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42nd International Chemistry Olympiad 2010, Japan

Chemistry: the key to our future

Contents
Constants, Formulae, and Periodic Table ...... 3
Theoretical Problems .... 4
Advanced Level Fields ...... 5
Problem 1: Equilibrium constant ..... 6
Problem 2: Speed of sound ... 7
Problem 3: Structures of nanomaterials ..... 8
Problem 4: Vibrational states of Cl2 ..... 9
Problem 5: Raman spectroscopy ..... 10
Problem 6: Internuclear distance of a hetero-nuclear diatomic molecule . 12
Problem 7: Atomic and molecular orbitals . 13
Problem 8: Electronic structure of polyene . 14
Problem 9: Electronic structure of condensed matter ...... 17
Problem 10: Carbon dioxide I ... 18
Problem 11: Carbon dioxide II ...... 19
Problem 12: Synthesis of titanium dioxide ......... 20
Problem 13: Born-Haber cycle ......... 21
Problem 14: Solid state structure ........ 22
Problem 15: Oxide-ion conductors ...... 23
Problem 16: Silver smelting and refining ........ 24
Problem 17: Cobalt(II) complexes ....... 26
Problem 18: Red-ox titration .........27
Problem 19: Iron-making and crystal structure ...... 28
Problem 20: Gibbs energy of oxidation reaction ....... 29
Problem 21: Quantitative composition analysis of volcanic gas ......... 31
Problem 22: Vibrational and rotational spectra of volcanic gas ...... 32
Problem 23: Introduction of macromolecular chemistry ....... 33
Problem 24: Reduction of carbonyl compounds ....... 37
Problem 25: Kiliani-Fischer synthesis ..... 38
Problem 26: Glycolysis ...... 39
Problem 27: Menthol synthesis ........ 40
Problem 28: Structure studies of urushiol ...... 41
Preparatory Problems

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future
Problem 29: Synthesis of Tamiflu ........ 43
Problem 30: Nuclear magnetic resonance (NMR) spectra of isomers of C4H8 44
Problem 31: Nuclear magnetic resonance (NMR) spectrum of [18]annulene

45

Practical Problems ........ 46


Advanced Level Fields ..............47
Problem 32: Colloid titration: titration of a cationic surfactant with polyanion ... 48
Problem 33: Analysis of zinc-aluminum alloy by EDTA titration . 50
Problem 34: Preparation of urea-hydrogen peroxide ...... 53
Problem 35: Separation of a dye mixture using thin-layer chromatography
(TLC) . 55
Problem 36: Hydrolysis of ethyl acetate over a solid acid catalyst ..... 59
Problem 37: Synthesis of a zinc ferrite ....... 61
Problem 38: Identification of polymers and small organic molecules by
qualitative analysis ...... 63
Problem 39: Synthesis of 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylic
acid diethyl ester (Hantzsch ester) ....... 65
Problem 40: Reduction of a ketone with sodium borohydride ..... 68

Preparatory Problems

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Constants and Formulae


Avogadro
constant:

NA = 6.022 x 1023 mol1 Ideal gas equation:

pV = nRT

Gas constant:

R = 8.314 J K1 mol1

Gibbs energy:

G = H TS

Faraday constant:

F = 96485 C mol1

o
r G o = RT ln K = nFE cell

Planck constant:

h = 6.626 x 1034 J s

Nernst equation:

E = Eo +

Speed of light:

c = 3.000 x 108 m s1

Logarithm:

ln x = 2.303 log x

Zero of the Celsius


scale:

273.15 K

Lambert-Beer law:

A = log

RT Pox
ln
zF Pred

I0
= cl
I

In equilibrium constant calculations, all concentrations are referenced to a standard


concentration of 1 mol L-1. Consider all gases ideal throughout the exam.

Periodic Table with Relative Atomic Masses


1

18

He

1.01

13

14

15

16

17

4.00

10

Li

Be

Ne

6.94

9.01

10.81

12.01

14.01

16.00

19.00

20.18

11

12

Na Mg
22.99

24.30

10

11

12

13

14

15

16

17

18

Al

Si

Cl

Ar

26.98

28.09

30.97

32.06

35.45

39.95

31

32

19

20

21

22

23

24

25

26

27

28

29

30

Ca

Sc

Ti

Cr

Mn

Fe

Co

Ni

Cu

Zn

39.10

40.08

44.96

47.87

50.94

52.00

54.94

55.85

58.93

58.69

63.55

65.38

69.72

37

38

39

40

41

42

43

44

45

46

47

48

49

Ru

Rh

Pd

Ag

Cd

In

35

36

Br

Kr

72.64

74.92

78.96

79.90

83.80

50

51

52

53

54

Sn

Sb

Te

Xe

Rb

Sr

Zr

87.62

88.91

91.22
72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

57-71

Hf

Ta

Re

Os

Ir

Pt

Au

Hg

Tl

Pb

Bi

Po

At

Rn

69

70

55

56

Ba

132.91 137.33
87

88

Fr

Ra

92.91

95.96

Tc

34

Se

85.47

Cs

Nb Mo

33

As

Ga Ge

101.07 102.91 106.42 107.87 112.41 114.82 118.71 121.76 127.60 126.90 131.29

178.49 180.95 183.84 186.21 190.23 192.22 195.08 196.97 200.59 204.38 207.2 208.98
89-103

104

105

106

107

108

109

110

111

Rf

Db

Sg

Bh

Hs

Mt

Ds

Rg

60

61

62

63

57

58

59

La

Ce

Pr

Nd Pm Sm Eu

138.91 140.12 140.91 144.24

89

90

91

92

93

Ac

Th

Pa

Np

Preparatory Problems

232.04 231.04 238.03

64

65

66

67

68

Gd

Tb

Dy

Ho

Er

Tm Yb

71

Lu

150.36 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.05 174.97
94

95

96

97

Pu Am Cm Bk
-

98

Cf
-

102

103

Es Fm Md No

99

Lr

100
-

101
-

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Theoretical Problems

Preparatory Problems

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Advanced Level Fields


Theoretical
Solid state structures: metals, metal salts
Thermodynamics: electrochemical cells, the relationship between equilibrium constants,
electromotive force and standard Gibbs energy, the variation of the equilibrium constant
with temperature
Quantum chemistry: quantized energy, related spectroscopy
Electronic structures: atomic and molecular orbitals, electrons and electrical conductivity
Nuclear Magnetic Resonance (NMR):

interpretation of 1H NMR spectra; chemical shifts,

multiplicities, coupling constants and integrals


Chemistry of saccharides: equilibrium between linear and cyclic forms, pyranoses and
furanoses, and Haworth projection and conformational formulae, reactions

Preparatory Problems

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 1:

Equilibrium constant

Answer the following questions using the standard potential, E, values given in the table.
Half reaction

a)

E/V (298 K)

Sn2+ + 2e Sn

0.14

Sn4+ + 2e Sn2+

+0.15

Hg22+ + 2e 2Hg

+0.79

Hg2Cl2 + 2e 2Hg + 2Cl

+0.27

Calculate the equilibrium constant, K, for the following reaction at 298 K


2+
Sn(s) + Sn4+(aq)
2Sn (aq)

K=
b)

Calculate the solubility, S, of Hg2Cl2 in water at 298 K (units for S, mol kg1). The
mercury cation in the aqueous phase is Hg22+.

S=
c)

mol kg1

Calculate the voltage, E, of a fuel cell by using the following reaction involving two
electrons.
H2(g) +

1
2

O2(g) H2O(l) rG = 237.1 kJ mol1

E =

Preparatory Problems

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 2:

Speed of sound

The heat capacity, CV, m, of 1 mole of monoatomic gases such as helium at a


constant-volume condition is expressed by the following equation:
CV , m =

3
R
2

Here, R is the gas constant. The CV, m value corresponds to the increase in the energy of
flying motion of gaseous atoms per unit temperature, and the flight speed of the atoms is
expected to reduce to zero (0) at 0 K.
a)

Derive the mean flight speed, v, of gaseous atoms with molar mass M at temperature
T.

v=

The speed of sound, vs, in monoatomic gases is proportional (and roughly equal) to the
flight speed, v, of the gaseous atoms. The speeds of sound in He (helium) and Ar (argon) at
room temperature are 1007 m s1 and 319 m s1, respectively.
b)

Estimate the speed of sound in Ne (neon), vs(Ne), at room temperature.

vs(Ne) =

Preparatory Problems

m s1

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 3:

Structures of nanomaterials

Fullerenes are a group of well-known novel


nanomaterials

with

hollow

spherical

structures; these nanomaterials are novel


allotropes of carbon. Fullerenes with n
carbon atoms have 12 pentagons and
(n/2-10) hexagons, where n is an even
number and 20 or more.
Answer
assuming

the
that

following
the

questions

length

of

by
each

carbon-carbon bond in fullerene is 0.14 nm


and that the carbon atoms are point
masses.
a) Calculate the surface area of fullerenes
with n carbon atoms in terms of nm

Fig. 1 Structure of a large C1500 fullerene

(1 nm2 10-18 m2).


b) Calculate the radius of fullerenes (in nm) as a function of n by considering the fullerene
molecule as a perfect sphere.
c) Figure 1 shows a large fullerene with C1500. One of hypothetical applications of these
large fullerenes is as a molecular balloon that can float in air. At 300 K and 101325 Pa,
the density of these hollow spherical molecules can be smaller than that of air (80% N2
and 20% O2). Calculate the minimum number of carbon atoms and the minimum radius
of the fullerene (in nm) required to satisfy this condition. Here, the fullerene molecule is
rigid enough to retain its structure under air pressure and is considered to be a perfect
hollow sphere.

Preparatory Problems

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 4:

Vibrational states of Cl2

The wavenumber (cm1), the reciprocal of the wavelength, is often used as a measure of
energy and is equal to the energy of a photon with the corresponding wavelength. The
following figure shows the emission spectrum of gaseous Cl2 excited at 73448 cm1. The
spectrum shows a sequence of peaks, and each peak corresponds to the fluorescence at
the vibrational state with the quantum number v (= 0, 1, 2,...).

...

Eex =
73448
cm1

1
0

rClCl

a)

Calculate the approximate energy spacing between the adjacent vibrational energy
levels at the ground electronic state of Cl2, Ev, in kJ mol1. You can choose any pair of
adjacent peaks for calculation.

Ev =

Preparatory Problems

kJ mol1

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 5:

Raman spectroscopy

The vibration in a diatomic molecule can be considered analogous to the stretching and
compression of a spring, as shown in Figure I. The strength of this hypothetical spring is
expressed by the force constant, k, which is large for strong bonds and small for weak
bonds. Quantum mechanical analysis of the vibrational motion of diatomic molecules
shows that the vibrational energy can be expressed in discrete values. The vibrational
energy Ev is expressed by the following equation:

Ev =

h
2

k
1
v +

h: Plancks constant

Here, v is the vibrational quantum number, which can be any integral value 0, 1, 2,, and
represents the reduced mass of the molecule (

1
1
1
=
+
: m1 and m2 are the atomic
m1 m2

masses).
When the molecule is irradiated with intense radiation such as laser light, light with energy
different from that of the incident radiation is scattered; this optical phenomenon is called
Raman scattering. In this optical process, the difference between the energy of the Raman
scattering light and the incident laser light is the vibrational energy of the molecule, as
shown in Figure II.

Preparatory Problems

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future
a) Obtain the ratio of the reduced masses of H2, N2, and O2.
H 2 : N 2 : O2 = 1 : a : b
b) Wavelength (nm) and frequency (s-1 = Hz) are used to characterize light (radiation).
In spectroscopy, the wavenumber (cm-1), which corresponds to the number of waves
per cm, is also employed frequently. Calculate the frequency and wavenumber of green
light at 500 nm.
Frequency =
Wavenumber =

s-1

c
d

cm-1

c) The energy difference between v = 0 and v = 1 for H2 is 4160 cm-1. Obtain the
wavelength of Raman scattering light when H2 is irradiated with laser light at 500 nm.
The wavelength of Raman scattering light =

nm

d) Assuming that the force constant for O2 is twice that for H2, estimate the energy
difference between v = 0 and v = 1 for O2. Obtain the wavelength of Raman scattering
light when O2 is irradiated with laser light at 500 nm.
The energy difference =

cm-1

The wavelength of Raman scattering light =

Preparatory Problems

nm

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Chemistry: the key to our future

Problem 6:

Internuclear distance of a
hetero-nuclear diatomic molecule

Structure of simple molecules has been determined by spectroscopy, where the


interaction between the radiation and the molecules is observed as a function of
wavelength. The rotational spectrum of molecules appears in the far infrared or microwave
region. Since microwave frequencies can be measured very precisely, internuclear
distance of a diatomic molecule with a permanent dipole moment can be determined with
high accuracy. A spectrum for the H35Cl molecule is shown in Fig. 1. The rotational lines
are separated by = 6.26 1011 s-1.
According to the simple model of a rotating diatomic molecule, the rotational energy,
EJ, is discrete, which can be written as
EJ =

h2
8 2 R e

J (J + 1) J = 0,1, 2, ...

where and Re are reduced mass1 and internuclear distance, respectively. The
rotational energy depends on the quantum number J. Under irradiation of microwave,
transitions between rotational levels from the rotational state J to the rotational state J are
allowed, if
J 'J " = 1 .

Calculate internuclear distance, Re, of H35Cl.


J J:

3 2
2 1

4 3
5 4

1 0

6.26

12.52

18.78

25.04

31.30

x10-11 (s-1 )

Fig. 1

Note
1.

Reduced mass, , is the effective inertial mass appearing in the two-body problem. For two
bodies, one with mass, m1, and the other with mass m2, it is given by

1
1
+
.
m1 m2

Preparatory Problems

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Chemistry: the key to our future

Problem 7: Atomic and molecular orbitals


a) It is known that molecular orbitals of H2+ are represented by the linear

combination of

atomic orbitals (LCAO). The molecular orbitals are

a 1s A 1s B
b 1s A + 1s B
where 1sA is a ground-state hydrogen orbital centered on nucleus A, and 1sB is centered on
nucleus B. The energies for the molecular orbitals are shown in Figure 1 as a function of
the internuclear distance of H2+. (Note that the potential energy between an electron and a
proton is set zero, when an electron and proton is fully separated.) Write which energy
curve is for a .

Energy / eV

(2)

Internuclear distance / nm
0
E1

0.1

0.2

(1)

Fig. 1
b) Write the internuclear distance of stable H2+.
c) The two energy curves in Fig. 1 converge at E1 as the internuclear distance becomes
infinity. Write which physical parameter of the hydrogen atom the energy |E1| equals to.

Preparatory Problems

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 8:

Electronic structure of polyene

The straight-chain polyene (CHCHCHCHCHCH) is a chemical moiety


present in the molecules that absorb visible light. Let us consider the behavior of
electrons in the straight-chain polyene.
First, for the sake of simplicity, we use the Hckel
approximation to assess the electrons of 1,3-butadiene,
which contains four carbon atoms. We define the normal to
the carbon-backbone plane as the z-axis and the atomic
orbital (2pz orbital) of each carbon atom as i (i = 1, 2, 3, 4).
The molecular orbital k is expressed as the linear
combination of these atomic orbitals according to the

Fig. 1 Illustration of the


chemical
structure
of
1,3-butadiene. Each carbon
atom is numbered.

following equation:

k = cii

(1)

The coulomb integral is defined as and the resonance integral between adjacent atoms is
defined as , where is the energy of the 2pz orbital of an isolated carbon atom, and can
be determined from the overlap between adjacent 2pz orbitals. The eigenenergy k and
the corresponding molecular orbital are obtained by the variation method, as shown in the
following sets:

1 = 1.62

1 = 0.371 0.60 2 + 0.603 0.37 4

(2)

2 = 0.62

2 = 0.601 0.37 2 0.373 + 0.60 4

(3)

3 = + 0.62

3 = 0.601 + 0.37 2 0.373 0.60 4

(4)

4 = + 1.62

4 = 0.371 + 0.60 2 + 0.603 + 0.37 4

(5)

a) Draw the energy levels of the molecular orbitals, and indicate

the electrons in the ground state using arrows while


considering the spin direction.
b) Using and , calculate the photon energy necessary for

excitation from the ground state to the first excited state of


1,3-butadiene.
Preparatory Problems

Fig. 2: Illustration of
molecular orbitals
of ethylene. Solid
circle represents a
node.
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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future
c) Draw the highest occupied molecular orbital (HOMO) and the lowest unoccupied

molecular orbital (LUMO) of 1,3-butadiene on the basis of the example for ethylene
shown in Fig. 2, i.e., draw four 2pz orbitals perpendicular to a horizontal line and indicate
the sign for each orbital in black and white. Further, represent nodes by using solid circles.
Note that you do not need to consider the differences in the contribution of each 2pz
orbital to the molecular orbitals.
Next, consider the behavior of electrons in a system where the number of carbon atoms is
extremely large, i.e., polyacetylene. Consider a one-dimensional (1D) chain of a certain
number (N) of 2pz orbitals that are aligned perpendicular to the chain with a spacing of a. If
we assume a periodic boundary condition of Na along the chain, the energy state of the
electrons can be described by the following equation:

E k = + 2 cos ka

k=

2p


, p = 0, 1, 2, k <
a
Na
a

(6)

d) Calculate the energy width between the maximum and the minimum -electron energy

levels.
e) Since the energy-level spacing of the 1D chain is extremely small, the energy levels form

continuum states. Therefore, thermal excitation from HOMO to LUMO is easily induced
at room temperature. Although such thermally excited electrons are mobile in the chain
and can contribute to electric conductivity,
pure polyacetylene is a poor conductor of
electricity. This is because the carbon atoms
in polyacetylene are not arranged with a
periodicity of a; instead, these atoms are
arranged with a periodicity of 2a because of
the alternating arrangement of single and
double bonds. If the HOMO and LUMO of
the 1D chain with periodicities of a and 2a
are assumed as shown in Fig. 3(a) and (b),
respectively, how do the energy levels of the
HOMO and LUMO alter when the periodicity
changes from a to 2a? Choose the correct
answer from the following choices.
Preparatory Problems

Fig. 3Illustration for the LUMO and


the HOMO of the 1D chain with a
periodicity of a (upper) and 2a (lower).
15

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

(a)

HOMO is destabilized, while LUMO is stabilized.

(b)

HOMO is stabilized, while LUMO is destabilized.

(c)

Both HOMO and LUMO are stabilized.

(d)

Both HOMO and LUMO are destabilized.

f) The 1D chain with a periodicity of 2a shows a gap between continuum states, which

results in the formation of a filled valence band and an unfilled conduction band, as
illustrated in Fig. 4. Since the valence band is filled with
electrons and no unoccupied states are available for
conduction, polyacetylene is an insulator. When a chemical
substance is added to polyacetylene, the valence electrons
become mobile. This chemical is obtained by oxidation of
an aqueous solution of an alkali halide, and the number of
inner-shell electrons in its constituent atoms is the same as
that in argon. Write the chemical formula of this substance.

Preparatory Problems

Fig. 4Illustration for the


continuum
electronic
states of the 1D chain
with a periodicity of 2a.

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 9:

Electronic structure of condensed


matter

The electronic structure of condensed matter is usually


different from that of an isolated atom. For example, the
energy levels of a one-dimensional (1D) chain of Na atoms
are illustrated in Figure 1. Here, the energy-level changes of
the 3s-derived states of Na are shown. The energy-level
spacing decreases as the number of Na atoms (N)
increases. At an extremely large N, the energy-level
spacing becomes negligibly smaller than the thermal
energy, and the set of 3s-derived levels can be considered
as a band of energy levels (last image in Figure 1). Na 3s
electrons occupying the band of energy levels delocalize
over the chain leading to a metallic character. Therefore,
the 3s electrons can be assumed to be free particles
confined in a 1D box.
d) The eigenenergy of the free particles confined in a 1D
box is described as

En =

n2h2
8mL2

Fig. 1

( n = 1, 2, 3, )

where n is the quantum number, h is the Planck constant, m is the weight of the
electron, and L is the length of the 1D Na chain. Assuming that the chain length L =

a0(N-1), where N is the number of Na atoms and a0 is the nearest-neighbor interatomic


distance, calculate the energy of the highest occupied level.
e) We assume that 1.00 mg of Na forms a 1D chain with a0 = 0.360 nm. Calculate the
energy width from the lowest occupied level to the highest occupied level.
f) If the thermal energy at room temperature is assumed to be 25 meV, how many Na
atoms are required when the energy gap between the highest occupied level and the
lowest unoccupied level is smaller than the thermal energy (25 meV)? Calculate the
least number of Na atoms required assuming that the number is even.

Preparatory Problems

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 10:

Carbon dioxide I

Oxidation and combustion of organic compounds are exothermic reactions. The heat of
reaction due to the combustion of fossil fuels such as oil, coal and natural gas has been
utilized as main sources of energy.
a)

Calculate the heat of reaction, H, due to the complete combustion of 1 mol of


methane at 298 K in the atmosphere, using the following data of the standard
enthalpy of formation of methane, carbon dioxide and water.

b)

Methane

74.82 kJ mol-1

Carbon dioxide

393.5 kJ mol-1

Water

285.8 kJ mol-1

In a laboratory, we can generate carbon dioxide from calcium carbonate and


hydrochloric acid. Calculate the volume, V (unite, mL), of generated carbon dioxide
from 10.0 g of calcium carbonate and 50.0 mL of 1.00 mol L-1 aqueous hydrochloric
acid at 298 K and 1013 hPa, assuming that the reaction proceeds completely and the
generated carbon dioxide acts as an ideal gas.

Preparatory Problems

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 11:

Carbon dioxide II

Solid carbon dioxide is called Dry Ice. The Dry Ice is molecular crystal and the unit cell
thereof is a face center cubic structure consisting of carbon dioxide molecules.
a)

Calculate a density of Dry Ice, , when the edge length of the cubic unit cell of Dry
Ice is 0.56 nm.

b)

Calculate the number of carbon dioxide molecules, N, in the cuboid Dry Ice of 20 cm
10 cm 5.0 cm.

Preparatory Problems

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 12:

Synthesis of titanium dioxide

One of the important minerals for a raw material of titanium dioxide is ilmenite (FeTiO3). A
model process of the synthesis of titanium dioxide (sulfate process) is divided into the
following processes, (A)-(D).
(A)

Iron (II) sulfate and titanyl sulfate (TiOSO4) aqueous solution is prepared by
dissolving ilmenite in a concentrated sulfuric acid with heating.
(B) Iron (II) sulfate heptahydrate is precipitated by controlling the concentration of the
solution and cooling it.
(C) After the precipitate of iron (II) sulfate heptahydrate is filtered out, titanium hydroxide
(TiO(OH)2) is precipitated by heating the filtered solution and subsequently carrying
out hydrolysis reaction.
(D) Titanium dioxide is prepared by the calcination of titanium hydroxide.
The obtained Iron (II) sulfate is utilized as the source of some ferrite. The surplus sulfate
acid is neutralized with limestone (calcium carbonate). The obtained gypsum (calcium
sulfate dihydrate) is utilized as a by-product.
a)

Natural ilmenite ore contains lots of impurities. Assuming that the titanium content is
35.0 mass% in the natural ilmenite ore when titanium is converted into titanium
dioxide and that the impurities in the ore contain no titanium component except for
ilmenite, calculate the mass of ilmenite, m, in 1000 kg of the natural ilmenite ore.

b)

Show the chemical reaction which proceeds through the processes (A) and (B)
described above as the form of one chemical formula.

c)

Show the chemical reaction through all of the processes (A)-(D) described above as
the form of one chemical formula.

d)

In a laboratory, 25.0 mL of concentrated sulfuric acid (18.0 mol L-1) was used in order
to obtain titanium dioxide from 10.0 g of pure ilmenite. Calculate the minimum amount
of calcium carbonate in terms of mass, m, that is necessary for neutralizing the
surplus sulfuric acid when all of the processes (A)-(D) proceed completely.

