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Table of contents

Dear participants! ................................................. ........................................ 4

Inorganic chemistry ................................................ .................................... 5

Task 1 (for grade 9) .............................................. ..................................... 5

Task 2 (for grade 9) .............................................. ................................... 6

Task 3 (for grades 9 and 10) .......................................... ................................... 7

Task 4 (for grades 9 and 10) .............................................. ............................ eight

Task 5 (for grades 9 and 10) .............................................. ............................ 9

Task 6 (for grades 9, 10 and 11) ....................................... ...................... eleven

Task 7 (for grades 9, 10 and 11) ....................................... ...................... 14

Task 8 (for grades 9, 10 and 11) ....................................... ...................... sixteen

Organic chemistry ................................................ ...................................... eighteen

Task 1 ................................................. ................................................. .. eighteen

Task 2 .................................................. ................................................. .... nineteen

Task 3 ................................................. ................................................. .. 21

Chemistry and Life .................................................. ................................................. 23

Task 1 ................................................. ................................................. .. 23

Task 2 ................................................. ................................................. .. 24

Physical chemistry ................................................ .................................... 27

Task 1 (for grades 9 and 10) .............................................. ......................... 27

Task 2 (for grades 9, 10 and 11) ....................................... ...................... 28

Task 3 (for grades 9, 10 and 11) ....................................... ...................... thirty

Task 4 (for grades 9, 10 and 11) ....................................... ...................... 33

Table of ionic radii, Å.................................................... ...................... 36

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Dear participants!

The second theoretical round includes four blocks of tasks:

"Inorganic Chemistry", "Organic Chemistry", "Chemistry and Life" and
"Physical chemistry". Each task is worth 25 points. To your asset

four (4) problems solved by you with a maximum

result.
Required condition:
- participants from 9 classes choose tasks from at least two (2)
various blocks;
- participants from 10 classes choose tasks from at least three (3)
different blocks, and from the block "Inorganic Chemistry" you can
select only tasks 3, 4, 5, 6, 7 and 8;
- participants from 11 classes choose one problem from each block,
moreover, only tasks can be selected from the "Inorganic chemistry" block
6, 7 or 8, only tasks can be selected from the Physical Chemistry block
2, 3 or 4

Good luck!

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Inorganic chemistry
Task 1 (for grade 9)
A simple substance A reacts with a simple gaseous substance B with

the formation of a mixture of liquid substances C, D and E. The introduction of any of the products

in excess water leads to the formation of substance A, the release of gas F and

an aqueous solution of a strong acid G. During the hydrolysis of substances C, D and E

the mass ratio A : F is 0.50, 1.50, and 2.50, respectively, and the ratio

masses F : G invariably.

A B
H Phosphorus I
C
M J+F
C
H2O
O2 (V2O5 )

H2O B
A+B E A + G+F camphor
K H2O G+L
H2O
I
H H2O
D J G+F

Phosphorus reacts with substances A and B to give solid products H and I

respectively. Gas F was first treated with substance I, distilled from

the reaction mixture a colorless liquid J, which was affected by H, which

led to the formation of D. The introduction of substance J into water does not lead to precipitation

A, but accompanied by the selection of F and G.

If F is reacted with B in the presence of catalytic amounts

camphor, liquid K is formed , which does not give A and F during hydrolysis , but in

in an aqueous solution, in addition to G , substance L was found.

Oxidation of substance F in the presence of V2O5 leads to substance M,

whose action on C is an industrial method for obtaining J. Dissolution

gaseous M in water is usually not conductive, we refrain from describing this

process and we.

All the substances described, with the exception of B, G and I, contain the element A.

1. Determine the substances A–M, confirm the answer with a calculation. Compose

reaction equations.
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2. Explanation of the ability of D to dissolve substance A.

3. Suggest a method for the quantitative regeneration of B from solution G.

4. Why is M not dissolved in water?

Task 2 (for grade 9)

Mineral transformations
In ores, the deposit of which was recently discovered on the island
New in the Arkhangelsk region, contains X1 mineral. He imagines
dark shiny crystals. With prolonged calcination X1 on
air emits a gas with a pungent odor and, depending on the temperature

yellow (substance X2) (p-tion 1) or orange (X3) powder is formed

(district 2). When heated in a sealed ampoule in an oxygen atmosphere X1
turns into white matter X4 (p-tion 3), insoluble in water and
acid solutions, but reacting with a concentrated solution

sodium hydroxide (p-tion 4). Heating X2 with charcoal leads to the release
substance X5 in the form of droplets at the bottom of the crucible (r-tion 5). x5 can be converted to

solution when treated with a solution of sodium in liquid ammonia (p-tion 6). At
slow evaporation of ammonia from the resulting solution stand out

crystals of substance X6, which are decomposed by water with the release of gas Y
(district 7). In the interaction of X4 with a solution of X6 in liquid ammonia
substance X5 is formed (p-tion 8).
Name the element X that is part of these substances. Determine
unknown substances, write down the reaction equations, if it is known that from 1 g
X1 forms 1.268 g of X4, while X6 contains 4.7% sodium. In structure
substance X6 there are particles consisting of 9 X atoms connected
with each other into a polyhedron.

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The scheme of the described transformations:

Task 3 (for grades 9 and 10)

Among the products of the interaction of silver-white metal X and volatile
liquid Y in a sealed evacuated ampoule found red
crystals Z1 and orange crystals Z2.
Z1 reacts with methyl bromide to form substance A. When
the interaction of Z2 with methyl bromide, in addition to A , Z3 is formed . Substance A
is a white crystals, soluble in excess of methyl bromide.
Substance Z3 dissolves in a small amount of water to form
solution from which Z4 crystals can be isolated. It is known that 1 g
Z4 can be converted to Z3 by treating it with 2.695 g of thionyl bromide.
Under the action of hydrobromic acid, substances Z1 and Z2 are converted into
solution of substance Z4.

1) Determine the unknown substances if it is known that Z1 and Z2 are

binary substances. Write down the reaction equations.
2) What is formed when Z1 interacts with water, if there is no
Is there gas release? Write down the reaction equation.
3) When X and Y interact , the formation of at least
measure of two substances - Z5 and Z6. Determine their simplest formulas if
it is known that when adding 0.200 g of Z5 and Z6 to a solution of silver nitrate
0.272 g and 0.239 g of a precipitate, insoluble in
acids.

4) Draw the possible structural formulas of substances A, Z2, Z3 (in

melt), Z5, Z6, knowing that in A and Z3 all atoms of the element X have
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coordination number (CN) 4, in Z5 - only a part of the X atoms has a CN of 4, and in Z2

and Z6 some of the X atoms are in an octahedral environment.

