Problem 1.

Clathrate gun (12%)

Question 1 2 3 4 5 6 Total
Marks 2 1 3 5 6 2 19

The only gun that is able to kill all living people in one shot

On the floors of oceans and seas there are vast reserves of methane
in the form of clathrate compounds called methane hydrates. These
reserves can be mined and serve as a source of energy or of raw
materials for organic synthesis. However, scientists are seriously
worried about the possibility of spontaneous decomposition of
hydrates caused by the raising ocean temperature. It is believed that
if a sufficient amount of methane is released into the atmosphere,
then the oceans will warm up quicker due to the greenhouse effect,
further accelerating the decomposition of clathrates. Due to the
explosion of the resulting methane-air mixture and/or changes in the composition of the
atmosphere, all living creatures may become extinct. This apocalyptic scenario is called a
clathrate gun.

Upon decomposition of 1.00 g of a methane hydrate with a fixed composition at 25 °C

and atmospheric (101.3 kPa) pressure, 205 mL of methane is released.

1. Determine n (not necessarily integer) in the formula of methane hydrate, CH4nH2O.

pV 101300  205
By the ideal gas law, the amount of methane    6  8.38 103 mol,
RT 10  8.314  298.15
1  8.38 103 16
then the amount of water in hydrate    4.81102 mol. The ratio of
18
amounts of water and methane is 4.81102 / 8.38 103  5.75 , i.e. the composition of
methane hydrate is CH4·5.75H2O or xCH4·5.75xH2O, where x is any natural number.

CH4·5.75H2O 2p

Real methane hydrate has a non-stoichiometric composition close to CH4·6H2O. At

atmospheric pressure, methane hydrate decomposes at –81 °C. However, under high
pressures (e.g. on the ocean floor) it is stable at much higher temperatures.
Decomposition of methane hydrate produces gaseous methane and solid or liquid water
depending on temperature.

2. Write down the equation of decomposition of 1 mole of CH4·6H2O producing solid

water (ice) H2O(s).

CH4·6H2O = CH4 + 6H2O 1p

4
The enthalpy of this process equals 17.47 kJ·mol–1. Assume that the enthalpies do not
depend on temperature and pressure, the volume change upon decomposition of hydrate
is equal to the volume of released methane, and methane is an ideal gas.

3. At what external pressure does decomposition of methane hydrate into methane and
ice take place at –5 °C?

Decomposition of methane hydrate can be viewed as a phase transition, which obeys

dp H RT 6M ( H 2O( s ) ) M (CH 4  6 H 2O )
Clausius-Clapeyron equation:  . V    . The
dT T V p  ( H 2O( s ) )  (CH 4  6H 2O)
difference between two last terms is negligibly small in comparison with the first term.
1 H
Thus, we can write the following equation: dp  dT . The dependence of the
p RT 2
 H  1 1  
pressure from temperature is thus given by p  p0 exp      . Substituting T0 =
 R  T0 T  
192.15 К, T = 268.15 К, p0 = 1 atm, we find that p = 22 atm or 2.2 MPa.

p = 2.2 MPa 3p

4. What is the minimum possible depth of pure liquid water at which methane
hydrates can be stable?
To answer this question, you should first deduce at which minimum temperature methane
hydrate can coexist with liquid water. Choose the correct answer.

 272.9 К  273.15 К  273.4 К 2p

At the minimum possible depth, the sum of pressures of atmosphere and water column is
equal to the dissociation pressure of methane hydrate. The temperature should be as low
as possible, but it cannot be less than the melting point of water at the corresponding
pressure. Thus, the temperature and pressure should correspond to the point of
coexistence of water, ice, methane hydrate and gaseous methane. Since the melting point
of water decreases with increasing pressure, the correct answer is 272.9 К.
Substituting T = 272.9 К into the equation from the previous question, we obtain p =
2.58 MPa. The height of the water column can be calculated using a formula
p  patm
h , where g = 9.8 m·s–2. From here h ≈ 250 m.
g  ( H 2O )

h = 250 m 3p (1p for the correct pressure, 1p

for a correct formula for h, 1p for a correct answer)

Large methane hydrate stocks on the floor of Baikal lake, the largest freshwater lake in
Russia and in the world, have been discovered in July 2009 by the crew of a deep-
submergence vehicle «Mir-2». During the ascent from the depth of 1400 m methane
hydrate samples started to decompose at the depth of 372 m.

5
5. Determine the temperature in Baikal lake at the depth of 372 m. The enthalpy of
fusion of ice is 6.01 kJ·mol–1.
From the Hess’s law, the enthalpy of the process CH4·6H2O = CH4 + 6H2O(l) is equal to
17.47 + 6·6.01 = 53.53 kJ·mol–1.
2p

From the previous question we know that at T0 = 272.9 К and p0 = 2.58 MPa there is an
equilibrium between methane, water and methane hydrate.
2p for the idea of starting from the triple point

Since that we can calculate the temperature of decomposition T at pressure p =

1 1 R p
9.8·1000·372 + 101000 = 3746600 Pa using the equation   ln 0 . We obtain
T T0 H p
T = 277.3 К, or about 4°C (which is in agreement with the measured temperature of
Baikal water at such depth).
2p

T = 277.3 К Total 6p

Total amount of methane in hydrates on Earth is no less than 5·1011 tons.

6. By how many degrees would the Earth atmosphere heat up, if such amount of
methane is burned by reacting with atmospheric oxygen? The enthalpy of combustion of
methane is –889 kJ·mol–1, the total heat capacity of the Earth’s atmosphere is about
4·1021 J·К–1.

500 109 103

Upon burning of methane,  889 103  2.78 1022 J of heat is released. Earth
0.016
atmosphere will heat up by 2.78 1022 / 4 1021  7 К.

