German Problems 2014

46.
International
Chemistry Olympiad
Vietnam 2014
National German
Competition
Volume 20
Chemistry Olympiad 2014
Preface
To become a member of the German IChO-team you have to be successful in

four rounds of a national competition which is led by PD Dr. Sabine Nick.
The problems to be solved in the 1st round are sent to all high schools. To
solve the problems the students may use all resources available, e.g. text-
books etc.
All those students who solve about 70% of the tasks correctly will receive the
problems of the 2nd round, which are to be solved in the same way as men-
tioned above. These problems are the most difficult ones in the whole competi-
tion.
The top 60 of the participants of the 2nd round are invited to the 3rd round, a
one-week chemistry camp. Besides lectures and excursions to chemical plants
or universities there are two written theoretical tests of 5 hours each.
The top 15 of the 3rd round are the participants of the 4th round, a one-week
practical training. There are two written five-hour tests - one theoretical and
one practical - under the same conditions as at the IChO. Here the team is se-
lected.
In this booklet all problems of the selection procedure and their solutions are
collected. Future participants should use this booklet to become acquainted
with the problems of the competition. Therefore the solutions to the problems
given in this booklet are more detailed than the answers we expect from the
students in the competition.
In the appendix you find tables of historical interest.
Wolfgang Hampe
This booklet including the problems of the 46th IchO and the latest statistics
is available as of September 2014 from
http://www.icho.de (”Aufgaben”)
Contents
Part 1: The problems of the four rounds

Contact addresses ............................................................ 4
First round (problems solved at home) ..................... 6
Second round (problems solved at home) ..................... 12
Third round, test 1 (time 5 hours) ........................................ 20
Third round, test 2 (time 5 hours) ........................................ 28
Fourth round, theoretical test (time 5 hours) ...................................... 40
Fourth round, practical test (time 5 hours) ....................................... 55
Part 2: The solutions to the problems of the four rounds

First round ............................................................ 60
Second round ............................................................ 64
Third round, test 1 ............................................................ 71
Third round, test 2 ............................................................ 78
Fourth round, theoretical test .......................................................... 87
Part 3: The problems of the IChO

Theoretical problems ............................................................ 99
Practical problems ............................................................ 115
Solutions ............................................................ 129
Part 4: Appendix
Tables on the history of the IChO .................................................. 141
3
Contact addresses:
IPN University of Kiel, z.H. PD Dr. Sabine Nick tel: +49-431-880-3116

Olshausenstraße 62 fax: +49-431-880-5468
24098 Kiel email: nick@ipn.uni-kiel.de
IPN University of Kiel, z.H. Monika Barfknecht tel: +49-431-880-3168

Olshausenstraße 62 fax: +49-431-880-5468
24098 Kiel email: barfknecht@ipn.uni-kiel.de
Wolfgang Hampe tel: +49-431-79433

Habichtweg 11
24222 Schwentinental email: Hampe@t-online.de
Association to promote the IChO

(Association of former participants and friends of the IChO)
Internet address: www.fcho.de
4
Problems
Part 1
The problem set of the four rounds
5
Problems Round 1
First Round
Problem 1-1 Chemistry and Horses

There is a typical smell in stables caused by a compound A formed by bacterial decomposition
of urea contained in the urine of horses.
a) What is compound A? Write down the equation for the decomposition of urea.
A horse produces 10 to 50 mL of urine per kg body mass per day. The content of urea de-
pends on the protein content of the fodder and amounts to an average of 5 mmol/L (3.3 – 6.7
mmol/L).
b) Which mass of compound A can be theoretically formed in a stable with 23 horses having
a body mass of 550 kg each?
(Use 35 mL/kg body weight as amount of urine and  = 1000 kg/m3 as the approximate
density of the urine of horses.)
In the 19th century many scientists were engaged in the analysis of natural materials and
compounds including the excretions of people and animals.
Justus v. Liebig, a famous German chemist, published in 1829 in a journal called Poggendorfs
Annalen: "Mixing urine of horses with an excess of hydrochloric acid leads after some time to a
yellow-brownish crystalline precipitate. By washing with water the unpleasant smell of the pre-
cipitate does not vanish."
He had prepared a new compound B, the composition of which he published as follows
Nitrogen 7.337 parts in 100 parts Carbon 63.032 parts in 100 parts
Hydrogen 5.000 parts in 100 parts Oxygen 24.631 parts in 100 parts.
c) Determine the empirical formula of B.
Liebig's discovery was path breaking as the former assumption that compound B could be
benzoic acid was refuted because the compound contained nitrogen. Five years later Liebig
revised his results and published new results of an analysis (compound B'):
Nitrogen 7.816 /100 Carbon 60.742 /100

Hydrogen 4.959 /100 Oxygen 26.483 /100.
Compound B' dissolves well in hot water. B' reacts with zinc forming hydrogen amongst other
compounds and forms a lot of metallic salts. When heated with mineral acids or with bases B'
decomposes to benzoic acid and an amino acid.
d) Determine compound B'. What is the name of B'? Draw its line-bond structure.
6
Problems Round 1
If compound B' is heated to decomposition a resin like residue and benzoic acid form besides a
compound C with the molecular formula C7H5N. Liebig describes C as a "... liquid, yellowish,
pleasant smelling, ammonia containing oil which shows great similarity to fatty oils."
e) What is compound C? How can ammonia be generated from C? Draw a reaction scheme
which illustrates the forming of ammonia.
A young girl, Mareike, finds a plastic bag near to the box of her horse. It contains white pow-
der. Part of the powder has already fallen out of the bag and lies directly in front of the box.
Nobody knows which kind of powder this is. So Mareike takes a part of it and gives it to her
older sister who just finished her PhD in chemistry. She remembers from her first years of uni-
versity how to analyze an inorganic powder and delivers the following result:
weißes
white Pulver
powder
H 2O
yellow Flammenfärbung
gelb flame coloration clear
klare weißer
white Flammenfärbung
flame coloration
pink Lösung Rückstand
residue red
rot
rosa
solution
(cobalt glass)
(Kobaltglas)
1. verd.
1. dil. HCLHCl 1. verd.
dil. HNO
HNO33 evolution of gas which
2. BaClsol.
-Lsg. AgNO33-Lsg.
2. AgNO dil.
verd.HCL
HCl Gasentwicklung,
2. BaCl 2 2 clouds Ba(OH)2 sol.
sol. trübt Ba(OH)2-Lösung
white
weißer white
weißer
precipitate
Niederschlag precipitate
Niederschlag
NH
NH33-Lsg.
sol.
clear
klare clear
klare
Lösung
solution solution
Lösung
dil.
verd.HNOHNO 3 3
NH
NH4NO3
4 NO 3
1.
1. titan yellow sol.
Titangelb-Lsg.
sol.
(NH4)2SO4-Lsg.
2. dil. NaOH sol. (NH Mo77OO2424··44HH2O
(NH4) 6Mo 2O
2. verd. NaOH
a wenig, weißer
little white roter
red Farblack
lake yellow
gelber
Niederschlag
precipitate Niederschlag
precipitate
Filtrieren
filtration
clearklare
solution
Lösung
sol.
(NH4)2C2O4-Lsg.
white
weißer
precipitate
Niederschlag
(unlöslichininAcOH
insoluble AcOH,
löslich
soluble in in stärkeren
strong acids Säuren)
Mareike is relieved because her sister did not find anything dangerous.
f) Which ions are in the powder if only the reactions and observations mentioned in the
scheme are taken into account? Which salts could be theoretically existent in the powder?
7
Problems Round 1
Problem 1-2 Redox Reactions

The redox reaction is an important type of chemical reactions.
a) Explain the concept of "redox reactions" shortly. In doing so use the reaction of sodium
with water as an example. Write down the relevant reaction equation(s) and apply oxida-
tion numbers.
b) Which of the following equations represent a redox reaction?
i) HCl + H2O H3O+ + Cl–
ii) Cl2 + 2 HI I2 + 2 HCl
iii) 2 Al + AlCl3 3 AlCl
iv) Cr2O72– + H2O 2 HCrO4–
v) [Fe(H2O)6]3+ + 3 SCN– [Fe(H2O)3(SCN)3] + 3 H2O
vi) Cr2O72– + 4 H2O2 + 2 H+ 2 CrO(O2)2 + 5 H2O
vii) [Ti(OH)2(H2O)4]2+ + H2O2 [Ti(O2) · aq]2+ + 6 H2O
viii) 2 AsH3 2 As + 3 H2
Batteries are galvanic elements, electrochemical cells in which redox reactions take place.
c) Write down the main difference between primary and secondary galvanic elements.
To harness the energy of a chemical reaction so as to produce an electric current has a long
tradition. Small vessels made of clay were excavated from a settlement near to Bagdad (dated
250 BC to 225 AD). They contained a copper cylinder and an iron rod.
Until today it's not clear whether these vessels point to the use of galvanic elements in those
times.
d) Which metal could have served as anode, which as cathode if these vessels had been used
to provide electrical power?
Write down the chemical half equations (anode and cathode).
(E0 (Cu/Cu2+) = +0.34 V, E0 (Fe/Fe2+) = –0.41 V)
e) Name two more preconditions for the construction of an electrical power providing battery.
f) What is the cell potential of the Bagdad battery under standard conditions?
The table on the next page presents some standard half-cell potentials in aqueous solutions at
298 K.
8
Problems Round 1
Reduced form Oxidized Form E° [V]

2+ -
Zn +2e Zn -0.76
Fe3+ + 3 e- Fe -0.04
+ -
2H +2e H2  0.00
Cu2+ + 2 e- Cu +0.34
-
I2 + 2 e 2 I- +0.54
Fe3+ + e- Fe2+ +0.77
-
Cl2 + 2 e 2 Cl- +1.36
g) Which statements concerning the respective experiments are correct? Use the data from
the table to find your answer.
i) Granulates of zinc are given into diluted hydrochloric acid:

1. Chlorine evolves.
2. Hydrogen evolves.
3. Nothing happens.
4. Zinc dissolves.
ii) Splinters of copper are given into diluted hydrochloric acid:

1. Chlorine evolves.
2. Hydrogen evolves.
3. Nothing happens.
4. Copper dissolves.
iii) A solution of iron(III) ions is mixed with a solution of potassium iodide:

1. Iodine forms.
2. Iron precipitates.
3. Nothing happens.
4. The solution turns blue.
In the separation scheme of cations cobalt and nickel are Ni2S3 Co2S3
precipitated as sulfides. For further identification the sul-
NiS CoS
fides are dissolved in H3CCOOH/H2O2 or conc. HNO3.
schwarz black
black schwarz
h) Is the dissolving of NiS and CoS a redox reaction?
Account for your answer!
dissolving
in CH in
3COOH + H2O2
CH3COOH + H2O2
lösen
i) Why is it better to use H3CCOOH/H2O2 instead of
conc. HNO3?
Ni2+ Co2+
9
Problems Round 1
Problem 1-3 Thermal Degradation of a Compound

In order to synthesize a coordination compound a mixture of 1 mmol of copper(I) bromide and
1 mmol of 2,5-dimethyl pyrazine was stirred in acetonitrile. A solid X precipitated. X was sepa-
rated, dried and subjected to an elementary analysis with the following results:
C: 28.65%, N: 11.12%, H: 3.21%.
Additionally the content of copper and bromine were detected by atomic absorption spectros-
copy (AAS): Cu: 25.25%, Br: 31.75%.
a) Find the empirical formula, the molecular formula and the molar mass of X!
For further characterization of X the thermal properties were detected by using differential
thermal analysis (DTA) and thermogravimetric analysis (TG) simultaneously coupled with mass
spectrometry (MS). The results are shown in the following image.
In the MS measurement only the fragment with the highest m/Z rate is shown.
m, T and stream of ions in discretionary units
- 21.5%
- 10.7%
endothermic
- 10.8%
Temperature/°C
Image of the DTA, TG and MS-trend-scan curve of compound X (each loss of mass in the TG curve refers to the origi-
nal existing mass)
b) Which information about the thermal reactivity (behavior at heating) of X provides
i) the TG curve concerning the loss of mass,

ii) the DTA curve concerning the heat of reaction of the events,
iii) the MS-trend-scan-curve concerning the leaving components?
c) Determine the composition (molecular formula) of the compounds which form after the
first, second and third step of the splitting-off.
(Hint: Compare the experimental with the theoretically possible loss of weight.)
10
Problems Round 1
Problem 1-4 An Organic Riddle

Below you find the scheme of the synthesis of compound F. F is an intermediate in the produc-
tion of compound H. H is a natural product which can be synthesized as well as obtained from
natural resources.
a) Draw the line-bond structures of A, B, E, F and G!

(Hint: In step A to B as well as in step E to F 1 mol of hydrogen reacts with 1 mol of A
and E, respectively.)
b) Propose a mechanism for the reaction of C to D.
H
O
C Na/NH3(fl) H2/Kat.
+ A B
C
O O
H
+
NaOEt / EtOH OC2H5
– G
H
C
+ O O O
C
Al(iOPr)3 (kat.) O
H2/Kat. H T
F E
Na/NH3(fl) – CO2
D C
F reacts with t-butyl acetate under cleavage of t-butanol to form H.
c) Draw the line-bond structure of H and write down its name.
d) Which is the natural source of H?
If F is treated with an aqueous solution of acid two compounds I and J are formed which have
the same molecular formula as F:
H+/H2O
F I + J
e) Draw the line-bond structures of I and J and write down their names. Explain why both
compounds form.
11
Problems Round 2
Second Round (homework)
Problem 2–1 An Inorganic Riddle

A compound X has to be found which contains a metal M in the oxidation state +IV.
X crystallizes from an aqueous solution as a monohydrate. The percentage by weight of
M in the monohydrate of X is about 18 %.
X is insoluble in water and decomposes when heated. X shines metallically black-violet.
In solid X the metal M has an octahedral surrounding of oxygen. The simplest oxide of M
crystallizes in a sodium chloride structure.
The compounds A, B and C are necessary to synthesize X.
Compound A forms white, non-hygroskopic crystals. A can be obtained by oxidation of

sodium iodate or sodium iodide with chlorine or bromine in alkaline aqueous solution. A
exists as an ortho form ("water rich"). The molar mass of A is higher than 250 g/mol
and the stoichiometric ratio of sodium and oxygen in A is n(Na):n(O) = 1:2.
B is an ionic compound. Its anion is a strong oxidation agent and can be obtained by
oxidizing sulfates or hydrogen sulfates by very strong oxidation agents (fluorine or in an
electrochemical way). The cation shows yellow flame coloration.
An aqueous solution of compound C shows the following reactions:

 With an aqueous solution of NaOH a precipitate forms, which does not dissolve in
an excess of NaOH but is soluble in acids.
 With barium chloride a white precipitate forms, which does not dissolve in acids.
 With sulfur hydrogen a black solid precipitates from an ammoniac solution of C.
 There is no coloring with an aqueous solution of potassium cyanate.
a) Determine the molecular formulae of the compounds A, B and C.
b) What is the oxidation state of sulfur in the anion of B? Account for your answer.
c) Write down the molecular formula of X and the reaction equation of the formation of
X · H2O. Assign oxidation numbers to all atoms and ions of the reaction equations.
d) What do you expect compound X to be, diamagnetic or paramagnetic? Account for

your answer using an orbital diagram. Which factors have an impact on the occupa-
tion of the orbitals?
Metal M and titanium are the main components of one representative of a modern class
of alloys.
e) Under which name is this alloy known? Which extraordinary property does this kind
of alloys have?
12
Problems Round 2
Problem 2-2 An Organic Synthesis

The following scheme shows the synthesis of the compound K:
1. NaOC2H5
C2H5OH, H+ 2. H+ H+, T
A B C D
CH2N2
N
H Ag2O (kat.)
G F E
p-TsOH (kat.) – N2
O – H2 O
H+/H2O NaOC2H5 T
H I J K
– C 4 H9 N – H 2O
p-TsOH: H3C SO3H
 K contains at least one carbon ring.

 K forms a precipitate with dinitrophenylhydrazine.
 The test of K with Fehling's solution is negative.
 1 mol of K adds bit by bit 1 mol of bromine (Br2).
 The elementary analysis of K gives the following result:
80.44 % of C, 9.82 % of H, 9.74 % of O.
Further information:
 A is an unbranched dicarboxylic acid.

 A consists of nearly 50 % of carbon.
 A reacts with ethanol in the molar ratio n(A):n(ethanol) = 1 : 2.
 D has the molecular formula C5H8O.
 In the reaction C  D a gaseous compound forms as side product (not shown in
the scheme).
 F is a cyclic compound.
 The 1H-NMR of F shows three groups of protons (1.74 ppm, 1.88 ppm, 2.22 ppm),
13
the C-NMR shows carbon in four different chemical surroundings (23.8 pppm, 26.5
ppm, 40.4 ppm, 208.5 ppm)
 The reaction F  G is performed in toluene using a water separator.
 I has the molecular formula C11H18O2.
 The compounds E and J are intermediates which cannot be separated.
13
Problems Round 2
a) Determine the structural formulae of A through K!
b) Mark all stereogenic centers in J with a star. Draw 3D images of all stereoisomers
and identify at each stereogenic center whether it has an S- or an R-confirmation.
Which kind of stereoisomerism do you find between the stereoisomers?
(Hint: in front of the paper plane behind the paper plane)
c) Sketch the mechanism of the following reactions shortly. Under which name are the
reactions (i, iii und iv) and the combination of iii and iv well-known?
i) B  C ii) C  D iii) G  H iv) I  J
d) Give the reason why compound F is not made to react directly with ethyl vinyl ke-
tone but in a "detour reaction" via compound G.
e) In the reaction of I with sodium ethanolate to form J several constitutional isomers

may form as products. Draw images of these constitutional isomers. Account for the
fact that in the end exclusively J is formed.
Problem 2 -3 Spectroscopy
Modern chemists have available to them a powerful array of instrumental techniques for
determine molecular structures. Interactions between electromagnetic radiation and
molecules can be probed by two techniques: IR and Raman spectroscopy.
a) Describe the fundamental difference between these two techniques with regard to
the origin of measured frequencies.
An important difference between these two methods is that different selection rules ap-
ply. IR spectroscopy requires that there is a change in dipole moment during the vibra-
tion while the requirement of Raman spectroscopy is that the polarizibility of the mole-
cule must change during the vibrations.
The number of vibrational normal modes (z) of a molecule containing N atoms is easy to
be calculated:
Linear molecules z=3N–5

Non-linear molecules z=3N–6
b) Sketch all possible vibrations of the molecules i) and ii) and 4 possible vibrations of
the molecule iii)
i) H2O ii) N2 iii) BF3
and indicate whether they are IR and/or Raman active. Give a plot for each vibra-
tion.
14
Problems Round 2
Example CO2 symmetric stretch
antisymmetric stretch
bending mode
bending mode
(upward and downward movement
with respect to the paper plane)
c) How many peaks do you expect in the IR spectrum of carbon dioxide? Account for
your decision!
d) In the calculation of the number of normal modes in a linear molecule 5 is subtract-
ed from 3N, at non-linear molecules 6. Explain why.
We expect the spectrum to provide information about vibrations in a molecule. The reso-
lution of such spectra is often bad, i.e. the absorption bands are very broad. The reason
is that vibrational transition is accompanied by different transitions in the rotational en-
ergy.
It is possible to avoid rotation by cooling the sample down. This can be done by expan-
sion in a carrier gas into vacuum. In this case the pressure in a system of reservoir and
chamber has to obey the following equation:
with = isentropic expansion factor of the gas which can be related to the degrees of
freedom.
e) Calculate the maximal pressure in the chamber for such an expansion with a reser-
voir pressure of 650 mbar and helium as gas.
CH3
S-(–)-Limonene was studied in a series of measurement. It was
expanded in a chamber with helium as carrier gas. The mixture
into the chamber was detected by Raman spectroscopy. Vibra-
tions of different conformers were observed.
f) How many and which kind of vibrations do you expect in H3C CH2
S-(–)-limonene? Fig. 1: S-(–)-Limonene
The assignment of the vibrations to the different conformers is conducted by quantum

chemical calculations. It is possible to determine the temperature of expansion using the
ratio of intensities of the conformers.
15
Problems Round 2
Conformer A Conformer B
Fig. 2: Conformers of S-(–)-limonene: equatorial conformer A and axial conformer B.
The energetically more favorable is the (pseudo) equatorial conformer A. There are two
more conformers which are energetically nearly equal to each other. They differ only in
the rotation of the isopropylene group ("rotamers"). The energy of the axial conformer B
lies considerably below these two conformers.
The calculated difference in energy between A and B is 6,475 · 10–5 Hartree.
g) Calculate the energy difference in kJ/mol and eV! Is the transition A  B at room
temperature (25°C) possible? Explain by using the probability of the existence of B
at this temperature (Boltzmann distribution).
h) If the ratio of intensities (i(A):i(B)) is 7:1, what is the expansion temperature?
i) Why is the equatorial arrangement in ring systems mostly more favorable than the
axial?
j) Which reason could account for the fact that in the case of limonene conformer B is
more favorable than the two rotamers?
Acetone and its dimer were inspected in the same way. The dimer of acetone may have
one of the two arrangements shown below:
Dimer 1: Dimer 2:
Fig. 3: Possible dimers of acetone
It was predicted in comparison with quantum mechanical calculations which kind of di-
mer should be present. At high temperature and low concentration only the monomer
was detected while at low temperature and high concentration the dimer was detected,
too.
16
Problems Round 2
The symmetry of a molecule is important for spectroscopy because it gives information

which vibrations can be observed. The symmetry elements are merged in so called point
groups. Generally the Schoenflies notation is used for molecules.
k) Determine the point group (in Schoenflies notation) of acetone and the two consid-
ered dimers. Use a drawing to sketch the respective symmetry elements.
The C=O bond tends to form dimers. It can be detected by its stretching vibration. Fig.4
shows this region at different temperatures and concentrations. Fig 5 is the result of
theoretical calculations of C=O stretching modes of acetone and its two considerable
dimers.
Fig. 4: A region of the Raman spectrum of acetone at different temperatures and concentrations.
Wave number/cm-1
Fig. 5: Calculated wave numbers of acetone and acetone dimers
l) Which of the two considered dimers is presumably the real dimer of acetone?
17
Problems Round 3 test 1 + 2
Problems Round 3
Test 1 Göttingen 2014: Problems 3-01 to 3-10

Test 2 Göttingen 2014: Problems 3-11 to 3-20
time 5 hours.
your name write it on every answer sheet.
relevant calculations write them down into the appropriate boxes.
otherwise you will get no points
atomic masses use only the periodic table given.
constants use only the values given in the table.
answers only in the appropriate boxes of the answer
sheets, nothing else will be marked.
draft paper use the back of the pages of the problem
booklet, but everything written there will not
be marked.
problem booklet you may keep it.
Good Luck
18
Problems Round 3 test 1 + 2
Useful formulas and data
G0 = H0 - T·S0 G0 = - E·z·F G0 = - R·T·ln K

 H0
G = G0 + R · T· ln Q ln (Kp1/Kp2) = ·(T1-1 - T2-1)
R
p·V = n·R·T for ideal gases and osmotic pressure
RT
Nernst equation : E = E0 + ·ln (cOx/cRed)
z F
RT
for metals E = E0 + ·ln (c(Mez+/c0)
z F
RT
for non-metals E = E0 + ·ln (c0/c(NiMez-)
z F
 0
RT c( H ) / c
for hydrogen E = E0 + ·ln
F ( p( H 2 ) / p0 )1 / 2
with c0 = 1 mol/L, p0 = 1.000∙105 Pa
Rate laws 0. order c = co - k·t

1. order c = co· e k 1 t
2. order c-1 = k2·t + co-1
Arrhenius equation: k = A ∙ e-Ea/(R∙T) A pre-exponential factor
Ea activation energy
Law of Lambert and Beer: A = ·c·d A absorbance
 molar absorption coefficient
d length of the cuvette
c concentration
Transmission T = Absorbance A = lg with I Intensity
Speed of light c = 3.000∙108 ms-1

Gas constant R = 8.314 JK-1mol-1
Faraday constant F = 96485 Cmol-1
Avogadro constant NA = 6.022·1023 mol-1
Planck constant h = 6.6261∙10-34 Js
po = 1.000·105 Pa 1 atm = 1.013·105 Pa 1 bar = 1·105 Pa

1 Å = 10-10 m
A periodic table was provided.
19
Round 3 Test 1
Third Round Test 1
Problem 3-01 Multiple Choice

With one or more correct answers even if the question is written in singular.
a) In an experiment magnesium reacts with a diluted solution of hydrogen chloride:

Mg(s) + 2 HCl(aq)  MgCl2(aq) + H2(g).
By which measurement during the process of the reaction could the rate reaction
determined best?
B the pH value C the concentra-
A the mass of Mg D the volume of H2
of the solution tion of MgCl2
b) Which of the center atoms in the following species obeys the octet rule?
A NO B BH4- C PCl5 D BF3 E XeF4
c) Which of the following statements about oxygen containing compounds is correct?

A KNO3 is a salt without oxidizing ability.
B Oxygen in PbO2 has the oxidation number -1, thus it is a peroxide.
C C and Si are in the same group so that both, CO2 and SiO2, are gaseous at 298 K.
D The oxidation number of oxygen in OF2 is +2
E H2O2 has oxidizing ability but no reducing ability.
d) Ozone can be prepared from oxygen by silent discharge (dielectric-barrier discharge)

in an ozonizer. 10 mL of oxygen give a mixture of 9.3 mL (at standard conditions).
Which volume of ozone is formed?
A 0.35 mL B 0.7 mL C 1.05 mL D 1.4 mL E 2.8 mL
e) A colorless sample of a gas may contain CO2, SO2, HCl and HI. The sample was
passed through a proper amount of chlorine water and reacted completely without
any gas left. Then the colorless solution was acidified and seperated into two test
tubes. Solutions of AgNO3 and BaCl2, respectively, were added. In both test tubes a
white precipitate was found. Which of the following statements is correct?
A The sample contains CO2.
B The sample contains SO2.
C The sample may contain HCl.
D The sample may contain HI.
E The precipitates in the test tubes may be AgCl and BaSO4, respectively.
f) Which of the following statements about halides and their hydrogen acids are cor-
rect?
A The order of electron affinity is F > Cl > Br > I.
B The order of electronegativity is F > Cl > Br > I.
C The order of polarity of the molecules is HF > HCl > HBr > HI.
D The order of acid strength is HF > HCl > HBr > HI.
E The order of amount of bond enthalpy is HF > HCl > HBr > HI.
20
Round 3 Test 1
g) Each of the following five compounds contains 5 carbon atoms. Which of them has
the lowest boiling temperature?
A B C D E
Problem 3-02 Stoichiometric Calculations I

1.000 g of a mixture of potassium chromate and potassium dichromate is dissolved in
water. The solution is filled up to 100.0 mL. Approximately 0.5 g of potassium iodide and
20 mL of diluted sulfuric acid are added to 10.0 mL of this solution.
Ions of iodide reduce both chromate as well as dichromate to form chromium(III) ions
(Cr3+) and elementary iodine (I2).
a) Write down balanced equations for both reactions.
The elementary iodine is titrated with thiosulfate solution (c = 0.100 mol/L)

Consumption: 18.40 mL.
b) Determine the mass of potassium chromate in the original mixture.
c) Account for the fact that the mass of the added potassium iodide is given only
roughly without concern for the accuracy of the result.
1.00 g of magnesium oxalate (MgC2O4 · x H2O, denoted A) is heated in a slow stream of

nitrogen. In doing so the mass of A is reduced as shown in the figure below. Compound
B and C are formed. It is known that between 100°C and 250°C only water splits off.
1,00
0,50
d) Write down the equation for the reaction B  C.

e) Determine x as an integer!
21
Round 3 Test 1
Problem 3-03
a) Use the "Valence Shell Electron Pair Repulsion Theory" (VSEPR theory) to predict the
structure of the following molecules and draw 3-D structures:
PCl5 BrF3 BrF5 BF4- SF4 XeF2
Name the type of each structure.
(Example: The type of the SnCl 3- structure is AX3E with A = central atom, X = lig-
and, E = electron pair)
The trigonal bipyramidal OsO2F3+ cation exists under certain conditions.
b) Draw all possible geometrical isomers of this cation.
Problem 3-04 Complex Compounds

The three compounds A, B and C form at room temperature white crystalline solids. In
all of these three compounds you find n(Pt):n(Cl):n( NH3) = 1:2:2.
A is soluble in polar solvents such as ethanol, while B is soluble in petroleum ether (a
mixture of hydrocarbons) and carbon tetrachloride.
A and B are non-electrolytes while C is a strong electrolyte.
One of these compounds is used in cancer therapy.
a) Draw the structural formulae of A, B and C.
b) Account for the fact that A dissolves in polar solvents, B in non-polar solvents.
c) Write down the electron configuration of the Pt2+ ion.
Problem 3-05 Alkali Metals

The metals of the first group of the periodic table are very reactive.
a) Account for this fact. Which redox ability do they show?
Alkali metals (except for lithium) evaporate already at moderate temperatures. Atoms
and diatomic molecules exist in the gas phase.
b) Show using an MO diagram that dimers of sodium may exist (take only the outer
occupied orbitals into consideration). Determine the bond order.
All alkali metals form oxides Me2O, peroxides Me2O2 and hyperoxides MeO2 (Me = alkali
metal). The stability differs from one alkali metal to the other.
c) Draw Lewis structures of the anions. Give an example for a system which is isoelec-
tronic to the peroxide anion.
22
Round 3 Test 1
There are double oxides Me4O of potassium, rubidium and cesium in which peroxides are
found as well as hyperoxides.
d) How is it possible to describe Me4O6, as a combination of these to oxides? (Example:

Fe3O4 can be written as FeO · Fe2O3.)
Oxides and hydroxides of alkali metals are used as carbon dioxide absorbers by fire de-
partments, at diving and even in astronautics. Lithium hydroxide saved the life of the
crew of Apollo 13 when there was too much carbon dioxide in their cabin.
e) Write down the equations for the reaction of the following compounds with carbon
dioxide.
i) LiOH ii) Na2O2 iii) KO2
Lithium cations show a very small ionic mobility in water compared to the other ions (see
table below). In cation exchangers the adsorption of alkali cations occurs in the order
Li+ < Na+ < K+ < Rb+ < Cs+. Cesium is added fastest, lithium quite slowly.
Mobility of selected ions in water at 25 °C in 10–8 m2 s–1 V–1
Ag+ Ca2+ H+ K+ Na+ Li+ NH4+ [N(CH3)4]+ Rb+ Cs+
6.42 6.17 36.23 7.62 5.19 4.01 7.63 4.65 7.92 8.00
f) Which property seems to be responsible for the different mobility of the ions men-
tioned in the table? Give a reasonable explanation for the small mobility of lithium
cations in aqueous solution.
The following image shows the flow chart of the Solvay process. In this process all reac-
tion steps are attuned so many reagents are in a circular flow.
Limestone
Calcination
Filtrate
g) For which product is the Solvay process set up? Write an equation of the total reac-
tion.
23
Round 3 Test 1
The Solvay process is based on the pair of salts NaCl/NH4HCO3, the position of tis equi-
librium is used for a salt converting reaction. While NaCl is added to the process
NH4HCO3 is gained in the flow of the reactions.
h) Write down an equation of the equilibrium reaction of this pair of salts. Which posi-
tion of the equilibrium is favored? Write an equation for the formation of NH 4HCO3
using the information given in the flow chart.
i) Write down the equation of the calcination reaction.
j) What is calcium hydroxide used for? Write a reaction equation.
Problem 3-06 Acids

A weak acid is dissolved in a buffer solution of pH = 8.8. The total concentration of the
acid is 2.0·10-2 mol/L. The anion A- is coloured and has an absorbance coefficient of  =
21 L·mol-1· cm-1 at the relevant wave length.
In a cuvette with d = 1.0 cm 60 % of the incoming light of the relevant wave length is
absorbed.
a) Calculate the pKa value of the acid HA.
20 mL of 3-chlorbutanoic acid (c = 1.00 mol/L) is titrated with a solution of sodium hy-

droxide (c = 1.00 mol/L) until the equivalence point is reached.
b) Determine the pH value at the equivalence point.
c) Write down the appropriate indicator.
The indicator methyl orange changes its colour at pH  3.7.
d) Determine how much solution of sodium hydroxide in the titration (in b) of 3-

chlorobutanoic acid is necessary to change the colour of this indicator.
pKa(3-chlorobutanoic acid) = 4.05
Problem 3-07 Qualitative Analysis

Seven test tubes contain diluted solutions of the following compounds: Ammonia, barium
nitrate, lead acetate, potassium iodide, copper sulfate, sodium hydroxide (10 %), silver
nitrate.
Reactions were carried out between these solutions. The observations are listed in the
table below.
24
Round 3 Test 1
A B C D E F G
white white
A - - - turbidity turbidity
white pr.
light
yellow pr. light yel- brown pr.
B
dis. low pr. - - T: violet
vapors
white pr.
C - dis.
white pr. white pr.
brown pr.
D brown pr.
dis. -
blue pr.
E - T: black
blue pr.
F
dis.
pr. A precipitate was formed.

dis. The precipitate dissolved in an excess of one of the components.
T Attitude when heated. - No visible reaction
March the substances listed above to the letters.

