Country Participant code

4th Olympiad of Metropolises

Chemistry

Theoretical Problems

September 4, 2019
Moscow, Russia

Chemistry. Theoretical problems. Official English version 1

 Country Participant code

Instructions
 Begin only when the START command is given. You have 5 hours to work on the
problems.
 Use only the pen and calculator provided.
 All results must be written in the appropriate boxes within the text. Anything written
elsewhere will not be graded. Use the reverse of the problem pages if you need scratch
paper.
 Write relevant calculations in the appropriate boxes when necessary. If you provide only
correct end results for complicated questions, you will receive no score.
 Raise your hand if you have any questions concerning the text of the problems.
 Raise your hand if you need a restroom break.
 The official English version of this examination is available on request only for clarification.

Recommendations
*0 Read the text carefully. Try to understand properly: a) what is given to you, b) what is
required from you.
*1 All the problems contain questions of various complexity including very simple ones. Try to
answer as many questions as you can. Try to leave as few empty spaces in the answer sheets
as you can.
*2 In the calculations, use the atomic masses from the Periodic table given to you.

Good luck!

Chemistry. Theoretical problems. Official English version 2

 Country Participant code

Constants

Avogadro constant NA = 6.022·1023 mol–1

Gas constant R = 8.314 J K–1 mol–1

Elementary charge e = 1.60210–19 C

Speed of light c = 2.998108 ms–1

Planck constant h = 6.62610–34 Js

Zero of the Celsius

273.15 K
scale:

Consider all gases ideal.

Periodic table with relative atomic masses

1                               18
1 2
H He
1.008 2 13 14 15 16 17 4.003
3 4   5 6 7 8 9 10
Li Be B C N O F Ne
6.94 9.01 10.81 12.01 14.01 16.00 19.00 20.18
11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
22.99 24.30 3 4 5 6 7 8 9 10 11 12 26.98 28.09 30.97 32.06 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.10 40.08 44.96 47.87 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.38 69.72 72.63 74.92 78.97 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.95 - 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba 57-71 Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9 137.3 178.5 180.9 183.8 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 - - -
87 88 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
Fr Ra 89-103 Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
- - - - - - - - - - - - - - - - -
                                   
57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
138.9 140.1 140.9 144.2 - 150.4 152.0 157.3 158.9 162.5 164.9 167.3 168.9 173.0 175.0
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
- 232.0 231.0 238.0 - - - - - - - - - - -

Chemistry. Theoretical problems. Official English version 3

 Country Participant code

Problem 1. Kremlin stars (10 marks)

Question 1 2 3 4 5 6 7 8 Sum
Points 6 2 2 10 2 4 2 2 30
Result

The Kremlin towers crowned with red stars are among the best known symbols of Moscow. For the
first time, ruby glass stars appeared on the towers in 1937. According to chemical analysis, ruby
glass contains sodium, potassium, silicon, oxygen, sulfur, selenium, cadmium and the unknown
element X.

1. The color of the glass is caused by nanoparticles formed during heating of a sample of the
finished glass. Excluding element X from consideration, propose three possible formulas for
nanoparticles containing two or three elements in this glass.

1)

2)

3)

Element X is introduced into the glass in the form of substance X1, which is a white powder,
insoluble in water. Hydrochloric acid converts it to X 2. Addition of ammonium carbonate solution
to the solution of X2 leads to the formation of a white crystalline precipitate X 3. Heat treatment of
X3 (10.00 g) gives X1 (7.41 g). Other products of this reaction are carbon dioxide and 0.99 g of
colorless liquid X4 widely used as a solvent.

