Problems & Solutions

CHEMISTRY FOR A BETTER TOMORROW

July 25, 2020

52nd International Chemistry Olympiad, Istanbul, TURKEY

Instructions

• Only write with pen. Your calculator should be non-programmable.

• This examination has 9 problems.
• You will have 5 hours to solve the exam.
• Begin only when the START command is given.
• All results must be written in the appropriate boxes in pen in the designated areas on
the answer sheets. Use the back of the exam sheets if you need scratch paper.
Remember that answers written outside the answer boxes will not be graded.
• Write relevant calculations in the appropriate boxes when necessary. Full marks will
be given for correct answers only when your work is shown.
• The invigilator will announce a 30-minute warning before the Stop command.
• You must stop working when the STOP command is given. Failure to stop writing
will lead to the nullification of your exam.
• The official English version of this examination is available on request only for
clarification.

• You are not allowed to leave your working place without permission. If you need any
assistance (broken calculator, need to visit a restroom, etc), raise hand and wait until
an invigilator arrives.

GOOD LUCK!
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52nd International Chemistry Olympiad, Istanbul, TURKEY

Problems & Grading Information

Problem Title Total % of

Score Total
Score
1 Two Beauties of Turkey: the Van Cat and 24 8
the Ankara Cat
2 A Tale of a Reactive Intermediate 77 10
3 (±)-Coerulescine 51 8
4 Symmetry Does Matter! 66 10
5 Konya, Carrot, Beta-Carotene, Vitamin-A, 100 14
Immune System, Vision
6 Thermodynamics through an Interstellar 80 12
Journey
7 Phthalocyanines 85 12
8 Boron Compounds and Hydrogen Storage 58 14
9 Quantification of Heavy Metal Ions 100 12
TOTAL 641 100

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52nd International Chemistry Olympiad, Istanbul, TURKEY

Table of Contents

Authors ....................................................................................................................................... 4
Physical Constants and Equations .............................................................................................. 5
Periodic Table of Elements ........................................................................................................ 6
1
H-NMR Chemical Shifts ........................................................................................................... 7
Typical Coupling Constants ....................................................................................................... 7
13
C-NMR Chemical Shifts .......................................................................................................... 8
IR Absorption Frequency Table ................................................................................................. 8
Problem 1. Two Beauties of Turkey: the Van Cat and the Ankara Cat ................................... 10
Problem 2. A Tale of a Reactive Intermediate ......................................................................... 17
Problem 3. (±)-Coerulescine..................................................................................................... 27
Problem 4. Symmetry Does Matter! ......................................................................................... 35
Problem 5. Konya, Carrot, Beta-Carotene, Vitamin-A, Immune System, Vision.................... 44
Problem 6. Thermodynamics through an Interstellar Journey ................................................. 52
Problem 7. Phthalocyanines ..................................................................................................... 65
Problem 8. Boron Compounds and Hydrogen Storage ........................................................... 74
Problem 9. Quantification of Heavy Metal Ions ...................................................................... 84

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52nd International Chemistry Olympiad, Istanbul, TURKEY

Authors

ALANYALIOĞLU, Murat, Atatürk University

AYDOĞAN, Abdullah, İstanbul Technical University
BURAT, Ayfer Kalkan, İstanbul Technical University
DAĞ, Ömer, Bilkent University
DAŞTAN, Arif, Atatürk University
KILIÇ, Hamdullah, Atatürk University
METİN, Önder, Koç University
ÖZTÜRK, Turan, İstanbul Technical University
SARAÇOĞLU, Nurullah, Atatürk University
TÜRKMEN, Yunus Emre, Bilkent University
ÜNLÜ, Caner, İstanbul Technical University
YILMAZ, İsmail, İstanbul Technical University
YURTSEVER, Mine, İstanbul Technical University

Editor: SARAÇOĞLU, Nurullah, Atatürk University

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52nd International Chemistry Olympiad, Istanbul, TURKEY

Physical Constants and Equations

Avogadro's number, 𝑁𝐴 = 6.0221 × 1023 𝑚𝑜𝑙 −1

Boltzmann constant, 𝑘𝐵 = 1.3807 × 10−23 𝐽𝐾 −1
Universal gas constant, 𝑅 = 8.3145 𝐽𝐾 −1 𝑚𝑜𝑙 −1 = 0.08205 𝑎𝑡𝑚 𝐿 𝐾 −1 𝑚𝑜𝑙 −1
Speed of light, 𝑐 = 2.9979 × 108 𝑚𝑠 −1
Planck's constant, ℎ = 6.6261 × 10−34 𝐽 𝑠
Faraday’s constant, 𝐹 = 9.6485 × 104 𝐶 𝑚𝑜𝑙 −1
Mass of electron, 𝑚𝑒 = 9.1093 × 10−31 𝑘𝑔
Standard pressure, 𝑃 = 1 𝑏𝑎𝑟 = 105 𝑃𝑎
Atmospheric pressure, 𝑃𝑎𝑡𝑚 = 1.01325 × 105 𝑃𝑎 = 760 𝑚𝑚𝐻𝑔 = 760 𝑡𝑜𝑟𝑟
Zero of the Celsius scale, 273.15 𝐾
1 picometer (pm) = 10−12 𝑚; 1Å = 10−10 𝑚; 1 nanometer (nm) = 10−9 𝑚
1 𝑒𝑉 = 1.6 × 10−19 𝐽
1 𝑐𝑎𝑙 = 4.184 𝐽
1 𝑎𝑚𝑢 = 1.6605 × 10−27 𝑘𝑔
Charge of an electron: 1.6 × 10−19 𝐶
Ideal gas equation: 𝑃𝑉 = 𝑛𝑅𝑇
Enthalpy: 𝐻 = 𝑈 + 𝑃𝑉
Gibbs free energy: 𝐺 = 𝐻 − 𝑇𝑆
𝛥𝐺 = ∆𝐺 0 + 𝑅𝑇𝑙𝑛𝑄
0
∆𝒓 𝑮𝟎 = −𝑅𝑇𝑙𝑛𝐾 = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙
Entropy change:
𝑞
∆𝑆 = 𝑟𝑒𝑣 , where qrev is heat for the reversible process
𝑇

𝑉
∆𝑆 = 𝑛𝑅𝑙𝑛 𝑉2 (for isothermal expansion of an ideal gas)
1
0 𝑅𝑇 𝐶𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛
Nernst equation: 𝐸=𝐸 + 𝑙𝑛
𝑛𝐹 𝐶𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛
ℎ𝑐
Energy of a photon: 𝐸 = 𝜆
Integrated rate law
Zeroth-order: [𝐴] = [𝐴]0 − 𝑘𝑡
First-order: 𝑙𝑛[𝐴] = 𝑙𝑛[𝐴]0 − 𝑘𝑡
1 1
Second order: = [𝐴] + 𝑘𝑡
[𝐴] 0
−𝐸𝑎 /𝑅𝑇
Arrhenius equation: 𝑘 = 𝐴𝑒
Equation of linear calibration curve: 𝑦 = 𝑚𝑥 + 𝑛
Lambert–Beer equation: 𝐴 = 𝜀𝑙𝑐

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52nd International Chemistry Olympiad, Istanbul, TURKEY

Periodic Table of Elements

1 18
1 atomic number 2
H 2 Symbol 13 14 15 16 17 He
1.008 atomic weight 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 3 4 5 6 7 8 9 10 11 12 Al Si P S Cl Ar
22.99 24.31 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 - - - - - - - - - - -

Copyright © 2018 International Union of Pure and Applied Chemistry

Reproduced by permission of the International Union of Pure and Applied Chemistry

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52nd International Chemistry Olympiad, Istanbul, TURKEY

1
H-NMR Chemical Shifts

Typical Coupling Constants

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52nd International Chemistry Olympiad, Istanbul, TURKEY

13
C-NMR Chemical Shifts

IR Absorption Frequency Table

Functional Absorption Frequency

Type of Vibration Intensity
Group Region (cm–1)
Alcohol
(stretch, H-bonded) 3600–3200 strong, broad
O–H
(stretch, free) 3700–3500 strong, sharp
C–O (stretch) 1150–1050 strong
Alkane
stretch 3000–2850 strong
C–H
bending 1480–1350 variable
Alkene
stretch 3100–3010 medium
=C–H
bending 1000–675 strong
C=C stretch 1680–1620 variable
Alkyl Halide
C–F stretch 1400–1000 strong
C–Cl stretch 800–600 strong
C–Br stretch 600–500 strong
C–I stretch 500 strong
Alkyne
C–H stretch 3300 strong, sharp
variable, not present in
CC stretch 2260–2100 symmetrical
alkynes
Amine
medium (primary amines have
two bands; secondary amines
N–H stretch 3500–3300
have one band, often very
weak)

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52nd International Chemistry Olympiad, Istanbul, TURKEY

C–N stretch 1360–1080 medium-weak

N–H bending 1600 medium
Aromatic
C–H stretch 3100–3000 medium
C=C stretch 1600–1400 medium-weak, multiple bands
Carbonyl
C=O stretch 1820–1670 strong
Acid
C=O stretch 1725–1700 strong
O–H stretch 3300–2500 strong, very broad
C–O stretch 1320–1210 strong
Aldehyde
C=O stretch 1740–1720 strong
C–H stretch 2850–2820 & 2750–2720 medium, two peaks
Amide
C=O stretch 1690–1640 strong
stretch 3500–3100 unsubstituted have two bands
N–H
bending 1640–1550
Anhydride
C=O stretch 1830–1800 &1775–1740 two bands
Ester
C=O stretch 1750–1735 strong
C–O stretch 1300–1000 two bands or more
Ketone
acyclic stretch 1725–1705 strong
stretch 3-membered - 1850 strong
stretch 4-membered - 1780 strong
cyclic stretch 5-membered - 1745 strong
stretch 6-membered - 1715 strong
stretch 7-membered - 1705 strong
,-
stretch 1685–1665 strong
unsaturated
conjugation moves absorptions to lower wavenumbers
aryl ketone stretch 1700–1680 strong
Ether
C–O stretch 1300–1000 (1150–1070) strong
Nitrile
CN stretch 2260–2210 medium
Nitro
1560–1515 &
N–O stretch strong, two bands
1385–1345

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

Problem 1 Question 1.1 1.2 1.3 Total

8% of the total Points 14 4 6 24

Problem 1. Two Beauties of Turkey: the Van Cat and the Ankara
Cat

The most beautiful of cats, the Van cat is a pure breed living only in Lake Van basin. Another
endemic cat breed is the Ankara cat. They are called Angora cats. Their most important
feature is their two different eye colors.

Van cat Ankara cat Nepeta cataria (catnip)

Just like people, cats can sometimes be stressed and angry. Just as people are made happy by
melatonin, the stress of cats can be reduced and they can be made happy thanks to a natural
product. Nepetalactone is an organic compound isolated from the plant catnip (Nepeta
cataria), which acts as a cat attractant. Nepetalactone is a ten-carbon bicyclic monoterpenoid
compound derived from isoprene with two fused rings: a cyclopentane and a lactone.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

Cat eating catnip in the garden Cat's dream

Nepetalactone

Total synthesis of nepetalactone:

1.1. The above scheme describes the total synthesis of nepetalactone. Draw structures of A–
G, without stereochemical details.

Hints:
• Compound A has strong and sharp band at 3300 cm−1 in the IR spectrum.
• A, B, and F are monocyclic, while C, D, E, and G are bicyclic compounds.
• F has one doublet at ~ 9.8 ppm in the 1H-NMR spectrum.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

Reactions of nepetalactone:

The above scheme includes a few reactions of one of the enantiopure nepetalactone 1 isomers.
Three of the reaction products (5, 6, and J) are used as insect repellents in industry.

1.2. For the relationship between 5 and 6, which of the following is/are true? Tick the box
next to the correct answer(s) on your answer sheets.

☐ Enantiomers
☐ Diastereomers
☐ Identical
☐ Stereoisomers

Reaction of 1 with DDQ gives highly conjugated compound H. Also, thermal reaction of
compound H with p-quinone gives I with molar mass of 226.28 g/mol.

1.3. Draw the structures of H, I, and J indicating stereochemistry.

Hints:
• During the formation of I, sequential pericyclic reactions and an oxidation reaction
(due to the presence of O2) take place, and a well-known gas forms during the reaction.
• J has a strong and very broad band between 3300 and 2500 cm–1 in the IR spectrum.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

Solution:

Total synthesis of nepetalactone:

1.1. Draw the structures of A–G without stereochemical details.

A B

2 points for correct answer.

2 points for correct answer.

1 point if propargylation position is not correct.

Zero points for allene structure as it is not
consistent with hints given.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

C D

2 points for correct answer.

1 point for unconjugated enone. 2 points for correct answer.
Both E and Z isomers will receive full points
1 point if condensation position is not correct.

E F

2 points for correct answer. 2 points for correct answer.

1 point for a product via 1,4-reduction.

2 points for correct answer.

1 point for enol form of F.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

Reactions of nepetalactone:

1.2. For the relationship between 5 and 6, which of the following is/are true? Tick the box
next to the correct answer(s).

☐ Enantiomers
4 points (total) for the two correct answers (2
☒ Diastereomers points for each correct answer).
☐ Same compounds 2 points (total) if there is one mistake.
0 points if there are more than one mistakes.
☒ Stereoisomers

1.3. Draw the structures of H, I, and J indicating stereochemistry.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

H I

2 points for correct answer. 2 points for correct answer.

