GKL/N06/P3/solutions

- 1 -
GCE A Level Chemistry November 2006
Paper 3 Answers

1 (a) Analysis: Note all the state symbols. They are the keys to which are the competing species
for cathode and anode. Note also that this is an electrolytic cell. Thus, all the reactions are
feasible. You just need to predict the products formed at anode and cathode.

(i) NaBr (l) Cathode: Na
+
Anode: Br

Cathode (Reduction): Na
+
+ e Na
Anode (Oxidation) : 2Br

Br
2
+ 2e

At the cathode, sodium metal is produced. At the anode, bromine gas is produced.

(ii) NaBr (aq) Cathode: Na
+
, H
2
O Anode: Br

, H
2
O

From Data Booklet,
Na
+
+ e Na E
u
= -2.71V
2H
2
O + 2e H
2
+ 2OH

E
u
= -0.83V
E
u
H2O/H2
is less negative than E
u
Na+/Na
, thus H
2
O undergoes reduction preferentially.

Br
2
+ 2e 2Br

E
u
= +1.07V
O
2
+ 4H
+
+ 4e 2H
2
O E
u
= +1.23V
E
u
Br2/Br-
is less positive than E
u
O2/H2O
, thus Br

undergoes oxidation preferentially.

Cathode (Reduction): 2H
2
O + 2e H
2
+ 2OH

Anode (Oxidation) : 2Br

Br
2
+ 2e

At the cathode, hydrogen gas is produced. At the anode, bromine gas is produced.

(iii) CuF
2
(aq) Cathode: Cu
2+
, H
2
O Anode: F

, H
2
O

From Data Booklet,
Cu
2+
+ 2e Cu E
u
= +0.34V
2H
2
O + 2e H
2
+ 2OH

E
u
= -0.83V
E
u
Cu2+/Cu
is more positive than E
u
H2O/H2
, thus Cu
2+
undergoes reduction preferentially.

F
2
+ 2e 2F

E
u
= +2.87V
O
2
+ 4H
+
+ 4e 2H
2
O E
u
= +1.23V
E
u
O2/H2O
is less positive than E
u
F2/F
, thus H
2
O undergoes oxidation preferentially.

Cathode (Reduction): Cu
2+
+ 2e Cu
Anode (Oxidation) : 2H
2
O O
2
+ 4H
+
+ 4e

At the cathode, copper metal is produced. At the anode, oxygen gas is produced.
GKL/N06/P3/solutions
- 2 -
(b) Analysis: A undergoes oxidation to give a triatomic gas which has 3 atoms in a gaseous
molecule. I have pressure, volume and temperature I can use PV = nRT.
KF (aq) + HF(aq) Cathode: K
+
, H
+
, H
2
O Anode: F

, H
2
O
(i)
0 . 54
)
1000
00 . 1
)( 10 90 . 3 (
) 282 )( 31 . 8 )( 900 . 0 (

) 282 )( 31 . 8 (
900 . 0
)
1000
00 . 1
)( 10 90 . 3 (
4
4
=

=
=
=
=
Mr
Mr
RT
Mr
m
PV
nRT PV


(ii) Molecular Formula : F
2
O
Shape: bent or V-shaped
O
F F



2 (a) Analysis: Readily react with electron pair donors remind you that B atom of BX
3
is
electron deficient.

(i) Description of shape: BF
3
is trigonal planar in shape.
F B
F
F

Explanation: B atom has three bonded pairs and no lone pairs. Therefore, to minimise
repulsion between the bonded pairs, BF
3
takes the shape of trigonal planar.

(ii)
B N
F
F
F
CH
3
CH
3
CH
3

Explanation: B atom and N atom each has 3 covalent bonds to F atoms and CH
3
alkyl
groups respectively. Since B atom requires 2 electrons to form an octet while N atom has
a lone-pair of electrons, they form a dative bond with N atom donating electrons to B.

(b)(i) Relative atomic mass of an element is the average mass of one atom of the element
compared to 1/12 the mass of one atom of
12
C.



