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07

NANYANG JUNIOR COLLEGE

Promotional Examination
H2 CHEMISTRY

9746/02

Paper 2

26 September 2007

JC 1/2007

1 hour

Mark Scheme

2
1

Sodium halides such as NaF and NaCl, while having similar appearances and
physical properties, have completely different practical uses in real life. NaCl
is the main ingredient in table salt while NaF is commonly used in toothpaste.
The table below shows the melting points and lattice energy data for NaF,
NaCl and MgCl2:
Table 1
Lattice Energy / kJ mol-1
Experimental
Calculated
Percentage
value
value
discrepancy
923
910
1.43

Compound

Melting
Point /
C

NaF

996

NaCl

801

786

769

2.21

MgCl2

714

2526

2326

8.60

(a) With reference to their structure and bonding, compare the melting points
of NaF and NaCl and account for the difference.
[3]
o Both have giant ionic structures
o with strong electrostatic attraction between oppositely charged
ions.
o Cl- is larger than F-,
o hence interionic distance is larger for NaCl
o Ionic bonds are weaker in NaCl,
o hence melting point is lower.
Every pt mark. Round down to nearest whole number

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3
The lattice energy of an ionic compound can be determined in two ways, by
using experimental data in a Born-Haber cycle, or from theoretical
calculations. However, the two methods yield lattice energy data that do not
necessarily agree. This is due to the fact that theoretical calculations are
based on the assumption that the compounds are purely ionic.
Table 1 shows the percentage discrepancy between experimental lattice
energy and calculated lattice energy for NaF, NaCl and MgCl2.
(b) Explain why MgCl2 has a larger percentage discrepancy between its
experimental and calculated lattice energy, compared to NaCl.
[2]

Mg2+ is smaller and more highly charged than Na+ (higher charge
density)
Cl- is large and easily polarised
Mg2+ is able to polarize the electron cloud of Cl- to a greater extent
Hence MgCl2 possess greater covalent character

Every pt mark. Round down to nearest whole number

NaCl is also the raw material used to produce chlorine. Industrially, chlorine
gas is produced by the electrolysis of concentrated sodium chloride solution
(commonly known as brine).
The industrial process is carried out in a particular diaphragm cell, as shown
below:
Figure 1

Concentrated
NaCl(aq)

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4
In this particular industrial diaphragm cell (Figure 1), the cost of electricity is
$22 / dm3 of chlorine gas produced at room temperature and pressure. The
operating current of the cell is 1.50 x 103 A.
(c) Calculate the hourly chlorine gas production (in moles) in this industrial
diaphragm cell.
[2]
Q = I t = 1.50 x 103 x 3600 = 5.4 x 106 C - 1 mk
ne = 5.4 x 106 / 96500 = 55.95 mol
Since 2Cl- Cl2 + 2e
nCl2 = 55.95 / 2 = 27.97 mol - 1 mk (no ecf)

(d) Hence, deduce the hourly electricity cost incurred during the operation of
this industrial diaphragm cell.
[1]
VCl2 = 27.97 x 24.0 = 671.28 dm3
Hourly electricity cost = 671.28 x 22 = $14768 - 1 mk (ecf)

(e) Using relevant data from the Data Booklet, explain the need to use
concentrated sodium chloride solution, rather than dilute sodium chloride
solution in the production of chlorine.
[2]
E
+1.36
+ 0.40

2ClCl2 + 2e
O2 + 2H2O + 4e

4OH-

1 mk

As E (O2/OH-) is less positive, OH- will be oxidized preferentially if dilute

sodium chloride is used.
Hence concentrated sodium chloride is required to ensure oxidation of
Cl-.
1 mk for explanation

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5
Using relevant data from the Data Booklet, explain why the same diaphragm
cell cannot be used to produce fluorine from either dilute or concentrated
aqueous NaF.
[1]
2F-

F2 + 2e

+2.87

E (F2/F-) is too positive. Hence F- will not be oxidized even when

concentrated NaF is used.
(f) The chlorine gas produced is an important raw material in the production
of chlorine dioxide (ClO2) which is used as a disinfectant during water
treatment. The oxidising action of ClO2 is as follows:
Cl (aq) + 2H2O(l)

ClO2(aq) + 4H+(aq) + 5e

= + 1.50 V

Use relevant data from the Data Booklet to predict the reaction, if any,
when acidified chlorine dioxide is added to aqueous tin(II) sulphate.
[2]
Calculate the E cell for the reaction and write a balanced equation.

