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Preparatory problems for
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the 56th International
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Chemistry Olympiad 2024

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Riyadh, Saudi Arabia

Exclusive sponsor Organizing partners

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Preparatory problems for the 56th International Chemistry Olympiad

Copyright © 2024 by the 56th International Chemistry Olympiad, Some rights reserved.
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Editor: Gábor Magyarfalvi

This work is licensed under the Creative Commons Attribution—NonCommercial-Share Alike 4.0
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International License. To view a copy of this license, visit http://creativecommons.org/licenses/by-nc-

sa/4.0/ Any of the conditions can be waived if you get permission from the copyright holder.

56th International Chemistry Olympiad

King Abdulaziz and his Companions Foundation for Giftedness and Creativity
P O Box: 300820
Riyad 11372
Saudi Arabia
Phone: 00966112826166
E-mail: icho2024.science@mawhiba.org.sa
Web: www.icho2024.sa
Contents
PREFACE............................................................................................................................................... 5
PROBLEM AUTHORS AND REVIEWERS ..................................................................................... 6
FIELDS OF ADVANCED DIFFICULTY ............................................................................................ 7
CONSTANTS AND FORMULAE ........................................................................................................................... 8
PERIODIC TABLE WITH RELATIVE ATOMIC MASSES ...................................................................................... 9
SPECTROSCOPICAL DATA ............................................................................................................................... 10

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THEORETICAL PROBLEMS .......................................................................................................... 11
1. TWO ACIDS ................................................................................................................................................. 12
Solution.............................................................................................................................................................15

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2. MALIC ACID ................................................................................................................................................ 18
Solution.............................................................................................................................................................20
3. HYDRAZINE SALTS ..................................................................................................................................... 25

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Solution.............................................................................................................................................................26

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4. CCM ........................................................................................................................................................... 28
Solution.............................................................................................................................................................30
5. CARBON CAPTURE ..................................................................................................................................... 32
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Solution.............................................................................................................................................................34
6. NANOPARTICLES........................................................................................................................................ 36
Solution.............................................................................................................................................................38
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7. ADIABATIC REACTOR ................................................................................................................................ 40

Solution.............................................................................................................................................................42
8. NITROGEN OXIDES ..................................................................................................................................... 46
Solution.............................................................................................................................................................47
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9. STATIN DRUGS ........................................................................................................................................... 49

Solution.............................................................................................................................................................52
10. MINIONS AND BERRIES ........................................................................................................................... 54
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Solution.............................................................................................................................................................56
11. CLOCK REACTIONS .................................................................................................................................. 59
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Solution.............................................................................................................................................................61
12. CRYSTAL VIOLET ..................................................................................................................................... 64
Solution.............................................................................................................................................................66
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13. ALUMINIUM IN LATTICES ....................................................................................................................... 69

Solution.............................................................................................................................................................70
14. SULFIDE MINERALS ................................................................................................................................. 71
Solution.............................................................................................................................................................73
15. BEAUTY AND INFINITY ........................................................................................................................... 75
Solution.............................................................................................................................................................77
16. BORON CLUSTERS ................................................................................................................................... 80
Solution.............................................................................................................................................................82
17. MOFS: THE ULTIMATE COORDINATION NETWORK........................................................................... 84
Solution.............................................................................................................................................................86

56th IChO Preparatory Problems 3

 18. BLACK GOLD ............................................................................................................................................ 88
Solution.............................................................................................................................................................91
19. NITROGEN FIXATION .............................................................................................................................. 94
Solution.............................................................................................................................................................96
20. BROMINATION......................................................................................................................................... 98
Solution.......................................................................................................................................................... 100
21. NMR PUZZLE ........................................................................................................................................101
Solution.......................................................................................................................................................... 103
22. ORGANONITROGEN COMPOUNDS: THE COMPOUNDS OF LIFE .........................................................104
Solution.......................................................................................................................................................... 106

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23. NMR CLUE ............................................................................................................................................108
Solution.......................................................................................................................................................... 109
24. NEUROTRANSMITTERS .........................................................................................................................110
Solution.......................................................................................................................................................... 113

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25. HENNA ...................................................................................................................................................115
Solution.......................................................................................................................................................... 117
26. NATURAL PRODUCTS SYNTHESES ........................................................................................................119

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Solution.......................................................................................................................................................... 121

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27. PRZEWALSKIN B: MEDICINE FOR THE HEART ...................................................................................122
Solution.......................................................................................................................................................... 124
28. POLYMERS .............................................................................................................................................125
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Solution.......................................................................................................................................................... 127
29. POLYMER FUNCTIONALIZATION ..........................................................................................................129
Solution.......................................................................................................................................................... 131
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30. POLYURETHANE NETWORK .................................................................................................................132

Solution.......................................................................................................................................................... 133
LABORATORY PROCEDURES AND SAFETY .........................................................................135
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31. IDENTIFICATION WITH A BATTERY .....................................................................................................136

Solution.......................................................................................................................................................... 138
32. DIRECTION OF REDOX PROCESSES .......................................................................................................140
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Solution.......................................................................................................................................................... 145
33. OXALIC ACID CONTENT OF TURMERIC .................................................................................................149
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Solution.......................................................................................................................................................... 154
34. TITRATION WITH A PH METER ............................................................................................................156
Solution.......................................................................................................................................................... 161
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35. ANALYSIS OF A COPPER ALLOY ............................................................................................................163

Solution.......................................................................................................................................................... 166
36. TITRATIONS WITH HYPOCHLORITE .....................................................................................................168
Solution.......................................................................................................................................................... 171
37. TLC EXPERIMENTS WITH XANTHINE ALKALOIDS ..............................................................................172
Solution.......................................................................................................................................................... 177
38. DETERMINATION OF THE EUGENOL CONTENT OF CLOVES ................................................................178
Solution.......................................................................................................................................................... 181

56th IChO Preparatory Problems 4

Preface
The scientific committee of the 56th International Chemistry Olympiad is excited to
announce that the 56th International Chemistry Olympiad Preparatory Problems have
been released. It is expected that these problems will assist the students in their
preparation for the Olympiad. It is intended to align both the theoretical and practical
problems with the core IChO syllabus (www.ichosc.org/regulations, Appendix C) while
reducing topics that go beyond the core syllabus. However, advanced topics have been

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included in this year’s preparatory problems, as shown in the listing later.
This scientific committee has provided 30 theoretical problems and 8 practical tasks to

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illustrate the depth of these fields. Our goal is to provide challenging and interesting
problems, similar in style to those on the final exam, yet these problems are long and
numerous. The committee is welcoming comments and questions from the mentors at the
icho2024.science@mawhiba.org.sa email address.

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Through this international scientific event, young people around the world can learn
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about chemistry and inspire one another. In addition to inspiring young people to pursue
careers in the fundamental sciences, this competition influences public attitudes toward
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chemistry, an important branch of science. Moreover, you will learn about the culture and
history of the host country as well as meet people from all over the world.
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The scientific committee of the 56th International Chemistry Olympiad

Riyadh, Saudi Arabia, January 2024
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Acknowledgments
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Thank you to all the authors who prepared both preparatory and competition problems
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for the 56th International Chemistry Olympiad. During months of hard work, they created
a booklet that would be of assistance to young chemists taking part in the Olympiad. The
IChO Steering Committee members, scientific reviewers, and language proofreaders have
helped us with a splendid job.

56th IChO Preparatory Problems 5

Problem authors and reviewers
Core committee members
Prof. Abdullah Mohammad Al-Mayouf, King Saud University, Chairman
Prof. Gábor Magyarfalvi, Eötvös Loránd University, Vice chairman
Abdullah Jassim Al-Abdulghani, University of Wisconsin–Madison
Nasser Abdullah Al-Obaid, King Abdullah University of Science and Technology
Dr. Ahmad Al-Saleh, King Saud University
Prof. Kuo Wei Huang, King Abdullah University of Science and Technology

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Prof. Gabor Lente, University of Pécs
Prof. Petra Menova, University of Chemistry and Technology, Prague

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Authors and reviewers
Hashim Al Khunaizi, UCLA and ARAMCO

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Prof. Hamad Alkhathlan, King Saud University
Mohammad Almagweshi, SABIC
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Bader Almulhim, King Abdullah University of Science and Technology
Prof. Sarah Al-Rashood, King Saud University
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Dr. Zainab Al-Saihati, ARAMCO
Salman Alsharif, King Abdullah University of Science and Technology
Dr. Éva Dóka, Institute of Oncology, Budapest
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Dr. Dayana Gulevich, Eberhard Karls University of Tübingen, Germany

Dr. Sarolta Igaz, freelancer, teacher
Dr. Essam Jameah, SABIC
Dr. Dmytro Kandaskalov, Université Marseilles
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György Kóczán, Eötvös Loránd University, Hungary

Dr. Katalin Perényi, Hungarian Institute for Forensic Sciences
Dr. Zsuzsanna Sánta, freelancer, teacher
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Andrei Shved, ETH Zürich

Dr. Ákos Szabó, HUN-REN Research Centre for Natural Sciences, Budapest
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Dr. Zsófia Szalay, Gedeon Richter Plc.

Attila Villányi, Apáczai Csere János Secondary School, Budapest
Péter Zagyi, Németh László Secondary School, Budapest
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56th IChO Preparatory Problems 6

Fields of advanced difficulty
Theoretical
• Solid state structures, unit cell types, cell parameters,
• Analysis of complex reactions using steady-state and quasi-equilibrium
approximations, mechanisms of catalytic reactions (also as applied to kinetics of
enzyme catalysis),
• Basic concepts of molecular orbital theory, electron configurations, bond orders,

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orbitals in homonuclear diatomics, interpretation of MO schemes provided for
more complex systems,

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• Interpretation of 1H NMR spectra: chemical shift, multiplicity (including coupling
to other nuclei with I >1/2), integrals,
• Basics of polymer science, polymerization mechanisms, polydispersity, polymer

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functionalization, GPC chromatography,
Practical

•
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Synthesis techniques: thin layer chromatography
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Familiarity with the following advanced topics will not be expected in the exams:
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Calculation of kinetic isotope effects,

Crystal field theory and ligand field theory (beyond the fact that d orbitals can be split and
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can be part of molecular orbitals),

Mechanistic and stereochemical details of cycloadditions,
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Pericyclic reactions other than Diels-Alder reactions,

Mechanistic details of metal catalyzed cross-coupling reactions,
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No other cross-coupling reactions besides the examples presented in the preparatory are
expected to be known without further explanation.
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For NMR spectroscopy of nuclei other than 1H, students only need to be able to determine
the number of chemical environments present, and do not need to know information
about chemical shifts or coupling.
Use of spreadsheet software,
Solving higher-order equations

56th IChO Preparatory Problems 7

Constants and formulae

Zero of the Celsius

Avogadro constant: N A = 6.022·1023 mol–1 273.15 K
scale:

Gas constant: R = 8.314 J K–1 mol–1 Faraday constant: F = 96485 C mol–1

Ionic product of
𝐾𝐾𝑤𝑤 = 10−14 Planck-constant: h = 6.626·10–34 J s

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water at 298.15 K :

Ideal gas equation: pV = nRT Enthalpy H = U + pV

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𝐼𝐼0
Beer-Lambert law: 𝐴𝐴 = log = 𝜀𝜀𝜀𝜀𝜀𝜀 Gibbs energy: G = H – TS
𝐼𝐼
[A– ]

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−E Henderson–
Arrhenius equation: k = A e RTa pH = pKa + log
Hasselbalch equation: [AH]

Speed of light: c = 3.000·108 m s–1 nt Integrated rate laws

Zeroth order:
[A] = [A] 0 – kt
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𝑜𝑜
∆𝑟𝑟 𝐺𝐺 𝑜𝑜 = −𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 = −𝑛𝑛𝑛𝑛𝐸𝐸𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 First order: ln[A] = ln[A] 0 – kt
∞
𝑎𝑎 1 1
+ kt
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� 𝑎𝑎 𝑟𝑟 𝑘𝑘 = for |𝑟𝑟| < 1 Second order: =

1 − 𝑟𝑟 [A] [A]0
𝑘𝑘=0
Consider all gases ideal throughout the exam.
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In equilibrium constant calculations all concentrations are referenced to a standard

concentration of one mol per dm3.
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56th IChO Preparatory Problems 8

Periodic table with
relative atomic masses
1 18
1 2
H He
1.008 2 13 14 15 16 17 4.003
3 4 5 6 7 8 9 10
Li Be B C N O F Ne

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6.94 9.01 10.81 12.01 14.01 16.00 19.00 20.18
11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
22.99 24.30 3 4 5 6 7 8 9 10 11 12 26.98 28.09 30.97 32.06 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

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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

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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 Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9
87
Fr
137.3
88
Ra
57-71

89-
103
178.5
104
180.9
105
183.8
106
186.2
107
Rf Db Sg Bh Hs Mt Ds Rg Cn Nh
190.2
108
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192.2
109
195.1
110
197.0
111
200.6
112
204.4
113
207.2
114
Fl
209.0
115
Mc Lv
-
116
-
117
Ts Og
-
118
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- - - - - - - - - - - - - - - - -

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
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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 - - - - - - - - - - -
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56th IChO Preparatory Problems 9

Spectroscopical data
1H NMR

Chemical shifts of hydrogen (in ppm /TMS)

phenols

alcohols

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alkenes

aromatics alkynes

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carboxylic acids CH 3 —NR 2 CH 3 —SiR 3

aldehydes CH 3 —OR ketones

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CH 3 —CR 3

11.0 10.0 9.0 8.0 7.0

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Visible light
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750 nm
red
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400 nm 620 nm
purple orange
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480 nm 590 nm
blue yellow
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530 nm
green

56th IChO Preparatory Problems 10

Theoretical Problems

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56th IChO Preparatory Problems 11

1. Two acids
Ali received a lab project to investigate two diprotic carboxylic acids, B and C.
Part I.
According to his observation compound B is a white solid material that is slightly soluble
in water. Ali made 200 cm3 of stock solution from 1.2000 g of compound B, and he titrated
25.00 cm3 of the stock solution with 0.1000 mol/dm3 NaOH solution. He has found a pH
meter therefore he could monitor the pH change of the solution as a function of the volume

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of NaOH solution added. The graph below shows his experimental results.
pH

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pHb

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5.51

pHa

2.97
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pHx

4.51 9.02 13.53 18.04

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V (NaOH, mL)

Based on the graph Ali could determine many things about the dicarboxylic acid (B) and
its solution. (In this concentration range, the volumes of the solutions are additive.) Let us
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follow his work.

1.1. Calculate the molar mass of compound B.
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1.2. Determine K a,1 (B) and K a,2 (B), the acid dissociation constants of compound B
based on the diagram.
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Using the molar mass of compound B, he deduced its molecular formula. He then searched
for K a data and, with the aid of his initial findings, successfully identified the structure.
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He realized that one of the dissociation constants obtained from the diagram is probably
not very reliable. To improve accuracy, he decided to use the literature value of K, the
cumulative acid dissociation constant for the H 2 A ⇌ 2 H+ + A2– reaction which in the case
of B is 3.99∙10–9.
1.3. Reproduce his reasoning presented below by marking the correct alternatives
in the sentence below and reproduce his estimate calculation.
K ax (x is 1 or 2) based on the graph is probably inaccurate due to the following two
factors: the total concentration of the acid in the titrated solution was relatively too
(high/low) while the K ax value in question was relatively too (large/small).

56th IChO Preparatory Problems 12

1.4. Calculate the value that is marked as pH a on the diagram (the first equivalence
point). Use the most accurate data for calculation. Give your answer with two
decimal places.
1.5. Using appropriate approximations, calculate the pH of the initial stock solution
(pH x on the graph) and the pH of the second equivalence point, pH b . Give your
answer with two decimal places.
Ali wants to set up a titration using B for his fellow students using acid-base indicator. He
has found the following data of the indicators:

Name pH range of color

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change
Thymolphthalein 9.3–10.5
Phenolphthalein 8.3–10.0

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Cresol red 7.2–8.8
Bromothymol 6.0–7.6
blue

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Methyl red 4.4–6.2
Methyl orange 3.1–4.4
Thymol blue 1.2–2.8 nt
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1.6. Choose the best indicator for the titration.
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Part II.
Compound C is also white, but it has excellent solubility in water. Although the name was missing
on the bottle, the acid dissociation constants were written on it:
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K a,1 (C) = 6.03∙10–4, K a,2 (C) = 1.41∙10–5

Ali made 200 cm3 of solution from 1.1700 g of the dry, anhydrous compound C and 25.00 cm3 of
the stock solution was titrated with the same NaOH solution as before while he monitored the pH
by the pH meter. The following graph has been made according to his experimental values.
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From the data of the titration Ali determined that molar mass of compound C is 150 g mol–1.
pH

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8.60

4.03

2.33

9.75 19.50
V (NaOH, mL)

56th IChO Preparatory Problems 13

Ali wants to set up a titration of C as well using acid base indicator.
1.7. Choose a suitable indicator from the list above.
1.8. Calculate the concentration ratio of the three species originating from the acid at
pH = 4.03. Give the result as [H 2 A] : [HA–] : [A2–] = ….:……:1
1.9. Calculate the percentage of the H+ ions originating from the second
deprotonation step of C in the initial solution (at pH = 2.33).
Part III.
It is known that both acids contain C, H and O atoms only. One of the two unknown

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compounds is optically inactive, but there are two chirality centers, and the other one is
an aromatic compound.

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1.10. Draw the possible structures of the two unknown acids (with stereochemistry
and R/S notation for chiral centers where necessary).

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56th IChO Preparatory Problems 14

Solution
1.1.
Titrated as a diprotic acid: n(NaOH) = 0.100 mol dm–3 ∙ 0.01804 dm3 = 1.804∙10–3 mol
n(acid) = n(NaOH)/2 = 9.02∙10–4 mol
200
In the total stock solution: 25
∙ 9.02∙10–4 mol = 7.216∙10–3 mol

M(acid) = 1.200 g / 7.216∙10–3 mol = 166 g mol–1

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1.2.

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At pH = 5.51 [HA–] = [A2–] ⇒ pH = pK a,2 ⇒ K a,2 = 10–5.51 = 3.09∙10–6
At pH = 2.97 theoretically [HA–] = [H 2 A] ⇒ K a,1 = 10–2.97 = 1.07∙10–3

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1.3. nt
K ax (x is 1 or 2) based on the graph is probably inaccurate due to the following two factors:
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the total concentration of the acid in the titrated solution was relatively too (high/low)
while the K ax value in question was relatively too (large/small).
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Better estimate calculation:

K a = K a,1 ∙ K a,2 → K a,1 = 3.99∙10–9 / 3,09∙10–6 = 1.29∙10–3
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1.4.
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pK a,1 = –log(1.29∙10–3) = 2.89

At pH a an ampholyte solution exists, where pH = ½ (pK a,1 + pK a,2 ) = ½ (2.89 + 5.51) = 4.20
nf

1.5.
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Concentration of stock solution: c 1 = 7.216∙10–3 mol / 0.200 dm3 = 0.03608 mol dm–3
[HA–] ≈ [H+] (because K a,1 much larger than K a,2 )
[H 2 A] = c 1 – [H+] ([H+] can’t be neglected compared to the initial concentration, but
the second deprotonation can be.)
K a,1 = [H+]2 / (c 1 – [H+])
2
�𝐻𝐻 + �
= 1.29∙10–3
0.03608−⟦𝐻𝐻 + ⟧

56th IChO Preparatory Problems 15

From the equation: [H+] = 0.00621 mol dm–3
pH x = 2.21
At that point of the titration there is 9.02∙10–4 mol Na 2 A in the solution.
The volume of the solution is: 25.00 cm3 + 18.04 cm3 = 43.04 cm3
c 2 = 9.02∙10–4 mol / 0.04304 dm3 = 0.02096 mol dm–3
A2– + H 2 O = HA– + OH– K h = K w /K a,2 = 3.24∙10–9
The 2nd step of the hydrolysis can be neglected (K h,2 = 7.75∙10–12, that is too small.)

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[HA–] ≈ [OH–]
[A2–] ≈ c 2 – [OH–] ≈ c 2 (K h is too small.)

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⟦𝑂𝑂𝑂𝑂 – ⟧2
= 3.24∙10–9
0.02096

[OH–] = 8.24∙10–6 mol dm–3

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pOH = 5.08 ⇒ pH b = 8.92

1.6.
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The acid can only be titrated as diprotic. Phenolphthalein has the right color change range.
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1.7.
Phenolphthalein is again the best for the titration. Cresol red should also work with a
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slightly more acidic color change than the end point.

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1.8.
2
�H+ � �H+ �
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α H = [H 2 A] : [HA–] : [A2–] = : : 1.00 = 1.024 : 6.62 : 1.00

𝐾𝐾1 𝐾𝐾2 𝐾𝐾2
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1.9.
�H+ �
[HA–] : [A2–] = 𝐾𝐾2
: 1.00 = 332 : 1

[A2− ] 1
[HA− ]+2[A2− ]
= 332+2 = 2.99∙10–3 ≈ 0.3%

1.10.

56th IChO Preparatory Problems 16

Considering the molar masses and the two carboxylate groups, only B can be aromatic,
and it is one of the benzenedicarboxylic acids, phthalic acid.

B:
The meta and para isomers cannot be excluded by the students based on the limited data
available. Actually, the first and second dissociation constants of the other two isomers

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are closer to each other than of the ortho isomer in which the interaction between the two
carboxylic groups increases the first and decreases the second dissociation constant.
Based on the molar masses and two chirality centers with symmetry, C must be (2R,3S)-

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tartaric acid.

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C: ,
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56th IChO Preparatory Problems 17

2. Malic acid
Malic acid is a diprotic organic acid found in apples and other fruits. It is also prepared in
the chemical industry by the following two-step process, for which balanced chemical
equations are given.
1 n-butane + 3.5 O 2 → 1 maleic anhydride + 4 H 2 O
1 maleic anhydride + 2 H 2 O → 1 malic acid
The 1H NMR spectrum of maleic anhydride contains one singlet. The 13C NMR spectrum of

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the compound contains two lines, a relatively intense one, and a less intense one
downfield from the other.

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2.1. Give the molecular and structural formulas of the three organic compounds.
2.2. Give the number of the lines in the 13C NMR spectrum of malic acid.

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Apple juice is a nice drink itself but is also used to make apple cider vinegar in a two-step
process. In the first, fermentation produces ethanol from the sugars in apple juice.
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Interestingly, malic acid is also fermented in this step into ethanol. In the second, ambient
oxygen oxidizes the ethanol to acetic acid in the presence of microbes. It can be assumed
that all the sugars present in apple juice are simple hexoses that have the same formula
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as glucose and are fermented very similarly.
2.3. Give the balanced chemical equations of the reactions of the apple cider vinegar
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preparation process.
The structure of malic acid contains one asymmetric carbon atom, so the molecule is
chiral. In apples, only the enantiomer called L-malic acid occurs, in which the asymmetric
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carbon atom has S configuration in the CIP convention. The other enantiomer, D-malic
acid is the mirror image.
2.4. Give the stereostructures of the two enantiomers using wedge–dash notation (
id

; ).
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Interestingly, chemical vendors sell three different kinds of malic acid: they are called L-
(−)-Malic acid, D-(+)-Malic acid, and racemic DL-Malic acid .
2.5. Match the product to the properties given in the table.
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product identifier properties

(D, L, DL)
price: 0.50 euros/g; melting point range: 101 - 103 °C
price: 0.10 euros/g; melting point range: 131 - 133 °C
price: 30 euros/g; melting point/range: 98 – 102 °C

2.6. Identify the product produced directly by the industrial method shown above.

56th IChO Preparatory Problems 18

In a small family business producing apple cider vinegar from apple juice, one day the
final product did not contain any alcohol but tasted sweet rather than sour. The chief
chemist discovered that the same apple juice was used as in the previous day when
everything went OK. There was a pH-meter in good working order in the small lab and
some equipment for acid-base titrations. To discover what went wrong, a few
experiments were carried out. The chief chemist also remembered some important facts
that were established by earlier investigations when the business was started:
• The acidity of apple juice is practically only caused by malic acid.
• The acidity of proper apple cider vinegar is practically only caused by

ne
acetic acid.

• Neither apple juice, nor apple cider vinegar contains any metals in
concentrations comparable to those of their major organic components

Ju
(not even potassium and sodium).
First, the 2.00 cm3 of the proper apple cider vinegar produced on the previous day was

il
titrated with 0.1000 mol/dm3 sodium hydroxide solution using phenolphthalein as an
indicator. The end point was reached at 21.72 cm3. Then a sample was prepared by
nt
mixing 2.00 cm3 of the proper apple cider vinegar with 10.86 cm3 of 0.1000 mol/dm3
sodium hydroxide solution and enough water to bring the final volume to 25.00 cm3. The
pH of this solution was measured as 4.76.
lu
2.7. Calculate the acetic acid content of proper apple cider vinegar in g/dm3 units,
and then estimate the pK a of acetic acid.
tia

Next, 10.00 cm3 of apple juice was titrated with 0.1000 mol/dm3 sodium hydroxide
solution using phenolphthalein as an indicator. The end point was reached at 11.01 cm3.
In this case, two samples were prepared for pH measurement. In the first, 10.00 cm3 of
en

apple juice was mixed with 3.67 cm3 of 0.1000 mol/dm3 sodium hydroxide solution and
the final volume was adjusted to 25.00 cm3: the pH was measured as 3.67. In the second,
10.00 cm3 of apple juice was mixed with 7.35 cm3 of 0.1000 mol/dm3 sodium hydroxide
id

solution and the final volume was adjusted to 25.00 cm3: the pH was measured as 4.95.
2.8. Calculate the malic acid content of apple juice in g/dm3 units, and then estimate
nf

the two pK a values of malic acid.

2.9. Based on the data already available, estimate the sugar content of apple juice in
Co

g/dm3 units assuming that the volume of the solution does not change
significantly during fermentation. Assume 100% efficiency in all steps.
Then it was time to analyze the sweet batch obtained. 5.00 cm3 of this solution was diluted
to 100.00 cm3, the pH of the resulting solution was 3.03. Then another 5.00 cm3 of the
solution was mixed with 5.00 cm3 of 0.1000 mol/dm3 NaOH first and diluted to 100.00
cm3. The pH of the resulting solution was 4.52.
2.10. Calculate the concentrations of acetic and malic acids in the sweet batch in g/dm3
units.
2.11. Calculate the concentration of sugars in the in the sweet batch in g/dm3 units.

56th IChO Preparatory Problems 19

Solution
2.1.
molecular formula structural formula

n-butane C 4 H 10

ne
maleic
C4H2O3
anhydride

Ju
il
malic acid C4H6O5

nt
lu
2.2.
4 lines as there are 4 different carbon atoms (all of them are singlets under proton
tia

decoupling)

2.3.
en

Fermentation of sugars:
C 6 H 12 O 6 → 2C 2 H 5 OH + 2CO 2
id

Fermentation of malic acid:

nf

C 4 H 6 O 5 → C 2 H 5 OH + 2CO 2
Oxidation of ethanol:
Co

C 2 H 5 OH + O 2 → CH 3 COOH + H 2 O

2.4.

L-Malic acid D-Malic acid

56th IChO Preparatory Problems 20

2.5.
L-(−)-Malic acid 0.50 euros/g
DL-Malic acid 0.10 euros/g
D-(+)-Malic acid 30 euros/g
Note: the first and the third products have the same melting points, so they are
enantiomers. Therefore, the second product is the racemic malic acid. The first product is
a lot less expensive as it occurs in nature in an enantiomerically pure form, which is not
true for the third one.

ne
2.6.

Ju
Racemic DL-Malic acid

il
2.7.

nt
1:1 acid-base reaction, 0.1000 mol/dm3 · 21.72 cm3/2.00 cm3 = 1.086 mol/dm3
1.086 mol/dm3 · 60.05 g/mol = 65.21 g/dm3
lu
pK: equilibrium concentrations in the 25.00 cm3 sample
[H+] = 10–4.76 mol/dm3 = 1.738 · 10–5 mol/dm3
tia

[Na+] = 0.1000 mol/dm3 · 10.86 cm3/25.00 cm3 = 0.04344 mol/dm3

As the solution is acidic, the concentration of hydroxide ion is very low. From charge
en

balance:
[CH 3 COO–] = [Na+] + [H+] = 0.04346 mol/dm3
id

[CH 3 COOH] = 1.086 mol/dm3 · 2.00 cm3/25.00 cm3 – [CH 3 COO–] = 0.04342 mol/dm3
K a = [H+][CH 3 COO–]/[CH 3 COOH] = 1.740 · 10–5 mol/dm3
nf

pK a = 4.76
Remark: In the present case a shorter solution is possible by noting that the added NaOH
Co

neutralizes exactly 50% of the acetic acid. If [Na+] >> [H+] then the equilibrium
concentrations of acetate and acetic acid are practically equal, so pK a = pH. However, the
conditions of using the simplified formula (Henderson-Hasselbalch equation) need to be
satisfied.

2.8.
1:2 acid-base reaction, 0.1000 mol/dm3 · 11.01 cm3/10.00 cm3 / 2 = 0.05505 mol/dm3
0.05505 mol/dm3 · 134.09 g/mol = 7.382 g/ dm3

56th IChO Preparatory Problems 21

pK calculations:
In both measured samples, the analytical concentration of malic acid is:
[C 4 H 6 O 4 ] + [C 4 H 5 O 4 –] + [C 4 H 4 O 4 2–] = 0.05505 mol/dm3 · 10.0 cm3/25.00 cm3 = 0.02202
mol/dm3
From the dissociation equilibria:
[C 4 H 5 O 4 –] = 0.02202 mol/dm3 · K a1 [H+]/([H+]2+ K a1 [H+]+ K a1 K a2 )
[C 4 H 4 O 4 2–] = 0.02202 mol/dm3 · K a1 K a2 /([H+]2+ K a1 [H+]+ K a1 K a2 )

ne
From the first pH measurement:
[H+] = 10–3.67 mol/dm3 = 2.138 · 10–4 mol/dm3

Ju
[Na+] = 0.1000 mol/dm3 · 3.67 cm3/25.00 cm3 = 0.01468 mol/dm3
As the solution is acidic, the concentration of hydroxide ion is very low. From charge
balance:

il
[C 4 H 5 O 4 –] + 2[C 4 H 5 O 4 2–] = [Na+] + [H+] = 0.01489 mol/dm3
nt
0.02202 mol/dm3 · (K a1 [H+] + 2K a1 K a2 )/([H+]2+ K a1 [H+]+ K a1 K a2 ) = 0.01489 mol/dm3
(K a1 · 2.138 · 10–4 mol/dm3 + 2K a1 K a2 )/((2.138 · 10–4 mol/dm3)2+ K a1 · 2.138 · 10–4
lu
mol/dm3 + K a1 K a2 ) = 0.6762
3.091 · 10–8 mol2/dm6 – K a1 · 6.923 · 10–5 mol/dm3 – K a1 · K a2 · 1.3238 = 0 (Eq. 1)
tia

From the second pH measurement:

[H+] = 10–4.95 mol/dm3 = 1.122 · 10–5 mol/dm3
en

[Na+] = 0.1000 mol/dm3 · 7.35 cm3/25.00 cm3 = 0.02940 mol/dm3

As the solution is acidic, the concentration of hydroxide ion is very low. From charge
id

balance:
[C 4 H 5 O 4 –] + 2[C 4 H 5 O 4 2–] = [Na+] + [H+] = 0.02941 mol/dm3
nf

0.02202 mol/dm3 · (K a1 [H+] + 2K a1 K a2 )/([H+]2+ K a1 [H+]+ K a1 K a2 ) = 0.02941 mol/dm3

(K a1 · 1.122 · 10–5 mol/dm3 + 2K a1 K a2 )/((1.122 · 10–5 mol/dm3)2+ K a1 · 1.122 · 10–5
Co

mol/dm3 + K a1 K a2 ) = 1.3356
1.681 · 10–10 mol2/dm6 + K a1 · 3.765 · 10–6 mol/dm3 – K a1 · K a2 · 0.6644 = 0 (Eq. 2)
Eq.1 and Eq. 2 are two equations with two unknowns, which can be solved:
(1.681 · 10–10 mol2/dm6 + K a1 · 3.765 · 10–6 mol/dm3 – K a1 · K a2 · 0.6644) · 1.3238 – (3.091
· 10–8 mol2/dm6 – K a1 · 6.923 · 10–5 mol/dm3 – K a1 · K a2 · 1.3238) · 0.6644 = 0
–2.031 · 10–8 mol2/dm6 + K a1 · 5.098 · 10–5 mol/dm3 = 0
K a1 = 3.984 · 10–4 mol/dm3 (pK a1 = 3.40)

56th IChO Preparatory Problems 22

For K a2
1.681 · 10–10 mol2/dm6 + 3.984 · 10–4 mol/dm3· 3.765 · 10–6 mol/dm3 – 3.984 · 10–4
mol/dm3· K a2 · 0.6644 = 0
K a2 = 6.302 · 10–6 mol/dm3 (pK a2 = 5.20)
Remark: Here a shorter line of thought is possible based on the observation that 1/3 and
2/3 equivalents of NaOH are added to malic acid. But this approach yields pK a values that
are slightly off because the two acid dissociation steps are not sufficiently separated.

ne
2.9.
In apple cider vinegar, the concentration of acetic acid is 1.086 mol/dm3, 0.05505

Ju
mol/dm3 of which comes the fermentation of malic acid. Therefore, the original sugar
concentration is (1.086 mol/dm3 – 0.05505 mol/dm3) / 2 = 0.5155 mol/dm3. So, the mass
concentration is 0.5155 mol/dm3 · 180.16 g/mol = 92.87 g/dm3

il
2.10.
nt
Denote the analytical concentration of acetic acid c A , the analytical concentration of malic
lu
acid c M . As we know the acid dissociation constants, the concentrations of the
deprotonated forms can be given at a known pH:
[CH 3 COO–] = c A · K a /([H+]+ K a )
tia

[C 4 H 5 O 4 –] = c M · K a1 [H+]/([H+]2+ K a1 [H+]+ K a1 K a2 )
[C 4 H 4 O 4 2–] = c M · K a1 K a2 /([H+]2+ K a1 [H+]+ K a1 K a2 )
en

At pH 3.03, [H+] = 9.333 · 10–4 mol/dm3

[H+] = [CH 3 COO–] + [C 4 H 5 O 4 –] + 2[C 4 H 4 O 4 2–]
id

9.333 · 10–4 mol/dm3 = c A /20 · 0.01830 + c M /20 · 0.2986 + c M /20 · 0.004032 (Eq. 3)
nf

At pH 4.52, [H+] = 3.030 · 10–5 mol/dm3 and [Na+] = 0.1000 mol/dm3 · 5.00 cm3/100.00
cm3 = 0.005000 mol/dm3
Co

[H+] + [Na+] = [CH 3 COO–] + [C 4 H 5 O 4 –] + 2[C 4 H 4 O 4 2–]

0.005030 mol/dm3 = c A /20 · 0.3648 + c M /20 · 0.7788 + c M /20 · 0.3240 (Eq. 4)
Eq. 3 and Eq. 4 are two equations with two unknowns, they can be solved:
0.3648 · 9.333 · 10–4 mol/dm3 – 0.01830 · 0.005030 mol/dm3 = 0.3648 · (c A /20 · 0.01830
+ c M /20 · 0.2986 + c M /20 · 0.004032) – 0.01830 · (c A /20 · 0.3648 + c M /20 · 0.7788 +
c M /20 · 0.3240)
2.484 · 10–4 mol/dm3 = 0.004511c M
c M = 0.05507 mol/dm3

56th IChO Preparatory Problems 23

From 0.005030 mol/dm3 = c A /20 · 0.3648 + 0.05507 mol/dm3/20 · (0.7788 + 0.3240)
c A = 0.1093 mol/dm3

2.11.
Malic acid was not fermented at all, and only a small amount of the sugars was fermented.
0.1093 mol/dm3 acetic acid formed from the fermentation of 0.05465 mol/dm3 of sugar
(roughly 10% of the normal value), so there is still 0.5155 mol/dm3 – 0.05465 mol/dm3 =
0.4608 mol/dm3 of sugar in the product, which is 83.02 g/dm3.

ne
Ju
il
nt
lu
tia
en
id
nf
Co

56th IChO Preparatory Problems 24

3. Hydrazine salts
Hydrazine (N 2 H 4 ) is a weak diprotic base (K b1 = 8.5∙10–7; K b2 = 8.9∙10–16). It can form
various anhydrous salts with sulfuric acid. The second acid dissociation constant of
sulfuric acid is K a2 = 1.02∙10–2.
3.1. Provide the theoretically conceivable empirical formulas of anhydrous salts.
3.2. Starting from aqueous solutions, two of these salts can be expected to form.
Identify these two salts? Why doesn’t the aqueous procedure work for the other

ne
salts?
3.3. Calculate the pH of the 0.1 M solutions of these salts?

