2010 GCE A Level Chemistry Paper 9647/03

Question 1: 14 marks (most popular)

Question 2: 14 marks (least popular)
Question 3: 11 marks
Question 4: 14 marks
Question 5: 10 marks
Total P3: 49 53 / 80 (norm)
Highlighted parts are questions where students did not do well. Refer to Cambridge report for
details on why students did not do well. They should also be the parts that the lecture should
focus on (if there is time constraint.)
1 (a) (i) Entropy of a chemical system measures the degree of disorder in a
system. It gives a measure of the extent to which particles and energy
are distributed within the system.
[1]
(ii) The mixing of Cl
2
and N
2
will result in an increase in the entropy of
the system as there are now more ways in which the energy can be
distributed among the molecules.
[1]
The heating of Cl
2
to a higher temperature means that there are more
ways for the energy to be distributed among the molecules. Thus,
the particles will move more randomly and at higher speeds. Thus,
entropy will increase.
[1]
The chemical reaction between Cl
2
and I
2
to form ICl
3
will result in a
decrease in entropy as there is a reduction in the number of
molecules of gas in a chemical reaction by 1 mol. There are now less
particles moving randomly and less ways to distribute the energy.
[1]
There will be an increase in entropy during photolysis as the number
of particles in gaseous state increase by 1 mol. Each molecule is
split into two chlorine radicals.
[1]
(b) (i) For reaction of hydrogen with chlorine, the reaction is explosive in
sunlight, but slow in the dark below 200
o
C.
For reaction of hydrogen with bromine, the reaction is slow at 300
o
C
with Pt catalyst.
The rate of reaction for H
2
with Cl
2
is faster than that between H
2
and
Br
2
.
[1]
(ii) It is expected that the rate of reaction of hydrogen with fluorine will be
higher. The reactivity of the halogen with hydrogen decreases down
the Group as the oxidizing power of the halogens decreases down the
group.
[1]
(c) (i) Cl
2
in liquid CCl
4
, uv light, r.t.p [1]
(ii) Free radical substitution
Initiation step:
Cl
2
2 Cl (slow step, uv light)
Propagation step:
Cl + C
2
H
6
C
2
H
5
+ HCl
C
2
H
5
+ Cl
2
C
2
H
5
Cl + Cl
Termination step:
2 Cl Cl
2
2 C
2
H
5
CH
3
CH
2
CH
2
CH
3
C
2
H
5
+ Cl C
2
H
5
Cl
[1]
[1]

[1]


[1]
(iii) This is because in the first propagation step, in the abstraction of
hydrogen radical from alkane to form HI, this reaction is highly
endothermic. (Bond energy of HI = 299 kJ mol
1
vs Bond energy of
HCl = 436 kJ mol
1
) Therefore, it is not possible for the reaction to
occur.
[1]
(d)
A
Cl
B
Cl
Cl
OR
Cl
Cl
C D
Br
Br

[1]
[1]
[1]
[1]
(e) (i) CFCs are inert, non-toxic OR can be liquefied under pressure and
is easily volatilised when pressure is released
[1]
(ii) CFCs, when reaching the ozone layer, undergoes homolytic fission
between C-Cl bond under the action of uv radiation via photolysis.
This forms Cl radicals which attack the ozone via a radical
mechanism, resulting in a chain reaction of destruction of ozone
molecules.
[1]
(iii) Presence of C-H bonds in alkanes makes it flammable. Thus, alkanes
may undergo combustion at high pressure conditions.
[1]
2 (a) (i)
for a weak acid, HA H A
+
+ where K
a
=
[ ][ ]
[ ]
H A
HA
+

pK
a
= log K
a

[1]

[1]
(ii)
pH1
HO
2
C CO
2
H
NH
3
+

[1]

pH3
HO
2
C CO
2
-
NH
3
+
OR
HO
2
C CO
2
H
NH
2

[1]



pH7
-
O
2
C CO
2
-
NH
3
+

Note: the electron-donating alkyl group on CO
2
H reduces the acidic
strength of CO
2
H, thus it will be protonated later.
[1]

pH11
-
O
2
C CO
2
-
NH
2

[1]
(b) (i) Quarternary and tertiary structure of a protein will be altered.
This occur because denaturation breaks the weak bonds holding
the secondary, tertiary and quaternary structure, but not the covalent
bonds within primary structure, resulting in a more disordered
arrangement. Such action is normally done by salts, acids or
enzymes. The weak bonds that are broken are the side chain
interactions, which include van der waals forces of attraction,
hydrogen bonds, ionic bonds and disulphide bonds.
[1]
[1]
(ii) by metal ions such as Ca
2+
,
it disrupts the ionic bonds between the charged R groups of the
amino acids by forming new ionic bonds with the carboxylate anions.

