1.

(a) (i) For solution A :

HL = H+ + L-

Initial 0.15 0 0
At eqm. 0.15-x x x

x2
1.38x10-4 =
0.15  x

Assuming that x « 0. 15
x2 = 2.07 x 10-5
[H+] = 4.55 x 10-3
pH = 2.34 (Accept answers from 2.3 to 2.4)

For solution B

All OH- ions will react with lactic acid to form sodium lactate

HL = H+ + L-

Initial (0.15-0.05) 0 0.05

At eqm. (0.1 - y) y 0.05 + y

y (0.05  y ) y (0.05  y )
1.38x10-4 = (0.15  0.05)  y  (0.1  y )

Assuming that y « 0.05

[H+] = y = 2.76 x 10-4

pH = 3.56 (Accept answers from 3.5 to 3.6)

(ii) The pH of solution A drops (or changes) to greater extent/there is a smaller drop
in pH for solution B because B is a buffer solution The H+ added will react with
the lactate present to form lactic acid and hence drop in pH is relatively small.
(Accept any correct description of the buffer action.)

(iii) At the equivalence point, all acid is converted to the salt. The pH at equivalence
point is the same as the pH of an aqueous solution of the salt
(Accept appropriate calculation with a calculated pH in the range of 8.5 to 8.6)

For the two solutions, the concentrations of lactate formed at the equivalence
points are the same .’. their pHs are the same.

(b) PV = nRT
PV=mRT
M = mRT/PV
= RT/P

(Award '/2 marks if only PV = nRT is given.)

M = 1.15 x 103 x8.31x298/ 95.3 x 103

= 29.9 g (mol-1) (Accept answers from 29.8 to 30.0 g)
 (1 mark for numerical answer; 1/2 mark for unit)

Since C has a valence of 4 and H has a valence of 1

.’. molecular formula C2H6. (Accept deducation with the CnH2n+2 as an argument.)

© (i)

(ii)

2. (a) (i) In diamond, the C atoms are held by C-C single covalent bonds , whereas in
graphite the interaction between C atoms within the same layer is covalent bond
with multiple bond character sideway overlap of the unhybridized p-orbital
strengthens the covalent bond.
In graphite, the attraction between the layers of C atoms is van der Waals' forces
The stronger interaction will lead to a shorter C-C distance
Therefore the C-C distances are :
between layers of graphite > between C atoms in diamond > within layers of
graphite

(ii) In diamond, the C-C bonds are strong. The strong directional character of covalent
bond restricts the relative motion between C atoms .’. Diamond is hard.
In graphite, the C atoms are held in layer structure. The weak attraction force .
between layers allows the layers to slip over each other.
.’. graphite is soft and can be used as lubricant

(b) (i) For 1 st order reaction

1 a
ln
k ( a  x)
(Accept any forms of 1st order equation)

ln 2
and k  9
 5.46 x10 10 y 1
1.27 x10

(Accept any correct indication of the decay constant in the calculation.)

1 1 9
t 10
ln( )
5.46 x10 1
 = 4.2 x 109 y
(Accept answers from 4.1 x 109 to 4.3 x 109 y.)
(1 mark for numerical answer; ½ marks for unit)

(ii) There is no serious escape of 40Ar from the sample

(c) (i) (1) H = -242 x 1000 / 18

_ =13.4 MJ kg-1/-1.34 x 104 kJ kg-1

(2) RC[CH3H(l)] =Hf[CO2(g)] + 2Hf[H2O(l)] - Hf[CH3H(l)]

= -394 + 2(-242) - (-239)

= -639 kJ mol-1

H= -639xl000/ (32+1.5x32) (or H= -639xl000 /(44+2x18) )

-8.0 MJ kg-1/ -8.0 x 103 kJ kg-1

( deduct 1/2 marks for omitting the sign )

(ii) Effectiveness of fuel

(1): -13.4 / 18 = / -13.4x104 / 18 = -744

 8.0  8.0 x10 3

 0.3 /  300
(2) : 1 1
( 44  2 x18) ( 44  2 x18)
3 3

Based on the above data, H2(g) is the more effective fuel.

(Correct calculation is a pre-requisite for the correct deduction.)