ClO2(aq) + 4H+(aq) + 5e
Sn4+ + 2e
Sn2+

cell =

Cl (aq) + 2H2O(l)

E
+ 1.50
+0.15

1.50 0.15 = +1.35 V (> 0, feasible) - 1 mk

2ClO2(aq) + 8H+(aq) + 5Sn2+ 2Cl (aq) + 4H2O(l) + 5Sn4+

1 mk (no ecf)

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6
2

It is important for industrial chemists to find methods that give maximum yield
while minimising costs. One of the very important factors to consider is the
reaction conditions, namely, temperature and pressure.
The diagram below shows how the percentage (%) yield of a particular
reaction can vary with pressure and temperature.
Figure 2
%
yield

(a) (i) From Figure 2, predict with reasons, whether the reaction is
exothermic or endothermic.
[2]

Exothermic
Increasing the temperature favours the backward reaction more /
results in lesser yield.
Endothermic reaction is the backward reaction.
ALL 3 points 2 m, Exo + 1 point 1 m, Exo only 1 m

(ii) Use Figure 2 to suggest conditions which favour a high yield of the
product.
[1]
Low temp, high pressure
1 or 0 marks

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7
(b) The Haber Process is a very important industrial process which produces
ammonia, and feedstock for the production of nitrogen fertilizer and
explosives,
N2 (g) + 3H2 (g)

2NH3 (g)

A plant operates at around 700 K and 250 atm. The molar ratio of nitrogen
and hydrogen employed is 1:3.
The percentage of ammonia in the equilibrium mixture was found to be 20%.
(i) Find the equilibrium partial pressures of nitrogen, hydrogen and
ammonia gases.
[2]
Method 1:
Initial amt
Change in amt
Eqm amt

N2 (g) + 3H2 (g)

1
3
-x
- 3x
1-x
3-3x

2NH3 (g)
0
+ 2x
2x

n (total) = 1-x+3-3x+2x = (4 2x) mol

2x / 4 2x = 0.2
x = 1/3
PN2 = 1/5 (250) = 50 atm
PH2 = 3/5 (250) = 150 atm
PNH3 = 1/5 (250) = 50 atm
Method 2:
PN2 = 0.20 x 250 = 50 atm
PH2 = (250 50) = 150 atm
PNH3 = (250 50) = 50 atm
mole fraction 1 mark
Partial Pressures- 1 mark
(ii) Hence, calculate the value of Kp at 700 K.
Kp = PNH32 / (PN2 x PH23)
= 1.48 x 10-5 atm-2

[1]

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8
(iii) A method to increase yield is to cool the reaction mixture such that NH3
condenses into a liquid and is drained away as it forms. How does this
method increase the yield?
[1]
As NH3 is removed, by LCP, POE will be shifted to the right to form
more NH3 to minimize the effect in the drop in the amt of NH3.
(c) Apart from studying the reaction conditions, it is also very important to
know the energetics of the reaction.
(i) Given:
2NH3(g) +

O2(g) 2NO2(g) + 3H2O(l) H = 585.2 kJ mol1

N2(g) + 2O2(g) 2NO2(g)

H = + 180.8 kJ mol1

and Hc (H2(g)) = 286.0 kJ mol1

Draw an energy cycle to determine the enthalpy change of reaction in
the Haber Process,
2NH3 (g)
[2]
N2 (g) + 3H2 (g)
H
N2 (g) + 3H2 (g) 2NH3 (g)
+5/2 O2

+5/2 O2

2NO2 (g) + 3H2O (l)

- 1 mark for missing state symbols / not balanced equation

(ii) Hence, state the value of enthalpy change of reaction for the Haber
Process:
[1]
H = +180.8 + 3(-286.0) (-585.2) = - 92 kJ mol-1
(iii) State whether entropy increases or decreases in the Haber Process.
Explain your answer.
[2]
Entropy decreases, no. of gaseous particles on the LHS > RHS, less
no. of ways to arrange the gaseous particles.
1 mark for stating decrease, 1 mark for explain

