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General Certificate of Education

June 2007
Advanced Level Examination
CHEMISTRY
CHM5
Unit 5 Thermodynamics and Further Inorganic Chemistry
Monday 25 June 2007

9.00 am to 11.00 am

For this paper you must have

a calculator.

For Examiners Use

Question

Time allowed: 2 hours

Instructions
Use blue or black ink or ball-point pen.
Fill in the boxes at the top of this page.
Answer all questions in Section A and Section B in the spaces
provided. 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.
Mark allocations 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.
Your answers to the questions in Section B should be written 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.

Mark

Question

Mark

3
4
5
6
7
8

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.

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SECTION A
Answer all questions in the spaces provided.

1 Consider the incomplete BornHaber cycle and the table of data below.

Mg2 (g) + 2Cl (g)

Mg(s) + Cl2(g)

MgCl2(s)
Name of standard enthalpy
change

Substance to which
enthalpy change refers

Enthalpy of atomisation
Enthalpy of atomisation
Enthalpy of formation
First ionisation enthalpy
Electron affinity
Enthalpy of lattice formation

chlorine
magnesium
magnesium chloride
magnesium
chlorine
magnesium chloride

Value of enthalpy change

/ kJ mol1
+121
+150
642
+736
364
2493

(a) Complete the Born-Haber cycle above by writing the appropriate chemical formulae,
with state symbols, on the dotted lines.
(4 marks)
(b) Use the cycle and the values given in the table to calculate the second ionisation
enthalpy of magnesium.
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(3 marks)
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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

39.1

Potassium

12

40.1

11

Mg

Magnesium

Na

Sodium

24.3

23.0

Beryllium

Lithium

Be

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

Nd

144.2

75

Rhenium

Re

186.2

44

Pm

144.9

76

Osmium

Os

190.2

Sm

150.4

77

Iridium

Ir

192.2

45

Rhodium

Rh

102.9

27

Cobalt

Co

58.9

Pa
Protactinium

Th

Thorium

91

231.0

232.0

92

Uranium

238.0

60

93

Neptunium

Np

237.0

61

94

Plutonium

Pu

239.1

62

Praseodymium Neodymium Promethium Samarium

Pr

140.9

74

Tungsten

183.9

42

Molybdenum Technetium Ruthenium

Mo

95.9

59

90

Mn

54.9

Li
Lithium

6.9

Chromium Manganese

Cr

52.0

58

Cerium

Ce

140.1

73

Tantalum

Ta

180.9

41

Niobium

Nb

92.9

23

Vanadium

50.9

atomic number

relative atomic mass

Key

95

Americium

Am

243.1

63

Europium

Eu

152.0

78

Platinum

Pt

195.1

46

Palladium

Pd

106.4

28

Nickel

Ni

58.7

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

Al

Cf

252.1

66

Dysprosium

Dy

162.5

81

Thallium

Tl

204.4

49

Indium

In

114.8

31

Gallium

Ga

13
69.7

Aluminium

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

5
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.

Li

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

10

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

Neon

Ne

2
20.2

Helium

4.0

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

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Bond

Wavenumber/cm1

CH

28503300

CC

7501100

16201680

16801750

CO

10001300

OH (alcohols)

32303550

OH (acids)

25003000

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(c) The standard enthalpies of hydration of the Mg2+ and the Cl ions are 1920 kJ mol1
and 364 kJ mol1, respectively. Use this information and data from the table in part (a)
to calculate the enthalpy of solution of magnesium chloride.
.............................................................................................................................................
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.............................................................................................................................................
.............................................................................................................................................
(3 marks)
(d) The standard enthalpy of solution of ammonium chloride, NH+4Cl, is +15 kJ mol1.
(i) Explain why ammonium chloride dissolves spontaneously in water even though
this process is endothermic.
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
(2 marks)
(ii) A 2.0 g sample of ammonium chloride is dissolved in 50 g of water. Both
substances are initially at 20 C.
Calculate the temperature change and the final temperature of the solution.
Assume that the specific heat capacity of the solution is 4.2 J K1 g1.
Temperature change .................................................................................................
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
Final temperature of solution ...................................................................................
(5 marks)
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2 Data for the following reaction, which represents the reduction of aluminium oxide by
carbon, are shown in the table below.
Al2O3(s) + 3C(s) 2Al(s) + 3CO(g)
Substance

