46th INTERNATIONAL

CHEMISTRY OLYMPIAD
2014
UK Round One
STUDENT QUESTION BOOKLET
*****

The time allowed is 2 hours.

Attempt all 5 questions.
Write your answers in the special answer booklet.
In your calculations, please write only the essential steps in the answer booklet.
Always give the appropriate units and number of significant figures.
You are provided with a copy of the Periodic Table.
Do NOT write anything in the right hand margin of the answer booklet.
The marks available for each question are shown below; this may be helpful when
dividing your time between questions.

Question

Total

Marks
Available

13

18

16

65

Some of the questions will contain material you will not be familiar with. However, by logically
applying the skills you have learnt as a chemist, you should be able to work through the
problems. There are different ways to approach the tasks even if you cannot complete certain
parts of a question, you may still find subsequent parts straightforward.
1

56
137.34

Ra

88

55
132.91

Fr

87

+Actinides

*Lanthanides

89

Ac+

72
178.49

57
138.91

59
140.91

Pa
91

58
140.12

Th

90
232.01
92
238.03

60
144.24

Nd

93

Np

61

Pm

75
186.2

Re

94

Ir

97

Bk

1 nm = 1 109 m

96

Cm

Am

66
162.50

Pb

Er

100

Fm

Te

34
78.96

Se

16
32.06

101

Md

69
168.93

84

Cl

Yb

No
102

85

Lu

Lr
103

86

Rn

54
131.30

Xe

36
83.80

Kr

18
39.95

Ar

10
20.18

71
174.97

At

53
126.90

35
79.904

Br

17
35.45

70
173.04

Po

52
127.60

Tm

83
208.98

Bi

51
121.75

Sb

33
74.92

As

15
30.97

68
167.26

82
207.2

67
164.93

99

Sn

32
72.59

Ge

50
118.69

Ho

Es

Si
14
28.09

0 C = 273 K

98

Cf

Tl
81
204.37

Dy

80
200.59

Hg

49
114.82

In

Cd
48
112.40

31
69.72

Ga

30
65.37

65
158.93

Tb

79
196.97

Au

64
157.25

95

Ag
47
107.87

Gd

78
195.09

Pt

46
106.4

Pd

29
63.55

63
151.96

Eu

77
192.2

62
150.4

Pu

Rh
45
102.91

Sm

76
190.2

Os

44
101.07

Ru

NA = 6.02 1023 mol1

Pr

74
183.85

Ce

73
180.95

Ta

Hf

La*

43

Tc

28
58.71

Zn

Ba

42
95.94

Mo

27
58.93

Cu

12

Cs

41
92.91

40
91.22

39
88.91

Nb

26
55.85

Ni

11

38
87.62

Zr

25
54.94

Co

10

37
85.47

24
52.00

Fe

Sr

23
50.94

Mn

Rb

22
47.90

21
44.96

Cr

20
40.08

19
39.102

Ti

Sc

Ca

13
26.98

Al

9
19.00

Ne

12
24.31

8
16.00

Mg

7
14.01

11
22.99

6
12.01

Na

5
10.81

4
9.01

3
6.94

symbol
atomic number
mean atomic mass

Be

17

Li

16

2
4.003

15

1
1.008

14

He

13

18

1. This question is about controlling phosphate levels

Although phosphorus compounds are essential in our diet,
too much phosphate ion, PO43, in our blood can be
harmful. One treatment for high phosphate levels uses a
drug called Fosrenol, the active ingredient of which is
lanthanum carbonate.
Once the chewed tablet is swallowed, the carbonate first
reacts with the hydrochloric acid present in the stomach.
Then the lanthanum ions react with any phosphate ions
present to give a precipitate of lanthanum phosphate.
Lanthanum phosphate is essentially completely insoluble
in water.
All lanthanum compounds in this question contain
lanthanum in the +3 oxidation state.

(a)

(i)

Give an equation for the reaction between lanthanum carbonate and hydrochloric
acid.