Preparatory Problems

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 13:

Born-Haber cycle

Energy is produced by the formation of 1 mol of ion pairs from gaseous ions which
approach each other from infinity. This evolved energy at 0 K under normal atmospheric
pressure is defined as the lattice energy. The lattice energy of an ionic crystal is indirectly
obtained by applying Hesss law to its enthalpy of formation.

a)

Illustrate a Born-Haber cycle of potassium chloride (KCl) and calculate its lattice
energy by use of the following thermodynamic data.
Enthalpy of formation of KCl (s)

- 437 kJ mol-1

Enthalpy of sublimation of K (s)

89 kJ mol-1

Ionization energy of K (g)

419 kJ mol-1

Enthalpy of dissociation of Cl2 (g)

242 kJ mol-1

Electron affinity of Cl (g)

- 349 kJ mol-1

The marks of g and s represent gas and solid state, respectively.

Preparatory Problems

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 14: Solid state structure


The unit cell of the CaF2 crystal structure is shown in the Figure. The addition of a small
amount of Y2O3 to CeO2 with the CaF2 crystal structure and heating give a solid solution
Ce1-xYxO2-y, in which Ce4+ and Y3+ are homogeneously distributed at the cation sites and
oxygen vacancies are formed at the anion sites. Here, the valence of the cerium ions is
assumed to be constant at +4.
a)

Indicate how many cations and anions are


Ce4+

present in the CaF2 structure unit cell?

O2

a
b)

What is the ratio (%) of oxygen vacancies to the anion sites in the solid solution
synthesized with the molar ratio of CeO2 : Y2O3 = 0.8 : 0.1.?

c)

Calculate the number of oxygen vacancies contained in 1.00 cm3 of the above solid
solution. Here, the unit cell volume a3 is 1.36 x 10-22 cm3.

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 15:

Oxide-ion conductors

Oxides with a CaF2 crystal structure containing a high concentration of oxygen vacancies
show oxide-ion conduction when heated at high temperatures, and these oxides are often
called solid electrolytes. A cell using a solid electrolyte with porous Pt electrodes on both
sides can be applied to oxygen sensors, oxygen pumps and fuel cells etc.
In the oxygen pump, oxygen molecules are reduced to oxide ions at the cathode, and the
oxide ions move to the anode and are oxidized to oxygen molecules at the anode, by an
applied voltage. Meanwhile, when the oxygen partial pressures are different at two
electrodes which are not short-circuited, an electromotive force is generated between both
electrodes, and this phenomenon is used for the oxygen sensor.
a)

Represent reaction formulas at the cathode and the anode during oxygen pumping.

b)

An electric current of 1.93 A was flowed for 500 s to move oxygen ions from the
cathode to the anode. Calculate the volume of oxygen gas (mL) produced at the
anode at 800 C under 1.01 x 105 Pa. Given your answer to two significant figures.

c)

Calculate the electromotive force (V) when the ratio of the oxygen partial pressures

P1 and P2 at both electrodes is maintained to be P1/P2 = 100 at 800 C. Electronic


conduction of the solid electrolyte can be ignored.

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 16:

Silver smelting and refining

The Iwami-Ginzan Silver Mine in Japan produced a large volume of silver from the
sixteenth to the seventeenth centuries. The ores included natural silver and argentite (silver
sulfide).

To obtain pure silver from the ores, galena (lead sulfide) was used for the

smelting. In the method, the silver ore was mixed with lead sulfide and then melted in a
container. During the heating process, an alloy of silver and lead was formed and pooled at
the bottom of the container due to the high density of the alloy. The obtained alloy was put
on an unglazed porous ceramic sheet and heated under an air flow. The alloy was melted
and formed a droplet on the sheet. Lead in the alloy reacted chemically with the air and
was removed from the alloy. The other impurities were also removed simultaneously and
silver metal could be obtained.
a)

Write the 2-step chemical reactions from lead sulfide to lead metal. Lead sulfide is
heated under an air flow in the first step of the process, and then heated while
blocking the air in the second step. You should provide the possible two routes with
the different intermediate compounds in your answer.

b)

If the same procedure is carried out with the presence of silver sulfide, an alloy of
silver and lead is obtained. Write the chemical reactions between silver sulfide and the
intermediate compounds of question 1. In general, the composition of the alloy can be
changed continuously and the chemical formula of the alloy cannot be written
stoichiometrically. Answer the question assuming the chemical formula of the
obtained alloy to be AgPb2.

c)

Write the chemical reaction for lead in the alloy during the heating process of the alloy
in the air at about 800 C.

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Chemistry: the key to our future
d)

Which is the reason that best describes why the lead compound obtained in question
3 can be removed from the alloy. Choose one from the following choices.

A: The lead compound reacts chemically with the ceramic sheet and is removed from the
alloy.
B: The lead compound wets the ceramic sheet and is sponged into the porous ceramics
due to a capillary action.
C: The lead compound evaporates and is removed from the alloy.
D: The lead compound is separated from the silver due to the low density of the
compound.
E: The lead compound is separated from the silver due to the high density of the
compound.

e)

What happens, if gold is included in the ores? Choose one from the following choices.

A: Silver is oxidized when gold is precipitated.


B: Gold is precipitated at the bottom of the alloy and can be separated from silver.
C: Gold covers the surface of the alloy and can be separated from silver.
D: Gold is precipitated at the center of the alloy and can be separated from silver.
E: Gold remains in the silver metal as a uniform alloy and cannot be separated from
silver.

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Chemistry: the key to our future

Problem 17:

Cobalt(II) complexes

Cobalt chloride is widely used as an indicator of silica gel activity. The dried state is shown
by a blue color and the red color indicates the absorption of water. In the case of pure
compounds, cobalt(II) chloride anhydrate is blue and the hexahydrate is red. The aqueous
solutions of both compounds are shown by a red color. On the other hand, the ethanol
solution of cobalt(II) chloride anhydrate is shown by a blue color. The color changes to red
with the addition of water.
a)

Write the coordination number and the coordination structure of the cobalt complex in
the ethanol solution of cobalt(II) chloride anhydrate.

b)

The blue color remains when an amount of water double that of the cobalt chloride
was added to the ethanol solution of cobalt(II) chloride anhydrate. Write the chemical
formula of the major cobalt complex in the solution.

c)

Write the chemical reaction when a large amount of water is added to the solution.

d)

Write the coordination number and the coordination structure of the cobalt complex in
the aqueous solution.

e)

If a certain amount of water is added to the ethanol solution, the solution becomes
violet. Explain the color change if a small amount of concentrated hydrochloric acid is
added to the violet solution.

f)

Explain the color change if the temperature of the violet solution decreases.

g)

Write the chemical formula of the cobalt complex in cobalt(II) chloride hexahydrate.

g)

Write the chemical formula of the cobalt complex in cobalt(II) chloride hexahydrate.

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 18:

Red-ox titration

The chromium content of a stainless steel (a Fe-Cr alloy) sample was analyzed by the
following procedure. Answer the questions a) - f). Here, the atomic weight of Cr is assumed
to be 52.00.
i)

0.1000 g of a stainless steel sample is dissolved into 20 mL of heated sulfuric acid


(1.8 mol L-1).

ii)

4 mL of conc. nitric acid is added to the solution and heated for 10 min, when the color
of the solution changes from blue to green.

iii)

10 mL of 0.5% silver nitrate aqueous solution and 6 g of ammonium persulfate


((NH4)2S2O8) are simultaneously added to the solution,It is heated for 20 min until the
decomposition of ammonium persulfate is terminated, when color of the solution turns
orange.

iv)

10 mL of 5% NaCl aqueous solution is added.

v)

20 mL of 1.00x10-1 mol L-1 ammonium iron(II) sulfate (FeSO4(NH4)2SO4) aqueous


solution is added with a volumetric pipette.

vi)

2.00x10-2 mol L-1 potassium permanganate (KMnO4) aqueous solution is titrated using
a burette. When the color of the solution becomes light purple, it is presumed to be the
final point.

a)

Describe the chemical reaction in process ii).

b)

Trivalent chromium ion exists in the solution after process ii). What kind of form will
the chromium ion take after process iii)?

c)

Describe the reaction which occurs in process iv). Also mention the purpose of the
process.

d)

Describe the ionic reaction which occurs between heavy metal ions in process v).
What color will the solution become in the process?

e)

Describe the reaction which occurs in process vi).

f)

The titrated amount in process vi) was 12.00 mL. Derive the chromium content of this
stainless steel sample.

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Chemistry: the key to our future

Problem 19:

Iron-making and crystal structure

Iron is generally produced from an iron ore resource by reducing it with carbon. The main
production process is through a blast furnace (BF) and a convertor. Pig iron (molten Fe-C
alloy) is produced by feeding iron ore resource, subsidiary materials (CaO) and cokes from
the top of the BF and by blowing heated air from the bottom. Then, molten steel is
obtained by oxidizing the pig iron in a vessel such as a convertor in order to remove
impurities as well as carbon. Answer the questions a) - e), with the provision that carbon
content of the pig iron is 4.50 mass% and that a coke contains 90.0 mass% C, 7 mass%
SiO2, 3 mass% Al2O3. The gas constant is 8.314 J K-1 mol-1), and the atomic weights of C,
O, Ca and Fe are 12.0, 16.0, 40.1 and 55.8, respectively. The density of iron is 7.90 g cm-3
at room temperature.
a)

The main component of an iron ore is Fe2O3 and it will be reduced to form Fe and CO2
by (i) CO gas produced by the reaction between the cokes and the heated air or (ii)
carbon in the cokes. Describe each chemical reaction.

b)

Iron ore also contains gangue (impurity materials), such as 7 mass%SiO2 and 3
mass%Al2O3 other than 90 mass%Fe2O3. It will react with the gangue in the coke
and the subsidiary material CaO, forming the oxide melts which will be exhausted as
slag. How many kg of the slag is produced as a byproduct to obtain 1 kg of pig iron?
Assume that the subsidiary material is added so that the mass of CaO is equal to that
of SiO2.

c)

In a convertor process, carbon is eliminated by blowing O2 gas onto pig iron. When
the molar amounts of CO and CO2 are identical, what is the volume (L) of O2 gas
required for the complete removal of carbon from 1.00 kg of pig iron at 27 oC and
2.026105 Pa?

d)

When 1.00 kg of iron is produced from iron ore through BF and a convertor only via
process (i) in the question a), how many kg of CO2 is generated? Assume that the
CO gas (the same molar amount of CO2) generated from the convertor is oxidized and
exhausted as CO2. In the calculation, include the CO2 generated in the calcinations
of CaCO3 to produce the subsidiary material of CaO.

e)

The crystal structure of iron is body center cubic (bcc). Derive the atomic radius of
iron at room temperature.

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 20:

Gibbs energy of oxidation reaction

Answer the following questions on the Gibbs energy of oxidation reactions.


a)

Fill the blanks in the following sentences with suitable terms or chemical formulae.

When metal M is oxidized by one mole of oxygen gas to form an oxide MmOn (m, n:
integers), the reaction can be expressed as (
i
). The standard Gibbs energy
o
change of this reaction, G , can be expressed as (
ii
) in terms of standard
o
(
iii
) change, H , and standard (
iv
) change, So , of this reaction at
an absolute temperature T. On the other hand, when a pure metal M and a pure oxide
MmOn are in equilibrium state at an absolute temperature T, the oxygen partial pressure pO2
can be derived as (
v
) using Go and the gas constant R. The diagram where
Go values for various oxidation reactions are drawn as a function of absolute temperature
is called an Ellingham Diagram (Figure 1). As can be seen in the figure, most relations are
drawn by a straight line and the metals existing in the lower part tend to be (
vi
)
compared to those in the upper part.

Gibbs energy of oxidation reactions


(kJ/mol-O2)

00
200
-200
400
-400
600
-600
800
-800
1000
-1000
1200
-1200
-1400

+ O2
4 Cu

uO
=2C 2

2 Fe +

O2 =

2 FeO

C + O2 = CO2
Fe 3O 4
= 1/2

3/2

O
Fe + 2

O2
Mn +

Si +

O2 =

2C

+O

= 2C

nO
=2 M

S iO 2

i O3
2 /3 T 2
=
O2
l 2O 3
Ti +
4 /3
/3 A
2
gO
O 2=
l+
2M
A
=
3
4/
O2
g+
2M
Ca O
=2
2
O
a+
2C

500

1000

1500

2000

500 Temperature
1000 1500(K) 2000

Figure 1. Gibbs energy of oxidation reaction temperature diagram.


(Ellingham Diagram)
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Chemistry: the key to our future

b)

When both the reactants and the products are in the condensed state (solid or liquid)
in Figure 1, the slope of each line in the diagram shows an almost identical value. The
line is horizontal in the case of CO2 gas, and the slope shows a different sign with the
same absolute value in the case of CO gas. Explain why.

c)

Describe the chemical reaction when Cu2O is reduced by Al.

d)

Derive the heat of the reaction in the above question c) per mole of Al.

e)

Show the points through which any lines of constant oxygen partial pressure pO2 and
those with a constant value of the ratio of CO gas partial pressure to CO2 gas partial
pressure pCO/pCO2 pass, respectively, in Figure 1.

f)

When solid FeO is reduced to Fe by flowing CO gas at 1000 K in equilibrium state,


how much % of the CO gas will be consumed?

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 21:

Quantitative composition analysis


of volcanic gas

Answer the questions a) - c) on composition determination of fumarolic gas.


Before sampling fumarolic gas, 20 mL of 5 mol L-1 NaOH solution was loaded in a syringe
and air was removed from the syringe. A titanium tube was inserted into a fumarole and the
tube was sufficiently heated by the hot fumarolic gas to prevent condensation of fumarolic
gas in the tube. By connecting the titanium tube with the syringe using a rubber tube, the
fumarolic gas was introduced into the syringe by slow drawing. During the sampling
procedure, the syringe was cooled with a wet towel. After completing the gas collection, the
syringe was equilibrated with the surrounding mountain atmosphere condition (0 C, 1013
hPa) and the volumes of gas and liquid components recorded from the scale on the syringe
were 50.0 mL and 38.0 mL, respectively.
A 10 mL aliquot was collected from the 38.0 mL solution in the syringe, and all the sulfur
species were oxidized to sulfate ion using an oxidant. After adding diluted HCl into the
solution and making the solution slightly acidic, the addition of 20 mL of 10% BaCl2 solution
to the solution resulted in a white precipitate. The precipitate was dried and weighed to be
0.30 g.
The volume of 1 mol of a gas is assumed to be 22.4 L in the standard condition (0 C and
1013 hPa).
a)

Calculate the volume component of water vapor (in %) in the collected fumarolic gas
assuming that the volume of NaOH solution did not change by absorption of gases
other than water vapor. The density of NaOH solution was at a constant, 1.0 g mL-1,
during the experiment.

b)

Calculate the quantity of sulfur (in mol) contained in the fumarolic gas collected into
the syringe. Moreover, calculate the total volume (in mL) of H2S and SO2 gas
components in the standard condition (0 C, 1013 hPa). Give the answer to two
significant figures.

c)

Molar ratios of H2S to SO2 are estimated utilizing the reactivity difference between
H2S and SO2 gases. Fumarolic gas is bubbled into a testing tube which contains 30
mL of 0.03 mol L-1 KIO3-KI solution and 3 mL of 4M HCl solution. Describe the
chemical reaction equations occurring for H2S and SO2 gases, respectively.

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 22:

Vibrational and rotational spectra


of volcanic gas

Recently, the chemical composition of fumarolic gas has been determined using remote
spectroscopic methods. The figure shown below is an infrared absorption spectrum
(vibration-rotation spectrum) of fumarolic gas. X and Y in the figures represent two
hydrogen halide species. Y is known to dissolve silicate.

Transmittance

Transmittance

2820

2840

2860

-1

2880

Wavenumber (cm )

X
Y
2000

2500

3000

3500

4000

4500

-1

Wavenumber (cm )
Figure Infrared absorption spectrum of fumarolic gas obtained from a remote observation using an
FTIR equipped with a telescope. X and Y denote hydrogen halides.

a)

Describe chemical formula of X and Y.

b)

As shown in the inset, the absorption bands of X split. This split is caused by the
isotopic composition of the halogen in X has an isotope abundance ratio of 3:1. List
the two isotopes in order of decreasing abundance.

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 23:

Introduction to macromolecular
chemistry

The presentation of concepts of macromolecules (often called polymers) in 1925 by the


Nobel Prize chemist, Dr. H. Staudinger (Germany), opened a fascinating world of new
organic materials presently utilized as plastics, fibers, rubbers and so on.
Macromolecules are roughly classified into two categories, vinyl and non-vinyl polymers.
Unlike the former, which are usually prepared from corresponding vinyl monomers (=
-olefins) by the chain polymerization processes in the presence of initiators or catalysts,
the latter are usually obtained by the step polymerizations of (combination of) bifunctional
monomers, such as H2N-R-COOH (to give polyamides), HO-R-COOH (polyesters),
H2N-R-NH2 + HOOC-R-COOH (polyamides), HO-R-OH + HOOC-R-COOH (polyesters),
etc. As easily understood from the last two instances of the step polymerization between
the bifunctional monomers, the stoichiometric balance of component monomers is one of
the most important factors in obtaining high molecular weight polymers.
When the elementary processes of step polymerization are reversible, such as
esterification equilibria, it is also a matter of importance to shift the equilibria rightward.
Here, wed like to discuss the relation between the equilibrium state and the length of
polymers derived from the stoichiometric mixture of bifunctional monomers. Eq.(1) is a
typical example of an esterification reaction where the equilibrium constant is relatively
small, such as 4.20 at 78 oC (boiling temperature of ethanol).

CH3COOH

(acetic acid)

HOCH2CH3
(ethanol)

CH3CO-OCH2CH3

H2 O

(1)

(ester: ethyl acetate)

a) When the esterification reaction of eq.(1) is equilibrated from each 1.00 mol of
starting material, calculate the amount of ethyl acetate (g).

Replace the monofunctional molecules in eq.(1) with a dicarboxylic acid and a diol, the
corresponding polycondensation reaction may produce linear chain polyesters.
Although the polycondensation is composed of multi-step equilibria, the representation is
often simplified as eq.(2) supposing the same equilibrium constant in each step.
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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

HOOC-R1-COOH + HO-R2-OH HO-[COR1CO-OR2O]n-H + (2n-1)H2O


(dicarboxylic acid)

(diol)

(2)

(polyester)

The length of polymer chain is very important in respect to material chemistry. The long
chain polymers may provide enough mechanical strength to fabricate textiles and thin films.
In turn, the shorter ones are useful as adhesives, coatings, detergents, etc. In order to
discuss on the polymer length, it is easier to think about the degree of polymerization
(abb. )*1) rather than the molecular weight of which calculation is dependent on the
structures of R1 and R2. For instance in eq.(2), is equal to for the dicarboxylic acid
or the diol, whereas it is 2n for the polyester (note that the structure in the brackets is
already dimer)*2).

Because a polymer is a mixture of long, middle and short chain

molecules, is the averaged number*1). The HO- and -H groups attached out of the
brackets in eq.(2) are known as the end groups, and the -COR1CO-OR2O- group is known
as the repeating unit of which the structure is already a dimeric conjunction as described.
Therefore, the unit molecular weight, u, in the case of eq.(2) is defined as follows ;

u molecular weight of the repeating unit

(3)

When the average molecular weight of a polymer is represented by *3), the relationship
among , and u is given as follows ;

weight of end groups/u

(4)

As understood from the calculation in a), when the equilibrium constant of the
designated reaction is relatively small, considerable amounts of starting materials remain
unreacted even at the equilibrium state. The quantity of product can be determined by the
analysis of the consumption of functional groups. Before making discussions, we define
the degree (extent) of reaction, , as follows ;
degree of reaction
[amount of unreacted functional groups][amount of initial functional groups]

Preparatory Problems

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future
For instance, in eq.(1), starting from each 1.00 mol of bifunctional monomers and reaching

0.80 after being reacted for a certain period, then 0.80 mol of the ester is obtained.
In organic syntheses, 100 is equal to the yield (%). If one can achieve 0.80,
it is generally satisfactorily high yield. However, 0.80 is not good enough in the step
polymerization syntheses. As represented below, 0.80 means concomitant success
4 out of 5-times with one failuer, meanwhile.

(- and - represent the

dicarboxylic acid and diol residues, respectively.). is ended with 5.0, in this case.
-----

or

-----

OK

OK

OK

OK

fail

OK

OK

OK

OK

fail

Consequently, should be realized to prepare the polymers with large .

Dr.

Wallace H. Carothers (USA) had studied the relationship between and , and
presented eq.(6) in conclusion.

1/(1)

Carothers eq.

(6)

Although even amateurs can easily prepare vinyl polymers, such as polystyrene, with
106 (corresponding to 104) by the chain polymerization of -olefin monomers,

exquisitely fabricated commercial polycondensation polymers, such as nylon-6,6 or PET


[=poly(ethylene terephthalate), or poly(oxyethyleneoxyterephthaloyl)], carry of merely
1~8 x 104. Typically, of ordinary PET is 4.000 x 104, corresponding to 416.3 (cf.

u 96.09), where the value of the polycondensation between terephthalic acid and
1,2-ethanediol should exceed 0.9976

[since 416.3 1/(1 ) from eq.(6)].

It is

understood that much effort is necessary for the production of step polymerization polymers
with high or .
As estimated in a), elaborative work is necessary to accomplish the reaction condition of

since is relatively small in the case of esterification polycondensation.

The

by-product removal in accordance with the reaction progress is one of the schemes to
realize . For easier consideration, let us simplify eq.(2) into eq.(7); starting from
each (exactly) 1 mol of -COOH (of dicarboxylic acid) and -OH (of diol), mol of ester
linkage is formed at the equilibrium, whereas each mol of -COOH and -OH groups
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Chemistry: the key to our future
remain unreacted.

To shift the equilibrium rightward, the quantity of water should be

diminished from mol to a negligibly small amount, w mol.

-COOH of dicarboxylic acid -OH of diol


1

-CO-O- of polyester water

(7)

(w)

b) Represent by using and w.


c) From the eq. derived in b) and the Carothers eq., represent as a function of
/w.

If logically permitted, the equation should be simplified as far as

possible, considering and .


d) Calculate the upper limit of w in order to accomplish 100, supposing
[-COOH]0 [-OH]0 1.00 mol and 4.00.

The answer should be given as

three significant figures.

Footnotes
-----------------------------------------------------------------------------------------------------------------------*1) It is usually represented as the number-average degree of polymerization and
abbreviated by n.
*2) In the case of polymers derived from bifunctional monomers carrying different
kinds of functionalities such as H2N-R-COOH or HO-R-COOH, because the
repeating unit in such a polymer structure, H-[HN-R-CO]n-OH or H-[O-R-CO]n-OH,
is monomeric, the value of n directly corresponds to .
*3) It is usually represented as the number-average molecular weight (molecular
mass) and abbreviated by n.

