1994 A-level Chemistry paper II marking scheme

1.(a)(i) PAVA =nART

PBVB = nBRT [1m]
PA/PB = nA/nB(VB/VA) [1m]
= 1/2(1/2) = 1/4 [1m]
or PA = 1/4PB or PB = 4PA (1m)
(ii) P(CO2) < PA [1m]
Gas pressure is produced by the collision of gas molecules on wall of container [1m]. At low pressure,
the attraction / intermolecular force / van der Waal's force between CO2 molecules is a dominated
force, so the collision force on the wall is reduced.
2+ 2+
(b) FeNCS (aq) ions absorb visible light in electromagnetic spectrum, hence FeNCS (aq) can be
determined by measuring the absorbance of the solution. [1m]
Calibrate a colorimeter by measuring the absorbance of several solutions which contained known
2+
concentrations of FeNCS (aq) [1/2m + 1/2m]
-
(In these solutions, the NCS ions are in excess, so that Fe3+ ions present can be considered as existing
2+
in the complex form, FeNCS )
3+ -
By mixing comparable volumes of standard Fe (aq) and NCS (aq) solutions and measuring the
2+ 3+ - 2+
[FeNCS (aq)] formed with the colorimeter, [Fe (aq)], [NCS (aq)] and [FeNCS (aq)] at equilibrium can
be found. [1/2m + 1/2m]
Hence, the equilibrium constant
2+ 3+ -
Kc = [FeNCS ] / ([Fe (aq)][NCS (aq)]) [1m]
can be determined.
(c)(i)

The graph of log [C] versus t is not a straight line

∴ order ≠ 1 [1/2m]
The graph of 1/[C] versus t is a straight line
∴ order = 2 [1/2m]
[2m for the two graphs]
(ii) For second order reaction,
1994 AL CHEM P II – Page 1
 1/[C] = 1/[C]o - kt
From the slope of graph,
-2 -3 -1
k=1.997x10 (mol dm ) s [1m for ans.; 1m for unit]
-2 -2 -3 -1 -1
(1.95 x 10 to 2.05 x 10 (mole dm ) s )

(iii) Arrhenius Equation

ln k = C - Ea/RT
ln k = C - Ea/R(1/298) ...... (1)
ln k + ln 2 = C - Ea/R(1/306) ......(2)
(2) - (1)
ln 2 = Ea/R(1/298 - 1/306) [1m]
∴ Ea = 65.7 kJ [1/2m for answer; 1/2m for unit]

2.(a)(i) ∆H298 = -393.5 + 2(-285.9) - (-75.0) [1m]

= -890.3 kJ [1/2m for answer; 1/2m for unit]
(ii) CH4(g) + 2O2(g) à 2H2O(g) + CO2(g) ∆H= -801.7 kJ
-) CH4(g) + 2O2(g) à 2H2O(l) + CO2(g) ∆H = -890.3 kJ
2H2O(l) à 2H2O(g) ∆H = 88.6 kJ [1m]
∆Hvaporization(H2O) = +44.3 kJ [1m]
(iii) ∆Hcomb.[C(diamond)] = -395.4 kJ mol .
-1

∆Hcomb.[C(graphite)] = -393.5 kJ mol .

-1

∴ graphite is relatively more stable allotrope [1m]

Conversion from diamond to graphite involves the rearrangement atoms in giant covalent network
would require a high activation energy. ∴ conversion does not occur at room temperature. [1m]

(b)(i) In H3PO4, the intermolecular force is H-bond. [1m]

The structure of H3PO4 is
OH
/
O=P-O-H [1/2m]
\
OH
(or H3PO4 is capable of forming 3-H-bonds with its neighbours 1/2m) With strong intermolecular forces,
H3PO4 has a high viscosity [1/2m]
(ii) In ice the intermolecular attraction is H-bond, each H2O molecule is tetrahedrally surrounded by 4 other
H2O molecules or (C.N. = 4) [1/2m + 1/2m]
i.e. an open structure [1/2m]
In liquid water, the molecules are packed closer together
∴ water has a higher density than ice [1/2m]
For the endothermic reaction,
H2O(s) H2O(l)
Increase in pressure, shifts the equilibrium to the right [1m]
∴ m.p. of ice decreases with increases in pressure
(c)(i)

[1m for labelling the two axes; 1/2m for the line drawn]
Mole fraction of F = 4/(4+1) = 4/5 [1/2m]
From the graph,
V.P. of mixture = 1.8Po [1m]
or, by calculation
PE = 0.2 Po PF = 0.8(2Po)
= 1.6Po
∴ V.P. of mixture = 1.8Po (1m)
1994 AL CHEM P II – Page 2
 (ii) If deviation is negative P < 1.8Po
If deviation is positive P > 1.8Po [1m]
Explanation: In case of negative (positive) deviation, the interaction between E and F is stronger
(weaker) than the average of interaction between E and E and between F and F. [1m]
The molecules have a smaller (greater) chance to escape, [1m] thus resulting in a lower
(higher) vapour pressure.
(Max. 2m, if only one of the cases is discussed.)

