INTERNATIONAL CHEMISTRY

OLYMPIADS

1986 - 1994

Problems and Solutions

edited by Marco Ziegler

Triple Medallist ICHO 1990, 1991, 1992

University of Fribourg, Switzerland

1993

by Marco Ziegler

This version is free of charge and may be distributed freely. Comments, corrections and other
intersting problems that will be incorprated in a larger problem compilation should be sent to
Marco.Ziegler@Unifr.ch1. Table of Contents

Problems

1. Analytical chemistry p. 3
2. Inorganic chemistry p. 5

3. Physical chemistry p. 12

4. Technical chemistry p. 19

5. Organic chemistry p. 21

6. Biochemistry p. 29

Solutions

1. Analytical chemistry p. 32

2. Inorganic chemistry p. 34

3. Physical chemistry p. 41

4. Technical chemistry p. 47

5. Organic chemistry p. 53

6. Biochemistry p. 62
Problems

1. Analytical chemistry

IChO Veszprém - Budapest 1987

emf
(V)

C
B
A

v(cm3)
0 2.47 ? 10.00

Fig. 1 Potentiometric titration curve

25.00 ml of a neutral solution containing potassium chloride and potassium cyanide are potentiometrically titrated with
a standard 0.1000 molar silver nitrate solution at 25°C using a silver electrode and a normal calomel half-cell with KNO3
- salt bridge. The protonation of cyanid ions is negligible. The potentiometric curve obtained (emf (V)) vs. burette
readings (in ml) is shown in Fig. 1.

a) The end point of the reaction taking place during the titration are marked with A, B and C. Write the balanced ionic
equation for each reaction.
b) What volume of the titrant is required to reach point B ?
c) Calculate the concentrations of KCl and KCN in the sample solution.
d) Calculate the emf readings at the points A and C in volts.
- -
e) What is the molar ratio Cl /CN in the solution and in the precipitate at point C ?

Data:
o +
E (Ag /Ag): 0.800 V
o
E (Calomel): 0.285 V
-15.8 2 2
Ksp(AgCN): 10 mol /l
[Ag(CN )-2]
β2 = = 1021.1 mol-2 l2
[Ag+ ][CN- ]2
-9.75 2 2
Ksp(AgCl): 10 mol /l

IChO Helsinki 1988

Chloride ions are analytically determined by precipitating them with silver nitrate. The precipitate is undergoing
decomposition in presence of light and forms elemental silver and chlorine. In aqueous solution the latter disproportionates
to chlorate (V) and chloride. With excess of silver ions, the chloride ions formed are precipitated whereas chlorate (V)
ions aren’t.
a) Write the balanced equations of the reactions mentioned above.
b) The gravimetric determination yielded a precipitate of which 12% by mass was decomposed by light. Determine the
size and direction of the error caused by this decomposition.
c) Consider a solution containing two weak acids HA and HL, 0.020 molar and 0.010 molar solutions respectively. The
acid constants are 1⋅10-4 for HA and 1⋅10-7 mol/l for HL. Determine graphically the pH of the solution using a
logarithmic diagram, log C = f(-log[H+]). Calculate the pH of the solution.
d) M forms a complex ML with the acid H2L with the formation constant K1. The solution contains an other metal ion
N that forms a complex NHL with the acid H2L. Determine the conditional equilibrium constant, K’1 for the complex
ML in terms of [H+] and K values.

[M’] = total concentration of M not bound in ML

[L’] = the sum of the concentrations of all species containing L except ML
[ML]
K1 =
[M][L]
[ML]
K1′ =
[M ′][L ′]
[NHL]
K NHL =
[N][L][H +]
In addition to K1, the acid constants Ka1 and Ka2 of H2L as well as the formation constant KNHL of NHL are known. You
+
may assume that the equilibrium concentration [H ] and [N] are known, too.

IChO Pittsburgh 1992

The minimum concentration of chloride ions needed in oyster beds for normal growth is 8 ppm (8 mg/l).
To 50.00 ml a sample of bay water a few drops of a K2CrO4-solution are added. The sample is then titrated with 16.16 ml
of a 0.00164 M AgNO3-solution when a bright red-orange precipitate starts to form.

a) What is the molar concentration of chloride in the sample ? Does the water contain sufficient chloride for the normal
growth of oysters ?
b) Write a balanced equation for the reaction of the analyte with the titrant.
c) Write a balanced net-ionic equation that describes the reaction responsible for the colour change at the endpoint of
the titration. Which compound produces the brick-red colour ?
d) The concentration of chromate at the endpoint is 0.020 M. Calculate the concentration of chloride in the solution
when the red precipitate is formed.
e) For this titration to work most efficiently, the solution being titrated must be neutral or slightly basic. Write a balanced
equation for the competing reaction that would occur in acidic medium influencing the observed endpoint of this
titration.

Typically, a buffer is added to the solution being titrated to control the pH. Suppose the pH of the sample of bay water
was 5.10, thus too acidic to perform the analysis accurately.

f) Select a buffer from the list that would enable you to establish and maintain a pH of 7.20 in aqueous medium. Show
the calculations which leads your choice.

Buffer systems Ka of weak acid

-4
1. 0.1 M lactic acid / 0.1 M sodium lactate 1.4 ⋅10
-5
2. 0.1 M acetic acid / 0.1 M sodium acetate 1.8 ⋅ 10
-8
3. 0.1 M sodium dihydrogen phosphate / 0.1 M sodium hydrogen phosphate 6.2 ⋅ 10
-10
4. 0.1 M ammonium chloride / 0.1 M ammonia 5.6 ⋅ 10

g) Using the selected buffer system, calculate the number of grams of weak acid and of conjugated base you would
need to dissolve in distilled water to prepare 500 ml of a stock solution buffered at a pH of 7.2.
h) The chloride concentration in another 50.00 ml sample was determined by the Vollhard method. In this method an
+
excess of AgNO3 is added to the sample. The excess Ag is titrated with standardized KSCN, forming a precipitate of
AgSCN. The endpoint is signalled by the formation of the reddish-brown
 FeSCN2+ complex that forms when Ag+ is depleted. If the excess Ag+ from the addition of 50.00 ml of 0.00129 M
AgNO3 to the water sample required 27.46 ml of 1.41 10-3 M KSCN for titration, calculate the concentration of
chloride in the bay water sample.

In natural waters with much higher concentration of Cl-, it can be determined gravimetrically by precipitating them as
AgCl. A complicating feature of this method is the fact that AgCl is susceptible to photodecomposition as shown by the
reaction: AgCl (s) → Ag (s) + ½ Cl2 (g). Furthermore, if this photodecomposition occurs in the presence of excess Ag+,
the following additional reaction occurs:

3 Cl2 (g) + 3 H2O + 5 Ag+ → 5 AgCl + ClO3- + 6 H+

i) Will the apparent weight of AgCl be too high or too low ? Explain your answer showing by how many grams the two
values will differ.

-10 -12
data: Ksp for AgCl = 1.78 ⋅ 10 Ksp for Ag2CrO4 = 1.00 ⋅ 10

IChO Peruggia 1993

The reflux of bile and duodenal matter is suspected to be the major cause of gastritis and medical therapy is based on
treatment with antiacida that, by binding bile acids and lysolecithin, buffer the pH of gastric juces. The separation of two
bile acids, i.e. cholic acid (CA) and glycocholic acid (GCA) was achieved with high performance liquid chromatography
(HPLC). Two chromatographic columns (A and B, respectively) were selected on the basis of published literature data.
The retention times (t) of the two acids, of a substance not retained and of a compound used as internal standard (i.s.)
are shown on the Table 1. Both columns are 25 cm long and show an efficiency of 2.56 ⋅ 104 theoretical plates per meter
(N/m). In actual analysis, an artificial gastric juice was extracted with appropriate solvents and the final solution (1mL)
contained 100% of the two acids present in the original mixture. 100 µL of the extract added with 2.7 µL of internal
standard were analyzed by HPLC using the selected column. The response factors (F) of CA and GCA with respect to the
i.s. and chromatographic peak areas of the two compounds are reported in the Table given below.

Column A
t (sec) Column B
t (sec)
F
Area
Unretained compound 120 130
Cholic Acid (CA) 380 350 0.5 2200
Glycocholic Acid (GCA) 399 395 0.2 3520
Internal standard (i.s.) 442 430 2304

Note that:

R = ( N / 4) ⋅ [(α − 1) / α] ⋅ [ K'/( K' +1)]

α = t '2 / t 1' = ( t 2 − t 0 ) / ( t 1 − t 0 )
K' = t '2 / t 0 = ( t 2 − t 0 ) / t 0

a) Using R, α and K’ values, demonstrate which of the two chromatographic columns would be best to use, considering
that an accurate determination requires the best possible (baseline) separation of all compounds (do not take into
account the unretained compound) ?

b) Calculate the amounts of each acid in the extract solution.

IChO Oslo 94

Lactic acid is formed in the muscles during intense activity (anaerobic metabolism). In the blood, lactic acid is neutralized
by reaction with hydrogen carbonate ions. This will be illustrated by the following calculations:

Lactic acid, written HL, is monoprotic, and the acid dissociation constant is KHL = l.4 x l0-4.
The acid dissociation constants for carbonic acid are: Ka1 = 4.5 x 10-7 and Ka2 = 4.7 x 10-11. All carbon dioxide remains
dissolved during the reactions.

a) Calculate the pH of a 3.00 x 10-3 M solution of HL.

b) Calculate the value of the equilibrium constant for the reaction between lactic acid and hydrogen carbonate ions.

c) 3.00 x 10-3 mol of lactic acid (HL) is added to 1.00 L of 0.024 M solution of NaHCO3 (no change in volume, HL
completely neutralized). Calculate the pH of the solution of NaHCO3 before HL is added. Calculate the pH of the
solution after the addition of HL.

d) The pH of the blood in a person changed from 7.40 to 7.00 due to the lactic acid which formed during physical
activity. Let an aqueous solution having pH = 7.40 and [HCO3-] = 0.022 M represent blood in the following calculation
and in f). Calculate the number of moles of lactic acid which must be added to 1.00 L of this solution so that the pH
becomes7.00.

e) In a saturated aqueous solution of CaCO3(s) the pH is measured as 9.95. Calculate the solubility of calcium carbonate
in water and show that the calculated value for the solubility product constant Ksp is 5 x 10-9.

f) Blood contains calcium ions. Calculate the maximum concentration of „free“ calcium ions in the solution given in d).
(pH = 7.40, [HCO3-] =0.022 M)

2. Inorganic chemistry

IChO Leiden 1986

Compounds containing divalent platinum with the general formula PtX2 (amine)2 (X = Cl2, SO42-, malonate, etc.) have
met a lot of scientific interest because of their biological activity, particularly in view of their properties in the treatment
of tumours. The best known compound used clinically is PtCl2(NH3)2. This compound, in which platinum is coordinated
in a planar square, has two geometrical isomers of which only one shows the antitumour activity.

a) Sketch the spatial structures of the two possible isomers.

b) How many isomers has PtBrCl(NH3)2 ? Sketch all of them.

It is possible to replace the amine ligands by one ligand containing two donor atoms (N). Then one obtains a chelating
ligand, such as 1,2-diaminoethane (en).

c) Show graphically that PtBrCl(en) has only one stable structure.

The ligand en can be substituted via methylation to form dmen or pn (racedmic).

