Practical Problems

Problemi pratici
Analisi qualitativa
ST
THE 1 INTERNATIONAL CHEMISTRY OLYMPIAD, Prague, 1968
PRACTICAL PROBLEMS
PROBLEM 1 (Practical)
There are ten test tubes in the rack at your disposal (1 – 10) and each test tube
contains one of aqueous solutions of the following salts: Na2SO4, AgNO3, KI, Ba(OH)2,
NH4Cl, Ag2SO4, Pb(NO3)2, NaOH, NH4I, KCl.
For identification of the particular test tubes you can use mutual reactions of the
solutions in the test tubes only.
Determine in which order the solutions of the salts in your rack are and write
chemical equations of the reactions you used for identification of the salts.
Each of the six test tubes (A – F) in the rack contains one of the following
substances:
benzoic acid, salicylic acid, citric acid, tartaric acid, oxalic acid and glucose.
Determine the order in which the substances in the test tubes are placed in your rack
and give chemical reactions you used for identification of the substances.
For identification of the substances the following aqueous solutions are at your
disposal: HCl, H2SO4, NaOH, NH4OH, CuSO4, KMnO4, FeCl3, KCl, and distilled water.
THE COMPETITION PROBLEMS FROM THE INTERNATIONAL CHEMISTRY OLYMPIADS, Volume 1 10

Edited by Anton Sirota,
IChO International Information Centre, Bratislava, Slovakia
ND
THE 2 INTERNATIONAL CHEMISTRY OLYMPIAD, Katowice, 1969
PRACTICAL PROBLEMS
a) Three numbered test-tubes (1-3) contain mixtures of two substances from the
following pairs (4 variants):
1. ZnSO4 - NaBr NaCl - Ca(NO3)2 MgSO4 - NH4Cl
2. AlCl3 - KBr CaCl2 - NaNO3 ZnCl2 - (NH4)2SO4
3. KNO3 - Na2CO3 KCl - MgSO4 NH4Cl - Ba(NO3)2
4. MgCl2 - KNO3 K2CO3 - ZnSO4 Al(NO3)3 - NaCl
b) Each of the test-tubes numbered 4 and 5 contains one of the following substances:
glucose, saccharose, urea, sodium acetate, oxalic acid.
Problem:
By means of reagents that are available on the laboratory desk determine the
content of the individual test-tubes. Give reasons for both the tests performed and your
answers and write the chemical equations of the corresponding reactions.
Note:
For the identification of substances given in the above task, the following reagents
were available to competing pupils: 1 N HCl, 3 N HCl, 1 N H2SO4, concentrated H2SO4,
FeSO4, 2 N NaOH, 20 % NaOH, 2 N NH4Cl, 2 N CuSO4, 2 N BaCl2, 0,1 N AgNO3, 0,1 %
KMnO4, distilled water, phenolphtalein, methyl orange. In addition, further laboratory
facilities, such as platinum wire, cobalt glass, etc., were available.

RD
THE 3 INTERNATIONAL CHEMISTRY OLYMPIAD, Budapest, 1970
PRACTICAL PROBLEMS
An unknown sample is a mixture of 1.2-molar H2SO4 and 1.47-molar HCl. By means of

available solutions and facilities determine:
1. the total amount of substance (in val) of the acid being present in 1 dm3 of the solution,
3
2. the mass of sulphuric acid as well as hydrochloric acid present in 1 dm of the sample.
By means of available reagents and facilities perform a qualitative analysis of the

substances given in numbered test tubes and write down their chemical formulas.
Give 10 equations of the chemical reactions by which the substances were proved:
5 equations for reactions of precipitation,
2 equations for reactions connected with release of a gas,
3 equations for redox reactions.

TH
THE 4 INTERNATIONAL CHEMISTRY OLYMPIAD, Moscow, 1972
PRACTICAL PROBLEMS
Determine unknown samples in ten numbered test tubes using reagents and facilities
available on the laboratory desk. Write chemical equations for the most important
reactions that were used to identify each substance. In case that the reactions take place
in solutions, write equations in a short ionic form.
On June 10th, a mixture of formic acid with an excess of ethanol was prepared. This
mixture was kept in a closed vessel for approximately one month. Determine quantitatively
the composition of the mixture on the day of the competition, using only reagents and
facilities available on the laboratory desk. Calculate the amounts of the acid and ethanol in
per cent by mass which were initially mixed together.

TH
THE 5 INTERNATIONAL CHEMISTRY OLYMPIAD, Sofia, 1973
PRACTICAL PROBLEMS
The following solutions of salts are available in twelve numbered test-tubes: AgNO3,
BaCl2, (NH4)2CO3, NaCl, KI, ZnCl2, NH4Cl, Pb(NO3)2, Al(NO3)3, CrCl3, Cr(NO3)3, Hg(NO3)2.
The numbering of the test tubes does not correspond to the order of the salts given
above. Prove the content of the test tubes by means of the least number of operations. In
your answer align the proper salt with each number of the test tube. Write chemical
equations for the reactions.
Six test tubes contain the following compounds:
Na2CO3 or NaHCO3 NiCl2 or CuCl2
AgNO3 or Pb(NO3)2 ZnCl2 or Al(NO3)3
ZnSO4 or KI NH4NO3 or Ba(NO3)2
The numbers of the test tubes do not correspond to the order of the compounds. Prove the
content of each test tube by available reagents. Describe the reactions by chemical
equations.
There are three test tubes marked by numbers 1, 2, and 3. Prove the content of each
test-tube by means of available reagents and write the proper formula of the compound to
each number. Write chemical equations for the reactions.

TH
THE 6 INTERNATIONAL CHEMISTRY OLYMPIAD, Bucuresti, 1974
PRACTICAL PROBLEMS
PROBLEM 1 (practical)
Test tubes with unknown samples contain:
- a salt of carboxylic acid,
- a phenol,
- a carbohydrate,
- an amide.
Determine the content of each test tube using reagents that are available on the
laboratory desk.
Determine cations in solutions No 5, 6, 8 and 9 using the solution in test tube 7.
Without using any indicator find out whether the solution in test tube 7 is an acid or a
hydroxide.
____________________
SOLUTION
Test tube: No 5 - NH+4 ; No 6 - Hg2+; No 7 - OH-; No 8 – Fe3+ ; No 9 – Cu2+
The solution in test tube No 10 contains two cations and two anions.
Prove those ions by means of reagents that are available on the laboratory desk.
____________________
SOLUTION
The solution in test tube No 10 contained: Ba , Al , Cl , CO 32−
2+ 3+ -

TH
THE 7 INTERNATIONAL CHEMISTRY OLYMPIAD, Veszprém, 1975
PRACTICAL PROBLEMS
Aqueous solutions of the following compounds: AgNO3, HCl, Ag2SO4, Pb(NO3)2,
NH3 and NaOH are available in numbered bottles. Allow to react each of them with others
and align the numbers of the bottles with formulas of the compounds.
Attention! The use of any other reagent is not permitted. In performing the reactions
3
do not use the whole volume of the solutions. A few cm of the solution should remain in
each bottle after your work is finished. It is advisable to make a draft at first but only those
solutions will be evaluated by the jury that will be written in the Table.
Write your observations into the squares of the Table bellow the diagonal using the
following uniform symbols:
white precipitate : ↓
coloured precipitate: ↓↓
formation of a complex soluble in water: [ ]
evolution of a gas: ↑
Write into the corresponding squares above the diagonal the chemical formulas of
the precipitate, the complex ion or gas which are formed by the corresponding reactions.
Write into the last line of the Table the final results obtained on the basis of your
experiments.
Number of
1 2 3 4 5 6
sample
1
Formula of
compounds

TH
A solid compound is in each of the numbered test-tubes. It might be chloride, iodide,
oxide, hydroxide, sulphide, sulphate or carbonate, each combined with one of the
+ 2+ 2+ 2+ 2+ 3+ 2+ 2+ 2+ 3+ 3+
following cations: Ag , Pb , Cu , Cd , Sb(V), Sn , Fe , Co , Ni , Mn , Cr , Al ,
2+ 2+
Zn , Ba .
Problem:
Write the chemical formula for each solid compound given as a sample. You can
use only reagents that are available on your laboratory desk.
Attention! In carrying out reactions do not use the whole quantity of the sample. A
small portion of the sample is to remain in each test tube. Only those results will be
evaluated that will be written in the Table below.
Table:
Compound
Number of sample Formula Number of sample Formula
1 6
2 7
3 8
4 9
5

TH
Three samples are found in sealed ampoules. All of them are aromatic compounds:
a hydrocarbon, a phenol, and an aldehyde.
Determine the group of compounds to which your numbered samples belong, using
only the reagents which are at your disposal.
Attention! Be careful when opening the ampoules. The identification of the samples
based upon physical characteristics only (colour, smell), is not sufficient. Only those
results will be taken into account that will be written in the Table below.
Table:
No of Reagent Observation Type of

sample compound

TH
THE 8 INTERNATIONAL CHEMISTRY OLYMPIAD, Halle, 1976
PRACTICAL PROBLEMS
A sample contains two of the following cations: Ag+, Pb2+, Fe2+, Cr3+, Co2+, Al3+,
Mn , and one of the following anions: SO 24− , Cl − , NO 3− .
2+
Prove the cations and anions in the sample by means of the following reagents:
2 N-HCl, concentrated H2SO4, 2 N-H2SO4, 2 N-HNO3, 2 N-CH3COOH, NaOH, NH4OH,
H2O2, Na2CO3, KNO3/Na2CO3, NH4SCN, Na2B4O7, NaF, C2H5OH, BaCl2, AgNO3, NH4Cl,
(NH4)2Fe(SO4)2, alizarin B.
Write the results into the attached table in the following way:
a) into the column "Reagent" write the formula of the reagent which was needed to prove
whether the cation or anion is present or absent in the sample;
b) into the column "+/−" mark the presence or absence of an ion, proved in the sample,
by the sign "+" and "−" , respectively.
A solution contains sodium oxalate and oxalic acid.
Determine how many milligrams of sodium oxalate and oxalic acid are contained in
the solution under investigation.
-3
The following solutions are at your disposal: KMnO4 (c = 0.01972 mol dm ), NaOH
-3
(c = 0.1019 mol dm ), concentrated H2SO4, and a solution of phenolphthalein.
TH
Four unknown organic aliphatic compounds of a general formula A−CH2−B are

numbered from 1 to 4, and given as samples. Some of them may be in an aqueous
solution.
Perform the following experiments:
1. Determine the pH value of the solution.
2. Allow the sample to react with hydrochloric acid.
3. Reaction with alkali hydroxide (basic hydrolysis − 5 minutes boiling under a reverse
cooler) and a subsequent proof of halides.
Moreover, the following data are at your disposal:
a) One of the compounds under investigation forms an intra-molecular anhydride.
b) The content of carbon and hydrogen (in mass %) as well as the relative molecular
mass are known for the same compound, the data being given, however, in an
arbitrary order which does not correspond to the numbering of samples.
Determine the functional groups A and B for each substance using results of your
experiments as well as the available data.
Write your results into the attached table; mark positive results with sign "+" whereas
the negative ones with sign "−".
TH
THE 11 INTERNATIONAL CHEMISTRY OLYMPIAD, Leningrad, 1979
PRACTICAL PROBLEMS
3
10 numbered test tubes, 20 cm each, contain 0.1 M solutions of the following
substances: barium chloride, sodium sulphate, potassium chloride, magnesium nitrate,
sodium orthophosphate, barium hydroxide, lead nitrate, potassium hydroxide, aluminium
sulphate, sodium carbonate. Using only these solutions as reagents, determine in which of
the numbered test tubes each of the above given substances, is found.
Draw up a plan of the analysis and write equations of the reactions to be carried out.
Do not forget to leave at least 2 cm3 of the solutions in each test tube for checking. If in
the course of the analysis an additional quantity of a solution is needed, you may ask the
teacher to give it to you but in such case you will lose some points.
____________________
SOLUTION
Table:
BaCl2 Na2SO4 KCl Mg(NO3)2 Na3PO4 Ba(OH)2 Pb(NO3)2 KOH Al2(SO4)3 Na2CO3
___ ___ ___ ___

BaCl2 ↓ ↓ ↓ ↓ ↓
___ ___ ___ ___ ___ ___
Na2SO4 ↓ ↓ ↓
___ ___ ___ ___ ___ ___ ___ ___
KCl ↓
___ ___ ___ ___ ___
Mg(NO3)2 ↓ ↓ ↓ ↓
___ ___ ___ ___
Na3PO4 ↓ ↓ ↓ ↓ ↓
___ ___ ___
Ba(OH)2 ↓ ↓ ↓ ↓ ↓ ↓
___
Pb(NO3)2 ↓ ↓ ↓ ↓ ↓ ↓ ↓ ↓
___ ___ ___ ___ ___ ___
KOH ↓ ↓ ↓
___ ___ ___
Al2(SO4)3 ↓ ↓ ↓ ↓ ↓ ↓
___ ___ ___ ___
Na2CO3 ↓ ↓ ↓ ↓ ↓
TH
Using the table, the entire problem cannot be solved at once: all the precipitates are
white and there are substances that form the same number of precipitates. From the
number of precipitates only KCl (1), Mg(NO3)2 (4), and Pb(NO3)2 (8) can be determined
immediately.
Furthermore, Na2SO4 and KOH (giving three precipitates each) can be differentiated
via the reaction with Mg(NO3)2 (Mg(OH)2).
Ba(OH)2 and Al2(SO4)3 (giving 6 precipitates each): through the reaction with KOH
(Al(OH)3).
BaCl2, Na3PO4 and Na2CO3 (giving 5 precipitates each): first the reaction with
Na2SO4 indicates BaCl2. Then the reaction with BaCl2: Al2(SO4)3 yields AlCl3 (BaSO4
precipitate is flittered off). Evolution of CO2 and formation of Al(OH)3 in the reaction with
AlCl3 solution indicates Na2CO3.
TH
THE 12 INTERNATIONAL CHEMISTRY OLYMPIAD, Linz, 1980
PRACTICAL PROBLEMS
Qualitative organic analysis
Four different substances that all occur in the nature, are present in 4 test tubes.
Find two substances that form basic components of fodders and human foodstuff. Only
these two substances are to be identified. Propose the names and structural formulae for
those two substances on the basis of combustion tests, solubility experiments,
identification of the functional groups and the determination of the melting point.
As an aid the following can be used:
A table of melting points, the Thiele apparatus for melting point determination, a solubility
scheme and the following reagents:
diethyl ether, NaHCO3 (5 %), NaOH (2 M), HCl (2 M), H2SO4 conc., H3PO4 conc., ethanol,
Tollens' reagents, (an ammoniac Ag solution), Fehling's solution I and II, phenylhydrazine
hydrochloride, β-naphthol, NaNO2 (solid) Ca(OH)2 sat., FeCl3 (5 %), ice, 2,4-dinitrophenyl-
hydrazine, ninhydrine solution (1 % alk.), Seliwanoff's reagent (resorcinol/HCl),
phloroglucine.
The requirements: An exact description of the experiments, reaction equations (or

reaction schemes where the equation cannot be given) for the reaction required for the
identification, the names and the structural formulae of the two test substances.
APPENDIX 1
Determination of the melting point by the Thiele apparatus
A finely pulverized sample is placed in a capillary that is sealed at one side, to a
height of 2 – 4 mm. To fill the capillary, it is immersed in the sample. The sample is
cautiously wiped off the capillary walls and the content of the capillary is brought to the
bottom by cautious tapping. Then the capillary is placed in the opening so that the sample
is at the height of the mercury bead of the thermometer. As the heat transmitter, suitable
high-boiling silicone oil is used in this apparatus.
TH
To determine the melting point of an unknown organic substance, an approximate melting

range is sought first. Thus the heating is carried out according to the figure at about 5
°C/min. For an exact determination another sample i s brought about 10 °C below the
determined melting range at about 5 °C/min and then the temperature is very slowly,
1 – 2 °C/min., brought to complete melting. The tem perature, at which the substance is
clearly melted, is taken as the melting point.
APPENDIX 2
Tables of melting points (MP, in °C) and boiling po ints (BP, in °C)
Compound MP BP Compound MP BP
ALDEHYDES
Pentanal - 103 Acrolein - 52
Benzaldehyde - 179 Furfurol - 161
Salicylaldehyde - 196 o-Chlorobenzaldehyde 11 214
o-Nitrobenzaldehyde 44 - α-Naphthaldehyde 34 -
p-Dimetylamino- 74 - Vanillin 81 -
bemzaldehyde
ALCOHOLS
terc.-Butanol 25 82 Propanol-1 - 97
n-Pentanol - 136 Ethyleneglycol - 197
Cyclohexylalcohol - 160 Butanediol-1,4 - 230
Triphenylcarbinol 165 - Glycerine - 290
AMINES
Diethylamide - 56 Morpholine - 130
Cyclohexylamine - 134 α-Naphthylamine 50 300
Aniline - 184 p-Bromoaniline 66 -
Diphenylamine 54 - m-Nitraniline 114 -
o-Phenylenediamine 102 - p-Aminophenol 186 D -
ACIDS
Palmitic acid 63 - n-Valeric acid - 186
Stearic acid 70 - Oleic acid 14 222
Oxalic acid (. 2 H2O) 101 - Mandelic acid 118 -
Acetylsalicylic acid 135 - Benzoic acid 122 -
Phthalic acid 203 - Malonic acid 135 -
Anthranilic acid 146 - S-Naphthoic acid 185 -
Glycine 232 D - p-Hydroxybenzoic acid 215 -
TH
HALOGENDERIVATIVES
n-Butyl bromide - 100 p-Dichlorobenzene 53 -
Cyclohexyl iodide - 179 p-Bromotoluene 28 185
Trichloroethylene - 67 Hexachlorobenzene 230 -
KETONES
Diethyl ketone - 102 Methylisobutyl ketone - 118
Cyclohexanone - 156 Acetophenone 20 202
Benzophenone 49 - p-Bromoacetophenone 51 -
Benzil 95 - dl-Camphor 178 -
CARBOHYDRATES
d-Ribose 95 D - β-Maltose 165 -
α-d-Glucose 146 D β-d-Fructose
Saccharose 180 - α-Lactose
HYDROCARBONS
n-Heptane - 99 Pentene-2 - 36
cis-Decaline - 194 Cyclohexene - 84
Cumol - 216 Diphenyl 70 -
Anthracene 216 - Styrene - 146
MERCAPTANS – THIOPHENOLS
n-Amylmercaptan - 126 p-Thiocresol - 200
Thiophenol - 169 p-Bromothiophenol 74 -
PHENOLS
p-Cresol 36 200 o-Nitrophenol 45 -
α-Naphthol 94 - Resorcinol 110 -
Pyrocatechol 105 - β-Naphthol 123 -
Picric acid 122 - Phloroglucine 218 -
ACID DERIVATIVES
Acetyl bromide - 77 Acetamide 82 -
Butyric acid chloride - 102 N-Methylacetanilide 102 -
4-Nitrobenzoylchloride 73 - Urea 132 -
Butyric acid ethylester - 121 Sodium formate 255 -
Malonic acid - 199 Al-Acetate 200 – 320 -
diethylester D
Palmitic acid cetylester 54 - Ba-Propionate ca. 300 -
D after the number denotes decomposition.
TH
APPENDIX 3
Solubility scheme
in H2O
soluble insoluble
in 5 % NaOH
soluble insoluble
in 5 % HCl
in ether in 5 % soluble insoluble

NaHCO3
in conc.
H2SO4
soluble insoluble soluble insoluble

insoluble soluble
in conc.
H3PO4
soluble insoluble
S1 S2 A1 A2 B M N1 N2 I
S1: Substances with higher volatility;

All low molecular alcohols, aldehydes, ketones, acids, amines, nitriles and acid
chlorides.
S2: Substances with low volatility, often distillable without decomposition: polyols, salts,
hydroxyaldehydes and hydroxyketones, carbohydrates, amino- and hydroxyl acids.
A1: Substances with low volatility: higher molecular acids, nitrophenols.
A2: Substances with high boiling points: Phenols, primary and secondary nitro
compounds, sulfonamides, weak acids.
B: Substances with high boiling points, distillable with water vapour: Basic compounds,
amines (with maximum of a few aryl groups), hydrazine.
M: Low volatility substances:
Neutral compounds, tertiary nitro compounds, nitroaniline, azo- and azoxy
compounds, nitrito-, nitrato-, sulphuric-, and phosphoric acid esters.
TH
N1: Substances with small volatility:

Alcohols, aldehydes, methyl ketones and esters with less than 9 C atoms, neutral
compounds, ethers, olephins.
N2: Substances with a very low volatility:
Alcohols, aldehydes, ketones, esters and thioalcohols with more than 9 C atoms,
neutral compounds, ethers, olephins.
I: Substances with low boiling point:
Inert compounds, hydrocarbons, halogenoalkanes.
APPENDIX 4
Preparation of the reagents
Tollen's reagent
3 3
Mix 0.5 cm 2 M NaOH + 1 cm 0.1 M AgNO3 in 2 M NH3.
Fehling's reagent
I: 1.73 g CuSO4 . 5 H2O in 25 cm3 of water
II: 8.5 g Seignette salt + 2.5 g NaOH in 25 cm3 H2O
Seliwanoff's reagent
3 3 3
125 g resorcinol is dissolved in 250 cm of diluted HCl (83 cm conc. HCl + 167 cm H2O),
preparing only a necessary amount.
Phenylhydrazine solution
0.5 g of phenylhydrazine hydrochloride + 0.5 cm3 glacial acetic acid in 2 cm3 H2O are
shaken until a clear solution is obtained.
2,4-dinitrophenylhydrazine solution,
2 cm3 of conc. H2SO4 are added to 0.4 g of 2,4-dinitrophenylhydrazine and then, with
stirring and shaking, 3 cm3 of H2O are added. To the warm solution, 10 cm3 of 95 %
ethanol are added.
____________________
TH
SOLUTION
In the four test tubes, pure sodium chloride, D-fructose, palmitic acid (hexadecanoic acid),
and vanillin were present. D-fructose, as a building block of cane sugar, and palmitic acid,
as the building block of most animal and plant fats, were identified.
a) Fructose
Melting range: 102 – 105 °C
Combustion test: Carbonizes during combustion with caramel smell.
Solubility: Readily soluble in water, insoluble in diethyl ether.
Identification of the functional groups:
Aldehydic group:
1. With Fehling's reagent
The oxidation of the carbonyl group with simultaneous reduction of Cu(II) to Cu(I).
–CHO + 2 [Cu(C4H4O6)2] + 5 OH → –COOH + Cu2O ↓ + 3 H2O + 4 C4H4O2-
2- -
6
2. With Tollen's reagent

The oxidation to the carboxyl group with simultaneous reduction of Ag(I) to Ag.
–CHO + 2 [Ag(NH3)2]+ + 2 OH- → –COOH + 2 Ag + 4 NH3 + H2O
Osazone formation (indication of monoses)
CH2OH HC=O HN-NH2 HC=N-NH-

+ C6H5NH2 + NH3 + 2 H2O
C O or HC OH + 3 HC=N-NH-
R R R
Ketose Aldose Phenyl- Osazone

hydrazine
Test for ketohexoses (Saliwanoff's reaction)

Ketohexoses form, with heating in acidic solution, 5-hydroxy-methylfurfural that condenses
with resorcinol to red-coloured substances.
TH
CH2OH
C O
OH
HO-CH
+ red coloration
HC - 3 H2O CHO
OH HOCH2
OH
O
HC OH
CH2OH
Test for pentoses (Tollens test)

Pentoses, in contrast to hexoses, form furfural in acidic solution that condenses with
phloroglucine to give red coloured substances.
CHO
OH
HC OH
+ red colouration
HC - 3 H2O CHO
OH
HO OH
O
HC OH
CH2OH
Name: The above reactions, the solubility behaviour and the melting range indicate that
this substance is D-fructose, a building block of cane sugar.
CH2OH
C O When giving the configuration, use the Fischer

projection.
HO-CH
HC OH
HC OH
CH2OH
TH
b) Palmitic acid
Melting range: 60 – 63 °C
Combustion test: Burns with yellowish, slightly smoking flame.
Solubility: Insoluble in water, very well soluble in 2 M NaOH, less soluble in 5 %
NaHCO3.
Identification of the functional groups:
2+
From alkaline solution a colourless substance is precipitated by Ca :
2 R-COO- + Ca2+ → (R-COO)2Ca
On the basis of flammability the solubility behaviour and the precipitation of the
calcium salt from alkaline solution one can conclude that the substance is an organic
carboxyl acid. The melting range indicates palmitic acid = hexadecanoic acid.
CH3-(CH2)14-COOH
TH
In 10 reagent bottles are 10 different pure metal samples. By evaluating the solubility
and by the following identification, only the six following elements are to be specified by
their sample numbers:
calcium, iron, aluminium, zinc, magnesium, tin.
It is expected to specify:
a) the symbol of the identified metal and the corresponding bottle number,
b) a reaction equation for dissolution of each of the six metals,
c) an unambiguous verbal proof or a proof in the form of a chemical equation.
The following chemicals are at disposal:

HCl conc., HCl (2 M), H2SO4 (2 M), CH3COOH (2 M), NaOH (2 M), NH3 (2 M), NH4SCN
(0.2 M), CH3COONa (conc.), 3 % H2O2, Na2CO3 (0.2 M), H2S (0.1 M), Na2HPO4 (0.2 M),
K4Fe(CN)6 (0.2 M), K3Fe(CN)6 (0.2 M), morin (in CH3OH), quinalizarine (in C2H5OH),
urotropine (20 %), dithizone (in CCl4), (NH4)2C2O4 (0.2 M), distilled water.
SOLUTION
a) See the list at the end.
b) Ca + 2 H2O → Ca(OH)2 + H2
Ca + 2 H3O → Ca
+ 2+
+ H2 + 2 H2O
Fe + 2 H3O+ → Fe2+ + H2 + 2 H2O
Al + 3 H3O+ → Al3+ + 3/2 H2 + 3 H2O

Al + NaOH + 3 H2O → Na+ + [Al(OH)4 ]− + 3/2 H2
Zn + 2 H3O+ → Zn2+ + H2 + 2 H2O

Zn + 2 NaOH + 2 H2O → 2 Na+ + [Zn(OH)4 ]2− + H2
Mg + 2 H2O → Mg(OH)2 + H2
Mg + 2 H3O+ → Mg2+ + H2 + 2 H2O
TH
Sn + 2 H3O+ → Sn2+ + H2 + 2 H2O

Sn + 2 NaOH + 2 H2O → 2 Na+ + [Sn(OH)4 ]2− + H2
c) Ca2+: white precipitate with (NH4)2C2O4;

2+
Fe : blue with K3[Fe(CN)6]
or after oxidation with H2O2: blue with K4[Fe(CN)6] or red with NH4SCN, or
brown precipitate with NaOH;
3+
Al : green fluorescence with morine (in dilute acetic acid);
2+
Zn : white precipitate with H2S (in acetic acid),
with dithizone red coloration of the organic phase;
Mg2+: with quinalizarine light blue lacquer (alkali solution);
Sn2+: with H2S deep brown precipitate (weakly acidic solution),
blue fluorescence of the outer wall of a glass bottle filled with cold water
that was immersed in an Sn2+ solution (acidified with HCl),
in the flame of a Bunsen burner ("light test").
TH
THE 13 INTERNATIONAL CHEMISTRY OLYMPIAD, Burgas, 1981
PRACTICAL PROBLEMS
Fourteen numbered test tubes contain solutions of pure inorganic substances. Each
test tube contains only one substance. The samples contain the following ions:
cations K+, Na+, Hg2+

+ + 2+ 2+ 3+
2 , Ag , NH4 , Ba , Sr , Fe ;
anions OH–, NO3- , Cl–, SCN–, I–, CO32- , Cr2O72- , CrO2- 4- 3-

4 , Fe(CN)6 , Co(NO 2 )6 .
Determine the contents of the test tubes. In addition to reactions between samples,
the only other possible reagent is a solution of hydrochloric acid with a concentration of 2
mol dm-3.
Fill in the following information on the sheet provided:
1. The chemical formulae of the individual samples and the numbers of the
corresponding test tubes.
2. The chemical formulae in ionic form on the basis of which you demonstrated the
presence of individual cations present in the samples.
TH
Determine the samples in the test tubes using the following reagents:
FeCl3 (2.5 % aqueous solution), water, 2,4-dinitrophenylhydrazine, Lucas' reagent (ZnCl2
– HCl), NaOH (5 % aqueous solution), NaHCO3 (5 % aqueous solution), HCl (conc.),
2+
Fehling's solution (an alkaline aqueous solution containing Cu ions; this is prepared
immediately prior to use by mixing identical volumes of Fehling's solutions I and II),
Tollen's reagent (prepared immediately prior to use by mixing identical volumes of 10 %
-3
solution of AgNO3 and an NaOH solution with a concentration 2 mol dm . Finally,
ammonia is added dropwise to complete dissolution of silver dioxide.
Write the results of your observations during testing the unknown substances with
the reagents into the table provided.
Write the (IUPAC) names and structural formulae for the substances in the test
tubes.
Write the chemical equations for the reactions on the basis of which the individual
substances were identified. Write only a reaction scheme where this not possible.
TH
THE 14 INTERNATIONAL CHEMISTRY OLYMPIAD, Stockholm, 1982
Each of 8 numbered test tubes contains a solution of one salt. In the solutions the
following positive ions can be found (a maximum of one in each test tube):
Ag , Al , Cu , Na , NH+4 , and Zn2+
+ 3+ 2+ +
and the following negative ions (at most one in each test tube)
– – – –
Br , Cl , I , NO3– , OH , and S3O32- .
A test plate, test tubes in a rack, dropping pipettes, indicator paper, and a gas
burner are also provided.
Determine by means of mutual reactions which salt is dissolved in each test tube.
Confirm your conclusions by carrying out as many reactions as possible. It may be
necessary to use combinations of solutions and reagents.
Give a list of numbers and corresponding formulae of the substances, indicate the
formation of a precipitate by a downward arrow, and gas evolution by an upward arrow in
the square array provided for reporting the reactions.
Write chemical equations for all the reactions observed.
____________________
SOLUTION
Numbers of Chemical equation for the observed reaction
solutions mixed
1+2 NH+4 + OH– → NH3(g) + H2O
2 OH + 2 Ag → Ag2O(s) + H2O
– +
2+3
2+3+1 Ag2O(s) + 4 NH+4 + 2 OH– → 2 Ag(NH3 )+2 + 3 H2O
2+4 Zn2+ + 2 OH– → Zn(OH)2(s) ↔ Zn(OH)2(s) + 2 OH– → Zn(OH)2-

4
2+5 Al3+ + 3 OH– → Al(OH)3(s) ↔ Al(OH)3(s) + OH– → Al(OH)-4
Reactions to distinguish Zn2+ from Al3+:

Numbers of Chemical equation for the observed reaction
solutions mixed
4 + 4 NH4 → Zn(NH3 )4 + 4 H2O
Zn(OH)2- + 2+
2+4+1
2+5+1 Al(OH)-4 + 2 NH+4 → Al(OH)3(s) + NH3 + H2O
2+6 Cu2+ + 2 OH– → Cu(OH)2(s)
TH
Cu(OH)2(s) + 4 NH+4 + 2 OH → Cu(NH3 )2+

–
2+6+1 4 + 4 H2O
Ag + Cl → AgCl(s)
+ –
3+4
Ag + Br → AgBr(s)
+ –
3+6
Ag + I → AgI(s)
+ –
3+7
2 Ag+ + S2O32- → Ag2S2O3(s) ↔ Ag2S2O3(s) + 3 S2O32- →
3+8
→ 2 Ag(S2O3 )3-
2
Reactions to distinguish Cl– from Br– and from I–
3+4+1+2 AgCl(s) + 2 NH+4 + 2 OH– → Ag(NH3 )+2 + Cl– + H2O
AgCl(s) + 2 S2O32- → Ag(S2O3 )3-

–
3+4+8 2 + Cl
3+6+1+2 AgBr(s) does not dissolve

AgBr(s) + 2 S2O32- → Ag(S2O3 )3-
–
3+6+8 2 + Br
3+7+8 AgI(s) does not dissolve

→ 2 CuI(s) + I2
2+ –
6+7 2 Cu +4I
I2(s) + 2 S2O32- → 2 I + S4O62-
–
6+7+8
1 2 3 4 5 6 7 8
1 ↑
2 ↑ ↓ ↓ ↓ ↓
3 ↓ ↓ ↓ ↓ ↓
4 ↓ ↓
5 ↓
6 ↓ ↓ ↓
7 ↓ ↓
8 ↓
TH
List of numbers and corresponding formulae for the substances:

1. NH4NO3 5. Al(NO3)3
2. NaOH 6. CuBr2
3. AgNO3 7. NaI
4. ZnCl2 8. Na2S2O3
TH
THE 15 INTERNATIONAL CHEMISTRY OLYMPIAD, Timisoara, 1983
PRACTICAL PROBLEMS
In test tubes A, B, C, and D there are four benzene derivatives containing one or two
functional groups of three distinct types. Identify the functional groups of compounds A, B,
C, and D using the available reagents.
– Justify your choice by writing down the identification reactions.
– Using as reagents the four compounds A, B, C, and D synthesize four organic dyes
and write the equations for the reactions performed.
____________________
SOLUTION
The four compounds are as follows:
COOH
-NH2 -OH -OH H2N- -COOH
A B C D
The identification reactions:
a) With H2SO4:
-NH2 + H2SO4 NH3+ HSO4-
H3N+ COO- + H2SO4 H3N+ COOH HSO4-
b) With NaOH:
_
-OH + NaOH O Na+ + HOH
TH
COOH COONa
-OH + NaOH OH + HOH
_ _
H3N+ COO + NaOH H2N COO Na+ + HOH
c) With NaHCO3:
COOH COONa
-OH + NaHCO3 OH + CO2 + HOH
d) With NH2 SO3H
_ + _ +
O 3S NH3 + NaNO2 + H2SO4 O 3S N N + NaHSO4 + 2 HOH
_ + NaOH
O3S N N + OH HO3S N N OH
(orange)
COOH COOH
_ + NaOH
O3S N N + -OH HO3S N N OH
(orange)
_ + H2SO4
O3S N N + NH2 HO3S N N NH2
(orange)
II. e) With β-naphthol:

+ _
NH2 + NaNO2 + H2SO4 N N HSO4
TH
OH OH
+ _ NaOH
N N HSO4 + N N + Na2SO4
+ HOH
yellow - orange
_ +
HOOC NH2 + NaNO2 + H2SO4 OOC N N + NaHSO4 + 2 HOH
OH OH
_ + NaOH
OOC N N + NaOOC _ N N + HOH
red
The following dyes can be obtained:

+ _ NaOH
N N HSO4 + OH N N OH
(red - orange)
COOH COOH
+ NaOH
N N + -OH N N OH
(red - orange)
+ _
HOOC N N HSO4 + OH HOOC N N OH
(red - orange)
COOH COOH
+ _
N N HSO4 + -OH HOOC N N OH
HOOC
(red - orange)
TH
Six test-tubes contain aqueous solutions of FeSO4, H2SO4, Mn(NO3)2, H2O2, Pb(NO3)2,
NaOH.
a) Identify the content of each test-tube without using other reagents. Write the results in
tabular form. Write the equations for the chemical reactions used for the identification.
b) After identification, perform four reactions each time using three of the identified
compounds and write the equations.
____________________
SOLUTION
FeSO4 H2SO4 Mn(NO3)2 H2O2 Pb(NO3)2 NaOH

1) Fe(OH)2 ↓
white-
FeSO4
greenish
_ _ Fe(OH)SO4 PbSO4 ↓ ↓
yellowish white Fe(OH)3 ↓
brown-
redish
2)
_ _ _ PbSO4 ↓ _
H2SO4 white
3) Mn(OH)2 ↓
white
Mn(NO3)2 _ _ _ _ ↓
MnMnO3 ↓
brown black
4)
Fe(OH)SO4 _ _ _ _
H2O2 yellowish
5) PbSO4 ↓
PbSO4 ↓ _ _ _
Pb(NO3)2 white white
6) Fe(OH)2 ↓ Mn(OH)2 ↓ Pb(OH)2 ↓

white- white white
NaOH
greenish ↓ ↓
↓ MnMnO3 ↓ Pb(OH)24−
_ _
Fe(OH)3 ↓ brown black
brown-
redish
TH
Reactions Observation
(1) + (4) FeSO4 + H2O2 → 2 Fe(OH)SO4 Colour change
3+
- yellowish (Fe )
(1) + (5) FeSO4 + Pb(NO3)2 → PbSO4 ↓ + Fe(NO3)2 Appearance of a white
precipitate.
(1) + (6) FeSO4 + 2 NaOH → Fe(OH)2 ↓ + Na2SO4 Appearance of a greenish white
precipitate Fe(OH)2 which after
Fe(OH)2 + ½ O2 + H2O → Fe(OH)3 oxidation by air turns into a
reddish brown precipitate
Fe(OH)3.
(2) + (5) H2SO4 + Pb(NO3)2 → PbSO4 ↓ + 2 HNO3 Appearance of a white
precipitate PbSO4.
(3) + (6) Mn(NO3)2 + 2 NaOH → Mn(OH)2 + 2 NaNO3 Appearance of a white
precipitate Mn(OH)2 which after
2 Mn(OH)2 + ½ O2 → MnMnO3 + 2 H2O oxidation by air coverts into a
Mn(OH)2 + ½ O2 → MnO2 + H2O brown-black precipitate
MnMnO3 which eventually
changes into MnO2 – a black-
brown precipitate.
(5) + (6) Pb(NO3)2 + 2 NaOH → Pb(OH)2 + 2 NaNO3 Appearance of a white
precipitate Pb(OH)2 which
Pb(OH)2 + 2 NaOH → Na2Pb(OH)4 dissolves in excess reagent.
b)
(1) + (2) + (4) 2 FeSO4 + H2O2 + H2SO4 → Fe2(SO4)3 + 2 H2O Colour change → yellowish
(Fe3+)
(1) + (4) + (6) 2 FeSO4 + H2O2 + 4 NaOH → Fe(OH)3 + Appearance of a brown-reddish
precipitate Fe(OH)3
+ 2 Na2SO4
(3) + (4) + (6) Mn(NO3)2 + H2O2 + 2 NaOH → MnO2 + 2 NaNO3 Appearance of a brown
precipitate MnO2
+ 2 H2O
(5) + (4) + (6) Pb(NO3)2 + H2O2 + 2 NaOH → PbO2 + 2 NaNO3 Appearance of a brown
precipitate PbO2.
+ 2 H2O
TH
THE 19 INTERNATIONAL CHEMISTRY OLYMPIAD, Veszprém – Budapest, 1987
PRACTICAL PROBLEMS
You are required to investigate seven inorganic compounds.
Your test-tube rack is numbered 1 to 9. Two of the positions are empty. Each of the
seven test-tubes provided contains only one compound in aqueous solution. Using only
these solutions, pH indicator paper, and test-tubes, you are to identify as many of the ions
present as you are able.
For your information, record in the table the observations you make on mixing the
solutions. Use the following symbols:
elimination reactions: ↓ precipitate; ↑ gaseous product;
↓s precipitate soluble in the excess of a precipitating agent.
colours: w - white or colourless, b - blue, g - green, y - yellow, p - pink, r - red, br - brown.
pH: a - acidic, b - alkaline, n - neutral.
Equipment:
A home-made rack contained 9 test-tubes with the unknown solutions, 30 empty
Wassermann-tubes and one small beaker containing the pH indicator paper. Into each
solution a dropper was inserted, and thus, the test-tubes need not to be removed from the
rack while handling them. According to the original plan the following nine unknown
solutions were expected to be given to the participants: CoCl2, Fe(SCN)3, NH4OH, KI,
AgNO3, Na2HAsO4, HgCl2, NiCl2, CuCl2.
During the discussion of the International Jury it became known that in some
countries the corresponding laws forbid the pupils in secondary schools to handle mercury
and arsenic compounds. For this reason these two compounds were removed from the
rack and consequently the number of ions to be detected - and the marks available - were
reduced to 12 (from the original 15). (Under these conditions the alkali and nitrate ions
cannot be detected.)
The order of the test-tubes varied individually, but the first two contained invariably
red solutions (CoCl2 and Fe(SCN)3), while the last two were the green NiCl2 and CuCl2
symbolizing the Hungarian national colours, red-white-green.
____________________
TH
SOLUTION
The ions of the remaining seven solutions can easily be identified by mutual
reactions. Out of the 21 possible reactions, 12 are common positive reactions. Additional
information is available from the colour of 4, and the smell of one solution.
AgNO3: reacts with all the six compounds;
NH3: with the exception of iodide it gives a characteristic reaction with all the others
salts;
- +
Fe(SCN)3: its colour and reaction with NH3, I , Ag are characteristic;
CoCl2: can be detected from its colour and by adding NH3 or Ag+;
KI: can be identified by its reaction with Ag+ and from the evolution of I2 due to an
addition of Fe3+ or Cu2+;
- +
CuCl2: can be detected from its colour and reaction with NH3, I and Ag ;
NiCl2: has a characteristic colour and reacts with NH3 and Ag+.
ND
THE 22 INTERNATIONAL CHEMISTRY OLYMPIAD, Paris, 1990
Qualitative Analysis
Equipment:
Five flasks are labelled 2.1 through 2.5. Each contains an aqueous solution of a colourless
metal nitrate. Except for silver nitrate, the concentrations of the nitrates used to prepare
-3
these solutions, are all 0.1 mol dm .
The solutions are: aluminium(III) nitrate

calcium(II) nitrate
lead(II) nitrate
silver(I) nitrate
zinc(II) nitrate
Moreover, available are pH indicator paper and the following three reagents of a
concentration of about 5 mol dm-3, contained in flasks labelled 2.6 through 2.8.
2.6 : hydrochloric acid,
2.7 : aqueous ammonia solution,
2.8 : sodium hydroxide solution.
Beware: these solutions are all concentrated and corrosive.
Tasks:
2.1 Carry out reactions between each reagent and each solution. For each of the
solutions 2.1 through 2.5, record your observations for each reaction observed.
2.2 Write the name of the cation contained in each of the solutions 2.1 through 2.5 in the
corresponding space on the answer sheet.
2.3 For each cation identified, write the equation for each reaction observed.
_______________
SOLUTION
2.1 Aluminium(III) nitrate
- Al3+ + HCl → no reaction
- Al3+ + 3 NH3 + 3 H2O → Al(OH)3 ↓ + 3 NH+4
- Al3+ + 3 OH– → Al(OH)3 ↓
Edited by Anton Sirota
ND
- Al(OH)3 + OH– → [Al(OH)4]– (aq)
calcium(II) nitrate
- Ca2+ + HCl → no reaction
+ 2 OH → Ca(OH)2 ↓
2+ –
- Ca
lead(II) nitrate
- Pb2+ + 2 Cl– → PbCl2 ↓ (in cold solutions)
- Pb2+ + 2 NH3 + 2 H2O → Pb(OH)2 ↓ + 2 NH+4
- Pb2+ + 2 OH– → Pb(OH)2 ↓

Pb(OH)2 + 2 OH → [Pb(OH)4]
– 2–
(aq)
silver(I) nitrate
Ag + Cl → AgCl ↓
+ –
-
Ag + NH3 + H2O → AgOH ↓ + NH+4 (or Ag2O)
+
-
AgOH + 2 NH3 → [Ag(NH3)2] (aq) + OH

+ –
Ag + OH → AgOH ↓
+ –
-
2 AgOH → Ag2O + H2O
zinc(II) nitrate
+ HCl → no reaction
2+
- Zn
+ 2 NH3 + 2 H2O → Zn(OH)2 ↓ + 2 NH+4
2+
- Zn
Zn(OH)2 + 4 NH3 → [Zn(NH3)4] (aq) + 2 OH

2+ –
+ 2 OH → Zn(OH)2 ↓
2+ –
- Zn
Zn(OH)2 + 2 OH → [Zn(OH)4] (aq)
– –
TH
THE 27 INTERNATIONAL CHEMISTRY OLYMPIAD, Beijing, 1995
PRACTICAL PROBLEMS
Identification of Unknown Solutions
You are supplied with five different solutions contained in five test tubes labelled as
A, B, C, D and E, respectively. The solution in each test tube contains one of the following
compounds:
NH4Cl (NH4)2SO4 NaNO3 MgCl2 Na2SO4
Identify these solutions.
Reagents
-3
H2SO4 (conc.) H2SO4 (6 mol dm )
-3
HNO3 (conc.) HNO3 (6 mol dm )
-3
HCl (conc.) HCl (6 mol dm )
-3
Ba(OH)2 (satd.) NaOH (6 mol dm )
-3 -3
BaCl2 (0.5 mol dm ) Ba(NO3)2 (0.5 mol dm )
NOTES:
(1) You can only select the provided reagents and use a procedure as simple as
possible to complete your task. You are getting a mark not only according to the
correct identification, but also to the number of steps you have taken.
(2) You have to carry out the whole analysis by using the provided amount of these
unknown solutions. Supplement of them will be available, but it will reduce the mark
you obtain.
TH
THE 29 INTERNATIONAL CHEMISTRY OLYMPIAD, Montreal, 1997
Organic qualitative analysis
You have six bottles containing six different organic compounds. From the list of
eight compounds given below, identify the contents of each bottle using the reagents
available.
Many of these compounds have strong odours. To prevent the laboratory from
becoming too odorous, you must keep each bottle tightly capped when it is not in use.
Dispose of any waste produced in the bottle labelled “ORGANIC WASTE” at your station.
Also place used litmus paper in this bottle. Keep the waste bottle capped when not in use.
Chemicals Available
litmus paper, red and blue
aqueous ceric ammonium nitrate
aqueous chromic-sulfuric acid
aqueous 2,4-dinitrophenylhydrazine
aqueous 0.2% KMnO4
acetone (2-propanone)
Possible Unknowns*
2-butanone
1-decene
2,3-diamino-2,3-dimethylbutane
hexane
3-methyl-1-butanol
2-methyl-2-butanol
nonanal
propanoic acid
*Several of the unknowns are present as dilute aqueous solutions.

This will not interfere with the test results.
ST
THE 31 INTERNATIONAL CHEMISTRY OLYMPIAD, Bangkok, 1999
Isolation and Identification of an Essential Oil from Natural Source
In this experiment, you will steam distil and determine the structures of the main
essential oil (S) from a given natural source and a product from its chemical conversion
(unknown Y).
To determine the structures, you have to use organic qualitative analysis to identify
any functional groups present in the compounds by using the reagents at your station.
NMR data will be given only after the functional group test is completed.
Chemicals Available:
Sample (1 g in a vial)
Unknown Y (in a vial)
Anhydrous Na2SO4 (in a plastic vial), dichloromethane, ceric ammonium nitrate solution,
2,4-Dinitrophenylhydrazine (labelled as 2,4-DNP), 2 % aq. NH3, 5 % aq. AgNO3, 5 % aq.
HCl, 5 % aq. NaOH, 5 % aq. NaHCO3, 1 % FeCl3 in EtOH, 0.2 % aq. KMnO4,
decolourised with easily oxidised functional groups, acetone (for washing).
Procedure:
1. Apparatus: Assemble a distillation apparatus using a 25 cm3 round bottomed flask
3
for distillation and a 10 cm round bottomed flask to collect the distillate. Heat the sand
bath to approximately 150 °C before proceeding the next step.
Simplified Steam Distillation: Mix 1 g of ground sample with 15 cm3 of water in the 25
3
cm round bottomed flask and allow the sample to soak in the water for about 10 minutes
before distillation. Do not forget to put in a magnetic bar, turn on the water in the
condenser and stirring motor, heat the mixture (the temperature of the sand bath should
not be below 170 °C) to provide a steady rate of distillation. At least 5 cm3 of distillate
must be collected. Hot plate must be turned off after distillation is finished. Disassemble
the apparatus and rinse the condenser with acetone. Be sure that the condenser is dry
before using in the next step
ST
Extraction of the Essential Oil: Transfer the distillate to a 15 cm3 capped centrifuge
3
tube and add 1 cm of dichloromethane to extract the distillate. Cap the tube securely and
shake vigorously, cool in ice. Allow the layers to separate.
3
Using a Pasteur pipette, transfer the dichloromethane layer to a 10 cm test tube.
3
Repeat this extraction with fresh 1 cm dichloromethane twice and combine with the first
extract.
Drying: Dry the dichloromethane extract by adding anhydrous Na2SO4 and stir
occasionally for 10 minutes.
Evaporation: With a clean, dry cotton plugged Pasteur pipette transfer the organic
layer to a dry 5 cm3 conical vial. Use approximately 1 cm3 of clean dichloromethane to
wash Na2SO4 using the dry cotton plugged Pasteur pipette, then transfer into the vial. Be
careful not to transfer any of the Na2SO4 into the vial. Use Hickman still head and dry
condenser to distil the dichloromethane from the solution until the volume is reduced to
1 cm3. Discard the distilled dichloromethane from the Hickman still head with a Pasteur
pipette or a syringe to a vial (for recovered dichloromethane) and keep the residue for
functional group analysis.
Functional Group Analysis: Carry out the functional group analysis of the residue
solution (1 cm3) by using the appropriate reagents at your station. (Note: dichloromethane
is immiscible with water.)
Tollen’s Reagent: add 1 drop of 5 % aq. AgNO3 in a small test tube followed by
1 drop of 5 % aq. NaOH, brown precipitate will appear. Add 2 % aq NH3 to the tube until
all the precipitate dissolved. The solution is ready for the test.
2. Structure elucidation of the main essential oil (S)

Reaction of the main essential oil (S) with CH3I in the presence of K2CO3 gives
compound X (C11H14O2). Oxidation of X gives unknown Y (C10H12O4) as the main product
and CO2.
3. Structure elucidation of the unknown Y:

Identify the functional groups of unknown Y (provided in a conical vial) by using the
reagents at your station and fill in your results in the answer sheet. Indicate the functional
group(s) present or not present.
ST
Hand in your copy of answer sheet PART I (Demonstrator copy) of functional group
1 1
analysis and ask for H NMR spectra. H NMR spectra will be given only when the
functional group analysis is completed.
4. Draw the structure which represents the main component in the essential oil (S) that
1
was distilled from the sample. Assign each proton from the provided H NMR spectra by
labelling the peak number on the proton in the structure in the answer sheet.
5. Draw the structures of compound X and unknown Y. Assign each proton of unknown
1
Y from the provided H NMR spectra in the same manner as in (4).
_______________
SOLUTION
1. It was expected to obtain at least 5 cm3 of distillate.
2. Functional group analysis of the distilled essential oil:
Reagents Positive Negative
test test
0.2 % KMnO4
1 % FeCl3
2,4-DNP
Ceric ammonium nitrate
Tollen's Reagent
Functional groups in S Present Not

present
-C=C-
-OH (alcoholic)
-OH (phenolic)
-CHO
-CO-
-COOH
3. Funcional group analysis of the unknown compound Y:

Reagents Positive Negative
test test
5 % HCl
5 % NaOH
5 % NaHCO3
0.2 % KMnO4
1 % FeCl3
2,4-DNP
Ceric ammonium nitrate
Tollen's Reagent
ST
Functional groups Present Not

in Unknown Y present
-C=C-
-OH (alcoholic)
-OH (phenolic)
-CHO
-CO-
-COOH
4. The structure which represents the main essential oil (S):
5. The structure of compound X and unknown Y:

Compound X Compound Y
ST
NMR spectrum of the main essential oil (S):

(See peak number in the given 'H NMR spectrum)
Peak Chemical shift No. of proton(s) Multiplicity

No. (δ, ppm)
1 3.31 2H d
2 3.84 3H S
34 5.0 – 5.1 2H m
5 5.6 1H S
5.9 – 6.0 1H m
6 6.7 2H S
d or m
7 6.87 1H d
NMR assignment of the main essential oil (S):
NMR spectrum of the unknown Y:

(See peak number in the given 'H NMR spectrum. Labile proton does not appear in the
spectrum.)
ST
Chemical
Peak shift No. of proton(s) Multiplicity
No. (δ, ppm)
1 3.59 2H s
2 3.86 3H s
3 3.88 3H s
4 6.81 3H s
NMR assignment of the main essential oil (S):
TH
THE 36 INTERNATIONAL CHEMISTRY OLYMPIAD, Kiel, 2004
Qualitative and Quantitative Analysis of a Superconductor
Introduction
Superconductors based on lanthanum cuprate (La2CuO4) have the general compo-
sition of LaxM(2-x)CuO4 (M = Ca, Sr, Ba).
This problem consists of two parts:
- the qualitative determination of the alkaline earth metal(s)
- the quantitative determination of lanthanum and copper.
Read the burette as accurately as possible. Report your results on the answer sheets.
Answer the additional questions and write the results with adequate accuracy.
The qualitative and quantitative parts of this experiment may be done in any order.
Procedures
2.1 Qualitative determination of the alkaline earth metal(s)
(If the hood is occupied start with the titration 2.2)
In this experiment you have to use the superconductor as a solid (LaxM(2-x)CuO4; No. 14).
At the beginning, lanthanum has to be separated as an insoluble residue.
All steps must be carried out in the hood!
Dissolve the complete sample in a beaker in about 5 cm3 of perchloric acid (No. 22) by
3
heating the mixture. Add 5 cm of demineralized water afterwards.
Cool down the solution until it is lukewarm.
Add about 5 cm3 of demineralized water and then ammonia solution (No. 17), until
the reaction mixture shows a basic reaction. Lanthanum precipitates as hydroxide and
copper forms an intense blue-coloured tetraammine complex. The precipitate is filtered off
and washed with a small amount of demineralized water.
An excess of ammonium-carbonate solution (No. 18) is added to the filtrate and the
mixture is being boiled for some minutes. The alkaline earth metal(s) will precipitate as
carbonate(s). The precipitate is filtered off and washed a few times with a small amount of
demineralized water.
TH
Then, the precipitate is dissolved in acetic acid (No. 16). Add sodium acetate (No. 9)
and an excess of potassium-dichromate solution (No. 23). In the presence of barium,
yellow BaCrO4 precipitates. After boiling the mixture for one minute barium chromate is
filtered off and washed with demineralized water.
(If there is no barium chromate precipitation, proceed in a way as if there were
precipitation.)
Ammonia solution (No. 17) is added to the clear filtrate until it is basic. Add an
excess of ammonium-carbonate solution (No. 18) and boil the mixture for some minutes.
In the presence of strontium and/or calcium, white carbonate(s) precipitate(s).
The precipitate is filtered off and washed a few times with demineralized water.
Then it is dissolved in a mixture of about 2 cm3 of demineralized water and a few drops of
hydrochloric acid (No. 3). This solution is devided between two test tubes:
• Saturated calcium-sulfate solution (No. 21) is added to one of the test tubes. In the
presence of strontium a small amount of white strontium sulfate precipitates. To
accelerate the precipitation, you can grind the inner surface of the test tube with a
glass rod for a few minutes.
• Ammonium-sulfate solution (No. 20) is added to the second test tube. In the
presence of strontium and/or calcium, white sulfate(s) precipitate(s). The precipitate
is filtered off and washed with a very small amount of demineralized water.
1 cm3 of ammonium-oxalate solution (No. 19) is added to the filtrate. In the presence
of calcium, white calcium oxalate precipitates after a few minutes.
Preparation of the superconductor parent solution

There is a superconductor solution (LaxM(2-x)CuO4 in perchloric acid; No. 13) in a
volumetric flask.
Fill it up with demineralized water to a volume of 250.0 cm3. From now on this solution is
called “parent solution”.
2.2 Quantitative determination of the total content of lanthanum and copper

Transfer 25.00 cm3 of the parent solution into an Erlenmeyer flask. Add about 5-6
piled spatula of sodium acetate (CH3COONa; No. 8) and 2 micro spatula of xylenol orange
indicator (No. 15) to this solution and make up with demineralized water to a volume of
TH
3
about 75 cm . The pH-value has to be about pH 6 before the determination, otherwise
add more sodium acetate.
Titrate the solution with Na2-EDTA solution (No. 7). The color of the solution changes
from light violet to intensely light-green. (In between, the color changes a few times.)
Repeat this procedure as many times as necessary.
2.3 Quantitative determination of the copper content

3 3
Transfer 25.00 cm of your parent solution (No. 13) into the 100 cm volumetric flask
3
and fill up with demineralized water to a volume of 100.0 cm . For each titration, transfer
25.00 cm3 of this solution into an Erlenmeyer flask and add sodium hydroxide solution
(No. 6), until the solution shows an alkaline reaction. During this procedure, a blue
precipitate forms. Add sulfuric acid (No. 12) until the blue precipitate dissolves. The
solution has to be acidic (pH 1-2) and will contain a small amount of a white precipitate.
Add 10 cm3 of sodium-iodide solution (No. 9), and swirl the Erlenmeyer flask for
about 1 minute. Titrate the solution with sodium-thiosulfate solution (No. 10). Add some
starch solution (No. 11) as an indicator just before the end of the titration. At the end, the
solution has to be colourless for at least 60 seconds.

_______________
SOLUTION
2.1 Which alkaline earth metal(s) can be found in the superconductor? Mark only one
box!
Ca Sr Ba
Ca and Sr Ca and Ba Sr and Ba
Ca and Sr and Ba
Complete the following reaction equations:
Ca2+ + C2O24− CaC2O4
+ CO23−
2+
Sr SrCO3
TH
2 Ba 2+ + Cr2O72− + H2O 2 BaCrO4 + 2 H

+
2.2 Quantitative determination of the total content of lanthanum and copper.

-3 3
Appropriate consumption of 0.1000 mol dm EDTA solution: V = 11.60 cm
3
(accoding to 100 cm of superconductor solution)
2.3 Quantitative determination of the copper content.

-3 3
Appropriate consumption of 0.01000 mol dm Na2S2O3 solution: V = 10.50 cm
3
(according to 100 cm of superconductor solution)
2+ -
2 Cu +4I I2 + 2 CuI
I2 + 2 S2O32−
- 2-
2 I + S4O6
2.4 Mass (in mg) of copper in your parent solution,

mass (in mg) of lanthanum in your parent solution.
-1 -1
[M(Cu) = 63.55 g mol ; M(La) = 138.91 g mol ]
Amount of copper:
10,50 cm × 0.01 mol dm × 4 × 10 × 63.55 g mol = 266.9 mg
3 -3 -1
Amount of lanthanum:
[11.60 – (10.50 / 10 × 4)] cm × 0.1 mol dm × 10 × 138.91 g mol = 1028 mg
3 -3 -1
Mass Cu: m(Cu) = 266.9 mg

Mass La: m(La) = 1028 mg
2.5 Assume a fictive consumption of 39.90 cm3 of 0.1000 mol dm-3 EDTA solution and
3 -3
35.00 cm of 0.01000 mol dm Na2S2O3 solution. Calculate the coefficient x in the
formula LaxM(2-x)CuO4 (M = Ca and/or Sr and/or Ba) and give the exact formula of the
superconductor
TH
Consumption for lanthanum = [39.90 – (35.00/10 × 4)] cm3 = 25.90 cm3

Consumption for copper = (39.90 – 25.90) cm3 = 14.00 cm3
n(La) : n(Cu) = 25.90 : 14.00 = 1.85 : 1
coefficient x: 1.85 formula: La1.85Ba0.15CuO4
TH
THE 37 INTERNATIONAL CHEMISTRY OLYMPIAD, Taipei, 2005
Identification of Unknown Inorganic Samples
Note
(1) This practical exercise is a kind of “spot test”. You can do it on the pallet or on a
sheet of black film (for white precipitate).
(2) Please check all items written in the equipment and reagent list.
(3) Please check carefully the code number of the unknown sample with the Check List
accompanied with your unknown samples.
(4) The volume of each unknown solution is about 1.5 cm3 (about 30 drops). No more
reagents or samples will be provided.
(5) Be sure to confirm your results before writing your answers in the blanks of the
Answer Sheet.
(6) Make sure the switch on the battery box is closed.
(7) You will get 8 points for each correct identification.
Introduction
There are 12 unknown samples in your plastic bag;9 unknown solutions are in
droppers and 3 unknown solids are in vials. All unknown samples are numbered with a 3
digit code. Please check the number with the List of Unknown Inorganic Samples
carefully, then write your student code, and name on the list. (The list is accompanied with
your unknown samples) Each vial contains about 20 mg of crystals or powder of one pure
compound. Each dropper contains about 1.5 cm3 solution of one pure compound
dissolved in distilled water. The concentration of unknown solutions is in the range of 0.05
to 0.5 M (mol dm-3).
The unknown samples are as follows:
HCl H2O2 H2SO4 ZnCl2 NH4SCN

K4Fe(CN)
NaOH Na2CO3 Na2SO3 BaCl2
6
Note
1) Two unknown samples are duplicates.
TH
2) The crystal water (. H2O) is omitted in the formulas listed above.
2.1 Use the four reagents provided and mutual reactions among the unknown samples,
and the simple electrolysis apparatus to identify each unknown sample, and write
your answer (3 digit code) in the blanks of your answer sheet.
2.2 In this practical work, you have performed a series of tests to identify (or confirm) the
unknowns. Show the reactions involved by way of chemical equations.
A. Write the electrolysis equation that would help you confirm that an unknown
sample is ZnCl2.
B. Write one equation that shows how to clean the deposit of Zn on the electrode
(limited to the items provided in this task).
_______________
SOLUTION
2.2A Zn2+(aq) + 2 Cl–(aq) → Cl2(g) (anode) + Zn(s) (deposit on cathode)
2.2B Zn(s) + 2 H+(aq) → H2(g) + Zn2+(aq)

or
Zn(s) + 2 OH–(aq) + 2 H2O(l) → H2(g) + [Zn(OH)4]2–(aq)
TH
THE 38 INTERNATIONAL CHEMISTRY OLYMPIAD, Gyeongsan, 2006
Qualitative Analysis of Organic Compounds
In this experiment your task is to identify seven solid unknowns from the list of
compounds on page 7 that are common drugs in everyday life and valuable agents in
organic chemistry. To achieve this, perform chemical tests on unknowns according to the
following procedures and analyze your results.
Procedure
Helpful Comments
a) The weight of a spatula tip-full of a solid is about 15~20 mg.
b) Wipe spatula cleanly with Kimwipe between uses.
c) After adding any reagent described below to a solution of an unknown sample, mix
the contents thoroughly and observe the resulting mixture carefully.
d) To get full marks, you should perform all the tests and fill out the table.
Test 1: Solubility test

To a test tube, add a spatula tip-full (15~20 mg) of an unknown sample and 1 cm3 of
CH3CN. Shake the test tube and report the solubility. Repeat the test with 1M HCl, water,
and 1M NaOH.
Test 2: 2,4-DNPH test

Place about 15~20 mg of an unknown sample in a test tube and dissolve with 2 cm3 of
95 % EtOH. (For the water soluble unknowns, dissolve about 15~20 mg of an unknown in
1 cm3 of water.) Add five drops of the 2,4-dinitrophenylhydrazine solution in concentrated
sulphuric acid and 95% ethanol (labelled as 2,4-DNPH).
Test 3: CAN test

Mix 3 cm3 of the cerium(IV) ammonium nitrate solution in dilute HNO3 (labelled as CAN)
with 3 cm3 of CH3CN in a test tube. In another test tube add about 15~20 mg of an
unknown sample in 1 cm3 of the mixed solution. (For the water soluble unknown samples,
dissolve about 15~20 mg of an unknown sample in 1 cm3 of water first, and then add 1
3
cm of CAN.) If there is a colour change in the solution, the solution may contain alcohol,
phenol or aldehyde.
TH
Test 4: Bayer test

3
In a test tube, dissolve about 15~20 mg of an unknown sample in 2 cm of CH3CN. (For
3
the water soluble unknown samples, dissolve about 15~20 mg of an unknown in 1 cm of
water.) To the solution, slowly add five drops of the 0.5 % KMnO4 solution, drop by drop
while shaking.
Test 5: pH test
3
In a test tube, dissolve about 15~20 mg of an unknown sample in 2 cm of 95 % EtOH.
(For the water soluble unknown samples, dissolve about 15~20 mg of an unknown sample
in 1 cm3 of water). Measure the pH of the solution with pH paper.
Test 6: Iron(III) chloride test

Take the solution from Test 5 and add five drops of a 2.5 % FeCl3 solution.
Results
1. Record your test results in the answer sheet. Write O if soluble and X if insoluble for
the solubility tests. Write (+) for the positive reactions and (–) for the negative
reactions for tests 2 ~ 4 and 6. Write a, b and n for acidic, basic or neutral,
respectively, for pH test 5.
2. Based on your test results, identify the most plausible structures for the unknown
compounds from the provided list of compounds. Write the compound initial in
appropriate box.
Possible Unknown Compounds (next page):
TH
Caution:
Handle all unknown solutions as if they were toxic and corrosive. Discard them
only in the appropriate waste container.
The heat gun heats the expelled air up to 500 °C. D o not direct the stream
towards combustible materials or body parts. Be careful with the hot nozzle.
Always place a single piece of pumice into liquids before heating to avoid
bumping. Never point the mouth of a heated test tube towards a person.
You have eight unknown aqueous solutions. Each solution contains only one
compound. The same ion may appear in more than one solution. Every compound
formally consists of one type of cation and one type of anion from the following list:
Cations: H+, NH4+, Li+, Na+, Mg2+, Al3+, K+, Ca2+, Cr3+, Mn2+, Fe2+, Fe3+, Co2+, Ni2+, Cu2+,
Zn2+, Sr2+, Ag+, Sn2+, Sn4+, Sb3+, Ba2+, Pb2+, Bi3+
Anions: OH–, CO32- , HCO-3 , CH3COO–, C2O2- - - – 2- - 2-

4 , NO2 , NO3 , F , HPO 4 , H2PO 4 , SO 4 ,
HSO-4 , S2–, HS–, Cl–, ClO-4 , MnO-4 , Br–, I–
You have test tubes and heating at your disposal but no additional reagents apart
from distilled water and pH paper.
Identify the compounds in the solutions 1-8. You can use the solubility table for some of
the anions on the next page. If you are unable to identify an ion exactly, give the narrowest
selection possible.
Remarks: The unknown solutions may contain minor impurities arising from their
exposure to air. The concentration of all solutions is around 5 % by mass so you can
expect clearly observable precipitates from the main components. In some cases,
precipitation does not occur instantaneously; some substances may remain in an
oversaturated solution for a while. Don’t draw negative conclusions too hastily, wait 1-2
minutes where necessary. Always look carefully for all signs of a reaction.
Keep in mind that heating accelerates all processes, increases the solubility of most
substances, and may start reactions that do not take place at room temperature.
_______________
TH
SOLUTION
The solutions received by the students contain the following compounds in eight test-
–
tubes: AgNO3, BaI2, KHCO3, MgSO4, NaHS, NaOH, NH4ClO4, Pb(CH3COO 2 (Pb(OAc)2).
There were eight sets of samples differing in order of the compounds in particular test
tubes.
The problem can be approached in many ways. A systematic solution is given here
for one of the sets of test tubes with the following order of the compounds:
Test tube
1 2 3 4 5 6 7 8
No
Compound AgNO3 KHCO3 NH4ClO4 NaOH NaHS Pb(OAc)2 BaI2 MgSO4
All solutions are colourless (NaHS may be slightly yellowish because of polysulfide
impurity). Solutions 1, 3, 6, 7, and 8 are practically neutral (pH paper reading about 5-6).
Solution 2 is basic (pH = 9) while solutions 4 and 5 are very strongly basic (pH > 11).
We can exclude all ions that only form coloured compounds in aqueous solutions:
Cr , Fe2+, Fe3+, Co2+, Ni2+, Cu2+, and MnO4–. (In principle we should also exclude Mn2+
3+
but its solutions have a very light pink colour that might be mistaken for colourless. The
yellowish solution is strongly basic hence its colour cannot be attributed to iron.) The
+ 2+ 4+ 3+ 3+ –
compounds of H , Sn , Sn , Sb , Bi , and HSO4 with the possible counter-ions could
only exist in markedly acidic solutions; therefore they can also be safely excluded.
Thus the list of possible ions is:
Cations: NH4+, Li+, Na+, Mg2+, Al3+, K+, Ca2+, Mn2+, Zn2+, Sr2+, Ag+, Ba2+, Pb2+.
Anions: OH–, CO32–, HCO3–, CH3COO–, C2O42–, NO2–, NO3–, F–, PO43–, HPO42–, H2PO4–,
SO42–, S2–, HS–, Cl–, ClO4–, Br–, I–.
The unknown solutions react with each other as follows (↓ = precipitate; ↑ = volatile
product; “no change” means even when boiled, unless indicated otherwise):
TH
1 2 3 4 5 6 7 8
AgNO3 KHCO3 NH4ClO4 NaOH NaHS Pb(OAc)2 BaI2 MgSO4
1        
AgNO3
↓ light
yellow
2       
↑
KHCO3
neutral,
odourles
3 no
↓ white
    
crystals 
change
NH4ClO4 (*)
boiling:
4 ↓
no
↑ basic,
    
brown- odour of
change
NaOH black ammo-
nia
↓ black boiling:
↑ basic,
5 solution
no
odour of
no    
NaHS change change
turns NH3,
acidic H2S
↓ white
6 ↓ white no ↓ black   
↑ ↓ white
crystals change
Pb(OAc)2 neutral,
odourles
7 ↓ yellow
↓ white
no no no 
↓ yellow 
change change change
BaI2 ↑ (**)
8 ↓ white
no
no
no

change ↓ white change ↓ white ↓ white
crystals change
MgSO4 (***) (****)
(*): upon boiling, the formation of NH3 is detectable by its odour and by pH paper.
(**): gas bubbles are usually not observed when 2 is in excess.
(***): upon boiling, an odourless gas evolves and a white precipitate forms.
(****): upon boiling, a white precipitate forms and the odour of H2S appears.
TH
+ –
2 Ag + 2 HCO3 = Ag2CO3 + CO2 + H2O
2+ –
Pb + 2 HCO3 = PbCO3 + CO2 + H2O
2+ –
Ba + 2 HCO3 = BaCO3 + CO2 + H2O
2+ –
Mg + 2 HCO3 = MgCO3 + CO2 + H2O (more accurately, basic carbonates of
variable composition are formed)
Ag+ + I– = AgI; 2 Ag+ + SO42– = Ag2SO4; Ag+ + CH3COO– = CH3COOAg
2+ – 2+ – 2+ 2–
Pb + 2 OH = Pb(OH)2; Pb + 2 I = PbI2; Pb + SO4 = PbSO4
K+ + ClO4– = KClO4; Ba2+ + SO42– = BaSO4; Mg2+ + 2 OH– = Mg(OH)2
+ –
2 Ag + 2 OH = Ag2O + H2O
2 Ag+ + HS– = Ag2S + H+; Pb2+ + HS– = PbS + H+; CH3COO– + H+ = CH3COOH
NH4+ + OH– = NH3 + H2O
NH4+ + HCO3– = NH3 + CO2 + H2O
Two groups of the observed phenomena give instant clues to the identification of
some of the ions.
First, the reactions of 2 are often accompanied with the formation of a colourless and
odourless gas that can only be CO2. Thus 2 contains CO32– or HCO3–.
Second, there are only 3 dark precipitates that can be formed from the given ions:
Ag2O, Ag2S, and PbS. This fact, together with the pH of the solutions, instantly identifies
the cation of 1 as Ag+, the cation of 6 as Pb2+, the anion of 4 as OH–, and the anion of 5
as sulfide or hydrosulfide (confirmed by the distinct smell of the solution).
The choice between the latter two can be made by measuring the pH of the solution
formed in the reaction of 5 with an excess of 1 or 6. In the case of 1, the reaction mixture
is strongly acidic. Thus the anion of 5 is HS–.
The evolution of CO2 in the reaction with Ag+ and Pb2+ also identifies the anion of 2
as HCO3–. (in accord with the moderately basic pH)
The reaction of 3 and 4 yields ammonia. 4 is obviously not a solution of NH3 itself.
Thus the cation of 3 is NH4+.
2+4 form either a precipitate or ammonia. The cations of 2 and 4 are Na+ or K+.
2+5 do not form either a precipitate or ammonia. The cation of 5 is an alkali metal.
3 is the only solution that does not give a precipitate with Ag+. Accordingly, it can be
ammonium nitrate, fluoride, or perchlorate. But it does give a precipitate with 2, a
hydrocarbonate of Na+ or K+. Thus the anion of 3 is ClO4– and the cation of 2 is K+. 4 does
+
not give a precipitate with NH4ClO4. The cation of 4 is Na .
TH
+
5 does not give a precipitate either with NH4ClO4 (K ) or with a mixture of KHCO3
and NaOH (Li+). The cation of 5 is Na+.
7 forms no precipitate or ammonia with NaOH but gives a precipitate with KHCO3. 7
cannot be an alkali metal perchlorate because it forms yellow precipitates with 1 and 6.
Thus the cation of 7 is Ba2+ and the anion of 7 is I–.
– –
At room temperature 8 gives a precipitate with OH but not with HS which means it
can only be a salt of a Group 2A metal. Thus the reaction of 8 with BaI2 is obviously one
between Ba2+ and the anion of 8. The latter is very likely SO42– but HCO3– and H2PO4– are
also theoretically possible. The solution of 8 is unchanged upon boiling and gives a white
+ – – 2–
precipitate with Ag . This excludes both HCO3 and H2PO4 . Thus the anion of 8 is SO4 .
This instantly identifies the cation of 8 as Mg2+.
6 is a soluble compound of lead. The anion could be CH3COO–, NO2–, NO3–, or
ClO4–. The slight odour of acetic acid might give a clue. Unlike 1, the reaction of an excess
of 6 with HS– does not yield a markedly acidic solution which shows that 6 is a salt of a
+
weak acid. If 6 were a nitrite, it would give a yellowish precipitate with Ag . It would also
react with NH4ClO4 upon heating with the evolution of N2 (and nitrogen oxides from the
reaction with HS– would also be noticeable). The absence of these reactions indicates that
the anion of 6 is CH3COO–.
– –
Soluble salts of silver are even less numerous, the only choices are NO3 , F , and
–
ClO4 . The anion can be examined if one removes the silver ions from the solution of 1
with an excess of NaOH. The Ag2O precipitate quickly separates from the solution which
can be easily poured off. This solution, containing the anion of 1, does not give a
precipitate with BaI2 which rules out F–. The solubility of KClO4 is quite significant;
therefore the absence of a precipitate with KHCO3 is inconclusive. The anion of 1 is
therefore either NO3– or ClO4–.
Code: XXX-01
Labware
Item Quantity
All tasks, on the table of common use
Latex gloves of different sizes, choose your size -
General equipment for all tasks, for each student, on the table
Test tube rack (60 holes) 1
Paper tissue (can ask for extra) 5
Permanent marker 1
Glass stirring rod, 20 cm 1
Polypropylene funnel, diam. 3.5 cm 1
Soft plastic cup 3
Strong plastic cup 1
All tasks, for each student in the soft plastic cup
Caps for polystyrene test tubes 22
Task 1, for each student, on the table
Rack for centrifuge tubes (21 holes) 1
Container with a screw cap for waste,1 dm , labeled “Liquid
3
1
Waste, Test 1”
Paper filters in zip-bag 5
Task 1, for each student, in the strong plastic cup
Pasteur pipettes 20
Task 1, for each student, in the 60-hole rack
Polystyrene test tubes, 10 cm3 35
48th IChO Practical Tasks, Official English version 3

Code: XXX-01
Chemicals
Name State Conc. Q-ty Placed in Labeled
All tasks, for each student, on the table
Wash bottle,
Distilled water Liquid - 1 dm3 H2O dist.
1 dm3
Glass bottle with
Hexane Liquid - 25 cm3 Hexane
screw cap, 50 cm3
Amber plastic
Sodium
Aqueous solution 1M 80 cm 3 bottle with screw NaOH
hydroxide
cap, 125 cm3
Glass bottle with
Nitric acid* Aqueous solution 2M 150 cm3 dropper cap, HNO3
250 cm3
Task 1, for each student, in the 21-hole rack
Centrifuge tubes, Unknown
5 unknowns Aqueous solution - 45 cm3
50 cm3 No ___
Centrifuge tube,
Silver nitrate Aqueous solution 0.1 M 25 cm3 AgNO3
50 cm3
Aluminium Centrifuge tube,
Aqueous solution 0.3 M 25 cm3 Al2(SO4)3
sulfate 50 cm3
Centrifuge tube,
Barium nitrate Aqueous solution 0.25 M 25 cm3 Ba(NO3)2
50 cm3
Iron(III) Aqueous acidic Centrifuge tube,
0.2 M 25 cm3 Fe(NO3)3
nitrate (HNO3) solution 50 cm3
Potassium Centrifuge tube,
Aqueous solution 0.1 M 25 cm3 KI
iodide 50 cm3
Potassium Centrifuge tube,
Aqueous solution 0.1 M 25 cm3 KIO3
iodate 50 cm3
Magnesium Centrifuge tube,
Aqueous solution 0.2 M 25 cm3 MgCl2
chloride 50 cm3
Sodium Centrifuge tube,
Aqueous solution 0.2 M 25 cm3 Na2CO3
carbonate 50 cm3
Centrifuge tube,
Sodium sulfite Aqueous solution 0.2 M 25 cm3 Na2SO3
50 cm3
Centrifuge tube,
Ammonia* Aqueous solution 1M 25 cm3 NH3(aq)
50 cm3
* Nitric acid and ammonia solutions are needed in a subsequent task.

Code: XXX-01
Task 1
You have 10 different compounds dissolved in water in 5 unknown solutions. Each
numbered container contains two of the following compounds in aqueous solution
(every compound is used, and each compound is used only once):
AgNO3, Al2(SO4)3, Ba(NO3)2, Fe(NO3)3, KI, KIO3, Na2CO3, Na2SO3, MgCl2, NH3
You are given HNO3 solution, NaOH solution, hexane and the aqueous solutions of the 10
pure compounds listed above.
You can use empty test tubes and any of the liquids provided (including the unknowns)
to identify the unknown samples. A funnel and filter paper can be used for separation.
Identify the compounds in the solutions 1-5. Give the number of the solution that
contains the individual compounds on the answer sheet. Indicate two
observations caused by a chemical reaction for each compound in your
unknown mixtures by giving the letter code of the appropriate observation
(choose one or more from the list), and write appropriate balanced ionic
equation(s) that explain the observation. At least one of the reactions has to be
specific for clearly identifying the compound from this selection of unknowns.
Note: After the STOP signal close all the centrifuge test tubes containing the unknown
mixtures with the blue caps labeled with the student code and leave these in the rack.

Code: XXX-01
Task 1 13% of the total

7 7 7 7 7 7 7 7 7 7 Sum: 70
Only fill out this table when you are ready with all your assignments. Use the following
observation codes:
A - Formation of white precipitate F - Brown color in the organic phase
B - Formation of colored precipitate G - Purple color in the organic phase
(red, brown, yellow, black etc.)
C - Dissolution of precipitate H - Formation of colored gas
D - Color change in the solution I - Formation of colorless and odorless gas
E - Formation of colored solution J - Formation of colorless and odorous gas
K – Change in the color of precipitate
Compound No. of Formula of Observation Balanced net ionic equation(s)

unknown reaction code(s)
partner(s)
NH3
Fe(NO3)3
Al2(SO4)3
AgNO3
KIO3

Code: XXX-01
Compound No. of Formula of Observation Balanced net ionic equation(s)

unknown reaction code(s)
partner(s)
Na2CO3
MgCl2
Na2SO3
Ba(NO3)2
KI
Replacements:
Item Quantity Lab assistant’s Student’s
signature signature

Code: XXX-01
5p for locating each compound, 1 p for each relevant equation. Altogether 10x7p.
Subpoints for 1p: 0.4p for correct observation with appropriate reagent(s); 0.6p for the
relevant balanced ionic equation (-0.1p for minor typos; maximum of -0.3p for poor
balancing; maximum of 0.3p for an equation in other than ionic form)
The unknowns are identical mixtures for every student in different order. Most are
mixed in 1:1 ratio by volume.
Characteristic reactions are marked with bold letters. One of these or equivalent has to
be shown on the answer sheet.
NH3
AgNO3, B) 2 Ag+ + 2 OH− = Ag2O + H2O (if Ag+ is not mixed with Fe3+)
C) Ag2O + H2O + 4 NH3 = 2 [Ag(NH3)2]+ + 2 OH− (if Ag+ is not with Fe3+)
Fe(NO3)3, B) Fe3+ + 3 OH−= Fe(OH)3
Al2(SO4)3, A) Al3+ + 3OH− = Al(OH)3 (or [Al(H2O)6]3+ + 3 OH− = Al(OH)3 + 6
H2O)
MgCl2, A) Mg2+ + 2 OH− = Mg(OH)2
NaOH, J) NH4+ + OH− = NH3 + H2O
(KIO3) + AgNO3, C) AgIO3 + 2 NH3 = [Ag(NH3)2]+ + IO3−
Fe(NO3)3
NaOH, B) Fe3+ + 3 OH− = Fe(OH)3
NH3, B) Fe3+ + 3 OH− = Fe(OH)3
KI, D) or E) 2 Fe3+ + 2 I− = 2 Fe2+ + I2
MgCl2, E) Fe3+ + Cl− = [FeCl]2+ (or Fe3+ + 3 Cl− = FeCl3 etc.)
Al2(SO4)3
NaOH, A) Al3+ + 3 OH− = Al(OH)3 (or [Al(H2O)6]3+ + 3 OH− = Al(OH)3 + 6 H2O)
C) Al(OH)3 + OH− = [Al(OH)4]−
(NaOH +) [Al(OH)4]− + H+ = Al(OH)3 + H2O
HNO3 A)
Ba(NO3)2, A) Ba2+ + SO42− = BaSO4
Na2CO3, A) Al3+ + 3 OH− = Al(OH)3 (or [Al(H2O)6]3+ + 3 OH− = Al(OH)3 + 6 H2O)

Code: XXX-01
AgNO3
NaOH, B) 2 Ag+ + 2 OH− = Ag2O + H2O
KI, B) Ag+ + I− = AgI
NH3, B) 2 Ag+ + 2 OH− = Ag2O + H2O (if Ag+ is not mixed with Fe3+)
C) Ag2O + H2O + 4 NH3 = 2 [Ag(NH3)2]+ + 2 OH− (if Ag+ is not with Fe3+)
MgCl2, A) Ag+ + Cl− = AgCl
Na2CO3, A) 2 Ag+ + CO32− = Ag2CO3
or B)
Na2SO3, A) 2 Ag+ + SO32− = Ag2SO3
C) Ag2SO3 + 3 SO32− = 2 [Ag(SO3)2]3−
KIO3, A) Ag+ + IO3- = AgIO3
KIO3
Na2SO3 + HNO3, B) or E) 5 SO32− + 2 IO3− + 2 H+ = I2 + 5 SO42− + H2O
(+ hexane, G)
KI + HNO3, B) or E) 5 I− + IO3− + 6 H+ = 3 I2 + 3 H2O
(+ hexane, G)
AgNO3, A) Ag+ + IO3− = AgIO3
Ba(NO3)2, A) Ba2+ + 2 IO3− = Ba(IO3)2
Na2CO3
HNO3, I) CO32− + 2 H+ = H2O + CO2
Ba(NO3)2, A) Ba2+ + CO32− = BaCO3
+ HNO3, C), I) BaCO3 + 2 H+ = Ba2+ + H2O + CO2
AgNO3, A) or B) 2 Ag+ + CO32− = Ag2CO3
+ HNO3, C), I) Ag2CO3 + 2 H+ = 2 Ag+ + H2O + CO2
MgCl2, A) Mg2+ + CO32− = MgCO3
+ HNO3, C), I) MgCO3 + 2 H+ = Mg2+ + H2O + CO2
MgCl2
NaOH, A) Mg2+ + 2 OH− = Mg(OH)2
NH3, A) Mg2+ + 2 OH− = Mg(OH)2
AgNO3, A) Ag+ + Cl− = AgCl
Na2CO3, A) Mg2+ + CO32− = MgCO3
Fe(NO3)3, E) Fe3+ + Cl− = [FeCl]2+ (or Fe3+ + 3 Cl− = FeCl3 etc.)
Na2SO3
HNO3, J SO32− + 2 H+ = H2O + SO2
KIO3 + HNO3, B) or E) 5 SO32− + 2 IO3− + 2 H+ = I2 + 5 SO42− + H2O
(+hexane, G)
Ba(NO3)2, A) Ba2+ + SO32− = BaSO3
+ HNO3, C) BaSO3 + 2 H+ = Ba2+ + SO2 + H2O
AgNO3, A) 2 Ag+ + SO32− = Ag2SO3
C) Ag2SO3 + 3 SO32− = 2 [Ag(SO3)2]3−
KI + KIO3 , D) I2 + SO32− + H2O = 2 I− + SO42− + 2 H+

Code: XXX-01
Ba(NO3)2
Al2(SO4)3, A) Ba2+ + SO42− = BaSO4
KIO3, A) Ba2+ + 2 IO3− = Ba(IO3)2
Na2CO3, A) Ba2+ + CO32− = BaCO3
Na2SO3, A) Ba2+ + SO32− = BaSO3
+ HNO3, C) BaSO3 + 2 H+ = Ba2+ + SO2 + H2O
KI
Fe(NO3)3, E) or D) 2 Fe3+ + 2 I− = 2 Fe2+ + I2
AgNO3, B) Ag+ + I− = AgI
KIO3, + HNO3, B) or E) 5 I− + IO3− + 6 H+ = 3 I2 + 3 H2O
(+hexane, G)

Code: XXX-01
Labware
Item Quantity
Paper tissue 5
Permanent marker 1
Soft plastic cups 3
Tasks 2 and 3, for each student, on the table
Container with a screw cap for waste,3 dm3, labeled “Liquid Waste, 1
Tests 2&3”
Storage box labeled “Task 2” 1
Laboratory stand with double burette clamp 1
Burette, 25.00 cm3 2
Graduated pipette, 10.0 cm 3 1
Bulb (Mohr) pipette, 10.00 cm3 1
Erlenmeyer flask, 100 cm 3 2
Graduated cylinder, 10.0 cm 3 2
Brush 1
Polypropylene funnel, 5.5 cm 1
Task 2, for each student, in the storage box “Task 2”
Pipette filler 1
Pasteur pipettes for indicators 2
Task 3, for each student, get from the lab assistants
Alcohol lamp 1
Test tube holders, wooden 1
Glass test tubes 10
Pasteur pipettes 10

Code: XXX-01
Chemicals
Glass bottle
Aqueous
Nitric acid 2M -* with dropper HNO3
solution
cap, 250 cm3
Glass bottle
Water sample Aqueous To be Water
100 cm3 with screw
solution solution determined sample
cap, 100 cm3
Glass bottle
Sodium Aqueous 9 mg/dm3 in F−, 9
50 cm 3 with screw
fluoride solution fluoride mg/dm3
cap, 50 cm3
Zirconyl Acidic 0.055% ZrOCl2, Glass bottle
Zirconyl
Alizarin aqueous 0.028% 10 cm 3 with screw
Alizarin
indicator solutions Alizarin Red S cap, 25 cm3
Glass bottle NaCl,
Sodium Aqueous
0.0500 M 50 cm3 with screw 0.0500
chloride solution
cap, 50 cm3 M
Ammonium Aqueous
Glass bottle,
iron(III) sulfate acidic 20 g/dm3 10 cm3 Fe3+ ind.
15 cm3
dodecahydrate solution
Amber glass
Aqueous To be
Silver nitrate 200 cm 3 bottle, AgNO3
solution determined
250 cm3
See exact Glass bottle NH4SCN,
Ammonium Aqueous
concentration 100 cm3 with screw X.XXXX
thiocyanate solution
on the label cap, 100 cm3 M
Potassium Aqueous Glass bottle,
10% 5 cm3 K2CrO4
chromate solution 15 cm3
Glass bottle
Ethanol Liquid 95 % 150 cm 3 with dropper C2H5OH
cup, 250 cm3
Organic
Liquid Syringes,
unknowns 1 to - 0.5 cm3 1 to 8
2 cm3
8
Potassium Aqueous Amber glass
0.13 % 5 cm3 KMnO4
permanganate solution bottle, 50 cm3
Ammonium 2.0 M HNO3
HDPE bottle,
cerium(IV) aqueous 28.6 % 5 cm3 Ce(IV)
30 cm3
nitrate reagent solution
Glass bottle,
Acetonitrile Liquid - 45 cm3 CH3CN
50 cm3

Code: XXX-01

Sulfuric acid
2,4-Dinitrophe- solution in
HDPE bottle,
nylhydrazine aqueous 3% 20 cm3 DNPH
30 cm3
reagent ethanol
0.5 M HCl
Iron(III) HDPE bottle,
aqueous 2.5 % 1 cm3 FeCl3
chloride 30 cm3
solution
Hydroxylamine Ethanolic HDPE bottle, NH2OH
0.5 M 10 cm3
hydrochloride solution 30 cm3 HCl
Sodium Aqueous HDPE bottle,
6M 5 cm3 NaOH
hydroxide solution 30 cm3
Hydrochloric Aqueous HDPE bottle,
1M 25 cm3 HCl
acid solution 30 cm3
*In the quantity left after doing Task 1.
Periodic table with relative atomic masses
1 18
1 2
H He
1.008 2 13 14 15 16 17 4.003
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
6.94 9.01 10.81 12.01 14.01 16.00 19.00 20.18
11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
22.99 24.30 3 4 5 6 7 8 9 10 11 12 26.98 28.09 30.97 32.06 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.10 40.08 44.96 47.87 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.38 69.72 72.63 74.92 78.97 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.95 - 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba 57-71 Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9 137.3 178.5 180.9 183.8 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 - - -
87 88 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
Fr Ra 89-
103 Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
- - - - - - - - - - - - - - - - -
57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
138.9 140.1 140.9 144.2 - 150.4 152.0 157.3 158.9 162.5 164.9 167.3 168.9 173.0 175.0
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
- 232.0 231.0 238.0 - - - - - - - - - - -

Code: XXX-01
Task 3
Identifying flavors and fragrances
Tourists coming to Georgia admire many specialties, local cuisine occupying one of the
top positions in the list of adventures. Excellent meat, fresh vegetables and greens, ripe
fruits, home-made jams… What else is needed to satisfy true gourmets? Of course,
unique flavors and fragrances!
You are given 8 samples of unknown organic compounds (labeled 1 to 8), which are
industrially used as flavors and fragrances. All samples are pure individual compounds.
Their possible structures are found among A-M given here.
The organic compounds in your unknown samples are readily soluble in ether, and
insoluble in dilute aqueous NaOH and HCl. These compounds, but the unknown No. 6.
are insoluble in water, the latter being slightly soluble (3.5 g/dm3).
3.1. Perform test reactions described below to identify the samples 1-8. Indicate the
results of the tests by giving the Roman numeral of the appropriate observation
(choose one or more from the list). Fill in all cells of the table. Use + and – to
indicate positive and negative tests.
3.2. Identify the unknowns based on the test results and the information given
above. Write the structure codes (of A to M) of the identified samples in the
appropriate box.
Test procedures
KMnO4 test (Baeyer test)
Place appr. 1 cm3 of 95% ethanol in a plastic test tube and add 1 drop of an unknown.
Add 1 drop of KMnO4 solution and shake the mixture. Treat the test as positive if the
permanganate color disappears immediately after shaking.

