which of the following reagents reacts with Acetaminophen?
A Sodium carbonate
B Cold sodium hydroxide
C Alkaline aqueous iodine
D 2,4-dinitrophenylhydrazine
29
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uence shows the correct order off increasing
Which sequence in p
pKK b in an aqueo
aqueous solution of equal
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13
concentration?
A C 2 H 5 CONH 2 < C 6 H 5 NH 2 < C 2 H 5 NH 2 < C 2 H 5 NH 3 +
B C 2 H 5 NH 2 < C 6 H 5 NH 2 < C 2 H 5 NH 3 +< C 2 H 5 CONH 2
C C 2 H 5 NH 2 < C 6 H 5 NH 2 < C 2 H 5 CONH 2 < C 2 H 5 NH 3 +
D C 2 H 5 NH 3 +< C 2 H 5 CONH 2 < C 2 H 5 NH 2 < C 6 H 5 NH 2
30 There are three pK a values associated with glutamic acid: 2.1, 4.1 and 9.5.
The pH-volume curve obtained when 30 cm3 of NaOH is added to 10 cm3 of the protonated
form of glutamic acid of the same concentration is given below.
A B
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C D
Section B
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14
pick a tick against the statements that you consider to be correct).
A B C D
31 The radius and charge of each of the six ions are shown below.
radius / nm 0.14 0.18 0.15 0.14 0.18 0.15
The ionic solids JX, LY and MZ are of the same lattice type. Which of the following
statements are correct?
1 The melting point increases in the order LY < JX < MZ.
2 The numerical value of hydration energy of Xis smaller than that of Z2.
3 The solution containing M2+ ions is more acidic than the solution containing J+ ions.
Which of the following will increase the cell potential?
1 Adding iodine crystals into the anodic half cell.
33
2
3
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Adding
ng solid silver nitrate into the cathodichalf cell.
Increasing
ce
aq)/Br(aq)
asing the concentration of Br 2 (aq) in the Br 2 (aq)/Br
easing
From the position of the elements present in

n the
aq) half cell.
th Periodic Table and the physical properties
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15
of the compounds, which compounds are covalent?
1 (CH 3 ) 2 SiCl 2 b.p. 70C
2 GeCl 4 b.p. 86C
3 AlBr 3 b.p. 265C
The oxides of titanium, iron and nickel are used as catalysts in the industries.
Which properties are titanium, iron and nickel likely to have in common?
1 similar ionic radii
2 high melting points
3 variable oxidation states
With reference to the two half equations below, which statements are correct?
[Fe(CN) 6 ]3 + e [Fe(CN) 6 ]4
Fe3+ + e Fe2+
1 [Fe(CN) 6 ]3is more stable than Fe3+
2 [Fe(CN) 6 ]4 is a stronger reducing agent than Fe2+
3 Both [Fe(CN) 6 ]3 and Fe3+ can oxidize MnO 4 2 to MnO 4
36 Propene is found to react with chlorine in the presence of aqueous sodium bromide and
sodium nitrate. Which of the following are not possible products of the reaction?
1 CH3 CH CH2
Br Br
2 CH3 CH CH2
ONO 2 Cl
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re
3 CH3 CH CH2
O
OH Cl
nses A to D should be selected on

The responses n the
th basis of
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16
A B C D
1, 2 and 3 1 and 2 only 2 and 3 only 1 only is
are correct are correct are correct correct
37 Which of the following reactions will not give a good yield of the desired product?
38 The three compounds E, F and G have the following structures?
HO
COOCH3
N
N
N
N CH CH2 N
OH O
E F G
Which statements about E, F and G are correct?
1 E and G have the same empirical formula.
2 E and F are isomers
3 The Mr of F is exactly twice that of G
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17
39 The energy profile for the following reaction is shown below. [D = 2H]
H H

C6H5 C Cl + OH C6H5 C OH + Cl
D D
energy
X
reactants
products
Reaction pathway
Which conclusions can be drawn?
1 The product has no effect on the rotation of plane polarised light.
2 The rate of reaction can be increased by increasing concentration of OH.
3 The structure of the transition state at point X is
C6H5
HO C Cl
H D
40 Which groups within an amino acid are able to form a cross-chain link to stabilise the
tertiary structure of a protein?
1 CH 2 CONH 2
2 NH2
H CH2 CH2 CH2 NH C
NH
3 H CH2
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tr
re N
H
~ END OF PAPER ~
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2
Section A
consider to be correct and shade your choice on the answer sheet provided.
1 For indoor air quality safety standards, the maximum safe tolerance level of carbon
monoxide gas is 6 104 m3 of carbon monoxide in 1 m3 of air. Given that a typical room
measures
4 m by 4 m by 3 m, calculate the number of molecules of carbon monoxide present in the
room at this tolerance level at room temperature and pressure?
A 1.13 1024
B 7.22 1023
C 1.51 1022
D 7.22 1020
Answer: B
For 1 m3 of air, 6 x 104of CO is allowed

For 4 4 3 = 48 m3 of air, volume of CO = 48 x 6 x 104= 0.0288 m3 = 28.8 dm3
Number of moles of CO = 28.8 / 24 = 1.20 mol
Number of molecules
= 1.20 (6.02 1023)
= 7.22 1023
2 Soluble mercury compounds such as mercury(II) nitrate are highly toxic. One removal
method involves the treatment of wastewater contaminated with mercury(II) nitrate with
sodium sulfide to produce solid mercury(II) sulfide and sodium nitrate solutions.
Calculate the mass of mercury(II) sulfide formed when 0.020 dm3 of 0.100 mol dm3
sodium sulfide reacts with 0.050 dm3 of 0.010 mol dm3 mercury(II) nitrate?
A 0.117 g B 0.133 g C 0.280 g D 0.466 g
Answer: A
Balanced equation:
Hg(NO 3 ) 2 (aq) + Na 2 S(aq) HgS(s) + 2NaNO 3 (aq)
No. of moles of Na 2 S
= 0.020 0.100 = 2.00 103mol
No. of moles of Hg(NO 3 ) 2
= 0.050 0.010 = 5.00 104 mol
2.00 103mol of Na 2 S will require 2.00 103 mol of Hg(NO 3 ) 2 for complete reaction.
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Since 5.00 0 104 mol of Hg(NO 3 ) 2 is useded (lesser than 2.00
2 103 need
needed), thus Hg(NO 3 ) 2
is limiting.
No. of moles es of HgS = 5.00 10 044mol
mo
Mass of HgS gS
S
= (5.00 10 044) (201
1 + 32.1)
32 1) = 0
0.11655
11655 g
= 0.117 g
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3
3 Gaseous particle X hasa proton number n, and a charge of +1.

Gaseous particle Y has a proton number (n+1), and is isoelectronic with X.
Which statement about X and Y is correct?
A When placed in an electric field, the angle of deflection for X is the same as that of
Y.
B X requires more energy than Y when a further electron is removed from each
particle.
C X releases more energy than Y when an electron is added to particle.
D X has a larger radius than Y.
Answer: D
Particle X
Number of protons n
Number of electrons n-1
Thus Xhas a charge of +1
Particle Y
Number of protons n+1
Number of electrons n-1
Thus Y has a charge of 2
A is incorrect.

