H2 Chemistry

2012 A-level Paper 3 Answer Scheme (QUESTION & MARK SCHEME)

1

TOS

(a)

Aluminium oxide is amphoteric in nature due to its high charge density of Al3+
polarizing O2- , causing Al2O3 to be ionic with partial covalent character.

[5]

9.1 (h)

[1]

3 (b)(ii)

[1]

3 (c)

Al2O3 , like MgO acts like a base/ reacts with acid:

Al2O3 (s) + 6HCl(aq) 2AlCl3 (aq) + 3H2O (l)
MgO (s) + 2HCl(aq) MgCl2 (aq) + H2O (l)
Al2O3 , like P4O10 acts like an acid/ reacts with base:
Al2O3 (s) + 2OH- (aq) + 3H2O (l) 2[Al(OH)4]- (aq)
P4O10 (s) + 12OH- (aq) 4PO43- (aq) + 6H2O (l)
Note: Accept ionic / balanced chemical equations.
Explanation is not limited to Al2O3 being amphoteric. More specific reason for
the acidic/basic nature required. Students need more effort in remembering
equations.

(b)

(i)

Some students do not draw the valence of Cl completely. Arrow need not be
shown, focus is on drawing dot and cross diagram.

(ii)

Shape of AlCl3 = trigonal planar

Some students misread the questions and put tetrahedral, thinking it is Al2Cl6.

(iii)

By LCP, an increase of temperature results in the equilibrium position to shift to

the right to favour the endothermic reaction that will absorb the excess heat .
Hence, more AlCl3 (g) will be formed.

[2]

7 (b)

4 (c)

Some students do not give reason for the shift of eqm.

(iv)

PV = nRT
PV = (mRT)/Mr
Mr = mRT/PV
= (1.5 8.31 500)/ [1.16 105 250 10-6]
= 214.9
Wrong calculation made due to conversion of units. Mr must be expressed in 1
d.p.

[1]

(v)

214.913 = 267 x + 133.5 y

x+y=1
y= 1-x
214.913 = 267 x + 133.5 (1-x)
214.913 = 267 x + 133.5 133.5x
133.5x = 81.413
x= 0.6098
y= 0.3902
Quite a handful of students were unable to manipulate the expression
mathematically.

[2]

(vi)

PAl C l

= mole fraction Ptotal

= 0.6098 1.16 105
= 7.08 104 Pa
P A l C l = 0.3902 1.16 105 = 4.53 104 Pa
2

[1]

4 (c)

[3]

7e

(vii)

Kp =

P2A l C l / P A l C l
3

= 2.89 X 104 Pa

Students used the wrong values for the partial pressures. Some expressed Kp
in terms of concentrations. Units were wrongly derived for some despite the
simplicity of the expression.

(c)

(i)

[2]

Compound A

Compound B

10.2 (f)
(i)

(ii)

Add alkaline iodine to each unknown, warm the mixture.

Compound A: brown I2 decolourised, yellow ppt of triiodomethane formed.
Compound B: brown I2 solution remains unchanged, no yellow ppt formed.
(observations)

Product of Compound A:

[2]

10.5 (e)

[3]

6 (d) (ii)

and CHI3

Some students used KMnO4(aq), heat to oxidized benzylic H of B without

knowing both A and B will react.
2

(a)

(i)

Cl2/ Cl half cell

I 3 / I half cell
direction of electron flow or polarity of the electrode and salt bridge
The iodine/iodide half cell was often incorrectly drawn as a gaseous setup.

(ii)

The oxidizing powers of chlorine and iodine can be measured through the
above setup at 298K, 1 atm by measuring the potential difference, Ecell
between the half cells of Cl2(g)/Cl (aq) and I2(s)/I (aq) with a voltmeter.
Cl2 + 2e
I2 + 2e

[3]

6 (d) (ii)

2Cl E = +1.36 V
2I E = +0.54 V

Ecell = +1.36 0.54

= +0.82 V [Since Ered Cl2/Cl is more positive than Ered I2/I (with quoted data
booklet values)
This shows that chlorine has a greater oxidizing power than iodine .
Students do not quote values and calculate the E0 cell. Few commented about
the greater oxidizing power of iodine.
Examiners Report:

(b)

(iii)

Cl2 + 2e
2Cl E = +1.36 V
I2 + 2e
2I E = +0.54 V
Overall: Cl2 (g) + 2I (aq)
I2 (aq) + 2Cl (aq)
Note: State symbols are not required and no need to quote.

[1]

6 (h)

(i)

Fe3+ + e
Fe2+ E = +0.77 V
I2 + 2e
2I E = +0.54 V
Overall: 2Fe3+(aq) + 2I - (aq)
I2 (aq) + 2Fe2+ (aq) Ecell = +0.23 V
Note: no need to quote.
The equilibrium sign was missing.