Definition : n = (ii /i), where i and i

are the molecular weight and the number of the i-th macromolecular thread,
respectively.

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 24:

Reduction of carbonyl compounds

Reduction of the one of the carbonyl groups in compound A gives compound B, which
contains two stereoisomers, B1 and B2. After separation of these isomers, the reductions
of carbon-carbon bond are carried out to give compound C, as a mixture of two kinds of
stereoisomers, respectively from B1 and B2.

By the separation of the isomers, four kinds

of products Cij (i, j = 1, 2) are obtained. Furthermore, these four products are applied to
the reduction of another carbonyl group to give compound D, which is again a mixture of
two kinds of stereoisomers in each reaction.

After the separation of stereoisomers of each

reaction, eight kinds of products Dijk (i, j, k = 1, 2) are obtained.


H

O
A

a)

OH
O

OH

OH

HO
C

Are there any identical compounds in the eight kinds of products Dijk (i, j, k = 1, 2)?
If so, draw the structures of all the compounds that meet the requirements.

b)

Are there any compounds, in which optical rotation is principally zero degrees, in the
eight kinds of products Dijk (i, j, k = 1, 2)? If so, draw the structures of all the
compounds that meet the requirements.

c)

Are there any compounds which are a pair of optical isomers in the eight kinds of
products Dijk (i, j, k = 1, 2)? If so, draw the structures of all the compounds that
meet the requirements.

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 25:

Kiliani-Fischer synthesis

D-Arabinose is predominantly found in the cyclic form, which is in equilibrium with a minute
amount of the open form. Treatment of D-arabinose with hydrogen cyanide (HCN) yields a
diastereomeric mixture of cyanohydrins A and B. Hydrolysis of cyanohydrins A and B
yields their corresponding carboxylic acids, which lactonize on heating and form the
5-membered lactones C and D (the planar structures of the lactones are shown below),
respectively. The lactones C and D can be reduced with sodium amalgam (or sodium
borohydride) to yield D-mannose and D-glucose, respectively. This chain-extension
procedure is known as Kiliani-Fischer synthesis.

hydrolysis

reduction

C
OH

O
HO
HO

OH
OH

HO

HCN

HO
HO
HO

HO O
OH

D-mannose

O
O
HO

D-arabinose

hydrolysis
B

OH
reduction

HO
HO
HO

O
OH

OH

D-glucose

a) Draw a Fischer projection of the open-form D-arabinose.


b) Draw Fischer projections of the cyanohydrins A and B.
c) Draw stereostructures of the lactones C and D.

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 26:

Glycolysis

Glucose is used as an energy source for short-term activity in most organisms. Glucose is
metabolized into pyruvic acid via a series of reactions catalyzed by various enzymes.
OH
HO

HO

2
OH

O
COOH

pyruvic acid

OH
glucose

The first half of the metabolic pathway proceeds as follows. The first step is the
phosphorylation of -glucose to form -glucose-6-phosphate (1). Next, 1 is transformed
into open-form glucose-6-phosphate (2), which isomerizes to open-form
fructose-6-phosphate (4). This isomerization reaction occurs through the tautomer A of 2
and 4. Phosphorylation of 4 affords fructose-1,6-diphosphate (5), which cleaves into
carbonyl compounds B and C by retro-aldol reaction. Compounds B and C are able to
interconvert via the common tautomer as similar to 2 and 4, and both produce pyruvic acid.
OPO32HO

OPO32HO

HO

O
OH

HO

OH

3
OH OH

HO
HO
2

OPO32-

OPO32-

OPO32HO

OH
CHO

OH

HO

OH
O

OH

HO

OH

B+C

OPO32-

HO
O

A
a)
b)
c)
d)

A solution of glucose was treated with an equal amount of phenylhydrazine in acetic


acid. Draw the structure of the major product.
Draw Fischer projections of glucose-6-phosphate (2) and fructose-6-phosphate (4),
respectively.
Draw the structure of tautomer A.
Draw the structures of carbonyl compounds B and C.

Preparatory Problems

39

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 27:

Menthol synthesis

(-)-Menthol is a major component of the taste and fragrance of peppermint and is widely
used in cakes, cosmetics, and tooth powder, etc. (-)-Menthol is anodyne and is used as
medicine. (-)-Menthol can be supplied from natural resources such as peppermint oil, but is
now synthesized industrially as shown below. It is said that the synthesis supplies about 1/3
of the world demand of (-)-menthol. A key step of the synthesis is 1,3-asymmetric hydrogen
migration reaction from amine A to enamine B. A rhodium catalyst with a chiral bidentate
ligand developed by Ryoji Noyori (Nobel Prize Winner, 2001, Chemistry) can precisely
distinguish enantiotopic hydrogens, HR and HS, and selective migration of Hs provides
optically pure enamine B.
HR HS

Li, (C2H5)2NH

HS HR

chiral Rh catalyst

N(C2H5)2
myrcene

N(C2H5)2

H3O+

H2, Ni catalyst

ZnBr2

CHO

OH

OH

C
(-)-menthol
chiral Rh catalyst
Ph2
P
S
Rh
S
P
Ph2

a)

Which molecules include two enantiotopic hydrogens (HA and HB) that are
stereochemically similar to two hydrogens (HR and HS) of amine A? Select your
answer(s) from all the symbols of the following molecules D-I.
O
HA

OH
HB

b)
c)
d)
e)

Ph = phenyl
S : solvent

H A HB
E

H A HB
HO

HA HB
OH

OH

H A HB

OH
F

HO

OH
HA HB
I

Propose a reasonable reaction mechanism of hydrolysis of enamine B to aldehyde C.


Draw the most stable conformer of (-)-menthol.
Treatment of (-)-menthol with dilute sulfuric acid causes a dehydration reaction.
Predict the major product.
(-)-Menthol is a monoterpene composed of two isoprene units. Surround the isoprene
unit of (-)-menthol in a line.

Preparatory Problems

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 28:

Structure studies of urushiol

Japanese lacquer (Urushi in Japanese) is a natural paint that has been used since ancient
times and is made from the sap of the lacquer tree. Japanese lacquer is glossy and
beautiful and is used for lacquer ware and traditional craft objects. The major component of
the sap of the lacquer tree is urushiol. Oxidation and polymerization of urushiol catalyzed
by the enzyme (laccase) contained in a lacquer tree solidify the sap of the lacquer.
The chemical structure of urushiol has been studied from the beginning of 20th century and
was determined by Professor Rikou Majima in 1918. Urushiol was a mixture of compounds
with similar chemical structures, and even determination of its molecular formula is very
difficult because it was very unstable substance that polymerized easily. Since destructive
distillation of urushiol gave a mixture of catechol (1) and unsaturated hydrocarbons,
urushiol seemed to be catechol derivatives with unsaturated alkyl chains. In addition,
treatment of urushiol with dimethyl sulfate afforded dimethylurushiol. Furthermore, catalytic
hydrogenation of urushiol under ordinary hydrogen pressure just developed by Willsttter at
that time provided pure hydrourushiol as crystals, and the molecular formula of
hydrourushiol was determined as C21H36O2. This advanced structure studies of urushiol
greatly.

urushiol

OH
OH

catecol (1)

a)

O
H3CO S OCH3
O

H2
catalyst
hydrourushiol (C21H36O2)

dimethylurushiol
H2
catalyst
dimethylhydrourushiol

If the saturated alkyl chain of urushiol is one kind and is not branched, there are two
possible structures for hydrourushiol. Draw each structure. Show the alkyl group such
as (CH2)n-CH3.

b)

To determine the structure of hydrourushiol, the following two syntheses (I) and (II)
were performed. Among synthesized compounds B and D, compound D was identical
to dimethylhydrourushiol derived from natural urushiol. Thus, the location of the

Preparatory Problems

41

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future
unsaturated alkyl group of urushiol was determined. Draw the structure of the
synthetic intermediates A and C.

(I)

OCH3
OCH3
CH3(CH2)13COCl

OCH3
OCH3

AlCl3

CH3(CH2)9C

(II)

Clemmensen
reduction

H2

CNa

(CH2)2COCl

c)

Zn-Hg, HCl

Zn-Hg, HCl

Clemmensen
reduction

catalyst

To determine a number and a position of the double bonds of the unsaturated alkyl
chain of urushiol, ozonolysis of dimethylurushiol was carried out. Because urushiol
was a mixture, various carbonyl compounds were provided by this experiment
(question 4, see below). However, carbonyl compounds with three carbons
(OHC-CH2-CO2H and HOOC-CH2-COOH) are not detected by this experiment. This is
because both carbonyl compounds decompose as in the following equations. Show
the chemical formula of E, F, and G.
OHC CH2 COOH

HOOC CH2 COOH

d) Carbonyl compounds obtained by ozonolysis of dimethylurushiol are shown below.

You may assume that all of the double bonds and benzene rings were cleaved. Based
on the experiment results, draw three structures of urushiol among possible urushiols.
Show the unsaturated alkyl chain to determine the position of the double bond as in
(CH2)nCH=CH(CH2)nCH3. You do not need to consider the geometry of the double
bond (cis or trans).

dimethylurushiol

O3

Preparatory Problems

HOOC(CH2)7COOH

CH3(CH2)5COOH

(COOH)2

CO2

HOOC(CH2)4COOH

CH3(CH2)5CHO

CH2CO2H

CH3CHO HCOOH

HCHO

42

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 29:

Synthesis of Tamiflu

Shikimic acid is not only an important intermediate in biosynthesis, but also a useful
chiral reagent leading to the production of various valuable medicines because the
molecule of shikimic acid contains several chiral carbons.
Tamiflu is now a specific medicine for the inhibition of influenza virus propagation, and
can be synthesized starting from shikimic acid which was derived from natural Star anise
(Illicium verum). A part of the synthetic scheme is shown below.
CO2H

CO2C2H5
[a]

[c]

[b]

OH

HO

OH

HO

OH

OH

OH

O
O

C2H5

shikimic acid

C2H5

CO2C2H5

C2H5

NH

N3

O
OH

CO2C2H5
[f]

C2H5

C2H5

[A]

O
OSCH3
O

CO2C2H5

[e]

[d]

C2H5

O
OSCH3
O

C2H5

C2H5

OH

C2H5

O
C2H5

CO2C2H5
Et3SiH/TiCl4

CO2C2H5

CO2C2H5

CO2C2H5

C2H5
C2H5

C2H5
N3

C2H5

NH2

NH2 H3PO4

NHCOCH3
TamifluTM

a) Show chemical reagents necessary for the transformations of a, b, c, d, e, and f


in the above scheme.
b) Show the reaction mechanism for the transformation of b.
c) Show the molecular structure of intermediate A.
d) How many stereoisomers are possible in the molecular structure of Tamiflu?

Preparatory Problems

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 30:

Nuclear magnetic resonance (NMR)


spectra of isomers of C4H8

There are six isomers of C4H8.

a)

Draw the structural formulas of all the isomers.

b)

One of the isomers has only one singlet peak in its proton NMR spectrum. Name this
isomer.

c)

One of the isomers has two singlet peaks in its proton NMR spectrum. Name this
isomer. Also estimate the area ratio of the two peaks.

Preparatory Problems

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 31:

Nuclear magnetic resonance (NMR)


spectrum of [18] annulene

[18]Annulene is an aromatic compound containing 18 carbon atoms. The annulene


molecule has an almost planar structure with 6 inner hydrogens (Hin) and 12 outer
hydrogens (Hout). The 1H NMR spectra of [18]annulene at 213 K and 383 K are shown in
Fig. 1.
Hout
Hin

[18]annulene

Fig.1
a)

In the spectrum obtained at 213 K, estimate the area ratio of the peaks at 9.3 and -3.0
ppm.

b)

Explain why the spectrum obtained at 383 K has only one singlet peak while that
obtained at 213 K has two multiplet peaks.

c)

Estimate the position of the singlet peak in the spectrum obtained at 383 K.

Preparatory Problems

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Practical Problems

Preparatory Problems

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Advanced Level Fields


Practical
1. Synthesis techniques: filtrations, drying of precipitates, thin layer chromatography
2. Theory and practice of extraction with immiscible solvents

Safety
The safety (S) and risk (R) phrases associated with the substances used are provided in

each problem. See Appendix B of the Regulations for the meanings of the phrases.
The experiments are designed to be carried out only in properly equipped chemical

laboratories under competent supervision.


Safety cautions must be provided by the Mentors. Major cautions are shown below.
9 Protect the eyes and body in an appropriate manner.
9 Never pipette solutions using mouth suction.
9 Use a fume hood if indicated.
Disposal procedures are not included in the Preparatory Problems, as regulations are

different in each country.

Preparatory Problems

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 32:
Colloid titration: titration of a cationic surfactant with
polyanion
Colloid titration was first proposed by Hiroshi Terayama in 1948 and has been
developed primarily in Japan. Colloid titration is based on the interactions of charged
colloids (charged polymers, polycations, and polyanions) with inversely-charged colloids
(charged polymers and molecules capable of forming colloids). The reactions employed
for colloid titration entail rapid precipitation, which leads to a cloudy suspension.
Precipitation is completed when the positive and negative charges are equal. The end
point of colloid titration is detected by changes in the color of dyes upon interaction with
colloidstypically the adsorption and desorption of dyes on colloids as well as the
association of dyes with colloids. Colloid titration can be employed for the quantitative
analysis of various colloidal species, such as surfactants, as well as for the determination of
the charges of natural colloids, such as clay particles and humic acid.
In this experiment, you will determine the amount of a cationic surfactant,
benzyldimethyltetradecylammonium chloride, using standard potassium poly(vinylsulfate)
(PVSK). The end point is detected using bromochlorophenol blue (BCPB). BCPB is
initially associated with the cationic surfactant, and its color changes upon release from the
cationic surfactant, which completely interacts with PVSK at the end point.
Chemicals
0.25 mol L-1 acetic acid
benzyldimethyltetradecylammonium chloride (Zephiramine, Zeph; preferably with a
concentration ranging from 5 10-5 to 8 10-5 mol L-1)
bromochlorophenol blue (BCPB; indicator)*
0.0025 mol L-1 potassium poly(vinylsulfate) (PVSK; titrant)**
0.01 mol L-1 sodium hydroxide (NaOH)
* Prepare by dissolving the required amount of BCBP in 5 mL of 0.01 mol L-1 NaOH
solution and diluting it with 200 mL of water.
** The concentration is defined as being that of its monomer unit, C2H3SO4K. Its
equivalent weight is 162.2, provided that the purity (degree of esterification) of PVSK
is 100%.
Glassware
beaker (300 mL)
burette (25 mL)
conical beaker (200 mL)
volumetric pipette (10 mL)

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Chemistry: the key to our future
Procedures
(1) Dissolve 0.048 g of BCPB in 5 mL of 0.01 mol L-1 NaOH solution in a 300 mL beaker,
and dilute it with 200 mL of water. The final concentration of BCPB should be ~4 10-4
mol L-1.
(2) Take precisely an aliquot (10 mL) of the Zeph sample solution at about 1.0 10-4 mol L-1
and add it to a 200 mL conical beaker using a volumetric pipette; then add 1 mL of 0.25
mol L-1 acetic acid and 1 mL of the BCPB solution. Check the pH of the solution using
pH test paper. If the pH is not around 3.3, add acetic acid or NaOH solution to achieve
the desired pH of 3.3.
(3) The initial color is blue. Carefully drop the standard PVSK solution into the sample
solution while stirring continually. Before the end point is reached, the solution may
become somewhat cloudy. If the solution becomes cloudy, drop the standard PVSK
solution in slowly. At the end point, the color should change to yellow.
(4) Read the volume of the PVSK solution added.
Questions
1. Calculate the Zeph concentration in mg L-1. The reaction ratio of the monomer unit of
PVSK to Zeph is 1:1.
2. Why does the solution become cloudy, as the end point is approached? Why does the
solution become clear again after the end point is reached?

Substance
acetic acid
benzyldimethyltetradecylammonium
chloride (Zephiramine)
bromochlorophenol blue (BCPB)
potassium poly(vinylsulfate) (PVSK;
or poly(vinyl sulfate) potassium salt)
sodium hydroxide

Preparatory Problems

-1

0.25 mol L
~5-810-5 mol L-1
aq. solution
solid
0.0025 mol L-1
aq. solution
0.01 mol L-1
aq. solution

R phrases
10-35

none listed

S phrases
23-26-45
36/37/39-4561
none listed

36/37/38

26-36

35

26-37/39-45

21/22-34-50

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 33:
Analysis of zinc-aluminum alloy by EDTA titration
Alloys containing aluminum and zinc as primary alloying elements have been developed
in Japan for use in industry. The most famous exampleextra super duralumin
7075is the strongest aluminum alloy used in aircraft manufacturing. Recently, a novel
zinc-aluminum alloy that exhibits an interesting mechanical property has also been
developed. The alloy exists as a solid at room temperature but is easily spread like a
starch syrup under appropriate mechanical tension.
This property is known as
super-plasticity, which facilitates industrial uses of the alloy, including use as a
high-performance and semi-permanent seismic damper for protecting buildings from
earthquakes. This unique property arises from the alloys fine-grained microstructure
containing 7%50% aluminum by weight.
Composition is a fundamental parameter for developing such advanced alloys. In this
experiment, assuming the composition assay of this type of alloy, you will be given a test
solution which simulates a digested sample of the alloy; 50 mL of the solution contains
3035 mg of zinc and 1015 mg of aluminum, and is acidified to pH 1 using hydrochloric
acid. You will be required to determine the concentrations of Zn2+ and Al3+ in the sample
solution by titration utilizing ethylenediaminetetraacetic acid (EDTA) as a chelating agent.
Masking and back-titration techniques should also be employed.
Chemicals
test solution (prepare as described above)
0.1 mol L-1 acetic acid solution
ammonium fluoride
0.01 mol L-1 ethylenediamine-N,N,N',N'-tetraacetic acid, disodium salt, dihydrate
(EDTA2Na2H2O) standard solution (accurately prepared)
10% (w/v) hexamethylenetetramine (hexamine) solution
0.1% methyl orange (MO) solution
0.1% xylenol orange (XO) ethanol/water (20/80) solution
0.01 mol L-1 Zn2+ standard solution (accurately prepared using ZnSO47H2O)
Apparatuses and glassware
burette (25 mL, 1 rack)
Erlenmeyer flask (200 ml 5)
hot-plate 1
magnetic stirrer 1
Pasteur pipette (dropper) 4
pipette (10 mL 2, 30 mL 1)
safety bulb 1
stirring bar (coated with Teflon) 4

Preparatory Problems

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future
Procedures
(1-1) Pipette 10 mL of the sample solution into a 200 mL Erlenmeyer flask and place a
stirring bar in the flask. Start stirring the solution on a magnetic stirrer and add a few
drops of MO indicator. Add 30 mL of a 0.01 mol L-1 EDTA standard solution. To
adjust the pH of the mixture to ca. 3.5, introduce (dropwise) a 10% hexamine solution
into the flask until the MO indicator shows a slight color change, from red to orange.
Place the flask on a hot-plate and boil the mixture for a few minutes; then place the
flask in an ice bath to cool the mixture. After cooling, place the flask on the magnetic
stirrer and add a few drops of the XO indicator solution to the mixture.
(1-2) Adjust the pH to ca. 5.5 as follows: stir the mixture gently, deliver the 10% hexamine
solution dropwise into the flask until the XO indicator changes color from yellow to
slightly purplish, and then, add a 0.1 mol L-1 acetic acid solution in drops until a clear
yellow color reappears. Next, titrate the mixture using 0.01 mol L-1 Zn2+ standard
solution until the color turns to purple. The volume of titrant used in step 1-2 is
defined as A mL. (Caution: Do not discard the titrated mixture; you will need to titrate
it continuously in step 2-1.)

Note:
Determining the end point is somewhat difficult, since the color changes gradually
from yellow to purple as the end point is approached. When the color is close to
purple, read the burette and then add another drop of titrant; if there is a perceptible
color change, read the burette again and add another drop. Repeat this process
until a drop of titrant causes no color change, and then record the preceding burette
reading. If EDTA is still present, the yellow color will return; add more titrant until the
color remains purple for at least one minute.
(2-1) Add ca. 1.0 g of NH4F to the titrated mixture in step 1-1, and heat it on the hot-plate
until the mixture boils; note that heating results in the mixtures color returning to
yellow. Remove the flask to an ice bath, and after the mixture cools, place the flask
on the magnetic stirrer. If the clear yellow color has disappeared after cooling, add a
0.1 mol L-1 acetic acid solution dropwise until the color reappears. Next, titrate the
mixture again using a 0.01 mol L-1 Zn2+ standard solution. The volume of the titrant
used in step 2-1 is defined as B mL.

Preparatory Problems

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Chemistry: the key to our future
Questions:
1. In steps 1-1 and 1-2, why is the pH adjusted to ca. 3.5 and ca. 5.5 in a stepwise
manner? Explain the reason considering the difference in the stability of each
metal-EDTA and -hydroxyl complex.
2. What is the role played by the ammonium fluoride added to the mixture in step 2-1?
3. Show the formula for calculating the concentration of the Al3+ and Zn2+ ions in the
sample solution based on the results of each titration (A and B).
4. Calculate the concentrations of Al3+ and Zn2+ ions in the sample solution in mol L-1.
5. Assuming that the alloy contains only Al and Zn, calculate the composition of the alloy
in percent by weight.

Substance
acetic acid

0.1mol L-1
aq. solution

ammonium fluoride
ethylenediamine-N,N,N',N'0.01mol L-1
tetraacetic acid, disodium salt, aq.
solution
dihydrate
Hexamethylenetetramine
10% aq. solution
methyl orange
0.1% aq. solution
ethanol
liquid
0.1% ethanol
xylenol orange
(20%) / aq. solution
0.01mol
L-1
ZnSO47H2O
aq. solution

Preparatory Problems

R phrases

S phrases

10-35

23-26-45

23/24/25

26-45

none listed

none listed

11-42/43
25
11

16-22-24-37
45
7-16

none listed

none listed

22-41-50/53

22-26-39-4660-61

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Chemistry: the key to our future

Problem 34:
Preparation of urea-hydrogen peroxide
Hydrogen peroxide (H2O2), which can oxidize a variety of inorganic and organic
compounds under mild reaction conditions, is widely used in industry, particularly the
chemical industry. Because water is the only degradation product of H2O2, it is an
environmentally friendly oxidant. The adduct of hydrogen peroxide with urea through
hydrogen bonding is considered to be a useful solid form of hydrogen peroxide
(urea-hydrogen peroxide: UHP). UHP is an inexpensive and safe oxidant similar to
aqueous hydrogen peroxide. Since UHP is a stable solid, it is more convenient to use
than aqueous hydrogen peroxide.
In this experiment, you will prepare UHP by mixing urea and aqueous hydrogen
peroxide. UHP will be obtained as white needle crystals via slow evaporation. The
hydrogen peroxide content will be determined by redox titration using potassium
permanganate.
Chemicals
30% hydrogen peroxide
manganese dioxide
0.02 mol L-1 potassium permanganate (after standardization)
urea
Apparatuses and glassware
beaker (100 mL)
burette (25mL)
conical flask (300 mL)
Erlenmeyer flask (10 mL)
filter paper
graduated pipette
test tube
volumetric flask (100 mL)
volumetric pipette (10 mL)
water bath on a heating plate
watch glass (preferably ca. 20 cm in diameter)

Preparatory Problems

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Chemistry: the key to our future
Procedures
(1) Pipette about 3.4 mL of 30% hydrogen peroxide into a 10 mL Erlenmeyer flask using a
volumetric pipette and add 1.2 g of urea (hydrogen peroxide : urea = 3 : 2 molar ratio).
Heat a water bath to 60 C (taking care to regulate the temperature to avoid hydrolysis
of urea). Place the Erlenmeyer flask containing the mixture in the water bath and
heat it for a few minutes to yield a clear, colorless solution. Transfer the solution to a
watch glass for slow evaporation.
(2) Needle-like crystals will gradually develop from the solution. After the crystallization
is completed, place the needle-like crystals on a filter paper to remove the moisture.
Weigh the crystals.
(3) Place about 0.1 g of the crystals in a test tube and add water. Put a trace of
manganese dioxide in the test tube to confirm the formation of an oxygen bubble.
(4) Accurately weigh approximately 0.62 g of the crystals and transfer them to a 100-mL
beaker. Add 50 mL of water to dissolve the crystals. Transfer the solution to a
100-mL volumetric flask and dilute it with water to the 100 mL mark. Pipette 10 mL of
the solution into a 300-mL conical flask. Add 200 mL of water and 20 mL of diluted
sulfuric acid (10%).
(5) Titrate the solution with standard 0.02 mol L-1 potassium permanganate until a faint
pink color persists for 15 s. Be sure to add the standard 0.02 mol L-1 potassium
permanganate slowly to prevent the formation of manganese dioxide. As a blank test,
the same titration should be done without the crystals.
Questions
1. Calculate the hydrogen peroxide contents (mass %) in the crystals.
2. Write a balanced equation for the reaction.
3. Calculate the theoretical yield of urea-hydrogen peroxide.
4. Calculate the percentage yield.