1 point for a conjugated oxidation product via a

five-membered ring.

2 points for correct answer.

1 point without stereochemical detail.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

Problem 2 Question 2.1 2.2 2.3 2.4 2.5 2.6 2.7 Total
10% of the total Points 7 9 8 16 5 4 28 77

Problem 2. A Tale of a Reactive Intermediate

Arynes constitute a special class of reactive intermediates. The first experimental evidence for
the structure of an aryne (benzyne) was demonstrated in 1953 via the elegant labeling
experiments by John D. Roberts and coworkers.

In one such experiment, chlorobenzene, whose carbon at position 1 was labeled with
radioactive 14C, was reacted with KNH2 in liquid NH3 to give nearly equal amounts of
isotopic isomers A and B along with the inorganic salt C. This reaction proceeds via the
formation of aryne intermediate D.

2.1. Draw the structure of A, B and D, and provide the formula of C. Indicate the position(s)
of 14C-labeled carbon(s) with an asterisk (*) whenever applicable.”

Analysis of the 14C-labeled product(s) was achieved via degradation experiments (the 14C-
labeled carbons are not shown on the structures). Radioactivities of the intermediates and final
products were examined.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

2.2. Tick the appropriate boxes on the answer sheet for the intermediates and products that
you expect to exhibit radioactivity.

Considering only A: Considering only B:

☐ Compound 1 ☐ Compound 1
☐ BaCO3 (Batch 1) ☐ BaCO3 (Batch 1)
☐ Compound 2 ☐ Compound 2
☐ BaCO3 (Batch 2) ☐ BaCO3 (Batch 2)

With the aim of facilitating aryne formation, Kobayashi and co-workers developed a fluoride-
induced aryne generation protocol. Using this method, benzene derivative 3 is reacted with
furan (4) in the presence of CsF, resulting in the formation of E, F, and G.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

• Combustion analysis of E revealed the following atom content: 75.8% carbon, 5.8%
hydrogen, and 18.4% oxygen.
• E does not have a proton that is exchangeable with D2O in 1H-NMR spectroscopy.
• F is an ionic compound.

2.3. Determine the structures of E, F, and G (without stereochemical details).

In the absence of a nucleophile or a trapping agent, arynes can undergo [2+2]-type

cyclodimerization or [2+2+2]-type cyclotrimerization reactions under suitable conditions. The
aryne derivative that is obtained when 3 is treated with one equivalent of CsF in MeCN can
give, in principle, four different dimerization and trimerization products (H–K).

• H has two planes of symmetry.

• I is expected to exhibit 21 signals in its 13C-NMR spectrum.
• I and J both exhibit an m/z value of 318.1 in their mass spectra.

2.4. Determine the structures of H–K.

When 5 is reacted with -ketoester 6 in the presence of 2 equivalents of CsF at 80 °C, L is

obtained as the major product. The 1H-NMR and 13C-NMR data for L, in CDCl3, are as
follows:

• 1
H-NMR: δ 7.79 (dd, J = 7.6, 1.5 Hz, 1H), 7.47–7.33 (m, 2H), 7.25–7.20 (m, 1H), 3.91
(s, 2H), 3.66 (s, 3H), 2.56 (s, 3H) ppm.

• C-NMR: δ 201.3, 172.0, 137.1, 134.4, 132.8, 132.1, 130.1, 127.5, 51.9, 40.2, 28.8
13

ppm.

2.5. Determine the structure of L.

2.6. In the reaction shown in task 2.5, which of the statement(s) in the answer sheet
describe(s) the function of CsF?

• The pKa values of HF and -ketoester 6 in dimethyl sulfoxide (DMSO) are about 15
and 14, respectively.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

☐ F– hydrolyzes the trifluoromethanesulfonate (O3SCF3) group of 5.

☐ F– attacks the –SiMe3 group of 5.
☐ F– acts as a base to deprotonate 6.
☐ F– acts as a nucleophile and attacks the ester group of 6.

Diazapyrone derivative 8 was shown to be a useful reactant for the construction of a variety of
cyclic frameworks. Its preparation from phenylglyoxylic acid (7) and its use in two different
reactions are described below.

• Q and T are gases under ambient conditions.

• O and P are constitutional isomers.
• Q does not have any signals in its IR spectrum.
• Heating 1 mol of R at 85 °C generates 1 mol of reactive intermediate S.
• Reaction of 8 with two equivalents of S gives U, Q, and T.

Note:
equiv= equivalent
cat= catalyst

2.7. Determine the structures of M–U.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

Solution:

14
2.1. Draw the structures of A−D. Indicate the position(s) of C-labeled carbon(s) with an
asterisk (*) whenever applicable.

A B

2 points.
1 point if labeled carbon is not shown or if its
position is incorrect. 2 points.
1 point if labeled carbon is not shown or if its
position is incorrect.
If unlabeled aniline is given as an answer for both
A and B, then only 1 point will be given in total
for A and B.
C D

2 points.
2 points for different resonance forms of A
1 point. including the circle representation for
0 points if only cation or anion is written. aromaticity.
1 point if labeled carbon is not shown or if its
position is incorrect.

2.2. Tick the appropriate boxes on the answer sheet for the intermediates and products that
you expect to exhibit radioactivity.

Considering only A: Considering only B:

☐ Compound 1 ☒ Compound 1
☒ BaCO3 (Batch 1) ☐ BaCO3 (Batch 1)

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

☐ Compound 2 ☐ Compound 2
☐ BaCO3 (Batch 2) ☒ BaCO3 (Batch 2)

Solution: only BaCO3 (Batch 1) Solution: Compound 1 and BaCO3 (Batch 2)

3 points for the correct answer. 6 points (total) for the two correct answers (3
0 points for one or more mistakes. points for each correct answer).
3 points (total) if there is one mistake.
0 points if there are more than one mistakes.
Note: The answer to this task will depend on the student’s structural assignment of compounds A and
B in task 2.1

2.3. Determine the structures of E, F, and G (without stereochemical details).

E F

CsO3SCF3 or Cs+ CF3SO3– or CsOTf

2 points.
4 points.
2 points if the product of [2+2] reaction between
aryne and furan is written.
0 points if ring-opened naphthol product is
written.
G

(CH3)3SiF or Me3SiF

2 points.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

2.4. Determine the structures of H–K.

H I

4 points.

4 points.
J K

4 points.

4 points.

2.5. Determine the structure of L.

5 points

The following isomer will also receive full points:

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

2 points for the following structures:

or

2.6. In the reaction shown in task 2.5, which of the statement(s) in the answer sheet
describe(s) the function of CsF?

☐ F– hydrolyzes the trifluoromethanesulfonate (O3SCF3) group of 5.

☒ F– attacks the –SiMe3 group of 5.
☒ F– acts as a base to deprotonate 6.
☐ F– acts as a nucleophile and attacks the ester group of 6.

The correct statements are the 2nd and 3rd statements.

4 points (total) for the two correct answers (2 points for each correct answer).
2 points (total) if there is one mistake.
0 points if there are more than one mistakes.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

2.7. Determine the structures of M–U.

M N

4 points. 4 points.

The following tautomer will receive full points: The following tautomer will receive full points:

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

O and P Q

2 points.

and

6 points (3 points for each isomer)

R S

3 points.
3 points.

3 points will be given for the following answers:

T U

2 points.

4 points.

2 points for the following answer:

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

Problem 3 Question 3.1 3.2 3.3 3.4 3.5 3.6 3.7 Total
8% of the total Points 8 16 4 8 5 5 5 51

Problem 3. (±)-Coerulescine

A spiro compound is typically an organic compound containing rings linked together by one
common atom (spiroatom) as carbon atom with bold in figure below. The spiro[pyrrolidin-
3,3′-oxindole] ring system is a structural framework incorporated in several cytostatic
alkaloids and unnatural compounds. Coerulescine (1) and horsfiline are the simplest prototype
members of this subfamily that can be synthesized by the route shown below.

Claisen rearrangement, which is a [3,3]-sigmatropic rearrangement, is a powerful carbon–

carbon bond-forming reaction in which an allyl vinyl ether is converted thermally to an
unsaturated carbonyl compound as shown in the Scheme below. When compound A is heated,
it undergoes Claisen rearrangement to give carbonyl compound B.

For this entire task, your answers can be given without any stereochemical details.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

3.1. Draw the structures of A and B.

• A is an inseparable mixture of cis/trans isomers.

• B has IR absorption at 1726 cm–1.

3.2. Draw structures for C, D, E, and F.

• D–F have a bicyclic structure.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

3.3. Choose the correct order of steps for the transformation of F to G.

☐ Imine formation, then reduction, then amidation

☐ Amidation, then imine formation, then reduction
☐ Reduction, then amidation, then imine formation

3.4. Draw structures for G and H (both spiro compounds).

3.5. Draw the structure of the intermediate produced by treatment with n-BuLi in the step H
→ coerulescine (1).

Coerulescine (1), on treatment with N-bromosuccinimide (NBS), gives the bromo derivative,
which upon heating with sodium methoxide in the presence of cuprous iodide gives horsfiline
(I) in 60% yield.

3.6. Choose the correct structure for compound I consistent with the following selected 1H-
NMR data: δ 7.05 (d, J = 1.4 Hz, 1H), 6.78 (d, J = 8.0 Hz, 1H), 6.72 (dd, J = 8.0, 1.4 Hz, 1H)
ppm.

☐ ☐ ☐ ☐

3.7. When the allyl ether of 2 naphthol is heated a sigmatropic rearrangement is initiated.
Write the structure of major product isolated from this reaction.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

Solution:

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

3.1. Draw the structures of A and B.

A B

4 points.
4 points.

3.2. Draw structures for C, D, E, and F.

C D

4 points.
4 points.

E F

4 points. 4 points.

3 points will be given for the following answer: 4 points will be given for the following answer:

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

3.3. Choose the correct reaction order for the transformation of F to G.

☒ Imine formation, then reduction, then amidation

☐ Amidation, then imine formation, then reduction 4 points for correct answer.
☐ Reduction, then amidation, then imine formation 0 points for incorrect answer.

3.4. Draw structures for G and H.

G H

4 points. 4 points.

3.5. Draw the structure of the intermediate for the reaction with n-BuLi in the step H →
coerulescine.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

5 points for the correct structure.

3.6. Choose the correct structure for compound I consistent with the following selected 1H-
NMR data: δ 7.05 (d, J = 1.4 Hz, 1H), 6.78 (d, J = 8.0 Hz, 1H), 6.72 (dd, J = 8.0, 1.4 Hz, 1H)
ppm.

5 points.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

☐ ☒ ☐ ☐
5 points for correct (second structure) answer.
2 points for third structure.
0 points for incorrect answer.

3.7. When the allyl ether of 2 naphthol is heated a sigmatropic rearrangement is initiated.
Write the structure of major product isolated from this reaction.

5 points for the correct identification of major product.

3 points for keto-form (enone) of major product structure.
2 points for minor product structure.
1 points for keto-form (enone) of minor product structure.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

Problem 4 Question 4.1 4.2 4.3 4.4 4.5 4.6 4.7 Total
10% of the
total Points 12 6 6 16 9 9 8 64

Problem 4. Symmetry Does Matter!

There are numerous reactions in organic chemistry that proceed through cyclic transition
states and these are classified as pericyclic reactions. Woodward–Hoffmann rules, developed
by Robert B. Woodward and Roald Hoffmann, are used to rationalize stereochemical aspects
and the activation energy of pericyclic reactions.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

Woodward–Hoffmann rules
Electrocyclic reactions Cycloadditions
Number of Photochemical Photochemical
Thermal () Thermal ()
electrons (h) (h)
4n Conrotatory (con) Disrotatory Disfavored Favored
(n = 1, 2, ..)
4n+2 Conrotatory
Disrotatory (dis) Favored Disfavored
(n = 1, 2, ..)

4.1. Fill in the table for reactions (i)–(iii) or products 2–5:

Reaction Product [? + ?] cycloaddition  or h

i 2
ii 3
4
iii
5
There are three possible benzotropone isomers. Although two of the benzotropone isomers
were isolated, 3,4-benzotropone (1) has not been isolated. Its instability is attributed to the o-
quinoidal structure of 1 because it has no sextet electron system in the benzene ring.

13
4.2. Draw the structures of stable benzotropone isomers A (with 6 signals in its C-NMR)
and B (with 11 signals in its 13C-NMR).

4.3. When the following tetraene is reacted under photochemical conditions, symmetry-
allowed product(s) of three different ring sizes can form according to the Woodward–
Hoffmann rules. Tick the correct answer in each row.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

☐ ☐

☐ ☐

☐ ☐

Prof. Dr. Aziz Sancar

The Nobel Prize in Chemistry 2015 was awarded jointly to the Turkish scientist Aziz Sancar,
Swedish scientist Tomas Lindahl, and American scientist Paul Modrich for their “mechanistic
studies of DNA repair”. Pyrimidine bases found in DNA may undergo a photochemical [2+2]-
cycloaddition reaction (see above figure) with UV light that reaches a person’s skin, causing
damage to DNA, which may ultimately lead to skin cancer. The research by Professor Aziz
Sancar focused on the DNA repair mechanism for this type of damage.

Thymine (T) is one of the nucleobases that can undergo such a photochemical reaction with
UV light. Let us assume that we have a solution of free thymine that was subjected to UV
irradiation.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

4.4. Considering stereochemistry, draw the structures of all possible products of this reaction
between two free thymine (T) molecules. Circle the compound(s) which is/are chiral.
Drawing only one enantiomer of an enantiomeric pair is sufficient. Please note that only C=C
bonds participate in this reaction.