Code: XXX-01
3.3. Write the reaction scheme for a positive Baeyer test with one of the compounds
A-M.
Cerium(IV) nitrate test

Place 2 drops of the Ce(IV) reagent into a glass test tube, add 2 drops of acetonitrile and
then 2 drops of an unknown (the sequence is important!). Shake the mixture. In the case
of positive test the mixture color promptly changes from yellow to orange-red.
Note 1. Use only glass test tubes to perform the test. In case you need to wash the glass
test tubes, carefully choose the appropriate solvent. Use caps to prevent the strong odor.
Note 2. Comparison with blank (no unknown) and reference (with ethanol) tests is
recommended for adequate interpretation.
Note 3. Ce(IV) ions initially form brightly colored coordination compounds with
alcohols. Complexes formed from primary or secondary alcohols react further (within
15 seconds to 1 hour) with the disappearance of the color.
2,4dinitrophenylhydrazine (2,4-DNPH) test

Add only 1 drop of an unknown to 1 cm3 of 95% ethanol in a plastic test tube. Add 1 cm3
of the DNPH reagent to the prepared solution. Shake the mixture and let it stand for
1-2 min. Observe formation of yellow to orange-red precipitate if the test is positive.
3.4. Write the reaction scheme for a positive 2,4-DNPH test with one of the
compounds A-M.
Ferric hydroxamate test

Ask a lab assistant to light up your alcohol lamp. Mix 1 cm3 of 0.5 mol/dm3 ethanolic
hydroxylamine hydrochloride solution with 5 drops of 6 mol/dm3 sodium hydroxide
aqueous solution in a glass test tube. Add 1 drop of an unknown and use the alcohol
lamp to heat the mixture to boiling while gently swirling the test tube to avoid splashes
of the reaction mixture. Allow it to cool down slightly and add 2 cm3 of 1 mol/dm3 HCl
solution. Add 1 drop of 2.5% iron(III) chloride solution. Observe appearance of magenta
color if the test is positive. Close the alcohol lamp with the cap when finished.
Note 1. Use glass test tubes only to perform the test; use the test tube holder when
heating. In case you need to wash the glass test tubes, use an appropriate solvent.
Stopper the test tubes with a green cap after completing the test to prevent a strong
odor.
Note 2. Fe(III) ions form a colored 1:1 complex with hydroxamic acids (R-CO-NHOH).
3.5. Write the reaction scheme for a positive ferric hydroxamate test with one of the
compounds A-M.
Note: After the STOP signal reattach the corresponding needles on the syringes with the
unknown compounds, and place them into the plastic cup and leave them on the
table.

Code: XXX-01

3.1. 3.2. 3.3. 3.4. 3.5. Sum
32 16 4 4 4 60
3.1. Indicate the results and observations of tests by giving the Roman numerals of
the appropriate observations in the table. Fill in all cells of the table. Use + and –
to indicate positive and negative tests. Choose one or more codes from the list
below.
I – Immediate disappearance of purple VI - Formation of a yellow or orange-red
color precipitate
II – Slow disappearance of purple color VII - Appearance of orange or red color in
solution
III - Disappearance of yellow color VIII - Appearance of magenta color
IV – Formation of a brown or black IX - The unknown compound is insoluble in
precipitate ethanol
V - Formation of a white precipitate X – no visible changes
Sample No. 1 2 3 4 5 6 7 8
Baeyer test result (+/–) + – + – – – – +

I, I, II, II, I,
Baeyer test observations (I-X) X X X
IV IV IV IV IV
Ce(IV) nitrate test result (+/–) + + – – – – – –

X
III,
Ce(IV) nitrate test observations (I-X) VII VII III X or X III
V
III
2,4-DNPH test result (+/–) – – – + – – – –
2,4-DNPH test observations (I-X) X X X VI X X X X
Fe(III) hydroxamate test result (+/–) – – – – + – – +

X
Fe(III) hydroxamate test
X X X X VIII X or VIII
observations (I-X)
IX

Code: XXX-01
3.2. Write the structure codes (of A to M) of the identified samples in the
appropriate boxes when you are certain in your assignments.
Sample No. 1 2 3 4 5 6 7 8
Structure code A B E G C H I D
3.3. Write the reaction scheme for a positive Baeyer test with one of the compounds
A-M.
OH
KMnO4
HO
OH - MnO2 OH
Or analogous 4p
3.4. Write the reaction scheme for a positive 2,4-DNPH test with one of the
compounds A-M.
O
NO2
DNPH H
N
N
NO2
4p
3.5. Write the reaction scheme for a positive ferric hydroxamate test with one of the
compounds A-M.
O NH2OH O FeCl3 O
OH FeCl2
O N HN
H O
magenta color
Or analogous 4p (any 1:1 hydroxamate – Fe(III) complex is acceptable)

Code: XXX-01
The problem can be approached in many ways. A systematic solution for one variant of
the unknown compounds encoding is given below (other variants are processed
similarly).
Step 1. Solubility data analysis.

The data given allow excluding compounds K (presence of phenol-like moiety) and M
(presence of azine nitrogen) soluble in aqueous NaOH and aqueous HCl, respectively.
Step 2. Tests for the functional groups.
2.1 Unsatured compounds excluding those aromatic give positive Baeyer test, and those
with keto- or aldehyde group give positive 2,4DNPH test
2.2 For avoiding mistakes in true-positive / false-positive interpretation the precise
description of true-positive tests is given in the test procedures.
2.3 The information given in the Notes after the test procedures CLEARLY indicates the
following prompts:
Note Prompt
Comparison with blank (no unknown) and The cerium(IV) nitrate test is one for
reference (with ethanol) tests is alcohols
recommended for adequate interpretation
of the test.
Brightly colored Ce(IV) coordination Red color appearing as a result of a
compounds bearing Csp3-O→Ce(IV) moiety positive cerium(IV) nitrate test can
have the formation constant in the range of disappear due to further oxidation of
0.51 (MeOH, kinetically unstable) to 2.76 alcohols by Ce(IV) in the case of primary
(t-BuOH, kinetically stable). and secondary alcohols
Brightly colored Fe(III)-hydroxamic acids The ferric hydroxamate test is the one for
coordination compounds have the the compounds capable of forming the
formation constants K1 ~ 42; K2 ~ 2.5; K3 ~ hydroxamic acids in the reaction with
1.2∙10−2 (for acetohydroxamate in NH2OH. ONLY ESTERS are appropriate
ethanol–water 1:1 mixture). candidates for the positive test. Amides (J)
do not afford hydroxamic acid under
NH2OH treatment, thus giving negative
test.

Code: XXX-01
The results of the experimental work can be summed up in the hereunder table.
Ferric
# of sample KMnO4 Ce(NH4)2(NO3)6 2,4DNPH Hydroxamate
Test
1 + + – –
2 – + – –
3 + – – –
4 – – + –
5 – – – +
6 – – – –
7 – – – –
8 + – – +
Analysis of the table allows unanimously identifying A, B, E, C, and G. L (Ferric

hydroxamate and 2,4DNPH), J (2,4-DNPH and Cerium(IV) nitrate test), and F (KMnO4 and
2,4DNPH tests) can be excluded from further consideration, since these provide for two
positive tests each.
Ferric
Ce(NH4)2(NO
# Structure KMnO4 2,4DNPH Hydroxamate
3)6
Test
1 + + – –
OH
OH
2 – + – –
3 + – – –
4 – – + –
O
5 – – – +
O
6 ? – – – –
7 ? – – – –
O
8 + – – +
O
Step 3. Choosing of right structures of the samples 6 and 7 based on additional data given.
Among all compounds in the list, only H and I cannot give any positive test, the attribution
requiring consideration of the solubility data. Sample 7 in the above table is soluble in
ether only (attributed as I), whereas Sample 6 is partially soluble in water (attributed as
H).

Code: XXX-01
The final assignment is given below.

Sample
1 2 3 4 5 6 7 8
No
Structure
A B E G C H I D
code
1 points for each test (1p  4 tests  8 unknowns=32p)

2 points for each correct assignment (2p 8 unknowns=16p)

Titolazione
acido-base
RD
PRACTICAL PROBLEMS
An unknown sample is a mixture of 1.2-molar H2SO4 and 1.47-molar HCl. By means of

available solutions and facilities determine:
1. the total amount of substance (in val) of the acid being present in 1 dm3 of the solution,
3
2. the mass of sulphuric acid as well as hydrochloric acid present in 1 dm of the sample.
By means of available reagents and facilities perform a qualitative analysis of the

substances given in numbered test tubes and write down their chemical formulas.
Give 10 equations of the chemical reactions by which the substances were proved:
5 equations for reactions of precipitation,
2 equations for reactions connected with release of a gas,
3 equations for redox reactions.

TH
PRACTICAL PROBLEMS
Determine unknown samples in ten numbered test tubes using reagents and facilities
available on the laboratory desk. Write chemical equations for the most important
reactions that were used to identify each substance. In case that the reactions take place
in solutions, write equations in a short ionic form.
On June 10th, a mixture of formic acid with an excess of ethanol was prepared. This
mixture was kept in a closed vessel for approximately one month. Determine quantitatively
the composition of the mixture on the day of the competition, using only reagents and
facilities available on the laboratory desk. Calculate the amounts of the acid and ethanol in
per cent by mass which were initially mixed together.

TH
A crystalline sodium carbonate loses a part of water when stored for a long time, i.
e. its water content is not constant. After a long storage it has an average content of
crystal water.
A solution of Na2CO3 is in the test-tube and the mass of Na2CO3 . x H2O used in its
preparation is marked on the test-tube.
Determine the content of crystal water per mole of sodium carbonate in the sample.
Make calculations with an accuracy of 0.01 mol.
Procedure:
Transfer the solution from the test tube quantitatively into a 100 cm3 volumetric flask
and dilute it up to the mark with distilled water free of carbon dioxide (having been boiled
and cooled to room temperature). Measure 10.00 cm3 of the solution into a 100 cm3
Erlenmeyer flask and dilute it to about 30 cm3 with the above mentioned distilled water.
Add 2 – 3 drops of methyl orange indicator and titrate with a 0.1-molar HCl volumetric
solution to a colour transition of the indicator. On boiling for 1 – 2 minutes the carbon
dioxide dissolved in the solution is expelled. If the colour of the solution changes to
yellow, cool it and titrate again to the colour transition of the indicator. Calculate the
carbonate content in the sample from the total consumption of the 0.1-molar HCl solution.
Ar(Na) = 22.99; Ar(C) = 12.01; Ar(O) = 16.00; Ar(H) = 1.01.

TH
PRACTICAL PROBLEMS
2+
-3
-3
TH
THE 9 INTERNATIONAL CHEMISTRY OLYMPIAD, Bratislava, 1977
If a known excess of hydroxide solution with a known concentration is added to a
weighed sample of ammonium salt and the liberated ammonia is removed by boiling, it is
possible to determine the unreacted quantity of hydroxide by titration with a volumetric
solution of an acid.
Procedure:
Three samples of an ammonium salt, weighed with accuracy of 0.001 g, are at your
disposal. Introduce each of them into a 250 cm3 Erlenmeyer flask. Add 50.0 cm3 of a 0.2-
normal sodium hydroxide solution to each sample. Put several boiling stones into each
mixture and heat the flasks slowly on a small flame till there is no more ammonia in the
liberating vapours. After expelling ammonia, cool the solution to the laboratory
temperature, add 2 or 3 drops of indicator solution (Bromothymol blue) and titrate with a
0,2-normal volumetric solution of oxalic acid to the first lasting yellow colour of the
solution.
Problems:
3.1 Calculate the molar mass of ammonium salt from the experimental data.
3.2 The sample is a salt of a monobasic inorganic acid. Consider which one.
3.3 Calculate the absolute and relative error of your determination.
3.4 Give reactions by means of which ions of the salt can be proved in the solution.
TH
THE 10 INTERNATIONAL CHEMISTRY OLYMPIAD, Torun, 1978
PRACTICAL PROBLEMS
Four aqueous solutions are available on the laboratory desk. These are solutions of
-3
HCl, NaOH, NH3, and CH3COOH whose concentrations are approximately 1 mol dm . The
concentration of HCl solution is the only one that is exactly determined and known.
Using the volumetric solution of HCl, determine the exact concentrations of the other
solutions. A burette, pipette, titration flasks and indicators methyl orange and
phenolphthalein are at your disposal. Perform twice each titration and calculate the mean
value for concentration. The third determination is needed to be carried out only in such a
case when the results of the previous two titrations differ more than by 2 %.
Now you will perform the following thermochemical measurements of neutralisation
heat evolved in the reactions of the above given solutions of acids and bases:
a) Measure quantitatively exactly 50.0 cm3 of the hydrochloric acid solution into a beaker.
Measure into another equal beaker a volume of NaOH solution that contains such a
number of moles of NaOH as that of HCl being present in the first beaker. Then
measure the temperatures of both solutions with a precision of 0.2 K. Pour quickly the
content of the first beaker into the other using the thermometers as a glass stick and stir
the resulting solution with the thermometer. Determine the final highest temperature of
the mixture.
b) Perform analogous measurement with the following pairs of acids and bases:
HCl − NH3, CH3COOH − NaOH, CH3COOH − NH3.
Problems:
1.1 What indicators have been used for the individual determinations? Give
approximately pH regions in which the mentioned indicators show colour transitions.
Give reasons for the use of the individual indicators using only ionic equations for the
reactions which are characteristic of specific properties of salts being formed in the
individual neutralisation reactions. Calculate the concentrations of all solutions under
investigations.
TH
1.2 Write the calorimetric equation in its general form by means of which the
neutralisation heat can be calculated. Calculate the thermal effect for each
neutralisation reaction under investigation and give the value in relation to one mole
of the water formed.
Densities of the solutions are as follows:

ρ(HCl) = 1.02 g cm-3
ρ(NaOH) = 1.04 g cm-3
ρ(NH3) = 0.99 g cm-3
ρ(CH3COOH) = 1.01 g cm-3
In the calculations consider the specific heat capacity value for the solutions equal to
4.19 J g-1 K-1 whereas the heat capacity of glass and thermometer may be neglected.
1.3. Have you obtained equal results in all four cases? If not, order the particular reaction
systems according to the decreasing value of reaction heat. What reactions cause
the above mentioned differences? Express the reactions by means of chemical
equations.
1.4 The exact methods showed that neutralisation heat in the reaction of the strong acid
with a strong base (i. e. the reaction heat when 1 mole of water is formed from H+
- -1
and OH ions) is equal to 57.57 kJ mol . Calculate the relative error of your
determination.
____________________
SOLUTION
1.1. In titrating a strong acid with a strong base, both phenolphthalein and methyl orange
can be used as acid-base indicators. The drop on the titration curve covers the colour
changes of both indicators (pH values from 4 – 10).
Only phenolphthalein can be used in the case when a weak acid is titrated with a
strong base because the neutralisation occurs at higher pH values (the colour
transition of phenolphthalein is in the region of pH = 8 – 10). A salt formed undergoes
hydrolysis (more precisely its anion) and the solution exhibits a basic reaction:
-
CH3COO + H2O CH3COOH + OH-
TH
In titrating a strong acid with a weak base or vice versa, methyl orange is used (pH =
3 – 4.5) and due to hydrolysis the resulting solution shows an acidic reaction:
+
NH+4 + 2 H2O NH3 . H2O + H3O
The exact concentrations of the aqueous solutions of sodium hydroxide and

ammonia are determined by titrations with the volumetric solution of hydrochloric
acid. The exact concentration of the acetic acid solution is then determined by a
titration with the sodium hydroxide solution.
1.2 When the specific heat capacities of glass and thermometer are neglected the
neutralisation heat can be then calculated according to a simple relation:
∆Hneutr. = (m1 + m2) c (T2 − T1)
m1 − mass of the first solution,
m2 − mass of the second solution,
c − specific heat capacity of the solutions,
T1 − temperatures of the solutions before mixing,
T2 − temperatures of the solutions after mixing.
If the temperatures of the solutions before mixing are not equal then T1 will be the
mean temperature of both. Finally, the neutralisation heat value should be related to
1 mole of water formed.
1.3 The results obtained for the neutralisation of a strong base with a weak acid and vice
versa, as well as for the reaction of a weak acid with a weak base, are lower than
those obtained for the neutralisation of a strong acid with a strong base. A part of the
heat is consumed for ionisation of a weak electrolyte:
CH3COOH + H2O CH3COO− + H3O+
A similar equation can be written for NH3.H2O.
TH
Volumetric determination of sodium carbonate and sodium hydrogen carbonate
simultaneously.
A) Procedure:
1. Determination of the precise concentration of an HCl solution (0.1 mol dm-3) using
borax Na2B4O7 . 10 H2O as a standard.
Principle:
An aqueous solution of sodium tetraborate reacts with hydrochloric acid to form
trihydrogenboric acid.
Procedure:
25.00 cm3 of a standard borax solution with a concentration of about 0.05 mol
dm-3 (the exact borax concentration is written on the label on the volumetric flask; the
solution needs not be diluted with water to a volume of 100 cm-3) is transferred into a
titration flask, 1 to 2 drops of methyl red are added and the solution is titrated to the
first orange coloration of the yellow solution. The titration should be carried out at least
twice. The consumption of hydrochloric acid should be designated by symbol V1.
2. Volumetric determination of Na2CO3 and NaHCO3 simultaneously.
Procedure:
The sample in a volumetric flask (250 cm3) should be diluted to the mark with
distilled water from which the carbon dioxide has been removed by boiling, and mix.
a) Part of the solution (25 cm3) is titrated with an HCl solution using methyl orange (2
drops) to the first red coloration of the originally yellow solution. The sample is
boiled 2 to 3 minutes to release carbon dioxide. Then the solution is cooled and
the titration is continued to a clear red coloration of the solution. The titration
should be carried out at least twice. The consumption of hydrochloric acid should
be designated as V2 (average of titration values).
b) A further part of the sample (25.00 cm3) is transferred to an Erlenmeyer flask and
mixed with 25.00 cm3 of the NaOH solution with a concentration of 0.1 mol dm-3.
Add 10 cm3 of a 10 % solution of BaCl2 and 2 drops of phenolphthalein. Excess
hydroxide should be titrated immediately in the presence of a white precipitate
formed, using an HCl solution whose precise concentration has been determined
TH
c) in part 1. The consumption of hydrochloric acid should be denoted as V3 (average

values of at least two titrations).
d) Carry out the same titration as in part b) without the sample (blank). The
consumption of HCl is designated as V4 (average of two titrations).
Use the results of the above experiments to calculate the amounts of Na2CO3 and
NaHCO3 in the sample.
B) Results
The results should be written into the form provided in which you should note the
following:
a) The ionic equation for the reaction according to which the concentration of the HCl
solution was determined.
b) The ionic equation for the reaction used in the determination of Na2CO3 and NaHCO3
simultaneously.
c) The volume of hydrochloric acid consumed in the titration of 25.00 cm3 of borax
solution.
d) Calculation of the HCl concentration (in mol dm-3).
e) Consumption of the HCl solution – V2, V3, and V4.
f) Mass amounts of Na2CO3 and NaHCO3 in the sample in grams.
-1
M(Na2CO3) = 105.989 g mol
-1
M(NaHCO3) = 84.007 g mol
TH
PRACTICAL PROBLEMS
A pH buffer solution has a well defined acidity which changes only very slightly
upon addition of moderate quantities of strong acid or base. The larger is the
quantity of acid or base that must be added to a certain volume of a buffer solution
in order to change its pH by a specific amount, the better is its action. A buffer
solution is prepared by mixing a weak acid and its conjugate base in appropriate
amounts in a solution. An example of a useful buffer system in aqueous solution is
the phosphate system.
Your task is to prepare a phosphate buffer with properties specified by the
following two conditions:
(1) pH = 7.20 in the buffer solution,
(2) pH = 6.80 in a mixture of 50.0 cm3 of the butter solution and 5.0 cm3
hydrochloric acid with a concentration of 0.100 mol dm-3.
Chemicals and equipment

Aqueous solution of phosphoric acid, sodium hydroxide solution of known
concentration, hydrochloric acid (0.100 mol dm-3), solution of bromocresol green,
distilled water.
Burettes, pipettes (25 and 5 cm3), Erlenmeyer flasks (100 and 250 cm3),
volumetric flask (100 cm3), beaker, and funnel.
Procedure
Determine the concentration of the phosphoric acid solution by titration with a
sodium hydroxide solution using bromocresol green as an indicator (pH range
3.8 < pH < 5.4).
Make a buffer solution by mixing calculated volumes of phosphoric acid and
sodium hydroxide solutions in the volumetric flask and filling the flask to the mark
with distilled water.
TH
Mix in an Erlenmeyer flask 50.0 cm3 of the buffer solution with 5.0 cm3 of the
hydrochloric acid.
Hand in your answer sheet to the referee who will also measure the pH of your
two solutions and note your results.
The pKa values for phosphoric acid are:
pKa1 = 1.75, pKa2 = 6.73, pKa3 = 11.50
____________________
SOLUTION
The buffer solution must contain
-3
H2PO-4 (concentration a mol dm ) and
-3
HPO2-
4 (concentration b mol dm ).
The concentrations should satisfy the condition

b 10−6.73
=
a 10−7.20
After addition of HCl the condition will be
50.0 b - 0.50 10-6.73
=
50.0 a + 0.50 10-6.80
From these equations,
a = 0.0122 b = 0.0361
-3
Total concentration of the phosphate system = 0.0483 mol dm
+ -3 -3
Total concentration of Na = (a + 2 b) mol dm = 0.0844 mol dm
If the concentration of both phosphoric acid and sodium hydroxide solution are 0.500
-3 3
mol dm , then 100.0 cm buffer solution will require:
0.0483 × 0.1000
volume of H3PO4 solution = 3
= 9.7 cm3
0.500 dm
0.0844 × 0.1000
volume of NaOH solution = 3
= 16.9 cm3
0.500 dm
TH
A solution in a graduated flask contains a mixture of oxalic acid and ammonium
oxalate.
One of the bottles denoted X, Y, and Z contains a solution of a calibration substance
with reducing character at a concentration of 0.1000 mol dm-3.
You are required to solve the following tasks:
a) Determine the quantity of oxalic acid and of ammonium oxalate in the solution in the
graduated flask. (The result will be given in grams.)
b) Write the formula for the substance with reducing character and the equations of the
chemical reactions which led to its determination.
In order to carry out the analyses the following solutions are available:
HCl (c = 0.1000 mol dm-3), NaOH (c = 2 mol dm-3), KMnO4 (c = 0.02 mol dm-3), 25 %
-3
H2SO4, HNO3 (c = 2 mol dm ), 5 % BaCl2, 5 % AgNO3, 5 % Hg2(NO3)2, phenol-
phthalein 0.1 %, methyl red 1 %.
c) Describe the procedure used in the individual steps, indicators employed and partial
results.
Mr(H2C2O4) = 90.04
Mr((NH4)2C2O4) = 124.11
____________________
SOLUTION
ANSWER SHEET:
A1 – Identification of the solution with the reducing substance X, Y, Z: Fe(NH4)2(SO4)2
A2 – Identification reactions for the ions of the substance
- Fe2+ + 2 NaOH → Fe(OH)2 + 2 Na+
- NH+4 + NaOH → NH3 ↑ + H2O + Na+
- 4 NH3 + 2 Hg2(NO3)2 + H2O → O(Hg)2NH2.NO3 + 3 NH4OH
4 + BaCl2 → BaSO4 + 2 Cl
–
- SO2-
B1– Preparation of the 0.1 M NaOH solution

. . . . . . . . . . . . . . . . cm3 in 200.0 cm3
TH
B2 – Concentration of the NaOH in its solution: . . . . . . . . . . . M

Indicator used: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
C – Concentration of KMnO4 in its solution . . . . . . . . . . . . . M
D1 – Mass of oxalic acid in the initial solution . . . . . . . . . . . . g

Indicator used . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
D2 – Mass of ammonium oxalate in the initial solution . . . . . . . . . . . . . g
Solution
A1 – 1-2 cm3 of solution X, Y and Z are put into three test tubes. 6 N H2SO4 and a drop of
KMnO4 solution are added. The solution which loses colour is the one with reducing
character.
A2 – Establishment of the formula:
. . . . . . . . + NaOH – greenish white precipitate ⇒ Fe2+
. . . . . . . . + NaOH at the upper end of the test-tube, filter paper with a drop of
Hg2(NO3)2 , black spot ⇒ NH+4
. . . . . . . . + BaCl2 – white precipitate ⇒ SO2-

4
. . . . . . . . + AgNO3 + HNO3 ⇒ Cl– is absent

Accordingly the substance used is Fe(NH4)2(SO4)2.
The chemical reactions:
Fe2+ + 2 Na+ + 2 OH– → Fe(OH)2 + 2 Na+
NH+4 + Na+ + OH– → NH3 + H2O + Na+
4 NH3 + 2 Hg2(NO3)2 → O(Hg)2NH2 . NO3 + 2 Hg + 3 NH4NO3
+ 2 Cl– → BaSO4 + 2 Cl–

2+
SO2-
4 + Ba
B1 – 5 cm3 2 M solution ⇒ 100 cm3 0.1 M solution

B2 – V cm3 0.1000 N HCl + 0.1 N NaOH in the presence of phenolphthalein.
C – V cm3 solution X + 10.0 cm3 H2SO4 + H2O is titrated at elevated temperature with
KMnO4.
TH
3
D1 – The solution which is to be analyzed is filled to the mark; V cm of this solution is
titrated with NaOH in the presence of methyl red. The quantity of oxalic acid (moles
and g) is calculated.
D2 – V cm3 solution to be analyzed + 10.0 cm3 6 N H2SO4 + H2O are heated and titrated
with KMnO4 solution.
The total amount of oxalate is calculated (in mol).
The difference gives the amount of ammonium oxalate (moles and g).
TH
PRACTICAL PROBLEMS
Determination of the relative molecular mass of a weak acid by acid-base titration in a
non-aqueous solvent
Weak acid whose dissociation constants, Ka, are smaller than 1 × 10

-7
can be
satisfactorily titrated in ethanol or in a mixture of ethanol and benzene, using a standard
ethanolic solution of potassium hydroxide or potassium alkoxide in the presence of
phenolphthalein or thymolphthalein as an indicator.
Task:
Determine the molecular weight (chemical equivalent) of a weak monobasic acid by
titration with potassium ethoxide in ethanolic solution using phenolphthalein as an
indicator (the acid has the general formula CxHyOz).
Chemicals and equipment:

Standard solution of potassium ethoxide in ethanol of concentration c = 0.1000 mol dm-3
Indicator: 0.1% solution of phenolphthalein in ethanol
Solvent: A mixture of ethanol and benzene
1.000 g of sample, accurately weighed,
3 titration flasks of volume 200 or 500 cm3, one 25 cm3 burette, one 50 cm3 pipette, one
250 cm3 volumetric flask, one 100 cm3 measuring cylinder, small funnels, beakers, filter
paper.
Procedure:
You are provided with 1.000 g of the monobasic acid CxHyOz. This sample is labelled
with a number. This should be written clearly at the top of your answer paper.
Carefully transfer all the acid into the graduated (volumetric) flask and fill the solution
in the flask with ethanol up to 250 ml. A portion of 50.00 ml of this solution should be
titrated with the 0.1000 M alcoholic solution of potassium ethoxide using 5 drops of
phenolphthalein as indicator. The first titration should be a rough titration for estimating the
TH
approximate volume necessary to determine the endpoint. Subsequent titrations should

be carried out with precision, using the same quantity of indicator each time.
Record all titration values. An extra titration should be carried out to eliminate any
error that might be due to the action of the potassium hydroxide on the solvent, indicator
or ethanol. This type of titration is known as a blank titration, its value should be recorded
and used to correct the results of previous titrations. Care should be taken to use the
same quantity of indicator as in previous titrations.
The correct titration values should be used to calculate the relative molecular mass
(molecular weight) of the sample.
Note: The waste material containing organic solvents must not be discharged in a
sink. Use labelled containers for this purpose.
Questions:
1) Suggest the name and formula of a common, monobasic acid which corresponds to
the value you determined experimentally for your sample.
2) Write a general equation for the neutralisation of a monocarboxylic acid with:
i) potassium ethoxide,
ii) potassium hydroxide.
3) During the titration of some weak carboxylic (fatty) acids, similar to the titration that
you have carried out, turbidity or cloudiness is observed. Suggest an explanation for
this turbidity.
4) How would you produce 1 dm3 of a standard solution of 0.1 M potassium ethoxide?
Which compound would you use, as a standard solution?
5) Why are the titrations of weak acids carried out in non-aqueous media?
6) Name another solvent which is suitable for use in the titration of weak acids.
7) How would you recover the organic solvent used in your experiment?
8) Sketch a schematic titration curve (pH as a function of volume) for the titration of 20
ml of a 0.1 M aqueous solution of a weak monobasic acid with a standard aqueous
solution of 0.1 M potassium hydroxide.
9) Calculate the pH of 0.1 M aqueous solution of an acid which has a dissociation
constant of 1 × 10-7.
TH
THE 18 INTERNATIONAL CHEMISTRY OLYMPIAD, Leiden, 1986
Analysis of the Nickel Salt:
For the analysis of the salt, only one sample solution is prepared. The determination
of the components is achieved by titrating each time 25 ml of the sample solution in
duplicate.
For the determination of the ammonia and chlorine content a back titration is carried
out. For that purpose a certain amount of reagent is added in excess. The total amount of
reagent, available for the sample, is determined by following the same procedure for 25 ml
of a blank solution. This titration should not be carried out in duplicate.
Prepare the following solutions:
A) Sample solution:
Pipette 25.0 ml of 1.6 M nitric acid into a volumetric flask of 250 ml. Add a sample of
about 1.2 g of the amminenickel(II) chloride and dilute with water to a volume of 250 ml.
B) Blank solution:
Pipette 25.0 ml of the same 1.6 M nitric acid and dilute it with water to a volume of
250 ml.
Note:
1) For the chlorine determination use conical (Erlenmeyer) flasks with a ground glass
stopper.
2) The nitric acid contains a small amount of hydrochloric acid. The total acid content is
1.6 M.
a) Determination of the ammonia content

Titrate the solutions with a standard solution of NaOH (about 0.1 M). Indicator:
methylred, 0.1 % solution in ethanol.
Calculate the percentage of ammonia in the salt.
b) Determination of the nickel content
Add about 100 ml of water, 2 ml of ammonia solution (25 %) and 5 drops of murexide
solution to the nickel solution, which now should have a yellow colour. Titrate the solution
with a standard solution of EDTA (about 0.025 M) until a sharp colour change from yellow
to violet is observed. Calculate the percentage of nickel in the salt.
THE COMPETITION PROBLEMS FROM THE INTERNATIONAL CHEMISTRY OLYMPIAD, Volume 1 364
TH
c) Determination of the chlorine content

Execute the titration as quickly as possible after the addition of the reagent!
Add to each solution 25 ml of 0.1 M silver nitrate solution. Add about 5 ml of toluene,
shake vigorously, add indicator and titrate with the standard solution of ammonium
thiocyanate (-rhodanide, about 0.05 M) until a permanent colour change to red is
observed. At the end of the titration, shake vigorously again. The red coloration should
persist.
Indicator: 1 ml of a saturated solution of iron(III) sulphate.
Calculate the percentage of chlorine in the salt.
Data: Relative atomic masses: H = 1, Cl = 35.5, Ni = 58.7, N = 14.
Questions:
Calculate from the results obtained the molar ratio of the components to two decimal
points and enter this on the report form in the format: Ni : Cl : NH3 = 1.00 : x : y.
ST
Analysis
Determination of Mass of a given Sample of 2-Ethanoyl-oxybenzoic Acid (Acetylsalicylic
Acid, or Aspirin) by Volumetric Back Titration after Hydrolysis with Excess of Sodium
Hydroxide.
Reagents
Aqueous solution of sodium hydroxide (about 0.5 mol dm-3)
Standard aqueous solution of hydrochloric acid (0.4975 mol dm-3)
Ethanolic phenolphthalein solution (indicator dropping bottle II)
Deionised/distilled water
Part 1:
Determine accurately the concentration of the about 0.5 mol dm-3 sodium hydroxide
solution using the standard hydrochloric acid solution. (Record the answer as mol dm-3
with four places after decimal point.)
Procedure:
Pipette 20.00 cm3 of the sodium hydroxide solution into a 300 cm3 Erlenmeyer flask
and dilute it to about 100 cm3 with deionized water. Titrate the obtained solution with the
standard 0.4975 mol dm-3 hydrochloric acid solution using the phenolphthalein indicator.
Repeat the procedure to produce three acceptable values and calculate the mean volume.
Part 2:
Determine accurately the mass of aspirin in Erlenmeyer flask I. Record your answer in g
with three places after the decimal point.
Procedure:
Pipette 50.00 cm3 of your standardized sodium hydroxide solution into the
Erlenmeyer flask I (with a ground glass joint) which contains your unknown mass of
aspirin. Add 3 – 5 boiling stones to the flask and boil the reaction mixture for 15 minutes
using a reflux condenser and the electrical hot plate. After cooling, remove the reflux
ST
condenser and rinse it with a small quantity of deionised water into Erlenmeyer flask I.
3
Pour the whole solution into a 100.0 cm volumetric flask and fill it exactly to the mark with
3 3
deionised water. Pipette 20.00 cm of this solution into a 300 cm Erlenmeyer flask and
3
dilute to about 100 cm with deionised water. Back titrate the residual sodium hydroxide
-3 3
with the standard hydrochloric acid solution (0.4975 mol dm ) using a 10 cm burette and
phenolphthalein indicator. Repeat the volumetric procedure to produce three acceptable
values and calculate the mean volume.
Questions:
1) Write the balanced chemical equation for the ester hydrolysis of aspirin by sodium
hydroxide using structural formulae. Note that 1000 cm3 aqueous solution of 0.5000
mol dm-3 sodium hydroxide is equivalent to 0.0450 g of aspirin.
2) Calculate the mass of aspirin that you were given.
_______________
SOLUTION
1.
COOH COONa
OCOCH3 OH
+ 2 NaOH + CH3COONa + H2O
TH
THE 25 INTERNATIONAL CHEMISTRY OLYMPIAD, Perugia, 1993
Analysis
Citric acid (2-hydroxy-1,2,3-propanetricarboxylic acid) is widely distributed in plants
and in animal tissues. Lemon juice contains from 5 to 8% of this acid. It is produced by
mycological fermentation on an industrial scale using crude sugar solutions, such as
molasses, and stains of Aspergillus niger.
It is utilized as an acidulant and antioxidant in several beverages.
-3
a) Standardization of NaOH solution (ca 0.1 mol dm ) by potassium hydrogen
phthalate
Procedure:
A preweighed quantity (2.050 g) of potassium hydrogen phthalate is in the 100 cm3
volumetric flask B. Dilute this sample with water to the mark. Phenolphthalein indicator
(2 - 3 drops) is added to an aliquot of 25.0 cm3 of the resulting solution and the solution is
then titrated with the NaOH solution that has to be standardized.
Give the concentration of the NaOH solution.
b) Titrimetric determination of citric acid

Procedure:
The unknown sample of citric acid is in the 100 cm3 volumetric flask C. Dilute the
sample with water to the mark. Transfer 25.0 cm3 of the resulting solution into a 250 cm3
Erlenmeyer flask and dilute with water. Add 2 – 3 drops of phenolphthalein indicator and
titrate with the previously standardized NaOH solution.
Give the mass of citric acid.
_______________
TH
SOLUTION
Marks were given accordingly to determined mass of citric acid.
Some additional points were given for correct calculations.
TH
THE 26 INTERNATIONAL CHEMISTRY OLYMPIAD, Oslo, 1994
PRACTICAL PROBLEMS
Determination of Fatty Acids
A mixture of an unsaturated monoprotic fatty acid and an ethyl ester of a saturated
3
monoprotic fatty acid has been dissolved in ethanol (2.00 cm of this solution contain a
1) 2)
total of 1.00 g acid plus ester). By titration the acid number , the saponification number
and the iodine number3) of the mixture shall be determined. The acid number and the
saponification number shall be used to calculate the number of moles of free fatty acid and
ester present in 1.00 g of the sample. The iodine number shall be used to calculate the
number of double bonds in the unsaturated fatty acid.
Note: The candidate must be able to carry out the whole exam by using the delivered
amount of unknown sample (12 cm3). There will be no supplementation.
1) Acid number: The mass of KOH in milligram that is required to neutralize one gram of
the acid plus ester.
2) Saponification number: The mass of KOH in milligram that is required to saponify one
gram of the acid plus ester.
3) Iodine number: The mass of iodine (I) in g that is consumed by 100 g of acid plus
ester.
Relative atomic masses:
Ar(I) = 126.90 Ar(O) = 16.00
Ar(K) = 39.10 Ar(H) = 1.01
1) Determination of the Acid Number

Reagents and Apparatus
Unknown sample, 0.1000 M KOH, indicator (phenolphthalein), ethanol/ether (1 : 1
mixture), burette (50 cm3), Erlenmeyer flasks (3 x 250 cm3), measuring cylinder (100 cm3),
graduated pipette (2 cm3), funnel.
TH
Procedure:
3 3
Pipette out aliquots (2.00 cm ) from the unknown mixture into Erlenmeyer flasks (250 cm ).
3
Add first ca. 100 cm of an ethanol/ether mixture (1:1) and then add the indicator (5 drops).
Titrate the solutions with 0.1000 M KOH.
Calculate the acid number.
2) Determination of the Saponification Number

Unknown sample, 0.5000 M KOH in ethanol, 0.1000 M HCl, indicator (phenolphthalein),
volumetric flask (50 cm3), round bottom flask (250 cm3), Liebig condenser, burette (50
cm3), Erlenmeyer flasks (3 x 250 cm3), volumetric pipette ( 25 cm3), volumetric pipette (10
cm3), graduated pipette (2 cm3), funnel, glass rod. The round bottom flask and Liebig
condenser are to be found in the fume hoods.
Procedure
3 3
Pipette out a 2.00 cm aliquot of the unknown sample into a round bottom flask (250 cm )
and add 25.0 cm3 0.5000 M KOH/EtOH. Reflux the mixture with a heating mantle for 30
min in the fume hood (start the heating with the mantle set to 10, then turn it down to 5
after 7 min.). Bring the flask back to the bench and cool it under tap water. Transfer
quantitatively the solution to a 50 cm3 volumetric flask and dilute to the mark with a 1:1
mixture of ethanol/water. Take out aliquots of 10 cm3 and titrate with 0.1000 M HCl using
phenolphthalein as indicator (5 drops).
Calculate the saponification number.
3) Determination of the Iodine Number

In this experiment iodobromine adds to the double bond.
I Br
C C + IBr C C
The Hanus solution (IBr in acetic acid) is added in excess. After the reaction is complete,
excess iodobromine is reacted with iodide forming I2, (IBr + I- → I2 + Br-) which in turn is
determined by standard thiosulphate solution.
TH
Warning: Be careful when handling the iodobromine solution. Treat any spill immediately
with thiosulphate solution.

Unknown sample, 0.2000 M Hanus solution, dichloro-methane, 15 % KI solution in distilled
water, distilled water, 0.2000 M sodium thiosulphate, starch indicator, Erlenmeyer flasks (3
3 3 3
x 500 cm ), buret (50 cm ), graduated pipette (2 cm ), measuring cylinders (10 and 100
3 3
cm ), volumetric pipette (25 cm ), aluminium foil.
Procedure
Pipette out aliquots (1.00 cm3) of the unknown mixture into Erlenmeyer flasks (500 cm3)
and add 10 cm3 of dichloromethane. With a pipette add 25.0 cm3 Hanus solution, cover
the opening with aluminium foil and place your labelled flasks in the dark in the cupboard
(under the fume hood) for 30 min. with occasionally shaking. Add 10 cm3 of the 15 % KI
solution, shake thoroughly and add 100 cm3 of dist. water. Titrate the solution with 0.2000
M sodium thiosulphate until the solution turns pale yellow. Add starch indicator (3 cm3)
and continue titration until the blue colour entirely disappears.
Calculate the iodine number.
4) Use the results from 1) 2) and 3) to:

i) Calculate the amount of ester (in mol) in 1 g of the acid plus ester.
ii) Calculate the number of double bonds in the unsaturated acid.
TH
THE 30 INTERNATIONAL CHEMISTRY OLYMPIAD, Melbourne, 1998
Analysis of a Mixture of Cobalt(III) Complexes
When the complex [Co(NH3)5NO2]Cl2 is prepared in the laboratory, it often contains a

considerable amount of [Co(NH3)6]Cl3 by-product.
In this exercise, you must determine the amount of [Co(NH3)5NO2]Cl2 in a sample
that also contains only [Co(NH3)6]Cl3 as a by-product, using a cation-exchange procedure.
The cation exchange resin used in this exercise is a cross-linked polystyrene resin of the
strong acid type. It contains –SO3H groups from which the H+ can be exchanged. When a
solution containing 1 mol of Mn+ is allowed to react with the resin this liberates n mol of H+.
In this exercise, the solution resulting from ion exchange of the mixture of the two different
complex cations is used to titrate a standardised NaOH solution.
Preparation of the cation exchange resin

You are provided with about 10 g of wet resin in the H+ form. Wash the resin using the
following procedure to remove all traces of free acid:
1. Transfer your resin to a 250 cm3 beaker, washing it from the container with about 50
3
cm of water, then let the resin settle. This will take a few minutes.
2. Carefully pour off (decant) as much of the acidic solution as possible into a ‘waste’
beaker. Try to minimise loss of any of the resin in this process. Wash the resin with
~20 cm3 portions of distilled water and test a drop of washing solution using a glass
rod and pH paper until the excess acid is completely removed (pH ~5). You should
not need to use more than 200 cm3 of water to do this.
3. Drain off all but enough water to leave the resin just covered with water.
Be sure to put all your acidic wash solutions into a waste bottle labelled “acid waste”
- not down the sink! Do not allow the resin to dry out.
Preparation and standardisation of approximately 0.0125 M NaOH

4. Prepare 250.0 cm3 of approximately 0.0125 M NaOH by accurately diluting your
~0.125 M NaOH with distilled water in a volumetric flask.
5. With the standard 0.01253 M HCl that is provided, titrate 25.00 cm3 aliquots of the
diluted NaOH solution, using phenolphthalein indicator.
TH
Analysis Procedure
3
You are provided with approximately 40 cm of a 0.00500 M solution of HCl that
contains 0.2000 g of a mixture of the cobalt(III) complexes [Co(NH3)5NO2]Cl2 and
3
[Co(NH3)6]Cl3 in 40.00 cm .
6. Use a pipette to transfer a 25.00 cm3 aliquot of the cobalt complex solution into a
3 3
250 cm beaker (beaker No 1) and add ~25 cm water.
7. Use a plastic spoon to add about half (~5 g) of your wet resin to the cobalt(III)
solution and allow to stand for at least 5 minutes for ion-exchange to take place,
+
liberating H . You should occasionally gently swirl the mixture to hasten the ion-
exchange process.
8. Carefully wash the acidic solution into a second 250 cm3 beaker (beaker No 2) with
about 20 cm3 of distilled water. Try to leave as much as possible of the resin behind.
Notice that the solution is now much lighter in colour, indicating that most, but not all
of the cobalt complex mixture is stuck to the resin. You must now remove the last
traces of cobalt(III) from solution (liberating more acid in the process), with a second
batch of resin.
9. Add most of the remainder of your resin (~4 g) to the solution in beaker No 2 and
again allow to stand for at least 5 minutes to allow the cation exchange to take place,
liberating more H+.
At the end of this process, the solution should be colourless - if not, (perhaps you did
not wait long enough for ion-exchange to take place) repeat the ion-exchange and
washing steps with the last portion (~1 g) of your ion-exchange resin.
10. Filter the two resin samples through a carefully washed filter paper, and collect the
acidic filtrate in a 100 cm3 volumetric flask. Carefully wash the resin with small
portions of water into the volumetric flask and make up to the mark with water.
11. With this acid solution titrate 25.00 cm3 aliquots of your standardized NaOH solution.
Calculate the number of moles of H+ liberated by the 25 cm3 aliquot of your mixture
of cobalt(III) complexes and report the percentage of [Co(NH3)5NO2]Cl2 that is
present in your sample.
Molar masses in g mol-1: Co 58.93; N 14.01; H 1.01; Cl 35.45; O 16.00.

_______________
TH
SOLUTION
Model solution
Standardization of 0.0125 M NaOH
-3
Concentration of standard HCl in bottle: 0.01253... mol dm
Titration number 1 2 3
aliquot of NaOH 25.00 25.00 25.00
3
initial burette reading (cm ) 13.60 17.40 10.35
3
final burette reading (cm ) 37.75 41.50 34.45
volume of standard KMnO4 (cm3) 24.15 24.10 24.10
Average titre (cm3) 24.12
c(NaOH) = 0.01250 mo! dm-3 × 0.02412 dm3 = 0.01206 mol dm-3
Aliquot of cobalt complex solution used for ion-exchange: 25 cm3

3
initial burette reading (cm ) 26.25 16.10 3.80
final burette reading (cm3) 48.50 38.40 26.20
Average titre (cm3) 22.32
Calculations
c(H+) collected in 100 cm3 flask:
c(H+) = 0.01206 mol dm-3 × (25.00 cm3) / (22.32 cm3) = 0.01351 mol dm-3
total n(H+) collected from column:
n(H+) = 0.01351 mol dm-3 × 0.100 dm3 = 1.351×10–3 mol
n(H+) from aliquot put onto column:
n(H+) = 0.00500 mol dm-3 × 0.02500 dm3 = 1.250×10–4 mol
n(H+) ion-exchanged from complexes in aliquot put onto column:
n(H+) = 1.351×10-3 mol – 1.250×10-4 mol = 1.226×10-3 mol
let y = mass [Co(NH3)5NO2]Cl2 in 25.00 cm3 aliquot of mixture added to column mass of
mixture added to column = (25.00 cm3 / 40 cm3) × 0.2000 g = 0.1250 g
TH
then mass [Co(NH3)6]CI3 in aliquot = (0.1250 - y) g

n(H+) ion-exchanged from [Co(NH3)5NO2]Cl2:
n(H+) = 2 y / 261.00 g mol-1 = 0.007663x mol
+
n(H ) ion-exchanged from [Co(NH3)6]Cl3:
+ -1
n(H ) = 3 (0.1250 – y) g / 267.50 g mol = (0.001402 – 0.011214 y) mol
Thus, 0.007663 y + (0.001402 – 0.011214 y) = 0.001226 or y = 0.04956 g
% [Co(NH3)5NO2]CI2 = 100 (0.04956 g / 0.1250 g) = 39.6 %
TH
Reverse-phase Chromatography:
Acid-Base Titration of Acetic Acid and Salicylic Acid
Acetic acid (AA) and salicylic acid (SA) are slightly different in polarity and thus can
be separated on a reverse-phase cartridge using distilled water as eluent. AA is eluted
first. The total amount of AA and SA in a mixed solution will be determined by titration.
Then, AA and SA will be separately determined following chromatographic separation.
2-1. Determination of the Total Amount of AA and SA in a Mixed Acid (MA) Solution
a) Titrate 10 cm3 of distilled water with the NaOH (< 5 mM) solution provided.
Report blank acidity in 1 cm3 of distilled water in terms of the volume of the
NaOH solution. Take this blank acidity into account for all solutions in
subsequent data analyses. Show corrections in the calculation part in the
answer sheet.
b) Standardize NaOH solution with 2.00 cm3 of the standard KHP (potassium
hydrogen phthalate) solution (1.00 x 10-2 M) provided. Repeat and report the
concentration of the NaOH solution. Show how you accounted for the blank
acidity.
c) Withdraw 1.00 cm3 of Solution MA and determine the total acidity. Repeat and
report the total number of moles of AA and SA combined in 1.00 cm3 of
Solution MA.
2-2. Reverse-phase Separation and Titration

a) Elute a new C-18 cartridge with about 10 cm3 of distilled water using 10 cm3
syringe.
b) Load 1.00 cm3 of Solution MA onto the cartridge. Collect the liquid eluting at the
outlet in tube 1 (Fraction 1).
c) Elute with 1 cm3 of distilled water. Collect the eluent in a test tube (Fraction 2).
Repeat until Fraction 20 is collected. You will have 20 test tubes with about 1
cm3 liquid in each tube.
TH
d) Titrate acidity in each test tube. Report volume of the NaOH solution consumed
and the amount of acid(s) in each test tube. Make a graph in the answer sheet
(Fig. 2-2) showing the amount of acid(s) in each test tube.
e) Blank acidity and the background (due to leaching out of residual materials
from the column) must be subtracted. In determining the amount of eluted AA,
disregard tubes containing only trace amounts of acids. Tube 2 and 3 contain
most AA. Calculate the total amount of AA eluted by adding the amount of AA
in tubes. Similarly calculate the total amount of SA eluted. Indicate, in Fig. 2-2,
which fractions you used to get the amount of each acid.
f) Calculate the mole percent of AA in solution MA.
TH
Determination of Carbonate and Hydrogen Phosphate in an Abrasive Sample
Na2CO3, CaCO3 and Na2HPO4 are the main constituents of abrasive powders. In this
task you will have to determine carbonate and hydrogen phosphate ions in an abrasive
sample by two acid-base titrations.
First, the exactly known amount of hydrochloric acid (taken in an excess) is added to
the sample. As a result, hydrogen phosphates are transformed into H3PO4, whereas
carbonates into CO2 which is further removed by boiling. Calcium ions initially present in
the sample pass into the solution. Because of possible interference in subsequent
analysis, they are precipitated as CaC2O4 and filtered off prior to the titration.
Next, the phosphoric acid formed is subjected to two titrations with pre-standardized
NaOH solution and two different indicators: Bromocresol Green (BCG) and
Thymolphthalein (TP). First, H3PO4 (and excess of HCl) is titrated to H2PO4− ion, the
endpoint lying in slightly acidic medium (pH of ~4.5). It corresponds to the colour change
of BCG from yellow to blue. The second titration proceeds till HPO24− is formed. The
endpoint of the second titration corresponds to the color change of TP from colourless to
blue (moderately alkaline medium, pH of ~10).
The content of CO23− ions in the sample is calculated by finding the difference between:
a) the amount of the titrant equivalent to the initial amount of HCl (taken for the
sample dissolution) and
b) the amount of the titrant corresponding to the second endpoint (TP).
The content of HPO24− is calculated by finding the difference between the amounts of
the titrant consumed to achieve two endpoints (TP and BCG).
Procedure
Step 1. Dissolution of the sample and removal of CO2
To the sample of the abrasive powder in a beaker covered with watch glass add
3
10.00 cm (exactly, with a pipette! Carefully, not removing the glass and avoiding losses
-3
because of splashing!) of ca. 1 mol dm HCl (see the exact concentration of the acid on
the label). After the most intensive stage of gas evolution is completed, heat
TH
carefully the solution in the beaker (covered with watch glass) on a heating plate until the
gas evolution stops. Then bring the solution to boiling and boil it carefully for 2 – 3 min.
Step 2. Precipitation of calcium

Remove the beaker from the plate; wash the steam condensate from the watch glass
down to the beaker with distilled water. Add 1 – 2 cm3 of 15 % K2C2O4 solution with
measuring cylinder. Put the beaker aside until the most part of the precipitate is formed
(usually takes 10 to 20 min). Spend this time for standardization of the titrant solution of
NaOH (see the procedure hereunder).
Step 3. Standardization of NaOH solution

Place with a pipette 10.00 cm3 of HCl solution into a 100 cm3 volumetric flask, make
up to the mark with distilled water and mix. Fill the burette with NaOH solution. Transfer
with a pipette 10.00 cm3 of the diluted HCl solution from the volumetric flask to an
Erlenmeyer flask. Add 1 – 2 drops of Thymolphthalein solution and titrate with NaOH
solution until blue coloration stable on swirling for 5 – 10 s appears.
Here and after. Repeat the titrations as necessary. It is desirable that the highest and the
lowest titrant volume values differ not more than by 0.10 cm3. Report all the final volume
3
values with 0.01 cm accuracy.
2.1 a Complete the table in the Answer Sheet.
2.1 b Calculate the concentration of NaOH solution (in mol dm-3).
Step 4. Filtering off calcium oxalate

After the most part of CaC2O4 precipitates filter the precipitate off collecting the
filtrate into a 100 cm3 volumetric flask. Slight turbidity in the filtrate is admissible, since
small amounts of calcium oxalate do not interfere in the titration. Wash the filter with
distilled water; make up the solution in the flask to the mark with distilled water and mix.
Put the used filter into the waste basket.
Step 5. Sample titration against Bromocresol Green

Transfer with a pipette a 10.00 cm3 aliquot of the sample solution coming from the
TH
step 4 from the volumetric flask to an Erlenmeyer one, and add 3 drops of BCG solution.
Prepare in another Erlenmeyer flask a reference solution by adding 3 drops of 15 %
3
NaH2PO4 solution and 3 drops of BCG solution to 15 – 20 cm of distilled water. Titrate the
sample solution with NaOH solution until the colour coincides with that of the reference
solution.
2.2 Complete the table in the Answer Sheet.
Step 6. Sample titration against thymolphthalein

3
Transfer with a pipette a 10.00 cm aliquot of the sample solution coming from the step 4
from the volumetric flask to an Erlenmeyer one. Add 2 drops of TP solution and titrate with
NaOH solution until blue coloration stable on mixing for 5 – 10 s appears.
2.3 Complete the table in the Answer Sheet.
Step 7. Calculations
2.4 Calculate the mass of CO32- in the sample.
2.5 Calculate the mass of HPO2-

4 in the sample.
Step 8. Additional questions to the problem

Answer the additional questions in the Answer Sheets.
2.6a Indicate one reaction (write down the equation) for a process interfering in the
2+
sample analysis you have carried out in the presence of Ca .
2.6b A list of mistakes possible at different steps is given in the table in the answer sheet.
Indicate which of the mistakes can lead to errors in CO32- and/or HPO2-
4 content
determination. Use the following symbols: “0” if no error is expected, “+”or “–“ if the
result is higher (positive error) or lower (negative error) than the true one.
_______________
SOLUTION
2.1 a, 2.2, 2.3
The values of the final volumes V1,f, V2,f, and V3,f, (as reported in the Answer Sheet)
were graded according to a scheme approved by the International Jury.
TH
The values of ∆Vexpected and ∆Vacceptable (in cm3) are listed in the table below.
∆V, cm3
expected acceptable
V1,f 0.10 0.25
V2,f 0.15 0.40
V3,f 0.15 0.40
2.1 b Calculation of NaOH concentration

c (HCl) × V (HCl) × V (aliquot) 1.214 mol dm-3 × 10.00 cm3 × 10.00 cm3
c(NaOH) = =
V (flask) × V (NaOH) 100.0 cm3 × V1,f cm3
2.4 Calculation of the mass of CO32-
c(NaOH) × (V1,f − V3,f ) × V (flask)

m( CO32- ) = M( CO32- ) × 1/2 × =
V (aliquot)
c (NaOH) mol dm-3 × (V1,f − V3,f ) cm3 × 100.0 cm3

= 60.01 g mol × 1/2 × × 0.001dm3 /cm3 =
-1
3
10.00 cm
2.5 Calculation of the mass of HPO2-

4
c(NaOH) × (V3,f − V2,f ) × V (flask)

4 ) = M( HPO 4 ) ×
m( HPO2- 2-
=
V (aliquot)
c (NaOH) mol dm-3 × (V3,f -V2,f ) cm3 × 100.0 cm3

= 95.98 g mol × × 0.001 dm3 /cm3 =
-1
3
10.00 cm
2.6 a
+ H2PO-4 → CaHPO4 + H
2+ +
Ca
or
4 → Ca3(PO4)2 + 2 H
2+ +
3 Ca + 2 HPO2-
TH
Determination of the Langelier Saturation Index of a pool water

The Langelier Saturation Index (LI) is a measure of swimming pool water corrosivity
as well as its ability to dissolve or deposit calcium carbonate. If LI is approximately zero,
the water is considered “balanced”. If the index LI is a positive number, the water tends to
deposit calcium carbonate and is scale-forming. If the index LI is a negative number, the
water is corrosive and dissolves calcium carbonate. The LI is a combination of the physical
values factors taken from Table 1 and can be calculated by the formula:
LI = pH + FT + FD + FA – FTDS
-0,8 -0,4 -0,1 0 0,1 0,4 0,8

Aggressive water Danger of Acceptable Excellent Acceptable Danger of scaling Formation of
causing corrosion corrosion balance balance balance and deposits scale and
of metallic parts deposits
etc
pH : pH value
FT : Temperature factor
FD : Calcium hardness (CH) factor
FA : Total alkalinity (TA) factor
FTDS: Total dissolved solids (TDS) factor
Table 2.1 Values and corresponding factors

Calcium Total Total
hardness alkalinity dissolved
Temperature,
о FT (CH), FD (TA), FA solids (TDS), FTDS
С -3 3 -3
mg dm mg dm mg dm
CaCO3 CaCO3 NaCl
0 0.0 5 0.3 5 0.7 0 12.0
3 0.1 25 1.0 25 1.4 - -
8 0.2 50 1.3 50 1.7 1000 12.1
12 0.3 75 1.5 75 1.9 - -
16 0.4 100 1.6 100 2.0 2000 12.2
19 0.5 150 1.8 125 2.1 - -
24 0.6 200 1.9 150 2.2 3000 12.25
29 0.7 250 2.0 200 2.3 - -
IChO International Information Centre, Bratislava, Slovakia, 2014
TH
Table 2.1 continued
34 0.8 300 2.1 300 2.5 4000 12.3

41 0.9 400 2.2 400 2.6 - -
53 1.0 600 2.35 800 2.9 5000 12.35
- - 800 2.5 1000 3.0 - -
- - 1000 2.6 - - 6000 12.4
In this task you will have to determine the LI value of a given water sample. Note that
hardness is expressed as the equivalent to the concentration of CaCO3 (expressed in
mg dm-3). Total alkalinity, being the acid equivalent to the total amount of carbonate and
hydrogen carbonate, can also be expressed in mg dm-3 of CaCO3, whereas TDS is
recalculated as concentration of NaCl (mg dm3).
Chemicals
• EDTA, standard aqueous solution, c = 0.0443 mol dm–3,

• HCl, standard aqueous solution, c = 0.0535 mol dm–3,
• Methyl orange, 0.1% in water,
• Murexide, indicator, solid mixture with NaCl (1 : 250 by mass),
• Sample of water.
Procedures
Calcium hardness is determined by complexometric titration with EDTA (Na2H2Y).
This is performed in a strongly alkaline medium to mask magnesium (large amounts of
Mg2+ interfere due to the co-precipitation of calcium with Mg(OH)2; moreover, the
complexometric indicator is also adsorbed on Mg(OH)2, which impairs the observation of
its colour change). When the alkali is added, titration should be carried out immediately to
avoid the deposition of CaCO3.
2.1 Write down equation of the reaction occurring during titration with Na2H2Y.
Procedure for determination of calcium

a) Put the standard solution of EDTA (precise exact concentration c = 0.0443 mol dm–3)
in the burette.
b) Pipette a 20 cm3 aliquot of the water sample into an Erlenmeyer flask.
3 –3 3
c) Add 3 cm of NaOH solution (c = 2 mol dm ) with the 10 cm measuring cylinder.
TH
d) Add murexide indicator with spatula to obtain noticeably pink solution.

e) Within few minutes titrate the mixture with EDTA solution until the indicator colour
changes from pink to purple.
2.2 Fill in the table 2.2.

Table 2.2
Titration No
Volume of EDTA solution
Initial reading of the burette, cm3

Final reading of the burette, cm3
Consumed volume, cm3
Accepted volume, cm3:
2.3 Calculate the hardness of the water sample in mg dm–3 of CaCO3. Write down the
result in Table 2.4 (see question 2.11).
Measurement of pH
Locate a pH meter in the lab (or ask your lab assistant).
3
a) Place about 70 -- 90 cm of the water sample into a clean Erlenmeyer flask.
b) Remove the protective cap from the pH-meter (keep the cap standing, since there is
solution in it).
c) Rinse the electrode with distilled water using a plastic wash bottle.
d) Turn the pH meter on by sliding the ON/OFF switch.
e) Immerse the electrode in the solution to be tested and stir gently by swirling the flask.
f) Place the flask on the table and wait until the reading stabilizes (not more than 1 min).
g) Read and record the pH value.
h) Switch the pH meter off, rinse the electrode with distilled water and place the
protective cap back.
2.4 Write down the pH value in Table 2.4 (see question 2.11).
2.5 Which form of carbonic acid predominates in your water sample?
Confirm your choice with calculation and tick one box.
Carbonate Hydrogen carbonate Carbonic acid
TH
Note: The dissociation constants of carbonic acid are as follows:

–7
K1 = 4.5 · 10 ;
K2 = 4.8 · 10–11.
2.6 Write down the ionic equation of the predominant reaction of titration of the water
sample with HCl solution.
Determination of the total alkalinity

To obtain the value of the total alkalinity the water sample should be titrated to
H2CO3. An acid-base indicator used is methyl orange, which starts changing its colour
from yellow to orange at pH of about 4.5.
a) Rinse the burette with distilled water and fill it with the standard HCl solution (exact
concentration of HCl is 0.0535 mol dm–3).
3
b) Pipette a 50.0 cm aliquot of water sample into an Erlenmeyer flask and add 3 drops
of methyl orange solution.
c) If the sample is orange prior to addition of the acid the total alkalinity is zero. If the
solution is yellow titrate it with the standard acid solution until the first noticeable
colour change towards orange is observed. Record the volume of the titrant used.
2.7 Fill in the Table 2.3.

Table 2.3
Titration No
Volume of the standard HCl
solution
Accepted volume, cm3 ______
2.8 Calculate the total alkalinity (in mg dm–3 CaCO3). Write down the result in Table 2.4
(see question 2.11).
TH
2.9 Temperature measurement

Read the thermometer located at the table of common use and write down the value
into Table 2.4 (see question 2.11).
2.10 TDS determination in the water sample with the test strip.
a) Fill a beaker with the water sample to a level of about 3 cm of height. Immerse the
strip into water; be sure that the yellow band on the top of the strip does not touch the
liquid.
b) Wait for 3 - 4 minutes until the yellow band turns completely brown. Take the reading
as shown in the picture hereunder. Give it to one decimal digit.
c) Report the reading.
d) Find your TDS concentration as that of NaCl in mg dm–3 in the table to the right of the
picture.
e) Write down the concentration of NaCl in Table 2.4 (see question 2.11).
NaCl
Reading conc.,
mg dm–3
1.4 360
1.6 370
1.8 420
2.0 430
2.2 470
2.4 530
2.6 590
2.8 660
3.0 730
3.2 800
3.4 880
3.6 960
3.8 1050
4.0 1140
4.2 1240
4.4 1340
4.6 1450
4.8 1570
5.0 1700
TH
2.11 Fill in all the blank boxes in the Table 2.4. Calculate LI and write down the result in
Table 2.4. Take the values of the factors to the accuracy of two decimal digits.
Table 2.4. Calculation of LI of the water sample
Water sample Number ______
CH, TA, TDS,

–3 –3 –3
mg dm mg dm t, °C pH mg dm
CaCO3 CaCO3 NaCl LI
FD FA FT FTDS
Theoretical questions. Water balance correction.

If LI significantly deviates from zero, it is needed to be adjusted to zero.
Imagine you are given a sample of pool water analyzed as you have done above.
–3 –3
The results of the analysis are as follows: CH = 550 mg dm , FD = 2.31, TA = 180 mg dm ,
FA = 2.26, t = 24 ˚C, FT = 0.6; TDS = 1000 mg dm–3, FTDS = 12.1, pH = 7.9, LI = 0.97.
The pool serviceman added 10 cm3 of 0.0100 mol dm–3 solutions of reagents (NaHCO3,
NaOH, NaHSO4, CaCl2, EDTA (disodium salt dihydrate) and HCl) to 200 cm3 of different
pool water samples (one reagent for one sample).
2.12 Decide whether CaSO4 is deposited upon addition of NaHSO4.
Yes No
Tick one box and confirm your choice with calculation.
Note: CaSO4 solubility product is 5·10–5. Assume that no precipitate of CaCO3 is
formed upon addition of any of the above reagents.
2.13 Fill in the hereunder table 2.5 by showing the trends of changes resulting from
addition of each reagent to this particular water sample (use “+” if the factor
increases, “–“ if it decreases, and “0” if it does not change).
TH
Table 2.5
Reagent pH FA FD FTDS LI
NaHCO3
NaOH
NaHSO4
CaCl2
Na2H2Y
HCl
_______________
TH
SOLUTION
2– 2+ 2- +
2.1 H2Y + Ca = CaY + 2 H
Reactions with other forms of EDTA are also acceptable.
2.5 We observe pH ~8 ⇒ this is carbonic acid - hydrogen carbonate buffer, then:

[HCO3– ] K
= +1 = 45
[H2CO3 ] [H ]
i.e. ~ 98 % of hydrogen carbonate
2.6 HCO3– + H+ = H2CO3 (or H2O + CO2)
VEDTA × cEDTA 200 2.2 × 0.05

2.12 [Ca2+ ] = = = 0.00524 mol dm–3
20 200 + 10 20 × 200
210
0.01 × 10
When NaHSO4 is added, [SO42–] = = 0.000476 mol dm–3
(200 +10)
Then [Ca ] [SO4 ] = 0.00524 × 0.000476 = 2.5 · 10

2+ 2– –6
< Ksp
⇒ no precipitate of CaSO4 is formed.
Your answer (tick one) Yes □ No

2.13
NaHCO3 + + 0 + +
NaOH + + 0 + +
NaHSO4 – – 0 + –
CaCl2 0 0 + + +
Na2H2Y – – – + –
HCl – – 0 0 –
GBR-1
INTERNATIONAL CHEMISTRY OLYMPIAD / SLOVAKIA & CZECH REPUBLIC, 2018
Chemicals
For all problems
Chemicals Labelled as GHS hazard statements1
Deionised water in:
Wash bottle (bench)
Water Not hazardous
Plastic bottle (bench)
Plastic canister (hood)
For Problem P1 (in white basket if not stated otherwise)

Ethanol, 100 cm3 in wash bottle (bench) Ethanol H225, H319
2-Acetonaphthone:
Standard A H302, H315, H319, H335,
approx. 0.002 g in glass vial, standard for TLC
H411
0.500 g in glass vial Reactant A
2,4-Dinitrophenylhydrazine, containing 33% (w/w) of
DNPH H228, H302
water, 0.300 g in glass vial
Bleach solution, containing 4.7% of NaClO, 13.5 cm3 in
Bleach H290, H314, H400
amber glass bottle
Ethyl acetate, 15 cm3 in amber glass bottle EtOAc H225, H319, H336
Eluent for thin layer chromatography, hexanes/ethyl H225, H304, H315, H336,
TLC eluent
acetate 4:1 (v/v), 5 cm3 in amber glass bottle H4112
5% Na2CO3, aqueous solution, 20 cm3 in plastic bottle 5% Na2CO3 H319
H290, H314, H319, H335
20% HCl, aqueous solution, 15 cm3 in plastic bottle 20% HCl
and others
For Problem P2 (in green basket)

8 mmol dm−3 luminol in 0.4 mol dm−3 NaOH aqueous Luminol
H290, H315, H319
solution, 50 cm3 in plastic bottle in NaOH
2.00 mmol dm−3 CuSO4 aqueous solution, 25 cm3 in
Cu Not hazardous
plastic bottle
2.00 mol dm−3 H2O2 aqueous solution, 12 cm3 in small
H2O2 conc. H302, H315, H318
plastic bottle
0.100 mol dm−3 cysteine hydrochloride aqueous
Cys conc. Not hazardous
solution, 12 cm3 in small plastic bottle
Water, 50 cm3 in plastic bottle Water Not hazardous
1 See page 3 for the definition of the GHS hazard statements.

2 The GHS hazard statements for hexanes.
PRACTICAL PROBLEMS, THE QUEEN’S ENGLISH VERSION 4

GBR-1
For Problem P3 (in grey basket if not stated otherwise)

Sample of mineral water, 400 cm3 in plastic bottle
Sample Not hazardous
(bench)
3 mol dm−3 NH4Cl / 3 mol dm−3 NH3 solution in water,
Buffer H302, H319, H314, H400
15 cm3 in plastic bottle
NaCl, solid, 10 g in plastic bottle NaCl H319
Eriochrome black T, indicator mixture in plastic bottle EBT H319
Bromothymol blue, indicator solution in plastic bottle BTB H302, H315, H319
5.965 × 10−3 mol dm−3 disodium ethylenediamine
tetraacetate standard solution, 200 cm3 in plastic bottle EDTA H302, H315, H319, H335
(bench)
0.2660 mol dm−3 NaOH standard solution, 250 cm3 in
NaOH H314
plastic bottle (bench)
Strong acidic cation exchange resin, in H+ form, 50 cm3
of swollen material washed with deionised water in plastic Catex H319
bottle
Equipment
For all problems (on shelf if not stated otherwise)
Shared equipment Quantity
Paper wipes 1 box for 2–4
Waste paper basket (bench, close to sink) 1 for 4
Nitrile gloves (hood) 1 box for lab
Personal equipment
Safety goggles 1
Pipette stand (bench) 1
Bulb pipette filler 1
Glass beaker, 100 cm3,
containing: glass rod, plastic spoon,
1 (each)
spatula, tweezers, marker, pencil, ruler

UV lamp (hood) 1 for up to 12
Vacuum source (plastic stopcock with vacuum hose, bench) 1 for 2
Personal equipment
Hotplate stirrer (bench) with:
Temperature probe, 1 (each)
Crystallising dish, with metallic paperclip

GBR-1
Laboratory stand (bench) with:

Clamp holder with small clamp 1 (each)
Clamp holder with large clamp
Organic waste plastic bottle (bench) 1
Open metal ring 1
Round bottom flask, 50 cm3, with magnetic stir bar 1
Measuring cylinder, 10 cm3 1
Reflux condenser 1
Separating funnel, 100 cm3, with stopper 1
Conical flask without ground joint, 50 cm3 1
Conical flask with ground joint, 50 cm3 1
Glass funnel 1
Suction flask, 100 cm3 1
Rubber adapter for filter funnel 1
Fritted (sintered) glass filter funnel, porosity S2 (white label) 1
Fritted (sintered) glass filter funnel, porosity S3 (orange-red
1
label)
Glass beaker, 50 cm3, with Petri dish lid 1
Glass beaker, 150 cm3 1
TLC graduated capillary spotter, 5 l 3
Zipped bag with 5 pH indicator strips and 1 pH scale 1
Zipped bag with 2 TLC plates 1
Glass Pasteur pipette 4
Rubber bulb 1
Glass vial labelled Student code B for the product of the
1
haloform reaction
Glass vial labelled Student code C for the product of the
1
reaction with Brady’s reagent
For Problem P2 (in green basket if not stated otherwise)

Personal equipment Quantity
Stopwatch 1
Digital thermometer and card with its calibration constant 1
Volumetric flask, 50 cm3 1
Bulb pipette, 5 cm3 (bench, in pipette stand) 1
Graduated pipette, 5 cm3 (bench, in pipette stand) 3
Plastic bottle labelled H2O2 dil. for diluted stock solution of
1
H2O2, 50 cm3
Plastic bottle labelled Cys dil. for diluted stock solution
1
cysteine.HCl, 50 cm3
Black plastic test tube, 15 cm3 1

GBR-1
Capless centrifuge tube, 1.5 cm3 1

Plastic beaker, 25 cm3 1
Conical flask, 100 cm3 1

White sheet of paper
1 (each)
Burette clamp
Burette, 25 cm3
Glass funnel 1
Titration flask (kind-of-round, flat bottomed flask), 250 cm3 2
Fritted (sintered) glass filter funnel, porosity S1 (blue label) 1
Plastic Pasteur pipette, narrow stem, nongraduated 2
Plastic Pasteur pipette, thick stem, graduated 1
Zipped bag with 5 absorbing paper strips 1
Waste catex plastic bottle (bench) 1

GBR-1
Question 3.1 3.2 3.3 3.4 3.5

Points 3 20 2 2 16
Practical Score
Problem 3
13% of the total Question 3.6 3.7 3.8 3.9 3.10 Total
Points 4 20 2 4 2 75
Score
Problem P3. Mineral water identification

Many mineral and thermal water springs are registered in Slovakia. Mineral waters with a balanced
composition and natural or modified carbon dioxide content are sold for daily consumption. These
waters do not contain nitrites, nitrates, phosphates, fluorides and sulfides and are also free of iron
and manganese.
The mass concentration of the most important ions is reported on the packaging.
Your task is to identify the trade brand (from Table P3.1) of your mineral water sample.
Note: CO2 has been removed from the sample.
Table P3.1. Mass concentrations of ions in selected Slovak mineral waters. (As reported by the supplier.)
Mass concentration of ion, mg dm−3
No. Trade brand
Ca2+ Mg2+ Na+ K+ Cl− SO42− HCO3−
1 Kláštorná 290 74 71 16 15 89 1 341
2 Budišská 200 50 445 50 25 433 1 535
3 Baldovská 378 94 90 0 78 215 1 557
4 Santovka 215 67 380 45 177 250 1 462
5 Slatina 100 45 166 40 104 168 653
6 Fatra 45 48 550 16 36 111 1 693
7 Ľubovnianka 152 173 174 5 10 20 1 739
8 Gemerka 376 115 85 0 30 257 1 532
9 Salvator 473 161 214 30 116 124 2 585
10 Brusnianka 305 101 187 35 59 774 884
11 Maxia 436 136 107 18 37 379 1 715

GBR-1
Notes:
 Use the prescribed symbols in the notations of calculations.
 You are provided with a swollen cation exchange resin (Catex) in its H+ form. Use a thick stem
Pasteur pipette for transferring it. You can add more deionised water to the resin if necessary (it
should not dry out).
 Concentrations of the standard solutions:
c(NaOH) = 0.2660 mol dm−3 c(EDTA) = 5.965 × 10−3 mol dm−3
Procedure
1.a Measure 5.00 cm3 of the catex into the graduated cylinder (volume
V1). Then using deionised water transfer the catex quantitatively into
a titration (kind-of-round, flat bottomed) flask. Add an appropriate
amount of deionised water so that the suspension can be swirled well
and the colour of the solution over the catex can be observed.
1.b Add 3–4 drops of the bromothymol blue indicator (BTB) and about
1 g (half a spoon) of solid NaCl. When NaCl dissolves, titrate all the
suspension with the standard sodium hydroxide solution (volume V2)
from yellow to blue. Close to the equivalence point, titrate slowly and ← Catex level (5.00 cm3)
swirl well so that any analyte inside the catex skeleton may diffuse
into the solution. Repeat the experiment as necessary.
1.c After the titration, decant and discard most of the aqueous solution
in the titration flask above the catex and transfer the suspension to the Waste catex container.
P3.1 Write down all the chemical reactions which occur in Step 1. Use R–H as a formula for the
catex in a H+ form and HInd for the indicator.

GBR-1
P3.2 Enter the experimental and accepted values from Step 1 into the table.
(You do not need to fill in all the rows.)

Analysis Catex volume NaOH consumption
No. V1 [cm3] V2 [cm3]
2 5.00
Accepted value V2
4 significant figures
P3.3 Using the accepted value of V2, calculate the ion exchange volume capacity Qv(H+) in
mmol cm−3.
Calculation:
If you cannot find the Qv(H+) value, use 1.40 mmol cm−3 for further calculations.
2.a Using a graduated cylinder, measure 5.00 cm3 of the swollen catex (volume V3). Transfer the
measured catex quantitatively into the 250 cm3 beaker. Using a pipette, add 50.00 cm3 of your
sample (volume V4). Swirl the mixture occasionally for about 5 minutes. Use the conical flask as
a stand for the funnel and to collect the filtrate. Then filter the catex through a fritted (sintered)
funnel (porosity S1) and wash it with deionised water to a neutral pH (check with pH paper).
Discard the filtrate.
2.b Using deionised water, transfer the catex quantitatively from the funnel into a titration flask.
2.c Add 3–4 drops of bromothymol blue indicator and about 1 g (half a spoon) of solid NaCl and
titrate the suspension with the standard sodium hydroxide solution (volume V5) from yellow to
blue. Repeat the experiment as necessary.
2.d After the titration, decant and discard most of the aqueous solution in the titration flask above
the catex and transfer the suspension to the Waste catex container.

GBR-1
P3.4 Write down the equations for the ion exchange reactions. Monovalent and divalent ions should
be abbreviated M+ and M2+, respectively.
Catex NaOH
Analysis Sample volume
volume consumption
No. V4 [cm3]
V3 [cm3] V5 [cm3]
2 5.00 50.00
Accepted value V5
P3.6 Assuming that all the ions in your solution are M+ ions, calculate, for the accepted value of V5,
the molar concentration of cations (as M+ molar concentration) in mineral water, c*(M+), in
mmol dm−3.
Calculation:
If you cannot find the c*(M+) value, use 35.00 mmol dm−3 for further procedure.

GBR-1
In the next step, you are going to perform complexometric analysis to determine the concentration
of Ca2+ and Mg2+ together (hereinafter written as M2+).
3. Pipette 10.00 cm3 (V6) of the sample into the titration flask and add approx. 25 cm3 of deionised
water. Adjust pH by adding 3 cm3 of the buffer solution. Add some Eriochrome black T indicator
(EBT, on the tip of the spatula) and titrate with the standard EDTA solution from wine red to blue
(V7).
(You do not need to fill in all the rows)

Analysis Sample volume EDTA consumption,
3
No. V6 [cm ] V7 [cm3]
2 10.00
Accepted value V7
P3.8 For the accepted volume of V7, calculate the molar concentration of M2+ cations in mineral
water, c(M2+) in mmol dm−3.
Calculation:
If you cannot find the c(M2+) value, use 15.00 mmol dm−3 for further solution.
4. Use Table P3.2 in the next identification procedure.
P3.9 In Table P3.2, write down experimentally found values from tasks P3.6 and P3.8 and tick ()
all the lines with an approximate match (±10%) of the found parameter c(M2+) and c*(M+) with
the data from the table.