Angle of deflection

Y has double the charge of X DVFRPSDUHGWRKRZHYHUWKHDWRPLFPDVVRIY is

not double that of X (X and Y are consecutive elements as deduced from their proton
numbers). Thus their charge/mass ratios will not be the same.
B is incorrect. As X has one less proton than Y, it has a smaller nuclear charge. As both
particles are isoelectronic (same number of inner shell electrons), shielding effect will be
the similar. Effective nuclear of X will be smaller. The valence electrons of X will be less
strongly attracted to the nucleus. Thus less energy is needed to remove the outermost
electron.
C is incorrect. X releases lesser energy than Y when an electron is added. The attractive
force between the incoming electron and the nucleus is weaker than that for Y as X has
smaller effective nuclear charge.
D is correct.Same explanation as Option B. X has a smaller nuclear charge (fewer protons

than Y) and the same shielding effect as Y (same number of inner shell electrons).
Effective nuclear of X will be smaller. The valence electrons of X will be less strongly
attracted to the nucleus. Thus the radius of X is larger than that of Y.
t d li
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1731 trendyline
4
4 Covalent bonds are formed by orbital overlap. The shape of unsaturated hydrocarbon
molecules can be explained in terms of hybridisation of orbitals.
Which bond is not present in the molecule shown below?
H
C C H
H
C C
H C
H
H
A bond formed by 2sp3 2sp2 overlap.
B bond formed by 2sp3-2sp overlap.
C bond formed by 1s-2sp overlap.
D bond formed by 2p-2p overlap.
Answer: B
4 5
H
C C H
H 2 3
C C
1
H C
H
H
A is correct. There is a ERQGIRUPHGE\VS3 2sp2 overlap present between C1-C2.
B is incorrect. There isnt any ERQGIRUPHGE\VS3-2spoverlap present.
C is correct. There is a ERQGIRUPHGE\V-2sp overlap present between hydrogen atom

and C5.
D is correct. There is a bond formed by 2p-2p overlap present between C2-C3 and C4-
C5.
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1732 trendyline
5
5 Which statement about graphite is not correct?
A The carbon-carbon bonds in graphite are shorter than those in diamond.
B It can act as a good lubricant due to the weak forces of attraction between the layers
of atoms.
C Carbon to carbon distances between the planes of hexagonal rings are smaller than
those within the planes.
D It acts as a good conductor of electricity in the direction parallel to the planes

containing hexagonal rings of carbon.
Answer: C
A is true. The carbon-carbon bonds in graphite are formed by sp2-sp2 overlap whereas
carbon-carbon bonds in diamond are formed by sp3-sp3 overlap. sp2-sp2 overlap is more
effective than sp3-sp3 overlap due to the greater s-character, thus the C-C bond length in
graphite is shorter.
B is true. The weak id-id forces between the layers allow the layers to slide past one
another, thus graphite is a good lubricant.
C is false. Carbon to carbon distances between the planes of hexagonal rings (weak id-id
interactions) are longer than those within the planes (strong C-C covalent bonds).
D is true. Within each layer, each carbon atom is covalently bonded to three other carbon
atoms using 3 of the 4 valence electrons. The presence of delocalised electrons between
the layers accounts for graphite being a good conductor when a potential difference is
applied along the layer. It does not conduct across the layer.
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1733 trendyline
6
6
Gas T
Gas U
Gas T Gas U
A H 2 (g) at 298 K CO 2 (g) at 298 K
B CH 4 (g) at 298 K NH 3 (g) at 298 K
C O 2 (g) at 500 K O 2 (g) at 298 K
D N 2 (g) at 298 K N 2 (g) at 500 K
Answer: D
From graph, Gas T deviates more from ideality than Gas U.
A is incorrect. Deviation of CO 2 from ideal gas behaviour is larger than that of H 2 . CO 2 has
a greater number of electrons than O 2 , thus the electron cloud is more polarisable,
resulting in stronger instantaneous dipole-induced dipole interactions between CO 2
molecules.
B is incorrect. Deviation of NH 3 from ideal gas behaviour is larger than that of CH 4 . There
is stronger hydrogen bonding between NH 3 molecules than instantaneous dipole-induced
dipole interactions between CH 4 molecules.
C is incorrect. Deviation of O 2 (g) at 298 K from ideal gas behaviour is larger than that at
500 K. At higher temperatures, particles in a gas possess large kinetic energy and are able
to overcome intermolecular forces of attraction such that these attractions can be
considered to be insignificant and negligible.
D is correct. Deviation of N 2 (g) at 500 K from ideal gas behaviour is smaller than that at
298 K. At higher temperatures, particles in a gas possess large kinetic energy and are able
to overcome intermolecular forces of attraction such that these attractions can be
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consideredd to be insignificant and negligible.
negligib
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7
7 The polymerisation of propene to form polypropene occurs readily at room temperatures.
What will be the signs of G, H and S for the polymerisation reaction at

roomtemperature?
G H S
A +
B + +
C +
Answer: D
4XHVWLRQVWDWHVWKDWWKHUHDFWLRQLVVSRQWDQHRXVDWURRPWHPSHUDWXUHWKXV*LVQHJDWLYH
The overall reaction involves the breaking of a C-&ERQGDQGWKHIRUPDWLRQRI&-&

ERQG6LQFHWKHERQGLVVWURQJHUWKDQWKHERQGWKHHQHUJ\UHOHDVHGIURPWKH
IRUPDWLRQRIWKHERQGLVJUHDWHUWKDQWKHHQHUJ\DEVRUEHGIRUWKHEUHDNLQJRIWKHERQd.
Thus H is negative.
7KHVLJQIRU6LVQHJDWLYHDVWKHUHLVDGHFUHDVHLQWKHQXPEHURIPROHFXOHVWKXVWKHUH
are fewer ways of arranging the molecules, level of disorderliness decreases.
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8 The rate off the redox reaction between hydrochloric acid
ac and Mg
Mg + 2HCl MgCl
MgCl 2 + H 2
can be followed
llowed
owed by measuring the time taken for the same volume of hydrogen to be
produced from a range of hydrochloric acid concentrations
co
concentrations.
1735 trendyline
8
To find the order with respect to hydrochloric acid, which would be the most suitable graph
to plot using the data?
A [HCl] against time
1
B [HCl] against
time
C Volume H 2 against time
1
D Volume H 2 against
time
Answer: B
A is incorrect.Using graph of [HCl] against time, the order ofreaction with respect to
hydrochloric acid cannot be found but only the instantaneous rate of reaction can be found
by finding drawing tangent and calculate the gradient to the tangent at different time.
B is correct.The rate equation proposed is Rate = k[HCl]n. Since question has mentioned
that time taken for the same volume of hydrogen to be produced, 1/time will thus be
deemed as rate.If order of reaction with respect to hydrochloric acid is 1 (n=1), the
appropriate graph, rate = [HCl] against 1/time (also deemed as rate) will be a straight line
with positive gradient and the gradient = k.
C is incorrect.As the question mentioned that the data collected is time taken to produce
the same volume when different concentrations of hydrochloric acid, the graph of volume of
hydrogen against time will be the same even different concentrations of hydrochloric acid is
used.
D is incorrect.As the question mentioned that the data collected is time taken to produce
the same volume when different concentrations of hydrochloric acid, the graph of volume of
hydrogen against 1/time will be the same despite that different concentrations of
hydrochloric acid are used.
9 The numerical value of the solubility product of nickel(II) carbonate is 6.6 109 while that
of silver carbonate is 2.1 1011 at 25 C.
A Addition of silver nitrate increases the solubility of silver carbonate.
B The solubility of silver carbonate is higher than the solubility of nickel(II) carbonate.
C Addition of nitric acid to a solution containing nickel(II) carbonate increases the
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y
solubility product of nickel(II) carbonate.
D Nickel(II)
el((II
el II) carbonate precipitates first when sodium carbonate is added to a solution
containing
in g equal concentrations of nickel(II)
ainin nickel(
nickel(II
II) and silver ions.
Answer: B
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9
A is incorrect.
Ag 2 CO 3 (s) 2Ag+(aq) + CO 3 2-(aq) ---- (1)
AgNO 3 (s) Ag+(aq) + NO 3 -(aq)
Addition of silver nitrate increases [Ag+] in eqm 1, the position of eqm 1 shifts LHS,
the solubility should decrease.
B is correct
2
K sp [Ag ] 2 [CO 3 ] 2.1 10 11
K sp (2s) 2 (s)
2.1 10 11
s3 1.73 10 4 moldm 3
4
2
K sp [Ni 2 ][CO 3 ] 6.6 10 9
s 6.6 10 9 8.14 10 5 moldm 3

