The International

Virtual Chemistry Olympiad

IVChO 2021
First edition (April 23, 2021)
Preface
This paper is the result of a collaboration between 8 people from 5 different countries gathered
on the same Discord Server. It was created in the spirit of making a challenging Chemistry
Olympiad paper, whilst also keeping in mind that each problem was to be entertaining and
educating in its specific topic. All problems were designed after the following three guidelines:

1. The problems should be interesting

2. The reader should finish the problem having learnt something
3. The problem should be challenging

Each author has represented their individual country at the International Chemistry Olympiad
(IChO), or studies chemistry at graduate level.
This paper is not meant to be timed and includes questions to challenge people at every level,
whether they have achieved an international gold medal in chemistry or are currently training
to be selected to represent their country. The set contains 15 questions spread on the topics
Physical, Organic, Inorganic, Polymers and Biochemistry as well as Analytical Chemistry. We
hope that you will use this paper to explore new horizons in chemistry and cultivate your
creativity. The editors team and task authors wish that you will enjoy the problems. Good
luck!

Contributing Authors

Name Country Discord

Stabell Denmark Stabell#6680
Thombrom Denmark Thombrom#1771
doubleone44 Netherlands doubleone44#3565
Edward USA Idontknoweither#0886
Maestron Israel Maestron#6831
Tomasz Poland Tomasz#4849
apc1234567 USA apc1234567#2989
Vish USA Vish#7047

Edited in LATEX by: Tomasz & Stabell & Thombrom & Maestron
Logo made by: Thombrom

Page 1 of 48
CONTENTS

Contents
1 Physical Chemistry 3
Problem 1: Role of kinetics in determination of mechanism . . . . . . . . . . . . . 4
Problem 2: Fun with Particles in Boxes . . . . . . . . . . . . . . . . . . . . . . . 6
Problem 3: Ozone is no laughing matter . . . . . . . . . . . . . . . . . . . . . . . 14

2 Organic Chemistry 16
Problem 4: Asymmetric Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Problem 5: Indinavir . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Problem 6: The Secret Clownzhu Property . . . . . . . . . . . . . . . . . . . . . 23
Problem 7: Stereoisomer Enumeration and Burnside’s Lemma . . . . . . . . . . . 27
Problem 8: Mysterious Rearrangement . . . . . . . . . . . . . . . . . . . . . . . . 32

3 Inorganic Chemistry 33
Problem 9: Hot atom inorganic synthesis . . . . . . . . . . . . . . . . . . . . . . 34
Problem 10: A Quick Determination of Bidentate Ligands . . . . . . . . . . . . . 36
Problem 11: Minerals, bioceramics, fireworks, flares and ignis fatuus . . . . . . . . 39
Problem 12: Short and Challenging Inorganic Puzzles . . . . . . . . . . . . . . . . 42

4 Polymers and Biochemistry 43

Problem 13: Organic and inorganic polymers . . . . . . . . . . . . . . . . . . . . 44

5 Analytical Chemistry 46
Problem 14: Alloy composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47

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1 PHYSICAL CHEMISTRY

Physical Chemistry

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1 PHYSICAL CHEMISTRY

Question 1 2 3 4 5 6 Total
Theoretical
Points 2 1 8 8 4 12 35
Problem 1
Score

Problem 1: Role of kinetics in determination of mechanism

Author: Tomasz, Poland
Remark. In this problem order of production of X with respect to Y is equal to n if rate of
formation of X is equal to A[Y]n where A does not depend on [Y] (but it can depend on
reaction conditions or concentrations of other reactants).
In this problem we will explore pyrolysis of acetaldehyde. This reaction sparked interest of
physical chemists as orders of production of some products are fractional. We will investigate
how this information may help to understand mechanisms and elementary processes involved.
It is known that there are six main elementary processes proceeding when pure acetaldehyde
is heated to around 500 °C:

CH3 CHO −−→ CH3 + CH3 CO (1)

CHO −−→ CO + H (2)
H + CH3 CHO −−→ H2 + CH3 CO (3)
CH3 + CH3 CHO −−→ CH4 + CH3 CO (4)
CH3 CO −−→ CH3 + CO (5)
2 CH3 −−→ C 2H6 (6)

During all experiments considered concentration of acetaldehyde was kept constant.

It is known that there are 2 main products of pyrolysis.

1) Determine main products of pyrolysis.

2) Indicate which reaction(s) correspond to initiation, propagation and termination.

Analytical solution of system of differential equations arising from aforementioned mechanism

does not exist. However, steady state approximation can be used to significantly simplify
underlying equations.

3) Write down all equations that can be inferred from steady state approximation. Indicate,
which equation corresponds to which reactant.

4) Using equations from previous point, determine orders of formation of (non radical)
side products with respect to acetaldehyde.

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1 PHYSICAL CHEMISTRY

Experimental data show that both main products are formed with order 3
2 (with respect to
acetaldehyde).

5) Using this information show that reaction (4) is much faster than reaction (1).

One of side products of acetaldehyde pyrolysis not included in presented mechanism is ace-
tone. You may assume that acetone is produced in only one elementary process (7) which shall
be included in mechanism (1)–(6). Reaction (7) is much slower than reactions (1)–(6), so
you may assume that introduction of (7) does not alter balance in steady state approximation.
Experimental evidence indicate that acetone production order with respect to acetaldehyde
is 23 .

6) Using all information inferred from previous parts of problem, determine possible mech-
anism of formation of acetone (reaction (7)). Consider all cases and exclude ones that
contradict information given.

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1 PHYSICAL CHEMISTRY

Question 1 2 3 4 5 6 7 8 9 10 Total
Theoretical
Points 5 5 5 5 5 5 12 5 5 5
Problem 2
Score
Question 11 12 13 14 15 16 17 18 19 20
Points 8 3 3 15 5 5 8 6 6 6
Score
Question 21 22 23 24 25 26 27 28 29 30
Points 3 3 3 9 9 3 9 9 3 8 181
Score

Problem 2: Fun with Particles in Boxes

Author: Idontknoweither, USA
Introduction
In this problem we will explore variations of the Particle in a Box. We will first start with an
introduction of basic concepts from quantum mechanics, and then look at the standard 1D
particle in a box, a 3D box, and a 1D box with a finite potential.
The following may be helpful:

• Time-Independent Schrodinger’s Equation in one dimension:

~2 ∂ 2
− ψ(x) + V (x)ψ(x) = Eψ(x)
2m ∂x 2
• Time-Dependent Schrodinger’s Equation in one dimension:

~2 ∂ 2 ∂ψ(x,t)
− 2
ψ(x,t) + V (x)ψ(x,t) = i ~
2m ∂x ∂t
• Time-Independent Schrodinger’s Equation in three dimensions:

~2
Å 2
∂2 ∂2
ã
∂
− + + ψ(x,y ,z) + V (x,y ,z)ψ(x,y ,z) = Eψ(x,y ,z)
2m ∂x 2 ∂y 2 ∂z 2
• Solutions to Second Order Linear Differential Equations:

y 00 + k 2 y = 0 =⇒ y = c1 sin(kx) + c2 cos(kx)

y 00 − k 2 y = 0 =⇒ y = c1 e −kx + c2 e kx

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1 PHYSICAL CHEMISTRY

Background on Quantum Mechanics

One postulate of quantum mechanics is that the state of a quantum system is completely
determined by its wavefunction ψ(x,t). In addition, this wavefunction ψ(x,t) must satisfy
the Time-Dependent Schrodinger Equation (TDSE).