Compound A %X, Z2 Z3
mass 39.66 Z1 58.97 52.69 32.39

Task 4 (for grades 9 and 10)

"-Just think about it! Rumata muttered. - Still
the whole Earth imagines that the most difficult problems
deals with null physics…”
It's Hard to Be a God, Boris and Arkady Strugatsky
Element X forms a large number of molecular halides.
In addition to simple halides containing one X atom in the molecule,
there are more complex ones, for example, isostructural A (fluoride) and B
(chloride). Both compounds can be obtained in one step from oxide B
(the mass fraction of oxygen is 59.68%), which is obtained by heating
mixtures of simple substance X with oxide G of element X (their stoichiometric
the ratio corresponds to the ratio: per 6.440 mass parts G 1
mass part X) (r-tion 1). Further, during the reaction of B with sulfur tetrafluoride
A is formed (p-tion 2), and when higher chloride X is passed over B (gas at
n. y.) it turns out B (r-tion 3).
B is able to react with acetylene (p-tion 4), the resulting product
D contains 6.81% carbon by mass. as an intermediate
this reaction produces E (12.68% C) (p-tion 5).
B gives interesting adducts with tetramethylammonium chloride (p-tion 6)
(product G is a salt containing a doubly charged anion, upon its formation
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bonds in B do not break), and phosphorus pentachloride (p-tion 7) (product H -

contains the same anion).
1. Determine element X and encrypted connections A - Z. Give
your calculations.

2. Write down the equations of reactions 1 - 7.

3. Give the structural formulas D, E, salt anion Zh.

And it can be obtained in another way. When passing higher fluoride X
over a simple substance formed by the element X, at 1850 ° C and pressure
less than 1 mm Hg. Art. a diatomic unstable particle is formed And (p-tion 8),
which further upon condensation with higher fluoride X at a temperature
about -190 ° C gives A (r-tion 9) with an admixture of K (r-tion 10) - another
fluoride X containing 25.45% X by mass. When the temperature rises
up to ÿ50 °ÿ K decomposes with the formation of a yellow solid substance L and A
(at the same time, from 5.097 g K , with a quantitative course of the process, we get
3.145 g L) (district 11). The structure of molecules L is a substituted structure
the simplest hydrogen compound X.
4. Determine the substances I, K, L. Note that the L molecule contains 20
atoms.

5. Write down the equations of reactions 8 - 11.

6. Draw the structural formulas for K and L.

Task 5 (for grades 9 and 10)

Two silver-white metals (I and II) belong to the same group
Periodic system. Both metals dissolve in aqua regia (p-tion 1
and 2) with the formation of compounds A and B , respectively, differing
stoichiometric composition.

When a concentrated ammonia solution is added to solution A

first, a pink precipitate of compound B (p-tion 3) precipitates, which then
dissolves in excess ammonia to form a colorless solution
compounds G (p-tion 4). If a dilute solution is added to a solution D
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hydrochloric acid, almost immediately an orange precipitate of substance D

(district 5).
izb.
HNO3 conc. + HCl conc. NH3 aq. NH3 aq. HCl dil.
I
t
o A V G D

If a solution of potassium chloride is added to a solution of compound B ,

yellow precipitate of a poorly soluble compound E (p-tion 6). With careful
heating E with a solution of hydrazinium sulfate (avoiding large
excess of the latter) a red solution of the compound G is formed (p-tion 7).
Boiling Y with a solution of ammonium acetate leads to the formation of a yellow
draft W (district 8). If F is heated with a concentrated solution
ammonia, first a green precipitate And, which, with further
When heated, it dissolves in excess ammonia to form a colorless solution.
compounds K. When gaseous chlorine is passed through acidified
hydrochloric acid a cold solution of K precipitates a light yellow precipitate
substances L (p-tion 9).
izb.
HNO3 conc. + HCl conc. KCl (N2H6)SO4 NH3 aq. NH3 aq. Cl2
II o
B E o
F o
AND
o
TO L
t t t t

CH3COO(NH4)
W
to

Additionally known:

• Compounds F and G contain three elements each, and

the content of metal II in E is 40.14% (by mass);

• compounds B and I have a similar stoichiometric composition (they differ

metals only) and contain two coordination spheres;

• in addition to the reaction shown in the scheme, and can also be obtained in
exchange reaction between aqueous solutions of compounds Zh and K;
• compounds Z and I have the same quantitative composition;

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• compounds H, I, K (excluding crystallization water) and L have one

and the same qualitative composition;

• compound D consists of four elements and contains 43.36% of metal I

and 22.83% nitrogen;

• compound K has a stoichiometric composition similar to G (they differ

only metals), but K, unlike G, contains a molecule
water of crystallization;

• compounds D and G also have a similar stoichiometric composition

(they differ only in metals), but D molecules , unlike Z, have
zero dipole moment.
Questions:

1. What metals I and II are discussed in the problem? Write down the formulas of substances

A–L, highlighting the inner sphere in square brackets in these complex

connections. Support your answer with calculations.

2. Write the equations of reactions 1 - 9 given in the text of the problem.

3. Give the structural formulas of compounds D and H.
4. Compounds V and Z-K have their own historical names.
Bring them.
5. Compound H is used in medical practice in the treatment
oncological diseases. Try to briefly explain the mechanism
the effects of this medicine (1-2 sentences).

Task 6 (for grades 9, 10 and 11)

One of the least known, but nonetheless one of the most
interesting areas of chemistry - the chemistry of nitrides. The difficulty of understanding this

area lies, first of all, in the fact that often it is not necessary
even talk about the oxidation states of atoms in nitrides, since many

nitrides are electron-rich (they contain free electrons and

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conductive), or contain nitrogen to an unusual degree

oxidation.

A number of binary compounds can be obtained from binary salt A. For

to obtain substance B , 1.31 g of A in decalin (C10H18) was heated to a temperature

boiling point (190 °C) (p-tion 1). An hour later, the vessel was cooled and received almost

black solid B. The completeness of the reaction was monitored by

the volume of released nitrogen, which, after the complete conversion of A to B

amounted to 606 ml at 300 K and 1 atm.

All obtained solid B was heated to 350 °C in a 50.0 ml ampoule,

which was initially filled with argon to a pressure of 1 atm at

temperature of 300 K. After decomposition of B with the formation of brown

substance B (p-tion 2), the total pressure in the ampoule was 574.9 kPa at

temperature 350 °C.