Write equations of each of the reactions B and C, B and G, C and E, C and F, D and F, E
and G, F and G. Identify the aggregation state and the hydration using (s), (l), (g), (aq).
Problem 3-08 Electrophilic Substitution

Methyl chloride reacts with benzene in the presence of aluminum trichloride to form me-
thyl benzene (toluene).
a) Complete the species A to D in the following reaction schemes:
CH3X + AlCl3 A– + [ B + ]
CH3
[ B+ ] + [C1+] [C2+] [C3+] + D+
Toluene reacts with a mixture of conc. nitric acid and sulfuric acid (nitrating acid) to form
a mixture of different nitrotoluenes with the following composition:
25
Round 3 Test 1
2-nitrotoluene 63 %, 3-nitrotoluene 3%, 4-nitrotoluene 34 %.
b) Account for the different yields using the resonance structures during the different
possible ways of substitution and the influence of the methyl group.
4-Nitrotoluene reacts with nitrating acid.
c) Which compound is predominantly formed? Give the name of the compound and the
structural formula. Account for the increased yield by using the directing effect of
the already present substituent.
4-Methylphenol reacts with bromine in the presence of iron(III) bromide. A mixture of

products is formed, in which one compound preponderates.
d) Plot the structural formula and give the name of this compound. Account for the
higher yield (compared to the other products) of the favored product.
Problem 3-09 Reactions of Esters

Ethyl propanoate (C5H10O2) can react in many different ways:
H2O/OH–
Ethylpropanoat S
NH3
Ethylpropanoat T
LiAlH4
Ethylpropanoat U
RMgX
Ethylpropanoat V (X = Cl, Br, I; R = Alkyl)
S, T, U and V represent the products generated from the propane unit.
a) Complete the compounds S to V. Write down the family of each of these compounds.
The hydrolysis of esters is a nucleophilic substitution reaction. Two typical intermediate

steps are
O
1. R1 C OR2 + OH– X–
2. X– Y + Z–
b) Complete the formulae of the compounds X–, Y and Z– of the hydrolysis!
The reaction mechanism of the ester hydrolysis can be investigated by an isotopically

labelled oxygen (18O) in the ester group (R1CO18OR2).
c) Which result of the investigation would back the formation of your intermediates in
b)?
26
Round 3 Test 1
The ester ethyl-2-pentenoate (C7H12O2) reacts with lithium aluminum hydride dissolved
in ether followed by a reaction with water. Two products Q and R form. Compound Q
decolors a solution of bromine.
d) Write down the reaction equation of the hydration of ethyl-2-pentenoate! Give the
names of the compounds Q and R.
O
1. LiAlH4
2. H2O
O W
CH3
The following lactone reacts with lithium aluminum hydride, too.
e) Give the structural formula and the name of W.
Problem 3-10 Isomeric Compounds

There are several kinds of isomers which can be classified into constitutional isomers and
stereoisomers. Furthermore stereoisomers can be subdivided into configurational iso-
mers (enantiomers and diastereomers) and conformational isomers (conformers).
a) Give an example of a pair of

i) constitutional isomers, ii) conformers,
iii) enantiomers, iv) diastereomers.
b) To which category do cis-trans isomers (E/Z isomers) belong?
c) On the answer sheet there are the structural formulae of several compounds. Mark
all stereogenic centers with an asterisk (*).
To indicate the three-dimensional arrangement (configuration) OH

of an enantiomer the R/S nomenclature is used in most cases.
C
The compound shown on the right has an R configuration. Cl
H
CH3
d) Write down the R/S rules which determine the R configuration of this compound.
e) Determine the configuration of the following compounds:
i) ii) iii) iv) v)

Cl Cl H OH NH2
Cl C1 Br
C C H C COOH H C CH3
H H H3C C2 OH
H 3C H3C
C 2 H5 OH CH3 CN
H
27
Problems Round 3 Test 2
Third Round Test 2
Problem 3-11 Multiple Choice

With one or more correct answers even if the question is written in singular.
a) In which example does the (formal) oxidation state +VI occur?

A Fe4[Fe(CN)6]3 B K2Cr2O7 C CoAl2O4 D Na2FeO4 E Cr(C6H6)2
b) Which element does show flame coloration in the visible range?

A Cu B Ba C Mg D Zn E As
c) In which compound in solid state do you find ions?

A FeCl3 B BCl3 C HgCl2 D ZnCl2 E AgCl
d) All compounds below show an acidic reaction in aqueous solution. Which of them
does not react as a Brönsted acid?
A H2SO4 B H3PO4 C H3BO3 D H4SiO4 E H2CrO4
e) Which compound does react amphoteric?

A Be(OH)2 B Cu(OH)2 C Zn(OH)2 D Ca(OH)2 E Ba(OH)2
f) In the Fehling probe a diluted solution of copper(II) sulfate (Fehling 1) and a basic
solution of potassium sodium tartrate (Fehling II) are used. Testing the following
compounds which of them leads to a positive reaction?
A B C D E
O O O O O
C C C C C
H OH H 3C OH H 3C H H 3C CH3 H
g) Which compounds can be gained from natural fats by saponification followed treat-
ment with acid?
A
O
OH
O
OCH3
B
O
O– Na+
C
D E
HO OH HOOC COOH
OH COOH
28
Problem 3-12 Smoking

In order to determine the amount of carbon monoxide in the smoke of cigarettes it is
oxidized by iodine(V) oxide. In doing so iodine is formed among others. The reaction
takes place in methanol. Iodine(V) oxide forms a colourless, iodine a brownish solution.
The iodine formed in the reaction can be detected quantitatively by photometry.
Standard solutions are used to find the absorption coefficient.
Stand solution I contains 1.00·10-3 mol/L of I2. The standard solutions II, III and IV were
prepared in the following way: 50.0 mL, 25.0 mL and 15.0 mL, respectively, of standard
solution I were given into a 100 mL volumetric flasks and filled with methanol up to the
calibration mark. The following results of the measurement in a photometer and a 1 cm
cuvette were reported:
Standard solution I II III IV

Absorbance 0.89 0.44 0.23 0.13
a) Determine the absorption coefficient.
As shown in the figure 500 mL of smoke are taken

from a cigarette (p = 102.4 kPa,  = 30 °C) and
passed sufficiently slowly through an absorption bottle
with 100 mL of a solution of iodine(V) oxide in metha-
nol. In the beginning the solution was colourless, in the
end it showed a brownish colour.
The absorbance of this solution was 0.69 (under the same conditions as above).
b) Calculate the content (vol.%) of CO in the smoke of cigarettes.
Problem 3-13 Stoichiometric Calculations II

The following equation is usually given to describe the decomposition of manganese(II)
nitrate:
Mn(NO3)2  MnO2 + 2 NO2.
Actually the manganese oxide formed is not stoichiometric with an oxygen/manganese
ratio n(O):n(Mn) < 2.
In an experiment 52.04 % loss of mass was observed after heating manganese(II) ni-
trate at 200 ° C.1
a) Give the empirical formula of oxide formed i.e. determine x in MnO x. Which other
nitrogen containing gas besides NO2 was formed in this reaction? Calculate the ratio
of volume of the gases formed.
1
From Hungary National Competition 2012
29
Cyanide can be determined indirectly by titration with EDTA. (EDTA = ethylenediamine

tetraacetic acid binds 1 mol of metal ion per 1 mol of EDTA.)
An exactly known amount of Ni 2+ ions is added in excess to a cyanide ions containing

solution to react in the following way: Ni 2++ 4 CN-  Ni(CN)42-. Ni(CN)42- does not re-
act with EDTA while Ni2+ does.
In an analysis 20.0 mL of a solution of Ni 2+ were added to 20.0 ml of a cyanide solution.

To titrate this mixture 21.3 mL of a solution of EDTA (c = 0.0100 mol/L) were needed.
In another experiment 17.1 mL of a solution of EDTA were needed to titrate 10.0 mL of
the Ni2+ solution used in the analysis.
b) Determine the concentration of CN- in the original cyanide solution.
Problem 3-14 Ring Flip of Chair Conformations

The chair conformation of a six membered ring is an important structural element of or-
ganic chemistry. The ring flip of a chair, which is a change in conformation, takes place
via different intermediate steps. The following potential diagram describes such a flip.
a) Apply the respective terms and conformations (drawing and respective letter) to the
empty boxes of the image on the next page.
b) Give a value of the activation energy EA for the chair flip. Which conformers can be
isolated?
Term: Term:
Term:
Term: Term:
Term: Term:
Fig: Potential diagram of the chair flip of cyclohexane
30
Conformations:
A B C D E F
Terms: Chair, half-chair, boat, twist boat.
In an investigation to determine the activation energy of the chair flip of compound 1 the
1
H-NMR signals of the two protons Ha and Hb were detected at different temperatures.
The chair conformations 1-A and 1-B are shown in the following figure:
c) Fill in Ha and Hb, respectively, in the empty boxes of both presentations of 1-B (the
presentation on the right hand side is a rotated presentation of 1-B in the middle).
What happens to Ha and Hb in the process of chair flip?
In the 1H-NMR spectrum at 25 °C as well as at – 55 °C the two diastereotopic protons Ha

and Hb of compound 1 offer one singlet at δ = 6.54 ppm. When the sample is cooled
down to –84 °C two signals with a distance of 182 Hz are observed.
An excerpt of the spectra of the signals of the protons H a and Hb at different tempera-
tures is given in following chart:
Fig: 1H-NMR spectrum (500 MHz in CD3OD) of 1 at different temperatures
31
d) Account for this behavior at -84 °C and – 55 °C.
The rate constant k(T) of the chair flip at different temperatures can be found by simula-
tion processes using the shape of the NMR graph and the distance of the two signals.
Table: Rate constants k(T) achieved from simulation processes

/°C –55 –63 –65 –67 –71 –77 –80
k/s-1 2000 540 400 356 200 70 40
The rate constant k(T) is the mean frequency of transition for the equilibrium
1-A 1-B.
e) Draw a diagram ln[(k/s-1)/(T/K)] against 1/(T/K) and determine the equation of the
graph.
The Eyring equation explains the reaction rate k of a chemical reaction depending on the
free standard Gibbs energy of activation ΔG‡.
Eyring equation k = kB/h ∙ T ∙ e- ΔG‡/RT

with kB = Boltzmann constant, h = Planck constant
k = 2.084∙1010 s-1 ∙ (T/K) ∙ e- ΔG‡/RT respectively
-1 ‡
ln k/s = 23.76 + ln T/K - ΔG /RT (1)
‡ ‡ ‡
ΔG = H - T ∙ S (2)
f) Determine ΔG‡ for the chair flip at -63 °C.

Take ln = -6200 · + 30.00 as the equation of the graph in e).
Problem 3-15
Given the following data for the dehydrogenation of ethane:
G°900 K = 22.39 kJ/mol S°900 K(H2) = 163.0 J·mol-1·K-1
S°900 K(ethane) = 319.7 J·mol-1·K-1 S°900 K(ethene) = 291.7 J·mol-1·K-1
a) Write down the reaction equation for the dehydrogenation.
b) Calculate Kp900 for the dehydrogenation reaction at 900 K.
c) Determine the enthalpy of hydrogenation HHyd of ethene at 900 K.
d) What is the composition (in % of vol.) of the reaction mixture if you let ethane pass
over a catalyst for dehydrogenation? The total pressure in equilibrium is 1013 hPa.
(If you could not solve b) take Kp900 = 6.00·10-2.)
e) Calculate Kp at 600 K. Assume that the enthalpy of dehydrogenation in the interval

600 K ≤ T ≤ 900 K is independent of temperature.
32
(If you could not solve b) take K p900 = 6.00·10-2, if you could not solve c) take a
HHyd with |HHyd| = 140 kJ/mol.)
f) Compare the values of Kp at 900 K and 600 K and give a short comment.
Problem 3-16 Iron

Given the reaction scheme on the next page.
a) Complete the reaction scheme (only the iron species have to be filled in).
If necessary use the excerpt from the electrochemical series:
E° in V
Fe Fe2+ + 2 e– -0,44
S2– 1
/8 S8 + 2 e– -0,14
Fe Fe3+ + 3 e– -0,04
H2 2 H+ + 2 e– 0,00
2 I– I2 + 2 e– +0,54
Fe2+ Fe3+ + e– +0,77
2 Cl– Cl2 + 2 e– +1,36
Reaction scheme:
Scheme taken from "Allgemeine und Anorganische Chemie" (Binnewies, Jäckel, Willner, Rayner-Canham),
published in Spektrum Akademischer Verlag, Heidelberg, 2004 Elsevier GmbH München.
33
Potassium hexacyanoferrates(II, III) are well known compounds of iron, in which iron is
octahedral coordinated. Often the common names yellow respectively red potassium
prussiate are used. One of them is thermodynamically and kinetically more stable.
b) Which prussiate should be more stable according to its electron configuration? Which
of them is a better oxidant? Account for your answers!
The photo shows two track layers using the ther-

mit welding process to bond railway lines.
c) Which mixture is used in this process? What

are the reaction products of this process?
Write down a balanced reaction equation.
Source of the image:

http://www.vol.at/gleisbaustelle-feldkirch-
schaan-am-samstag-fertig/3620704
If iron(III) chloride is dissolved in water the solution reacts acidic.
d) Give reaction equations which explain this fact.
There are three different modifications of iron, which can be converted into each other
by changing the temperature. -Iron crystallizes with abody-centered cubic pattern, -
iron has a cubic close packed structure.
e) Draw the images of unit cells of these two structures and determine the number Z of
iron atoms in each cell.
The different packing should cause different densities of - and -iron.
f) Calculate the density of iron in both structures using r(Fe) = 126 pm as average
radius of iron.
Problem 3-17 Electrochemistry

1.40 g of pure lead(II) sulfate was added to 150 cm3 of water and stirred until the equi-
librium is installed above the deposit of lead(II) sulfate at the bottom.
Then a lead electrode and a reference electrode (EoRef = 0.238 V) were inserted. The
voltage measured amounted to ΔE = 0.478 V (T = 298 K).
a) Calculate the solubility product of lead sulfate.
The same sample of lead sulfate was not given into water but instead into 150 cm 3 of
sulfuric acid with pH= 3. Assume for simplification that sulfuric acid protolyses totally.
34
(Use in this part of the problem Ksp = 2.00·10-8 as solubility product of lead sulfate.)
b) Which voltage between the lead electrode and the reference do you expect?
Eo(Pb/Pb2+) = -0.126 V
Problem 3-18 Analysis of an Organic Compound

The following plots on the next page show the mass spectrum and the 1H NMR spectrum
of an unknown compound X.
a) Determine the formula of X.
b) Which fragments of X are represented by m/e = 45; m/e = 31 and m/e = 29?
c) Assign the signals in the 1H NMR spectrum to the respective H atoms of substance X.
Mass spectrum of X (m/e = 46 is the

molecular peak)
Source: NIST Chemistry WebBook
(http://webbook.nist.gov/chemistry
1
H NMR spectrum of X in CDCl3. Source: SDBSWeb : http://sdbs.db.aist.go.jp (National Institute of
Advanced Industrial Science and Technology, 27.01.14)
35
There is a structural isomer Y of compound X .
d) What is compound Y? How many signals with their multiplicity do you expect in a
1
H-NMR-Spektrum of Y? (Do not state the chemical shift!)
e) How many signals of the following 8 compounds in a 1H NMR spectrum do you ex-
pect? (Do not state multiplets!)
i) ii) iii) iv)
CH3 CH2Cl CH3 CHCl CH3 CH3 CHCl CH2Cl CH3 CH2 CH2Cl
v) vi) vii) viii)

H3C H H3C H Cl H H3C H
C C C C C C C C
H3C H Br H H H H CH3
Problem 3-19 Radical Addition to Alkenes: Polymers

In the radical addition to alkenes to form polymers you may distinguish three steps:
Initiation:
H H H H

R + C C R C C
H H H H
Propagation:
H H H H

R C C +n C C A
H H H H
Termination:
2A B or 2A C+D
a) Write down the structural formulae of A to D.
Dibenzoyl peroxide is used to initiate the polymerization of ethene

O
C O
O C
O
Benzoyl peroxide
b) Write the equation for the initiation reaction and the first step of the propagation.
c) Show the monomer units you would use to prepare the following polymers:
36
OCH3 OCH3 OCH3
i) CH2 CH CH2 CH CH2 CH

n
CH2 CH2 CH2 CH2 CH2 CH2

ii)
n
Cl Cl Cl Cl Cl Cl
iii) CH CH CH CH CH CH
n
The polymerization of a substituted vinyl monomer can lead to a polymer with numerous
chirality centers. The polymer having all substituents on the same side of the zigzag
backbone is called isotactic, the one in which the substituents alternate regularly on op-
posite sides of the backbone is called syndiotactic, and the one having the substituents
randomly orientated is called atactic.
The monomer propene forms polypropylenes the properties of which differ depending on
the tacticity: Atactic polypropylene dissolves in heptane but isotactic polypropylene does
not.
d) Draw 3-D structures of isotactic, syndiotactic and atactic polypropylene.
(Hint: in front of the paper plane, behind the paper plane).
1,3-Butadiene polymerizes in two different structures with a regular sequence of the

structural units.
e) Draw the structural formulae of both polymers.
Problem 3-20 Reactions of Aldehydes and Ketones

Given the following reaction schemes.
O
C
H
+
OH
O
c CH2NH2
C A
H
+ HCN A
OH
d COOH
a)
Draw the structural formulae of the compounds A and B and of the reagents c and d.
37
b) Name the kind of reaction for the formation of A starting with benzaldehyde.
Show the reaction mechanism using structural formulae and arrows which show the
movements of the electrons.
Alcohols, too, react with aldehydes and ketones. At first hemiacetals are formed and
then acetals:
H+ H+
Aldehyde/ketone + alcohol hemiacetal acetal
The formation of an acetal is performed in several steps:

O
H+ + R'OH
R C H K Hemiacetal
Halbacetal LL + H+
+ H+
OR'
+ R'OH
H+ + R C H N M
– H2O
OR'
c) Complete the structural formulae K to N.
d) How can the equilibrium of the synthesis be shifted to the formation of the acetal?
Alcohols with more than one -OH group like glycerol (propane-1,2,3-triol) react with ke-
tones to form acetals, too.
e) Write down the equation for the reaction of acetone and glycerol.
Consider the following reactions of benzaldehyde:

O
1. NaBH4
C
H 2. H2O
O
O
C
H NH2OH / H+
P
O
1. H3CMgBr
C
H 2. H2O / H+
Q
O
1. N2H4
C
H 2. OH– / T
R
– N2, – H2O
O
C
H NaOH
2 S + T
38
f) Draw the structural formulae of O to T.
The last reaction of e) when benzaldehyde reacts to S and T is an example for a Canniz-
zaro reaction. In this reaction carbon disproportionates. Aldehydes without a hydrogen
atom in  position react in this way.
The first step of the Cannizzaro reaction gives a tetrahedral intermediate.
g) Show the mechanism of the Cannizzaro reaction taking the given example of benzal-
dehyde. Use structural formulae and arrows which show the movement of the elec-
trons.
h) Account for the reason why carbonyl compounds with hydrogen in  position do not
undergo a Cannizzaro reaction.
39
Problems Round 4 (theoretical)
Fourth Round (theoretical problems)

(A periodic table and the same list of formulae and data as in the third round were provided)
4–1 Structure of Solids

There are two close-packed structures, cubic and hexagonal. Two layers of these struc-
tures are shown below:
close-packed cubic close-packed hexagonal
a) Complete the plots on the answer sheet by adding three adjacent spheres () of the
next layer.
Besides the close-packed structures there are two more packings of spheres in which
metals crystallize. The elementary cells of the three cubic packings are plotted in the
table below.
Elementary Denotation Coordination Metal atoms

cell number per cell
b) Complete the missing data!
Close-packed structures do not only play a prominent role in the structures of solid met-
als, they also can be used to derive the structures of many salts. For example, one kind
of ions forms a close-packed structure while the counterions are arranged in the octahe-
dral and tetrahedral interstices.
c) Draw a tetrahedral and an octahedral interstice into the given structures on the an-
swer sheet.
d) How many tetrahedral and octahedral interstices do you find in a close-packed cubic
structure with n spheres?
40
In the crystal of sodium chloride, both Na + and Cl- ions

form a close-packed cubic lattice. The symmetry of the
crystals can be seen well under a microscope. The coordi-
nation numbers are (6,6).
Below you find an elementary cell of sodium chloride, where the cations are generally
arranged in the interstices. The length of the edge is 562 pm.
e) Determine the empirical formula of this elementary cell.
f) Calculate the radii of the chloride and the sodium ions. Assume for simplification,
that the smaller kind of ions is inserted in a way that the bigger ones are in contact
with the nearest of each other.
4-2 Complexes, Ligands and trans-Effect

A
a) What is the meaning of the term "complex" in chemistry? Complete the missing
terms on the answer sheet.
Complexes differ very much in their stability. Especially stable coordination compounds
form if polydentate ligands coordinate with a metal ion.
b) Plot images of metal complexes (Me: metal) which show the spatial arrangement of
the ligands given below.
(If there is the possibility to coordinate more than one ligand plot only one. If there
are isomers the plot of one is sufficient.
i) Ethylenediamine (1,2-Diaminoethane), C2H8N2

ii) Oxalato, C2O42–
iii) Ethylenediamminetetraceto, C10H12N2O84–
iv) 18-Crown-6, C12H24O6
41
In aqueous solutions ligands can displace each other. The following reactions of nickel
complexes are given:
[Ni(H2O)6]2+ + 6 NH3 [Ni(NH3)6]2+ + 6 H2O
[Ni(H2O)6]2+ + en + 4 NH3 [Ni(en)(NH3)4]2+ + 6 H2O
[Ni(H2O)6]2+ + 2 en + 2 NH3 [Ni(en)2(NH3)2]2+ + 6 H2O
[Ni(H2O)6]2+ + 3 en [Ni(en)3]2+ + 6 H2O
(en = Ethylenediamine)
c) Which complex on the right hand side of the equations should have the least, which
one the highest complex stability?
Account for your answer using the (thermodynamic) chelate effect!
Existing ligands have an essential influence on the products of nucleophilic substitutions

of square-planar complexes.
When in a square-planar complex [MeLX3] ligand X is substituted by ligand Y two prod-
ucts may occur.
d) Plot the structures of these products.
Ligands show a different ability to direct into trans position (<: smaller ability of trans
directions as):
F–, H2O, OH– < NH3 < py < Cl– < Br– < I–, SCN–, NO2– < PR3 > H–, NO, CO, CN–, C2H4
This so-called trans effect is due to kinetic reasons and describes the influence of a lig-
and on the displace rate in its trans position.
A well-known example is cis-platinum (cis-[PtCl2(NH3)2], which is used as a drug against
certain tumors.
[Pt(NH3)4]2+, [PtCl4]2–, NH3 and HCl are to your disposal.
e) Create a way to synthesize the cis and the trans isomer considering the trans effect.
B
Many poorly soluble salts can be dissolved by formation of their ammine complexes.
Nickel hydroxide e.g. is not soluble in an excess of a solution of sodium hydroxide but in
a concentrated solution of Ammonia it dissolves as [Ni(NH3)6]+2.
f) Calculate the minimum concentration of free NH3 in mol/L, which is necessary to

produce a solution of c([Ni(NH3)6]+2) = 0.1 mol/L.
KL(Ni(OH)2) = 3.2 · 10–17, KD([Ni(NH3)6]+2) = 10–8.7 (KD: Instability constant)
C Salt X contains a hexaquocomplex and a metal with the oxidation state +III. In an
aqueous solution it reacts acidic. The water-free salt can sublimate while the water
containing salt decays into one solid and two gaseous products when heated.
42
If you lead the gaseous products through two U-tubes, one filled with calcium chloride
the other one filled with granulated sodium hydroxide the total amount of gas is ab-
sorbed.
830 mg of the water containing salt is decayed by heating. The gain in mass of the calci-
um chloride containing U-tube is 281 mg, that of the sodium hydroxide containing U-
tube 376 mg.
g) Determine X!
Problem 4-3 Kinetics2

A
Sulfuryl dichloride (SO2Cl2) is a compound widely used as chlorinating/sulfonating com-
ponent. At room temperature, SO2Cl2 is a colorless liquid with a pungent ordour and a
boiling point of 70 °C. It decomposes to SO2 and Cl2 when heated to or above 100 °C.
An empty container was filled with SO2Cl2. Its decomposition was followed by monitoring
the change in total pressure at 375 K. The following data were obtained:
time in s 0 2500 5000 7500 10000
total pressure in atm 0.500 0.527 0.553 0.576 0.599
a) By graphical approach show that the decomposition is a first order reaction and cal-
culate the rate constant.
When the decomposition reaction is carried out at 112 °C (starting again with p 0 = 0.5
atm), the total pressure is found to be 0.78 atm after 1 h.
b) Calculate the activation energy of the decomposition reaction.
B
In many calculations using H° and S° it is assumed that these values do not change for
temperatures which are not too far away from 298 K.
Standard values for substances of part A:
Cl2 SO2 SO2Cl2
fH° in kJ/mol 0 -296.8 -354.8
S° in J/(K·mol) 223.1 248.2 311.1
c) Using the Gibbs equation calculate G for the decomposition reaction at 400 K as-
suming that H and S have the same values as at 298 K. Determine Kp from the
calculated value of G.
2
Some ideas and data from "Preparatory Problems 2011, Turkey"
43
Actually these properties of state change with temperature according to the following
(simplified) equations:
Cl2 SO2 SO2Cl2
fH°(T) in kJ/mol -10.2 + 34.2·10-3·T/K -309.1 + 41.4·10-3·T/K -369.2 + 48.2·10-3·T/K
S°(T) in J/(K·mol) 28.3 + 34.2·lnT/K 12.34 + 41.4·lnT/K 36.5 + 48.2·lnT/K
d) Calculate G for the decomposition reaction at 400 K using the relevant equations.
Determine Kp from the calculated value of G, too. Judge whether the assumption of
c) is justified in this case.
C
The reaction S2O82-(aq) + 3 I-(aq)  2 SO42-(aq) + I3-(aq)
follows the rate law v= = k · c(S2O82-) · c(I-).
The following mechanism is proposed:

k1
I- + S2O82-  IS2O83-
k
IS2O83- 2
 2 SO42- + I+
k
I+ + I- 3
 I2
k
I2 + I- 4
 I3-
e) Check whether the mechanism is consistent with the given rate law. Assume that
the steady state approximation can be applied to all intermediates.
Problem 4-4 Distributions

The distribution of a weak monoprotic acid between water (w) and ether (e) follows the
equation:
= KD (1).
HAe: Molecules of the acid in ether

HAw: Molecules of the acid in water
In this case KD = 5.4 is given.
1 L of a diluted weak acid HA is strongly acidified with hydrochloric acid. Then the acid
HA is extracted with 500 mL of ether. Hydrochloric acid does not dissolve in ether.
a) Which molar fraction of the acid HA can be extracted in this way?

