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CHEMISTRY
CHM5
Unit 5 Thermodynamics and Further Inorganic Chemistry
(including Synoptic Assessment)
Friday 24 January 2003 Afternoon Session
In addition to this paper you will require:
a calculator.
Mark
Number
1
2
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 marked.
The Periodic Table/Data Sheet is provided on pages 3 and 4. Detach this
perforated sheet at the start of the examination.
3
4
5
6
7
8
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.
The following data may be required.
APW/0103/CHM5
Total
(Column 1)
Total
(Column 2)
TOTAL
Examiners Initials
Mark
LEAVE
MARGIN
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SECTION A
Answer all questions in the spaces provided.
(a)
At high temperatures, aluminium chloride exists in the vapour phase as the molecule
AlCl3. On cooling, two molecules of AlCl3 combine by co-ordinate bonding to form
molecules of Al2Cl6.
(i)
State the shape of the AlCl3 molecule and give the bond angle.
Shape .................................................................................................................................
Bond angle ........................................................................................................................
(ii)
Sketch the structure of Al2Cl6 and mark on your sketch the value of one of the
bond angles.
(iii)
(b)
(i)
(ii)
Describe what you would observe when aqueous sodium carbonate is added to
aqueous aluminium chloride. Write an equation for the reaction.
Observations .....................................................................................................................
.............................................................................................................................................
Equation ............................................................................................................................
.............................................................................................................................................
(7 marks)
13
APW/0103/CHM5
APW/0103/CHM5
Lanthanides
89
Actinium
Ac
227
57
Lanthanum
La
138.9
39
Yttrium
88.9
21
Scandium
Sc
45.0
90 103 Actinides
* 58 71
88
Radium
Francium
87
Ra
226.0
223.0
Fr
56
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
Pr
140.9
74
Tungsten
183.9
42
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
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
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
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.
Li
1
6.9
Hydrogen
1.0
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
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
APW/0103/CHM5
Bond
Wavenumber/cm1
CH
28503300
CC
7501100
16201680
16801750
CO
10001300
OH (alcohols)
32303550
OH (acids)
25003000
LEAVE
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(a)
Write equations for the reactions which occur when the following compounds are added
separately to water. In each case, predict the approximate pH of the solution formed
when one mole of each compound is added to 1 dm3 of water.
Sodium oxide
Equation ......................................................................................................................................
pH of solution formed ................................................................................................................
Sulphur dioxide
Equation ......................................................................................................................................
pH of solution formed ................................................................................................................
(4 marks)
(b)
When silicon dioxide and carbon are heated in a stream of chlorine gas, silicon
tetrachloride and carbon monoxide are formed.
(i)
(ii)
(iii)
Explain, in terms of their structure and bonding, why silicon tetrachloride has a
lower melting point than phosphorus pentachloride.
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
(7 marks)
11
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Use the data in the table below to answer the questions which follow.
Substance
Hf / kJ mol
1
Fe2O3(s)
1
S / J K mol
(a)
824.2
87.4
Fe(s)
0
C(s)
0
27.3
CO(g)
CO2(g)
110.5
393.5
197.6
213.6
5.7
The following equation shows one of the reactions which can occur in the extraction of
iron.
Fe2O3(s) + 3CO(g)
(i)
2Fe(s) + 3CO2(g)
Calculate the standard enthalpy change and the standard entropy change for this
reaction.
Standard enthalpy change ................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
Standard entropy change .................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
(ii)
APW/0103/CHM5)
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(b)
The reaction shown by the following equation can also occur in the extraction of iron.
Fe2O3(s) + 3C(s)
2Fe(s) + 3CO(g)
H = +492.7 kJ mol1
(c)
Calculate the temperature at which the standard free-energy change, G , has the same
value for the reactions in parts (a) and (b).
.......................................................................................................................................................
.......................................................................................................................................................
.......................................................................................................................................................
.......................................................................................................................................................