(ii)

Give an ionic equation for the formation of lanthanum phosphate.

Lanthanum carbonate may be prepared by simply mixing aqueous solutions of lanthanum

nitrate and sodium carbonate.
(b)

Write a balanced equation for this reaction.

The lanthanum carbonate precipitated by the previous reaction is usually the octahydrate. The
first sample of pure anhydrous lanthanum carbonate was prepared by dissolving lanthanum
oxide in aqueous trichloroethanoic acid to form lanthanum trichloroethanoate. Heating this
solution for six hours gave the desired carbonate, trichloromethane, and carbon dioxide.
(c)

(i)

Draw the displayed formula for trichloroethanoic acid.

(ii)

Give the equation for the reaction between lanthanum oxide and trichloroethanoic
acid.

(iii)

Give the equation for the formation of lanthanum carbonate.

The lanthanum carbonate contained in the Fosrenol tablets is prepared by mixing aqueous
solutions of lanthanum chloride and ammonium hydrogencarbonate. During this reaction,
carbon dioxide gas is given off.
(d)

Give an equation for this reaction.

Fosrenol is sold in different sizes of tablet, 1000 mg, 750 mg, and 500 mg. The number
refers to the mass of lanthanum ions contained in the tablet.
(e)

(i)

Calculate the mass of lathanum carbonate dihydrate contained in the 1000 mg

tablet.

(ii)

Calculate the mass of phosphate ion removed after taking a single 1000 mg tablet
of Fosrenol.
3

2. This question is about a sodium street lamp

Many of our streets are lit
by the extremely energy
efficient low-pressure
sodium discharge lamps.
The light appears mainly
yellow, but a spectroscope
reveals a number of
colours present, each with
a particular frequency.
Careful analysis of the
spectrum enables us to
determine the first
ionization energy of
sodium.

The so-called ground state of an atom is where all the electrons are in their lowest possible
energy levels.
(a)

Give the complete electronic configuration for the ground state of sodium in terms of the
relevant s and p sub-shells.

The valence-shell electron is the electron easiest to remove from a neutral sodium atom.
(b)

What is the valence-shell electron of sodium?

The familiar yellow colour of a sodium flame is actually due to an excited electron in a sodium
atom essentially falling from a 3p orbital to the 3s. The wavelength for this transition is
589.8 nm.
The energy, E, (in joules) corresponding to light of wavelength

(m) is given by the equation:

h is Plancks constant = 6.626 1034 J s

where

c is the speed of light = 2.998 108 m s1.

(c)

Calculate the energy for the 3p to 3s transition in:

(i)

J (atom1)

(ii)

kJ mol1.

The atomic emission spectrum of sodium includes a series of lines which all fall on a straight
line when (1 / wavelength) is plotted against (1 / n2), where n is the integer shown in the
following table.
Wavelength / nm

466.6

498.0

568.1

818.1

The origin of the linear relationship is due to fact that the (1 / n2) is proportional to the
ionization energy (I.E.) of an excited sodium atom after the valence electron has been
promoted to the nd shell:

where k is an arbitrary constant, and n is the principal quantum number, e.g. n =1 for the 1s
shell; 2 for the 2s and 2p shell; 3 for the 3s, 3p and 3d shell and so on.
[Note for the graph, n cannot be one or two since there is no 1d or 2d shell.]
(d)

What does this ionization energy of the excited nd electron tend to as the electron is
removed from successively higher d shells? Circle one of the following answers in the
answer booklet.
one

zero

infinity

the constant k

Each of the atomic emission lines included in the table and graph are due to transitions where
the valence electron drops from an excited d shell to the 3p shell in the neutral sodium atom.
(e)

(f)

Give an expression for the energy change of these transitions in terms of I.E.(nd), and
I.E.(3p) (the ionization energy of the excited sodium atom after the valence electron has
been promoted to the 3p).

