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General Certificate of Education

June 2009
Advanced Level Examination
CHEMISTRY
CHM5
Unit 5 Thermodynamics and Further Inorganic Chemistry
Thursday 18 June 2009

9.00 am to 11.00 am

For this paper you must have

a calculator.

For Examiners Use

Question

Mark

Question

Mark

Time allowed: 2 hours

1
Instructions
Use black ink or black ball-point pen.
Fill in the boxes at the top of this page.
Answer all questions.
Answer the questions in Section A and Section B in the spaces
provided. Answers written in margins or on blank pages will not
be marked.
All working must be shown.
Do all rough work in this book. Cross through any work you do not
want to be marked.
The Periodic Table/Data Sheet is provided on pages 3 and 4. Detach
this perforated sheet at the start of the examination.
Section B questions are provided on a perforated sheet. Detach this
sheet at the start of the examination.
Information
The maximum mark for this paper is 120.
The marks for questions are shown in brackets.
This paper carries 20 per cent of the total marks for Advanced Level.
You are expected to use a calculator where appropriate.
Write your answers to the questions in Section B in continuous prose,
where appropriate.
You will be assessed on your ability to use an appropriate form and
style of writing, to organise relevant information clearly and
coherently, and to use specialist vocabulary, where appropriate.

2
3
4
5
6
7
8
9

Total (Column 1)
Total (Column 2)
TOTAL

Examiners Initials

Advice
You are advised to spend about 1 hour on Section A and about
1 hour on Section B.

(JUN09CHM501)

APW/Jun09/CHM5

CHM5

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SECTION A
Answer all questions in the spaces provided.

1 Use the following enthalpy data to answer the question.

H / kJ mol1
Mg(s) Mg(g)

+ 150

Mg(g) Mg+(g) + e

+ 736

Mg+(g) Mg2+(g) + e

+ 1450

O(g)

+ 248

1
2 O2(g)

O(g) + e O(g)

142

O(g) + e O2(g)

+ 844

Mg(s) + 12 O2(g) MgO(s)

1

602

(a) Define the term standard enthalpy of formation.

.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
(3 marks)

(b) Suggest why the enthalpy change for the process represented by the equation below is
endothermic.
O(g) + e O2(g)
.............................................................................................................................................
(1 mark)

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(03)

89

90 103 Actinides

Actinium

Ac

227

57

Lanthanum

La

138.9

39

Yttrium

88.9

21

Scandium

Sc

45.0

Lanthanides

88

* 58 71

87

Ra

Radium

Fr

223.0

Francium

56

226.0

55

Ba

Barium

132.9

Cs

38

137.3

37

Caesium

Sr

Strontium

Rb

85.5

Rubidium

20

87.6

19

Ca

Calcium

Potassium

12

40.1

39.1

Magnesium

Sodium

11

Mg

23.0

Na

24.3

Be

Beryllium

Li

9.0

II

72

Hafnium

Hf

178.5

40

Zirconium

Zr

91.2

22

Titanium

Ti

47.9

24

25

Tc

98.9

26

Ru

101.1

Iron

Fe

55.8

43

44

45

Sm

150.4

77

Iridium

Ir

192.2

46

Eu

152.0

78

Platinum

Pt

195.1

Protactinium

Th

Thorium

91

Pa

59
231.0

92

Uranium

238.0

60

93

Neptunium

Np

237.0

61

94

Plutonium

Pu

239.1

62

95

Americium

Am

243.1

63

Pm

144.9

76

Osmium

Os

190.2

Palladium

Pd

106.4

28

Nickel

Ni

58.7

Europium

Nd

144.2

75

Rhenium

Re

186.2

Rhodium

Rh

102.9

27

Cobalt

Co

58.9

Praseodymium Neodymium Promethium Samarium

Pr

140.9

74

Tungsten

183.9

42

Molybdenum Technetium Ruthenium

Mo

95.9

58

90

Mn

54.9

Li
Lithium

6.9

Chromium Manganese

Cr

52.0

232.0

Cerium

Ce

140.1

73

Tantalum

Ta

180.9

41

Niobium

Nb

92.9

23

Vanadium

50.9

atomic number

relative atomic mass

Key

47

96

Curium

Cm

247.1

64

Gadolinium

Gd

157.3

79

Gold

Au

197.0

Silver

Ag

107.9

29

Copper

Cu

63.5

30

Cf

252.1

66

Dysprosium

Dy

162.5

81

Thallium

Tl

204.4

49

Indium

In

114.8

31

Gallium

Ga

13
69.7

50

Es

(252)