3. (a) (i) k / s-1 ln(K) T/K 1 /T / k-1

2.46 x 10-5 -10.61 273 3.66 x 10-3
4.75 x 10-4 -7.65 293 3.41 x 10-3
5.76 x 10-3 -5.16. 313 3.19 x 10-3
5.48 x 10-2 -2.90 333 3.00 x 10-3
Slope = -Eact/R

Eact = -R(slope) = -(8.31 JK-1 mol-1) (-11646 K) = 96.8 kJ mol-1

(Accept answers from 87.0 to 106.0 kJ mol-1 error in sign is not acceptable and the
answer must be accompanied with the graph.)
(1 mark for numerical answer, 1/2 marks for the unit)
 (ii) From the graph
At 353k: ln k =-0.92
i.e. k = 0.40 s-1

(Accept answers from 0.35 to 0.44 s -1; rate constant obtained by numerical
calculation is also acceptable.)

(1 mark for numerical answer; 1/2. marks for unit)

For first order reaction

k = ln2 / t1/2

t1/2 = 1.73 s
(Accept answers from 1.56 to 1.90 s)
(1 mark for numerical answer; 1/2 marks for unit.)

(iii) Titrate the cone. of the dicarboxylic acid using a standard solution of an alkali
or measure the volume of CO2 liberated/the gas pressure at a fixed volume

(b) (i)

(1 mark for the curves, '/2 marks for each axis; 1/2 marks to indicate the relative
temperature of the two curves.)

(ii) At a higher temperature (T2), the portion towards high kinetic energy is much
larger (refer to the curves in (i)). More particles would have sufficient energy to
overcome Ea, and to react.
Increasing the number of effective reactant increases the rate of reaction.

(iii)
 (1/2 marks for each axis; 1/2 marks for each curve, the curve for the catalysed reaction
should have a hump; 1/2 marks for labelling the reactants, products and
intermediate; 1/2 marks for showing a lower energy state for the product (i.e.,
indication of an exothermic reaction.)

The presence of a catalyst causes the reaction to take place via an alternative fiction
pathway with a lower activation energy. Lowering the kinetic barrier increases
the rate of reaction.

4. (a) (i) (I) At anode

Pb(s) + SO42-(aq) --> PbSO4(s) + 2e

At cathode
PbO2(s) + SO42-(aq) + 4H+(aq) + 2e -> PbSO4(s) + 2H2O(l)

(II) Pb(s) + PbO2(s) + 2SO42-(aq) + 4H+(aq) -> 2PbSO4(s) + 2H2O(l)

standard e.m.f. = +1.69 - (-0.36) V

= +2.05 V

(-2.05 V is also acceptable when the overall equation is written in the

reverse order)

(ii) . Pb(s) PbSO4(s) | H2SO4(aq) |PbSO4(s) | PbO2(S) | Pb(s) E ° = +2.05 V

or [Pb(s) + SO42-(aq)] | PbSO4(s) | H2SO4(aq) | [PbSO4(s) + 2H2O(l)]

[PbO2(s) + SO42-(aq) + 4H+(aq)] | Pb(s) E ° = +2.05 V

(1 mark for the sequence of the species; 1 mark for E ° . No mark deduction
for omitting state; -2.05 V is only acceptable when the cell diagram is written
in the reverse order.)

(iii) (I) During discharge, SO42- anal H+ (or H2SO4) are removed from the solution

The reduction potential of the anodic reaction becomes less negative, while
that of the cathodic reaction becomes less positive
 (II) The products of the electrochemical reactions remain in the system
or, the cathodic and anodic reactions are reversible with no side products. Upon
charging, the reverse reaction can occur.

(b) (i) No. of moles of HOAc in H2O No. of moles of HOAc in alcohol

Initial 0.5 x 0.1 0

At eqm. 0.05 - x x

0.05  x
3.05  0.1
x
0.2
x = 0.0198 (Accept answers from 0.019 to 0.020)

efficiency of ethanoic acid extraction

= 0.0198 / 0.05 = 39.6%

(Accept answers from 39.0 to 40.0%)

(ii) First extraction

No: of moles of HOAc No. of moles of HOAc
in H2O in alcohol

Initial 0.05 0
At eqm. 0.05 – y1 y1

0.05  y1
3.05  0.1
y1
0.1

0.1 y, = 0.0123 (Accept answers from 0.012 to 0.013)

Second extraction
No. of moles of HOAc No. of moles of HOAc
in H2O in alcohol
Initial (0.05 - 0.0123) 0
At eqm. 0.0377 - y2 y2

0.05  y 2
3.05  0.1
y2
0.2
y2 = 9.3 x 10-3

(Accept answers from 9.0 x 10-3 to 1.0 x 10-2)

efficiency of ethanoic acid extraction

 = (12.3+9.3)x10-3 x100%
0.05
= 43.3%
(Accept answers from 43.0 to 44.0%)

There is a surplus of 3.7% extraction effciency by using two 100 cm3 portions of
the alcohol instead of using 200 cm3 in a single batch. .’. (ii) is a better extraction
method.