Finally, when B is heated to 900 ° C, a black-green color is obtained.

substance G (district 3). Unit cell of the crystal lattice ÿ

has a volume of 217.2 Å3 (1 Å = 10–8 cm), and the density of crystalline G is 2.16 g/cm3 .
A unit cell contains 3 formula units .

When substances B - G are dissolved in water, solutions are obtained that have

alkaline environment, and in all cases, except for substance A, when dissolved

gas is released (districts 4, 5, 6).

To determine the composition of B , 1.000 g of B was taken and dissolved in excess

hydrochloric acid (p-tion 7). The amount of nitrogen released in this case after

drying was 140 ml at 300 K and 1 atm. The remaining solution at

reaction with an excess of alkali and boiling releases ammonia (p-tion 8), which

completely absorbed 20.00 ml of 0.6791 M hydrochloric acid solution. On the

titration of unreacted hydrochloric acid with ammonia went

10.49 ml of 0.2131 M NaOH solution. This method allows you to install

mass fraction of nitrogen in nitride B.

1. Determine the mass fraction of nitrogen and element M in B. Answer

confirm by calculation.
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2. Set the formulas of substances A - D. Confirm the composition of all substances

calculation.

3. Which of the substances A - G is electron-rich? how many

free electrons per formula unit of this substance?
4. Write the equations of reactions 1 - 8.
Until 2000, there was an opinion that there was another binary
compound in the series A, B, C , D, which, it was believed, is obtained with further
heating G to 1050 °C. However, as it was found out by chemists from
Cornell University, during this process it turned out
three- element substance D, the formation of which was due to
impurities in the reagents. D contains 72.88% metal and 23.15% nitrogen
mass.

5. Define the formula D if it is known that D contains two types

anions, one of which is isoelectronic to the anion of salt A.
In 2012, during the decomposition of A under pressure (12 GPa and 800 °C)
obtained ionic compound E, which is unstable in humid air.
Substance E contains one type of anion, all of which are
diatomic, the length of

NN bond in this anion, which was 0.1202 nm. Bond lengths in

nitrogen and hydrazine molecules are 0.1095 nm and 0.1449 nm, respectively.
6. Suggest composition E, justify your answer. How is resilience changing?
compounds similar in composition to E, but containing elements,
located in the same group of the periodic system as M. Write
equation for the reaction of E with water.

7. Draw the structural formulas (indicating the multiplicity of the bond)

anions of compounds A, E and a two-element anion of compound D.

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Task 7 (for grades 9, 10 and 11)

inorganic aromatics
Borazine (B3N3H6) was obtained in 1926 and thus became the first
synthesized substance from the class of inorganic aromatic

connections. Since then, interest in the synthesis of other inorganic cycles,

having aromaticity, increased significantly. It is about such
compounds formed by elements X, Y and Z, and will be discussed in this
task. Y and Z are elements of the same small period, and X is in the same
group c Y. It is also known that X, Y and Z form simple substances A, B and
C molecular structure, respectively, the number of atoms in molecules
which correlates as 1 : 2 : 4.
Tasks:
1. Give the structural formula of borazine, as well as the name and
structural formula isoelectronic to him and having a similar
structure of an organic compound.

2. Decipher the elements X, Y and Z, and also depict the spatial

the structure of the corresponding simple substances A, B and C. Justify your answer.

For quite a long time, chemists tried to obtain an aromatic

anion Xn ÿ (n is the number of X atoms ). Interest was associated, in particular, with
potential application of substances based on it in the space industry.
Her interests include the search for high-energy compounds, in connection with which
especially attractive was the salt D, consisting entirely of the element X,
which is included in equal amounts both in the cation and in its anion. Data
ions were obtained from derivatives of the binary compound E containing
97.66 wt. % element X, according to the scheme below. F, G and I - also
binary compounds, and G exists as a mixture of cis- and trans - isomers, and the
mass fraction of fluorine in H is 47.03%. Cs + Xn is an

the only reaction product.

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3. Decipher compounds D–I, indicating their structural formulas (for

ionic compounds - the structural formulas of the cation and anion, for G -

structures of both isomers). Give the equation for the reaction of interaction

F with F2. What is the reason for the interest of the space industry in salt D and the like
connections?

The structural analog of Xn ÿ is the anion Yn ÿ , which, for example,

can be isolated in salt J (contains 5.20 wt % sodium). At all

Recently it was also possible to obtain one more analogue of the considered

aromatic anions - a "mixed" anion that is part of the salt K and

consisting of both X and Y atoms . The ratio of the mass fractions of X

and Y in K is 1.13, and in the synthesis of this salt, we used

an anthracene-based compound serving as the source of the "Y2" fragment.

4. Decipher compounds J and K by indicating the structural formulas of the constituents

them cations and anions.

Another example of an inorganic aromatic ion with

a similar structure is a doubly charged cation based on only

elements X and Z, which is part of the salt N. This salt can be obtained from

equivalent amounts of hexafluoroarsenates L and M having the same

qualitative composition, however, the mole fraction of Z in M is 8.88% higher than in L.

5. Decipher the compounds L–N, indicating the structural formulas of the constituents
them cations and anions.

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Task 8 (for grades 9, 10 and 11)

2 2ÿ
4ÿÿ
Triple connections ABC can3

crystallize in the perovskite structure only when

a certain ratio of bond lengths A–C and B–C

(depending on the radii of type A, B and C ions - r(A), r(B)
and r(ÿ)), which is characterized by the factor
tolerance t:
rA
ÿ rÿCÿ ÿÿ
t ÿ
, where r- radii for ions with CN=6
2 ÿrÿBÿr Cÿ ÿ ÿÿ

The perovskite structure can form when t lies within

0.8ÿ1.0. The closer t is to unity, the denser the packing of ions and
the more stable is the perovskite structure. When t goes beyond the specified
limits, the perovskite structure ceases to exist and is replaced by others

structural types.

1) Based on the formula for calculating t , determine which oxides

elements, in addition to barium, during sintering with TiO2 can form
compounds with a perovskite structure. Use the ion table
radii.
2) Why calcium titanate (CaTiO3) in nature more often crystallizes in
orthorhombic cell (one of the distortions of the cubic cell), and not in
cubic (perovskite structure)? Justify your answer by calculating t.
3) If type A cations are removed in the unit cell ABO3 , and cations
type B is replaced by metal cations X, then
get a different struct type (also
cubic, Y lattice), v which
oxide crystallizes (a = 3.734 Å, ÿ = 7.47 g/cm3 ).
Set Y oxide formula
and the oxidation state of the metal X in it, and
also suggest a way to synthesize Y from X into

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minimum number of stages.