A broad range of halogenated derivatives of norbornadiene (N) are known in the literature.
Tribromo-norbornadiene (C7H5Br3) has six achiral isomers. Three of these isomers (6, 7, and
8) are given below.

13
4.5. How many signals do you expect from the C-NMR spectra of 6, 7, and 8? Fill in the
following boxes.

6 7 8

4.6. Draw structures of the remaining achiral tribromo-norbornadiene (C7H5Br3) isomers (C,
D, and E) in addition to 6–8 over the given figures in the boxes.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

C D E

The NMR spectrum of ether 9 is complex. Two MeO– groups are different as are all the
hydrogen atoms on the rings. However, diphenol 10 has a very simple NMR spectrum and
there are only three types of protons (marked as a, b, and c). A reasonable average structure
responsible for all resonance structures and its symmetry is shown as 11.

4.7. How many signals do you expect from the 13C- and 1H-NMR spectra of 12 and 13?

Solution:

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

4.1. Fill in the table for reactions (i)–(iii) or products 2–5:

Reaction Product [? + ?] cycloaddition  or h

i 2 [10 + 10] ([6 + 6] is also h
acceptable).
1 point.
2 points.
ii 3 [8 + 2] ([4 + 2] is also 
acceptable).
1 point.
2 points.
4 [10 + 8] ([6 + 4] is also 
acceptable).
1 point.
2 points.
iii
5 [10 + 8] ([6 + 4] is also 
acceptable).
1 point.
2 points.

13
4.2. Draw the structures of stable benzotropone isomers A (with 6 signals in its C-NMR)
and B (with 11 signals in its 13C-NMR).

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

A B

3 points.
3 points.

4.3. When the following tetraene is reacted under photochemical conditions, symmetry-
allowed product(s) can form according to the Woodward–Hoffmann rules. Tick the correct
answer(s).

☐ ☒

☒ ☐

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

☒ ☐

6 points if all the answers are correct.

2 points if there is one mistake.
0 points if there is more than one mistake.

4.4. Considering stereochemistry, draw the structures of all possible products of this
reaction. Circle the compound(s) which is/are chiral. Drawing only one enantiomer of an
enantiomeric pair is sufficient. Please note that only C=C bonds participate in
this reaction.

3 points for each correct structure (12 points in total).

0 points for each structure when there is missing stereochemical information.

4 points (in total) for the correct determination of chirality for the two chiral compounds (2 points
each).
2 points if there is one mistake in the determination of chirality.
0 points if there is more than one mistake in the determination of chirality.

13
4.5. How many signals do you expect from the C-NMR spectra of 6, 7, and 8? Fill in the
following boxes.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

6 7 8

13
4 signals in 13C-NMR
5 signals in C-NMR 13
4 signals in C-NMR 3 points.
3 points. 3 points.

4.6. Draw open structures of the remaining achiral (meso) tribromo-norbornadiene (C7H5Br3)
isomers (C, D, and E) in addition to 6–8 over the given figures in the boxes.

C D E

3 points. 3 points.
3 points.

4.7. How many signals do you expect from the 13C- and 1H-NMR spectra of 12 and 13?

12 13

4 signals in 13C-NMR (2 points). 10 signals in 13C-NMR (2 points).

2 signals in 1H-NMR (2 points). 5 signals in 1H-NMR (2 points).

Problem 5 Question 5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 Total
14% of the total Points 13 13 15 8 12 10 17 12 100

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

Problem 5. Konya, Carrot, Beta-Carotene, Vitamin-A, Immune

System, Vision

Mevlana (Rumi) was a great mystic and Sufi poet who lived out his days in Konya in the 13 th
century. The indirect relevance of Konya to chemistry is that the city provides 65% of the
country’s carrot production, from which one of the essential vitamins (vitamin A) is obtained.

Carrot is an important source of β-carotene, which gives the vegetable its orange color. This
molecule is a red-orange pigment naturally found in plants and fruits and is a provitamin A
carotenoid. It is converted to vitamin A, which is essential for normal growth and
development, the immune system, and vision function.

Figure 1. Ball and stick representation of the structure of β-carotene. The gray and white
spheres represent the carbon and hydrogen atoms, respectively. The numbered carbon atoms
belong to the linear conjugated π-segment of the molecule.

β-Carotene has an extended polyene chain of 22 carbon atoms. It is a conjugated π-system,

having alternating single and double bonds. Its experimental maximum absorption wavelength
(λmax) is 455 nm. We assume that all the bonds between C1 and C22 are conjugated bonds.
There are 22 π-electrons in the molecule (Figure 1).

To a crude approximation, the electrons in the C-2pz orbitals, which are perpendicular to the
molecular plane, are assumed to move along the entire molecule, without interacting with each
other. They are like independent particles confined in a molecule moving along the x-axis in
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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

one dimension. These characteristics of π-electrons make them eligible for being treated by
the simplest model called the particle in one-dimensional box model.

The wave function and the energies of the quantized levels for an electron moving in a one-
dimensional box with infinite potential walls are given as follows:
2 𝑛𝜋𝑥
𝛹𝑛 (𝑥) = √ sin Eq.1
𝐿 𝐿
where n is the quantum number, n=1,2,3,4,…. ∞, and L is the box length.
𝑛2 ℎ 2
𝐸𝑛 = Eq.2
8𝑚𝑒 𝐿2

In two dimension, within the framework of independent particle approximation, the

wavefunction is expressed as a product of one-dimensional wavefunctions, and the energy is
expressed as a sum of one-dimensional energies. The energy levels of the two dimensional
rectangular box is given as follows:
𝑛𝑥 2 𝑛𝑦 2 ℎ2
𝐸𝑛𝑥,𝑛𝑦 = [ 2 + 2] { } Eq. 3
𝐿𝑥 𝐿𝑦 8𝑚
𝑒
where nx, ny are the quantum numbers and they are positive integers. Lx, Ly are the dimensions
of the box in the 2D model. They are positive numbers.

5.1. Which two of the sentences given below are correct? Tick only one answer which
includes correct sentences in your answer sheet.

The β-carotene molecule is orange in color because

i) it absorbs in the visible region of the electromagnetic spectrum.

ii) HOMO →LUMO transition occurs by absorption of IR photon.

iii) the spacing between the 22nd and the 23rd energy levels is equal to the energy of the IR
photon at the orange wavelength.
iv) it absorbs green/blue light and it transmits red/yellow color.
v) it absorbs in the UV-Vis region since the molecule has no net dipole moment.

Although it is highly unrealistic, let us assume that the conjugated segment of the molecule is
linear and treated with the particle in a one-dimensional box model as shown in figure 2. In
this case, the length of the box can be approximated as L=1.40×nC (in Å), where nC is the
number of carbon atoms in the conjugated segment.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

Use this information to answer the questions 5.2–5.6.

Figure 2. Schematic representation of the conjugated line segment made up carbon atoms of
β-carotene in a one-dimensional box of length L.

5.2. Calculate the energies (in J) of the lowest two energy levels
5.3. Draw the wavefunctions of the lowest two energy levels with proper labelling the x-axis.
5.4. Sketch the energy level diagram up to n = 4 showing the relative spacing.
5.5. What is the total π-energy (in J) of the molecule?
5.6. Calculate the wavelength (in nm) at which the transition between the highest occupied
and lowest unoccupied energy levels occurs.
Use the particle in a two-dimensional box model to answer questions 5.7–5.8.

Figure 3. Schematic representation of the conjugated carbon atoms of β-carotene in a two-

dimensional box.

Assume that the conjugated segment is made up of conjugated bonds that are all-trans to each
other. The motion of the π-electrons is studied in the two-dimensional rectangular box with
the dimensions Lx = 26.0 Å, Ly = 3.0 Å (Figure 3).

5.7. Calculate the energies (in J) of the highest occupied and the lowest unoccupied energy
levels and the wavelength (in nm) at which the transition between these energy levels occurs.
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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

5.8. What should be the Lx value (in Å) in order for the molecule to absorb light at the
experimental λmax=455 nm if Ly is kept constant at 3.0 Å. (Assume that the quantum numbers
for homo and lumo are the same as in the question 5.7.)

Solution:

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

5.1. Which two of the sentences given below are correct? Tick only one answer which
includes correct sentences in your answer sheet.
☐ a) i and ii ☐ b) i and iii ☒ c) i and iv ☐ d) i and v
☐ e) ii and iii ☐ f) ii and iv ☐ g) ii and v ☐ h) iii and iv
☐ j) iii and v ☐ k) iv and v
13 points for the correct answer.

5.2. Calculate the energies (in J) of the lowest two levels.

Calculation:
𝐿 = 1.40 × 22 = 30.8 Å

𝑛2 ℎ 2
𝐸𝑛 = 8𝑚 2
= 𝑛2 (6.351 × 10–21) J E1 = 6.351 × 10–21 J E2 = 2.540 × 10–20 J
𝑒𝐿

13 points. 3 points for correct box length, 5 points for each correct energy value.
No partial credit will be given.

5.3. Draw the wavefunctions of the lowest two energy levels with proper labelling the x-axis.

15 points. 3 points for labelling the x-axis and 6 points for the correct drawing of the wavefunctions.
No partial credit will be given.

5.4. Sketch the energy level diagram up to n = 4 showing the relative spacing.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

8 points. The lowest 4 energy levels, the energy scale and the relative spacing between the
energy levels must be shown.

5.5. Calculate the total π-energy (in J) of the molecule?

Calculation:
𝒐𝒄𝒄𝒖𝒑𝒊𝒆𝒅 𝒍𝒆𝒗𝒆𝒍𝒔

𝑬𝝅(𝒕𝒐𝒕𝒂𝒍) = 𝟐 ∑ 𝑬𝒊
𝒊=𝟏
Eπ (total) = 2 × (E1+E2+E3+E4+E5+E6+E7+E8+E9+E10+E11) = 6.427 × 10–18 J

12 points for the correct answer. 4 points if the multiplication by 2 is forgotten.

No partial credit will be given.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

5.6. Calculate the wavelength (in nm) at which the transition between the highest occupied
and lowest unoccupied energy levels occurs.

Calculation:
The quantum numbers for the highest occupied and lowest unoccupied energy levels are 11
and 12, respectively.
𝟏𝟐𝟐 𝒉𝟐 𝟏𝟏𝟐 𝒉𝟐 𝟐𝟑𝒉𝟐 𝒉𝒄
∆𝑬 = 𝑬𝟏𝟐 − 𝑬𝟏𝟏 = 𝑬𝒏 = 𝟖𝒎 − 𝟖𝒎 = 𝟖𝒎 = then,
𝒆 𝑳𝟐 𝒆𝑳
𝟐
𝒆𝑳
𝟐 𝝀

𝟖𝒎𝒆 𝒄𝑳𝟐
𝝀= =1360 nm
𝟐𝟑𝒉

10 points for the correct answer.

If wavelength expression is written correctly but the result is calculated wrongly then 3 points will be
deducted.
1 point will be deducted for incorrect unit.

5.7. Calculate the energies (in J) of the highest occupied and the lowest unoccupied energy
levels and the wavelength (in nm) at which the transition between these energy levels occurs.

Calculation:

𝒏𝒙 𝟐 𝒏𝒚 𝟐 𝒉𝟐 𝒏 𝟐 𝒏𝒚 𝟐
𝑬𝒏𝒙,𝒏𝒚 = [ 𝟐 + 𝟐 ] {𝟖𝒎 } = [𝟐𝟔𝒙 𝟐 + ] 6.025 × 10–18 J, where Lx and Ly should be in Å.
𝑳𝒙 𝑳𝒚 𝒆 𝟑𝟐

The quantum numbers and the energies of the highest occupied and the lowest
unoccupied energy levels are:

nx = 11, ny = 1 and nx = 12, ny = 1

𝟏𝟏𝟐 𝟏𝟐
E11,1 = [𝟐𝟔𝟐 + 𝟑𝟐 ] 6.025 × 10–18 J = 17.48 × 10–19 J

𝟏𝟐𝟐 𝟏𝟐
E12,1 = [𝟐𝟔𝟐 + 𝟑𝟐 ] 6.025 × 10–18 J = 19.53× 10–19 J

The transition wavelength is:

ΔE = E12,1 – E11,1= (19.53 – 17.48) × 10–19 J = 2.050 × 10–19 J

ΔE = Ephoton = (hc)/λ and λ = (hc)/ΔE = 9.69 × 10–7 m, λ = 969 nm

17 points for the correct answer.

12 points for correct energies
5 points for the correct wavelength
1 point will be deducted for incorrect unit.
No partial credit will be given.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

5.8. What should be the Lx value (in Å) in order for the molecule to absorb light at the
experimental λmax if Ly is kept constant at 3.0 Å. (Assume that the quantum numbers for homo
and lumo are the same as in the question 5.7.)

