UNIVERSITY OF TARTU

THE GIFTED AND TALENTED DEVELOPMENT

CENTRE

TH
55
ESTONIAN NATIONAL
CHEMISTRY OLYMPIAD

Edited by
UNO MÄEORG
JAAK NERUT

Translated by
OLEG LEBEDEV

TARTU 2008
Võti puhtasse keskkonda

Maagaas Eestis

Liivalaia 9, 10118 Tallinn

Telefon: 630 3003, faks: 631 3884
e-post: info@gaas.ee, www.gaas.ee
 CONTENTS

National Theoretical Examination ....................................................................... 4

National Theoretical Examination: 12th Grade ................................................. 4
National Theoretical Examination: 11th Grade ............................................... 11
National Theoretical Examination: 10th Grade ............................................... 18
National Practical Examinations ....................................................................... 24
9th and 10th Grade – Determination of nitrite content by permanganometric
titration........................................................................................................... 24
11th and 12th Grade – Synthesis of Hydrobenzoin ......................................... 25

3
 National Theoretical Examination

National Theoretical Examination: 12th Grade

1. In 1961 Marcus found a guide to qualitative chemical analysis and prepared

the task in identification of the composition of the mixture of oxides for course
mates. The scheme of the analysis is shown below. At the present time atomic
emission spectroscopy is used for the analysis of the same mixture.
Write the balanced equations for the reactions 1-10 taking place during the
analysis of the mixture consisting of CuO, ZnO and Fe2O3. Write the equation
for the reaction 2, if NH4OH is present i) not in excess and ii) in excess. 15 p
+ KHSO4
(alloyage)
CuO, ZnO, Fe2O3
1.
2. + NH4OH
white double salt (saturated, excess)
6. + K4[Fe(CN)6]
3. + HCl 4. + (NH4)2HPO4
MSO4
+ Na2S2O3 MPO4
5. 9. + HCl
M2S
7. + conc. HNO3
8. 10. + K4[Fe(CN)6]
+ K4[Fe(CN)6] brownish
precipitate blue precipitate

2. In 1886 C. Winkler, a German chemist, was experimenting with mineral

I −II
argyrodite. He found that argyrodite contained silver ( Ag ), sulfur ( S ) and the
substance that could not be identified at once. After the weeks of
experimenting it became clear that this new substance was a new element Х
which properties were identical with the element which existence and the
properties had been predicted by Mendeleev 15 years ago.
1.00 g of argyrodite was burned in air until SO2 stopped emitting, a solid
residue was dissolved in nitric acid. For determination of Ag+ ions, 100.0 cm3
0.100 M potassium cyanate solution was added which excess was titrated
back with 9.69 cm3 0.100 M Fe3+ containing solution. SO2 was passed through
Ba(OH)2 solution, 1.156 g of a precipitate was formed. The insoluble in nitric
acid part of А was found to be an amphoteric oxide, which was soluble in both
concentrated HCl and in NaOH solutions (colourless substances were formed).
a) Calculate the masses and amounts of the following substances (in moles)
i) silver and ii) sulfur. (4.5)

4
 b) Write the symbol of element Х and determine the formula of argyrodite.
(5.5)
c) Write the equations of the reactions i) A+ conc.HCl →, ii) A + NaOH(aq) →.
(2) 12 p

3. Human blood is colored red because hemoglobin,

transporter of oxygen, contains iron in oxidized form.
Octopus blood has another color because it contains
oxidized form of another element. The unit cell of the
crystal system for another element is given on the
picture. Crystal system consists of identical tiny boxes,
called unit cells. An atom can belong to several unit
cells at once, for instance, 1/8 of the atoms centered at the apexes and 1/2 of
the atoms positioned at the face centers belong to the given unit cell. The
density of the element is 8920 kg/m3 and the length of the unit cell edge is =
3.62·10-8 cm.
a) How many atoms does the unit cell contain? (1)
b) Calculate the volume of the unit cell and the volume occupied by the atoms
in the unit cell. (Vsphere = 4/3πr3) (5)
c) Using calculations, determine whether the element is present in octopus
blood. What color does the octopus blood have? (3) 9 p

4. The annual consumption of electricity in Estonia is approximately 10000 GWh.

Ecofriendly solar and wind energies depend on season. In addition, the energy
should be somehow conserved in order to apply ecofriendly energy. For the
purpose of retaining the annual energy reserve in Estonia:
a) How many meters are necessary in order to lift Lake Peipsi (25 km3)?(3)
b) How many degrees are necessary to heat Lake Peipsi? (2)
c) How many kg of Н2 should be reserved to convert the energy into electricity
using fuel cell? (2)
d) How many kg of the mixture of deuterium and tritium (1:1) is needed if the
energy is obtained from it by the process of transformation into helium?
(3) 10 p
Assume that power efficiency is 100% in all cases.
Constants: g = 9.8 [m·s-2 = N·kg-1 = J·m-1·kg-1 = W·s·m-1·kg-1],
heat capacity of water is 4181 J·kg-1·K-1 and enthalpy of formation of water is
286.6 kJ·mol-1, speed of light is 3.00·108 m·s-1, Ar(4He) = 4.0026,
Ar(2H) = 2.0141, Ar (3H) = 3.0160, Ar (1n) = 1.0087, G - giga (109).

