IChO-2015

Preparatory problems

47th International Chemistry Olympiad(IChO-2015)
Moscow State University
Baku Branch
Azerbaijan

Edited by: Vadim Eremin, Alexander Gladiline-mail:vadim@educ.chem.msu.ru
alexander.gladilin@simeon.ru

Released

January 31, 2015

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IChO-2015

Contributing authors

Moscow State University, Baku Branch, Azerbaijan
M. Beklemishev
A. Drozdov
A. Dubenskiy
V. Eremin
A. Gladilin
E. Karpova
I. Kas’yanov
M. Korobov
M. Kovalchuk
E. Lukovskaya
P. Matveev
V. Nikitina
A. Prokhorova
G. Rusakova
E. Skokan
I. Trushkov
V. Zelikman

Medical clinics No 33, Ufa, Russia
B. Garifullin

Belarusian State University, Minsk, Belarus’
Yu. Halauko

Aix-Marseille University, Marseille, France
D. Kandaskalov

Kazan’ Federal University, A.Butlerov Institute of Chemistry, Russia
I. Sedov

Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Kiev
D. Volochnyuk

Multidisciplinary Lyceum, Vologda, Russia
A.Z. Lisitsyn
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PREFACE
Dear friends!
We are happy to present you the Booklet of Preparatory problems. Members of the Science
Committee really did their best to prepare interesting tasks. The set covers all major parts of modern
chemistry. All the tasks can be solved by applying a basic knowledge of chemistry, even in case aproblem refers to a topic of advanced difficulty. Still, we expect it will take some time and efforts ofyours to find the correct answers. Thus, most probably we know how you will spend some of yourtime in the coming months. We wish you much pleasure while working with this set of problems.
And never forget that
LIFE IS A HUGE LAB!
Note to mentors
In addition to the problems, you will find in the Booklet:
 The list of topics of advanced difficulty The Safety rules and recommendations set by the IChO International Jury The hazard warning symbols, their designations and explanations
Worked solutions will be posted at the website by the end of May, 2015.
We pay great attention to safety. In the section preceding the practical preparatory problems you
will find safety precautions and procedures to be followed. At the registration in Baku we will ask
every head mentor to sign a form stating that his/her students are aware of the safety rules andadequately trained to follow them. Prior to the Practical Examination all students will have to readand sign safety instructions translated into their languages of choice.
Despite our great proof reading efforts, some mistakes and misprints are still possible. We
appreciate your understanding and will be happy to get your feedback. Please address yourcomments to icho2015@msu.az. You may also write your comments on our website
http://www.icho2015.msu.az/. Please explore our official website on a regular basis, sincecorrections/upgrades of the preparatory problems, if any, will posted there.
On behalf of the Steering Committee (SC), we encourage you to visit its recently launchedhomepage https://www.ichosc.org/. You can also directly access SC by writing a letter to
sc@ichosc.org.
Sincerely yours,
Members of the IChO-2015 Science Committee

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Contents
Contributing authors
PrefacePhysical constants, formulas, and equations
Topics of advanced difficulty

2
3
5
6

Theoretical problems
Problem 1.
Problem 2.
Problem 3.
Problem 4.
Problem 5.
Problem 6.
Problem 7.
Problem 8.
Problem 9.
Problem 10.
Problem 11.
Problem 12.
Problem 13.
Problem 14.
Problem 15.
Problem 16.
Problem 17.
Problem 18.
Problem 19.
Problem 20.
Problem 21.
Problem 22.
Problem 23.
Problem 24.
Problem 25.
Problem 26.

Brayton cycle
Liquefied natural gas
Carnot cycle
Quasi-equilibrium model
The Second Law of thermodynamics applied to a chemical reaction
Catalytic transformation of a single molecule on a single nanoparticle
Esterification of a dicarboxylic acidThree elements
Simple experiments with copper(II) chloride
An element typical for Azerbaijan mud volcanoes expelled water
The Prussian blue
Substitution in square planar complexes
Redox equilibria in aqueous solutions
Determination of acetylsalicylic acid purity
Chemical dosimeter
Determination of water in oil
Oxidation and inspiration
Essential ozone
Two in one
Antitussive “narcotine”
Pyrrolizidine alkaloids
Delightful odor of truffle
Synthesis of large rings. The magic or routine work?
What Time is it in Baku or Cheating the Death
Number One Enzyme
Holy War against Four Horsemen of the Apocalypse

SAFETY RULES AND REGULATIONS ADOPTED AT IChO

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8
10
10
13
15
17
17
18
18
19
19
19
20
21
23
24
26
28
29
29
30
31
31
33
36
38

Practical problems
Problem 27.
Problem 28.
Problem 29.
Problem 30.
Problem 31.
Problem 32.
Problem 33.
Problem 34.

Determination of nickel in nickel and copper-nickel alloys
by complexometric titration
Titrimetric determination of lead and silver in their mixture
Complexometric determination of iron, chromium, and zinc in an alloy
Synthesis of 3-(4-methylbenzoyl)propionic acid
Synthesis of 4-(4-methylphenyl)-4-hydroxybutanoic acid
Synthesis of diethyl ester of succinic acid
Kinetic studies of Norfloxacin oxidation with permanganate
in alkaline medium
Temperature dependence of the reaction rate of disproportionation

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48
51
53
57
61
65
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Physical Constants, Formulas, and Equations
Avogadro's constant: NA = 6.0221  1023mol–1
Universal gas constant: R = 8.3145 J∙K–1∙mol–1
Faraday’s constant: F = 96485 C∙mol–1
Standard pressure, p = 1 bar = 105 Pa
Atmospheric pressure: 1 atm = 1.013 bar
Zero of the Celsius scale, 273.15 K
1 nanometer (nm) = 10–9 m
The First Law of thermodynamics: U = Q – W 1
Reversible adiabatic process for an ideal gas: pV 1 R /CV = const
Work made by an ideal gas in an adiabatic process: W = nCV (T1 – T2)
Work made by an ideal gas in a reversible isothermal process: W = nRT ln

p1
p2

Gibbs energy: G = H – TS
Relation between equilibrium constant, standard electromotive force and standard Gibbs energy: G 
 nFE  = exp 
K = exp   RT 
 RT 
c
Dependence of Gibbs energy of reaction on concentrations: G = G  RT ln prod
creag

Dependence of electrode potential on concentrations: E = E 

RT coxln
nF credYou may use the First Law written in IUPAC convention: U = Q + W (in this case, work is positive if it is done on
the system)
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Topics of advanced difficulty
Theoretical
1. The First Law of thermodynamics: thermodynamic cycles, adiabatic processes, work of adiabatic
processes.
2. The Second Law of thermodynamics: spontaneous chemical reactions. Dependence of Gibbs
energy of reaction on concentrations. Relation between equilibrium constant, electromotive force andstandard Gibbs energy. Latimer diagrams.
3. Integrated rate law for first order reactions, half-life, mean life time. Analysis of complex reactions
using steady-state and quasi-equilibrium approximations, mechanisms of catalytic reactions,determination of reaction order for complex reactions.
4. Inorganic complexes: structure and isomerism. Crystal field theory. Trans-effect.
5. Preparation and chemical properties of carbonyl compounds.
6. Oxidoreductase- and transferase-catalyzed reactions in metabolism of nucleotides and xenobiotics.

Practical
1. Advanced procedures in organic synthesis: heating under reflux, vacuum filtration, vacuum
distillation, determination of refraction index, use of a nomogram.
2. Kinetics of chemical reactions: photometric studies and analysis of experimental data with theEnglish version of Microsoft Excel software.

Note. The hereunder topics met in the Preparatory problems:

Clapeyron equation for phase transition

Rate of heterogeneous reactions

Claisen rearrangement



Determination of a melting pointCalculation of solubility in the presence of complexing agents

Rotary evaporationLiquid-liquid extraction

Deciphering a compound structure using NMR and mass spectrum data

are inalienable parts of the proposed tasks. We do not expect students to get an advanced training in
the above skills and concepts, since these will not appear neither in the Practical, nor in the
Theoretical Exam set.
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Theoretical problems
Problem 1. Brayton cycle
Students have made a device capable to operate in a mode that is close to the ideal Brayton cycle.
This thermodynamic cycle has once been proposed for development of internal combustion engines.
The device consists of a cylinder with 1 mole of helium fitted with a computer-controlled movablepiston. A Peltier element which can heat or cool the gas is mounted in the cylinder wall. The device
can operate in the following modes: 1) reversible adiabatic expansion or compression, 2) reversible
isobaric cooling or heating.

Through a number of cooling and compression steps, helium is going from the initial state with thepressure of 1 bar and the temperature of 298 K into the final state with the pressure of 8 bar and thetemperature of 298 K. (The total number of cooling and compression stages can be from two up to
infinity).

1. What is the minimum work that should be done on the gas for this? Compare this value to thework during a reversible isothermal compression.
2. What is the maximum work that can be done on the gas in this process?
3. Let the process be accomplished in three steps. At each step helium is first cooled and thencompressed. At the end of each step the pressure increases twice and the temperature returns to thevalue of 298 K. What is the total heat removed from the gas by a Peltier element?

Once the gas is compressed, it is returned to the initial state (1 bar and 298 K) in two stages (heatingand expansion).
4. What is the range of possible values of the formal efficiency η for the resulting cycle? η is theratio of the useful work done by the gas to the amount of heat given to the gas during the heatingstage.
5. In one of the experiments, the gas has been compressed from 1 bar and 298 K to 8 bar and 298 K
in several steps (like in question 3). At the end of each step the pressure is increased by x times andthe temperature returns to 298 K. Then helium has been returned to the initial state in two stages –heating and expansion. Theoretical value of η for this cycle is 0.379. How many steps were used?
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In fact, Peltier elements also consume electric energy during the cooling stage. Assume that they
consume as much energy as is removed from the gas.

6. What is the maximum possible efficiency of the considered cycle, taking into account energy
consumption during cooling?
Hint: in reversible adiabatic process for helium pV 5/ 3  const . Isochoric molar heat capacity ofhelium is 3/2R.

Problem 2. Liquefied natural gas
Liquefied natural gas (LNG) is being produced in the world in increasing amounts. It has a highenergy density in comparison with the compressed natural gas, so that liquefaction is advantageous
for transportation over long distances, especially by sea. The main component of LNG (> 95%) ismethane. The dependence of the boiling point of methane on pressure is well described by theempirical equation:log (p/bar) = 3.99 – 443 / (T/K – 0.49)

1. What is the boiling point of methane at atmospheric pressure?
A typical cryogenic tank for marine transportation of the LNG has a volume of 40 000 m3, in which
it is stored at –159 °C. This tank has no external cooling, and the pressure inside it is kept constant.
Initially the tank is fully loaded with 16 800 tons of liquid methane, but during the sailing time it
partially evaporates. The evaporated gas can be used as a fuel in the engine of the marine vessel.

2. Estimate how many times larger is the energy density per unit volume of liquefied methane thanthat of gaseous methane in cylinders under 300 bar pressure at room temperature (298 K). (Thecompressibility factor of methane at these conditions is close to 1, and thus the ideal gas law can beapplied.)8

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2

lg(p/bar)1.5liquid1

0.5

gas+liquid
0

-0.5

gas
-1
-2

-1

0

1

2

3

4

5

6

7

8

U/(kJ·mol-1)
A phase diagram of methane given above is plotted in the coordinates ‘logarithm of pressure in bars
(log p) – internal energy (U)’. It is based on the experimental data [Setzmann and Wagner, 1991].
The area encircled by black dots (data points) corresponds to equilibrium coexistence of liquid andgaseous methane, while out of it methane is either completely liquid or completely gaseous. Using
the diagram, answer the following questions:3. What is the enthalpy of vaporization of methane under conditions of its transportation?
4. What percent of methane will evaporate after 15 days of sailing, given that the total heat leakage
through the cryogenic tank is 50 kW?
5. For long term storage of LNG, it was suggested not to discharge evaporating methane but to seal
the tank. A pilot experiment has been conducted with the same tank initially filled with liquidmethane (at temperature –159 °C) up to exactly a third of its volume. After 9 months of storage, thepressure inside the tank grew up to 16.4 bar. Which part of methane has evaporated inside the tank?
Assume that the heat leakage is the same as in the previous question.
6. What can be the maximum temperature of the liquefied methane? What would be the pressure in
the reservoir containing it?

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Problem 3. Carnot cycle
In the following graph, a reversible Carnot cycle for an ideal gas is shown in «pressuretemperature» coordinates. A cycle consists of two isotherms and two adiabates.

6

p/bar

5

4
3
2
1
0

250

300

T/K

350

400

Using this graph, calculate the following magnitudes or show that it is impossible:
1. The useful work of the cycle.
2. The efficiency η of the cycle.
3. The isochoric molar heat capacity of a gas.
4. The number of atoms in the molecule of a gas.

Hint: in reversible adiabatic process for an ideal gas, pV

1 R /CV  const where CV is the isochoric

molar heat capacity.

Problem 4. Quasi-equilibrium model
Equilibrium constants are often included into the rate equations for complex chemical reactions. For
some rapid reversible steps the ratio of concentration of products to concentration of reactants is
assumed to be equal to equilibrium constant, though reaction as a whole still proceeds and chemical

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equilibrium is not attained. This is quasi-equilibrium approximation. The concept of quasiequilibrium makes rate equations much simpler which is vitally important for complex reactions.

