Inorganic Chemistry 2: Table of Contents

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Table of contents
Inorganic chemistry 2
Solution of problem 1 (Elnyakov D.D.) ........................................ .......... 2
Solution of problem 2 (Seryakov S.A.) ........................................ ............ 5
Solution of problem 3 (Motornov V.A.) ........................................ ......... 7
Solution of problem 4 (Motornov V.A., Lebedeva O.K.) .................................. 11
Solution of problem 5 (Kovalenko A.D.) ........................................ ...... thirteen
Solution of problem 6 (Kirilenko N.Yu., Dolzhenko V.D.)................................. 17
Solution of problem 7 (Bushkov N.S.) ........................................ ........... twenty
Solution of problem 8 (Karnaukhov T.M., Dolzhenko V.D.) .................. 23
Organic chemistry 29
Solution of problem 1 (Andronov V.A.) ........................................ ....... 29
Solution of problem 2 (Zima A.M.) ........................................ ............... 31
Solution of problem 3 (Plodukhin A.Yu.) ........................................ ...... 34
Solution of problem 4 (Salnikov O.G.).................................................. ...... 37
Chemistry and life 41
Solution of problem 1 (Rodkina N.V., Bacheva A.V.)....................... 41
Solution of problem 2 (Dikhtyar Yu.Yu.) ........................................ ......... 44
Physical chemistry 48
Solution of problem 1 (Gulevich D., Kuramshin B.K.).................................. 48
Solution of problem 2 (Zima A.M.) ........................................ ............... 49
Solution of problem 3 (Karnaukhov T.M.) ........................................ ...... 52
Solution of problem 4 (Salnikov O.G.).................................................. ...... 55
Solution of problem 5 (Sedov I.A.) ........................................ .............. 59
one
© TsPMK Higher School of Chemistry
Inorganic chemistry
Solution of problem 1 (Elnyakov D.D.)
1. Assume that the liquid is an aqueous solution. The gas released at the first electrode (anode) is
apparently chlorine, since when it is passed through an aqueous solution of KI, a brown color appears and
then disappears, which corresponds to the oxidation of I– into I2 (with the formation of the triiodine ion I3–
, giving a brown color) and then into IO3 - (see the reaction equations below). An alternative,
oxygen, oxidizes the iodide ion too slowly for the solution to acquire a noticeable color in a short time. At
the same time, no gas evolution was observed at the second electrode (cathode) at the beginning of the
experiment, and its mass increased. This means that the process of reduction of a certain metal ion took
place on it. That is, the initial liquid is an aqueous solution of low-active chloride
metal.
Let the charge of this metal ion be +m, and its molar mass ÿ M. The cathodic process
ÿ
equation: Mem+ + me = Me
The beginning of gas evolution at the cathode (obviously, hydrogen) at the time
t1 indicates that the process of metal reduction proceeded during the first 5
min. 30 sec. electrolysis. Find the number of electrons that were
passed through the solution during this time:
It
n ÿe_ _ÿ
Q ÿ
0.2 A 3090 s
ÿ
ÿÿ ÿ ÿ
0.006405 moth,
F F 96485 C/ mol
where Q is the total charge transferred by electrons during the flow
cutting solution of electric current with force I in time t.
The mass of the formed metal is:
one 0.006405
m (Me) ÿ(Me)
ÿ ÿÿ
M m ÿ(e) - M
ÿÿ ÿ
0.2048 g , hence,
m
M = 31.97502 m.
m M, g/mol Me m M, g/mol Me
+1 ÿ 32 S +3 ÿ 96 Mo
+2 ÿ 64 Cu +4 ÿ 128 ÿ
At this point, enumeration of m values can be stopped, since ions with a charge greater than +4 in
an aqueous solution are unstable.
The standard electrode potential of the Mo3+/Mo pair is higher than that of the standard hydrogen
electrode. That is, during the electrolysis of an aqueous solution of molybdenum (III) chloride salt, hydrogen
immediately begins to be released at the cathode.
Thus, the aqueous solution contains copper (II) chloride in an amount of 2
0.006405 / 2 = 0.0032025 mol.

However, a contradiction arises.
First, the masses of precipitates that form when solution X is mixed with solutions of
Na3PO4 and (CH3COO)2Pb, calculated on the basis of the assumptions made earlier, are
smaller than those specified in the condition.
3CuCl2 + 2Na3PO4 = Cu3(PO4)2ÿ + 6NaCl
0.0032025
m(Cu3(PO4)2) = ÿ(Cu3(PO4)2)ÿM(Cu3(PO4)2) = ÿ =0.4078 g, 382
3
CuCl2 + (CH3COO)2Pb = PbCl2ÿ + (CH3COO)2Cu
m(PbCl2) = n(PbCl2)ÿM(PbCl2) = 0.0032025 mol ÿ 278 g/mol = 0.8903 g
Secondly, after the end of copper evolution at the cathode, chlorine continues to evolve
at the anode. That is, the number of Cl– ions turns out to be greater than could be formed during
the dissociation of CuCl2.
All this suggests that, in addition to CuCl2 , solution X also contains
one chloride, and the active metal.
Let the formula of the chloride of an unknown metal be AClk, and the formula of its phos
fata ÿ A3(PO4)k, where +k is the charge of the metal ion. Then:
2AClk + k(CH3COO)2Pb = 2(CH3COO)kA + kPbCl2ÿ
3AClk + kNa3PO4 = A3(PO4)kÿ+ 3kNaCl
1.2541 g ÿ 0.8903 g
ÿex.(PbCl2) = = 0.001308 mol
g 278.1
mole
m(A3(PO4)k) = ÿ(A3(PO4)k)ÿM(A3(PO4)k), where A is the molar mass of the metal.

On the other hand, m(A3(PO4)k) = 0.5080 g ÿ 0.4078 g = 0.1002 g,
then:
After transforming the resulting equality, we have: A = 6.6·k.

m M, g/mol Me Comment
+1 6.6 ~Li Possible solution.
+2 13.2 ÿ ÿ
+3 19.8~Ne inert gas

+4 26.4 ~Al ÿ
Thus, in addition to copper (II) chloride, solution X also contains chlorine

lithium oxide in the amount of 0.001309 mol ÿ 2 = 0.002618 mol.
C(CuCl2) = 0.0032025 mol / 0.05 L = 0.06405 mol/L
C(LiCl) = 0.002618 / 0.05 L = 0.05236 mol/L
2. Let us write down the equations of cathodic and anode processes, as a result of which
gaseous products were released:
3
Anode:
2Clÿ = Cl2ÿ + 2eÿ (between t0 and tx)
2H2O = O2ÿ + 4H+ + 4eÿ (between tx and t2)
Cathode:
2H2O + 2eÿ = H2ÿ + 2OHÿ (between t1 and t2)

where tx is the moment of time when Clÿ ions “ended” in the solution .
The amount of chlorine formed:
n(Cl2) = n(CuCl2) + 0.5n(LiCl) = 0.0045115 mol
The number of electrons that were passed during this time through the
creation:
n(eÿ ) = 2n(Cl2) = 0.0045115 mol ÿ 2 = 0.00903 mol

Therefore, the moment of time corresponding to the end of the selection
chlorine:
0.00903 mol 96485 C/mol ÿ
tx = ÿ
4360 s
0.2 A
The amount of oxygen formed during the time interval from tx to t2:
At ÿ
0.2 n(O2)ÿÿ
4360 ÿ c
2 one
= ÿ
= 5.1822ÿ10ÿ7 (t2 – 4360) mol
96485 /Cl mol 4
The amount of hydrogen formed during the time interval from t1 to t2:
0.2 A t ÿ ÿÿ
2
3090 ÿ c one
n(H2) =
ÿ
= 1.03644ÿ10ÿ6 (t2 – 3090) mol

96485 /Cl mol 2
By the condition n(Cl2) + n(O2) = n(H2). Let's make an equation:

0.0045115 + 5.1822ÿ10ÿ7 (t2 ÿ 4360) = 1.03644ÿ10ÿ6 (t2 ÿ 3090)
Where t2 = 10526 sec. = 175 min. 26 sec.
3. Reaction equations:
1) CuCl 2
ÿÿÿÿ ÿ Cu + Cl
email current
2
ÿ
2) 2LiCl + 2HO2
email current
ÿÿÿÿÿ diaphragm ÿ
2LiOH + Cl +2 H 2
ÿ
2H O 2 ÿÿÿÿ
2
H + Oÿ4)3)Cl2 + 3KI(e) =
email current
2 2
ÿ
2KCl + KI3
5) I2 + 5Cl2 + 6H2O = 2HIO3 + 10HCl,
count also: 2KI3 + Cl2 = 2KCl + 3I2ÿ
6) 3CuCl2 + 2Na3PO4 = Cu3(PO4)2ÿ + 6NaCl
7) 3LiCl + Na3PO4 = Li3PO4ÿ + 3NaCl
8) CuCl2 + (CH3COO)2Pb = PbCl2ÿ + (CH3COO)2Cu
9) 2LiCl + (CH3COO)2Pb = PbCl2ÿ + 2CH3COOLi
4
Grading system:
1. Establishing the composition of liquid X:

Conclusion that chlorine is released at the anode - 2 points
Conclusion that a low-active metal is released on the cathode up to t1 - 1 point
Conclusion that hydrogen is released on the cathode after t1 - 1 point
13 points
Calculation-based determination of copper - 3 points
Conclusion that liquid X is a mixture of copper chlorides and active metal - 2 points
Calculation-based determination of lithium - 3 points

Calculation of concentrations of CuCl2 (0.5 points) and LiCl (0.5 points) - 1 point
2. For finding the time during which the electric

3 points
Trolysis (t2) - 3 points
3. Equations of chemical reactions:

For equations of electrode processes - 1 point for each equation in molecular form
or 0.5 points for each scheme of the oxidation or reduction process - 3 points
For each of the two equations explaining the appearance and disappearance of a
9 points
brown color when chlorine is passed through an aqueous solution of potassium
iodide, 1 point - 2 points
For each of the four equations of reactions that occur when liquid X is mixed with
aqueous solutions of sodium phosphate and lead (II) acetate, 1 point each - 4 points
TOTAL: 25 points
Solution of problem 2 (Seryakov S.A.)

Animal + plane = "mouse" + "Yak" = "arsenic".
1. Judging by the description and the above scheme of transformations, B is an acid oxide (formed
by the interaction of A with O2), C is the corresponding acid (hydration product of B), G is the hydrogen
compound A (obtained by reduction of A with zinc and subsequent treatment with HCl) . We reject the
possibility that A is a halogen, since halogens are not oxidized by oxygen. Since acid C is capable of
being oxidized (the action of HNO3), and can also be semi-
5
When D is reduced with an iodide ion, nonmetal A forms 2 acids in different oxidation states.
Both acids are acid stable in the absence of oxidizing/reducing agents. On reflection and
taking into account the historical background, as well as the toxicity of all A compounds, we
can conclude that this is arsenic. A = As.
Reaction equations:
1. 4As + 3O2 = As4O6 (or As2O3)
2. As4O6 + 6H2O = 4H3AsO3
3. H3AsO3 + 2HNO3 = H3AsO4 + 2NO2 + H2O
4. H3AsO4 + 2KI + H2SO4 = H3AsO3 + H2O + I2 + K2SO4
5. H3AsO4 + 5HCl (tº) = AsCl3 + Cl2 + 4H2O
6. AsCl3 + 6NaOH = Na3AsO3 + 3NaCl + 3H2O
7. 2Na3AsO3+ 3H2SO4 = 2H3AsO3 + 3Na2SO4
8. 3Zn + 2As = Zn3As2
9. Zn3As2 + 6HCl = 3ZnCl2 + 2AsH3
10. 2AsH3 (tº) = 2As + 3H2
Substances:
A = As, B = As4O6 (As2O3) C = H3AsO3 D = H3AsO4
E = AsCl3 F = Zn3As2 G = AsH3
2. Determine the ratio C: O in compound H:
C: O = (21.24/12): (7.08/16) = 1.77: 0.4425 = 4: 1. Based on oxygen, we determine the
estimated molar mass of the compound M = 16/0.0708 = 226 g/mol. Since in potassium
acetate C: O = 1: 1, such a significant decrease in the proportion C: O in the substance H
compared with the acetate ion, as well as the fact that carbon dioxide is released in the
reaction, can be explained by the decarboxylation of the acetate ion , in this case, carbon
atoms are included only in the CH3 groups. Let us determine the remainder of the molar
mass (minus 1 oxygen atom and four CH3 groups). Bridge \u003d 226 - 16 - 4 15 \u003d 150
g / mol, which corresponds to twice the molar mass of arsenic. Taking into account the
trivalent nature of arsenic, the formula has the form [(CH3)2As]2O. Education Equation:
2AsCl3 + 6CH3COOK + H2O = [(CH3)2As]2O + 4CO2 + 2CH3COOH + 6KCl.

3. Arsenic in AsCl3 has 4 valence orbitals of 4s- and 4p sublevels filled, in contrast to
Al, which has a vacant orbital in AlCl3. The formation of dimers for AlCl3 in the gas phase is
a way to saturate the valence orbitals with electrons; this is not necessary for arsenic.
4. A heavier analog of arsenic is antimony. A gray spot formed as a result of the

thermolysis of arsine in a glass tube, when dissolved
6
ion in sodium hypochlorite gives a clear solution, and the decomposition product of stibine under the
same conditions will give an insoluble yellowish precipitate:
2As + 5NaClO + 3H2O = 2H3AsO4 + 5 NaCl
2Sb + 5NaClO + xH2O = Sb2O5ÿxH2O + 5 NaCl
(other oxidizing agents can be used, for example, a mixture of hydrogen peroxide and ammonia).
Grading system
1. 7 substances - 1 point each,

17 points
10 reactions - 1 point each
2. correct formula of substance H - 1.5 points

3 points
reaction equation - 1.5 points each
3. Correct explanation 2 points
4. Reaction equations (with explanations) - 1.5 points each 3 points
TOTAL: 25 points
Solution of problem 3 (Motornov V.A.)

