A competition to select the team to represent the

UNITED KINGDOM
at the
XXXVth INTERNATIONAL CHEMISTRY
OLYMPIAD
STUDENT QUESTION BOOKLET

Round I - 2003

* * * * *

„ The time allowed is 2 hours.

„ Attempt all 8 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.

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.
 H He
1 2
1.008 4.003

Li Be symbol B C N O F Ne
3 4 atomic number 5 6 7 8 9 10
6.94 9.01 mean atomic mass 10.81 12.01 14.01 16.00 19.00 20.18

Na Mg Al Si P S Cl Ar
11 12 13 14 15 16 17 18
22.99 24.31 26.98 28.09 30.97 32.06 35.45 39.95

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
39.102 40.08 44.96 47.90 50.94 52.00 54.94 55.85 58.93 58.71 63.55 65.37 69.72 72.59 74.92 78.96 79.904 83.80

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
85.47 87.62 88.91 91.22 92.91 95.94 101.07 102.91 106.4 107.87 112.40 114.82 118.69 121.75 127.60 126.90 131.30

Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
132.91 137.34 138.91 178.49 180.95 183.85 186.2 190.2 192.2 195.09 196.97 200.59 204.37 207.2 208.98

Fr Ra Ac+
87 88 89

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
*Lanthanides 58 59 60 61 62 63 64 65 66 67 68 69 70 71
140.12 140.91 144.24 150.4 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
+Actinides
90 91 92 93 94 95 96 97 98 99 100 101 102 103
232.01 238.03
1. This question is about heating a cup of coffee

Nescafé have recently launched a self-

heating can of coffee. To heat up the
coffee, a button is pressed which mixes
the heating ingredients – a very dilute
solution of sodium / potassium
hydroxide and calcium oxide. The can
then warms up 210 ml (210 cm3) of
coffee by approximately 40 °C.

(a) Write an equation for the reaction between calcium oxide and water.

(b) The rate of the heating may be controlled by altering the pH of the solution. How would
you expect the rate of reaction to vary in acidic, basic and neutral conditions?
[Your answer should simply be the words ‘acidic’, ‘basic’ and ‘neutral’ in the order in
which they affect the rate of reaction, fastest first.]

(c) Given the standard enthalpies of formation of calcium hydroxide, calcium oxide and
water are –1003, –635 and –286 kJ mol–1 respectively, calculate the standard molar
enthalpy change for the reaction in (a).

(d) Assuming that the heat capacity for the coffee is the same as that of water,
4.18 J K–1 g –1, calculate the energy needed to warm 210 ml of coffee by 40 °C.

(e) Hence calculate the minimum mass of calcium oxide needed in the can to function as
specified.
2. This question is about Reinecke's salt

When ammonium dichromate(VI) is added gradually to molten ammonium thiocyanate,

Reinecke’s salt is formed. It has the formula NH 4[Cr(SCN) x(NH3)y] and the following
composition by mass:

Cr 15.5 %
S 38.15 %
N 29.2 %.

(a) Calculate the values of x and y in the above formula.

(b) Calculate the oxidation number of chromium in the complex.

(c) Suggest a shape for the complex anion.

(d) Draw two possible structures for the anion and state the type of isomerism it exhibits.
3. This question is about Green Chemistry

Increasing concerns over the use and generation of hazardous

substances in chemical processes has encouraged some chemists to
look for more environmentally friendly ways to make chemical products.
To help evaluate a process environmentally, chemists often use the
term ‘percentage atom economy’, where

% Atom Economy = RMM of desired product x 100

RMM of all products

An environmentally friendly chemical process would normally be expected to have a high

% atom economy, indicating that a high proportion of the starting materials end up as part of
the final product, hence reducing the amount of waste. Efforts are constantly being made to
increase the % atom economy of chemical processes. As an example, the manufacture of
ethene oxide (C2H4O) for many years was via the classical chlorohydrin route:

C2H4 + Cl2 + H2O ClCH2CH2OH + HCl

ClCH2CH2OH + Ca(OH) 2 + HCl C2H4O + CaCl2 + 2H2O

(a) i) Write a balanced equation for the overall reaction.

ii) Calculate the % atom economy for this process.

The modern petrochemical route involves the following reaction:

C2H4 + ½ O2 C2H4O

(b) Calculate the % atom efficiency of this process.

Ibuprofen, a non-steroidal anti-inflammatory drug, was first synthesised by Boots using a six-
step process, with a % atom economy of 40%. When the patent expired in the 1980’s,
several companies began developing new methods for the preparation of ibuprofen. The
BHC Company synthesis, which proved highly successful, is shown below:

HF, (CH3CO)2O H2 / Ni CO, Pd

CH3CO2H
O HO HO2 C
Ibuprofen
Step 1 involves the use of ethanoic anhydride, (CH3CO)2O.

(c) i) Calculate the % atom economy of the BHC Company process.

ii) State the purpose of the HF in step 1.
iii) What happens to the % atom economy if the ethanoic acid is reused?
4. This question is about redox equations

By considering the relevant half equations, write balanced equations for the following
chemical reactions:

(a) zinc metal decolourizing copper(II) sulfate solution

(b) chlorine water turning sodium bromide solution orange

(c) magnesium ribbon reacting with dilute hydrochloric acid

(d) manganese(IV) oxide reacting with concentrated hydrochloric acid to produce a yellow-
green gas and a solution of manganese(II) chloride

(e) sodium sulfate(IV) (sulfite) decolourizing an acidified solution of potassium

manganate(VII)

(f) tin(II) chloride turning orange acidified potassium dichromate(VI) green

(g) acidified potassium manganate(VII) reacting with a lemon-yellow solution of iron(II)

ethanedioate.
5. This question is about the combining proportions of the elements

Understanding the proportions in which the elements combine was a crucial step in
developing the atomic theory of matter. The picture above shows an experiment performed
in the 1660s in which antimony was heated using the sun’s rays to form an oxide.

In the experiment, ‘ye Artist’ reported that ‘12 grains of antimony increased to 15 grains of
calx’, (a grain is an old measure of mass). Given the crudeness of the experiment, this value
is remarkably close to the theoretical yield of 14.4 ‘grains’.

(a) Calculate the formula of the oxide formed.

In another experiment published in 1673, Robert Boyle measured the increase in mass when
zinc metal is heated in air. He describes the experiment thus:

We took a Drachm of filings of Zink and kept it in a Cupelling-fire about three Hours.
Then it look’d as if the filings had been calcin’d. This being weigh’d in the same
scales gain’d full six grains.

(b) Given that there are 60 grains in a Drachm, calculate the mass of product (in grains)
that would have been produced assuming a yield of 100%.

Assuming that Boyle’s measurements are accurate, only a fraction, α, of the zinc must have
been converted to the oxide. (α is a fraction between 0 and 1; 0 meaning none of the zinc
reacted and 1 meaning all reacted).

(c) Calculate the value of α and hence the masses of zinc oxide and unreacted zinc metal
at the end of the experiment.
6. This question is about hydroxylamine and its reaction with iron(III) ions

Hydroxylamine, NH2OH, is a base and a reducing agent; it reacts with hydrochloric acid to
form the salt hydroxylammonium chloride, NH3OH+Cl–, and with Fe3+ ions to produce Fe2+ .

1.00g of hydroxylammonium chloride was dissolved in distilled water and made up to a total
volume of 250 cm3. A 25.0 cm3 aliquot of this solution was added to a solution containing an
excess of both iron(III) ions and sulfuric acid. The mixture was then boiled and allowed to
cool. It was then titrated against a solution of 0.0200 mol dm –3 potassium manganate(VII),
KMnO4, which oxidizes the Fe2+ ions back to Fe3+ and is itself reduced to Mn 2+ ions;
28.9 cm 3 of the potassium manganate(VII) solution was required.

(a) Draw the structure for hydroxylammonium chloride, NH3OH+Cl–. Include on your
diagram the approximate values of the bond angles.

(b) Calculate the ratio of the number of moles of Fe3+ ions to the number of moles of
hydroxylammonium chloride which have reacted together.

(c) Calculate the oxidation number of the nitrogen in hydroxylammonium chloride and
hence in the product.

(d) Suggest which of the following is the nitrogen-containing product formed from the
hydroxylammonium chloride:
N2, NO, N2O, N2O4, NH3.

(e) Write a balanced equation for the reaction between hydroxylammonium chloride and
iron(III) ions.
7. This question is about the synthesis of Rohypnol

Rohypnol is a trade name for the compound

flunitrazepam whose structure is shown in the box
below. It is a controversial sedative which has been
misused to `spike' people's drinks.

Flunitrazepam was first synthesised from

(2-fluoro)-methylbenzene as outlined below.

F
reflux Br2 A NaCN B H2SO 4 (aq) C SOCl2 D
UV light C7 H6BrF C8H6FN C8H7FO2 C8H6 ClFO
CH3
C7H7F
benzene
AlCl 3
F F

– NH3 phenylhydrazine
Fischer indole E
NH – H2O
N synthesis N C14H11FO
H

C20 H14 FN C20H17FN2

ozonolysis with O 3
(oxidises alkene
carbons to carbonyls) O
Br
H2SO 4 (aq) Br NH3
F G + H I J
C20H14FNO 2 C7H6 O2 C13H10FNO C15H11BrFNO 2 C15H13FN2O 2
(by-product)

– H2O
NO2
F
CH3I conc. H 2SO4 / HNO 3 K
L
C15H11FN2O
C15H10FN3 O3
N N CH3

O
Flunitrazepam or
'Rohypnol'
C16H12FN3 O3

Draw the structures for the reagent phenylhydrazine and compounds A to L.

8. This question is about polonium

Polonium is a radioactive group VI element,

discovered in 1898 by Marie Curie. It occurs
naturally in trace amounts in some uranium
ores but is now made by neutron irradiation of
209
Bi. This produces short-lived 210Bi which
decays to polonium by the emission of a beta-
particle (an electron):

209
83 Bi + 01n → 210
83 Bi + γ 210
83 Bi → 210
84 Po + −10β

Polonium-210 has a half life of 138 days and

decays by emitting an alpha particle (a helium
nucleus).

(a) What is the electronic configuration of polonium?

(b) What nuclide is formed when polonium-210 decays?

Due to its very short half life and the impedance of the alpha-particles it emits, metallic
polonium and its compounds are self heating; 1g of metal produces 141 W. This led to its
use in Radioisotope Heater Units (RHUs) to keep satellites warm and functioning in space,
and in Radioisotope Thermal Generators (RTGs) to produce electrical power. More recently,
plutonium-238 has been used instead of polonium. 238Pu has a much longer half-life but
produces less power (0.56 W g–1).

(c) What will be the power output of 210Po after 1 year?

(d) After 5 years, the power output of 238Pu is approximately 96% of its initial value.
Estimate the half life of plutonium-238.

Polonium is unique amongst the elements in being the only one to have a simple cubic
structure with each atom lying at the corner of a cube.

(e) Given that the density of polonium-210 is 9.142 g cm–3, calculate its atomic radius.

[The Avogadro number, NA = 6.022 × 1023 mol–1.]

Olympiad Round 1 2003 – Mark Scheme

1. Heating a cup of coffee

(a) CaO + H2O à Ca(OH) 2 (1)

(b) acidic, neutral, basic (1)

-1
(c) ? rH = - 1003 + 635 + 286 = - 82 kJ mol (1) fig + sign

(d) To warm 1g by 1°C requires 4.18 J

210g by 40°C requires 4.18 x 210 x 40 J = 35.1 kJ (1)

(e) 1 mol CaO provides 82 kJ

We need 35.1 kJ = 35.1 / 82 mol = 0.428 mol
Taking RMM for CaO as 56, minimum mass required = 56 x 0.428 = 24.0 g (1)
(Actual mass used in cans = 70g)

Total 5

2. Reinecke’s Salt

(a) Cr (Ar = 52.0) is 15.5% of total

Therefore total = 100 X 52.0 = 335.5
15.5

For 5 38.15 x 335.5 = 128

100

128 = 4 = x
32

Therefore NH4[Cr (SCN) 4(NH3)y] = 335.5

Therefore 18 + 52 + 4 x 58.1 + 17y = 335.5
Therefore 17y = 33.5
X=4 y=2 (1, 1)

(b) +1 + Cr + 4 x -1 + 2 x 0 = 0 (1)
Therefore Cr = + 3

(c) Octahedral (1)

(d) Two octahedral structures, one with 2NH3 groups adjacent, one with them opposite

Geometrical (1) for 2 shapes

(1) for geometric
or cis/trans

Total 6
3. Green Chemistry

(a) (i) C2H4 + Cl2 + Ca(OH )2 à C2H4O + CaCl2 + H2O extra H2O ok (1)

(ii) % atom economy = 44 x 10 (not 23.6)

44 + 111 + 18
= 25.4 (1)

(b) 100% (1)

(c)(i) Mr ibuprofen = 206

% atom economy = 206 x 100 = 77.4
206 + 60 (1)
(ii) Catalyst (1)

(iii) goes up to 100% (needed) (1)

Total 6

4. Redox Equations Any suitable equation

2+ 2+
(a) Zn(s) + Cu (aq) à Zn (aq) + Cu(s) (1)
- -
(b) Cl2(aq) + 2Br (aq) à 2 Cl (aq) + Br2(aq) (1)
+ 2+
(c) Mg(s) + 2H (aq) à Mg (aq) + H2(g) (1)
+ - 2+
(d) MnO2(s) + 4H (aq) +2Cl à Mn (aq) + 2H2O(l) + Cl2(g) (1)

2- + - 2- 2+
(e) 5SO3 (aq) + 6H (aq) + 2MnO 4(aq) à 5SO4 (aq) + 2Mn (aq) + 3H2O(l ) (1)
2+ + 2- 3+ 4+
(f) 3Sn (aq) + 14H (aq) + Cr2O7 (aq) à 2Cr (aq) + 3Sn (aq) + 7H2O(l ) (1)
- + 2+ 2- 2+
(g) 3MnO 4(aq) + 24H (aq) + 5Fe (aq) + 5C2O4 (aq) à 3Mn (aq)
3+
+12H2O(l) + 5Fe (aq) + 10 CO2(g) (2)

Do not penalise
State symbols

Total 8
5. Combining Proportions

(a) 12 grains of Sb give 14.4 grains of oxide

12 grains Sb combine with 2.4 grains of oxygen
suppose conversion factor for grains to grams = k

moles of Sb = 12k / 121.8 if used (1)

moles of O = 2.4k / 16.0

molar ration Sb : O = (12/121.8) : (2.4/16.0) = 0.9852 : 0.15 = 1:1.5 = 2:3

Formula = Sb2O3 (2 marks if answer alone given) (1)

(b) 1 mol Zn forms 1 mol ZnO

65.4g Zn forms (65.4 + 16.0) g ZnO = 81.4g
increase in mass by 81.4 / 65.4
so 60 grains should produce (60 x 81.4) / 65.4 grains = 74.5(8) grains (2)

(c) Total mass at end = unreacted Zn + ZnO

60 grains Zn should give 74.58 grains ZnO

If fraction of Zn reacting is a, amount of Zn used is 60 a grains which forms 74.58 a

grains of ZnO.
Amount of Zn left = 60 – 60 a
Total mass at end = 60 – 60 a + 74.58 a = 65 grains = 60 + 14.58 a

a = (66 – 60) / 14.58 = 0.41(15) (2)

Mass of unreacted Zn = 60 - 60 a = 35(•31) grains (1)

Mass of ZnO = 74.58 a = 30(•69) grains (1)

Total 8
6. Hydroxylamine and its reaction with iron (III) ions

(a)

(1)

+
H 104-110 o
O

N Cl
-
H
H
H

108-110 o no marks for

structure except
if no angles - then
1 mark.
(1)

+ - 3 -3
(b) Original NH3OH Cl solution 1g in 250cm = 4gdm
-3
= 4.00 = 0.0576 mol dm
69.5
3
25cm aliquot contains 25 x 0.0576 = 0.00144 moles
1000
3 -3 -
28.9cm of 0.0200 mol dm MnO 4 contains 28.9 x 0.0200 = 0.000578 moles (1)
1000
- 2+
1 mole MnO 4 = 5 moles Fe
2+
Therefore No. of moles Fe = 5 x 0.000578 = 0.00289 moles
+ - 2+
Ratio NH3OH Cl : Fe = 1:2 (1)

(c) x + 3 – 2 + 1 = +1 Therefore x = -1
oxidation state of N = -1
3+ 2+
As Fe à Fe , and ratio is 2:1
then oxidation state of product goes up by 2 to +1 (1)

(d) Product must be N2O (1)

+ - 3+ - 2+ +
(e) 2NH3OH Cl + 4Fe à N2O + H2O + 2Cl + 4Fe + 6H (2)

Total 8
7. Rohypnol

F F F F
reflux Br2 NaCN H2SO4 (aq)
UV light
CH3 CH2
A B C
Br CN
HO O

F F
F
benzene H 2N NH
SOCl2
phenylhydrazine
AlCl3
NH
D O N
Cl O
E
Fischer indole
F synthesis F
F
O OH

H2SO4 (aq) O3
+

F
O NH
H O NH2 G O
N
H

O
Br
Br

F F F
NH3
– H2O

N NH
O HN O O HN O
K
I J
O
Br H 2N

NO2 NO2
F F

conc. H2SO4 / HNO3 CH3I

N NH N N
L CH3

O O
Flunitrazepam
or
Rohynol

1 mark for each of A à L + phenylhydrazline Total 13

8. Polonium

2 2 6 2 6 10 2 6 10 14 2 6 10 2 4
(a) 1s 2s 2p 3s 3p 3d 4s 4p 4d 4f 5s 5p 5d 6s 6p (1)

14 10 2 4
exact ordering is irrelevant [Xe] 4f 5d 6s 6p is also acceptable
206
(b) Pb
82
(1)

(c) half life = 138 days. 1 year = 365 / 138 half lives = 2.645 half lives. Power output after
-1
one year = 141 x (0.5 2.645) = 22.5(4) W g (2)

(d) after x half lives, power drops to 0.96 of initial, so [0.5x ] = 0.96 taking logs: x(ln0.5) =
In(0.96), x = 0.05889 half lives in 5 years so time for one half life = 5 / x = 84.899 years =
85 years (2)

(e)

1 unit cell contains 8 x 1/8 atoms = 1 (1)

volume of unit cell = (2r)3 where r = radius
9.142 g = 1 cm 3 = 1 x 10-6m 3 (1)
mass of 1 atom = 210 g / 6.022 x 1023 = 3.487 x 10-22
volume occupied by 1 atom
= (2r)3 = (1 x 10-6 / 9.142) x 3.487 x 10-22m 3 (1)
= 3.814 x 10-29m 3

so r = 13
2
3.8143 × 10 −29 = 1.68(3) x 10-10m = 168pm

(168pm x 2 = 2 unless (3 for ans)

they can say Total 9
336 diameter)
 A competition to select the team to represent the

UNITED KINGDOM
at the
XXXVIth INTERNATIONAL CHEMISTRY
OLYMPIAD
STUDENT QUESTION BOOKLET

Round I - 2004

* * * * *

„ The time allowed is 2 hours.

„ Attempt all 7 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.

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.
 H He
1 2
1.008 4.003

Li Be symbol B C N O F Ne
3 4 atomic number 5 6 7 8 9 10
6.94 9.01 mean atomic mass 10.81 12.01 14.01 16.00 19.00 20.18

Na Mg Al Si P S Cl Ar
11 12 13 14 15 16 17 18
22.99 24.31 26.98 28.09 30.97 32.06 35.45 39.95

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
39.102 40.08 44.96 47.90 50.94 52.00 54.94 55.85 58.93 58.71 63.55 65.37 69.72 72.59 74.92 78.96 79.904 83.80

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
85.47 87.62 88.91 91.22 92.91 95.94 101.07 102.91 106.4 107.87 112.40 114.82 118.69 121.75 127.60 126.90 131.30

Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
132.91 137.34 138.91 178.49 180.95 183.85 186.2 190.2 192.2 195.09 196.97 200.59 204.37 207.2 208.98

Fr Ra Ac+
87 88 89

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
*Lanthanides 58 59 60 61 62 63 64 65 66 67 68 69 70 71
140.12 140.91 144.24 150.4 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
+Actinides
90 91 92 93 94 95 96 97 98 99 100 101 102 103
232.01 238.03
 1. This question is about redox reactions

Give half-equations for the following

reactions in aqueous acid solution.
In each case, indicate whether the
reaction is an oxidation or a
reduction by ticking the appropriate
box in the answer booklet.

(a) FeCl3 to FeCl2

(b) HCl to H2 Redox

[f. RED(UCTION + OX(IDATION.]
(c) K2MnO4 to KMnO4
A reversible reaction in which one species is
(d) SO42– to S2O82– oxidized and another reduced; usu. attrib.,
indicating (some connection with) such a
(e) NO3– to NO2 reaction, or a simultaneous oxidation and
reduction, as redox couple, electrode,
(f) H2O2 to O2 indicator, potential, reaction, etc.
Oxford English Dictionary
(g) Cr2O72– to Cr3+
 2. This question is about pollution and the Taj Mahal

You should need to refer to the following solubility data to help answer this question.

Substance CaCO3 CaSO4 BaCO3 BaSO4

Solubility in water
1.3 x 10–4 4.5 x 10–2 9.1 x 10–5 9.4 x 10–6
/ mol dm–3

Although calcium carbonate is effectively insoluble in pure water, it reacts with acidic
rainwater, thereby accelerating the erosion of marble and limestone monuments.

(a) Give the equation for the reaction between calcium carbonate and carbonic acid,
H2CO3(aq).

In addition to this reaction, the pollutant SO2 forms SO3 in the atmosphere, which then
dissolves in rainwater forming sulfuric acid. This slowly converts calcium carbonate into
solid calcium sulfate.

(b) i) Write the equation for the reaction between calcium carbonate and sulfuric acid.

ii) Why does the conversion of calcium carbonate into calcium sulfate accelerate the
erosion of marble and limestone?

The life of monuments like the Taj Mahal is now being extended by treatment with an
aqueous mixture of barium hydroxide, Ba(OH)2 and urea, CO(NH2)2. As this solution
soaks into the porous marble / limestone, the urea slowly hydrolyses forming ammonia
and carbon dioxide. The carbon dioxide released reacts with the barium hydroxide
forming barium carbonate.

(c) Write the equation for the hydrolysis of urea.

(d) i) Write the equation for the reaction between barium hydroxide and carbon dioxide.

ii) Why does the formation of barium carbonate slow down the rate of erosion of the
monument?

Finally, surface barium carbonate on the treated monument can react with sulfur dioxide
in the air, forming a layer of barium sulfate, and carbon dioxide.

(e) i) Give the equation for the reaction between barium carbonate and sulfur dioxide, in
the presence of oxygen.

ii) Will this secondary reaction speed up or slow down the erosion process?
Explain briefly.
 3. This question is about dissolved oxygen in water

Aquatic life can only survive

because of the oxygen gas
dissolved in the water;
without it, the water rapidly
becomes toxic due to
decaying organic matter.
Hence it is important to
monitor the dissolved oxygen
concentration (DOC) in rivers
and lakes – if this falls below
5 mg dm–3, most species of
fish cannot survive.

One of the most accurate methods for measuring the DOC in water is the Winkler
method. Under alkaline conditions Mn2+ is rapidly oxidised to Mn3+ by dissolved oxygen,
producing a pale brown precipitate of Mn(OH)3. A sample of river water is shaken with
excess alkaline Mn2+, and the resulting pale brown precipitate is then reacted with an
excess of potassium iodide, which it oxidises to iodine. The iodine is then determined by
a titration with sodium thiosulfate (Na2S2O3) solution of known concentration.

(a) Write balanced symbol equations for:

i) the oxidation of Mn(OH)2 to Mn(OH)3 by aqueous oxygen,
ii) the oxidation of KI by Mn(OH)3,

The equation for the reaction between sodium thiosulfate and iodine is:

2Na2S2O3 (aq) + I2 (aq) Na2S4O6 (aq) + 2NaI (aq)

(b) Suggest an indicator for the iodine-thiosulfate titration.

25.0 cm3 of a sample of river water treated in this way required 25.0 cm3 of 0.00100
mol dm–3 sodium thiosulfate solution.

(c) Calculate the concentration of the dissolved oxygen in mg dm–3.

Nitrate(III) ions are found to interfere with this method since they too can oxidise iodide
ions to iodine. During the reaction, a colourless gas is given off, which instantly turns
brown on exposure to the air.

(d) What is the colourless gas? Give a balanced equation for its reaction in air.

(e) Write a balanced equation for the oxidation of iodide ions by nitrate(III) ions.

In a modification of the Winkler method to prevent the interference by nitrate(III) ions, a

solution of sodium azide, NaN3, is added to the river water. During this reaction, two
gases are evolved: nitrogen and N2O.

(f) Write a balanced equation for the reaction between nitrate(III) ions and azide ions in
aqueous acid.
 4. This question is about Agent Orange

Agent Orange was the name given to the

powerful defoliant used during the Vietnam
War. It consisted of a 1:1 mixture of two
herbicides, ‘2,4-D’ and ‘2,4,5-T’.

Shown below is a route for synthesising

2,4,5-T.

1. Heat with NaOH in 1. Heat with NaOH and

methanol / H2O solvent chloroethanoic acid at
under pressure 140 ˚C
1,2,4,5-tetrachlorobenzene X 2,4,5-T
2. Acidify 2. Acidify

The proton NMR spectra for the starting material, 1,2,4,5-tetrachlorobenzene, the
intermediate X, and 2,4,5-T are shown over the page.

After the first step in the synthesis, if the reaction mixture is acidified not with normal
acid, H3O+, but with deuterated acid, D3O+, then the signal at 5.8 ppm in the 1H NMR
spectrum of X disappears. [Deuterium, D, is the 2H isotope of hydrogen.]

(a) Draw the structure of 1,2,4,5-tetrachlorobenzene.

(b) Suggest a structure for the intermediate X.

(c) Give the systematic name for intermediate X.

(d) Draw the structure for X if the reaction mixture had been acidified with D3O+ instead
of H3O+.

(e) Draw the structure of chloroethanoic acid.

(f) Suggest a structure for 2,4,5-T.

(g) On your structure, indicate as far as you are able which hydrogens correspond to which
signals (A, B, C or D) in the 1H NMR spectrum of 2,4,5-T.

Whilst 2,4,5-T is a highly effective herbicide, its commercial use has been discontinued
due to the presence of an incredibly toxic impurity called Dioxin which may be formed
from intermediate X during the synthesis of 2,4,5-T.

2 mol X + 2 mol NaOH 1 mol Dioxin + 2 mol NaCl + 2 mol H2O

The 1H NMR spectrum of Dioxin shows just a single peak at 7.2 ppm.

(h) Suggest a structure for Dioxin.

 1H NMR spectrum of
1,2,4,5-tetrachlorobenzene 2H

solvent (CDCl3)
(H2O)

14 13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

1H NMR spectrum of X

1H 1H 1H
solvent

(H2O)

14 13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

1H NMR spectrum of 2,4,5-T

2H

solvent
(DMSO)
1H 1H 1H

A B C D

14 13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

[The faint lines are the integrals used in working out the relative numbers of hydrogens.]
 5. This question is about tin pest

Tin can exists as two stable allotropes:

β-tin or white tin, which is metallic, and
α-tin or grey tin, which is a non-metal.
The conversion from one form to the
other occurs at a critical temperature,
Tc. The conversion from the metallic
form to the powdery non-metallic form is
known as tin pest or tin disease, partly
because the accompanying change in
density may cause ‘warts’ to form on the
surface.
The organ at the Royal Albert Hall
contains 150 tonnes of tin!

Tin pest has been suggested as the cause of organ pipes disintegrating in certain cold
churches (previously thought to be the work of the devil), and even as a possible reason
for the failure of Captain Scott’s expedition to the South Pole, when the tin solder used in
the fuel cans deteriorated.

The question refers to the change: white tin grey tin

You should use the following data.

atomic distance to
Δf H S density
–1 –1 nearest neighbour
/ kJ mol–1 / J K mol / g cm–3
/ pm
white tin 0 51.4 7.31 302
grey tin – 2.09 44.1 5.75 280

(a) Calculate the standard enthalpy change, ΔrH , for the change.

It is possible to calculate the standard entropy change, ΔrS , for this reaction in a similar
way to the above using the standard entropy values, S , given in the table.

(b) Calculate ΔrS for this reaction.

The feasibility of any chemical process at an absolute temperature T can be determined

by calculating the change in the Gibbs energy, ΔrG, for the process at that temperature,
where
Δ rG = Δ rH – T Δ rS .

If ΔrG is less than zero, the process can take place; if is greater than zero, it cannot.

(c) Calculate ΔrG for the change white tin grey tin at room temperature, 25 °C.

(d) Which allotrope of tin is stable at room temperature? Justify your answer.

(e) Calculate the temperature, Tc, at which both allotropes are in equilibrium.

(f) Calculate the percentage increase in volume as white tin converts to grey tin.

(g) Which allotrope possesses the greater coordination number? Justify your answer.
 6. This question is about a supernova

The electronic ground state (i.e. the lowest

electronic state) of a hydrogen atom may be
written 1s1 indicating that the single electron
resides in the 1s orbital. If sufficient energy is
given to the atom, the electron may be promoted
from the 1s orbital to a higher energy orbital,
such as the 2p orbital or the 3p orbital.

The energy of an electron in a hydrogen atom (or

any ionized atom with nuclear charge Z and with
just one electron remaining) is given by the
following equation:
Z2
E n = − RH Supernova remnant E0102-72
n2 as photographed by the UV / x-
The energy of a free, ionized electron is zero; ray telescope Chandra.
electrons in the atom have lower energy, hence
the minus sign.

In the equation, Z is the number of protons in the nucleus (Z = 1 for hydrogen);

n is the principal quantum number (n = 1 for the 1s orbital, 2 for the 2s and 2p orbitals,
3 for the 3s, 3p and 3d orbitals, etc.);
RH is the Rydberg constant equal to the ionization energy of a hydrogen atom
(RH = 2.179 × 10–18 J).

(a) Calculate the energy of an electron in a 2p orbital in an excited hydrogen atom.

(b) Calculate the energy needed to promote the electron in a hydrogen atom from the 1s
orbital to the 2p orbital.

(c) Calculate the ionization energy of a helium ion, He+.

When an electron returns from a higher energy orbital to a lower one, energy is given out
as light (the cause of the familiar flame colours). The frequency of the light, f, (in Hz) is
related to the energy of the transition, ΔE, by the equation:

ΔE=hf (where h is Planck’s constant = 6.626 × 10–34 J s).

(d) Calculate the frequency of light for the electronic transition in a hydrogen atom from a
2p orbital to the 1s orbital (the so-called Hydrogen Lyman-α line).

Supernova remnant E0102-72, located some 200,000 light years away, has been found
to contain more than a billion times the amount of oxygen contained in the Earth's
oceans and atmosphere. At the incredibly high temperatures in the supernova (many
millions of Kelvin), the oxygen atoms are multiply ionized to single electron species, O7+.
The oxygen was detected by the specific frequency of its Lyman-α line (the transition
n = 2 to n = 1).

(e) Calculate the frequency of the O7+ Lyman-α line.

(f) Another element present in large quantities has its Lyman-α line at 2.471 × 1017 Hz.
What element is this?
 7. This question is about ‘asparagus-pee’
It has long been known that after eating asparagus,
many people can detect an odd odour in their urine.
(Whether or not a person can actually smell it is
apparently genetic.)
In the 19th century it was thought that the
compound responsible for the smell in so-called
‘asparagus-pee’ was methanethiol, CH3SH.
In a more recent study, no methanethiol was
detected in the vapour from asparagus-pee but two
other sulfur-containing compounds, A and B, were
identified by mass spectrometry. The M+ ion for
compound A is at m/e = 102; for compound B, m/e =
150.

For comparative purposes, compounds A and B were also prepared in the laboratory
from propenoic acid by the following routes.

O O

N
+ CH3SH + R C R A + R C R
OH N N N
(DCC) H H

by-product
O

+ H 2S W
OH

W + CH3I X
O

N
X + CH3SH + R C R B + R C R
N N N
(DCC) H H

by-product

Compound A reacts with HBr to give Y and with Br2 to give two isomers, Z1 and Z2.

Y is not optically active and has two peaks for its M+ ion at m/e = 182 and 184 (1:1 ratio).

Z1 and Z2 are enantiomers (optical isomers) and their M+ ions have m/e = 260, 262, and
264 (ratio 1:2:1).

(a) State the role of the reagent ‘DCC’: i) catalyst; ii) hydrating agent;
iii) dehydrating agent; iv) hydrogenating agent or v) dehydrogenating agent.

(b) Suggest structures for compounds A, B, W, X, Y, Z1, and Z2.

(c) Both A and B may be hydrolysed in water, releasing methanethiol, (hence the earlier
suspicion of this compound). Write balanced equations for the hydrolysis reactions of
both A and B.

[Naturally occurring bromine is a 1:1 mixture of 79Br and 81Br]

 A competition to select the team to represent the

UNITED KINGDOM

at the

XXXVIth INTERNATIONAL CHEMISTRY

OLYMPIAD

ANSWER BOOKLET FOR MARKERS

Round I - 2004

* * * * *
Olympiad Round 1 2004 – Mark Scheme

1. This question is about redox reactions

(a) Fe3+ + e– à Fe2+ reduction

(b) 2H+ + 2e– à H2 reduction

(c) MnO 4 2– à MnO4 – + e– oxidation

(d) 2SO4 2– à S2 O82– + 2e– oxidation

(e) NO3 – + 2H+ + e–à NO2 + H2O reduction

(f) H2 O2 à O2 + 2H+ + 2e– oxidation

(g) Cr2 O72– + 14H+ + 6e– à 2Cr3+ + 7H2 O reduction

1 mark for each correct reaction (=7)

2 marks if all oxidation and reduction correct
Take off 1 mark for a single mistake.

Total 9

2. This question is about pollution and the Taj Mahal

(a) CaCO3 + H2CO3 à Ca(HCO3 )2

(b) i) CaCO3 + H2 SO4 à CaSO4 + H2CO3

ii) CaSO4 is more soluble than CaCO3 .

(c) CO(NH2 )2 + H2O à CO2 + 2NH3

(d) i) CO2 + Ba(OH)2 à BaCO3 + H2 O

ii) BaCO3 is even less soluble than CaCO3 .

(e) i) 2BaCO3 + 2SO2 + O 2 à 2BaSO4 + 2CO2

ii) Slow down, because BaSO4 is least soluble of all/ The reaction

consumes SO2 , thus less H2 SO4 is formed.

Total 8
3. This question is about oxygen dissolved in water

(a) i) 4Mn(OH)2 + O2 + 2H2 O à 4Mn(OH)3

ii) KI + Mn(OH)3 à ½ I2 + Mn(OH)2 + KOH (2)

(b) Starch (1)

(c) 25.0 cm3 of 0.00100 mol dm–3 Na2 S2 O3 contains 2.50×10–5 moles

This reacts with 1.25×10–5 mol I2, which is formed from 2.50×10–5 mol

Mn(OH)3. 2.50×10–5 mol Mn(OH)3 is formed from 6.25×10–6 mol O2 . Mass

O2 = 6.25×10–6 × 32 = 0.200 mg in 25.0 cm3 . Therefore concentration of O2 =

8.00 mg dm–3 (2)

(d) The colourless gas is NO.