1) If ψ(x) is a solution to Time-Independent Schrodinger Equation, we can derive that

ψ(x,t) = ψ(x)e −iEt/~ is a valid solution to the TDSE through separation of variables.
Verify that ψ(x,t) does indeed satisfy TDSE.

We call the solutions ψ(x) to the TISE stationary states, since they do not change with
time.

2) Suppose that we have stationary states ψn (x) with energies En . Show that the function

cn ψn (x)e −iEn t/~

X
Ψ(x,t) =

also satisfies the TDSE.

As shown above, sums of solutions (also called superpositions) to the TDSE remain solutions
to the TDSE, and so we can add any combination of stationary states to make valid quantum
states. Thus, finding the stationary states is critical to solving TDSE.
Let us now see how we can find properties of a quantum system. A postulate of quantum
mechanics is that each classical observable variable, for example, position or momentum,
corresponds to a linear Hermitian operator [These terms are defined below].
We will additionally define an inner product of wavefunctions as follows:
Z ∞
hψ1 , ψ2 i = ψ1∗ (x)ψ2 (x) dx
−∞

where ψ ∗ refers to the complex conjugate of ψ.

Definition 1.1
An operator is a function that takes in a function as an input and returns another function
as output. For example, dxd
is an operator. Likewise, multiplying a function by x is also
an operator.
An operator Ô is Hermitian if it satisfies hψ1 ,Ôψ2 i = hÔψ1 , ψ2 i∗ for all functions ψ1 , ψ2 .
An operator Ô is Linear if it satisfies Ô(ψ1 + ψ2 ) = Ôψ1 + Ôψ2 and Ô(cψ1 ) = c Ôψ1 .

3) Show that dx
d
is not Hermitian.
Hint: Consider suitable functions on which the definition of Hermicity fails.

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Claim 1.2
The quantum analogs of some classical operators are as follows:

• The position operator is simply to multiply by the position. x̂ = x.

• The momentum operator is defined as pˆx = −i ~ ∂x ∂
.
• The energy operator is the left side of the Schrodinger equations, and is known as
∂2
the Hamiltonian. In one dimension, the Hamiltonian is Ĥ = − ∂x 2 + V (x).

Now let’s look at the interaction between operators, functions, and measurement.
Definition 1.3
If applying an operator Ô to a function ψ results in the same function ψ multiplied by a
constant, then we call the function ψ an eigenfunction of Ô and we call the associated
constant its eigenvalue. Each operator has a set of eigenvalues associated with it.

Example 2.4
The function ψ = e 5x is an eigenfunction of the operator Ô = d
dx , since Ôψ = 5ψ. The
corresponding eigenvalue is 5.

d2
4) Show that sin x, cos x, e x , e ix are all eigenfunctions of the operator Ô = dx 2 , and find
their corresponding eigenvalues.

To measure a property of a quantum system Ψ(x,t), first write Ψ(x,t) as a superposition of

eigenfunctions of that operator. The measurement will then result in one of the eigenvalues,
and will also change that quantum system’s wavefunction to be exactly equal to the eigen-
function which was measured (known as collapsing the wavefunction). The probability of
each output eigenvalue is proportional to the square of the magnitude of the coefficient of
the corresponding eigenfunction. Note that coefficients can be complex numbers as well.

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1 PHYSICAL CHEMISTRY

Example 2.5
Suppose that we have a wavefunction Ψ(x) = sin(kx) and we want to measure its
momentum.
First, we want to find momentum eigenfunctions (with eigenvalue p). These are functions
which satisfy the following:
∂ψ
−i ~ = pˆx ψ = pψ
∂x
This is a first order differential equation with solutions ψ = e ipx/~ for some p.
Then, we can write Ψ as a superposition of momentum eigenstates. We have that

e ikx − e −ikx 1 1
sin(kx) = = e i(k~)x/~ − e i(−k~)x/~
2 2 2
so Ψ is the sum of two momentum eigenstates with eigenvalues ±k~. The squares of
the magnitudes of the coefficients in front of the functions are equal, so we conclude
that measuring the momentum of this quantum state will result in k~ or −k~ with equal
probability.

When we solved the equation for momentum eigenstates, note that we omitted the constant
that the solution is multiplied by (the mathematical solution is ψ = Ce ipx/~ for any constant
C). In fact, we can generally ignore coefficients if we work with one specific solution (in a
superposition, the ratios between coefficients of different states matter, so we can’t drop
constants liberally there). The underlying quantum system not dependant on the coefficient,
since the eigenvalues of the system don’t change. Usually, we choose coefficients such that
the wavefunctions are normalized, or that hψ, ψi = 1.
Some complicated math tells us that we can choose eigenfunctions ψi to be linearly inde-
pendent functions such that hψi , ψj i = 0 if i 6= j and hψi ,ψi i = 1, for all i,j. This set of
eigenfunctions is known as a orthonormal basis, and are generally easier to work with.

5) Suppose we have a wavefunction Ψ(x,0) as a superposition of orthonormal eigenfunc-

tions: X
Ψ(x,0) = cn ψn (x)
Show that |cn |2 = 1 if and only if hΨ,Ψi = 1 (i.e. Ψ is normalized). This means that
P

during measurement of Ψ, each eigenvalue is chosen with probability exactly equal to

|cn |2 .

For the remainder of this problem we will generally assume that wavefunctions are normal-
ized.

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Claim 1.6
From the TISE, we note the following helpful properties for wavefunctions ψ:

• ψ must be continuous everywhere.

• ψ 0 must also be continuous everywhere, unless the potential V (x) abruptly changes
to ∞.
• ψ must be equal to 0 where the potential V (x) is infinite.

Finally, another helpful way to look at results of measurements is to look at their expected
value. We can find the expected value without expanding our wavefunction as a superposi-
tion.
Definition 1.7
We define the expectation value of a Hermitian operator Ô on a wavefunction ψ as

hÔiψ = hψ, Ôψi

6) Show that this definition of expectation value is consistent with the standard definition
and the probabilistic interpretation defined above, assuming an orthonormal basis of
eigenfunctions.
The Standard Particle in a Box
The standard particle in a 1D Box is defined by the potential
(
0 0≤x ≤a
V (x) =
∞ x 6∈ [0,a]

7) Find ALL eigenfunctions and eigenvalues of the Hamiltonian in this potential

» (i.e. solve

TISE in this potential). Show that the normalized eigenfunctions are ψn = 2a sin nπx
a
2 2 2
on [0,a] and 0 elsewhere, with energies En = ~2maπ n
2 .

Hint: Write the Schrodinger equation inside the box to find the general form of the
wavefunction inside the box. Continuity of the wavefunction at the boundary will allow
you to directly find the constants resulting from the Schrodinger equation.

8) Show that the eigenfunctions found above are orthonormal.

9) Show, using integration, that the average position of the particle is always in the middle
of the box. In other words, show that
L
hx̂i =
2
for all eigenfunctions. Does this mean that hx̂i = L
2 for all superpositions of particle in
a box eigenfunctions as well?

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1 PHYSICAL CHEMISTRY

10) Solely based on the form of the momentum operator p̂, explain why hp̂i = 0 for all
particle in a box wavefunctions. Confirm this with integration.