1. A is a binary compound, that is, it consists of 2 elements. When A reacts with carbon
monoxide, a simple substance 3 is formed, which stains starch. It can be assumed that Z is I2, then
A contains iodine, X - iodine. In addition to Z , gas I is formed, which is part of the air, with a molar
mass
M DH MH 221.83 22.016
AND
ÿ ÿ
ÿ ÿ G ÿ
44.01 G
, which corresponds to CO2. Means
mole mole
The second element in A is oxygen.

Let's determine the composition of iodine oxide (I2Ox):
2 ÿ
M I
=>
2 ÿ
M I
ÿÿ
ÿ I
ÿ
) 2 126.905 (1 0.7604)
ÿÿ
ÿ ÿ
x ÿ
(one
ÿ ÿ
5 .
I
2 ÿMÿ ÿx IM O M OI
ÿ
ÿ 15.999 0.7604 ÿ
A - I2O5
The composition of compound A can also be established using enumeration if at least one of the
elements is correctly assumed.
In I2O5, iodine is in the +5 oxidation state; when chlorine is passed through an alkaline solution,
it is oxidized to +7. In this case, according to the condition of the problem, salt B is formed . Salt B is
the sodium salt of acid K, about which it is known that it forms an average silver salt L. Let us calculate
the molar masses of B and L per one iodine atom:
G G
ÿ ÿ126.905 / 0.4318 ÿ 293.90 ;
MB ÿ MI / mole mole
7
ML ÿ126.905 G
/ 0.1665 ÿ 762.19 G .
mole mole
Since salt B is formed in an aqueous solution, it is logical to assume that in

the composition of B and L , in addition to metal cations, also includes oxygen.
Composition L – AgxIOy, then 126.905 ÿ107.87 ÿ x ÿ15.999 ÿ y ÿ 762.19 , footprints
Therefore, y ÿ 39.71ÿ 6.742 ÿ x :
xyxy
1 32.97 4 12.74
2 26.22 5 6.00
3 19.48 6 -0.75
That is, L - Ag5IO6. Then the acid K is H5IO6.
5-
Let us now determine the composition of B. Anion IO6 has a molar mass
222.90 moleG , means cations account for 293.90 ÿ 222.90 ÿ 71 G
mole
, which corresponds
corresponds to 3 sodium cations and 2 protons: 22.99 ÿ3 ÿ 2 ÿ1.008 ÿ 71 G . Means

mole
composition B is Na3H2IO6.
Metal Y occurs naturally as oxide M, for which nMO is known
ÿÿ
share of metal. Assume the composition of the oxide Y2On, then M Y ÿ
21 ÿÿ
n MY n MY
1 13.73 5 68.66
2 27.46 6 82.39
3 41.20 7 96.13 Mo
4 54.93 Mn 8 109.86
Molybdenum does not form an oxide of the composition Mo2O7, the only
reasonable answer is MnO2, which actually occurs in nature as the mineral pyrolusite.
Thus, M is MnO2 and Y is Mn. Salt B precipitates with barium salts, it can be assumed
that B is manganese (II) sulfate.
G G
MB ÿ MMn / ÿ ÿ 54.938 / 0.1984 ÿ 276.91
mole mole
Subtract the mass of MnSO4 from the resulting mass: 276.91ÿ151.00 ÿ125.91 G
,
mole
the remainder corresponds to 7 water molecules. C - MnSO4 7H2O.

The condition indicates that G is a crystalline hydrate, and for analysis, the Young
Chemist heated this compound, it can be assumed that at 150 ÿÿ, the weight loss is
associated only with water.
During the interaction of Na3H2IO6 and MnSO4 7H2O in the reaction mixture, the
eight
NaOH and NaOCl are present. It is known that hypochlorite is a strong oxidizing agent, and
since iodine is already in the highest oxidation state,
only manganese can change the oxidation state.
To analyze the resulting compound, the Young Chemist passed sulfur dioxide, which
is a reducing agent, through its solution. In compound D, the oxidizing agent can be
periodate ions and a manganese ion.
After reduction, the Young Chemist added an excess of silver nitrate to the solution,
and a yellow precipitate D - AgI precipitated, which can be confirmed by the calculation
volume:
M
D ÿ MI /
ÿ ÿ126.905 G
/ 0.5405 ÿ 234.79 G
ÿM _ .
mole mole AgI
0.1452 G
ÿ ÿ ÿ
0.618 mmol
AgI G
234.79
mole
From the same amount of salt G , 0.0179 g of L is precipitated by ammonium sulfide .

Transition metal sulfides are poorly soluble; the solution contains manganese ions, which
allows us to conclude that L is MnS.
0.0179 G
ÿ ÿ ÿ
0.206 mmol
MnS G
87.00
mole
That is, in the resulting compound, the molar ratios Mn: I = 1: 3.

When reduced with sulfur dioxide, manganese was reduced to Mn+2, and iodine to Iÿ1
, sulfur is oxidized to SO4 2ÿ. When barium chloride is added, a precipitate E -
BaSO4 with a mass of 0.6252 g precipitates.
ÿ 2
2.68
ÿ
0.6252 G SO4
ÿ BaSO4 ÿ ÿ
2.68 mmol ; ÿ ÿ thirteen
_ G ÿ 0.206
233.39
mole Mn 2 ÿ
In redox reactions, the number of donated electrons

ÿ4 ÿ6 2e
always equal to the number received. In the electron half- 2 are involved
2ÿ
reaction, and since 1 mol of Mn produces 13 mol of SO4 in the second half-reaction
26 electrons must participate:
n_ ÿ 7 ÿ 26e _ 2ÿ ÿ
one
Mn ÿ I ÿÿÿÿMn
33 ÿI ,
i.e., the oxidation state of Mn in ÿ is +4.
So, 0.25 g of crystalline hydrate G contains 0.206 mol of Mn+4. This allows
calculate the molar mass G per 1 Mn atom:
0.25 G G
MG ÿ ÿ 1213 .
ÿ
3 mole
0.206 10 ÿ
mole
The mass fraction of water in this compound is
9
0.5000 0.3664 ÿ
ÿ
H2
O
ÿ ÿ
0.2672 , per 1 atom of manganese is the composition
0.5000
lays
G
1213 ÿ
0.2672
mole
nH O 2
ÿ
G
ÿ
eighteen water molecules.
eighteen
mole
In addition, this substance contains Mn + 4, 3 IO6 5- , x Na+ and possibly

but, y H + : NaxHyMn(IO6)3.
To comply with the condition of electroneutrality x + y + 4 = 5 3. => x + y = 11.
M xG
ÿÿ
M y MMMM Na
ÿÿ
HMn
3ÿÿÿ ÿÿÿ5
eighteen
HO
ÿ
IO6 _ 2
G
ÿ
_ x54.938 3 222.90
22.99 1.008 ÿ ÿ ÿ18ÿ 18.015
ÿy 1213 ÿ
mole
22.99x ÿ1.008 ÿ(11ÿ x) ÿ165.092

21.982x ÿ154.004
x ÿ 7; y = 4
*
i.e. G - Na7H4Mn(IO6)3 18H2O or Na7[Mn(HIO6)2(H2IO6)] 18H2O
A I2O5 F MnS
B Na3H2IO6 C W I2
MnSO4 7H2O D and CO2
Na7[Mn(HIO6)2(H2IO6)] 18H2O C H5IO6
D AgI R Ag5IO6
E BaSO4 M MnO2
1) I2O5 + H2O ÿÿ 2HIO3
2) HIO3 + 5NaOH + Cl2 ÿÿ Na3H2IO6 + 2NaCl + 2H2O
3) 3 Na3H2IO6 + NaClO + MnSO4 ÿÿ

Na7[Mn(HIO6)2(H2IO6)] + NaCl + Na2SO4 + H2O
150ÿC
4) Na7[Mn(HIO6)2(H2IO6)] 18H2O ÿÿÿÿ
Na7[Mn(HIO6)2(H2IO6)]+18 H2O
5) Na7[Mn(HIO6)2(H2IO6)] + 13 SO2 + 8 H2O ÿÿ

3 NaI + MnSO4 + 2 Na2SO4 + 10 H2SO4
6) Ag+ + I– ÿÿ AgIÿ
7) Ba2+ + SO4 2– ÿÿBaSO4 ÿ
*
Levason W., Specer M.D., Webster M.// Inorg. Chem. (1992) V.31, no.12, pp.2575-2579.
doi:10.1021/ic00038a049
10
8) Mn2+ + S2– ÿÿ MnSÿ
9) I2O5 + 5 CO ÿÿ I2 + 5 CO2
3. It is necessary to dry in an inert atmosphere, as manganese sulfide can
be oxidized by atmospheric oxygen:
tÿC
3MnS + 5O2 ÿÿÿ Mn3O4 + 3SO2
or
tÿC
4MnS + 7O2 ÿÿÿ 2Mn2O3 + 4SO2
Grading system:
1 Elements X and Y 1 point each 2 points
Substances A - M 0.5 points each 6 points
Calculation of the composition A, B, C , D, L, M for 1 point 6 points
2 Reaction equations for 1 point 9 points
3 Answer to the question -1 point 2 points
Reaction equation - 1 point
TOTAL: 25 points
Solution of problem 4 (Motornov V.A., Lebedeva O.K.)

1. Element A is a non-metal capable of forming many acids in different oxidation states (reactions 4,
5), in addition, reactions 1 and 2 indicate that several atoms of element A are included in a number of
acids. Such a non-metal can be phosphorus or sulfur, but phosphorus acids and salts do not dissolve silver
bromide (reaction 3). Thus, element A is sulfur (S).
2. A2 - acid anhydride, sulfur can have two of them: SO2 and SO3, which correspond to sulfurous
and sulfuric acids, respectively. The stable acid X3 is sulfuric acid - (H2SO4), so A2 is sulfur oxide (VI)
- SO3.
Sulfuric acid salts are obtained from the acid salt X2 in the presence of an oxidizing agent (iodine)
(reaction 4). Then it is logical to assume that X2 acid is an unstable sulfurous acid. Acid X1 contains
two
sulfur atom, since when it decomposes at temperatures below zero, two substances containing sulfur are
obtained: A1 and sulfuric anhydride A2 (reaction 2). Then the binary gaseous substance A1 must contain
sulfur and hydrogen, i.e. A1 is hydrogen sulfide H2S. Salt A3 is sodium thiosulfate Na2S2O3.
Let us determine the composition of A4. The dissolution of silver bromide occurs due to the
formation of a complex salt. Salt contains silver, sulfur, sodium,
eleven
oxygen. If the complex contains one silver atom, then the molar mass will be 108/0.1932 =
559 g/mol. The sulfur content in 1 mole of salt will be 559 0.3435 = 192 g, which corresponds
to 6 moles of sulfur in one mole of salt. The thiosulfate ion can act as a ligand; in this case,
9 moles of oxygen will fall on 6 moles of sulfur, i.e., the [Ag(S2O3)3] particle is included in
5ÿ
the composition of A4 . A4 -
this is Na5[Ag(S2O3)3]. The structure of the binuclear complex of silver with thiosulfate
10ÿ(*)
[Ag2(S2O3)6] is described in the literature. .
Let us determine the composition of sodium salt
A5. The ki slots that sulfur forms are basically two main
ones. Then the molar mass of the salt will be M(A5) =
46 / 0.2643 = 174 g/mol. The acid residue accounts for
174 ÿ 46 = 128 g. If the anion contains 1 sulfur atom,
then the number of oxygen atoms is 6, which cannot
be. If there are 2 sulfur atoms, then they have 4 oxygen atoms. The composition of the
S2O4 2ÿ anion. If we assume the presence of 3 sulfur atoms, then the composition of the
S3O2 anion is 2ÿ, but in this case, reaction 6 is impossible. Thus, A5 is sodium dithionite
Na2S2O4, and acid X4 is dithionic acid H2S2O4.
In the interaction of equimolar amounts of ammonia and SO3 , sulfamic acid

H[NH2SO3] - X5 is obtained . Its potassium salt is potassium sulfamate K[NH2SO3] - A6.
X1 H2S2O3 A1 H2S
X2 H2SO3 ÿ2 SO3
X3 H2SO4 A3 Na2S2O3
ÿ4 H2S2O4 ÿ4 Na5[Ag(S2O3)3]
X5 H[NH2SO3] A5 Na2S2O4
A6K [NH2SO3]
3. Reaction equations
ÿ ÿ
2 ÿ
ÿ ÿ
ÿ
1) 2HS 4HSO 3S O 3H2O 3 23
ÿÿ5ÿC, Et2O †
2) H2S2O3 ÿÿÿÿ ÿÿ H2S + SO3
AgBr3NaSO3
ÿtvÿ
ÿ ) 2 2 3(p p) ÿ
ÿ
Na [Ag(SO)]
5 2 3NaBr(p
3 (p p) p) ÿ
ÿ ÿ
ÿ
HSO ÿ I ÿ HO ÿ HSO ÿ 2H ÿ 2I
ÿ ÿ ÿ
4) 3 2 2 4
* Chan EJ, Skelton BW, White AH // Z. anorg. allg. Chem., (2008) Bd. 634, pp. 2825–2844.
doi:10.1002/zaac.200800316
† M. Schmidt // Z. anorg. allg. Chem. (1957), Bd. 289, pp. 141-157,
12
5) Zn + 2SO2 = ZnS2O4
6) 2Na2 S2O4 ÿ Na2 S2O3 ÿ Na2 SO3 ÿSO2
7) NH3 + SO3 = H[NH2SO3]
8) H[NH2SO3] + KHSO4 + Ca(OH)2 = K[NH2SO3] + CaSO4 + 2H2O
4.
2-
SO3 S2O4
(SO3)3 OO _______ H[NH2SO3]

S
O O
O S S O
O
O O
Grading system:
1 Establishment of element A 4 points
2 Establishment X1-X3, X5, A1-A3, A5, A6 1 point each Establishment 9 points
X4, A4 2 points each 4 points
3 Reaction equations 1–8 0.5 points each 4 points
4 Structural formulas of A2, A2 trimer, X4 acid anion and X5 acid, 1 point each 4 points
TOTAL: 25 points
Solution of problem 5 (Kovalenko A.D.) 1.