I.E.(3p) in J (atom1).

(i)

Use the graph to determine

(ii)

What is the ionization energy of the ground state of sodium in kJ mol1?

3. This question is about spot cream

The drug tazarotene (sold under the trade names of
Zorac or Tazorac) can be prescribed as a cream that
can be applied to the skin to help to treat acne and
certain other skin conditions. It is commonly sold as a
0.05% cream by mass.

(a)

The molar mass of tazarotene is 351.46 g mol1. Assuming that tazarotene cream has a
density of 0.90 g cm3, calculate the concentration of tazarotene in the cream in mol dm3.

The synthesis of tazarotene is shown below. Not all of the reaction by-products are shown.
The synthesis begins with the conversion of 2-chloro-5-methylpyridine to Ester B.

(b) Draw the structure of Compound A and Ester B.

The second part of the synthesis begins with thiophenol, which is converted into Compound I
by a number of steps.

(c)

Draw the structures of Compounds D, E, F and I, and anions C and G.

6

(d) How would you classify the reaction of Compound H into Compound I?
Circle one of the following answers in the answer booklet.
Oxidation

Reduction

Addition

Elimination

Substitution

Finally, Compound I is treated with a very strong base to form anion J.

Anion J can be reacted with Compound B to form tazarotene.

(e)

Suggest a structure for Anion J.

(f)

How many signals would you expect to see in the 13C NMR spectrum of tazarotene?

Tazarotene is actually a pro-drug, meaning it is metabolised to its active form when inside the
body.
The active form has a molar mass of 323.41 g mol1 and two fewer signals in its 13C NMR
spectrum than tazarotene.
(g) Suggest a structure for the active form of the drug.

4. This question is about bombardier beetles

Bombardier beetles get their name from the defence
mechanism that they have when attacked, whereby
they shoot a hot chemical spray at their attackers. In
their abdomen they have two separate chambers, one
containing an aqueous solution of hydrogen peroxide
and the other an aqueous solution of an organic
compound, denoted here as A.
When the beetle is attacked, fluid from both chambers is squirted into a mixing chamber which
contains enzymes. One of these enzymes, catalase, catalyses the breakdown of hydrogen
peroxide into oxygen and water.
(a)

(i)

Write a balanced equation for this reaction.

(ii)

How would you classify this reaction? Circle one of the following answers in the
answer booklet.

Oxidation

Reduction

Disproportionation

Hydrolysis

Dehydration

Some of the intermediates produced during the breakdown of hydrogen peroxide react with the
organic compound, A, to give a product B. The overall equation for the reaction can be
considered as the result of A reacting with all of the oxygen produced by the equation in part
(a)(i) as in the equation below.
A + O2 B + H2O
(b)

Write an overall equation for the reaction of hydrogen peroxide with A to form B.

The temperature of the mixture ejected from bombardier beetles has been measured to reach
the boiling point of water, considerably hotter than the beetles body temperature, which
matches the surroundings (20 C).
(c)

(i)

Calculate the amount of energy needed to heat 1 dm3 of this mixture by this
amount. Assume the specific heat capacity of the mixture is the same as that of
pure water, 4.18 J g1 K1 and that the density of the mixture is the same as that of
pure water, 1.00 g cm3.

(ii)

Assuming equal volumes of the two solutions are mixed, what is the minimum
concentration of the hydrogen peroxide solution in the beetles hydrogen peroxide
chamber?
The standard enthalpy change for the overall reaction (your answer to part (b)) per
mole of A is 203 kJ mol1.

Compound A is a 1,2,4-trisubstituted benzene, shown

on the right, where there are substituents present at the
positions labelled with an X.

(d)

How many possible structures are there of this 1,2,4-trisubstituted benzene when:
(i)

All of the X substituents are different from each other?

(ii)

Two of the X substituents are identical?