Account for the acidification with hydrochloric acid.
The extraction is more effective if the sample of ether is divided in n smaller portions
with equal size followed by an extraction one after another.
b) Determine in how many parts 500 mL of ether have to be divided to extract at least
89 % of the acid HA.
44
The distribution coefficient KD for two immiscible solvents S1 and S2 (see equation (1))
for a compound A refers to compound A. If there are dissociation, dimerisation and com-
plexation the calculation is more complicated.
In 100 mL of a buffer solution of pH = 3.0 a monoprotic acid HA (pKS = 2.89) is dis-

solved. A part of the acid is extracted with 50 mL of ether. Let K D be 4.3.
After the extraction there are 0.0432 mol of the acid in the sample of ether.
c) Determine the initial total concentration of the acid HA in the buffer solution.
Assume that the pH value of the buffer solution is the same before and after the ex-
traction and that there is no protolysis of HA in ether.
In case of c) the distributions coefficient D is often used:
D=
d) Calculate D for the acid HA under the conditions of c).
e) Derive a formula for D containing only Ka, KD and c(H+).
[Ni(en)(NH3)4]2+ + 6 H2O
[Ni(H2O)6]2+ + 2 en + 2 NH3 [Ni(en)2(NH3)2]2+ + 6 H2O
[Ni(H2O)6]2+ + 3 en [Ni(en)3]2+ + 6 H2O
(en = Ethylenediamine)
c) Which complex on the right hand side of the equations should have the least, which
one the highest complex stability?
Account for your answer using the (thermodynamic) chelate effect!
Existing ligands have an essential influence on the products of nucleophilic substitutions

of square-planar complexes.
When in a square-planar complex [MeLX3] ligand X is substituted by ligand Y two prod-
ucts may occur.
d) Plot the structures of these products.
Ligands show a different ability to direct into trans position (<: smaller ability of trans
directions as):
F–, H2O, OH– < NH3 < py < Cl– < Br– < I–, SCN–, NO2– < PR3 > H–, NO, CO, CN–, C2H4
This so-called trans effect is due to kinetic reasons and describes the influence of a lig-
and on the displace rate in its trans position.
A well-known example is cis-platinum (cis-[PtCl2(NH3)2], which is used as a drug against
certain tumors.
45
[Pt(NH3)4]2+, [PtCl4]2–, NH3 and HCl are to your disposal.
e) Create a way to synthesize the cis and the trans isomer considering the trans effect.
B
Many poorly soluble salts can be dissolved by formation of their ammine complexes.
Nickel hydroxide e.g. is not soluble in an excess of a solution of sodium hydroxide but in
a concentrated solution of Ammonia it dissolves as [Ni(NH3)6]+2.
f) Calculate the minimum concentration of free NH3 in mol/L, which is necessary to

produce a solution of c([Ni(NH3)6]+2) = 0.1 mol/L.
KL(Ni(OH)2) = 3.2 · 10–17, KD([Ni(NH3)6]+2) = 10–8.7 (KD: Instability constant)
C
Salt X contains a hexaquocomplex and a metal with the oxidation state +III. In an aque-
ous solution it reacts acidic. The water-free salt can sublimate while the water containing
salt decays into one solid and two gaseous products when heated.
If you lead the gaseous products through two U-tubes, one filled with calcium chloride
the other one filled with granulated sodium hydroxide the total amount of gas is ab-
sorbed.
830 mg of the water containing salt is decayed by heating. The gain in mass of the calci-
um chloride containing U-tube is 281 mg, that of the sodium hydroxide containing U-
tube 376 mg.
g) Determine X!
4-5 Ligand Field Theory and Magnetism

Following the ligand field theory there is a splitting of the d orbitals when a complex is
formed. The strength of the field splitting caused by the ligand as well as the central
atom is essential concerning the question whether a high- spin or a low-spin complex is
formed.
a) Which d electron configurations can form high-spin and low-spin complexes in an

octahedral ligand field? Give a short explanation.
b) Add the d electrons to the given orbital scheme on the answer sheet. Which magnet-
ic property (para- or diamagnetic) do you expect?
For paramagnetic first-row transition metal complexes the magnetic moment  in units
of Bohr magneton (BM) is reasonably well approximated by the spin-only formula
theo = √ BM n: Number of unpaired electrons.
46
c) Calculate the spin only magnetic moments for metal centers with 1, 2, 3, 4 and 5
unpaired electrons.
By comparing the theoretical magnetic moment (theo) with the experimentally gained
data (exp) you can find out whether a compound is a high-spin or a low-spin complex.
exp can be calculated by a complex formula which can be simplified for the case below:
exp = 2.83·√ BM C: Curie constant

The Curie constant can be determined by detecting the susceptibility  at different tem-
peratures with a magnetic balance (Gouy balance):
= T: Temperature : Susceptibility
The susceptibility of an octahedral manganese(II) complex was detected as follows:
T in K 2 10 20 30 60 90 120 220 270 300
 in cm3·mol-1 1.804 0.442 0.226 0.152 0.076 0.051 0.038 0.021 0.017 0.015
d) Determine the Curie constant (with two decimals) by plotting 1/ vs. T
e) Calculate exp.
f) Is this manganese (II) complex a high-spin or a low-spin complex? Account for your
answer.
Problem 4-6 Uranium

A
Radioactive decay reactions can be systemized by general equations. In case of electron
capture the number of nucleons does not change but the atomic number is reduced by
1:
+ 
a) Write such general equations of the change in the number of nucleons and the
-
atomic number for the - and -decay.
238
Today natural uranium consists of several isotopes. The most long-life ones are U
9 235 8
(99.275 % of mass, t½ = 4.468·10 a) and U (0.720 % of mass, t½ = 7.038·10 a).
The other isotopes have a considerably shorter half-life.
235 238
b) At what point of time in the past (tx) was the mass of U half of the mass of U?
238 235 232

When U und U came into being more radionuclides such as Th (t½=1.405·1010 a)
237
and Np (t½=2.14·106 a) were formed. All these isotopes undergo -decay.
47
234
A further radioactive isotope, U, with a fraction of about 0,005 % can be found in nat-
ural uranium. It does not originate from the time of formation of the earth, but is formed
continuously by the decay of one of the four isotopes mentioned above. A radioactive
234
equilibrium has established itself in which the concentration of U is constant, that
means that the formation- and decay rates are the same.
234 
c) From which of the isotopes mentioned above is U formed by a series of - und -
decays? Write down the path of formation.
234
d) Calculate the half-life of U.
B
Uranium is interesting, too, as partner in chemical reactions. There are a lot of oxidation
states in uranium ions.
Standard potentials of half reactions:
U3+ + 3 e-  U Eo = -1.798 V
UO22+ + 4 H+ + 6 e-  U + 2 H2O Eo = -1.444 V
U4+ + e-  U3+ Eo = -0.607 V
UO22+ + e-  UO2+ Eo = +0.062 V
UO22+ + 4 H+ + 2 e-  U4+ + 2 H2O Eo = +0.327 V
UO2+ + 4 H+ + e-  U4+ + 2 H2O Eo = +0.620 V
e) Attach the oxidation state of uranium to each species.
A small amount of uranium is given into a strong monoprotic acid HX (c = 1 mol/l) in the
presence of hydrogen with p = 1 bar and T = 298 K. You may assume that the conjugat-
ed base X- does not react with uranium or one of its ions. To answer the following ques-
tion you may consider the reactions in a respective galvanic cell with the concentration
of the specific uranium species of 1 mol/L.
f) Determine the destiny of the small amount of uranium. Write down equations of all
proceeding reactions. Account for the reactions by comparing the potentials of the
relevant half-cells. Give the potential of the correspondent cell.
Problem 4–7 Total Synthesis of Capsaicin
Paprika and especially chili were grown as early as 7000

B.C. in middle and south America. After the discovery of
America by Columbus first plants were brought to Eu-
rope. Today chili is ingredient of the traditional cuisine of
many countries all over the world. Active ingredients ob-
tained from chili can be used as medicine, for plant pro-
Fruit of the species tection and for non-fatal weapons like tear gas and pep-
Carolina Reaper – the
hottest chili of the world per spray.
48
The ingredient which is responsible for the pungency of chili is the alkaloid Capsaicin (8-
methyl-N-vanillyl-6-nonenamide):
a) Mark and enumerate the functional groups of capsaicin.
b) Determine the configuration of the double bond using the E,Z designation.
The pungency of chili is indicated by the so called Scoville scale. A measured amount of
alcohol extract of the capsaicin oil of the dried pepper is produced, after which a solution
of sugar and water is added incrementally until the "heat" is just barely detectable by a
panel of tasters; the degree of dilution gives its measure on the Scoville scale called
Scoville Heat unit (SHU). Today the pungency is detected by HPLC. 1ppm of capsaicin
(referred to mass) corresponds to 16 SHU.
c) Calculate the content (in ppm und μg/g) of capsaicin for the hottest known chili
(species Carolina Reaper) which has 2 200 000 SHU (for comparison: pure capsaicin
has 16 000 000 SHU).
Often natural compounds are produced in a larger scale by total synthesis – i.e. a syn-
thesis starting with simple composed organic compounds which can be received easily.
Such a total synthesis of capsaicin which was developed 1989 by Kaga et al. uses vanil-
lin, the main ingredient of vanilla flavor, as starting material:
Thionyl chloride
Total synthesis of capsaicin from vanillin (Kaga, 1989)
The first step is the reaction of the carbonyl group with ammonia and methanoic acid
which is produced in situ by heating ammonium formate. The carbonyl group is nucleo-
philicly attacked; the generated hydroxyl group is protonated and then cleaved as water.
The produced carbocation is reduced by methanoic acid, carbon dioxide escapes as side
product. Thus in the first step a nitrogen containing product with the empirical formula
C8H11NO2 is formed.
d) Draw the structural formula of 1.
49
e) Using structural formulae give the mechanism of the formation of the carbocation in
the reactive above. Show with the help of resonance structures (including nitrogen)
how the cation is stabilized.
The second component of the total synthesis is formed from 6-bromohexanoic acid 2
which can be bought. Compound 2 reacts with triphenylphosphine to the corresponding
triphosphonium salt 3. 3 reacts with isobutyl aldehyde 4 and tBuOK in DMF. The product
(Z)-5 isomerizes when treated with a mixture of nitrous acid and nitric acid to form (Е)-
5.
f) Plot the structural formulae of (Z)-5 and (Е)-5 an. Which kind of isomers are these
compounds?
Subsequently (Е)-5 is brought to reaction with thionyl chloride to form the acid chloride
6 (C10H17ClO).
g) Write down the reaction equation.
In the last step the compounds 1 and 6 react in a condensation reaction. The desired
product capsaicin is gained as a salt. Free capsaicin can be obtained by treating this salt
with a solution of sodium hydrogen carbonate.
h) Plot the structural formula of 7.
i) Give the mechanism of the reaction of 1 and 6.
j) Why is it not possible to synthesize capsaicin directly from 1 and (Е)-5?
k) What is the name of the bond which is formed in the reaction between 1 and 6? Can
you expect a free rotation (analog to the rotation of a C-C bond in ethane) in this
kind of bond? Account for your answer.
Problem 4-8 Stereoselective Reactions

There are a lot of stereoselective reactions for a chemist to synthesize molecules with
several stereogenic centers. Thereby it is possible to insert new stereogenic centers or to
use stereogenic centers already existing in the molecule to form new ones.
The synthesis shown below is a part of a total synthesis of a natural compound with a lot
of stereogenic centers:
50
H2 Sharpless
Lindlar-cat. Epoxidation
1. Aldol reaction with
2. removal of the
auxiliary and the
protecting groups
In the first step the alkyne1 which is supplied with the protecting group SG1 is reduced
to the cis-alkene 2.
In the second step a Sharpless epoxidation on alkene 2 follows. By using specific rea-
gents it can be processed in a way that both epoxides are available (showing to the front
or to the back). In this case the (2S,3R)-enantiomer 3 was produced (numbers starting
from the carbon with the free OH group).
a) Draw the structural formula of the alkyne 2.
In the next reaction step the epoxide is stereo- and regioselectively opened in position 3
by introducing an ethylene group with the help of triethylene aluminum (AlEt 3) in di-
chloromethane (DCM) as solvent.
This reaction is a nucleophilic attack from the back side.
b) Draw the structural formula of compound 4.

(Hint: in front of the paper plane, behind the paper plane, in the
paper plane)
c) Give the configuration of the stereogenic centers in 4 using CIP sequence rules.
The enantiomer 4‘ of compound 4 shall be synthesized.
d) Which of the reactions up to this point have to be changed? Draw the synthesis
scheme upto this new compound 4' starting from 1.
Subsequently the protecting groups SG2 and SG3 are introduced, SG1 removed and the
alcohol oxidized to an aldehyde.
Then a stereoselective aldol reaction with the carboxylic acid ester 6 is performed which
is supplied with a so called auxiliary group (Aux). This is a group which can be attached
51
to a molecule for a stereoselective reaction so that only a specific stereoisomer is

formed.
During the aldol reaction the ester 6 is at first deprotonated to form an enolate and then
the aldehyde 5 is added. This procedure leads to a (5R,6R)-configuration independent
of the configuration of the other stereogenic centers in the molecule.
The empirical formula of the molecule after removing the auxiliary and the protecting
groups SG2 and SG3 is C10H20O5. Compound 7 contains three OH groups and a free car-
boxylic acid.
e) Draw the structural formula of compound 7.
f) What do you get if the sequence of reactions is performed with the enantiomer 4‘,
the enantiomer or a diastereomer of product 7? Account for your answer!
Problem 4-9 Natural Material from the Ocean
Dysidavaron A is a compound which was extracted from Dysidea avara, a sponge living
in the Mediterranean. The total synthesis was performed only recently.
The synthesis starts with 3,5-dihydroxytoluene which is modified in four steps to form
compound 2. Compound 2 reacts with ketone 3 in a reductive, stereoselective alkylation
to form compound 4. Thereby ketone 3 performs a nucleophilic substitution reaction at
compound 2. (See clue concerning the reagents at the end of the problem.)
1.) Et2SO4, Isobutene,

1.) Isobuten,
OH Anisol, TfOH, DCM,
60 °C -78 °C
2.) NBS, 2.) NBS, AIBN,

OH CHCl3, CCl4, 77 °C,
1
-60 °C h 2
a) Draw the structural formulae of the compounds 1 and 2! (Hint: Look at compound 4
accurately).
One of the reactions with NBS is a radical substitution, the other one an electrophilic
substitution.
52
b) Give the conditions of the different substitutions. In which position of the molecule
(aromatic nucleus or side chain) does the particular reaction occur?
In the further course of reaction a ring closure takes place with the help of the catalyst
Pd(OAc)2 and the ligand 5: t-BuONa,
Pd(OAc)2,
5. Toluene,
70 °C
In the following the resulting ketal is transformed into compound 6. Then 6 reacts in a
Wittig reaction to compound 7. 7 does not contain any carbonyl group.
HCl (c = 3 mol/L)/ H
OEt
THF, RT
O
O
6 O Ot-Bu
Ph3PCH3Br,
t-BuOK,
t-BuOK,
Toluol, 90 °C
Toluene, 70 °C
HCl (c = 5 mol/L)/ H
THF,70 °C, 50 h OEt
7 8 OH
c) Draw the structural formula of 6! (Hint: The t-Bu- and the Et-groups are stable under
the given reaction conditions.)
d) Draw the structural formula of compound 7!
There are two reactions in the last step of the reaction sequence to synthesize 8 shown
above: a t-Bu group is cleaving off and a rearrangement to form a more stable product
takes place.
e) Is it a kineticcally or a thermodynamically more stable product? Account for your

answer using the given reaction conditions.
53
In the last step to form the natural compound Dysidavaron A the aromate in compound
8 is oxidized to a quinone ring.
O2,
H Salcomin,
OEt DMF, RT
OH
C23H28O3
f) Draw the structural formula of Dysidavaron A.
Clue to the abbreviations and reagent:

NBS: N-Bromosuccinimide is a reagent for mild bromation. It works without catalyst.
TfOH: Trifluoromethane sulfonic acid, pKs=-20
DCM: Dichloromethane
AIBN: Azo-bis-(isobutyronitrile). It decomposes at temperatures above 25 °C
and is a radical initiator.
THF: Tetrahydrofuran
54
Problems Round 4 (practical)
Fourth Round (practical problems)
4-10 Synthesis of an Organic Compound

In this experiment a polycyclic aromatic compound is brought to reaction with maleic
acid anhydride:
O
O O
Equipment:
Stand with boss and clamps (2x), 2 round bottom flasks (100 mL), 2 cork rings, reflux
condenser, magnetic stirrer plate with stirring bar, crystallization dish for an oil bath,
spatula, Büchner funnel with 3 filter papers, balanced beaker (100 mL) with number to
deliver the product, TLC chamber, 1 TLC plate, filter paper for saturation of the chamber,
2 small vessels to prepare the solutions, 2 capillary tubes for TLC spotters, measuring
cylinder (25 mL), zipper bag to place the TLC plate, tweezers, pencil.
Chemicals:
Anthracene (1 g)
Maleic acid anhydride (0,4 g)
Xylene
Silicone oil for oil bath
Acetic ester
Cyclohexane
Anthracene for TLC
Safety precautions:
Wear eye protection and protective clothing.
Procedure:
Synthesis
Anthracene and maleic acid anhydride are given into 15 to 20 mL of xylene and then
stirred for 30 minutes by heating using the reflux condenser. The yellow solution in the
beginning should become nearly colourless. Then the solution should cool down. Thereby
a solid precipitates. The solid is filtered off by using the Büchner funnel and then recrys-
tallized in acetic ester. The recrystallized product is filtered off with the Büchner funnel
and then dried for 10 to 15 minutes in the drier at 70 °C.
TLC investigation
Dissolve a small amount of anthracene and of the product in acetic ester using the two
small vessels (it is not necessary to get a clear solution). Mark two start points on the
TLC plate using the pencil and spot one of them with a bit of the solution of anthracene,
the other one with a bit of the solution of the product using the capillary tubes provided.
55
Run a TLC in the TLC chamber which is saturated with the solvent (cyclohexane:acetic
ester 1:1). Mark the solvent front with the pencil as well as the spots using UV light at
366 nm. Determine the Rf values.
Place the TLC plate in the zipper bag.
Disposal:
Put all chemicals and the filter papers into the provided waste boxes.
Problems:
a) Which kind of reaction is performed in this experiment?
b) Plot the structural formula of the product.
c) Determine your yield in % of the theoretical yield.
d) Deliver your product in the provided balanced beaker to the instructor. Insert the
number of your beaker into the answer sheet.
e) Sketch the TLC plate on the answer sheet and deliver the plate in the zipper bag to
the instructor.
f) How do the two compounds differ in the UV light at 366 nm and why?
4-11 Alkalimetric Identification of an Organic Acid

In this problem you get a sample of a solution of an organic acid. You have to titrate the
acid and find out which acid you got.
Your volumetric flask contains one of the three acids shown below. All of them have
nearly the same pKa value and the endpoint of the titration can be determined with the
given indicator. The mass of the solid dissolved in your flask will be given to you by the
instructor.
Benzoic acid 3-Methylbenzoic acid Gallic acid monohydrate

COOH COOH
COOH
HO OH
CH3 OH
C7H6O2 C8H8O2 C7H6O5 · H2O

M = 122.12 g/mol M = 136.15 g/mol M = 188.13 g/mol
Equipment:
Volumetric flask (100 mL) with the sample of the solution, volumetric pipette (20 mL), 2
Erlenmeyer flasks, small beaker, pipette control, burette (25 mL), stand with boss and
clamps, spatula, micro spatula.
56
Chemicals:
Solution of a given amount of an organic acid

Standard solution of sodium hydroxide, c(NaOH) = 0.01 mol/L
Tashiro indicator
Demineralized water
Procedure:
If there is solid in your sample dissolve it by addition of demineralized water. Then fill
the volumetric flask up to the calibration mark. The solution has to be mixed well.
Determination of the content of the acid

Exactly 20 mL of the solution are transferred to an Erlenmeyer flask and then filled up to
appr. 100 mL. Add 5 to 10 drops of the Tashiro indicator solution and titrate the violet
solution until it is purely green.
Disposal:
Give all solutions into the provided waste boxes.
Problems:
a) Insert the number of your sample into the answer sheet.
b) Record the consumption of the standard solution of sodium hydroxide and calculate
the concentration of the acid in mol/L.
c) Compare your result with the weight of the acid dissolved in your solution and de-
termine which of the three solutions you had got.
4-12 Complexometric Determination of Calcium and Magnesium

At first calcium is titrated using calcon-carboxylic acid as indicator. Then the indicator is
destroyed by cooking with a solution of hydrogen peroxide. Afterwards magnesium is
determined using indicator buffer pellets (indicator Eriochrome Black T + ammonium
acetate).
Equipment:
Volumetric flask (250 mL) with solution of the sample, volumetric pipette (25 mL), 2
Erlenmeyer flasks, small beaker, pipette control, stand with boss and clamps, spatula,
micro spatula.
Chemicals:
Solution of calcium and magnesium compounds

Standard solution of Na2EDTA·2 H2O, c(Na2EDTA) = 0.05 mol/L
57
Indicator buffer pellets
Solution of ammonia, w(NH3) = 25 %

Calcon-carboxylic acid (s), trituration with sodium chloride,
w(C21H14N2O7S) = 0.2 %
Solution of sodium hydroxide, w(NaOH) = 15 %
Solution of hydrogen peroxide, w(H2O2) = 35 %
Hydrochloric acid, c(HCl) = 2 mol/L

Demineralized water
Safety precautions:
Use conc. solution of ammonia under the hood. Be cautious when using conc. solution of
hydrogen peroxide.
Procedure:
Fill the volumetric flask up to the calibration mark. The solution has to be mixed well.
Determination of calcium
Exactly 25 mL of the sample are transferred to an Erlenmeyer flask und and then filled
up to appr. 100 mL. 2 mL of the solution of sodium hydroxide are added. After add-
ing a tip of a spatula of the Calcon-carboxylic acid trituration the solution is titrated
with standard solution of Na2EDTA·2 H2O until the change of colours from pink to
sky-blue. This colour has to persist for at least 1 minute.
Determination of magnesium
Appr. 1 mL of the solution of hydrogen peroxide is added to the solution after the deter-
mination of calcium. The solution is heated on a magnetic stirrer until the solution und
the turbidity are discoloured (the solution should not cook too long). Precipitated magne-
sium hydroxide is dissolved with a small amount of hydrochloric acid. It does not matter
if the clear solution has a light colouring. After adding a buffer pellet and 1 to 2 mL of
ammonia the solution is titrated with the standard solution of Na2EDTA·2 H2O, until the
change of colours from red to green.
Disposal:
The titrated solution has to be neutralized and can be given into the sink together with
the rest of the solution of Na2EDTA.
Problems
a) Insert the number of your volumetric flask into the answer sheet.
b) Record the consumption of the standard solution of Na2EDTA for both determina-
tions.
c) Calculate the mass concentration (mg/L) of calcium ions in your sample.
d) Calculate the mass concentration (mg/L) of magnesium calcium ions in your sample.
58
Answers
Part 2
The answers to the problems of the four rounds
The solutions are more detailed than expected from the pupils. That may
facilitate their comprehension in case of mistakes.
59
Answers Round 1
Answers Round 1
Solution to problem 1-1:
a) A = Ammonia (NH2)2CO + H2O CO2 + 2 NH3
b) M(CH4N2O) = 60.06 g/mol. M(NH3) = 17.031 g/mol

1 L of urine ≙ 1 kg of urine ≙ 0.005 kg of urea.
m(urea) = 550 kg/horse · 35·10-3 L/kg · 23 horses · 0.005 mol/L · 60.06 g/mol
m(urea) = 132.96 g
1 mol of CH4N2O ≙ 2 mol of NH3, 132.96 g of CH4N2O ≙ 132.96/60.06 mol = 2.214 mol
2.214 mol CH4N2O give 4.428 mol of NH3 ≙ 75.4 g of NH3.
c) n(C) : n(H) : n(O) : n(N) = : : : = 5.428 : 4.960 : 1.539 : 0.524
= 10.35 : 9.47 : 2.94 : 1.00  Empirical formula: C20H19O6N2

(or C21H19O6N2)
d) n(C) : n(H) : n(O) : n(N) = : : : = 5.058 : 4.920 : 1.655 : 0.558
= 9.07 : 8.82 : 2.97 : 1.00  Empirical formula: C9H9O3N

B' is an acid which hydrolyses to benzoic acid and an amino acid. 7 C atoms belong to benzoic
acid; the remaining 2 C atoms form the amino acid which thus can only be the simplest amino
acid, glycine, C2H5NO2.
B' is an acid amide of benzoic acid, hippuric acid (benzamidoacetic acid, N-benzoylglycine):
O H H
C C O
N C
H OH
e) C is benzonitrile. Basic or acidic hydrolysis of C yields an amide, which is subsequently hydro-

lyzed to benzoic acid and ammonia:
O O
N
C
NaOH
NaOH or HCl
oder HCl NH2 H2O OH
+ NH3
f) The white powder contains the following ions:

Na+, K+, Ca2+, Mg2+, CO32–, Cl–, SO42–, PO43– (H2PO4–, HPO42–).
According to the solubility the following salts are possible components of the powder:
Na2SO4, K2SO4, NaCl, KCl, CaCO3, MgCO3, Ca3(PO4)2, CaHPO4, Ca(H2PO4)2, Mg3(PO4)2,
MgHPO4, Mg(H2PO4)2, MgO, CaO.
Remark: The white powder is a typical dietary supplement for horses. Composition:
CaCO3, CaHPO4, NaCl, KCl, MgO, Na2SO4. In this problem supplements like vitamins and trace
elements are not considered.
60
Answers Round 1
Solution to problem 1-2
a) In a redox reaction electrons are (formally) transferred. In the process the respective oxida-
tion numbers are increased/decreased. In the reaction of sodium with water the sodium at-
oms release an electron each and are oxidized, the hydrogen atoms of water are reduced by
these electrons and form elementary hydrogen.
0 +I -II +I –II +I 0
2 Na + 2 H2O 2 NaOH + H2
b) Only the equations ii) and iii) represent redox reactions.
In vi) (and analogous in vii) there is no change of the oxidation number. Hydrogen peroxide
becomes attached to the chromium center as a peroxide dianion.

