6.

(a)

Consider the following reaction.

H2O (g)

C (s)

H2 (g)

+ CO(g )

H = + 130KJmol-1

(i)

Write an expression of Kp for the reaction.

(ii)

State and explain how the amount of carbon monoxide and the value of Kp
will change (if any) if the temperature is increased.

[4]
(b)

(i)

Define buffer solution.

(ii)

Give one example where the control of pH is important.

[3]
(c)

(i)

A mixture of aqueous ammonia, NH3 and aqueous ammonium chloride

forms a buffer solution. Using suitable equations explain how the buffer
solution functions.

(ii)

Derive an expression for solubility, Ksp of barium hydroxide.

[8]

PCO PH

6 (a) (i)

PH

2O

Kp =
[NOTE: In a heterogenous system,the partial pressure of solid is not
included in the expression for Kp]
(ii)
The forward reaction is endothermic.
When the temperature is increased, the position of equilibrium will shift to
the right to absorb the heat supplied.
Hence, the amount of carbon monoxide and the value of Kp increase.

(b) (i)
(ii)

(c) (i)

1
1
1
4

Buffer solution is a solution whose pH remains almost unchanged when a

small amount of acid or alkali is added to it.

HCO3 - / CO3 2- is the buffer system in human blood and maintains the pH at
around 7.4.
A fluctuation of + 0.4 unit can be fatal.
This fluctuation can be brought about during illness or when taking drugs or
when given injections that are either alkaline or acidic in nature.

Ammonia dissociates partially in water:

NH3 + H2O
NH4+ +

OH- (1)

1
3

Ammonium chloride dissociated completely in water:

NH4Cl
NH4+
+
Cl-

In the presence of ammonium chloride , the equilibrium (1) above will be

displaced towards the left-hand side (due to the presence of the common
NH4+ ion).
Hence ,a mixture of aqueous ammonia and ammonium chloride contains a
large amount of undissociated NH3 molecules and the NH4+ ions.
When a small amount of acid is added to the mixture, the H + added will
react with the NH3 molecules to form NH4+ ions:
NH3 + H+ (added) NH4+
When a small amount of base is added,the OH- will react with the NH4+ ions
to form undissociated NH3 molecules:
OH- (added) + NH4+ NH3 + H2O
In both cases,the H+ or OH- added is removed. Therefore, the pH of the
solution remains unchanged.

1
1

1
1
1
9

Ba(OH)2(s)
Ba2+ (aq) + 2OH-(aq)
Ksp = [Ba2+][OH-]2

Total

1.

15 m

In the Contact Process for the production of sulphuric acid, highly purified sulphur dioxide and
oxygen react together to form sulphur trioxide. The process is carried out in the presence of
vanadium(V) oxide at about 700K and at a pressure of 120kPa

2SO2(g) + O2(g)
Under these conditions, the partial pressures of sulphur dioxide and sulphur trioxide at
equilibrium are 33kPa and 39 kPa, respectively.
(a)

Determine

2SO3(g)

(i)
the partial pressure
(ii) the mole fraction
of oxygen in the equilibrium mixture.
(i)

(ii)

[3]
(b)

(i)

Write an expression for the equilibrium constant, Kp, for the reaction.

__________________________________________________________________
_
(ii)

Calculate the value of the equilibrium constant, Kp, and state its unit.

[3]
(c)

What would be the effect on the production of SO3 if

(i)
no vanadium(V) oxide is used
__________________________________________________________________
_
__________________________________________________________________
_
__________________________________________________________________
_
(ii)

inert gas is added at constant pressure.

__________________________________________________________________

_
__________________________________________________________________
_
__________________________________________________________________
_

[4]
Question

Answer

Mark

1(a)(i)

P(O2) = 120 kPa - 33 kPa - 39 kPa = 48 kPa

1 mark

(a)(ii)

x(O2) = P(O2) / PT
= 48 / 120
= 0.4

1 mark

(b)(i)

Kp = P(SO3)2 / P(SO2)2 P(O2)

1 mark

(b)(ii)

Kp = (39 kPa)2 / (33 kPa)2 (48 kPa)

= 0.029 kPa-1

1 mark
1 mark

(c)(i)

Yield of SO3 is unchanged.