5. Radical reactions are extensively used in organic I

chemistry. The synthesis of hirsutene that was
separated from mycelium of fungus specie Coriolus
consors is discussed in this problem. Hirsutene is A

5
 hydrocarbon that consists of three five-membered cycles and contains one
double bond. It is obtained from compound А using the radical reaction. The
initiator of the reaction is AIBN (2,2´-azobis-isobutyronitrile, Mr = 164.2), which
is decomposed at 60 ºC with formation of radical В.
a) Draw the structure of hirsutene. (2)
b) Draw the structures of AIBN and radical В. Write the balanced equation of
the AIBN decomposition reaction. (3) 5 p

6. The fact is that doctors do not always have an opportunity to use general
anesthesia, in these cases surgeries are realized using local anesthesia. The
history of local anesthetics began with alkaloid cocaine which was separated
from South American plant Erythroxylon coca. Cocaine had been used in
medicine since the 19th century, but at the beginning of the CH3 COOH
20th century it was banned as a strong drug. N
When cocaine is hydrolyzed, ecgonine (on the picture) and H
OH
there are formed two substances with relatevely simple
structures: saturated alcohol А and aromatic monoprotic H
carboxylic acid В. When a certain quantity of alcohol А is oxidized, according
to the conditions it is possible to obtain 75.0 g of aldehyde or 115.0 g of acid.
20.0 g of 30.0% NaOH solution are needed for neutralization of 18.3 g of
acid В.
a) Using calculations, determine the formulas of alcohol А and acid В, draw
the structure of cocaine. (5)
Using the structure of cocaine as the basis, chemists tried to prepare
synthetical analogs of local anesthetics that were not drugs. One of these first
analogs which is being used till now was procaine. It can be obtained by the
reaction of p-aminobenzoic acid with amino alcohol R2NCH2CH2OH in which
%(N) = 12 %, and R is saturated hydrocarbon radical.
b) Using calculations, determine the formula of amino alcohol R2NCH2CH2OH
and draw the structure of procaine. (3)
Anesthesiophore is the active group of a molecule that confers the anesthetic
effect.
c) Using the similarity of the structures of cocaine and procaine, suggest the
general structure of the anesthesiophore for cocaine and majority of its
analogs. (1) 9 p

Solutions

1. 1. (Cu,Zn)O + KHSO4 = (Cu,Zn)SO4 + KOH

Fe2O3 + 3KHSO4 = Fe2(SO4)3 + 3KOH
2. i) 2CuSO4 + 2NH4OH = (CuOH)2SO4↓ + (NH4)2SO4

6
 ZnSO4 + 2NH4OH = Zn(OH)2↓ + (NH4)2SO4
Fe2(SO4)3 + 6NH4OH = 2Fe(OH)3 + 3(NH4)2SO4
ii) (CuOH)2SO4 + (NH4)2SO4 + 6NH4OH = 2[Cu(NH3)4]SO4 + 8H2O
Zn(OH)2 + (NH4)2SO4 + 2NH4OH = 2[Zn(NH3)4]SO4 + 4H2O
3. [(Zn,Cu)(NH3)4]SO4 + 4HCl = (Cu,Zn)SO4 + 4NH4Cl
4. Fe(OH)3 + (NH4)2HPO4 = FePO4↓ + 2NH4OH + H2O
5. 2CuSO4 + 2Na2S2O3 + 2H2O = Cu2S↓ + S↓ + 2H2SO4 + 2Na2SO4
ZnSO4 + Na2S2O3 ≠
6. 3ZnSO4 + 2K4[Fe(CN)6] = K2Zn3[Fe(CN)6]2↓ + 3K2SO4
7. Cu2S + 6 konts. HNO3 = 2Cu(NO3)2 + H2S↑ + 2NO2↑ + 2H2O
8. 2Cu(NO3)2 + K4[Fe(CN)6] = Cu2[Fe(CN)6]↓ + 4KNO3
9. FePO4 + 3HCl = FeCl3 + H3PO4
10. 4FeCl3 + 3K4[Fe(CN)6] = Fe4[Fe(CN)6]3↓ + 12KCl

2. a) i) Ag+ + KSCN = AgSCN + K+

Fe3+ + 3KSCN = Fe(SCN)3 + 3K+
1 3 0,01 mol 3 3 0,01 mol 1 dm 3
n(Ag) = ( ⋅ 100 cm ⋅ − ⋅ 9,69 cm ⋅ ) =
1 1 dm 3 1 1 dm 3 1000 cm3
= 0,00709 mol
107,9 g
m(Ag) = 0,007093 mol ⋅ = 0,765 g
1 mol
ii) SO2 + Ba(OH)2 = BaSO3↓ + H2O
1 1 mol
n(S) = ⋅ 1,156 g ⋅ = 0,00532 mol
1 217,4 g
32,06 g
m(S) = 0,005317 mol ⋅ = 0,171 g
1 mol
b) We have to find the amount of Ag2S in argyrodite and the amount of
remaining sulfur:
n( Ag) 0,007093 mol
n( Ag 2 S) = = = 0,003547 mol
2 2
n(S, rem)=0,005317 mol-0,003547 mol=0,001770 mol
The oxidation state of element X is positive.
m( X) = 1 g − 0,7653 g − 0,1705 g = 0,06420 g
Atomic mass of element X in compound XiSj is:

7
 m(X) j 0,06420 g j
A(X)= = × =36,27 g/mol
i/j×n(S,rem) i 0,001770 mol i
Potential compounds are X2S, XS, X2S3, XS2 etc. and j/i ratio is 0.5, 1, 1.5,
2 etc. Possible atomic masses of X are (os = I), 36.3 (II), 54.4 (III), 72.5 (IV),
90.6 (V) etc. Tetravalent Ge as well as GeS2 may be the only possible
correct answers .
0,001770 mol
n(GeS 2 ) = = 0,0008850 mol
2
Ag2S : GeS2 = 0.003547 : 0.0008850 = 4 : 1
The formula of argyrodite is Ag8GeS6.
c) i) GeO2 + 4HCl = GeCl4 + 2H2O
ii) GeO2 + 2NaOH = Na2GeO3 + H2O
The properties of germanium (Latin Germania for Germany) were similar to
the element ekasilicon that Mendeleev predicted to exist. The discovery
was an important confirmation of the idea of element periodicity.

