64.

Chemistry Olympiad
Final competition 2018
Theoretical tasks and solutions

TASK 1

The impact of protonation on precipitation equilibria

A laboratory team’s task was to evaluate the solubility product constant for a salt of a weak, diprotic
acid MX. To perform these calculation the team prepared two saturated solution of MX salt, one of
pH=7.0 and the second of pH = 6.0. It was found out that the concentration of M2+ ion in the first
solution was equal to 0.001 mol∙dm−3 while in the second one it was equal to 0.01 mol∙dm−3. Negative
logarithms of the dissociation constants of the H2X weak acid are equal: pKa1 = 10.0 and pKa2 = 13.0.
Assume that the M2+ cation does not exhibit any acidic properties and does not form any complexes
with neither HX− nor X2− ions.
Problems:
a. Derive the equation for the total concentration of H+ ions in the solution of H2X as a function of
the total concentration of this acid and its dissociation constants.
In the next step do the justified simplifications and calculate the pH of the H2X solution with the
total concentration of the acid equal to 0.1 mol∙dm−3.
b. Derive the equation for the solubility product constant of the MX salt as a function of M2+ and
H+ concentrations.
c. Calculate the solubility product constant of the MX salt using the data provided in the
introduction and using both solutions with different pH values.

An interesting example of an almost insoluble salt of a weak, diprotic acid is PbCO3. Negative
logarithm of the solubility product constant for this salt is equal to 12.8, while negative logarithms of
dissociation constants of the carbonic acid are equal to pKa1 = 6.4 and pKa2 = 10.3. The solubility of
this salt depends also on a reaction that can be written down in a simplified form as::

Pb2+ + H2O ⇄ Pb(OH)+ + H+ pKa = 7.9

1
Problems:
d. Derive the equation for the solubility product constant of the PbCO3 taking into account the
different acid-base equilibria for both anions and cations.
e. Calculate the solubility of that salt in water (pH = 7.0) and compare it to the solubility of that
salt calculated without taking into account the acid-base equilibria.

TASK 2

Electrides or not electrides?

Scientists have noticed already at the beginning of the XIX century that alkali metals can be
dissolved in liquid ammonia. The process results in the change of liquid’s colour from colourless
to dark navy. Detailed investigations of the obtained solutions’ structure revealed that at low metal
concentrations there are solvated cations in the solution, e.g. Na(NH3 )+6 in case of sodium
dissolution, and solvated electrons – e(NH3 )−
6
– localised in relatively large voids of the solvent
structure. Similar phenomena take place upon alkali metals dissolution in some organic solvents
(e.g. primary amines or dimethyl ether). The formed ionic compounds in which electrons are
anions are called electrides.
In other words electrides consist of cations and electrons which are not bound to any atomic cores.
The solvents used for the synthesis of electrides must be able to solvate
O free electrons and cannot be prone to reduction (for instance, due to kinetic
O O hindrances). Organic compounds which form stable complexes with alkali
metal cations are often added to the solvents in order to increase the alkali
O O metals solubility. 1,4,7,10,13,16-hexaoxocyclooctadecane – a crown ether
O denoted 18C6 and whose structure is presented in the scheme is one of
such compounds.
Samples of metallic caesium and 18C6 crown ether mixed in 1:1 molar ration were prepared and
dissolved in dimethyl ether at −15°C. Deeply coloured solution was obtained and a portion of
trimethylamine of similar quantity to that of dimethyl ether was added to it. Subsequently,
dimethyl ether was evaporated from the solution until dark blue, needle-shaped crystals of
compound A began to precipitate at −10°C. Analogous synthesis was carried out but the molar
ration of caesium to 18C6 crown ether was 1:2,3 and black, shiny, plate-like crystals of compound
B were formed. Both compound are stable at room temperature in vacuum.
123 mg of compound A were carefully reacted with water at low temperature. Care was taken so
that the temperature would not rise and the formed organic compounds would not decompose.
3,84 mL of colourless, flammable gas X whose density is almost 15 times smaller than the density
of air were evolved. The volume was measured at 25°C and 1000 hPa. Then, the obtained solut ion
was titrated with hydrochloric acid solution of 0.0100 mol∙L −3 concentration and 31.0 mL of
2
titrant were used. The solution was evaporated to dryness after titration and the residue was
dissolved in 2.0 mL of deuterated water D 2O together with 1.0 mmol of tert-butyl alcohol (t-
BuOH). The obtained solution was analysed by 1H NMR at room temperature. No signals coming
from dimethyl ether or trimethylamine were observed in the spectrum and the ratio of peak areas
coming from 18C6 crown ether protons and protons from t-BuOH methyl groups was 0.826. In the
course of analogous analysis of 138 mg of compound B 2.59 mL of gas X were evolved, 20.9 mL
of 0.0100 mol∙L−3 hydrochloric acid solution were used and the intensity ratio of signals coming
from 18C6 crown ether methylene groups and from t-BuOH methyl groups in the 1H NMR
spectrum was 1.11. No peaks coming from other substances were observed in the 1H NMR
spectrum either. There are two signals in the 133Cs NMR spectrum of solid compound A whereas
there is only one in the spectrum of solid compound B. It was also found that compound A is
diamagnetic while compound B is paramagnetic. The band gap of both compounds was
determined and they were both found to be semiconductors.
Problems:
a. Write down the name and chemical formula of gas X.
b. Write the structural formula of tert-butyl alcohol. How many signals coming from methyl group
protons are there in the 1H NMR spectrum of this alcohol’s solution recorded at room
temperature? How many signals are there in the 1H NMR spectrum of 18C6 crown ether
recorded at room temperature? What would be the intensity ratio of the signals coming from
methyl group protons of tert-butyl alcohol and 18C6 crown ether, if they were mixed in 1:1
molar ratio? Justify your answers.
c. Write down the empirical (sum) formulae of compound A and B. Justify your answer and
confirm it with appropriate calculations.
d. Write down the ions present in compounds A and B. Which of the compounds are electrides?
Justify your answer.
e. Write down the equations in molecular form of chemical reactions of compounds A and B with
water. Write also appropriate half reactions and name the oxidising and reducing agents in each
reaction.
f. Write down the equation in molecular form of the chemical reaction taking place in absence of
oxygen and moisture between compound A and anhydrous gold(III) chloride dissolved in
dimethyl ether. Red colloidal solution is formed as a result of this reaction.

Denote the crown ether molecule 18C6 to simplify your answers.

