Task 1.

Exotic carbon

Carbon is the 11th most abundant element on planet Earth according to the John Emsley
Handbook, and its chemistry is one of the "young" fields of chemical science. Most of this element
is found in organic compounds, while a smaller proportion is found in minerals (carbonates, coal,
diamond). But in this task we will talk about carbon compounds, which you are unlikely to meet
in ordinary life.
To synthesize the first of such materials, you will need to take the most common allotropic
modification of carbon and mix it with molten potassium in the atomic ratio K:C = 1:8 at 180°C
in an inert atmosphere. A saturated bronze-colored substance A was extracted from the mixture
and then stirred in anhydrous tetrahydrofuran for 5 days. The system was centrifuged and the
supernatant (liquid remained after precicpitation) was mixed with degassed water to obtain
substance B as a colloidal solution.

Determine what substances A and B are, if it is known that the latter is an allotropic modification
of carbon.

Which allotropic modification of carbon was used to prepare substance A?

What is the role of potassium in the process of producing B from carbon?

Why pre-degassing of water at the B stage is necessary?

 Task 2. Anesthesia or analgesia?

Anesthesia or analgesia may be required during or recovering from surgical procedures in

medical practice. Accordingly, doctors may use analgesics or anesthetics.
Analgesics eliminate only sensitivity to pain, leaving, for example, sensitivity to temperature
changes and tactile sensitivity. The most commonly used class of analgesics are NSAIDs - non-
steroidal anti-inflammatory drugs. This class of substances includes, for example, tolmetin
(substance X), which is produced according to the following scheme.

Additionally:
- 3 signals are observed in the 1H NMR spectrum of substance A;
- Substance F does not contain oxygen, and the mass fraction of hydrogen in it is 8.64%;

Give the structural formulae of substances A-I and X. Confirm the formula F by calculation.
Anesthetics are medical agents that inhibit virtually all types of sensitivity except tactile
sensitivity. They include various "caines" (lidocaine, articaine), opioid analgesics (morphine), and
several others.
Anesthetics also include sodium thiopental (substance Y), known to many as sodium
pentothal. This compound is part of the lethal injection for death penalty. Sodium pentothal is
produced according to the following process.

Additionally, substance Y is known to have one cycle with two nitrogen atoms and possesses
a "thio-version" of the amide-imide tautomerism.
Give structural formulae of substances J-N and Y.

Sodium pentothal is not only an effective anesthetic, but also, like many other barbituric acid
derivatives, has a narcotic effect. Because of this, intelligence departments of different countries
in the 20th century showed interest in this compound. What was sodium pentothal supposed to
be used for?
 Task 3. Pyrotechnics

Nowadays, pyrotechnics is a part of any celebration. On the other hand, calculating the
necessary characteristics for pyrotechnic mixtures is not an easy task. Problems arise at the stage
of writing the equations of the chemical reactions taking place, because the combustion of the
mixture can follow several paths at once.
Black powder - a mechanical mixture of finely ground sulfur, coal and potassium nitrate is
still the most popular pyrotechnic mixture. A distinctive feature of black powder is the fact that it
can burn without access to oxygen. For simplicity of calculations it is suggested to consider that
the ratio of coefficients in the equation of combustion of gunpowder coincides with the ratio of
mole fractions of the components themselves in the mixture. A sample of black powder containing
74.82% KNO3, 13.33% C and 11.85% S was received by the laboratory for investigation. It was
found that combustion of this mixture produced a solid sulfur-containing substance X and two
sulfur-free gases Y and Z, with gas Y being lighter than Z.

Identify substances X-Z and write the equation of the combustion reaction of the tested
gunpowder.

One of the main characteristics of any pyrotechnic mixture is the specific heat of combustion
of the mixture and the specific volume of gases released during combustion. The table below
summarizes the thermochemical characteristics of the mixture components and combustion
products X, Y, Z.

Substance ΔfH°298, kJ/mol S°298, J/mol·K

KNO3(solid) -494,5 132,9
S(rhombic, solid) 0 31,9
С(graphite, solid) 0 5,7
X(solid) -387,0 113,0
Y(gas) 0 191,5
Z(gas) -393,5 213,7
 Calculate the specific heat of combustion (in kJ/kg) of black powder, as well as the specific
volume of gases (L/kg at 1 atm and 25°C) released during combustion of this pyrotechnic
mixture. For simplicity of calculations, assume that thermodynamic characteristics of
substances do not depend on temperature.

For something to burn successfully, there are three components - oxidizer, fuel, and
temperature. If you remove even one of the components, the flame will go out.

At what minimum temperature is this reaction thermodynamically possible?