Substance
hydrogen peroxide
manganese dioxide
potassium permanganate
urea

Preparatory Problems

30% aq. solution


solid
0.02 mol L-1
aq. solution
solid

R phrases
22-41
20/22

S phrases
26-39
25

51/53

61

none listed

none listed

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 35:
Separation of a dye
chromatography (TLC)

mixture

using

thin-layer

Since ancient times, organic dyes have been used for coloring cloth and leather.
Numerous species of plants and animals have been used as sources of natural dyes. The
extraction and purification of dyes as well as the dyeing process itself are sophisticated
chemical processes. The first human-made (synthetic) organic dye, mauveine, was
discovered as late as the 19th century. Since then, however, thousands of synthetic dyes
have been used for various purposes extending beyond coloring, including indispensable
uses for digital photo-recording media such as compact discs (CDs) and digital versatile
discs (DVDs). The apparent color of a dye solution comes from the absorption of light
preferred by the dye molecule. When a dye solution in a transparent vessel is seen
against a white background, the complementary color of its absorption can be recognized.
In this experiment, you will learn the basic principles and procedures for separating and
distinguishing individual dyes from their mixture.
Chemicals
organic dyes (respective names of dyes intentionally hidden)
A

B
CH2CH3

CH2CH3
H3CH2C

Cl

CH2CH3

Na
O 3S

Na

Na

CO2H

H2C

N
CH2CH3

Cl

SO 3

SO 3

CH2

CH2CH3

Cl

OCH3

OCH3

methanol
developer (mixture of methanol and water (90/10 = v/v))
Apparatuses and glassware
glass capillary
TLC plates

Code

Stationary phase

P-1

Silica modified by octadecylsilyl ligands

P-2

Silica modified by anion-exchange ligand

P-3

Silica modified by cation-exchange ligand

wide-mouth bottle with cap (developing chamber) ( 3)


Preparatory Problems

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future
*If P-2 and P-3 plates are not available, prepare them from modified silica gel and
calcium sulphate (CaSO41/2H2O; binder) (you can use silica gel with calcium sulphate
instead of pure calcium sulphate). Typically, slurry modified silica gel and calcium
sulphate in a methanol/water mixture (2/18) and homogenize the slurry using an electric
blender. Spread the slurry on a glass plate. Dry and then activate it at 110-130 C.
Procedures
Using a pencil, draw a starting line approximately 10 mm above the shorter edge of a
silica gel plate.
(1) Draw cross marks on the line as chromatography starting points.
(2) Use a glass capillary to collect some of the sample solution, spot the solution lightly
on one of the starting points, and dry the spot with a dryer, if necessary. Repeat this
operation a few times to concentrate the sample in a small spot, measuring less than
2 mm in diameter.
(3) Pour developing solvent into the respective wide-mouth bottles about 5 mm in
height.
(4) Close the caps and wait a few minutes until the bottles are saturated with solvent
vapor.
(5) Open the cap of one bottle and grip the upper edge of a TLC plate with tweezers.
Place the TLC plate in the bottle so that the bottom of the plate is immersed in the
solvent and the top of the plate is leaning against the wall of the bottle. The solvent
should be drawn straight up.
(6) Finish the development when the solvent front reaches about 10 mm below the
upper edge of the TLC plate.
(7) Take the TLC plate out and immediately mark the front line of the developing solvent
with a pencil.
(8) Record the shapes and colors of the spots.
(9) Use the same steps to develop the other TLC plates.

Fig. 35.1 TLC plate placed in a bottle with a


cap.

Preparatory Problems

Fig. 35.2 TLC plate and developed spots.

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Chemistry: the key to our future
Questions
I. TLC results
1. From the spots recorded on the TLC plates, calculate the Rf value of each dye on each
plate.
Rf = a/b
a = distance from the starting point to the center of gravity of the sample spot.
b = distance from the starting point to the front of the developing solvent.
2. Determine the color of dyes A, B, and C by considering the nature of the surface of the
TLC plate and the properties of the molecules (acidic or basic and hydrophilic or
hydrophobic) anticipated by the structural formulae.
3. Explain concisely how you reached your conclusion.
II. Absorption spectra
The apparent color of a dye solution comes from the light absorption preferred by the
dye molecule. We can obtain more in-depth information on dyes from their optical
absorption spectra. The figure shows the absorption spectrum obtained by measuring the
3.30 10-6 mol L-1 solution of one of dyes AC using a cuvette with a 10-mm optical path
length. Maximum absorbance (0.380) is observed at 545 nm, which corresponds to the
wavelength of yellow-green light.

0.40

Absorbance

0.35
0.30
0.25
0.20
0.15
0.10
0.05
0.00
400

450

500

550

600

650

700

Wavelength / nm

Fig. 35.3 Absorption spectrum of a dye.


The following are questions concerning the phenomena of light absorption and the
BeerLambert law.
1. Calculate the molar absorption coefficient of the dye at 545 nm.
2. Calculate the % transmittance of the dye solution at 545 and 503 nm (the absorbance
is 0.100 at 503 nm). Then calculate the % transmittance that will be measured at
Preparatory Problems

57

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

3.

each wavelength when the dye solution is diluted by 50%. By comparing these
results, estimate which wavelength of the light source results in a more sensitive
change in transmittance when the concentration of the dye solution is modified.
Calculate both the absorbance and % transmittance obtained for the original dye
solution at 545 nm using a cuvette with a 30-mm path length.

Substance
methanol

liquid

silica
silica modified by octadecylsilyl
ligands (ODS-modified silica)
Silica modified by anion-exchange
ligands
Silica modified by cation-exchange
ligands
Dye A
Dye B
Dye C

solid

R phrases
11-23/24/25-39
/23/24/25
none listed

solid

none listed

22-24/25

solid

36/37/38

26

solid

34

solid
solid
solid

22-41
68
none listed

Preparatory Problems

S phrases
7-16-36/3745
none listed

26-36/37/39
-45
26-39
36/37
none listed

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42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 36:
Hydrolysis of ethyl acetate over a solid acid catalyst
A catalyst is a key material used in efficient chemical conversions. Today, about 90%
of chemical processes use catalysts. Large-scale catalytic processes are employed, for
example, in oil refining and petrochemical processes. In the petroleum industry, soluble
liquid acids, such as sulfuric acid, are often used as catalysts in homogeneous systems.
Since liquid acids are difficult to recover, however, insoluble solid acids are welcome for use
in environmentally benign processes.
Various solid materials are capable of releasing H+ ions into liquids, and such materials
can be utilized as solid acid catalysts. H+-type cation-exchange resins are typical
examples of solid acids. In this experiment, you will examine the catalysis of an H+-type
cation-exchange resin for hydrolysis of ethyl acetate.
+
1
2
R1COOR2 + H2O H

R COOH + R OH

Chemicals
Amberlyst-15 (H+ form, dry)
ethyl acetate (reactant)
phenolphthalein (0.5 wt.% solution in ethanol/water (1/1))
0.02 mol L-1 sodium hydroxide (NaOH) standard solution
(concentration accurately determined)
Apparatuses and glassware
burette (25 mL)
Erlenmeyer flasks (100 mL 6)
glass vials (10 mL 6; must be dried)
graduated pipette (5 mL)
magnetic stirrer
stirring bar
Pasteur pipette (dropper)
reflux condenser
silicone plug
thermometer
three-necked flask (250 mL)
volumetric pipettes (1 mL and 3 mL)
water bath
Procedure
(1) Assemble the experimental setup as shown in Fig. 36.1. The chemicals will be
charged through the unequipped neck.
(2) Charge water (100 mL) and Amberlyst-15 (1.0 g) into the three-necked flask. Then
heat and stir the solution.
(3) When the solution reaches a constant temperature of 60 C, add ethyl acetate (5 mL) to
Preparatory Problems

59

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future
the flask. This will be the start time of the reaction.
(4) Charge six Erlenmeyer flasks with cold water (50 mL) and add a few drops of
phenolphthalein to each flask. Keep the flasks at room temperature.
(5) Fill a 25-mL burette with the 0.3 mol L-1 NaOH solution.
(6) Ten minutes after the start of the
reaction, stop stirring the mixture in
order to settle out the catalyst, and
transfer about 5 mL of the solution to a
glass vial using a graduated pipette.
Immediately, transfer 3 mL of the
solution to an Erlenmeyer flask charged
with water with a volumetric pipette.
(You can directly transfer the solution
from the reactor to the Erlenmeyer flask,
depending on your skill level). Stir the
solution again.
(7) Repeat procedure (6) at intervals of 10
min until 60 min have elapsed from the
start of the reaction. Then similarly
prepare five more samples for titration
in Erlenmeyer flasks.
(8) Titrate six samples in the Erlenmeyer
flasks with the NaOH solution. It is
recommended that you calculate the
amount of the NaOH solution required
Fig. 36.1 Experimental setup.
for complete hydrolysis of ethyl acetate
prior to the titration.
Analysis
1. Determine the concentration of acetic acid in the solution at each reaction time t, defined
as Ct, from the titration results. The density of ethyl acetate is 0.900 g cm-3.
Cc
against t, where Cc is the expected concentration for complete
2. Plot log10
Cc Ct
hydrolysis.
3. Estimate the first-order rate constant from the plot.

Substance
ethyl acetate
Amberlyst-15
phenolphthalein
sodium hydroxide

Preparatory Problems

liquid
solid (granular)
0.5 wt.% solution in
ethanol/water (1/1)
0.3 mol L1
aq. solution

R phrases
11-36-66-67
36

S phrases
16-26-33
26-36

10

7-16

36/38

26

60

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 37:

Synthesis of a zinc ferrite

Ferrites were invented by Yogoro Kato and Takeshi Takei in Japan in 1930. They are
magnetic mixed oxides of iron and divalent metals (M) expressed as MFe2O4. A
representative example of ferrites is Fe3O4, where M2+ = Fe2+, and many divalent cations
can form ferrites with Fe3+ cations. Today, ferrites are very important magnetic materials
used in electronics.
Ferrites are also important in waste water treatment, where they are used for the
removal of heavy metal cations. This is related to the synthetic process of ferrites.
Ferrites can easily be prepared by a wet precipitation technique from a solution containing
M2+ and iron (Fe2+ and/or Fe3+) cations under oxidative conditions and with a controlled pH
and temperature. In this experiment, you will prepare a ferrite, ZnFe2O4, from a solution of
Zn2+ and Fe2+.
O , OH
II
III
(ZnIIxFe1
Zn2+ , Fe2+ 2
x )Fe2 O 4
Chemicals
acetic acidsodium acetate buffer solution (pH 4)
iron(II) sulfate heptahydrate (FeSO47H2O)
sodium hydroxide (2 mol L-1 solution)
zinc sulphate heptahydrate (ZnSO47H2O)
Apparatuses and glassware
air pump (flow rate 100 mL min-1) and tubing
Bchner funnel
Erlenmeyer flask (200 mL)
glass microfiber filter (to capture particles of ca. 0.3 m)
graduated pipette (2 mL)
hot-plate magnetic stirrer
magnet
pH test paper (effective for pH 711)
stirring bar
thermometer
suction flask
tweezers
Procedures
(1) Assemble the experimental setup as shown in Fig. 37.1.
(2) Dissolve FeSO47H2O (2.0 g) in water (40 mL) in the Erlenmeyer flask.
(3) Start stirring the solution.
(4) Dissolve ZnSO47H2O (0.20 g) in the solution.
(5) Start air bubbling through the glass tube (see Fig. 1).
(6) Heat the solution until the temperature reaches 6575 C. Add around 6 mL of the
sodium hydroxide solution and confirm that the solution pH reaches 911. If not, add
Preparatory Problems

61

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

(7)

(8)
(9)

(10)

(11)
(12)

(13)

more of the solution until the pH has reached 911. The time when the pH is
adjusted is the reaction start time.
Add the sodium hydroxide solution at appropriate intervals to maintain the pH at 911
while maintaining the solutions temperature. The color of the precipitate will
gradually turn deep black.
One hour after the start of the reaction, stop stirring, air bubbling, and heating.
Place the magnet on the outer
wall of the flask and confirm that
the
magnet
attracts
the
precipitate.
Separate the precipitate by
suction filtration using a glass
microfiber filter.
Recover the
precipitate appropriately (it may
be difficult to recover the fine
particles that stick to the flask
wall).
Wash the precipitate with the
acetate buffer (50 mL).
Wash the precipitate with water,
and then dry it at around 80 C in
an air oven.
Fig. 37.1 Experimental setup.
Weigh the precipitate.

Questions
1. Provide the theoretical yield of ferrite in grams.
2. Calculate the percentage yield of ferrite.
3. What analytical techniques can be used to detect the unreacted ferrous and zinc ions
in the washing procedure (11)?
4. Choose the species that would be precipitated with ferric ions to form ferrites in a way
similar to Zn2+ (ionic radius 0.074 nm) (the values in parentheses are ionic radii of the
cations):
Al3+ (0.051 nm), Ba2+ (0.134 nm), Ca2+ (0.099 nm), Cs+ (0.167 nm), Cu2+ (0.072 nm),
Hg2+ (0.110 nm), Mg2+ (0.066 nm), Ni2+ (0.068 nm)

Substance
acetic acidsodium acetate buffer
liquid
solution (pH 4)
iron(II) sulfate heptahydrate
solid
2 mol L1
sodium hydroxide
aq. solution
zinc sulfate heptahydrate

Preparatory Problems

solid

R phrases

S phrases

none listed

none listed

22

36/37/39

34

26-37/39-45

22-41-50/53

22-26-39-46
-60-61

62

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 38:
Identification of polymers and small organic molecules
by qualitative analysis
Simple chemical tests are often utilized for qualitative analyses of inorganic and organic
compounds. Identification of unknown compounds requires a wide range of chemical
knowledge. In order to identify inorganic compounds, unknown compounds are classified
on the basis of their behavior to reagents which bring about acid-base, and/or redox
reactions, sometimes producing precipitations. For organic compounds, the chemical
reactions of functional groups present in the molecule are used for identification purposes.
For polymeric compounds, the additional effects characteristic of macromolecules should
be taken into consideration in order to identify the compounds.
Suppose that a polymer solution with a functional group A in each repeating unit is
mixed with a solution of a chemically complementary polymer with a functional group B,
and that there are attractive interactions between A and B. Due to the presence of a large
number of the repeating units, the intermolecular attractive interactions inherent in
polymers are stronger than those of the corresponding small molecules. Combining such
polymers forms a polymer-polymer complex. The complex usually shows lower solubility
than the individual polymers, and precipitation of the complex is often observed.
In this experiment, you will have five unknown aqueous solutions (AE), each
containing one of the compounds below (all of which are used). Carry out the following
experiments and answer the questions.
CH3
CH2 C

HO CH2 CH2 OH HOOC CH2 CH2 COOH

COOH n
poly(methacrylic acid)

ethylene glycol

CH2 CH

succinic acid
NH2 HCl

SO3Na n
poly(sodium 4-styrenesulfonate) aniline hydrochloride
Chemicals
anhydrous sodium carbonate (granular)
0.5 mol L-1 aniline hydrochloride solution
0.5 mol L-1 ethylene glycol solution
poly(allylamine hydrochloride) (MW = 56,000) solution
(monomer unit concentration: 0.1 mol L-1)
Preparatory Problems

63

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future
poly(ethylene oxide) (MW = 400,000) solution
(monomer unit concentration: 0.1 mol L-1)
poly(methacrylic acid) (MW = 100,000) solution
(monomer unit concentration: 0.1 mol L-1)
poly(sodium 4-styrenesulfonate) (MW = 70,000) solution
(monomer unit concentration: 0.1 mol L-1)
0.2 mol L-1 succinic acid solution
Glassware
graduated pipettes
test tubes
Procedures & Questions
(1) Identify the compound in each solution from the results of procedures a) and b) below.
a) Add a small amount of anhydrous sodium carbonate (ca. 20 mg per 1 mL of
solution) to each solution.
b) Add the poly(allylamine hydrochloride) solution (approximately 1:1 in volume) to
each solution. If no precipitation is observed, add a small amount of anhydrous
sodium carbonate (ca. 10 mg per 1 mL solution).
(2) Give the equations for the reaction of aniline hydrochloride with anhydrous sodium
carbonate and for the reaction of succinic acid with anhydrous sodium carbonate.
(3) Is it possible to identify the compound by utilizing poly(ethyleneimine hydrochloride)
instead of poly(allylamine hydrochloride)? Explain.
(4) Mix the poly(ethylene oxide) solution with an equal amount of the poly(methacrylic acid)
solution. Then add a small amount of anhydrous sodium carbonate. Report on the
changes in appearance of the mixed solution and interpret these results.

Substance
anhydrous sodium carbonate

Solid
( granular)

aniline hydrochloride

solid

ethylene glycol
poly(allylamine hydrochloride)
poly(ethylene oxide)
poly(methacrylic acid)
poly(sodium 4-styrenesulfonate)
succinic acid

liquid
solid
solid
solid
solid
solid

Preparatory Problems

R phrases

S phrases

36

22-26

23/24/25-40-41-43-4
8/23/24/25-50-68
22
22-43
none listed
none listed
none listed
37/38-41

26-27-36/37/
39-45-61-63
none listed
36/37
none listed
none listed
none listed
26-36/37/39

64

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 39:
Synthesis of 1,4-dihydro-2,6-dimethylpyridine-3,
5-dicarboxylic acid diethyl ester (Hantzsch ester)
1,4-Dihydropyridine and its derivatives (1,4-DHPs) are ubiquitous in nature and
common to a number of bioactive molecules that include antitumor, antimutagenic, and
antidiabetic agents. 1,4-DHPs are also known as therapeutic agents of an important class
of calcium channel blockers. Recently, 1,4-DHPs have played a new role in organic
chemistryas alternative hydrogen sources. They have been used instead of gaseous
hydrogen to reduce various organic compounds containing C=C, C=N, and C=O bonds,
with or without the aid of appropriate catalysts.
A Hantzsch 1,4-DHP ester (or simply a Hantzsch ester), represented by
1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylic acid diethyl ester, is one such compound
in which synthesis is accomplished conveniently by a one-pot multi-component reaction of
commercially available reagents. In this experiment, you will synthesize the Hantzsch
ester according to the scheme illustrated below.
N
N
N

10 H2O

6
H

+
H

4 NH4OH

hexamethylenetetramine
O H
O
2

H3C

+
OCH2CH3

+
H

NH4OH

(NH4)2CO3

H O

CH3CH2O

water, heat

ethyl acetoacetate

H3C

OCH2CH3
N
H

CH3

Hantzsch ester

Chemicals
ammonium carbonate
anhydrous sodium sulfate
1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylic acid diethyl ester
ethyl acetate
ethyl acetoacetate
hexamethylenetetramine (hexamine)
toluene
Apparatuses and glassware
Bchner funnel
glass capillary
Erlenmeyer flasks (25 mL and 100 mL)
filter paper
Preparatory Problems

65

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future
graduated pipette
hot-plate magnetic stirrer (magnetic stirrer with heating plate)
magnetic stirring bar
suction flask
test tube (100 mL)
thermometer
thin layer chromatography plate
(silica gel 60 F254; layer thickness: 0.25 mm on a glass support)
UV lamp equipped with short and long waves (254 and 365 nm)
water aspirator (or diaphragm vacuum pump)
wide-mouth bottle with cap (developing chamber)

Procedure
(1) In a fume hood, enter 1.30 g of ethyl acetoacetate and 50 mL of water into a 100-mL
Erlenmeyer flask. Add 1.00 g of ammonium carbonate powder and place the magnetic
stirring bar in the flask; stir at room temperature on a hot-plate magnetic stirrer until the
ethyl acetoacetate is completely dissolved. Add 7.00 g of hexamethylenetetramine
and place a cork stopper on the flask. Heat the mixture to 70 C (use a thermometer)
while stirring on a preheated hot-plate magnetic stirrer. After heating for 1 h, cool the
mixture to room temperature by removing it from the hot-plate stirrer.
(2) As the mixture cools down, take a small portion of the reaction mixture using a glass
capillary and load it to make two spots in the center and right positions on a thin layer
chromatography (TLC) plate. Load an appropriate amount of ethyl acetoacetate in the
center and left positions, so that there are three spots on the plate, the central of which
spots contains both the reaction mixture and ethyl acetoacetate. Develop the TLC
plate using hexane/ethyl acetate (2/1) as a developer. Use a pencil to trace the
outlines of the spots detected using a UV lamp (254 and 365 nm).

Development chamber

TLC Plate

X X+Y Y

X:
Y:

ethyl acetoacetate
reaction mixture

Fig. 39.1 TLC plate placed in a Fig. 39.2 Spots on the TLC plate before
bottle with a cap.
development.
(3) After a crystalline product has been precipitated out of the reaction mixture, filter the
product through a Bchner funnel under reduced pressure, wash the solid product
obtained with small portions of water, and dry it in order to weigh the product. Identify
Preparatory Problems

66

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future
the product with the authentic Hantzsch ester by TLC analysis as described above. Use
hexane/ethyl acetate (2/1) as a developer.
(4) Place the filtrate and your magnetic stirring bar in a 100-mL test tube. Add 10 mL of
ethyl acetate to the test tube and stir the solution vigorously for 30 s over a magnetic
stirrer. Stop stirring and wait for the solution to separate into two layers. Transfer the
upper organic layer into a 25-mL Erlenmeyer flask using a graduated pipette. Repeat
the extraction twice using ethyl acetate (2 5 mL) and add anhydrous sodium sulfate (1
g) to the Erlenmeyer flask to dry the combined organic layer. Check the organic layer
with TLC to determine whether or not it still contains the Hantzsch ester.
Questions
1. Determine the total experimental yield of the isolated Hantzsch ester in grams.
2. Provide the theoretical yield of the Hantzsch ester in grams.
3. Calculate the percentage yield of the Hantzsch ester.
4. Determine the Rf values for the Hantzsch ester and ethyl acetoacetate.
5. Explain why the ethyl acetoacetate becomes soluble in the aqueous ammonium
carbonate solution.
6. Identify the origin of the C-4 carbon in the Hantzsch ester.