I. Consider kinetics of a complex reactionkeff
A  B CD

The following mechanism was proposed
k1
k3
k2

 AB 
A  B 
 AB* 
 CD

k1

The rates of the forward and reverse reaction of the first step are almost equal,
r1  r1i.e., quasi-equilibrium is reached.
1. Calculate keff, if k1 / k–1 = 10 M–1, k2 = 20 s–1.
Metallic platinum loses its mass interacting with the flow of atomic fluorine at T = 900 K. Partialpressure of F in the incident flow near the surface is 10–5 bar, see Fig.1.

PtF2,
PtF4, FPF = 10-5 bar

Incident
flow, ρInc

Desorbed
flow, ρDes

Pt

T=900K

Fig. 1. Gasification of Pt by a flow of atomic fluorine

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No solid products of interaction of Pt with F were found on the surface. Gaseous species PtF4 и PtF2
were detected in the flow desorbed from the surface. The ratio

2
pPtF
2

pPtF4

was equal to 10–4 bar and did

not vary with the change of the incident atomic fluorine flow.

Use the data in the Table to answer the following questions:2.1. Find the maximum partial pressure of molecular fluorine near the platinum surface under the
given experimental conditions. Assume first that gasification does not proceed.
2.2. Why is the ratio

2
pPtF
2

pPtF4

= 10–4 bar constant near the surface?

2.3. Make the necessary assumptions and estimate the partial pressure of atomic fluorine in thedesorbed flow.
2.4. Put forward the quasi-equilibrium model to account for the rate of gasification of Pt withatomic fluorine,
rPt 

dnPt
{mol of Pt / Pt surface area / time}dt

Make use of the dimensionless equilibration probability,, which is equal to the fraction of incident
fluorine flow involved in gasification. Consider other steps of gasification as quasi-equilibrium. The
flow ρi of each gaseous species i is related to its partial pressure pi asi  cpi(mi )1/2

where mi is a molecular mass, c is constant.
2.5. Estimate the equilibration probability  under the experimental conditions, described in the
Table.
2.6. How many grams of Pt will be gasified from 1 cm2 of the Pt surface in 15 minutes, if theincident flow of atomic fluorine is 21018 atoms/cm2/s?

Table
ReactionKр (900 К), bar–1

Gaseous species

р(900 K), bar

2F(g) = F2(g)1.7103

PtF2

210–6Pt(s) + 2F(g) = PtF2(g)

5108

PtF4

410–8

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Problem 5. The Second Law of thermodynamics applied to a chemical reaction
When does chemical reaction proceed spontaneously? The Second Law gives the answer.
Consider a system, a chemical reactor in Fig. 1. Pressure р and temperature Т inside the reactor are
kept constant. There is no transfer of matter into or out of the system.
p = constСА В 
Т, nA,nB = const

Fig. 1. Chemical reaction inside a reactor
According to the Second Law, every spontaneous process in such a reactor leads to the decrease of
the Gibbs free energy, Gsystem, i.e. ΔGsystem < 0.
If the chemical reaction, e.g., А + В = С (a), is the only process inside the reactor
GSystem  GReaction (a )(a )(1)

(a )  nC  n A  nB

where ΔGReaction and Δξ are the Gibbs free energy and the extent of reaction (a), respectively,
ΔnA, ΔnB, ΔnC are changes of the numbers of moles of A, B, C in the reaction (a).
1.1. Relate Δξ to Δni of reactants and products of the following reaction

1
C6 H12O6  O2 = CO2  H 2O
6(b)1.2. Prove that, according to the Second Law, ΔGReaction < 0 for any single spontaneous chemical
reaction in the reactor (Fig.1).

2. The Gibbs free energy of the chemical reaction (a) is:13

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GReaction  GReaction  RT ln[C]0[A][B](2)

where [C], [A], [B] are time variant concentrations inside the reactor in the course of spontaneous
reaction. Using the law of mass action, relate GReaction to the ratio of rates of forward r1 and reverse
r–1 reaction (a). Consider both reactions as elementary ones.
3.1. Derive the expression (2) for Greaction of the following chemical transformations:(a')H2(g) + Br2(g) = 2HBr(g)(a'')

H(g) + Br2(g) = Br(g) + HBr(g)(a''')

CaCO3(s) = CaO(s) + CO2(g)3.2. For which of these reactions the relation between GReaction and r1, r–1 derived in Problem 2 isvalid?
4. The observed rate of chemical reaction, robs, is defined as robs = r1 – r–1.
Let reaction (a) proceed spontaneously. At a certain momentrobs / r1 = 0.5,

[A] = 0.5 M, [B] = 1 M, [C] = 2 M.

Find the equilibrium constant, K, of the reaction (a), T=298K.

5. Plot robs as a function ofa) r1, at GReaction = const;b) r1, at r–1 = const;c) GReaction, at r1 = const.

6. Which thermodynamic and kinetic parameters of a chemical reaction are influenced by acatalyst? Put plus (+) into the cell of the Table if a catalyst may cause a change of the corresponding
parameter, (–) otherwise.

Table
robs

r1

r1/r–114

GReaction

robs/r1

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Problem 6. Catalytic transformation of a single molecule on a single
nanoparticle
Use of catalytic nanoparticles opens new ways to study and to understand catalysis. The exiting
measurements were performed at Cornell University (NY, USA). The researchers observed thecatalytic transformation of single molecules on the surface of a spherical nanoparticle (d = 6 nm)
formed by Au atoms.
The experimental design is shown in Fig.1. The dissolved А was transformed into dissolved В inthe presence of Au nanoparticles, adsorbed on the glass slide.

Laser light

Fluorescence

A

B

Solutiond = 6 nmFig.1. The experimental design
The reaction product В is a fluorescent molecule while the reagent A is not. Continuous laser light
producing fluorescence was focused within a small surface area containing a single Au nanoparticle. The time dependence of fluorescence on the wavelength characteristic for B, adsorbed on
the Au nanoparticle is shown in Fig.2.

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Intensity of fluorescence

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2

1

Time

Fig. 2. Time dependence of intensity of fluorescence coming from a single cluster

The fluorescence of B in the solution could not be detected under the experimental conditions. The
same intensity of fluorescence was observed periodically for the time intervals τ 2. The fluorescence
disappeared during the time intervals τ1 between the peaks (see Fig.2). The researchers have
performed their measurements for long periods of time and for many different single Au
nanoparticles. As a result the averaged values of [τ1] and [τ2] were obtained.
Answer the following questions about this experiment and the conclusions made by its authors.
1. Estimate the number of the Au atoms in a single nanoparticle if it’s density is equal the bulk
density of Au, 19.32 g/cm3. What fraction of Au atoms is involved in the catalysis if catalytically
active is the surface layer with the depth equal to two atomic diameters of Au (dAu = 0.350 nm)?

2. The resolution of the instruments made it possible to measure the fluorescence emitted from 1
μm2 area. The number density of Au nanoparticles on the glass slide was 0.035 particleμm–2. What
was the probability (%) of observing fluorescence from a single Au nanoparticle?

3. The authors claimed that each peak in Fig. 2 corresponds to the fluorescence of a single moleculeВ adsorbed on Au nanoparticle. What was the main argument of the authors?

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Consider adsorption of А on Au nanoparticles to be a fast reversible process. Let m catalytic sites
exist on the surface of a single nanoparticle. The fraction of catalytic sites occupied by molecules A,
is equal toА 

Kads [A]1  Kads [A]

4. Relate [τ1] and [τ2] to the rates of catalytic production/desorption of a single molecule B on/froma single Au nanoparticles.
5. Plot [τ1]–1 and [τ2]–1 as a function of concentration of А in the solution.
6. How will [τ1]–1 and [τ2]–1 change with the increase of nanoparticle diameter from 6 to 12 nm?

Problem 7. Esterification of a dicarboxylic acid
Dicarboxylic acid is mixed with ethanol in a molar ratio 1 : X (X > 1) in the presence of a catalyzer.
The system reached equilibrium. The equilibrium constants for the formation of monoester from anacid and ethanol and that for the formation of diester from monoester and ethanol are the same: K1= K2 = 20.
1. At what X the yield of monoester is maximal?
2. Find the maximum yield.
3. Answer the questions 1 and 2 at arbitrary K1 and K2.

Problem 8. Three elements
Three elements – A, B, and C form three binary compounds. Each element has the same valence inthese compounds. The mass fraction of A in the compound with B is 75%, and the mass fraction of
B in the compound with C is 7,8%. Determine the mass fraction of C in the compound with A andfind all the elements.

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Problem 9. Simple experiments with copper(II) chloride
Copper(II) chloride forms brown crystals soluble in water.
1. The color of the solutions depends on concentration. Explain this fact.
2. Draw the structure of at least three copper containing species that can be present in the solution.
3. To the aliquots of the copper chloride(II) solution in the test tubes (a) zinc powder and thesolutions of (b) sodium iodide, (c) sodium nitrate, (d) sodium sulfide were added dropwise. Whatchanges happen if they are? Provide equations. In what cases copper is completely or partly
reduced?
4. Suggest a synthetic route to copper chloride(II) starting from copper(II) sulfate aqueous solution.

Problem 10. An element typical for Azerbaijan mud volcanoes expelled water
Azerbaijan is famous for mud volcanoes. About 400 active mud volcanoes are present in thisregion, both onshore and offshore - more than half the total throughout the world. Mud volcanoes
come in a variety of shapes and sizes, but those most common in Azerbaijan have several smallcones, or vents, up to about four meters in height. Mud volcanic eruptions in Azerbaijan normallylast for less than a few hours, and are characterized by vigorous extrusion of mud breccias,
hydrocarbon gases, and waters. Bakhar is a mud volcano with a high seep activity in the dormant
period. The reservoirs formed by the volcanoes’ activity contain the expelled waters. Those of
Bakhar volcano have a composition with Na and Cl as dominant ions. The analyzed waters areenriched in metals and in an element X that causes flame coloration. Its’ concentration in seeping
water of 250 ppm represents a 55-fold enrichment in comparison to seawater. Being concentrated,the expelled water gives the white crystals, among them the compound Y, one of the main sourcesof X. The common oxide of X contains 31.0% of the element, whereas the compound Y – 11.3%
only.

1. What are the element X and the compound Y?
2. Calculate the mass of Y that can be obtained from 1 L of expelled water.
3. The mass loss under gentle heating of Y is 37.8%. Draw a possible structure of anion in Y,
knowing that it contains two different types of X atoms (three- and four-coordinated).

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Problem 11. The Prussian blue
The Prussian blue is a component of black and bluish inks for printing. The precipitate formed upon
the dropwise addition of potassium ferrocyanide to the ferric chloride solution contains 34.9%(mass) of iron.

1. Give a formulae of the precipitate and write the chemical equation. (Use 55.8 for atomic mass ofiron).
2. Using the crystal field theory show the d-orbital splitting pattern for all Fe atoms in the Prussianblue.
3. What causes the intense color of the pigment?
4. What product initially forms from potassium ferrocyanide and ferric chloride solution in the
inverse-mixing-order route? Give the equation.

Problem 12. Substitution in square planar complexes
For platinum (II) and (IV) a large number of complexes is known. For most of them the isomers
were isolated.

1. Explain what is the reason for the existence of different isomers and draw the structures for allPt(NH3)2Cl2Br2 species.
2. The reaction of thiourea with [Pt(amine) 2Cl2] isomers results in different products. Explain thisfact and give the reaction scheme.
3. Give an example of PtX(amine)Cl2 isomeric complexes reacting with thiourea with the formationof one and the same product.
4. Explain why do the reactions of [PtCl4]2– and [AuCl4]– with iodide result in different products.

Problem 13. Redox equilibria in aqueous solutions
Using the Latimer diagrams (pH = 0):19

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1.401 V1.692 V+
[Au(H2O)6]  [Au(H2O)6]  Au
3+

0.926 V
1.154 V
[AuCl4]¯ [AuCl2]¯  Au

0.810 V
0.960 V
[AuBr4]¯[AuBr2]¯  Au

answer the following questions:

1. Is Au(I) stable to disproportionation in aqueous solutions in the absence and in the presence ofchloride and bromide ions? Support your answer by calculations.
2. Is it possible to oxidize gold powder by pure oxygen (р(О2) = 1 atm, EO ,H  /H O = 1.229 V) in the22

aqueous solution in the presence of chloride ions?
3. At what pH interval is it possible to oxidize gold powder by hydrogen peroxide ( EH O ,H  /H O =2

2

2

1.763 V) in the presence of chloride-ions? Assume that the activities of all ions in the solution
except H+ are 1.

Problem 14. Determination of acetylsalicylic acid purity
Aspirin – acetylsalicylic acid – is used to treat pain and to reduce fever, at low doses, to prevent
heart attacks, strokes, and blood clot formation. It is one of the most widely used medications in theworld, with an estimated 80 billion of tablets of it being consumed each year. Aspirin tablets can becontaminated with salicylic acid – the reagent for synthesis of acetylsalicylic acid. The content ofsalicylic acid is controlled in accordance with national pharmacopoeias. It must not exceed 0.1–
0.3 %. Redox titration using bromine as an oxidation agent is one of the possible techniques todetermine salicylic acid in aspirin.

4.4035 g portion of powdered aspirin tablets was dissolved in 250.0 mL volumetric flask. For redox
titration, reagent (bromine) was generated in situ (in the same titration flask). Bromide-bromate
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IChO-2015

mixture was made of potassium bromide (0.5950 g) and potassium bromate (0.1670 g) in 100 mLof water. 25.00 mL aliquot was transferred to a titration flask, also sulfuric acid and 20.00 mL of theabove mixture was added. The volume was made up to 50.0 mL with water. Flask was corked up
and stirred for 10 min.

1. Write the balanced equations of the reactions described.
2. At what maximal pH bromide will react with bromate? The standard redox potentials are:
E2BrO ,H  /Br = 1.52 V, EBr /2Br  = 1.09 V.
3

2

2

Solution obtained after filtration of the reaction mixture was titrated against a 0.02015 М solution of
NaAsO2 and a mean titre of 9.93 mL was obtained.