Ju
il
nt
lu
tia
en
id
nf
Co

56th IChO Preparatory Problems 25

Solution
3.1.
In theory, salts with the following compositions, containing two types of ions, can exist:
(N 2 H 5 )(HSO 4 ), empirical formula N 2 H 6 SO 4
(N 2 H 5 ) 2 (SO 4 ), empirical formula N 4 H 10 SO 4
(N 2 H 6 )(HSO 4 ) 2 , empirical formula N 2 H 8 S 2 O 8

ne
(N 2 H 6 )(SO 4 ), empirical formula N 2 H 6 SO 4

Ju
3.2.
The salt with the empirical formula N 2 H 6 SO 4 can be described as (N 2 H 5 )(HSO 4 ) in

il
solution. It is easily shown that the equilibrium:

N2 H62+ + SO2− -
+
4 ⇌ N2 H5 + HSO4
nt
is strongly shifted to the right due to the high equilibrium constant of the process.
lu
𝐾𝐾𝑤𝑤
𝐾𝐾 = = 1.1 ∙ 103
𝐾𝐾𝑎𝑎2 ⋅ 𝐾𝐾𝑏𝑏2
tia

The preparation of N 2 H 6 (HSO 4 ) 2 would also be problematic because the concentration of

N2 H62+ ions is very low compared to N2 H5+ ions. Their concentration ratio is low even at
pH 1.
en

[N2 H62+ ] 𝐾𝐾𝑏𝑏2 +

= [H ] = 8.9 ∙ 10−3
[N2 H5+ ] 𝐾𝐾𝑤𝑤
id

That is because the diprotonated hydrazine is a rather strong acid.

𝐾𝐾
nf

K a = 𝐾𝐾 𝑤𝑤 = 11.2
𝑏𝑏2

We only expect (N 2 H 5 )(HSO 4 ) and (N 2 H 5 ) 2 (SO 4 ) as feasible in solution. [Actually, in the

Co

solid (N 2 H 6 )(SO 4 ) was detected.]

3.3.
Let us first calculate the pH of the 0.1 mol/dm3 (N 2 H 5 )(HSO 4 ) solution. In the first
approximation, neglect the hydrolysis of the N2 H5+ ion. This seems justified because it is
very weak both as an acid and as a base. In this case, the pH is practically determined only
by the hydrolysis of the HSO 4 – ion.
[H+ ]2
K a2 = 𝑐𝑐−[H+], giving [H+] = 2.72∙10–2, and pH = 1.56

56th IChO Preparatory Problems 26

If we consider the hydrolysis of the N2 H5+ ion, it suffices to account for the presence of
[N 2H+5 ] 𝐾𝐾𝑏𝑏1
N2 H62+ . The N 2 H 4 concentration is still negligible, because [N2 H4 ]
= 𝐾𝐾 ⋅ [H + ] = 2.3∙106 at
𝑤𝑤
the estimated pH.
Writing down the usual system of equations (equilibrium constants, charge and mass
balance), we arrive at the following third-order equation:
𝐾𝐾𝑏𝑏2 𝐾𝐾𝑏𝑏2 𝐾𝐾𝑏𝑏2 ⋅ 𝑐𝑐 1
⋅ [𝐻𝐻 + ]3 + ( + + ) ⋅ [𝐻𝐻 + ]2 + [𝐻𝐻 + ] − 𝑐𝑐 = 0
𝐾𝐾𝑤𝑤 ⋅ 𝐾𝐾𝑎𝑎2 𝐾𝐾𝑤𝑤 𝐾𝐾𝑤𝑤 ⋅ 𝐾𝐾𝑎𝑎2 𝐾𝐾𝑎𝑎2
From this [H+] = 2.71∙10–2 mol/dm3, and pH = 1.57. So, the neglect of the hydrolysis was

ne
justified.

Ju
Some simplifications can be made when calculating the pH of 0.1 mol/dm3 (N 2 H 5 ) 2 (SO 4 )
[N2 H2+
6 ]
solution. The protonation of N2 H5+ is certainly negligible, because the [N2 H+
ratio was
5]
already very small at pH 1.

il
If we consider the low basicity of sulfate ions and disregard their protonation, then the
nt 𝐾𝐾
system simplifies to the pH of a 0.2 mol/dm3 weak acid. (K a = 𝐾𝐾 𝑤𝑤 = 1.18∙10–8)
𝑏𝑏1
lu
[H+] = �𝐾𝐾𝑎𝑎 ⋅ 𝑐𝑐 = 4.86∙10–5, pH = 4.3

If we do not neglect the protonation of sulfate and the deprotonation of N2 H5+ ions, then
the system of equations gives another third-order equation.
tia

𝐾𝐾𝑏𝑏1 𝐾𝐾𝑏𝑏1 ⋅ 𝑐𝑐 1 𝐾𝐾𝑏𝑏1 𝑐𝑐

⋅ [H + ]3 + ( + + ) ⋅ [H + ]2 + (1 − )[H + ] − 2𝑐𝑐 = 0
𝐾𝐾𝑤𝑤 ⋅ 𝐾𝐾𝑎𝑎2 𝐾𝐾𝑤𝑤 ⋅ 𝐾𝐾𝑎𝑎2 𝐾𝐾𝑎𝑎2 𝐾𝐾𝑤𝑤 𝐾𝐾𝑎𝑎2
en

Here [H+] = 1.48∙10–5 mol/dm3, and pH = 4.83. Here the simplifications caused a sizable
difference. Although only a small portion of the sulfate ions gets protonated, the resulting
shift in the hydrazonium deprotonation yields a noticeable pH shift.
id
nf
Co

56th IChO Preparatory Problems 27

4. CCM
Caustic calcined magnesia (CCM) is a valuable product from Saudi Arabia, primarily
composed of magnesium oxide. CCM with lower purity finds use in industrial applications
like wastewater treatment, while higher-purity CCM serves roles in pharmaceuticals,
cattle feed supplements, fertilizers, adhesives, tires, and magnetic materials.
Ali was tasked with quickly determining the mass percentage composition of a CCM
sample. His measuring equipment (a balance and a thermometer) and chemicals were
very limited, so he was thinking about a thermochemical method for this analysis. He was

ne
informed that the CCM sample had detectable quantities of calcium oxide and silicon
dioxide alongside magnesium oxide. He also located the necessary data.

Ju
∆ f H°∆ ∆ f H° cp
(kJ mol–1) (kJ mol–1) (kJ kg–1 K–1)

CaO(s) –636 H+(aq) 0.0 H 2 O(l)* 4.178

il
MgO(s) –602 Cl–(aq) –168 CaO(s) 0.918
SiO 2 (s)
HCl(g)
H 2 O(l)
–854
–92.5
–286
Ca2+(aq)
Mg2+(aq) nt–543
–462
MgO(s)
SiO 2 (s)
0.877
0.736
lu
CaCl 2 (s) –796 ∆ r H°(kJ mol–
1)

MgCl 2 (s) –641 H (aq) + OH (aq) = H 2 O(l)

+ – –56.0
tia

* He assumed that all aqueous solutions have the same specific heat capacity as the water.
To begin, he set up a calorimeter with improvised isolation and proceeded to measure its
heat capacity the following way. He introduced 200 cm3 of 0.500 M HCl solution (density:
en

1.007 g cm–3) into the calorimeter and 300 cm3 of 0.400 M NaOH solution (density:
1.016 g cm–3) into a separate beaker. Both solutions were initially at 24.2 °C. After pouring
the alkaline solution into the calorimeter, he observed the highest temperature reached
id

after the reaction, which was recorded as 26.3 °C.

4.1. Calculate the heat capacity of the calorimeter Ali improvised.
nf

Subsequently, Ali carefully weighed out a 12.81 g sample of the CCM. Following a thorough
cleaning of the calorimeter, he introduced 500 cm3 of 2.000 M hydrochloric acid (density:
Co

1.033 g cm–3) into it and waited for the temperature to stabilize at 24.4 °C (consistent with
the lab temperature). He then added the CCM sample into the hydrochloric acid, stirring
the solution until it reached its peak temperature of 40.5 °C. Following this reaction, Ali
filtered the contents of the calorimeter. After washing and drying, he isolated a solid
insoluble material with a mass of 0.51 g.
4.2. Write balanced ionic equations for the relevant processes happening during the
dissolution of CCM in hydrochloric acid. Calculate their standard enthalpy
change.
Ali started to analyze his result and the various factors determining it.

56th IChO Preparatory Problems 28

4.3. Based on Ali’s experimental data, calculate the mass percentage MgO content of
the CCM sample.
4.4. Identify the factor with the smallest effect on the value of MgO content if
neglected in the calculation?
◻ Heat capacity of the calorimeter
◻ Warming of the undissolved solid
◻ Warming of the aqueous solution
◻ Reaction of CaO with hydrochloric acid

ne
4.5. Calculate the final observed temperature if his CCM sample in the same
experiment was pure magnesia?

Ju
Ali became quite suspicious after carrying out the same calculations. He was happy to
locate some phenolphthalein solution. He managed to devise a method using the very
same tools and chemicals as in the thermochemical experiment and measure the MgO

il
content more accurately.
4.6. Write down such a procedure.
nt
lu
tia
en
id
nf
Co

56th IChO Preparatory Problems 29

Solution
4.1.
200 cm3 0.500 M HCl solution contains 0.100 mol H+,
300 cm3 0.400 M NaOH solution contains 0.120 mol OH–,
0.100 mol H+ is the limiting agent, therefore: Q = 0.100 mol · (56 kJ mol–1) = 5.60 kJ
200 cm3 of hydrochloric acid: m 1 = 200 cm3 · 1,007 g cm–3 = 201.4 g

ne
300 cm3 of NaOH solution: m 2 = 300 cm3 · 1.016 g cm–3 = 304.8 g
Total mass of the final solution: m 1 + m 2 = 506.2 g.

Ju
Temperature change: ∆T = 26.3 °C – 24.2 °C = 2.1 °C = 2.1 K
5600 J = 4.178 J g–1 K–1 · 506.2 g · 2.1 K + C(calorimeter) · 2.1 K

il
C(calorimeter) = 552 J K–1

4.2.
nt
lu
MgO(s) + 2 H+(aq) = Mg2+(aq) + H 2 O(l)
∆ r H 1 = –462 + (–286) – (–602) = –146 kJ mol–1
tia

CaO(s) + 2 H+(aq) = Ca2+(aq) + H 2 O(l)

en

∆ r H 2 = –543 + (–286) – (–636) = –193 kJ mol–1

id

4.3.
There was 0.51 g SiO 2 in the CCM sample. The mass of MgO–CaO was:
nf

12.81 g – 0.51 g = 12.30 g.

Co

The mass of the final solution: 500 cm3 · 1.033 g cm–3 + 12.30 g = 528.8 g.
Temperature change: ∆T = 40.5 °C – 24.4 °C = 16.1 °C = 16.1 K
Q = 4.178 J g–1 K–1·528.8 g·16.1 K + 552 J K–1·16.1 K + 0.736 J g–1 K–1·0.51 g·16.1 K
Q = 35 570 J + 8887 J + 6.04 J = 44 463 J = 44.463 kJ
If there are x mol of MgO and y mol of CaO in the mixture:
40.3x + 56.1y = 12.3
146x + 193y = 44.463

56th IChO Preparatory Problems 30

From these equations: x = 0.2919
m(MgO) = 0.2919 mol · 40.3 g mol–1 = 11.76 g
w(MgO) = 11.76 g : 12.81 g = 0.92 → 92 w% MgO

4.4.
Warming of the undissolved solid

ne
4.5.
12.81 g of pure MgO dissolution would result in 46.408 kJ released.

Ju
Taking the heat capacity of the whole system into account, this means a temperature
increase of 16.8 °C.

il
Since the temperature is reported to one decimal, the procedure is very sensitive to the
accuracy of the temperature change measured. The calculated MgO content is not very
nt
reliable unless the thermal measurements were much more accurate.
lu
4.6.
With the help of the phenolphthalein solution the excess of the HCl solution used to
tia

dissolve the sample could be determined:

Using a balance and knowing the density of the acid and base solution, one can measure
out an excess of acid solution (measuring the mass of the container with and without the
en

acid) and the mass of the added CCM sample.

If one uses the solutions used for the heat capacity measurement and starts adding NaOH
id

solution dropwise after the dissolution of CCM, one can observe when the excess acid is
neutralized, and the mixture turns basic (pink with phenolphthalein).
nf

The mass of the added NaOH solution at that point will allow the calculation of the acid
amount needed to dissolve the CCM. Since the balance can reliably measure 0.01 g, the
results are much more reliable.
Co

E.g.:
Measuring out the 12.81 g sample from the 92% MgO or from pure MgO and dissolving
them in 200 cm3 of 2.000 M HCl solution will result in mixtures that require 246.4 cm3
and 205.3 cm3 from the 0.400 M NaOH solution for neutralization. The difference between
the masses of these solutions will be measured quite accurately.

56th IChO Preparatory Problems 31

5. Carbon capture
Carbon capture, storage and utilization is an important area of technological research. A
few years ago, a water-fed electrolyzer was reported to achieve a current density of
420 mA/cm2 for CO generation without difficulty. The cell design is as follows:
The key is the central ion exchange
membrane, in which certain ions are
mobile. On either side of this membrane
is a GDL - a gas diffusion layer. This is a

ne
partially wettable porous material on
whose surface a catalyst is deposited. Optimally, both the gas and the electrolyte enter
and leave the pores and electricity is conducted through the layer.

Ju
5.1. What could be this cheap, modifiable, inert, porous, and conductive layer on the
cathode side?

il
This carrier is activated on the cathode side by a silver nanoparticle catalyst. On the anode
side, the gas diffusion layer is a porous Ti-film with an IrOx nanoparticle catalyst on its
surface. nt
Humidified carbon dioxide is passed through the cathode space wetted with a neutral
lu
solution, while a more concentrated (1 M) KOH solution is usually passed through the
anode space.
tia

5.2. Give the expected cathode and anode electrode reactions (in a form appropriate
for the pH of solutions). Give is the net reaction of electrolysis?
The material of the ion exchange membrane is indeed
en

crucial. Commonly used porous polymers in

electrochemistry, such as Nafion or SPEEK (structures
are on the figure on the right) present practical
id

challenges in this system.

If these membrane materials were employed, two ions
nf

could permeate them, leading to undesirable

outcomes. One ion can alter the pH at the cathode,
influencing product composition through an
Co

alternative electrode reaction. On the other hand, if

the other ion flows through the membrane, the
cathode space would maintain a near-neutral pH, but the solid filling the pores would
hinder extended electrolysis.
5.3. Identify these two ions and the direction in which they could flow across the
membranes.
Write down the side reaction mentioned for one of them and the formula of the
solid that would form in the pores due to the flow of the other ion.

56th IChO Preparatory Problems 32

 If the ion-exchange membrane is made of the polymer on
the left, the situation improves. Additional chemical
reactions are still likely to happen in the cathode space due
to the high concentration of carbon dioxide.
5.4. Name the ions and the direction in which they can flow
through this separation membrane.

ne
In the cagse of continuous operation (after one hour), steady-state operation of the system
is established and the two-component gas leaving the anode space will have only 1/3 as
the oxygen mole fraction.

Ju
5.5. Name the other component in the gas. Determine, based on the stoichiometry of
the chemical and electrochemical processes involved, which of the various ions
capable of passing through the membrane serves as the primary charge carrier.

il
5.6. In the case of ideal electrochemical selectivity, calculate the fraction of the CO 2

5.7.
nt
input that is converted to CO in this steady state?
Calculate the minimum CO 2 volume flow rate with a 100 cm2 electrode and a
lu
steady current density of 420 mA/cm2. The temperature of the gas at atmospheric
pressure is 60°C.
tia
en
id
nf
Co

56th IChO Preparatory Problems 33

Solution
5.1.
graphite

5.2.
cathode:

ne
CO 2 + H 2 O + 2e− = CO + 2 OH− or 3 CO 2 + H 2 O + 2e− = CO + 2 HCO 3 − or 2 CO 2 + 2e− = CO +
CO 3 2−

Ju
anode:
4 OH− = O 2 + 2 H 2 O + 4e− or 2 H 2 O = O 2 + 4 H+ + 4e−

il
net:
2 CO 2 = 2 CO + O 2
nt
lu
5.3.
Protons or potassium ions would be able to permeate the membrane from the anode to
the cathode.
tia

If protons decreased the pH at the cathode, then hydrogen evolution could start more
easily:
en

2 H+ + 2e− = H 2
The precipitation of solid KHCO 3 in the pores of the cathode could be the other challenge.
id

5.4.
nf

Anions in the system, i.e.: OH−, HCO 3 −, CO 3 2− could get through this membrane from the
cathode to the anode.
Co

5.5.
The other component must be CO 2 from the anions diffusing through the membrane.
Thus, hydroxide cannot be the primary charge carrier.
If one mol of oxygen is produced on the anode, then 4 moles of acid are also produced.
That would produce 4 moles of CO 2 if hydrocarbonate anions or 2 moles if carbonate ions
were the main carriers of charge. Thus, carbonate ions are the main carriers of charge
through the membrane:

56th IChO Preparatory Problems 34

2 CO 3 2− = 2 CO 2 + O 2 + 4e− vs 4 HCO 3 − = 4 CO 2 + O 2 + 2 H 2 O + 4e−

5.6.
Half of the CO 2 will get reduced, the other half will be transported through the membrane
as carbonate.

5.7.

ne
The current flowing through the 100 cm2 electrode is 42 A.
That is 0.435 mmol of electrons in a second and the same amount of CO 2 reacting:

Ju
4 CO 2 (cathode) = 2CO(cathode) + 2 CO 2 (anode) + O 2 (anode)
Under these conditions 0.435 mmol of ideal gas is 11.9 cm3. that means a 42.8 dm3/hour
flow of the gas.

il
Reference: nt
Endrődi, B., Samu, A., Kecsenovity, E. et al. Operando cathode activation with alkali metal
lu
cations for high current density operation of water-fed zero-gap carbon dioxide
electrolysers. Nat Energy 6, 439–448 (2021). https://doi.org/10.1038/s41560-021-
00813-w
tia
en
id
nf
Co

56th IChO Preparatory Problems 35

6. Nanoparticles
Nanoparticles have attracted growing scientific interest in recent decades. Physical,
optical and electronic properties of nanoparticles in comparison with bulk phases of
similar chemical composition are fundamentally determined by their size. However, this
size is never uniform, as particles of varying sizes are present in any real sample. As a
result, the size cannot be characterized by a simple number, not even by an average.
Typically, the size distribution of nanoparticles needs to be determined experimentally.
A simplified model of nanoparticle size distribution is the following. Monomer unit M 1 is

ne
assumed to be engaged in a series of equilibrium reactions in which growing
nanoparticles are produced. M i denotes the particle with exactly i monomeric units in it.
The equilibria are described by the following general reaction:

Ju
M𝑖𝑖 + M1 ⇌ M𝑖𝑖+1
As a first approach, the equilibrium constants (K) of all such processes are assumed to be

il
equal, so independent of the value of i.
[M𝑖𝑖+1 ]
[M𝑖𝑖 ][M1 ]
= 𝐾𝐾 nt
lu
Imagine an experiment in which initial concentration of M 1 (before the formation of any
nanoparticles) was T, and the molar mass M 1 is W.
6.1. Derive a formula that gives the average molar mass of the nanoparticles formed
tia

as a function of T, W, and K.
Hint: you might need the formula to sum an infinite geometric series:
en

∞
𝑎𝑎
� 𝑎𝑎 𝑟𝑟 𝑘𝑘 = for |𝑟𝑟| < 1
1 − 𝑟𝑟
𝑘𝑘=0
id

The size of the individual nanoparticles is not proportional to their mass. If the particle
shape is assumed to be approximately spherical, then the size of a particle (d i ) is
nf

proportional to the cube root of the molar mass, which is directly proportional to i, the
number of monomeric units in it. So overall:
Co

3
𝑟𝑟𝑖𝑖 = 𝑟𝑟0 √𝑖𝑖
Here, r 0 is a constant representing the hypothetical size of the 'nanoparticle' containing a
single monomeric unit.
Distributions are frequently illustrated using histograms, which are bar diagrams. The x-
axis of the histogram displays ranges of the property of interest, while the height of the
bars is proportionate to the probability of finding the property within the specified range.

56th IChO Preparatory Problems 36

6.2. Utilizing spreadsheet software, create two histograms based on the outlined
system. Set T = 1 mol dm⁻³ and K = 10⁶ mol⁻¹ dm³ for the calculations. The first
histogram should depict the distribution of molar masses of the nanoparticles,
with a range width of 100W. This implies the first column represents the molar
mass range 0–100W, the second 100W–200W, and so forth. The second
histogram should display the distribution of nanoparticle sizes, with r₀ as the
width of the range.

ne
Ju
il
nt
lu
tia
en
id
nf
Co

56th IChO Preparatory Problems 37

Solution
6.1.
From the equilibrium constant:
[M𝑖𝑖+1 ] = 𝐾𝐾[M𝑖𝑖 ][M1 ]

So generally,

[M𝑖𝑖+1 ] = [M1 ](𝐾𝐾[M1 ])𝑖𝑖

ne
The total concentration of nanoparticles is (a known formula for the sum of the geometric series
is used):
[M ]
∑∞ ∞ 𝑖𝑖
𝑖𝑖=0[M𝑖𝑖+1 ] = [M1 ] ∑𝑖𝑖=0(𝐾𝐾[M1 ]) = 1−𝐾𝐾[M
1

Ju
1]

In equilibrium, K[M 1 ] < 1 is always true (i.e. the decrease in concentration of M 1 cannot stop
before this condition becomes true).

il
Mass conservation for the nanoparticles is stated as follows:

𝑇𝑇 = ∑∞ ∞
nt
𝑖𝑖=0(𝑖𝑖 + 1)[M𝑖𝑖+1 ] = [M1 ] ∑𝑖𝑖=0(𝑖𝑖 + 1)(𝐾𝐾[M1 ])
𝑖𝑖

We have already used the formula for the sum of a geometric series, which is:
lu
1
∑∞ 𝑖𝑖
𝑖𝑖=0(𝐾𝐾[M1 ]) = 1−𝐾𝐾[M1 ]

There is a clever re-arrangement of the sum that needs to be calculated:

tia

∑∞ 𝑖𝑖 0 1 2 3 0
𝑖𝑖=0(𝑖𝑖 + 1)(𝐾𝐾[M1 ]) = (𝐾𝐾[M1 ]) + 2(𝐾𝐾[M1 ]) + 3(𝐾𝐾[M1 ]) + 4(𝐾𝐾[M1 ]) + ⋯ = ((𝐾𝐾[M1 ]) +

(𝐾𝐾[M1 ])1 + ⋯ ) + ((𝐾𝐾[M1 ])1 + (𝐾𝐾[M1 ])2 + ⋯ ) + ((𝐾𝐾[M1 ])2 + (𝐾𝐾[M1 ])3 + ⋯ ) + ⋯ =
en

∑∞ 𝑖𝑖 ∞ 𝑖𝑖 2 ∞ 𝑖𝑖
𝑖𝑖=0(𝐾𝐾[M1 ]) + 𝐾𝐾[M1 ] ∑𝑖𝑖=0(𝐾𝐾[M1 ]) + (𝐾𝐾[M1 ]) ∑𝑖𝑖=0(𝐾𝐾[M1 ]) + ⋯ =

1 2
�∑∞ 𝑖𝑖 ∞ 𝑖𝑖
𝑖𝑖=0(𝐾𝐾[M1 ]) ��∑𝑖𝑖=0(𝐾𝐾[M1 ]) � = �1−𝐾𝐾[M ]�
id

Therefore:
nf

[M ]
1
𝑇𝑇 = (1−𝐾𝐾[M 2
1 ])
Co

Rearranging:
1
𝐾𝐾 2 [M1 ]2 − �2𝐾𝐾 + � [M1 ] + 1 = 0
𝑇𝑇

The physically meaningful root is:

1 1 2
2𝐾𝐾+ −��2𝐾𝐾+ � −4𝐾𝐾2 1 1 1 1 1
𝑇𝑇 𝑇𝑇
[M1 ] = = + − � +
2𝐾𝐾2 𝐾𝐾 2𝐾𝐾2 𝑇𝑇 𝐾𝐾 𝐾𝐾𝐾𝐾 𝐾𝐾2 𝑇𝑇 2

The average molar weight of the nanoparticles is their total mass divided by the total amount of
substance:

56th IChO Preparatory Problems 38

 𝐾𝐾 𝐾𝐾 𝐾𝐾 1 1
1− − + � +
𝑇𝑇𝑇𝑇 𝐾𝐾 2𝐾𝐾2 𝑇𝑇 𝐾𝐾 𝐾𝐾𝐾𝐾 𝐾𝐾2 𝑇𝑇2 2𝐾𝐾𝐾𝐾√𝐾𝐾𝐾𝐾+1−𝐾𝐾𝐾𝐾
𝑊𝑊ave = [M1 ] = 𝑊𝑊𝑊𝑊 = 𝑊𝑊
1 1 1 1 1 2𝐾𝐾𝐾𝐾+1−2√𝐾𝐾𝐾𝐾+1
1−𝐾𝐾[M1 ] + − � +
𝐾𝐾 2𝐾𝐾2 𝑇𝑇 𝐾𝐾 𝐾𝐾𝐾𝐾 𝐾𝐾2 𝑇𝑇2

6.2.
A sample Google sheet is available at http://bit.ly/icho56nano.
The first histogram:

0.10

ne
0.08

Ju
probability

0.06

0.04

il
0.02

0.00
nt
lu
0 500 1000 1500 2000 2500 3000 3500 4000 4500
molar mass (W)
tia

The second histogram:

0.14
en

0.12

0.10
probability

id

0.08

0.06
nf

0.04

0.02
Co

0.00
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
size (r0)

56th IChO Preparatory Problems 39

7. Adiabatic reactor
A constant-volume adiabatic reactor is primarily a theoretical construct that helps in
understanding the concepts of thermodynamics. In a reactor like this no heat exchange is
possible with the environment, and the overall volume is constant, so if chemical reactions
occur, other parameters like temperature and pressure change in response. This reactor
also helps to some extent imagine what happens during gas explosions.
Imagine the burning of carbon monoxide in a constant-volume adiabatic reactor. The fixed
volume is 1.00 m3, 50.0 mol carbon monoxide and 50.0 mol oxygen is fed into the reactor

ne
at the beginning, the initial temperature is 298 K.
You can assume that all gases and their mixture follow the ideal gas law. Note, that the

Ju
molar entropy of an ideal gas has the following temperature and pressure dependence:
𝑇𝑇 𝑝𝑝
𝑆𝑆𝑚𝑚 (𝑝𝑝, 𝑇𝑇) = 𝑆𝑆𝑚𝑚 (𝑝𝑝0 , 𝑇𝑇0 ) + 𝐶𝐶𝑝𝑝 ln − 𝑅𝑅 ln
𝑇𝑇0 𝑝𝑝0

il
Use the following data:

O 2 (g)
C p (Jmol−1K−1)
29.4
ont
𝑆𝑆298
205.2
o
(Jmol−1K−1) Δ f𝐻𝐻298 (kJ mol−1)
lu
CO(g) 29.1 197.7 −110.5
CO 2 (g) 37.1 213.8 −393.5
tia

The constant pressure molar heat capacities are independent of temperature above
298 K.
7.1. Give the balanced chemical equation of the reaction and its standard enthalpy
en

(Δ r H°).
The amount of carbon dioxide formed in the reaction is n CO2 mol.
id

7.2. Give the stoichiometrically possible maximum value of n CO2 ?

7.3. Using n CO2 as an independent variable derive expressions that give certain
nf

thermodynamic properties of the system. Where it is not possible to give an

expression for the property itself, give the expression for the change in the
Co

property relative to the initial conditions.

a) the internal energy (U) of the system
b) the temperature (T) of the system
c) the pressure (p) of the system
d) the reaction quotient (Q)
e) the enthalpy of the system (H)
f) the entropy of the system (S)
g) the Gibbs free energy of the system (G)
h) the equilibrium constant of the reaction (K) at the given temperature (already
obtained as T)

56th IChO Preparatory Problems 40

7.4. Use spreadsheet software to calculate each property for n CO2 = 1 mol, 2 mol,
3 mol,
On the spreadsheet, find the n CO2 value at which the system is in equilibrium
Which of the previously listed properties has an extremum in the equilibrium?

ne
Ju
il
nt
lu
tia
en
id
nf
Co

56th IChO Preparatory Problems 41

Solution
7.1.
2CO(g) + O 2 (g) → 2CO 2 (g)
∆H° 298 = 2 · (−393.5) − 2 · (−110.5) = −566.0 kJ/mol

7.2.

ne
50 mol

Ju
7.3.
a) Only the change in the internal energy can be calculated. This is zero at any point as the

il
system is isolated (first law of thermodynamics).

nt
b) ∆U° 298 = ∆H° 298K − p°∆V° 298 = −566.0 kJ/mol − ∆nR · 298 K
lu
∆n = −1 mol, so ∆U° = −563.5 kJ/mol
𝑛𝑛CO = 50 mol − 𝑛𝑛CO2
tia

𝑛𝑛O2 = 50 mol − 0.5𝑛𝑛CO2

For each gas, C V = C p − R
en

From the constant internal energy:

J
0 = −563500 ∙ 0.5 𝑛𝑛CO2 + 𝐶𝐶𝑉𝑉,CO2 ∙ 𝑛𝑛CO2 ∙ Δ𝑇𝑇 + 𝐶𝐶𝑉𝑉,CO ∙ 𝑛𝑛CO ∙ Δ𝑇𝑇 + 𝐶𝐶𝑉𝑉,O2 ∙ 𝑛𝑛O2 ∙ Δ𝑇𝑇
mol
id

kJ
563.5 ∙ 0.5 𝑛𝑛CO2
Δ𝑇𝑇 = mol
nf

�𝐶𝐶𝑝𝑝,CO2 − 𝑅𝑅�𝑛𝑛CO2 + �𝐶𝐶𝑝𝑝,CO − 𝑅𝑅�(50 mol − 𝑛𝑛CO2 ) + �𝐶𝐶𝑝𝑝,O2 − 𝑅𝑅�(50 mol − 0.5 𝑛𝑛CO2 )
Co

J
281750 ∙ 𝑛𝑛
Δ𝑇𝑇 = mol CO2
J J
2095 − 2.55 ∙ 𝑛𝑛
mol mol K CO2
T = 298 K + ∆T

c)
𝑅𝑅𝑅𝑅
𝑝𝑝 = (50 mol − 0.5𝑛𝑛CO2 )
𝑉𝑉

56th IChO Preparatory Problems 42

d)
𝑝𝑝CO2 2
� 𝑝𝑝° � (𝑛𝑛CO2 )2 𝑉𝑉𝑉𝑉° (𝑛𝑛CO2 )2 ∙ 1.203 ∙ 104 mol K
𝑄𝑄 = = =
𝑝𝑝CO 2 𝑝𝑝O2 (𝑛𝑛CO )2 (𝑛𝑛O2 )𝑅𝑅𝑅𝑅 (50 − 𝑛𝑛CO2 )2 (50 − 0.5𝑛𝑛CO2 )𝑇𝑇
� 𝑝𝑝° � � 𝑝𝑝° �

e) Only the change can be calculated from the initial conditions

∆H = ∆U + ∆(pV)

ne
∆U is already known to be zero, therefore:
∆H = (p − p 298 ) · 1.00 m3

Ju
p 298 is the initial pressure, can be obtained from the ideal gas law (248 kPa)

il
f) The absolute entropy can be calculated (3rd law of thermodynamics)