3.(a)(i) From the graph

+
When [Ag (aq)] = 1.0 M, e.m.f. of cell = +0.46 V [1m]
∴ Standard electrode potential of Ag(s)|Ag (aq) half-cell = +0.46 + (0.34) V
+

= + 0.80 V
[1/2m for answer, 1/2m for unit]
(ii)(I) From the graph, when e.m.f. = +0.27 V,
+
log10 [Ag (aq)] = -3.2 (-3.1 to -3.3) [1/2m]
+ -4 -3
i.e. [Ag (aq)] = 6.31 x 10 mol dm [1/2m]
-4 -4 -3
(7.94 x 10 to 5.01 x 10 mol dm )
+ -
(II) Ksp[AgBrO3] = [Ag (aq)][BrO3 (aq)] [1m]
-4
= (6.31 x 10 )(0.1)
-5 2 -6
= 6.31 x 10 mol dm [1m]
-5 -5 2 -6
(5.01 x 10 to 7.94 x 10 mol dm )
(b)(i) The dissociation of water
+ -
2H2O(l) H3O (aq) + OH (aq)
is an endothermic process / ∆H = +ve [1m]
+
Increase in temperature, the equilibrium shifts to the right [1/2m] and hence [H3O (aq)] increases. In
pure water, [H3O (aq)] at 323 K is higher than that at 298 K, ∴ pH of pure water at 323 K is less than
+

7.0. [1/2m]
(ii) Acid-base indicators are weak acids/bases.
The dissociation of which can be represented by:
+ -
HIn(aq) + H2O(l) H3O (aq) + In (aq) [1m]
The colour of an indicator depends on the relative concentrations of the acidic form. HIn and the
alkaline form In-(aq) which are of different colours. [1/2m]
The dissociation constant Ki for different acid-base indicators are different, [1/2m] thus they change
colour over different pH range.
The pH range of methyl orange is below 7, [1/2m]
while that of phenolphthalein is above 7, [1/2m]
∴ at pH 7, methyl orange shows its alkaline colour, while phenolphthalein shows its acidic colour.
+ -
(c)(i) Ka = [H ][PrCOO ] / [PrCOOH]
+ -
Assuming [H ] = [PrCOO ], [PrCOOH] = 0.1 M
-5 + 2
1.5 x 10 = [H ] / 0.1 [1m]
-3
[H+] = 1.225 x 10 M
pH = 2.91 [1m]
(ii) Assuming [PrCOOH] = 0.05 M
-
[PrCOO ] = 0.05 M
-5 +
1.5 x 10 = [H ] x 0.05/0.05 [1m]
+ -5
[H ] = 1.5 x 10 M
pH = 4.82 [1m]
( > 2 d.p. or < 2 d.p. -1/2m)
(iii) After addition of 1.0 x 10-3 moles solid NaOH
-3
[PrCOOH] = 0.05 - 1.0 x 10 }
- -3
[PrCOO ] = 0.05 + 1.0 x 10 } [1m]
-5 +
1.5 x 10 = [H ](0.051) / (0.049) [1m]
-5
[H+] = 1.44 x 10 M
pH = 4.84 [1m]
(> 2 decimal places or < 2 decimal places -1/2m)

4.(a) Heating conc. HCl in the presence of manganese(IV) oxide [1/2m + 1/2m]
∆
MnO2(s) + 4HCl(aq) à MnCl2(aq) + 2H2O(l) + Cl2(g) [1m]
or add conc. HCl to solid KMnO4 (1/2m + 1/2m)
- + 2+
10HCl + 2MnO4 + 6H à 5Cl2 + 8H2O + 2Mn (1m)
Pass the Cl2 produced through cold water to remove HCl, [1m] dry the gas by passing through conc.
H2SO4 and collect by downward delivery [1/2m + 1/2m]
1994 AL CHEM P II – Page 3
 The experiment should be carried out in a fume cupboard. [1m]
(b) The anomalous boiling point of HF is due to extensive H-bonding between HF molecules [1/2m + 1/2m]

(diagram showing H-bonds in HF) [1m]