2. What class of compounds does X1 belong to?

Class of X1 –

3. Write down the formula of substance X4.

X4 –

4. Determine the formulas of X1 and X3, name element X. Show your calculations.

Chemistry. Theoretical problems. Official English version 4

 Country Participant code

Calculations

X1 –

X3 –

X–

5. Give the formula of substance Х2.

X2 –

6. Write down the reactions of X1 with HCl and NaOH.

7. What phenomenon is responsible for the color of the Kremlin stars? Choose one answer.
1) electronic transitions in a semiconductor nanoparticle
2) surface plasmon resonance
3) d-d transitions in a metal ion
4) light absorption by defects in glass

Number of the correct answer: __________

Chemistry. Theoretical problems. Official English version 5

 Country Participant code

8. The figure below presents the absorption spectra of three glasses. Which of them
corresponds to the red ruby glass Kremlin stars?

Number of the correct spectrum: __________

Chemistry. Theoretical problems. Official English version 6

 Country Participant code

Problem 2. Who planted scorpion, or Chemist’s nightmares after reading detective stories
(10 marks)

Question 1 2 3 4 Sum
Points 1 4 1 5 11
indane Result

For many years, qualitative reactions were among the most important methods for determining the
structure of organic compounds. Ninhydrin test for amines is still a widely used qualitative reaction.
Ninhydrin (A) – monohydrate of indane-1,2,3-trione – as well as its reaction with amino acids were
discovered by Siegfried Ruhemann in 1910. In 1954 it was shown that ninhydrin is an excellent
reagent for visualization of latent fingerprints. It is still in use for this purpose.

1. Write down the structural formula of ninhydrin taking into account that in this case
“hydrate” means the structure where water molecule is added to one of the carbonyl groups.

Ninhydrin, А

Ninhydrin test can be described by the following scheme:

O HO O
H2O A N
R
A + OH B C D E
 2 H2O  CO2  RCHO  2 H2O
NH2
OO

2. Decipher this scheme: write down the structural formulas of compounds B–E, taking into
account that С and D are position isomers; D can exist in either trans- or cis-form but С has
no geometrical isomers.

B C

D E

Chemistry. Theoretical problems. Official English version 7

 Country Participant code

Typically, primary amines undergo the above transformations affording bright-blue or purple
products. Secondary amines can participate only in some of these transformations producing yellow
or orange products.

3. Using the general formula of secondary amines RCH 2NHR', suggest the possible structural
formula(s) for such products.

Possible structural formula(s)

In 2018, the compound F was isolated as a white powder from the venom of Mexican scorpion
Megacormus gertschi. Ninhydrin test produced no intense coloring; the structure of F was
determined by modern physico-chemical methods. Thus, high-resolution mass spectrometry
analysis gave the exact molecular weight for monoprotonated F – 318.1450. Experiments on the
H/D exchange showed that F contains three protons that can be easily substituted by deuterium (–
OH or –NH group). NMR method demonstrated the presence of one –OH group, two –OMe groups
and one –CH2CH2– fragment. These and some other data enabled to determine the structure of F
which was then proved by counter synthesis according to the scheme below.
NH2

SO2Cl
MeO CHO N
2)
O N
1) LDA HO Et3N NaOH H
MeO G H I J F
OMe
DCC, HOBt
DIPEA

Here, Me is methyl, Et is ethyl, LDA is lithium diisopropylamide (strong base), DCC/HOBt/DIPEA

is the system used for the coupling of amines and carboxylic acids (DCC is
dicyclohexylcarbodimide, HOBt is 1-hydroxybenzotriazole, DIPEA is diisopropylethylamine).

4. Decipher the scheme of the F synthesis; write down the structures of compounds F–J.

G H I

J F

Chemistry. Theoretical problems. Official English version 8

 Country Participant code

Problem 3. Personal electric transport for a big city (10 marks)

Question 1 2 3 4 5 6 Sum
Points 4 3 3 5 2 8 25
Result

In recent years, personal electric vehicles – bikes, bicycles, monowheels, scooters, and even cars
have become very popular in large cities, including Moscow. All of them use rechargeable batteries,
which convert chemical energy of redox reactions into electrical work.