1 mark

Rates of both forward and backward reactions are very slow.

1 mark

Addition of inert gas reduces the total pressure on the equilibrium mixture.

1 mark

Equilibrium shifts to the left, yield of SO3 is reduced.

1 mark

(c)(ii)

5.

(a)

1 mark

Using suitable examples, explain the terms Arrhenius acids and Bronsted-Lowry acids.
[4]

(b) Ethanoic acid dissociates in water:

CH3COOH

H 2O

CH3COO-

H2O+

Write the expression for the Ka for ethanoic acid. What is the relationship between Ka and
pKa?
[2]
(c)

A buffer solution was prepared by dissolving 0.15 mole of sodium ethanoate in 1 dm3 of
0.10 mol dm-3 ethanoic acid. (pKa = 4.74)
(i)
(ii)
(iii)

Question
5(a)

Define buffer solution.

Calculate the pH of the buffer solution above.
Calculate the change in pH when 1.0 cm3 of 1.0 mol dm-3 hydrochloric acid is added
to 100 cm3 of the buffer solution.
[9]
Answer

Mark

Arrhenius acids are compounds that dissociate to give H+ ions when

dissolved in water.
HCl (aq) H+ (aq) + Cl- (aq)

1 mark

Bronsted-Lowry acids are proton acceptors.

1 mark

1 mark

1 mark
HNO3 + H2O H3O+ + NO3-

Ka

5(b)

[CH 3 COO ][H ]

1 mark

[CH 3 COOH]

1 mark

pKa = - log Ka
5(c )(i)
5(c)(ii)

A buffer solution is a solution of which the pH does not change significantly

on the addition of a little acid or base.

4.74 log

1 mark
1 mark

0.1
0.15

1 mark

pH =
= 4.92
5(c )(iii)

1
1000

No. of moles of H+ added =

= 1 x 10-3 mol.

1 mark

No of moles of CH3COOH in 100 cm3 = 0.01 mol

OR
No of moles of CH3COO - in 100 cm3 = 0.015.

1 mark

[ CH3COO -] +
Initial /mol
Final/mol

0.015
0.015 - 0.001

0.011

[H+ ]
0.001
0

[ CH3COOH]
0.01
0.01+ 0.001

1000
101

[ CH3COOH]final =
OR

1 mark
-3

= 0.1089 moldm .

0.014
[ CH3COO -]final =

1000
101

1 mark

= 0.1386 moldm-3 .

1 mark

0.1089
0.1386

1 mark

Final pH = 4.74 log

= 4.84
hence, change in pH = 4.92 - 4.84
= 0.08
Total

15 marks

(b)

Sucrose has been used as a feedstock in the production of alcohol for use as a motor fuel.
The initial reaction is hydrolysis catalysed by dilute hydrochloric acid.
C12H22O11 +

C6H12O6 + C6H12O6

H2O

sucrose

glucose

fructose

The following result were obtained :

Experiment
I
II
III
(i)
(ii)
(iii)
(iv)

Initial [HCl]
/mol dm-3
0.10
0.10
0.20

Initial [sucrose]
/mol dm-3
0.10
0.15
0.10

Initial rate
/mol dm-3
0.024
0.036
0.048

Deduce the order of reaction with respect to both HCl and sucrose.
Write the initial rate equation and calculate the rate constant for the reaction.
Determine the half-life of sucrose.
Explain how dilute HCl increases the initial rate of hydrolysis of sucrose.
[9]

5(b)(i)

Rate = k [HCl]m[sucrose]n

1m

m
n
0.36 k[0.10] [0.15]

0.024 k[0.10] m [0.10] n

(1 + 1) m

n=1

m=1

1m

0.48 k[0.20] [0.10]

0.024 k[0.10] m [0.10] n

5(b)(ii)

Rate = k [HCl][sucrose]

k =

0.048
0.20 0.10

1m
1m
-1

= 2.4 mol dm

5(b)(iii)
(1 + 1) m

ln 2
k
t1/2 =
5(b)(iv)

6.

