Winter 1997 CH3 Mark Scheme

1
1. (a) The standard reduction potential for the MnO
4

|Mn
2+
electrode is given by
MnO
4

(aq) + 8H
+
(aq) + 5e

Mn
2+
(aq) + 4H
2
O(1) E = + 1.51 V
why is a reference electrode necessary to measure E ?
potential of single electrode cant be measured/
second electrode has a potential/
second electrode needed (1)|
have to measure potential difference (1)
need a source or sink of electrons (1) (max 2)
(2)
(b) The standard reduction potential for the Cl
2
|Cl

electrode is given by
Cl
2
(g) + e

Cl

(aq) E = 1.36 V
(i) Combine this half equation with the one in (a) to give the reaction of
manganate(VII) ions with chloride ions.
MnO
4

+ 8H
+
+ 5e

Mn
2+
+ 4H
2
O
5Cl

5/2CI
2
+ 5e

(1) for correct multiplication
MnO
4

+ 5CI

+ 8H
+
Mn
2+
+ 5/2CI
2
+ 4H
2
O (1) or doubled
if the final equation is given with no working then (2)
if the equation is the wrong way round but everything else is
correct then (1) only)
(2)
(ii) State, giving a reason whether you would expect this reaction to occur under
standard conditions.
E = 1.51 1.36 V = 0.15 V (1) or cell potential is positive
(some valid comparison of the 2 E values required)
E > 0 so reaction feasible (1)
a clear statement that the cell has a positive potential is required
the 2nd mark is consequential on the 1st ie if E
cell
is ve then no reaction or
equilibrium far to the left should be given for (max 1)
if no restriction because E<0.3V given then (max 1)
(2)
(iii) Given that
MnO
2
(s) + 4H
+
(aq) + 2e

Mn
2+
(aq) + 2H
2
O(1) E = + 1.23V
comment on the fact that the reaction of MnO
2
with hot concentrated HCI is a
standard laboratory method for the preparation of chlorine.
E = 1.23 1.36 V = .0.3V not possible (1)
some quantitative evidence is needed but calculation not necessary
reaction conds. are not standard (1)
eg conc HCl / or temperature/concentration of CI

ions/removal of CI
2

(. E > 1.23) (1)
(3)
(Total 9 marks)

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Winter 1997 CH3 Mark Scheme
2

2. (a) The following table shows some physical properties of two s-block metals.
Metal
caesium
barium
Hardness
very soft
quite hard
1.9
3.51
Density/g cm
3
Melting
temperature/C
28.7
714

(i) Suggest reasons for the differences in the physical properties of caesium and
barium as shown in the table. The metals have the same crystal structure.
comment on size or charge or number of electrons being used (1)
comment on forces between atom / strength of metallic bonding (1)
relate the above to hardness or m.p. or density (1)
(3)
(ii) Caesium gets its name from the blue colour it or its salts impart to a Bunsen flame.
What process within the atom is responsible for the emission of this colour?
electron transition from high/excited to low/ground energy level (1)
electron transition only ()
(1)
(iii) If the light emitted from excited caesium atoms is passed through a spectrometer,
what would you expect to see?
line (spectrum) (1) not band
(1)
(b) Sodium burns in excess oxygen to give a yellow solid. Y.
(i) Y contains 58.97% sodium. Find its empirical formula.
Na Na
58 97
23
41 03
16
2 56 2 56
0 1 0
. . . .
( ) =

= NaO (1) consequential on working above
just the answer (1) only
if the reverse method is used and correct this is acceptable (i.e. start
assuming NaO)
(2)
(ii) The relative molecular mass of Y is 78. what is its molecular formula?
Na
2
O
2
(1)
(1)
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Winter 1997 CH3 Mark Scheme
3

(iii) If Y is reacted with ice-cold dilute sulphuric acid, a solution of Z is obtained which
will react with potassium manganate(VII) solution. Describe the experimental
procedure you would use to determine the mole ratio in which Z and potassium
manganate(VII) react together.
known mass of Y () + H
2
SO
4
known volume ()
pipette known volume / transfer an aliquot () into conical flask
titrate / comment on use of burette () with standard () KMn
0
4
solution
to first permanent pink () colour
or
known mass of Y () and use of all of it (1)
titrate () with standard () KMnO
4

to permanent pink colour ()
(3)
(Total 11 marks)

