Preparatory Problems: 46 International Chemistry Olympiad (Icho - 2014)

Preparatory Problems
46th International Chemistry Olympiad (IChO - 2014)
Editorial Board
Nguyen Tien Thao, Editor in Chief
Nguyen Minh Hai
Nguyen Van Noi
Truong Thanh Tu
Hanoi University of Science, Vietnam National University, Hanoi

Tel: 0084 435406151; Fax: 0084 435406151 Email: icho2014prep@hus.edu.vn
July 17th, 2014 (Revised)

46th International Chemistry Olympiad Preparatory Problems
Hanoi, Vietnam - 2014
Contributing Authors
Le Minh Cam, Hanoi National University of Education
Vu Viet Cuong, Hanoi University of Science, VNU-Hanoi
Pham The Chinh, Institute of Chemistry, VAST
Nguyen Huu Dinh, Hanoi National University of Education
Tran Thi Da, Hanoi National University of Education
Nguyen Van Dau, Hanoi University of Science, VNU-Hanoi
Dao Phuong Diep, Hanoi National University of Education
Pham Huu Dien, Hanoi National University of Education
Nguyen Hien, Hanoi National University of Education
Hoang Van Hung, Hanoi National University of Education
Nguyen Hung Huy, Hanoi University of Science, VNU-Hanoi
Tu Vong Nghi, Hanoi University of Science, VNU-Hanoi
Trieu Thi Nguyet, Hanoi University of Science, VNU-Hanoi
Do Quy Son, Vietnam Atomic Energy Institute
Ta Thi Thao, Hanoi University of Science, VNU-Hanoi
Nguyen Tien Thao, Hanoi University of Science, VNU-Hanoi
Lam Ngoc Thiem, Hanoi University of Science, VNU-Hanoi
Ngo Thi Thuan, Hanoi University of Science, VNU-Hanoi
Vu Quoc Trung, Hanoi National University of Education
Dao Huu Vinh, Hanoi University of Science, VNU-Hanoi
Acknowledgements
We would like to express our deep gratitude to the members of the International Steering
Committee for their valuable comments and suggestions and to Dr. Vu Viet Cuong, Dr. Nguyen
Hung Huy, and Dr. Pham Van Phong for their kind collaborations.
Sincerely yours,
Editors
Chemistry: The flavor of life 2

Preface
We are happy to provide Preparatory Problems for the 46 th International
Chemistry Olympiad. These problems were prepared with reliance on
fundamental topics firmly covered in high school chemistry courses along
with some advanced topics for the chemistry olympiad competition. These
topics are listed under “Topics of Advanced Difficulty”, and their
applications are given in the problems. Solutions will be sent to Head
Mentors on February 20th, 2014 and updated on www.icho2014.hus.edu.vn on
May 31st, 2014. Although a lot of efforts have gone to making this Booklet,
some mistakes, typos may still be there. We welcome any comments,
corrections, or questions about the problems to icho2014prep@hus.edu.vn.
We hope that these problems will be motivating for students to participate

in the IChO-2014 competition. We believe that IChO-2014 will not only be a
chemistry competition, but also a pleasant time for you to know about
Vietnamese culture.
We look forward to seeing you in Hanoi and at Hanoi University of Science,
Vietnam National University in Hanoi.
Hanoi, January 31st, 2014

Editor in Chief
Nguyen Tien Thao
46th IChO Preparatory Problems, Hanoi, Vietnam, July 2014, 3

July 17th, 2014 (Revised)
Contents
Fields of Advanced Difficulty 6
Physical Constants, Symbols and Conversion Factors 7
Part 1. Theoretical Problems 8
Problem 1. Polar and non-polar molecules 8
Problem 2. Calculations of lattice energy of ionic compounds 10
Problem 3. A frog in a Well 12
Problem 4. Electrons in a 2,3-Dimensional Box 14
Problem 5. Tug of war 16
Problem 6. Radiochemistry 17
Problem 7. Applied thermodynamics 19
Problem 8. Complex compounds 20
Problem 9. Lead compounds 24
Problem 10. Applied electrochemistry 26
Problem 11. Phosphoric acid 27
Problem 12. Kinetic chemistry 28
Problem 13. Kinetics of the decomposition of hydrogen peroxide 30
Problem 14. Magnetism of transition metal complexes 31
Problem 15. Structure and synthesis of Al-Keggin ion 34
Problem 16. Safrole 35
Problem 17. Imidazole 38
Problem 18. Small heterocycles 39

Problem 19. Vitamin H 41
Problem 20. No perfume without jasmine 44
Problem 21.Vietnamese cinnamon 47
Problem 22. Cinnamic acid 49
Problem 23. Tris(trimethylsilyl)silane and azobisisobutyronitrile 50
Problem 24. (-)-Menthol from (+)-δ-3-carene 52
Problem 25. Cefalotin 53
Problem 26. A heterocyclic compound 55
Problem 27. Lotus 56
Problem 28. NMR Spectra 59
Problem 29. IR Spectra 60
Part 2. Practical Problems 62
Practical Problems, Safety 62
Problem 30. Condensation between valinin and benzylamine 63
Problem 31. Synthesis of eugenoxy acetic acid 65
Problem 32. Complexometric titration 68
Problem 33. Determination of zinc and lead in zinc oxide powder 72
Problem 34. Preparation of copper(II) acetylacetonate 76
Problem 35. Kinetic analysis of the hydrolysis of aspirin 79
Problem 36. Complex formation of ferric ion and salicylic acid 85
Appendices 90

Fields of Advanced Difficulty

Theoretical
Kinetics: Integrated first- and second-order rate equation; analysis of moderately

complex reactions mechanisms using the steady state approximation, the use of the
Arrhenius equation.
Thermodynamics: Electrochemical cells, the relationship between equilibrium

constants, electromotive force and standard Gibbs energy, the variation of the
equilibrium constant with temperature.
Quantum mechanics: Particle-in-a-box calculations, orbital-overlaps, spin-orbit

coupling.
Spectroscopy: Interpretation of IR spectra and relatively simple 1H, 13C, and 27Al
NMR spectra: chemical shifts, multiplicities, coupling constants and integrals.
Advanced Inorganic: Trans effect; the use of simple crystal field theory to explain
electronic configurations in octahedral and tetrahedral complexes; calculation of
the magnetic moment using the spin-only formula, solid state structures, packing
arrangement.
Advanced Organic: Stereoselective transformations; aromatic nucleophilic

substitution; polycyclic aromatic compounds and heterocycles.

Practical
Basic synthesis techniques: Thin layer chromatography, Extraction, Filtration,
Drying, Titration.
UV – Vis spectroscopy.
Physical Constants, Symbols and Conversion Factors
Avogadro's constant, NA = 6.0221×1023 mol–1

Boltzmann constant, kB = 1.3807×10–23 J∙K–1
Universal gas constant, R = 8.3145 J∙K–1∙mol–1 = 0.08205 atm∙L∙K–1∙mol–1
Speed of light, c = 2.9979×108 m∙s–1
Planck's constant, h = 6.6261×10–34 J∙s
Faraday constant, F = 9.64853399×104 C
Mass of electron, me = 9.10938215×10–31 kg
Standard pressure, P = 1 bar = 105 Pa
Atmospheric pressure, Patm = 1.01325×105 Pa = 760 mm Hg = 760 Torr
Zero of the Celsius scale, 273.15 K
1 picometer (pm) = 10–12 m; 1Å = 10-10 m; nanometer (nm) = 10–9 m
1 eV = 1.6 × 10-19 J

Periodic Table of Elements with Relative Atomic Masses
1
18
1 2
H He
1.008 2 13 14 15 16 17 4.003
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
6.941 9.012 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 24.31 3 4 5 6 7 8 9 10 11 12 26.98 28.09 30.97 32.07 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.10 40.08 44.96 47.87 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.38 69.72 72.64 74.92 78.96 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.96 [98] 101.07 102.91 106.42 107.87 112.41 114.82 118.71 121.76 127.60 126.90 131.29
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.91 137.33 138.91 178.49 180.95 183.84 186.21 190.23 192.22 195.08 196.97 200.59 204.38 207.2 208.98 (209) (210) (222)
87 88 89 104 105
Fr Ra Ac Rf Ha
(223) 226.0 (227) (261) (262)
58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
140.12 140.91 144.24 (145) 150.36 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.05 174.97
90 91 92 93 94 95 96 97 98 99 100 101 102 103

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
232.04 231.04 238.03 237.05 (244) (243) (247) (247) (251) (254) (257) (256) (254) (257)
PART 1. THEORETICAL PROBLEMS
Problem 1. Polar and non-polar molecules
In chemistry, a molecule is considered non-polar when its positive charge

center and negative charge center coincide, i.e. the charge distribution is
symmetrical in the molecule. On the other hand, when a molecule has two distinct
centers for positive and negative charges, it is considered polar.
This charge distribution property is measured by a quantity called the dipole
moment which is defined as the magnitude of the charge q and the distance l
between the charges:

Hanoi, Vietnam - 2014  
  ql
The dipole moment is a vector pointing from the positive charge center to the
negative one.
The dipole moment is often expressed in debyes (D). The relationship between
debyes (D) and coulomb meters (C∙m) in SI units is as follows: 1 D = 3.33×10–30
C∙m.
1. The dipole moment is closely related to the molecular geometry. In order to

calculate the net dipole moment  of multi-atomic molecules, we can add the
dipole moment vectors for individual bonds. In this case, an individual bond is
considered to have its own dipole moment called the bond moment.
For a non-linear molecule with three atoms, ABC, the net dipole moment  can be
 
calculated by adding vectors in which  1 and  2 are the bond moments for AB and
AC bonds, and  is the bond angle. Determine the general equation for calculating
the net dipole moment.
2. The directions of the individual bond moments should be considered.

2.1 The molecule of CO2 is linear. Calculate the net dipole moment  of the
molecule.
2.2 A non-linear molecule of A2B such as H2S has the net dipole moment   0.
Determine  for H2S if SH = 2.61×10–30 C∙m and the bond angle  = 92.0o.
3. The bond angle HCH in the formaldehyde molecule is determined

experimentally to be approximately 120o; the bond moments for C-H and C-O
bonds are μ CH = 0.4 D and μ C O = 2.3 D, respectively.

3.1 Determine the orbital hybridization of C and O atoms, and plot the
overlaps of orbitals in the formaldehyde molecule.
3.2 Calculate the net dipole moment (μ) of the formaldehyde (D), given the order
of the electronegativity as χO  χC  χH . (Hints: Electronegativity is the ability of
an atom in a molecule to attract shared electrons to itself).
4. The dipole moments of water and dimethylether in gaseous state are determined
as 1.84 D, and 1.29 D, respectively. The bond angle formed by two bond moments
of O-H in the water molecule is 105o. The bond angle formed by two bond
moments of O-C in the ether molecule is 110o.
Estimate the bond angle formed by the bond moments of O-H and C-O in the
methanol molecule, given that the dipole moment of methanol molecule is 1.69 D.
Assume that individual bond moments are unchanged in different molecules.
Problem 2. Calculations of lattice energy of ionic compounds
1. Lithium is the lightest metal and does not exist in pure form in nature due to its
high reactivity to water, moisture, oxygen... Lithium readily forms ion with a 1+
charge when reacting with nonmetals. Write down the following chemical
reactions at room temperature:
1.1 Lithium reacts with water.
1.2 Lithium reacts with halogens, e.g. Cl2.
1.3 Lithium reacts with dilute sulfuric acid and concentrated sulfuric acid.
2. The change in enthalpy of a particular reaction is the same whether it takes place
in one step or in a series of steps (Hess’s law). Use the following data:
Sublimation enthalpy of Li(s), ΔSH = 159 kJ∙mol–1.
Ionization energy of Li(g), I = 5.40 eV.

Dissociation enthalpy of Cl2, ΔDH = 242 kJ∙mol–1.
Electron affinity of Cl(g), E = -3.84 eV.
Formation enthalpy of LiCl(s), ΔfH = – 402.3 kJ∙mol–1.
rLi   0.62 Å; rCl  1.83 Å; NA = 6.02×1023 mol–1.

2.1 Establish the Born-Haber cycle for lithium chloride crystal.

2.2 Calculate the lattice energy Uo (kJ∙mol-1) using the Born-Haber cycle.
3. In practice, experimental data may be employed to calculate lattice energies in

addition to the Born-Haber cycle. One of the semi empirical formulae to calculate
the lattice energy Uo for an ionic compound, which was proposed by Kapustinskii,
is as follows:
U0 = - 287.2
Z Z  
1 
0.345 

r  r  r  r 
where:  is the number of ions in the empirical formula of ionic compound,

r+ and r- are the radii of the cation and anion, respectively, in Å,
Z+ and Z- are cation and anion charges, respectively,
-1
U0 is the lattice energy, in kcal·mol .
–1
Use the Kapustinskii empirical formula to calculate U o (in kJ·mol ) of LiCl
crystal, given that 1 cal = 4.184 J.
4. Based on the results of two calculation methods in sections 2 and 3, choose the
appropriate box:
According to the Born-Haber cycle and Kapustinskii empirical formula

for lithium chloride crystal structure, both methods are close to the
experimental value.

Only the calculated result of the Born-Haber cycle is close to the
experimental value.
Only the calculated result of the Kapustinskii empirical formula is close
to the experimental value.
Data: Given the experimental value of lattice energy for LiCl is 849.04 kJ/mol.
5. In the formation of LiCl crystal, it is found out that the radius of lithium cation is
smaller than that of chloride anion. Thus, the lithium ions will occupy the
octahedral holes among six surrounding chloride ions. Additionally, the body edge
+
length of LiCl cubic unit cells is 5.14 Å. Assume that Li ions just fit into
octahedral holes of the closest packed chloride anions.
+ -
5.1 Calculate the ionic radii for the Li and Cl ions.
5.2 Compare the calculated (theoretical) radii with the experimental radii given
below, and choose the appropriate box:
Both calculated radii of lithium and chloride ions are close to the
experimental values.
Only the calculated radius of lithium ion is close to the experimental value
Only the calculated radius of chloride ion is close to the experimental value.
+ –
The experimental radii of Li and Cl are 0.62 Å and 1.83 Å, respectively.
Problem 3. A frog in a well
The energy levels of an electron in a one-dimensional box are given by:

h2
En  n 2 n: 1, 2, 3…
8mL2
in which h is the Planck’s constant, m is the mass of the electron, and L is the
length of the box.
1. The  electrons in a linear conjugated neutral molecule are treated as
individual particles in a one-dimensional box. Assume that the  electrons are
delocalized in the molecular length with the total number of N  electrons and
their arrangement is governed by the principles of quantum mechanics.
1.1 Derive the general expression for ΔE LUMO – HOMO when an electron is excited
from the HOMO to the LUMO.
1.2 Determine the wavelength  of the absorption from the HOMO to the LUMO.
2. Apply the model of  electrons in a one-dimensional box for three dye

molecules with the following structures (see the structural formula). Assume
that the  electrons are delocalized in the space between the two phenyl groups
with the length L is approximately equal to (2k + 1)(0.140) nm, in which k is
the number of the double bonds.
a) 1,4-diphenyl-1,3-butadiene
(denoted as BD)
b) 1,6-diphenyl-1,3,5-hexatriene
(denoted as HT)
c) 1,8-diphenyl-1,3,5,7-octatetraene
(denoted as OT)
2.1 Calculate the box length L (Å) for each of the dyes.