On fig. the structure of methylammonium triiodoplumbate (II) is shown on the left,

CH3NH3PbI3 crystallizing in the perovskite structure. To the present

moment, the use of this compound in solar cells allowed

achieve 22% efficiency in converting solar energy into

electric.

4) Get in the minimum number of steps CH3NH3PbI3, based on lead,

potassium iodide, methylamine and necessary inorganic reagents.

Write the corresponding reaction equations.

+
5) Calculate t for CH3NH3PbI3 (r(CH3NH3 ) = 1.80 Å) and evaluate
the possibility of existence for this compound of other crystalline

modifications.

CH3NH3PbI3 decomposes when heated above 50 °C, which is

a consequence of the nature of the methylammonium cation. Work is underway to replace this

unstable cation by much more stable organic or

inorganic cations.

6) Offer a stable singly charged inorganic cation for

substitution for an organic cation in CH3NH3PbI3. Support your answer by calculating t.

7) Is it possible to replace a singly charged cation (at least theoretically) with

doubly charged (whether organic or inorganic)? If yes, how

in this case, to comply with the condition of electrical neutrality of the elementary cell?
How should this doubly charged cation be located in

elementary cell so that the cubic lattice is preserved?

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Organic chemistry
Task 1
The ABC of Ultraviolet
"I liked them at first
Blue eyes, but whiteness ... "

A. S. Pushkin, "The Stone Guest"

As early as the end of the 19th century, it was believed that pale skin was characteristic

aristocrats, and a swarthy one testifies to a peasant origin. V

In the 20th century, the opinion about tanned skin changed dramatically, and tanning became

popular. However, it has now been convincingly proven that the excess
ultraviolet radiation can cause premature aging and
even skin cancer. Used to protect skin from sun exposure

special creams - complex mixtures containing inorganic (like

as a rule, titanium dioxide and zinc oxide, not more than 8%) and organic

substances that can absorb either UV-A (315–400 nm) or UV-B

(280–315 nm) radiation. Only a few of the substances provide
simultaneous protection against UV radiation in the range from 280 to 400 nm.
One of these substances is cinoxate I, the synthesis of which is given in
diagram below.

1. Write the structural formulas of compounds A–F, taking into account that
hydrocarbon A contains 91.3% carbon by mass.
2. What substances X and Y are discussed in the problem? Suggest their structure
if it is known that X from Y is obtained selectively.

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In recent years, cinoxate has been replaced by a combination of different

organic substances, each of which takes on part of the radiation, but
in total, they cover the entire ultraviolet spectrum. One of
the most common and persistent substances is avobenzone II,
absorbs the entire spectrum of UV-A radiation. Strengthen the protective function
creams can be by introducing additional substances that protect against UV
B rays, for example, by adding homosalate III.
3. Write the structural formulas of substances G, H, J–L and components
cream of avobenzone II and homosalate III, if K is known to have a cyclic
structure.

Task 2
At present, cardiovascular diseases are the most
common cause of death in people around the world. One way
prevention of cardiovascular disease is to reduce the level
cholesterol in the blood, for which the so-called statins are actively used

- inhibitors of 3-hydroxy-3-methylglutaryl-coenzyme A reductase,

an enzyme that catalyzes the rate-limiting step in cholesterol biosynthesis.
Some statins can be isolated from natural sources, others
are obtained synthetically, for example, atorvastatin (X), first obtained in
1985. It went on sale in 1996 and during this time ranked first
place in the world among all medicines in terms of sales. On the below
The scheme shows the final stages of the synthesis of atorvastatin (in
the form of calcium salt used in practice).

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1. Give the structural formulas of compounds A–C and X if the structure contains
atorvastatin has four aromatic rings, one of which

contains a heteroatom.
In 2003, an analogue of atorvastatin, pitavastatin (Y), appeared on the market.
also used as the calcium salt. Below is the synthesis scheme
pitavastatin, carried out in 2015 by scientists from the University
Fudan in Shanghai.

2. Give the structural formulas of compounds D–Q.

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Task 3
Platonic molecules
In Euclidean space, there are only five regular
polyhedra, also called Platonic solids - tetrahedron, octahedron,
cube (hexahedron), icosahedron and dodecahedron:

1. Which of the Platonic solids can theoretically have organic

analogues with the same carbon frame?
Below are the schemes for the synthesis of compounds X, Y, Yÿ and Z, framework

which contains one of the above polyhedra.

To obtain X , the [2+2]-cycloaddition product A is subjected to
irradiation at liquid nitrogen temperature. This creates a connection
B, which has a five-membered cycle. Bromination product B,
substance C, contains three types of hydrogen atoms in a ratio of 1: 1: 1, and D -
two types of hydrogen atoms in a ratio of 1 : 1. Under irradiation , D was
the release of a gas lighter than air.

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2. Give the structural formulas of compounds A–D and X.

3. Give the structural formulas of compounds E–K, Y, Yÿ and Z.

what:

• Substance G is a salt of a highly symmetrical cation;

• In the 13C NMR spectrum of substance J , only two signals are observed at 0.1 and

171.6 ppm, and in the 13C NMR spectrum of Y , two signals are observed at 0 and –20.5

ppm. In the 1H NMR spectrum, both substances give only one signal at 0.1 ppm

Upon receipt of K , a substance is released that is generally accepted

the standard in 1H NMR spectroscopy for measuring chemical shifts.

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Chemistry and Life

Task 1
Spectral methods in literary criticism

Four characters from the same literary work donated blood to

analysis. Of the blood samples of each of them were sufficient for study with

using modern instrumental methods, the number of allocated

various chemical compounds (1, 2, 3, 4, each character has only

one substance). The results of studies of these substances, as well as substance 2' -

the product of catalytic dehydrogenation of substance 2 are given in the table.

(In the lists of NMR signals, s is a singlet, d is a doublet, t is a triplet, m is a multiplet,

hm is the group of multiplets).