3. Write the balanced equations of the reactions described.
4. Calculate the percentage of salicylic acid in tablets by mass.
5. Do the tablets meet the regulatory requirements?

Problem 15. Chemical dosimeter
Chemical dosimeters are widely used for remote determination of high-level doses of radiation.
Most common type of dosimeter is a ferrous-ferric sulfate dosimeter. When ionizing radiation
passes through the solution, lots of products (radicals, ions, and molecules) are formed. Most ofthem can oxidize Fe2+ into Fe3+.
1.1. Choose the electronic configuration of Fe2+ cation:А) 3d64s0

B) 3d54s0

C) 3d44s2

D) 3d54s1

1.2. Write the balanced equations for oxidation of Fe2+ with the following particles:А) H2O+B) ОН·С) H2O2

The resulting solution is then titrated and the amounts of Fe(II) and Fe(III) are calculated. For these
purpose, permanganatometric and iodometric titrations can be used.

2.1. Write down the balanced redox equation for the reaction between:
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IChO-2015

а) iron(II) sulfate and potassium permanganate in acidic media;b) iron(III) sulfate and potassium iodide;с) sodium thiosulfate and iodine.
2.2. Calculate concentrations of cations Fe2+ and/or Fe3+in each of the following cases:а) To titrate 20.00 mL of Fe(II) solution, 12.30 mL of 0.1000 М potassium permanganate
solution was spent.
b) 1.00 mL of solution containing Fe(III) was diluted up to 20.00 mL, to resulted solution an
excess of potassium iodide solution was then added. The iodine formed was titrated with 4.60 mL
sodium thiosulfate solution (0.0888 M).
с) An aliquot 5.00 mL was titrated with 0.1000 М potassium permanganate solution, theaverage volume being equal 7.15 mL. After that, an excess of potassium iodine solution was added
to the flask. Titration of the resulting solution required 13.70 mL of 0.4150 М sodium thiosulfate.

Frequently, chemical dosimeters are used for measuring doses near nuclear reactors where large
amounts of various radionuclides are accumulated.
3.1. Match mother and daughter radionuclide, indicate the type of decay (α or β–) in each case:Mother radionuclide:a) 60Cob) 90Src) 226Rad) 137Cse) 212Po

Daughter radionuclide:
90

1) Zr

2) 137Xe 3) 214Rn

4) 222Rn 5)137Ba 6) 60Ni 7) 60Fe

8) 208Pb 9) 90Y

Radioactivity A is directly proportional to the number of particles N of a substance (A = λN), where
λ is the decay constant related to half-life by the equation λ = ln2 / T1/2. Radioactivity is measured inbecquerel (symbol Bq) units: 1 Bq is one decay per second.

3.2. Using values of half-lives, calculate (in GBq) radioactivity of samples containing:a) 1.3141 g 226RaCl2b) 1.0 mg 90Sr(NO3)2 and 0.5 mg 137CsNO3
T1/2(226Ra) = 1612 years, T1/2(90Sr) = 29 years, T1/2(137Cs) = 30 years.
3.3. Explain why 226Ra is dangerous for humans?
3.4. It is well known that radionuclide 64Cu decays to 64Ni (this is attributed to electron capture,process when nuclei absorb inner electron) and 64Zn (β– decay). Half-life for electron capture is 20.8
hours, for β– decay is 32.6 hours.
22

IChO-2015a) Calculate the average half-life of 64Cu.
b) How much time is required for radioactivity of a 64Cu sample to decrease by 10 times?

Problem 16. Determination of water in oil
Oil is the most important mineral for Azerbaijan. From chemist’s point of view it is a mixture of agreat number of substances of different nature – both organic and inorganic. At all stages of
petroleum refining, it is important to control the content of inorganic impurities, including water, inoil. One of the popular chemical methods for the determination of water in various organic matrices
is named Karl Fischer titration. The method is based on the reaction described by R. Bunsen:
I2 + SO2 + H2O  HI + H2SO4

1.1. Indicate the oxidant and reductant in the reaction.
1.2. Put the coefficients in this reaction. Sum of the least integer coefficients is
A) 14

B) 9

C) 7

D) 10

Reagent which was proposed by the German chemist Karl Fischer is a mixture of pyridine, sulfur
dioxide, iodine, and methanol. In this case, the following reactions occur during titration:
SO2 + CH3OH + H2O + I2  2HI + CH3OSO3H
Py + HI  PyH+I–
Py + CH3OSO3H  PyH+ CH3OSO3–
2.1. What is the role of pyridine in the composition of Fisher reagent?
2.2. What substance(s) could be used instead of pyridine?
A) ImidazoleB) PyrrolC) HydrazineD) Butylamine

2.3. However, the above composition of titrant may lead to various side reactions. Write thepossible reactions taking place between the components of the Fisher reagent and the following
substances:a) Aldehydes, RC(O)Hb) Ketones, RC(O)Rc) Mercaptans, RSHd) Organic peroxides, ROOH
Indicate if an overestimation or underestimation of the water content is observed in each case.
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IChO-2015

3.1. Fischer reagent is to be standardized prior to use, i.e. it is necessary to set amount of watercorresponding to one volume of a titrant. The reagent was prepared by the following procedure: 49
g of iodine were dissolved in 158 g of pyridine, then 38.5 g of liquid sulfur dioxide was introduced
while cooling. Thereafter, mixture was diluted up with methanol to 1 liter.
a) Using the above data, calculate the theoretical titre of the Fischer reagent (in mg/mL).
b) Calculate the practical titre (in mg/mL) of Fischer reagent, if to reach the endpoint for thetitration of 5 g of a mixture of methanol and water (water content of 1% by volume), 19 mL oftitrant was spent.
c) Why do the results obtained differ?
d) Calculate the water content (in %) in the sample of sour oil, if the content of mercaptan insulfur recalculation is 1 wt.% and titration of 1.00-g sample of sour oil dissolved in methanol
required 7.5 mL of titrant.

3.2. The modern version of water determination in different samples is coulometric Karl Fischer
titration. During the titration iodine is generated electrochemically and the water content is definedas the total amount of current passing through the coulometer. Titration is stopped when thegeneration of iodide stops in the system.
a) Using Faraday's law, calculate the mass fraction of water in the oil sample (10.0 g), if
375.3 Coulombs passed through a coulometer.
b) 1.000 g portion of sugar was dissolved in 15 mL of methanol and chloroform mixture.
Calculate the molar and mass fractions of water and sugar, if for a coulometric titration of sugar a
total charge of 567.2 Coulombs was required, while 31.1 Coulombs were required to titrate solvent.

Problem 17. Oxidation and inspiration
With every breath, I breathe in so much of inspiration.
I feel if there is one thing as free and as important as oxygen, it's inspiration.
(Sharad Sagar)
Oxygen is not only chemical element but also the essential element of life. Its most stable form,
dioxygen, O2, constitutes 20.8% of the volume of the Earth’s atmosphere. All forms of oxygen areable to oxidize various compounds, especially organic ones. The type of oxygen-containing
functionalities in organic compounds could be efficiently determined by IR spectroscopy. Thus,
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IChO-2015
C=O groups are characterized by intense absorption at 1750-1660 cm–1 and O–H group ischaracterized by absorption in the region of 3600-3000 cm–1.

The most typical oxidation of saturated hydrocarbons with O 2 is the burning process. However,some reaction have been developed producing various oxygenated products. For example, Gif
reaction (which received this name in honor of Gif-sur-Yvette where Prof. Derek Barton wasworking when he disclosed this transformation) represents the oxidation of saturated hydrocarbons
with air oxygen at room temperature. Thus, the oxidation of adamantane leads to three products:

Products X and Y are isomers. The compound Y can be easily transformed to Z. IR spectra of thecompounds X and Y contain a band around 3300 cm–1, while IR spectrum of compound Z contains
band 1720 cm–1.

1. Write down the structural formulae of compounds X–Z.

Without catalysts O2 has, fortunately, very low reactivity. Otherwise, all living organisms should beoxidized by air. A wide variety of oxidizing reagents have been developed for selective orundiscriminating oxidation of various functional groups in high yield. Below 7 organic molecules
are given. They were synthesized by oxidation with 7 indicated reagents.

These oxidation reactions proceed without C–C cleavage.

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IChO-2015

2. Put the correspondence between the products and the oxidants and determine the starting organic
compounds.

Examples of the chemoselective oxidation of the same substrate with different oxidants affording
different reaction products are given below.

Compounds I, J, and K react with Ag(NH3)2OH solution producing the metallic silver precipitation.
Compound H could be formed by oxidation of J. The treatment of 1.44 g of L with metallic sodium
produces 0.224 L (P = 1 atm, T = 273 K) of hydrogen gas.

3. Write down the structural formulae of compounds H–L.

Problem 18. Essential ozone

Until NMR became the main method for the determination of structures of organic molecules, theozonolysis reaction, disclosed by Schönbein in 1840, was intensively used for the ascertainment of
the unsaturated bond(s) position(s) in molecules. Imagine that you are in a similar situation (butwith modern reagents). You have found that some hydrocarbon C10H16 participates in thetransformations given in Scheme 1.

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IChO-2015

Scheme 1

1. Determine the structural formulae of the hydrocarbon C10H16 and the molecules A–D accounting
for the fact that compounds C and D are isomers of the initial hydrocarbon; the ozonolysis of C
followed by the treatment of the reaction mixture with alkaline H 2O2 produces a single productwhile the same transformations of D afford two compounds.
Some other hydrocarbon E (ωC = 90.6%) under ozonolysis (1. O3, CH2Cl2, –78 oC; 2. Me2S) forms
three carbonyl compounds – F (C2H2O2), G (C3H4O2), and H (C4H6O2) in a ratio of 3:2:1. Initialhydrocarbon E doesn’t decolorize bromine water.

2. Write down the structural formulae of hydrocarbon E and products of its ozonolysis F–H.

Hydrocarbon I having center of symmetry was used as an initial material in the total synthesis ofpentalenene (Scheme 2):

The ozonolysis of hydrocarbon I furnishes a single compound P or Q depending on the treatment of
the ozonolysis product. Under treatment with I 2 and NaOH, compound Q forms a yellow precipitatecontaining 96.7% of iodine. Under basic conditions compound Q is transformed into compound R
containing 4 types of hydrogen atoms (4 signals in 1H NMR spectrum with integral intensity of27

IChO-2015

signals 1:1:2:2). Molecular formula of R is C5H6O. Molecule of compound N has bicyclic
framework containing R as a fragment. Molecule of O consists of three rings.

3. Descript the scheme of the synthesis of pentalenene.

Problem 19. Two in one
Ellagic acid and its family exhibit antioxidant, anti-cancer, and other types of biological activity.
Very recently, the first total synthesis of nigricanin, one of the ellagic acid congeners, wasdescribed (Scheme 1).

Decipher this scheme. Write down the structural formulae of compounds A–K accounting for thefacts that F and G are isomers; molecular formulae of D and E are C21H17IO4 and C37H31IO7,
respectively.

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IChO-2015

Problem 20. Antitussive “narcotine”(-)-α-Noscapine is an alkaloid isolated from Papaver somniferum L. in 1817 by P. Robiquet which
named this compound as “narcotine”. This agent demonstrates significant painkilling andantitussive activities. It is also used for treatment of cancer, stroke, anxiety, and so on. Clinicallyused (-)-α-noscapine is provided through extraction from natural sources or resolution of synthetic
racemic compound. There are some syntheses of (±)-α-noscapine. One of them is given in thescheme below.

Decipher this scheme. Write down the structural formulae of compounds A–I if G is a tricyclic
compound.

Problem 21. Pyrrolizidine alkaloids
Pyrrolizidine alkaloids and their unnatural analogues occupy the important place in organic
chemistry due to a broad variety of physiological activities. Polyhydroxylated pyrrolizidines form a
sub-class of these alkaloids, members of which are often referred to as aza-sugars (or imino sugars)
and inhibit various glycosidases that can be useful for the treatment of diabetes, influenza, HIV andother diseases. The synthesis of dihydroxypyrrolizidine alkaloid, ()-turneforcidine, is given in the
Scheme 1. In this scheme E is an unstable intermediate which spontaneously undergoes the Claisen
rearrangement producing F.

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IChO-2015

Scheme 1

Epimer of turneforcidine at C(7) atom, ()-platynecine, was synthesized by the reaction sequence
given in Scheme 2. It is noteworthing that K is the product of [2+2]-cycloaddition.

Scheme 2

Decipher these schemes. Write down the structural formulae of compounds A–M as well as of ()platynecine.

Problem 22. Delightful odor of truffle
For many people the taste and odor of truffles are so delightful that truffles cost more than theirweight in gold. The compound X is responsible for the divine smell of the black truffle. The
treatment of 0.108 g of compound X with the acidified solution of HgSO4 leads to the formation ofsome precipitate Z. The treatment of the formed organic compound A with the excess ofAg(NH3)2OH afforded 0.432 g of metallic silver. Gas formed as a result of the burning of 0.648 g ofcompound X was divided into two equal parts. One part was passed through the Ba(OH)2 solution,
3.075 g of precipitate was formed. Another part was passed through NaOH solution. After sometime the excess of BaCl2 solution was added. It led to the formation of 3.171 g of precipitate.

Write down the structural formulae of compounds X, Z, A. Determine the weight of the precipitate
Z. Assume that all reactions proceed with 100% yield.