(a)

t1/2 = 0.29 s
HCl reduces the Ea of the reaction
more molecules achieve energy Ea
or
more number / higher frequency of effective collisions

1m
1m

What do you understand by the Bronsted-Lowry theory of acids and bases?

[2]

(b)

For each of the following reactions C and D

(i)
identify the two acids and the two bases present;

(ii)

suggest with reasons, which ion or molecule is the stronger acid and which the
stronger base.

NH3 +

H2O

NH4

HO

Kc = 1.8 10-5mol dm-3

C6H5O-

C6H5OH + CH3COO-

CH3COOH

Kc=1.3 106 mol dm-3

[5]
(c)

(i)
(ii)

Define the pH,

Calculate the pH of 1 10-3 mol dm-3 of hydrochloric acid and 1 10-3mol dm-3 of
calcium hydroxide
[4]
(d) An iron (III) salt was added to a solution of HA with pH5, so as to make a solution of
0.01 mol dm-3 with respect to Fe 3+ ion.
(i)
Calculate the minimum concentration of OH- ions required to cause precipitation of
iron (III) hydroxide from 0.01 mol dm-3 solution of Fe3+ ion.
[The solubility product of iron(III) hydroxide at the temperature of experiment is 8
10-38 mol4 dm-12. Ionic product of water Kw= 1 10-14mol2dm-6]
(ii)

Hence determine whether iron (III) hydroxide precipitate formed in the experiment
describe above.

[9]
6(a)
6(b)(i)

Acids are proton donors and bases are proton acceptors

C:

1m

acids - H2O and NH4+

Bases NH3 and OH-

D: acids CH3CO2H and C6H5OH

Bases- C6H5O- and CH3CO26(b)(ii)

The position of equilibrium lies more to the left since K c is small.

There are greater proportions of NH3 and H2O compared to NH4+ and OH- .
Hence, NH4+ is a stronger acid than H2O and OH- is a stronger base than NH3.
The position of equilibrium lies more to the right since the K c is large. There are
greater proportions of C6H5OH and CH3CO2- compared to C6H5O- and CH3CO2H
Hence CH3CO2H is a stronger acid than C6H5OH and C6H5O- is a stronger base
than CH3CO2-.

6(c)(i)

6(c)(ii)

pH of a solution is represented by the log of the hydrogen concentration in mol dm 3

or
pH = - log 10[H+]

1m

(1 + 1) m

(1 + 1) m

1m

pH = -log 10-3 = 3

Ca(OH)2

Ca2+ +

[OH-] = 2 10-3 mol dm-3

pH = 14 + log [ 2 10 -3]
= 14 2.7
= 11.3
6(d)(i)

(1 + 1) m

Ksp = [ Fe3+] [OH-]3

2OH-

(1 + 1) m

= 8 10-38
[OH-]3 = 8 10-38
0.01
[OH ] = 2 10-22 mol dm-3
6(d)(ii)

(1 + 1) m

pH = 5 means [H+] = 10-5 mol dm-3

[OH-] = 10-9 mol dm-3 > 2 10-22 mol dm-3
Therefore a precipitate of iron (III) hydroxide should be formed

(1 + 1) m
Total

5Acidity regulators are food additives that have a buffering action on the pH of foodstuffs. Mixtures
of citric acid and its sodium salt are often used for this purpose.
C5H7O5CO2H

C5H7O5CO2- + H+

Ka = 7.4 x 10-4 moldm-3 citric acid

(a) The concentration of citric acid in lemon juice is 0.22 moldm-3. Assuming that no other acid
is present, calculate the pH of lemon juice.
[7]
(b) Write equations to show how the citric acid/ sodium citrate buffer system
regulates the acidity on the addition of
(i)
(ii)

H+ ions,
OH- ions
[2]

(c) Calculate the pH of a solution containing 0.10 mol dm-3 citric acid and 0.30 mol dm-3 sodium
citrate.
[2]
(d) Define the term Kw and explain why , at 25O C, water has a pH of 7
[4]