One of
Substance stereo 2 2' 3 4
isomers 1
Mass
spectrometry: 90 136 132 130 156, 154
molecular ion (m/
z)
5.40 (1H, m),
7.38 (2H, d), 7.92 (2H,
4.70 (2H, *), 4.10 (2H, t),
2.08–1.79 7.15 (2H, d), m), 7.57
1H NMR 8.17 (1H, t), 2.05 (3H, s),
5.35 (1H, d), (1H, m),
2.76 (2H, m), (6H, hm), 1.68 (1H, m),
(ÿ, ppm) 5.03 (1H, d), 7.47 (2H,
1.15 (3H, t) 1.73 (3H, s), 1.52 (2H, m),
2.36 (3H, s), m), 4.70
1.65 (3H, s), 0.92 (6H, d)
2.15 (3H, s) (2H, s)
1.47 (1H, m)
150.1, 133.7, 191.1,
143.2, 138.5,
120.8, 108.5, 172.2, 63.6, 134.2,
13C NMR 179.6, 19.7, 137.3, 129.0,
41.2, 30.9, 37.3, 25.1, 134.0,
(ÿ, ppm) 12.5 125.5, 111.7,
30.7, 28.1, 22.5, 21.1 128.9,
22.0, 21.2
23.5, 20.8 128.5, 46.0
17O NMR
199 - -
355, 197 540
(ÿ, ppm)
* - two overlapping signals
1. Define the structure of all encrypted connections.

2. For each compound, give the formulas of all possible

stereoisomers.

3. What is the ratio of signal intensities in the mass spectrum

connections 4?

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4. What is the operating frequency of the NMR spectrometer used for

registration spectra, if the distance between one of the pairs of neighboring
signals in the 1H spectrum of compound 3 is 1230 Hz?
5. Write the name of each of the characters.

Task 2
Medications for good mood
I guess we all get sad at some point. Sometimes it goes without a trace, and
sometimes it starts to cause inconvenience in life. But in this case your
psychological health can be improved with the help of pharmacological
drugs.

The key syndrome of depression is anxiety and low mood.

But the problem is not only this, clinical depression is accompanied by
more severe symptoms. Then antidepressants come to the rescue,

including from the class of selective reuptake inhibitors. The thing is

that the "hormone of happiness" serotonin (like other neurotransmitters) from
synaptic vesicle enters the synaptic cleft, where

perceived by the receptors of another neuron, after which it can either

be destroyed by special enzymes, or pass further into the body
another neuron, or be captured back, which most often happens
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with depression. The reuptake inhibitor blocks the return of the neurotransmitter to
the cage he came from. Thus, in the synaptic cleft
more serotonin accumulates and the severity of associated
him effects.
1. The diagram shows the biosynthesis of serotonin from aromatic
amino acids A. Name the amino acid A and decipher the structures AB.

2. Amino acid A is not produced in the human body and others

animals, while being found, for example, in beans, dark chocolate,
nuts. The daily human need for amino acid A is 2 g,
content in chocolate 0.21% (by weight). Calculate what percentage of
daily energy requirement will be received by the student, if replenished
amino acid deficiency Will he solve it exclusively with chocolate? Consider
that 1 g of dark chocolate contains 5.46 kcal, the daily energy requirement
3000 kcal.

One of the most famous antidepressant class of inhibitors

serotonin reuptake inhibitor (SSRI) is Prozac. His active
substance - fluoxetine.
3. Below is a scheme for the synthesis of Fluoxetine. Decipher
CF structures .

Another "blockbuster" antidepressant of the same class is

Zoloft and its active ingredient Sertraline.

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4. Decipher the scheme of sertraline synthesis, depict the structural

formulas of substances G–M. Take into account that at the stage of transformation I–
J two reactions proceed simultaneously.

The most modern drugs are selective

serotonin and norepinephrine reuptake inhibitors (SNRIs).
One of the brightest representatives of antidepressants of the SNRI class is
Velaxin and its active ingredient Venlafaxine.
5. Decipher the synthesis scheme below, indicating the structural
formulas of substances N–Q. Please note that at the stage of obtaining O
selective reduction occurs, and the P–Q transformation proceeds through
formation of an intermediate.

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Physical chemistry

Task 1 (for grades 9 and 10)

Decomposition of copper sulfate

During the decomposition of metal sulfates, oxides are formed

corresponding metal and substance A. Substance A, however, at

elevated temperature decomposes into B and C. Consider the process

decomposition of anhydrous copper (II) sulfate at elevated temperature.

When copper sulfate is heated, two reversible processes occur:

CuSO4 ÿ CuO + ÿ(g) (K1),

2A(g) ÿ 2B(g) + C(g) (K2).

1. Define formulas A, B and C.

2. Write down the expressions for the equilibrium constants K1 and K2.

3. Derive expressions for the pressures of gases A, B and C in the vessel into which

an excess of copper sulfate is placed, after reaching equilibrium in the atmosphere

argon.

4. How will the pressures A, B and C change if the pressure in this

vessel a) by adding argon at a constant temperature, b)

heating the vessel at a constant total volume? Explain the answer.

Additionally, it is known that the thermal effects of both reactions have

the same sign.

Into a 1.00 L vessel filled at 273 K with pressurized argon

100 mmHg Art., placed a sample of CuSO4 and heated to a temperature of 1050 K.

After reaching equilibrium, it turned out that the mass of the solid phase

decreased by 0.3869 g, and the pressure in the vessel turned out to be 108.59 kPa.

5. Determine the equilibrium constants K1 and K2 at a given temperature.

6. It is known that the difference between the enthalpies of reactions (1) and (2) is

27 kJ/mol. Determine at what temperature during the decomposition of sulfate

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copper in an inert atmosphere, the amount of B formed will be 5 times

more than A.

Upon further heating of the vessel, copper sulfate decomposed

completely, and the mass of the solid phase has ceased to change. However, starting from

temperature of about 1400 K, the mass of the solid phase began to decrease again.
7. Write a reaction equation that explains the decrease in mass
solid phase at this temperature.
8. How will the pressures A, B and C change in the vessel during this
reactions? Explain the answer.

Additional Information
1) The equilibrium constant K is expressed in terms of gas pressures expressed
in bar (1 bar = 105 Pa = 750 mmHg). Solid
substances are not included in the expression for the equilibrium constant.

2) The equilibrium constant K is related to the change in enthalpy and entropy

reactions:

ÿ ln = ÿ° ÿ ÿ°.

Task 2 (for grades 9, 10 and 11)

Kinetics of the phosgene formation reaction
The kinetics of the CO + Cl2 ÿ COCl2 reaction in the gas phase was studied
Bodenstein in 1924. He studied the temperature dependence
rate constants and reaction orders by substances. This reaction is like
It turned out that it proceeds by a radical chain mechanism.

To establish the order of the reaction, a series of experiments was carried out.
First, the half-life of chlorine was measured at various
initial concentrations (from 0.005 M to 0.01 M) and the same initial
CO concentrations (0.2 M). It was found that the half-life
chlorine does not depend on its initial concentration.

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In another experiment at a temperature of 450 K, the following was obtained:

dependence of CO concentration on time. Initial chlorine concentration

was equal to 1.50 M.

s(CO), mmol/L 5.00 4.06 3.31 2.69

Time, s 0 120 240 360
1. Determine the reaction order for CO and for chlorine. Calculate Constant

speed at 450 K.