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9
3

Nitrosyl chloride is a yellow gas obtained as a decomposition product of aqua

regia, a mixture of hydrochloric acid and nitric acid. The resulting mixture was
historically used to dissolve gold. In modern times, it can be produced by the
direct combination of nitrogen monoxide and chlorine gas according to the
equation:
H = +138 kJ mol1

2NO(g) + Cl2(g) 2NOCl(g)

(a)(i) On the axes below, sets of initial reactant concentrations and

hypothetical rate equations are given. For each set of conditions,
sketch the corresponding graph for the given axes.
[4]
Set 1:
rate = k [NO] [Cl2]
[NO] = 0.01 mol dm3
[Cl2] = 1.00 mol dm3

Set 2:
rate = k [Cl2]
[NO] = 1.00 mol dm3
[Cl2] = 0.01 mol dm3

rate

rate

[NO] / mol dm3

Set 3:
rate = k [Cl2]
[NO] = 0.01 mol dm3
[Cl2] = 1.00 mol dm3
[NO]

Set 4:
rate = k [NO] [Cl2]
[NO] = 0.01 mol dm3
[Cl2] = 0.01 mol dm3
[Cl2]

time
1 mark for each graph

[NO] / mol dm3

time

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10
(b) Investigation of the actual reaction gives the following results.
Initial concentrations of
reactants / mol dm3

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Relative rate of
formation of NOCl

[NO]

[Cl2]

0.10

0.10

0.20

0.10

0.30

0.20

18

(i) Deduce the order of reaction with respect to NO.

[1]

Comparing experiments 1 and 3,

When [NO] increases by 2 times, the relative rate increases by 4 times.
Hence, the order of reaction with respect to NO = 2
1 mark for correct order of rxn with correct explanation
(ii) Deduce the order of reaction with respect to Cl2.

[1]

rate = k[NO]2[Cl2]x
Comparing experiments 1 and 3,
18 k(0.30)2 (0.2) x
=
1 k(0.10)2 (0.1) x
18 = 9 (2)x
x
=1

Hence, the order of reaction with respect to Cl2 = 1

1 mark for correct order of rxn with correct explanation

(iii) Write the rate equation for the reaction.

rate = k[NO]2[Cl2]
ECF: rate equation based on answers to (i) & (ii)

[1]

11
(iv) The activation energy for the reaction is +223 kJ mol1, sketch and label
a reaction pathway diagram for the reaction in the axis provided.
[2]

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Energy / kJ mol-1

+223

2NOCl
+138
2NO + Cl2

Reaction pathway
Half-mark for each of the following; total round down
Correct Ea = +223
correctly labeled Reactants
Correct H = +138
correctly labeled Products
4 Compounds with the molecular formula C5H11Br show two types of isomerism,
structural and optical.
(a) The full structural formula of one of the isomers is given below. Draw its
structural formula (condensed).
[1]

Br

C
H

H
H

H
H

H
One of the following: (do not penalize if Br is bracket)
CH3C(CH3)BrCH2CH3
or (--BrC2H5)
Structural formula (condensed): .
or (--BrC2H5)
(CH3)2CBrCH2CH3
CH3CH2CBr(CH3)2

or (C2H5C--)

CH3CH2C(CH3)Br(CH3)

or (C2H5C--)

12
(b) In the boxes below, draw structural formulae for four other structural
isomers (at least one must be optically active).
[4]
H

H H H H
1-bromopentane

Br

Br

C* C

H H H H
2-bromopentane

Br

Br

H H H H
3-bromopentane

C
H

C* C

H
H
C

2-bromo-3-methylbutane
H
Br

C* C

C
H

1-bromo-2-methylbutane

Br
H

H
H

C
H

H
1-bromo-2,2-dimethylpropane

1-bromo-3-methylbutane

Br

1 mark for any structure (can be condensed, skeletal, full, displayed)

(c) Using your answer in (b), draw diagrams to illustrate how one of the above
molecules gives rise to optical isomerism.
[1]

C2H5
BrH2C

H
CH3

CH(CH3)2

C2H5
H
H3C

CH2Br

H3C

1-bromo-2-methylbutane

H3C

H
Br

CH(CH3) 2
H
Br

CH3

2-bromo-3-methylbutane

CH2CH2CH3

CH2CH2CH3

H
H
Br
Br
2-bromopentane

End of Paper

CH3

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