ΔT = 7 K. 2p

6
 Problem 2. Break down photosynthesis – the Hill reaction (11%)

3 4
Question 1 2 5 6 Total
a b c a b
Points 1 2 2 2 3.5 1 2 3 2.5 19

In the history of photosynthesis research, there were some breakthrough experiments

which added much to our knowledge of this very complex process. One of such
experiments was performed in 1930s by an English biochemist Robert Hill. In this
problem, we consider some of his data together with the data of more recent experiments.

1. In plants, under illumination, carbon dioxide is reduced to carbohydrates (denote as

{CH2O}) and oxygen is produced. Write the overall equation of photosynthesis in plants.
H2O + CO2 = {CH2O} + O2 1p
(0 p for the unbalanced reaction)
Total: 1p

Much of the photosynthesis takes place in chloroplasts – organelles found in plant cells
and containing chlorophyll – the light-absorbing substance. Hill isolated chloroplasts
from the cells by grinding the leaves in the sucrose solutions. The cell-free chloroplasts
did not produce oxygen under illumination even in the presence of CO2. However, upon
adding potassium ferrioxalate K3[Fe(C2O4)3] (with the excess of potassium oxalate) to the
chloroplast suspension Hill observed oxygen liberation under illumination even without
CO2.

2. Hill’s experiment enabled to determine the source of oxygen during photosynthesis.

Write the formulas of the oxidant and the reducing agent in the photosynthesis inside the
plant cells and in the cell-free chloroplasts (the Hill reaction).

Natural photosynthesis Hill reaction

Oxidant Reducing agent Oxidant Reducing agent

CO2 H2 O K3[Fe(C2O4)3] H2 O
(0.5 p) (0.5 p) (0.5 p) (0.5 p)

Total: 2p

Hill measured the amount of evolved oxygen using muscle haemoglobin (Hill denoted it
Hb) which binds all molecular oxygen in a 1:1 ratio to form HbO2. The initial
concentration of Hb was 0.610–4 M. Kinetic curves corresponding to different
ferrioxalate concentrations are shown in the figure (the upper curve corresponds to
2.010–4 M).

7
 The fraction of bound haemoglobin HbO2 (with respect
to the initial amount of Hb) as function of time.
Crosses denote the end of reaction
(Figure 2a from the original Hill’s paper: R. Hill. Oxygen produced by
isolated chloroplasts. – Proc. R. Soc. B, 1939, v. 127, pp. 192-210)

3. a. From the figure, estimate the Fe / O2 mole ratio at the end of reaction. Do not take
into account the iron from Hb.
b. Write the equation of Hill reaction assuming that it proceeds with a high yield.
c. Using the table of standard electrode potentials, determine the Gibbs energy of
the Hill reaction at T = 298 K, oxygen pressure 1 mm Hg, pH = 8 and standard
concentrations of other species. Is this reaction spontaneous at such conditions?

Half-reaction E, V
O2 + 4H+ + 4e  2H2O +1.23
CO2 + 4H+ + 8e  {CH2O} + H2O –0.01
Fe3+ + e  Fe2+ +0.77
Fe3+ + 3e  Fe0 –0.04
[Fe(C2O4)3]3– + e  [Fe(C2O4)3]4– +0.05
[Fe(C2O4)3]4– + 2e  Fe + 3C2O42– –0.59

a. Calculations

The upper curve in the saturation limit gives ~ 75% of HbO2

n(Fe) / n(O2) = c(Fe) / c(HbO2) = 2.010–4 / (0.750.610–4) = 4.4 : 1 2p

b. Ratio ~ 4:1 shows that Fe(III) is reduced to Fe(II), which in the presence of
excess oxalate exists as a complex:

2H2O + 4[Fe(C2O4)3]3–  O2 + 4[Fe(C2O4)3]4– + 4H+. 2p

8
(1 p if Fe is given as Fe3+, without ligands)
с. Calculations
[Fe(C2O4)3]3– + e  [Fe(C2O4)3]4– E1 = 0.05 V
O2 + 4H+ + 4e  2H2O E1 = 1.23 V
emf: E = E1 – E2 = –1.18 V
(0 p if Fe3+ + e  Fe2+ half-reaction is used) 1p
 1 4
 
G = G  RT ln pO2 [H  ]4 =  4  96500  ( 1.18)  8.314  298  ln 
 750
10 8   =

= 2.57  10 J/mol = 257 kJ/mol
5
2p
The reaction is
spontaneous not spontaneous

 0.5 p
The reaction is highly endoergic and, hence, not spontaneous. Light is
necessary.

Now, the name “Hill reaction” denotes photochemical oxidation of water by any oxidant
other than carbon dioxide which is sensitized by plant cells or isolated chloroplasts.

In another experiment (1952), quinone in an acid solution was used as an oxidant in the
Hill reaction initiated by light flashes in the Chlorella algae. Experimental data are
shown in the figure. The volume of oxygen (in mm3, at temperature 10 oC and pressure
740 mmHg) per one gram of chlorophyll per one flash was determined as a function of
light intensity for natural photosynthesis and for isolated chloroplasts. It was found that
the maximum yield of oxygen is the same for natural photosynthesis and the Hill
reaction.