Various colors of compounds of element X, its application in metal
urgy and the production of galvanic cells indicate that element X is a transition metal. Dark purple
crystals, used in the laboratory as a starting compound and in everyday life as an antiseptic, resemble
potassium permanganate. The molar mass A = 54.938 / 0.3476 = 158.0 g/mol, which corresponds to
the molar mass of potassium permanganate. Then A is KMnO4 and X is Mn. The fact that X is
manganese can be arrived at by calculation, using the numerical data for the binary substance B (oxide,
since it is formed by the action of conc. sulfuric acid on A ). Let the composition of oxide B be X2On,
then we obtain the equation: X 2 M ( )
0.4955 ÿ r
, whence Mr(X) = 7.86n.
2 M (r ) X16 ÿ n
thirteen
The only reasonable option is obtained at n = 7, i.e. M(X) = 55 g/mol - manganese.
Thus, the interaction of potassium permanganate with concentrated sulfuric acid results in
an oily liquid, manganese(VII) oxide. B - Mn2O7.
When potassium permanganate reacts with concentrated hydrochloric acid, manganese is

reduced. The oxidation state of manganese in compound C depends on the reaction conditions;
in the presence of potassium chloride, complex manganese chloride can be formed. Let's find
the molar mass of C: 54.938/0.1588 = 345.96 g/mol. This does not correspond to integer hydrate
of manganese (II) chloride, nor potassium-manganese (III) chloride K2MnCl5. When decomposed
160 ml 1.25 ÿ mole

l
nii C stands out \u003d 0.1 mol of chlorine (yellow-green suffocated
1000 2 ÿ
14.9 g
gas), as well as 74.5 = 0.2 mol KCl. Subtract from Mr(C) twice the mass
G
mole
KCl and the mass of Cl2, we get 345.96 - 71 - 2 74.5 = 125.96 - the molar mass of MnCl2, which
means C - K2MnCl6, potassium hexachloromanganate (IV).
K2MnCl6 is unstable in an aqueous solution; it can decompose with the release of chlorine
and potassium chloride. However, manganese (II) and (III) hydroxides are unstable in an alkaline
environment, and are oxidized by atmospheric oxygen to manganese oxide IV.
D – MnO2, manganese oxide IV.
Compounds E and F are obtained by reacting KMnO4 and MnO2 with KOH, respectively.
In addition, when E is fused with KOH in a nitrogen atmosphere , F is obtained, and when heated
in a nitrogen atmosphere, E decomposes into F and MnO2. It follows from this that the oxidation
state of manganese in E is greater than in F. In addition, placing F in water obviously leads to
disproportionation into E (green solution) and D (MnO2). That is, the oxidation state of manganese
in F is intermediate between that in E and MnO2. But E is stable only in alkaline solution and,
upon acidification, also disproportionates to permanganate (crimson coloration) and manganese
dioxide. Considering all this, E is K2MnO4, potassium manganate (VI), and then in F the oxidation
state of manganese is +5, that is, F is K3MnO4, potassium manganate (V).
The reaction A ÿ G is a reduction reaction. When potassium permanganate reacts with

strong reducing agents in an acid medium, manganese is reduced to the +2 oxidation state.
Then G is manganese(II) acetate. Molar mass G = 54.938/0.2242 = 245.0 g/mol. This is more
than Mr(Mn(CH3COO)2),
14
This means that a crystalline hydrate is formed. Establish its hydrate composition. Subtract
the mass of manganese and acetate ions and divide by the molar mass of water, we get
(245.0 - 55.0 - 2 59.0) / 18.0 = 4 - four water molecules. Then G – Mn(CH3COO)2 4H2O.
The interaction of manganese acetate with potassium cyanide results in the formation
of a manganese cyanide complex. Molar mass J = 54.938 / 0.1303 = 421.63 g/mol, we find
the number of water molecules, for this we subtract the mass of manganese, potassium and
cyanide anions and divide by the molar mass of water, we get:
(421.63 – 54.938 – 6 26.025 – 4 39.098)/18.0 = 3 – three water molecules.
Then J – K4[Mn(CN)6] 3H2O.
When the K4Mn(CN)6 complex interacts with metallic aluminum in an alkaline medium,
the manganese ion is reduced to the +1 oxidation state, which is possible due to the stability
of the cyanide environment of the manganese ion [Mn(CN)6]
5- .
K – K5[Mn(CN)6].
If you add oxalic acid to a solution of a manganese (II) salt, a sparingly soluble
manganese oxalate will precipitate, L - manganese (II) oxalate. Establish its hydrate
composition. Molar mass L = 54.938/0.3069 = 179.00 g/mol, subtract
mass of manganese and oxalate anion and divide by the molar mass of water, we get
(179.00 – 54.938– 88.0)/18.0 = 2 – two water molecules. Then L is MnC2O4 2H2O.
The reaction L ÿ M is the co-proportionation of manganese in the oxidation states +2
and +7 with the formation of a manganese(III) trisoxalate complex. Let us find the hydrate
composition of this complex. The molar mass is M = 54.938/0.112 = 490.52 g/mol,
subtracting the masses of manganese, potassium, and three oxalate anions and dividing by
the molar mass of water, we obtain (490.52 – 54.938 – 3 39.098 –
3 88.02)/18.0 = 3 – three water molecules. Then M – K3[Mn(C2O4)3] 3H2O.
The reaction G ÿ H is the synthesis of manganese carbonyl, H is Mn2(CO)10 (for the
justification of the formula, see step 3 of the solution), as indicated by a high CO pressure.
Three ethylaluminum acts as a reducing agent.
Reaction equations:
1) 2KMnO4 + 2H2SO4 (conc.) = Mn2O7 + 2KHSO4 + H2O
2) 2KMnO4 + 16HCl(conc.) + 2KCl = 2K2MnCl6 + 3Cl2 + 8H2O
3) K2MnCl6 + 3O2 + 4KOH = MnO2 + 2KClO3 + 4KCl + 2H2O
0
700 C
4) 4MnO2 + 12KOH + O2 ÿÿÿÿ 4K3MnO4 + 6H2O
0
100 C
5) 4KMnO4 + 4KOH ÿÿÿÿ 4K2MnO4 + O2 + 2H2O
0
700 ÿ
6) 4K2MnO4 + 4KOH ÿÿÿÿ
N2
4K3MnO4 + O2 + 2H2O
15
0
520 ÿ
7) 3K2MnO4 ÿÿÿÿ
N2
2K3MnO4 + MnO2 + O2
0
100 C
8) 4KMnO4 + 5C2H5OH + 7CH3COOH + 5H2O ÿÿÿÿ
4Mn(CH3COO)2 4H2O + 4CH3COOK

200 bar
9) 6Mn(CH3COO)2 + 4(C2H5)3Al + 30CO ÿÿÿÿ
3Mn2(CO)10 + 4Al(CH3COO)3 + 6C4H10
10) Mn(CH3COO)2 + 6KCN + 3H2O = K4[Mn(CN)6] 3H2O + 2CH3COOK
11) 3K4[Mn(CN)6] + Al + 4KOH = K5[Mn(CN)6] + K[Al(OH)4]
12) Mn(CH3COO)2 + K2C2O4 + 2H2O = MnC2O4 2H2O + 2CH3COOK
13) 3KMnO4 + 4MnC2O4 + 9K2CO3 + 21H2C2O4= 7K3[Mn(C2O4)3] 3H2O + 17CO2
2. Equations of the mentioned reactions:
K2MnCl6 = MnCl2 + Cl2 + 2KCl
3Cl2 + 6KOH = KClO3 + 5KCl + 3H2O
2K3MnO4 + 2H2O = K2MnO4 + MnO2ÿ + 4KOH, after neutralization of the formed
alkali, potassium manganate also disproportionates:
3K2MnO4 + 2H2O = 2KMnO4 + MnO2ÿ + 4KOH
3. During the formation of carbonyls, the atoms of 3d-metals tend to complete the 18-electron
shell, while one CO molecule provides the central atom with 2 electrons. One atom of
7
manganese(0) - 3d - may not attach
more than 5 CO molecules, since then the number of electrons will be 7 + 2 5 = 17. Complex
particles Mn(CO)5 are unstable and dimerize, since each manganese atom in the resulting
dimer will receive 18 electrons, so the formula H is Mn2(CO)10. The structure of the carbonyl
Mn2(CO)10 is shown in the figure. Five CO molecules form a tetragonal pyramid with a
manganese atom at its base. There are no bridging CO atoms in the molecule, there is a Mn-
Mn bond with a length of 2.93 Å (1 Å = 10–8 cm). Two tetragonal pyramids are located on
the same axis with their bases to each other and rotated relative to each other by 45°.
sixteen
Grading system:
1. Reaction equations 1 - 13 for 1 point.

20 points
Establishing the composition of A, B, C, G, J, L and M by 1 point.
2. Four reaction equations for 1 point. 4 points
3. Correct structure - 1 point.

(the pyramid turn is not taken into account, the full score is given for the 1 point
dimeric structure)
TOTAL: 25 points
Solution of problem 6 (Kirilenko N.Yu., Dolzhenko V.D.)

1. Metal X is part of the shape memory alloy, when dissolved in hydrochloric acid it forms violet
solutions, when oxidized with oxygen it gives oxide, which is used as a white pigment, its salts in an
acidic environment with peroxide are yellow. All of the above features
fit titanium.
If the listed properties are not enough to identify the metal, we will carry out calculations. When
a metal is oxidized with oxygen, oxide A is formed, sintering with which metal X makes it possible to
obtain B. Since no other elements are introduced, B is an oxide. Let's try to identify the metal
8n : ÿ_
ÿ ÿ
according to its mass fraction in X2On oxide. MX ÿ
one
ÿ
nMX _ nMX _
1 15.95 oxygen 5 79.76 bromine

2 31.90 sulfur 6 95.71 molybdenum
3 47.86 titanium 7 111.66
4 63.81 copper 8 127.62 tellurium
Oxygen, sulfur and bromine can be discarded because X is a metal. For tellurium, the +8 oxidation
state is unattainable. B is a metal oxide in a low oxidation state, so copper and molybdenum are also not
suitable. Thus, the rest
only titanium is available.
Let us calculate the molar masses of compounds E, G, H, J per 1 atom

tana:
Substance ÿ(X), % M, g/mol

E 3.33 1437.5
17
F 41.9 115.9
H 20.9 229.0
I 19.2 249.3
J 26.9 177.9
When titanium is oxidized in air, TiO2 (A) is formed, which is included as a
pigment in "titanium white". The interaction of metal oxides with coal and chlorine at
high temperature is a method for obtaining chlorides. In this case, TiCl4 (C) is formed.
Titanium tetrachloride is completely hydrolyzed by water to titanic acid, which is
hydrated titanium (IV) oxide TiO2 nH2O. Judging by the calculated molar mass , F is ÿ
titanic acid TiO2 2H2O, H4TiO4 or Ti(OH)4.
Titanium, when interacting with non-oxidizing acids, is oxidized to an oxidation

state of +3, forming the corresponding salts. When dissolved in hydrochloric acid,
TiCl3 (D) is formed. Titanic acid dissolves in hydrofluoric acid to form complex acid
H2TiF6 (G). The interaction of hydrogen peroxide with transition metal ions can lead
to the formation of peroxo complexes of various compositions. In the composition
of the yellow precipitate, along with the peroxo group O2
2-
may include fluoride ions and ions
ammonium, which are formed when ammonia is added to a hydrofluoric acid solution.
From the indication that the substance is diamagnetic, the oxidation state of titanium is
+4. Thus, the precipitate composition can be represented as: (NH4)x[TiFy(O2)z], with
x = 2z + y – 4. Then the molar mass of the compound H will be
det is equal to:
MH ÿ17 ÿ(2z ÿ y ÿ 4) ÿ 47.867 ÿ19 y ÿ 32z ÿ 36 y ÿ 66z ÿ 20.113 ÿ 229.0

y ÿ (229.0 ÿ 66z ÿ 20.113)/36 ÿ 6.920 ÿ1.833z
zyzy
1 5.087 3 1.420
2 3.253 4 -0.413
Only z = 1 corresponds to the integer value y = 5, which means that the composition of the
substance is (NH4)3[TiF5(O2)] (H).
When cyclopentadienyl sodium (NaCp) reacts with titanium tetrachloride (TiCl4) ,
an exchange reaction occurs in which chloride ions are replaced by cyclopentadienyl
anions, and the driving force of this reaction is the formation of a precipitate of sodium
chloride, which is insoluble in nonpolar THF. The composition of the resulting compound
should correspond to the formula Ti(Cp)nCl4–n.
MI ÿ (5 ÿ12 ÿ 5) ÿ n ÿ 35.453 ÿ(4 ÿ n) ÿ 47.867 ÿ 249.31
eighteen
249.31 35.453 4 47.867

ÿ
ÿÿ
59.63
n_ ÿ ÿ 2
ÿ ÿ5ÿ35.453
5 12 29.55
So the composition of I is Ti(C5H5)2Cl2.