[1]

6 (h)

(ii)

[Fe(CN)6]3 (aq) + e

[2]

6 (f)

[Fe(CN)6]4(aq) E = +0.36 V

[Fe(H2O)6]3+ + e

[Fe(H2O)6]2+

E = +0.77 V

In the presence of CN, the Fe(III) ion is less oxidizing than it is in water as the
Ered is more negative.
Thus, equilibrium shifts left.
Many students misinterpreted question and focused on how CN stablised the
Fe3+ as it is a stronger ligand.
Examiners Report:

(c)

The hydrolysis of C2H5X will increases in reactivity (C2H5Cl < C2H5I). This is
because the bond length of CCl < CI, hence, it is more difficult to break
the CCl bond > CI bond. This is due to the greater orbital overlap between
C and Cl as compared to C and I, hence, stronger bond strength.
Some quote values from the data booklet which is not required of the
questions. Explanation was not given in relation to bond strength.

[1]

10.3 (c)

(d)

(i)

[2]

10.3 (a)
(i)

(ii) *

[2]

10.3 (a)
(i)
10.4 (d)
(ii)

Examiners Report:

(e)

(i)

H2SO4 (aq), heat (acidic hydrolysis) or NaOH(aq), heat (alkaline hydrolysis)

[1]

(ii)

For NaOH (aq), Heat (alkaline hydrolysis)

For phenylbutazone:

For phenobarbital:

For H2SO4(aq), Heat (acidic hydrolysis)

For phenylbutazone:

For phenobarbital:

[4]

Few students give hydrolysed products depending on medium specified in (e)

(i).

(a)

(i)

M(NO3)2 (s) MO (s) + 2NO2 (g) + O2 (g)

[1]

9.2 (c)

(ii)

As the cationic radius of M2+ increases down the group, the charge remains
constant down the group but the charge density of the cation decreases down
the group. Hence, the polarizing power of the cation decreases and M2+ is less
able to distort the electron cloud of the anion. N-O covalent bond is
respectively less weakened. Hence, more energy is required to decompose the
compound down the group as the thermal stability of the nitrates increases.

[2]

9.2 (c)

Students must differentiate between the explanation of Fajans rule for ionic
with covalent compounds with this explanation for ease of thermal
decomposition.

(b)

(i)

[2]

Students were unable to draw information from the step questions. Arrows were

incorrectly drawn.
Examiners Report:

(ii)

Overall: 2N2O5 4NO2 + O2

Wrong balancing of equations.

[1]

(iii)

Working: (no marks)

N2O5 NO2 + NO3
2NO3 N2O6
N2O6 2NO2 + O2

[2]

10.2 (c)

[2]

8 (b) (iii)

[1]

10.2 (g)
(i)

Arrows were drawn incorrectly. Students do not realise this is a free radical reaction.
The nitrogen oxide structures were also drawn incorrectly.

(iv)

The first step is the slow step because this is a first order reaction with respect to N2O5
where one 1 mole of N2O5 will be in the rate determining step.
Reason for slow step were given incorrectly by many students.

(c)

(i)

When N2O5 is in solution, there is presence of the electrophile NO2+ and NO3-. Since,
there is H+ as a by-product of electrophilic substitution, which will possibly react with
NO3-, hence, HNO3 (nitric acid) could be formed.
Only some students were able to use their understanding from electrophilic
substitution mechanism to predict nitric acid.

(ii)

[2]

10.2
(g) (i)

[1]

5 (e)
(i)

-Arrows, intermediate, slow

-H+ reacting with NO3The last step to show how nitric acid is formed is usually not shown.
Examiners Report:

(d)

(i)

+92.5 = +33.2 + X (+5.0)

X = + 64.3 kJ mol-1
Hf of NO3 = + 64.3 kJ mol-1

(ii)

Y= 2(+33.2) 2(+64.3)
Y = 62.2 kJmol-1
H of reaction 2 = 62.2 kJmol-1

[2]

5 (e)
(i)

[4]

5 (i)
5 (l)

Some students included BE(O=O) in the calculation, which showed conceptual deficiency.

(e)

For reaction 1 and 2, the S is positive (due to the increase in the no. of moles of gaseous
molecules hence more disorderliness)
Since H is positive for reaction 1 and using G = H TS , G is negative and
spontaneous only at higher temperatures. For reaction 2, H is negative hence G is
negative and more spontaneous at all temperatures. Hence reaction 2 is likely to be more
spontaneous.
Explanations given were not adequately elaborated, especially in comparing the signs.

(a)

(b)

(i)

Particle
1 +
H
DT+
He2+

Charge/Mass
1/1

1/3
2/4

Angle
+ 15
- 7.5
+ 5
+ 7.5

[3]

2 (b)

[1]

2 (b)

x/12 => 5
x/12 = 1/3
x=4
The overall charge of particle R is +4.