H2N N or H2N N

dmen pn (racemic)
d) Give spatial structures of all isomers of the following compounds: PtCl2(dmen), PtCl2(pn), PtBrCl(dmen) and PtBrCl(pn).
H2N N or H2N N

dmen pn (racemic)
These compounds can isomerize in aqueous solution through dissociation of a ligand and transient replacement of the
stronger ligands by the weak ligand water. Cl- and Br- are replaced relatively easily, but it is more difficult to replace the
amine ligands, which usually requires heating.

e) Considering each of the isomers in the previous questions a-d, indicate which isomers can be converted to another
at room temperature. Give both the original molecule and the products.
f) PtCl2(en) reacts with Br- in a molar proportion of 1:2 at room temperature. Which compound would you expect to form
in what proportion ? You can assume that the Pt-Br and Pt-Cl bonds are equally strong and that there is no perturbing
influence from hydrolysis.

H2O
H3N
O NH3
Pt

N
N

H2N N N

sugar

g) Using the equation to express chemical equilibrium, show that hydrolysis hardly ever occurs in blood but that is does
occur in the cells. Note: PtCl2(NH3)2 hydrolyses to Pt(NH3)2(H2O)22+ and 2 Cl-. In cells the Cl- concentration is low,
in blood it is fairly high.

After hydrolysis in the tumour cell a reactive platinum ion is formed to which two NH3 groups are still bound, which were
found in the urine of patients treated with this compound. The reactive platinum ion appears to be bound to cellular
DNA, where the bonding occurs via guanine to one of the N-atoms.

As a result of the two reactive sites of platinum and the two unreactive NH3 ligands, it can form a second bond to DNA
in addition. Research has shown that this happens in particular with a second guanine base from the same strand of
DNA.

h) Show by calculation which of the two isomers in question a) can form this bond. (note: Pt-N distance - 210 pm, DNA
base distance = 320 pm).

IChO Leiden 1986

The compound Na5P3O10 is used as an additive for detergents to bind the Ca2+ and Mg2+ ions present in water in order
to prevent the precipitation of their fatty acid salts on the laundry.

a) Draw the structure of the ions (P3O10)5- and (P3O9)3- assuming that P-P bonds do not occur.
b) Assuming an octahedral coordination of the Mg2+ ion give a drawing of the Mg(P3O10)(H2O)n)3- ion also indicating
the value for n.

The complex ions of Mg2+ and Ca2+ and triphosphate are well soluble in water. They are, among other things, responsible
for the wild growth of algae in surface waters. They could be removed by precipitation as an insoluble compound.
c) Give some possibilities (ions) to precipitate the triphosphates bound to Ca2+ or Mg2+.
d) Calculate the number of grams of Na5P3O10 necessary in a washing machine of 20 liters to reduce the amount of Ca2+
in city water (0.225 g/l) to an acceptable maximum of 0.02 g/l. Effects of the pH, the precipitation of Ca(OH)2 and
possible effects by other positive ions can be neglected. The following data is given:

[Ca 2+ ][P3 O105-

]
K1 = 3-
= 1.0 • 10-6
[Ca P3 O10]

Molar mass of Na5P3O10 is 366 g, the atomic mass of Ca is 40 g/mol.

IChO Veszprém - Budapest 1987

500 mg of a hydrated sodium salt of phosphoric acid are dissolved in 50.0 ml of 0.1 molar sulphuric acid. This solution is
diluted with distilled water to 100.0 ml and 20.0 ml thereof are titrated with 0.100 molar NaOH solution using thymolphthalein
as indicator. The average of the burette reading is 26.53 ml. The pH at the end- point is 10.00. The cumulative protonation
constants are given by

[H n POn-3
4 ]
Kn =
[ PO4 ][H+ ]n
3-

where pK1 = -11.70; pK2 = -18.6; pK3 = -20.6. Relative atomic masses are: Na = 23.0 and P = 31.0

a) Calculate the percentage distribution, by moles, of all protonated HnPO4 n-3 species at the end point.
b) What is the stoichiometric formula of the salt ?

IChO Helsinki 1988

Upon heating of a mixture of A and fluorine (molar ratio 1:9, high pressure) to 900 °C three compounds (B, C and D) are
formed. All three products are crystalline solids with melting points below 150 °C. The fluorine content of C is found to
be 36.7% and that of D 46.5% (by weight). When B is treated with anhydrous HOSO2F at -75°C a compound E is formed:
B + HOS2F → E + HF
E is a solid which is stable for weeks at 0°C, but decomposes in days at room temperature. The electron density
distribution of E obtained through X-ray diffraction studies is shown on two intersecting, mutually perpendicular planes
(see Fig. 2). The numbers indicated on the maps relate to the electron density in the neighbourhood of the atoms of E as
a function of the spatial coordinates. The maxima found in these maps coincide with the locations of the atoms and the
values are approximately proportional to the number of electrons in the atom in question.

a) Show where the maxima lie by drawing the contour curves around the maxima, connecting points of equal electron
densities. Label each maximum to show the identities of the atoms in E.
b) When 450.0 mg of C was treated with an excess of mercury, 53.25 ml of A was liberated at a pressure of 101.0 kPa at a
temperature of 25°C. Calculate the relative atomic mass of A.
c) Identify A, B, C, D and E.
d) Use the valence-shell electron-pair repulsion theory (VSEPR) to propose electron-pair geometries for B and C. Using
the two electron density maps, sketch the molecular geometry of E.

The original mixture was hydrolysed in water. B reacts to A while liberating oxygen and producing aqueous hydrogen
fluoride. Hydrolysis of C leads to A and oxygen (in molar ratio of 4:3) and yields an aqueous solution of AO3 and
hydrogen fluoride. D hydrolyses to an aqueous solution of AO3 and hydrogen fluoride.

e) Write the equations for the three hydrolysis reactions.

f) Quantitative hydrolysis of a mixture of B,C and D gives 60.2 ml of gas (measured at 290 K and 100 kPa). The oxygen
content of this gas is 40.0% (by volume). The amount of AO3 dissolved in water is titrated with an aqueous 0.1 molar
FeSO4 solution and 36.0 ml used thereby. During the titration Fe2+ is oxidized to Fe3+ and AO3 is reduced to A.
Calculate the composition (% by moles) of the original mixture of A, B, C and D.
 Y-direction

(pm)

600

500

400

300

200

100

-100

-200

1 2 2 1 1 2 2 2 1 2 1 2 1 2
1 2 1 2 1 1 2 1 3 1 1 2 1 2
2 2 1 1 2 1 2 4 26 3 1 2 1 2
3 1 2 1 2 2 3 9 32 11 2 2 1 2
1 2 1 1 2 2 4 20 58 21 3 1 2 1
-300 -200 -1002 2 0 1 100
1 2 2001 3300 10 33 11 4 2 2 2
1 1 2 2 1 2 2 8 19 6 3 3 1 1
1 1 2 1 2 2 5 3 6 3 2 1 2 1
1 2 2 1 4 17 20 16 3 2 2 3 1 2
1 1 2 4 12 33 76 36 13 4 3 1 2 1
2 1 2 6 36 100 220 101 31 6 1 2 1 2
1 2 4 13 61 149 356 152 62 15 6 1 2 1
2 2 1 6 31 105 232 90 26 7 3 1 1 2
1 1 2 6 12 36 65 28 10 4 2 1 1 2
2 2 1 2 7 15 15 13 6 1 2 1 1 2
1 1 1 3 5 3 6 2 1 1 1 2 2 1
1 2 2 6 14 6 3 1 1 2 2 2 1 2
2 2 3 11 23 10 3 8 2 1 2 1 2 2
2 2 7 19 32 16 2 1 2 2 1 1 2 2
1 2 3 9 25 12 3 2 2 2 2 1 1 2
2 2 1 4 13 5 6 4 2 1 1 1 2 1
1 1 1 2 6 10 33 11 1 2 1 1 1 2
1 2 1 4 11 22 80 23 5 2 1 2 1 2
1 2 9 8 30 52 104 49 16 1 2 3 1 2
1 1 2 3 12 21 75 23 6 2 1 2 1 1
1 2 1 2 4 9 36 11 2 2 1 1 2 2
1 1 2 4 15 5 6 4 1 1 2 1 1 2
2 2 3 11 24 18 4 2 1 2 1 2 1 2
1 2 6 17 52 19 6 3 1 2 1 2 2 1
2 1 3 8 23 8 4 1 2 1 2 1 1 2
2 2 1 4 13 5 2 2 1 1 3 2 1 2
1 1 2 1 2 1 1 1 2 1 1 2 2 1
1 2 1 1 2 2 1 2 2 1 1 2 2 1

X direction (pm)

Z-direction
(pm)
400

300

200

100

-100

-200

-300

-400

1 2 1 1 2 2 2 1 1 1 2 2 2 2
1 2 1 1 2 1 1 2 2 2 1 2 1 1
1 2 2 1 1 1 2 2 1 1 1 2 2 1
1 1 2 2 2 1 2 1 1 1 1 2 1 1
1 2 2 2 1 2 1 1 2 1 2 1 1 2
1 1 2 2 2 1 1 2 1 2 1 2 1 1
2 2 2 2 1 1 2 2 1 1 2 2 2 1
1 1 2 1 1 1 2 2 2 1 1 2 2 1
2 2 1 1 1 2 3 2 1 1 2 2 1 1
1 2 2 1 1 2 2 1 2 2 2 1 1 1
2 2 2 2 1 1 2 1 1 2 2 3 1 2
1 1 1 2 1 1 2 4 11 3 2 1 1 1
1 1 2 2 1 1 1 8 21 9 3 2 1 2
1 2 1 1 2 3 4 10 50 19 3 2 1 2
1 1 2 2 2 5 6 10 23 9 2 1 1 2
1 1 1 2 4 8 33 8 10 3 1 1 2 1
1 2 1 3 9 21 74 22 5 1 2 2 2 2
1 2 9 8 20 58 194 49 16 1 2 3 1 2
1 1 3 2 11 23 81 23 13 1 1 1 1 2
1 2 1 3 3 12 37 11 4 2 2 2 1 2
1 1 1 2 1 3 7 5 15 4 2 3 1 1
2 1 2 2 2 2 4 10 24 9 3 1 2 2
1 1 2 1 2 3 8 19 52 18 3 2 2 2
2 2 2 1 1 2 3 9 21 8 3 2 2 1
3 2 1 1 2 1 2 4 12 3 1 1 1 1
2 1 2 2 1 1 2 2 2 1 2 2 2 2
1 2 2 2 1 1 1 2 2 1 2 1 1 2
2 2 1 1 2 2 2 2 1 1 2 2 1 2
1 2 1 1 2 1 1 2 1 1 2 2 2 2
2 1 1 2 2 2 1 3 1 2 2 3 3 1
1 1 1 2 2 2 2 1 3 2 1 1 2 1
2 1 1 2 2 2 1 1 2 1 2 1 1 1
1 2 1 1 2 2 2 2 1 1 2 2 2 1

-300 -200 -100 0 100 200 300

X-direction (pm)

Fig. 2 Electron density distribution of compound E

IChO Halle 1989

To determine the solubility product of copper(II) iodate (Cu(IO3)2 by iodometric titration in an acidic solution (T=25 °C)
20.00 ml of a saturated aqueous solution 30.00 ml of a 0.10 molar sodium thiosulphate solution are needed.

a) Write the sequence of balanced equations for the above described reactions.
b) Calculate the initial concentration of Cu2+ and the solubility product of copper(II) iodate. Activity coefficients can be
neglected.