𝑆𝑆 = 𝑛𝑛CO2 �𝑆𝑆°CO2,298 + 𝐶𝐶𝑝𝑝,CO2 ∙ ln nt

𝑇𝑇
298 K
+ 𝑅𝑅 ∙ ln
(100 mol − 0.5𝑛𝑛CO2 )100 kPa
𝑛𝑛CO2 ∙ 𝑝𝑝
�+
lu
𝑇𝑇 (100 mol − 0.5𝑛𝑛CO2 )100 kPa
+(50 mol − 𝑛𝑛CO2 ) �𝑆𝑆°CO,298 + 𝐶𝐶𝑝𝑝,CO ∙ ln + 𝑅𝑅 ∙ ln �+
298 K (50 mol − 𝑛𝑛CO2 )𝑝𝑝

𝑇𝑇 (100 − 0.5𝑛𝑛CO2 )100 kPa

tia

+(50 mol − 0.5𝑛𝑛CO2 ) �𝑆𝑆°O2,298 + 𝐶𝐶𝑝𝑝,O2 ∙ ln + 𝑅𝑅 ∙ ln �

298 K (50 mol − 0.5𝑛𝑛CO2 )𝑝𝑝
en

g) Only the change can be calculated:

∆G = ∆H − ∆(TS) = (p − p 298 ) · 1.00 m3 + 298 K · S 298 − T · S
id

h) The equilibrium constant of the reaction can be calculated from the standard molar
nf

Gibbs energy change of the process. This is not the same as the one calculated in the
previous point (i.e. it cannot be dependent on amounts of substances).
Co

∆G° = ∆H° − T∆(S°)

𝑇𝑇
∆𝐺𝐺° = ∆H°298 + Δ𝐶𝐶𝑝𝑝 (𝑇𝑇 − 298 K) + 𝑇𝑇∆S°298 + 𝑇𝑇Δ𝐶𝐶𝑝𝑝 ∙ ln
298 K
Here ∆S° 298 is the standard entropy change of the reaction at 298 K, it can be calculated
directly from the given standard entropy values as −173.0 J/(mol K). ∆Cp is the molar heat
capacity change of the reaction, −13.4 J/(mol K). Then the equilibrium constant is:
∆𝐺𝐺°
𝐾𝐾 = exp �− �
𝑅𝑅𝑅𝑅

56th IChO Preparatory Problems 43

7.4.

n CO2 T (K) p (kPa) Q H − H 298 (kJ) S (kJ/K) G − G 298 (MJ) K

(mol)
0 298 248 0 0 19.97 0.00 1.50 · 1090
1 433 358 2.34 · 10−4 110 20.71 −2.90 1.86 · 1059
2 567 467 7.51 · 10−4 219 21.22 −5.87 9.15 · 1042
3 702 575 1.44 · 10−3 327 21.60 −8.89 7.43 · 1032
4 837 682 2.26 · 10−3 434 21.91 −12.0 1.01 · 1026
5 972 788 3.22 · 10−3 541 22.16 −15.1 1.05 · 1021
6 1108 893 4.30 · 10−3 646 22.36 −18.2 1.75 · 1017
7 1243 998 5.51 · 10−3 750 22.53 −21.3 1.87 · 1014

ne
8 1379 1101 6.88 · 10−3 853 22.67 −24.5 7.53 · 1011
9 1515 1203 8.41 · 10−2 955 22.80 −27.6 7.98 · 109
10 1651 1304 1.01 · 10−2 1056 22.90 −30.8 1.76 · 108
11 1787 1404 1.20 · 10−2 1156 22.99 −34.0 6.83 · 106

Ju
12 1924 1503 1.42 · 10−2 1256 23.06 −37.2 4.15 · 105
13 2060 1602 1.66 · 10−2 1354 23.13 −40.3 3.62 · 104
14 2197 1699 1.93 · 10−2 1451 23.18 −43.5 4.24 · 103

il
15 2334 1795 2.23 · 10−2 1547 23.22 −46.7 6.33 · 102
16 2471 1890 2.57 · 10−2 1642 23.26 −49.9 1.16 · 102
17
18
19
2608
2746
2883
1984
2077
2169
2.95 · 10−2
3.38 · 10−2
3.87 · 10−2
nt
1736
1829
1922
23.29
23.31
23.33
−53.1
−56.2
−59.4
2.51 · 101
6.33
1.81
lu
20 3021 2260 4.42 · 10−2 2013 23.340 −62.5 5.75 · 10−1
21 3159 2350 5.06 · 10−2 2103 23.346 −65.7 2.02 · 10−1
22 3297 2440 5.78 · 10−2 2192 23.347 −68.8 7.68 · 10−2
23 3435 2528 6.60 · 10−2 2280 23.343 −72.0 3.15 · 10−2
tia

24 3574 2615 7.55 · 10−2 2367 23.336 −75.1 1.38 · 10−2

25 3712 2700 8.64 · 10−2 2453 23.32 −78.2 6.40 · 10−3
26 3851 2785 9.91 · 10−2 2538 23.31 −81.3 3.13 · 10−3
en

27 3990 2869 1.14 · 10−1 2622 23.29 −84.4 1.60 · 10−3

28 4129 2952 1.31 · 10−1 2704 23.27 −87.4 8.57 · 10−4
29 4268 3034 1.51 · 10−1 2786 23.24 −90.5 4.76 · 10−4
30 4408 3115 1.75 · 10−1 2867 23.22 −93.5 2.74 · 10−4
id

31 4547 3195 2.04 · 10−1 2947 23.19 −96.5 1.63 · 10−4

32 4687 3273 2.39 · 10−1 3026 23.15 −99.5 9.95 · 10−5
33 4827 3351 2.80 · 10−1 3103 23.12 −103 6.25 · 10−5
nf

34 4967 3428 3.31 · 10−1 3180 23.08 −106 4.02 · 10−5

35 5107 3503 3.95 · 10−1 3255 23.04 −108 2.64 · 10−5
Co

36 5248 3578 4.74 · 10−1 3330 22.99 −111 1.78 · 10−5

37 5389 3651 5.74 · 10−1 3404 22.95 −114 1.22 · 10−5
38 5529 3724 7.04 · 10−1 3476 22.90 −117 8.47 · 10−6
39 5671 3795 8.74 · 10−1 3547 22.85 −120 6.00 · 10−6
40 5812 3865 1.10 3618 22.79 −123 4.32 · 10−6
41 5953 3935 1.42 3687 22.74 −126 3.15 · 10−6
42 6095 4003 1.88 3755 22.68 −129 2.33 · 10−6
43 6236 4070 2.55 3822 22.62 −131 1.75 · 10−6
44 6378 4136 3.62 3888 22.56 −134 1.32 · 10−6
45 6520 4201 5.43 3954 22.49 −137 1.01 · 10−6
46 6663 4265 8.84 4017 22.42 −139 7.84 · 10−7
47 6805 4328 16.4 4080 22.35 −142 6.13 · 10−7

56th IChO Preparatory Problems 44

 48 6948 4390 38.4 4142 22.28 −145 4.83 · 10−7
49 7090 4451 160 4203 22.20 −147 3.85 · 10−7
50 7233 4510 -- 4263 22.10 −150 3.08 · 10−7

The equilibrium lies where the entropy has a maximum (second law of thermodynamics), this is
close to n CO2 = 22 mol. The Q = K condition is also satisfied close to this point. It is notable that the
Gibbs free energy of the system would keep decreasing even at higher conversions. This is a
reminder of the fact that the minimum of G characterizes equilibrium conditions at constant
temperature and pressure, while the present reactor is adiabatic.

ne
Ju
il
nt
lu
tia
en
id
nf
Co

56th IChO Preparatory Problems 45

8. Nitrogen oxides
The nitrogen oxides stand out among non-metal oxides, as there is at least one binary
molecular oxide corresponding to each oxidation state between +1 and +5.
8.1. Give a molecular formula and a Lewis structure (one resonance structure is
sufficient) of the simplest oxide for each oxidation state.
For some oxidation states, multiple oxides are possible. For example, when brown gas A
is cooled down, a colorless liquid of compound B is formed, which is a dimer of A. For

ne
practical calculations, the volume of the liquid is negligible as compared to the volume of
the gas.
8.2. Determine A and B. Give the molecular formula and a Lewis structure of B.

Ju
Let us consider the chemical equilibrium 2 A(g) ⇌ B(g) (reaction 1) and the following
data (assume them to be independent of temperature):

il
Δ f Ho / kJ/mol So / J/(mol⋅K)

B(g)
A(g)
9.16
33.18
nt 304.29
219.85
lu
8.3. Calculate the equilibrium constant of reaction 1 at 25 °C.
1 mol of A is put into an empty container, it is closed with a fixed volume of 25 dm3 and
tia

thermostated at 25 °C.
8.4. Calculate the equilibrium pressure of the system.
en

The standard atmospheric boiling point of B is at 21.69 °C. Δ𝐻𝐻𝑣𝑣𝑣𝑣𝑣𝑣 = 22.96 kJ/mol, Δ𝑆𝑆𝑣𝑣𝑣𝑣𝑣𝑣 =
J
77.9 mol⋅K for the evaporation of B. Assume them to be independent of temperature.
id

8.5. Calculate the enthalpy of formation of B(l).

8.6. Calculate the entropy change of the reaction 2 A (g) = B (l) (reaction 2).
nf

We can assume that the entropy change of reaction 2 is independent of temperature

between −10 and 22 °C.
Co

8.7. Calculate the equilibrium constant of reaction 2 at 0 °C.

1 mol of A is put into an empty container, it is closed with a fixed volume of 25 dm3 and
thermostated at 0 °C.
8.8. Calculate the equilibrium pressure of the cooled system.

56th IChO Preparatory Problems 46

Solution
8.1.

Oxidation state of +1: N 2 O N N O

Oxidation state of +2: NO N O

O N N O
Oxidation state of +3: N 2 O 3
O

Oxidation state of +4: NO 2 O N O

ne
O O
Oxidation state of +5: N 2 O 5 N N
O O O

Ju
8.2.

il
O N O
A: NO 2

B: N 2 O 4
O

O
N N
O

O
nt
lu
8.3.
tia

𝑜𝑜 kJ
Δ𝐻𝐻𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = Δ𝑓𝑓 𝐻𝐻(𝐁𝐁) − 2Δ𝑓𝑓 𝐻𝐻(𝐀𝐀) = (9.16) − 2(33.18) = −57.2
mol
en

𝑜𝑜 J
Δ𝑆𝑆𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = 𝑆𝑆(𝐁𝐁) − 2𝑆𝑆(𝐀𝐀) = (304.29) − 2(219.85) = −135.41
mol⋅K
kJ
id

𝑜𝑜 𝑜𝑜 𝑜𝑜
Δ𝐺𝐺𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = Δ𝐻𝐻𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 − 𝑇𝑇Δ𝑆𝑆𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = (−57.2) − (298.15)(−0.13541) = −16.83
mol
𝑜𝑜
Δ𝐺𝐺𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 16830
nf

𝐾𝐾 = exp �− � = exp � � = 887

𝑅𝑅𝑅𝑅 (8.3145)(298.15)
Co

8.4.

𝑝𝑝𝐵𝐵 𝑝𝑝° 𝑦𝑦𝐵𝐵 𝑝𝑝° 𝑛𝑛𝐵𝐵 𝑛𝑛𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑝𝑝°𝑉𝑉 𝑛𝑛𝐵𝐵 𝑝𝑝°𝑉𝑉

𝐾𝐾 = = � �= � �= � � = 887
(𝑝𝑝𝐴𝐴 ) 2 (𝑦𝑦𝐴𝐴 ) 𝑝𝑝𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡
2 (𝑛𝑛𝐴𝐴 ) 2 𝑛𝑛𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑅𝑅𝑅𝑅 (𝑛𝑛𝐴𝐴 )2 𝑅𝑅𝑅𝑅
𝑥𝑥 (1)(25)
𝐾𝐾 = � � = 887
(1 − 2𝑥𝑥) (0.08314)(298.15)
2

Solving for x gives 0.488. Therefore, n total = 1−x = 0.512 mol

56th IChO Preparatory Problems 47

 𝑛𝑛𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑅𝑅𝑅𝑅 (0.512)(8.3145)(298.15)
𝑝𝑝𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = = (10−5 ) = 0.508 bar = 50.8 kPa
𝑉𝑉 (0.025)

8.5.
Consider the following reaction B(l) → B(g):

Δ𝐻𝐻𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = Δ𝑓𝑓 𝐻𝐻(𝐁𝐁(𝑔𝑔)) − Δ𝑓𝑓 𝐻𝐻�𝐁𝐁(𝑙𝑙)� = (9.16 𝑘𝑘𝑘𝑘/𝑚𝑚𝑚𝑚𝑚𝑚) − Δ𝑓𝑓 𝐻𝐻�𝐁𝐁(𝑙𝑙)� = 22.96 kJ/mol

∴ Δ𝑓𝑓 𝐻𝐻�𝐵𝐵(𝑙𝑙)� = −13.8 kJ/mol

8.6.

ne
The provided reaction is the sum of the two reactions:

Ju
2𝐀𝐀 = 𝐁𝐁(𝑔𝑔)
𝐁𝐁(𝑔𝑔) = 𝐁𝐁(𝑙𝑙)
J J J

il
∴ Δ𝑆𝑆𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = −135.4 − 77.9 = −213.3
mol ⋅ K mol ⋅ K mol ⋅ K

8.7.
nt
lu
kJ
Δ𝐻𝐻𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = Δ𝑓𝑓 𝐻𝐻(𝐁𝐁(l)) − 2Δ𝑓𝑓 𝐻𝐻�𝐀𝐀(g)� = −13.8 − 2(33.18) = −80.16
mol
kJ
tia

Δ𝐺𝐺𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = Δ𝐻𝐻𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 − 𝑇𝑇Δ𝑆𝑆𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = (−80.16) − (273.15)(−0.2133) = −21.9

mol
Δ𝐺𝐺𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 21.9 ∙ 103
𝐾𝐾 = exp �− � = exp � � = 15400
en

𝑅𝑅𝑅𝑅 (8.3145)(273.15)

8.8.
id

With such a Gibbs energy change, the reaction is also expected to go to completion. The
equilibrium vapor pressure of B(l) at 0 °C can be obtained by considering B(l) = B(g):
nf

𝑝𝑝 −(22960) 1 1
ln � �= � − �
101.325 kPa 8.3145 273.15 21.69 + 273.15
Co

ΔG = ΔH − TΔS = (22.96) − (273.15)(0.0779) = 1.68 kJ/mol

K = exp(−ΔG/(RT)) = exp(−1.68·1000/(8.3145·273.15)) = 0.477
p B = K · p° = 0.477 bar = 47.7 kPa
However, even if the entire system is only composed of N 2 O 4 (g) at 273.15 K in 25 dm3,
the pressure is still only 45.4 kPa, so there is no condensed phase, and the pressure is 45.4
kPa.

56th IChO Preparatory Problems 48

9. Statin drugs
Statins are the drugs of first choice for management of many lipid disorders. All statins
interfere with the conversion of 3-hydroxi-3-methyl-glutaryl coenzyme A (HMG-CoA) to
the cholesterol precursor mevalonate by HMG-CoA reductase, an early and rate-limiting
step in cholesterol synthesis. Statins competitively inhibit HMG-CoA reductase by binding
to the enzyme and sterically inhibiting substrate binding.
The family of statins contains some very effective pharmaceutical compounds, a few of
which are shown in the drawing below.

ne
Ju
il
fluvastatin cerivastatin
nt
lu
tia

atorvastatin pravastatin
en
id

rosuvastatin
nf

Table 1. Thermodynamic properties of the substrates at 37 °C.

Co

ΔrH /
K I / nM Δ r H / kJ/mol
kcal/mol
Atorvastatin 14 −4.3 −18.1
Cerivastatin 5.7 −3.3 −13.9
Fluvastatin 256 - -
Pravastatin 103 −2.5 −10.5
Rosuvastatin 2.3 −9.3 −39.1

56th IChO Preparatory Problems 49

K I is the equilibrium constant for the dissociation of the enzyme-inhibitor complex. Δ r H is
the binding enthalpy for the inhibitor and in can be assumed to be temperature
independent.
Efficacy and selectivity of the drug substance depends on the strength of binding to the
target enzyme. Thus, a binding study is usually carried out for larger active substance
families. In a series of experiments the initial activity of the enzyme is measured by
spectrophotometry at different substrate concentrations, and the results are evaluated
using the formula of initial rate according to Michaelis-Menten kinetics (v I is the initial
rate of the reaction, K M and v max are coefficients depending on the reaction between the
enzyme and substrate, c and [I] 0 are the initial concentrations of substrate and inhibitor,

ne
respectively):
𝑐𝑐 [𝐼𝐼]
𝑣𝑣𝐼𝐼 = 𝑣𝑣𝑚𝑚𝑚𝑚𝑚𝑚 ∙ where 𝐾𝐾′ = 𝐾𝐾𝑀𝑀 �1 + �

Ju
𝐾𝐾 ′ + 𝑐𝑐 𝐾𝐾𝐼𝐼

In the present study the binding of the drug molecule was characterized by the ratio v I /v 0 ,
where v 0 is the initial rate in the absence of inhibitor at the given substrate (HMG-CoA)

il
concentration. Under the experimental conditions of the study K M = 70 μM and all
experiments were carried out at 37 °C.
nt
Results of the study were present on the diagrams A, B and C (v I /v 0 vs. [I]/μM) but
unfortunately the names of the active substances disappeared from the graphs.
lu
tia
en
id
nf
Co

56th IChO Preparatory Problems 50

9.1. Match the diagrams with the active substances taking into account that at this
level of precision multiple drugs can belong to the same diagram.
9.2. Estimate the order of magnitude of substrate concentration in the
spectrophotometry experiments.
Enthalpy change of the binding was determined by calorimetric titration. A solution with
known concentration of the enzyme was titrated with the solution of the drug substance.
In order to evaluate the results, the molar heat effect (with respect to substrate) versus
molar ratio of substrate was shown on a diagram (bottom part of the next figure) but,
unfortunately labelling was lost again. However, it was noted that in the case of

ne
Fluvastatin the enthalpy change was below the detection limit of the equipment
(practically it is 0 kJ/mol).

Ju
il
nt
lu
tia

9.3. Match diagrams with the drugs above (one molecule to each diagram)
en

9.4. Determine the equilibrium constant for the association of each pharmaceutical
compound at 25 and at 37 °C.
id

9.5. Estimate the (overall) ratio of drug molecules necessary to obtain a solution at
37 °C where the concentration of free (unbound) drug molecules are equal if the
nf

enzyme is present
i. in a catalytic amount.
Co

ii. in excess.

56th IChO Preparatory Problems 51

Solution
9.1.
𝑣𝑣𝑚𝑚𝑚𝑚𝑚𝑚 𝑐𝑐
[𝐼𝐼] 𝑐𝑐 𝑐𝑐
𝑣𝑣𝐼𝐼 𝐾𝐾𝑀𝑀 �1 + 𝐾𝐾 � + 𝑐𝑐 𝐾𝐾 + 𝑐𝑐 �1 + 𝐾𝐾 � 𝐾𝐾𝐼𝐼 �1 + 𝐾𝐾 �
𝐼𝐼 𝑀𝑀 𝑀𝑀 𝑀𝑀
= 𝑣𝑣𝑚𝑚𝑚𝑚𝑚𝑚 𝑐𝑐 = = = 𝑐𝑐
𝑣𝑣0 [𝐼𝐼] [𝐼𝐼] 𝑐𝑐
𝐾𝐾𝑀𝑀 + 𝑐𝑐 𝐾𝐾𝑀𝑀 �1 + 𝐾𝐾 � + 𝑐𝑐 𝐾𝐾 + �1 + 𝐾𝐾 � [𝐼𝐼] + 𝐾𝐾𝐼𝐼 �1 + 𝐾𝐾𝑀𝑀 �
𝐼𝐼 𝐼𝐼 𝑀𝑀

Therefore, the higher 𝐾𝐾𝐼𝐼 , the less steep the decay of 𝑣𝑣𝐼𝐼 /𝑣𝑣0 .

ne
A is the steepest decay. It should belong to Rosuvastatin and Cerivastatin (same order of
magnitude).

Ju
C is the least steep decay. It should belong to Fluvastatin and Pravastatin (same order of
magnitude).
B is in the middle. It should belong to Atorvastatin.

il
9.2.
nt
lu
Consider diagram B belonging to Atorvastatin:
𝑣𝑣𝐼𝐼
([I] = 0.15 μM) = 0.2
𝑣𝑣0
tia

𝑐𝑐 𝑐𝑐
𝐾𝐾𝐼𝐼 �1 + (14 nM) �1 +
𝐾𝐾𝑀𝑀 � 70 μM�
𝑐𝑐 = 𝑐𝑐 = 0.2
[𝐼𝐼] + 𝐾𝐾𝐼𝐼 �1 + � (150 nM) + (14 nM) �1 + �
en

𝐾𝐾𝑀𝑀 70 μM
Solving for 𝑐𝑐 gives 117.5 μM (magnitude of 100 μM).
id

9.3.
nf

a. Pravastatin b. Cerivastatin c. Atorvastatin d. Rosuvastatin

Co

9.4.
1 1
𝐾𝐾𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 (𝑇𝑇) = =
𝐾𝐾𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 (𝑇𝑇) 𝐾𝐾𝐼𝐼 (𝑇𝑇)
Δr 𝐻𝐻 1 1
𝐾𝐾(𝑇𝑇2 ) = 𝐾𝐾(𝑇𝑇1 ) exp �− � − ��
𝑅𝑅 𝑇𝑇2 𝑇𝑇1

56th IChO Preparatory Problems 52

 K I (37 °C) / nM Δ r H / kJ/mol K assoc (37 °C) / nM-1 K assoc (25 °C) / nM-1

Atorvastatin 14 −18.1 0.0714 0.0947

Cerivastatin 5.7 −13.9 0.1754 0.2179
Fluvastatin 256 - 0.0039 0.0039
Pravastatin 103 −10.5 0.0097 0.0114
Rosuvastatin 2.3 −39.1 0.4348 0.8004

ne
9.5.
i. For a catalytic amount of the enzyme, the enzyme-inhibitor complex does not really
change the amount of inhibitor, so a 1:1:1:1:1 mixture is needed.

Ju
ii. For an excess of enzyme, the free inhibitor concentration is proportional to K ass . So, the
amounts used need to be inversely proportional to K ass .

il
Reference: nt
Binding Thermodynamics of Statins to HMG-CoA Reductase, Teresa Carbonell and
lu
Ernesto Freire, Biochemistry 2005 44 (35), 11741-11748,
https://doi.org/10.1021/bi050905v
tia
en
id
nf
Co

56th IChO Preparatory Problems 53

10. Minions and berries
Dr. Nefario after getting tired of doing evil, started a new project preparing his own brand
of berry juice. Unfortunately, the product was a complete flop on the market, so he started
a quality check on the process.
It turned out that the flavor compound berrine coming from the fruits is oxidized to
diberrine during cooking by the moxone additive they used. Their research showed that
when 75% of the berrine is used up, then the juice will become unpalatable due to the
bitter taste of diberrine.

ne
The reaction takes place according to the following overall reaction:
2 berrine + moxone → diberrine

Ju
During their experiments they changed the quantity of the fruit and the added moxone.
After starting cooking, they took samples from the mixture every minute and determined

il
the initial rate of formation of diberrine. Every batch of juice was 100 dm3. The fruit
contains 8.0 mass% berrine, and we can suppose that all of it is liberated at the start of

experiment fruit (kg)

nt
cooking. Moxone was added as 1.0 mol/dm3 solution.
moxone diberrine formation rate
lu
(dm3) (10–5 mol dm−3 min−1)
1 10.0 2.6 4.36
2 5.0 2.6 2.19
tia

3 20.0 2.6 8.75

4 10.0 10.4 17.42
5 10.0 5.2 8.80
en

10.1. Determine the reaction order of the components and give the rate equation of
the reaction, based on the initial rate data.
id

In a different series of experiments, a great excess of moxone was used when monitoring
the formation of diberrine.
nf

10.2. Identify the shapes of the detected kinetic curves?

The observed rate constants were the following in experiments with different oxidizer
Co

concentrations:
moxone
k obs (h-1)
(mol/dm3)
0.040 0.180
0.100 0.460
0.160 0.747
0.220 1.020
0.280 1.320
0.340 1.560
0.400 1.838

56th IChO Preparatory Problems 54

Make a diagram to determine the rate constant of the reaction.

ne
Ju
1 kg of berries and 11 dm3 of moxone stock solution were mixed in a 100 dm3 batch of

il
juice. Berrine has a molar mass of 365 g/mol.
10.3.

10.4.
nt
Calculate the berrine concentration in this experiment when 5 minutes have
passed after the start of the cooking?
Calculate the duration of cooking before the juice becomes unpalatable when
lu
using a concentration of 0.100 mol/dm3 moxone (still in high excess).
Normally the cooking was run at 108 °C. In one experiment the minion responsible set the
tia

temperature to 120 °C. The activation energy of the reaction is 58.60 kJ/mol. Moxone was
also in excess here in a concentration of 0.22 mol/dm3.
10.5. Determine if the juice remained tasty after 35 minutes of cooking?
en
id
nf
Co

56th IChO Preparatory Problems 55

Solution
10.1.
1 𝑑𝑑[berrine] 𝑑𝑑[moxone] 𝑑𝑑[diberrine]
𝑣𝑣 = − =− = = 𝑘𝑘 ∙ [berrine] ∙ [moxone]
2 𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑
no. fruit moxone diberrine formation berrine moxone k (M-1min-1) k (M-1h-1)
(kg) (dm3) rate (M) (M)
(10–5 mol dm−3 min−1)
1 10.0 2.6 4.36 0.0219 0.026 0.077 4.59

ne
2 5.0 2.6 2.19 0.0110 0.026 0.077 4.59
3 20.0 2.6 8.75 0.0438 0.026 0.077 4.61
4 10.0 10.4 17.42 0.0219 0.104 0.076 4.59

Ju
5 10.0 5.2 8.80 0.0219 0.052 0.077 4.64

10.2.

il
pseudo-first order reaction → increasing exponential curves for the diberrine
concentration
𝑘𝑘 = 4.61 ± 0.07𝑀𝑀−1 ℎ−1
nt
lu
The second order rate constant can be determined as the slope of the k obs vs [moxone]
plot or numerically as the average of the k obs /[moxone] values in the table in question
10.2.
tia

Obviously, manual plotting on a paper grid will result in a chart different than a computer-
drawn version and certain level of scatter is expected between the students. However,
maximum points can be given if the contestants follow the general rules of plotting and
en

evaluate the data accordingly.

id
nf
Co

56th IChO Preparatory Problems 56

10.3.
This experiment is somewhat similar to exp.4 in Part 1, except that only 1/10 of berrine
is used in order to ensure pseudo-first order conditions.
1000 ∗ 0.08
[berrine]0 = 365 = 2.19 ∙ 10−3 𝑀𝑀
100
11 ∗ 1
[moxone]0 = = 0.110 𝑀𝑀
100
Moxone is present in a 50-fold excess → pseudo-first order behavior is a valid assumption.

ne
Estimated k obs based on the data from Part 2:
𝑘𝑘𝑜𝑜𝑜𝑜𝑜𝑜 = 𝑘𝑘 ∙ [moxone] = 0.507 h−1 = 8.45 ∙ 10−3 min−1

Ju
Stoichiometry has to be considered at this point, 2 moles of consumed berrine yields 1
mole of product. It is a key information that the product formation is monitored in the
experiments.

il
Therefore:

𝑣𝑣 = −
1 𝑑𝑑[berrine] 𝑑𝑑[diberrine]
2 𝑑𝑑𝑑𝑑
=
𝑑𝑑𝑑𝑑
nt
= 𝑘𝑘 ∙ [berrine] ∙ [moxone] = 𝑘𝑘𝑜𝑜𝑜𝑜𝑜𝑜 [berrine]
lu
𝑑𝑑[berrine]
= −2𝑘𝑘𝑜𝑜𝑜𝑜𝑜𝑜 [berrine]
𝑑𝑑𝑑𝑑
tia

−3 ∙5
[berrine] = [berrine]0 𝑒𝑒 −2𝑘𝑘𝑜𝑜𝑜𝑜𝑜𝑜 𝑡𝑡 = 2.19 ∙ 10−3 ∙ 𝑒𝑒 −2∙8.45∙10 = 2.01 ∙ 10−3 M
This represents 8% conversion.
en

An alternative possibility is to calculate the initial rate of diberrine formation in such a

solution:
1 𝑑𝑑[berrine] 𝑑𝑑[diberrine]
id

𝑣𝑣0 = − = = 𝑘𝑘 ∙ [berrine]0 ∙ [moxone]0 = 1.85 ∙ 10−5 M ∙ min−1

2 𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑
At t = 5 min ∆[diberrine] = 9.25 ∙ 10−5 M
nf

∆[berrine] = −2∆[diberrine] = −1.85 ∙ 10−4 M

Co

[berrine]5min = 2.00 ∙ 10−3 M

10.4.
1 𝑑𝑑[berrine]
𝑣𝑣 = − = 𝑘𝑘𝑜𝑜𝑜𝑜𝑜𝑜 [berrine]
2 𝑑𝑑𝑑𝑑
𝑑𝑑[berrine]
= −2𝑘𝑘𝑜𝑜𝑜𝑜𝑜𝑜 [berrine]
𝑑𝑑𝑑𝑑
[berrine] = [berrine]0 𝑒𝑒 −2𝑘𝑘𝑜𝑜𝑜𝑜𝑜𝑜 𝑡𝑡 = 0.25[berrine]0

56th IChO Preparatory Problems 57

 𝑒𝑒 −2∙0.460∙𝑡𝑡 = 0.25
𝑡𝑡 = 1.51 h ≈ 90 min

10.5.
T (°C) T (K) k (M-1h-1)
1 108 381.15 4.61
2 120 393.15 8.11

ne
𝐸𝐸𝑎𝑎
ln 𝑘𝑘1 = ln 𝐴𝐴 −

Ju
𝑅𝑅𝑇𝑇1
𝐸𝐸𝑎𝑎
ln 𝑘𝑘2 = ln 𝐴𝐴 −
𝑅𝑅𝑇𝑇2

il
𝑘𝑘2 𝐸𝐸𝑎𝑎 1 1
ln
𝑘𝑘1
= � − �
𝑅𝑅 𝑇𝑇1 𝑇𝑇2
𝑘𝑘2 = 8.11 M −1 h−1
nt
lu
𝑘𝑘𝑜𝑜𝑜𝑜𝑜𝑜 = 1.784 h−1
for the consumption of berrine:
tia

𝑘𝑘𝑜𝑜𝑜𝑜𝑜𝑜 ′ = 3.568 h−1

ln 2
𝑡𝑡1 ′ = = 0.194 h
en

2 𝑘𝑘𝑜𝑜𝑜𝑜𝑜𝑜 ′
75% conversion takes 2 half-lives: ⇒ t = 0.384 h = 23 min
id

OR:
[berrine] = [berrine]0 𝑒𝑒 −2𝑘𝑘𝑜𝑜𝑜𝑜𝑜𝑜 𝑡𝑡 = 0.25[berrine]0
nf

𝑒𝑒 −2∙1.784∙𝑡𝑡 = 0.25
𝑡𝑡 = 0.389 h ≈ 23.3 min
Co

⇒ after 35 min, the juice is no longer consumable.

𝐸𝐸𝑎𝑎�
𝐴𝐴 = 𝑘𝑘𝑒𝑒 𝑅𝑅𝑅𝑅 = 5.0 ∙ 108 M −1 h−1

56th IChO Preparatory Problems 58

11. Clock reactions
Clock reactions show a sudden change in some property (typically color) after a period of
induction. In iodine clock reactions iodide containing solutions are mixed with an oxidizer
in the presence of thiosulfate and starch. After some time, the solution will suddenly turn
blue due to the starch-iodine complex forming.
Measuring the time needed for this reaction gives an opportunity to study the iodide –
oxidizer reactions, determining reaction orders and rate constants based on initial
reaction rates.

ne
The reaction between Fe(III) ions and iodide can be studied in this way. When the blue
color appears that shows that the thiosulfate present was all used up. If a small quantity

Ju
of thiosulfate is used, we can suppose that the concentration of other reagents will not
change. Based on this and the stoichiometry of the reactions, we can use the following:
2− 2−
Δ[Fe 3+ ] Δ[S 2 O 3 ] [S 2 O 3 ]0

il
v0 ≈ − =− =
Δt Δt Δt (1)

n
v0 = k[Fe 3+ ]0 [I − ]0 =
m

Δt
2−
[S 2 O 3 ]0 nt (2)
lu
The following was found for the Δt period when the three concentrations were changed:
[S 2 O 3 2–] 0 [KI] 0 [Fe(NO 3 ) 3 ] 0
tia

Δt (s)
(mmol∙dm–3) (mmol∙dm–3) (mmol∙dm–3)
variable 20.0 6.5 Δt = 2.32∙104[S 2 O 3 2–] 0
0.2 variable 8.5 Δt = 1.54∙10–3 ([I–] 0 ) –1.98
en

0.25 13.0 variable Δt = 5.01∙10–2 ([Fe3+] 0 ) –1.05

11.1. Give the balanced equation for the reaction of Fe(III) and I–.
id

11.2. How does the initial rate depend on the initial thiosulfate concentration?
11.3. Give the individual and the overall reaction orders? Give the rate equation.
nf

11.4. Give the unit of the rate constant? Calculate the rate constant from the three sets
of experiments. Considering that a 10% margin of error is often acceptable in
Co

reaction kinetics, assess the quality of these experiments.

The following mechanism was proposed:
k1
I– + Fe3+ FeI2+ (3)
k-1

k2
I– + FeI2+ Fe2+ + I 2 – (4)
k-2
k3
I 2 – + Fe3+ I 2 + Fe2+ (5)

56th IChO Preparatory Problems 59

Supposing a steady state for the FeI2+ and I 2 – intermediates, the following rate equation
was derived, but the result is not fully correct. One of the elements in the denominator is
not necessary.

d[I 2 ] k1 k 2 k 3 [I − ]2 [Fe 3+ ]
= (6)
dt k −1 k − 2 [Fe 2+ ] k 2 k − 2 [Fe 2+ ][I − ]
3+
+ k k
−1 3 + 3+
+ k 2 k 3 [I − ]
[Fe ] [Fe ]
11.5. Derive the right rate equation to identify the unnecessary element.

ne
Ju
il
nt
lu
tia
en
id
nf
Co

56th IChO Preparatory Problems 60

Solution
11.1.
2Fe3+ + 2I− = 2Fe2+ + I2

11.2.