1 1
3. a) N = 6 ⋅ + 8 ⋅ = 3 +1= 4
2 8
b) Vunit cell =a 3 =(3,62×10-8 cm)3 =4,70×10-23 cm3
We have to find connection between the length of the unit cell a and the
atomic radius r:
2a
(r + 2r + r ) = a 2 + a 2 = 2a 2 = 2a => r=
4
4 16 2a 3 16 2 2 a3
Vatom = 4 ⋅ π r 3 = π ( ) = ⋅ π = 2 π a3 =
3 3 4 3 64 6
2
= π ⋅ 4,70 ⋅ 10 - 23 cm3 = 3,48 ⋅ 10 −23 cm3
6
2 3 1
%occupied = π a ⋅ 3 ⋅100 = 74,0 %
6 a
m m
c) munit cell = Vunit cell ⋅ ρ M = unit cell = unit cell
nunit cell N / N A
−23 8,92 g 1 6,02 ⋅ 10 23
M = 4,7 ⋅ 10 cm ⋅ 3
⋅ ⋅ = 63,1 g / mol
cm3 4 1 mol
Element is copper. Octopus blood is colored blue.

109 Wh 3600 s 1 J
4. E (Estonia) = 10000 GWh ⋅ ⋅ ⋅ = 3,6 ⋅1016 J
1 GWh 1 h 1W ⋅1 s
1 m kg 1 km 3 1 m3
a) h = 3,6 ⋅ 10 16
J⋅ ⋅ ⋅ ⋅ = 147 m = 150 m
9,8 J 25 km 3 10 9 m3 10 3 kg

8
 1 kg K 1 km 3 1 m3
b) ΔT = 3,6 ⋅ 10 J ⋅
16
⋅ ⋅ ⋅ = 0,34 K
4181 J 25 km 3 10 9 m3 10 3 kg
c) H2 + 1/2O2 = H2O
1 mol 1 kJ 2 g 1 kg
m(H2 ) = 3,6 ⋅ 1016 J ⋅ ⋅ 3 ⋅ ⋅ 3 = 2,5 ⋅ 10 8 kg
286,6 kJ 10 J 1 mol 10 g
3 2 4 1
d) H + H = He + n E = Δmc 2
1 s2
Δm = 3,6 ⋅ 10 J ⋅
16
= 0,4 kg
(3 ⋅ 10 8 m)2
2,0141 + 3,0160
m( 3 H + 2 H) = 0,4 kg ⋅ = 107 kg = 110 kg
2,0141 + 3,0160 − 4,0026 − 1,0087
5. a)

b)
60 °C .
+ N2
2
N N
CN CN CN
AIBN B

6. a) СnH2n+2O → СnH2nO → СnH2nO2

75 115
n(СnH2nO) = n(СnH2nO2) = => n = 1
14n + 16 14n + 32
A – CH3OH, methanol
RCOOH + NaOH = RCOONa + H2O
1 1 mol
n(RCOOH) = ⋅ 20 g ⋅ 0,3 ⋅ = 0,15 mol
1 40 g
18,3 g
M(RCOOH) = = 122 g / mol
0,15 mol
M(R) = (122 − 45) g / mol = 77 g / mol R is benzene ring (C6H5-)
B – C6H5COOH, benzoic acid
Cocaine can be considered as the product of CH3 COOCH3
double esterification of ecgonine: methanol N H
reacts with carboxyl group and benzoic acid O
reacts with hydroxyl group. O
H

9
 14
b) R2NCH2CH2OH %(N) = = 0,12 => M(R) = 29
2M(R) + 59
R is ethyl group (C2H5-)
(C2H5)2NCH2CH2OH
Reaction of amino alcohol with p- H3C CH2
aminobenzoic acid gives procaine N CH2 CH2 O NH2
as the product H3C CH2 O
c) The comparison of the structures of R1 R3
cocaine and procaine shows that the N n
O R5
probable structure of the anesthesiophore R2 R4 O
is

10
 National Theoretical Examination: 11th Grade

1. A beaker with 12.00 g of CuSO4 was set aside on vacation. One week later
precisely 1/3 of the salt transformed into pentahydrate (CuSO4·5H2O). 90.00
cm3 of water were casually slooshed into the beaker during cleanup after
vacation. After that all the charge was transferred into a flask filled with 300.0
cm3 0.0400 М NaOH solution. A formed precipitate was separated and heated
until a red substance was formed and its mass remained stable.
a) Calculate the mass of the salt in the beaker one week later. (2)
b) Calculate the percentage of CuSO4 in the formed solution. (1)
c) Write all the reactions taking place and name the compounds that contain
copper. Calculate the mass of the substance after heating. (7)10 p

2. Hydrocarbon contains 87.27% carbon by mass, the relative density in gas

phase with respect to hydrogen is less than 75. The structure consists of
secondary and tertiary carbon atoms only and at least two six-membered
cycles.
a) Using calculations, determine the empirical formula and draw the structure
of hydrocarbon. (5.5)
b) How many monochloro derivatives are formed during nonselective
chlorination in sunlight? (1.5) 7 p

3. A. Einstein made a riddle and he claimed that only 2% of the world’s

population could solve it. The following problem is a chemical analog of the
riddle. There is a run of 5 pots with food colorings on a shelf and it is
necessary to determine which substance is present in colored marchpane. The
facts of the puzzle are given below.
Indigo carmine is colored blue. Curcumine is found in curcuma (spice).
Riboflavin contains four OH-groups. The substance colored red stands on the
left of the substance colored orange. The substance colored red is E-isomer.
Lemonade contains the substance which is classified as salt. The substance in
the flask right in the center contains two intramolecular hydrogen bonds. The
wine-colored substance is carotenoid. Licopine is first on the left. The
substance related to vitamins
stands next to the substance and pot nr. 1 2 3 4 5
is contains in melon. The color
substance present in almond name
stands next to the substance structure, group
class
related to carotenoids. The food coloring
substance that is polyphenol

11
 contains carbonyl group. Licopine stands next to the substance colored yellow.
Carmoisine is azo compound. The substance related to vitamins stands next
to the substance that contains ten methyl groups. Fill the gaps in the table.10 p