IChO Halle 1989

O O Cl O
Cl Cl Cl Cl
+ PCl 5 + POCL3 + HCl
P P P
Cl N Cl Cl N Cl

I II III IV

O O Cl O
Cl Cl Cl Cl
+ PCl 5 + POCL3 + HCl 32
P P P P labelled
Cl N Cl Cl N Cl
phosphorus pentachloride (half-life t1/2 = 14.3 days) is used to study the electrophilic attack of a PCl4+ cation on
nitrogen or on oxygen. The reaction is carried out in CCl4 and the solvent and product IV distilled off.

Samples of III (remaining in the distillation flask), of IV (in the distillate) and samples of the starting material II are
hydrolyzed by heating with a strong sodium hydroxide solution. The phosphate ions formed are precipitated as ammonium
magnesium phosphate. Purified samples of the three precipitates are then dissolved by known volumes of water and the
radioactivity measured.

a) Write the balanced equations for the reaction of red phosphorus forming PCl5
b) Write the reaction equations for complete hydrolysis of the compounds II and III using sodium hydroxide.
c) How long does it take in order to lower the initial radioactivity to 10-3 of the initial value?
d) Write two alternative mechanisms for the reaction of labelled PCl4+ with the anion of I.
e) After hydrolysis the precipitated ammonium magnesium phosphates show the following values for radioactivity:
II. 2380 Bq for 128 mg of Mg(NH4)PO4
III. 28 Bq for 153 mg of Mg(NH4)PO4
IV. 2627 Bq for 142 mg of Mg(NH4)PO4

Using these data, what can you say about the nucleophilic centre attacked by PCl4+?

Data:

H3PO4: pK1 = 2.2, pK2 = 7.2, pK3 = 12.4

solubility product of Mg(NH4)PO4:pKsp = 12.6
equilibrium concentration of NH4+ = 0.1 mol/l

f) Calculate the solubility for Mg(NH4)PO4 at pH equal to 10 under idealized conditions (activity coefficients can be
neglected).

IChO Paris 1990

The mineral apatite is a mixture of tricalcium diphosphate Ca3(PO4)2, calcium sulphate, calcium fluoride, calcium carbonate
and silica. An elemental analysis gave the following result:

CaO P2O5 SiO2 F SO3 CO2

% by mass 47.3 28.4 3.4 3.4 3.5 6.1

A sample of m0 g of this mineral is treated with 50.0 ml of a solution containing 0.500 mol/L phosphoric acid and 0.100
mol/l sulphuric acid. The mixture is completely dehydrated by heating up to 70 °C. Toxic gases are emitted thereby. m1
g of dry residue is obtained. In these conditions, only phosphate Ca(H2PO4)2 is formed, silica and silicate do not react.
1.00 g of this residue is treated with 50.0 ml of water at 40 °C, filtered, dried and m2 g obtained. This new residue is mainly
containing gypsum (CaSO4 °2H2O) whose solubility between 20 °C and 50 °C is equal to 2.3 g/l.

a) Write the balanced equations for all reactions. From what mass of apatite should one start if the reactions are
stoichiometric?
b) Starting with m0 g of apatite, m1 = 5.49 g of residue are obtained. What mass should theoretically have been
obtained? This result is due to the presence of two products that are not expected to be in the residue. Which
product are these?

Traditionally, the yield is expressed as percentage of oxide. The phosphorous content is expressed as if it were P2O5. If
n2 is the amount of soluble product obtained, n1 the amount of substances added as acid, n0 the amount of apatite
added, the yield is:

n2
r exp = 100 ⋅
n1 + n0

c) m2 = 0.144 g of residue is obtained on the filter. Calculate rexp.

d) The experimental yield is over 100 %. Calculate a value of r nearer to the real yield.

IChO Paris 1990

a) Consider a 1.00⋅10-2 solution of copper(II) nitrate. The pH of this solution is 4.65. Give the equation for the formation
of the conjugate base of the hydrated Cu2+ ion and calculate the pKa of the corresponding acid-base pair. The
solubility product of copper(II) hydroxide is Ksp = 10-20 . At what pH would Cu(OH)2 precipitate from the solution
under consideration? Justify your calculation, showing that the conjugate base of this hydrated Cu2+ ion is present
in negligible quantity.
b) Write down the equation for the disproportionation of copper(I) ions and calculate the corresponding equilibrium
constant. E10(Cu+/Cu) = 0.52 V, E20(Cu2+/Cu+) = 0.16 V. Calculate the composition in mol/l of the solution obtained
on dissolving 1.0⋅10-2 mol of copper(I) in 1.0 l of water. Name two chemical species which also disproportionate in
aqueous solution; write down the equations and describe the experimental conditions under which disproportionation
is observed.
c) Consider the stability of copper(I) oxide (Cu2O) in contact with a 1.00⋅10-2 mol/l solution of Cu2+ ions. The stability
product of copper(I) oxide is Ksp = [Cu+][OH-] = 10-15
Quote a simple experiment allowing the observation of the precipitation of Cu2O.
d) The dissociation constant of the complex ion [Cu(NH3)2]+ is KD = 10-11. Calculate the standard electrode potential
of the couple:

[Cu( NH3 )2 ]+ + e- → Cu + 2 NH3

e) The emf of the couple [Cu(NH3)4]2+ + 2e- _ Cu = 4 NH3 is E30 = - 0,02 V. Calculate the dissociation constant of the
complex ion [Cu(NH3)4]2+. Deduce from it the emf of the couple:

[Cu( NH3 )4 ]2+ + e- → [Cu( NH3 )2 ]+ + 2 NH3

Does the disproportionation of the cation [Cu(NH3)2]+ take place?

IChO Lodz 1991

a) Show that 0.1 mol of Tl2S dissolves in a 1M solution of any strong monoprotic non-coordinating acid.
b) Show that 0.1 CuS dissolves in a 1M HNO3 but not in a 1M HCl solution.
Information:

Assume that Cu2+ ions don’t form stable complexes with chloride ions in aqueous solutions.

E0(S/S2-) = - 0.48 V E0(NO3-/NO(aq)) = 0.96 V

pKa(H2S) = 7 pKa(HS-) = 13
Ksp(Tl2S) = 10-20 Ksp(CuS) = 10-35
R = 8.314 J K-1 mol-1 F = 96487 C mol-1

IChO Lodz 1991

Type II electrodes are made of a metal covered with a sparingly soluble salt of the metal that are dipped into a soluble salt
solution containing an anion of the sparingly soluble salt. The silver/silverchloride (Ag, AgCl/Cl-) and the calomel
electrode (Hg, Hg2Cl2/Cl-) are examples of such electrodes. The standard emf of a cell built of those electrodes (-)
Ag,AgCl/Cl-/Hg2Cl2/Hg (+) is E0 = 0.0455 V. at T = 298 K. The temperature coefficient for this cell is dE0/dT = 3.38⋅10-4
V/K.

a) Give the equations of the reactions taking place at both the cell electrodes and the overall cell reaction.
b) Calculate the Gibbs free energy change (∆G0) for the process taking place in the cell. What does its sign imply ?
c) Calculate the enthalpy change for the process taking place at 298 K, given ∆S = n F dE/dT.
d) Knowing the standard potential of Ag/Ag+ electrode is E0 = 0.799 V and the solubility product of AgCl Ksp = 1.73⋅10-
10
, calculate the standard electrode potential value of the silver/silver chloride electrode. Derive an expression
showing the dependence between E0 (Ag/Ag+) and E0 (Ag, AgCl/Cl-).
e) Calculate the solubility product of Hg2Cl2 knowing that the standard potential of the calomel electrode is E0 = 0.798
V.

IChO Pittsburgh 1992

Many streams drain in areas where coal or metallic ores are mined. These streams have become acidic and contain high
concentrations of dissolved iron and sulfate, due to sulfur-containing ores being exposed to the atmosphere or to
oxygenated waters. The most common sulfur-containing mineral is pyrite, FeS2, in which the oxidation state of iron is +2.
As the iron-rich streams mix with other waters, the dissolved iron precipitates as goethite, FeO(OH), which coats the
stream bottom while the water remains acidic.

a) Draw the electron dot structure that illustrates the bonding in the S22--ion, showing all valence electrons.
b) Write a balanced chemical equation to show how hydrogen ions (H+) are genrated during the oxidation of pyrite to
form iron(II) ions and sulphate.
c) Write a balanced equation to show how many additional moles of hydrogen are generated when iron(II)ions are
oxidized to form the mineral goethite, FeO(OH).
d) Calculate how many moles of pyrite would be required to bring 1.0 litre of pure water to a pH of 3.0 if the pyrite was
completely converted into FeO(OH) and H+. Neglect the formation of HSO4-.
e) The concentration of iron as Fe(II) in a stream is 0.00835 M. At a very narrow point in the stream it empties into a large
pond, with a flow rate of 20.0 l/min. The water in this stream is sufficiently aerated that 75% of the iron(II) is oxidized
to Fe(III) which immediately precipitates as Fe(OH)3 later aging to became Fe2O3. What mass of Fe2O3 will be
deposited on the bottom of the pond in two years ?

IChO Pittsburgh 1992

Diatoms, microscopic organisms, produce carbohydrates from carbon dioxide and water by normal photosynthesis: 6
CO2 + 6 H2O + solar energy → C6H12O6 + 6 O2
During the first five years of life whales gain 75 kg of mass per day by feeding on krill. The whale must consume ten times
this mass of krill each day. The krill must consume 10.0 kg of diatoms to produce 1.0 kg of krill.
a) Assuming that the mass gain in the first years of a whale’s life is due to the consumption of carbohydrates, calculate
the volume of CO2 at 0 °C and 101kPa that must be used by the diatoms to produce the carbohydrates consumed by
 a blue whale in its first five years of life.
b) There is 0.23 mL of dissolved CO2 per l sea water (at 24 °C and 101kPa). If diatoms can completely remove carbon
dioxide from the water they process, what volume of water would they process to produce the carbohydrates
required by a blue whale during the first five years of life ?
c) 3% of the mass of a 9.1⋅104 kg adult whale is nitrogen. What is the maximum mass of NH4+ that can become available
for other marine organisms if one adult whale dies ?
d) 18% of a adult whale’s mass is carbon which can be returned to the atmosphere as CO2 being removed from there by
weathering of rocks containing calcium silicate.

CaSiO3 (s) + 2 CO2 + 3 H2O (l) → Ca2+ (aq) + 2 HCO3- (aq) + H4SiO4 (aq)

What are the maximum number of grams of CaSiO3 that can be weathered by the carbon dioxide produced from the
decomposition of 1000 blue whales, the number estimated to die annually ?