2.2 Determine the wavelength  (nm) of the absorption for the molecules
of the investigated dyes.
3. Recalculate the box length L (Å) for the three dye molecules, assuming that the
 electrons are delocalized over the linear conjugated chain which is presented
as a line plotted between the two phenyl groups (see the structural formula).
The bond angle C – C – C is 120 o and the average length of C – C bond is 0.140
nm.
4. Give the following experimental data on the wavelength  of absorption.
Substance BD HT OT
 (nm) 328.5 350.9 586.1
4.1 Determine the box length L (Å) of the linear conjugated chain for each of the
three investigated dyes.
4.2 Tabulate the values of the box length L for the dyes calculated above by the
three different methods, denoted as 1, 2, and 3. Choose the method which is the
most fit to the experimental data.
Problem 4. Particles in 2, 3 - Dimensional Box
1. In Problem 3, the energy E of particle in one- dimensional box is calculated as:

h2
E =n 2
8 mL2
where h is Planck’s constant; m is the mass of the particle; L is the box length;
n is the quantum number, n = 1, 2, 3…

An electron in a 10 nm one-dimensional box is excited from the ground state to a
higher energy level by absorbing a photon of the electromagnetic radiation with a
wavelength of 1.374×10-5 m.
1.1 What is the energy gap (ΔE) of the two mentioned states?
1.2 Determine the final energy state for this transition.
2. The treatment of a particle in a one- dimensional box can be extended to a two-

dimensional box of dimensions Lx and Ly yielding the following expression for
energy:
h2  n 2x n 2y 
E=  2  2 
8m  Lx L y 
The two quantum numbers independently can assume only integer values.
Consider an electron confined in a two-dimensional box that is L x = 8.00 nm in the
x direction and Ly = 5.00 nm in the y direction.
2.1 What are the quantum numbers for the first three allowed energy levels? Write
the first three energy, Exy, in order of increasing energy?
2.2 Calculate the wavelength of light necessary to move an electron from the first
excited state to the second excited one.
3. Similarly, the treatment of a particle in a one-dimensional box can be extended

to a rectangular box of dimensions Lx, Ly, and Lz, yielding the following expression
for energy:
h2  n 2x n 2y n 2z 
E=  2  2  2 
8m  Lx L y Lz 

The three quantum numbers nx, ny, and nz independently can assume only
integer values. An oxygen molecule is confined in a cubic box of volume 8.00 m 3.
Assume that the molecule has an energy of 6.173 × 10–21 J; temperature T = 298 K.
1
3.1 What is the value of n  (n x2  n y2  n z2 ) 2 for this molecule?
In a rough approximation to estimate the energy gap of this system, assume that the
two closest energy levels correspond to n and n + 1.
3.2 What is the energy separation between the levels n and n + 1?
4. In quantum mechanics, an energy level is said to be degenerate if it corresponds

to two or more different measurable states of a quantum system. Consider a
particle in a cubic box. What is the degeneracy of the level that has energy 21/3
times that of the lowest level?
Problem 5. Tug of war

“Tug of war is a sport that directly pits two teams against each other in a test of
strength. This is also a traditional game of Vietnamese people”
The following table gives the standard molar Gibbs energy at different
temperatures for the reaction (1) below:
SO3(g) SO2 (g) + ½ O2 (g) (1)
T/oC 527 552 627 680 727

ΔrGo /kJ∙mol–1 21.704 20.626 14.210 9.294 4.854
1. Use the Van Hoff’s equation to estimate the lnKp1 at each temperature.
2. Plot lnKp1 against 1/T to determine the value of Δ rHo in kJ∙mol–1 assuming that
ΔrnxHo does not vary significantly over the given temperature range.

3. Using the best-fit line to plot a lnK p1 versus 1/T, determine the Kp2 for the
following reaction (2) at 651.33 oC:
2SO3(g) 2SO2 (g) + O2 (g) (2)
4. An amount of 15.19 g of iron (II) sulfate was heated in an evacuated 1.00 L

container to 651.33 oC, in which the following reactions take place:
FeSO4 (s) Fe2O3 (s) + SO3 (g) + SO2 (g) (3)
2SO3(g) 2SO2 (g) + O2 (g) (4)
When the system has reached equilibrium, the partial pressure of oxygen is of
21.28 mmHg. Calculate the equilibrium pressure of the gases and the value of K p3
for the reaction (3) at equilibrium.
5. Calculate the percentage of FeSO4 decomposed?
Problem 6. Radiochemistry
Zircon (ZrSiO4) is a mineral found abundantly in placer deposits located in the

central coast of Vietnam. Besides being widely utilized in the ceramic industry,
zircon is also used as a raw material for the manufacture of zircaloy which is used
to build fuel rods that hold the uranium dioxide (UO 2) fuel pellets in nuclear
reactors. Zircon ore contains a trace amount of uranium, and it is not a viable
source of uranium in practice. However, zircon crystals make a perfect storage
medium to avoid the loss of uranium and lead (Pb) isotopes because of its stable
crystal structure. This allows developing uranium-lead dating method.
There are 3 naturally occurring decay series:
- The thorium series begins with 232Th and ends up with 208Pb.
- The uranium series (also referred to as the uranium-radium series) is headed
by 238U. The half-life (t1/2) of 238U is 4.47 × 109 years.

- The actinium series is headed by 235U with the half-life of 7.038 ×
108 years.
204
Four stable isotopes of Pb exist in nature: Pb, 206Pb, 207Pb, and 208
Pb. The natural
abundance of each isotope is shown in the following table.
204 206 207 208
Pb Pb Pb Pb
1.4 24.1 22.1 52.4
An analysis of a zircon mineral sample gives the following mass ratios of U and Pb
isotopes:
m(238U) : m(235U) : m(206Pb) : m(204Pb) = 99.275 : 0.721 : 14.30 : 0.277
1. Indicate the stable isotope of Pb which is not involved in the above decay series.
238 235
2. Determine the mass ratio of U to U when the zircon mineral was first
formed. Assume that the mineral already contained natural Pb right at the onset of
its formation.
3. Production of uranium from low-grade will encounter many difficulties, notably
large concentration of impurities and low concentrations of uranium in leach
solutions. Various technological advances have been applied to overcome the
aforementioned problems; these include fractional precipitation, liquid-liquid
extraction, or ion exchange methods.
In an experiment to extract uranium from sample of low uranium content using
diluted H2SO4, in the preliminary treated leach solutions, the concentration of
uranyl sulfate (UO2SO4) is 0.01 M and the concentration of iron(III) sulfate
(Fe2(SO4)3) goes up to 0.05 M. The separation of uranium from iron and other
impurities can be carried out by the fractional precipitation method.
Calculate the pH necessary to precipitate 99% of Fe 3+ without losing uranium
ions. Assume that the adsorption of uranium onto Fe(OH) 3 is negligible. Under the

experimental conditions, the solubility product values for UO 2(OH)2 and Fe(OH)3
are 1.0 × 10–22 and 3.8×10–38, respectively.
4. One of the proper methods to obtain a rich uranium solution is the liquid-liquid
extraction with the organic phase containing the extracted agent of
tributylphosphate (TBP) diluted in kerosene. When extracting uranium in the form
of uranyl nitrate (UO2(NO3)2) under appropriate conditions, the relationship
between the concentrations of uranium in water and organic phases is given by:
Corg .
Distribution coefficient: D = C = 10
aq
where: Corg and Caq are the equilibrium concentrations (M) of UO 2(NO3)2 in organic
and aqueous phases, respectively.
Calculate the mole percentage (in comparison with the initial concentration) of
UO2(NO3)2 remaining in the aqueous phase after extracting 1.0 L of the solution
(with an initial concentration of 0.01 M) with 500 mL of organic solvent.
5. Propose a scheme to extract 96% of UO 2(NO3)2 from 1.0 L of the aqueous phase
into 500 mL of the organic phase. Assume that the distribution coefficient remains
constant throughout the extraction process (D = 10).
Problem 7. Applied thermodynamics
1. In applied thermodynamics, Gibbs free energy plays an important role and can
be calculated according to the following expression:
∆Go298 = ∆Ho298 – T∆So298
∆Go298 - standard free energy change
∆Ho298 - standard enthalpy change

∆So298 - standard entropy change
The burning of graphite is represented by two reactions:
C (graphite) + ½ O2 (g) → CO (g) (1)
C (graphite) + O2 (g) → CO2 (g) (2)
The dependence of ∆Ho, ∆So on temperature is as follows:
Reaction (1): ∆HoT (1) (J∙mol-1) = –112298.8 + 5.94T;
∆SoT (1) (J∙K-1∙mol-1) = 54.0 + 6.21lnT
Reaction (2): ∆HoT (2) (J∙mol-1) = – 393740.1 + 0.77T;
∆SoT (2) (J∙K-1∙mol-1) = 1.54 – 0.77lnT
Based on the above data:
1.1 Derive the expression for the Gibbs free energy as a function of temperature,
∆GoT = f(T) for each reaction.
1.2 Predict the changes of ∆GoT with an increase in temperature.
2. Assume that at 1400 oC, during the course of reactions (1) and (2), CO gas might
continue to react with O2 to form the final product CO2.
2.1 Write down the reaction (3) for the formation of CO2 from CO gas.
2.2 Calculate ∆GoT (3).
2.3 Determine the equilibrium constant Kp for reaction (3) at the given temperature.
3. In an experiment, NiO powder and CO gas were placed in a closed container

which was then heated up to 1400 oC. When the system reached equilibrium, there
were four species present: NiO(s), Ni(s), CO(g) and CO 2(g). The mole percentages
of CO and CO2 are 1 % and 99 %, respectively, and the pressure of the system is
1.0 bar (105 Pa).
3.1 Write down the reactions in the above experiment.
3.2 Based on the experimental results and the above thermodynamic data, calculate
the pressure of O2 in the equilibrium with NiO and Ni at 1400 oC.

Problem 8. Complex compounds
Ethylenediamine tetraacetic acid (EDTA) is used as a reagent to titrate the

metal ions in the complexometric titration.
EDTA is a tetraprotic acid, abbreviated as H4Y, with the structure:
As EDTA is sparingly soluble in water, a more soluble sodium form, Na 2H2Y, is

usually used and H2Y2− is commonly known as EDTA. EDTA forms strong 1:1
complexes with most metal ions Mn+.
1. How many atoms of an EDTA molecule are capable of binding with the metal
ion upon complexation?
1.1 Check in the appropriate box.
2 4 6 8
1.2 Draw the structure of the complex of a metal ion M2+ with EDTA.
2. Complexation reaction between Y4− form of EDTA and metal ion Mn+ has a large
formation constant (stability constant) β:
[ MY ( 4  n )  ]
M n+
+Y 4−
MY (4−n)− 
[ M n  ][Y 4  ]
Besides complexation reaction between Y4− form of EDTA and metal ion Mn+,
other processes in the solution also develop such as formation of hydroxo
complexes of the metal ion, acid-base equilibrium of H 2Y2−… To account for such

processes conditional formation constant β’ is used for the calculations.
β’ is determined from β as the following expression:
β = β.α M n+ .α Y 4-
[Y 4 ]
where: α Y4- and α M n+ are fractions of Y4– ( α Y 4- 
[Y]'
) and free metal ion Mn+ (
[M] ), with [Y]’ and [M]’ being the total concentrations of all forms of Y4−
α M n+ 
[M]'
and Mn+, excluding MY(4−n)−. Given that: H4Y has pKa1 = 2.00; pKa2 = 2.67; pKa3 =
6.16; and pKa4 = 10.26 (pKa values for H5Y+ and H6Y2+ are ignored).
pK s(Mg(OH) ) =10.95; log  MgY 2  8.69
2
Mg2+ + H2O MgOH+ + H+ *

β = 1.58×10-13; (pKa = -logKa; pKs = -logKs)
In a typical experiment, 1.00 mL of 0.10 M MgCl2 solution and 1.00 mL of 0.10 M
Na2H2Y solution are mixed together. pH of the resulting solution is adjusted to
10.26 by an NH3/NH4+ buffered solution.
2.1 Calculate conditional formation constant (’) of the MgY2− complex at pH =
10.26 given that acid-base equilibrium of H 2Y2− and formation of mononuclear
hydroxo complex of Mg2+ occur in the solution.
2.2 Does the Mg(OH)2 precipitate in this experiment? Check in the appropriate box.
Precipitation No precipitation
3. In order to titrate metal ions by EDTA, the conditional formation constant (’)
of the complex metal – EDTA (MY (4−n)−) must be large enough, usually ’  1.00 ×
108 - 1.00 × 109. To determine the concentrations of Mn 2+ and Hg2+ in an analytical
sample, two experiments are carried out.