Combustion analysis of Compound A indicates that it contains only carbon, hydrogen and
oxygen.
In compound A, stretching in some of the bonds contained in the X substituents contributes to
characteristic peaks in the IR spectrum of this compound (shown below).
These characteristic peaks are marked I and II on the spectrum.
(e)

Suggest which bond stretches are responsible for I and II.

In compound A, two of the three X substituents are the same (i.e. the substituents are Xa, Xa
and Xb).
The 13C NMR spectrum of compound A contains seven signals.
The 1H NMR spectrum of compound A is shown below.
Peaks III and IV in the 1H NMR spectrum disappear on addition of D2O to the sample.

(f)

(i)

Suggest an identity for the two identical substituents (Xa and Xa).

(ii)

Suggest an identity for the other substituent (Xb).

The protons on the benzene ring in compound A (H1, H2 and H3) can be
assigned by analysis of their coupling constants in the 1H NMR spectrum.
The splitting that is observed in the spectrum due to coupling between two
non-equivalent benzene ring protons in a 1,2-relationship to each other, is
considerably larger than the splitting observed due to coupling between
two non-equivalent benzene ring protons in a 1,3-relationship.
The splitting due to coupling between two non-equivalent benzene ring
protons in a 1,4-relationship is generally too small to be observed.
(g)

Assign one of the signals III-VIII in the 1H NMR spectrum of A to each of the protons H1,
H2 and H3.

Bombardier beetles also use a simpler organic compound, C for the same purpose.
Compound C is a relative of compound A where one of the X substituents is replaced by a
hydrogen atom, making a disubstituted benzene.
The 1H NMR spectrum of compound C only contains two signals.
(h)

Suggest a structure for compound C and hence also a structure for compound A.

Compound C is oxidised to D in the same way that compound A is oxidised to B.

The 1H NMR spectrum of compound D only contains one signal.
(i)

Suggest a structure for compound B and a structure for compound D.

10

5. This question is about fire and ice

Water is able to form a range of cage structures called
clathrates which can contain many small molecules; a
common example is methane hydrate (CH4)x(H2O)y. Methane
hydrates potentially offer a valuable supply of methane to
satisfy our demand for natural gas. Large reserves of methane
hydrates have been found at the bottom of Lake Baikal in
Russia.

(a)

Write the balanced equation for the combustion of methane in excess oxygen.

A 100 g sample of methane hydrate, in the form known as clathrate structure II, (CH4)x(H2O)y
was burnt in excess oxygen in a sealed container. After the reaction had completed and the
products had cooled, 116.92 g of water was recovered from the container, and the gas, when
shaken with excess limewater, gave 84.73 g of CaCO3.
(b)

(c)

(i)

Determine the empirical formula of the methane hydrate in structure II. The molar
mass of CaCO3 is 100.09 g mol1.

(ii)

The molar mass of the hydrate was 2835.18 g mol-1. Determine the molecular
formula of the methane hydrate in structure II.

6.67 1011 kg of methane is estimated to be at the bottom of Lake Baikal. Determine the
volume the gas would occupy if it were to escape the lake during the winter, at 19.0 C.
Use the ideal gas equation pV = nRT where p is the pressure in Pascal, V is the volume
in m3, T is the temperature in Kelvin and R is 8.31 J K1 mol1. [1 atm = 1.0 105 Pa]

The methane hydrate at the bottom of Lake Baikal is found as clathrate structure I having the
formula (CH4)8(H2O)46 and a molar mass of 957.07 g mol1.
(d)

(i)

Determine the percentage by mass of methane within the methane hydrate.

(ii)

Using your answer to part (d)(i) to determine the mass of methane hydrate found at
the bottom of Lake Baikal.

(iii)

The density of methane hydrate crystals is 0.95 g cm3. Calculate the volume of
methane hydrate crystals at the bottom of Lake Baikal.

Clathrate structure I

Clathrate structure II

11

The smallest repeating unit of methane hydrate that contains all the symmetry of the crystal is
known as the unit cell. The unit cell for methane hydrate is a cube that entirely contains 8
methane molecules and 46 waters.
(e)

(i)

What is the mass of a single unit cell?