IChO Pittsburgh 1992

The Pourbaix diagrams of water, nitrogen and manganese are depicted in Fig. 3.

a) Which species of nitrogen is predominant in a1) O2-rich lakes of pH ~ 6 , a2) O2-depleted lakes of pH ~ 3 b)Which
species of manganese is predominant in b1) O2-rich lakes of pH ~ 6, b2) highly O2-depleted lakes of pH ~ 12 ?
c) People often find that clear, slightly acidic (pH ~ 5) water drawn from wells deposits a black manganese-containing
solid on standing in toilet bowls. What is the chemical formula of the black solid ? What is the corresponding species
of manganese found in well water while it is still underground ?
d) Which of the two species of nitrogen oxidize Mn (s) to Mn2+ (aq) according to the Pourbaix diagrams ? Which one
of this actually (in practice) does not oxidize Mn (s) at room temperature ?
e) Which of the following compounds oxidize NH3 (aq) or NH4+ (aq) to N2 (g) ?
Mn, Mn(OH)2, Mn2+, Mn3O4, Mn2O3, MnO2, MnO42-, MnO4-

We shall discuss the properties of the two salts ammonium permanganate, NH4MnO4, and ammonium manganate,
(NH4)2MnO4, which is a rarely known salt.

f) Are the salts NH4MnO4 and (NH4)2MnO4 thermodynamically stable ?

g) Write the balanced equation of the decomposition of both salts to give MnO2, Mn and N2.
h) Is it dangerous to grind together h1) potassium nitrate and manganese metal, h2) KNO3 and MnO2 ?
i) The standard reduction potential for the reduction of MnO4- to MnO2 is 1.692 V. Applying the Nernst equation,
calculate the reduction potential for the reduction of 0.00100 M MnO4- at a pH = 4.0.
Fig. 3 Pourbaix diagrams of H2O, N and Mn

IChO Peruggia 93
131I is a radioactive isotope of iodine (e- emitter) used in nuclear medicine for analytical procedures to determine thyroid
endocrine disorders by scintigraphy. The decay rate constant, k, is 9.93 10-7 s-1.

a) Write the decay reaction of 131I

b) Calculate the half-life of 131I expressed in days
c) Calculate the time necessary (expressed in days) for a sample of 131I to reduce its activity to 30% of the
original value.
d) Knowing that a Geiger counter detects activities of the order of 10-4 µc, calculate the the minimum amount of
131I which could be detected by this counter. Note that 1 Curie (c) is the amount of radioisotopes that produces 3.7
⋅ 1010 disintegrations per second.

IChO Oslo 1994

Sulfur forms many different compounds with oxygen and halogens (sulfur as the central atom). These compounds are
mainly molecular, and many are easily hydrolysed in water.
a) Write Lewis structures for the molecules SCl2, SO3, SO2ClF, SF4, and SBrF5. Show all non-bonding electrons.

b) Carefully draw the geometries of the same 5 molecules. (Disregard small deviations from „ideal“ angles.)

c) A compound, consisting of sulfur (one atom per molecule), oxygen, and one or more of the elements F, Cl, Br, and I,
was examined. A small amount of the substance was reacted with water. It was completely hydrolyzed without any
oxidation or reduction, and all reaction products dissolved. 0.1M solutions of a series of test reagents were added to
separate, small portions of a diluted solution of the substance.

State which ions were being tested for in the following tests:

I) Addition of HNO3 and AgNO3.

ii) Addition of Ba(NO3)2.

iii) Adjustment to pH = 7 with NH3 and addition of Ca(NO3)2

Write the equations for the possible reactions in the following tests:

iv) Addition of KMnO4 to an acidified solution of the substance followed by addition of Ba(NO3)2

v) Addition of Cu(NO3)2.

d) In practice, the tests in c) gave the following results:

i) A yellowish precipitate
ii) No precipitate
iii) No visible reaction
iv) The main features were that the characteristic colour of KMnO4 disappeared, and a white precipitatew a s
formed upon subsequent addition of Ba(NO3)2
v) No precipitate

Write the formulae of the possible compounds, taking the results of these tests into account.

e) Finally, a simple quantitative analysis was undertaken: 7.190 g of the substance was weighed out and dissolved in
water to give 250.0 mL solution. To 25.00 mL of this solution, nitric acid, and enough AgNO3 to secure complete
precipitation, was added. The precipitate weighed 1.452 g after washing and drying. Determine the formula of the
compound.

f) Write the equation describing the reaction of the compound with water.
If you have not arrived at a formula for the compound, use SOClF for this equation.

IChO Oslo 1994

a) Nitrogen in agricultural materials is often determined by the Kjeldahl method. The method involves a treatment of the
sample with hot concentrated sulphuric acid, to convert organically bound nitrogen to ammonium ion. Concentrated
sodium hydroxide is then added, and the ammonia formed is distilled into hydrochloric acid of known volume and
concentration. The excess hydrochloric acid is then back-titrated with a standard solution of sodium hydroxide, to
determine nitrogen in the sample.

Calculate the percentage by mass of nitrogen in the sample.

b) Calculate the pH of the solution during the titration in a), after 0 mL, 9.65 mL, 19.30 mL and 28.95 mL of sodium
hydroxide have been added. Disregard any volume change during the reaction of ammonia gas with hydrochloric
acid.

Ka for ammonium ion is 5.7 x 10-10

c) Draw the titration curve based on the calculations in b).

d) State the pH range of the indicator which could be used for the back titration.

e) The Kjeldahl method can also be used to determine the molecular weight of amino acids. In a given experiment, the
molecular weight of a naturally occurring amino acid was determined by digesting 0.2345 g of the pure acid, and
distilling the ammonia into 50.00 mL of 0.1010 M hydrochloric acid. A titration volume of 17.50 mL was obtained for
the back titration with 0.1050 M sodium hydroxide. Calculate the molecular weight of the amino acid based on one
and two nitrogen groups in the molecule, respectively.

3. Physical chemistry

IChO Leiden 1986

In order to explain why dyes are coloured, they can be considered as rod-like, one-dimensional molecules over which the
electrons are distributed. The wave lengths of the electrons should fit to the available space, which is the length l. When
absorbing light, an electron makes a transition from a lower to a higher energy state. The energy difference is given by:

h⋅c h
∆E = where γ =
γ p

a) Give a general expression for possible wavelengths of the electron as a function of the length l.

In the ‚particle in the box‘ model, only the variations in the kinetic energy of the electrons are considered.

b) Give an expression for the possible energies that electrons in the molecule can have (as a function of l).
c) Show that for a chain of length l with k electrons, the longest wavelength absorption occurs at:

8 mcl 2
γ = for even values of k
h(k +1)
d) Derive an expression for the wavelength of the first electronic transition as a function of the number of C-atoms for
even values of n.
e) Calculate the minimum number of C-atoms (conjugated systems) to obtain a visible colour. C-C bond length is 142 pm.

The retina in the human eye contains rhodopsin, a light absorbent.

7 11 15
1 9 13 O
2 6 8 10 12 14
59º 39º
3
4 5

The C-atoms 7 through 12 are planar. The angle between the bonds C5-C6, C7-C8, C11-C12 and C13-C14 is about 39°.
According to the ‚particle in the box‘ theory fragment C7 through C12 should absorb at about 213 nm. In reality the
absorption of retinal occurs at 308 nm.

f) Give a reason for the longer wavelength that is observed in praxis using the above mentioned theories.
g) When retinal is bound to opsin to form rhodopsin, the absorption occurs around 600 nm. Which atoms must be
forced into one plane by the protein ? Show by calculation that it’s true.
IChO Helsinki 1988
A typical family car has four cylinders with a total cylinder volume of 1600 cm3 and a fuel consumption of 7.0 l per 100 km
when driving at a speed of 90 km / h. During one second each cylinder goes through 25 burn cycles and consumes 0.4
g of fuel. Assume that fuel consists of 2,2,4 - trimethyl - pentane, C8H18. The compression ratio of the cylinder is 1:8.

a) Calculate the air intake of the engine (m3/s). The gasified fuel and air are introduced into the cylinder when its volume
is largest until the pressure is 101.0 kPa. Temperature of both incoming air and fuel are 100 °C. Air contains 21.0 % (by
volume) of O2 and 79.0 % of N2. It is assumed that 10.0 % of the carbon forms CO upon combustion and that nitrogen
remains inert.
b) The gasified fuel and the air are compressed until the volume in the cylinder is at its smallest and then ignited.
Calculate the composition (% by volume) and the temperature of the exhaust gases immediately after the combustion
(exhaust gases have not yet started to expand). The following data is given:

Compound Hf (kJ / mol) Cp (J / mol K)

O2(g) 0.0 29.36
N2(g) 0.0 29.13
CO(g) -110.53 29.14
CO2(g) -395.51 37.11
H2O (g) -241.82 33.58
2,2,4 - trimethylpentane -187.82

c) Calculate the final temperature of the leaving gases assuming that the piston has moved to expand the gases to the
maximum volume of the cylinder and that the final gas pressure in the cylinder is 200 kPa.

d) To convert CO(g) into CO2(g) the exhaust gases are led through a bed of catalysts with the following work function:

n(CO) 1 n(CO) T
= k v e- T 0
n(CO2 ) 4 n(CO2 )1

where [n(CO) / n(CO2)]1 is the molar ration before the catalyst, v is the flow rate in mol / s and T the temperature of the
gases entering the catalyst (the same as the temperature of the leaving exhaust gases). T0 is a reference temperature (373
K) and k is equal to 3.141 s / mol. Calculate the composition (% by volume) of the exhaust gases leaving the catalyst.

IChO Helsinki 1988

The periodic system of the elements in our three-dimensional world is based on the four electron quantum numbers n =
1,2,3,....; l = 0,1,....,n-1, m = 0, ±1, ±2,...., ±1; and s = ±1/2. In Flatlandia, a two-dimensional world, the periodic system is
thus based on three electron quantum numbers: n = 1,2,3,...; m1 = 0, ±1, ±2, ...., ± (n-1); and s = ±1/2 where m1 plays the
combined role of l and m of the three dimensional world. The following tasks relate to this two-dimensional world, where
the chemical and physical experience obtained from our world is supposed to be still applicable.

a) Draw the first four periods of the Flatlandian periodic table of the elements. Number them according to their nuclear
charge. Use the atomic numbers (Z) as symbols of the specific element. Write the electron configuration for each
point.
b) Draw the hybrid orbitals of the elements with n = 2. Which element is the basis for the organic chemistry in Flatlandia?
Find the Flatlandian analogous for ethane, ethene and cyclohexane. What kind of aromatic ring compounds are
possible ?
c) Which rules in Flatlandia correspond to the octet and the 18-electron rules in the three dimensional world?
d) Predict graphically the trends in the first ionization energies of the Flatlandian elements with n = 2. Show graphically
how the electronegativities of the elements increase in the Flatlandian periodic table.
e) Draw the molecular orbital energy diagrams of the neutral homonuclear diatomic molecules of the elements with n =
2. Which of these molecules are stable in Flatlandia?
f) Consider simple binary compounds of the elements (n=2) with Z=1. Draw their Lewis structure, predict their geometries
and propose analogs for them in the three dimensional world.
g) Consider elements with n≤3. Propose an analog and write the chemical symbol from our world for each of these
Flatlandian elements. On the basis of this chemical and physical analog predict which two-dimensional elements are
solid, liquid or gaseous at normal pressure and temperature.
IChO Halle 1989
A mixture of gases containing mainly carbon monoxide and hydrogen is produced by the reaction of alkanes with steam:

CH 4 + 0.5 O2 → CO + 2 H2 ∆H = - 36 kJ mol-1
CH 4 + H2 O → CO + 3 H2 ∆H = 216 kJ mol-1

a) Using equations (1) and (2) write down an overall reaction (3) so that the net enthalpy change is zero.

b) The synthesis of methanol from carbon monoxide and hydrogen is carried out either

1. in two steps, where the starting mixture corresponding to equation (3) is compressed from 0.1⋅106 Pa to 3 ⋅ 106 Pa,
and the mixture of products thereof compressed again from 3 ⋅ 106 Pa to 6 106 Pa
or
2. in one step, where the mixture of products corresponding to equation (3) is compressed from 0.1 ⋅ 106 Pa to 6 ⋅ 106
Pa.