From the above calculation it is seen that the solubility of silver carbonate is higher
than that of nickel(II) carbonate.
C is incorrect.Solubility product is only affected by temperature. Therefore addition

of nitric acid cannot change the magnitude of solubility product.
D is incorrect.
Assuming [Ni2+] = [Ag+] = 0.100 moldm-3
2
K sp [Ni2 ][CO3 ] 6.6 10 9
2 6.6 10 9
[CO3 ] 6.6 10 8 moldm 3
0.100
K [Ag ] 2 [CO 2 ] 2.1 10 11
sp 3
2.1 10 11
[CO 2 ] 2.1 10 9 moldm 3
3
0.100 2
Since lower [CO 3 2-] needed to see first trace of silver carbonate is lower than that
of nickel (II) carbonate, silver carbonate should be precipitated out first.
10 What is the pH of 10 cm3 of 0.05 moldm3 sodium benzoate?
[K a of benzoic acid = 6 105moldm3]
A 6.46
B 7.46
C 8.46
D 9.46
Answer: C
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y
Let the saltt B be the benzoate salt.
s
B + H 2 O BH
H + OH
1737 trendyline
10
Kb K w
Ka
14
1 10
6 10 6
1.6667 10 10 moldm 3
[OH ][BH]
Kb 1.6667 10 10
[B ]
[OH ] 2
1.6667 10 10
[B ]
[OH ] 1.6667 10 10 0.05
2.8868 10 6 moldm 3
pOH log(2.8868 10 6 ) 5.5395
pH 14 5.5395 8.46
11 A sample of 20.0 cm3 of 0.20 moldm3 iron(II) sulfate is titrated against 0.05 moldm3
potassium manganate(VII) in the presence of excess fluoride ions. It is found that 20.0
cm3 of the manganate(VII) solution is required to reach the end-point.
What is the oxidation number of manganese at end-point?
A +3
B +4
C +5
D +6
Answer: A
MnO 4 - + 8H+ + (7-n)e Mnn+ + 4H 2 O

Fe2+ Fe3+ + e
20
no of mol of electrons gained by Mn (7 - n) 0.05 0.00100 mol
1000
20
no of mol of electrons lost by Fe 0.20 0.00400 mol
1000
no of mol of eletctrons lost by Fe no of mol of electrons gained by Mn
(7 - n) 4
n3
Thus the new oxidation state of Mn is +3.
Alternative method:
0.00400 mol of Fe2+ lost 0.00400 mol of electron to Mn
0.00100 mol of MnO 4 - gained 0.00400 mol of electron from Fe2+
1 mol of MnO 4 - gained 0.004/0.001 = 4 mol of electron from Fe2+
trendyline
all oxidation state of Mn in MnO 4 - is +7 and tthe Mn gained 4 electrons, thus the
The original
new oxidation
tion state is +3
+3.
12 Anodisation
n is a process to increase corrosion resistance and surface h
hardness in
aluminium objects.
1738 trendyline
11
A possible set up for the process is shown as below:
Which of the following statements about the anodisation of aluminium is true?
A Aluminium dissolves at the anode.
B Hydrogen gas is liberated at the anode.
C Water is oxidised at the anode to form oxygen gas.
D Replacing the electrolyte with NaOH(aq) will cause the reaction to cease.
Answer: C
A is not true. In this electrolytic process, water is oxidised in preference to aluminium.

Therefore, aluminium is not oxidised hence it is not dissolved.
B is not true. At anode, water from electrolyte is oxidised to oxygen gas.

2H 2 O O 2 + 4H+ + 4e
C is true. The purpose of the process is to allow water from the electrolyte to be oxidised
to form oxygen gas.
2H 2 O O 2 + 4H+ + 4e
Oxygen liberated then reacts with the aluminium object at the anode to form the protective
layer of aluminium oxide.
4Al + 3O 2 2Al 2 O 3
D is not true. During the process, hydroxide ions from electrolyte can be oxidised to form
oxygen gas at the anode. Therefore, the process does not stop.
4OH- 2H 2 O + O 2 + 4e
13 Which of the following elements forms an oxide with a giant structure and a chloride which
is readily hydrolysed?
C
trendyline
on
Silicon
um
m
Barium
Sodium
1739 trendyline
12
D Phosphorus
Answer: A
A is correct. The oxide of silicon, SiO 2 , exists as a giant covalent structure while the
chloride of silicon, SiCl 4 , hydrolyses in water to form SiO 2 and HCl.
B is incorrect. Barium oxide has a giant ionic lattice structure and barium chloride does not
undergo hydrolysis.
C is incorrect. Similar explanation to B.
D is incorrect. Phosphorus pentoxide has a simple molecular structure although

phosphorus pentachloride undergoes hydrolysis readily.
Structure of P 4 O 10
14 An element in Period 3 has the following properties:
- Its first ionisation energy is larger than both the elements before and after it across the
period.
- It conducts electricity.
- It reacts slowly with cold water but react readily with steam to give a gas.
Which statement about this element is not correct?
A It has a high melting and boiling point.
B It forms an oxide that produces a solution that is acidic when added to water.
C It forms a chloride that produces a solution that isslightly acidic when added to water.
trendyline
D xidation
idation state in compounds usually follows tthe group number
Its oxidation numbe it belongs to in the
odic Table.
Periodic Tabl
Answer: B
The element
ent is magnesium
magnesium.
1740 trendyline
13
A is correct. The strong metallic bonding in magnesium results in its high melting and
boiling point.
B is incorrect. Magnesium oxide is basic in nature and does not produce H+.
C is correct.When dissolved in water, hydrated Mg2+ is formed. Due to its relatively high
charge density, Mg2+ partially hydrolyses in water.
[Mg(H 2 O) 6 ]2+ [Mg(H 2 O) 5 (OH)]+ + H+
D is correct. It has an oxidation state of +2.
15 The following report appeared in a newspaper article.
Drums of bromine broke open after a vehicle crash on the motorway. Traffic was diverted
aspurple gaseous bromine drifted over the road (it is denser than air), causing irritation to
drivers eyes. Firemen sprayed water over the scene of the accident, dissolving the
bromineand washing it away.
What is wrong with the report?
A Bromine does not dissolve in water.
B Bromine does not vapourise readily.
C Bromine is less dense than air.
D Bromine is not purple.
Answer: D
A is correct. Bromine dissolves in water to form an orange solution.
B is correct. Bromine has a relatively high boiling point due to its big and polarisable
electron cloud and hence stronger instantaneous dipoleinduced dipole forces.
C is correct. Bromine has a molecular weight of 160 grams per mole, which is denser than
air, which has a molecular weight of 28 grams per mole (mainly nitrogen gas).
D is incorrect. Bromine exists as a red-brown gas.
16 When crystalline potassium chromate(VI) was dissolved in water, a yellow solution Q was
formed. Addition of dilute sulfuric acid to Q gave an orange solution R. When hydrogen
sulfide was bubbled through solution R, there was a color change in the solution and
yellow sulfur was produced.
A
trendyline
Which process
ocess did not occur in the above experiment
Ligand
nd
d exchange
h
experiment?
1741 trendyline
14
B Redox reaction
C Precipitation
D Acid-base
Answer: A
K 2 CrO 4 dissolves in water to give Q, CrO 4 2-.