Experiment 1: Add 25.00 mL of 0.040 M EDTA solution to 20.00 mL of the
analytical solution. Adjust the pH of the resulting solution to 10.50. Titrate the
excess EDTA with a suitable indicator and 12.00 mL of 0.025 M Mg 2+ solution is
consumed.
Experiment 2: Dissolve 1.400 gram of KCN into 20.00 mL of the analytical
solution (assuming that the volume is unchanged upon dissolution) and then add
25.00 mL of 0.040 M EDTA solution. Titrate the excess EDTA in the resulting
mixture at the pH of 10.50; 20.00 mL of 0.025 M Mg2+ solution is consumed.
3.1 Prove that: in the experiment 2, Hg2+ cannot be determined by titration with
EDTA in the presence of KCN in solution (or Hg2+ is masked in the complex
form of Hg(CN)42-).
3.2 Write down chemical equations for the reactions in the two experiments and
calculate molar concentrations of Mn2+ and Hg2+ in the analytical solution.
Given that: log  HgY  21.80; log  Hg (CN )  38.97; pK a ( HCN )  9.35
2 2
4
2+
a 4
(Other processes of Hg are ignored; the pK values of H Y are provided in
question 2 ).
4. In the titration of polyprotic acids or bases, if the ratios of consecutive

4
dissociation constants exceed 1.00×10 , multiple titrations are possible with an
error less than 1%. To ensure the allowed error, only acids or bases with
-9
equilibrium constants larger than 1.00×10 can be titrated. To find the end-point,

pH range of the indicator must be close to that of the equivalence point
EP
(pH ); the point at which the stoichiometric amounts of analyte and titrant has
2 2
reacted. Titrate 10.00 mL of 0.25 M Na H Y solution by 0.20 M NaOH solution in
a typical experiment.
4.1 Write down the chemical equation for the titration reaction.
EP
4.2 Determine the value of pH .
4.3 Choose the most suitable indicator (check in the appropriate box) for the above
titration from the following: bromothymol blue (pH = 7.60); phenol red (pH =
8.20); phenolphtalein (pH = 9.00).
Bromothymol blue Phenol red Phenolphtalein
4.4 Titration error q defined as the difference between the titrant amount added and
the titrant amount needed to reach the equivalence point is expressed as:
C NaOHV1  C NaOHV2 V  V2
q  100%  1  100%
C NaOHV2 V2

NaOH 1 2
where C is the NaOH concentration; V : End-point volume of NaOH; V :
equivalence point volume of NaOH.
Calculate the consumed volume of NaOH solution and the titration error if the final
pH is 7.60.
Problem 9. Lead compounds
209 208 207 206

1. Consider the following nuclide: Bi(I), Pb(II), Pb(III), Pb(IV). Which
238
nuclide is the last member of the decay series for U? Check in the appropriate
box.
(I) (II) (III) (IV)
2. There are three natural decay series. They begin with Th-232(I), U-238(II), U-
235(III) and end with Pb-208, Pb-206, Pb-207. In which decay chain are there 6 α
decays and 4 β decays? Choose the correct answer by checking in the appropriate
box.
(I) (II) (III) None

3. Pb(NO3)2 solution is slowly added into 20.00 mL of a mixture
consisting of 0.020 M Na2SO4; 5.0×10−3 M Na2C2O4; 9.7×10−3 M KI; 0.05 M KCl
and 0.0010 M KIO3. When the bright yellow precipitate of PbI 2 begins to form,
21.60 mL of Pb(NO3)2 solution is consumed.
3.1 Determine the order of precipitation?
3.2 Calculate the concentration of Pb(NO3)2 solution?
Given that: pK s(PbSO 4 ) = 7.66; pK s(Pb(IO3 )2 ) = 12.61; pK s(PbI2 ) = 7.86; pK s(PbC2O 4 )

= 10.05; pK s ( PbCl )  4.77 . (Other processes of the ions are ignored).
2
4. One of the common reagents to detect Pb 2+ species is K2CrO4, giving yellow

precipitate PbCrO4, which is soluble in excess of NaOH. The solubility of PbCrO 4
depends not only on pH but also on the presence of coordinating species... Given
that the solubility of PbCrO4 in 1 M acetic acid solution is s = 2.9×10 −5 M,
calculate the solubility product Ksp of PbCrO4.
pK a ( CH 3COOH )  4.76; lg  Pb ( CH   2.68; lg  Pb ( CH 3COO ) 2  4.08;
3 COO )
pK a ( HCrO  )  6.5
4
Pb2+ + H2O PbOH+ + H+ *β = 10-7.8

Cr2O72- + H2O 2CrO42- + 2H+ K = 10-14,64
5. Lead-acid battery, commonly known as lead battery consists of two lead plates a
positive electrode covered with a paste of lead dioxide and a negative electrode
made of sponge lead. The electrodes are submersed in an electrolyte consisting of
water and sulfuric acid H2SO4. Write the chemical equations for processes on each
electrode, overall reaction as the battery discharges and the cell diagram.
0
Given that: EPb 2  0.126 V ;
0
EPbO / Pb 2
 1.455 V ; pK a ( HSO  )  2.00;
/ Pb 2 4
RT
pK s ( PbSO4 )  7.66; at 25 oC: 2.303  0.0592 V
F
6. Calculate:

0 0
6.1 E PbSO4 /Pb ; E PbO2 /PbSO4
6.2 The potential V of the lead battery if CH 2SO4  1.8 M.
Problem 10. Applied electrochemistry

1. Reduction-oxidation reactions have played an important role in chemistry due to
their potential to be valuable sources of energy for technology and life. Write down
chemical equations for the following reactions:
1.1 Oxidation of glucose (C6H12O6) with KMnO4 solution in the presence of
sulfuric acid to form gaseous CO2.
1.2 Oxidation of FeSO4 with KMnO4 in an acidic medium (sulfuric acid) to form
Fe2(SO4)3.
1.3 Based on the reaction in section 1.2, determine the anodic reaction and
cathodic reaction and the relevant cell diagram.
1.4 Derive the expression for electromotive force E of the cell.
2. In the thermodynamics point of view, Gibbs free energy G at constant P, T
condition is closely related to electromotive force E of a redox reaction according
to below expression:
G
G  n F E  E  
nF
where: n – number of electrons transferred,

F – Faraday constant.
The correlation of the standard reduction potential between Mn ions in acidic
medium is:

0 0
MnO4   MnO42 E
0.56V

3 ?
MnO2 E

4?
Mn 3   Mn 2
1.51V
+1.7V +1.23V
MnO42
2.1 Determine the standard reduction potential of the pair MnO2
MnO2
2.2 Determine the standard reduction potential of the pair
Mn 3
3. A process is spontaneous if Gibbs free energy is negative. Based on the
thermodynamic data:
3.1 Determine Gibbs free energy of the following reaction:
3MnO42- + 4H+ 2MnO4- + MnO2 + 2H2O
3.2 Is the reaction spontaneous?
3.3 Calculate Kc for the reaction.
Problem 11. Phosphoric acid

A is a solution of H3PO4 with pH of 1.46.
1. Calculate the molar concentrations of all species in solution A. Given that Ka
values for H3PO4 are 7.2×10−3; 6.3×10−8 and 4.2×10−13, respectively.
2. Mixing of 50 ml of solution A and 50 ml of 0.4 M NH3 solution results in 100
ml of solution B. Calculate pH of solution B ( pK NH  9.24 ).


4
3. 100 ml of solution B is mixed with 100 ml of 0.2 M Mg(NO 3)2 solution.

Determine if precipitate of NH4MgPO4 forms. The hydrolysis of Mg2+ is ignored
and precipitation of NH4MgPO4 is assumed to be the only reaction, given that Ksp =
2.5×10−13.
4. Calculate the solubility (mol·L−1) of Ca3(PO4)2, given Ksp = 2.22×10−25.
(Hint: The hydrolysis of Ca2+ is ignored).

Problem 12. Chemical Kinetics
Thermal decomposition of dinitrogen pentoxide (N2O5) in the gas phase has time-
independent stoichiometry.
2 N2O5 (g) → 4 NO2 (g) + O2 (g) (1)
A kinetic measurement for N2O5 at 63.3 oC is shown in Figure 1 below.
4.00E-03
[N2O5]
Time [N2O5]/
3.50E-03
−3
(s) mol∙dm
3.00E-03
0 3.80×10−3
50 3.24×10−3 2.50E-03
-3
[N 2 O5 ]/mol.dm
100 2.63×10−3
150 2.13×10−3 2.00E-03
225 1.55×10−3
1.50E-03
350 9.20×10−4
510 4.70×10−4 1.00E-03
650 2.61×10−4
800 1.39×10−4 5.00E-04
0.00E+00
0 100 200 300 400 500 600 700 800 900
Time/ s
Figure 1. Concentration of N2O5 versus time.

1. What is the half-life (t1/2) for the decomposition of N2O5 at 63.3 oC?
2. The reaction order for the reaction (1) can be determined by plotting of ln
[N2O5]0/[N2O5]t versus time or {[N2O5]0/[N2O5]t -1} versus time.
2.1 Plot the graphs into the two figures below to determine the reaction order?

2.2 Write down the rate law and integrated rate equation.
3.5
3
ln{[N2 O5 ]0 /[N2 O5 ]t}
2.5
1.5
0.5
0
0 100 200 300 400 500 600 700 800 900
Time/ s
Figure 2. A re-plot of the data in Figure 1 as function of ln {[N2O5]0/[N2O5]t} versus time

30
25
20
{[N2O5 ]0 /[N2O5 ]t}-1
15
10
0
0 100 200 300 400 500 600 700 800 900
Time/ s
Figure 3. A re-plot of the data in Figure 1 as function of {[N2O5]0/[N2O5]t -1} versus time
3. Determine the rate constant for the reaction (1).
4. The rate constant k for (1) at 45 oC is of 5.02×10-4 s−1. Calculate the activation
energy (Ea) and pre-exponential factor (A) for the reaction (1) assuming that the
activation energy and pre-exponential factor are temperature independent.
5. The following mechanism is proposed for the reaction (1):

k1
N2O5 k-1 NO2 + NO3 (2)

k2
NO2 + NO3 NO2 + O2 + NO (3)
k3
NO + NO3 2 NO2 (4)
Using this mechanism, derive the rate law for -d[N 2O5]/dt assuming that the
intermediate concentrations can be treated by the steady-state approximation.
Problem 13. Kinetics of the decomposition of hydrogen peroxide
In order to decompose hydrogen peroxide (H2O2) with iodide ion as catalyst in

neutral solution, the 3 % H2O2 solution (which approximately corresponds to 30 g
of H2O2 in 1 L of solution) is mixed with 0.1 M KI solution and water at different
volumetric ratios; and the volume of the oxygen gas released VO (mL) is 2
measured.
Experiment VH 2 O2
(mL) VKI (mL) VH 2 O ( mL) VO2 (mL / min)
at 298 K and 1 atm

1 25 50 75 4.4
2 50 50 50 8.5
3 100 50 0 17.5
4 50 25 75 4.25
5 50 100 0 16.5
-
1. Determine the reaction order with respect to H2O2, and I , respectively.
2. Write down the chemical reaction, and determine the rate law.
3. Calculate the molarity of H2O2 at the beginning of the experiment #4 and after 4 min.
4. The reaction mechanism involves a series of the following steps:
H2O2 + I− 
k1
H2O + IO− (1)
IO− + H2O2 
k2
O2 + I− + H2O (2)

Do the two above steps have the same rate or different rates? Which step
determines the overall rate of the oxygen release? Justify your answer.
Problem 14. Magnetism of transition metal complexes
A transition metal complex containing diamagnetic ligands can be overall

diamagnetic (all electrons are paired) or paramagnetic (having unpaired
electron(s)) depending on the electronic configuration of the central metal ion, the
nature of the ligand, and geometry of the ligand sphere. The magnitude of
paramagnetism of a metal complex is commonly reported in terms of the effective
magnetic moment (μeff) which can be obtained from the experimental measurement
of molar magnetic susceptibility (χm) and is commonly expressed in Bohr
magneton (BM).
Theoretically, the magnetic moment is contributed by two components, the spin
angular momentum and the orbital angular momentum. For many complexes of
first row d-block metal ions, however, the contribution of the second component
can be ignored. Thus, the so-called spin only magnetic moment can be determined
by the number of unpaired electrons, n:
1. The observed effective magnetic moment of two octahedral complexes,

K4[Mn(CN)6].3H2O and K4[Mn(SCN)6] are 2.18 BM and 6.06 BM, respectively.
1.1 Calculate number of unpaired electrons in each complex. Which complex is
low spin? Which complex is high spin?
1.2 Rationalize your answers by applying crystal field theory.

2. Calculate the μ (spin only) of complex [Ni(H2O)6]Cl2.
3. In practice, the experimentally observed μeff value of [Ni(H2O)6]Cl2 is 3.25 BM.

This is not surprising due to the fact that magnetic moment of octahedral
complexes of Ni2+ (d8) usually does not obey the spin only formula. In these cases,
the contribution of orbital angular momentum should be taken into account. The
simplification of spin-orbit coupling model can be applied to calculate their
magnetic moment:
where λ is spin-orbit coupling constant of Ni2+ and has the value of -315 cm−1
Δoct is the crystal-field splitting parameter
Calculate the effective magnetic moment of [Ni(H2O)6]Cl2 taking into account
spin–orbit coupling. Δoct of [Ni(H2O)6]2+ is 8500 cm-1.
4. Dibenzoylmethane (DBM) is a well known chelating κ-O,O-ligand which can

form stable complexes with many transition metal ions.
DBM
Reaction of Ni(CH3COO)2.4H2O with DBM in EtOH - H2O solution gives light

green crystalline complex A which loses 6.8 % of mass on heating at 210 oC in the
air to form green solid B. The substance B is quantitatively converted to brown
prismatic crystals C by re-crystallization in dry toluene. B and C are two
polymorphic forms and their inter-conversion is reversible. The X-ray single
crystal structure of C shows a square planar geometry with the chemical

composition of [Ni(DBM)2]. While B is paramagnetic with effective
magnetic moment of 3.27 BM, the complex C is diamagnetic. When B and C are
kept in the air, they slowly convert to A. This happens much faster in the presence
of some organic solvents (Inorg. Chem., 2001, 40, 1626-1636).
4.1 Draw the splitting diagram of the d orbitals of Ni 2+ in C and confirm its
diamagnetic property.
4.2 What is the molecular formula of A? Assume that A is a mononuclear
complex.
4.3 The effective magnetic moment of A is 3.11 BM (Synth. React. Inorg. Met. Org.
Chem., 2009, 39, 694-703). What is the most suitable molecular geometry of A?
(Assuming that If A is an octahedral complexes, Δoct of A is similar to that of

[Ni(H2O)6]2+).
4.4 Draw all possible isomers of A.
4.5 What do you expect for the molecular geometry of B?
Problem 15. Structure and synthesis of Al-Keggin ion
1. A molecular dimer of aluminum chloride in gas phase has the structure:

1.1 What is the hybridization of the Al atoms in a dimer?
1.2 Determine the distance between two Al atoms.
2. Aluminum chloride dissociates in basic solution yielding several Al-polycations.