GBR-1
Table P3.2
Mineral water Supplier data Match with the experiment
Total
equivalent
c(M2+) c(M+)
concentration Conformity Conformity
No. Trade brand −3 −3
[mmol dm ] [mmol dm ] of cations for c(M2+) for c*(M+)
c*(M+)
[mmol dm−3]
Your exp. values XXX XXX XXX
1 Kláštorná 10.30 3.50 24.1
2 Budišská 7.06 20.63 34.7
3 Baldovská 13.32 3.91 30.5
4 Santovka 8.13 17.67 33.9
5 Slatina 4.35 8.25 16.9
6 Fatra 3.11 24.32 30.5
7 Ľubovnianka 10.92 7.70 29.5
8 Gemerka 14.13 3.70 32.0
9 Salvator 18.46 10.07 47.0
10 Brusnianka 11.79 9.03 32.6
11 Maxia 16.50 5.11 38.1
P3.10 Based on your results, decide which mineral water is in your sample. Tick () the cross-
reference number(s) of the mineral water(s).
No. Trade brand No. Trade brand
1 Kláštorná 7 Ľubovnianka
2 Budišská 8 Gemerka
3 Baldovská 9 Salvator
4 Santovka 10 Brusnianka
5 Slatina 11 Maxia
6 Fatra 12 other

XXX-X
Question 3.1 3.2 3.3 3.4 3.5

Points 3 20 2 2 16
Practical Score
Problem 3
Points 4 20 2 4 2 75
Score

and manganese.
No. Trade brand
1 Kláštorná 290 74 71 16 15 89 1 341
2 Budišská 200 50 445 50 25 433 1 535
3 Baldovská 378 94 90 0 78 215 1 557
4 Santovka 215 67 380 45 177 250 1 462
5 Slatina 100 45 166 40 104 168 653
6 Fatra 45 48 550 16 36 111 1 693
7 Ľubovnianka 152 173 174 5 10 20 1 739
8 Gemerka 376 115 85 0 30 257 1 532
9 Salvator 473 161 214 30 116 124 2 585
10 Brusnianka 305 101 187 35 59 774 884
11 Maxia 436 136 107 18 37 379 1 715
PRACTICAL PROBLEMS, OFFICIAL ENGLISH VERSION 22

XXX-X
Notes:
• Use the prescribed symbols in the notations of calculations.
• You are provided with a swollen cation exchange resin (Catex) in its H+ form. Use a thick stem
Pasteur pipette for transferring it. You can add more deionized water to the resin if necessary (it
• Concentrations of the standard solutions:
Procedure
V1). Then using deionized water transfer the catex quantitatively into
a titration flask. Add an appropriate amount of deionized water so that
the suspension can be swirled well and the colour of the solution over
the catex can be observed.
Ion exchange
R–H + NaCl ⇆ R–Na + HCl
1 point for the correct equation
Neutralization
HCl + NaOH ⇆ NaCl + H2 O
Indication
HInd + OH– ⇆ Ind– + H2 O

XXX-X

No. V1 [cm3] V2 [cm3]
1 e.g. 19.00
2 5.00 e.g. 19.50
3 e.g. 19.70
Accepted value V2
e.g. 19.40
Maximum 20 points based on the agreement between the master and accepted values V2 (specified in Marking
notes; the number of replications is not evaluated).
mmol cm−3.
Calculation:
+ V2 × c(NaOH) 19.40 cm3 × 0.2660 mol dm–3

Qv (H ) = = = 1.032 mmol cm–3
V1 5.0 cm3
1 point for the correct calculation procedure
1 point for correct result
sample (volume V4). Swirl the mixture occasionally for about 5 minutes. Use the Erlenmeyer flask
as a stand for the funnel and to collect the filtrate. Then filter the catex through a fritted funnel
(porosity S1) and wash it with deionized water to a neutral pH (check with pH paper). Discard the
filtrate.
2.b Using deionized water, transfer the catex quantitatively from the funnel into a titration flask and
discard the filtrate.

XXX-X
Ion exchange from the sample
R–H + M+ ⇆ R–M + H+
2 R–H + M2+ ⇆ R2 –M + 2 H+
2 points – 1 point for each correct equation or 2 points for the correct general equation with Mn+
Catex NaOH
volume consumption
No. V4 [cm3]
V3 [cm3] V5 [cm3]
1 e.g. 13.00
2 5.00 50.00 e.g. 13.20
3 e.g. 13.10
Accepted value V5
e.g. 13.10
P3.6 Consider that all the ions in your solution are M+ ions. For the accepted value of V5, calculate
the total amount of cations (as M+ molar concentration) in 1 dm3 of mineral water. Show the
calculation of the total equivalent concentration of cations, c*(M+) in mmol dm−3.
Calculation:
* + V3 × Qv (H+ )ionex – V5 × c(NaOH)

c (M ) =
V4
5.00 cm3 × 1.032 mol dm–3 – 13.10 cm3 × 0.2660 mol dm–3
c* (M+ ) =
50.00 cm3
c* (M+ ) = 33.51 mmol dm–3
3 points for the correct calculation procedure
1 point for correct result including unit

XXX-X
3. Pipette 10.00 cm3 (V6) of the sample into the titration flask and add ca. 25 cm3 of deionized water.
Adjust pH by adding 3 cm3 of the buffer solution. Add some Eriochrome black T indicator (EBT,
on the tip of the spatula) and titrate with the standard EDTA solution from wine red to blue (V7).
No. V6 [cm3] V7 [cm3]
1 e.g. 14.20
2 10.00 e.g. 14.25
3 e.g. 14.25
Accepted value V7
e.g. 14.25
Calculation:
V7 × c(EDTA)
c(M2+ ) =
V6
14.25 cm3 × 5.965 mmol dm–3
c(M2+ ) = = 8.500 mmol dm–3
10.00 cm3

4. Use Table P3.2 in next identification procedure.
P3.9 In Table P3.2, write down experimentally found values from tasks P3.6 and P3.8 and tick (✓)
all the lines with approximate match (±10%) of the found parameter c(M2+) and c*(M+) with the
data from the label.

XXX-X
Table P3.2
Total
equivalent
c(M2+) c(M+)
c*(M+)
[mmol dm−3]
Your exp. values 8.50 XXX 33.51 XXX XXX
1 Kláštorná 10.30 3.50 24.1
2 Budišská 7.06 20.63 34.7 ✓
3 Baldovská 13.32 3.91 30.5 ✓
4 Santovka 8.13 17.67 33.9 ✓ ✓
5 Slatina 4.35 8.25 16.9
6 Fatra 3.11 24.32 30.5 ✓
7 Ľubovnianka 10.92 7.70 29.5
8 Gemerka 14.13 3.70 32.0 ✓
9 Salvator 18.46 10.07 47.0
10 Brusnianka 11.79 9.03 32.6 ✓
11 Maxia 16.50 5.11 38.1
Maximum 4 points. For each column: 2 points if correctly marked, 1 point if partially marked.
P3.10 Based on your results, decide which mineral water is in your sample. Tick (✓) the cross-
4 ✓ Santovka 10 Brusnianka
5 Slatina 11 Maxia
6 Fatra 12 other
2 points if consistent with the results marked in Table 3.2 (Kláštorná or Ľubovnianka, if values from P3.6 and
P3.8 are accurate)

XXX-X
Marking notes
P3.2 Full points if relative deviation is lower than ±1.5% of the master value.
Acquired points are calculated from the following equation:
Score = 32.0 – 8.0 × |(V2student – V2master) / V2master| × 100,
0 points if relative deviation is higher than ±4.0% of the master value.
V2master = 13.10, 17.20, or 20.65 cm3
V5master = from 7.54 to 16.12 cm3
V7master = 17.15 or 18.41 cm3
Replaced chemicals and equipment

Signature
Item or incident Penalty
Student Lab assistant
0 pt

Titolazione
complessometrica
TH
Determination of the solubility product of lead(II) chloride
Shake solid lead(II) chloride:
a) with water,
b) with three solutions of sodium chloride of different concentrations,
until equilibrium is attained. Then determine the lead ion concentration by titration with
EDTA. Calculate the solubility product of lead(II) chloride.
Equipment and chemicals

Volumetric flask (100 cm3), pipettes (20 cm3 and 10 cm3), graduated cylinder (100 cm3 and
25 cm3), 4 Erlenmeyer flasks (200 – 250 cm3) with stoppers, spatula, 4 filter funnels, filter
papers, thermometer, 4 Erlenmeyer flasks (100 cm3), titrating flasks (200 – 250 cm3),
beakers, stand with burette (50 cm3), burette funnel, wash bottle with distilled water, glass
rod.
Standard solutions of sodium chloride (0.1000 mol dm-3) and EDTA (0.01000
mol dm-3), solid lead(II) chloride, xylenol orange solution in a dropping bottle (0.5 % in
-3
water), solid hexamine (urotropine), nitric acid (2.5 mol dm ) in a dropping bottle.
Procedure
1. Prepare 100 cm3 of sodium chloride solutions with concentrations of 0.0600 mol dm-3,
0.0400 mol dm-3, and 0.0200 mol dm-3, respectively. Place the solutions in Erlenmeyer
flasks with stoppers. Place 100 cm3 of water in the fourth flask with a stopper. Add 5
spatulas of solid lead(II) chloride (about 2 g) to each, stopper the flasks and shake
vigorously. Let the flasks stand for 30 minutes. Shake them occasionally. Prepare for
filtration and titration in the meanwhile.
2. Measure the temperatures of the lead(II) chloride solutions and report them in the table
of results. Filter the solutions through dry filters into small, dry Erlenmeyer flasks.
3. Using a pipette, transfer 10.00 cm3 of the filtrate into a titration flask. Dilute with
approximately 25 cm3 of water, add 3 drops of xylenol orange (indicator) and 5 drops of
nitric acid. Then add 5 spatulas (about 0.5 g) of solid hexamine (a weak base) and swirl
gently until the solution is clear. Titrate with EDTA.
TH
4. Calculate the concentration of lead ions and that of chloride ions in the solutions and
give the solubility product Ks. Report the results in the table.
5. Answer the questions in the answer sheet.
Questions
3.1 Give the structure of EDTA. Mark those atoms which can coordinate to a metal ion with
an asterisk (*).
3.2 Give the equation for the filtration reaction. EDTA may be written as H2X2-.
____________________
SOLUTION
A typical result:
c(NaCl) Temperature Volume EDTA [Pb2+] [Cl– ] Ks
(mol dm-3) (°C) solution (cm3) (mol dm-3) (mol dm-3)
0.0600 21 18.7 0.0187 0.0974 1.77 × 10-4
0.0400 21 22.7 0.0227 0.0854 1.66 × 10-4
0.0200 21 27.8 0.0278 0.0756 1.59 × 10-4
- 21 34.2 0.0342 0.0684 1.60 × 10-4
Answers to the questions:
3.1 *
HOOC - CH2 *
CH2 - COOH
* *
N - CH2 - CH2 - N
CH2 - COOH
HOOC - CH2
* *
3.2 H2Y2- + Pb2+ → PbY2– + 2 H+
TH
duplicate.
A) Sample solution:
B) Blank solution:
250 ml.
Note:
stopper.
1.6 M.

TH

persist.
Questions:
TH
THE 24 INTERNATIONAL CHEMISTRY OLYMPIAD, Pittsburgh, 1992
PRACTICAL PROBLEMS
Effects of CO2 on Solubility
Calcium carbonate is a partially soluble material commonly known as limestone,
marble, chalk, or calcite. In the presence of CO2-rich groundwater, calcium carbonate
dissolves to form cavities and caves in limestone formations.
In this experiment you will determine the solubility of calcium carbonate in an
aqueuos solution saturated with carbon dioxide and in solution free of carbon dioxide. The
[Ca2+] will be determined by complexometric titration with EDTA (ethylenediamine-
tetraacetic acid).
a) Procedure for the determination of [Ca2+]

1. Calibrate your pH meter.
2. Measure and record the pH of the sample equilibrated with solid CaCO3 and CO2
gas.
3. Filter all your sample into a second 250 cm3 plastic bottle to remove any suspended
CaCO3. Quickly cap the bottle when the filtering is complete.
4. Uncap the bottle long enough to measure and record the pH of the filtered solution
and recap the bottle until you are ready for the next step.
5. As rapidly as possible, transfer three 25 cm3 aliquots of this sample to three
Erlenmeyer flasks. Recap the sample bottle after removing each 25 cm3 aliquot.
6. Add 15 drops of 6 M HCl to each of the three flasks with stirring. Any CaCO3 that
may have formed should dissolve. Before proceeding with the next step, make sure
there is no solid CaCO3 in the Erlenmeyer flasks. If a flask has some solid present,
then more stirring is necessary.
7. To one, and only one flask, add 5 cm3 of a pH 10 NH3 buffer. Proceed immediately
with steps 8 - 10.
8. Add 20 drops of 0.001 M Mg2+/EDTA4- solution to the flask in order for the indicator to
function properly.
9. Add 5 drops of Calmagite indicator to the sample.
TH
10. Titrate the sample with an approximately 0.01 M EDTA solution provided (to be
standardized as directed below) to a colour change from red to blue. You may wish
to make a reference for colour with water, buffer, two drops EDTA and indicator.
11. Quickly repeat steps 7 - 10 for each remaining flask, one at a time.
12. After steps 1 - 11 have been completed to your satisfaction, transfer the remaining
filtered, saturated solution from step 3 to a suitable beaker. Heat this solution to 96 –
o
99 C and allow it to remain at that temperature, with magnetic stirring, for 5 minutes.
A stirrer setting on 6 is adequate, and an initial high setting of heat will be required.
You should see CO2 being evolved and some CaCO3 may precipitate.
13. At the end of the five minutes heating period, use the beaker tongs to remove the
beaker from the hot plate and place it in an ice bath. Allow the solution to cool to
room temperature.
14. Measure and record the pH of the cooled solution.
15. Filter the solution to remove any suspended CaCO3.
3
16. Transfer three 25 cm aliquots of this filtered solution to three Erlenmeyer flasks. Add
about 25 cm3 of deionized water to each flask, followed by 15 drops of 6 M HCl.
17. Titrate each sample according to steps 7 - 11.
b) Procedure for standardization of EDTA

1. Weigh approximately 0.35 g of dried primary standard CaCO3, (molar mass 100.09
-1
g mol ) which will be found in the weighing bottle in the desiccator. Note: CaCO3 is
hygroscopic.
3 3
2. Add 25 cm of deionized water to the CaCO3, then carefully add 5 cm of 6 M HCl.
Quickly cover with a watch glass.
3. When the CaCO3 has dissolved, quantitatively transfer the solution to a 250 cm3
volumetric flask and dilute to the mark.
4. Transfer three 25 cm3 aliquots of the standard Ca2+ solution to three Erlenmeyer
flasks.
5. Proceed to titrate each sample according to steps 7 - 11, following each step in
sequence.
TH
Tasks:
-3
1.1 Calculate the solubility of calcium carbonate (expressed in mol dm ) in a solution
saturated with both CaCO3 and CO2 and in solution free of CO2.
1.2 List all the ionic species that increase in concentration as a result of the dissolving of
CaCO3 in water.
1.3 Given below are brief descriptions of two solutions. Circle the one in which the
concentration of CO32- would be highest:
a) a solution produced by dissolving CaCO3(s) in CO2 -saturated water
b) a solution produced by dissolving CaCO3(s) in CO2 -free water
1.4 Will the solubility of CaCO3 increase or decrease in a solution from which the CO2
has been removed?
_______________
SOLUTION
1.1 The results of the titration (volumes of titrants, mass of CaCO3) and calculation of the
concentration of the standardized EDTA solution were required to be written on the
Answer Sheet.
Moreover, it was necessary to measure and record pH values of the sample at steps
2, 4, and 14.
It was expected to show the calculation of the solubility of CaCO3 in its saturated
solutions containing CO2 and in those without CO2.
The other tasks to be solved:

1.2 The ionic species mentioned above are as follows: Ca2+, HCO3- , OH-.
1.3 Correct answer: (b) A solution produced by dissolving CaCO3(s) in CO2-free water.
1.4 The solubility of CaCO3 will decrease.
TH
PRACTICAL PROBLEMS
2+ 2+
Determination of Mg and Ca in Bottled Water
-9
• The Ksp for calcium oxalate is 2.3×10 and the Ksp for magnesium oxalate is
8.6×10-5.
• In a solution buffered to maintain pH 10, Calmagite indicator is pink when bound to
Mg2+ and blue in the absence of available magnesium ions. Calcium ions are not
bound by Calmagite.
• EDTA binds to Mg2+ and Ca2+ even in the presence of Calmagite. The stoichiometry
of the EDTA-metal complex formed with both Mg2+ and Ca2+ is 1:1.
• Molar masses: M(Ca) = 40.08 g mol-1 M(Mg) = 24.31 g mol-1
Chemicals Available
3
500 cm sample of “Bottled Water”
aqueous buffer (pH 10)
Calmagite indicator
aqueous saturated ammonium oxalate
aqueous ethylenediaminetetraacetic acid
aqueous standardized* Mg2+
distilled water
*0.928 mg Mg2+/cm3 solution, 0.0382 moles Mg2+/dm3
Procedure
A. Precipitation of calcium ions
Precipitate the calcium ions in a 25.00 cm3 aliquot of the “Bottled Water” sample by
accurately adding approximately 0.50 cm3 of saturated ammonium oxalate solution (from
the common burettes in each lab room). Carefully swirl the solution to ensure uniform
mixing. Allow at least 45 minutes for complete precipitation to occur.
TH
B. Standardization of the EDTA solution

3
Using distilled water, dilute 5.00 cm of the standardized magnesium solution to a
3 3 3
final volume of 100.0 cm . Add 40 cm of distilled water, 5 cm of pH 10 buffer solution,
3
and some Calmagite indicator to 5.00 cm of diluted magnesium solution. Titrate this
sample with EDTA solution to a clear blue end point.
Repeat as necessary.
2+ 2+
C. Titration of Mg and Ca
Add 40 cm3 of distilled water, 5 cm3 of pH 10 buffer solution, and some Calmagite
indicator to 5.00 cm3 of the “Bottled Water” sample. Titrate this sample with EDTA solution
to a clear blue end point.
D. Titration of Mg2+
Add 40 cm3 of distilled water, 5 cm3 of pH 10 buffer solution, and some Calmagite
indicator to 5.00 cm3 of the calcium-free “Bottled Water” sample prepared in part A. The
presence of a small amount of calcium oxalate will not interfere with your titration. Titrate
this sample with EDTA solution to a clear blue end point.
Calculations
Calculate the concentration of Mg2+ (in mg dm-3) in the “Bottled Water” sample.
Calculate the concentration of Ca2+ (in mg dm-3) in the “Bottled Water” sample.
RD
THE 33 INTERNATIONAL CHEMISTRY OLYMPIAD, Mumbai, 2001
Estimation of Mn(II) and Mg(II) Present in the Given Sample
In this experiment, estimation of the amounts of Mn (II) and Mg (II) present in the
given sample is carried out by complexometric titration using standard Na2EDTA solution.
Total metal ion content is obtained from the first titration. At this stage, by using adequate
solid NaF, selective and quantitative release of EDTA present in Mg-EDTA complex is
achieved. The EDTA thus released is bound again by the addition of a known excess of
standard Mn (II) solution. The unused Mn (II) is estimated by a back titration using the
same standard Na2EDTA solution. From these two different titre values, individual
amounts of metal ions present can be obtained. Both the titrations are performed using a
buffer (pH = 10) and Erichrome black T indicator.
The sample in duplicate is given in two 250 cm3 conical flasks (labelled as Trial
I and Trial II). Perform the titrations for both and record your readings on the answer
sheet.
Procedure
Two burettes (25 cm3) are supplied to you. Fill one with the given standard Na2EDTA
solution and the other with the given standard Mn (II) solution.
Titration 1
To the sample solution (supplied in the 250 cm3 conical flask), add all of the solid
hydroxylamine hydrochloride given in one vial followed by 50 cm3 of distilled water. With
the help of a measuring cylinder, add 10 cm3 buffer solution (pH = 10) and one metal
spatula full of the solid indicator. Shake the contents of the flask thoroughly and titrate the
solution against the standard Na2EDTA solution until the colour changes from wine red to
blue. Record your burette reading (A cm3). Ensure that you shake the contents of the flask
thoroughly throughout the titration.
Titration 2
To the same flask, add all of the solid NaF given in one vial and shake the contents
well for a minute. To this add 20 cm3 of the given standard Mn (II) solution from the other
burette. The addition of the Mn (II) solution should be done in small increments (2 – 3 cm3)
with thorough shaking. After addition of the total Mn (II) solution, shake the contents for
two to three minutes. The colour of the solution will change from blue to wine red. Titrate
RD
the excess of Mn (II) in the solution against the standard Na2EDTA solution till the colour
3
changes from wine red to blue. Record your burette reading (B cm ).
Repeat the same procedure for Trial II.
_______________
SOLUTION
The results of the titration (volumes) were required to be written on the Answer
Sheet.
2.2 Give the balanced chemical equation for the reactions of Mg(ll) and Mn(ll) with
Na2EDTA . (Use the symbol Na2HY for Na2EDTA.)
Answer: Mg2+ + H2Y2- → MgY2- + 2 H+
Mn2+ + H2Y2- → MnY2- + 2 H+
2.3 Give the equation for the release of EDTA by the addition of NaF to the MgEDTA
complex.
Answer: MgY2- + 2 F– → MgF2 + Y4-
2.4 Calculate the amount of Mg (II) and Mn (II) in gram for any one of the two trials.
(Show the main steps in your calculation.)
2.5 The colour change at the end point (wine red to blue) in Titration 1 is due to
a) the formation of metal-indicator complex,
b) the release of free indicator from metal-indicator complex,
c) the formation of metal-EDTA complex.
[Mark X in the correct box.]
Correct answer is (b).
TH
Introduction
Procedures
3
TH
precipitation.)

volumetric flask.

TH
3

3 3
3

_______________
SOLUTION
box!
Ca Sr Ba
Ca and Sr and Ba
+ CO23−
2+
Sr SrCO3
TH
2 Ba 2+ + Cr2O72− + H2O 2 BaCrO4 + 2 H

+

-3 3
3

-3 3
3
2+ -
2 Cu +4I I2 + 2 CuI
I2 + 2 S2O32−
- 2-
2 I + S4O6

-1 -1
[M(Cu) = 63.55 g mol ; M(La) = 138.91 g mol ]
Amount of copper:
10,50 cm × 0.01 mol dm × 4 × 10 × 63.55 g mol = 266.9 mg
3 -3 -1
[11.60 – (10.50 / 10 × 4)] cm × 0.1 mol dm × 10 × 138.91 g mol = 1028 mg
3 -3 -1

3 -3
superconductor
TH

n(La) : n(Cu) = 25.90 : 14.00 = 1.85 : 1
ST
THE 41 INTERNATIONAL CHEMISTRY OLYMPIAD, Cambridge, 2009
Analysis of a Copper(II) Complex

You are provided with a sample of an inorganic copper(II) complex, the anion of
which is made from copper, chlorine, and oxygen. The counter ion is the tetramethyl
ammonium cation. There is no water of crystallisation. You are required to determine
proportions of copper ions and chloride ions by titration and hence determine the
composition of the complex.
Chemicals
• Inorganic complex: three samples of approximately 0.1 g, accurately pre-weighed in
vials labelled ‘Sample 1’, ‘Sample 2’, ‘Sample 3’.
vials labelled ‘Sample 4’, ‘Sample 5’ and ‘Sample 6’.
• pH 10 ammonia buffer, 10 cm3.
• Murexide indicator, solution in H2O, 10 cm .
3
• EDTA disodium salt, aqueous solution, c = 0.0200 mol dm–3, 150 cm3.
• Ethanoic acid, 10 cm3.
• 2,7-Dichlorofluorescein indicator, solution in 7 : 3 EtOH : H2O), 10 cm .
3
• Dextrin, 2 % solution in H2O, 25 cm3.

• Silver nitrate, aqueous solution, c = 0.1000 mol dm–3, 150 cm3.
Procedure
Titration to determine the proportion of copper ions
(a) You are provided with three accurately pre-weighed samples of copper complex,
each of approximately 0.1 g. These are labelled "Sample 1", "Sample 2", "Sample 3",
together with the exact mass of the copper complex. Take the first of these, note
down the mass of the sample and quantitatively transfer the contents to a 250 cm3
conical flask using approximately 25 cm3 of water.
(b) Add pH 10 ammonia buffer solution until the precipitate which forms initially just
redissolves (about 10 drops).
(c) Add 10 drops of the murexide indicator.
ST
–3
(d) Titrate with the 0.0200 mol dm EDTA solution until the solution turns violet and the
colour persists for at least 15 seconds. Record the volume of solution used in the
titration.
(e) Repeat if necessary with samples 2 and 3.
Note: You will be marked only on a single value you report in the answer booklet. This
may either be an average value, or a single value you feel most confident in.
2.1 Calculate the volume of EDTA solution needed to react completely with 0.100 g of
complex.
2.2 Give an equation for the titration reaction.
2.3 Calculate the percentage by mass of copper in the sample.
You will need to wash out your burette before you start the titration for the
determination of chloride ions. Any remaining EDTA solution may be disposed of into the
waste containers labelled ‘EDTA’.
Titration to determine the proportion of chloride ions present

(f) You are provided with three accurately pre-weighed samples of copper complex
(g) Add 5 drops of ethanoic acid, followed by 10 drops of dichlorofluorescein indicator
and 5 cm3 dextrin (2 % suspension in water). Shake the bottle well before adding the
dextrin suspension.
(h) Titrate with the 0.1000 mol dm–3 silver nitrate solution, swirling constantly until the
white suspension turns pink and the colour does not disappear after swirling.
(i) Repeat if necessary.
may either be an average value, or the value you feel most confident in.
2.4 Calculate the volume of silver nitrate solution needed to react completely with
0.200 g of complex.
ST

2.6 Calculate the percentage by mass of chloride ions in the sample.
The percentage of carbon, hydrogen and nitrogen in the complex was determined by
combustion analysis and found to be as follows:
Carbon: 20.87 %; Hydrogen: 5.17 %; Nitrogen: 5.96 %.
2.7 Mark in the answer booklet, which element in the complex has the greatest
percentage error in the determination of its proportion.
Cu Cl O C H N
2.8 Determine the formula of the copper complex. Show your working.
_______________
ST
SOLUTION
2.1 Full marks if answer is Vcorr. ± 0.1 cm3. Zero marks if answer is less than (Vcorr. – 0.5
3 3
cm ) or greater than (Vcorr. + 0.5 cm ), linear point scale is applied in between.
→ [Cu(EDTA)]
2+ 4– 2–
2.2 Cu + EDTA
× V(EDTA) (in dm ) = (0.0200 mol dm × V) mol
–3 3 –3
2.3 n(EDTA) = 0.0200 mol dm
× V) mol
2+ –3
n(Cu ) = (0.0200 mol dm
m(Cu) = M(Cu) × n(Cu) = 63.55 g mol × (0.0200 mol dm × V) mol
–1 –3
m (Cu)
% Cu = × 100
m(sample)
2.4 Full marks if answer is Vcorr. ± 0.1 cm3.
Zero marks if answer is less than (Vcorr. – 0.5 cm3) or greater than (Vcorr. + 0.5 cm3),
linear point scale is applied in between.
2.5 Ag+ + Cl– → AgCl
2.6 n(Ag+) = 0.100 mol dm–3 × V(Ag+) (in dm3) = (0.100 mol dm–3 × V) mol
n(Cl–) = (0.100 mol dm–3 × V) mol
m(Cl) = M(Cl) × n(Cl) = 35.45 g mol-1 × (0.100 mol dm–3 × V) mol
m (Cl)
% Cl = × 100
m(sample)
2.7 If the percentage of oxygen is calculated by subtracting all the others from 100, it has
all the errors from the determination of the other elements combined. In practice this
leads to a large error which affects the subsequent calculation of the formula unless
this point is appreciated.
Cu Cl O C H N
2.8 Full marks if the formula is correctly calculated from the student data and the large
error in oxygen is taken into account (either by using one of the proportions of the
other elements to determine the elemental ratios, or by a consideration of charge
balance).
ND
THE 42 INTERNATIONAL CHEMISTRY OLYMPIAD, Tokyo, 2010
Polymers in Analysis
Polymers can be used in various analyses. In this task, you are first required to
analyze a polysaccharide using a polymer-polymer interaction, which will then be utilized
to identify polymers in the second part.
I. Analysis of Polysaccharide by Colloid Titration

-
You are provided with a solution of a polysaccharide containing sulfonate (-SO3 ) and
-
carboxylate (-COO ) groups. You are asked to determine the concentrations of these two
groups by colloid titration under the basic and acidic conditions based on the differences
in the protonation behaviour of these acid groups. A back-titration technique is utilized.
When these acid groups are ionized, the polysaccharide becomes a polyanion. Upon
addition of polycation, poly(diallyldimethylammonium) (provided as its chloride salt,
PDAC), it forms a polyion complex. PDAC solution is standardized using the standard
solution of potassium poly(vinyl sulphate) (PVSK). At the endpoint of colloid titration, the
number of anionic groups becomes equal to that of cationic groups.
Chemicals
3
• Polysaccharide solution, 50 cm
• Poly(diallyldimethylammonium chloride), (PDAC), aqueous solution
Formula:
CH2 CH2
N+
H3C CH3
Cl- n
• Potassium poly(vinyl sulfate) aqueous solution, c = 0.0025 mol dm–3; (monomer unit
concentration)
Formula:
CH2 CH
O
O S O
O-K+ n
–3
• sodium hydroxide, aqueous solution, c = 0.5 mol dm
–3
• toluidine blue, C15H16N3SCl, (TB), aqueous solution, c = 1 g dm
• Solutions X-1 – X- 5 for Part II.
ICHO International Information Centre, Bratislava, Slovakia, 2014
ND
Procedure
3 3
(1) Take precisely 20 cm of the PDAC solution using a volumetric pipette into a 100 cm
conical beaker. Add 2 drops of toluidine blue (TB) into the conical beaker. Titrate the
resulting blue solution with the standard solution of PVSK (c = 0.0025 mol dm–3 -
monomer unit concentration). At the endpoint the colour turns purple. Note that the
solution becomes gradually turbid as the endpoint approaches. The endpoint is
determined when the colour remains purple for 15 – 20 seconds. Repeat if necessary.
3.1 Report the PVSK solution volume (z cm3) consumed in the standardization of PDAC.
3
Record your reading to 0.05 cm .
_____
(2) Take precisely 5 cm3 of the polysaccharide solution and 20 cm3 of the PDAC solution
using volumetric pipettes into a conical beaker. Add 0.4 cm3 of NaOH solution (c = 0.5
mol dm–3) and 2 drops of TB to the solution. Titrate the resulting blue solution with the
PVSK standard solution in a similar manner. Repeat if necessary.
(The appearance of coagulation may be different, depending on the pH of the solution.)
3.2 Report the PVSK solution volume, (x cm3) consumed in the titration under basic
conditions. Record your reading to 0.05 cm3.
3.3 Mark the acid group(s) ionized under the basic conditions on the answer sheet.
_____
(3) Repeat procedure (2) above with the addition of 0.5 cm3 of HCl solution (c = 0.5
mol dm–3 ) instead of NaOH solution (c = 0.5 mol dm–3).
3.4 Report the PVSK solution volume (y cm3) consumed in the titration under acidic
conditions. Record your reading to 0.05 cm3.
3.5 Mark the acid group(s) fully ionized under acidic conditions on the answer sheet.
3.6 Calculate the concentrations of the –SO3– (or –SO3H) groups and the –COO– (or –
COOH) groups (in mol dm–3) in the given polysaccharide solution.

_____
II. Identification of compounds
You are provided with five solutions (1 – 5) and each solution contains one of the
compounds below (all of which are used). The concentration is 0.05 mol dm-3 (for
polymers, monomer unit concentration). Your task is to identify all the compounds by
carrying out the following procedures.
ND
HOCH2CH2OCH2CH2OCH2CH2OH
(TEG)
CH3
CH2CH2O CH2 C
n
COONa n
(PEO) (PMANa)
CH2 CH CH2 CH2
N+
SO3Na n H3C CH3 n
Cl-
(PSSNa) (PDAC)
Abbreviations:
TEG = triethylene glycol;
PEO = poly(ethylene oxide);
PMANa = poly(sodium methacrylate);
PSSNa = poly(sodium 4-styrenesulfonate);
PDAC = poly(diallyldimethylammonium chloride) MW. stands for molecular weight.
Helpful comments
i) Aggregates observed in part I could be observed when mixing two polymer solutions
in an appropriate combination in which an interaction takes place between the two
polymers. They can be utilized to identify polymer samples.
ii) The volume of a solution measuring 5 mm in height from the bottom of the vial is
approximately 1 cm3. Remember that you have only 10 cm3 of each solution.
Procedures
(4) Mix similar volumes of two solutions together in a vial.
(5) If necessary, you can acidify the resulting mixture. Ten drops of hydrochloric acid
(c = 0.5 mol dm-3) from a plastic Pasteur pipette are sufficient for this purpose.
ND
3.7 Identify the compound in each solution based on the experimental results. Mark one
of the five boxes to indicate your identification of the samples.
Sample
1 TEG PEO PMANa PSSNa PDAC

_________________
ND
SOLUTION
I. Analysis of Polysaccharide by Colloid Titration
3
3.1 V = 20.06 cm ; z = 20.06
3
3.2 Sample A: V = 13.14 cm ; x = 13.14
3
Sample B: V = 12.07 cm x = 12.07
3
Sample C: V = 10.91 cm x = 10.91
3.3 Under basic conditions: The acid groups are –SO3H and –COOH.
3.4 Sample A: V = 15.26 cm3 ; y = 15.26

Sample B: V = 14.61 cm3 y = 14.61
3
Sample C: V = 13.59 cm y = 13.59
3.5 Under acidic conditions: The acid group is –SO3H.
3.6 The concentrations (in mol dm–3) of:

–SO3- (or –SO3H) groups = 0.0005 (z – y)
–COO– (or –COOH) groups = 0.0005 (y – x )
II. Identification of compounds

PMANa and PSSNa are polyanions and they interact with a polycation (PDAC)
–
to form a precipitate. Under acidic conditions the carboxylate (–COO ) groups in
PMANa undergo protonation and PMANa changes to protonated poly(metacrylic
acid) (PMA). The resulting carboxy groups (–COOH) interact with the ether oxygen
atoms in PEO through hydrogen bonding to form a precipitate. Since the protonated
PMA is no longer a polyanion, the precipitate (the complex between PMANa and
PDAC) disappears after the addition of HCl.
On the other hand, PSSNa does not exist as a protonated form even under
acidic condition.
The expected results of mutual reactions are summarized in the table below.
The signs in upper rows correspond to the reactions before addition of HCl while
those in lower rows to the reactions after addition of HCl.
ND
TEG PEO PMANa PSSNa PDAC
TEG
PEO –
–
PMANa – –
– +
PSSNa – – –
– – –
PDAC – – + +
– – – +
Note: (+) precipitation is formed; (–) no precipitation occurs (or the precipitation
disappears)
RD
THE 43 INTERNATIONAL CHEMISTRY OLYMPIAD, Ankara, 2011
PRACTICAL PROBLEMS
Analysis of Chloride Mixtures
Introduction
Composition of a solution containing only MgCl2 and NaCl can be determined by an
indirect titration method by performing a precipitation titration to determine the total
amount of chloride present, followed by a complex formation titration to determine the
amount of magnesium ions. A common precipitation titration technique used to determine
the amount of chloride ions present in a solution is the Fajans method. In this
argentometric procedure, silver nitrate is used as the titrant to precipitate the chloride ions
present in the solution. The end point is detected through the use of an adsorption
indicator, typically dichlorofluorescein, a weak organic acid. Prior to the end point, silver
chloride particles are negatively charged because of the adsorption of excess chloride ions
present in solution. The indicator anions are repelled by the negatively charged surface of
the silver chloride particles imparting a yellow-green colour to the solution. Beyond the
equivalence point, however, silver chloride particles adsorb silver ions. Thus a positively
charged layer is formed and it attracts the dichlorofluoresceinate ions displaying a pink-red
colour. Dextrin is used to stabilize the silver chloride particles against the coagulation.
On the other hand, the amount of magnesium ions present in a solution can be
determined by complexometric titration with ethylenediaminetetraacetic acid, EDTA. As a
hexadentate ligand, EDTA forms chelates with all metal ions, except alkali metal ions, in a
1 : 1 mole ratio regardless of the charge of the cation. Eriochrome Black T (EBT) is a
common indicator used for EDTA titrations. When pH > 7.00 EBT imparts a blue colour to
the solution in the absence of metal ions and forms a red colour when coordinated to
metal ions.
In this experiment the chloride content of the solution containing MgCl2 and NaCl will
be determined by Fajans method. Magnesium ion concentration will be determined by
EDTA titration.
RD
3
A 100 cm solution prepared by dissolving MgCl2 and NaCl in water is given as the
3
unknown sample. The task is to determine the mass concentration (in g/100 cm ) of both
MgCl2 and NaCl in the unknown solution.
Reagents
• Unknown solution, 100 cm3
• Dextrin in Eppendorf tubes (3) in a zipper bag
• Dichlorofluorescein, indicator
• AgNO3 solution, c = 0.1 mol dm-3 *), 100 cm3
• EDTA solution, c = 0.01 mol dm-3 *), 100 cm3
• pH 10 buffer (NH3/NH4Cl), 5 cm3
• Eriochrome Black T, indicator
_______________
*) The exact value of the concentration is given on the label.
A. Determination of total chloride concentration by Fajans method

1. Using a 10 cm3 pipette, transfer 10.0 cm3 aliquot from the bottle labelled as unknown
solution into a 250 cm3 Erlenmeyer flask. Complete the volume to approximately
100 cm3 by adding distilled water.
2. Take one of the Eppendorf tubes given in the zipper bag labelled as “dextrin” and
transfer all its content into the Erlenmeyer flask.
3. Add 5 drops of dichlorofluorescein indicator solution.
4. Record the exact concentration of AgNO3 in standard solution.
5. Fill one of the burettes with the standard AgNO3 solution.
6. Titrate the unknown solution until the whole solution has pink-red colour.
7. Record the volume of AgNO3 used in cm3.
8. Use the same Erlenmeyer flask when repeating the titration. Before doing this, pour the
content of Erlenmeyer flask into the “Aqueous Waste” container and rinse it twice with
distilled water.
B. Determination of Mg2+ by direct titration with EDTA

1. Fill the second burette with the standard EDTA solution.
2. Record the exact concentration of EDTA in standard solution.
RD
3 3
3. Using a 25 cm pipette, transfer a 25.0 cm aliquot of the unknown solution into a
3 3
250 cm Erlenmeyer flask. Complete the volume to approximately 100 cm by adding
distilled water.
3 3
4. Using a 1 cm pipette, add 1.0 cm of pH 10 buffer.
5. Add 3 – 4 drops of EBT indicator solution.
6. Titrate the unknown solution with standard EDTA solution until the colour changes
from red to blue.
3
7. Record the volume of EDTA solution used, in cm .
water.
Treatment of Data
1.1 Determine the amount of Cl– ions (in mmol) in 100 cm3 of the unknown solution.
2+ 3
1.2 Determine the amount of Mg ions (in mmol) in 100 cm of the unknown solution.
1.3 Calculate the concentration of both MgCl2 and NaCl in g/100 cm3 in the unknown
solution.
_______________
RD
SOLUTION
1.1 – 1.3
Some distribution graphs were proposed by the organizer and approved by the
International Jury that could be applied for evaluating of accuracy of the titrations
and, consequently, for awarding points.
For determinations of amounts of substance of Cl– and Mg2+ ions, as well
concentrations of both MgCl2 and NaCl in the unknown solution, simple
stoichiometric calculations can be applied.
TH
Determination of the Langelier Saturation Index of a pool water

The Langelier Saturation Index (LI) is a measure of swimming pool water corrosivity
as well as its ability to dissolve or deposit calcium carbonate. If LI is approximately zero,
the water is considered “balanced”. If the index LI is a positive number, the water tends to
deposit calcium carbonate and is scale-forming. If the index LI is a negative number, the
water is corrosive and dissolves calcium carbonate. The LI is a combination of the physical
values factors taken from Table 1 and can be calculated by the formula:
LI = pH + FT + FD + FA – FTDS
-0,8 -0,4 -0,1 0 0,1 0,4 0,8

Aggressive water Danger of Acceptable Excellent Acceptable Danger of scaling Formation of
causing corrosion corrosion balance balance balance and deposits scale and
of metallic parts deposits
etc
pH : pH value
FT : Temperature factor
FD : Calcium hardness (CH) factor
FA : Total alkalinity (TA) factor
FTDS: Total dissolved solids (TDS) factor
Table 2.1 Values and corresponding factors

Calcium Total Total
hardness alkalinity dissolved
Temperature,
о FT (CH), FD (TA), FA solids (TDS), FTDS
С -3 3 -3
mg dm mg dm mg dm
CaCO3 CaCO3 NaCl
0 0.0 5 0.3 5 0.7 0 12.0
3 0.1 25 1.0 25 1.4 - -
8 0.2 50 1.3 50 1.7 1000 12.1
12 0.3 75 1.5 75 1.9 - -
16 0.4 100 1.6 100 2.0 2000 12.2
19 0.5 150 1.8 125 2.1 - -
24 0.6 200 1.9 150 2.2 3000 12.25
29 0.7 250 2.0 200 2.3 - -
TH
Table 2.1 continued
34 0.8 300 2.1 300 2.5 4000 12.3

41 0.9 400 2.2 400 2.6 - -
53 1.0 600 2.35 800 2.9 5000 12.35
- - 800 2.5 1000 3.0 - -
- - 1000 2.6 - - 6000 12.4
In this task you will have to determine the LI value of a given water sample. Note that
hardness is expressed as the equivalent to the concentration of CaCO3 (expressed in
mg dm-3). Total alkalinity, being the acid equivalent to the total amount of carbonate and
hydrogen carbonate, can also be expressed in mg dm-3 of CaCO3, whereas TDS is
recalculated as concentration of NaCl (mg dm3).
Chemicals
• EDTA, standard aqueous solution, c = 0.0443 mol dm–3,

• HCl, standard aqueous solution, c = 0.0535 mol dm–3,
• Methyl orange, 0.1% in water,
• Murexide, indicator, solid mixture with NaCl (1 : 250 by mass),
• Sample of water.
Procedures
Calcium hardness is determined by complexometric titration with EDTA (Na2H2Y).
This is performed in a strongly alkaline medium to mask magnesium (large amounts of
Mg2+ interfere due to the co-precipitation of calcium with Mg(OH)2; moreover, the
complexometric indicator is also adsorbed on Mg(OH)2, which impairs the observation of
its colour change). When the alkali is added, titration should be carried out immediately to
avoid the deposition of CaCO3.
2.1 Write down equation of the reaction occurring during titration with Na2H2Y.
Procedure for determination of calcium

a) Put the standard solution of EDTA (precise exact concentration c = 0.0443 mol dm–3)
in the burette.
b) Pipette a 20 cm3 aliquot of the water sample into an Erlenmeyer flask.
3 –3 3
c) Add 3 cm of NaOH solution (c = 2 mol dm ) with the 10 cm measuring cylinder.
TH
d) Add murexide indicator with spatula to obtain noticeably pink solution.

e) Within few minutes titrate the mixture with EDTA solution until the indicator colour
changes from pink to purple.
2.2 Fill in the table 2.2.

Table 2.2
Titration No
Volume of EDTA solution

Accepted volume, cm3:
2.3 Calculate the hardness of the water sample in mg dm–3 of CaCO3. Write down the
result in Table 2.4 (see question 2.11).
Measurement of pH
Locate a pH meter in the lab (or ask your lab assistant).
3
a) Place about 70 -- 90 cm of the water sample into a clean Erlenmeyer flask.
b) Remove the protective cap from the pH-meter (keep the cap standing, since there is
solution in it).
c) Rinse the electrode with distilled water using a plastic wash bottle.
d) Turn the pH meter on by sliding the ON/OFF switch.
e) Immerse the electrode in the solution to be tested and stir gently by swirling the flask.
f) Place the flask on the table and wait until the reading stabilizes (not more than 1 min).
g) Read and record the pH value.
h) Switch the pH meter off, rinse the electrode with distilled water and place the
protective cap back.
2.4 Write down the pH value in Table 2.4 (see question 2.11).
2.5 Which form of carbonic acid predominates in your water sample?
Confirm your choice with calculation and tick one box.
TH
Note: The dissociation constants of carbonic acid are as follows:

–7
K1 = 4.5 · 10 ;
K2 = 4.8 · 10–11.
2.6 Write down the ionic equation of the predominant reaction of titration of the water
sample with HCl solution.
Determination of the total alkalinity

To obtain the value of the total alkalinity the water sample should be titrated to
H2CO3. An acid-base indicator used is methyl orange, which starts changing its colour
from yellow to orange at pH of about 4.5.
a) Rinse the burette with distilled water and fill it with the standard HCl solution (exact
concentration of HCl is 0.0535 mol dm–3).
3
b) Pipette a 50.0 cm aliquot of water sample into an Erlenmeyer flask and add 3 drops
of methyl orange solution.
c) If the sample is orange prior to addition of the acid the total alkalinity is zero. If the
solution is yellow titrate it with the standard acid solution until the first noticeable
colour change towards orange is observed. Record the volume of the titrant used.
2.7 Fill in the Table 2.3.

Table 2.3
Titration No
Volume of the standard HCl
solution
Accepted volume, cm3 ______
2.8 Calculate the total alkalinity (in mg dm–3 CaCO3). Write down the result in Table 2.4
(see question 2.11).
TH
2.9 Temperature measurement

Read the thermometer located at the table of common use and write down the value
into Table 2.4 (see question 2.11).
2.10 TDS determination in the water sample with the test strip.
a) Fill a beaker with the water sample to a level of about 3 cm of height. Immerse the
strip into water; be sure that the yellow band on the top of the strip does not touch the
liquid.
b) Wait for 3 - 4 minutes until the yellow band turns completely brown. Take the reading
as shown in the picture hereunder. Give it to one decimal digit.
c) Report the reading.
d) Find your TDS concentration as that of NaCl in mg dm–3 in the table to the right of the
picture.
e) Write down the concentration of NaCl in Table 2.4 (see question 2.11).
NaCl
Reading conc.,
mg dm–3
1.4 360
1.6 370
1.8 420
2.0 430
2.2 470
2.4 530
2.6 590
2.8 660
3.0 730
3.2 800
3.4 880
3.6 960
3.8 1050
4.0 1140
4.2 1240
4.4 1340
4.6 1450
4.8 1570
5.0 1700
TH
2.11 Fill in all the blank boxes in the Table 2.4. Calculate LI and write down the result in
Table 2.4. Take the values of the factors to the accuracy of two decimal digits.
Table 2.4. Calculation of LI of the water sample
Water sample Number ______
CH, TA, TDS,

–3 –3 –3
mg dm mg dm t, °C pH mg dm
CaCO3 CaCO3 NaCl LI
FD FA FT FTDS
Theoretical questions. Water balance correction.

If LI significantly deviates from zero, it is needed to be adjusted to zero.
Imagine you are given a sample of pool water analyzed as you have done above.
–3 –3
The results of the analysis are as follows: CH = 550 mg dm , FD = 2.31, TA = 180 mg dm ,
FA = 2.26, t = 24 ˚C, FT = 0.6; TDS = 1000 mg dm–3, FTDS = 12.1, pH = 7.9, LI = 0.97.
The pool serviceman added 10 cm3 of 0.0100 mol dm–3 solutions of reagents (NaHCO3,
NaOH, NaHSO4, CaCl2, EDTA (disodium salt dihydrate) and HCl) to 200 cm3 of different
pool water samples (one reagent for one sample).
2.12 Decide whether CaSO4 is deposited upon addition of NaHSO4.
Yes No
Tick one box and confirm your choice with calculation.
Note: CaSO4 solubility product is 5·10–5. Assume that no precipitate of CaCO3 is
formed upon addition of any of the above reagents.
2.13 Fill in the hereunder table 2.5 by showing the trends of changes resulting from
addition of each reagent to this particular water sample (use “+” if the factor
increases, “–“ if it decreases, and “0” if it does not change).
TH
Table 2.5
NaHCO3
NaOH
NaHSO4
CaCl2
Na2H2Y
HCl
_______________
TH
SOLUTION
2– 2+ 2- +
2.1 H2Y + Ca = CaY + 2 H
Reactions with other forms of EDTA are also acceptable.
2.5 We observe pH ~8 ⇒ this is carbonic acid - hydrogen carbonate buffer, then:

[HCO3– ] K
= +1 = 45
[H2CO3 ] [H ]
i.e. ~ 98 % of hydrogen carbonate
2.6 HCO3– + H+ = H2CO3 (or H2O + CO2)
VEDTA × cEDTA 200 2.2 × 0.05

2.12 [Ca2+ ] = = = 0.00524 mol dm–3
20 200 + 10 20 × 200
210
0.01 × 10
When NaHSO4 is added, [SO42–] = = 0.000476 mol dm–3
(200 +10)
Then [Ca ] [SO4 ] = 0.00524 × 0.000476 = 2.5 · 10

2+ 2– –6
< Ksp
⇒ no precipitate of CaSO4 is formed.
Your answer (tick one) Yes □ No

2.13
NaHCO3 + + 0 + +
NaOH + + 0 + +
NaHSO4 – – 0 + –
CaCl2 0 0 + + +
Na2H2Y – – – + –
HCl – – 0 0 –
NTT VN-123
Practical Code: Task 1 2 3 4 5 6 7 8 9 10 Total

Problem 3
Examiner Mark 0 25 2 25 3 4 3 2 5 2 71
13 % of the
total Grade
Practical Problem 3. Analysis of a hydrated zinc iron(II) oxalate double salt
Zinc iron(II) oxalate double salt is a common precursor in the synthesis of zinc
ferrite which is widely used in many types of electronic devices due to its interesting
magnetic properties. However, such double salts may exist with different compositions
and different amount of water depending on how the sample was synthesized.
You will analyze a pure sample of hydrated zinc iron(II) oxalate double salt (Z) in
order to determine its empirical formula.
Procedure
The concentration of the standard KMnO4 is posted on the lab walls.
Bring a clean 250 mL beaker to the lab assistant who will be waiting by the
balance. You will receive a pure sample of Z for analysis. Accurately weigh between
0.7-0.8 g of the pure sample Z onto the weighing paper (m, grams). This should then
be immediately quantitatively transferred into your 250 mL beaker for analysis, and its
mass recorded in table below.
Task 3.1: Record the mass of the sample of pure Z taken.
Mass of sample, m (gram) Lab assistant’s signature
------------------ ---------------------
Analysis of Z
- Using the 100 mL graduated measuring cylinder, measure ca. 30 mL of 30 wt%
H2SO4 solution and add it into the 250-mL beaker containing your accurately
weighed pure sample of Z. To speed up the dissolving of your sample you may use
The 46th IChO – Practical Examination. Official English version 22/28

NTT VN-123
the hotplate stirrer to warm up the mixture, but be careful not to boil it. You
should not use the digital thermometer as the acid may damage it. After the solid
has dissolved, remove the beaker from the hotplate stirrer and cool it to close to
room temperature. After the solution has cooled, quantitatively transfer it into the
100 mL volumetric flask. Add distilled water up to the 100 mL–mark. We will
now call this solution C.
- Use an appropriately labeled beaker to transfer the standardized KMnO4 solution
into the burette graduated with brown marks.
- Use another appropriately labeled beaker to transfer the standardize EDTA solution
into the burette graduated with blue marks.
Titration with KMnO4

a) Using the 5 mL graduated pipette add 5.00 mL of the solution C into a 250 mL
conical flask.
b) To this conical flask add about 2 mL of 30 wt% H2SO4 solution, about 3 mL of
3.0 M H3PO4 solution, and about 10 mL of distilled water. Heat the mixture on the
hot plate stirrer until hot, but be careful not to boil it.
c) Titrate the hot solution with the standardized KMnO4 solution, recording your
burette readings in the table below. At the end point of the titration, the pink color
of the solution appears. Repeat the titration as desired and report your accepted
volume of KMnO4 solution consumed (V1 mL) in the table.
Task 3.2: Record volumes of standardized KMnO4 solution consumed

(You DO NOT need to fill in the entire table)
Titration No
1 2 3 4
Initial reading of the burette of KMnO4, mL
Final reading of the burette of KMnO4, mL
Consumed volume of KMnO4, mL
Accepted volume, V1 = ________ mL

NTT VN-123
Task 3.3: Can aqueous HCl or HNO3 be used instead of H2SO4 for the dissolving of
sample Z and the subsequent analyses?
HCl YES NO
HNO3 YES NO
Titration with EDTA
- Clean both the 250 mL beakers ready for the next part of the experiment. Pipette
10.00 mL of solution C into a 250 mL beaker. Heat and stir the solution on the
hotplate stirrer, but be careful not to boil it. Add ca. 15 mL of 20 wt% NaOH
solution to the beaker and keep it on the hotplate for ca. 3-5 min in order to
complete the precipitation of iron hydroxide, and to convert all Zn2+ ions into the
ionic complex [Zn(OH)4]2-.
- Using a glass funnel and the large quantitative filter paper, filter the hot suspension
directly into the 250 mL conical flask. From this point take care with the
volumes as you will be preparing a standard solution of exactly 100 mL from
the filtrate. As it is filtering, prepare some warm distilled water in a 250 mL
beaker (ca. 50 mL). Wash the precipitate on the filter paper (at least 5 times) with
small portions (ca. 5 mL) of the warm distilled water. Cool the filtrate down and
then quantitatively transfer it into the 100 mL volumetric flask via a glass funnel.
Add distilled water to make up to the 100 mL mark. This will now be referred to as
solution D.
- Pipette 10.00 mL of solution D into a 250 mL conical flask. Add ca.10 mL
ammonia buffer solution (pH = 9 – 10) and a small quantity of the ETOO indicator
using the glass spatula spoon. Mix well to obtain a purple solution. Titrate the
solution with the standardized 2.00 × 10–3 M EDTA solution, recording your
burette readings in table below. At the end point, the color of the solution turns
blue. Repeat the titration as desired and report your accepted volume of EDTA
solution consumed (V2 mL) in the table.

NTT VN-123
Task 3.4: Record the volumes of EDTA solution consumed

Titration No
1 2 3 4
Initial reading of the burette of EDTA, mL
Final reading of the burette of EDTA, mL
Consumed volume of EDTA, mL
Accepted volume,V2 = ________ mL
Determination of the empirical formula of Z
Task 3.5: Calculate the number of moles of Zn2+, n Zn , present in 100 mL of solution
2+
C.
n Zn 2 + (mol): ……………
Task 3.6: Give the ionic equations for the reduction-oxidation reactions taking place
in the titration with KMnO4.

NTT VN-123
Task 3.7: Calculate the number of moles of Fe2+, nFe , present in 100 mL of solution
2+
C. [YOU WILL NEED THE PRECISE CONCENTRATION OF KMnO4

POSTED ON THE WALLS IN YOUR LAB]
V1, mL = …………………………………….
n Fe2 + (mol): …………………………
Task 3.8: Calculate the number of moles of C2O42- anion, nC O , in 100 mL of 2−

2 4
solution C.
nC O 2− = ………………………………………….
2 4

NTT VN-123
Task 3.9: Calculate the number of moles of water, nH O , in the original sample of Z
2
taken for analysis.
Task 3.10: Give the empirical formula of Z:

GBR-1
Chemicals
For all problems
Deionised water in:
Wash bottle (bench)
Water Not hazardous

2-Acetonaphthone:
Standard A H302, H315, H319, H335,
H411
DNPH H228, H302
Bleach H290, H314, H400
amber glass bottle
TLC eluent
H290, H314, H319, H335
and others

H290, H315, H319
Cu Not hazardous
plastic bottle
H2O2 conc. H302, H315, H318
plastic bottle


GBR-1

(bench)
Buffer H302, H319, H314, H400
(bench)
NaOH H314
bottle
Equipment
Personal equipment
Safety goggles 1
1 (each)

Personal equipment

GBR-1

Open metal ring 1
Reflux condenser 1
Glass funnel 1
1
label)
Rubber bulb 1
1
haloform reaction
1

Stopwatch 1
1
H2O2, 50 cm3
1

GBR-1


1 (each)
Burette clamp
Burette, 25 cm3
Glass funnel 1

GBR-1
Question 3.1 3.2 3.3 3.4 3.5

Points 3 20 2 2 16
Practical Score
Problem 3
Points 4 20 2 4 2 75
Score

and manganese.
No. Trade brand
1 Kláštorná 290 74 71 16 15 89 1 341
2 Budišská 200 50 445 50 25 433 1 535
3 Baldovská 378 94 90 0 78 215 1 557
4 Santovka 215 67 380 45 177 250 1 462
5 Slatina 100 45 166 40 104 168 653
6 Fatra 45 48 550 16 36 111 1 693
7 Ľubovnianka 152 173 174 5 10 20 1 739
8 Gemerka 376 115 85 0 30 257 1 532
9 Salvator 473 161 214 30 116 124 2 585
10 Brusnianka 305 101 187 35 59 774 884
11 Maxia 436 136 107 18 37 379 1 715

GBR-1
Notes:
 Use the prescribed symbols in the notations of calculations.
 You are provided with a swollen cation exchange resin (Catex) in its H+ form. Use a thick stem
Pasteur pipette for transferring it. You can add more deionised water to the resin if necessary (it
 Concentrations of the standard solutions:
Procedure
V1). Then using deionised water transfer the catex quantitatively into
a titration (kind-of-round, flat bottomed) flask. Add an appropriate
amount of deionised water so that the suspension can be swirled well
and the colour of the solution over the catex can be observed.

GBR-1

No. V1 [cm3] V2 [cm3]
2 5.00
Accepted value V2
mmol cm−3.
Calculation:
sample (volume V4). Swirl the mixture occasionally for about 5 minutes. Use the conical flask as
a stand for the funnel and to collect the filtrate. Then filter the catex through a fritted (sintered)
funnel (porosity S1) and wash it with deionised water to a neutral pH (check with pH paper).
Discard the filtrate.
2.b Using deionised water, transfer the catex quantitatively from the funnel into a titration flask.

GBR-1
Catex NaOH
volume consumption
No. V4 [cm3]
V3 [cm3] V5 [cm3]
2 5.00 50.00
Accepted value V5
P3.6 Assuming that all the ions in your solution are M+ ions, calculate, for the accepted value of V5,
the molar concentration of cations (as M+ molar concentration) in mineral water, c*(M+), in
mmol dm−3.
Calculation:

GBR-1
3. Pipette 10.00 cm3 (V6) of the sample into the titration flask and add approx. 25 cm3 of deionised
water. Adjust pH by adding 3 cm3 of the buffer solution. Add some Eriochrome black T indicator
(EBT, on the tip of the spatula) and titrate with the standard EDTA solution from wine red to blue
(V7).

3
No. V6 [cm ] V7 [cm3]
2 10.00
Accepted value V7
Calculation:
4. Use Table P3.2 in the next identification procedure.
P3.9 In Table P3.2, write down experimentally found values from tasks P3.6 and P3.8 and tick ()
all the lines with an approximate match (±10%) of the found parameter c(M2+) and c*(M+) with
the data from the table.

GBR-1
Table P3.2
Total
equivalent
c(M2+) c(M+)
c*(M+)
[mmol dm−3]
Your exp. values XXX XXX XXX
1 Kláštorná 10.30 3.50 24.1
2 Budišská 7.06 20.63 34.7
3 Baldovská 13.32 3.91 30.5
4 Santovka 8.13 17.67 33.9
5 Slatina 4.35 8.25 16.9
6 Fatra 3.11 24.32 30.5
7 Ľubovnianka 10.92 7.70 29.5
8 Gemerka 14.13 3.70 32.0
9 Salvator 18.46 10.07 47.0
10 Brusnianka 11.79 9.03 32.6
11 Maxia 16.50 5.11 38.1
P3.10 Based on your results, decide which mineral water is in your sample. Tick () the cross-
4 Santovka 10 Brusnianka
5 Slatina 11 Maxia
6 Fatra 12 other

XXX-X
Question 3.1 3.2 3.3 3.4 3.5

Points 3 20 2 2 16
Practical Score
Problem 3
Points 4 20 2 4 2 75
Score

and manganese.
No. Trade brand
1 Kláštorná 290 74 71 16 15 89 1 341
2 Budišská 200 50 445 50 25 433 1 535
3 Baldovská 378 94 90 0 78 215 1 557
4 Santovka 215 67 380 45 177 250 1 462
5 Slatina 100 45 166 40 104 168 653
6 Fatra 45 48 550 16 36 111 1 693
7 Ľubovnianka 152 173 174 5 10 20 1 739
8 Gemerka 376 115 85 0 30 257 1 532
9 Salvator 473 161 214 30 116 124 2 585
10 Brusnianka 305 101 187 35 59 774 884
11 Maxia 436 136 107 18 37 379 1 715

XXX-X
Notes:
• Use the prescribed symbols in the notations of calculations.
• You are provided with a swollen cation exchange resin (Catex) in its H+ form. Use a thick stem
Pasteur pipette for transferring it. You can add more deionized water to the resin if necessary (it
• Concentrations of the standard solutions:
Procedure
V1). Then using deionized water transfer the catex quantitatively into
a titration flask. Add an appropriate amount of deionized water so that
the suspension can be swirled well and the colour of the solution over
the catex can be observed.
Ion exchange
R–H + NaCl ⇆ R–Na + HCl
Neutralization
HCl + NaOH ⇆ NaCl + H2 O
Indication
HInd + OH– ⇆ Ind– + H2 O

XXX-X

No. V1 [cm3] V2 [cm3]
1 e.g. 19.00
2 5.00 e.g. 19.50
3 e.g. 19.70
Accepted value V2
e.g. 19.40
mmol cm−3.
Calculation:
+ V2 × c(NaOH) 19.40 cm3 × 0.2660 mol dm–3

Qv (H ) = = = 1.032 mmol cm–3
V1 5.0 cm3
1 point for correct result
sample (volume V4). Swirl the mixture occasionally for about 5 minutes. Use the Erlenmeyer flask
as a stand for the funnel and to collect the filtrate. Then filter the catex through a fritted funnel
(porosity S1) and wash it with deionized water to a neutral pH (check with pH paper). Discard the
filtrate.
2.b Using deionized water, transfer the catex quantitatively from the funnel into a titration flask and
discard the filtrate.

XXX-X
Ion exchange from the sample
R–H + M+ ⇆ R–M + H+
2 R–H + M2+ ⇆ R2 –M + 2 H+
2 points – 1 point for each correct equation or 2 points for the correct general equation with Mn+
Catex NaOH
volume consumption
No. V4 [cm3]
V3 [cm3] V5 [cm3]
1 e.g. 13.00
2 5.00 50.00 e.g. 13.20
3 e.g. 13.10
Accepted value V5
e.g. 13.10
P3.6 Consider that all the ions in your solution are M+ ions. For the accepted value of V5, calculate
the total amount of cations (as M+ molar concentration) in 1 dm3 of mineral water. Show the
calculation of the total equivalent concentration of cations, c*(M+) in mmol dm−3.
Calculation:
* + V3 × Qv (H+ )ionex – V5 × c(NaOH)

c (M ) =
V4
5.00 cm3 × 1.032 mol dm–3 – 13.10 cm3 × 0.2660 mol dm–3
c* (M+ ) =
50.00 cm3
c* (M+ ) = 33.51 mmol dm–3
3 points for the correct calculation procedure

XXX-X
3. Pipette 10.00 cm3 (V6) of the sample into the titration flask and add ca. 25 cm3 of deionized water.
Adjust pH by adding 3 cm3 of the buffer solution. Add some Eriochrome black T indicator (EBT,
on the tip of the spatula) and titrate with the standard EDTA solution from wine red to blue (V7).
No. V6 [cm3] V7 [cm3]
1 e.g. 14.20
2 10.00 e.g. 14.25
3 e.g. 14.25
Accepted value V7
e.g. 14.25
Calculation:
V7 × c(EDTA)
c(M2+ ) =
V6
14.25 cm3 × 5.965 mmol dm–3
c(M2+ ) = = 8.500 mmol dm–3
10.00 cm3

4. Use Table P3.2 in next identification procedure.
P3.9 In Table P3.2, write down experimentally found values from tasks P3.6 and P3.8 and tick (✓)
all the lines with approximate match (±10%) of the found parameter c(M2+) and c*(M+) with the
data from the label.

XXX-X
Table P3.2
Total
equivalent
c(M2+) c(M+)
c*(M+)
[mmol dm−3]
Your exp. values 8.50 XXX 33.51 XXX XXX
1 Kláštorná 10.30 3.50 24.1
2 Budišská 7.06 20.63 34.7 ✓
3 Baldovská 13.32 3.91 30.5 ✓
4 Santovka 8.13 17.67 33.9 ✓ ✓
5 Slatina 4.35 8.25 16.9
6 Fatra 3.11 24.32 30.5 ✓
7 Ľubovnianka 10.92 7.70 29.5
8 Gemerka 14.13 3.70 32.0 ✓
9 Salvator 18.46 10.07 47.0
10 Brusnianka 11.79 9.03 32.6 ✓
11 Maxia 16.50 5.11 38.1
Maximum 4 points. For each column: 2 points if correctly marked, 1 point if partially marked.
P3.10 Based on your results, decide which mineral water is in your sample. Tick (✓) the cross-
4 ✓ Santovka 10 Brusnianka
5 Slatina 11 Maxia
6 Fatra 12 other
2 points if consistent with the results marked in Table 3.2 (Kláštorná or Ľubovnianka, if values from P3.6 and
P3.8 are accurate)

XXX-X
Marking notes
V2master = 13.10, 17.20, or 20.65 cm3
V5master = from 7.54 to 16.12 cm3
V7master = 17.15 or 18.41 cm3
Replaced chemicals and equipment

Signature
Item or incident Penalty
0 pt

Titolazione
iodometrica
TH
You are required to determine the concentrations of hydrochloric acid and potassium
iodate in the diluted solution containing both.
Procedure:
A solution containing potassium iodate and hydrochloric acid has already been
measured into the volumetric flask provided. Fill the flask to the mark with distilled water
using the wash bottle, close it with a stopper and shake it thoroughly. Fill the burette with
the standard sodium thiosulphate solution using one of the beakers provided. (The exact
concentration of the thiosulphate is given on the label of the bottle.)
a) First titration
3
Pipette a 10.00 cm aliquot (portion) of the solution from the volumetric flask into a
glass stoppered conical flask. Dilute it with 10 cm3 of distilled water, add 1 g (a small
spatula end-full) of potassium iodide and acidify with 10 cm3 of 10 % sulphuric acid using
a measuring cylinder. Titrate immediately the iodine formed with the standard sodium
thiosulphate solution until the solution in the flask is pale yellow. Add with a pipette 1 cm3
of starch indicator solution and continue the titration to completion. Repeat the titration
twice more and record your readings on the result sheet.
b) Second titration
Pipette a 10.00 cm3 aliquot of the solution into another glass stoppered conical flask,
dilute with 10 cm3 of distilled water, add 1 g of solid potassium iodide, and leave to stand
for 10 minutes. Then titrate the iodine formed using the standard sodium thiosulphate
solution, adding 1 cm3 of starch indicator solution when the mixture is pale yellow. Repeat
the titration twice more, recording your readings on the result sheet.
Task:
Calculate the concentration of the HCl and the KIO3 in the solution that you prepared
by dilution (in mol dm-3).
____________________
TH
SOLUTION
The reaction:
- - +
IO3 + 5 I + 6 H = 3 I2 + 3 H2O
occurs to be quantitative both with respect to IO3- and H+. Consequently the first titration
(in the presence of sulphuric acid) is suitable for the determination of iodate, while the
second one for the determination of the hydrochloric acid content.
ND
Titration of Oxygen Dissolved in Water
(Winkler's method)
In aqueous alkaline solution, dissolved oxygen oxidizes manganese(II) hydroxide to
hydrated manganese(III) oxide (written as Mn(OH)3 for simplification). In acidic solution,
manganese(III) ions oxidize iodide ions to iodine. The iodine formed is titrated with a
sodium thiosulphate solution.
Data:
Redox couple Electrode potentials (in V)
at pH = 0 at pH = 14
Mn3+ / Mn2+ 1.51
Mn(OH)3 / Mn(OH)2 0.13
O2 / H2O 1.23 0.39
I2 / I- 0.62 0.62
S4O62- / S2O32- 0.09 0.09
Solubility products: Ksp(Mn(OH)2) = 1×10-13
Ksp(Mn(OH)3) = 1×10-36
Gas constant: R = 8.315 J K-1mol-1
Procedure:
Preliminary remarks: To reduce volume variations, the reagents are added either as solids
(sodium hydroxide pellets ...), or as concentrated solutions (sulphuric acid).
1. The water to be tested is stored in a large container located on the general-use
bench. Place two glass beads into a 250 cm3 ground top Erlenmeyer (conical) flask.
Fill it to the rim with the water to be tested. At this stage of the manipulation the
ND
Erlenmeyer flask should be standing in the basin provided to avoid overflow of water
onto the bench. Measure the temperature of the water.
2. Add to the water, avoiding any loss of reagent:
a) 2 g of manganese(II) chloride, preweighed within a decigram and contained in
the bag.
b) about 8 pellets of sodium hydroxide (yielding a basic medium, pH = 14). The
pellets will be found on the general-use bench.
3. Stopper the Erlenmeyer flask, avoiding air bubbles, and swirl it until complete
dissolution of the sodium hydroxide and of the manganese chloride has occurred. A
brown precipitate forms.
4. Let the flask stand for at least 30 minutes.
5. Open the Erlenmeyer flask, add concentrated sulphuric acid dropwise, stirring with a
glass rod until the solution is definitely acidic (check with the pH indicator paper);
make sure that nearly all the precipitate has disappeared.
Sulphuric acid will be found on the general-use bench.
6. Add to the Erlenmeyer flask 3 g of potassium iodide, preweighed within a decigram
and contained in a bag. Stopper the flask and shake it until the potassium iodide has
dissolved. The solution should now be clear.
7. Remove a 50 cm3 sample of the solution and titrate it with a X mol dm-3 sodium
thiosulphate solution (the numerical value of X will be shown on the board). For this
titration, the endpoint can be determined using the indicator thiodene which is
equivalent to starch. A small quantity of this solid indicator should be dissolved in the
solution being titrated just prior to the endpoint.
Questions:
3.1 Justify that the oxidation of manganese(II) by dissolved oxygen is possible only in
alkaline solution.
3.2 Write the equation of the reaction between:
- dissolved oxygen and manganese(II) hydroxide (in alkaline solution),
- manganese(III) ions and iodide ions,
- iodine and thiosulphate.
3.3 Record the volume of thiosulphate required to reach the endpoint.
ND
3.4 Derive an expression that relates the dissolved oxygen concentration in water
(expressed as mol dm-3) to the volume in cm3 of thiosulphate added at the endpoint.
Determine that concentration for the water tested.
3 o
Deduce the volume of oxygen (in cm ), determined at 0 C and at a pressure of 101,325
Pa, contained in a litre of water (measured at ambient temperature). Give the
temperature of the water.
_______________
SOLUTION
3.1 E0(O2/H2O) > E0(Mn(III)/Mn(II) at pH = 14
3.2 O2 + 4 e– + 2 H2O → 4 OH–

Mn(OH)2 + HO– → Mn(OH)3 + e–
O2 + 4 Mn(OH)2 + 2 H2O → 4 Mn(OH)3
2 I → I2 + 2 e
– –
Mn3+ + e– → Mn2+
2 I– + 2 Mn3+ → I2 + 2 Mn2+
I2 + 2 e – → 2 I–
2 S2O32- → S4O62- + 2 e–
I2 + 2 S2O32- → 2 I + S4O62-
–
3.4 1 mol O2 ≙ 4 mol Mn(II) ≙ 4 mol Mn(III)

–
4 mol Mn(III) ≙ 4 mol I ≙ 2 mol I2
2 mol I2 ≙ 4 mol S2O32-
c( S2O32- ) × V( S2O32- ) = 4 × c(O2) × 50
TH
PRACTICAL PROBLEMS
Determination of Fatty Acids
A mixture of an unsaturated monoprotic fatty acid and an ethyl ester of a saturated
3
monoprotic fatty acid has been dissolved in ethanol (2.00 cm of this solution contain a
1) 2)
total of 1.00 g acid plus ester). By titration the acid number , the saponification number
and the iodine number3) of the mixture shall be determined. The acid number and the
saponification number shall be used to calculate the number of moles of free fatty acid and
ester present in 1.00 g of the sample. The iodine number shall be used to calculate the
number of double bonds in the unsaturated fatty acid.
Note: The candidate must be able to carry out the whole exam by using the delivered
amount of unknown sample (12 cm3). There will be no supplementation.
1) Acid number: The mass of KOH in milligram that is required to neutralize one gram of
the acid plus ester.
2) Saponification number: The mass of KOH in milligram that is required to saponify one
gram of the acid plus ester.
3) Iodine number: The mass of iodine (I) in g that is consumed by 100 g of acid plus
ester.
Relative atomic masses:
Ar(I) = 126.90 Ar(O) = 16.00
Ar(K) = 39.10 Ar(H) = 1.01
1) Determination of the Acid Number

Unknown sample, 0.1000 M KOH, indicator (phenolphthalein), ethanol/ether (1 : 1
mixture), burette (50 cm3), Erlenmeyer flasks (3 x 250 cm3), measuring cylinder (100 cm3),
graduated pipette (2 cm3), funnel.
TH
Procedure:
3 3
Pipette out aliquots (2.00 cm ) from the unknown mixture into Erlenmeyer flasks (250 cm ).
3
Add first ca. 100 cm of an ethanol/ether mixture (1:1) and then add the indicator (5 drops).
Titrate the solutions with 0.1000 M KOH.
Calculate the acid number.
2) Determination of the Saponification Number

Unknown sample, 0.5000 M KOH in ethanol, 0.1000 M HCl, indicator (phenolphthalein),
volumetric flask (50 cm3), round bottom flask (250 cm3), Liebig condenser, burette (50
cm3), Erlenmeyer flasks (3 x 250 cm3), volumetric pipette ( 25 cm3), volumetric pipette (10
cm3), graduated pipette (2 cm3), funnel, glass rod. The round bottom flask and Liebig
condenser are to be found in the fume hoods.
Procedure
3 3
Pipette out a 2.00 cm aliquot of the unknown sample into a round bottom flask (250 cm )
and add 25.0 cm3 0.5000 M KOH/EtOH. Reflux the mixture with a heating mantle for 30
min in the fume hood (start the heating with the mantle set to 10, then turn it down to 5
after 7 min.). Bring the flask back to the bench and cool it under tap water. Transfer
quantitatively the solution to a 50 cm3 volumetric flask and dilute to the mark with a 1:1
mixture of ethanol/water. Take out aliquots of 10 cm3 and titrate with 0.1000 M HCl using
phenolphthalein as indicator (5 drops).
Calculate the saponification number.
3) Determination of the Iodine Number

In this experiment iodobromine adds to the double bond.
I Br
C C + IBr C C
The Hanus solution (IBr in acetic acid) is added in excess. After the reaction is complete,
excess iodobromine is reacted with iodide forming I2, (IBr + I- → I2 + Br-) which in turn is
determined by standard thiosulphate solution.
TH
Warning: Be careful when handling the iodobromine solution. Treat any spill immediately
with thiosulphate solution.

Unknown sample, 0.2000 M Hanus solution, dichloro-methane, 15 % KI solution in distilled
water, distilled water, 0.2000 M sodium thiosulphate, starch indicator, Erlenmeyer flasks (3
3 3 3
x 500 cm ), buret (50 cm ), graduated pipette (2 cm ), measuring cylinders (10 and 100
3 3
cm ), volumetric pipette (25 cm ), aluminium foil.
Procedure
Pipette out aliquots (1.00 cm3) of the unknown mixture into Erlenmeyer flasks (500 cm3)
and add 10 cm3 of dichloromethane. With a pipette add 25.0 cm3 Hanus solution, cover
the opening with aluminium foil and place your labelled flasks in the dark in the cupboard
(under the fume hood) for 30 min. with occasionally shaking. Add 10 cm3 of the 15 % KI
solution, shake thoroughly and add 100 cm3 of dist. water. Titrate the solution with 0.2000
M sodium thiosulphate until the solution turns pale yellow. Add starch indicator (3 cm3)
and continue titration until the blue colour entirely disappears.
Calculate the iodine number.
4) Use the results from 1) 2) and 3) to:

i) Calculate the amount of ester (in mol) in 1 g of the acid plus ester.
ii) Calculate the number of double bonds in the unsaturated acid.
TH
Determination of Copper(II) Content in Cu(gly)2 . x H2O

The Cu(II) content in Cu(gly)2 . x H2O crystals prepared yourself can be determined
by iodometry with starch solution as indicator. Based on the data obtained one can
calculate
the moles of hydrate in Cu(gly)2 . x H2O.
Reagents:
Standard KIO3 (see the label on the bottle to get the accurate concentration)
H2SO4 (1.0 mol dm-3) as indicator.
KI (0.6 mol dm-3)
-3
KSCN (2 mol dm )
Starch (0.5 %)
Na2S2O3 (to be standardized)
1. Standardization of Na2S2O3 solution

Procedure
3
(1) Transfer 25.00 cm of standard KIO3 solution to an Erlenmeyer flask.
(2) Add 5 cm3 of water, 10 cm3 of KI solution and 5 cm3 of H2SO4 (1.0 mol dm-3) to the
flask.
(3) Titrate immediately with Na2S2O3 solution.
(4) Add 2 cm3 starch solution when the colour of the titrand turns pale yellow.
(5) Continue titrating until the blue colour of the solution disappears.
(6) Proceed with step (1) – (5) twice parallel.
2. Determination of Cu(II) content in Cu(gly)2.xH2O

(1) Weigh 1.0 – 1.2 g (precision of ±0.0002 g) of Cu(gly)2 . x H2O with a dry 100 cm3
beaker as the container.
(2) Dissolve it with 40 cm3 of water and 8 cm3 of H2SO4 (1.0 mol dm-3).
(3) Transfer the above solution quantitatively to a 100 cm3 volumetric flask and dilute to
the mark.
TH
3 3
(4) Transfer 25.00 cm of the Cu(II) solution to an Erlenmeyer flask, add 50 cm of water
3
and 10 cm of KI solution to the flask.
(5) Titrate immediately with standardized Na2S2O3 solution.
3 3
(6) Add 2 cm of starch solution and 3 cm of KSCN solution to the flask when the colour
of the titrand turns from brown to pale yellow.
(7) Titrate continuously until the blue colour of the solution disappears.
(8) Proceed with steps (4) – (7) twice parallel.
_______________
SOLUTION
The following values were required to be written on the Answer Sheet :
Part 1
• Volumes of Na2S2O3 solution
• Calculation of the concentration of Na2S2O3 solution.
Part 2
• Mass of the product.
• Volumes of Na2S2O3 solution
• Mass % of Cu(II) in Cu(gly–)2 . x H2O. Calculation.
• The value of x in the formula of the product. Calculation.
Other Tasks:
1. Write two equations for chemical reactions taking place during the standardization of
Na2S2O3 solution.
2. Write the equation for the reaction between Cu2+ and I–.
Solutions of the tasks:

1. IO3- + 5 I- + 6 H3O+ → I2 + 9 H2O
I2 + 2 S2O32- → 2 I- + S 4O62-
+ 4 I → 2 CuI + I2
2+ –
2. 2 Cu
TH
PRACTICAL PROBLEMS
Iodometric Determination of the Concentration of Copper(II) and Iron(III) in a

Sample of Technological Solution
Reagents
• K2Cr2O7, 0.008333 M
• KI, 20 % by mass.
• HCl, 1 M
• H2SO4, 1 M
• Na4P2O7, 5 % by mass.
• Starch, 1 % by mass.
• Na2S2O3 (should be standardized)
• The solution to be analyzed in 100 cm3 volumetric flask.
Procedure
1. Standardization of Na2S2O3 solution
3 3
(1) 10 cm of 1 M solution of H2SO4 and 2 cm of 20 % KI solution are placed into
an Erlenmeyer flask (the solution remains colourless).
(2) 10.00 cm3 of K2Cr2O7 solution is added.
(3) The Erlenmeyer flask is covered with a watch glass and kept in a dark place for
3 to 5 min.
(4) 100 cm3 of water is added to the flask.
(5) The mixture is titrated immediately with Na2S2O3 solution until the colour of
mixture changes to pale yellow. Then 10 drops of starch solution are added.
The titration continues until blue colour disappears completely.
(6) It is recommended to repeat the titration (steps 1 through 5) two more times.
Do the following and fill in the answer sheet form
1.1 Write the reactions involved in the procedure of standardization of Na2S2O3 solution
1.2 Calculate the concentration of Na2S2O3 solution, and write your calculations.
TH
2. The determination of copper

(1) The solution to be analyzed in a 100 cm3 volumetric flask is diluted with water to the
mark and stirred
3
(2) A 10.00 cm aliquot of the solution is placed into an Erlenmeyer flask.
3 3 3
(3) 20 cm of 5 % solution of Na4P2O7, 7 cm of 1 M solution of HCl, and 10 cm of 20 %
solution of KI are added. A precipitate may form upon the addition of Na4P2O7.
(4) The Erlenmeyer flask is covered with a watch glass and left in a dark place for 3 - 5
min.
suspension changes to pale yellow. Then, 10 drops of starch solution are added.
The titration continues until the colour of suspension becomes clear white.
1.3 Write the reactions involved in the procedure of determination of Cu2+ ion.
1.4 Calculate the mass of copper in the solution under analysis, and write your
calculations.
3. The determination of total amount of copper and iron

(1) A 10.00 cm3 aliquot of the solution prepared in the item 2(1) is placed into an
Erlenmeyer flask.
(2) 2 cm3 of 1 M HCl solution and 10 cm3 of 20 % KI solution are added.
(3) The Erlenmeyer flask is covered with a watch glass and kept in a dark place for 3 to
5 min.
suspension changes to pale yellow. Then, 10 drops of starch solution are added.
The titration continues until the colour of suspension becomes clear white.
1.5 Write the reactions involved in the procedure of determination of Fe3+ ion.
1.6 Calculate the mass of iron in the solution under analysis, and write your calculations.
_______________
TH
SOLUTION
1.1
Equations:
Cr2O72- + 6 I- + 14 H+ = 2 Cr 3+ + 3 I2 + 7 H2O
I2 + 2 S2O32- = 2 I- + S4O62-
i
1.3
Equations:
2 Cu2+ + 4 I- = 2 CuI + I2
4 Fe3+ + 3 P2O74- = Fe4 (P2O7 )3 ↓
I2 + 2 S2O32- = 2 I- + S 4O62-
1.5
Equations:
2 Fe3+ + 2 I- = 2 Fe2+ + I2
2 Cu2+ + 4 I- = 2 CuI + I2
I2 + 2 S2O32- = 2 I- + S 4O62-
ND
THE 32 INTERNATIONAL CHEMISTRY OLYMPIAD, Copenhagen, 2000
PRACTICAL PROBLEMS
This experiment includes one preparation of a metal complex salt and two analyses
of a provided sample of the same compound. The compound is a “classic” within inorganic
photo chemistry.
Preparation of Potassium tris(oxalato)manganate(III) Hydrate,

K3[Mn(C2O4)3]·xH2O
Note 1: The [Mn(C2O4)3]3– ion is photosensitive and should therefore be protected from
light as far as possible. Also, the thermal stability of the title compound is low.
Note 2: Before starting the synthesis, write down the thermometer reading in ice-water.
The synthesis comprises a reduction of manganese(VII) to manganese(II) with oxalic

acid at 70 – 75 °C. After the addition of the suffi cient amount of potassium ions in form of
potassium carbonate, manganese(III) is formed by the addition of manganese(VII) at a
temperature below 2 °C.
2 MnO-4 (aq) + 8 C2O4H2(aq) → 2 Mn2+(aq) + 10 CO2(g) + 3 C2O2-
4 (aq) + 8 H2O(l)
C2O4H2(aq) + CO32- (aq) → C2O2-

4 (aq) + CO2(g) + H2O(l)
4 (aq) + 4 C2O4H2(aq) →
2+
4 Mn (aq) + MnO-4 (aq) + 11 C2O2-
→ 5 [Mn(C2O4)3]3–(aq) + 4 H2O(l)
3 3
Dissolve 5.00 g of C2O4H2 · 2 H2O in 35 cm of water in a 150 cm beaker by heating
to 70 °C. Slowly add 1.00 g of KMnO 4 with magnetic stirring. The temperature must not
exceed 70 - 75 °C. When the mixture is colourless, add 1.10 g of K2CO3 in small portions
and cool the mixture in ice. When the temperature of the mixture has fallen to 25 - 30 °C,
add 25 g of crushed ice. Meanwhile, cool the hotplate with a beaker containing ice.
ND
Maintain the temperature of the reaction mixture not more than 2 °C above your reported
temperature of ice-water while adding 0.24 g of KMnO4 in small portions with vigorous
stirring. Stir for another 10 min and filter off the white precipitate and unmelted ice, if any,
3 3
using the 60 cm filter syringe (see procedure A). Collect the filtrate in a 250 cm beaker
3
cooled in ice. Add 35 cm of ice-cold ethanol to the cherry-red filtrate (just swirl the beaker;
stirring will lead to the formation of tiny crystals), wrap the beaker in aluminium foil and
cool it in ice for 2 h (swirl the beaker three or four times during this period).
Clean the filter - first with 4 M HCl, then with water. Collect the cherry-red crystals by
3
filtration using a 60 cm filter syringe, then wash them two times 5 cm3 of ethanol and
then two times with 5 cm3 of acetone, and dry the product in air and protect it from light for
at least one hour. A brown vial with lid should be taken to be tared by the lab assistant.
When dry, the product is placed in the vial. Write name and student code on the vial. Then
close the vial and take it and your answer sheet to the lab. assistant who will weigh your
sample. The theoretical yield is 7.6 mmol.
1.1 Record the yield in grams.
1.2 Suggest a molecular formula of the white precipitate which is removed in the first
filtration.
__________
Analysis of the Provided Sample of K3[Mn(C2O4)3] · x H2O for Oxidizing

Ability
Note 3: The burette contains a cleanser and should therefore be rinsed 3 - 4 times with
water before use.
Manganese(III) is reduced to manganese(II) by iodide ions and the triiodide ions

formed are then titrated with thiosulfate.
-
2 MnIII(aq) + 3 I–(aq) → 2 MnII(aq) + I3 (aq)
I3- (aq) + 2 S2O32- (aq) → 3 I–(aq) + S4O2-

6 (aq)
3 3
In a 250 cm conical flask dissolve 1.0 g of KI in 25 cm of demineralized water and
3
add 10 cm of 4 M HCl. Immediately after an accurately preweighed sample (approx. 200
mg) of the provided complex is transferred (as much as possible is poured directly into the
ND
liquid in small portions before the residue is washed down) quantitatively with
demineralized water to the flask. Titrate the I3- formed with the standardized, approx.
3
0.025 M Na2S2O3 solution. When the brown colour has faded to light yellow, add 2 cm of
starch indicator solution and continue the titration until the colour changes from blue to
colourless.
1.3 Calculate the molar mass of the analyzed compound from the titration data.
__________
Analysis of the Provided Sample of K3[Mn(C2O4)3] · x H2O for Reducing

Ability
Note 4: The burette should be rinsed 2 - 3 times with water before this titration.
Manganese(III) is reduced to manganese(II) by the oxalate ligands, and excess

oxalate is titrated with permanganate.
3– +
2 [Mn(C2O4)3] (aq) + 10 H (aq) → 2 Mn2+(aq) + 2 CO2(g) + 5 C2O4H2(aq)
+
5 C2O4H2(aq) + 2 MnO-4 (aq) + 6 H (aq) → 10 CO2(g) + 2 Mn2+(aq) + 8 H2O(l)
Transfer an accurately preweighed sample (approx. 200 mg) of the provided

3 3
complex quantitatively with demineralized water to a 250 cm conical flask. Add 25 cm of
2 M sulphuric acid and heat the solution to 75 – 80 °C . Without further heating, titrate with
the standardized, approx. 0.025 M KMnO4 solution. Near the end of the titration add the
titrant slowly, until one drop gives the solution a rose colour which does not fade on
standing for 0.5 min.
The results of the two types of analysis may differ by up to 10 %. Use only the result
from the titration with KMnO4 for the following calculation.
1.5 Calculate the value of x in the formula K3[Mn(C2O4)3] · x H2O and the yield of your
preparation in percent of the theoretical yield.
TH
Introduction
Procedures
3
TH
precipitation.)

volumetric flask.