67

Holmium

Ho

164.9

82

Lead

Pb

207.2

Tin

Sn

118.7

32

Germanium

Ge

14
72.6

Silicon

Si

28.1

Carbon

12.0

IV

97

98

99

Berkelium Californium Einsteinium

Bk

247.1

65

Terbium

Tb

158.9

80

Mercury

Hg

200.6

48

Cadmium

Cd

112.4

Zinc

Zn

65.4

Aluminium

Al

27.0

Boron

10.8

III

100

Fermium

Fm

(257)

68

Erbium

Er

167.3

83

Bismuth

Bi

209.0

51

Antimony

Sb

121.8

33

Arsenic

As

15
74.9

Phosphorus

31.0

Nitrogen

14.0

The atomic numbers and approximate relative atomic masses shown in the table are for use in the examination unless stated
otherwise in an individual question.

Lithium

1
6.9

Hydrogen

1.0

The Periodic Table of the Elements

101

Mendelevium

Md

(258)

69

Thulium

Tm

168.9

84

Polonium

Po

210.0

52

Tellurium

Te

127.6

34

Selenium

Se

16
79.0

Sulphur

32.1

Oxygen

16.0

VI

102

Nobelium

No

(259)

70

Ytterbium

Yb

173.0

85

Astatine

At

210.0

53

Iodine

126.9

35

Bromine

Br

17
79.9

Chlorine

Cl

35.5

Fluorine

19.0

VII

He

103

Lawrencium

Lr

(260)

71

Lutetium

Lu

175.0

86

Radon

Rn

222.0

54

Xenon

Xe

131.3

36

Krypton

Kr

18
83.8

Argon

Ar

39.9

10

Neon

Ne

2
20.2

Helium

4.0

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Gas constant R = 8.31 J K1 mol1

Table 1
Proton n.m.r. chemical shift data
Type of proton

/ppm

RCH3

0.71.2

R2CH2

1.21.4

R3CH

1.41.6

RCOCH3

2.12.6

ROCH3

3.13.9

RCOOCH3

3.74.1

ROH

0.55.0

Table 2
Infra-red absorption data

(04)

Bond

Wavenumber/cm1

CH

28503300

CC

7501100

16201680

16801750

CO

10001300

OH (alcohols)

32303550

OH (acids)

25003000

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5
1

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(c) Use the data from the table and the incomplete BornHaber cycle below to calculate
the standard enthalpy of lattice formation for magnesium oxide.
Mg2+(g) + O2(g)
Mg2+(g) + O(g) + 2e
2+

Mg (g) +

1
2 O2(g)

+ 2e

Mg2+(g) + O(g) + e

Mg+(g) + 12 O2(g) + e
Mg(g) + 12 O2(g)
Mg(s) + 12 O2(g)
MgO(s)

.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
(3 marks)
1

(d) The enthalpies of lattice formation for calcium oxide and for barium oxide are
3513 kJ mol1 and 3152 kJ mol1 respectively. Suggest why the lattice enthalpy for
CaO is more negative than that for BaO
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
(2 marks)

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6
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DO NOT WRITE ON THIS PAGE

ANSWER IN THE SPACES PROVIDED

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7
2

(a) Barium oxide reacts with water to form aqueous barium hydroxide.

(a) (i)

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Write an equation for this reaction.