A typical Al-Keggin ion with the molecular formula of [Al13O28H24.12H2O]Cln was
formed at a hydrolysis ratio [OH-]/[Al3+] of 1.5 to 2.5. It is only composed of
tetrahedral and octahedral Al cations. The 27Al NMR spectrum of an Al13 ion is
shown below. The sharp signal at 64 ppm is due to the very symmetrical
environment of the corresponding Al atom(s) in the Keggin cation.
2.1 Determine the absolute value of (n) in the Al13 Keggin ion.
2.2 Assign 27Al NMR signals in the spectrum to the appropriate Al cation(s) in the
right figure.
2.3 In an Al13-Keggin ion, Al tetrahedron(s) is(are) only linked with other Al atoms
by the oxygen bridge. Propose the structural formula for the Al13-Keggin ion.
2.4 Determine the number of oxygen atoms bridging adjacent octahedra.
2.5 Write down the overall equation to prepare Al-Keggin ions from the reaction
between NaOH and AlCl3 solution.
3. Al13-Keggin ions have recently been prepared by solid - solid interaction
referred to as mechanochemical synthesis [J. Catal. 245 (2007) 346; Inorg. Chem.

Commun. 11 (2008) 1125]. A mixture of (NH4)2CO3/[Al(H2O)6]Cl3 was
blended together in a silicon carbide crucible (with the inner volume of 15 cm 3) in

the presence of three hardened silicon carbide balls (with the radius of 0.542 cm) in
atmospheric condition (25 oC, 1 atm). The milling was kept for a period of time at
25 oC until the pressure gauge remains at constant value of 2.50 atm (Hint: The
volume of solids is negligible).
3.1 Write down the overall reaction between aluminum hexahydrate chloride and
ammonium carbonate to yield the Al13 -Keggin ions.
3.2 Determine the number of molecular Al13-Keggin cations in the crucible.
Problem 16. Safrole
Safrole (4-allyl-1,2-methylendioxybenzene) is obtained from oil extracted from

sassafras, an evergreen tree growing in the central and northern regions of
Vietnam. Safrole has interesting functionality and chemical reactivity suggesting
its use as an efficient and versatile natural synthon in the synthesis of numerous
biologically active compounds. [PtCl(Safrole-1H)(Pyridine)] is a complex with a
similar activity to the anticancer drug Cisplatin. [PtCl(Safrole-1H)(Pyridine)] has
been synthesized for the first time by chemists at the Department of Chemistry,
Hanoi National University of Education. The reaction scheme is given below.
O EtOH, Heat
K[PtCl3(C2H4)] + K[PtCl3(C10H10O2)] (A)
O (1)
(Safrole) (2) EtOH,H2O
Pyridine, EtOH
(C) [PtCl(C10H9O2)(C5H5N)] [Pt2Cl2(C10H9O2)2] (B)
(3)
Some spectral signals of uncoordinated safrole and coordinated safrole in A, B and

C are given below.

3 8 IR
O 2 4 9
1
7
O 1
5
10
absorption, H NMR signals of aromatic protons, δ (ppm)
6
νC9-C10 , cm-1
Uncoordinated 1630
Coordinated in
1510
A
Coordinated in
1495
B

Coordinated in
1500
C
1. Write balanced equations for the three reactions in the above scheme.
2. What information about the coordination of safrole with Pt in A, B and C can be
obtained from the IR and 1H NMR data?
3. Draw the structures of A, B and C, given that in C pyridine is in the cis-position
with respect to the allyl group of safrole.
4. What is the driving force of each of the reactions (1), (2) and (3)?
5. Why does reaction 3 not seem to obey the trans effect?
Problem 17. Imidazole
Heterocyclic chemistry is one of the most important fields of organic chemistry

and biochemistry. Approximately 55% of publications in organic chemistry are
related to the field, and the number of heterocyclic compounds recently found is
far more than that of homocyclic compounds. The five-membered ring compounds
with two heteroatoms are often present in many substances that are important for
life. For example, imidazole ring is present in the essential amino acid, histidine,
and its decarboxylation product, histamine. Histidine residues are found at the
active sites of ribonuclease and of several other enzymes and play a vital part in the
structure and binding functions of hemoglobin. Several drugs are based on the
imidazole ring such as nitroimidazole, cimetidine, azomycin, metronidazole,
midazolam.

1. Draw the structures of 1,3-diazole (imidazole, C3H4N2), imidazol-1-ide anion,
imidazolium cation, 1,3-oxazole (oxazole, C3H3NO) and 1,3-thiazole (thiazole,
C3H3NS). Which structure(s) can be considered aromatic?
2. Arrange imidazole, 1,3-oxazole and 1,3-thiazole in decreasing order of melting

and boiling points and justify your order.
3. Using structural formulae, write down equations for the ionization of imidazole,
oxazole, and thiazole in water. Arrange the substances in decreasing order of base
strength and justify your answer.
4. Propose a reaction mechanism showing the catalytic behavior of imidazole in

hydrolyzing RCOOR’ without a participation of OH –. Justify this behavior based
on the structure of imidazole.
5. Propose a reaction mechanism for the formation of 1,1’-carbonyldiimidazole
(C7H6N4O, CDI) from imidazole and phosgen (COCl2).
6. Explain why the C=O IR stretching frequency in 1,1’-carbonyldiimidazole is

100 cm–1 higher than that of 1,1’-carbonyldipyrrolidine (CO(C4H8N)2).
7. Write down reaction equations for the preparation of CDI (a) using a mixture of
4 mol imidazole and 1 mol phosgene and (b) using a mixture of 2 mol imidazole, 1
mol phosgene, and 2 mol NaOH. Explain why reaction (a) is preferable.
8. CDI is often used for the activation of carbonyl group for the coupling of amino
acids in peptide synthesis.
8.1 Use curly arrow mechanisms to complete the scheme below, showing the
formation of the active compound G from CDI and Alanine.

O
O
N N C N N A D O
C F N N C R C E
O H B E (G) O
H3C HC C
NH2 O
8.2 Propose a reaction mechanism for the formation of dipeptide Ala-Gly from G
and Glycine.
Problem 18. Small heterocycles
Heterocyclic compounds containing the CF3 group are interesting targets of

advanced researches to generate biologically active compounds. It is quite difficult
to bring the trifluoromethyl group into saturated heterocyclic structures, especially
heterocycles containing nitrogen. However, these heterocycles bearing CF3 groups
have several promising applications. Therefore, studies of such compounds have
been carried out by many chemists.
Trifluoroacetaldehyde (A) was treated with ethanol and then refluxed with
benzylamine in toluene to afford compound B (C9H8NF3). The reaction of
compound B with ethyl diazoacetate in diethyl ether with boron trifluoride etherate
(BF3.Et2O) as a catalyst at -78 oC for 4 hours provided compound C (C13H14NO2F3).
The reduction of compound C by LiAlH4 in THF at room temperature for 2 hours
formed compound D. Then, D reacts with hydrogen in the presence of Pd(OH) 2 as

a catalyst in CH2Cl2 at room temperature for 60 hours to obtain E (C4H6NOF3).
Compound E was then allowed to react with 2 equivalents of tosyl chloride (TsCl)
in dicloethane with Et3N and an amount of 4-dimethylaminopyridine (DMAP) as
catalyst. The reaction was carried out at room temperature for 2 hours, then 3 hours
of reflux, to furnish compound F. F reacted with 1.2 equivalents of phenol in the
presence of K2CO3 in DMF to form compound G (C17H16NSO3F3).
A derivative of G can be synthesized according to the following diagram:
O O BnNH2 3 NaBH4
CH3COOH CH3CH2OH
H I
CHCl3 (C13H14NO2F3) THF
F3C OC2H5
1.1 equi SOCl2 2.2 equi LiHMDS

CH2Cl2
I K L (C11H12NF3)
N2, THF
1. Complete synthetic schemes from B to L.

2. Write reaction mechanisms from B to C.
3. Write reaction mechanisms from F to G.
Note:
BnNH2: benzylamine, C6H5CH2NH2;

Bn: Benzyl, C6H5CH2-, THF: tetrahydrofuran
LiHMDS: Lithium bis(trimethylsilyl)amide, Et: C2H5-;
Equi: equimolarity
Problem 19. Vitamin H

Vitamin H or biotin is a highly effective growth promoter which plays an

important role in many organisms, for instance baker’s yeast (Saccharomyces
corevisiae). Human beings have different demand in biotin depending on age. Lack
of biotin can lead to diseases such as dermatitis, absence of appetite, fatigue,
muscular pain and nerve perturbance.
Biotin was first found in 1901 by Wildiers as a growth-promoting vitamin of
yeasts. Thereafter, it was found in egg yolk (by Kögl, 1936) and in liver (by Szent-
Györgyi, 1936). The absolute configurations of chiral carbons of biotin were
established by Trotter and Hamilton in 1966 by the single-crystal X-Ray
diffraction. The molecule of biotin has three chiral carbons. Hence, there are
theoretically eight diastereomers. Only the (3aS, 4S, 6aR)-(D)-(+)-biotin, however,
shows the high bioactivity.
O
1 2
HN NH
(R) 6a 3a (S)
6 5 (S)
S 4 COOH
(D)-(+)-Biotin
In 1982, researchers from Hoffmann-La Roche published an elegant synthesis

procedure for (D)-(+)-Biotin from the methyl ester of the amino acid L-Cysteine
with the following steps.
1. The thiol group of the methyl ester of L-cysteine was transformed into a
disulfide S-S bond (compound A) in an oxidation reaction. A was then treated with
hex-5-inoyl chloride to give compound B which was subsequently reduced by
Zn/CH3COOH to afford a thiol. This compound was cyclized by the addition of the

–SH group to the terminal alkyne under atmospheric condition, resulting in the
formation of C with a ten-membered ring containing a (Z) C=C double bond. Write
down the structural formulae of A, B and C in the hereunder scheme.
Cl
2
S
O Zn, AcOH
MeO2C B C (C10H15NO3S)
6a R C5H5N, CH2Cl2 Không khí, 25°C
o
NH2 Air, 25 C
0°C
A
2. The reduction of C by diisobutylaluminium hydride ((i-Bu)2AlH, DIBAL)

resulted in the formation of (D). The condensation reaction between D and
benzylhydroxylamine in dichloromethane produced nitrone E (a nitrone is an
organic compound which contains a > C=N+-O- group). E underwent a 1,3-dipolar
intramolecular cyclization reaction to afford polycyclic compound F of which the
two heterocycles, isoxazolidine (1,2-oxazolidine) and tetrahydrothiophene, shared
a common bond. The cyclization reaction resulted in the (S) configurations of the
two carbons at the common bond and the (R) configuration of the carbon
connected to the oxygen. Write down the structural formulae of D, E and F.
(i-Bu)2AlH Ph NHOH 
C D (C9H13NO2S) E (C16H20N2O2S) F
PhMe, -78°C CH2Cl2 PhMe
3. When F was reduced with Zn powder in acetic acid, the N-O bond of the
heterocycle isoxazolidine was broken to give compound G. The reaction between
G and chloroformate in the presence of Na2CO3 in THF resulted in the formation
of compound H. The treatment of H in a hot solution of Ba(OH) 2 in dioxane,
followed by an acidic work-up yielded the bicyclic δ-hydroxy acid I containing all

the chiral centers of (D)-(+)-Biotin but with an “excessive” -OH group.
Draw the structures of G, H and I and explain the formation of I from H.
1) Ba(OH)2
Zn, AcOH, H2O ClCO2Me Dioxan, H2O
F G (C16H22N2O2S) H (C18H24N2O4S) I (C17H22N2O4S)
70°C Na2CO3, THF 2) H3O
4. I was treated with SOCl2 to yield the corresponding chloride acid K, given that
the configuration of the carbon attached to the “excessive” -OH is maintained in K.
Ester L was formed when K was reacted with methanol. L was reduced with
NaBH4 in dimethylformamide at 80oC to give ester M which was hydrolyzed in
aqueous acidic solution of HBr to give optically pure (D)-(+)-Biotin. Draw the
structures of I, K, L and M and the intermediates to explain the influence of the
sulfur atom on the stereochemical outcome of K.
Problem 20. No perfume without jasmine
The Spanish jasmine originated from the valleys of Himalaya. This so called
Jasminum grandiflorum L., which was grafted on the wild Jaminum officinale L,
has the possibility to resist against the cold of the mountain climate. In 1962, E.
Demole and E. Lederer successfully isolated and clearly determined the structures
of the important flavor component of the essential oil of jasmine. It was actually a
mixture of two diastereomers (Z)-(3R,7R) methyl jasmonate and (Z)-(3R,7S)
methyl jasmonate with the structures shown below.

COOMe COOMe
O O
(Z)-(3R,7R) metyl
methyljasmonat
jasmonate (Z)-(3R,7S) metyl
methyljasmonat
jasmonate
Due to its important role in perfume industry as well as its limited natural resource,
the synthesis of jasmonates has attracted interest of many chemists. The first
synthesis of optically pure (Z)-(3R,7S)-methyl jasmonate was carried out in 1990
by Helmchen with the following steps:
1. The first step in the synthesis is a Diels-Alder reaction between cyclopentadiene

A and ester B of fumaric acid with (S)-ethyl lactate to yield C.
O COOEt
O
+ O  LiOH
C D (C9H10O4)
THF/H2O
A EtOOC O
B
A cyclo-addition reaction, a kind of pericyclic reaction, involves bonding

between the termini of two π systems to produce a new ring (scheme below). The
product has two more σ bonds and two less π bonds than the reactants. The Diels-
Alder reaction, or so called [4+2], is a common thermally activated cycloaddition
whose stereoselectivity is syn addition. In this concerted syn addition, the
stereochemical relationships among the substituents are retained in the product(s).

+
The hydrolysis of C in basic solution followed by an acidification step resulted in

the formation of D. Draw the structures of C and D.

