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23rd Chemistry Olympiad of the Baltic States

Daugavpils, Latvia

April 24-26, 2015

University of Daugavpils University of Latvia JSC OlainFarm

http://du.lv/en http://www.lu.lv/eng/ http://olainfarm.lv/en/

THEORETICAL EXAMINATION, ENGLISH

(used for clarification only)
"ScientiaVinces"

" Through knowledge you win "

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Introduction
General information
• You can only start to work once the START command is given.
• You are given 5 hours to complete your theoretical work and fill the answer sheets. You
will be notified 15 minutes before the end of theoretical examination. You must stop working
once the “STOP” signal is given. If you are late 5 min or more, your work will be disqualified
and you will be given 0 points for theoretical examination.
• Write your code (found on your working place, same as yesterday) in designated areas on
ALL of your answer sheets.
• All results should be written in boxed areas in answer sheets. Information written in other parts
of answer sheets will not be graded.White sheets provided are draft papers and it will not be
graded. If you need more draft paper just ask assistants.
• Ask assistant if you need English version of problems. It can be used for clarification only.
• Do not leave the examination room without permission.
• Number of decimal places in calculations must be in accordance with significant figures (±1
significant figure is acceptable) error and data analysis principles. You will be penalized once
with minus 1 point for inaccurate calculations in whole theoretical examination, even if your
solution are correct in all other aspects.

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Problem 1. Copper Man (6 points)

“Copper Man” was a Chilean copper miner who was entrapped in a copper mine in 550 AD and
subsequently copperized (coated in copper). The mummy has become a subject of interest in
archeology, metallurgy, and more recently, art.

1. Under the right conditions, charcoal dust can promote reaction that could lead to Copper Man’s
coating. Assume that Copper Man is coated in Cu2O and Cu0, which originated from Cu2+ salts in the
copper mine. State the role of charcoal in this reaction (mark correct answer with X):

reducing agent
oxidizing agent
catalyst
insulator
none of above

2. Consider the following reactions and reduction potentials:

Cu2O + 2H+ + 2e–→ 2Cu + H2O E0red = 0.471 – 0.059(pH)

CuO + 2H+ + 2e–→ Cu + H2O E0red = 0.570 – 0.059(pH)

a. For neutral (pH =7.0) environment, construct a Latimer diagram for the above couples and
calculate the potential for the CuO/Cu2O.

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3. Chalcanthite, the pentahydrate of copper sulfate, was the mineral that Copper Man was harvesting
from the mine.

In order to extract copper from the chalcanthite, Copper Man heated the chalcanthite to >700 °C in
the presence of Na2O, at which point a violent explosion would occur due to the following reactions:

4CuSO4 + 4Na2O → 4Na2SO4 + 2Cu2O + O2 React. I

Cu2O + CO → 2Cu0 + CO2 React. II

Calculate the Gibbs free change energy for these reactions using the half-reaction standard potentials.
(Hint: For CO2 + 2e– → CO + O2– you can use E0red = 0.11 V, and for O2 + 4e–→ 2O2– you can use
E0red = 1.23 V)

∆G for reaction I:

∆G for reaction II:

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For an exhibition, you must recreate Copper Man using a galvanic cell. Consider thePourbaix
diagram of copper.

4. Draw a diagram of a two-compartment galvanic cell that incorporates Copper Man as an electrode in
solution X coupled to a metal Y electrode in a solution of same metal ions. Label all components
including the electrodes (cathode and anode), the electrolyte species, and the reactions occurring at
the electrodes.

a. Choose the main component of the solution X:

CuCl2
Na2CuO2
Cu(OH)2
CuCl

b. Choose metal Y suitable for copper plating in the galvanic cell?

Zn
Ag
Na
Au

c. Draw diagram and write labels here:

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d. Reaction on cathode:

e. Reaction on anode:

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Problem 2. Determination of water content (10 points)

Very small water quantities can be measured with different methods: Karl Fischer titration, nuclear
magnetic resonance, infrared spectroscopy, gas chromatography, UV-Vis spectroscopy.