Substance
ammonium carbonate
anhydrous sodium sulfate
1,4-dihydro-2,6-dimethylpyridine-3,5dicarboxylic acid diethyl ester
ethyl acetate
ethyl acetoacetate
hexamethylenetetramine (hexamine)
hexane

liquid

Preparatory Problems

solid
solid

R phrases
22
none listed

S phrases
none listed
none listed

solid

36/37/38

26

liquid
liquid
solid

11-36-66-67
36
11-42/43
11-38-48/2051/53-62-6567

16-26-33
26
16-22-24-37
9-16-29-3336/37-61-62

67

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

Problem 40:
Reduction of a ketone with sodium borohydride
Alcohols are ubiquitous in biologically active organic compounds as well as industrially
useful materials. A key method of preparing alcohols in synthetic organic chemistry is to
reduce carbonyl compounds such as aldehydes and ketones. A variety of reagents have
been developed for such conversions, and one of the most common reagents used in
laboratories is sodium borohydride. This reagent is a mild and selective reducing agent
for ketones and aldehydes. Reduction of cyclohexanone (A) with sodium borohydride
gives cyclohexanol (B), for example, with a good yield and as a single product (eq. 1).
(C)
to
Sodium
borohydride
can
also
reduce
4-tert-butylcyclohexanone
4-tert-butylcyclohexanol, a mixture of two isomers D and E (eq. 2). This can be
understood based on the existence of two approach pathways for the hydride in sodium
borohydride, i.e., the axial and equatorial directions.
In this experiment, you will reduce the 4-tert-butylcyclohexanone (C) with sodium
borohydride and analyze the products on thin layer chromatography (TLC).
O

O
NaBH4

CH3
CH3

(1)
B

CH3

OH

NaBH4

CH3
CH3
CH3 H

OH
D

OH

CH3
CH3
CH3 H

(2)

Chemicals
anhydrous sodium sulfate
anisaldehyde stain (10% p-anisaldehyde and 5% H2SO4 in methanol)
ethyl acetate
ethanol
hexane
sodium borohydride
sulfuric acid
4-tert-butylcyclohexanone
Apparatuses and glassware
crystallization dish
Erlenmeyer flask (30 mL)
filter paper
glass capillary
Preparatory Problems

68

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future

glass funnel
magnetic stirrer
magnetic stirring bar (1.5 cm long)
oven (or hot-plate)
test tube (diameter: ca. 2 cm, height: ca. 20 cm or taller)
TLC plate (silica gel 60; layer thickness: 0.25 mm, on a glass support)
tweezers
water bath
wide-mouth bottle with cap (developing chamber)
wide-mouth bottle (anisaldehyde stain container)
graduated pipette

Procedures
(1) Inside a fume hood, add 4-tert-butylcyclohexanone (1.0 g) and ethanol (1 mL) to a test
tube fitted with a stirring bar. Place the test tube in a water bath on a magnetic stirrer.
Stir the mixture to form a clear solution at room temperature (ca. 25 C). Add sodium
borohydride (0.1 g) to the resulting solution, in a few portions. Take care to regulate the
temperature.
(2) Monitor the progress of this reaction with TLC according to the procedure described in
Problem 39 above. Develop TLC plates with an developer of hexane/ethyl acetate =
4/1. Dip the TLC plates fully in the anisaldehyde stain solution stored in a wide-mouth
bottle for a few seconds. Take the plates out of the solution and heat them in an oven
at 150 C or above for 15 min (or heat them on a hot-plate until the spots become
visible). Use tweezers for these processes. Check the completion of the reaction by
TLC.
(3) Remove the water bath. Add water (3 mL) and hexane (3 mL) to the reaction mixture.
Vigorously stir the entire mixture for 5 min. Then transfer the upper layer (organic
phase) to an Erlenmeyer flask using a graduated pipette.
(4) Add hexane (3 mL) to the test tube with the remaining lower layer (aqueous phase) and
stir the mixture vigorously for 5 min. Transfer the upper layer (organic phase) to the
same Erlenmeyer flask using the graduated pipette. Repeat this extraction process
again.
(5) Add anhydrous sodium sulfate (1 g) to the Erlenmeyer flask containing the organic
phase. Filter this mixture using filter paper and a glass funnel to remove the solids.
Transfer the filtrate to a crystallization dish. Rinse the residual solids with hexane (2
mL). Transfer the washing to the crystallization dish.
(6) Evaporate the ethanol and hexane in the fume hood at room temperature (it will take
several hours) to obtain a white solid. Weigh the amount of solids.

Preparatory Problems

69

42nd International Chemistry Olympiad 2010, Japan


Chemistry: the key to our future
Questions
1. Calculate the theoretical yield of this reaction product.
2. Report the experimental yield, and calculate the percentage yield of this reaction
product.
3. Sketch the TLC plate for the completed reaction and provide Rf values.
4. In this reduction, the steric environment is different for both faces
H
of the carbonyl group of 4-tert-butylcyclohexanone. Thus, two
reduced alcohol compounds, i.e., cis- and trans-alcohols against
O
CH3
the tert-butyl group, are generated. Since sodium borohydride
CH3
is a relatively small reagent, a hydride preferentially approaches it
H
CH3 H
C
from the axial direction. Which is the alcohol for the prominent
spot on the TLC, D or E?

Substance
anhydrous sodium sulfate
anisaldehyde
ethanol
ethyl acetate

solid
liquid
liquid
liquid

hexane

liquid

methanol

liquid

sodium borohydride

solid

15-24/25-34

4-tert-butylcyclohexanone
sulfuric acid

solid
liquid

36/37/38
35

Preparatory Problems

R phrases
none listed
22-36/37/38
11
11-36-66-67
11-38-48/2051/53-62-6567
11-23/24/25-3
9/23/24/25

S phrases
none listed
26-36
7-16
16-26-33
9-16-29-33-3
6/37-61-62
7-16-36/37-4
5
22-26-36/37/
39-43-45
26-36
26-30-45

70

42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

Instructions
Ensure that your name and student code are written in the spaces provided at the top
of each answer sheet.
You have 5 hours to work on the problems.
Use only the pen and the calculator provided.
All results must be written in the appropriate boxes. Anything written elsewhere will
not be graded. Use the reverse of the sheets if you need scratch paper.
Write any relevant calculations in the appropriate boxes when necessary. If you
provide no working and only the correct result for a complicated calculation, you will
receive no marks.
Numerical answers are meaningless without the appropriate units. You will be heavily
penalized if units are not given where required.
You must stop work immediately when the STOP command is given. A delay in doing
this may lead to your disqualification from the exam.
When you have finished the examination, you must put your papers into the envelope
provided, and seal the envelope by yourself.
Do not leave your seat until permitted by the supervisors.
This examination has 22 pages. The answer booklet comprises 17 pages.
The official English version of this examination is available on request only for
clarification.

Theoretical Problems

1/32

42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

Constants and Formulae


Avogadro
constant:

NA = 6.022 x 1023 mol1

Ideal gas equation:

pV = nRT

Gas constant:

R = 8.314 J K1 mol1

Gibbs energy:

G = H TS

Faraday constant: F = 96485 C mol1

o
r G o = RT log e K = nFE cell

Planck constant:

h = 6.626 x 1034 J s

Nernst equation:

E = Eo +

Speed of light:

c = 2.998 x 108 m s1

Energy of a
photon:

E=

Zero of the
Celsius scale:

273.15 K

Lambert-Beer law:

A = log 10

hc

c
RT
log e ox
zF
c red

= h
I0
= cl
I

In equilibrium constant calculations all concentrations are referenced to a standard


concentration of 1 mol L-1. Consider all gases ideal throughout the exam.

Theoretical Problems

2/32

42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

Periodic table with relative atomic masses


1

18

He

1.01

13

14

15

16

17

10

Li

Be

Ne

6.94

9.01

10.81

12.01

14.01

16.00

19.00

20.18

11

12

13

14

15

16

17

18

Al

Si

Cl

Ar
39.95

Na Mg

4.00

22.99

24.30

10

11

12

26.98

28.09

30.97

32.06

35.45

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36

Ti

Cr

Mn

Fe

Co

Ni

Cu

Zn

As

Se

Br

Kr

50.94

52.00

54.94

55.85

58.93

58.69

63.55

65.38

69.72

72.64

74.92

78.96

79.90

83.80

41

42

43

44

45

46

47

48

49

50

51

52

53

54

Tc

Ru

Rh

Pd

Ag

Cd

In

Sn

Sb

Te

Xe

K
39.10

Ca Sc

40.08 44.96 47.87

37

38

39

40

Rb

Sr

Zr

85.47

87.62 88.91 91.22

55

56

Cs

Ba

132.91 137.33
87

88

Fr

Ra

5771
89103

Nb Mo
92.91

95.96

Ga Ge

101.07 102.91 106.42 107.87 112.41 114.82 118.71 121.76 127.60 126.90 131.29

72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

Hf

Ta

Re

Os

Ir

Pt

Au

Hg

Tl

Pb

Bi

Po

At

Rn

69

70

178.49 180.95 183.84 186.21 190.23 192.22 195.08 196.97 200.59 204.38 207.2 208.98
104

105

106

107

108

109

110

111

Rf

Db

Sg

Bh

Hs

Mt

Ds

Rg

60

61

62

63

57

58

59

La

Ce

Pr

Nd Pm Sm Eu

138.91 140.12 140.91 144.24

89

90

91

92

93

Ac

Th

Pa

Np

232.04 231.04 238.03

Theoretical Problems

64

65

66

67

68

Gd

Tb

Dy

Ho

Er

Tm Yb

71

Lu

150.36 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.05 174.97
94

95

96

97

Pu Am Cm Bk
-

98

Cf
-

102

103

Es Fm Md No

99

Lr

100
-

101
-

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

Problem 1

8% of the total

1a 1b 1c 1d 1e 1f 1g 1h 1i Task 1
2 4 2 1 1 1 3 2 1
17
In 1894, Lord Rayleigh reported that the mass of chemically prepared nitrogen was
different from that of nitrogen extracted from the atmosphere, as shown in Tables 1 and 2.
Later, this difference was attributed to the presence of argon in atmospheric nitrogen. The
masses of gases were measured by using a glass vessel with a known volume under
atmospheric pressure (1.013 105 Pa).
Table 1. Mass of Chemical Nitrogen in the Vessel
From nitric oxide
From nitrous oxide
From ammonium nitrite purified at a red heat
From urea
From ammonium nitrite purified in the cold

2.3001 g
2.2990 g
2.2987 g
2.2985 g
2.2987 g

Mean

2.2990 g

Table 2. Mass of Atmospheric Nitrogen in the Vessel


O2 was removed by hot copper (1892)
O2 was removed by hot iron (1893)
O2 was removed by ferrous hydrate (1894)

2.3103 g
2.3100 g
2.3102 g

Mean
a)

2.3102 g

Calculate the volume V [m3] of the vessel used by Rayleigh from the mean mass of
chemical nitrogen, which must have been pure nitrogen.
Assume that the
measurements were carried out at a temperature of 15.0 C.
The amount n of the pure nitrogen (chemical nitrogen), M = 28.02 g mol1, is
m 2.2990
=
= 8.205 102 mol.
[or equivalent] (1 pt)
n=
M
28.02
nRT
Then, from the ideal gas law, V =
p

8.205 102 8.314 288.15


1.013 10

= 1.940 103 m3.

V=

Theoretical Problems

(1 pt)

m3

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

b)

Estimate the mole fraction x of argon in Rayleigh's atmospheric nitrogen, by


assuming that argon and nitrogen were the only constituents. Use the mean masses
of the atmospheric and chemical nitrogen for the calculation.
The equation for the ratio of the mass of atmospheric nitrogen to the mass of
chemical nitrogen is
28.02(1 x ) + 39.95 x 2.3102
=
.
[or equivalent] (1 pt)
28.02
2.2990
Transformation gives
(2.3102 2.2990) / 2.2990
x=
28.02
[or equivalent] (2 pt)
39.95 28.02
= 1.14 102 (or 1.14%)
(1 pt)
x=

Ramsay and Clve discovered helium in cleveite (a mineral consisting of uranium oxide
and oxides of lead, thorium, and rare earths; an impure variety of uraninite) independently
and virtually simultaneously in 1895. The gas extracted from the rock showed a unique
spectroscopic line at around 588 nm (indicated by D3 in Figure 1), which was first
observed in the spectrum of solar prominence during a total eclipse in 1868, near the wellknown D1 and D2 lines of sodium.
587

588

589

D3

590 nm

D2

He

D1

Na

Figure 1. Spectral lines around 588 nm


c)

Calculate the energy E [J] of a photon with the wavelength of the D3 line of helium
shown in Figure 1.
According to Figure 1, the wavelength of the D3 line is approximately 587.7 nm (no
punishment if 587.8 or 588 is used).
hc
The corresponding photon energy is E =

6.626 10

34

2.998 10

(1 pt)

587.7 109
= 3.380 1019 J.

(1 pt)

E=
Theoretical Problems

J
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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

Figure 2 shows an energy diagram of the atomic orbitals of helium. The arrows indicate
the "allowed" transitions according to the spectroscopic principle.

3.6

E / 1018 J

3.4

3.2

3d
3.6

[D]

[ E]

[C]

2p

3.4

3.2

2s

[ B]
[ A]

3.0

0.0

3p

3s

3.0

1s

Figure 2. Energy diagram of atomic orbitals of helium


when an electron resides in the 1s orbital.
d)

Identify the transition relevant to the D3 line of helium among the transitions [A] to [E]
indicated in Figure 2. Mark one on the answer sheet:
[E] The energy, 3.382 1019 J, matches with the energy of the transition [E]
between the 2p and 3d orbitals.
(1 pt)
19
cf.) Energy difference [10 J] = [A]:33.6, [B]:36.9, [C]:5.1, [D]:2.8, [E]:3.4

e)

Which equation explains the occurance of helium in cleveite among [A] to [D] below?
Mark one on the answer sheet:
[A]

238

U 234Th +

[B] UHe2 U + 2He


[C]

240

U 240Np +

[D]

235

U + n 95Y + 139I + 2n

[A] Considering that the particle is the nucleus of helium, -decay [A] is the
relevant source of helium in such rocks. No compound of He such as UHe2
in [B] is known to be stable at ambient temperature. [C] is a radio active
decay of 240U in the thorium series. [D] is a nuclear fission reaction of 235U
occuring in nuclear reactors. The correct answer is [A].
(1 pt)

Theoretical Problems

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

Argon is also found in minerals such as malacon.


f)

Which equation explains the occurance of argon in rocks among [A] to [D] below?
Mark one on the answer sheet.
[A] ArF2 Ar + F2
[B] ArXe Ar + Xe
[C]

40

K 40Ar + /+ (electron capture / positron emission)

[D]

126

I 126Ar +

[C] [C] is a well-known radioactive decay reaction occurring with a half-life of the
order of the age of the earth. No stable compound of Ar, such as ArF2 or
ArXe, can be expected. Products of [D] should be 126Xe + . The correct
answer is [C].
(1 pt)

One of the strongest evidences for the monoatomicity of argon and helium is the ratio of
the heat capacity under constant pressure to that at constant volume, = Cp / CV, which is
exactly 5/3 (1.67 0.01) for a monoatomic gas. The ratio was derived from the
measurement of speed of sound vs by using the following equation, where f and are the
frequency and wavelength of the sound, and R, T, and M denote the molar gas constant,
absolute temperature, and molar mass, respectively.
vs = f =

RT
M

For an unknown gas sample, the wavelength of the sound was measured to be = 0.116
m at a frequency of f = 3520 Hz (Hz = s1) and temperature of 15.0 C and under
atmospheric pressure (1.013 105 Pa). The density of the gas for these conditions was
measured to be 0.850 0.005 kg m3.
g)

Calculate the molar mass M [kg mol1] of this gas.


nM
.
V
By combining with the ideal gas law gives:
RT 0.850 8.314 288.15
M=
=
p
1.013 105
2
= 2.01 10 kg mol1. (20.1 g mol1)

The density is given by =

(1 pt)

[or equivalent]

(1 pt)
(1 pt)

M=

Theoretical Problems

[or equivalent]

kg mol1

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

h)

Calculate the heat capacity ratio for this gas sample.

From the equation for the sonic velocity, f =

M
2.01 102
(3520 0.116)2
( f )2 =
RT
8.314 288.15

RT
M

[or equivalent]

= 1.40
(or, using

(1 pt)
(1 pt)

0.850
(3520 0.116)2 = 1.40)
= , = ( f )2 =
5
RT p
p
1.013 10

i)

Which is this gas among [A] to [D]? Mark one on the answer sheet:
[A] HCl
[B] HF
[C] Ne
[D] Ar
[B] From M = 20.1 g mol1, this gas must be HF or Ne.
From = 1.4 ( 5/31.67), this is NOT a monoatomic gas (i.e., HCl or HF).
Thus, this gas must be [B] HF.
(1 pt)
Note: It is not possible to distinguish between HF (M = 20.01) and Ne (M = 20.18)
from the molar mass only, which is 20.100.12 by taking into account the
uncertainty of (0.005 / 0.850 = 0.6%). However, the precision of =
1.40 is enough to exclude the possibility of monoatomic gas ( = 5/31.67).

Theoretical Problems

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

Problem 2
2a
4

2b
4

2c
4

2d
3

6% of the total
2e
5

Task 2
20

Crystal structure of alkali metal halide


In crystals of ionic compounds, cations are generally arranged in the interstices of the
closest packed lattice of anions. The structure of an ionic crystal such as sodium chloride
becomes stable when the cations are in contact with the nearest anions.
a)

In the crystal of sodium chloride, both Na+ and Cl- ions form a face-centered cubic
lattice. Give the numbers of Na+ and Cl- ions in a unit cell and the coordination
numbers of Na+ and Cl- ions in sodium chloride crystal.

Number of ions

Na+:

Cl-:

Coordination number

Na+:

Cl-:

[Total 4 pts]
[2 pt] Both number of Na+ and Cl- ions are correct.
[1 pt] Each coordination number of Na+ and Cl- ions is correct.
b)

The ionic radii of Na+ and Cl- ions in the crystal of sodium chloride are 0.102 nm and
0.181 nm, respectively. Calculate the density [kg m-3] of the sodium chloride crystal.

[Total 4 pts]
Length of lattice l: l = 0.102 2 + 0.181 2 = 0.566 nm [2 pt]
Density :
( 22.99 + 35.45) 4
=
= 2.1408 10 6 g m 3 = 2.14 10 3 kg m 3
23
9 3
( 0.566 10 ) 6.022 10
[1 pt for the equation of density, 1 pt for final answer.]
Density of NaCl crystal (kg m-3): 2.14 103 kg m-3

Theoretical Problems

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

Born-Haber cycle and lattice enthalpy


In ionic inorganic compounds such as sodium chloride, the heat of lattice formation from
gaseous ions is very high, and the contribution of the change in entropy is small. Therefore,
the lattice formation enthalpy is estimated from enthalpy data by using a Born-Haber cycle.
c)

The figure below shows the Born-Haber cycle of NaCl. The labels g and s
represent gas and solid states respectively. Show chemical equations in the A and
F steps.
Na+ (g) + Cl (g) + eD: Dissociation of Cl2 (g)

E: Electron gain by Cl (g)

C: Ionization of Na (g)

B: Sublimation of Na (s)

F: Dissociation of NaCl (s)

A: Formation of NaCl (s)


from elemental substances.
NaCl (s)
A: Na (s) + 1/2Cl2 (g) NaCl (s) [2 pt]
F: NaCl (s) Na+ (g) + Cl- (g)

d)

[2 pt]

Calculate the enthalpy of the lattice formation of NaCl [kJ mol-1] by using the following
enthalpy data of the respective steps in the above Born-Haber cycle.
Formation of
NaCl (s)

Sublimation
of Na (s)

Ionization of
Na (g)

411 kJ mol-1

109 kJ mol-1

496 kJ mol-1

Dissociation
of Cl2 (g)
242 kJ mol-1

Electron gain
by Cl (g)
349 kJ mol-1

[Total 3 pts]
Enthalpy conservation condition: A + B + C + D/2 = F E [1 pt]
From the above equation, (411) + 109 + 496 + (242/2) = F + 349,
thus, F=788 [1 pt]
The lattice formation enthalpy of NaCl is F, thus, 788 kJ mol-1 [1 pt]
Lattice formation enthalpy of NaCl (kJ mol-1): 788 kJ mol-1

Theoretical Problems

10/32

42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

Synthesis of sodium carbonate by the ammonia-soda process (Solvay process)


Sodium carbonate (anhydrous soda ash) is a raw material in the manufacture of glass,
medicaments, alkaline detergents, etc.
e)

The total chemical reaction in the ammonia-soda process is represented as follows:


2NaCl + CaCO3 Na2CO3 + CaCl2
This reaction between sodium chloride and calcium carbonate does not proceed
directly. The process comprises the following five reactions involving ammonia:
CaCO3
[A]+[B]
NaCl + NH3 + [ B ] + H2O [ C ] + [ D ]

2[C]
Na2CO3 + H2O + [ B ]

[ A ] + H2O [ E ]
[ E ] + 2 [ D ] CaCl2 + 2H2O + 2NH3
where represents applying heat treatment. Insert the chemical formulas of the
appropriate compounds in the blank spaces [ A ][ E ] in the above reactions.

A: CaO
B: CO2
C: NaHCO3
D: NH4Cl
E: Ca(OH)2
[Total 5 pts]
1 pt for one correct chemical formula.

Theoretical Problems

11/32

42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

Problem 3
3a 3b 3c 3d
2 3
1 3

7% of the total
Task 3
9

The chemical oxygen demand (COD) refers to the amount of oxidizable substance, such
as organic compounds, in a sample solution, and it is used as an indication of water quality
in seas, lakes, and marshes. For example, the COD of service water is kept below
1 mg L-1. The COD (mg L-1) is represented by mass of O2 (mg) which accepts the same
amount of electrons which would be accepted by the strong oxidizing agent when 1 L of a
sample solution is treated with it. An example of the operation is presented below.
******************************************************
Analytical Operation
A 1.00-L sample solution was acidified with a sufficient amount of sulfuric acid, and
chloride ions were removed by the addition of silver nitrate solution. To the sample solution,
1.00 10-1 L of 5.00 10-3 mol L-1 potassium permanganate solution was added, and the
mixture was heated for 30 min. Further, 1.00 10-1 L of 1.25 10-2 mol L-1 disodium
oxalate (Na2C2O4 or NaOOC-COONa) standard solution was added, and the mixture was
stirred well. Oxalate ions that remained unreacted were titrated with 5.00 10-3 mol L-1
potassium permanganate solution; 3.00 10-2 L of the solution was used for the titration.
******************************************************
a)

Give the equation of the redox reaction of potassium permanganate and disodium
oxalate.

2KMnO4 + 5Na2C2O4 + 8H2SO4 2MnSO4 + 5Na2SO4 + K2SO4 + 10CO2+ 8H2O


or
2KMnO4 + 5H2C2O4 + 3H2SO4 2MnSO4 + 10CO2 + 8H2O + K2SO4
or
2 MnO4- + 5C2O42- + 16H+ 2Mn2+ + 10CO2 + 8H2O
[Total 2 pts]

b)

Calculate the amount of O2 (mg) that will oxidize the same number of moles of
oxidizable substance as 1.00 10-3 L of 5.00 10-3 mol L-1 potassium
permanganate does.