QUESTION
5 (a)

ANSWER
C5H7O4CO2H
Initial conc/moldm-3
Eq. conc/moldm-3

MARK

C5H7O4CO2- + H+
:
:

0.22
0.22 x

[C 5 H 7 O 4 CO 2 ][ H ]
[C 5 H 7 O 4 CO 2 H]

0
x

0
x

1m

1m

Ka =
1m

15 m

( x )( x )
(0.22 x )
7.4 x 10

-4

1m

=
1m

Assuming x << 0.22 , 0.22 x 0.22 (since Ka is small )

1m

x2
0.22
7.4 x 10-4 =

1m

x = 1.28 10 -2 moldm-3.
pH = - log [ H +]
= - log (1.28 10 -2 )
= 1.89
5 (b)

C5H7O4CO2-

+ H+ C5H7O4CO2H

1m
1m

C5H7O4CO2H + OH- C5H7O4CO2- + H2O

5 (c)

[salt ]
[acid ]
pH = pKa + log
1m

(0.30)
(0.10)

1m

= - log ( 7.4 10 -4 ) + log

= 3.61
5 (d)

Consider the self ionization of water

H2O H+ + OH+

1m

Kw = [ H ][ OH ]

1m

At 25 oC , Kw = 1 10 -14 mol2dm-6.
For every 1 H+ ion formed,1 OH- is also formed. Therefore, [ H+ ] = [ OH- ]
[ H+ ] 2 = 1 10 -14 mol2dm-6.
[ H+ ] = 1 10 -7 moldm-3.
pH

1m

= - log [ H +]
= - log (1 10 -7 )

1m

= 7
Jumlah

15 m

(c) One reaction which occurs in air polluted with nitrogen oxides is shown below.
2NO (g) + O2 (g) 2NO2 (g)
Five experiments were carried out to find the relationship between the initial concentration
of NO and of O2 and the initial rate of formation of NO2.
Initial concentrations/moldm-3
Experimen
t
1
2
3
4
5

[NO]
0.001
0.001
0.001
0.002
0.003

[O2]
0.001
0.002
0.003
0.003
0.003

Initial rate of
formation of NO2
/ moldm-3
7 x 10-6
14 x 10-6
21 x 10-6
84 x 10-6
189 x 10-6

What is the order of the reaction with respect to each of the reactants?
(i)
(ii)

NO
O2
[4]

(d) What equation for the rate determining step does this suggest?
[1]
(e) Le Chateliers principle predicts that the highest equilibrium yield of ammonia in the Haber
process,
N2 (g) + 3H2 (g)

2NH3 (g)

H = - 92 kJmol-1,

should occur at a high pressure and at a low temperature. In practice, however, these
conditions are not used.
(i)

What are the typical values of pressure and temperature used industrially, and what
factor other than Le Chateliers principle effect this choice?
[3]

(ii)

Why are the gases passed through a tower packed with lumps of iron?
[2]

8 (b)
8 (c)(i)

3NO2 (g) + H2O (l) 2HNO3 + NO (g)

Comparing experiments 4 and 3, where concentration of O2 is kept constant
n
0.002
=
84 x 10-6 .
0.001
21 x 10-6
2n
n

8 (c)(ii)

=
=

4
2

second order

Comparing experiments 2 and 1, where concentration of NO is kept

constant
n

1m

1m

1m

0.002
0.001
2n
n

14 x 10-6 .
7 x 10-6

=
=
=

2
1

1m

first order

1m

2NO (g) + O2 (g) 2NO2 (g)

8 (d )

1m

8 (e)(i)

- 450oC , 200 atm

- Rate of reaction

8 (e)(ii)

Iron serves as a catalyst.

It helps to establish the equilibrium faster.

(1+1) m
1m
1m
1m

7 (a) The following data were collected for the reaction between hydrogen and nitric oxide at
700 oC:
2H2(g) + 2NO(g)
2H2O(g) + N2(g)
Experiment

[H2]/mol dm-3

[NO]/ mol dm-3

0.010

0.025

0.0050

0.025

0.010

0.0125

Initial rate/mol dm-3s-1

2.4
1.2
0.60

(i)
(ii)
(iii)
(b)

10-6
10-6
10-6

Calculate the order of reaction with respect to H2 and NO.