2. The reaction between D and I2 in KI solution gave rise to the
formation of the five-membered ring lactone of the endo –COOH group. When
heated under basic condition, E underwent a decarboxylation-cyclization reaction
to produce compound F. The hydrolysis in basic medium followed by oxidation
with NaIO4/RuO4 transformed F into γ-keto acid G. Write down the structures of E
to G.
KI3 KOH 1. NaOH
D E F G
DMSO, 175°C 2. NaIO4, RuO4
-CO2
3. G was reacted with HI to yield compound H containing only five-membered

rings. When H was reduced by Zn/KH2PO4 in tetrahydrofuran, it transformed into
carboxylic acid I which was then oxidized in a Bayer-Villiger rearrangement with
meta-chloroperoxybenzoic acid (m-CPBA) to give the major product K. K was
treated with oxaloyl chloride, followed by a Pd/BaSO 4 catalyzed reduction with H2
(Rosenmund reduction) to give L. Compound M was separated from the Wittig
reaction mixture between L and the yield Ph3P =CHOCH3. Draw the structures of
the compounds from G to L.
HI Zn m-CPBA
G H (C8H9IO3) I (C8H10O3) K (C8H10O4)
KH2PO4, THF/H2O
1. (COCl)2 Ph3P=CHOMe
L (C8H10O3) O
2. H2, Pd/BaSO4
O OMe
M
4. Hydrolysis of M in THF/H2O solution of acetic acid produced N which

underwent a Wittig reaction with the ylide Ph 3P = CHCH2CH3 to form O. The
hydrolysis of O in basic solution, followed by a neutralization step and then

treatment with diazomethane resulted in the formation of P. In the last step, the
target molecule, (Z)-(3R,7S)-methyl jasmonate Q, was obtained in the oxidation
reaction of P with pyridinium dichromate. Draw the structures of compounds from
N to P.
1. NaOH
Ph3P
AcOH 2. H Py2Cr2O7
M N (C9H12O3) O P Q
THF/H2O CH2Cl2
3. CH2N2
Problem 21. Vietnamese cinnamon
Cinnamomum loureiroi, also known as Vietnamese cinnamon, is an evergreen

tree grown in the central and northern regions of Vietnam. Aromatic bark of the
tree has medicinal and culinary value. Essential oil of the bark contains
cinnamaldehyde ((2E)-3-phenylprop-2-enal) as the main component.
Mild oxidation of cinnamaldehyde with NaClO2 affords an acid A. A undergoes
subsequent esterification with ethanol to form ethyl cinnamate (B). Refluxing ethyl
cinnamate and 80% hydrazine hydrate solution for 10 h gives C (C9H10N2O).
Refluxing C and p-nitrobenzaldehyde in ethanol for 12 h affords D (C16H13N3O3).
NaClO2 EtOH/H+, Reflux
Cinnamaldehyde A C11H12O2 (B)
N2H4.H2O Reflux, 10 h
p-O2NC6H4CHO
C16H13N3O3 (D) C9H10N2O (C)
EtOH, Reflux, 12 h
1
H NMR spectra of C and D are given below (the multiplicity and relative intensity
is shown for each signal).

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

2. Assign 1H NMR signals in the first spectrum to appropriate proton groups of C.

3. Propose a reaction mechanism for the formation of C from B.
4. Among four given below structures, select one for D and give the reasons for
your selection.
NO2 NO2
NO2 NO2
H O
HC O O
N O HC N N
N HC
N HC N N N
(D1) (D2) (D3) (D4)
5. Assign 1H NMR signals in the second spectrum to appropriate proton groups of D.
Problem 22. Cinnamic acid
1. Ultraviolet irradiation of trans-cinnamic acid ((E)-3-phenylprop-2-enoic acid) in

solution yielded a mixture of cis-cinnamic and trans-cinnamic acids. trans-
Cinnamic acid can be crystallized in two forms: α-form or β-form. Ultraviolet
irradiation of crystalline trans-cinnamic acid in the α-form yielded α-truxillic acid
(2,4-diphenylcyclobutane-1,3-dicarboxylic acid). Ultraviolet irradiation of
crystalline trans-cinnamic acid in the β-form yielded β-truxinic acid (2,3-
diphenylcyclobutane-1,4-dicarboxylic acid). α-Truxillic acid possesses a
symmetric center. In β-truxinic acid, the two phenyl groups are on the same side of
the cyclobutane ring, and the two carboxyl groups are on the opposite sides.
1.1 Propose a reaction mechanism for the isomerization of trans-cinnamic acid.

1.2 Draw the structure of α-truxillic acid and all its diastereoisomers.
1.3 Draw the structure of β-truxinic acid and all its diastereoisomers. Show the
structures which have enantiomers.
1.4 Suggest how the different packing arrangements of trans-cinnamic acid in the
α- and β- crystal forms leads to the different structures of α-truxillic and β-
truxinic acid.
1.5 Why does cinnamic acid not dimerize in solution upon ultraviolet irradiation?
2. Hydrolysis of α-truxilline (C38H46N2O8, an alkaloid obtained from Truxillo coca)

gives α-truxillic acid, methanol and an acid A (C9H15NO3). Oxidation of A with
pyridinium chlorochromate (PCC) leads to B, which is readily decarboxylated to
form optically inactive ketone C (C8H13NO). Oxidation of C with potassium
permanganate gives N-methylsuccinimide.
O
PCC - CO2 KMnO4/H2O
A C9H15NO3) B C C8H13NO) N CH3
2.1 Propose the structures of A, B, C. Are A, B optically active or not? Explain.

Why C is optically inactive?
2.2 Propose the structure of α-truxilline. Is α-truxilline optically active or not? Explain.
Problem 23. Tris(trimethylsilyl)silane and azobisisobutyronitrile
In the late eighties, Chatgilialoglu and coworkers introduced

tris(trimethylsilyl)silane, (TTMSS or (TMS)3SiH) as a radical-based reducing
agent for functional group modifications and a mediator for sequential radical

reactions. The use of (TMS)3SiH allows reactions to be carried out under mild
conditions with excellent yields of products and remarkable chemo-, regio-, and
stereoselectivity. (TMS)3SiH is an effective reducing agent for the removal of a
variety of functional groups. Examples of dehalogenation (Cl, Br and I) and
reductive removal of chalcogen groups (SR and SeR) are well known. The most
popular thermal initiator is azobisisobutyronitrile, {AIBN, [(CH 3)2C(CN)]2N2}
under heating conditions in toluene.
1. Reactions using TTMSS and AIBN are given in the hereunder examples.
1.1 Radical cyclisation was studied using two different reducing agents: tributyltin
hydride (TBTH, Bu3SnH) and tris(trimethylsilyl)silane (TTMSS).
Ts Ts
R N R N
TTMSS or Bu3SnH
Br AIBN, toluene, 80 oC
R'O2C R'O2C
1.2 Radical introduction of a side chain (alkylation)
2. TTMSS has found multiple applications in the organic synthesis described in the
below reactions:
2.1 The compound (I) was converted to B and C via the radical intermediate A.

I TTMSS / AIBN
(I) A B C
Benzene, reflux
Reductive product Cyclisation product
2.2 The compound (II) was converted to D.

Br TTMSS
O AIBN,
D
O O
(II)
2.3 The compound (III) was converted to E, and then through several steps to
afford (±) - vindoline
N3 N
I
TTMSS / AIBN
E Et
Toluene, to OAc
MeO N OBn OMe N
Me Me HO CO2Me
(±)-Vindoline
(III)
2.4 Horsfiline (J) is an oxindole alkaloid found in the plant Horsfieldia superba,
which has analgesic effects. The method for horsfiline synthesis from the
compound (IV) was described below:
Bn
Bn N
N O O
TTMSS / AIBN + H+ MeO
F G I
Benzene, - N2
NMe
MeO I
J
N3 (+/-)-Horsfiline
(IV)

Write down the structural formulae of all compounds A to I given in the above reactions.
Problem 24. (–)-Menthol from (+)-δ-3-Carene
Carene, or δ-3-carene, is a bicyclic monoterpene which occurs naturally as a

constituent of turpentine. (+)-δ-3-Carene has the required structural features to
serve as a starting material for (-)-menthol.
The procedure of preparation of (-)-menthol from (+)-δ-3-carene was described as follows.
Catalytic isomerization of δ-3-carene provides the needed (+)-δ-2-carene (A)
which then was pyrolysed to cleave the cyclopropane ring. The resultant 2,8-
menthaldien (B) had the right stereochemistry at C1 and C4 of (–)-menthol.
Treatment of the unconjugated diene B with 1 equivalent mole of HCl gives C and
then, dehydrochlorination leads to a conjugated diene (D).
CH3
HCl HO-
S A B C D
R
H 3C
CH3
1S, 6R-(+)-delta-3-Carene
Treatment of D with hydrogen chloride affords 8-chloro-3-p-menthene (E) which

then reacted with sodium acetate and acetic acid to give mixed (cis/trans) pulegol
esters (F) via allylic displacements. Hydrolysis of F affords (-)-cis and (+)-trans-
pulegol (G).

Because the absolute configuration of C-1 is fixed in this system,
reduction of either pulegol isomer provides menthol isomers which can be readily
equilibrated to predominently (-)-menthol.
CH3
HCl AcONa HO- H2

D E F G
AcOH
HO
(-)-Menthol
Write down the structural formulae of the compounds A to G.
Problem 25. Cefalotin

Cefalosporin is a β-lactam group antibiotic. Cefalotin, a derivative of
cefalosporin, has stronger activities on gram (-) and gram (+) bateria, but lower
toxicity. Therefore, it has been studied and applied into medical treatment.
Cefalotin has been synthesized from L-cisteine according to the following diagram:

HO2C acetone t-BuOH
tBuOH CH2N2
H B C D
H2 N SH COCl2
C6H11NO2S C11H19NO4S C12H21NO4S
MeO2C
N
N
CO2Me Pb(OAc)4 MeOSO2Cl
E F G
NaOAc, MeOH NaN3
C16H27N3O8S C12H21NO5S C12H20N4O4S
OHC
CHCO2CH2CCl3
Al(Hg) Al(O-iBu)3 OHC
H I K
C11H18N2O3S C18H23Cl3N2O7S
S CH2COCl
CF3CO2H B 2 H6 Ac2O
L M N O
C10H9Cl3N2O4S
CO2H
O CH2OAc
Pyridine Zn N
P O
AcOH N S
S H
Cefalotin
1. Complete the above synthetic scheme.

2. Write down a reaction mechanism from K to L.
3. How many optical isomers of cefalotin should be expected?
Problem 26. Heterocyclic compounds
Recently, several transformations of levulic acid (4-oxopentanoic acid) have
been reported in the Journal of Chemistry (Vietnam). One of them is the synthesis

of three hydrazides (RCONHNH2) from levulic acid in which R is one of
the followings:
CH2
N N
O
Ph
Compound A Compound B Compound C

Assuming that you have: inorganic chemicals, levulic acid, other acyclic
organic compounds, benzene derivatives (PhCHO, PhNCS, 3-
NO2C6H4SO3Na), catalysts (piperidine, TsOH), and solvents.
1. Provide the synthetic scheme to obtain A. What is the purpose of 1,3-dioxolane

ring formation? Write down the reaction equation to prepare TsOH from toluene.
2. Provide the synthetic scheme to obtain B. What is the reation mechanism using
PhNCS? Write down the reaction equation to synthesize PhNCS from aniline?
3. Provide the synthetic scheme to obtain C. What is the role of 3-O2NC6H4SO3Na?

Write down the reaction equation to prepare 3-O2NC6H4SO3Na from benzene.
Using signals from proton nuclear magnetic resonance spectroscopy to prove that
the reaction with 3-O2NC6H4SO3Na has occurred?
4. The three hydrazides (A, B, and C) are reacted with PhCHO to generate
corresponding products (E, F, and G). Draw a common reaction mechanism for
these transformations. If 4-NO2C6H4CHO or 4-Me2NC6H4CHO was used instead of
PhCHO, would the reactions be more difficult or easier to proceed?
Problem 27. Lotus
Lotus is known as the scientific

name of Nelumbo nucifera. Recently,

Vietnamese researchers collaborating with Canadian scientists discovered the
ability to promote the production of insuline in β cells of nuciferine, which may be
used to treat the Hypoglycemia. (K. Hoa Nguyen, H.Dien Pham, B.L. Gregoire
Nyomba et al. J. of Ethnopharmacology, 2012, 142, 488-495). There are some
ways to synthesize nuciferine from different reactants, but the synthetic procedures
are almost very complicated and the reaction yield is very low. Chia-Fu Chang et
al. at Changhua National University (Taiwan) reported a procedure to synthesize
the nuciferine through 3 steps using a benzaldehyde derivative in Nef reaction,
Pictet-Spengler reaction and radical cyclization (Synth. Commun., 2010, 40, 3452-3466,).
1.NaOH
R2CHNO2 2.H2SO4 R2CO + 1/2N2O
- Nef ‘s reaction (John Ulric Nef, 1894):
The mechanism of Nef’s reaction:
- -
O R1 O R1 R1
- + H+
N+ + OH N+ O + 1/2N2O
- H2O -
- H2O
O R2 O R2 R2
1.NaOH
CH3CH2NO2 CH3CHO + 1/2 N2O
2.H2SO4
Example:
- The radical cyclization reaction:

Radical initiator: AIBN [azobisisobutyronitrile, Me2C(CN)N=NC(CN)Me2]
The Pictet-Spengler addition-cyclization (Amé Pictet, Theodor Spengler, 1911): is
the condensation reaction and then cyclization between β-arylethylamine and
aldehyde or ketone in the presence of acid catalyst with heating. Example:

+ o
NH2 RCHO, H , t
NH
NH NH
R
The reaction scheme for the synthesis of nuciferine is:

Step 1: Synthesis of N-methoxycarbonyl amine.
NHCOOMe
MeO CHO LiAlH4
CH3NO2 MeO
A1 THF A2 (a3)
AcONH4 (A3)
(C10H11O4N) 0 oC (C10H15O2N)
MeO AcOH
MeO
Step 2: Synthesis of arylacetaldehyde.
CHO
CH3NO2 NaBH4 (b3) CHO
B1 B2 (B3)
AcONH4
(C8H6O2NBr) CH2Cl2 (C8H8O2NBr)
Br AcOH Br
Step 3: Synthesis of nuciferine
MeO
AlBN,
BF3-OEt2 Bu3SnH LiAlH4
N
A3 + B 3 X1 X2 MeO Me
CH2Cl2/CHCl3 (1:1) - HBr THF
(C20H22O4NBr) (C20H21O4N)
Nuciferine
1. Determine the structural formulae for A1, A2, B1, B2, X1, X2, reaction conditions
for (a3), (b3).

2. Indicate the reaction mechanism for the formation of A1 from 3,4-
dimethoxybenzaldehyde (step 1); X1 from A3 + B3 (step 3).
3. Determine the structural formulae for two isomers of Y1a, Y1b and compound Y2
based on the schematic conversion below:
Y1a + Y1b 1. CH3I excess/Ag2O CHCl3, NaOH 50% Y2

2. Heated
Nuciferine
(C20H23O2N) Bu4NCl (C20H21O3N)
Problem 28. NMR Spectra
1. At room temperature, the NMR spectrum of cyclohexane shows only a single

resonance signal. As the temperature of the sample is lowered, the sharp single
signal broadens until at -61.0 °C it begins to split into two broaden signals. As the
temperature is lowered further to -90 °C, each of the two signals begins to give a
splitting pattern of its own. Explain the origin of these two families of signals.

