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General Certificate of Education

June 2008
Advanced Level Examination
CHEMISTRY
Unit 4 Further Physical and Organic Chemistry
Thursday 12 June 2008

CHM4

1.30 pm to 3.00 pm

For this paper you must have

a calculator.

For Examiners Use

Question

Time allowed: 1 hour 30 minutes

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 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.

Mark

Question

Mark

3
4
5
6
7
Total (Column 1)
Total (Column 2)
TOTAL

Information
The maximum mark for this paper is 90.
The marks for questions are shown in brackets.
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.

Examiners Initials

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

(JUN08CHM401)

APW/Jun08/CHM4

CHM4

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SECTION A
Answer all questions in the spaces provided.

1 In this question you are required to calculate the pH values of some acidic solutions.
Give all values of pH to 2 decimal places.
1

(a) Calculate the pH of 0.0380 mol dm3 hydrochloric acid.

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

(b) Calculate the pH of the solution formed when 100 cm3 of pure water are added to
100 cm3 of this 0.0380 mol dm3 hydrochloric acid.
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
(2 marks)

(c) HX is a weak BrnstedLowry acid.

(c)

(i) Explain the terms weak and BrnstedLowry acid as applied to HX.
Weak ..........................................................................................................................
...................................................................................................................................
BrnstedLowry acid ................................................................................................
...................................................................................................................................

(c)

(ii) Write an expression for the dissociation constant, Ka, for the acid HX.
...................................................................................................................................
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...................................................................................................................................

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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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APW/Jun08/CHM4

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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(c) (iii) The pH of 0.0630 mol dm3 solution of HX is 3.48

Calculate the value of Ka for HX.
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
(6 marks)

(d) An aqueous buffer solution which contains 0.0550 mol of a different weak acid, HA,
and 0.0250 mol of NaA in 100 cm3 of solution has a pH of 4.20
The value of Ka for the acid HA is 2.87 105 mol dm3 at 25 C.

(d)

(i) Deduce the pH of the solution formed when 100 cm3 of pure water are added to
100 cm3 of this buffer solution.
...................................................................................................................................

(d)

(ii) Calculate the pH of the solution formed when 10.0 cm3 of 0.130 mol dm3
aqueous sodium hydroxide are added to 100 cm3 of the original buffer solution.
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
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...................................................................................................................................
...................................................................................................................................
(6 marks)

15

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(a) The table below shows the results of three experiments to investigate the rate of
reaction between compounds A and B. All three experiments were carried out at the
same temperature.
Experiment 1

Experiment 2

Experiment 3

Initial concentration of A/mol dm3

3.90 102

7.80 102

7.80 102

Initial concentration of B/mol dm3

9.60 102

2.40 102

1.20 102

Initial rate/mol dm3 s1

5.00 105

5.00 105

2.50 105

Use the data in the table to deduce the order of reaction with respect to A and the order
of reaction with respect to B.
Order with respect to A .....................................................................................................
Order with respect to B .....................................................................................................
(2 marks)
2

(b) The reaction between compounds C and D at a given temperature is first order with
respect to C and second order with respect to D.

(b)

(i) Write a rate equation for this reaction.

...................................................................................................................................

(b)

(ii) When the initial concentration of C is 2.50 102 mol dm3 and the initial
concentration of D is 6.65 102 mol dm3, the initial rate of reaction is
1.45 104 mol dm3 s1. Calculate the value of the rate constant at this
temperature and deduce its units.
Calculation ...............................................................................................................
...................................................................................................................................
...................................................................................................................................
Units of rate constant ...............................................................................................
(4 marks)

3 The equation for the catalytic decomposition of hydrazine into its elements is shown below.
N2H4(g)
3

N2(g) + 2H2(g)

(a) A sample of hydrazine and a catalyst were placed in a container and heated to a given
temperature. In the equilibrium mixture of gases produced at a total pressure of
150 kPa, the mole fraction of hydrazine was 0.22

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3

(a)

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(i) Calculate the partial pressure of hydrazine under these conditions.

...................................................................................................................................
...................................................................................................................................

(a)

(ii) Hence, calculate the partial pressure of nitrogen and the partial pressure of
hydrogen in the mixture.
Partial pressure of nitrogen ......................................................................................
...................................................................................................................................
Partial pressure of hydrogen ....................................................................................
...................................................................................................................................
(5 marks)

(b) A different mixture of hydrazine, nitrogen and hydrogen was prepared and allowed to
reach equilibrium in the presence of a catalyst at a temperature T. In this new
equilibrium mixture, the partial pressure of hydrazine was 75.0 kPa, the partial
pressure of nitrogen was 27.0 kPa and the partial pressure of hydrogen was 48.0 kPa.

(b)

(i) Write an expression for the equilibrium constant, Kp, for the decomposition of
hydrazine.
...................................................................................................................................
...................................................................................................................................