-II
O
+VI -II +I -I +I +VI –II -I +I,-II
O O -I 2– +
Cr2O7 + 4 H2O2 + 2 H  2 CrO5 + 5 H2O
Cr
+VI
InOviii) the electronegativity
O of arsenic and hydrogen are equal. Thus the oxidation numbers in
the compound as well as in the elements are 0

c) Primary elements cannot be recharged, secondary elements can.
d) Copper as cathode: Cu2+ + 2 e–  Cu, iron as anode: Fe  Fe2+ + 2 e–
e) Separation of the anode chamber from the cathode chamber by a porous barrier,
electrolyte/salt solution.
f) 0.34 V – (-0.41 V) = 0.75 V
g) Correct answers: i) 2, 4; ii) 3; iii) 1.
h) Yes, in this case dissolving is a redox reaction:
CoS + 4 H2O2 CoSO4 + 4 H2O
NiS + 4 H2O2 NiSO4 + 4 H2O
3 CoS + 2 HNO3 + 6 H+ 3 Co2+ + 2 NO + 3 S + 4 H2O
3 NiS + 2 HNO3 + 6 H+ 3 Ni2+ + 2 NO + 3 S + 4 H2O
Oxygen and nitrogen, respectively, are reduced, sulfur is oxidized. The metal ions do not
change their oxidation state.
i) In the reaction with conc. HNO3 elementary sulfur forms which does not dissolve and may
disturb the following analytic steps (or has to be separated). Nitrogen oxides may occur.
Hydrogen peroxide oxidizes sulfur up to sulfate.

a) n(C) : n(N) : n(H) : n(Cu) : n(Br) =
: : : : = 2.386 : 0.794 : 3.185 : 0.397 : 0.397
Empirical formula: C6N2H8CuBr

Molecular formula: (CuBr)(C6H8N2)
Molar mass: M(C6N2H8CuBr) = 251.59 g/mol
61
Answers Round 1
b) i) TG curve: The compound decomposes in three steps loosing mass in each of them. In
each step a solid compound should form.
ii) DTA curve: Each step is an endothermic reaction.
iii) MS-trend-scan curve: In each step a fragment with m/Z = 108 splits off.
m/Z = 108 ≙ M(2,5-dimethyl pyrazine).  In each of the three steps
2,5-dimethyl pyrazine is split off..
c) M(C6H8N2) = 108.14 g/mol
Theoretically possible loss of weight:
Splitting-off of 1 mol of dimethyl pyrazine: m = · 100% = 42.98%
Splitting-off of ½ mol of dimethyl pyrazine: m = ½ · 42.98% = 21.49 %

Splitting-off of ¼ mol of dimethyl pyrazine m = ¼ · 42.98% = 10.74 %
 1. Step: splitting-off of ½ dimethyl pyrazine product: (CuBr)2(C6H8N2)

2. Step: splitting-off of ¼ dimethyl pyrazine product: (CuBr)4(C6H8N2)
3. Step: splitting-off of ¼ dimethyl pyrazine product: (CuBr)

a)
H
O C OH OH
Na/NH3(fl) H2/Kat.
+ C
H
A B
O O
+
NaOEt / EtOH OC2H5
– C2H5OH
H
G
C
OH HO + O O O
C Al(iOPr)3 (kat.)
H2/Kat. O
H T
Na/NH3(fl) – CO2
F E D C
b) Reaction of C to D (in the middle: Claisen rearrangement):

O O H
OH O O O O
O O O
– CO2
C D
62
Answers Round 1
c) Linalyl acetate
O
O
OH O
+
O
– t-BuOH
F H
d) Linalyl acetate is a component of lavender oil, clary sage oil, bergamot oil.
e) Linalool (F) may undergo an allyl rearrangement to form the isomers nerol and geraniol:
C+
+
CH2
+ H+
– H2O
+ H2O
– H+
OH
OH
H+/H2O +
OH
F I/J J/I + H2O

Nerol Geraniol – H+
+
C+ CH2
63
Answers Round 2
Answers Round 2
Solution of problem 2-1
a) A: Na3H2IO6
B: Na2S2O8
C: NiSO4
Remark: Nickel sulfate crystallizes from an aqueous solution with 6 or 7 molecules of crystal
water and is sold as such a compound.
b) Oxidation state of sulfur: +VI.
Two of the oxygen atoms are peroxidic and thus possess the formal oxidation state –I.
2– 2–
O O O O
peroxidic peroxidic
peroxidisch peroxidisch
S S O or S S O
O O O O
O O
O O O O
c) Compound X: NaNiIO6
+II,+VI,–II +I,+I,+VII,–II +I, +VI, –II +I,–II +I,+IV,+VII–II, +I,–II +I, +I,+VI,–II +I,+VI,–II
NiSO4 + Na3H2IO6 + Na2S2O8 + H2O NaNiIO6 · H2O + 2 NaHSO4 + Na2SO4

or
+II +I,+VII,–II +VI,–II +I +I,–II +I,+IV,+VII –II, +I,–II +I,+VI,–II
Ni2+ + H2IO63– + S2O82– + Na+ + H2O NaNiIO6 · H2O + 2 HSO4–
Percentage of nickel
M(NaNiIO6 · H2O)= 322.5993 g/mol w(Ni) = (58,69/322,60) · 100% w(Ni) = 18.19 %
d) You may expect diamagnetism for a Ni(IV) compound (no unpaired electron).
Nickel has the oxidation state +IV and thus a d6 system.
Whether there is a low spin or a high spin configuration depends on the splitting of the ligand
field.
The splitting is influenced by the ligands (in this case oxygen – situated in the middle of the
spectrochemical series), by the metallic center (in this case nickel - rather small splitting (3d
system), the higher the quantum number, the higher the splitting) and by the charge of the
central atom (in this case high charge – great splitting). In this case the charge should be
crucial:
Energy
Energy
(High spin) (Low spin)

Small splitting High splitting
Remark: There are actually Ni(III) centers in this compound (especially after aging) thus you
can observe a small amount of paramagnetism.
64
Answers Round 2
e) The alloy is known as nitinol, a shape memory alloy. If it is deformed it will recover to the
original shape when heated.

a) At first A has to be found.
Dioic acid Molecular formula %C
HOOC-COOH C2H4O4 26.68
HOOC-CH2-COOH C3H4O4 34.63
HOOC-CH2-CH2-COOH C4H6O4 40.68
HOOC-CH2-CH2-CH2-COOH C5H8O4 45.46
HOOC-CH2-CH2-CH2-CH2-COOH C6H10O4 49.31
HOOC-CH2-CH2-CH2-CH2-CH2-COOH C7H12O4 52.50
A is probably adipic acid C6H10O4.

COOH COOC2H5
1. NaOC2H5 H5C2OOC O
C2H5OH, H+ 2. H+
C
HOOC H5C2OOC
A B
H+, T
O
HO O
CH2N2
Ag2O (kat.) CH2N2
– N2
F E D
, p-TsOH (kat.)
N – H2O
H
O O
–
N N+ O H+/H2O
– C4H9N O
I
NaOC2H5
G H
T
O – H2O O
HO
K J
65
Answers Round 2
b) J is a bicyclic compound with 3 stereogenic centers, thus it has 8 stereoisomers.
6 4
7 5
3 *
10 2 *
8
9 1 O * O
HO HO
H Enantiomers
Enantiomere H H Enantiomers
Enantiomere H
R S R S
S R S R
S R R S
O O O O
HO HO HO HO
H Enantiomers
Enantiomere H H Enantiomers
Enantiomere H
R S R S
R S R S
S R R S
O O O O
HO HO HO HO
All stereomers which are not enantiomers are diastereomers.
c) i) Well-known as Dieckmann condensation (intramolecular Claisen condensation, R =

C2H5):
R R
– R R
O O O O
O O O O
–
+ O R
H
O R O R O R
– ROH – RO–
– O
O O O
B C
ii)
O H
H5C2OOC O O C O OH O
H , T
+
– C2H5OH
– CO2
C
Enol
Enol D Ketone
Keton
iii) Well-known as Michael addition of a nucleophile (enamine) to an a,ß unsaturated carbon-

yl compound:
–
N N+ N+ O
O
–
G H
66
Answers Round 2
iv) Intramolecular aldol reaction:
O –
O Na+
NaOC2H5
H H
O – C2H5OH
O
–
I OC2H5
C2H5OH
O – NaOC2H5
HO O
– O
+
Na
J
A combination of iii and iv (Michael addition followed by an intramolecular aldol reaction) is

denoted as Robinson annulation.
d) If cyclohexanone reacts directly with ethyl vinyl ketone in the presence of a base there is the
risk of a multiple alkylation i.e. the alkylation product may react with more ethyl vinyl ketone
to form the respective ,‘-di-alkylation products.
First of all ethyl vinyl ketone is in not stable in a basic solution, it tends to polymerize. Thus
the yield of the wanted product is normally very small.
The synthesis via the enamine has the advantage that basic conditions are not necessary. The
polymerization of the ethyl vinyl ketone is suppressed and the product of the alkylation (an
iminium ion) cannot react again with ethyl vinyl ketone so that there is no multiple alkylation.
e) Compound I contains two carbonyl groups, both of them can be deprotonated to form an eno-
late. Thus there may be four different products in an intramolecular aldol addition. All these
reactions are reversible so that at the end the thermodynamic most stable product is formed.
Two of the four aldol adducts contain strained four membered rings and thus are instable.
Another product has a bicyclic structure from which water cannot be eliminated. The only sta-
ble product the aldol adduct J with two six membered rings free of strain and the possibility of
splitting off of water.
67
Answers Round 2
Possible enolates from I:

OH OH O O
O O OH OH
HO O
OH
O O
HO HO
O
Product
Produkt J J four membered rings
Vierring Vierring Bicyclic structure, no elimination
Bicyclus
of water possible
keine H2O-Abspaltung möglich

a) IR spectroscopy: IR radiation is shone through a sample and certain frequencies are ab-
sorbed. The molecules gain vibrational energies. The transmitted frequencies are determined
in a plot.
Raman spectroscopy: The sample is irradiated with an intense beam of monochromatic light,
most conveniently running in the visible spectrum. Most of the scattered photons have the
same frequency as the original from the laser but a small amount of the photons (Raman pho-
tons) are absorbed by the molecules and afterwards emitted with different frequencies. The
shift in energy between the Raman photons and the original laser photons is equal to the dif-
ference in energy of two vibrational energy levels.
Thus IR spectroscopy is a direct method to detect molecule vibrations whereas Raman spec-
troscopy is an indirect method.
b) i) z=3·3–6=3
Raman aktive Raman aktiv
IR aktive IR aktiv
Raman aktive
IR aktive
ii) z=3·2–5=1
Raman aktive IR inaktive
iii) z=4·3–6=6
Raman active Raman active

IR active IR active
68
Answers Round 2
Raman active Raman inactive

IR inactive IR active
Raman active Raman active

IR active IR active
c) Only three signals are expected because you find a change in the dipole moment only at the
asymmetric stretching mode and in the bending modes.
Remark: The two binding modes are degenerated. Thus there are only two signals observed.
(2350,1 cm–1 und 667,5 cm–1, Phys. Rev., Vol. 41, S. 291–303, 1932).
d) To describe the vibrational movements of the atoms you have to consider their original posi-
tion in the coordinate system as well as their new positions caused by the vibration.
The positions of N atoms are defined by 3N coordinates (x, y, z). Here the position of the total
molecule in space is determined (translation) as well as its orientation with respect to the co-
ordinate system (rotation).
The orientation of a linear molecule is given in one direction  two coordinates are sufficient
to describe the position of the molecular axis. That means that you have to subtract three
modes of translation and two modes of rotation to get the vibrational modes (-5).
In non-linear molecules one more rotation mode is possible, that means that you have to
subtract three modes of translation and three modes of rotation to get the vibrational modes
(-6).
e) = Number of degrees of freedom of helium: 3  He = 5/3 = 1.67
pchamber ≤ preservoir · = 650 mbar · = 543 mbar
f) Limonene has the molecular formula C10H16  N = 26.

z=3N–6  number of vibrations z = 3 · 26 – 6 = 72
Kind of vibrations: C-H stretching (2700-3100 cm–1), C=C stretching (1700-1800 cm–1) and
skeleton vibrations (below von 1500 cm–1)
–18
g) 1 Hartree = 4.360 · 10 J  E(B) – E(A) = E = 6.475 · 10–5 Hartree = 2.823 · 10 –22
J
–22 –23
For 1 mol: 2.8231 · 10 J · 6.022 · 10 mol-1 = 170.00 J = 0.17 kJ/mol
1 eV = 96.485 kJ/mol  E = 1.762 · 10–3 eV
The transition A  B is possible at room temperature.
That can be justified by the Boltzmann distribution at 25°C:

= N1 = number of molecules of B, N2 = number of molecules of A,
kB = Boltzmann's constant = 8.314 JK-1mol1
 = = 0.934
69
Answers Round 2
Both states are nearly equally occupied. 100 molecules of the ground state (A) correspond to
93 molecules of the excited state (B), e.g. the energetically unfavorable conformer B occurs
nearly as often as the favored A.
h) Using the Boltzmann distribution again:

 
=  ln ( )=-  T=-
( )
T= = 10.5 K
( )
i) Axial substituents in a ring system are relatively close to each other. Thus they show repul-
sion due to steric effects. The larger the substituent the stronger is this repulsion. There is
much more space in equatorial positions thus larger substituents prefer this position.
j) The stability of B with regard to the two rotamers is due to the intramolecular interaction of
the isopropylene group with the double bond of the ring. If the methylene unit of the isopro-
pylene group points in the direchtion of the double bond a weak hydrogen bridge bond occurs
(methylene group = donator, double bond = acceptor).
k)
l) The center of the band of the monomer can be estimated from fig. 4: 1740 cm–1.
From the calculation you can see that dimer 1 differs by  20 cm–1 from the monomer, dimer
2 by  20 cm–1. Thus you can assign the dimer peak at 1721 cm–1 to dimer 1.
70
Answers Round 3 Test 1

a) D b) B c) D d) D e) B,C E f) B,C,E g) C
a) 6 I- + 2 CrO42- + 16 H3O+  3 I2 + 2 Cr3+ + 24 H2O

6 I- + Cr2O72- + 14 H3O+  3 I2 + 2 Cr3+ + 21 H2O
b) In the mixture: m1 = mass of chromate with M1 = 194.2 g/mol
m2 = mass of dichromate with M2 = 294.2 g/mol
n1 · 194.2 g/mol + n2 · 294.2 g/mol = 1.000 g (ni = amounts)
n2 = - · n1 n2 = 3.399 ·10-3 mol - 0.660 · n1 (1)
I2 + 2 S2O32-  2 I- + S4O62-
n(S2O32-) = 18.40 mL · 0.100 mol/L = 1.840·10-3 mol
 n(I2) = 0.920·10-3 mol
n(I2) = 1.5 · n1/10 + 3 · n2/10 (2)
-3 -3
(1) in (2): 0.920·10 mol = 0.15 · n1 + 0.3 · (3.399 ·10 mol - 0.660 · n1)
-3 -3
 n1 = 2.077·10 mol m1 = 2.077·10 mol · 194.2 g/mol = 0.403 g
c) In the solution for the reactions mentioned in a) there is an excess of potassium iodide. Only
the mass of iodide which has reacted to iodine is necessary for the exact calculation. This
mass is determined accurately by the titration with thiosulfate.
d) MgC2O4  MgO + CO2 + CO
e) B = MgC2O4 with M(MgC2O4) = 112.3 g/mol
From the figure: m(B) = 0.75 g  n(MgC2O4) = = 6.68·10-3 mol
n(H2O) = = 0.0139 mol
n(MgC2O4) : n(H2O) = 6.68·10-3 : 0.0139 = 1.00 : 2.08 x=2

a)
Formula, type PCl5 AX5 BrF3 AX3E2 BrF5 AX5E
Structure (Trigonal dipyramid) (Distorted T-form) (Distorted tetragonal
pyramid)
Cl F
F 
F F
Cl
Br
P Cl F Br F F
Cl
F
Cl
 = 81.9°, Br lies below
Angle FBrF = 86.2° the plain of the 4 equa-
torial F
71
Formula, type BF4- AX4 SF4 AX4E XeF2 AX2E3

Structure (Tetrahedron) (Distorted tetrahedron) (linear)
F
F
F
F
S
F Xe
B F
F F F
F
Angle FSF(equ.) = 101°
Angle FSF (axial) = 173°
The angles and the statements in brackets are not expected.
b)

a)
A B C
Cl NH3 NH3 2+ Cl 2–
Cl Pt NH3 Cl Pt Cl NH3 Pt NH3 Cl Pt Cl
NH3 NH3 NH3 Cl
b) A is a polar compound which can be dissolved in polar solvents.

B is a non-polar compound thus it can be dissolved in non-polar solvents.
c) [Xe]4f145d8
d) It has to be a low-spin complex because of the diamagnetic behavior (no unpaired electrons)
of the compounds.
a) Alkali metals own only one valence electron and have small first ionization energies.
Thus they tend to reach noble gas configuration by releasing an electron.
They react as strong reducing agents.
72
b)
Energy
Bond order =
Explanation (not expected in this detailedness): Starting with two 3s atomic orbitals with a single
electron in each of them two  molecular orbitals arise. One is bonding, the other one antibonding.
There are two electrons in the bonding MO, the antibonding MO is empty. This leads to a single
bond of both atoms.
2– – 2–
2–
c) O O O O O F2 is isoelectronic to O2 .

d) Me2O2 · 2 MeO2
e) i) 2 LiOH + CO2 Li2CO3 + H2O

ii) 2 Na2O2 + 2 CO2 2 Na2CO3 + O2
iii) 4 KO2 + 2 CO2 2 K2CO3 + 3 O2
bzw. 4 KO2 + 2 H2O + 4 CO2 4 KHCO3 + 3 O2
f) The ion mobility depends on the size of the ions: Big cations show a smaller mobility than
smaller ones. Lithium cations show a small mobility because of their large hydration sheet.
g) Formation of sodium carbonate:

CaCO3 + 2 NaCl Na2CO3 + CaCl2
h) NH4HCO3 + NaCl NH4Cl + NaHCO3 the right hand side is favored

NH3 + CO2 + H2O NH4HCO3
i) 2 NaHCO3 Na2CO3 + CO2 + H2O
j) Calcium hydroxide is used for the recovery of ammonia:

Ca(OH)2 + 2 NH4Cl CaCl2 + 2 NH3 + 2 H2O
a) A = ·c·d with absorbance A = lg and I = 0.4·I0

-1
 c(A-) = - lg 0.4 /(21 L mol cm-1 · 1 cm) c(A-) = 1.9·10
-2
mol/L
+ -8.8
pH = 8.8  c(H ) = 10 mol/L
Ka = with c0 = 1 mol/L Ka =
Ka = 3.0·10-8 pKa = - lg Ka pKa = 7.5

b) Using 20 mL of NaOH solution 40 mL of a solution of the sodium salt of 3-chlorobutanoic acid
(c = 0.5 mol/L) are formed (3-chlorobutanoic acid will be denoted as HR).
73
R- is a weak base with Kb = 10-14 / 10-4.05 Kb = 10-9.95
10-9.95 = x mol/L = c(HR) = c(OH-) « c(R-) = 0.50 mol/L
10-9.95 = x2 / 0.5 x = 7.49·10-6 c(OH-) = 7.49·10-6 mol/L

 pOH = 5.13 pH = 14 – 5.13 pH  8.9
c) Phenolphthalein
d) pH = pKa + lg  pH = pKa + lg
n(R-) = V(NaOH) · c(NaOH) = V(NaOH) · 1 mol/L

-
n(HR) = V0(HR) · c0(HR) - n(R ) = 20 mmol - V(NaOH) · 1 mol/L
 3.7 = 4.05 + lg
 V(NaOH) = mL V(NaOH) = 6.2 mL

A: Barium nitrate B: Potassium iodide C: Lead acetate D: Silver nitrate
E: Sodium hydroxide F: Ammonia G: Copper sulfate
B and C: 2 KI (aq) + Pb(OAc)2 (aq) PbI2 (s) + 2 KOAc (aq)

PbI2 (aq) + 2 KI (aq) K2[PbI4] (aq)
B and G: 4 KI (aq) + 2 CuSO4 (aq) 2 CuI (s) + I2 (aq/g) + 2 K2SO4 (aq)
C and E: Pb(OAc)2 (aq) + 2 NaOH (aq) Pb(OH)2 (s) + 2 NaOAc (aq)

Pb(OH)2 (s) + NaOH (aq) Na[Pb(OH)3] (aq)
C and F: Pb(OAc)2 (aq) + 2 NH3 (aq) + 2 H2O (l) Pb(OH)2 (s) + 2 NH4OAc (aq)
D and F: 2 AgNO3 (aq) + 2 NH3 (aq) + H2O (l) Ag2O (s) + 2 NH4NO3 (aq)
Ag2O (s) + 2 NH3 (aq) + H2O (l) 2 [Ag(NH3)2]OH (aq)
E and G: 2 NaOH (aq) + CuSO4 (aq) Cu(OH)2 (s) + Na2SO4 (aq)

T
Cu(OH)2 (s) CuO (s) + H2O
F and G: 2 NH3 (aq) + CuSO4 (aq) + 2 H2O (l) Cu(OH)2 (s) + (NH4)2SO4 (aq)
Cu(OH)2 (s) + 4 NH3 (aq) [Cu(NH3)4](OH)2 (aq)
74

a)
CH3Cl + AlCl3 [AlCl4]– + CH3+
A B
CH3 CH3 CH3

H H + H
CH3+ +
+ +
B C1,2,3 C1,2,3 C1,2,3
CH3
+ H+
b) The so called  complex is an intermediate in the reactions.

ortho-substitution
CH3 CH3 CH3

NO2 NO2 NO2
H H + H
+ +
para-substitution
CH3 CH3 CH3
+ +
H NO2 H NO2 H NO2
meta-substitution
CH3 CH3 CH3
+ +
H H + H
NO2 NO2 NO2
In the ortho- and para-substitution there are resonance structures with a positive partial
charge at the carbon atom with the methyl substituent. These structures are stabilized by the
+I effect of the methyl group. Thus the production of the ortho and the para product are fa-
vored.
Remark: In text books you can find explanation using hyperconjugation. This is not expected
in this problem.
c) Main product: 2,4-Dinitrotoluene (1-Methyl-2,4-dinitrobenzene) CH3

NO2
The methyl group directs the bromine substituent into 2 and 6 position (ortho-
position to methyl), the nitro group into the 2 and 6 position, too, (meta posi-
tion to the nitro group). So both substituents direct in the same position.
NO2
75
d) Main product: 2-Bromine-4-methylphenol (2-Brom-p-kresol) OH

Br
The hydroxyl group directs the bromine substituent into 2 and 6 position (ortho-
position to the hydroxyl group). Against this the methyl group directs into 3 and
CH3
5 position (ortho-position to the methyl group). As the hydroxyl group has a
stronger reactivity 2-bromine-4-methylphenol is formed with a higher yield.

O O
a) S= H3C CH2 C OH Acid TH
=3C CH2 C NH2 Amide
OH
U= H3C CH2 CH2 OH Alcohol V=
H3C CH2 C R Alcohol
R
b)
–
O O
1. R1 C OR2 + OH– R1 C OR2
OH
–
X
–
O O
2. R1 C OR2 R1 C OH + R2O–
OH
– Y Z–
X
c) The isotopically labelled oxygen atom should only be found in the alcohol not in the acidic
part.
d)
O 1. LiAlH4
2. H2O H3C CH2 CH CH CH2OH + C2H5OH
H3C CH2 CH CH C O CH2 CH3
Q R
2-Pentene-1-ol Ethanol
Remark: Lithium aluminum hydride does not react with the C=C double bond.
e)
O
1. LiAlH4 OH
2. H2O
O H3C CH CH2 CH2 CH2 OH
CH3 W 1,4-Pentane diol
76
a) i) C2H6O: H3C – CH2 – OH and CH3 – O – CH3
H3C CH3:
ii) H HH
H H
C C
H
H H H H
H
H
staggered
staggered eclipsed
eclipsed
Cl Cl
iii)
C C
H C2H5
H3C H3C
C2H5 H
H H
H H H Cl
iv) Br C Cl Br C Cl
C C C C or
Cl Cl Cl H H3C C OH HO C CH3
H H
cis-Isomer (Z) trans-Isomer (E)
b) Cis-trans-isomers are diastereomers.
c)
H3C CH2 CH3

Cl CH3 CH3
*
* * CH3
H3C CH2 CH CH3 * *
*
O CH3
CHO
O OH OH * CH OH
* HOOC CH CH COOH * CH OH
* CH3 * *
CH2OH
d) Rule 1: Look at the four atoms directly attached to the chirality center and rank them accord-
ing to atomic number. The atom with the highest atomic number is ranked first, the atom with
the lowest atomic number is ranked fourth: Cl > O > C > H.
Rule 2: Orientate the molecule so that the group with the lowest priority (H) points directly
back, away from us. The three remaining substitutes radiate towards us like the spokes of a
steering wheel.
Rule 3: If a curved arrow drawn from the highest to the second highest to the third highest
(123) is clockwise the chirality center has an R configuration. If the arrow is counter-
clockwise it has an S configuration..
e) i) R ii) R iii) 1S, 2S iv) S v) R
77
Answers of Round 3 Test 2
a) B,D b) A,B.E c) A,D,E d) C e)A,B,C f) A,C g) A,D

a) =
Solution No. I II III IV

c in mol/L 1.00·10-3 0.50·10-3 0.25·10-3 0.15·10-3
 in L·mol-1·cm-1 890 880 920 867
-1 -1
Mean value  = 889 L·mol ·cm
b) Oxidation of CO: 5 CO + I2O5  I2 + 5 CO2
c(I2) = c(I2) = 0.69/889 mol/L c(I2) = 7.76·10-4 mol/L

 n(I2) in 100 mL solution = 7.76·10-5 mol
 n(CO) = 3.88·10-4 mol
V(CO) = V(CO) = m3
V(CO) = 9.55·10-6 m3 = 9.55 mL ≙ 1.9 %

a) Let m = 178.96 g (≙ 1 mol of Mn(NO3)2) react
178.96 g · 52.04 % = 93.13 g
 m(MnOx) = 85.83 g with 54.94 g of manganese and 30.89 g of oxygen
n(O) = = 1.93 mol x = 1.93
It has to be a gas richer in oxygen than NO2: N2O5

Balance for the reaction of 1 mol of Mn(NO3)2)
amount of nitrogen: n(NO2) + 2·n(N2O5) = 2 mol
amount of oxygen: x mol + 2·n(NO2) + 5·n(N2O5) = 6.00 mol with x = 1.93
2 · n(NO2) + 5 · n(N2O5) = 4.07 mol
- 2 · n(NO2) - 4 · n(N2O5) = - 4.00 mol
n(N2O5) = 0.07 mol and n(NO2) = 1.86 mol
V(NO2) : V(N2O5) = n(NO2) : n(N2O5) = 1.86 : 0.07  25.6 : 1
b) Concentration of Ni2+:
10.0 mL · c(Ni2+) = 17.1 mL · 0.0100 mol/L  c(Ni2+) = 0.0171 mol/L
n(Ni2+) in 20.0 mL : 20.0·10-3 L · 0.0171 mol/L = 3.42·10-4 mol
excess of Ni2+: 21.3 mL · 0.0100 mol/L = 2.13·10-4 mol
Ni2+ bound by CN- = 3.42·10-4 mol - 2.13·10-4 mol = 1.29·10-4 mol
n(CN-) in 20 mL = 4 · n(Ni2+) bound by CN- = 5.16·10-4 mol
c(CN-) = 5.16·10-4 mol/(20.0·10-3 L) = 0.0258 mol/L
78

a)
Half-chair Half-chair
A B
Boat
F C
Twist boat Twist boat
D
Chair Chair
b) Read from the diagram: EA  42-43 kJ/mol,

boat and twist-boat conformers can be isolated.
c) In the process 1-A 1-B the protons Ha and Hb change their positions.
d)
For each of the two protons Ha und Hb a singlet is observed at deep temperatures (-84 °C). The
chair flip is slower than the time necessary for one NMR measurement (lifetime of the NMR signal).
Thus for these two protons different signals can be detected.
At a higher temperature (-55 °C) only one singlet is observed. The chair flip now is much quicker
than the NMR measurement. A singlet can be detected if t(chair flip) ≪ t(NMR measurement).
e) (In e) and f) the units are omitted in order to arrange the calculations more clearly.)
/°C T/K k/s-1 1/(T/K) · 103 ln

- 55 218 2000 4.59 2.216
- 63 210 540 4.76 0.944
- 65 208 400 4.81 0.654
- 67 206 356 4.85 0.547
- 71 202 200 4.95 - 0.010
- 77 196 70 5.10 - 1.030
- 80 193 40 5.18 - 1.574
79
2.5
2.0
1.5
1.0
0.5
ln(k/T)
ln[(k/s-1)/(T/K)]
0.0
-0.5
-1.0
ln = -6233 · + 30.74
-1.5
-2.0
0.0045 0.0046 0.0047 0.0048 0.0049 0.0050 0.0051 0.0052
1/(T/K)
1/T
Fig.: Graph ln[(k/s-1)/(T/K)] against 1/(T/K) with linear fit
f) (2) G‡ = H‡ - T ∙ S ‡

inserted in (1) ln k/s-1 = ln T/K + 23.76 - ΔG‡/(RT):
ln = -(H‡/R) + 23.76 + S‡/R
By comparison with the given equation ln = -6200 · +30.00 you get:
i) H‡/(R/T-1) = 6200  H‡ = 51.55 kJ/mol

ii) 30 = 23.76 + S‡/R  S‡ = 51.88 J K-1 mol-1
G‡ = 51.55 kJ/mol – (273 – 63) K · 51.88/1000 kJ K-1 mol-1 G‡ = 40.66 kJ/mol

a) C2H6 C2H4 + H2

b) Kp900 = Kp900 = Kp900 = 5.02·10-2
c) C2H4 + H2 C2H6
S°hyd = S°900 K(ethane) - S°900 K(ethene) - S°900 K(H2)
-1 -1 -1 -1
S°hyd = 319.7 J·mol ·K - 291.7 J·mol ·K - 163.0 J·mol-1·K-1 = -135 J·mol-1·K-1
-1 -1
H° = G° + T·S° H°hyd = - 22.39 kJ/mol + 900 K · (-135 J·mol ·K )
H°hyd = - 143.9 kJ/mol
d) C2H6 C2H4 + H2
ni before the reaction in mol 1 0 0
ni in equilibrium in mol 1-x x x =1+x
pi in equilibrium ·ptotal ·ptotal ·ptotal
 Kp900 = with ptotal = 1.013·105 Pa and p0 = 1.000·105 Pa
5.02·10-2 = · 1.013 x = 0.22
80
 p(H2) = p(ethene) = · ptotal = 0.18 · ptotal p(ethane) = · ptotal = 0.64 · ptotal
 V(H2) = V(ethene) ≙ 18 % each V(ethane) ≙ 64 %


e) ln(Kp600/Kp900) = · (T1-1 – T2-1) ln(Kp600) = ·(600-1 – 900-1) + ln 5.02·10-2
ln(Kp600) = - 12.6 Kp600 = 3.4·10-6

f) Kp600 < Kp900
The dehydrogenation is endothermic. For an endothermic reaction increasing the temperature
increases the value of the equilibrium constant and thus the equilibrium moves towards the
products (Le Chatelier's principle).
a)
no reaction no reaction
Fe2+ or FeS
Fe2+ or FeI2
Remark: Only one species is asked in each box. In some cases the species are built more compli-
cated than written down.
b) In yellow prussiate K4[Fe(CN)6] iron exists in the oxidation state II. This corresponds to 24
electrons or 6 valence electrons respectively. The cyanide ligands add 6 x 2 = 12 electrons
and in doing so a noble gas configuration is formed (36/18 electrons). In red prussiate one
electron is missing to form the stable noble gas configuration. Thus it is more unstable and a
better oxidant.
c) The mixture contains iron(II) oxide and elementary aluminum. The products are iron and
aluminum oxide: Fe2O3 + 2 Al  Al2O3 + 2 Fe
Remark: In this process a temperature of about 2400°C is reached at which iron is liquid.
81
d) FeCl3 + 6 H2O [Fe(H2O)6]3+ + 3 Cl–