...................................................................................................................................
(1 mark)

(a) (ii)

Calculate the pH of the solution formed by reacting 2.00 g of BaO with water
and making up to 100 cm3 of solution at 298 K. Give your answer to two
decimal places.
(Kw = 1.00 1014 mol2 dm6 at 298 K)
...................................................................................................................................
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(5 marks)

(b) State why the pH of a solution formed by adding an excess of magnesium hydroxide to
water is lower than the pH of the solution formed in part (a) (ii).
.............................................................................................................................................
.............................................................................................................................................
(1 mark)

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8
3

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(a) Give the equation that relates the free-energy change for a reaction to the enthalpy
change and the entropy change.
.............................................................................................................................................
(1 mark)

(b) Consider the following equation that represents the first step in the extraction of
titanium.
TiO2(s) + 2C(s) + 2Cl2(g) 2CO(g) + TiCl4(g)

(b) (i)

H = 30 kJ mol1

Deduce the sign of the entropy change for this reaction and explain your answer.
Sign of entropy change ..............................................................................................
Explanation ..............................................................................................................
...................................................................................................................................
...................................................................................................................................
(3 marks)

(b) (ii)

Use your answers to part (a) and part (b) (i) to explain why this reaction will be
feasible at all temperatures.
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
(2 marks)

(b) (iii) Give one reason why, despite being feasible at all temperatures, the reaction is
carried out at 900 C.
...................................................................................................................................
(1 mark)

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9
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(c) The following data refer to the second step in the extraction of titanium.
TiCl4(g)

Na(l)

NaCl(s)

Ti(s)

Standard enthalpy of formation, Hf / kJ mol1

720

411

Standard entropy, S / J K1 mol1

329

58

72

30

(c) (i)

Use the data from the table to calculate values for the enthalpy change and the
entropy change for the following reaction.
TiCl4(g) + 4Na(l) 4NaCl(s) + Ti(s)
Value of H ..............................................................................................................
...................................................................................................................................
...................................................................................................................................
Value of S ................................................................................................................
...................................................................................................................................
...................................................................................................................................
(5 marks)

(c) (ii)

Use your answers to part (c) (i) to calculate the temperature above which this
reaction is not feasible.
(If you have been unable to calculate answers to part (c) (i) you may assume that
the enthalpy change has the value 812 kJ mol1 and the entropy change has the
value 312 J K1 mol1. These are not the correct values.)
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
(3 marks)

15

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10
4

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(a) In terms of electrons, state what happens to the oxidising agent in a redox reaction.
.............................................................................................................................................
(1 mark)

(b) State the value of the standard electrode potential for the following half-equation.
Give a reason why it has this value.
H+(aq) + e

1
2 H2(g)

Value of E .........................................................................................................................
Reason ................................................................................................................................
(2 marks)
4

(c) Consider the electrochemical cell shown below. The aqueous mixture in the right-hand
part of the cell contains the oxidising agent and the reducing agent for that part of the
cell.
V
Zn

ZnSO4(aq)

Salt bridge

Electrode X

K2Cr2O7(aq),
H2SO4(aq) and
Cr2(SO4)3(aq)

State the purpose of the salt bridge and of the electrode X. Identify the substance or
substances from which each of these is made.
Purpose of salt bridge.........................................................................................................
.............................................................................................................................................
Salt bridge is made from.....................................................................................................
Purpose of electrode X .......................................................................................................
.............................................................................................................................................
Electrode X is made from ...................................................................................................
(4 marks)

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11
4

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(d) Give the oxidation state of chromium in K2Cr2O7

.............................................................................................................................................
(1 mark)

(e) Write half-equations for the reactions at each electrode and an overall equation for the
cell reaction.
Positive electrode half-equation
.............................................................................................................................................
Negative electrode half-equation
.............................................................................................................................................
Overall equation for cell reaction
.............................................................................................................................................
(3 marks)

(f) Give the conventional representation (cell diagram) for this cell.
.............................................................................................................................................
(1 mark)

12

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12

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5 The following compounds can be distinguished by observing what happens in test-tube

reactions.
For each pair, suggest a suitable reagent that could be added separately to each compound.
Describe what you would observe in each case. Write an equation or equations where
required.
5

(a) MgCl2(aq) and BaCl2(aq)

Reagent ...............................................................................................................................
Observation with MgCl2(aq) ..............................................................................................
Observation with BaCl2(aq) ...............................................................................................
(3 marks)

(b) CH3COOH(aq) and CH3COCH3(aq)