To explain the experimentally determined orders of the reaction according to

reagents were proposed two mechanisms (A and B), shown below. For

their interpretation, one can use approximate methods of chemical

kinetics: quasi-stationary approximation, according to which the velocity

formation of unstable radical particles is equal to the rate of their

consumption, and the quasi-equilibrium approximation, according to which for

some reversible stages, there is a constant ratio

concentrations of reagents and products, corresponding to the value of the constant

balance of this stage.

A) Cl2 ÿ 2Clÿ (K is the equilibrium constant) (1)

ÿlÿ + CO ÿ COClÿ (k2) (2)

Clÿ + COClÿ ÿ COCl2 (k3) (3)

B) Cl2 ÿ 2ÿlÿ (K is the equilibrium constant) (1)

Clÿ + CO ÿ COClÿ (k2, kÿ2) (2, -2)

Cl2 + COClÿ ÿ COCl2 + ÿlÿ (k3) (3)

Clÿ + COClÿ ÿ COCl2 (k4) (4)

Clÿ +COClÿ ÿ CO + Cl2 (k5) (5)

2. Derive expressions for the rate of phosgene formation for

mechanisms A and B. When withdrawing, you must use

quasi-stationary approximation for unstable radical particles, and

if the equilibrium constant is specified, then the quasi-equilibrium approximation for

the corresponding reaction. In the equations you received,

contain only the rate constants and concentrations of chlorine and CO.
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3. Determine the reaction orders for the reactants for mechanism A.

4. What values can take the order of the reaction in CO and in Cl2 for
mechanism B at different ratios between the rate constants and
balance?
5. At what ratios between the equilibrium and rate constants
orderings in substances for mechanism B will coincide with experimentally
certain (i.e., with those calculated by you in paragraph 1)? Learn what is needed
give two different answers. For each option, write down
expression for the effective rate constant.
6. It was found that k4 and k5 have similar values. Which of the two
the options you proposed in paragraph 4 are actually implemented?
7. Which of the following substances: oxygen, benzoyl peroxide (C6H5COO)2, chloride

nitrosyl (NOCl) - will increase the rate of formation of phosgene in this

reactions? Explain the answer.

Additional Information. For reactions of different order

the dependences of the concentration of the reagent on time in a general form are known:
one one

n order (n ÿ 1): ÿ1
ÿ

ÿ1 = ( ÿ 1) ,

1st order: ln = .

Task 3 (for grades 9, 10 and 11)

How to grow a crystal
In a faceted crystal, the natural phenomenon itself is, as it were,
sets a ready-made, well-formulated problem ...
I. I. Shafranovsky
Once, on a special course in chemistry, inquisitive schoolchildren Anton and
Lisa bet which of them will be able to grow a larger
single crystal. Immediately after class, without wasting time, they decided
prepare the necessary solutions for this.

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– To grow a single crystal, you first need to get a crystal

seed, - said Anton, slowly rereading the lines of the school manual,
- ... take an electric stove, a 100 ml glass and cook 50 ml in it
saturated at 40ÿ CuSO4 solution.
- You did not say how much reagent is required for this? - stopped
his Lisa.

- It's obvious, - Anton grinned, writing out from the reference book
analytical chemistry some value. Then he weighed CuSO4ÿ5H2O,
dissolved the sample in a glass of water when heated and began to cool
the resulting solution to room temperature.
- The crystals are falling! - Lisa was delighted, - I'll take for seed
the biggest.
“That won’t help you,” Anton smiled, removing
crystal.

After that, the schoolchildren weighed 17 g of CuSO4ÿ5H2O, dissolved

samples in 100 ml glasses, adding 50 ml of water to them, then
dipped into the seed solutions. Lisa left the resulting solution in
glass open, and Anton decided to cheat and gave his glass with a solution
familiar student Maxim, who promised to put him in an old
laboratory box. The schoolboy thought that growing a single crystal in
dry boxing will allow him to easily get ahead of Lisa.
Three days later, Maxim returned the solution to Anton. However, the crystal
the glass turned out to be quite small, which surprised the student very much. Unwilling
to give way to Lisa in the dispute, Anton decided to quickly find a new way on the Internet

accelerated growth of single crystals. In the first 5 minutes of searching, he opened

a site on which the author suggested adding to the crystals when growing crystals
a little sulfuric acid solution. “Great, this method will do.”
Anton hastily decided. However, there was no sulfuric acid in the laboratory,
so he added a few drops of hydrochloric acid to his glass
and left.
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The next day, returning to the chemistry room, Anton found

what a night his crystal completely dissolved! "Horror! All urgently needed
fix it before it's too late...” the schoolboy thought and began to calculate.

After spending a little time thinking, Anton took a glass and prepared
the same stock solution as four days ago. After which he placed
a glass with the prepared solution into an empty glass with a volume of 250 ml, and
prepared a saturated solution of RbCl in 10 ml of water in an external beaker.
The outer glass was hermetically sealed by Anton with a lid.

1. Calculate what mass of CuSO4 ÿ 5H2O the guys needed when

receiving seeds.

2. Estimate the mass of Lisa and Anton's crystals three days after the start
experiment. Here and below, assume that room temperature and
air humidity does not change and is 25 ÿ and 80% respectively.
Before the experiment, the dry box was completely filled with argon, after the experiment in

he was balanced. Box volume 400 l, inner diameter

a glass with a volume of 100 ml is 47 mm. The contribution of the mass of the seed to the mass

crystal must be neglected.

3. Suggest at least one reasonable reason why Anton
hoped for a faster growth of his single crystal in boxing than in
open glass. What did he not learn?
4. Suggest at least one factor why Anton's crystal
dissolved after adding hydrochloric acid to the solution, and explain it
influence on the system in terms of thermodynamics. Argued
explain whether the student could “save” his crystal if he
followed the instructions from the site and took sulfuric acid?
5. Estimate the crystal of what mass Anton will receive after reaching
its system of thermodynamic equilibrium, that is, the establishment in
external glass of water vapor pressure equal to saturated.

6. How long should the equilibrium be established in Anton's system,

so that he could win the dispute with Lisa at this moment?
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Reference data

CuSO4: solubility 22.3 g per 100 g water (25 °C), 28.5 g per 100 g water

(40 °ÿ), take the density of saturated solutions equal to 1.2 g/cm3 .

RbCl: solubility 94 g per 100 g water (25°C).