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IChO-2015

Problem 23. Synthesis of large rings. The magic or routine work?
The synthesis of large rings is a challenging problem of the synthetic organic chemistry. On thecontrary, Nature solves this problem efficiently. Thus, various fungus produce macrolactone
polyketides. One of them, Macrosphelide A, attracts attention as potent, orally bioavailable inhibitorof the interaction between cancer and endothelial cells. A number of syntheses of this molecule wasreported. One of them was based on the utilization of lactic (2-hydroxypropionic) acid derivative
according to Scheme below.

1. Decipher this scheme. Write down the structural formulae of compounds A-L.
2. Write down the IUPAC name of compound E.

Problem 24. What Time is it in Baku or Cheating the Death
One looking at the puddle, sees in her dirt, and another – reflected in her star
Immanuel Kant
People use acronyms for convenience sake. Still, sometimes the meanings are not absolutely
unambiguous. Thus, AZT generally standing for Azerbaijan time has acquired an alternative
meaning in pharmacology denoting one of the most usable anti-HIV drugs. Nucleoside A1, a major
component of nucleic acids, was used as a starting material in AZT synthesis. Under complete
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IChO-2015

combustion with subsequent condensation of water A1 gives a gas undergoing an 11-fold volume
decrease when bubbled through the 1 M KOH solution.

1.

What are the building blocks of nucleosides?

2.

Deduce the structures of all of A1 to A4. Note that: When arranged in any order the numbers of atoms in A1 are not described by either arithmetic
or geometric progression
 all the synthetic steps are SN-type reactions
 A4 is a binary compound (85.8 % N by mass)
 O is the heaviest element in both A3 and AZT

3.

How many stereoisomers of AZT do exist?

4.

Give the full wording for the pharmaceutical AZT acronym.

5.

Propose the mechanism of AZT antiviral action.

Metabolism of AZT is diverse and includes several pathways (X, Y, and Z) shown in the hereunderscheme (all balanced equations). X, the major of these, leads to a higher soluble product B1
excreted with urine. Y provides the cytotoxic product B2 with the same number of atoms as that in
AZT. Z is found in patients infected with a specific bacteria, the product B4 retaining the AZT-type
activity.

6.

Draw the structures of B1-B4.

"Dallas Buyers Club", a movie from 2013, received numerous awards including three Oscars. It isbased on a true story describing ambiguous results of the first clinical AZT trials. The protagonist
suffering from AIDS lacks a positive effect from AZT and switches over to drugs unauthorized by
US FDA. One of the latter is based on the substance D.
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IChO-2015

D (51.17 % C by weight) and nucleoside N (a major component of nucleic acids; 47.57 % C by
weight) differ by one atom only. Under complete combustion with subsequent condensation ofwater, the mixture of D and N of any composition gives gaseous products undergoing a 7-folddecrease of their total volume when bubbled through the 1 M KOH solution. It was found that D
imitates AZT with respect to the mechanism of its action.

7.

Calculate the number of C and N atoms in D without deciphering its structure.

8.

Draw the structures of D and N.

9.

Do you support the “Dallas Buyers Club” principal character in his belief that D possesses amajor clinical advantage over AZT? Comment why physicians used to administer AZT and D in a
combination.

The compound D turns out to be a prodrug. Its active metabolite M (17.23 % P and 35.62 % O bymass) is produced by a number of manufacturers for research (non-clinical) purposes only.

10. Draw the structure of M.
Note: If you feel like watching the above movie, check the film rating system accepted in yourcountry.

Problem 25. Number One Enzyme
Enzymes rule over in biochemical processes. Enzyme Commission (EC) numbers have been
proposed in order not to be lost in the vast variety of biocatalysts. This is a four-level classification
based on the types of enzymatic reactions, each specific reaction being described by four numbers
separated by periods. Number 1 of 6 top-level EC numbers is attributed to oxidoreductases,
enzymes catalyzing oxidation/reduction reactions (transfer of H and O atoms or electrons from one

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IChO-2015

substance to another). These reactions are of a great importance for both energy transformation andxenobiotic metabolism.

Changes of the oxidation state of a molecule can be achieved in different ways, which makes
possible a more detailed classification of oxidoreductases. Many of these require a cofactor orcoenzyme. Thus, dehydrogenases remove two hydrogen atoms from an organic substrate and passthem over to a suitable acceptor like nicotinamide adenine dinucleotide {phosphate} (NAD+{NADP+}) or flavin adenine dinucleotide (FAD).

1.

Write down the equation of ethanol oxidation involving NAD + as the coenzyme. Show thechanges in the nicotinamide moiety.

2.

Sometimes the route of dehydrogenase reaction is determined by the coenzyme/cofactor

involved. Predict the structures of A1–A3 in the following scheme if it is known that 1.00 g of A3
gives 7.52 g of silver precipitate under Tollens` reagent treatment.

Oxygenases catalyze direct addition of oxygen atoms originating from O2 to an organic substrate.
These enzymes are further subdivided into mono- and di-oxygenases depending on the number ofincorporated atoms (one and two, respectively). In the case of monooxygenases the other oxygen
atom is reduced to water by an appropriate reactant. Cytochrome P-450-dependent monooxygenase
is an exceptionally important representative of the class.

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IChO-2015

An aromatic compound B1 contains 77.75% C and 14.80% O by mass. B1 metabolism in rat liver
microsomes develops in two ways (see on the hereunder scheme). B2 reveals 4 signals in 1H-NMR
spectrum. B2 and B3 undergo color changes when added to 1% FeCl3 solution, whereas the B1color is unaffected by such treatment. All of B1 to B4 are composed of the same elements. B4 is a
gas under STP.

3.

Decipher B1 to B4. Write down the balanced equations.

Under oxygen deficiency B1 partially converts into B5, an isomer of B2. This transformation
requires a vitamin as the oxygen acceptor. Further oxidation of B5 leads to B6 characterized by 2
signals in 1H-NMR spectrum.

4.

Draw the structures of B5 and B6 as well as of both forms of the vitamin.

Like dehydrogenases, oxidases remove hydrogen atoms from an organic substrate transferring theseeither to the molecular oxygen or X, which finally results in water formation in both cases. The
phenol oxidation can be described by the following equation:
2Phenol + X = Y + 2H2O
The reaction develops via a free radical intermediate and leads to a mixture of isomers of Y (77.4 %C by mass).

5.

Decipher X. Draw the isomers of Y that show a sole peak in the phenolic region of 1H-NMR

spectra at low temperatures.

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IChO-2015

Problem 26. Holy War against Four Horsemen of the Apocalypse
For centuries the Caspian Sea is widely known for its oil fields. Nowadays it attracts ever increasing
attention of researches as a treasury of biological resources, in particular, of algae which can beconsidered as virtually inexhaustible source of unique chemicals. These studies are in line with theglobal fight of Enlightened Humanity against the four Horsemen of the Apocalypse  Conquest,
War, Famine, and Death.

Substances X and Y have been isolated from red algae Asparagopsis armata. These substances are
rarely found in nature and belong to the same class of organic compounds. A sample of 1.000 g of
Y was combusted in an excess of oxygen at high temperature followed by complete absorption ofcolorless gaseous (25С, 1 atm) mixture of products with an excess of aqueous calcium hydroxide
solution leading to 1.620 g of a white precipitate. Addition of the supernatant to an excess of silver
nitrate solution provided 1.786 g of a colored precipitate.

It is also known that: cooling of Y combustion products from 150 down to 0С does not result in any condensed
phase;
 white precipitate is an individual compound; the molar masses of each of X and Y are less than 275 g/mol; the number of atoms of any element in the molecules of X and Y does not exceed 3.

1.

Without revealing the molecular formula, deduce which elements may be found in Y.

2.

Without revealing the molecular formula of Y, write down the equation that includes numbersof atoms in the molecule as unknowns. Can this equation be of help in establishing the Y
composition?

3.

Determine the molecular formula of Y using all the data provided.

4.

Will the substitution of silver nitrate by silver oxide in ammonia solution in the above

experiment change the weight and color of the precipitate? To support the answer, calculate thesolubility of AgBr (Ksp = 5.410–13) in 1.0 M NH3 taking into account that the two first stepwise
formation constants of silver-ammonia complexes are 103.32 and 103.92, respectively.

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IChO-2015

Subjecting 1.000 g of X to the described above analysis sequence results in a colored gaseous(250С, 1 atm) mixture of products leading to 0.756 g of a white individual precipitate after passing
the mixture through an excess of aqueous calcium hydroxide solution. Addition of silver nitratesolution to the supernatant also provides a colored precipitate.

It is known that molecules of Y and X differ by one element, Y having one atom more. X can exist
as a mixture of enantiomers, whereas Y reveals geometric isomerism. Furthermore, Y reacts with
0.1 M aqueous KOH solution at room temperature.

5.

Deduce the molecular formula and draw the structure of X.

6.

Draw all possible geometric isomers of Y.

7.

Based on theoretical considerations decide which of the Horsemen of the Apocalypse can bepotentially defeated by X and Y?

Substance Z (41.00% O by weight) belongs to the same class of compounds as X and Y. However,Z has been only detected in leaves of some plants, and never in algae.

Combustion of a 1.000-g sample of Z in a large excess of oxygen followed by complete absorptionof colorless gaseous (25С, 1 atm) products with an excess of aqueous calcium hydroxide solution
leads to 3.065 g of a white precipitate. By contrast, no precipitate formed when the supernatantfrom the previous test was added to an excess of silver oxide in ammonia solution.

It is also known that: one of the gaseous products of Z combustion has the density of 1.43 g/L (measured at 34C,
750 Torr); the number of atoms of any element in the molecule of Z does not exceed 3.

8.

Find the molecular and structural formulae of Z.
Both Z and its sodium salt are highly toxic to all mammals.

9.

Knowledge of the area of organisms producing Z as well as of its metabolic pathway inmammals can be considered as a weapon against some of the Horsemen of the Apocalypse.
Comment which of these, in your mind.

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IChO-2015

SAFETY RULES AND REGULATIONS ADOPTED AT IChO
Extracts from the Regulations of the International Chemistry Olympiad (IChO)§ 12 Safety(1) During the experimental part, the competitors must wear laboratory coats and eye protection.
The competitors are expected to bring their own laboratory coats. Other means of protection forlaboratory work are provided by the organizer.
(2) When handling liquids, each student must be provided with a pipette ball or filler. Pipetting by
mouth is strictly forbidden.
(3) The use of acutely toxic substances (GHS hazard statement H300, H310, H330) is strictly
forbidden. The use of toxic substances is not recommended, but may be allowed if special
precautions are taken. Substances with GHS hazard statements H340, H350, H360 (provenmutagens, carcinogens, and teratogens) must not be used under any circumstances (seeAppendix B for definitions of these categories).
(4) Detailed recommendations involving students´ safety and the handling and disposal ofchemicals can be found in Appendices A 1, A 2, and B.
a) Appendix A 1: Safety Rules for Students in the laboratory.
b) Appendix A 2: Safety Rules and Recommendations for the Host Country of the IChO.
c) Appendix B contains a reference to the hazard symbols and statements of the Globally
Harmonized System of Classification of Chemicals (GHS), the use of which is expected inlabeling and classifying materials used at the IChO.

APPENDIX A
A 1: SAFETY RULES FOR STUDENTS IN THE LABORATORY
All students of chemistry must recognize that hazardous materials cannot be completely avoided.
Chemists must learn to handle all materials in an appropriate fashion. While it is not expected thatall students participating in the International Chemistry Olympiad know the hazards of every
chemical, the organizers of the competition will assume that all participating students know thebasic safety procedures. For example, the organizers will assume that students know that eating,drinking or smoking in the laboratory or tasting a chemical is strictly forbidden.
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IChO-2015

In addition to the common-sense safety considerations to which students should have beenpreviously exposed, some specific rules, listed below, must also be followed during the Olympiad.
If any question arises concerning safety procedures during the practical exam, the student should
not hesitate to ask the nearest supervisor for direction.
Rules regarding personal protection
1. Eye protection must be worn in the laboratories at all times. If the student wears contact lenses,
full protection goggles must also be worn. Eye protection will be provided by the host country.
2. A laboratory coat is required. Each student will supply this item for himself/herself.
3. Long pants and closed-toed shoes are recommended for individual safety. Long hair and loose
clothing should be confined.
4. Pipetting by mouth is strictly forbidden. Each student must be provided with a pipette bulb or
pipette filler.
Rules for Handling Materials
1. Specific instructions for handling hazardous materials will be included by the host country in
the procedures of the practical exam. All potentially dangerous materials will be labeled using
the GHS symbols. Each student is responsible for recognizing these symbols and knowing their
meaning (see Appendix B).
2. Do not indiscriminately dispose chemicals in the sink. Follow all disposal rules provided by thehost country.
A 2:

SAFETY RULES AND RECOMMENDATIONS FOR THE HOST COUNTRY OF
THE INTERNATIONAL CHEMISTRY OLYMPIAD

Certainly it can be assumed that all students participating in the IChO have at least modest
experience with safety laboratory procedures. However, it is the responsibility of the International
Jury and the organizing country to be sure that the welfare of the students is carefully considered.
Reference to the Safety Rules for Students in the Laboratory will show that the students carry someof the burden for their own safety. Other safety matters will vary from year to year, depending onpractical tasks. The organizers of these tasks for the host country are therefore assigned
responsibility in the areas listed below. The organizers are advised to carefully test the practical39

IChO-2015

tasks in advance to ensure the safety of the experiments. This can best be accomplished by having
students of ability similar to that of IChO participants carry out the testing.
Rules for the Host Country (see also A 1):
1. Emergency first-aid treatment should be available during the practical examination.
2. Students must be informed about the proper methods of handling hazardous materials.
a) Specific techniques for handling each hazardous substance should be included in thewritten instructions of the practical examination.
b) All bottles (containers) containing hazardous substances must be appropriately labeledusing internationally recognized symbols (see Appendix B).
3. Chemical disposal instructions should be provided to the students within the written instructionsof the practical examination. Waste collection containers should be used for the chemicals
considered hazardous to the environment.
4. The practical tasks should be designed for appropriate (in other words, minimum) quantities ofmaterials.
5. The laboratory facilities should be chosen with the following in mind:a) Each student should not only have adequate space in which to work, but should be in safe
distance from other students.
b) There should be adequate ventilation in the rooms and a sufficient number of hoods whenneeded.
c) There should be more than one emergency exit for each room.
d) Fire extinguishers should be nearby.
e) Electrical equipment should be situated in an appropriate spot and be of a safe nature.
f)There should be appropriate equipment available for clean-up of spills.