Q undergoes acid-base reaction to give R, Cr 2 O 7 2-. R undergoes redox reaction with H 2 S
where sulfur was precipitated.
17 Chlorine compounds show oxidation states ranging from 1 to +7.
What are the reagents and conditions necessary for the oxidation of chlorine gas into
acompound containing chlorine in the +5 oxidation state?
A Cold dilute NaOH
B Hot concentrated NaOH
C Concentrated H 2 SO 4 at room temperature
D AgNO 3 (aq) followed by NH 3 (aq) at room temperature
Answer: B
A is incorrect. The compound formed is NaOCl and the oxidation state of chlorine in the
compound is +1.
B is correct. The compound formed is NaClO 3 and the oxidation state of chlorine in the
compound is +5.
C is incorrect. No reaction occurs between chlorine gas and sulfuric acid.
D is incorrect. Cl 2 + H 2 O HClO + HCl

Ag+ + ClAgCl
AgCl + 2NH 3 [Ag(NH 3 ) 2 ]+Cl
Cl in product does not have oxidation state of +5.
A Transition elements form many coloured compounds.
trendyline
B sition
ition elements or their compounds are wide
Transition widely used as catalysts.
cataly
C sition elements form one or more stable ions with partially fill
Transition filled d-orbitals.
D sition elements exhibit more than one oxidation state in their compounds.
Transition
Answer: C
1742 trendyline
15
Atransition element is defined as a d-block element which forms one or more stable ions
with partially filled d-orbitals.
19 How many stereoisomers does a molecule of Nandrolone has?

O
O C
O
Nandrolone
A 8 B 16 C 32 D 64
Answer: D
A chiral carbon has four different groups attached to it. Nandrolone has 6 chiral carbons.
Double bond within a ring cannot exhibit cis-trans isomerism.
Total number of stereoisomers = 26 = 64
20
trendyline
The structure
ure
re of compound Z is as seen below:
1743 trendyline
16
OH
Compound Z
It is completely reacted with hot concentrated H 2 SO 4 to form compound Y. What is the total
number of isomers of Y?
A 2 B 3 C 4 D 5
Answer: C
This is an elimination reaction. The OH group and a H atom on a adjacent C atom are
removed to form an alkene.
similar -H bonded to C=C, no cis-trans similar -CH3 bonded to C=C, no cis-trans

CH3
H H
C
CH3
OH
trans-isomer cis-isomer
21 2methylpropanoic acid can be synthesised from 1chloropropane through a series of

reactions.
synthesis?
A PCl 5 , acidified KMnO 4
B ethanolic KCN, dilute HCl
trendyline
C aqueous
ou KOH, HCl,
eous HCl, ethanolic KCN,
N, dilute HCl
HC
Cl
D ethanolic
olic KOH, HBr, ethanolic KCN, dilute H 2 SO 4
nolic
Answer: D
1744 trendyline
17
Cl alcoholic KOH
reflux HBr(g), room temp

1-chloropropane
Br
dil H2SO4 , heat

CN
alcoholic KCN, reflux
COOH
2-methylpropanoic acid
22 Which statement about ethanal and propanone is not correct?
A Both give a positive tri-iodomethane test.
B Both react with 2,4-dinitrophenylhydrazine reagent.
C Both may be prepared by the oxidation of an alcohol.
D Both react with hot acidified sodium dichromate(VI).
Answer: D
A is correct. Both compounds contain H C CH3 structure and will produce a yellow ppt,
CHI 3 with aqueous alkaline iodine.
O
B is correct. Both compounds contain H C H functional group and will will produce an
orange ppt with 2,4-DNPH.
C is correct. Ethanal is an aldehyde that can be prepared by the oxidation of a primary

alcohol. Propanone is a ketone that can be prepared by the oxidation of a secondary
alcohol.
D is incorrect. Cr 2 O 7 2can only oxidise ethanal but not propanone. Aldehydes can be
further oxidised to carboxylic acids but ketones cannot be further oxidised.
23 When sodium iodide in propanone is added to an optically active sample of

2-bromobutane, a sodium bromide precipitate is formed after 13 minutes upon heating.
trendyline
NaI
NaI + CH 3 CHBrCH H 3 CH 3 CH
HBrC 2 CH CHICH
CH 2 CH 3 + NaBr(s)
NaBr(
NaBr(s
The experiment
ment was repeated several times and the rate equation was found to be
iment
Rate = k[CH 3 CHBrCH 2 CH 3 ][Na

][NaI]
[NaI]
1745 trendyline
18
A The mechanism involves a reactive intermediate.
B The organic product sample obtained rotates the plane of polarised light.
C A similar experiment, using 1-bromobutane, will produce a precipitate in less than 13

minutes.
D A similar experiment, using 2-chlorobutane, will take more than 13 minutes to

produce a precipitate.
Answer: A
A is incorrect. The rate equation shows that both reactants are involved in the rate-
determining step. Hence, it is S N 2 mechanism where no intermediate is formed.
B is correct. The reactant is chiral and all its molecules undergo an inversion of
configuration to remain as a chiral compound. The product will display optical activity.
For example, the starting optically active sample contains 40% (+) and 60% (-) isomers.
After S N 2 reaction, the product sample obtained will contain 60% (+) and 40% (-) isomers
which is still optically active and rotate the plane of polarised light.
C2 H5 C2 H5 C2 H5
- - - *C
I C Br I C Br I + Br-
Cl
H H
CH3 H CH3 CH3
C is correct. 1-bromobutane is a primary halogenoalkane while 2-bromobutane is a

secondary halogenoalkane. With a primary halogenoalkane, the attacking nucleophile
experiences less steric hindrance when attacking the C+and reacts more readily and the
precipitate is produced faster.
D is correct. The CCl bond is shorter than the CBr bond and has higher bond energy.
More energy is needed to break the bond and the rate of reaction of 2-chlorobutane will be
slower than that of 2-bromobutane.
24 Which reagent can be used to distinguish between compounds R and S under suitable
conditions?
trendyline
1746 trendyline
19
CH3 O
HO C C
H O CH2 Br
HO C C
CH3 H
CHO
R S
A Acidified potassium dichromate (VI)
B Alkaline copper(II) solution
C Sodium metal
D Phosphorus pentachloride
Answer: B
A cannot be used for the distinguishing test as it will oxidise the secondary alcohol and
aldehyde in R as well as the aldehyde in S. Orange acidified K 2 Cr 2 O 7 will turn green.
B can be used for the distinguishing test. R is an aliphatic aldehyde and reacts to form a
brick red precipitate of Cu 2 O. S is an aromatic aldehyde and will not be able to reduce
alkaline copper(II) solution.
C cannot be used for thedistinguishing test. Na will react with -OH groups in both R and S
and give off H 2 gas.
D cannot be used for thedistinguishing test. PCl 5 will react with -OH groups in both R and S
to produce white fume of HCl.
25 The two-stage reaction sequence given shows a possible mechanism for the reaction
between phenoxide ion and ethanoyl chloride.
CH3 CH3 CH3
PhO C O PhO C O PhO C O
Cl Cl Cl
where Ph = phenyl
How should the overall reaction be classified?
A trophilic addition
Electrophilic additio
B eophilic addition
Nucleophilic
C trophilic substitution
Electrophilic
1747 trendyline
20
Answer: D
In the first step, PhO behaves as a nucleophile by attacking the attacking the C+ that is
attached to O and Cl atoms.
At the end of the reaction, the Cl has left the molecule after being substituted.
26 Cyanohydrins can be made from carbonyl compounds by generating CN ions from HCN in
the presence of a weak base.
1 1
R R OH
CN--
C O + HCN C
R2 R2 CN

In a similar reaction, CH 2 COOCH 3 ions are generated from CH 3 COOCH 3 by strong bases.
Which compound can be made from an aldehyde and CH 3 COOCH 3 ?
A CH 3 CH(OH)COOCH 3
B CH 3 COOCH 2 CH(OH) CH 3
C CH 3 CH 2 CH(OH)CH 2 COOCH 3
D (CH 3 ) 2 C(OH)CH 2 COOCH 3
Answer: C
A is incorrect. The nucleophile used is COOCH 3 .
B is incorrect. The nucleophile used is CH 3 COOCH 2 .
C is correct. The nucleophile used is CH 2 COOCH 3 and it reacts with an aldehyde

CH 3 CH 2 CHO.