9
 (Figure 1 from: H. Ehrmantraut, E. Rabinovitch. Kinetics of Hill reaction.
– Archives of Biochemistry and Biophysics, 1952, v. 38, pp. 67-84)

4 a. Determine the reaction order of a photochemical Hill reaction with respect to

light intensity at low and high intensity. For each case choose one of three values:

Reaction order:

Low intensity High intensity

0 1  2 0  1 2

(0.5 p – for each correct choice, total – 1p)

b. How many chlorophyll molecules participate in the formation of one oxygen

molecule in the saturation limit of the Hill reaction? (The molecular mass of chlorophyll
is about 900 Da).
Calculations

n(Chl) / n(O2) = 1/900 / [(1210–6(740/760) 101.3)/(8.314283)] = 2200 2p

(1 p if similar ratio is obtained with other gas conditions, for example 1 atm or
room temperature, 0.5 p for the correct amount of Chl, 1 p for the correct
amount of oxygen)

10
 The quantum requirement of the light redox reactions is defined as the average number of
light photons (not necessarily integer) needed for the transfer of one electron from a
reducing agent to an oxidant. The isolated chloroplasts were irradiated during 2 hours by
a monochromatic light (wavelength 672 nm) with the energy input 0.503 mJ/s, and the
total volume of oxygen formed was 47.6 mm3 (under the same conditions as in question
4).

5. Calculate the quantum requirement for the Hill reaction.

Calculations

Total energy absorbed: E = 0.50310–3  36002 = 3.62 J

Energy of one mole of photons: Em = hcNA /  =
= 6.6310–343.001086.021023 / (67210–9) = 1.78105 J/mol
n(phot) = E / Em = 2.0310–5 mol 1p
n(O2) = PV / RT = (740/760)101.347.610–6 / (8.314283) =
2.0010–6 mol. 1p
Formation of one O2 molecules requires the transfer of 4 electrons:
n(e) = 8.0010–6 mol
Quantum requirement: n(phot) / n(e) = 2.5. 1p

Total: 3p

6. Try to make conclusions from the above experiments (questions 2-5). For each of
the following statements choose either “Yes” or “No”.

Yes No
In natural photosynthesis, water oxidation and CO2
reduction are separated in space. 
In chloroplasts, O2 is produced from CO2. 
Oxidation of water in chloroplasts requires light
illumination. 
Most of chlorophylls in chloroplasts participate directly
in the photochemical O2 production. 
In isolated chloroplasts, every absorbed photon causes
transfer of one electron. 

(0.5 p for each correct answer, total – 2.5 p)

11
Problem 3. Diverse permanganatometry (10%)

Quest. 1 2 3 4 5 Total
Marks 2 2 14 7 9 34
The amount of many reducing agents can be determined by permanganatometric titration
in alkaline medium allowing permanganate ion reduction to manganate.
1. Write down the ionic reaction equation for formate titration with permanganate in
an aqueous solution containing ~0.5 M NaOH.
2MnO4– + HCOO– + 3OH– = 2MnO42– + CO32– + 2H2O Total: 2p
If unbalanced 2 p
1p

Titration with permanganate in alkaline medium is often supplemented by addition of a

barium salt, which leads to precipitation of manganate as BaMnO4.
2. Which side redox processes involving manganate is suppressed by the barium salt?
Write down an example of equation of the corresponding reaction.
MnO42– + 2H2O + 2e– = MnO2 + 4OH–
OR
3MnO42– +2H2O = MnO2 + 2MnO4– + 4OH– 2p
Total: 2 p
If unbalanced 1 p

10.00 mL (VMn) of 0.0400 М (сMn) KMnO4 solution was placed in each of flasks А, В,
and С and different reactions were conducted in each flask.

3. To flask A, a sample solution containing crotonic acid (CA) СН3–СН=СН–СООН, an

alkali and barium nitrate (both in an excess) were added, and the reaction mixture was
incubated for 45 min. It is known that crotonic acid loses 10 electrons under the
experiment conditions.
a) Write down the total ionic reaction equation.
С4H5O2– + 10MnO4– + 14OH– + 12Ba2+ = 10BaMnO4 + CH3COO– + 2BaCO3 +
8H2O
4p
If unbalanced 3 p
If CO2 is evolved 3p

8.00 mL (VCN) of 0.0100 М (cCN) potassium cyanide solution was further added to the
incubated mixture. This resulted in completion of the following reaction:
2Ba2+ + 2MnO4– + CN– + 2OH– = 2BaMnO4 + CNO– + H2O
BaMnO4 precipitate was then filtered off, and the excess of cyanide in the filtrate was
titrated with 0.0050 M (cAg) AgNO3 solution till detectable precipitation was observed.
Note that both CN– and CNO– are analogs of halide ions, but CNO– affords soluble silver
salt.
b) Give the formula for the complex formed when Ag+ ions were initially added to the
cyanide solution (until the precipitate was formed).
b) (before the endpoint was attained):
[Ag(CN)2]– 2p

c) Give the formula of the precipitate formed.

29
(after the endpoint):
Ag+ + Ag(CN)2– = Ag[Ag(CN)2], or Ag+ + CN– = AgCN
So, AgCN or Ag[Ag(CN)2] is the answer. 2p

d) Derive the formula for calculating the amount of crotonic acid in the sample solution.
Calculate the mass of crotonic acid (in mg) if 5.40 mL (VAg) of the silver salt solution
was consumed for the titration to the endpoint.
Permanganate left after the reaction with crotonic acid: сMnVMn – 10nCAmmol. 1p
Cyanide consumed for the residual permanganate: ½(сMnVMn – 10nCA) mmol. 1p
Cyanide excess: cCNVCN – ½(сMnVMn – 10nCA) 1p

For the correct silver-cyanide stoichiometry (1:2):