[Fe(H2O)6]3+ + H2O [Fe(H2O)5(OH)]2+ + H3O+
e)
cubic body-centered cubic close packed
f) Density:  =
-Iron:
Space diagonal: ds = a· √ (a = edge length of the cube)
ds = 4·r(Fe)  4 · r(Fe) = a ·√
 a= with r(Fe) = 126 pm = 126 · 10–10 cm
√
 edge length of the cube: a = 2.91 · 10–8 cm
volume of the cell : Vcell = a3 Vcell = 2,46 · 10–23 cm3
with Z = 2: d= = 7.54 g·cm-1
-Iron:
Face diagonal: df = a · √ (a = edge length of the cube)
df = 4·r(Fe)  4 r(Fe) = a · √
 a= with r(Fe) = 126 pm = 126 · 10–10 cm

√
 edge length of the unit cell: a = 3.56 · 10–8 cm

volume of the cell : Vcell = a3 Vcell = 4.53 · 10–23 cm3
with Z = 4: = = 8.19 g·cm-1

a) There are two possibilities for the potential of the lead electrode:
E(Pb2+/Pb) = (0.238 – 0.478) V = -0.240 V or E(Pb2+/Pb) = (0.478 + 0.238) V = +0.716 V.
As the value of the lead concentration is very small only the first value has to be considered.
-0.240 V = -0.126 V + · ln [c(Pb2+)/(1 molL-1)]
ln [c(Pb2+)/(1 molL-1)] = ln c(Pb2+) = -8.879
c(Pb2+) = c(SO42-) = 1.393·10-4 mol/L Ksp(PbSO4) = 1.94·10-8

b) pH = 3,00  c(H3O+) = 1.0·10-3 mol/L  c(SO42-) = ½· 1.0·10-3 mol/L
*
Ksp = c(SO42-) · c(Pb2+)/(1 mol/L)2 2.00·10-8 = ½· 1.0·10-3 ·c(Pb2+)/(1 mol/L)
c(Pb2+) = 4.0·10-5 mol/L
82
EPb-electrode = -0.126 V + · ln 4.00·10-5 EPb-electrode = -0.256 V

o
E =E Ref - EPb-electrode E = 0.494 V
* In the strict sense you have to consider the amount of SO42- resulting from the dissolution
of lead sulfate, yet the difference is very small:
c(Pb2+) · [c(Pb2+) + ½· 1.0·10-3 mol/L] = 2.00·10-8 (mol/L)2  c(Pb2+) = 3.72·10-5 mol/L
E*Pb-electrode = -0.126 V + · ln 3.72·10-5 E*Pb-electrode = -0.257 V
E* = 0.495 V

a) X = CH3CH2OH
b) Fragments in the mass spectrum
m/e = 45 m/e = 31 m/e = 29
+ + + +
H3C CH O H H3C CH O H H2C OH H2C OH H3C CH2+
c) Peaks in the 1H NMR spectrum:

Quartet at 3.7 (3.687) ppm: signal of the CH2 group
Triplet at 1.2 (1.226) ppm: signal of the CH3 group
Singlet at 2.6 (2.61) ppm: Signal of the OH group
d) Y = Dimethyl ether. In the 1H-NMR a singlet is expected.
e) i) 2 ii) 2 iii) 4 (the two H atoms of the CH2Cl group are diastereotopic because of the
adjacent stereogenic center) iv) 3 v) 2 vi) 3 vii) 3 viii) 2

a)
H H H H H H H H
 
R C C +n C C R C C C C
H H H H H H n H H
A
H H H H H H H H H H H H

2 R C C C C R C C C C C C C C R
H H n H H H H n H H H H H H n
A B
H H H H H H H H H H H H

2 R C C C C R C C C C + R C C C C H
H H n H H H H n H H H H n H H
A C/D C/D
83
b)
O O H
H
C  H H C C 
O O C
+ C C H
H
H H
O H O H H
H H H
C C H H C C C 
O C

O C C
+ C C
H H H H
H H H H
c)
i) ii) iii)
H OCH3 H Cl H H
C C H2C CH2 C C C C
H H Cl H Cl Cl
d)
H CH3 H CH3 H CH3 H CH3 H CH3
isotactic:
H H H H H H H H H H
H CH3 CH3 H H CH3 CH3 H H CH3
syndiotactic:
H H H H H H H H H H
H CH3 H CH3 H CH3 CH3 H CH3 H
atactic:
H H H H H H H H H H
e)
H H H H H H
C C C C
C C C C
H H H H H H
H H H H
H H H H
C C C C
C C C C
H H H H
84
a)
A B c d
OH
OH LiAlH4 H+ / H2O
H
CN
O
b) Nucleophilic addition.
O O–
C C
H H
–
+ C N CN
O– OH
C C
H H
+ H C N + –
C N
CN CN
(Remark: The reaction of HCN with aldehydes and ketones is known as cyanohydrin reaction.)
c)
K L M N
OH OH H H +
O+ R C H
R C H R C H
+ R C H OR'
OR'
OR'
d) The equilibrium can be shifted towards the product by withdrawal of water using a water sep-
arator.
e)
H3C
O OH O OH
H + H3C
+ HO OH
H3C CH3 – H2O O
f)
O P Q
OH OH OH
N
C H C CH3
C
H H H
85
R S/T T/S
CH2 OH O
CH3 C C
H
O– Na+
H
g)
–
O O
C C H
H
+ –
OH OH
– –
O O
H
C H C C H
O
O H O + H C
OH
h) Aldehydes with a hydrogen in  position form enols when they are treated with a base. Thus a
Cannizzaro reaction cannot occur.
86
Answers Round 4 (theoretical)

a)
close-packed cubic close-packed hexagonal
b)
Elementary Denotation Coordination Metal atoms
cell number per cell
primitive cubic 6 1
body centered cubic 8 2
face-centered cubic 12 4
c)
Tetrahedral interstice Octahedral interstice
d) In each el. cell: 4 octahedral interstices and 4 atoms  n octahedral interstices

In each el. cell: 8 tetrahedral interstices and 4 atoms  2n tetrahedral interstices
1
e) Chloride anions: 8 x /8 + 3 x ½ = 4
Sodium cations: 12 x ¼ + 1 = 4
Thus the formula of the elementary cell is Na4Cl4
f) √( ) ( )
 rCl = 198.7 pm
562,0 pm = 2 · rCl + 2 · rNa
 rNa = 82,3 pm
Remark: The assumption that the chloride anions are in contact to each other leads to a size too
large for them and to a too small size of the sodium cations.

87
a)
Central atom Charge
Ligand Coordination number
b)
i) ii) iii) iv)
H H O O O
H H O
C C C C O
– O O
H 2N NH2 O O– O
Me Me Me
N
O
Me
O O
N O O
O O
c) The gain in entropy arising from the fact that the number of molecules increases from left to
right is highest for the formation of the trien complex, lowest (not changing) for the formation
of the hexammine complex. Thus [Ni(en)3]2+ should be most stable, [Ni(NH3)6]2+ least stable.
d)
L X L Y
Me Me
X Y X X
trans cis
e) Chlorine is strongly trans directing 
Synthesis of the cis product:
2– –
Cl Cl Cl Cl Cl NH3
+ NH3 + NH3
Pt Pt Pt
– Cl– – Cl–
Cl Cl Cl NH3 Cl NH3
Synthesis of the trans product:

2+ +
H3N NH3 H3N Cl H3N Cl
+ Cl– + Cl–
Pt Pt Pt
– NH3 – NH3
H3N NH3 H3N NH3 Cl NH3
f) The following equilibria have to be taken into account:

Ni(OH)2 Ni+ + 2 OH– KL = 3.2 · 10–17
Ni+ + 6 NH3 [Ni(NH3)6]+2 KB = 1/KD = 5.01 · 108
In total:
Ni(OH)2 + 6 NH3 [Ni(NH3)6]+ + 2 OH– K = KL · KB = 1.6 · 10–8
To form c([Ni(NH3)6]+2) = 0.1 mol/L you need 0.1 mol Ni(OH)2 to dissolve
 c(OH–) = 0.2 mol/L
( )
= 1.6·10-8  = 1.6·10-8  c(NH3) = 7.9 mol/L
88
g) The acidic reaction and the possibility of sublimation point to a salt of a hydrated metal ion as
iron(III) chloride or aluminum(III) chloride. Both of them sublimate as water-free compounds
as dimers and cannot be dehydrated undecomposed.
T
[Me(H2O)6]A3 Me(OH)3 + 3 HA + 3 H2O
T
2 Me(OH)3 Me2O3 + 3 H2O
Total:
T
2 [Me(H2O)6]A3 Me2O3 + 6 HA + 9 H2O
0.830 g 0.376 g 0.280 g
0.280 g H2O 0.0155 mol
0.0155 mol · 6/9 = 0.0103 mol 0.376 g HA
 M(HA) = = 36.50 g · mol–1  M(A) = 35.5  A = Cl
0.830 g 0.0155 mol · 2/9 = 0.00344 mol
M([Me(H2O)6]Cl3 = = 241.28 g · mol–1
 M(Me) = 26.93 g/mol  Me = Al Formula of the salt: [Al(H2O)6]Cl3
a) For a reaction of first order ln(p(SO2Cl2)/p0) = f(t) is a linear function.

At first p(SO2Cl2) (x) has to be determined:
SO2Cl2(g)  SO2(g) + Cl2(g)
p0 – x x x ptotal = p0 + x with p0 = 0.5 atm
Timet in s 0 2500 5000 7500 10000

x in atm 0 0.027 0.053 0.076 0.099
p(SO2Cl2) in atm 0.500 0.473 0.447 0.424 0.401
ln(p(SO2Cl2)/p0) 0 -0.555 -0.112 -0.165 -0.221
0.00
-0.05
The plot is linear:
ln(p(SO2Cl2)/p0) = - k · t
-0.10
 k=-
ln(p/p0)
-0.15
k= = 2.21·10-5 s-1
-0.20
-0.25
0 2500 5000 7500 10000
t in s
b) 112 °C = 385 K ptotal = 0.78 atm  x = 0.28 atm p(SO2Cl2) = 0.22 atm
k=- =- k = 2.28·10-4 s-1
89
k=A·  ln = Ea = 280 kJ/mol
c) G = H - T·S
G = (-296.8 + 354.8) kJ - 400 K·(248.2 + 223.1 - 311.1) J/(K·mol)
G = [58.0 - 0.4·160.2] kJ/mol = -6.08 kJ/mol
lnKp = - G/(R·T) lnKp = 6080/(8.314·400) = 1.83 Kp = 6.23
d) H = [-10.2 - 309.1 + 369.2 + 400 K·10-3·(34.2 + 41.4 – 48.2)] kJ/mol = 60.86 kJ/mol
S = [28.3 + 12.34 - 36.5 + ln400·(34.2 + 41.4 - 48.2)] J/(K·mol)
S = 168.3 J/(K·mol)
G = [ 60.86 - 0.4·168.3] kJ/mol = -6.46 kJ/mol
lnKp = 6460/(8.314·400) = 1.943 Kp = 6.98 The assumption is justified.
e) v= = k4 · [I2] · [I-]
= k3 · [I+] · [I-] – k4 · [I2] · [I-] = 0  k4 · [I2] · [I-] = k3 · [I+] · [I-]
= k2 · [IS2O83-] - k3 · [I+] · [I-] = 0  k4 · [I2] · [I-] = k2 · [IS2O83-]
= k1 · [I-] [S2O82-] - k2 · [IS2O83-]  k4 · [I2] · [I-] = k1 · [I-] [S2O82-]
Thus the mechanism is consistent with the rate law.
a) Let co be the initial concentration of the acid HA in water.
= 5.4 5.4·c(HAw)= c(HAe) (1)
and because the total amount of acid is constant

Ve∙c(HAe)+ Vw∙c(HAw)= Vw∙c0 ,  0.5 L ∙c(HAe) + 1 L ∙c(HAw)= 1 L ∙c0 ,
 c(HA)e = 2∙c0 - 2∙c(HA)w (2)
(1) and (2)  c(HAw)= = 0.27∙c0 ,
27 % of the acid stay in the aqueous phase, 73 % are extracted.

The given law is only valid for the species HA, not for particles like A - and others. The condi-
tion for a correct result in part a) is that the acid in the aqueous phase (and in ether, too) ex-
ists completely as HA molecules. This can be achieved be decreasing the pH value in the
aqueous phase with hydrochloric acid.
b) The volume of one portion of ether is 0.5 L/n.
1. Extraction: 0.5/n ∙c1(HAe) + c1(HAw) = c0
c1(HAe) = 2n·c0 – 2n·c1(HAw)
inserted in (1): c1(HAw) · 5,4 = 2n·c0 – 2n·c1(HAw)
 c1(HAw)= · c0 (3)
In the second extraction the initial concentration of the aqueous phase is c1(HAw)
2
 c2(HAw)= · · c0 = ( ) · c0
90
n
After n extractions the concentration in the aqueous phase is cn(HAw) = ( ) · c0
After the last extraction cn(HAw) has to be smaller than 0.110: cn(HAw) ≤ 0.110· c0
n 1 2 3 4 5 6
cn(HAw) /c0 0.27 0.18 0.146 0.127 0.115 0.108
n=6
c) c(HAe) = 0.0432 mol/50 mL c(HAe) = 0.864 mol/L

4.3·c(HAw)= c(HAe)  c(HAw) = 0.201 mol/L
( )
KS =  10-2.89 =  c(A-) = 0.259 mol/L
c0(HA) = 10 · [n(HA) in 50 mL of ether + n(HA) in 100 mL of water + n(A-) in 100 mL of water)]/L
c0(HA) = 10 · [0.0432 + 0.0201 + 0.0259] mol/L = 0.892 mol/L
d) With the results of c) you get D= D = 1.88
e) Equation (1)  D= with c(HAe) = KD ∙ c(HAw)
( )
and KS =  c(A-) =
( )
 D= or D = KD ·
a) High- and low-spin complexes are possible between four and seven electrons in the d orbital.
Only in these cases different fillings of the molecular orbitals are possible.
b)
Fe3+ Octahedral field Tetrahedral field
high-spin
magnetic property paramagnetic paramagnetic
low-spin
Co3+ Octahedral field Tetrahedral field
high-spin
low-spin
magnetic property diamagnetic paramagnetic
91
Mn3+ Octahedral field Tetrahedral field
high-spin
low-spin
magnetic property paramagnetic diamagnetic
c)
Number of unpaired electrons n 1 2 3 4 5
Magnetic moment theo (in BM) 1,73 2,83 3,87 4,90 5,92
d) Plot of = ·T

T in K 2 10 20 30 60 90 120 220 270 300

-3
1/ in cm ·mol 0,55 2,26 4,24 6,58 13,16 19,61 26,32 47,62 58,82 66,67
70
60
1/in cm-3 mol
50
40
30
20
10
0
0 50 100 150 200 250 300
Temperature in K
Slope 1/C = 0.22 cm-3·mol  C = 4.55 cm3·K·mol–1
e) exp = 2.83·√ BM exp = 6.04 BM
f) It has to be a high-spin complex with five unpaired electrons because exp and theo are in good
agreement.
Remark:
The spin-only formula is not expected to give precise agreement with experimental data.

a) -decay:   + –
-decay:  +
92
b) m0 = mass tx years ago

99.275 = m0(238U)· 0.720 = m0(235U) ·
m0(238U) = 99.275 · m0(235U) = 0.720 ·
 ½ · 99.275 · = 0.720 · with k = ln2 / t1/2
 tx = ln /( - ) tx = 5.102·109 a
c) The mass numbers only change by -decay, namely by 4 units.

 

238
U  234
Th  234
Pa  234
U
234 238 234
d) The formation rate of U from U is the same as the decay rate of U. The rate law is that
of a reaction of first order: - = k·n.
 n234·k234 = n238·k238
n234 · = n238 ·
t1/2(234U) = t1/2(238U) ·
t1/2(234U) = 4.468·109 a · t1/2(234U) = 2.25·105 a
e) U (0) U3+ (+III) U4+ (+IV) UO2+ (+V) UO22+ (+VI)

f) The given conditions are standard conditions thus the standard potentials can be used to de-
termine the spontaneous reaction. The standard reduction potentials are the potentials in
comparison to a standard hydrogen half cell (2 H+ + 2 e  H2 Eo = 0,000 V).
The half cell with the positive potential represents the cathode where a spontaneous reduction
takes place.
E°cell = Eo(cathode) - Eo(anode), G = - n·F·E°
Thus the following reactions proceed:
1. Two reactions of uranium with the acid have to be taken into account:
2 U + 6 H+  2 U3+ + 3 H2 E0cell = + 1.798 V G < 0
+ 2+ 0
U + 2H + 2 H2O  UO2 + 3 H2 E cell = + 1.444 V G < 0
Irrespective which process is preferred neither U3+ nor UO2+ are final products.
2. U3+ oxidizes spontaneously to form U4+:

2 U3+ + 2 H+  2 U4+ + H2 E0 cell = +0.607 V G < 0
2+ + 4+
and UO2 is reduced spontaneously to form UO2 or U :
2+
2 UO2 + H2  2 UO2++ 2 H+ E0 cell l = +0.062 V G < 0 or
2+ + 4+ 0
UO2 + 2H + H2  U + 2 H2O E cell = +0.327 V G < 0
3. UO2+ in turn is reduced to U4+:

2 UO2+ + 6 H+ + H2  2 U4+ + 4 H2O E0 cell = +0.620 V G < 0
4+ +
U is the only species which cannot react spontaneously with H or H2, thus it will be the pre-
dominant specie under these conditions.
E°cell = E°(2 H+/H2) – E°(U4+/U) = 0 V – x V

U4+ U3+ U 4x = -0.607 + 3·(-1.798)
-0.607 -1.798
x = -1.500  E°cell = 1.500 V
x
93
a) Functional groups
А - Phenolic hydroxyl group D – Amide group

В – Methoxy group Е – Double bond
С –Polysubstituted benzene F – Hydrocarbon chain
Remark: The hydrocarbon chain is often neglected as a functional group though it is of great
importance for the hydrophobic properties of natural compounds.
b) (E)-Isomer
c) =  x  1.38·105 ppm
1 ppm corresponds to 1g/g = 10–6 g / g

The species Carolina Reaper contains 1,38∙105 μg Capsaicin /g.
d)
Vanillylamine
4-(Aminomethyl)-2-methoxyphenol
(Names not requested)
e)
f)
Cis-trans isomers
94
g)
h)
i)
j) Reasons why the reaction of 1 and 5 does not lead directly to capsaicin:
 5 reacts as an acid and protonates the amino group and in so doing decreases its nucleo-
philic character.
 The hydroxyl group is a poor leaving group and has to be converted in a better one (e.g.
chloride).
k) In the reaction of 1 and 6 an amide bond is formed.
The rotation is hindered by the resonance stabilization
which leads to a partial double bond:
a) b)
c) 2R, 3S
d) Only the Sharpless epoxidation has to be changed:
95
Sharpless
Epoxidation
Remark: If the reduction of the alkyne is changed a diastereomer to 4 is synthesized:

Sharpless
Epoxidation
The opening at position 3 uses the existing stereogenic centers and has no influence on the
desired change.
e)
f) The aldol reaction introduces the two new stereogenic centers independent of the other stere-
ogenic centers in the molecule. Thus a diastereomer to product 7 is formed.

a)
b) The first reaction (with NBS in CH3Cl at -60 °C) favors the electrophilic substitution at the ar-
omatic ring. Often these electrophilic substitutions are carried out with Br2 and FeBr3 as cata-
lyst. In this case a catalyst was not necessary.
96
The second reaction (with NBS, the radical initiator AIBN in CCl4 at 77 °C = boiling tempera-
ture of CCl4) favors the radical substitution at the side chain.
c)
d)
e) It is the thermodynamically more stable product (higher substituted double bond) which is
favored by the long reaction time und the raised temperature. The rearrangement takes place
only at the H2C= group at the left 6-membered ring. A comparable rearrangement at the H2C=
group at the bridge above the 8-membered ring would lead to an extreme ring tension.
f)
97
46th International Chemistry Olympiad
July 25, 2014
Hanoi, Vietnam
EXAMINATIONS
98
IChO Hanoi: Theoretical Test
Theoretical Test
Physical Constants, Units, Formulas and Equations
Avogadro's constant NA = 6.0221  1023 mol–1
Universal gas constant R = 8.3145 J∙K–1∙mol–1
Speed of light c = 2.9979  108 m∙s–1
Planck's constant h= 6.6261  10–34 J∙s
Standard pressure p = 1 bar = 105 Pa
Atmospheric pressure 1 atm = 1.01325  105 Pa = 760 mmHg
Zero of the Celsius scale 273.15 K
Mass of electron me = 9.1094  10–31 kg
1 nanometer (nm) = 10–9 m ; 1 angstrom (Å) = 10–10 m

1 electron volt (eV) = 1.6022  10–19 J = 96485 J∙mol–1
Energy of a light quantum with wave- E = hc / 

length 
Energy of one mole of photons Em = hcNA / 
Gibbs energy G = H – TS
 G 
Relation between equilibrium constant K = exp   
and standard Gibbs energy  RT 
 
K 2 H 0  1 1 
ln    
R  T1 T2 
van’t Hoff equation in integral form
K1
Relationship between internal energy, ∆U = q + w
heat and work
 dU 
Molar heat capacity at constant volume Cv ,m   
 dT  v
Change in internal energy from T1 to T2
assuming constant Cv,m U(T2)=U(T1)+nCv,m(T2–T1),
Spin only formula relating number of
unpaired electrons to effective magnet- eff  n(n  2) B.M.
ic moment
A periodical table was provided

99
Problem 1 Particles in a box: polyenes
In quantum mechanics, the movement of π electrons along a neutral chain of conjugated

carbon atoms may be modeled using the ‘particle in a box’ method. The energy of the π
electrons is given by the following equation:
n2h2
En 
8mL2
where n is the quantum number (n = 1, 2, 3, …), h is Planck’s constant, m is the mass of
electron, and L is the length of the box which may be approximated by L = (k + 2)×1.40
Å (k being the number of conjugated double bonds along the carbon chain in the mole-
cule). A photon with the appropriate wavelength  may promote a π electron from the
highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital
(LUMO). An approximate semi-empirical formula based on this model which relates the
wavelength , to the number of double bonds k and constant B is as follows:
(k  2) 2
λ (nm) = B  Equation 1
(2k  1)
1. Using this semi-empirical formula with B = 65.01 nm calculate the value of the
wavelength  (nm) for octatetraene (CH2 = CH – CH = CH – CH = CH – CH = CH2).
2. Derive Equation 1 (an expression for the wavelength  (nm) corresponding to the
transfer of an electron from the HOMO to the LUMO) in terms of k and the funda-
mental constants and hence calculate theoretical value of the constant B calc..
3. We wish to synthesize a linear polyene for which the excitation of a π electron from
the HOMO to the LUMO requires an absorption wavelength of close to 600 nm. Using
your expression from part 2, determine the number of conjugated double bonds (k)
in this polyene and give its structure. [If you did not solve Part 2, use the semi-
empirical Equation 1 with B = 65.01 nm to complete Part 3.]
4. For the polyene molecule found in Part 3, calculate the difference in energy between
the HOMO and the LUMO, ΔE, (kJ·mol–1).
In case Part 3 was not solved, take k = 5 to solve this problem.
The model for a particle in a one-dimensional box can be extended to a three

dimensional rectangular box of dimensions Lx, Ly, and Lz, yielding the following
expression for the allowed energy levels:
h 2  nx2 n y nz2 
2
En x , n y , n z   
8m  L2x L2y L2z 
The three quantum numbers nx, ny, and nz must be integer values and are independent
of each other.
5a. Give the expressions for the three different lowest energies, assuming that the box is
cubic with a length of L.
100
5b. Levels with the same energy are said to be degenerate. Draw a sketch showing all
the energy levels, including any degenerate levels that correspond to quantum num-
bers having values of 1 or 2 for a cubic box.
Problem 2 Dissociating Gas Cycle
Dinitrogen tetroxide forms an equilibrium mixture with nitrogen dioxide:
N2O4(g) 2NO2(g)
1.00 mole of N2O4 was put into an empty vessel with a fixed volume of 24.44 dm 3. The
equilibrium gas pressure at 298 K was found to be 1.190 bar. When heated to 348 K, the
gas pressure increased to its equilibrium value of 1.886 bar.
1a. Calculate ∆G0 of the reaction at 298K, assuming the gases are ideal.
1b. Calculate ∆H0 and ∆S0 of the reaction, assuming that they do not change significantly
with temperature.
If you cannot calculate ∆H0, use ∆H0 = 30.0 kJ·mol–1 for further calculations.
The tendency of N2O4 to dissociate reversibly into NO2 enables its potential use in ad-
vanced power generation systems. A simplified scheme for one such system is shown
below in Figure (a). Initially, "cool" N2O4 is compressed (1→2) in a compressor (X), and
heated (2→3). Some N2O4 dissociates into NO2. The hot mixture is expanded (3→4)
through a turbine (Y), resulting in a decrease in both temperature and pressure. The
mixture is then cooled further (4→1) in a heat sink (Z), to promote the reformation of
N2O4. This recombination reduces the pressure, thus facilitates the compression of N 2O4
to start a new cycle. All these processes are assumed to take place reversibly.
q in
(a)
1 X 2 3 Y 4
work out
1 Z 4
q out
To understand the benefits of using reversible dissociating gases such as N 2O4, we will
focus on step 3 → 4 and consider an ideal gas turbine working with 1 mol of air (which
we assume to be an inert, non-dissociating gas). During the reversible adiabatic expan-
sion in the turbine, no heat is exchanged.
2. Give the equation to calculate the work done by the system w(air) during the rever-
sible adiabatic expansion for 1 mol of air during stage 3 → 4. Assume that Cv,m(air)
101
(the isochoric molar heat capacity of air) is constant, and the temperature changes
from T3 to T4.
3. Estimate the ratio w(N2O4)/w(air), in which w(N2O4) is the work done by the gas during
the reversible adiabatic expansion process 3 → 4 with the cycle working with 1 mol
of N2O4. T3 and T4 are the same as in Part 2. Take the conditions at stage 3 to be T 3
= 440 K and P3 = 12.156 bar and assume that:
(i) The gas is at its equilibrium composition at stage 3;
(ii) Cv,m for the gas is the same as for air;
(iii) The adiabatic expansion in the turbine takes place in a way that the composi-
tion of the gas mixture (N2O4 + NO2) is unchanged until the expansion is
completed.
Problem 3 High-valent Silver Compounds

Silver chemistry is dominated by Ag (I) compounds. Compounds of silver in higher oxida-
tion state (from +2 to +5) are not very abundant due to their instability with respect to
reduction. High-valent silver compounds are very reactive and can be synthesized from
Ag(I) compounds in electro-chemical oxidations or in chemical oxidations using powerful
oxidizing agents.
In some peroxodisulphate (S2O82-) oxidations catalyzed by Ag+, black solid (A) with the
composition AgO can be isolated.
1a. Choose the appropriate magnetic behavior of A if it exists as AgIIO.
Single crystal X - ray studies reveal that the lattice of A contains two nonequivalent Ag
atom sites (in equal proportions) of which one denoted as Ag1 and the other denoted as
Ag2. Ag1 shows a linear O atom coordination (O-Ag-O) and Ag2 shows a square-planar O
atom coordination. All O atoms are in equivalent environments in the structure. Thus, A
should be assigned as AgIAgIIIO2 rather than AgIIO.
1b. Assign the oxidation number of Ag1 and Ag2.