4. Phosphoric acid is a triprotic acid for which K1 = 7.6 · 10−3, K2 = 6.2 · 10−8,
K3 = 4.4 · 10−13.
a) Draw a sketch of the titration curve of phosphoric acid titrated with NaOH
solution (a plot of pH vs V(NaOH), without calculations) (2)
3
A certain amount of 0,10 M NaOH solution was added to 50 cm 0,010 M
H3PO4 solution in order to equalize the amounts of NaH2PO4 и Na2HPO4.
b) Calculate the рН of the initial solutions (NaOH и H3PO4). (4)
c) Determine what is a weak acid and its corresponding salt in the formed
solution. (1)
d) Calculate the рН of the formed solution and the volume of added NaOH
solution, mark it on the graph. (2.5)
e) Calculate the change of the pH of the formed solution if 5.0 mg of solid
NaOH is added. (3.5) 13 p

5. Acid А consists of 3 elements. A metal wire was inserted into the flask with
75.0 g of 16.4% acid A aqueous solution. As a result, 0.672 dm3 (n.c.) of
hydrogen was produced and a salt solution was formed. When an excess of
AgNO3 was added to the solution, 25.81 g of a white precipitate formed. The
precipitate contained 75.26% silver by mass. No change of the mass of the
wire was detected during the analysis.
a) Detemine the composition of the white precipitate and calculate the formula
of acid А. (6)
b) What metal is the wire made from? (3)
c) Write the equations of all the reactions which take place.
(2)11 p

6. Analyzed copolymer consists of monomer units of 1398 ethene molecules

(CH2CH2), 466 α-methylstyrene molecules (C6H5C(CH3)CH2) and 699 propene
molecules (CH3CHCH2).
a) Assume that monomer units are positioned in the order of increasing
molecular masses in the elementary unit of an ideal polymer. i) Estimate the
molar mass of the polymer and ii) write the formula of the elementary unit of
the polymer (symbols: monomer units of Е – ethene, S – α-methylstyrene
and Р – propene), iii) find the number of the elementary units in the polymer
molecule. (3.5)
Actually, a polymer consists of chains of varying lengths which are
characterized by average molar mass. Average molar mass Mav can be found

12
 by measuring of osmotic pressure Π of a Π (Pa) 55.68 111.4 167.0
3
diluted solution of polymer. Osmotic c (mg/cm ) 2 4 6
pressure Π (Pa) is directly proportional to
the concentration of the solution (c,
g/m3): Π = RTc / M av , whereby R is gas constant and Т is the temperature. The
results of the measurement (25 °C) are show in the table.
b) Sketch a plot of Π/RT vs. c, find the slope (give the units) and Mav. Is
average polymer molecule longer in comparison with ideal molecule? (4)
c) How many carbon atoms are there in average polymer chain if the structure
of the elementary unit is the same as in ideal polymer? (1.5) 9 p

Solutions

1 1 mol 5 18 g
1. a) m(CuSO 4 ) = 12 g + ⋅ 12 g ⋅ ⋅ ⋅ = 14,26 g
3 159,5 g 1 1 mol
12 g
b) %(CuSO 4 ) = ⋅ 100 = 11,51
14,26 g + 90 cm 3 ⋅ 1 g / cm 3
c) CuSO4 + 5H2O = CuSO4·5H2O copper(II) sulfate pentahydrate
CuSO4 + 2NaOH = Cu(OH)2↓ + Na2SO4 copper(II) hydroxide
to
Cu(OH)2 = CuO + H2O↑ copper(II) oxide
1 mol
n(CuSO 4 ) = 12 g ⋅ = 0,07524 mol
159,5 g
1 1dm3 0,04 mol
n(CuSO4 , NaOH from)= ⋅ 300 cm3 ⋅ ⋅ =0,00600 mol
2 1000 cm3 1dm3
CuSO4 is in excess.
1 1 79,5 g
m(CuO) = ⋅ ⋅ 0,006 mol ⋅ = 0,477 g
1 1 1 mol

x ⋅ 12,01
2. a) M(C xHy ) = = 13,76 x
0,8727
y = 13,76 x − 12,01x = 1,75x
x : y = x : 1.75x = 1 : 1.75 = 4 : 7
The simplest empirical formula is C4H7.
M(C xHy )
ρH = 75 <
2
2
M(C xHy )
Taking into account that ρH = 75 < and the structure consits of at
2
least two six-membered cycles, the formula of hydrocarbon is C8H14.

13
 b) Two different monochloro derivatives are formed. One of them can appear
in the form of two enantiomers.
Cl2 Cl Cl
+
hν H
2 enantiomers

3. Table
1 2 3 4 5
Color Yellowish-
Dark-red Yellow Blue Red
orange
Name Licopine Riboflavin Indigo carmine Carmoisine Curcumine
Structure,
-CH3 (10 u) -OH (4 u) N-H·····O=C E-isomer C=O
group
Class Azo
Carotenoid Vitamine Salt Polyphenol
compound
Food coloring Melon Almond Limonade Marchpane Curcuma

Carmoisin is present in marchpane

E100 Curcumine E101 Riboflavin

O O O
H3C N
NH

HO OH H3C N N O
OMe OMe OH

OH
HO

OH
E122 Carmoisine E132 Indigo carmine
-
SO3 O H
-O S NaO3S
3 N

N SO3Na
HO H O
E160d Licopine

14
4. a) Titration curve of phosphoric acid. Titration curve has three steps because
phosphoric acid is a triprotic acid.
14
12
10 pH = pK2 = 7,21
8
pH