2cAgVAg = cCNVCN – ½(сMnVMn – 10nCA). 1p
Thus, nCA = (2cAgVAg – cCNVCN + ½сMnVMn)/5 1p
nCA = (2×0.005×5.40 – 0.0100×8.00 + 0.5×0.0400×10.00)/5 = 0.0348 mmol, so
mCA = 0.0348×86.09 = 3.00 mg (МCA = 86.09 g/mol). 1p
For the wrong silver-cyanide stoichiometry (1:1):
cAgVAg = cCNVCN – ½(сMnVMn – 10nCA) (1p)
nCA = (cAgVAg – cCNVCN + ½сMnVMn)/5 (1p)
nCA = (0.005×5.40– 0.0100×8.00 + 0.5×0.0400×10.00)/5 = 0.0290 mmol, so
mCA = 0.0290×86.09 = 2.49 mg (1p)
Total for both cases (6p)

4. Another sample of crotonic acid and alkali (in an excess) were added to flask В, this
mixture lacking barium salt. An excess of KI (instead of cyanide) was added as a
reducing agent. The mixture was further acidified, and the iodine evolved was titrated
with 0.1000 М (cS) thiosulfate solution. 4.90 mL (VS1) of the titrant was used to reach the
endpoint.
Derive the formula for calculating the amount of crotonic acid in this experiment.
Calculate the mass of crotonic acid (in mg).
schematically
10MnO4– + 1Crotonate  10MnO42– + products 0p
Permanganate left after the reaction with crotonic acid сMnVMn – 10nCAmmol 0p
Manganate formed: 10nCA mmol 1p
Reactions occurred after iodide addition:
2MnO4– + 10I– + 16H+  2Mn2+ + 5I2 +8H2O and 1p
–
MnO4 + 4I + 8H  Mn + 2I2+4H2O
2– + 2+ 1p
Amount of the iodine evolved (mmol I2):
2.5nKMnO4 left + 2nK2MnO4. = 2.5(сMnVMn – 10nCA) + 2·10nCA. 1p
2Na2S2O3 + I2 = Na2S4O6 + 2NaI
nNa2S2O3 = 2nI2 = 5(сMnVMn – 10nCA) + 40nCA 1p
Thus, 5(сMnVMn – 10nCA) + 40nCA = cSVS1,
And nCA = ½сMnVMn – 0.1cSVS1 1p
nCA = 0.5×0.0400×10.00 – 0.1×0.1000×4.90 = 0.151 mmol,
mCA = nCAMCA = 13.00 mg. 1p
Total: 7 p

30
 5. A sample containing tin(II) was added to flask С, and the medium was adjusted to
weak alkaline. Tin(II) was quantitatively oxidized to Sn(OH)62–, whereas a precipitate
formed as a result of permanganate reduction. The precipitate was isolated, washed off,
dried at 250С, weighed (the mass of the water-free precipitate (mprec), representing a
binary compound, was of 28.6 mg), and dissolved in H2SO4 in the presence of an excess
of potassium iodide. The evolved iodine was titrated with 0.1000 М thiosulfate solution.
2.5 mL (VS2) of the latter was consumed to attain the endpoint.

a) Write down the reaction of precipitation. Confirm it wih calculations.

Tin(II) reduction with permanganate in weak alkaline medium led to an insoluble
binary manganese compound. Drying conditions suggest it is either one of
manganese oxides or their mixture.
The amount of equivalent is just the same for thiosulfate, iodine and the precipitate. 1p
neq = Vs2 cS = 0.1000×2.5 = 0.25 mmol
Meq = 28.6 mg / 0.25 mmol = 114.4 g/mol. This is the so called molar mass of the 1p
equivalent of the precipitate.

Let us consider possible cases.

 If MnO2 was formed ( scheme: 2MnO4– + 3Sn(II)  2MnO2 + 3Sn(IV),
MnO2 + 4H++2I–  I2 + Mn2+ +2H2O, I2 + 2S2O32– 2I– + S4O62–), the molar mass
of its equivalent in the reaction with iodide would be:
86.94 / 2 = 43.47 g/mol. 1p
 If Mn2O3 was formed (Mn2O3 + 2I– +6H+ I2 + 2Mn2+ +3H2O), the molar
mass of its equivalent in the reaction with iodide would be: 157.88/4 = 78.9 g/mol. 1p
 In the experiment, the molar mass of the equivalent is even higher, thus
manganese compounds, not oxidizing iodide, can be present in the precipitate (i.e.
manganese (II). The only possible variant is manganese(II, III) oxide (Mn3O4 + 2I–
+8H+ I2 + 3Mn2+ + 4H2O). The molar mass of the latter: 228.9/2 = 114.4 g/mol. 2p

Reaction:
6MnO4– + 13Sn(OH)42– + 16H2O = 2Mn3O4 + 13Sn(OH)62– + 6OH– 1p

Total for 5a 7p

b) Calculate the mass of tin in the sample (in mg) referred to the metal.
Tin amount equals 13/2 of that of Mn3O4, or
nSn =28.6 / 228.9  13/2 = 0.812 mmol 1p
mSn = 96.4 mg.

31
 Problem 4. Two binding centers – competition or cooperation? (10%)

1 2
Question Total
1.1 1.2 2.1 2.2 2.3 2.4
Marks 3 2 8 3 6 6 28

Many chemical reactions in living organisms include the formation of “host-guest” complexes
where the host molecule reversibly binds one or several guest molecules. Consider a host molecule
H with two binding centers – say, a and b which have different affinities for the guest molecules G:

⎯→ HGa [ HGa ]
H+G 
⎯ Ka =
[ H ][G ]
⎯→ HGb [ HGb ]
H+G 
⎯ Kb = Kb  Ka.
[ H ][G ]
where HGa and HGb denote a complex where guest is bound to a center and b center, respectively.
Ka and Kb are the binding constants for the centers a and b, brackets denote molar concentrations.
Attachment of one G molecule to H can change the binding ability of the second centre.
This change is described by the “interaction factor”  which reflects the influence of one binding
center on another and is defined as follows:
⎯→ HG2 [ HG2 ]
HGa + G  ⎯ = K b
[ HGa ][G ]
where HG2 is the completely bound complex.