5. (a) (i) a : sp3 ; b : sp2 ; c : sp2 ; d : sp

(Deduct 1/2 marks for each extra structure.) 1/2 marks for each bond angle
(ii)

(b) (i) acts as a filter for harmful ultraviolet radiation from the sun
(ii) In the stratosphere, CFCs absorb UV radiation to give Cl•

hv
CF2Cl2 ------- •CF2Cl + •Cl

The following free radical (chain) reaction then occurs and each •Cl produced can
cause the removal of a large no of O3
Cl • + O3  ClO•. + O2
ClO• + O3  Cl•+ 2O2

(iii) O3 reacts with unburnt HCs and NO 2 (from automobile exhaust) giving rise to the
formation of photochemical smog
or, O3 is toxic/has adverse effects on the respiratory system
6. (a) (i) The interaction between polymer chains of PE is van der Waals' force while that
between Nylon 6:6 is H-bond

The higher tensile strength of nylon is due to its stronger attraction

(ii) C-C linkage in PE is non-.polar .’. not readily attacked by acids/has no reaction
with acids

the amide linkage in nylon hydrolyse in acids to give –NH3+ and COOH groups
causing shortening of the chain

(iii) alkaline conditions/enzyme

(b) (i) nitrogen oxides, carbon monoxide, unburnt hydrocarbons

 (ii) The converter contains the metal catalysts Rh/ Pt/ Pd
which catalyse the following reactions. Air is introduced into the converter to
oxidize CO & unburnt HCs to CO2
2NO(g) + 2CO(g)  N2(g) + 2CO2(g)
2CO(g) + O2(g)  2CO2(g)
C7H16(g) + 11O2(g)  7CO2(g) + 8H2O(g)
(Accept any equation showing the oxidation of an alkane with 6 to 10 carbons)

© (i)

(ii) Use IR spectroscopy

Absorption at 2500 to 3300 cm-1 indicates the presence of O-H of the carboxylic
acid
Absorption at 1680 to 1750 cm1- indicates the presence of C=O of the acid and the
ester
or, Chemical tests
treat compound with Na2CO3 / NaHCO3
evolution of CO2(g) indicates the presence of -CO2H

Warm compound with dilute acid. Smell of vinegar indicates the presence of an
ethanoyl ester

7. (a)
8. (a) (I)
For the d-block elements, the energy difference the 3d and the 4s subshells is
small. A halfly filled d subshll has extra stability and thus the ground state a
configuration of Cr is 3d5 4s1 instead of 3d4 4s2.

(b) (i) The colour of the solution changes from yellow to orange

2CrO42- + 2H+  Cr2O72- + H2O

(ii) A blue ppt. is formed

Cu2+ + 2OH-  Cu(OH)2
and the ppt. dissolves in excess NH3 to give a deep blue solution
Cu(OH)2 + 4NH3 --> Cu(NH3)42+ + 2OH-

(iii) Solution turns yellow and then purple/pink/violet (due to excess MnO4-

MnO4- + 8H+ + 5Fe2+  Mn2+ + 4H2O + 5Fe3+

(c) (i) (I) equilibrium position will shift to right

because the no. of moles of gas on the right is smaller than that on the left

(II) equilibrium position will shift to left

because the reaction is exothermic

(ii) Dissolve SO3 in conc. H2SO4 to form oleum / H2S2O7

H2SO4(l) + SO3(g)  H2S2O7(l)

Add water to oleum to give conc. H2SO4 H2S2O7(l) + H2O(l)  2H2SO4(l)

(d) (i) (I) Cl2 + 2OH- -> Cl- + ClO- + H2O

 (II) 3Cl2 + 6OH- --> ClO3- + 5Cl- + 3H2O

(ii) The reaction of I2 and NaOH is the same at 298 K and 343 K

3I2 + 6OH-  IO3- + 5I- + 3H2O

because the disproportation of IO- to give IO3- and I- is rapid at all temperature