[S2 O3 2− ]0
𝑣𝑣0 = = 4.31 ∙ 10−8 mol ∙ dm−3 ∙ s −1

ne
△ 𝑡𝑡

Ju
The ratio is constant. ⇒ The initial rate is independent from the concentration of
thiosulfate.

il
11.3.
From the reaction time expressions:
n = 1.98 ≈ 2, m = 1.05 ≈ 1
nt
lu
The reaction is net third order:
𝑣𝑣 = 𝑘𝑘[I − ]2 [Fe3+ ]
tia

11.4.
en

M ∙ s −1 = dimension(𝑘𝑘) ∙ M 3
dimension(𝑘𝑘) = M −2 ∙ s−1
id

1
1 2.32 ∙ 104 = 𝑘𝑘 = 16.58 M −2 ∙ s−1
nf

𝑘𝑘[I − ]20 [Fe3+ ]0

[S2 O3 2− ]
𝑘𝑘 = 15.28 M −2 ∙ s−1
Co

2 −3
1.54 ∙ 10 =
𝑘𝑘[Fe3+ ]0

[S2 O3 2− ]
3 5.01 ∙ 10−2 = 𝑘𝑘 = 29.53 M −2 ∙ s−1
𝑘𝑘[I − ]20

The spread of the k values around the mean is much higher than the 10% threshold ⇒ not
acceptable.

56th IChO Preparatory Problems 61

11.5.
𝑑𝑑[I − ]
= −𝑘𝑘1 [I− ][Fe3+ ] + 𝑘𝑘−1 [FeI2+ ] − 𝑘𝑘2 [I − ][FeI2+ ] + 𝑘𝑘−2 [Fe2+ ][I2− ]
𝑑𝑑𝑑𝑑
𝑑𝑑[Fe3+ ]
= −𝑘𝑘1 [I− ][Fe3+ ] + 𝑘𝑘−1 [FeI2+ ] − 𝑘𝑘3 [Fe3+ ][I2− ]
𝑑𝑑𝑑𝑑
𝑑𝑑[Fe2+ ]
= 𝑘𝑘2 [I− ][FeI2+ ] − 𝑘𝑘−2 [Fe2+ ][I2− ] + 𝑘𝑘3 [Fe3+ ][I2− ]
𝑑𝑑𝑑𝑑
𝑑𝑑[I2 ]
= 𝑘𝑘3 [Fe3+ ][I2− ]

ne
𝑑𝑑𝑑𝑑
Steady-state intermediates: FeI2+ and [I2− ]
𝑑𝑑[FeI2+ ]

Ju
= 𝑘𝑘1 [I − ][Fe3+ ] − 𝑘𝑘−1 [FeI2+ ] − 𝑘𝑘2 [I− ][FeI2+ ] + 𝑘𝑘−2 [Fe2+ ][I2− ] = 0
𝑑𝑑𝑑𝑑
𝑑𝑑[I2− ]
= 𝑘𝑘2 [I − ][FeI2+ ] − 𝑘𝑘−2 [Fe2+ ][I2− ] − 𝑘𝑘3 [Fe3+ ][I2− ] = 0

il
𝑑𝑑𝑑𝑑
Based on the steady-state conditions for the two species:

2+
[FeI ]𝑠𝑠𝑠𝑠 =
𝑘𝑘1 [I − ][Fe3+ ] + 𝑘𝑘−2 [Fe2+ ][I2− ]𝑠𝑠𝑠𝑠
𝑘𝑘−1 + 𝑘𝑘2 [I − ]
nt
lu
𝑘𝑘2 [𝐼𝐼 − ][FeI2+ ]𝑠𝑠𝑠𝑠
[I2− ]𝑠𝑠𝑠𝑠 =
𝑘𝑘−2 [Fe2+ ] + 𝑘𝑘3 [Fe3+ ]
tia

These two equations can be combined and solved for [I2− ]𝑠𝑠𝑠𝑠 :

2+
[I2− ]𝑠𝑠𝑠𝑠 (𝑘𝑘−2 [Fe2+ ] + 𝑘𝑘3 [Fe3+ ]) 𝑘𝑘1 [I− ][Fe3+ ] + 𝑘𝑘−2 [Fe2+ ][I2− ]𝑠𝑠𝑠𝑠
[FeI ]𝑠𝑠𝑠𝑠 = =
en

𝑘𝑘2 [I− ] 𝑘𝑘−1 + 𝑘𝑘2 [I − ]

[I2− ]𝑠𝑠𝑠𝑠 (𝑘𝑘−2 [Fe2+ ] + 𝑘𝑘3 [Fe3+ ]) 𝑘𝑘−2 [Fe2+ ][I2− ]𝑠𝑠𝑠𝑠 𝑘𝑘1 [I − ][Fe3+ ]
− =
𝑘𝑘2 [I− ] 𝑘𝑘−1 + 𝑘𝑘2 [I − ] 𝑘𝑘−1 + 𝑘𝑘2 [I − ]
id

𝑘𝑘−2 [Fe2+ ] + 𝑘𝑘3 [Fe3+ ] 𝑘𝑘−2 [Fe2+ ] 𝑘𝑘1 [I− ][Fe3+ ]

[I2− ]𝑠𝑠𝑠𝑠 � − �=
nf

𝑘𝑘2 [I− ] 𝑘𝑘−1 + 𝑘𝑘2 [I− ] 𝑘𝑘−1 + 𝑘𝑘2 [I− ]

𝑘𝑘−2 [Fe2+ ] + 𝑘𝑘3 [𝐹𝐹𝐹𝐹 3+ ]

[I2− ]𝑠𝑠𝑠𝑠 � ∙ (𝑘𝑘−1 + 𝑘𝑘2 [I− ]) − 𝑘𝑘−2 [Fe2+ ]� = 𝑘𝑘1 [I − ][Fe3+ ]
Co

𝑘𝑘2 [I− ]
𝑘𝑘−2 �Fe2+ �𝑘𝑘−1 +𝑘𝑘−2 �Fe2+ �𝑘𝑘2 [I− ]+𝑘𝑘3 �Fe3+ �𝑘𝑘−1 +𝑘𝑘3 �Fe3+ �𝑘𝑘2 [I− ]−𝑘𝑘−2 �Fe2+ �𝑘𝑘2 [I− ]
[I2− ]𝑠𝑠𝑠𝑠 = 𝑘𝑘1 [I − ][Fe3+ ]
𝑘𝑘2 [I− ]

[I2− ]𝑠𝑠𝑠𝑠 (𝑘𝑘−1 𝑘𝑘−2 [Fe2+ ] + 𝑘𝑘−1 𝑘𝑘3 [Fe3+ ] + 𝑘𝑘2 𝑘𝑘3 [Fe3+ ][I− ]) = 𝑘𝑘1 𝑘𝑘2 [I− ]2 [Fe3+ ]
𝑘𝑘1 𝑘𝑘2 [I− ]2 [Fe3+ ]
[I2− ]𝑠𝑠𝑠𝑠 =
𝑘𝑘−1 𝑘𝑘−2 [Fe2+ ] + 𝑘𝑘−1 𝑘𝑘3 [Fe3+ ] + 𝑘𝑘2 𝑘𝑘3 [Fe3+ ][I− ]

56th IChO Preparatory Problems 62

The overall rate then:
𝑑𝑑[I2 ] 𝑘𝑘1 𝑘𝑘2 𝑘𝑘3 [I− ]2 [Fe3+ ]2
= 𝑘𝑘3 [Fe3+ ][I2− ]𝑠𝑠𝑠𝑠 =
𝑑𝑑𝑑𝑑 𝑘𝑘−1 𝑘𝑘−2 [Fe2+ ] + 𝑘𝑘−1 𝑘𝑘3 [Fe3+ ] + 𝑘𝑘2 𝑘𝑘3 [Fe3+ ][I− ]
𝑑𝑑[I2 ] 𝑘𝑘1 𝑘𝑘2 𝑘𝑘3 [I − ]2 [Fe3+ ]
=
𝑑𝑑𝑑𝑑 [Fe2+ ]
𝑘𝑘−1 𝑘𝑘−2 + 𝑘𝑘−1 𝑘𝑘3 + 𝑘𝑘2 𝑘𝑘3 [I− ]
[Fe3+ ]
compared to the given expression, the third term is extra in the denominator:

ne
𝑑𝑑[I2 ] 𝑘𝑘1 𝑘𝑘2 𝑘𝑘3 [I − ]2 [Fe3+ ]
=
dt 𝑘𝑘−1 𝑘𝑘−2 [Fe2+ ] 𝑘𝑘2 𝑘𝑘−2 [Fe2+ ][I− ]
+ 𝑘𝑘−1 𝑘𝑘3 + + 𝑘𝑘2 𝑘𝑘3 [I− ]
[Fe3+ ] [Fe3+ ]

Ju
Reference:

il
Kinetics and Mechanism of Iodide Oxidation by Iron(III): A Clock Reaction Approach,
nt
Petar B. A. Vrkljan, Jurica Bauer, and Vladislav Tomisic, Journal of Chemical Education
2008 85 (8), 1123, https://doi.org/10.1021/ed085p1123
lu
tia
en
id
nf
Co

56th IChO Preparatory Problems 63

12. Crystal violet
Crystal violet (or gentian violet
or methyl violet 10B), is known
for its antiseptic and fungicide
effects and is commonly used
for staining Gram positive
bacteria. In aqueous solution
crystal violet (CV) dissociates

ne
into the cation shown in the
figure and chloride ions. The compound has a vivid violet color. In the presence of NaOH,
crystal violet forms a colorless carbinol product.

Ju
The reaction is represented by the following simple equation:
CV + + OH − = CVOH

il
Due to the compound’s intense color, the kinetic study of this reaction can be carried out
by spectrophotometry at 595 nm. The rate law can be written:
𝑣𝑣 = 𝑘𝑘[CV]𝑎𝑎 [OH − ]𝑏𝑏
nt
lu
A set of experiments was carried out at 30.0 °C using the following mixtures:
Exp. no. c(CV), mol/dm3 V(CV), cm3 c(NaOH), mol/dm3 V(NaOH), cm3
#1 1.82∙10−5 5 0.08 5
tia

#2 1.82∙10−5 5 0.12 5
#3 1.82∙10−5 5 0.16 5
#4 1.82∙10−5 5 0.32 5
en

Performing the measurements in a 1.000 cm pathlength cuvette, the following kinetic

curves were recorded:
id
nf
Co

56th IChO Preparatory Problems 64

12.1. Calculate the initial concentrations of the reactants in each reaction mixture.
12.2. Calculate the molar absorption coefficient of CV at 595 nm (you can assume that
the products do not absorb at this wavelength).
12.3. Determine a and b (the partial orders of the reactants) and give the rate law of
the reaction. Calculate the rate constant (k), using the same units as the chart and
the table.
12.4. Calculate the concentration of CV in experiment #3 at 6 minutes.
The k rate constant follows the Arrhenius law in this temperature range and its numeric

ne
value is 22.78 at 45 °C, in the same unit as calculated in Part 3.
12.5. Calculate the Arrhenius parameters (pre-exponential factor (A) and activation
energy (E a )).

Ju
6 cm3 of 2.75∙10−5 mol/dm3 crystal violet solution is mixed with 14 cm3 of
3.86∙10−4 mol/dm3 KMnO 4 solution. The optical pathlength of the cell is 0.6 cm,
ε 595 (KMnO 4 ) = 1875 M−1cm−1. Assume that the volumes are additive, no chemical reaction

il
takes place in the cell and the solution is completely homogenized.
12.6. nt
Calculate the absorbance of the mixture at 595 nm and the corresponding
percentage light absorption.
lu
Crystal violet belongs to the family of triphenyl-methyl dyes. A study revealed that
triphenyl-methyl (trityl) radicals react with thiophenol producing triphenyl methane and
phenyl trityl thioether according to the scheme below: (’I’: hexaphenyl ethane)
tia

𝑘𝑘1
I ⇌ 2 (C6 H5 )3 C ∙ (1)
𝑘𝑘−1
en

𝑘𝑘2
(C6 H5 )3 C ∙ +C6 H5 SH ⇌ (C6 H5 )3 CH + C6 H5 S ∙ (2)
𝑘𝑘−2
id

𝑘𝑘3
(C6 H5 )3 C ∙ +C6 H5 S ∙ �� C6 H5 SC(C6 H5 )3 (3)
nf

Substitution of the thiol hydrogen with tritium (3T) in thiophenol leads to a significant
decrease in the overall reaction rate.
Co

12.7. Which elementary step is expected to be most affected by the described isotope
exchange? What is expected to happen with the overall reaction rate when one
of the carbon atoms in the aromatic ring of thiophenol is changed to 13C?

56th IChO Preparatory Problems 65

Solution
12.1.
Mixture concentrations
[CV] (M) [NaOH] (M) excess (fold)
#1 9.10∙10−6 0.04 4396
#2 9.10∙10−6 0.06 6593
#3 9.10∙10−6 0.08 8791
#4 9.10∙10−6 0.16 17582

ne
NaOH is in high excess ⇒ CV will determine the order

Ju
𝑣𝑣 = 𝑘𝑘[CV]𝑎𝑎 [OH − ]𝑏𝑏 = 𝑘𝑘𝑜𝑜𝑜𝑜𝑜𝑜 [CV]𝑎𝑎
𝑘𝑘𝑜𝑜𝑜𝑜𝑜𝑜 = 𝑘𝑘[OH − ]𝑏𝑏

il
12.2.

𝐴𝐴 = 𝐴𝐴0 𝑒𝑒 −𝑘𝑘𝑜𝑜𝑜𝑜𝑜𝑜 𝑡𝑡
nt
lu
𝐴𝐴0 = 0.805
[CV]0 = 9.1 ∙ 10−6 M
tia

𝜀𝜀595 (𝐶𝐶𝐶𝐶) = 88462 M −1 cm−1

en

12.3.

𝑎𝑎 = 1 Exponential curves are observed.

𝑘𝑘𝑜𝑜𝑜𝑜𝑜𝑜 = 𝑘𝑘[OH − ]𝑏𝑏
id

k obs is linearly proportional to [NaOH]

𝑏𝑏 = 1
nf

𝑣𝑣 = 𝑘𝑘[CV][OH − ]
Potential plots (not required):
Co

lg𝑘𝑘𝑜𝑜𝑜𝑜𝑜𝑜 = lg𝑘𝑘 + 𝑏𝑏 lg[OH − ]

[NaOH](M) k obs (min−1) lg[OH−] lgk obs
#1 0.04 0.311 −1.398 −0.507
#2 0.06 0.466 −1.222 −0.332
#3 0.08 0.621 −1.097 −0.207
#4 0.16 1.242 −0.796 0.094

56th IChO Preparatory Problems 66

 ne
[NaOH](M) k obs (min−1) k (M−1min−1)
#1 0.04 0.311 7.78
#2 0.06 0.466 7.77

Ju
#3 0.08 0.621 7.76
#4 0.16 1.242 7.76
𝑘𝑘𝑎𝑎𝑎𝑎𝑎𝑎 = 7.77 M min = 0.130 M−1 s −1
−1 −1

il
12.4.

𝑘𝑘𝑜𝑜𝑜𝑜𝑜𝑜 = 0.621 min−1

nt
lu
𝑡𝑡 = 6 min
𝐴𝐴 = 𝐴𝐴0 𝑒𝑒 −𝑘𝑘𝑜𝑜𝑜𝑜𝑜𝑜 𝑡𝑡
tia

𝐴𝐴 = 0.805𝑒𝑒 −0.621∙6 = 0.0194

𝐴𝐴
[CV] = = 2.19 ∙ 10−7 M
en

e𝑙𝑙
OR:
id

[CV] = [CV]0 𝑒𝑒 −𝑘𝑘𝑜𝑜𝑜𝑜𝑜𝑜 𝑡𝑡 = 9.1 ∙ 10−6 𝑒𝑒 −0.621∙6 = 2.19 ∙ 10−7 M

nf

12.5.

T (°C) k (…...) T(K)

Co

30 7.77 303.15
45 22.78 318.15

𝑘𝑘45 𝐸𝐸𝑎𝑎 1 1
ln =− � − �
𝑘𝑘30 𝑅𝑅 318.15 303.15
𝐸𝐸𝑎𝑎
− = −6916.0
𝑅𝑅
𝐸𝐸𝑎𝑎 = 57.5 kJ/mol

56th IChO Preparatory Problems 67

 ln 𝐴𝐴 = 24.9 A = 6.52∙1010 M −1 min−1
Arrhenius plot’s equation:
1
ln 𝑘𝑘 = −6916.0 + 24.9
𝑇𝑇

12.6.

c 0 (M) 2.75∙10−5 3.86∙10−4 A total 0.741

V (ml) 6 14 I/I 0 0.182

ne
ε(M−1cm−1) 88273 1875 I/I 0 % 18.2
l (cm) 0.6 0.6 Absorption % 81.8
c (M) 8.25∙10−6 2.70∙10−4

Ju
A 0.437 0.304

12.7.

il
The forward reaction with k 2 will be affected most.

nt
In the case of 13C substitution, no significant effect is seen, because the aromatic ring does
not participate in the reaction.
lu
tia
en
id
nf
Co

56th IChO Preparatory Problems 68

13. Aluminium in lattices
Metallic aluminium under standard conditions forms a face-centered cubic (FCC) crystal
with a density of 2.710 g/cm3. Interestingly, it undergoes several structural changes
under extreme pressures.
At a pressure of 213 GPa the FCC structure is still stable, but the unit cell dimension is
changed to 324.6 pm. When the sample is further compressed between diamond anvils to
above 310 GPa, a transformation to a body-centered cubic (BCC) structure with a unit cell
size of 250.5 pm was detected.

ne
13.1. Calculate and compare the densities (g/cm3) of the different modifications
under extreme pressures.

Ju
13.2. Calculate the metallic radius of Al in the three structures.
The unit cell for a family of magnetic alloys is shown on the

il
figure. If the alloys contain Al, then the Al atoms usually
take up the positions labeled with Z. The other two metals
nt
in the alloy are usually transition metals.
Interesting variations arise from the possibility that in
lu
some cases all (dark and light) blue positions are taken by
X atoms, and in other cases only the dark blue positions.
13.3. Identify the lattice (primitive cubic, FCC, BCC,
tia

something else) formed by the Z atoms only. Identify the lattice formed by the
blue (both dark and light) atoms only.
13.4. Determine the empirical formula of the alloy if all blue positions contain X as
en

shown on the figure. Consider the Z atoms: How many X, how many Y and how
many Z atoms are nearest neighbors with a Z atom?
id

13.5. Identify the lattice formed by the dark blue atoms. Determine the empirical
formula of the alloy if the X atoms are only present in the dark blue positions.
nf

An aluminium containing semiconductor has the following

unit cell. The lattice constant is 613.5 pm, the density of the
Co

material is 4.277 g/cm3.

13.6. Determine the empirical formula of this
semiconductor. Identify the other element.

56th IChO Preparatory Problems 69

Solution
13.1.
FCC has 4 Al atoms/cell, BCC 2 atoms /cell.
Using the cell sizes and the contents, the densities of the high-pressure modifications are
5.240 and 5.700 g/cm3. Density increases with pressure, not surprisingly.

ne
13.2.
In FCC, the face diagonal of the unit cell corresponds to 4 atomic radii. In BCC, the body
diagonal is equal to 4 radii.

Ju
For the two high-pressure forms the radii are thus 114.8 and 108.5 pm.
One can calculate the unit cell dimensions of Al under standard conditions: 404.4 pm.

il
Atomic radius is thus 143.0 pm.

13.3.
nt
lu
Z – FCC
X – Primitive cubic
tia

13.4.
en

X 2 YZ
8 X, 6 Y, 12 Z
id

13.5.
nf

FCC
Co

XYZ

13.6.
1 mol of unit cells weigh 594.7 g. There are 4-4 atoms in a cell. Subtracting the Al atoms,
the other atom has a molar mass of 121.7 g/mol. The empirical formula is AlSb.

56th IChO Preparatory Problems 70

14. Sulfide minerals
Element substitutions and crystal defects are common in most complex sulfide minerals,
resulting in variable compositions in natural samples. However, specimens with relatively
pure compositions identifiable as compounds do exist. While not mined in large
quantities, many complex sulfide minerals are present in copper ores and are reasonably
well-documented due to the significance of copper. These minerals will be discussed in
this task.
In minerals of the chalcopyrite group, which are structurally equivalent to chalcopyrite

ne
(CuFeS 2 ), iron atom substitution is most prevalent. Some variants with a pure
composition in such substitution structures have only been identified in microscopic
samples.

Ju
Two of these minerals/compounds, which can be derived by complete substitution of
iron, have a sulfur content of 32.5 % (A) and 26.5 % (B) by weight.

il
14.1. Give the empirical formula of A and B.

nt
Mineral C can be derived from mineral B by an additional element substitution and has a
sulfur content of 22.4%.
lu
14.2. Give the formula of C.
Significant copper ore minerals include enargite (D) with a theoretical composition of
Cu 3 AsS 4 and bornite (E) with a composition of Cu 5 FeS 4 . Neither structure has an S-S bond,
tia

there are no S atoms close to each other in the lattice. Each crystal has chemically
equivalent atoms of the same kind (e.g., all Cu atoms in E are identical).
14.3. Give the conventional oxidation numbers of the elements in D and E.
en

14.4. Write balanced equations for the reactions of the two minerals if
- they undergo roasting in air with excess oxygen (resulting in black metal oxides,
id

including magnetite)
- react with an excess of bleach solution.
nf

The figure shows the structure of the elementary cell of

enargite.
Co

14.5. Find the coordination number of Cu (brown), As

(purple) and S (yellow) atoms. Find the number of
formula units per elementary cell.
Two additional minerals, F and G, are derived from the same
elements as enargite. Mineral F has an ideal composition
with a sulfur content of 18.8%, featuring a relatively simple composition. On the other
hand, mineral G presents challenges in determining the ideal composition due to wide
substitution possibilities and a relatively complex structure (its empirical formula mass
is close to 1500 g/mol). Its ideal sulfur content is 28.18%. The World Mineralogical
Association last fine-tuned the data and classification of this mineral in 2019.

56th IChO Preparatory Problems 71

14.6. Identify the ideal empirical formulas of F and G.
In the crystal structure of G, Cu(I), Cu(II), thioarsenite (AsS 3 3−) and sulfide ions can be
identified.
14.7. Give the proportions of these ions in G.
Lautite is a rare copper arsenosulfide. In it, the coordination number of all atoms is 4.
Three projections of the elementary cell:

ne
Ju
il
nt
lu
tia

14.8. Give the empirical formula of the mineral. Identify the homonuclear bonds found
en

in the crystal. How many of these homonuclear bonds are there in an elementary
cell?
id
nf
Co

56th IChO Preparatory Problems 72

Solution
14.1.
32.5 % sulfur in CuXS 2 means that M(CuXS 2 ) = 2 M(S)/0.325 = 197.3 g/mol.
M(X) = 69.7 g/mol. So, A is CuGaS 2 .
The analogous calculation for B leads to the CuInS 2 formula.

ne
14.2.
A substitution in CuInS 2 will lead to XInS 2 . The molar mass calculated from the sulfur
content, 286.3 g/mol points to AgInS 2 . C is expected to be AgInS 2 .

Ju
Interestingly there is a formula with CuTbS 2 that fits the same molar mass. Quite often
one finds multiple elements fitting such puzzles numerically, but usually the chemistry is
questionable in those cases. CuTbS 2 is actually reported in the literature, however.

il
14.3. nt
Sulfur is expected to be sulfide, oxidation number −2 in both minerals.
lu
Equivalence of the atoms limits the oxidation numbers in bornite to Cu: +1, Fe: +3.
In enargite the possibilities are Cu: +1 and As: +5 (in line with conventional oxidation
tia

numbers). Cu: +2 would mean As: +2, which would be unusual for an element in group 15.
en

14.4.
Black oxides would be CuO and Fe 3 O 4 .
id

Roasting:
4 Cu 3 AsS 4 + 25 O 2 = 12 CuO + 2 As 2 O 3 + 16 SO 2
nf

6 Cu 5 FeS 4 + 43 O 2 = 30 CuO + 2 Fe 3 O 4 + 24 SO 2
Reaction with bleach:
Co

2 Cu 3 AsS 4 + 35 OCl− + 22 OH− = 6 Cu(OH) 2 + 2 AsO 4 3− + 8 SO 4 2− + 35 Cl− + 5 H 2 O

2 Cu 5 FeS 4 + 37 OCl− + 16 OH− + 5 H 2 O = 10 Cu(OH) 2 + 2 Fe(OH) 3 + 8 SO 4 2− + 37 Cl−
The net equations are naturally also acceptable.

14.5.
Coordination numbers: 4 – 4 -4
2 formula / cell: 6 Cu, 2 As and 8 S atoms

56th IChO Preparatory Problems 73

14.6.
18.8 % S content for F implies a molar mass of 170.5 g/mol for a composition with one S
atom. That fits nicely to CuAsS.
For G, the molar mass per one S atom is 113.8 g/mol based on the sulfur content. With 13
S atoms this gets close to the specified value (1478.4 g/mol) and fits the Cu 12 As 4 S 13
empirical formula.

14.7.

ne
Thioarsenite (AsS 3 3−) and sulfide ions must be in 4:1 ratio to reproduce the empirical
formula.

Ju
If the number of Cu2+ ions in the empirical formula is x, then charge balance gives:
2x + (12−x) = 14
Thus x = 2, and there are 2 Cu(II) and 10 Cu(I) ions in the empirical formula.

il
14.8.
nt
lu
Formula: CuAsS

As-As bonds are found, 4 in each unit cell.

tia

There are 12 tetrahedral atoms in each cell, and thus 12x4/2 = 24 bonds.
Of these there are 4-4-4 of each As-As, As-S and As-Cu bonds and 12 Cu-S bonds.
en
id
nf
Co

56th IChO Preparatory Problems 74

15. Beauty and Infinity
Part I
The largest sand desert on Earth, the Rub’al Khali (‫ٱﻟﺮﺑْﻊ ْٱﻟﺨَﺎﻟِﻲ‬
‫ ) ﱡ‬covers the southeastern part
of Saudi Arabia. The most common constituents of sand grains are silica (SiO 2 ) and R R

various silicates. Indeed, silicon and oxygen are the two main elements of Earth’s crust in
various minerals. Olivine, (Mg,Fe) 2 SiO 4 and garnet, (Mg,Fe,Mn) 3 Al 2 Si 3 O 12 or
R R R R 10TR R R R R R R R10T

Ca 3 (Al,Cr,Fe) 2 Si 3 O 12 are only two examples of the many silicate minerals. The bracketed
10TR R R R R R R R10T

elements signify a variable composition crystal structure with different atoms taking a

ne
certain crystal position. For olivine, this means that specimens with any x = 0-1 exist for
(Mg 1−x Fe x ) 2 SiO 4 .
R R R R R R R R

Ju
15.1. Express the formula of the garnet variant with the lowest silica content as a
combination of oxides.
Several skeletal structures of

il
polysilicate ions are
represented on the figure,
showing SiO 4 tetrahedra. nt
lu
15.2. Find the corresponding charge for each of the four structures in the Figure.
Structures a and c can be extended to a 1D, structure d to a 2D polymeric ion.
tia

Find the empirical formula for the polymeric ions.

Some silicates are beautiful gemstones, displaying a
spectrum of colors. Recent findings in the southwest of Saudi
en

Arabia, in the Bisha area include beryls, belonging to the

mineral family of emeralds and aquamarines.
Emerald and aquamarine share the same beryl structure and
id

have specific green and blue colors. Pure beryl is colorless

and consists of Si, O, Al and Be. 0.2024 g of beryl contains 0.0635 g of Si and 0.0102 g Be.
nf

Another mineral, sky blue bazzite has the same stoichiometry as beryl, but the Al is
replaced by another metal. The Si mass fraction in bazzite differs by 6.25% when
compared to the Si mass fraction in beryl.
Co

15.3. Find the formula of these two minerals: beryl and bazzite.
15.4. Identify the color of light absorbed by emerald: a) No absorption in the visible
spectrum, b) Green color light, c) Red color light, d) Emerald color light.
Part II
In industrial processes, pure silicon, a primary semiconductor in the electronics industry,
is derived from silane (SiH 4 ), itself obtained through the reduction of SiO 2 . Additionally,
on a smaller scale, silane can be produced from certain silicon derivatives such as silicon
halides (SiF 4 , SiCl 4 ) or metal silicides like Mg 2 Si.

56th IChO Preparatory Problems 75

 1) LiH SiF4
[H] 2) LiAlH4
SiO2 SiH4 SiCl4
3) HCl Mg2Si

15.5. Write balanced equations for the three numbered reactions of silane formation.
These reactions can yield Si containing byproducts. From the byproducts, let us consider
A, B, and C, each unique for one of the three reactions. Their molecular mass increases in
order: B, C, A. Compound A contains 93.3 % Si by mass. The mass spectrum of compound
B can be used to obtain an average molar mass of 101 g/mol. Also, B possesses two planes

ne
of symmetry. Finally, C contains 73.1% halogen by mass.
15.6. Identify the unknown compounds A, B and C and assign them to their respective
reactions.

Ju
15.7. Among the SiX 4 molecules (SiH 4 , SiF 4 , SiCl 4 ), determine a) the one with the
lowest melting point, and b) the one with the highest Lewis acidity.

il
Part III

nt
SiH 4 is highly flammable in O 2 containing atmospheres. The final product is SiO 2 ,
however, in a less oxidative atmosphere like N 2 O gas, partial oxidation of silane can yield
lu
valuable products. Significant elementary reactions of the radical mechanism of this gas-
phase reaction are below. The 1st and the 6th steps are very slow.
𝑘𝑘1
N2 O �⎯⎯⎯� N2 +O
tia

𝑘𝑘2
O+SiH4 �⎯⎯⎯� SiH3 +OH
𝑘𝑘3
OH+SiH4 �⎯⎯⎯� SiH3 +H2 O
en

𝑘𝑘4
SiH3 +N2 O �⎯⎯⎯� SiH3 O+N2
𝑘𝑘5
SiH3 O+SiH4 �⎯⎯⎯� SiH3 OH+SiH3
𝑘𝑘6
id

SiH3 +SiH3 O �⎯⎯⎯� H3 SiOSiH3

15.8. Categorize steps 1, 4 and 6 with respect to their role in the chain reaction
nf

mechanism.
15.9. Write the net chemical reaction.
Co

15.10. Find the kinetic law and reaction orders for the net reaction when N 2 O is in
excess. Use the steady-state approximation for the intermediates.
15.11. Identify the coordinate system that would result in a linear graph:
a) ln [SiH 4 ] vs. t, b) log[SiH 4 ] vs. t, c) 1/[SiH 4 ] vs. t, d) 1/[SiH 4 ]2 vs. t, e) none of these

56th IChO Preparatory Problems 76

Solution
15.1.
Fe 3 Al 2 Si 3 O 12 or Ca 3 Fe 2 Si 3 O 12 have the heaviest variable substituents, and the latter has
the highest molar mass, and thus the lowest silica content. 3CaO·Fe 2 O 3 ·3SiO 2 is the oxide
decomposition.

15.2.

ne
From the picture we see that each Si atom is surrounded by 4 oxygen atoms. If an O atom
is connected only to 1 Si atom thus it will have charge -1. In order we will have charges: -

Ju
10, -18, -20, -22
Structure a) is a chain silicate fragment: (SiO2−
3 )𝑥𝑥

il
6− )
Structure c) is a double chain silicate fragment: (Si4 O11 𝑥𝑥

Structure d) is a sheet silicate fragment: (Si2 O2−

5 )𝑥𝑥
nt
lu
15.3.
In this sample of beryl, the total mass of O and Al is 0.1287g. The ratio between these 4
atoms is the next:
tia

0,0102 0,0635 𝑥𝑥 0,1287−𝑥𝑥

𝑛𝑛𝐵𝐵𝐵𝐵 : 𝑛𝑛𝑆𝑆𝑆𝑆 : 𝑛𝑛𝑂𝑂 : 𝑛𝑛𝐴𝐴1 = 9
: 28
: 16 : 27
en

Using electroneutrality:
𝑛𝑛𝐵𝐵𝐵𝐵 ⋅ (+2) + 𝑛𝑛𝑆𝑆𝑆𝑆 ⋅ (+4) + 𝑛𝑛𝑂𝑂 ⋅ (−2) + 𝑛𝑛𝐴𝐴𝐴𝐴 ⋅ (+3) = 0
id

0,0102 0,0635 𝑥𝑥 0,1287 − 𝑥𝑥

⋅2+ ⋅4+ ⋅ (−2) + � � ⋅ 3 = 0 ⇒ 𝑥𝑥 = 0.1086
9 28 16 27
0,0102 0,0635 0,1086 0,0201
nf

𝑛𝑛𝐵𝐵𝐵𝐵 : 𝑛𝑛𝑆𝑆𝑆𝑆 : 𝑛𝑛𝑂𝑂 : 𝑛𝑛𝐴𝐴1 = : : : = 3: 6: 18: 2

9 28 16 27
Thus, beryl is Be 3 Al 2 Si 6 O 18
Co

Bazzite is Be 3 X 2 Si 6 O 18 and we don’t know if element X is lighter or heavier than Al.

𝑚𝑚(𝑆𝑆𝑆𝑆) 0.0635 6⋅28.09
The Si mass fraction is 𝜔𝜔 = 𝑚𝑚(𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏) = 0.2024 = 537.5
= 0.3136. If we replace Al by X, the
bazzite molar mass will change by 2a g/mol where a is the molar mass difference between
X and Al.
If the mass fraction of Si decreases and increases:
6 ⋅ 28.09
= 0.3136 ⋅ (1 − 0.0627) ⇒ 𝑎𝑎 = 17.94 ⇒ 𝑀𝑀(𝐗𝐗) = 44.95 ⇒ Sc
537.5 + 2𝑎𝑎

56th IChO Preparatory Problems 77

 6 ⋅ 28.09
= 0.3136 ⋅ (1 + 0.0627) ⇒ 𝑎𝑎 = −15.88 ⇒ 𝑀𝑀(𝐗𝐗) = 11.11 ⇒ almost B
537.5 + 2𝑎𝑎
Boron is different in size and chemistry (e.g., not a metal) from Al, but scandium is rather
similar and can substitute Al in a lattice easily.
Thus, bazzite is Be 3 Sc 2 Si 6 O 18

15.4.
The mineral absorbs the light, thus we should search for the complementary color of

ne
green. That is red: green and emerald are very close thus emerald cannot be a
complementary color to green.