6
pH = 2,24
4
2
0
7,25
0 5 10 15
V(NaOH) /cm3
b) NaOH solution pH = 14 − pOH = 14 + log [OH- ] = 14 + log 0,1 = 13
H3PO4 solution
[H+ ][H2PO -4 ]
H3PO4 = H2PO4- + H+ K1 =
[H3PO 4 ]
-
Mass balance: cacid = [H3PO4] + [H2PO4 ]
Charge balance: [H+] = [H2PO4-]
From the first expression: [H3PO4] = cacid - [H2PO4-] = cacid - [H+]
[H + ]2 K1 K2
K1 = => [H + ] = - + 1 + K1cacid
cacid − [H + ] 2 4
[H+ ] = -0,0076/2 + 0,0076 2 / 4 + 0,0076 ⋅ 0,01 = 0,0243
pH = − log 0,0571 = 2,24
c) In the formed buffer solution NaH2PO4 can be considered as a weak acid
and Na2HPO4 as its cooresponding salt.
[salt]
d) pH=pK 2 +log
[weak acid]
[NaH2PO4] = [Na2HPO4] => pH = pK 2 = − log(7.6 ⋅ 10 −3 ) = 7.21
The reactions taking place in the solution:
NaOH + H3PO4 = NaH2PO4 + H2O
NaH2PO4 + NaOH = Na2HPO4 + H2O
1 1 1
V(NaOH) = ( + ) ⋅ 50 cm3 ⋅ 0,01 M ⋅ = 7,5 cm3
1 2 0,1 M

15
 1 1dm3 mol
e) n(NaH 2 PO4 )initial =n(Na 2HPO 4 )initial = ×50 cm3× ×0,01 =
2 1000 cm3 dm3
= 2,5 ⋅ 10 −4 mol = 0,25 mmol
1mol
n(NaOH)added = 0,005 g ⋅ = 1,25 ⋅10−4 mol = 0,125 mmol
40 g
(0,25 + 0,125) mmol
pH = 7,21 + log = 7,69
(0,25 - 0,125) mmol
ΔpH = 7,69 − 7,21 = 0,48

n ⋅ A r ( Ag)
5. a) AgnX %( Ag) = = 0,7526 => A r ( X ) = 35,46n
n ⋅ A r ( Ag) + A r ( X )
The correct answer is n = 1 and X – Cl. The white precipitate is AgCl.

Acid А consits of H, Cl and unknown element Y.

1 mol
N(Cl) = N( AgCl) = 25,81 g ⋅ = 0,18 mol
143,3 g
1 mol
N(H) = 2N(H2 ) = 2 ⋅ 0,672 dm 3 ⋅ = 0,06 mol
22,4 dm 3
Because N(H) : N(Cl) = 1 : 3, A – HxYyCl3x
The general equation of the reaction:
m HxYyCl3x + 3x M = mx/2 H2 + 3x MClm + my Y
x
M( A ) = 75 g ⋅ 0,164 ⋅ = 205x g / mol
0,06 mol
205 − 1,008 − 3 ⋅ 35,45 97,642
If x = 1, A r ( Y ) = =
y y
If y = 1, Y – Tc, If y = 2, Y – Ti, ...
Both the answers are not correct with respect to the statements of the
problem.
2 ⋅ 97,642 195,284
If x = 2, A r ( Y ) = =
y y
If y = 1, Y – Pt, If y = 2, Y – Tc, If y = 3, Y = Tc, ...
A – H2[PtCl6] (Other answers are not correct with respect to the
statements of the problem)

b) 6M + mH2[PtCl6] = 6MClm + mH2↑ + mPt↓

Because no change of the mass of the wire was detected
1 195,08 g
m(M) = m(Pt ) = ⋅ 0,06 mol ⋅ = 5,8524 g
2 1 mol

16
 1
M(M) = 5,8524 g ⋅ = 32,51m g / mol
6 / m ⋅ 0,03 mol
If m = 2, M – Zn (Other values are not correct with respect to the
statements of the problem)
c) 3Zn + H2[PtCl6] = 3ZnCl2 +H2↑ + Pt↓
ZnCl2 + 2AgNO3 = Zn(NO3)2 + 2AgCl↓

28 g 118 g 42 g g
6. a) i) M ideal = 1398 ⋅ + 466 ⋅ + 699 ⋅ = 123 500
1mol 1mol 1mol mol
ii) E : P : S 1398 : 699 : 466 6:3:2
6E-3P-2S
28 g 118 g 42 g g
iii) M unit = 6 ⋅ + 2⋅ + 3⋅ = 530
1mol 1mol 1mol mol
123 500 g/mol
Number of the elementary units= =233
530 g/mol
Π 55,68 N 1 mol ⋅ 1 K 1 mol
b) = ⋅ ⋅ = 0,0225 3
RT m 2
8,314 N ⋅ m ( 273,15 + 25) K m
Π (Pa) 55.68 111.4 167.0 0.08
3
c (mg/cm ) 2 4 6
0.07
Π/RT 0.0225 0.0449 0.0674
0.06
Π/RT (mol/m )
3

mol
Slope = (0,0449-0,0225) 3 ⋅ 0.05
m
1 cm3 1m3 103 mg 0.04
⋅ ⋅ 6 ⋅ = 0.03
(4-2) mg 10 cm 1g
= 1,12 ⋅10−5 mol/g 0.02
1g 0.01
Mav = =89300 g/mol 0
1,12×10-5 mol
Average polymer chain is shorter 0 1 2 3 4 5 6 7
than in ideal molecule. c (mg/cm3)
c) The number of carbon atoms in the
repeating unit is (6 + 2 + 3) · 2 = 22.
89 300 g/mol
Number of units= =168
530 g/mol
N(C) = 168 ⋅ 22 = 3710

17
 National Theoretical Examination: 10th Grade

1. a) Write the electronic configuration of molybdenum. (1)

b) What type are chemical bonds in the following substances: i) HClO4,
ii) NaClO4, iii) Cs? (1.5)
c) Write the structural formula of H2S2O3 and find the oxidation states of all the
atoms. (1.5)
d) Calculate the i) molarity, ii) molality of 6.00 % HCl solution (1.028 g/cm3).
(3)
3
e) How many gas molecules are there in the volume of 1 cm at 1 Torr, 20 °C?
1 atm = 760 Torr. (3) 10 p