11) Define xˆ2 = x̂ x̂ and similarly for pˆ2 . Find hxˆ2 i and hpˆ2 i for the lowest-energy state
(ground state) of the particle in a box.
»
12) Heisenberg’s Uncertainty Principle says that ∆x∆p ≥ ~2 , where ∆x = hxˆ2 i − hx̂i2
and similarly for p. Show that this principle is satisfied for the ground state.

13) An energy measurement is taken on Ψ(x,0) = 12 ψ1 + 21 ψ2 + √12 ψ3 . What are the possible
outcomes of the measurement, and what are the probabilities of each outcome?

14) An energy measurement is taken on

(
Ax(a − x) x ∈ [0,a]
Ψ=
0 x 6∈ [0,a]

where A is a constant you must determine for wavefunction normalization. What are
the possible outcomes of the measurement, and what are the probabilities of each
outcome?
Hint: Ψ is a superposition of infinitely many eigenfunctions. To find the corresponding
coefficients of the wavefunctions, write Ψ as follows:
…
X 2  nπx 
Ψ= cn sin
a a
Then, multiply both sides by sin kπx


a and integrate from 0 to a. All the terms on the
right should cancel out except for the term where k = n, allowing you to find each
individual cn .

In the previous problem, we looked at a wavefunction that was not an eigenfunction. We can
calculate the expected value of the Hamiltonian as hĤiΨ as usual. This energy will be greater
than the ground state energy we calculated earlier, which is summarized in the Variational
Principle:
Theorem 1.8 (Variational Principle)
Let Egs be the energy of the ground state. Then, for any wavefunction Ψ, We have that
Z ∞
hĤiΨ = Ψ∗ ĤΨ dx ≥ Egs .
−∞

15) Prove the Variational Principle (assuming an orthonormal basis).

2
16) Show that the average energy of the wavefunction above is 5 ma
~
2 . Prove that this is not

less than the ground state energy, by using π = g = 10.

2

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1 PHYSICAL CHEMISTRY

π6
17) Using the fact that |cn |2 = 1, show the purely mathematical fact that
P P∞ 1
n=1 n6 = 945 .

A 3D Particle in a Box
Now let’s move into the third dimension. We will still deal with a similar potential, but now
we will work in 3 dimensions:
(
0 (x,y ,z) ∈ ([0,a],[0,b],[0,c])
V (x,y ,z) =
∞ elsewhere

18) One way to solve the TISE here is to write Ψ = ψ1 (x)ψ2 (y )ψ3 (z). With this substi-
tution, show that ψ1 ,ψ2 ,ψ3 each individually have to satisfy the 1D particle in a box
Schrodinger equation.
»
19) Verify that ψn1 n2 n3 = abc
8
sin n1aπx sin n2bπx sin n3cπz is an energy eigenfunction in

this potential. Show that this wavefunction satisfies hψ,ψi = 1 and that it is continuous
everywhere. What is the associated energy eigenvalue?
Particle in a Finite Box
We will now investigate a particle in a finite box, where the potential doesn’t go to infinity at
the ends. This will be defined slightly differently than before such that the potential is now
even: (
−V0 −a ≤ x ≤ a
V (x) =
0 x 6∈ [−a,a]

20) Show that inside the box, the wavefunction ψ must satisfy ψ = A cos kx + B sin kx,
and that outside the box, the wavefunction ψ must satisfy ψ = Ce −κx + De κx for some
constants A,B,C,D. Determine k and κ in terms of the known parameters a, m, E, V0 .

21) Argue, on grounds of feasibility, that D = 0 for the right side of the wavefunction
outside the box, and that C = 0 on the left side of the wavefunction.

Let’s now move to unitless parameters before going into exact solutions. Define η = ka and
2
ξ = κa, such that η and ξ essentially serve as proxies for k and κ. Further, define z02 = 2mV 0a
~2 ,
so that z0 serves as a proxy for the depth of the well.

22) Show that η 2 +ξ2 = z02 . Express the energy of the system in terms of known parameters
(including z0 ), as well as η and ξ.

We will investigate the even solutions first, and then the odd solutions.

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1 PHYSICAL CHEMISTRY

23) Argue that the even solutions must have the following form:

κx
Ce
 x < −a
ψ = A cos kx x ∈ [−a,a]

 −κx
Ce x >a

24) Use the fact that the wavefunction and its derivative must be continuous at a and −a
to show that ξ = η tan η will be a valid even solution to this problem.

25) Sketch a graph of the two defining equations η 2 + ξ2 = z02 and ξ = η tan η in the
first quadrant for representative z0 . Use this graph to determine the number of even
solutions in the finite box for z0 = 3π
2 .

Now let’s tackle the odd solutions.

26) Argue that the odd solutions must have the following form:

κx
−Ce
 x < −a
ψ = A sin kx x ∈ [−a,a]

 −κx
Ce x >a

27) Use the fact that the wavefunction and its derivative must be continuous at a and −a
to show that ξ = −η cot η will be a valid odd solution to this problem.

28) Sketch a graph of the two defining equations η 2 + ξ2 = z02 and ξ = −η cot η in the first
quadrant for representative z0 . What is the minimum value of z0 such that the finite
well will have an odd solution?

The union of the even and odd solutions represents a full set of solutions to this problem.

29) Argue that when the solutions are ordered in terms of energy, they alternate even/odd.

30) Sketch the 4 lowest energy wavefunctions in the finite well, assuming that z0 is suffi-
ciently large to admit these solutions.

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Question 1 2 3 4 5 6 Total
Theoretical
Points 5 5 5 5 5 5 35
Problem 3
Score

Problem 3: Ozone is no laughing matter

Author: doubleone44 (Netherlands), Vish (USA)
N2 O, commonly known as laughing gas is known to mediate the formation of ozone in the
lower troposphere. We’re given the following mechanism:

N2 O + O 2 → N 2 O 3 k1
N2 O3 + ∆ → NO2 + NO k2
NO2 + hv → NO + O k3
O + O 2 → O3 k4

1) Find the rate for the production of ozone due to N2 O

2) In terms of the rate constants presented (k1 , k2 , k3 , k4 ), find an expression for kobs1
(Hint: Not all rate constants need to be used)

N2 O is also known to mediate the decomposition of ozone into oxygen as well with the help
of an alkyl catalyst. We give the following mechanism:

N2 O + O3 → N2 O4 k5
N2 O4 + R → 2 NO + RO2 k6
RO2 + NO → RO + NO2 k7
RO + hv → R + O k8
NO2 + hv → NO + O k9
O + O 3 → 2 O2 k10

3) Assuming steady state equilibrium for N2 O4 , NO2 and O to be of low constant concen-
tration, find the rate for the production of oxygen

4) In terms of all rate constants presented in (k5 − k10 ), find an expression for kobs2 (Hint:
Not all rate constants need to be used)

Often the concentrations of O3 and O2 are present at much larger concentrations than N2 O
in the atmosphere.

5) Given this information, which of the following graphs, when plotted against time, is
linear

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1 PHYSICAL CHEMISTRY

• A. arcsin([N2 O])
• B. arctan([N2 O])
• C. arccos([N2 O])
• D. ln([N2 O])

6) To what order is the half life dependent on [N2 O]?