6. It is recommended that one supervisor be available for every four students in the laboratory toadequately ensure safe conditions.
7. The organizers should follow international guidelines for the use of toxic, hazardous or
carcinogenic substances in the IChO.

40

IChO-2015

APPENDIX B
HAZARD WARNING SYMBOLS AND HAZARD DESIGNATIONS
Chemicals used in the IChO laboratory experiments need to be labeled according to the Globally
Harmonized System of Labeling of Chemicals (GHS) standard developed by the United Nations.
The organizing country should use the locally legislated GHS system (pictograms, hazard
statements, etc.) if it exists. If such rules do not exist, the original GHS directives(http://www.unece.org/trans/danger/publi/ghs/ghs_welcome_e.html)

and

the

GHS

documentation by the chemical providers should be used

GHS HAZARD STATEMENTS
Code

Hazard Statement
Physical Hazards

H225

Highly flammable liquid and vapor

H232

May form combustible dust concentrations in air

H260

In contact with water releases flammable gases which may ignite spontaneously

H271

May cause fire or explosion; strong oxidizer

H272

May intensify fire; oxidizer

H290

May be corrosive to metals
Health hazards

H301

Toxic if swallowed

H302

Harmful if swallowed

H303

May be harmful if swallowed

H304

May be fatal if swallowed and enters airways

H311

Toxic in contact with skin

H314

Causes severe skin burns and eye damage

H315

Causes skin irritation

H316

Causes mild skin irritation

H317

May cause an allergic skin reaction

H318

Causes serious eye damage

H319

Causes serious eye irritation

H320

Causes eye irritation
41

compliantIChO-2015

H332

Harmful if inhaled

H333

May be harmful if inhaled

H335

May cause respiratory irritation

H336

May cause drowsiness or dizziness

H351

Suspected of causing cancer

H361

Suspected of damaging fertility or the unborn child

H373

May cause damage to organs through prolonged or repeated exposure
Environmental hazards

H400

Very toxic to aquatic life

H402

Harmful to aquatic life

H410

Very toxic to aquatic life with long lasting effects

H411

Toxic to aquatic life with long lasting effects

H412

Harmful to aquatic life with long lasting effects

42

IChO-2015

PRACTICAL PROBLEMS
Problem 27. Determination of nickel in nickel and copper-nickel alloys bycomplexometric titration
Nickel forms single-phase solid solutions with some metals such as copper, iron, and chromium.
Nickel and copper feature unrestricted mutual solubility. Copper-nickel alloys, also referred to as
cupronickels, possess different properties depending on their composition. The most usedcupronickels contain 10 to 45% of nickel.

The main properties of copper-rich alloys (70–90% of copper) include high resistance to corrosion,
electrical conductivity, ductileness, strength at elevated temperatures. These features make thealloys highly sought in various industrial applications: construction of sea water corrosion-resistantfacilities including oil rig platforms (which is of particular importance for Azerbaijan!), condenser
systems in desalination plants, cooling circuits, and ammunition. Small amounts of other elements
are usually added for specific purposes; the two most popular alloys for marine applications containup to 2% iron and manganese. The alloy composed of copper with 45% nickel content provide foralmost exactly constant resistance regardless of temperature, and is thus used in the production ofthermocouples and resistance wires in high precision resistors. The copper-nickel alloy containing
25% nickel with an additive of 0.05-0.4% manganese is commonly used in manufacturing coins andmedals.

Precipitation of nickel as dimethylglyoximate followed by its weighing is widely used for accurate
determination of this metal in steels and alloys. Nickel can also be assayed by treatment of a Ni 2+
containing solution with KI and KCN followed by titration with silver nitrate.

Only metal ions (Zn(II), Cu(II), Ca(II) or Mg(II)) rapidly forming EDTA complexes can be
determined by direct titration with EDTA. Since the EDTA complex of nickel(II) is formed slower,
the back titration is used in the latter case: EDTA is added in an excess and the unreacted EDTA isback titrated with Ca(II) or Mg(II), the metals that also form colored complexes with a suitableindicator (such as Eriochrome black T), still less stable than the nickel one.

43

IChO-2015

In this task you will precipitate nickel from its ammonia solution with dimethylglyoxime in thepresence of citric or tartaric acid as a masking agent* and then determine the metal content bycomplexometric titration with Eriochrome black T as the indicator.**

Notes.
*At this stage, gravimetric determination of nickel as dimethylglyoximate may be carried out.
However, it requires drying to constant weight, which may be time consuming.
**The method gives best results with the alloys containing less than 0.5 mass % of Cu.
Chemicals and reagents:















Alloy sample, ~0.5 g, or test solution (a solution containing about 1 g L–1 of Ni2+, 0.5-0.7 g L–1
Fe3+, 5-6 g L–1 Cu2+)
Diluted nitric acid (1: 1, v/v)
Diluted hydrochloric acid (1: 1, v/v)
Diluted sulfuric acid (1: 1, v/v)
Citric acid or tartaric acid
Ammonia solution, concentrated
Dimethylglyoxime (10 g L–1 in ethanol)
Ammonium chloride, 10%
Sodium hydroxide (200 g L–1)
Hydrogen peroxide solution, 3%
Eriochrome black T (as a mixture with NaCl, 1:100 w/w)
Standard 0.05 M EDTA solution: dissolve 18.61 g of solid ethylenediamine tetraacetate
disodium dihydrate in 500 mL of distilled water, place the mixture into a measuring flask anddilute to 1 L.
Ammonia – ammonium chloride buffer solution, pH 10: dissolve 70 g of solid NH4Cl in 600
mL of concentrated (~15 M) ammonia and dilute to 1 L with distilled water.
Magnesium sulfate solution (0.05 M): dissolve 12.33 g of solid magnesium sulfate
heptahydrate in 500 mL of distilled water and dilute to 1 L.
Substance

Name

State

HNO3

Nitric acid
Ethylenediamine tetraacetate
disodium dihydrate,
Na2H2EDTA×2H2O
Hydrochloric acidSulfuric acid
Citric acid
Tartaric acid
Ammonia
Dimethylglyoxime
Ammonium chloride
Sodium hydroxideaqueous solution

C10H14N2O8Na2
×2H2O
HCl
H2SO4
C6H8O7C4H6O6NH3C4H8N2O2
NH4Cl
NaOH

44

solid
aqueous solution
aqueous solution
solid
solid
aqueous solution
solution in ethanol
aqueous solution
aqueous solution

GHS Hazard
Statement
H290, H314, H318
H302, H315, H319,
H335
H314, H318
H319
H315, H319, H335
H314, H400
H232
H302, H319
H314

IChO-2015

H2O2

Hydrogen peroxideaqueous solution

C20H12N3O7SNa
NaCl

Eriochrome black T
Sodium chloride
Magnesium sulfate
heptahydrate

solid
solid

H271, H302, H314,
H333, H402
H319
Not classified

solid

Not classified

MgSO4*6H2O

Equipment and glassware:















Analytical balance (± 0.0001 g)
Glass beaker, 250 and 400 mL
Watch glass
Hotplate stirrer
Volumetric flask, 500 and 100 mL
Paper filters (3 ea.)
FunnelpH Indicator paper
Burette, 25 or 50 mL (2 ea.)
Funnels (to fill the burettes)
Volumetric pipette, 10 mL
Erlenmeyer flask, 100 mL (3 ea.)
Graduated cylinders, 10 and 25 mL
Wash bottle with distilled water

Procedure
A. Standardization of MgSO4 solution
1)

Fill a burette with the standard Na2H2EDTA solution. Transfer 5.00 mL of the solution into

the 100-mL Erlenmeyer flask. Adjust pH to 10 with the ammonium buffer solution (3–4 mL). Add
20–30 mg of the Eriochrome black T indicator.
2)

Fill the other burette with MgSO4 solution. Titrate the prepared EDTA solution with MgSO 4

under continuous stirring until the blue color sharply turns into purple (the change must be
irreversible). Record the volume of MgSO4 solution consumed in titration. Repeat the titration until
your get consistent results.
The concentration of MgSO4 solution (M) is found from the following equation:
C1=V0·C0/V1,

where V0 is the volume of Na2H2EDTA taken for titration, mL,
V1 is the volume of magnesium sulfate consumed in titration, mL,
C0 – the concentration of Na2H2EDTA solution.

45

IChO-2015

B. Dissolution of the alloy sample (the experiment should be carried out under a fume hood)(Skip this stage and proceed to part C if you are analyzing a test solution rather than an actual
alloy sample)
1) Accurately weigh out the alloy sample, place it into a 250-mL beaker and carefully dissolve in
15 mL of nitric acid (diluted with water, 1:1 v/v). Cover the beaker with the watch glass.
2) Gently heat the solution and boil it on a hot plate until dissolution is complete (the residual
volume should be of about 5 mL). Transfer the solution into the 500-mL volumetric flask, rinse thewatch glass and the beaker with distilled water, add the wash water to the volumetric flask, anddilute to the mark using the wash bottle.
3) If the alloy sample cannot be totally dissolved (as it may contain W and/or Si), heat the mixture
to dryness, add 10 mL of HCl (1:1 v/v) and heat to dryness again. Dissolve the dry residue in 10 mLof concentrated HCl and dilute it with 100 mL of distilled water. Filter off the precipitated tungstic
acid using two filters and a long-stem funnel. Wash the precipitate with hot diluted HCl solution(1:10 v/v) until no Ni2+ ions are detected in wash waters (test with dimethylglyoxime).
4) If the sample contains more than 0.1 mass % of Si, add 10 mL of H 2SO4 (1:1 v/v) and evaporate
till abundant evolving of sulfuric acid fumes. Cool the slurry and carefully add about 10 mL of cold
water. Then add 100 mL of hot water and dissolve the residue under heating. Filter off the
precipitated silicic acid with filter paper and wash the precipitate with hot water. Transfer thefiltrate obtained after W and/or Si separation to a 500-mL volumetric flask and dilute to the mark.

C. Precipitation of nickel dimethylglyoximate
1) Transfer 50.00 mL of the test solution into the 400-mL beaker, adjust the volume with water to
200 mL and add 6–8 g of solid tartaric or citric acid. Heat the solution on the hot plate until
dissolution of the acid is complete. Neutralize the mixture to pH 4–5 with 5–10 mL of ammonia
solution (check against the pH indicator paper).
2) Add 25 mL of the dimethylglyoxime solution in ethanol dropwise under intensive stirring, add
2–3 mL of the concentrated ammonia solution to obtain pH 10 and then the other 2–3 mL portion of
the same solution to provide for NH3 excess. You will observe the precipitation of nickel
dimethylglyoximate.
3) If iron hydroxide precipitates as the solution turns alkaline, add more tartaric or citric acid.
4) Heat the solution with the precipitate on the hot plate until boiling (do not allow boiling!) andstore it in a warm place for 40–50 min.

46

IChO-2015

5) Filter the precipitate using the filter paper and wash it with 4–5 portions of hot distilled water.
Then wash the precipitate off to the 400-mL beaker, first with 30–50 mL of HCl (1:1 v/v) and thenhot water. If you failed dissolving the precipitate, heat the solution and slightly boil it with stirring.
6) Cool the solution down to room temperature, transfer to a 100-mL volumetric flask and dilute to
the mark with distilled water.
D. Determination of Ni2+
1) Transfer 10.00 mL of the prepared Ni2+ solution into the 100-mL Erlenmeyer flask. Adjust pH to
10 with the ammonium buffer solution (4–6 mL) and add 10.00 mL of the standard Na2H2EDTA
solution from the burette. Add 20–30 mg of the Eriochrome black T indicator to obtain a blue
colored solution.
2) Fill the burette with the standard MgSO4 solution and take the initial reading of the burette.
Titrate the blue nickel(II) solution with the standard MgSO 4 solution until the color becomespermanently purple. Take the final reading of the burette. Repeat the titration until your get
consistent results.
3) Calculate the amount of Na2H2EDTA spent for Ni2+ titration based on the volumes of theNa2H2EDTA solution added and the MgSO4 solution consumed in the titration.

Questions and Data Analysis
1.

Write down the balanced chemical equations for the reactions occurring: when the sample of the alloy is dissolved in nitric acid; when the test solution is titrated with the magnesium sulfate solution.

2.

Explain the role of citrate or tartrate when in the process leading to nickel

dimethylglyoximate? Write down the corresponding chemical equations.

3.

Explain the necessity of the nickel dimethylglyoximate precipitation. How do Сu and Mg

present in the test mixture interfere with the determination of nickel? Write down appropriate
chemical equations.

4.

Explain why the pH value of the titrated solution should be kept below 10. In calculations,use the following constants of complex formation: K[Ni(EDTA)]2– = 4.2×1018, K([Mg(EDTA)]2– =4.9×108.
47

IChO-2015

5.