2. Molecular motor (proton turbine) is a moving power for some bacteria. It is

powered by the flow of escaping H+ ions. Proton turbine gives 20 kJ of energy
per one mol of protons to a bacteria cell in physiological conditions.
a) A bacterial colony of 109 units lives in a human digestive tract. Calculate the
energy produced by the moving colony during one minute if each bacteria
releases 107 protons during this time. (1.5)
b) Calculate the change of the pH if all emitted protons are equally dispersed
in the volume of human body (70 dm3) (assume that the initial pH = 7 and
buffer systems do not function). (3)
c) If a human could transform the energy of proton turbine into work, how
many minutes would a usual 100 W bulb work using 1 dm3 of concentrated
sulphuric acid (17.5 M) as a fuel? (1 J = 1 W · 1 s) (2.5) 7 p

3. Methanol (octane rating 113) is used in high perfomance automobile engines.

A student tried to understand why methanol is used instead of petrol. For this
purpose he calculated the enthalpies of combustion per gram for both the
compounds. Assume that petrol consits of isooctane ∆ o
fH
(octane rating 100) only. Substance
(kJ/mol)
a) Write the structure and the systematic name of
isooctane. (1) H2O (l) -285.8
b) Write the chemical equations for the total burning of CO2 (g) -393.5
methanol and isooctane and calculate the standard CH OH (l) -238.4
3
enthalpies of combustion per mol and gram. (6)
c) The student compared the enthalpies of combustions, C8H18 (l) -259.3
but he did not understand why methanol is used.
Explain why methanol is used as a fuel. Prompt: octane rating, chemical
equations. (2) 9 p

4. There are seven pure metals in numbered flasks: Fe, Hg, Na, Al, Ca, Au and
Sn. Metals in the flasks 1 and 3 do not produce hydrogen if treated with diluted

18
 HCl solution. It is dangerous to let metal 1 contact with metal 3 because an
alloy is easily formed. Metals 4 and 6 react vigorously with water. Metals 2
(with heating), 4, 5 and 6 react with alkali aqueous solution. Metal 7 has a
smaller density and a higher melting point than metal 3. Metal 2 has a smaller
density than metal 7 and it has a lower melting point than metal 3. Metals 2, 4
and 5 are liquids at 1000 °C; there are equal numbers of solids ang gases at
this temperature.
a) Identify the metals in each flask. Arrange the metals in the order of
increasing i) density and ii) melting point. (5.5)
b) Write the equations of the the reactions of the metals with i) diluted
hydrochloric acid and ii) alkali aqueous solution. Write the names of the
formed complexes. (6)
c) Give the general name of metal 1 alloys with other metals. (0.5) 12 p

5. A number of people have to eat food with a low sodium content because of
high blood pressure. LoSalt company sells the salt that contains approximately
66.6 % KCl and 33.4 % NaCl. A student was interested to determine the
composition of the mixture. For this purpose he weighed 1.00 g of the heated
salt, transferred it into a 100.0 cm3 flask and added distilled water to the mark.
For the titration of 10.00 cm3 of this solution 29.60 cm3 of 0.05000 M AgNO3
solution was required. Potassium chromate indicator was used.
a) Write the equations of the reactions of i) chloride ion and AgNO3 and
ii) silver ion and potassium chromate. What happens if the solution is
overtitrated? (3)
b) Calculate the KCl content (in per cent) in the salt. (5.5)
c) How many per cent is the difference between actual and labelled KCl
content? (0.5) 9 p

6. A powder of light-red pigment C can be prepared combining salts A and B

aqueous solutions. Salt B is used in the glass and soap manufacture and it
can be obtained by the heating of soda. Salt A is a hygroscopic binary
compound (%(X) = 54.6) which can be obtained by the reaction of iron triad
metal Y and gaseous halogen X2. Pigment C can be also synthesized by
heating of salt A , D or E solution (all salts contain the same metal) and
compound F. Salt D contains one of the anions present in aqua regia. Salt E
anion originates from acetic acid. Compound F was the first organic substance
prepared from inorganic materials. In industry F is obtained by the reaction of
NH3 and CO2.
a) i) Using calculations, determine metal Y. ii) Write the formulas for A-F, X2 ,Y
and name the compounds. (6)
b) Write the following chemical equations: i) decomposition of soda, ii) X2 + Y
→ A, ii) A + B → C, iii) 2NH3 + CO2 → F + …. (2)

19
 Violet pigment K which cation contains %(N) = 19.20, %(Z) = 75.28 and
%(H) = 5.52 is used in cosmetics. Pigment is obtained by the reaction of acid
M, acid salt N (%(N) = 12.18%) and brownish-black oxide O (%(Z) = 63.19 %).
Salt N contains salt M anion. Acid M is added in small portions into cold drinks.
Metal os is III and phosphorus os reaches maximum in pigment K.
c) i) Using calculations, determine metal Z and the formula of pigment K if
anion consists of O and P. ii) Write the formulas and names for M-O, Z.
(5) 13 p

Solutions

1. a) 1s2 2s22p6 3s23p6 3d104s24p6 4d55s1

b) i) all bonds (H-O, Cl=O, Cl-O) are polar covalent
ii) polar covalent bond: Cl=O and Cl-O, ionic bond: Na+ClO4-
iii) metallic bond
oa = -II
H O S
S oa = VI
c) H O O os(H) = I os(O) = -II
1 mol 1 1,028 g 1000 cm3 mol
d) i) c = m ⋅ 0,06 ⋅ ⋅ ⋅ ⋅ = 1,69 = 1,69 M
36,5 g m 1 cm3 1 dm 3 dm 3
1 mol 1 1 1000 g mol
ii) c m = m ⋅ 0,06 ⋅ ⋅ ⋅ ⋅ = 1,75 = 1,75 m
36,5 g m 1 − 0,06 1 kg kg
m – mass of the solution
pV 3 1000 cm
3
1 1 Torr ⋅ cm 3
e) R = = 760Torr ⋅ 22,4 dm ⋅ ⋅ ⋅ = 62360
nT 1 dm 3 1 mol 273 K mol ⋅ K

pV 1 mol ⋅ K 1 1
N= ⋅ NA = 1 Torr ⋅ 1 cm 3 ⋅ 3
⋅ ⋅ 6,02 ⋅ 10 23 = 3 ⋅ 1016
RT 62360 Torr cm 293 K mol