2NO + O2 à 2NO2 (1)

(e) NO2 – + I– + 2H+ à NO + ½ I2 + H2O (1)

(f) HNO2 + HN3 à N2 + N 2O + H2 O (2)

or 2HNO2 + 4HN3 à 6N2 + N 2O + 3H2 O

Total 9
4. This question is about Agent Orange

(a) (b)
Cl Cl

Cl OH

Cl Cl

Cl Cl

(1) (1)

(c) 2,4,5–trichlorophenol (1)

(d) (e)
Cl

OD
O

Cl HO

Cl Cl

(1) (1)

(f), (g) 2 for structure, 2 for assignment (4)

Cl O

B O
OH
D A
C
Cl

Cl B and C may be the other way round

h) (2)
Cl O Cl

Cl O Cl
 Total 11

5. This question is about tin pest

(a) ? ?H? = – 2.09 kJ mol–1 1 for value, 1 for units (2)

(b) ? ?S? = 44.1 – 51.4

= – 7.30 J K-1 mol-1 1 for value, 1 for units (2)

(c) 25?C = 298 K

? ?G = ? ?H – T? ?S
= –2090 – (298 × – 7.3)
= 85.4 J mol-1 (2)

1 mark for using 25 instead of 298 = -1.91 kJ mol–1

1 mark for using 2.09 instead of 2090 = 2.17 kJ mol–1

(d) White because ? ?G > 0 at room temperature (1)

(e) T = (? ?H –? ?G) / ? S?
= (–2090 – 0) / – 7.3
= 286K (13?C) (1)

(f) Volume of 1 g white tin = 1/7.31 = 0.137 cm3

Volume of 1 g grey tin = 1/5.75 = 0.174 cm3
Percentage volume increase
= [(0.174 – 0.137) / 0.137] × 100 = 27.1 % (1)

(g) White tin will have a great coordination number because it is denser so the
atoms are more tightly packed/ there is a larger distance to its nearer
neighbours which implies it has more neighbours
(1)

Total 10
6. This question is about a supernova

(a) E = –RH Z2 /n2

= – 2.179×10–18 × ¼

= – 5.45×10–19 J (1)

(b) E= – 5.45×10–19 – (–2.179×10–18 )

= 1.63×10–18 J (1)

(c) I.E. = 0 – (–2.179×10–18 × 4/1)

= 8.72×10–18 J (1)

(d) f = 1. 63×10–18 /6.626×10–34

= 2.47×1015 Hz (1)

(e) ?E= – RH Z2 ( 1/n2 2 – 1/n1 2 )

= – 2.179×10–18 × 64 × (1/4 – 1)

= 1.05×10–16 J

f= ?E/h= 1.05×10–16 /6.626×10–34

= 1.58×1017 Hz (3)

lose 1 mark for using Z=7

(gives ?E= 8.01 × 10-17 Hz , f = 1.58×1017 Hz )

(f) ?E= hf = 6.626×10–34 × 2.471×1017

= 1.64×10–16 Hz (1)

?E= – RH Z2 ( 1/n2 2 – 1/n1 2 )

= – RHZ2 ( -3/4 )

Z= v(4/3 × ?E/RH)

= v(4/3 × 1.63×10–16 /2.179×10–18 )

= 10 The element is Neon (1)

Total 9
7. This question is about ‘asparagus –pee’

(a) (iii) dehydrating agent

(1)

(b)
O O
A B

S S S

O O
W X

HS OH S OH

O
Y

Br S

Z1 Br O Z2 Br O

S S

Br Br (7)

(c)

O O
A
+ H2O + CH 3SH
S OH

O O
B

+ H2 O
S S S OH + CH 3SH

O O
OR

+ 2H2O + 2CH 3SH

S S HO OH

(2)

Total 10
Total for paper 66
 A competition to select the team to represent the

UNITED KINGDOM
at the
XXXVIIth INTERNATIONAL
CHEMISTRY OLYMPIAD
STUDENT QUESTION BOOKLET

Round I - 2005

* * * * *
„ The time allowed is 2 hours.
„ Attempt all 6 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.

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.
 H He
1 2
1.008 4.003

Li Be symbol B C N O F Ne
3 4 atomic number 5 6 7 8 9 10
6.94 9.01 mean atomic mass 10.81 12.01 14.01 16.00 19.00 20.18

Na Mg Al Si P S Cl Ar
11 12 13 14 15 16 17 18
22.99 24.31 26.98 28.09 30.97 32.06 35.45 39.95

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
39.102 40.08 44.96 47.90 50.94 52.00 54.94 55.85 58.93 58.71 63.55 65.37 69.72 72.59 74.92 78.96 79.904 83.80

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
85.47 87.62 88.91 91.22 92.91 95.94 101.07 102.91 106.4 107.87 112.40 114.82 118.69 121.75 127.60 126.90 131.30

Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
132.91 137.34 138.91 178.49 180.95 183.85 186.2 190.2 192.2 195.09 196.97 200.59 204.37 207.2 208.98

Fr Ra Ac+
87 88 89

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
*Lanthanides 58 59 60 61 62 63 64 65 66 67 68 69 70 71
140.12 140.91 144.24 150.4 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
+Actinides
90 91 92 93 94 95 96 97 98 99 100 101 102 103
232.01 238.03
 1. This question is about carbon oxides

In addition to the two most

common oxides – carbon
monoxide and carbon
dioxide – a few other
compounds may be formed
containing carbon and
oxygen only. Each oxide
may be prepared by the
dehydration of the
appropriate acid.

Carbon dioxide may be prepared by the reaction between an acid, such as hydrochloric
acid, and a carbonate, such as calcium carbonate. Simply protonating the carbonate
should yield carbonic acid, but this is unstable and readily loses water to form carbon
dioxide.

(a) i) Give the equation for the reaction between calcium carbonate and hydrochloric acid
to form carbon dioxide.

ii) Draw the structure of carbonic acid.

Carbon monoxide may be prepared by dehydrating methanoic acid with concentrated

sulfuric acid at about 140 °C.

(b) i) Write the equation for the reaction between methanoic acid and sulfuric acid.

ii) Draw a ‘dot and cross’ structure for carbon monoxide.

iii) Is the bond between the carbon and oxygen in carbon monoxide best described as
a single, double or triple bond?

Poisonous carbon monoxide may be detected by its ability to reduce an aqueous solution
of palladium(II) chloride to black metallic palladium (Pd).

(c) Write the equation for the reaction between aqueous palladium(II) chloride and carbon
monoxide.

‘Carbon suboxide’ is a foul-smelling gas obtained by fully dehydrating propan-1,3-dioic

acid.

(d) i) Draw the structure of propan-1,3-dioic acid and write a balanced equation for this
acid forming carbon suboxide and water.

ii) Draw a structure for carbon suboxide.

A fourth oxide of carbon has the formula C12O9 and may be obtained by fully dehydrating
mellitic acid [ benzene hexacarboxylic acid – C6(COOH)6 ].

(e) Draw a structure for benzene hexacarboxylic acid and for C12O9.
 2. This question is about diiodine pentoxide

Diiodine pentoxide, I2O5, is a white

crystalline powder that has the useful
property of reacting quantitatively with
carbon monoxide to yield iodine and
one other product.

(a) Suggest an equation for the reaction between I2O5 and carbon monoxide.

A 150 cm3 sample of gas (at room temperature and pressure, r.t.p.) that was known to
contain carbon monoxide was repeatedly passed over excess I2O5 at 170 °C. The I2O5
became coloured with iodine. The iodine generated required exactly 8.00 cm3 of 0.100
mol dm–3 sodium thiosulfate solution to react with it. This reaction is:

I2 (aq) + 2 Na2S2O3 (aq) 2 NaI (aq) + Na2S4O6 (aq)

(b) Calculate the percentage by volume of carbon monoxide present in the sample of gas.
[Assume 1 mol of any gas occupies 24.0 dm3 at r.t.p.]

Diiodine pentoxide readily absorbs water and is sometimes supplied in a hydrated form,
HxIyOz. If this is heated to 200 °C it loses 1.766% of its mass to form pure I2O5.

(c) Calculate the empirical formula of the impure form, and write the equation for its
dehydration.

I2O5 is an acid anhydride and reacts with excess water to produce the parent acid. This
is analogous to the reaction between ethanoic anhydride and water to form ethanoic
acid.

(d) Suggest the formula for the simple parent acid of I2O5, and write the equation for its
formation from I2O5. What is the oxidation state of the iodine in I2O5?

(e) Suggest a structure for the parent acid and hence a structure for I2O5.

(f) The parent acid of I2O5 may be formed by reacting iodine, chlorine and water.
Suggest an equation for this reaction.
 3. This is a question about ants

The ‘simplest’ carboxylic acid is called

methanoic acid and has formula
HCOOH. It occurs naturally in ants and
used to be prepared by distilling them!
This gave rise to the earlier name for
methanoic acid – formic acid – after the
Latin word formica for ant.

When an ant bites, it injects a solution

containing 50% by volume of methanoic
acid. A typical ant may inject around
6.0 × 10–3 cm3 of this solution.
A Formica rufa worker ant, just after biting the
photographer!

(a) i) When you are bitten by an ant it does not inject you with all of its methanoic acid but
keeps a little in reserve. Assuming a ‘typical ant’ injects 80% of its methanoic acid,
what is the total volume of pure methanoic acid contained in a ‘typical ant’?
ii) How many ‘typical ant’ ants would have to be distilled to produce 1.0 dm3 of pure
methanoic acid?
Bicarbonate of soda (sodium hydrogencarbonate) is often used to treat ant stings.
(b) i) Write the equation for the reaction between sodium hydrogencarbonate and
methanoic acid.
ii) Given that the density of methanoic acid is 1.2 g cm–3, how many moles of
methanoic acid does the ‘typical ant’ inject?

iii) What mass of sodium hydrogen carbonate would be needed to neutralise

completely the sting from this ant?
(c) As soon as the methanoic acid is injected it dissolves in water in the body to produce a
solution of methanoic acid. Assuming that it dissolves immediately in 1.0 cm3 of water
in the body calculate the concentration of the methanoic acid solution that is formed.
[You may ignore the volume of the methanoic acid itself in this calculation.]
The pH of a solution is related to the concentration of hydrogen ions as follows:

pH = – log [H+]
where [H+] stands for the concentration of hydrogen ions in mol dm-3.
(d) The pH of the methanoic acid solution produced above was 2.43. What is the
concentration of hydrogen ions in this solution?
Methanoic acid is a weak acid and so is only partly ionised in solution

HCOOH(aq) HCOO–(aq) + H+(aq)

(e) Calculate the percentage of methanoic acid molecules which are ionised in this
solution.
The acid dissociation constant, Ka, is a measure of how ionised a weak acid is. For
methanoic acid it is defined by the following expression where again square brackets
written round a formula mean the concentration of that substance in mol dm–3

Ka = [HCOO–][H+] / [HCOOH].

(f) Calculate the acid dissociation constant for methanoic acid.

4. This question is about the NMR spectra of NanoPutians

In June 2003, a research paper was

published announcing the synthesis
of the smallest representations of the
O O
human form: 2 nm tall
anthropomorphic molecules,
nicknamed ‘NanoPutians’ by their
creators.

The molecules synthesised included

‘NanoKid’, ‘NanoBaker’ and
‘NanoAthlete’. The compound
shown to the right was called
‘NanoBalletDancer’ and has the
formula C41H50O2.

40 41 When assigning an NMR spectrum, the

first step is to identify how many atoms
39 38 37 29
35 there are in unique environments.
34 O 36 O 28
32 26
33 27
Both carbon atoms (13C) and hydrogen
21
31
30 22
20 25 atoms (1H) give NMR signals. Each
24
atom in a different environment will give
23 19 14 16 rise to one signal.
18 12
9 13 15
17 For example, in the structure of
10 8 NanoBalletDancer, carbon atoms 37
11 7 and 39 are equivalent; we may write
6
(37 ≡ 39). Hence, although there are
5
two carbon atoms (37 and 39) which
4 have one oxygen atom attached, only
3 one signal would be observed in a 13C
2 NMR spectrum due to these carbon
1 atoms since they are equivalent.

(a) Which carbon atoms making up the benzene rings are equivalent? Write down w ≡ x,
y ≡ z etc for any equivalent atoms. How many signals in total would be observed due to
benzene-ring carbons in a carbon NMR spectrum of NanoBalletDancer?

(b) List the groups of equivalent triple bond carbons in NanoBalletDancer. How many
signals would be seen in total in the 13C spectrum due to triple bond carbon atoms?

(c) How many different methyl groups (–CH3 groups) are there in NanoBalletDancer?
Again, list them in groups.

(d) How many different carbon environments are there in NanoBalletDancer – i.e. how
many signals would be seen in total in the 13C NMR spectrum?
 Similarly, in 1H NMR, the total number of signals depends on the number of different
environments of hydrogen atoms in a structure. There are 13 different environments of
hydrogens in NanoBalletDancer; their signals are labelled A–M in the spectrum below.
The numbers of hydrogen atoms in each unique environment is given under the label.
Hydrogen atoms in similar environments all have similar chemical shifts. For example,
all the hydrogens on the benzene rings occur in the same region of the spectrum, i.e.
they have a similar chemical shift.
However, 1H NMR is complicated by coupling. If a hydrogen is within three bonds of
another hydrogen which is in a different environment, instead of appearing as a single
peak, its signal is split into a number of peaks. In general, if the hydrogen under
consideration is within three bonds of n hydrogens in a different environment from the
one under consideration, it will be split into (n + 1) peaks. The ratio of the area under the
peaks is given by Pascal’s triangle as outlined below.
observed ratio for a hydrogen coupling to
1 0 hydrogens

1 : 1 1 hydrogen

1: 2 : 1 2 hydrogens

1 : 3: 3 : 1 3 hydrogens

1 : 4: 6 :4 :1 4 hydrogens

The signal for a given hydrogen is not split by any hydrogens which are in the same
environment as it is in.
(e) Into how many peaks will the signal from a hydrogen that couples with 5 other
hydrogens be split? What will the ratio of the peaks be?
It is possible to assign the 1H NMR spectrum of NanoBalletDancer by considering the
numbers of hydrogens in different environments, their chemical shifts, and their coupling
patterns. For example, the signal at 7.15 ppm (B) is due to the hydrogen atoms on
carbons 19 and 23.
(f) On the table in your answer sheet, assign (as far as possible) which signals are due to
which hydrogen atoms. The assignment for signal B has already been filled in on the
answer sheet. (For some signals, it might not be possible to decide between two
alternative assignments – in which case just write ‘... or ...’ on the answer sheet.)
The 1H NMR spectrum K
18H
of NanoBalletDancer

L
H 6H
I
4H
4H M
3H
E F
2H 2H G
J
2H
3H

B C
2H 2H

A D solvent
1H 1H

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
 5. This question is about the Breathalyser

Some self-test breathalyser kits use

the redox reaction between ethanol
and acidified potassium dichromate
to estimate blood alcohol.
The alcohol gets into the blood by
absorption through the stomach wall;
most is broken down in the liver to
carbon dioxide and water – the rest
leaves the body through sweat, in the
breath and by excretion in urine.

Alcohol concentration in the blood can be estimated by analysing the alcohol in the
breath because an equilibrium is set up between the alcohol in the blood and the alcohol
in the air in the lungs:
CH3CH2OH(Blood) CH3CH2OH(Breath)
At body temperature, the concentration of alcohol in the blood is about 2300 times that in
the breath.

(a) i) On your answer sheet, complete the half equation for the oxidation of ethanol to
ethanoic acid:
___ CH3CH2OH + ___ H2O ___ CH3CO2H + ___ H+ + ___ e–

ii) On the answer sheet, complete the half equation for the reduction of the dichromate
ion in acid solution.
___ Cr2O72– + ___ e– + ___ H+ ___ Cr3+ + ___ H2O

iii) Combine these to give an overall equation for this reaction.

iv) Assuming that the acid used is sulfuric acid and the dichromate salt is potassium
dichromate, write a balanced equation for the reaction.

The breathalyser kit consists of a plastic bag that is inflated with 1000 cm3 of breath and
a glass tube containing the dichromate crystals. When the bag is connected to the tube
and the breath is expelled through the tube the crystals change colour as they are
reduced. The proportion of the crystals that change colour indicates the amount of
alcohol present.

The current legal maximum blood alcohol concentration when driving in Britain is 80 mg
per 100 cm3 of blood.

(b) i) What is the corresponding breath alcohol concentration in μg per 1000 cm3 of breath?

ii) Assuming that the tube must be able to test breath at least three times over the legal
limit, what mass of potassium dichromate should the tube contain?

iii) What colour change would you expect for a positive result?
6. This question is about the synthesis the new wonder-drug ‘Rimonabant’

In September 2004 the drug company

Sanofi-Synthelabo announced a new
compound to help fight both obesity
and smoking. The structure of the
drug rimonabant (to be marketed
under the trade name Acomplia) is
given below together with an outline of
its synthesis.

Draw the structures for the starting

materials chlorobenzene and propanoyl
chloride, and compounds A – F.

AlCl3 (catalyst)
chlorobenzene + propanoyl chloride A + HCl

strong lithium base

A B
-H C9H8ClO Li

OC2H5
B + C2H5O C + Li C2H5O

O
H
H N
N H
Cl
C + D + 2H2O

Cl

KOH (in methanol)

D + E + C2H5OH + KCl
then dilute HCl

E + SOCl2 F + SO2 + HCl

O
H
N
N N
N H H
F + N + HCl
N

Cl
Cl

rimonabant
Cl
The Chemistry Olympiad Committee would like to thank the following people for their
help and advice in the preparation of this paper:

The experts from JAWS anthill for the factual information on ants and for the photograph
of the Formica Rufa worker ant. www.anthill.org.uk

Professor James M. Tour and his research group for the kind loan of a sample of
NanoBalletDancer.
Chanteau and Tour, Synthesis of Anthropomorphic Molecules: The NanoPutians
Journal of Organic Chemistry, 2003, Vol 68(23), p8750-8766

The NMR department of the University of Cambridge, Department of Chemistry for

running the 700 MHz 1H NMR spectrum of NanoBalletDancer.

The synthesis of Rimonabant is taken from

A. Makriyannis et al, Structure-Activity Relationships of Pyrazole Derivatives as
Cannabinoid Receptor Antagonists
Journal of Medicinal Chemistry, 1999, Vol. 42(4), p769-776
 A competition to select the team to represent the

UNITED KINGDOM

at the

XXXVIIth INTERNATIONAL CHEMISTRY

OLYMPIAD

ANSWER BOOKLET FOR MARKERS

Round I - 2005

* * * * *
Olympiad Round 1 2005 – Mark Scheme
1. This question is about carbon oxides

(a) i) CaCO3 (s) + 2HCl (aq) Ca2+ (aq) + 2Cl–(aq) + H2O + CO2 (g)
(state symbols not required; CaCl 2 also fine) (1)

ii)
O

C
HO OH (1)

(b) i) HCOOH + H2SO4 CO (g) + H2O + H2SO4 (1)

ii)
x
x
x o
x C o O oo
o
o (1)

iii) TRIPLE bond (1)

(c) i) Pd2+ (aq) + CO + H2O CO2 (g) + Pd (s) + 2H+ (aq) (1)

(d) i)
O H
O

C C C

HO OH
H
propan-1,3-dioic acid

C3H4O4 2H2O + C3O2

(2)

ii) (1)
O C C C O
(e)
O
O OH
OH O O
O

O
O OH
O
HO O
O

O
O OH O
HO O O
benzene hexacarboxylic acid C12O9
(2)

Total: 11
2. This question is about diiodine pentoxide

(a) I2O5 + 5 CO ? I2 + 5 CO2 (1)

(b) Amount of S2O32- = 8.00 cm3 × 0.100 mol dm-3 = 8.00 × 10-4 mol
∴Amount of I2 = 4.00 × 10-4 mol
∴Amount of CO = 2.00 × 10-3 mol
∴Volume of CO = 2.00 × 10-3 mol × 24 dm3 mol-1 = 48 cm3
∴Percentage by volume of CO = 48 cm3/150 cm3 × 100% = 32% (2)

(c) Molar mass of I2O5=(2×126.90 g mol-1)+(5×16.00 g mol-1) = 333.80 g mol-1.

To form 1 mol of I2O5, mass of anhydride required
= 333.80 g / (1-0.01766) = 339.80 g.
The mass loss of (339.80 - 333.80 = 6.00) g is equivalent to 1/3 of a mole of
water, so 3 moles of I2O5 must be produced for each mole of water eliminated,
making the equation H2I6O16 ? 3 I2O5 + H2O
The empirical formula of the parent acid is therefore HI3O8.
(It is actually HIO3.I2O5.) The equation for the dehydration is:
2 HI3O8 ? 3 I2O5 + H2O (2)

(d) Parent acid: HIO3.

Equation for formation is: I2O5 + H2O ? 2 HIO3
Oxidation state of iodine in I2O5: +5 (2)

(e)
I O O
OH I I
O
O O O
O
Accept chemically sensible alternatives. (2)

(f) I2 + 5 Cl2 + 6 H2O ? 2 HIO3 +10 HCl

(Appreciation that chlorine is oxidising iodine up to its +V oxidation state, and itself
being reduced to chloride reveals the I2:Cl2 stoichiometry. The other numbers follow
straightforwardly.) (1)

Total: 10
3. This question is about ants

(a) i) ) 6.0 x 10-3 x 0.5 x 100 / 80 = 3.75 x 10-3 cm3 so accept 3.8 x 10-3 cm3

ii) 1000 / 3.75 x 10-3 = 2.7 x 105

(b) i) HCOOH + NaHCO3 ? HCOONa + H2O + CO2

ii) 6.0 x 10-3 x 0.5 x 1.2 / 46 = 7.8 x 10-5 moles

iii) 7.8 x 10-5 x 84 = 6.6 x 10-3 g = 6.6 mg

(c) 7.8 x 10-2 mol dm-3

(d) 3.7 x 10-3 mol dm-3

(e) 3.7 x 10-3 / 7.8 x 10-2 x 100 = 4.8 %

(f) (3.7 x 10-3)2 / (7.8 x 10-2 – 3.7 x 10-3) = 1.8 x 10-4 mol dm-3 (also accept 1.9 x 10-
4
). This means pKa = 3.73.

1 mark for each part

Total: 9
 4. This question is about the NMR spectra of NanoPutians

(a) 6 ≡ 8, 9 ≡ 11, 19 ≡ 23, 20 ≡ 22

8 signals in total due to benzene ring carbons (2)

(b) 4 ≡ 13, 5 ≡ 12, 24 ≡ 30, 25 ≡ 31

4 signals in total due to triple bond carbons (2)

(c) 1 ≡ 16, 27 ≡ 28 ≡ 29 ≡ 33 ≡ 34 ≡ 35, 40 (unique), 41 (unique)

4 signals in total due to methyl group carbons (3)

(d) 23 different environments (i.e. 23 different signals)

(2 marks for the correct answer. 1 if the answer given is 22)

(e) signal split into 6, ratio 1: 5 : 10 : 10 : 5 : 1 (1)

(f)
1
H NMR Signal Hydrogen(s) on Carbon(s)

A 7

B 19, 23

C 9, 11

D 36

E 17

F 37 and 39

G 37 and 39

H 3, 14

I 2, 15

J 40 or 41

K 27, 28, 29, 33, 34, 35

L 1, 16

M 41 or 40

(6)

Total: 16
5. This question is about the Breathalyser

(a) i) CH3CH2OH + H2O ? CH3CO2H + 4H+ + 4e– (1)

ii) Cr2O72–- + 6e– + 14H+ ? 2Cr3+ + 7H2O (1)

iii) 3CH3CH2OH + 2Cr2O72–- + 16H+ ? 3CH3CO2H + 4Cr3+ +11H2O (2)

iv) 3CH3CH2OH + 2K2Cr2O7 + 8H2SO4 ? 3CH3CO2H + 2Cr2(SO4)3 + 2K2SO4 +

11H2O
(1)

(b) i) Blood alcohol = 800mg/1000cm3

Breath alcohol = 800/2300mg/1000cm3 = 0.348mg/1000cm3 = 348µg/1000cm3
(1)

ii) Max mass ethanol = 3 x 348 = 1.044mg/1000cm3

∴ Max amount = 2.27 x 10–5mol
Moles K2Cr2O7 required = 2/3 x 2.27 x 10–5
Mr (K2Cr2O7) = 294
∴ Mass needed = 2/3 x 2.27 x 10–5 x 294 = 4.45mg
(3)

iii) Orange to green (1)

Total: 10
 6. This question is about the synthesis of the new wonder-drug 'Rimonabant'

Cl O

Cl

chlorobenzene propanoyl chloride

O O Li O Li
B

Cl Cl Cl
A B allow structure with
negative charge on carbon

OC 2H5

OC2H 5 N
N
O
O
Cl
Cl
C D
Cl

Cl

O O

OH Cl

N N
N N

Cl Cl
Cl Cl

E F

Cl Cl
(1 mark for each structure
2 bonus marks if all correct)

Total: 8
Total for paper 64 (plus 2 possible bonus marks)
 38th INTERNATIONAL

CHEMISTRY OLYMPIAD

2006
UK Round One

STUDENT QUESTION BOOKLET

* * * * *
„ The time allowed is 2 hours.
„ Attempt all 7 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.

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.
 H He
1 2
1.008 4.003

Li Be symbol B C N O F Ne
3 4 atomic number 5 6 7 8 9 10
6.94 9.01 mean atomic mass 10.81 12.01 14.01 16.00 19.00 20.18

Na Mg Al Si P S Cl Ar
11 12 13 14 15 16 17 18
22.99 24.31 26.98 28.09 30.97 32.06 35.45 39.95

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
39.102 40.08 44.96 47.90 50.94 52.00 54.94 55.85 58.93 58.71 63.55 65.37 69.72 72.59 74.92 78.96 79.904 83.80

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
85.47 87.62 88.91 91.22 92.91 95.94 101.07 102.91 106.4 107.87 112.40 114.82 118.69 121.75 127.60 126.90 131.30

Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
132.91 137.34 138.91 178.49 180.95 183.85 186.2 190.2 192.2 195.09 196.97 200.59 204.37 207.2 208.98

Fr Ra Ac+
87 88 89

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
*Lanthanides 58 59 60 61 62 63 64 65 66 67 68 69 70 71
140.12 140.91 144.24 150.4 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
+Actinides
90 91 92 93 94 95 96 97 98 99 100 101 102 103
232.01 238.03
1. This question is about sherbet lemons

Sherbet lemons are sweets which

consist of a flavoured sugar shell
filled with sherbet.

The sherbet contains sodium

hydrogencarbonate and tartaric
acid (2,3-dihydroxybutanedioic
acid).

(a) Assuming all the sugar present is sucrose, C12H22O11, write an equation for the
complete combustion of the sugar.

(b) The standard enthalpy change of combustion of sucrose is –5644 kJ mol–1. Calculate
the energy released when one sweet containing 6.70 g of sucrose is completely burnt.

(c) A man needs to consume about 2500 dietary calories per day. Given that 1kJ ≡ 0.239
dietary calories, how many sweets must a man consume in order to meet his daily
calorific requirement?

Sherbet produces a slight fizzing sensation in the mouth when the tartaric acid reacts with
the sodium hydrogencarbonate to make carbon dioxide. In a laboratory experiment, one
sherbet lemon sweet produced 6.00 cm3 of carbon dioxide.

(d) Calculate the minimum masses of tartaric acid and sodium hydrogencarbonate
necessary to produce this volume of carbon dioxide.
[Assume 1 mol of any gas occupies 24.0 dm3 at r.t.p.]

A carbon atom bonded to four different groups is called a chiral centre or an asymmetric
carbon atom. A molecule which contains just one chiral centre exists as two stereoisomers
(isomers containing the same groups attached to the same atoms). These stereoisomers
are non-superimposable mirror images of each other called enantiomers. If a molecule
contains more than one chiral centre, the number of stereoisomers increases and some of
the stereoisomers may be superimposable on their mirror images.

(e) By making the appropriate substitutions for a, b, c, and d in the structure shown below,
draw all the different stereoisomers of tartaric acid, indicating clearly which (if any) are
enantiomers.
HO2C CO 2H
C C
b c
a d

(f) Citric acid is used to flavour sherbet lemons. Its formula may be written
HOOCCH2.C(OH)(COOH).CH2COOH. How many asymmetric carbon atoms does this
molecule contain?
2. This question is about the redox chemistry of vehicle pollution

The unwanted pollutants from the

exhausts of vehicles include unburnt
hydrocarbons (HCs), carbon monoxide
and oxides of nitrogen, mainly NO and
NO2.
The first two pollutants arise if there is
insufficient oxygen present to oxidise
them fully. The oxides of nitrogen are
formed in larger quantities if too much
oxygen is present.

(a) Write an equation for the complete combustion of petrol, assuming that the only
hydrocarbon present is octane, C8H18.

Any unburnt hydrocarbons and carbon monoxide may be removed by being oxidised, either
by oxygen or water. Platinum and / or palladium metal is used to catalyse these oxidation
reactions.

(b) Write an equation for the oxidation of CO by i) oxygen and ii) water.

The nitrogen oxides must be removed by being reduced to nitrogen gas. Any carbon
monoxide present can accomplish this, as can any hydrogen gas present. These reduction
reactions are catalysed by rhodium metal.

(c) Write an equation for the reduction of NO by i) carbon monoxide and ii) hydrogen.

To help maintain a stable oxygen : fuel ratio, so-called ‘oxygen-storage materials’ are used.
One commonly used is ceria which exists as an equilibrium mixture of cerium(III) and
cerium(IV) oxides.

(d) Write an equation for this equilibrium. (The symbol for cerium is Ce.)

The combustion of diesel is less efficient than that of petrol. Despite an excess of oxygen,
unburnt hydrocarbons, CO and even solid carbon are produced. Whilst the first two
pollutants may be removed as before in the catalytic converter, the carbon formed would
simply block it up were it not removed. At the operating temperatures within the catalyst,
very little of the carbon reacts with oxygen; it is, however, oxidised by nitrogen dioxide, NO2,
forming CO2 and NO.

(e) Write an equation for the reaction between carbon and NO2.

In order to remove the oxides of nitrogen emitted from the catalyst, further
reducing agent is added. One such reducing agent is ammonia, prepared
by the decomposition of an aqueous solution of urea, H2NCONH2. The
urea solution is known commercially as ‘AdBlue’.

(f) Draw the structure for urea indicating the approximate angles for the N–C–O and the
H–N–H bonds.

(g) Write an equation for the production of ammonia from urea and water.

(h) Write an equation for the reaction between ammonia and i) NO and ii) NO2.

(i) On your answers for parts b, c, d, e and h underline with a single line the atom(s) which
undergo oxidation and underline with a double line those atom(s) which undergo
reduction.
3. This question is about acyl chlorides and related functional groups

Acyl chlorides, RCOCl, are highly reactive

compounds which rapidly react with water
to give carboxylic acids, and with alcohols
to give esters.

Other oxochlorides containing bonds to

chlorine and double bonds to oxygen
such as phosphoryl chloride (phosphorus
trichloride oxide, POCl3) and thionyl
chloride (sulfur dichloride oxide, SOCl2)
react in an analogous fashion.

(a) Write a balanced equation for the reaction between ethanoyl chloride and water.

(b) Write a balanced equation for the reaction of propanoyl chloride with ethanol.

Phosgene (carbonyl chloride, COCl2), which can be thought of as a diacyl chloride, reacts
similarly with alcohols. It is often used in synthesis, despite its toxicity. It has been used in
the synthesis of Carbaryl, a broad-spectrum insecticide.
CONHCH3
OH O

COCl2 CH3NH2
A
C11H7O2Cl
Carbaryl

(c) Draw the structure for compound A.

(d) Draw the structures of phosphoryl chloride and thionyl chloride, clearly indicating their
shapes. What are the oxidation states of the phosphorus and the sulfur in these
compounds?

(e) Write an equation for the reaction between thionyl chloride and water.

(f) Give the structure of the phosphate ester formed when 1 mole of POCl3 reacts with i) 1
mole of methanol and ii) 2 moles of methanol.

1 mole of POCl3 reacts with 3 moles of water to produce phosphoric acid, H3PO4. When pure
phosphoric acid is heated with POCl3 another phosphorus-containing acid, B, is produced.
The addition of aqueous silver nitrate to a solution of acid B produces a white precipitate
which contains 71.3% by mass silver and 10.2% by mass phosphorus, the remainder being
oxygen.

(g) Suggest a structure for the acid B and write an equation for its formation from
phosphoric acid and POCl3, given that the only other product is HCl.
4. This question is about the thermal decomposition of copper(II) sulfate

Thermogravimetry is an analytical technique

which involves heating a substance and
measuring the change in mass.

The graph below shows the change in mass

as copper(II) sulfate pentahydrate,
CuSO4.5H2O, is heated.

Decomposition takes place where the

gradient is steepest leaving various
decomposition products indicated by A to F in
the diagram.

10
A
Percentage mass loss

20
B
30
C
40

50 D

60
E
70 F

80

90

100
200 400 600 800 1000
Temperature / oC

(a) Using the data from the graph, suggest formulae for compounds A, B, and C.

(b) On heating E, a redox reaction occurs to form F. Identify E and F and write an equation
for this reaction.

(c) Compound D is formed when exactly half of C has decomposed to form E. What is the
empirical formula of D?
5. This question is about emergency oxygen supplies
Rather than carrying heavy high-pressure
oxygen cylinders, most aeroplanes rely on
chemically generated oxygen in the event of
an emergency.

These generators are typically composed of a

mixture of sodium chlorate(V), NaClO3, iron
filings and barium peroxide, BaO2. Once
initiated, the sodium chlorate(V) undergoes
thermal decomposition producing oxygen
gas. The iron combines with some of the
oxygen to produce enough heat to sustain
the reaction.

(a) Write a balanced equation for the decomposition of sodium chlorate(V).

The barium peroxide removes toxic side products which include chlorine and chloric(I) acid,
HClO. Barium chloride and oxygen are common products in these two reactions.

(b) Write a balanced equation for the reaction between i) barium peroxide and chlorine and
ii) barium peroxide and chloric(I) acid.

When a mask is deployed, the flow rate of oxygen gas is designed to change over time as
the aeroplane falls to a safe altitude. Shown below is the manufacturer’s specification for the
flow rate from one such oxygen generator.
Oxygen flow (per person) / dm3 min-1

4.0
3.6

3.0

2.0

1.2
1.0
0.7

0.0
3.5
0 1 2 3 4 5 6 7 8 9 10 11 12
Time / min
Ten seconds after being activated, the flow rate is at its maximum of 3.6 dm3 min –1. This
lasts for approximately 50 seconds before falling as shown in the graph.

(c) Use the graph to estimate the total volume of oxygen produced by the generator.

(d) Calculate the mass of sodium chlorate needed to produce 60 dm3 of oxygen.
[Assume 1 mol of any gas occupies 24.0 dm3 at r.t.p.]

A portable, self-contained closed-circuit breathing apparatus contains a chemical supply of

oxygen similar to that in an aeoroplane. It also contains a means to remove exhaled carbon
dioxide. Very often potassium superoxide (KO2) is used for this. KO2 reacts with water,
liberating further oxygen, and the by-product of this reaction absorbs the CO2.

(e) Write down the oxidation state of the oxygen in i) CO2 ii) BaO2 and iii) KO2.

(f) Give the equations for the reactions i) between potassium superoxide and water and
ii) between the by-product and carbon dioxide.
6. This question is about the synthesis of Viagra TM

The reaction scheme shown opposite is

based on the first synthesis of sildenafil.
CE
This is the active ingredient in Viagra, the
drug used for the treatment of “male
erectile dysfunction”.
NS
O
Note that the by-products are not
necessarily indicated in this scheme. RE
D

(a) Draw structures for the intermediates B, D, E, F, G, I, and J.

(b) i) Suggest suitable reagent(s) for the conversion of B to C.

ii) Suggest a suitable reagent for the formation of F from E.

(c) In the formation of I from H, the first step in the mechanism is a deprotonation by the
sodium hydroxide solution. On the answer sheet, indicate clearly which hydrogen is
removed by the base.

(d) Deduce the structure for N-methylpiperazine, the reagent needed to convert J to
sildenafil.

Compound A is actually prepared by the reaction between hydrazine, N2H4, and reagent K
according to the balanced equation below.

K + N2H4 A + 2 H2 O

(e) i) Draw the structure for hydrazine.

ii) Suggest a structure for K.

 H
N N

O (CH3)2SO4
B
C10H16N2O2
O A
C9H14N2O2
?