What is the most stable form of EDTA at pH 10? Compare the molar fractions of HEDTA 3–

and EDTA4–. Note that H4EDTA is a weak acid with the following acidity constants: K1 = 1.0·10–2,
K2 = 2.1·10–3, K3 = 6.9·10–7, K4 = 5.5·10–11.
6. Derive the formulae for calculation of the Ni2+ concentration in the test solution. Calculate themass fraction of Ni in the alloy.

Problem 28. Titrimetric determination of lead and silver in their mixture
Lead and silver are often both present in alloys (such as tin-lead-silver or lead-silver), which aresuccessfully applied in bearing assembly, ballast, casting, step soldering, and radiation shielding.
The alloys usually contain 30–90 % of lead and 1–5 % of silver. Redox titration was found to be a
precise standardless method allowing determination of these metals.

In this work, you will determine lead and silver in a solution by redox titration.
Chemicals and reagents:









A sample of lead and silver containing alloy, or test solution simulating a dissolved alloy (astandard solution containing about 500–1000 mg Pb and 70–190 mg Ag in 0.1 L)
Ammonia aqueous solution (25% ammonium solution and water, 1:1 v/v)
Oxalic acid, saturated solution at room temperature
Potassium permanganate, 0.0100 M standard solution
Sulfuric acid, 1 M solution
Nitric acid, 4 M solution
Ammonium iron(III) sulfate, saturated solution
Ammonium thiocyanate, 0.0100M standard solution.

Substance

Name

State

NH3
C2H2O4

Ammonia
Oxalic acidaqueous solution
aqueous solution

KMnO4

Potassium permanganate

aqueous solution

H2SO4
HNO3
NH4Fe(SO4)2
NH4SCN

Sulfuric acid
Nitric acid
Ammonium iron(III) sulfate
Ammonium thiocyanate

aqueous solution
aqueous solution
aqueous solution
aqueous solution
48

GHS Hazard
Statement
H314, H400
H314, H318
H272, H302, H400,
H410
H314, H290
H290, H314, H318
H315, H319
H332, H412

IChO-2015

Equipment and glassware:













Analytical balance (± 0.0001 g)
Hot plate
Filter paper or glass filter
Burette, 25 mL (2 ea.)
Funnels (to fill the burettes)
Volumetric pipette, 10.00 mL
Pipette filler
Erlenmeyer flask, 100 mL
Volumetric flask, 100 mL
Glass beaker, 100 and 250 mL
Graduated cylinders
Waste bottle for oxalate solution

ProcedureA.

Decomposition of the alloy sample(Optional and may be omitted; if so, a model solution of metal salts is to be prepared; see
Chemicals and reagents for the solution composition)

Take a precise weight of the metal (~250 mg) and place it in a beaker. Carefully add 5 mL ofconcentrated nitric acid (to be done under a fume hood because of gaseous NO 2 evolvement). Heatthe beaker slightly on the hot plate to provide for an effective dissolution. When the digestion iscomplete evaporate the solution to near dryness to remove the major part of the acid (avoid
evaporating to dry salts, since hydrolysis may occur. If still so, add a minimal amount of HNO3 todissolve the residue). Allow the beaker cooling down to room temperature.

ATTENTION! Nitric acid is very corrosive! You will have to deal with hot solutions in the above
and subsequent steps. Be careful and beware of steam!

B1. Separation of lead
Using the hot plate, remove the excess of the acid by evaporating the solution obtained at stage A todryness and dissolve the residue in water (skip this step if a model test solution is used rather than areal alloy solution). Bring the solution to boiling, then add about 10 mL of the saturated solution ofoxalic acid and observe a precipitate formation. Avoid large excess of oxalic acid. To partiallydissolve the precipitate, add aqueous ammonia solution (1:1 v/v) dropwise.

49

IChO-2015

ATTENTION! The ammonia solution is corrosive and has a very strong smell! Keep the bottle
stoppered when not in use.

C. Determination of lead
Heat the solution above the precipitate on the hot plate to remove the excess of ammonia, and cool
the mixture quickly under the running tap water. Filter the slurry through the glass filter. Keep thefiltrate for next step. Wash the filter cake with cold water and then dissolve it in hot 0.5 M HNO3
adding the acid in small portions. Collect the obtained solution in the 100-mL volumetric flask andmake it up to the mark with water. Titrate oxalate in the prepared solution (take 10.00 mL aliquots)
with 0.0100 M solution of potassium permanganate.

ATTENTION! Oxalate solutions are toxic. Do not pour the solutions down a sink. Instead, dispose
these in a special waste bottle.

D. Determination of silver
Add 10 mL of 4M nitric acid solution and 1–2 mL of saturated iron(III) ammonium sulfate solution
to the filtrate (from step C). Use burette to add the standard solution of ammonium thiocyanate until
vanishing reddish-brown color is observed. Shake the flask and continue titrating until the color isstable.
Questions and Data Analysis
1.

Write down balanced chemical equations for the reactions that take place upon:a) formation of the precipitate (step B),b) partial dissolution of the precipitate in ammonia (step B),c) dissolution of lead oxalate (step C),d) oxalate titration with permanganate (step C).

2.

Explain the role of iron(III) at step D.

3.

Calculate the lead and silver content in the sample (starting alloy or test solution).

50

IChO-2015

Problem 29. Complexometric determination of iron, chromium, and zinc in an
alloy
Ferrochrome is an alloy of iron and chromium mostly (over 80% of world consumption) used instainless steel production. To improve the corrosion resistance of steel it is often coated with zinc,
the process being referred to as galvanization. It is of extreme importance to accurately control thecontents of zinc, iron, and chromium in the resultant galvanized steel. Typically samples of steel are
dissolved in concentrated nitric acid and the content of major components in the obtained solution isdetermined by different methods.

Analysis of multicomponent systems is often hindered by the interference between the components.
Various separation techniques (precipitation, extraction) or masking are the usual steps towards
avoiding such interference. Still, nowadays researches are mainly focused at analytical methods
allowing sequential determination of components in the same solution without any separation
procedures. These methods are typically based on simple manipulations like changing the pH.

In this task you will apply one of such methods for sequential determination of iron(III),
chromium(III) and zinc(II) simultaneously present in an aqueous solution.

Chemicals and reagents:









Test solution simulating a digested sample of galvanized steel (a standard solution containing
Fe3+, Zn2+ and Cr3+ ions within the concentration range of 0.1–0.3 M)
Hydrochloric acid, 1 M
Na2H2EDTA standard solution, 0.025 М
Acetate buffer solution, pH 5.5–6.0, 1.7 М in acetate
Copper(II) sulfate standard solution, 0.025 M
Ethanol, 96%
Distilled water
Indicators:- aqueous solution of 5-sulfosalicylic acid, 5% (w/w)- solution of 1-(2-pyridylazo)-2-naphthol (PAN) in ethanol, 0.1% (w/w)- universal pH indicator paper

Substance

Name

State

GHS Hazard
Statement

C10H14N2O8Na2Ethylenediamine tetraacetate
disodium dihydrate,
Na2H2EDTA

aqueous solution

H302, H315, H319,
H335

51

IChO-2015

HCl

Hydrochloric acidaqueous solution

C2H3NaO2

Sodium acetate

aqueous solution

CuSO4
C7H6O6S

Copper(II) sulfate
5-Sulfosalicylic acid
1-(2-Pyridylazo)-2-naphthol(PAN)aqueous solution
aqueous solution

H314, H318
H303, H316, H320,
H333
H301, H400, H410
H315, H319

ethanol solution

Not classified

C15H11N3O

Equipment and glassware:










Hot plate
Funnels (to fill the burettes)
Paper filters
Volumetric flask, 100 mL
Volumetric pipettes, 1 and 10 mL
Burette, 25 or 50 mL (2 ea.)
Erlenmeyer flask, 200 mL (3 ea.)
Graduated cylinder, 10 mL (2 ea.)
Glass dropper

Procedure
A. Sample preparation
Prepare 100 mL of your working solution by a 10-fold dilution of the test solution provided. Use
the 100 mL volumetric flask and distilled water. The Fe3+, Zn2+ and Cr3+ ions content in theworking solution would be within the concentration range of 0.01 – 0.03 M.
B. Determination of Fe3+
Place 10.00 mL of the working solution into a 200 mL Erlenmeyer flask, add about 20 mL of
distilled water and adjust the pH to 1 by adding about 5 mL of 1M HCl (check the pH value against
the indicator paper). Finally, supplement 1 mL of 5% aqueous solution of sulfosalicylic acid (theindicator) and mix thoroughly.

Titrate the flask contents with 0.025 M EDTA standard solution until the color changes from violet
to yellow-green. Record the volume of the standard solution (V 1, mL). Repeat the titration asnecessary.
C. Determination of Zn2+
Adjust the pH of the solution obtained in step B to 5–6 by adding 5–6 mL of the acetate buffer
solution, then add 3–5 drops of PAN solution (the indicator), 2 mL of ethanol (by cylinder) and mix
thoroughly.
52

IChO-2015

Titrate the flask contents with 0.025 M EDTA standard solution until the color changes from pink
to yellow-green. Record the volume of the standard solution (V 2, mL). Repeat the titration asnecessary.
D. Determination of Cr3+
Direct titration of Cr3+ with EDTA solution is impossible because of the low rate of complex
formation. Thus, the method of back titration is used: an excess of EDTA standard solution is
introduced, and the unreacted EDTA is titrated with Cu2+.

Supplement an excess of 0.025 M standard solution of EDTA (20 mL) to the solution obtained instep C, mix thoroughly and boil the mixture for 5 min. Add 3-5 drops of PAN solution (theindicator) to the cooled mixture and mix thoroughly.

Titrate the flask contents with 0.025 M CuSO4 standard solution until the color changes from winered to blue-violet. Record the volume of the standard solution (V 3, mL). Repeat the titration asnecessary.

Questions and Data Analysis
1.

Write down balanced chemical equations for the reactions that take upon:a) the sample of alloy is dissolved in concentrated nitric acidb) the working solution is titrated with Na2H2EDTA

2.

Derive the formulae for calculation of the Fe3+, Zn2+ and Cr3+ concentration in the test

solution. Calculate the concentrations of the ions.

3.

Calculate the molar fraction of H2EDTA2– at pH 1. EDTA is a weak acid with the following

acidity constants: K1 = 1.0·10–2, K2 = 2.1·10–3, K3 = 6.9·10–7, K4 = 5.5·10–11.

Problem 30. Synthesis of 3-(4-methylbenzoyl)propionic acid
The Friedel-Crafts reactions are a family of processes (acylation, alkylation, and some other lessimportant) developed by C. Friedel and J. Crafts in 1877 at the Sorbonne.
53

IChO-2015

The Friedel-Crafts acylation allows introducing of an acyl group into the aromatic ring with asuitable acylating agent (acyl halide or carboxylic acid anhydride) and a strong Lewis acid as acatalyst. Nowadays it is an important synthetic method providing aromatic and alkyl-aromatic
ketones, which are important intermediates in the production of pharmaceuticals, dyes and othervaluable compounds.
O

O

CH3
AlCl3

O

O

+
OH
H3C

O

The Friedel-Crafts alkylation is less sought, since may lead to a mixture of polyalkylated products.
Remarkably, a solution comes from the Friedel-Crafts acylation, since the acylation products arereadily reduced to the corresponding alkanes (e.g. via Clemmensen or Wolff-Kishner reactions).

Chemicals and reagents









Toluene (dry), 25 g
Succinic anhydride, 5 g
Aluminium chloride anhydrous, 13.3 g
Dichloromethane (Methylene chloride), 100 mL
Hexane, 75 mL
Hydrochloric acid, concentrated, 25 mL
Sodium sulfate, calcined, 20 g
Distilled water, 100 mL

Substance

Name

State

C7H8

TolueneliquidC4H4O3

Succinic anhydride

solid

AlCl3

Aluminium chloride

solid

CH2Cl2

Dichloromethane

liquidC6H14n-HexaneliquidHClHydrochloric acidaqueous solution

54

GHS Hazard
Statement
H225,H304, H315,
H336, H361, H373
H302, H319, H335
H315, H319, H335,
H402
H302, H315, H320,
H351
H225, H304, H315,
H335, H336,H361,
H373, H411
H302, H314, H318,
H335, H402

IChO-2015

NaSO4

Sodium sulfate

Solid

H317

Equipment and glassware

























Laboratory stand with clamps
Three-necked flask, 250 mL
Reflux condenser with breather tube
Dropping funnel, 100 mL
Magnetic stirrer with heating
Teflon magnetic stir bar
Hoses
Thermometer with a tapered joint
Tapered joint stopper
Ice bath
Graduated cylinder, 50 mL
Beaker, 100 mL
Separating funnel, 250 mL
Rotary evaporator
Paper filter
Fritted glass filter, porosity 2-3
Bunsen flask for vacuum filtration
Glass rod
Melting point apparatus
Capillary for melting point determination (2-3 ea.)
Glass tube for capillary filling
SpatulaTeflon sleeves for tapered joints or vacuum grease
Analytical balances (± 0.001 g)

ProcedureA.

Assembly of the apparatus

Assemble the apparatus as shown in the hereunder picture. Equip every joint with the Teflon sleeveor apply vacuum grease.

55

IChO-2015

5

6

4

7

1

11

9

2

B.

5
8

3

6

4

7

1

10

8

3

9

2

Preparation of the reagents and synthesis of the productFix the three-necked flask at the laboratory stand over the magnetic stirrer. Place 25 g of toluene
and 5 g of succinic anhydride into the flask and equip it with the reflux condenser with a breathertube, the dropping funnel and the stir bar. Start stirring the mixture. Use the neck left open to add
13.3 g of the finely-powdered anhydrous aluminum chloride in portions at continuous stirring.
When finished, fix the neck with the thermometer so that its tip is submerged into the reaction
mixture. Switch on heating. Close the neck with the stopper and vigorously stir the reaction mixture
for 1 h at 60 °C.
C.