Use the following values of molar masses in your calculations (g∙mol−1):
H – 1.008; C – 12.01; O – 16.00; Cs – 132.91.
Gas constant R = 8.3145 J∙mol−1∙K−1
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 TASK 3

Determination of the polymer molecular weight by the measurements of osmotic pressure

The equation describing the dependence of osmotic pressure π on concentration of solution c,
resembles in its form the ideal gas equation (Clapeyron equation). Just as the Clapeyron equation
describing the relationship p(V) is fulfilled only for gases of low density, the equation π(c) describes
well only the very dilute solutions (c → 0). It means that the dependence of osmotic pressure of real
solutions on their concentrations is not linear and shows significant deviations from the well-known
equation.
The osmotic pressure for polymer solutions of known concentrations as measured against a pure
solvent can be used to determine the average molecular weight, Mav, of dissolved polymer. However,
since different results of measured molecular weights are usually obtained for different
concentrations, it is necessary to perform several measurements for a set of concentrations, ci,
calculate the resulting apparent molecular masses, Mi, and extrapolate these values to the
concentration c = 0. The dependence of M(c) is obviously not linear, so, if we do not know the exact
relation of M(c), then a simple extrapolation of the values Mi to c = 0 is not possible.
A reaction of radical polymerization of styrene was carried out to determine the dependence of
polymer molecular weight on duration time of the polymerization. In the flask, under atmosphere of
pure argon, the amount of 10.414 g of degassed and inhibitor-free styrene and small amount of
benzoyl peroxide as the initiator of the radical chain reaction (in a molar ratio of 1:100) were placed.
The reaction was carried out at 120° C and after an appropriate time delay, the reacting mixture was
rapidly quenched in ice to stop the reaction.
The post-reaction mixture was divided into several samples, which were subjected to further testing.
The sample of 5.678 g was evaporated under vacuum at a sufficiently low temperature, yielding 3.456
g of dry polymer. Each of the four successive samples of the post-reaction mixture with identical
polymer concentrations, c, and masses, m, listed below in Table 1 were dissolved in toluene in the
measuring flasks and diluted with toluene to the volume of 100 cm3. The solutions were used for the
measurements of their osmotic pressure against the pure solvent, i.e. toluene. The difference in the
levels of liquids in both arms of the osmometer, h, was measured. The results are summarized in
Table 1.
Table 1
1 2 3 4
m [g] 1.200 0.900 0.600 0.300

h [cm] 3.57 2.26 1.17 0.43

4
The experiments were carried out at t = 30.85 °C. The density of toluene at this temperature is
d = 0.8566 g∙cm−3 and it can be assumed that the density of polymer solutions is the same. Due to the
very small diameter of the capillaries in the arms of the osmometer, we omit the effect of diluting the
solution with a solvent passing through the semi-permeable membrane; the h values given in Table 1
are already corrected for the capillarity effect.
Note: benzoyl peroxide is decomposed to benzene during the reaction; in osmometric measurements,
it can be assumed that the molecules of styrene and toluene are of the same size.
In the calculations, take the following values of molar masses (g∙mol−1): C – 12.010, H – 1.008; the
value of the gravitational acceleration is g = 9.81 m/s2.
Problems:
a. For all four given solutions calculate the concentration, c in g∙dm−3, of polymer and the osmotic
pressure π, determined in individual measurements. Put the results into Table 2 in the solutions
sheet.
b. Using the grates in sheets, make a plot of the calculated dependence π(c) inserting also the point
at c = 0. Note: on the scale with resolution 1 you can insert points with a precision of ± 0.1.
c. From the equation describing the dependence of π(c), drive the formula for the dependence of the
molecular weight, M, of the polymer on π, c and T.
d. Calculate the molecular weight Mi of the polymer at each of the four experiments and insert the
results in Table 2 on the first page of the solution sheet.
e. Find the function f(M), which is a linear function of the concentration c and allows for an
extrapolation of f(M) to c = 0. Calculate the values of function f(Mi) for each individual
concentration of polystyrene and place them in Table 2.
Note: analysis of the results have shown that the dependence of the osmotic pressure of polystyrene
solutions on their concentration has the form: π(c) = A∙c + B∙c2.
f. Similarly to the b., plot the calculated values of f(Mi) as a function of the concentration c. Draw the
straight line as close as possible to all points and extrapolate this linear dependence to the
concentration c = 0.
g. From the two most distant points on the graph of f(M) plotted as a function of the concentration
c (plot from f.), calculate the parameters "a" and "b" of the straight line approximating
experimental points and used for extrapolation to the concentration c = 0. Calculate the value of
function f(M) for c = 0 and the resulting mean value of the average molecular mass, Mav, of
polystyrene.
Hint: instead of calculating the parameters of the straight line through the two chosen points, you
can apply for all four points the linear regression function available in the calculator.

5
 h. Calculate the degree of polystyrene polymerization as the ratio of the calculated average molecular
weight of polystyrene Mav to the molecular weight of the monomer Mm. Calculate the extent of the
reaction, λ, achieved in the system at the moment of "freezing" of the polymerization reaction.
Note: the extent of reaction, λ, is defined as the ratio of the number of moles of substrate or product
that has been used or produced in the reaction till the moment when the reaction is stopped to the
appropriate stoichiometric coefficient:

λ = (nz − n0)/z
where: nz - number of moles of the particular reactant z at the moment of stopping the reaction,
n0 - initial number of moles of the reactant (for the product n0 = 0), z - stoichiometric coefficient of
the reactant (for the substrate a negative value should be taken).

TASK 4

Identification of aromatic compounds

Benzene, five-membered and six-membered heterocyclic aromatic compounds belong to most
important structural motifs present in many relevant organic compounds - synthetic as well as
naturally occurring products.
Six aromatic or heteroaromatic compounds (A-F) along with products of further reactions are
described below. Selected information based on the nuclear magnetic resonance (NMR) useful for
identification process are shown in the table:

Compound: A B, B1, B2 C D, D1 D2 E F G H I X
Number of signals in
13 4 7 5 7 4 2 2 6 9 13 16
C NMR spectra
1
H NMR spectra (in CDCl3): Signals in the range of 0-5 ppm are present only for compounds B,
D1, D2, F and X.

I) Compounds A and B are hydrocarbons having the same composition. They contain 93.5% of
carbon, and the molecular mass do not exceed 200 g∙mol−1. A and B do not decolourise bromine
water, however react with bromine in the presence of iron. Moreover, only B can be oxidized when
heated with Na2Cr2O7 or KMnO4 solutions, to form products B1 and B2 with molecular mass of 198
and 216 g∙mol−1 respectively.
a. Determine molecular formula of hydrocarbons A and B.
b. Draw the structures of hydrocarbons A and B.
c. Draw the structures of compounds B1 and B2.

6
II) Compounds C and D have a molecular weight of 122 g∙mol−1 and beside carbon and hydrogen
contains also oxygen (26.2%). They can be easily separated by extraction of C with diluted solution
of NaOH. Compound C also reacts with thionyl chloride to form C1. Reaction of D with NaBH4, and
selective reduction with hydrogen on palladium catalyst leads to achiral product D1 with molecular
weight of 126 g∙mol−1. In 1H NMR spectra of D1 there are three multiplets with relative intensity
1:1:1 in the range of 6-7.5 ppm. Further reduction of D1 with hydrogen on nickel catalyst with acid
additive resulted in formation of product with molecular weight of 130 g∙mol−1 and D2 with 128
g∙mol−1. The 13C NMR spectra of D2 shows four peaks, and at proton spectrum only signals with
chemical shifts below 5 ppm are present. In addition, compounds D reacts with cyclopenta-1,3-diene.
d. Determine molecular formula of compounds C and D.
e. Draw the structures of compounds C and C1.
f. Draw the structures of compounds D, D1 and D2.
III) Compounds E and F exhibit basic properties, and beside carbon and hydrogen contains 41.2% mas.
and 25.9% mas. of nitrogen respectively. They molecular masses do not exceed 130 g∙mol−1, and 13C
NMR spectra shows only two signals for each compound. Moreover, E is also a weak acid (slightly
stronger then water), and reacts with 2 moles of C1 in the presence of NaOH solution with ring
opening and formation of product G and simple carboxylic acid salt. G contains 10.5% of nitrogen
and has a molecular weight of 266 g∙mol−1. Compound F heated with excess of B1 forms product H
with molecular weight of 468 g∙mol−1, which has no basic properties.
g. Determine molecular formula of compounds E and F.
h. Draw the structures of compounds E and F.
i. Draw the structures of compounds G and H.