H3C

SOCl2 conc H2SO4 / HNO3 N N

E D
O
C8H10N3O3Cl C8H11N3O4

OH C
C8H12N2O2

? O Cl H3C
N N
O O

H2 / Pd H2N
F G O NH
C8H12N4O3 C8H14N4O H
C17H22N4O3
O

NaOH in
O O C2H5OH / H2O

S
( H2O)
N N N-methylpiperazine Cl OH
J I
O
C17H20N4O2
C17H19SN4O4Cl

N N
H

O
N

N
S

sildenafil O O
C22H30SN6O4
7. This question is about the spectra of haloalkanes

Haloalkanes have been used as aerosol

propellants and refrigerants but are now
largely banned due to the damage they
cause to the ozone layer. Halon 1211
was once commonly used in fire
extinguishers (now only found in fighter
jets) and ‘Halothane’ is an inhalational
general anaesthetic.

Further examples of haloalkanes are

given in the table below.

Common name Structural formula

A CFC-113 Cl2FC-CClF2

B CFC-113a Cl3C-CF3

C HFC-134a F3C-CH2F

D CFC-11 (Freon-11, R-11) CCl3F

E CFC-12 (Freon-12, R-12) CCl2F2

F CFC-13 CClF3

G Halon 1211 CBrClF2

H Methylene bromide CH2Br2

Whilst naturally occurring carbon and fluorine exist as essentially the single isotopes 12C and
19
F, chlorine consists of 75% 35Cl and 25% 37Cl; bromine consists of 50% 79Br and 50% 81Br.
The presence of chlorine and bromine atoms in molecules therefore leads to characteristic
patterns for molecular ions in mass spectrometry. As an example, the mass spectrum of
CFC-13 (F) includes peaks at m/z = 104 (CF335Cl•+) and 106 (CF337Cl•+) with intensity ratio
3:1.

(a) Calculate the m/z values and relative intensities for the molecular ion peaks of
CFC-12 (E).

(b) Sketch the mass spectrum for the molecular ion peaks of Halon 1211 (G). Indicate the
relative intensity of each peak and which ion(s) are responsible for them.

A sample of methylene bromide (H) was enriched with deuterium (2H). On analysis it was
found that half of the hydrogen content of the sample was deuterium. In the mass spectrum
there are molecular ion peaks with m/z values of 172, 173, 174, 175, 176, 177 and 178.

(c) Calculate the relative intensities of these molecular ion peaks.

NMR spectroscopy is a technique which reveals the number of different environments of
certain nuclei in a molecule. NMR active nuclei such as 1H, 13C and 19F are routinely
studied. As an example, the two hydrogen atoms in methylene bromide (H) are equivalent
and hence would give rise to a single peak in the 1H NMR spectrum. The same is true for
the hydrogens in HFC-134a (C).

(d) In your booklet, complete the table indicating the number of different fluorine
environments for the each of the compounds A-G.

(e) The anaesthetic Halothane has the formula C2HBrClF3 and shows one signal in its 19F
NMR spectrum. Draw the two possible three-dimensional structures for Halothane.

The intensity of a signal in a 1H or 19F NMR spectrum is proportional to the number of nuclei
in that particular environment.

(f) For each compound with more than one signal in its 19F NMR spectrum, indicate in the
appropriate column of the table the expected intensity ratio.

NMR spectra are complicated by coupling between nuclei. If an NMR-active nucleus is

within three bonds of another similar nucleus which is in a different chemical environment, its
signal will be split into a number of peaks instead of appearing as a single peak. If a nucleus
couples to n NMR-active nuclei, its signal will split into a total of (n+1) peaks.

(g) The 19F NMR spectrum of one of the haloalkanes from the table is shown below. In
your answer booklet draw the structure of the haloalkane and indicate with an arrow
which fluorines give rise the signals X and Y.

x 300
x 300
X Y

-67 -68 -69 -70 -71 -72 ppm

Acknowledgements

The Chemistry Olympiad Committee would like to thank the following people for their help
and advice in the preparation of this paper:

The Environmental Catalysts and Technologies department of Johnson Matthey Catalysts.

The World War II poster of phosgene is reproduced courtesy of the National Museum of
Health and Medicine, Armed Forces Institute of Pathology, Washington, D.C. Further
chemistry-related posters may be found on their website:

www.nmhm.washingtondc.museum

Molecular Products Ltd for their helpful advice on chemical oxygen generators.

www.molecularproducts.co.uk

Marshall Aerospace for the loan of the emergency oxygen system used in the photograph.

www.marshallaerospace.com

The graph of the oxygen flow rate has been redrawn from a data sheet produced by the
manufacturers Scott Aviation, a division of Scott Aviation Inc.

www.scottaviation.com

The synthesis of sildenafil is taken from:

“Sildenafil (VIAGRATM), a potent and selective inhibitor of type 5 cGMP phosphodiesterase
with utility for the treatment of male erectile dysfunction”
Nicholas K. Terrett, Andrew S. Bell, David Brown and Peter Ellis
Bioorganic & Medicinal Chemistry Letters, 1996, Vol 6 p1819-24.

The NMR department of the University of Cambridge, Department of Chemistry for running
the 19F NMR spectrum for question 7.

The photography department of the University of Cambridge, Department of Chemistry for

the photographs used in this paper.
 38th INTERNATIONAL CHEMISTRY OLYMPIAD

UK Round One - 2006

MARKING SCHEME
Notes
Chemical equations may be given as sensible multiples of those given here.

State symbols do not need to be included in the chemical equations to obtain the
mark(s).

Answers should be given to an appropriate number of significant figures

although the marker should only penalise this once.

Total 78 marks.

Question 1
Answer Marks

(a) C12H22O11 + 12O 2 12CO2 + 11H2O 1

(b) Allow 110 kJ or 111kJ (rounded to 3 sig fig) 1

(c) 95 sweets [Allow ecf from (b)] 1

(d) Mass of sodium hydrogencarbonate = 0.0210g 1

Mass of tartaric acid = 0.0188g 1

2 marks for all 3 structures shown correctly. 1 further mark for

(e) enantiomers correctly identified.

HO2C CO 2H
C C
HO H
H OH
------------------------------
HO2C CO 2H HO2C CO 2H 3
C C C C
H OH H H
HO H HO OH

enantiomers

(f) None 1

9 marks
Question 2
Answer Marks

(a) C8H18 + 12½O2 8CO2 + 9H2O 1

i) CO + ½O2 CO2
(b) 1
for both
ii) CO + H2O CO2 + H2 equations
correct

i) NO + CO ½N2 + CO2
(c) 1
for both
ii) NO + H2 ½N2 + H2O equations
correct

(d) Ce2O3 + ½O2 2CeO 2 1

(e) C + 2NO2 CO2 + 2NO 1

1 mark for structure shown correctly. 1 mark for both bond angles
correct.
(f)
H
o
120-123 N H 2

O C

N H

H o
107-120

(g) CO(NH2)2 + H2O CO2 + 2NH3 1

(h) i) 2NH3 + 3NO 2½ N2 + 3H2O 1

ii) 4NH3 + 3NO2 3½ N2 + 6H2O 1

Award marks here provided that candidates have a minimum of 5

(i) of the 8 equations correct. Allow 4 marks for all 8 redox changes
correct, 3 marks for 7, 2 marks for 6 and 1 mark for 5 redox 4
changes correct.

See underlining (b), (c), (d), (e) and (h) above

14 marks
Question 3
Answer Marks

(a) CH3COCl + H2O CH3COOH + HCl 1

(b) CH3CH2COCl + CH3CH2OH CH3CH2COOCH2CH3 + HCl 1

C
O Cl
1

(c)

1 mark for each structure with correct shape indicated.

1 mark for both oxidation states correct.
O
S
Cl 3
P O
(d) Cl Cl
Cl
Cl
Tetrahedral Pyramidal
P = +5 S = +4

(e) SOCl2 + H2O SO2 + 2HCl 1

SOCl2 + 2H2O H2SO3 + 2HCl [allow either answer]

O
(f) i)
P 1
OCH 3
Cl
Cl

O
ii)
P 1
OCH3
Cl
OCH3

O O
(g)

P P 2
HO O OH
HO OH

5H3PO4 + POCl3 3H4P2O7 + 3HCl

11 marks
Question 4
Answer Marks

(a)
A: CuSO4.3H2O 1

B: CuSO4.H2O 1

C: CuSO4 1

(b) E: CuO 1

F: Cu2O 1

2CuO Cu2O + ½O 2 1

(c) D: Cu2SO5 1

7 marks

Question 5
Answer Marks

(a) NaClO 3 NaCl + 1½O2 1

i) BaO 2 + Cl2 BaCl2 + O2 1

(b)

ii) BaO 2 + 2HClO BaCl2 + 1½O2 + H2O 1

(c) 15dm 3 1

(d) Allow 117g or178g 1

2 marks for all 3 oxidation states correct. 1 mark for 2 correct

i) -2

(e) ii) -1 2

iii) -½

(f) i) 2KO2 + H2O 2KOH + 1½O2 1

ii) 2KOH + CO2 K2CO3 + H2O 1

[Allow also KOH + CO2 KHCO3]

9 marks
Question 6
Answer Marks
Allow 1 mark for each correct structure. Give credit where the
(a) candidate has identified the relevant part of the structure correctly –
do not deduct marks for trivial errors in copying the remainder of the
molecule.

H3C
H3 C
N N
N N
O
O

O
OH NO2
B D
H3C H3C
N N N N

O O

Cl NO 2 NH2 NO 2
E F

H 3C
N N

H3C N N
H
N N
O
O

NH2 NH2 G
I

H 3C
N N

N N
H

Cl
S

O O J
Question 6 continued
Answer Marks

(b) i) HCl(aq) 1

ii) NH3 1

(c) H3C
N N
O

H2N
O NH 1
H
O

(d) CH3
N
1
N
H

(e) i) H
N N
H
H H 1

allow any diagram showing correct structure

O O
ii)
O 1

13 marks
Question 7 Marks

C35Cl2F2+ = 120 C35Cl3 7ClF2+ = 122 C37Cl2F2+ = 124 1

(a) ratio 9:6:1 1

(b)

1 mark for peaks at correct masses , 1 mark for correct relative intensities
and 1 mark for the formulae of the ions indicated correctly (allow mark if
‘+’ sign omitted - as here).

(c) ratio 1 : 2 : 3 : 4 : 3 : 2 : 1 1

Number of different
Structural
Common name fluorine
formula
environments

A CFC-113 Cl2FC-CClF 2 2

B CFC-113a Cl3C-CF3 1
3 marks
(d) for all 7
correct, 2
C HFC-134a F3C-CH2F 2 marks for
6 correct,
CFC-11 (Freon-11, R- 1 mark for
D CCl3F 1 5 correct
11)

CFC-12 (Freon-12, R-
E CCl2F2 1
12)

F CFC-13 CClF 3 1

G Halon 1211 CBrClF 2 1

Question 7 continued Marks

1 mark for structure showing -CF3 group. 1 mark for mirror images shown
correctly.

Br Br 2
(e)
Cl Cl
F 3C H CF 3
H

Structural Expected
Common name
formula intensity ratio

A CFC-113 Cl2FC-CClF 2 1 : 2

B CFC-113a Cl3C-CF3

2
(f) C HFC-134a F3C-CH2F 3 : 1

CFC-11 (Freon-11, R-
D CCl3F
11)

CFC-12 (Freon-12, R-
E CCl2F2
12)

F CFC-13 CClF 3

G Halon 1211 CBrClF 2

F Cl
Y
X
Cl F 2
(g) Cl F Allow 1 mark for the correct structure and 1
mark for correct identification of fluorines.

15 marks
 39th INTERNATIONAL

CHEMISTRY OLYMPIAD

2007
UK Round One

STUDENT QUESTION BOOKLET

* * * * *
„ The time allowed is 2 hours.
„ Attempt all 6 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.

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.
 H He
1 2
1.008 4.003

Li Be symbol B C N O F Ne
3 4 atomic number 5 6 7 8 9 10
6.94 9.01 mean atomic mass 10.81 12.01 14.01 16.00 19.00 20.18

Na Mg Al Si P S Cl Ar
11 12 13 14 15 16 17 18
22.99 24.31 26.98 28.09 30.97 32.06 35.45 39.95

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
39.102 40.08 44.96 47.90 50.94 52.00 54.94 55.85 58.93 58.71 63.55 65.37 69.72 72.59 74.92 78.96 79.904 83.80

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
85.47 87.62 88.91 91.22 92.91 95.94 101.07 102.91 106.4 107.87 112.40 114.82 118.69 121.75 127.60 126.90 131.30

Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
132.91 137.34 138.91 178.49 180.95 183.85 186.2 190.2 192.2 195.09 196.97 200.59 204.37 207.2 208.98

Fr Ra Ac+
87 88 89

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
*Lanthanides 58 59 60 61 62 63 64 65 66 67 68 69 70 71
140.12 140.91 144.24 150.4 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
+Actinides
90 91 92 93 94 95 96 97 98 99 100 101 102 103
232.01 238.03
1. This question is about launching the space shuttle

To launch the space shuttle, two propulsion

systems are used. Most of the thrust for the first
two minutes of flight comes from the two reusable
solid rocket boosters. The so-called ‘external
tank’ provides the remainder of the thrust needed
to get the shuttle into orbit.

The external tank is filled with liquid hydrogen

and liquid oxygen which react to form water. The
solid rocket boosters use a mixture of aluminium
powder and ammonium perchlorate, NH4ClO4,
together with an iron oxide catalyst and an
organic binder.

(a) Write the equation for the reaction between hydrogen and oxygen.

(b) The external tank has a mass of 27 tonnes (27,000 kg) when empty and 745 tonnes
when full. Assuming these are present in the correct stoichiometric proportions,
calculate the masses of hydrogen and oxygen in the external tank.

(c) In practice, the actual masses of hydrogen and oxygen used are 104 and 614 tonnes
respectively. Given that the densities of liquid hydrogen and oxygen are 0.0708 and
1.141 g cm–3, calculate the volumes of these liquids needed and hence the total
capacity of the external tank in m3.

The reaction that takes place during the combustion of the solid rocket booster fuel has been
summarized as:

10Al(s) + 6NH4ClO4(s) 4Al2O3(s) + 2AlCl3(s) + 12H2O(l) + 3N2(g)

(d) Given the following standard enthalpies of formation, calculate the standard enthalpy
change at 298 K for this reaction as given.

NH4ClO4(s) Al2O3(s) AlCl3(s) H2O(l)

Δf H / kJ mol–1 –295.3 –1675.7 –704.2 –285.8

(e) Given that 450 tonnes of solid propellant are used in the solid rocket boosters in total,
and that aluminium is the limiting reagent present at 16% in the mixture, calculate the
energy released when this is reacted according to the above equation.
2. This question is about geometric shapes in chemistry

Phosphorus exists as a number of allotropes, the

most reactive being white phosphorus. This was
first prepared in the 17th century from the
reduction of the phosphate present in urine.

Solid white phosphorus contains P4 molecules,

with each P atom at the vertex of a regular
tetrahedron.
cuboctahedron

(a) Draw the structure of a molecule of P4, showing all the chemical bonds.

(b) How many edges are there in total in a regular tetrahedron?

White phosphorus spontaneously ignites in air to form a mixture of phosphorus(III) oxide and
phosphorus(V) oxide.

(c) Write an equation for the formation of i) phosphorus(III) oxide and ii) phosphorus(V)
oxide from the elements.

The structure of each oxide is also based on a regular tetrahedron. The phosphorus atoms
remain at the vertices but are no longer bonded to each other. Instead the P atoms are
joined by bridging oxygens.

(d) Draw the structure of phosphorus(III) oxide.

Phosphorus(V) oxide has a further oxygen atom bonded to each phosphorus atom at the
vertex of the tetrahedron.

(e) Draw the structure of phosphorus(V) oxide.

Each oxide reacts with water to form an acid – phosphorus(V) oxide forms phosphoric(V)
acid, H3PO4.

(f) Draw the molecular structure of phosphoric(V) acid, showing all of the bonds.

(g) Write the equation for the reaction forming phosphoric(V) acid.

A quantitative method for determining phosphate levels in aqueous solution involves adding
ammonium molybdate, (NH4)2MoO4, to form a precipitate of ammonium molybdophosphate.
The structure of this solid is based on a cuboctahedron (shown above). A molybdenum
atom lies at each vertex of the cuboctahedron and these are joined by oxygen atoms with
every edge of the cuboctahedron being bridged by an oxygen atom. A further oxygen atom
is joined to every vertex. A single phosphate unit lies at the centre of the structure with each
of its four oxygen atoms coordinating to three molybdenum atoms.

(h) Calculate the oxidation state of molybdenum in ammonium molybdate.

(i) How many i) vertices and ii) edges are there in a cuboctahedron?

(j) Calculate the number of i) molybdenum atoms and ii) oxygen atoms in the
molybdophosphate ion.

(k) Given that no atom changes its oxidation state during the formation of ammonium
molybdophosphate, calculate the overall charge of the molybdophosphate ion and
hence the formula of ammonium molybdophosphate.
3. This question is about phosphate levels in our environment

Excess phosphate is undesirable in our water supply

since it promotes the growth of algae. High phosphate
levels in the blood (hyperphosphataemia), caused by an
inability of the kidneys to filter out excess phosphate from
food, cause a range of bone diseases. A safe level of
phosphate in blood serum is <1.8 mmol dm–3.

To determine the concentration of phosphate ions in

solution, ammonium molybdophosphate (formed by the
addition of ammonium molybdate, (NH4)2MoO4, to
phosphate ions) is titrated with NaOH using a
phenolphthalein indicator. One mole of ammonium
molybdophosphate contains one phosphate unit and
requires 23 moles of NaOH in the titration before the end
point is reached.

(a) Which two of the following statements explain why so many moles of hydroxide are
needed per mole of ammonium molybdophosphate? Circle the correct options in the
answer booklet.

A Sodium hydroxide is a weak alkali

B Ammonium molybdophosphate has a very high molecular mass
C The molybdenum-containing species is acidic
D Phosphate ions are acidic
E The molybdophosphate ion contains many molybdenums

(b) 10.0 cm3 of treated blood serum was reacted with excess ammonium molybdate and
the precipitated ammonium molybdophosphate required 17.25 cm3 of 0.0100 mol dm–-3
NaOH. Calculate the concentration of phosphate in the blood serum in mol dm–-3.

(c) The degree to which a phosphate ion is protonated in aqueous solution depends on the
pH. Use the following data to calculate which form of phosphate is prevalent in blood
serum at pH 7.4.
–
H3PO4 (aq) H+ (aq) + H2PO4 (aq) Ka1 = 7.9×10–3 mol dm–3
– 2–
H2PO4 (aq) H+ (aq) + HPO4 (aq) Ka2 = 6.2×10–8 mol dm–3
2– 3–
HPO4 (aq) H+ (aq) + PO4 (aq) Ka3 = 4.4×10–13 mol dm–3

Lanthanum carbonate (marketed as FosrenolTM) is currently being used to treat

hyperphosphataemia; aluminium sulfate has been used to control phosphate levels in ponds.
Both LaPO4 and AlPO4 are essentially insoluble in water and are therefore removed as
precipitates.

(d) Write the equation for the reaction between lanthanum carbonate and the hydrochloric
acid present in the stomach.

The saturated concentrations of these phosphates can be worked out from their solubility
products (Ksp):
3–
Ksp(LaPO4) = [La3+(aq)]sat[PO4 (aq)]sat = 7.08×10–27 mol2 dm–6
3–
Ksp(AlPO4) = [Al3+(aq)]sat[PO4 (aq)]sat = 9.84×10–21 mol2 dm–6

(e) Calculate the concentration of a saturated solution of lanthanum phosphate.

(f) If an equimolar solution of aluminium and lanthanum ions is added slowly to a solution
containing phosphate ions, which phosphate would precipitate first?
4. This question is about the analysis of a flame-retardant

Retardol C, Pyroset TKC and Proban CC

are three trade names given to a flame-
retardant used to produce crease-
resistant and flame-retardant finishes on
textiles such as those used to make
nightclothes for children.
–
The flame-retardant is a salt , X+ Y ,
prepared by the reaction between
phosphine, PH3, and methanal in dilute
–
aqueous acid. The anion Y simply
depends on which acid was used in the
preparation.

(a) Draw the structures of phosphine and methanal, clearly indicating the geometry of each
molecule.
The mass spectrum of X+ (down to 50 m/z) is shown over the page, together with the proton
and phosphorus-31 NMR spectra. The carbon-13 NMR spectrum of X+ (not shown) shows
there is just one environment of carbon atom in the cation.

(b) By inspection of the 1H NMR spectrum, suggest the number of environments of

hydrogen atoms in X+. What is the ratio of the number of hydrogen atoms in the
different environments?

When the sample is mixed with a little D2O instead of H2O, the signal at 6.25 ppm in the 1H
NMR spectrum disappears.

(c) What functional group does this suggest may be present in X+?

The 31P NMR spectrum shows one signal split into a multiplet due to coupling to hydrogens.

(d) How many hydrogen nuclei is the phosphorus coupling to?

The mass spectrum shows the molecular ion and a number of fragmentation peaks.

(e) i) The fragmentation process shows consecutive losses of a 30 mass unit. Suggest
the formula for the fragment lost.
ii) Suggest a formula for the X+ ion.

iii) A mass spectrum of the D2O solution of X+ no longer shows a peak at 155, but
instead shows a peak at a higher m/z. At what value of m/z would you expect this new
peak to come?

(f) i) Suggest a structure for the cation X+, clearly indicating its geometry.

ii) Suggest a structure for the ion at m/z = 65.

5. This question is about the synthesis of Tamiflu TM

Tamiflu is the anti-

influenza drug currently O
being used to treat so-
called ‘Bird-flu’. Its O
structure is shown on the O O
right. The bold wedged
bond is coming out of the
N TamifluTM
plane of the paper, the
hashed bonds are going H C16H28N2O4
into the plane. NH2

In order to increase its solubility, Tamiflu is actually sold as the phosphate salt.
(a) On the structure in your answer booklet, circle the atom which will be protonated in the
salt.
One of the problems in the synthesis of the drug is ensuring the correct stereochemistry at
each of the stereogenic (chiral) centres in the structure.

(b) i) On the structure in your answer booklet, mark with an asterix each chiral centre.
ii) What is the total number of stereoisomers possible for this structure?
Two syntheses of Tamiflu which have been tried start from the naturally occurring products
Quinic acid and Shikimic acid.

HO OH
HO COOH
COOH

Shikimic acid
Quinic acid
HO HO C7H10O5
C7H12O6
OH OH

Shikimic acid has the advantage of already having the double bond in place but quinic acid
has the advantage of being much cheaper.
One of the problems using either acid is trying to control which of the –OH groups reacts in a
given step. The first step starting from quinic acid is therefore to protect the two –OH groups
on the same side of the ring on adjacent carbon atoms by forming a so-called acetal group
by the acid-catalysed reaction with propanone:
OH OH
HO propanone O
COOH COOH
/ H+ cat

HO
O A
– H2O
OH OH

C7H12O6 C10H16O6

The next steps in the synthesis are outlined below. Inorganic by-products are not shown in
the scheme.
O O
S
ethanol Cl CH3 SO2Cl2
A + catalyst
B C + base D + E + F
C10H16O6 C13H22O8S major unwanted C13H21ClO7S
product isomer left over
intermediate
D reacts with an excess of pentan-3-one to give G as shown below.
O

O
pentan-3-one O
D + + H
/ H catalyst
O G C3H6O
C15H24O7S
O
S
O O

(c) Draw the structures of compounds B, C, D, E and F and for the by-product H, showing
the correct stereochemistry by the use of bold and hashed bonds as appropriate.

G may easily be prepared from the more expensive Shikimic acid as outlined below.
Inorganic by-products are not shown.
O O
S
SOCl2 ethanol pentan-3-one Cl CH3
Shikimic acid I J + K G
/ H catalyst

(d) Draw the structures of compounds I, J, and K showing the correct stereochemistry as
appropriate.

The acetal in G may be opened up under reducing conditions to give mainly L (shown
below). On treatment with base L cyclises to give M which contains a 3-membered ring.
The new ring is opened up with sodium azide yielding a mix of isomers, N and O either of
which yields the same cylic compound P on treatment with trimethylphosphine. Further
treatment with sodium azide opens the new ring to give mainly Q which upon acylation and
hydrogenation finally yields neutral Tamiflu as outlined below.

O O O
reductive acetal O base
G opening
M + S
H3C O
HO L
O C15H26O7S
S Na N3
O O + weak acid

P
O N + O
P + N2 + P
isomers
C14H23NO3 C14H23N3O4

Na N3
O O
+ weak acid
O
O H2 / Ni Tamiflu
Q + R
C16H28N2O4
C14H24N4O3 OH C16H26N4O4

(e) On the structure in your answer booklet, circle the most acidic proton in L which is
removed by the base.

(f) Draw the structures of compounds M, N, O, P, Q and R again showing the correct
stereochemistry as appropriate.
6. This question is about chlorine dioxide

Chlorine dioxide, ClO2, was the first

oxide of chlorine to be discovered.
Although unstable as a liquid or gas, it
is now produced on a very large scale
for the bleaching of wood pulp and for
water treatment. More recently, it has
been used to remove mould from
houses flooded following Hurricane
Katrina in New Orleans.

A mobile chlorine dioxide generator

used for decontamination

(a) Draw a ‘dot & cross’ diagram of a ClO2 molecule showing the outershell electrons. Give
an estimate of the O-Cl-O bond angle.

Chlorine dioxide was first obtained by Humphry Davy by the very hazardous
disproportionation of chloric acid, HClO3, formed by adding concentrated sulfuric acid to a
solid chlorate such as KClO3. The other products of this disproportionation reaction are
water and perchloric acid, HClO4.
(b) i) Give the oxidation states of chlorine in ClO2, HClO3 and HClO4.
ii) Using these oxidation states, or otherwise, write a balanced equation for the
formation of ClO2 from HClO3.
iii) Give the structure of a molecule of perchloric acid. What is the bond angle in the
perchlorate ion?

For safety reasons, chlorine dioxide is usually generated where it is to be used. For pulp
bleaching, ClO2 is made by the partial reduction of NaClO3 under acidic conditions using a
variety of reducing agents, for example, sulfur dioxide.

(c) Write a balanced equation for the formation of ClO2 by this reaction, using sulfuric acid
for acidification (there is only one other product).

In the laboratory, ClO2 is produced by the reaction between NaClO3 and oxalic acid,
(COOH)2, again in the presence of sulfuric acid. This also generates CO2, which dilutes the
ClO2.

(d) Write a balanced equation for the formation of ClO2 by this reaction.

The company Sabre produce their ClO2 by oxidising sodium chlorate(III) with chlorine gas.

(e) i) Suggest the formula for sodium chlorate(III).

ii) Write a balanced equation for the formation of ClO2 from chlorine and sodium
chlorate(III).
Acknowledgements

The Chemistry Olympiad Committee would like to thank the following people / organisations
for their help and advice in the preparation of this paper.

Information and photographs concerning the space shuttle is freely available from NASA:

www.nasa.gov

Shire Pharmaceuticals Group plc:

www.shire.com

The spectra in Question 4 were run by the NMR and mass spectrometry departments of the
University of Cambridge, Department of Chemistry.

The cartoon used in Question 4 is taken from ‘The Boy’s Playbook of Science’ by John
Henry Pepper, 1881.

The synthesis of TamifluTM is taken from:

“Practical Total Synthesis of the Anti-Influenza Drug GS-4104” John C. Rohloff et al.
Journal of Organic Chemistry, 1998, Vol 63 p4545-4550.

The cartoon used in the Tamiflu question was drawn by Anthony Lim, a first year chemistry
student at the University of Cambridge.

The picture of the chlorine dioxide generator is courtesy of Sabre Technical Services, LLC
and copyright 2007 Sabre Technical Services, LLC.

www.sabretechservices.com
 39th INTERNATIONAL CHEMISTRY OLYMPIAD

UK Round One - 2007

MARKSCHEME
Notes

Chemical equations may be given as sensible multiples of those given here.

State symbols do not need to be included in the chemical equations to obtain the mark(s).
Answers should be given to an appropriate number of significant figures although the
marker should penalise this only once.
As a general rule, markers should aim to reward correct chemistry. Errors cannot be
ignored but markers should ensure that candidates are not penalised for trivial errors.
Total mark: 73

Question 1 Mark

(a) H2 + ½ O2 H2O 1

(b) Mass of hydrogen = 80 t 1

Mass of oxygen = 638 t 1

(c) Volume of hydrogen = 1470 m3 Volume of oxygen = 538 m3

2
3
Total tank capacity = 2010 m

2 marks if total tank capacity correct. If incorrect, allow 1 mark for volume of H2
or O2 correct.

(d) - 9769 kJ mol–1 1

(e) 2.6 MJ (2.6 x 109 kJ) 2

Don’t penalise if – sign present; allow 1 for correct working even if final answer
incorrect.

Marks = 8
Question 2 Mark

(a)
P
P 1
P
P
(b) Number of edges: 6 1

(c) i) P4 + 3O2 P4O6 (allow mark for any correctly balanced 1

equation giving P2O3 or P4O6 )

ii) P4 + 5O2 P4O10 (allow mark for any correctly balanced 1

equation giving P2O5 or P4O10 )

(d) Structure of phosphorus(III) oxide: (e) Structure of phosphorus(V) oxide:

O
P

O O P
O O O 1+1
P P O
O
P P
P O
O O
O O P
O O
O

(f) O

P 1
OH
HO
OH (stereochemistry not required)

(g) P4O10 + 6H2O 4H3PO4 (allow balanced equation from P2O5 ) 1

(h) Oxidation state of molybdenum: + 6 (sign not essential for mark) 1

(i) (i) Number of vertices: 12 (ii) Number of edges: 24 1+1

(j) (i) Number of Mo atoms: 12 (ii) Number of O atoms: 40 1+2

(allow 1 mark for 36 O atoms)

(k) Overall charge of the molybdophosphate ion: – 3 1

Formula of ammonium molybdophosphate: (NH4)3Mo12O40P 1

(allow variants e.g. N3H12Mo12O40P)

Marks = 16
Question 3 Mark

(a) C&E 1

(b) Concentration of phosphate: 7.5 x 10– 4 mol dm–3 2

(2 marks for fully correct answer, allow 1 mark for correct working if final answer
incorrect)

(c) Form of phosphate: HPO42– 1

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

(2 marks if completely correct; 1 mark if incorrect equation but formula for

La2(CO3)3 is correct)

(e) 8.41 x 10–14 mol dm–3 1

(f) LaPO4 1

Marks = 8

Question 4 Mark

(a) O
P
H 1+1
H C
H pyramidal not planar H H planar

(b) Number of environments of hydrogen: 2 Ratio: 1:2 1+1

(c) Functional group: -OH (or alcohol, hydroxyl) 1

(d) Number of hydrogen nuclei: 8 1

(e) (i) Formula for fragment: CH2O 1

(ii) Formula for the X+ ion: C4H12O4P (allow correct variants) 1

(iii) m/z value: 159 1

(f) (i) Structure for X+: (ii) Structure for ion at m/z = 65:
H H
H OH OH
H
1+1

OH
P
HO P
H
H H
H
H H
H H OH
H

Marks = 11
Question 5 Mark

O
O O
(a) 1
N T amif luTM
H C16H 28N 2O4
NH2 Atom/group indicated should
be circled

O
O * O
(b) (i) 1
*
* Tamif lu TM
N
H C 16H 28N2O4
NH 2

(ii) Total number of stereoisomers: 23 = 8 1

For parts (c), (d) and (f): for each of the structures, award 1 mark if
completely correct as shown below. Deduct ½ mark (for each structure) if
stereochemistry incorrect.
(c)
OH
O O
OH 1
O O O
O

O
O O
S

OH B O
O
C 1

O
O

O
O O 1
O

O
O

O O
S
S 1
O O
O D O E
Question 5 continued Mark

(c)
Cl
1
O O

O
O
O
O
S 1
O
O F H

(d)
O O

HO Cl HO O 1

HO HO

OH I OH J
1

O O
1
O

OH K

(e) O

O
O
1
HO

O
S
O O

(f) M
O

O 1
O

O
Question 5 continued Mark

(f) N (or O)
O

O 1
O

HO

N3

O (or N)
O
1
O
O

N3

OH

P
O
1
O
O

HN

Q
O
1
O
O

H 2N

N3

R
O
1
O
O O

C
N

H N3

Mark = 19
Question 6 Mark

(a)
1

Bond angle: 110 – 120o 1

(actual angle: 117.4)

(b) (i) Oxidation state of chlorine in ClO2: + 4

Oxidation state of chlorine in HClO3: + 5

2
Oxidation state of chlorine in HClO4: + 7

Award 2 marks for all 3 correct, 1 mark for 2 correct

(ii) 3HClO3 2ClO2 + HClO4 + H2O 1

(iii) Structure: Bond angle: 109.5o (109o 28’)

O 1
(allow 109o)
H
Cl
O 1
O
O

(H2SO4)
(c)
2NaClO3 + SO2 2ClO2 + Na2SO4 Allow as ionic 1

2NaClO3 + (COOH)2 + H2SO4 2ClO2 + 2CO2 + 2H2O

(d) + Na2SO4 1
Allow as ionic: 2ClO3– + (COOH)2 + 2H+ 2ClO2 + 2CO2 + 2H2O

(e) (i) NaClO2 1

(ii) 2NaClO2 + Cl2 2ClO2 + 2NaCl 1

Marks
= 11
 40th INTERNATIONAL

CHEMISTRY OLYMPIAD

2008

UK Round One

STUDENT QUESTION BOOKLET

*****
ƒ The time allowed is 2 hours.
ƒ Attempt all 6 questions.
ƒ Write your answers in the special answer booklet.
ƒ In your calculations, please write only the essential steps in
the answer booklet.
ƒ Always give the appropriate units and number of significant
figures.
ƒ You are provided with a copy of the Periodic Table.
ƒ Do NOT write anything in the right hand margin of the
answer booklet.

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.
 H He
1 2
1.008 4.003

Li Be symbol B C N O F Ne
3 4 atomic number 5 6 7 8 9 10
6.94 9.01 mean atomic mass 10.81 12.01 14.01 16.00 19.00 20.18

Na Mg Al Si P S Cl Ar
11 12 13 14 15 16 17 18
22.99 24.31 26.98 28.09 30.97 32.06 35.45 39.95

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
39.102 40.08 44.96 47.90 50.94 52.00 54.94 55.85 58.93 58.71 63.55 65.37 69.72 72.59 74.92 78.96 79.904 83.80

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
85.47 87.62 88.91 91.22 92.91 95.94 101.07 102.91 106.4 107.87 112.40 114.82 118.69 121.75 127.60 126.90 131.30

Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
132.91 137.34 138.91 178.49 180.95 183.85 186.2 190.2 192.2 195.09 196.97 200.59 204.37 207.2 208.98

Fr Ra Ac+
87 88 89

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
*Lanthanides 58 59 60 61 62 63 64 65 66 67 68 69 70 71
140.12 140.91 144.24 150.4 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
+Actinides
90 91 92 93 94 95 96 97 98 99 100 101 102 103
232.01 238.03
1. This question is about the preparation of pure silicon for solar cells

Thousands of tonnes of silicon are produced

each year to be used in solar cells. First,
metallurgical grade silicon, MGS, is made by
reducing quartz (SiO2, the major component of
sand) with carbon in the form of coke and
charcoal.
The MGS produced is typically between 98.5
and 99.5 % pure – nowhere near pure enough for
the electronics industry. Typical impurities include
metals such as iron and aluminium.
sand purified silicon
(a) Write an equation for the reaction between quartz and carbon to form silicon.
High purity silicon can be made from silane (SiH4) and its derivatives. In one such scheme,
silicon is first reacted with HCl at 300 °C to form trichlorosilane and hydrogen. The
trichlorosilane is then reduced in a hydrogen environment to form pure silicon.
(b) i) What is the bond angle in silane?
ii) Write the equation for the reduction of trichlorosilane with hydrogen.

This method is rather energy intensive – a more environmentally friendly method has
recently been developed which requires a tenth of the energy. In this method ethanol reacts
with silicon to form triethoxysilane and hydrogen. Upon heating, the triethoxysilane forms
silane gas and tetraethoxysilane in a disproportionation reaction. The silane gas can be
decomposed at high temperatures to give pure silicon.