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2 ORGANIC CHEMISTRY

Organic Chemistry

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2 ORGANIC CHEMISTRY

Question 1 2 3 4 5 Total
Theoretical
Points 5 11 1 8 16 41
Problem 4
Score

Problem 4: Asymmetric Synthesis

Author: Maestron, Israel
“How would you like to live in Looking-glass House, Kitty? I wonder
if they’d give you milk in there? Perhaps looking-glass milk isn’t good
to drink. . . ” Lewis Carroll, Through the looking-glass and what Alice
found there, Macmillan, 1872.
Nature is asymmetric: some flowers, like that in the picture,
are characterized with a spiral structure that spins in only one
direction; many natural molecules, like carbohydrates and amino
acids, have common configurations. In fact, you are probably
using either your right or left hand to solve this problem (un-
less you are ambidextrous). Indeed, nature is the largest re-
source of enantiomerically pure molecules (often referred to as chi-
ral pool), from which asymmetric syntheses begin. In this prob-
lem you will investigate techniques in asymmetric synthesis and will
see them in action by completing the total syntheses of two natural
molecules.

An important strategy in asymmetric synthesis is the use of chiral auxiliary, which is an

enantiomerically pure compound that can be attached to a starting compound in order to run
a diastereselective reaction. Because of the enantiomeric purity of the chiral auxiliary, the
reaction results in only one enantiomer. The chiral auxiliary can then be removed to obtain
the target molecule.

1) Corey’s chiral auxiliary was used in the synthesis of prostaglandin PGF2α. PGs are
important chemical messengers that regulate many physiological activities, such as
blood circulation, blood pressure, growth, sleep, and more. Draw the 3D representation
of compounds A and B. Explain why only one enantiomer of B is obtained.

2) Find the structural formulas of compounds C–M. Designate the stereochemistry in your
answers.

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oxidative cleavage 1)H2 O2 , OH –

Et3 N
A AlCl3
B C 2)KI3
D

Ac2 O

CrO3 · 2 Py H2 , Pd/C n-Bu3 SnH, AIBN

I NaH
H G F PhH
E

Zn(BH4 )2

K2 CO3 TsOH i-Bu2 AlH 1)

J K DHP
L M 2)AcOH

• The 1 H-NMR analysis of B shows two signals in the region 4.5-6.5 ppm.
• The IR spectrum of B shows a pick in 1745cm−1 , while that of C doesn’t have a pick
there and instead shows absorption at 1715cm−1 .
• C has the formula C15 H16 O2 .
• The first step in the formation of D is a well known rearrangement, which is followed
by iodolactonization in basic solution.
• DHP stands for 3,4-Dihydropyran.

Organometallic catalysis is widely used in the preparation of enantiomerically pure compounds.

The Sharpless epoxidation (used to form epoxides from allylic alcohols) is an example of this
catalysis, where a chiral ligand affects the kinetics of the reaction and leads to the formation
of unequal amounts of enantiomers. In this problem the chiral complexes of Ti-(+)-DET or
Ti-(–)-DET are examined.

3) A common ligand that is used in the Sharpless epoxidation is the diethyl ester of tartar-
taric acid (DET). Draw its stereoisomers and indicate the configurations of the chiral
centers.

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A major problem in numerous asymmetric syntheses is the non-linear effect, which occurs
when the enantiopurity of the catalyst doesn’t correspond with the enantiopurity of the
product.
The following Sharpless epoxidation reaction was predicted to form a pure sample of the (s)-
enantiomer from pure (+)-DET. However, as observed from the graph, the (R)-enantiomer
was accumulated as well.

t-BuOOH, Ti(Oi – Pr)4

L-(+)-diethyl tartrate

Concentr ati on of P r oduct (M)

(S)-enatiomer
0.4
(R)-enatiomer

0.2

5 10 15 20 25 30 35 40 T ime (h)

4) The activation energy for the production of the (R)-enantiomer using Ti-(+)-DET
(ER+ ) is 108 (kJ/mol). Calculate the activation energy for the production of the (R)-
enantiomer using Ti-(–)-DET (ER− ) and find the temperature in which the enantiomeric
excess (ee) of the aforementioned reaction is 90%. It is known that the reaction takes
place at 298K and that the pre-exponential factor can be considered to be equal between
the different reactions. Furthermore, this reaction forms a racemic mixture of products
if a racemic mixture of DET is used.

Another type of enantioselective reactions is asymmetric allylation. The diagram below rep-
resents the transition state of the asymmetric allylation of a certain aldehyde (RCHO) with
(–)-Ipc2 BCH2 CH – CH2 . The reaction proceeds through the more stable intermediate with a
chair configuration, which affects the chirality of the new chiral center.

Page 19 of 48
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Compounds belonging to the lauroxane family of C15 acetogenins possess interesting struc-
tural properties that caught the attention of several chemists in the field of asymmetric
synthesis. One of these compounds, isolaurallene, was isolated from the algae laurencia nip-
ponica yamada on the coasts of Japan and contains a nine-membered cyclic ether, as well as
a bromoallene residue.

5) Find the structural formulas of compounds A–O, as well as isolaurallene (notice that
A–O represent different compounds than in tasks 1–2). Indicate the stereochemistry
where possible.

NaN(SiMe3 )2 NaBH4 , H2 O (COCl)2 , DMSO

A THF, 25 o C
B Et3 N, CH2 Cl2
C

1)(4 – d Icr)2 BCH2 CH – CH2 2)Ac2 O, Et3 N

t-BuOOH, Ti(Oi – Pr)4 PPTS Et3 SiOTf HBr

H L-(+)-diethyl tartrate
G EtOH
F CH2 Cl2
E H2 O
D

K2 CO3 1)NaIO4 , 2)Ph3 P – CHCO2 Et t-BuOOH, Ti(Oi – Pr)4

I MeOH
J 3)i-Bu2 AlH
K L-(+)-diethyl tartrate
L

NCS Ph3 P

LiCuBr2 C7 H7 SO2 Cl LDA

O N THF
M

1)PPTS, MeOH 2)CBr4 , Ph3 P, toluene

Isolaurallene

• Compound G has the formula C24 H44 O5 Si.

• PPTS stands for pyridinium p-toluenesulfonate:

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2 ORGANIC CHEMISTRY

Question 1 2 Total
Theoretical
Points 20 80 100
Problem 5
Score

Problem 5: Indinavir
Author: Thombrom, Denmark
Indinavir, also traded under the name Crixivan, is a protease inhibitor which is used in the
treatment of HIV/AIDS. The drug disrupts reproduction of HIV viruses, thus leading to a
decrease in the viral load. Currently, however, it is not recommended for use in HIV/AIDS
treatment due to various side effects. We will in this problem look at the synthesis of
Indinavir.
The two synthesis presented in this problem starts with
materials A, B, C, D, E and F. These are reasonably
simple chemicals which can be bought in bulk for cheap
prices.
The bicycle A is a product of oil-refining and has the
chemical formula C9 H8 . The molecule B has the chem-
ical formula C3 H7 O2 Cl and the reaction of B to J cre-
ates a ring. C is of acidic nature and is commonly
found in the bark of a specific tree used in cooking.
D is the mono-boc-protected variant of one of the most
common bidentate ligands. E has a chemical formula
of C6 H12 O2 Cl2 and it’s 1 H NMR can be written as
δ5.6(1H, d), δ4.6(1H, d), δ3.7(4H, m), δ1.3(6H, t). Fi- Figure 5.1: The stucture of Indinavir
nally F is the (S) isomer of a γ-lactone with the chem-
ical structure C5 H8 O3 .

1) Provide the structures of A-F, including stereochemistry where applicable.

Two different synthetic routes to Indinavir is presented below in figure 5.1, where T represents
the structure of Indinavir. In the reaction from J to K, lipase is used to hydrolyze only the R
isomer. It is also known that the structure of R is tricyclic.