0
Saturated water vapor pressure (°C) = 0.0313 atm.

To estimate the height of the water layer evaporated from the surface in

open atmosphere, calculate as exp(mm) = . ÿ(ÿ)ÿ

ÿ

, where

0
- air humidity, (atm) is the pressure of saturated water vapor above

clean water, (days) – evaporation time.

The pressure of saturated water vapor over the solution in the considered
0 ÿ

solutions can be taken as = , where is the mole fraction of water among

all particles in solution.

Task 4 (for grades 9, 10 and 11)

Enzymatic catalysis and the Eyring equation

It is well known that most often the rate of enzyme-catalyzed

reactions is described by the Michaelis–Menten equation:

kES
cat [ ] [0 ]
v ÿ
,
KSM
ÿ [ ]

where v is the reaction rate, [S] is the concentration of the substrate (substance,

undergoing a chemical transformation by the action of an enzyme)

[]E
0 is the total concentration of the enzyme in solution (both in free and

substrate-bound form) kcatis the conversion rate constant

enzyme-bound substrate into the reaction product, KM is the constant

Michaelis characterizing the affinity of the substrate for the enzyme.

Study of the kinetics of pyrophosphate anion hydrolysis in weakly acidic

buffer solution in the presence of 0.66 nM pyrophosphatase enzyme at

various temperatures depending on the concentration of pyrophosphate

led to the following results:

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[S], ÿ 2.00ÿ10-6 8.00ÿ10-6 1.80ÿ10-5 3.20ÿ10-5 5.00ÿ10-5

v, Mÿsÿ1 (25 °C) 4.96ÿ10-8 1.19ÿ10-7 1.72ÿ10-7 2.33ÿ10-7 2.90ÿ10-7
v, Mÿsÿ1 (45 °C) 2.72ÿ10-7 8.59ÿ10-7 1.55ÿ10-6 2.21ÿ10-6 2.77ÿ10-6

[S], ÿ 7.20ÿ10-5 9.80ÿ10-5 1.28ÿ10-4 1.62ÿ10-4 2.00ÿ10-4

v, Mÿsÿ1 (25 °C) 3.51ÿ10-7 4.34ÿ10-7 5.28ÿ10-7 6.37ÿ10-7 7.50ÿ10-7
v, Mÿsÿ1 (45 °C) 3.51ÿ10-6 4.08ÿ10-6 4.88ÿ10-6 5.48ÿ10-6 6.40ÿ10-6

1. What is the hydrolysis product?

2. Determine the rate constants of pyrophosphate anion hydrolysis
in the form of a complex with pyrophosphatase ( kcat
) and in the absence of the enzyme at 25 and

45°C.

To describe the dependence of the reaction rate on temperature, instead of

ÿ
Ea

empirical Arrhenius equation kAeÿ RT often use the equation

ÿ ÿ
ÿS
ÿH
kT ÿ

BR RT ee
k Eyring
ÿ

h which has a theoretical justification. In that

equation kB ÿÿ
1.38 10
ÿ

23
JÿK
ÿ1
is the Boltzmann constant, h 6.63 10ÿ 34 Jÿs -
ÿ ÿ

ÿ ÿ
Planck's constant, andÿH
and S ÿ ÿ enthalpy and entropy of activation, which

are often taken to be independent of temperature (with not too large

changing it).
3. Give expressions that allow you to calculate the activation energy
process when using the Arrhenius equation and the enthalpy of activation
when using the Eyring equation, if two values of the constants are known

reaction rates k1 and k2 at temperatures T1 and T2.

4. If the values of the rate constants are known for several

temperatures, then to determine the activation parameters, one can construct

dependence graph in certain coordinates. To minimize

the error of the obtained data, it is necessary that this dependence be
linear, therefore, when analyzing the kinetics using the Arrhenius equation
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use coordinates lnk vs 1/ T. What coordinates should

to use in the case of the Eyring equation?

5. Using the Eyring equation, estimate the values of enthalpy, entropy

and Gibbs energy (at 25 °C) of activation of hydrolysis of the pyrophosphate anion in the form

complex with the enzyme and in the absence of the enzyme. Is it possible to conclude that

enzymatic catalysis in this case has an enthalpic or

entropic nature?

6. Choose the correct statement:

a) the enzyme reduces the enthalpy of hydrolysis

b) the enzyme increases the entropy of hydrolysis

c) both statements a) and b) are true

d) both statements a) and b) are false

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Table of ionic radii, Å

Ion cf* Radius Ion cf* Radius Ion cf* Radius
Ag+1 2 0.67 CD+2 12 1.31 Cu+2 4 0.57
Ag+1 4 1.02 Ce+3 6 1.01 Cu+2 6 0.73
Ag+1 6 1.15 Ce+3 eight 1.143 Cu+3 6(HC) 0.54
Ag+2 4 0.79 Ce+3 10 1.25 Dy+2 6 1.07
Ag+2 6 0.94 Ce+3 12 1.34 Dy+2 eight 1.19
Ag+3 4 0.67 Ce+4 6 0.87 Dy+3 6 0.912
Ag+3 6 0.75 Ce+4 eight 0.97 Dy+3 eight 1.027
Al+3 4 0.39 Ce+4 10 1.07 Er+3 6 0.89
Al+3 6 0.535 Ce+4 12 1.14 Er+3 eight 1.004
As+3 6 0.58 Cl-1 6 1.81 Eu+2 6 1.17
Au+1 6 1.37 Co+2 4(BC) 0.58 Eu+2 eight 1.25
Au+3 4 0.68 Co+2 6(BC) 0.745 Co+2 Eu+2 10 1.35
Au+3 6 0.85 6(HC) 0.65 Eu+3 6 0.947
Au+5 6 0.57 Co+3 6(BC) 0.61 Eu+3 eight 1.066
Ba+2 6 1.35 Co+3 6(HC) 0.545 Cr+2 F -one
4 1.31
Ba+2 8 1.42 6(BC) 0.8 F -one
6 1.33
Ba+2 10 1.52 Cr+2 6(HC) 0.73 Fe+2 4(BC) 0.63
Ba+2 12 1.61 Cr+3 6 0.615 Fe+2 4(BC) 0.64
Be+2 4 0.27 Cr+4 4 0.41 Fe+2 6(BC) 0.78
Be+2 6 0.45 Cr+4 6 0.55 Fe+2 6(HC) 0.61
Bi+3 6 1.03 Cr+5 4 0.345 Fe+2 8(BC) 0.92
Bi+3 eight 1.17 Cr+5 6 0.49 Fe+3 4(BC) 0.49
Bi+5 6 0.76 Cr+6 4 0.26 Fe+3 6(BC) 0.645
Br-1 6 1.96 Cr+6 6 0.44 Fe+3 6(HC) 0.55
Ca+2 6 one
Cs+1 6 1.67 Fe+3 8(BC) 0.78
Ca+2 8 1.12 Cs+1 eight 1.74 Fe+4 6 0.585
Ca+2 10 1.23 Cs+1 10 1.81 Fe+6 4 0.25
Ca+2 12 1.34 Cs+1 12 1.88 Ga+3 4 0.47
CD+2 4 0.78 Cu+1 2 0.46 Ga+3 6 0.62
CD+2 6 0.95 Cu+1 4 0.6 Gd+3 6 0.938
CD+2 8 1.1 Cu+1 6 0.77 Gd+3 eight 1.053