H H
H
H H H
H H H
H
H H
2. In cis-1-bromo-4-tert-butylcyclohexane, the proton on carbon-1 is found to give

resonance at 4.33 ppm. In the trans isomer, the resonance of the C1 hydrogen is at
3.63 ppm. Why do these compounds have different chemical shift values for the
C1 hydrogen? Justify why this difference cannot be observed in the 4-
bromomethylcyclohexanes except at very low temperatures.
Problem 29. IR spectra
1. Substitution of an amino group on the para position of acetophenone shifts the

C=O frequency from about 1685 to 1652 cm −1, whereas a nitro group attached to
the para position yields a C=O frequency of 1693 cm −1. Explain the shift for each
substituent from the 1685 cm−1 base value for acetophenone.
2. Conjugation of a C=C double bond with either a carbonyl group or another
double bond provides the multiple bond with more single-bond character (through
resonance, as the following example shows), a lower force constant K, and thus a

lower frequency of vibration. For example, the vinyl double bond in styrene gives
an absorption band at 1630 cm−1. Esters show a very strong band for the C=O
group that appears in the range of 1750–1735 cm −1 for simple aliphatic esters. The
C=O band is shifted to lower frequencies when it is conjugated to a C=C or phenyl
1 K
group (Hint:  
2c 
, µ, reduced mass; c, speed of light).
Assign a structure to each of the spectra shown. Choose from the following 5-
carbon esters.


Part 2. PRACTICAL PROBLEMS

THE SAFETY RULES AND REGULATIONS
Regulations of the International Chemistry Olympiad (IChO)
Safety
(1) During the experimental part, the competitors must wear laboratory coats and
eye protection. The competitors are expected to bring their own laboratory coats.
Other means of protection for laboratory work are provided by the organizer.
(2) When handling liquids, each student must be provided with a pipette ball or
filler. Pipetting by mouth is strictly forbidden.
(3) The use of acutely toxic substances (GHS hazard statement H300, H310, H330)
is strictly forbidden. The use of toxic substances is not recommended, but may be
allowed if special precautions are taken. Substances with GHS hazard statements
H340, H350, H360 (proven mutagens, carcinogens, and teratogens) must not be
used under any circumstances (see Appendix B for definitions of these categories).
(4) Detailed recommendations involving students´ safety and the handling and
disposal of chemicals can be found in Appendices A 1, A 2, and B.
a) Appendix A 1: Safety Rules for Students in the laboratory.
b) Appendix A 2: Safety Rules and Recommendations for the Host Country of the
IChO.
c) Appendix B contains a reference to the hazard symbols and statements of the
Globally Harmonized System of Classification of Chemicals (GHS), the use of
which is expected in labeling and classifying materials used at the IChO.

Problem 30. Condensation between vanillin and benzylamine
1. Introduction
Vanillin is a phenolic aldehyde with the molecular formula C8H8O3. Thus, it has
three types of functional groups including aldehyde, ether, and phenol. This
compound is often used as a flavoring agent in foods, beverages, and
pharmaceuticals. Vanillin is the primary component of the extract of
the Vanilla planifolia. It is known that the aldehyde functional group in vanillin
can be easily converted into enamine derivatives or imides through the
condensation reaction between vanillin and amines. The products are synthones
which are widely applied in the synthetic organic chemistry and pharmaceuticals.
H2N
CHO N
OCH3 CH2Cl2, 
OCH3
OH OH
Molecular Weight: 152.1 Molecular Weight: 241.3
2. Chemicals and Reagents

- Vanillin: 1-2 g
- Benzylamine,
- Dichloromethane: 20 mL,
- Sodium sulfate, Na2SO4
3. Equipment and Glassware

- Erlenmeyer flasks, 250 mL
- Graduated cylinders, 10, 25, 50 mL

- Beral pipets,
- Beakers, 50 mL,
- Hot plate,
- Spatulas,
- Büchner funnel with filter flask and filter paper, separating funnel.
- Melting point apparatus and capillary tubes,
- Small vials with caps,
- Vials with caps, 20 mL
- Thin layered chromatography (TLC) spotters,
- TLC plates (silica with fluorescent indicator A254),
- Chamber for TLC development,
- Magnetic stirrer,
- Ice water bath.
4. Experimental procedure
1. Add 1.0 g of vanillin into a dry 50-mL flask then add 10 mL of dichloromethane
solvent into the flask. The mixture is stirred for 10 min at room temperature, and
then 0.7 g of benzylamine and 2.0 g of Na 2SO4 are simultaneously added into the
flask.
2. The reaction mixture is further stirred at reflux condition (65-67 oC) for 90 min.
Cool the flask to room temperature.
3. Dilute the resultant mixture with 40 mL and swirl the flask.
4. Transfer the mixture into a separating funnel and then extract with 30 mL of
dichloromethane. Extract the organic phase 2 times more with 30 mL of
dichloromethane.

5. Dry the extracting organic fraction with MgSO4. Filter the organic
fraction through a Buchner funnel. Discard the solid and collect the filtrate.
6. Remove the solvent in the filtrate by rotary evaporation to obtain the product(s).
7. Determine the purity of the crude product by thin layer chromatography method.
Use precoated silica gel plates (Silica Gel PF-254) and visualize the spots by UV-
light. Use ethyl acetate: heptane 15:85 mixture as an eluent.
Note: It is recommended to carry out the experiment under a hood.
5. Questions and Data analysis:
1. Weight the obtained product.
2. Draw the mechanism of imine formation.
3. What is the role of Na2SO4 in the present experiment?
Problem 31. Synthesis of eugenoxy acetic acid
1. Introduction
Eugenoxyacetic acid (IUPAC name: 2-methoxy-4-(2-propenyl)phenoxyacetic)
is an odorless, colorless and non-cytotoxic compound. It has shown anti-viral and
anti-bacteria properties and is therefore used as antioxidant food preservative in
food industry. Recently, eugenoxyactetic acid and its ester derivatives such as
methyl and ethyl esters have been found to be the ability to inhibit lipid increasing
which leads to their potential application in the treatment of human
hyperlipidaemia. In addition, eugenoxyacetic acid acts as a promising plant growth
promoter due to their auxin (aryloxyacetic) structural characteristics.

The nature and living organism friendly properties of eugenoxyacetic are the result
of the combination of acetic moiety which is present in vinegar and eugenol moiety
which is the main constituent of the essential oil obtained from clove oil.
OCH3 OCH3
H2C=HCH2C O H H2C=HCH2C O CH2COOH
Eugenol Eugenoxyacetic acid
Clove is an aromatic plant in the family Lamiaceae which is native to tropical areas
and widespread as a cultivated plant. In Vietnam, there are two species of clove,
Ocimum sanctum L. and Ocimum gratissimum L., which have been used in many
tradtional medicinal purposes without adverse effects.
In this practical problem, eugenoxyacetic acid will be synthesized from eugenol
as shown in the scheme below:
OCH3 OCH3
1) NaOH
H2C=HCH2C OH H2C=HCH2C OCH2COOH
2) ClCH2COONa, 80 - 90oC
3) HCl
2. Chemicals and apparatus

- Clove essential oil,
- Monochloroacetic acid,
- NaOH,
- Na2CO3
- Aqueous HCl solution,
- Distilled water.
3. Apparatus and glassware

- Erlenmayer flask: 50 mL,

- Magnetic stirrer with heater,
- Magnetic bar,
- Beaker: 100 mL,
- Beaker: 250 mL,
- Glass filter: 25 mL,
- Glass filter: 50 mL,
- Vacuum filter set (vacuum pump, Filter flask),
- Dropping funnel,
- Spatula,
- Glass rode,
4. Experimental procedure:
Step 1
1. Dissolve 0.6 g NaOH in 3.0 ml distilled water in a 50 mL-Erlenmayer flask and
then add 2.0 mL clove essential oil. Keep the flask in the water bath at 80-90 oC
while stirring with the magnetic stirrer.
2. Dissolve carefully 1.0 g monochloroacetic acid in 5.0 mL distilled water in a 25
mL beaker; stir the solution with the spatula. Add Na 2CO3 slowly just to the
alkaline reaction (Solution A).
Step 2
1. Add slowly the solution A to an Erlenmayer flask and keep stirring the mixture
at 90-95 oC for 60 min. Cool the reaction mixture with water to room temperature,
and then acidify with HCl 1:1 to the acidic reaction (test by litmus paper) (Solution B).
2. Add a small amount of crushed ice (5-10 g) to the solution B and stir until the
yellow oil turns to the solid. Isolate the solid by filtration with suction in to a
sintered glass crucible. Wash the solid with water to obtain the crude product as
pale yellow solid.
Step 3

1. Purify the product as follows: transfer the crude product to a 250 mL beaker, add
80-100 mL hot water (about 90 oC) to the beaker and continue boiling for 5-10
min. Cool the solution with water and ice-cold water.
2. Isolate the product by filtering with suction into a sintered glass crucible and
wash the solid several times to obtain white needles. Dry the solid in the drying
oven for 60 min. Weigh the dried product.
5. Questions and data analysis:

1. Write down the reactions occurring in step 1a, 1b and 2.
2. Calculate the reaction yield.
3. Propose a mechanism for the reaction in step 2.
4. Explain why the reaction must be conducted in alkaline medium? Should an
excess amount of alkaline be used in the reaction?
5. Compare the possibilities of the chlorine atom in monochloroacetic acid and
those in alkyl chlorides to be substituted.
6. If the pure product obtained in the experiment above (mp. 72 oC) is re-
crystallized in benzene, its mp. Will rise to 100.5 oC. Suggest an explanation for
this observation and propose method to test your explanation.
7. When eugenoxyacetic acid is refluxed in KOH solution, and acidified with HCl
(1:1) solution, an isomer of eugenoxyacetic acid, isoeugenoxyacetic acid can be
obtained in the form of two stereoisomers. Determine the structures of these two
isomers and explain the formation of isoeugenoxyacetic acid with a suitable
reaction mechanism.
Problem 32. Complexometric titration of iron, aluminum, and

magnetism in the aqueous solution

1. Introduction
Complexometric titration is one of the most common methods of volumetric
analysis in chemical laboratories. In this method, the most widely used complexing
agent is disodium salt of ethylenediaminetetraacetic acid (EDTA). EDTA is a
polyprotic acid (H4Y). The solution Na2H2Y is used as a standard solution for
titration of metal ions (Mn+):
Mn+ + H2Y2- + 2H2O → MYn-4 + 2H3O+
The formation constant (Kf) of MYn-4 depends on the nature of metal ions. For example:
Metal ions Kf Titrated at pH
3+ 25.1
Fe 10 2.0
3+ 2+ 2+ 16.13
Al , Pb , Zn 10 4.0 – 5.0
2+ 8.69
Mg 10 9.0 – 10.0
Metal ions can be titrated separately due to the formation of MY n-4 complex with
conditional formation constant at a suitable pH condition. In practical, the
metallochromic indicators are usually used for the detection of the end point. These
indicators are the color complexing agents for the metal ions. The color of the
indicator differs from that of the metal-ion-complex and metal indicator complex
(Mind) is much less stable than metal-EDTA-complex. Therefore, the titration of a
metal ion solution is carried out with a given indicator at suitable pH of the
solution:
MInd + H2Y2- → MYn-4 + Ind
This task is to help participants to use techniques of the volumetric analysis for
the determination of metal cations.
2. Chemicals and reagents
- Standard solutions of 0.050 M EDTA (from Na2H2Y.2H2O),
- 0.050 M Zn(NO3)2,
- Buffer solutions of 1M CH3COOH and 1 M NaCH3COO (pH = 4.7),
- Solution of 2 M NH3 + 2 M NH4 Cl (pH = 9.2),
- Solution of 1M HCl,

- Solution of 1M NaOH,
- Distilled water,
- Indicators: xylenol orange (1% in KCl),
- Eriochrome black T (ET – 00) (1% in KCl); The congo red (pH indicator);
universal pH indicator paper; 5% solution of sulfosalicylic acid.

- Burette: 50 mL,
- Volumetric pipette: 25 mL,
- Erlenmeyer flask: 250 mL,
- Graduated cylinder: 10 mL,
- Glass beaker: 250 ml,
- Funnels and filter papers (the red tape),
- Droppers,
- Hot plate.
Step 1. Sample preparation
Prepare a sample solution containing three ions of Fe3+, Al3+, and Mg2+ within
concentration range of 0.01 M to 0.1 M.
Step 2. Titration of iron, aluminum, and magnesium ions
1. Titration of Fe3+
Add 5.00 mL of the sample solution into an Elenmeyer flask. Adjust the pH of
the solution to 2 using NaOH or HCl solution with the Congo red paper. Heat the
solution to 80 - 90 oC on a hot plate and then add 0.5 mL of sulfosalicylic acid as

indicator. The solution is titrated with EDTA solution to a colorless to
yellow end point. Record the volume of the standard solution (V1 mL).
2. Titration of the total amount of Fe3+and Al3+
Add 25.00 mL of the sample solution into an Elenmeyer flask. Add 50 mL of
EDTA standard solution into the flask. Heat the solution to 80 - 90 oC and add 10 -
15 mL of the buffer solution CH 3COOH/ NaCH3COO and a small amount of
xylenol orange. Titrate the remaining amount of EDTA with the Zn 2+ standard
solution until the solution changes from red to yellow at the end-point. Record the
volume of the standard solution (V2 mL).
3. Titration of Mg2+
Take 25.00 mL of the sample solution to a glass beaker Add slowly the NH 3 +
NH4Cl buffer solution while stirring the mixture. After the precipitation reaction is
complete, add 5 mL of buffer solution and swirl the mixture. Filter the solution to
an Elenmeyer flask through filter paper with a funnel. Wash the precipitate (3-4
times) with warm water. Finally, titrate Mg 2+ with standard EDTA solution using
ET – 00 until the solution changes from white red to blue. Record the volume of
the standard solution (V3 mL).
5. Questions and Data analysis
1. Write down the chemical reactions in each individual step of the titration.
2. Derive the formulae for calculating the concentrations of Fe3+, Al3+and Mg2+ in
the sample solution.
3. Calculate the concentrations of each ion in the sample solution.