An inadequate laboratory employee decided to use a provided sample of gunpowder to make a

quick tea. Calculate the mass of gunpowder required to heat 200 g of water from 25°C to
100°C, taking into account that only 40% of the heat released by the combustion of
gunpowder goes to heat the water. The specific heat capacity of water is 4.2 kJ/kg∙°C. Give
your answer in grams, rounded to the nearest tenth.
 Task 4. 3D in inorganic chemistry

«...If nothing exists apart from singular

things, and there are innumerable such things, how
is it possible to attain knowledge of this
innumerable multitude??»
Aristotle, “Metaphysics”.
From organic chemistry we know very well that covalent bonds can be multiple: double,
triple. For a long time, the multiplicity of bonds, to put it simply, remained the privilege of
organics, until in 1963, a chemist from MIT, Frank Albert Cotton did not publish the result of X-
ray structural analysis of one of the rhenium salts (salt Cs3X). He found that its anion was a trimer
containing three rhenium atoms in the form of an equilateral triangle. In addition, it turned out that
the Re - Re distance in this compound is noticeably shorter than in other rhenium compounds and
shorter than the bonds in metallic rhenium. Then, with the help of quantum-chemical calculations,
he was able to establish the multiplicity of the Re - Re bond in this compound - it turned out to be
equal to two.
In addition, in 1963, the Journal of Structural Chemistry of the USSR Academy of Sciences
published an article studying other rhenium compounds (in particular, the K2Y salt), where a very
short Re – Re distance in the Y2- anion was indicated. Two years later, Cotton and Harris published
a more detailed paper on this compound, showing that it actually contains a quadruple Re – Re
bond, corresponding to one sigma bond, two pi bonds, and one delta bond.

The diagram above encodes the compounds described and the intermediates of the synthesis
chains. To solve the chain below you are given a number of hints:

• In compound A, the rhenium is in the +5 oxidation state;

• During the transformation of A into B, the metal decreases its oxidation degree, and B
has a structure similar to Cs3Y (a similar polygon of metal atoms);
 • Compound C is an acid;
• Compound K2Y contains no oxygen atoms;
• X3- and Y2- anions are binary.
However, there is another number between 2 and 4 - 3. Scientists have known the triple
bond in an inorganic compound for a long time - it exists in molecular nitrogen. The occurence
of a triple "metal - metal" bond remained unknown for quite a long time, but it was found by
Cotton and Chisholm in metal M compounds.
Metal M is known to have a molecular mass multiple of 16 (when rounded to integers). In
addition, disulfide of this metal is used as a dry lubricant (W(M) = 60%).

Hints:

• In compound E, the metal M is in the oxidation state +5;

• During the transformation of E to F, the metal lowers its oxidation state;
• Compounds G and H have gross formulas like M2Z6, where Z is some group of atoms.
Identify compounds A – H, Cs3X, K2Y and metal M. Prove your answers by calculations
(where possible).
Give structures of compounds G, H and anions X3- и Y2-.

What do compounds G and H structurally resemble?

It is known that around the same time the presence of multiple bonds in compounds with the so-
called "Chinese lantern" structure was established. Picture this structure and give examples of
such compounds.
 Task 5. Flashing image warning

Epilepsy is a chronic neurological disease manifested by the body's predisposition to the sudden
onset of seizures. The factors that provoke the onset of epilepsy in a person may be different:
hereditary, congenital or acquired.
Neurobiological research often requires provoking epilepsy in experimental animals (most
often in mice). For this purpose, special chemical substances - epileptogens - are used. One of the
most frequently used epileptogens is compound Z, synthesized according to the scheme below.

Additionally:

• Substance X6 contains 6 cycles;

• The mechanism of transformation of X11 to X12 is similar to SN2, but there is no inversion
of the stereogenic center.
Give structural formulas of substances X1 – X13 and Z taking into account stereochemistry.
 Explain the regiochemistry of the reaction X4 to X5.

Task 6. Titration
The determination of sodium carbonate and sodium hydrogen carbonate in the presence of
both is carried out by means of the Walder titration method, i.e. using two indicators. The method
is described below.
The 0,232 g mixture of Na2CO3 and NaHCO3 is dissolved in a 50.0 mL measuring flask
and mixed well. Pipette 10.00 ml of the solution into a 100 ml conical flask for titration, add 5
drops of phenolphthalein and titrate with HCl solution from a burette until discoloration occurs
from one drop of titrant. The volume of HCl (V1) is measured. Then add 2 drops of methyl orange
to the solution titrated with phenolphthalein and titrate it with HCl solution until the color changes
from pure yellow to orange. The volume of HCl (V2) is measured.

№ of experiment V1, ml V2, ml

1 8.1 20.5
2 8.2 20.4
3 8.3 20.6
4 8.2 20.5

It is known that the pH of the phenolphthalein transition lies in the region of 8.2-9.8, and the pH
of the methyl orange transition lies in the region of 3.1-4.4. In addition, the basicity constants
(Kb) of the carbonate ion and the hydrocarbonate ion are 2∙10-4 and 2.2∙10-8, respectively.
Determine which volume of titrant corresponds to the content of which component and explain
why.
The concentration of the acid is known: CHCl = 0.122 M. Calculate the concentrations (in moles
per litre) of both salts in measuring flask and their mass fractions in the initial mixture, taking
into account that the equivalence factor for both reagents is 1. Note that the data must be
averaged.