Ju
15.5.
Mg 2 Si + 4HCl → 2MgCl 2 + SiH 4

il
SiF 4 + 4LiH → 4LiF + SiH 4
SiCl 4 + LiAlH 4 → SiH 4 + LiAlCl 4 nt
lu
15.6.
A contains more than 90% of Si indicating that the remaining element could only be
tia

hydrogen. SiH 2 corresponds to the composition, but the high molar mass (the highest of
all) means that it is an oligomer or polymer cyclic compound (SiH 2 ) x where x is 6 or more
. A polymer could only be formed from Mg 2 Si where Si-Si bonds can be present already.
en

Molecule B has two planes of symmetry, so it can be SiH 2 X 2 (SiH 4 or SiY 4 are not
byproducts). X as Cl gives the right molar mass, thus B is SiH 2 Cl 2 , a byproduct of the
second reaction.
id

Molecule C has ω Hal =73.1% and the halogen must be fluorine as the remaining reaction
starts from SiF 4 . The molar mass of the compound is also higher than 101 g/mol and can
nf

be calculated as
19𝑛𝑛
Co

𝑀𝑀 = 0.731 = 26𝑛𝑛,

where n is the number of F atoms. Very curiously n= 1 is close LiF, but its molar mass is
smaller than 101 g/mol, and it does not contain Si atoms. At the same time n = 4 is close
to SiF 4 , one of the reactants. The combination of the two could also be a byproduct:
2LiF+SiF 4 →Li 2 [SiF 6 ]
So C is Li 2 [SiF 6 ]

56th IChO Preparatory Problems 78

15.7.
The lowest melting point belongs to SiH 4 as a very light molecule with only weak
intermolecular interactions (Si and H have a similar electronegativity). The strongest
Lewis acid is SiF 4 due to the inductive effect of F.

15.8.
Step 1 is chain initiation.
Steps 4 is chain propagation.
Step 6 is chain termination.

ne
15.9.
SiH 4 + N 2 O →SiH 3 (OH)+ N 2

Ju
15.10.

il
For unbranched chain reactions, there are two useful rules of thumb that accelerate the
kinetic derivations:
nt
i. The rate of the initiation and termination steps are equal (as the chain carriers must be
in steady state). In this case:
lu
k 1 [N 2 O] = k 6 [SiH 3 ][SiH 3 O]
ii. The rates of all propagation steps are equal to the rate of product formation (as the
tia

stoichiometry of the overall reaction must be shown by the chain):

v = k 4 [SiH 3 ][N 2 O] = k 5 [SiH 3 O][SiH 4 ]
en

From the second condition:

𝑘𝑘5 [SiH3 O][SiH4 ]
[SiH3 ] =
𝑘𝑘4 [N2 O]
id

Substituting this into the first condition:

nf

𝑘𝑘1 𝑘𝑘4
[SiH3 O] = [N2 O]�
𝑘𝑘5 𝑘𝑘6 [SiH4 ]
Co

The rate of product formation:

𝑘𝑘1 𝑘𝑘4 𝑘𝑘5

ν = 𝑘𝑘5 [SiH3 O][SiH4 ] = � [SiH4 ]0.5 [N2 O]
𝑘𝑘6

v = k[N 2 O][SiH 4 ]0.5=k’[SiH 4 ]0.5

15.11.
The reaction order with respect to silane is 0.5, so none of the proposed coordinates
gives a linear dependence.

56th IChO Preparatory Problems 79

16. Boron clusters
The chemistry of boron-based cluster anions is undergoing a revival thanks to their high
stability, kinetic inertness, and easy functionalization.
A synthesis starts by heating NaBH 4 with equimolar amount of B 2 H 6 to produce
compound A. A reaction was accompanied by the evolution of a combustible gas
equimolar with A. After that, compound A was heated up to 165 °C in diglyme (bis(2-
methoxyethyl) ether) with 1.5 equivalent of B 2 H 6 in a sealed air-free reactor to produce
a salt B containing a doubly charged cluster anion and the same combustible gas.

ne
Compound B has 1:1 B:H ratio and a 24.5% by weight Na content.
16.1. Give the formulas of A and B and the balanced reactions of their formation.

Ju
Functionalizing boron clusters can be done using a wide range of reagents. One of the
functionalization reactions is halogenation, forming weakly coordinating anions that
activate their counter cations.

il
The cesium salt prepared by ion exchange from compound B was suspended in 1:1 water-
nt
methanol solvent mixture. Then the suspension was cooled down using an ice bath and
halogen C was added slowly. After that, the reaction mixture was heated up to 90 °C under
reflux. After quenching the small excess of halogen using sodium sulfite, the solvent was
lu
removed using rotary evaporator and product D was recrystallized using hot water,
which is another cesium salt with a doubly charged anion. It has 19.6% by weight cesium
and 9.6% by weight boron besides halogen.
tia

16.2. Give the formulas of C and D and the balanced reactions of the formation of D and
the quenching of excess C.
en

These clusters can serve as scaffolds for multifunctional nanomolecules with a well-
defined structure. Using varied linkers and functional groups, the size and functionality of
the nanomolecules can be tuned. A recent work showed great promise with covalently
id

attached saccharides as functional groups that can bind with proteins.

The synthesis was pursued according to the synthesis scheme below:
nf

1. OAc
2K+
O 2-
AcO
Co

AcO SH
OAc
E K3PO4 linker HO
1. , base S OH
[Bu4N]2[B12(OH)12] [B12(linker)12] OH
O
2. Fe3+ F 2. deprotection G
OH
= B-linker-thiosugar =B

56th IChO Preparatory Problems 80

The synthesis starts by reacting the tetrabutylammonium salt of the perhydroxylated
clusters in the presence of a base with compound E (C 13 H 6 BrF 5 ) in a polar solvent.
Compound E shows two doublets around 7.5 ppm and a singlet around 4.5 ppm in its 1H-
NMR spectrum and 3 different signals in 19F-NMR. The attachment reaction of linker E is
reasonably fast and complete on all cluster atoms. Subsequent functionalization is carried
out on the neutral molecule F produced by reaction with Fe(III)-chloride.
16.3. Give the structure of E and F. Use ⊗ to symbolize the cluster and only draw out
one of the attached groups.
F was reacted with 1-thio-β-D-glucose tetraacetate (and other thiols) in the presence of

ne
K 3 PO 4 to introduce biologically relevant functionality. The rapid and complete
functionalization reaction was monitored by 19F-NMR because the pure product only has
2 different fluorine environments. The final product obtained after deprotecting the
glucose is a dipotassium salt of the decorated cluster, G.

Ju
Thiols were always used in excess, because they serve in another role besides the
attachment of functionality to the cluster.

il
16.4. Determine the minimum amount of thiol needed by 1 mol of F. What is an

16.5.
nt
appropriate reagent to deprotect the glucose residue?
Draw the structure of a linker in G indicating only the B and S atoms from the rest
lu
of the molecule.
The glucose-coated nanomolecules show a much higher affinity towards lectin (a
carbohydrate binding protein) than individual glucose molecules. Gold nanoparticles
tia

coordinated with 1-thio-β-D-glucose molecules also strongly bind to lectin.

16.6. What molecules potentially present in biological samples could affect the
stability of the coordinated gold nanoparticles, but not the functionalized borate
en

clusters?
id
nf
Co

56th IChO Preparatory Problems 81

Solution
16.1.
Hydrogen gas is the byproduct.
A: Na[B 3 H 8 ]
NaBH 4 + B 2 H 6 → Na[B 3 H 8 ] + H 2
B: Na 2 [B 12 H 12 ],

ne
2 Na[B 3 H 8 ] + 3 B 2 H 6 → Na 2 [B 12 H 12 ] + 11 H 2
Calculations: Since the compound is a salt with anion that has −2 charge, it has two sodium

Ju
cations per formula. Assuming that the compound has the formula Na 2 B x H x , since 24.5%
by weight is Na, one can make the following equation:
22.99 ∙ 2

il
∙ 100% = 24.5%
22.99 ∙ 2 + 𝑥𝑥 ∙ (10.81 + 1.008)
x = 12. nt
lu
16.2.
C is Br 2 , D is Cs 2 [B 12 Br 12 ].
tia

Since the compound contains Cs, B, and halogen with -2 anion, the general formula is
Cs 2 [B x Hal y ],
en

If halogen % by weight is 70.8%, one can solve for x using the relationship between the
number of moles of Cs and B (assuming that we have 100 g of the compound):
19.6 2 9.6
id

= ∙
132.9 𝑥𝑥 10.811
x = 12.
nf

For the halogen, one can use the same reasoning giving:
19.6 2 70.8 960.13
Co

= ∙ ⇒ 𝑀𝑀 =
132.9 𝑦𝑦 𝑀𝑀 𝑦𝑦
using y = 12 gives 80 g mol-1, which corresponds to bromine (Br).
Formation of D:
Cs 2 [B 12 H 12 ] + 12 Br 2 → Cs 2 [B 12 Br 12 ] + 12 HBr
Quenching reaction:
Br 2 + SO 3 2- + H 2 O → 2 Br- + SO 4 2- + 2 H+

56th IChO Preparatory Problems 82

16.3.
Br 0

F
F O F
F
F F
F F F
F
E F

= B-linker =B

ne
⊗(−CH 2 −p-C 6 H 4 −C 6 F 5 ) 12 is another representation of F.

Ju
16.4.
12 equivalents of thiol are needed for functionalization.

il
The thiol also reduces the neutral boron cluster into the dianion (2 e- needed). As 1 thiol
nt
furnishes 1 e-, at least 14 eq. of the thiol are needed.
lu
MeONa in MeOH is a possible deprotecting agent.
tia

16.5.

B
en

O F
F
id

F S
F
G
nf

16.6.
Co

Thiols, e.g. cysteine can also bind to the gold and crowd out the sulfur-coordinated
functional parts of the nanoparticle. The covalent bonds in the boron-based nanoparticle
keep the nanoparticle intact.

Reference: Qian, E., Wixtrom, A., Axtell, J. et al. Atomically precise organomimetic cluster
nanomolecules assembled via perfluoroaryl-thiol S N Ar chemistry. Nature Chem 9, 333–
340 (2017). https://doi.org/10.1038/nchem.2686

56th IChO Preparatory Problems 83

17. MOFs: The Ultimate
Coordination Network
Metal Organic Frameworks (MOFs) are coordination polymers typically built up from a
transition metal and an organic linker featuring multiple coordinating functional groups.
They play a significant role in hydrogen or ammonia storage and catalysis due to their
large cavities and high porosity. The wide range of linker variations in size, shape, and
coordinating functional group, coupled with the diverse metals available, results in

ne
numerous MOFs with distinct properties and applications. Their cavities make them
excellent for storing various gases (hydrogen, ammonia, carbon dioxide, etc.).
The copper-based MOF-a holds promise in ammonia storage. The synthesis of the

Ju
structure starts by combining copper(II) salt A with an equimolar amount of the double
linker B in DMF (N,N-dimethylformamide), resulting in a blue solution. This solution is
stirred for 16 hours at 90°C, leading to the formation of a green-blue precipitate. After

il
filtration, the precipitate was washed three times with DMF, followed by soaking in

nt
methanol for 24 hours. This soaking process is repeated with fresh methanol before final
storage in a separate portion of methanol.
To analyze A, slow heating was applied under a flow of inert gas, and the weight loss was
lu
monitored. Around 120 °C, a 19.4% weight loss was observed, attributed to water loss.
After reaching 250 °C, a black material C remained, and a reddish gas mixture evolved.
The total mass loss up to this point, including water, amounted to 65.8% by weight.
tia

Switching the gas flow to hydrogen, and continuing heating, the black material lost 20.1%
weight and copper was left behind.
en

17.1. Give the formula of A and C. Support your result by calculations.

Linker B is a symmetrical molecule containing only 3 elements and has a molar mass of
172 g/mol. It has an inversion center, and it does not decolorize bromine water. Titrating
id

the distinctly acidic solution of 0.500 g of B needed 11.6 mL of 0.500 M NaOH solution. B
has 3 different signals in 13C-NMR.
nf

17.2. Draw the structure of B. Does it have any stereoisomers?

One method to estimate the surface area of a porous material consists of flooding nitrogen
Co

gas on the evacuated sample and monitoring pressure and adsorption. For MOF-a, the
nitrogen uptake flattened out around 5.0·10−3 mol/g before further increase. This region
is interpreted to correspond to the formation of a monolayer on the surface.
17.3. Calculate the specific surface area of MOF-a in m2/g if we know that the cross-
sectional surface area of a nitrogen molecule is 0.162 nm2.
MOF-a has a unique metal coordination environment resulting in a 3D framework. Each
copper atom is linked to 4 oxygen atoms from 4 different linkers in an approximately
square planar way. That places two Cu atoms in each other’s vicinity, and an oxygen atom
from a 5th linker is attached to each copper.

56th IChO Preparatory Problems 84

When ammonia, nitrogen, and hydrogen adsorptions were tested at room temperature,
MOF-a adsorbed significant amounts of ammonia compared to nitrogen and hydrogen as
summarized on the graph below. The green solid becomes blue on exposure to ammonia
(solid circles), and on desorption (empty circles) it turns purple. Two levels are marked
on the graph for their importance. Level 2 corresponds to saturation with ammonia and
Level 1 is the endpoint of desorption at 1 mbar pressure at room temperature. Careful
heating resulted in the reconstruction of the original MOF-a.

ne
Ju
il
nt
lu
17.4. Calculate the number of ammonia molecules coordinating to each Cu atom in the
structure corresponding to Level 1 and 2. MOF-a has 27.2% by weight of copper.
tia

X-ray measurements established that both structures are one-dimensional (i.e. have a
straight linear arrangement of linked Cu atoms) and the copper atoms in both structures
have two oxygen atoms from two ligands coordinated.
en

17.5. What are the primary coordination environments of the copper atoms in the two
structures?
id
nf
Co

56th IChO Preparatory Problems 85

Solution
17.1.
Answer: A is Cu(NO 3 ) 2 .2.5H 2 O, C is CuO.
Calculations: Since C has 79.9% by weight of copper, one can calculate the molar mass of
the leftover by calculating the molar mass per mol of copper giving us the following
63.5
relationship for the rest of the molar mass: 0.799 − 63.5 = 16 g/mol (oxygen).

ne
As for A, since we know the % by weight for water loss and the overall loss, we can find
the loss of the other elements, which is 55.2% by weight, since we know that copper forms
79.9% of what is left from A (34.2%), Cu forms 27.3% of the overall % by weight of A.

Ju
Using this information with the 19.4% of water, the rest of the elements forms 53.3% by
63.5 1
weight. Using all these data points, the molar mass of the anion is: 0.273 ∙ 53.3% ∙ 2 =
62 g mol-1 , which implies the existence of nitrate since reddish gas (NO 2 ) is formed from

il
the TGA.

19.4 g /18 g mol−1

nitrate: 80.6 g /187.5 g mol−1 = 2.5.
nt
The amount of water can be calculated from the molar ratio between the water and copper
lu
A is Cu(NO 3 ) 2 .2.5H 2 O
tia

17.2.
O O
en

C 8 H 12 O 4 , trans- HO OH .
Acidity and neutralization by NaOH mean that the linker has carboxylic acid groups (2 of
id

them since it is a double linker).

0.5 M ∙0.0116 dm3
Using the titration calculations: = 2.
nf

0.5 g /172 g/mol

This implies that what is left of the molar mass is: 172 – 90 (2 CO 2 H) = 82 g mol-1. Since it
Co

is an organic linker with C, H, and O, the rest of the molar mass can be attributed to C 6 H 10 .
Therefore, the chemical formula is C 8 H 12 O 4 .
Since the molecule does not decolorize bromine water, it does not have any double bonds
and is symmetric with 3 carbon environments, it has to be a cyclohexane with 2 carboxylic
acid groups trans to each other in positions 1 and 4.
A cis-stereoisomer exists.
O O O O

HO OH HO OH

56th IChO Preparatory Problems 86

17.3.
After converting everything to the correct units,
SA = 0.0050 mol g-1 · 6.02 · 1023 mol-1 · 0.162 · 10-18 m2 = 490 m2 g-1.

17.4.
Level 2 is around 17 mmol of adsorbed ammonia per 1 g of MOF-a. So, by converting units
0.017 mol NH3 100 g 𝐌𝐌𝐌𝐌𝐌𝐌−𝐚𝐚 63.5 g Cu mol NH3
of the uptake: · · =4 .
1 g 𝐌𝐌𝐌𝐌𝐌𝐌−𝐚𝐚 27.2 g Cu 1 mol Cu mol Cu

ne
Therefore, 4 molecules of NH 3 are there per Cu center in the structure corresponding to
Level 2. Level 1 has approximately half as much ammonia absorbed, and thus 2 ammonia
molecules per Cu center.

Ju
17.5.

il
The Cu atoms will have 2 O atoms opposite each other in both structures to allow for the
nt
1D structures. The level 1 structure has a square planar coordination sphere with 2
ammonia molecules and 2 linker O atoms in trans positions.
lu
The structure corresponding to Level 2 has octahedral coordination with 4 square planar
ammonia molecules and two axial oxygens from the linker.
tia

Reference:
Snyder, B.E.R., Turkiewicz, A.B., Furukawa, H. et al. A ligand insertion mechanism for
en

cooperative NH 3 capture in metal–organic frameworks. Nature 613, 287–291 (2023).

https://doi.org/10.1038/s41586-022-05409-2
id
nf
Co

56th IChO Preparatory Problems 87

18. Black gold
“Black gold” has nothing to do with the actual element Au or its compounds. It is a name
which refers to oil, also known as petroleum: “black” due to the color of crude oil and
“gold” as it is a very valuable resource nowadays.
Saudi Arabia has the second-largest proven petroleum reserves in the world. The country
actively produces, exports, and refines petroleum crude oil. Gasoline and diesel are the
products of petroleum that are used as fuels for vehicles. Due to the nature of engine
combustion phenomena, burning these fuels in automotive engines contributes to the

ne
emission of air pollutants. Among them are unburned hydrocarbons (UHC), particulate
carbon (C), carbon monoxide (CO), and nitrogen oxides (NO x ).

Ju
18.1. Choose the major products of gasoline combustion when the air supply is 10 kg
per 1 dm3 of fuel. Use octane C 8 H 18 (density ρ = 0.703 g/cm3) as the model
compound for gasoline.

il
□ UHC □C □ CO □ CO 2 □ H2 □ H2O □ H2O2

nt
The formula NO x represents two nitrogen oxides: NO and NO 2 . These gases are formed in
engines from atmospheric nitrogen and oxygen due to high temperatures achieved during
the combustion of fuels. Although NO and NO 2 are relatively simple compounds, they have
lu
rather complicated structures and bonding. First of all, both compounds are radical
species, for which the commonly used octet rule doesn’t apply.
tia

18.2. For the NO 2 molecule:

a) Draw the Lewis structures of two resonance forms,
b) Indicate the N–O bond order,
en

c) Indicate the hybridization of N atom,

d) Indicate the geometry of the molecule.

The correct N–O bond order in NO molecule can’t be

id

determined using Lewis structures with the typical

two-center two-electron bonds. Instead, the
nf

molecular orbital (MO) diagram can provide the

answer.
Co

18.3. For the NO molecule:

a) Fill in the atomic (AO) and molecular (MO)
orbitals in the provided MO diagram with the
electrons.
b) Calculate the N–O bond order.
c) Compare the dissociation energies of NO,
NO+ and NO–.

56th IChO Preparatory Problems 88

It is mandatory now in most countries that all the vehicles sold are equipped with a special
device that converts harmful exhaust gases from the engine into less harmful ones. This
device is called a catalytic converter as it has a heterogeneous redox catalyst, which is
usually a mixture of precious metals.
18.4. Give the formulas for the target products of catalytic conversion of UHC, C, CO and
NO x .

More than half of metal M mined is used by the automotive industry to produce catalytic
converters. This has a drastic influence on the price of this metal: although there are rarer
elements than metal M, some of them actually cost less because of the lower demand.

ne
Organic compound HL is used to precipitate metal M from solutions in the form of a ML 2
complex for recovery, purification, and gravimetric purposes. The content of metal M in
ML 2 is 31.61% by mass (wt.%, mass fraction, ω) and 3.23% by number of atoms (at.%,

Ju
atomic percent, χ). The HL molecule consists of 2 nitrogen atoms, 2 oxygen atoms and 2
other elements, and has a degree of unsaturation (also known as “double bond
equivalent”) of 2.

il
18.5. Determine the molecular formula of HL and metal M.
nt
Below is the simplified MO diagram for ML 2 with the most important interactions shown.
The interaction between d orbitals of metal cation M2+ and high-lying filled orbitals of the
lu
ligands L– leads to the splitting of d orbitals.
d x2−
E y2
tia

z
en

x y
id

d z2

d xz d
yz
nf

d orbitals of M2+ d xy
Co

−
8 high-lying filled orbitals of 2L

−
2
N N N N
M
N N N N

18.6. Fill in the MO diagram with electrons of M2+.

Note: If you haven’t found metal M in the previous question, take any platinum group
metal and note it on the diagram.

56th IChO Preparatory Problems 89

ML 2 is a square planar complex, where M2+ is coordinated to all 4 sp2-hybridized N atoms.
Therefore, 8 high lying filled ligand orbitals considered here are the following:
Combinations of sp2-hybrid orbitals:
N N N N N N N N
N N N N N N N N

ne
φ1 φ2 φ3 φ4
Combinations of p orbitals:
N N N N N N N N

Ju
N N N N N N N N

il
φ5 φ6
nt φ7 φ8
lu
18.7. In the table below:
a) Draw each d orbital of the metal (note the coordinate system),
b) Indicate the interacting orbital(s) φ i of appropriate symmetry and the type of
tia

overlap between these orbitals (σ, π, or δ).

d orbital Drawing Interacting orbital(s) φ i Overlap

en

dxy
id

dxz
nf
Co

dyz

d z2

dx2−y2

56th IChO Preparatory Problems 90

Solution
18.1.
Combustion reactions of octane producing C, CO and CO 2 :
C 8 H 18 + 4.5O 2 → 8C + 9H 2 O
C 8 H 18 + 8.5O 2 → 8CO + 9H 2 O
C 8 H 18 + 12.5O 2 → 8CO 2 + 9H 2 O
Mole ratio between the supplied O 2 (mole fraction in air 𝜒𝜒(O2 ) = 21%) and C 8 H 18 :

ne
𝑛𝑛(O2 ) 𝑚𝑚(air) 𝜒𝜒(O2 )𝑀𝑀(C8 H18 ) 10000 g 0.21 ∙ 114 g mol−1
= ∙ = ∙ = 11.7
𝑛𝑛(C8 H18 ) 𝑉𝑉(C8 H18 ) 𝑀𝑀(air)ρ(C8 H18 ) 1000 cm3 29 g mol−1 ∙ 0.703 g cm−3

Ju
As 8.5 < 11.7 < 12.5, the products of combustion are CO, CO 2 and H 2 O.

il
18.2.
a) Lewis structures:

N
nt N
lu
O O O O

b) N–O bond order: 1.5

tia

c) Hybridization of N: sp2
d) Geometry: bent (V-shaped)
en

18.3.
id

a) MO diagram:
AO MO AO
nf

(N) (NO) (O)

E
4σ*
Co

2π∗
2p
2p
3σ
1π

2s 2σ*

2s

1σ

56th IChO Preparatory Problems 91

 𝑁𝑁𝑒𝑒− (bonding)−𝑁𝑁𝑒𝑒− (antibonding) 8−3
b) N–O bond order: 2
= 2
= 2.5

c) The values of the bond orders in NO, NO+ and NO– are equal to 2.5, 3 and 2, respectively.
Thus, dissociation energy increases in the row: NO– < NO < NO+.

18.4.
CO 2 , H 2 O, N 2

ne
18.5.
There are 4 nitrogen and 4 oxygen atoms in complex ML 2 , as well as carbon and hydrogen.

Ju
Therefore, the composition of ML 2 is MC 2x H 2y N 4 O 4 , and HL should be C x H y+1 N 2 O 2 .
From the atomic percent of metal M:

il
1 1
χ(𝐌𝐌) = = = 0.0323
nt
1 + 2𝑥𝑥 + 2𝑦𝑦 + 4 + 4 2𝑥𝑥 + 2𝑦𝑦 + 9
𝑥𝑥 + 𝑦𝑦 = 11
lu
From the degree of unsaturation of HL:
2𝑁𝑁(C) + 2 − 𝑁𝑁(H) + 𝑁𝑁(N) 2𝑥𝑥 + 2 − (𝑦𝑦 + 1) + 2
DU = DBE = = =2
tia

2 2
2𝑥𝑥 − 𝑦𝑦 = 1
Solving the system of equations:
en

𝑥𝑥 = 4, 𝑦𝑦 = 7
The molecular formula of HL is C 4 H 8 N 2 O 2 (dimethylglyoxime).
id

From the mass fraction of metal in ML 2 :

nf

𝑀𝑀
ω(𝐌𝐌) = = 0.3161
𝑀𝑀 + 12.01 ∙ 2𝑥𝑥 + 1.008 ∙ 2𝑦𝑦 + 14.01 ∙ 4 + 16.00 ∙ 4
Co

𝑀𝑀 + 230.2 = 3.164𝑀𝑀
𝑀𝑀 = 106.4 ⇒ 𝐌𝐌 = Pd
Molecular formula of HL: C 4 H 8 N 2 O 2
Metal M: Pd

56th IChO Preparatory Problems 92

18.6.
d x2−
E y2

d z2

d xz d
yz

ne
d orbitals of M2+ d xy

Note: This is an MO diagram, as opposed to more commonly taught CFT diagrams.

Ju
Students are only expected to interpret these diagrams, not to build them from scratch.

il
18.7.
d orbital Drawing nt Interacting orbital(s) φ i Overlap
lu
dxy N N none none
M
N N
tia

dxz N N
φ7 π
M
N N
en

dyz φ6 π
N N
id

M
N N
nf

d z2 N N φ1 σ
M
Co

N N

dx2−y2 N N φ4 σ
M
N N

56th IChO Preparatory Problems 93

19. Nitrogen fixation
Dissociating the N 2 molecule requires 945 kJ/mol. The high bond energy results in
nitrogen being inert and not very reactive. In the early 20th century, Haber and Bosch
pioneered a method involving N 2 reacting with H 2 to produce NH 3 . However, their
process requires high pressure and temperature to break the strong N≡N bond.
Overcoming this challenge is crucial as it would mark a significant advancement in
artificial nitrogen fixation.
To understand this reaction, it's important to grasp the basics of nitrogen orbitals and

ne
bonding.
19.1. Draw the MO diagram of N 2 . Indicate the HOMO and LUMO of the molecule.

Ju
One approach to break the N≡N bond is to connect nitrogen atoms with an organometallic
species that's similar in terms of electronic structure. This concept predicting interactions
between metals and main group elements is called the isolobal analogy.

il
For instance, the CH 3 fragment and Mn(CO) 5 are isolobal because they both possess a
nt
single unpaired electron. They are also one electron away from a closed shell: 8 electrons
for carbon and 18 electrons for manganese.
lu
tia

The looped arrow is used to denote two species that are isolobal.
en

In the nitrogen fixation context, we will employ a molybdenum complex D that is isolobal
to the nitrogen atom in N 2 .
To synthesize this complex, we start with MoCl 5 based on the scheme below:
id

Sn Sn THF
MoCl5 MoCl4(OEt2)2 MoCl3(THF)3
nf

Et2O THF O
Co

19.2. Give the oxidation state of Mo and the d-electron count in each of the three
compounds.

The next schemes show the steps to synthesize the ligand for the complex and the
combination of the ligand and the metal.

56th IChO Preparatory Problems 94

 Ac2O
O HBF4 tBuNH2 1. n-BuLi, -100 °C

OH 90 °C
A BF4 CH3CN
B 2. Et2O
+
C8H11O C12H19N

(0.33 equiv.)
MoCl3(THF)3
C D
Et2O, -100 °C
C12H18NLi OEt2

ne
- Compound A 1H NMR: 7.69 ppm (s, 2H), 2.80 ppm (s, 6H), 2.65 ppm (s, 3H).
- Compound B 1H NMR: 6.36 ppm (s, 2H), 6.32 ppm (s, 1H), 3.89 ppm (br s, 1H), 2.17 ppm
(s, 6H), 1.29 ppm (s, 9H).

Ju
19.3. Give the structures of compounds A, B, C and D. Hint: A is aromatic.
Finally, when exposed to nitrogen gas, 2 equivalents of D will cleave the N≡N to produce

il
the complex F, through the intermediate E. (r.t. = room temperature)

D
2 equiv.
N2
nt
Et2O, -35 °C
E
warm to r.t.
F
2 equiv.
lu
19.4. Provide the constitution (connectivity) of intermediate E and the structure of
complex F. Use 'L' instead of drawing the entire ligand.
tia

19.5. Show the isolobal analogy of the D complex synthesized with the N atom,
considering the d-electron count and the number of ligands in the complex.
en
id
nf
Co

56th IChO Preparatory Problems 95

Solution
19.1.

LUMO

HOMO

ne
Ju
il
19.2.
MoCl 5 – oxidation state: +5, d1
MoCl 4 (OEt 2 ) 2 – oxidation state: +4, d2
nt
lu
MoCl 3 (THF) 3 – oxidation state: +3, d3
tia

19.3.
en

N N
NH NLi
• Et2O Mo
id

O N
nf

A B C D
Co

Note: mechanism of transformation of A to B (not required, for illustration only).

56th IChO Preparatory Problems 96

19.4.
L
L L
Mo

N N

Mo Mo
L L L L
L L

ne
E F
E is an intermediate. The constitution is showing the connectivity. Bonding was not

Ju
requested.

il
19.5.

nt
D contains Mo(III) with three ligands. That implies a d3 electron configuration on the
metal with three unpaired electrons, just as the N atom has three unpaired electrons.
lu
tia
en
id
nf
Co

56th IChO Preparatory Problems 97

20. Bromination
The addition of bromine to alkenes occurs through a so-called bromonium ion
intermediate:

Et Br
Br2 H Br Br Et
H H Et Me + H
H Et H
Me H Br H Me Br
Me
Br

ne
The positively charged bromine atom occupies one side of the intermediate, so the
bromide ion can only attack from the other side. This means that the process is
stereospecific, i.e., not all stereoisomers that are theoretically possible are formed. For

Ju
example, in the case of (E)-pent-2-ene, only molecules with the stereostructures shown
above are formed.
If the bromine atoms could not only enter from the opposite side (so-called anti-position),

il
the other two possible stereoisomers shown below could also be formed during the
bromination of (E)-pent-2-ene:

Me
H
ntBr
+
Br H
Et
lu
H H
Br Et Me Br

In the following question, the bromine addition to hydrocarbon molecules with eight
tia

carbon atoms and only one double bond is investigated.

20.1. Give the structure of one alkene molecule that doesn’t contain a ring and one
alkene molecule that does contain a ring for which the particular statement is true
en

if such a molecule exists. If no such molecule exists, write an X.

Does not contain ring Contains ring
id

a) During bromine addition,

only one of the three
possible stereoisomers is
nf

formed.
Co

b) During bromine addition,

two of the three possible
stereoisomers are
formed, and they are
enantiomers.

c) During bromine addition,

both of the two possible
stereoisomers are
formed, and they are
enantiomers.

56th IChO Preparatory Problems 98

 d) During bromine addition,
both of the two possible
stereoisomers are
formed, and they are
diastereomers.

e) The product of bromine

addition has no
stereoisomers.

ne
However, other products can also result from the bromination process. If the reaction

Ju
takes place in an aqueous medium, the bromonium ion produced in the first step may be
attacked by a water molecule instead of the bromide ion. The resulting cation is
deprotonated, and overall, a hydroxy group is incorporated into the molecule. In aqueous

il
solution, this so-called bromohydrin is the main product, in which a bromine atom and a
hydroxy group are present at the 1,2 positions.
nt
During the formation of bromohydrin, regioselectivity plays a role in addition to
stereospecificity. The water molecule is more likely to attack the higher order (more
lu
substituted) carbon atom of the bromonium ion.
20.2. Which main product(s) do you expect to be formed during the bromination of
tia

1-methylcyclohex-1-ene in an aqueous solution? Show the stereostructure using

wedge–dash notation ( ; ).
Br2
en

H2O/ACN
id
nf
Co

56th IChO Preparatory Problems 99

Solution
20.1.
Does not contain ring Contains ring
a) During bromine addition,
only one of the three
C 3H 7
possible stereoisomers is C 3H 7
formed.

ne
b) During bromine addition,
two of the three possible
stereoisomers are C 3H 7

Ju
formed, and they are C 3H 7
enantiomers.

il
c) During bromine addition,
both of the two possible
stereoisomers are
formed, and they are
ntC6H13
lu
enantiomers.

d) During bromine addition,

tia

both of the two possible

stereoisomers are
formed, and they are
en

diastereomers.

e) The product of bromine

C 3H 7
addition has no
id

stereoisomers. C 3H 7
nf

Other structures that fulfill the statements are acceptable.

Co

20.2.

OH OH

Br Br

56th IChO Preparatory Problems 100

21. NMR puzzle
One day Dr. Preping found a sealed container in his lab, filled with a white powder. The
label only said has disappeared. He did not want to dispose of it, so he tried to figure out
what it was. Upon dissolving the powder in water, he experienced intensive bubbling and
the solution turned slightly basic afterwards. When he dissolved the powder in alcohol,
he experienced gas evolution again, but less intensive than before. He could not observe
melting in the range of his apparatus (up to 300 °C). The compound could not be dissolved
in ether and was only slightly soluble in THF. He asked for the help of Prof. Speclock, who

ne
examined the filtrate of the THF suspension, and found an interesting group of signals in
the 1H NMR spectrum. See the figure. (The numbers at the bottom are integrals of the
respective signals.)

Ju
il
nt
lu
tia

She immediately knew what the unknown compound could be. She showed Dr. Preping
en

the following table.