1c. What is the coordination number of O atoms in the lattice of A?
1d. How many AgI and AgIII bond to one O atom in the lattice of A?
1e. Predict the magnetic behavior of A. Check the appropriate box below.
1f. The compound A can also be formed on warming a solution of Ag+ with peroxodisul-
phate. Write down the equation for the formation of A.
102
Among the silver oxides which have been crystallographically characterized, the most
surprising is probably that compound A is not a Ag IIO. Thermochemical cycles are useful
to understand this fact. Some standard enthalpy changes (at 298 K) are listed:
Standard enthalpy st 1st electron 2nd electron

1 ionization 2nd ionization 3rd ionization
Atom of formation affinity affinity
(kJ·mol–1) (kJ·mol–1) (kJ·mol–1)
(kJ·mol–1) (kJ·mol–1) (kJ·mol–1)
Cu(g) 337.4 751.7 1964.1 3560.2
Ag(g) 284.9 737.2 2080.2 3367.2
O(g) 249.0 -141.0 844.0
Compounds ΔHof (kJ·mol–1)

I III
Ag Ag O2 (s) –24.3
CuIIO (s) –157.3
The relationship between the lattice dissociation energy (Ulat) and the lattice dissociation
enthalpy (ΔHlat) for monoatomic ion lattices is H lat  U lat  nRT , where n is the number
of ions in the formula unit.
2a. Calculate Ulat at 298 K of AgIAgIIIO2 and CuIIO. Assume that they are ionic com-
pounds.
If you cannot calculate the Ulat of AgIAgIIIO2 and CuIIO, use following values for further
calculations: Ulat of AgIAgIIIO2 = 8310.0 kJ·mol–1; Ulat of CuIIO = 3600.0 kJ·mol–1.
The lattice dissociation energies for a range of compounds may be estimated using this
simple formula:
1
 1  3
U lat  C   
 Vm 
Where: Vm (nm3) is the volume of the formula unit and C (kJ·nm·mol–1) is an empirical
constant which has a particular value for each type of lattice with ions of specified
charges.
The formula unit volumes of some oxides are calculated from crystallographic data as the
ratio between the unit cell volume and the number of formula units in the unit cell and
listed as below:
Oxides Vm (nm3)
CuIIO 0.02030
AgIII2O3 0.06182
II III
Ag Ag 2O4 0.08985
2b. Calculate Ulat for the hypothetical compound AgIIO. Assume that AgIIO and CuIIO
have the same type of lattice, and that Vm (AgIIO) = Vm (AgIIAgIII2O4) – Vm (AgIII2O3).
2c. By constructing an appropriate thermodynamic cycle or otherwise, estimate the en-

thalpy change for the solid-state transformation from AgIIO to 1 mole of AgIAgIIIO2.
103
(Use Ulat AgIIO = 3180.0 kJ·mol-1 and Ulat AgIAgIIIO2 = 8310.0 kJ·mol-1 if you cannot
calculate Ulat AgIIO in Part 2b).
2d. Indicate which compound is thermodynamically more stable by checking the appro-
priate box on the answer sheet.
When AgIAgIIIO2 is dissolved in aqueous HClO4 solution, a paramagnetic compound (B) is

first formed then slowly decomposes to form a diamagnetic compound (C).
3. Given that B and C are the only compounds containing silver formed in these reac-
tions, write down the equations for the formation of B and C.
Oxidation of Ag+ with powerful oxidizing agents in the presence of appropriate ligands
can result in the formation of high-valent silver complexes. A complex Z is synthesized
and analyzed by the following procedures:
An aqueous solution containing 0.500 g of AgNO3 and 2 mL of pyridine (d = 0.982 g/mL)
is added to a stirred, ice-cold aqueous solution of 5.000 g of K2S2O8. The reaction mix-
ture becomes yellow, then an orange solid (Z) is formed which has a mass of 1.719 g
when dried.
Elemental analysis of Z shows the mass percentages of C, H, N elements are 38.96%,
3.28%, 9.09%, respectively.
A 0.6164 g Z is added to aqueous NH3. The suspension is boiled to form a clear solution
during which stage the complex is destroyed completely. The solution is acidified with
excess aqueous HCl and the resulting suspension is filtered, washed and dried (in dark-
ness) to obtain 0.1433 g of white solid (D). The filtrate is collected and treated with ex-
cess BaCl2 solution to obtain 0.4668 g (when dry) of white precipitate (E).
4a. Determine the empirical formula of Z and calculate the percentage yield in the prepa-
ration.
4b. Ag (IV) and Ag (V) compounds are extremely unstable and found only in few fluo-
rides. Thus, the formation of their complexes with organic ligands in water can be
discounted. To confirm the oxidation number of silver in Z, the effective magnetic
moment (µeff) of Z was determined and found to be 1.78 BM. Use the spin only for-
mula to determine the number of unpaired electrons in Z and the molecular formula
of Z. (Z contains a mononuclear complex with only one species of Ag and only one
type of ligand in the ligand sphere.)
4c. Write down all chemical equations for the preparation of Z, and its analysis.
(Formation of Z, Destruction of Z with NH3, Formation of D, Formation of E)
Problem 4. Zeise’s Salt

Zeise's salt, K[PtCl3C2H4], was one of the first organometallic compounds to be reported.
W. C. Zeise, a professor at the University of Copenhagen, prepared this compound in
104
1827 by reacting PtCl4 with boiling ethanol and then adding potassium chloride (Method
1). This compound may also be prepared by refluxing a mixture of K 2[PtCl6] and ethanol
(Method 2). The commercially available Zeise's salt is commonly prepared from K 2[PtCl4]
and ethylene (Method 3).
1a. Write balanced equations for each of the above mentioned preparations of Zeise's
salt, given that in methods 1 and 2 the formation of 1 mole of Zeise’s salt consumes
2 moles of ethanol.
Mass spectrometry of the anion [PtCl 3C2H4]– shows one set of peaks with mass numbers
325-337 and various intensities.
1b. Calculate the mass number of the anion which consists of the largest natural abun-
dance isotopes (using given below data).
Isotope
Natural abundance in % 0.8 32.9 33.8 25.3 7.2 75.8 24.2 98.9 1.1 99.99
Some early structures proposed for Zeise’s salt anion were:
In structure Z1, Z2, and Z5 both carbons are in the same plane as dashed square. (You
should assume that these structures do not undergo any fluxional process by interchang-
ing two or more sites.)
2. NMR spectroscopy allowed the structure for Zeise’s salt to be determined as struc-
ture Z4. For each structure Z1-Z5, indicate in the table below how many different
environments of hydrogen atoms there are, and how many different environments of
carbon atoms there are.
For substitution reactions of square platinum(II) complexes, ligands may be arranged in

order of their tendency to facilitate substitution in the position trans to themselves (the
trans effect). The ordering of ligands is:
CO, CN-, C2H4 > PR3, H- > CH3-, C6H5-, I-, SCN- > Br- > Cl- > Py > NH3 > OH-, H2O
In the series above a left ligand has stronger trans effect than a right ligand.
Some reactions of Zeise’s salt and the complex [Pt2Cl4(C2H4)2] are given below.
105
3a. Draw the structure of A, given that the molecule of this complex has a center of
symmetry, no Pt-Pt bond, and no bridging alkene.
3b. Draw the structures of B, C, D, E, F and G.
3c. Suggest the driving force(s) for the formation of D and F by choosing one or more of
the following statements (for example, i and ii):
i) Formation of gas ii) Formation of liquid
iii) Trans effect iv) Chelate effect
Problem 5. Acid-base Equilibria in Water

A solution (X) contains two weak monoprotic acids (those having one acidic proton); HA
with the acid dissociation constant of KHA = 1.74 × 10–7, and HB with the acid dissocia-
tion constant of KHB = 1.34 × 10–7. The solution X has a pH of 3.75.
Titration of 100 mL solution X requires 100 mL of NaOH solution (0.220 mol/L) for com-
pletion.
1. Calculate the initial (total) concentration (mol·L –1) of each acid in the solution X.
Use reasonable approximations where appropriate. [K W = 1.00 × 10–14 at 298 K.]
2. Calculate the pH of the solution Y which initially contains 6.00×10 -2 mol/L of NaA and
4.00×10-2 mol/L of NaB.
Adding large amounts of distilled water to solution X gives a very (infinitely) dilute solu-
tion where the total concentrations of the acids are close to zero.
3. Calculate the percentage of dissociation of each acid in this dilute solution.
A buffer solution is added to solution Y to maintain a pH of 10.0. Assume no change in

volume of the resulting solution Z.
4. Calculate the solubility (in mol·L–1) of a substance M(OH)2 in Z, given that the anions
A– and B– can form complexes with M2+:
M(OH)2 M2+ + 2OH– Ksp = 3.10 ×10-12
M2+ + A– [MA]+ K1 = 2.1 × 103
[MA]+ + A– [MA2] K2 = 5.0 × 102
106
M2+ + B– [MB]+ K’1 = 6.2 × 103

[MB]+ + B– [MB2] K’2 = 3.3 × 102
Problem 6. Chemical Kinetics

The transition-metal-catalyzed amination of aryl halides has become one of the most
powerful methods to synthesize arylamines. The overall reaction for the nickel-catalyzed
amination of aryl chloride in basic conditions is:
in which NiLL’ is the nickel complex catalyst. The reaction goes through several steps in
which the catalyst, reactants, and solvent may be involved in elementary steps.
To determine the reaction order with respect to each reactant, the dependence of the
initial rate of the reaction on the concentrations of each reagent was carried out with all
other reagents present in large excess. Some kinetic data at 298 K are shown in the ta-
bles below. (Use the given grids on the answer sheet if you like)
[ArCl] (mol·L-1) 0.1 0.2 0.4 0.6
Initial rate (mol·L-1·s–1) 1.88 × 10-5 4.13×10-5 9.42 × 10-5 1.50 × 10-4
[NiLL’] (mol·L-1) 6 × 10–3 9 × 10–3 1.2 × 10–2 1.5 × 10–2

Initial rate (mol·L-1·s–1) 4.12 × 10–5 6.01 × 10–5 7.80 × 10–5 1.10 × 10–4
[L’] (mol·L-1) 0.06 0.09 0.12 0.15

-1 –1
Initial rate (mol·L ·s ) 5.8 × 10–5 4.3 × 10–5 3.4 × 10–5 2.8 × 10–5
6a. Determine the order with respect to the reagents assuming they are integers.
To study the mechanism for this reaction, 1H, 31

P, 19
F, and 13
C NMR spectroscopy have
been used to identify the major transition metal complexes in solution, and the initial
rates were measured using reaction calorimetry. An intermediate, NiL(Ar)Cl, may be iso-
lated at room temperature. The first two steps of the overall reaction involve the dissoci-
ation of a ligand from NiLL’ (step 1) at 50 oC, followed by the oxidation addition (step 2)
of aryl chloride to the NiL at room temperature (rt):
6b. Using the steady state approximation, derive an expression for the rate equation for
the formation of [NiL(Ar)Cl].
The next steps in the overall reaction involve the amine (RNH2) and tBuONa. To deter-
mine the order with respect to RNH2 and tBuONa, the dependence of the initial rates of
107
the reaction on the concentrations of these two reagents was carried with the other rea-
gents present in large excess. Some results are shown in the tables below.
[NaOtBu] (mol·L-1) 0.2 0.6 0.9 1.2

-1 –1 –5 –5 –5
Initial rate (mol·L ·s ) 4.16 × 10 4.12 × 10 4.24 × 10 4.2 × 10–5
[RNH2] (mol·L-1) 0.3 0.6 0.9 1.2

-1 –1 –5 –5 –5
Initial rate (mol·L ·s ) 4.12 × 10 4.26 × 10 4.21 × 10 4.23 × 10–5
6c. Determine the order with respect to each of these reagents, assuming each is an
integer. (Use the grids if you like.)
During a catalytic cycle, a number of different structures may be involved which include
the catalyst. One step in the cycle will be rate-determining.
A proposed cycle for the nickel-catalyzed coupling of aryl halides with amines is as fol-
ows:
6d. Use the steady-state approximation and material balance equation to derive the rate
law for d[ArNHR]/dt for the above mechanism in terms of the initial concentration of
the catalyst [NiLL’]0 and concentrations of [ArCl], [NH2R], [NaOtBu], and [L’].
6e. Give the simplified form of the rate equation in 6d assuming that k 1 is very small.
d[ArNHR]/dt = - d[ArCl]/dt = ...
Problem 7. Synthesis of Artemisinin

(+)-Artemisinin, isolated from Artemisia annua L.
(Qinghao, Compositae) is a potent antimalarial effective
against resistant strains of Plasmodium. A simple route
for the synthesis of Artemisinin is outlined below.
First, pyrolysis of (+)-2-Carene broke the cyclopropane ring forming, among other pro-
ducts, (1R)-(+)-trans-isolimonene A (C10H16), which then was subjected to regioselective
hydroboration using dicyclohexylborane to give the required alcohol B in 82% yield as a
108
mixture of diastereomers. In the next step, B was converted to the corresponding γ,δ-
unsaturated acid C in 80% yield by Jones’ oxidation.
7a. Draw the structures (with stereochemistry) of the compounds A-C.
The acid C was subjected to iodolactonization using KI, I 2 in aqueous. NaHCO3 solution to
afford diastereomeric iodolactones D and E (which differ in stereochemistry only at C 3 ) in
70% yield.
7b. Draw the structures (with stereochemistry) of the compounds D and E.
The iodolactone D was subjected to an intermolecular radical reaction with ketone X us-
ing tris(trimethylsilyl)silane (TTMSS) and AIBN (azobisisobutyronitrile) in a catalytic
amount, refluxing in toluene to yield the corresponding alkylated lactone F in 72% yield
as a mixture of diastereomers which differ only in stereochemistry at C7 along with com-
pound G (~10%) and the reduced product H, C10H16O2 (<5%).
7c. Draw the structures (with stereochemistry) of compound H and the reagent X.
The keto group of F reacted with ethanedithiol and BF3•Et2O in dichloromethane (DCM) at
0 oC to afford two diastereomers: thioketal lactones I and J in nearly quantitative yield
(98%). The thioketalization facilitated the separation of the major isomer J in which the
thioketal group is on the opposite face of the ring to the adjacent methyl group.
7d. Draw the structures (with stereochemistry) of the compounds I and J.
109
The isomer J was further subjected to alkaline hydrolysis followed by esterification with
diazomethane providing hydroxy methyl ester K in 50% yield. The hydroxy methyl ester
K was transformed into the keto ester L using PCC (Pyridium Chloro Chromate) as the
oxidizing agent in dichloromethane (DCM).
A two-dimensional NMR study of the compound L revealed that the two protons adjacent
to the newly-formed carbonyl group are cis to each other and confirmed the structure of
L.
7e. Draw the structures (with stereochemistry) of the compounds K and L.
The ketone L was subjected to a Wittig reaction with methoxymethyl triphenylphos-

phonium chloride and KHMDS (Potassium HexaMethylDiSilazid - a strong, non-nucleo-
philic base) to furnish the required methyl vinyl ether M in 45% yield. Deprotection of
thioketal using HgCl2, CaCO3 resulted in the key intermediate N (80%). Finally, the com-
pound N was transformed into the target molecule Artemisinin by photo-oxidation fol-
lowed by acid hydrolysis with 70% HClO4.
Ph3P(Cl)CH2OCH3 HgCl2, CaCO3 1. O2, h

L M N Artemisinin
KHMDS 2. HClO4
7f. Draw the structures (with stereochemistry) of the compounds M and N.
Problem 8. Star Anise

Illicium verum, commonly called Star anise, is a small native evergreen tree grown in
northeast Vietnam. Star anise fruit is used in traditional Vietnamese medicine. It is also a
major ingredient in the making the flavor of ‘phở’, a Vietnamese favorite soup.
Acid A is isolated from the star anise fruit. The constitutional formula of A has been de-
duced from the following sequence of reactions:
110
(I): this overall process results in alkene cleavage at the C=C bond, with each carbon of
this becoming doubly bonded to an oxygen atom.
(II): this oxidative cleavage process of 1,2-diols breaks C(OH)–C(OH) bond and produc-
es corresponding carbonyl compounds.
8a. Draw the structures for the compounds Y 1 and Y2 and hence deduce the structure of
Y3 and A, B, C, D, given that in A there is only one ethylenic hydrogen atom.
Anethole, a main component of star anise oil, is an inex-

pensive chemical precursor for the production of many
pharmaceutical drugs.
Treating anethole with sodium nitrite in acetic acid gives a crystalline solid E
(C10H10N2O3). The IR spectrum of E shows there is no non-aromatic C=C double bond.
The 1H NMR spectrum of E is given below.
3H 3H
2H 2H
8b. What differences in the structure between E and anethole can be obtained from the
1
H NMR data? Pick one ore more of the statements below
i) E contains a cis-C=C ethylenic bond while that of anethole is trans.
ii) E cannot contain a non-aromatic C=C bond.
iii) E is the adduct of anethole and N2O2.
iv) E is the adduct of anethole and N2O3.
111
v) E does not contain two trans ethylenic protons as anethole.
On heating at 150 oC for several hours, E is partially isomerized into F. Under the same
conditions, F gives the identical equilibrium mixture to that obtained from E. On heating
with phosphorus trichloride, both E and F lose one oxygen atom giving compound G.
Compounds E and F have the same functional groups.
The chemical shifts of methyl protons in E, F and G are given below.

E F G
CH3-O 3.8 ppm 3.8 ppm 3.8 ppm
CH3-C 2.3 ppm 2.6 ppm 2.6 ppm
8c. Suggest structures for E, F and G, assuming that they do NOT contain three-
membered rings.
A simplified structure for compound E is shown below; the R group does not change
throughout the rest of this question. Compound E is nitrated and subsequently reduced
with sodium dithionite to H. Treatment of H with sodium nitrite and hydrochloric acid at
0–5 oC and subsequently reduced with stannous chloride to provide I (R–C7H9N2O). One-
pot reaction (three component reaction) of H, benzaldehyde and thioglycolic acid
(HSCH2CO2H) leads to the formation of J. Reaction of I and methyl phenyl ketone in the
presence of ZnCl2 affords K.
8d. Give the structures for H, I, J and K.
112
Problem 9. Heterocycle Preparation

Tetramethylthiurame disulfide (TMTD) is emerging as a useful reagent to prepare many
sulfur-nitrogen functional groups and heterocycles in organic chemistry. The reactions of
TMTD with primary amines, as well some corresponding post-transformations of the re-
sulting product(s) are presented in the following schemes:
(1)
(2)
(3)
(4)
(5)
Similar transformations of benzohydrazides (containing nucleophilic NH 2 group) and

TMTD have been observed.
In the synthetic scheme below, the thiocarbamoylation reaction of an aryl hydrazine with
TMTD produces compound C containing a heterocyclic moiety from p-aminobenzoic acid.
During the formation of C from B, an intermediate B' was observed. This intermediate
tautomerizes to B''. C can be formed from B' or B''.
113
9a. Give the structures of A, B, and C.
9b. Suggest a structure for the tautomer B’’ and give a curly-arrow mechanism for the
formation of C.
Compound C was then converted to F by the following pathway:
[The group R remains exactly the same throughout the rest of the question.]
9c. Draw the structures of E, and F. (You do not need to draw the structure for the
R group from this point.)
E was only obtained when D was slowly added to the solution of excess N 2H4 in dioxane.
If N2H4 was added to the solution of D in dioxane instead, a major side product D’
(R2C14H12N4S2) was formed.
9d. Give the structure of D’.
Slightly heating D with ethanolamine (HOCH2CH2NH2) in dioxane for 2 hours yielded G

(R–C9H11N2OS).
9e. Draw the structural formula of G.
9f. Heating G in the presence of p-toluenesulfonic acid as the catalyst could form a
number of different five-membered heterocyclic products.
i) Draw 2 structures that have different molecular formulae.
ii) Draw 2 structures that are constitutional isomers.
iii) Draw 2 structures that are stereoisomers.
114
IChO Hanoi: Practical Test
Practical Test
23. July 2014
List of chemicals
The concentration indicated on the label is approximate. The exact values are
indicated in the table.
Chemical/Reagent Quantity Placed in Labeled Safety

Practical Problem 1
0.100 M KI solution 120 mL Glass bottle 0.1 M KI H320
Solution #A1 contains KI,
H314, H302,
Na2S2O3, and starch indicator in 40 mL Glass bottle Solution #A1
H315, H319
distilled water
Solution #B1 contains Fe(NO3)3, H314, H315,
40 mL Glass bottle Solution #B1
HNO3 in distilled water H319, H335
Solution #A2-1 contains 5.883
10–4 M Na2S2O3, KNO3, and 360 mL Glass bottle Solution #A2-1 H314 H272
starch indicator in distilled water
Solution #B2 contains 0.1020 M
H314, H272,
Fe(NO3)3 and HNO3 in distilled 100 mL Glass bottle Solution #B2
H315, H319
water.
H2O (Practical Prob-
Distilled water 1L Glass bottle
lem 1)
Practical Problem 2
Artemisinin 1.000 g Small bottle Artemisinin
Sodium borohydride, NaBH4 0.53 g Small bottle NaBH4 H301-H311
CH3OH 20 mL Glass bottle Methanol H225, H301
n-Hexane 30 mL Bottle n-Hexane H225
cerium staining reagent for TLC 3-5 mL Bottle Ceri reagent
CH3COOH 1 mL 1.5 mL vial Acetic Acid H226, H314
Ethyl acetate 5 mL Glass bottle Ethyl acetate
Bag of NaCl for salt bath 0.5 kg Ice bath NaCl bag
CaCl2 in drying tube 5-10 g Tube CaCl2 H319
Practical Problem 3
~ 30 wt.% H2SO4, solution in
40 mL Bottle ~30 wt.% H2SO4 H314
water
1.0010–2M KMnO4, aqueous
50 mL Bottle ~0.01 M KMnO4, H272, H302,
solution
2.0010-3M EDTA, aqueous solu-
40 mL Bottle 2.0010-3 M EDTA H319
tion
pH = 9-10 Buffer aqueous Solu- pH = 9-10 Buffer
40 mL Bottle H302 , H319
tion, NH4Cl + NH3 Solution
~20 wt.% NaOH, aqueous solu-
20 mL Plastic bottle ~20 wt.% NaOH, H314
tion
~3 M H3PO4, solution in water 15 mL Bottle ~3 M H3PO4 H314
Indicator: ETOO, solid in KCl ca. 0.5 g Plastic bottle ETOO H301
115
List of Glassware and Equipment
Problem Item on every working place Quantity

Hotplate stirrer 1
Magnetic stirring bar (seek in Kit #1) 1
Plastic wash bottle filled with distilled water (refill if necessary from
1
the 1 L glass bottle of distilled water provided)
1-L glass beaker for inorganic waste liquid 1
250-mL conical flask for organic waste liquid 1
1
Pipette rack with:
1
1-mL graduated pipette
5-mL graduated pipette (One for Problem 1; another labeled 2
Practical Problems 1-3
‘MeOH’ for Problem 2)

10-mL graduated pipette 1
10-mL volumetric pipette 1
25-mL graduated pipette 1
Pasteur pipette and bulb 2
Glass spatula spoon 2
Cleaning brush 1
Large glass stirring rod
1
Glass funnel
1
Bag of paper towels 1
Goggles 1
Digital thermometer 1
Three-way pipette bulb with a little rubber adapter for bigger pipettes 1
Ceramic Büchner funnel with fitted rubber bung 1
Büchner flask 1
Pair of rubber gloves 1
One cotton glove 1
Practical Problem 1 (KIT # 1)
Digital stop watch 1
KIT
#1
Insulating plate for the hotplate stirrer labeled I.P. 1

100-mL glass beaker 6
5-mL graduated measuring cylinder 1
50-mL graduated measuring cylinder 2
100-mL two-neck round bottom flask with plastic stopper (in ice bath) 1
100-mL conical (Erlenmeyer) flask 1
Hair dryer 1
Petri dish with cover containing 1 TLC plate, 2 capillaries in paper
1
holder
KIT # 2
Plastic pot for ice bath 1

Stand & clamp 1
TLC developing chamber with glass lid 1
Tweezers 2
Metal spatula 1
Very small test tubes for TLC in container 2
Zipper store bag (containing cotton wool, round filter paper, watch
1
glass for Problem 2 labeled with WHITE student code)
Empty Petri dish with cover 1
116

50-mL glass beaker (for transferring EDTA and KMnO4 solutions to
burettes)
2
25-mL burette with BLUE graduation marks 1
25-mL burette with BROWN graduation marks 1
250 mL glass beaker 2
KIT # 3
250 mL conical flask (Erlenmeyer flask) 2

100 mL volumetric flask with stopper 2
10 mL glass graduated measuring cylinder 1
100 mL glass graduated measuring cylinder 1
Burette stand & clamp 1
Reel of pH paper 1
Zipper store bag (containing a large round filter paper for the glass
funnel)
1
Items on the tables for the common use:
Electronic balance with 0.1-mg resolution (6-8 students/each)
Attention: You MUST do the experiments in the order

Problem 1, 2 and then 3
(this is in order to control
the temperature of the magnetic stirrer properly).
117
Practical Problem 1. The oxidation of iodide by iron(III) ions – a kinetic

study based on the thiosulfate clock reaction
Clock reactions are commonly used as demonstrations by chemical educators owing to

their visual appeal. Oxidation of iodide by iron(III) ions in a weakly acidic medium is a
reaction that can be transformed into a clock reaction. In the presence of thiosulfate and
starch, chemical changes in this clock reaction can be presented by the following equa-
tions:
Reaction (1) is a fast reversible equilibrium which occurs in the reaction mixture giving a
reservoir of iron(III) and thiosulfate ions. After being produced in reaction (2), iodine in
the form of triiodide ion (I3–), is immediately consumed by thiosulfate in reaction (3).
Therefore, no iodine accumulates in the presence of thiosulfate. When thiosulfate is total-
ly depleted, the triiodide ion accumulates and it may be detected by use of starch indica-
tor according to reaction (4).
The kinetics of reaction (2) is easily investigated using the initial rates method. One has
to measure the time elapsed between mixing the two solutions and the sudden color
change.
For the oxidation of iodide by iron(III) ions (reaction 2), the reaction rate can be defined
as:
d  Fe3+ 
v  (5)
dt
The initial reaction rate can then be approximated by:
  Fe3+ 
v0    (6)
t
with Δ[Fe3+] being the change in the concentration of iron(III) ions in the initial period of
the reaction. If Δt is the time measured, then Δ[Fe3+] is the change in iron(III) ion con-
centration from the moment of mixing to the moment of complete thiosulfate consump-
tion (assume that the reaction rate does not depend on thiosulfate concentration). There-
fore, from the reactions' stoichiometry it follows:
 Fe3+   S2O32  (7)

0
and consequently:
S2O32 
v0  0 (8)
t
118
The initial thiosulfate concentration is constant and significantly lower than that of
iron(III) and iodide ions. The above expression enables us to determine the initial reac-
tion rate by measuring the time required for the sudden color change to take place, Δt.
The rate of reaction is first order with respect to [Fe3+], and you will determine the order
with respect to [I–]. This means the initial reaction rate of reaction can be expressed as:
v0  k[Fe3 ]0[I ]0y (9)
where k is the rate constant and y is the order with respect to [I–].
We assume that the reaction rate does not depend on the thiosulfate concentration, and
that the reaction between Fe3+ and S2O32- is negligible. You have to observe carefully the
color changes during the clock reaction and to determine the reaction order with respect
to [I–], and the rate constant of clock reaction.
Experimental Set-up
Instructions for using the digital timer (stopwatch)

1. Press the [MODE] button until the 00:00:00 icon is displayed.
2. To begin timing, press the [START/STOP] button.
3. To stop timing, press the [START/STOP] button again.
4. To clear the display, press the [SPLIT/RESET] button.
PRECAUTIONS
 To minimize fluctuations in temperature only use the distilled water on your bench
(in the wash bottle and in the glass 1 L bottle).
 The heating function of the heating magnetic stirrer must be TURNED OFF (as
shown in Figure 1 below) and be sure that the stirrer plate is not hot before starting your
experiment. Put the insulating plate (labeled I.P.) on top of the stirrer plate for added
insulation.
 Start the stopwatch as soon as the solutions #A and #B are mixed. Stop the
stopwatch as soon as the solution suddenly turns dark blue.
 Magnetic stirrer bar (take it with the provided tweezers) and beakers should be
washed and rinsed with distilled water and wiped dry with paper towel to reuse.
General Procedure
Solution # A (containing Na2S2O3, KI, KNO3 and starch) is first placed in the beaker and
is stirred using the magnetic bar. The rate of stirring is set at level 8 as indicated in Fig-
ure 1. Solution #B (containing Fe(NO3)3 and HNO3) is quickly added into solution #A and
the stopwatch is simultaneously started. The time is recorded at the moment the solution
suddenly turns dark blue. The temperature of the solution is recorded using the digital
thermometer.
119
Insulating
plate (I.P.)
Figure 1. The apparatus employed for kinetic study of the clock reaction.
1. Practice run to observe the color changes