Calculate the work of compression, Wa, according to the two step reaction for 100 ml of starting mixture and calculate
the difference in the work of compression between the reactions 1. and 2.

Assume for calculations a complete reaction at constant pressure. Temperature remains constant at 500 K, ideal gas
behaviour is assumed.

To produce hydrogen for the synthesis of ammonia, a mixture of 40.0 mol CO and 40.0 mol of hydrogen, 18.0 mol of
carbon dioxide and 2.0 mol of nitrogen are in contact with 200.0 mol of steam in a reactor where the conversion
equilibrium

CO + H2 O ←
 _
→ CO2 + H2 is established.

c) Calculate the number of moles of each gas leaving the reactor.

IChO Paris 1990

a) Show that burning zinc sulphide in air according to

ZnSsolid + 1.5 O2 → ZnOsolid + SO2 (gas) ∆ r H(1350K) = - 448.98 kJ mol-1

is self-sustaining at 1350 K, i.e that the heat produced is sufficient to bring the reactants from ambient temperature to
the heat temperature.

b) Starting with a stoichiometric mixture of one mole zinc blende only containing ZnS and a necessary quantity of air at
298 K, calculate the temperature to which the mixture would raise at 1350 K under standard pressure. Is the reaction
self-sustaining? Air is considered to be a mixture of oxygen and nitrogen in a volume ration equal to 1:4.

c) In fact, zinc blende is never pure and always mixed with a gangue consisting of silica SiO2. Assuming that the gangue
does not react, calculate the minimum ZnS content of the mineral so that the reaction would be self-sustaining. Give
the answer is grams of ZnS per hundred grams of zinc blende.

Data:

Standard molar heat capacities (in J K-1 mol-1):

ZnS(solid): 58.05 ZnO(solid): 51.64

SO2(gas): 51.10 O2(gas): 34.24
N2(gas): 30.65 SiO2(solid): 72.50

Molar masses (in g mol-1): ZnS: 97.5

SiO2: 60.1

IChO Paris 1990

Nitramid NO2NH2 decomposes slowly in aqueous solution according to

NO2 NH 2 → N 2 O(g) + H 2 O

with the experimental kinetic law

a) What is the apparent order of reaction in a buffered solution ?

mechanism 1:

NO2NH2 k1 N2O + H2O

 → (rate limiting step)

mechanism 2:
+ /
k2 / k2
NO2NH2 + H3O ← → NO2NH3+ + H2O (rapid equilibrium)
+ k3 +
NO2NH3  → N2O + H3O (rate limiting step)

mechanism 3:
k4 /k4/ - +
NO2NH2 + H2O ← → NO2NH + H3O (rapid equilibrium)
- k5 -
NO2NH  → N2O + OH (rate limiting step)
+ - k6
H3O + OH  → 2 H2O (very fast reaction)

b) Which of the following mechanisms is the most appropriate for the interpretation of this kinetic law. Justify your
answer.
c) Show the relationship between the experimentally observed rate constant and the rate constants in the selected
mechanism.
d) Show that hydroxyl ions catalyze the decomposition of nitramid.
e) The decomposition is studied in a buffered solution of constant volume V at a constant temperature by measuring
the partial pressure of the gas N2O, insoluble in water, in a constant volume of the same value V above the solution.
The following results are obtained:

t(min) 0 5 10 15 20 25
p(Pa) 0 6800 12400 17200 20800 24000

After a sufficiently long time, the pressure stabilises at 40000 Pa. Express the pressure P as a function of time and the
+
constant k‚ such that k‚ = k / [H3O ]. Verify graphically that the kinetic law is confirmed by these experimental results.
Calculate k‘, giving its units.
IChO Lodz 1991
The energy of stable states of the hydrogen atom is given by: En = -2.18 ⋅ 10-18 n-2 J-1 where n denotes the principal
quantum number.

a) Calculate the energy differences between n = 2 (first excited state) and n = 1 (ground state) and between n = 7 and n
= 1.
b) In what spectral range are the Lyman series lying ?
c) Can a single photon emitted in the first and/or sixth line of the Lyman series ionize
1) another hydrogen atom in its ground state ?
2) a copper atom in the Cu crystal ?

The electron work function of Cu is φCu = 7.44 ⋅ 10-19.

d) Calculate the de Broglie wavelength of the electrons emitted from a copper crystal when irradiated by photons from
the first line and the sixth line of the Lyman series.

IChO Pittsburgh 1992

The paramagnetic gas NO2 can dimerize to give the diamagnetic gas N2O4: 2 NO2 (g) → N2O4 (g)

a) With a diagram, show the bonding present in NO2 (g) using the concept of resonance if necessary. Use dots to
represent electrons.
b) Show, with bonding diagrams, how two molecules of NO2 (g) combine to give a molecule of N2O4 (g).
c) At 298 K, the ∆Go of formation for N2O4 (g) is 98.28 kJ, whereas for NO2 (g) it is 51.84 kJ. Starting with one mole of
N2O4 (g) at 1.0 atm and 298 K, calculate what fraction will be decomposed if the total pressure is kept constant at 1.0
atm and the temperature is maintained at 298 K.
o
d) If ∆H for the reaction N2O4 (g) → 2 NO2 (g) is 53.03 kJ, at what temperature would the fraction of N2O4 decomposed
be double the one calculated in part c) ?
e) The dissociation of N2O4 (g) to give NO2 (g) is a first order process with a specific rate constant of 5.3 104 s-1 at 298
K. Starting with an initial concentration of 0.10 M, how many seconds would it take for 20 % of the original N2O4 to
decompose ?
f) The association of NO2 (g) to give N2O4 (g) is a second-order process with a specific rate constant of 9.8 106 L mol-
1 -1
s at 298 K. Calculate the concentration equilibrium constant, Kc, at 298 K for the reaction 2 NO2 (g) → N2O4 (g)

IChO Pittsburgh 1992

The concentration of carbon dioxide in the atmosphere has increased substantially during this century. The [CO2] is
expected to be about 440 ppm (440 ⋅ 10-6 atm) in the year 2020.

a) Calculate the concentration, in mol/l, of CO2 dissolved in distilled water equilibrated with the atmosphere in the year
2020. What is its pH-value ?

b) Calculate the enthalpy of reaction between CO2 (aq) and H2O.

c) Will the pH increase or decrease if the temperature of an equilibrated solution of CO2 in water is increased and the
concentration of dissolved CO2 maintained constant ?

Data:

Henry’s Law constant for CO2 at 298 K: 0.0343 l mol-1 atm-1

Thermodynamic values, in kJ/mol at 298 K are:

∆Gof ∆H o f
CO2 (aq)-386.2 -412.9
H2O (l) -237.2 -285.8
HCO3- (aq) -587.1 -691.2
H+ (aq) 0.00 0.00
IChO Peruggia 93
Poisoning by carbon monoxide produced by ill-adjusted heating systems is a serious problem. In a methane burner the
following reactions occur:

CH4 O2 Co2 CO H2O

∆H f (kJmol-1)
o -74.9 0 -393.5 -110.5 -241.8
So (JK-1mol-1) 186.2 205.0 213.6 197.6 188.7

a) Calculate the equilibrium constants of both reactions at T = 1500 K, assuming that the values of ∆Ho and ∆S o
are independant of temperature.
b) Find the relationship between the mole numbers of oxygen and carbon monoxide at equilibrium (T = 1500 K, P =
1 atm) when air is admitted into the burner in such amount that the mole ration CH4/O2 is 2:1. Assume the following
volume composition for air: 80% N2 and 20% O2. Make the approximation that nCH4 = 0 at equilibrium and justify
it on the basis of the answers to question a).
c) Calculate the equilibrium mole fraction (x) of CO in the conditions given in b). Assume that the mole fraction of
CO is very small in comparison with that of CO2 and consequently the total number of molesdoes not appreciably vary
during the combustion. Justify this assumption.
d) Repeat the calculations of items b) and c) assuming that twice the amount of air (compared to the
conditions of questions b) is admitted into the burner (4 mol O2 / 1 mol CH4).
e) Calculate the concentrations of CO (expressed as ppm by volume) in the fumes after condensation of w a t e r
vapour under the conditions of questions b) and d), assuming that the composition does not change during the
cooling from 1500 K to room temperature and neglecting the contributions of water vapour in the composition of the
gas phase.

IChO Oslo 1994

Platinum(IV) oxide is not found in the nature, but can be prepared in a laboratory. Solid platinum(IV) oxide is in equilibrium
with platinum metal and oxygen gas at 1 atm (101.3 kPa) at 650 °C.

a) This suggests that the conditions on the Earth, when platinum minerals were formed, were:

1. pO2 = 1 atm, t = 650 °C;

2. pO2 < 1 atm, t < 650 °C;
3. pO2 > 1 atm, t < 650 °C;
4. pO2 < 1 atm, t > 650 °C;
5. pO2 > 1 atm, t > 650 °C

Mark the most probable altemative [ 1 ] - [ 5 ] on the answer sheet.

b) What are ∆G and Kp for the formation of platinum(IV) oxide at 1 atm oxygen pressure and 650 °.C?

The preparation of platinum(IV) oxide involves boiling a solution which contains hexachloroplatinate(IV) ions with
sodium carbonate. In this process PtO2.nH2O is formed and is subsequently converted by filtration and heat treatment
to platinum(IV) oxide. In the following we assume n=4. PtO2.4H2O (or Pt(OH)4.2H2O) can be dissolved in acids and
strong bases.

c) Write the balanced equations for the preparation of platinum(IV) oxide according to the procedure given above.
d) Write the balanced equations for the dissolution of PtO2.4H2O in both hydrochloric acid and sodium hydroxide.

Platinum is mainly found in nature as the metal (in a mixture or alloyed with other precious metals). Hexachloroplatinate(IV)
ions are formed by dissolving platinum in aqua regia. Aqua regia is a mixture of concentrated hydrochloric and nitric
acids in proportion 3:1. Upon mixing, this forms nitrosyl chloride (NOCl) and atomic chlorine. The latter is believed to be
the active dissolving component.
The hexachloroplatinate(IV) ions can be precipitated as diammonium hexachloroplatinate(IV). By thermal decomposition
of this compound, finely powdered platinum and gaseous products are formed.

e) Write the balanced equations for the formation of aqua regia and its reaction with platinum.
f) Write the balanced equation for the thermal decomposition of diammonium hexachloroplatinate(IV) at elevated
 temperature.

From diammonium hexachloroplatinate(IV) we can prepare Pt(NH3)2Cl2 which occurs in the cis (∆Hfo= -467.4 kJ/mol,
∆Gfo =-228.7 kJ/mol) and trans ∆Hfo = -480.3 kJ/mol, ∆Gfo = -222.8 kJ/mol) forms.

g) The occurrence of the isomers shows that the geometry of Pt(NH3)2Cl2 is

1. linear ?
2. planar ?
3. tetrahedral ?
4. octahedral ?

h) Indicate whether the cis or trans isomer is thermodynamically more stable. If you choose cis, mark [ 1 ] on the answer
sheet. If you choose trans, mark [ 2 ].

Platinum is used as a catalyst in modern automobiles. In the presence of the catalyst, carbon monoxide ∆Hfo = -110.5 kJ/
mol, ∆Gfo = -137.3 kJ/mol) reacts with oxygen to form carbon dioxide ∆Hfo = -393.5 kJ/mol, ∆Gfo = -394.4 kJ/mol).