In Karl Fischer titration a mixture of iodine, pyridine (Py), sulfur dioxide and methanol is used. In the
presence of water following reactions take place:

SO2 + CH3OH + H2O + I2 →2HI + CH3OSO3H

Py + HI → PyH+I−

Py + CH3OSO3H → PyH+CH3OSO3−

Usually, the limiting component of the reaction is iodine.

As Karl Fischer titrant is somewhat unstable, the practical titre (mass of analyte per volume of titrant) is
often determined right before the analyses of a sample. An analyst weighted 260.3 mg of pure water and
filled the 100 ml volumetric flask with acetonitrile that does not contain any water. 10.00 ml of the
sample was taken for analyses and 6.20 ml of titrant was spent to reach the endpoint.

1.1 Calculate the titre (mg/ml) of the Karl Fischer titrant.

The same titrant was used to determine the water content of commercial acetonitrile. 20.00 ml of the
commercial acetonitrile was titrated with 5.12 ml of titrant. Density of acetonitrile is 0.786 g/ml.

1.2 Determine the water content in commercial acetonitrile (% and ppm).

A coulometric Karl Fischer titration is used in a laboratory, where one of the reagents I2 is generated
electrochemically from I-. It was of interest what the bias of the coulometric titration is. 4.113 g of
acetonitrile (containing an unknown amount of water) was analyzed with coulonometric Karl Fischer
method and 138.7 C was passed through coulometer (1 C = 1 A·s). 143.2 mg of water was weighted into

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100 ml volumetric flask and filled with the same acetonitrile to mark. 2.714 g of the sample was taken for
analyses and 145.3 C was used for complete titration of the sample.

1.3 Calculate the bias for this titration. Faraday constant F = 96500 C/mol.

The same procedure was repeated with 1.356 g of water weighted into 100 ml volumetric flaks. For
titrating 1.194 g of this sample 306.7 C was used.

1.4 Calculate the bias for this titration.

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1.5 Explain why can two titrations have a significantly different bias in this case.

Karl Fischer titration can also be used for water determination in solid samples if these can be dissolved
in appropriate solvent. However, some building material such as cement, chalk, ceramic materials can not
be analysed in this way due to occurring side reactions.

Therefore, infrared spectroscopy was used. Two chalk based reference materials containing 2.1 mg/kg
and 17.2 mg/kg of H2O were measured with attenuated total reflectance (ATR) method. At peak
maximum absorptions observed were 0.045 and 0.371 AU (absorption units).

2.1 What side reaction occurs for these materials and how does it influence the bias of Karl Fischer
method.

2.2 With IR-ATR method also a chalk sample was analysed and absorbance of 0.276 AU was recorded at
the peak maximum. Based on the Lambert–Beer law calculate the water content in the chalk sample.
Lamber Beer law: A=εlc, where A is the absorption at wavelength λ, ε is the molar attenuation coefficient
at wavelength λ, l is the optical path length and c is the analyte concentration. Assume that optical path
length is the same for all three measured materials.

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Problem 3. Some simple physical chemistry (9 points)

1. An equilibrium is reached in 0.10 M AgNO3 and x M NH3·H2O solution:

Ag+ + NH3⇔ [Ag(NH3)]+, K1 = 2.09·103 M−1

[Ag(NH3)]+ + NH3⇔[Ag(NH3)2]+, K2 = 8.32·103 M−1

At what x the concentration of [Ag(NH3)]+ is maximal? Calculate the value of x.

2. Equal amounts of KIO3 and KI (0.10 M each) react in a solution of H2SO4 at an initial pH value of
3.00.

½I2 + e−⇔I− E1° = +0.54 V

IO3− + 6H+ + 5e−⇔½I2 + 6H2O E2° = +1.20 V

Calculate the pH value of the solution at equilibrium.