MI ÿ MJ ÿ 71 , which corresponds to two chlorine atoms, which means that the composition of J is
Ti(C5H5)2.
It follows from the condition that in compound E , the titanium cation is in the vicinity of
the formation of six molecules of acetonitrile, since only they have a nitrogen atom in their composition
[Ti(CH3CN)6] k+. The composition of the anion should include iodine, let us calculate the
molar mass of the anions: 1437.5 – 47.867 – (12.011 2 + 14.007 + 3) 6 = 1143.5, which
correspond to nine iodine atoms, and since the composition of all anions must be identical,
and the degree +9 oxidation is impossible for titanium,* it remains to be assumed that
compound E corresponds to the composition [Ti(CH3CN)6](I3)3
in favor of the oxidation state
tana +3 is also indicated by the fact that this compound is paramagnetic.
If the composition of the compounds was determined not on the basis of calculations, then under
we fix the composition:
ÿ(X), ÿ(X),
Substance M, g/mol Substance M, g/mol
% %
V Ti2O3 143.80 66.6 H (NH4)3[TiF5(O2)] 228.973 20.9
E [Ti(CH3CN)6](I3)3 1436.32 3.33 I Ti(C5H5)2Cl2 248.96 19.2
F TiO2 2H2O 115.93 41.3 J Ti(C5H5)2 178.053 26.9
tÿC
1. Ti + O2 ÿ ÿÿ TiO2
1600ÿC
2. 3TiO2 + Ti ÿÿ ÿÿ 2Ti2O3
tÿC
3. TiO2 + 2C + 2Cl2 ÿ ÿÿ TiCl4 + 2CO
4. 2Ti + 6HCl ÿÿ 2TiCl3 + 3H2

CH3CN
5. 2Ti +9 I2 + 12CH3CN ÿÿÿÿÿ 2[Ti(CH3CN)6](I3)3
6. TiCl4 + 4H2O ÿÿ TiO2 2H2O + 4HCl

tÿC
7. TiO2 2H2O ÿ ÿÿ TiO2 + 2H2O
8. TiO2 2H2O + 6HF ÿÿ H2[TiF6] + 4H2O

pHÿ6
9. H2[TiF6] + H2O2 + 4NH3 H2O ÿÿ ÿÿ (NH4)3[TiF5(O2)] + NH4F + 4H2O
THF
10. TiCl4 + 2NaC5H5 ÿÿÿÿ Ti(C5H5)2Cl2 + 2NaCl
* Hathaway BJ, Holah DG// J. Chem. soc. (1965), pp. 537-541; doi:10.1039/JR9650000537
nineteen
THF
11. Ti(C5H5) 2Cl2 + 2NaC10H8 ÿÿÿÿ Ti(C5H5)2 + 2NaCl+2C10H8
3. In an alkali solution, titanic acid is partially dissolved due to
formation of oxo-hydroxo- or hydroxo-complexes, for example:
TiO2 2H2O + 2NaOH(conc) ÿÿ Na2[Ti(OH)6]

Titanium oxide is inert and with alkali solutions at room temperature
practically unresponsive.
If TiO2 is heated in a 40% NaOH solution, 110°ÿ, for 20 hours, Na2Ti2O4(OH)2 is released from
*
the solution upon dilution .
Under the conditions of hydrothermal synthesis (500°ÿ, 0.1 GPa), TiO2 noticeably
is created and titanates of various compositions crystallize from the solution
†
(Na2Ti3O7, Na16Ti10O28) .
When oxide is fused with alkali, mixed titanium oxides are formed
sodium, for example:
tÿC
TiO2 + 2NaOH ÿ ÿÿ Na2TiO3 + H2O
4. Titanium is a fairly common element in the earth's crust, although it is scattered. There is a huge
number of titanium minerals, the most famous are ilmenite (FeTiO3), perovskite (CaTiO3), rutile (TiO2),
anatase (TiO2), titanite (CaTiSiO5).
Grading system:
1 Determination of metal X and substances A–J – 0.5 points each 11.5 points
Calculation of composition B, E, F, G, H, J by 1 point
2 Reaction equations for 1 point 11 points
3 Equations of reactions with alkali 1 point each 2 points
4 Any mineral - 0.5 points 0.5 points
TOTAL: 25 points
Solution of problem 7 (Bushkov N.S.)

1. Gas X, one of the components of air - most likely nitrogen or oxygen. In the problem we are talking
about very strong oxidizing agents - it is logical to assume that they contain oxygen or fluorine. We are
given mass fractions of a heavier element
* Jianjun Y., Zhensheng J., Xiaodong W., Wei L., Jingwei Z., Shunli Z., Xinyong G., Zhijun Z.//
Dalton Trans. (2003), no. 20, pp. 3898-3901; doi:10.1039/B305585J
†Ilyushin G.D. // Crystal chemistry (2006), V. 51, No. 4, p. 760 .; doi:10.1134/S1063774506040304
twenty
ment in a binary substance and in the product of its reaction with gas X in a ratio of 1:1. This allows
us to calculate the molar mass of compound Y using the formula:
where is the atomic mass of the heavier element, and n is the number of its atoms in the compound
nenie.
If we assume that X is nitrogen, then ÿ(ÿ) = 28 g/mol, Ar = 171.29/n, we do not obtain

reasonable options. If we assume that X is oxygen, then M(X) = 32 g/mol, Ar = 195.15/n, most likely
n = 1, and the element is platinum, then the second element accounts for 114 g/mol, which
corresponds to 6 fluorine atoms (this is quite consistent with the data on the high oxidizing ability of
this compound), i.e. Y - PtF6. The reaction of platinum hexafluoride with oxygen, as is well known,
leads to dioxygenyl hexafluoroplatinate (V), i.e. I is [O2][PtF6]. From the mass loss data, which
correspond to the loss of one fluorine atom, we obtain that Y1 is PtF5, and Y2, the second product
of its disproportionation, is most likely platinum tetrafluoride PtF4. It is quite well known that
experiments with platinum hexafluoride and the synthesis of the first salt of the dioxygenyl cation
preceded the preparation of noble gas compounds. Based on the expected data on the content of
platinum (most likely, platinum is also the heaviest element in this salt) in “salt II”, and also on the
fact that the reaction with gas A was assumed, most likely, in a ratio of 1: 1 (the condition indicated
that the reaction is similar to the reaction with gas X), we obtain, = 131.3 g/mol, which corresponds
to xenon, that M(A) =
i.e. A - Xe, and the element Z - Xe, i.e. the problem is really about compounds of noble gases (this
is also indirectly indicated by the fact that these compounds until a certain moment seemed unusual
to scientists) . Then “salt II” has the formula XePtF6, and given the supposed analogy with
dioxygenyl hexafluoroplatinate, the structure most likely assumed for the salt is Xe+ [Pt2F6]
. Three xenon binary compounds with the same element

ment, obtained from the same initial substances with changing conditions - most likely fluorides.
Using the data on the mass fraction of xenon in these compounds, we obtain that indeed B - XeF2,
C - XeF4, D - XeF6. All xenon fluorides are obtained by direct synthesis from xenon and fluorine.
21
Salt III, as indicated in the condition, can be formally considered as a product of the addition
of two PtF6 molecules and one xenon molecule, i.e., the gross formula is XePt2F12. It is also
indicated that the oxidation state of xenon is the same as in difluoride B, i.e. +2, from which it is
ÿ
logical to assume the formula [XeF] + [PtF11] .
The hydrolysis of XeF4 apparently results in disproportionation into atomic xenon and
compound E, which contains xenon in a higher oxidation state. The fact that xenon is not released
during the hydrolysis of XeF6 suggests that E is a derivative of xenon in the oxidation state (+6).
Using the data on the xenon mass fraction, we obtain that the molar mass of the compound per
one xenon atom is 131.29/0.6654 = 179.29 g/mol, which corresponds to
XeO3. When reacting with a lack of alkali, a monosubstituted salt is formed, i.e., most likely F -
NaHXeO4. The maximum oxidation state for xenon is +8, i.e. G is a salt, which can be formally
represented as xNa2O yXeO4. Using data on the mass fraction of xenon in this salt (one atom of
xenon accounts for 131.29/0.4113 = 319.2 g/mol, which corresponds to x : y = 2 : 1), i.e., the salt
formula is Na4XeO6. Concentrated sulfuric acid reacts with barium perxenate on cooling and
probably acts simultaneously as a strong acid and as a dehydrating agent, giving H -XeO4.
A -Xe _____ F – NaHXeO4 _____ III - [XeF][Pt2F11]

B – XeF2 C – XeF4 H –GXeO4
– Na4XeO6
D– X - O2
XeF6 I – [O2][PtF6] Y -PtF6
Y1 – PtF5
E – XeO3 II – Xe[PtF6] 2. Reaction Y2 – PtF4
equations:
one) Pt + 3F2 = PtF6
2) 2PtF6 = 2PtF5 + F2ÿ
3) 2PtF5= PtF6 + PtF4
4) O2 + PtF6 = [O2][PtF6]
5) Xe + PtF6= Xe[PtF6]
6) Xe + F2= XeF2
7) Xe + 2F2= XeF4
8) Xe + 3F2= XeF6
9) Xe + 2PtF6= [XeF][Pt2F11]
10) 3XeF4 + 6H2O = 2XeO3 + 12HF + Xeÿ 11)
XeF6 + 3H2O = 6HF + XeO3
12) NaOH + XeO3= NaHXeO4
13) 4NaHXeO4 + 8NaOH = 3Na4XeO6 + Xeÿ + 3H2O
22
14) Ba2XeO6 + 2H2SO4 = 2BaSO4ÿ + 2H2O + XeO4ÿ 3. The

oxidation state of oxygen +1/2, platinum +5, fluorine –1 4. According to
Gillespie, XeF2 has the AB2E3 type, the coordination polyhedron is a trigonal bipyramid, the
linear, XeF4 —type AB4E2, coordination polyhedron—octahedron, geometry of the molecule—flat
square , XeF6—
type AB6E, coordination polyhedron is a one capped octahedron, geometry of the molecule is a
distorted octahedron.
Xenon fluorides are compounds with a three-center four-electron bond, relatively "unusual" for
"classical chemistry". Therefore, the existence of these molecules has greatly enriched the knowledge
of chemists about
covalent bonds.
5. The xenon atom and the oxygen molecule have close ionization energies,
+
therefore obtaining a compound with an O2 ion led to the assumption that
it is possible to obtain a similar compound with the Xe+ ion .
Grading system:
For each of the 15 substances - 0.5 points (if the composition of ions is
one. 7.5 points
incorrectly indicated for salts I - III - 0 points).
2. Reaction equations - 1 point each 14 points
3. Correct oxidation states 0.5 points
The correct geometry of each molecule is 0.5 points.

4. Mention of a three-center four-electron bond - 2 points
0.5 points
5. Correct answer 1 point
TOTAL: 25 points
Solution of problem 8 (Karnaukhov T.M., Dolzhenko V.D.)

1. Since the isotope of element X is formed by the decay of uranium nuclei, it must be lighter
than 238. There are not many radioactive elements (having no stable isotopes) lighter than uranium.
Numerous historical facts suggest that element X is technetium. If it is difficult to guess about this
from a rather lengthy description, you can use the calculations. When a simple substance is heated in
excess of oxygen, an oxide is formed.
23
2M X
Denoting the oxide C as X2On, we get ÿ
X
ÿ
,
2MMXOnÿ
M
X
similarly for XClm chloride: ÿ
X
ÿ
MM m ÿ
XCl
ÿ
X
ÿ
15.999 ÿ X
ÿ
35.453
M ÿ
n =14.129n M ÿ
m =24.729m
X X
2(1
ÿ
ÿ )
ÿ
ÿ
X one
X
n Mx Oxide n Mx Oxide m Mx 1 14.13 N2O 5 70.65 Ga2O5 Chloride
one 24.729 MgCl
2 28.26 SiO 6 84.77 2 49.458
3 42.39 7 98.90 Tc2O7 8 3 74.187 AsCl3
4 56.52 113.0 CdO4 4 98.916 TcCl4
Only technetium is suitable, because only it forms Tc2O7 oxide and chloride
TcCl4, in which the mass fractions of the metal correspond to the condition of the problem.
Let's define the element Z. To do this, we write the equation of the nuclear reaction, as a
result of which technetium was first obtained. According to the condition, as a result of it, the
most common isotope is formed, the atomic mass of which can be obtained by rounding off
the tabular value, i.e. 99Tc:
2
m ZD Tc 99
ÿ 1 ÿnÿ
one
q 43 0
From the general form of the reaction, we obtain that m = 98, q = 42. This corresponds to
isotope 98Mo. Thus element Z is molybdenum.
The equation for a nuclear reaction, carried out by Segre and Perrier:
98 2 99
0n
one
42Mo ÿ Dÿ Tc ÿ . 43one
2. Let x be the number of alpha decays and y the number of beta decays of the 235U
nucleus. The overall equation for the nuclear reactions of the conversion of 235U to 99Tc can be
written as
235
xye 99 Tc He ÿ42ÿ ÿ 0 .
92U 43 ÿ
one
The mass changes only due to alpha decays: x = (235 - 99) / 4 => x = 34.
During alpha decay, the nuclear charge decreases by 2, and during beta decay, they increased
counts on 1: 92 - 2x + y = 43 => 24 + y = 43 => y = 19.
Thus, the 235U nucleus undergoes 34 alpha decays and 19 beta decays.
Let us determine the isotope formed along with technetium in the fission of 235U.
The equation of this nuclear reaction in general form is written as
235 99 m one
U
92 43 ÿ Tc ÿ E ÿ q 0n
whence m = 135, q = 49. Thus, along with technetium in this reaction

24
135In isotope is formed:

235 99 135
0n
one
92Uÿ Tc 43
ÿ In ÿ 49
3. In paragraph 1, we have already determined the composition of substances A -

Tc2O7 and C - TcCl4. The dissolution of higher technetium oxide in KOH and an
aqueous solution of ammonia yields F – KTcO4 and ÿ – NH4TcO4, respectively.
Technetium fluoride B has a molecular structure in the gas and solid phases and kn = 6,
from which it can be concluded that B is TcF6. When B interacts with NO, an ionic
compound is formed, and the k.h. Tc changes in this case. The increase in mass is then:
ÿ m 0.2769 0.2427
ÿ
G
ÿ
(98.906 18.998ÿ 6) 30
ÿÿ
, which corresponds
ÿ
TcF 6
0.2427 mole
one NO molecule. i.e. Composition L – NO+ [TcF6 – ]* .