Comments:
Note all the units when using
PV=nRT

Mr has no units; Molar mass has
units of gmol
1

Comments: Answer is not F
3
or O
3
as their Mr deviates
from 54. Since species at anode are F

and H
2
O. H
2
O
preferentially oxidised to give O
2
gas. It is not difficult to
relate the triatomic gas with O and F atoms.
Comments: Dont miss out the
explanation
Comments: Note the direction of dative bond.
Remember to draw in the lone-pair.
GKL/N06/P3/solutions
- 3 -
3 Either
(a)
Analysis: You must show rates of reaction. Thus, you must draw rate of reactions against
time graph.


(b)(i)
2
2
) )( (
) (
4 2
3 2
NO O N
O N
p
P P
P
K = units: atm
1


(b)(ii) From the data given, substitute in the partial pressures of the gases at equilibrium.

1
2
2
0370 . 0
) 50 . 1 )( 75 . 0 (
) 25 . 0 (

= = atm K
p


(c)(i) When temperature is increased, position of equilibrium will shift to the left. This is because
by Le Chateliers Principle, the reverse reaction is favoured as it is endothermic and will
absorb the additional heat.

(c)(ii) When pressure is increased, by Le Chateliers Principle, the equilibrium shifts to reduce
pressure by decreasing the number of gaseous molecules. As forward reaction involves
reduction of gaseous molecules, position of equilibrium shifts to the right.

3 Or
(a)














Comments:
Initial rate for forward reaction is very fast
since initial partial pressures of reactants are
high. Initial rate of reverse reaction is 0 as
initial partial pressure of product is 0 atm.

As dynamic equilibrium is established, rate of
forward reaction = rate of reverse reaction
the graph will be horizontal at the same point.
Comments: Note K
p
is in terms of partial
pressure and not concentration!
E
A
E
A
Area
<<
Area
<<
E
A

E
A

Number of molecules
with energy
Energy
T
1
Comments:
Be careful not to
draw the graph
for temperature.

Your answers
should always
make reference to
your graph!
Comments: Units in this case cannot be Pa
1
as
the units given in the question is atm.
GKL/N06/P3/solutions
- 4 -
Shaded area under the graph represents the number of molecules with energy greater
or equal to the activation energy, E
a
.
Addition of suitable catalyst lowers the activation energy from E
A
to E
A
by
providing an alternative pathway.
Thus, from the sketch, number of molecules with energy greater than or equal to the
lowered activation energy, E
A
, will increase.
This increases the frequency of effective collision and rate of reaction increases.
Catalyst thus speeds up a chemical reaction.

(b) Analysis: Which reaction has highest and which has lowest activation energy Highest
activation energy involves bond breaking while lowest activation energy involves bond
forming.


CH
4
CH
3
H +
I Breaking of CH bond
CH
3
Cl + CH
3
Cl
II Forming of CCl bond
Cl
2
2Cl III Breaking of ClCl bond

From Data Booklet,
Bond Bond energy / kJmol
1

CH 410
ClCl 244
Reaction II requires the lowest activation energy while reaction I requires the highest
activation energy.
Explanation: Reaction II was a bond formation reaction and thus has a very low
activation energy. Since CH bond has a higher energy than ClCl bond, larger amount
of energy is needed to break the CH bond as compared to ClCl bond. Thus, reaction I
associate with a higher activation energy.

(c) Analysis: Fe
2+
and H
2
O
2
are both in aqueous states Fe
2+
acting as homogeneous
catalysis Fe
2+
will have a oxidation state change

From Data Booklet,
Fe
3+
+ e Fe
2+
---(1) E
u
= +0.77V
O
2
+ 2H
+
+ 2e H
2
O
2
---(2) E
u
= +0.68V
H
2
O
2
+ 2H
+
+ 2e 2H
2
O ---(3) E
u
= +1.77V

Using the given half equations (2) & (3) and (1), the suggested mechanism can be
proposed:

H
2
O
2
+ 2H
+
+ 2Fe
2+
2H
2
O + 2Fe
3+
E
u
cell
= +1.77 (+0.77) = +1.00V
2Fe
3+
+ H
2
O
2
O
2
+ 2H
+
+ 2Fe
2+
E
u
cell
= +0.77 (+0.68) = +0.09V

Since both steps in the mechanism have E
u
cell
> 0, reactions are spontaneous under
standard conditions are thus the mechanism is a feasible one.
GKL/N06/P3/solutions
- 5 -









4 (a)(i) Na atom has to lose 1 electron while O atom has to gain 2 electrons to achieve an octet.
Thus, 2 Na atoms are needed to provide electrons for 1 O atom, resulting in Na
2
O.

(Alternatively) Na atom will form Na
+
ion while O atom will form O
2
ion. Therefore, to
balance the charges on the ions, 2 Na+ ion will attract 1 O
2
ion to give a formula of
Na
2
O.

Si atom has 4 valence electrons while O atom has 6 valence electrons. Si atom needs to
share 4 electrons while O atom needs to share 2 electrons to form an octet. Therefore, each
Si atom shares 4 electrons with 4 O atoms while each O atom shares 2 electrons with 2 Si
atoms in a macromolecular structure.





(a)(ii) Na
2
O + H
2
O 2NaOH pH > 12
Na
2
O is a basic oxide which will react with water to form a strongly alkaline, sodium
hydroxide.

P
4
O
10
+ 6H
2
O 4H
3
PO
4
pH < 2
P
4
O
10
is an acidic oxide which will react with water to form phosphoric acid H
3
PO
4
.




(b) Analysis: Gallium is in Group III of the periodic table and thus will have very similar
chemistry as Aluminium. Since Al
2
O
3
is amphoteric, Ga
2
O
3
should be amphoteric.


Ga
2
O
3
+ 2NaOH + 3H
2
O 2NaGa(OH)
4


Explanation: Ga
2
O
3
is an amphoteric oxide similar to Al
2
O
3
. Thus, it is able to undergo
acid-base reaction with NaOH to give a salt, sodium galliate.



Comments: Your answer should not focus on oxidation numbers as oxidation numbers of
elements are a result of the formulae of their oxides.
Comments: Your pH values should be extreme and not merely greater than or less than 7.
Comments: You can also begin with Fe
3+
as the catalyst.
2Fe
3+
+ H
2
O
2
O
2
+ 2H
+
+ 2Fe
2+
H
2
O
2
+ 2H
+
+ 2Fe
2+
2H
2
O + 2Fe
3+

An easy guideline to decide for a suitable homogeneous catalyst is to check if its E
u
value is
in between the E
u
values of the half equations. In this context, since E
u

Fe3+/Fe2+
is between
E
u
H2O2/H2O
and E
u
O2/H2O2
, it is therefore a suitable catalyst.
GKL/N06/P3/solutions
- 6 -
(c) Let M be the Group I metal.
M
2
O + 2HCl 2MCl + H
2
O
Ar. the from lithium is M
6.8 x
29.6 16 2x
M. of Ar the be Let x
6 . 29
00338 . 0
100 . 0
O M of moles of No.
O M of Mass
00338 . 0 00675 . 0
2
1
O M of moles of No.
00675 . 0
1000
13.50
0.500 used HCl of moles of No.
2
2
2

=
= +
= = =
= =
= =
Mr
mol
mol


5 Either
(a)(i)
When silver nitrate is added to sodium chloride, white ppt is observed.
When silver nitrate is added to sodium bromide, cream ppt is observed.
When silver nitrate is added to sodium iodide, yellow ppt is observed.

(a)(ii) Description: When aqueous ammonia is added to the precipitates, the white ppt dissolves,
while the cream ppt is sparingly soluble and the yellow ppt is insoluble.