TH
3

3 3
3

_______________
SOLUTION
box!
Ca Sr Ba
Ca and Sr and Ba
+ CO23−
2+
Sr SrCO3
TH
2 Ba 2+ + Cr2O72− + H2O 2 BaCrO4 + 2 H

+

-3 3
3

-3 3
3
2+ -
2 Cu +4I I2 + 2 CuI
I2 + 2 S2O32−
- 2-
2 I + S4O6

-1 -1
[M(Cu) = 63.55 g mol ; M(La) = 138.91 g mol ]
Amount of copper:
10,50 cm × 0.01 mol dm × 4 × 10 × 63.55 g mol = 266.9 mg
3 -3 -1
[11.60 – (10.50 / 10 × 4)] cm × 0.1 mol dm × 10 × 138.91 g mol = 1028 mg
3 -3 -1

3 -3
superconductor
TH

n(La) : n(Cu) = 25.90 : 14.00 = 1.85 : 1
Student Code AAA-1
Practical Problems
"Bonding the World with Chemistry"

49th INTERNATIONAL CHEMISTRY OLYMPIAD
Nakhon Pathom, THAILAND
Practical problems (official English version), 49th IChO 2017, Thailand 1

Student Code AAA-1
Practical Exam
Task 1B

Student Code AAA-1
Chemicals and Equipment (Task 1B)
I. Chemicals and materials (the actual labeling for each is given in bold font)
Health Statementsa
Solution A (KIO3 10.7042 g in 5.00 dm3), 60 cm3 H272-H315-H319-H335
in a plastic bottle
Solution B (Saturated Ca(IO3)2 solution), 50 cm3 in H272-H315-H319-H335
a plastic bottle
Solution C (Saturated Ca(IO3)2 in unknown dilute H272-H315-H319-H335
3
KIO3 solution), 50 cm in a plastic bottle
Solution of Na2S2O3 200 cm3 in a plastic bottle
KI 10% (w/v), 100 cm3 in a plastic bottle H300+H330-H312-H315-H319-
H335
HCl 1 mol dm-3, 100 cm3 in a plastic bottle H290-H314-H335
3
Starch solution 0.1% (w/v), 30 cm in a dropping
glass bottle
Distilled water, 500 cm3 in a wash bottle
Distilled water, 1000 cm3 in a plastic gallon
aSee page xx for definition of Risk and Safety Phrases
II. Equipment and labwares

Personal Labwares Quantity
Beaker, 100 cm3 2
Beaker, 250 cm3 1
Erlenmeyer flask, 125 cm3 9
Transfer pipette, 5.00 cm3 2
Transfer pipette, 10.00 cm3 1
Measuring cylinder, 10.0 cm3 1
Pasteur pipette 1
Rubber bulb for Pasteur pipette 1
Glass funnel, 7.5 cm diameter 2
Plastic funnel, 5.5 cm diameter 1
Filter paper in a zipped bag 3
Burette, 50.0 cm3 1
Burette stand and clamp 1
O-ring with bosshead 2

Student Code AAA-1
Task 1B a b c Total
a1 a2 a3 b1 b2 b3 c1 c2 c3
Total 1 5 1 6 1 2 6 1 3 26
Score
Accounted for 13% of Total Score

Task 1B: Calcium iodate
Calcium iodate is an inorganic salt composed of calcium and iodate ions. Ca(IO3)2 is
sparingly soluble in water. Equilibrium is established between the undissolved salt and
saturated solution of the salt.
Ca(IO3)2 (s) Ca2+(aq) + 2 IO3- (aq)
Titration data will be used to determine the concentration of iodate ions in a saturated
solution of Ca(IO3)2 and then to determine the value of Ksp for Ca(IO3)2.
The concentration of iodate ion will be determined by titration with a standard solution
of sodium thiosulfate (Na2S2O3), in the presence of potassium iodide (KI). Starch will be used
as an indicator.
Part a is associated with the standardization of Na2S2O3. Part b is the determination of
Ksp for Ca(IO3)2.
In Part C, solid Ca(IO3)2 is dissolved in an unknown dilute KIO3 solution. After
standing for 3 days, equilibrium is also established between the undissolved salt and saturated
solution of the salt. The concentration of iodate ion will be determined using the same
titrimetric method, and then used to calculate the concentration of the dilute KIO3 solution.
Part a
Standardization of Na2S2O3
1. Fill the burette with Na2S2O3 solution.

2. Pipette 10.00 cm3 of standard KIO3 solution (provided as solution A, KIO3 10.7042 g
in 5.00 dm3) into an Erlenmeyer flask. Add 10 cm3 of 10%(w/v) KI and 10 cm3 of 1
mol dm-3 HCl into a flask. The solution should turn dark brown as I2 is formed.
3. Titrate with Na2S2O3 solution until the solution has turned pale yellow. Add 2 cm3 of
0.1%(w/v) starch solution. The solution should turn dark blue. Titrate carefully to the
colorless endpoint. Record the volume of Na2S2O3 solution.

Student Code AAA-1
a1) Balance relevant chemical equations.
-
…… IO3 (aq) + …… I-(aq) + …... H3O+ (aq)  …… I2(aq) + …… H2O(l)
……I2 (aq) + …… S2O32-(aq)  …… I-(aq) + …… S4O62-(aq)
a2) Record volume of Na2S2O3 solution.

(You do not need to fill in the entire table)
Titration no.
1 2 3
Initial reading of the burette of Na2S2O3 solution, cm3
Final reading of the burette of Na2S2O3 solution, cm3
Consumed volume of Na2S2O3 solution, cm3
Accepted volume, cm3; V1 =
a3) Calculate the concentration of the Na2S2O3 solution.
Concentration of Na2S2O3 , mol dm-3: …………… (answer in 4 digits after decimal point)
(If the student cannot find the concentration of Na2S2O3, use the concentration of 0.0700 mol
dm-3 for further calculations.)

Student Code AAA-1
Part b
Determination of Ksp of Ca(IO3)2
1. You are provided with the filtrate of the filtered saturated solution of Ca(IO3)2.
(Solution B)
2. Pipette 5.00 cm3 of the filtrate into an Erlenmeyer flask. Add 10 cm3 of 10% (w/v) KI
and 10 cm3 of 1 mol dm-3 HCl into a flask.
3. Titrate with Na2S2O3 solution until the solution has turned pale yellow. Add 2 cm3
0.1% (w/v) starch solution. The solution should turn dark blue. Titrate carefully to the
b1) Record volume of Na2S2O3 solution.

Titration no.
1 2 3
b2) Calculate the concentration of the IO3- solution.
Concentration of IO3- , mol dm-3: …………………(answer in 4 digits after decimal point)

Student Code AAA-1
b3) Calculate value of Ksp for Ca(IO3)2.
Ksp for Ca(IO3)2 = ……………………………………(answer in 3 significant figures)
(If the student cannot find Ksp, use the value of 710-7 for further calculations.)
Part c
Determination of concentration of unknown dilute KIO3 solution
1. You are provided with the filtrate of the filtered saturated solution of Ca(IO3)2 dissolved
in the unknown dilute KIO3 (provided as solution C).
2. Pipette 5.00 cm3 of the filtrate solution into an erlenmeyer flask. Add 10 cm3 of 10%
(w/v) KI and 10 cm3 of 1 mol dm-3 HCl into a flask.

Student Code AAA-1
c1) Record volume of Na2S2O3 solution
Titration no.
1 2 3
c2) Calculate the concentration of the IO3- in solution C.
Concentration of IO3-, mol dm-3: ……………………(answer in 4 digits after decimal point)

Student Code AAA-1
c3) Calculate the concentration of the unknown dilute KIO3 sample.
Concentration of IO3- , mol dm-3: ……………… (answer in 4 digits after decimal point)

Student Code AAA-1
Task 1B a b c Total
a1 a2 a3 b1 b2 b3 c1 c2 c3
Total 1 5 1 6 1 2 6 1 3 26
Score
a1) Balance relevant chemical equations.
-
…1… IO3 (aq) + …5… I-(aq) + …6... H3O+ (aq)  …3… I2(aq) + …9… H2O(l) (0.5 points)
…1…I2 (aq) + …2… S2O32-(aq)  …2… I-(aq) + …1… S4O62-(aq) (0.5 points)
a2) Record volume of Na2S2O3 solution.

Titration no.
1 2 3
Accepted volume, cm3; V1 = 12.08 ± 0.20 (5 points)
a3) Calculate the concentration of the Na2S2O3 solution.
(CIO3-  V IO3-)  6 = C S2O32-

VS2O32-
(0.0100  10.00)  6 = 0.0497

12.08
Concentration of Na2S2O3 , mol dm-3: …0.0497… (answer in 4 digits after decimal point)
(1 point)
(If the student cannot find the concentration of Na2S2O3, use the concentration of 0.0700 mol
dm-3 for further calculations.)

Student Code AAA-1
Part b
Determination of Ksp of Ca(IO3)2
1. You are provided with the filtrate of the filtered saturated solution of Ca(IO3)2.
(Solution B)
2. Pipette 5.00 cm3 of the filtrate into an Erlenmeyer flask. Add 10 cm3 of 10% (w/v) KI
and 10 cm3 of 1 mol dm-3 HCl into a flask.
b1) Record volume of Na2S2O3 solution.

Titration no.
1 2 3
b2) Calculate the concentration of the IO3- solution.
(C S2O32-  V S2O32-)  1 = C IO3-

V IO3-  6
(0.0497  13.20)  1 = 0.0219

5.00  6
Concentration of IO3- , mol dm-3: …0.0219…………(answer in 4 digits after decimal point)

(1 point)

Student Code AAA-1
b3) Calculate value of Ksp for Ca(IO3)2.
CCa2+ = C IO3-
2
= 0.0219 = 0.0110
2
Concentration of Ca2+ , mol dm-3: ………0.0110…………………….
Ksp = [Ca2+][IO3-]2
Ksp = (0.0110)  (0.0219)2

= 5.28  10-6
Ksp for Ca(IO3)2 = ……5.28  10-6……………(answer in 3 significant figures) (2 points)

(If the student cannot find Ksp, use the value of 710-7 for further calculations.)
Part c
Determination of concentration of unknown dilute KIO3 solution
1. You are provided with the filtrate of the filtered saturated solution of Ca(IO3)2 dissolved
in the unknown dilute KIO3 (provided as solution C).
2. Pipette 5.00 cm3 of the filtrate solution into an erlenmeyer flask. Add 10 cm3 of 10%
(w/v) KI and 10 cm3 of 1 mol dm-3 HCl into a flask.
c1) Record volume of Na2S2O3 solution

Titration no.
1 2 3

Student Code AAA-1
c2) Calculate the concentration of the IO3- in solution C.
(C S2O32-  V S2O32-)  1 = C IO3-

V IO3-  6
(0.0497  14.43)  1 = 0.0239

5.00  6
Concentration of IO3-, mol dm-3: …0.0239………(answer in 4 digits after decimal point)

(1 point)
c3) Calculate the concentration of the unknown dilute KIO3 sample.
Ksp = 5.28  10-6 = [Ca2+]

[IO3-]2 (0.0239)2
= 0.00924
Concentration of Ca2+, mol dm-3: ………0.00924 …………………………….
[KIO3]sample = [IO3-]in soln.C - [IO3-]solubilized Ca(IO3)2
= 0.0239 - (2  [Ca2+])
= 0.0239 - (2  0.00924)
Concentration of IO3 , mol dm : …0.0542..
- -3
(answer in 4 digits after decimal point)
= 0.0796 (3 point)

Titolazione
permanganometrica
TH
PRACTICAL PROBLEMS
2+
-3
-3
TH
Determine the mass of potassium permanganate in the solution you are given. You
are provided with hydrochloric acid of a given concentration, a potassium hydroxide
solution of an unknown concentration, an oxalic acid solution of an unknown
concentration, and a sulphuric acid solution (2 N).
Equipment and reagents:

A burette for titration, indicators (methyl orange, lithmus, phenolphthalein), pipettes
(volumes 10, and 15 or 20 cm3), 2 volumetric flasks (250 cm3), 2 titration flasks (100 – 150
cm3).
TH
Titrimetric determination of potassium peroxodisulfate (K2S2O8)
A) Principle
To the sample (K2S2O8) a measured amount of a Fe(II) solution is added in an excess.
The excess of the Fe(II) is determined using a standard KMnO4 solution.
B) Procedures
1) Determination of the concentration of the Fe(II) solution, [Fe(NH4)2(SO4)2]
To a titration vessel, 25.0 cm3 Fe(II) solution, 10 cm3 H3PO4 (ca. 3.7 mol dm-3) and 10
cm3 H2SO4 (ca. 1 mol dm-3) are added and titrated with the KMnO4 solution to a pink
colouration. The concentration of KMnO4 in the solution is exactly 0.02 mol dm-3. Two
titrations are carried out and the consumption of the KMnO4 solution is recorded. The
mean value (= V1) is to be given.
2) Determination of peroxodisulfate in the same solution
a) The dissolved sample is diluted with distilled water to 100 cm3 in a standard flask
and mixed.
3 3
b) 25.0 cm of this solution are transferred to a titration vessel and mixed with 10 cm
H3PO4 (ca. 3.7 mol dm-3), 10 cm3 H2SO4 (ca. 1 mol dm-3) and 25.0 cm3 of the Fe(II)
solution. The mixture is allowed to stand for 5 minutes and titrated with the KMnO4
solution (0.02 mol dm-3) to a pink colourization. Two titrations are carried out and the
consumption of the KMnO4 solution is recorded. The mean value (= V2) is to be
given.
C) Calculation and evaluation
I) Reaction equations: To be given:
Partial equations with electron balance
Overall equations
1) Reaction of peroxodisulfate with Fe(II):
Partial:
a) S2O82- ...................................
b) Fe2+ ...................................
c) Overall reaction:
TH
2) Reaction of Fe(II) with permanganate:

Partial:
2+
a) Fe ...................................
b) MnO-4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
c) Overall reaction:
II) The concentration of the Fe(II) solution

3 3
1) Give the consumption of the KMnO4 solution (cm ) for 25.0 cm of the Fe(II) solution
(= V1); See Procedure 1.
2) Calculate the concentration of the Fe(II) solution in mol dm-3.
III) Determination of K2S2O8

1) Give the consumption of the KMnO4 solution in the back-titration of the excess Fe(II)
solution in cm3 (= V2); See Procedure 2.
2) How many mg K2S2O8:
-3
3) Calculate the concentration of K2S2O8 in the sample solution in mol dm .
____________________
SOLUTION
I/1/a S2O82- + 2 e- → 2 SO2-
4
b) Fe2+ → Fe3+ + e- /. 2
S2O82- + 2 Fe2+ → 2 SO2-
3+
c) 4 + 2 Fe
I/2/a Fe2+ → Fe3+ + e- /. 2

MnO-4 + 8 H+ + 5 e- → Mn2+ + 4 H2O
5 Fe2+ + MnO-4 → 5 Fe3+ + Mn2+ + 4 H2O
II/1 V1 cm3 KMnO4 (0.02 mol dm-3) / 25 cm3 Fe(II)

V1 × 0.02 × 5
2. c (Fe2+ ) = = ........ mol/l
25
3 -3
III/1 V2 cm KMnO4 solution (0.02 mol dm ) for the back titration
TH
2.
(V1 − V2 ) × 0.02 × 5 270.33
α) × = ........ mg K 2S2O8
1000 2
25 × c (Fe2+ ) − V2 × 0.02 × 5 270.33

β) × = ........ mg K 2S2O8
1000 2
3.
(V1 − V2 ) × 0.02 × 5 40
α) × = ........ mol K 2S2O8 / dm3
1000 2
25 × c (Fe2+ ) − V2 × 0.02 × 5 40
β) × = ........ mol / dm3
1000 2
TH
A solution in a graduated flask contains a mixture of oxalic acid and ammonium
oxalate.
One of the bottles denoted X, Y, and Z contains a solution of a calibration substance
with reducing character at a concentration of 0.1000 mol dm-3.
You are required to solve the following tasks:
a) Determine the quantity of oxalic acid and of ammonium oxalate in the solution in the
graduated flask. (The result will be given in grams.)
b) Write the formula for the substance with reducing character and the equations of the
chemical reactions which led to its determination.
In order to carry out the analyses the following solutions are available:
HCl (c = 0.1000 mol dm-3), NaOH (c = 2 mol dm-3), KMnO4 (c = 0.02 mol dm-3), 25 %
-3
H2SO4, HNO3 (c = 2 mol dm ), 5 % BaCl2, 5 % AgNO3, 5 % Hg2(NO3)2, phenol-
phthalein 0.1 %, methyl red 1 %.
c) Describe the procedure used in the individual steps, indicators employed and partial
results.
Mr(H2C2O4) = 90.04
Mr((NH4)2C2O4) = 124.11
____________________
SOLUTION
ANSWER SHEET:
A1 – Identification of the solution with the reducing substance X, Y, Z: Fe(NH4)2(SO4)2
A2 – Identification reactions for the ions of the substance
- Fe2+ + 2 NaOH → Fe(OH)2 + 2 Na+
- NH+4 + NaOH → NH3 ↑ + H2O + Na+
- 4 NH3 + 2 Hg2(NO3)2 + H2O → O(Hg)2NH2.NO3 + 3 NH4OH
4 + BaCl2 → BaSO4 + 2 Cl
–
- SO2-
B1– Preparation of the 0.1 M NaOH solution

. . . . . . . . . . . . . . . . cm3 in 200.0 cm3
TH
B2 – Concentration of the NaOH in its solution: . . . . . . . . . . . M

Indicator used: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
C – Concentration of KMnO4 in its solution . . . . . . . . . . . . . M
D1 – Mass of oxalic acid in the initial solution . . . . . . . . . . . . g

Indicator used . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
D2 – Mass of ammonium oxalate in the initial solution . . . . . . . . . . . . . g
Solution
A1 – 1-2 cm3 of solution X, Y and Z are put into three test tubes. 6 N H2SO4 and a drop of
KMnO4 solution are added. The solution which loses colour is the one with reducing
character.
A2 – Establishment of the formula:
. . . . . . . . + NaOH – greenish white precipitate ⇒ Fe2+
. . . . . . . . + NaOH at the upper end of the test-tube, filter paper with a drop of
Hg2(NO3)2 , black spot ⇒ NH+4
. . . . . . . . + BaCl2 – white precipitate ⇒ SO2-

4
. . . . . . . . + AgNO3 + HNO3 ⇒ Cl– is absent

Accordingly the substance used is Fe(NH4)2(SO4)2.
The chemical reactions:
Fe2+ + 2 Na+ + 2 OH– → Fe(OH)2 + 2 Na+
NH+4 + Na+ + OH– → NH3 + H2O + Na+
4 NH3 + 2 Hg2(NO3)2 → O(Hg)2NH2 . NO3 + 2 Hg + 3 NH4NO3
+ 2 Cl– → BaSO4 + 2 Cl–

2+
SO2-
4 + Ba
B1 – 5 cm3 2 M solution ⇒ 100 cm3 0.1 M solution

B2 – V cm3 0.1000 N HCl + 0.1 N NaOH in the presence of phenolphthalein.
C – V cm3 solution X + 10.0 cm3 H2SO4 + H2O is titrated at elevated temperature with
KMnO4.
TH
3
D1 – The solution which is to be analyzed is filled to the mark; V cm of this solution is
titrated with NaOH in the presence of methyl red. The quantity of oxalic acid (moles
and g) is calculated.
D2 – V cm3 solution to be analyzed + 10.0 cm3 6 N H2SO4 + H2O are heated and titrated
with KMnO4 solution.
The total amount of oxalate is calculated (in mol).
The difference gives the amount of ammonium oxalate (moles and g).
TH
PRACTICAL PROBLEMS
Determination of Calcium by Precipitation with Oxalate Followed by Titration with
Permanganate.
In this exercise, you must determine the amount of calcium ion in a solution that
contains both calcium and magnesium, by selectively precipitating only the calcium as
calcium oxalate, then quantitatively removing the precipitate from the solution by filtration.
4 → CaC2O4 (s)
Ca2+ + C2O2-
The precipitate must then be re-dissolved in acid:

CaC2O4 (s) + 2 H → Ca
+ 2+
+ H2C2O4
The liberated oxalic acid is titrated with standard permanganate solution:
5 H2C2O4 + 2 MnO-4 + 6 H → 10 CO2 + 2 Mn
+ 2+
+ 8 H2O
Formation of the calcium oxalate precipitate

3 3
1. Use a 25.00 cm pipette and 250.0 cm volumetric flask to accurately dilute (by a
factor of 10), the calcium/magnesium solution that has been provided for you.
Analyse two samples of the dilute calcium/magnesium solution. You have sufficient
reagents for three analyses, but you must plan your time and use of equipment
carefully. Take each of your samples through the following procedure:
3 3
2. Transfer a 25.00 cm aliquot of the dilute calcium/magnesium solution into a 250 cm
3 3
beaker, add approximately 10 cm of 3 M H2SO4 and about 50 cm of water.
CARE! 3 M H2SO4 is very corrosive! The following steps involve hot (nearly boiling)
solutions. Be careful and beware of steam!
3. Cover the beaker with a watch glass and gently heat on a hotplate until the solution
is very hot, but not boiling.
4. Remove the beaker from the heat, then carefully add solid ammonium oxalate (1.5 g)
and swirl the beaker until most of the ammonium oxalate dissolves.
CARE! Oxalate solutions are toxic. Do not wash solutions that contain oxalate down the
sink. Place them in the “Permanganate/Oxalate residues” bottle at the end of your
bench.
TH
5. Add 5 –10 drops of methyl red indicator to the beaker, then while the solution is hot,
increase the pH of the solution by slowly adding 1 : 1 ammonia solution with constant
stirring, until the colour just changes from pink to orange. If you add too much
ammonia, the solution will turn yellow. To correct this problem, add 1 drop of 3 M
H2SO4 to lower the pH again, then repeat the pH adjustment with ammonia solution.
CARE! 1 : 1 ammonia solution is corrosive and has a very strong smell! Keep the bottle
stoppered when not in use.
6. Allow the solution to stand for at least 60 minutes to quantitatively precipitate the
calcium oxalate. Do not stir the solution during this time.
You should complete Laboratory Task 2 during this waiting period.

Do not proceed to the next step until you are confident that precipitation is complete.
Filtration of the calcium oxalate precipitate

7. Prepare a filter paper in a filter funnel supported in the neck of a 250 cm3 conical
flask. Rinse the paper with a few cm3 of water then decant most of the supernatant
solution from step 6. into the filter funnel. Collect the filtrate in the conical flask. Use
a wash bottle to rinse the watch glass into the filter funnel.
8. Test the filtrate for the presence of calcium ion by adding a drop of ammonium
oxalate test solution to a drop of the filtrate on a black plastic sheet. If a white
precipitate (or cloudiness) is formed, the calcium oxalate precipitation in step 6 was
unfortunately not complete. Perhaps the pH was not adjusted correctly or insufficient
time was allowed for precipitation. Depending on the time you have left, you may
start the analysis again or you may continue with the present experiment.
9. If there is no detectable calcium ion in the filtrate, use a wash bottle to carefully wash
the calcium oxalate precipitate into the filter. Use the rubber “policeman” on the end
of a glass rod to remove the last traces of precipitate from the beaker, and rinse
these into the filter.
10. Wash the precipitate 4 times with approximately 10 cm3 portions of water, collecting
the washings in the conical flask.
TH
11. Discard the combined filtrates from the previous steps into the residue bottle labeled
“Permanganate/Oxalate residues” then carefully rinse the conical flask with water
into the residue bottle.
3
12. Wash the precipitate one more time with 10 cm of water. Collect this filtrate in the
conical flask and test it for the presence of oxalate by adding a drop of saturated
calcium nitrate solution to a drop of the filtrate on a black plastic sheet. If a white
precipitate (or cloudiness) is formed, continue washing and testing until the washings
are free from oxalate.
13. When the precipitate is free of oxalate, discard the washings and rinse and drain the
conical flask.
NOTE! Show your demonstrator your precipitates. You must ask your demonstrator
to sign your results sheet before proceeding to the next step.
14. Use a glass rod to break a small hole in the bottom of the filter paper and wash the
precipitate through the hole into the conical flask with approximately 20 cm3 water.
Take care to rinse the rod and the creases of the filter paper.
15. Use a Pasteur pipette to dissolve any traces of calcium oxalate that remain in the
paper with 25 cm3 3 M sulphuric acid, collecting the acid in the conical flask. Finally,
rinse the paper with ~ 20 cm3 water.
Titration with permanganate

16. Make the volume up to about 100 cm3 with water, heat the solution to about 60 °C,
then when all the calcium oxalate precipitate is dissolved, carefully titrate the hot
solution with standard potassium permanganate solution.
CARE! It is not necessary to measure the temperature of the solution with a
thermometer. 60 °C is uncomfortably hot to touch.
17. Discard the titrated solution into the residue bottle labelled “Permanganate/Oxalate
residues”.
Calculate the average concentration of calcium ion in the original

calcium/magnesium solution that was provided.
TH
-1
Molar masses in g mol : Ca 40.08, Mg 24.31, Mn 54.94, C 12.01, O 16.00.
_______________
SOLUTION
Model solution
Analysis of calcium/magnesium solution
Permanganate titration
-3
Concentration of standard KMnO4 solution: 0.02039 mol dm
initial burette reading (cm3) 0.90 0.80 3.00
final burette reading (cm3) 28.55 28.45 30.80
3
Average titre (cm ) 27.70
In a 25 cm3 aliquot of dilute Ca/Mg solution:

n(KMnO4) required to titrate oxalate from dissolved calcium oxalate precipitate
n(KMnO4) = 0.0198 mol dm-3 × 0.0277 dm3 = 5.485×10–4 mol
n(oxalate) from dissolved calcium oxalate precipitate:
n(oxalate) = 5/2 × 5.485×10–4 mol = 1.371×10–3 mol
n(Ca2+) from dissolved calcium oxalate precipitate = n(oxalate) = 1.371×10–3 mol
c(Ca) = 1.371×10–3 mol / 0.02500 dm3 = 0.0548 mol dm-3
In original Ca/Mg solution:
c(Ca) = 0.0548 mol dm-3
ND
PRACTICAL PROBLEMS
photo chemistry.

K3[Mn(C2O4)3]·xH2O

4 (aq) + 8 H2O(l)
C2O4H2(aq) + CO32- (aq) → C2O2-

4 (aq) + CO2(g) + H2O(l)
4 (aq) + 4 C2O4H2(aq) →
2+
4 Mn (aq) + MnO-4 (aq) + 11 C2O2-
→ 5 [Mn(C2O4)3]3–(aq) + 4 H2O(l)
3 3
ND
3 3
3
3
filtration.
__________

Ability
water before use.

-
I3- (aq) + 2 S2O32- (aq) → 3 I–(aq) + S4O2-

6 (aq)
3 3
3
ND
3
colourless.
__________

Ability

3– +
+

3 3
NTT VN-123
Practical Code: Task 1 2 3 4 5 6 7 8 9 10 Total

Problem 3
Examiner Mark 0 25 2 25 3 4 3 2 5 2 71
13 % of the
total Grade
Practical Problem 3. Analysis of a hydrated zinc iron(II) oxalate double salt
Zinc iron(II) oxalate double salt is a common precursor in the synthesis of zinc
ferrite which is widely used in many types of electronic devices due to its interesting
magnetic properties. However, such double salts may exist with different compositions
and different amount of water depending on how the sample was synthesized.
You will analyze a pure sample of hydrated zinc iron(II) oxalate double salt (Z) in
order to determine its empirical formula.
Procedure
The concentration of the standard KMnO4 is posted on the lab walls.
Bring a clean 250 mL beaker to the lab assistant who will be waiting by the
balance. You will receive a pure sample of Z for analysis. Accurately weigh between
0.7-0.8 g of the pure sample Z onto the weighing paper (m, grams). This should then
be immediately quantitatively transferred into your 250 mL beaker for analysis, and its
mass recorded in table below.
Task 3.1: Record the mass of the sample of pure Z taken.
Mass of sample, m (gram) Lab assistant’s signature
------------------ ---------------------
Analysis of Z
- Using the 100 mL graduated measuring cylinder, measure ca. 30 mL of 30 wt%
H2SO4 solution and add it into the 250-mL beaker containing your accurately
weighed pure sample of Z. To speed up the dissolving of your sample you may use

NTT VN-123
the hotplate stirrer to warm up the mixture, but be careful not to boil it. You
should not use the digital thermometer as the acid may damage it. After the solid
has dissolved, remove the beaker from the hotplate stirrer and cool it to close to
room temperature. After the solution has cooled, quantitatively transfer it into the
100 mL volumetric flask. Add distilled water up to the 100 mL–mark. We will
now call this solution C.
- Use an appropriately labeled beaker to transfer the standardized KMnO4 solution
into the burette graduated with brown marks.
- Use another appropriately labeled beaker to transfer the standardize EDTA solution
into the burette graduated with blue marks.
Titration with KMnO4

a) Using the 5 mL graduated pipette add 5.00 mL of the solution C into a 250 mL
conical flask.
b) To this conical flask add about 2 mL of 30 wt% H2SO4 solution, about 3 mL of
3.0 M H3PO4 solution, and about 10 mL of distilled water. Heat the mixture on the
hot plate stirrer until hot, but be careful not to boil it.
c) Titrate the hot solution with the standardized KMnO4 solution, recording your
burette readings in the table below. At the end point of the titration, the pink color
of the solution appears. Repeat the titration as desired and report your accepted
volume of KMnO4 solution consumed (V1 mL) in the table.
Task 3.2: Record volumes of standardized KMnO4 solution consumed

Titration No
1 2 3 4
Initial reading of the burette of KMnO4, mL
Final reading of the burette of KMnO4, mL
Consumed volume of KMnO4, mL
Accepted volume, V1 = ________ mL

NTT VN-123
Task 3.3: Can aqueous HCl or HNO3 be used instead of H2SO4 for the dissolving of
sample Z and the subsequent analyses?
HCl YES NO
HNO3 YES NO
Titration with EDTA
- Clean both the 250 mL beakers ready for the next part of the experiment. Pipette
10.00 mL of solution C into a 250 mL beaker. Heat and stir the solution on the
hotplate stirrer, but be careful not to boil it. Add ca. 15 mL of 20 wt% NaOH
solution to the beaker and keep it on the hotplate for ca. 3-5 min in order to
complete the precipitation of iron hydroxide, and to convert all Zn2+ ions into the
ionic complex [Zn(OH)4]2-.
- Using a glass funnel and the large quantitative filter paper, filter the hot suspension
directly into the 250 mL conical flask. From this point take care with the
volumes as you will be preparing a standard solution of exactly 100 mL from
the filtrate. As it is filtering, prepare some warm distilled water in a 250 mL
beaker (ca. 50 mL). Wash the precipitate on the filter paper (at least 5 times) with
small portions (ca. 5 mL) of the warm distilled water. Cool the filtrate down and
then quantitatively transfer it into the 100 mL volumetric flask via a glass funnel.
Add distilled water to make up to the 100 mL mark. This will now be referred to as
solution D.
- Pipette 10.00 mL of solution D into a 250 mL conical flask. Add ca.10 mL
ammonia buffer solution (pH = 9 – 10) and a small quantity of the ETOO indicator
using the glass spatula spoon. Mix well to obtain a purple solution. Titrate the
solution with the standardized 2.00 × 10–3 M EDTA solution, recording your
burette readings in table below. At the end point, the color of the solution turns
blue. Repeat the titration as desired and report your accepted volume of EDTA
solution consumed (V2 mL) in the table.

NTT VN-123
Task 3.4: Record the volumes of EDTA solution consumed

Titration No
1 2 3 4
Initial reading of the burette of EDTA, mL
Final reading of the burette of EDTA, mL
Consumed volume of EDTA, mL
Accepted volume,V2 = ________ mL
Determination of the empirical formula of Z
Task 3.5: Calculate the number of moles of Zn2+, n Zn , present in 100 mL of solution
2+
C.
n Zn 2 + (mol): ……………
Task 3.6: Give the ionic equations for the reduction-oxidation reactions taking place
in the titration with KMnO4.

NTT VN-123
Task 3.7: Calculate the number of moles of Fe2+, nFe , present in 100 mL of solution
2+
C. [YOU WILL NEED THE PRECISE CONCENTRATION OF KMnO4

POSTED ON THE WALLS IN YOUR LAB]
V1, mL = …………………………………….
n Fe2 + (mol): …………………………
Task 3.8: Calculate the number of moles of C2O42- anion, nC O , in 100 mL of 2−

2 4
solution C.
nC O 2− = ………………………………………….
2 4

NTT VN-123
Task 3.9: Calculate the number of moles of water, nH O , in the original sample of Z
2
taken for analysis.
Task 3.10: Give the empirical formula of Z:

47th International Chemistry Olympiad. Baku, Azerbaijan, July 20-29, 2015. ABC-1
TASK 2. Analysis of the solution of a chromium – vanadium alloy (12 points)
Quest. # Q1 Q2 Q3a Q3b Q4a Q4b Q5a Q5b Q6 Total

Marks 32 32 1 1 3 2 4 10 5 90
Antiferromagnetic materials show a good prospect in the development of memory devices for ultra-
high-density data storage, the world’s smallest magnetic memory bit using only 12 atoms being one of
prime examples. Vanadium – chromium alloys exhibit antiferromagnetic properties at subzero
temperatures. It is obvious that composition of alloys used in various hi-tech applications should be
accurately controlled.
In this task, you will analyze an aqueous solution simulating the product of digestion of vanadium –
chromium alloy sample. The task consists of two parts:
I. Oxidation of vanadyl (VO2+) to vanadate (VO3-) in the test solution using potassium
permanganate, followed by determination of vanadium (note that chromium (III) is not oxidized
under these conditions).
II. Oxidation of the test solution with ammonium persulfate, followed by titrimetric determination
of the total content of vanadium and chromium with Mohr’s salt (Ammonium iron(II)
sulfate).
Procedure
Note!
- The amount of vanadium and chromium should be calculated and reported in mg per
100 mL of the test solution.
- Start doing this task with Part A, since you will need time to oxidize the test solution to
be analyzed in Part C.
- The 10.00-mL volumetric pipette has two graduation lines. You should pipette a
volume between the two lines.
Part A. Preparation of the solution for determination of vanadium and chromium total content
1. Transfer a 10.00-mL aliquot of your test solution into the 150-mL beaker and add 20 mL of 1M
sulfuric acid using the 25-mL graduated cylinder.
2. Add 6–8 drops of the 0.3% solution of silver nitrate (the catalyst) and heat the mixture on the
hotplate to 70–80°С (position 3), until condensate on the beaker wall appears.
15
Practical examination. Official English version.
3. Add 20 mL of the 10% ammonium persulfate solution to the heated mixture using the 100-mL
graduated cylinder.
4. Continue heating and observe the appearance of yellow color, indicating the formation of
dichromate.
Note! You can perform the determination of vanadium (Part B, 1 – 6), while the mixture is being
heated.
5. Keep heating the mixture for 10-15 min (position 3) after appearance of the yellow color to
decompose the excess of ammonium persulfate (the decomposition is over when you see no
small bubbles in the solution).
6. Cool the solution to ambient temperature.
7. Transfer quantitatively the solution from the 150-mL beaker into the 100-mL volumetric flask,
dilute to the mark with distilled water, stopper the flask and mix thoroughly.
Part B. Titrimetric determination of Vanadium

1. Transfer a 5.00-mL aliquot of the test solution into an Erlenmeyer flask using the graduated
pipette.
Note! The 5.00-mL graduated pipette is self-draining.
2. Carefully add 0.03 M potassium permanganate solution dropwise, shaking the flask after adding
each drop until light pink color appears. Make sure that the light pink color is stable. Remove the
excess of potassium permanganate by adding 0.03 M oxalic acid solution dropwise. Shake the
flask after each drop until the light pink color changes to pale blue. Let the solution stand for
about 1 min to make sure that the pink color has disappeared completely.
3. Transfer 10 mL of the 1M H2SO4 solution into the Erlenmeyer flask using the 25-mL graduated
cylinder.
4. Add 2–3 (not more!) drops of the indicator into the Erlenmeyer flask and shake it vigorously.
Let the flask stand for 2–3 min and observe the purple color appearance.
5. Fill the burette with the Mohr’s salt solution. Use the 100-mL plastic beaker labeled “Waste” to
drain the excess of Mohr’s salt solution from the burette, record the initial reading.
6. Titrate the solution in the Erlenmeyer flask with the Mohr’s salt solution until the color changes
to pure light green through brownish-grey one.
7. Take the final reading of the burette. Repeat as necessary.
16
Q1. Fill in Table 2.

Table 2. Determination of vanadium
Titration № 1 2 3
Initial reading of the burette, mL
Final reading of the burette, mL
Consumed volume, mL
Accepted volume, V1 _____mL
Part C. Titrimetric determination of vanadium and chromium total content in the test solution
1. Wash the 10.00-mL volumetric pipette with distilled water, rinse with the solution prepared in
100-mL volumetric flask (obtained in part A).
2. Pipette a 10.00-mL aliquot into an Erlenmeyer flask, add 10 mL of 1M H2SO4 solution using the
25-mL graduated cylinder.
3. Add 3–4 drops of the indicator. Vigorously shake the flask and let it stand for 3–4 min. Observe
appearance of red color.
5. Titrate the solution in the flask with the Mohr’s salt solution until the color changes to light
yellow-green.
Table 3. Determination of vanadium and chromium total content

Titration No 1 2 3
Consumed volume, mL
17
Part D. Questions and Data Analysis
Q3. Write down the balanced chemical equations for the reactions that take place upon:
a) oxidation of the test solution with potassium permanganate
b) titration of vanadate with Mohr’s salt
a)
b) = VOSO4
a) oxidation of the test solution with ammonium persulfate
b) titration of the oxidized test solution with Mohr’s salt
a)
b)
Q5. Calculate the a) V(IV) and b) Cr(III) concentrations in the test solution. Calculate the amount
of the metals in mg per 100 mL of test solution.
a) Your work: Vanadium:
b) Your work: Chromium:
18
Q6. This protocol can not be applied to the determination of vanadium and chromium in steels, if
the steel was digested by conc. HCl. Give equations of two reactions to explain the reasons behind.
19
TASK 2. Analysis of the solution of a chromium – vanadium alloy (12 points)
Quest. # Q1 Q2 Q3a Q3b Q4a Q4b Q5a Q5b Q6 Total

Marks 32 32 1 1 3 2 4 10 5 90
Antiferromagnetic materials show a good prospect in the development of memory devices for ultra-
high-density data storage, the world’s smallest magnetic memory bit using only 12 atoms being one of
prime examples. Vanadium – chromium alloys exhibit antiferromagnetic properties at subzero
temperatures. It is obvious that composition of alloys used in various hi-tech applications should be
accurately controlled.
In this task, you will analyze an aqueous solution simulating the product of digestion of vanadium –
chromium alloy sample. The task consists of two parts:
I. Oxidation of vanadyl (VO2+) to vanadate (VO3-) in the test solution using potassium
permanganate, followed by determination of vanadium (note that chromium (III) is not oxidized
under these conditions).
II. Oxidation of the test solution with ammonium persulfate, followed by titrimetric determination
of the total content of vanadium and chromium with Mohr’s salt (Ammonium iron(II)
sulfate).
Procedure
Note!
- The amount of vanadium and chromium should be calculated and reported in mg per
100 mL of the test solution.
- Start doing this task with Part A, since you will need time to oxidize the test solution to
be analyzed in Part C.
- The 10.00-mL volumetric pipette has two graduation lines. You should pipette a
volume between the two lines.
Part A. Preparation of the solution for determination of vanadium and chromium total content
1. Transfer a 10.00-mL aliquot of your test solution into the 150-mL beaker and add 20 mL of 1M
sulfuric acid using the 25-mL graduated cylinder.
2. Add 6–8 drops of the 0.3% solution of silver nitrate (the catalyst) and heat the mixture on the
hotplate to 70–80°С (position 3), until condensate on the beaker wall appears.
16
3. Add 20 mL of the 10% ammonium persulfate solution to the heated mixture using the 100-mL
graduated cylinder.
4. Continue heating and observe the appearance of yellow color, indicating the formation of
dichromate.
Note! You can perform the determination of vanadium (Part B, 1 – 6), while the mixture is being
heated.
5. Keep heating the mixture for 10-15 min (position 3) after appearance of the yellow color to
decompose the excess of ammonium persulfate (the decomposition is over when you see no
small bubbles in the solution).
6. Cool the solution to ambient temperature.
7. Transfer quantitatively the solution from the 150-mL beaker into the 100-mL volumetric flask,
dilute to the mark with distilled water, stopper the flask and mix thoroughly.
Part B. Titrimetric determination of Vanadium

1. Transfer a 5.00-mL aliquot of the test solution into an Erlenmeyer flask using the graduated
pipette.
Note! The 5.00-mL graduated pipette is self-draining.
2. Carefully add 0.03 M potassium permanganate solution dropwise, shaking the flask after adding
each drop until light pink color appears. Make sure that the light pink color is stable. Remove the
excess of potassium permanganate by adding 0.03 M oxalic acid solution dropwise. Shake the
flask after each drop until the light pink color changes to pale blue. Let the solution stand for
about 1 min to make sure that the pink color has disappeared completely.
3. Transfer 10 mL of the 1M H2SO4 solution into the Erlenmeyer flask using the 25-mL graduated
cylinder.
4. Add 2–3 (not more!) drops of the indicator into the Erlenmeyer flask and shake it vigorously.
Let the flask stand for 2–3 min and observe the purple color appearance.
6. Titrate the solution in the Erlenmeyer flask with the Mohr’s salt solution until the color changes
to pure light green through brownish-grey one.
17

Table 2. Determination of vanadium
Titration № 1 2 3
Consumed volume, mL
Part C. Titrimetric determination of vanadium and chromium total content in the test solution
1. Wash the 10.00-mL volumetric pipette with distilled water, rinse with the solution prepared in
100-mL volumetric flask (obtained in part A).
2. Pipette a 10.00-mL aliquot into an Erlenmeyer flask, add 10 mL of 1M H2SO4 solution using the
25-mL graduated cylinder.
3. Add 3–4 drops of the indicator. Vigorously shake the flask and let it stand for 3–4 min. Observe
appearance of red color.
5. Titrate the solution in the flask with the Mohr’s salt solution until the color changes to light
yellow-green.
Table 3. Determination of vanadium and chromium total content

Titration No 1 2 3
Consumed volume, mL
18
Master Value (M.V.)
Max grade
y A B z
If A< Value < B, then Grade = Maxgrade

If Value < y, then Grade = 0, If Value > z, then Grade = 0
−y
Maxgrade ∗ Value
A− y
If y < Value < A, then Grade =
Maxgrade ∗ z −zValue
−B
If B < Value < z, then Grade =
For Parts B and C (max marks 32 for each titration)
Parameter Part B Part C

A M.V.-2.5% M.V.-3.5%
B M.V.+2.5% M.V.+3.5%
y M.V.-7.5% M.V.-10%
z M.V.+7.5% M.V.+10%
19
Part D. Questions and Data Analysis
a) oxidation of the test solution with potassium permanganate
b) titration of vanadate with Mohr’s salt
a) 2KMnO4 + 10VOSO4 + 12H2O = 2MnSO4 + 10HVO3 + K2SO4 + 7H2SO4 1 mark
b) 2HVO3 + 2FeSO4 + 3H2SO4 = 2VOSO4 + Fe2(SO4)3 + 4H2O 1 mark
a) oxidation of the test solution with ammonium persulfate
b) titration of the oxidized test solution with Mohr’s salt
a) Cr2(SO4)3 + 3(NH4)2S2O8 + 7H2O = H2Cr2O7 + 3(NH4)2SO4+ 6H2SO4 1.5 mark
2VOSO4 + (NH4)2S2O8 + 4H2O = 2HVO3 +(NH4)2SO4 +3H2SO4 1.5 mark
b) H2Cr2O7 + 6FeSO4 + 6H2SO4 = Cr2(SO4)3 +3Fe2(SO4)3 + 7H2O 1.5 mark
2HVO3 + 2FeSO4 + 3H2SO4 = 2VOSO4 + Fe2(SO4)3 + 4H2O 0.5 mark
Q5. Calculate the a) V(IV) and b) Cr(III) concentrations in the test solution. Calculate the amount
of the metals in mg per 100 mL of test solution.
a) Your work: Vanadium:
a) , mol L-1 3 marks
b) , mg 1 mark
b) Your work: Chromium:
a) , mol L-1
4 marks
b) , mol L-1 2 marks
c) mol L-1 2 marks
d) , mg 2 marks
20
Q6. This protocol can not be applied to the determination of vanadium and chromium in steels, if
the steel was digested by conc. HCl. Give equations of two reactions to explain the reasons behind.
Fe + 2HCl → FeCl2 + H2↑

2FeSO4 + (NH4)2S2O8 → Fe2(SO4)3 + (NH4)2SO4
2Cl- + S2O82- → Cl2 + 2SO42-
(decrease of the amount of ammonium persulfate due to its reaction with excess of iron(II) in
steels)
2.5 marks
+ – – –
Ag + Cl → AgCl↓; AgCl + Cl → AgCl2
(reaction between the catalyst and chloride)
2.5 marks
21
Titolazione
argentometrica
TH
duplicate.
A) Sample solution:
B) Blank solution:
250 ml.
Note:
stopper.
1.6 M.

TH

persist.
Questions:
TH
Volumetric Determination of Bromide by Back-titration with Thiocyanate after
Precipitation with Silver Ions in Excess
Moments worth considering:

• The candidates must consider the number of significant figures that will be
reasonable in the results.
• The candidates must be able to carry out the whole analysis by using the delivered
portions of silver nitrate and potassium thiocyanate. Supplementation of these two
solutions will not be available.
• Only one 25 cm3 pipette will be at disposal for each candidate.
Principle
Bromide is precipitated as silver bromide after a known amount of silver ions has
been added in excess.
Ag+(aq) + Br-(aq) → AgBr(s) (faint yellow-green)
The excess of silver ions is titrated with thiocyanate with a known concentration, after a
previous standardization of the thiocyanate solution.
During the titration of the following reaction takes place resulting in the precipitation
of silver thiocyanate:
Ag (aq) + SCN-(aq) → AgSCN(s)
+
(white)
Fe(III) is added as indicator producing a red-coloured ion at the equivalence point:
Fe3+(aq) + SCN-(aq) → FeSCN2+(aq) (red)
a) Procedures
Every candidate has got a 0.5 dm3 brown bottle with screw cap, containing the
potassium thiocyanate solution (about 0.08 M) and also a 0.25 dm3 brown bottle with
screw cap, containing the silver nitrate solution. The concentration of this solution is
0.1000 M. The exact concentration of the KSCN solution is to be determined by the
candidates.
TH
i) Determination of bromide in the unknown sample solution

3
Fill the 250 cm volumetric flask containing the bromide sample solution to the mark
with water. Transfer three 25.00 cm3 portions (pipette) of the sample solution to three
3
Erlenmeyer flasks. Add about 5 cm of 6 M nitric acid (measuring cylinder) to each flask.
3 3
Transfer 25.00 cm (pipette) of the accurately known silver solution and about 1 cm of
iron(III) indicator (ind.) (measuring cylinder) to each solution.
Titrate the contents of the three aliquots with the potassium thiocyanate solution. The
end-point of the titration is detected when the solution (including the precipitate) becomes
permanently very faint brownish. It is important to shake the contents vigorously near the
end-point and rinse the walls of the flask with water. The colour should be stable for at
least one minute.
ii) Standardization of the potassium thiocyanate solution

3
Transfer 25.00 cm (pipette) of the silver nitrate solution to an Erlenmeyer flask, add
about 5 cm3 of 6 M nitric acid and about 1 cm3 of the iron(III) indicator solution and about
3
25 cm of water (use measuring cylinders for these solutions). Titrate the contents with the
thiocyanate solution and determine the end-point according to the instruction given in the
"Determination" procedure.
Atomic mass: Ar(Br) = 79.90
b) Exercise
At the equivalent point the solution is saturated with respect to both AgBr and
AgSCN. Find the molar concentration of free (unprecipitated) Br- in this solution:
Ksp(AgBr) = 5.00×10-13 Ksp(AgSCN) = 1.00×10-12
Ignore the effect of pH and Fe(III) species.
Note:
On the answer sheet, not only the required final results shall be given, but also
examplifications of how the calculations are carried out.
TH
When potassium hexacyanoferrate(II), K4[Fe(CN)6] is added to a solution containing
zinc ions, an insoluble precipitate forms immediately. Your task is to find out the
composition of the stoichiometric precipitate that contains no water of crystallization.
The precipitation reaction is quantitative and so quick that it can be used in a
titration. The end point can be detected using redox indication, but first the concentration
of the potassium hexacyanoferrate(II) solution has to be determined.
Preparation of K4[Fe(CN)6] solution and determination of its exact concentration

Dissolve the solid K4[Fe(CN)6].3H2O (M = 422.41 g/mol) sample in the small
Erlenmeyer flask and quantitatively transfer it into the 100.00 cm3 volumetric flask. Take
10.00 cm3 portions of the hexacyanoferrate(II) solution. Add 20 cm3 1 mol/dm3 sulfuric
acid and two drops of the ferroin indicator solution to each sample before titration. Titrate
3 4+
with the 0.05136 mol/dm Ce solution. Repeat titration as necessary. Cerium(IV) is a
strong oxidant under acidic conditions forming Ce(III).
2.1 Report the Ce4+ solution volumes consumed.
2.2 Give the equation for the titration reaction. What was the mass of your
K4[Fe(CN)6].3H2O sample?
The reaction between zinc ions and potassium hexacyanoferrate(II)

Take 10.00 cm3 of the hexacyanoferrate(II) solution and add 20 cm3 1 mol/dm3
sulfuric acid. Add three drops of indicator solution (diphenyl amine) and two drops of
K3[Fe(CN)6] solution. The indicator only works if the sample contains some
hexacyanoferrate(III), [Fe(CN)6]3–. Titrate slowly with the zinc solution. Continue until a
bluish violet colour appears. Repeat titration as necessary.
2.3 Report the zinc solution volumes consumed.
2.4 Interpret the titration answering the questions on the answer sheet.
Mark the correct answer:
The diphenyl amine indicator changes in colour at the end point
a) because the concentration of the Zn2+ ions increases.
b) because the concentration of the [Fe(CN)6]4– ions decreases.
c) because the concentration of the [Fe(CN)6]3– ions increases.
d) because the indicator is liberated from its complex.
TH
Which form of the indicator is present before the end point?

a) Oxidized
b) Reduced
c) Complexed to a metal ion
At the beginning of the titration the redox potential for the hexacyanoferrate(II) -
hexacyanoferrate(III) system is lower than the redox potential of the diphenyl amine
indicator.
a) True
b) False
2.5 Determine the formula of the precipitate.

_______________
SOLUTION
4+
2.1 Ce consumptions:
3
Full marks if V1 is within 0.15 cm of the expected value recalculated from the
K4[Fe(CN)6] mass. Zero marks if deviation is more than 0.50 cm3. Linear scale is
applied in between.
2.2 The titration reaction:
Ce4+ + [Fe(CN)6]4– = Ce3+ + [Fe(CN)6]3–
Ce4+ + Fe2+ = Ce3+ + Fe3+
2.3 Zinc consumptions:
Full marks (25 pts.) if V2 is within 0.15 cm3 of the expected value recalculated from
K4[Fe(CN)6] mass, zinc concentrations and empirical ratio. Zero marks if the
deviation is more than 0.50 cm3. Linear scale is applied in between.
2.4 Solutions: b), b), a)
2.5 Determine the formula of the precipitate. Show your work.
The mole ratio of the zinc : hexacyanoferrate(II) in the precipitate can be evaluated
as:
n(Zn) 10 c (Zn) V2 M
=
n(Fe(CN)6 ) m
Values for c(Zn) are distributed according to a certain plan.
TH
The empirical ratio obtained from the experiments is 1.489.
Calculating the zinc/hexacyanoferrate(II) ratio:

Cations are needed to make the precipitate neutral and only potassium is present.
The precipitate is K2Zn3[Fe(CN)6]2.
Any other reasonable calculation giving the same result is accepted.
Hydrogen instead of potassium (H2Zn3[Fe(CN)6]2 or KHZn3[Fe(CN)6]2) is also
acceptable.
ST
Analysis of a Copper(II) Complex

You are provided with a sample of an inorganic copper(II) complex, the anion of
which is made from copper, chlorine, and oxygen. The counter ion is the tetramethyl
ammonium cation. There is no water of crystallisation. You are required to determine
proportions of copper ions and chloride ions by titration and hence determine the
composition of the complex.
Chemicals
vials labelled ‘Sample 1’, ‘Sample 2’, ‘Sample 3’.
vials labelled ‘Sample 4’, ‘Sample 5’ and ‘Sample 6’.
• pH 10 ammonia buffer, 10 cm3.
• Murexide indicator, solution in H2O, 10 cm .
3
• EDTA disodium salt, aqueous solution, c = 0.0200 mol dm–3, 150 cm3.
• Ethanoic acid, 10 cm3.
• 2,7-Dichlorofluorescein indicator, solution in 7 : 3 EtOH : H2O), 10 cm .
3
• Dextrin, 2 % solution in H2O, 25 cm3.

• Silver nitrate, aqueous solution, c = 0.1000 mol dm–3, 150 cm3.
Procedure
Titration to determine the proportion of copper ions
(a) You are provided with three accurately pre-weighed samples of copper complex,
(b) Add pH 10 ammonia buffer solution until the precipitate which forms initially just
redissolves (about 10 drops).
(c) Add 10 drops of the murexide indicator.
ST
–3
(d) Titrate with the 0.0200 mol dm EDTA solution until the solution turns violet and the
colour persists for at least 15 seconds. Record the volume of solution used in the
titration.
(e) Repeat if necessary with samples 2 and 3.
may either be an average value, or a single value you feel most confident in.
2.1 Calculate the volume of EDTA solution needed to react completely with 0.100 g of
complex.
2.3 Calculate the percentage by mass of copper in the sample.
You will need to wash out your burette before you start the titration for the
determination of chloride ions. Any remaining EDTA solution may be disposed of into the
waste containers labelled ‘EDTA’.
Titration to determine the proportion of chloride ions present

(f) You are provided with three accurately pre-weighed samples of copper complex
(g) Add 5 drops of ethanoic acid, followed by 10 drops of dichlorofluorescein indicator
and 5 cm3 dextrin (2 % suspension in water). Shake the bottle well before adding the
dextrin suspension.
(h) Titrate with the 0.1000 mol dm–3 silver nitrate solution, swirling constantly until the
white suspension turns pink and the colour does not disappear after swirling.
(i) Repeat if necessary.
may either be an average value, or the value you feel most confident in.
2.4 Calculate the volume of silver nitrate solution needed to react completely with
0.200 g of complex.
ST

2.6 Calculate the percentage by mass of chloride ions in the sample.
The percentage of carbon, hydrogen and nitrogen in the complex was determined by
combustion analysis and found to be as follows:
Carbon: 20.87 %; Hydrogen: 5.17 %; Nitrogen: 5.96 %.
2.7 Mark in the answer booklet, which element in the complex has the greatest
percentage error in the determination of its proportion.
Cu Cl O C H N
2.8 Determine the formula of the copper complex. Show your working.
_______________
ST
SOLUTION
2.1 Full marks if answer is Vcorr. ± 0.1 cm3. Zero marks if answer is less than (Vcorr. – 0.5
3 3
cm ) or greater than (Vcorr. + 0.5 cm ), linear point scale is applied in between.
→ [Cu(EDTA)]
2+ 4– 2–
2.2 Cu + EDTA
× V(EDTA) (in dm ) = (0.0200 mol dm × V) mol
–3 3 –3
2.3 n(EDTA) = 0.0200 mol dm
× V) mol
2+ –3
n(Cu ) = (0.0200 mol dm
m(Cu) = M(Cu) × n(Cu) = 63.55 g mol × (0.0200 mol dm × V) mol
–1 –3
m (Cu)
% Cu = × 100
m(sample)
2.4 Full marks if answer is Vcorr. ± 0.1 cm3.
Zero marks if answer is less than (Vcorr. – 0.5 cm3) or greater than (Vcorr. + 0.5 cm3),
linear point scale is applied in between.
2.5 Ag+ + Cl– → AgCl
2.6 n(Ag+) = 0.100 mol dm–3 × V(Ag+) (in dm3) = (0.100 mol dm–3 × V) mol
n(Cl–) = (0.100 mol dm–3 × V) mol
m(Cl) = M(Cl) × n(Cl) = 35.45 g mol-1 × (0.100 mol dm–3 × V) mol
m (Cl)
% Cl = × 100
m(sample)
2.7 If the percentage of oxygen is calculated by subtracting all the others from 100, it has
all the errors from the determination of the other elements combined. In practice this
leads to a large error which affects the subsequent calculation of the formula unless
this point is appreciated.
Cu Cl O C H N
2.8 Full marks if the formula is correctly calculated from the student data and the large
error in oxygen is taken into account (either by using one of the proportions of the
other elements to determine the elemental ratios, or by a consideration of charge
balance).
RD
PRACTICAL PROBLEMS
Analysis of Chloride Mixtures
Introduction
Composition of a solution containing only MgCl2 and NaCl can be determined by an
indirect titration method by performing a precipitation titration to determine the total
amount of chloride present, followed by a complex formation titration to determine the
amount of magnesium ions. A common precipitation titration technique used to determine
the amount of chloride ions present in a solution is the Fajans method. In this
argentometric procedure, silver nitrate is used as the titrant to precipitate the chloride ions
present in the solution. The end point is detected through the use of an adsorption
indicator, typically dichlorofluorescein, a weak organic acid. Prior to the end point, silver
chloride particles are negatively charged because of the adsorption of excess chloride ions
present in solution. The indicator anions are repelled by the negatively charged surface of
the silver chloride particles imparting a yellow-green colour to the solution. Beyond the
equivalence point, however, silver chloride particles adsorb silver ions. Thus a positively
charged layer is formed and it attracts the dichlorofluoresceinate ions displaying a pink-red
colour. Dextrin is used to stabilize the silver chloride particles against the coagulation.
On the other hand, the amount of magnesium ions present in a solution can be
determined by complexometric titration with ethylenediaminetetraacetic acid, EDTA. As a
hexadentate ligand, EDTA forms chelates with all metal ions, except alkali metal ions, in a
1 : 1 mole ratio regardless of the charge of the cation. Eriochrome Black T (EBT) is a
common indicator used for EDTA titrations. When pH > 7.00 EBT imparts a blue colour to
the solution in the absence of metal ions and forms a red colour when coordinated to
metal ions.
In this experiment the chloride content of the solution containing MgCl2 and NaCl will
be determined by Fajans method. Magnesium ion concentration will be determined by
EDTA titration.
RD
3
A 100 cm solution prepared by dissolving MgCl2 and NaCl in water is given as the
3
unknown sample. The task is to determine the mass concentration (in g/100 cm ) of both
MgCl2 and NaCl in the unknown solution.
Reagents
• Unknown solution, 100 cm3
• Dextrin in Eppendorf tubes (3) in a zipper bag
• Dichlorofluorescein, indicator
• AgNO3 solution, c = 0.1 mol dm-3 *), 100 cm3
• EDTA solution, c = 0.01 mol dm-3 *), 100 cm3
• pH 10 buffer (NH3/NH4Cl), 5 cm3
• Eriochrome Black T, indicator
_______________
*) The exact value of the concentration is given on the label.
A. Determination of total chloride concentration by Fajans method

1. Using a 10 cm3 pipette, transfer 10.0 cm3 aliquot from the bottle labelled as unknown
solution into a 250 cm3 Erlenmeyer flask. Complete the volume to approximately
100 cm3 by adding distilled water.
2. Take one of the Eppendorf tubes given in the zipper bag labelled as “dextrin” and
transfer all its content into the Erlenmeyer flask.
3. Add 5 drops of dichlorofluorescein indicator solution.
4. Record the exact concentration of AgNO3 in standard solution.
5. Fill one of the burettes with the standard AgNO3 solution.
6. Titrate the unknown solution until the whole solution has pink-red colour.
7. Record the volume of AgNO3 used in cm3.
distilled water.
B. Determination of Mg2+ by direct titration with EDTA

1. Fill the second burette with the standard EDTA solution.
2. Record the exact concentration of EDTA in standard solution.
RD
3 3
3. Using a 25 cm pipette, transfer a 25.0 cm aliquot of the unknown solution into a
3 3
250 cm Erlenmeyer flask. Complete the volume to approximately 100 cm by adding
distilled water.
3 3
4. Using a 1 cm pipette, add 1.0 cm of pH 10 buffer.
5. Add 3 – 4 drops of EBT indicator solution.
6. Titrate the unknown solution with standard EDTA solution until the colour changes
from red to blue.
3
7. Record the volume of EDTA solution used, in cm .
water.
Treatment of Data
1.1 Determine the amount of Cl– ions (in mmol) in 100 cm3 of the unknown solution.
2+ 3
1.2 Determine the amount of Mg ions (in mmol) in 100 cm of the unknown solution.
1.3 Calculate the concentration of both MgCl2 and NaCl in g/100 cm3 in the unknown
solution.
_______________
RD
SOLUTION
1.1 – 1.3
Some distribution graphs were proposed by the organizer and approved by the
International Jury that could be applied for evaluating of accuracy of the titrations
and, consequently, for awarding points.
For determinations of amounts of substance of Cl– and Mg2+ ions, as well
concentrations of both MgCl2 and NaCl in the unknown solution, simple
stoichiometric calculations can be applied.
Code: XXX-01
Instructions
 You have a 15 minute reading time before you start work. Begin reading only
when the START command is given.
 Follow the safety rules announced in the preparatory tasks. You get one warning
for violations. On the second warning you will get disqualified.
 Wear your lab coat and safety goggles while in the lab. Ask your lab assistant for
the gloves of your size when you need them.
 Use only the pen, marker pen and calculator provided. Do not write with the
marker on paper; use it only to label glass or plastic labware.
 Make sure that your student code is on every answer sheet.
 All answers must be written in the appropriate boxes on the answer sheet.
Anything written elsewhere will not be graded. Use the reverse of the exam
sheets if you need scratch paper.
 You have no access to sinks in the lab. You are provided with a sufficient quantity
of labware. Only a few items need to be used again. Wash these carefully with
appropriate solvent into the waste container. Use the brush if needed. Distilled
water and paper tissues are freely available.
 Liquid waste is to be put into the container labeled “LIQUID WASTE”. Do not put
rubbish (tissues, plastic, etc.) in this container, but into the waste baskets in the
lab.
 Chemicals and labware are not supposed to be refilled or replaced. Each such
incident (other than the first in the entire exam, which you will be allowed) will
result in the loss of 1 point from your 40 practical points.
 Raise your hand if you have a safety question or you need a restroom break or
drinking water.
 When you have finished the examination, put your answer sheet into the
envelope provided and leave it on the table. Do not seal the envelope.
 You must stop your work immediately when the STOP command is given. A delay
in doing this may lead to cancellation of your exam. Do not leave your place until
permitted by the lab assistants. You can keep the task text.
 The official English version of this examination is available on request only for
clarification.
Instructions specific for Part II

 The working time for Part II (Task 2 and 3) is 200 minutes.
 Start Part II with Task 2. When you are ready to start with Task 3, tell the lab
assistant, and you will receive the chemicals and labware for Task 3. Reagents for
Task 2 will be taken away from you at this point.
 Part II of the exam (Task 2-3) contains 10 pages, its answer sheets have 7 pages.
 Ask the lab assistants when you need your alcohol lamp lighted. Heat only glass
test tubes. Close the alcohol lamp with the cap when finished.

Code: XXX-01
Labware
Item Quantity
Paper tissue 5
Permanent marker 1
Soft plastic cups 3
Tasks 2 and 3, for each student, on the table
Container with a screw cap for waste,3 dm3, labeled “Liquid Waste, 1
Tests 2&3”
Laboratory stand with double burette clamp 1
Burette, 25.00 cm3 2
Bulb (Mohr) pipette, 10.00 cm3 1
Erlenmeyer flask, 100 cm 3 2
Graduated cylinder, 10.0 cm 3 2
Brush 1
Polypropylene funnel, 5.5 cm 1
Pipette filler 1
Pasteur pipettes for indicators 2
Task 3, for each student, get from the lab assistants
Alcohol lamp 1
Test tube holders, wooden 1
Glass test tubes 10
Pasteur pipettes 10

Code: XXX-01
Chemicals
Glass bottle
Aqueous
Nitric acid 2M -* with dropper HNO3
solution
cap, 250 cm3
Glass bottle
Water sample Aqueous To be Water
100 cm3 with screw
solution solution determined sample
cap, 100 cm3
Glass bottle
Sodium Aqueous 9 mg/dm3 in F−, 9
50 cm 3 with screw
fluoride solution fluoride mg/dm3
cap, 50 cm3
Zirconyl Acidic 0.055% ZrOCl2, Glass bottle
Zirconyl
Alizarin aqueous 0.028% 10 cm 3 with screw
Alizarin
indicator solutions Alizarin Red S cap, 25 cm3
Glass bottle NaCl,
Sodium Aqueous
0.0500 M 50 cm3 with screw 0.0500
chloride solution
cap, 50 cm3 M
Ammonium Aqueous
Glass bottle,
iron(III) sulfate acidic 20 g/dm3 10 cm3 Fe3+ ind.
15 cm3
dodecahydrate solution
Amber glass
Aqueous To be
Silver nitrate 200 cm 3 bottle, AgNO3
solution determined
250 cm3
See exact Glass bottle NH4SCN,
Ammonium Aqueous
concentration 100 cm3 with screw X.XXXX
thiocyanate solution
on the label cap, 100 cm3 M
Potassium Aqueous Glass bottle,
10% 5 cm3 K2CrO4
chromate solution 15 cm3
Glass bottle
Ethanol Liquid 95 % 150 cm 3 with dropper C2H5OH
cup, 250 cm3
Organic
Liquid Syringes,
unknowns 1 to - 0.5 cm3 1 to 8
2 cm3
8
Potassium Aqueous Amber glass
0.13 % 5 cm3 KMnO4
permanganate solution bottle, 50 cm3
Ammonium 2.0 M HNO3
HDPE bottle,
cerium(IV) aqueous 28.6 % 5 cm3 Ce(IV)
30 cm3
nitrate reagent solution
Glass bottle,
Acetonitrile Liquid - 45 cm3 CH3CN
50 cm3

Code: XXX-01

Sulfuric acid
2,4-Dinitrophe- solution in
HDPE bottle,
nylhydrazine aqueous 3% 20 cm3 DNPH
30 cm3
reagent ethanol
0.5 M HCl
Iron(III) HDPE bottle,
aqueous 2.5 % 1 cm3 FeCl3
chloride 30 cm3
solution
Hydroxylamine Ethanolic HDPE bottle, NH2OH
0.5 M 10 cm3
hydrochloride solution 30 cm3 HCl
Sodium Aqueous HDPE bottle,
6M 5 cm3 NaOH
hydroxide solution 30 cm3
Hydrochloric Aqueous HDPE bottle,
1M 25 cm3 HCl
acid solution 30 cm3
*In the quantity left after doing Task 1.
Periodic table with relative atomic masses
1 18
1 2
H He
1.008 2 13 14 15 16 17 4.003
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
6.94 9.01 10.81 12.01 14.01 16.00 19.00 20.18
11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
22.99 24.30 3 4 5 6 7 8 9 10 11 12 26.98 28.09 30.97 32.06 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.10 40.08 44.96 47.87 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.38 69.72 72.63 74.92 78.97 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.95 - 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba 57-71 Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9 137.3 178.5 180.9 183.8 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 - - -
87 88 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
Fr Ra 89-
103 Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
- - - - - - - - - - - - - - - - -
57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
138.9 140.1 140.9 144.2 - 150.4 152.0 157.3 158.9 162.5 164.9 167.3 168.9 173.0 175.0
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
- 232.0 231.0 238.0 - - - - - - - - - - -

Code: XXX-01
Task 2
Determination of fluoride and chloride content in mineral water
Georgia is world famous for its splendid mineral waters. Many of these are used to cure
various diseases. Manufacturers have to carefully control the ionic composition of waters,
fluoride and chloride being among the most important ions.
Visual colorimetric detection of fluoride

The method of fluoride determination is based on the decrease in the color intensity of
zirconium(IV)-Alizarin Red S complex in the presence of fluoride ions due to formation
of a more stable colorless complex. The equilibrium is achieved in about 20 minutes
after the reagent addition. The fluoride concentration is determined visually by
comparing the color developed in the sample with those in the calibration solutions.
Transfer 9.0 cm3 of mineral water from the sample into the plastic test tube labeled “X”.
Calculate how much of the 9.0 mg/dm3 standard fluoride solution you will need to
prepare a set of calibration solutions with the following fluoride ion content: 0.0; 1.0;
2.0; 3.5; 5.0; 6.5; 8.0 mg/dm3 (calculate for 9.0 cm3 of each solution).
Using the 1.0 cm3 and 10.0 cm3 graduated pipettes, add the
calculated amounts of the standard fluoride solution to the test-
tubes, then add 1.0 cm3 of Zirconyl Alizarin indicator into each test
tube, and bring the volume in each calibration test tube to the 10.0
cm3 mark with distilled water (the mark is shown in the figure with
the arrow).
2.1.1. Report the fluoride volumes used in your dilutions.

Mix the obtained solutions in the test tubes. Set the tube rack aside for at least 20
minutes.
2.1.2. Compare the color of the sample and the calibration solutions looking on them
from the top down and from the front. Select the concentration of the standard
that is closest to the fluoride concentration of the water sample.
Note: the rack with the test tubes will be photographed by the lab staff after the whole
exam is finished.
Standardization of silver nitrate solution by the Mohr method

Transfer 10.0 cm3 of the standard 0.0500 mol/dm3 NaCl solution into an Erlenmeyer
flask using the bulb (Mohr) pipette. Add approximately 20 cm3 of distilled water and
10 drops of 10% aqueous K2СгО4 solution.

Code: XXX-01
Fill a burette with the silver nitrate solution. Titrate the contents of the flask with the
silver nitrate solution while vigorously mixing the solution containing the precipitate
formed. The final titrant drops are added slowly with vigorous swirling of the flask. The
titration is complete when the faint color change visible on titrant addition does not
disappear in the pure yellow suspension. Take the final burette reading. Repeat the
titration as necessary.
2.2.1. Report your volumes on the answer sheet.
2.2.2. Write balanced chemical equations for the titration of NaCl with AgNO3 and for
the end-point indication reaction.
2.2.3. Calculate the concentration of the AgNO3 solution from your measurement.
2.2.4. The Mohr titration method requires a neutral medium. Write down equations
for the interfering reactions that take place at lower and at higher pH.
Chloride determination by the Volhard method

Wash the bulb (Mohr) pipette with distilled water. Wash the Erlenmeyer flasks first with
a small portion of the ammonia solution left over from Task 1 to help removing the
silver salt precipitate and then with distilled water. (In case you used up all the ammonia
solution in the first task, you can get a refill without penalty.)
Transfer a 10.0 cm3 aliquot of the mineral water from the sample into an Erlenmeyer
flask using the bulb (Mohr) pipette. Add 5 cm3 of 2 mol/dm3 nitric acid using a
graduated cylinder. Add 20.00 cm3 of the silver nitrate solution from the burette and mix
well the suspension. Add appr. 2 cm3 of the indicator (Fe3+) solution with the Pasteur
pipette.
Fill the second burette with the standard ammonium thiocyanate solution (see the exact
concentration on the label). Titrate the suspension with this solution while vigorously
swirling. At the end point one drop produces a faint brown color that is stable even after
intense mixing. Take the final burette reading. Repeat the titration as necessary.
Note. The AgCl precipitate exchanges Cl− ions with SCN– ions from the solution. If you
titrate too slowly or with breaks, the brown color disappears with time, and too much
titrant is spent for the titration. Therefore when approaching the endpoint you should
add the titrant at a constant slow rate swirling the flask constantly so that the suspension
would stay white. The appearance of faint brown color will mean reaching the endpoint.
2.3.2. Write down balanced chemical equations for the back titration with NH4SCN
and that for the end-point indication reaction.
2.3.3. Calculate the chloride concentration (in mg/dm3) in the water sample from your
measurements.
2.3.4. If Br−, I−, and F− ions are present in the sample in addition to chloride, the
concentration of which ion(s) will contribute to the result of the Volhard
titration?

Code: XXX-01
2.3.5. When trying to determine the concentration of Cl− in the presence of other
halides, an analyst added some potassium iodate and sulfuric acid to the sample
and boiled the solution. Afterwards he reduced the excess of iodate to iodine by
boiling the sample with phosphorous acid H3PO3. What interfering anions were
removed by this operation? Write the chemical equations for the reactions of
these ions with iodate.

Code: XXX-01

2.1.1 2.1.2 2.2.1 2.2.2 2.2.3 2.2.4 2.3.1 2.3.2 2.3.3 2.3.4 2.3.5 Sum
2 15 30 2 2 2 30 2 4 2 4 95
2.1.1. Report the fluoride volumes used in your dilutions.