D is obtained by the interaction of Cl2
and Tc, taken in molar ratio
0.10 0.14
: ÿ
1:1 , which allows the
70.906 98.906
to divide the composition
D - TcCl2. C has a polymeric structure
(†) (see figure), however, this compound Fragment of the TcCl4 structure
dissolves slowly in THF, while the c.h. remains

equal to 6, redox reactions in the indicated
conditions are not to be expected, so (†) K is

[TcCl4(THF)2]
(see picture).
XeF6 interacts with Tc2O7 at 0.3164
0.1332
molar ratio : ÿ
245.278 309.805
3:1, this gives compound M, which does not Structure of [TcCl4(THF)2]
contain Tc and contains 7.17% oxygen. The
composition of this compound may include oxygen, fluorine and xenon: XeOxFy .
xM ÿ
ÿ
O O ÿXe =>
ÿ ÿÿ x M y M_ ÿÿ
ÿ
O Fÿ _
M y Mÿ ÿ ÿÿ ÿ )M
ÿ
M x Xe O F (one OO
*
JH Holloway, H. Selig// J. Inorg, Nucl. Chem. (1968), V.30, pp. 473-478, doi:10.1016/0022-
1902(68)80474-9
† A. Hagenbach, E. Yegen, U. Abram // Inorg. Chem. (2006) V.45, no.18 , pp. 7331-733
DOI: 10.1021/ic060896u
25
0.0717
x ÿ
ÿ
ÿ131.29 18.998
ÿ
yÿ 0.6338 0.0917 y ÿ
ÿ
ÿ
(1 0.0717) 15.999
yx
1 0.72
2 0.82
3 0.91
4 1.00
Thus, M is XeOF4.
Recovery of Tc in the reaction with XeF6
it is not necessary to assume, it means that a
simple exchange reaction proceeds between them and I
is technetium oxofluoride. Its composition can
set using the molar ratios of the reactants. As
a result of the interaction of 3 mols of XeF6
Fragment of the TcO2F3 structure
with 1 mol of Tc2O7 , 3 mols of XeOF4 are
formed, while 3 oxygens are “torn off” from Tc2O7 and 6 fluorines are “released”,
(*)
from which follows the composition I - TcO2F3(see picture).
In the interaction of XeF6 with Tc2O7 in the molar ratio
0.5273 0.1332
: 5:1, an HF-soluble salt is formed. i.e. 1 mol XeF6
ÿ
245.278 309.805
interacts with 1 mol of TcO2F3, redox reaction is impossible , c.h. [TcO2F2]
+
, in which the c.h. of technetium is 4. Dal
the most extreme substitution of oxygen TcF3O2 for fluorine with the formation
of TcOF5 contradicts the statement that an ionic compound is formed, which means
ÿ
J - XeF 5TcO
][ F 24(*) ] .
ÿ
[ It is known that G and H are isostructural , formed as a result of reduction

(addition of potassium iodide), these compounds, along with technetium, contain
chlorine and potassium. Upon receipt of G , potassium iodide and KTcO4 are taken in
0.74 0.3
molar ratio : ÿ
3:1 , which corresponds to the recovery
166.003 202.00
Tc to oxidation state +4. Calculate the ratio of molar masses of G and H:
*HPA Mercier, GJ Schrobilgen // Inorg. Chem. (1993), v. 32 , No. 2, pp. 145–151;

doi:10.1021/ic00054a006
26
MH 0.0787 / 0.75
ÿ ÿ
1.049(3) . Suppose that one of the encrypted
M 0.1
G
compounds is K2TcCl6, then the molar mass of the other compound
389.82 ÿ1.049(3) ÿ 409.05 G or 389.82 /1.049(3) ÿ 371.49 moleG .
mole
Since the compounds are isostructural, differences are possible in the cation, but apart from
K+ and H+ , there are no other cations in the second route of H synthesis . Let us consider variants
+ +
with the replacement of the potassium cation by H3O, H5O2 :
Substance M, g/mol Substance M, g/mol
(H3O)KTcCl6 369.75 (H5O2)KTcCl6 387.76
(H3O)2TcCl6 330.65 (H5O2)2TcCl6 348.66

(H3O)KTcCl6 has a similar molar mass, but then one would have to assume that during
its recrystallization , K2TcCl6 precipitates,
although the concentration of potassium ions in the solution during recrystallization is lower
than in the initial reaction mixture.
Another possible option explaining the isostructural nature of G and H is the substitution
of the chloride ion. Since the reaction proceeds in water, the only possible anion is the
hydroxide anion. Indeed, then G is K2[TcCl5(OH)]* , H is K2[TcCl6].
M (K2 [TcCl5 ( Oh
G
)]) ÿ 371.37 , mol
Reaction equations:
450ÿC
1. 4Tc + 7O2(ex.) ÿÿ ÿÿ 2Tc2O7
2. Tc2O7 + 2NH3 + H2O ÿ 2NH4TcO4
3. Tc2O7 + 2KOH ÿ 2KTcO4 + H2O
600ÿC
4. 2NH4TcO4 + 7H2 ÿÿ ÿÿ 2NH3 + 8H2O + 2Tc
450ÿC, p
5. Tc + 2Cl2(ex.) ÿÿÿÿÿ TcCl4
450ÿC
6. Tc + Cl2 ÿÿ ÿÿ TcCl2
400ÿC, p
7. Tc + 3F2(ex.) ÿÿÿÿÿ TcF6
8. TcF6 + NO ÿ NO+ [TcF6] -
tÿC
9. TcCl4 + 2THF ÿ ÿÿ [TcCl4(THF)2]
tÿC
10. 2NH4TcO4 + 4KCl + 16HCl(conc.) ÿ ÿÿ 2NH4Cl + 2K2TcCl6 + 8H2O + 3Cl2ÿ
11. 2KTcO4 + 6KI + 14HCl(conc.) ÿ 2K2[TcCl5(OH)] + 6H2O + 4KCl + 3I2
*M. Elder, JE Fergusson, GJ Gainsford, JH Hickford, BR Penfold// J. Chem. soc. A (1967),

pp. 1423-1425; doi:10.1039/J19670001423
27
tÿC
12. K2[TcCl5(OH)] + HCl(conc.) ÿ ÿÿ K2TcCl6 + H2O
HF
13. Tc2O7 + 3XeF6 ÿÿÿÿlÿÿ 2TcO2F3 + 3XeOF4
HF ÿ ÿ
14. TcO2F3 + XeF6 ÿÿÿÿlÿÿ [TcO

][ XeF
5F 24 ]
4. The compound [TcCl4(THF)2] has 2 isomers:
.
cis-[TcCl4(THF)2] trans-[TcCl4(THF)2]
Scoring system:
1 Element X - 1 point, Z - 0.5 points 2 points
Synthesis reaction equation X – 0.5 points
2 Determination of the number of alpha and bat decays - 1 point 1.5 points
Decay reaction equation for 235U – 0.5 points
3 Substances A - M 0.5 points each 20.5 points
Reaction equations (14 pcs) 1 point each
4 Isomers of [TcCl4(THF)2] 1 point
TOTAL: 25 points
28
Organic chemistry
Solution of problem 1 (Andronov V.A.)
1. At the first stage, the Grignard reagent is added to the carbonyl group of the
aldehyde to form an alcoholate, after the neutralization of which alcohol A is obtained.
At the next stage, alcohol A interacts with the orthoester of acetic acid. Protonation of
the orthoester leads to the elimination of the alcohol molecule with the formation of a
relatively stable carbocation, which then reacts with the alcohol group of compound A.
Repeated protonation and elimination of the methanol molecule leads to the formation
of a molecule containing the allylvinyl ether fragment, which is necessary for the flow
[3, 3] -sigmatropic rearrangement (Claisen rearrangement). The resulting ester B is
reduced by the action of lithium aluminum hydride to alcohol C, which is oxidized to
aldehyde X by the action of a complex of chromium trioxide with pyridine. The structure
of X can be written, however, without knowledge of these reactions, since the
systematic name of this compound is given in the condition. Since X was obtained by
oxidation of compound C, it can be concluded that C is the corresponding alcohol,
which was obtained by the reduction of compound B, for which the empirical formula is
given in the condition, from the analysis of which it follows that this is the methyl ester
of the corresponding acid.
2. The second chain begins with the reaction of 2-methylfuran with butyllithium.
Since the lithium cation is coordinated to the oxygen atom of furan, deprotonation
occurs at the ÿ-position; as a result, 5-methyl-2-
furyllithium. It reacts with 1,4-dibromobutane via the SN2 mechanism to form 2-(4-
bromobutyl)-5-methylfuran (D). The fact that only one bromine atom enters the
substitution reaction clearly follows from the empirical formula of compound E. It also
follows from this formula that D reacts with two ethylene glycol molecules (13 carbon
atoms and 4 oxygen atoms). It is known that furan can be hydrolyzed to form a 1,4-
diketone. In this case, both hidden
29
The carbonyl groups of the furan ring react with ethylene glycol in an acid medium
to form the corresponding diketal.
The resulting bromide E reacts with triphenylphosphine to give phosphonium salt

F, which reacts with Wittig with aldehyde X to give compound G containing two C–
C double bonds. Under the action of acid, the acetal protection is destroyed and
carbonyl groups are released. The gross formula H confirms the structure of this
product. Its treatment with alkali causes aldol-crotonic condensation with the
formation of cyclopentenone I. Which atoms are involved in it can be understood
from the open structure of the intermediate. Next, MeLi is added to the carbonyl
group. At the next stage, carbocation cyclization occurs when the cation formed
upon protonation of the alcohol group in J
attacks the C–C double bond, the new cation attacks the next C=C bond, etc.
Then the cationic intermediate is hydrolyzed to a ketone. On the next
stage is ozonation followed by reductive splitting. The synthesis is completed by
intramolecular aldol-crotonic condensation.
thirty
Grading system:
1. Structural formulas A–C – 2 points each, structural formula ÿ – 1 point 7 points
2. Structural formulas D–L – 2 points each. 18 points
TOTAL: 25 points
Solution of problem 2 (Zima A.M.)

1. The structures of all intermediates of the first chain can be determined by considering the open
structure of compound F, the direct precursor of artemisinin. At the first stage of the chain, the carboxyl
group of artemisinic acid is methylated under the action of CH2N2 , followed by selective hydrogenation
of the sterically most accessible double bond on a Wilkinson catalyst. The resulting product B is then
subjected to ozonolysis followed by reductive treatment with dimethyl sulfide, which is used to obtain
aldehydes and ketones. The addition of 1,3-propanedithiol to C is used to protect the carbonyl group and
may result in the formation of a thioacetal or thioketal. Because the keto group remains in F, it did not
react in the next step. Therefore, it was the thioketal that was obtained. Trimethyl ester of orthoformic
acid under acid-
31
This catalysis first produces an acetal, which cleaves off methanol to form an enol
ether. A solution of mercury(II) chloride is necessary for the hydrolysis of thioketal. The
hydrolysis is carried out under very mild conditions so as not to cleave the enol ester.
At the final stage of the synthesis, F is oxidized with singlet oxygen generated by
irradiation in the presence of the Rose Bengal dye at a low temperature, which, after
hydrolysis with perchloric acid, gives artemisinin (Z).
2. Consider the scheme for obtaining B from isopulegol. The first stage of this
transformation is hydroboration followed by borane oxidation by the action of H2O2.
This variant of alkene hydration yields the product contrary to the Markovnikov rule,
which makes it possible to obtain primary alcohol G. Next, the primary alcohol is
selectively benzylated (which is clearly seen from the nearest open structural formula),
after which the secondary alcohol is oxidized with pyridinium chlorochromate to ketone
H. The resulting ketone under the action of a strong base (lithium dialkylamide) is
deprotonated at a more accessible methylene group, and the enolate ion is alkylated,
turning into I. The oxidizing agent m CPBA first leads to the formation of an epoxide,
which is converted in situ to a diketone, shown in the scheme in the condition. The
three subsequent stages are Wittig reactions (phosphorus ylides are given as reagents,
although the corresponding phosphonium salts and bases are actually used). During
the conversion of J to K , an enol ester is formed, the hydrolysis of which gives a new
carbonyl compound, which enters into the following Wittig reaction. The transformation
of L into M is the formation of a six-membered ring by the reaction of alkene metathesis
under the action of Grubbs' catalyst. This reaction was repeatedly encountered in the
sets of tasks of the Final Stage. In addition, the structure of compound B, which is
easily established during the analysis of the first chain, helps to establish this
transformation. At the last stage of syn-
32
thesis B , the benzyl protecting group is sequentially removed, the alcohol is oxidized to acid
with the Jones reagent, and the acid is methylated dia
zomethan.
The second part of the chain shows the synthesis of B from citronellal. At the first
stage, the enolate ion of citronellal is added according to Michael to the ÿ-carbon atom of
vinyl methyl ketone to form the product N containing two carbonyl groups. Further, under
the action of alkali, intramolecular aldol condensation occurs, leading to the formation of a
six-membered ring. Since the obtained product O enters the Grignard reaction at the next
stage, it can be concluded that this is an unsaturated ketone. What does the Grignard
reagent in this case add according to the type 1,2-
addition to the keto group, which is clearly seen from the position of methyl in product B.
As a result, after neutralization, unsaturated alcohol P is formed. It is convenient to analyze
the next fragment of the chain from the end, that is, from compounds R and S. formation of
a carboxyl group, therefore, substance S must contain a carbonyl or hydroxyl group.
However, since it is clear from the previous steps that the compound R obtained by the
hydroboration reaction is an alcohol, the only reasonable option for S is an aldehyde. It was
obtained by Svern oxidation (oxalyl chloride and DMSO)
33
substance R. The alcohol, in turn, was formed as a result of hydration of the least substituted double
bond (since the sterically hindered 9-borabicyclo[3.3.1]nonane is used) against the Markovnikov rule,
which means that the initial compound Q contains a terminal double bond. The absence of a hydroxyl
group in Q, as well as the degree of its unsaturation, can be determined from the empirical formula given
in the condition. The step of conversion of P to Q under the action of tin(IV) chloride is an acid catalyzed
cyclization proceeding through the formation of an allyl cation obtained by splitting off a water molecule
from protonated P. Q.
Grading system:
1. Structural formula B - 1 point. Structural 5.5 points
formulas ÿ–E – 1.5 points each.
2. Structural formulas G–S – 1.5 points each 19.5 points
TOTAL: 25 points
Solution of problem 3 (Plodukhin A.Yu.)