D is incorrect. The nucleophile used is CH 2 COOCH 3 but it reacts with a ketone
CH 3 COCH 3
27 Two common drugs administered when a patient experiences headache or fever are
paracetamol and aspirin.
COOH
trre
ttrendyline
re yl
ylilin
y
O
O
HO NH
O
paracetamol
1748 trendyline
21
aspirin
A solution of the two drugs was hydrolysed using hot aqueous sodium hydroxide.
Which organic product would be produced?
A B
COO -
O
O N
H
O
O
C D
O
O NH2
Answer: D
Alkaline hydrolysis of the amide bond in paracetamol produces the following:
O
HO NH O- NH2 + O
O-
Alkaline hydrolysis of the ester bond in aspirin produces the following:
COOH COO -
O-
O O- + O
O
28 Acetaminophen is a drug used in headache remedies. It has the following structure:
Acetaminophen
trendyline
Which of the
he following reagents reacts with Acetaminophen
Acetaminophen??
A um carbonate
Sodium
B Cold sodium hydroxide
1749 trendyline
22
C Alkaline aqueous iodine
D 2,4-dinitrophenylhydrazine
Answer: B
A has no reaction. There is no COOH present to react with the sodium carbonate.
B will react with the acidic phenol group in acetaminophen in a neutralisation reaction.
C has no reaction. The H

C CH3 structure is present but no C or H is directly bonded to
C=O for the reaction to occur.
D has no reaction. The aldehyde and ketone functional groups are not present.
29 Which sequence shows the correct order of increasing pK b in an aqueous solution of equal
concentration?
A C 2 H 5 CONH 2 < C 6 H 5 NH 2 < C 2 H 5 NH 2 < C 2 H 5 NH 3 +
B C 2 H 5 NH 2 < C 6 H 5 NH 2 < C 2 H 5 NH 3 +< C 2 H 5 CONH 2
C C 2 H 5 NH 2 < C 6 H 5 NH 2 < C 2 H 5 CONH 2 < C 2 H 5 NH 3 +
D C 2 H 5 NH 3 +< C 2 H 5 CONH 2 < C 2 H 5 NH 2 < C 6 H 5 NH 2
Answer: C
Increasing pK b means becoming less basic.
The electron donating C 2 H 5 group in C 2 H 5 NH 2 makes the lone pair of electrons on N atom
most available for donation to a proton and therefore the strongest base.
In C 6 H 5 NH 2 , the lone pair of electrons on N atom is delocalised into the benzene ring,
making it less available for donation to a proton. Phenylamine is therefore a weaker base
trendyline
than aliphatic
atic amines..
tic amines
In C 2 H 5 CONH
ONH
N 2 , the lone pair of electrons on N atom is delocalised over
ove the carbonyl C=O
and hence e not available for donation to a proton.
proton
H 3 + , th
In C 2 H 5 NH there are no lone
l pair
i off electrons
l t on the
th N atom
t ffor d
donation to a proton.-
1750 trendyline
23
NH 3 + is an acidic group with a proton for donation.
30
There are three pK a values associated with glutamic acid: 2.1, 4.1 and 9.5.
The pH-volume curve obtained when 30 cm3 of NaOH is added to 10 cm3 of the protonated
form of glutamic acid of the same concentration is given below.
trendyline
1751 trendyline
24
A B
C D
Answer: C
The protonated form of glutamic acid and its associated pK a values are:
-COOH with pKa of 2.1 is the most acidic. -NH 3 + is an electron withdrawing group and
disperses the negative charge of -COO- of its conjugate base and stabilises it. -NH 3 + is
closer to -COOH with pKa of 2.1 than -COOH with pKa of 4.1. Hence, the dissociation of
the carboxylic acid with pKa of 2.1 occurs to a larger extent.
trendyline
carboxylic acid (-COO
Adding NaOH
(-
(-COO -
((--NH 3 +) as the co
c acid is more acidic than protonated amine (-NH
Carboxylic conjugate base of the
OO ) is resonance stabilised. Hence, the dissociation of the carboxylic
N 3 +.
acid occurss to a larger extent than -NH
-NH
aOH would result in three equivalence

enc points being obtained a
as shown in the
1752 trendyline
25
graph.
The 1st equivalence point is achieved when 10 cm3 of NaOH was added:
+ OH + H2O
At point S, the 2nd equivalence point is achieved when 20 cm3 of NaOH was added:
+ OH + H2O
The 3rd equivalence point is achieved when 30 cm3 of NaOH was added:
+ OH + H2O
trendyline
1753 trendyline
26
Section B
pick a tick against the statements that you consider to be correct).
A B C D
31 The radius and charge of each of the six ions are shown below.
radius / nm 0.14 0.18 0.15 0.14 0.18 0.15
The ionic solids JX, LY and MZ are of the same lattice type. Which of the following
statements are correct?
1 The melting point increases in the order LY < JX < MZ.
2 The numerical value of hydration energy of Xis smaller than that of Z2.
3 The solution containing M2+ ions is more acidic than the solution containing J+ ions.
Answer: A
Option 1 is correct. JX, LY and MZ are ionic solids, thus their melting points are
determined by the strength of electrostatic forces of attraction between the oppositely
charged ions. The larger the magnitude of the lattice energy, the higher the melting point.
+
Lattice energy +
+
Lattice energy for JX, LY and MZ are: 3.57, 2.78 and 13.3 respectively. Thus melting point
increases in the order LY < JX < MZ.
Option 2 is correct. Numerical value of hydration energy is dependent on the charge

density of the ion . Charge density of X is 1/0.14 = 7.14 while that of Z is 2/0.15 =