1.1. Determine the range of values (or one value, if necessary) of  which correspond to three
possible ways of interaction between binding centers: a) cooperation (binding by one center
facilitates subsequent binding); b) competition (first binding complicates the second); c)
independence (no interaction).

Cooperation:  > 1 1 pt (0.5 pt – for value, not range)

Competition: 0 <  < 1 1 pt (0.5 pt without zero; 0.5 pt – for value, not range)
Independence:  = 1 1 pt
Total 3 pts

⎯
1.2. Find the equilibrium constant for the process: HGb + G 
⎯→ HG2 in terms of binding
constant(s) and interaction factor.

Calculations:
[ HG2 ] [ HG2 ] [ HGa ] K
K= =  = K b  a = K a
[ HGb ][G ] [ HGa ][G ] [ HGb ] Kb
K = Ka 2 pts
 2.1. The solution was prepared with the initial concentrations [H]0 = 1 M and [G]0 = 2 M. After the
reactions were completed, the concentration of H decreased by 10 times and that of G by 4 times.
For these host and guest, Kb = 2Ka. Determine the concentrations of all other species in the solution
and find the binding constant Ka and the factor .

Calculations:
From Kb = 2Ka it follows: [HGb] = 2[HGa] 1 pt
Material balance with respect to H: [H] + [HGa] + [HGb] + [HG2] = [H]0 = 1 M, or
0.1 + 3[HGa] + [HG2] = 1 M 0.5 pt
Material balance with respect to G: [G] + [HGa] + [HGb] + 2[HG2] = [G]0 = 2 M, or
0.5 + 3[HGa] + 2[HG2] = 2 M. 0.5 pt

Solving the system of two equations, we find: [HGa] = 0.1 M, [HG2] = 0.6 M, hence [HGb] = 0.2
M.
[ HGa ] 0.1
Ka = = =2
[ H ][G ] 0.1  0.5
[ HG2 ] 0.6
= = =3
[ HGa ][G ]Kb 0.1  0.5  4

[HGa] = 0.1 M [HGb] = 0.2 M [HG2] = 0.6 M

(1 pt for [HGa], 2 pts for [HG2], and [HGb] is not marked if [HGb] = 2[HGa] was given 1 pt,
otherwise 1 pt)

Ka = 2 1 pt

=3 2 pts
Total 8 pts
If you could not answer this question, for further calculations use reference values Ka = 3.14 and 
= 2.72.

2.2. Find the correct order of standard molar Gibbs energies of formation of host H and all host-
guest complexes from H and G. In the scheme below, write the corresponding chemical formula
near every line.
1 pt – for the highest G(H),
1 pt – for the lowest G(HG2)
1 pt – for G(HGa) > G(HGb)
Total 3 pts

2.3. Some amount of G was added to 1 mole of H and the mixture was dissolved in water to obtain
1 liter of the solution. The number of the totally bound molecules HG2 in the solution is equal to the
total number of single-bound molecules HG. Find the initial amount of G (in mol). The constants
Ka and Kb and the factor  are the same as in question 2.1.

Calculations:

1) [HG2] = [HGa] + [HGb] = 3[HGa]

[ HG2 ] 3
= Kb = 12 , = 12 , [G] = 0.25 M
[ HGa ][G ] [G ]
2) Material balance with respect to H: [H] + 3[HGa] + [HG2] = 1 M
[H] + 6[HGa] = 1 M
[H] + 12[H][G] = 1 M
[H] = 0.25 M.
3) [HGa] = Ka[H] [G] = 0.125 M.
[HG2] = 3[HGa] = 0.375 M.
4) Material balance with respect to G: [G]0 = [G] + 3[HGa] + 2[HG2] = 1.375 M

n0(G) = 1.375 mol

Correct determination of [G], [H], [HGa], [HG2] – 1 pt for each concentration
n0(G) – 2 pts
Total 6 pts
 2.4. What would be the equilibrium composition of the solution if: a)  = 0; b)  is very large ( →
). The constants Ka and Kb as well as the initial concentrations of H and G are the same as in
question 2.1.

=0
Calculations:
In this case, no HG2 is formed.
Material balance with respect to H: [H] + [HGa] + [HGb] = 1 M, or
[H] + 3[HGa] = 1 M
Material balance with respect to G: [G] + [HGa] + [HGb] = 2 M, or
[G] + 3[HGa] = 2 M
[ HGa ]
Equilibrium constant: Ka = =2
[ H ][G ]
Solving the system of three equations, we get:
[H] = 0.129 M [G] = 1.129 M [HGa] = 0.290 M [HGb] = 0.580 M
[HG2] = 0
1 pt for each concentration except HGb, maximum – 4 pts
→
Calculations (or arguments):
In this case, formation of HG2 is practically irreversible, so only HG2 is present in the solution.
[H] = 0 [G] = 0 [HGa] = 0 [HGb] = 0
[HG2] = 1 M
2 pts
(any calculation which gives similar result – full mark)
Total 6 pts
Problem 5. Coupling of chemical reactions (10%)
1 2
Question 3 Total
1.1 1.2 1.3 2.1 2.2
Marks 4 6 4 3 6 2 25

I.Prigogine (left) N. Shilov W. Ostwald

When in the system one reaction allows another one to proceed they say that these two reactions are
coupled. Ilya Prigogine, Nobel prize winner in chemistry (1977) in his books widely used the
concept of “coupled reactions”. Coupling of reactions is an essential feature of living systems,
including human body.