1. Define the halide Q. Its formula can be represented as MeHaln, where n=1, 2, 3... Knowing the
mass fraction of the metal, it can be expressed using at
the formula below: ÿ

. From here we get:
. Solving this relation, we come to the conclusion that n = 2,

ÿ ÿ
Hal is chlorine (M = 35.453), and the metal is palladium (M = 106.42). Then mo-
34
The polar mass of the salt Z is 106.42ÿn/0.3617 = 294 ÿn g/mol, where n is the number of
palladium atoms in Z. Co-crystallization of PdCl2 and another chloride results in the
formation of a complex salt of the MmPdnClp type. At n = 1, m atoms of the second metal
and p atoms of chlorine account for approximately 187.8 g/mol. The only possible solution
is p = 4, m = 2, M is sodium, i.e. Z is Na2PdCl4. The molecular weight of the complex with
triphenylphosphine (M ÿ 262.3) is 106.42ÿn/0.1516 = 702ÿn. This mass corresponds to the
PdCl2(PPh3)2 complex.
The palladium complexes have a square-planar geometry. For PdL1 2L complex
2
2 possible two isomers with the same cis and trans positions
output ligands.
2. The first stage - iodination of para-bromobenzene (ÿ6H4Br2) leads to A. The

transformation of A into B is the Sonogashira reaction. Compound B has the gross formula
C18H20Br2. From this we can conclude that compound A contains two iodine atoms,
which are replaced by an alkyne (C6H10) in the course of the Sonog Shira reaction. Thus,
aryl iodides enter into the cross-coupling reaction faster than aryl bromides. Conclusion
about the position in the benzene ring of iodine atoms, a,
therefore, acetylene groups can also be made based on the rules of orientation in
electrophilic substitution reactions (ortho-/para-orientation by halogen atoms), taking into
account steric effects (preferential attack on the more accessible para-position with respect
to the first introduced iodine atom) . In addition, this conclusion is confirmed by a schematic
representation of "per child".
The transformation of B into C is the formylation reaction (the exchange of one

bromine atom for lithium and the reaction of the aryllithium compound with N,N-
dimethylformamide), which is confirmed by the empirical formulas B and C. The
transformation of C into D is the formation of a cyclic acetal (the standard reaction for
protection of the aldehyde group in organic synthesis by the action of ethylene glycol).
Further, the exchange of bromine for lithium and the transformation of the aryllithium
compound into aryl iodide (which clearly follows from the empirical formula E).
Bromination of para-nitroaniline in acetic acid leads to 2,6-
dibromo-4-nitroaniline, which is confirmed by the empirical formula G. It also follows from
this formula that, at the next stage, the nitro group is replaced by a hydrogen atom. This
transformation proceeds through the formation of a diazonium salt with
35

+
the next group substitution –N2 to the hydride ion from hypophosphorous
slots. When nitrobenzene G was treated with tin(II) chloride, it was reduced to aniline
H, which was converted via the diazonium salt to the corresponding iodide. The
Sonogashira reaction is then repeated twice. First, iodide enters the reaction, then
fragments of aryl bromide. Under the influence
KHF2 removes the silyl group to form hydrocarbon L, whose molecular formula
corresponds to a trisubstituted benzene ring containing two pentyn (ÿ5ÿ7) and one
ethynyl (ÿ2ÿ) fragments. The synthesis of the “nanore byon” completes the connection
of its “upper” and “lower” halves using the Sonogashira reaction.
36
Grading system:
1. Molecular formulas Q, R, Y, Z– 1 point each. Structural formula 5 points
of complex Y (one of two possible options) – 1 point.
2. Structural formulas ÿ–L – 1.5 points each; 20 points
structural formula of "nanochild" (N) - 2 points
TOTAL: 25 points
Solution of problem 4 (Salnikov O.G.)

1. The starting compound has the molecular formula C7H10O3, while compound B has
ÿ8H12O4. It will be appreciated here that the formation step B is the hydrolysis of the ester group. This
means that at the stage of formation of A , 2 carbon atoms, 4 hydrogen atoms and 1 oxygen atom are
introduced into the molecule. It is easy to conclude that at this stage the carbonyl group of the parent
compound reacts with ethylene glycol to form a ketal (protection of the keto group). Acid B then reacts in
the presence of dicyclohexylcarbodiimide (condensing agent, see condition) to form ester C, which has
(R)-hex-5-en-2-ol
the formula C14H22O4. The transformation of C into
With v
D is accompanied by the eliminationatoms
of 2 carbon
and 4
hydrogen atoms. In addition, only at this stage, the formation of a cycle is possible (according to the
condition, decarestrictin G is a 10-membered lactone). It can be assumed that at this stage, two alkene
fragments of the C molecule interact with each other with the elimination of ethylene and the formation of
a new C=C bond, which leads to the formation of a 10-membered cycle. Indeed, the reagent used has
already been encountered more than once in the problems of the All-Russian Olympiad dedicated to the
metathesis of alkenes. The action of an acid in the presence of acetone removes the ketal protection in
compound D (the ethylene glycol released in this process forms a ketal with acetone), and then the C=C
bond is dihydroxylated with OsO4 and N-methylmorpholine-N-oxide (stereochemistry in the final product
and in the C– E is not evaluated). When a water molecule is bound by carbodiimide, an oxygen atom is
attached to a positively charged carbon atom, and hydrogen atoms are attached to two nitrogen atoms,
forming
dicyclohexylurea.
37
2. At the first stage of the synthesis of decarestrictin L, 1,2,5,6-diepoxyhexane is

treated with one equivalent of NaAlH2(OCH2CH2OMe)2 (trade names for this reagent
are Red-Al or Vitride). This is a substituted aluminum hydride, so it must have reducing
properties. It reduces one of the two epoxy groups to alcohol. The reaction proceeds
according to a mechanism related to the SN2 mechanism, that is, the hydride ion attacks
the less substituted carbon atom. The resulting secondary alcohol is protected with tert
-butyldiphenylsilyl chloride (TBDPSCl). In the next step, the epoxy group of the product F
is opened with a dianion formed from (phenylthio)acetic acid by the action of a strong
base of lithium diisopropylamide (LDA). This reaction also proceeds according to the SN2
mechanism, that is, the nucleophile attacks the less substituted carbon atom of the
epoxide. Acidification of the reaction mixture leads to the formation of hydroxy acid G,
the carboxyl group of which is further methylated with diazomethane CH2N2. In the next
step, sulfide H
oxidized to sulfoxide with meta-chloroperbenzoic acid (m CPBA). Heating eliminates the

sulfonic acid to form the unsaturated ester I. Subsequent alkylation of the hydroxy group
with benzyloxymethyl chloride (BOMCl) gives compound J.
38
Removing the silyl protection with tetrabutylammonium fluoride makes it possible

to obtain alcohol K, which, under the action of a base, enters into an intramolecular
Michael addition reaction. In this case, a second cycle is formed (the first is the benzene
ring). In the next step, the ester group is reduced with lithium aluminum hydride. The
resulting primary alcohol M is oxidized according to Svern. Then, from the aldehyde N
by the addition of methylmagnesium bromide, a secondary alcohol is obtained
O, the oxidation of which by the CrO3–pyridine system gives ketone P. On the last
the synthesis steps remove the protective group by hydrogen reduction on a palladium
catalyst in an acidic medium (hydrogen reduces the benzyl group to toluene and
alcohol, and the acid hydrolyzes the hemiacetal formed in this case). The given gross
formula helps to give the correct answer.
39
Grading system:
1. Structural formulas A–E and decarestrictin G – 1 point each. Structural formula 7 points
of the product formed from Cy– N=C=N–Cy – 1 point
2. Structural formulas of F–P and decarestrictin L – 1.5 each 18 points

points
TOTAL: 25 points
40
Chemistry and life

Solution of problem 1 (Rodkina N.V., Bacheva A.V.)
1. Condensation of phthalimide with tert-butyl chloroacetate (Gabriel synthesis)
gives substance A, and its treatment with sodium amide in ethyl formate leads to
formylation of the active methylene group (Claisen condensation) and 2-phthalimido-ÿ-
oxopropionic acid tert-butyl ester (ve entity B).
Condensation of aldehydes with 1,2-aminothiols gives thiazolidines. Using an

appropriately protected derivative of formylglycine B and D-penicillamine, penicilloic
acid C containing a protecting group is obtained. The phthalimide group is removed by
the action of hydrazine, the resulting amine E is acylated with phenylacetyl chloride to
give compound F, after which the protective tert-butyl ester function is removed by
treatment with anhydrous hydrogen chloride. The resulting dicarboxylic acid G was
treated with 1 equiv of KOH to give the potassium salt at the stronger carboxy group
next to the imino group in the ring. Such a salt serves as a convenient protecting group
in a reaction in which a ÿ-lactam ring is formed by the action of dicyclohexylcarbodiimide
to form penicillin G.
41
2. The structure of the ACV tripeptide, isopenicillin N and chiral centers in the
structure of penicillin G are shown in the diagram:
3. Since this atom must attack the hydrolysable bond, it is a nucleophile. The
best nucleophile that is part of amino acids is the OH group of serine or threonine,
that is, the atom is oxygen. –SH group of cysteine can also take part in hydrolysis,
then the atom is sulfur. Both answers are accepted.
4. Arginine reacts with glyceraldehyde-3-phosphate, giving N-carboxyethyl
arginine, in which, in the next step, an internal amide, or in other words, a ÿ-lactam
cycle, is formed by the action of synthetase (substance I). The enzyme in this case
formally takes away water, using it to hydrolyze ATP.
42
Deoxyguanidinoproclavamic acid (substance I) reacts with 2-ketoglutarate in the presence

of oxygen under the action of clavaminate synthase and is converted into
guanidinoproclavamic acid (substance II). Hydroxylation occurs at the carbon atom
adjacent to the carboxyl group. Doga
it can be given that alcohol is obtained, and not a ketone, by counting the hydrogen atoms in the
starting and final substance.
At the next stage, hydrolysis of the guanido function to an amine occurs under the
action of amidinohydrolase with the formation of proclavamic acid (substance III).
Further, proclavamic acid is oxidized with the closure of the second cycle and
the formation of dihydroproclavamic acid (substance IV)
Then clavamic acid (substance V) is formed, comparing the composition of substances

IV and V, you can guess the presence of a double bond in the product, and the position of
the double bond can be determined by looking at the final product, clavulano
acid:
At the next stage, an aldehyde group is formed from the amino group, and the resulting
43
clavaldehyde (substance VI). The formation of the aldehyde function can be judged from the composition of
the reactants and by-products, which are shown under the arrow. And at the last stage, the aldehyde is
reduced to alcohol and clavulanic acid is obtained:
Grading system:
1 Structural formulas of substances AG and penicillin G (8 for 16 points
mule) 2 points each

2 ACV tripeptide structure 1 point, three chiral centers of penicillin G 1 point 2 points
3 Indication of an oxygen or sulfur atom 4 Structural 1 point
formulas of substances I–VI (6 formulas) 1 point each 6 points

TOTAL: 25 points
Solution of problem 2 (Dikhtyar Yu.Yu.)

1. Butlerov's formosa reaction (up to five-membered sugar) is shown in
diagram below:
2. The decoding of substances by their names occurs as follows

principle:
Substance (7) —cyanoacetylene—suggests the idea that the substance must contain both a triple
bond with two carbons and a cyano group. The gross formula of this compound allows you to accurately
determine the structure and
confirm the guess.
Substance (8) is a cyanamide, which means that it must simultaneously contain a cyano and an
amino group. The gross formula also confirms that it is simply an amino group with a cyano group.
44
Substance (9) - glyceraldehyde - is essentially a trihydric alcohol (glycerol), but

with one aldehyde group (instead of one hydroxyl).
Substance (10) - glycoaldehyde - is consonant with ethylene glycol (dihydric

alcohol), but there must also be an aldehyde group.
Substance (11) is obtained from (10) and (8) by condensation with elimination of
water. Let's use the formula to calculate the degree of unsaturation. So, for a compound
.V
of composition ÿxHyNzOn, the formula will look like our case CH = 3, which tells us that
there are either three cycles in the molecule, or two cycles and one double bond, or one
cycle and two double bonds, or one triple bond and one double (one triple bond is worth
2 units of the formal degree of unsaturation, all other elements - a cycle, a double bond
- are worth one unit). It seems most logical to build one cycle with two double bonds,
because the final product itself is
holds cycles, and the number of carbons does not allow us to come up with a structure
with two unstressed cycles at once. Compound (12) is obtained from (11) and (9) by
condensation. CH = 3. Based on the structure (11) , it is logical to assume that the
compound formed has two cycles and one double bond, moreover, 2'-3'-cyclic phosphate
is formed already through one compound. And since the addition of the phosphate
group occurs only at the last stage (substance (13) in (1)), it is logical to assume that it
is at this stage that the analogue of the sugar backbone is formed. Obtaining (13) from
(7) and (12) occurs in exactly the same way. The reaction of obtaining substance (4)
from (9) and (10) is, in fact, the form Butlerov reaction discussed at the beginning of the
problem. Getting (6) and (5) is a hydration reaction. Substance (3) can even be simply
guessed based on simple logic: first, sugar (4) was obtained, a nitrogenous base (3)
was added to it to obtain (2), and finally, after the addition of a phosphate group, the
target compound was obtained.
45
3. Substance (16) is guessed by replacing the hydroxyl in (10) with a thiol group.
Also, the substance (15) is very similar to (11) with the only difference that instead of
oxygen, sulfur enters the five-membered cycle. Substance formula (16) is obtained by
calculating the molar mass of the compound with respect to carbon. In this way,
it turns out that if there is one carbon in the molecule, then the remaining atoms
account for 15 g/mol, which corresponds to one nitrogen and hydrogen. One could
also go in the opposite direction: according to the condition of the problem, (17) is the
product of oligomerization (16) with the addition of one water molecule. From the
formula ÿ4H6N4O we subtract one molecule of water H2O and get ÿ4H4N4, which corresponds to
(HCN)4. Substance (18) is a Schiff base obtained from the amino group of substance
(17) and the aldehyde group of compound (9). Substance (19) is best established
from (19'). One can guess that the deoxy group is somehow tied to sulfur, otherwise
what is the point of using a thio analog (10) to obtain a deoxy derivative? Carbons
numbered 3, 4 and 5 carry hydroxyl
46
functions and can remain only from matter (9).
Grading system:
1 Formosa Butlerov reaction 4 points
2 Substances 7 - 10 2 points each, 16 points
Substances 2 - 6 and 11 - 13 1 point each
3 Substances 14–19 0.5 points each 5 points

Substance 19' - 1 point
Correct numbering of carbon atoms - 1 point
TOTAL: 25 points
47
Physical chemistry
Solution of problem 1 (Gulevich D., Kuramshin B.K.)