IV) Compounds A, C and E were utilized in the synthesis of antifungal drug X, illustrated at the
scheme:

E
SOCl2 A 1) NaBH4 (excess)
C C1 I J X
AlCl3 2) SOCl2

j. Draw the structures of compounds I, J and X.

Use atomic masses of elements (g∙mol−1): H - 1; C – 12; N – 14; O - 16

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 TASK 5

Bacteria with off-on switch

Bioorthogonal reactions are organic reactions that can performed on biomolecules present in living
organisms without perturbing the basic function of those organisms. Bioorthogonal chemistry is focused
on developing reactions that can be carried out in water, at physiological pH (6.5-8), at temperature of 30-
37 °C, and in a selective manner, preferably without catalyst, and without toxic by-products. A typical
bioorthogonal reaction is carried out between two functional groups, which normally do not occur in
Nature. To carry out the reaction in a living bacterial cell, one of the reacting group must be beforehand
introduced into bacterial biomolecule (e.g. polysaccharide or protein). In this problem, you will get
familiar with one of the known biorthogonal reactions and learn how it can be used to control light
emitting properties (fluorescence) of bacteria.
To carry out bioorthogonal metabolic labelling of green fluorescent protein (GFP-1) in bacterial cells, an
unnatural amino acid X was synthesized as depicted (Fig. 1).

Fig.1
The starting point for the synthesis of amino acid X was natural proteinogenic aromatic amino acid A.
Amino acid A subjected to a mixture of concentrated nitric and sulfuric acid gave para-substituted
derivative B. Derivative B was treated with di-tetr-butyl dicarbonate to yield compound C. Compound C
was reacted with hydrogen on a palladium catalyst to give compound D (M=280,32 g∙mol-1). Compound
D reacts with compound K leading to derivative E. A by-product of this reaction is volatile compound
with pungent odour. Derivative E is deprotected under acidic conditions to yield amino-acid X
(M=274,28 g∙mol-1).

Fig.2
The first step of the synthesis of compound K (mol. Formula C4H6N4S) is refluxing thiohydrocarbazide in
methanol, to yield monomethylated derivative J (Fig. 2). Condensation of derivative J with
trimethylacetate in ethanol, in the presence of triethylamine, followed by addition of sodium nitrite in the
presence of acid as a mild oxidant, leads to compound K as the main product. Compound K is a cyclic,
aromatic compound, which does not undergo dimerization in the presence of mild oxidants. In the proton

8
NMR spectrum of compound K there are two signals (singlets od equal intensities, for both δH is below 4
ppm) and in the carbon spectrum there are 4 signals.

Fig.3
Aminoacid X was added to growth medium, in which genetically engineered E.coli strain was cultured.
The bacteria incorporated single amino acid X into GFP-1 protein that they expressed. Such modified
GFP-1 protein did not emit light (was non-fluorescent; Fig. 3). Next, compound Y was added to the
bacterial culture. Just after 1 minute fluorescence of the bacteria was observed, indicating that a rapid
chemical reaction occurred with participation of the modified GFP-1 protein. The first step of this reaction
is [4+2] cycloaddition between amino acid X present in the protein and compound Y, leading to the
formation of GFP-2 adduct that contains a modified amino acid Z’. GFP-2 protein spontaneously
converts into GFP-3 that contains amino acid Z, and a non-toxic gas is released during this process.
MALDI-MS analysis revealed that conversion of GFP-1 into GFP-3 results in a change of protein
molecular mass by 124 g∙mol-1. The structure of compound Y, not showing its stereochemistry, is
depicted in Fig. 3. The double bond in compound Y has E configuration, and one of the substituents in the
cyclopropane ring has configuration trans relative to other substituents. Finally, catalytic hydrogenation of
compound Y leads to mezo compound.

Problems:
a. Draw structural formula for compounds B, C, and D. You do not need to show the
stereochemistry.
b. Draw structural formula for compounds E, K, and X. You do not need to show the
stereochemistry.
c. Draw the structural formula of Y clearly showing its stereochemistry.
d. Draw a scheme for the reaction between protein GFP-1 and compound Y. In your scheme, use
skeletal formula of amino acids Z and Z’ (you do not need to show stereochemistry). Depict
the protein schematically in such way that amino acid X is fully shown, including the peptide
bonds it engages in. N-terminal part of the protein label as R1 and C-terminal as R2. If you
cannot draw the protein, draw the same reaction for the free amino acid X Draw the structure
of appropriate isomer of chloronicotinic acid, oxidation product of compound X.

9
e. Rapid reaction between amino acid X and compound Y is ensured by the presence of double
bond of E-configuration in compound Y. This is related to (choose one answer):
A. Steric hindrance
B. Electronic effects
C. Angular strain
D. Lack of interactions with the hydroxyl group

f. Reaction between compounds X and Y is often called inverse electron demand Diels-Alder reaction
(iEDDA). This is because:

A. The participating diene is electron-rich, whereas the dienophile is electron-poor.

B. The participating diene is electron-poor, whereas the dienophile is electron-rich.
C. The LUMO orbital of the diene has much higher energy than HOMO of the dienophile.
D. The LUMO orbital of the dienophile has much higher energy than HOMO of the diene.

g. The Diels-Alder reaction is usually reversible. What makes the reaction analyzed in this problem
irreversible, especially, at low reagent concentrations present in the living cells?

10
 Solutions of theoretical Tasks
SOLUTION OF TASK 1
a.
H2X ⇄ HX− + H+ pKa1 = 10.0
HX-⇄ X2− + H+ pKa2 = 13.0
Ka1 and Ka2 dissociation constants are defined as:
Ka1 = [HX−][H+] / [H2X]
Ka2 = [X2−][H+] / [HX−]
and the total concentration of H+ ions [H+]c is equal to the concentration of both stages of dissociation:
[H+]c = [H+]1 + [H+]2
[H+]1 can be calculated on the basis of the first step of dissociation solving the quadratic equation:
[H+]12 + Ka1·[H+]1 – Ka1·c = 0

−𝑲𝐚𝟏 + √𝑲𝐚𝟏 𝟐 + 𝟒𝑲𝐚𝟏 · 𝒄

[𝐇 + ]𝟏 =
𝟐
[H+]1 = 3.1·10−6 mol∙dm−3
Calculating [H+]2 is more complex, as it depends on the first step of dissociation. We can, however,
note that:
[H+]2 = [X2−]
and the concentration of of [HX−] ion can be written as:
[HX−] = [H+]1 – [H+]2
Substituting these equations into the Ka2 equation gives us::
([H + ]1 + [H + ]2 )[H+ ]2
𝐾a2 =
[H + ]1 − [H+ ]2

And finally:

[𝐇 + ]𝟐 = 𝟏/𝟐(−𝑲𝐚𝟐 − [𝐇 + ]𝟏 + √(𝑲𝐚𝟐 + [𝐇 + ]𝟏 )𝟐 + 𝟒𝑲𝐚𝟐 [𝐇 + ]𝟏

where:

−𝑲𝐚𝟏 + √𝑲𝐚𝟏 𝟐 + 𝟒𝑲𝐚𝟏 · 𝒄

[𝐇 + ]𝟏 =
𝟐

11
 If the difference between [H+]1 and [H+]2 concentration values is large (meaning that Ka2 is a lot
smaller than [H+]1 or Ka2 is a lot smaller than Ka1), which we can note as [H+]1 + [H+]2 ≈ [H+]1 then
Ka2 ≈ [H+]2,
so:
[H+]c = [H+]1 + [H+]2 ≈ [H+]1 + Ka2
and finally:
[H+]c = 3.1·10−6 mol∙dm−3+ 10−13 mol∙dm−3 ≈ 3.1·10−6 mol∙dm−3
pH = 5.5
b.
MX ⇄ M2+ + X2−
KS0 = [M2+][X2−]
In the absence of ions of insoluble salt we can note that:
[M2+] = S and [X2−] = S, to yield KS0 = S2
S = (KS0)1/2
X2− ion is, however, a weak base described by the following equilibria:
H2X ⇄ HX−+ H+ pKa1 = 10.0
− 2− +
HX ⇄ X + H pKa2 = 13.0

described by the following dissociation constants Ka1 and Ka2:

Ka1 = [HX−][H+] / [H2X] czyli [H2X] = [HX−][H+] / Ka1
Ka2 = [X2−][H+] / [HX−]
Solving the second equation we get: [HX−] = [X2−][H+] / Ka2
Solving the first equation we get: [H2X] = [HX−][H+] / Ka1 = [X2−][H+]2 / Ka1Ka2.
If the solubility products constant of the MX salt is equal to KS0 = [M2+][X2−], then the actual
molar solubility S of this salt can be describes as::
[M2+] = S
[H2X] + [HX−] + [X2−] = S

Using the second equation we get:

[X 2− ][H+ ] [X 2− ][H+ ]2 [H + ] [H + ]2
𝑆 = [X 2− ] + ( )+( ) = [X 2− ] (1 + + )
𝐾a2 𝐾a1 𝐾a2 𝐾a2 𝐾a1 𝐾a2
𝑆
[X 2− ] =
[H + ] [H + ]2
1+ +
𝐾a2 𝐾a1 𝐾a2
And finally the solubility products constant of the MX salt is equal to:

12
 𝑺
𝑲𝑺𝟎 = 𝑺 ·
[𝐇 + ] [𝐇 + ]𝟐
𝟏+ +
𝑲𝐚𝟐 𝑲𝐚𝟏 𝑲𝐚𝟐
c. Using the equation derived above at pH = 7.0 we get:

𝑆 −3
10−3
𝐾𝑆0 = 𝑆 · ( ) = 10 · ( ) = 𝟏𝟎−𝟏𝟓
[H + ] [H + ]2 10−7 (10−7 )2
1+ + 1 + −13 + −10 −13
𝐾a2 𝐾a1 𝐾a2 10 10 10
d. Using the same equation at pH = 6.0 we get:

𝑆 −2
10−2
𝐾𝑆0 =𝑆·( + + 2 ) = 10 · ( −6 2 ) = 𝟏𝟎−𝟏𝟓
[H ] [H ] 10 −6 (10 )
1+ + 1 + −13 + −10 −13
𝐾a2 𝐾a1 𝐾a2 10 10 10

e. For anions all equation were already derived above. In the case of M2+ cation we find the
following equilibrium:
Pb2+ + H2O ⇄ Pb(OH)+ + H+ pKa = 7.9
Ka = [Pb(OH)+][H+] / [Pb2+] czyli [Pb(OH)+] = Ka·[Pb2+] / [H+]
Since lead ions exist in two forms, the molar solubility is equal to the sum of their concentrations:
[Pb2+] + [Pb(OH)+] = S
Using this equation we get:
[Pb2+ ]𝐾a 𝐾a
𝑆 = [Pb2+ ] + = [ Pb2+ ]
(1 + )
[H + ] [H + ]
𝑆
[Pb2+ ] =
𝐾a
(1 + )
[H + ]
For anions we have:
[H2X] + [HX−] + [X2−] = S
To finally yield:

2− ]
[X 2− ][H+ ] [X 2− ][H+ ]2 2−
[H + ] [H+ ]2
𝑆 = [X +( )+( ) = [X ] (1 + + )
𝐾a2 𝐾a1 𝐾a2 𝐾a2 𝐾a1 𝐾a2

𝑆
[X 2− ] =
[H + ] [H+ ]2
1+ +
𝐾a2 𝐾a1 𝐾a2

13
Using the equation derived for the concentrations of M2+ and X2- ions we can write the final equation
for the solubility product constants as:
𝑆 𝑆
𝐾𝑆0 = ·
𝐾a [H+ ]
[H + ]2
1+ 1 + +
[H + ] 𝐾a2 𝐾a1 𝐾a2
f. Using the equation derived above we get:
𝐾𝑆0
𝑆2 =
𝐾 [H + ] [H+ ]2
(1 + a+ ) (1 + + )
[H ] 𝐾a2 𝐾a1 𝐾a2
2
10−12,8
𝑆 = = 4.4 · 10−8
10−7.9 10−7 10−14
(1 + ) (1 + −10.3 + −6.4 −10.3 )
10−7 10 10 10
S = 2.1·10-5 mol∙dm−3

Without using the acid-base equilibria for ions the solubility of that salt in water would be equal to:
S = (KS0)1/2 = 4·10−7 mol∙dm−3

SOLUTION OF TASK 2
a. X – hydrogen, H2
b. The structural formula of tert-butyl alcohol:

OH

All methyl groups rotate freely around the C−C bond axis at room temperature in solution and
hydroxyl group also rotates around the C−O bond. Consequently, all methyl group protons are
equivalent and there is only one signal (singlet) coming from them in the 1H NMR spectrum.
Similarly methylene groups of 18C6 crown ether also rotate freely in solution at room
temperature and all protons in the 18C6 molecule are equivalent and give rise to one signal (also
singlet).
When t-BuOH and 18C6 are mixed in a 1:1: molar ratio, the molar ratio of methyl group protons
of t-BuOH and 18C6 ether protons equals (1 ∙ 9)a : (1 ∙ 24) = 0,375. This ratio is equal to the
intensity ratio of respective signals in the 1H NMR spectrum.
a
– the number of moles of a particular compound multiplied by the number of equivalent nuclei
of a given type
c. It follows from the information concerning the 1H NMR spectra for samples resulting from
compounds A and B dissolution in water that they consist of caesium and 18C6 crown ether only.