Reagent ...............................................................................................................................
Observation with CH3COOH(aq).......................................................................................
Observation with CH3COCH3(aq) .....................................................................................
Equation either with CH3COOH(aq) or with CH3COCH3(aq)
.............................................................................................................................................
(4 marks)

(c) KF(aq) and KCl(aq)

Reagent ...............................................................................................................................
Observation with KF(aq) ....................................................................................................
Observation with KCl(aq)...................................................................................................
(3 marks)

(d) CrCl3(aq) and FeCl2(aq)

Reagent ...............................................................................................................................
Observation with CrCl3(aq)................................................................................................
Observation with FeCl2(aq)................................................................................................
(3 marks)

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(e) AlCl3(aq) and MgCl2(aq)

Reagent ...............................................................................................................................
Observation with AlCl3(aq) ................................................................................................
Observation with MgCl2(aq) ..............................................................................................
Equation(s) with AlCl3(aq) .................................................................................................
.............................................................................................................................................
(4 marks)

17
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SECTION B
Detach this perforated sheet.
Answer all questions in the spaces provided on page 14 and pages 1720 of this booklet.
6

(a) Define the term electronegativity.

(b) Explain why the bonding in sodium chloride is ionic but there is covalent bonding in
anhydrous aluminium chloride.
(3 marks)

(c) The table below shows the melting points of some Period 3 chlorides.

Melting point / K

(2 marks)

MgCl2

SiCl4

PCl5

987

203

435

By considering the structures and the bonding involved explain the following.
6

(c)

(i) MgCl2 has a high melting point.

(c)

(ii) SiCl4 is a liquid at room temperature but PCl5 is a solid with a higher melting
point.
(5 marks)

(d) Write equations for the reactions that occur when each of MgCl2, SiCl4 and PCl5 is
added to separate samples of water.
(3 marks)

(a) State the meaning of each of the terms ligand and co-ordination number as they apply
to transition metal complex ions.
(2 marks)

(b) Explain why transition metal ions are usually coloured.

(c) The colour of an aqueous solution containing pink [Co(H2O)6]2+(aq) ions can be
changed by

(c) (i)

changing the ligand but keeping the co-ordination number the same

(3 marks)

(c) (ii)

changing both the co-ordination number and the ligand

(3 marks)

(c) (iii) changing the oxidation state.

(2 marks)

(3 marks)

(4 marks)

In each case, identify the reagent or reagents required to bring about the change, give
the formula of the cobalt-containing ion formed and state its colour.

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8

(a) State the meaning of each of the terms rate of reaction and catalyst.

(2 marks)

(b) Identify the main feature of transition metal ions that enables them to act as good
catalysts for redox reactions.
Explain how and why Fe2+(aq) ions are able to catalyse the reaction between I(aq)
(6 marks)
ions and S2O82(aq) ions. Illustrate your answer with equations.

(c) For each of the following processes, suggest a catalyst and write an equation for the
overall reaction.

(c) (i)

the cracking of octane to form 2,2-dimethylbutane and one other product

(2 marks)

(c) (ii)

the removal of nitrogen monoxide from the exhaust gases of a petrol engine
(2 marks)

(c) (iii) the acylation of benzene.

(a) Bromine molecules react with propene at room temperature. Outline a mechanism for
this reaction.
(4 marks)

(b) Bromine atoms are involved in the reaction between bromine and methane to form
bromomethane. Write equations for the two propagation steps in this reaction.
(2 marks)

(c) When heated, bromine molecules can be atomised as shown in the equation below.
Br2(g)

(3 marks)

2Br (g)

In an experiment, 6.30 g of bromine in a sealed container of volume 2.00 dm3 were

heated to a high temperature. Under these conditions, at equilibrium, 20% of the
bromine is converted into atoms.
9

(c) (i)

Write an expression for the equilibrium constant, Kc, for this reaction.

(1 mark)

(c) (ii)

Calculate a value for Kc under these conditions.

(c) (iii) Suggest what happens to the value of Kc when the reaction is carried out at a
higher temperature. Explain your answer.
(3 marks)

(5 marks)

END OF QUESTIONS

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