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3. α-halogenation of aldehydes and ketones is autocatalytic reaction, i.e. the byproduct H+ is the catalyst
for that reaction:

R'COR + X2 = RCORX + H+ + X−

The reaction rate is expressed as:

r = k[R'COR][X2][H+]

If the initial concentrations [R'COR]0 = [X2]0, at what concentration [X2] is reached the maximum rate of
the reaction? Hint: d(xn)/dx = nxn−1.

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Problem 4. Harpoons and collisions (12points)

When modeling the path of a single atom A, it is useful to use it as a point of reference and “freeze” all
the other species in their own places. Therefore, we only have to consider any other particles when they
collide with the atom whose path we are modelling. If a centre of another species B is located in such a
way that the atom A will hit it, it is said to be in the collision tube of the atom A.

Theareaofthecrosssecti
onofthecollisiontube(σ)

1.Given that a golf ball with a radius of 2.3 cm is touching a basketball with a radius of 12.5 cm, calculate
the distance between their centres.

2. Hence, calculate the radius (R, in meters) and area (σ, in square meters)of the cross section of the
collision tubecreated by a gaseous potassium atom moving through bromine gas. The radius of a
potassium atom is 243 pm and the “radius” of a bromine molecule is 165 pm.

The collision tube as a model is used in the kinetic theory of gases. By applying this model, a useful
equation for the rate constant of second order reactions can be obtained:
𝐸𝐸 𝐴𝐴
𝑘𝑘2 = 𝜎𝜎𝑐𝑐̅𝑁𝑁𝐴𝐴 𝑒𝑒 −𝑅𝑅𝑅𝑅 ,
where𝑐𝑐̅ is the average effective velocity of the gas molecules. The pre-exponential term describes the
number of collisions occurring, while the exponential term describes the proportion of successful
collisions

3. Write down the more popular form of this equation and name the scientist who proposed it

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4. A second order reaction has a rate constant of 1000 L mol-1 s-1, an effective cross sectional area of the
collision tube of 1.0*10-18 m2, and average effective velocity of gas molecules of 100 m s-1 in standard
conditions. What is the activation energy of the reaction in kJ mol-1?

5. Consider a reaction whose activation energy is 0 J. Mark each correct statement with a + sign and each
incorrect statement with a - sign. (Note: each incorrect answer will incur negative marks, with the total for
this question not less than 0)
An appropriately selected catalyst would speed up this reaction
Every reactantatom/molecule has sufficient energy for the reaction
The reaction enthalpy change has to be zero or negative
The reactants of such a reaction are likely to be charge free and only contain paired electrons

6. Referring back to the beginning of the problem, calculate the k (L mol-1 s-1) of the reaction between
gaseous potassium and bromine at 800°C. Assume that the activation energy of the reaction is 0 J.
8𝑘𝑘 𝐵𝐵 𝑇𝑇
𝑐𝑐̅ = � , where kB is the Boltzmann constant (1.38 × 10-23 m2 kg s-2 K-1) and µ is the reduced mass of
𝜋𝜋𝜋𝜋
𝑚𝑚 1 𝑚𝑚 2
the particles involved (𝜇𝜇 = 𝑚𝑚 ).
1 +𝑚𝑚 2

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However, the measured k of the reaction is larger than the calculated value at 1.0×1012L mol-1 s-1, which
seemingly suggests that more species react than actually collide. This is because of the so-called harpoon
mechanism – the potassium atom “shoots” an electron into the bromine molecule even before the
collision takes place. This occurs due to the fact that the cross-sectional area ignores the effect of the
geometry of collisions on the reaction, as it assumes that all collisions in most cases are equal.