(c) i) Write the equation for the disproportionation of triethoxysilane.

ii) Air must be excluded from the process to avoid the spontaneous ignition of the
silane gas. Suggest an equation for this reaction.

An earlier method used to purify the silicon was zone refining. In this technique, a bar of
impure silicon is melted at one end and then the melt zone is gradually moved along the bar,
allowing the silicon to re-solidify behind this zone. Since the impurities are more soluble in
the liquid silicon rather than the solid, as the silicon re-solidifies, the impurities become more
concentrated in the moving melt zone and hence end up in the last region that re-solidifies.

During zone refining, the concentration, Cx, of a given impurity at position x in the re-
solidified bar is given by:
C x = kC 0 (1 − x ) k −1

where C0 is the initial concentration of impurity (usually expressed in number of atoms of

impurity per million atoms); x is distance along the bar from the start, expressed as a fraction
between 0 and 1; k is a constant known as the distribution coefficient whose value depends
on the particular impurity. For aluminium, k = 2.00 x 10–3; for iron, k = 8.00 x 10–6.

(d) i) If the initial concentration of aluminium impurity is 3300 ppm atoms, calculate the
maximum local concentration of aluminium remaining (in ppm) after one melting,
assuming the last 5% of the silicon bar is discarded.
ii) Assuming the only impurity present is iron at 1300 ppm atoms, calculate the
minimum percentage of the silicon that would need to be discarded in order to reach
the level desirable for photocells, <10 ppm.
2. This question is about the kinetics of Vitamin D production in mushrooms

Vitamin D is essential for healthy bone structure.

Mushrooms are a rich source of ergosterol, a
precursor of vitamin D2. Cultivated mushrooms
grown in the dark have little vitamin D2, but when
exposed to UV light, ergosterol is converted into
vitamin D2.

In a kinetics experiment, different mushroom

varieties were irradiated with UV light for varying
periods of time and then analysed for their
concentrations of ergosterol and vitamin D2.

CH 3
H 3C CH3
CH3
CH 3
H 3C CH3 CH 3
CH 3
CH 3
CH3
UV light

CH 2
HO

Ergosterol HO Vitamin D 2

(a) Circle all the chiral centres on the structure of ergosterol in your answer booklet.

(b) During the reaction, one of the hydrogens from the methyl group marked with an arrow
on the structure of ergoesterol above is transferred to a different carbon in the product.
On the structure of vitamin D2 in your answer booklet, circle the carbon atom to which
the hydrogen is transferred.

The kinetics of production of vitamin D2 from ergosterol were expected to be of the form:

rate of production of vitamin D2 = k x [ergosterol]a

where k is the rate constant for the particular mushroom;

[ergosterol] is the concentration of the reactant ergosterol;
a is the order of reaction with respect to the concentration of ergosterol.

The concentrations of vitamin D2 in oyster mushrooms and button mushrooms after

irradiating the mushrooms for different periods of time are shown over the page. Both
graphs are linear.
(c) By examining the graphs, what is the value of a, the observed order of reaction with
respect to [ergosterol]?

minus one zero one two three

(Circle the correct answer in your answer booklet.)

(d) From the graph, determine the rate constant for the production of vitamin D2 from oyster
mushrooms. Include the correct units in your answer.

(e) Estimate the amount of vitamin D2 in 10 g of dried button mushrooms that have been
irradiated for 1 hour.

The rate constant for the production of vitamin D2 is found to vary with temperature
according to the Arrhenius equation:

k ( T ) = A × e ( − Ea RT )

where k (T ) is the rate constant at temperature T;

A is a constant;
Ea is the activation energy for the reaction;
T is the temperature in K;
R is the gas constant = 8.314 J K–1 mol–1.

(f) Given that the rate constant for the production of vitamin D2 from shiitake mushrooms at
35 °C is twice that at 25 °C, calculate the activation energy for the reaction.
3. This question is about mercury fulminate

Mercury(II) fulminate, HgC2N2O2, has been known as a

super-sensitive explosive for 300 years, but – being so
difficult to handle – its crystal structure was only
determined in 2007. To avoid setting off an explosion,
the compound had to be synthesised in the dark in a
process that the researchers describe as “quite tricky”.

On detonation mercury(II) fulminate decomposes forming

three products: two of these are gases, two are elements.

(a) Write the equation for the detonation of mercury(II) fulminate.

(b) Calculate, using an energy cycle or otherwise, the standard enthalpy change of reaction
for this detonation using the following standard enthalpies of formation, ΔfH .

[Note that not all of the data are required.]

compound HgC2N2O2 HgO CO CO2 NO NO2

ΔfH / kJ mol–1 +386 −91 −111 −394 +90 +33

Mercury(II) fulminate can be described as organometallic, meaning that it has a metal-

carbon bond. The fulminate ion is a triatomic ion with a charge of minus one. The infrared
spectra of fulminates include a bond stretch in the triple-bond region.

(c) Suggest a structure for mercury(II) fulminate, showing the number and type of bonds
between the atoms.

Mercury(II) cyanate is an isomer of mercury(II) fulminate. In fact cyanates and fulminates

were the first known examples of isomers in chemistry. Mercury(II) cyanate is not
organometallic but its infrared spectrum does contain a bond stretch in the triple-bond
region.

(d) Suggest the structure of mercury(II) cyanate, showing the number and type of bonds
between the atoms.

Protonation of cyanates yields cyanic acid, which isomerises to form isocyanic acid, HNCO.
This then spontaneously trimerises to form cyanuric acid, (HNCO)3. There are two different
structures for cyanuric acid which both exist in equilibrium. In both structures the three
atoms for any given element occupy symmetrically equivalent positions; one structure
appears to be aromatic.

(e) Showing all bonds, draw the two possible structures for cyanuric acid.
 4. This question is about aluminium chemistry and rat poison

Aluminium metal reacts with various non-metals

to form simple, binary compounds. The reaction
with phosphorus forms aluminium phosphide,
AlP. This compound has been used as a
rodenticide.

The type of bonding in aluminium compounds

depends on which element it is bonded to. For
example, aluminium oxide is predominantly ionic,
whereas aluminium chloride (empirical formula
AlCl3) shows characteristics of covalent bonding.

(a) How many electrons are around each Al atom in a covalently bonded AlCl3 molecule?
In the vapour phase at 150-200 oC, aluminium chloride exists as a molecule, A, which has
an Mr of 266.66.

(b) i) What is the molecular formula of A?

ii) Suggest a structure for A.

iii) How many electrons are around each Al atom in your structure of A?

Aluminium phosphide is hydrolysed by water to generate the highly toxic gas phosphine,
PH3. Phosphine is similar in structure to anmmonia, and like NH3, PH3 can act as a ligand
using its lone pair.
(c) Write an equation for the hydrolysis of AlP.

There has been interest in various compounds containing Al-P covalent bonds as precursors
for AlP. When equal moles of iBu2AlH and Ph3SiPH2 are dissolved in solvent at 25oC,
hydrogen gas is evolved and a white crystalline solid B is produced (iBu = (CH3)2CHCH2-;
Ph = C6H5-).

(d) How many electrons are around Al in the covalently bonded iBu2AlH?

The mass spectrum of B gives a peak with highest m/z value at 864.

(e) i) Using your answer to (b) as a guide, suggest a structure for compound B.

ii) Compound B shows isomerism. Draw structures to indicate the three-dimensional

shape of two geometric isomers of B.

When warmed, B is converted to C with the evolution of methylpropane. The 31P-NMR

spectrum of C showed it to have a single environment for phosphorus, and 13C-NMR showed
equal numbers of iBu- and Ph3Si- groups. Further analysis showed the compound to have
four Al and four P atoms in the molecule.
(f) Suggest a structure for compound C.

When C is heated to temperatures above 150oC, it starts to decompose, yielding Ph3SiH and
a gas D. By 500oC, all that remains is aluminium phosphide.

(g) Identify the gas D.

5. This question is about toxins from cone snails

Cone snails are predators that use venom

to capture prey. The toxic species in the
venom are polypeptides. Cone snail
toxins are of pharmaceutical interest as
starting points for the development of new
anaesthetics. A number of research
groups are working towards identifying
the amino acid sequences of new cone
snail toxins.
The cone snail Conus textile

Polypeptides are polymers of amino acids; the structures and relative masses of some
amino acids are shown below:

When amino acids form a polypeptide, an amide bond is made and water is lost:
SH
SH O
H
N
OH + OH OH
+ H2O
H2N
H2N H2N O
O O

In biological systems the function of a polypeptide depends on the order of the amino acids
in the sequence. By convention, a polypeptide is drawn starting with the amine group on the
left, hence the sequence of the polypeptide shown above is cysteine-leucine NOT leucine-
cysteine.
Polypeptides are often sequenced using mass spectrometry. In a mass spectrometer the
polypeptide breaks into fragments with the amide bonds being the most likely to be broken.
By comparing the masses of the different ions formed it is possible to work out the amino
acid sequence. The major ions seen in the fragmentation of an isoleucine-leucine-glycine
polypeptide are shown below:
In all parts of this question you should use the mass of the most common isotopes of each of
the elements: 12 for C, 14 for N, 16 for O and 1 for H.

(a) i) What is the mass of the isoleucine-leucine-glycine polypeptide?

ii) What is the mass of Ion 1?
iii) What is the mass of Ion 2?

A polypeptide, X, of mass 976 was isolated from a cone snail. It was found by chemical
analysis to have the following amino acid composition:
2 x cysteine, 1 x aspartic acid, 1 x glutamic acid, 1 x glutamine, 1 x glycine, 1 x isoleucine,
1 x leucine and 1 x proline.

(b) How many unique polypeptide sequences can be formed using all these amino acids?

The fragmentation mass spectrum of X and the 1H NMR spectrum of the third amino acid in
the sequence are shown below. Under the conditions used for the NMR spectrum no peaks
are seen for the NH2 and COOH protons.

6 protons.

Two overlapping peaks,

one from 1 proton, the
other from 2 protons.
1 proton.

4.0 3.5 3.0 2.5 2.0 1.5 δ (ppm)

(c) The last two amino acids in the sequence are glutamic acid-glycine. What is the
sequence of the first 7 amino acids? [The structures and masses of the amino acids
are shown at the top of the previous page.]
 6. This question is about the synthesis of Fexofenadine.

Antihistamines are taken to reduce

the effects of allergic reactions in the
body. The drug fexofenadine is used
to treat sneezing, runny nose and
itchy eyes experienced by hay fever
sufferers, without causing
drowsiness.

Fexofenadine, structure shown below, is sold as the hydrochloride salt with each tablet
containing 112 mg of fexofenadine as 120 mg of the salt with HCl.
(a) i) On the structure in your answer booklet, circle the atom which will be protonated in
the salt.
ii) Given that 112.00 mg of fexofenadine is actually contained in 120.14 mg of the salt,
calculate the relative molecular mass of fexofenadine.

iii) Given your answer to part (ii), suggest what common organic group R is in the
structure of fexofenadine below.
A synthesis of Fexofenadine is shown below.

O
CH3 I intermediate A CH3 I Cl
CN B Cl C
in the presence C 9H 9N C 10 H 11 N AlCl3 C 14 H 16 ClNO
X of base

NaBH 4
(a carbonyl
reducing agent)

NH intermediate E
RMgBr RMgBr F D
O
H3 C C6 H 10 NOR f ollowed by dilute acid C6 H11NOR 2 C 14 H 18 ClNO
O

CO 2H

N
R
HO OH
heat with dilute acid G
R Fexofenadine C 20 H 28 N2 O2 R2

(R is a common organic hydrocarbon group)

(b) Draw out the structure of starting material X and indicate which hydrogen atoms are
removed by the base in the first step of the synthesis.
(c) Draw the structures of compounds / intermediates A to G.
Acknowledgements & References
References for questions

Q1. “Purification of metallurgical grade silicon by a solar process” G. Flamant et al.

Solar Energy Materials & Solar Cells, 2006, p2099-2106
and
“Historical overview of silicon crystal pulling development” Werner Zulehner
Materials Science and Engineering, B73, 2000, p7-15

Q2. “Kinetics of the conversion of ergosterol in edible mushrooms” Viraj J. Jasinghe et al.
Journal of Food Engineering, 2007, Vol 79 p864-869.

Q3. “The Crystal and Molecular Structure of Mercury Fulminate” W. Beck et al.
Zeitschrift für anorganische und allgemeine Chemie, 2007, Vol 633 p1417-1422.

Q4. “New Aluminum Phosphide Precursor” Alan H. Cowley et al.

Angewandte Chemie International Edition, 1990, Vol 29 p1409-1410.

Q5. “A vasopressin/oxytocin-related conopeptide with g-carboxyglutamate at position 8”

Carolina Möller and Frank Marí
Biochemical Journal, 2007, Vol 404 p413-419.

Q6. “A new synthesis of carboxyterfenadine (fexofenadine) and its bioisosteric tetrazole

analogs”, B. Di Giacomo et al.
Il Farmaco, 1999, Vol 54 p600-610.

The Chemistry Olympiad Committee would like to thank the following people /
organisations for their help and advice in the preparation of this paper.

David Paul and Bruce Livett at the University of Melbourne for the picture of the cone snail.

Anthony Lim, a second year Natural Sciences student at the University of Cambridge, for the
cartoon used in question 4.

The photography department of the University of Cambridge, Department of Chemistry for

the photographs used in questions 1, 2, and 6.

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
production network spans 73 manufacturing facilities in 19 countries throughout the world.
The chemicals INEOS produce enhance almost every aspect of modern life.
 41st INTERNATIONAL

CHEMISTRY OLYMPIAD

2009

UK Round One

STUDENT QUESTION BOOKLET

*****
ƒ The time allowed is 2 hours.
ƒ Attempt all 6 questions.
ƒ Write your answers in the special answer booklet.
ƒ In your calculations, please write only the essential steps in
the answer booklet.
ƒ Always give the appropriate units and number of significant
figures.
ƒ You are provided with a copy of the Periodic Table.
ƒ Do NOT write anything in the right hand margin of the
answer booklet.

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.
 H He
1 2
1.008 4.003

Li Be symbol B C N O F Ne
3 4 atomic number 5 6 7 8 9 10
6.94 9.01 mean atomic mass 10.81 12.01 14.01 16.00 19.00 20.18

Na Mg Al Si P S Cl Ar
11 12 13 14 15 16 17 18
22.99 24.31 26.98 28.09 30.97 32.06 35.45 39.95

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
39.102 40.08 44.96 47.90 50.94 52.00 54.94 55.85 58.93 58.71 63.55 65.37 69.72 72.59 74.92 78.96 79.904 83.80

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
85.47 87.62 88.91 91.22 92.91 95.94 101.07 102.91 106.4 107.87 112.40 114.82 118.69 121.75 127.60 126.90 131.30

Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
132.91 137.34 138.91 178.49 180.95 183.85 186.2 190.2 192.2 195.09 196.97 200.59 204.37 207.2 208.98

Fr Ra Ac+
87 88 89

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
*Lanthanides 58 59 60 61 62 63 64 65 66 67 68 69 70 71
140.12 140.91 144.24 150.4 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
+Actinides
90 91 92 93 94 95 96 97 98 99 100 101 102 103
232.01 238.03
1. This question is about environmentally friendly fireworks

Recent research on fireworks has sought to reduce

the quantity of heavy metal salts used for
colouration, and perchlorate or chlorate(VII), an
oxidiser that is also toxic. By employing a fuel that
generates less smoke, less metal salt is required
for the same visual effect.
Replacing the carbon and hydrogen in fuels by
nitrogen can cut the smoke evolved, but many
compounds containing mostly nitrogen are
dangerously unstable. However, one compound
finding favour as a fuel is dihydrazinotetrazine
(shown below) which, despite its high nitrogen
content, is remarkably stable.

H2N N N
NH NH
N N NH2
dihydrazinotetrazine

(a) i) By considering the bonding in the ring suggest why this compound is so stable.

ii) It is possible to record nitrogen NMR spectra, due to the presence of the NMR-
active 15N isotope. Predict the number of signals you would expect to see in the 15N
NMR spectrum in dihydrazinotetrazine by working out how many different nitrogen
environments are present in the molecule.

iii) When dihydrazinotetrazine is burnt in excess oxygen the products are nitrogen gas
and two other substances. Write a balanced equation for this combustion in excess
oxygen.

Octanitrocubane is another potential fuel. Its structure has a cage of carbon atoms at the
corners of a cube with each carbon atom bonded to a nitro group (−NO2). Due to bond
strain, the molecule is difficult to make and less stable than dihydrazinotetrazine.

(b) i) How many degrees smaller is the C−C−C bond angle in octanitrocubane compared
with that in a straight-chained alkane?

ii) Give a balanced chemical equation to show that no additional oxygen – and
therefore no (toxic) oxidiser – is required when octanitrocubane is used as a fuel.

(c) Another nitrogenated fuel is the polymer nitrocellulose whose repeat unit is shown
below. Give the empirical formula of nitrocellulose, and hence write an equation for the
combustion of this formula unit in excess oxygen.

O2NO
O
O
n
O2NO ONO2
2. This question is about the unnecessary production of carbon dioxide

Outdoor flames, such as patio heaters and the

Olympic flame, contribute to global warming.
This is not only due to the heat released, but also
due to the carbon dioxide produced from the
combustion of hydrocarbons.

Most patio heaters are powered by small

cylinders of propane gas. A typical patio heater
designed to produce 15 kW of energy runs from a
cylinder containing 13 kg of propane. A
‘completely full’ cylinder at a pressure of 140 psi
(9.52 atmospheres) is in fact only filled to about
87% capacity with liquid propane, the remaining
volume being taken up by propane vapour. The
standard enthalpy change of combustion of
propane is –2220 kJ mol–1.

Assume 1 mole of a gas occupies 24 dm3 under

the conditions of this question.

(a) i) Calculate the number of moles of propane contained in a cylinder.

ii) Calculate the mass of carbon dioxide produced when all of the propane in a cylinder
is burnt completely.

iii) Calculate the total amount of heat energy released by combustion of all the propane
in a cylinder.

iv) Calculate the rate at which propane must leave the cylinder (in cm3 s–1) to produce
15 kW (ie 15 kJ s–1).

v) Estimate the equilibrium pressure when the cylinder is only ‘half full’.

Because pure propane gas is odourless, small amounts of another compound are usually
added so that gas leaks can be detected. An example of such an odorant is ethyl mercaptan
(ethanethiol, C2H5SH); this is chosen since the human nose can detect its presence at levels
of only about 0.02 ppb (parts per billion).

(b) i) Draw a diagram to show how the atoms are bonded together in ethyl mercaptan and
predict the bond angle around the sulphur atom.

ii) Calculate the mass of ethyl mercaptan which must be added to 13 kg of propane to
produce 0.02 molecules of it per billion (109) molecules of propane.

The Olympic flame on top of the Bird’s Nest Stadium which burned throughout the Beijing
Olympics consumed 6000 m3 of methane per hour and was kept alight for 16 days.

(c) Calculate the total mass of carbon dioxide produced from the flame during the
Olympics, assuming complete combustion.
3. This question is about the chemistry of matches

The heads of strike-anywhere matches contain a

mixture of phosphorus sesquisulfide P4S3 and
potassium chlorate(V) KClO3. When the match is
struck across a rough surface the heat of friction
is sufficient to ignite the phosphorus
sesquisulfide; the potassium chlorate(V)
decomposes to provide the oxygen needed for
combustion.

(a) i) Write an equation to show the combustion of phosphorus sesquisulfide into

phosphorus(V) oxide and sulfur dioxide.

ii) Write an equation to show the decomposition of potassium chlorate(V) into

potassium chloride and oxygen.

iii) Hence or otherwise write a single equation to show the reaction that takes place
between these two substances when a match-head ignites.

iv) Calculate the mass ratio in which phosphorus sesquisulfide and potassium
chlorate(V) should be combined on the match-head.

v) Given the following standard molar enthalpy changes of formation, calculate the
standard enthalpy change for the reaction in part (iii).

KCl (s) KClO3 (s) SO2 (g) P4S3 (s) P4O10 (s)
-1
ΔfH kJ mol –436.7 –397.7 –296.8 –154.0 –2948

Phosphorus sulfides can be made by heating white phosphorus with sulfur. When this
reaction is carried out at low temperature a range of products from P4S3 to P4S10 are
produced. 31P NMR spectroscopy has been used to determine the structures of many of the
phosphorus sulfides:

In 31P NMR spectroscopy the number of peaks seen corresponds to the number of
different P environments, for example P4S3 has two different P environments so
shows two peaks in the 31P NMR spectrum.

(b) Using the structures above, predict how many peaks would be seen in the 31P NMR
spectrum of: i) P4S4 ii) P4S5 iii) P4S6.

P4S4 has, in fact, been shown to exist in two different isomeric forms. You are given
the structure of one isomer above. The second isomer shows only one peak in the
31
P NMR spectrum.

(c) Suggest a structure for the second isomer of P4S4.

4. This question is about stopping diarrhoea

The active ingredient in

anti-diarrhoea medicines
such as imodium, is
loperamide, whose
structure is given below.
As with many drugs,
loperamide is often sold
as the hydrochloride salt
since this is more soluble
in water.

(a) On the structure in your answer booklet, circle the atom in loperamide which will be
protonated in the salt.

A synthesis of loperamide is shown below.

O

O epoxyethane
base intermediate
Ph anion B
O anion C
Ph
ester A

Ph = phenyl, -
loss of C 2H 5O
C 6H 5-

SOCl2 HBr cyclic ester

F E
D
C 16 H14 BrClO

NH(CH3 )2
OH
OH
Cl
Cl
NH
H N
O
G
C 18 H20BrNO Loperamide N
Ph Ph
(b) (i) Ester A may be made by treating a mixture of an alcohol and a carboxylic acid with a
catalytic quantity of concentrated sulfuric acid. Give the structures of the alcohol and
carboxylic acid.

(ii) Ester A is deprotonated by a base to give the anion B. Draw the structure of A and
indicate clearly which proton is removed by the base to form anion B.

Anion B then opens up the three-membered ring of epoxyethane to form an intermediate,

anion C. This intermediate then cyclizes and eliminates ethoxide, C2H5O–, to form ester D.

(c) Draw the structures of anion C and cyclic ester D.

Ester D reacts with bromide which opens the ring to give carboxylic acid E. E then reacts
with SOCl2 to give F.

(d) Draw the structures of compounds E and F.

F reacts with dimethylamine to form G. Two isomeric structures may be drawn for G; either
an open-chain amide, or a cyclic bromide salt. There are ten signals in the 13C NMR
spectrum of the cyclic bromide salt.

(e) Suggest structures for G in (i) the amide form and (ii) the bromide salt form.
5. This is a question about arsenic.

Arsenic, As, atomic number 33, is an

element infamous for its toxic compounds.
The presence of naturally occurring
arsenic compounds in groundwater
currently affects millions of people
throughout the world.
A number of different techniques for
removing arsenic compounds from water
have been developed, but research to
improve these methods is ongoing.

Marsh gas test

In 1836 British chemist James Marsh developed the first reliable test for the detection of
arsenic(III) oxide. In the Marsh test arsenic(III) oxide is first converted to arsine gas (AsH3)
which is then ignited leaving a silvery-black deposit of arsenic.

a) i) Draw the structure of arsine indicating the geometry.

ii) Write a balanced equation for the combustion of arsine as used in this test.

Arsine is formed when arsenic(III) oxide is reacted with zinc and sulfuric acid.

b) i) Give the formula for arsenic(III) oxide.

ii) Write a balanced equation for the reaction of arsenic(III) oxide with zinc and sulfuric
acid.

The Marsh test is no longer used to detect arsenic; today spectroscopic methods allow the
concentration of arsenic in a sample to be determined rapidly and with great sensitivity.

In groundwater the most prevalent arsenic species at high pH is HAsO42–.

c) i) What is the oxidation number of arsenic in HAsO42–?

ii) Draw a diagram to show the three-dimensional structure of HAsO42–.

HAsO42– can be removed from water by adsorption on to particles of iron(III) hydroxide. The
variation in the concentration of aqueous HAsO42– with adsorption time can be described by
the equation:

[HAsO42– (aq)]t = [HAsO42– (aq)]0 e–(kt)

where [HAsO42–(aq)]t is the concentration of aqueous HAsO42– at time t, [HAsO42–(aq)]0 is the

initial concentration of aqueous HAsO42– and k is the rate constant for the adsorption
reaction. The rate constant is related to the half-life of the reaction (t1/2) by the equation:

ln 2
t1/2 =
k

The graph to the right shows how the

concentration of aqueous HAsO42– varies
with adsorption time at 40 oC. According
to the World Health Organization the safe
level for dissolved arsenic species in
water is < 10μg dm–3.

d) i) Using the graph, determine the rate constant for the adsorption of HAsO42– on to
iron(III) hydroxide particles stating the units.

ii) In a different water sample it took 55 minutes for the concentration of aqueous
arsenic to reach the safe level. What was the initial concentration of aqueous HAsO42–?

Under certain conditions the equilibrium constant, K, for the adsorption of HAsO42– can be
defined as:

[HAsO 24-(adsorbed) ]
K=
[HAsO 24-(aq) ]

At 20 oC the value of K is 186.

e) If the initial concentration of aqueous HAsO42– was 30 μg dm–3, what is the

concentration of aqueous HAsO42– at equilibrium at 20 oC?
6. This question is about revealing a hidden van Gogh painting

In 2008, a team of Dutch analytical chemists

used a technique called Synchrotron Radiation
Based X-ray Fluorescence Elemental Mapping to
discover a hidden van Gogh painting. The
original painting of a woman's head had been lost
when van Gogh painted his 'Patch of Grass' over
the top.
The technique works by firing monochromatic,
high-energy X-rays at the target. This causes
core electrons, such as those in the 1s shell, to
be knocked out. Electrons from other shells drop
down to replace the lost electron, and energy is
given out in the form of a lower-energy X-ray.
Measuring the exact frequency of the emitted X-
ray can tell us which element is present.

The painting of a woman's head

hidden under the Patch of Grass.
The energy, En, of an electron in a hydrogen atom, or a one-electron ion, is given by the
equation:
Z2
E n = − RH
n2

where RH is a constant known as the Rydberg constant, Z is the nuclear charge (Z = 1 for
hydrogen) and n is the principal quantum number of the shell the electron is in. If the
electron is in the 1s shell, n = 1; if in the 2s or 2p, n = 2; if in the 3s, 3p, or 3d, n = 3 etc.

When dealing with the energies of electrons in atoms, a convenient unit is the electron volt,
eV, where 1eV ≡ 1.6022 ×10–19 J. Expressed in these units, RH = 13.6 eV. The Avogadro
constant = 6.022×1023 mol–1.

(a) i) What is the energy, in eV, of the electron in a hydrogen atom when in the 1s orbital?

ii) What happens to the energy of the electron as it is moved into higher shells, further
from the nucleus, so that the atom just becomes ionized? Tick the correct box in the
answer booklet.

The energy of the electron tends to:

– infinity –13.6 eV –1 eV zero +1 eV + 13.6 eV + infinity

iii) Calculate the ionization energy of a hydrogen atom in kJ mol–1.

For atoms or ions with more than one electron, the charge an electron experiences is less
than the full nuclear charge Z since the electrons shield one another.

The equation may be modified to become:

(Z − S ) 2
En = − RH
n2
where S is a shielding constant.
The quantity ( Z – S ) is sometimes known as the effective nuclear charge, Zeff , that an
electron experiences.

(b) Given the first ionization energy of sodium is 495.8 kJ mol–1, calculate Zeff for an
electron in the valence shell of a sodium atom.

An X-ray fluorescence spectrum recorded from the van Gogh painting is shown below.

The peaks marked Kα are due to transitions from the 2p shell to the 1s shell. For such
transitions, S is taken to be 1.

(c) Calculate the atomic number, and hence element symbol A, which gives rise to the line
marked Kα(A) in the spectrum.

The lines marked Lα are due to transitions from the 3d shell to the 2p shell. For such
transitions, S may be taken to be 7.4.

(d) i) Calculate the atomic number and hence element B, which gives rise to the peak
marked Lα(B) in the spectrum.

ii) This peak is especially strong in the region around the lips of the face in the portrait
since a red pigment (the sulfide) is used in that area. Suggest the formula of the
pigment.

(e) i) The peak at 10500 eV is due to the Kα transition for element C and the Lα transition
for element D. Calculate the atomic numbers and hence give the symbols of these
elements.

ii) Element C is present in a green pigment called known as Scheele's green. It has the
formula (A C H Ox). Given that element C is the +3 oxidation state, suggest a formula
for Scheele's green.

(f) Calculate the energy for the Kα transition of antimony, Sb.

In actual fact, the peak in the spectrum due to the Kα transition is slightly different from the
calculated value. Comparison with known compounds tells us that this is because the
compound contains Sb in its highest oxidation state.

(g) One possible pigment is Naples yellow which has the formula (D2Sb2O7). What is the
oxidation state of element D in this compound?
Acknowledgements & References

References for questions

Q1 Pyrotechnics For The Planet Chemical & Engineering News, 2008, Vol 86, p 14-18.

Q4 Synthetic antidiarrheal agents. 2,2-Diphenyl-4-(4'-aryl-4'-hydroxypiperidino)butyramides

R. A. Stokbroekx et al. Journal of Medicinal Chemistry 1973, Vol 16, p 782-786.

Q5 Kinetic and thermodynamic aspects of adsorption of arsenic onto granual ferric

hydroxide. K. Banerjee et al. Water Research, 2008 Vol 42, p 3371-3378.

Q6 Visualization of a Lost Painting by Vincent van Gogh Using Synchrotron Radiation

Based X-ray Fluorescence Elemental Mapping. J. Dik et al.
Analytical Chemistry, 2008, Vol 80, p 6436-6442.

The Chemistry Olympiad Committee would like to thank the following people /
organisations for their help and advice in the preparation of this paper.

Joris Dik of Delft University of Technology for helpful advice and for the permission to use
the image of the van Gogh painting.

The photography department of the University of Cambridge, Department of Chemistry for

the photographs used in question 4.

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
production network spans 73 manufacturing facilities in 19 countries throughout the world.
The chemicals INEOS produce enhance almost every aspect of modern life.
 41st INTERNATIONAL CHEMISTRY OLYMPIAD

UK Round One - 2009

MARKING SCHEME

Notes
Chemical equations may be given as sensible multiples of those given here.
Formulae can be given by any conventional method (i.e. structural or molecular).

State symbols do not need to be included in the chemical equations to obtain the
mark(s).

Answers should be given to an appropriate number of significant figures

although the marker should only penalise this once.

Total 64 marks.

Question 1
Answer Marks

(a) i) It is aromatic / the bonds in the ring are conjugated / there are 1
alternate single and double bonds in the ring / the electrons in the ring
are delocalised / very similar to benzene

ii) 3 peaks 1

iii) C2H6N8 + 7/2 O2 → 2 CO2 + 3 H2O + 4 N2 or 1

2 C2H6N8 + 7 O2 → 4 CO2 + 6 H2O + 8 N2

(b) i) 19⁰ or 19.5⁰ or 19⁰28’ 1

ii) C8N8O16 → 8 CO2 + 4 N2 1

(c) C6H7N3O11 + 9/4 O2 → 6 CO2 + 7/2 H2O + 3/2 N2 or 2

4 C6H7N3O11 + 9 O2 → 24 CO2 + 14 H2O + 6 N2

7 marks

Note: Tests are to be taken under controlled conditions. Students must not have access to
the information contained in this marking scheme prior to, or during, the test.
Question 2
Answer Marks

(a) i) Moles = 13000/44.1 = 295 1

ii) Mass = 3 x 295 x 44.0 = 38900 g = 38.9 kg 1

(accept 39 kg)

iii) Heat energy = 2220 x 295 = 655000 kJ = 655 MJ

1

iv) 1 mol s-1 = 2220 kJ s-1 = 2220 kW, so 15 kW 1

= 15/2220 mole s-1 =15x24000/2220 =162 cm3 s-1

v) Still 140 psi (or 9.52 atm) 1

(b) i) Sensible bonding diagram with all single covalent bonds 1

Accept a bond angle anything between 90o - 105.5o 1

ii) Mass = 295 x 0.02 x 10-9 x 62.1 = 0.000000366 g 1

= 0.000366 mg
= 3.66 x 10-7 g
(accept 3.7 or 4.0 x 10-7 g)

(c) 6000 m3 CH4 = 6000 x 103 dm3 = 6000 x 103 / 24 moles, so we 1

get 6000 x 103 / 24 moles CO2 = (6000 x 103 / 24) X 44 g CO2
per hour. So in 16 days we get (6000 x 103 / 24) X 44 x 24 x 16
= 4224 x 106 g = 4224 tonnes
(accept 4200 tonnes)

9 marks

Question 3
Answer Marks

(a) i) P4S3 + 8O2 → P4O10 + 3SO2 (accept 2P2O5 + 3SO2) 1

ii) 2KClO3 → 2KCl + 3O2 1

iii) 3P4S3 + 16KClO3 → 3P4O10 + 9SO2 + 16KCl (accept 6P2O5) 1

iv) P4S3 / KClO3 = 660 / 1961 = 1 / 2.97 1

Note: Tests are to be taken under controlled conditions. Students must not have access to
the information contained in this marking scheme prior to, or during, the test.
 v) ΔrHØ = ( (3 x –2948) + (9 x –296.8) + (16 x –436.7 ) ) 2

– ( (3 x –154.0) + (16 x –397.7 ) )

= -11700 kJ mol-1

(b) i) 3 peaks 1

ii) 4 peaks 1

iii) 3 peaks 1

(c) 2

(accept any other reasonable structure, that fits with the data
and with elements in correct valencies)

11 marks

Question 4
Answer Marks

(a)

(b) i) O
Ph 1
OH HO
Ph
carboxylic acid alcohol

ii) O
H 1
Ph
O
Ph

Note: Tests are to be taken under controlled conditions. Students must not have access to
the information contained in this marking scheme prior to, or during, the test.
(c) O
O O
2
Ph
O O
Ph Ph Ph
anion C cyclic ester D

(d) O O
Br Br 2
OH Cl
Ph Ph Ph Ph
E F

(e) i) O
Br 1
N
Ph Ph
open-chain amide

ii) O
2
N Br
Ph Ph
cyclic bromide salt

10 marks

Question 5
Answer Marks

(a) i) It must be clear from the structure that arsine is not planar. Structures 1
similar to those shown below would be acceptable:

ii) 4AsH3 + 3O2 → 4As + 6H2O 1

(b) i) As2O3 1

ii) As2O3 + 6Zn + 6H2SO4 → 2AsH3 + 6ZnSO4 + 3H2O 1

(c) i) +5 or (V) 1

Note: Tests are to be taken under controlled conditions. Students must not have access to
the information contained in this marking scheme prior to, or during, the test.
 ii) Both the bonding and geometry must be clear, structures such as those 1
shown below would be acceptable:

(d) i) From the graph the t1/2 is 8 mins 1

k = ln2 / t1/2 therefore k = 0.087 min-1 (0.0014 s-1 or 0.144 x 10-3 s-1)
Accept values for t1/2 in the region of 7 to 9 mins ( k = 0.08 to 0.1 min-1)
also accept correct values for k given in s-1.

ii) [HAsO42- (aq)]t = [HAsO42- (aq)]0exp-(kt) 2

10 = [HAsO42- (aq)]0exp-(0.09*55)
[HAsO42- (aq)]0 = 1400 μg dm-3

For k = 0.08 min-1, [HAsO42- (aq)]0 = 800 μg dm-3 whilst for k = 0.1 min-1,
[HAsO42- (aq)]0 = 2400 μg dm-3. Full marks should be given for values
within this range.