Explanation: AgX (s) Ag
+
(aq) + X

(aq) --- (1)

Ag
+
(aq) + 2NH
3
(aq) Ag(NH
3
)
2
+
(aq) --- (2)

Ag
+
reacts with aqueous ammonia to form soluble Ag(NH
3
)
2
+
complex. [Ag
+
] decreases
and thus position of equilibrium in (1) will shift to the right to increase [Ag
+
]. Since
K
sp
(AgCl) > K
sp
(AgBr) > K
sp
(AgI),
solubilities of silver halides differ in aqueous ammonia.

(b) When KI (aq) is added to Pb
2+
solution, yellow ppt of PbI
2
is formed. PbI
2
is a sparingly
soluble salt.
2KI (aq) + Pb
2+
(aq) PbI
2
(s) + 2K
+
(aq)

When more KI (aq) is added, the excess I

(aq) will form a soluble complex with PbI

2

causing the precipitate to redissolve.
PbI
2
(s) + 2I

(aq) [PbI
4
]
2
(aq)

(c)(i) 10HNO
3
+ I
2
2HIO
3
+ 10NO
2
+ 4H
2
O

(c)(ii)
12.4g 3(16.0)] 14.0 [1.0 0.197 HNO of Mass
197 . 0 0197 . 0
1
10
HNO of moles of No.
0197 . 0
2(127.0)
5.00
reacted I of moles of No.
3
3
2
= + + =
= =
= =
mol
mol

Comments:
Do not always assume that 1
mole of acid 1 mole of base
in any acid-base reaction.
Write and balance the
equation to confirm.

In this case, 2 moles of acid
1 mole of base. Be careful!
GKL/N06/P3/solutions
- 7 -
5 Or
(a)(i)
H
2
+ Cl
2
2HCl

(a)(ii) Reactions with hydrogen become less vigorous down the group (from chlorine to iodine).
Cl
2
reacts rapidly and explodes with H
2
in the presence of light while Br
2
reacts slowly
and required heating at 200C in the presence of catalyst. I
2
has no reaction with H
2

unless heated strongly.

Explanation: This is because down the group, HX bond strength becomes weaker. From
Data Booklet, B.E (HCl) > B.E (HBr) > B.E (HI). Thus, reaction is less spontaneous
with formation of less stable product.







(a)(iii) From Data Booklet,
Cl
2
+ 2e 2Cl

E
u
= +1.36V
I
2
+ 2e 2I

E
u
= +0.54V
4Cl
2
+ Na
2
S
2
O
3
+ 5H
2
O 2NaHSO
4
+ 8HCl

Oxidation of S
2
O
3
2
to S
4
O
6
2
by Cl
2
, E
u
cell
= +1.36 (+0.09) = +1.27V > 0
Oxidation of S
4
O
6
2
to SO
2
by Cl
2
, E
u
cell
= +1.36 (+0.51) = +0.85 V > 0
Oxidation of SO
2
to SO
4
2
by Cl
2
, E
u
cell
= +1.36 (+0.17) = +1.19 V > 0

I
2
+ 2Na
2
S
2
O
3
Na
2
S
4
O
6
+ 2NaI

Oxidation of S
2
O
3
2
to S
4
O
6
2
by I
2
, E
u
cell
= +0.54 (+0.09) = +0.45V > 0
Oxidation of S
4
O
6
2
to SO
2
by I
2
, E
u
cell
= +0.54 (+0.51) = +0.03 V (no oxidation)

Oxidation of S
4
O
6
2
to SO
2
by Cl
2
can occur more favourably under standard conditions
than with I
2
as shown by the E
u
cell
values (+0.85V compared with +0.03V). Therefore,
further oxidation occurs with Cl
2
but not for I
2
, resulting in the different products formed.