2) Solve for the structures G-S and include stereochemistry where applicable.

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2 ORGANIC CHEMISTRY

Figure 5.2: Scheme to produce Indinavir ( T)

PCL3
DME EDC

HOBt
Im P3NO

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2 ORGANIC CHEMISTRY

Question 1 2 3 4 5 6 Total
Theoretical
Points 5 11 1 8 16 0
Problem 6
Score
Question 7 8 9 10 11
Points 0 0 0 0 0 41
Score

Problem 6: The Secret Clownzhu Property

Author: apc, USA
Part I: Alkenes as Electrophiles
The allyl cation is well known to be quite stable when compared to other carbocations.
Therefore, an alkene which can be induced to give an allyl cation or some analogous structure
will act as an electrophile. A very famous example of such a reaction is the noted Tsuji-Trost
reaction, which stabilizes the allyl cation via an organometallic complex.

1) Draw the structure of compound A.

2) Draw the structure of the organometallic intermediate formed in this reaction, taking
care to observe electron counting rules.

Alkenes may also be electrophilic when attached to electron withdrawing groups, particularly
those which can stabilize a carbanion. The classic example is of conjugate addition to an
α,β-unsaturated carbonyl. Such a mechanistic step was featured in the following peculiar
method of synthesizing 1,4-diketones.

3) Identify the structure of compound B, and provide a reasonable mechanism for both
steps of this transformation. Hint: Silica is a Lewis acid.

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2 ORGANIC CHEMISTRY

Part II: Alkenes as Nucleophiles

Alkenes contain an electron rich π-bond, and this π-bond is often nucleophilic or electron
rich, especially when conjugated with a lone pair on an adjacent heteroatom. As an example,
enamines will react with electrophiles, or can be oxidised to give radicals.

Macmillan et al. developed an interesting way to alkylate ketones, which utilized Ce(NO3 )6 (NH4 )2
as an oxidant, and allyl-TMS as the alkylating agent. A secondary amine is used as an
organocatalyst, and may be abbreviated as NHR2 .

4) Provide a mechanism for this reaction.

5) Why is TMS an ideal functional group to place at the allylic position?

Part III: Reaction Schemes

Recently, a transition metal cross-coupling involving vinyl azides was developed. It is the first
step in the following scheme.

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2 ORGANIC CHEMISTRY

Compound X has the following spectrum: 1 H NMR: δ 1.40 (9H, s), 5.0 (1 H, dd (J = 16,
1.2 Hz)), 5.1 (1H, dd (J = 11, 1.2 Hz)), 6.1 (1 H, ddd (J = 16, 11, 9.0 Hz)) 6.3 (1H, d
(J = 9.0 Hz)), 7.3 (5H, m). Compound X reacts with concentrated acid, releasing CO2 and
isobutylene.

6) Decipher the structure of X.

7) Decipher the structures of compounds C-F.

8) Propose a mechanism for the conversion of X to C. Hint: Ir is similar to Pd in that it

can stabilize an allyl cation. Vinyl azides can be nucleophilic.

Finally, an interesting synthesis that combines many of the above ideas is the total synthesis
of (−)-Sordarin, a potential antifungal agent (structure shown on right). The synthesis is
shown below.

Notes:

• The step B → C involves the oxidation of a hydroxyl group to a hydroxyl radical.

• The step B → C involves a ring expansion.
• Conditions I-IV are simple transformations, followed by workup.
• Conditions V may involve multiple steps.
• Compound P is glycosylated to give (−)-Sordarin.

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2 ORGANIC CHEMISTRY

9) Decipher the structures of compounds A-N, with stereochemistry.

10) Propose conditions I-V.

11) Provide a detailed mechanism for the conversion of B to C, which explains the role of
AgNO3 .

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2 ORGANIC CHEMISTRY

Question 1 2 3 4 5 6 7 Total
Theoretical
Points 0 0 0 0 0 0 0 0
Problem 7
Score

Problem 7: Stereoisomer Enumeration and Burnside’s Lemma

Author: Idontknoweither, USA
Introduction
Let’s first start with a classic problem:

1) Draw the structure of all 9 isomers of inositol (1,2,3,4,5,6-cyclohexanehexol), and in-

dicate which, if any, are pairs of enantiomers.

But where does this number 9 come from? It turns out that we can actually calculate this
through purely mathematical means. In this problem we will develop a method to count the
number of stereoisomers with help from group theory, the mathematical study of symmetry.
We will first start with this inositol system, introduce the mathematical theory behind it, and
then apply it to rings (CH(OH))n of arbitrary size.
Background on Group Theory
We define a symmetry group to be the set of all symmetry operations on a certain geometric
figure. Symmetry operations are operations on a geometric figure which overall do not
change how a figure looks. For example, rotational and reflectional symmetry are the possible
symmetry operations on a 2D object.
If we label the vertices of an object, and then apply a symmetry operation, we end up with a
(possibly) different set of labels on the vertices. We say that two symmetry operations are
the same if the result of applying them on the labeled figure is the same.
Example 7.1
The cyclic group Cn refers to only the rotational (not reflectional) symmetries of a n-
sided regular polygon. For example, C4 is a group with 4 possible elements: doing nothing,
rotating 90 degrees, rotating 180 degrees, and rotating 270 degrees.

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2 ORGANIC CHEMISTRY

Example 7.2
The dihedral group Dn refers to the rotational and reflectional symmetries of a n-sided
regular polygon. Let’s look at D4 , which is the group of symmetries of a square.
It turns out that there are 8 possible symmetries of a square, with four reflections, three
rotation, and the identity operation of doing nothing, which are shown below:

Identity (do nothing) Rotate 90 degrees Rotate 180 degrees Rotate 270 degrees

H reflection D’ reflection V reflection D reflection

2) While it may seem like we have 8 independent operations in D4 , it turns out that we
can actually represent these 8 operations with compositions of just two operations, the
90-degree rotation operation r, and the reflection operation about the vertical axis s.
Write out all 8 possible symmetries in D4 as compositions of the rotation operation
r and reflection operation s. (For example, the operation of rotating 180 degrees is
simply r 2 , as we apply a 90 degree rotation twice to get a 180 degree rotation.)

This abstraction into symbols allows us now to apply algebraic results to this geometric
problem.
Claim 2.3
The dihedral group Dn has 2n elements. Further, the elements can all be written as
powers of r and s. Note that this group is not commutative (r s 6= sr ) since the order in
which applying the symmetry operations matters. Algebraically, the dihedral group can
be represented by all possible products of r and s, satisfying r n = 1, s 2 = 1, and s = r sr.

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2 ORGANIC CHEMISTRY

Burnside’s Lemma
Burnside’s Lemma allows us to count the number of possible colorings of a figure, up to
symmetries. Given a symmetry operation σ, there are colorings of a figure that would result
in the same figure after applying the operation σ. Let the number of colorings that don’t
change after be denoted as n(σ). Then, Burnside’s Lemma tells us that the total number of
colorings, up to symmetry, is
1X
n(σ)
n σ
where the sum runs over all symmetries σ.
Example 7.4
Suppose that we wanted to color the vertices of a square one of n colors, up to rotational
symmetry only. We want to count the number of possible colorings.
Then, the relevant symmetry group is C4 . We have four operations in C4 – the do nothing
operation, the 90 degree rotation, the 180 degree rotation, and the 270 degree rotation.
Let’s calculate n(σ) for each of these operations.