(e) [HAsO42- (aq)]t=0 = [HAsO42- (aq)]eq + [HAsO42- (adsorbed)]eq 2

2- 2-
[HAsO ]
4 (aq) t = 0 − [HAsO ]
4 (aq) eq
Therefore: K = 2-
[HAsO 4 (aq) eq]
Rearranges to give:
[HAsO 24-(aq) ] t = 0 30
[HAsO 2-
]
4 (aq) eq = = = 0.16 μg/dm 3
1+ K 1 + 186

11 marks

Question 6
Answer Marks

(a) i) –13.6 eV Must have minus sign 1

ii) zero 1

–1
iii) 1300 kJ mol 1

(b) 2
3 3
Z eff
− 495.8 × 10 = −1312 × 10 × 2
32
Z eff = 1.84
(2 for correct answer; partial credit of 1 if expression is correct)
Note: Tests are to be taken under controlled conditions. Students must not have access to
the information contained in this marking scheme prior to, or during, the test.
 (Z − S ) 2
(c) energy of electron in 2p shell = − 13.6 ×
22
(Z − S ) 2
energy of electron in 1s shell = − 13.6 ×
12
energy released on transition from 2p to 1s
3
= × 13.6 × ( Z − 1) 2 = 8000
4
( Z − 1) = 28
Z = 29 element is copper, Cu 2

(Z − S ) 2
(d) i) energy of electron in 3d shell = − 13.6 ×
32
(Z − S ) 2
energy of electron in 2p shell = − 13.6 ×
22
energy released on transition from 3d to 2p
⎛ 1 1 ⎞
= ⎜ 2 − 2 ⎟ × 13.6 × ( Z − 7.4) 2 = 10000
⎝2 3 ⎠
( Z − 7.4) = 72.8
Z = 80 element is mercury, Hg 2

ii) HgS 1
(accept other possible mercury sulfide formulae)

(e) i) for C, energy released on transition from 2p to 1s

3
= × 13.6 × ( Z − 1) 2 = 10500
4
( Z − 1) = 32
Z = 33 element is arsenic, As 1
for D energy released on transition from 3d to 2p
⎛ 1 1 ⎞
= ⎜ 2 − 2 ⎟ × 13.6 × ( Z − 7.4) 2 = 10500
⎝2 3 ⎠
( Z − 7.4) = 74.6
Z = 82 element is lead, Pb 1

ii) CuAsHO3 (this assumes +2 oxidation state for Cu) 2

(f) for antimony, Sb, energy released on transition from 2p to 1s 1

3
= × 13.6 × (51 − 1) 2 = 25500 eV
4
(g) Balancing oxidation states: 1
( 2 x) + ( 2 × 5) + (7 × −2) = 0 implies x = +2
[ formula is Pb2Sb2O7 ]

16 marks

Total Marks 64

Note: Tests are to be taken under controlled conditions. Students must not have access to
the information contained in this marking scheme prior to, or during, the test.
 42nd INTERNATIONAL

CHEMISTRY OLYMPIAD

2010

UK Round One

STUDENT QUESTION BOOKLET

*****
 The time allowed is 2 hours.
 Attempt all 6 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.

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 18

H He
1 2 13 14 15 16 17 2
1.008 4.003

Li Be symbol B C N O F Ne
3 4 atomic number 5 6 7 8 9 10
6.94 9.01 relative atomic mass 10.81 12.01 14.01 16.00 19.00 20.18

Na Mg Al Si P S Cl Ar
11 12 13 14 15 16 17 18
22.99 24.31
3 4 5 6 7 8 9 10 11 12 26.98 28.09 30.97 32.06 35.45 39.95

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
39.102 40.08 44.96 47.90 50.94 52.00 54.94 55.85 58.93 58.71 63.55 65.37 69.72 72.59 74.92 78.96 79.904 83.80

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
85.47 87.62 88.91 91.22 92.91 95.94 101.07 102.91 106.4 107.87 112.40 114.82 118.69 121.75 127.60 126.90 131.30

Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
132.91 137.34 138.91 178.49 180.95 183.85 186.2 190.2 192.2 195.09 196.97 200.59 204.37 207.2 208.98

Fr Ra Ac+
87 88 89

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
*Lanthanides 58 59 60 61 62 63 64 65 66 67 68 69 70 71
140.12 140.91 144.24 150.4 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
+Actinides
90 91 92 93 94 95 96 97 98 99 100 101 102 103
232.01 238.03
 1. This question is about a substitute for the perfume ingredient ambergris

Ambergris, a metabolic product of the

sperm whale, was for many years one of the
most valuable ingredients in fine fragrances.
Recently, it has been replaced with
synthetic equivalents such as Ambrox®
which possesses a powerful amber-type
fragrance. Many different research groups
have proposed methods for synthesising
Ambrox from natural products found in
plants. A synthesis starting with (–)-drimenol
extracted from the bark of the Chilean tree
Drimys winteri is outlined below:

O O
OH S
Cl
+ pyridine
(a base) A KCN B H+/H 2O C

90 % C16H28O3S 60 % C16H25N 84 % C16H26O2

C15H 26O
(-)-drimenol p-toluenesulfonic acid 75 %

O
O i) LiAlH4
p-toluenesulfonic acid D ii) H +/H2O O
85 % C16H30O2 86 %

C16H28O
Ambrox C16H26O2

(a) Given that ten tonnes of Ambrox are produced every year, calculate the number of
moles produced per year.

(b) Draw the structures of compounds A to D.

The yield of each step in the synthesis is shown beside the arrows in the scheme.

(c) (i) What is the overall percentage yield of Ambrox in this synthesis?

(ii) What mass of (–)-drimenol would be needed each year if all of the commercially
synthesised Ambrox was made using this method?

(iii) Given that Drimys winteri bark contains 0.5 % by mass of (–)-drimenol calculate the
mass of bark that would be needed each year if all of the commercially synthesised
Ambrox was made using this method.
2. This question is about the analysis of a copper-containing complex.

In the practical exam for the 2009

International Chemistry Olympiad
held in Cambridge, students were
asked to analyse compound X, a
compound containing copper(II).
This compound consists of ions:
the negatively charged ion is a
complex ion containing copper,
chlorine and oxygen. The
positive counter ion in compound
X is the tetramethylammonium
ion, (CH3)4N+. The students were
asked to determine the formula of
the negative ion, using two
titrations.

The first titration was used to determine the proportion of copper ions in the complex. In this
titration, the complex was reacted with EDTA solution. EDTA reacts with copper ions
according to the equation:

Cu2+(from the complex) + EDTA4–(aq) → [CuEDTA]2– (aq)

The end-point of this titration was determined using an indicator called murexide, and one of
the UK team found that 0.1000 g of X required 21.70 cm3 of 0.02000 mol dm–3 EDTA
solution for complete reaction.

(a) Calculate the % by mass of copper in compound X.

The second titration determined the proportion of chloride ions in the complex. The chloride
ions from the complex were titrated against 0.1000 mol dm–3 silver(I) nitrate solution, and the
student found that 0.2000 g of X required 21.70 cm3 of silver nitrate.

(b) i) Give a balanced equation that shows the reaction that takes place in this titration.

ii) Calculate the % by mass of chlorine in compound X.

The proportions by mass of carbon, hydrogen and nitrogen in compound X were determined
by combustion analysis. The results were found to be C 20.87%, H 5.17%, and N 5.96%.

(c) i) Which of the six elements in compound X has the greatest percentage error in the
determination of its proportion? Circle the element in the answer booklet.

ii) Ignoring this element, because of this uncertainty, determine the simplest whole
number ratio of the remaining five elements in X.

iii) Hence determine the formula of the negative ion in X.

3. This question is about halogen fluorides

Chlorine trifluoride, ClF3, is one of the most reactive

substances known: it causes sand and asbestos to
explode and it reacts with xenon. It has been
investigated as a rocket fuel; its reactions with
every known fuel are so fast that no ignition delay
has ever been measured.

(a) ClF3 is used to turn uranium into uranium hexafluoride, UF6, which is used to separate
the isotopes of uranium. Chlorine monofluoride, ClF, is a side-product in this reaction.
Write a balanced equation for the reaction between uranium and chlorine trifluoride.

(b) ClF3 is a powerful oxidising agent. In the answer booklet circle each atom / ion on the
left hand side of the equation that is oxidised in the reaction between chlorine trifluoride
and silver chloride.

2AgCl(s) + 2ClF3(l) 2AgF2(s) + Cl2(g) + 2ClF(g)

Iodine forms the fluorides IF, IF3, IF5 and IF7. Their standard enthalpy changes of formation
are shown in the table.

IF IF3 IF5 IF7

−1
ΔfH / kJ mol −95.4 −486 −843 −962.5

When the oxidation number of iodine is between 0 and +7 there is a possibility that it will
disproportionate to the compound with iodine in its next highest oxidation number, and
elemental iodine. For example, IF3 might disproportionate to give IF5 and I2.

(c) i) Give the equations for the theoretical disproportionation reactions of IF, IF3 and IF5.

ii) Calculate the standard enthalpy change for each of these reactions.

iii) Only one of IF, IF3 and IF5, does not disproportionate – suggest which one.
4. This question is about salting roads in winter

In winter in the U.K. a lot of money is spent

on gritting roads to keep them safe during
cold weather. The salt that is applied melts
the ice. This question looks at the
chemistry behind the salting.

The freezing point of a solution differs from

that of pure water and is one of a number of
so-called colligative properties of a solution.
These are properties that, to a good
approximation, depend only on the relative
number of solute molecules or ions
dissolved in the solution but not on their
properties. Which phase exists at which
temperature depends on a quantity called
the chemical potential (μ). The phase with
the lowest chemical potential is the most
stable.

The graph below is a sketch of how the chemical potential of the three phases of pure water
varies with temperature at standard pressure; each line shows how the chemical potential
varies for one of the phases of water – solid, liquid, or gas.

A
chemical potential

temperature

(a) i) Which line corresponds to which phase of pure water?

ii) Mark in the appropriate places on the graph in the answer booklet the values of two
temperatures that you know exactly.

The presence of salt affects the chemical potential. It is assumed that the salt dissolves only
in the liquid phase of water and so the chemical potentials of the solid and gaseous phases
are not affected by the salt. In the liquid phase, the chemical potential of a salt solution at a
particular temperature is given by the expression below, where xw is the fraction of water in
the salt solution (in terms of moles), R is the gas constant (8.314 J K−1 mol−1), and T is the
temperature in Kelvin.

μ(solution) = μ(pure water) + RT loge xw

(b) i) Sketch a line on a graph in the answer booklet that corresponds to the chemical
potential of a salt solution.

ii) Hence circle in the answer booklet how the boiling point of a salt solution will
compare to that of pure water:

lower than water the same as water higher than water

For the purpose of the following calculations, the mole fraction of ions, xi, is given by:

number of moles of anions + number of moles of cations

xi =
number of moles of water + number of moles of cations + number of moles of anions

(c) i) Given the density of pure water is 1.00 g cm−3, work out its concentration in mol dm−3.

ii) Calculate the mole fraction of ions (xi) in a 3.00 mol dm−3 solution of sodium chloride.
You may assume there is no volume change upon dissolving the salt in water.

The freezing point of salt solutions of various concentrations can be estimated using the
following expression,
xi RTm 2
∆T =
∆mH 

where ∆T is the depression in freezing point

xi is the mole fraction of ions
Tm is the melting point of pure water in Kelvin = 273 K
ΔmH is the standard enthalpy change of melting for pure water = 6.01 kJ mol−1
R is the gas constant = 8.314 J K−1 mol−1.

(d) i) Calculate ∆T and hence the freezing point of a 3.00 mol dm−3 solution of sodium
chloride.

ii) In reality, the salt is often present in excess on the roads and so the maximum
freezing point depression is limited by the maximum solubility of the salt in water at low
temperatures. The most concentrated solutions of sodium chloride remain liquid down
to temperatures of −21.1 °C. What concentration of sodium chloride is this?

In Russia, temperatures are so low that sodium chloride is unable to keep roads ice-free and
calcium chloride is used instead. In a calcium chloride solution water molecules become
strongly coordinated to the calcium ions and so are no longer free in solution. On average, 9
molecules of water are bound per calcium ion. These bound water molecules are no longer
counted towards the number of moles of water in the mole fraction calculation but you may
still assume there is no volume change upon dissolving the salt in water.

(e) Calculate the freezing point of a 3.00 mol dm−3 solution of calcium chloride.
5. This question is about the metal osmium in organic reactions

In 2004 it was reported that a terrorist attack NATURAL HISTORY OF OSMIUM.

that planned to use osmium tetroxide THIS is another new metal discovered by Mr. Ten-
(OsO4) had been foiled. However, although nant. The name of osmium is given to it on account of
osmium tetroxide is highly toxic, it is unlikely the oxid of it being exceedingly volatile, and diffusing, on
to be used for such a purpose due to the being volatilized, a peculiar pungent odour. This metal
high cost of this rare element (around £100 likewise exists in the black powder, mixt with the ore of
per gram of OsO4). Nonetheless, osmium platina. . 
compounds are used in certain organic
reactions. From “System of Theoretical and Practical
Chemistry” by Fredrick Accum, 1808

In aqueous solution, osmium can exist as a number of species.

(a) Write down the oxidation number of the osmium atom in the following species:

i) OsO2 ii) OsO4 iii) OsO42–

An osmium species is able to catalyse the following transformation of an alkene into a diol
where the two OH groups are on adjacent carbon atoms.

(b) How would you classify the reaction above? Circle the correct answer in the answer
booklet.

Hydration Dehydration Oxidation Reduction Isomerisation

(c) Only one of the osmium species in part (a) is able to catalyse this reaction. Based on
your classification of the reaction in part (b), which one of the osmium species do you
think is used as the catalyst?

This reaction is very useful as there is a precise stereochemical outcome due to the way that
the new C–O bonds are formed. Both new C–O bonds are formed simultaneously on the
same face of the double bond. The first step is the formation of a cyclic compound where
the osmium species can attack the double bond on either face.

osmium species osmium species

attacks from below attacks from above

(d) What is the oxidation number of the osmium atom in the cyclic species?

After hydrolysis, the new OH bonds end up either both on the top face, or both on the bottom
face. This means that only certain stereoisomers can be formed.
(e) The diol below can exist as four possible stereoisomers. For each one, draw the
alkene that would need to be treated with the osmium species to form that
stereoisomer.

i) ii) iii) iv)

(f) i) How many stereoisomers are there for the following diol?

Circle in the answer booklet:

1 2 3 4

ii) Draw the structure of each stereoisomer and the corresponding alkene needed to
make it.

In certain molecules with two double bonds it is possible for one of the oxygens that is added
to end up bonded to two carbon atoms, and in doing so form a ring. This reaction has a
defined stereochemical outcome as well. Of the four new C-O bonds that are formed, bonds
1 and 2 are formed simultaneously on the same face of double bond A, and bonds 3 and 4
are formed simultaneously on the same face of double bond B.

(g) The cyclic product from the reaction of the following molecule with the appropriate
osmium species can exist as 16 stereoisomers. In the answer booklet write the
numbers of the stereoisomers that can be formed from this reaction given the
information above.
6. This question is about gold leaf

Gold atoms crystallise in the cubic

arrangement shown in the figure on the right. C
The gold atoms, which are assumed to be
spherical, are shown at half-radius size (rather
than touching their neighbours) to illustrate the
structure more clearly. The lattice structure
can be built up from these cubic ‘building
blocks’ – known as unit cells. Atoms are A
located at the corner positions and in the B
centre of the faces. The cube is shown as a
thin outline; the thicker ‘bonds’ indicate which
atoms are, in reality, in contact.

Avogadro’s constant is 6.02 × 1023 mol–1. Gold has only one isotope, which has a relative
mass of 197. The density of gold is 19.3 g cm–3.

(a) Calculate the mass (in g) of one gold atom.

The cube shown in wireframe in the figure has its corners at the centre of the atoms
occupying those corner positions. The faces of the cube pass through the centre of the
atoms found in the centre of the faces.

(b) By considering the fraction of each atom actually inside the unit cell, calculate the
number of atoms within the unit cell.

(c) Bearing in mind that the atoms are in contact across the diagonal of a face of the cube,
find expressions, in terms of the radius of the gold atom, r, for :

i) the length of the edge of the unit cell, i.e. the distance between the centres of atoms
A and B;

ii) the volume of the unit cell;

iii) the length of the unit cell body diagonal, i.e. the distance between the centres of the
atoms A and C.

(d) Calculate the molar volume of gold in cm3 mol−1.

(e) Given that the volume of a sphere is 4/3 πr3, calculate what fraction of the volume of
the unit cell is occupied by gold atoms.

(f) Bearing in mind your answer to part (e), calculate the radius of a gold atom.

A small mass of gold can be hammered out to cover an extremely large area with gold foil.
The most efficient way of stacking layers of gold atoms has three layers in the length of the
unit cell body diagonal, i.e. the thickness of one layer is one third of the distance A to C.

(g) The great golden Dome of the Rock in Jerusalem is a hemisphere of diameter 21 m.
The late King Hussein of Jordan donated 80 kg of gold to cover the outside of the
dome.

i) Given that the surface area of a sphere is 4πr2, calculate the average thickness in cm
of the gold on the dome.

ii) Hence calculate the average number of layers of gold atoms covering the surface of
the dome.
Acknowledgements & References

References for questions

Q1 Formal Synthesis of Ambrox and 9-epiambrox

M. Cortés, V. Armstrong, M. E. Reyes, J. López and E. Madariaga
Synthetic Communications 26(10) 1996

Q5 A General Oxidative Cyclisation of 1,5-Dienes

T. J. Donohoe and S. Butterworth
Angewandte Chemie Int Ed. Engl. 2003, 42, 948-951.

Q6 Picture of the Dome of the Rock from flickr

www.flickr.com/photos/battyward/2050268080

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
production network spans 73 manufacturing facilities in 19 countries throughout the world.
The chemicals INEOS produce enhance almost every aspect of modern life.
 42nd INTERNATIONAL CHEMISTRY OLYMPIAD

UK Round One - 2010

MARKING SCHEME

Notes
Chemical equations may be given as sensible multiples of those given
here.

Formulae can be given by any conventional method (i.e. structural or

molecular).

State symbols do not need to be included in the chemical equations to

obtain the mark(s).

Answers should be given to an appropriate number of significant figures

although the marker should only penalise this once in the whole paper.

Total 61 marks.

Note: Tests are to be taken under controlled conditions. Students must not have access to
the information contained in this marking scheme prior to, or during, the test.
Question 1
Answer Marks
(a)
Ambrox (C16H28O) has a molar mass of
((16*12.01)+(28*1.008)+(1*16)) = 236.384 g mol-1. 1 mark

10000000 g produced every year, therefore (10000000/236.384) =

4.2x104 moles of Ambrox are produced each year.

(b)

1 mark
per
correct
structure

Accept structures with the nitrile

group shown as CN

Accept structures with the

carboxyl group shown as COOH.

(c) i) The percentage yields for each step are combined to give an overall 1 mark
yield of 24.87 %.

ii) Number of moles of (-)-drimenol needed = (number of moles of 1 mark

Ambrox produced in a year)/(overall yield) = (42304.5/0.2487) =
170102.5 moles of (-)-drimenol

(-)-drimenol has a molar mass of ((15*12.01)+(26*1.008)+(1*16)) =

222.358 g mol-1.

The mass of (-)-drimenol needed is therefore (222.358*170102.5) =

38 tonnes.

Also accept correctly worked solutions using the candidate’s

answers to (a) and (c) i).

Do not penalise candidates for rounding values in the intermediate

part of the calculation.

iii) The mass of bark needed = (mass of (-)-drimenol)/(proportion of (-)- 1 mark

Note: Tests are to be taken under controlled conditions. Students must not have access to
the information contained in this marking scheme prior to, or during, the test.
 drimenol in bark) = 37.825/0.005 = 7.6x103 tonnes.

Also accept correctly worked solutions using the candidate’s answer

to (c) ii).

Question 2
Answer Marks

(a) % Cu = 27.58% 2
marks

(b) i) Ag+ + Cl- → AgCl OR AgNO3 + Cl- → AgCl + NO3- 1 mark

ii) % Cl = 38.46% 2
marks

(c) i) Oxygen 1 mark

ii) C:H:N:Cu:Cl = 8:24:2:2:5 2

marks
2 marks or nothing.

iii) [Cu4Cl10O]4- 1 mark

Question 3
Answer Marks

(a) U + 3ClF3 UF6 + 3ClF 1 mark

(b) The Ag and Cl in AgCl should be circled. 1 mark

(c) i) 3IF I2 + IF3 5IF3 I2 + 3IF5 7IF5 I2 + 5IF7 3

marks
ii) 3IF I2 + IF3
ΔrHθ= −3ΔfHθ(IF) + ΔfHθ(IF3) = (286.2 – 486) kJ mol−1 = –199.8
kJmol−1

5IF3 I2 + 3IF5 3
ΔrHθ = −5ΔfHθ(IF3) + 3ΔfHθ(IF5) = (2430 – 2529) kJ mol−1 = –99 kJ marks
mol−1

7IF5 I2 + 5IF7
ΔrHθ = −7ΔfHθ(IF5) + 5ΔfHθ(IF7) = (5901 – 4812.5) kJ mol−1 = +1088.5
kJ mol−1

iii) IF5 doesn’t disproportionate. 1 mark

Note: Tests are to be taken under controlled conditions. Students must not have access to
the information contained in this marking scheme prior to, or during, the test.
Question 4
Answer Marks
A = Water vapour (or gas), B = Ice (or solid), C = Liquid water 1 mark
(a) i) (or liquid)

ii)
Chemical A
Potential

2 marks
C
0 oC 100 oC
Temperature

Both correct (2 marks). One mark for each correct temperature

(can be either in oC or K). Must indicate clearly that temperatures
correspond to the point on the graph where the lines intersect to get
the marks.

(b) i) Chemical
A
Potential

Chemical C 1 mark
Potential of a
Salt Solution
Temperature

(1 mark) Accurate positioning is not required but line they have

drawn must be below line C at all points.

ii) Higher than Water 1 mark

(c) i) RMM (H2O) = 18.016 1 mark

Density of H2O = 1000 g dm−3
Concentration of Water = Density/RMM = 55.5 mol dm−3

ii) Concentration of NaCl = 3.00 mol dm-3

Concentration of ions = 6.0 mol dm-3 1 mark
Concentration of H2O = 55.5 mol dm-3
Mole fraction of ions (xi) = 6.0/(6.0 + 55.5)
= 0.10

Note: Tests are to be taken under controlled conditions. Students must not have access to
the information contained in this marking scheme prior to, or during, the test.
 2
xi RTm
(d) i) ΔT = 2 marks
ΔmH Θ
∆T = (0.0976 x 8.314 x 273 x 273)/6010
∆T = 10.1 K
Freezing Point = −10.1 oC or 262.9 K

All correct (2 marks) [Error Carried Forward – Answer should be

103.1 x Answer to part c) ii)] If enthalpy is used in kJ without
converting then 1 mark.

ΔT Δ m H Θ
ii) xi = 2
RTm
xi = (21.1 x 6010)/(8.314 x 273 x 273)
xi = 0.205 2 marks
xi = [ions]/([ions] + [water])
0.205 = [ions]/([ions] + [55.5])
Rearranging, [ions] = 14.31 mol dm-3
Concentration of NaCl = 7.16 mol dm-3

All correct (2 marks) Correct calculation of xi (1 mark). If xi

incorrect but correct calculation to work out [NaCl] from xi (1 mark)

Concentration of CaCl2 = 3.0 mol dm-3

(e) Concentration of ions = 9.0 mol dm-3
Concentration of H2O total = 55.5 mol dm-3
Concentration of Free H2O = 55.5 – (9 x 3.0)
= 28.5 mol dm-3
Mole fraction of ions (xi) = 9.0/(9.0 + 28.5)
= 0.240
xi RTm
2 2 marks
ΔT =
ΔmH Θ
∆T = (0.240 x 8.314 x 273 x 273)/6010
∆T = 24.7 K
Freezing Point = −24.74 oC or 248.3 K

All correct (2 marks). If [ions] of 6.0 mol dm-3 used or failure to

account for bound water but all else correct (1 mark). (Final answer
should be xi x 103.1). If more than one mistake made in calculation
of xi no marks.

Note: Tests are to be taken under controlled conditions. Students must not have access to
the information contained in this marking scheme prior to, or during, the test.
Question 5
Answer Marks
All correct = 1
(a) i) +4 ii) +8 iii) +6 2 correct = ½

(b) Oxidation 1 mark

(c) OsO4 1 mark

(d) +6 1 mark

(e) i) ii) All correct = 2

2 correct = ½
iii) iv)
(f) i) 3 1 mark

DIOL ALKENE

(f) ii)

(1 mark) for each correct pair of diol and alkene to a maximum

of (3 marks) if all correct. If meso compound is drawn twice do
not penalise again if answer to f) i) is 4. No marks are awarded 3 marks
for correct diol with incorrect or missing alkene, or for alkene
on its own.
(g) 5 8 9 12
All correct (2 marks); (½ mark for each correct number). If
more than four numbers are given then (minus ½ mark) for 2 marks
each additional answer above the first four down to a minimum
of zero.

Note: Tests are to be taken under controlled conditions. Students must not have access to
the information contained in this marking scheme prior to, or during, the test.
Question 6
Answer Marks

(a) Mass of a gold atom = 197 g mol−1 / 6.02 ×1023 mol-1 = 3.27 × 10−22 g 1 mark

(b) Number of atoms in unit cell = (8 × 1/8) + (6 × 1/2) = 4 1 mark

(c) i) If a is the length of the unit cell edge and r is the radius of an atom: 1 mark
a√2 = 4r

length AB = 4r / √2 = 2√2 × r

ii) volume of unit cell = 32r3 / √2 = 16√2 × r3 1 mark

iii) length of body diagonal a√3 = 2√6 × r 1 mark

(d) Molar volume of gold = 197 g mol−1 / 19.3 g cm−3 = 10.2 cm3 mol-1 1 mark

(e) Fraction = 4 × volume of gold atom / unit cell volume 1 mark

= (4 × 4/3 πr3) / (16√2 × r3) = π√2 / 6 = 0.74

Can accept π√2 / 6

(f) Radius of gold atom = [(volume of gold atom) / (4/3)π]1/3 1 mark

= [(10.2 cm3 mol-1 / 6.02 × 1023 mol-1) × 0.74 / (4/3)π]1/3
= 1.44 × 10−8 cm

(g) i) Surface area of dome = ½ × 4π(21 m / 2)2 = 693 m2 1 mark

Volume of gold = 80 000 g / 19.3 g cm−3 = 4 145 cm3 = 0.004 145 m3

Average thickness of gold = 0.004 145 m3 / 693 m2 = 6.0 × 10−6 m =

6.0 × 10−4 cm

ii) Thickness of a layer of gold atoms = (2√6 × r) / 3 = 2.35 × 10−8 cm 1 mark

Number of layers of gold atoms = 6.0 × 10−4 cm / 2.35 × 10−8 cm =
2.5 × 104

Only penalise once for error carried forward

Note: Tests are to be taken under controlled conditions. Students must not have access to
the information contained in this marking scheme prior to, or during, the test.
 43rd INTERNATIONAL
CHEMISTRY OLYMPIAD
2011

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 in the right hand margin of the answer booklet.

Some questions may contain unfamiliar material. 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.
 H He
1 2
1.008 4.003

Li Be symbol B C N O F Ne
3 6.94 4 9.01 atomic number 5 6 7 8 9 10
mean atomic mass 10.81 12.01 14.01 16.00 19.00 20.18

Na Mg Al Si P S Cl Ar
11 12 13 14 15 16 17 18
22.99 24.31 26.98 28.09 30.97 32.06 35.45 39.95

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
39.102 40.08 44.96 47.90 50.94 52.00 54.94 55.85 58.93 58.71 63.55 65.37 69.72 72.59 74.92 78.96 79.904 83.80

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
85.47 87.62 88.91 91.22 92.91 95.94 101.07 102.91 106.4 107.87 112.40 114.82 118.69 121.75 127.60 126.90 131.30

Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
132.91 137.34 138.91 178.49 180.95 183.85 186.2 190.2 192.2 195.09 196.97 200.59 204.37 207.2 208.98

Fr Ra Ac+
87 88 89

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
*Lanthanides 58 59 60 61 62 63 64 65 66 67 68 69 70 71
140.12 140.91 144.24 150.4 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
+Actinides 90 91 92 93 94 95 96 97 98 99 100 101 102 103
232.01 238.03
1. This question is about a popular snack food.

The ingredients of a ‘salt and vinegar flavour baked corn snack’ are listed as:
• maize
• vegetable oil
• flavouring
• salt
A small bag typically contains 22 g of the snack.
The snack was analysed as follows:
Calorimetry
A 2.0 g sample of the snack was burnt completely. The temperature of the water in the
calorimeter rose by 20.9 oC. The calorimeter contained 500 g of water.
Titration
The crushed contents of a whole small bag of the snack were washed with distilled water
to dissolve all of the salt. The resulting solution was made up to 250 cm3 in a volumetric
flask.
A 25.0 cm3 portion of this solution was titrated against 0.100 mol dm-3 aqueous silver
nitrate(V) using potassium chromate(VI) as the indicator.
8.20 cm3 of aqueous silver nitrate(V) solution were required to reach the red-brown end
point.

The specific heat capacity of water is 4.18 J K-1 g-1

1kJ ≡ 0.239 dietary calories

a) Calculate the number of dietary calories in a typical small bag of the snack. [2]
b) Give the chemical formula for (i) silver nitrate(V) and (ii) potassium chromate(VI). [2]
c) Write an ionic equation for the titration reaction and calculate the mass of sodium
chloride in a typical small bag of the snack. [3]

The ‘sharp’ taste of the snack comes from citric acid. The IUPAC recommended name for
citric acid is 2-hydroxypropane-1,2,3-tricarboxylic acid.

d) Draw the skeletal structure for citric acid. [2]

A carbon atom bonded to four different groups is called a chiral centre or an asymmetric
carbon atom.

e) How many chiral centres does a molecule of citric acid contain? [1]
2. This question is about calcium carbide.

Calcium carbide, CaC2, also known as calcium acetylide, is produced in large quantities
around the world, mostly in the Far East. Calcium carbide has been used in a variety of
ways, including as a component in self-igniting maritime distress flares.

Use the following information about calcium carbide to help you answer questions (a)–(g)
below.

• Calcium carbide is formed from the reaction between lime (calcium oxide) and coke
(carbon) at about 2000 oC. The side-product of this reaction is a toxic gas, A, that is a
reducing agent.
• The lime used in the production process commonly contains a small amount of calcium
phosphate(V) as an impurity. In the reaction with coke, this impurity reacts to form
compound B (a simple ionic compound of calcium and phosphorus) as well as gas A.
• Calcium carbide reacts with excess water to form a colourless, flammable gas, C. A
white solid is also formed which is slightly soluble in water to give a colourless alkaline
solution. Gas C is a hydrocarbon containing 92.3% carbon by mass. The relative
molecular mass of C is shown to be 26.
• The addition of calcium carbide to water generates an unpleasant smell. It is now
known that it is actually the reaction of water with compound B that produces this
smell.

a) Draw a ‘dot-cross’ diagram of the carbide ion, C22-. [2]

b) Which two well-known diatomic gases are iso-electronic (same number of electrons) with [2]
the carbide ion?

c) Write a balanced equation for the formation of calcium carbide and gas A from lime and
coke. [1]

d) Calculate (i) the empirical formula and (ii) the molecular formula of hydrocarbon C. [2]

e) Write a balanced equation for the reaction of calcium carbide with water. [1]

f) Write a balanced equation for the reaction between calcium phosphate(V) and coke to
form gas A and compound B. [2]

g) Suggest the identity of the molecule responsible for the unpleasant odour that is produced
when compound B reacts with water. [1]
3. This question is about explosives.
CH3
Explosives are often associated with O2N NO2
causing destruction and harm, but O2N NO2 N N
explosives have also played a major role
in civil engineering for hundreds of years.
N
‘Blasters’ (explosives engineers) need a
good understanding of geology and the NO2 NO2
science of explosives to be able to
design explosions ‘to order’. TNT RDX

Explosions occur when reactions proceed so that heat is generated more rapidly than it
can be dispersed.
Some high explosives have the general formula CaHbNcOd. The oxidiser (O) and the fuel
(C, H) are present in the same molecule. Nitrogen atoms are present so that there is the
highly exothermic production of hot N2 gas.

a) Find an expression for d (in terms of a, b and c) that must be satisfied for an explosive
CaHbNcOd to decompose to form CO2, H2O and N2 only. [2]

The oxygen balance of an explosive is the mass of oxygen either in excess (i.e. the
balance is positive) or in deficit (i.e. the balance is negative) of that required for complete
oxidation of C and H.
The oxygen balance is expressed as a percentage of the molar mass of the explosive.

b) Write a general expression for the oxygen balance of CaHbNcOd. [2]

c) Calculate the oxygen balance for RDX, whose structure is given above. [2]

When the explosive does not contain enough oxygen, there is incomplete oxidation of C
and/or H. In the case of nitrated aromatic compounds, the reaction products are given by
the following set of ‘rules’:
• carbon atoms react with the available oxygen to form CO
• N atoms combine to form N2
• 1/3 of the CO produced is converted to C+CO2
• 1/6 of the original CO produced reacts with any available H in the compound to
form C + H2O

d) Write the equation for the explosion of TNT. [2]

e) Calculate the mass of TNT that will explode to produce 1.0 dm3 of gas at room
temperature and pressure. [The molar volume of any gas = 24 dm3 at RTP] [2]
4. This question is about solving a puzzle using spectroscopy.

If required, use the information on the next page to help you answer this
question.

Your task is to identify compounds 1-7 using the information given below.
In your answer booklet, you should draw the skeletal formula of each compound and give
the systematic names of compounds 1- 4. [13]
• Compounds 1-7 all have the same molecular formula, C4H10O, but have different
chemical, structural and spectroscopic properties.
• Compounds 5, 6, and 7 have lower boiling points than compounds 1-4.
• Compounds 1-4 have a broad absorption at 3300 cm-1 in their infra-red spectra.
• Compound 2 can exist as optical isomers.
• The 1H NMR spectrum of compound 3 is shown below:

• The 1H NMR spectra of compounds 4 and 5 each consist of two distinct signals.

• The 1H NMR spectrum of compound 5 gives the following data:

Chemical Shift Splitting Relative intensity
ppm pattern
1.21 triplet 3
3.47 quartet 2

• The 13C NMR spectrum of compound 6 contains four distinct signals, whereas the 13C
NMR spectrum of compound 7 shows only three.
Information about NMR spectroscopy (for Q4).

NMR spectroscopy is a technique that reveals the number of different environments of

certain nuclei in a molecule.
Thinking about the symmetry present in a molecule is important when interpreting NMR
spectra.
Both carbon atoms (13C) and hydrogen atoms (1H) give NMR signals (i.e. are NMR-active
nuclei).Each NMR-active nucleus in a different molecular environment will give rise to one
signal with a characteristic chemical shift (measured in ppm).
The relative intensity of each signal in a spectrum is proportional to the number of nuclei in
a particular molecular environment.
1
H NMR is complicated by coupling. If a hydrogen nucleus is within three bonds of another
hydrogen nucleus which is in a different molecular environment, instead of appearing as a
single peak, its signal is split into a number of peaks.
If a hydrogen nucleus couples to n other hydrogen nuclei, its signal will split into a total of
(n+1) peaks.

For example, the spectrum for compound 3 shown opposite, indicates that there are 4
different 1H environments. The relative intensities of the peaks are 2:1:1:6.
The splitting patterns for peaks A, B and C are shown in larger scale.
5. This question is about the synthesis of phenobarbital

Barbiturates are derivatives of barbituric acid which act as central nervous system
depressants. Barbiturates are used in the treatment of seizure disorders. One example of
a barbiturate that has been used as an anti-convulsive for many years is phenobarbital.
Phenobarbital can be synthesised from two compounds, A and G:
O

NaOEt HN NH

Compound A + Compound G

O O

Phenobarbital

a) Compound A can be found as a metabolite in human urine.