(3 marks)
15
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Use the standard electrode potential data in the table below to answer the questions which
follow.
E /V
Ce4+(aq) + e
MnO4(aq)
+ 2H (aq) +
Fe
(a)
Mn2+(aq) + 4H2O(l)
+1.51
2e
2Cl(aq)
+1.36
VO2+(aq)
Fe2+(aq)
+0.77
H2SO3(aq) + H2O(l)
+0.17
+ 8H (aq) + 5e
3+(aq)
SO24 (aq)
+1.70
Cl2(g) +
VO2+(aq)
Ce3+(aq)
+ 4H (aq) + 2e
+ H2O(l)
+1.00
Name the standard reference electrode against which all other electrode potentials are
measured.
.......................................................................................................................................................
(1 mark)
(b)
(ii)
APW/0103/CHM5
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(c)
2+
Pt|H2SO3(aq), SO2
4 (aq)||MnO4(aq), Mn (aq)|Pt
Calculate the e.m.f. of this cell and write an equation for the spontaneous cell reaction.
Cell e.m.f. .....................................................................................................................................
Equation ......................................................................................................................................
.......................................................................................................................................................
.......................................................................................................................................................
(3 marks)
(d)
(i)
Which one of the species given in the table is the strongest oxidising agent?
.............................................................................................................................................
(ii)
Which of the species in the table could convert Fe2+(aq) into Fe3+(aq) but could
(e)
Use data from the table of standard electrode potentials to deduce the cell which would
have a standard e.m.f. of 0.93 V. Represent this cell using the convention shown in
part (c).
.......................................................................................................................................................
(2 marks)
12
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APW/0103/CHM5
10
(a)
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(b)
(c)
(d)
(e)
APW/0103/CHM5
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11
SECTION B
Answer all questions in the space provided on pages 13 to 20 of this booklet.
(a)
Water, copper(II) ions and nitrogen dioxide are formed when copper metal reacts with
concentrated nitric acid.
Write half-equations for the reactions occurring and use these to construct an overall
ionic equation for the reaction.
(3 marks)
(b)
When copper reacts with dilute nitric acid, gaseous nitrogen monoxide is formed as
shown by the following equation.
3Cu + 8HNO3
Calculate the volume of nitrogen monoxide, measured at 330 K and 98.0 kPa, which is
formed when 1.25g of copper metal reacts completely with an excess of dilute nitric acid.
(6 marks)
(c)
(a)
The strength of adsorption onto the active sites on the surface of a heterogeneous
catalyst helps to determine the activity of the catalyst.
Explain how heterogeneous catalysts work, give one example of a reaction catalysed in
this way and discuss why different catalysts have different activities.
(8 marks)
(b)
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12
The conversion of compound A into compound B can be achieved in two steps as shown
below.
CH3
|
CH3 C CH2Br
|
H
Step 1
CH3
|
CH3 C CH3
|
Br
Step 2
The intermediate compound, X, has an absorption at 1650 cm1 in its infra-red spectrum.
(a)
(2 marks)
(b)
For each step in this conversion, give the reagents and essential conditions required and
outline a mechanism.
(11 marks)
(c)
Show how the number of peaks in their proton n.m.r. spectra would enable you to
distinguish between compounds A and B.
(2 marks)
(a)
The lone pair of electrons on the nitrogen atom is involved in the separate reactions of
ammonia with hydrogen chloride, silver chloride and ethanoyl chloride.
Write equations for the reaction of ammonia with each of these compounds. State the
role of ammonia in each of these reactions.
(7 marks)
(b)
Explain, in terms of the forces between particles, why the following compounds, which
have similar relative molecular masses, have different melting points.
Compound
Formula
Mr
Melting point/K
Pentane
CH3(CH2)3CH3
72
143
Butanone
CH3CH2COCH3
72
187
Propanoic acid
CH3CH2CO2H
74
252
(8 marks)
END OF QUESTIONS
APW/0103/CHM5