Lithium-ion batteries, where Li+ ions are transferred from the negative electrode to the positive one
through the electrolyte are most popular as compared to similar sodium-, magnesium-, and
aluminum-ion batteries. Specific capacity defined as the ratio of the transferred charge Q to the
mass m of the charge carriers and measured in milliampere-hours per gram (1 mAh/g = 3.6 C/g) is
one of the important characteristics of ion batteries.

1. Without calculations, arrange the above mentioned ionic batteries in the descending order of
their specific capacities. Calculate the specific capacity Q/m of the first battery in this
sequence.

Sequence:

Calculation:

Q / m = ________ mAhg–1

Almost all lithium batteries use a graphite matrix intercalated with lithium as the negative electrode,
lithium atoms being stored between the graphene layers. The figure below shows a fragment of the
crystal structure of a stoichiometric compound of lithium and carbon. The light lines limit the unit
cell with the volume of 59.5 A3 (1 A = 10–10 m). Lithium atoms are located on vertical edges,
whereas carbon atoms on edges and faces in horizontal planes.

Chemistry. Theoretical problems. Official English version 9

 Country Participant code

2. Determine the formula of this compound. Calculate the density of lithium in it (in gcm–3).

Calculation

Formula:

Density of lithium: _________ gcm–3

3. Mixed lithium-cobalt oxide is a common material for the positive electrode. Using the
formulas of the electrodes CLix and Li1–xCoO2, write down the equations of the cathode and
anode half-reactions taking place during the battery discharge, and the overall reaction
equation.
Note: reduction occurs on cathode.

Cathode:

Anode:

Overall reaction:

Chemistry. Theoretical problems. Official English version 10

 Country Participant code

A solution of a lithium salt in an organic solvent (like propylene carbonate) is a typical electrolyte
in lithium-ion batteries:
O
O
O
propylene carbonate

4. Characterize the solvent by ticking appropriate boxes. Suggest the reaction for its direct
synthesis from carbon dioxide.

protic aprotic polar nonpolar chiral

Reaction equation:

5. In E-bikes, a modified positive electrode LiNixMnyCo1–x–yO2 is used in the batteries.

Determine x and y (with two decimal places) given the mass content of the metals in the
electrode: Li – 7.19%, Ni – 20.08%, Mn – 18.79%.

Calculation:

x = _____ y = _____

Electric vehicles do not pollute the city air directly. However, electric energy is not absolutely
“green”, because carbon dioxide is released into the atmosphere during its production by fuel
combustion. Compare the environmental friendliness of three vehicles: a E-bike, an electric car, and
a conventional car with the following characteristics:

Power capacity Distance on a Fuel Average price in

Vehicle of the battery, single battery consumption, Moscow, million
kWh charge, km L / 100 km roubles
E-bike 0.47 45 – 0.035
Electric car 50 400 – 4.5
Conventional car – – 10 1

Chemistry. Theoretical problems. Official English version 11

 Country Participant code

6. For each of the vehicles, calculate the mass of CO2, released into the air (either by the
vehicle itself or during electric energy production) per 1 km distance.

Additional information:
Assume that the gasoline formula is C8H18.
Take the gasoline density as 750 g/L.
Electric energy is produced by methane combustion; take the efficiency of heat
transformation into electric energy as 30%.
1 kWh = 3600 kJ.

Substance CH4(g) CO2(g) H2O(g)

fH298, kJmol–1 –75 –394 –242

Calculation:

m(CO2):

E-bike Electric car Conventional car

____ g ____ g ____ g

You can decide yourself which vehicle is more convenient for you personally and which is most
eco-friendly.

Chemistry. Theoretical problems. Official English version 12

 Country Participant code

Problem 4. Deicing reagents (10

marks)

Question 1 2 3 Sum
Points 4 4 8 16
Result

Removing ice from roads and sidewalks or making them less slippery is vital to keep cities safe in
winter. Depending on temperature and the amount of ice, several strategies are used to tackle this
problem. These include mechanical removal, dispersion of traction providers (e.g. granite crumbs or
sand), and use of anti-ice reagents. In this problem we will focus on the latter option and analyze it
using chemical thermodynamics.