7. Assess how the transfer of the electron impacts the size of the particles and thus the cross-sectional area
of the collision tube! (Note: each incorrect answer will incur negative marks, with the total for this
question not less than 0)
7.1. What is the effect of ionisation of the K atom on its size?
A. It increases, as loss of the charge of one electron weakens the attraction between nucleus and the
electron cloud
B. It increases, as loss of the 4s orbital weakens the shielding experienced by other orbitals, thus
diffusing them
C. It decreases, as the lost electron is the only one in 4th energy level
D. It decreases, as the volume of the orbital the electron occupies is lost

7.2.What is the effect of electron transfer to the bromine molecule on its size?
A. It increases, as the new electron occupies a bonding molecular orbital
B. It increases, as the new electron occupies a anti-bonding molecular orbital
C. It decreases, as the new electron occupies a bonding molecular orbital
D. It decreases, as the new electron occupies a non-bonding molecular orbital

7.3. What is the net effect of the electron transfer on the cross-sectional area of the collision tube?
A. It increases
B. It decreases
C. Insignificant effect
D. Not enough data to assess

The modified reactive cross section area 𝜎𝜎 ∗ which should be used for reactions proceeding by a harpoon
mechanism can be calculated from radius 𝑅𝑅ℎ∗ using equation:

𝜎𝜎 ∗ = 𝜋𝜋(𝑅𝑅ℎ∗ )2 .

Rh describes the separation of centres of reacting species. There are three contributions to the energy of
interaction between the colliding species: ionization energy of potassium (abbreviated as I), electron
affinity of bromine gas (EEA) and Coulombic interaction (CI) energy between the ions when they have
been formed given by equation:
𝑒𝑒 2
CI = − .
4𝜋𝜋𝜀𝜀 0 𝑅𝑅ℎ

𝑅𝑅ℎ∗ is a distance when all these three contributions to the energy are in balance and following equation is
obeyed:
0 = I - EEA + CI

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8. Calculate the radius 𝑅𝑅ℎ∗ and reactive cross section area 𝜎𝜎 ∗ , if it is given that I = 420 kJ∙mol−1,
EEA= 250 kJ∙mol−1, and vacuum permittivity constant 𝜀𝜀0 = 8.854∙10–12C2∙N-1∙m-2 and elementary charge
𝑒𝑒 =1.602∙10–19C.

Usually to describe such a reactions a steric factor P is introduced, which connects reactive cross section
area 𝜎𝜎 ∗ with collision cross section area 𝜎𝜎 so that 𝜎𝜎 ∗ = 𝑃𝑃𝑃𝑃.

9. Calculate the steric factor P:

10. Now calculate the k (in L mol-1 s-1) of the same reaction at 800°C using 𝜎𝜎 ∗ instead of 𝜎𝜎:

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Problem 5. “Lucy in the Sky with Diamonds”(12points)

Back in the days of 1967, this famous song by the Beatles was released. It did not take long for hippies to
notice that an abbreviation would be LSD. This, one of the most widely known chemical substances was
first synthesized even earlier – in 1938 by a Swiss chemist Albert Hofmann and up to around 1980 it was
used as a psychiatric drug or for research purposes.

Today you will have a chance to synthesize (on paper!) this highly biologically active compound, that
boasts of a tetracyclic carboskeleton. Such an arrangement was and still is quite problematic if one tries to
come up with a synthesis route from very simple starting materials, hence you will begin your synthesis
from already bicyclic indole-3-propionic acid.

H
H O
N
N O
S
OH

p --TSA
1. KOH, (t--Bu)4NHSO4, Brr2
THF, DCM
2 . t--BuCOCl ,
11 E t2O, DCM
22
TH
T HFF, D M
DCM
C OO H 1, 2--ethanndiol,
p--TSA
O beennzzeennee
HCl 1. MeNH2, CHCl3
6 55 O
O HN
44 2. HCl, acetonne
3
H2O THF

Tss N
Et3N, LiBrr (--)--di bennzzoyl--L--t arrtarric aci d C
77 8 tt--B K, tt--B
BuuOK BuuOH TH
H, T HFF
9
CHCl3 MeCN, H2O +
(rrac.) (+)
O

N 1. NaOH
Et2 NH
22.. H
HCl
HN
11+11 3. CDI, DMF
11ra0c. HCl , H2O
rref luxx
N (+) (r ac.)
H +)--L
(+ LSD
D
O

COOH O
Ph O N N
N
O Ph
P h N
O H
COOH N
N
(--)--dibennzzoyl--L--tarrtarric acid midazzol e
CDI -- carrbod iim
Hints: compound 1 is known to be tricyclic; compound 7 is known to be tetracyclic; (rac.) denotes
racemate, compound 9 has one stereocenter.