Spin Natural Spin Natural

id

Isotope quantum abundance Isotope quantum abundance

number (%) number (%)
1H ½ 99.99 29Si −½ 4.69
nf

2H 1 0.0115 31P ½ 100

6Li 1 7.42 32S 0 99.24
Co

7Li 3/2 92.58 33S 3/2 0.76

10B 3 19.9 35Cl 3/2 75.53
11B 3/2 80.1 37Cl 3/2 24.47
12C 0 98.93 47Ti 5/2 7.28
13C ½ 1.07 49Ti 7/2 5.51
14N 1 99.64 117Sn ½ 7.61
15N −½ 0.36 119Sn ½ 8.58
16O 0 99.96 121Sb 5/2 57.21
17O −5/2 0.04 123Sb 7/2 42.79
19F ½ 100 203Tl ½ 29.5
27Al 5/2 100 205Tl ½ 70.5

56th IChO Preparatory Problems 101

21.1. Suggest a formula for the unknown compound X. (Give your explanation!)
Dr. Preping was very happy because he wanted to perform the following reactions and he
had been looking for the necessary reagent in his lab for a long time. Now he understood
that he hadn’t been able to find it because it was labelled ‘compound X’ the whole time.
When carrying out the reactions, he was again absentminded a bit and could not
remember which reactants he used for which flask. He knew only that he used all the
amines and aldehydes once (see table). Prof. Speclock helped again. Based on the 1H NMR
spectra of the amine products (A, B, C) it was obvious which flask contained which
compound.

ne
NH2
+
CHO
N
R2 X H
N
R2

Ju
R1 R2
R1 R1

il
R1 R2

p-I H

p-MeO
nt o-Br
lu
p-Me p-F
tia

A: 1H NMR δ 2.19 (3H, s), 3.7 (1H, br. s), 4.32 (2H, s), 6.86 (2H, d), 6.92 (1H, t), 7.05 (2H, d), 7.23
(1H, d), 7.28 (1H, t), 7.45 (1H, d) ppm.
B: 1H NMR δ 3.6 (1H, br. s), 3.71 (3H, s), 4.25 (2H, s), 6.59 (2H, d), 6.74 (2H, d), 7.32 (5H, m) ppm.
en

C: 1H NMR δ 4.31 (2H, s), 4.8 (1H, br, s), 6.41 (2H, d), 7.02 (2H, t), 7.29 (2H, dd), 7.52 (2H, d) ppm.

21.2. Give the structures for A, B, C.

id

The next week he attempted the same synthesis using a new combination of his amines
and aldehydes listed above. He obtained a colored compound D with totally different
nf

characteristics. It gave the 1H NMR spectrum listed below.

D: 1H NMR δ 2.35 (3H, s), 7.14 (2H, d), 7.23 (2H, d), 7.45 (3H, m), 7.88 (2H, d), 8.44 (1H, s) ppm.
Co

21.3. Identify compound D and consider the possible reasons for its formation.

56th IChO Preparatory Problems 102

Solution
21.1.
NaBH 4
2 isotopes of the atom attached to H in intensity ratio (4x100):(7x15)=400:105=80:20
The spin numbers: I 1 = (4-1)/2 = 3/2, I 2 = (7-1)/2 = 3. Only nucleus B fits.
The reaction that uses this reagent is a reduction.

ne
We cannot identify the cation, but sodium is a common borohydride.

Ju
21.2.
Br F
H H H
N

il
N N

A
O
nt
B
I
C
lu
21.3.
tia

The reduction step did not take place due to e.g., the presence of water in the reaction
mixture or Dr. Preping just forgot to add the reducing agent.
en

D
id
nf
Co

56th IChO Preparatory Problems 103

22. Organonitrogen Compounds:
The Compounds of Life
Nitrogen-containing compounds, such as amino acids, proteins, dyes, and medicines play
a crucial role in different aspects of our everyday lives. We shall explore some of their
classes in this task.
Amines are used as organic bases, for example in polymer and drug synthesis. Historically,

ne
amines were made using the Gabriel synthesis, which was developed by Siegmund Gabriel
in 1887. In this reaction, a primary alkyl halide reacts with potassium phthalimide in an
S N 2 reaction, which is followed by reaction with hydrazine. Gabriel synthesis is a key step
in the synthesis of the 2,3-dihydro-1H-indolizinium salt as shown below.

Ju
O

K N

il
Cl [Pd] catalyst N2H4
O
A nt I
B C
C11H13N
lu
N
tia

BF4
en

2,3-dihydro-1H-indolizinium salt
id

Palladium-catalyzed cross-coupling reaction

(Sonogashira coupling)
nf

+ [Pd] (cat.)
R1 H R2 X R1 R2
base
Co

Note: More commonly, the reaction employs a palladium catalyst as well as copper co-catalyst.

22.1. Draw the structures of compounds A–C.

22.2. Determine the number of signals in the 1H NMR spectrum of the final compound
(indolizinium salt)?

56th IChO Preparatory Problems 104

Amino acids are the building blocks of proteins. They can be synthesized from 2-oxoacids
as shown below in the synthesis of amino acid E. The synthesis yields racemic E.
O
D E
NH4Cl NaBH4
OH
O

22.3. Draw the structures of compounds D and E.

22.4. Draw the two enantiomers of E and assign the R/S configuration of the chirality
center(s).

ne
Many commercial medicines contain nitrogen atoms. Finasteride 474 is a medicine used
to treat hair loss in men. Its synthesis is shown below.
O

Ju
OH
NaIO4
KMnO4 NH3
H F G

il
H H C19H28O5 C19H27NO3
O

O
OH
nt
lu
H2, Pt
H
DCC
H
H H NH2
C23H38N2O2
tia

O N
H H

O H
N
en

O O DCC
Se Se
O H N C N
id

H H
O N
H H
nf

Finasteride 474

22.5. Draw the structures of compounds F, G, and H.

Co

22.6. Name the two functional groups containing nitrogen in Finasteride 474.
22.7. Label all the stereogenic centers in Finasteride 474 with an asterisk and assign
their R/S configuration.
22.8. Identify the role of DCC in the reaction leading to H.

56th IChO Preparatory Problems 105

Solution
22.1.

O
O
H 2N
N
N
O
O
A B C

ne
22.2.

Ju
11 NMR signals

il
22.3.
O

NH
O

OH
NH2
OH
nt
lu
D E
tia

Note: E can also be drawn as zwitterion

O

O
en

NH3

E
id

22.4.
nf

O O

OH OH
Co

NH2 NH2

(S)- (R)-

56th IChO Preparatory Problems 106

22.5.

O O O H
OH OH N

O H H
H
HO H H H H
H H
O O N O N
H H H

F G H

ne
Note: G can also be drawn as an N-acyl imine structure

Ju
22.6.
Lactam and amide. Note: A lactam is also an amide, so the answer amide is sufficient.

il
22.7.
O H
N
nt
lu
S S
R H S

R H H S
tia

O N S
H H
en

22.8.
Amide coupling reagent / dehydrating agent / activator of the carboxylic acid
id
nf
Co

56th IChO Preparatory Problems 107

23. NMR clue
In the following reactions all the steps are routinely used basic transformations, so only
the end product X was isolated, and the intermediates were not. Unfortunately, the 1H
NMR spectrum of X proved to be too complicated, so compound 7 was also investigated.
This spectrum was also too crowded but contained a characteristic signal corresponding
to an amide-type NH showing triplet multiplicity.
O

ne
O N K

OH Cl OBn MsCl O
H 2N
1 2

Ju
CF3
C11H12F3NO3 C12H14F3NO5S

il
NH2NH2
3 4
Boc2O
5 H2, Pd/C
6
C19H15F3N2O4 C11H13F3N2O2
nt C16H21F3N2O4
MW = 228.2
lu
O O
acylation Ph dil. HCl (aq.) Ph
tia

NC8H13F3NO2 NC3H5F3N
Ph
O 7 Ph
O X
en

Bn MsCl Boc2O
O
id

O O
S Cl
O O O O
nf

23.1. Determine the structures of compounds 1-7 and X.

Co

Y, a constitutional isomer of X has also been prepared. The aliphatic part of its 1H NMR is
listed: 2.02 (2H, d), 3.65 (1H, m), 4.11 (1H, dd), 4.18 (1H, dd) ppm.
23.2. What is the structure of Y? How can we explain that only X and not Y is formed
in the first synthesis?

56th IChO Preparatory Problems 108

Solution
23.1.
O
O O O CF3
OH OMs N
BnO N BnO N BnO N
H H H
CF3 CF3 O

1 2 3

ne
O CF3 O CF3 CF3
NH2 NHBoc NHBoc

Ju
BnO N BnO N H 2N
H H

4 5 6

il
Ph
O

N
CF3
NHBoc
Ph
O

N
CF3
ntNH2
lu
Ph O Ph O
7 X
tia

23.2.
en

O
NH2
Ph N
CF3
Ph O
id

Y
nf

In the conversion of 2 to 3 the strong base caused an intramolecular attack and resulted
in an intermediate product containing a 3-membered ring (2’). The ring opening occurred
Co

from a different position.

O

O
O -OMs- +
+
-H H
2 BnO N
OMs O N
CF3 3
CF3 OBn
2'

56th IChO Preparatory Problems 109

24. Neurotransmitters
Information is transmitted between neurons using neurotransmitters, chemicals that
carry messages from one nerve cell across space to the next nerve. Catecholamines are
neurotransmitters released by neurons and the adrenal gland. Dopamine, for example,
induces feelings of pleasure, satisfaction and motivation.
HO NH2

HO

ne
Dopamine

Other examples of catecholamines include epinephrine (D) and norepinephrine, derived

from the amino acid phenylalanine. The following scheme shows a synthetic route to

Ju
epinephrine (D), starting from catechol. D is stable under acid/alkaline hydrolysis
conditions.

il
CH3
ClCH2COCl N
HO H
AlCl3
ntA B NaBH4

HO
catechol
lu
H2
CH3
C Pd (cat.)
D +
tia

epinephrine

24.1. Draw the structures of compounds A–D.

en

The synthetic route above leads to a racemic epinephrine. However, our body produces it
as a single enantiomer of (R)-configuration. Using chiral resolution, it is possible to isolate
id

one enantiomer from a racemic mixture.

OH
1. HOOC
nf

COOH
OH
-tartaric acid
D (R)-D
Co

L-(+)

2. NH3
racemic enantiomerically pure
epinephrine epinephrine

24.2. Explain how the chiral resolution works and draw the structure of (R)-D.
Another group of neurotransmitters is derived from lipids. Anandamide is a fatty acid-
based neurotransmitter, first isolated and identified by William A. Devane in 1992. It is
present in the brain and binds to cannabinoid receptors. The name anandamide is derived
from the Sanskrit word ananda, which means joy, bliss, delight. It is responsible for
calmness and dream states.

56th IChO Preparatory Problems 110

 O
HO
N
H

Anandamide

Anandamide has a short-duration neurological effect and has attracted scientists to use
its structural variants as therapeutic agents to treat neuropathic pain. A series of

ne
anandamide analogues were synthesized by solid phase synthesis technique, in which the
starting material is attached to a solid support. After a sequence of reactions building
larger molecules, the product can be easily separated from the reaction mixture by a

Ju
simple filtration. Then, the solid support is removed by an appropriate reagent.
The synthetic scheme below depicts the preparation of an analogue (M) of anandamide.
Solid support is represented as a black ball. CuI and NaI serve as catalysts.

il
Copper-catalyzed cross-coupling reaction

R1 +
nt
(Sonogashira coupling)

R2 X
CuI (cat.)
lu
H R1 R2
base
Note: More commonly, the reaction employs a palladium catalyst as well as copper co-catalyst.
tia

Cl
OH
en

O OH PBr3
CH2OH
DIC, DMAP
E CuI, NaI, K2CO3
F G
id

PBr3 TFA
OH
H I J K
nf

CuI, NaI, K2CO3 CuI, NaI, K2CO3

Co

H2
SOCl2
L Lindlar cat.
M
N DIC DMAP TFA
H

N
O
N C N
F3C OH
N

56th IChO Preparatory Problems 111

24.3. What is the role of DIC? Select all that apply.
a) Base
b) Acid
c) Catalyst
d) Coupling reagent
e) Solvent

24.4. What is the role of DMAP? Select all that apply.

a) Base

ne
b) Acid
c) Catalyst
d) Coupling reagent

Ju
e) Solvent

24.5. Draw the structures of compounds E–M.

il
nt
lu
tia
en
id
nf
Co

56th IChO Preparatory Problems 112

Solution
24.1.
O O CH3
HO Cl HO N

HO HO
A B

ne
OH CH3 OH
H
HO N HO N
CH3

Ju
HO HO

C D

il
24.2.
nt
Chiral resolution is the process of separating the two enantiomers found in a racemic
lu
mixture. The process involves reacting the racemic mixture with an enantiomerically pure
chiral molecule and thereby producing two different diastereomers. Since diastereomers
differ from one another with respect to their physical properties, they can be separated
tia

using e.g. crystallization, distillation or column chromatography on silica. Finally, the title
compound has to be liberated. Since epinephrine is a base, it reacts readily with an acid
to form salt. Salts crystallize easily and therefore crystallization can be used to separate
the two diastereomers. In the final step, (R)-epinephrine is obtained from its salt by the
en

addition of a base.
OH
H
id

HO N
CH3

HO
nf

(R)-epinephrine
Co

24.3.
d) Coupling reagent
24.4.
a) Base and c) Catalyst

56th IChO Preparatory Problems 113

24.5.
O O
OH
CH2O CH2O

E F

O O
OH
Br
CH2O CH2O

G H

ne
O
Br
CH2O

Ju
I
O

il
CH2O

J nt
lu
O
O
HO
N
K
tia

N
en

L M
id
nf
Co

56th IChO Preparatory Problems 114

25. Henna
Henna is an essential product in the Saudi
Arabian and Middle Eastern cultures.
Traditionally, women use henna to make
gorgeous ornaments on their hands, arms and
feet for special occasions such as weddings
and the two Eid holidays. Henna is a red or
brown dye that is typically obtained from

ne
dried leaves of the henna tree (Lawsonia
inermis). Henna leaves contain a dye molecule
that is called lawsone. This molecule binds to

Ju
the keratin in the skin and hair and the colour
lasts for 2 to 6 weeks.
Lawsone exists in three tautomeric forms that are in equilibrium. The

il
1,4-naphthoquinone structure is the most stable form, followed by A and then B, which is
the least stable.
O nt
A B
lu
OH
O
tia

Lawsone

25.1. Draw the structures of lawsone tautomers A and B.

en

A short route to lawsone and other similar naphthoquinones was described by Heerding
and Moore, proceeding via 4-aryl-3-tert-butoxy-4-hydroxycyclobutenones as illustrated
below.
id

25.2. Draw the missing compounds C, D, and E in the total synthesis of lawsone.
Hint: D contains a hydroquinone motif.
nf

O 1. Li

C MeCN
D
Co

tBu O O Reflux
2. NH4Cl

O
Ag2O
E
TFA

K2CO3 OH
O
TFA O Lawsone

F3 C OH

56th IChO Preparatory Problems 115

Naphthoquinone-based 1,2,3-triazole I was shown to have potent trypanocidal and
antitumor activities. This compound can be synthesized starting from lawsone according
to the scheme below. E contains two condensed six-membered rings. The final step is the
azide–alkyne cycloaddition, which proceeds according to the scheme in the box.
O
Na2CO3 O

F
Br H2O2
OH
OH NEt3 OH
O C15H14O3 HO O

ne
NaOH/Na2CO3
CuSO4
CuSO4

Ju
Na-ascorbate O
O N
I NaN3
G
H
N N Br2

OH

il
O
O
O
J nt
lu
azide-alkyne cycloaddition CuSO4 N
Na-ascorbate N N R
R N N N + R'
R'
tia

25.3. Draw the missing compounds F–I in the total synthesis of triazole J.
en
id
nf
Co

56th IChO Preparatory Problems 116

Solution
25.1.
OH O

O O
O O
A B

ne
Ju
25.2.
OH O
O

il
Ph
tBu tBu
tBu O O O
OH

C
OH

D
nt O

E
lu
Mechanism (not required, shown for deeper understanding):
tia

O 1. Li O tBu C O
∆ O
tBu O O 2. NH4Cl tBu O
OH HO
en

C
id
nf

O OH O
Ag2O
tBu tBu tBu
Co

K2CO3
O O O
O OH OH

E D

56th IChO Preparatory Problems 117

25.3.

O O O
Br N3

OH O O
O O O

F G H I

ne
References:
Regiospecific synthesis of hydroxyquinones and related compounds from 3-tert-

Ju
butoxycyclobutene-1,2-dione, Julia M. Heerding and Harold W. Moore, The Journal of
Organic Chemistry 1991 56 (12), 4048-4050, https://doi.org/10.1021/jo00012a046
Molecular hybridization as a powerful tool towards multitarget quinoidal systems:

il
synthesis, trypanocidal and antitumor activities of naphthoquinone-based 5-iodo-1,4-
nt
disubstituted-, 1,4- and 1,5-disubstituted-1,2,3-triazoles, S. B. B. B. Bahia, W. J. Reis, G. A.
M. Jardim, F. T. Souto, C. A. de Simone, C. C. Gatto, R. F. S. Menna-Barreto, S. L. de Castro, B.
C. Cavalcanti, C. Pessoa, M. H. Araujo and E. N. da Silva Júnior, Med. Chem. Commun.,
lu
2016, 7, 1555, https://doi.org/10.1039/C6MD00216A
tia
en
id
nf
Co

56th IChO Preparatory Problems 118

26. Natural products syntheses
Part A
Vernolepin is a highly functionalized elemanolide dilactone isolated from sweet bitterleaf
(Vernonia hymenolepis) that grows in tropical Africa. Thanks to its platelet anti-
aggregating and irreversible DNA polymerase inhibiting properties, it may serve as
antitumor agent. Compound E serves as a key intermediate in the total synthesis of
vernolepin. It can be prepared in several steps, starting with a series of cycloaddition
reactions as shown below.

ne
OMe
1.

Ju
TMSO
+
∆
A +
B
CO2Me 2. H C12H14O3
C8H10O2

il
1. NaOH(aq)
C
nt
Br2
D
DBU
E
lu
2. H
+
C11H12O3 NaHCO3 C11H11BrO3 C11H10O3
tia

OH TMS DBU
O
Me N
en

O Me Si N
H
O Me
O
Vernolepin
id

26.1. Draw the structures of compounds A−E (stereochemistry is not required).

nf

Hints:
1) B contains two fused rings and two carbon–carbon double bonds.
Co

2) E contains two carbon–carbon double bonds.

Part B
(+)-Cassaine is a toxic compound which is found in the tree genus Erythrophleum. Since
ancient times, it has been used as an ordeal poison by African tribes and as an arrow
poison by the Casamance people of Senegal. It inhibits Na+, K+-ATPase, thereby changing
the force and energy of cardiac muscle contractions. One synthetic route to (+)-cassaine
is depicted below.

56th IChO Preparatory Problems 119

 O O
O
O O Cs2CO3, CsI MeO N

MeO
SnMe3 + F 18-C-6
O OTBS
C19H35ClINO3Si I
SnMe3

Pd2(dba)3, AsPh3 1. toluene, ∆

G H 1. NaBH4

(iPr)2NEt 2. H2O, ∆ 2. MOMCl, (iPr)2NEt

C26H45NO4Si

ne
O
O O O

Ju
N N
H
OTBS H
H

il
MOMO H
H
HO O
H
nt (+)-Cassaine
lu
TBS 18-C-6 dba

O O
Si
O O
tia

O O
MOMCl O
en

O Cl 18-crown-6 dibenzylideneacetone
id

26.2. Draw the structures of compounds F–H, including stereochemistry.

Hints:
nf

1) G was synthesized by a palladium-catalyzed cross-coupling reaction.

Palladium-catalyzed cross-coupling reaction
Co

(Stille coupling)
(cat.)
Pd0
R1 Sn(Alkyl)3 + 2
R X R1 R2 + X Sn(Alkyl)3
ligand

2) The first reaction from G to H is a Diels–Alder reaction.

26.3. Explain the role of 18-C-6.
26.4. Identify all chirality centers in (+)-cassaine. Label them with an asterisk and
assign R/S configuration to each of them.

56th IChO Preparatory Problems 120

Solution
26.1.
O O
CO2Me CO2H
CO2Me O O

O O Br
O O
A B C D E

ne
26.2.

Ju
O O
O O O O
Cl N N
O
MeO N H

il
I O
OTBS
Si O H
OTBS

F
ntG
O
H

H
lu
26.3.
tia

18-crown-6 functions as a ligand for cesium cations, making the naked anion more naked
(nucleophilic).
26.4.
en

O O
N
S
R
id

* H * R
S * *
* *H S
HO O
nf

H
R
Co

Reference:
Total Synthesis of (+)-Cassaine via Transannular Diels−Alder Reaction, Serge Phoenix,
Maddi Sridhar Reddy, and Pierre Deslongchamps, Journal of the American Chemical
Society 2008 130 (42), 13989-13995, https://doi.org/10.1021/ja805097s

56th IChO Preparatory Problems 121

27. Przewalskin B: Medicine for the
heart
(±)-Przewalskin is a diterpenoid found in a Chinese plant Salvia przewalskii, a member of
the Labiatae plants family. Many species of this widely distributed genus have been used
for centuries as folk medicine to treat a variety of illnesses. Przewalskin, first isolated in
2007, is used to treat cardiovascular diseases. Zhixiang Xie’s group outlined the total
synthesis shown below.

ne
CHO
O O 1. N2H4, KOH OHC OTBS
A B C

Ju
2. HCl LiHDMS

il
O O COOMe O COOMe
CH3C(OMe)3
TBAF

H
OH
nt
CH3CH2COOH

H
+

H
lu
D E F
O
O
tia

OH
NaBH4 O
DBU
G + H I
H
en

C16H22O2
Przewalskin B

TBS LiHMDS TBAF DBU

id

F
Si Si N
Si N
nf

N
Li N
Co

Compound A is made regioselectively via a Diels–Alder cycloaddition reaction. Then, A is

reduced using Wolff–Kishner reduction and deprotected using HCl. Aldol condensation
between B and protected aldehyde gave C which, after deprotection with TBAF, afforded
a bicyclic intermediate D. The next step provided an inseparable mixture of stereoisomers
E and F. The oxo group in both E and F can be reduced using NaBH 4 to yield stereoisomers
G and H, respectively. This gives a new chirality center, which has the (S) configuration in
both G and H.

56th IChO Preparatory Problems 122

27.1. Draw the structures of compounds A, B, C, G, and H (stereochemistry in A, B, and
C is not required).
27.2. What is the stereochemical relation between compounds E and F?
When the reduced functional group in in G and H is treated with the base DBU, it can form
a cyclic ester if the other group is on the same face of the ring.
27.3. Draw the structure of I. Identify which compound(s) can form a cyclic ester: G,
H, both, neither?

ne
Ju
il
nt
lu
tia
en
id
nf
Co

56th IChO Preparatory Problems 123

Solution
27.1.

O O O O
OTBS

H H H
OHC CH3

A B C

ne
Ju
OH COOMe OH COOMe

il
H H

G + H nt
lu
27.2.
They are diastereomers.
tia

27.3.
en

O
O
id

H
nf

I
Co

Cyclic ester I is formed from compound G.

Reference:
Total Synthesis of (±)-Przewalskin B, Mingxing Xiao, Lin Wei, Liqi Li, and Zhixiang Xie, The
Journal of Organic Chemistry 2014 79 (6), 2746-2750,
https://doi.org/10.1021/jo500047q

56th IChO Preparatory Problems 124

28. Polymers
Polymerization processes play a crucial role in the petrochemical and manufacturing
industries, allowing the creation of complex polymers that were previously inaccessible,
thanks to techniques like olefin metathesis.
28.1. For each polymerization reaction below, draw the draw the repeating units of the
resulting polymers. In addition, classify each polymerization as step growth,
chain growth, or living polymerization.

ne
O
a)
H 2N ∆
OH

Ju
O
Sn(OR)2
b) O

il
c) H 2N O nt NH2
lu
+
O O

O O
tia

O O
O
O
en

O
O
d)
∆
id
nf
Co

56th IChO Preparatory Problems 125

 Mes N N Mes O
1. Cl H
Mes = 3 S
C
N Ru
O
Cl Ph
N

(Grubbs catalyst)
e)
2. HO OH

H 3C CH3
excess

ne
Mes N N Mes

Ju
1. Cl
N Ru
Cl Ph
N

il
(Grubbs catalyst)
f)

Ph Ph
100 equiv.
2.
nt
lu
Me Me
100 equiv.
tia

You have a mixture of polystyrenes with three different architectures (linear, cyclic, and
graft). Suppose that, despite the different architectures, these polystyrenes have exactly
the same overall number- and weight-average molecular weights.
en

x
id

O N O
nf

nl nc
ng
Co

linear cyclic graft

28.2. What do you expect the gel-permeation chromatography (GPC) data to look like?
Draw the expected concentration signal and explain.

56th IChO Preparatory Problems 126

Solution
28.1.
O O
H H
a) N or N
H OH step growth
n n

ne
O O
b) or O
O n chain
n
growth

Ju
O O

c) N N step growth

il
O n

O
O
nt
lu
O n or n chain
d)
growth
tia

OH
en

e) Ph or living polymerization
n n
id

Ph
or
f)
10
nf
10

10
10
0
0

0
0

Ph Ph Me Me Ph Ph Me Me
Co

living polymerization

56th IChO Preparatory Problems 127

28.2.

ne
Ju
il
GPC (also called size-exclusion chromatography, SEC) separates objects based on their

nt
size (hydrodynamic radius). This trends with molecular weight, but also reflects the shape
of the molecule. For these three polystyrenes, M n and M w are identical, but the
architectures are different. We should expect the different polystyrenes to elute at
lu
different times. The cyclic polymer should have the most compact conformation in
solution, so it experiences the most pore volume and elutes latest. The linear polymer
should have a random coil conformation and elute first.
tia
en
id
nf
Co

56th IChO Preparatory Problems 128

29. Polymer functionalization
The term "click chemistry" is a collective name for organic chemical reactions that allow
the linking of two molecules with high specificity and efficiency under relatively mild
reaction conditions. One of the most characteristic examples of this reaction family is the
Cu(I)-catalyzed azide-alkyne cycloaddition. In this process, an azide group and a carbon-
carbon triple bond form a 1,2,3-triazole ring, covalently linking species carrying two
different functional groups.
B

ne
N3 + B
A N
N
A N

Ju
In the following, we utilize this reaction for the functionalization of poly(vinyl chloride)
(PVC). This is achieved by replacing some of the Cl atoms with azide groups, followed by
quantitatively introducing them into azide-alkyne cycloaddition with a slight excess of

il
added propargyl-poly(dimethylsiloxane)-monomethyl ether. The reaction sequence is
illustrated in the scheme below:
nt O
Si
O
lu
n
NaN3
P1 x y P2
- NaCl Cl N3
tia

29.1. Draw the polymer structures P1 and P2 using the notations provided in the
scheme.
The propargyl-poly(dimethylsiloxane)-monomethyl ether, the substantially higher
en

molecular weight partially azidated PVC, the cycloaddition reaction mixture at the end of
the reaction, and the purified P2 product were all examined using gel permeation
chromatography. The obtained chromatograms are presented below.
id

Mn / (g/mol) A
A 640
D
nf

B 192400
C 3950
D 70800
Co

B
C

10 15 20 25

elution volume / ml

56th IChO Preparatory Problems 129

29.2. Match the measured samples with the obtained gel permeation chromatography
curves.
29.3. Estimate the average number of poly(dimethylsiloxane) side chains per PVC
molecule in the purified P2 product.
29.4. Calculate the excess (in mol%) of propargyl-poly(dimethylsiloxane)-
monomethyl ether that was added to the azidated PVC in the functionalization
reaction.

ne
Ju
il
nt
lu
tia
en
id
nf
Co

56th IChO Preparatory Problems 130

Solution
29.1.

P1 x+y
Cl

P2 x y

ne
Cl N
N
N
O
Si O

Ju
n

29.2.

il
A: propargyl-poly(dimethylsiloxane)-monomethyl ether
B: purified P2
nt
lu
C: mixture at the end of the reaction
D: partially azidated PVC
tia

29.3.
en

n = (192400 g/mol - 70800 g/mol) / 640 g/mol = 190

id

29.4.
Let there be 1 P2 chain per x unreacted poly(dimethylsiloxane) chain
nf

Then the average molar mass:

<M> = ((1 · 192400 g/mol) + (x · 640 g/mol)) / (1 + x) = 3950 g/mol
Co

x = 56.9, so 56.9/190 = 30% was the excess of added propargyl poly(dimethylsiloxane)-

monomethyl ether.

56th IChO Preparatory Problems 131

30. Polyurethane network
We aim to create a novel polyurethane network using hexamethylene diisocyanate (HDI,
OCN-(CH 2 ) 6 -NCO), poly(ethylene glycol) (HO-(CH 2 CH 2 O) n -H, M n = 500 g/mol), and a
"homemade" polyol crosslinker. Initially, we convert the hydroxyl groups of the cross-
linking polyol into acetates using acetic anhydride. Subsequently, the obtained product,
i.e., the acetylated polyol, along with the initial polyol, undergoes gel permeation
chromatography. The results are as follows:

M n / g/mol M w / g/mol Ip

ne
Sample 1 1383 2531 1.83
Sample 2 1240 2232 1.80

Ju
For the polyurethane synthesis, we mix 1.6820 g of HDI, 4.0000 g of poly(ethylene glycol),
and a sufficient amount of cross-linking polyol to ensure an equal number of hydroxyl and

il
isocyanate groups.
30.1.
nt
Determine the average number of hydroxyl groups per molecule in the cross-
linking polyol.
lu
30.2. Calculate the mass of cross-linking polyol required for the polyurethane
synthesis?
The reaction between isocyanate and hydroxyl groups is modeled by the following
tia