F− content (mg/dm3) 0.0 1.0 2.0 3.5 5.0 6.5 8.0
Calculated volume of
F− solution (cm3)
2p
2.1.2. Circle the concentration of the standard that is closest to the fluoride
concentration of the water sample. 15p, 5p for adjacent values.
F− content (mg/dm3) 0.0 1.0 2.0 3.5 5.0 6.5 8.0
2.2.1. Report your titration volumes.
Titration no. 1 2
Initial burette reading, cm3
Final burette reading, cm3
Volume spent, cm3
Your accepted volume, V1: cm3 30p on a sliding scale
2.2.2. Write a balanced chemical equation for the titration of NaCl with AgNO3 and
that for the end-point indication reaction.
Titration reaction:
Cl– + Ag+ ⟶ AgCl↓
CrO42–+ 2 Ag+ ⟶ Ag2CrO4↓
Indication reaction:
2p
2.2.3. Calculate the concentration of the AgNO3 solution from your measurement.
Your work:
c(Ag+) = c(Cl–)10.0 cm3 / V1
2p
c(Ag+):

Code: XXX-01
2.2.4. The Mohr titration method requires a neutral medium. Write equations for the
interfering reactions that take place at lower and at higher pH.
Low pH: 2 CrO42–+ 2 H+ ⟶ Cr2O72–+ H2O (dichromic or chromic acids also accepted),
or Ag2CrO4 + H+  2Ag+ + HCrO4–

High pH: 2 Ag+ + 2 OH– ⟶ Ag2O + H2O
2p
2p
Titration no. 1 2
Initial burette reading, cm3
Final burette reading, cm3
Volume spent, cm3
Your accepted volume, V2: cm3 30p on a sliding scale
2.3.2. Write a balanced chemical equation for the back titration with NH4SCN and that
for the end-point indication reaction.
Titration reaction:
Ag+ + SCN– ⟶ AgSCN↓
SCN– + Fe3+ ⟶ Fe(SCN)2+ or analogous reaction
Indication reaction:
2p
2.3.3. Calculate the chloride concentration (in mg/dm3) in the water sample from your
measurements.
Your work:
c(Cl–) = [20.00 cm3 c(Ag+) − V2 c(SCN–)] M(Cl)/ 10.00 cm3
4p, 3p if in different unit
c(Cl–): mg/dm3

Code: XXX-01
2.3.4. If Br−, I−, and F− ions are present in the sample in addition to chloride, the
concentration of which ion(s) will contribute to the result of the Volhard
titration? Tick the appropriate box(es).
 Br–  I–  F–  none
Br−, I− 2p, 1p if 1 mistake committed
2.3.5. When trying to determine the concentration of Cl− in the presence of other
halogens, an analyst added some potassium iodate and sulfuric acid to the
sample and boiled the solution. Afterwards he reduced the excess of iodate to
iodine by boiling the sample with phosphorous acid H3PO3. What interfering
anions were removed by this operation?
 Br–  I–  F–  none
Br−, I− 2p
Write the reaction equations of these ions with iodate.
5I– + IO3– + 6H+  3I2 + 3H2O

10Br– + 2IO3– + 12H+  5Br2 + I2 + 6H2O (IBr also accepted)
2p
Replacements:
Item Quantity Lab assistant’s Student’s
signature signature

Code: XXX-01
Grading scheme for the titration results
Master Value (M.V.)
Max grade
y A B z
If A< Value < B, then Grade = Max grade
If Value < y, then Grade = 0, If Value > z, then Grade = 0
If y < Value < A, then Grade = Max grade  (Value – y)/(A – y)
If B < Value < z, then Grade = Max grade  (z – Value)/(z – B)
Max
Question M.V., mL A, mL В, mL y, mL z, mL
grade
2.2.1. 10.0 9.9 10.15 9.8 10.4 30p
2.3.1. Theoretical values 0.1 +0.3 0.3 +0.8 30p

Spettrofotometria
UV-Vis
TH
THE 20 INTERNATIONAL CHEMISTRY OLYMPIAD, Espoo, 1988
The spectrophotometric determination of the concentration, acid constant Ka2 and pKa2 of
H2X
Apparatus:
3 3
7 volumetric flasks (100 cm ), 2 beakers (50 cm ), 1 capillary pipette (Pasteur), 1 pipette
3 3
(10 cm ; graduated in intervals of 0.1 cm ), 1 washing bottle, 1 glass rod, 1 container for
waste materials, funnel.
Reagents:
Compound NaHX, aqueous stock solution of Na2X (0.00100 mol dm-3), aqueous solution
of sodium perchlorate (1.00 mol dm-3), aqueous solution of HCl (0.1 mol dm-3), aqueous
solution of NaOH (0.1 mol dm-3).
Procedure:
a) Weigh accurately 183.5 ± 0.5 mg of NaHX and dissolve it in water in a volumetric
flask and dilute up to the 100 cm3 mark. Pipette 15.0 cm3 of this solution into another
3
100 cm volumetric flask and fill up to the mark with water to obtain the stock solution
of NaHX. If you do not use your own material, you will get the NaHX from the service
desk.
b) Prepare 5 solutions, numbered 1-5, in the remaining five 100 cm3 volumetric flasks.
These solutions have to fulfil the following requirements:
- The total concentration of ([X2-] + [HX-]) in each solution must be exactly 0.000100
mol dm-3.
- The concentration of sodium perchlorate in each solution must be 0.100 mol dm-3
to maintain constant ionic strength. The solutions are prepared by pipetting into
each volumetric flask 1-5 the accurate volumes of the NaHX and Na2X stock
solutions, adding a required volume of sodium perchlorate solution and filling up to
the mark with water.
- Solution 1 is prepared by pipetting the required amount of the stock solution of

3
NaHX. Add ca. 3 cm of HCl (aq) with the pipette to ensure that the anion is
completely in the form HX-, before adding the sodium perchlorate solution.
TH
- Solution 5 is prepared by pipetting the required amount of the stock solution of

3
Na2X which is provided for you. Add ca. 3 cm of the NaOH(aq) to ensure that the
2-
anion is completely in the form X , before adding the sodium perchlorate solution.
- The three remaining solutions 2-4 are prepared by pipetting the stock solutions of
NaHX and Na2X in the following ratios before adding the sodium perchlorate
solution:
Solution No. Ratio NaHX(aq) : Na2X(aq)
2 7:3
3 1:1
4 3:7
c) Take the five volumetric flasks to the service centre where their UV-vis spectra will
be recorded in the region 300-500 nm for you. In another service centre the accurate
pH of each solution will be recorded. You may observe the measurements.
d) From the plot of absorbance vs. wavelength, select the wavelength most appropriate
for the determination of pKa2 of H2X, and measure the corresponding absorbance of
each solution.
e) Calculate the pKa2 of H2X from the pH-absorbance data when the ionic strength
I = 0.1 and the temperature is assumed to be ambient (25 oC). Note that:
[H+][ X -] c H + × c X 2 -
K a2 = =
[HX -] c HX -
(A A HX- )[H+] [ +]
K a2 = or A = A x2- - (AA HX- ) H
( A X2- - A) K a2
0.509 × I
pf H + =
1+ I
f) Which of your prepared solutions shows the largest buffer capacity? Calculate this
buffer capacity, P, by any suitable method. You may use the equations given:
 K a [H ]C 
+
P = 2.3 ×  [OH-] + [H+] + 
 (K a+ [H+])2 
TH
 [ 2-] [ -] 
P = 2.3 ×  K w+ + [H+] + X HX 
 [H ] C 
C is the total concentration of the acid.
Kw = 2.0 × 10-14 at I = 0.1 and 25 °C.
TH
THE 34 INTERNATIONAL CHEMISTRY OLYMPIAD, Groningen, 2002
Determination of Iron in Iron Pills

Introduction
Iron is an essential component of hemoglobin, transporting oxygen in the blood to all
parts of the body. It also plays a vital role in many metabolic reactions. Iron deficiency can
cause anaemia resulting from low levels of hemoglobin in the blood. Iron deficiency is the
most widespread mineral nutritional deficiency worldwide. One way to reduce iron
shortage is by treatment with iron pills. The active ingredient in the iron pill to be
examined, is iron(II) present as iron(II) fumarate. Besides this organic iron(II) compound
the pill contains other compounds such as binding agents. The structure of fumaric acid is:
Iron(II) and 1,10-phenanthroline form an orange/red coloured complex

2+
[(C12H8N2)3Fe] . The absorbance of this complex, determined at 510 nm in a buffer
solution (pH=8) is a measure for the iron content of the iron pill. Since 1,10-phenanthroline
only binds to iron(II) and iron(II) is readily oxidized to iron(III), hydroxylammonium chloride
is added to reduce all iron(III) to iron(II). A simplified reaction scheme is:
2 NH2OH + 4 Fe3+ → N2O + 4 H+ + H2O + 4 Fe2+
1,10-Phenanthroline
Procedure
The weight of the iron pill is determined with an accuracy of 1 mg using a balance.
The pill is carefully pulverized in a mortar and transferred quantitatively into a 100 cm3
beaker with the aid of a small amount of distilled water. Hydrochloric acid (5 cm3, 4 M) is
added. The content of the beaker is heated up to approximately 60 °C on a hotplate. The
solution turns a yellow colour.
TH
The beaker is then placed in an ultrasonic bath for at least 5 minutes. The beaker is
kept in place by styrofoam. The suspension is filtered by suction using a Hirsch funnel
containing a small layer of moistened hi-flow filter aid pressed onto the filter. The hi-flow
filter aid is washed with ample distilled water. The filtrate is carefully transferred into a
3
volumetric flask (250 cm ) and the final volume adjusted by adding distilled water and with
regular mixing. An amount of 10 cm3 is pipetted from this solution and transferred into a
3
volumetric flask of 100 cm . Again the volume is adjusted with distilled water while mixing
the content of the flask.
3
From this solution, 10 cm is pipetted and transferred into a volumetric flask of 100
cm3. Subsequently, 1,10-phenanthroline solution (10 cm3) and hydroxylammonium
chloride solution (1 cm3) are added. Then the volume is adjusted with buffer solution (pH
8).
The absorbance of this solution is measured with a spectrophotometer at 510 nm
against water as a blank in a 1.000 cm cell.
Calculate the amount of iron in the iron pill on basis of the known molar absorptivity
(extinction coefficient, ε) of the iron(II)phenanthroline complex at 510 nm. The molar
absorptivity of the iron(II)phenanthroline complex at 510 nm is 11100 M-1cm-1.
Important
In order to eliminate deviations in absorbance typically connected to the
spectrophotometer used, a correction factor is denoted on the spectrophotometer you will
be using for your experiment. The absorbance observed must be multiplied by this factor
in order to obtain the correct absorbance of the solution of the iron complex.
_______________
SOLUTION
The competitors were expected to show the following data, tables, graphs or calculations:
1. Weight of the iron pill in mg.
2. Reading of the spectrophotometer and corrected absorbance.
3. Calculation of the concentration of iron(II)phenanthroline complex in the cell in
mmol dm-3.
4. Calculation of the total amount of iron(II) in the pill in mg.
5. Calculation of the iron content of the pill in weight %.
TH
PRACTICAL PROBLEMS
Reverse-phase Chromatography: Spectrophotometric Analysis
Chromatographic separation followed by spectrophotometric analysis is one of the
most widely practiced analytical techniques in chemical laboratories around the world. For
example, organic compounds in a complex mixture are often analyzed by reverse-phase
liquid chromatography with spectrophotometric detection. In reverse-phase chromato-
graphy, hydrophobic interactions between the stationary phase material (usually octadecyl
group) and the non-polar moiety of the analyte is utilized. The chromatogram can be
simplified and the compound of interest selectively determined by proper choice of the
detector wavelength. In this part of the Practical Test, spectrophotometric analysis of
dyes, with and without separation, will be performed.
Food Red No. 40 Methyl Violet 2B
1.1 Spectrophotometric Analysis of R and B in a Mixed Solution

a) Measure absorbance of both Solutions R (3.02×10-5 M) and B (1.25×10-5 M)
(Fig. A & B). Fill in the Table in the Answer Sheet with your measurements.
Draw absorption spectra for the red dye in red ink and for the blue dye in blue
ink (Fig. 1.1).
b) Repeat absorbance measurements for Solution MD. Solution MD is a mixture
of Solution R and B in a certain ratio. Add the spectrum in black ink to Fig. 1.1.
TH
c) Based on the Beer-Lambert law, determine the molar concentration of both

dyes in Solution MD using the data in the Table. Do not determine the fraction
of one dye by subtracting the fraction of another dye from 1.
1.2 Chromatographic Separation Followed by Spectrophotometric Analysis

a) Elute the cartridge with about 10 cm3 of Solution E using 10 cm3 syringe (Fig.
C).
b) Load 1.00 cm3 of solution MD onto the cartridge (Fig. D).
c) Using 1 cm3 syringe, elute with Solution E (Fig. E). Collect the solution eluting
through the outlet in a 10 cm3 volumetric flask. Repeat until the red compound is
completely eluted and collected.
d) Fill the flask to the 10 cm3 mark with Solution E and mix. Call this Solution F.
e) Obtain the absorption spectrum of solution F as in Experiment 1.1. Dilution
takes place during elution. Therefore, multiply the measured absorbance by 10
when drawing the spectrum for Solution F. Draw spectrum with broken line in
Fig. 1.1 in red ink.
f) Dilute Solution R as necessary and construct a calibration curve, at a
wavelength of your choice, for analysis of the red dye (R) in Solution F. Draw a
calibration curve in the answer sheet (X-axis, concentration; Y-axis, absorbance,
Fig. 1.2). Indicate the wavelength used. The calibration curve must have three
points in addition to the origin. Mark the position of Solution F on the calibration
curve.
g) Report the concentration of R in the original Solution MD.
h) Compare this concentration with the value you obtained in Experiment 1-1 and
report the recovery (amount eluted/amount loaded) associated with
chromatography.
TH
PRACTICAL PROBLEMS
Ion-exchange chromatography of amino acids
Ion-exchange chromatography is an important analytical and preparative method,
which allows fractioning of charged substances. Interaction of ionic groups of the
substances with counterions attached to the resin is behind the method. In this task you
will have to carry out separation of a given mixture of three amino acids followed by
quantitative assay of individual amino acids eluted from the column by using specific
chromogenic reactions. Since queues of students are possible at spectrophotometers, we
strongly suggest you starting the exam with Problem 1.
O O NH2 O
N
OH HS OH HN NH OH
NH2 NH2 NH2
N
H
His Cys Arg
Three amino acids (see the structures above) are present in the mixture. These are
histidine, cysteine, and arginine. Cross-linked sulfonated polystyrene is used as a cation-
exchange resin (see the picture of the system below). At the beginning of the experiment
the column is equilibrated with Eluent 1 (pH 4.9).
Procedure
Chromatography. Step 1
Apply the given solution of a mixture of amino acids to the column. First, open the
stopcock to allow the solvent in the column draining into the Erlenmeyer flask labelled
“Waste” so that the solvent is level with the top of packing material, still preventing the
resin surface from drying off. Close the stopcock and carefully add the analyzed solution
to the top of the column by using a syringe. Open the stopcock and let the sample soak
inside the gel (drain the solvent into the “Waste” flask). Close the stopcock and add about
3
1 cm of Eluent 1 (corresponds to ~ 1 cm of liquid in the column) by carefully releasing the
TH
tubing clamp. Attach the top joint tightly, fixing the column with one hand and the adaptor
with the other (be sure that the joint is fitted closely to the column). Replace the “Waste”
flask at the stand with the test tubes in the rack. Release the tubing clamp and open the
stopcock to let the eluent flow down through the column. Proceed with elution. (Always
pen the stopcock to start elution and close the stopcock to stop it).
Collect the fractions in the test tubes up to the volume of 2.5 cm3 (as shown in the
Picture). If needed, label them with marker. After collecting each 4 to 8 fractions stop
elution and carry out qualitative analysis of the collected samples.
tubing clamp
Eluent
plastic
stopcock
2.5 mL
Qualitative analysis of samples

Qualitative assay of amino acids is based on the reaction of their α-amino groups
with sodium 2,4,6–trinitrobenzene sulfonate (TNBS):
TH
NO2 O 2N
NH2 + O
Na HOOC NH
-
HOOC + O S NO2 + NaHSO3
R R NO 2
O
NO2 O 2N
The assay is carried out in the wells of a polystyrene plate, each well corresponding
3 3
to a definite test tube. Before starting the assay, mix 1 cm of TNBS solution with 10 cm
of carbonate buffer solution and place 0.1 cm3 of the resulting mixture into half of the plate
wells (from A1 to H5). Then add 0.1 cm3 of the analyzed fraction into a well. Start with A1
well and continue with B1, C1, etc (move top to bottom and left to right). If an amino acid
is present in the analyzed fraction, intense yellow coloration will develop in the
corresponding well within 3 min. Use the coloration in the first well as the reference. To
reliably estimate the coloration, place the plate on the white sheet of paper.
Note: all aliquots of 0.1 cm3 should be added by using the pipettor. We expect you to use
one tip for all fractions of a single peak.
1.1 a Draw the profile of coloration intensity (qualitatively) on the plate sketch in the
Answer Sheet. Use the following symbols: (-) – no coloration, 1 – weak coloration,
2 – moderate coloration and 3 – intense coloration. Keep drawing the profile during
the whole chromatography process.
Continue collecting fractions and analyzing them until you get at least two wells with
coloration as in A1 well, which will indicate that the first amino acid has left the column
completely (end of the first peak).
As soon as you are finished with collecting the first peak, change to Eluent 2. To do
so, close the stopcock, fix the tubing clamp (Important!), disconnect the tubing leading to
the bottle with Eluent 1 and connect the tubing leading to the bottle with Eluent 2. Attach
the top joint tightly.
TH
1.1 b Indicate when the eluents have been changed by drawing lines between the
corresponding wells on the plate sketch.
Continue elution, collecting fractions and carrying out qualitative analysis of samples as
described above.
As soon as you are finished with collecting the second peak, change to Eluent 3 as
described in Step 2. Continue chromatography until the third amino acid leaves the
column completely.
Stop chromatography by closing the stopcock and fixing the clamp.
Based on the results of qualitative analysis, choose the fractions which contain the
amino acids.
1.1 Write down in the Answer Sheet the labels of wells corresponding to the chosen
fractions.
1.2 Combine the fractions from each peak and measure the volumes of combined
fractions using a measuring cylinder. Report the volumes of combined fractions
excluding amounts used for the qualitative analysis. Write down the obtained
results in the Answer Sheet.
Pour combined fractions in the amber glass vials labelled “Peak 1”, “Peak 2”, “Peak
3”. Prepare samples for quantitative spectrophotometric analysis as described below.
When finished with Practical exam, close the vials and leave them on the table. The
combined fractions will be subsequently analyzed by lab staff.
Spectrophotometric analysis
For each probe, you should submit two cells to the operator. Prepare the probes as
follows.
Important! When storing, always put cell in the cell holder! All cells have 2 ribbed and 2
working vertical surfaces. While operating with cells, do not touch working surfaces,
otherwise you may get incorrect values of absorbance.
TH
Assay 1 (peak 1). Cysteine concentration is determined by the Ellmann reaction:
NO2
-
O
O O - -
O S O
- +
O NH3 +
H3N S
+ -
O
-
S OH
-
S +
O SH
O S
-H2O O
-
O NO2
O NO2
NO2
Test tube A1 (Reference).

Place 0.1 cm3 of Eluent 1 from plastic microtube into a test tube and add 2.9 cm3 of
Ellmann reagent (DTNB).
Test tube B1 (Sample).
3 3
Place 0.1 cm of the analyzed solution into a test tube and add 2.9 cm of Ellmann
reagent (DTNB).
Mix the contents of the test tubes thoroughly and transfer each mixture to the
corresponding cells labelled A1 (for reference) and B1 (for sample).
Assay 2 (peak 2). Determination of histidine concentration is based on the ability of

imidazole moiety to react with diazonium compounds (Pauli reaction).
Place 2.8 cm3 of Tris-HCl buffer solution into a test tube, add 0.1 cm3 of Eluent 2
from plastic microtube and 0.1 cm3 of Pauli reagent.
Place 2.8 cm3 of Tris-HCl buffer solution into a test tube, add 0.1 cm3 of the analyzed
solution and 0.1 cm3 of Pauli reagent.
Mix the contents of the test tubes thoroughly and transfer each mixture to the
corresponding cells labelled A2 (for reference) and B2 (for sample).
Assay 3 (peak 3). Determination of arginine concentration is based on the ability of

guanidinium moiety to react with some phenols under alkaline and oxidative conditions
TH
(Sakaguchi reaction).

3 3
Place 0.1 cm of Eluent 3 into a test tube and add 1.5 cm of 10 % NaOH solution,
3 3
1 cm of 8-hydroxyquinoline solution and 0.5 cm of sodium hypobromite solution.
3 3
Place 0.1 cm of the analyzed solution into a test tube and add 1.5 cm of 10 %
NaOH solution, 1 cm3 8-hydroxyquinoline solution and 0.5 cm3 of sodium hypobromite
solution.
Shake the test tubes vigorously for 2 min (Important!) and observe formation of
orange colour. Add 0.2 cm3 of 8 M urea solution to each test tube, mix the contents and
transfer about 3 cm3 of each mixture to the corresponding cells labelled A3 (for reference)
and B3 (for sample).
All mixtures should be analyzed by spectrophotometry not earlier than 10 min and
not later than 2 h after preparation. Submit the set of 6 cells to the spectrophotometer
operator. In case of a queue at the spectrophotometer, ask the operator to put your
student code on the list at the signboard. You will be invited by the operator in due time.
Meanwhile, you can answer the theoretical question and start fulfilling Problem No 2.
In case your sample(s) have not been subjected to studies within the proper time
interval (which is quite improbable), prepare the sample(s) afresh.
Get the print-offs with the spectra of your samples and check it. Sign the print-offs
and get the operator’s signature.
1.3 Determine absorbance at the corresponding wavelengths and calculate the content
(in mg) of each amino acid in the mixture you were given. The optical length is 1.0
cm. Complete the Answer Sheets taking into account that one mole of each amino
acid gives one mole of the corresponding product.
Reference data:
The values of extinction coefficients: Molar masses of the amino
Product of Ellmann reaction: 13600 M-1cm-1 acids.
at 410 nm Cysteine: 121 g mol-1
Product of Pauli reaction: 6400 M-1cm-1 at 470 nm Histidine: 155 g mol-1
Product of Sakaguchi reaction: 7700 M-1cm-1 Arginine: 174 g mol-1
at 500 nm
TH
1.4 Draw three resonance structures of the species responsible for mixture coloration as
a result of Ellmann reaction.
_______________
SOLUTION
1.2 – 1.3
Aλ n V M
Content of an amino acid = ,
εl
Aλ is the absorbance of the sample calculated from the spectra, l is the optical length
(1.0 cm), n is the dilution factor determined as a ratio of the aliquot of analyzing solution
(0.1 cm3) and the final volume of the sample in the cells, V is the volume of the combined
fraction from the corresponding peak, and M is the molar mass of the amino acid.
Content of each amino acid is determined by using the following plot (values
recalculated from volumes reported by students and absorbance values recorded by
spectrophotometer).
Marks
Pmax
min min max max

macc mexp mexp macc
% mass determined
1.4 As it is given in the task text, mixed disulfide and 2-thio-5-nitrobenzoic acid are
formed in the reaction.
TH
NO2
-
O
O O - -
O S O
- +
O NH3 +
H3N S
+ -
-
O S OH
-
S +
O SH
O S
-H2O O
-
O NO2
O NO2
(I) (II)
NO2
Under slightly alkaline conditions, thiol group of (II) dissociates, and thiophenolate-
anion is formed. Resonance structures can be realized for this compound:
-
O - -
- COO COO
O -
- O O
O + - +
+ N S N S
N S - -
O O
O
The electronic structure of asymmetrical disulfide (I) does not differ considerably
from that of the original Ellmann reagent. Therefore, it can be concluded that the
compound responsible for coloration is thiophenolate-anion (a form containing C=S
bond).
ND
Determination of Fe(II) and Fe(III) by visual colorimetry

In this experiment, you are required to determine Fe(II) and Fe(III) in a given sample
solution which simulates a dissolved magnetite ore by visual colorimetric analysis involving
a colour reaction between Fe(II) and 2,2’-bipyridine (bpy) to form an intensely red
2+
complex, Fe(bpy)3 .
2+
The amount of Fe(bpy)3 complex can be quantified by visual colorimetric
measurement using Nessler tubes. This is a quite simple technique that was employed
before photoelectric instruments were generally available, but an accuracy of less than ±
5% can be achieved. In this technique, a pair of Nessler tubes is used; one is filled with a
reference solution, and the other is filled with a solution to be tested. The depths of
colours of the two solutions are balanced by adjusting the heights of liquid columns of the
solutions.
When the colours look the same, the concentration can be calculated from that of
the reference solution with a known concentration and the height of the column of each
solution based on the Lambert-Beer law:
A=εcl
where A is the absorbance, c is the concentration, l is the pass length and ε is the molar
absorption coefficient. First, you will learn to employ this technique by conducting
measurements A and B, and then you will determine the concentrations of Fe(II) and
Fe(III) with measurements C and D.
Chemicals
• Sample solution
• Standard Fe(bpy)32+ solution 1 containing 2.0 mg of iron in 1 dm3 of the solution.
• Standard Fe(bpy)32+ solution 2 containing 3.0 mg of iron in 1 dm3 of the solution.
• Acetate buffer solution, pH 4.6, 1 : 1 mixture of acetic acid and sodium acetate.
• Disodium hydrogen phosphate solution, c = 0.1 mol dm-3.
• 2,2’-bipyridine aqueous solution, w = 0.2 %.
• Sodium thioglycolate.
ND
Procedures
3 3
(1) Add 5 cm of acetate buffer solution, 5 cm of disodium hydrogen phosphate solution
3 3
(to mask Fe(III)), 5 cm of 2,2’-bipyridine solution and 10.00 cm of sample solution into
a 50 cm3 volumetric flask using appropriate pipettes for each and dilute the resulting
3
solution with water to the 50 cm mark. Then stopper the flask and mix the solution
well. Allow it to stand for at least 20 min to fully develop colour. This solution is named
“sample 1.”
3 3 3
(2) Add 5 cm of acetate buffer solution, 5 cm of 2,2’-bipyridine solution and 5.00 cm of
3
sample solution into a 50 cm volumetric flask. Then add 20 mg of sodium thio-
glycolate powder (in excess) to reduce Fe(III) to Fe(II). Dilute the solution with water to
the 50 cm3 mark, stopper the flask and mix the solution well. Allow it to stand for at
least 20 min. This solution is named “sample 2.”
(3) Perform visual colorimetric measurements A – D based on the “Instructions for visual
colorimetric measurement” shown below.
Instructions for visual colorimetric measurement

Set a pair of Nessler tubes on a Nessler tube
rack placed on an LED light box (do not remove it
from the bag at any time) and turn on the light (see
Fig. 2.1). Pour the provided “standard Fe(bpy)32+
solution 1” into one tube to an appropriate height
(70 – 90 mm is recommended) from the bottom
(etched marks on the tube indicate fixed heights
from the bottom in mm) and use this as a reference
for measurements A – D. Pour the solution to be
measured into the other tube, and then compare its
depth of colour with that of the reference solution by
looking downward through the solutions toward the
LED light box.
Adjust the height of the liquid column of the Fig. 2.1
Visual colorimetric measurement:
test solution by adding or removing the solution i: Nessler tube;
with a graduated pipette until the depth of colour Ii: Nessler tube rack; iii: LED light
box in a zipper storage bag;
in the two tubes is identical. Estimate your Iv: power switch.
ND
reading to at least 1 mm.

Note that the depths of colour in a certain range may be recognized as identical to
human eyes. The appropriate value for the height of the test solution, h, should be
determined by taking the range into the consideration. For example, if you adjust the
height of the liquid column of the test solution only by increasing (or decreasing) the
volume, you could reach a lower (or higher) value than the true one. A possible way to
estimate the true value is to take an average between the values of lower and higher
limits.
Measurement A:
Perform a measurement using “standard Fe(bpy)32+ solution 1” as both the reference
and the test solutions. In this measurement, pour the reference solution into a Nessler
tube to achieve an appropriate height, and then pour the test solution into the other
Nessler tube until the colours of the two solutions match each other. (When the colours
match, the heights should ideally be the same.) Then add more test solution until you
recognize that the colours have become different from each other. Report both the lower
and higher limits of the height of the liquid column of test solution with the same depth of
colour as the reference solution.
2.1 Report your results for measurement A using the table provided on the answer
sheet.
Measurement B:
2+
Perform a measurement of “standard Fe(bpy)3 solution 2” as a test solution using
“standard Fe(bpy)32+ solution 1” as a reference.
2.2 Report your results for measurement B using the table provided on the answer
sheet.
Measurement C:
2.3 Perform the measurement of sample 1.
Report your results for measurement C using the table provided on the answer
sheet.
Measurement D:
2.4 Perform the measurement of sample 2.
ND
Report your results for measurement D using the table provided on the answer
sheet.
2.5 Express the concentration, c, of the test solution, using the concentration of the
reference solution, c’, and the heights of each liquid column, h and h’.
2.6 Calculate the concentrations of Fe(II) and Fe(III) in the original sample solution in
-3
mg dm .
_________________
ND
SOLUTION
2.1– 2.4
The competitors were requested to summarize their results in four tables for
measurements A, B, C, and D, respectively. It was necessary to record the height,
h’, (in mm) of the standard solution and the height, h, of the test solution.
A distribution graph was proposed and applied for evaluations of the
competitors’ results.
c ' h'
2.5 c=
h
2.6 For Fe2+:

2.0 mg dm-3 × h'C × 50 cm3
2+
c(Fe ) =
hC × 10 cm3
-3 2+
c (Fe2+ ) : concentration, (mg dm ), of Fe in the sample solution,
hC: experimental height, (mm), of the liquid column of the test solution in the
measurements C,
h’C: experimental height, (mm), of the liquid column of the standard solution in
the measurements C.
3+
For Fe :
2.0 mg dm-3 × h'D × 50 cm3
c(Fe3+ ) = – c (Fe3+ )
hD × 5 cm 3
-3 3+
c (Fe3+ ) : concentration, (mg dm ), of Fe in the sample solution,
hD : experimental height, (mm), of the liquid column of the test solution in the
measurements D,
h’D : experimental height, (mm), of the liquid column of the standard solution in
the measurements D.
2+ 3+
Concentrations of Fe and Fe used for particular original sample solutions:
2+ -3 3+ -3
c(Fe ) / mg dm c(Fe ) / mg dm
Sample 1 8.16 18.0
Sample 2 8.60 19.0
Sample 3 9.08 17.7
Student Code AAA-1
Chemicals and Equipment (Task 1A).
I. Chemical and materials (the actual labeling for each is given in bold font)
Hazard Statementsa
Instrument check solution, 80 cm3 in a plastic bottle
2.00  10-4 mol dm-3 Methyl orange indicator solution, H301
30 cm3 in a wide mouth glass bottle
1.00  10-3 mol dm-3 Bromothymol blue indicator
solution, 30 cm3 in a wide mouth glass bottle
Methyl red indicator solution, 10 cm3 in a wide mouth H225-H319-H371
glass bottle
1 mol dm-3 HCl, 30 cm3 in a plastic bottle H290-H314-H335
1 mol dm-3 NaOH, 30 cm3 in a plastic bottle H290-H314
buffer solution A, 110 cm3 in a plastic bottle
Unknown solution X, 50 cm3 in a plastic bottle
Unknown solution Y, 50 cm3 in a plastic bottle
Unknown solution Z, 50 cm3 in a plastic bottle
aSee page 34 for definition of Health Statements

Shared Equipment Quantity
UV-Visible spectrophotometer 1 per 2 students
Personal Labwares Quantity
Beaker, 25 cm3 2
Volumetric flask, 25.00 cm3 9
Measuring pipette, 2.00 cm3 2
Pasteur pipette 6
Rubber bulb for Pasteur pipette 6
Pipette filler bulb (3-way) 1
Pipette tray 1
Test tube (13 x 100 mm) 6
Test tube rack 1
Plastic cuvette, optical path length = 1.00 cm 1
Waste bottle, 1 dm3 1
Sticker label set in a zipped bag 1

Student Code AAA-1
Task 1A a b c Total
13% a1 a2 b1 b2 b3 c1 c2
Total 12 2 6 1 1 2 2 26
Score
Accounted For 13% of Total Score

Task 1A: Acid-base indicator and its application for pH measurement
Acid-base indicators are weak acids (or bases) that exhibit different colors when they
are present in solution as their acidic form (HIn, color 1) or as their basic form (In-, color 2).
They undergo the following reaction in dilute aqueous solution.
HIn H+ + In-
As the pH of a solution containing the indicator changes, the equilibrium shown above will be
driven either towards reactants (HIn), or products (In-) causing the solution color to change
depending on the concentration of each form present. In strongly acidic solution, most of the
indicator will be present in the HIn form (color 1) and in strongly basic solutions, most of the
indicator will be in the In- form (color 2). At intermediate pH values, the solution color will
be a mix of color 1 (absorption at wavelength 1) and color 2 (absorption at wavelength 2),
depending on the relative amounts of HIn and In- present.
By monitoring the absorbance values at two wavelengths, the concentrations of HIn and In -
can be calculated by using the following expressions.
Aλ1total = Aλ1HIn + Aλ1In-

=  λ1HIn b[HIn] +  λ1In-b[In-]
Aλ2total = Aλ2 HIn + Aλ2In-
=  λ2HIn b[HIn] +  λ2In-b[In-]
where b is pathlength of solution and  is the molar absorptivity.

At a certain pH value, the relative amounts of HIn and In- in solution are related to the acid
dissociation constant (Ka) of the indicator, as shown in the following equation.
Ka = [H+][In-]
[HIn]
Therefore, for a given pH value, acid dissociation constant (Ka) of the indicator can be
calculated when the relative amounts of HIn and In- in solution are known.

Student Code AAA-1
Experimental Set-up
Instructions for using a spectrophotometer

1. Set a spectrophometer to measure the absorbance at the desired wavelength following the
procedure shown in the diagram.
2. Wipe the outside of a cuvette containing distilled water and insert the cuvette into the sample
compartment.
3. Adjust the zero absorbance using water.
4. Remove the cuvette, replace water in the cuvette by sample solution to be analyzed. Make
sure to tap out any bubbles and wipe the outside of the cuvette before placing the cuvette
into the sample compartment.
5. Read the absorbance value of the sample.
Note: When changing the wavelength, make sure to adjust zero absorbance using “water”.
Spectrophotometer No.
Sample Compartment Screen
Keypad

Student Code AAA-1
Step 1: Press 1
1 Press [1] 2
1 Press
Press 1[1]
icon on the keypad to select Photometric mode 2
Press [1] icon on the touchscreen to select
[1] icon
PressNote: P
Photometric theon
mode
If themenu
main touchscreen
as shown intothe
select
left picture is not displayed on the
Photometric mode si
screen, press [return] on the keypad.
Note : If the main menu as shown in the left picture is not displayed
1 Press
on Note [1]
: If the press
the screen, [return]ason
main menu the keypad.
shown in the left picture is not displayed 2 Press [1]
on the screen, press [return] on the keypad.
Press [1] icon on the touchscreen to select
Photometric mode Press [1] on the touchscreen to
single wavelength mode
Note : If the main menu as shown in the left picture is not displayed
2 Press
Step 2: [1]
on the screen, press [return] on the keypad.
Press 1
elect
[1] on
PressPress the touchscreen
1 icon to select
on the keypad Photometric
to select Photometric mode single
e is not displayed
3 Setwavelength mode
the wavelength
3 Set the wavelength
3 SetPress [GOTO WL] on the keypad to set the
the wavelength 4 Get the Abso
Press [GOTO WL] on the keypad to set the
wavelength
Press [GOTO WL] 3: Rinse with water 1 - 2 me
Step on Set
wavelength the wavelength
the keypad to set the
Rinse with water 1 - 2 me
wavelength Rinse with water 1 - 2 me Fill the solu on around ¾
Place cuvette conta
Press [GO TO WL] on the keypad to set the wavelength Fill the solu on around ¾
of cuve Fill
e height & Wipe
the solu with
on around paper
¾
Press number on the keypad of cuve e height & Wipe with paper of cuve e height sample compartme
& Wipe with paper
2 onPress
Press
Press number number [1]
on the keypad
the keypad
Note : Press number
For example, if the on thewavelength
desired keypad is 432 nm,
[AUTO ZERO] on t
Note : For example, if the desired wavelength is 432 nm, Place cuvette conta
en to select Note4 3: keypad.
2For
onexample, if the desired wavelength is 432 nm,
press 4press
3 2 on the
Press
press 4 43 [1]
2 on onGet the Absorbance value
the keypad.
the the touchscreen to select Photometric
keypad. solution in the sam
2 Press [1] Note: For example, if the desired wavelength is 432, press 4 3 2 on the keypad. measure the absor
set
ftselecttheis not displayed
picture
Press
Press [ENTER]
[1]Press on the
on thePress keypad
[ENTER]
touchscreen on keypad
the
to select keypad
Photometric
d.
Rinse with water 1 - 2 me [ENTER] on the
re is not displayed
single wavelength [ENTER]
Press mode on the
Place cuvettekeypad
containing water in the
of cuve e height & Wipe with paper
[GO TO WL]  4 3 2  [ENTER] press
Fill the solu on around ¾ Note : If the Abs is not displayed on the screen, press [F1] on the
sample compartment and
Repeat Step 3-4 to measure the absorbance at
keypad to switch between %T & Abs.　
Note : If the Abs[AUTO ZERO]
is not displayed on the screen,
onthe
the press [F1] on the
keypad another
[F1] wavelength Repeat
NoteNote:
keypad : Ifswitch
to the
If Abs
the is notisdisplayed
Abs
between %T Abs.on
　 on
not&displayed screen, press
the screen, on
press the
[F1] on the keypad Step
to 3-4 to measure
s 432 nm, keypad to switch
switch between
Place
between %T &Abs
cuvette
%T and Abs. 　
containing sample Repeat Step 3-4 to measure
another wavelength
solution in the sample compartment to another wavelength
measure the absorbance
4 Get the Absorbance value
4 Get the Absorbance value
pad to set the
to set the
Rinse with DI water
Rinse with water 1 - 2 me Step 4: Get the absorbance value
press [F1] on the Rinse with water 1 - 2 me Place cuvette containing water in the
Repeat
FillFillthe Step
solution 3-4
Fill the solu to
around measure
on around
¾ of ¾ the absorbance
Place at compartment
cuvette containing
sample
water in the
and press
the solu
of on around
cuve ¾
e height & Wipe with paper sample Place
compartment andcuvette
press containing water in the sample
another
the cuvette wavelength
of cuve e height & Wipe with paper
height and wipe [AUTO ZERO]
[AUTO ZERO] oncompartment
the keypad on the keypad
with paper
and press [AUTO ZERO] on the keypad.
elength is 432 nm,
is 432 nm, Place cuvette containing sample
Place cuvette containing sample
Placecompartment
solution in the sample
solution cuvette containing
in the sample sampletosolution in the
to compartment
sample compartment to measure the absorbance
d
n, press [F1] on the
screen, press [F1] on theRepeat Step 3-4 to measure
Repeat the absorbance
Step at
3-4 to measure the absorbance at another wavelength
another Repeat Step 3-4 to measure the absorbance at
wavelength
another wavelength

Student Code AAA-1
General Information
In 0.1 mol dm-3 HCl, indicators are in the acidic form (HIn) only.
In 0.1 mol dm-3 NaOH, indicators are in the basic form (In-) only.
There will be no mark for the answer in the dotted line box.
NOTE:
Students are suggested to check the spectrophotometer before use by measuring the
absorbance values of the instrument check solution at two different wavelengths, i.e., 430 and
620 nm.
Spectrophotometer No. ________ is used throughout the experiment.
Record the absorbance values of the instrument check solution

A (at 430 nm) A (at 620 nm)
Measured value ________________ ________________

Guided value 0.220 – 0.260 0.450 – 0.510
In case that the measured values are within the guided values, students can proceed with
further experiments. If not, students can ask for assistance.
Part a
Absorbance measurement of an acid-base indicator (methyl orange) in strong acid and
strong base
1. Pipette 1.50 cm3 of 2.00  10-4 mol dm-3 methyl orange indicator solution into a 25.00-
cm3 volumetric flask, add 2.5 cm3 of 1 mol dm-3 HCl into the flask and make up to the
volume using distilled water. Record the absorbance at 470 and 520 nm.
cm3 volumetric flask, add 2.5 cm3 of 1 mol dm-3 NaOH into the flask and make up to the
3. Calculate the molar absorptivities at 470 and 520 nm of acidic and basic forms of methyl
orange.

Student Code AAA-1
a1) Record the absorbance values of methyl orange in acid and basic solutions
(You do not need to fill the entire table.)
methyl orange in acidic form A (at 470 nm) A (at 520 nm)
Replicate 1
Replicate 2
Replicate 3
Accepted value
(3 digits after decimal point) _____________ _____________
methyl orange in basic form A (at 470 nm) A (at 520 nm)
Replicate 1
Replicate 2
Replicate 3
Accepted value
a2) Calculate the molar absorptivities of the acidic form and basic form of methyl orange
(unit, dm3 mol-1 cm-1)
Blank area for calculation

Student Code AAA-1
The molar absorptivities of methyl orange are as follows: (unit, dm3 mol-1 cm-1)
acidic form (HIn) basic form (In-)

methyl orange  HIn
470
520HIn 470In- 520In-
____________ ____________ ____________ ____________
Part b
Absorbance measurement of an acid-base indicator (bromothymol blue) in buffer
solution
Bromothymol blue is an acid-base indicator which shows yellow color when it is present as an
acidic form (HIn) and it shows blue color when it is present as a basic form (In-). The
absorption maximum of the bromothymol blue in the acidic form is at 430 nm and that in the
basic form is at 620 nm. The molar absorptivities of bromothymol blue in the acidic form are
16,600 dm3 mol-1 cm-1 at 430 nm and 0 dm3 mol-1 cm-1 at 620 nm. The molar absorptivities of
bromothymol blue in the basic form are 3,460 dm3 mol-1 cm-1 at 430 nm and 38,000 dm3 mol-1
cm-1 at 620 nm.
1. Pipette 1.00 cm3 of 1.00 × 10-3 mol dm-3 bromothymol blue indicator solution into a
25.00-cm3 volumetric flask, and make up to the volume using solution A. (Note: solution
A is a buffer solution pH = 7.00)
2. Record the absorbance at 430 and 620 nm.
3. Calculate the concentrations of the acidic form and basic form of bromothymol blue
indicator solution in the volumetric flask.
4. Calculate the acid dissociation constant of bromothymol blue.
b1) Record the absorbance values of bromothymol blue in buffer solution

bromothymol blue in buffer solution A (at 430 nm) A (at 620 nm)
Replicate 1
Replicate 2
Replicate 3
Accepted value

Student Code AAA-1
b2) Calculate the concentrations of the acidic form and basic form of bromothymol blue
indicator in the resulting solution
The concentrations of the acidic form and basic form of bromothymol blue in the resulting
solution are as follows:
[HIn], mol dm-3 [In-], mol dm-3
___________________ ___________________
(3 significant figures) (3 significant figures)
b3) Calculate the acid dissociation constant of bromothymol blue from this experiment.
The acid dissociation constant of bromothymol blue from this experiment is as follows:
The acid dissociation constant = ___________________________ (3 significant

figures)

Student Code AAA-1
Part c
Determination of solution pH by using acid-base indicator (methyl red)
Methyl red is an acid-base indicator which shows reddish-pink color when it is present as an
acidic form (HIn) and it shows yellow color when it is present as a basic form (In-). The molar
absorptivities of methyl red in the acidic form are 9,810 dm3 mol-1 cm-1 at 470 nm and 21,500
dm3 mol-1 cm-1 at 520 nm. The molar absorptivities of methyl red in the basic form are 12,500
dm3 mol-1 cm-1 at 470 nm and 1,330 dm3 mol-1 cm-1 at 520 nm. The pKa of methyl red is 4.95.
Note: There is no need to accurately measure the volumes used in this part, as it does not affect
the accuracy of the results obtained.
1. Fill a test tube to one quarter with solution of unknown pH X. Add three drops of methyl
red into the solution and mix thoroughly. Record the color.
2. Fill a test tube to one quarter with solution of unknown pH Y. Add three drops of methyl
3. Fill a test tube to one quarter with solution of unknown pH Z. Add three drops of methyl
Record the color change of indicator in sample solutions (no mark)
indicator Color observed
in sample X in sample Y in sample Z
Methyl red
c1) Select one solution from the three sample solutions, of which the pH can be determined
spectrophotometrically by using methyl red as an indicator.
 Sample X  Sample Y  Sample Z
4. Use a measuring cylinder to transfer 10 cm3 of the selected unknown solution into a
beaker. Add three drops of methyl red indicator into the solution and mix thoroughly.
Record the absorbance at 470 and 520 nm.
5. Calculate the concentration ratio of basic form and acidic form of methyl red in the
solution.
6. Calculate the pH of the selected unknown solution.

Student Code AAA-1
Record the absorbance values of the resulting solution
selected unknown solution A (at 470 nm) A (at 520 nm)
c2) Calculate the concentration ratio of the basic form and acidic form of methyl red indicator
in an unknown solution and the pH value of the unknown solution
The concentration ratio of the basic form and acidic form of methyl red indicator in an unknown
solution and the pH value of the unknown solution are as follows:
sample [In-] / [HIn] pH
_________________ _____________
(2 digits after decimal point) (2 digits after decimal point)

Student Code AAA-1
General Instructions.
General Information
In 0.1 mol dm-3 HCl, indicators are in the acidic form (HIn) only.
In 0.1 mol dm-3 NaOH, indicators are in the basic form (In-) only.
There will be no mark for the answer in the dotted line box.
NOTE:
Students are suggested to check the spectrophotometer before use by measuring the
absorbance values of the instrument check solution at two different wavelengths, i.e., 430 and
620 nm.
Spectrophotometer No. ________ is used throughout the experiment.
Record the absorbance values of the instrument check solution

A (at 430 nm) A (at 620 nm)
Measured value ________________ ________________

Guided value 0.220 – 0.260 0.450 – 0.510
In case that the measured values are within the guided values, students can proceed with
further experiments. If not, students can ask for assistance.
Part a
Absorbance measurement of an acid-base indicator (methyl orange) in strong acid and
strong base
cm3 volumetric flask, add 2.5 cm3 of 1 mol dm-3 HCl into the flask and make up to the
cm3 volumetric flask, add 2.5 cm3 of 1 mol dm-3 NaOH into the flask and make up to the
3. Calculate the molar absorptivities at 470 and 520 nm of acidic and basic forms of methyl
orange.

Student Code AAA-1
a1) Record the absorbance values of methyl orange in acid and basic solutions
methyl orange in acidic form A (at 470 nm) A (at 520 nm)
Replicate 1
Replicate 2
Replicate 3
Accepted value
(3 digits after decimal point) 0.318 0.538
(SD = 0.009) (SD = 0.011)
methyl orange in basic form A (at 470 nm) A (at 520 nm)
Replicate 1
Replicate 2
Replicate 3
Accepted value
(SD = 0.009) (SD = 0.004)
a2) Calculate the molar absorptivities of the acidic form and basic form of methyl orange
(unit, dm3 mol-1 cm-1)

Student Code AAA-1
The molar absorptivities of methyl orange are as follows: (unit, dm3 mol-1 cm-1)
acidic form (HIn) basic form (In-)

methyl orange  HIn
470
520HIn 470In- 520In-
____________ ____________ ____________ ____________
Part b
Absorbance measurement of an acid-base indicator (bromothymol blue) in buffer
solution
Bromothymol blue is an acid-base indicator which shows yellow color when it is present as an
acidic form (HIn) and it shows blue color when it is present as a basic form (In-). The
absorption maximum of the bromothymol blue in the acidic form is at 430 nm and that in the
basic form is at 620 nm. The molar absorptivities of bromothymol blue in the acidic form are
16,600 dm3 mol-1 cm-1 at 430 nm and 0 dm3 mol-1 cm-1 at 620 nm. The molar absorptivities of
bromothymol blue in the basic form are 3,460 dm3 mol-1 cm-1 at 430 nm and 38,000 dm3 mol-1
cm-1 at 620 nm.
1. Pipette 1.00 cm3 of 1.00 × 10-3 mol dm-3 bromothymol blue indicator solution into a
25.00-cm3 volumetric flask, and make up to the volume using solution A. (Note: solution
A is a buffer solution pH = 7.00)
2. Record the absorbance at 430 and 620 nm.
3. Calculate the concentrations of the acidic form and basic form of bromothymol blue
indicator solution in the volumetric flask.
4. Calculate the acid dissociation constant of bromothymol blue.
b1) Record the absorbance values of bromothymol blue in buffer solution

bromothymol blue in buffer solution A (at 430 nm) A (at 620 nm)
Replicate 1
Replicate 2
Replicate 3
Accepted value
(SD = 0.006) (SD = 0.014)

Student Code AAA-1
b2) Calculate the concentrations of the acidic form and basic form of bromothymol blue
indicator in the resulting solution
The concentrations of the acidic form and basic form of bromothymol blue in the resulting
solution are as follows:
[HIn], mol dm-3 [In-], mol dm-3
___________________ ___________________
(3 significant figures) (3 significant figures)
b3) Calculate the acid dissociation constant of bromothymol blue from this experiment.
The acid dissociation constant of bromothymol blue from this experiment is as follows:
The acid dissociation constant = ___________________________ (3 significant figures)

Student Code AAA-1
Part c
Determination of solution pH by using acid-base indicator (methyl red)
Methyl red is an acid-base indicator which shows reddish-pink color when it is present as an
acidic form (HIn) and it shows yellow color when it is present as a basic form (In-). The molar
absorptivities of methyl red in the acidic form are 9,810 dm3 mol-1 cm-1 at 470 nm and 21,500
dm3 mol-1 cm-1 at 520 nm. The molar absorptivities of methyl red in the basic form are 12,500
dm3 mol-1 cm-1 at 470 nm and 1,330 dm3 mol-1 cm-1 at 520 nm. The pKa of methyl red is 4.95.
Note: There is no need to accurately measure the volumes used in this part, as it does not affect
the accuracy of the results obtained.
1. Fill a test tube to one quarter with solution of unknown pH X. Add three drops of methyl
2. Fill a test tube to one quarter with solution of unknown pH Y. Add three drops of methyl
3. Fill a test tube to one quarter with solution of unknown pH Z. Add three drops of methyl
Record the color change of indicator in sample solutions (no mark)
indicator Color observed
in sample X in sample Y in sample Z
Methyl red
c1) Select one solution from the three sample solutions, of which the pH can be determined
spectrophotometrically by using methyl red as an indicator.
 Sample X  Sample Y  Sample Z
4. Use a measuring cylinder to transfer 10 cm3 of the selected unknown solution into a
beaker. Add three drops of methyl red indicator into the solution and mix thoroughly.
Record the absorbance at 470 and 520 nm.
5. Calculate the concentration ratio of basic form and acidic form of methyl red in the
solution.
6. Calculate the pH of the selected unknown solution.

Student Code AAA-1
Record the absorbance values of the resulting solution
selected unknown solution A (at 470 nm) A (at 520 nm)
c2) Calculate the concentration ratio of the basic form and acidic form of methyl red indicator
in an unknown solution and the pH value of the unknown solution
The concentration ratio of the basic form and acidic form of methyl red indicator in an unknown
solution and the pH value of the unknown solution are as follows:
sample [In-] / [HIn] pH
_________________ _____________
(2 digits after decimal point) (2 digits after decimal point)

Cinetica
TH
PRACTICAL PROBLEMS
You will follow the concentration change of one of the reactants by the method of
comparative visual colorimetry. From data obtained experimentally plot graphically the
change of the reactant concentration in dependence on time.
Procedure:
1. Making of the comparative colorimetric scale of bromine solution
Measure with a syringe into 10 identical test-tubes the following quantities of bromine
water (0.01-molar): into the first one – 10.0 cm3; 2nd – 9.0 cm3; 3rd – 8.0 cm3, ....... 9th –
2.0 cm3; into the tenth one – 1.0 cm3. Then add to all the test-tubes (except the first one)
3
distilled water to reach a total volume of 10.0 cm in each. Seal the test-tubes with
stoppers and mix the solutions. Put the test-tubes in a stand with a white background.
Finally calculate the concentration (in mol dm-3) of bromine in the solutions in all test-
tubes.
2. Reaction of bromine solution with formic acid

3 3
Carry out the reaction by mixing 100.0 cm of bromine solution with 1.0 cm of 1.00-
molar solution of formic acid. Immediately after mixing transfer 10.0 cm3 of the resulting
solution to the test-tube identical with that used for colorimetric scale. By comparing the
colour shade of the reaction mixture (in one-minute intervals) with that of the solutions in
the scale, investigate changes of bromine concentration in dependence on time.
Put the data in a table containing time (t) and concentration of Br2.
Task:
Plot the bromine concentration in dependence on time a read the half-time of the
reaction from the diagram.
Questions:
1.1 Write the equation for the reaction of bromine with formic acid assuming that the
reactants are in stoichiometric amounts.
TH
1.2 In analytical chemistry a volumetric solution of bromine can be prepared by

dissolving a mixture of bromate and bromide in acid medium. Explain this mode of
preparation by means of a chemical equation in ionic form.
____________________
SOLUTION
Questions:
1.1 HCOOH (aq) + Br2 (aq) → CO2 (g) + 2 H (aq) + 2 Br− (aq)
+
1.2 BrO3- + 5 Br− + 6 H+ → 3 Br2 + 3 H2O
TH
PROBLEM 2 (practical))
The values of standard reduction potentials are given for the following redox
systems:
2 S 2 O 32− / S 4 O 26− E10 = 0.17 V
2 I− / I2 E 20 = 0.535 V
2 SO 24− / S 2 O 82− E 30 = 2.05 V
Problems:
2.1 Set in order the oxidation forms of the above given redox systems from the weakest
to the strongest oxidising agent (write into Table 1)
In a similar way order the reduction forms from the weakest to the strongest reducing
agent.
2.2 In the bellow given equations mark by arrows the expected possible course
(direction) of the chemical reaction (Table 1).
-
2 I + S4O2- 2-
6 = I 2 + 2 S 2 O3
2 I- + S2O82- = I2 + 2 SO2-
4
2 S2O32- + S2O82- = S4O2- 2-

6 + 2 SO 4
2.3 On the assumption that solutions of the same concentration are used, is it possible
to tell without making any experiment which of the given reactions would run at a
higher rate and which ones at a lower rate?
In order to confirm your hypothesis given under 3, perform the following three
qualitative experiments:
Experiment 1
Pour 20.0 cm3 of a 0.10-molar solution of Na2S2O3 into an Erlenmeyer flask and quickly
add under intense stirring 1.0 cm3 of a 0.10-molar iodine solution.
Experiment 2
Measure 20.0 cm3 of a 0.10-molar solution of (NH4)2S2O8 into an Erlenmeyer flask and
quickly add under intense stirring 4.0 cm3 of a 0.10-molar potassium iodide solution.
Experiment 3
Put 20.0 cm3 of a 0.10-molar solution of (NH4)2S2O8 into an Erlenmeyer flask and then
quickly add under intense stirring 2.0 cm3 of a 0.10-molar sodium thiosulphate solution.
TH
Since both the reactants and reactant products are colourless, the course of the
reaction can be followed indirectly. For that purpose, add to the solution after 1 – 2
minutes two or three drops of a 0.10-molar iodine solution. If the result of your experiment
is surprising, perform experiment No 3 again but allow solutions of Na2S2O3 and
(NH4)2S2O8 to react for 10 minutes.
Order the reactions from experiments No 1 – 3 (into Table 3) according to their
increasing reaction rate and then answer the question whether it is possible on the basis
of known values of the standard reduction potentials to guess, at least qualitatively, the
reaction rate for the reaction mixture containing two pairs of redox systems.
Conclusions made on the above experiments make it possible to investigate the
influence of concentration of each of the starting substances on the rate of the reaction
between I− and S2O82- ions.
Perform experiment No 4 according to the following instructions:
Experiment 4
a) Measure successively into a 250 cm3 Erlenmeyer flask: 25.0 cm3 of a 0.20-molar
3
potassium iodide solution, 10.0 cm of a 0.01-molar sodium thiosulphate solution, 5.0
cm3 of a starch paste, and stir the content of the flask.
b) Measure 25.0 cm3 of a 0.20-molar (NH4)2S2O8 solution into a 100 cm3 beaker. Pour
the content of the beaker quickly into the flask, press a stop-watch and stir the content
of the flask. Measure the time till the moment when the solution becomes blue.
Perform analogously experiment No 4 three times over, using the bellow given
volumes of the 0.20-molar potassium iodide solution, while the volumes of Na2S2O3
and (NH4)2S2O8 solutions as well as that of the starch paste remain unchanged.
Moreover, add to the solution the bellow given volumes of a 0.20-molar potassium
nitrate solution so that the volume of the resulting solution is always the same. Explain
the use of potassium nitrate in this case.
4 (ii): 15.0 cm3 0.20-molar KI + 10.0 cm3 0.20-molar KNO3
3 3
4 (iii): 10.0 cm 0.20-molar KI + 15.0 cm 0.20-molar KNO3
3 3
4 (iv): 5.0 cm 0.20-molar KI + 20.0 cm 0.20-molar KNO3
2.4 List the results of experiments No 1-4 briefly and clearly in the attached Tables.
Write formulas of the corresponding substances above the arrows in Table 1 (as
required under 2.1) and mark the expected course of the mentioned chemical
reactions by arrows in the equations.
TH
For a qualitative evaluation of reaction rate (Table 2) use terms such as: very rapid,
rapid, slow, very slow.
Fill in Table 3 exactly according to the titles of the columns.
2.5 Calculate the reaction rate according to the formula:
∆c (S2O82− )
v =
-3 -1
(mol dm s )
∆τ
∆c (S 2 O 82 − ) - concentration change of S 2 O 82 − in a time interval.
Plot (on the attached mm-paper) the dependence of reaction rate on the
concentration of I anions at a constant concentration of S 2 O 82 − anions in the

-
solution.
2.6 Making use of the knowledge gained from the preceding experiment and the
solutions which are at your disposal, suggest another experiment which would make
it possible to investigate the reaction rate dependence on concentration of
S 2 O 82 − anions at a constant concentration of I anions in the solution.

-
Considering Table 3, fill in Table 4. Mark the columns in the Table, suggest a plan of
the experiment and list experimental results as well as the calculated values.
Similarly as before, plot the dependence under investigation on a mm-paper.
2.7 Write a general relation for the reaction rate dependence on the concentration of
reactants and then using the diagrams attached, calculate the values for the reaction
rate constant for both cases and determine their mean value.
____________________
SOLUTION
2.1 S 4 O 26 − I2 S 2 O 82 −
Increase of oxidising properties of oxidised forms
SO 24 − I− S 2 O 32 −
Increase of reducing properties of reduced forms
2.2 The expected course of the chemical reactions:
2 I− + S 4 O 26 − ← I2 + 2 S 2 O 32 − (a)
2 I− + S 2 O 82 − → I2 + 2 SO 24 − (b)
TH
2 S 2 O 32 − + S 2 O 82 − → S 4 O 26 − + 2 SO 24 − (c)
2.3 The formulation of any hypothesis either supporting or neglecting the possibility of
predicting the reaction rate, should be accepted as correct.
Results of experiments Nos 1-3:
1 - reaction (a) is very rapid;
2 - reaction (b) is slow;
3 - reaction (c) is very slow, its course can hardly be observed.
Conclusion: The known differences between the values of standard reduction
potentials of two pairs of redox systems do not allow to guess even
qualitatively the proper relations between the rates of the
corresponding reactions.
2.4 You are required to fill in the following data into Table 3:
- volumes of individual solutions,
- the total volume of the solution (65 cm3),
- calculated values for I- and S 2 O 82 − concentrations,
- reaction time,
- calculated values for the reaction rate.
The addition of 0.20-molar KNO3 solution is needed to keep the constant ionic
strength of the resulting solution.
In plotting the reaction rate in dependence on the values of [I-]2 (at the constant
concentration of S 2 O 82 − anions) we get a straight line crossing the beginning of the
coordinate system.
Table 4 should be filled in analogously as Table 3 where, moreover, the individual
columns should be specified.
Solutions for the experiment are prepared in the same way but the solution of KI (25
cm3) will form a constant addition, whereas those of (NH4)2S2O8 and (NH4)2SO4 will
form a changeable addition in the resulting solution and the other conditions are
equal. Ammonium sulphate plays the same role in the solution as potassium nitrate
in the preceding experiment.
In this case the reaction rate versus the concentration of S 2 O 82 − anions is plotted (at
a constant concentration of I- anions) to give also a straight line crossing the

beginning of the coordinate system.
TH
2.5 The rate of the reaction:
v = k [ S 2 O 82 − ] [I−]2
a) [I−] = const ⇒ v = k’ [ S 2 O 82 − ]
k'
k=
[I- ] 2
k’ is the slope of the straight line.
b) [ S 2 O 82 − ] = const v = k” [I−]2
k” = k [ S 2 O 82 − ]
k"
k =
[S 2 O 82 - ]
k” is the slope of the straight line.

The values of the rate constants obtained from the procedures a) and b) should be
theoretically equal. If they partly differ, calculate the mean value of the rate constant.
ND
Kinetics of an SN1 Reaction
In an aqueous ethanolic solution, tert-butyl chloride (2-chloro-2-methylpropane)
undergoes an SN1 nucleophilic substitution reaction leading to the formation of
2-methylpropan-2-ol and hydrochloric acid:
tert-BuCl + H2O = tert-BuOH + HCl
The rate of the reaction is given by

d [HCl]
= k1 [tert BuCl]
dt
The aim of this experiment is to determine the rate constant k1 at ambient temperature.
Procedure:
1. Using a pipette transfer 2.0 cm3 of tert-butyl chloride (flask 4.1 on the general-use
3
bench) into a clean and dry 250 cm ground neck Erlenmeyer (conical) flask.
2. As soon as possible add 148 cm3 (measure with the graduated cylinder) of the
aqueous ethanol solution standing on the general-use bench (flask 4.2).
3. Stopper the Erlenmeyer flask and stir vigorously using the magnetic stirrer. Start your
timer. Note carefully the temperature, T(0), of the solution.
4. After approximately 5, 15, 25, 35, 45, 55 min (determined accurately), transfer 10.0
cm3 samples using a pipette into 20 cm3 of a mixture of ice and acetone
(propanone).
Add 2 drops of bromothymol blue and titrate the liberated acid with a solution of Y
mol dm-3 aqueous sodium hydroxide (Y will be shown on the board).
Questions:
4.1 The concentrations of tert-BuCl at time t = 0 and at time t are linked by the following
relationship:
[tertBuCl]0
ln = k1.t
[tertBuCl] t
Establish the theoretical expression:
ln V∞ = k t
V∞ − V
1
ND
where V stands for the volume of sodium hydroxide used at time t and V(8) for the
corresponding value at t(8).
t ∞ = t (8); V∞ = V (8)
o -3
4.2 Calculate V(8) (density of tert-BuCl at 20 C: 850 kg m , molar mass of tert-BuCl:
92.5 g mol-1).
4.3 Fill in the table on the answer sheet whose columns will be:
V ∞ , ln V ∞
t (min), V (cm3 ), V ∞, V,
V∞ − V V∞ − V
Draw the curve
ln V ∞ = f (t)
V∞ − V
4.4 Determine the value of k1 (give the value of t(0)).

_______________
SOLUTION
4.1 t-BuCl + H2O → t-BuOH + HCl
t=0 (t-BuCl)0
t (t-BuCl) (t-BuCl)0 – (t-BuCl)
t(8) (t-BuCl)0
d (HCl) (t − BuCl)
=− = k1 (t − BuCl)
dt dt
(t − BuCl )0
ln = k1 t
(t − BuCl )
t:
V (NaOH) × c (NaOH) V × Y × 10 −2
c(HCl) = c0(t-BuCl) – c(t-BuCl) = =
V (HCl) 10
t(8)
aY
c(HCl) = c0(t-BuCl) =
10
(a − V ) Y
c(t-BuCl) =
10
ND
c0 (t-BuCl) a
ln = ln = k1 t
c (t-BuCl) a −V
1.70
4.2 n0(t-BuCl) = M(t-BuCl) = 92.5 g mol-1
92.5
10
Y × a × 10 × n0 (t-BuCl)
-3
=
150
170
a(ml) = −3
Y × 10 × 15 × 92.5
ST
PRACTICAL PROBLEMS
A Kinetic Study of the Acid Catalyzed Reaction Between Acetone and Iodine in
Aqueous Solution
+
The reaction between acetone and iodine in aqueous solution is catalyzed by H .
H+
CH3-CO-CH3 (aq) + I2 (aq) CH3-CO-CH2I (aq) + H+(aq) + I–(aq)
In this experiment, the kinetics of the iodination is measured to determine the rate law of
the reaction. The rate equation for the loss of I2(aq) has been shown to have the form
d[I2 ]
Rate = - = k [CH3COCH3 ]x [I2 ]y [H+ ]z
dt
+
where H ions are the catalyst.
In order to determine the rate constant k and the kinetic orders x, y and z, the initial
rate of reaction is measured.
Initial rate = k [CH3COCH3 ]0x [I2 ]0y [H+ ]0z
+
where [ ]0 are the initial concentrations of acetone, I2 and H , respectively.
If the initial rates are measured for various initial concentrations of the reactants then
the order with respect to each reactant can be obtained.
The initial rate is obtained by measuring the decrease in the I2(aq) concentration
after a short time interval (7.0 min. in this experiment) after the start of the reaction.
Aqueous sodium acetate solution is added to stop the reaction after 7 minutes. The
+
acetate ion reacts immediately with the H to produce acetic acid and so reducing the
+
concentration of H . The reaction is thus stopped as there is no catalyst present.
Since the reaction does not come to a complete halt, the solution should be titrated
immediately after the addition of the sodium acetate solution.
The remaining iodine I2 (aq) is determined by titration with sodium thiosulphate,
Na2S2O3. As the end point of the titration is approached, starch indicator is added and the
titration is continued until the blue colour disappears.
ST
Chemicals
3
1. Aqueous iodine solution in 0.4 M KI 80 cm
3
2. 0.100 M aq. HCl 50 cm
3
3. 0.50 M aq. CH3COONa 80 cm
3
4. Standard 0.02 M Na2S2O3(aq) solution 200 cm
(the exact concentration will be announced at the beginning of practical part)
3
5. Aqueous acetone (50% by volume) 50 cm
(Density of pure acetone; 0.787 g cm-3, MW. = 58.08)
6. Starch indicator 7 cm3
Procedure
A. Standardization of Iodine Solution

1. Pipet 5.00 cm3 of aqueous iodine into a clean 125 cm3 Erlenmeyer flask.
3
2. Add 10 cm of distilled water using graduated cylinder.
3. Titrate the iodine with the standard 0.02 M sodium thiosulphate solution until the
colour of the solution is pale yellow.
4. Add 3 – 4 drops of starch indicator and continue the titration until the blue colour
disappears.
5. Record the initial and the final volumes of the thiosulphate solution and the volume
used in the answer sheet.
6. Repeat the titration as necessary (Steps 1 to 5).
7. Give the titre volume for calculation in the answer sheet.
8. Calculate the iodine concentration.
B. A kinetic study of acid catalyzed reaction between acetone and iodine in aqueous
solution
1. Label the stoppered flasks as follows: Flask I, II, III and IV.
2. To each respective flask add the following volumes of distilled water, 0.100 M
hydrochloric acid and 50 % acetone:
ST
Volume (cm3)
Flask No. water 0.100 M HCl 50 % acetone
I 5.00 5.00 5.00
II 0.0 5.00 5.00
III 0.0 5.00 10.00
IV 0.0 10.00 5.00
Stopper each flask immediately after addition of the solutions.

3. Measure out 10 cm3 of 0.50 M aq. CH3COONa into the graduated cylinder.
4. Set the stop-watch to 0.0000 display.
5. Pipet 5.00 cm3 of iodine solution into the stoppered Flask No. I.
Start the stop-watch as soon as the first drop of iodine solution is added.
6. Stopper the flask and swirl continuously.
7. Just before 7.0 min, remove the stopper, at 7.0 min, immediately pour 10 cm3 of
sodium acetate solution (from step 3) into the reaction flask. Shake well.
8. Titrate the remaining iodine with standard thiosulphate solution.
9. Record the volume of the thiosulphate solution.
10. Repeat the above steps (Steps 3 to 9) for Flask II, III and IV but add in step 5 the
I2(aq) solution to each flask as indicated:
Flask II: 10.00 cm3 I2 solution

Flask III: 5.00 cm3 I2 solution
Flask IV: 5.00 cm3 I2 solution
Calculations
B-1. Calculate the initial concentrations (M) of iodine, acetone and HCl solutions in
Flasks I to IV, assuming volumes are additive.
B-2. Calculate concentrations of iodine (M) remaining in Flasks I to IV at 7.0 minutes.
B-3. Calculate the initial reaction rate for Flasks I to IV in M s-1.
B-4. The rate of reaction has the form
d[I2 ]
Rate = - = k [CH3COCH3 ]x [I2 ]y [H+ ]z
dt
ST
Calculate the reaction orders x, y and z from the initial rates and the initial
concentrations of acetone, iodine and HCl. The values of x, y and z should be
rounded off to the nearest integer and fill in the answer sheet. Write rate equation or
rate law.
B-5. Calculate the rate constant, k, for Flasks I to IV with proper unit.
B-6. Give the mean value of the rate constant.
_______________
SOLUTION
The competitors were required to perform the following tasks:
In part A: Using the concentration of standard Na2S2O3 solution (in bottle) and titration
results it was required to calculate the concentration of iodine in the solution. Results were
expected to be shown in a table in the answer sheet.
In part B: The following calculations B1 – B5 were required to be shown in the answer

sheet:
B-1. Calculation for initial concentrations (M) in the solution mixtures.
B-2. Calculation of the concentration (M) of iodine remaining in flasks I to IV at 7 minutes.
B-3. Calculation of initial rate of disappearance of I2 at 7 minutes in flasks I to IV.
d [I2 ] c(I2 )initial − c (I2 )7 min
Rate of disappearance of iodine (M s ) = − =
-1
dt 7 × 60 s
B-4. Calculation of x, y, and z in the rate equation:
d [I2 ]
rate = − = k [CH3COCH3 ]x [I2 ]y [H+ ]z
dt
In comparing the rates in solutions II : I, III : I, and IV : I one can calculate the
following values:
x = 1; y = 0; z=1
+
The rate equation has the form: rate = k [CH3COCH3] [H ]
B-5. Calculation of the rate constants for solution mixtures I to IV and the mean value of
the rate constant.
RD
Determination of the Rate Constant for the Redox Reaction between Ethanol and
Chromium (VI)
The oxidation of alcohols by chromium (VI) forms the basis for analysis of breath
samples for measuring alcohol content. A dilute solution of K2Cr2O7 in the presence of a
strong acid (3.6 M HCI here) is a source of HCrO-4 which is the oxidant involved in the
reaction.
In this experiment, the rate of the reaction between HCrO-4 and CH3CH2OH is
determined titrimetrically. Under the given experimental conditions, the rate law reduces to
x
rate = k[ HCrO-4 ]
where x is the order of the reaction.

At any given time, [ HCrO-4 ] is obtained by iodometric titration.
Procedure
3
You are given 100 cm of standard K2Cr2O7 solution in HCI in a bottle. Transfer all
the absolute ethanol given in a vial into this bottle and stopper it. Mix the contents
thoroughly, start the stopwatch immediately and regard this as time t = 0. Fill the burette
with this solution.
3
After every 10 minutes, start to draw 10 cm of this solution to a clean conical flask
3
containing 4 cm of the given KI solution. The solution will turn brown. Titrate this solution
with the given standard Na2S2O3 solution until the colour changes to pale greenish yellow.
3
Add 2 cm of starch indicator and continue the titration until the colour changes from blue
to pale green. Record the burette reading in the answer sheet. Repeat this procedure at
10 minutes intervals to obtain four readings.
_______________
SOLUTION
The results of the titration (volumes) were required to be written on the Answer Sheet.
RD
3.1 Write down the possible oxidation products in the reaction of HCrO-4 and CH3CH2OH.
Solution: Acetic acid, CH3COOH

Acetaldehyde, CH3CHO
3.2 Write the chemical equation for the reaction between HCrO-4 and Kl:
Solution: 2 HCrO-4 + 6 I + 14 H → 3 l2 + 2 Cr
– + 3+
+ 8 H2O
3.3 Write down the balanced chemical equation involved in the titration.
Solution: I2 + 2 S2O32- → 2 I + S4O62-
– -
-3
3.4 Give the main steps for the calculation of HCrO-4 concentration (mol dm ) for any
one titration reading.

3.5 Give concentrations of HCrO-4 at different times (in a table attached).
3.6 Plot the graph of log [ HCrO-4 ] vs. time.
3.7 From the nature of the graph determine the order (x) of the reaction with respect to
HCrO-4
3.8 Determine the rate constant for the reaction.
THE 44TH INTERNATIONAL CHEMISTRY OLYMPIAD, Washington, 2012
PRACTICAL PROBLEMS
Kinetics, Isotope Effect, and Mechanism of Iodination of Acetone

Discoveries about the mechanisms of chemical reactions underlie advances in
catalysis and synthesis. One of the most powerful tools for probing reaction mechanisms
is the study of kinetics because the ways in which reaction rates vary with reaction
conditions follow directly from the mechanism of reaction. A second powerful tool is the
study of isotopically substituted molecules. While isotopes impart similar reactivity, there
are slight differences in reaction rates as a function of nuclear mass.
In this task you will use both kinetics and isotope effects to provide information about
the iodination of acetone in acidic aqueous solution:
O O
+ I3- + R+ + 2I-
I
R3C CR3 R3C C
R2
R = H or D
The reaction takes place with a rate law
Rate = k [acetone]m [I3− ]n [H+ ]p
where the rate constant k and the integer reaction orders m, n, and p are for you to
determine. You will also compare the reactivity of acetone with that of acetone-d6, where
1 2
the six atoms of protium ( H) have been replaced by deuterium ( H, D), to determine the
isotope effect (kH / kD) of the reaction. From these data you will make inferences about the
mechanism of this reaction.
Please read the whole description of this task and plan your work before you begin.
Chemicals
–3 *) 3
• HCl, aqueous solution, c = ~2 mol dm , 50 cm
–3 *) 3
• KI3, aqueous solution, c = ~0.01 mol dm , 10 cm , labelled “I2”,
–1 –3 3
• Acetone, (CH3)2CO, M = 58.08 g mol , density = 0.791 g cm , 10 cm ,
–1 –3 3
• Acetone-d6, (CD3)2CO, M = 64.12 g mol , density = 0.872 g cm , 3.0 cm
_______________
*)
The exact concentration is indicated on the label.
Procedure
Reaction rates are dependent on temperature. Record the temperature in the room
you are working in (ask the room assistant).
Measure the volumes of hydrochloric acid, distilled water, and potassium triiodide
solution (labelled as “I2”) that you choose into the reaction vessel. The initial
concentrations of the reagents in the reaction mixtures should be in the ranges given
below (you need not explore the full ranges given, but your values should not be
significantly outside these ranges):
[H+]: between 0.2 and 1.0 mol dm–3
[I3–]: between 0.0005 and 0.002 mol dm–3
[acetone]: between 0.5 and 1.5 mol dm–3
To initiate the reaction, add the chosen volume of acetone to the solution containing
the other reagents, quickly cap the reaction vessel, start the timer, shake the vial
vigorously one time, then put it aside on a white background. Report the volumes of
reagents that you use in table 1.1. When setting up and running a reaction do not hold or
touch the vial below the level of liquid in it. The progress of the reaction can be monitored
visually by watching the disappearance of the yellow-brown colour of the triiodide ion.
Record the time required for the colour to disappear. When the reaction is complete, set
aside the vessel, and leave it sealed so that you do not expose yourself to iodoacetone
vapours.
Repeat as often as desired with different concentrations of reagents. Report the
concentrations of the reagents that you use in table 1.3.
Hint: Change one concentration at a time.
Once you have studied the rate of reaction of acetone, you should examine the rate
of reaction of acetone-d6. Note that while you have an ample supply of acetone, you will be
given only 3.0 cm3 of acetone-d6 because of the greater expense of the isotopically
labelled material. Therefore, any refilling of acetone-d6 will be accompanied by a one
point penalty. When you need to use this reagent, raise your hand and the lab supervisor
will open the sealed ampoule for you. The reactions of deuterium-substituted compounds
are generally slower than those of protium-substituted compounds. You would thus be well
advised to use reaction conditions that promote faster reactions when working with
(CD3)2CO.
When you have finished your work:
a) empty the water bottle and place it along with any unused equipment back to the box
labelled “Kit #1”,
b) place used pipettes and sealed used vials in designated containers under the hoods,
c) use a container labelled “Broken Glass Disposal” to dispose of all parts of the empty
ampoule.
You may clean up your area after the STOP command has been given.
1.1 Record your results for acetone, (CH3)2CO, in the table below. You need not fill the
entire table.
Table 1.1
Run Volume HCl Time to
Volume Volume I3– Volume disappearance
solution,
# H2O, cm3 solution, cm3 (CH3)2CO, cm
3
cm3 of I3– , s
etc.
1.2 Record your results for acetone-d6, (CD3)2CO, in the table below. You need not fill
the entire table.
Table 1.2
Run Volume HCl Time to
Volume Volume I3– Volume disappearance
solution, 3 3 3
# 3 H2O, cm solution, cm (CD3)2CO, cm
cm of I3– , s
1d
2d
3d
etc.
1.3 Use the following tables to calculate concentrations and average rates for the
reactions you studied. Assume that the volume of each reaction mixture is equal to
the sum of volumes of its constituent solutions. You need not use all of your runs in
your calculation of k (parts 1.5 and 1.6), but you must indicate which run or runs you
used in your calculation by checking the appropriate box in the right-hand column.
Table 1.3
(CH3)2CO:
Average rate of
+ – Initial disappearance of Run used in
Run # Initial [H ], Initial [ I ],
3
[(CH3)2CO], calculating kH?
mol dm–3 mol dm–3 –3 I3– ,
mol dm –3 –1 Yes No
mol dm s
1
2
3
etc.
Table 1.4
(CD3)2CO:
Average rate of
+ – Initial disappearance of Run used in
Run # Initial [H ], Initial [ I ],
3
–3 [(CD3)2CO], calculating kD?
mol dm mol dm
–3
–3 I3– ,
mol dm –3 –1 Yes No
mol dm s
1d
2d
3d
1.4 Give the integer reaction order in acetone, triiodide, and hydrogen ion.
d[I3– ]
rate = − = k [(CH3 )2 CO] m [I3– ] n [H + ] p
dt
m= n= p=
1.5 Calculate the rate constant kH for the reaction of acetone, (CH3)2CO, and indicate the
units.
1.6 Calculate the rate constant kD for the reaction of acetone-d6, (CD3)2CO, and calculate
the value of kH / kD (the isotope effect of the reaction).
From the kinetic and isotope effect data you may draw certain conclusions about the
reaction mechanism. Shown below is a reasonable mechanism for the iodination of
acetone. One reaction is the rate-determining step with all previous steps rapidly achieving
an equilibrium that strongly favours the reactants.
1.7 In the box in the first column on the right next to each step, place a check mark ()
if your experimentally measured rate law (part 1.4) is consistent with that step being
rate-determining and a mark (X) if your measured rate law is inconsistent with that
step being rate-determining.
In the box in the second column on the right next to each step, place a check mark
() if your experimentally measured isotope effect (part 1.6) is consistent with that
step being rate-determining and a mark X if your measured isotope effect is
inconsistent with that step being rate-determining.
Rate Rate
determining step determining step
consistent with consistent with
rate law? isotope effect?
O OH+
+ H3 O +
+ H2O
OH
OH+
+ H 2O + H3O+
OH OH+
+ I 3- I
+ 2I-
OH+ O
+ H2O I
+ H3O+
I
_______________
SOLUTION
1.4 m = 1; n = 0; p=1
1.5 kH = 2.8 ± 0.4 · 10
–5 3 –1 –1
dm mol s
1.6 kD = 4.3 ± 0.6 · 10–6 dm3 mol–1 s–1
kH / kD = 6.5 ± 0.4
1.7
Rate Rate
determining step determining step
consistent with consistent with
rate law? isotope effect?
O OH+
+ H3 O + X

+ H2O
OH
OH+
+ H 2O + H3O+
OH OH+
+ I 3- I
+ 2I- X X
OH+ O
+ H2O + H3O+
I I X X
NTT VN-123
PRACTICAL EXAMINATION
Practical Code: Question 1 2 3 4 5 6 Total

Problem 1
Examiner Mark 2 4 50 2 2 10 70
14 % of the
total Grade
Practical Problem 1. The oxidation of iodide by iron(III) ions – a kinetic

study based on the thiosulfate clock reaction
Clock reactions are commonly used as demonstrations by chemical educators

owing to their visual appeal. Oxidation of iodide by iron(III) ions in a weakly acidic
medium is a reaction that can be transformed into a clock reaction. In the presence of
thiosulfate and starch, chemical changes in this clock reaction can be presented by the
following equations:
Fe3+ (aq) + S2O32-(aq) [Fe(S2O3)]+(aq) (1) f ast
2Fe3+(aq) + 3I-(aq) 2Fe2+(aq) + I3- (aq) (2) slow
I3-(aq) + 2S2O32- (aq) 3I- (aq) + S4O62- (aq) (3) f ast
2I3- (aq) + starch starch - I-5 + I- (aq) (4) f ast
Reaction (1) is a fast reversible equilibrium which occurs in the reaction mixture
giving a reservoir of iron(III) and thiosulfate ions. After being produced in reaction
(2), iodine in the form of triiodide ion (I3–), is immediately consumed by thiosulfate in
reaction (3). Therefore, no iodine accumulates in the presence of thiosulfate. When
thiosulfate is totally depleted, the triiodide ion accumulates and it may be detected by
use of starch indicator according to reaction (4).
The kinetics of reaction (2) is easily investigated using the initial rates method. One
has to measure the time elapsed between mixing the two solutions and the sudden
color change.
For the oxidation of iodide by iron(III) ions (reaction 2), the reaction rate can be
defined as:
d ⎡⎣ Fe3+ ⎤⎦
v=− (5)
dt

NTT VN-123
The initial reaction rate can then be approximated by:

Δ ⎡⎣ Fe3+ ⎤⎦
v0 ≈ − (6)
Δt
with Δ[Fe3+] being the change in the concentration of iron(III) ions in the initial period
of the reaction. If Δt is the time measured, then Δ[Fe3+] is the change in iron(III) ion
concentration from the moment of mixing to the moment of complete thiosulfate
consumption (assume that the reaction rate does not depend on thiosulfate
concentration). Therefore, from the reactions' stoichiometry it follows:
−Δ ⎡⎣ Fe3+ ⎤⎦ = ⎡⎣S2O32− ⎤⎦ (7)

0
and consequently:
⎡⎣S2O32− ⎤⎦
v0 ≈ 0
(8)
Δt
The initial thiosulfate concentration is constant and significantly lower than that of
iron(III) and iodide ions. The above expression enables us to determine the initial
reaction rate by measuring the time required for the sudden color change to take place,
Δt.
The rate of reaction is first order with respect to [Fe3+], and you will determine the
order with respect to [I–]. This means the initial reaction rate of reaction can be
expressed as:
v0 = k [Fe3+ ]0 [I − ]0y (9)
where k is the rate constant and y is the order with respect to [I–].
We assume that the reaction rate does not depend on the thiosulfate concentration, and
that the reaction between Fe3+ and S2O32- is negligible. You have to observe carefully
the color changes during the clock reaction and to determine the reaction order with
respect to [I–], and the rate constant of clock reaction.

NTT VN-123
Experimental Set-up
Instructions for using the digital timer (stopwatch)

1. Press the [MODE] button until the 00:00:00 icon is displayed.
2. To begin timing, press the [START/STOP] button.
3. To stop timing, press the [START/STOP] button again.
4. To clear the display, press the [SPLIT/RESET] button.
PRECAUTIONS
¾ To minimize fluctuations in temperature only use the distilled water on your
bench (in the wash bottle and in the glass 1 L bottle).
¾ The heating function of the heating magnetic stirrer must be TURNED OFF
(as shown in Figure 1 below) and be sure that the stirrer plate is not hot before starting
your experiment. Put the insulating plate (labeled I.P.) on top of the stirrer plate for
added insulation.
¾ Start the stopwatch as soon as the solutions #A and #B are mixed. Stop the
stopwatch as soon as the solution suddenly turns dark blue.
¾ Magnetic stirrer bar (take it with the provided tweezers) and beakers should be
washed and rinsed with distilled water and wiped dry with paper towel to reuse.
General Procedure
Solution # A (containing Na2S2O3, KI, KNO3 and starch) is first placed in the beaker
and is stirred using the magnetic bar. The rate of stirring is set at level 8 as indicated in
Figure 1. Solution #B (containing Fe(NO3)3 and HNO3) is quickly added into solution
#A and the stopwatch is simultaneously started. The time is recorded at the moment
the solution suddenly turns dark blue. The temperature of the solution is recorded
using the digital thermometer.
Insulating
plate (I.P.)
Figure 1. The apparatus employed for kinetic study of the clock reaction.

NTT VN-123
1. Practice run to observe the color changes

- There is no need to accurately measure the volumes used in this part – just use the
marks on the beaker as a guide.
- Pour ca. 20 mL of solution # A1 (containing KI, Na2S2O3, and starch in water) to a
100-mL graduated beaker containing a magnetic stirrer bar. Place the beaker on top
of the insulating plate on the magnetic stirrer.
- Pour ca. 20 mL of solution # B1 (containing Fe(NO3)3 and HNO3 in water) in
another 100 mL graduated beaker.
- Quickly pour the solution # B1 into solution # A1 and start stopwatch
simultaneously. Stop stopwatch when the color of the mixture changes. There is no
need to record this time. Answer the following questions.
Task 1.1: Write down the molecular formula of the limiting reactant for the given
clock reaction.
Task 1.2: What are the ions or compounds responsible for the colors observed in this
experiment? Tick the appropriate box.
Color Compound
Fe3+
[Fe(S2O3)]+
Purple Fe2+
starch-I5-
I3 -
Fe3+
[Fe(S2O3)]+
Dark blue Fe2+
starch-I5-
I3 -

NTT VN-123
2. Determination of the order with respect to [I–] (y), and the rate constant (k)
In this section, Δt is determined for different initial concentrations of KI according
to the table below. The experiment is repeated as necessary for each concentration of
KI.
Hint: Use 25 mL graduated pipette for solution #A2-1, 10 mL graduated pipette for
KI, 5 mL graduated pipette for solution #B2, and one of the burettes for water (you
will need to refill the burette from the wash bottle for each measurement).
- Prepare 55 mL of solution # A2 in a 100 mL beaker containing a magnetic stirrer
bar and place it on top of the insulating plate on the stirrer. Solution #A2 contains
solution #A2-1, KI, and distilled water (see the table below for the volume of each
component).
- Add 5 mL of solution # B2 in another 100 mL beaker.
Quickly pour prepared solution #B2 into solution #A2. Determine the time (Δt)
necessary for the color change by a stopwatch. The temperature of the solution is
recorded.
Task 1.3: Record the time (Δt) for each run in the table below. (You DO NOT need
to fill all three columns for the runs.) For each concentration of KI, record your
accepted reaction time (Δtaccepted) and temperature. You will be only graded on your
values of Δtaccepted and Taccepted.
55 mL of solution #A2
N Δtaccepted Taccepted
o 0.100M Run 1 Run 2 Run 3 (s) (ºC)
#A2-1 H2O
KI
(mL) (mL) Δt T Δt T Δt T
(mL)
(s) (ºC) (s) (ºC) (s) (ºC)
1 20.4 31.6 3.0
2 20.4 30.1 4.5
3 20.4 28.6 6.0
4 20.4 27.4 7.2
5 20.4 25.6 9.0

NTT VN-123
When you are satisfied you have all the necessary data for Problem 1, before
continuing further with the analysis, it is strongly recommended that you start the
practical procedure for Problem 2 since there is a reaction time of one hour in that
Problem.
Task 1.4: Fill in the table below and plot the results in the graph.
Hint: Make sure your data is graphed as large as possible in the provided space.
No. 1 2 3 4 5
ln([I-]0 / M) - 5.30 - 4.89 - 4.61 - 4.42 - 4.20
Δtaccepted (s)
ln(Δtaccepted / s)

NTT VN-123

NTT VN-123
Task 1.5: Draw the best fit line on your graph and use this to determine the order
with respect to [I–] (y).
y = ………………………………
Task 1.6: Complete the table below and calculate k for each of the concentrations of
iodide. Report your accepted value for the rate constant, giving the appropriate unit.
Remember that the order with respect to [Fe3+] is equal to one.
Δtaccepted [Fe3+]0 [I-]0 [S2O32-]0

No k
(s) (×10-3 M) (×10-3 M) (×10-3 M)
1 5.0
2 7.5
3 10.0
4 12.0
5 15.0
kaccepted = ………………….