(b)

(ii) Calculate the value of Kp at this temperature and deduce its units.
Calculation ...............................................................................................................
...................................................................................................................................
...................................................................................................................................
Units .........................................................................................................................
(4 marks)

(c) The gas mixture from part (b) was transferred to a different container of half the
original volume. When equilibrium was re-established at temperature T, the partial
pressure of hydrazine had more than doubled. Explain why halving the volume has
not simply doubled the partial pressure of hydrazine.
.............................................................................................................................................
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(2 marks)
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(a) A polymer is formed when propane-l,3-diamine reacts with pentanedioic acid. Name
the type of polymerisation reaction which occurs and draw the structure of the
repeating unit of the polymer formed.
Type of polymerisation .......................................................................................................
Repeating unit

(3 marks)
4

(b) The repeating unit shown below represents the polymer commonly known as
poly(vinyl acetate) or PVA.
CH2

CH
O
C

CH3
4

(b)

(i) Draw the structure of the monomer which is used to make PVA.

(b)

(ii) Draw the repeating unit of the polymer formed when PVA reacts with an excess
of aqueous sodium hydroxide.

(2 marks)

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(c) The amino acids alanine and serine are shown below.
H
H2N

C
CH3
alanine

H
COOH

H2N

COOH

CH2OH
serine

(c)

(i) Draw the structures of the two dipeptides formed by the reaction of alanine with
serine.

(c)

(ii) Draw the structure of the zwitterion of serine.

(c) (iii) Draw the structure of the organic compound formed when alanine reacts with
methanol in the presence of a small amount of concentrated sulphuric acid.

(c) (iv) Draw the structure of the organic compound formed when one molecule of
serine reacts with two molecules of ethanoyl chloride.

(6 marks)
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5 Consider the reaction sequence shown below.

Reaction 1
C4H8

HBr

a
CH3

H
C

CH2

b
CH3

Br
E
5

(a)

Reaction 2
NH3

CH3

CH2

CH3

NH2
G

(i) Name the mechanism for Reaction 1.

...................................................................................................................................

(a)

(ii) Compound F is the only product formed in Reaction 1. Deduce the structure of
compound E.

(2 marks)
5

(b) Name and outline a mechanism for Reaction 2.

Name of mechanism ...........................................................................................................
Mechanism

(5 marks)
5

(c) Compound G is a primary amine with molecular formula C4H11N

In Reaction 2, the percentage conversion of F into G is 53.4%.

(c)

(i) Calculate the mass of G formed in Reaction 2 from 10.0 g of F.

...................................................................................................................................
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...................................................................................................................................
...................................................................................................................................

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5

(c)

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(ii) Suggest a reason, other than experimental technique, for the relatively low
percentage conversion of F into G in Reaction 2.
...................................................................................................................................
...................................................................................................................................
(4 marks)

(d) Predict the total number of peaks in the proton n.m.r. spectrum of F. State the splitting
pattern of the peak for the protons labelled a and the splitting pattern of the peak for
the protons labelled b.
Total number of peaks ........................................................................................................
Splitting pattern of the peak for the protons labelled a ....................................................
Splitting pattern of the peak for the protons labelled b ....................................................
(3 marks)

(e) Draw the structure of the following isomers of G.

(e)

(i) The isomer which is a primary amine and has two peaks in its proton n.m.r.
spectrum.

(e)

(ii) The isomer which is a secondary amine and has four peaks in its proton n.m.r.
spectrum.

(e) (iii) The isomer which is a tertiary amine.

(3 marks)
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SECTION B
Detach this perforated sheet.
Answer both questions in the space provided on page 12 and pages 15-20 of this booklet.

6 Propanoyl chloride, CH3CH2COCl, reacts with water and with benzene.

6

(a) Write a balanced equation for the reaction of propanoyl chloride with water.
Name and outline a mechanism for this reaction.
(6 marks)

(b) Write a balanced equation for the overall reaction of propanoyl chloride with benzene.
Identify a suitable catalyst for this reaction. Write equations to show how this catalyst
reacts and how it is regenerated.
Name and outline a mechanism for the reaction involving benzene.
(8 marks)

Turn over for the next question

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(a) Describe, by giving reagents and stating observations, how you could distinguish
between the compounds in the following pairs. Use one simple test-tube reaction for
each pair.

(a)

and

(i)

P
CH3
7

(a)

(ii)

H3C

OH

H3C

and

(a) (iii)

H3C

CH3

CH3

CH3

H3C

and

CH2OH

OH

CH2CH3

(9 marks)

(b) Compound T in part (a)(iii) has a mass spectrum with a peak at m/z = 57
Draw the structure of the ion responsible for this peak and write an equation for the
fragmentation of the molecular ion of T to produce this species.
(3 marks)

(c) Identify a solvent used for samples in proton n.m.r. spectroscopy.

Give the names of compounds V and W, shown below, and describe how they can be
distinguished using their proton n.m.r. spectra.
O
H3C

H3CO
C

O
H3C

O
C

C
O

H3CO

W
(4 marks)

END OF QUESTIONS

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