• For the do-nothing operation, we know that all the figures will remain the same
after we apply the operation. Since we can color each vertex n colors, we have n4
total squares that are unchanged after applying this operation.
• For the 90 degree rotation operation, we know that all the vertices will shift 90
degrees after we apply the operation. If the figure is unchanged after application
of this rotation, then the figure must all be the same color. There are n colors, so
there are n possible figures that remain unchanged after applying this operation.
• For the 180 degree rotation, each vertex will shift 180 degrees after each operation.
This means that opposite vertices should be the same color, but the whole square
doesn’t necessarily need to be. There are thus n · n = n2 figures that remain
unchanged after applying this operation.
• For the 270 degree rotation, similar analysis to the 90 degree rotation shows that
there are n possible figures.

Thus, Burnside’s lemma tells us the total number of squares up to rotational symmetry
is 41 (n4 + n + n2 + n).

3) Suppose that we wanted to color the vertices of a square one of n colors, up to rotational
and reflectional symmetry. Count the number of possible colorings in terms of n.
Hint: the relevant symmetry group here is D4 . The calculations for the purely rotational
symmetries are exactly the same as those above.

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The Inositol and general (CH(OH))n systems

Let’s now think about how we can enumerate stereoisomers of the (CH(OH))n system, in
terms of colorings. Assume that the system is completely flat. We can color a vertex one of
two colors, corresponding to whether the OH is up or down in the molecule. And, we want
to find the symmetry operations of this system up to rotation (not reflection, as this would
result in flipping stereochemistry).
However, this system’s symmetry group is not simply Cn , since we can also rotate the molecule
about a line through the plane in which it was located on (this symmetry operation was not
present in Cn or Dn !). When we perform this type of rotation, note that this operation also
flips all the colorings would have flipped (since those that were previously DOWN are now
UP, and vice versa).

4) Show that for a given n, the relevant symmetry group has 2n operations. Briefly describe
them.
Example 7.5
Let’s analyze the systems when n = 3 and when n = 4.
When n = 3, we have 6 symmetry operations - the one do-nothing operation, the two
planar rotations, and the 3 rotations through a vertex and an edge.
The do-nothing operation has 23 = 8 configurations that don’t change, the two planar
rotations each have 2 configurations that don’t change (the all cis up/down isomers),
and the rotations through the vertices have 0 configurations that don’t change (since
the vertex which the rotation axis goes through must change from UP to DOWN upon
applying this symmetry, so there is no symmetry that changes). The total number of
6 = 2 isomers. And indeed, the all-cis isomer
configurations is then 12, for a total of 12
and the trans isomer are the only two possible isomers of this system.
When n = 4, we have 8 symmetry operations - the one do-nothing operation, the three
planar rotations, 2 rotations through a pair of opposite vertices, and 2 rotations through
2 edges.
The do-nothing operation has 24 = 16 configurations, the 90/270 degree rotations have
2 configurations, the 180 degree rotation has 4 configurations, the 2 rotations through
vertices have 0 configuratoins, and the 2 rotations through edges have 4 each. So, the
total number is 18 (16 + 2 · 2 + 4 + 4 · 2) = 4. Indeed, there are 4 isomers of this system
(all cis, three on one side, two on one side from one edge, two on diagonally opposite
carbons).

5) Verify that the inositol system has 9 possible isomers with the same method.

Now let’s extend this to the arbitrary system. This is our main result.

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2 ORGANIC CHEMISTRY

6) Show that the total number of isomers is equal to

Ç n
å
1 n n/2 X
·2 + 2gcd(n,k)
2n 2 k=1

for even n, and equal to Ç å

n
1 X
2gcd(n,k)
2n k=1

for odd n.

With this result, we can actually show a purely mathematical fact:

7) Show that 2p−1 ≡ 1 (mod p) for any odd prime p. This is a special case of Fermat’s
little theorem.
Hint: Consider the number of isomers of a system with a prime number of carbons.
This quantity must be an integer.

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2 ORGANIC CHEMISTRY

Question 1 2 Total
Theoretical
Points 60 40 100
Problem 8
Score

Problem 8: Mysterious Rearrangement

Author: Maestron, Israel
When the aromatic hydrocarbon X, in the presence of element Y, is irradiated, compound A is
obtained (ω(Y) = 46.78%). Compound A further reacts with the bicyclic pyridine derivative
C (ω(N) = 9.03%); for this, a catalytic amount of NaI is also taken. The resulted salt D
then reacts with another salt Z, in which the mass fraction of one of the elements is 95.83%,
to obtain the molecular product E. The 1 H-NMR spectrum of E contains only 3 signals in
the region of 4.5- 6.5 ppm with a relative intensity of 1:1:1, and only 2 signals in the region
0-3 ppm with a relative intensity of 1:1. Upon heating, compound E isomerizes to a new
compound F, which also contains only 3 signals in the region of 4.5-6.5 ppm with a relative
intensity of 1:1:1, but 2 signals in the region of 0-3 ppm with a relative intensity of 1:3.
Notes:

• CoF3 is a strong oxidant that “replaces” all C-H bonds with C-F bonds.
• In your calculations use molar masses rounded to the closest integer.

1) Deduce the structural formulas of the unknown compounds if it is known that the
treatment of C with CoF3 and further treatment with a small excess of MeLi gives a
2,4,6-trimethyl pyridine derivative.

2) Write a mechanism for the transformation of E into F.

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3 INORGANIC CHEMISTRY

Inorganic Chemistry

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3 INORGANIC CHEMISTRY

Question 1 2 3 4 Total
Theoretical
Points 11 4 13 2 30
Problem 9
Score

Problem 9: Hot atom inorganic synthesis

Author: Tomasz, Poland
A is simple salt with K+ cations and B is compound which does not contain carbon and
it’s aqueous solution is strongly acidic. When solution of B is electrolysed, colored gas C is
the only gaseous product. Then this gas is passed through solution of A, the color of the
solution changes (however, the solution attains different colour than aqueous solution of C).
Obtained solution was labelled D. D precipitates with silver nitrite and when KOH is added
to D, colorless solution E is obtained. It contains 4 anionic species. Let F be the anhydrous
potassium salt of one of anions in E. Oxygen content in F is 22%.
Aqueous solution of C was prepared and it is observed that the solution is also colored.
However, introduction of KOH gives colorless solution.
Excess of B is introduced to the solution of F and solid G was crystallized. After moderate
heating this solid attained characteristic odour.
Isotopically-labelled F was prepared, mass of the molecule where approximately 2 u greater
than average molecular mass of F. After some time H was isolated. If G was prepared from
labelled F, after some time I was isolated.
H is highly explosive in gas phase, but stable when dissolved in water. Upon basification
aqueous solution releases two gases (which are also products of explosion of H) and at least
one new ionic species is formed.
I is unstable gas, decomposing to other gases when heated to around 80 °C, all products of
decomposition have density lower than 6 g/L under 105 Pa and 273.15 K.

1) Determine compounds corresponding to letters A–I. You do not have to indicate iso-
topes.

2) At least one process described in the problem is nuclear rather than purely chemical.
Determine the type of this nuclear process and indicate which nucleus(nuclei) transforms
into which nucleus(nuclei).

3) Write balanced equations of non-nuclear chemical reactions occurring in all described

processes. Include decomposition of H and I. Assume that after basification of solution
of H same volumes of both gases are released.