(Accept alternative answers such as in HCl, HBr, HI there are no extensive H-bonds.)
(c) Highest O.S. of I = +7 [1m]
-
Example: IF7, IO4 [1m]
(d)(i) NaCl + H2SO4(l) à NaHSO4 + HCl [1m]
(ii) NaI + H2SO4 à HI + NaHSO4
8HI(g) + H2SO4(l) à I2(s) + H2S(g) + 4H2O(l) [1m]
or 2HI(g) + H2SO4(l) à I2(s) + SO2(g) + 2H2O(l) (1m)
HI, being a stronger reducing agent than HCl, will be oxidized by conc. H2SO4 to give I2. [1/2m + 1/2m]
-
(e)(i) ∵ NH2NH2 : IO3 = 1 : 1
- -
In the reduction of IO3 , O.S. of I decreases from +5 (in IO3 ) to +1 (in ICl) [1/2m]
∴ In the oxidation of NH2NH2, 4 moles of e should be released from each mole of NH2NH2 [1/2m]
-

In 1 mole of NH2NH2 there are 2 moles of N atoms.

∴ O.S. of N in the reaction product is 0. [1/2m]
The colourless gas is probably N2 [1/2m]
- + -
(ii) IO3 + 5H + HCl + 4e à ICl + 3H2O [1m]
+) NH2NH2 à ICl + N2 + 3H2O [1m]
- +
IO3 + H + HCl + NH2NH2 à ICl + N2 + 3H2O [1m]
- + -
Or, IO3 + 5H + HCl + 4e à ICl + 3H2O (1m)
+) NH2NH2 à ICl + N2 + 3H2O (1m)
- 2+ +
IO3 + NH3NH3 + HCl à ICl + N2 + 3H2O + H (1m)

5.(a)(i) Elements with valence electrons in d-orbitals [1/2m + 1/2m]

(ii)

[1m] each
2+
(iii) Mn with half-filled 3d orbitals is relatively stable. [1m]
Removing e disturbs this stable configuration: relative high energy is required. ∴, Mn is not readily
- 2+
3+
oxidized to Mn . [1m]
2+ 6
Fe with an electronic configuration of d , after removal of an e- from the outermost shell will attain the
relatively stable e- configuration with half-filled 3d orbitals. ∴, the Fe ions are easily oxidized to Fe .
2+ 3+

[1m]
(iv) Variable oxidation states of d-block elements [1m] allow electron transfer between reactants and
products by means of catalyst changing betwen two oxidation states. [1m]
Any one example of transition metals or its compound as catalyst
V2O5
e.g. 2SO2 + O2 à 2SO3 [1m]
(example must involve redox process, accept Haber process, but not accept hydrogenation of alkene.)
(v)

[1m]
-
(b)(i) MnO4 is unstable in the presence of sunlight / undergoes photodecomposition; [1m]
it will decompose to form a brown solid / MnO2 [1m]
(ii) Cobalt(II) chloride, in anhydrous state is blue [1/2m] in colour. After absorption of water / forming
complex with water, [1m] it changes colour to pink. [1/2m]
3+
(iii) In aqueous solution, Fe exists as aquo-complex.
-
Addition of OH causes the formation of a brown ppt.
3+ -
[Fe(H2O)6] + 3OH à Fe(OH)3(s) + 6H2O(l) [1m]
- 3+ 3- 3+
In the presence of excess CN , Fe forms a very stable complex [Fe(CN)6] , concentration of free Fe
ions is lowered [1m]
∴ addition of 2M NaOH cannot cause [Fe ][OH ] to exceed the Ksp of Fe(OH)3. [1m]
3+ - 3

1994 AL CHEM P II – Page 4

6.(a) Sodium hydrogencarbonate in the self-raising flour undergoes thermal decomposition to give CO2 gas.
[1m]
∆
2NaHCO3(s) à Na2CO3(s) + CO2(g) + H2O(g)
[1/2m for product; 1/2m for balanced equation]
The CO2 gas produced causes the cakes to rise. [1m]
+ -
(b) The small size of Li ion and the relatively large HCO3 ions do not favour the formation of a stable crystal
lattice. [1m]
- +
(accept explanation in terms of the polarization of HCO3 ion by Li ion)
+
The highly exothermic hydration energy of Li ion, causes lithium hydrogencarbonate to exist in solutions
only. [1m]
(c) 2PbO2(s) à 2PbO(s) + O2(g) [2m]
(Award 1 mark for an unbalanced equation)
(d)(i) Tin(II) chloride hydrolyses in water to give insoluble Sn(OH)Cl [1/2m + 1/2m]
SnCl2 + H2O Sn(OH)Cl + HCl [1m]
thus the solution appears cloudy.
+
Addition of H shifts the equilibrium to the left, the solution becomes clear. [1m]
- 2-
Addition of OH forms Sn(OH)4 [1m]
(Since Sn(OH)2 in amphoteric), thus the solution becomes clear.
-
(ii) Hydrolysis of SnCl4 involves the attack e pairs in H2O: on the vacant lower energy d orbitals of Sn [1m]