The reactions of potassium permanganate and O2 are as follows:


MnO4- + 8H+ + 5e- Mn2+ + 4H2O
O2 + 4H+ + 4e- 2H2O
Theoretical Problems

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

Hence, 1 mol of KMnO4 amounts to 1.25 mol of O2.


5 5.00 10-3 (mol L-1) 10-3 (L) = 4 X / 32 (mol)
where X is the amount of O2 (g).
Thus, X = 2.00 10-4 g.

c)

2.00 10-1 mg

[Underlined (or equivalent)


equation: 2 pt]
[1 pt]
[Total 3 pts]

From the following choices, select the most appropriate reason for the removal of
chloride ions:
[A] Some of the chloride ions react with potassium permanganate, resulting in an
error in COD.
[B] Some of the chloride ions react with disodium oxalate, resulting in an error in
COD.
[C] Some of the chloride ions react with organic compounds in the sample solution,
resulting in an error in COD.
[D] A color is developed during titration, resulting in an error in COD.
[A]
[Total 1 pt]

d)

Calculate the COD (mg L-1) of the sample solution described in the analytical
operation above.

The amounts of electron used for reduction and oxidation are equal, then
5 5.00 10-3 (mol L-1) (1.00 10-1 + A) (L) =
2 1.25 10-2 (mol L-1) 1.00 10-1 (L) + X
(1)
[Underlined (or equivalent)
where A (mL) is the amount of potasium permanganate
equation: 2 pt]
used for the final titration, and X (mol) is the amount of
electron for the oxidizable substance.
Eq.(1) gives X = 2.50 10-2 A.
At A = 3.00 10-2 (L), X = 7.50 10-4 (mol).
Hence, COD = (32/4) (g mol-1) 7.50 10-4 (mol) 103(mg/g) 1/1(L-1)
= 6.00 mg L-1.
[1 pt]
[Total 3 pts]
or
The amount of potasium permanganate consumed for the oxidizable substance, B (mL), is
5 5.00 10-3 (1.00 10-1 + A B) = 2 (1.25 10-2) (1.00 10-1).
[2 pt]
-2
-2
At A = 3.00 10 L, B equals to 3.00 10 L.
From the solution to question b) above,
COD = (2.00 10-1) / (1.00 10-3) (mg/L) 3.00 10-2 (L) 1/1(L-1) = 6.00 mg L-1. [1 pt]
[Total 3 pts]

Theoretical Problems

13/32

42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

Problem 4
4a 4b 4c 4d
2 3 2 1

6% of the total
Task 4
8

The rechargeable lithium ion battery has been developed in Japan.


The standard electromotive force of the battery is 3.70 V. Assume that the half-reaction at
the cathode is
CoO2 + Li+ + e- LiCoO2,
and the half-reaction at the anode is
LiC6 6C + Li+ + e-.
a)

Write the total reaction equation of the battery and calculate the value of the standard
Gibbs energy of the reaction [kJ mol-1].

Total reaction equation:


CoO2 + LiC6 LiCoO2 + 6C

(1 pt)

The standard Gibbs energy of the reaction:


G0 = nFE0 = 1 96485 C mol-1 3.70 V = 357 kJ mol-1

b)

(1 pt)

The battery cell is constructed using LiCoO2 and graphite (C) as the electrode
materials. Calculate the mass of the anode in the completely charged state and that
in completely discharged state if 10.00 g of LiCoO2 and 10.00 g of graphite (C) are
present initially.

In the completely charged state: 10.71 g


(2 pt)
The amount of LiCoO2 is 10.00/97.87 = 0.1022 mol.
The amount of C is 10.00/12.01 = 0.8326 mol, which is larger than 0.1022 mol 6 =
0.6132 mol.
Thus, the mass in the completely charged state of the anode is 10.00 + 0.1022 6.94 =
10.709 g = 10.71 g.
In the completely discharged state: 10.00 g

Theoretical Problems

(1 pt)

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

c)

Calculate the maximum energy generated per mass of the lithium ion battery cell [kJ
kg-1]. Assume that the correct ratio for complete reaction between the cathode and
anode materials is used and the sum of the mass of electrodes is 50.0% of the total
mass of the battery cell. In comparison, the energy density of lead-acid batteries used
for vehicles is about 200 kJ kg-1.

The mass of 1 mol LiCoO2 is 97.87 g


The mass of 6 mol C is 12.01 6 g = 72.06 g
The total mass of the electrode is (97.87 + 72.06) g = 169.93 g
The mass of the cell is 169.93 / 0.500 g = 340 g
The maximum energy generated is 357 kJ.
Thus, the maximum energy per unit mass of the cell is 1050 kJ kg-1
d)

(2 pts)

Because an aqueous solution cannot be used as an electrolyte, an organic solution is


used in the lithium ion battery cell. Give the chemical formula of the gas generated if
water is present in the electrolyte.

H2 or H2 and O2 (1 pt)

Theoretical Problems

15/32

42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

Problem 5

7% of the total

5a-1 5a-2 5b 5c 5d 5e 5f Task 5


1
1
2 2 3 4 5
18

When an atom X absorbs radiation with a photon energy greater than the ionization
energy of the atom, the atom is ionized to generate an ion X+ and the electron (called a
photoelectron) is ejected at the same time. In this event, the energy is conserved as
shown in Figure 1, that is,
Photon energy (h) = ionization energy (IE) of X + kinetic energy of photoelectron.
When a molecule, for example, H2, absorbs short-wavelength light, the photoelectron is
ejected and an H2+ ion with a variety of vibrational states is produced. A photoelectron
spectrum is a plot of the number of photoelectrons as a function of the kinetic energy of
the photoelectrons. Figure 2 shows a typical photoelectron spectrum when H2 in the
lowest vibrational level is irradiated by monochromatic light of 21.2 eV. No
photoelectrons are detected above 6.0 eV. eV is a unit of energy and 1.0 eV is equal to
1.6 10-19 J.

Kinetic energy of
photoelectron

IE
h

Figure 1. Schematic diagram of


photoelectron spectroscopy.

Theoretical Problems

Photoelectron spectrum of H 2

h = 21.2 eV

Intensity (arb.)

X+

6.0

5.0
4.0
Kinetic energy of photoelectron (eV)

3.0

Figure 2. Photoelectron spectrum of H2. The energy of the


incident light is 21.2 eV.

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42nd International Chemistry Olympiad


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a-1)

Determine the energy difference EA1 (eV) between H2 (v = 0) and H2+ (v ion = 0) to
the first decimal place. v and v ion denote the vibrational quantum numbers of H2 and
H2+, respectively.

a-2)

Determine the energy difference EA2 (eV) between H2+ (v ion = 0) and H2+ (v ion = 3)
to the first decimal place.

a-1) & a-2)


The spectral peak at 5.8 eV in Fig. 2 corresponds to the electron with the highest kinetic
energy, which is generated by the reaction H2(v = 0) H2+(vion = 0) + e. Accordingly,
EA1 = 21.2 eV 5.8 eV = 15.4 eV
One can estimate from Fig. 2 that the energy difference EA2 between H2+ (v ion = 0) and
H2+ (v ion = 3) is approximately 0.8 eV.

EA1 (eV) = 15.4 eV

1 pt

EA2 (eV) = 0.8 eV

1 pt

b)

The electronic energy levels E nH of a hydrogen atom are given by the equation
E nH =

Ry
n2

(n = 1, 2, 3 )

Here n is a principal quantum number, and Ry is a constant with dimensions of energy.


The energy from n = 1 to n = 2 of the hydrogen atom is 10.2 eV. Calculate the
ionization energy EB (eV) of the hydrogen atom to the first decimal place.
The ionization energy corresponds to n = . Accordingly,
3
E n =2n =1 = Ry
4
E n = n =1 = Ry
Thus, the energy required for the ionization is 4/3 times larger than the transition energy of
the Lyman line.
4
EB = 10.2 eV = 13.6 eV
3
EB (eV) = 13.6 eV
2 pts

Theoretical Problems

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c)

The energy threshold for the generation of two electronically excited hydrogen atoms
H* (n = 2) from H2 (v = 0) has been derived to be 24.9 eV by an experiment.
Determine the bond energy EC (eV) of H2 to the first decimal place.

24.9 eV = the binding energy of a hydrogen molecule + 10.2 eV + 10.2 eV.


Thus, the binding energy of a hydrogen molecule = EC = 4.5 eV.
EC (eV) = 4.5 eV

d)

2 pts

Considering an energy cycle, determine the bond energy ED (eV) of H2+ to the first
decimal place. If you dont have the values for EB and EC, then use 15.0 eV and 5.0
eV for EB and EC, respectively.

From Figure 3 below,


ED = EB + EC EA1 =13.6 + 4.5 15.4 = 2.7 eV.
ED (eV) = 2.7 eV

e)

3 pts

Calculate the threshold energy EE (eV) of the following dissociative ionization


reaction to the first decimal place:
H
H* (n = 2) + H+ + e- .
2
If you dont have the values for EB and EC, then use 15.0 eV and 5.0 eV for EB and
EC, respectively.

H + H+ + eED = 2.7 eV

H2+ + e-

EB=13.6 eV
EA1=15.4 eV

H+H
EC=4.5 eV

H2

From Figure 3 above, the threshold energy for the dissociative ionization reaction
H2 H* (n = 2) + H+ + e is EB + EC + 10.2 eV = 13.6 + 4.5 + 10.2 = 28.3 eV.
EE (eV) = 28.3 eV
4 pts

Theoretical Problems

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f)

When H2 absorbs monochromatic light of 21.2 eV, the following dissociation


process occurs at the same time.

21.2
eV

H (n = 1) + H (n = 1)

Two hydrogen atoms move in opposite directions with the same speed. Calculate
the speed u (m s-1) of the hydrogen atoms generated in the above reaction. H2 is
assumed to be at rest. If you dont have the value for EC, then use 5.0 eV for EC.

The excess energy is 16.7 eV (= 21.2 eV 4.5 eV). Because two hydrogen atoms are
generated upon photodissociation, half of this excess energy is released as translational
energy of the hydrogen atoms.
1
mu 2 = 8.35 eV = 1.34 10 -18 J
2
(2 pts)
1.008 10 -3 kg mol -1
27
m=
= 1.67 10 kg
6.022 10 23 mol -1
Then,
u 2 = 1.6 10 9 m 2 s -2 u 4.0 10 4 m s -1
u (m/s) = 4.0 104 m/s

Theoretical Problems

5 pts

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Problem 6

6 % of the total

6a 6b 6c 6d Task 6
5 4 6 11
26

Read the description of four kinds of isomeric organic compounds of A, B, C, and D. All
have C8H10O and contain a benzene ring. Answer the questions that follow. If there are
stereoisomers, give all structural formulas. Note that any wrong isomers will be penalized.
z

(1)At room temperature, a piece of sodium metal was added to A, B, and C in test
tubes and the evolution of hydrogen gas was observed only in the case of C.

When an iron(III) chloride aqueous solution was added to C and D, no coloration was
observed in C, whereas D was colored.

A was oxidized when (2)aqueous potassium permanganate was added to it and the
mixture was heated; the acidification of the heated mixture and its isolation afforded
benzoic acid.

Lets imagine that (3)a hydrogen atom in the benzene ring is replaced by a chlorine
atom, it is possible to obtain four kinds of monochlorinated structural isomers from B,
while only two kinds of such isomers can be obtained from D.

Hydrogenation of the benzene ring in C and D using a catalyst gave saturated


alcohol(s). It was found that the saturated alcohol(s) obtained from C has no
stereogenic carbons, but the one(s) from D has stereogenic carbon(s).

a)

Among all the isomeric organic compounds of C8H10O having a benzene ring, give
the structural formulas of all the isomers that do NOT yield hydrogen gas in the
underlined procedure (1), in which a piece of sodium is added to the neat samples in
the case of the liquid samples and to the concentrated solution of the samples in an
aprotic solvent in the case of the solid ones.
O

1pt each
wrong isomer: -1pt each
total pts 0 (not negative)

b)

Among all the isomeric organic compounds of C8H10O having a benzene ring, give
the structural formulas of all the isomers that yield benzoic acid in the underlined
procedure (2).

Theoretical Problems

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42nd International Chemistry Olympiad


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OH
OH

OH

1pt each
wrong isomer: -1pt each
total pts 0 (not negative)

c)

Among all the isomeric organic compounds of C8H10O having a benzene ring, give
the structural formulas of all the isomers that could yield four different monochlorinated structural isomers when the underlined transformation in (3) is performed.
OH

OH

OH

OH

1pt each
wrong isomer: -1pt each
total pts 0 (not negative)
d)

Give the structural formulas of A, B, C, and D. When several isomers can be


considered, give the structural formulas of all of them.

B
O

1pt
wrong isomer: -1pt each
total pts 0 (not negative)

1pt each
wrong isomer: -1pt each
total pts 0 (not negative)

OH

OH

2pts each
wrong alcohol/phenol: -1pt each
ether: -2pts each
total pts 0 (not negative)

Theoretical Problems

OH

OH

2pts each
wrong alcohol/phenol: -1pt each
ether: -2pts each
total pts 0 (not negative)

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

Problem 7

7% of the total

7a 7b 7c 7d Task 7
4 9 6 5
24
Certain varieties of puffer fish, Fugu in Japanese, are highly prized as foods in Japan.
Since the viscera (especially ovaries and livers) of the fish contain a potent toxin
(tetrodotoxin), food poisoning often results from its ingestion. Studies on tetrodotoxin (1)
have been performed from the beginning in the 20th century; its chemical structure was
elucidated in 1964.
O

HO
H
H
N
N
H HO

H2N

O
OH

O
H

OH

OH

tetrodotoxin (1)

a)

The guanidine group in tetrodotoxin exhibits strong basicity. The guanidinium ion
resulting from protonation on the guanidine group is stabilized by the existence of the
following resonance. Draw two resonance structures B and C.
NHR1

NHR2

H2N
A

C
NHR1

NHR1
H 2N

NHR2

H2N

NHR2

2 pts each.
b)

Many derivatization reactions were performed in structure studies of tetrodotoxin.


Treatment of tetrodotoxin (1) with ethanolic potassium hydroxide upon heating
afforded quinazoline derivative 2, which provided an insight into the nature of the
fundamental skeleton of tetrodotoxin. The reaction mechanism can be described as
follows. First, tetrodotoxin is hydrolyzed into carboxylate 3. Then the hydroxyl group
highlighted with a frame is eliminated by the base to give intermediate D. A retroaldol reaction of D cleaves a carbon-carbon bond to provide intermediates E and F.
Finally, dehydration and aromatization from E produce quinazoline derivative 2. Draw
structures of the postulated intermediates D, E, and F.

Theoretical Problems

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

HO
H
H
N
N
H HO

H2N

H2O
base

O
OH

HO
H
H
N
N
H HO

H2N

H
H

H
1

OH

OH

OH OH
H

COO
OH
HO
OH
H
H

OH

HN
H2N
OH

OH
N
H

HO

H2N

intermediate E

dehydration &
aromatization

OH

base

base

base

OH

OH
OH
COO
3

3
dehydration
(-H2O)

OH

intermediate D

retro-aldol reaction

E
OH OH
H

OH OH
H

OH

HN

HN

OH
N
H

H2N

H2N

HO

O
COO

OH
N
H

OH
O

COO

3 pts each. Other stereoisomers are acceptable. Each free form is acceptable.
Tautomors concerning guanidine moiety are all acceptable. Enol form is acceptable.
E: dehydrated products and zwitterionic structure are acceptable.
c)

Although biosynthesis of tetrodotoxin still remains to be clarified, it is proposed that


tetrodotoxin may be biologically synthesized from L-arginine and isopentenyl
diphosphate. Among the carbons included in tetrodotoxin, circle all the carbons that
are expected to be of L-arginine origin.
NH2
H2N

COO

N
H

NH2

L-arginine

H 2N

O
O
P O P O
O
O

tetrodotoxin (1)

isopentenyl diphosphate

HO
H
H
N
N
H HO

O
OH

O
H

Theoretical Problems

OH

OH

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6 pts. 1 pt each for correct carbon. Deduct 1 pt for each carbon over 6. 0 pts for all
carbons circled.
In the 1990s, an alternative biosynthetic pathway of tetrodotoxin was proposed.
Condensation between 2-deoxy-3-oxo-D-pentose and guanidine provides
intermediate G with cyclic guanidine moiety (molecular formula C6H11N3O3).
Tetrodotoxin may be biologically synthesized from intermediate G and isopentenyl
diphosphate. Draw a structure of the postulated intermediate G showing the
stereochemistry.

d)

HO
O

NH2

OH
HN

G ( C6H11N3O3)

NH2

HO
OH

tetrodotoxin (1)

O
O
O P O P O
O
O

2-deoxy-3-oxo-D-pentose

isopentenyl diphosphate

CHO

G
OH

H
N

HO

NH
NH

OH

5 pts (enantiomer at C4, 3 pts, C4 stereochemistry is unclear, 3 pts).


OH
OH
HO

H
N

HO

HO
NH
NH

NH

NH
OH

OH
HO
HO

H
N

NH
N

acceptable

Each zwitterionic structure (and protonated structure) like below is acceptable.


OH
HO

H
N

NH2
NH

Tautomers concerning guanidine moiety are all acceptable.

Theoretical Problems

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

Problem 8
8a-1
2

8a-2
4

8a-3
3

8b-1
4

6% of the total
8b-2
7

Task 8
20

The esterification reaction between bi-functional molecules gives one of the typical linear
chain polymers as shown in eq.(1) by polycondensation (often called condensation
polymerization). The control of polymerization conditions and procedures determines the
length of polymer strands, i.e., the average degree of polymerization, X (note that X = 2n
in the present instance). Because X (and also n ) is an averaged number, it is not always
an integer but a value with decimal figures.
n HOOC-R1-COOH + n HO-R2-OH HO-[COR1CO-OR2O]n-H + (2n1)H2O (1)
X can be estimated from the consumption of functional groups (here, -COOH and -OH).
Let us define the degree of reaction, p, as p = (N0 - N) / N0 ( 1), where N0 and N denote
the total numbers of functional groups before and after the polymerization, respectively.
For each functional group of the dicarboxylic acid molecules (A) and diol molecules (B),
we add the suffixes of A or B such as NA0, NB0, NA or NB, respectively, i.e., N0 = NA0 +
NB0 and N = NA + NB. When the initial feed is unbalanced such as NA0 NB0, X is
expressed by pA and r as shown in eq.(2), where r = NA0 / NB0 ( 1) and pA = (NA0 NA) /
NA0. If r = 1, pA is identical to p and eq.(2) becomes the same to the Carothers equation.
X = (1 + r) / (1 + r - 2pAr)

(2)

a) Some nylon-6,6 sample was prepared by polycondensation between an equimolar


mixture of adipic acid (hexanedioic acid) and hexamethylenediamine (hexane-1,6diamine).
a-1) Show the chemical structure of this nylon-6,6 sample. [Caution: what are the end
groups when polycondensation was started from the equimolar mixture?]

HO-[CO(CH2)4CO-NH(CH2)6NH]n-H or equivalent structures are all OK.


Total 2 pts. -0.5 pt for lacking n, another -0.5 pt for lacking each of the end group(s).

Theoretical Problems

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a-2) When this nylon-6,6 sample carries an average molecular weight, M, of 5507.25
(g mol-1), give its X value to the second decimal place.

Calculation procedures must be shown by suitable equation(s) (otherwise, no


score will be provided):

The unit molecular weight, Mu, is calculated to be,


Mu = (12.01 12 + 1.01 22 + 14.01 2 + 16.00 2) / 2 = 226.36 / 2 = 113.18
X = (5507.25 - 18.02) / Mu = (5507.25 - 18.02) / 113.18 = 48.50, or
X = 2n = 2 [(5507.25 - 18.02) / 226.36] = 48.50
X = 48.50

Black parts are prewritten in the answer boxes (same to all questions in Problem 8).
Underlined (or equivalent) calculation procedures are required. Total 4 pts. -1 pt for
calculation mistakes.
a-3) Give the p value necessary to prepare this nylon-6,6 sample of M = 5507.25
(g mol-1) to the fifth decimal place. If you get no numerical answer in a-2), use
52.50 instead.

From eq.(3) at r = 1 (Carothers eq.), X = 48.50 = 1 / (1 - p), then p = 0.979381


0.97938
p = 0.97938 (0.98095 when X = 52.50.)

Total 3 pts. -1 pt for calculation mistakes.


b) The low-molecular-weight polyester (oligoester) is prepared from the mixture of 36.54
(g) of adipic acid (hexanedioic acid) and an unknown amount [W (g)] of butane-1,4-diol
(Bdiol). Under the condition of pA, the oligoester with X = 11.00 carrying Bdiol units
in both chain ends is obtained.
b-1) Show the precise chemical structure of this oligoester of X = 11.00.

[HO(CH2)4O]1.000-[CO(CH2)4CO-O(CH2)4O]5.000-H or
HO(CH2)4O-[CO(CH2)4CO-O(CH2)4O]5.000-H is accurate, however,
is acceptable.
HO(CH2)4O-[CO(CH2)4CO-O(CH2)4O]5-H
Total 4 pts, -1 pt for lacking the number of unit repeating or writing n instead of 5.00
(or 5). Another -1 pt for lacking HO- and/or -H end group(s). No point if lacking the leftmost HO(CH2)4O- group.

Theoretical Problems

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b-2) Calculate the unknown amount, W (g), to the first decimal place.
Calculation procedures must be shown by suitable equation(s) (otherwise, no
score will be provided):

Mw(adipic acid) = 146.16, Mw(Bdiol) = 90.14


Ans.1 Since X = 11.00, the oligoester contains 5.00 units of adipate and 6.00 units of
Bdiol. [cf) 5.00 + 6.00 = 11.00 = X] When pA1, the initial molar feed ratio of the
monomers is equal to the molar composition of the resulting oligoester.
[adipic acid]0 / [Bdiol]0 = 5.00 / 6.00, W = 90.14 (6.00 / 5.00) (36.54 / 146.16) =
27.042 27.0 (g)
Ans.2 From eq.(2), when pA1, X = (1 + r) / (1 - r). Therefore,
11.00 = [1 + {(36.54 / 146.16) / (W / 90.14)}] / [1 - {(36.54 / 146.16) / (W / 90.14)}]
= [(W / 90.14) + 0.2500] / [(W / 90.14) - 0.2500]
11.00 [(W / 90.14) - 0.2500] = [(W / 90.14) + 0.2500], 10.00 (W / 90.14) = 3.000
W = 3.000 90.14 / 10.00 = 27.042 27.0 (g)
W = 27.0 (g)

Either calculation procedures are acceptable. Underlined (or equivalent) calculation


procedures are required. Total 7 pts, -1 pt for calculation mistakes.

Theoretical Problems

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Problem 9

7% of the total

9a 9b 9c 9d 9e 9f Task 9
4 2 8 4 8 8
34

-Cyclodextrin (CyD), which is a cyclic oligosaccharide of six (1 4) linked -Dglucopyranoside units, can be topologically represented as toroids (Figure 1). -Dglucopyranoside units in CyD are usually in the most stable chair conformation.

CyD

Figure 1. Space filling model of CyD. Left:


view through the hole. Right: side
view.