4) I can be synthesized from its decomposition products. Choose the most suitable con-
ditions for this task:

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3 INORGANIC CHEMISTRY

(a) heating to 200 °C

(b) cooling to 50 K
(c) passing through concentrated aqueous H2 SO4
(d) passing through concentrated aqueous NaOH
(e) UV radiation
(f) electric discharge

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3 INORGANIC CHEMISTRY

Question 1 2 3 4 5 6 Total
Theoretical
Points 1 1 1 1 1 1
Problem 10
Score
Question 7 8 9 10 11 12
Points 1 1 1 1 1 1 12
Score

Problem 10: A Quick Determination of Bidentate Ligands

Author: Vish, USA
Scientist Shelker is experimenting with a metal ion M2+ . He knows that M2+ binds to
bidentate ligand Ln to form complex [MLx ]2+nx . To figure out the identity of this complex,
Shelker performs a couple of experiments on the sample. He makes s series of solutions,
where the sum of concentrations of M2+ and Ln is always constant and equals 5 · 10−4 M.
He then proceeds to take the absorbances of these solutions at a wavelength of 470 nm in
a 1 cm cell. Scientist Shelker notices that the max absorbance of the complex occurs at
470 nm. (Note: Assume the absorbances of M2+ and Ln to be negligible at 470 nm.) The
absorbance A corresponding to mole fraction XM2+ is presented in table below:
XM2+ A XM2+ A XM2+ A
0.10 0.155 0.40 0.455 0.70 0.207
0.20 0.334 0.50 0.397 0.80 0.108
0.30 0.464 0.60 0.310 0.90 0.032

1) What is the color of the complex?

2) Given the data, find the value of x.

3) Calculate the molar absorbance coefficient ε.

The formation of the complex is given by the equation:

M2+ + xLn −−→ [MLx ]2+nx Kf .

4) Find the value of Kf .

Scientist Shelker wishes to learn more about his ligand L. He proceeds to perform Electrospray
Ionization Photoelectron Spectroscopy on two complexes, A and B. Both are similar but differ
in the coordinated metal. From the results, he was able to obtain the following diagrams:

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3 INORGANIC CHEMISTRY

Complex A Complex B

Scientist Shelker later found out that complex B underwent Jahn–Teller distortions where
the z axis was elongated, while complex A underwent no distortions.

5) Identify the geometries of complexes A and B.

6) Label all of the d orbital in complexes A and B.

7) Considering the geometry of B and the Crystal Field Theory, what is the strength of
Ln .

After Scientist Shelker had made observations of the properties of ligand Ln , he decided to
find out its identity. He knows that when small portions of metal M2+ and Ln are combined,
a precipitate Mc Ld forms.
Shelker performed a series of tests where he measured the heat released when different mole
fractions of M2+ and Ln were combined. The graph of his results is displayed below:

0.4

0.3

0.2

0.2 0.3 0.4 0.5 0.6 0.7 0.8

8) What are the values of n, c and d?

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3 INORGANIC CHEMISTRY

After finding the charge of the compound, scientist Shelker conducted a series of experiments
to find out the chemical formula of Ln . He knows that ligand forms compounds Bec Ld and
Bac Ld , which decompose under heat. The decomposition can be modeled by the following
equations at 250 °C:

Bec Ld −−→ X + Y + Z
Bac Ld −−→ Y + W .

At temperatures greater than 500 °C W decomposes further:

W −−→ Z + I .

Through experimental analysis, Shelker found that Y and Z are gasses and X is a binary
compound. After additional analysis, Shelker determined the percent composition by mass of
Be in X to be 36.03%.

9) Find the chemical formula of X.

Scientist Shelker was also able to find the percent composition by mass of compound Ba in
W to be 69.57%.

10) Given the cation and anion in W to be in 1:1 ratio, what is the chemical formula of W?

11) Identify gases Y and Z, given that they contain same elements.

12) Identify compound Ln .

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3 INORGANIC CHEMISTRY

Question 1 2 3 4 Total
Theoretical
Points 30 4 2 4 37
Problem 11
Score

Problem 11: Minerals, bioceramics, fireworks, flares and ignis fatuus

Author: Tomasz, Poland
Mineral X is a mineral with excellent biocompatibility and used widely in medicine as ceramic,
polymer, granules and a variety of other forms. It can be also found in rocks, either pure or
mixed with other minerals. Pure X is white, although X-containing rocks have all possible
colors due to different dopants.
X decomposes on heating to 1600 °C with mass loss of 1.8%. Two white solid phases are
detected in decomposition products: A (94.3% of mass) and B (5.7% of mass). When A
is heated with SiO2 and carbon, two gases D and E are released and solid C is formed. D
resublimates when cooled to room temperature and forms white waxy solid.
D has numerous applications, ranging from military industry to farming and is a crucial
substrate to countless industrial processes.
E has density lower than 1.3 g/m3 . It burns in oxygen giving gas F as the only product.
When F is bubbled through suspension of C in water forms solid G and SiO2 . G on heating
decomposes to B and F.
H is a solid substance used in fireworks and naval flares. There are different methods of
production of H.
In the first synthesis, D reacts with B in 1100 °C to give A and solid H. The second method
is heating A with carbon to 1200 °C to give H and E.
H reacts with D producing I (this reaction is reversed by heating pure I). Both H and I react
with water. H gives sparingly soluble white solid K and insoluble gas J. Side products of this
reaction are gas L and hydrogen. Hydrolysis of I yields K and L. Heating of K gives B as the
only solid product.
J is combustible even underwater and it’s mixture with L is explosive. J is likely to be the
main cause of ignis fatuus (Latin: giddy flame, also known as will-o’-the wisp) phenomenon.
In an electric discharge in J small amounts of L are formed and other gaseous products.
The only products of burning J are water and solid M which dissolves in water to give acidic
solution N. N has also plentiful uses, e.g. in food industry. There are other syntheses of N
known, one of them is dissolving D in aqueous KOH to give O (which is slightly acidic) which
can be transformed to N with very simple reaction.
When B is dissolved in aqueous N and the solution evaporates, A precipitates.

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3 INORGANIC CHEMISTRY

∆
B + D A + H
X

∆ C
∆

H + E B
A + B

∆
∆ SiO2 , C ∆
H2 O
z }| { I L + K
E + D + C

∆ O2 L ( + other products) D

F KOH, H2 O

H2 O
H K + J ( + L + H2 ) O
H2 O
∆ O2 ?
G + SiO2
H2 O
M N
∆
D, H2 O
B + SiO2
A
1) Determine substances A–O.

2) Determine formula of X and support your answer with equation of its decomposition.

3) Ingis fatuus were seen over an abandoned cemetery in the woods and J was detected
there. Choose the most probable source of J:
(a) Wooden coffins decomposition;
(b) Human bones decomposition;
(c) Stone grave reacting with soil;
(d) Human skin decomposition;
(e) Grave candles remains.

4) Choose all suitable conditions for transformation O→N:

(a) UV radiation/H2 O2 ;

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3 INORGANIC CHEMISTRY

(b) Prolonged heating under inert atmosphere;

(c) Concentrated HCl;
(d) Anodic reaction on Pt anode (hydrogen standard cathode separated by diaphragm);
(e) Cathodic reaction on graphite cathode (hydrogen standard anode separated by
diaphragm);
(f) Bubbling H2 S.