14
 One may calculate the amount of crown ether in the sample of compounds A and B basing on the
intensity ration of the signals coming from tert-butyl alcohol protons and crown ether protons.
There is 1.0 mmol of tert-butyl alcohol i.e. 9.0 mmol of methyl group protons in the analysed
solution. Given that the signal intensity ratio is 0.826, there are 0.826 ∙ 9.0 = 7.43 mmol of crown
ether protons in 123 mg of compound A. One 18C6 crown ether molecule contains 24 protons.
Therefore, 123 mg of compound A contains 7.43 / 24 = 0.310 mmol of 18C6 ether. The 18C6
ether molar mass of the formula C12H24O6 equals 264.31 g∙mol−1 which indicated that 123 mg of
compound A contains 0.310 mmol ∙ 264.31 g∙mol−1 = 81.9 mg of 18C6 ether and 41.1 mg of
caesium which amount to 0.309 mmol.
Thus, the Cs:18C6 molar ratio is 0.309 mmol : 0.310 mmol ≈ 1:1 and the empirical (sum) formula
of compound A is Cs(18C6) or Cs(C12H24O6).
In case of compound B analysis there is also 9.0 mmol tert-butyl alcohol methyl group protons in
the solution, but there are 9.0 ∙ 1.11 = 9.99 mmol of 18C6 ether methylene group protons which
amounts to 9.99 / 24 = 0.416 mmol of 18C6 ether. Such an amount of ether weighs 0.416 mmol ∙
264.31 g∙mol−1= 110 mg. There are 28 mg of caesium in 138 mg of compound B.
Therefore, the Cs:18C6 molar ratio is 0.211 mmol : 0.416 mmol ≈ 1:2 and the empirical (sum)
formula of compound B is Cs(18C6)2 or Cs(C12H24O6)2.
Any other correct reasoning allowing for the unequivocal determination of compounds A and B
empirical formulae will receive maximum number of points.
d. In the course of compound B analysis 2.59 mL of hydrogen were evolved. The number of moles of
hydrogen can be calculated using Clapeyron equation:
𝑝𝑉
𝑝𝑉 = 𝑛𝑅𝑇 ⇒ 𝑛 =
𝑅𝑇
100000 Pa ∙ 2.59 ∙ 10−6 m3
𝑛= = 0.104 mmol
8.3145 J ∙ mol−1 ∙ K −1 ∙ 298.15 K
Hydrogen is formed as a result of hydronium cations reduction which proceeds according to the
following half reaction:
2H2O + 2e− → H2 + 2OH−
0.208 mmol of electrons had to react for 0.104 mmol of gaseous hydrogen to be formed. This
indicates that there is 0.208 mmol/0.211 mmol = 1,0 mol of electrons per 1 mol of caesium in
compound B. Moreover, the presence of only one peak in the 133Cs NMR spectrum indicates that
there is only one kind of caesium nuclei in this compound and the information about the
paramagnetic properties of compound B shows that it contains unpaired electrons. One may,
therefore, conclude that compound B contains caesium cations complexed by the crown ether:

15
 Cs(18C6)+2 lub Cs(C12 H24 O6 )+2 ) and electrons e− instead of anions. Compound B is an electride
with formula [Cs(18C6)+2 , e−].

Analogously, in case of compound A analysis 3.84 mL of hydrogen were formed. This amounts to
100000 Pa ∙ 3.84 ∙ 10−6 m3
𝑛= = 0.155 mmol
8.3145 J ∙ mol−1 ∙ K −1 ∙ 298.15 K
Here 0.310 mmol of electrons had to react for such an amount of hydrogen to be evolved. This
means that there is 0.310 mmol / 0.309 mmol = 1.0 mol of electrons per 1 mol of caesium in
compound A. Compound A is paramagnetic which indicates that all electrons are paired therein.
There are two signals in the 133Cs NMR spectrum. One must come from nuclei of caesium cations
complexed by crown ether: Cs(18C6)+2 (or Cs(C12 H24 O6 )+2 ). The second one comes from caesium
nuclei in a different chemical environment. Given that there are electron pairs in the compound,
one may conclude that there is one electron pair per one such caesium atomic core. Thus, the
second signal comes from caeside anions Cs−. In the compound A structure there are no free
electron pairs instead of anions, because there is a second signal in the 133Cs NMR spectrum in
addition to the signal coming from cations. The signal stemming from caeside anions is displaced
relative to the signal coming from Cs(18C6)+2 cations because the electron pair is localised on the
6s orbital which implies non-zero probability of finding these electrons on the caesium nucleus of
the caeside anion. Summing up, compound A is not an electride but a salt with formula
[Cs(18C6)+2 , Cs− ].

This is an example of quite a big group of alkali metal alkalides obtained using a series of
complexing agents forming stable chelates with these metal cations.
e. The reaction of compound A with water:

[Cs(18C6)+2 ,Cs− ](s) + 2H2O(l) → 2CsOH(aq) + 2 18C6(aq) + H2(g)

Half reactions: Agent

− + −
oxidation: Cs → Cs + 2e reducing: Cs−
reduction: 2H2O + 2e− → H2 + 2OH− oxidising: H2O
The reaction of compound B with water:

2[Cs(18C6)+2 ,e− ](s) + 2H2O(l) → 2CsOH(aq) + 4 18C6(aq) + H2(g)

(or [Cs(18C6)+2 ,e− ](s) + H2O(l) → CsOH(aq) + 2 18C6(aq) + ½ H2(g))

Half reactions: Agent

oxidation: isolated electrons from electride are the reducing: e−
reducing agent
reduction: 2H2O + 2e− → H2 + 2OH− oxidising: H2O

16
 The following equations are also correct:

[Cs(C12 H24 O6 )+2 ,Cs− ](s) + 2H2O(l) → 2CsOH(aq) + 2C12H24O6(aq) + H2(g)

2[Cs(C12 H24 O6 )+2 ,e− ](s) + 2H2O(l) → 2CsOH(aq) + 4C12H24O6(aq) + H2(g)

or:
2Cs(C12H24O6)(s) + 2H2O(l) → 2CsOH(aq) + 2C12H24O6(aq) + H2(g)
2Cs(C12H24O6)2(s) + 2H2O(l) → 2CsOH(aq) + 4C12H24O6(aq) + H2(g)
f. Gold(III) cations are reduced by caeside anions to metallic gold according to the following
equation:

2AuCl3(ether) + 3[Cs(18C6)+2 ,Cs− ](ether) → 2Au(ether) + 3[Cs(18C6)+2 ,Cl− ](ether) + 3CsCl(ether)

or
2AuCl3(ether) + 6Cs(C12H24O6)(ether) → 2Au(ether) + 3Cs(C12H24O6)2Cl(ether) + 3CsCl(ether)
or another equivalent equation.
Using this method one may obtain metal nanoparticles with diameters ranging from 1 to 19 nm.

SOLUTION OF TASK 3
Table 2:
1 2 3 4
c (g∙dm−3) 7.304 5.478 3.652 1.826

π (Pa) 300 190 98 36

Mi (g∙mol−1) 61500 72860 93830 127700

M−1∙105 / (mol∙g−1) 1.6260 1.3724 1.0658 0.7834

a. From the mass of the post-reaction mixture contained in V = 100 cm3 of the solution and knowing the
ratio of the polymer mass to the mass of the reaction mixture we calculate the concentration c:
c = m∙3.456∙/(V∙5.678). (1)
An osmotic pressure, π, in the present experiments is a hydrostatic pressure of the solution column
raised in a capillary of the osmometr to the height h. We use the formula:
π = d∙g∙h (2)
where: d - density of the solution at a given temperature (here, the density of toluene), g - acceleration
of gravity, and h - difference in levels of the liquid column in the arms of the osmometer. The
calculated values of c and π (after conversion of units) are inserted in Table 2 above.