Problem 33. Determination of zinc and lead in zinc oxide powder
1. Introduction
Zinc oxide ZnO, a soft, white or faintly yellowish-white is used in the
vulcanization of rubber, ceramics, paints, and many other products.
Zinc oxide is produced by burning zinc metal in air as follows:
Zn (s)  Zn(l) Zn (g)
2 Zn (g) + O2  2 ZnO (s)

Purity of the given zinc has an influence on the quality of zinc oxide powder.
There is a very wide range of commercial grades of zinc oxide depending on
content of impurities. For example, zinc oxide powder -Grade 2 (having greater
than 60 wt.% of Zn) produced by electro-thermal process contains less than 4%
Ca; 0.4% Fe; 8% Pb.
This task is to determine the percentage of zinc and lead in commercial zinc
oxide powder by EDTA and dichromate solution.
2. Materials and Reagents

- Zinc oxide powder,
- Sulfuric acid solution, H2SO4 (aq), 4 M,
- Nitric acid solution, HNO 3 (aq), 6 M
- 0.025 M EDTA standard solution (from Na2H2Y.2H2O),
- Sodium thiosulfate: 0.02 M solution (from Na2S2O3∙5H2O),
- Ferrous sulfate: 0.025 M solution (from FeSO4.7H2O),
- Mixture of HCl and NaCl: Dissolve 320 g of NaCl in 200 mL of distilled
water, add 100 mL of concentrated HCl 37 wt.% and dilute to 1.0 L with
distilled water,

- Solution of 5% (w/v) K2Cr2O7 (aq),
- Mixture of potassium iodide and thiocyanate, KI+ KSCN, 10% w/v,
- Mixture of CH3COOH 2 M and NH4CH3COO 1M,
- Ammonia solution NH3 6 M,
- 200 mL of pH 10 buffer solution of NH3/NH4Cl,
- Eriochrome Black T (ET-00) indicator, 1% (w/w) in NaCl(s),
- Diphenylamine sulfonate indicator, 0.2% (w/w) in water,
- Starch indicator, 1% in water. This solution is prepared daily by mixing 0.5 g
soluble starch with 2-3 mL distilled water and then pouring the starch into 50
mL boiling distilled water with stirring. Continue heating the solution until the
solution is nearly transparent. Cool solution to room temperature before use.

- Analytical balance (± 0.0001 g)
- Hotplate
- Erlenmeyer flask, 250 mL
- Volumetric flask, 100 mL
- Volumetric pipette, 10.00 mL
- Burette 25 mL
- Glass beaker 250 mL
- Whatman Filter paper, Grade 2V, 110 mm.
Step 1
1. Place 0.50 g of a powder sample in a 100 mL glass beaker. Add 10 mL of 4 M
H2SO4 into the beaker. Place the beaker on a hot plate and begin heating the
mixture in the hood. Set the hot plate at medium heat. As a portion of solid

dissolves, the yellowish residues still remains in the beaker. Add slowly 3 mL of
HNO3 solution into the beaker and keep heating the solution until white
precipitate appears. Evaporate the solution in the beaker until white fumes of SO 3
forms, and then stop heating. Cool the solution to the room temperature (Hint: in
hood).
Filter the cooled solution by using filter paper to a 100 mL volumetric flask;
rinse the beaker and filter paper with 1 % H 2SO4 several times; make up the
filtrate to the mark with distilled water and shake well (solution A).
2. Place the funnel together with the filter paper on a 250 mL Erlenmeyer flask.
Pour slowly a hot mixture of 20 mL of CH 3COOH+ NH4CH3COO through the
white precipitate on the filter paper until it is dissolved. Wash the filter paper
with distilled water to get solution B.
Step 2
1. Add 10.00 mL of solution (A) and 5 mL of NH3 solution into a 250 mL
Erlenmeyer flask using pipettes and swirl to mix. Then, add 10 mL of NH 3/NH4Cl
buffer solution (pH = 10) to the mixture.
Add ET-00 indicator and about 10 mL of deionized water. Titrate carefully with
the EDTA standard solution until the color changes from wine red to blue. Record
the volume of EDTA used for this titration.
(Hint: Adjust the size of the aliquot on Zn2+ as necessary to stay within titration range).
2. Add the solution B and 5 mL of 10 % NaCH3COO into a 250 mL beaker. Heat
the mixture slowly (taking at least 10 minutes) to 90 oC and then add gently 10 mL
of K2Cr2O7 solution. Cool the mixture to room temperature and keep further at this
condition for 1 hour. Filter the precipitate through a Whatman filter paper. Wash
the precipitate with warm distilled water until the filtrate is almost colorless.
Transport the funnel with filter paper to a 250 mL Erlenmeyer flask. Dissolve
the yellow precipitate with 15 mL of warm mixture HCl +NaCl. Rinse the filter
paper with distilled water to get the solution C.

Add about 5 mL of 4 M H2SO4, 5 mL of 4 M H3PO4, and 10 mL of
distilled water to the solution C. Drop 8 droplets of diphenylamine sulfonate
indicator in the solution C. Titrate carefully with the standard ferrous solution until
the color changes from violet to green. Record the volume of ferrous solution used.
(Hint: Solution C can also be titrated using the iodometric titration).
5. Questions and Data Analysis

1. Give balanced chemical equations for the reactions when:
1.1 The zinc oxide powder dissolves in sulfuric acid and nitric acid to form a
white solid.
1.2 The white precipitate is dissolved in a mixture of CH 3COOH 2 M-
NH4CH3COO 1 M to form a complex product X.
1.3 The product X reacts with K2Cr2O7(aq) to form a yellow precipitate.
1.4 The yellow precipitate dissolves in the mixture of HCl and NaCl.
1.5 The solution C is titrated with Fe2+ and/or iodometric titration.
2. Calculate the mass percentage of Zn and Pb in the powder.
3. In iodometric titration, S2O32- is used to titrate I2 produced in the reduction of
H2Cr2O7 by I-. Why do we not use S2O32- for titration of the H2Cr2O7?
4. PbCrO4 is completely precipitated in the medium with pH of at least 5 (acetic
acid- acetate buffer).
4.1 Does the addition of 100 mL of 1.0×10–4 M Pb(OAc)2 to 20 mL of 1.0×10–3
M K2CrO4 lead to a precipitate formation, given that Ksp for PbCrO4 is 1.8×10-
14
?
4.2 Find the equilibrium concentration of Pb 2+ remaining in solution after the
PbCrO4 precipitates.
Problem 34. Preparation of copper(II) acetylacetonate
1. Introduction

Acetylacetone (Hacac) is the simplest of the beta-diketones.
O O
Hacac commonly exists in two tautomeric forms, ketone and enol, which can
rapidly interconvert in solution as well as in the gas phase.
O O O OH
Ketone form Enol form

In aqueous solutions, Hacac is in equilibrium with hydrogen ions (H +) and with
acetylacetonate (enolate) ions (acac-). The dissociation constant Ka is 1.51×10-9.
+ H2O -
+ H3O+
O OH O O
Acetylacetone can form stable complexes with many transition metal ions. In most
of the structurally characterized complexes, Hacac that is singly deprotonated acts
as a bidentate ligand, and binds to the metal via both two oxygen donor atoms to
form six-membered chelate ring.
O O O O O O
Mn+ Mn+ Mn+
Acetylacetone is known to form neutral complexes with about 60 metals and is

among the most versatile and most used chelating ligand in coordination
chemistry.
Copper (II) acetylacetonate can be synthesized in a ligand exchange reaction:
2acac- + [Cu(H2O)6]2+ [Cu(acac)2].nH2O + (6-n) H2O
- Acetylacetone

- 0.2 M CuSO4 aqueous solution
- 25% NH3 solution
- Diluted HCl solution
- Diluted NH3 solution
- Universal indicator papers
- Chemicals for determination of Cu content.
3. Apparatuses and Glassware:

- Glass beakers: 100 mL, 50 mL,
- Pipette: 5 mL,
- Graduated cylinder: 50 mL,
- Rubber bulb,
- Watch glass,
- Glass rod,
- Magnetic stirrer,
- Sintered glass funnel,
- Vacuum pump,
- Wash bottle,
- Analytical balance with readability of 0.001 g.
4. Experimental procedure:
Step 1. Preparation of copper (II) acetylacetonate:
1. Use 25 mL of 0.2 M CuSO4 aqueous solution to calculate the quantities of
chemicals required for synthesis of the complex.
2. Prepare the ammonium acetylacetonate (NH4acac) solution: Add slowly 25%

NH3 aqueous solution (d = 0.90 g.cm-3) into liquid acetylacetone in a 50 mL glass
beaker with a molar ratio Hacac : NH 3 of 1.0 : 0.9. A white solid appears for
seconds and then dissolves completely to obtain a clear solution.
3. Prepare the copper (II) acetylacetonate: Add the freshly prepared NH4acac
solution (with a 50% excess) into a 100 mL glass beaker in which 25 mL of 0.2 M
CuSO4 aqueous solution and a stirring bar are placed. Start stirring the solution on
a magnetic stirrer and adjust the pH of the mixture to 3-4 by the addition of dilute
solutions of HCl and NH3. The pale blue solid of copper (II) acetylacetonate is
precipitated. The reaction mixture is stirred for additional 30 min to complete the
precipitation. The formed solids are collected on sintered glass funnel by a vacuum
filtration, washed 3 times with small portions of distilled water and then
transported to a watch glass and dried at 120oC for 30 min. Weigh the product on
the analytical balance with the readability of 0.001 g.
Step 2. Determination of the Cu content in the complex
1. Students propose an appropriate procedure to determine the Cu content in the
product. (Hints: The Cu2+ concentrations can be determined by iodometric
titration, complexometric titration with EDTA…).
5. Questions and Data analysis

1. Calculate the copper content in the complex. Suggest an appropriate molecular
formula of copper (II) acetylacetonate and then calculate the percentage yield of
the synthesis of the complex.
2. In the Step 1(3), why is the excess of NH 4acac used? Why does the pH need to
be adjusted to 3-4?
3. Propose the molecular structure of copper (II) acetylacetonate.

Problem 35. Kinetic analysis of the hydrolysis of aspirin
1. Introduction
Aspirin (acetylsalicylic acid) is an ester of salicylic acid. It has been widely used in
medicinal treatment. It is an effective analgesic (pain killer) that can reduce the mild
pain of headache, toothache, neuralgia (nerve pain), muscle pain and joint pain (from
arthritis and rheumatism). Aspirin behaves as an antipyretic drug (it reduces fever),
and an anti-inflammatory agent capable of reducing the swelling and redness
associated with inflammation. It is an effective agent in preventing strokes and heart
attacks due to its ability to act as an anti-coagulant.
Aspirin can be easily synthesized in laboratory by the esterification reaction between
salicylic acid and acetic anhydride as shown in the reaction below:
O O O
H H
CH3
O O O
+ O + H3C
CH3 OH
O
OH O
O CH3
Salicylic acid Acetic anhydride Acetylsalicylic acid Acetic acid

In acidic or basic media, aspirin is hydrolyzed to give its active form – salicylic
acid. The hydrolysis reaction of aspirin, however, takes place in basic condition much
faster than in acidic condition. This illustrates a very important principle: the stability
of drugs and their mechanisms strongly depend on the pH condition of the body.
In general, the hydrolysis of esters may be catalyzed by either acid or base. The
detailed mechanism of hydrolysis reactions has been the subject of an enormous
research effort, since they are of such fundamental importance. The generally

accepted mechanism of acid-base-catalyzed hydrolysis is known; however many
researchers particularly in biotechnology are applying this fundamental knowledge in
new and more complicated systems.
This experiment deals with both the synthesis of aspirin and kinetic study of the
hydrolysis of aspirin under a basic condition. Working with synthesis of aspirin, the
preparative method uses acetic anhydride and an acid catalyst, concentrated sulfuric
acid, to speed up the reaction with salicylic acid. Then the hydrolysis of aspirin will be
studied under pseudo-order conditions. This will allow the order with respect to
aspirin concentration to be determined. The order with respect to the concentration of
hydroxide ions will be given and from this data you will be asked to draw conclusions
about the mechanism.

- Pure salicylic acid CH3CO2C6H4CO2H
- Acetic anhydride CH3C2O3CH3
- Concentrated sulfuric acid H2SO4
- Absolute ethanol C2H5OH,
- Standard NaOH solution.

- UV-Vis Spectrophotometer
- Thermostat
- Stirrer hotplate
- Analytical balance (± 0.0001 g)
- Beaker glass, 100 mL
- Erlenmeyer flask, 100 mL

- Pipette, 5 mL
- Büchner flask (Filter flask)
- Büchner filter
- Filter paper
- Glass rod
- Stopwatch
Step 1. Synthesis of acetyl salicylic acid

1. Prepare a bath using a 400 mL beaker filled about half-way with water. Heat to boil.
2. Weigh 2.0 g salicylic acid using an analytical balance and place it in a 100 mL
Erlenmeyer flask. Use this quantity of salicylic acid to calculate the theoretical or
expected yield of aspirin.
3. Carefully add 5.0 mL of acetic anhydride by pipette to the Erlenmeyer flask
containing the acid.
4. Add about 5-6 drops of concentrated sulfuric acid as catalyst.
Caution! Acetic anhydride could irritate your eyes. Sulfuric acid could cause burns
to the skill. Handle both chemicals with care.
5. Mix the reagents and then place the Erlenmeyer flask in boiling water bath. Heat
for 15 min. The solid will completely dissolve. Swirl the solution occasionally.
6. Add 10.0 mL water to the Erlenmeyer flask, shake the flask thoroughly, and then
place it in an ice bath for 10-15 min to crystallize out the entire product,
acetylsalicylic acid. Collect the crystals by filtration under vacuum. If the
crystallization takes place slowly, scratch gently inside the flask with a glass rod.