[1]

(iii) by weak acid,
it disrupts the ionic bonds holding the tertiary and quaternary
structures.
The weak acid will dissociate to cause carboxylate anions or amino
groups to be protonated.
CO
2

+ H
+
CO
2
H
NH
2
+ H
+
NH
3
+


[1]

[1]
(iv)
2
[ ]
[ ][ ]
c
gluconic acid
K
GDL H O
=
Amount of GDL =
1.00
178
= 0.005618 mol
Initial [GDL] =
0.005618
50
1000
=0.1124 mol dm
3

0.0670
(0.1124 0.0670)(55.5)
=

c
K =0.0266 mol
1
dm
3

[1]





[1]


[1]
(c) (i)
HO O
O
OH
Br
Br
Br
Br
Br
OH
OR
HO O
O
OH
Br
Br
Br
Br
Br
Br

[1]+[1]
For type
of rxn
(easy E.S
+ E.A)
(ii) HO O
OH
OH
HO O
O
OH

Compound F Compound G

Diadzein undergoes reduction of alkene and ketone with H
2
and Ni to
form F. A secondary alcohol is formed.
F has three hydroxyl groups, and thus able to react with three moles
of sodium via redox reaction.
F dissolves in NaOH(aq) as it contains phenolic groups which can
undergoes neutralization with NaOH(aq)
F undergoes oxidation with K
2
Cr
2
O
7
to form a ketone in G.
G undergoes condensation with 2,4-DNPH to form hydrozone.
[1] + [1]
for each
structure

[1] for all
chiral C

[1] for
reasons
3 (a) (i)
Cathode: O
2
(g) + 4H
+
(aq) + 4e 2 H
2
O (l)
[1]
(ii) Cathode x 3 + Anode x 2
Overall: 2 CH
3
OH + 3O
2
2 CO
2
+ 4H
2
O
[1]
[1]
(iii) E
o
cell
= E
o
red
E
o
CO2/CH3OH
1.18 = 1.23 E
o
CO2/CH3OH
E
o
CO2/CH3OH
= +0.05 V


[1]
(iv) Methanol cell is portable, easy storage and less flammable as
methanol is liquid. Thus, it need not be stored under pressure, unlike
hydrogen gas.
[1]
(b) (i)
CH
3
CH
2
OH(l) + 3O
2
(g) 2CO
2
(g) + 3H
2
O (l)
[1]
(ii) G = H TS
= (1367000) 298(140)
= 1339280 J mol
1

= 1340 kJ mol
1

[1]
(iii) Oxidation: CH
3
CH
2
OH(l) + 3H
2
O(l) 2CO
2
(g) + 12H
+
(aq) + 12e
cell
G
E
zF
C
C
A
=

z = 12




[1]

[1]
1339280
12(96500)
cell
E
C

= = +1.16V
(c) (i) H = bond breaking bond forming
= [(C-C)+5(C-H)+(C-O)+(O-H)+3(O=O)] [4(C=O)+6(O-H)]
= [(350)+5(410)+(360)+(460)+3(496)] [4(805)+6(460)]
= 1272 kJ mol
1


[1]

[1]
(ii) The enthalpy change of vapourisation of water and ethanol is not
considered in the calculation for (c)(i)
OR
The bond energies are of average values.
[1]
(d) (i) C
x
H
y
OH + Na C
x
H
y
O

Na
+
+ H
2

Amount of H
2
produced = (Amount of J used)
=
10.9
24000
= 0.0004542 mol
Amount of J used = 0.0009084 mol
C
x
H
y
OH +
1
4
y
x
| |
+
|
\ .
O
2
xCO
2
+
1
2
y + | |
|
\ .
H
2
O
Amount of CO
2
absorbed by NaOH(aq) =
109
24000
= 0.004542 mol
Comparing mole ratio C
x
H
y
OH xCO
2

0.0009084 : 0.004542
1 : 5
x = 5

In the combustion of the alcohol,
V(O
2
) used + V(CO
2
) produced = 54.4 cm
3
(i.e. reduction in volume)
V(O
2
) used = 109 + 54.4 = 163.4 cm
3