TASK 3. Kinetic determination of Diclofenac (DCF) (13 points)
Quest. # Q1 DCF curves DCF Control Reaction order Total

Marks 10 40 20 10 80
Kinetic methods with spectrophotometric detection for assaying drugs have been intensively developed
during the last decade due to a number of obvious advantages, including inherent simplicity, cost-
effectiveness, availability in most quality control laboratories, and improved selectivity. In this task you
will:
• Perform kinetic determination of Diclofenac (DCF) in a medicine by following the progress of
the drug oxidation reaction.
• Determine the reaction order with respect to DCF
Q1. Spectral changes in the course of DCF oxidation with KMnO4 are given in Fig. 4, (1 to 10 reflects
the reaction progress). Complete the table below suggesting which wavelengths can be applied for
photometric kinetic determination of DCF. In each case, indicate the direction of the absorbance
changes (denote increasing with ↑ and decreasing with ↓).
Fig. 4. DCF oxidation with KMnO4
# Wavelength, nm Yes or No and direction

1 420
2 480
3 520
4 580
5 610
20
Procedure
Part A. Assembling of laboratory equipment

Assemble the laboratory equipment as shown in Fig. 5. Connect the photometer (1), 525 nm (fixed
wavelength) and thermostat (2) to the Netbook via USB slots. Connect the thermostat to the cable
labeled “Thermo” to the power supply at your work place via the power adapter. Put the optical cuvette
(3) on top of the magnetic stirrer (4), pass the cuvette through the photometer from aside (not possible
from top down) and place the thermostat over the cuvette from top down (Fig. 5b).
Fig. 5. Laboratory equipment
Hints!
- Plug in your Netbook to the mains before switching on.
- Plug in all the equipment (the photometer and thermostat) before switching on the Netbook.
Switch on the mouse.
- If only one window (hereafter referred to as Pattern) instead of two appears after launching
the software, quit and re-launch the program.
21
- Do not unplug ANY device from the USB slot while carrying out the measurements. If it still
happens, you will see a warning on the screen. Quit and re-launch the program.
- If your Netbook falls asleep, click the «Setup» button in the Measurements window on the
absorbance plot pattern when reverting to the measurements.
- In case you see chaotic temperature changes on the screen, stop and re-start the measurement.
Part B. Plotting of the calibration curve

All measurements needed to plot the calibration curve are carried out at 30 °C with constant KMnO4 and
H2SO4 initial concentrations. The DCF concentration is varied by using 4 different aliquots (of 0.2, 0.4,
0.6, and 0.8 mL) of the DCF stock solution.
1) Transfer 5 mL of 1M H2SO4 solution using the graduated cylinder and 0.2 mL of DCF stock
solution using the 2 mL pipette into the 100 mL volumetric flask, dilute to the mark with
distilled water, stopper the flask and mix thoroughly.
2) Carry over the flask contents into the cuvette, put the medium-size stir-bar and switch on the
magnetic stirrer. Adjust the stirring speed regulator to the mark shown on Fig. 5a to provide for
intensive mixing.
3) Launch the «Chemistry-Practicum» software on the Netbook. The software will detect the
external devices (sensors) automatically. You will see two plot patterns (that of
absorbance/extinction/optical density, D vs. t, s; and that of temperature, T °C vs. t, s) on the
display.
4) Set the following parameters in the Menu bars of the corresponding plot patterns (Fig. 6):
- Click the icon next to the button («Fixes X-axis maximum on screen») on the
absorbance plot pattern. The entire plot will always fit to the screen;
- Click the button («Sets the Y range») on the absorbance plot pattern and set the absorbance
range (the ordinate axis) from -0.1 to 1.1.
- Type “2” (instead of “1”) in the box of the measurements interval on the absorbance plot pattern.
- Choose «Precisely» in the «Precisely/Roughly» window on the temperature plot pattern, then
click on the «T = X» button and set the required temperature of 30 °C in the pop-up window.
- Calibrate the photometer by clicking the «Setup» button in the Measurements window on the
absorbance plot pattern.
22
Fig. 6. “Chemistry-Practicum” software interface
Note! Setting the parameters (step 4) is needed only prior to the first measurement.
5) Click the button («Start measure for chosen sensors») to switch on the thermostat and
observe the lamp heating up the solution in the cuvette. Follow the current temperature reported
in the line above the plot. Wait until the thermostat lamp switches off, reflecting the set up
temperature is attained. Stop the measurements by clicking button (is activated and turns to
red-orange when the measurement is on).
6) Click any part of the absorbance plot pattern to activate it. Take 2 mL of the KMnO4 solution
using the 2 mL pipette. Click the button («Start measure for chosen sensors») in the Menu
bar of the Measurements window and quickly blow out (press the pipette piston) the
permanganate solution from the pipette into the cuvette.
Note! Make sure the temperature in the cuvette equals 30 °C before adding the KMnO4 solution!
7) Observe the progress of the kinetic curve on the screen. Continue measurement for 50 s after
adding the KMnO4 solution, then terminate the measurement by clicking the «Stop
measurements» button.
23
8) Save the data by clicking the button («Export all the data collected in an external file») in
the Menu bar of the absorbance plot pattern, choose the Desktop and type the file name “DCF2”
(change the name to “DCF4”, or “DCF6”, or “DCF8” in the subsequent experiments).
Note!
- Use only the names of the given format!
- Always save the data on your Desktop before starting the next experiment, otherwise the
current data set will be lost after the next click on the button.
- Make sure absorbance plot pattern is active when exporting the data. Otherwise, you will
export invalid results. In case no pattern is chosen, you will get a warning.
9) Empty the cuvette into the Waste bottle, wash thoroughly the cuvette with distilled water. Use
black magnet from the outer side of the cuvette to avoid your stir-bar being dropped into the
Waste bottle while washing. Wipe carefully the external surfaces of the cuvette with the napkin.
Also, use the napkin to dab the thermostat lamp.
10) Repeat the steps 1), 2) 5)-9) with the other volumes of the DCF stock solution.
Part C.
1. Studying of the DCF containing medicine (“Control”)
1) Wash the volumetric flask and prepare the mixture as described above using a 0.4 mL aliquot of
the medicine (“Control”) instead of the DCF stock solution.
2) Repeat the steps 1), 2), 5)-9) described in Part B. When saving the data, name the file
“DCFmed”.
3) Repeat the measurement of the “Control” as necessary.
2. Experimental data analysis

1) Open the Excel file on your memory stick in Excel. One by one open your saved data files in
Notepad by double clicking on them on Desktop. Choose Edit/Select All in the Menu bar, then
right click and copy the selected data into the Excel sheet with the corresponding name (the
volume of DCF added or “DCFmed”) and choose Edit/Paste in the Menu bar. You will see the
experimental data on the Excel sheet (time, s, in column A, and absorbance in column B).
24
2) Ignore the values before the maximum. Select columns A and B, and plot the data. Use the
“Insert Scatter” icon shown on Fig. 7.
Figure 7. Position of the “Insert Scatter” icon
3) Choose the initial linear section of the remaining curve (15 to 20 data points), apply linear
approximation by adding the linear trend line and bring the parameters to the chart area. Make
sure that the R2 value exceeds 0.98. If needed, decrease the number of the experimental data
points plotted removing later data points. Still always search for the most wide range of the
experimental data providing for the target R2 value. Determine the value of the initial rate of
absorbance change, v0.
Note! You will get zero point for this part of the task if less than 12 values are included in the plotted
data range.
4) Analyze similarly the experimental data obtained with the other DCF concentrations and with the
medicine solution “Control” (“DCFmed” file).
5) Calculate the DCF concentrations in the reaction mixtures (in mg/L). Write down the DCF
concentrations and initial rates in appropriate cells of the “Results” Excel sheet.
6) Plot the calibration graph on the “Results” sheet and use it to determine the DCF concentration
in the analyzed mixture prepared from the medicine (“Control”). Fill in the appropriate cells of
the “Results” Excel sheet with the coefficients of linear approximation of the calibration graph.
Calculate the DCF concentration in the medicine.
7) Write down the accepted value in the cell F10 of the “Results” sheet.
8) On the “Results” Excel sheet, graphically determine the reaction order with respect to DCF and
write down the exact obtained value in the cell I3.
9) Once finished, save your file and invite your Lab assistant to demonstrate that you have got
experimental data in the Excel file. Sign and get the Lab assistant’s signature.
Note! Only the data saved on the memory stick will be considered as the result of the Task.
25
Data present in Excel on the memory stick (to be ticked by the Lab assistant)
Yes No Student Lab assistant
______________ ______________
REPLACEMENTS WITH PENALTY
Item Quantity Student’s signature Lab assistant’s signature
26
TASK 3. Kinetic determination of Diclofenac (DCF) (13 points)
Quest. # Q1 DCF curves DCF Control Reaction order Total

Marks 10 40 20 10 80
Kinetic methods with spectrophotometric detection for assaying drugs have been intensively developed
during the last decade due to a number of obvious advantages, including inherent simplicity, cost-
effectiveness, availability in most quality control laboratories, and improved selectivity. In this task you
will:
• Perform kinetic determination of Diclofenac (DCF) in a medicine by following the progress of
the drug oxidation reaction.
• Determine the reaction order with respect to DCF
Q1. Spectral changes in the course of DCF oxidation with KMnO4 are given in Fig. 4, (1 to 10 reflects
the reaction progress). Complete the table below suggesting which wavelengths can be applied for
photometric kinetic determination of DCF. In each case, indicate the direction of the absorbance
changes (denote increasing with ↑ and decreasing with ↓).
Fig. 4. DCF oxidation with KMnO4
# Wavelength, nm Yes or No and direction

1 420 Yes ↑ 2 marks
2 480 No 2 marks
3 520 Yes ↓ 2 marks
4 580 No 2 marks
5 610 Yes ↑ 2 marks
22
Procedure
Part A. Assembling of laboratory equipment

Assemble the laboratory equipment as shown in Fig. 5. Connect the photometer (1), 525 nm (fixed
wavelength) and thermostat (2) to the Netbook via USB slots. Connect the thermostat to the cable
labeled “Thermo” to the power supply at your work place via the power adapter. Put the optical cuvette
(3) on top of the magnetic stirrer (4), pass the cuvette through the photometer from aside (not possible
from top down) and place the thermostat over the cuvette from top down (Fig. 5b).
Fig. 5. Laboratory equipment
Hints!
- Plug in your Netbook to the mains before switching on.
- Plug in all the equipment (the photometer and thermostat) before switching on the Netbook.
Switch on the mouse.
- If only one window (hereafter referred to as Pattern) instead of two appears after launching
the software, quit and re-launch the program.
23
- Do not unplug ANY device from the USB slot while carrying out the measurements. If it still
happens, you will see a warning on the screen. Quit and re-launch the program.
- If your Netbook falls asleep, click the «Setup» button in the Measurements window on the
absorbance plot pattern when reverting to the measurements.
- In case you see chaotic temperature changes on the screen, stop and re-start the measurement.
Part B. Plotting of the calibration curve

All measurements needed to plot the calibration curve are carried out at 30 °C with constant KMnO4 and
H2SO4 initial concentrations. The DCF concentration is varied by using 4 different aliquots (of 0.2, 0.4,
0.6, and 0.8 mL) of the DCF stock solution.
1) Transfer 5 mL of 1M H2SO4 solution using the graduated cylinder and 0.2 mL of DCF stock
solution using the 2 mL pipette into the 100 mL volumetric flask, dilute to the mark with
distilled water, stopper the flask and mix thoroughly.
2) Carry over the flask contents into the cuvette, put the medium-size stir-bar and switch on the
magnetic stirrer. Adjust the stirring speed regulator to the mark shown on Fig. 5a to provide for
intensive mixing.
3) Launch the «Chemistry-Practicum» software on the Netbook. The software will detect the
external devices (sensors) automatically. You will see two plot patterns (that of
absorbance/extinction/optical density, D vs. t, s; and that of temperature, T °C vs. t, s) on the
display.
4) Set the following parameters in the Menu bars of the corresponding plot patterns (Fig. 6):
- Click the icon next to the button («Fixes X-axis maximum on screen») on the
absorbance plot pattern. The entire plot will always fit to the screen;
- Click the button («Sets the Y range») on the absorbance plot pattern and set the absorbance
range (the ordinate axis) from -0.1 to 1.1.
- Type “2” (instead of “1”) in the box of the measurements interval on the absorbance plot pattern.
- Choose «Precisely» in the «Precisely/Roughly» window on the temperature plot pattern, then
click on the «T = X» button and set the required temperature of 30 °C in the pop-up window.
- Calibrate the photometer by clicking the «Setup» button in the Measurements window on the
absorbance plot pattern.
24
Fig. 6. “Chemistry-Practicum” software interface
Note! Setting the parameters (step 4) is needed only prior to the first measurement.
5) Click the button («Start measure for chosen sensors») to switch on the thermostat and
observe the lamp heating up the solution in the cuvette. Follow the current temperature reported
in the line above the plot. Wait until the thermostat lamp switches off, reflecting the set up
temperature is attained. Stop the measurements by clicking button (is activated and turns to
red-orange when the measurement is on).
6) Click any part of the absorbance plot pattern to activate it. Take 2 mL of the KMnO4 solution
using the 2 mL pipette. Click the button («Start measure for chosen sensors») in the Menu
bar of the Measurements window and quickly blow out (press the pipette piston) the
permanganate solution from the pipette into the cuvette.
Note! Make sure the temperature in the cuvette equals 30 °C before adding the KMnO4 solution!
7) Observe the progress of the kinetic curve on the screen. Continue measurement for 50 s after
adding the KMnO4 solution, then terminate the measurement by clicking the «Stop
measurements» button.
25
8) Save the data by clicking the button («Export all the data collected in an external file») in
the Menu bar of the absorbance plot pattern, choose the Desktop and type the file name “DCF2”
(change the name to “DCF4”, or “DCF6”, or “DCF8” in the subsequent experiments).
Note!
- Use only the names of the given format!
- Always save the data on your Desktop before starting the next experiment, otherwise the
current data set will be lost after the next click on the button.
- Make sure absorbance plot pattern is active when exporting the data. Otherwise, you will
export invalid results. In case no pattern is chosen, you will get a warning.
9) Empty the cuvette into the Waste bottle, wash thoroughly the cuvette with distilled water. Use
black magnet from the outer side of the cuvette to avoid your stir-bar being dropped into the
Waste bottle while washing. Wipe carefully the external surfaces of the cuvette with the napkin.
Also, use the napkin to dab the thermostat lamp.
10) Repeat the steps 1), 2) 5)-9) with the other volumes of the DCF stock solution.
10 marks maximum for each of 4 measurements. Students data will be recalculated by Science
Committee. 40 marks in total.
26
Part C.
1. Studying of the DCF containing medicine (“Control”)
1) Wash the volumetric flask and prepare the mixture as described above using a 0.4 mL aliquot of
the medicine (“Control”) instead of the DCF stock solution.
2) Repeat the steps 1), 2), 5)-9) described in Part B. When saving the data, name the file
“DCFmed”.
3) Repeat the measurement of the “Control” as necessary.
2. Experimental data analysis

1) Open the Excel file on your memory stick in Excel. One by one open your saved data files in
Notepad by double clicking on them on Desktop. Choose Edit/Select All in the Menu bar, then
right click and copy the selected data into the Excel sheet with the corresponding name (the
volume of DCF added or “DCFmed”) and choose Edit/Paste in the Menu bar. You will see the
experimental data on the Excel sheet (time, s, in column A, and absorbance in column B).
2) Ignore the values before the maximum. Select columns A and B, and plot the data. Use the
“Insert Scatter” icon shown on Fig. 7.
Figure 7. Position of the “Insert Scatter” icon
3) Choose the initial linear section of the remaining curve (15 to 20 data points), apply linear
approximation by adding the linear trend line and bring the parameters to the chart area. Make
sure that the R2 value exceeds 0.98. If needed, decrease the number of the experimental data
points plotted removing later data points. Still always search for the most wide range of the
experimental data providing for the target R2 value. Determine the value of the initial rate of
absorbance change, v0.
27
Note! You will get zero point for this part of the task if less than 12 values are included in the plotted
data range.
4) Analyze similarly the experimental data obtained with the other DCF concentrations and with the
medicine solution “Control” (“DCFmed” file).
5) Calculate the DCF concentrations in the reaction mixtures (in mg/L). Write down the DCF
concentrations and initial rates in appropriate cells of the “Results” Excel sheet.
6) Plot the calibration graph on the “Results” sheet and use it to determine the DCF concentration
in the analyzed mixture prepared from the medicine (“Control”). Fill in the appropriate cells of
the “Results” Excel sheet with the coefficients of linear approximation of the calibration graph.
Calculate the DCF concentration in the medicine.
20 marks maximum (including 8 marks for data obtained and calculations). To be graded similarly
to the procedure in Task 1.
The grading scheme takes into account two values re-measured by the Science Committee: R-squared
value (R2) and obtained concentration of the control solution (Conc).
• If the value obtained is within region A, 100% of 12 marks
• If the value obtained is within region B, 0.1926*Conc-154.2857 (%) of 12 marks
• If the value obtained is within region C, 400*R2-372 (%) of 12 marks
• If the value obtained is within region D, -0.1926*Conc+188.5714 (%) of 12 marks
Master value – 890.1 mg/L
7) Write down the accepted value in the cell F10 of the “Results” sheet.
28
8) On the “Results” Excel sheet, graphically determine the reaction order with respect to DCF and
write down the exact obtained value in the cell I3.
10 marks for the determination of the reaction order
9) Once finished, save your file and invite your Lab assistant to demonstrate that you have got
experimental data in the Excel file. Sign and get the Lab assistant’s signature.
Note! Only the data saved on the memory stick will be considered as the result of the Task.
Data present in Excel on the memory stick (to be ticked by the Lab assistant)
Yes No Student Lab assistant
______________ ______________
REPLACEMENTS WITH PENALTY
Item Quantity Student’s signature Lab assistant’s signature
29
GBR-1
Chemicals
For all problems
Deionised water in:
Wash bottle (bench)
Water Not hazardous

2-Acetonaphthone:
Standard A H302, H315, H319, H335,
H411
DNPH H228, H302
Bleach H290, H314, H400
amber glass bottle
TLC eluent
H290, H314, H319, H335
and others

H290, H315, H319
Cu Not hazardous
plastic bottle
H2O2 conc. H302, H315, H318
plastic bottle


GBR-1

(bench)
Buffer H302, H319, H314, H400
(bench)
NaOH H314
bottle
Equipment
Personal equipment
Safety goggles 1
1 (each)

Personal equipment

GBR-1

Open metal ring 1
Reflux condenser 1
Glass funnel 1
1
label)
Rubber bulb 1
1
haloform reaction
1

Stopwatch 1
1
H2O2, 50 cm3
1

GBR-1


1 (each)
Burette clamp
Burette, 25 cm3
Glass funnel 1

GBR-1
Practical Question 2.1 2.2 2.3 2.4 2.5 2.6 Total

Problem P2 Points 30 30 7 3 4 6 80
13% of the total Score
Problem P2. A glowing clock reaction

Luminol is a well-known source of chemiluminescence. In the presence of a suitable redox catalyst,
e.g. Cu2+, it may react with oxidising agents, most commonly H2O2, forming products in excited
electronic states. These release the excess energy by the emission of blue light:
NH2 O NH2 O NH2 O
NH H2O2/Cu2+ O N O
- ON + N2 + h (425 nm)
NH HO O
Luminol O O O
The procedure may be modified into a clock reaction, in which the light appears after a certain
induction time. By adding cysteine, Cu(II) is reduced to Cu(I) and captured in a Cu(I)–cysteine
complex that does not facilitate the luminol oxidation. However, the inhibition is only temporary.
A cycle of reactions fuelled by H2O2 leads to the gradual oxidation of cysteine:
NH2 NH 2
2 HS H2O2 HOOC S
COOH S COOH
HO-
NH2
Cysteine Cystine
Eventually, all cysteine is consumed, Cu(I) is reoxidised to Cu(II), and its catalytic activity is restored.
This is indicated by a flash of blue chemiluminescence. The time it takes until the flash appears can
be used to study the rates of the Cu-catalysed cysteine oxidation.
Procedure
Caution: Always keep all your solutions and pipettes away from hotplates!
Reasonable temperature changes are not a problem, because your results will be marked based on
the actual reaction temperatures that you report. You will not lose any points if your data is recorded
at various temperatures. However, you must avoid excessive heat, e.g. placing the solutions or the
pipettes near a hotplate.
Note: Report all the values with the requested number of significant figures or decimal places.
Excessive rounding may make it impossible to distinguish a correct answer from an incorrect one.
General structure of the experiment

In Part I, you will dilute two stock solutions that are provided as concentrates. In Part II, you will
measure the reaction times of the clock reaction for two different concentration sets, as defined in
the table below:

GBR-1
Volume in the black test tube In the centrifuge tube
Water Luminol in NaOH Cys dil. Cu H2O2 dil.
Conc. set #1 3.00 cm3 2.50 cm3 3.30 cm3 0.50 cm3 0.70 cm3
It is recommended that before you start measuring the data to be graded, you should get familiar
with the procedure in a trial run.
Because the reaction rate depends on temperature, you must record the actual temperatures in all
replicates. The temperatures in the reaction mixtures should be measured IMMEDIATELY AFTER
you have recorded the reaction time required to produce the blue flash.
In data evaluation, each temperature recorded from the thermometer’s display must be corrected by
summing it with the thermometer’s calibration constant. This constant is printed on a piece of paper
in the basket for Problem 2.
Then, each reaction time t(x °C) observed at x °C (corrected) must be converted to the time t(25 °C)
that would be observed at 25 °C. This normalisation of reaction times to 25 °C is a simple
multiplication of t(x °C) with a normalisation coefficient nx→25:
t(25 °C) = nx→25 t(x °C)
The values of the normalisation coefficients nx→25 corresponding to various temperatures are listed
in Table P2 at the end of this task.
I. Dilution of the concentrated stock solutions

Solutions of H2O2 (2.00 mol dm−3) and cysteine (0.100 mol dm−3) are provided as concentrates,
labelled H2O2 conc. and Cys conc. Using the 5 cm3 bulb pipette and the 50 cm3 volumetric flask,
dilute 5.00 cm3 of each to 50.00 cm3 with deionised water and store the diluted solution in the bottles
labelled H2O2 dil. and Cys dil.
For measuring the solution volumes in the following steps, label one graduated pipette for each of
the bottles. The 5 cm3 pipettes are for Luminol in NaOH, Cys dil., and Water. The 1 cm3 pipettes
are for Cu (2.00 mmol dm−3) and H2O2 dil.
II. The clock reaction procedure

Note: Read the entire Section II carefully before starting the experiment.
1. Place the black test tube inside the conical flask serving as a stand. Using the assigned pipettes,
charge the test tube with the prescribed volumes of Water, Luminol in NaOH and
Cys dil. solution.
2. Place the small centrifuge tube inside the small plastic beaker and charge it with the prescribed
volumes of Cu solution and H2O2 dil. solution.
3. Without delay, insert the small centrifuge tube inside the black test tube – gently, without
mixing the two solutions!

GBR-1
4. Close the test tube with its screw-on cap. Make sure that the tube is closed tightly, because you
will be shaking it. Caution: Do not force the cap beyond its end-point, because the tube will
start leaking. If this happens, you must ask for a replacement immediately (penalty rules apply).
5. Have the stopwatch ready in your hand, in timing mode. The moment you begin shaking the test
tube, start timing. You must shake vigorously during the initial 10 seconds, so that the two
solutions mix perfectly. It is crucial that you do not cut down the shaking time.
6. Return the test tube into the conical flask, open the lid and watch the solution inside closely. It
may help to shield away the daylight with your hand. Eventually, you will see a flash of blue light
through the whole solution. At that moment, stop timing.
7. Immediately, insert the metal probe of the digital thermometer into the black test tube. Wait for
the reading to stabilise (typically 10–30 s) and record the reaction time and the reaction
temperature.
8. Using tweezers, remove the small centrifuge tube from the black test tube. After each experiment,
empty and wash both tubes and dry them with paper wipes.
Measured data and their evaluation

P2.1 In the following table, record your experimental results for concentration set #1. To the
displayed temperature add the thermometer’s calibration constant. Look up the value of the
normalisation coefficient nx→25 for each temperature in Table P2 and calculate the reaction
times normalised to 25 °C. In an unlikely case that your temperatures are not listed in Table
P2, get the value of nx→25 from the lab assistant.
Note: In a titration, the concordant values are within ±0.1 cm3. Here, concordant values of the
normalised times for concentration set #1 are within ±2.3 s.
(Use as many replicates as you consider necessary, you do not need to fill in all the
rows. Points will be awarded for the accepted value only.)
Displayed Corrected Reaction time

Reaction time
temperature temperature normalised to 25 °C
Repli- [s]
[°C] [°C]
cate 1 decimal [s]
1 decimal 1 decimal
place 3 significant figures
place place
2
Conc.
set #1 3
Accepted value of the normalised reaction time

for concentration set #1

GBR-1
P2.2 In the following table, record your experimental results, the corrected temperature and
calculate the reaction times normalised to 25 °C for concentration set #2.
Note: Here, concordant values of the normalised times for concentration set #2 are within ±3.0 s.
(Use as many replicates as you consider necessary; you do not need to fill in all the
rows. Points will be awarded for the accepted value only.)

Reaction time
temperature temperature normalised to 25 °C
Repli- [s]
[°C] [°C]
cate 1 decimal [s]
1 decimal 1 decimal
place place
2
Conc.
set #2 3
Accepted value of the normalised reaction time

P2.3 Based on the procedure and on the concentrations of the stock solutions (specified in the list
of chemicals and in Part I. of the Procedure), calculate the initial concentrations of cysteine,
copper and H2O2 in both concentration sets.
Express the accepted reaction times (t1 and t2) from P2.1 and P2.2 in minutes and calculate
the corresponding reaction rates (v1 and v2), expressed as the rates of the consumption of
the cysteine concentration, in mmol dm−3 min−1. You can assume that the rate of cysteine
consumption during the reaction is constant.
If you cannot find the reaction rate, use the value 11.50 for conc. set #1 and 5.500 for conc.
set #2 in further calculations.
Initial concentrations
Accepted
[mmol dm−3]
reaction time Reaction rate
3 significant figures [min] [mmol dm−3 min−1]
4 significant 4 significant figures
Copper
Cysteine H2O2 figures
[Cu]
Conc. set #1
Conc. set #2

GBR-1
P2.4 Assuming the rate equation can be expressed as

v = k [H2 O2 ]p
use your experimental data to calculate the partial reaction order p with respect to H2O2. Write
down your answer with 2 decimal places and show your calculation.
Answer: p=
Calculation:
An expression of the rate law of cysteine consumption that is closer to reality is more
complicated and takes the following form:
v = k1 [H2 O2 ][Cu] + k2 [Cu]
P2.5 Using the data from P2.3, evaluate the dependence of v on [H2O2] as a linear function to find
the slope and the intercept. Write down both answers with 4 significant figures. If you cannot find
constants a and b, use the value 11.50 for both a and b in further calculations.
Answers (do not include the calculation, but include units):
v = a[H2 O2 ] + b a= b=
P2.6 Use the numeric values from P2.5 to evaluate the rate constants k1 and k2. Write down their
values with 3 significant figures.
Answers (including units):

k1 = k2 =
Calculations:

GBR-1
Table P2. Normalisation coefficients nx→25 for converting reaction times measured at various temperatures
to times representing the reactions at 25.0 °C.

XXX-X
Practical Question 2.1 2.2 2.3 2.4 2.5 2.6 Total

Problem P2 Points 30 30 7 3 4 6 80
Problem P2. A glowing clock reaction

Luminol is a well-known source of chemiluminescence. In the presence of a suitable redox catalyst,
e.g. Cu2+, it may react with oxidizing agents, most commonly H2O2, forming products in excited
electronic states. These release the excess energy by the emission of blue light:
The procedure may be modified into a clock reaction, in which the light appears after a certain
induction time. By adding cysteine, Cu(II) is reduced to Cu(I) and captured in a Cu(I)–cysteine
complex that does not facilitate the luminol oxidation. However, the inhibition is only temporary.
A cycle of reactions fuelled by H2O2 leads to the gradual oxidation of cysteine:
Eventually, all cysteine is consumed, Cu(I) is reoxidized to Cu(II), and its catalytic activity is restored.
This is indicated by a flash of blue chemiluminescence. The time it takes for the flash to appear can
be used to study the rates of the Cu-catalyzed cysteine oxidation.
Procedure
Caution: Always keep all your solutions and pipettes away from hotplates!
Reasonable temperature changes are not a problem, because your results will be marked based on
the actual reaction temperatures that you report. You will not lose any points if your data is recorded
at various temperatures. However, you must avoid excessive heat, e.g. placing the solutions or the
pipettes near a hotplate.
Note: Report all the values with the requested number of significant figures or decimal places.
Excessive rounding may make it impossible to distinguish a correct answer from an incorrect one.
General structure of the experiment

In Part I, you will dilute two stock solutions that are provided as concentrates. In Part II, you will
measure the reaction times of the clock reaction for two different concentration sets, as defined in
the table below:

XXX-X
Volume in the black test tube In the centrifuge tube
Water Luminol in NaOH Cys dil. Cu H2O2 dil.
It is recommended that before you start measuring the data to be graded, you should get familiar
with the procedure in a trial run.
Because the reaction rate depends on temperature, you must record the actual temperatures in all
replicates. The temperatures in the reaction mixtures should be measured IMMEDIATELY AFTER
you have recorded the reaction time required to produce the blue flash.
In data evaluation, each temperature recorded from the thermometer’s display must be corrected by
summing it with the thermometer’s calibration constant. This constant is printed on a piece of paper
in the basket for Problem 2.
Then, each reaction time t(x °C) observed at x °C (corrected) must be converted to the time t(25 °C)
that would be observed at 25 °C. This normalization of reaction times to 25 °C is a simple
multiplication of t(x °C) with a normalization coefficient nx→25:
t(25 °C) = nx→25 t(x °C)
The values of the normalization coefficients nx→25 corresponding to various temperatures are listed
in Table P2 at the end of this task.
I. Dilution of the concentrated stock solutions

Solutions of H2O2 (2.00 mol dm−3) and cysteine (0.100 mol dm−3) are provided as concentrates,
labelled H2O2 conc. and Cys conc. Using the 5 cm3 bulb pipette and the 50 cm3 volumetric flask,
dilute 5.00 cm3 of each to 50.00 cm3 with deionized water and store the diluted solution in the bottles
labelled H2O2 dil. and Cys dil.
For measuring the solution volumes in the following steps, assign one graduated pipette for each of
the bottles. The 5 cm3 pipettes are for Luminol in NaOH, Cys dil., and Water. The 1 cm3 pipettes
are for Cu (2.00 mmol dm−3) and H2O2 dil.
II. The clock reaction procedure

Note: Read the entire Section II carefully before starting the experiment.
1. Place the black test tube inside the Erlenmeyer flask serving as a stand. Using the assigned
pipettes, charge the test tube with the prescribed volumes of Water, Luminol in NaOH and
Cys dil. solution.
2. Place the small centrifuge tube inside the small plastic beaker and charge it with the prescribed
volumes of Cu solution and H2O2 dil. solution.
3. Without delay, insert the small centrifuge tube inside the black test tube – gently, without
mixing the two solutions!

XXX-X
4. Close the test tube with its screw-on cap. Make sure that the tube is closed tightly, because you
will be shaking it. Caution: Do not force the cap beyond its end-point, because the tube will
start leaking. If this happens, you must ask for a replacement immediately (penalty rules apply).
5. Have the stopwatch ready in your hand, in timing mode. The moment you begin shaking the test
tube, start timing. You must shake vigorously during the initial 10 seconds, so that the two
solutions mix perfectly. It is crucial that you do not cut down the shaking time.
6. Return the test tube into the Erlenmeyer flask, open the lid and watch the solution inside closely.
It may help to shield away the daylight with your hand. Eventually, you will see a flash of blue light
through the whole solution. At that moment, stop timing.
7. Immediately, insert the metal probe of the digital thermometer into the black test tube. Wait for
the reading to stabilize (typically 10–30 s) and record the reaction time and the reaction
temperature.
8. Using tweezers, remove the small centrifuge tube from the black test tube. After each experiment,
empty and wash both tubes and dry them with paper wipes.
Measured data and their evaluation

P2.1 In the following table, record your experimental results for concentration set #1. To the
displayed temperature add the thermometer’s calibration constant. Look up the value of the
normalization coefficient nx→25 for each temperature in Table P2 and calculate the reaction
times normalized to 25 °C. In an unlikely case that your temperatures are not listed in Table
P2, get the value of nx→25 from the lab assistant.
Note: Just as the tolerance for correct values in titration is ±0.1 cm3, the tolerance for correct values
of the normalized times in the concentration set #1 is ±2.3 s.
(Use as many replicates as you consider necessary, you do not need to fill in all the rows.
Points will be awarded for the accepted value only.)

Reaction time
temperature temperature normalized to 25 °C
Repli- [s]
[°C] [°C]
cate 1 decimal [s]
1 decimal 1 decimal
place place
1 57.1 27.5 27.4 68.3
2 56.0 27.7 27.6 68.0

Conc.
set #1 3 55.7 27.8 27.7 68.2
Accepted value of the normalized reaction time

68.2

XXX-X
P2.2 In the following table, record your experimental results, the corrected temperature and
calculate the reaction times normalized to 25 °C for concentration set #2.
Note: Just as the tolerance for correct values in titration is ±0.1 cm3, the tolerance for the correct
values of the normalized times in the concentration set #2 is ±3.0 s.
(Use as many replicates as you consider necessary; you do not need to fill in all the rows.
Points will be awarded for the accepted value only.)

Reaction time
temperature temperature normalized to 25 °C
Repli- [s]
[°C] [°C]
cate 1 decimal [s]
1 decimal 1 decimal
place place
1 71.9 27.9 27.8 86.6
2 70.6 27.9 27.8 85.1

Conc.
set #2 3 72.5 27.8 27.7 86.8
Accepted value of the normalized reaction time

86.2
P2.3 Based on the procedure and on the concentrations of the stock solutions (specified in the list
of chemicals and in Part I. of the Procedure), calculate the initial concentrations of cysteine,
copper and H2O2 in both concentration sets.
Express the accepted reaction times (t1 and t2) from P2.1 and P2.2 in minutes and calculate
the corresponding reaction rates (v1 and v2), expressed as the rates of the consumption of
the cysteine concentration, in mmol dm−3 min−1. You can assume that the rate of cysteine
consumption during the reaction is constant.
If you cannot find the reaction rates, use the value 11.50 for conc. set #1 and 5.500 for conc.
set #2 in further calculations.
Initial concentrations
Accepted
[mmol dm−3]
reaction time Reaction rate
3 significant figures [min] [mmol dm−3 min−1]
4 significant 4 significant figures
Copper
Cysteine H2O2 figures
[Cu]
Conc. set #1 14.0 1.137 2.902

3.30 0.100
Conc. set #2 8.00 1.437 2.296

XXX-X
P2.4 Assuming the rate equation can be expressed as

v = k [H2 O2 ]p
use your experimental data to calculate the partial reaction order p with respect to H2O2. Write
down your answer with 2 decimal places and show your calculation.
Answer: p = 0.42
Calculation:
p
2.902 mmol dm–3 min–1 = k (14.0 mmol dm–3 )
p
2.296 mmol dm–3 min–1 = k (8.00 mmol dm–3 )
2.902 14.0 p
= ( )
2.296 8.00
log 1.264
p=
log 1.75
An expression of the rate law of cysteine consumption that is closer to reality is more
complicated and takes the following form:
v = k1 [H2 O2 ][Cu] + k2 [Cu]
P2.5 Using the data from P2.3, evaluate the dependence of v on [H2O2] as a linear function to find
the slope and the intercept. Write down both answers with 4 significant figures. If you cannot
find constants a and b, use the value 11.50 for both a and b in further calculations.
Answers (do not include the calculation, but include units):
v = a[H2 O2 ] + b a = 0.1010 min−1 b = 1.488 mmol dm−3 min−1
P2.6 Use the numeric values from P2.5 to evaluate the rate constants k1 and k2. Write down their
values with 3 significant figures.
Answers (including units):

k1 = 1.01 min−1 mmol−1 dm3 k2 = 14.9 min−1
Calculations:
k1 [Cu] = a  k1 = a / [Cu] = 0.1010 min−1 / (0.100 mmol dm−3)
k2 [Cu] = b  k2 = b / [Cu] = 1.488 mmol dm−3 min−1 / (0.100 mmol dm−3)

XXX-X
Marking notes
Incorrect number of significant figures and decimal places will not be penalized.
P2.1 Maximum 30 points, evaluated as follows:
1) The reported reaction temperature is combined with the individual calibration constant of the
thermometer to find the correct temperature. The correct temperature is used to normalize the
reported reaction time to a value that would be measured at 25 °C, according to Table P2. This is
for informative feedback on the contestant’s raw data, or to be used if the Accepted Value was
based on incorrect normalization – see point 4).
2) The interval of Accepted Values deserving full marks (30 points) is the interval of answers collected
when the procedure is performed correctly:
Master Value (determined in parallel experiments during the exam): 67.7 s.
The width of the full-marks interval (determined from a sample of 95 results from students trained
to perform the procedure correctly): MV ±3.5% (±2.4 s).
3) Values not totally correct should receive less than full marks. The number of points received for an
incorrect answer decreases linearly with the distance from the interval delineating correct answers.
The minimum of 0 points is for unacceptably incorrect values, i.e. beyond MV ±7.0% (±4.8 s).
4) If contestant’s calculation of the corrected temperature and of the normalized reaction time is
missing or involves errors, a substitute Accepted Value is taken for grading. This is based on the
correctly normalized reaction times calculated from contestant’s raw data - see point 1), following
the contestant’s choice of Accepted Value or taking the mean if the choice cannot be identified.
P2.2 Maximum 30 points, evaluated as in P2.1:
Master Value (determined in parallel experiments during the exam): 88.9 s.
Full marks (determined as for P2.1): within MV ±3.5% (±3.1 s)
0 points: beyond MV ±7.0% (±6.2 s)
P2.3 Maximum 7 points total:
1 point for each correct concentration, 0 points for incorrect answers
0.5 point for each correct conversion of a reaction time to minutes, 0 points for incorrect answers
1 point for each correct calculation of the rate of cysteine consumption, 0 points for incorrect answers
2 points for correct calculation (showing at least one formula that can be evaluated to yield the result)
1 point for correct value of the result
2 points for each correctly calculated parameter including correct unit, 1 point for each correct
numerical value with incorrect or no unit, 1 point for each incorrect numeric value including correct
unit, 0 points for each incorrect value with incorrect or no unit
2 points for correct calculation (showing the formulas that can be evaluated to yield the results)
2 points for each correct rate constant including correct units, 1 point for each correct numeric value
with incorrect or no unit, 1 point for each incorrect numeric value including correct unit, 0 points for
each incorrect value with incorrect or no unit.

Sintesi organica
TH
THE 16 INTERNATIONAL CHEMISTRY OLYMPIAD, Frankfurt am Main, 1984
PRACTICAL PROBLEMS
Nitration of phenacetine (4-ethoxyacetanilide) with nitric acid in acetic acid as solvent
Caution:
Both acetic acid and 65 % nitric acid attack the skin. If it happens, the skin must be
rinsed with water immediately and washed with a saturated aqueous solution of sodium
carbonate. Vapours of nitric acid damage the respiratory tract; moreover, nitric gases
evolved in the reaction flask are very toxic.
The glass joints of the various apparatus must be only slightly greased.
Apparatus:
250 ml four-necked flask with laboratory stirrer, thermometer, reflux condenser with gas
vent, water bath, Bunsen burner.
Preparation:
40 ml of acetic acid are placed with a glass syringe pipette in the four-necked round
bottom flask. 2.0 g of phenacetine are then dissolved in the acetic acid. Also, 2.5 ml 65 %
nitric acid are added by using a glass syringe pipette under an effective hood. This mixture
is heated for five minutes in a water bath at 90 oC.
Isolation and purification:

The hot water bath is replaced by ice water. After ca. 10 minutes the gas vent is
removed and ca. 120 ml of distilled water are added through the reflux condenser into the
flask in order to dilute the original solution. Stirring is continued until a temperature of ca.
5 oC is reached.
The precipitated solid is filtered off and then washed with a total of 100 ml of cold
water and finally dried at 60o C for 2.5 hours in a drying oven.
TH
Evaluation of the experiment:

a) Melting points:
The melting point of phenacetine and its reaction product are to be determined and
o
recorded in the note book. The melting point of phenacetine is higher than 120 C and that
of the product is higher than 80o C.
b) Thin-layer chromatogram:
The relative position of the spots of the starting compound and its reaction product
must be recorded. In order to reach it, little portions of the both samples must be dissolved
in 1-2 ml of acetone. The solutions must be placed on the plate by using a capillary tube.
To develop the chromatogram, a mixture of 90 ml toluene, 25 ml acetone, and 5 ml acetic
acid is used.
After drying the spots are circled with a pen. The Rf -values must be recorded.
c) Developing reagent:
The developed TLC-plate must be sprayed under a hood with the available reagent
solution consisting of iron(III) chloride and potassium hexacyanoferrate(III).
Interpretation of the results:

1.1 Which nitration product(s) has (have) been formed? The discussion should focused
on the relative position of the spots in your chromatogram; describe your arguments
in the note book.
1.2 Explain why such "mild conditions" have been used here for the nitration reaction.
Explain why the nitration reaction has proceeded in spite of these "mild conditions".
1.3 Explain the observed colour reaction of phenacetine with the developing reagent.
1.4 Make a brief proposal, how the filtrate should be prepared to avoid environmental
damage.
Chemicals:
Acetic acid (analysis grade)
Nitric acid (analysis grade); w = 65 % by mass
Phenacetine (analysis grade)
Toluene (analysis grade)
TH
Acetone (analysis grade)

Developing reagent: 100 ml solution
200 ml solution
700 ml distilled water.
____________________
SOLUTION
a) Melting points:
4-ethoxy-N-acetylphenylamin (phenacetine) : 135 °C
4-ethoxy-2-nitroacetanilide : 103 °C (theoretic al value)
b), c) Documentation, Thin-layer chromatogram
Interpretation of the results:

1.1 The Rf -value of the nitration product is almost twice as great as that of the
starting compound phenacetine. Although nitration has occurred, the molecules
exhibit less dipolar character that indicates intramolecular hydrogen bridges. This is
only possible if the acetylamino and nitro groups are located in 1.2-positions.
In accordance with the +M-effect of the acetyl amino group one should expect
that the nitro group would be favoured in a (free) ortho-position because of the
lowered activation energy. On the other hand, one would not expect multiple nitration
because of the "mild reaction conditions" (see below) and also because of the
electron withdrawing mesomeric effect (-M-effect) and the inductive electron
withdrawal (-I-effect) of the nitro group that has entered the molecule.
Nitration product: 4-Ethoxy-2-nitroacetanilide

The melting point confirms this observation.
1.2 The nitration reaction is carried out relatively rapidly, at relatively low temperature in
dilute solution and without using fuming nitric acid or "nitration acid".
Instead of sulphuric acid concentrated acetic acid is used. The molecules of the
latter compound neither protonate the HNO3 sufficiently nor do they do solvate the
TH
+
NO2 ions. As a result, the equilibrium reactions
+ –
HONO2 + HONO2 H2O -NO2 + O-NO2
and
H2O+-NO2 +
NO2 + H2O
are shifted far to the left. This effect is counterbalanced by the high reactivity
(+M-effect) of phenacetine.
1.3 Phenacetine is oxidized by iron(III) ions and a molecule of p-quinone type and iron(II)
ions are formed. The iron(II) ions react immediately with the hexacyanoferrate(III)
ions to give Turnbull's Blue.
1.4 Neutralization with sodium or potassium hydroxide solution, use of calcium hydroxide
solution and argumentation:
NO3--ions, CH3COO- ions and 4-ethoxy-2-nitroacetanilide are removed by biological
metabolism.
TH
PRACTICAL PROBLEMS
Synthesis of a derivative (NaHX) of the sodium salt of an organic acid
Apparatus:
3 3 3
1 beaker (250 cm ), 2 beakers (50 cm ), 1 pipette (10 cm ; graduated at intervals of 0.1
cm3), 1 measuring cylinder (50 cm3), 1 capillary pipette (Pasteur pipette), 1 thermometer,
1 filter crucible (G4), apparatus for suction filtering, 1 glass rod.
Reagents:
Sodium salt of 1-naphtol-4-sulfonic acid (S), (sodium 1-naphtol-4-sulfonate),
(M = 246.22 g mol-1), sodium nitrite (M = 69.00 g mol-1), aqueous solution of HCl (2 mol
dm-3), deionised water, absolute ethanol.
Procedure:
Mix the given lot of technical grade starting material, labelled I, (contains 1.50 g of
sodium 1-naphtol-4-sulfonate, S) and 0.6 g of NaNO2 with about 10 cm3 of water in 50 cm3
beaker. Cool in ice bath (a 250 cm3 beaker) to the temperature 0 – 5 °C. Keeping the
temperature in the 0 – 5 °C range, add dropwise 5 c m3 of 2 M HCl (aq) to the reaction
mixture. Stir for ten more minutes in an ice bath to effect the complete precipitation of the
yellow-orange salt NaHX . n H2O. Weigh the filter crucible accurately (± 0.5 mg). Filter the
product with suction in the crucible and wash with a small amount (ca. 5 cm3) of cold water
and then twice (about 10 cm3) with ethanol. Dry the product in the filter crucible at
110 °C for 30 minutes. Weigh the air-cooled anhydro us material together with the crucible
and present it to the supervisor.
Calculate the percentage yield of NaHX (M = 275.20 g mol-1).
The purity of the product NaHX influences your results in Problem 2!
Question:
Write the reaction equation using structural formulae.
ST
PRACTICAL PROBLEMS
Synthesis
Preparation of 2-Ethanoyloxybenzoic Acid (Acetylsalicylic Acid, also known as Aspirin) by
Ethanoylation (Acetylation) of 2-Hydroxybenzoic Acid (Salycilic Acid) with Ethanoic
Anhydride (acetic anhydride).
Relative atomic masses: C: 12.011; O: 15.999; H : 1.008
Reagents
2-hydroxybenzoic acid (melting point 158 °C)
Ethanoic anhydride (boiling point 140 °C)
Phosphoric acid (85 % H3PO4)
Ethanol
Deionised/distilled water
Procedure
In a 100 cm3 Erlenmeyer flask mix 2.760 g of 2-hydroxybenzoic acid (from weighing
bottle A) with 5.100 g of ethanoic anhydride (from flask B), and with cautious swirling add
5 – 7 drops of 85 % phosphoric acid. Heat the flask to 70 – 80 °C in a beaker of near
boiling water and maintain the mixture at this temperature for 15 minutes. Remove the
flask from the water bath and, with gentle swirling, add dropwise 1 cm3 of deionised water
to the still hot flask; then immediately add 20 cm3 of the cold deionised water all at once to
the reaction flask. Place the flask in an ice bath. If no crystals are deposited, or if oil
appears, gently scratch the inner surface of the flask with a glass rod while the flask
remains in the ice bath.
Using a Büchner funnel, filter the product under suction. Rinse the flask twice with a
small amount of cold deionised water. Recrystallize the crude product in the 100 cm3
Erlenmeyer flask using suitable amounts of water and ethanol. If no crystals form or if oil
appears, scratch gently the inner surface of the flask with a glass rod. Filter the
crystals under suction and wash with a small amount of cold deionised water. Place the
ST
crystals on the porous plate to draw water from them. When the crystals have been air
dried, transfer the product to the small glass dish labeled C. This dish has previously been
weighed. The dish containing the product should be given to a technician who will dry it in
an oven for 30 minutes at 80 °C.
A technician should then weigh the cooled dish containing your product in your
presence. Record the mass. The melting point will subsequently be taken by a technician
to check the purity of your product.
Questions:
1. Write the balanced chemical equation for the reaction using structural formulae.
2. What is the percentage yield?
_______________
SOLUTION
1.
COOH COOH
OH OCOCH3
+ (CH3CO)2O + CH3COOH
ND
PRACTICAL PROBLEMS
Synthesis involving Carbanions Chalcone
The aim of this experiment is to condense acetophenone and benzaldehyde in a
mixed aldol condensation. After spontaneous dehydratation, an α,β - unsaturated ketone
is obtained: the chalcone, 1,3-diphenylprop-2-en-1-on.
a) Starting the condensation reaction

3
In a 250 cm ground neck Erlenmeyer (conical) flask, dissolve about 5 g of
potassium hydroxide, KOH, (50 pellets) in 30 cm3 of water, then add slowly under stirring
3 3
20 cm of ethanol. From the automatic dispensers, add 9.6 g (0.08 mol = 9.5 cm ) of
acetophenone and 8.5 g (0.08 mol = 8.5 cm3) of benzaldehyde. Set up a condenser in the
vertical reflux position and reflux vigorously while stirring the mixture with the magnetic
stirrer for an hour.
b) Isolation of the crude chalcone

After refluxing, cool the contents of the Erlenmeyer flask in an ice bath. The chalcone
should crystallize. If crystals do not appear, scratch the inside wall of the flask with a glass
rod. Collect the crystals in a Büchner funnel, wash them with a little ice cold ethanol, then
air dry and weigh the crystals.
c) Recrystallization of the chalcone

Recrystallize this crude chalcone from ethanol, using a 100 cm3 beaker. Use the
heating plate located in the hood (fume chamber). When the crystallization is over (wait
long enough and scratch if necessary), collect the crystals in a Büchner funnel, and air dry
them.
ND
Give your entire product to the supervisor who will measure its mass and
melting-point.
Do not breathe the vapour while recrystallizing and measuring the melting point. It
contains irrigating chalcone!!!
Questions:
1.1 Write the mechanism for this reaction.
1.2 Give the mass of the crystals of the crude chalcon obtained and calculate the yield of
crude product.
1.3 Calculate the yield of recrystallized product based on starting material and calculate
the efficiency of the recrystallization process.
_______________
SOLUTION
1.1
O O
(-) (-)
+ OH + H2O
(-)
O O O O
(-)
+
(-)
O O O OH
(-)
+ H2O + OH
ND
O OH O
(-)
+ OH + HOH
H
OH
(-)
TH
PRACTICAL PROBLEMS
Synthesis
Cholesterol (1) is a natural sterol metabolite present in animal and vegetal
organisms. This compound can be oxidized by Jones' reagent into its corresponding
3-ketoderivative (2). The latter, when treated with bases, undergoes isomerization of the
carbon-carbon double bond leading to α,β-unsaturated ketone (3).
The conversion of ∆5-3β-hydroxy steroids into their corresponding ∆4-3-ketones is an
important reaction in steroid chemistry and represents the last step of the synthesis of a
variety of commercial hormones.
You will be marked for the purity of the product (3).
Procedure:
a) Dissolve your pre-weighed sample of cholesterol (386 mg, 1 mmol) contained in a 50
cm3 flask A with acetone (20 cm3) warming gently the flask in a bath tub of hot water.
When the sample is completely dissolved, cool the flask containing the solution to
the temperature by cold water.
b) Add dropwise 0.40 cm3 of Jones' reagent to the solution, gently swirling the flask in a
bath of cold water. The formation of a green precipitate [Cr2(SO4)3] is observed
during the addition of Jones' reagent.
c) Remove the green precipitate by filtration with paper filter.
d) Add slowly water (10 cm3) to the clean filtrate. The ketone (2) begins to precipitate.
e) Filter the precipitate over the Büchner funnel under reduced pressure, washing the
crystals with small portions of a 2 : 1 acetone/water mixture.
f) Dissolve the ketone (2) in methanol (15 cm3). Add to the solution just one drop of 5
% methanolic NaOH solution and warm the mixture in a bath of hot water for 10 min.
TH
The ∆ -3-ketosteroid (3) precipitates spontaneously, upon addition of water (ca. 2

4
g)
3
cm ) to the cooled reaction mixture. Filter the crystals over the Büchner funnel under
reduced pressure and recrystallize the product by methanol. If you do not get the
crystals, add a few drops of water. Remember! You are getting a mark for the purity,
not the yield.
h) Dry carefully the crystals on a porous plate. Determine the melting point of the
ketone (3) and write its value on your student's report. Taking into account the
correction reported on the top of the thermometer (see example at the end).
i) Put the crystals in the plastic vial B, write on it your personal identification number
(see the left corner of your badge), and deliver it to one of the supervisors.
The melting point of the ketone (3) will be checked by the lab supervisors.
_______________
SOLUTION
Points were given accordingly to the amount of product.
Some additional points were given for melting point measurements.
TH
Qualitative Determination of Paracetamol in a Sample of Unknown Drug
Introduction
Three organic compounds are most widely used as pain relieving drugs:
acetylsalicylic acid (ortho-acetoxybenzoic acid), phenacetine (para-ethoxyacetanilide), and
paracetamol (para-hydroxyacetanilide). Paracetamol is now the most popular, being the
base of a large number of well known patented pharmaceuticals (panadol, solpadeine,
coldrex, calpol, efferalgan etc.), as it is now considered as the safest and highly efficient
drug.
You were given a sample of unknown drug which claims to contain paracetamol.
Your task is to prove or disprove this claim experimentally. To do this you shall have to
prepare an authentic sample of para-hydroxyacetanilide, and run a thin layer
chromatography test.
Reagents
• Para-aminophenol, 3.10 g in a weighing beaker

• Acetic anhydride, 4.00 cm3 in an Erlenmeyer flask
• Ethanol
• Eluent (heptane : ethyl acetate : ethanol = 41 : 47 : 12 by volume)
• Sample of unknown drug in a test tube, 1 % solution in ethanol
• Water (use tap water for all purposes)
Procedure
Preparation of para-hydroxyacetanilide
A 50 cm3 round bottom flask is equipped with reflux condensor and installed on a
laboratory stand over a hot plate. Note that the space between the top of hot plate and the
bottom of flask be about 1-1.5 cm. Use two clamps to properly support the flask and
condenser. Remove the hot plate. Do not switch on the hot plate until you finish with
adding reagents and reassembling the apparatus. With reflux condensor temporarily
removed, 3.10 g of para-aminophenol is placed to the flask using a funnel (use a glass rod
TH
3
to push it through the funnel, if necessary). Water (10 cm ) is then added through the
3
same funnel. The condenser is mounted back, and acetic anhydride (4.00 cm ) is carefully
poured to the reaction mixture through the condenser (attention! acetic anhydride has a
strong irritating smell. In case of spill immediately wash hands with water and ask the
supervisor to help with the disposal of spilled compound). Carefully stir the contents by
slightly relieving clamps and waving the flask 2 - 3 times. Be careful as the mixture and the
flask gets very hot due to the reaction heat. Place back the hot plate and switch it on. The
reaction mixture is heated for 15 minutes beginning from the time when you switch on the
hot plate. Then, the heater is switched off and removed from the apparatus. The mixture is
allowed to cool first by immersing the flask into a bath with cold tap water. You may do this
immediately after you remove the plate as the flask is made of highly durable glass. After
approximately five minutes unattach the condenser and pour the contents into an empty
3
100 cm pyrex glass beaker. Put the beaker into a metal dish filled with ice and water.
Accurately rub the walls of beaker with spatula and observe the crystallization of crude
product as small white crystals.
Assemble a suction filtration device: put the frit filter onto a rubber ring and a heavy-
wall flask. Connect the flask to a suction vacuum pump and turn on water in the pump by
turning tap. (Attention! Never turn off the water tap if your device is under vacuum. First
always disconnect the flask from vacuum pump by carefully pulling off the rubber tubing
from the inlet.)
The crystalline precipitate is quantitatively moved onto a filter by spatula. Remaining
solid can be washed with small portions of ice cold water (as small as possible, as the
compound possesses an essential solubility in water, and the losses of dissolved
compound must not outweigh the losses due to incomplete transfer of product to the
filter). The product in the filter is carefully washed with 2 - 3 portions of 2 - 3 cm3 of cold
water by a) connecting the vacuum suction flask to the atmosphere; b) addition of water
and careful mixing it with the precipitate using a spatula; c) reapplying vacuum;
d) pressing the precipitate with flat tip of a glass rod to squeeze out as much water as
possible.
Several crystals of material are used for chromatography test (see below). All other
precipitate is moved to a sheet of filtering paper in a Petri dish, and spread out over the
filter in a thin layer, and allowed to dry on a shelf to exclude accidental spill. For rapid
drying it is critical to spread it as thin as possible, to break all large pieces, and to stir it
TH
and spread again every 3-5 minutes to expose all wet crystals to air. It is established after
a numerous repetition of this procedure, that after 30 min the product contains no more
than 5 % of water. Such wetness is considered as insignificant for evaluating the results of
the preparation.
Chromatography test
(If for some reason you have failed to obtain para-hydroxyacetanilide, you can obtain a
sample for chromatography from your supervisor.)
While still wet several crystals of the material obtained by you are dissolved in a tube
in 1 - 2 cm3 of ethanol. The unknown drug is already dissolved in ethanol and given to you
as 1 % solution. These solutions are used for thin layer chromatography, as follows:
Prepare a sheet of chromatography plate covered with silica. Using a sharp pencil
draw a start line and marks for sample spots. A small spot of each solution is placed on a
chromatography plate using a capillary. The spots are allowed to dry for 1-2 minutes.
The plate is immersed into a beaker containing the eluent and allowed to be eluted.
Use forceps to move the plate in and out of the beaker. After the elution, remove the plate
from the flask, mark the front of eluent, and allow it to dry under the hood for 5 minutes.
Examine the chromatogram under UV light in a special cabinet. Outline the dark spots (if
there are any) with a sharp pencil.
Weighting of sample
After you complete the chromatography, your product usually is almost dry and is
ready for weighting. Ask you supervisor to weight an empty weighing beaker. Put the dry
product into a weighted beaker and give it to the supervisor for weighting. Weights are
written in your answer sheet by the supervisor. Calculate the weight of the product.
2.1 Draw the structures of three main pain relieving drugs mentioned above.
2.2 Draw the reaction equation involved in the preparation of para-hydroxyacetanilide.
Calculate the stoichiometric amounts of reagents needed for the reaction. How much
acetic anhydride is taken in excess over the stoichiometry? The density of acetic
anhydride is 1.08 g cm-3.
2.3 Calculate the yield of product obtained by you.
2.4 Calculate and compare the values of Rf of unknown drug and your product.
2.5 Is it likely that paracetamol is contained in the sample of drug?
TH
SOLUTION
2.1
Acetylsalicylic acid Phenacetine Paracetamol
OCOCH3 OC2H5 OH
COOH
NHCOCH3 NHCOCH3
2.2
OH OH
+ (CH 3CO)2O = + CH3COOH
NH2 NHCOCH3
2.5 Yes, the sample is likely to contain paracetamol.
TH
Synthesis of the Substituted Dihydro-1,3-benzoxazine (C)
O
H3C N
Benzoxazines have long been recognized as useful biologically-active compounds.

One such compound (C) will be prepared using the three-step synthesis described below.
All of the product obtained in Step I should be used in Step II and similarly all of the
product from Step II should be used in Step III. You will be evaluated on both the yield
and purity of the final product.
Chemicals available
3 3
5 cm reaction vial containing 2.5 cm of ethanolic 1-amino-4-methylbenzene (0.22 g),
vial containing 0.25 g of 2-hydroxybenzaldehyde,
vial containing 0.1 g of sodium borohydride,
vial containing 0.042 g of paraformaldehyde,
test tube containing dilute ethanolic KOH,
3
(50 mg of KOH dissolved in 10 cm of ethanol),
wash bottle containing dry ethanol,
Ice is available in each laboratory room.
Molar masses:
M(H) = 1.008 g mol-1 M(C) = 12.011 g mol-1 M(N) = 14.007 g mol-1
M(O) = 15.999 g mol-1 M(Na) = 22.990 g mol-1 M(B) = 10.811 g mol-1
TH
Procedure
STEP I
H O
CH3 C
OH H
+ C
N CH3
OH
NH2
(i) (ii) A
3
1. Place the small magnetic stirbar in the 5 cm reaction vial containing solution (i) and
stir.
2. Add the 2-hydroxybenzaldehyde from vial (ii) dropwise to the stirred solution in vial
(i). After a short period of time a yellow solid will crystallize out. This is intermediate
product A.
3. Isolate the yellow solid (A) by vacuum (suction) filtration and wash it with ice-cold
ethanol.
STEP II
H
C NaBH 4
N CH3 (iii) NH CH3
OH OH
A B
3
1. Add the impure Product A from Step I to a 5 cm reaction vial containing
3
approximately 1.5 cm of ethanol.
2. Surround the vial with ice/water, and stir the reaction vigorously with the spatula
while carefully adding small amounts of sodium borohydride (iii) over a period of
about
5 minutes until the bright yellow colour disappears. The reaction will bubble.
Note that you have been given more sodium borohydride than is required for this
reaction.
3. Isolate the intermediate Product B by vacuum (suction) filtration, wash it with ice-cold
ethanol, and air dry the solid for approximately 5 minutes.
TH
STEP III
(CH 2 O) n
NH CH 3 N CH3
OH (iv)
O
B C
3
1. Dissolve all of the paraformaldehyde (iv) in approximately 2.5 cm of ethanolic
3
potassium hydroxide (v) in a 5 cm vial. Stir to dissolve all of the solid.
2. Add all of product B from Step II to the vial. Stir and gently reflux the mixture for 15
minutes. A clear solution should be obtained.
3. Concentrate the solution by carefully boiling off some of the ethanol leaving
3
approximately 1 cm in the vial and allow the vial to cool. The crystals which form
are the required product C.
4. Isolate the crude product C by vacuum (suction) filtration and air dry the crystals.
5. Recrystallize the crude product from ethanol. Air dry the crystals for 15 minutes.
6. Determine the melting point* and then mass of the final product.
7. Place all of your remaining product in the numbered vial labelled “PRODUCT C” and
hand it in for evaluation.
* Note: A melting point is always recorded as a range -- from when the crystals first
begin to melt until the last crystal has melted. The melting point apparatus should be
allowed to cool to approximately 50 degrees before you use it. The supervisors will be
rechecking both your reported melting point and mass for product C.
ND
Synthesis of Amino Acid Methyl Ester Hydrochloride
In the synthesis of peptides, one amino acid is reacted with another to form an amide
bond between them. In order to ensure that the individual amino acids do not form amide
bonds with themselves and that only one product is formed, the amino group in the first
amino acid and the carboxyl group in the second amino acid are masked before the
peptide synthesis.
The procedure described below can be used for masking the carboxylic acid groups
in amino acids before peptide formation.
CH 3OH
NH2 NH3 , Cl –
SOCl2
HO HO
COOH COOCH3
The experiment should be performed in a ventilated hood since thionyl chloride is an

irritant and since irritating gases are evolved during the reaction.
Thionyl chloride is a corrosive acid chloride. Avoid contact with skin and eyes.
Splashes in eyes or on skin should be flushed immediately with water. Thionyl chloride in
larger amounts reacts violently with water.
Procedure
3
Absolute methanol (2.0 cm ) is transferred quickly to a dry test tube which is then
closed with a piece of aluminium foil. The foil is used as a lid throughout the subsequent
manipulations with the tube. This protects the content from moisture from the air. The
methanol is cooled in an ice-bath for 1 – 2 min. Thionyl chloride, handle with care, see
above (0.52 cm3) is drawn up into a 1 cm3 graduated syringe with polyethylene tube tip, as
described in separate procedure B, and is cautiously added to the methanol over a period
of approximately 5 min.
The mixture is kept at 0 °C for approx. 2 min. ( S)-Serine (0.210 g, weighed sample
provided) is added and the mixture is kept at room temperature for approx. 2 min before
gently heating to boiling (using a sand bath) for 10 min. All material should then have
dissolved.
ND
The mixture is cooled in an ice-bath for approx. 2 min. Dry tert.-butyl methyl ether (10
3
cm ) is then added. The inside wall of the test tube is scratched at the surface region of
the solution with a glass spatula for about 1 min. and the test tube is then left in the ice-
bath for a further 5 –15 min for crystallization. The separated crystals are then isolated by
filtration as described in separate procedure A. The filtrate is collected in a 100 cm3
beaker.
The crystals are washed two times on the filter, each time with 1 cm3 of tert.-butyl
methyl ether. The filter cake is finally pressed with the piston, and the crystals are pre-
dried by pumping air through the filter cake with the piston.
The solid is then collected on a piece of filter paper in order to absorb residual
solvent. When dry, the residue is placed in a tarred plastic sample tube with lid (Eppendorf
tube) found in the box. The sample tube is then closed and weighed.
PROCEDURE A
Filtration procedures
3
Modified syringes are used for filtration in the laboratory tasks. A 60 cm syringe with
a disc of porous polypropylene is used in task 1, while a 10 cm3 syringe with a disc of
filtration paper is used in task 2. The procedure is sketched on Fig. 1.
Fig. 1: Micro-scale filtration in plastic syringe
ND
Procedure:
1. Fill the syringe from above with suspension to be filtered. The syringe can be filled to
the level of the hole. Replace piston.
2. Close hole and press piston for filtration.
3. Stop before passing the hole.
4. Open hole and draw piston back.
5. Repeat steps 2-4 a couple of times.
6. Remove piston and place filter paper on top of the filter cake.
7. Press piston against filter cake.
8. Push filter cake out with straightened- out paper clip.
Filtration procedure for practical problem 1

The provided filter syringe to be used in this experiment is made from a 60 cm3
standard medical polypropylene syringe from which the piston has been temporarily
removed and a 3 mm hole drilled at the 35 cm3 mark. With a plastic spatula a disc of
porous polypropylene, which fits tightly inside the syringe, is pressed down to be
positioned at the base of the syringe. The mixture to be filtered is applied without the
piston inserted. Drops of solution may be moved downwards by tapping the syringe
against a solid surface,
The piston is now placed in the syringe and gently pressed down while keeping the
hole closed with a finger so to promote the passage of solvent through the filter. When the
piston reaches just above the hole, the finger is removed from the hole, and the piston is
drawn back again to the top position. This cycle can then be repeated a couple of times,
until the filter cake looks dry. Remember to close the drilled hole, then the piston is moved
downwards and to open the hole, when the piston is moved upwards. The filter cake can
be washed and the washing solution pressed out using similar cycles.
Solvent remaining in the outlet can be sucked up with a small piece of tissue paper.
The solid is then removed from the syringe and collected on a piece of weighing paper for
drying.
ND
Filtration procedure for practical problem 2

3
The provided filter syringe to be used in this experiment is made from a 10 cm
standard medical polypropylene syringe from which the piston has been temporarily
removed and a 3 mm hole drilled at the 5.5 cm3 mark. A piece of filter paper which fits
snugly in the syringe is pressed down to the bottom with the piston. Filtration and washing
are then performed as described for task 1. Before removing the filter cake the piston is
withdrawn. A piece of filter paper fitting the syringe is then pressed all the way down to the
filter cake using the piston. The filter cake is pressed by means of the piston. Then the
piston is then drawn back and out the syringe (slowly, until the hole is reached).
This leaves the filter cake between two pieces of filter paper. Solvent remaining in the
outlet can be sucked up with a small piece of tissue paper.
The filter cake is cautiously pushed out of the syringe using an straightened-out metal
paper clip introduced through the outlet of the syringe. The solid material is then removed
from the syringe, if possible as a coherent plug. The residue is collected on a piece of filter
paper for drying by using a small metal spatula. Filter paper from the filtration can be fixed
with the paper clip tip while adhering solid is removed using the spatula.
PROCEDURE B
Fig. 2. Measuring volumes of liquids using a syringe
Procedure:
1. Suck up a slight excess of liquid in syringe.
ND
2. Turn syringe upside down; the tip of the tube is kept in the storage nottle. Air in the
syringe is accumulated at its top.
3. Air in the syringe is removed by pressing the piston. Press further until desired
volume of liquid is left in the syringe. The tip of the tube is kept in the storage bottle.
4. Turn the syringe, place tip of the tube in the receiver flask and press piston until
desired volume of liquid has left the syringe.
RD
PRACTICAL PROBLEMS
Preparation of 2-Iodobenzoic Acid
This laboratory task involves preparation of 2-iodobenzoic acid from 2-aminobenzoic
acid. The procedure consists of diazotization of 2-aminobenzoic acid followed by reaction
with KI (in H2SO4).
Procedure
1) Quantitatively transfer the given sample of solid 2-aminobenzoic acid into a 100 cm3
beaker placed in the ice-bath. Add 7.2 cm3 of H2SO4 (2.6 M) (labelled H2SO4) and
mix the contents thoroughly for 1 minute with the help of a glass rod. Cool the
solution for 5 minutes.
2) Using a measuring cylinder, measure out 4.4 cm3 of supplied cooled NaNO2 solution
from the vial placed in the ice-bath.
3) With the help of a dropper, slowly add the cooled NaNO2 solution to the acid solution
with constant gentle stirring using a glass rod to obtain an almost clear solution
(3 – 5 minutes).
4) Remove the beaker from the ice bath and then slowly add 9.4 cm3 of KI solution from
the stoppered tube, with stirring.
5) Get hot water from the laboratory expert. Keep the beaker in hot water for 5 minutes.
3
6) Filter the crude product and wash it thoroughly with distilled water (10 cm ). Collect
the washings along with the main filtrate.
7) Neutralize the combined filtrate by gradually adding the given solid Na2CO3 until
effervescence ceases. Dispose of the filtrate in the appropriate plastic bucket.
Purification of the crude product

Place the funnel containing the precipitate on a 100 cm3 conical flask. Pour about 15 to 20
cm3 of the supplied NaHCO3 solution (using test tube) over the filter paper so as to
dissolve the precipitate completely.
8) Add the supplied charcoal powder to the filtrate and mix it thoroughly. Filter the
solution to remove charcoal.
RD
9) Add dilute H2SO4 gradually to the filtrate till effervescence ceases. Filter the purified
3
product. Use 10 -15 cm distilled water to wash the precipitate. Keep the filter paper
with the product on a watch glass.
10) Cover the product with the same funnel and hand over the product to the laboratory
expert for drying (for a minimum of one hour).
Towards the end of the practical session have the product weighed by the laboratory
expert and record the same.
_______________
SOLUTION
• The calculated theoretical yield (based on 2 aminobenzoic acid) in g.
• The yield obtained as a percentage of the theoretical yield.
• Colour of the product obtained.
Tasks:
Write down the balanced chemical equations for:
(a) diazotization of 2-aminobenzoic acid using NaNO2 and H2SO4.
(b) the reaction of Kl with the diazotized product.
__________
Solutions of the tasks:
a)
b)
TH
PRACTICAL PROBLEMS
Enzymatic Hydrolysis of Methyl N-Acetyl-phenylalaninate
α-Chymotrypsin, a protease enzyme recognizing derivatives of natural α-amino
acids, catalyses the hydrolysis of esters. In this experiment the enzymatic hydrolysis of
racemic methyl N-acetyl-phenylalaninate A is investigated (Scheme).
The rate of formation of N-acetyl-phenylalanine B can be monitored by titration with 0.100

M NaOH in the presence of propyl red as a pH indicator.
Procedure
Note: the required amount of α-chymotrypsin will be supplied in a sample vial by the
laboratory assistant on request.
Racemic methyl N-acetyl-phenylalaninate A [500 mg, the exact mass (± 1 mg) is
indicated on the label of the vial marked as NacPheOMe] is transferred quantitatively into
a 50 cm3 Erlenmeyer flask and dissolved in methanol (~ 2.5 cm3). Subsequently, propyl
red (0.02 % solution in ethanol; 4 drops) is added. The kinetic experiment is started by
adding α-chymotrypsin (10.0 cm3 of a 0.05 % solution in distilled water) in one portion
(start the stopwatch).
When the reaction mixture turns pink, it is immediately titrated with 0.100 M NaOH
TH
until the colour changes to yellow. When the pink colour reappears, add just enough titrant
to restore the pale yellow colour, swirling the flask continually during the addition. You only
need to record the reading on the burette every 5 minutes. (Note: at the beginning colour
changes occur very frequently.)
Monitor the reaction for 75 minutes. A graph showing the amounts of NaOH consumed in
cm3 versus time is constructed, in order to visualize the kinetic course of this enzymatic
reaction.
_______________
SOLUTION
The competitors were expected to show on the answer sheet the following data, tables,
graphs or calculations:
1. Amount of the starting racemic methyl N-acetyl-phenylalaninate A (in mg and mmol).
2. Table with time measured and the total consumption of NaOH in cm3.
3. A graph of the total consumption of NaOH vs time.
4. Calculation of the amount of 0.100 M NaOH consumed in this experiment in mmol.
5. Calculation of the degree of hydrolysis of
methyl N-acetyl-(R,S)-phenylalaninate A in mol %.
TH
Synthesis of Benzylhydantoin
Introduction
α-Amino acids are the building blocks for peptides and proteins. They are also
frequently used as starting material for the synthesis of pharmaceuticals. In this
experiment natural S-phenylalanine A is converted in two steps into benzylhydantoin C,
which is a useful intermediate for the preparation of various physiologically active
derivatives.
Procedure
STEP 1
Retain a tiny amount of starting material A for the TLC analysis (see below). A long-
necked round-bottomed flask is charged with (S)-phenylalanine A (500 mg, 3 mmol, the
exact amount is indicated on the label of the vial), sodium cyanate (300 mg, 4.6 mmol),
water (3 cm3) and a stirring bar. Two drops of aqueous sodium hydroxide (1 M) are
added to the stirred suspension. The flask is equipped with a condenser (distillation
column) and the reaction mixture is heated to 80 oC on a sand bath while stirring
magnetically.
Important
In order to reach the appropriate temperature in time and not lose too much time,
start the electric heating of the sand bath immediately at the beginning of this
experiment. Check the temperature of the sand bath regularly and carefully with a
thermometer.
After heating the reaction mixture at 80 oC for at least 30 minutes, the resulting clear
solution is cooled to room temperature and poured into a small Erlenmeyer flask. Rinse
the round-bottomed flask with a little water. The solution is acidified by dropwise addition
TH
of hydrochloric acid (4 M) to pH < 3 with magnetic stirring. Some water is added to the
resulting white suspension in order to facilitate stirring.
The white precipitate is then filtered off by suction, washed with ample water (on the
filter) and then washed twice with a small amount of di-isopropyl ether to remove most of
the adhering water. The urea derivative B is left on the filter under suction for at least 3
minutes to remove as much solvent as possible.
A small amount of the obtained urea derivative B is retained for TLC-analysis later.
STEP 2
The urea derivative B is now transferred into a long-necked round-bottomed flask
and hydrochloric acid (4 M, 3 cm3) is added. A stirring bar is introduced and the
suspension is stirred thoroughly whilst heating at 80 oC on a sand bath. A clear solution
is obtained. After a reaction time of 30 minutes, the reaction mixture, which may already
contain some precipitate, is cooled to room temperature. The obtained suspension is
filtered by suction, washed thoroughly with water and finally washed twice with a small
amount of di-isopropyl ether. The product is left on the filter under suction for at least 3
minutes. It is then collected on a filter paper and dried in the air for at least 30 minutes.
The final product C, its precursor B and starting material A (see above) are subjected
to TLC-analysis. For this purpose small amounts of either compound are dissolved in a
tiny amount of pure acetone. Small samples of these solutions are applied to a TLC plate,
using the supplied capillary tubes. The analysis is carried out with two TLC plates in one
run. The TLC-plates are developed with a solution of 2% formic acid in ethyl acetate as
the eluent. After the elution the TLC-plates are analysed using a UV-lamp. The starting
line, solvent front and the UV-active spots are clearly marked with a pencil. Copy the
diagram in the box on the answer sheet. The Rf values are determined. Finally, the TLC-
plate with the best analysis is wrapped in parafilm and placed in a plastic bag with a
sealing strip.
The final product C is transferred into a sample vial of which the empty weight has
been pre-determined (weight is indicated on the label). Weigh the vial with product and
calculate the yield of the product C.
The examination committee will check the quality of the benzylhydantoin that you
have prepared by determining its melting point using an automatic melting point
apparatus.
_______________
TH
SOLUTION
The competitors were expected to show the following data, tables, graphs or
calculations on the answer sheet:
1. Mass of your starting material A (see label on the vial) in mg.
2. Amount of benzylhydantoin C obtained.
3. Calculation of the yield of benzylhydantoin C in %.
4. Rf value of urea derivative B.
5. Rf value of benzylhydantoin C.
6. A copy of the TLC diagram with indication of the front base line of the solvent.
7. Conclusions from the TLC analysis:
Compound B: is pure; contains some A; contains several contaminants.
Compound C: is pure; contains some B; contains some A and B;
contains several contaminants.
8. Appearance of benzylhydantoin C: white colour, yellowish colour, sticky, crystalline,
powder.
9. Melting point of benzylhydantoin C was determined by the examination committee.
10. The TLC plate was necessary to pack in an envelope and leave it to a laboratory
superviser.
TH
THE 35 INTERNATIONAL CHEMISTRY OLYMPIAD, Athens, 2003
PRACTICAL PROBLEMS
Synthesis of the Dipeptide N-acetyl-L-prolinyl-L-phenylalanine Methyl Ester
(Ac-L-Pro-L-Phe-OCH3)
Introduction
Peptide synthesis is now a well-refined art and many of their synthetic procedures
can be readily adapted to the elementary laboratory. Interest in peptides, always high, has
heightened even more with the recent discovery of the importance of the so-called “opiate”
peptides as well as of other biological active peptides.
In this experiment the one-pot procedure for synthesizing the title dipeptide from its
components, suitably protected amino acids, is described.
Reactions
STEP 1
O CH3 O
C N-methylmorpholine(NMM)1
N O C
OH + CH CH2 O N
C DCM2, -15 0C to -20 0C O
O C CH CH3
O C CH C O
3 Cl 3 CH3
A OCH2CH
CH3
isobutylchloroformate mixed anhydride
N-Acetyl-L-Proline
activated intermediate
STEP 2
O O
O
+ NMM.HCl
C C N OCH3
N N
O N-methylmorpholine
Cl-H3+NCHCOOCH3 H
O C CH C O O C CH + CO2
3 -15 0C to -20 0C 3
O +
(CH3)2CHCH2 C CH3
B +
L-Phenylalanine methyl ester Ac-L-Pro-L-Phe-OCH3 CHCH2OH
activated CH3
intermediate hydrochloride
Mr= 318.37
TH
CH3
N
1
N-methylmorpholine (NMM) =
2 O
DCM = Dichloromethane
Procedure
STEP 1
Place the 1.50 g (0.0095 mol) sample of N-acetyl-L-proline (labelled AcPro), which
3 3
you have been given, into a 50-cm round-bottom flask. Add 20 cm dichloromethane
(labelled DCM) in the graduated cylinder. Use some of the 20 cm3 DCM to wash out the
AcPro vial and add the remaining DCM also into the round-bottomed flask. Plug the flask
with a septum, clamp it loosely to a support stand and cool it to –15 °C to –20 °C in the
ice/sodium chloride cold bath provided by the supervisor. Allow approximately 5 minutes
for cooling. Add 1.2 cm3 (0.0109 mol) of N-methylmorpholine (labelled NMM) to the flask,
by means of a syringe. Then, slowly add 1.5 cm3 (0.0116 mol) isobutyl-chloroformate
(labelled IBCF) to the flask by means of a second syringe. During the addition, swirl the
reaction mixture gently by hand, and continue swirling for another 10 min. The
o o
temperature should remain in the range –20 to –15 C.
STEP 2
Remove the septum and quickly add all the L-phenylalanine methyl ester
hydrochloride (2.15 g, 0.0100 mol), (labelled HCl·H2NPheOCH3) using the polypropylene
3
powder funnel. Plug the flask again with the septum. Immediately add 1.2 cm (0.0109
mol) of N-methylmorpholine (labelled NMM) using a third syringe, while the reaction
mixture is swirled by hand. ATTENTION: Leave the needle part of the syringe in the
septum for the remainder of the reaction. Allow the reaction to proceed for 60 min at
–15 °C to –20 °C, swirling periodically by hand.
During this waiting period you are highly advised to start working on the Analytical
Chemistry experiment.
After 60 min at –20 oC to –15 oC, remove the 50 cm3 round-bottomed flask from the
3
ice/sodium chloride bath and place the flask in the 250 cm beaker and let it warm up to
TH
3
room temperature. Transfer the contents of the flask into the 50 cm separating funnel by
means of the glass funnel. Rinse the flask with a small amount of dichloromethane (3 – 5
3
cm ), which is in a vial (labelled DCM). Wash the organic layer successively with two 20
3 3
cm portions of 0.2 M aqueous HCl solution, two 20 cm portions of 1 % aqueous
NaHCO3 solution (read caution comment in next paragraph) and finally one 10 cm3 portion
of saturated solution of sodium chloride (labelled brine).
Important
After each washing allow the separating funnel to stand for enough time, so that the
two phases separate completely. Also, take into consideration that the organic phase
(DCM) is always the lower layer and contains the product. All the aqueous washings are
collected in the same Erlenmeyer flask (empty if necessary).
CAUTION: Keep in mind, also, that during washing with 1 % NaHCO3, the CO2
liberated is exerting pressure on the separating funnel stopper, so be sure to let the gas
out through the stopcock before and after each shaking, while holding the funnel upside
down.
3 3
Before continuing, wash the glass funnel, the 50 cm cylinder and the 50 cm round-
bottom flask with water and then dry them with acetone. Your supervisor will show you
where to dispose of the water and the acetone.
Pour the organic layer into a clean 50 cm3 Erlenmeyer flask. Add the anhydrous
sodium sulphate, which is in a vial labelled Na2SO4, to the Erlenmeyer flask containing the
organic layer. The organic phase should become clear. Filter it through the cleaned and
dried funnel, whose stem you have previously stuffed with a small piece of cotton to trap
any solids, into the cleaned and dried 50 cm3 round-bottom flask. Rinse the Erlenmeyer
flask with a small amount of dichloromethane (3 – 5 cm3). Removal of the organic solvent
is done under reduced pressure, using a rotary evaporator apparatus. This will be done for
you by a laboratory supervisor, who will add 20 cm3 of diethylether to the residue in your
flask, which will cause precipitation of your product. After cooling for 5 minutes in the ice
bath, scrape the walls of the flask with a spatula, filter by suction the crystallized dipeptide
3
through a fritted glass funnel. Wash twice with diethylether (5 cm each time).
TH
Leave the product on the filter under suction for at least 3 minutes. Then collect it on
weighing paper, weigh it in the presence of a supervisor and then transfer it into a sample
vial and label it with your student code. Write the mass of your product (C) on the label
and on your answer sheet (on the next page).
During the reaction between the phenylalanine methylester B and the activated
mixed anhydride intermediate (step 2) the formation of the desired dipeptide product C is
usually accompanied by a by-product the correct structure of which is one of the three
structures I, II, III given below. Circle the Roman numeral corresponding to the correct
structure.
O
H3C
CH O
H3C C H2 CH2
H2 O
CH2 H3C C CH O
N H2 CH O N
H3C C CH O H3C H
O CH O N
H CH3 N
H3C
CH3 O
O H3C
I II III
TLC- Analysis
You have two Eppendorfs, one empty and one with a tiny amount of substance B.
Put a small amount of C into the empty Eppendorf, and dissolve both B and C in a few
drops of methanol. Use the supplied capillary tubes to apply small samples of these
solutions to the TLC plate. Develop the TLC plate with a solution of chloroform-methanol-
acetic acid (7 : 0.2 : 0.2) as eluant. The appropriate amount of eluant has been placed in
the proper vial by the supervisor.
After the elution, analyze the TLC-plate using a UV-lamp. Clearly mark the starting
line, solvent front and the UV-active spots.
Draw the diagram in the box on the answer sheet. Determine the Rf values.
Finally place the TLC-plate in a small plastic bag with a sealing strip and put it in an
envelope provided by the supervisor. Write your student code on the envelope.
The examination committee will check the quality of the N-acetyl-L-prolinyl-L-
phenylalanine methyl ester that you have prepared by determining its angle of optical
rotation and consequently its specific rotation, [a]tD, using an accurate polarimeter
apparatus.
_______________
TH
SOLUTION
The following values were required to be written in the Answer Sheet
• Mass of Ac-L-Pro-L-Phe-OCH3 obtained (product C).

• The yield of Ac-L-Pro-L-Phe-OCH3 C.
• The TLC diagram with indication of the base line and the front of the solvent.
• Rf value of L-phenylalanine methyl ester hydrochloride (material B) and that of Rf
value of Ac-L-Pro-L-Phe-OCH3 (product C).
• Conclusions from the TLC analysis:

Compound C:
- Is pure,
- Contains some B,
- Contains several contaminants,
- No conclusion.
• Specific rotation of the dipeptide Ac-L-Pro-L-Phe-OCH3 C (to be measured later by

the examination committee)
T
[a] D
= 45 °
• The correct structure of the by-product: II.
TH
PRACTICAL PROBLEMS
Two-Step Organic Synthesis of 2,2-Bis(p-phenyleneoxyaceticacid)propane
(Bisphenol A bis(carboxymethyl)ether)
Introduction
In the first step the sodium salt of bisphenol A results as an intermediate from the alkaline
hydrolysis of a polycarbonate. By adding an acid this salt is converted into the free 2,2-
bis(4-hydroxyphenyl)propane (bisphenol A).
O
CH3
O
O C O
CH3
n
CH3
NaOH, H2O H3O+, H2O n HO C OH
CH3
In the second step bisphenol A reacts with sodium chloroacetate to form the phenolic
ether, bisphenol A bis(carboxymethyl)ether.
CH3
ClCH2COONa, NaOH, H2O H3O+, H2O
HO C OH
CH3
C CH2 CH3
HO O C O O
CH3 H2C C
OH
TH
• In each step the product has to be isolated.