Hf / kJ mol1

S / J K1 mol1

Al2O3(s)

1669

51

C(s)

Al(s)

28

CO(g)

111

198

(a) Calculate the values of H , S and G for the above reaction at 298 K and
suggest why this reaction is not feasible at 298 K.
H .....................................................................................................................................
.............................................................................................................................................
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S ......................................................................................................................................
.............................................................................................................................................
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G .....................................................................................................................................
.............................................................................................................................................
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Reason why this reaction is not feasible at 298 K .............................................................
.............................................................................................................................................
(8 marks)

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(b) Calculate the temperature above which this reaction is feasible.

(If you have been unable to calculate values for H and S in part (a) you may
assume that they are +906 kJ mol1 and +394 J K1 mol1 respectively. These are not
the correct values.)
.............................................................................................................................................
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(2 marks)
(c) The reaction between aluminium oxide and carbon to form aluminium and carbon
monoxide does not occur to a significant extent until the temperature reaches a value
about 1000 K above that of the answer to part (b). Give one reason for this.
.............................................................................................................................................
(1 mark)
(d) State the method used to reduce aluminium oxide on an industrial scale. Give the
essential conditions for this industrial process.
Method ...............................................................................................................................
Conditions ..........................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
(3 marks)

14

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3 The table below shows some standard electrode potentials.

E /V
Fe3+(aq) + e Fe2+(aq)

+ 0.77

Cr3+(aq) + e Cr2+(aq)

0.41

Fe2+(aq) + 2e Fe(s)

0.44

Zn2+(aq) + 2e Zn(s)

0.76

Cr2+(aq) + 2e Cr(s)

0.91

(a) Predict the products, if any, when the following substances are mixed. In each case
use E values from the table to explain your answer.
(i) iron metal with aqueous zinc(II) ions
Products, if any .........................................................................................................
Explanation ..............................................................................................................
...................................................................................................................................
(ii) aqueous iron(III) ions with aqueous chromium(II) ions
Products, if any .........................................................................................................
Explanation ..............................................................................................................
...................................................................................................................................
(5 marks)
(b) Calculate the e.m.f. of the following standard cell and deduce an equation for the
overall cell reaction.
Zn(s)|Zn2+(aq)||Cr3+(aq),Cr2+(aq)|Pt
e.m.f. ...................................................................................................................................
Equation .............................................................................................................................
(2 marks)

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(c) Chromium(III) ions are weakly acidic in aqueous solution as shown by the following
equation.
[Cr(H2O)6]3+(aq)

[Cr(H2O)5(OH)]2+(aq) + H+(aq)

The value of Ka for this reaction is 1.15 104 mol dm3.

Calculate the pH of a 0.500 mol dm3 solution of [Cr(H2O)6]3+(aq).
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
(5 marks)
(d) State what you would observe after addition of the following reagents to separate
aqueous solutions containing [Cr(H2O)6]3+ ions.
In each case give the formula of the chromium-containing product.
(i) an excess of NaOH(aq)
Observation(s) ..........................................................................................................
...................................................................................................................................
Formula of product ...................................................................................................
(ii) Na2CO3(aq)
Observation(s) ..........................................................................................................
...................................................................................................................................
Formula of product ...................................................................................................
(5 marks)

17

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(a) Give the meaning of the term electronegativity.

.............................................................................................................................................
.............................................................................................................................................
(2 marks)
(b) State and explain the trend in electronegativity across Period 3 from Na to Cl.
Trend ..................................................................................................................................
Explanation ........................................................................................................................
.............................................................................................................................................
(3 marks)
(c)

(i) Name the main type of bonding in each of the oxides MgO and P4O10
Bonding in MgO .......................................................................................................
Bonding in P4O10 .....................................................................................................
(ii) Explain how the type of bonding in P4O10 can be predicted by a consideration of
electronegativity.
...................................................................................................................................
...................................................................................................................................
(3 marks)

(d) Write equations for the reaction of Na2O and of SO2 with water.
Equation for Na2O .............................................................................................................
Equation for SO2 ................................................................................................................
(2 marks)
(e) Write an equation for the reaction of MgO with dilute hydrochloric acid.
.............................................................................................................................................
(1 mark)
(f) Write an equation for the reaction of P4O10 with an excess of aqueous sodium
hydroxide.
.............................................................................................................................................
.............................................................................................................................................
(1 mark)

12
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SECTION B
Detach this perforated sheet.
Answer all questions in the spaces provided on pages 13 to 20 of this booklet.