Calculation:

𝟏𝟐𝟐 𝟏𝟐 𝟏𝟏𝟐 𝟏𝟐 𝒉𝟐 𝟐𝟑 𝟏.𝟑𝟖𝟔 × 𝟏𝟎−𝟏𝟖

𝜟𝑬 = [ 𝟐 + 𝟐 − 𝟐 − 𝟐 ] {𝟖𝒎 } = [ 𝟐 ] 6.025 × 10–18 = (Lx is in Å)
𝑳𝒙 𝑳𝒚 𝑳𝒙 𝑳𝒚 𝒆 𝑳𝒙 𝑳𝒙 𝟐

𝟏.𝟑𝟖𝟔 × 𝟏𝟎−𝟏𝟖 𝟔.𝟔𝟐𝟔 × 𝟏𝟎−𝟑𝟒 × 𝟐.𝟗𝟗𝟖 × 𝟏𝟎𝟖

ΔE = Ephoton = (hc)/λ → 𝟐 =
𝑳𝒙 𝟒𝟓𝟓 × 𝟏𝟎−𝟗

Lx = 1.782 × 10–9 m Lx = 17.82 Å

12 points for the correct answer.

No partial credit will be given.
1 point will be deducted for incorrect unit.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

Question 6.1 6.2 6.3 6.4 6.5 6.6 6.7 6.8 Total
Problem 6 Points 5 12 6 3 6 6 5 3 80
12% of the total Question 6.9 6.10 6.11 6.12 6.13
Points 8 6 6 8 6

Problem 6. Thermodynamics through an Interstellar Journey

Part 1
In a hypothetical universe, an unknown amount of diborane participates in the following
reaction:

B2H6(g) + 6 H2O(l) → 2 H3BO3(s) + 6 H2(g)

Assume that in this hypothetical universe, H3BO3(s) obtained from this reaction was
completely sublimed at 300 K. The necessary energy for sublimation was obtained through
work released by one cycle of an ideal heat engine in which one mole of monoatomic perfect
gas flows through the cycle described in the pressure (p) – volume (V) diagram below:

• A→B; isothermal reversible expansion receiving 250 J by heat transfer (qH) at a

temperature of 1000 K (TH) from a hot source.
• B→D; reversible adiabatic expansion.
• D→C; isothermal reversible compression at a temperature of 300 K (TC) releasing
some amount of heat (qC) to a cold sink.
• C→A; reversible adiabatic compression.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

After heat transfers, the remaining energy is released as work (w). Also, qH and qC are related
to TC and TH as follows:

|𝑞𝐻 | 𝑇𝐻
=
|𝑞𝐶 | 𝑇𝐶

The efficiency of the cycle can be found by work released by cycle (w) divided by heat
absorbed by cycle (qH).

You are provided with the change in enthalpies of the following reactions at 300 K.

(1) B2H6(g) + 6 Cl2(g) → 2 BCl3(g) + 6 HCl(g) 𝚫𝐫 𝐇(𝟏) = −𝟏𝟑𝟐𝟔 𝐤𝐉 𝐦𝐨𝐥−𝟏

(2) BCl3(g) + 3 H2O(l) → H3BO3(g) + 3 HCl(g) 𝚫𝐫 𝐇(𝟐) = −𝟏𝟏𝟐. 𝟓 𝐤𝐉 𝐦𝐨𝐥−𝟏

(3) B2H6(g) + 6 H2O(l) → 2 H3BO3(s) + 6 H2(g) 𝚫𝐫 𝐇(𝟑) = −𝟒𝟗𝟑. 𝟒 𝐤𝐉 𝐦𝐨𝐥−𝟏

1 1
(4) 2 H2(g) + Cl2(g) → HCl(g) 𝚫𝐫 𝐇(𝟒) = −𝟗𝟐. 𝟑 𝐤𝐉 𝐦𝐨𝐥−𝟏
2

6.1. Calculate the molar enthalpy of sublimation (in kJ mol-1) for H3BO3 at 300 K.

6.2. Calculate the ΔrU (internal energy) in terms of kJ mol-1 at 300 K for the reactions (2) and
(4) given above (assume ideal gas behavior for each gaseous species in each reaction).

6.3. Calculate the amount of overall work produced by a heat engine (|w|) in terms of J and
the amount of overall heat released to the cold sink (|qC|) in terms of J.

6.4. Calculate the efficiency of the heat engine described above.

6.5. Calculate the entropy change (ΔS) for A→B and D→C processes in the heat engine in
terms of J K −1.

6.6. Calculate the Gibbs energy change (ΔG) in terms of J for A→B and D→C processes in
the heat engine.

6.7. Calculate the ratio of pressure at point A to the pressure at point B in the cycle (standard
pressure: 1 bar).

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

6.8. Calculate the amount of H2(g) (in moles) produced according to the reaction given at the
beginning of the task for one cycle of the engine.

Part 2
Interstellar journeys can be done by using diborane as rocket fuel. Combustion of diborane is
shown below:

B2H6 (g)+ 3O2 (g) → B2O3 (s) + 3H2O (g)

Combustion of diborane is experimented in a 100 L closed container at different temperatures

and the equilibrium amounts were recorded.

8930 K 9005 K
B2H6(g) 0.38 mol 0.49 mol
H2O(g) 0.20 mol 0.20 mol

Partial pressure of O2 (g) was stabilized to 1 bar and kept constant at all conditions. Assume
that in this hypothetical universe; ΔrS° and ΔrH° are independent of temperature, the standard
molar entropy (S°) of B2O3(s) does not change with pressure, all the gas species behave as an
ideal gas, and all species remain in the same phase, without any further decomposition before
or after reaction, at all temperatures then:

6.9. Calculate Kp (pressure based equilibrium constant) at 8930 K and 9005 K.

6.10. Calculate ΔrG° of the reaction in terms of kJ mol-1 at 8930 K and 9005 K. (If you failed
to find Kp, please use Kp (8930 K) =2, Kp (9005 K) = 0.5)

6.11. Calculate ΔrG°(in terms of kJ mol−1 ), ΔrH° (in terms of kJ mol−1 ), and ΔrS°
(in terms of J mol−1 K −1)of the combustion reaction at 298 K. (If you failed to find Kp, please
use Kp (8930 K) =2, Kp (9005 K) = 0.5)

6.12. Tick the correct answer in the table by determining whether combustion reactions are
favored or not at given T below under standard pressure (1 bar).

favored Unfavored
298 K ☐ ☐
8930 K ☐ ☐
9005 K ☐ ☐
9100 K ☐ ☐

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

6.13. Calculate the ΔfH ( kJ mol–1) and S°( kJ mol–1 K–1) of H2O(g) using the values given in
the table below. (ΔfH = enthalpy of formation, S° = standard entropy)

(If you fail to find ΔrH° and ΔrS° of the combustion, please use ΔH° = 1000 kJ mol-1, ΔS°=
150 J K-1 mol-1)

ΔHf (298 K) S° (298 K)

B2H6 (g) 36.40 kJ mol–1 0.23 kJ mol–1 K–1
O2 (g) 0.00 kJ mol–1 0.16 kJ mol–1 K–1
B2O3 (s) –1273 kJ mol–1 0.05 kJ mol–1 K–1

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

Solution:

6.1. Calculate the molar enthalpy of sublimation (in kJ mol-1) for H3BO3 at 300 K.

Calculation:
Hess rule:
𝜟𝑯(𝟑) – 𝟐 × 𝜟𝑯(𝟐) + 𝟏𝟐 × 𝜟𝑯(𝟒)– 𝜟𝑯(𝟏) = − 𝟐 × 𝜟𝑯𝒔𝒖𝒃 (𝑯𝟑 𝑩𝑶𝟑 )
𝜟𝑯𝒔𝒖𝒃 (𝑯𝟑 𝑩𝑶𝟑 ) = 𝟐𝟓 𝒌𝑱 𝒎𝒐𝒍−𝟏

5 points.

2 points will be deducted if student forgets to divide by 2 in last step

3 points will be deducted if Hess rule is applied correctly, but the answer is incorrect due to
miscalculation.
If the answer is incorrect due to any other reason, Zero point will be given
If any other unit than asked unit is used in the answer, 0.5 points will be deducted.

6.2. Calculate the ΔrU (internal energy) in terms of kJ mol-1 at 300 K for the reactions (2) and
(4) given above (assume ideal gas behavior for each gaseous species in each reaction).

Calculation:

𝛥𝑈 = 𝛥𝐻 – 𝛥(𝑃𝑉) = 𝛥𝐻 – (𝛥𝑛𝑔𝑎𝑠 )𝑅𝑇

𝑅𝑇 = 8.3145 𝐽 𝑚𝑜𝑙 −1 𝐾 −1 × 300 𝐾 = 2.494 𝑘𝐽 𝑚𝑜𝑙 −1
𝛥𝑈 = 𝛥𝐻 – (𝛥𝑛𝑔𝑎𝑠 ) × 2.494 𝑘𝐽 𝑚𝑜𝑙 −1
𝛥𝑈(2) = −112.5 𝑘𝐽 – (3 𝑚𝑜𝑙) × 2.494 𝑘𝐽 𝑚𝑜𝑙 −1 = −120.0 𝑘𝐽
𝛥𝑈(4) = −92.3 𝑘𝐽 – (0) × 2.494 𝑘𝐽 𝑚𝑜𝑙 −1 = −92.3 𝑘𝐽

6x2=12 points.
For each calculation considering that the logic for solving this question is correctly established;
1 point will be deducted if the answer is not correct in due to miscalculation.
If the logic for solving this question is not established correctly, no points will be given.
If any other unit than asked unit is used in the answer, 0.5 points will be deducted.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

6.3. Calculate the amount of work produced by a heat engine (w) in terms of J and the
amount of heat released to the cold sink (qC) in terms of J.

Calculation:

|𝑞𝐻 | 𝑇𝐻 250 𝐽 1000 𝐾

= → = → |𝑞𝐶 | = 75 𝐽
|𝑞𝐶 | 𝑇𝐶 𝑞𝐶 300 𝐾
|𝑤| = 𝑞𝐻 − |𝑞𝐶 | = 250 𝐽 − 75 𝐽 = 175 𝐽

For w= 3 points, for 3 qc=3 points, in total 6 points.

If qc is incorrect due to miscalculation, 1 point will be deducted.
If w is incorrect due to miscalculation, 1 point will be deducted.
If w is incorrect due to incorrect qc calculated in this section, zero point will be deducted.
If w is incorrect due to incorrect qc calculated in this section and there are miscalculations, 1 point will
be deducted.
If any other unit than asked unit is used in the answer, 0.5 points will be deducted.

6.4. Calculate the efficiency of the heat engine described above.

Calculation:

|𝑤| 175 𝐽
𝒆𝒇𝒇𝒊𝒄𝒊𝒆𝒏𝒄𝒚 = = = 𝟎. 𝟕𝟎
|𝑞𝐻 | 250 𝐽

3 points.
If efficiency is in correct due to miscalculation, 1 point will be deducted.
If efficiency is incorrect due to incorrect w obtained in 6.3, zero point will be deducted.
If efficiency is incorrect due to incorrect w obtained in 6.3 and there are miscalculations, 1
point will be deducted.
If any unit is used in the answer, 0.5 points will be deducted.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

6.5. Calculate the entropy change (ΔS) for A→B and D→C processes in the heat engine in
terms of J K −1.

Calculation:

𝑑𝑞𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒
𝛥𝑆 =
𝑇

For A→B
250 𝐽
𝜟𝑺𝑨→𝑩 = = 𝟎. 𝟐𝟓 𝑱 𝑲−𝟏
1000 𝐾

For D→C
−75 𝐽
𝜟𝑺𝑫→𝑪 = = − 𝟎. 𝟐𝟓 𝑱 𝑲−𝟏
300 𝐾
3 points for A→B, 3 points for D→C, in total 6 points.
If 𝜟𝑺𝑨→𝑩 is incorrect due to miscalculation, 1 points will be deducted.
Since qH is provided in the question, If 𝜟𝑺𝑨→𝑩 is incorrect due to any other reason, no points
will be given
If 𝜟𝑺𝑫→𝑪 is incorrect due to miscalculation, 1 points will be deducted.
If 𝜟𝑺𝑫→𝑪 is incorrect due to incorrect qc obtained in 6.3, Zero point will be deducted.
However, if there are miscalculations, 1 points will be deducted.
If any other unit than asked unit is used in the answer, 0.5 points will be deducted.

6.6. Calculate the Gibbs energy change (ΔG) in terms of J for A→B and D→C processes in
the heat engine.

Calculation:

𝛥𝐺 = 𝛥𝐻 – 𝑇𝛥𝑆, 𝑓𝑜𝑟 𝑖𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙 𝑝𝑟𝑜𝑐𝑒𝑠𝑠𝑒𝑠 𝛥𝐻 = 0, 𝑡ℎ𝑒𝑛 𝛥𝐺 = – 𝑇𝛥𝑆

∆𝑮𝑨→𝑩 = − 0.25 𝐽 𝐾 −1 × 1000 𝐾 = − 𝟐𝟓𝟎 𝑱

∆𝑮𝑫→𝑪 = −(−0.25 𝐽 𝐾 −1 ) × 300 𝐾 = 𝟕𝟓 𝑱

3 points for A→B, 3 points for D→C, in total 6 points.

If ∆𝑮𝑨→𝑩 is incorrect due to miscalculation, 1 points will be deducted.
If ∆𝑮𝑫→𝑪 is incorrect due to miscalculation, 1 points will be deducted.
If ∆𝑮𝑨→𝑩 is incorrect due to incorrect ∆𝑺𝑨→𝑩 obtained in 6.5, zero point will be deducted. But
if there are miscalculations, 1 points will be deducted.
If ∆𝑮𝑫→𝑪 is incorrect due to incorrect ∆𝑺𝑫→𝑪 obtained in 6.5, zero point will be deducted. But
if there are miscalculations, 1 points will be deducted.
If 𝛥𝐻 is not considered to be zero, no points will be given.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

If any other unit than asked unit is used in the answer, 0.5 points will be deducted.