(ii)

Using the density of methane hydrate (0.95 g cm3) calculate the length of an edge
of the cubic unit cell.

Although the methane and water molecules are not spheres, we can treat them as spheres,
and an effective spherical radius can be estimated for them: 0.14 nm for water and 0.21 nm for
methane.
The formula for the volume of a sphere, V, is given below.

(iii)

Determine the volume of methane and the volume of water within a unit cell.

(iv)

Work out the percentage of space in the crystal that is occupied with molecules.

When (CH4)8(H2O)46 is burnt in excess oxygen at 298 K, the enthalpy change of combustion is
6690.4 kJ mol1.
(f)

Use the data below to determine the enthalpy change when methane hydrate is formed
from methane and water at 298 K.
Standard enthalpy changes of formation at 298 K in kJ mol1:
CH4: 74.8, H2O: 285.8, CO2: 393.5

12

Acknowledgements & References

References for questions
Q1
Process for the preparation of lanthanum carbonate dehydrate
P. R. Muddasani et al., United States Patent US 2012/0058200
The Rare Earth Metals and their Compounds. XII. Carbonates of Lanthanum,
Neodymium and Samarium
M. L. Salutsky and L. L. Quill, J. Am. Chem. Soc., 72, 3306-7, 1950.
Q2
Images from Department of Chemistry, University of Cambridge
Q3
Contemporary Drug Synthesis
J.-J. Li et al., Wiley-Blackwell, 2004
The image is from Shutterstock.
Q4
A Biomimetic Study of the Explosive Discharge of the Bombardier Beetle
N. Beheshti & A. C. McIntosh, Int. Journal of Design & Nature, 1, 1-9, 2006.
Chemical Defence of a Primitive Australian Bombardier Beetle (Carabidae):
Mystropomus regularis
T. Eisner et al., Chemoecology, 2, 29-34,1991.
Photograph from Patrick Coin (Wikipedia)
The 1H NMR spectrum and IR spectrum were adapted from those available from Sigma
Aldrich.
Q5
Image of burning methane hydrate from:
http://energy.gov/articles/new-methane-hydrate-research-investing-our-energy-future
Images of crystal structures from Steve Dutch at the University of WisconsinGreen Bay:
http://www.uwgb.edu/dutchs/Petrology/Clathrate-1.HTM
http://www.uwgb.edu/dutchs/Petrology/Clathrate-2.HTM
Further details about clathrate structures can be found at:
http://www.lsbu.ac.uk/water/clathrat2.html

The UK Chemistry Olympiad is supported by

INEOS is a leading global manufacturer of petrochemicals, specialty chemicals and oil
products. It comprises 19 businesses each with a major chemical company heritage. The
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13

46th INTERNATIONAL
CHEMISTRY OLYMPIAD
2014
UK Round One
MARK SCHEME
Although we would encourage students to always quote answers to an appropriate number
of significant figures, do not penalise students for significant figure errors. Allow where a
students answers differ slightly from the mark scheme due to the use of rounded/nonrounded data from an earlier part of the question.
For answers with missing or incorrect units, penalise one mark for the first occurrence in
each question and write UNIT next to it. Do not penalise for subsequent occurrences in the
same question.