- There is no need to accurately measure the volumes used in this part – just use the
marks on the beaker as a guide.
- Pour ca. 20 mL of solution # A1 (containing KI, Na2S2O3, and starch in water) to a
100-mL graduated beaker containing a magnetic stirrer bar. Place the beaker on top
of the insulating plate on the magnetic stirrer.
- Pour ca. 20 mL of solution # B1 (containing Fe(NO3)3 and HNO3 in water) in another
100 mL graduated beaker.
- Quickly pour the solution # B1 into solution # A1 and start stopwatch simultaneously.
Stop stopwatch when the color of the mixture changes. There is no need to record
this time. Answer the following questions.
Task 1.1: Write down the molecular formula of the limiting reactant for the given clock
reaction.
Task 1.2: What are the ions or compounds responsible for the colors observed in this
experiment? Tick the appropriate box.
Color Compound
 Fe3+
 [Fe(S2O3)]+
Purple  Fe2+
 starch-I5-
 I3-
 Fe3+
 [Fe(S2O3)]+
Dark blue  Fe2+
 starch-I5-
 I3-
120
2. Determination of the order with respect to [I–] (y), and the rate constant (k)
In this section, Δt is determined for different initial concentrations of KI according to the
table below. The experiment is repeated as necessary for each concentration of KI.
Hint: Use 25 mL graduated pipette for solution #A2-1, 10 mL graduated pipette for KI, 5
mL graduated pipette for solution #B2, and one of the burettes for water (you will need
to refill the burette from the wash bottle for each measurement).
- Prepare 55 mL of solution # A2 in a 100 mL beaker containing a magnetic stirrer bar
and place it on top of the insulating plate on the stirrer. Solution #A2 contains solu-
tion #A2-1, KI, and distilled water (see the table below for the volume of each com-
ponent).
- Add 5 mL of solution # B2 in another 100 mL beaker.
Quickly pour prepared solution #B2 into solution #A2. Determine the time (Δt) necessary
for the color change by a stopwatch. The temperature of the solution is recorded.
Task 1.3: Record the time (Δt) for each run in the table below. (You DO NOT need to fill
all three columns for the runs.) For each concentration of KI, record your ac-
cepted reaction time (Δtaccepted) and temperature. You will be only graded on
your values of Δtaccepted and Taccepted.
55 mL of solution #A2
Δtaccepted Taccepted
No Run 1 Run 2 Run 3
#A2-1 H2O KI (s) (ºC)
(mL) (mL) Δt T Δt T Δt T
(mL)
(s) (ºC) (s) (ºC) (s) (ºC)
1 20.4 31.6 3.0
2 20.4 30.1 4.5
3 20.4 28.6 6.0
4 20.4 27.4 7.2
5 20.4 25.6 9.0
When you are satisfied you have all the necessary data for Problem 1, before
continuing further with the analysis, it is strongly recommended that you start
the practical procedure for Problem 2 since there is a reaction time of one hour
in that Problem.
Task 1.4: Fill in the table below and plot the results in the graph.
Hint: Make sure your data is graphed as large as possible in the provided space.
No. 1 2 3 4 5
ln([I-]0/M) - 5.30 - 4.89 - 4.61 - 4.42 - 4.20
Δtaccepted (s)
ln(Δtaccepted / s)
121
Task 1.5: Draw the best fit line on your graph and use this to determine the order with
respect to [I–] (y).
Task 1.6: Complete the table below and calculate k for each of the concentrations of
iodide. Report your accepted value for the rate constant, giving the appro-
priate unit. Remember that the order with respect to [Fe3+] is equal to one.
No Δtaccepted (s) [Fe3+]0 (×10-3 M) [I-]0 (×10-3 M) [S2O32-]0 (×10-3 M) k

1 5.0
2 7.5
3 10.0
4 12.0
5 15.0
kaccepted = ………………….
Practical Problem 2. Synthesis of a derivative of Artemisinin

Artemisinin (also known as Quinghaosu) is an antimalarial drug isolated from the yellow
flower herb Artemisia annua L., in Vietnam. This drug is highly efficacious against the
chloroquine-resistant Plasmodium falciparum. However, artemisinin has a poor solubility
in both oil and water so that one needs to prepare its new derivatives to improve the
applicability of this drug. The reduction of artemisinin is an attractive method to synthe-
size new derivatives of artemisinin as shown in Scheme 1.
Scheme 1
In this practical exam you are going to reduce artemisinin to product P and check its pu-
rity using Thin-Layer Chromatography (TLC).
Experimental Set-up
- The experimental set-up is shown in Figure 2.1.
- By moving the finger clamp, you can adjust the position of the two-neck round-bottom
flask.
122
2 3
1: Digital thermometer; 2: Plastic Stopper; 3: CaCl2 drying tube; 4: Ice Bath

Figure 2.1. Reaction system for Problem 2
Procedure
Step 1. Synthesis of a Derivative of Artemisinin
1. Prepare an ice bath with a temperature between –20 and –15 oC by mixing ice and
sodium chloride in the plastic pot (approximate ratio of NaCl : crushed ice = 1 scoop :
3 scoops). Use the digital thermometer to monitor the temperature. Place the bath on
the magnetic stirrer. Put a layer of three tissues between the bath and the stirrer.
2. Connect the CaCl2 drying tube to the small neck of the round-bottom flask and close
the other neck with the plastic stopper.
3. Place a magnetic stirring bar into the dry round-bottom flask and set up the reaction
system onto the clamp-stand so that the system is immersed in the ice bath. Monitor
the temperature using the digital thermometer.
4. Setting aside a tiny amount (ca. 2 mg) of artemisinin for TLC analysis, open the stop-
per and add the 1 gram of artemisinin through the bigger neck.
5. Use the glass funnel to add 15 mL of methanol (measured using the 50-mL graduated
cylinder). Close the stopper and turn on the magnetic stirrer. (Set the magnetic stir-
rer to level 4). Start the stopwatch to keep track of the time.
6. After ca. 5 min stirring, open the stopper and add carefully 0.53 g of NaBH 4 in small
portions over 15 min using a spatula. Close the stopper in between addition. (Cau-
tion: Adding NaBH4 rapidly causes side-reactions and overflowing). Keep stirring for
50 min. Maintain the temperature of the ice bath below –5 oC; remove some of the
liquid and add more NaCl-crushed ice mixture if necessary. Cool the vial containing
the 1 mL of acetic acid in the ice bath.
During this waiting time, you are advised to finish calculations from Problem
1, answer the questions below, and prepare further experimental steps.
123
7. Prepare 50 mL of ice-cold distilled water (cooled in the ice bath) in the 100 mL- coni-
cal flask. Measure ca. 20-22 mL n-hexane in the 50 mL measuring cylinder and cool it
in the ice bath. After the reaction is complete, keep the reaction flask in the ice bath
below 0 oC. Remove the CaCl2 tube, open the stopper, and add gradually ca. 0.5 mL
of the cold acetic acid from the vial into the reaction flask until the pH is between 6
and 7. (Use the glass rod to spot the reaction mixture on to the pH paper.) With stir-
ring, slowly add the 50 mL of ice cold water over 2 min. A white solid precipitates in
the reaction flask.
8. Assemble the vacuum filtration apparatus. Put a filter paper onto the Büchner funnel,
wet the filter paper with distilled water and open the vacuum valve. Transfer the reac-
tion mixture on to the filter, and remove the stirring bar from the reaction flask using
the spatula. Wash the product three times with portions of 10 mL ice-cold water
(cooled in the ice bath). Wash the product two times with portions of 10 mL ice-cold
n-hexane (cooled in the ice bath). Continue to use the pump to dry the solid on the
filter. After ca. 5 min, carefully transfer the dried powder on to the watch glass la-
beled with your code and put into the labeled Petri dish. Turn off the vacuum valve
when you do not use it! Note: Your sample will be collected, dried and weighed later
by the lab assistant.
Task 2.1 The recording of your yield –will be performed after the exam by the lab as-
sistants.
Step 2. TLC Analysis of the product

1. Check your TLC plate before use. Unused damaged plates will be replaced upon re-
quest without penalty. Use the pencil to draw the start front line, and the line where
the solvent front will be run to exactly as shown in Figure 2.2. Write your student
code on the top of the TLC plate in pencil.
Figure 2.2. Instruction of TLC plate preparation
124
2. Dissolve ca. 1 mg of artemisinin (a spatula tip) in ca. 0.5 mL of methanol in the la-
beled very small test tube (use the labeled 5 mL graduated pipette). Dissolve ca. 1
mg of the product in ca. 1 mL of methanol in the labeled test tube.
3. Spot the artemisinin solution and the product solution on the TLC plate using two dif-
ferent glass capillary spotters so the finished plate is as shown in Figure 2.2.
4. Prepare the TLC developing chamber. Use the 5 mL graduated cylinder to make 5 mL
of a mixture of n-hexane/ethyl acetate (7/3, v/v) as the solvent system. Pour the
mixture of n-hexane/ethyl acetate into the chamber (Note: The solvent level should
not reach the spots on the plate if prepared as shown). Cover and swirl the chamber
and allow it to stand for 2 min.
Figure 2.3. A TLC plate placed in the TLC developing chamber and instruction for R f
calculation of compound A
5. Insert the TLC plate upright into the TLC developing chamber. Wait until the solvent
system reaches the pre-drawn solvent front line. (Note: You are advised to work on
some question below while you wait for the TLC to run.)
6. When the solvent front reaches the line, remove the TLC plate using the tweezers and
then dry the solvent using the hair dryer set at level 1.
7. Dip the piece of cotton wool into the cerium staining reagent, taking care not to let
the tweezers come into contact with the solution since the metal stains the plate.
Carefully apply the stain to the whole TLC plate.
8. Heat the TLC plate using the hair dryer set at level 2 (Attention: Do NOT set the hair
dryer to COLD) until the blue spots of artemisinin and the product appear on the TLC
plate.
9. Ask the lab assistant to take a photo of your final TLC plate together with your stu-
dent code.
10. Circle all the visualized spots and calculate the Rf values of both artemisinin and the
product (See instruction in Fig. 2.3). Store your TLC plate in the Petri dish.
Task 2.2: Fill the values of Rf in Table and determine the ration.
Task 2.3: Check the total number of developed spots on the TLC plate.
125
Step 3. Identifying the reaction product P

The reduction of artemisinin leads to the formation of two stereoisomers (P). Comparing
the 1H-NMR spectrum (in CDCl3) of one of these isomers with the spectrum of artemisinin
shows an extra signal at δH = 5.29 ppm as a doublet, and also an extra signal as a broad
singlet at δH = 2.82 ppm.
Task 2.4: Suggest structure for P. (You do not need to draw the stereochemistry of the
compounds).
Task 2.5: P is mixture of two stereoisomers. What is their stereochemical relationship?

Check the appropriate box below.
Practical Problem 3.
Analysis of a hydrated zinc iron(II) oxalate double salt
Zinc iron(II) oxalate double salt is a common precursor in the synthesis of zinc ferrite
which is widely used in many types of electronic devices due to its interesting magnetic
properties. However, such double salts may exist with different compositions and differ-
ent amount of water depending on how the sample was synthesized.
You will analyze a pure sample of hydrated zinc iron(II) oxalate double salt (Z) in order
to determine its empirical formula.
Procedure
The concentration of the standard KMnO4 is posted on the lab walls.
Bring a clean 250 mL beaker to the lab assistant who will be waiting by the balance. You
will receive a pure sample of Z for analysis. Accurately weigh between 0.7-0.8 g of the
pure sample Z onto the weighing paper (m in g). This should then be immediately quan-
titatively transferred into your 250 mL beaker for analysis, and its mass recorded in table
below.
Task 3.1: Record the mass of the sample of pure Z taken.
126
Analysis of Z
- Using the 100 mL graduated measuring cylinder, measure ca. 30 mL of 30 wt.% H2SO4
solution and add it into the 250-mL beaker containing your accurately weighed pure
sample of Z. To speed up the dissolving of your sample you may use the hotplate stir-
rer to warm up the mixture, but be careful not to boil it. You should not use the digi-
tal thermometer as the acid may damage it. After the solid has dissolved, remove the
beaker from the hotplate stirrer and cool it to close to room temperature. After the
solution has cooled, quantitatively transfer it into the 100 mL volumetric flask. Add
distilled water up to the 100 mL–mark. We will now call this solution C.
- Use an appropriately labeled beaker to transfer the standardized KMnO 4 solution into
the burette graduated with brown marks.
- Use another appropriately labeled beaker to transfer the standardize EDTA solution
into the burette graduated with blue marks.
Titration with KMnO4

a) Using the 5 mL graduated pipette add 5.00 mL of the solution C into a 250 mL conical
flask.
b) To this conical flask add about 2 mL of 30 wt.% H2SO4 solution, about 3 mL of 3.0 M
H3PO4 solution, and about 10 mL of distilled water. Heat the mixture on the hot plate
stirrer until hot, but be careful not to boil it.
c) Titrate the hot solution with the standardized KMnO4 solution, recording your burette
readings in the table below. At the end point of the titration, the pink color of the so-
lution appears. Repeat the titration as desired and report your accepted volume of
KMnO4 solution consumed (V1 mL) in the table.
Task 3.2: Record volumes of standardized KMnO4 solution consumed.
Task 3.3: Can aqueous HCl or HNO3 be used instead of H2SO4 for the dissolving of
sample Z and the subsequent analyses?
Titration with EDTA

- Clean both the 250 mL beakers ready for the next part of the experiment. Pipette
10.00 mL of solution C into a 250 mL beaker. Heat and stir the solution on the hot-
plate stirrer, but be careful not to boil it. Add ca. 15 mL of 20 wt.% NaOH solution to
the beaker and keep it on the hotplate for ca. 3-5 min in order to complete the pre-
cipitation of iron hydroxide, and to convert all Zn 2+ ions into the ionic complex
[Zn(OH)4]2-.
- Using a glass funnel and the large quantitative filter paper, filter the hot suspension
directly into the 250 mL conical flask. From this point take care with the volumes as
you will be preparing a standard solution of exactly 100 mL from the filtrate. As it is
filtering, prepare some warm distilled water in a 250 mL beaker (ca. 50 mL). Wash
127
the precipitate on the filter paper (at least 5 times) with small portions (ca. 5 mL) of
the warm distilled water. Cool the filtrate down and then quantitatively transfer it into
the 100 mL volumetric flask via a glass funnel. Add distilled water to make up to the
100 mL mark. This will now be referred to as solution D.
- Pipette 10.00 mL of solution D into a 250 mL conical flask. Add ca.10 mL ammonia
buffer solution (pH = 9 – 10) and a small quantity of the ETOO indicator using the
glass spatula spoon. Mix well to obtain a purple solution. Titrate the solution with the
standardized 2.00 × 10–3 M EDTA solution and record your burette readings in the ta-
ble below. At the end point, the color of the solution turns blue. Repeat the titration
as desired and report your accepted volume of EDTA solution consumed (V 2 mL) in
the table.
Task 3.4: Record the volumes of EDTA solution consumed.
Determination of the empirical formula of Z
Task 3.5: Calculate the number of moles of Zn 2+, n Zn 2  , present in 100 mL of solution C.
Task 3.6: Give the ionic equations for the reduction-oxidation reactions taking place in
the titration with KMnO4.
Task 3.7: Calculate the number of moles of Fe2+, nFe 2 , present in 100 mL of solution C.
[YOU WILL NEED THE PRECISE CONCENTRATION OF KMnO4 POSTED ON THE

WALLS IN YOUR LAB]
Task 3.8: Calculate the number of moles of C2O42- anion, nC O2 , in 100 mL of solution C.
2 4
Task 3.9: Calculate the number of moles of water, nH 2O , in the original sample of Z tak-
en for analysis.
Task 3.10: Give the empirical formula of Z.
128
IChO Hanoi: Solutions Theoretical Test
Solutions to the theoretical Problems
Solution to problem 1.
1.  = 65.01 · mit k = 4;  = 260.0 nm
2. E= E = ELUMO - EHOMO = h· = 


E = [(k+1)2 – k2 ] = [2 k +1] mit L = (k+2) · 1,40 Å:
E = =  =

= m
 = 6.462 ·10-8 · m = 64.62 · nm  Bcalc = 64,6 nm
3. With λ = 600 nm we have = 9,825 =

2
k – 14,57 k – 5,285 = 0 k1= 14,92 (k2 = -0.355)
k = 15  the formula of polyene is CH2 = CH – (CH = CH)13 – CH = CH2
4. E = ELUMO - EHOMO = [2 k +1]
E = kJ·mol-1
E = 1851 · kJ·mol-1
For polyene with k = 15 ; ΔE = 199 kJ·mol–1.
5a. Lx = Ly = Lz ; Exyz =
E111 = =
E112 = = = E121 = E211
E122 = = = E212 = E221
5b. E111: only a single state.

E112: triple degenerate, either nx, ny or nz can equal to 2.
E122: triple degenerate, either nx, ny or nz can equal to 1.
E222: single state.
Energy diagram (cubic box):
E222
E122
Energy
E112
E111
129
1a. N2O4 2 NO2
Initial molar number 1 0
At equilibrium 1-x 2·x
ntotal,equi. = 1 - x + 2x = 1 + x Ptotal,equi = Pini(1 + x)
ntotal,equi. = = = 1.174 mol
1.174 = 1 + x x = 0.174
At equilibrium:
p(N2O4) = · ptotal = · 1.190 bar = 0.837 bar
p(NO2 = · ptotal = · 1.190 bar = 0.353 bar
K298 = = = 0.1489
At 298 K:
G° = -R·T·lnK298 = (-8.3145 · 298 · ln 0.1489) J·mol-1 = 4719 J·mol-1 = 4.72 kJ·mol-1
1b. ∆G0 at 348 K:
ntotal,equi. = = = 1.593 mol
1.593 = 1 + x x = 0.593
At equilibrium:
p(N2O4) = · ptotal = · 1.886 bar = 0.482 bar
p(NO2 = · ptotal = · 1.886 bar = 1.404 bar
K348 = = = 4.0897
At 348 K:
G° = -R·T·lnK348 = (-8.3145 · 348 · ln 4.0897) J·mol-1 = -4075 J·mol-1 = -4.07 kJ·mol-1
∆G0348 = -4.07 kJ·mol-1 = ∆H° – 348 K ·∆S° (1)

∆G0298 = 4.72 kJ·mol-1 = ∆H° – 298 K ·∆S° (2)
(2) - (1)  ∆S° = 0.176 kJ·mol–1·K–1
∆H0 = 4.720 + 298 × 0.176 ∆H0 = 57.2 kJ·mol–1
2. ∆U = q + w; work done by turbine w(air)=-w
q = 0, thus w(air) = ∆U = Cv,m(air)[T3-T4]

3. ln = ·[ ]= ·[ ]
 ln K440 = 5.542 K440 = 255.2
N2O4 2 NO2
Initial molar number 1 0
At equilibrium 1-x 2·x
ntotal,equi. = 1 - x + 2x = 1 + x Ptotal,equi = 12.156 bar
At equilibrium:
p(N2O4) = · 12.156 bar p(NO2 = · 12.156 bar
K440 = = = 255.2  =
130
= 20.99  = 20.99 4 x2 = 20.99 – 20.99 x2
 x = 0.92 ntotal = 1 + x = 1.92

wN 2O4
wN 2 O4 = 1.92 · Cv,air · (T3 – T4)   1.92
wair
1a. Paramagnetic
1b. Oxidation number of Ag1 : +1 Oxidation number of Ag2 : +3
1c. The coordination number of O atoms: 3
I
1d. Number of Ag = 1
Number of AgIII = 2
1e. Diamagnetic
The AgI is d10 hence diamagnetic; the AgIII is square planar d8 also diamagnetic
1f. S2O82- (aq) + 2 Ag+(aq) + 2 H2O (l)  2 SO42-(aq) + AgIAgIIIO2 (s) + 4 H+(aq)
2a. Ulat of AgIAgIIIO2:
ΔHlat (AgIAgIIIO2) = 2 ΔHof (O2-) + ΔHof (Ag+) + ΔHof (Ag3+) –ΔHof (AgIAgIIIO2)
= [(2×249 – 2 × 141 + 2 × 844) + (284.9 + 737.2) + (284.9 + 737.2 +
2080.2 + 3367.2 ) – (–24.3)] kJ·mol–1
= 9419.9 kJ·mol–1
U lat (AgIAgIIIO2) = ΔHlat (AgIAgIIIO2) – 4·R·T
= (9419.9 – 10.0 ) kJ·mol–1 = 9409.9 kJ·mol–1
Ulat of CuIIO:
ΔHlat (CuIIO) = ΔHof (O2–) + ΔHof (Cu2+) – ΔHof (CuIIO)
= [(249 – 141 + 844) + (337.4 + 751.7 + 1964.1) – (–157.3)] kJ·mol–1
= 4162.5 kJ·mol–1
U lat (CuIIO) = ΔHlat (CuIIO) – 2·R·T = (4162.5 – 5.0) kJ·mol–1 = 4157.5
2b. Vm (AgIIO) = Vm (AgIIAgIII2O4) - Vm (AgIII2O3) = (0.08985 – 0.06182) nm3 = 0.02803 nm3

From the relationship Ulat = C×(Vm)–1/3 we have
[ ]1/3
Ulat (AgIIO) = 4157.5 · √ kJ·mol-1 = 3733.6 kJ·mol-1
2c.
ΔHrxn = 2·Ulat (AgIIO) + 4·R·T + IE3 – IE2 – Ulat(AgIAgIIIO2) – 4·R·T

= (2 × 3733.6 + 3367.2 – 2080.2 – 9409.9)
= – 655.7 kJ·mol–1
2d. AgIAgIIIO2
131
3. For B: AgIAgIIIO2 (s) + 4 HClO4 (aq)  2Ag(ClO4)2 (aq) + 2 H2O (l)

For C: 4Ag(ClO4)2 (aq) + 2 H2O (l)  4 AgClO4 (aq) + 4 HClO4 (aq) + O2 (g)
4a.
- n(Ag) in 0.6164 g of Z = n(AgCl) = 0.001 mol
- n(SO42-) from 0.6160 g of Z = n(BaSO4) = 0.002 mol
- Mass percentage of Ag = 0.001 · 107.87/0.6164 · 100 % = 17.50 %
- Mass percentage of SO42- = 0.002 · 96.06/0.6164 · 100 % = 31.17 %
- From EA:
n(Ag2+): n(SO42-): n(C): n(H): n(N) = : : : : = 1 : 2 : 20 : 20 : 4
The empirical formula of Z is: C20H20AgN4O8S2
Yield = · 100 % = 94.7 %
4b.
- √ = 1.78 (n is number of unpaired electron of Ag)
- n = 1, corresponds to AgII (d9)
- Most rational molecular formula of Z is [AgII(Py)4](S2O8)
4c. Formation of Z:
2 Ag+ (aq) + 8 Py (l) + 3 S2O82– (aq)  2 [AgII(Py)4](S2O8) (s) + 2 SO42– (aq)
Destruction of Z with NH3:

[AgII(Py)4](S2O8)(s) + 6 NH3(l)  [Ag(NH3)2]+(aq) + ½ N2(g) + 2 SO42-(aq)+3 NH4+(aq) + 4 Py(l)
(All reasonable N –containing products and O2 are acceptable)
Formation of D:
[Ag(NH3)2]+ (aq) + 2 H+ (aq) + Cl– (aq)  AgCl (s) + 2 NH4+ (aq)
Formation of E:
Ba2+(aq) + SO42– (aq)  BaSO4 (s)
1a. PtCl4 + 2 C2H5OH  H[PtCl3C2H4] + CH3CH=O + HCl + H2O
H[PtCl3C2H4] + KCl  K[PtCl3C2H4] + HCl
K2[PtCl6] + 2 C2H5OH  K[PtCl3C2H4] + CH3CH=O + KCl + 2 HCl + H2O
K2[PtCl4] + C2H4  K[PtCl3C2H4] + KCl
1b. 195 + 3×35 + 2×12 + 4×1 = 328
2.
Number of different environments Number of different environ-
Structure
of hydrogen ments of carbon
Z1 2 2
Z2 2 2
Z3 2 2
Z4 1 1
Z5 2 1
3a.
A
132
3b.
B C D
E F G
3c.
Structure D F
Driving force(s) i iii and iv
1. HA H+ + A– and HB H+ + B– and H2O H+ + OH–
+ + – – –
Amount of H : [H ] = [OH ] + [A ] + [B ]
In the acidic solution (pH = 3.75), [OH–] can be neglected, so:
[H+] = [A–] + [B–] (1)
KHA = and [HA] = [HA]i – [A–] (where [HA]i is the initial concentration)
 [H+] · [A–] = KHA · [HA] = KHA · ([HA]i - [A–])
 [A–] = and, similarly, [B–] =
Substitution into Eq.(1): [H+] = +
Since KHA, KHB are much smaller than [H+], thus: [H+] = +
1.74 × 10–7 · [HA]i + 1.34 · 10–7 · [HB]i = [H+]2 = (10–3.75 )2

1.74 × [HA]i + 1.34 × [HB]i = 0.316 (2)
Neutralization reactions:
HA + NaOH  NaA + H2O and HB + NaOH  NaB + H2O
nHA + nHB = nNaOH
 ([HA]i + [HB]i) · 0.1 L = 0.220 mol/L · 0.1 L
[HA]i + [HB]i = 0.220 mol/L (3)
Solving Eq.(2) and Eq.(3) gives: [HA]i = 0.053 mol/L and [HB]i = 0.167 mol/L
Concentration of HA = 0.053 mol/L Concentration of HB = 0.167 mol/L
2. Solution Y contains 0.06 mol/L of NaA and 0.04 mol/L of NaB. The solution is basic, OH– was
produced from the reactions:
NaA + H2O HA + OH– Kb,A = Kw/KHA = 5.75 ·10-8
–
NaB + H2O HB + OH Kb,B = Kw/KHB = 7.46 ·10-8
H2O H+ + OH– Kw = 1.00 10-14
and we have [H ] + [HA] + [HB] = [OH–]
+
In the basic solution, [H+] can be neglected, so:

[HA] + [HB] = [OH–] (4)
Kb,A = and [A–] = 0.06 – [HA]
133
 [HA] = and, similarly, [HB] =
Substitution into Eq. (4): + –
Assume that Kb,A and Kb,B are much smaller than [OH–] (*), thus:
[OH–] 2 = (5.75 · 10 –8 × 0.06 + 7.46 · 10 –8 × 0.04) (mol/L)2
[OH–] = 8.02 · 10 –5 mol/L (the assumption (*) is justified)
So pOH = 4.10 and pH = 9.90
3. HA in the dilute solution: [A–] = α × [HA]i [HA] = (1 - α ) × [HA]i

+ –7
[H ] = 10 mol/L
Substitution of these equilibrium concentrations into KHA expression:
 
KHA =  = 1.74 · 10-7   = 0.635
 

Similarly, for HB: = 1.34 · 10-7   = 0.573

 percentage of dissociation of HA = 65.5 %
percentage of dissociation of HB = 57.3 %
4. Equilibria in the solution:

M(OH)2 M2+ + 2OH– Ksp = 3.10 ×10-12
H2O H+ + OH– Kw = 1.00 × 10-14
M2+ + A– [MA]+ K1 = 2.10 × 103
[MA]+ + A– [MA2] K2 = 5.00 × 102
M2+ + B– [MB]+ K’1 = 6.20 × 103
[MB]+ + B– [MB2] K’2 = 3.30 × 102
Solubility of M(OH)2 = s = [M2+] + [MA+] + [MA2] + [MB+] + [MB2]
pH of Z = 10.0
[M]2+ = = = 3.10 · 10-4 mol/L
At pH = 10.0:
[A-]total = = 0.06 mol/L
[MA+] = K1 · [M2+] · [A–] = 2.1 · 103 · 3.10 · 10–4 ·[A–] = 0.651 ·[A–] (5)
2+ - 2 – 2
[MA2] = K1 · K2 · [M ] · [A ] = 325.5 · [A ] (6)
– - +
[A ]total = [A ] + [MA ] + 2 · [MA2] = 0.06 mol(L (7)
Substitute Eq. (5) and Eq. (6) into Eq. (7):
[A–] + 0.651 · [A–] + 2 · 325.5 × [A–]2 = 0.06
 [A-] = 8.42× 10 –3
mol/L
Substitute this value into Eq. (5) and Eq. (6):
[MA+] = 0.651 · [A–] = 5.48 × 10 –3
mol/L
– 2 –2
[MA2] = 325.5 · [A ] = 2.31 × 10 mol/L
Similarly,
[B–]total = 0.04 mol/L
[MB+] = K1 · [M2+] · [B–] = 6.2 · 103 · 3.10 · 10–4 ·[B–] = 1.92 ·[B–] (8)
134
MB2] = K1 · K2 · [M2+] · [B-]2 = 634.3 · [B–]2 (9)

[B–]total = [B-] + [MB+] + 2 × [MB2] = 0.04 M (10)
Substitute Eq. (8) and Eq. (9) into Eq. (10):
[B–] + 1.92 · [B–] + 2 · 634.3 · [B–]2 = 0.04
 [B–] = 4.58 × 10–3 mol/L
Substitute this value into Eq. (8) and Eq. (9):
[MB+] = 1.92 ·[B–] = 8.79 · 10 –3
mol/L
– 2 –2
[MB2] = 634.3 · [B ] = 1.33 · 10 mol/L
Thus, solubility of M(OH)2 in Z is s’
–4 –3 –2 –3 –2 –2
s’ = 3.10 · 10 + 5.48 · 10 + 2.31 · 10 + 8.79 · 10 + 1.33 · 10 = 5.10 · 10 mol/L
–2
Solubility of M(OH)2 in Z = 5.10 · 10 mol/L.
6a.
[ArCl] in mol·L-1 Initial rate in 0.00016
mol·L-1·s–1
0.1 1.88 · 10-5
0.00014
0.2 4.13 · 10-5 0.00012