6.7. Calculate the ratio of pressure at point A to the pressure at point B in the cycle.

Calculation:

𝑑𝑞𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑉𝐵
∆𝑆 = = 𝑛𝑅𝑙𝑛
𝑇 𝑉𝐴
𝑉
0.25 𝐽 𝐾 = 1 𝑚𝑜𝑙 × 8.314 𝐽 𝑚𝑜𝑙 −1 𝐾 −1 𝑙𝑛 𝑉𝐵
−1
𝐴
𝑉𝐵 𝑉𝐵
𝑙𝑛 = 0.03007 → = 1.03
𝑉𝐴 𝑉𝐴
𝑉𝐵 𝑃𝐴 𝑷𝑨
= → = 𝟏. 𝟎𝟑
𝑉𝐴 𝑃𝐵 𝑷𝑩

5 points.
𝑉𝐵
If student can find up to 𝑙𝑛 with correct value and calculate no further, 3 points will be
𝑉𝐴
deducted
𝑉𝐵
If student can find up to 𝑙𝑛 with incorrect value and calculate no further, 3.5 points will be
𝑉𝐴
deducted
𝑉𝐵
If student can find up to with correct value and calculate no further, 2 points will be deducted
𝑉𝐴
𝑉𝐵
If student can find up to with incorrect value and calculate no further, 2.5 points will be
𝑉𝐴
deducted
𝑃
If student gets incorrect 𝑃𝐴 due to miscalculation, 1.5 points will be deducted.
𝐵
If student uses incorrect ∆𝑆 obtained from 6.5 or given in the question, no points will be
deducted.
If any unit is used in the answer, 0.5 points will be deducted.

6.8. Calculate the amount of H2(g) (in moles) produced during the formation of boric acid.
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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

Calculation:

𝟎. 𝟏𝟕𝟓 𝒌𝑱
= 𝟕 × 𝟏𝟎−𝟑 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝑯𝟑 𝑩𝑶𝟑 𝒊𝒔 𝒔𝒖𝒃𝒍𝒊𝒎𝒂𝒕𝒆𝒅
𝟐𝟓 𝒌𝑱 𝒎𝒐𝒍−𝟏

(𝟕 × 𝟏𝟎−𝟑 ) × 𝟑 = 𝟐𝟏 × 𝟏𝟎−𝟑 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝑯𝟐 𝒊𝒔 𝒈𝒆𝒏𝒆𝒓𝒂𝒕𝒆𝒅

3 points.
If student gives incorrect answer due to miscalculation in any step, no points will be given.
If student gives incorrect answer due to incorrect w obtained in 6.3, no points will be deducted. If there
are miscalculations, the grading scheme given above will be applied.
If student gives incorrect answer due to incorrect sublimation enthalpy obtained in 6.1, no points will
be deducted. If there are miscalculations, the grading scheme given above will be applied.
If any other unit than asked unit is used in the answer, 0.5 points will be deducted.

6.9. Calculate Kp (pressure based equilibrium constant) at 8930 K and 9005.

Calculation:

𝑛𝑅𝑇 𝑛 × 0.08205 𝐿 𝑎𝑡𝑚 𝑚𝑜𝑙 −1 𝐾 −1 × 𝑇

𝑃𝑉 = 𝑛𝑅𝑇 → 𝑃 = →𝑃=
𝑉 100 𝐿

At 8930 K,
0.38 𝑚𝑜𝑙 × 0.08205 𝐿 𝑎𝑡𝑚 𝑚𝑜𝑙 −1 𝐾 −1 × 8930 𝐾
𝐹𝑜𝑟 𝐵2 𝐻6 (𝑔) → 𝑃𝐵2 𝐻6 (𝑔) = = 2.784 𝑎𝑡𝑚
100 𝐿
= 2.821 𝑏𝑎𝑟
0.20 𝑚𝑜𝑙 × 0.08205 𝐿 𝑎𝑡𝑚 𝑚𝑜𝑙 −1 𝐾 −1 × 8930 𝐾
𝐹𝑜𝑟 𝐻2 𝑂(𝑔) → 𝑃𝐻2 𝑂(𝑔) = = 1.465 𝑎𝑡𝑚
100 𝐿
= 1.484 𝑏𝑎𝑟

At 9005 K,
0.49 𝑚𝑜𝑙 × 0.08205 𝐿 𝑎𝑡𝑚 𝑚𝑜𝑙 −1 𝐾 −1 × 9005 𝐾
𝐹𝑜𝑟 𝐵2 𝐻6 (𝑔) → 𝑃𝐵2 𝐻6 (𝑔) = = 3.618 𝑎𝑡𝑚
100 𝐿
= 3.666 𝑏𝑎𝑟

0.20 𝑚𝑜𝑙 × 0.08205 𝐿 𝑎𝑡𝑚 𝑚𝑜𝑙 −1 𝐾 −1 × 9005 𝐾

𝐹𝑜𝑟 𝐻2 𝑂(𝑔) → 𝑃𝐻2 𝑂(𝑔) = = 1.478 𝑎𝑡𝑚
100 𝐿
= 1.498 𝑏𝑎𝑟
(𝑃𝐻2𝑂(𝑔) )3 (1.484)3
𝑲𝒑 𝒂𝒕 𝟖𝟗𝟑𝟎 𝑲 = = = 𝟏. 𝟏𝟓𝟗
(𝑃𝑂2(𝑔) )3 × 𝑃𝐵2𝐻6 (𝑔) (1)3 × 2.821
(𝑃𝐻2𝑂(𝑔) )3 (1.498)3
𝑲𝒑 𝒂𝒕 𝟗𝟎𝟎𝟓 𝑲 = = = 𝟎. 𝟗𝟏𝟕
(𝑃𝑂2(𝑔) )3 × 𝑃𝐵2𝐻6 (𝑔) (1)3 × 3.666

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

2x4 points for Kp.

For each calculation of Kp,
If answer is incorrect due to miscalculation, 1 point will be deducted.
If answer is incorrect due to incorrect 𝑃𝐵2 𝐻6 (𝑔) calculated in this part, no points will be deducted.
However, if there are miscalculation, 1 point will be deducted.
If answer is incorrect due to incorrect Kp calculated in this part, no points will be deducted.
If answer is incorrect due to miscalculation and incorrect Kp, 1 point will be deducted.

6.10. Calculate ΔrG° of the reaction in terms of kJ mol-1 at 8930 K and 9005 K (use three
decimal places for your result).
(If you failed to find Kp, please use Kp (8930 K) =2, Kp (9005 K) = 0.5)

Calculation:

The equilibrium constant is determined by gaseous species, Kp is going to be used to calculate

ΔG°:

𝛥𝐺° = −𝑅𝑇𝑙𝑛𝐾𝑝

𝚫𝐆° 𝐚𝐭 𝟖𝟗𝟑𝟎 𝐊 = −8.3145 J mol−1 K −1 × 8930 𝐾 𝑙𝑛1.159 = −𝟏𝟎. 𝟗𝟓𝟔 𝒌𝐉 𝐦𝐨𝐥−𝟏

𝚫𝐆° 𝐚𝐭 𝟗𝟎𝟎𝟓 𝐊 = −8.3145 J mol−1 K −1 × 9005 𝐾 𝑙𝑛0.917 = 𝟔. 𝟒𝟖𝟖 𝒌𝐉 𝐦𝐨𝐥−𝟏

3 points for each ΔG°, in total 6 points.

For each ΔG°;
If ΔG° is incorrect due to miscalculation, 1 points will be deducted.
If student uses incorrect value for Kp obtained from 6.9 or provided in this question, no points
will be deducted. If there are miscalculations, if there are miscalculations, 1 point will be
deducted.
If any other unit than asked unit is used in the answer, 0.5 points will be deducted.

6.11. Calculate ΔrG°(in terms of kJ mol−1 ), ΔrH° (in terms of kJ mol−1 ), and ΔrS°
(in terms of J mol−1 K −1)of the combustion reaction at 298 K.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

(If you failed to find Kp, please use Kp (8930 K) =2, Kp (9005 K) = 0.5)

Calculation:

𝛥𝐺° = 𝛥𝐻° − 𝑇𝛥𝑆°

𝛥𝐺°(8930 𝐾) = −10956 𝐽 𝑚𝑜𝑙 −1 = 𝛥𝐻° − 8930 𝐾 × 𝛥𝑆°

𝛥𝐺°(9005 𝐾) = 6488 𝐽 𝑚𝑜𝑙 −1 = 𝛥𝐻° − 9005 𝐾 × 𝛥𝑆°

𝜟𝑺° = −𝟐𝟒𝟗. 𝟏 𝑱 𝒎𝒐𝒍−𝟏 𝑲−𝟏

𝜟𝑯° = −𝟐𝟐𝟑𝟕. 𝟏 𝒌𝑱 𝒎𝒐𝒍−𝟏

𝜟𝑮°(𝟐𝟗𝟖 𝑲) = −2237.1 𝑘𝐽 𝑚𝑜𝑙 −1 − 298 𝐾 × (−0.2491 𝑘𝐽 𝑚𝑜𝑙 −1 𝐾 −1 )

= −𝟐𝟏𝟔𝟐. 𝟗 𝒌𝑱 𝒎𝒐𝒍−𝟏

2 points for ° , 2 points for 𝜟𝑯°, 2 points for 𝜟𝑮°(𝟐𝟗𝟖 𝑲) , in total 6 points.
For ΔS° and ΔH°, if student gives incorrect answer due to miscalculation, 1 point will be deducted.
********************************************************************************
Students may calculate ΔS° after finding ΔH° by using;
∆𝑟 𝐻° ∆𝑟 𝑆°
𝑙𝑛𝐾 = − +
𝑅𝑇 𝑅
If student gives incorrect answer due to miscalculation, 1 point will be deducted.
If student gives incorrect answer due incorrect ΔH° obtained by in this part, zero point will be
deducted. If there are miscalculations, 1 point will be deducted.
********************************************************************************
For ΔG°, if student gives incorrect answer due to miscalculation, 1 point will be deducted.
For ΔG°, if student gives incorrect answer due to incorrect ΔS° obtained in this part, zero point will be
deducted. If there are miscalculations, 1 point will be deducted.
For ΔG°, if student gives incorrect answer due to incorrect ΔH° obtained in this part, zero point will be
deducted. If there are miscalculations, 1 point will be deducted.
For ΔG°, if student gives incorrect answer due to incorrect ΔS° and ΔH° obtained in this part, zero
point will be deducted. If there are miscalculations, 1 point will be deducted.

If student uses any incorrect value for 𝛥𝐺° and/or Kp obtained from 6.9 and 6.10 or given in this
question, no points will be deducted. If there are miscalculations, If there are miscalculations,
1 point will be deducted.

Students who solved this problem by using;

𝐾2 ∆𝑟 𝐻° 1 1
𝑙𝑛 =− ( − )
𝐾1 𝑅 𝑇2 𝑇1
Correct answers obtained by using this equation will be graded over 6 points with 2 points for 𝜟𝑺° , 2

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

points for 𝜟𝑯°, 2 points for 𝜟𝑮°(𝟐𝟗𝟖 𝑲)

However;
For ΔH°, if student gives incorrect answer due to miscalculation, 1 point will be deducted.
For ΔS°, if student gives incorrect answer due to miscalculation, 1 point will be deducted.
For ΔS°, if student gives incorrect answer due incorrect ΔH° obtained by using equation above, zero
point will be deducted. If there are miscalculations, 1 point will be deducted.
********************************************************************************
Students may calculate ΔS° after finding ΔH° by using;
∆𝑟 𝐻° ∆𝑟 𝑆°
𝑙𝑛𝐾 = − +
𝑅𝑇 𝑅
If student gives incorrect answer due to miscalculation, 1 point will be deducted.
If student gives incorrect answer due incorrect ΔH° obtained by in this part, zero point will be
deducted. If there are miscalculations, 1 point will be deducted.
********************************************************************************
For ΔG°, if student gives incorrect answer due to miscalculation, 1 point will be deducted.
For ΔG°, if student gives incorrect answer due to incorrect ΔH° obtained in this part, zero point will be
deducted. If there are miscalculations, 1 point will be deducted.
For ΔG°, if student gives incorrect answer due to incorrect ΔS° obtained in this part, zero point will be
deducted. If there are miscalculations, 1 point will be deducted.
For ΔG°, if student gives incorrect answer due to incorrect ΔS° and ΔH° obtained in this part, zero
point will be deducted. If there are miscalculations, 1 point will be deducted.
If student uses any incorrect value for 𝛥𝐺° and/or Kp obtained from 6.9 and 6.10 or given in this
question, no points will be deducted. If there are miscalculations, the grading scheme above
will be applied

If any other unit than asked unit is used in the answer, 0.5 points will be deducted.

6.12. Tick the correct answer on the table by determining whether combustion reactions are
favored or not at given T below under standard pressure (1 bar).

Favored Unfavored
298 K ☒ ☐
8930 K ☒ ☐
9005 K ☐ ☒
9100 K ☐ ☒

8 points. Each correct answer is 2 points.