How one reaction makes another one to occur? In this problem we are going to discuss several
possible mechanisms of coupling.

(I) “Chemical coupling”

“On Chemical coupling” was the title of the dissertation defended by Russian chemist N.Shilov in
1905. N. Shilov was the graduate student of famous professor W. Ostwald. Dr. Shilov described the
following set of reactions.
The substance А does not react with Ac. In the presence of the third reagent (called inductor), In,
however, the reaction of А with Ac takes place:

A + Aс ⎯⎯⎯⎯⎯⎯
In the absence of In
→ no reaction! (1)
A + Ас ⎯⎯⎯⎯⎯⎯⎯
→ Р1
In the presence of In
(2)

In is not a catalyst! Its concentration decreases in the course of the reactions.

According to the scheme proposed by Shilov, Ас reacts not with A itself, but with the intermediate
product R of the reaction of А with In. There is another, competing reaction of R that forms P2.
 k (3a )
(a ) A + In ⎯⎯⎯⎯ →R
k (3b)
( b) R ⎯⎯⎯⎯ → P2 (3)
k (3c)
(c) R + Ас ⎯⎯⎯⎯ → P1

 and  are stoichiometric coefficients. Other stoichiometric coefficients and reaction order with
respect to all reactants in all three reactions are unity.

n Ас
In the Shilov’s experiments the ratio of the consumed amounts of Аc and In, I = increased up
n In
to the constant value with the increasing initial concentration [Ac]0 at [In]0 = const.

1.1. What was this limiting constant value of I at [Ac]0 → , [In]0 = const?

Brief explanation

The value of I should increase with the increase of [Ac]0 at [In]0 = const, because the larger fraction
of the intermediate product R will enter the reaction (3c). The maximum value of I will be achieved
if all R reacts in (3c), therefore I = 1/β.

I = 1/ 4 points (2 points if only I = 1/ is given!)

1.2. Derive an expression for I using the steady-state approximation if necessary. Plot the graph of I
vs [In]0 at [Ac]0 = const. Assume that In was completely consumed and Аc was in excess..

Calculations
Shilov’s mechanism includes the initial reaction

A + In → R (3a)

and two competitive reactions

R + Ac → P1 (3c)
R → P2 (3b)

The rates of conversion of In and Ас are determined by the rates of the reactions (3а) and (3c),
respectively:
 k (3a )[ A][ In ]
k (3c)[ Ac] 
r (3с) k (3с)[ R][ Ac] k (3c)[ Ac] + k (3b) k (3c)[ Ac]
= = =
r (3a ) k (3a )[ A][ In ] k (3a )[ A][ In] k (3c)[ Ac] + k (3b)

in steady-state approximation for [R]. We see that the ratio of two rates does not depend on the
initial concentration [In]0 and I will also not depend on it. This gives the straight line parallel to
the [In]0 axis on the graph.

Graph

0
[Ac] = const
I =nAc/nIn

[In]0

6 points (2 points for the graph + 4 points for the steady-state equations)

What if Shilov’s mechanism is not valid and In is a conventional catalyst of the reaction (2)?
Simultaneously In reacts with А and its concentration decreases. The reaction scheme in this case is

(a ) A + In ⎯⎯
→ P2
In, catalysis (4)
(b) A + Ас ⎯⎯⎯⎯⎯⎯→ P1

1.3. What is the limiting value of I for the reaction scheme (4) at [Ac]0 → , [In]0 = const?

Brief explanation
In this case I will permanently increase with the increase of [Ac]0 →  at [In]0 = const. The rate
of the reaction (4b) may be so high that conversion of In in reaction (4а) will be negligible.
Hence I → ∞ if [Ac]0 →  at [In]0 = const.

I =  (infinity) 4 points (2 points if only I =  (infinity) is given).

(II) «Kinetic coupling»

The standard Gibbs energy of the gas-phase reaction

k5
⎯⎯⎯
Br + H 2 ⎯⎯ ⎯→ HBr + H (5)
k−5
is positive, G(5) = 66 kJmol–1 at Т = 600 К.

r5
2.1. What is the ratio of the rates of forward and reverse reactions, , at this temperature, standard
r−5
pressures of H2 and HBr and equal pressures of H and Br?

Calculations
The standard Gibbs energy of reaction (5) at 600К is 66 kJ/mol. The equilibrium constant is
K = e −66000/8.314/600 = 1.8  10−6 = k5 / k −5 . 1 point
Reaction is considered at standard pressures of all the reactants and products. The ratio of the rates
of forward and reverse reactions is
r5 k [Br][H 2 ] k
= 5 = 5 = 1.8  10−6
r−5 k−5 [HBr][H] k−5

r5
= 1.810–6 2 points
r−5
Total – 3 points
If you could not answer this question, for further calculations use reference value r5/r–5 = 3.1410–7.

Reaction (5) proceeds in the forward direction due to the reaction (6) which simultaneously occurs
in the system:

k5
⎯⎯⎯
Br + H 2 ⎯⎯ ⎯→ HBr + H (5)
k−5
k6
H + Br2 ⎯⎯→ HBr + Br (6)

k5, k–5, k6 are rate constants of forward and reverse reaction (5) and forward reaction (6),
respectively.

This is the kinetic coupling of two reactions.