I) Is the reaction spontaneous at 25 °C? [ 1 ] yes or [ 2 ] no. Is the reaction endothermic or exothermic? If you choose
endothermic, mark [ 1 ] on the answer sheet. If you choose exothermic, mark [ 2 ]. Calculate ∆So for the reaction.
Determine whether the entropy of the reaction system [ 1 ] increases or [ 2 ] decreases.
j) Derive an expression for the temperature dependence of the equilibrium constant in this case.

The overall catalytic reaction is simple, whereas the reaction mechanism in the gas phase is very complicated, with a
large number of reaction steps. With platinum as the catalyst the significant reaction steps are:

1. (i) adsorption of CO and adsorption/dissociation of O2 ([∆H = -259 kJ per mol CO + O),

2. (ii) their activation (105 kJ per mol CO + O) and
3. (iii) the reaction to and the desorption of CO2 (∆H = 21 kJ per mol CO2).

A one-dimensional energy-diagram for the platinum catalyzed oxidation of carbon monoxide to dioxide can be represented
as:

[Image]

k) Mark the correct alternative of [ 1 ] - [ 4 ] on the answer sheet.

IChO Oslo 1994

a) When an ideal, monatomic gas expands reversibly from volume V1 to volume V2, work
V2
w = − ∫ PdV
V1

is performed on the system by the surroundings. In this equation, w is the work and P is the pressure of the gas.
Determine the work performed when one mole ideal gas expands isothermally from V1 = 1.00 dm3 to V2 = 20.0 dm3 at
temperature T = 300.0 K. Given: The gas constant R = 8.314 J K-1 mol-1

b) Determine how much heat must be added to the gas during the process given under a).

c) The gas will perform less work in an adiabatic expansion than in an isothermal expansion. Is this because the
adiabatic expansion is characterized by (check the square you think is most important).
1. The volume of the gas is constant
2. The expansion is always irreversible
3. No heat is supplied to the gas

d) The cyclic process shown schematically in Figure 1 shows the four steps in a refrigeration system with an ideal gas
as working medium. Identify the isothermal and adiabatic steps in the process. Here, TH and TC represent high and
low temperature, respectively. Specify for each step whether it is adiabatic or isothermal.
4. Technical chemistry

IChO Leiden 1986

-1
The equilibrium constant of the reaction A(g) + 2 B(g) → 2 C(g) is Kp = 10.0 MPa . The starting materials are supplied
at 25 °C and heated to 100 °C where complete equilibration takes place. Below 100 °C the reaction rate is negligibly small.
The whole process is executed continuously in a stationary state. The boiling points at 0.1 MPa of A, B and C are 40 °C,
80 °C and 60 °C, respectively. The three compounds have the same heat of evaporation: q J/mol. The heat capacities of
A,B and C may be neglected. A schematic diagram of a distillation is shown below (Fig. 4).

top product, liquid

bottom product, liquid

Fig. 4 Schematic diagram of a distillation

The total heat used at each of the two distillations is 3q J/mol (of the top product). Apart from distillation columns (each
with its own evaporator and condenser) the pieces of apparatus shown of Fig. 5 are available.

cooler/condenser

heater/evaporator

R reactor
Fig. 5 Pieces of apparatus available

a) Draw a flow diagram of the process in which all flows are given (flow sheet) and in which the starting materials are
used as efficiently as possible using as few pieces of apparatus as possible.
b) Express the equilibrium constant in terms of the degree of conversion and of total pressure for the case that the feed
to the reactor is stoichiometric. What is the value of the degree of conversion when total pressure is 0.100 MPa?
c) Number all flows. Calculate the composition of each flow in mol/s for a rate of production of 1 mole of C per second
under the conditions of part b.
d) In what respect can the reaction conditions influence the composition of the mixture that leaves the reactor? (Refer
to question b)
e) The process requires energy. For the conditions of b explain where energy should be supplied in the flow diagram
drawn in part a. Derive an expression for the total energy needed.

IChO Veszprém - Budapest 1987

Treating waste water in a sewage plant, 45 % of its carbohydrate (CH2O)n is completely oxidized, 10 % undergoes
anaerobic decomposition by fermentation (two components) and the rest remains in the sludge. The total gas formation
is 16 m3 per day (25 °C, 100 kPa).

a) What is the amount of carbohydrate remaining in the sludge measured in kg per day ?
b) Given the heat of combustion of methane (- 882 kJ / mol), calculate the amount of energy that can be produced by
combustion of the methane formed.
c) Knowing the concentration of the carbohydrate in the waste water to be 250 mg/ l, calculate the daily amount of waste
water processed in the plant in m3 of water per day.

IChO Halle 89
Sulphur dioxide is removed from waste gases of coal power stations by washing with aqueous suspensions of calcium
carbonate or calcium hydroxide. The residue formed is recovered.

a) Write all reactions as balanced equations.

b) How many kilograms of calcium carbonate are daily consumed to remove 95% of the sulphur dioxide if 10000 m3/h of
waste gas (corrected to O °C and standard pressure) containing 0.15% sulphur dioxide by volume are processed?
How many kilograms of gypsum are recovered thereby ?
c) Assuming that the sulphur dioxide is not being removed and equally spread in an atmospheric liquid water pool of
5000 m3 and fully returned on earth as rain, what is the expected pH of the condensed water ?
d) If a sodium sulphite solution is used for absorption, sulphur dioxide and the sulphite solution can be recovered.
Write down the balanced equations and point out possible pathways to increase the recovery of sulphur dioxide
from the liquid phase.

Information

Protolysis of sulphur dioxide in aqueous solution is described by:

SO2 + 2 H2 O → H3 O+ + HSO-3

The acidity constant Ka is equal to Ka = 10-2.25 mol/l. Assume ideal gases and a constant temperature of 0 °C at standard
pressure. M[CaCO3] = 100 g/mol; M[CaSO4] = 172 g/mol

IChO Paris 1990

Hydrogenation of benzene to cyclohexane is performed in continuous reactors. The reaction is as follows:

C6 H6 + 3 H2 → C6 H12 ∆ H0 = - 214kJ / mol at 200 ° C

Two different types of reactors are examined: continuous plug flow reactor and continuous stirred reactor (Fig. 6): In the
continuous plug flow reactor, reactants are introduced and mixed in the inlet of the reactant (F1, F2); each slice of
reaction medium (grey shaded zone in the diagram) moves along the inside without mixing with the others and exits from
the reactor (F3). When the flow has stabilized, concentrations and conditions are time-independent but dependent on
the location in the reactor. In the continuous stirred reactor, stirring is perfect and instantaneous. When the flow is
stabilized, concentration and conditions are time-independent and identical at every point of the reactor.

Fig. 6 Continuous plug flow and continuous stirred reactor

The differential yield of hydrogenation (Y) is given by

Y = - d([C6H12])/d([C6H6]).

The proportion of benzene already hydrogenated is given by p = [C6H12]/([C6H12]+[C6H6]). The relationship between
p and Y is shown in Fig. 7.

The aim is to hydrogenate almost all the benzene, i.e. 0.9 ≤ p ≥ 1 with the best mean yield
Y = - ∆([C6H12])/∆([C6H6]).

a) What is the value of p in a continuous stirred reactor leading to the maximal mean yield of hydrogenation? What is
the maximal value of Y?
b) For a continuous plug flow reactor, give a rough value of Y for 0.9 ≤ p ≤ 1:
Y = 0.97, 0.98, 0.99 or 1.00 ?
c) Represent by grey shading the quantities of benzene lost in installation P (plug flow reactor) and installation MP
(stirred reactor + plug flow reactor).
d) Give the amount of benzene annually lost in installation P and MP assuming an annual consumption of 100000 tons
of benzene.
y

1.00

0.99

0.98

0.97

0.96
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
[C6H12]/([C6H12]+[C6H6])

Fig. 7 relationship between p and Y

IChO Lodz 1991

Sulphuric acid is produced by catalytic oxidation of SO2 to SO3, absorption of SO3 in concentrated sulphuric acid
forming oleum (containing 20% SO3 by mass) and appropriate dilution hereafter. The gas leaving the catalyst chamber
contains nitrogen, oxygen, a trace of SO2 and 10 % (by volume) of SO3.
SO3 is converted into sulphuric acid (98 % by mass) and/or oleum.

a) Assuming that oleum is the only product formed, calculate the mass of water which is required for 1000 m3 of gas
leaving the catalyst chamber (273 K, 101.3 kPa) and determine the mass of oleum produced hereby.
b) Assuming that only 98 % sulphuric acid is produced, calculate the necessary mass of water and the mass of product
produced thereby.
c) In the industry both 98 % sulphuric acid and oleum are produced in a mass ratio of x = m1/m2, where m1 denotes the
mass of oleum, m2 the mass of 98 % sulphuric acid. Find an expression y = f(x) to describe the relation between the
mass of water consumed for 1000 m3 gas. Show that the results of a) and b) are in good agreement with your
mathematical expression.
5. Organic chemistry

IChO Leiden 1986

The high efficiency of catalysis by enzymes is mainly due to an enzyme-reactant complex in which the reacting group is
placed in a favourable position for the reaction with respect to the catalyzing groups of the enzyme. Studies are carried
out with model compounds in which a catalyzing group has been introduced in the proximity of the reaction centre of the
molecule. As an example we consider the hydrolysis of the amide bond in compound A. This reaction proceeds in water
at 39 °C and pH = 2 more than a million times faster than the hydrolysis of compound B.

NH NH
N

O O
O
OH HO

O A O B O C

log khyd

-2

-3

0 1 2 3 4 5 6 7 pH

Fig. 8 Relation between the rate constant khyd and pH for the hydrolysis of A

The relation between the rate constant khad and pH for the hydrolysis of A at 39 °C is shown in figure 8.
Further observations

Addition of water to the iso-imide C gives a rapid reaction, which initially yields A. Subsequently, hydrolysis of A
occurs.
13 18
The amid carbonyl group in A is labelled with C and the hydrolysis is allowed to take place in H2 O at pH = 2 and 39
°C. The diacid formed upon hydrolysis is isolated, converted into the di-silver salt and completely decarboxylated with
bromine in a anhydrous reaction medium. The formed carbon dioxide is a mixture of particles of masses 44, 45, 46 and 47
which are formed in equal amounts.

a) Why is the hydrolysis of A so much faster then that of B ?

b) Explain why the rate of hydrolysis of A is independent of pH on the range between pH = 0 to pH = 2.
c) Why does khyd decrease so rapidly at pH-values higher than 3.
d) Give a detailed reaction mechanism for the hydrolysis of A. Indicate which step in the reaction is rate determining.
e) Show that the observations further made are consistent with the reaction mechanism given under d.

IChO Leiden 1986

Bacterial conversion of saccharose leads to (S) - (+) - 2 - hydroxypropanoic acid (L - (+) - lactic acid), which forms a cyclic
ester out of two molecules. This dilactide can be polymerized to a polylactide, which is used in surgery.

a) Give the spatial structures and Fischer projection of L - (+) - lactic acid and its dilactide
b) Sketch the structure of the polylactide discussed above (at least three units). What is its tacticity (iso-, syndio- or
atactic) ?
c) Draw the isomeric dilactides formed out of racemic lactic acid. Show the configuration of the chiral centres.