[1m]
In C, there is no low energy vacant 3d orbitals for the incoming water molecule ∴ No low energy
hydrolysis reaction path for CCl4. [1m]
(e) Reaction with acidified KMnO4 [1m for method]
-
SnCl2 decolorizes the purple colour of MnO4
while SnCl4 does not. [2m for observation]
or pass H2S(g) into aqueous solutions of the two chlorides (1m)
SnCl2 gives a brown ppt. while (1m)
SnCl4 gives a yellow ppt. (1m)

7.(a) Structural isomerism - occurence of more than one structure for a given molecular formula. [1/2m
+1/2m]
Stereoisomerism - occurence of more than one configuration (different arrangements of groups in space)
for a given structural formula. [1/2m + 1/2m]
Examples to illustrate the two types of isomers. [1/2m + 1/2m]
(b)(i)

Empirical formula of G is C2H4O

Since, relative molecular mass of G is between 80 to 100
∴ molecular formula of G is C4H8O2 [1m]
G is a sweet smelling liquid ∴ it is an ester [1m]
Possible structures of G (any 3 of the structure shown below):

(any 3) [2m]
(ii) Structure possesses a chiral carbon. [1m]

1994 AL CHEM P II – Page 5

 H H H3C H
H2C CHCH2 C *
CH3 H3C HC CH C* CH3 H2C C C* CH3
Cl Cl Cl

H CH3
H2C CH C* C2H5 H2C CH C* CH2Cl
Cl H
(iii) J reacts with PCl5 to give HCl
∴ J carries an -OH group [1/2m]
Strong oxidation of J gives , J is a 1,2-disubstituted aromatic compound. [1m]
Mild oxidation of J gives a ketone,
J is a 2° alcohol [1/2m]
Possible structures of J

[2m]
Iodoform test / I2 in NaOH [1m]
Observation:

and will gives a pale yellow ppt. while will not [1m]

8.(a) (Any chemically reasonable transformation are acceptable.)

(i)

[3m]
(ii)

[3m]
(iii)
O O CH3 O
NaOH
CH3CH2 C CH2CH3 CH3CH2 C CH
_ CH3CH2 C CH2CH3
O CH3 OH
O CH3 O CH3
CH3CH2 C C C CH2CH3
H H
CH3CH2 C C C CH2CH3 H2/Ni CH3CH2 C C C CH2CH3 CH2CH3
H conc.H2SO4
CH2CH3 CH2CH3 180oC
[OUT]
(b)(i) e.g. CH3CH2Br
_
H3C CH3
CH3
C Br NC C Br NC C
_ H H + Br
CN H H H H

[3m]
-
(ii) No, HCN is a weak acid, it ionizes only slightly in water. In HCN(aq), [CN (aq)] is low, hence rate of
SN2 reaction with R-Br is low.[2m]
(c)(i) 4,5-dimethylhex-1-ene [1m]
1994 AL CHEM P II – Page 6
 (ii) propyl butanoate [1m]
(iii) 4-hydroxyhexan-3-one

9.(a)(i) P:

[1m]
(ii) Q:

(iii) R:
[1m]

(iv)

[1m]
- +
(v) U & V: (CH3)3CCOO Na & (CH3)3CCH2OH [2m]
2
(b)(i) There are 4 C-H bonds and 1 C=C bond is an ethene molecule. The C's in ethene are sp hybridized.
2
The C-H bond is formed by overlapping of a sp hybrid oribtal with an atomic orbital of H. [1m]
The C=C bond consisted of a sigma bond and a pi bond. These bonds are formed by the overlapping
of two unhybridized p orbitals on C's respectively. [1m]

2
Since for sp hybridization, the hybrid orbitals are arranged on a triangular plane.
∴ Ethene molecule is planar and C-C-H bond angles are 120° [1m]
or C=C π bond (1/2m) by overlapping of Pz orbitals (1/2m)
C-C σ bond (1/2m) by overlapping of sp orbitals (1/2m)
2

shape - planar (1/2m); triangular or the angle is 120° (1/2m)

1994 AL CHEM P II – Page 7

(ii)

(iii)

[2m]
(iv) The structure of PVC can be represented by

The attraction between polymer chain of PVC is dipolar attraction while that between PE polymers is
van der Waal's force which is weaker when compared with former. Hence PVC is more rigid and more
durable than PE. [1m]
(v) Incineration of PVC produces CO2, H2O ... and also HCl(g) which causes more serious pollution
problem than the incineration of PE (no HCl is produced). [1m]

1994 AL CHEM P II – Page 8