(Drying and weighing will be done by the organizer.)
• For the product of step 2 three melting point tubes have to be filled.
(Filling of the melting point tubes in step 1 will be done by the organizer.)
(The melting points will be determined by the organizer.)
• When the organizer receives your labelled beaker A of step 1 you will get 2.00 g of
bisphenol A as starting material for the second step.
• Answer the additional questions on the answer sheet P1.
• Do not remove the Ceran plate from the magnetic stirrer.
Procedures
Step 1: Preparation of bisphenol A by alkaline hydrolysis of a polycarbonate
Preparation:
• Put the pre-weighed 2.54 g of polycarbonate (No. 1), 4.0 g of sodium hydroxide (No. 5)
and 3 cm3 of demineralized water into a 100 cm3 Erlenmeyer flask with ground-glass
joint.
• Close the flask with a plastic plug and swirl it gently so that the solution does not
contact the ground-glass joint. For aeration open the plastic plug occasionally. Strong
heating can be observed, as the sodium hydroxide partially dissolves.
• Remove the plastic plug after swirling for about 4 minutes, add a magnetic stirring bar
and put the flask onto a heating plate. Put a reflux condenser above the neck of the
flask. Use a Teflon coupling as a connection between flask and condenser. Fix the
apparatus tightly to a stand.
• Finally, add 20 cm3 of ethanol (No. 2) through the condenser while stirring the reaction
mixture.
• Heat the reaction mixture under reflux for 60 minutes. In the beginning adjust the
thermostat of the heating plate to maximum. When the mixture starts boiling reduce
the heat carefully, so that the mixture is kept under gentle reflux.
• A white precipitate is formed on heating.
During this waiting period you are highly advised to start working on the analytical
chemistry experiment.
TH
Isolation:
• Stop heating after one hour, allow the reaction mixture to cool down to ambient
temperature, remove the condenser, add 25 cm3 of demineralized water and transfer
3 3
the reaction mixture into a 400 cm beaker. Rinse the Erlenmeyer flask with 25 cm of
demineralized water and add this to the contents of the beaker.
•
3
Finally, fill up to 150 cm with demineralized water.
• If the reaction mixture is not clear, the mixture has to be filtered over fibre glass into an
Erlenmeyer flask.
•
3
Add slowly 15 cm of hydrochloric acid (No. 3) stirring the mixture simultaneously with
a glass rod. A rather oily or sometimes crystalline precipitate is formed.
• Ask your instructor for some seed crystals of bisphenol A (No. 27) in order to
accelerate the crystallization.
• Stir the reaction mixture thoroughly with the glass rod. For a quantitative crystallisation
continue stirring from time to time till the supernatant aqueous solution is nearly clear.
•
3
Collect the crude product by vacuum filtration, wash it twice with 10 cm portions of
demineralized water and transfer it quantitatively into the tared and labelled beaker A.
• For drying and weighing deliver your labelled beaker A into the instructor room.
• Afterwards you will get a small jar filled with 2.00 g of bisphenol A (No. 28), your
starting material of the second step.
• On delivery of your product and on receipt of the starting material you have to sign.
Even if you do not have any bisphenol A, please bring the empty beaker A to the
instructors’ room in order to get the starting material for step 2.
Step 2: Reaction of Bisphenol A with Chloroacetic Acid

forming 2,2-Bis(p-phenyleneoxyacetic acid)propane
(Bisphenol A bis(carboxymethyl)ether)
Preparation:
• Pour all the bisphenol A (No. 28) you have received from the organizer when you had
finished step 1 into a 100 cm3 Erlenmeyer flask with ground-glass joint.
• Add 10 cm3 of an aqueous sodium-hydroxide solution (No. 6), 1 cm3 of demineralized
water and a magnetic stirring bar.
TH
• Put the flask onto a heating plate. Put a reflux condenser above the neck of the flask.
Use a Teflon coupling as a connection between flask and condenser. Fix the
apparatus tightly to a stand.
• Heat the reaction mixture with gentle stirring until a clear solution is formed.
• Remove the heating plate and the condenser and add 5.0 g of the sodium salt of
chloroacetic acid (No. 4) to the reaction mixture.
• After reconnecting the flask with the reflux condenser, heat the mixture to reflux with
vigorous stirring for 30 min.
• Initially a clear solution is formed on heating. In some cases a colorless solid
precipitates. If the complete mixture becomes solid in the course of the reaction,
heating must be stopped.
• After that, 50 cm3 of ethanol (No. 2) are added carefully through the condenser
(beware of sudden boiling!). The mixture is stirred and heated under reflux for
5 minutes. A colourless solid precipitates, or the crystallisation which has already
started is completed.
Isolation:
• After leaving it to cool down for 5 minutes, transfer the reaction mixture with another
50 cm3 of ethanol (No. 2) quantitatively to a beaker. The reaction mixture should be
stirred vigorously.
• The magnetic stirring bar is removed and the reaction mixture is filtered through a
suction filter. Solids which separate in the filtrate are rejected. Rinse the beaker with
3 3
10 cm of ethanol (No. 2). The precipitate is washed twice with 10 cm portions of
ethanol (No. 2). (The filtrate must be disposed of in the organic solvent waste!)
• Transfer the precipitate quantitatively into a beaker, add a stirring bar and dissolve it in
150 cm3 of demineralized water. The mixture must be stirred vigorously. Larger lumps
of the solid must be crushed with the spatula.
• If the solution is not clear, it has to be filtered over a folded filter paper into an
Erlenmeyer flask.
• The slow addition of 5 cm3 of hydrochloric acid (No. 3) to the stirred reaction mixture
results in the formation of a white precipitate.
• Collect the crude product by vacuum filtration, wash it twice with 10 cm3 portions of
demineralized water and transfer it quantitatively into the tared and labelled beaker B.
TH
• Take a small sample of the product with a micro spatula, crush it and dry it on a shard.
Fill three melting point tubes with the homogenized, dried sample. For a close-packed
and 5 mm high filling use the 75 cm glass tube and the measure.
• Put all three melting point tubes into the test tube B, which is labelled with your student
code, and give it together with your labelled beaker B with the product to the instructor.
On delivery you have to sign.
_______________
SOLUTION
1.1 You started with 2.54 g of polycarbonate. Determine the theoretical yield of
bisphenol A in g.
M1(polycarbonate) = M1(C16H14O3)nH2 ≈ M1(C16H14O3) = 254.30 g mol-1
m1 = 2.54 g
M2 (C15H16O2) = 228.31 g/mol
m2 = m1 × M1 × M2
–1
Theoretical yield of bisphenol A: 2.28 g
1.2 Determine your theoretical yield of bisphenol A bis(carboxymethyl)ether in g based

on 2.00 g bisphenol A.
M2 (C15H16O2) = 228.31 g/mol
m2 = 2.00 g
M3 (C19H20O6) = 344.39 g/mol
m3 = m2 × M2 × M3
–1
Theoretical yield of bisphenol A bis(carboxymethyl)ether: 3.02 g
1.3
Unwanted by-products are possible in the second step. Write down the structural
formulas of two most probable unwanted by-products.
1. Bisphenol A reacts only once with sodium chloroacetate (monosubstitution):
CH3
HO C O O
CH3 H2C C
OH
TH
2. Alkaline hydrolysis of sodium chloroacetate:
H O O
H2C C
OH
TH
PRACTICAL PROBLEMS
The Synthesis of D,L-Phenylglycine and Its Enantiomeric Resolution

One of the enantiomeric forms of phenylglycine is an important raw material for the
preparation of β-lactam antibiotics. Industrial production of optically active phenylglycine is
prepared by the Andeno process. The starting benzaldehyde was treated with HCN/NH3
following hydrolysis to give the racemic D,L-phenylglycine. The desired enantiomeric
phenylglycine was then resolved by (+)-camphorsulfonic acid [(+)-CSA].
O
CHO OH
1. HCN, NH 3 Rh catalyst
2. Hydrolysis HCOONH 4
D,L-Phenylglycine
O
(Andeno Process)
Benzaldehyde D,L-phenylglycine Benzoylformic acid
In this experiment, you are going to synthesize racemic D,L-phenylglycine (also

referred to as R- and S-isomers, respectively) from an alternative method called reductive
amination. Treatment of benzoylformic acid under Rh metal catalyzed conditions gives
D,L-phenylglycine. The racemic D,L-phenylglycine is resolved by the treatment of (+)-CSA
in water. The solubility of D-phenylglycine•(+)-CSA salt is 5.75 g/100g H2O, while that of
L-phenylglycine•(+)-CSA salt is >150 g/100g H2O at 25 °C. The chemical yield and the
optical purity of the diastereomeric salt will be measured.
EXPERIMENTAL PROCEDURE
Step 1. Preparation of D,L-phenylglycine
The following pre-weighted chemicals can be used directly without further weighing:
Benzoylformic Acid; Ammonium Formate; Rh Catalyst; (+)-camphorsulfonic acid [(+)-
CSA].
1. To a 50 mL round-bottomed flask is added a magnetic stirring bar, pre-weighed
(approximate 1.80 g, exact mass will be on your sample bottle, write down the mass
TH
on your answer sheet and get the lab assistant to confirm the weight.) of
benzoylformic acid (NOTE: irritant, do not contact with skin), 7.57 g of ammonium
formate (HCO2NH4), 37.2 mg of Rh catalyst (NOTE: the catalyst is wrapped in a
3
weighing paper in a plastic bag. Handle with care!) and 22 cm of the pre-mixed
solvents at ambient temperature.
2. Put a reflux condenser (use the Teflon sleeve; you can trim off 1 cm from the smaller
end for a better fit) into the neck of the flask and plug the condenser with a septum.
For pressure equilibration, put a needle in the septum before starting the heating.
Clamp the apparatus tightly to the stand in your hot plate/stirrer. Put the flask onto a
hot water bath [hot water provided by the organizer] and stir the reaction mixture
gently. (NOTE: the solvent is air cooled, so there is no tap water running through the
condenser.) The temperature of the water bath needs to be maintained in the range
of 68 to 72 °C by adjusting the thermostat of the h ot plate/stirrer.
3. The mixture will become cloudy and the color of the solution will change from clear
yellowish to dark-greenish when the product starts to precipitate (generally requiring
25 ~ 35 minutes). The hot water bath should then be removed and the solution
allowed to stir in the water bath (ambient temperature) for an additional 10 minutes.
4. Add 15 cm3 of deionized water to the resulting mixture and stir for 10 minutes.
5. Pre-weigh the bigger fritted glass funnel (labelled with your student code), and get
the lab assistant to confirm the weight. Use the stir bar retriever to remove the stir
bar. Collect the product by filter suction through a fritted glass funnel under a
reduced pressure (rotary aspirator apparatus). Wash the solid four times thoroughly
3
with ethanol (10 cm each). For each washing, break the aspirator pressure, use a
glass rod to perturb the solid when adding ethanol, and reapply the rotary aspirator.
6. For rapid drying, you have to spread the product over the fritted glass funnel. For
drying, give the fritted glass funnel to the lab assistant. The product is dried in the
oven at 100 °C for 1.5 hour.
During the drying period you can start working on Experiment 2 (analytical
experiment) and you will be notified when your product is ready. Step 2 of
experiment 1 will need at least 1 hour.
7. Weigh the dried product [(D,L)-phenylglycine], record the data and calculate the
chemical yield (based on the starting benzoylformic acid). Get the lab assistant to
1
confirm the weight. The purity of the product will be determined by H NMR spectrum
TH
1
analysis. Turn in the product in a vial (blue label with H NMR and your student
code) to the lab assistant, and receive a new batch of D,L-phenylglycine for step 2.
Step 2. Enantiomeric Resolution of D,L-phenylglycine by (+)-Camphorsulfonic Acid

[(+)-CSA]
3
1. To a 25 cm round-bottomed flask add the pre-weighed sample of D,L-phenylglycine
provided (The exact mass will be on your sample bottle, write down the mass on your
answer sheet and get the lab assistant to confirm the weight). To this, add the pre-
weighed (+)-camphorsulfonic acid [(+)-CSA] (1.80 g). Clamp the apparatus tightly to
a stand in a magnetic stirrer. Add deionized water (4 cm3) and place the flask in a
hot water bath and heat it to a temperature in the range of 90 ~ 100 °C. Keep the
mixture at this temperature for 10 minutes until it turns clear.
2. Remove the hot water bath and allow the mixture to cool down to ambient
temperature for 10~15 minutes. With the flask plugged with a septum, cool the flask
in ice bath (Styroform) for 15 minutes. Crystals should appear in about 20 minutes, if
not, you may ask for seed crystals to induce the crystallization.
3. Pre-weigh the smaller fritted glass funnel (labelled with your student code), and get
the lab assistant to confirm the weight. Collect the product by filtering the solution
through a fritted glass funnel under a reduced pressure. Wash the solid thoroughly
two times with ice cooled distilled water (5 cm3 each).
4. For drying, give the fritted glass funnel to the lab assistant. The product will be dried
over in oven at 100 °C for 20 min. You will be noti fied when your product is ready.
Weigh the product, and get the lab assistant to confirm the weight. Record the data
and calculate the chemical yield (based on starting D,L-phenylglycine).
5. The optical purity of the diastereomeric salt will be measured using an accurate
polarimeter apparatus by the examination committee. Transfer the dried product to a
sample vial (pink label labelled with [α]D and your student code) and give the sample
vial to the lab assistant. The organization committee will weigh an appropriate
amount of the product (0.055 ~ 0.065g) for measurement of optical purity.
_______________
TH
SOLUTION
1.4 Structural formula (A) and stereochemical formula (B) of the isolated phenylglycine:
(Task appeared in the answer sheet only.)
NH2 COOH
OH OH
H NH2
O O
Ph
A B
TH
PRACTICAL PROBLEMS
Synthesis of α-D-glucopyranose pentaacetate
OH OAc
O O
OH
Ac 2O OAc
OH
HO HClO 4 Ac O OAc
OH OAc
Caution: Use gloves while manipulating acetic acid and acetic anhydride.
Let the lab supervisors know if any is spilled.
Add and mix 12 cm3 of pure acetic acid to 12 cm3 of acetic anhydride (provided in an
Erlenmeyer flask) and add 3.00 g glucose (acetic anhydride is in excess). Add with a
Pasteur-pipette 5 drops of 30% HClO4 dissolved in acetic acid. After the addition of the
catalyst the solution might warm up considerably.
Let the mixture rest covered for 10 minutes and swirl it from time to time. Pour the
reaction mixture into 100 cm3 of water in a beaker. Scratch the wall of the beaker with a
glass rod to initiate crystallization, and let it crystallize for 10 minutes. Filter and wash the
product two times with 10 cm3 of water using the syringe and the porous polypropylene
filter disc.
Filtration using a plastic syringe
1 2,3 6 9
TH
1. Pull out the piston. Fill the syringe from above with the suspension to be filtered. The
syringe can be filled to the level of the hole. Replace piston.
2. Cover the hole with your finger and press in the piston as far as the hole.
3. Open the hole and draw the piston back. Do not draw in air through the filter.
4. Repeat steps 2-3 a few times to expel the liquid.
5. Repeat steps 1-4 until all solids are on the filter.
6. Press the piston against the filter cake and squeeze out the liquid.
3
7. Wash the product twice with 10 cm of water repeating steps 1-4.
8. Press the piston against the filter cake and squeeze out the water.
9. Pull the piston out with the hole closed to lift out the filter cake. (Pushing with the
end of the spatula can help.)
1.1 Place your product in the open Petri dish marked with your code. Leave it on your
table. The organizers will dry it, weigh it and check it for purity.
1.2 Calculate the theoretical yield (mass) of your product in g. (M(C) = 12 g mol-1,
M(O) = 16 g mol-1, M(H) = 1.0 g mol-1
Synthesis of α-D-glucopyranose pentaacetate from β-D-glucopyranose pentaacetate

An alternative synthesis of α-D-glucopyranose pentaacetate starts from readily
available β-D-glucopyranose pentaacetate. In this experiment we will study the kinetics of
this reaction with thin layer chromatography.
OAc
OAc
OAc O
O
Ac 2O OAc
OAc
ZnCl 2 Ac O OAc
Ac O
OAc
OAc
Add 1.5 cm3 acetic anhydride to 50 mg of anhydrous ZnCl2 (preweighed in a test

tube). Add 100 mg of pure β-D-glucopyranose pentaacetate (BPAG) and swirl until
dissolved. Take three drops from this mixture into an Eppendorf tube, add 0.5 cm3
methanol and save it.
Place the test tube in the heating apparatus under the hood closest to your desk.
Place the test tube in the heating block preadjusted to 70ºC. Mix the contents of the test
tube from time to time. During the reaction take three drops of sample from the mixture
TH
with a Pasteur pipet after 2, 5, 10, and 30 minutes. Mix immediately each sample with 0.5
3
cm of methanol to stop the reaction in an Eppendorf tube.
Prepare a silica TLC plate with the collected samples to study the reaction kinetics.
Apply the necessary reference compounds as well to help identification of the spots on the
plate. Mark the spots with a pencil, and develop the plate in isobutyl acetate/ isoamyl
acetate (1:1) eluent. Heat the plates with a heat-gun (under the hood!) to visualise the
spots (the colour is stable). You can ask for a second plate without penalty points if
needed for proper evaluation.
1.3 Copy your plate on the answer sheet and place your plate in the labelled zip lock
bag.
1.4 Interpret your experiment and choose the correct answer.
The acetylation reaction of glucose is exothermic.
a) Yes
b) No
c) Cannot be decided based on these experiments
The isomerisation reaction of β-D-glucopyranose pentaacetate can be used for the

preparation of pure α-D-glucopyranose pentaacetate.
a) Yes
b) No
c) Cannot be decided based on these experiments
_______________
SOLUTION
1.1 Yield of the product in g, measured by the organizer.
The samples are dried by the organisers. The typical yield is 70 %.
Purity is checked by solubility (acetone) and TLC. If there is no insoluble material
and no impurity is detectable by TLC, the full points for the yield are received.
1.1 Calculation of the theoretical yield of the product in g:
C6H12O6 → C16H22O11
TH
3.00 g × 390 g mol-1

m= = 6.50 g
180 g mol-1
1.3 The developed TLC plate was expected to be sketched on the answer sheet.
Full points were given if both standards and all samples are present.
1.4 Solutions: a), a).
ST
PRACTICAL PROBLEMS
An Environmentally Friendly Aldol Condensation

In attempts to become more environmentally friendly, increasing attention is being
paid to minimising the large amounts of solvents used in chemical reactions. In the
following experiment, an aldol condensation reaction is carried out in the absence of
solvent.
O
MeO CHO
+ NaOH
A
MeO C18H18O4
or C18H16O3
Chemicals
• 3,4-dimethoxybenzaldehyde, 0.50 g pre-weighed in vial,
• 1-indanone, 0.40 g pre-weighed in vial,
• NaOH, 0.10 g pre-weighed in vial,
• HCl, aqueous solution, c = 3.0 mol dm–3, 10 cm3 in a bottle,
• Diethyl ether : Heptane (1:1), 25 cm3 in a bottle,
• Ethyl ethanoate, 1 cm3 in a small vial,
• Sample of 1-indanone dissolved in ethyl ethanoate, 1.0 cm3 in small vial,
• Sample of 3,4-dimethoxybenzaldehyde dissolved in ethyl ethanoate, 1.0 cm3 in small

vial,
• Ethyl alcohol (9:1 mixture with H2O): 100 cm3 in a bottle.
ST
Procedure
(a) Add 3,4-dimethoxybenzaldehyde (DMBA 0.50 g, 3.0 mmol) and 1-indanone (0.40 g,
3
3.0 mmol) to a 25 cm beaker. Use a metal spatula to scrape and crush the two
solids together until they become a clear oil.
(b) Add NaOH (0.1 g, 2.5 mmol) to the reaction mixture, crush any lumps formed and
continue scraping and crushing until the mixture becomes solid.
3
(c) Allow the mixture to stand for 20 minutes. Then add 4 cm of aqueous HCl solution
–3
(c = 3 mol dm ) and scrape around the beaker so as to dislodge all product from the
walls. Use a flat-ended glass rod to crush any lumps present.
1.1 Measure and record the pH of the solution.
(d) Isolate the crude product using vacuum filtration through a Hirsch funnel. Rinse out
the beaker with 2 cm3 of aqueous HCl solution (c = 3 mol dm–3) and pour over the
crude product in Hirsch funnel to wash, continuing to pull air through the solid for
10 minutes to facilitate drying.
1.2 Report the mass of the crude product (which may still be a little wet), using the vial
labelled ‘CPA’ as a container.
(e) Take a TLC to assess whether the reaction is complete, using Et2O : heptane
(1 : 1) as the eluant. Solutions of both starting materials in ethyl ethanoate are
provided. The crude product is soluble in ethyl ethanoate.
[Note: Three TLC plates are provided. You may use them all, but you must only
submit one in your labelled Ziploc bag. This should be the plate that you draw in
your answer booklet.]
1.3 Using UV light to visualize, draw around the spots on the plate in pencil to show
where they are, copy your plate onto the answer sheet, and place your plate in the
Ziploc bag labelled with your student code.
Determine and record the relevant RF values.
(f) Using a 100 cm3 conical flask with a stir bar in the bottom, recrystallize the product
from a mixture of EtOH : H2O (9 : 1). (N.B. A hot filtration, using the glass funnel
provided, is required as part of this process to remove small amounts of insoluble
ST
impurities.) Any lumps may be crushed using the flat-ended glass rod. Allow the
conical flask containing the filtered solution to cool to room temperature and then
cool in an ice bath (use the polystyrene tray to make the ice bath in) for one hour
before filtration through a Büchner funnel to collect your product. Suck air through for
10 minutes to dry the product. Place your product in the vial marked with your code
and labelled ‘RPA’.
1.4 Report the mass of the purified product.
Product A could have one of the two formulae: C18H18O4 or C18H16O3.

1.5 Draw the structure of every geometrical and/or stereoisomer with formula:
i) C18H18O4 ,
ii) C18H16O3
that could be formed in this reaction. Indicate how many peaks you would expect in
13
total in the C NMR spectrum of each.
13
1.6 The C NMR spectrum for A is shown in the practical instructions. Peaks due to the
solvent, CDCl3, are marked with an asterisk. With the aid of the spectrum, decide
which is the correct formula for A. Mark on the answer sheet one of the two boxes
below to indicate which you have chosen:
C18H18O4: ❑ C18H16O3: ❑
1.7 Report the mass and calculate the percentage yield of the purified product, based on
the formula you gave for its structure.
_______________
ST
SOLUTION
1.1 Values of pH = 1 – 2 are accepted.
1.2 Because the sample is not completely dry, often this mass is above 100 % of that
expected. Usual range is 800 – 1000 mg (94 – 117 %). Zero points for any less than
400 mg (product has been lost).
1.3 Evaluation:
Maximum points if both standards plus crude product are present and no starting
materials remain and student has co-spotted crude product with one or both starting
materials and solvent front is marked and plate is not over- or under-loaded.
Minus points if:
- plate has no co-spots,
- substantial amount of either or both starting materials remain,
- over- or under-loading occurs which does not interfere with evaluation,
- over- or under-loading occurs and does interfere with evaluation,
- over- or under-loading occurs and prevents evaluation,
- any sample is missing.
The relevant RF values:
Chemical RF
3,4-DMBA 0.16 – 0.25

1-Indanone 0.34 – 0.43
CPA 0.11 – 0.20
Maximum points if both starting materials and reaction product are present with Rf
values which fall within those given.
Minus points if:
- RF values are missing for one or more chemicals,
- both starting materials and reaction product are present with RF values which fall
outside those given due to the plate running too long or the student having marked
the solvent front incorrectly,
- both starting materials and reaction product are present with RF values which fall
outside those given, due to an inability to calculate RF values.
ST
1.4 For C18H18O4 :
13
Structure Number of C NMR signals expected:
18
18
18
18
For C18H16O3 :
Structure Number of 13C NMR signals expected:
18
18
ST
1.5 C18H16O3:
1.6 Mass: 0.5 g (example mass of product)
Calculation:
–1
For formula C18H18O4: Molar mass = 298.324 g mol
Expect: 0.3 mmol maximum = 0.895 g
0.5 g
× 100 = 56 %
0.895 g
–1
For formula C18H16O3: Molar mass = 280.308 g mol
Expect: 0.3 mmol maximum = 0.841 g
0.5 g
× 100 = 59.5 %
0.841 g
YIELD:
The samples were also weighed by the organizer, before and after drying for one
hour in a vacuum desiccator. Sample purity was then checked by 1H and 13
C NMR.
The evaluations of the results were adapted to the results obtained by the above
measurements.
ND
PRACTICAL PROBLEMS
Reaction of Hantzsch Ester with Urea Hydrogen Peroxide

In this experiment, you are required to synthesize a pyridinedicarboxylate derivative
from 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylic acid diethyl ester (1,4-DHP or
Hantzsch ester) by oxidation with urea hydrogen peroxide (UHP), an environmentally-
friendly oxidant.
O
H H
N N
O O
CH3CH2 H H O O
CH2CH3
O O UHP O O H CH3CH2 CH2CH3
O O
H
H3C N CH3
H H3C N CH3
KI
1,4-DHP
Chemicals
• Hydrochloric acid, c = 0.5 mol dm , 50 cm
–3 3
• 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylic acid diethyl ester, C13H19NO4;

(1,4-DHP), powder, 1 g
• 1,4-DHP for TLC, 3 mg
• Ethanol, C2H5OH, 10 cm3
• Ethyl acetate, CH3COOC2H5, 25 cm3
• Heptane, C7H16, 20 cm3
• Potassium iodide, KI, 150 mg
• Sodium metabisulfite, Na2S2O5, 1 g
• Sodium hydrogen carbonate, saturated aqueous solution, 25 cm3
• Urea hydrogen peroxide, CH4N2O•H2O2, (UHP), 1 g
Procedures
3
(1) Place a 22 mm magnetic stirring bar in a 100 cm test tube. Fix the test tube on a
magnetic stirrer using a clamp. Add 1,4-DHP (1 g) (labelled as 1,4-DHP powder), and
ND
3 3
potassium iodide (150 mg) to the test tube, followed by ethanol (5 cm ), with a 5 cm
graduated pipette.
(2) Add 1 g UHP (wear gloves) and stir the mixture. (Caution: this reaction is exothermic.)
(3) For thin layer chromatography (TLC) analysis, prepare a mixture of ethyl acetate and
heptane (1 : 2 in volume) using a measuring glass and place an appropriate amount of
3
the mixture in a TLC developing chamber. Add 1 cm of ethyl acetate to the vial
(labelled as 1,4-DHP TLC) to dissolve 1,4-DHP (3 mg).
(4) Check your TLC plates before using. If they are damaged, they can be replaced
without penalty. Draw a start line on the lower portion of a TLC plate with a pencil (see
Fig. 1.1).
(5) During the reaction, the reaction mixture becomes clear (usually within 20 min). When
the reaction mixture becomes clear (the precipitates may form when it cools, but
precipitates will not affect the TLC analysis), take a small portion of the mixture using a
glass capillary and load it to make two spots in the centre and right positions on the
TLC plate. Load an appropriate amount of the 1,4-DHP solution prepared in procedure
(3) in the centre and left positions, so that there are three spots on the plate, with the
centre spot containing both the reaction mixture and 1,4-DHP (see Fig. 1.1). Develop
the TLC plate in the TLC chamber (see Figs. 1.1 and 1.2). Mark the solvent front with
the pencil. Visualize the spots using a UV lamp (254 nm) and draw a line around the
UV-active spots on the TLC clearly with the pencil. Assess the completion of the
reaction based on the TLC results. Repeat the TLC analysis after ten minutes, if you
find significant amounts of 1,4-DHP in the reaction mixture. [Note that you will perform
TLC analysis again in procedure (8).] Place the last TLC plate in a zipper storage bag
marked “A.”
X X+Y Y
Fig. 1.1 Spots on the TLC plate before Fig. 1.2 TLC plate placed in the TLC
development; developing chamber.
X: 1,4-DHP, Y: Reaction mixture.
ND
(6) Set up the suction filtration equipment (see Fig. 1.3). Connect the suction flask to the
diaphragm vacuum pump. Place a Büchner funnel fitted with a rubber adapter onto
the suction flask. Place a glass microfiber filter sheet on the funnel.
Fig. 1.3 Suction filtration equipment:

i - Büchner funnel; ii - rubber adopter;
iii - suction flask; iv - diaphragm vacuum
pump.
3 3
(7) Add water (5 cm ) to the reaction mixture using a 10 cm plastic graduated cylinder.
Add sodium metabisulfite (1 g), transfer the contents of the tube (including the stirring
3 3
bar) into a 200 cm conical beaker and wash the test tube with water (30 cm ). Place
the 200 cm3 conical beaker on the magnetic stirrer and stir the solution. Add saturated
sodium hydrogen carbonate solution in small portions using a 2 cm3 graduated pipette
until the pH of the aqueous phase becomes just over 7 (check the pH with pH test
paper). Filter the precipitate formed through the Büchner funnel with suction using the
diaphragm vacuum pump, and wash the precipitate with a small portion of water. Suck
air through the precipitates for a minute to dry the product.
(8) Transfer the filtrate from the suction flask to a 300 cm3 conical beaker. Transfer the
filtrate (2 cm3) to a 10 cm3 test tube using a 2 cm3 graduated pipette. Place a 10 mm
magnetic stirring bar in the test tube and fix it securely with the clamp. Add 1 cm3 of
ethyl acetate to the test tube using a 2 cm3 graduated pipette and stir the solution
vigorously for 30 seconds on the magnetic stirrer. Stop stirring and wait for the solution
to separate into two layers. Analyze the upper layer by TLC to see if there is any
product remaining in the filtrates. Spot the filtrates on the plate in the same way as
procedure (5). Mark the solvent front and the spot(s), if any. Place the TLC plate in a
zipper storage bag marked “B.” If you detect the product on the TLC plate, add more
saturated sodium hydrogen carbonate solution.
ND
(9) At this stage, if you find a precipitate formed, filter and wash it. If you find no
precipitate, skip this filtration process.
(10) Suck air through the precipitate for 10 minutes to dry the product. Place your product
and the glass microfiber filter sheet in the crystallization dish. Cover the dish with the
lid marked with your code. Avoid placing the stirring bar in the dish. Place the
crystallization dish with the lid in a zipper storage bag marked “C.”
1.1 Copy (sketch) the TLC plate in bag “A” on your answer sheet.
1.2 Determine and record the Rf values (to the 2nd decimal place) of the spots on the
TLC plate in bag “A.”
1.3 Draw the structural formula of the organic cation before adding sodium hydrogen
carbonate.
1.4 What is (are) the final product(s) derived from UHP? Give the chemical formula(e) of
the product(s).
1.5 Submit the following:
i) TLC plate in bag “A”.
ii) TLC plate in bag “B”.
iii) Your product and filter paper in the crystallization dish placed in bag “C”.
_______________
ND
SOLUTION
1.1 Indication of the solvent front line and the base line is expected.
Some points will be subtracted if:
i) there are less than three spots loaded on the base line,
ii) the spots are not separated on the TLC after development,
iii) the solvent front line and/or the base line is missing.
1.2
Spot Rf value
1,4-DHP 0.32 – 0.42
Product 0.61 – 0.71
1.3
O O
CH3CH2 CH2CH3
O O
+
H3C N CH3
H
1.4 H2O and CH4N2O
1.5 The following rules for evaluation of the practical results in this problem were
suggested by the organizer and approved by the International Jury:
Evaluation of the TLC plates.

Points will be subtracted:
- if the outline to be drawn with a pencil around the UV-active spots, is unclear or
missing,
- if the solvent front line and/or base line is missing.
Evaluation of the product and filter paper in the crystallization dish (in bag “C”).
i) A technician should weigh the product and calculate the percent yield after
drying at 60 °C.
ii) In most cases the sample is pure and dissolved in CDCl3 completely. The
special calculation based on the percent yields and an approved graph is
ND
1
applied only if no 1,4-DHP or by-products are observed in the H NMR
spectrum and the product is completely soluble in CDCl3.
iii) If there are peaks of 1,4-DHP (ca δ 2.19 ppm) and the corresponding pyridine
product (ca δ 2.85 ppm) in the H NMR spectrum and the percent yield is 100 %
1
or less, the actual percent yield is calculated by an equation proposed by the

organizer and approved by the International Jury.
iv) Some points subtraction is suggested:
1
- if insoluble material remains after the addition of CHCl3 for H NMR
measurements,
- if by-products are detected evidently in the 1H NMR spectrum.
RD
Synthesis, purification and separation of a diastereomeric mixture
Nature has many compounds in the form of a single enantiomer or diastereomer
such as sugars, amino acids, steroids, etc. Some of these compounds are biologically
active and used as drugs. Therefore, the asymmetric synthesis of organic compounds is
important. One of the methods for the asymmetric synthesis of organic compounds
employes a metal-catalyst, in which the metal is coordinated to a chiral organic molecule
named as chiral ligand. In this experiment two chiral ligands will be synthesized.
H H
CH 3 CH 3
O Br O O O
N N
H
Et3N H 2N CH 3
H + H
Fe Br Fe Br Fe Fe
CHCl3, rt CHCl3, rt
(R)-1-phenylethanamine
2,3-dibromo-1-
ferrocenylpropan-1-one fraction A fraction B
Chemicals
• 2,3-dibromo-1-ferrocenylpropan-1-one, 0.50 mmol, labelled as “Rxn RB”
• Triethylamine, 1.0 mmol in 1.0 cm3 of CHCl3, label: “V 1”
3
• (R)-1-phenylethanamine, 1.0 mmol in 0.5 cm of CHCl3, label: “V 2”
• 2,3-dibromo-1-ferrocenylpropan-1-one, reference starting material for TLC, label: “SM”
• Heptane : ethyl acetate mixture in a volume ration 3 : 2, 500 cm3, label: “ELUENT”,
A. Synthesis
1. Using a syringe, transfer through the septum the triethylamine solution in vial 1 (V 1)
to the 10 cm3 round bottom reaction flask (Rxn RB) containing 0.50 mmol
2,3-dibromo-1-ferrocenylpropan-1-one.
2. Stir the mixture at room temperature for 30 minutes using the magnetic stirrer at 600
rpm (as marked on the stirrer).
3. After 30 minutes, transfer through the septum the (R)-1-phenylethanamine solution
in vial 2 (V2) to the reaction flask using the same syringe.
4. Stir the mixture for additional 60 minutes at room temperature.
RD
5. After 60 minutes turn off the magnetic stirrer and perform a thin layer
chromatography, TLC, analysis as follows:
i) Check your TLC plates before use. Damaged plates will be replaced upon
request without penalty.
ii) Draw a start line on the lower portion of TLC plate with a pencil (Fig. 3.1).
iii) Apply starting material from the vial labelled as SM two times to the spot on the
left and then two times to the spot in the middle of plate. To the same plate,
apply the reaction mixture (RM) taken from the reaction flask once to the spot on
the right and then once to the spot in the middle as shown in Figure 3.1 (use a
different capillary tube for each sample).
iv) Develop TLC plate in the TLC chamber with the eluent. Mark the solvent front
with the pencil (Fig. 3.2).
v) When the TLC plate is dry, place it in a zipper storage bag marked as TLC1.
Figure 3.1. TLC plate Fig. 3.2 TLC plate placed in the
TLC developing chamber.
B. Flash Column Chromatography

1. Remove the stopper, open the valve, and bring the eluent level at top of column to
the upper level of silica gel. (Fig. 3.3).
2. Close the valve and load the content of reaction flask on the top of flash column
using a Pasteur pipette.
3. Rinse the reaction flask with 0.5 cm3 eluent taken from the bottle labelled as
ELUENT using a clean syringe. Using the same Pasteur pipette, load the washings
also on the top of column.
4. Open the valve of the column and let the solvent run down to the upper level of silica
gel.
RD
3
5. Close the valve and add 1.0 cm eluent by a Pasteur pipette. Open the valve. When
3
the eluent is at the upper level of silica gel, add 2 - 3 cm eluent slowly without
closing the valve.
6. Fill the column by adding more eluent.
CAUTION: Be careful during the addition of eluent; do not disturb silica gel.
Figure 3.3. Flash Column Chromatography
7. In order to speed up the purification, apply little pressure by connecting the pressure
applying bulb with an adapter on top of the column.
CAUTION: Be careful not to apply too much pressure. Add eluent time to time to
avoid silica gel run dry.
8. You are expected to collect two major fractions A and B. Discard any material which
elutes before major fraction A and between A and B into the container labeled as
Organic Waste.
RD
3
9. Collect the first major fraction into a 100 cm Erlenmeyer flask and label it as
fraction A.
3
10. Collect the second major fraction into a 250 cm Erlenmeyer flask and label it as
fraction B.
11. After collecting fraction B stop the elution by closing the valve.
C. Analysis. Perform
1 Perform another TLC by applying the starting material (SM) two times to the spot on
the left, apply fraction A two times to the spot in the middle, and then fraction B five
times to the spot on the right. After development, when the TLC plate is dry, place it
in a zipper storage bag marked TLC2.
2. Measure the volume of fraction A using 50 cm3 graduated cylinder and record the
volume to your answer sheet.
3. Measure the volume of fraction B using 250 cm3 graduated cylinder and record the
volume to your answer sheet.
4. Using a 2 cm3 pipette transfer 2.0 cm3 of fraction A into the 10 cm3 volumetric flask
and complete the volume to 10 cm3 by adding eluent. After shaking the flask, fill out
the UV-visible cell (at least ¾ of its volume) by using a Pasteur pipette. Ask the
assistant to measure the absorbance at 450 nm using the spectrophotometer and
record the result to your answer sheet.
5. Using fraction B, fill out (at least ¾ of its volume) the other UV-visible cell by a
Pasteur pipette (no need for dilution). Ask the assistant to measure the absorbance
at 450 nm using the spectrophotometer and record the result to your answer sheet.
Treatment of Data
3.1 Copy (sketch) the TLC1 plate on your answer sheet.
3.2 Copy (sketch) the TLC2 plate on your answer sheet.
3.3 Calculate and record the Rf values of the spots (fraction A, fraction B, and starting
material SM) using the TLC2 plate.
3.4 The molar extinction coefficient, molar absorptivity, ε, is 404 M-1cm-1 for A and 400
M-1cm-1 for B at 450 nm (M = mol dm-3). Calculate in percent:
i) the yield of fraction A based on the starting material.
ii) the yield of fraction B based on the starting material.
_______________
RD
SOLUTION
3.1 – 3.2
Maximum points are given:
- for the appearance of three spots loaded on the base line,
- for the well developed and separated spots on the TLC,
- for the solvent front line and the base line,
- for the accurate presentation of the sketch of the TLC,
- in part 3.2, moreover, for the absence of fraction B in fraction A and vice versa.
3.3 Maximum points if calculated and recorded Rf values fall within those given in the
following table:
Spots Rf value
Fraction A 0.40 – 0.50
Fraction B 0.20 – 0.30
Starting material SM 0.65 – 0.75
3.4 Points were awarded in accordance with some distribution graphs proposed by the
organizer and approved by the International Jury. The graphs were applied for
fraction A and B, when evaluating their volumes, absorbance and yields.
TH
PRACTICAL PROBLEMS
Synthesis of 2,4-dinitrophenylhydrazones
Hydrazones belong to the class of imines, which contain a nitrogen-nitrogen single
bond adjacent to a carbon-nitrogen double bond. Hydrazones are formed when NH2-
containing hydrazine reacts with aldehydes or ketones under appropriate conditions.
Because the hydrazone derivatives of the carbonyl compounds are often stable,
crystalline, highly coloured solids, they are used to confirm the identity of aldehydes and
ketones.
In this task you will have to identify two substituted benzaldehydes (shown
below) by studying the products of their reactions with 2,4-dinitrophenylhydrazine.
O
O
CH3
O
O
OH H3C
Reagents
• 2,4-Dinitrophenylhydrazine
• Sulfuric acid, concentrated
• Aldehyde solution, 1 mmol in ethanol
• Ethanol
• NaOH solution
• Acetone
TH
Procedure
Equip one 50 cm3 beaker with a magnetic bar. Fix the beaker on the stirrer using the
metal ring attached to the stand. Place the content of vial (200 mg of
2,4-dinitrophenylhydrazine) into the beaker and start stirring carefully. Only in the presence
of your lab assistant, carefully pour one sample of concentrated sulfuric acid
3 3 3
(1 cm ) onto the solid. Using pipettes add 1.6 cm of water and 4 cm of ethanol to the
reaction mixture. Then using a pipette add dropwise the content of the aldehyde solution
bottle (either “aldehyde 1” or “aldehyde 2”, each contains 1.00 mmol of the aldehyde).
Bright precipitate starts forming at once. Continue stirring for 10 min, then add 10 cm3 of
water and stir for another 3 min.
Separation and purification of the product

Using scissors carefully cut out a filter paper circle, ca. 1 cm bigger in diameter than
that of the glass filter. Wet the filter circle with water, and carefully put it on the filtering
surface. The paper filter should fit evenly and tightly. If you fail to cut out an even circle,
take a new filter from the table of common use and repeat cutting out. Assemble
apparatus. Remove the stirring bar from the beaker using the spatula and transfer the
reaction product onto the filter. Turn on the water-jet pump and filter out the precipitate.
Put a little amount of water in the beaker and transfer the leftover product onto the filter.
Wash the solid on the filter with water until the pH of the drops coming out the funnel are
neutral. Then wash the solid twice with ethanol using no more than 3 cm3 each time.
(Note: Hydrazone is slightly soluble in ethanol.)
Dry out the solid on the filter with working water-jet pump, loosening and squeezing
the product with a glass rod from time to time. After ca. 20 - 30 min transfer carefully the
dried powder into the self-made filter paper box for the final drying in the air. Put the box
with the product in a safe place (e.g. on the shelf). Turn off the water-jet pump when you
do not use it!
As soon as your products seem dry, we advise you weigh them to avoid queuing at
the balances. To collect the products, use the plastic tubes with your student code. Fill in
the answer box below.
Note: The products you synthesized will be further re-examined by lab staff.
TH
Repeat the above procedures with the other aldehyde.
Plastic tube 1 Plastic tube 2
Mass of empty tube __________ mg Mass of empty tube _________ mg
Mass of tube with product______ mg Mass of tube with product ______ mg
Mass of product __________ mg Mass of product _________ mg
Tasks:
1.1 Write down the structures of 2,4-dinitrophenylhydrazine and both products.
1.2 What kind of stereoisomerism (if any) is possible for these hydrazones? Tick the
appropriate box.
R/S E/Z threo/erythro manno/gluco D/L
1.3 What is the role of sulfuric acid in 2,4-dinitrophenylhydrazone formation? Tick the
appropriate box.
stoichiometric reagent catalyst reducing agent oxidizing agent
1.4 How would the rate of the reaction change, if the synthesis is carried out in neutral
medium? Tick the appropriate box.
highly increase slightly increase

no change the reaction would proceed very slow
1.5 How would the rate of the reaction change, if it is carried out in alkaline medium?
Tick the appropriate box.
highly increase slightly increase

no change the reaction would not proceed
TH
Characterization
Place small amount (“on the tip of a spatula”) of each product in an individual 25 cm3
3
beaker. Add 10 cm of acetone to each beaker. The best results will be obtained if the
3
colours and their intensities in each beaker are similarly yellow. Pour 5 cm of NaHCO3
solution into each beaker. Stir the resulting mixtures with the glass rod using different
ends.
1.6 Record your observations of the solutions colour change. Tick the appropriate box.
The colour does not change in either beaker.

The colour changes significantly in both beakers.
The colour changes significantly only in one beaker.
Add 2 cm3 of NaOH solution to each of the resultant mixtures from the question 1.6.
Stir the reaction mixtures with the glass rod.
1.7 Record your observations of the solutions colour change in the box.
The colour does not change in either beaker.
The colour changes significantly in both beakers.
The colour changes significantly only in one beaker.
1.8 What structural features of your products explain the colour change in the reaction
with NaHCO3? Tick the appropriate box.
the presence of MeO group at position 4 in the benzene ring;
the presence of MeO group at position 3 in the benzene ring;
the presence of the OH group at position 4 in the benzene ring;
the presence of both MeO and OH groups.
1.9 Which of the listed processes is responsible for the colour change observed in the
reaction of 2,4-dinitrophenylhydrazones with aqueous NaOH? Tick the appropriate
box.
alkaline hydrolysis dehydration hydration
deprotonation dehydrogenation
TH
1.10 Draw the structures of the main organic species present in each test reaction medium
in the answer boxes below.
Initial aldehyde: Initial aldehyde:

O O
CH3
O
O
OH H3C
NaHCO3 NaHCO3
NaOH NaOH
1.11 Put the numbers 1 or 2 under each structure. Calculate the percent yields of both
hydrazones
_______________
TH
SOLUTION
1.1 2,4-dinitrophenylhydrazine
H
N
H2N
O2N NO2
Product 1:
H
N
N
MeO O2N NO2
Product 2:
H
N
N
HO O2N NO2
OMe
1.2 E/Z
1.3 catalyst
1.4 the reaction would proceed very slow
1.5 the reaction would not proceed
1.6 The colour changes significantly only in one beaker.
1.7 The colour changes significantly in both beakers.
1.8 the presence of the OH group at position 4 in the benzene ring;
1.9 deprotonation
TH
1.10
Initial aldehyde: Initial aldehyde:
O O
CH3
O
O
H3C OH
Product 1 in NaHCO3 Product 2 in NaHCO3
H H
N N
N N
O O2N NO2
MeO O2N NO2
OMe
Product 1 in NaOH Product 2 in NaOH
N N
N N
O O2N NO2 O O2N NO2
H3C OMe
NTT VN-123
Practical Code: Task 1 2 3 4 5 Total

Problem 2
Examiner Mark 35 15 20 4 2 76
13 % of the
total Grade
Practical Problem 2. Synthesis of a derivative of Artemisinin
Artemisinin (also known as Quinghaosu) is an antimalarial drug isolated from

the yellow flower herb Artemisia annua L., in Vietnam. This drug is highly efficacious
against the chloroquine-resistant Plasmodium falciparum. However, artemisinin has a
poor solubility in both oil and water so that one needs to prepare its new derivatives to
improve the applicability of this drug. The reduction of artemisinin is an attractive
method to synthesize new derivatives of artemisinin as shown in Scheme 1.
Scheme 1
In this practical exam you are going to reduce artemisinin to product P and
check its purity using Thin-Layer Chromatography (TLC).
Experimental Set-up
- The experimental set-up is shown in Figure 2.1.
- By moving the finger clamp, you can adjust the position of the two-neck round-
bottom flask.

NTT VN-123
2 3
1: Digital thermometer; 2: Plastic Stopper; 3: CaCl2 drying tube; 4: Ice Bath

Figure 2.1. Reaction system for Problem 2
Procedure
Step 1. Synthesis of a Derivative of Artemisinin
1. Prepare an ice bath with a temperature between –20 and –15 oC by mixing ice and
sodium chloride in the plastic pot (approximate ratio of NaCl : crushed ice = 1
scoop : 3 scoops). Use the digital thermometer to monitor the temperature. Place
the bath on the magnetic stirrer. Put a layer of three tissues between the bath and
the stirrer.
2. Connect the CaCl2 drying tube to the small neck of the round-bottom flask and
close the other neck with the plastic stopper.
3. Place a magnetic stirring bar into the dry round-bottom flask and set up the reaction
system onto the clamp-stand so that the system is immersed in the ice bath. Monitor
the temperature using the digital thermometer.
4. Setting aside a tiny amount (ca. 2 mg) of artemisinin for TLC analysis, open the
stopper and add the 1 gram of artemisinin through the bigger neck.
5. Use the glass funnel to add 15 mL of methanol (measured using the 50-mL
graduated cylinder). Close the stopper and turn on the magnetic stirrer. (Set the
magnetic stirrer to level 4). Start the stopwatch to keep track of the time.
6. After ca. 5 min stirring, open the stopper and add carefully 0.53 g of NaBH4 in
small portions over 15 min using a spatula. Close the stopper in between addition.
(Caution: Adding NaBH4 rapidly causes side-reactions and overflowing). Keep
stirring for 50 min. Maintain the temperature of the ice bath below –5 oC; remove

NTT VN-123
some of the liquid and add more NaCl-crushed ice mixture if necessary. Cool the
vial containing the 1 mL of acetic acid in the ice bath.
During this waiting time, you are advised to finish calculations from Problem 1,
answer the questions below, and prepare further experimental steps.
7. Prepare 50 mL of ice-cold distilled water (cooled in the ice bath) in the 100 mL-
conical flask. Measure ca. 20-22 mL n-hexane in the 50 mL measuring cylinder
and cool it in the ice bath. After the reaction is complete, keep the reaction flask in
the ice bath below 0 oC. Remove the CaCl2 tube, open the stopper, and add
gradually ca. 0.5 mL of the cold acetic acid from the vial into the reaction flask
until the pH is between 6 and 7. (Use the glass rod to spot the reaction mixture on
to the pH paper.) With stirring, slowly add the 50 mL of ice cold water over 2 min.
A white solid precipitates in the reaction flask.
8. Assemble the vacuum filtration apparatus. Put a filter paper onto the Büchner
funnel, wet the filter paper with distilled water and open the vacuum valve.
Transfer the reaction mixture on to the filter, and remove the stirring bar from the
reaction flask using the spatula. Wash the product three times with portions of 10
mL ice-cold water (cooled in the ice bath). Wash the product two times with
portions of 10 mL ice-cold n-hexane (cooled in the ice bath). Continue to use the
pump to dry the solid on the filter. After ca. 5 min, carefully transfer the dried
powder on to the watch glass labeled with your code and put into the labeled Petri
dish. Turn off the vacuum valve when you do not use it! Note: Your sample will
be collected, dried and weighed later by the lab assistant.
Task 2.1 – the recording of your yield –will be performed after the exam by the
lab assistants.
Step 2. TLC Analysis of the product

1. Check your TLC plate before use. Unused damaged plates will be replaced upon
request without penalty. Use the pencil to draw the start front line, and the line
where the solvent front will be run to exactly as shown in Figure 2.2. Write your
student code on the top of the TLC plate in pencil.

NTT VN-123
Figure 2.2. Instruction of TLC plate preparation
2. Dissolve ca. 1 mg of artemisinin (a spatula tip) in ca. 0.5 mL of methanol in the

labeled very small test tube (use the labeled 5 mL graduated pipette). Dissolve ca. 1
mg of the product in ca. 1 mL of methanol in the labeled test tube.
3. Spot the artemisinin solution and the product solution on the TLC plate using two
different glass capillary spotters so the finished plate is as shown in Figure 2.2.
4. Prepare the TLC developing chamber. Use the 5 mL graduated cylinder to make 5
mL of a mixture of n-hexane/ethyl acetate (7/3, v/v) as the solvent system. Pour the
mixture of n-hexane/ethyl acetate into the chamber (Note: The solvent level should
not reach the spots on the plate if prepared as shown). Cover and swirl the
chamber and allow it to stand for 2 min.
Watch glass
Developing chamber A
TLC plate b a
Solvent
a
Calculate Rf (A) =
b
Figure 2.3. A TLC plate placed in the TLC developing chamber and instruction for Rf
calculation of compound A

NTT VN-123
5. Insert the TLC plate upright into the TLC developing chamber. Wait until the
solvent system reaches the pre-drawn solvent front line. (Note: You are advised to
work on some question below while you wait for the TLC to run.)
6. When the solvent front reaches the line, remove the TLC plate using the tweezers
and then dry the solvent using the hair dryer set at level 1.
7. Dip the piece of cotton wool into the cerium staining reagent, taking care not to let
the tweezers come into contact with the solution since the metal stains the plate.
Carefully apply the stain to the whole TLC plate.
8. Heat the TLC plate using the hair dryer set at level 2 (Attention: Do NOT set the
hair dryer to COLD) until the blue spots of artemisinin and the product appear on
the TLC plate.
9. Ask the lab assistant to take a photo of your final TLC plate together with your
student code.
10. Circle all the visualized spots and calculate the Rf values of both artemisinin and
the product (See instruction in Fig. 2.3). Store your TLC plate in the Petri dish.
Task 2.2: Fill the values of Rf in Table below.
Rf, Artemisinin Rf, Product Rf Artemisinin/Rf Product
---------------------- -------------------------- --------------------------
Task 2.3: Check the total number of developed spots on the TLC plate:
1 2 3 4 5

NTT VN-123
Step 3. Identifying the reaction product P

The reduction of artemisinin leads to the formation of two stereoisomers (P).
Comparing the 1H-NMR spectrum (in CDCl3) of one of these isomers with the
spectrum of artemisinin shows an extra signal at δH = 5.29 ppm as a doublet, and also
an extra signal as a broad singlet at δH = 2.82 ppm.
Task 2.4: Suggest structure for P. (You do not need to draw the stereochemistry of the
compounds).
P
Task 2.5: P is mixture of two stereoisomers. What is their stereochemical

relationship? Check the appropriate box below.
Z/E Isomers Enantiomers Diastereomers Constitutional Isomers

TASK 1. Tuning bromination selectivity by catalysis (15 points).
Quest. # Q1 Q2 Q3 Q4 Q5 Q6 Total
Marks 2 39 4 2 1 2 50
Selectivity of chemical reactions is one of the most challenging problems of contemporary research. In
many cases, reaction conditions and the catalysts applied are keys to achieving high selectivity of
organic reactions. In this task, you will study one of such cases. 3-Methylthiophene can theoretically be
transformed into four monobrominated derivatives T1-T4, which have been actually synthesized and
characterized in detail. Structures of T1-T4 and the values of refractive indexes are given in Table 1.
Table 1. Structures and refractive indexes of monobrominated thiophenes.

Designation A B T3 T4
Br
Structure Br Br
S
S S S
Br
nD20 1.5961 1.5706 1.5786 1.5795
The selective synthesis of each of T1-T4 can be performed using 3-methylthiophene as the starting
material. T1 and T2 can be obtained by direct bromination using different catalysts, whereas T3 and T4
are the products of “one pot” multistep synthesis (see Scheme 1).
NBS, CCl4 NBS, CCl4
T2 T1
AIBN cat. HClO 4 cat.
1. 3.5 eq. Br2 , S

NaOAc, 1. BuLi, TMEDA,
H 2O, 100 °C Et 2 O, rt
T4 T3
2. Zn dust 2. CBr4 , -70 °C
NBS = N Br AIBN = NC N N CN
N
TMEDA = N
Scheme 1. Selective synthesis of monobrominated thiophenes.
8
Q1. Assign the structures given in Scheme 1 with T1, T2 to the structures given in the Table 1. Fill
in the boxes below with one of A-B.
T1 T2
In this task, you will:

- Synthesize a monobrominated thiophene derivative using one of the catalysts from the list
below;
- Measure the product refractive index (nD)
- Compare the results obtained with literature data and decide on the product structure and the
catalysts given.
List of possible catalysts
- HClO4 in CCl4
- AIBN in CCl4
PROCEDURE
Note!
- Apparatuses used in this task are shown in Fig. 1 and 2.
- Always equip every joint with the Teflon sleeve. Immediately place every piece of the used
glassware in the corresponding container. Always keep the container tightly closed.
- You can use cotton gloves when handling hot things!
Step 1. Clamp the three-necked flask on the laboratory stand on top of the hot-plate magnetic stirrer.
(Fig.1). Apply the dropping funnel and the reflux condenser to the corresponding necks and put the big
magnetic stir-bar into the flask through the open neck. Ask your lab assistant to switch on water supply
in the reflux condenser (Do not do it yourself!). Transfer NBS quantitatively into the flask using
spatula and big plastic funnel. Transfer ~15 mL of CCl4 into the 25 mL glass beaker. Pour ~2/3 of the
solvent volume from the beaker into the flask. Shake the Catalyst and quantitatively add it through the
same plastic funnel into the flask. Add the rest of the solvent from the beaker to the flask. Close the
open neck with the stopper. Put the flask into the ice bath filled with water and ice to ~ 2/3 of its
volume. Start stirring the mixture.
9
Fig. 1. Set up needed to implement Steps 1-4 of the synthesis. Refer to page 4-5 for the numbers
Step 2. Using the big plastic funnel quantitatively transfer the solution of 3-methylthiophene to the
dropping funnel with tap closed. Apply a piece of the cotton wool to the open end of the dropping
funnel and reflux condenser. Under vigorous stirring, add the solution of 3-methylthiophene dropwise
during ~ 3 min. Replace the dropping funnel by a glass stopper. Use the Teflon sleeve. Remove the ice
bath. Dry the plate and bottom of the flask with napkin.
Step 3. Wrap up the flask with aluminum foil. Switch on the heater (position 3). Bring up the
mixture to boiling and boil it for 10 min. Prepare the ice bath (~2/3 of the volume) while the mixture
boils.
Step 4. Switch off the heater and carefully (hot!) remove the hot-plate magnetic stirrer aside. Dip
the flask equipped with the condenser and stoppers into the ice bath for 3-5 min. Keep gently swirling
the flask from time to time to provide the faster cooling. Then remove the reflux condenser and load
0.02 g of K2CO3 using the big funnel applied to the open neck. Close the neck with a glass stopper and
shake the flask several times. Turn off the water supply and unscrew the adaptors of the tubings from
the reflux condenser. Let the residual water leak out of the condenser and immediately place it into the
container for the used glassware. Remove the clamp keeping the flask in the ice bath.
Step 5. Weigh the 10 mL receiver flask for product with the glass stopper, both marked with your
student code. Write down the value in the answer sheet. Put the small magnetic stir-bar in the 50 mL
pear-shaped distillation flask. Screw on the adaptors with tubings to the Liebig condenser and fix it on
the stand with the red clamp. Turn on the water supply yourself and make sure there is no water leakage.
10
Step 6. Assemble the distillation apparatus as shown on Fig. 2 supplying all the joints with the teflon
sleeves and clips. First, attach two 10 mL and one 50 mL receiver flasks to the distilling receiver cow.
Then connect the vacuum hose to the cow and complete assembling. Fix the apparatus over the
magnetic stirrer to adjust it on height. Use the adjustable lab jack lift support.
Step 7. Remove the hot-plate magnetic stirrer aside. Insert the fritted glass filter into the Claisen
distillation adapter using the rubber spacer. Turn on the water-jet pump and switch on the digital
manometer. Remove the three-necked flask from the ice bath and dry it with a napkin. Carefully transfer
the reaction mixture from the three-necked flask to the filter (Attention! If you do it too fast, the
mixture can be partially sucked into the curved part of the adaptor). When finished, turn off the
pump and replace the filter with a glass stopper, use the teflon sleeve.
Step 8. Tightly wrap up the flask and distillation adaptor with aluminum foil up to the thermometer
joint. Bring back the magnetic stirrer and turn on stirring and heating (position 6). Do not turn on the
water-jet pump! Collect the distilled solvent into the 50 mL receiver. When the solvent distillation is
over, turn off heating and stirring and carefully (hot!) remove the hot-plate magnetic stirrer aside.
Replace the receiver flask containing the distilled solvent by a new 10 mL receiver. Close the 50 mL
flask with a glass stopper and deliver it to your lab assistant.
11
Step 9. Remove the foil and put the pear-shaped bottom flask into the ice bath for 2-3 min to bring
the temperature below ambient. Remove the ice bath; dry the flask with a napkin. Bring back the
magnetic stirrer under the flask (Attention! The hot-plate may be still hot!). Turn on stirring. Wrap up
the flask tightly with aluminum foil. Switch on the water-jet pump. When vacuum is stabilized (follow
the reading of the digital manometer), turn on the heater (position 6). Observe the initial stage of the
targeted product distillation and collect the first 3-5 drops into an attached receiver flask not labeled
with your student code. Then rotate the cow and collect the targeted product into the receiver flask with
your student code. Write down the product boiling point and pressure reading from the digital
manometer into the answer sheet.
Step 10. When the targeted product is collected, turn off the heater, remove the foil and carefully
(hot!) remove the hot-plate magnetic stirrer aside. Cool down the apparatus to ambient temperature
using the ice bath. Ask your lab assistant to disconnect the vacuum line. Disconnect the receiver
flask with the targeted product and immediately close it with the glass stopper labeled with your student
code. Do not attempt to drag the teflon sleeve out if it remains in the receiver. Place the flask into the
50 mL plastic beaker labeled “For the receiver with the product”. Immediately attach a new receiver
instead of the removed one and apply the joint clip. Leave the apparatus as it is.
Step 11. Measure the refraction index (before weighing) following the instruction below. Record
the temperature from the refractometer.
Weigh the receiver with the targeted product closed with the labeled stopper. Calculate the mass and
yield of the product (take the mass of the teflon sleeve equal to 149 mg). The molar masses of 3-
metylthiophene and the product equal 98 and 177 g mol-1, respectively.
Q2. Write down all the result in the hereunder Table.
# Parameter /Characteristics Value Units
1 Mass of the receiver flask with the glass stopper, g

both marked with student code
2 Mass of the product g
3 Yield of the product %
4 Refraction index for the product -
5 Temperature recorded from the refractometer °C
6 Boiling point of the product °C
7 Pressure at the Boiling point mmHg
12
Deliver the product to your lab assistant and get it signed.
The targeted product delivered: ____________________________
Student signature ___________________ Lab assistant signature ___________________________
REFRACTO 30GS – OPERATING INSTRUCTIONS
Fig. 3. Using the Refracto 30GS
1. To switch Refracto 30GS on, press and hold “ESC” button (1) until the display appears. The
instrument is ready for operation. It switches off automatically if not operated for 10 min.
2. Clean the cell and glass rod with a napkin wetted with the solvent from the washing bottle
labeled “cleaning solvent”. Dry both with another napkin.
3. Make sure the sample to be measured has reached ambient temperature and is homogeneous.
4. Apply 2-3 drops of the sample onto the measuring cell (2) using the glass rod.
5. To start the measurement press and hold the ok button (3) until the beep.
6. Take the value of the refraction index and the temperature from digital display (4) and write
down the result in the answer sheet.
7. Clean up the cell and the glass rod.
13
Q3. By comparing the obtained and literature data, draw the structure of the product and catalyst
given.
The Product obtained The Catalyst given
Q4. Draw the structure of the 3-methylthiophene-based reactive intermediates behind the selectivity
in the case of T1 and T2.
T1 T2
Q5. Write down the product (T1 or T2) formed as a result of direct bromination of 3-
methylthiophene with NBS under the given conditions / catalyst used.
ZnBr2
Dibenzoyl peroxide
LiBr in AcOH
Visible light or UV light
Q6. In the synthetic pathways to T3 and T4, draw the structures of the compounds formed in the
first steps of each pathways shown on Scheme 1.
T3 T4
14
TASK 1. Tuning bromination selectivity by catalysis (15 points).
Quest. # Q1 Q2 Q3 Q4 Q5 Q6 Total
Marks 2 39 4 2 1 2 50
Selectivity of chemical reactions is one of the most challenging problems of contemporary research. In
many cases, reaction conditions and the catalysts applied are keys to achieving high selectivity of
organic reactions. In this task, you will study one of such cases. 3-Methylthiophene can theoretically be
transformed into four monobrominated derivatives T1-T4, which have been actually synthesized and
characterized in detail. Structures of T1-T4 and the values of refractive indexes are given in Table 1.
Table 1. Structures and refractive indexes of monobrominated thiophenes.

Designation A B T3 T4
Br
Structure Br Br
S
S S S
Br
nD20 1.5961 1.5706 1.5786 1.5795
The selective synthesis of each of T1-T4 can be performed using 3-methylthiophene as the starting
material. T1 and T2 can be obtained by direct bromination using different catalysts, whereas T3 and T4
are the products of “one pot” multistep synthesis (see Scheme 1).
NBS, CCl4 NBS, CCl4
T2 T1
AIBN cat. HClO 4 cat.
1. 3.5 eq. Br2 , S

NaOAc, 1. BuLi, TMEDA,
H 2O, 100 °C Et 2 O, rt
T4 T3
2. Zn dust 2. CBr4 , -70 °C
NBS = N Br AIBN = NC N N CN
N
TMEDA = N
Scheme 1. Selective synthesis of monobrominated thiophenes.
8
Q1. Assign the structures given in Scheme 1 with T1, T2 to the structures given in the Table 1. Fill
in the boxes below with one of A-B.
B T1 A T2
2 marks
In this task, you will:

- Synthesize a monobrominated thiophene derivative using one of the catalysts from the list
below;
- Measure the product refractive index (nD)
- Compare the results obtained with literature data and decide on the product structure and the
catalysts given.
List of possible catalysts
- HClO4 in CCl4
- AIBN in CCl4
PROCEDURE
Note!
- Apparatuses used in this task are shown in Fig. 1 and 2.
- Always equip every joint with the Teflon sleeve. Immediately place every piece of the used
glassware in the corresponding container. Always keep the container tightly closed.
- You can use cotton gloves when handling hot things!
Step 1. Clamp the three-necked flask on the laboratory stand on top of the hot-plate magnetic stirrer.
(Fig.1). Apply the dropping funnel and the reflux condenser to the corresponding necks and put the big
magnetic stir-bar into the flask through the open neck. Ask your lab assistant to switch on water supply
in the reflux condenser (Do not do it yourself!). Transfer NBS quantitatively into the flask using
spatula and big plastic funnel. Transfer ~15 mL of CCl4 into the 25 mL glass beaker. Pour ~2/3 of the
solvent volume from the beaker into the flask. Shake the Catalyst and quantitatively add it through the
same plastic funnel into the flask. Add the rest of the solvent from the beaker to the flask. Close the
open neck with the stopper. Put the flask into the ice bath filled with water and ice to ~ 2/3 of its
volume. Start stirring the mixture.
9
Step 2. Using the big plastic funnel quantitatively transfer the solution of 3-methylthiophene to the
dropping funnel with tap closed. Apply a piece of the cotton wool to the open end of the dropping
funnel and reflux condenser. Under vigorous stirring, add the solution of 3-methylthiophene dropwise
during ~ 3 min. Replace the dropping funnel by a glass stopper. Use the Teflon sleeve. Remove the ice
bath. Dry the plate and bottom of the flask with napkin.
Step 3. Wrap up the flask with aluminum foil. Switch on the heater (position 3). Bring up the
mixture to boiling and boil it for 10 min. Prepare the ice bath (~2/3 of the volume) while the mixture
boils.
Step 4. Switch off the heater and carefully (hot!) remove the hot-plate magnetic stirrer aside. Dip
the flask equipped with the condenser and stoppers into the ice bath for 3-5 min. Keep gently swirling
the flask from time to time to provide the faster cooling. Then remove the reflux condenser and load
0.02 g of K2CO3 using the big funnel applied to the open neck. Close the neck with a glass stopper and
shake the flask several times. Turn off the water supply and unscrew the adaptors of the tubings from
the reflux condenser. Let the residual water leak out of the condenser and immediately place it into the
container for the used glassware. Remove the clamp keeping the flask in the ice bath.
Step 5. Weigh the 10 mL receiver flask for product with the glass stopper, both marked with your
student code. Write down the value in the answer sheet. Put the small magnetic stir-bar in the 50 mL
pear-shaped distillation flask. Screw on the adaptors with tubings to the Liebig condenser and fix it on
the stand with the red clamp. Turn on the water supply yourself and make sure there is no water leakage.
10
Step 6. Assemble the distillation apparatus as shown on Fig. 2 supplying all the joints with the teflon
sleeves and clips. First, attach two 10 mL and one 50 mL receiver flasks to the distilling receiver cow.
Then connect the vacuum hose to the cow and complete assembling. Fix the apparatus over the
magnetic stirrer to adjust it on height. Use the adjustable lab jack lift support.
Step 7. Remove the hot-plate magnetic stirrer aside. Insert the fritted glass filter into the Claisen
distillation adapter using the rubber spacer. Turn on the water-jet pump and switch on the digital
manometer. Remove the three-necked flask from the ice bath and dry it with a napkin. Carefully transfer
the reaction mixture from the three-necked flask to the filter (Attention! If you do it too fast, the
mixture can be partially sucked into the curved part of the adaptor). When finished, turn off the
pump and replace the filter with a glass stopper, use the teflon sleeve.
Step 8. Tightly wrap up the flask and distillation adaptor with aluminum foil up to the thermometer
joint. Bring back the magnetic stirrer and turn on stirring and heating (position 6). Do not turn on the
water-jet pump! Collect the distilled solvent into the 50 mL receiver. When the solvent distillation is
over, turn off heating and stirring and carefully (hot!) remove the hot-plate magnetic stirrer aside.
Replace the receiver flask containing the distilled solvent by a new 10 mL receiver. Close the 50 mL
flask with a glass stopper and deliver it to your lab assistant.
11
Step 9. Remove the foil and put the pear-shaped bottom flask into the ice bath for 2-3 min to bring
the temperature below ambient. Remove the ice bath; dry the flask with a napkin. Bring back the
magnetic stirrer under the flask (Attention! The hot-plate may be still hot!). Turn on stirring. Wrap up
the flask tightly with aluminum foil. Switch on the water-jet pump. When vacuum is stabilized (follow
the reading of the digital manometer), turn on the heater (position 6). Observe the initial stage of the
targeted product distillation and collect the first 3-5 drops into an attached receiver flask not labeled
with your student code. Then rotate the cow and collect the targeted product into the receiver flask with
your student code. Write down the product boiling point and pressure reading from the digital
manometer into the answer sheet.
Step 10. When the targeted product is collected, turn off the heater, remove the foil and carefully
(hot!) remove the hot-plate magnetic stirrer aside. Cool down the apparatus to ambient temperature
using the ice bath. Ask your lab assistant to disconnect the vacuum line. Disconnect the receiver
flask with the targeted product and immediately close it with the glass stopper labeled with your student
code. Do not attempt to drag the teflon sleeve out if it remains in the receiver. Place the flask into the
50 mL plastic beaker labeled “For the receiver with the product”. Immediately attach a new receiver
instead of the removed one and apply the joint clip. Leave the apparatus as it is.
Step 11. Measure the refraction index (before weighing) following the instruction below. Record
the temperature from the refractometer.
Weigh the receiver with the targeted product closed with the labeled stopper. Calculate the mass and
yield of the product (take the mass of the teflon sleeve equal to 149 mg). The molar masses of 3-
metylthiophene and the product equal 98 and 177 g mol-1, respectively.
Q2. Write down all the result in the hereunder Table.
# Parameter /Characteristics Value Units
1 Mass of the receiver flask with the glass stopper, g

both marked with student code
2 Mass of the product g
3 Yield of the product %
4 Refraction index for the product -
5 Temperature recorded from the refractometer °C
6 Boiling point of the product °C
7 Pressure at the Boiling point mmHg
12
Deliver the product to your lab assistant and get it signed.
The targeted product delivered: ____________________________
Student signature ___________________ Lab assistant signature ___________________________
The grading scheme takes into account two values re-measured by the Science Committee: mass of the
Product (m, g) and its refraction index (nD) (Fig. 1).
100
80
60
%
e,
Grad
40
5
20
4
3 0
1.62
2 1.60
m,
1.58
g
1
1.56
0 1.54 nD
1.52
Fig. 1. The 3D diagram.

There are several regions (A-D) on the hereunder projection of the 3D diagram (Fig. 2).
A
5.0
4.5
4.0
3.5 B D
3.0
m, g
2.5
2.0
1.5 C
1.0
0.5
0.0
-0.5
1.52 1.54 1.56 1.58 1.60 1.62

nD
Figure 2. Mass-nD plot.
• If the value obtained is within region A, 100% of 30 marks

• If the value obtained is within region B, 2202.643*nD-3355.95 % of 30 marks
• If the value obtained is within region C, 28.57143*m % of 30 marks
• If the value obtained is within region D, -2380.95*nD+3841.1905 % of 30 marks
13
Refraction index measurement skills: 4 marks if a student’s result differs from the re-measured value not
more than by 0.4 %.
Weighing skills: 2 marks if a student’s result differs from the re-weighed value not more than by 0.02%.
Correct calculation of mass: 1 mark.
Correct calculation of yield: 1 mark.
Measurement of the Boiling point: 1 mark
REFRACTO 30GS – OPERATING INSTRUCTIONS
Fig. 3. Using the Refracto 30GS
1. To switch Refracto 30GS on, press and hold “ESC” button (1) until the display appears. The
instrument is ready for operation. It switches off automatically if not operated for 10 min.
2. Clean the cell and glass rod with a napkin wetted with the solvent from the washing bottle
labeled “cleaning solvent”. Dry both with another napkin.
3. Make sure the sample to be measured has reached ambient temperature and is homogeneous.
4. Apply 2-3 drops of the sample onto the measuring cell (2) using the glass rod.
5. To start the measurement press and hold the ok button (3) until the beep.
6. Take the value of the refraction index and the temperature from digital display (4) and write
down the result in the answer sheet.
7. Clean up the cell and the glass rod.
14
Q3. By comparing the obtained and literature data, draw the structure of the product and catalyst
given.
The Product obtained The Catalyst given
HClO4
Br
1 mark
S 0 mark, if inconsistent with Q1
3 marks
Q4. Draw the structure of the 3-methylthiophene-based reactive intermediates behind the selectivity
in the case of T1 and T2.
T1 T2
H H .
+
Br Br
CH 2
+ S
S S
1 mark for any of the structures 1 mark
Q5. Write down the product (T1 or T2) formed as a result of direct bromination of 3-
methylthiophene with NBS under the given conditions / catalyst used.
ZnBr2 T1
Dibenzoyl peroxide T2
LiBr in AcOH T1
Visible light or UV light T2
0.25 marks each, 1 mark in total
Q6. In the synthetic pathways to T3 and T4, draw the structures of the compounds formed in the
first steps of each pathways shown on Scheme 1.
T3 T4
Br Br
S S
Li Br
1 mark 1 mark
15
Student Code AAA-1
Chemicals and Equipment (Task 2).
I. Chemicals and materials
Chemicals Labeled as Health Statements a

3-Pentanone (MW 86.13),
A H225-H319-H335-H336
~0.86 gb in a vial
p-chlorobenzaldehyde (MW140.57),
B H302-H315-H319-H335
~3.5 gc in a vial
Ethanol, 200 cm3 in a wash-bottle Ethanol H225-H319
-3
2 mol dm NaOH solution in water
2N NaOH H290-H314
(labelled as 2N NaOH), 25 cm3 in a bottle
a
See page 34 for definition of Health Statements
b
You will need to weigh the vial containing 3-pentanone right before using. The exact value
can be calculated based on the information given on the label.
c
The exact value is indicated on the label.

Student Code AAA-1

Balance Shared 12 per room
Water aspirator Shared 2 per bench
Foam bucket filled with ice Shared 1 per row (Refill could be
requested)
Personal Equipment Quantity
Hotplate stirrer with temperature probe 1
Stand 1
Clamps 2
100-cm3 Round bottom flask 1
3
Measuring cylinder, 50 cm 1
Air condenser 1
3
Crystallizing dish, 250 cm 1
3
125-cm Erlenmeyer flask 2
3
Buchner funnel, 25 cm 1
Watch glass 1
Pasteur pipettes (droppers) 5
Rubber bulbs 2
Suction rubber 1
Rubber support ring 1
Magnetic bar 1
Filter papers 3 (pack in 1 zipped bag)
Spatula 1
Stirring Rod 1
Forceps 1
Plastic joint clips 1
Wash Bottle (filled with EtOH) 1 (can be refilled)
Nitrile gloves 2 (exchange size if needed)
Towels 2
Paper clip 1
“Waste Task 2”, 500 cm -glass bottle
3
1
Vial labeled “Student code” for submitting 1
product.
Goggles 1

Student Code AAA-1
Task 2 a b
Total
a1 a2 a3 b1
Total 2 2 2 18 24
Score
Task 2: Elaborating Carbon Framework

The core structure of organic molecules is mostly based on carbon-carbon skeleton.
Carbon-carbon bond formations have played a vital role in the construction of complex
structures from smaller starting materials. Therefore, the synthetic transformations to
efficiently achieve carbon-carbon bond formation has long been of interest. In this experiment,
you are required to transform commercially available p-chlorobenzaldehyde and 3-pentanone
to a more elaborated structure.
Important Notes:
 Ethanol can be refilled with no penalty.
 All weighing processes require verification from lab supervisor. The supervisor will
need to sign in the student’s answer sheet for grading. No mark will be given for
unverified values.
 Total of 18 points of this exam score will be based on the quality and quantity of the
product submitted. We could not give any score on this part if the product is not
submitted for grading.
 1
H-NMR and melting point determination techniques will be used by the grader to
verify the quality of your product.
Part a
1. Take the vial containing 3-pentanone (A) (Code Axxx, For example: A305) and unwrap
the parafilm. Weigh the vial with caps. Record the weight in the answer sheet question
a1.
2. Setup a water bath by filling water in the 250 cm3-crystallizing dish and heat to 55±2°C.
Add paper clip into the water bath and let it stir so that the heat could be distributed
evenly.
3. Ensure a magnetic stirring bar is in the 100-cm3 round bottom flask. Transfer the pre-
weighed 3-pentanone (labeled as A) and p-chlorobenzaldehyde (labeled as B) to the
flask. Add 50 cm3 ethanol to the mixture and swirl to dissolve.

Student Code AAA-1
4. Measure 15 cm3 of 2 mol dm-3 NaOH (labeled as 2N NaOH) using a measuring cylinder
and add to the reaction mixture. Be careful not to wet the ground joint with NaOH
solution.
5. Setup the reaction as shown in Figure 1. The reaction flask is placed in the 55±2°C
water bath. Attach the air condenser to the reaction flask with plastic joint clip. Heat
the reaction mixture while stirring for 30 minutes using the water bath.
Figure 1: Set up needed for heating the reaction with water bath.
6. Remove the reaction flask from the water bath. (Be careful! The flask might be hot.)
Place the flask on the rubber supporting ring.
7. (Important) Detach the probe from the hotplate/stirrer to avoid over-heating of the hotplate in
the recrystallizing steps. After you detach the probe, inform the supervisor to check and submit
the probe to the supervisor.
8. Prepare the ice bath by replacing the warm water in the 250 cm3-crystalizing dish with
ice and small amount of water. Place the reaction flask on the ice bath to cool down the
reaction. Solid should be observed. (Suggestion: If you do not observe any solid within
5 minutes, you may use a stirring rod to scratch the side of the flask. This could induce
precipitation.)
9. Keep the mixture cool for approximately 20 minutes to allow complete precipitation.
10. Set up the suction filtration equipment (Figure 2). Connect the suction flask to the water
aspirator. Place a Buchner funnel fitted with a rubber adapter onto the suction flask.
Place a filter paper at the center of the funnel. Filter the precipitate via suction filtration
and wash the precipitate with small amount of cold ethanol. Let air suck through the
precipitates for 2-3 minutes to dry the product.

Student Code AAA-1
Figure 2: Set up needed for suction filtration.
11. Disconnect the vacuum (before turning off the water aspirator). Bring your equipment
back to your space and keep the common area clean. Collect the crude precipitates from
the filter paper and transfer to the Erlenmeyer flask. Careful not to scrape the paper
too hard as you may obtain small pieces of paper as contaminant. Student may use
Ethanol to rinse the Buchner funnel.
12. Place ethanol in a separate Erlenmeyer flask and heat it gently on a hotplate. (Student
may set the temperature mark at 100-120°C) Before heating, please make sure that
the temperature probe is detached from the hotplate.
13. Recrystallize the product from hot ethanol. You can follow the procedure below.
Add small amount of hot ethanol to the flask containing crude solid while swirling.
Continue addition of hot ethanol (swirling after each addition) until the solid is
completely dissolved. During the dissolution process, keep the flask hot at all times by
resting it on the hotplate. Be careful that the flask may be hot. You may use paper
towels or towels provided to wrap around the flask while swirling. Once the dissolution
is complete, set the flask containing the dissolved compound on a benchtop and let the
flask cool down to room temperature without disturbance. The crystalline product
should be observed. If not, you may use the stirring rod to scratch the side of the flask
to induce crystallization. Place the flask into the ice bath to complete crystallization.
14. Filter the recrystallized product via suction filtration (See step 10 for suction filtration
protocol) and wash the product with small amount of cold ethanol. Let air suck through
the precipitates for 2-3 minutes. Disconnect the vacuum. Let the purified product air-
dry on the benchtop for at least 15 minutes.

Student Code AAA-1
15. Weigh the vial (without cap) labeled with your student code provided. Record the value
in the answer sheet question a1.
16. Transfer the recrystallized product to the pre-weighed vial. Determine and record the
mass of the purified product in the answer sheet question a1.
17. Fill the information on the label of the product vial. Place the product-containing vial
on the benchtop. The supervisor will pick up your vial and sign on your answer sheet
question b after the “Stop command”. The student also must sign the answer sheet
question b for grading. Once both supervisor and student sign, place the vial into a
zipped bag and submitted for grading.
These following items should be left on your bench:

 The exam/answer booklet (this booklet) placed in an exam envelope
 The vial labeled “Student Code” with filled information

Student Code AAA-1
Supervisor will place a label here

when randomly distributed the compounds:
Axxx (For example: A567) = Code of vial containing 3-pentanone

Tared (w/caps): Mass of (vial + label + caps) before adding 3-pentanone
Bxxx (For example: B567) = Code of vial containing p-chlorobenzaldehyde
Net: Mass of p-chlorobenzaldehyde
a1) Use the information provided in the label above along with your experimental data for
your calculation. Write down all the results in this Table.
Mass of 3-pentanone in the vial provided (must weigh with caps) = ________________
*Signature of the supervisor is required for grading
Mass of pentan-3-one = _____________________________

Mass of p-chlorobenzaldehyde (copy from the label):_________________________
Mass of the empty vial for product:____________________________

Mass of the vial with the recrystallized product:_____________________________

Mass of the recrystallized product:_____________________

Student Code AAA-1
a2) Write 4 plausible aromatic compounds that may occur from this reaction. Stereoisomers
are excluded.

Student Code AAA-1
a3) Given the 400MHz 1H-NMR (in CDCl3) of the product below, write the structure of the
product.
Frequency
H2O
CHCl3 TMS
Integral 8 2 2 6
2 2 2
Integrals are for all protons presented in the molecule.

Student Code AAA-1
Part b
b1) Your submitted product will be characterized and graded for its %yield and purity.
Provide information of the product you submitted.
Status: Solid Liquid
Signature of Supervisor: ___________________________(Signed when submitted)
Signature of Student: _____________________________ (Signed when submitted)

Student Code AAA-1
Task 2 a b
Total
a1 a2 a3 b1
Total 2 2 2 18 24
Score
a1) Use the information provided in the label above along with your experimental data for
your calculation. Write down all the results in this Table.
Mass of 3-pentanone in the vial provided (must weigh with caps) = ________________
Mass of pentan-3-one = _____________________________1 point

Mass of p-chlorobenzaldehyde (copy from the label):_________________________
Mass of the empty vial for product:____________________________

Mass of the vial with the recrystallized product:_____________________________

Mass of the recrystallized product:_____________________ 1 point

Student Code AAA-1
a2) Write 4 plausible aromatic compounds that may occur from this reaction. Stereoisomers
are excluded.
0.5 point each, maximum 2 points

Student Code AAA-1
a3) Given the 400MHz 1H-NMR (in CDCl3) of the product below, write the structure of the
product.
Frequency
H2O
CHCl3 TMS
Integral
8 2 2 6
2 2 2
Integrals are for all protons presented in the molecule.
2 points.

GBR-1
Chemicals
For all problems
Deionised water in:
Wash bottle (bench)
Water Not hazardous

2-Acetonaphthone:
Standard A H302, H315, H319, H335,
H411
DNPH H228, H302
Bleach H290, H314, H400
amber glass bottle
TLC eluent
H290, H314, H319, H335
and others

H290, H315, H319
Cu Not hazardous
plastic bottle
H2O2 conc. H302, H315, H318
plastic bottle


GBR-1

(bench)
Buffer H302, H319, H314, H400
(bench)
NaOH H314
bottle
Equipment
Personal equipment
Safety goggles 1
1 (each)

Personal equipment

GBR-1

Open metal ring 1
Reflux condenser 1
Glass funnel 1
1
label)
Rubber bulb 1
1
haloform reaction
1

Stopwatch 1
1
H2O2, 50 cm3
1

GBR-1


1 (each)
Burette clamp
Burette, 25 cm3
Glass funnel 1

GBR-1
Practical Question 1.1 1.2 yield m.p. Total

Problem P1 Points 4 16 20 10 50
Problem P1. Haloform reaction with bleach

Chemical test reactions have been developed as a means of identifying functional groups in
unknown compounds. In this task, you will explore two examples of chemical test reactions on
a preparatory scale, starting from (2-naphthyl)ethanone (A, 2-acetonaphthone):
 The haloform reaction is a transformation typical for methyl ketones which react with basic
aqueous hypohalite solution and provide a carboxylic acid (product B) and a haloform
(trihalomethane).
 The reaction of Brady’s reagent (acidic solution of 2,4-dinitrophenylhydrazine) with the
carbonyl group of an aldehyde or ketone results in the formation of an orange hydrazone
precipitate (product C).
NO2
H
N
O H2N
CHCl 3 1. NaClO (aq)
+ (Bleach) CH 3 NO2
Product C
Product B 2. HCl (aq) HCl, H2O/EtOH (orange precipitate)
(white precipitate) A (Brady's reagent)
P1.1 Draw the structures of products B and C.
Product B Product C
Notes:
 The total score will be based on the Rf values of compounds A and B calculated from the
submitted TLC plate 1 and on the quality and quantity of the submitted products B and C.
 The quality of your products will be graded based on the TLC and melting points.
 The amount of the provided hypochlorite solution is not sufficient to convert all reactant A to
product B. You will recover the residual reactant A by an acid-base extraction and isolate it after

GBR-1
the reaction with Brady's reagent as hydrazone C. The grading is based on the combined yield of
products B and C.
Procedure
I. Haloform reaction
1. Turn on the stirrer and adjust the speed to 540 rpm. Immerse a temperature probe, resting the
wire on the upper clamp, into the bath almost to the bottom and set the temperature to 80 °C.
2. Transfer the 0.500 g of 2-acetonaphthone from the vial labelled Reactant A into a 50 cm3
(teardrop-shaped) round bottomed flask that contains a magnetic stir bar. Measure 3 cm3 of
ethanol (from the wash bottle) in a measuring cylinder and use it to transfer the remaining reactant
A quantitatively into the round bottomed flask using a glass Pasteur pipette.
3. Place the round bottomed flask into the hot water bath. Attach an air reflux condenser (water
connection is not needed) and secure it in the upper part by a loosely attached large clamp, as
shown in Figure 1. Let compound A dissolve with stirring.
Reflux condenser
Temperature probe
Round bottom flask with a stir bar

Hot water bath with metallic clip
Laboratory stand
Figure 1. Setup for heating the reaction mixture in a water bath.
4. When the bath temperature reaches 75 °C, slowly add all the NaClO solution (Bleach) to the
reaction mixture through the top opening of the condenser using the glass funnel. Heat the
reaction mixture with stirring for 60 minutes between 75 and 80 °C.
5. Then turn off the heating of the hotplate stirrer. Loosen the upper clamp a bit and lift the reaction
flask over the water bath. (Caution! Touch only the clamps, the flask is hot.) Allow the reaction
mixture to cool down for 15 minutes.
II. Workup of the reaction mixture

1. Place a separating funnel into a metal ring and place a 50 cm3 conical flask without a ground joint
under it. Using the glass funnel, pour the cooled reaction mixture into the separating funnel.
Remove the stir bar from the glass funnel with tweezers. Measure 5 cm3 of ethyl acetate (EtOAc)
and use it to rinse the reaction flask. Add the washings into the separating funnel using a glass
Pasteur pipette.

GBR-1
2. Perform the extraction. Allow the layers to separate. Collect the aqueous layer into the 50 cm3
conical flask without a ground joint. Using the glass funnel, pour the organic layer through the top
neck into the 25 cm3 conical flask. Keep both phases!
3. Using the glass funnel, pour the aqueous phase from the 50 cm3 conical flask back to the
separating funnel. Measure another 5 cm3 of ethyl acetate and repeat the extraction (step No.
II.2). Combine the organic phases together in the 25 cm3 conical flask. Keep both phases!
4. Prepare your TLC plate. Check it before use. Unused damaged plates will be replaced upon
request without penalty. Use a pencil to draw the start line and mark the positions for spotting the
samples. Write number 1 in a circle and your student code on the top of the TLC plate as shown
in Figure 2. Dissolve the given sample of 2-acetonaphthone in a vial (Standard A) in approx. 2
cm3 of ethanol (about 1 full glass Pasteur pipette). Mark three spot positions and label them A,
O1, and O2. Spot 1 l (one mark of the 5 l capillary spotter) of standard A and the combined
organic phase from step II.3 (O1). You will add spot O2 later.
1 Student code ca. 0.5 cm

Eluent front line
cm 7 cm 7 cm cm
5 5
0. 0. 0. 0.
Start line
A O1 O2 0.7 cm
Standard A Organic phase

Organic phase
before basic extraction after basic extraction
Figure 2. Instructions for the TLC plate preparation.
5. Extract the combined organic phases twice with 5 cm3 of 5% Na2CO3 solution. Collect the
aqueous phase into the same 50 cm3 conical flask without a ground joint containing the
aqueous phase from the first extraction.
6. Wash the organic phase in the separating funnel with 5 cm3 of deionised water. Add the
aqueous phase to the combined aqueous extracts. Pour the organic layer (O2) through the
top neck into a 50 cm3 ground-joint conical flask. Spot 1 l of the solution O2 on your TLC
plate prepared in step II.4 (Plate 1).
7. Perform a TLC analysis. Take a 50 cm3 beaker and load it with approx. 2 cm3 of the TLC
eluent. Insert the TLC plate, cover the beaker with a Petri dish and let the eluent reach
approximately 0.5 cm bellow the top edge of the plate. Using tweezers, take the TLC plate
out, draw the eluent front line and let the plate air-dry. Place the TLC plate under the UV lamp
in the hood. With a pencil, circle all the visualised spots and calculate the Rf values of reactant
A and product B. Store your TLC plate in a plastic bag.
Note 1: Product B may tail on the TLC plate. Therefore, avoid excessive loading of the sample.