Use the information below and in the introduction above to determine the molecular formula of
compound A. Show clearly the important steps in your working. [4]

• Combustion of a 0.250g sample of compound A produces 0.178g of CO2 and 0.146g

of H2O.
• A further 0.250g sample of compound A, when boiled with an excess of alkali,
liberates all the nitrogen as ammonia, NH3. The ammonia generated in this reaction
is sufficient to neutralise 40.8cm3 of 0.200 mol dm-3 aqueous hydrochloric acid.
• Mass spectrometry shows that compound A has a relative molecular mass of 60.

Compound G can be synthesised as follows:

[Note: NBS is N-bromosuccinimide - a source of bromine radicals and Et = ethyl]

CH3

NBS 1. Mg, Et2O

Compound B Compound C
CCl4 C7H7Br 2. CO2 C8H8O2
3. H+

SOCl2
O

EtO OEt EtOH Compound D

Compound F Compound E
C13H16O4 C10H12O2 C8H7ClO
NaOEt

NaOEt
EtBr (NaOEt is a strong base)

Compound G
C15H20O4

b) In your answer booklet, draw the structural formulae of compounds A – G. [7]

 43rd INTERNATIONAL CHEMISTRY OLYMPIAD
UK Round One - 2011

MARKING SCHEME
Notes:
Chemical equations may be given as sensible multiples of those given here.
Formulae can be given by any conventional method (i.e. structural or molecular)
unless a particular format is specified by the question.
State symbols do not need to be included in chemical equations to obtain the
mark(s).
Answers should be given to an appropriate number of significant figures although the
marker should only penalise this once (on the whole paper).

Total marks for paper = 55

Question 1
Answer Marks
a) Heat energy transferred to the water for 2.0 g snack
= 500 x 4.18 x 20.9 J = 43681 J (or 43.7 kJ) 1
Whole bag of snack = (43681* x 22/2.0)/1000
= 480 kJ
= 115 dietary calories.
Allow 2 or 3 sf. Correct answer scores 2 marks without reference to 1
working. *Allow ecf from first marking point.
b) (i) AgNO3 1
(ii) K2CrO4 1
c) Ag+ + Cl– Æ AgCl [Allow equation with spectator ions] 1

Moles silver (nitrate) = (8.20/1000) x 0.100 = 8.20 x 10-4

Allow ecf from equation.
Moles (sodium) chloride from small bag of snack = 8.20 x 10-4 x 10
Mass sodium chloride in small bag snack = (8.20 x 10-4 x 10) x 58.44
= 0.479 g (3sf)
Correct answer scores 2 marks without reference to working. 2
Allow 1 mark if correct answer but given to 2 or 4 sf.
O OH
d) O O
2
HO OH
OH

Allow any clear representation of the correct structure for 1 mark if

not skeletal.
e) None 1

10 marks

Note: Tests are to be taken under controlled conditions. Students must not have access to
the information contained in this marking scheme prior to, or during, the test.
Question 2
Answer Marks
a) x
C x Cx
x 2
1 mark for bond pairs shown
1 mark for lone pair (any dot-cross equivalent) on each carbon
b) Nitrogen / N2 1
Carbon monoxide / CO 1
c) CaO + 3C Æ CaC2 + CO 1
d) (i) C = 92.3/12.01 = 7.69 moles 1
H = 7.7 / 1.008 = 7.64 moles
Empirical formula = CH (RMM = 13)
(ii) Since RMM = 26, molecular formula of C is C2H2 1
e) CaC2 + 2H2O Æ Ca(OH)2 + C2H2 1
Allow ecf from d(ii). Do not allow CaO as product.
f) Ca3(PO4)2 + 8C Æ 8CO + Ca3P2 2
1 mark for formula of calcium phosphate(V) correct
1 mark for equation balanced
g) phosphine, PH3 or diphosphine, P2H4 1
Allow name or formula.

11 marks

Note: Tests are to be taken under controlled conditions. Students must not have access to
the information contained in this marking scheme prior to, or during, the test.
Question 3
Answer Marks
a) (CaHbNcOd → a CO2 + b/2 H2O + c/2 N2)
d = 2a + b/2 2
Award 1 mark for 2a and 1 mark for b/2
b) O balance = 16 × (d – 2a – b/2) x 100%
(12a + b + 14c + 16d) 2
Allow 1 mark if correct but ‘x 100’ missing
c) O balance = - [100 × (3 × 16) / 222.14] = -21.6%
Award 1 mark for correct sign, 1 mark for magnitude. 2
Allow ecf (both number and sign) from expression in (a).
d) C7H5N3O6 → 3 CO + 3 C + CO2 + 3/2 H2 + 3/2 N2 + H2O
Allow 1 mark if equation is incorrect but correct products are shown 2
and equation is balanced.
e) Amount of gas = 1/24 mol.
Molar ratio TNT: gas = 1:7 [Allow ecf from (d)] 2
Amount of TNT = 1/7 × 1/24 mol = 1/168 mol = 0.0060 mol
Mass of TNT = 227.14 g mol-1 × 1/168 mol = 1.35 g
Award 2 marks for correct answer (with ecf if necessary) without
working.

10 marks

Note: Tests are to be taken under controlled conditions. Students must not have access to
the information contained in this marking scheme prior to, or during, the test.
Question 4
Answer Marks
Award 1 mark for any clear representation (even if not skeletal) for
each correct structure in the correct box. Award an additional mark
(for structures 1-4) if the name matches the structure drawn.
If incorrect structure is drawn in a box (e.g. butan-2-ol is drawn in box
1) but name matches the structure drawn – award 1 mark.
See additional note below.
1 = butan-1-ol 1

OH
1
2 = butan-2-ol 1

1
OH
3 = 2-methylpropan1-ol [Initial ‘2’ can be omitted] 1

1
OH
4 = 2-methylpropan-2-ol [Initial ‘2’ can be omitted] 1

1
OH
5=
1
O

6=
O 1

7=
O 1

Add 2 extra marks to candidate’s total for this Q if all structures 2

correctly drawn as skeletal. Award 1 additional mark for four or more
structures correctly drawn as skeletal.

13 marks

Note: Tests are to be taken under controlled conditions. Students must not have access to
the information contained in this marking scheme prior to, or during, the test.
Question 5
Answer Marks
a) • Moles A = 0.250/60 = 4.2 x 10–3
• Moles C = moles CO2 = 0.178/44.01 = 4.0(4) x 10–3
• Moles H = 2 x moles H2O = 2 x (0.146/18.016) = 16.2(1) x 10–3
• Moles N = moles NH3
= moles HCl = (40.8/1000) x 0.200 = 8.16 x 10–3
• Mass of C + H + N in sample of A
= (4.04 x 10–3 x 12.01)+(16.21 x 10–3 x 1.008)+(8.16 x 10–3 x
14.01) = 0.179(2)g
• Mass of O in A = 0.250 – 0.179(2) = 0.071g 4
• Moles of O in A = 0.071/16 = 4.4 x 10–3
• This gives empirical formula of A = CH4N2O
• Mr (A) = 60, so molecular formula of A is also CH4N2O
• [Or .. CH4N2 = 44, Mr(A) = 60; molecular formula of A = CH4N2O]

1 mark for calculating moles A, C and H; 1 mark for calculating

moles N; 1 mark for deducing oxygen as missing element; 1 mark for
final formula
b) A: O Allow any clear representation of
correct structures. Award 1 mark
for each correct structure
H2N NH2

CH2Br CH2CO2H
B: C:

D: CH2COCl E: CH2CO2Et

F: O O G: O O

EtO OEt EtO OEt

11 marks

Note: Tests are to be taken under controlled conditions. Students must not have access to
the information contained in this marking scheme prior to, or during, the test.
 44th INTERNATIONAL

CHEMISTRY OLYMPIAD

2012

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.

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 18

H He
1 2 13 14 15 16 17 2
1.008 4.003

Li Be symbol B C N O F Ne
3 4 atomic number 5 6 7 8 9 10
6.94 9.01 relative atomic mass 10.81 12.01 14.01 16.00 19.00 20.18

Na Mg Al Si P S Cl Ar
11 12 13 14 15 16 17 18
22.99 24.31
3 4 5 6 7 8 9 10 11 12 26.98 28.09 30.97 32.06 35.45 39.95

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
39.102 40.08 44.96 47.90 50.94 52.00 54.94 55.85 58.93 58.71 63.55 65.37 69.72 72.59 74.92 78.96 79.904 83.80

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
85.47 87.62 88.91 91.22 92.91 95.94 101.07 102.91 106.4 107.87 112.40 114.82 118.69 121.75 127.60 126.90 131.30

Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
132.91 137.34 138.91 178.49 180.95 183.85 186.2 190.2 192.2 195.09 196.97 200.59 204.37 207.2 208.98

Fr Ra Ac+
87 88 89

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
*Lanthanides 58 59 60 61 62 63 64 65 66 67 68 69 70 71
140.12 140.91 144.24 150.4 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
+Actinides
90 91 92 93 94 95 96 97 98 99 100 101 102 103
232.01 238.03
1. This question is about sulfur chemistry

Sulfur forms many cyclic allotropes with different

ring sizes. In the solid state, the most stable
allotrope of sulfur is a form of S8. In the gas phase,
all ring sizes from S3 to S12 have been detected.

In the gas phase, the different ring sizes are in equilibrium; the equation for the equilibrium
between S7(g) and S8(g) is given below:
8S7(g) 7S8(g)

(a) Given that the S–S bond strength in S7 is 260.0 kJ mol−1 and in S8 is 263.3 kJ mol−1,
calculate the enthalpy change for the forward reaction.

When dissolved in an organic solvent, S6, S7 and S8 were all detected in equilibrium in the
following proportions by mass:

ring size S6 S7 S8

% by mass 0.32 0.76 98.92

(b) i) Calculate the amount, in moles, of S7 and S8 at equilibrium when 1.00 g of sulfur is
dissolved in 1.00 dm3 of solvent.

ii) Give the expression for the equilibrium constant for the reaction between S7 and S8
as written above.

iii) Calculate the value of this equilibrium constant.

In the solid phase, S8 crystallises in two well known forms: orthorhombic and monoclinic.
The enthalpy changes of combustion of these two forms are as follows:

ΔcH (S8, orthorhombic, 298 K) = −296.8 kJ mol−1, ΔcH (S8, monoclinic, 298 K) = −297.1 kJ mol−1

(c) i) Determine the enthalpy change at 298 K for the reaction

S8(s, orthorhombic) S8(s, monoclinic).

ii) Which is the more stable form at 298 K?

Sulfur also forms an 8-membered ring in a compound with nitrogen, S4N4, which forms gold-
coloured crystals.

(d) In S4N4, nitrogen and sulfur atoms alternate in the ring. The nitrogen atoms form three
bonds; two of the sulfur atoms form two bonds, two form four bonds. Draw the
structure of S4N4 assuming there are no cross-links within the ring.

(e) An alternative form of the S4N4 structure is based on the same arrangement of atoms
except there is a bond between both pairs of opposite sulfur atoms. Every sulfur atom
has four bonds in this structure; nitrogen atoms again have three bonds. Draw this
alternative structure of S4N4 (but do not attempt to draw the 3D structure).

(f) If S4N4 gas is passed over silver metal it yields a linear polymer, poly(sulfur nitride), that
conducts electricity and is a superconductor at very low temperatures. The polymer
contains just two types of bond: N−S and N=S. Each N atom has three bonds; each S
has two or four. Draw a repeat unit of this polymer.
2. This question is about controlling your hair

Human hair consists largely of proteins (polypeptides),

such as keratin. Keratin is unusual in that it contains a
very large proportion of the sulfur-containing amino acid
cysteine.

The sulfur content of hair may be found by complete

alkaline hydrolysis, followed by oxidation to convert all
the sulfur to sulfate. This may be measured by
precipitating it out as barium sulfate.

A 1.00 g sample of hair is hydrolysed and the sulfur content converted to sulfate. Aqueous
barium chloride is added until no more precipitation takes place, taking the total volume to
2.50 dm3. On filtration of the mixture at 20 °C, 260 mg of BaSO4 is recovered after drying.

(a) i) Calculate the percentage by mass of sulfur in the sample of human hair to 3
significant figures. Assume that all the sulfur is converted to BaSO4 precipitate.

ii) With such a small quantity of precipitate, account must be taken of its solubility in
water: 2.40 mg dm−3 at 20 °C. Calculate the percentage by mass of sulfur to 3
significant figures taking this solubility into account.

Cysteine is unique amongst amino acids in being able to form covalent cross-links between
amino acids at two different points in a peptide chain. These covalent cross-links are called
disulfide bonds, and two cysteine residues that have become linked in this way form a
cystine residue. These disulfide bonds are responsible for the majority of the structural
strength of hair.

(b) How would you classify this reaction of two cysteine residues to form a cystine residue?

(i) Dehydration (ii) Hydrolysis (iii) Oxidation (iv) Reduction

 Both hair-perming lotions and hair removal cream use chemicals
that break these disulfide bonds and so decrease hair strength.
Both of these methods can use salts of thioglycolic acid in order to
break the disulfide bonds.
Thioglycolic acid

Thioglycolic acid has two acidic protons. The pKa values for the dissociation of these two
protons are 3.67 and 10.31.

pKa = − log10Ka Ka = [H+][A−]/[HA] pH = − log10[H+]

(c) Draw the predominant form of thioglycolic acid that is present in aqueous solution at
i) pH 0 ii) pH 7 iii) pH 14

(d) Calculate the percentage of mono-anion and percentage of di-anion present at pH 9.0.
You may assume that these are the only two species present at this pH.

The chemical reaction carried out by the thioglycolic acid takes place in two steps:

Step 1: Ker-S-S-Ker + RS-H Ker-S-S-R + Ker-S-H

Step 2: Ker-S-S-R + RS-H R-S-S-R + Ker-S-H

The following abbreviations are used:

RS-H: thioglycolic acid (all forms, mono-anion, di-anion etc.)
Ker-S-S-Ker: a cystine residue in keratin protein
Ker-S-H: a cysteine residue in keratin protein.

(e) Write an equation for the overall chemical reaction.

As the initial disulfide bond cleavage is slow, it is often found that Step 1 is the rate
determining step of the reaction. Usually the thioglycolic acid is present in a large excess
and there is rapid diffusion into the hair. Under these reaction conditions the cleavage of the
disulfide bonds follows second-order kinetics given by the equation below, but the
concentration of thioglycolate is in a large excess and so remains essentially unchanged
during the course of the reaction at concentration [RSH] 0. (The rate constant, k, is pH
dependent and increases with increasing pH.)

(f) On the graph, which

line best corresponds
with how the
concentration of
Ker-S-S-Ker varies
with time?
In practice it is not possible to measure the number of Ker-S-S-Ker linkages directly.
However, to a good approximation, the number of linkages is proportional to the tensile
stress of a strand of hair, a property that can easily be measured mechanically. This allows
the following equation to be derived relating the tensile stress, F, to the initial tensile stress,
F0, and the time, t :

Some strands of hair were treated with 0.16 mol dm–3 thioglycolate solution buffered at pH
9.0 for a period of one hour at 298 K.

(g) Use the graph below to calculate a value for the rate constant, k, at 298 K. Give the
appropriate units.

(h) Olympiad Perm Solution is a

pH 9.0 solution containing ammonium
thioglycolate and is available in 500 cm3
bottles. What is the mass of
ammonium thioglycolate in one bottle of
Olympiad Perm Solution?
3. This question is about chemistry general knowledge

(a) Put the following elements in the order in which they were discovered. Put the longest-
known element first.
Ar O P Pu S

(b) Rank the following molecules in the order of their boiling point from 1 to 6. Rank the
lowest-boiling-point "1" and the highest "6".
C2H5OC2H5 C2H5OH HOCH2CH2OH CH3CHO C4H10 H2O

(c) Write the chemical formula that best describes the following.
(i) Fool’s gold (ii) Epsom salts (iii) Laughing gas

(d) What are the systematic names for the following chemicals?
(i) Acetone (ii) Toluene (iii) Sodium hypochlorite

(e) What is the colour change when zinc oxide is heated?

(f) Look at the chemical structures shown below. In the questions that follow, each
compound should be assigned only once.

i) Which naturally occurring stimulant would you find in your tea?

ii) Which might you take with a cup of tea if you have a headache?

iii) Which compound might you add to your tea if you liked it sweet?

iv) Which compound might you add to your tea if you liked it sweet but were on a low
sugar diet?

v) Which compound would you never add to a cup of tea?

4. This question is about the synthesis of top-selling drug Lipitor

With annual sales worth billions of pounds, for many years Pfizer's cholesterol-lowering drug
Lipitor has been the best-selling pharmaceutical in the world. The first steps of a multi-stage
synthesis of Lipitor are shown below.

Given in the boxes are the most characteristic IR stretching frequencies of the intermediates
in the synthesis. No stretches due to any C–C or C–H bonds are included; stretching
frequencies due to single bonds other than bonds to hydrogen do not show up in the range
listed. You are not expected to know these stretching frequencies, but through careful
reasoning, you should be able to use them to help work out the structures of the unknowns.

Note that not all the by-products are shown in the reaction schemes.

(a) Give the structures for the compounds B to G and, over the course of the whole
question, complete the table of IR absorptions found in compounds A to M.

absorption ~ 3300
? 2250-2275 ? 1700-1740
/ cm–1 (broad)
C=O in a
bond ? ? N–H ?
small ring

Ester H is deprotonated by strong bases to

give the reactive carbon nucleophile, anion I.
The R group in the structure is an alkyl chain
which remains unchanged throughout the
entire synthesis.

(b) Draw the structure for the anion I.

The synthesis continues as shown below:

(c) Give the structures for the compounds J, K and L.

In a separate branch of the synthesis, N reacts with phenylamine to give compound O. This
may be deprotonated in base to give another carbon nucleophile, anion P. Anion P reacts
with benzaldehyde to give Q ; Q then dehydrates to give compound S. S reacts with
fluorobenzaldehyde in the presence of a catalyst to give compound T.

(d) Give the structures of phenylamine and 4-fluorobenzaldehyde.

(e) Suggest structures for O, anion P, and compounds Q and S.

In the final stage of the synthesis, T and M are brought together to give compound U which
on hydrolysis in aqueous acid gives the target, the drug Lipitor.

(f) Suggest a structure for compound U.

5. This question is about the world's smallest powered car

In November of 2011, the premier

scientific journal Nature published an
article titled "Electrically driven directional
motion of a four-wheeled molecule on a
metal surface". Essentially, this paper
reported the synthesis and observations
of the world's smallest powered car – the
"Nano-car".

On completion of the synthesis, the sample was analysed using NMR and mass
spectrometry. Not surprisingly, the group did not submit their precious material for
combustion analysis!

(a) i) Give an equation for the complete combustion of nano-car.

ii) Calculate the percentage by mass of carbon, hydrogen and nitrogen that would be
predicted were the analysis to be performed. Give your answers to two decimal places.

Crucial in the design of the molecule are the hexyl and methyl groups shown explicitly in the
structure above. It is because of these that the aromatic "wheels" of the car are actually
arranged at an angle, straining the double bond that attaches them to the rest of the
structure. This double bond can break, rotate and reform when sufficient electronic energy
is provided using the tip of a scanning tunnelling microscope.

The carbon atoms to which the methyl groups are attached are chiral centres – each has
four different groups attached to it. These are marked with an asterisk in the structure
above.

The car is made up of four rotor units. A

separate rotor unit exists as optical isomers –
non-superimposable mirror images called
enantiomers. Chemists distinguish between
them with the labels "R" and "S" as shown on
the right. The "wheels" on each enantiomer
turn in opposite directions as shown (as
viewed as if standing next to the car facing the The bold wedge comes out of the paper;
wheel). the hashed bond goes into the plane.
In the synthesis of the car, a number of different stereoisomers were formed. These are
shown in cartoon form below, in the arrangements the chemists detected on a surface of
copper atoms (as viewed from above).

(b) In your answer booklet, assign the label "R" or "S" to each rotor unit in the cars A-F in
the boxes provided. The top left rotor in each car has already been assigned.

(c) Which of the cars A-F are optical isomers?

(d) Before being deposited on the copper surface, rotation is possible about the triple
bonds linking the two halves of the car. Taking this into account, which of the cars A-F
are the same molecule when free from the surface?

(e) By considering the directions of rotation for the four rotor units in each car, and
assuming that all four rotors are active simultaneously, complete the table in the answer
booklet, indicating whether each car will :

• spin round on the copper surface clockwise

• spin round on the copper surface anti-clockwise

• remain stationary on the copper surface

• move forwards over the copper surface.

Acknowledgements & References

References for questions

Q1
Composition of Elemental Sulfur in Solution
Fred N. Trebbe et al., J. Am. Chem. Soc., 104, 4971-4972, 1982.

Elemental Sulfur
Beat Meyer,Chemical Reviews, 76, 367-388, 1976.

Q2
The kinetics of disulfide bond reduction in hair by ammonium thioglycolate and
dithioglycolic acid,
Melissa Manuszak et al., J. Soc. Cosmet. Chem., 47, 49-58, 1996.

Kinetic studies of hair reduction using a single fiber technique

Randall Wickett J. Soc. Cosmet. Chem., 34, 301-316, 1983.

Q5
Electrically driven directional motion of a four-wheeled molecule on a metal surface,
Tibor Kudernac et al., Nature, 479, 208–211, 2011.

http://www.rsc.org/chemistryworld/News/2011/November/09111103.asp

http://www.youtube.com/watch?v=P-aitePKCkM

http://goo.gl/fnJrN

See also the RSC publication "The Mole" issue 1, January 2012 p9.

The UK Chemistry Olympiad is supported by

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products. It comprises 19 businesses each with a major chemical company heritage. The
production network spans 73 manufacturing facilities in 19 countries throughout the world.
The chemicals INEOS produce enhance almost every aspect of modern life.
 44th INTERNATIONAL CHEMISTRY OLYMPIAD
UK Round 1 - 2012
MARK SCHEME
Question 1 2 3 4 5 Total

Mark 9 14 17 23 17 80

Question 1
Answer Marks
a) (i) Breaking bonds in 8 moles of S7 (g): 8 × 7 × 260.0 kJ mol−1 = 14560.0 kJ mol−1
Making bonds in 7 moles of S8 (g): 7 × 8 × 263.3 kJ mol−1 = 14744.8 kJ mol−1 1
Enthalpy change of reaction = (14560.0 − 14744.8) kJ mol−1 = −184.8 kJ mol−1
b) (i) Amount S7 = 0.0076 g / (7 × 32.06) g mol−1 = 3.387 × 10−5 mol
Amount S8 = 0.9892 g / (8 × 32.06) g mol−1 = 3.857 × 10−3 mol 1
7 8
(ii) Kc = [S8] / [S7] 1
−3 7 −5 8 18
(iii) Value for Kc [3.857 × 10 ] / [3.387 × 10 ] = 7.34 × 10
(Ignore any units) 1
(allow error carried forward from part b(i)
c) (i) ΔrHo(298 K) = (−296.8 − (−297.1)) kJ mol−1 = (+)0.3 kJ mol−1 1
(ii) The most stable form is orthorhombic
1
Allow monoclinic if the answer given in c(i) is negative
d) N S N
S S 1
N S N
e) N S N
S S 1
N S N
f)
N S N S N S N S
1
or or either in reverse order
 Total for Question 1 9
Question 2
Answer Marks
a) (i) Amount of S in moles = amount of BaSO4 = 0.260 g / (137.34 + 32.06 +
4(16.00)) g mol−1
1
= 1.114 mmol
% of sulfur by mass = 1.114 mmol × 32.06 g mol−1 × 100% = 3.57%
(ii) Mass of BaSO4 (aq) in 2.50 dm3 = 2.4 mg dm−3 × 2.50 dm3 = 6.0 mg
Total mass of BaSO4 in 2.50 dm3 = 6.0 mg + 260 mg = 266 mg 1
% of sulfur by mass in human hair = (0.266 g / 0.260 g) × 3.57% = 3.65%
b) Oxidation 1
c) (i) pH 0 (ii) pH 7 (iii) pH 14
3

d) Via pKa = pH – log10 ([A2−]/[HA−]) Or via Ka = [H+] ([A2−]/[HA−])

10.31 = 9 − log10 ([A2−]/[HA−]) Ka/[H+] = ([A2−]/[HA−])
1
log10 ([A2−]/[HA−]) = − 1.31 ([A2−]/[HA−]) = (10-10.31/10-9)
([A2−]/[HA−]) = 0.049 ([A2−]/[HA−]) = 0.049
Then… [A2−] + [HA−] = 100 %
1
So [A2−] = 4.67 % and therefore [HA−] = 95.3 %
e) Ker-S-S-Ker + 2 RS-H → R-S-S-R + 2 Ker-S-H 1
f) Line C 1
−3 −3 −1
g) Gradient of graph allowed between 3.83 × 10 to 4.16 × 10 min
k is then calculated by gradient / 0.16
This corresponds to range of acceptable value for the rate constant k
Minimum k = 3.99 × 10−4 mol−1 dm3 s−1 or 2.40 × 10−2 mol−1 dm3 min−1 2
Maximum k = 4.34 × 10−4 mol−1 dm3 s−1 or 2.60 × 10−2 mol−1 dm3 min−1
2 marks for correct value with correct units; 1 mark if correct but units
missing / wrong; 1 mark if units correct but value is calculated (correctly) from
gradient outside range; 0 marks correct units with incorrect answer.
h) Gradient of graph allowed between 1.23 × 10−2 to 1.27 × 10−2 min−1
Using k from part (g), concentration is calculated by dividing gradient by k.
Concentration = 0.499 mol dm−3
Molar mass of ammonium thioglycolate = (14.01 + 4 × 1.008) + (2 × 12.01 + 2 ×
16.00 + 3 × 1.008 + 32.06) = 109.146 g mol−1
2
Amount in one bottle = 0.500 × 0.499 × 109.146 = 27.2 g
2 marks: One of these is for calculating a correct concentration given their k in
part (g), and one for a correct mass from their concentration. Any answer
close to 27g where the correct method has been used should be given full
credit.
Total for Question 2 14
Question 3
Answer Marks
a) Longest-known Most recently discovered
S P O Ar Pu
All elements in correct order scores 2 marks 2
If the correct order can be achieved by moving one element to any new
position in the candidate's answer, award 1 mark
b)
C2H5OC2H5 C2H5OH HOCH2CH2OH CH3CHO C4H10 H2O
3 4 6 2 1 5
2

All answers correct scores 2 marks

If the correct order can be achieved by moving one compound to a new
position, award 1 mark
c) (i) FeS2 (give 1 mark for FeS) 2
(ii) MgSO4 or MgSO4.7H2O 1
(iii) N2O 1
d) (i) Propanone 1
(ii) Methylbenzene 1
(iii) Sodium chlorate(I) 1
e) White to yellow 1
f) (i) C 1
(ii) E 1
(iii) B 1
(iv) A 1
(v) D 1
Total for Question 3 17
Question 4
Answer Marks
a) B

absorption ~ 3300 2250- 1700- 6

–1 1775 3374
/ cm (broad) 2275 1740
C=O in a
bond O–H C≡ N N–H C=O
small ring
One mark for correct structure for G; one mark for each correct entry in table
b) Anion I

2 marks (1 mark for this alternative)

Question 4 continued
Answer Marks
c) J

d) Phenylamine

4-fluorobenzaldehyde
2
Question 4 continued
Answer Marks
e) O

(Full credit should be given if phenyl rings are shown as C6H5, or Ph)
f) U

Total for Question 4 23

Question 5
Answer Marks
a) (i) C132H120N2 + 164O2  132CO2 + 60H2O + 2NO2
1
or C132H120N2 + 162O2  132CO2 + 60H2O + N2
(ii) Mr = (132 × 12.01) + (120 × 1.008) + (2 × 14.01) = 1734.30
% of C = ((132 × 12.01) / 1734.30) × 100% = 91.41 %
1
% of H = ((120 × 1.008) / 1734.30) × 100% = 6.97%
% of N = ((2 x 14.01) / 1734.30) × 100% = 1.62 %
b)

If top right box on every car is correctly assigned – 2 marks

If top right box on every car is incorrectly assigned – 1 mark (for consistent error)
Mark the bottom left and bottom right boxes in the same way
c) “B and F” is awarded 2 marks
“B and F; A and C” is awarded one mark 2
Any other answer is awarded no marks
d) A, C and E. Any other answer is awarded no mark 1
e)
A B C D E F

(i) Spin clockwise ✓

(ii) Spin anti-clockwise ✓

6
(iii) Remain stationary ✓ ✓ ✓

(iv) Move forwards ✓

One mark for each car/letter/column
Note that if B is marked as ‘anti-clockwise’ and F is marked as ‘clockwise’, this
combination scores 1 mark for consistent error.
Total for Question 5 17
 45th INTERNATIONAL

CHEMISTRY OLYMPIAD

2013

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 1 2 3 4 5 Total

Marks 9 13 9 15 17 63
Available

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
 1 18

H He
1 2 13 14 15 16 17 2
1.008 4.003

Li Be symbol B C N O F Ne
3 4 atomic number 5 6 7 8 9 10
6.94 9.01 relative atomic mass 10 . 8 1 12 . 0 1 14.01 16.00 19.00 20.18

Na Mg Al Si P S Cl Ar
11 12 13 14 15 16 17 18
22 . 9 9 24.31
3 4 5 6 7 8 9 10 11 12 26 . 9 8 28.09 30.97 32.06 35.45 39.95

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
3 9 .1 0 2 40.08 44.96 47.90 50.94 52.00 54.94 55.85 58.93 58.71 63.55 65 . 3 7 69 . 7 2 72.59 74.92 78.96 79.904 83 . 8 0

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54

2
85.47 87.62 88.91 91.22 92.91 95.94 101.07 102.91 106.4 107.87 112.40 114.82 118.69 121.75 127.60 126.90 131.30

Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
132.91 137.34 138.91 178.49 180.95 1 8 3. 8 5 186.2 190.2 192.2 1 95 . 0 9 19 6 . 9 7 200.59 204.37 207.2 208.98

Fr Ra Ac+
87 88 89

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
*Lanthanides 58 59 60 61 62 63 64 65 66 67 68 69 70 71
14 0 . 1 2 140.91 144.24 150.4 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
+Actinides
90 91 92 93 94 95 96 97 98 99 100 101 102 103
232.01 238.03
1. This question is about rocket fuels

The Mars Curiosity rover’s landing in August 2012 was achieved

using variable thrust mono propellant hydrazine rocket thrusters.
Hydrazine, N2H4, is popular with NASA as it produces no carbon
dioxide.

The hydrazine is passed over a suitable catalyst and decomposes to

its elements. The rapid production of the hot gaseous elements is
what provides the thrust. Ammonia can be formed as an intermediate
during the decomposition.

(a) Write a balanced equation for hydrazine decomposing to ammonia and nitrogen gas.

(b) Hydrazine may be obtained from the reaction between ammonia and hydrogen peroxide.

2NH3(g) + H2O2(l) → N2H4(l) + 2H2O(l) ∆rHo = −241.0 kJ mol−1

Work out the standard enthalpy change for the decomposition of hydrazine to its elements.
The standard enthalpy changes of formation in kJ mol−1 are:

NH3: −46.1; H2O2: −187.8; H2O: −285.8

(c) The first ever rocket-powered fighter plane, the Messerschmitt Me 163, was powered by the reaction
between a hydrazine-methanol mixture, known as ‘C-Stoff’, and hydrogen peroxide (‘T-Stoff’).

(i) Hydrogen peroxide reacts with the hydrazine as shown in the equation.

N2H4(l) + 2H2O2(l) → N2(g) + 4H2O(l)

State the oxidation number of nitrogen and oxygen in the reactants and products.

(ii) Hydrogen peroxide oxidises the methanol to carbon dioxide and water.
Write a balanced equation for this reaction.

(iii) The fighter plane would hold 225 litres of hydrazine and 862 litres of methanol. Use the following
standard enthalpy changes and densities to calculate the heat energy evolved under standard
conditions for the combustion of this quantity of rocket fuel. Assume that all the hydrazine and
methanol are fully combusted.

∆cHo (N2H4) = −622.2 kJ mol−1 Density of N2H4 = 1.021 g cm−3

∆cHo (CH3OH) = −726.0 kJ mol−1 Density of CH3OH = 0.7918 g cm−3

(d) Hydrazine is also commonly combined with dinitrogen tetroxide, N2O4, in rocket fuels. This forms a
hypergolic mixture, i.e. the reactants ignite spontaneously on contact. NASA used N2H4 / N2O4 in
many space vehicles and it is likely to be used in next-generation vehicles.

(i) Reactions used in rocketry produce chemically stable products (making the reaction exothermic)
that are formed as gases (which provide thrust). Suggest the reaction products that are formed in
the reaction between N2H4 and N2O4.

(ii) Pure N2O4, when warmed, initially decomposes not into its elements but instead forms a brown
gas. Suggest the identity of this brown gas.

(e) A derivative of hydrazine with formula C2H8N2 was used in rocket fuels in the Apollo missions. It has
two nitrogen atoms that are in different chemical environments and two carbon atoms that are in the
same chemical environment. Draw the structure of C2H8N2.

3
2. This question is about Great Britain being better than any other country at cycling

One of the most successful British sports

at the London 2012 Olympics was cycling.
British cyclists won eight gold, two silver
and two bronze medals. In addition,
Bradley Wiggins became the first ever
Briton to win the Tour de France.

(a) Bronze medals contain copper. A 0.800 g sample of a bronze medal was dissolved in hot
concentrated nitric acid. After cooling and dilution, an excess of potassium iodide solution was added
and the solution was made up to 250.0 cm3. A 25.00 cm3 aliquot of this solution required 12.20 cm3 of
0.100 mol dm−3 sodium thiosulfate solution in the presence of starch indicator.

Calculate the percentage by mass of copper in the bronze medal.

2Cu2+(aq) + 4I−(aq) → 2CuI(s) + I2(aq)

I2(aq) + 2S2O32−(aq) → 2I−(aq) + S4O62−(aq)

(b) All medals that were won at London 2012 had a diameter of 85 mm and were 7 mm thick. The silver
medal was made up of 92.5% silver and 7.5% copper, by mass.

Calculate the mass of a silver medal. Assume that the density of the alloy varies proportionally to its
composition by mass.

Densities in g cm−3: Ag, 10.49; Cu, 8.96

(c) Gold medals are made of gold, silver and copper. A 5.000 g sample of a gold medal was warmed with
excess concentrated nitric acid. An undissolved residue was separated by filtration, washed, dried
and weighed. Its mass was 0.067 g. Then an excess of dilute hydrochloric acid was added to the
solution in nitric acid. The precipitate formed was separated by filtration, washed, dried and weighed.
Its mass was 6.144 g.

Calculate the percentage by mass of gold, silver and copper in the gold medal.

The GB cyclists have individually designed bikes, which have to cope with the demands placed on them
whilst being as light as possible. One way a light bike could be achieved is by altering the gas used to
inflate the bike tyres.

4
You may assume that for the remainder of this question that gases behave as ideal gases and that they
follow the ideal gas law:
pV = nRT

where p = pressure in Pa
V = volume in m3
n = number of moles
R (the gas constant) = 8.31 J K−1 mol−1
T = temperature in Kelvin

The tyres on a bike are approximately the

shape of a torus. The equation for the
volume of a torus, V, is given below.

π2rd2
V =
2

r = distance from centre of torus to

centre of tyre tube

d = diameter of tyre tube

(d) A typical bike may have a wheel diameter of 66 cm and a tyre diameter of 23 mm.

Calculate the volume of a tyre, in m3.

If you are unable to calculate the volume of a tyre, you may use the value of 0.001 m3 in the subsequent
parts of this question.

(e) (i) The air pressure used in the tyres is typically 120 psi, much higher than atmospheric pressure.

1 psi = 6895 Pa.

Calculate the number of moles of gas in a tyre, at 25 °C.

(ii) Assuming air is a mixture of 80 % nitrogen gas and 20 % oxygen gas, calculate the total mass of
air in both tyres on a bike.

(iii) In cycling the smallest of changes can make the difference between winning and losing. The
small reduction in mass upon inflating tyres with helium instead of air would be worth considering
if it was not for that fact that the very small helium atoms escape through the rubber of tyres much
more rapidly.

Calculate the reduction in mass of the bike if both tyres were inflated with helium instead of air.