equation. Moving forward, we disregard changes in volume and temperature, and assume
equal reactivity between identical groups in different chemical environments:
~~~NCO + HO~~~ → ~~~NHCOO~~~
en

You can model the time evolution of the process using a simple kinetic law with an order
of 1 for each reactant.
id

After 3 hours of the reaction, a sample was withdrawn, and the subsequent GPC result is
as follows:
nf

M n / g/mol M w / g/mol Ip
Sample 3 1227 3288 2.68
Co

30.3. Calculate the conversion after 3 hours?

Crosslinking polymers leads to gelation, a sudden increase in viscosity. A simple model
predicts that this gel point occurs when M n becomes infinitely high.
30.4. Identify the conversion corresponding to the gel point in this model.
30.5. Determine the reaction time at which the reaction reaches the gel point.

56th IChO Preparatory Problems 132

Solution
30.1.
If one hydroxyl group is converted to an acetate ester, it results in a molecular weight increase of
ΔM(ac) = 42.036 g/mol.
Therefore, on average, (1383 g/mol – 1240 g/mol) / 42.036 g/mol = 3.4 hydroxyl groups are
present in one polyol molecule.

ne
30.2.
M(HDI) = 168.196 g/mol

Ju
n(-NCO) = 0.02 mol
n(-OH, from PEG) = 0.016 mol

il
m(polyol) = (0.02 mol – 0.016 mol) / 3.4 * 1240 g/mol = 1.4588 g

30.3.
nt
lu
The number-average molecular weight at time t is calculated using the formula:
M n (t)=m total /n total,t
tia

Therefore, after 3 hours,

n total,3h =(1.6820 g + 4.0000 g+ 1.4588 g)/1227 g/mol = 0.00582 mol
en

Initially, there were

(0.02 mol/2) + (0.016 mol/2) + ((0.02 mol –0.016 mol)/3.4) = 0.01918 moles
id

Therefore, the number of molecules decreased by 0.01336 moles in 3 hours, indicating

the amount of isocyanate groups (and hydroxyl groups) reacted.
nf

The conversion is χ(3h) = 0.01336 mol/0.02 mol = 66.8%

Co

30.4.
The gel point is reached when M n →∞, implying that n total →0.
Therefore, 0.01918 mol – χ crit ×0.02 mol = 0.
Solving for the conversion at the gel point (χ crit ), we find χ crit = 95.88%.

56th IChO Preparatory Problems 133

30.5. The rate equation, since [-NCO]=[-OH]:
𝑑𝑑[-NCO]
− = 𝑘𝑘 ⋅ [-NCO] ⋅ [-OH] = 𝑘𝑘 ⋅ [-NCO]2
𝑑𝑑𝑑𝑑
The integrated form:
1 1 1
= = + 𝑘𝑘 ⋅ 𝑡𝑡
[-NCO] �1– 𝜒𝜒(3ℎ)� ⋅ [-NCO]0 [-NCO]0

From this, denoting the system volume as V: [-NCO] 0 = 0.02 mol /V:
𝑘𝑘/𝑉𝑉 = 33.5341 (1/(h mol))

ne
Time at the gel point (t(gel)):
1 1 1

Ju
𝑡𝑡(gel) = ⋅� − �=
33.5341 (1/(h mol)) (1– 0.9588) ⋅ 0.02 mol 0.02 mol
= 34.7 h = 2082 min

il
nt
lu
tia
en
id
nf
Co

56th IChO Preparatory Problems 134

Laboratory Procedures and Safety
Participants in the IChO must be prepared to work in a chemical laboratory and be aware
of all relevant rules and safety procedures. The organizers will strictly enforce the safety
rules during the event. See Appendix A and B of the IChO regulations for details.
The preparatory problems were created with students in mind who have limited
experience in the laboratory. Detailed instructions on certain procedures are provided in
the problem set for the benefit of these students. However, it's important to note that
these step-by-step instructions or detailed instructions for the procedures in the practical

ne
part of the IChO syllabus will not be part of the actual exams.
Nonetheless, all experiments demand competent supervision and appropriately equipped

Ju
laboratories. Students should, under no circumstances, attempt these experiments on
their own.
Detailed safety and disposal instructions going beyond the GHS hazard codes of the

il
chemicals used are not provided as regulations can significantly differ among countries.
Mentors should adapt the instructions with great care according to local regulations. Hints
nt
for the setup of the experiments are included in the solutions that are shared only with
the mentors in the preparation period.
lu
Students will be provided with eye protection by the organisers. These must be worn
during the laboratory exam. Contact lenses are prohibited. The goggles can be worn with
prescription glasses. The dress code in the labs requires covered legs and closed shoes.
tia

Students are welcome to bring and use their own lab coats. Organizers will also hand out
lab coats. IChO experience in similar cases shows that a good fit cannot be guaranteed a
due to sizing inconsistencies between countries.
en
id
nf
Co

56th IChO Preparatory Problems 135

31. Identification with a battery
You find on your desk:
− 1 test tube stand
− 9 numbered test tubes with unknowns
− 10 empty test tubes
− 3 small crystallization dishes
− a simple circuit: a 9 V battery with a LED light and steel wires
− universal indicator solution

ne
− 1 color scale for the indicator
− 3 filter papers
−

Ju
tissues
You can only use these in addition to calculator and pen. Wash all equipment very
carefully before reuse.

il
The following materials are in the nine numbered test tubes:

−
−
distilled water nt
boric acid (B(OH) 3 ), 0.1 mol/dm3 aqueous solution
lu
− mannitol (hexane-1,2,3,4,5,6-hexol), 0.1 mol/dm3 aqueous solution
− KNO 3 , 0.1 mol/dm3 aqueous solution
− KI, 0.1 mol/dm3 aqueous solution
tia

− H 3 PO 4 , 1 mol/dm3 aqueous solution

− KH 2 PO 4 , 0.1 mol/dm3 aqueous solution
− K 2 HPO 4 , 0.1 mol/dm3 aqueous solution
en

− Na 3 PO 4 , 0.1 mol/dm3 aqueous solution

Answer the following questions and identify the content of the test tubes.
id

The conductivity of solutions arises from the movement of ions in an electric field. As ion
concentrations increase, conductivity also increases. In aqueous solutions, oxonium and
hydroxide ions exhibit the highest conductivity.
nf

Boric acid is a weak acid, and surprisingly only B(OH) 4 – ions can be found in its aqueous
solution besides the ions of water.
Co

31.1. Give a balanced ionic equation of the reaction between boric acid and water.
Draw the structure of the product anion.
In a 0.1 mol/dm3 aqueous boric acid solution, the concentration of B(OH) 4 – ions was
measured. The results indicate that the quantity of B(OH) 4 – ions in the solution is
equivalent to 0.0085% of the dissolved boric acid.
31.2. Calculate the pH of 0.1 mol/dm3 boric acid.

56th IChO Preparatory Problems 136

The addition of mannitol to boric acid solution results in the formation of a monovalent
complex acid, which exhibits a strength similar to acetic acid.

31.3. Calculate the pH of 0.1 mol/dm3 acetic acid. K a = 1.8 · 10–5.

31.4. Provide the anode and cathode reactions occurring during the electrolysis of KI

ne
solution and phosphoric acid solution between steel electrodes.
31.5. Identify the positive wire (red or black) without disassembling the equipment.

Ju
Which experiment and observation helped you to decide?
31.6. Carry out experiments and assign the test tube number to the solutions. Give the
observation(s) that helped you to identify the solutions.

il
GHS codes nt
Please note that the table of Globally Harmonized System (GHS) hazard codes provided
lu
for the chemicals used in these experiments is intended as a reference only. There is no
guarantee that the information provided is perfect or complete. The list does not replace
the need for professional attention to local regulations and the safety information
tia

provided by the actual suppliers of the chemicals.

Chemical GHS Hazard code
en

H 3 BO 3 aqueous solution H360FD

mannitol aqueous solution No hazard
KNO 3 aqueous solution H272
KI aqueous solution H372
id

H 3 PO 4 , aqueous solution H314

KH 2 PO 4 aqueous solution No hazard
nf

K 2 HPO 4 aqueous solution No hazard

Na 3 PO 4 aqueous solution H315, H319
Co

56th IChO Preparatory Problems 137

Solution
31.1.
B(OH) 3 + 2 H 2 O = B(OH) 4 – + H 3 O+
B(OH) 4 – is tetrahedral.

31.2.
[H+] = 0.0085·0.01·0.1 mol/dm3 = 8.5·10–6 mol/dm3

ne
pH = 5.1

Ju
31.3.
[H+]2 = 1.8·10–5·0.1 (mol/dm3)2

il
pH = 2.9

31.4. nt
lu
Cathode Anode

H 3 PO 4 2 H + + 2 e– = H 2 H 2 O = ½ O 2 + 2 H + + 2 e–
tia

KI H 2 O + 2 e– = H 2 + 2 OH– 3 I– = I 3 – + 2 e–

31.5.
en

When electrolyzing the KI solution, a brown discoloration is observed at the positive

electrode.
id

31.6.
nf

Test tube Observation(s) necessary for unambiguous identification

pH ≈ 6-7, does not conduct

Co

Water
added to boric acid, the pH does not change

pH ≈ 5
Boric acid shows weak conductivity, faint light
mixed with mannitol turns more acidic

pH ≈ 6-7
Mannitol does not conduct
mixed with boric acid, it makes it turn more acidic

56th IChO Preparatory Problems 138

 pH ≈ 6-7
KNO 3 conducts
no browning at anode

pH ≈ 6-7
KI conducts
browning at anode

H 3 PO 4 pH ≈ 2-3

ne
pH ≈ 4-5
KH 2 PO 4 conducts

Ju
no change in pH with mannitol

il
K 2 HPO 4 pH ≈ 9-10

Na 3 PO 4 pH ≈ 12-13
nt
lu
Hints for the preparations:
tia

When preparing the experiment, mannitol can be substituted with any available sugar
alcohol or appropriate polyol.
en

The photo below shows a simple setup for the circuit without the cover around the battery
that hides the battery polarity. The components in this setup are a diffused 5mm red LED
and a 10 kOhm resistor.
id
nf
Co

56th IChO Preparatory Problems 139

32. Direction of redox processes
Redox reactions can always be broken down into two half reactions: oxidation and
reduction. E.g. for the reaction
Cu2+ + Zn = Cu + Zn2+
the two half reactions are:
Cu2+ + 2 e– = Cu and Zn = Zn2+ + 2 e–

ne
Each half reaction can be assigned a standard electrode potential value. By comparing
these values, it is possible to predict the likely redox processes. The fundamental rule is
that the oxidized form of the system with a higher standard potential oxidizes the reduced

Ju
form of the system with a lower potential.
Cu2+ + 2 e– = Cu E° = +0.34 V
Zn2+ + 2 e– = Zn E° = –0.76 V

il
(By convention, half reactions are written in the direction of reduction.)
Here, then, Cu2+ can oxidize Zn.
nt
lu
It is crucial to note that the standard potential is associated with standard conditions
aligned with the balanced equation of the half reaction, and therefore, it corresponds to
the unit concentration of each indicated substance. The electrode potential is influenced
tia

by the concentration of other species, including hydrogen ions. For example, reduction of
the dichromate ion to the chromium(III) ion:

Cr2 O2– + – 3+
7 + 14 H + 6 e = 2 Cr + 7 H2 O E° = 1.33 V
en

In this case, the concentration of hydrogen ions also affects the electrode potential. The
standard electrode potential given above is valid for [H+] = 1 mol/dm3, i.e., for strongly
id

acidic media. If the hydrogen ion concentration is lower, then the electrode potential will
also be smaller.
nf

What does that mean? Let's see an example.

The standard electrode potential of the Br 2 + 2 e– = 2 Br– half reaction E° = +1.09 V.
Co

Does dichromate oxidize bromide? Based on standard electrode potentials, yes. This
prediction works well in strongly acidic conditions, where the standard electrode
potential is around 1.33 V. However, if the pH increases, the potential for the
dichromate/chromium(III) reaction decreases. Generally, reducing the concentration of
species on the left side of the reduction equation leads to a decrease in the electrode
potential.
Indeed, the following reaction takes place in a strongly acidic medium, but not at a pH
close to neutral:

Cr2 O2– + – 3+
7 + 14 H + 6 Br = 2 Cr + 7 H2 O + 3 Br2

56th IChO Preparatory Problems 140

To put it simply, we could say that for the reaction to take place as the equation shows, an
acidic medium is needed.
When solving this task, you will need to apply these principles.

Part A What do potentials say about reactions?

You find on your desk some aqueous reagent solutions in test tubes. Predict what reaction
you expect to occur for each of the two half reactions specified in tasks 1 and 3. Then show
experimentally that you have drawn the right conclusion. Carefully describe what and

ne
how you did the reaction and what your observations were.
The available reagents are the following substances in aqueous solution: bromine water,
potassium bromate, potassium bromide, potassium chloride, chlorine water, hydrochloric

Ju
acid, tin(II) chloride, tin(IV) chloride.
The standard electrode potentials (E°):

il
BrO–3 + 6 H+ + 5 e– = ½ Br2 + 3 H2 O +1,52 V
Cl2 + 2 e– = 2 Cl– +1,36 V
Br2 + 2 e– = 2 Br–
Sn4+ + 2 e– = Sn2+
nt
+1,07 V
+0,15 V
lu
32.1. Identify the reactants that you think will undergo a redox reaction for the
bromine/bromide and tin(IV)/tin(II) couples. Perform the reaction and provide
tia

details of your experiment along with your observations.

32.2. Write down the balanced equation of the reaction taking place.
en

32.3. Identify the reactants that you think will undergo a redox reaction for the
chlorine/chloride and bromate/bromine couples. If allowed (some chemicals are
classified in many jurisdictions as forbidden for students), perform the reaction
id

and provide details of your experiment along with your observations.

32.4. Write down the balanced equation of the reaction taking place.
nf
Co

Part B What do reactions say about potentials?

You will study the following half reactions and find the order of their standard electrode
potentials.
32.5. Balance the half reactions. Fill in the table with the expected observations.

Is there a visible change when

No Half reaction
reduction takes place? If yes, what?

1 IO 3 − + e− = I2

56th IChO Preparatory Problems 141

 2 I2 + e− = I−

3 Co2+ + e− = Co(s)

4 Cl 2 + e− = Cl−

5 Fe3+ + e− = Fe2+

6 C6H6O6 + e− = C6H8O6

ne
7 MnO 4 − + e− = Mn2+

The C 6 H 8 O 6 in the table denotes ascorbic acid, and C 6 H 6 O 6 dehydroascorbic acid.

Ju
In test tubes you will find the following solutions.

il
32.6. Fill the second column.

No
ntAre these oxidized or reduced forms of the
above pairs?
lu
1 acidified KIO 3 solution
tia

2 KI solution

3 CoSO 4 solution
en

4 acidified MnSO 4 solution

5 acidified ascorbic acid solution

id

6 chlorine water
nf

7 FeCl 3 solution
Co

Conduct experiments on the seven provided solutions to establish the order of redox pairs
(1-7) based on their standard electrode potential. All anticipated reactions, based on
standard potentials, indeed occur in these systems without any significantly slow
reactions. You do not need to consider the possibility of other redox processes when
solving the task.
32.7. Report your work using the template below. Indicate which solutions you have
mixed (with formulae) and report your observations (even if there was no visible
change). Be sure to indicate for each experiment the relation between standard
potentials that it proves.

56th IChO Preparatory Problems 142

 Solutions mixed: Observation:

Did a reaction (Reaction) The relation of

take place? potentials this
experiment
+/-
proves:
>

ne
32.8. Put the numbered redox pairs (1-7) in increasing order according to their
standard potential.

Ju
Equipment and material list
test tube stand

il
test tubes with a dropper containing the following solutions:
nt
bromine water, 0.25 mol/dm3 KBrO 3 , 0.1 mol/dm3 KBr, 0.1 mol/dm3 KCl, chlorine water,
0.1 mol/dm3 HCl, 0.25 mol/dm3 SnCl 2 (with HCl added to stop hydrolysis), 0.25 mol/dm3
lu
SnCl 4 (with HCl added to stop hydrolysis), 1:1 mixture of 0.25 mol/dm3 KIO 3 and 0.1
mol/dm3 HCl, 0.1 mol/dm3 KI, 0.5 mol/dm3 CoSO 4 , 1:1 mixture of 0.25 mol/dm3 MnSO 4 and
0.1 mol/dm3 HCl, 1:1 mixture of 0.1 mol/dm3 ascorbic acid and 0.1 mol/dm3 HCl, chlorine
tia

water, 0.5 mol/dm3 FeCl 3 (with HCl added to stop hydrolysis)

15 empty test tubes
en

GHS codes
id

Please note that the table of Globally Harmonized System (GHS) hazard codes provided
for the chemicals used in these experiments is intended as a reference only. There is no
guarantee that the information provided is perfect or complete. The list does not replace
nf

the need for professional attention to local regulations and the safety information
provided by the actual suppliers of the chemicals.
Co

Chemical GHS Hazard code

bromine water H302, H314, H400, H410
0.25 mol/dm3 KBrO 3 H272, H302, H315, H319, H335, H350,
H410
0.1 mol/dm3 KBr No hazard
0.1 mol/dm3 KCl No hazard
chlorine water H290, H314, H400
0.1 mol/dm3 HCl H290, H314, H335
0.25 mol/dm3 SnCl 2 H290, H302, H314, H317, H335, H373,
H412

56th IChO Preparatory Problems 143

0.25 mol/dm3 SnCl 4 H314, H412
1:1 mixture of 0.25 mol/dm3 KIO 3 and H272, H302, H319
0.1 mol/dm3 HCl
0.1 mol/dm3 KI H372
0.5 mol/dm3 CoSO 4 H302, H317, H334, H341, H350i, H360F,
H372, H400
1:1 mixture of 0.25 mol/dm3 MnSO 4 and H373, H411
0.1 mol/dm3 HCl
1:1 mixture of 0.1 mol/dm3 ascorbic acid No hazard
and 0.1 mol/dm3 HCl
chlorine water H302, H315, H319, H331, H335, H400

ne
0.5 mol/dm3 FeCl 3 H290, H302, H314

Ju
il
nt
lu
tia
en
id
nf
Co

56th IChO Preparatory Problems 144

Solution
32.1.
Elemental bromine oxidizes tin(II) according to the standard potentials.
When dropping bromine water into Sn(II) chloride solution, the color disappears.

32.2.

ne
Br 2 + Sn2+ = 2 Br− + Sn4+

Ju
32.3.
Bromate can oxidize chloride in acidic media (has a higher standard potential).

il
nt
When potassium bromate is added to hydrochloric acid, the solution slowly turns yellow.
Instead of hydrochloric acid, other chloride-containing solutions (KCl, SnCl 4 ) do the same
if acidified, but in the case of SnCl 2 , tin(II) is oxidized, not chloride.
lu
32.4.
tia

2 BrO 3 − + 10 Cl− + 12 H+ = Br 2 + 5 Cl 2 + 6 H 2 O
en

32.5.

Is there a visible change when

id

No Half reaction
reduction takes place? If yes, what?
Turns yellow or brown, or even a
nf

1 IO 3 − + 5 e− + 6 H+ = 0,5 I 2 + 3 H 2 O solid (iodine) can precipitate (any of

these is an acceptable answer)
Co

2 I 2 + 2 e− = 2 I− Loses color.

A solid forms or the solution loses

3 Co2+ + 2 e− = Co(sz)
color (either is acceptable)
Loses color, loses smell, or no
4 Cl 2 + 2 e− = 2 Cl− apparent change (either of the three is
acceptable)

5 Fe3+ + e− = Fe2+ Turns very faint green from yellow

56th IChO Preparatory Problems 145

 6 C 6 H 6 O 6 + 2 e− + 2 H + = C 6 H 8 O 6 nothing

7 MnO 4 − + 5 e− + 8 H+ = Mn2++ 4 H 2 O Loses color.

32.6.

Are these oxidized or reduced forms of the above pairs?

acidified KIO 3 solution oxidized

ne
KI solution reduced

Ju
CoSO 4 solution oxidized

acidified MnSO 4 solution reduced

il
acidified ascorbic acid
reduced
solution
chlorine water oxidized
nt
lu
FeCl 3 solution oxidized
tia

32.7.
There could be other ways to find the right order. It needs to be checked whether all
en

relations are established. Experiments that have no observable change are necessary for
a complete solution.
Solutions mixed: Observation:
id

Cl 2 + MnSO 4 NO purple color

nf

Did a reaction (Reaction) The relation of

take place? potentials this
experiment
Co

-
proves:
7>4
Solutions mixed: Observation:
Cl 2 + I 2 or excess Cl 2 + KI The color of (produced) iodine disappears
(with an excess of chlorine)

56th IChO Preparatory Problems 146

Did a reaction (Reaction) The relation of
take place? potentials this
5 Cl 2 + 2 I 2 + 6 H 2 O = 2 IO 3 – + 10 Cl– + 12 H+
experiment
+
proves:
4>1
Solutions mixed: Observation:
FeCl 3 + I 2 or FeCl 3 excess + KI The color of (produced) iodine does not
disappear (with an excess of reagent)

ne
Did a reaction (Reaction) The relation of
take place? potentials this
experiment
-

Ju
proves:
1>5

il
Solutions mixed: Observation:
FeCl 3 + KI Iodine is produced (and no further reaction)
Did a reaction (Reaction)
take place?
nt The relation of
potentials this
lu
2 Fe3+ + 2 I– = I 2 + 2 Fe2+
experiment
+
proves:
tia

5>2
Solutions mixed: Observation:
en

IO 3 – + C 6 H 8 O 6 in excess or I 2 + C 6 H 8 O 6 The color of (produced) iodine disappears

(with an excess of reagent)
Did a reaction (Reaction) The relation of
id

take place? potentials this

I 2 + 2 C 6 H 8 O 6 = 2 I– + C 6 H 6 O 6 + 2 H+
experiment
+
nf

proves:
2>6
Co

Solutions mixed: Observation:

CoSO 4 + C 6 H 8 O 6 NO change
Did a reaction (Reaction) The relation of
take place? potentials this
experiment
-
proves:
6>3

56th IChO Preparatory Problems 147

32.8.
3 < 6 < 2 < 5 < 1 < 4 < 7

Hints for the preparations:

Bromate is classified in many jurisdictions as forbidden for students, while other
countries use bromates rather freely. Based on your location, 32.3 should be a practical
or theoretical question.

ne
Ju
il
nt
lu
tia
en
id
nf
Co

56th IChO Preparatory Problems 148

33. Oxalic acid content of turmeric
Turmeric is a characteristic spice used in Arabic cuisine in large amounts. Recent research
indicates that care must be exercised with the overuse of spices, because some of them
might naturally contain toxic compounds in addition to beneficial components. Turmeric,
for instance, contains large amounts of oxalic acid. Oxalic acid is excreted by urine and
may combine with Ca2+-ions to form a Ca-oxalate precipitate, that in serious cases can
block the kidneys. You will determine oxalic acid in turmeric in this experiment.
Oxalic acid is determined by permanganate using the following reaction (the equation is

ne
not balanced):
HOOC–COOH + H+ + MnO 4 – ⟶ CO 2 + H 2 O + Mn2+

Ju
The reaction between oxalate ions and permanganate ions is slow at the beginning, but
Mn2+ ions have a catalytic effect. The titration is thus made in hot solution and Mn2+ is
added at the beginning. Turmeric of course contains several other compounds that may

il
react with permanganate, so a separation needs to be done before titration to selectively
dissolve oxalic acid from turmeric.
nt
In the first step of the separation, we mix turmeric with water to dissolve the highly water-
soluble oxalic acid. Many other components are not soluble (fats, oils, aromatic
lu
compounds, etc.). The solid parts are removed by filtration. The filtrate contains oxalic
acid together with other compounds. In the next step, we selectively precipitate oxalic
acid with CaCl 2 solution. The majority of the interfering compounds will remain in
tia

solution. We separate the calcium oxalate by filtration. Finally, we dissolve the precipitate
in 20% H 2 SO 4 and titrate it with permanganate.
For the filtrations, we will use a small
en

plastic funnel placed directly into an

Erlenmeyer flask. The solution is collected
into the flask. We put a filter paper cone
id

we made of a square sheet of filter paper

into the funnel. For this, we fold the paper
nf

into halves twice, and cut it in a quarter-

circle line with scissors. Finally, we open
the paper to get a closed cone.
Co

Pour the mixture into the funnel. Wash all

the solid material onto the filter. To
remove all soluble compounds, wash the solids with the recommended amount of solvent.

Sample preparation steps

1. Weigh 1-1.5 g of turmeric into an Erlenmeyer flask with the precision of 0.001 g.
2. Pour 10 cm3 of distilled water over the turmeric. Mix it with occasional swirling. Let it
stand for at least 15 minutes.

56th IChO Preparatory Problems 149

3. Transfer the mixture onto a filter that is placed over a clean Erlenmeyer flask.
4. After about 3 minutes add 5 cm3 of water to the original Erlenmeyer flask and wash any
remaining solids onto the filter. This will also be washing the solids that were already on
the filter.
5. Repeat this washing after an additional 3 minutes with a fresh 5-cm3 aliquot of water.
6. Wait until no more water drips down from the filter. You can speed up the process by
folding and slightly pressing the filter paper with your gloved fingers. Be careful not to
tear the filter paper. Try to gain as much solution from the solids as possible.

ne
7. Dispose of the filter paper and remove the funnel.
8. Add 1 cm3 of 1 mol/dm3 CaCl 2 solution to the liquid. After a few seconds clearly visible
crystals of Ca-oxalate are formed. Wait an additional minute to let the crystals grow for

Ju
easier filtration.
9. Make a second filter paper cone. In this step we will use the crystals on the filter paper,
so we can use the first "dirty" flask to collect the "mother liquor" (the liquid phase).

il
10. Pour the liquid with the precipitate onto the filter.
nt
11. As in step 4, wash the precipitate two times with 5 cm3 of water. Use washing water
to transfer all the crystals onto the filter.
lu
12. Once there is no more liquid remaining on the filter, put the funnel in a clean
Erlenmeyer flask that will be used for the titration.
tia

13. We will use 20% sulfuric acid to dissolve Ca-oxalate. Use a disposable plastic dropper
for this. Use the graduation on the dropper to measure the volume. Use three times 3 cm3
of sulfuric acid. The next portion should be added only after the previous portion has
en

already run down. Use your dropper to mix the liquid in the funnel to achieve fast and
complete dissolution. Be cautious not to puncture the filter paper. Sulfuric acid is
corrosive!
id

14. When finished with the filtration, use your tweezers and a beaker to transfer the filter
paper to the waste basket. Sulfuric acid drops on your clothes result in unavoidable
nf

holes!

Titration
Co

In this task we will use weight measurement instead of burettes. Pour the permanganate
solution into a beaker and put a plastic dropper into it. Weigh the mass of the beaker (with
the solution and the dropper) with 0.001 g precision. You will use the dropper to titrate
the sample solution. Be cautious not to pour out or waste drops of your permanganate
solution. During the titration always mix the contents of the Erlenmeyer flask well. The
permanganate ions have a very strong color that will indicate the endpoint of the titration:
at the equivalence point the solution is faint pink (the color should be constant for at
least 10 seconds).

56th IChO Preparatory Problems 150

When equivalence is reached, the beaker, dropper and the remaining permanganate
solution are weighed again. The difference in masses gives the consumed mass.
The composition of the KMnO 4 solution is cca 0.32 wt. %; the exact value is on the flask.
Before starting the titration add 1 cm3 of 1 mol/dm3 MnSO 4 solution to catalyze the
oxidation process and heat the contents of the flask (e.g., with a heat gun) to approx. 50 °C.
Plan your work! Perform as many titrations as you feel necessary. We suggest preparing
several samples at the same time as the sample preparation is a long process.
33.1. Report your results in the table.

ne
Beaker + dropper + permanganate solution
Mass of turmeric
(g) mass before titration mass after titration
(g) (g)

Ju
il
nt
lu
Report your accepted result: ……………………………….. g titrant / 1 g turmeric
tia

33.2. Calculate the oxalic acid content in turmeric in mass percent.

33.3. Consider your findings. Is a high spice intake of 10 g per portion potentially risky
en

for kidney health? The recommended daily oxalic acid consumption is under 50
mg.
Usually in permanganometric titrations sulfuric acid is added to the sample just before
id

titration.
33.4. Why not in this procedure?
nf

Imperfect washing of the calcium oxalate can cause errors if chloride ions remain in the
sample.
Co

33.5. Give the balanced equation of the reaction responsible for the error. Will this
error cause higher or lower oxalic acid content?
Cinnamon, like turmeric, has a high oxalic acid content, but due to the high calcium
content of this spice, a significant part of oxalic acid occurs in the form of calcium oxalate.
33.6. Select the necessary modification of the procedure to measure the total oxalic
acid content of cinnamon?
 No changes to the procedure are required.
 In the first dissolution step, 20% sulfuric acid should be used, the rest is unchanged.

56th IChO Preparatory Problems 151

  In the first dissolution step, 2 mol/dm3 hydrochloric acid should be used, the rest
is unchanged.
 In the first dissolution step, 2 mol/dm3 NaOH solution is used, the rest is
unchanged.
 In the first dissolution step, 20% sulfuric acid is used. The sample is neutralized
before adding 1 cm3 of CaCl 2 solution.
 In the first dissolution step, 2 mol/dm3 hydrochloric acid is used. The sample is
neutralized before adding 1 cm3 of CaCl 2 solution.

ne
Lactic acid (CH 3 -CHOH-COOH), a harmless alternative, can be used to dissolve calcium
oxalate instead of the corrosive sulfuric acid solution.
33.7. Can we replace sulfuric acid with lactic acid in this procedure? Give reasons for

Ju
your answer.
A key part of this measurement is the separation of oxalic acid from the thousands of other
compounds in turmeric. The number of components is decreased by dissolving only

il
water-soluble compounds from turmeric, filtering only compounds giving precipitates
nt
with calcium ions, dissolving only calcium compounds soluble in sulfuric acid, and then
measuring compounds reacting with permanganate.
lu
33.8. Will the following compounds from turmeric be present during the titration? Will
they influence the results? Complete the table with your answers.
Is it
tia

Does it
present
Component influence Explanation if no influence
during the
results?
titration?
en

The Ca salt of alanine dissolves in

alanine   water.

 
id

sulfate ion

glycerol tristearate (“fat”)  

nf

glycerol  
stearic acid (saturated)*  
Co

oleic acid*
(monounsaturated)*
 

curcumin**  
* The water solubility of fatty acids varies between 0.3 and 0.6 g/dm3.
** Curcumin is the yellow dye found in turmeric used as a natural food coloring. Even at a concentration of
0.1 μg/cm3 it shows an intense yellow color.

56th IChO Preparatory Problems 152

Equipment and material list
All solutions and the water used must be thermally equilibrated with the room, so they have to be
prepared and diluted in advance.
On each desk:
2 g turmeric
filter paper
100 cm3 of cca. 0.32 wt. % KMnO 4 solution, exact composition on the flask
10 cm3 of 1 mol/dm3 CaCl 2 solution
50 cm3 of 20% sulfuric acid solution
6 Erlenmeyer flasks (100 cm3)

ne
3 plastic funnels
distilled water
2 graduated plastic Pasteur pipettes (1 cm3)

Ju
5 graduated plastic Pasteur pipettes (3 cm3)
2 beakers (100 cm3)
25 cm3 volumetric cylinder

il
Tweezers
goggles
paper tissue
Shared:
nt
lu
mg accuracy balances (1 for 5 students)
scissors
filter paper
tia

gloves

GHS codes
en

Please note that the table of Globally Harmonized System (GHS) hazard codes provided
for the chemicals used in these experiments is intended as a reference only. There is no
guarantee that the information provided is perfect or complete. The list does not replace
id

the need for professional attention to local regulations and the safety information
provided by the actual suppliers of the chemicals.
nf

Chemical GHS Hazard code

KMnO 4 solution H272, H302, H400
Co

1 mol/dm3 CaCl 2 solution No hazard

20% H 2 SO 4 H290, H314, H315, H318, H319

56th IChO Preparatory Problems 153

Solution
33.1.
Let the obtained consumption be m g permanganate solution for 1 g turmeric.

33.2.
In m g permanganate solution, we get 0.3161·10–2·m g KMnO 4 .

ne
n(permanganate) : n(oxalic acid) = 2:5
1 g turmeric contains:

Ju
0.3161 ⋅ 10−2 ⋅ 𝑚𝑚 5
⋅ ⋅ 𝑀𝑀[(COOH)2 ]
𝑀𝑀(KMnO4 ) 2

il
oxalic acid.

nt
The oxalic acid content of turmeric is 0.450m wt. % oxalic acid.
lu
33.3.
Typical results in our samples were 1.3 wt. % oxalic acid. For 10 g of turmeric that is
tia

130 mg of oxalic acid, way above the recommended amount.

33.4.
en

The calcium oxalate was already dissolved in sulfuric acid.

id

33.5.
nf

10 Cl– + 2 MnO 4 – + 16 H+ = 5 Cl 2 + 2 Mn2+ + 8 H 2 O

This error would result in oxalic acid content being higher than the real value.
Co

33.6.
In the first dissolution step, 2 mol/dm3 hydrochloric acid is used. The sample is
neutralized before adding 1 cm3 of CaCl 2 solution.

33.7.
No, because permanganate would also oxidize excess lactic acid.

56th IChO Preparatory Problems 154

33.8.
Is it
Does it
present
Component influence Explanation if no influence
during the
results?
titration?

The Ca salt of alanine dissolves in

alanine   water.

sulfate ion   Permanganate does not oxidize it.

glycerol tristearate („fat”)   Insoluble in water.

ne
glycerol   Does not precipitate with Ca2+.

 

Ju
stearic acid Permanganate does not oxidize it.

oleic acid  
 

il
curcumin Poorly soluble in water as observed.

Hints for the preparation:

nt
lu
The permanganate solution can be the often used 0.02 M solution.
The graduated plastic Pasteur pipettes are quite useful and reasonably accurate tools, but
students might not notice the graduations and their marks.
tia
en
id
nf
Co

56th IChO Preparatory Problems 155

34. Titration with a pH meter
In chemistry competitions, we are familiar with using the color change of dye indicators
to determine the endpoint during acid-base titrations. Nowadays, digital pH meters have
become more affordable, and simple handheld devices are readily available in
supermarkets and often cheaper than a roll of indicator paper. In this experiment, we
explore how acid-base reactions can be monitored using a pH meter.
These simple devices are similar, but their operation and shape can be variable. All have
a fragile measuring sensor, a glass electrode at the bottom. This goes into the solution

ne
studied.
Use the manual or description of the device you have. These manuals will write about the

Ju
operation of the pH meters, buttons, immersion levels, cleaning of the sensor, and the
protection of the device. Your instructors should have calibrated the device before the
experiment to make sure you get accurate results.

il
Affix the pH meter to a stand enabling easy, continuous readout of a 150 cm3 volume of
solution.
Using a micropipette
nt
lu
To deliver solutions, you will employ a micropipette instead of pipettes and burettes. This
device enables the precise and rapid measurement of small volumes (0.200-1.000 cm3).
Instructions for using the micropipette:
tia

1. Attachment of pipette tip: The liquid is not drawn directly into the pipette but
into a single-use plastic pipette tip fitted at the end of the apparatus (1 in the
en

figure). The liquid should only touch the pipette tip. Ensure a tight, well-closing
contact to prevent dripping (I). Use a pipette tip for measuring only one type of
solution.
id

2. Volume adjustment: Adjust the volume to be measured by turning the push knob
(2). The current value can be read on the display (3) on the side of the pipette in
nf

microliters (e.g., 750 means 0.75 cm3).

3. Air displacement: Depress the piston (II) until the first impact (A) to displace air
Co

from the pipette.

4. Drawing the solution: Immerse the tip in the liquid (III) and slowly release the
knob to draw up the set volume into the pipette tip. Draw the solution slowly
(about 1-2 seconds) to prevent splattering. Ensure that the tip is below the level of
the solution throughout the withdrawal. The solution should never touch the
pipette body (IV).

56th IChO Preparatory Problems 156

 5. Dispensing the liquid: Introduce the liquid into the target vessel by pressing
down on the plunger (V). If the piston is pushed further until the final impact (B)
after the first impact, the entire amount of liquid is removed from the tip. Ensure
that the tip does not touch the solution in the beaker during emptying to avoid
contamination. Hold the tip above the solution during emptying, spraying the
liquid forcefully into the beaker to mix quickly.
6. Changing solutions: If you switch to a new solution during pipetting, replace the
tip with a clean one. Use a separate button to detach the tip from the pipette (4,
VI). For feeding the same solution again, you can reuse the same tip. Be cautious
not to accidentally draw solution inside the pipette. If this happens, seek

ne
assistance.

Ju
il
nt
lu
tia
en
id
nf
Co

Measurement of hydrochloric acid and acetic acid solutions

Use the micropipette to measure 1.000 cm3 of hydrochloric acid into the 250 cm3 beaker.
Add distilled water to the beaker until it reaches the 150 cm3 mark. Place a glass rod in
the beaker, stir, and position the pH meter in the stand to the appropriate height.
Add 3 drops of phenolphthalein indicator to the contents of the beaker and turn on the pH
meter.

56th IChO Preparatory Problems 157

Add 0.3 cm3 portions of 0.500 mol/dm3 NaOH solution to the contents of the beaker until
the pH reaches 11. It is essential to mix the contents of the beaker with the glass rod after
each addition. Read the pH when the value no longer significantly changes on the display.
The final stabilization of the last digit by 1-2 units practically does not affect the results,
so do not wait for the value to stabilize for more than a few seconds.
After each addition, record the volume and the measured pH value in a table on a separate
sheet. Observe and note the color changes of the indicator. Once finished with the
measurements, wash the beaker with distilled water, rinse the pH meter and the glass rod,
then repeat the measurements with 1.000 cm3 of acetic acid solution.

ne
Graph the results of the two measurements (measured pH vs. added volume of NaOH
solution) on the same chart (use graph paper) and mark the indicator's color change
range. Identify and mark the equivalence point on the plotted graphs, and read the

Ju
corresponding volume, which may not precisely align with any of the added volumes).
34.1. Calculate the concentration of the two solutions.