17
 It should be noted that the unreacted molecules of styrene present in the solution (as well as the
negligible amount of benzene produced in decomposition of benzoyl peroxide) will behave like
toluene (solvent) due to their very close molecular sizes. In these measurements they behave as the
substances which are not osmotically active and do not contribute to the measured osmotic
pressure. The osmotic pressure measured is solely due to the presence of large polymer molecules.

Fig.1. Dependence of osmotic pressure on concentration of the polystyrene solutions.

b. The graph π(c) should look as shown above in Figure 1 (competitors do not have to plot a
fitted curve describing the relationship π(c) = A∙c + B∙c2).
c. The data given in the problem are: concentration of polystyrene, c [g∙dm−3], osmotic pressure π [Pa], and
temperature t [° C]. Temperature of the experiment in Kelvin scale is T = 30.85 ° C + 273.15 K = 304.00 K.
The osmotic pressure π as a function of molar concentration, cm, is described by the formula:
π = cm∙R∙T (3)
The molar concentration, cm, we calculate as: cm = c/M, where M is the molecular weight (in
[g∙mol−1]) of the polystyrene. Inserting above expression into formula (3) we get:
π = c∙R∙T/M (4)
Transformation of equation (4) to the form „M as a function of c” leads to:
M = c∙R∙T/π (5)
d. Using equation (5), we calculate the "apparent" molecular weight, Mi, of the polystyrene and
introduce them into the Table 2.
e. Taking advantage of the given note: π(c) = A∙c + B∙c2 we can write an equality of this relationship
and the relationship described by equation (4):
π = c∙R∙T/M = A∙c + B∙c2 (6)
After dividing of both sides of the equation (6) by c (with the assumption that c ≠ 0) it can be
noticed that the inverse of the molecular weight must be described by a straight line:

18
 M−1 = a + b∙c , (7)
where: a = A/R∙T and b = B/R∙T .
The function we were looking for is f(M) = M−1(c). We calculate the inverse values of Mi and
place them in Table 2.
f. We make a graph f(M) = M−1(c). The calculated points show a linear dependence on the
concentration of polystyrene. We extrapolate a straight line through experimental points to the
value of M−1(c = 0), as shown in Figure 2 below.

Fig. 2. Dependence of the inverse "apparent" molecular weight 1/M(c) on the concentration of
polystyrene
g. The equation of the straight line calculated with a least squares method has the form:
M−1 = a + b∙c (8)
and the parameters of this equation are: a = 0.5033∙10−5 mol∙g−1 and b = 0.1553∙10−5 mol∙g−1∙K−1.
The value of M−1 at the concentration c = 0 is equal to the constant „a”, which gives the average
value of the actual molecular weight of polystyrene equal to:
Mav = 198700 g∙mol−1.
The straight line calculated from the two extreme points In Fig. 2 has the parameters a = 0.5025∙10−5
mol∙g−1 i b = 0.1538∙10−5 mol∙g−1∙K−1. The reciprocal of the "a" parameter gives an average
molecular weight of 199000 g∙mol−1. The small difference between these two calculations
indicates good linearity M−1(c).
h. The reaction of polymerization can be written as:

 C8H8 + 2 H* → H−(C8H8)−H
The molecular weight of styrene is Mm = 104.144 g∙mol−1. The degree of styrene polymerization is
therefore:

19
  = Mav/Mm = 198700/104.144 ≈ 1908
The extent of the reaction, λ, we calculate from the definition taking into account the number of
moles of styrene, which has reacted until the reaction was frozen:

λ = (nz – n0)/ (10)

where: nz - number of moles of styrene at the moment of stopping the reaction, n0 - initial number
of moles of styrene,  - stoichiometric coefficient of the reactant (here: styrene for which we take a
negative value as for the substrate). The number of moles used for the reaction is
n0 = 10.414g/104.144 g∙mol−1 = 0.100 mole.
The remaining amount of unreacted styrene is calculated as:
nz = 10.414g∙(1−3.456/5.678)/104.144 g∙mol−1 = 0.039 mol
The extent of the reaction is therefore:
λ = – (0.039 −0.100)/1908 = 3.19∙10−5 mole.

SOLUTION OF TASK 4
a. Molecular formula of A and B – C12H10

b. and c.
O O O
CO2H CO2H

(biphenyl) (acenaphthene)
A B B1 B2
d. Molecular formula of C and D – C7H6O2

e. and f.

CO2H
CHO
O
(benzoic acid) ((E)-3-(2-furyl)acrolein)
C D (or isomerZ)

COCl O
OH
O O

C1 D1 D2

20
g. Molecular formula of E – C3H4N2 Molecular formula of F – C6H8N2

h.
N NH2

N (1,4-diaminobenzene)
H (imidazole) H2N

E F

i.
O O

N N
N N
H H
O O O O
G
H
(or isomer-E)
j.
N
Cl
O
N

I J X (Bifonazole)

SOLUTION OF TASK 5

a. i b.

21
c.

d.

e. C.

f. B.
g. The irreversibility of the reaction ensures spontaneous conversion of the Z 'adduct present in
GFP-2 into the Z adduct present in GFP-3 with the disconnection of the volatile N2 molecule,
which shifts the equilibrium towards the final product (Z).

Seitchik et al. J. Am. Chem. Soc., 2012, 134 (6), pp 2898–2901

22
 64 Chemistry Olympiad
Final competition 2018
Practical tasks and solutions

TASK 1
Malonyl dichloride purity determination
Acyl chlorides are synthesised in the substitution reaction of hydroxyl group by chloride ions. The
reaction involves heating an acid with thionyl chloride and proceeds according to the following
equation:
RCOOH + SOCl2  RCOCl + SO2 + HCl
The final product may be contaminated with the unreacted organic acid or with hydrochloric acid. The
potentiometric titration curve of an acetone-aqueous solution containing the products of pure malonyl
dichloride (propanedioic acid dichloride) hydrolysis with a standard sodium hydroxide solution is
shown in the figure.

You receive a 200-mL volumetric flask denoted with letter P with a solution of technical malonyl
dichloride in water. Malonyl dichloride is highly hygroscopic which makes it difficult to prepare a
precisely weighed amount of it.
You have a standard solution of hydrochloric acid at your disposal with the concentration given on the
bottle and sodium hydroxide solution with a concentration of ca. 0.1 mol∙L−1. There is also burette
23
with a funnel, 25-mL volumetric pipette, two Erlenmeyer flasks, two beakers and graduated cylinder
on your table.
All the participants have methyl orange and phenolphthalein at their disposal.
The data for a few points from a conductometric titration of a sample with an identical composition as
yours have been given in a table on your answer sheet. The titrant concentration was exactly the same
as that of yours.
REMARK: Assume that the sample of technical malonyl dichloride contains only one substance
treated as a contamination.
Problems:
a. Using the potentiometric titration curve and your knowledge in organic chemistry, write down the
names of the substances present in the titrated solution. Write down the equation of malonyl
dichloride hydrolysis.
b. Determine the sodium hydroxide solution concentration with a precision of four significant digits
using the given procedure. Justify your choice of indicator.
c. Using the available glassware and substances determine the total number of acids’ millimoles
in the flask P expressing it as the amount of hydronium ions.
d. Sketch the conductometric titration curve using the data given in the table on your answer
sheet. Determine the equations of lines corresponding to the titration of particular components
and find the lines’ intersection point. Calculate the number of millimoles of the substances in
flask P.
e. Basing on the results of titration answer what was the contamination in the malonyl dichloride
sample. Determine the millimoles number of the contaminant in flask P.
f. Calculate the weight percentage of malonyl dichloride in the hydrolysed sample.