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Ion cf* Radius Ion cf* Radius Ion cf* Radius

Ge+2 6 0.73 Lu+3 6 0.861 Nb+5 4 0.48
Ge+4 4 0.39 Lu+3 eight 0.977 Nb+5 6 0.64
Ge+4 6 0.53 Mg+2 4 0.57 Nb+5 eight 0.74
hf+4 4 0.58 Mg+2 6 0.72 Nd+2 eight 1.29
hf+4 6 0.71 Mg+2 eight 0.89 Nd+3 6 0.983
hf+4 eight 0.83 Mn+2 eight 0.96 Nd+3 eight 1.109

Hg+1 6 1.19 Mn+2 4(BC) 0.66 Mn+2 Nd+3 12 1.27

Hg+2 2 0.69 5(BC) 0.75 Ni+2 4 0.55

Hg+2 4 0.96 Mn+2 6(Sun) 0.83 Ni+2 6 0.69

Hg+2 6 1.02 Mn+2 6(NS) 0.67 Mn+3 Ni+3 6(BC) 0.6

Hg+2 8 1.14 6(VS) 0.645 Mn+3 6(NS) Ni+3 6(NS) 0.56

Ho+3 6 0.901 0.58 Mn+4 0.39 Ni+4 6(NS) 0.48
Ho+3 8 1.015 4 O-2 1.38 4

Ho+3 10 1.12 Mn+4 6 0.53 O-2 6 1.4

I
-one
6 2.2 Mn+5 4 0.33 O-2 eight 1.42
In+3 4 0.62 Mn+6 4 0.255 OH-1 2 1.32
In+3 6 0.8 Mn+7 4 0.25 OH-1 4 1.35
In+3 eight 0.92 Mn+7 6 0.46 OH-1 6 1.37
Ir+3 6 0.68 Mo+3 6 0.69 Os+4 6 0.63
Ir+4 6 0.625 Mo+4 6 0.65 Os+5 6 0.575
Ir+5 6 0.57 Mo+5 4 0.46 Os+6 6 0.545
K+1 6 1.38 Mo+5 6 0.61 Os+7 6 0.525
K+1 eight 1.51 Mo+6 4 0.41 Os+8 4 0.39
K+1 10 1.59 Mo+6 6 0.59 Pb+2 4 0.98
K+1 12 1.64 N-3 4 1.46 Pb+2 6 1.19
La+3 6 1.032 Na+1 4 0.99 Pb+2 eight 1.29
La+3 eight 1.16 Na+1 6 1.02 Pb+2 10 1.4

La+3 10 1.27 Na+1 eight 1.18 Pb+2 12 1.49

La+3 12 1.36 Na+1 12 1.39 Pb+4 4 0.65
Li+1 4 0.59 Nb+3 6 0.72 Pb+4 6 0.775
Li+1 6 0.76 Nb+4 6 0.68 Pb+4 eight 0.94
Li+1 eight 0.92 Nb+4 eight 0.79 Pd+2 4 0.64

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Ion CN* Radius Ion CN* Radius Ion CN* Radius

Pd+2 6 0.86 Sm+2 8 1.27 Tl+1 eight 1.59
Pd+4 6 0.615 sm+3 6 0.958 Tl+1 12 1.7
Pr+3 6 0.99 sm+3 8 1.079 Tl+3 4 0.75
Pr+3 eight 1.126 sm+3 12 1.24 Tl+3 6 0.885
Pr+4 6 0.85 Sn+4 4 0.55 Tl+3 eight 0.98
Pr+4 eight 0.96 Sn+4 6 0.69 Tm+2 6 1.03
Pt+2 4 0.6 Sn+4 8 0.81 Tm+3 6 0.88
Pt+2 6 0.8 Sr+2 6 1.18 Tm+3 8 0.994
Pt+4 6 0.625 Sr+2 eight 1.26 V+2 6 0.79
Ra+2 8 1.48 Sr+2 10 1.36 V+3 6 0.64
Ra+2 12 1.7 Sr+2 12 1.44 V+4 6 0.58
Rb+1 6 1.52 Ta+3 6 0.72 V+4 eight 0.72
Rb+1 8 1.61 Ta+4 6 0.68 V+5 4 0.355
Rb+1 10 1.66 Ta+5 6 0.64 V+5 6 0.54
Rb+1 12 1.72 Ta+5 eight 0.74 W+4 6 0.66
Re+4 6 0.63 Tb+3 6 0.923 W+5 6 0.62
Re+5 6 0.58 Tb+3 8 1.04 W+6 4 0.42
Re+6 6 0.55 Tb+4 6 0.76 W+6 6 0.6
Re+7 4 0.38 Tb+4 8 0.88 Y+3 6 0.9
Re+7 6 0.53 Tc+4 6 0.645 Y+3 eight 1.019
Rh+3 6 0.665 Tc+7 4 0.37 Yb+2 6 1.02
Rh+4 6 0.6 Tc+7 6 0.56 Yb+2 8 1.14
Ru+3 6 0.68 Te+4 4 0.66 Yb+3 6 0.868
Ru+4 6 0.62 Te+4 6 0.97 Yb+3 8 0.985
Ru+5 6 0.565 Te-2 6 2.21 Zn+2 4 0.6
Ru+8 4 0.36 Ti+2 6 0.86 Zn+2 6 0.74
-2
S 6 1.84 Ti+3 6 0.67 Zn+2 eight 0.9
Sb+3 6 0.76 Ti+4 4 0.42 Zr+4 4 0.59
Sc+3 6 0.745 Ti+4 6 0.605 Zr+4 6 0.72
Sc+3 eight 0.87 Ti+4 eight 0.74 Zr+4 eight 0.84
Se-2 6 - 1.98 Tl+1 6 1.5
*
CN - coordination number, BC - high-spin state, LS - low-spin state, 1Å = 10–8 cm

38