6.13. Calculate the ΔfH ( kJ mol–1) and S°( kJ mol–1 K–1) of H2O(g) using the values given in
the table below. (ΔfH = enthalpy of formation, S° = standard entropy)

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

(If you fail to find ΔrH° and ΔrS° of the combustion, please use ΔH° = 1000 kJ mol-1, ΔS°=
150 J K-1 mol-1)

Calculation:

B2H6 (g)+ 3O2 (g) → B2O3 (s) + 3H2O (g)

∆𝐻° = [∆𝐻𝑓 (𝐵2 𝑂3 (𝑠)) + 3 × ∆𝐻𝑓 (𝐻2 𝑂(𝑔))] − [∆𝐻𝑓 (𝐵2 𝐻6 (𝑔)) + 3 × ∆𝐻𝑓 (𝑂2 (𝑔))]

∆𝑆° = [𝑆°(𝐵2 𝑂3 (𝑠)) + 3 × 𝑆°(𝐻2 𝑂(𝑔))] − [𝑆°(𝐵2 𝐻6 (𝑔)) + 3 × 𝑆°(𝑂2 (𝑔))]

∆𝑯𝒇 (𝑯𝟐 𝑶(𝒈)) = −𝟑𝟎𝟗. 𝟐 𝒌𝑱 𝒎𝒐𝒍−𝟏

𝑺°(𝑯𝟐 𝑶(𝒈)) = 𝟎. 𝟏𝟑𝟕 𝐤𝐉 𝐦𝐨𝐥−𝟏 𝐊 −𝟏

3 points for ∆𝑯𝒇 (𝑯𝟐 𝑶(𝒈)), 3 points for 𝑺°(𝑯𝟐 𝑶(𝒈)), in total 6 points.
If ∆𝑯𝒇 (𝑯𝟐 𝑶(𝒈)) is in correct due to miscalculation, 2 points will be deducted.
If 𝑺°(𝑯𝟐 𝑶(𝒈)) is in correct due to miscalculation, 2 points will be deducted.
No points will be deducted if wrong values are obtained for ∆𝐻° and ∆𝑆° from 6.11 or the
values provided here. If there are miscalculations, 2 points will be deducted for each.

If any other unit than asked unit is used in the answer, 0.5 points will be deducted.

Question 7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9 Total
Problem 7
85
12% of the total Points 4 8 6 8 8 14 19 12 6

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

Problem 7. Phthalocyanines

Emeritus Professor Özer

Bekaroğlu

The term phthalocyanine (Pc) takes its origin from the Greek “naphtha”, which means rock
oil, and “cyanine”, which means dark blue. Turkish scientist Özer Bekaroğlu can be regarded
as the pioneer of Pc chemistry in Turkey.

Metal-free phthalocyanine (1, H2Pc) is a large planar macrocyclic compound with the formula
(C8H4N2)4H2.

7.1. How many π-electrons are there in the bold region of the H2Pc molecule in compound 1
shown above?

Pcs containing one or two metal ions are called metallo-phthalocyanines (MPcs) and they
exhibit different geometries as given above.

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7.2. Complete the table in your answer sheet by determining the coordination number of
central ions in 2–5.

Central ion Copper ion Titanium Silicon ion Cerium ion

ion
Coordination number

7.3. Complete the table in your answer sheet by determining the oxidation number of each
metal (Cu, Ti, and Ce) in 2, 3, and 5.

Metal in compounds 2 3 5
Oxidation number

7.4. Complete the table in your answer sheet by determining the geometry of compounds 2–5.

Geometry Compound

Octahedral

Square prism

Square pyramidal

Square planar

7.5. Complete the table in your answer sheet by determining the magnetic property of
compounds 2–5.

• Use the letter "p" for paramagnetic property and letter "d" for a diamagnetic property.

Compound Magnetic property

7.6. Write the ground-state electron configuration of the silicon (Si) ion in the compound 4
and find all the quantum numbers for the 2p electrons in its ground state.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

Electron configuration:

n l m1 ms

Quantum numbers for 2p electrons:

Metal-free phthalocyanine (1, H2Pc) is commonly formed through the cyclotetramerization of

phthalonitriles. On the other hand, Pcs having different substituents are called asymmetric,
which can be prepared by the statistical cyclization of two different phthalonitriles. This
method has no selectivity and the product is a mixture of all possible isomers.
7.7. Draw the possible products that may occur in the statistical cyclization method by using
F and G. If there are any stereoisomers label as cis- or trans-.

• F and G represent two different symmetrical phthalonitriles.

• One of the products is F4 as given below.
• Draw other products similar to the format of F4.

Pcs are used as photosensitizers in the photodynamic therapy (PDT) of cancer due to their
strong absorption in the visible spectrum and high molar absorption coefficients. PDT consists
of three essential components: photosensitizer, light, and oxygen. None of these is
individually toxic, but together they initiate a photochemical reaction resulting in the
generation of cytotoxic singlet oxygen (1O2) that can destroy cancer cells.

• The multiplicity of an energy level is defined as 2S+1

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

• If the two spins are parallel (↑↑), S = 1, and if the two spins are antiparallel (↑↓), S = 0.

7.8. Draw the molecule orbital (MO) diagram of the lowest energy singlet state of dioxygen
(1O2) and calculate bond order.
• There are no unpaired electrons in that state!

7.9. If the wavelength of the light needed to excite triplet oxygen into singlet oxygen is 1270
nm, calculate the energy (in kJ/mol) needed for this transition process.

Solution:

7.1. How many π-electrons are there in the bold region of the H2Pc molecule in compound 1
shown above?

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

The number of π-electrons in an H2Pc: 18 π-electrons

4 points for correct answer.

0 points if the number of electrons is not correct.

7.2. Complete the table in your answer sheet by determining the coordination number of
central ions in 2–5.

Central ion Copper ion Titanium Silicon ion Cerium ion

ion
Coordination number 4 5 6 8
2 points for each correct answer (8 points in total).
0 points if the answer is not correct.

7.3. Complete the table in your answer sheet by determining the oxidation number of each
metal (Cu, Ti, and Ce) in 2, 3, and 5.

Metal in compounds 2 3 5
Oxidation number +2 +4 +4
2 points for each correct answer (6 points in total).
0 points if the answer is not correct.

7.4. Complete the table in your answer sheet by determining the geometry of compounds 2–5.

Geometry Compound

Octahedral 4

Square prism 5

Square pyramidal 3

Square planar 2
2 points for each correct answer (8 points in total).
0 points if the answer is not correct.

7.5. Complete the table in your answer sheet by determining the magnetic property of
compounds 2–5.

Compound Magnetic property

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

2 p

3 d

4 d

5 d
2 points for each correct answer (8 points in total).
0 points if the answer is not correct.

7.6. Write the ground-state electron configuration of the silicon (Si) ion in the compound 4
and find all the quantum numbers for the 3p electrons in its ground state.

Electron configuration: Si4+: [He] 2s22p6

2 points for writing electron configuration. (0 points if the electron configuration is not correct.)
n l m1 ms
2 1 +1 +1/2
2 1 0 +1/2
2 1 -1 +1/2
Quantum numbers for 2p electrons: 2 1 +1 -1/2
2 1 0 -1/2
2 1 -1 -1/2
2 points for each correct quantum set (12 points in total).
0 points if one of the quantum number is not correct in the
set.

7.7. Draw the possible products that may occur in the statistical cyclization method by using
F and G. If there are any stereoisomers label as cis- or trans-.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

Products:

3 points for each of the structures (15 points in total).

2 point for each of the streoisomers (4 points in total).
0 points if the products or isomers are not correct.

7.8. Draw the molecule orbital (MO) diagram of the lowest energy singlet state of dioxygen
(1O2) and calculate bond order.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

MO diagram:

9 points for one of the correct MO diagrams (correct number of electrons 3 points, correct number
and ordering of energy level of the MOs 3 points, correct arrangement of electrons 3 points).

Bond order: (8 – 4)/2 = 2

3 points.
0 points if the bond order is not correct.

7.9. If the wavelength of the light needed to excite triplet oxygen into singlet oxygen is 1270
nm, calculate the energy (in kJ/mole) needed for this transition process.

Calculation:

1 nm = 1 × 10–9 m and 1270 nm = 1.270 × 10–6 m

𝑬=𝒉×𝒄÷𝝀

E = (6.6261 × 10–34 J s) (2.9979 × 108 ms–1) ÷ 1.270 × 10–6 m = 1.564 × 10–19 J and

1.564 × 10–22 kJ

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

4 points.

For 1 mol, multiply by Avogadro’s constant = (1.564 × 10–22 kJ) (6.0221 × 1023 mol–1)

= 94.19 kJ/mol

2 points.
0 points if the calculation is not correct.

Question 8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 Total
Problem 8
Points 3 3 4 4 4 4 6 3
14% of the total
Question 8.9 8.10 8.11 8.12 8.13 8.14 8.15 8.16

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Points 2 3 2 4 4 4 2 2 58
Question 8.17
Points 4

Problem 8. Boron Compounds and Hydrogen Storage

Sodium borohydride (NaBH4 ) and ammonia borane (BNH6 ) are the most studied chemical
hydrogen storage materials. In this question, you will explore the chemistry of boron and the
use of boron compounds as hydrogen storage materials.

Borax (Na2 B4 O7 ∙ nH2 O) is a boron mineral that is produced by ETI Mining Company in
Turkey. NaBH4 can be synthesized by the reduction of anhydrous borax with metallic sodium
under high-pressure hydrogen gas in the presence of silicon dioxide (silica) at 700 oC, namely
the Bayer process. In this process, all hydrogen is stored in NaBH4. On the other hand, it has
been shown that ammonia borane (BNH6 ) can be synthesized by the reaction of NaBH4 and
ammonium sulfate in dry tetrahydrofuran (THF) at 40 C (Hint: BNH6 synthesis must be
conducted in a well-ventilated fume-hood because flammable gas is generated as one of the
by-products). While NaBH4 is an ionic compound, ammonia borane is a Lewis acid–base
adduct.

8.1. Write a balanced chemical equation for the synthesis of NaBH4 from anhydrous borax.

8.2. Write a balanced chemical equation for the synthesis of ammonia borane from NaBH4.

8.3. Draw the molecular geometry of the BH4− ion and BNH6 molecule.

8.4. Calculate the hydrogen content of NaBH4 and BNH6 as a percentage by mass (wt%).

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

The hydrogen stored in both compounds can be released via hydrolysis reactions in the
presence of a suitable catalyst at room temperature. Upon the hydrolysis reactions, 4 and 3
moles of H2 gas are released from the hydrolysis of 1 mole of NaBH4 and BNH6 , respectively,
along with metaborate anion including B-O bonds.

8.5. Write the balanced chemical equations for the hydrolysis of NaBH4 and BNH6 .

One of the simplest stable borates is diboron trioxide (B2O3). Higher borates such as B3 O3− 6
having cyclic structures containing B-O-bonds can be formed. Since B2 O3 is an acidic
compound, it is easily reacted with water to produce boric acid (H3 BO3 ). On the other hand,
the high temperature and high-pressure reaction of B2O3 with ammonia yields two-
dimensional boron nitride, which consists of planar graphite-like sheets of alternating B and N
atoms.

8.6. Write the balanced chemical equations for the synthesis of boric acid and boron nitride.

8.7. Draw the molecular structures of the B3 O3−

6 ion, boric acid, and a single two-dimensional
boron nitride sheet. Hint: show at least 10 B atoms in the boron nitride structure.

Furthermore, B-H compounds, called boranes, are an important class of boron compounds.
The simplest stable borane is diborane (B2 H6 ) and many of the higher boranes can be
prepared by the pyrolysis of diborane. Diborane can be synthesized via metathesis of a boron
halide and a hydride source.

8.8. Write a balanced chemical equation for the synthesis of diborane from the reaction of
BF3 and LiBH4. Hint: both products are boron compounds.

8.9. Draw the molecular geometry of the diborane molecule. Hint: there is no B-B bond in
the structure.

BH3 (borane) is an unstable and highly reactive molecule. Therefore, it is not possible to
isolate it as BH3 under ordinary conditions. However, it can be stabilized via its reaction with
carbon monoxide to yield borane carbonyl (BH3 CO) compound, which is an adduct of borane.
The preparation of BH3 CO plays an important role in exploring the chemistry of boranes as it
indicates the likely existence of the borane molecule.

8.10. Sketch the Lewis dot structure of BH3 − CO molecule by showing the formal charges.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

8.11. Which of the statements given in your answer sheet is observed in the C − O bond of a
CO molecule upon the bond formation between BH3 and CO? Tick the correct box.

☐ It gets longer because there will be -back donation from BH3 to CO.
☐ It gets longer because CO donates -bonding electrons to BH3.
☐ No or slight change on it because CO donates its mainly non-bonding electrons to BH3.
☐ It gets shorter because CO donates * anti-bonding electrons to BH3.

Borazine consists of single and double bonded cyclic B − N units and hydrogen atoms
attached to these atoms with the molecular formula B3 N3 H6 and is isostructural to benzene.
Borazine can be synthesized by using a two-step procedure including the synthesis of
symmetrically trisubstituted chlorine derivatives of borazine (B3 N3 H3 Cl3 ) from the reaction of
ammonium chloride and boron trichloride, and then reduction of B3 N3 H3 Cl3 with LiBH4 in
THF.

8.12. Write the balanced chemical equations for the two-step synthesis of borazine starting
from ammonium chloride in THF (tetrahydrofuran). Hint: THF stabilizes one of the products
by forming a Lewis acid-base adduct.