(iv) SF6 is one of the densest substances that would still remain in the gas phase at this pressure.

What would be the increase in mass if the bike tyres were filled with SF6?

5
3. This question is about chemistry general knowledge based on coloured compounds

Chemists recognise many substances by their colour.

This question tests your knowledge about the colour of a

range of chemicals that you will have come across as
part of your studies of chemistry.

(a) In the answer booklet, a number of colours are listed. For each colour, if one of the substances below
is that colour, give its letter. If that colour cannot be made using a single substance, give the letters of
two substances that will produce this colour when mixed. A substance may be used more than once.

Choose from A = CaCl2(s) F = FeSO4.7H2O(s)

B = CuO(s) G = K2Cr2O7(s)
C = Cu2O(s) H = NaOH(aq)
D = CuSO4(s) I = VSO4.7H2O(s)
E = Al2O3(s) J = ZnCl2(s)

(b) A student was provided with 7 unknown aqueous solutions. Each solution contained only one
substance and all solutions were different.
The student mixed pairs of solutions in an attempt to identify each of the substances. The results from
these tests are shown below. A blank cell shows where no observable results were obtained.

Analyse the results and assign the following substances as solutions T-Z.

barium chloride dissolved chlorine gas iron(II) sulfate lead(II) nitrate

(i.e. chlorine water)

silver nitrate sodium carbonate sodium iodide

T U V W X Y Z

Bright yellow White precipitate White precipitate White precipitate White precipitate
T precipitate formed formed
–
formed formed formed

Bright yellow Yellow precipitate

U precipitate formed
–
formed
– – Brown solution

White precipitate
White precipitate White precipitate White precipitate
V formed
– formed (darkened
formed formed
–
in daylight)

White precipitate White precipitate

Yellow precipitate Off-white White precipitate
W –
formed
formed (darkened
precipitate formed formed
formed (darkened
in daylight) in daylight)

Dirty green
White precipitate White precipitate Off-white precipitate formed
X formed
–
formed precipitate formed (turned brown on
–
standing)
Dirty green
White precipitate White precipitate White precipitate precipitate formed Pale yellow
Y formed
–
formed formed (turned brown on solution
standing)

White precipitate
White precipitate Pale yellow
Z formed
Brown solution – formed (darkened –
solution
in daylight)

6
4. This question is about GPs giving out too many drugs

The drugs diazepam (Valium®) and alprazolam (Xanax®)

belong to a family of compounds called benzodiazepines
which were once hailed as the answer to many ailments. In
1988, The Committee on Safety of Medicines advised GPs to
limit their prescriptions of these drugs due to their overuse;
however, in England in 2010 more than 6.6 million
benzodiazepine prescriptions for anxiety were dispensed.
Heath Ledger, Michael Jackson and Whitney Houston are
among some of the many people that are believed to have
died from drug overdoses that involved benzodiazepines.

The synthesis of diazepam from 4-chloroaniline is shown below. The percentage yield for each step is also
shown. By-products are not always shown.

7
(a) (i) Calculate the overall percentage yield for the conversion of 4-chloroaniline to diazepam.

(ii) A patient was prescribed diazepam for three years at a dose of 5 mg, four times a day.

Calculate the mass of diazepam this was, and hence the mass of 4-chloroaniline needed to make
the drug for this patient.

(b) Draw the structures of intermediates A – H in the synthesis of diazepam.

In the liver it was found that diazepam underwent a demethylation reaction. The product of this
demethylation reaction was used as inspiration for the synthesis of the drug alprazolam.

(c) The synthesis of alprazolam is shown below. Draw the structures of intermediates I, J and K

(d) In the final stage of the synthesis, compound L is treated with a

chemical called ‘DEAD’ to convert it into alprazolam. DEAD
stands for diethyl azodicarboxylate.

How would you classify the reaction of L to alprazolam using one

of the terms below?

Tick the correct answer in your answer booklet.

Isomerisation Hydrolysis Condensation Oxidation Reduction

8
5. This question is about getting big muscles

Creatine has recently become one of the most widely used nutritional
supplements among athletes. Although there is much debate about
which of the advertised beneficial effects of creatine are actually true, the
use of creatine is generally believed to lead to a short-term gain in body
mass/muscle size. The structure of creatine is shown below.

In the body, creatine is converted into phosphocreatine which is used as

an energy reserve in the muscles that can be rapidly mobilised to
convert adenosine diphosphate (ADP) back into adenosine triphosphate
(ATP) – the body’s energy currency – in times of need.

(a) Creatine is often sold in capsules labelled as ‘Pure Creatine Monohydrate’.

Write the molecular formula of creatine monohydrate.

(b) Creatine is synthesised naturally in organisms from three amino acids: glycine, methionine and
arginine.

In your answer booklet, for each of the carbon atoms in creatine (labelled as 1-4), suggest which
carbon atom of the three amino acids it came from (labelled as A-M)

(c) Like amino acids, creatine exists in different ionised forms depending on the pH of the solution it is in.
This causes the overall charge on the molecule to vary. Draw the most common form of creatine at
each of the following pHs (the overall charge on the molecule at each pH is given).

(i) pH 1 (ii) pH 7 (iii) pH 12

(overall charge = + 1) (overall charge = neutral) (overall charge = − 1)

The chemical structure of creatine and these amino acids can be analysed by 1H NMR.

As these are polar molecules, the NMR spectra are run in D2O solvent. In D2O, protons attached to
nitrogen or oxygen atoms undergo rapid exchange with deuteriums from the solvent. This means that by
the time the NMR is run, all N-H bonds have been replaced by N-D bonds and all O-H bonds by O-D
bonds. As signals from deuterium atoms are not observed in 1H NMR spectra, no signals from N-H or O-H
groups in the molecule are seen in the spectrum.

The number of signals observed depends on the symmetry of the molecule. Each hydrogen atom in a
unique environment gives rise to a signal at a different chemical shift in the spectrum. Occasionally,
signals from two different environments can appear on top of one another when the difference in chemical
shifts between the environments is very small.

The area under each signal is proportional to the number of protons in that environment. This is shown by
an integral trace (the stepped line on the spectrum). The height of each step is proportional to the area
under that signal.
9
The appearance of the signals can be complicated by coupling. If the
hydrogen atom(s) are within three bonds of another hydrogen which is in a
different environment, instead of appearing as a single peak, its signal is n Intensities of
split into a number of peaks. If the hydrogen under consideration is within peaks
three bonds of n hydrogens in a different environment from itself, it will be 0 1
split into (n + 1) equally spaced peaks. The ratio of the area under the 1 1:1
peaks is given by the number in Pascal’s triangle (shown on the right). 2 1:2:1
Due to rapid exchange of any protons/deuteriums bonded to oxygen or 3 1:3:3:1
nitrogen atoms with the solvent, no coupling is seen to protons/deuteriums 4 1:4:6:4:1
bonded to oxygen or nitrogen atoms.

(d) Consider the amino acid methionine.

Complete the table in the answer booklet for carbons C, D and F in

methionine to suggest the appearance of the overall signal from the protons
bonded to that carbon atom.

(e) Usually all protons attached to the same carbon atom are in the same chemical environment;
however, this is not always the case. Two protons on the same carbon atom that are in different
chemical environments are called diastereotopic protons.

These are most often observed where the carbon under consideration is bonded to an asymmetric
carbon atom. An asymmetric carbon atom has four different chemical groups attached to it.

Consider glycine, methionine and arginine. In these three amino acids, write the letters of all such
carbons whose diastereotopic protons would be observed as different signals in their spectra.

In the body, creatine is in equilibrium with a cyclic molecule called creatinine, by the following equation.
The position of equilibrium varies with pH.

Creatinine is a metabolic waste product that is not used by the body. It is filtered out in the kidneys.

The 1H NMR spectrum in D2O of a creatine/creatinine solution is shown below. Three signals are
observed. Creatinine gives rise to signal A. Creatine gives rise to signal B. Both creatine and creatinine
give rise to signal C.

10
(f) Suggest a structure for creatinine.

(g) Assuming this sample has reached equilibrium, calculate a value for the equilibrium constant, K, at
this pH and temperature. Show clearly how you worked this out. You may ignore the concentration of
water in your calculation.

(h) A problem with creatine supplementation is that a lot of the creatine taken does not get absorbed by
the body. Recently, supplements containing derivatives of creatine have been marketed. These are
usually more lipophilic (dissolve more easily in fats) in an effort to improve uptake into the body.

The 1H NMR spectrum in D2O of one of these supplements is shown below. Some regions of the
spectrum have been expanded on the left hand side of the figure to help with your analysis.

This supplement exists in an ionised form at pH 1 but does not exist in an ionised form at pH 12.

Suggest a structure for this supplement.

11
 Acknowledgements & References

Q1

The Curiosity Mars rover image is courtesy of NASA.

Q2

Information on the composition of the medals was taken from www.london2012.com.

The Bradley Wiggins image is courtesy of Getty Images.

Q3

The image of the test tubes is courtesy of iStockphoto.

Q4

The Independent Thursday 29th December 2011 Doctors sued for creating 'Valium addicts' Nina Lakhani

The image of diazepam is courtesy of Paul Brown and Alamy.

Heterocycles 1981 16 1491-1494

Journal of Medicinal Chemistry 1977 20 1694-1697

Journal of Medicinal Chemistry 1979 22 1-7

Journal of Organic Chemistry 1980 45 1675-1681

Tetrahedron Letters 1971 12 1609-1612

Q5

John Gallacher is thanked for providing an image of his arm.

The University of Oxford is thanked for use of their NMR facilities.

The creatine supplements analysed were from Precision Engineered Ltd.

Biochemical Journal 1928 22 920-929

Journal of the Chemical Society, Perkin Transactions II 1985 1465-1467

The UK Chemistry Olympiad is supported by INEOS. 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 production network spans 73 manufacturing facilities in 19
countries throughout the world. The chemicals INEOS produce enhance
almost every aspect of modern life.

12
 45th INTERNATIONAL CHEMISTRY OLYMPIAD

UK Round 1 - 2013

MARK SCHEME

Question 1 2 3 4 5 Total

Mark 9 13 9 15 17 63

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 student’s answers differ slightly
from the mark scheme due to the use of rounded/non-rounded data from an earlier part of the question.

For answers with missing or incorrect units, penalise 1 mark for the first occurrence in each question. Do
not penalise for subsequent occurrences in the same question.

Question 1

(a) 3N 2 H 4 (l) → 4NH 3 (g) + N 2 (g) 1

[Ignore state symbols]

(b) ∆ r Ho = ((2 × 46.1) + 187.8 − (2 × 285.8) + ∆ f Ho (N 2 H 4 )) kJ mol−1 = −241.0 kJ mol−1

∆ f Ho (N 2 H 4 ) = 50.6 kJ mol−1

Decomposition enthalpy = −50.6 kJ mol−1 1

[Positive answers of correct magnitude do not score credit.]

(c) (i) N2H4 H2O2 N2 H2O

Ox. state of N –2 0
Ox. state of O –1 −2 1

[No partial credit given]

1
 (ii) CH 3 OH(l) + 3H 2 O 2 (l) → CO 2 (g) + 5H 2 O(l) 1

[Ignore state symbols]

(iii) Amount of hydrazine = 225000 cm3 × 1.021 g cm−3 / 32.052 g mol−1

= 7167 mol

Amount of methanol = 862000 cm3 × 0.7918 g cm−3 / 32.042 g mol−1

= 21301 mol 1

[Both amounts needed for one mark]

Heat energy evolved from hydrazine = 7167 mol × 622.2 kJ mol−1

= 4.459 x 106 kJ

Heat energy evolved from methanol = 21301 mol × 726.0 kJ mol−1

= 15.465 x 106 kJ

Total heat energy evolved from oxidation of rocket fuel = 19.9 x 106 kJ 1

[Correct answer scores both marks. Accept −19.9 x 106 kJ]

(d) (i) N 2 and H 2 O 1

[Half a mark each. Accept ‘nitrogen and water’.]

(ii) NO 2 1

[Accept ‘nitrogen dioxide’.]

(e) (CH 3 ) 2 N−NH 2 1

This is known in the trade as UDMH (unsymmetrical dimethylhydrazine)

Total 9

Question 2

(a) Amount of S 2 O 3 2− = 0.0122 dm3 × 0.100 mol dm−3 = 1.22 × 10−3 mol

Amount of Cu = 1.22 × 10−2 mol

Mass of Cu = 1.22 × 10−2 mol × 63.55 g mol−1 = 0.775 g

Percentage of Cu by mass = 100 % × 0. 775 g / 0.800 g = 96.9 % 1

(b) Volume of medal = πr2h = π × (4.25 cm)2 × 0.7 cm = 39.72 cm3 1

Density of medal = (0.925 × 10.49 g cm−3) + (0.075 × 8.96 g cm−3) = 10.38 g cm−3

Mass of medal = 39.72 cm3 × 10.38 g cm−3 = 412 g 1

[Correct answer scores both marks.]

2
(c) Mass of Au = 0.067 g

Amount of Ag = amount of AgCl = 6.144 g / (107.87 + 35.45) g mol−1 = 4.287 × 10−2 mol
Mass of Ag = 4.287 × 10−2 mol × 107.87 g mol−1 = 4.624 g
Mass of Cu = 5.000 g − 0.067 g − 4.624 g = 0.309 g

Percentage of Au by mass = 100 % × 0.067 g / 5.000 g = 1.34 % 1

Percentage of Ag by mass = 100 % × 4.624 g / 5.000 g = 92.5 % 1
Percentage of Cu by mass = 100 % × 0.309 g / 5.000 g = 6.18 % 1

[One mark awarded for each correct percentage. Allow error carried forward in the copper
percentage. Allow minor differences due to rounding.]

(d) d = tyre diameter = 0.023 m

r = (wheel diameter / 2) – (tyre diameter / 2) = 0.33 m – 0.0115 m 1
= 0.3185 m

[One mark for correct value of r]

volume = π2 × 0.3185 m × (0.023 m)2 / 2

1
= 8.314 × 10−4 m3

[Correct answer scores both marks.]

(e) (i) p = 8.27 × 105 Pa; V = 8.31 × 10−4 m3; T = 298 K

n = pV/RT 1

[One mark for correct method.]

n = (8.27 × 105 Pa × 8.31 × 10−4 m3) / (8.314 J K−1 mol−1 × 298 K) 1

n = 0.278 mol

[Correct answer scores both marks; n = 0.334 mol if value of 0.001 m3 used for volume.]

(ii) N 2 = 28.02 g mol−1; O 2 = 32.00 g mol−1

mass in one tyre = ((0.8 × 28.02 g mol−1) + (0.2 × 32.00 g mol−1)) × 0.278 mol
mass in one tyre = 8.011 g

mass of air in both tyres = 8.011 g × 2

= 16.02 g 1

[Mass = 19.25 g if value of 0.001 m3 used for volume. Allow any approximations that are
more accurate than this, for example if the student has decided to use 78% N 2 , 21% O 2 ,
1% Ar.]

(iii) He = 4.003 g mol−1

mass = 2 × 0.278 mol × 4.003 g mol−1

mass = 2.226 g

mass reduction = 16.02 g − 2.226 g

mass reduction = 13.79 g 1

[Error carried forward: accept answer from (e)(ii) minus 2.226 g or answer from (e)(ii)
minus 2.674 g if 0.001 m3 used for volume.]

3
 Although this mass reduction is small, it is significant enough to be considered.
Unfortunately being very small, helium escapes through the rubber of tyres much more
easily and so is rarely used.

(iv) SF 6 = 32.06 g mol−1 + (6 × 19.00 g mol−1) = 146.06 g mol−1

mass = 2 × 0.278 mol × 146.06 g mol−1

mass = 81.209 g

mass increase = 81.209 g − 16.02 g 1

mass increase = 65.19 g

[Error carried forward: accept 81.209 g minus answer from (e)(ii), or 97.568 g minus
answer from (e)(ii) if 0.001 m3 used for volume.]

Total 13

Question 3

(a)
Red C
Orange G
Yellow G H
Green F
Blue D H
Violet I

[Award half a mark for each colour. For yellow and blue both letters are needed to score 3
the half mark for that colour.]

(b)
T lead(II) nitrate
U sodium iodide
V barium chloride
W silver nitrate
X sodium carbonate
Y iron(II) sulfate
Z chlorine water/dissolved chlorine gas
6
All 7 correct = 6 marks 5 or 6 correct = 5 marks 4 correct = 4 marks
3 correct = 3 marks 2 correct = 2 marks 1 correct = 1 mark

[Ignore spelling errors as long as substance is recognisable. Oxidation states not needed.
Accept if correct chemical formulae have been written instead of words.]

Total 9

Question 4

(a) (i) 10.8 % 1

More modern syntheses have considerably improved upon this overall yield.

4
 (ii) Mass of diazepam per dose = 5 × 10−3 g

Total mass of diazepam = 5 × 10−3 g × 4 × 365 × 3

Total mass of diazepam = 21.9 g [Allow an extra day added for a leap year.]

Amount of diazepam = 21.9 g / 284.734 g mol−1

Amount of diazepam = 0.0769 mol

Amount of 4-chloroaniline = 0.0769 mol / 0.108

Amount of 4-chloroaniline = 0.712 mol 1
Molecular formula of 4-chloroaniline = C 6 H 6 NCl
M r of 4-chloroaniline = (6 × 12.01 g mol−1) + (6 × 1.008 g mol−1) + 35.45 g mol−1 +
14.01 g mol−1
M r of 4-chloroaniline = 127.568 g mol−1

Mass of 4-chloroaniline = 0.712 mol × 127.568 g mol−1

Mass of 4-chloroaniline = 90.8 g
1
[Correct answer scores both marks. Error carried forward: accept answers based on
incorrect answer to (a)(i)]

(b) Structure of A

[If bromine atom is in wrong position on benzene ring, no credit is given here, but full credit is
awarded in B, D, E and F provided rest of structure correct.]

Structure of B

Structure of C

5
 Structure of D

Structure of E

Structure of F

Structure of G

Structure of H

[Allow stereoisomer with other geometry around C=N bond.]

6
(c) Structure of I

Structure of J

[Accept either structure. Also allow stereoisomer with other geometry around the top C=N bond
in the right hand structure.]
The left structure is believed to be the predominant one.

Structure of K

[Accept either structure and also any stereoisomers with alternative geometries around C=N
bonds not in the ring.]
The left structure is believed to be the predominant one.

(d)
Isomerisation Hydrolysis Condensation Oxidation Reduction
✓ 1

DEAD is also sometimes known as DEADCAT.

Total 15

Question 5

(a) C 4 H 9 N 3 O 2 .H 2 O or C 4 H 11 N 3 O 3 1
[Accept answers where order of elements is different.]

7
(b)
Carbon Atom Carbon Atom
in Creatine in Amino Acid
1 H
2 C
3 A
4 B 3

All four correct = 3 marks Three correct = 2 marks Two correct = 1 mark

(c) (i)

[Any one of the three resonance structures shown above is worth 2 marks i.e. the extra
proton must be on the uppermost nitrogen as drawn in the diagram for 2 marks. Either of
the two structures shown below should be awarded 1 mark.]
The uppermost nitrogen is protonated as this maintains the delocalisation present in the
neutral guanidinium group in the conjugate base form.

(ii)

[The first structure is chemically correct, but any one of the three structures shown above
is worth 1 mark. – The mark for protonating the correct nitrogen is awarded in part (i).
Allow the other two resonance forms for the guanidinium group in the structure on the left
as in part (i)]

(iii)

(d)
Carbon Singlet 1:1 doublet 1:2:1 triplet 1:3:3:1 1:4:6:4:1 No signal
atom quartet quintet observed
C ✓ 1

D ✓ 1

1
F ✓

8
(e) E and K 1

[Award half a mark each. If other letters are written minus half a mark for each other letter
down to zero.]

(f) [Any one of the five alternatives below is to be awarded the mark.]
The percentage of each tautomer is solvent dependent, although the top two are by far the
most important. In protic solvents, hydrogen-bonding favours the top left structure.

(g) K = [Creatinine] / [Creatine]

K = Integral height of signal A / Integral height of signal B
K=4 1

[This has no units. Award values between 3.5 and 5.0 the mark. There must be evidence of
working/using the correct integral method to gain the mark.]
Creatinine is favoured at more acidic pHs and creatine at more alkaline pHs.

(h)

3
[The correct structure is to be awarded 3 marks. The hydrochloride salt of this molecule
(protonated on any one nitrogen) should also be awarded 3 marks.
Incorrect structures may score 2 marks if they obey any two of the three criteria below,
and 1 mark for obeying any one of the criteria.]

■ A total of 10 C−H protons in the molecule.

This shows the student has successfully used the integrals in the spectrum to calculate
the number of hydrogens.
■ The presence of a discrete ethyl group in the molecule.
This shows the student has understood the coupling patterns in the NMR.
■ The presence of an ester functional group in place of the carboxylic acid.
This shows the student has understood the ionisation states of the molecule at different
pHs.

Total 17

9
UK Chemistry Olympiad 2013

Round 1 - Examiners' Report

The members of the RSC Olympiad Working Group would like to thank teachers for administering Round
1, marking the papers and submitting the scores using the new online system which significantly
increased the efficiency of processing candidates' scores. The quality of marking on the sample of papers
seen by the working group was very high with some teachers annotating scripts to show why marks had
or had not been awarded. There was also evidence on some scripts of internal moderation before
scripts were submitted to the RSC, which was pleasing to see.

We were pleased to see 113 new schools participating in the competition for the 1st time and we look
forward to seeing them continue to participate in future years. There was a significant increase in
entries this year for round 1 with almost a 1000 more entries this year compared to 2012.

This was certainly a challenging paper, as indicated by the thresholds required for Gold, Silver and
Bronze certificates (see graph at end of document for full details of mark breakdown). Questions 4 and 5
proved to be the more demanding questions for students. Many candidates found managing their time
very hard, causing them to rush the final two questions, possibly missing accessible marks.

Question 1

This question was accessible to all students, including those in the lower sixth form (or equivalent). This
question about amount of substance and energetics was generally well answered, with most students
scoring some marks. Oxidation numbers were well understood. The main errors were the incorrect use
of positive and negative signs. Part c iii highlighted the need for many students to carefully check units
during and after calculations.

Question 2

This physical chemistry question examined amount of substance, gases and volumetric analysis.

Many candidates successfully negotiated the quantity algebra but slipped up with trivial points like
molar masses for oxygen and nitrogen gases and remembering to double the volume of gas in a bike
tyre to obtain the gas volume for the whole bike. During moderation of the best scripts, many students
were awarded Error Carried Forward marks that had not been awarded by their teachers.
Question 3

This question was written to assess students' knowledge of common coloured compounds and ions. In
general, part b was answered more confidently than part a.

Only the highest achieving students scored full marks on part a, with many students not realising that
CuSO4 is white unless it is hydrated. Many students were not familiar with VSO4 (or V2+ more generally)
but were sometimes able to assign this to the colour violet by a process of elimination. Some students
suggested two or more substances because they felt a redox reaction might be necessary to obtain the
correct colour but redox reactions were not necessary for any colour.

Part b was based on a practical task that is commonly seen in the International Olympiad Final and
proved to be challenging for the majority of students, despite the fact that they would have come across
the majority of these reactions as part of their course. Students who applied a logical approach, starting
with the reactions that produced a 'tell-tale' observation (i.e. other than a white precipitate) fared
better than most.

Question 4

The first mark of the question proved tricky with many candidates not using the idea of moles in
conjunction with yield to determine the mass of 4-chloroaniline. The most successful approach followed
the normal skills required in the Olympiad with many candidates deducing the structures of A-F. Many
candidates scored marks with error carried forward in this section which showed good deductive
reasoning and logic. Students who persevered with this question were often able to access marks
towards the end of the question, despite finding the middle parts of the question hard. A large
proportion of candidates easily determined the reaction classification in the final part of the question.

Question 5

Miscounting hydrogen atoms and ignoring the water in the monohydrate were common errors when
working out the molecular formula in part a. Many students could correctly identify which amino acid
made up which part of the creatine molecule. Not many students realised that the integration data on
the NMR trace could be used to calculate a value for Kc. Only the very best candidates were able to
propose a sensible structure for the final part of the question.

Supported by an unrestricted educational grant from

 UK Chemistry Olympiad 2013 Round 1 Marks

200
NO AWARD (0-11) BRONZE (12-19)
1481 Candidates 1471 Candidates
32.4% 32.2%

150
Number of Candidates

SILVER (20-30)
1297 Candidates
28.4%

100

50
GOLD (31+)
325 Candidates
7.1%

0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60 62
Mark
 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 1 2 3 4 5 Total
Marks
9 9 13 18 16 65
Available

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
 1 18
H He
1 2
1.008 2 13 14 15 16 17 4.003

Li Be symbol B C N O F Ne
3 4 atomic number 5 6 7 8 9 10
6.94 9.01 mean atomic mass 10.81 12.01 14.01 16.00 19.00 20.18

Na Mg Al Si P S Cl Ar
11 12 13 14 15 16 17 18
22.99 24.31 3 4 5 6 7 8 9 10 11 12 26.98 28.09 30.97 32.06 35.45 39.95

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
39.102 40.08 44.96 47.90 50.94 52.00 54.94 55.85 58.93 58.71 63.55 65.37 69.72 72.59 74.92 78.96 79.904 83.80

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
85.47 87.62 88.91 91.22 92.91 95.94 101.07 102.91 106.4 107.87 112.40 114.82 118.69 121.75 127.60 126.90 131.30

Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
132.91 137.34 138.91 178.49 180.95 183.85 186.2 190.2 192.2 195.09 196.97 200.59 204.37 207.2 208.98

Fr Ra Ac+
87 88 89

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
*Lanthanides 58 59 60 61 62 63 64 65 66 67 68 69 70 71
140.12 140.91 144.24 150.4 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
+Actinides
90 91 92 93 94 95 96 97 98 99 100 101 102 103
232.01 238.03

2
NA = 6.02 × 1023 mol–1 1 nm = 1 × 10−9 m 0 °C = 273 K
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:

where h is Planck’s constant = 6.626 × 10–34 J s

c is the speed of light = 2.998 × 108 m s–1.

(c) Calculate the energy for the 3p to 3s transition in:

(i) J (atom–1)

(ii) kJ mol–1.

4
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

n 6 5 4 3

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) 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).

(f) (i) Use the graph to determine I.E.(3p) in J (atom–1).

(ii) What is the ionization energy of the ground state of sodium in kJ mol–1?

5
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 mol−1. Assuming that tazarotene cream has a
density of 0.90 g cm−3, calculate the concentration of tazarotene in the cream in mol dm−3.

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 mol−1 and two fewer signals in its 13C NMR
spectrum than tazarotene.

(g) Suggest a structure for the active form of the drug.

7
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 + ½O2 → 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 beetle’s 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 g−1 K−1 and that the density of the mixture is the same as that of
pure water, 1.00 g cm−3.

(ii) Assuming equal volumes of the two solutions are mixed, what is the minimum
concentration of the hydrogen peroxide solution in the beetle’s hydrogen peroxide
chamber?
The standard enthalpy change for the overall reaction (your answer to part (b)) per
mole of A is −203 kJ mol−1.

8
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.

9
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) (i) Determine the empirical formula of the methane hydrate in structure II. The molar
mass of CaCO3 is 100.09 g mol−1.

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

(c) 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 K−1 mol−1. [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 mol−1.

(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 cm−3. 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 cm−3) 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 mol−1.

(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 mol−1:
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 Wisconsin–Green 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
production network spans 73 manufacturing facilities in 19 countries throughout the world.
The chemicals INEOS produce enhance almost every aspect of modern life.

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
student’s answers differ slightly from the mark scheme due to the use of rounded/non-
rounded 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 1 2 3 4 5 Total
Marks
9 9 13 18 16 65
Available
1. This question is about controlling phosphate levels

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

1
State symbols not required

(ii) La3+ + PO43− → LaPO4

1
State symbols not required

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

1
State symbols not required

(c) (i)

Do not accept a molecular formula. Accept if O‒H bond not drawn out,
but all other bonds must be drawn out.

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

1
State symbols not required

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

1
State symbols not required

(d) 2LaCl3 + 6NH4HCO3 → La2(CO3)3 + 6NH4Cl + 3CO2 + 3H2O

1
State symbols not required

(e) (i) Amount of La3+ = 1000 mg / 138.91 g mol−1 = 7.20 × 10−3 mol
Amount of La2(CO3)3·2H2O = 3.60 × 10−3 mol
Molar mass of La2(CO3)3·2H2O = (2 × 138.91 + 3 × 12.01 + 11 × 16.00
+ 4 × 1.008) g mol−1 1
−1
= 493.88 g mol
Mass of La2(CO3)3·2H2O = 493.88 g mol−1 × 3.60 × 10−3 mol
= 1780 mg (or 1.78 g)

(ii) Amount of La3+ = 7.20 × 10−3 mol = Amount of PO43−

Molar Mass of PO43− = (30.97 + 4 × 16.00) g mol−1 = 94.97 g mol−1
Mass of PO43− removed = 7.20 × 10−3 mol × 94.97 g mol−1
1
= 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 9
2. This question is about a sodium street lamp

(a) 1s2, 2s2, 2p6, 3s1 1

(b) 3s 1

(c) (i) Energy = 6.626 × 10−34 J s × 2.998 × 108 m s−1 / 589 × 10−9 m
1
= 3.37 × 10−19 J (atom−1)

(ii) Energy per mole = 3.37 × 10−19 J × 6.02 × 1023 mol−1

= 2.03 × 105 J mol−1
1
= 203 kJ mol−1
Allow ECF from (c)(i)

(d) one Zero infinity the constant k 1

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

Note this answer is negative as energy is given out. Award one mark for 2
the expression: Energy change = I.E. (3p) − I.E. (nd)

(f) (i) Intercept = 0.00245 nm−1 (Allow values from 0.00243-0.0247 nm−1)
I.E. (3p) = 6.626 × 10−34 J s × 2.998 × 108 m s−1 × 2.45 × 106 m−1 1
= 4.87 × 10−19 J (atom−1)

(ii) Ionisation energy of sodium = I.E. (3p) + ΔE (3s→3p)

I.E. (3p) = 4.87 × 10−19 J (atom−1) × 6.02 × 1023 mol−1
= 293 kJ mol−1
Ionisation energy of sodium = 293 kJ mol−1 + 203 kJ mol−1 1
= 496 kJ mol−1
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 mol−1

Question Total 9
3. This question is about spot cream

(a) Effective density of tazarotene = 0.90 g cm−3 × 0.0005 = 0.00045 g cm−3

= 0.45 g dm−3
1
Concentration of tazarotene = 0.45 g dm−3 / 351.46 g mol−1
= 0.00128 M (or 1.28 mM)

(b)

(c)

1
 1

The alkyne C‒H bond does not have to be explicitly drawn in (as in
normal skeletal structure drawing).

(d) Oxidation Reduction Addition Elimination Substitution 1

(e)

(f) 20 signals 1
(g)

Question Total 13
4. This question is about bombardier beetles

(a) (i) 2H2O2 → 2H2O + O2

1
State symbols not required

(ii) Oxidation Reduction Disproportionation Hydrolysis Dehydration 1

(b) Combining 2H2O2 → 2H2O + O2 and A + ½O2 → B + H2O gives

1
H2O2 + A → B + 2H2O

(c) (i) Amount of energy = specific heat capacity ×temp. change ×mass of water
= 4.18 J g−1 K−1 × 80 K × 1000 g 1
= 334 kJ

(ii) Conc. of H2O2 in mixed solution = energy needed per litre / enthalpy
change per mole of H2O2
= 334 kJ dm−3/ 203 kJ mol−1
= 1.65 mol dm−3
2
Therefore with equal volumes mixed, conc. of H2O2 initially must be
double this value = 3.30 mol dm−3
Award one mark for the value of 1.65 mol dm−3, and one mark for the
realisation of the need to double the concentration. Allow ECF from (c)(i).

(d) (i) 6 1

(ii) 3 1

(e) Peak I O‒H 1

Peak II C‒H 1

(f) (i) ‒OH (or hydroxyl) 1

(ii) ‒CH3 (or methyl) 1

(g) H1 V
H2 VII
2
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

(a) CH4 + 2O2 → CO2 + 2H2O

1
State symbols not required

(b) (i) Amount of CH4 = amount of CO2 = amount of CaCO3

Amount of CaCO3 = 84.73 g / 100.09 g mol−1 = 0.847 mol
Amount of H2O = 116.92 g / 18.016 g mol−1 = 6.49 mol
(CH4)x(H2O)y + 2xO2 → xCO2 + (2x+y)H2O
So x = 0.847 mol, and 2x+y = 6.49 mol 3
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 mol−1;

therefore 2835.18 g mol−1 / 354.40 g mol−1 = 8 1
Molecular formula is (CH4)24(H2O)136

(c) Amount of CH4 = 6.67 × 1014 g / 16.04 g mol−1 = 4.16 × 1013 mol
V = nRT/p = 4.16 × 1013 mol × 8.31 J K−1 mol−1 × 254 K / 1.0 × 105 Pa 1
= 8.78 × 1011 m3

(d) (i) Mass % of methane in methane hydrate =

(8 × 16.04) g mol−1/ 957.07 g mol−1 1
= 13.4%

(ii) Mass of Baikal methane hydrate = 6.67 × 1014 g / 0.134 = 4.98 × 1015 g
1
Allow ECF from (d)(i)

(iii) Volume of methane hydrate = 4.98 × 1015 g / 0.95 g cm−3

= 5.24 × 1015 cm3 (or 5.24 × 109 m3) 1
Allow ECF from (d)(ii)

(e) (i) Unit cell mass = 957.07 g mol−1 / 6.02×1023 mol−1

1
= 1.59 × 10−21 g

(ii) Volume of unit cell = 1.59 × 10−21 g / 0.95 g cm−3 = 1.67 × 10−21 cm3
Length of unit cell edge = (1.67 × 10−21 cm3)⅓ = 1.19 × 10−7 cm 1
One mark for correct volume of unit cell. Allow ECF from (e)(i)
 (iii) Volume of methane in unit cell = 8 × 4/3 × π × (0.21 × 10−9 m)3
= 3.10 × 10−28 m3
1
Volume of water in unit cell = 46 × 4/3 × π × (0.14 × 10−9 m)3
= 5.29 × 10−28 m3

(iv) Percentage of space occupied =

(3.10 × 10−28 + 5.29 × 10−28) m3 / 1.67 × 10−27 m3 1
= 50%

(f) ΔfHo (CH4)8(H2O)46 = 8ΔfHo(CO2) + 62ΔfHo(H2O) − ΔcHo (CH4)8(H2O)46

= (8(−393.5) + 62(−285.8) − (−6690.4)) kJ mol−1
= −14177.2 kJ mol−1
Forming methane hydrate from methane and water has the enthalpy
change
8CH4 + 46H2O → (CH4)8(H2O)46 3
o −1 −1
ΔrH = (−14177.2 − 8(−74.8) − 46(−285.8)) kJ mol = −432 kJ mol
Final answer scores full marks. One mark for a correct value for
ΔfHo (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 ΔfHo (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
 UK Chemistry Olympiad 2014
Examiners’ Report, Round 1, 2014

The members of the RSC Olympiad Working Group would like to thank teachers for their
hard work supporting students and the Royal Society of Chemistry to run Round 1 of the
competition. The members of the working group were pleased to receive letters and emails
from teachers about the administration, content and demand of the Round 1 paper and have
taken on board this welcome feedback.
We were delighted to see another significant increase in participation in 2014. This year,
5682 students’ marks were entered into the online score submission system, which
represents a 24% increase from entries in the 2013 competition. We were especially pleased
to see that 135 schools had participated for the first time. The RSC will, as usual, be
awarding the INEOS prize to the best performing new state school – the student who
achieves the highest mark from an eligible school (not entered more than once in the past
five years) has won £1000 for their school chemistry department to spend on enhanced
equipment or materials to help promote chemistry.
Whilst the paper has always been written with upper sixth form students in mind, we
encourage ambitious lower sixth form students to enter if they have been able to cover the
required topics in their independent study. This year we received entries from some students
in Year 11 and one student in Year 7! His score was very respectable indeed.