(b) NaClO
3
reduces to ClO
2
oxidation number of chlorine reduces from +5 to +4
HCl oxidises to Cl
2
oxidation number of chlorine increases from 1 to 0
HCl reacts to NaCl

oxidation number of chlorine remains at 0
Comments: Many of you will try to correlate to E
u
values or bond length. Note that E
u

values only apply to aqueous solution (not for reactions between gases). Bond lengths
will not provide a complete answer as it does not tell anything about stability of product.
Comments: Many of you will be keen to add up all the sulphur E
u
values and used the sum
of E
u
values to prove that E
u
cell
> 0 for Cl
2
but not I
2
. This is a BIG CONCEPTUAL
ERROR!! Looking individually at each step of further oxidation, each halogen is oxidising
S
2
O
3
2
to S
4
O
6
2
. Then, each halogen will further oxidise S
4
O
6
2
to SO
2
. Every step is a
totally different redox reaction. You cant conveniently add them up and take a short cut.
GKL/N06/P3/solutions
- 8 -
(c)(i) 4BrF
3
+ 3SiO
2
3SiF
4
+ 2Br
2
+ 3O
2


(c)(ii)
15.2g 3(19.0)] 9.9 7 [ 0.111 BrF of Mass
111 . 0 0832 . 0
3
4
BrF of moles of No.
0832 . 0
2(16.0)] 8.1 2 [
5.00
reacted SiO of moles of No.
3
3
2
= + =
= =
=
+
=
mol
mol


6 (a)(i) Condition: uv light (optional: excess C
2
H
6
)

(a)(ii) This is a free-radical substitution reaction because an H atom is substituted with a Br
atom to give the product. This is brought by Br- free radical which has an unpaired
electron when Br
2
undergo homolytic fission under uv light.

(a)(iii) This is a homogeneous catalysis as the catalyst, gaseous Br- free radical, is in the same
phase as the gaseous reactants.




(b)(i) Dehydrobromination Elimination reaction of HBr
Reagents and conditions: ethanolic KOH, reflux

(b)(ii)
D
hot concentrated
KMnO
4
CO
2
+
+ H
3
C C
O
OH H
3
C C
O
C
O
OH

D undergoes oxidative cleavage to give 3 parts. C=C bonds undergo oxidative cleavages to
give C=O bonds. Thus, D must have 2 C=C bonds.

CH
2 C
CH
3
CH CH CH
3
D

C undergoes elimination of 2HBr to give D. C has 2 Br atoms which is a result of free
radical substitution. 2H atoms must have been substituted by 2 Br atoms. Thus, B must
be an alkane.
B
H
3
C CH
CH
3
CH
2
CH
2
CH
3

(Answers will be acceptable for D: 3-methylpenta-1,3-diene and B: 3-methylpentane)
Comments: Br - is used and regenerated in the propagation step.
GKL/N06/P3/solutions
- 9 -
(b)(iii) Any 2 of the following structures.
CH
2
CH
CH
3
CH CH
2
CH
3
Br Br
CH
3
C
CH
3
CH
2
CH CH
3
Br Br
CH
2
CH
CH
3
CH
2
CH CH
3
Br Br
CH
3
C
CH
3
CH CH
2
CH
3
Br Br

(b)(iv) D will have 2 stereoisomers.
C C
CH
3
C
H H
H
2
C
CH
3
C C
H C
H CH
3
H
2
C
CH
3
cis
trans


8 Either
(a)
Step I: Cl
2
, uv light
Step II: Cl
2
, AlCl
3
, in the absence of light
Step III: KMnO
4
, dilute H
2
SO
4
, reflux
Step IV: PCl
5
, anhydrous / SOCl
2
, anhydrous

(b) Ease of hydrolysis (in ascending order): J < H < K

Description:
J H K
Cl H
3
C

C
H
Cl
H
o+
o

C Cl
O
o+ o
o
CCl bond is very strong
due to delocalisation of the
lone-pair of electron of Cl
into the t electron cloud of
benzene. Thus, the C atom is
C atom of CCl bond has
only 1 electronegative
atom (Cl) bonded directly
to it. Thus, the C atom is

Carbonyl carbon has 2
electronegative atoms (O
and Cl) bonded directly to
it. Thus, the C atom is
Least electron deficient Electron deficient Most electron deficient
J is least susceptible to
nucleophilic attack by H
2
O.
H is susceptible to
nucleophilic attack by
H
2
O.
J is most susceptible to
nucleophilic attack by H
2
O.