1-2. According to the Mendeleev–Clapeyron equation
pV 101325 0 .043 ÿ
ÿ ()
YA = 0.68 mol.
ÿÿ
RT 8. 314 773 ÿ
Since 100 g of substance A underwent decomposition, then ÿm at stage II of the process

is the mass of YA. Then M(YA) = 19.2 / 0.68 = 28 g/mol, therefore, YA -
CO.
You can calculate the molar mass of A: M(A) = 28.0 / 0.192 = 146 g/mol
Hence ÿ(ZA) = 146 0.301 = 44 g/mol. Therefore, ZA is CO2.
This is consistent with the fact that ZA is absorbed by the Ba(OH)2 solution to form a
precipitate:
Ba(OH)2 + CO2 = BaCO3ÿ+ H2O.
Since XA is split off at temperatures of 150–200°C, it can be assumed that XA is H2O.
Based on the sequence of elimination of H2O, CO, and CO2 , we assume that A is the
metal oxalate hydrate MeC2O4ÿnH2O. Accordingly, CA is MeC2O4, DA is MeCO3, and EA is
MeO.
Then M(MeO) = 146 - 18n - 28 - 44 = 74 - 18n.
At n = 1, we get ÿ(MeO) = 56 g/mol, which corresponds to CaO.
Therefore, A is CaC2O4ÿH2O, CA is CaC2O4, DA is CaCO3, EA is CaO.
This conclusion is supported by the titration data:
o
CaC2O4 + H2SO4(conc.) ÿtÿCÿ CaSO4 + H2C2O4

2KMnO4 + 5H2C2O4 + 3H2SO4 = 2MnSO4 + K2SO4 + 10CO2 + 8H2O.
C KMnO KMnO
ÿ
V ÿ
Vm
f to
. .
ÿ
. 0.01 20.2 100 5/ 2

ÿ ÿ ÿ
2 ÿ 2ÿ eq
ÿCO ÿCa ÿ 4 4
= 5.05 ÿ 10ÿ3 mol.
ÿ
ÿ 24 ÿÿ ÿ ÿ
V al . ÿ
1000 10 1000
ÿ
Then the weight of the test sample should be equal to m = 5.05ÿ10ÿ3 ÿ M(CaC2O4ÿH2O)
= 0.7373 g, which coincides with the mass of substance A taken
for titration.
The mass loss (a) at the first stage due to the elimination of water will be:
a = (18/146)ÿ100% = 12.3%.
3. Based on the same values of thermal effects and close values of ÿm at stages II and III,
we can conclude that CB is also calcium oxalate. The weight loss upon splitting off the CV is: a
+ 1.2% = 12.3 + 1.2 = 13.5%.
In this way,
M (X
) B ÿ
0.135 .
M ÿ( M
X
B) (CaCO)24
48
Hence M(XB) = 20 g/mol. So XB is D2O, then B is CaC2O4ÿD2O.

Total: A is CaC2O4ÿH2O, B is CaC2O4ÿD2O, CA and CB are CaC2O4, DA and Dÿ are
CaCO3, EA and EB - CaO, XA - H2O, XB - D2O, YA and YB - CO, ZA and Zb - CO2.
4.
o
I) CaC2O4ÿD2O ÿtÿCÿ CaC2O4 + D2O;
o
II) CaC2O4 ÿtÿCÿ CaCO3 + CO;

o
III) CaCO3 ÿtÿCÿ CaO + CO2.

5.
ÿfH°298(D2O) = ÿrH°298(I) – ÿfH°298(CaC2O4) + ÿfH°298(CaC2O4ÿD2O);

ÿfH°298(CaC2O4) = ÿfH°298(CaCO3) + ÿfH°298(CO) – ÿrH°298(II);
ÿfH°298(CaCO3) = ÿfH°298(CaO) + ÿfH°298(CO2) – ÿrH°298(III).
Then
ÿfH°298(D2O) = ÿrH°298(I) –[ÿfH°298(CaO) + ÿfH°298(CO2) – ÿrH°298(III) + ÿfH°298(CO) –
o
ÿrH°298(II)] + ÿfH 298(CaC2O4 D2O) =
= 37.7 ÿ (ÿ635 + (ÿ394) ÿ 177 + (ÿ111) ÿ 35) + (ÿ1685) = ÿ295.3 kJ/mol.
Grading system
1. Definition of unknown substances: XA - 2 points, SA - 1 point, DA - 1 point, EA - 1 7 points
point, YA - 1 point, ZA - 1 point 2. Definition of A -2 points, reaction equations

2 × 1 point 3 Definition of unknown substances: B - 1 point, XB - 2 points, 4 points
8 points
CB, DB, EB, YB, ZB 1 point each

4. Reaction equations 3 × 1 point 5. 3 points
o
Calculation of ÿfH 298 (XB) 3 points
TOTAL: 25 points
Solution of problem 2 (Zima A.M.)

1. The first part of the problem deals with
levels of organization of the structure of a new class of
porous materials MOFs (Metal Organic Frameworks) by
the example of the DUT-49 framework, whose abbreviation
stands for Dresden University of Technology (after the
name of the university where it was obtained). Interest in
the organization of the structure of MOFs is due to the
wide possibilities of designing these mathematical
Building DUT-49
49
rials, which in turn determines the diversity of their properties.

As can be seen from the figure given in the condition of the problem, fragment B of the
DUT-49 framework includes 6 fragments A located at the vertices of the octahedron. Therefore, B
will contain 2 6 = 12 X atoms and 4 6 = 24 COOÿ ,
and, consequently, 24 0.25 = 6 residues of the acid L(COOH)4. 2. In the elementary cell C ,
fragments B occupy the vertices of the cube and the midpoints of its sides. Moreover, each
B located at the vertex simultaneously belongs to eight cubes, and B in the middle of the face
belongs to two. Therefore, in total, the unit cell will include 8 0.125 + 6 0.5 = 4 fragments B.
3. Find how the molar mass of fragment B is related to the density of DUT-49.
We get that , where
. From the first paragraph of the decision, it can be seen that fragment B is described
-
formula X12L6(COO)24, so M(X) = . Received
the value occupies an intermediate position between the molar masses of zinc and
copper. The blue color of the DUT-49 crystals, indicated in the condition, makes it
possible to make an unambiguous choice in favor of X=Cu copper.
4. To obtain a linear form of dependence a(p) , it is necessary to raise the left and right parts
of the expression given in the condition to the power of ÿ1. Then
we get that .
The most accurate method for finding there will be a graph
depending on . However, other methods can also be used, for example
measures, find the coefficients for two known points (it is better to take the extreme values in the
table below). Let us find the maximum adsorption by the graphical method. To do this, we will
create a table with the values and :
1/ p, atm-1 20.0 10.0 6.67 5.00 4.00
1/ÿ(N2), g/mmol 0.323 0.169 0.116 0.0909 0.0752
Since the condition states that the experiment is carried out at the boiling point of liquid
nitrogen, the pressure of saturated nitrogen vapor will be 1 atm. Plotting a five-point graph allows
you to get a coefficient
or .
From the reference data for the problem, it can be seen that in order to find the pore
volume of the sample, it is necessary to use the formula . So
50
0.35
. 1/a = 0.0155 1/p + 0.0133
0.30
Let us calculate the specific surface area 0.25
of the DUT-49 framework using the formula . Then 0.20
0.15
0.10
. 0.05
0.00
Among porous frameworks, DUT-49 has 0 2 4 6 8 10 12 14 16 18 20 22
one of the highest specific surface area and 1/ p, 1/atm
belongs to the group of MOFs with values
. For a visual representation of such large values

surface area of DUT-49 can be compared with, for example, the area of a football field,
which is 7140 m2 . It can be seen that these values
are quantities of the same order.
5. It can be seen from the linearized Langmuir equation that an increase in methane
pressure should lead to an increase in its adsorption. However, the value of methane
adsorption at 0.10 exceeds the neighboring values at 0.05 and 0.15. It was this fact that
caused the surprise of scientists, allowing them to think about the instrumental error.
However, since the condition of the problem states that the researchers established the
cause of this discrepancy and this is not an experimental error, we will calculate the pore
volume of the framework based on the data on the adsorption of meta
on the. In this case, we get , which is significant from
differs from the value obtained by the nitrogen adsorption method ( ). Prior to the
experiment, it was assumed that the pore volume of the sample would not change, and we
methane gas will occur at values .
The researchers explained this difference in methane adsorption by a change in the

structure of the DUT-49 material with a decrease in the total pore volume of the sample
(the transition of DUT-49op to DUT-49cp), i.e., DUT-49 belongs to the so-called
“walking” frames, as evidenced by the heading of the problem statement.
The discovered unusual effect was called "negative gas adsorption" and was
published by a group of scientists in the journal Nature in 2016 as the first example of a
decrease in adsorption with increasing gas pressure (Krause1, S., Bon1, V., Senkovska, I.,
et al. A pressure-amplifying framework materi al with negative gas adsorption transitions //
Nature. - 2016. - V. 532. - P. 348–352.). Also, in addition to this article, two videos were
recorded demonstrating the change in the structure of the DUT-49 frame.
51
WITH
H4
Structure change from DUT-49op to DUT-49cp

Grading system
1. Number of X atoms per B 1 point
Number of fragments L(COOÿ )4 2 points
2. Number of fragments B in C 2 points
3. Establishment of metal X 4 points
4. Linearization of the Langmuir equation 2 points
Maximum adsorption 4 points
Total pore volume 2 points
Specific surface area of DUT-49 2 points
5. Explanation of the reasons for the surprise of scientists 2 points
Expected adsorption value for methane 2 points
Conclusion about changing the frame structure 2 points
TOTAL: 25 points
Solution of problem 3 (Karnaukhov T.M.)

1. Since the task asks about spontaneous adsorption, the change in the Gibbs energy is less than
zero (ÿrG <0). During the process, the gas molecule is "fixed" on a solid surface, so the entropy
decreases (ÿrS <0). In order for the inequality ÿrG = ÿrH – TÿÿrS <0 to hold for ÿrS <0, it is necessary
that ÿrH <0. Thus, upon spontaneous adsorption, the enthalpy also decreases. The determining factor is
the one that provides a negative value for the change in the Gibbs energy. In the case of adsorption, this
factor is enthalpy.
2. Since adsorption is an exothermic process (ÿrH < 0), then, according to
52
principle of Le Chatelier, adsorption proceeds to a greater extent with a decrease in

temperature.
K [ A-Z ]
3. ÿ
, where [AZ] and [Z] are the concentrations of occupied and unoccupied centers
PZ
A []
ÿ
on the surface, respectively; PA - gas pressure A. The degree of filling according to

surfaces
[ AZ ] [ AZ ]
ÿ ÿ ÿ
,
[ Z] 0 ÿ
[ [] ZAZ ]
where [Z]0 is the concentration of all active surface centers. Expressing con
centering of unoccupied centers from the expression for the equilibrium constant, semi
tea
[ A-Z ]
[ Z] ÿ
;
KPA _
ÿ
[ A-Z ] KP ÿ
A
one
ÿ = ÿ ÿ
[ AZ ] one
KP ÿ ÿ
A
one
ÿ [ AZ ] ÿ one
KP ÿ
KP ÿ
A A
4. The reaction rate is equal to the rate of product formation, i.e. CO2: V =
k3[ZO][ZCO].
Let us express the surface concentrations [ZO] and [ZCO] in terms of the pressures
reagents and the total concentration of surface centers: [
ZCO ]
K1
_
ÿ
;[ ]ZCO K1P ZCO [ ]
ÿ
PZ
CO [ ]
ÿ
2
[ ZO ]
K2 _ ÿ
22 ;[ ]ZO KPZ ÿ
2 O []
PZ
O2 [ ]
ÿ
[ ] [ÿ Z ]ÿ [ÿK1PCO
Z [ ] 0ÿ ZCO ][ (1 ÿ Z
] ÿÿZO
K2PO 2
)
one
[ Z] ÿ ÿ
[ Z] 0
one ÿÿ KPKP
COone 2 O2
KP CO
[ ZCO ] ÿ one ÿ
[ Z] 0
one ÿÿ KPKP
CO one 2 O2
KP2 O2
[ ZO ] ÿ ÿ
[ Z] 0
one ÿÿ KPKP
CO one 2 O2
Thus, the expression for the reaction rate will be written as
53
KPKP
2 O2
_
ÿ
one CO 2
V = k3[ZO][ZCO] = k3 ÿ
[ Z] 0
2
(one
ÿÿ KPKP
CO one 2 O2 )
At low pressures of the initial reagents 1 COKP ÿ KP << 2O2

1, and
_ expression
The value for the reaction rate will be written as V = k3 K2PO2 ÿK1PCO . Then flog
the CO dock is 1 and the oxygen order is ½.
5. Because
[ ZO ] KP2 O2
ÿ ZO ÿ ÿ
,
0Z[] one ÿÿ KPKP
CO one 2 O2
[ ZCO ] KP CO
ÿ ÿ ÿ one
,
ZCO
0Z[] one ÿÿ KPKP
CO one 2 O2
then
KPKP ÿ
21 O2 CO 2 2ÿ
Vk3
ÿ
[ Z] k0Z [ ] ÿ
ÿ ÿ
k ÿ ÿ ,
ÿ
2 thirty ZO ZCO eff ZO ZCO

ÿ ÿKPKP
(one
one CO 2 O2 )
2
i.e. keff = kthirty
[Z] .
6. No, it is not, since the Langmuir model implies the reversibility of the process,
and the “adsorption” of flies on Velcro can be considered irreversible. A consequence
and sign of this is the possibility of filling the Velcro with flies even at their low
concentration, if the experiment is carried out for a considerable time. In the case of
Langmuir adsorption for any duration
experiment, the filling cannot exceed the equilibrium value.
Note: If the Velcro is bad, then the process will be reversible. So
both negative and positive, but justified answers are accepted.
54
Grading system
1. Signs of thermodynamic functions Determining 3×1 point 4 points
factor 1 point
2. Influence of temperature, explanation 1 + 1 point 2 points
3. Expression for the equilibrium degree of filling 3 points
4. Concentrations of [ZCO], [ZO] 3 + 3 points 11 points
Reaction rate Orders at low 2 points
pressures 3 points
5. Expression for keff 2 points
6. Reasonable answer 1 point 3 points

Explanation 2 points
TOTAL: 25 points
Solution of problem 4 (Salnikov O.G.)