Question

Total

Marks
Available

13

18

16

65

1. This question is about controlling phosphate levels

(a)

(i)

La2(CO3)3 + 6HCl 2LaCl3 + 3H2O + 3CO2

State symbols not required

(ii)

La3+ + PO43 LaPO4

State symbols not required

2La(NO3)3 + 3Na2CO3 La2(CO3)3 + 6NaNO3

(b)

State symbols not required

(c)

(i)
1
Do not accept a molecular formula. Accept if OH bond not drawn out,
but all other bonds must be drawn out.
(ii)

La2O3 + 6CCl3CO2H 2La(CCl3CO2)3 + 3H2O

State symbols not required

(iii)

2La(CCl3CO2)3 + 3H2O La2(CO3)3 + 6CHCl3 + 3CO2

State symbols not required
2LaCl3 + 6NH4HCO3 La2(CO3)3 + 6NH4Cl + 3CO2 + 3H2O

(d)

State symbols not required

(e)

(i)

Amount of La3+ = 1000 mg / 138.91 g mol1 = 7.20 103 mol

Amount of La2(CO3)32H2O = 3.60 103 mol
Molar mass of La2(CO3)32H2O = (2 138.91 + 3 12.01 + 11 16.00
+ 4 1.008) g mol1
= 493.88 g mol

Mass of La2(CO3)32H2O = 493.88 g mol1 3.60 103 mol

= 1780 mg (or 1.78 g)
(ii)

Amount of La3+ = 7.20 103 mol = Amount of PO43

Molar Mass of PO43 = (30.97 + 4 16.00) g mol1 = 94.97 g mol1
Mass of PO43 removed = 7.20 103 mol 94.97 g mol1

= 684 mg (or 0.684 g)

Allow ECF when an incorrect amount of La3+ from (e)(i) has been used
correctly in this calculation.
Question Total

2. This question is about a sodium street lamp

(a)

1s2, 2s2, 2p6, 3s1

(b)

3s

(c)

(i)

Energy = 6.626 1034 J s 2.998 108 m s1 / 589 109 m

= 3.37 1019 J (atom1)

(ii)

Energy per mole = 3.37 1019 J 6.02 1023 mol1

= 2.03 105 J mol1

= 203 kJ mol1
Allow ECF from (c)(i)
(d)

Note this answer is negative as energy is given out. Award one mark for
the expression: Energy change = I.E. (3p) I.E. (nd)

Zero

infinity

Energy change = I.E. (nd) I.E. (3p)

(e)

(f)

the constant k

one

(i)

Intercept = 0.00245 nm1 (Allow values from 0.00243-0.0247 nm1)

I.E. (3p) = 6.626 1034 J s 2.998 108 m s1 2.45 106 m1

= 4.87 1019 J (atom1)

(ii)

Ionisation energy of sodium = I.E. (3p) + E (3s3p)

I.E. (3p) = 4.87 1019 J (atom1) 6.02 1023 mol1
= 293 kJ mol1
Ionisation energy of sodium = 293 kJ mol1 + 203 kJ mol1

= 496 kJ mol1
Allow ECF from (c)(ii) or (f)(i), as long as they have shown that these
two quantities must be added together, and both in the units of kJ mol1
Question Total 9

3. This question is about spot cream

(a)

Effective density of tazarotene = 0.90 g cm3 0.0005 = 0.00045 g cm3

= 0.45 g dm3
Concentration of tazarotene = 0.45 g dm3 / 351.46 g mol1

= 0.00128 M (or 1.28 mM)

(b)

(c)

The alkyne CH bond does not have to be explicitly drawn in (as in

normal skeletal structure drawing).
(d)

Oxidation

Reduction

Addition

Elimination

Substitution

(e)

(f)

20 signals

(g)

Question Total

13

4. This question is about bombardier beetles

(a)

(i)

2H2O2 2H2O + O2

State symbols not required

(ii)

Oxidation

Reduction

Disproportionation

Hydrolysis

Dehydration

Combining 2H2O2 2H2O + O2 and A + O2 B + H2O gives

(b)

H2O2 + A B + 2H2O
(c)

(i)

1
1

Amount of energy = specific heat capacity temp. change mass of water

= 4.18 J g1 K1 80 K 1000 g

= 334 kJ
(ii)