8.13. Draw the molecular structures of borazine and its symmetrically trisubstituted chlorine
derivative.

Catalysts are substances that accelerate the rate of reactions by allowing them to proceed in a
lower energy pathway. The catalytic activity of the catalysts is generally determined by the
turnover frequency (TOF), which is calculated by dividing the molar amount of the product to
the mole of active catalyst and the time (TOF = mole product/(mole catalyst x time)). A
typical hydrolysis of BNH6 was carried out in 10.0 mL of water by using 100.0 mM BNH6
and 5.0 mg of CuPt/C catalyst (CuPt alloy nanoparticles supported on carbon black
containing 8.2 wt% Pt atom). 67.25 mL of hydrogen gas was generated in 5 minutes.

8.14. Assuming the catalytic reaction is performed under standard conditions (1 atm and
273.15 K), calculate the TOF (𝑚𝑖𝑛−1) of the CuPt/C catalyst in terms of only Pt atoms in
the hydrolysis of BNH6 by considering the volume of the hydrogen gas generated.

As a result of detailed crystal analysis of a synthesized Cux Pt y alloy nanoparticles (the

subscripts indicate molar percentages of the atoms in the alloy structure), it was determined
that the face centered cubic (fcc) unit cell was formed by Pt atoms and the Pt atoms on the
face of the fcc unit cell are supposed to be replaced with Cu atoms to form Cux Pt y

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

displacement alloy nanoparticles. According to this information, answer the following

questions.

8.15. Determine the composition of the alloy nanoparticles by finding x and y in the Cux Pt y .

8.16. Sketch the shape of the described crystal unit cell of Cux Pt y alloy nanoparticles by
showing the position of all atoms on the unit cell.

8.17. Another alloy has a Cu2 Pt1 composition. Assume that this alloy also has a fcc unit cell
with an edge length of 380 pm, but the Cu and Pt atoms are randomly distributed in the atomic
positions. Calculate the density of this alloy in g/cm3.

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Solution:

8.1. Write a balanced chemical equation for the synthesis of NaBH4 from anhydrous borax.

𝑁𝑎2 𝐵4 𝑂7 + 16𝑁𝑎 + 8𝐻2 + 7𝑆𝑖𝑂2 → 4𝑁𝑎𝐵𝐻4 + 7𝑁𝑎2 𝑆𝑖𝑂3 (3 points)

No partial point will be given if the stoichiometry is incorrect

No penalty will be given for writing another silicate product if the balanced chemical equation is
correct.

8.2. Write a balanced chemical equation for the synthesis of ammonia borane (BNH6 ) from
NaBH4.

2𝑁𝑎𝐵𝐻4 + (𝑁𝐻4 )2 𝑆𝑂4 → 2𝐵𝑁𝐻6 + 2𝐻2 + 𝑁𝑎2 𝑆𝑂4 (3 points)

No partial point will be given if the stoichiometry is incorrect.

-1 point if molecular formula of the side product (Na2SO4) is written incorrectly.
-1 points if the hydrogen gas is not written in the product side

8.3. Draw the molecular geometry of the BH4− ion and BNH6 molecule

(2 points) (2 points)
-1 point if the molecular geometry is not shown

8.4. Calculate the hydrogen content of NaBH4 and BNH6 as a percentage by mass (wt%).

4×(𝐴𝑤 (𝐻)) 4.032

𝑤𝑡% 𝐻 (𝑁𝑎𝐵𝐻4 ) = 𝑀 × 100 = = 10.65% (2 points)
𝑤 (𝑁𝑎𝐵𝐻4 ) 37.83

6×(𝐴𝑤 (𝐻)) 6.048

𝑤𝑡% 𝐻 (𝐵𝑁𝐻6 ) = × 100 = = 19.59% (2 points)
𝑀𝑤 (𝐵𝑁𝐻6 ) 30.87

No partial point given if any mistake occurs.

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8.5. Write the balanced chemical equations for the hydrolysis of NaBH4 and BNH6 .

𝑁𝑎𝐵𝐻4 + 2𝐻2 𝑂 → 𝑁𝑎𝐵𝑂2 + 4𝐻2 (2 points)

𝐵𝑁𝐻6 + 2𝐻2 𝑂 → 𝑁𝐻4 𝐵𝑂2 + 3𝐻2 (2 points)

No partial points will be given if the total stoichiometry is incorrect

No penalty for writing NaBO2 as Na+ + BO2- or NH4BO2 as NH4+ + BO2-
No penalty for writing other borates if the stoichiometry is correct
8.6. Write the balanced chemical equations for the synthesis of boric acid and boron nitride.

𝐵2 𝑂3 + 3𝐻2 𝑂 → 2𝐻3 𝐵𝑂3 (2 points)

ℎ𝑖𝑔ℎ 𝑇/ℎ𝑖𝑔ℎ 𝑃
𝐵2 𝑂3 + 2𝑁𝐻3 → 2𝐵𝑁 + 3𝐻2 𝑂 (2 points)

No partial points will be given if the total stoichiometry is incorrect.

No penalty if the high T/high P on the reaction arrow is missed.

8.7. Draw the molecular structures of the B3 O3−

6 ion, boric acid, and a single two-dimensional
boron nitride sheet (Hint: show at least 10 B atoms).

(2 points)
(2 points) (2 points)

No point if the cyclic structure is -1 point if the trigonal planar -No point if less than 10 B
not shown geometry is not shown atoms are represented in the
-1 point if the charges on oxygen structure
atoms are missed -1 point if the continuing part is
not shown
𝐁𝟑 𝐎𝟑−
𝟔 Boric acid Boron nitride

8.8. Write a balanced chemical equation for the synthesis of diborane from the reaction of
BF3 and LiBH4. (Hint: both products are boron compounds)

3𝐿𝑖𝐵𝐻4 + 4𝐵𝐹3 → 2𝐵2 𝐻6 + 3𝐿𝑖𝐵𝐹4 (3 points)

No partial point will be given if the stoichiometry is incorrect

-1 point if molecular formula of the side product (LiBF4) is written incorrectly.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Problems & Solutions

8.9. Draw the VSEPR molecular geometry of the diborane molecule (Hint: there is no B-B
bond in the structure).

(2 points)
-1 point if the 3D structure is not shown
No point if a B-B bond is presented in the structure

8.10. Sketch the Lewis dot structure of BH3 CO molecule by showing the formal charges.

(3 points)
-1 point if the formal charges are not represented or represented incorrectly.
No penalty will be given if the arrow is not represented.

8.11. Which of the following statements is observed in the C − O bond of a CO molecule upon
the bond formation between BH3 and CO?

☐ It gets longer because there will be -back donation from BH3 to CO.
☐ It gets longer because CO donates -bonding electrons to BH3.
☒ No or slight change on it because CO donates its mainly non-bonding electrons to BH3.
☐ It gets shorter because CO donates * anti-bonding electrons to BH3.

(2 points)
No point if more than one box is clicked.

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8.12. Write the balanced chemical equations for the two-step synthesis of borazine starting
from ammonium chloride in THF. (Hint: THF stabilizes one of the products).

3𝑁𝐻4 𝐶𝑙 + 3𝐵𝐶𝑙3 → 𝐵3 𝑁3 𝐻3 𝐶𝑙3 + 9𝐻𝐶𝑙 (2 points)

𝑇𝐻𝐹
𝐵3 𝑁3 𝐻3 𝐶𝑙3 + 3𝐿𝑖𝐵𝐻4 → 𝐵3 𝑁3 𝐻6 + 3𝐿𝑖𝐶𝑙 + 3𝑇𝐻𝐹 ∙ 𝐵𝐻3 (2 points)

No partial point will be given if the total stoichiometry is wrong.

-1 point for each if molecular formula of the side products is written incorrectly.

8.13. Draw the molecular structures of borazine and its symmetrically trisubstituted chlorine
derivative.

(2 points) (2 points)

No point will be given if the cyclic structure is not shown

No point will be given if the Cl atoms are bonded to N atoms in B3N3H3Cl3 molecule
-1 point for each molecule if the cyclic structure is shown but the double bonds are not
Mesomeric structures will also be accepted

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8.14. Assuming the catalytic reaction is performed under standard conditions, calculate the
TOF of the CuPt/C catalyst in terms of only Pt atoms in the hydrolysis of BNH6 by
considering the volume of the hydrogen gas generated.

67.25 𝑚𝐿
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐻2 𝑔𝑎𝑠 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 = = 3.0 𝑚𝑚𝑜𝑙 = 3 × 10−3 𝑚𝑜𝑙 (1 point)
22.41 𝑚𝐿

0.005×8.2
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑃𝑡 = [( )/195.1] = 2.1 × 10−6 𝑚𝑜𝑙 (1 point)
100

3×10−3 𝑚𝑜𝑙 𝐻2
𝑇𝑂𝐹 = (2.1×10−6 𝑚𝑜𝑙 𝑃𝑡)×5.0 𝑚𝑖𝑛
= 286 𝑚𝑖𝑛−1 (2 points)

(4 points in total)

No partial point given if any mistake occurs in the calculation of TOF.

8.15. Determine the composition of the alloy nanoparticles by finding x and y in the Cux Pt y

In a regular fcc unit cell,

8×1
𝐶𝑜𝑟𝑛𝑒𝑟𝑠 = 8 = 1 𝑃𝑡 𝑎𝑡𝑜𝑚
6×1
𝐹𝑎𝑐𝑒𝑠 = = 3 𝑃𝑡 𝑎𝑡𝑜𝑚𝑠
2
After the replacement surface Pt atoms with Cu atoms,

8×1
𝐶𝑜𝑟𝑛𝑒𝑟𝑠 = = 1 𝑃𝑡 𝑎𝑡𝑜𝑚 (1 point)
8
6×1
𝐹𝑎𝑐𝑒𝑠 = = 3 𝐶𝑢 𝑎𝑡𝑜𝑚𝑠 (1 point)
2

Alloy composition = 𝐶𝑢3 𝑃𝑡 (2 points), Cu75Pt25 is also accepted

(4 points in total)

No penalty will be given if the calculation of Pt atoms in a regular fcc unit cell or after
replacements is not shown.

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8.16. Sketch the shape of the described crystal unit cell of CuxPty alloy nanoparticles by
showing the position of all atoms on the unit cell.

(2 points)

–1 point if the number of atoms represented in the crystal unit is written incorrectly.
No point if the crystal unit cell structure is wrong

8.17. Another alloy has a Cu2Pt1 composition. Assume that this alloy also has a fcc unit cell
with an edge length of 380 pm, but the Cu and Pt atoms are randomly distributed in the atomic
positions. Calculate the density of this alloy in g/cm3.

Actual unit cell composition: Cu2.66Pt1.33 (1 point)

𝑉 = 𝐴3
𝑎 = 380 𝑝𝑚 = 3.80 × 10−8 𝑐𝑚
𝑉 = (3.80 × 10−8 )3 = 54.87 × 10−24 𝑐𝑚3 (1 point)

𝑚 [(2.66 × (𝐴𝑤 (𝐶𝑢)) + 1.33(𝐴𝑤 (𝑃𝑡)]/𝑁𝐴

𝑑= =
𝑉 54.87 × 10−24 𝑐𝑚3
[(2.66 × (63.54) + (195.1)𝑥1.33]/6.02 × 1023
= −24
= 12.97 𝑔/𝑐𝑚3
54.87 × 10
(2 points)
(4 points in total)
1 point will be given if the density is calculated by not considering the actual alloy composition of
Cu2.66Pt1.33 in the given fcc unit cell.

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Problem 9 Question 9.1 9.2 9.3 9.4 9.5 9.6 9.7 9.8 Total
12% of the total Points 5 5 8 16 5 6 25 30 100

Problem 9. Quantification of Heavy Metal Ions

For the quantitative analysis of heavy metal ions in a factory’s wastewater pool, the following
steps have been applied by an analyzer at 298 K:
Step 1) 10-mL samples of each were obtained from five different regions in a wastewater
pool, mixed in a 100-mL beaker, and then stirred for 5 minutes using a magnetic stirrer.
Step 2) 10-mL of sample solution was taken from the 100-mL beaker and 142 mg of Na2SO4
was added while stirring, followed by transfer to a three-electrode cell as seen in Figure 1a. In
this electrochemical cell, Pt wire, Ag/AgCl (3 M KCl), and Pt foil served as the working,
reference, and counter electrodes, respectively.
Step 3) These electrodes were connected to a potentiostat and a constant potential of –0.50 V
vs. Ag/AgCl for 14 minutes was applied as seen in Figure 1b (horizontal line). It is assumed
that 14 min. is sufficient to complete the expected electrochemical reactions.

(a) (b)

Figure 1. a) Electrochemical cell design; 1) Working electrode (Pt wire), 2) reference

electrode (Ag/AgCl, 3M KCl), 3) counter electrode (Pt foil), 4) cell tap, 5) electrochemical
cell, 6) 10-mL of sample solution. b) Potential change of working electrode as a function of
time. y-axis: potential/V vs Ag/AgCl, x-axis: time/min.

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Step 4) The electrodes were rinsed with distilled water, placed into another electrochemical
cell including 10-mL of 0.1 M H2SO4 solution, and potential was scanned between –0.50 and
+0.50 V as seen in Figure 1b (downward sloping line in 2 min.). Current vs. potential data for
this step are presented in Figure 2a, which is like an excellent view of Mount Ararat (Ağrı
Dağı), the highest mountain in Turkey (Figure 2b).

(a)

(b)

Figure 2. a) Potential scan of the working electrode as a function of current in 0.1 M H2SO4
solution after keeping it constant at a potential of –0.50 V in 10-mL of wastewater sample as
seen in Figure 1b (horizontal line). y-axis: current/A, x-axis: potential/V vs Ag/AgCl, b) A
view of Great and Little Ararat peaks.