1mol 107 20000 J

2. a) Q = 109 bakteria ⋅ 23
⋅ ⋅ = 3 ⋅10−4 J/min
6,02×10 bakteria 1min 1mol
1mol 1
b) c(H + ) = 109 bakteria ⋅ 23
⋅107 ⋅ 3
+ 10-7 M =
6,02×10 bakteria 70 dm
= 1,002 ⋅ 10 −7 M
ΔpH = − log(1,002 ⋅ 10 −7 ) − 7 = −10 −3
2 17.5 mol 20000 J 1 s 1 min
c) t = ⋅ 1 dm 3 ⋅ ⋅ ⋅ ⋅ = 120 min
1 1 dm 3 1 mol 100 J 60 s

20
3. a) 2,2,4-trimethylpentane
b) 2CH3OH (v) + 3O2 (g) = 2CO2 (g) + 4H2O (v)
2C8H18 (v) + 25O2 (g) = 16CO2 (g) + 18H2O (v)
1
Δ combustionHo (CH3OH) = ⋅[2 ⋅ (-393,5) + 4 ⋅ (-285,8)-2 ⋅ (-238,4)] =
2
= - 726,7 kJ/mol
1
Δ combustionHo (C8H18 ) = ⋅[16 ⋅ (-393,5) + 18 ⋅ (-285,8)-2 ⋅ (-259,3)] =
2
= -5460,9 kJ/mol
-726,7 kJ 1mol
Δ combustionHo (CH3OH) = ⋅ = −22,68 kJ/g
1mol 32,04 g
-5460,9 kJ 1mol
Δ combustionHo (C8H18 ) = ⋅ = −47,82 kJ/g
1mol 114,2 g
c) On the one hand, the enthalpy of combustion of isooctane per mass is twice
the enthalpy of combustion of methanol, hence, isooctane should be used
as a fuel because it is more thrifty. On the other hand, methanol is used
because
i) octane rating of methanol is higher and it does not detonate so easily.
Therefore in high perfomance engines the combustion of methanol goes
more smoothly and the effiency of engine is greater.
ii) less oxygen is needed to oxidize methanol in comparison with isooctane.
Hence, more methanol than isooctane is consumed during one
combustion cycle at constant volume and more energy is obtained during
one cycle if methanol is used.

4. Reaction with hydrochloric acid: 1 and 3 are Au and Hg. It is confirmed by the
formation of the amalgam. Hg has the ρ / g/cm3 mp/ ºC bp/ ºC
lowest melting point. Because metal 2 has Hg 13.5 -39 357
a lower melting point than metal 3, 3 must Na 0.97 98 883
be Au and 1 is Hg. From the given metals Sn 7.3 232 2602
Na and Ca react vigorously with water (4 Al 2.7 660 2519
and 6). With alkali aqueous solution react Ca 1.5 842 1484
Na and Ca (4 and 6, reaction with water)
Au 19.3 1064 2856
and Al and Sn (2 and 5) because they are
Fe 7.9 1538 2861
amphoteric metals. Heating is needed for
Sn - metal 2, and 5 is Al. Sn, Ca and Al are liquids at 1000 °C (because both
Na and Ca are not liquids, but Na has a lower melting point, hence one of
them - Na – is gas: the boiling point of Na is 883 °C), therefore metal 4 is Ca
and 6 is Na. Hg is gas at 1000 °C too, Au and Fe are solids. Metal 7 reacts
with HCl solution, but does not react with alkali, hence Fe – metal 7. Fe has a
lower density than Au (7,9 < 19.3 g/cm3), but it has a higher melting point

21
 (1538 > 1064 °C). Sn has a lower density than Fe (7.3 < 7.9 g/cm3) and a
lower melting point than Au (232 < 1064 °C).
a) 1 – Hg 2 – Sn 3 – Au 4 – Ca 5 – Al 6 – Na 7 – Fe
i) Na < Ca < Al < Sn < Fe < Hg < Au
ii) Hg < Na < Sn < Al <Ca<Au<Fe

b) i) M + 2HCl = MCl2 + H2↑ , kus M = Sn, Ca, Fe

2Na + 2HCl = 2NaCl + H2↑
2Al + 6HCl = 2AlCl3 + 3H2↑
ii) Sn + 2NaOH + 2H2O = Na2[Sn(OH)4] + H2↑
sodium tetrahydroxystannate(II)
Ca + 2H2O = Ca(OH)2 + H2↑
2Na + 2H2O = 2NaOH + H2↑
2Al + 6NaOH + 6H2O = 2Na3[Al(OH)6] + 3H2↑
sodium hexahydroxyaluminate
2Al + 2NaOH + 6H2O = 2Na[Al(OH)4] + 3H2↑
sodium tetrahydroxyaluminate
c) amalgams

5. a) i) Cl- + AgNO3 = AgCl↓ + NO3-

ii) 2Ag+ + K2CrO4 = Ag2CrO4 + 2K+
After the equivalence point silver ions react with chromate ions and red
silver chromate is formed.
1 100 cm3 1 dm 3 0,05 mol
b) n(Cl− ) = ⋅ 3
⋅ 29,60 cm 3
⋅ 3
⋅ = 0,0148 mol
1 10 cm 1000 cm 1 dm 3
m(KCl) 1 − m(KCl)
+ = 0,0148 m(KCl) = 0,625 g
74,56 58,44
0,625 g
%(KCl) = ⋅ 100 = 62,5
1g
c) Difference = (66,6 − 62,5) % = 4,1%

n ⋅ Mr ( X )
6. a) i) The general formula of salt A is YXn. Mr ( Y ) = ⋅ (1 − 0.546 )
0,546
Because halogen is gaseous, the salt is fluoride or chloride. Calculations
shows that no one of the iron triad fluorides is correct with respect to the
statements of the problem. CoCl2 is correct.
2 ⋅ 35,5
Mr ( Y ) = ⋅ (1 − 0.546 ) = 59
0,546
Y – Co
ii) A - CoCl2, cobalt(II) chloride
B – Na2CO3, sodium carbonate