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3 INORGANIC CHEMISTRY

Question 1 2 Total
Theoretical
Points 40 60 100
Problem 12
Score

Problem 12: Short and Challenging Inorganic Puzzles

Author: Maestron, Israel
Part I
A mixture of two gases with a volume of 4(L) (T = 298K, p = 1atm) was passed through
a column filled with excess of hot CuO. As a result, the mass of the column increased by
0.2590(g). The gas that exited the CuO-column was passed through another column with
excess of P2 O5 (a strong dehydrating agent). As a result, the mass of the column increased
by 2.6557(g).

1) Find the composition of the original mixture (what are the gases and their molar frac-
tions in the mixture?). All the aforementioned reactions happened at a temperature of
200o C. Bonus: Try to think why CuO was used to analyze the mixture and not other
oxides, such as MgO.

Part II
The compounds A, F, and I are members of the same class of compounds. Among them, A
is a well known salt. F and I have similar structures.
The electrolysis of the aqueous solution of A without a diaphragm (separation between the
anode and cathode in the solution) leads to salt B. The anhydrous form of A reacts with
concentrated sulfuric acid to form C. The aqueous solution of C can react with B to form the
gas D. F is formed when D reacts under heating with the lustrous element E. When F is added
to an aqueous solution, it immediately hydrolyses to form the precipitate G (ω(E) = 64.5%).
E can be regenerated by first reacting G with zinc powder in concentrated HCl solution. This
forms the gas H which decomposes upon heating to E. E can react with F2 to form I that
reacts with one equivalent of ClF3 to form J. The mass fraction of fluorine in J is 49.1%
(ω(F) = 49.1%). In the reaction I −−→ J, one of the main reactivity trends of I is observed.

s is B
oly
ctr
ele
E H2 O HCl to
A D↑ F G↓ Zn
H↑ E
H2 SO4
(conc.) F2
C
ClF3
J 1 eq
I

2) Find the unknown compounds and write the balanced reaction equations.

Page 42 of 48
4 POLYMERS AND BIOCHEMISTRY

Polymers and Biochemistry

Page 43 of 48
4 POLYMERS AND BIOCHEMISTRY

Question 1 2 3 4 5 6 7 8 9 Total
Theoretical
Points 6 4 2 6 2 4 10 2 2 38
Problem 13
Score

Problem 13: Organic and inorganic polymers

Author: Tomasz, Poland
Element X can be used to synthesize various inorganic and mixed organic-inorganic polymers.
In this problem we will explore synthesis of three such polymers.
X reacts with excess chlorine to give compound A which in turn reacts with simple salt B
to give mixture of compounds C1 and C2 which are separated by distillation. Simple gas is
a side product of this reaction. Interestingly, C1 and C2 contain same three elements and
mass fraction of each element is same in C1 and C2. Ratio of molar masses of C1 and C2
is 3:4. C1 contains planar ring. Below mass spectrum (electron ionization mode) of B is
presented.

1) Identify salt B. Assign 4 highest MS peaks to molecules/ions. Don’t forget to indicate

mass number of each nuclei.

2) Write down structural formulas of C1 and C2. You can ommit eventual stereochemistry.

Polymer P1 can be obtained by heating C1 in presence of AlCl3 catalyst. P1 reacts with

4-methoxybenzylamine, giving polymer P2 which does not contain chlorine.

3) Determine structures of repeating subunits of polymers P1 and P2 (including bonds to

neighboring subunits).

4) Suggest mechanism of formation of P1 explaining the role of AlCl3 . In your mechanism,

indicate initiation, chain propagation and termination.

5) Infer the structure of end groups of the polymer from the mechanism proposed in
previous task and write down the full formula of polymer formed from n molecules of
C1.

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4 POLYMERS AND BIOCHEMISTRY

Organic compound D contains only carbon, hydrogen (5.4%) and oxygen. C1 and D react
in mass proportion of 1:1.07. Neither C1 nor D contain 7-membered ring, but product E of
their reaction has two such rings. 1 H NMR spectrum o D is shown below. Broad peak in
5.5-6.6 ppm has area approximately 4 times greater than all other peaks (6.7-7.7) together.

6) Suggest structural formulas of D and E.

Organic compound F contains 76.6% of carbon and 17.0% of oxygen. It reacts with diluted
nitric acid to give mixture of isomers F1 and F2. E reacts with F (molar ratio 1:2) to give
G. H is formed from G by reaction with hydrogen over PtO2 . Molar mass of H is 719.57
g/mol. Finally, D reacts with BTDA i DMAC, to give polymer P3. Water (50 mg for every
gram of H consumed) is a side product of this reaction.
Hint. Selected physical properties of N1 and N2 are presented in the table.
F1 F2
melting point 112±1 °C 44±1 °C
boiling point 279±1 °C 215±1 °C

7) Decipher compounds F, F1, F2, G and H.

8) Explain differences in melting and boiling points of F1 and F2.

9) Determine the structure of repeating subunit in P3 (including bonds to neighboring

subunits).

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5 ANALYTICAL CHEMISTRY

Analytical Chemistry

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5 ANALYTICAL CHEMISTRY

Question 1 2 3 4 Total
Theoretical
Points 5 10 6 8 29
Problem 14
Score

Problem 14: Alloy composition

Author: Tomasz, Poland
X is an alloy containing only metals. A sample of X was dissolved in HNO3 . Resulting solution
was labelled A.
1 M NaOH gives white precipitate with A. After bubbling air through solution with precipitate,
a part of precipitate turned brown. 1 M HNO3 was added and white part of precipitate
dissolved. Solution was filtered and labelled B, while remaining brown precipitate was labelled
C.
B does not give any precipitate with excess ammonia–ammonium chloride solution (both
1 M). Excess 1 M NaOH gives white precipitate with B. This precipitate was filtered and
dissolved in diluted HCl, the pH was adjusted to 7 with NaOH and solution was electrolysed.
No solid deposit was found on cathode.
A solution of K3 [Co(CN)6 ] was prepared and a few drops of this solution and B were placed
on a test paper. Paper was dried and burned, part of ashes was green.
Concentrated aqueous HCl slowly dissolves C and a gas is released in the process.

1) Determine alloy constituents.

2) Write reaction equations corresponding to processes described in above qualitative anal-

ysis. It is sufficient to provide one reaction corresponding to burning test paper with
mixture of two solutions, the product of this reaction shall be responsible for green color
of the ashes and contain about 38% of cobalt.

Quantitative analysis was performed. 1.000 g sample of alloy was dissolved in minimal amount
of 1 M HNO3 , pH was adjusted to approximately 6 with NaOH and solution was diluted to
400 ml with distilled water. 25 ml of solution was pipetted to conical flask and diluted to 100
ml. 0.25 g of hydroxylammonium chloride and 10 ml of ammonia–ammonium nitrate buffer
(pH 10) was added. 30 mg of eriochrome black T – potassium nitrate (V) was introduced,
solution turned red. Solution was titrated with standard 0.050 M EDTA until permanent blue
color is obtained. Titration required 25.3 ml of titrant.
2.500 g of sodium fluoride was added and solution was vigorously stirred (white precipitate
appeared). Solution was titrated with 0.050 M MnSO4(aq) until it turned blue, this titration
required 8.2 ml of titrant.

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5 ANALYTICAL CHEMISTRY

5.00 ml of 15% KCN solution was introduced, the solution turned red again. It was titrated
with same MnSO4(aq) standard to blue color, 10.7 ml of titrant was consumed.

3) Write reaction equations corresponding to processes described in above quantitative

analysis.

4) Determine the alloy elemental composition.

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