CyD

a)

Give the absolute configuration (R or S) at stereogenic carbons C-2 and C-5 of Dglucose. Also, draw a stereostructure of the open chain form of D-glucose.

Absolute configuration at C-2:

Chain form:

1 pt

OH

HO
OH

Absolute configuration at C-5:

1 pt

OH

HO

H
OH

OH

or

OH

OH
OH

2 pts (carbon skeleton: 1 pt; others: 1 pt)

Theoretical Problems

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42nd International Chemistry Olympiad


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b)

Choose the most stable conformation from the four incomplete -D-glucopyranose
formulas given in the answer box and enclose it in a box. Also, add four OH groups
and four H atoms to complete the -D-glucopyranose formula.
H

H
OH

OH

H
O
O

OH
OH

Answer:

OH

H
HO

O
H

HO
H

2 pts (4C1 : 1 pt; -OH: 1 pt)

OH
OH

H
HO

H
OH

H
H
OH

OH

1 pts (4C1 : 0 pt; -OH: 1 pt)

OH

Others 0 pt

Theoretical Problems

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CyD in water is able to host hydrophobic molecules. When the host/guest (H/G)
stoichiometry is 1/1, the inclusion complexation can be given by the following equilibrium.

k1
k-1

HG

(1)

where k1 and k-1 are the rate constant for the forward and backward reaction, respectively.
The complexation of a guest to CyD causes a chemical shift change in 1H NMR spectra.
Figure 2 shows a part of 1H NMR spectra (signals from H-1 of CyD) showing the
chemical
shift
change
in
the
presence
of
varying
amounts
of
1,10-bis(trimethylammonium)decane diiodide (BTAD). The doublet peak at 5.06 ppm is
from H-1 of free CyD, while the doublet at 5.14 ppm is from H-1 of CyD complexed with
BTAD. (Note that the spectra given in Figure 2 were measured in the complexation
equilibrium state.)

BTAD

Figure 2. Expanded 1H NMR


spectra (signals from H-1 of
CyD) of solutions containing
5.010-3 mol L-1 CyD and
0-3.0 10-2 mol L-1 BTAD.

c)

In the spectrum of 5.0 x10-3 mol L-1/5.0 x10-3 mol L-1 CyD/BTAD, the relative peak
areas of the doublets at 5.06 and 5.14 ppm are 0.41 and 0.59, respectively. Calculate,
to 2 significant figures, the concentration equilibrium constant, K for the inclusion
complexation of CyD/BTAD.

[HG]
[CyD]0a5.14
5.0 x10-3 M 0.59
K = --------- = --------------------------------------------------------- = -------------------------- = 0.70 x103
[H][G] [CyD]0 a5.06 {[BTAD]0 [CyD]0 a5.14} (5.0x10-3 M 0.41)2
1 pt

3 pts

3 pts

1 pt

a5.06: relative area of the peak at 5.06 ppm = mole fracrion of free CyD
a5.14: relative area of the peak at 5.14 ppm = mole fracrion of CyD complexed with BTAD

K: 7.0 102

Theoretical Problems

8 pts in total
30/32

42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

Complexation of CyD with hexyltrimethylammonium bromide (HTAB) appears in NMR


spectra in a way different from the CyD/BTAD complexation. Figure 3 shows a part of 1H
NMR spectra (H-6 signal of HTAB) in CyD/HTAB solutions. The signal appears as one
triplet (not two triplets), which shifts depending on the concentration of CyD from the
position of free HTAB to the position of CyD/HTAB in proportion to the fraction of the
complex in the solution. The H-6 signals from free HTAB and HTAB complexed with CyD
are triplets at 0.740 ppm and 0.860 ppm, respectively.

HTAB

Figure 3. Expanded 1H NMR


spectra (H-6 signal of HTAB)
of
solutions
containing
-2
-1
1.010 mol L HTAB and
0-3.010-2 mol L-1 CyD.

d)

The signal of HTAB in CyD/HTAB solutions appears as one triplet, which shifts
depending on the concentration of CyD. Choose the rational interpretation(s) just
from these spectra.
hint: When a guest molecule move in and out of CyD rapidly and repeatedly, only
one signal of the guest is observed at the weighted average of the chemical
shifts of the free guest and the shift of the guest included in CyD.

a. k1 of CyD/HTAB > k1 of CyD/BTAD


b. k1 of CyD/HTAB < k1 of CyD/BTAD
c. K of CyD/HTAB > K of CyD/BTAD
d. K of CyD/HTAB < K of CyD/BTAD

4 pts (additional choice : 2 pts for each)

Theoretical Problems

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e)

The signals of HTAB in 1.0 x10-2 mol L-1/1.0 x10-2 mol L-1 CyD/HTAB are positioned
at 0.815 ppm. Calculate, to 2 significant figures, K for the complexation of
CyD/HTAB.

In 1.0 x10-2 mol L-1/1.0 x10-2 mol L-1 CyD/HTAB,


s10/10 sfree
0.815 0.740
f10/10 = ------------------- = ---------------------- = 0.625
scomplex sfree
0.860 0.740

3 pts
sfree, scomplex: chemical shift of HTAB in free, and complexed state
s10/10: chemical shift of HTAB in 10.0 mM/10.0 mM CyD/HTAB
f10/10: mole fraction of complexed HTAB in 10.0 mM/10.0 mM CyD/HTAB

[HG]
K = --------[H][G]
[HTAB]0 f10/10
1.0 x10-2 mol L-1 0. 625
= ---------------------------------------------------------- = ------------------------------------------{[CyD]0 f10/10 [HTAB]0}[HTAB]0(1 f10/10) [1.0 x10-2 mol L-1 (1 0. 625)]2
2 pts
2 pts
2
= 4.4 10
K: 4.4 102
f)

1 pt

8 pts in total

At 40.0 C and 60.0 C, K for the complexation of CyD/HTAB are 3.12 102 and
2.09 102 respectively. Calculate, to 2 significant figures, the enthalpy change, H
[kJ mol-1], and the entropy change, S [J K-1 mol-1]. (Ignore the temperature
dependence of H and S.)

From G= RT ln K,
G (40.0 oC) = 8.314 313.2 ln (3.12 102) = 14.94 103 J mol1
G (60.0 oC) = 8.314 333.2 ln (2.09 102) = 14.79 103 J mol1
2 pts each
From G=H-TS
14.94 103 = H 313.2 S
14.79 103 = H 333.2 S

2 pts

S = 7.5 J K1 mol1, H = 17 kJ mol1

S: 7.5 J K1 mol1
H: 17 kJ mol1

Theoretical Problems

1pt
1pt

8 pts in total

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42nd International Chemistry Olympiad


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Instructions
Examination Procedures
You have 5 hours to complete Tasks 1, 2, and 3.

You may perform the tasks in any

order you choose.


There will be an additional 15 minutes reading time before the start.
DO NOT begin working on the tasks until the START command is given.
When the STOP command is given at the end of the 5 hours, you must stop your
work on the tasks immediately. A delay in doing so may lead to your
disqualification from the examination.
After the STOP command has been given, wait in your lab space.
will check your lab space.

A supervisor

The following items should be left behind:

The problem booklet (this booklet)

The answer booklet

Your chosen TLC plates in zipper storage bags A and B with your student
code (from Task 1)

Your product and glass microfiber filter sheet in a crystallization dish with a
lid in zipper storage bag C with your student code (from Task 1)

Do not leave the examination hall until you are instructed to do so by the supervisors.

Safety
Safety is the most important issue in the laboratory. You are expected to follow the
safety rules given in the IChO regulations. Safety glasses and lab coats must be
worn at ALL TIMES.
If you behave in an unsafe manner, you will receive one warning before you are
asked to leave the laboratory. If required to leave due to a second warning, you will
receive a score of zero for the entire experimental examination.
NO eating or drinking is allowed in the laboratory.
In case of emergency, follow the instructions given by the supervisors.

Notes on the booklets and answer methods

Practical Problems

1 / 22

42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

The problem booklet comprises 23 pages including cover page.


The answer booklet comprises 6 pages.

Do not attempt to separate the sheets.

You should confirm your student code inscribed on the booklets and write your
name and student code on every answer sheet.
Use only the pen provided for filling in the answer sheets.

You may also use the

calculator and the ruler provided. Use the mechanical pencil provided only for
experiments in Task 1. Do not use the mechanical pencil for filling in the answer
sheets.
All results must be written in the appropriate areas on the answer sheets. Results
written elsewhere will not be graded.

If you need to do rough calculations, etc.,

use the back of the sheets.


You should take care to report answers to an appropriate number of significant
figures.
Keep your answer booklet in the envelope provided.

Take out the booklet only when

you write the answers. Do not seal the envelope.

Notes on the Examination


You may need to reuse some glassware during the examination.

If this is the case,

clean it carefully in the sink closest to you.


Contact a supervisor near you if you have any questions regarding the tasks or if you
need a refreshment/toilet break.
Use the labeled waste containers under the hood or near the windows for disposal of
liquids and solids. A waste container (plastic beaker) is also available on each
bench for aqueous waste. Discard used glass capillaries into a labeled plastic tube .
Replacement of chemicals and laboratory ware will be provided if necessary.
Other than the first, for which you will be pardoned, each such incident will result in
the loss of 1 point from your 40 practical points.

Refilling of washbottle water is

permitted with no loss of points.


An official English version of this examination is available upon request if you require
clarification.

Practical Problems

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

Periodic table with relative atomic masses


1

10

11

12

13

14

15

16

17

18

He

1.01

4.00

10

Li

Be

Ne

6.94

9.01

10.81

12.01

14.01

16.00

19.00

20.18

11

12

22.99

24.30

13

Na Mg
19

Ca

Sc

Ti

22

23

Cr

Mn

Fe

Co

Ni

Cu

Zn

39.10

40.08

44.96

47.87

50.94

52.00

54.94

55.85

58.93

58.69

63.55

65.38

41

42

92.91

95.96

37

20

21

Rb

Sr

38

39

Zr

85.47

87.62

88.91

91.22

57-71

Hf

55

Cs

56

Ba

72

132.91 137.33
87

Ra

Nb Mo
73

Ta

74

25

43

Tc
75

Re

26

44

Ru

27

45

Rh

28

46

Pd

29

47

Ag

30

48

Cd

Si

14

15

16

Cl

Ar

26.98

28.09

30.97

32.06

35.45

39.95

31

32

69.72

72.64

Ga Ge
49

In

50

Sn

33

104
89-103

105

106

107

76

Os

77

Ir

78

Pt

79

Au

108

109

110

Sg

Bh

Hs

Mt

Ds

Rg

60

61

62

63

58

Ce

59

Pr

Nd Pm Sm Eu

138.91 140.12 140.91 144.24


89

Ac
-

90

Th

91

Pa

92

232.04 231.04 238.03

35

36

Se

Br

Kr

74.92

78.96

79.90

83.80

52

53

51

Sb

Te

54

Xe

80

Hg

81

Tl

82

Pb

83

Bi

93

Np
-

84

85

86

Po

At

Rn

69

70

111

Db

57

18

101.07 102.91 106.42 107.87 112.41 114.82 118.71 121.76 127.60 126.90 131.29

Rf

La

34

17

As

178.49 180.95 183.84 186.21 190.23 192.22 195.08 196.97 200.59 204.38 207.2 208.98

88

Fr

40

24

Al

64

Gd

65

Tb

66

Dy

67

Ho

68

Er

Tm Yb

71

Lu

150.36 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.05 174.97
94

95

96

97

Pu Am Cm Bk

98

Cf
-

99

100

101

102

103

Es Fm Md No

Lr

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

Apparatuses
Apparatuses

Number

For multiple tasks (on the desk or in Box 1):


20-mL beaker for taking a small portion of liquid to rinse inside of
glassware

Paper

2-mL pipette bulb

5-mL pipette bulb

Pipette rack

200-mL plastic beaker for waste

Safety bulb

Spatula

Stand

100-mL washbottle

500-mL washbottle

For Task 1 (in Box 1, on the desk or on pipette rack):


Bchner funnel with rubber adapter

Clamp with muff (clamp holder)

200-mL conical beaker

300-mL conical beaker

Diaphragm vacuum pump with tubing and connecter

Glass capillary tube (in a plastic tube)

Glass microfiber filter sheet in a crystallization dish with lid

2-mL graduated pipette

5-mL graduated pipette

Magnetic stirrer

10-mm magnetic stirring bar

22-mm magnetic stirring bar

10-mL measuring glass

pH test paper (in a zipper storage bag)

10-mL plastic graduated cylinder

Plastic tube for used glass capillary

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Suction flask

10-mL test tube

100-mL test tube

TLC developing chamber with lid

TLC plate (in a zipper storage bag)

Tweezers

Zipper storage bags A and B for submission of TLC plates


Zipper storage bag C for submission of glass microfiber filter sheet in a
crystallization dish

1 for each
1

For Task 2 (in Box 2, on the desk or on pipette rack):


2-mL graduated pipette

5-mL graduated pipette

Label (in a zipper storage bag)

LED light box (in a zipper storage bag: do not remove from the bag at any
time.)

Nessler tube

Nessler tube rack

50-mL volumetric flask

5-mL volumetric pipette

10-mL volumetric pipette

For Task 3.1 (in Box 2 or on pipette rack):


Burette

Burette clamp

100-mL conical beaker

Glass funnel (for transferring chemicals to a burette)

1-mL graduated pipette

5-mL volumetric pipette

20-mL volumetric pipette

For Task 3.2 (in Box 2):


10-mL vial (in a zipper storage bag)
Plastic Pasteur pipette

10
1

Shared equipment:
Gloves of various sizes

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UV lamp
Cleaning tissue

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Chemicals on Each Desk


Chemical

Quantity

Container

R phrases

S phrases

Plastic bottle None listed

None listed

Vial

36/37/38

26

Vial

36/37/38

26

For multiple tasks (in Box 1):


0.5 mol L-1 hydrochloric acid
(0.5 mol L-1 HCl)

50 mL

For Task 1 (in Box 1):


1,4-dihydro-2,6-dimethylpyridine-3,5
1g
-dicarboxylic acid diethyl ester
(C13H19NO4; 1,4-DHP_powder)
1,4-DHP for TLC
3 mg
(1,4-DHP_TLC)
Ethanol (C2H5OH)

10 mL

Glass bottle

11

7-16

Ethyl acetate (CH3COOC2H5)

25 mL

Glass bottle

11-36-66-67

16-26-33

Heptane (C7H16)

20 mL

Glass bottle

11-38-50/53-6567

9-16-29-3360-61-62

Potassium iodide (KI)

150 mg

Glass bottle

None listed

None listed

Sodium metabisulfite (Na2S2O5)

1g

Glass bottle

22-31-41

26-39-46

Saturated sodium
hydrogencarbonate solution
(Sat. NaHCO3 solution)

25 mL

Glass bottle

None listed

None listed

1g

Vial

8-34

17-2636/37/39-45

30 mL

Plastic bottle None listed

None listed

Plastic bottle None listed

None listed

Plastic bottle None listed

None listed

Plastic bottle None listed

None listed

Urea hydrogen peroxide


(CH4N2OH2O2; UHP)
For Task 2 (in Box 2):
Sample solution (labeled as
Sample solution)

Standard Fe(bpy)32+ solution 1


(containing 2.0 mg of iron in 1 L
50 mL
solution) (labeled as Standard
Fe(bpy)32+ solution 1)
Standard Fe(bpy)32+ solution 2
(containing 3.0 mg of iron in 1 L
50 mL
solution) (labeled as Standard
Fe(bpy)32+ solution 2)
Acetate buffer solution
(pH 4.6, 1:1 mixture of acetic acid
50 mL
and sodium acetate;
CH3COOH-CH3COONa solution)

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

0.1 mol L-1 disodium


25 mL
hydrogenphosphate solution
(0.1 mol L-1 Na2HPO4)
0.2 %(w/v) 2,2-bipyridine aqueous
25 mL
solution
(0.2 %(w/v) C10N2H8)
Sodium thioglycolate
(C2H3NaO2S)

20 mg

Plastic bottle None listed

None listed

Plastic bottle None listed

None listed

Vial

36

22-38

For Task 3.1 (in Box 2 or on the desk):


Polysaccharide solution (labeled as
50 mL
Polysaccharide solution)

Plastic bottle None listed

None listed

Poly(diallyldimethylammonium
chloride) aqueous solution
(PDAC)
240 mL

Glass bottle

None listed

None listed

240 mL

Glass bottle

36/37/38

26-36

0.5 mol L-1 sodium hydroxide


aqueous solution
(0.5 mol L-1 NaOH)

50 mL

Plastic bottle 34

26-37/39-45

1 g L-1 toluidine blue (TB) aqueous


solution
(1 g L-1 C15H16N3SCl)

6 mL

Dropper
bottle

None listed

CH2

H3C

N+
Cl-

CH2

CH3

Potassium poly(vinyl sulfate)


aqueous solution (0.0025 mol L-1;
monomer unit concentration)
(0.0025 mol L-1 PVSK)
CH2 CH
O
O S O
O-K+ n

None listed

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42nd International Chemistry Olympiad


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For Task 3.2 (in Box 2):


Solution X-1 (X: A-H)

10 mL

Dropper
bottle

Solution X-2 (X: A-H)

10 mL

Dropper
bottle

Solution X-3 (X: A-H)

10 mL

Dropper
bottle

Solution X-4 (X: A-H)

10 mL

Dropper
bottle

Solution X-5 (X: A-H)

10 mL

Dropper
bottle

36/37/38

26-36

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Risk Phrases
Number

Special Risks

Contact with combustible material may cause fire.

11

Highly flammable

22

Harmful if swallowed

31

Contact with acids liberates toxic gas.

34

Causes burns

36

Irritating to eyes

38

Irritating to skin

41

Risk of serious damage to eyes

65

Harmful: may cause lung damage if swallowed.

66

Repeated exposure may cause skin dryness or cracking.

67

Vapors may cause drowsiness and dizziness.

36/37/38

Irritating to eyes, respiratory system and skin

50/53

Very toxic to aquatic organisms, may cause long term adverse effects in the
aquatic environment.

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Safety Phrases
Number

Safety Recommendations

Keep container tightly closed.

Keep container in a well ventilated place.

16

Keep away from sources of ignition - No Smoking.

17

Keep away from combustible material.

26

In case of contact with eyes, rinse immediately with plenty of water and seek
medical advice.

29

Do not empty into drains.

33

Take precautionary measures against static discharges.

36

Wear suitable protective clothing.

37

Wear suitable gloves.

39

Wear eye/face protection.

45

In case of accident or if you feel unwell, seek medical advice immediately. (Show
the label where possible.)

46

If swallowed, seek medical advice immediately and show the container or label.

60

This material and its container must be disposed of as hazardous waste.


Avoid release to the environment. Refer to special instructions/ material safety data
sheet.
If swallowed, do not induce vomiting: seek medical advice immediately and show
the container or label

61
62

24/25

Avoid contact with skin and eyes.

36/37/39

Wear suitable protective clothing, gloves and eye/face protection.

37/39

Wear suitable gloves and eye/face protection

Practical Problems

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

Task 1
Reaction of Hantzsch Ester with Urea Hydrogen Peroxide
In this experiment, you are required to synthesize a pyridinedicarboxylate derivative
from 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylic acid diethyl ester (1,4-DHP or
Hantzsch

ester)

by

oxidation

with

urea

hydrogen

peroxide

(UHP),

an

environmentally-friendly oxidant.
O
H
CH3CH2

O
H3C

O
N
H

CH2CH3

N
H

UHP

CH3

N
H

H
O

O O
H
KI

H CH3CH2

H3C

CH2CH3

CH3

1,4-DHP

Procedures
(1) Place a 22-mm magnetic stirring bar in a 100-mL test tube. Fix the test tube on a
magnetic stirrer using a clamp.

Add 1,4-DHP (1 g) (labeled as 1,4-DHP_powder), and

potassium iodide (150 mg) to the test tube, followed by ethanol (5 mL), with a 5-mL
graduated pipette.
(2) Add 1 g UHP (wear gloves) and stir the mixture.

(Caution: this reaction is

exothermic.)
(3) For thin layer chromatography (TLC) analysis, prepare a mixture of ethyl
acetate:heptane (1:2 in volume) with a measuring glass and place an appropriate
amount of the mixture in a TLC developing chamber. Add 1 mL of ethyl acetate to the
vial (labeled as 1,4-DHP_TLC) to dissolve 1,4-DHP (3 mg).
(4) Check your TLC plates before using.

If they are damaged, they can be replaced

without penalty. Draw a start line on the lower portion of a TLC plate with a pencil (see
Fig. 1.1).
(5) During the reaction, the reaction mixture becomes clear (usually within 20 min).

When

the reaction mixture becomes clear (the precipitates may form when it cools, but
precipitates will not affect the TLC analysis), take a small portion of the mixture using a

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glass capillary and load it to make two spots in the center and right positions on the TLC
plate. Load an appropriate amount of the 1,4-DHP solution prepared in procedure (3)
in the center and left positions, so that there are three spots on the plate, with the center
spot containing both the reaction mixture and 1,4-DHP (see Fig. 1.1).

Develop the

TLC plate in the TLC chamber (see Figs. 1.1 and 1.2). Mark the solvent front with the
pencil. Visualize the spots using a UV lamp (254 nm) and draw a line around the
UV-active spots on the TLC clearly with the pencil.

Assess the completion of the

reaction based on the TLC results. Repeat the TLC analysis after ten minutes, if you
find significant amounts of 1,4-DHP in the reaction mixture. [Note that you will perform
TLC analysis again in procedure (8).]

Place the last TLC plate in a zipper storage bag

marked A.

X X+Y Y

Fig. 1.1 Spots on the TLC plate


before development;
X: 1,4-DHP, Y: Reaction
mixture.

Fig. 1.2 TLC plate placed in the


TLC developing
chamber.

(6) Set up the suction filtration equipment (see


Fig. 1.3).

Connect the suction flask to the

diaphragm vacuum pump. Place a Bchner


funnel fitted with a rubber adapter onto the
suction flask.

Place a glass microfiber filter

sheet on the funnel.


(7) Add water (5 mL) to the reaction mixture
using a 10-mL plastic graduated cylinder.
Add sodium metabisulfite (1 g), transfer the
contents of the tube (including the stirring bar)
into a 200-mL conical beaker and wash the
Practical Problems

Fig. 1.3 Suction filtration equipment:


i, Bchner funnel; ii, rubber adopter; iii,
suction flask; iv, diaphragm vacuum
pump.

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test tube with water (30 mL). Place the 200-mL conical beaker on the magnetic stirrer
and stir the solution.

Add saturated sodium hydrogencarbonate solution in small

portions using a 2-mL graduated pipette until the pH of the aqueous phase becomes
just over 7 (check the pH with pH test paper).

Filter the precipitate formed through the

Bchner funnel with suction using the diaphragm vacuum pump, and wash the
precipitate with a small portion of water.

Suck air through the precipitates for a minute

to dry the product.


(8) Transfer the filtrate from the suction flask to a 300-mL conical beaker. Transfer the
filtrate (2 mL) to a 10-mL test tube using a 2-mL graduated pipette. Place a 10-mm
magnetic stirring bar in the test tube and fix it securely with the clamp.

Add 1 mL of

ethyl acetate to the test tube using a 2-mL graduated pipette and stir the solution
vigorously for 30 seconds on the magnetic stirrer.
to separate into two layers.

Stop stirring and wait for the solution

Analyze the upper layer by TLC to see if there is any

product remaining in the filtrates.