Deicing reagents do not really react with ice. Instead, they depress its melting point. For diluted
water solutions, the difference between their freezing temperature and that of pure water can be
estimated using the following equation:
RT02
Tm.p.   x
 fus H o
where ΔfusHo = 337 J/g is the enthalpy of fusion of water, T0 is its normal melting point (in K), R is
the universal gas constant, and x is the total molar fraction of all components of the solution except
water itself (note that possible dissociation should be taken into account in the calculation of x).

1. Sodium chloride, NaCl is one of the widely used deicing reagents. Calculate the mass of this
salt required to melt 7 mm thick ice on 1 m 2 of a sidewalk at –3oC. The density of ice is 0.91
g/cm3.

Calculations

m(NaCl) = _________ g

Chemistry. Theoretical problems. Official English version 13

 Country Participant code

The above equation is valid only for the diluted solutions. For larger salt : water ratios, phase
diagram should be used. For two most common reagents, NaCl and CaCl 2, the water-salt phase
diagrams for subzero temperatures are presented below. These phase diagrams are qualitatively the
same, the phases are shown in the inset.

Temperature (oC)
Solution

Solution Solution
+ ice + solid
salt

Ice + solid salt

Mass fraction of the salt in the system, %

Chemistry. Theoretical problems. Official English version 14

 Country Participant code

2. At what minimum temperatures NaCl and CaCl 2 can be used for ice melting? How much
salt (in grams) is required to melt 1 kg of ice at this temperature in each case?

NaCl: CaCl2:

Tmin = ______ oC Tmin = ______ oC

________________ g of salt / 1 kg of ice ________________ g of salt / 1 kg of ice

In real life, the thickness of ice film on the street varies and it is impossible to measure it directly
during dispersing deicing reagent. This reduces the efficiency of deicing procedure.

3. Assume that the thickness ice on the pavement ranges from 2 to 7 mm and that CaCl 2 is
distributed uniformly over it. Determine the lowest temperature at which it is possible to
melt the ice with any thickness in this range so that no ice or solid salt are left. How much
CaCl2 (in g/m2) is required for that?
Hint: convert the salt mass fractions on the diagram above into water/salt ratios. Temperature can
be determined graphically – you can place marks on the phase diagram.

Determination of temperature:

T = _________ oC

Calculation of CaCl2 consumption:

Mass of CaCl2 required = _____________ g / m2

Chemistry. Theoretical problems. Official English version 15

 Country Participant code

Problem 5. Photosynthesis under low-light conditions (10 marks)

Question 1 2 3 4 5 6 Sum
Points 4 7 7 3 1 3 25
Result

Photosynthetic organisms are well known for their unbelievable ability to adapt to adverse
conditions. For example, cyanobacteria living in deep sea do not have enough light because most
photons are absorbed by other photosynthetic creatures living closer to the water surface. In such
conditions, they attain an ability to utilize far-red light of low energy. This light is absorbed by
chlorophyll f (maximum of light absorption at 707 nm). It differs from the common chlorophyll a
(maximum of light absorption at 665 nm) by only one substituent. Energy absorbed by chlorophylls
f is transferred to chlorophylls a and further to reaction centers where it is converted to chemical
energy. The scheme for excitation energy transfer between the chlorophylls is shown below.

1. Determine the enthalpy of energy transfer from chlorophyll f to chlorophyll a. Is the process
endo- or exothermic?

Calculation

ΔrH = ____________ kJ/mol

Endo □ Exo □

Chemistry. Theoretical problems. Official English version 16

 Country Participant code

To determine the ratio of two types of chlorophyll in photosystem II they were extracted by
methanol. Absorbance (A) was determined at two different wavelengths in a cuvette with the
unknown length: A(665 nm) = 0.798 and A(707 nm) = 0.080. The absorption coefficients ε of both
chlorophylls are given in the table below.