22
 C – CoCO3, cobalt(II) carbonate
D – Co(NO3)2, cobalt(II) nitrate
E – Co(CH3COO)2, cobalt(II) acetate
F – (NH2)2CO, carbamide or urea
X2 – Cl2, chlorine
Y – Co, cobalt
to
b) i) 2NaHCO3 = Na2CO3 + H2O + CO2↑
ii) Co + Cl2 = CoCl2
iii) CoCl2 + Na2CO3 = CoCO3↓ + 2NaCl
iv) 2NH3 + CO2 = (NH2)2CO + H2O
c) i) The general formula of oxide O is Z2On
2 ⋅ Mr ( Z )
%( Z ) = = 0,6319 Mr ( Z ) = 13,73n
2 ⋅ Mr ( Z ) + n ⋅ 16
The correct answer is n = 4. Mn2O4 or MnO2 Z – Mn
The composition of cation K:
75,28
N(Mn) = = 1,37
54,94
19,2 5,52
N(N) = = 1,37 N(H) = = 5,47
14 1,01
N(Mn) : N(N) : N(H) = 1 : 1 : 4
III −III I
Cationic part of the pigment is [Mn( N H4 )] 4+
Taking into account that K anion contains also phosphorus and oxygen
we have to choose the subscripts according to the oxidation states.
K – Mn(NH4)P2O7
ii) M – H3PO4, phosphoric acid
14
N – NH4H2PO4, monoammonium phosphate %(N) = = 12,18
115
O – MnO2, manganese dioxide
Z – Mn, manganese

23
 National Practical Examinations

9th and 10th Grade – Determination of nitrite content by permanganometric

titration

Introduction
Potassium permanganate (KMnO4) is a strong oxidizing agent in acidic media,
which is used for different redox titrations. The major advantage of utilizing
KMnO4 as the titrant is that no indicator is needed due to its deep purple color.
KMnO4 is not a primary standard, therefore, the concentration of KMnO4 is
determined by titration with primary standard solution (for example, oxalic acid –
H2C2O4)

Determination of nitrite ions by permanganometric back titration

Theory
Nitrite ions (NO2-) are oxidized by KMnO4 to nitrate ions (NO3-). NO2-
determination by direct titration with KMnO4 is not accurate. For this reason the
analysis is realized using the following procedure. Firstly, NO2- ions present in the
solution are oxidized by an excess volume of KMnO4. Then oxalic acid solution is
added in excess. Excess volume of oxalic acid is determined by titration with
KMnO4 solution.

Procedure
For the analysis of the sample pipette 25.00 cm3 potassium permanganate
solution into a 300 cm3 Erlenmayer flask and add approximately 15 cm3 1:4
diluted sulphuric acid (use centrifugal glass for measurement 10 + 5 cm3).
Pipette 10.00 cm3 of the sample solution to the mixture. Cover the flask and leave
it to stand for 10-15 minutes for total nitrite ions oxidation.
Add 25.00 cm3 0.02500 M oxalic acid solution to the flask. Shake the solution
(avoid outflowing of the solution from the flask) and titrate an excess of oxalic acid
with potassium permanganate solution until the solution is pink in color. The
reaction is slow and pink color must be stable for some minutes in endpoint.
Titrate until three constant results are obtained.
For determination of the precise concentration of KMnO4 solution pipette
10.00 cm3 oxalic acid solution (precise concentration is written on the vessel) into
a 100 cm3 beaker, add 7-10 cm3 1:4 diluted sulphuric acid and heat the solution.
Do not allow the solution to boil because it can cause partial decomposition of
oxalic acid. Titrate the heated solution with potassium permanganate solution
until the solution is slightly pink in color. The solution must be hot during the
titration because it helps to form a catalyst (MnSO4). Despite heating, the reaction
can proceed slowly at first, but it is accelerated when some amount of oxalic acid
is reacted.
Titrate until three constant results are obtained.

24
 11th and 12th Grade – Synthesis of Hydrobenzoin

Sodium borohydride was discovered

in 1943 by H. I. Schlesinger and H. C.
Brown. Now it is one of cheapest and O NaBH4 OH
most employed reducing agents in O OH
organic synthesis.
In this problem you will examine easy
and convenient method of reduction
by sodium borohydride.

Bensiil Hüdrobensoiin
Procedure

Dissolve 0.5 g of benzil in 5 cm3 95% ethanol in a 50 ml Erlenmeyer flask. Then

add 0.2 g of sodium borohydride (in excess) at stirring.
The reaction mixture warms up moderately and yellow color disappears after 2-3
minutes. Attach a condenser and leave the mixture to stir for 10 minutes. Then
add 5 cm3 of destilled water and heat the mixture until boiling is achieved. Add
distilled water (ca 10 cm3) to the mixture until saturation is achieved (turbidity
appears) and cool the flask with a cold water bath.
Sparkling thin crystals of hydrobenzoin are formed. Collect the product via
vacuum filtration, wash the precipitate with small aliquots of cold water and dry
the product in air. If hydrobenzoin is precipitated when solid NaCl added to the
filtrate (until saturation is achieved), filter the product and weigh it separately.

TLC experiments

Determine the purity of the product by thin-layer chromatography on a silica gel

plate, using hexane and ethyl acetate mixture (3:1) as the eluting solvent.
Apply the spots of the product and starting material solutions separately on the
plate. Calculate Rf values of the product, starting material and some impurity (if it
is visible on the plate).

25
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