L - (+) - lactic acid is used for the preparation of the herbicide Barnon that is used against wild oats. In this case (+) - lactic
acid is esterified with 2 - propanol and then the hydroxyl group is treated with methanesulfonyl chloride. The product is
then submitted to a SN2 - reaction with 3 - fluoro - 4 - chloro - phenylamine, where the methanesulfonate group leaves as
-
CH3SO3 . Finally a benzoyl group is introduced with the help of benzoyl chloride.

d) Draw the Fischer projection of the various consecutive reaction products.

IChO Veszprém - Budapest 1987

Write the structural formulae of the compounds A to I in the following reaction sequence.

O
Mg/abs. ether 1. PBr3 NaCN
A B C D E
2. H2O

H2O/H2SO4 Friedel-Crafts H2
SOCl2
E F G H I
heat AlCl3 cat.

conc. H2SO4
I indene
heat
IChO Veszprem - Budapest 1987
a) What ratio of primary / secondary / tertiary products can statistically be expected in the high temperature chlorina-
tion of methylbutane? Assume that the reaction rate of the substitution is equal for all C-H bonds.
b) Which of the following alcohols: pentan-1-ol, pentan-2-ol and 2-methyl-butan-2-ol react with the following reagents
listed below ?
1) cold, concentrated sulphuric acid; 2) CrO3/H2SO4; 3) ZnCl2/HCl; 4) I2/NaOH
d) Which of the following aldohexose structures (Fig. 9) are 1) enantiomer pairs, 2) diastereomer pairs?
e) Two hydrocarbon compounds of the same molecular formula C4H8 easily react with hydrogen in presence of a
platinum catalyst. During ozonolysis only ethanal (acetaldehyde) is formed in both cases.
The 1H-NMR spectra of the two compounds show two types of protons in a ratio of 3 to 1. Draw the structures of the
described compounds.
f) Select the components of the group listed below that can be obtained during complete hydrolysis of lecithin (a
phospholipid): serine, phosphoric acid, sphingosine, choline, glycerol, myo-inositol,
phosphatidic acid and fatty acids).Which of the following carboxylic acid can be formed in the tricarboxylic acid
cycle (Krebs’ citric acid cycle): maleic acid (cis-butenedioic acid), mandelic acid (a-hydroxi-phenylethanoic acid),
malic acid (2-hydroxy-butanedioic acid), tricarb-allylic acid (propane-1,2,3-tricarboxylic acid), oxalacetic acid
(2-oxo-butanedioic acid), keto-glutaric acid (2-oxo-pentanedioic acid), fumaric acid (trans-butenedioic acid) and
acetoacetic acid (3-oxo-butanoic acid).
g) To which structures is the nicotinamide moiety (part) of NAD+ converted during the uptake of hydrogen to form
NADH (A, B or C) ?

CHO CHO CHO CHO

OH HO HO OH

HO HO OH OH

OH OH HO HO

OH OH HO HO

CH2OH CH2OH CH2OH CH2OH

A B C D

Fig. 9 Aldohexose structures

CONH2 CONH2 CONH2

NH+ N + H+ N + H+

A B C

IChO Helsinki 1988

A common compound A is prepared from phenol and oxidized to compound B. Dehydration of A with H2SO4 leads to
compound C and treatment of A with PBr3 gives D. In the mass spectrum of D there is a very strong peak at m/e = 83 (base
peak) and two molecular ion peaks at m/e 162 and 164. The ratio of intensities of the peaks 162 and 164 is 1.02. Compound
D can be converted to an organomagnesium compound E which reacts with a carbonyl compound F in dry ether to give
G after hydrolysis. G is a secundary alcohol with the molecular formula C8H16O.
a) Outline all steps in the synthesis of G and draw the structural formulae of the compounds A- G.
b) Which of the products A - G consist of configurational stereoisomeric pairs ?
c) Identify the three ions in the mass spectrum considering isotopic abundances given in the text.

IChO Helsinki 1988

Upon analyzing sea mussels a new bioaccumlated pollutant X was found as determined by mass spectroscopy coupled
to a gas chromatograph. The mass spectrum is illustrated in Fig 10. Determine the structural formula of X assuming that
it is produced out of synthetic rubber used as insulation in electrolysis cells that are used for the production of chlorine.
Give the name of the compound X. The isotopic abundances of the pertinent elements are shown in Fig. 11. Intensities
of the ions m/e = 196, 233, 268 and 270 are very low and thus omitted. Peaks of the 13C containing ions are omitted for
simplicity

100

50
M+

0
180 190 200 210 220 230 240 250 260

Element Mass Abundance Mass Abundance Mass Abundance

H 1 100.0 2 0.015
C 12 100.0 13 1.1
N 14 100.0 15 0.37
O 16 100.0 17 0.04
P 31 100.0
S 32 100.0 33 0.80 34 4.4
Cl 35 100.0 37 32.5
Br 79 100.0 81 98.0

Fig. 10 Mass spectrum and isotopic abundances

IChO Halle 1989

A chemically and biologically important class of organic compounds are carboxylic acids.

a) Draw the structural formulae of all isomeric cyclobutanedicarboxylic acids and give the corresponding systematic
names.
b) There are three stereoisomers, I,II and III. Draw perspective stereoformulas of I, II and III indicating the relative
configuration of each molecule.
c) Which pairs of stereoisomers I,II and III are diastereoisomers and which are enantiomers of each other ?
d) Which reaction can be used to determine the relative configuration of diastereoisomers?
e) How may the enantiomers of cyclobutane-1,2-dicarboxylic acid be separated ?
f) Indicate the absolute configuration of each asymmetric centre on the structures of the stereoisomers I, II and III
using the Cahn-Ingold-Prelog rules (R,S system).

Fats (lipids) contain a non-polar (hydrophobic) and a polar (hydrophilic) group.

g) Draw the structures of Z-octadec-9-enoic acid (oleic acid), octadecanoic acid (stearic acid) and hexadecanoic acid
(palmitic acid). Using the these three fatty acids draw a possible structure of a triacyl glyceride.
h) Write the equations for the hydrolysis reactions of your triacyl glyceride in NaOH(aq). Give the corresponding
mechanism.
i) Which of the following fatty acids, C21H43COOH, C17H35COOH or C5H11COOH is the least soluble in water.
k) Phospholipids are an important class of bio-organic compounds. Draw the structure of the phophatic acid derived
from your triacyl glyceride and mark the hydrophilic and hydrophobic groups.
l) Draw two possibilities for the association of six identical molecules of phopholipids in water.
m) Biomembranes consist of a phospholipid bi-layer. Draw such a structure. What other biomacromolecules are contained
in such biomembranes?

IChO Paris 1990

Synthesis of Haloperidol, a powerful neuroleptic

a) Give a simplified equation for the preparation of methyl 4 - chlorobenzoate starting from benzene and all necessary
inorganic substances. Diazomethane must be used in your synthesis.
b) How can γ-butyrolactone be converted into 4-hydroxybutanoic acid (K)? Convert K into 4-chlorobutanoyl chlorid
(L)!

Methyl 4 - chlorobenzoate is treated with an excess of vinylmagnesiumbromide in anhydrous ether. M is obtained after
hydrolysis. Treating M with an excess of HBr in anhydrous conditions in the presence of benzoyl peroxide, N is
obtained. N reacts with ammonia to form 4-(4-chlorophenyl)-4-hydroxypiperidine (O).

c) Write down the structure of M, N and O and indicate the mechanism of the reaction leading to M.
d) In the presence of moderate amounts of aluminium chloride, L reacts with fluorobenzene to yield mainly a ketone P
(C10H10OFCl). Sketch the structure of P and indicate the mechanism.
e) Give a chemical and physical test method for the determination of the carbonyl group. How can you make sure that
the carbonyl group does not belong to an aldehyde group?
f) P reacts with O on a 1 to 1 mole basis, in basic media, to give H that contains only one chlorine atom on the aromatic
ring. Give the structure of H which is haloperidol.
g) State the multiplicity of each resonance in the 1H NMR spectrum of K. Assume that all coupling constants between
protons and adjacent carbons are identical.

IChO Lodz 1991

A polymer X contains 88.25% C and 11.75% H. In dilute solutions it reacts with bromine and ozone. The thermal
degradation produces a volatile liquid Y in 58% yield. Y starts boiling at 34 °C and contains 88.24% C and 11.75% H.
Some higher boiling products are formed both from the cracking of X and from Diels-Alder-type cyclization of Y. The
vapour of Y was 34 times as dense as hydrogen. The product of bromination yields Y containing 82.5% bromine by mass.
Ozonolysis of Y followed by mild reduction gave A and B in a molar ration A:B = 2:1. Only compound B gave a positive
result for the iodoform reaction.

a) Determine the molecular formula and the molar mass of A, B and Y and show its structure.
b) Give an equation for the reaction of Y with bromine.

In the catalytic hydrogenation of 13.6 g of X, 0.2 mole of hydrogen was absorbed. Ozonolysis of X followed by mild
reduction yielded compound Z (80.0% C, 8.0% H).

c) Give the molecular formula of Z and the degree of unsaturation of X.

Compound Z gave a positive reaction with Fehling’s solution. Mild oxidation of Z gave an acid C of which a solution was
titrated with aqueous KOH. 0.116 g of C neutralized 0.001 mol KOH.
In the iodoform probe 2.90 g of C yielded 9.85 g of iodoform. In addition the alkaline filtrate yielded compound E upon
acidification.

d) What is the molar mass of C and what functional groups are present in Z?

When heated, E loses water to form F. Both E and F react with an excess of acidified ethanol to G (C8H14O4).

e) Sketch the structures of C, E, F, G and Z and give an unbalanced reaction scheme for E→F→G.

X exists in isomeric forms which are stereoregular. Show the structure (containing at least 3 monomer units) for two
possible stereoisomers of X.

IChO Lodz 1991

After passing 0.25 mol of hydrocarbon A over heated pumice (950 K) in an iron pipe, compound B in yield of 80 % (i.e.
15.4 g) and hydrogen, 2.4 l (295 K, 102 kPa) were obtained; B and hydrogen are the only products. A mixture of halogen
derivatives C, D, E, F and G is produced from B by reaction with a halogen in precence of a Lewis acid. C to G contain each
one halogen atom more then the preceeding compound. For the compounds C to F only one of the possible isomers is
formed. In compound G there is no such preference and its three isomers G1, G2 and G3 are found in the mixture.
Compounds C to F easily racemize, so that no optical isomerism occurrs. However racemization is difficult for G1, G2 and
especially for G3. In the mass spectrum of E only three isotopic peaks were observed. Their relative intensity is 1: 1: 0.3.

Information:

- kortho > kpara in compound B

- the effect of the first halogen in the ring: kpara > kortho
- compounds D and F have a center of symmetry
- the contribution of carbon and hydrogen isotopes in the mass spectrum of E are negligible
- natural abundance of halogen isotopes:
19
F = 100 %
35 37
Cl = 75.53 % Cl = 24.47 %
79 81
Br = 50.54 % Br = 49.46 %
127
I = 100 %

a) Give the structural formulas of A, B, C, D, E, F, G1, G2 and G3. Explain your choice for the halogen.
b) Draw and label stereo-formulas of the rotational isomers of D for ϕ = 0, π/2, 3π/2 where ϕ denotes the dihedral or
torsional angle in radians and ϕ = 0 describes the configuration with maximal energy.
c) Draw profiles of the energy changes as a function of the angle of rotation around the C-C bond for compounds C and
D.
d) Give G1, G2, G3 in their increasing difficulty of racemization. Explain your answer.
e) Draw stereo-formulas of the enantiomers of G3.
f) Suggest a chemical reaction or a biological method by which compounds like these can be destroyed.