Step 5) Another 10-mL of the sample solution prepared in step 1 was taken and the processes
explained in steps 2 and 3 were applied in that order. The electrodes were rinsed with distilled
water and placed into 10-mL of 0.1 M H2SO4 solution. Then the potential of the working
electrode was kept constant at +0.05 V for 14 minutes. It is assumed that 14 min. is sufficient
to complete the expected electrochemical reactions.
Step 6) After step 5 was performed, the solution in the electrochemical cell was placed in a
suitable oven to evaporate at 150 °C until dry solid was obtained.

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Step 7) 5-mL of ethylenediaminetetraacetic acid (EDTA, H4Y) (Figure 3) solution was added
to the solid obtained in step 6 and it was shaken to dissolve. It is known that 1-mL of EDTA
solution is equivalent to 3.85 mg/mL BaCO3. Then, pH of the solution was adjusted to 10.0.
Excess EDTA was titrated with standard 0.0010 M Ni(NO3)2 solution and it was observed that
95.60 mL of Ni(NO3)2 solution was consumed up to the endpoint.

Figure 3. Chemical structure of EDTA (H4Y).

• In water saturated with H2S, equilibrium concentration of [H2S] is 0.1 M.

• Ksp(NiS) = 4.0 × 10–20; Ksp(CuS) = 1.0 × 10–36
• Ka1(H2S) = 9.6 × 10–8; Ka2(H2S) = 1.3 × 10–14
•
Reaction E˚/V (at 298 K)
2𝐻2 𝑂(𝑙) + 2𝑒 − → 𝐻2 (𝑔) + 2𝑂𝐻 − (𝑎𝑞) −0.83
𝑁𝑖 2+ (𝑎𝑞) + 2𝑒 − → 𝑁𝑖(𝑠) −0.24
2𝐻 + (𝑎𝑞) + 2𝑒 − → 𝐻2 (𝑔) 0.00
𝐶𝑢2+ (𝑎𝑞) + 2𝑒 − → 𝐶𝑢(𝑠) +0.34
𝐴𝑔+ (𝑎𝑞) + 𝑒 − → 𝐴𝑔(𝑠) +0.80
𝑂2 (𝑔) + 4𝐻 + (𝑎𝑞) + 4𝑒 − → 2𝐻2 𝑂(𝑙) +1.23

9.1. Which of the following can be considered for peak 1 and peak 2 in Figure 2a,
respectively? Tick the correct box on the answer sheet.

9.2. Which of the statements is expected, if the potential is applied as –1.2 V instead of –0.5 V
at the first step (horizontal line) in Figure 1b? Tick the correct box on the answer sheet.

9.3. Calculate the scan rate of data presented in Figure 2a as mV/s at 298 K.

The potential of the following cell is measured as 0.437 V.

𝑃𝑡, 𝐻2 (0.92 𝑏𝑎𝑟)|𝐻𝐶𝑙(1.50 × 10−2 𝑀), 𝐴𝑔𝐶𝑙(𝑠𝑎𝑡)|𝐴𝑔

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9.4. Calculate the standard electrode potential value (V) of half-cell of 𝐴𝑔𝐶𝑙(𝑠) + 𝑒 − →
𝐴𝑔(𝑠) + 𝐶𝑙 − (𝑎𝑞) at 298 K. Note: You must show all works.

9.5. Which of the statements is the main purpose of step 5 in this analysis? Tick the correct
box on the answer sheet.

9.6. Write net ionic equations for the complexation and the back titration reaction of step 7 on
the answer sheet

9.7. Calculate Ni2+ concentration as mg/L in the wastewater of the factory. Note: You must
show all works.
9.8. Calculate the minimum pH value for starting the precipitation of Ni2+ ions in the solution
obtained in step 5 by passing H2S gas into the solution until saturation. If you cannot solve
question 9.7, use 20 mg/L Ni2+ sample for this question. Note: You must show all works.

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Solution:

9.1. Which of the following can be considered for peak 1 and peak 2 in Figure 2a,
respectively? Tick the correct box on the answer sheet.

☐ Peak 1: electrochemical reduction of Ni / Peak 2: electrochemical reduction of Cu

☐ Peak 1: electrochemical reduction of Cu / Peak 2: electrochemical reduction of Ni
☐ Peak 1: electrochemical reduction of Ni / Peak 2: electrochemical oxidation of Cu

☒ Peak 1: electrochemical oxidation of Ni / Peak 2: electrochemical oxidation of Cu

☐ Peak 1: electrochemical oxidation of Cu / Peak 2: electrochemical oxidation of Ni
5 points for correct answer.

9.2. Which of the statement is expected, if the potential is applied as –1.2 V instead of -0.5 V
at the first step (horizontal line) in Figure 1b? Tick the correct box on the answer sheet.

☐ NO evolution
☐ NO2 evolution
☐ Nitrogen evolution 5 points for correct answer.

☐ Oxygen evolution
☒ Hydrogen evolution

9.3. Calculate the scan rate of data presented in Figure 2a as mV/s.

Calculation:
We can calculate the scan rate using the slope of Figure 1b (downward sloping line)

Scan rate = 1000 mV/120 s = 8.33 mV/s

8 points.

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9.4. Calculate the standard electrode potential value of half-cell of 𝐴𝑔𝐶𝑙(𝑠) + 𝑒 − → 𝐴𝑔(𝑠) +
𝐶𝑙 − (𝑎𝑞). Note: You must show all works.

Calculation:
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑟𝑖𝑔ℎ𝑡 − 𝐸𝑙𝑒𝑓𝑡 (3 point)

𝐻𝑎𝑙𝑓 − 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛𝑠;
𝐴𝑔𝐶𝑙(𝑠) + 𝑒 − → 𝐴𝑔(𝑠) + 𝐶𝑙 − (aq)
2𝐻 + (𝑎𝑞) + 2𝑒 − → 𝐻2 (𝑔)
0.0592 𝑃𝐻
𝑜
𝐸𝑐𝑒𝑙𝑙 = (𝐸𝐴𝑔𝐶𝑙/𝐴𝑔 − 0.0592 log[𝐶𝑙 − ]) − (𝐸𝐻𝑜 +/𝐻2 − 𝑙𝑜𝑔 [𝐻 +2]2) (7 points)
2

𝑜 0.0592 0.92
0.437 = (𝐸𝐴𝑔𝐶𝑙/𝐴𝑔 − 0.0592 log 1.5 × 10−2 ) − (0.00 − 𝑙𝑜𝑔 (1.5×10−2)2 ) (4 points)
2

𝑜
𝐸𝐴𝑔𝐶𝑙/𝐴𝑔 =0.22 V (2 point)

–2 points for each calculation error.

–2 points for each wrong unit.

9.5. Which of the statements is the main purpose of step 5 in this analysis? Tick the correct
box on the answer sheet.

☐ Modification of Pt wire with Ni–Cu alloy film

☐ Modification of Pt wire with Ni film
☐ Electrochemical stripping of both Cu and Ni from Cu–Ni-modified Pt wire to the solution

☐ Electrochemical stripping of Cu from Cu–Ni-modified Pt wire to the solution

☒ Electrochemical stripping of Ni from Cu–Ni-modified Pt wire to the solution
5 points for correct answer.

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9.6. Write net ionic equations for the complexation and the back titration reaction of step 7 in
your answer sheet.

Complexation: 𝑁𝑖 2+ (𝑎𝑞) + 𝑌 4− (𝑎𝑞) → 𝑁𝑖𝑌 2− (𝑎𝑞) or

𝑁𝑖 2+ (𝑎𝑞) + 𝐻𝑌 3− (𝑎𝑞) → 𝑁𝑖𝐻𝑌 − (𝑎𝑞)
Back titration: 𝑁𝑖 2+ (𝑎𝑞) + 𝑌 4− (𝑎𝑞) → 𝑁𝑖𝑌 2− (𝑎𝑞) or
𝑁𝑖 2+ (𝑎𝑞) + 𝐻𝑌 3− (𝑎𝑞) → 𝑁𝑖𝐻𝑌 − (𝑎𝑞)
3 points for each correct answer.

9.7. Calculate Ni2+ concentration as mg/L in the wastewater of the factory. Note: You must
show all works.
Calculation:
5 pieces of 10-mL samples were collected and the total sample volume is 50-mL. 10-mL of
the part was taken from this 50-mL sample. (2 point)

EDTA titration; 3.85 mg BaCO3/mL EDTA

𝐵𝑎2+ (𝑎𝑞) + 𝑌 4− (𝑎𝑞) → 𝐵𝑎𝑌 2− (𝑎𝑞)

3.85 𝑚𝑔 𝐵𝑎𝐶𝑂3 1 𝑚𝑚𝑜𝑙 𝐸𝐷𝑇𝐴

197 𝑚𝑔 𝐵𝑎𝐶𝑂3 ×1 𝑚𝑚𝑜𝑙 𝐵𝑎𝐶𝑂3
1 𝑚𝑚𝑜𝑙 𝐵𝑎𝐶𝑂3
[𝐸𝐷𝑇𝐴] = = 0.01954 𝑀 𝐸𝐷𝑇𝐴 (8 points)
1 𝑚𝐿 𝐸𝐷𝑇𝐴

𝑁𝑖 +2 (𝑎𝑞) + 𝑌 −4 (𝑎𝑞) → 𝑁𝑖𝑌 −2 (𝑎𝑞)

0.01954 𝑚𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 0.0010 𝑚𝑚𝑜𝑙 𝑁𝑖 2+
𝑚𝑚𝑜𝑙𝑁𝑖 +2 = [( × 5.00 𝑚𝐿 𝐸𝐷𝑇𝐴) − ( × 95.60 𝑚𝐿 𝑁𝑖 2+ ×
1 𝑚𝐿 𝐸𝐷𝑇𝐴 1 𝑚𝐿 𝑁𝑖 2+
1 𝑚𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 1 𝑚𝑚𝑜𝑙 𝑁𝑖 2+
)] × 1 𝑚𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 = 0.0021 𝑚𝑚𝑜𝑙 𝑁𝑖 2+ (12 points)
1 𝑚𝑚𝑜𝑙 𝑁𝑖 2+

58.7 𝑚𝑔 𝑁𝑖2+ 50 𝑚𝐿
(0.0021 𝑚𝑚𝑜𝑙 𝑁𝑖 2+ × )×
1 𝑚𝑚𝑜𝑙 𝑁𝑖2+ 10 𝑚𝐿
𝐶𝑁𝑖 2+ = = 12.33 𝑚𝑔/𝐿 (3 points)
0.05 𝐿 𝑠𝑎𝑚𝑝𝑙𝑒
–3 points for each calculation error.
–3 points for each wrong unit.
–3 points for each wrong conversion factor.

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9.8. Calculate the minimum pH value for starting the precipitation of Ni2+ ions in the solution
obtained in step 5 by passing H2S gas into the solution until saturation. If you cannot solve
question 9.7, use 20 mg/L Ni2+ sample for this question. Note: You must show all works.

Calculation:

0.01233 𝑔 𝑁𝑖2+
0.0021 𝑚𝑚𝑜𝑙 𝑁𝑖 2+ 58.7 𝑔/𝑚𝑜𝑙
[𝑁𝑖 2+ ] = = 2.1 × 10−4 𝑀 or [𝑁𝑖 2+ ] = = 2.1 × 10−4 𝑀
10 𝑚𝐿 𝑠𝑎𝑚𝑝𝑙𝑒 1 𝐿 𝑠𝑎𝑚𝑝𝑙𝑒
(6 points)

𝑁𝑖𝑆 ⇄ 𝑁𝑖 2+ (𝑎𝑞) + 𝑆 2− (𝑎𝑞)

4.0 × 10−20 = 2.1 × 10−4 × [𝑆 2− ]
[𝑆 2− ] = 1.905 × 10−16 𝑀 (6 points)

[𝐻𝑆 − ][𝐻3 𝑂 + ]
𝐻2 𝑆 + 𝐻2 𝑂 ⇄ 𝐻𝑆 − + 𝐻3 𝑂+ 𝐾𝑎1 = 9.6 × 10−8 = (1 point)
[𝐻2 𝑆]

[𝑆 2− ][𝐻3 𝑂 + ]
𝐻𝑆 − + 𝐻2 𝑂 ⇄ 𝑆 2− + 𝐻3 𝑂+ 𝐾𝑎2 = 1.3 × 10−14 = (1 point)
[𝐻𝑆 − ]

0.1=[𝐻2 𝑆] + [𝐻𝑆 − ] + [𝑆 2− ] (1 points)

[𝐻2 𝑆] ≫ [𝐻𝑆 − ] + [𝑆 −2 ] and [𝐻2 𝑆] = 0.1 𝑀 (1 points)

[𝑆 2− ][𝐻3 𝑂 + ]2
𝐾𝑎1 × 𝐾𝑎2 = 1.25 × 10−21 = (7 points)
[𝐻2 𝑆]

1.905×10−16 [𝐻3 𝑂 + ]2
1.25 × 10−21 = (4 points)
0.1

[𝐻3 𝑂+ ] = 8.1 × 10−4 𝑀

𝑝𝐻 = 3.09 (3 points)

If Ni2+ concentration is taken 20 mg/L, the result is pH = 2.99

–3 points for each calculation error.

–3 points for each wrong unit.
–3 points for each wrong conversion factor.

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The End

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