Spot the filtrates on the plate in the same way as

procedure (5). Mark the solvent front and the spot(s), if any.

Place the TLC plate in a

zipper storage bag marked B. If you detect the product on the TLC plate, add more
saturated sodium hydrogencarbonate solution.
(9) At this stage, if you find a precipitate formed, filter and wash it.

If you find no

precipitate, skip this filtration process.


(10) Suck air through the precipitate for 10 minutes to dry the product. Place your product
and the glass microfiber filter sheet in the crystallization dish. Cover the dish with the
lid marked with your code.

Avoid placing the stirring bar in the dish.

Place the

crystallization dish with the lid in a zipper storage bag marked C.


a) Copy (sketch) the TLC plate in bag A on your answer sheet.
b) Determine and record the Rf values (to the 2nd decimal place) of the spots on the TLC
plate in bag A.
c) Draw

the

structural

formula

of

the

organic

cation

before

adding

sodium

hydrogencarbonate.
d) What is (are) the final product(s) derived from UHP?

Give the chemical formula(e) of

the product(s).
e) Submit the following:
i) TLC plate in bag A

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ii) TLC plate in bag B


iii) Your product and filter paper in the crystallization dish placed in bag C

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Task 2
Determination of Fe(II) and Fe(III) by visual colorimetry
In this experiment, you are required to determine Fe(II) and Fe(III) in a given sample
solution which simulates a dissolved magnetite ore by visual colorimetric analysis involving
a color reaction between Fe(II) and 2,2-bipyridine (bpy) to form an intensely red complex,
Fe(bpy)32+.
The amount of Fe(bpy)32+ complex can be quantified by visual colorimetric
measurement using Nessler tubes. This is a quite simple technique that was employed
before photoelectric instruments were generally available, but an accuracy of less than
5% can be achieved.

In this technique, a pair of Nessler tubes is used; one is filled with a

reference solution, and the other is filled with a solution to be tested. The depths of colors
of the two solutions are balanced by adjusting the heights of liquid columns of the solutions.
When the colors look the same, the concentration can be calculated from that of the
reference solution with a known concentration and the height of the column of each solution
based on the Lambert-Beer law:
A = cl
where A is the absorbance, c is the concentration, l is the pass length and is the molar
absorption coefficient.

First, you will learn to employ this technique by conducting

measurements A and B, and then you will determine the concentrations of Fe(II) and
Fe(III) with measurements C and D.
Procedures
(1) Add 5 mL of acetate buffer solution, 5 mL of disodium hydrogenphosphate solution (to
mask Fe(III)), 5 mL of 2,2-bipyridine solution and 10.00 mL of sample solution into a
50-mL volumetric flask using appropriate pipettes for each and dilute the resulting
solution with water to the 50-mL mark.

Then stopper the flask and mix the solution well.

Allow it to stand for at least 20 min to fully develop color.

This solution is named

sample 1.
(2) Add 5 mL of acetate buffer solution, 5 mL of 2,2-bipyridine solution and 5.00 mL of
sample solution into a 50-mL volumetric flask. Then add 20 mg of sodium thioglycolate
powder (in excess) to reduce Fe(III) to Fe(II). Dilute the solution with water to the

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50-mL mark, stopper the flask and mix the solution well. Allow it to stand for at least 20
min. This solution is named sample 2.
(3) Perform visual colorimetric measurements A D based on the Instructions for visual
colorimetric measurement shown below.
Instructions for visual colorimetric measurement
Set a pair of Nessler tubes on a Nessler tube rack placed on an LED light box (do not
remove it from the bag at any time) and turn on the light (see Fig. 2.1). Pour the
provided standard Fe(bpy)32+ solution 1 into one tube to an appropriate height (70
90 mm is recommended) from the bottom (etched marks on the tube indicate fixed
heights from the bottom in mm) and use this as a reference for measurements A - D.
Pour the solution to be measured into the other tube, and then compare its depth of
color with that of the reference solution by looking downward through the solutions
toward the LED light box.
Adjust the height of the liquid column of the
test solution by adding or removing the solution
with a graduated pipette until the depth of color
in the two tubes is identical.

Estimate your

reading to at least 1 mm.


Note that the depths of color in a certain
range may be recognized as identical to human
eyes.

The appropriate value for the height of

the test solution, h, should be determined by


taking the range into the consideration.

For

example, if you adjust the height of the liquid


column of the test solution only by increasing (or
decreasing) the volume, you could reach a lower
(or higher) value than the true one.

A possible

way to estimate the true value is to take an

Fig. 2.1 Visual colorimetric


measurement: i, Nessler tube; ii,
Nessler tube rack; iii, LED light
box in a zipper storage bag; iv,
power switch.

average between the values of lower and higher


limits.

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Measurement A:

Perform a measurement using standard Fe(bpy)32+ solution 1 as

both the reference and the test solutions.

In this measurement, pour the reference

solution into a Nessler tube to achieve an appropriate height, and then pour the test
solution into the other Nessler tube until the colors of the two solutions match each other.
(When the colors match, the heights should IDEALLY be the same.) Then add more test
solution until you recognize that the colors have become different from each other. Report
both the lower and higher limits of the height of the liquid column of test solution with the
same depth of color as the reference solution.
a) Report your results for measurement A using the table provided on the answer sheet.
Measurement B:

Perform a measurement of standard Fe(bpy)32+ solution 2 as a test

solution using standard Fe(bpy)32+ solution 1 as a reference.


b) Report your results for measurement B using the table provided on the answer sheet.
Measurement C:

Perform measurement of sample 1.

c) Report your results for measurement C using the table provided on the answer sheet.
Measurement D:

Perform measurement of sample 2.

d) Report your results for measurement D using the table provided on the answer sheet.
e) Express the concentration of the test solution, c, using the concentration of the
reference solution, c, and the height of each liquid column, h and h.
f) Calculate the concentrations of Fe(II) and Fe(III) in the original sample solution in mg
L-1.

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Task 3
Polymers in Analysis
Polymers can be used in various analyses.

In this task, you are first required to

analyze a polysaccharide using a polymer-polymer interaction, which will then be utilized to


identify polymers in the second part.
3.1 Analysis of Polysaccharide by Colloid Titration
You are provided with a solution of a polysaccharide containing sulfonate (-SO3-) and
carboxylate (-COO-) groups.

You are asked to determine the concentrations of these two

groups by colloid titration under the basic and acidic conditions based on the differences in
the protonation behavior of these acid groups. A back-titration technique is utilized.
When these acid groups are ionized, the polysaccharide becomes a polyanion.
Upon addition of polycation, poly(diallyldimethylammonium) (provided as its chloride salt,
PDAC), it forms a polyion complex. PDAC solution is standardized using the standard
solution of potassium poly(vinyl sulfate) (PVSK). At the endpoint of colloid titration, the
number of anionic groups becomes equal to that of cationic groups.
Procedures
(1) Take precisely 20 mL of the PDAC solution using a volumetric pipette into a 100-mL
conical beaker.

Add 2 drops of toluidine blue (TB) into the conical beaker. Titrate the

resulting blue solution with the 0.0025 mol L-1 PVSK (monomer unit concentration)
standard solution.

At the endpoint, the color turns purple.

becomes gradually turbid as the endpoint approaches.


when the color remains purple for 15-20 seconds.
1a)

Note that the solution

The endpoint is determined

Repeat if necessary.

Report the PVSK solution volume (in mL) consumed in the standardization of PDAC.
Record your reading to 0.05 mL.

(2) Take precisely 5 mL of the polysaccharide solution and 20 mL of the PDAC solution
using volumetric pipettes into another conical beaker.
and 2 drops of TB to the solution.

Add 0.4 mL of 0.5 mol L-1 NaOH

Titrate the resulting blue solution with the PVSK

standard solution in a similar manner.

Repeat if necessary.

(The appearance of

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coagulation may be different, depending on the pH of the solution.)


1b)

Report the PVSK solution volume (in mL) consumed in the titration under basic
conditions.

1c)

Record your reading to 0.05 mL.

Mark the acid group(s) ionized under the basic conditions on the answer sheet.

(3) Repeat procedure 2 above with the addition of 0.5 mL of 0.5 mol L-1 HCl instead of 0.5
mol L-1 NaOH.
1d)

Report the PVSK solution volume (in mL) consumed in the titration under acidic
conditions.

Record your reading to 0.05 mL.

1e)

Mark the acid group(s) fully ionized under acidic conditions on the answer sheet.

1f)

Calculate the concentrations of the -SO3- (or -SO3H) groups and the -COO- (or
-COOH) groups (in mol L-1) in the given polysaccharide solution.

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3.2

Identification of compounds
You are provided with five solutions (X-1~5, X designates your sample code,

which is a letter in the Roman alphabet from A to H), and each solution contains one of
The concentration is 0.05 mol L-1 (for

the compounds below (all of which are used).

polymers, monomer unit concentration). Your task is to identify all the compounds by
carrying out the following procedures.

HOCH2CH2OCH2CH2OCH2CH2OH
(TEG)
CH3
CH2CH2O

CH2 C
COONa n
(PMANa)

(PEO)

CH2 CH

SO3Na n

CH2

H3C

(PSSNa)

CH2
N+

Cl-

CH3

(PDAC)

[Abbreviations: TEG, triethylene glycol; PEO, poly(ethylene oxide);


PMANa, poly(sodium methacrylate); PSSNa, poly(sodium 4-styrenesulfonate);
PDAC, poly(diallyldimethylammonium chloride)

MW. stands for molecular weight.]

Helpful comments
1) Aggregates observed in Task 3.1 could be observed when mixing two polymer solutions
in an appropriate combination, in which an interaction takes place between the two
polymers.

They can be utilized to identify polymer samples.

2) The volume of a solution measuring 5 mm in height from the bottom of the vial is
approximately 1 mL. Remind that you have only 10 mL of each solution.

Practical Problems

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

Procedures
(1) Mix similar volumes of two solutions together in a vial.
(2) If necessary, you can acidify the resulting mixture.

Ten drops of hydrochloric acid (0.5

mol L-1 HCl) from a plastic Pasteur pipette are sufficient for this purpose.
Identify the compound in each solution based on the experimental results. For each
solution, mark one of the five boxes to indicate your identification.

You are also asked to

fill in the blanks with one of the letters in the Roman alphabet, from A to H, to indicate your
sample code.

===========================
(22,575 characters without spaces)

Practical Problems

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

NAME:
STUDENT CODE:

Task 1

13% of the total

Reaction of Hantzsch Ester with Urea Hydrogen Peroxide


1a

1b

1c

1d

1e
i

ii

iii

24

Total
40

a) Copy (sketch) the TLC plate in bag A on your answer sheet.


Indicate the solvent front line and the base line.
1) If there are less than three spots loaded on the
base line, 3 points will be subtracted.
2) If the spots are not separated on the TLC after
development, 2 points will be subtracted.
3) If the solvent front line and/or the base line is
missing, 1 point will be subtracted for each.

b) Determine and record the Rf values of the spots on the TLC plate in bag A.
Spot

Rf value

1,4-DHP

0.32-0.42

Product

0.61-0.71

Two points each will be awarded for Rf values (to the 2nd decimal place) in the ranges
shown above. No points will be awarded for values outside the ranges. A score of 1
will be given if the value is reported down to the 1st decimal place.

Practical Problems Answer Booklet

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NAME:

42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

c) Draw

the

structural

formula

of

STUDENT CODE:
the

organic

cation

before

adding

sodium

hydrogencarbonate.
If the correct structural formula is drawn as is shown below, 2 points will be
awarded.
O
CH3CH2

O
H3C

O
N

CH2CH3

CH3

d) What is (are) the final product(s) derived from UHP?

Give the chemical formula(e) of

the product(s).
If correct chemical formulae are written as shown below, 1 point each will be
awarded.
H2O and CH4N2O

e) Submit the following:


i) TLC plate in bag A
If the outline to be drawn with a pencil around the UV-active spots is unclear or
missing, 1 point will be subtracted.
ii) TLC plate in bag B
1) If the outline to be drawn with a pencil around the UV-active spots is unclear or
missing, 1 point will be subtracted.
2) If the solvent front line and/or the base line is missing, minus 1 point for each will
be subtracted.
iii) Your product and filter paper in the crystallization dish stored in bag C

Practical Problems Answer Booklet

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

NAME:
STUDENT CODE:

1) The scientific committee will measure the percent yield after drying at 60 C.
2) In most cases, the sample is pure and dissolved in CDCl3 completely.

The

following calculation based on the percent yields obtained will be applied only if
no 1,4-DHP or byproducts is observed in the 1H NMR spectrum and the product is
completely soluble in CDCl3.

If 80.0 %yield <92.0, 0-24 points


If 92.0 %yield < 99.0, 24 points.
If 99.0 %yield < 102.0, 24-0 points.

3) If there are peaks of 1,4-DHP (ca 2.19 ppm) and the corresponding pyridine
product (ca 2.85 ppm) in the 1H NMR spectrum and the percent yield is 100% or
less, the actual percent yield is calculated by the following equation:

Sample mass (g)


Theoretical yield (g)

(Integral at 2.85 ppm) x 251.3


(integral at 2.19) x 253.3 + (integral at 2.85 ppm) x 251.3

x 100

4) If insoluble material remains after the addition of CDCl3 for 1H NMR measurement,
6 points will be subtracted.
5) If byproducts are detected evidently in the 1H NMR spectrum, 6 points will be
subtracted.

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NAME:

42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

STUDENT CODE:

Task 2

11% of the total

Determination of Fe(II) and Fe(III) by visual colorimetry


2a
2

2b
2

2c
15

2d
15

2e
3

2f

Total

ii

45

a) Report your results for measurement A using the table provided on the answer sheet.
h' (height of Lower limit of Higher limit of h (estimated
standard
h /mm
h /mm
height of test
solution 1) /
solution)
/
mm
mm
Measurement A

Any value

Any value

Any value

Any value

Two points will be awarded, except when there is no answer.


b) Report your results for measurement B using the table provided on the answer sheet.
h' (height of standard h (estimated height of test
solution 1) / mm
solution) / mm
Any value

Measurement B

Any value

Two points will be awarded, except when there is no answer.


c) Report your results for measurement C using the table provided on the answer sheet.
h' (height of standard h (estimated height of test
solution 1) / mm
solution) / mm
sample 1: 1.23 h'
Measurement C

Experimental value of h'

sample 2: 1.16 h'


sample 3: 1.10 h'

Practical Problems Answer Booklet

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

NAME:
STUDENT CODE:

d) Report your results for measurement D using the table provided on the answer sheet.
h' (height of
solution 1) / mm

standard h (estimated height of test


solution) / mm
sample 1: 0.763 h'

Measurement D

Experimental value of h'

sample 2: 0.725 h'


sample 3: 0.749 h'

For 2c and 2d, a full score of 15 points will be awarded for values within a 5% error range.
A score of zero will be given if the absolute error is 15% or more. A linear point scale will be
applied for scores from zero to 15; points will be
calculated by the following equation:

h'2.0 (mg L1 )
MV =
c
P : Points (no negative value; zero if P < 0)
MV : Master value of h (mm)

10
Points

MV h MV 0.05

P = 15 1
(MV 0.15) (MV 0.05)

15

0
-20 -15 -10

-5

h : Experimental height of liquid column of the

10

15

20

% error

test solution (mm)


h : Experimental height of liquid column of reference solution (mm)
c : Concentration of Fe in correctly prepared test solutions (mg L-1)
for 2c, c = 1.63,1.72 and 1.82 for Sample 1, 2 and 3, respectively.
for 2d, c = 2.62, 2.76, and 2.67 for Sample 1, 2 and 3, respectively.

Practical Problems Answer Booklet

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

NAME:
STUDENT CODE:

e) Express the concentration of the test solution, c, using the concentration of the reference
solution, c, and the height of each liquid column, h and h.

c=

c ' h'
h

3 points. Any equivalent formula is acceptable.


f) Calculate the concentrations of Fe(II) and Fe(III) in the sample solution in mg L-1.

For Fe2+,
[Fe2+ ] =

2.0(mg L1 ) hC' 50(mL )


hC 10(mL)

[Fe2+]: concentration of Fe2+ in the sample solution (mg L-1)


hC: experimental height (mm) of the liquid column of the test solution in the
measurement C
hC : experimental height (mm) of the liquid column of the standard solution in
the measurement C
If the concentrations are calculated correctly from the experimental data, full
marks will be awarded 3 points.
For Fe3+
[Fe3+ ] =

2.0(mg L1 ) hD' 50(mL )


[Fe2+ ]
hD 5(mL )

[Fe3+]: concentration of Fe3+ in the sample solution (mg L-1)


hD : experimental height (mm) of the liquid column of the test solution in the
measurement D
hD : experimental height (mm) of the liquid column of the standard solution in
the measurement D
If the concentrations are calculated correctly from the experimental data, full
marks will be awarded 5 points.

Practical Problems Answer Booklet

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

NAME:
STUDENT CODE:

Concentrations of Fe2+ and Fe3+ in each original sample solution


[Fe2+] / mg L-1

[Fe3+] / mg L-1

Sample 1

8.16

18.0

Sample 2

8.60

19.0

Sample 3

9.08

17.7

Practical Problems Answer Booklet

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

NAME:
STUDENT CODE:

Task 3

16% of the total

Polymers in Analysis
3.1a

3.1b

3.1c

3.1d

3.1e

3.1f

3.2

Total

10

10

20

50

3.1
1a) Report the PVSK solution volume (in mL) consumed in the standardization of PDAC.

PVSK solution volume consumed in


the standardization of PDAC:

MV(z) = 20.06 mL

z mL
A full score of 4 points will be awarded if the answer is MV(z) 0.15 mL. (MV: Master Value)
A score of zero will be given if the answer is less than (MV(z) 0.5) mL or greater than
(MV(z) + 0.5) mL. A linear point scale will be applied for answers in between.
Two points will be subtracted if the value is not reported down to the 2nd decimal place (in
mL).
mark

0.5 0.4 0.3 0.2 0.1

0 0.1 0.2 0.3 0.4 0.5


V

1b) Report the PVSK solution volume (in mL) consumed in the titration of the
polysaccharide under basic conditions.

PVSK solution volume


under basic conditions:

consumed

Sample A: MV(x) = 13.14 mL


Sample B: MV(x) = 12.07 mL

x mL

Sample C: MV(x) = 10.91 mL

A full score of 10 points will be awarded if the answer is MV(x) 0.25 mL.
A score of zero will be given if the answer is less than (MV(x) 0.6) mL or greater than
(MV(x) + 0.6) mL. A linear point scale will be applied for answers in between.
Two points will be subtracted if the value is not reported down to the 2nd decimal place (in
mL). A score of zero will be applied if the value becomes negative after the subtraction.

Practical Problems Answer Booklet

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

NAME:
STUDENT CODE:

1c) Mark the acid group(s) ionized under basic conditions on the answer sheet.

conditions
basic

acid group
X -SO3H X COOH

Total 1 point.
1d) Report the PVSK solution volume (in mL) consumed in the titration of the
polysaccharide under acidic conditions.

PVSK solution volume consumed


under the acidic conditions:
y mL

Sample A: MV(y) = 15.26 mL


Sample B: MV(y) = 14.61 mL
Sample C: MV(y) = 13.59 mL

A full score of 10 points will be awarded if the answer is MV(y) 0.25 mL.
A score of zero will be given if the answer is less than (MV(y) 0.6) mL or greater than
(MV(y) + 0.6) mL. A linear point scale will be applied for answers in between.
Two points will be subtracted if the value is not reported down to the 2nd place of decimals
(in mL). A score of zero will be applied if the value becomes negative after the subtraction.
1e) Mark the acid group(s) ionized under acidic conditions on the answer sheet.

conditions
acidic

acid group
COOH
X -SO3H

Total 1 point.
1f) Calculate the concentrations of the -SO3- (or -SO3H) groups and the -COO- (or
-COOH) groups (in mol L-1) in the given polysaccharide solution.

-SO3- (or -SO3H) group:


0.0005(z - y)

mol L-1

-COO (or -COOH) group:


0.0005(y - x)

mol L-1

Total 4 points, 2 points for each.


A score of 2 is given to the values within (calculated value) 0.2. A score of 1 is given to
the values which were outside the above allowance ( 0.2 mol L-1) and within (calculated
value) 0.5 mol L-1.

Practical Problems Answer Booklet

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

NAME:
STUDENT CODE:

3. 2

Identify the compound in each solution based on the experimental results. For each
solution, mark one of the five boxes to indicate your identification. You are also asked to fill
in the blanks with one of the letters in the Roman alphabet, from A to H, to indicate your
sample code.

Sample code

-1

TEG

PEO

PMANa

PSSNa

PDAC

-2

TEG

PEO

PMANa

PSSNa

PDAC

-3

TEG

PEO

PMANa

PSSNa

PDAC

-4

TEG

PEO

PMANa

PSSNa

PDAC

-5

TEG

PEO

PMANa

PSSNa

PDAC

Before (upper rows) and after (lower rows) the addition of HCl
TEG
PEO
PMANa
PSSNa

PDAC

TEG
PEO
PMANa
PSSNa
PDAC

+
-

+
-

+
+

+: Precipitation, -: No precipitation (or the precipitate disappears)

Practical Problems Answer Booklet

10 / 12

42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

NAME:
STUDENT CODE:

PMANa and PSSNa are polyanions, and they interact with a polycation (PDAC) to
form a precipitate. Under acidic conditions, the carboxylate (-COO-) groups in PMANa
undergo protonation, and PMANa changes to protonated poly(methacrylic acid) (PMA).
The resulting carboxy (-COOH) groups interact with the ether oxygen atoms in PEO
through hydrogen bonding to form a precipitate. Since protonated PMA is no longer a
polyanion, the precipitate (the complex between PMANa and PDAC) disappears after the
addition of HCl.
On the other hand, PSSNa does not exist as the protonated form, even under
acidic conditions, and no precipitate is observed with PEO at a lower pH. Since TEG is a
small molecule, its interaction with PMA is not strong enough to form a precipitate.
1) For each correct answer, 4 points will be awarded.
2) If two or more boxes are marked for one sample, 0 points will be given for that sample
even if the correct answer is included in the marked compounds.
3) If the same box is marked for more than two samples, 0 points will be given for these
samples even if the correct answer is included in the marked samples.
Table List of samples in Task 3.2

TEG

PEO

PMANa

PSSNa

PDAC

A-3

A-2

A-1

A-4

A-5

B-2

B-1

B-5

B-3

B-4

C-1

C-5

C-4

C-2

C-3

D-5

D-4

D-3

D-1

D-2

E-3

E-2

E-1

E-4

E-5

F-2

F-1

F-5

F-3

F-4

G-1

G-5

G-4

G-2

G-3

H-5

H-4

H-3

H-1

H-2

Practical Problems Answer Booklet

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42nd International Chemistry Olympiad


Tokyo, July 19-28, 2010

NAME:
STUDENT CODE:

HOCH2CH2OCH2CH2OCH2CH2OH
(TEG)
CH3
CH2CH2O
(PEO)

CH2 CH

SO3Na n
(PSSNa)

CH2 C
COONa n
(PMANa)

CH2

H3C

CH2
N+

Cl-

CH3

(PDAC)

[Abbreviations: TEG, triethylene glycol; PEO, poly(ethylene oxide);


PMANa, poly(sodium methacrylate); PSSNa, poly(sodium 4-styrenesulfonate);
PDAC, poly(diallyldimethylammonium chloride)

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