Write the rate equation for the reaction.
Suggest a plausible mechanism that is consistent with the rate equation.
(Assume that the oxygen atom is the intermediate).

[6]
The Haber process for the preparation of ammonia is based on the following equilibrium.

N2(g) +
(i)

2NH3(g)

H = negative

How the position of equilibrium is change by increasing the temperature and

pressure.

(ii)

3H2(g)

The value of equilibrium constant, Kp for the above equilibrium at 550 oC is 1.5
-5
10 , what pressure must be applied to a mixture of nitrogen and hydrogen in molar ratio of 1:3 at 550
o
C so as to convert 50% of the mixture into ammonia at equilibrium? (All pressures are measured in
atm.)
[9]

7(a)(i)

Consider exp. 1 & 2,

2.4 10 6
1.2 10 6

0.010

0.0050

2n

2
=
n
= 1
The order of reaction with respect to H2 is first order.

Consider exp. 3 & 1,

0.60 10 6
2.4 10 6

0.0125

0.010

0 .5 n
0.25
=
n
=
2
The order of reaction with respect to NO is second order
7(a)(ii)

7(a)(iii)

7(b)(i)

7(b)(ii)

Rate = k[H2] [NO]2

slow
2NO
N2
fast
O + H2
H2O
H2

H2O

1
1

When the temperature is increased, the position of equilibrium would shift

to the left to absorb heat.

This is because the forward reaction is exothermic

When the pressure is increased, the position of equilibrium would shift

forward to reduce the number of molecules.

This is because the production of ammonia is accompanied by a decrease in

number of molecules.

1
1
1
1

For an aqueous solution of 0.20 mol dm-3 HX, which is 1% dissociated, calculate
(i)
the pH of solution,

(a)

______________________________________________________________
______________________________________________________________
[1]
(ii)

Ka of the acid.
______________________________________________________________
______________________________________________________________

[2]
(b) The following diagram shows the vapour pressure-molar composition curve for mixture of N2 + 3H2
propanone and trichloromethane at constant temperature.
Vapour
pressure

(i)

0.7
CH3Cl
Molar composition

Explain why the curve has the shape shown above?

________________________________________________________________
________________________________________________________________
________________________________________________________________
[2]

(ii)

What is the form of interaction between the molecules of the two substances?
________________________________________________________________
________________________________________________________________
[1]

(iii)

By using the axes below, draw boiling point-molar composition curves of the mixture
of the two liquids above.

Boiling
point

(iv)

CH3Cl
Molar composition

[1]
When these two liquids with the same molar quantities, and at the same temperature,
are mixed, how does the temperature change? Suggest a reason for your answer.
___________________________________________________________________
___________________________________________________________________

(v)

___________________________________________________________________
[2]
Draw on the axes below, the change in the vapour pressure with molar composition that
you would expect to be shown by a mixture of tetrafluoromethane(CF 4) and
tetrachloromethane (CCl4).
Vapour
pressure

CF4
Molar composition

1
[1]

2(a)(i)

[H+] = c = 0.20 0.01 = 0.002 mol dm-3

pH = log[H+]
pH = 2.70

2(a)(ii)
Ka

c 2
1

= 2.02
2(b)(i)

2(b)(ii)
2(b)(iii)

0.2 0.01
1 0.01

or =

10

1
or
1

1
1

mol dm -3

Stronger attractive forces between the propanone-trichloromethane

molecules than those existing in the respective pure liquids.

The molecules in the solution have less tendency to escape into the vapour
phase.

Hydrogen bonding

Boiling
point

1
vapour

vapour
liquid

2(b)(iv)

2(b)(v)

liquid

0.7
CH3Cl
Molar composition

The temperature of the mixture increases.

The intermolecular attractive forces formed in the mixture is stronger than

the intermolecular attractive forces broken in the component liquids.

Vapour
pressure

CF4
Molar composition

TOTAL

10