ε(665 nm), ε(707 nm),

Lmol–1cm–1 Lmol–1cm–1
Chlorophyll a 70000 0
Chlorophyll f 15900 71100

2. Calculate the ratio of chlorophyll a to chlorophyll f in the photosystem II.

Calculation

a/f = _______

Consider the excitation energy transfer between chlorophylls a and f as a reverse chemical reaction:
k1
F* + A  
 F + A*
 (1)
k1
where F and A are the chlorophylls f and a, respectively, asterisk denotes the excited electronic
state.
For the efficient energy transfer, the rate constant k1 of the direct process must be as close as
possible to the rate constant k–1 of the reverse transfer.

The ratio k1/k–1 is equal to the thermodynamic equilibrium constant K and, hence, it depends on the
standard reaction Gibbs energy ΔrGo. There are two general ways to reduce the Gibbs energy of the
process in photosystem II compared to that in isolated chlorophylls (where ΔrG  ΔrH from p.1):
1) to increase the process entropy ΔrS (hypothesis 1), 2) to decrease the reaction enthalpy ΔrH
(hypothesis 2).

Entropy increase is achieved by energy transfer from one chlorophyll f to a larger pool of
chlorophylls a. Assume that all chlorophylls a have the same energy and do not interact with each
other. The chlorophyll f is in equilibrium with all the chlorophylls a.

Chemistry. Theoretical problems. Official English version 17

 Country Participant code

3. Using the Boltzmann formula, calculate the entropy change ΔrS and the Gibbs energy ΔrG of
energy transfer in photosystem II at room temperature (298 K). If you could not calculate
enthalpy in p.1 and/or the a/f ratio in p.2, take the values 11.0 kJ/mol and 12, respectively.

Calculation

ΔrS = _______ J/(molK) ΔrG = _______ kJ/mol

In the photosystem II, the enthalpy of energy transfer can differ from that for isolated chlorophylls.
It can be determined from the temperature dependence of chlorophyll a fluorescence decay rate.
Under experimental conditions, the ratio kd(T2) / kd(T1) of fluorescence decay rate constants kd at two
different temperatures is equal to the equilibrium constant ratio K(T2) / K(T1) for the reaction (1).

4. Determine the enthalpy of energy transfer in photosystem II, if the fluorescence decay rate
constant is reduced by a factor of 1.46 when the temperature decreases from 30 oC to 5 oC.

Calculation

ΔrH = ________ kJ/mol

5. Choose a hypothesis which better explains the experimental data.

Hypothesis 1 □ Hypothesis 2 □ Both hypotheses can contribute □

6. At what minimal ratio a/f the spontaneous energy transfer from excited chlorophylls f to
chlorophylls a will be possible in the photosystem II at room temperature? Hint. rG must
be zero.

Chemistry. Theoretical problems. Official English version 18

 Country Participant code

Calculation

a/f = ______

Useful formulas:
Gibbs energy: G = H – TS.

H
Temperature dependence of equilibrium constant: ln K    const .
RT

Photon energy: E = hc/λ, where h is the Planck constant, c is the speed of light, λ is the wavelength.

Lambert-Beer law: A = εcl, where A is absorbance, ε is the absorbance coefficient, c is

concentration, l is the cuvette length.
If several compounds absorb light in the solution, the total absorbance is:
A = ε1c1l + ε2c2l +…
The Boltzmann formula: S = RlnW, where R is the ideal gas constant, W is the number of possible
states with the same energy.

Chemistry. Theoretical problems. Official English version 19

 Country Participant code

Problem 6. -Alanine, a metabolite and accessory food substance (10 marks)

Question 1 2 3 4 5 6 7 8 9 10 Sum
Points 1 2 2 5 2 3 3 4 2 1 25
Result

Promotion of healthy living and balanced nutrition is of real importance in today’s metropolises.
Surprisingly, more and more city people prefer biologically active accessory food substances rather
than balanced natural food. In this task we will consider metabolic pathways of a food substance -
alanine (-Ala, see the structure on schemes 1 and 2), gaining ever increasing attention of athletes.