Sodium hydroxide concentration determination

Fill the burette with sodium hydroxide solution. Transfer 25.00 mL of hydrochloric acid to
Erlenmeyer flasks. Dilute it with ca. 45 mL of water and add a few drops of an appropriate indicator.
Titrate until there is a noticeable and permanent change of indicator’s colour. Note the titration results
and calculate the millimoles number of the titrant used for the titration. Repeat the titration until you
get reproducible results. After the titration wash the burette with tap water and then with deionised
water. Calculate the sodium hydroxide solution concentration (with a precision of four significant
digits).
ATTENTION! Take a close look at the answer sheet. Plan your answers and write them in such
a way that they fit in the given space. Explain the abbreviations that you use.
Use the solution economically as you will not be given additional amounts.

24
 TASK 2
Solvent composition influence on solution’s colour. Spectrophotometric determination of water
Thiocyanate anions form coloured complexes with ions such as Fe(III), Co(II), Mo(V) and others.
Identification of cobalt(II) is an interesting case. Blue cobalt(II) complex is formed in aqueous
solutions for high concentrations of added thiocyanate anions. The method’s sensitivity depends on
the thiocyanate ions concentration. Introduction of acetone to the solution greatly increases the
reaction sensitivity. For low thiocyanate ion concentration aqueous solution is practically colourless
and the addition of acetone gives rise to intense blue colour. This testifies to the significant influence
of the solvent on the colour intensity (solvatochromism). Similar phenomena can be observed for
cobalt(II) chloride.
In the attached figures (attachment to problem 2) there are absorption spectra of:
- anhydrous cobalt(II) chloride solutions in ethanol with variable water content
- anhydrous cobalt(II) chloride solutions in ethanol with variable methanol content at room
temperature and after heating (og)
- thiocyanate cobalt(II) complex solutions in a mixture of acetone and ethanol (1:1) with
variable water content
- CI 42051 dye solutions in ethanol with variable water content
The influence of hydrochloric acid addition to the solutions on the spectra is also shown.
The following solutions are placed in ampoules denoted 1, 2 and 3: cobalt(II) chloride in ethanol,
thiocyanate cobalt(II) complex in ethanol-acetone mixture and CI 42051 dye in ethanol.
There is a vegetable sample in ampoule denoted S which contains water and ethanol. Sample mass
(without ethanol) is given on the ampoule. There is a sample of ethanol-acetone mixture containing
water in the graduated test tube denoted R.
You have the following solvents at your disposal: denatured anhydrous ethanol, methanol and
ethanol-acetone mixture. There are also a beaker, stirring rod, small funnel with filter paper, 25-mL
volumetric flask, 5 mL graduated pipette, test tube with a stopper, six test tubes and 6 polyethylene
Pasteur pipettes.
Attention! All the operations in this problem have to be carried out using dry glassware. Wet
glassware should be washed with denatured anhydrous ethanol.
Problems
a. Basing on the information from absorption spectra given in the attachment and at least two
experiments, identify the solutions in ampoules 1, 2 and 3.
b. Prepare a calibration curve for the relative absorbance decrease of a thiocyanate cobalt(II)
complex solution in water-ethanol-acetone mixture as a function of water content in the

25
 solution (use the given procedure). Determine the range in which the function is linear and find
the line equation. Repeat this for cobalt(II) chloride solution in ethanol.
c. Determine the method sensitivity and its quantification limit, assuming that the error associated
with preparing the water solution in organic solvent is negligible and the measurement error is
0.02 when absorbance equals 1.
d. Determine the mass of water in sample R and percentage of moisture in sample S, using the
given procedure.
e. Is selective determination of methanol in ethanol feasible? Justify your answer using the
attached figures.
Procedure
Add denatured ethanol to the sample in ampoule S, mix it with a mixing rod and leave until the
precipitate falls to the ampoule bottom. Transfer the solution from above the residue to the 25-mL
volumetric flask. Add ca. 7 mL of ethanol to the ampoule with precipitate, mix it and, after the
precipitate has fallen, transfer the solution to the flask. Repeat the residue washing. Fill the volumetric
flask up to the graduation mark with denatured ethanol. Filter the solution from the volumetric flask
to the dry graduated test tube. Throw away the first filtrate portion. Collect 5 mL of filtrate, add 2 mL
of cobalt(II) chloride ethanol solution and add ethanol up to 10 mL. Measure the solution absorbance
at 625 nm (due to technical reasons)*. The measured solution absorbance Asolution should be compared
to the absorbance of solution that does not contain water (the Aanhydr will be given by the person
operating the spectrophotometer). Calculate the relative absorbance decrease:

𝐴anhydr − 𝐴sol
∆𝐴rel =
𝐴anhydr

Determine the percentage of water in the studied solution using the calibration curve.
Add 2 mL of cobalt(II) thiocyanate complex in aceton-ethanol solution to the test tube R and fill with
acetone-ethanol mixture up to 15 mL. Measure the absorbance at 625 nm. Calculate the relative
decrease of absorbance according to the formula given above. Determine the percentage of water in
the studied solution using the calibration curve.

* One obtains the highest measurement sensitivity when measuring absorbance at max. When a peak
is broad one does not lose much sensitivity when measuring close to the maximum. In case of the
experiments described here max is 620 and 655 nm, respectively. Due to technical reasons tuning the
light wavelength on the available spectrophotometers would take too much time and the
measurements are carried out at an intermediate wavelength of 625 nm.

Remember about safety rules when doing experiments!

The total number of points for the laboratory tasks is 60.

Practical examination duration: 300 minutes.

26
 Solutions of laboratory Problems
SOLUTION OF LABORATORY TASK 1

Ad a. Malonyl dichloride hydrolyses in water yielding hydrochloric acid and maleic acid which is a
dicarboxylic acid. It follows from the potentiometric titration curve that the dissociation constants of
this acid Ka1 and Ka2 differ significantly. There are two abrupt changes in the titration curve, the first
one, poorly visible, at ca. 39 mL and the second 52 mL (the total titrant volume consumed to titrate
both acids). The difference between the first and second abrupt change is 13 mL which is 25% of the
total amount of titrant used. Summing up, there are two acids in the mixture – hydrochloric acid
(strong one) and maleic acid (weak one).
CH2(COCl)2 + 2H2O → CH2(COOH)2 + 2HCl

Ad b. I will use standard hydrochloric acid solution and phenolphthalein as an indicator to determine
the exact NaOH solution concentration. The hydrochloric acid concentration is 0.1057 mol/L. I will
carry out the titration until the first noticeable change of colour occurs. The colour will be compared
to a solution of HCl with the added indicator. The change of indicator colour should occur as close to
the equivalence point as possible which due to the possibility of NaOH solution contamination with
carbonates will be above pH=7. Methyl orange is a two-coloured indicator changing its colour in the
pH range 3.1 – 4.4 from red to yellow-orange. Addition of too much titrant do not cause a change in
colour and one is unable to say if an appropriate amount of titrant was added. The use of
phenolphthalein makes such observation possible (after addition of an excessive titrant amount the
solutions colour will be more intense). I repeat the titrations until I get similar results. I used on
average 28.20 mL of NaOH solution. I will calculate the NaOH concentration from the following
formula:
𝑐HCl ∙ 𝑉HCl 0.1057 ∙ 25.00
𝑐NaOH = = = 0.09371 mol ∙ L−1
𝑉0NaOH 28.20