(c)

(ii)

Mass number = 12
No. of neutrons = 12 6 = 6
No. of electrons = 6 4 = 2 to give overall +4.

[2]

2 (a)

(i)

Ionic radius: Si4+ < Na+ < Cl-- < P3- (quote from data booklet)

[3]

9.1 (a)

Na+ and Si4+ are isoelectronic hence, given the smaller nuclear charge of Na+, the shielding
effect being the same, the effective nuclear charge of Na+ is smaller than Si4+, hence, less
net electrostatic forces of attraction and larger in ionic size for Na+.
The anions are bigger in ionic size than cations because of the large inter-electronic
repulsion experienced by the electron cloud of the anion due to the presence of an extra
shell of electrons. P3 and Cl are isoelectronic, hence, given the smaller nuclear charge of

P3, the shielding effect being the same, the effective nuclear charge of P3 is smaller than
Cl, hence, less net electrostatic forces of attraction and larger in ionic size.
Quite a number of students did not get full credit for this questions; missing out the
isoelectronic character of the ions. Many did not explain why the anions are bigger than the
cations.
Examiners Report:

(ii)

Si > Na > P4 > Cl2 (implied through explanation)

Si exists as a giant covalent molecule, held by strong tetrahedral network of covalent bonds,
which require highest amount of energy to overcome and, hence, have highest melting
point.
Na exists as a giant metallic lattice, held by strong electrostatic forces of attraction between
the Na+ and the sea of mobile electrons. This requires less energy to overcome as
compared to the strong covalent bonds in Si, thus have a lower melting point.
P4 and Cl2 are simple covalent molecules, held by induced dipole-induced dipole attraction
(id-id) and require less energy to overcome than the metallic bonding in sodium. P4 has a
larger electron cloud than Cl2 hence, require more energy to overcome stronger id-id
compared to that of Cl2.
Many students did not compare why P4 and Cl2 have lower mpt than Na and why Na has
lower mpt than Si. They merely described the interactions.

Examiners Report:

[3]

9.1 (a)

(d) (i)

[2]

side chain ionic interaction

N C terminus ionic interaction.

Students fail to read questions properly and drew the conventional diagram of
polypeptide chain. Understanding of the question is crucial.

Examiners Report:

(ii)

[1] for each type of interaction formed

No need to use the amino acids specified in the tetrapeptide chain.

[3]

10.7 (n)

(e)

(i)

(ii)

Ester

[1]

10 (b)

[2]

10.7 (f)

(a)

Students swopped the first two steps which can be correct.

Examiners Report:

Note the drawing of the structure of CN-R vs NC-R.

[5]

10.5 (b)
10.3 (a)
(i)
10.6 (a)

(b) (i)

Geometric isomerism
Some students wrote steoreoisomerism for this part which is not specific enough.

[2]

10.4 (a)
(v)
10.1 (g)

(ii)

Concentrated H2SO4, 180C

[1]

10.4 (a)
(v)

(iii)

The higher the pKa, the lower the acidity.

[1]

7 (j)

The isomer, K produce the more stable mono-anion as it has a very low pKa 1.9. This
mono-anion is so stable that the second protonation does not take place very easily
given the high second pKa of K isomer.
Students rarely explain the second part about the high pKa value for the second
protonation.
Examiners Report:

(iv)

[2]

K [1]

This mono-anion K is more stable than J because intra-molecular hydrogen bonding is

formed between the COO- and the adjacent non ionized COOH. This makes the monoanion very stable, shifting the acid dissociation equilibrium to the right, resulting in strong
acidity.
OR

Very few students are able to recognize the H-bonding in the cis form of K.
Examiners Report:

3 (f)

(c)

Observatio
n

Deduction

L reacts with
NH3 to give
M

M gives salt
with NaOH

Neutralisation, forming carboxylate ion COONa+ or

M
decolorizes
Br2

M contains a double bond; electrophilic addition happens or

L is a neutral
compound
L does not
react with
Na metal
L does not
give a ppt
with 2,4
DNPH

L does not contain any alcohol or carboxylic group [no mark]

L does not contain any any alcohol or carboxylic group [no mark]
L does not contain carbonyl group, could have O=C-O- group [no
mark]

10.6 (h)
10.2 (d)
(1i)

[6]

L (acid anyhydride) derived from K due to the proximity of COOH to eliminate

water. [K and reason]

M
Reasons were not adequately given for the derivation of L, though most students get the
structure of L right.

(d)

[3]

This question was adequately answered by many students.

The End! All the Best for the A-Level 2013! =)

10.4 (a)
(iv)
10.5 (e)