3. The following table shows some physical properties of two s-block metals.
Metal
caesium
barium
Hardness
very soft
quite hard
1.9
3.51
Density/g cm
3
Melting
temperature/C
28.7
714

(a) Suggest reasons for the differences in the physical properties of caesium and barium as
shown in the table. The metals have the same crystal structure.
comment on size or charge or number of electrons being used (1)
comment on forces between atom / strength of metallic bonding (1)
relate the above to hardness or m.p. or density (1)
(3)
(b) Caesium gets its name from the blue colour it or its salts impart to a Bunsen flame. What
process within the atom is responsible for the emission of this colour?
electron transition from high/excited to low/ground energy level (1)
electron transition only ()
(1)
(c) If the light emitted from excited caesium atoms is passed through a spectrometer, what
would you expect to see?
line (spectrum) (1) not band
(1)
(Total 5 marks)

4. Sodium burns in excess oxygen to give a yellow solid. Y.
(a) Y contains 58.97% sodium. Find its empirical formula.
Na Na
58 97
23
41 03
16
2 56 2 56
0 1 0
. . . .
( ) =

= NaO (1) consequential on working above
just the answer (1) only
if the reverse method is used and correct this is acceptable (i.e. start
assuming NaO)
(2)
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Winter 1997 CH3 Mark Scheme
4

(b) The relative molecular mass of Y is 78. what is its molecular formula?
Na
2
O
2
(1)
(1)
(c) If Y is reacted with ice-cold dilute sulphuric acid, a solution of Z is obtained which will
react with potassium manganate(VII) solution. Describe the experimental procedure you
would use to determine the mole ratio in which Z and potassium manganate(VII)
react together.
known mass of Y () + H
2
SO
4
known volume ()
pipette known volume / transfer an aliquot () into conical flask
titrate / comment on use of burette () with standard () KMn
0
4
solution
to first permanent pink () colour
or
known mass of Y () and use of all of it (1)
titrate () with standard () KmnO
4

to permanent pink colour ()
(3)
(Total 6 marks)


5. (a) Electrolysis of brine under different conditions gives sodium chlorate(I); in this case the
sodium hydroxide and chlorine are allowed to mix t room temperature.
(i) Give the ionic equation for the reaction of chlorine with cold dilute aqueous sodium
hydroxide.
Cl
2
+ 2OH

OCl

+ Cl

+ H
2
0 (1) ignore Na
+
on either side
if ionic equation not given (0)
(1)
(ii) If the solution of sodium chlorate(I) is heated, the chlorate(I) ion disproprortionates.
Write the ionic equation for the reaction, and use it to explain the meaning of
disproportionation.
3OCl

2 Cl

+ Cl0
3

(1) include oxidation states of products (1)
same species both oxidised and reduced (1)
(3)
(b) Give one use for
any suitable specific uses
water sterilisation / manufacture of polymers / PVC / bleach
(1)
(c) Suggest how using a solution of sodium chlorate(I), or otherwise, you could distinguish
between separate aqueous solutions of potassium bromide and potassium iodide.
acidify or use of chlorine (1)
shake with immiscible organic solvent/hexane/CCl
4
(1)
brown colour shows Br

(1)
purple colour shows I

(1)
OR
equivalent using AgNO
3
() to solution of each or AgNO
3
drop by drop (1)
cream ppt from Br

() yellow ppt from I

()
add (conc) NH
3
(1)
AgBr dissolves () AgI insoluble ()
(4)
(Total 9 marks)

6. Electrolysis of brine under different conditions gives sodium chlorate(I); in this case the sodium
hydroxide and chlorine are allowed to mix t room temperature.
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5
(a) Give the ionic equation for the reaction of chlorine with cold dilute aqueous sodium
hydroxide.
Cl
2
+ 2OH