Conc. of H2O2 in mixed solution = energy needed per litre / enthalpy

change per mole of H2O2
= 334 kJ dm3/ 203 kJ mol1
= 1.65 mol dm3

Therefore with equal volumes mixed, conc. of H2O2 initially must be

double this value = 3.30 mol dm3
Award one mark for the value of 1.65 mol dm3, and one mark for the
realisation of the need to double the concentration. Allow ECF from (c)(i).
(d)

(e)

(f)

(g)

(i) 6

(ii) 3

Peak I

OH

Peak II

CH

(i) OH (or hydroxyl)

(ii) CH3 (or methyl)

H1

H2

VII

H3

VI

All correct: two marks, two correct: one mark, one correct: half a mark

(h)

(i)

Question Total 18

5. This question is about fire and ice

CH4 + 2O2 CO2 + 2H2O

(a)

State symbols not required

(b)

(i)

Amount of CH4 = amount of CO2 = amount of CaCO3

Amount of CaCO3 = 84.73 g / 100.09 g mol1 = 0.847 mol
Amount of H2O = 116.92 g / 18.016 g mol1 = 6.49 mol
(CH4)x(H2O)y + 2xO2 xCO2 + (2x+y)H2O
So x = 0.847 mol, and 2x+y = 6.49 mol

Therefore y = 6.49 (2 0.847) = 4.80 mol

Expressing as integers: x = 3, y = 17
Award one mark for correct calculation of the amount of CaCO3 and
H2O, one mark for correct algebraic expression or equivalent and one
mark for final answer. Correct final values score full credit.
(ii)

(CH4)3(H2O)17 Mr = 354.40 g mol1;

therefore 2835.18 g mol1 / 354.40 g mol1 = 8

Molecular formula is (CH4)24(H2O)136

Amount of CH4 = 6.67 1014 g / 16.04 g mol1 = 4.16 1013 mol

(c)

V = nRT/p = 4.16 1013 mol 8.31 J K1 mol1 254 K / 1.0 105 Pa

= 8.78 1011 m3
(d)

(i)

Mass % of methane in methane hydrate =

(8 16.04) g mol1/ 957.07 g mol1

= 13.4%
(ii)

Mass of Baikal methane hydrate = 6.67 1014 g / 0.134 = 4.98 1015 g

Allow ECF from (d)(i)

(iii)

Volume of methane hydrate = 4.98 1015 g / 0.95 g cm3

= 5.24 1015 cm3 (or 5.24 109 m3)

Allow ECF from (d)(ii)

(e)

(i)

Unit cell mass = 957.07 g mol1 / 6.021023 mol1

= 1.59 1021 g

(ii)

Volume of unit cell = 1.59 1021 g / 0.95 g cm3 = 1.67 1021 cm3
Length of unit cell edge = (1.67 1021 cm3) = 1.19 107 cm
One mark for correct volume of unit cell. Allow ECF from (e)(i)

(iii)

Volume of methane in unit cell = 8 4/3 (0.21 109 m)3

= 3.10 1028 m3

Volume of water in unit cell = 46 4/3 (0.14 109 m)3

= 5.29 1028 m3
(iv)

Percentage of space occupied =

(3.10 1028 + 5.29 1028) m3 / 1.67 1027 m3

= 50%
(f)

fHo (CH4)8(H2O)46 = 8fHo(CO2) + 62fHo(H2O) cHo (CH4)8(H2O)46

= (8(393.5) + 62(285.8) (6690.4)) kJ mol1
= 14177.2 kJ mol1
Forming methane hydrate from methane and water has the enthalpy
change
8CH4 + 46H2O (CH4)8(H2O)46
o

rH = (14177.2 8(74.8) 46(285.8)) kJ mol

3
1

= 432 kJ mol

Final answer scores full marks. One mark for a correct value for
fHo (CH4)8(H2O)46,one mark for the idea of using two cycles and one
mark for correct second cycle calculation. If mistake is made in
calculation of fHo (CH4)8(H2O)46 but then this answer is used correctly
in the second cycle this should be given two marks overall.
Question Total 16

Paper Total 65