Question 1
The examiners felt that this was a fairly straightforward opening question, although some
students struggled to balance the more complex chemical equations. There were some
unfortunate and trivial errors when students struggled to apply their understanding of
valency, giving rise to some incorrect formulae, such as NaCO3. Parts e(i) and (Iii) caused
some difficulty for weaker students.
Question 2
This question was well answered on the whole with many candidates scoring well on the first
part of the problem. The final ionisation energy calculation proved the most challenging
aspect. It was surprising to see that some students used subscripts in their electron
configuration notation, and the sub-level from which sodium loses an electron was often
given as 3s1 instead of 3s. Students sometimes quoted negative energy changes and in part
e gave the expression the wrong way around, losing one mark.
Question 3
Many students had difficulty calculating the correct concentration but it was noticed that
students who made an attempt at drawing structures of intermediates often scored some
marks. The examiners were pleased to see that students who struggled to get the correct
answer for the first structure were able to succeed with some of the later structures, because
organic synthesis questions in Round 1 are always written in such a way as to give students
a variety of access points into the question. Some students ignored the symmetry of the two
methyl groups when predicting the number of NMR peaks and it was noticed that classifying
the reaction type was not so well answered.
Question 4
This question was generally well answered at the start. In part c(ii) many students ignored the
dilution factor in their calculation. The majority of students were able to correctly assign the IR
peaks whereas for some using the nmr data was more challenging, there were a large
number of students able to identify compounds A and C. An important point to note is that
whereas the hydroquinones in the last part of the question (A and C) can be represented
with either alternating single and double bonds or a circle of delocalised electrons in the ring,
the quinones (B and D) are not aromatic structures and so double bonds must be drawn in
the correct places. A number of students who got this far fell into this error, as did some
teachers in their application of the mark scheme.

Question 5
Many students struggled to answer the combustion analysis part which was presented in a
slightly unfamiliar way and it was noted that some candidates were unable to finish the
question due to time pressures in the time allowed. However, it did allow for the more
mathematically minded lower sixth candidates to score high question marks with many being
able to answer beyond the initial combustion analysis section tackling the ideas on density
and % packing with ease. Most students who had managed their time effectively and were
able to tackle the Hess Law question were able to pick up some marks and this was
generally well attempted.

Supported by an unrestricted educational grant from

 UK Chemistry Olympiad Round 1 2014
300

NO AWARD (0-13)
2191 Candidates
38.6%
250
BRONZE (14-21)
1694 Candidates
29.8%

200
Number of Students

150
SILVER (22-34)
1377 Candidates
24.2%

100

GOLD (35+)
50 420 Candidates
7.4%

0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60 62 64
Score
 47th INTERNATIONAL
CHEMISTRY OLYMPIAD
2015
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 1 2 3 4 5 Total
Marks
9 17 20 14 15 75
Available

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
 1 18
H He
1 2
1.008 2 13 14 15 16 17 4.003

Li Be symbol B C N O F Ne
3 4 atomic number 5 6 7 8 9 10
6.94 9.01 mean atomic mass 10.81 12.01 14.01 16.00 19.00 20.18

Na Mg Al Si P S Cl Ar
11 12 13 14 15 16 17 18
22.99 24.31 3 4 5 6 7 8 9 10 11 12 26.98 28.09 30.97 32.06 35.45 39.95

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
39.102 40.08 44.96 47.90 50.94 52.00 54.94 55.85 58.93 58.71 63.55 65.37 69.72 72.59 74.92 78.96 79.904 83.80

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
85.47 87.62 88.91 91.22 92.91 95.94 101.07 102.91 106.4 107.87 112.40 114.82 118.69 121.75 127.60 126.90 131.30

Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
132.91 137.34 138.91 178.49 180.95 183.85 186.2 190.2 192.2 195.09 196.97 200.59 204.37 207.2 208.98

Fr Ra Ac+
87 88 89

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
*Lanthanides 58 59 60 61 62 63 64 65 66 67 68 69 70 71
140.12 140.91 144.24 150.4 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
+Actinides
90 91 92 93 94 95 96 97 98 99 100 101 102 103
232.01 238.03

NA = 6.022 × 1023 mol–1

1. This question is about the chemistry of touchscreens

In recent years there has been a surge in

demand for indium for touchscreen and
display equipment. The element is quite
rare so its price has rocketed. There are
worries that the global supply of the
element could run out. Its major use is the
electrically conducting transparent glass
ITO, indium tin oxide.

(a) Indium(III) oxide can be obtained by heating indium(III) hydroxide. Write an equation for
this reaction.

ITO glass is 90% indium(III) oxide, 10% tin(IV) oxide, by mass. The iPad shown above
contains about 27 mg of ITO glass in its touchscreen.

(b) (i) Calculate the mass of indium present in the ITO glass of the iPad touchscreen.

(ii) The indium content of ITO glass in touchscreens is taken to be about 700 mg per
square metre. Given that the density of ITO glass is about 7.15 g/cm3, calculate
the thickness of the ITO glass in the touchscreen.

Indium(III) oxide can take the cubic bixbyite crystal structure. The position of the indium ions
approximates to the face-centred cubic (FCC) unit cell shown in the illustration above. A unit
cell is the simplest repeat unit that contains all the symmetry of the crystal. In the FCC
structure the ions are centred on the corners of the cube and the centres of the faces.

Calculate how many indium ions are actually inside the cube. You will need to
(c)
consider the fractional occupancy of each ion in the cube.

The oxide ions occupy positions that are wholly inside the cube. Deduce how
(d)
many oxide ions are present in the cubic cell shown.
When indium(III) oxide is heated to 700 °C in air, its mass decreases by 11.5%.
(e)
Work out the formula of the compound produced.
When indium(III) oxide is heated with ammonia at 630 °C, the products are water
(f)
and a semiconductor. Suggest the formula of the semiconductor.

3
2. This question is about detecting molecules in space

In September 2014, the BBC announced that radio-

astronomers had discovered the ‘most complex
molecule’ to date in space. Found in ‘Sagittarius-
B2(N)’ – the largest star-forming region in our
Galaxy – this is the first molecule detected with a
branched carbon chain. The systematic name for
the molecule is 2-methylpropanenitrile. It was found
to be approximately 0.4 times as abundant as its
straight-chained isomer.
The molecule was detected from the radio signals
given out as it dropped from an excited energy level
to a lower one.

A nitrile is a molecule in which one of the carbons has a triple bond to nitrogen.

(a) (i) Draw the structure of 2-methylpropanenitrile.

(ii) Draw the structure and give the systematic name of another nitrile isomeric with
2-methylpropanenitrile.

Astronomers are now looking for the next series of nitriles with the formula C5H9N.

(b) Draw all the isomeric nitriles with the formula C5H9N.

Most of the molecules detected by radio-astronomers in less active regions of space tend to
have linear structures. The largest so far detected has the unlikely-looking formula HC11N.

(c) Draw the structure of the linear molecule with the formula HC11N.

The signals detected in the radio wave region of the electromagnetic spectrum are due to
transitions between rotational energy levels, each of which has a particular energy. Molecules
have many rotational energy levels available to them, each level with a different energy being
specified by the so-called rotational quantum number, J, which takes integer values from 0
upwards.
The energy (in joules) of the Jth rotational energy level, EJ, is given by the formula:
EJ = h × B × J (J+1)
where B = the rotational constant of the molecule (in Hz)
h = Planck’s constant = 6.626 × 10–34 J s.
and light of frequency f (Hz) has energy h × f (joules)
Two signals have been detected due to HC11N. One is due to the transition from rotational
energy level (J = 39) to (J = 38), the other due to the transition from level (J = 38) to (J = 37).

(d) Given the signal from (J = 39) to (J = 38) was observed at 13186.853 MHz, calculate:

(i) the rotational constant, B, for HC11N (in MHz).

(ii) the frequency (in MHz) for the transition from level (J = 38) to (J = 37).

4
One of the most abundant heteronuclear diatomic molecules detected in space is carbon
monoxide formed from 12C and 16O.

(e) Given the masses of 12C and 16O are 12.00 g mol–1 and 16.00 g mol–1 respectively,
calculate the mass (in kg) of a single atom of each of these elements.

When taking both masses of atoms into account in a diatomic molecule, we use the so-called
reduced mass, 𝜇𝜇 . For a diatomic molecule with masses 𝑚𝑚1 and 𝑚𝑚2 ,
𝑚𝑚1 × 𝑚𝑚2
𝜇𝜇 =
𝑚𝑚1 + 𝑚𝑚2

(f) Calculate the reduced mass of a molecule of 12C16O.

For a diatomic molecule, the rotational constant (in Hz) is given by the expression:
ℎ
𝐵𝐵 =
8𝜋𝜋 2 𝜇𝜇𝑟𝑟 2
where r is the bond length.

(g) (i) Given the signal from (J = 1) to (J = 0) for 12C16O was observed at
115271.204 MHz, calculate the bond length.

(ii) A signal thought to be due to 12C16O was observed at 806651.719 MHz. Given that
rotational transitions only take place between adjacent energy levels, determine the
transition in 12C16O consistent with this observation.

5
3. This question is about the performance-enhancing drug Ritalin®
The drug Ritalin® has long been used as a
treatment for attention-deficit hyperactivity
disorder (ADHD). More recently it has been
in the news as a possible performance-
enhancing drug taken by students studying
for exams. The structure of Ritalin is shown
below, where R represents a hydrocarbon
group.

Ritalin is synthesised according to the scheme below. Some of the characteristic IR

stretching frequencies of the intermediates are shown.

(a) The synthesis begins with the reaction of benzyl chloride and sodium cyanide to
form Compound A. Draw the structure of Compound A.
(b) Compound A is then deprotonated to form Anion B−. Draw the structure of
Anion B−.
(c) Draw the structures of Compounds C, D, E and F. For Compound F you do not need
to worry about the specific identity of R.

6
Ritalin is present in the tablets as the hydrochloride salt.
(d) On the structure of Ritalin in the answer booklet, circle the atom that is protonated in
the hydrochloride salt (the HCl salt).
(e) (i) The tablets contain 10.00 mg of the hydrochloride salt which corresponds to
8.647 mg of Ritalin. Using this information calculate the molar mass of Ritalin
(include your working).
(ii) Hence suggest an identity for the hydrocarbon group R.
(f) For each of the following IR stretching frequencies from this scheme, draw the
functional group responsible and indicate with an arrow which of the bonds are
vibrating.
(i) 1655 cm−1 (ii) 1715 cm−1 (iii) 1740 cm−1 (iv) 2260 cm−1
(v) 3000 cm−1 (very broad) (vi) 3180 and 3390 cm−1 (sharp)

Stereoisomers of a molecule are isomers that have the same connectivity between the
atoms but a different three-dimensional arrangement in space. The effectiveness of a
drug depends on its three-dimensional shape.

This synthesis leads to the production of a mixture of four stereoisomers of Ritalin, shown
below. Some of these isomers are more effective than others.

(g) By ticking the appropriate box or boxes in the answer booklet, indicate which of
these isomers are enantiomers (non-superimposable mirror images).

Some of the less effective stereoisomers can be converted into the more effective ones
by deprotonation of Ritalin with the alkoxide base –OR to give Anion G– as shown below.
Upon reprotonation a different stereoisomer can be formed.

(h) Draw the structure of Anion G−.

(i) By ticking the appropriate box or boxes in the answer booklet, indicate which of
these isomers could be interconverted via the intermediary of Anion G−.

7
4. This question is about hangovers

After the consumption of too much

alcoholic beverage, people
sometimes experience a hangover
the following day. There are a variety
of causes of a hangover, one of these
is the accumulation of the toxic
metabolites of ethanol in the body.

In the body, ethanol is first converted into acetaldehyde by the enzyme alcohol
dehydrogenase and then into acetic acid by the enzyme acetaldehyde dehydrogenase.

In the first step, ethanol reacts with nicotinamide adenine dinucleotide (NAD+) to form
acetaldehyde, a compound called NADH and H+.

(a) What happens to the NAD+ in this reaction? Circle the correct answer.
it remains
it is oxidised it is reduced it is hydrolysed it is isomerised chemically
unchanged
In most parts of the UK, the legal drink drive limit is 80 mg of ethanol per 100 ml of blood.
(b) What concentration of ethanol does this correspond to (in mol dm−3)? (1 ml = 1 cm3)

After drinking it is not permitted to drive until the concentration of ethanol has fallen below
this level. The reaction to remove ethanol involves the initial combination of the ethanol
and the alcohol dehydrogenase to form an enzyme-substrate complex, followed by the
conversion of this complex into products. The rate of this reaction (the rate of production of
acetaldehyde) has a complicated rate law (as shown below).

k cat [AD][C2 H5 OH]

rate=
K M +[C2 H5 OH]

where [AD] is the concentration of the alcohol dehydrogenase enzyme

kcat = 1.33 s−1 and is the rate constant for the conversion of the enzyme
substrate complex to products

KM = 1.00 × 10−3 mol dm−3 and is a measure of the ease of dissociation of the
enzyme substrate complex back to reactants. It has the units of
concentration.

8
It is often the case that the rate law above simplifies to a much simpler form.
(c) (i) Write down the simplified form of this rate law when the concentration of
ethanol is very much larger than the value of KM.
(ii) Write down the simplified form of this rate law when the concentration of
ethanol is very much smaller than the value of KM.
(d) Hence, or otherwise, write down the order of this reaction with respect to ethanol at
around or above the UK drink drive limit.

The graph shows how the blood

ethanol concentration of someone
who has drunk a lot of alcohol
varies over time.

(e) For the majority of the time that this person is sobering up, what is the rate of loss of
ethanol?
(i) In (mg / 100 ml) h−1
(ii) In mol dm−3 s−1
(f) What concentration of alcohol dehydrogenase enzyme does this person have?
(g) The half-life of this reaction is the time taken for the concentration of ethanol to fall to
half of its initial value. From the graph, how does the half-life vary over the majority
of the period this person is sobering up?
it is impossible to
it increases it is constant it decreases determine from the graph
(h) As well as ethanol, alcohol dehydrogenase will also metabolise other alcohols. The
following metabolites are highly toxic. For each of these suggest which highly
poisonous alcohol they came from.
(i) (ii)

(i) For one of these poisonous alcohols, alcohol dehydrogenase has a kcat = 1.10 s−1
and a KM = 3.2 × 10−2 mol dm−3. What can be concluded about the metabolism of
this alcohol? Tick all that apply.
• The maximum rate of metabolism is faster for ethanol
• The maximum rate of metabolism is faster for the poisonous alcohol
• The maximum rate of metabolism is the same for both
• A higher concentration of ethanol is needed for the reaction
to proceed at half of its maximum rate
• A higher concentration of the poisonous alcohol is needed for the reaction
to proceed at half of its maximum rate
• The same concentration of ethanol and the poisonous alcohol are needed for the
reactions to proceed at half of their maximum rate
• The metabolism of the poisonous alcohol follows a rate law different from that of
ethanol

9
5. This question is about making “green” jet fuel

“Solar-Jet” is a project designed to make

aviation fuel from carbon dioxide and water
using sunlight as the source of energy. The
key to the project is the conversion of
carbon dioxide and steam into syngas (a
mixture of CO and H2) with the removal of
O2 as a byproduct. This is achieved using
the energy from a solar reactor which
focuses and concentrates sunlight.

[In the following question assume the molar

volume of a gas is 24.0 dm3 mol-1 at RTP,
room temperature and pressure.]

(a) Write a chemical equation to represent the process of carbon dioxide and steam
forming syngas and oxygen.

Syngas can then be used to produce hydrocarbon fuels in a procedure called the Fischer-
Tropsch process. In this process the carbon monoxide and hydrogen are catalytically
converted into alkanes and water.

(b) (i) Give the formula for an alkane with n carbon atoms and use this to write a
general equation for the Fischer-Tropsch process.

(ii) Calculate the ideal ratio of carbon monoxide to hydrogen in order to form
dodecane (n = 12), a major component of jet-fuel.

Solar-Jet uses the following procedure to manufacture syngas and oxygen.

Step 1. Cerium(IV) oxide is heated to very high temperatures in the solar reactor
which reduces it non-stoichiometrically as shown below:
𝛿𝛿
CeO2(s) → CeO2-δ(s) + 2 O2(g)
where δ is a number much smaller than 1 and represents the number of moles of O
atoms that are lost to form oxygen molecules.
Step 2. The temperature in the solar reactor is lowered, steam and carbon
dioxide are passed into the solar reactor and are reduced to syngas.
During this process the CeO2-δ is oxidised back to CeO2.

(c) (i) Give the overall chemical equation for the reduction of carbon dioxide to carbon
monoxide with CeO2-δ.

(ii) Give the overall chemical equation for the reduction of steam to hydrogen with
CeO2-δ.

10
A laboratory prototype was set up containing 127 g of CeO2. The prototype was then run
under the following experimental conditions:
Run time: 26 minutes
Step 1.
Power of the solar radiation: 3.60 kW.
Total volume of oxygen evolved: 367 cm3 at RTP.

Run time: 34 minutes

Step 2.
Power of the solar radiation: 0.80 kW.

(d) (i) Using the information from Step 1, calculate the value of δ.

(ii) Predict the volume (at RTP) of syngas produced in Step 2.

Under the conditions of the experiment, the actual volume of syngas produced was found
to be 747 cm3 at RTP with a H2 : CO ratio of 1.70:1.

(e) (i) Calculate the amount (in moles) of hydrogen produced in the experiment.

(ii) Calculate the amount (in moles) of carbon monoxide produced in the
experiment.
The crucial factor in deciding whether the process is economically viable, is how efficiently
the solar energy is converted into ‘usable energy’. This may be defined as:

usable energy of syngas produced

efficiency =
total solar energy used

(f) Calculate the total amount of solar energy used to produce the syngas.
[ Remember 1 W = 1 J s-1. ]

The ‘usable energy’ may be taken to be the energy released when the syngas undergoes
complete combustion to form carbon dioxide and water at room temperature and pressure.
The standard enthalpy changes of combustion for H2 and CO are given below.

CO(g) H2(g)
Standard enthalpy change of
combustion, ΔcH / kJ mol–1 –283 –286

(g) (i) Calculate the energy released (the standard enthalpy change) when the sample
of syngas produced from the experiment undergoes complete combustion.

(ii) Calculate the efficiency of the solar-jet reactor for this run.

Petrol typically has lighter alkanes than jet-fuel. The average number of carbon atoms in
the petrol is n = 8 whereas in jet-fuel it is n = 12.

(h) (i) Given the standard enthalpy changes of combustion (ΔcH ) for heptane (n = 7)
and octane (n = 8) are –4816 and –5470 kJ mol–1 respectively, calculate ΔcH
of dodecane (n = 12).

(ii) By constructing an appropriate Hess’ cycle, calculate the standard enthalpy

change for the production of dodecane from syngas.

11
Acknowledgements & References
References for questions

Q1
The image is from the Royal Society of Chemistry

Q2
The image is from © Shutterstock.

Detection of a branched alkyl molecule in the interstellar medium: iso-propyl cyanide

A. Belloche et al., Science, 345, 1584, 2014.

Detection of HC11N in the cold dust cloud TMC-1

M. B. Bell et al., The Astrophysical Journal, 483, L61-L64, 1997.

Microwave Spectra of Molecules of Astrophysical Interest VII

F. Lovas and P. Krupenie, Journal of Physical and Chemical Reference Data, 3, 245, 1974.

Q3
The image is from Wikipedia.

Q4
The image is from © Shutterstock.

Evidence-based survey of the elimination rates of ethanol from blood with

applications in forensic casework
A. W. Jones, Forensic Science International, 200, 1, 2010.

Kinetic Properties of Human Liver Alcohol Dehydrogenase: Oxidation of Alcohols by

Class I Isoenzymes
F. W Wagner et al., Biochemistry, 22, 1857, 1983.

Q5
The image is from © ETH Zurich.

Syngas production by simultaneous splitting of water and carbon dioxide via ceria
redox reactions in a high-temperature solar reactor
P. Furler et al., Energy & Environmental Science, 5, 6098, 2012.

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
production network spans 73 manufacturing facilities in 19 countries throughout the world.
The chemicals INEOS produce enhance almost every aspect of modern life.

12
 47th INTERNATIONAL
CHEMISTRY OLYMPIAD
2015
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
student’s answers differ slightly from the mark scheme due to the use of rounded/non-
rounded data from an earlier part of the question.

In general error carried forward can be applied, we have tried to indicate where this may
happen in the mark scheme.

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.

Organic structures are shown in their skeletal form, but also accept displayed formulae as
long as the representation is unambiguous.

Comments in blue have been added to some questions, these are not required for the
marks, but may be of interest in subsequent discussion on the questions.

Question 1 2 3 4 5 Total
Marks
9 17 20 14 15 75
Available
1. This question is about the chemistry of touch-screens

(a) 2In(OH)3 → In2O3 + 3H2O

1
State symbols not required

(b) (i) Fraction of indium in In2O3

= (2 × 114.82) / {(2 × 114.82) + (3 × 16.00)} = 0.8271 1
Mass of In in touchscreen = 0.8271 × 0.90 × 27 mg = 20.1 mg

(ii) Volume of ITO touchscreen = 0.027 g / 7.15 g cm −3 = 0.00378 cm3

Area of ITO touchscreen = 20.1 mg / 700 mg m−2
= 0.0287 m2 or 287 cm2 1
3 2
Thickness of ITO touchscreen = 0.00378 cm / 287 cm
= 0.0000132 cm or 0.132 μm or 1.32 × 10−7 m 1
Correct answer scores full marks. Award 1 mark if area calculated
correctly. Allow error carried forward from (b)(i).

(c) Indium ions in cube = (8 × ⅛) + (6 × ½) = 4 1

(d) Oxide ions in cube = 3/2 × 4 = 6

1
They occupy ¾ of the tetrahedral holes.

(e) Molar mass of In2O3 = 277.64 g mol−1

The mass decrease corresponds to 0.115 × 277.64 g mol−1
= 31.93 g mol−1 1
This corresponds to the loss of two oxygen atoms per formula unit, 1
giving In2O.
Correct answer scores 2 marks. Award 1 mark if mass decrease is
calculated correctly.

(f) InN 1
The equation is In2O3 + 2NH3 → 2InN + 3H2O but this is not needed to
be given full credit.

Question Total 9
2. This question is about detecting molecules in space

(a) (i)
1

(ii) ½

Butanenitrile ½
Allow 1-Butanenitrile. ½ mark for structure, ½ mark for name.

(b)

All five structures correct scores 3 marks. Four correct structures scores
2 marks (it is thought that most students will draw only one of the two
enantiomers). Three correct structures scores 1 mark. Two correct
structures scores ½ mark. One correct structure scores 0 marks.
Incorrect or duplicated structures should be penalised at minus 1 mark
each, down to a minimum of 0 marks.

(c)
1

(d) (i) Energy of transition from (J+1)th level to Jth level (an emission)
= h × B × (J + 1) (J + 2) − h × B × J (J + 1)
= h × B × [(J 2 + 3J + 2) – (J 2 + J)]
= h × B × 2(J + 1) = h × f
B = f / 2(J + 1)
B = 13186.853 MHz / 2(38 + 1)
B = 169.0622179 MHz 2

Correct answer scores full marks. General formula does not have to be
derived, but is worth a credit of 1 mark and very useful for remainder of
question.
 (ii) h × f = h × B × 2(J + 1) (from part (d)(i))
f = B × 2(J + 1)
f = 169.0622179 MHz × 2(37 + 1)
f = 12848.72856 MHz 2
Correct answer scores full marks. General formula does not have to be
derived, but is worth a credit of 1 mark. Allow error carried forward from
(d)(i). Answer should be answer to (d)(i) multiplied by 76.

(e) Mass of one atom of 12

C = 12.00 g mol−1 / 6.02 × 1023 mol−1
= 1.993 × 10−23 g = 1.993 × 10−26 kg
1
Mass of one atom of 16
O = 16.00 g mol−1 / 6.02 × 1023 mol−1
= 2.658 × 10−23 g = 2.658 × 10−26 kg

(f) μ = 1.993 × 10−26 kg × 2.658 × 10−26 kg / (1.993 × 10−26 + 2 .658 × 10−26) kg

= 1.139 × 10−26 kg
1
Allow error carried forward from part (e)

(g) (i) f = B × 2(J + 1)

f = B × 2(0 + 1)
f = 2B
B = 57,636 MHz

r2 = 1.2783 × 10−20 m2
r = 1.13 × 10−10 m
Correct answer scores 3 marks. Statement f = 2B scores 1 mark, 3
correct calculation of B is worth the second mark. The third mark is for
the correct answer. Penalise 1 mark for incorrect or missing units, or if
out by power(s) of 10 due to mix up with cm/m etc.
(ii) f = B × 2(J + 1)
806651.719 MHz = 57635 MHz × 2(J + 1)
2(J + 1) = 14
(J + 1) = 7
J=6
Transition is from Level J = 7 to J = 6 2
Correct answer scores 2 marks. If they have calculated the correct value
of J but have labelled the transition the wrong way round i.e. J = 6 to J =
7 then award only 1 mark. If J has not been calculated numerically
correctly then 0 marks. Error carried forward is not credited here.

Question Total 17
3. This question is about the performance-enhancing drug Ritalin®

(a)

(b)

Full marks if both are drawn

(c)

Each correct structure scores 1 mark. If the R group in Compound F is

drawn in as CH3 then this is also acceptable.
(d)

The nitrogen atom must be the only atom circled.

(e) (i) Additional molar mass on forming HCl salt = (1.008 + 35.45) g mol−1
= 36.458 g mol−1
Number of moles of Ritalin must remain constant, therefore the following
equation can be set up where M is the molar mass of Ritalin.

M = 233.00 g mol−1
Working must be shown to get credit. This is because it is possible to
work backwards from part (e)(ii) to get the mass. Award 1 mark if the
concept of equating moles is shown, award the second mark if the
equation above is written explicitly. The final mark is for the correct
answer.

(ii) Molar mass of molecule without R group = 218 g mol−1

Molar mass of R group = (233 – 218) g mol−1 = 15 g mol−1
Indentity of R group = CH3 or Methyl or Me
1
The observant student might notice that the chemical name for Ritalin
(Methylphenidate Hydrochloride) on the box in the picture suggests the
identity of R, hence it is possible to score credit here even if part (e)(i) is
incorrect.
(f)

Award ½ mark for each. In each case must be both the correct functional
group and have the arrow(s) pointing to the correct bond(s) to obtain the
½ mark. The words in brackets are not needed. In the case of the amide
in part (vi) arrows must be drawn to both bonds to obtain the ½ mark.

(g)

All correct 2 marks. For each mistake minus 1 mark, down to a minimum
of zero. If both boxes have been ticked for any pair then 0 marks for this
part.
(h)

Full marks if both are drawn.

(i)

All correct 2 marks. For each mistake minus 1 mark, down to a minimum
of 0. If both boxes have been ticked for any pair then 0 marks for this 2
part.
If the anion below was drawn in part (h) then error carried forward can
be applied here, in which case the correct answers are (1 and 2) and (3
and 4).

Question Total 20
4. This question is about hangovers

(a)
1
No marks if more than one answer circled.

(b) Molar mass of ethanol = (2 × 12.01 + 6 × 1.008 + 16.00) g mol−1

= 46.068 g mol−1
Concentration = 80 mg / 100 cm3
= 800 mg dm −3 = 0.8 g dm −3
= 0.8 g dm −3 / 46.068 g mol−1
= 0.017 mol dm−3 or 0.017 M or 17 mM 1

(c) (i) If [C2H5OH] >> KM, then KM + [C2H5OH] ≈ [C2H5OH]

(ii) If KM >> [C2H5OH], then KM + [C2H5OH] ≈ KM

(d) Zero or 0 or Zeroth Order

At the UK drink drive limit [C2H5OH] is much greater than KM, meaning the
case in (c)(i) applies. This is why it is possible to roughly calculate how 1
long it will take someone to ‘sober up’ as the rate of loss of alcohol is
approximately constant.

(e) (i) This is obtained from the gradient of the graph in the period up to 18 h
where there is a constant gradient.
1
Gradient = 17.0 (mg / 100 cm3) h−1
Allow values between 15.5-18.5 (mg / 100 cm3) h−1
 (ii) From part (b) 80 mg / 100 cm3 = 0.0174 mol dm−3
Therefore 1 mg / 100 cm3 = 2.175 × 10−4 mol dm−3
17 (mg / 100 cm3) h−1 = 3.698 × 10−3 mol dm−3 h−1
2
= 1.03 × 10−6 mol dm−3 s−1
Allow error carried forward from (e)(i). Answer should be 6.04× 10−8
multiplied by the answer for part (e)(i). Also allow error carried forward
from (b) if the same wrong conversion factor has been used.

(f) From part (c)(i)

[AD] = rate / kcat
[AD] = 1.03 × 10−6 mol dm−3 s−1 / 1.33 s−1
1
[AD] = 7.74 × 10−7 mol dm−3
Allow error carried forward from (e)(ii). Answer should be the answer for
part (e)(ii) divided by 1.33.

(g)
1

(h) (i)
1
Structure or name acceptable for 1 mark

(ii)

Structure or name acceptable for 1 mark

(i)

Award 1 mark for each correct tick. If the last box is ticked, minus 1 mark
from the overall total for this part. Ticks in other boxes are not negatively
marked unless two or three contradictory statements have been ticked, in
2
which case 0 marks are scored for this question. The lowest mark
possible for this part is 0.
The maximum rate of metabolism occurs at high alcohol concentration
when the enzyme is saturated with substrate. In this case
and the alcohol with the higher kcat value is metabolised more quickly.
When KM = [C2H5OH] then

and the reaction proceeds at half the maximum rate. Therefore alcohols
with a high KM value must be present at higher concentration for the
reaction to proceed at half of its maximum rate.
Interestingly, as ethanol is a ‘better’ substrate for alcohol dehydrogenase
than either methanol (KM = 3.0 × 10−2 mol dm−3) or ethylene glycol
(KM = 3.2 × 10−2 mol dm−3), it is often used to treat cases of poisoning with
these substances as it is metabolised preferentially by the enzyme.

Question Total 14
5. This question is about making “green” jet fuel

(a) CO2 + H2O → CO + H2 + O2

1
State symbols not required

(b) (i) General formula for an alkane CnH2n+2

n CO + (2n+1) H2 → CnH2n+2 + n H2O 1
State symbols not required

(ii) n = 12, 2n+1 = 25, therefore ratio of CO:H2 = 12:25 1

(c) (i) CeO2-δ + δ CO2 → CeO2 + δ CO

1
State symbols not required

(ii) CeO2-δ + δ H2O → CeO2 + δ H2

1
State symbols not required

(d) (i) Number of moles of O atoms evolved = 2 × 367 cm3/24,000 cm3 mol−1
= 0.0306 mol
Number of moles of CeO2 = 127 g / 172.12 g mol−1
2
= 0.738 mol of CeO2
δ = 0.0306/0.738 = 0.0414
Award 1 mark for if the factor of 2 has been forgotten, i.e. 0.0207
scores 1 mark.

(ii) 2 × 367 cm3 = 734 cm3 1

(e) (i) (1.7/2.7) × 747 cm3/ 24,000 cm3 = 0.0196 mol of H2 ½

(ii) (1/2.7) × 747 cm3/ 24,000 cm3 = 0.0115 mol of CO ½

(f) (26 × 60 × 3.6 × 103) J + (34 × 60 × 0.80 × 103) J = 7,248 kJ 1

(g) (i) 0.0196 mol × −286 kJ mol−1 + 0.0115 mol × −283 kJ mol−1
= −8.87 kJ
1
Accept if magnitude is correct but minus sign is missing. Allow error
carried forward from part (e).

(ii) 8.87 kJ / 7248 kJ = 0.12%

1
Allow error carried forward from (f) and/or (g)(i).
(h) (i) From n=7 to n=8, 654 kJ mol−1 more heat energy evolved.
1
ΔcH for n=12 = −5470 − (4 × 654 kJ mol−1) = −8086 kJ mol−1

(ii)

2
−1 −1 −1
= (12 × −283 kJ mol ) + (25 x −286 kJ mol ) + 8,086 kJ mol
= −2,460 kJ mol−1
1 mark for correct construction of cycle and attempt at calculation with
mathematical error. Allow error carried forward from (h)(i).

Question Total 15

Paper Total 75
UK Chemistry Olympiad 2015

Examiners’ Report, Round 1, 2015

The members of the RSC Olympiad Working Group would like to thank teachers for their
hard work supporting students and the Royal Society of Chemistry to run Round 1 of the
competition. The members of the working group were pleased to receive letters and emails
from teachers about the administration, content and demand of the Round 1 paper and have
taken on board this welcome feedback.

We were delighted to see another significant increase in participation in 2015. This year,
6630 students’ marks were entered into the online score submission system, which
represents a 17% increase from entries in the 2014 competition. There were a number of
excellent entries from Lower 6th Students and it would be hoped that these students would
be strongly encouraged to enter the C3L6 written paper later in the summer.

We were especially pleased to see that 137 schools had participated for the first time. The
Royal Society of Chemistry will, as usual, be awarding the INEOS prize to the best
performing new state school – the student who achieves the highest mark from an eligible
school (not entered more than once in the past five years) has won £1000 for their school
chemistry department to spend on enhanced equipment or materials to help promote
chemistry. In addition prizes are awarded to the top performing student in the competition,
who achieved a score of 74/75. The top scoring Lower 6th chemist is also awarded a prize. It
was noted that many of the top scoring students had previously participated in the C3L6
Lower 6th written paper and it was pleasing to see that they have continued to participate in
chemistry competitions.

Whilst the paper has always been written with upper sixth form students in mind, we
encourage ambitious lower sixth form students to enter if they have been able to cover the
required topics in their independent study.

Question 1

The examiners felt that this was a fairly straightforward opening question. There were some
trivial errors with students not able to apply their understanding of valence and also using the
incorrect chemical symbol for indium, which gave rise to incorrect formulae. Less
mathematical students seem to find part b) more challenging but parts c) and d) were
generally well answered and many students seemed to have a good understanding of unit
cells. Again most students made good attempts at parts e) and f) and it was pleasing to see
what many wrote out the full balanced equation for part f) although this was not needed for
the mark to be awarded.

Question 2

Part a) was generally very well answered. It was noted that part b) only the very best
students scored full marks. The best students spotted 4 isomers but very few appreciated
that there were different enantiomers. Part c) was well answered provided that students
considered the valency of carbon. Even some of the top students failed to appreciate that
the transition energy was required EJ=39 - EJ=38, and there were a number of careless
mistakes with units.
Question 3

It was noted that students who attempted to draw the structures of the intermediates often
scored some marks, and that some students approached the question by working
backwards from the final product which was pleasing as organic synthesis questions used in
Round 1 are designed to give students a variety of access points into the question. The
higher ability students were able to deduce the functional groups and assigned the IR
frequencies correctly from information given in the question.

Question 4

This question asked students to apply Michaelis-Menten kinetics (a 2nd year university topic)
in a reasonably accessible way to one of the more prevalent examples of zero order
behaviour. Part a) was generally well answered by most students who recognised that NAD+
had been reduced. There was a good attempt at part b) by many students although part c)
onwards was often only tackled by the most able students. It was noted that even among the
top performing candidates, many thought that the reaction was 1st order in part d) but went
on to use the zero order expression later in the question. Many of the correct answers for the
calculations fell into the acceptable range as indicated on the mark scheme. Many
candidates were able to score marks for part f) despite not getting part d) correct. There
were many interesting spellings noted for the compound in h) and it was noted that H2O2
was often suggested by students, despite it not containing any carbon atoms. Part i) was
generally answered well, although students often ticked contradictory statements.

Question 5

It was noted that some students were unable to finish the question paper due to the
pressures of the time allowed, however, those students who did attempt this question scored
well on parts a), b) and e). A number of students were not able to cope with the concept of δ
in parts c) and d) and δ/2 often appeared in incorrect answers. Those students who did
attempt f) - h) often achieved very good marks, sometimes consequentially.

Supported by an unrestricted educational grant from