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1. Draw structures of compounds (do not forget stereoisomerism, where necessary) 1-11.
1 2 3

4 5 6

7 8 9

10 11

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2. Draw reaction mechanism of 8 + TsCH2NC: → 9.

From a biochemical standpoint, lysergic acid diethylamide binds to the serotonin receptors in the body,
but the hallucinogenic effect lasts for up to 6-8 hours, meaning that it's metabolism is quite fast. Studies
have shown that metabolism in human organisms proceeds through O-H-LSD intermediate. A mechanism
of O-H-LSD formation was proposed, but it seems that some information is missing.

O
H hydrolase
N OR
non-enzymatic
Cyt P450 addition of H 2O
HN N
X Y
H O
H
N

ENZ
HN N O-H-LSD
H
OH
O

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3. Decipher structures X and Y and suggest an enzyme (ENZ) for the final step. It is known, that
ENZ should belong to Oxidoreductases. Note:The substrate of the enzyme is not supposed to
be specified, e.g. the answers deaminase or oxidase is specific enough.
X Y

ENZ

Biochemists have shown that LSD and its precursor ergotamine ERG bind the same serotonin receptor to
it's active site.

4. Taking into account that LSD and ERG bind the same receptor site, outline
physiologically active part in each molecule.

LSD molecule ERG molecule

(depicted geometry is similar to geometry in 3D)

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5. Fit LSD molecule into the active site of serotonin receptor and show molecular
interactions.

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Problem 6. Easy grow, easy bloom (11points)

Carbofuran is one of the most toxic insecticides and, therefore, is banned in Canada and
European Union. However, this pesticide is still widely used in other countries to control the
amount of insects in potato, pumpkin, sunflower fields.
Carbofuran can be produced quite easily from many simple chemical substances, but the main
drawbacks of these processes are the expense of production and the toxicity of chemicals
involved in the syntheses. Although, in 1980s several alternative methods for carbofuran
production were invented, which are relatively safe and require cheap starting materials (acetone
in this case).The synthesis scheme of carbofuran, bicyclic compound, is given below.
(cat.) – catalyst, (eq.) – equivalent

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1. Draw the structures of compounds A and B and the mechanism of the reaction A → B.
A A→B

2. Draw the structures of C and D(D is a mixture of stereoisomers). Also write down all possible
compound Dstereoisomers,which can be produced in the reaction C → D, mark all the
streocenters with ‘*’ and indicate their configuration (R/S).
C Stereoisomers of D

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3. Draw the structure of compound E. Taking into account that the reaction D → E was carried
out using only enantiomerically pure compound D‘(one of D stereoisomers)with all the
stereocenters having only R configuration,draw the stereoisomer(-s) of compound E which
would be synthesized in the reaction D → E.
E Stereoisomer(-s) of E

4. Write down the structures of compounds F, G, H and I.

F G H I

5. Show the mechanism of the reaction G → H.

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6. Compound E heated with Pd/alumina catalyst in nitrogen atmosphere produces intermediateI

which further heated under the same conditions gives more stable compoundJand then, bicyclic
compoundK. These intermediates are not extracted in this synthesis but are further heated to
produce compound L. Draw the structures of compounds J, K and L.
J K L

7. Write down the systematic name for the compound J using IUPAC nomenclature.

8. In the reaction from J to K a second ring is formed. How thisring could be named separately?
A) oxyfurane
B) dehydrofurane
C) benzofurane
D) dihydrofurane
E) ketofurane

9. Finally, the last step gives us the final product, carbofuran. Draw the structure of carbofuran.

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