Amount of oxygen used =
163.4
24000
=0.006808 mol

Comparing mole ratio
1
4
y
x
| |
+
|
\ .
O
2
xCO
2

1
1
20
y | |
+
|
\ .
O
2
CO
2

0.006808 : 0.004542
1.50 : 1
1.5 =
1
1
20
y | |
+
|
\ .

y = 11













[1]















[1]
(ii) J undergoes oxidation with K
2
Cr
2
O
7
.
J must be either primary or secondary alcohol.
J undergoes elimination to form alkene K
Reasons
[max 2]

K undergoes vigorous oxidation to result in the cleavage of the
alkene bond to form ethanoic acid and propanone.
K
CH
3
C
CH
3
C
CH
3
H
J
CH
3
C CH
3
H
C
CH
3
H
OH






[1]+[1]
(iii) Concentrated H
2
SO
4
, reflux at 170 C [1]
(iv) K will not show geometrical isomerism as there are two methyl
groups attached on the same carbon involved in the C=C bond.

Note: Statements that are not acceptable:
(1) Methyl groups are on the same side of the double bond.
(2) There is a carbon with two methyl groups.
[1]
4 (a) Nucleon number is the total number of protons and neutrons in a
nucleus of an atom.
[1]
(b) In an electric field, the electron will be deflected to the positive
plate, while the proton will be deflected to the negative plate.
In an electric field, the angle of deflection for an electron is larger
than that of the proton as it is lighter than the proton.
[1]
(c) (i)
N O
X
X X
X
X
X X
X
X
X
OX
X

X
X
X X
X
X
O O O

NO
2
O
3

[1]+[1]
(ii) For O
3
, there are 2 bond pairs and 1 lone pair. The 3 electron pairs will
point towards the corners of an equilateral triangle. The lone pair-
bond pair repulsion > bond pair-bond pair repulsion because the
lone pair is closer to the oxygen than a bond pair. Thus, bond
angle is 115with the shape being bent.
[1]




For NO
2
, there are 2 bond pairs and 1 unparied electron. The 3
electron pairs will point towards the corners of an equilateral triangle.
The unpaired electron-bond pair repulsion is weaker than that of
the lone pair-bond pair repulsion in O
3
. Thus, bond angle is (any
value between O
3
and 170) with the shape being bent.
[1]




(iii) F, being a period 2 element, is not able to expand to accommodate
more than 8 valence electrons. To form FO
2
, F will need to form two
dative bonds. It would not do this as F is too electronegative for
dative bonding.
[1]



Cl, being a period 3 element, is able to use its 3d orbitals to
accommodate more than 8 valence electrons through the use of
energetically accessible 3d orbitals.
[1]


(d) (i) A sample of calcium is being held on a platinum wire that has been
repeatedly cleaned with hydrochloric acid to remove traces of previous
analytes. The sample is then burnt in a hot, non-luminous flame in the
presence of oxygen and the colour is being observed.
[1]



A brick red flame colour is observed. [1]
(ii) Oxides of Group II elements will react with water to form hydroxides.
As the Group II metal hydroxides goes down the group from
magnexium to barium, the solubility of the hydroxides increases.
This increases the extent of dissociation of the hydroxides, thus
resulting in the increase in the concentration of hydroxide ions,
and therefore the increase of the pH value from Mg to Ba.
[1]
(e)
Ba(O
3
)
2
+ H
2
O
5
2
O
2
+ Ba(OH)
2

[1]
(f) (i)
Amount of Na
2
S
2
O
3
=
15
0.100 0.001500
1000
mol =
Amount of I
2
= 0.000750 mol
[1]
(ii) Amount of O
3
= 0.000750 mol
Volume of O
3
= 0.000750 x 22.4 = 0.0168 dm
3
% O
3
=
16.8
100% 3.36%
500
=

[1]
[1]
(g) (i) For production of aldehyde, use acidified K
2
Cr
2
O
7
and heat/reflux
with distillation.
[1]

For production of carboxylic acid, use acidified K
2
Cr
2
O
7
and
heat/reflux
[1]
(ii)
L
From molecular formula, compound is unsaturated. To be able to react
with Br
2
(aq) indicates that a double bond is present, capable of
undergoing electrophilic addition.
M
Molecular formula is the same as L, indicating that it must contains a
cycloalkane in the compound as it does not react with Br
2
(aq),
indicating the absence of an alkene bond.
N
C
OH
CH
3
H
CH
3