13.3.
Thus the numerical value of hydration energy of Xis smaller than that of Z2.
Option 3 is correct. Charge density of M2+ is 2 / 0.15 = 13.3 while that of J+ is
trendyline
y
1 / 0.14 = 7.14
7 .Hence, M2+ has a higher
7.14.Hence, her charge density
de and thus a higher polarising
power.M2+draw
drawss electron density from the datively bonded
bonded water molecule
mo
mol towards itself
more and weaken the O-H O H bond to a greater extent.This
exten
extent.This
Th gives rise to a more acidic
solution.
1754 trendyline
27
Which of the following will increase the cell potential?
1 Adding iodine crystals into the anodic half cell.
2 Adding solid silver nitrate into the cathodichalf cell.
3 Increasing the concentration of Br 2 (aq) in the Br 2 (aq)/Br(aq) half cell.
Answer: C
Option 1 is incorrect. Adding iodine crystals remove thiosulfate ions through redox
reaction. [S 2 O 3 2-] decreases while [S 4 O 6 2-] will increase at the anode.
I 2 + 2S 2 O 3 2- S 4 O 6 2- + 2I-
The equilibrium at anode will be disturbed. According to Le Chateliers principle, the
position of equilibrium shift right to replenish the S 2 O 3 2- ions lost and to use up the S 4 O 6 2-
ions which were added from the above redox reaction. This makes E oxd (anode) to be more
positive.
S 4 O 6 2- + 2e 2S 2 O 3 2-
E cell becomes less positive as the E red (cathode) of same magnitude subtracts a larger
positive E oxd (anode) .
Option 2 is correct. Solid silver nitrate removes Br- ions in the cathode. This reduces [Br-].
Ag+(aq) + Br-(aq) AgBr(s)
The equilibrium at cathode will be disturbed. According to Le Chateliers principle, the
position of equilibrium will shift to right to replenish bromide ions which are precipitated
out. This makes E red (cathode) to be more positive.
Br 2 + 2e 2Br-
E cell = E red (cathode) - E oxd (anode)
E cell becomes more positive as the more positive E red (cathode) subtracts positive E oxd (anode)
which has the same magnitude.
trendyline
Option 3 iss correct.
c At the cathode,
Br 2 + 2e 2Br-
Increasing [Br [B 2 ] shifts the equilibrium at cathode towards
owards right. Le Chateliers
Chat principle
predicts that at position of equilibrium shifts to the right to use up the brom
bromine added. This
makes E red ed (cathode) to be more positive.
E cell = E red (cathode) - E oxd (anode)
1755 trendyline
28
E cell becomes more positive as the more positive E red (cathode) subtracts positive E oxd (anode)
which has the same magnitude.
33 From the position of the elements present in the Periodic Table and the physical properties
of the compounds, which compounds are covalent?
1 (CH 3 ) 2 SiCl 2 b.p. 70C
2 GeCl 4 b.p. 86C
3 AlBr 3 b.p. 265C
Answer: A
(CH 3 ) 2 SiCl 2 is covalent. This can be inferred from its low boiling point and that it resembles
(CH 3 ) 2 CCl 2 since both Si and C are in the same group.
GeCl 4 is covalent. Similar reasoning as above since both Ge and Si are in the same group.
AlBr 3 is covalent as its boiling point is relatively low.Al3+ has a high charge density and
polarises the electron cloud of Cl such that AlCl 3 is covalent. Since Bris more polarisable
due to larger electron cloud than Cl, AlBr 3 is likely to be covalent.
The oxides of titanium, iron and nickel are used as catalysts in the industries.
Which properties are titanium, iron and nickel likely to have in common?
1 similar ionic radii
2 high melting points
3 variable oxidation states
Answer: A
Titanium, iron and nickel belong to the first row of the d-block transition elements.
They have similar ionic radii due to the increase in shielding effect which is largely
cancelled out by the increase in nuclear charge. The effective nuclear charge remains
relatively constant across the first row of the d-block elements.
They have high melting points due to the strong metallic bonding, as both their 4s and 3d
electrons have similar energy and can be delocalised.
They have variable oxidation states as both the 3d and4s orbitals are similar in energy. The
4s and some (or all) of the 3d electrons can be removed without requiring too much
trendyline
energy.
1756 trendyline
29
With reference to the two half equations below, which statements are correct?
[Fe(CN) 6 ]3 + e [Fe(CN) 6 ]4
Fe3+ + e Fe2+
1 [Fe(CN) 6 ]3is more stable than Fe3+
2 [Fe(CN) 6 ]4 is a stronger reducing agent than Fe2+
3 Both [Fe(CN) 6 ]3 and Fe3+ can oxidize MnO 4 2 to MnO 4
Answer: B
[Fe(CN) 6 ]3 + e [Fe(CN) 6 ]4 E = + 0.36V
Fe3+ + e Fe2+ E = + 0.77V
Option 1 is correct.From the reduction potential values, it can be inferred that CN

stabilises the higher oxidation state of Fe (Fe3+) to a greater extent than H 2 O.
Option 2 is correct.The reduction potential of [Fe(CN) 6 ]3 is less positive than that of Fe3+,
hence [Fe(CN) 6 ]3 is a weaker oxidising agent than Fe3+.Thus [Fe(CN) 6 ]4 is a stronger
reducing agent than Fe2+.
Option 3 is incorrect. Reduction potential of MnO 4 /MnO 4 2 is +0.56V, hence the cell
potential for the reaction of [Fe(CN) 6 ]3 and MnO 4 is 0.20V. Since the cell potential is
negative, the reaction is non-spontaneous.
36 Propene is found to react with chlorine in the presence of aqueous sodium bromide and
sodium nitrate. Which of the following are not possible products of the reaction?
1 CH3 CH CH2
Br Br
2 CH3 CH CH2
ONO 2 Cl
3 CH3 CH CH2
Answer: D trendyline
OH
The reaction proceeds

d via
Cl
i electrophilic
l t hili addition,
dditi
iti during
d i which
hi h a carbocation
b intermediate is
1757 trendyline
30
formed.
H H Cl

slow ++
H C C C H + Cl Cl H C C C H
H H H H H H
The carbocation reacts with the different nucleophiles present, giving rise to only these
possible products.
37 Which of the following reactions will not give a good yield of the desired product?
trendyline
1758 trendyline
31
Answer: B
Both reactions 1 and 2 will not give a good yield of the desired product.
Reaction 1 is free radical substitution which can lead to multiple substitution due to the
numerous CH bonds present.
COOH
In reaction 2, COOHwill be formed by the oxidation of the two side chains of the
benzene structure.
38 The three compounds E, F and G have the following structures?
HO
COOCH3
N
N
N
N CH CH2
N
OH O
E F G
Which statements about E, F and G are correct?
1 E and G have the same empirical formula.
2 E and F are isomers
3 The Mr of F is exactly twice that of G
Answer: A
The molecular formua of E is C 12 H 10 N 2 O 2
The molecular formua of G is C 6 H 5 NO
Therefore, the empirical formula of E and G are the same, C 6 H 5 NO
The molecular formua of E is C 12 H 10 N 2 O 2
The molecular formua of F is C 12 H 10 N 2 O 2
Therefore, E and F have the same molecular formula but different structural formula. They
trendyline
rs.
are isomers.
Option 3 iss correct.

cular
ular formua of F iss C 12 H 10 N 2 O 2
The molecular
The molecular
cular
ular formua of G is C 6 H 5 NO
Since F hasas twice the number of atoms of each ea element in G, the M r of F is exactly twice
1759 trendyline
32
that of G.
trendyline
1760 trendyline
33
39 The energy profile for the following reaction is shown below. [D = 2H]
H H

C6H5 C Cl + OH C6H5 C OH + Cl
D D
energy
X
reactants
products
Reaction pathway
Which conclusions can be drawn?
1 The product has no effect on the rotation of plane polarised light.
2 The rate of reaction can be increased by increasing concentration of OH.
3 The structure of the transition state at point X is
C6H5
HO C Cl
H D
Answer: D
The graphs shows 2-steps in the mechanism. Hence, it is S N 1 mechanism.
H H

slow -
C6H5 C Cl C6H5 C+ + Cl
D D
H H
fast
C+ + C6H5 C OH
trendyline
C6H5 OH
D D
The carbocation
cation
ation intermediate formed is planar, allowing OHO to approac
approach from either side
of the plane,
e, forming equimolar amount of both enantiomers. Therefore,
Therefor the product does
Therefore
not displayy any optical activity due to the rotation
tat of polarised light canc
cancelling off each other
1761 trendyline
34
due to being equal but opposite in direction of rotation.
Option 2 is not correct.