Isolation of the productCool the flask down to room temperature and then place it in the ice bath. Fill the dropping funnel
with 60 mL of ice-cooled water. Add slowly (dropwise) all the water from the funnel to the reaction
mixture at constant vigorous stirring. When finished, add dropwise 25 mL of concentratedhydrochloric acid add 60 mL of dichloromethane. Transfer the reaction mixture to the separatory
funnel and tightly close it with the stopper.

Keep shaking the reaction mixture vigorously (turning the separatory funnel up and down) for a few
minutes, and then allow the phase separation. Add extra 10 mL of water and 10 mL ofdichloromethane if phase separation is not satisfactory. Segregate the well defined organic phase.
For better extraction, add 20 mL of dichloromethane to the aqueous phase and repeat separation as
described above two times. Combine the organic phases in the separatory funnel and wash with 30
mL of water. Pour out the organic phase and dry it over calcined Na 2SO4 for 1 h. Filter the56

IChO-2015

desiccant off using the paper filter or fritted glass filter. Evaporate the filtrate on the rotary
evaporator to approximately 20% of the original volume.

D.

Purification of the productTransfer the residue left after the rotary evaporation into the beaker and add 30 mL of hexane,
which will initiate the crystallization process. Place the beaker in the ice bath for 20 min tocomplete crystallization. Filter out the precipitate using the fritted glass filter and wash the productthree times with 15 mL of hexane each.

E.

Analysis of the productWeigh the product. Calculate the yield.

Place the non-sealed end of the capillary into the product crystals, then turn it the sealed end down
and throw several times down through a glass tube. Check that the sealed end side of the capillary isfilled with the product. Apply the ready capillary to the melting point apparatus and record themelting point of the product. Compare the value with the reference data and draw a conclusion
about the product purity.

Note. The resulting product, if pure, can be used as the starting compound in Problem 31.

Questions1.

Is it possible to introduce two acyl groups in the ring via the Friedel-Crafts electrophilic

substitution reaction? Propose the way to obtain 1,4-diacetylbenzene.

2.

Compare the activity of phenol, p-nitrophenol and p-methoxyphenol in the O-acylation

reaction in neutral medium (e.g. in THF). Suggest the reaction scheme of the most active compound(according to your choice) with propionic acid chloride.

3.

Why is the Friedel-Crafts acylation more often used as compared to the Friedel-Crafts

alkylation?

4.

Which other reagents (besides that considered in the Problem) can be used in the Friedel-

Crafts acylation?
57

IChO-2015

5.

Why are the ice-cooled water and concentrated hydrochloric acid added to the mixture once

the reaction is complete?

6.

Why aluminum chloride is taken in the two-fold excess?

Problem 31. Synthesis of 4-(4-methylphenyl)-4-hydroxybutanoic acid
The intermediate oxidation state of carbon in carbonyl compounds specifies its ability to take part inoxidation-reduction reactions. Depending on the selected reaction conditions the reduction of acarbonyl group can lead either to alcohols (primary in the case of aldehydes and secondary in thecase of ketones) or saturated hydrocarbons. The latter are typically formed as a result ofhydrogenation at elevated temperature and high pressure, still can also be obtained under relatively
mild conditions (e.g. via Clemmensen or Wolff-Kischner reactions).

Reduction of carbonyl compounds to alcohols can be successfully carried out by catalytichydrogenation. Still, the preference is nowadays given to other chemical processes due to thesimplicity of experimental procedures and accessibility of reagents. Hydride complexes ofaluminum (or boron) and alkaline metals are indispensable in organic synthesis due to their highreducing ability in a wide range of temperatures and the possibility of choosing appropriate
complexes applicable in solvents with different polarity. In this task you will get acquainted with
one of such reagents, sodium borohydride.
O

OHOO 1) NaOHOHO

2) NaBH4

2) HClH3C

H3C

O1) NaOHOH

H3C

Chemicals and reagents






β-(4-methylbenzoyl)-propionic acid, 4 g
Sodium borohydride, 0.8 g
Sodium hydroxide, 2.5 M aqueous solution, 24 mL
Hydrochloric acid, 6 М aqueous solution, 20 mL
Distilled water, 100 mL
Substance

Name

State
58

GHS Hazard

IChO-2015

Statement
C11H12O3β-(4-methylbenzoyl)propionic acid

solid

NaBH4

Sodium borohydride

solid

NaOH

Sodium hydroxideaqueous solution

HCl

Hydrochloric acidaqueous solution

H315, H319, H335
H260, H301+H311,
H314
H314
H302, H314, H318,
H335, H402

Equipment and glassware





















Laboratory stand with clamps
Three-necked flask, 250 mL
Reflux condenser with breather tube
Dropping funnel, 100 mL
Magnetic stirrer with heating
Teflon magnetic stir bar
Hoses
Thermometer with a tapered joint
Tapered joint stopper
Ice bath
Beaker, 100 mL (2 ea.)
pH indicator paper
Fritted glass filter, porosity 2-3
Glass rod
Melting point apparatus
Capillary for melting point determination (2-3 ea.)
Glass tube for capillary filling
SpatulaTeflon sleeves for tapered joints or vacuum grease
Analytical balances (± 0.001 g)

ProcedureA.

Assembly of the apparatus

Assemble the apparatus as shown in the picture in Problem 30. Equip every joint with the Teflon
sleeve or apply vacuum grease.

B.

Preparation of the reagents and synthesis of the productPrepare the solution of 0.8 g of sodium borohydride in 12 mL of water and pre-cool it to 0-5°C. Fix
the three-necked flask at the laboratory stand over the magnetic stirrer. Weigh out and admeasure
the required amounts of the reagents. Place 4 g of β-(4-methylbenzoyl)-propionic acid and 12 mL of
2.5 M aqueous solution of NaOH in the flask and equip it with the reflux condenser with a breathertube, the dropping funnel and the stir bar. Switch on stirring. Fix the unused neck with thethermometer so that its tip is submerged into the reaction mixture. Place the ice-water bath under59

IChO-2015

the flask. When the reaction mixture gets cooled down to 0-5°C, quickly add with intensive stirring
the pre-cooled sodium borohydride solution. Remove the ice-bath and let the reaction mixture warm
up to room temperature. Gently heat up the mixture to boiling and keep refluxing for 40 min. Thenadd 12 mL of 2.5 M aqueous solution of NaOH to the heated reaction mixture and continue
refluxing for another 20 min.

C.

Isolation of the productSwitch off the heating. Cool the flask down to room temperature and then place it in the ice-water
bath containing sodium chloride. Fill the dropping funnel with 15 mL of 6 M HCl and add the acidsolution slowly to the flask under vigorous stirring continuously monitoring the pH of the reaction
mixture with the pH indicator paper (capture a drop of the reaction mixture with the glass rod
through the neck of the flask and apply it to the test paper). Important! The temperature of thereaction mixture must not exceed 5°C. Instantly control the temperature keeping the tip of thethermometer submerged into the reaction mixture. Adjust the pH to 2 and observe precipitation ofwhite crystals. Filter out the product using the fritted glass filter and wash it 2-4 times with ice-coldwater until the pH of the filtrate attains 4-5.

Air-dry the resulting white precipitate on a filter paper for a few hours. To accelerate the process theprecipitate may be placed in a round-bottom flask and dried out on a rotary evaporator under
reduced pressure. Control the dryness of the product by determining its melting point.

E.

Analysis of the productWeigh the product. Calculate the yield.

Place the non-sealed end of the capillary into the product crystals, then turn it the sealed end down
and throw several times down through a glass tube. Check that the sealed end side of the capillary isfilled with the product. Apply the ready capillary to the melting point apparatus and record themelting point of the product. Compare the value with the reference data and draw a conclusion
about the product purity.

Questions60

IChO-2015

1.

What effects does an alkali produce on the starting materials and the reaction intermediates?

Write down the equation of sodium borohydride reaction with water in neutral medium. Suggest themechanism of the lactone disruption.

2.

Why does addition of the acid at the final stage of the synthesis lead to the productprecipitation?

3.

Consider an alkylaldehyde and a dialkyl ketone. Which carbonyl group is more readily

reduced with sodium borohydride? Justify your answer.

4.

The reaction considered in this Problem serves as an example of the selective reduction of aketo group in the presence of a carboxyl one. Propose a way how a carboxyl group can beselectively reduced in the presence a carbonyl group.

5.

A compound with the molecular formula C17H25NO2 is produced when the starting

compound is treated with cyclohexylamine (in equimolar amount to ketoacid) in methanol in thepresence of catalytic amounts of a strong acid followed by the addition of sodium borohydride.
Suggest the structures of the final and intermediate products as well as the mechanism of the firststage of the reaction.

Problem 32. Synthesis of diethyl ester of succinic acid
Esters are widespread in nature. In particular, these compounds are responsible for pleasant aromasof flowers, fruits and berries. Low molecular weight esters, flammable liquids with low boilingpoints, are applied as solvents for varnishes and paints, flavoring additives in food industry, etc.
Esters of higher monocarboxylic acids and higher alcohols are referred to as waxes. Fats andvegetable oils, vitally important storage compounds, are esters of polyhydric alcohol glycerol andhigher carboxylic acids.

Several synthetic schemes are available for ester preparation. The acid catalyzed esterification of acarboxylic acid and an alcohol is among the most used in laboratory practice. Since the reaction isreversible, special attention should be given to shifting the equilibrium towards the ester formation.
61

IChO-2015

This can be achieved by either introduction of dehydrating agents or removal of the products (ester
and/or water) from the reaction mixture. In the case of starting compounds with relatively low
boiling points azeotropic removal of water is possible. In this work you will follow the latterapproach to ester synthesis.
O

O
H2SO4

+ 2 H3C

HO

+

OH

OH

O

H3C

-2H2O

O
O

CH3

O

Chemicals and reagents:






Succinic acid, 18 g
Ethanol (absolute), 55 mL
Toluene (dry), 24 mL
Sulfuric acid (concentrated), 0.5 mL
Potassium carbonate (calcined), 25 g

Substance

Name

State

C4H6O4

Succinic acidsolid

C2H5OH

EthanolliquidC7H8Tolueneliquid

H2SO4

Sulfuric acidaqueous solution

K2CO3

Potassium carbonate

Solid

Equipment and glassware:















Graduated cylinders, 5 and 50 mL
Round-bottom flask, 250 mLLong Vigreux distilling column with a downward condenser
Vacuum adapter
Hoses for the condenser
Glass capillaries or boiling granules
Receiver flask, 100 mL
Thermometer with a tapered joint
Magnetic stirrer with heating or hot plate
Claisen flask (150 mL) with a downward condenser
Capillary for Claisen flask
Filter paper or fritted glass filter
Beaker, 100 mL
Three-way vacuum adapter
62

GHS Hazard
Statement
H319
H315, H320, H335,
H401
H225, H304, H336,
H361, H373, H401
H302, H314, H332,
H351
H315, H319, H335,
H336

IChO-2015










Receiver, 50 mL (3 ea.)
Water-jet air pump
Manometer
Analytical balances (± 0.001 g)
Refractometer
Teflon sleeves for tapered joints or vacuum grease
SpatulaPressure nomogram

ProcedureA.

Assembly of the apparatus

Assemble the apparatus as shown in the hereunder picture. Equip every joint with the Teflon sleeveor apply vacuum grease.

4

5

6

7

3
2
1

11
10

4
8

3

9

2

5

6

7
8
9

1

10

Note: the tip of the thermometer should be positioned slightly below the outlet to the condenser.

B.

Preparation of the reagents and synthesis of the productWeigh out and admeasure the required amounts of succinic acid (18 g), absolute ethanol (55 mL),
toluene (24 mL), and concentrated sulfuric acid (0.5 mL). Place all the materials into the 250 mL
round-bottom flask.

Heat the reaction mixture constantly monitoring the temperature. The fraction with the azeotropic
mixture of the alcohol, water and toluene should start distilling off at 74-80°C. Collect the distillate
in the 100 mL receiver flask and terminate distillation (turn off the heater plate and disconnect thereceiver flask with the collected distillate). Add 25 g of calcined K2CO3 to the receiver flask to dry
the distillate. Shake the flask and leave it for 1 h. Then separate the liquid from the desiccant by
63

IChO-2015

filtration through any filter enlisted in the “Equipment and glassware” section. Place the dried
distillate back to the reaction mixture in the round-bottom flask, switch on heating and collect once
again the fraction with the azeotropic mixture of the alcohol, water and toluene distilled off at 80°C.

C.

Vacuum distillation of the residue

Label and take weights of all empty 50 mL receiver flasks. Transfer the residue from the roundbottom flask to the Claisen flask and add glass capillaries or boiling granules. Assemble theapparatus for vacuum distillation as shown in the hereunder picture. Equip every joint with the
Teflon sleeve or apply vacuum grease. Connect the vacuum line to the vacuum adapter.

4

5

6

7

3
2
1

11

4
8

3

9

2

5

6

7
8
9

1

10

Distill the residue under vacuum using the water-jet pump. Collect the fractions into the receiverflasks. Maintain the rate of distillation of about 1-2 drops of the distillate per second. Once thetemperature reaches 103°C (as read on the thermometer) at 15 mm Hg, collect about 10 drops in thefirst receiver flask and change it to the second one by turning the adaptor. Collect the fraction up to
107°C at 15 mm Hg. Then change to the third receiver flask and switch off the heating. Let theapparatus cool down before disconnecting the vacuum line and letting air in.