(a) Explain why the ester methyl ethanoate has a lower boiling point than its isomer,
propanoic acid.
(2 marks)
(b) A polyester is formed when ethane-1,2-diol reacts with butanedioic acid. Draw the
structure of the repeating unit of this polymer.
Suggest why this polyester begins to melt at a higher temperature than poly(ethene)
which has molecules of a similar size to those in the polyester.
(4 marks)
(c) Outline a mechanism for the formation of an ester by the reaction between ethanoyl
chloride and an alcohol.
(4 marks)
(d) The ester ethyl ethanoate is hydrolysed when it is heated with water in the presence of
an acid catalyst. An equilibrium is established.
CH3COOCH2CH3(l) + H2O(l)

CH3COOH(l) + CH3CH2OH(l)

A 0.50 mol sample of ethyl ethanoate was heated with 4.0 mol of water. At equilibrium,
70 % of the ester was hydrolysed. Calculate a value of Kc for this reaction. (5 marks)

6 One characteristic property of transition metals is variable oxidation state.

(a) For each of the following processes, write two equations to show how the transition
metal catalyst reacts and is reformed. Identify the different oxidation states shown by
the transition metal catalyst in each process.
(i) the Contact Process catalysed by vanadium(V) oxide
(ii) the oxidation of ethanedioate ions by acidified potassium manganate(VII),
autocatalysed by Mn2+(aq) ions.
(6 marks)
(b) Cobalt(II) ions cannot easily be oxidised to cobalt(III) ions in water. Suggest why this
oxidation can be carried out in aqueous ammonia and identify a suitable oxidising
agent.
(3 marks)
(c) Metal ions Q2+ in acidified aqueous solution can be oxidised by aqueous potassium
dichromate(VI).
In a titration, an acidified 25.0 cm3 sample of a 0.140 mol dm3 solution of Q2+(aq)
required 29.2 cm3 of a 0.040 mol dm3 solution of potassium dichromate(VI) for
complete reaction.
Determine the oxidation state of the metal Q after reaction with the potassium
dichromate(VI).
(6 marks)
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7 The reaction scheme below shows a two-stage synthesis of ethane-1,2-diamine,

H2NCH2CH2NH2.
Reaction 1
H2C = CH2

Reaction 2
BrCH2CH2Br

H2NCH2CH2NH2

(a) Suggest a reagent for Reaction 1. Name and outline a mechanism for this reaction.
(5 marks)
(b) Suggest a reagent for Reaction 2. Name the type of mechanism involved and write an
equation for the overall reaction.
(3 marks)
(c) Draw the structure of the complex ion formed when aqueous cobalt(II) ions react with
an excess of ethane-1,2-diamine.
(2 marks)
(d) Ethane-1,2-diamine can be converted into the EDTA4 ion shown below.
OOCCH2

CH2COO

NCH2CH2N
OOCCH2

CH2COO

State why this ion can act as a multidentate ligand.

Write an equation for the reaction of EDTA4 with aqueous cobalt(II) ions. In your
equation represent the ligand by EDTA4
Explain why the EDTA4 ion readily displaces unidentate ligands such as water.
(5 marks)

(a) The compounds CH3CH2Cl and CH3CHCl2 can be distinguished by comparing their
proton n.m.r. spectra.
For each compound, describe its proton n.m.r. spectrum by giving the number of
peaks, the integration ratio and the splitting patterns.
(6 marks)
(b) The following pairs of compounds can be distinguished using the reagents indicated.
Each compound is in a separate aqueous solution. For each one of the compounds,
describe what you would observe and write equations for any reactions that occur.
(i) KBr and KI using chlorine water
(ii) BaCl2 and MgCl2 using dilute sulphuric acid
(iii) CoCl2 and CuCl2 using concentrated hydrochloric acid
(9 marks)

END OF QUESTIONS
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