1. In the structure of BorylCAT, there are spatially closely spaced
female nitrogen and boron atoms. Nitrogen has a lone pair (Lewis base), and boron
has a vacant orbital (Lewis acid) (therefore, compounds of this type are also called
frustrated Lewis pairs). Caught between
do acidic and basic centers, the field hydrogen molecule

is oriented and coordinated by one atom to nitrogen and the other to boron (although
the H–H bond is not completely broken in this case). The option with a broken H–H connection is also
counted as correct.
2. Since as a result of the reaction of two molecules one is obtained, the entropy of the reaction must
be negative (ÿrS° < 0). Since the equilibrium constant decreases with increasing temperature (i.e., the
equilibrium shifts to the left), the reaction is exothermic, that is, ÿrH ° < 0.
3. The most accurate way to find enthalpy and entropy is graphical. To do this, we transform the
expression for the dependence of the equilibrium constant on temperature to a linear form:
Next, we plot ln Kc versus 1000/T:
55
-
From the graph we get that –ÿrH°/R/1000 = 6.36 K, whence ÿrH° = 6.36 1000
8.314 = –52900 J/mol ÿ –53 kJ/mol. Similarly, we find ÿrS° = –18.5 8.314 = –154 J/mol/
K ÿ –150 J/mol/K. Also, these values can be found without plotting a graph, by solving a
system of equations for two selected temperatures from the table.
4. The activation energy for the dissociation of the BorylCAT complex with hydrogen
can also be found either graphically or by solving a system of equations for two
temperatures. In the graphical method, you first need to convert the Arrhenius equation
to a linear form:
Next, we plot the dependence of ln k2 on 1000/T:
From the graph we get –Ea / R/1000 =what

–11.6 K, Ea = 11.6 1000 8.314 where
= 96400 J/mol ÿ 96 kJ/mol.
56
5. The question requires finding the time after which [H2] = 1.01·[H2]ÿ:
It can be seen that the equilibrium time is much longer than the hydrogen bubbling time
(1 s); therefore, the use of the formula specified in the condition is permissible (the formula
was derived for the case when the initial hydrogen concentration in the solution is created
instantly).
6.a) In the first ampoule, thermodynamic equilibrium is established at a partial pressure
of hydrogen over the solution P(H2) = 5.0 bar. Hence, according to Henry's law, [H2]ÿ = 2.10
10–3 5.0 = 0.0105 mol/L. It is important to note that this concentration of hydrogen in the
solution is established taking into account its reversible reaction with BorylCAT. Let [AH2]ÿ =
y, then [A]ÿ = 0.05 – y. Using the expression
for the equilibrium constant, we obtain the equation
From here it is easy to get
For the first ampoule, the proportion of hydrogen bound into a complex with BorylCAT is
on the
b) In the second ampoule, a total gas pressure of 5.0 bar is first created above the
solution, and only then the system comes to thermodynamic equilibrium. It is important to note
that the ampoule initially contained argon at atmospheric pressure; therefore, at the initial
moment of time, the partial pressure of hydrogen over the solution is P0 = 4.0 bar. In this
case, after equilibrium is established, the partial pressure of hydrogen over the solution will be
lower, since part of the hydrogen will be in the solution in a free or bound form.
First, we find the volume of the gas phase in the ampoule. Ampoule inner radius = 3.14
2 20.3 0.1732 = 1.91 ml.
r = 5.0/2 – 0.77 = 1.73 mm. Then Vampoules = ÿ h r
The volume of the gas phase Vgas = 1.91 – 0.50 = 1.41 ml. Now we can find a common
amount of hydrogen in the system
57
After equilibrium is established, hydrogen is in the ampoule in three forms - in the gas
phase (ÿ(H2)gas) and in solution in free (ÿ(H2)solid) or bound (ÿ(AH2)) form.
where P is the equilibrium partial pressure of hydrogen. According to Henry's law [H2]ÿ =
2.10 10–3 P, then
ÿ(AH2) is found from the expression for the equilibrium constant, as was done
above for the first ampoule:
As a result, from the material balance for hydrogen, we obtain the equation
This equation is reduced to a quadratic one:
We solve the resulting quadratic equation:
Then
For the second ampoule, the fraction of hydrogen bound into a complex with BorylCAT is
on the
58
References: VV Zhivonitko, K. Sorochkina, K. Chernichenko, B. Kótai, T.

Földes, I. Papai, V.-V. Telkki, T. Repo, I. Koptyug, Phys. Chem. Chem. Phys., (2016), V. 18, pp. 27784–
27795.
Grading system
1. Explanation 1 point
2. Signs of enthalpy and entropy with explanation - 1 point each 3. Determination 2 points
of enthalpy and entropy 2 points each 4. Determination of activation energy 5. 4 points
Calculation of the time to establish equilibrium 6. Calculation for the first ampoule: 3 points
calculation of [H2]ÿ 2 points

2 points
ÿ calculation 2 points
(if 0.0105 M is taken as the total concentration of hydrogen in

solution,
then 1 point).
Calculation for the second ampoule: P0 value 1 point
Vgas calculation 1.5 points
Calculation of ÿ(H2)total 1 point
Expression for ÿ(H2)gas 1 point
Expression for ÿ(H2)rr 1 point
Expression for ÿ(AH2) 1 point
Solving a quadratic equation 1.5 points
ÿ calculation 1 point
TOTAL: 25 points
Solution of problem 5 (Sedov I.A.)

1. The difference between the energies of the absorbed and emitted light quanta is equal to the
energy of the transition from the zero to the n-th vibrational level:
hc hc
-ÿ
nhÿ ;
ÿ ÿ
one 2
c cÿ
ÿ .
one
ÿ ÿ
2 c cn ÿ
ÿÿ
ÿ
nÿ one
ÿ
one
2. The maxima correspond to transitions to levels with n = 1, 2, … Difference ), so the frequency
difference
of the emitted light is equal to ÿ.
59
3. Fluorescence is proportional to the concentration of unbound protein [P]:

FF [ P]
ÿ
0 ;
[ P] [PL]
ÿ
[ PL ]
ÿ ;K[ ] [PL]
P ÿ Lc ÿ; ÿ[ ] [PL] c .
P
ÿ
L
[ P][L]
Since the initial ligand concentration cL is much greater than the initial
[]P F0
protein concentration cP, then [ ] c L ÿL _ FF ÿ
0
ÿ
. To find
[ PKP
][] cÿ L one ÿ Kc L
F0
K, you should plot the dependence on cL, which
F is linear with
slope K:
F
0 ÿ
Kc L 1ÿ
.
F
According to the table, we get K = 1.63 104 . (Any correct calculation for
individual points without plotting is also accepted).
4. The fraction of P* molecules that return to the ground state with the
emission of a light quantum (radiative transition) is equal to the ratio of the rate of
this process to the sum of the rates of radiative and nonradiative transitions
k2 [P*]
_
k2
ÿ
.
k 1[P*] ck ÿ [P*] kck ÿ The total number of transitions of both types is not
L2 _ one L 2
depends on the ligand concentration and is determined by the intensity of the

exciting radiation. Therefore, fluorescence is proportional to the fraction of radiative
transitions:
k2
FF ÿ
;
0
kck
12 L
ÿ
F0k ÿ
one
cL 1. ÿ
Fk 2
5. Fluorescence in this case is proportional to the proportion of unbound protein

and the fraction of radiative transitions:
k2 one
F 0k1 ÿ ÿ
FF
ÿ
0
ÿ
c 1ÿ Kc L 1ÿ ÿ.
1 kck ÿ ÿKc
ÿ;
L ÿ ÿÿ
L2 _
one L
Fk ÿ 2
k '
Denote k ÿK
one
and expand the brackets:

2
F0
ÿ
KK c' KK
L
2 ÿcÿ
ÿ
'
ÿ
L
1. ÿ
F
The values of K and K' can be found by solving a system of two equations for
60
any pair of experimental points. On average, they are 770 and 5240. Since the equation is symmetrical,
both roots can correspond to the stability constant of the complex. (Answers corresponding to
experimental data at any pair of concentrations are counted).
Grading system:
1. For the right formula 5 points
2. For the correct answer 3 points
3. For the correct conclusion of the dependence of fluorescence on the concentration 6 points
ligand ions 4 points
For the correct value of the constant 2 points
4. For the correct conclusion 4 points
5. For the correct conclusion of the dependence of fluorescence on the concentration 7 points
ligand ions 5 points
For the correct value of one constant 1 point
For the correct value of the second constant 1 point
TOTAL: 25 points
61

Inorganic Chemistry 2: Table of Contents

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Inorganic Chemistry 2: Table of Contents

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Solution of problem 1 (Elnyakov D.D.) ........................................ .......... 2

Solution of problem 2 (Seryakov S.A.) ........................................ ............ 5

Solution of problem 3 (Motornov V.A.) ........................................ ......... 7

Solution of problem 4 (Motornov V.A., Lebedeva O.K.) .................................. 11

Solution of problem 5 (Kovalenko A.D.) ........................................ ...... thirteen

Solution of problem 6 (Kirilenko N.Yu., Dolzhenko V.D.)................................. 17

Solution of problem 7 (Bushkov N.S.) ........................................ ........... twenty

Solution of problem 8 (Karnaukhov T.M., Dolzhenko V.D.) .................. 23

Solution of problem 1 (Andronov V.A.) ........................................ ....... 29

Solution of problem 2 (Zima A.M.) ........................................ ............... 31

Solution of problem 3 (Plodukhin A.Yu.) ........................................ ...... 34

Solution of problem 4 (Salnikov O.G.).................................................. ...... 37

Chemistry and life 41

Solution of problem 1 (Rodkina N.V., Bacheva A.V.)....................... 41

Solution of problem 2 (Dikhtyar Yu.Yu.) ........................................ ......... 44

Solution of problem 1 (Gulevich D., Kuramshin B.K.).................................. 48

Solution of problem 2 (Zima A.M.) ........................................ ............... 49

Solution of problem 3 (Karnaukhov T.M.) ........................................ ...... 52

Solution of problem 4 (Salnikov O.G.).................................................. ...... 55

Solution of problem 5 (Sedov I.A.) ........................................ .............. 59

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© TsPMK Higher School of Chemistry

0.006405 / 2 = 0.0032025 mol.

m(A3(PO4)k) = ÿ(A3(PO4)k)ÿM(A3(PO4)k), where A is the molar mass of the metal.

After transforming the resulting equality, we have: A = 6.6·k.

+3 19.8~Ne inert gas

Thus, in addition to copper (II) chloride, solution X also contains chlorine

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2H2O + 2eÿ = H2ÿ + 2OHÿ (between t1 and t2)

n(eÿ ) = 2n(Cl2) = 0.0045115 mol ÿ 2 = 0.00903 mol

= 1.03644ÿ10ÿ6 (t2 – 3090) mol

By the condition n(Cl2) + n(O2) = n(H2). Let's make an equation:

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1. Establishing the composition of liquid X:

Conclusion that hydrogen is released on the cathode after t1 - 1 point

Calculation-based determination of lithium - 3 points

2. For finding the time during which the electric

3. Equations of chemical reactions:

Solution of problem 2 (Seryakov S.A.)

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2AsCl3 + 6CH3COOK + H2O = [(CH3)2As]2O + 4CO2 + 2CH3COOH + 6KCl.

4. A heavier analog of arsenic is antimony. A gray spot formed as a result of the

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1. 7 substances - 1 point each,

2. correct formula of substance H - 1.5 points

3. Correct explanation 2 points

4. Reaction equations (with explanations) - 1.5 points each 3 points

Solution of problem 3 (Motornov V.A.)

The second element in A is oxygen.

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Since salt B is formed in an aqueous solution, it is logical to assume that in

Therefore, y ÿ 39.71ÿ 6.742 ÿ x :

corresponds to 3 sodium cations and 2 protons: 22.99 ÿ3 ÿ 2 ÿ1.008 ÿ 71 G . Means

the remainder corresponds to 7 water molecules. C - MnSO4 7H2O.

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From the same amount of salt G , 0.0179 g of L is precipitated by ammonium sulfide .

That is, in the resulting compound, the molar ratios Mn: I = 1: 3.

In redox reactions, the number of donated electrons

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In addition, this substance contains Mn + 4, 3 IO6 5- , x Na+ and possibly

22.99x ÿ1.008 ÿ(11ÿ x) ÿ165.092

1) I2O5 + H2O ÿÿ 2HIO3

A -Xe _ F – NaHXeO4 _ III - [XeF][Pt2F11]