OCl

+ Cl

+ H
2
O (1) ignore Na
+
on either side
if ionic equation not given (0)
(1)
(b) If the solution of sodium chlorate(I) is heated, the chlorate(I) ion disproprortionates.
Write the ionic equation for the reaction, and use it to explain the meaning of
disproportionation.
3OCl

2 Cl

+ ClO
3

(1) include oxidation states of products (1)
same species both oxidised and reduced (1)
(3)
(Total 4 marks)

7. Suggest how using a solution of sodium chlorate(I), or otherwise, you could distinguish between
separate aqueous solutions of potassium bromide and potassium iodide.
acidify or use of chlorine (1)
shake with immiscible organic solvent/hexane/CCl
4
(1)
brown colour shows Br

(1)
purple colour shows I

(1)
OR
equivalent using AgNO
3
() to solution of each or AgNO
3
drop by drop (1)
cream ppt from Br

() yellow ppt from I

()
add (conc) NH
3
(1)
AgBr dissolves () AgI insoluble ()
(Total 4 marks)

8. The equilibrium reaction
3Fe(s) + 4H
2
O(g) Fe
3
O
4
(s) + 4H
2
(g)
was at one time used to make hydrogen; the tri-iron tetroxide was returned to the blast furnace to
be converted back to iron.
(a) Write the expression for K
p
for this reaction.
K
p H
p H
p
=
( )
( )
( )
2
4
2
4
0
1

( ) not essential e.g. ppH
2
4
acceptable
If square brackets used then (0)
if the 4s are cancelled then (0)
(1)
(b) Bauxite is an ore of aluminium; it consists of aluminium oxide with impurity mostly of
iron(III) oxide.
(i) Bauxite is first converted to pure aluminium oxide. Outline the chemical basis for
this purification.
react with hot aqueous (1) NaOH (1) not OH

ions
Al
2
O
3
soluble () since amphoteric () or forms AlO
2

impurities are not so dont dissolve (1) or are filtered off
blow in CO
2
or seed (1)
(5)
(ii) Give a labelled sketch of the electrolytic cell in which the aluminium is produced
from purified bauxite.
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molten
cryolite +
Al O
(1)
(1)
carbon anode (1)
cathode (1)
Al molten (1)
2 3

or Al
2
O
3
dissolved in cryolite to lower m.p. (2)
if just molten Al
2
O
3
+
(1) only
if cathode and anode labelled incorrectly but +ve and ve labelled correctly
then (1) out of (2) for the electrode marks same for the reverse of this
(5)
(Total 11 marks)

9. The equilibrium reaction
3Fe(s) + 4H
2
O(g) Fe
3
O
4
(s) + 4H
2
(g)
was at one time used to make hydrogen; the tri-iron tetroxide was returned to the blast furnace to
be converted back to iron.
Write the expression for K
p
for this reaction.
K
p H
p H
p
=
( )
( )
( )
2
4
2
4
0
1

( ) not essential e.g. ppH
2
4
acceptable
If square brackets used then (0)
if the 4s are cancelled then (0)
((Total 1 mark)

10. Bauxite is an ore of aluminium; it consists of aluminium oxide with impurity mostly of iron(III)
oxide.
(a) Bauxite is first converted to pure aluminium oxide. Outline the chemical basis for this
purification.
react with hot aqueous (1) NaOH (1) not OH

ions
A1
2
O
3
soluble () since amphoteric () or forms A1O
2

impurities are not so dont dissolve (1) or are filtered off
blow in CO
2
or seed (1)
(5)
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Winter 1997 CH3 Mark Scheme
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(b) Give a labelled sketch of the electrolytic cell in which the aluminium is produced from
purified bauxite.

molten
cryolite +
Al O
(1)
(1)
carbon anode (1)
cathode (1)
Al molten (1)
2 3

or A1
2
O
3
dissolved in cryolite to lower m.p. (2)
if just molten A1
2
O
3
+
(1) only
if cathode and anode labelled incorrectly but +ve and ve labelled correctly
then (1) out of (2) for the electrode marks same for the reverse of this
(5)
(Total 10 marks)


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