Let pressures of neutral molecules keep standard values p(H2) = p(Br2) = p(HBr) = 1 bar, and
pressures of radicals p(H), p(Br) reach steady-state values. Rate constant k6 is 10 times larger than
k–5.

r5
2.2. Calculate G(5) and under such conditions.
r−5

Calculations
The steady-state condition is the same for both radicals, e.g. for radical Н

d [H]
= k5 [Br][H 2 ] − k−5[HBr][H] − k6[H][Br2 ] = 0
dt
[H] k5[H 2 ]
=
[Br] k−5[HBr] + k6 [Br2 ]

The concentrations of all the neutral molecules are the same (they correspond to the pressure of 1
bar), therefore

[H] k5 k /k 1.8  10−6

= = 5 −5 = = 1.6  10−7 2 points
[Br] k−5 + k6 1 + k6 / k−5 1 + 10

The Gibbs energy of reaction (5) under such conditions is:

= 66 + 8.314  10−3  600  ln (1.6  10−7 ) = −12 kJ  mol −1

[H][HBr]
G = G + RT ln
[Br][H 2 ]
2 points
The ratio of rates is:

r5 k [Br][H 2 ] k [Br] k5 1 + k6 / k−5 k

= 5 = 5 = = 1 + 6 = 11 2 points
r−5 k−5 [HBr][H] k−5 [H] k−5 k5 / k−5 k−5

G(5) = –12 kJmol–1

r5
= 11
r−5
Total – 6 points
(III) ”Second law of thermodynamics restricts coupling”

According to the Second Law of thermodynamics, two simultaneously occurring chemical reactions
GSyst
should decrease the system’s Gibbs energy GSyst,  0.
t

One of these reactions may have positive Gibbs energy and still proceed in the forward direction
due to the coupling with the second reaction. This second reaction must have negative Gibbs energy
and the requirements of the Second law must be fulfilled! Consider the example.

The synthesis of urea under specific conditions

2NH3 + CO2 → (NH2)2CO + H2O (7)
G(7) = 46.0 kJmol–1

is supposed to be coupled with the complete oxidation of glucose (under the same conditions)

1/6 C6H12O6 + O2 → CO2 + H2O (8)

G(8) = –481.2 kJmol–1,
r(8) = 6.010–8 Mmin–1.

Both reactions are presented schematically. No other reactions are considered.

3. What is the maximum rate of the reaction (7) permitted by the Second Law if this reaction is
coupled to reaction (8)?

Calculations
According to the Second law the following condition has to be met:
GSyst
= G (7)  r7 + G (8)  r8  0
t
therefore

−G (8) 481.2

r7  r8 =  6.0  10−8 = 6.3  10−7 M  min −1
G (7) 46.0

This is the maximum possible rate of the coupled reaction.

r7(max) = 6.310–7 Mmin–1 2 points

 Problem 6. From one yellow powder to another: A simple inorganic riddle (10%)
Question 1 2 3 4 Total
Marks 8 8 3 5 24

The yellow binary compound X1 was completely dissolved in concentrated nitric acid by heating,
the gas evolved is 1.586 times denser than air. Upon adding an excess of barium chloride to the
solution formed a white solid X2 precipitates. It was filtered. The filtrate reacts with an excess of
silver sulfate solution forming a precipitate of two solids X2 and X3, also separated from solution by
filtration. To the new filtrate the solution of sodium hydroxide was being added drop-wise until the
solution became nearly neutral (about pH 7). At this time a yellow powder X4 (77.31 wt.% of Ag)
crystallized from the solution. The mass of X4 is nearly 2.4 times larger than that the mass of the
first portion of X2.

1. Determine the chemical formulae of X1 – X4.

Calculations:
The precipitate X2 formed by addition of barium chloride in acidic medium is barium sulfate
BaSO4. 1 pt
The precipitate X3 formed by addition of silver sulfate is silver chloride AgCl 1 pt

The yellow precipitate X4 formed by addition of alkali can be mercury oxide HgO or silver
phosphate Ag3PO4. The ratio of molar masses X4 : X2 is 0.931 for HgO : BaSO4 which is not
valid and 1.798 for Ag3PO4 : BaSO4 which gives 2.4 being multiplied by 4/3. So, the molar ratio
is 4Ag3PO4 : 3BaSO4 which corresponds to P : S = 4:3, i.e. to formula of X1 P4S3.

X1 = P4S3 X2 = BaSO4 X3 = AgCl X4 = Ag3PO4

2 pts for Ag3PO4
4 pts for P4S3 (0 pts without calculations)
Total – 8 pts

2. Determine the chemical formula of the gas and provide equations for all reactions in ionic or non-
ionic form.

Calculation
The gas evolved has a molar mass 1.586 × 29 = 46 g/mol, that is NO2. 1 pt
Chemical formula of the gas ________

Dissolution of X1
P4S3 + 38HNO3 = 4H3PO4 + 3H2SO4 + 38NO2+ 10H2O 2 pt
Formation of X2
 H2SO4 + BaCl2 = BaSO4+ 2HCl 1 pt
Formation of X2 and X3
Ag2SO4 + 2HCl = 2AgCl + H2SO4 1 pt
BaCl2 + Ag2SO4 = BaSO4 + 2AgCl 1 pt
Addition of NaOH and formation of X4
H2SO4 + 2NaOH = Na2SO4 + 2H2O 1 pt
2H3PO4 + 6NaOH + 3Ag2SO4 = 2Ag3PO4 + 3Na2SO4 + 6H2O 2 pts
(neutralization of H3PO4 and subsequent reaction with Ag2SO4 will also be accepted)

(50% of points for non-balanced reactions with correct products)

Total – 8 pts

3. In the structural unit of X1 all atoms of only one element are in equivalent positions. Draw the
structure of X1.

Phosphorus sulfide P4S3 is a molecular cage

3 pts
(Any reasonable structures with correct valencies of sulfur and phosphorus will also be accepted.
1 pt for the structure with non-equivalent atoms of both elements)