-1
0.4 9.42 · 10-5

Initial rate in mol L s
-1
0.00010
0.6 1.50 · 10-4
0.00008
0.00006
0.00004
Order with respect to [ArCl] = 1 0.00002
0.00000
0.1 0.2 0.3 0.4 0.5 0.6
-1
Concentration of ArCl in mol L
[NiLL’] Initial rate in 0.00011

in mol·L-1 mol·L-1·s–1
6 × 10–3 4.12 · 10-5 0.00010
9 × 10–3 6.01 · 10-5

0.00009
1.2 × 10–2 7.80 · 10-5
-1 -1
1.5 × 10–2 1.10 · 10-4 0.00008
0.00007
0.00006
Order with respect to [NiLL’] = 1

0.00005
0.00004
0.006 0.008 0.010 0.012 0.014

-1
Concentration of NiLL' in mol L
135
[L’] Initial rate 1/(Initial rate)

in mol·L-1 in mol·L-1·s–1 in mol-1·L·s 35000
-5
0.06 5.8 · 10 17240
0.09 4.3 · 10-5 23260
30000
0.12 3.4 · 10-5 29412
1/inital rate in mol Ls

2.8 · 10-5
-1
0.15 35710
25000
20000
Order with respect to [L’] = -1

15000
0.06 0.08 0.10 0.12 0.14
-1
Concentration of L' in mol L
[ ] [ ]
6b. rate = =
6c.
[NaOtBu] Initial rate in 0.00006

0.2 4.16 · 10-5
0.6 4.12 · 10-5
-1 -1
0.9 4.24 · 10-5

0.00004
1.2 4.20 · 10-5
0.00002
Order with respect to [NaOtBu] = 0

0.2 0.4 0.6 0.8 1.0 1.2
t -1
Concentration of NaO Bu in mol L
[RNH2] Initial rate in

0.00006
0.3 4.12 · 10-5

0.6 4.26 · 10-5 0.00005
-1 -1
-5
0.9 4.21 · 10
1.2 4.23 · 10-5

0.00004
0.00003
Order with respect to [RNH2] = 0 0.00002

0.2 0.4 0.6 0.8 1.0 1.2
-1
Concentration of RNH2 in mol L
136
6d. Using the mechanism depicted by Reaction (1) through (4), the rate equation:
= -k1 · [NiLL'] + k-1 · [NiL] · [L']
= k1 · [NiLL'] - k-1 · [NiL] · [L'] – k2 · [NiL] · [ArCl] + k4 · [NiL(Ar)NHR]

Apply the steady-state approximation to the concentrations for the intermediates:
=0
k1[NiLL’] = k-1[NiL][L’] + k2[NiL][ArCl] – k4[NiL(Ar)HNR] (1)
t
= k2[NiL][ArCl] – k3[RNH2][NaO Bu] [NiL(Ar)Cl] = 0
[NiL(Ar)Cl] = (2)
= k3[NiL(Ar)Cl] [NH2R] [NaOtBu] – k4[NiL(Ar)NHR] = 0
[NiL(Ar)NHR] = · [NiL(Ar)Cl] [NH2R] [NaOtBu] (3)
Substitute Equation (2) into Equation (3):
[NiL(Ar)NHR] = · [NH2R] [NaOtBu] · = · [ArCl] [NiL] (4)
Substitute Equation (4) into Equation (1):
k1[NiLL’] = k-1[NiL][L’] + k2[NiL][ArCl] – k4 · · [ArCl] [NiL] = k-1[NiL][L’] (5)
The material balance equation with respect to the catalyst is

[NiLL’]0 = [NiLL’] + [NiL] + [NiLAr(Cl)] + [NiLAr(Cl)NHR]
[NiLL’]0 = [NiL][L’] + [NiL] + + · [ArCl] [NiL]

[ ]
[NiLL’]0 = [NiL]
[ ]
[NiL] = [NiLL’]0 ·
(6)
Substituting Equation (6) into the differential rate for [ArCl], - = k2[ArCl][NiL], results
in the following predicted rate law expression for the reaction mechanism:
= = k2[ArCl][NiL] =
6e. = = k2[ArCl] [NiL] =
7a.
A B C
137
7b.
The acid C was converted to diastereomeric iodolactones D and E (epimeric at the chiral center
C3). Look at the number-indicated in the structure F in the next step.
D E
7c.
Because alkylated lactone F is known, we can deduce the reagent X as methyl vinyl ketone. H
is the reduced product of D.
X H
7d.
The keto group of lactone F reacted with ethanedithiol and BF3·Et2O in dichloromethane to afford
thioketal lactones, I and the major isomer J.
I J
7e.
Hydrolysis followed by esterification of J provided hydroxy ester K.
Oxidation of the hydroxy group in K by PCC resulted in the keto ester L in which two protons
adjacent to the carbonyl group are cis-oriented.
K L
7f.
The Wittig reaction of the ketone L resulted in the formation of methyl vinyl ether M.
Deprotection of the thioketal group forms the intermediate N.
M N
138
8a.
Y1 Y2 Y3
CH3OH
A B
C D
8b. E does not contain two trans ethylenic protons as anethole.

8c.
F G
E
8d.
H I
J K
9a.
A B C
139
9b.
9c.
E F
9d. 9e.
G
9f.
i)
E.g. H1 H2
ii)
E.g. H1 H3
iii)
E.g. H3 H4
H1 H2 H3 H4
140
About the History of the IChO
About the history of the International Chemistry-Olympiads

The idea of chemistry olympiads was born 1968 during an Czechoslovakian national
olympiad that was attended by observers from Poland and Hungary. These three
countries participated in the first IChO 1968 in Prague. The number of teams atten-
ding the IChO in the following years are shown in the plot below.
Number of teams attending the IChO
70
60
50
Number of Teams
40
30
20
10
0
1970 1980 1990 2000 2010
Year of Olympiad
The participating countries are shown in the following table.
141
Participating Delegations
•= host. + = participant. o = observer
Year  6 6 7 7 7 7 7 7 7 7 7 8 8 8 8 8 8 8 8 8 8 9 9 9 9 9 9 9 9 9 9
Country  8 9 0 2 3 4 5 6 7 8 9 0 1 2 3 4 5 6 7 8 9 0 1 2 3 4 5 6 7 8 9
Argentina + + + + +
Armenia
Australia o + + + + + + + + + + • +
Austria + + + + + + + + + + + + + + + + + + + + + + + +
Azerbaijan o o
Belarus + + + +
Belgium + + + + + + + + + + + + + + + + + + + +
Brazil o o +
Bulgaria + + + + + + + + + + • + + + + + + + + + + + + + + + + + +
Canada o o + + + + + + + + + + + • + +
China + + + + + + + + • + + + +
Chinese Taipei + + + + + + + +
Costa Rica
Croatia o o
Cuba + o + + + + + + + + + + +
Cyprus o + + + + + + + + + +
Czech Rep. + + + + + + +
Czechoslovakia • + + + + + + + • + + + + + + + • + + + + + + +
Denmark + + + + + + + + + + + + + + + + + +
DDR o + + + + + • + + + + + + + + + + + • +
Egypt
El Salvador
Estonia + + + + + +
Finland o + + + + + + + + + + • + + + + + + + + + + +
France o + + + + + + + + + • + + + + + + + + +
fYROM (Macedonia)
Georgia
Germany o + + + + + + + + + • + + + + + + + + + + + + + + +
Greece + + + + + + + + + + + + + + +
Hungary + + • + + + • + + + + + + + + + + + • + + + + + + + + + + + +
Iceland
India o o +
Indonesia o + + +
Iran + + + + + + +
Ireland o o + +
Israel
 Country 6 6 7 7 7 7 7 7 7 7 7 8 8 8 8 8 8 8 8 8 8 9 9 9 9 9 9 9 9 9 9
Year  8 9 0 2 3 4 5 6 7 8 9 0 1 2 3 4 5 6 7 8 9 0 1 2 3 4 5 6 7 8 9
142
Year  0 0 0 0 0 0 0 0 0 0 1 1 1 1 1
Country  0 1 2 3 4 5 6 7 8 9 0 1 2 3 4
Argentina + + + + + + + + + + + + + + +
Armenia o o + + + + + + + + +
Australia + + + + + + + + + + + + + + +
Austria + + + + + + + + + + + + + + +
Azerbaijan + + + + + + + + + + + + + + +
Belarus + + + + + + + + + + + + + + +
Belgium + + + + + ++ + + + + + + + +
Brazil + + + + + ++ + + + + + + + +
Bulgaria + + + + + ++ + + + + + + + +
Canada + + + + + ++ + + + + + + + +
China + + + + + + + + + + + + + +
Chinese Taipei + + + + + • + + + + + + + + +
Costa Rica o o + + + + +
Croatia + + + + + + + + + + + + + + +
Cuba + + + + + + + + + + + +
Cyprus + + + + + + + + + + + + + + +
Czech Rep. + + + + + + + + + + + + + + +
Czechoslovakia
Denmark • + + + + ++ + + + + + + + +
DDR
Egypt o o + + + ++ + +
El Salvador o o + +
Estonia + + + + + ++ + + + + + + + +
Finland + + + + + ++ + + + + + + + +
France + + + + + ++ + + + + + + + +
fYROM (Macedonia) o o + +
Georgia o o +
Germany + + + •
+ + + + + + + + + + +
Greece + + • +
+ + + + + + + + + + +
Hungary + + +
+ + + + + • + + + + + +
Iceland o o +
+ + + + + + + + + + + +
India + • + + + + + + + + + + + + +
Indonesia + + + + + + + + + + + + + + +
Iran + + + + + + + + + + + + + + +
Ireland + + + + + + + + + + + + + + +
Israel o o + + + + + + + + +
 Country 0 0 0 0 0 0 0 0 0 0 1 1 1 1 1
Year  0 1 2 3 4 5 6 7 8 9 0 1 2 3 4
143
Year  6 6 7 7 7 7 7 7 7 7 7 8 8 8 8 8 8 8 8 8 8 9 9 9 9 9 9 9 9 9 9
Country  8 9 0 2 3 4 5 6 7 8 9 0 1 2 3 4 5 6 7 8 9 0 1 2 3 4 5 6 7 8 9
Italy + + + + + o o + + + + + + + + + + + + +
Japan
Yugoslavia + + + + + + + + + +
Kazakhstan o o + +
Kenya o
Korea + + + + + + + +
Kuwait o o + + + + + + + + + + +
Kyrgyzstan o o +
Liechtenstein
Latvia + + + + + + + + +
Lithuania + + + + + + + + +
Malaysia
Mexico + + + + + + + +
Moldova
Mongolia
Montenegro
Netherlands + + + + + + • + + + + + + + + + + + + +
New Zealand + + + + + + + +
Nigeria
Norway o + + + + + + + + + + + + • + + + + +
Pakistan
Oman
Peru
Philippines o
Poland + • + + + + + + + • + + + + + + + + + + + + • + + + + + + + +
Portugal
Romania + + + • + + + + + + + + • + + + + + + + + + + + + + + + +
GUS/Russ.Fed + + + + • + + +
Saudi Arabia
Serbia
Singapore o + + + + + + + + + + +
Slovakia + + + + + + +
Slovenia + + + + + + + + +
South Africa
Spain o + + + +
 Country 6 6 7 7 7 7 7 7 7 7 7 8 8 8 8 8 8 8 8 8 8 9 9 9 9 9 9 9 9 9 9
Year  8 9 0 2 3 4 5 6 7 8 9 0 1 2 3 4 5 6 7 8 9 0 1 2 3 4 5 6 7 8 9
144
Year  0 0 0 0 0 0 0 0 0 0 1 1 1 1 1
Country  0 1 2 3 4 5 6 7 8 9 0 1 2 3 4
Italy ++ + + + ++ + + + + + + + +
Japan o + + ++ + + + • + + + +
Yugoslavia o
Kazakhstan ++ + + + ++ + + + + + + + +
Kenya o
Korea ++ + + + +• + + + + + + + +
Kuwait ++ + + + ++ + + + + + + +
Kyrgyzstan ++ + + + ++ + + + + + + + +
Latvia ++ + + + ++ + + + + + + + +
Liechtenstein o o o o o +
Lithuania ++ + + + ++ + + + + + + + +
Malaysia o ++ + + + + + + +
Mexico ++ + + + ++ + + + + + + + +
Moldova o o + + + + + + + +
Mongolia o o o + + + + + + + + +
Montenegro o o +
Netherlands ++ • + + ++ + + + + + + + +
New Zealand ++ + + + ++ + + + + + + + +
Nigeria o o o + + +
Norway ++ + + + ++ + + + + + + + +
0man o o
Pakistan o o + + + + + + + + +
Peru o o + + + + + + + + + +
Philippines
Poland ++ + + + +
+ + + + + + + + +
Portugal o o + + +
+ + + + + + + + +
Romania ++ + + + +
+ + + + + + + + +
GUS/Russ.Fed ++ + + • + + +
+ + + • + + +
Saudi Arabia o
+ o oo + + + + +
Serbia o + + o +
Singapore ++ + + + ++ + + + + + + + +
Slovakia ++ + + + ++ + + + + + + + +
Slovenia ++ + + + ++ + + + + + + + +
South Africa o
Spain ++ + + + ++ + + + + + + + +
 Country 0 0 0 0 0 0 0 0 0 0 1 1 1 1 1
Year  0 1 2 3 4 5 6 7 8 9 0 1 2 3 4
145
Year  6 6 7 7 7 7 7 7 7 7 7 8 8 8 8 8 8 8 8 8 8 9 9 9 9 9 9 9 9 9 9
Country  8 9 0 2 3 4 5 6 7 8 9 0 1 2 3 4 5 6 7 8 9 0 1 2 3 4 5 6 7 8 9
Sweden + + + + + + + + • + + + + + + + + + + + + + + + + +
Switzerland o + + + + + + + + + + + + +
Syria
Tajikistan
Thailand o + + + + + + + + + +
Turkey o + o + + + + + +
Turkmenistan o
UdSSR + • + + + + + + • + + + + + + + + + +
Ukraine + + + + + +
United Kingdom o o + + + + + + + + + + + + + + + + +
United States o o + + + + + + + + • + + + + + + +
Uruguay o o +
Uzbekistan
Venezuela o o + + + + + + +
Vietnam + + + +
 Country 6 6 7 7 7 7 7 7 7 7 7 8 8 8 8 8 8 8 8 8 8 9 9 9 9 9 9 9 9 9 9
Year  8 9 0 2 3 4 5 6 7 8 9 0 1 2 3 4 5 6 7 8 9 0 1 2 3 4 5 6 7 8 9
146
Year  0 0 0 0 0 0 0 0 0 0 1 1 1 1 1
Country  0 1 2 3 4 5 6 7 8 9 0 1 2 3 4
Sweden + + + + + ++ + + + + + + + +
Switzerland + + + + + ++ + + + + + + + +
Syria o o + + + + +
Tajikistan o o + ++ + + + + + + +
Thailand + + + + + ++ + + + + + + + +
Turkey + + + + + ++ + + + + • + + +
Turkmenistan o o + + + + + + + + + + + +
UdSSR
Ukraine + + + + + ++ + + + + + + + +
United Kingdom + + + + + ++ + + • + + + + +
United States + + + + + ++ + + + + + • + +
Uruguay + + + + + ++ + + + + + + + +
Uzbekistan o o + +
Venezuela + + + + + + + + + + + + + +
Vietnam + + + + + + + + + + + + + + •
 Country 0 0 0 0 0 0 0 0 0 0 1 1 1 1 1
Year  0 1 2 3 4 5 6 7 8 9 0 1 2 3 4
147
About the history of the IChO
Inofficial ranking since 1974

(set up by adding the points of the teams. up to position 50)
1974 1975 1976 1977 1978 1979 1980 1981 1982 1983 1984 1985 1986
1987 1988
IChO held in RO H DDR CS PL SU A BG S RO D CS NL H FIN
1 SU SU DDR CS SU PL PL H CS RO D SU NL SU RC
. RO H SU SU PL SU D CS D SU CS CS PL RC D
. CS PL H H D RO DDR PL PL D SU D D RO USA
. H BG PL PL DDR CS H BG NL CS H A SU CS PL
5 PL RO A S CS A A A A H A NL A D GB
. DDR DDR RO A H S RO D SU A GB H USA F DDR
. BG S BG D A H BG DDR H F PL DDR H GB N
. YU CS CS DDR RO D CS RO BG DDR USA PL BG PL RO
. S A S RO S BG S SU DDR PL RO USA F H H
10 D* D D BG BG FIN FIN NL S NL DK F RODDR SU
. YU YU YU TR DDR NL FIN F BG S GB CS NL I
. B B B FIN I S FIN GB NL RO GBUSA NL
. B F N N FIN BG S BG BG
. I RO DK F N DDR A CS
15 * hors concourse DK FIN BG S CDN S AUS
. YU S N FIN N FIN SGP
. I I I YU DK N F
. YU GR B B DK A
. YU GR FIN I FIN
20 B DK GR GR CDN
. C KWT C DK
. YU B C
. YU S
. CDN B
25 CH CH
. KWT KWT
(List of abbreviations see 152)
148
1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000
IChO held in DDR F PL USA I N RC RUS CDN AUS T DK
1 DDR RC RC RC RC RC RC IR H SGP USA RC
. D PL RO H TPE GB IR RC D USA ROK RUS
. RC D H PL USA USA RO RUS TR ROK RC USA
. BG USA PL USA I A A A TPE RC IR H
5 SU CS NL A GUS SGP D D IR H RO TPE
. H RO USA GUS H ROK GB USA RUS RA H A
. PL F I D D TPE SK UA ROK RUS TPE SK
. RO A D RO CDN CZ TPE CZ RC AUS UA BY
. CS DDR N F SGP GUS I H SGP D PL VN
10 I H GB I CZ IR CZ RO PL GB AUS TR
. NL GB CS SGP A D RUS GB USA PL VN SGP
. GB I SU CS RO H H TPE UA A D D
. A AUS A AUS P RO AUS BY AUS RO RA ROK
. USA SGP AUS NL NZ DK SGP SGP CDN TPE BY IR
15 S NL DK DK ROK I F RA RO SK T CZ
. F N SGP ROK LV T TR TR A NL F FIN
. N DK CDN GB IR NZ PL F T IR TR T
. AUS T BG CH DK UA USA I EST UA SGP MEX
. CDN FIN F T AUS AUS DK AUS CZ VN IND GB
20 DK CDN S LV NL F RA ROK VN LT GB AUS
. FIN BG T NZ LT PL ROK EST F TR RUS IND
. B C CH S SK NL UA CDN S BY MEX CDN
. C S LV LT F SK LT T BY F A RA
. GR CH LT N C CDN T VN NZ I IRL UA
25 CH B FIN CDN GB LT NL SK LV T NZ PL
. KWT GR C SLO T S CH CH RA FIN I NZ
. KWT GR BG BG N BG NL SLO CZ CDN BG
. CY B TPE B BG S NZ GB CDN LT F
. CY B S FIN NZ DK SK S NL DK
30 SLO FIN FIN EST EST PL LT BG SK NL
. GR SLO LV CDN SLO I N BG B
. CY GR CH MEX MEX DK MEX KZ RO
. MEX MEX MEX N LV NL CH DK KZ
. N SLO SLO N IRL SLO CH LT
35 CH B LV CY N EST CZ CH
. YV CY CY BG MEX CY FIN SLO
. CY GR B S CH LV B EST
. KWT TR GR LT CY DK S S
. YV FIN E E NZ CY YV
40 C YV B FIN GR EST CY
. KWT KWT GR BG KZ LV HR
. C FIN YV E SLO I
. YV GR IRL YV RI
. C B B BR N
45 KWT RI KS E AZ
. KWT YV N IRL
. C RI RI E
. GR LV
. ROU GR
50 C BR
149
2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012
IChO held in IND NL GR D TPE ROK RUS H GB J TR USA
1 RC RC RC RC ROK RC RC RC TPE RC RC TPE
. ROK T IR ROK VN TPE RUS RUS RC T ROK ROK
. USA TPE ROK RUS IR ROK TPE UA ROK ROK RUS RUS
. RUS ROK T UA RUS RUS PL ROK RUS J RI IND
5 IR A BY D AZ VN ROK T SGP TPE USA RC
. TR UA RUS PL TPE T D BY J H T SGP
. IND USA IND TPE T J T VN USA CZ SGP J
. AUS PL SGP H RA Pl IND TPE H SGP CDN D
. TPE IND D TR D IND H H IR USA H H
10 T D TPE VN IND D SK SGP GB IR IR UA
. SGP IR UA IND A SK LT KZ RO RUS TR RI
. PL H PL IR CZ DK USA A T TR IND USA
. RO RUS CDN RO UA SGP VN PL D LT CZ BY
. F CDN CZ LT PL BR GB IR IND D F VN
15 SK TR RO CZ AUS CDN BY IND PL PL J RO
. H AUS KZ USA TR AZ EST RO AUS GB TPE LIT
. VN GB VN SGP H UA UA AUS A IND D CZ
. CZ SGP EST CDN SK USA RI D BY RI SK KZ
. RA E GB AZ USA H IR SK VN RO KZ RA
20 BY SK AUS AUS GB CZ RO TR F A AUS PL
. C BY H KZ RO AUS AUS LT RI VN VN SK
. D VN SK GB BY IRL A EST TR SK RO IR
. GB FIN USA J SGP F KZ I LT CDN GB A
. UA F YV A J IR SGP GB UA EST BY GB
25 A LT IND BY RI A NZ CDN EST AUS PL AUS
. MEX CZ F SK LV TR CZ NZ CZ UA A IL
. DK KZ A T BG RI F BR SK F LT HR
. CDN LV I RA HR GB TR USA CDN RA EST BR
. EST NL TR EST MEX RO J LV I NZ RA CDN
30 RI RO AZ F KZ NL ARM RI RA BY UA NZ
. HR RA MEX NZ LT HR SLO F NZ KZ FIN TR
. I EST LT SLO F LT RA CZ TM BR SLO EST
. N HR NL HR EST KZ BR J MEX IL I LV
. BG BG FIN LV CDN SLO CDN DK KZ HR BR F
35 CY NZ HR NL I EST I RA IL SLO HR ARM
. KZ I J I DK RA MAL MEX BR FIN NZ I
. B DK DK CH SLO BR IL SLO HR DK TM NL
. LT SLO RA FIN FIN TJ IRL IL AZ NL LV TM
. NZ N GR RI NL LV NL AZ DK E S DK
40 CH YV LT S IRL MAL CH HR S I NL TJ
. E MEX E BG GR S S TM LV LV PE YVA
. FIN BR TM KS NZ IRL LV BG IRL BG PK BG
. SLO S BR E KS IL DK MGL FIN CR TJ SLO
. NL RI BG GR S FIN MD IRL N CH E CH
45 LV TM CH BR B IS E MAL E IRL MEX FIN
. BR B NZ TM BR I BG E NL MEX CH MEX
. S IRL IS CY CH CY TM S MGL MGL MGL MGL
. YV CH IRL YVA P N HR NL PE MAL IL T
. IRL C CY IRL IS TM PK CH PK N CY PK
50 GR CY KS IS N CH N ROU SLO S BG AZ
150
2013 2014 2015 2016 2017 2018 2019 2020 2021 2022 2023 2024
IChO held in RUS VN
1 RC SGP
. ROK UA
. TPE RUS
. USA VN
5 H TPE
. SGP RC
. RUS USA
. PL TR
. UA RO
10 IND T
. VN IR
. T PL
. BY ROK
. J RI
15 KZ J
. IR BY
. SK GB
. CZ D
. RI LT
20 D IND
. RO SK
. A CZ
. LIT H
. AUS AUS
25 GB UZ
. TR CDN
. NZ SRB
. HR RA
. F MEX
30 DK A
. MD NZ
. CDN EST
. LV KZ
. SLO MAL
35 RA KSA
. SRB HR
. BR DK
. EST BR
. UZ NL
40 AZ PK
. I F
. E I
. IL BG
. CY E
45 N SLO
. ARM TM
. PK LV
. CH CH
. BG PE
50 TJ N
151
List of abbreviations
A Austria LV Latvia
ARM Armenia LT Lithuania
AUS Australia MAL Malaysia
AZ Azerbaijan MD Moldova
B Belgium MEX Mexico
BG Bulgaria MGL Mongolia
BR Brazil N Norway
BY Belarus NL Netherlands
C Cuba NZ New Zealand
CDN Canada P Portugal
CH Switzerland PE Peru
CS Czechoslovakia PK Pakistan
CY Cyprus Republic PL Poland
CZ Czech Republic RA Argentina
D Germany RI Indonesia
DDR German Democratic Republic RC China
DK Denmark RO Romania
E Spain ROK South Korea
EAK Kenya ROU Uruguay
EST Estonia RUS Russian Federation
ET Egypt S Sweden
F France SGP Singapore
FIN Finland SK Slovakia
GB United Kingdom SLO Slovenia
GR Greece SRB Serbia
GUS Commonwealth of Independent States SU Soviet Union
H Hungary T Thailand
HR Croatia TJ Tadzhikistan
I Italy TM Turkmenistan
IL Israel TPE Chinese Taipei
IND India TR Turkey
IR Iran UA Ukraine
IRL Ireland USA United States of America
IS Iceland UZ Uzbekistan
J Japan VN Vietnam
KS Kyrgyzstan WAN Nigeria
KSA Saudi Arabia YU Yugoslavia
KWT Kuwait YV Venezuela
KZ Kazakhstan
152

German Problems 2014

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46.

To become a member of the German IChO-team you have to be successful in

In the appendix you find tables of historical interest.

Part 1: The problems of the four rounds

Part 2: The solutions to the problems of the four rounds

Part 3: The problems of the IChO

IPN University of Kiel, z.H. PD Dr. Sabine Nick tel: +49-431-880-3116

IPN University of Kiel, z.H. Monika Barfknecht tel: +49-431-880-3168

Wolfgang Hampe tel: +49-431-79433

Association to promote the IChO

The problem set of the four rounds

Problem 1-1 Chemistry and Horses

c) Determine the empirical formula of B.

Nitrogen 7.816 /100 Carbon 60.742 /100

Problem 1-2 Redox Reactions

b) Which of the following equations represent a redox reaction?

i) HCl + H2O H3O+ + Cl–

ii) Cl2 + 2 HI I2 + 2 HCl

iii) 2 Al + AlCl3 3 AlCl

iv) Cr2O72– + H2O 2 HCrO4–

v) [Fe(H2O)6]3+ + 3 SCN– [Fe(H2O)3(SCN)3] + 3 H2O

vi) Cr2O72– + 4 H2O2 + 2 H+ 2 CrO(O2)2 + 5 H2O

vii) [Ti(OH)2(H2O)4]2+ + H2O2 [Ti(O2) · aq]2+ + 6 H2O

Reduced form Oxidized Form E° [V]

i) Granulates of zinc are given into diluted hydrochloric acid:

ii) Splinters of copper are given into diluted hydrochloric acid:

iii) A solution of iron(III) ions is mixed with a solution of potassium iodide:

Problem 1-3 Thermal Degradation of a Compound

nal existing mass)

b) Which information about the thermal reactivity (behavior at heating) of X provides

i) the TG curve concerning the loss of mass,

Problem 1-4 An Organic Riddle

a) Draw the line-bond structures of A, B, E, F and G!

b) Propose a mechanism for the reaction of C to D.

F reacts with t-butyl acetate under cleavage of t-butanol to form H.

c) Draw the line-bond structure of H and write down its name.

d) Which is the natural source of H?

Second Round (homework)

Problem 2–1 An Inorganic Riddle

Compound A forms white, non-hygroskopic crystals. A can be obtained by oxidation of

An aqueous solution of compound C shows the following reactions:

a) Determine the molecular formulae of the compounds A, B and C.

d) What do you expect compound X to be, diamagnetic or paramagnetic? Account for

Problem 2-2 An Organic Synthesis

p-TsOH: H3C SO3H

 K contains at least one carbon ring.

 A is an unbranched dicarboxylic acid.

a) Determine the structural formulae of A through K!

(Hint: in front of the paper plane behind the paper plane)

i) B  C ii) C  D iii) G  H iv) I  J

e) In the reaction of I with sodium ethanolate to form J several constitutional isomers

Linear molecules z=3N–5

Example CO2 symmetric stretch

S-(–)-limonene? Fig. 1: S-(–)-Limonene

The assignment of the vibrations to the different conformers is conducted by quantum

Fig. 2: Conformers of S-(–)-limonene: equatorial conformer A and axial conformer B.

h) If the ratio of intensities (i(A):i(B)) is 7:1, what is the expansion temperature?

Fig. 3: Possible dimers of acetone

The symmetry of a molecule is important for spectroscopy because it gives information

Test 1 Göttingen 2014: Problems 3-01 to 3-10