1. With respect to α-alanine, -alanine is a (tick all correct answers):

 homologue  epimer  anomer
 structural isomer  diastereomer  enantiomer

2. Give the number of stereocenters (N) in α-Ala and -Ala.

α-Ala N = ___________ -Ala N = ___________

-Alanine is not found in proteins; still it is wide-spread in organisms being formed via different
pathways. A canonical amino acid А and compound В are important -Ala precursors (scheme 1).

OH
СO2 O NADH, H+ NAD+, H2O NH3, H2O2 O2, H2O
A C B (1 )
enzyme enzyme
decarboxylase dehydrogenase
oxidase
NH2
-Ala
Notes.
a) All steps in all schemes are balanced chemical reactions.
b) All dehydrogenases are enzymes (oxidoreductases) catalyzing redox reactions.
c) NAD(P)+ and NAD(P)H are oxidized and reduced forms of co-enzyme nicotinamide adenine
dinucleotide (phosphate), respectively.

3. Draw the structure of А with stereochemical details.

Chemistry. Theoretical problems. Official English version 20

 Country Participant code

В is composed of atoms of three elements and contains 37.84 % by mass of nitrogen.

4. Draw all possible structural isomers of B.

Calculation:

Isomers:

B was found to be a product of metabolism of natural polyamines. It has no asymmetric centers, and
only two types of hydrogen atoms bound to carbons are found in B as detected by 1Н NMR.

5. Draw the structures of В and С.

В С

6. Indicate the number of ionogenic groups in В and the type of constant(s) (acidity (a) or
basicity (b)) characteristic of B in its aqueous solution. Choose the рН range where the
uncharged form of В is prevailing.

The number of ionogenic groups ________ The type of constant(s) а b

The uncharged form of В is prevailing at pH: 1–4 6–9  11-14

Pyrimidine base uracil is another important β-Ala precursor (scheme 2). Besides β-Ala, this
metabolic pathway usually referred to as reductive uracil catabolism results in two gaseous products
E и F readily soluble in water:

Chemistry. Theoretical problems. Official English version 21

 Country Participant code

O OH OH
O
O
NADH, H+ NAD+ H2O H2O
NH
D NH NH2
E+F+ (2 )
enzyme enzyme NH2
NH O dehydrogenase amidase
-Ala
O
3-ureidopropionic acid

7. Draw the structures of D, Е, and F.

D E F

Alongside with reductive, the so-called oxidative uracil catabolism (scheme 3) leading to urea and
compound I is specific of some living things.

O
R, H2O RH2 H2O H2O
NH H2N NH2
G H +I (3 )
enzyme enzyme
NH O dehydrogenase amidase O (C 3H 4O 4)
R is a n e le c tr o n a c c e p to r , R H 2 is th e r e d u c e d a c c e p to r

8. Draw the structures of G, H, and I, if it is known that the amidase cleaves the ring in G at
the same bond as the enzyme catalyzing the transformation of D (scheme 2).

G H I

β-Ala is used as the accessory food substance, since it acts as a O

precursor of vitamin В5 and carnosine (β-alanyl-L-histidine). The latter N OH
significantly contributes to an enhanced muscle performance due to its
N NH2
strong buffer capacity at pH of about 7.0 (note that the initial L-histidine
H L - h is tid in e
is a much weaker buffer).

Chemistry. Theoretical problems. Official English version 22

 Country Participant code

9. Draw the structure of carnosine and encircle the group responsible for buffering at рН 7.0.

10. Draw the substance which being accumulated in hard working muscles would lead to рН
changes (and thus to lower catalytic activity of enzymes) if there were no carnosine in body.

Chemistry. Theoretical problems. Official English version 23