From the slow step of the mechanism, rate=k[C 6 H 5 CH(Cl)D]
Therefore, the rate of reaction is independent of [OH].
Option 3 is not correct.
C6H5
HO C Cl
H D
is the transition state from a S N 2 mechanism, and not S N 1.
40 Which groups within an amino acid are able to form a cross-chain link to stabilise the
tertiary structure of a protein?
1 CH 2 CONH 2
2 NH2
H CH2 CH2 CH2 NH C
NH
3 H CH2
N
H
Answer: A
All of the above shown are R groups of -amino acids which are used to stabilise the
tertiary structure of a protein.
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2
Answer all the questions. For

Examiners
Use
1 Planning (P)
The selective partial hydrogenation of alkynes, ZKLFK FRQWDLQ && WULSOH ERQGV, to cis-
alkenes represents an importance class of chemical transformations that have found
extensive uses such as in bioactive molecules, in lubricants as well as in the syntheses of
organic intermediates.
The partial hydrogenation of 5-decyne forms cis-dec-5-ene and the reaction is as shown :
H3C CH3
CH 3 CH 2 CH 2 CH 2 C&CH 2 CH 2 CH 2 CH 3 + H 2 H 1
The enthalpy change for hydrogenation of 5-decyne, H 1 cannot be measured directly in

the laboratory. You are required to plan an experiment to find the enthalpy change for
hydrogenation of 5-decyne, H 1 via Hesss Law.
The enthalpy change for the combustion of hydrogen is286 kJ mol1. 5-decyne and cis-
dec-5-ene are both liquids at standard conditions.
(a) Based on the given information and the equation above, state two enthalpy changes
that are necessary to calculate H 1 .
[1]
(b) Using the information given above and your answer in (a), you are required to write a
plan to determine a value for the enthalpy change for hydrogenation of 5-decyne, H 1 .
You may assume that you are provided with
liquid5-decyne
liquid cis-dec-5-ene
copper calorimeter
two spirit lamps with a 5 cm-wick each
deionised water
a lighter
thermometer
apparatus normally found in a school or college laboratory
Your plan
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n should contain the following:
a diagram
iagram
appropriate
set-up
agram of the experimental set
set--up
opriate quantities of chemicals and solutions
propriate
all essential
ti l experimental
i t l details
d t il
solution
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3
Diagram of the experimental set-up For

Examiners
Use
Procedure:
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[Turn over
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4
For
Examiners
Use

[7]
(c) List the measurements that have to be tabulated and recorded to calculate the value
of enthalpy change for hydrogenation of5-decyne, H 1 .In your answer, you need to
show how these measurements are used to obtain the value ofH 1 .
You may assume the specific heat capacity of water is 4.18 J g1K1 and density of
water is 1g cm3.
Tables used to tabulate and record experimental data:
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5
Treatment of results: For

Examiners
Use
[4]
[Total: 12]
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6
2 Eighty-five percent of all pharmaceutical agents and vitamins involve chlorine chemistry; For
Examiners
many drugs require chlorine, fluorine, or bromine to be effective. Use
Data about thehalides are given below.
Percentage of HX Boiling point Dipole K a ( HOX ) at

pK a
Halide (X) decomposed at of HX / oC moment of 298K
(HX)
2000oC CX/ D
F +3 6 x 105 19.5 1.82
Cl 7 4 x 101 84.2 1.08 2.9 x 108
Br 9 4 67.1 0.82 2.4 x 109
I 10 30 35.1 0.44
(a) Hydrogen halides decompose at high temperature according to the equation:
2HX(g) H 2 (g) + X 2 (g)
Userelevant data from the Data Booklet, explain the trend indicated by
percentagedecomposition of HX.
...
... [3]
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7
(b) The boiling point of HF is higher than the rest of the hydrogen halides despite it being For
Examiners
the smallest molecule. By means of a diagram, indicate the interaction between two Use
molecules of HF that leads to this significant difference.
[2]
(c) When dissolved in water, the hydrogen halides show different pK a values. Write
balanced equations to represent the extent of ionisation of HF and HI in water.
HF : .
HI :
[2]
(d) (i) Draw a diagram to illustrate the shapeof oxoacid, HOCl, indicating clearly the
bond angle.
[2]
(ii) Using the information from the table, state which of the two acids, HOCl or HOBr
is stronger?
. [1]
(iii) Hypoiodous acid has the formula HOI. Predict and explain whether HOI is a
stronger or weaker acid than the acid you identified in (d)(ii).
..
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..

..
..[2]

[Turn over
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8
(iv) Some solid NaOCl solution is dissolved in a solution of HOClat 298 K. The pH of For
Examiners
this mixture is determined to be 6.48. Calculate the ratio of OCl to HOCl in this Use
mixture.
[2]
(e) The halides can react with concentrated sulfuric acid.
(i) When concentrated sulfuric acid was warmed with sodium chloride, white fumes
of hydrogen chloride was evolved. Write a balanced equation for the reaction.
..[1]
(ii) The method described in e(i)cannot be used to prepare hydrogen iodide.

Describe what you would observe when sodium iodide is heated with
concentrated sulfuric acid. Explain the chemistry behind it, and give any relevant
equations.
..
..
..
..
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..

.

[5]
[Total: 20]
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9
3 (a) AlCl 3 is a compound of interest to scientists due to its industrial applications.For For
Examiners
example, AlCl 3 can react with molten aluminium to form AlCl(g). This is a useful Use
procedure as the AlCl formed can be used to recover useful metalloids from their
compounds.
Typically, the reaction has to be carried out in the presence of argon instead of air.
(i) The reaction has to be carried out in an atmosphere of argon. Suggest a reason
for the need of argon.
..[1]
Consider the reaction betweenAlCl 3 (g) and molten aluminium that was carried out at
1573K :
2Al(l) + AlCl 3 (g)3 AlCl(g) reaction 1
In the reaction vessel, 0.200 mol of AlCl 3 (g) was reacted with 0.400 mol of molten Al.
When the reaction system achieved equilibrium with a total pressure of 1.50atm, it
was determined that 0.200 mol of molten Al remained in the vessel.
(ii) Write an expression for the equilibrium constant, K p for reaction 1and hence
calculate its value at 1573K.
[3]

[Turn over
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10
The same reaction vessel was heated to 1700K rapidly in a way suchthat no reaction For
Examiners
took place during the short interval of heating. The reaction system was allowed to re- Use
establish equilibrium. It was found that the partial pressure of AlCl 3 (g) was 0.390 atm
when the equilibrium was re-established.
(iii) Using the information from a(ii), determine the partial pressures of AlCl 3 (g) and
AlCl(g) at the instant when the reaction was heated to 1700K, before the
equilibrium was re-established.You can assume that the gases behave ideally
and the volume of vessel is unchanged.
[2]
(iv) Using the calculated values from a(iii), calculate K p of the reaction at 1700K.
Hence, explain whether reaction 1 is endothermic or exothermic.
trendyline [4]
1771 trendyline
11
(v) The rate equation for reaction between Al and AlCl 3 is shown below. For
Examiners
Use
rate = k[AlCl 3 ][Al]
Suggest which of the two mechanisms shown is a possible mechanism for the
reaction.
Mechanism 1:
Al + AlCl 3 AlCl 2 + AlCl(slow)
Al+AlCl 2 2 AlCl(fast)
Mechanism 2:
AlCl 3 AlCl+ Cl 2 (slow)
2 Al +Cl 2 2 AlCl(fast)
..
..[1]
(b) Anhydrous AlCl 3 is often used as a catalyst in the Friedel-Crafts alkylation of benzene.
AlCl 3
C 6 H 6 + CH 3 CH 2 CH 2 Cl C 6 H 5 CH 2 CH 2 CH 3 + HCl reaction 2
(i) Explain why AlCl 3 can act as a catalyst in Friedel-Crafts alkylation.
...
..[1]
(ii) With the aid of an equation, explain the need to have anhydrous condition when
AlCl 3 is used for reaction 2.
..
..
..[2]
(iii) Use information from theData Booklet, calculate the enthalpy change of reaction
for reaction 2.
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[Turn over
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12
(iv) Describe the mechanism for the formation of C 6 H 5 CH 2 CH 2 CH 3 in reaction 2, For