IChO Pittsburgh 1992

Coniferyl alcohol which is not soluble is water or aqueous NaHCO3 has the molecular formula C10H12O3. It is isolated
from pine trees. A solution of Br2 in CCl4 is decolorized when added to coniferyl alcohol forming A (C10H12O3Br2). Upon
reductive ozonolysis vanillin (4-hydroxy-3-methoxybenzaldehyd) and B (C2H4O2) are produced. Coniferyl alcohol
reacts with benzoyl chloride (C6H5COCl) in the presence of a base to form C (C24H20O5). This product rapidly decolorized
KMnO4 (aq) and is insoluble in dilute NaOH.
Coniferyl alcohol reacts with cold HBr to form D (C10H11O2Br). Hot HI converting ArOR to ArOH and RI converts
coniferyl alcohol to E (C9H9O2I) and CH3I. In an aqueous base CH3I and coniferyl alcohol form F (C11H14O3), which is
not soluble in a strong base, but decolorizes Br2/CCl4-solution.

a) Draw the structures of compounds A-F including coniferyl alcohol.

b) There are a number of stereoisomers of A. Draw Fischer projections of all stereoisomers labelling each chiral centre
with the proper R or S designation giving the absolute configuration about the chiral centre.
IChO Pittsburgh 1992
Rose oil is obtained from steam distillation of roses. It contains a number of terpenes, one of which is geraniol, C10H18O
(A). Upon oxidation, geraniol can either give a ten-carbon aldehyde or a ten-carbon carboxylic acid. Reaction with two
moles of bromine gives a tetrabromide (C10H18OBr4) (B). Geraniol reacts with HBr to give two bromides of formula
C10H17Br.
When geraniol is vigorously oxidized, three products are obtained:

OH
O O O
OH
O
HO
O

a) Give the structure of geraniol (A), B and the two bromides of formula C10H17Br
b) Indicate which of the two bromides is formed in greater proportions.

IChO Pittsburgh 1992

Complete the following reactions and indicate their stereoselctivity (cis/trans) where appropriate.
a) O
∆
+ NaOH
O
isoamyl acetate, bee alarm pheromone

O
b) I2 / NaOH

2-heptanone, ant alarm pheromone

O
NaBH4

CH3CH2OH
O
CH3CH2MgBr H3O+

c) O3

Zn, H3O+

green peach aphid

pheromone

O3
H2O2, H3O+

d)
∆
H2O / H2SO4
OH

Na2Cr2O7, H2SO4

CH3COOH
e)
Br2/CCl4 HBr
(i) (iv) peroxide

KMnO4-, OH- BH3. ether

(ii) cold (v) H2O2, OH-

H3O+ H2, Pt
(iii) (vi)

IChO Peruggia 93
Frontalin is a pheromone of the western pine beetle with a composition C 67.58%, H 9.92%, O 22.50%. It is an acetal that
can be prepared starting from sodium diethylmalonate and 3-chloro-2-methylpropene. The resulting product A is
hydrolized by conc. potassium hydroxide and then decarboxylated by treatment with hot acetic acid to give a compound
B. The latter reacts with aq. NaHCO3 (gas evolution is observed) as well as with cold aq. KMnO4 which turns to a brown
color. The compound B is then converted by LiAlH4 into C (C6H12O).
Treatment of C with p-toluenesulfonyl chloride in pyridine and then sodium cyanid in dimethylsulfoxide affords D
(C7H11N). The subsequent reaction of D with methylmagnesium iodide, followed by hydrolisis, yields E (C8H14O). E
shows IR absorption at ca. 1700 cm-1. The epoxidation of E with metachloroperbenzoic acid then affords F (C8H14O2)
which, by treatment with diluted acids is converted to frontalin acetal G.

Question: Draw the structure of compounds A-G.

IChO Peruggia 93
By treatment with a optically active hydroborating agent (R2*BH) and subsequent oxidative work-up, 1-
methylcyclopentene affords a mixture of aclohols that rotates the plane of polarized light. [H.C.Brown, J.Org.Chem., 47,
5074, 1982]

a) Write the structures of the alcohols.

b) Assign the configurations (R,S) to the chiral centers.
c) Explain in a sentence why the obtained mixture of alcohols exhibits optical activity.

IChO Oslo 1994

a) What is the correct systematic name (IUPAC name) for the compound below?

(CH3)2CHCH(CH2CH3)(CH2CH2CH3)

1. 3-Isopropylhexane
2. 2-Methyl-3-propylpentane
3. Ethyl isopropyl propyl methane
4. 3-Hexylpropane
5. 3-Ethyl-2-methylhexane
b) How many isomers, including stereoisomers, containing only saturated carbon atoms, are there for C5H10?

c) Which one of the following compounds has a dipole moment significantly different from zero?

CN
OH
Br CH3
ClH2C CH2Cl NH

ClH2C CH2Cl HN
H3C Br
HO
NC CN

A B C D E

d) Which of the following is a pair of structural isomers?

Cl
CH3 Cl CH3 CH3
CH3

O
Cl O
Cl
A B C
CH3
H3C
CH3 CH3

H2C H3C
H3C
CH2
D E

e) Which of the following five options is the correct order of relative stabilities of cations a, b and c as written below?
Write the most stable first.

+ +

a b c

1. a > b > c
2. b > c > a
3. c > a > b
 4. a > c > b
5. b > a > c

f) What is the correct stereochemical descriptor of the optically active compound drawn below?

g) All the molecules drawn below are neutral compounds. Which one does not contain a formal positive charge and a
formal negative charge?

1. (CH3)3N-B(CH3)3
2. (CH3)2N-O-CH3
3. CH2=N=N
4. (CH3)3N-O
5. F3B-O(CH3)2

h) Which one of the IR-spectra shown on the next page corresponds to that of benzaldehyde?

[Image]

IChO Oslo 1994

An optically active compound A (C12H16O) has a strong IR-absorption at 3000-3500 cm-1, and two medium signals at 1580
and 1500 cm-1. The compound does not react with 2,4-dinitrophenylhydrazine (2,4-DNP). Upon treatment with I2/NaOH,
A is oxidized and gives a positive iodoform reaction.Ozonolysis of A (a. O3; b. Zn, H+) gives B (C9H10O) and C (C3H6O2).
Both B and C give precipitates when treated with 2,4-DNP, and only C gives a positive reaction with Tollen’s reagent
(Ag(NH3)2+). Nitration of B (HNO3/H2SO4) may give two mono-nitro compounds D and E, but in practice, only D is
formed. When the organic product from the Tollen’s reaction is acidified and then heated, compound F (C6H8O4) is
formed. F gives no IR absorption above 3100 cm-1.

a) Based on the above information draw the structural formulae for the compounds A-F and give the overall reaction
scheme, including the 2,4-DNP reaction and the products of the Tollen’s and iodoform reactions.

b) Draw C in an R-configuration. Transform this into a Fischer projection and state whether it is a D- or L-configuration.

6. Biochemistry

IChO Leiden 1986

In recombinant DNA technology specific endonucleases can recognize and hydrolyse the phosphoric ester bound in
each of both strands. Cla I for example hydrolyses the bond between two nucleotides in the sequence: 5'-pApT¦
pCpGpApT- 3'

a) Give the base sequence of the complementray strand in the 5' - 3' direction and indicate with arrows the location
where the hydrolysis by Cla I would occur.
b) How often on average will this sequence occur in one strand of DNA molecule of 105 base pairs? You can assume that
the four bases occur equally often and that they randomly distribute in the two chains.
 100
DNA treated with
ClaI

TaqI
50

0
260 280 300 320 340
T (K)

Fig. 111 Cleavage curve for DNA treated with ClaI and TaqI

Taq I hydrolyses a long double strand DNA molecule into fragments which are on average 256 base pairs long. The 3'
end of these fragments treated by cleavage turns out to be a thymine(T)- and the 5' end a cytosine(C) -end.

c) How long is the sequence recognized by Taq I ?

d) Give the two possible base sequences (in the direction 5' - 3') which form the recognition pattern for Taq I (must
obviously have some symmetry).

The DNA of a phage which occurs as a close circle contains only 5'- pApTpCpGpApT- 3' sequence in each of the two
strands. After treatment with ClaI an equilibrium is established: circular DNA → linear DNA

e) Give a schematic drawing of the circular and linear molecules. Indicate the bases adjacent to the cleaning site in both
strands. Indicate also the 3' and 5' ends. In Fig. 11 the percentage of linear DNA is given as a function of temperature,
measured in a solution of 0.15 M NaCl buffered with citrate at pH = 6.5. With Taq I as cleavage enzyme, the same
curve is obtained.
f) Is the reaction as written endothermic or exothermic? Explain your answer.
g) Show, considering the information given, which of the two base sequences of the answer to d) is the correct one.
h) What would look the curve for Taq I like if the recognition pattern had been the other possibility of d) ?

A large DNA molecule is cut into fragments with the aid of Cla I. One fragment is isolated, purified and mixed 1:1 with
phage DNA which was also cleaved with Cla I. Thereby recombinant molecules can be formed through the reaction:
phage-DNA + fragment DNA → recombinant-DNA

i) Would the enthalpy of this reaction be positive, negative or about zero ?. Explain your answer.
k) Which combination of temperature, DNA concentration and ionic strength (high or low in each case) will give the
maximum percentage of recombinant molecules ?

IChO Paris 1990

Stereochemistry of the dehydrogenation of succinate to fumarate

a) Write down structures for all the possible stereoisomers obtained by catalytic deuteration of maleic and fumaric acid.
How many isomers are there. Indicate those that are optically active. Establish a stereochemical relationship between
them (compare the isomers two by two). Which is the most stable conformation ? Draw Newman projections.
b) The proportion of dideuterated fumarate (obtained when each of the 2-3 dideuterated succinates is submitted to the
enzymatic reaction) is 4 % when using fumaric acid as starting molecule, but 48.5 % when using maleic acid.
c) On the basis of the Newman projections of the most stable conformations of each isomere, complete the following
table:
 2,3 dideuterosuccinate % of dideuterated fumarate
syn dehydrogenation % of dideterated fumarate
anti dehydrogenation
isomer I
isomer II
...

Assume that the percentages of dideuterated fumarate are 0 or 50% respectively.

d) Show the stereochemistry of the enzymatic dehydrogenation.

e) The 2,3 - dideuterofumarate reacts with fumarase to (2S, 3S)-2,3-dideuteromalate (through addition of water). Show
the stereochemical pathway of the reaction.
f) The acetylcoenzyme A, CH3COSCoA reacts with glyoxylate OHC-CO2- in the presence of malate synthease enzyme
to (S)-malate.
12
A similar reaction can proceed between an ester CH3COOR and an aldehyde R. It leads to a β-hydroxyester. Write the
steps of the mechanism.
g) The enzymatic reaction is carried out using acetylcoenzyme A which is obtained from acetic acid CHDTCOOH having
R-configuration. The formed (S)-malate is dehydrated (the reverse reaction of question c) by an enzymatic reaction.
What enzyme can be used? The major product is monotritiated fumarate (79%) with 21 % untritiated fumarate.Write
down the Fischer projections of the two possible structures of the major product (S)-malate arising from the acetyl-
coenzyme A which has a labelled acetyl group with R-configuration. What would be the products if the starting
material has a labelled acetyl group with S-configuration?