Comments: Cl
2
cannot be in aqueous
state!!
Comments: You might want to give your explanation in a table format for clarity.
GKL/N06/P3/solutions
- 10 -
(c)(i) An electrophile is a particle which is an electron pair acceptor.

(c)(ii) Cl
2
+ AlCl
3
AlCl
4

+ Cl
+


(c)(iii)
CH
3
Cl
+
CH
3
H Cl
+
CH
3
H Cl
+
CH
3
Cl
+ HCl + AlCl
3
slow
fast
(intermediate)
AlCl
4
-

8 Or
(a)
L
O C
O
H
3
C
O C
O
CH
2
P

(a)(ii)
O C
O
H
3
C
C
O
OH
PCl
5
C
O
Cl
H
3
C OH
room
temperature
room
temperature


(a)(iii) Analysis: Alcohol into Benzoic Acid Oxidation of benzene side chain
Conditions and reagents: KMnO
4
, dilute H
2
SO
4
, reflux






Comments: Note that
this is a guided
question worth only 3
marks. Thus, there is
no need to waste time
writing a detailed
mechanism. Show
only how the
electrophile attacks
the methylbenzene.
Comments: Note that carboxylic acid is not
reactive enough to react with phenol to give
ester.
GKL/N06/P3/solutions
- 11 -
(b)(i) Acidity (in ascending order): M < Q < N

Explanation:
M (alcohol) Q (phenol) N (carboxylic acid)
CH
2
O

C O

O
Alkyl group of the
alkoxide exerts an electron
donating effect. Thus, the
negative charge on
alkoxide ion is
Negative charge on O atom of
the phenoxide can be
delocalized into t electron cloud
of benzene. Thus, the negative
charge on phenoxide ion is
Carboxylate ion is
resonance stabilized.
Thus, the negative
charge on carboxylate
ion is
intensified dispersed most dispersed
Alkoxide ion is relatively Phenoxide ion is relatively Caboxylate ion is
least stable stable most stable
Alcohol thus Phenol thus Carboxylic acid thus
least favour favour most favour
dissociation of H
+
dissociation of H
+
dissociation of H
+






(b)(ii) Compound NaOH Na
2
CO
3

M No reaction No reaction
Q
Undergoes acid-base reaction to
give salt and water
No reaction
N
Undergoes acid-base reaction to
give salt and water
Undergoes acid-base reaction
to give salt and water


11 (a)(i) H
2
S + 3/2 O
2
SO
2
+ H
2
O

(a)(ii)
3
2
3 3
2
05 . 0 05 . 0
1
1
produced gas SO of Volume
05 . 0 1000
100
0.005
methane of 1000dm in S H of Volume
dm
dm
= =
= =


15 (a)(i)
1 1
1 1
122
122 . 0
) 360 ( 0 . 190 2 . 146
Using


=
= A
A =
A A = A
K Jmol
K kJmol S
S
S T H G
u
u
u u u



Comments: It is also good for this question to be presented clearly in a table form.
GKL/N06/P3/solutions
- 12 -
(b)(i) For reaction to be feasible, AG
u
< 0
K 1006
0 )
1000
83
( 5 . 83
0
0
>
<
+
+
< A A
< A
T
T
S T H
G
u u
u

Temperature at which this reaction becomes feasible will be 1006 K

(c) In (a)(i), 2 moles of gaseous reactants give 1 mole of gaseous product (An = 1). In
(b)(i), 1 mole of gaseous reactants give 2 moles of gaseous product (An = 1).Thus,
molecules become less disordered in (a)(i) whereas in (b)(i), molecules become more
disordered. This gives rise to the negative AS
u
in (a)(i) and the positive AS
u
in (b)(i).







Comments: Please always be careful that
AS
u
tends to be in Jmol
-1
K
-1
. Rem to
change the units to KJmol
-1
K
-1
before you
substitute into the formula.
Comments: Remember that you cannot just discuss number of molecule. AS
u
correlates
to number of MOLES of molecules.