Examiners
showing clearly the movement of electrons and partial charges. Use
[3]
One key limitation of the alkylation reaction is that a mixture of products tends to form
despite using only one type of halogenoalkane.For primary halogenoalkane, this is
due to the occurrence of a process known as hydride shift which results in
rearrangement of primary carbocation intermediates as shown :
H H H
hydride shift +
CH 3 CH 2 && CH 3 CH 2 &&+

H H H H
(v) Explain why hydride shift occurs for primary halogenoalkane.
..
..
..

..[3]
.
[Total: 22]
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13
4 (a) Cocaine, C 17 H 21 NO 4 , was first used as a local anaesthetic. It is also a powerful For
Examiners
stimulant. Its structure is as shown: Use
O
H3CO C*
O
NCH3
O
cocaine
(i) State the functional groups, other than phenyl ring, present in cocaine.
..[1]
(ii) State the hybridisation of the carbon atom labelled with the asterisk (*).
..[1]
(b) StudentXwas asked to suggest a suitable synthetic route to prepare cocaine from
methylbenzene and compound A.
O
HO C
NCH3
HO
compound A
Student X suggested the following steps:
Methylbenzene is oxidised with hot, acidified KMnO 4 to give

Step 1
benzoic acid.
Benzoic acid is converted into benzoyl chloride by reacting the
Step 2
resultant solution from step 1 with phosphorus pentachloride.
The resultant compound from step 3 is reacted with methanol in the
Step 4
presence of concentrated sulfuric acid at room conditions.
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[Turn over
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14
Explain why steps 2 and 4 of the synthetic route will not work. For
Examiners
Use

..
[2]
(c) Cocaine is sold in its protonated hydrochloride salt, known ascocaine hydrochloride.
Suggest a possible reason for this.
[1]
(d) Smoking cocaine is more stimulating than inhaling the salt as it is absorbed quickly by
the capillaries in the lung tissues. The salt is converted back to cocaine before
smoking.
(i) Suggest a suitable reagent to convert cocaine hydrochloride back into cocaine.
..[1]
(ii) Suggest a suitable solvent to extract cocaineand separate it from its salt.
..[1]
[Total: 7]
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1775 trendyline
15
5 An industrial method for the production of ethanol, C 2 H 5 OH, is outlined in the following flow For
Examiners
diagram. Use
ethene steam
reaction vessel
cooler
ethanol, ethene and water
ethene separatorA
dilute ethanol
separatorB water
concentrated ethanol
(a) (i) Unreacted ethene is removed in separator A. Suggest how the separated
ethene could be used to increase the efficiency of the overall process of the
manufacture of ethanol.
.....
.[1]
(ii) Name the process that takes place in separator B.
.....[1]
trendyline
(b) In the reaction
ction vessel, ethanol is produced in an exothermic
action exoth reaction.
(i) State the reagents and conditions

e th onditions for the industrial
industria preparation
reparation of ethanol from
ethene.
ne.
e.
...[2]

[Turn over
1776 trendyline
16
(ii) If 1.64 kg of ethanol is produced from 10.0 kg of ethene, calculate the percentage For
Examiners
yield of ethanol. Use
[2]
(c) Ethene is used to synthesise N-ethylpropanamide as shown in the following reaction

scheme:
CH 2 CH 2 CH 3 CH 3 CH 3 CH 2 Cl Q R CH 3 CH 2 COCl
step 1step 2
P N-ethylpropanamide
(i) Give the structural formulae of compounds P, Q and R.
Compound P:
Compound Q:
Compound R:
[3]
(ii) State the reagents and conditions for steps 1 and 2.
Step1: ..
Step2: .
trendyline
[2]
[Total: 11]
End of Paper
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2016 j2 h2 Chem Prelim-Updated-Pw

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JC2 Prelim Paper

ANGLO-CHINESE JUNIOR COLLEGE

Paper 1 Multiple Choice

READ THESE INSTRUCTIONS FIRST

Write in soft pencil.

Read the instructions on the Answer Sheet very carefully.

ACJC 2016 9647/01/Prelim/2016 [Turn over

What is the percentage purity of calcium carbonate?

A 27.8 % B 29.8 % C 30.4 % D 35.8 %

2 Use of the Data Booklet is relevant to this question.

3 Use of the Data Booklet is relevant to this question.

Deuterium, 21D, is an isotope of hydrogen.

first compound second compound

5 Which of the following bonds is not present in the following molecule?

A a bond formed by sp3sp2 overlap between two C atoms

A NO2+ < CO32 < SO42

A 18.7 B 74.9 C 93.5 D 149.8

11.1120 11.1 120103

9 Use of the Data Booklet is relevant to this question.

The results obtained are as shown.

positive electrode negative electrode e.m.f. /V

A R > Mg > P > Q

A The yield of the product(s) is greater than 50%.

Which of the following combinations could have given these results?

2NO(g) + 2H2(g) N2(g) + 2H2O(g)

A 1.5 B 4.5 C 6.0 D 9.0

Which of the options in Figure 2 correspond to element Z in Figure 1?

A MgCl2, PCl5, KCl

A Barium sulfate has a higher temperature of decomposition than magnesium sulfate.

17 Which statement about hydrogen halides is incorrect?

A The acidity of hydrogen halides increases down the group.

18 Use of the Data Booklet is relevant to this question.

A Fe(CN)63 does not oxidise I.

19 Aklavinone is a tetracycline antibiotic.

number of chiral centres number of sp2 hybridised number of sp3 hybridised

20 Methylcyclopentane reacts with bromine in the presence of UV light.

Which statement is true about this reaction?

A A possible rate determining step for this reaction is

B There are three possible monosubstituted products.

step 1 step 2 step 3

concentrated HNO3 and

concentrated HNO3 and

concentrated HNO3 and

concentrated HNO3 and

standard enthalpy change

ACJC 2016 9647/01/Prelim/2016 [Turn over

A that it is a better proton donor.

25 Propanone reacts with methylamine to form an imine as shown in the equation.

Similarly, propanone also reacts with hydroxylamine, NH2OH, to form an oxime.

type of reaction structural formula of the oxime

ACJC 2016 9647/01/Prelim/2016 [Turn over

26 Compound A is an example of a prostaglandin, which belongs to a group of physiologically

Which reagent will convert compound A to compound B efficiently?

A NaBH4 B LiAlH4/dry ether

27 Lactic acid, CH3CH(OH)CO2H, is found in sour milk.

A CH3CH(OH)CO2H + CH3OH o CH3CH(OCH3)CO2H + H2O

How many molesoles of NaOH will react with

ACJC 2016 9647/01/Prelim/2016 [Turn over

Which of the following statements about sorbitan monolaurate is correct?

30 Hydrocortisone is a steroid hormone produced by the adrenal gland and is released in

Which of the following statements about hydrocortisone is correct?

A When treated with an excess of hot concentrated acidified KMnO 4, it forms a

ACJC 2016 9647/01/Prelim/2016 [Turn over