34.2. Hydrochloric acid is a strong, acetic acid is a weak acid. How does this manifest

il
on the diagrams? What indicates that the strengths of the two acids are different?
34.3. nt
Estimate the pK a of acetic acid using the diagram.
Measurement of a mixture containing a strong and a weak acid
lu
In the second part of the task, you will determine the composition of a mixture consisting
of hydrochloric acid and para-nitrophenol (PNP). Pipette 1.000 cm3 of the unknown
tia

solution into the beaker. Add distilled water until the liquid level reaches the 150 cm3
mark. Add 3 drops of phenolphthalein indicator to the solution. Examine the solution by
incrementally adding 0.3 cm3 portions of 0.5000 mol/dm3 NaOH solution, recording the
pH until it reaches 11.
en

After each addition, record the volume and the measured pH value in a table on a separate
sheet. Graph the results of the measurements on a chart (use graph paper). Record the
id

volumes corresponding to the equivalence points.

34.4. Which step ('pH jump') corresponds to para-nitrophenol?
nf

 The first.
 The second.
Co

 Both.
 It is impossible to decide.
34.5. Calculate the HCl and PNP concentrations in the sample.
34.6. PNP is a weak acid. How does this manifest on the diagram?
The shade of the solution in alkaline medium is different compared to previous
measurements.
34.7. Explain this change? Hint: Conduct an experiment in a small beaker without using
indicators and pH measurement.

56th IChO Preparatory Problems 158

34.8. If solely relying on the indicator, which concentration could have been precisely
determined?
 None.
 Only the concentration of HCl.
 Only the concentration of PNP.
 Only the sum of the two concentrations.
 Both concentrations.
When measuring acid mixtures, a mixture of two indicators is often used.
34.9. Identify which indicator pair from the table below could substitute for a pH meter

ne
in the conventional titration of HCl-PNP mixtures. If not, provide the reason.
Indicator 1. Indicator 2. Verdict, explanation

Ju
Methyl orange Curcumin
(red−yellow, (yellow−burgundy,
3.1-4.1) 7.8-9.2)

il
Methyl red
(red−yellow,
4.4-6.2)
nt
Phenolphthalein
(colorless−pink,
8.3-9.8)
lu
Bromophenol blue Thymolphthalein
tia

(yellow−blue, (colorless−blue,
3.5-4.6) 9.3-10.5)
en

Congo red 4-nitrophenol

(blue−red, (colorless−yellow,
3.0-5.2) 5.4-7.5)
id

List of equipment and materials

nf

On each desk:
Co

150 cm3 approx. 0,5 mol/dm3 standard sodium hydroxide solution (with exact
concentration)
10 cm3 HCl solution, labelled HCl
10 cm3 CH 3 COOH solution, labelled acetic acid
10 cm3 HCl+ para-nitrophenol solution, label: unknown
pH meter with stand and holder
micropipette with 6 pipette tips
beaker 250 cm3
2 beakers of 100 cm3
2 glass rods

56th IChO Preparatory Problems 159

distilled water
goggles
plastic Pasteur pipette
paper towels
graph paper
Shared:
phenolphthalein indicator solution with dropper
gloves

ne
GHS codes
Please note that the table of Globally Harmonized System (GHS) hazard codes provided

Ju
for the chemicals used in these experiments is intended as a reference only. There is no
guarantee that the information provided is perfect or complete. The list does not replace
the need for professional attention to local regulations and the safety information

il
provided by the actual suppliers of the chemicals.

Chemical
nt GHS Hazard code
lu
0.5 mol/dm3 NaOH H290, H314, H315
HCl solution H290, H314, H335
Acetic acid solution H315, H319
para-nitrophenol solution
tia

H302, H312, H332, H373

phenolphthalein indicator solution H315, H341, H350, H361f
isopropanol H225, H336, H319
en
id
nf
Co

56th IChO Preparatory Problems 160

Solution
34.1.
The concentrations are 0.5V mol/dm3 if the volume consumed is V cm3.

34.2.
In the case of a weak acid, at approximately the same concentration, the initial pH is

ne
higher, and it rises more rapidly at the beginning of titration. The pH change near the
equivalence point is smaller and more prolonged. The equivalence point falls into the
basic range.

Ju
34.3.

il
If the solution is not very dilute, then at 50 % titration K a = [H+].
K a = 10–pH, pK a = pH (50%). nt
lu
34.4.
The second step.
tia

34.5.
en

If the volumes for the equivalence points are V 1 cm3 and V 2 cm3 then the HCl
concentration is 0.5V 1 mol/dm3 and the PNP concentration is 0.5(V 2 – V 1 ) mol/dm3.
id

34.6.
nf

We observe a distinct pH jump in the basic region that is well separated from the
hydrochloric acid equivalence. (The pH jump is also smaller and more prolonged
compared to the case of hydrochloric acid.)
Co

34.7.
Para-nitrophenol itself acts as an indicator: it is yellow in an alkaline environment.
Therefore, one can observe a change in the pink hue of phenolphthalein.

34.8.
Only the sum of the two concentrations.

56th IChO Preparatory Problems 161

34.9.
Indicator 1. Indicator 2. Verdict, explanation

Methyl orange Curcumin

(red−yellow, 3.1- (yellow−burgundy, Suitable
4.1) 7.8-9.2)

Methyl red Phenolphthalein Not suitable.

(red−yellow, 4.4- (colorless−pink, 8.3- The measurement of hydrochloric acid
6.2) 9.8) is inaccurate: it is overestimated

ne
Not suitable.
The color change of thymolphthalein
Bromophenol blue Thymolphthalein

Ju
is not seen next to the bromophenol
(yellow−blue, 3.5- (colorless−blue, 9.3-
blue color. The range of
4.6) 10.5)
thymolphthalein is inadequate (it is at
a higher pH).

il
Not suitable.

Congo red
(blue−red, 3.0-5.2)
nt
4-nitrophenol
(colorless−yellow, 5.4-
7.5)
The transition of Congo red is too
broad, and PNP is the measured
material itself, and we wouldn't even
lu
see the color change against the red
background.
tia

Hints for the preparations:

The HCl and acetic acid solutions were around 2 mol/dm3.
en

The HCl + PNP sample was prepared by dissolving 15-25 g of PNP in 80-100 cm3 of
isopropanol and adding 15-25 cm3 of cc. HCl solution.
Inexpensive, but usable stick pH meters can be obtained from aquarium or pool supply
id

stores or from global online retailers (available at around 20 USD on AliExpress and
Temu). Micropipettes are in the same price range at global online retailers. Calibration of
nf

the pH meters is still necessary and can be tedious for dozens of units.
We include a sketch for the setup with our pH meters.
Co

56th IChO Preparatory Problems 162

35. Analysis of a copper alloy
Brass and cupronickel are widely used copper alloys, e.g., in door handles and coins. You
will analyze a nitric acid solution of an alloy sample. First you will determine the copper
content using iodometry. Later you will measure the two metal ions together using
complexometry.
The iodometric determination of copper(II) is based on the low solubility of CuI. During
the titration the concentration of Cu(I) ions remains very low due to the low solubility of
CuI. Thus the Cu(II)/Cu(I) redox system can quantitatively oxidize iodide ions, despite the

ne
small difference in standard redox potentials. The iodine formed can be titrated with
sodium thiosulphate.

Ju
35.1. Give a balanced ionic equation for the reaction between copper(II) ions and
iodide ions and the reaction between iodine and thiosulfate ions.
Your unknown sample solution is in a 100.00 cm3 volumetric flask. Your instructor will

il
let you know if it was made from brass shavings or from a coin. Dilute it to the mark.
Pipette a 10.00 cm3 aliquot to a stoppered 200 cm3 Erlenmeyer flask and dilute to 50 cm3
nt
with distilled water. Acidify with 3 cm3 of 10% acetic acid and add about 2 g (a large
spatula) of potassium iodide. Stopper the flask and wait 15 minutes before you titrate the
lu
iodine formed with 0.01 mol/dm3 sodium thiosulphate. Use 10 drops of the starch
indicator towards the endpoint when the solution becomes faint yellow. Do not
overtitrate, because the excess thiosulfate can interfere with the second titration.
tia

Repeat as necessary and report your accepted average consumption.

35.2. Describe the color of the solution both before the titration and after adding the
indicator. Explain the source of the colors.
en

35.3. What happens if you leave the flask open after the titration is complete? Why?
Copper(I) is easily oxidized to copper(II). Atmospheric oxygen can complete the oxidation
id

instantaneously after making the solution basic with ammonia.

nf

Divalent and trivalent metal ions form stable 1:1 complexes with EDTA, making their
determination convenient.
Co

M2+ + Y4– = MY2–

The reaction can be followed with indicators that form complexes with the metal ion
participating in the reaction. The indicator works well if the Ind and MInd2+ forms have a
different color and if the metal ion forms a more stable complex with
ethylenediaminetetraacetate than with the indicator.
M2+ + Ind = MInd2+
At the beginning of the titration, the metal-indicator complex is present, and at the end of
the titration, the free color of the indicator appears.

56th IChO Preparatory Problems 163

Add 3 cm3 of conc. ammonia solution to the samples titrated with thiosulfate and dilute
to 100 cm3. Titrate with 0.02 M EDTA solution using murexide indicator until the color
change from yellow to purple is complete.
Repeat with your other samples and report your accepted average consumption.
35.4. What do you see after the addition of ammonia and why? What causes the color
of the solution?
35.5. Why do you have to titrate until the color change is complete?
35.6. Calculate the mass percent composition of the alloy.

ne
Equipment and material list

Ju
On each desk:
150 cm3 of 0.01 mol/dm3 thiosulfate solution with accurate concentration
150 cm3 of 0.02 mol/dm3 EDTA solution with accurate concentration

il
a 100 cm3 volumetric flask with the unknown sample
10 cm3 pipette
pipette bulb
burette (12 cm3)
nt
lu
distilled water
dropper
3 titrating flasks (200 cm3, with stopper)
2 beakers (100 cm3)
tia

goggles
tissue paper
Shared between several students:
en

gloves
10% acetic acid solution with graduated plastic dropper (3 cm3)
id

concentrated ammonia solution under the hood, with graduated plastic dropper (3 cm3)
pH paper
starch solution with graduated plastic dropper
nf

solid KI with a spatula (large end will deliver approximately 2 g of KI)

murexide indicator 0.2 m/m% in NaCl with a spatula
Co

GHS codes
Please note that the table of Globally Harmonized System (GHS) hazard codes provided
for the chemicals used in these experiments is intended as a reference only. There is no
guarantee that the information provided is perfect or complete. The list does not replace
the need for professional attention to local regulations and the safety information
provided by the actual suppliers of the chemicals.
Chemical GHS Hazard code
0.02 mol/dm3 Na 2 EDTA solution H332, H373
0.01 mol/dm3 Na 2 S 2 O 3 No hazard
10% acetic acid solution H315, H319

56th IChO Preparatory Problems 164

conc. ammonia H314, H318, H335, H400
KI H372
starch solution No hazard
murexide No hazard
CuSO 4 solution H319, H412
ZnSO 4 solution (optional) H319, H411
NiSO 4 solution (optional) H317, H334, H341, H350, H360, H372

ne
Ju
il
nt
lu
tia
en
id
nf
Co

56th IChO Preparatory Problems 165

Solution
35.1.
2 Cu2+ 4 I–= 2 CuI + I 2
2 S 2 O 3 2− + I 2 = 2 I− + S 4 O 6 2−

35.2.

ne
Before the titration the sample solution is turquoise blue due to the copper ions. After
adding the indicator, the solution is blue due to the iodine-starch complex.

Ju
35.3.

il
The solution will turn blue again because air slowly oxidizes iodide to iodine in acidic
media and the blue color of the starch-iodine complex appears.

35.4.
nt
lu
The precipitate dissolves, and the solution turns intensely blue. All the metals form
ammonia complexes, and the Cu(II)-ammonia complex is blue.
tia

35.5.
en

The endpoint of the titration is when all metal ions are in EDTA complex and there is no
more metal bound to the indicator. The color of the metal indicator complex must
disappear completely to reach the endpoint.
id
nf

35.6.
If the volumes consumed are V 1 and V 2 for the two titrations, then the copper mass
Co

percentage:
𝑀𝑀𝐶𝐶𝐶𝐶 𝑐𝑐𝑡𝑡ℎ𝑖𝑖𝑖𝑖 𝑉𝑉1
𝑤𝑤 =
𝑀𝑀𝐶𝐶𝐶𝐶 𝑐𝑐𝑡𝑡ℎ𝑖𝑖𝑖𝑖 𝑉𝑉1 + 𝑀𝑀𝑀𝑀2 (𝑐𝑐𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸 𝑉𝑉2 − 𝑐𝑐𝑡𝑡ℎ𝑖𝑖𝑖𝑖 𝑉𝑉1 )
Hints for the preparation:
The text does not strongly emphasize that the titrated samples from the first titration are
used in the second part. This is intentional to stress that students need to plan their work
in advance and prepare enough samples and finish the first titration before changing the
solution in the burette.

56th IChO Preparatory Problems 166

Due to safety guidelines in some countries and in the IChO regulations, solutions
containing nickel are not permitted in student laboratories. The procedure can utilize
brass in place of cupronickel in the unknowns.
Samples can be created by combining 0.1 mol/dm3 metal sulfate solutions. For a typical
63:37 brass composition, mix 12-13 cm3 of CuSO 4 with 7-8 cm3 of ZnSO 4 solution. For a
75:25 cupronickel composition, use about 15 cm3 of 0.1 M CuSO 4 and about 5 cm3 of 0.1
M NiSO 4 solution.
Instructors can also prepare the sample solutions by dissolving brass shavings or coins in
concentrated nitric acid (in a hood), followed by neutralization with sodium carbonate

ne
and dilution. In Saudi Arabia, pre 2016 silver-colored common coins were made from
cupronickel.

Ju
il
nt
lu
tia
en
id
nf
Co

56th IChO Preparatory Problems 167

36. Titrations with hypochlorite
The hypochlorite ion is a strong oxidant, and reactions involving hypochlorite proceed
rapidly with a well-defined stoichiometry. Despite these characteristics, direct titrations
using hypochlorite are not common. In the first part of this task, you will determine the
hypochlorite concentration by measuring the iodine it generates in acidic conditions. In
the second part you will explore the reaction between hypochlorite and iodide in alkaline
conditions, monitoring the temperature changes.
Use gloves when working with hypochlorite solutions!

ne
A. Precise determination of the concentration of a hypochlorite solution
Dilute 20.00 cm3 of the hypochlorite solution to 100.00 cm3 to get a stock solution. Take a

Ju
10.00 cm3 aliquot of the stock solution and add 25 cm3 0.10 mol/dm3 KI solution that you
mixed with 5 cm3 of 1 mol/dm3 sulfuric acid.
36.1.

il
The sulfuric acid is added to the hypochlorite sample together with the KI
solution, and not before. Explain the reason for this order.
nt
The iodine formed must be titrated immediately with the ~0.1 mol/dm3 sodium
thiosulfate solution. The exact concentration of the solutions can be found on the label.
lu
When the color of the iodine starts to fade, add 1 cm3 of starch solution and finish the
titration dropwise. Record the consumed volume of the thiosulfate solution and repeat
the titration as necessary.
tia

36.2. Balance the reaction equations. Calculate the hypochlorite concentration in the
original bleach solution.
en

OCl− + H+ + I− = Cl− + I 2 + H 2 O
S 2 O 3 2− + I 2 = I− + S 4 O 6 2−
id

Investigating the reaction of hypochlorite and iodide in alkaline media

nf

It is hard to keep track of the reactions of hypochlorite visually if the products are
colorless. However, there are many instrumental methods to detect the equivalence point.
Co

One of the easiest procedures is the measurement of the temperature change during the
reaction. If the reaction is conducted in a thermally well-isolated vessel (in this case a
foam cup) the evolved heat is assumed to warm only the solution itself.
For practical reasons it makes sense to keep the volume of the reaction mixture constant.
We can achieve this by mixing the two solutions in different ratios. A graph like the
following can be obtained for an exothermic reaction when plotting the maximum
temperature of the mixture as the function of the mixing ratio.

56th IChO Preparatory Problems 168

Tmax

ne
mixing ratio
Measure the temperature before mixing the solutions. Mix 36 cm3 of the two solutions
(hypochlorite solution and the 0.10 mol/dm3 KI) in different ratios using the two burettes

Ju
in the polystyrene cup. The solution with the higher volume needs to be the first one
measured. Stir the mixture with the thermometer while keeping track of the temperature.
The thermometer bulb (or sensing element) needs to be entirely below the surface of the

il
solution. Record the highest temperatures of every mixture and draw a graph. Repeat the
experiment a few times at different ratios until the ratio of the highest temperature can
be read off the graph precisely.
36.3.
nt
Determine the volume ratio at the equivalence point using the graph. Determine
lu
the molar ratio of the hypochlorite and iodide ions at this point?
Change of color in the reaction mixture can be caused by contaminants in small
tia

concentrations, so ignore the color when thinking about the possible products.
36.4. Give a balanced reaction equation for the reaction of hypochlorite and iodide in
alkaline media based on your results. Possible products are Cl 2 , Cl−, I 2 , OI−, IO 3 −,
en

IO 4 −.
36.5. The density (1.0 g/cm3) and heat capacity (4.18 J·g–1·K–1) of the solution are
similar to water. Calculate the reaction enthalpy based on your measurements.
id
nf

Equipment and material list

All solutions and the water used must be thermally equilibrated with the room, so they have to be
Co

prepared and diluted in advance.

On each desk:
250 cm3 diluted bleach in plastic bottle
250 cm3 of 0.10 mol/dm3 KI solution
60 cm3 of 0.1 mol/dm3 thiosulfate with accurate concentration
thermometer capable of measuring with an accuracy of 0.1 degree
100 cm3 volumetric flask
10 cm3 pipette
20 cm3 pipette
pipette bulb

56th IChO Preparatory Problems 169

2 burettes (25 cm3)
distilled water
dropper
3 titrating flasks
3 beakers (100 cm3)
25 cm3 volumetric cylinder
2 polystyrene foam cups (200 cm3, coffee cups)
goggles
tissue
Shared in groups:

ne
gloves
starch solution with graduated plastic dropper
1 mol/dm3 sulfuric acid solution with a 10 cm3 volumetric cylinder

Ju
GHS codes

il
Please note that the table of Globally Harmonized System (GHS) hazard codes provided
for the chemicals used in these experiments is intended as a reference only. There is no
nt
guarantee that the information provided is perfect or complete. The list does not replace
the need for professional attention to local regulations and the safety information
lu
provided by the actual suppliers of the chemicals.
Chemical GHS Hazard code
bleach H315, H319, H400
tia

0.1 mol/dm3 KI H372

0.1 mol/dm3 Na 2 S 2 O 3 No hazard
1 mol/dm3 H 2 SO 4 H290, H314, H315, H318, H319
en

starch solution No hazard

Hints for the preparations:

id

The bleach used was commercially available bleach containing 40 g/dm3 active chlorine
diluted to 2.5 times its original volume.
nf
Co

56th IChO Preparatory Problems 170

Solution
36.1.
The hypochlorous acid formed in acidic media will decompose.

36.2.
OCl− + 2 H+ + 2 I− = Cl− + I 2 + H 2 O

ne
2 S 2 O 3 2− + I 2 = 2 I− + S 4 O 6 2−
If the titration volume is V 1

Ju
n(S 2 O 3 2–) = 0.001V 1 ·c (c is the thiosulfate concentration)
n(I 2 ) = n(OCl–) = 0.0005V 1 · c (in 10.00 cm3 stock solution)

il
In the original solution [OCl–] = 0.25V 1 · c

36.3.
nt
lu
It makes sense to carry out experiments in the linear regime, away from the equivalence
point in order to get a reliable ratio. The equivalence point can be obtained as the
intersection of the two straight lines. Attempting to find the highest temperature amplifies
tia

the inaccuracy of the temperature measurements.

The expected mole ratio is n(OCl–) : n(I–) ≈ 3:1.
en

36.4.
id

3 OCl− + I− = 3 Cl– + IO 3 –
nf

36.5.
Co

The temperature change in the equivalence point is ΔT.

The mass of the solution is 36 g.
The heat released: Q = 4.18 J·g–1·K–1 · 36 g · ΔT
If the volume and concentration of hypochlorite at the equivalence is V 2 and c, then V 2 · c
mol of hypochlorite reacts.
The reaction enthalpy for the 3 OCl− + I− = 3 Cl– + IO 3 – reaction:
150.5 J ⋅ 𝐾𝐾 −1 ⋅ 𝛥𝛥𝛥𝛥
Δ𝑟𝑟 𝐻𝐻 = −3
𝑉𝑉2 ⋅ 𝑐𝑐

56th IChO Preparatory Problems 171

37. TLC experiments with xanthine
alkaloids
In this task, you will explore food items containing biologically active compounds known
as xanthine alkaloids. Cocoa, chocolate, coffee, cola nuts, and tea all contain similar
compounds that may have stimulant or mood-enhancing effects.

ne
Ju
caffeine: R1 = R2 = R3 = CH 3 , R8 = H theobromine: R1, R8 = H, R2 = R3 = CH 3

il
In analytical chemistry, separating compounds with closely
related structures is a
nt
challenge. Thin-layer
chromatography (TLC) is a highly effective method in these
situations, using adsorption equilibria on a solid surface for
dissolved
molecule

adsorbed
molecule
mobile phase
lu
the separation of mixtures.
stationary phase
In Figure 1, the interaction of two substances with a solid adsorption
surface (adsorbent) is illustrated. The substance denoted by
tia

desorption
solid circles () exhibits stronger binding to the surface,
whereas the substance marked with empty circles () has
strongly weakly
weaker binding. As a solvent flows along the surface, it adsorbed adsorbed
en

carries these two components at different rates, resulting in mobile phase flow
spatial separation. The component with stronger adsorption
() lags behind the weakly bound component ().
id

The technique employed is known as chromatography,

where the solid surface is referred to as the stationary phase,
nf

and the solvent is called the mobile phase or eluent.

To become acquainted with the technique, an initial TLC
Co

analysis is conducted using samples of theobromine and Figure 1

caffeine.
The stationary phase you use consists of a uniform layer of fine silica particles attached to
a thick aluminum foil. Handling of this composite sheet is similar to thicker paper,
allowing tasks like cutting with scissors and marking with a pencil. The separation takes
place on the white side of the sheet.
As the separation occurs on the surface, it is crucial to avoid touching the silica layer.
Finger grease can significantly alter the binding affinity of the surface. Therefore, always
handle the sheet by the edges or with tweezers.

56th IChO Preparatory Problems 172

i. Prepare a solution with the theobromine and caffeine samples you find in two
Eppendorf tubes. Dissolve them individually, adding 0.5-0.5 cm3 of 80% ethanol to each.
Note that theobromine is challenging to dissolve in any solvent. If there is any material
remaining undissolved in the tubes, use the clear portion of the solution.
ii. Draw a line approximately 1 cm from the
short edge of the sheet using a pencil (Figure 2).
This line, called the start line, is where we will
deposited
place the materials to be separated. Always samples
draw a thin line with a blunt, soft pencil to
minimize damage to the surface.

ne
start line
iii. To apply the samples, place a capillary into
the solution you wish to spot. A small amount of watchglass

Ju
the solution will rise into the tube due to
capillary action. Touch the tip of the capillary to
beaker
the plate, depositing the sample along the start
line. Be cautious when handling glass

il
solvent front
capillaries, as they can cause injuries. Keep "side view"
them organized in a beaker or next to the
nt
samples. Ideally, use one capillary per sample.
Dispose of used capillaries in the designated
eluent
start line
lu
collection bin, not in the trash, to avoid
potential injuries. Figure 2
tia

Mark the spots for the samples with a pencil. The spots should be evenly spaced from each
other and from the edge of the plate. Write the symbols for each component below the
start line using a pencil.
en

37.1. Why should you write below and not above the line? Why are you using a pencil,
and not a pen?
Apply a small amount from each sample, ensuring that the spot is as small as possible. It's
id

enough to briefly touch the capillary to the silica layer.

iv. Wait for the spots to dry completely (this may take 1-2 minutes). This is crucial because
nf

otherwise the separation will have problems. It is advisable to wait an additional minute
after the spots disappear.
Co

v. The eluent has already been prepared: we will use a mixture of chloroform,
dichloromethane, and isopropyl alcohol in a 4:2:1 volume ratio. Pour enough eluent into
a 100 ml beaker so that the solvent layer is about 0.75 cm deep. Add a filter paper strip as
a wick to assist evaporation. Cover the beaker with a watch glass.
vi. With tweezers, place the TLC plate into the beaker so that the start line is at the bottom,
and the plate leans against the wall of the container. It is important that the solvent level
in the beaker does not reach the start line (see Figure 2). Do not shake or move the beaker
from this point. Cover the beaker. It is essential that the beaker is fully covered while
the plate is inside.

56th IChO Preparatory Problems 173

vii. The eluent begins to absorb into the TLC plate due to capillarity (i.e., capillary forces
'move' the mobile phase). Ensure that the solvent forms a uniform front moving up
the plate parallel to the liquid level. If the solvent front is tilted sideways due to the
plate's position or eluent disturbance, start with a new plate.
viii. Wait for the solvent front to approach about 1 cm from the top edge of the plate, then
remove the plate from the beaker using tweezers. Lay it flat on the table, mark the position
of the solvent front with a pencil, and let the plate dry.
In this task, you are examining colorless substances, so do not be surprised that even after
the separation, the result is just a white plate. Fortunately, xanthine alkaloids absorb

ne
ultraviolet (UV) light, so their position on the TLC plate can be determined based on this.
The silica gel on the TLC plate has been mixed with a substance that glows green under
UV light. When we illuminate the plate with UV light, areas with xanthine alkaloids on the

Ju
silica gel's surface will not let the light through. In other places, the silica will glow green,
so we will see the samples as dark spots against a green background.
ix. Place the dried TLC plate under the UV lamp and outline the spots with a pencil.

il
If you feel that the separation was not successful, make and run a new plate.

nt
The so-called retention factor, or R f value, is used to
characterize individual components. This can be determined
Rf=B/A
solvent front
lu
by measuring the distance from the center of a component's
spot to the starting line and dividing it by the distance between A Rf=B'/A

the starting line and the final solvent front (see Figure 3). The B
B'
tia

R f value is thus a number between 0 and 1, typically given to

two decimal places. In the case of oval or elongated spots, start line

measure the distance from the center of the spot (the darkest
part).
en

37.2. Determine the R f value of the two alkaloids. Can caffeine and theobromine be
clearly distinguished using this method based on the R f values?
id

In your first real experiment, you will attempt to detect xanthine alkaloids in plant
samples (cocoa bean, coffee bean, green tea leaves).
nf

Grind an equal-sized piece of the provided three plant samples (e.g., a single coffee bean)
in a mortar, then continue grinding with 2-3 ml of 80% ethanol. Transfer the mixture
Co

(paste) into a test tube and heat it with a heat gun until boiling begins. Let the solid parts
settle, and from the clear solution, apply a sample to the TLC plate.
You can clean the mortar with dishwashing detergent. Wipe it dry before each new use.
Caution! The heat gun – actually a high-power hairdryer - blows very hot air, which can
easily cause burns. The airstream should never be directed towards yourself or another
person, and never blow onto flammable material! There should be no flammable material
near the heat gun! When placing the heat gun down, be careful as the metal nozzle
becomes very hot: avoid contact with tables, people, especially the power cable. The
teacher will demonstrate the use of the heat gun at the beginning of the practice.

56th IChO Preparatory Problems 174

As before, mark the start line on the TLC plate. Apply the three samples and the previously
prepared samples of the two compounds. Develop the TLC using the same eluent and
mark the components under a UV lamp. If you feel the separation was unsuccessful, repeat
the process.
37.3. Which alkaloids were you able to identify in the plant samples? Estimate which
sample contains more of a particular alkaloid and which one contains less.
If you observe carefully, in the case of the tea sample, there are three faint, distinctive-
colored spots visible even without UV light, which are not observed in the other two
samples.

ne
37.4. What color are these spots, and what is their R f value? Where could these
colored substances come from?

Ju
In the third part of the task, investigate the presence of alkaloids in processed products
(chocolates). Utilize the given samples (dark chocolate, white chocolate, and milk
chocolate) to prepare extracts, similar to the plant samples, and examine their alkaloid
content.

il
37.5. Which chocolates contain which alkaloids? Compare the alkaloid content of each

37.6.
product! nt
Based on your experimental results, which statement(s) is/are true?
lu
 White chocolate does not contain xanthine alkaloids.
 White chocolate does not contain xanthine alkaloids in amounts detectable by
tia

this method.
 White chocolate does not contain significant amounts of cocoa.
 All chocolates contain caffeine detectable by TLC.
en

At the end of the work, write your name on the three TLC plates corresponding to the
three subtasks and place them in the ziploc bag found on your desk. Write your name on
the bag. If you repeated experiments, submit only the plates you consider most successful.
id

List of equipment and materials

nf

On each desk:
Co

3 mg theobromine in Eppendorf tube

3 mg caffeine in Eppendorf tube
5 short test tubes
20 cm3 80% ethanol
10 cm3 eluent,4:2:1 chloroform: dichloromethane: isopropanol mixture
mortar and pestle
TLC chamber (beaker with watchglass cover and filter paper wick)
3 TLC plates (silica on Al) in ziploc bag
8 TLC capillaries
3 graduated plastic Pasteur pipettes (1 cm3)

56th IChO Preparatory Problems 175

tweezers
pencil and ruler
paper towels
goggles
Shared:
coffee beans, cocoa beans, green tea leaves, chocolate (dark, milk, white) samples
heat guns
UV lamp
dishwashing detergent and sponge

ne
container for used capillaries
gloves

Ju
GHS codes
Please note that the table of Globally Harmonized System (GHS) hazard codes provided

il
for the chemicals used in these experiments is intended as a reference only. There is no
guarantee that the information provided is perfect or complete. The list does not replace
nt
the need for professional attention to local regulations and the safety information
provided by the actual suppliers of the chemicals.
lu
Chemical GHS Hazard code
theobromine H302, H319
caffeine H302
tia

80% ethanol H225, H319

dichloromethane H351
H302, H315, H319, H331,
chloroform
en

H336, H351, H361d, H372

isopropanol H225, H336, H319
id
nf
Co

56th IChO Preparatory Problems 176

Solution
37.1.
Because if the writing is above the start line, then during the separation, the substances
have to pass through the graphite-contaminated layer, which can alter their binding.
Because the components of the ink would be smeared/separated by the eluent.

37.2.

ne
In a particular test the values were 0.49 for theobromine and 0.74 for caffeine. So they can
be distinguished from each other.

Ju
37.3.
Cocoa beans contain a significant amount of theobromine and a visible quantity of

il
caffeine, but much less compared to tea and coffee. Both tea and coffee contain caffeine
and do not show detectable amounts of theobromine. The caffeine content in the two
plants is approximately similar. nt
The size of the spots, and the intensity of the color (darkness) is reflects the quantity of
lu
the substance making up the spot.

37.4.
tia

yellow: 0.82
green: 0.92
en

green: 0.93
Tea comes from a leaf where photosynthesis takes place. These spots correspond to
id

photosynthetic pigments.
Specifically, these three are lutein, a type of carotenoid, and chlorophyll a and b, but you
nf

are not supposed to know that.

Co

37.5.
Dark chocolate contains a significant amount of theobromine and a detectable quantity of
caffeine. Milk chocolate has much less theobromine and no detectable caffeine. White
chocolate does not contain either.

37.6.
 White chocolate does not contain xanthine alkaloids in amounts detectable by this
method.
 White chocolate does not contain significant amounts of cocoa.

56th IChO Preparatory Problems 177

38. Determination of the eugenol
content of cloves
Clove, a popular spice in Eastern cuisine and a common fragrance ingredient, derives its
exotic scent from eugenol. In this task, we aim to determine the approximate eugenol
content in cloves through thin-layer chromatography (TLC).

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Eugenol
1. Weigh approx. 0.50 g of clove buds.
2. Add 2.0 cm3 of n-butanol and grind it in a porcelain mortar for at least 3 minutes.

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3. Allow insoluble parts to settle and decant the clean portion of the solution into a small
test tube using a Pasteur pipette. nt
4. Transfer 0.5 cm3 of this solution into a clean test-tube, and add 0.5 cm3 of butanol,
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creating a twofold dilution of the original extract. Label this sample as 1/2.
5. Repeat this dilution, creating a series of 1/4, 1/8 and 1/16 dilutions of the sample.
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6. Apply equal volumes (in practice: equal size spots) of the standard eugenol solution
(with 1 wt% concentration) and the dilution series of the unknown (1/2, 1/4, 1/8, 1/16)
to the "start line" of a clean silica TLC plate.
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7. Dry the plate with a heat gun. Be cautious! The heating should not be longer than 5
seconds!
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8. Develop the plate with dichloromethane as the eluent.

9. Mark the spots with a pencil under a UV lamp.
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The following figure helps in your work. If necessary, you can ask for a replacement plate.
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Hand in your plate. It will be graded.

The density of n-butanol is d = 0.810 g/cm3.
38.1. Calculate the approximate eugenol content of clove buds in wt%.
38.2. Determine the R f value of eugenol.
38.3. Why is it a problem if you use the heat gun for a longer time to dry the plate?

56th IChO Preparatory Problems 178

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List of equipment and materials

On each desk:
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test tube stand

5 short test tubes
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8 cm3 n-butanol
10 cm3 dichloromethane eluent
mortar and pestle
TLC chamber (beaker with Al foil cover and filter paper wick)
2 TLC plates (silica on Al)
6 TLC capillaries
6 graduated plastic Pasteur pipettes (1 cm3)
tweezers
pencil and ruler
paper towels
goggles

56th IChO Preparatory Problems 179

Shared:
balances
heat guns
clove
1 wt. % eugenol solution in n-butanol
UV lamp
container for used capillaries
gloves

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GHS codes
Please note that the table of Globally Harmonized System (GHS) hazard codes provided

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for the chemicals used in these experiments is intended as a reference only. There is no
guarantee that the information provided is perfect or complete. The list does not replace
the need for professional attention to local regulations and the safety information
provided by the actual suppliers of the chemicals.

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Chemical GHS Hazard code
n-butanol nt
H226, H302, H335,
H336, H315, H318
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dichloromethane H351
eugenol H317, H319
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56th IChO Preparatory Problems 180

Solution
Marking of the plate: missing marks, line or circles, slanting, spots missing, spots too big
result in a penalty.
38.1.
One of the dilutions spots will be matching the 1% solution in intensity. If that is the ¼
dilution, then the original solution contained w = 4% eugenol.
Taking the density of the first extract identical to butanol, that means 4% of 1.62 g =

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64.8 mg of eugenol, 12.9% of the clove mass.

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38.2.
The R f value can be graded. Typical values are around 0.78 for eugenol in this setup.

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38.3. nt
Eugenol, as a scent component, is also volatile.
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id
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56th IChO Preparatory Problems 181