4. Predict the products of X1 interaction with:

a) excess oxygen;
b) excess of hot concentrated sulfuric acid;
c) solid KClO3 with grinding.
Write down the reaction equations.

a) P4S3 + 8O2 = 2P2O5 + 3SO2 1 pt

b) P4S3 + 16H2SO4 = 4H3PO4 + 19SO2 + 10H2O 2 pts

(oxidation of sulfide to S instead of SO2 is full mark)

c) 3P4S3+ 16KClO3 = 16KCl + 6P2O5 + 9SO2 2 pts

(50% of points for non-balanced reactions with correct products)
Total – 5 pts
Problem 7. The Wilgerodt-Kindler (WK) reaction (13%)
Question 1 2 3 4 5 Total
Marks 6+3 4 4 10 3 30

Thio- (I) and dithiocarboxylic (II) acids are sulfur-containing analogs of carboxylic acids
in which one or two oxygen atoms of the carboxyl group are replaced by sulfur.
Thiocarboxylic acids exist as a mixture of tautomers Ia and Ib.

1. Using toluene and only reagents 1–6, propose the synthesis of acids I and II (all
reagents should be used).
1. 1) СS2; 2) H3O+ 2. SOCl2 3. Br2/hv
+
4. NaSH 5. KMnO4/H3O /t 6. Mg/ether

6 სწორად დაწერილი სტრუქტურა - თითო 1 ქულა

6 სწორად მისადაგებული რეაგენტები - თითო 0.5 ქულა

The Wilgerodt-Kindler (WK) reaction makes it possible to obtain compounds containing a

thiocarbonyl group. One of the reactants in the WK reaction is D which is obtained

according to the scheme:

2. Determine the structures of A–D if for C wC = 45.71%. wH = 10.48%, wN = 13.33%;

1
H NMR spectra of both A and B contain only one signal; D exists as a chair conformation.
The WK reaction can be demonstrated by the example of the interaction of ketone E
(CnHnO) with D in the presence of sulfur. The homologue of E, compound G, reacts
similarly. The aliphatic part of the 1H NMR spectrum of F contains a singlet (2H) and two
multiplets each of 4H, and H contains two triplets of 2H and two multiplets of 4H; there
are no singlets in the 1H NMR spectrum of G.

A B C

1 ქულა 1 ქულა
1 ქულა

1 ქულა

3. Determine the structures of E–H.

E F G

1 ქულა 1 ქულა

1 ქულა
 H

1 ქულა

The WK reaction was used in the synthesis of debromoaplysin X, a natural antioxidant:

4. Determine the structures the of K–R, X, CxHyI.

K L M

1 ქულა 1 ქულა 1 ქულა

 N O P

1 ქულა 1 ქულა
1 ქულა

Q R X

1 ქულა
1 ქულა
1 ქულა

CxHyI

1 ქულა

5. Indicate configurations (R/S) of chiral centers a–c in the given structure of precursor
of X.

ჯამში 3 ქულა
Problem 8. Odor retention agent (12%)
Question 1 2 Total
Marks 5 9 14
Natural ambergris is a waste product of cachalots, highly valued in perfumery and used as
an odor retention agent. One of the key components responsible for the smell of ambergris
is the natural terpenoid ambroxide X, which was obtained from the essential clary sage oil
component sclareolide Y.

1. Give the structural formulas of A – С, sclareolide Y, and ambroxide X.

A B Y
1 ქულა 1 ქულა 1 ქულა

C X
1 ქულა 1 ქულა

Later a synthetic scheme for the production of ambroxide from carvone was proposed.
 MgCl
1. O MeI 1. N2H4, 1. O3
D E t F
2. TMSCl TiCl4 BuOK 2. KOH, t 2. NaBH4
O

S-(+)-carvone
1. Li (изб.),
MnO2 ((CH3)2N)2CH2 NH3, EtOH 1. MsCl HF TsOH
G H I J K L X
Ac2O 2. TBDMSCl  , LiBr
C15H26O2 C22H44O2Si

2. Decode D – L. Note that the molecule of substance F contains three chiral centers.

D E F
1 ქულა 1 ქულა 1 ქულა

G H I
1 ქულა 1 ქულა 1 ქულა

J K L
1 ქულა 1 ქულა 1 ქულა
Problem 9. Fluorescent dyes (12%)
Question 1 2 3 Total
Marks 6 4 6 16
Visualizing single molecules in living cells has tremendous applications in deciphering
biochemical pathways as well as understanding diseases. Fluorescent dyes are used for this
aim. The general synthetic scheme of some classes of dyes are given below.
1. Decode A-F if F belongs to the class of cyanine dyes. F contains fragments C and D.

A B C
1 ქულა 1 ქულა 1 ქულა

D E F
1 ქულა 1 ქულა 1 ქულა
Fluorescein is another popular and historically important dye. In the 1800s, 80 tons of
fluorescein were used to confirm that the Danube and Rhein river intersect each other. It
can be prepared using one-step procedure. A fluorescein-structurally similar type of dye is
rhodamine dye JF549, which is nowadays popular for live-cell microscopy.

2. Decode H, I and JF549; propose one-step synthesis of fluorescein from phthalic

anhydride.

H I JF549
1 ქულა 1 ქულა 1 ქულა

One-step synthesis
1 ქულა

Attractive types of fluorophores are BODIPY and aza-BODIPY. The synthesis of the
BODIPY used for bio-conjugation is given below.

3. Decode K, L and Mand propose two step synthesis of aza-BODIPY from 2,4-
diphenylpyrrole.
K L M
1 ქულა 1 ქულა 1 ქულა

N
1 ქულა

Two-step synthesis
ორი რეაგენტი, თითო 1 ქულა, ჯამში 2 ქულა