Note. Use the pressure nomogram to recalculate the temperatures if you observe pressure other than
15 mm Hg.

Record the pressure and the temperature of distillation.

Attention!
Never use flat-bottomed flasks as receivers!
64

IChO-2015

Always wear protective glasses or mask when doing vacuum distillation!

D.

Analysis of the productWeigh the receiver flask with the required fraction and find the mass of the product. Calculate theyield.
Determine the refractive index nD20 of the product using the refractometer. If you perform themeasurement at a different temperature, reduce the obtained value to 20 oC.

Questions
1.

What is the role of toluene in the above process?

2.

Write down the reaction mechanism.

3.

Suppose 18O-labeled ethyl alcohol and 18O-labeled tert-butyl alcohols are involved into thereactions instead of unlabeled ethyl alcohol. Which compound(s) will be the 18O atom found inwhen the reactions with the labeled alcohols are complete? Prove your choice.

Problem 33. Kinetic studies of Norfloxacin oxidation with permanganate inalkaline medium
Norfloxacin [1-ethyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinoline carboxylic acid] is asynthetic fluoroquinolone antibacterial agent of broad spectrum characterized by high activity
against many gram-positive and gram-negative bacteria. As a result of constantly increasing
administration, fluoroquinolones are expected to enter environment via waste waters. These
substances are capable of bringing serious harm to aquatic life even if present in marginal
concentrations mainly by giving rise to drug-resistant bacteria. Development of advanced oxidation
processes leading to transformation of fluoroquinolones in water is an important task ofcontemporary chemistry.

Recently it was found that Norfloxacin (NF) can be oxidized by potassium permanganate in alkaline
medium according to the following reaction:

65

IChO-2015

O
COOH

F

+ 2 MnO4- + 2 OHN
HN

N

= A

+ 2 MnO42- + H2O

Product ofoxidation

NF

According to the mass action law, the reaction rate can be expressed as:
r = k[NF]1 [MnO4 ]2 [OH  ]3

where [NF], [MnO4–], [OH–] are the concentrations of Norfloxacin, permanganate and alkali,
respectively, and 1, 2, 3 are reaction orders with respect to the corresponding reagents.

In this task you will determine the reaction orders with respect to the involved reagents following
the reaction progress photometrically at 525 nm, the wavelength of maximum absorbance of
permanganate.

Chemicals and reagents:Potassium permanganate
Sodium hydroxide
Sodium perchlorate
Norfloxacin

Substance

Name

State

KMnO4

Potassium permanganate

aqueous solution

NaOH
NaClO4
C16H18FN3O3

Sodium hydroxide
Sodium perchlorate
Norfloxacin

aqueous solution
aqueous solution
aqueous solution

GHS Hazard
Statement
H272, H302, H400,
H410
H314
H271
Not classified

Equipment and glassware:








Analytical balance (± 0.0001 g)
Visible spectrophotometer (or photometer with fixed wavelength of 525 nm) equipped withthermostated cell holder
Spectrophotometer cells with 3.5 cm optical path length (you will need to recalculate
concentrations of the reagents if you use cells with different optical path length)
Tissue to clear cell surfaces
Thermostat
PC (or other computing techniques) with Microsoft Excel software (English version)
Volumetric flasks, 100 mL (4 ea.)66

IChO-2015






Graduated cylinder, 100 mL
Volumetric pipettes, 1, 2, 5, and 10 mL
Pipette filler
SpatulaProcedureA.

Preparation of stock solutions

Read the Procedure to the end and calculate the concentrations of stock solutions of potassium
permanganate, sodium hydroxide, sodium perchlorate, and Norfloxacin that will allow easy
preparation of the reaction mixtures to be analyzed. Prepare the stock solutions of potassium
permanganate, sodium hydroxide and sodium perchlorate in the volumetric flasks according tostandard procedures. Norfloxacin suffers from poor solubility in water at neutral pH values, thus
first dissolve it in a small amount (about 6 mL) of 0.3 M alkali (in the volumetric flask) and then
add water to attain the required concentration. Do not forget to account for the amount of alkali
introduced with the Norfloxacin solution when preparing the reaction mixtures. Close the flasks
containing the stock solutions with stoppers and place them into the thermostat pre-adjusted to 25oC.

Note. Norfloxacin is commercially available as a pure reagent. Also, it can be found as aningredient in medicines. In the latter case, it is recommended to check that the other ingredients do
not interfere with Norfloxacin when it is being oxidized by potassium permanganate.

B.

General design of the task

The experimental work consists of three parts as can be seen from the hereunder table:Part 1: KMnO4 concentration is varied, concentrations of all other reagents being constant(lines 1 to 5);Part 2: Norfloxacin (NF) concentration is varied, concentrations of all other reagents being
constant (lines 6 to 10);

Part 3: NaOH concentration is varied, concentrations of all other reagents being constant(lines 11 to 16).
[MnO4–].104 М[NF].103 М[OH–].102 М[ClO4–].102 М

1

0.4

1.0

5.0

5.0

2

0.8

1.0

5.0

5.0

3

1.0

1.0

5.0

5.0

4

2.0

1.0

5.0

5.0

67

kobs

IChO-2015

5

4.0

1.0

5.0

5.0

6

1.0

0.8

5.0

5.0

7

1.0

1.0

5.0

5.0

8

1.0

4.0

5.0

5.0

9

1.0

6.0

5.0

5.0

10

1.0

8.0

5.0

5.0

11

1.0

1.0

1.0

5.0

12

1.0

1.0

2.0

5.0

13

1.0

1.0

5.0

5.0

14

1.0

1.0

6.0

5.0

15

1.0

1.0

8.0

5.0

16

1.0

1.0

10.0

5.0

C.

Determination of the reaction orders

1) Adjust the temperature of the thermostated cell unit to 25 oC.

2) Place the flasks with the stock solutions in the thermostat and let the solutions attain the desired
temperature. Check the temperatures inside the flasks from time to time with the thermometer.
Always carefully wash the thermometer with water before placing it in the next flask.

3) When ready with the temperature of the solutions, use the spectrophotometer cell to prepare themixture containing KMnO4, NaOH, and NaClO4 in concentrations as indicated in the corresponding
line in the Table. Add the Norfloxacin solution last (note that its introduction initiates the reaction)and promptly place the cell into the thermostated cell holder.

Note. If a thermostated cell holder is not available, fulfill the task at room temperature having in
mind that temperature alterations will produce only slight effect on the results of kinetic studies.
4) Immediately start recording the absorbance at the wavelength of 525 nm. Continue measuring
till the absorbance remains constant (A∞).
5) Plot the obtained data as the dependence of log(At – A∞) on time (At is the reaction mixture
absorbance at time t).
68

IChO-2015

6) Carefully wash the cell with plenty of water, dry the cell and wipe the walls with clean tissue.

7) Use the initial straight part of the curve to calculate the observed rate constant of Norfloxacinoxidation. Write down the value in the Table.

8) Repeat steps 3-7 for all the lines of the Table.

D.

Questions and Data Analysis

1a.

Propose the structure of the oxidized product A based on data given below:
mass spectrum of the product A have peaks with m/z = 335, 321, and 64;

NMR spectra (aromatic region) of Norfloxacin and the product A are as follows:

3.5

8.37

3.0
2.5
2.0
6.87
6.89

7.77
7.81

1.5
1.0
0.5
0.0
1

8.5

8.0

7.5

7.0

H NMR spectrum (300 MHz, 5% NaOD/D2O, aromatic region) of Norfloxacin

69

6.5

IChO-2015

7.08
7.10

7.73
7.77
2.0

1.5

1.0

0.5

0.0
1

8.5

8.0

7.5

7.0

6.5

H NMR spectrum (300 MHz, 5% NaOD/D2O, aromatic region) of the product A.

1b.

Explain the 1H NMR spectral pattern of Norfloxacin in the aromatic region.

2.

Propose coordinates allowing determination of the reaction order with respect to a reagent.

3.

Using the found values of kobs and compositions of the mixtures, sketch the necessary plots

and determine the reaction orders with respect to permanganate, Norfloxacin, and alkali.

Note. You are expected to fulfill this item by using the English version of Microsoft Excel software.

4.

Write down the expression for calculation of the rate of Norfloxacin oxidation withpermanganate.

The mechanism of Norfloxacin oxidation by alkaline manganese(VII) is given hereunder (B and C
are intermediates of the process).

70

IChO-2015

K1
MnO4- + OH-[MnO4OH] 2K2
B

NF + [MnO4OH] 2k1
B

C + MnO42- + H2O

slow
C + [MnO4OH]2-

k2

A + MnO42-

fast

5a. Propose the structures of B and C. Note that C is a radical.
5b. Propose the expression for the rate of Norfloxacin oxidation with permanganate according to
the above scheme.

Problem 34. Temperature dependence of the reaction rate of disproportionation
Autocatalytic reaction is a chemical process in which at least one of the reactants turns out to bealso a product. The rate equations for autocatalytic reactions are fundamentally nonlinear. Oxidationof oxalic acid with permanganate is one of famous examples of such reactions. When no
manganese(II) ions are added into the system, the reaction initially proceeds slowly. Still, at aparticular moment the rate gradually increases because the product autocatalyzes the reaction.
Addition of a few crystals of MnSO4 greatly accelerates the reduction of purple permanganate
affording a grayish-brown complex ion A. This complex ion is characterized by an extremely low
stability in water and practically immediately starts decomposing via disproportionation giving
colorless products.

The progress of the disproportionation reaction can be followed photometrically at the wavelengthof 405 nm corresponding to the maximum absorbance of the trioxalomanganesate ion. Since
potassium permanganate is rapidly and quantitatively consumed in the reaction and all the rest
substances found in the reaction mixture are colorless, the measured value of the absorbance (A) is
proportional to the complex ion concentration (c) according to Beer-Lambert-Bouguer law:A=clwhere  is the molar extinction coefficient and l is the optical path length.
71

IChO-2015

Chemicals and reagents:Potassium permanganate
Manganese(II) sulfate
Oxalic acid

Substance

Name

State

KMnO4

Potassium permanganate

aqueous solution

MnSO4
C2H2O4

Manganese(II) sulfate
Oxalic acidaqueous solution
aqueous solution

GHS Hazard
Statement
H272, H302, H400,
H410
H373, H411
H314, H318

Equipment and glassware:













Analytical balance (± 0.0001 g)
Visible spectrophotometer (or photometer with fixed wavelength of 405 nm) equipped withthermostated cell holder
Spectrophotometer cells
Tissue to clear cell surfaces
Thermostat
Thermometer
PC (or other computing techniques) with Microsoft Excel software (English version)
Volumetric flask, 100 mL, with a tight stopper (4 ea.)
Graduated cylinder, 100 mL
Volumetric pipettes, 5 and 10 mL
Pipette filler
SpatulaProcedureA.

Preparation of stock solutions

Read the Procedure to the end and calculate the concentrations of stock solutions of potassium
permanganate, manganese(II) sulfate, and oxalic acid that will allow easy preparation of thereaction mixture to be analyzed. Prepare the stock solutions of potassium permanganate,manganese(II) sulfate, and oxalic acid in the volumetric flasks according to standard procedures.

B.

General design of the task

The reactions are carried out at five different temperatures, always with the same concentrations of
the reagents (0.012 M manganese(II) sulfate, 0.085 M oxalic acid, and 0.002 M potassium
permanganate). The disproportionation progress is always followed photometrically at the
wavelength of 405 nm by detecting the decrease of the complex ion concentration. The reactions are
72

IChO-2015

first conducted at a temperature between 20 and 25 oC. When changing to new conditions, thetemperature is always increased by about 10 oC. Carefully fix the actual temperatures studied. This
will be of importance in order to get reliable results when analyzing the experimental data.

C.

Determination of the temperature dependence of the reaction rate

1) Prepare the mixture containing MnSO4 and oxalic acid in the required concentrations in thevolumetric flask.

2) Adjust the temperature of the thermostated cell unit and that of the thermostat to the required
temperature. Place the flasks with the reaction mixture and potassium permanganate stock solution
in the thermostat and let the mixture and the solution attain the desired temperature. Check thetemperatures inside the flasks from time to time with the thermometer. Always carefully wash thethermometer with water before placing it in the next flask.

3) When ready with temperatures, add the required amount of potassium permanganate stock
solution and mix well for 2-3 s. Transfer the mixture promptly to the photometer cell, place the cell
into the cell holder and immediately start recording the absorbance.

Note. The thermostated cell holder is desirable, still can be omitted, since the reaction is completed
within a short period of time. As a result, the temperature alterations will produce only slight effecton the results of kinetic studies.

4) Continue recording the absorbance till the reaction mixture turns colorless.

5) Carefully wash the cell with plenty of water, dry the cell and wipe the walls with clean tissue.

6) Repeat the steps 2-5 for the other four temperatures.

D.

Questions and Data Analysis

1.

Choose the plot which corresponds to the autocatalytic reaction (c is the productconcentration, and t is time)73

IChO-2015

a

b

c

2. Propose the formula of the ion A if it known that its charge is –3 and it contains 17.22% ofmanganese.

3.

Write down the equation of the formation of A.

4.

Write down the equation of the disproportionation of A.

5.

Graphically determine the general reaction order by testing the first and second ordercoordinates and choosing which of these provide for the best fit.

6.

For each temperature studied, draw a plot in the coordinates chosen in i. 2 and determine thevalue of the rate constant. Hint: use the initial section of plot.

7.

Calculate the activation energy of the disproportionation reaction.

Note. You are expected to fulfill ii. 5-7 by using the English version of Microsoft Excel software.

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