Ad c. Using a volumetric pipette I transferred 25,00 mL of solution from flask P (1/8 of the total
sample) to an Erlenmeyer flask. I diluted it with water from a graduated cylinder and have approx. 70
mL of solution in the flask. I added a few drops of phenolphthalein and titrated the resulting solution
with NaOH solution until slight pink colour appeared. The volume of titrant used is denoted VNaOH. I
repeated the titration a few times until I got reproducible results. I calculated the average VNaOH which
equals to 32.70 mL. I calculated the number of hydronium ions millimoles in flask P according to the
following formula:
nH+ = 8∙cNaOH∙VNaOH = 8∙0.09371∙32.7 = 24.51 mmol

27
Ad d. I sketch the conductometric titration curve:
Example data

Titrant volume, mL Conductivity, mS

4.1 11.94
12.2 7.49
20.4 4.84
28.6 4.8

I calculate the x (titrant volume) coordinate of the two lines intersection:

-0.5494∙x + 14.192= -0.0049∙x +4.94  x = 16.99 mL
The first part of the curve (squares) corresponds to hydrochloric acid titration, whereas the second one
(diamonds) to maleic acid. Therefore, there are 16.99·8·cNaOH hydronium ions coming from
hydrochloric acid in flask P:
8∙cNaOH∙xNaOH = 8∙0.09371∙16.99 = 12.74 mmol of hydrochloric acid
Taking into account the total number of hydronium ions millimoles determined from the titration with
phenolphthalein one may calculate that in flask P there are also
8∙cNaOH∙(VNaOH – xNaOH)/2 = 4∙0.09371∙(32.70-16.99) = 5.89 mmol of maleic acid
formed as a result of malonyl dichloride hydrolysis.

Ad e. Basing on the results from point d. one may conclude that the sample of technical malonyl
dichloride contains hydrochloric acid as a contamination because 2·xNaOH > VNaOH. If 2·xNaOH = VNaOH
the sample would be pure malonyl dichloride and for 2·xNaOH < VNaOH the sample would be polluted
with maleic acid. The number of hydrochloric acid additive millimoles was equal to:

28
 nHCldom = 8∙cNaOH∙(2∙xNaOH - VNaOH) = 8∙0.09371∙(2∙16.99-32,70) = 0.96 mmol
If the maleic acid had been the additive, the number of such an additive millimoles would have been:
nmal dom = 4∙cNaOH∙( VNaOH – 2·xNaOH)

Ad f. In case of 2·xNaOH > VNaOH the number of maleic acid millimoles is equal to the number of
malonyl dichloride millimoles in the hydrolysed sample. The mass of technical malonyl dichloride
sample equals::
nClmal∙ MClmal+ nHCladd∙MHCl = 5.89∙140.92 + 0.96∙36.46 = 865.0 mg

The weight percentage of malonyl dichloride in the technical sample amounts to 95,95%.

If 2·xNaOH < VNaOH the number of malonyl dichloride moles is equal to the half of the hydrochloric
acid moles number in flask P.

SOLUTION OF LABORATORY TASK 2

An exemplary set of substances

Ampoule number 1 2 3

Coloured mixture CI 42051 dye Ethanol CoCl2 Ethanol-acetone Co(SCN)n

Ad a. The coloured mixtures presented in the attached figures exhibit varied sensitivity of colour
change with respect to the solvent composition. The system containing the CI 42051 dye is the least
sensitive to water content, the mixture containing thiocyanate cobalt(II) complex is more sensitive and
the ethanol solution of cobalt(II) chloride is the most sensitive. The last solution is also sensitive to
the methanol content but this solution changes colour to pink at room temperature and to blue after
heating (this is an example of thermochromism).
I take ca. 1 mL of every solution to dry test tubes and add a few drops of water to every test tube. The
first solution does not change colour despite the addition of ca. 1mL of water. The second one is
discoloured after addition of 1 drop of water, while the third one after addition of 5 drops of water.
The second solution is the only one to be discoloured after addition of ca. 1mL of methanol (it
becomes faintly pint) and after heating in hot water the blue colour comes back. One of the solutions
changes colour upon hydrochloric acid addition which confirms the identification of CI 42051 dye.
The observed phenomena allow one to conclude that there is CI 42041 dye solution in ampoule 1,
cobalt(II) chloride solution in ampoule 2 and thiocyanate cobalt(II) complex solution in ampoule 3.

Ad b. The calibration curve graphs for the measurements of absorbance at 625 nm for the thiocyanate
cobalt(II) complex in ethanol-acetone solution and cobalt(II) chloride in ethanol are shown in the
figure below.
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For the cobalt(II) chloride in ethanol system the dependence of relative absorbance decrease as a
function of water content is not linear in the whole studied range, but it is linear for water content in
the range 0-1%. The slope of the line is 0.5464. For the thiocyanate cobalt(II) complex in ethanol-
acetone mixture system the calibration curve is linear in the range 0-15% with a slope of 0.061.

Ad c. The slope of the calibration curve determines the spectrophotometric method sensitivity. The increase
in water content by 1% causes a relative decrease of absorbance of 0.546 unit for the cobalt(II) chloride in
ethanol system and 0.061 unit for the thiocyanate cobalt(II) complex in ethanol-acetone system. The
quantification limit in the linear range of the curve is 0.05% water content for ethanol with cobalt(II)
chloride and a much higher value of 0.71% water content for the thiocyanate cobalt(II) complex in ethanol-
acetone mixture system.

Ad d. A sample of 2.23 g was mixed with a few portions of ethanol and the resulting solution was
collected in a 25-mL volumetric flask. The flask was filled with ethanol up to graduation mark and filtered
to a 10-ml test tube. 5 mL of filtrate were collected, ethanol solution of cobalt(II) chloride was added and
ethanol was added up to 10 mL. After mixing the solution absorbance was measured at 625 nm.
Absorbance of the anhydrous solution was 0.785 and that of the studied solution 0.572. The relative
decrease of absorbance was 0.271. I calculate the water concentration in the solution basing on the
calibration curve equation and obtain 0.48%. Therefore, there are 48 mg of water in 10 mL of solution.
There are 25/5 as much water in the whole sample which is 240 mg. The water content in the whole
sample is 0.240·100%/2.23 = 10.8%.
I will determine the water content in sample R by measuring the absorbance of a solution resulting from
the addition of 2 mL of cobalt(II) thiocyanate solution and complementing the solution with acetone-
ethanol mixture up to 15 mL. The absorbance of anhydrous solution was 1.035, while that of the studied
solution 0.572. The relative absorbance decrease was 0.355. The water content calculated from the
calibration curve is 6.2% and the water mass in sample R is 0.062·15 = 0.93 g.

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Ad e. The decrease in cobalt(II) chloride ethanol solution absorbance caused by the presence of
methanol could serve as a basis for the methanol content determination in ethanol. However, the result
would be strongly affected by water. Heating of the solution could be a way to check whether that
absorbance decrease was caused by water. In case of methanol the blue colour returns which does not
take place in the presence of water.

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