N must undergo oxidation with alkaline aqueous iodine, thus having
[1]






[1]






[1]
the structure
C
OH
CH
3
H

5 (a)


In the electrochemical purification of copper

Anode: Crude copper
Cathode: Pure copper
Electrolyte used: Copper (II) sulphate

From the Data Booklet:
Ag
+
+ 2e Ag +0.80V
Cu
2+
+ 2e Cu +0.34V
2H
2
O + 2e H
2

+ 2OH

+1.23 V
Zn
2+
+ 2e Zn 0.76V

When an electric current is applied, both zinc and copper are oxidised
to Zn
2+
and Cu
2+
respectively since E

of Zn
2+
/Zn is less positive than
the E

of Cu
2+
/Cu.

Cu(s) Cu
2+
(aq) + 2e [including state symbols]
Zn(s) Zn
2+
(aq) + 2e

Silver, due to its more positive (E
u
) reduction potential will not be
oxidised.
Silver will drop to the electrolytic bed as elemental silver.

Zn
2+
and Cu
2+
migrate to the cathode.
Only Cu
2+
is reduced to copper due to its more favourable reduction
potential and higher concentration.

Cu
2+
(aq) + 2e Cu(s) [including state symbols]
[1] for
copper

[1] for
zinc

[1] for
silver

[1] for
quoting
E values













Zn
2+
remains in the solution.
(b) When NH
3
is first added to Cu
2+
(aq):
NH
3
+ H
2
O NH
4
+
+ OH
-

Cu
2+
(aq) + 2 OH
-
(aq) Cu(OH)
2
(s) --- (1)
blue ppt
Ionic product, [Cu
2+
][OH
-
]
2
> K
sp
of Cu(OH)
2

Blue ppt of Cu(OH)
2
is formed.

When excess NH
3
is added to Cu
2+
(aq):
[Cu(H
2
O)
6
]
2+
(aq) + 4NH
3
(aq) [Cu(H
2
O)
2
(NH
3
)
4
]
2+
(aq) + 4H
2
O(l) (2)
(excess)
NH
3
ligands replaces the H
2
O ligands, forming a more stable deep
blue [Cu(NH
3
)
4
(H
2
O)
2
]
2+
complex with Cu
2+
(aq).
[Cu
2+
] decreases as it is being used to form the complex
equilibrium position in (1) shifts left to increase [Cu
2+
]
Ionic product, [Cu
2+
] [OH
-
]
2
< K
sp
of Cu(OH)
2

Pale blue ppt,Cu(OH)
2
, dissolves.


[1]

[1]



[1]

[1]
(c) O
2-
+ NH
3
NH
2
-
+ OH
-

The colour of the solution is dark blue in colour.
[1]
[1]
(d) [Cu(H
2
O)
6
]
2+
+ 4Cl

[CuCl
4
]
2
(aq) + 6 H
2
O (l)
Ligand exchange reaction has occurred.
[Cl
-
] increases in concentrated hydrochloric acid, equilibrium
position will shift right to form yellow [CuCl
4
]
2-
complex.
Presences of both Cu
2+
(aq) and [CuCl
4
]
2-
in the equilibrium mixture
results in a yellow-green solution.

[1]



Solution remains blue when concentrated sulfuric acid is added as the
sulfate ions are weaker ligands.
[1]


Dilution of the yellow-green solution will reduce the [Cl

], hence by
LCP, the position of the equilibrium will shift to the left, producing
the original pale blue colour.
[1]
(e) (i)
4I

+ 2Cu
2+
I
2
+ 2CuI
[1]
(ii) E
cell
= 0.39 V
Reaction is thus not feasible.
[1]
(iii) CuI is insoluble in aqueous solutions.
Cu
2+
+ e Cu
+

Thus [Cu
+
] will be very low. Therefore, by LCP, the position of
equilibrium will shift towards the production of CuI, hence resulting
in the favouring of the forward reaction.
[1]
[1]
(f) (i) Pale blue solution will decolourised, and a brick-red precipitate
will be produced.
[1]
(ii) Positive result:


C
O
H
C C
H
C
H
C
H
H H
H
H
H
H

C
O
H
C C
H
C
C
H
H
H H
H H
H
H

Negative result:
C C C
H
C
H
H
H
H H
H
O
C
H
H
H


[1]





[1]