GBR-1
Note 2: In some cases, two additional spots of side products of a very low intensity may be seen
in combined organic phase O1 and O2. In this case, calculate the Rf value for the most intense
spot(s).
Note 3: If the organic layer O2 still contains both starting material A and product B, repeat the
extraction with the Na2CO3 solution and water (steps No. II.5 and II.6). In this case, submit also
another TLC plate after the repeated extraction (Plate 2), spotting only standard A and organic
phase O2. Mark number 2 in a circle and your student code on the top of this TLC plate. Use a
fresh batch of eluent to develop TLC Plate 2.
P1.2 Answer the following questions about your Plate(s). From Plate 1, calculate the Rf values of
standard A and product B. Provide the results rounded to 2 decimal places.
Based on the TLC analysis, your organic layer O1 contains:

YES NO
Starting material A  
Product B  
Based on the TLC analysis, your final organic layer O2 contains:

YES NO
Product B  
Calculation of the Rf(A)
Rf(A) =
Calculation of the Rf(B)
Rf(B) =
III. Reaction with Brady’s reagent

Attention: Use gloves! Brady’s reagent stains skin and all surfaces. Wash any spots immediately
with ethanol! Change your gloves if necessary.
Preheat the water bath to 80 °C. Insert a magnetic stir bar into the 50 cm3 ground-joint conical flask
containing the organic phase O2 from step II.6 and add 0.300 g of 2,4-dinitrophenylhydrazine
(DNPH). In a graduated cylinder, measure 10 cm3 of ethanol. Using a glass Pasteur pipette, rinse
the glass vial with 5 × 2 cm3 of ethanol to transfer all of the DNPH into the conical flask. Place the
conical flask into the hot water bath, attach a reflux condenser (similar setup as in Figure 1) pre-
rinsed with ethanol. Through the top opening of the condenser, add 3 cm3 of 20% HCl using the
glass funnel and stir the reaction mixture at 80 °C for 2 minutes. Fine orange crystals of product C
start to form. Then turn off the heating of the hotplate stirrer. Lift the reaction flask above the water
bath. (Caution! Touch only the clamps, the flask is hot.) Allow the reaction mixture to cool down for
15 min and then place it into a cold water bath (prepared by pouring cold tap water into a 150 cm3
beaker).

GBR-1
IV. Isolation of the products

1. Check the pH of the combined aqueous phase from step No. II.6. Acidify it by carefully adding
20% HCl solution, stirring the mixture with a glass rod (approx. 2 cm3 of the HCl solution should
be required), to the final pH of 2 (check with pH indicator strips). A white precipitate of product B
is formed.
2. Set up a vacuum filtration apparatus (Figure 3) using a glass fritted (sintered) funnel with porosity
S2 (with white label) and secure it to a laboratory stand with a small clamp. Connect the suction
flask to the vacuum source. Pour the suspension of product B (step No. IV.1) into the fritted
funnel, let the solid settle down, and then open the vacuum valve. Caution: notify the lab assistant
before and after handling the valve! Wash the solid twice with 6 cm3 of deionised water, until the
pH of the dropping filtrate is about 6. Let air suck through the precipitate for 5 minutes to pre-dry
the product. Disconnect the vacuum source. Use the spatula to transfer white product B to a glass
vial labelled Student code B and leave it uncovered on the bench to dry. Discard the filtrate to
the sink drain and wash the suction flask.
Note: Be careful not to scratch the fritted glass into your product!
Glass fritted funnel

Frit porosity S2 or S3
Rubber adapter
Attachment to vacuum source
Figure 3. Setup for suction filtration.
3. Set up a vacuum filtration apparatus with a glass fritted funnel with porosity S3 (with an orange-
red label) similarly as in IV.2. Pour the suspension of product C (step No. III) into the fritted funnel,
wait for a minute, and then open the vacuum valve. Do NOT stir or scratch the solid with the
spatula while filtering and washing, otherwise the solid may go through the filter. Wash the
precipitate three times with 5 cm3 of ethanol (15 cm3 in total) until neutral pH of the dropping
filtrate is reached. Let air suck through the precipitate for 5 minutes. Disconnect the vacuum
source. Use the spatula to transfer orange product C to a glass vial labelled Student code C and
leave it uncovered on the bench to dry. Collect the filtrate into Organic waste bottle.
Note: If the product goes through the fritted funnel, filter the suspension once more. If the product
still goes through, contact the lab assistant.
Your lab assistant will pick up following items and sign your answer sheet.
 Glass vials labelled Student code B and C with your products
 TLC plates in a zipped bag labelled with your Student code

GBR-1
Submitted items:
Product B 
Product C 
TLC Plate 1 
TLC Plate 2 (optional) 
Signatures: ___________________ __________________

XXX-X
Practical Question 1.1 1.2 yield m.p. Total

Problem P1 Points 4 16 20 10 50
Problem P1. Haloform reaction with bleach

Chemical test reactions have been developed as a means of identifying functional groups in
unknown compounds. In this task, you will explore two examples of chemical test reactions on
a preparatory scale, starting from (2-naphthyl)ethanone (A, 2-acetonaphthone):
• The haloform reaction is a transformation typical for methyl ketones which react with basic
aqueous hypohalite solution and provide a carboxylic acid (product B) and a haloform
(trihalomethane).
• The reaction of Brady’s reagent (acidic solution of 2,4-dinitrophenylhydrazine) with the
carbonyl group of an aldehyde or ketone results in the formation of an orange hydrazone
precipitate (product C).
P1.1 Draw the structures of products B and C.
2 points (1 point for intermediate hydrazine-

alcohol or the product with minor mistake in the
structure – forgotten group or hydrogen atoms in
2 points (1 point for 2-naphthoate) the side chain)
Product B Product C
Notes:
• The total score will be based on the Rf values of compounds A and B calculated from the
submitted TLC plate 1 and on the quality and quantity of the submitted products B and C.
• The quality of your products will be graded based on the TLC and melting points.
• The amount of the provided hypochlorite solution is not sufficient to convert all reactant A to
product B. You will recover the residual reactant A by an acid-base extraction and isolate it after

XXX-X
the reaction with Brady's reagent as hydrazone C. The grading is based on the combined yield of
products B and C.
Procedure
I. Haloform reaction
1. Turn on the stirrer and adjust the speed to 540 rpm. Immerse a temperature probe, resting the
wire on the upper clamp into the bath almost to the bottom and set the temperature to 80 °C.
2. Transfer the 0.500 g of 2-acetonaphthone from the vial labelled Reactant A into a 50 cm3 round
bottom flask that contains a magnetic stir bar. Measure 3 cm3 of ethanol (from the wash bottle) in
a measuring cylinder and use it to transfer the remaining reactant A quantitatively into the round
bottom flask using a glass Pasteur pipette.
3. Place the round bottom flask into the hot water bath. Attach an air reflux condenser (water
connection is not needed) and secure it in the upper part by a loosely attached large clamp, as
shown in Figure 1. Let compound A dissolve with stirring.
Figure 1. Setup for heating the reaction mixture in a water bath.
4. When the bath temperature reaches 75 °C, slowly add all the NaClO solution (Bleach) to the
reaction mixture through the top opening of the condenser using a small glass funnel. Heat the
reaction mixture with stirring for 60 minutes between 75 and 80 °C.
5. Then turn off the heating of the hotplate stirrer. Loosen the upper clamp a bit and lift the reaction
flask over the water bath. (Caution! Touch only the clamps, the flask is hot.) Allow the reaction
mixture to cool down for 15 minutes.
II. Workup of the reaction mixture

1. Place a separatory funnel into a metal ring and place a 50 cm3 Erlenmeyer flask without a ground
joint under it. Using a glass funnel, pour the cooled reaction mixture into the separatory funnel.
Remove the stir bar from the glass funnel with tweezers. Measure 5 cm3 of ethyl acetate (EtOAc)
and use it to rinse the reaction flask.. Add the washings into the separatory funnel using a glass
Pasteur pipette.

XXX-X
2. Perform the extraction. Allow the layers to separate. Collect the aqueous layer into the 50 cm3
Erlenmeyer flask without a ground joint. Using a small glass funnel, pour the organic layer through
the top neck into the 25 cm3 Erlenmeyer flask. Keep both phases!
3. Using a small funnel, pour the aqueous phase from the 50 cm3 Erlenmeyer flask back to the
separatory funnel. Measure another 5 cm3 of ethyl acetate and repeat the extraction (step No.
II.2). Combine the organic phases together in the 25 cm3 Erlenmeyer flask. Keep both phases!
4. Prepare your TLC plate. Check it before use. Unused damaged plates will be replaced upon
request without penalty. Use a pencil to draw the start line and mark the positions for spotting the
samples. Write number 1 in a circle and your student code on the top of the TLC plate as shown
in Figure 2. Dissolve the given sample of 2-acetonaphthone in a vial (Standard A) in ca. 2 cm3 of
ethanol (about 1 full glass Pasteur pipette). Mark three spot positions and label them A, O1, and
O2. Spot 1 l (one mark of the 5 l capillary spotter) of standard A and the combined organic
phase from step II.3 (O1). You will add spot O2 later.
Figure 2. Instructions for the TLC plate preparation.
5. Extract the combined organic phases twice with 5 cm3 of 5% Na2CO3 solution. Collect the
aqueous phase into the same 50 cm3 Erlenmeyer flask without a ground joint containing the
aqueous phase from the first extraction.
6. Wash the organic phase in the funnel with 5 cm3 of deionized water. Add the aqueous phase
to the combined aqueous extracts. Pour the organic layer (O2) through the top neck into a 50
cm3 ground-joint Erlenmeyer flask. Spot 1 l of the solution O2 on your TLC plate prepared
in step II.4 (Plate 1).
7. Perform a TLC analysis. Take a 50 cm3 beaker and load it with ca. 2 cm3 of the TLC eluent.
Insert the TLC plate, cover the beaker with a Petri dish and let the eluent reach approximately
0.5 cm bellow the top edge of the plate. Using tweezers, take the TLC plate out, draw the
eluent front line and let the plate air-dry. Place the TLC plate under the UV lamp in the hood.
With a pencil, circle all the visualized spots and calculate the Rf values of reactant A and
product B. Store your TLC plate in a plastic bag.
Note 1: Product B may tail on the TLC plate. Therefore, avoid excessive loading of the sample.

XXX-X
Note 2: In some cases, two additional spots of side products of a very low intensity may be seen
in combined organic phase O1 and O2. In this case, calculate the Rf value for the most intense
spot(s).
Note 3: If the organic layer O2 still contains both starting material A and product B, repeat the
extraction with the Na2CO3 solution and water (steps No. II.5 and II.6). In this case, submit also
another TLC plate after the repeated extraction (Plate 2), spotting only standard A and organic
phase O2. Mark number 2 in a circle and your student code on the top of this TLC plate. Use a
fresh batch of eluent to develop TLC Plate 2.
P1.2 Answer the following questions about your Plate(s). From Plate 1, calculate the Rf values of
standard A and product B. Provide the results rounded to 2 decimal places.
Based on the TLC analysis, your organic layer O1 contains:

YES NO
Product B  
0.5 point for correct observation about starting material on Plate 1 (in accordance with TLC)
0.5 point for correct observation about product B (in accordance with TLC)
Based on the TLC analysis, your final organic layer O2 contains:

YES NO
Product B  
0.5 point for correct observation about starting material on final plate (in accordance with
TLC)
0.5 point for correct observation about product B (in accordance with TLC)
Max 2 points for the correct preparation and development of the TLC plate 1:
(labelling of the plate with number 1 and student code, start line and eluent front line, initial
position of the spots, labels of the spots, developed spots in circles)
−0.5 points for any from the above missing, no negative total points
Calculation of the Rf(A) = distance of the spot from start line/distance between the
start and eluent front lines
Rf(A) = reported by the student
Rf(A)* Rf value calculated by the Scientific Committee (SciC) for the starting material based
on the submitted TLC plate 1
1 point for the calculation of the Rf value
1 point for the agreement with the SciC result:
Rf(A)* + 0.02 ≥ Rf(A) ≥ Rf(A)* − 0.02 1 point
Rf(A)* + 0.02 > Rf(A) 0 points
Rf(A)* − 0.02 < Rf(A) 0 points
Master value (MV) = 0.67 (determined from parallel data collected on practical exam day)
Max 4 points for the calculated Rf value
MV – 0.07 ≤ Rf(A)* ≤ MV + 0.07 4 points
MV − 0.07 > Rf(A)* > MV – 0.14
Rf (A)* –- (MV –- 0.14)
Number of points = ( ) × 4 points
0.07
MV + 0.07 < Rf(A)* < MV + 0.14

XXX-X
MV + 0.14– Rf (A)*
Number of points = ( ) × 4 points
0.07
MV + 0.14 ≤ Rf(A)* 0 points
MV – 0.14 ≥ Rf(A)* 0 points
Calculation of the Rf(B) = distance of the spot from start line/distance between the
start and eluent front lines
Rf(B) = reported by the student
Rf(B)* Rf value calculated by the Scientific Committee (SciC) for product B based on the
submitted TLC plate 1
1 point for the calculation of the Rf value
1 point for the agreement of the student’s and SciC result
Rf(B)* + 0.02 ≥ Rf(B) ≥ Rf(B)* − 0.02 1 point
Rf(B)* + 0.02 > Rf(B) 0 point
Rf(B)* − 0.02 < Rf(B) 0 point
Master value (MV) = 0.12 (determined from parallel data collected on practical exam day)
Max 4 points for the calculated Rf value

MV + 0.05 ≥ Rf(B)* ≥ MV – 0.05 4 points
MV – 0.05 > Rf(B)* > MV – 0.10
Rf (B)* – (MV – 0.10)
Number of points = × 4 points
0.05
MV + 0.05 < Rf(B)* < MV + 0.10
MV + 0.10– Rf (B)*
Number of points = × 4 points
0.05
Rf(B)* ≤ MV + 0.10 0 points
MV – 0.10 ≤ Rf(B)* 0 points
III. Reaction with Brady’s reagent

Attention: Use gloves! Brady’s reagent stains skin and all surfaces. Wash any spots immediately
with ethanol! Change your gloves if necessary.
Preheat the water bath to 80 °C. Insert a magnetic stir bar into the 50 cm3 ground-joint Erlenmeyer
flask containing the organic phase O2 from step II.6 and add 0.300 g of 2,4-dinitrophenylhydrazine
(DNPH). In a graduated cylinder, measure 10 cm3 of ethanol. Using a glass Pasteur pipette, rinse
the glass vial with 5 × 2 cm3 of ethanol to transfer all of the DNPH into the Erlenmeyer flask. Place
the Erlenmeyer flask into the hot water bath, attach a reflux condenser (similar setup as in Figure 1)
rinsed with ethanol. Through the top opening of the condenser, add 3 cm3 of 20% HCl using a funnel
and stir the reaction mixture at 80 °C for 2 minutes. Fine orange crystals of product C start to form.
Then turn off the heating of the hotplate stirrer. Lift the reaction flask above the water bath. (Caution!
Touch only the clamps, the flask is hot.) Allow the reaction mixture to cool down for 15 min and then
place it into a cold water bath (prepared by pouring cold tap water in a 150 cm3 beaker).
IV. Isolation of the products

1. Check the pH of the combined aqueous phase from step No. II.6. Acidify it by carefully adding
20% HCl solution, stirring the mixture with a glass rod (ca. 2 cm3 of the HCl solution should be
required), to the final pH of 2 (check with pH indicator strips). A white precipitate of product B is
formed.

XXX-X
2. Set up a vacuum filtration apparatus (Figure 3) using a glass fritted funnel with porosity S2 (with
white label) and secure it to a laboratory stand with a small clamp. Connect the suction flask to
the vacuum source. Pour the suspension of product B (step No. IV.1) into the fritted funnel, let
the solid set down, and then open the vacuum valve. Caution: notify the lab assistant before and
after handling the valve! Wash the solid twice with 6 cm3 of deionized water, until the pH of the
dropping filtrate is about 6. Let air suck through the precipitate for 5 minutes to pre-dry the product.
Disconnect the vacuum source. Use the spatula to transfer white product B to a glass vial labelled
Student code B and leave it uncovered on the bench to dry. Discard the filtrate to the sink drain
and wash the suction flask.
Note: Be careful not to scratch the fritted glass into your product!
Figure 3. Setup for suction filtration.
3. Set up a vacuum filtration apparatus with a glass fritted funnel with porosity S3 (with an orange
label) similarly as in IV.2. Pour the suspension of product C (step No. III) into the fritted funnel,
wait for a minute, and then open the vacuum valve. Do NOT stir or scratch the solid with the
spatula while filtering and washing, otherwise the solid may go through the filter. Wash the
precipitate three times with 5 cm3 of ethanol (15 cm3 in total) until neutral pH of the dropping
filtrate is reached. Let air suck through the precipitate for 5 minutes. Disconnect the vacuum
source. Use the spatula to transfer orange product C to a glass vial labelled Student code C and
leave it uncovered on the bench to dry. Collect the filtrate into Organic waste bottle.
Note: If the product goes through the fritted funnel, filter the suspension once more. If the product
still goes through, contact the lab assistant.
Your lab assistant will pick up following items and sign your answer sheet.
• Glass vials labelled Student code B and C with your products
• TLC plates in a zipped bag labelled with your Student code
Submitted items:
Product B 
Product C 
TLC Plate 1 
TLC Plate 2 (optional) 
Signatures: ___________________ __________________

XXX-X
Marking notes for evaluation of the yields and product quality

Combined yield of product B and C max 20 points
100% < y (after extended drying will be analyzed by SciC: NMR and insoluble residue).
89.0% ≤ y ≤.100.0% 20 points
y < 89.0% linear dependence:
(% C + % B) × 20 points
Number of points =
89.0%
Products quality total max 10 points
Compound B starting point of melting and melting point interval
Starting point of melting of compound B (max 4 points)

m.p.> 186.8 °C Will be evaluated for composition by SciC.
186.8 °C ≥ m.p. ≥ 183.2 °C 4 points
183.2 °C > m.p. > 181.0 °C
m.p.(B) – 181.0 °C
Number of points = 4 × ( )
2.2 °C
m.p. ≤ 181.0 °C 0 points
NMR spectrum of the sample will be recorded if the m.p. starts bellow 181.0 °C. Reduction of the
points for the yield will be applied according to the contents of impurities based on NMR spectra.
Solubility test of the sample will be performed if the sample doesn’t melt completely above 190 °C.
Reduction of the points for the yield will be applied according to the contents of insoluble impurities.
Melting point interval of compound B will be evaluated only if any points were granted for the
starting point of melting (max 4 points)
Interval ≤ 3.1 °C 4 points
3.1 °C < interval < 5.1 °C
5.1 °C – interval
Number of points = 4 × ( )
2.0 °C
Interval ≥ 5.1 °C 0 points
Purity of compound C (max 2 points)

Qualitative check by the determination of the melting point 240 °C < m.p. < 275 °C. The sample should
not melt below 240 °C (1 point) and no solid residue should remain at 275 °C (1 point).
NMR spectrum of the sample will be recorded if the m.p. starts bellow 240.0 °C. Reduction of the
points for the yield will be applied according to the contents of impurities based on NMR spectra. If
more than 10% of other compounds than the product are present, 0 points will be given for the yield
of product C.
Solubility test of the sample will be performed if the sample doesn’t melt completely above 275 °C.
Reduction of the points for the yield will be applied according to the contents of impurities based on
solubility test. If more than 10% of insoluble impurity is present, 0 points will be given for the yield of
product C.

Sintesi inorganica
TH
PRACTICAL PROBLEMS
Introduction:
The experimental assignment consists of the synthesis and subsequently, the analysis of
amminenickel(II) chloride: NiClx(NH3)y.
The synthesis proceeds in three steps:
a) Preparation of a solution of nickel nitrate from nickel and concentrated nitric acid
(green solution), time required about 20 min.
b) Preparation of amminenickel(II) nitrate (blue crystals)
c) Preparation of amminenickel(II) chloride (blue-violet crystals)
The analysis encompasses the determination of the percentages of the three
components (ammonia, nickel and chlorine) of the salt, according to the instructions
given in 2.
Synthesis of the nickel(II) salt:
All work on the synthesis must be carried out in the fume hood. Use of (safety) glasses is
obligatory. If necessary use other safety equipment, such as rubber gloves and pipetting
balloons.
a) Put a "dubbeltje" (Dutch coin of 10 c, containing 1.5 g of nickel), in a 100 ml conical
flask (Erlenmeyer flask) and add 10 ml of concentrated nitric acid (65 %). Fit the flask
with an "air cooled" condenser (no water) and heat the contents on a hot plate until a
violent reaction occurs. Continue heating carefully until all metal is dissolved. Cool the
green solution in an ice-water mixture.
Write in the report form the equation of the chemical reaction that has occurred.
b) Add, under continuous cooling, in small portions 25 ml of ammonia solution (25 %) to
the ice cold solution. As soon as about 15 ml has been added, salt crystals start to
precipitate. Having added all ammonia solution, filter the cold solution through a
sintered glass filtering crucible by applying a vacuum with an aspirator. Wash the
crystals three times with small portions of a cold ammonia solution (25 %). Remove as
much liquid as possible from the crystalline mass by maintaining the vacuum.
TH
c) Dissolve the moist crystalline mass in 10 ml of hydrochloric acid (18 %). Cool the blue
solution in an ice-water mixture and then add slowly 30 ml of a solution of 30 g
ammonium chloride in 100 ml of ammonia solution (25 %). This yields a blue-violet
coloured crystalline mass. Cool the mixture and filter as in b). Wash with ammonia
solution (25 %), then with ethanol and finally with diethyl ether. Leave the crystals on
air until all ether has evaporated. Determine the mass of the dry product and record
this on the report form.
TH
Preparation of cis-Copper-bis-Glycinate Hydrate [Cu(gly)2•xH2O]
Copper(II) amino acidate coordination compounds are monometric units for

synthesizing important biopolymers such as metalloenzymes like ceruloplasmin, on which
every living organism depends. In laboratory cis-copper-bis-glycinate hydrate can be
produced by the reaction of cupric hydroxide with glycine at a temperature of ca. 70 °C.
Reagents:
CuSO4⋅5 H2O(s)
NH3 (aq) (3 mol dm-3)

glycine(s)
95% ethanol,
acetone
-3
NaOH (2 mol dm )
BaCl2 (0.5 mol dm-3)
1. Preparation of Cu(OH)2
Procedure:
(1) Dissolve your pre-weighted sample of CuSO4⋅5 H2O (6.0 g) in 40 cm3 of water with a
250 cm3 beaker as a container.

(2) Add slowly 3 mol dm-3 ammonia solution to the CuSO4 solution, gently stirring, until
the precipitate is completely dissolved and the solution is turning blue-violet.
(3) Add 2 mol dm-3 NaOH solution to the above solution until no more precipitate
formed.
(4) Filter the precipitate over a Büchner funnel under reduced pressure. Wash the
precipitate with water until no SO2-
4 ion is detected in the filtrate.
(5) Collect Cu(OH)2 for the preparation of Cu(gly)2 . x H2O.
Write the equations for the main chemical reactions having taken place in the above
procedure.
TH
2. Preparation of cis-Copper-bis-Glycinate Hydrate

Procedure:
3
(1) Dissolve a pre-weighted sample of glycine (3.6 g) in 130 cm of water and then warm
the solution in a hot water bath (70 °C). Add the C u(OH)2 to the solution, stir gently
3
until the precipitate is dissolved. Perform a hot filtration and add 10 cm of
95 % ethanol.
(2) Cool the solution and when needle-like crystals appear, place it in the ice water bath
for 10 min.
(3) Filter the crystals over a Büchner funnel under reduced pressure, wash once with 10
cm3 of ethanol-water mixing solvent and then twice with 10 cm3 acetone, squeeze the
crystals as dry as possible on the funnel.
(4) Collect the crystals to a watch glass and dry it (consult your supervisor).
(5) Half an hour later weigh the product. Write the mass of product and the percentage
of yield on your student's report. Give the expressions for calculation to show how
you calculate.
_______________
SOLUTION
• The calculated theoretical yield in g.
• The yield obtained as a percentage of the theoretical yield.
Tasks:
Write down the balanced chemical equations used in the preparation.
Solution of the tasks:
1. Cu2+ + 2 NH3 + 2 H2O → Cu(OH)2 + 2 NH+4
Cu(OH)2 + 4 NH3 → [Cu(NH3)4]2+ + 2 OH–

Cu(OH)2 + 2 NH2CH2COOH → Cu(NH2CH2COO )2 + 2 H2O
–
2.
ND
PRACTICAL PROBLEMS
photo chemistry.

K3[Mn(C2O4)3]·xH2O

4 (aq) + 8 H2O(l)
C2O4H2(aq) + CO32- (aq) → C2O2-

4 (aq) + CO2(g) + H2O(l)
4 (aq) + 4 C2O4H2(aq) →
2+
4 Mn (aq) + MnO-4 (aq) + 11 C2O2-
→ 5 [Mn(C2O4)3]3–(aq) + 4 H2O(l)
3 3
ND
3 3
3
3
filtration.
__________

Ability
water before use.

-
I3- (aq) + 2 S2O32- (aq) → 3 I–(aq) + S4O2-

6 (aq)
3 3
3
ND
3
colourless.
__________

Ability

3– +
+

3 3
RD
Hydrogen generation from ammonia borane
Hydrogen has been considered as a clean and environmentally benign new energy
carrier in the way towards a sustainable energy future. An effective and safe storage of
hydrogen is one of the key issues of the hydrogen economy. Among the chemical
hydrides, considered as potent solid hydrogen storage materials, ammonia-borane
(H3N·BH3) has been attracting a great deal of attention due to its high hydrogen content
and stability under fuel cell operating conditions. Ammonia borane can release hydrogen
upon hydrolysis, (Equation 1):
H3N.BH3(aq) + 2 H2O(l) → NH4BO2(aq) + 3 H2(g) (1)
Aqueous solution of ammonia borane is stable and its hydrolysis occurs only in the
presence of a suitable catalyst. Recent studies have shown that palladium(0) nanoclusters
stabilized by water soluble polymers are highly active catalyst in the hydrolysis of ammonia
borane. Palladium(0) nanoclusters are generated in situ by the reduction of potassium
tetrachloropalladate(II) with ammonia borane in the presence of poly(4-styrenesulfonic
acid-co-maleic acid).
In this experiment, the catalytic hydrolysis of ammonia borane will be carried out
starting with potassium tetrachloropalladate(II) in a solution containing poly(4-
styrenesulfonic acid-co-maleic acid). Potassium tetrachloropalladate(II) will be used as
precatalyst, which will be reduced by ammonia borane and palladium(0) nanoclusters will
be formed and stabilized by poly(4-styrenesulfonic acid-co-maleic acid). These
nanoclusters will catalyze the hydrolysis of ammonia borane.
Chemicals
• Solution A: H3NBH3 , 29.5 mg dissolved in 10 cm3 H2O,
• Solution B: poly(4-styrenesulfonic acid-co-maleic acid), 137.7 mg in 9 cm3 H2O,
• Solution C: Potassium tetrachloropalladate(II), K2[PdCl4], 6.7 mg in 1 cm3 H2O.
RD
I. Preparation of the Experimental Set-up

1. Check that the experimental setup, shown below, is held on a support, the
graduated tube is connected to the Schlenk tube by Tygon tubing, and a stir bar is
in the Schlenk tube.
2. Make sure that the septum is off and the valve is open.
3. By changing the bulb height adjust the water level in the graduated tube to zero.
4. Close the valve on the Schlenk tube.
Bulb
Graduated
Syringe Tube
Septum
Valve
Schlenk
Tube
Stir Bar
Magnetic
Stirrer
Experimental Set-up
RD
II. Hydrolysis of ammonia borane
A. In the absence of catalyst

1. Transfer all of the ammonia-borane solution (Solution A) from the glass vial to the
Schlenk tube through the funnel,
2. Add the polymer solution (Solution B) from the glass vial to the Schlenk tube
through the funnel.
3. Close the Schlenk tube with the septum, turn the stirring on at 600 rpm (as marked
on the stirrer), and open the valve connecting to the graduated tube. Record the
water level as Vo at time zero. Start the timer.
4. Every minute read the total volume of gas produced and write in the Table given on
the answer sheet. Do this for 10 minutes. Stop the timer.
B. In the presence of catalyst

1. While stirring, transfer all of the potassium tetrachloropalladate(II) solution (Solution C)
from the glass vial to the Schlenk tube by injecting through the septum using a
2.0 cm3 syringe. Keep the syringe inserted in the septum throughout the experiment.
Start the timer.
2. Every minute read the total volume of gas produced and write in the Table given on
the answer sheet. Do this for 10 minutes. Stop the timer.
Treatment of Data
A. Reaction of ammonia-borane without catalyst
2.1 Plot the volume of gas recorded versus time in Graph 2.1.
2.2 Report the volume of gas evolved as Vuncatalyzed.
B. Reaction of ammonia-borane with catalyst

2.3 Plot the volume of the gas generated versus time in Graph 2.2.
2.4 Calculate the maximum amount of substance (mol) and the maximum volume (cm3)
of hydrogen gas which will be evolved theoretically from the hydrolysis of 29.5 mg
ammonia borane with a purity of 97 % w/w at 25 °C. The atmospheric pressure is
690 torr.
RD
2.5 Calculate the rate of hydrogen generation in your experiment

i) in cm3 H2/ min.
ii) in mmol H2/min by assuming that the temperature is 25 °C. The atmospheric
pressure is 690 torr.
2.6 Based on your experiment calculate the rate of hydrogen production per mole of
palladium in (mol H2)×(mol Pd) ×(min) . The purity of potassium tetrachloro-
-1 -1
palladate(II) is 98 % w/w.
_______________
RD
SOLUTION
3
2.1 Part A. The volume of the gas evolved stays within a range of 0 – 2 cm (maximum).
3
2.2 V(H2)uncatalyzed = 0 cm
2.3 Part B. The gas volume versus time data for the reaction of ammonia borane in the
presence of catalyst, are given in the table below.
Time 0 1 2 3 4 5 6 7 8 9
(min)
Volume
(cm3) 0 17 31 45 57 68 73 73 73 73
Graph of gas volume versus time in the presence of catalyst:
2.4 – 2.6
The required calculations are based on the experimental data obtained in practical
problem 2. The well known relations between the mass, molar mass, amount of
substance, and the volume of a gaseous substance at a certain pressure and
temperature, as well as the experimental volume data in dependence on time (part
2.3) should be used to solve the tasks 2.4 – 2.6.
Synthesis of a Salen Manganese Complex and Determining Formula of

the Product
Transition metal complexes of the 3d-block elements derived from the

bis(salicylidene)ethylenediamine (salen) ligand have proven to be efficient catalysts of
various redox reactions in organic synthesis.
N N
R OH HO R
(salen)H2, R = H
(salen*)H2, R = H, COOH, or SO3H
The ability of the salen ligand to stabilize higher oxidation states of 3d-block elements
is important in this sphere of chemistry. In particular, compounds of manganese in
oxidation states from II to V could be generated depending on the reaction conditions
when the manganese salen complex is prepared. In this task you are required to prepare a
manganese salen complex by reacting (salen)H2 with Mn(II) acetate in ethanol in the air in
the presence of lithium chloride. Under these conditions, you might have obtained a
complex of the formula (salen)MnClx, where x = 0, 1, 2, or 3.
You are expected to:
i) determine the mass of the product,
ii) characterize the purity of the material prepared using thin-layer chromatography (TLC),
iii) determine the metal oxidation state in the complex using an iodometric redox titration.
For the redox titration, you will be given a solution of a previously prepared analogue
of your compound, (salen*)MnClx, where manganese has the same oxidation state as in
the product and the substituent R on the benzene ring is either H, COOH, or SO3H.
Please read the whole description of this task and plan your work before you begin. Some
operations have to be performed in parallel in order to complete it in time.
Chemicals
Note: The exact values of masses and concentrations of the particular chemicals are
indicated on the labels.
• (salen)H2, ~1.0 g in a vial
N N
OH OH
• Mn(OOCCH3)2 · 4 H2O, ~1.9 g in a vial

• Lithium chloride, solution in ethanol, c = 1 mol dm–3
• Ethanol
• Acetone
• (salen*)MnClx, ~32 cm3 of a solution with a mass concentration of ~3.5 mg cm–3
N Cl N
x
Mn
R O O R
Both R groups are equal and can be either H, or COOH or SO3H.

• KI3, 50 cm3 of an aqueous solution in a bottle, labelled “I2”, c = ~0.010 mol dm–3.
• Ascorbic acid, 20 cm3 of an aqueous solution, c = ~0.030 mol dm–3.
• Starch, w = 0.01, 2 cm3 solution in water,
Procedure:
A. Synthesis of (salen)MnClx
B.
N N N Cl N
x
Mn
OH HO + Mn(OOCCH3)2 + O2 + LiCl O O
(salen)MnClx
(1) Place 2-3 crystals of (salen)H2 aside in a small vial to be used for the TLC
experiment later.
3
(2) Transfer the pre-weighed ~1.0 g sample of (salen)H2 provided into a 250 cm
3
Erlenmeyer flask charged with a stirring bar. Combine the reagent with 35 cm of
absolute ethanol.
(3) Place the flask on a hot plate/stirrer. Heat the contents with constant stirring until the
solid dissolves (usually, dissolution is complete when the ethanol is about to boil).
Then decrease the temperature setting to maintain the mixture close but below its
boiling point. Do not boil the mixture so that the neck of the flask remains cool. If the
flask is too hot to hold with bare hands, use a folded paper towel.
(4) Remove the flask from the hotplate and add to its content a pre-weighed ~1.9 g
sample of Mn(OAc)2 · 4 H2O. A dark brown colour will develop. Return the flask to the
hotplate immediately and continue heating and stirring for 15 min. Do not boil the
mixture so that the neck of the flask remains cool.
(5) Remove the flask from the hotplate and add to its contents the provided solution of
-3 3
LiCl (c = 1 mol dm ) in ethanol (12 cm , an excess). Return the flask to the hotplate
and continue heating and stirring for 10 min. Do not boil the mixture so that the neck
of the flask remains cool.
(6) After this time remove the flask from the hotplate and place it in an ice bath for
crystallization for 30 min. Every 5 min gently scratch the walls of the flask from inside
under the liquid level with a glass rod to accelerate crystallization of (salen)MnClx.
The first crystals may appear immediately upon cooling or after a period of only
10 – 15 minutes.
(7) Use vacuum line located inside the hood (the corresponding valve is labelled
“Vacuum”) and suction filter the crystalline solid formed using the small Hirsch funnel
and a suction flask. Use a transfer pipette to wash the solid with few drops of acetone
without disconnecting the flask from the vacuum line, and leave it on the filter (with
the suction on) for 10 – 15 min to air-dry.
(8) Transfer the solid product into a pre-weighed vial labelled “Product”, then determine
and record its mass, mp, in the box below. Record also the mass of the following
reagents used in the synthesis: (salen)H2, mS, and Mn(OOCCH3)2 · 4 H2O, mMn.
(9) Place the labelled vial with product into a zipper bag.
You are required to fill in the following table:
Mass of the empty vial for the product: _______________ g
Mass of the vial with the dried product: _______________ g
Mass of the product, mp: _______________ g
Mass of (salen)H2 from label on the vial (copy from the label), mS:
_______________ g
Mass of Mn(OOCCH3)2 · 4 H2O from label on the vial (copy from the label), mMn:
_______________ g
B. Volumetric analysis of a sample of (salen*)MnClx provided
HO OH
N Clx N O O N N O
Mn O
+ x/2 HOH2C Mn + x/2 HOH2C
R O O R R O O R
HO OH O O
(salen*)MnClx
+ xHCl
R = H, COOH, or SO3H
Procedure:
(1) Dispense 10.00 cm3 of the provided (salen*)MnClx solution into a 125 cm3
Erlenmeyer flask using the volumetric pipette.
(2) Add 5.00 cm3 of the ascorbic acid solution to this solution and mix well. Allow the
solution to stand for 3 – 4 minutes.
(3) To avoid oxidation of ascorbic acid with O2 do not delay and titrate the solution
immediately with the KI3 solution using 5 drops of a 1 % starch solution as indicator.
The blue or blue-green endpoint should persist for at least 30 sec.
(4) If time permits, perform 1 – 2 replicate titrations to improve the accuracy of your
determination.
Place results of your titration experiment(s) in table 2.1.
Table 2.1. Results of the titration experiment(s).
Initial volume reading Final volume reading

# Volume of KI3 solution
in burette of KI3 in burette of KI3 3
3 3 consumed, cm
solution, cm solution, cm
1
2
_____
2.1 Indicate the volume (selected or averaged) of KI3 solution consumed in cm3 that you
will use for calculations of molar mass of (salen*)MnClx.
Concentrations of (salen*)MnClx (in mg cm–3) and ascorbic acid (in mol dm–3) are
given on the labels of the particular bottles.
2.2 From your titration data and referring to the table 2.2 deduce:
i) the value of x,
ii) oxidation state of manganese,
iii) the identity of the substituent on the salen ligand (R = H, COOH, SO3H). Show
them in the template below.
N N
Clx
Mn
O O
x = ________
Manganese oxidation state: ______________
Table 2.2
(Theoretical molar
R x
mass)/x, g mol-1
H 1 357
H 2 196
H 3 143
COOH 1 445
COOH 2 240
Table 2.2 continued
COOH 3 172
SO3H 1 517
SO3H 2 276
SO3H 3 196
C. TLC characterization of (salen)MnClx

(1) Dissolve a few crystals of the (salen)MnClx that you have prepared in a few drops of
absolute ethanol using a small vial and a plastic transfer pipette for ethanol.
(2) Dissolve a few crystals of (salen)H2 in few drops of absolute ethanol using another
small vial.
(3) If necessary, use scissors (available from lab assistant upon request) to trim the TLC
plate so it is an appropriate height for the TLC chamber.
(4) Fold or trim a large circle of filter paper, and place it in the beaker so that it takes
almost the full height of the beaker. This is required to saturate the chamber with
ethanol vapour. Add ethanol to the beaker to wet the filter and cover the bottom with
a 3 – 4 mm thick layer of the solvent. Close the beaker with watch glass.
(5) Mark the start.
(6) Using the capillary tubes provided spot the TLC plate with both solutions.
(7) Run a TLC in the beaker covered with a watch glass for 10 – 15 min.
(8) Mark the solvent front as well as the coloured spots on the TLC plate using a pencil.
(9) Dry the TLC plate in air and place it back into a zipper bag.
_____
2.3 Calculate the Rf for both (salen)H2 and (salen)MnClx.
2.4 Sketch the TLC plate on your answer sheet.
2.5 Determine and record the Rf values for (salen)H2 and (salen)MnClx.
_______________
SOLUTION
2.2
N N
Clx
Mn
H O O H
x=1
Manganese oxidation state: 3
2.4 Evaluation of the TLC plate:

Maximum points:
- for the appearance of two spots on the start line,
- for the start and solvent front lines,
- for the clearly visible spots.
2.5 The relevant RF values:

Compound Rf
(salen)H2 0.58 – 0.68
(salen)MnClx 0.30 – 0.40
Altre tecniche
ND
THE 2 INTERNATIONAL CHEMISTRY OLYMPIAD, Katowice, 1969
Allow to react 10 cm3 of a 3 N HCl solution with the metal sample (competing pupils
were given precisely weighed samples of magnesium, zinc or aluminium) and collect the
hydrogen evolved in the reaction in a measuring cylinder above water. Perform the task by
means of available device and procedure.
In order to simplify the problem, calculate the mass of your metal sample from the
volume of hydrogen on the assumption that it was measured at STP conditions.

RD
THE 23 INTERNATIONAL CHEMISTRY OLYMPIAD, Lodz, 1991
2+
Determination of the formation (stability) constants of the complex ions [Cu(NH3)4] and
[Zn(NH3)4]2+
Equipment:
Two dry beakers with copper and zinc electrodes,
three bottles with aqueous solutions of CuSO4, ZnSO4 and NH3, respectively,
one beaker with strips of filter paper for making a salt bridge,
one beaker with an aqueous solution of KNO3,
three pipettes for delivering CuSO4, ZnSO4 and NH3 solutions,
digital voltmeter for the EMF measurements,
red and blue leads (conductors) for connecting cell electrodes to the digital voltmeter,
rubber pipette filler,
appropriately marked glass stirring rods.
a) Procedure for setting up the Daniell cell:

3
1. Into the dry beakers containing Cu and Zn electrodes deliver 20 cm of CuSO4 and
20 cm3 of ZnSO4 using marked pipettes in order to get Cu/Cu2+ and Zn/Zn2+
half-cells.
2. Wet the filter paper strip with KNO3 solution. The strip should only be moisten with
the solution. Then place the strip ends into the CuSO4 and ZnSO4 solutions.
3. Connect the leads to the electrodes (red to Cu electrode and blue to Zn electrode).
a)
voltameter
KNO3
bridge
Fig. 1
RD
b) Procedure for the EMF measurement of the Daniell cell (EA):

Put the appropriately marked glass rods (red - Cu, blue - Zn) into the CuSO4 and
ZnSO4 solutions. Having stirred the solutions gently with the rods, the rods should be left
in the solutions throughout the course of the experiment. Start the EMF measurement of
the cell by connecting the red lead to the voltmeter terminal (HI) and the blue one to the
negative terminal (LO). If the EMF value changes by no more than 0.001 V, record the
EMF (EA).
c) Procedure for the EMF measurement of the cell (EB) after the addition of the
complexing agent (NH3 solution) into the Cu/Cu2+ half-cell:
Fig. 2
3
Pipette 20 cm of aqueous NH3 solution into the CuSO4 solution. Stir the solution
with a glass rod gently until it becomes a clear dark blue. Leave the rod in the solution.
Measure and record the new EMF (EB), in the way described in part b).
elektrolyte bridge
Fig. 3
RD
d) Procedure for the EMF measurement of the cell (EC) after the addition of the
2+
complexing agent (NH3 solution) to the Zn/Zn half-cell:
2+ 3
Leave the Cu/[Cu(NH3)4] half-cell unchanged. Add 20 cm of NH3 solution to the
ZnSO4 half-cell. Carry out the EMF measurement of the cell in the way described in part
b). Write down the result (EC).
Theoretical considerations:
-1 -1
Gas constant R = 8.314 J K mol
Faraday constant F = 96 487 C mol-1
i) The concentrations of CuSO4, ZnSO4 and NH3 aqueous solutions written on the
bottles are expressed in mol kg-1. Therefore they must be converted into appropriate
-3
concentrations expressed in mol dm . The densities (d) of the solutions as functions
of temperature are respectively:
CuSO4: d1 = 1.0923 (kg dm-3) – 0.0002700 (kg dm-3K-1) T
-3 -3 -1
ZnSO4: d2 = 1.0993 (kg dm ) – 0.0002900 (kg dm K ) T
NH3 : d3 = 1.0740 (kg dm-3) – 0.0002800 (kg dm-3K-1) T
ii) In order to convert concentrations (ci) into ionic activities (ai), we need to calculate
activities of the ions using the equation ai = fi*ci . The activity coefficient values, fi, of
the ions involved are given in the answer sheet. The activity coefficient of ammonia
should be assumed to be 1.
iii) To simplify the calculations it should be assumed that after the addition of the excess
of complexing agent (NH3) only Cu2+aq, Zn2+aq, [Cu(NH3)4]2+, [Zn(NH3)4]2+ ions exist in
the respective solutions.
iv) Any diffusion potential occurring between both half-cells when the salt bridge is
applied may be neglected in practice.
Questions:
2.1 Calculate the values of the concentrations of Cu2+ and Zn2+ ions in the Daniell cell
before the introduction of the complexing agent (NH3).
2.2 Calculate the standard EMF value Eo of your Daniell cell using the Nernst equation.
RD
2.3 Calculate the concentrations of [Cu(NH3)4]2+ and NH3 in the B type cell, i.e. after the
addition of NH3 to the Cu/Cu2+ half-cell.
2.4 Determine the values of the thermodynamic formation (stability) constants KB and ln
2+
KB for the [Cu(NH3)4] ions.
2+
2.5 Calculate the concentrations of [Zn(NH3)4] and NH3 in the type C cell, i. e. after the
2+
addition of NH3 to the Zn/Zn half-cell.
2.6 Determine the values of the thermodynamic formation (stability) constant KC and ln
2+
KC for [Zn(NH3)4] ions.
_______________
SOLUTION
2.1 The mass of the solutions (kg) can be transformed to volumes of the solutions (dm3)
using the given densities. The concentrations are then given in units mol dm-3.
 RT   RT 
2.2 E =  E 0 (Cu2+ /Cu) + ln([Cu2+ ] × fCu 2+ )  −  E 0 (Zn2+ /Zn) + ln([Zn2+ ] × fZn2 + )  − Edif
 2F   2F 
For Edif = 0 :
RT [Cu ] × fCu 2 +
2+
E A = E (Cu /Cu) − E (Zn /Zn) +

0 2+ 0
ln 2+
2F [Zn2+ ] × fZn2 +
EA can be measured. All other data required are given in the text of the problem or in
the answer sheet.
2.3 Concentrations after the addition of NH3:

c (Cu2+ ) × V
2+
[ Cu(NH ) ] =
V + V1
3 4
(c (NH3 ) × V 1 ) − (4 c (Cu2+ ) × V )
[NH3] =
V + V1
2.4 After the addition of NH3 the following complex equilibrium is established:
2+
Cu + 4 NH3 Cu(NH3 )2+
4
4 ] × fCu(NH
[Cu(NH3 )2+ 2+
β4 = 3 )4
[Cu2+ ] × fCu2+ × [NH3 ]4
RD
Then the Nernst equation has the form:
RT [Cu(NH3 )4 ] × fCu(NH3 )2+4

2+
E = E (Cu /Cu) =
' 0 2+
ln
1
2F β 4 × [NH3 ]4
RT [Cu(NH3 )2+ 4 ] × fCu(NH3 )2+

EB = E '1 − E2 = E (Cu /Cu) − E (Zn /Zn) +
0 2+ 0 2+
ln 4
2F [Zn2+ ] × fZn2 + × β 4 × [NH3 ]4
From the above equation β4 or lnβ4 can be calculated since EB can be measured,
and all other data required are given in the text of the problem or in the answer
sheet.
2.5 and 2.6

The procedure in the calculation of β4 or lnβ4 for complex Zn(NH3 )2+
4 is analogical
as that shown in parts (2.3) and (2.4) for complex Cu(NH3 )2+
4 .
ST
The Critical Micelle Concentration of a Surfactant

Surfactants are used extensively in many everyday cleaning products, such as
shampoos or detergents for washing clothes. One such surfactant is SDS, sodium
n-dodecyl sulfate, CH3(CH2)11OSO3Na (Relative Molecular Mass: 288.37).
Very dilute aqueous solutions consist of solvated individual molecules of SDS.
However, if the concentration is gradually increased beyond a specific concentration, the
concentration of monomeric SDS does not change, but instead the surfactant begins to
form clusters known as micelles. It is these micelles that assist in the removal of grease
and dirt. The concentration at which the micelles form is called the critical micelle
concentration. This process is shown schematically in the figure below.
low SDS concentration high SDS concentration

free monomer only micelles and some free monomer
In this experiment, you will determine the critical micelle concentration of SDS by
measuring the conductivity of different concentrations of SDS.
Chemicals
• Sodium dodecyl sulphate, (99%), approximately 4.3 g, accurately pre-weighed in vial
labelled ‘SDS’.
• Conductivity solution ‘HI 70031’, 20 cm3 in pouch.
ST
Procedure
(a) You are provided with approximately 4.3 g SDS, accurately pre-weighed in a vial, a
3 3 3
250 cm volumetric flask, a 50 cm burette, 50 cm bulb pipette, a conductivity meter,
conductivity solution (used only for calibration), and a tall plastic vessel.
You need to measure the conductivity (σ, in µS cm ) of various concentrations of
–1
(b)
–3
aqueous SDS (c, up to 30 mmol dm ). [Note: You may assume that all volumes are
additive.]
3.1 Give the concentration of your stock SDS solution.
3.2 Use the table given in the answer booklet to record your results and plot a suitable
graph to determine the critical micelle concentration (CMC) on the paper provided.
3.3 State the concentration at which micelles begin to form (the critical micelle
concentration).
Notes
1) Solutions of SDS readily form bubbles if shaken.

3
2) The conductivity meter needs at least 50 cm of solution to be inside the plastic
vessel in order to work correctly.
3) To calibrate the conductivity meter:
• Switch the meter on by pressing the ON/OFF button once.
• Press and hold the ON/OFF button again, this time for about 3 seconds, until
you see the letters ‘CAL’ on the screen, indicating that the calibration mode has
been entered. Let go of the ON/OFF button and ‘1413’ will start blinking on the
display. To calibrate, carry out the next step immediately, before the meter has
reverted back to reading ‘0’ on the screen (meaning you have exited the
calibration mode)
• Immerse the probe in the pouch containing the ‘HI 70031’ calibration solution,
without exceeding the maximum immersion level.
• Stir gently and wait for about 20 seconds to confirm the reading.
• Once the display stops blinking, the meter is calibrated and ready for use.
• Rinse the meter with distilled water and dry before making measurements.
4) To record the reading:
• Switch the meter on by pressing the ON/OFF button.
• Immerse the probe in the sample without exceeding the maximum immersion
level and being above the minimum immersion level.
ST
• Stir gently and wait for the reading to stabilize. The meter automatically
compensates for temperature variations.
• The conductivity value of the sample will be shown on the LCD.
_______________
ST
SOLUTION
3.1 Correct concentration with correct units is expected - full points.
Correct concentration but with missing or incorrect units - 1/2 points.
_____
Note:
The evaluation of the graphs, constructed by competitors in this practical problem,
differs from that used for grading especially titration results in the other practical
problems. That is the reason why the evaluation in this particular case is given here
more in detail.
3.2 Number and spread of data points

The graph should show two distinct gradients and the point at which the gradients
change is the critical micelle concentration (CMC). The region where the
concentrations are lower than the point at which the gradients change is referred to
as “Region 1”; “Region 2” refers to the region where the concentrations are higher
than this point. The gradient change will be taken from the data presented. If no
–3
gradient change is obvious the literature value of 8.3 mmol dm will be used to
distinguish between the two Sections.
Maximum marks are allotted if:
a) in Region 1 at least three points are distributed with a spacing of approx
CMC/(n+1) mmol (where n is the number of points).
b) in Region 2 at least three points are distributed through a range of at least
10 mmol with a spacing of approx c/(n+1) mmol (where n is the number of points
and c the concentration range and c ≥ 10 mmol dm–3).
Indicating gradients
Straight lines plotted through experimental points with different gradients and
extended to identify crossing points are expected.
Alternative graphs with marks allotted are shown below.
Accuracy of data
A transparent overlay will be used to judge the accuracy of the experimental
measurements as plotted on the graph. If a systematic error in calculation can be
ST
determined from the table of data the graph will be re-plotted by the organisers for
the purposes of this part of the marking.
The overlay has a number of bands marked and the marking scheme has been
devised to reward careful experimental technique. There is one set of bands for
Region 1 and another for Region 2. The bands are numbered from the innermost
(band 1) to the outermost (band 5) (see Fig. 3.1).
The maximum number of points for each band is shown in the following table:
Band 1 2 3 4 5 Outside 5
Maximum
10 8 6 4 2 0
number of points
Alternative graphs with marks allotted
ST
Points will be awarded as follows:

If there are three or more points in a Region and 50 % are in band m (where m is the
number of the band) with none falling in band m+2 or beyond, the full marks for band
m are awarded.
If n, the number of points in the Region, is less than 3, only (n/3) of the relevant band
marks will be given (and rounded up to the nearest half-integer when necessary).
Fig. 3.1. Examples
In Region 1 all of the datapoints lie in Band 1 (cross hatched) so 10 points scored for
that Region.
In section 2 one of the three datapoints lies in Band 1 (not 50%) but two lie in band
2. The remaining point does not lie in Band 4 (m+2) so full 8 points are scored.
3.3 Correct concentration as read from graph with correct units is expected.
TH
Determination of the content of phosphoric acid in a cola drink
Apparatus:
500 ml round-bottom flask with stirrer, reflux condenser, heating mantle, magnetic stirrer,
water bath.
Preparation of the sample:

The content of a cola drink bottle is stirred for two or three minutes in a round-bottom
flask. Afterwards, 6.0 g powdered active charcoal are added. The entire suspension is
carefully heated to reflux and is maintained there for ten minutes. The glass joint of the
reflux condenser must not be greased!
The heating mantle is then exchanged with an ice water bath. After the sample has
been cooled to 20 oC, it is filtered through a double fluted filter paper. The initial filtrate
should be recycled several times.
Adjustment of the pH-meter:

The pH-meter is adjusted to the working electrode by using two buffer solutions.
Titration:
150 ml of the unknown solution are titrated using pH indication with a standardized
-3
sodium hydroxide solution (c(NaOH) = 0.0500 mol dm ).
The first equivalence point of the phosphoric acid is reached after about 6 ml of the
NaOH solution have been consumed. The titration is to be continued until more than
about 12 ml of sodium hydroxide solution have been added.
Results of the experiment:

a) Draw the titration curve and determine the first equivalence point.
b) Determine the pH value of the heated cola drink and the pH value at the first
equivalence point.
c) Calculate the concentration of phosphoric acid in the cola drink. Write the calculation
and the result in your report.
TH
Interpretation of the experiment:

1. Describe and explain your observations during the titration.
2. Is it possible that the active charcoal could have influenced your titration result? Give
reasons for your presumption.
Chemicals:
Powdered active charcoal
-3
Sodium hydroxide solution; c(NaOH) = 0.0500 mol dm
Buffer solutions
TH
By thermometric titration of a hypochlorite solution with a solution of propanone you
will find the equivalent amounts of the reactants and consequently, the reaction products.
Procedure:
For the reaction of a hypochlorite solution with a propanone use solutions tempered
at laboratory temperature (check). Put 100,0 cm3 of a hypochlorite solution into a
thermobeaker, insert a thermometer and keep adding a 4-molar solution of propanone in
1,0 cm3 portions from burette, stirring the reaction mixture continuously by means of the
thermometer (carefully, do not break!). Stir the reaction mixture thoroughly after each
addition and read the highest temperature reached. Keep on adding the propanone
solution as long as the temperature rises. Then add three more portions and finish the
experiment. Keep the reaction mixture for possible later use.
Problems:
2.1 Draw a titration curve from the data of the temperature changes and consumption of
propanone solution. Read the end point of the titration from the curve. Express the
equivalent amounts of the reactants in moles.
2.2 Write equation for the chemical reaction and name the product that is formed.
2.3 Suggest a calculation for the approximate value of the reaction heat from the data
obtained.
2.4 Consider the procedure of isolation of the product from the reaction mixture and give
the method of its identification.
2.5 The exact concentration of a hypochlorite solution can also by determined by
measuring the volume of oxygen released after catalytic decomposition of
hypochlorite. Illustrate the principle of this method by means of a chemical equation
and show schematically the procedure for the calculation.
____________________
SOLUTION
2.2 CH3COCH3 + 3 ClO− → CHCl3 + 2 OH− + CH3COO−
chloroform
TH
2.3 Calculation of heat evolved in the course of the reaction:

Q = m c ∆t
Q – reaction heat,
m – mass of the solution,
c – specific heat capacity of the solutions taking part in the reaction,
∆t – temperature difference (elevation of temperature)
On the basis of the data obtained in the task, it is possible to calculate Q value per
one mole of reactant.
2.4 The mixture contains:
reactants – (excess of about 3 cm3 of the 4-molar propanone solution),
products – CHCl3, OH−, CH3COO−.
Acetone and chloroform are separated from other substances in the aqueous
solution by means of a separatory funnel and a subsequent distillation.
Identification of chloroform: smell, density.
2.5 2 ClO− → O2
2 mol → 1 mol = 22.4 dm3
TH
PRACTICAL PROBLEMS
Four aqueous solutions are available on the laboratory desk. These are solutions of
-3
HCl, NaOH, NH3, and CH3COOH whose concentrations are approximately 1 mol dm . The
concentration of HCl solution is the only one that is exactly determined and known.
Using the volumetric solution of HCl, determine the exact concentrations of the other
solutions. A burette, pipette, titration flasks and indicators methyl orange and
phenolphthalein are at your disposal. Perform twice each titration and calculate the mean
value for concentration. The third determination is needed to be carried out only in such a
case when the results of the previous two titrations differ more than by 2 %.
Now you will perform the following thermochemical measurements of neutralisation
heat evolved in the reactions of the above given solutions of acids and bases:
a) Measure quantitatively exactly 50.0 cm3 of the hydrochloric acid solution into a beaker.
Measure into another equal beaker a volume of NaOH solution that contains such a
number of moles of NaOH as that of HCl being present in the first beaker. Then
measure the temperatures of both solutions with a precision of 0.2 K. Pour quickly the
content of the first beaker into the other using the thermometers as a glass stick and stir
the resulting solution with the thermometer. Determine the final highest temperature of
the mixture.
b) Perform analogous measurement with the following pairs of acids and bases:
HCl − NH3, CH3COOH − NaOH, CH3COOH − NH3.
Problems:
1.1 What indicators have been used for the individual determinations? Give
approximately pH regions in which the mentioned indicators show colour transitions.
Give reasons for the use of the individual indicators using only ionic equations for the
reactions which are characteristic of specific properties of salts being formed in the
individual neutralisation reactions. Calculate the concentrations of all solutions under
investigations.
TH
1.2 Write the calorimetric equation in its general form by means of which the
neutralisation heat can be calculated. Calculate the thermal effect for each
neutralisation reaction under investigation and give the value in relation to one mole
of the water formed.
Densities of the solutions are as follows:

ρ(HCl) = 1.02 g cm-3
ρ(NaOH) = 1.04 g cm-3
ρ(NH3) = 0.99 g cm-3
ρ(CH3COOH) = 1.01 g cm-3
In the calculations consider the specific heat capacity value for the solutions equal to
4.19 J g-1 K-1 whereas the heat capacity of glass and thermometer may be neglected.
1.3. Have you obtained equal results in all four cases? If not, order the particular reaction
systems according to the decreasing value of reaction heat. What reactions cause
the above mentioned differences? Express the reactions by means of chemical
equations.
1.4 The exact methods showed that neutralisation heat in the reaction of the strong acid
with a strong base (i. e. the reaction heat when 1 mole of water is formed from H+
- -1
and OH ions) is equal to 57.57 kJ mol . Calculate the relative error of your
determination.
____________________
SOLUTION
1.1. In titrating a strong acid with a strong base, both phenolphthalein and methyl orange
can be used as acid-base indicators. The drop on the titration curve covers the colour
changes of both indicators (pH values from 4 – 10).
Only phenolphthalein can be used in the case when a weak acid is titrated with a
strong base because the neutralisation occurs at higher pH values (the colour
transition of phenolphthalein is in the region of pH = 8 – 10). A salt formed undergoes
hydrolysis (more precisely its anion) and the solution exhibits a basic reaction:
-
CH3COO + H2O CH3COOH + OH-
TH
In titrating a strong acid with a weak base or vice versa, methyl orange is used (pH =
3 – 4.5) and due to hydrolysis the resulting solution shows an acidic reaction:
+
NH+4 + 2 H2O NH3 . H2O + H3O
The exact concentrations of the aqueous solutions of sodium hydroxide and

ammonia are determined by titrations with the volumetric solution of hydrochloric
acid. The exact concentration of the acetic acid solution is then determined by a
titration with the sodium hydroxide solution.
1.2 When the specific heat capacities of glass and thermometer are neglected the
neutralisation heat can be then calculated according to a simple relation:
∆Hneutr. = (m1 + m2) c (T2 − T1)
m1 − mass of the first solution,
m2 − mass of the second solution,
c − specific heat capacity of the solutions,
T1 − temperatures of the solutions before mixing,
T2 − temperatures of the solutions after mixing.
If the temperatures of the solutions before mixing are not equal then T1 will be the
mean temperature of both. Finally, the neutralisation heat value should be related to
1 mole of water formed.
1.3 The results obtained for the neutralisation of a strong base with a weak acid and vice
versa, as well as for the reaction of a weak acid with a weak base, are lower than
those obtained for the neutralisation of a strong acid with a strong base. A part of the
heat is consumed for ionisation of a weak electrolyte:
CH3COOH + H2O CH3COO− + H3O+
A similar equation can be written for NH3.H2O.
TH
You are required to estimate the heat (enthalpy) change on mixing a series of 5
liquids to produce equimolar mixtures and to explain the temperature changes.
Procedure:
1. A mixture of trichloromethane (chloroform) and propanone (acetone)
Measure 0.5 mol of trichloromethane in the measuring cylinder labelled A1 and
measure its temperature. Dry the thermometer with a piece of tissue paper. Measure 0.5
mol of propanone using measuring cylinder B1, pour it into a beaker and measure its
temperature. Record the average of the two temperatures as temperature t1 (to 0.1 oC).
Leave the thermometer in the beaker. Add the trichloromethane to the propanon, stir the
mixture carefully and follow the temperature changes until a maximum or minimum is
reached. Record this extreme temperature as temperature t2. Dispose the mixture into a
special bottle labelled "waste solution", dry the reaction beaker and the thermometer and
proceed to the next part of the experiment.
2. A mixture of methanol and propanone (acetone)

Measure 0.5 mol of propanone in measuring cylinder B1 and 0.5 mol of methanol in
measuring cylinder A2, and continue as in part 1.
3. A mixture of methanol and n-hexane

Measure 0.5 mol of methanol into measuring cylinder A2 and 0.5 mol of hexane into
measuring cylinder B2, and continue as in part 1.
4. A mixture of methanol and water

Measure 0.5 mol of methanol into measuring cylinder A2, measure its temperature
and pour it into the beaker. Rinse the cylinder thoroughly with distilled water and then
measure 0.5 mole of water using this measuring cylinder. Continue as instructed in the
above part 1.
TH
Tasks:
Calculate the enthalpy (heat) changes involved in the mixings on the basis of the
temperature changes observed. In your calculations you should neglect heat exchanges
with the surroundings as well as the heat capacity of the beaker and thermometer. Briefly
explain your results in terms of the molecular interactions in the pure liquids and in the
mixture, preferably using sketches.
Data:
Relative Density Molar heat capacity

Substance
molecular mass (g cm-3) (J K-1 mol-1)
methanol 32.04 0.79 80.61

chloroform 119.38 1.49 114.94
acetone 58.08 0.79 124.96
n-hexane 86.18 0.66 190.10
water 18.02 1.00 75.35
TH
Determination of molecular mass by viscometry

Viscosity coefficient is a measure of fluid resistance to flow. It can be determined by
measuring the rate of liquid flow through a thin capillary. Polymer solution viscosity grows
with increasing concentration. At constant concentration, stronger solvent-polymer
interactions result in more expanded polymer coils and, therefore, in higher viscosity.
Provided the density of the diluted solution of a polymer is equal to that of the solvent, the
reduced viscosity ηred of the polymer solution with concentration c (g cm–3) is defined as
follows:
ηred = t – t0 cm3 g–1  ,

 
t 0c
where t and t0 are the flow times of the solution and pure solvent, respectively.
Reduced viscosity for dilute polymer solutions depends on concentration as follows:
ηred (c ) = [η ] + k c ,
3 –1
with k, a parameter and [η], intrinsic viscosity (cm g ). The intrinsic viscosity [η] is
determined by extrapolation of the reduced viscosity to zero polymer concentration. In
general, the intrinsic viscosity is related to the molecular mass M of the polymer according
to the Mark-Kuhn-Houwink equation:
[η ] = K M α ,
where K and α are the constants for a particular solvent–polymer pair at a certain
temperature. Thus, M can be derived from the Mark-Kuhn-Houwink equation using
experimentally determined [η] and reference data for K and α.
How to work with viscometer

a) Mount the viscometer (see the picture below) attached so that its tubing (3) is
vertical, and the collection vessel (1) stands on the lab stand basement. Adjust the
fixing clamp as low as possible.
b) Put 10 cm3 of the liquid to be analyzed into the collection vessel (1) through the
tubing (2) using a pipette.
TH
1 – collection vessel
2 – supplementary tubing
3 – supplementary tubing
4 – measurement vessel
5 – collection vessel
6 – the match marks
7 - capillary
c) Place the pipette filler or rubber bulb on top of the tubing (3) and suck the liquid into
the measurement vessel (4) so that the liquid is drawn into the collection vessel (5).
When sucking the liquid, avoid the air bubbles in the capillary (7) and the vessels (4,
5), as these can cause significant experimental errors. The liquid meniscus should be
about 10 mm above the upper mark (6).
d) Zero the stopwatch, and remove the pipette filler or bulb out of the tube (3). The
liquid starts flowing down to the collection vessel (1).
e) Measure the flow time: start the stopwatch when the liquid meniscus passes the
upper match mark (6) and stop the stopwatch when the liquid meniscus passes the
lower match mark (6).
ATTENTION: Handle the viscometer with great care!

There will be no replacement if you have broken your viscometer!
If you break your viscometer tell the lab assistant. You may then attempt to do the
experiment using the 25 mL pipette and beaker in place of viscometer.
Clean the viscometer three times with tap water and once with distilled water before
you pass over to a new polymer sample. To do this, first wash it with tap water, and then
rinse with distilled water. There is no need to wash it with the polymer solution, the error
can occur but it is negligible.
TH
You are NOT requested to fill in all table cells in the Answer Boxes. Perform as many
measurements as you prefer for accurate averaging.
Chemicals
•
3
Poly(vinyl) alcohol, 40 cm each, 5 vials
Procedure
-3
You are provided with a set of aqueous solutions of polymers (0.01 g cm , stock
solutions). Three of P1-P4 are solutions of poly(vinyl alcohol), whereas the fourth one is
that of a partially hydrolyzed poly(vinyl acetate) containing ca. 10 % of non-hydrolyzed
units. It is unknown which of the P1 – P4 solutions is partially hydrolyzed poly(vinyl
acetate). Molecular masses of the polymers P1 – P4 are given in the Table.
Approximate molecular mass Sample code

26650 P2
50850 P1
65300 P4
91900 P3
Sample X is poly(vinyl alcohol) of an unknown molecular mass.

In this task you will have to identify which of P1 – P4 is the solution of partially
hydrolyzed poly(vinyl acetate) and determine the molecular mass of polymer X.
3.1 Write down the reaction scheme of poly(vinyl alcohol) preparation by hydrolysis of
poly(vinyl acetate).
Reaction scheme:
n
H2O, H+
O O
TH
3.2 Choose (tick appropriate box) which polymer shows the stronger interaction with
water and compare the viscosities of aqueous solutions of fully and partially
hydrolyzed poly(vinyl acetates). Assume that the concentration of the solutions and
the molecular masses of the polymers are the same.
Poly(vinyl alcohol)
Partially hydrolyzed poly(vinyl acetate)
Compare the viscosities:
η (poly(vinyl alcohol) _____ η (partially hydrolyzed poly(vinyl acetate)
(put either <. >, or ≈)
3.3 Measure the flow time of the pure solvent (distilled water). You are not requested to
fill all the boxes in the answer sheet.
3.4 Measure the flow times of the stock solutions of P1 – P4, and that of X. Calculate the
reduced viscosities. You are NOT requested to fill in all table cells in the Answer
Boxes. Perform as many measurements as you prefer for accurate averaging.
3.5 Encircle the solution out of P1, P2, P3, P4 which is the sample of partially hydrolyzed
poly(vinyl acetate). Hint: Take into account the given molecular masses of the
polymers P1 – P4.
Do not use this polymer in the next part of the experiment.
3.6 To determine the parameters of the Mark-Kuhn-Houwink equation and calculate the
unknown molecular mass of X choose and encircle two most appropriate solutions of
poly(vinyl alcohol) with different molecular masses. Assume that the absolute error of
intrinsic viscosity determination does not depend on the sample molar mass.
3.7 Using appropriate measuring glassware to prepare the solutions, measure the flow
time of a number of diluted solutions of three poly(vinyl alcohol) samples: that of an
unknown molecular mass (X), and the pair of poly(vinyl alcohols) chosen in 3.6, and
TH
calculate the corresponding reduced viscosities. When calculating the diluted

solutions concentration, assume that density of the polymer solutions is equal to that
of water. Determine the intrinsic viscosities for each of the examined samples.
Submit the graph paper with your plots together with the booklet. Note: if you would
like to plot the data referring to different samples on the same plot, make sure you
use clearly distinguishable symbols for each dataset. You are NOT requested to fill in
all table cells in the answer booklet.
Summary of experimental results (only fill in the measured values)
Sample P__ P__ X
Concentration (c), g cm–3: 0.01 0.01 0.01
Reduced viscosity (ηred), cm3 g–1
c (1st dilution), g cm–3:

3 –1
ηred, cm g
c (2nd dilution), g cm–3:
ηred, cm3 g–1
c (3rd dilution), g cm–3:
ηred, cm3 g–1
c (4th dilution), g cm–3:
ηred, cm3 g–1
c (5th dilution), g cm–3:
ηred, cm3 g–1
3.8 Write down the form of equation you would use to determine K and α .
Derive the K and α values for the aqueous solution of poly(vinyl alcohol).
3.9 By using the obtained K and α values, as well as the intrinsic viscosity of the X
solution, calculate the molecular mass of the polymer X. If you have failed to
determine K and α, use K = 0.1 cm3 g-1 and α = 0.5.
_______________
TH
SOLUTION
3.1
H2O, H+ * HO O
*
*
*
OH
O O
3.2
Poly(vinyl alcohol)
η (poly(vinyl alcohol) > η (partially hydrolyzed poly(vinyl acetate)
3.8 log [η ] = log K + α log M
3.9 Sample calculation:
23.7 = 0.1 × M 0.5 ⇒ 237 = M 0.5

M = 2372 = 56169 ≈ 56200
Sommario
Analisi qualitativa ......................................................... 1
1st P1 ..................................................................................................................................................................... 2
1st P2..................................................................................................................................................................... 2
2nd P1 .................................................................................................................................................................... 3
3rd P2.................................................................................................................................................................... 4
4th P1 .................................................................................................................................................................... 5
5th P1 .................................................................................................................................................................... 6
5th P2.................................................................................................................................................................... 6
5th P3.................................................................................................................................................................... 6
6th P1 .................................................................................................................................................................... 7
6th P2.................................................................................................................................................................... 7
6th P3.................................................................................................................................................................... 7
7th P1 .................................................................................................................................................................... 8
7th P2.................................................................................................................................................................... 9
7th P3.................................................................................................................................................................. 10
8th P1 ................................................................................................................................................................... 11
8th P3 .................................................................................................................................................................. 12
11th P1 ................................................................................................................................................................. 13
12th P1 ................................................................................................................................................................ 15
12th P2 ............................................................................................................................................................... 23
13th P1 ............................................................................................................................................................... 25
13th P2 ............................................................................................................................................................... 26
14th P2 ............................................................................................................................................................... 27
15th P1 ............................................................................................................................................................... 30
15th P3 ............................................................................................................................................................... 33
19th P1 ............................................................................................................................................................... 35
22nd P2 .............................................................................................................................................................. 37
27th P1 ............................................................................................................................................................... 39
29th P2 .............................................................................................................................................................. 40
31st P2 ................................................................................................................................................................ 41
36th P2 .............................................................................................................................................................. 47
37th P2 .............................................................................................................................................................. 52
38th P3 .............................................................................................................................................................. 54
40th P3 .............................................................................................................................................................. 56
48th P1 ............................................................................................................................................................... 63
48th P3 .............................................................................................................................................................. 72
Titolazione acido-base .................................................. 79

3rd P1 ................................................................................................................................................................. 80
4th P2 .................................................................................................................................................................. 81
7th P4 titolazione del carbonato di sodio ............................................................................................ 82
8th P2 titolazione dell’acido ossalico...................................................................................................... 83
9th P3 retrotitolazione di un sale d’ammonio ..................................................................................... 84
10th P1 ............................................................................................................................................................... 85
13th P3 titolazione simultanea di carbonato e bicarbonato di sodio ........................................ 88
14th P1 preparazione di un tampone fosfato ...................................................................................... 90
15th P2 titolazione dell’acido ossalico.................................................................................................... 92
17th P1 determinazione del peso molecolare relativo di un acido debole ................................ 95
18th P2 titolazione dello ione ammonio .................................................................................................. 97
21st P2 retrotitolazione dell’acido acetilsalicilico previa idrolisi ................................................ 99
25th P2 titolazione dell’acido citrico .................................................................................................... 101
26th P1 determinazione del numero di acidità e del numero di saponificazione .................103
30th P2 titolazione dei protoni liberati da una resina a scambio ionico ................................106
38th P2 titolazione di acidi acetico e salicilico (con separazione cromatografica) ........... 110
39th P2 determinazione di carbonati e idrogenofosfati in una polvere abrasiva ............... 112
45th P2 determinazione di alcuni parametri delle acque .............................................................. 116
50th P3 identificazione di un’acqua minerale con resine a scambio ionico ............................124
Titolazione complessometrica ......................................... 141

14th P3 determinazione del prodotto di solubilità del cloruro di piombo(II) .......................142
18th P2 titolazione del nichel ...................................................................................................................144
24th P1 solubilità del calcio carbonato in presenza di CO2 (titolazione del Ca2+) ..............146
29th P1 determinazione della durezza in una bottiglia d’acqua .................................................149
33rd P2 titolazione del magnesio e del manganese ......................................................................... 151
36th P2 titolazione del lantanio(III) in un superconduttore .......................................................153
41st P2 titolazione del rame in un suo complesso con indicatore muresside ........................158
42nd P3 titolazione colloidale ...................................................................................................................162
43rd P1 analisi di un miscuglio di cloruri (titolazione del magnesio) ........................................168
45th P2 determinazione di alcuni parametri delle acque ..............................................................172
46th P3 analisi di un sale doppio di zinco e ferro(II) ...................................................................180
50th P3 identificazione di un’acqua minerale con resine a scambio ionico ............................186
Titolazione iodometrica ................................................ 203

19th P3 titolazione dello iodato.............................................................................................................. 204
22nd P3 ossigeno disciolto con metodo di Winkler ......................................................................... 206
26th P1 determinazione del numero di iodio di un grasso ........................................................... 209
27th P3 determinazione del rame nel complesso Cu(gly)2 · x H2O ...........................................212
28th P1 titolazione degli ioni rameici (Cu2+) e ferrici (Fe3+) .....................................................214
32nd P1 titolazione del manganese(III) proveniente da un complesso ....................................217
36th P2 determinazione del rame in un superconduttore ............................................................ 220
49th P1B determinazione del prodotto di solubilità dello iodato di calcio ............................ 225
Titolazione permanganometrica (o altre ossidimetriche) ............ 238

8th P2 titolazione dell’ossalato............................................................................................................... 239
11th P2 titolazione del permanganato .................................................................................................. 240
12th P3 titolazione del persolfato ..........................................................................................................241
15th P2 titolazione dell’ossalato ............................................................................................................. 244
30th P1 titolazione indiretta del calcio previa precipitazione con ossalato ......................... 247
32nd P1 titolazione dell’ossalato proveniente da un complesso ...................................................251
46th P3 analisi di un ossalato doppio di zinco e ferro(II) ......................................................... 254
47th P2 determinazione del vanadio e del cromo in una lega .................................................... 260
Titolazione argentometrica ............................................ 271

18th P2 titolazione dei cloruri provenienti da un sale di nichel ................................................ 272
26th P2 retrotitolazione del bromuro con tiocianato .................................................................... 274
40th P2 titolazione del potassio esacianoferrato per precipitazione con zinco ................. 276
41st P2 titolazione dei cloruri provenienti da un complesso ....................................................... 279
43rd P1 analisi di un miscuglio di cloruri ............................................................................................ 283
48th P2 titolazione dei cloruri in un’acqua minerale con metodo di Volhard ....................... 287
Spettrofotometria UV-Vis ............................................ 298

20th P2 determinazione delle costanti acide di un acido debole diprotico .......................... 299
34th P3 determinazione del ferro in una pillola .............................................................................. 302
38th P1 analisi di un miscuglio prima e dopo separazione cromatografica ........................... 304
39th P1 analisi di amminoacidi con cromatografia ionica ............................................................. 306
42nd P2 determinazione del ferro(II) e ferro(III) per colorimetria a occhio nudo ........314
49th P1A analisi e utilizzo di un indicatore acido-base per misure di pH ............................319
Cinetica chimica........................................................ 335

9th P1 rapidità del cambiamento di colore di una soluzione ....................................................... 336
10th P2 determinazione dell’ordine della reazione tra tiosolfato e ioduro .......................... 338
22nd P4 cinetica di una SN1 .................................................................................................................... 343
31st P3 studio cinetico della α-iodurazione dell’acetone ............................................................. 346
33rd P3 determinazione della costante cinetica della redox tra etanolo e cromato ....... 350
44th P1 effetto isotopico e meccanismo della iodurazione dell’acetone ................................ 352
46th P1 redox tra I- e Fe3+: cinetica basata sulla clock reaction al tiosolfato ............... 358
47th P3 determinazione cinetica del Diclofenac (DCF) in un farmaco ................................... 366
50th P2 cinetica dell’ossidazione cuprocatalizzata del luminol ...................................................381
Sintesi organica ........................................................ 397

16th P1 nitrazione della fenacetina (4-etossiacetanilide) ........................................................... 398
20th P1 reazione tra 1-naftolo-4-solfonato di sodio e nitrito di sodio ............................... 402
21st P1 sintesi dell’aspirina ...................................................................................................................... 403
22nd P1 condensazione aldolica tra acetofenone e benzaldeide (sintesi del calcone)...... 405
25th P1 ossidazione del colesterolo ...................................................................................................... 408
28th P2 sintesi della para-idrossiacetanilide (paracetamolo) .....................................................410
29th P3 sintesi di un derivato della diidro-1,3-benzossazina ...................................................414
32nd P2 protezione del gruppo carbossilico in un amminoacido ..................................................417
33rd P1 sintesi dell’acido 2-iodobenzoico ........................................................................................... 422
34th P1 idrolisi enzimatica del N-acetil-fenilalaninato di metile ............................................ 424
34th P2 sintesi della benzilidantoina.................................................................................................... 426
35th P1 sintesi del dipeptide N-acetil-L-prolinil-L-fenilalaninato di metile ...................... 429
36th P1 sintesi del Bisfenolo A bis(carbossimetil)etere ............................................................... 434
37th P1 sintesi della D,L-fenilglicina e risoluzione enantiomerica ........................................... 440
40th P1 sintesi di α-D-glucopiranosio pentaacetato ...................................................................... 444
41st P1 condensazione aldolica in assenza di solvente .................................................................. 448
42nd P1 reazione di Hantzsch Ester con Urea Hydrogen Peroxyde (UHP) .......................... 454
43rd P3 sintesi, purificazione e separazione di un miscuglio di diastereoisomeri ............. 460
45th P1 sintesi di 2,4-dinitrofenilidrazoni ........................................................................................ 465
46th P2 sintesi di un derivato dell’Artemisinina.............................................................................. 472
47th P1 effetto della catalisi sulla selettività di bromurazione ............................................... 478
49th P2 elaborare scheletri di carbonio (un’insolita condensazione aldolica) ...................... 493
50th P1 reazione aloformio e separazione per estrazione con solvente ................................ 506
Sintesi inorganica ...................................................... 523

18th P1 preparazione dell’amminonichel cloruro................................................................................ 524
27th P2 preparazione del cis-rame-bis-glicinato idrato ............................................................. 526
32nd P1 preparazione del potassio tris(ossalato)manganato(III) idrato ............................... 528
43rd P2 generazione di idrogeno da ammonio-borano....................................................................531
44th P2 sintesi di un complesso salen-manganese .......................................................................... 536
Altre tecniche ......................................................... 543

2nd P2 calcolo dell’idrogeno sviluppato in una reazione di dissoluzione.................................. 544
23th P2 determinazione di una costante di stabilità tramite pila Daniell ............................ 545
41st P3 concentrazione critica di micella con misure conduttimetriche ................................ 550
16th P2 titolazione potenziometrica dell’acido fosforico in una cola ...................................... 556
9th P2 titolazione termometrica di una reazione aloformio ....................................................... 558
10th P1 titolazione termometrica di reazioni acido-base ............................................................ 560
19th P2 calcolo della variazione di entalpia di mescolamento .................................................... 563
45th P3 determinazione del peso molecolare tramite viscosimetria ....................................... 565

Practical Problems

Uploaded by

Copyright:

Available Formats

Practical Problems

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Practical Problems

Uploaded by

Copyright:

Available Formats

Problemi pratici

THE COMPETITION PROBLEMS FROM THE INTERNATIONAL CHEMISTRY OLYMPIADS, Volume 1 10

THE COMPETITION PROBLEMS FROM THE INTERNATIONAL CHEMISTRY OLYMPIADS, Volume 1 19

An unknown sample is a mixture of 1.2-molar H2SO4 and 1.47-molar HCl. By means of

By means of available reagents and facilities perform a qualitative analysis of the

THE COMPETITION PROBLEMS FROM THE INTERNATIONAL CHEMISTRY OLYMPIADS, Volume 1 33

THE COMPETITION PROBLEMS FROM THE INTERNATIONAL CHEMISTRY OLYMPIADS, Volume 1 47

THE COMPETITION PROBLEMS FROM THE INTERNATIONAL CHEMISTRY OLYMPIADS, Volume 1 61

Test tube: No 5 - NH+4 ; No 6 - Hg2+; No 7 - OH-; No 8 – Fe3+ ; No 9 – Cu2+

THE COMPETITION PROBLEMS FROM THE INTERNATIONAL CHEMISTRY OLYMPIADS, Volume 1 78

THE COMPETITION PROBLEMS FROM THE INTERNATIONAL CHEMISTRY OLYMPIADS, Volume 1 95

Number of sample Formula Number of sample Formula

THE COMPETITION PROBLEMS FROM THE INTERNATIONAL CHEMISTRY OLYMPIADS, Volume 1 96

No of Reagent Observation Type of

THE COMPETITION PROBLEMS FROM THE INTERNATIONAL CHEMISTRY OLYMPIADS, Volume 1 97

Four unknown organic aliphatic compounds of a general formula A−CH2−B are

___ ___ ___ ___

As an aid the following can be used:

The requirements: An exact description of the experiments, reaction equations (or

To determine the melting point of an unknown organic substance, an approximate melting

D after the number denotes decomposition.

in ether in 5 % soluble insoluble

soluble insoluble soluble insoluble

S1: Substances with higher volatility;

N1: Substances with small volatility:

2. With Tollen's reagent

Osazone formation (indication of monoses)

CH2OH HC=O HN-NH2 HC=N-NH-

Ketose Aldose Phenyl- Osazone

Test for ketohexoses (Saliwanoff's reaction)

Test for pentoses (Tollens test)

C O When giving the configuration, use the Fischer

The following chemicals are at disposal:

Fe + 2 H3O+ → Fe2+ + H2 + 2 H2O

Al + 3 H3O+ → Al3+ + 3/2 H2 + 3 H2O

Zn + 2 H3O+ → Zn2+ + H2 + 2 H2O

Sn + 2 H3O+ → Sn2+ + H2 + 2 H2O

c) Ca2+: white precipitate with (NH4)2C2O4;

cations K+, Na+, Hg2+

anions OH–, NO3- , Cl–, SCN–, I–, CO32- , Cr2O72- , CrO2- 4- 3-

Fill in the following information on the sheet provided:

2+3+1 Ag2O(s) + 4 NH+4 + 2 OH– → 2 Ag(NH3 )+2 + 3 H2O

2+4 Zn2+ + 2 OH– → Zn(OH)2(s) ↔ Zn(OH)2(s) + 2 OH– → Zn(OH)2-

2+5 Al3+ + 3 OH– → Al(OH)3(s) ↔ Al(OH)3(s) + OH– → Al(OH)-4

Reactions to distinguish Zn2+ from Al3+:

2+5+1 Al(OH)-4 + 2 NH+4 → Al(OH)3(s) + NH3 + H2O

2+6 Cu2+ + 2 OH– → Cu(OH)2(s)

Cu(OH)2(s) + 4 NH+4 + 2 OH → Cu(NH3 )2+

Reactions to distinguish Cl– from Br– and from I–

3+4+1+2 AgCl(s) + 2 NH+4 + 2 OH– → Ag(NH3 )+2 + Cl– + H2O

AgCl(s) + 2 S2O32- → Ag(S2O3 )3-

3+6+1+2 AgBr(s) does not dissolve

3+7+8 AgI(s) does not dissolve

List of numbers and corresponding formulae for the substances:

The identification reactions:

-NH2 + H2SO4 NH3+ HSO4-

H3N+ COO- + H2SO4 H3N+ COOH HSO4-

-OH + NaOH OH + HOH

-OH + NaHCO3 OH + CO2 + HOH

_ _ _ _

2,4dinitrophenylhydrazine (2,4-DNPH) test