7. Re-crystalize the crude product as follow: Dissolve the crude product in 10.0 mL
ethanol, then pour the ethanol solution into 60.0 mL warm water and place the
obtained solution in the ice water for 10-15 min. Filter off the product.
8. Dry the product in an oven at 100 oC for 30 min. Weigh the dried product.
Step 2. Hydrolysis of acetylsalicylic acid

1. Prepare 50.0 mL of a 5×10–3 M solution of salicylic acid in 20% ethanol and
approx. NaOH 5×10–3 M solution as follows:
i) Weigh out the required amount of salicylic acid (M = 138.1 g mol –1) in small
beaker on an analytical balance.
ii) Dissolve the weighed acid in 10.0 mL ethanol.
iii) Transfer this quantitatively into a 50 mL volumetric flask already containing
5.0 mL 5×10–2 M NaOH, wash the vial several times and add water to the mark.
2. Prepare 50.0 mL of a 5×10–4 M solution of salicylic acid as follows:
i) Place 10.0 mL ethanol in a 50 mL volumetric flask, add by pipette to this flask 5
mL solution prepared in step 1.
ii) Add a required amount of 5×10–3 M NaOH solution to fill up to the mark. Place
the flask in a heated bath at 37 oC.
3. Measure the absorbance at 295 nm. This will be the A∞ in the subsequent
calculation (Note: Before measuring the absorbance of salicylic acid, the UV-Vis
spectrophotometer should be zeroed with standard sample. Standard sample is a 5×10–
3
M NaOH solution containing 20% ethanol).
4. Prepare 50 mL of a 5×10-4 M solution of acetylsalicylic acid (2-
CH3CO2C6H4CO2H) as described in parts 1 and 2 above.
5. Place the reaction bottle in a thermostated bath at 37 oC. Start counting the reaction
time as soon as the solution is placed in the bath.

6. Five minutes after the start of the reaction, transfer a sufficient amount of
the reaction solution into 1 cm UV-Vis absorption cuvette and measure the
absorbance at 295 nm. Continue recording the absorbance and write down the
obtained experimental data in the table below:
Time/min 5 10 20 30 40 50 60 ∞
Absorbance
A
5. Question and data analysis:
1. Calculate the yield of the reaction.
2. Aspirin can irritate the stomach. What is usually done in the formulation of the drug
that reduces this side effect?
3. Calculate the concentration of NaOH in 5 × 10–4 M solution of aspirin.
4. Plot (A∞ - A) vs. t, ln(A∞ - A) vs. t, and vs. t on three separate charts.
From these plots determine the order with respect to acetylsalicylic acid.
5. Determine the value of the pseudo-order rate constant, kobs. Calculate the half-life of
the hydrolysis under the reaction condition used. For how many half-lives was the
reaction allowed to run?
6. In basic solution, acetylsalicylic acid exists as an anion.
COO-
O CH3
The following mechanism has been proposed to account for the base catalyzed
hydrolysis of aspirin. Based on the order with respect to aspirin, and given the order
with respect to [OH–] = 1, derive the rate law and indicate which of the following
reactions is the rate - determining step.

COO- COO-
+ OH- k1 (1)
O k-1 O
- CH3
O CH3 O
OH
-
COO COO- O
k2
+ H 3C C (2)
O OH
O-
- CH3
O
OH
COO- COO-
k3
+ H2O + OH- (3)
O- OH
Problem 36. Complex formation of ferric ion and salicylic acid
1. Introduction
In this simple experiment we will study the complex formation of Fe 3+ and

salicylic acid in the aqueous solution. The empirical formula of the complex will
be determined and also its stability constant can be estimated.

Several stable complexes between ferric ion and salicylic acid H 2Sal
have been known. Their structures and compositions are much dependent on pH.
In acidic solution, a violet complex is formed. At neutral pH, a different dark-red
complex forms, and in basic solution the complex that forms is orange. This
experiment will be carried out at pH of about 2. Under this condition, the
hydrolysis of ferric ion is largely suppressed. To simplify the calculations, we will
not consider to the dissociation of H 2Sal during the complex formation. Thus,
regardless of the structure of the complex, we can present the complex formation
equilibrium as:
Fe3+ + n H2Sal Fe3+(H2Sal)n
Thus, the stability constant Kf is defined as
[ Fe 3 ( H 2 Sal ) n ]
Kf  (1)
[ Fe 3 ][ H 2 Sal ] n
where the [Fe3+] and [H2Sal] refer to the concentrations of the free species.
The complex Fe3+(H2Sal)n absorbs most strongly at 528 nm (and neither Fe3+ nor
H2Sal absorb at this wavelength). Its concentration is related to the optical
absorbance through Beer’s law, which is:
A = ε×l× [Fe3+(H2Sal)n]
where ε is the molar extinction coefficient for the complex and l is the optical path length.
Job’s method can be used to find the empirical formula of the complex. Following
this method, equimolar solutions of Fe 3+ and H2Sal are prepared, and then mixed in
ratios of 1:9; 2:8 … 9:1. The total reagent concentrations therefore are the same in
each solution. Maximum amount of equilibrium complex will be formed when
the proportions of reagents employed correspond to the empirical formula of the
complex and can be deduced through the measurement of optical absorbance.

2. Chemicals and Reagents:
- A solution of 0.0025 M Fe3+ made by dissolving the appropriate amount of
ferric ammonium sulfate in 500 mL of 0.0025 M sulfuric acid.
- A solution of 0.0025 M salicylic acid made by dissolving the appropriate
amount of salicylic acid in 500 mL 0.0025 M sulfuric acid.
- Saturated solution of salicylic acid (about 50 mL) in 0.0025 M sulfuric acid.
3. Apparatuses and Glassware:

o Glass beaker: 100 mL, 50 mL
o Burette: 25 mL,
o Volumetric flask: 500 mL,
o Wash bottle,
o Electronic balance with readability of 0.0001 g,
o UV-vis spectrophotometer,
o Glass cuvettes.
Step 1. Determine the empirical formula of the complex by Job’s-method
1. Prepare in 100 mL beakers (should be dry and clean) a series of nine mixtures
of the 0.0025 M iron(III) and the 0.0025 M salicylic acid solutions, plus 10.0 mL
0.0025 M:
Mixture 1 2 3 4 5 6 7 8 9
VmL Iron(III) 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00

VmL
9.00 8.00 7.00 6.00 5.00 4.00 3.0 2.00 1.0
salicylic acid
VmL 0.0025 M
10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00
HCl
(Note: Use burette to take volumes of the solution)
2. Measure the absorbance of each mixture.

3. Plot absorbance versus volume of Fe3+. Absorbance should be highest for the
stoichiometric mixture.
Step 2. Determine the molar extinction coefficient ε of the complex
1. Pipette out 1.00, 2.00, 3.00, 4.00, 5.00, 6.00 mL of 0.0025 M iron(III) solution
into 5 beakers (100 mL). To each beaker add 10.00 mL of saturated salicylic acid
solution and enough 0.0025 M HCl solution to bring the total volume to 20.00 mL.
2. Measure the absorbance of each solution.
3. Plot absorbance versus [Fe3+] (Because the salicylic acid is in excess, it is
assumed that the concentration of iron equals the concentration of the complex).
4. Calculate ε from the linear plot.
Step 3. Determine the stability constant Kf

1. Prepare (in 100mL beakers) three mixtures of the same volumes of 0.0025 M
Iron(III) and the 0.0025 M salicylic acid solutions and plus 0.0025 M HCl solution
to total volume of 20 mL:
Mixture 1 2 3
VmL 0.0025 M Iron(III) 5.00 4.00 3.00
VmL 0.0025 M salicylic acid 5.00 4.00 3.00
VmL 0.0025 M HCl 10.00 12.00 14.00

2. Measure the absorbance of each solution.

3. Calculate the initial concentration of Fe(III) and H2Sal in each solution.
4. From the measured absorbance and observed  value determined in step 2(4)).
Calculate the concentration of the complex in each solution.
5. Calculate the equilibrium concentration of Fe(III) and H2Sal. Assume that:
[Fe3+]equilibrium = [Fe3+]initial - [Fe3+(H2Sal)n]
[H2Sal]equilibrium = [H2Sal]initial – n × [Fe3+(H2Sal)n]
6. Calculate the equilibrium constants Keq for each solution (using equation 1) and
determine an average value.
5. Questions and Analysis

1. What is the empirical formula of the complex?
2. The above complex is normally reported as [Fe(Sal)] + in which the salicylic
ligand is doubly deprotonated.
2.1 Write the chemical equation in the ionic form to the formation of [Fe(Sal)]+.
2.2 Let formulate the stability constant of the ion complex [Fe(Sal)] + from
observed Keq, [H+], Ka1 and Ka2 of H2Sal.
2.3 pKa1 and pKa2 values of H2Sal are 2.98 and 13.60, respectively (CRC Handbook of
Chemistry and Physics, CRC Press, 2003, pp. 1247) . Calculate the stability constant (Kf)
of the ion complex [Fe(Sal)] + for each solution (in section 2.3) and determine an
average value. Assume that the dissociation of H 2Sal can be ignored. (Hint: [H+]eq
= 0.0025 + 2 × n × [Fe3+(H2Sal)n]).
2.4. Comment on your Kf value and explain the probable errors?
---------------------------- END ------------------------------


APPENDICES
APPENDIX A
A 1: SAFETY RULES FOR STUDENTS IN THE LABORATORY
All students of chemistry must recognize that hazardous materials cannot be
completely avoided. Chemists must learn to handle all materials in an appropriate
fashion. While it is not expected that all students participating in the International
Chemistry Olympiad know the hazards of every chemical, the organizers of the
competition will assume that all participating students know the basic safety
procedures. For example, the organizers will assume that students know that
eating, drinking or smoking in the laboratory or tasting a chemical is strictly
forbidden.
In addition to the common-sense safety considerations to which students should
have been previously exposed, some specific rules, listed below, must also be
followed during the Olympiad. If any question arises concerning safety procedures
during the practical exam, the student should not hesitate to ask the nearest
supervisor for direction.
Rules regarding personal protection

1. Eye protection must be worn in the laboratories at all times. If the student wears
contact lenses, full protection goggles must also be worn. Eye protection will be
provided by the host country.
2. A laboratory coat is required. Each student will supply this item for
himself/herself.
3. Long pants and closed-toed shoes are recommended for individual safety. Long
hair and loose clothing should be confined.
4. Pipetting by mouth is strictly forbidden. Each student must be provided with
pipette bulb or pipette filler.
Rules for Handling Materials

1. Specific instructions for handling hazardous materials will be included by the
host country in the procedures of the practical exam. All potentially dangerous

materials will be labeled using the GHS symbols. Each student is
responsible for recognizing these symbols and knowing their meaning (see
Appendix B).
2. Do not indiscriminately dispose chemicals in the sink. Follow all disposal rules
provided by the host country.
A 2: SAFETY RULES AND RECOMMENDATIONS FOR THE HOST

COUNTRY OF THE INTERNATIONAL CHEMISTRY OLYMPIAD
Certainly it can be assumed that all students participating in the IChO have at least
modest experience with safety laboratory procedures. However, it is the
responsibility of the International Jury and the organizing country to be sure that
the welfare of the students is carefully considered. Reference to the Safety Rules
for Students in the Laboratory will show that the students carry some of the burden
for their own safety. Other safety matters will vary from year to year, depending on
practical tasks. The organizers of these tasks for the host country are therefore
assigned responsibility in the areas listed below. The organizers are advised to
carefully test the practical tasks in advance to ensure the safety of the experiments.
This can best be accomplished by having students of ability similar to that of IChO
participants carry out the testing.
APPENDIX B
HAZARD WARNING SYMBOLS AND HAZARD DESIGNATIONS

Chemicals used in the IChO laboratory experiments need to be labeled according
to the Globally Harmonized System of Labelling of Chemicals (GHS) standard
developed by the United Nations. The organizing country should use the locally
legislated GHS system (pictograms, hazard statements, etc.) if it exists. If such
rules do not exist, the original GHS directives
(http://www.unece.org/trans/danger/publi/ghs/ghs_welcome_e.html) and the GHS
compliant documentation by the chemical providers should be used.

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Preparatory Problems

46th International Chemistry Olympiad (IChO - 2014)

Hanoi University of Science, Vietnam National University, Hanoi

July 17th, 2014 (Revised)

Chemistry: The flavor of life 2

We hope that these problems will be motivating for students to participate

Hanoi, January 31st, 2014

46th IChO Preparatory Problems, Hanoi, Vietnam, July 2014, 3

July 17th, 2014 (Revised)

Chemistry: The flavor of life 4

46th IChO Preparatory Problems, Hanoi, Vietnam, July 2014, 5

Fields of Advanced Difficulty

Kinetics: Integrated first- and second-order rate equation; analysis of moderately

Thermodynamics: Electrochemical cells, the relationship between equilibrium

Quantum mechanics: Particle-in-a-box calculations, orbital-overlaps, spin-orbit

Advanced Organic: Stereoselective transformations; aromatic nucleophilic

Chemistry: The flavor of life 6

Physical Constants, Symbols and Conversion Factors

Avogadro's constant, NA = 6.0221×1023 mol–1

46th IChO Preparatory Problems, Hanoi, Vietnam, July 2014, 7

90 91 92 93 94 95 96 97 98 99 100 101 102 103

PART 1. THEORETICAL PROBLEMS

Problem 1. Polar and non-polar molecules

In chemistry, a molecule is considered non-polar when its positive charge

Chemistry: The flavor of life 8

1. The dipole moment is closely related to the molecular geometry. In order to

2. The directions of the individual bond moments should be considered.

3. The bond angle HCH in the formaldehyde molecule is determined

46th IChO Preparatory Problems, Hanoi, Vietnam, July 2014, 9

Chemistry: The flavor of life 10

2.1 Establish the Born-Haber cycle for lithium chloride crystal.

3. In practice, experimental data may be employed to calculate lattice energies in

where:  is the number of ions in the empirical formula of ionic compound,

According to the Born-Haber cycle and Kapustinskii empirical formula

46th IChO Preparatory Problems, Hanoi, Vietnam, July 2014, 11

Problem 3. A frog in a well

The energy levels of an electron in a one-dimensional box are given by:

Chemistry: The flavor of life 12

2. Apply the model of  electrons in a one-dimensional box for three dye

46th IChO Preparatory Problems, Hanoi, Vietnam, July 2014, 13

Problem 4. Particles in 2, 3 - Dimensional Box

1. In Problem 3, the energy E of particle in one- dimensional box is calculated as:

Chemistry: The flavor of life 14

2. The treatment of a particle in a one- dimensional box can be extended to a two-

3. Similarly, the treatment of a particle in a one-dimensional box can be extended

46th IChO Preparatory Problems, Hanoi, Vietnam, July 2014, 15

4. In quantum mechanics, an energy level is said to be degenerate if it corresponds

Problem 5. Tug of war

SO3(g) SO2 (g) + ½ O2 (g) (1)

T/oC 527 552 627 680 727

Chemistry: The flavor of life 16

4. An amount of 15.19 g of iron (II) sulfate was heated in an evacuated 1.00 L

Zircon (ZrSiO4) is a mineral found abundantly in placer deposits located in the

46th IChO Preparatory Problems, Hanoi, Vietnam, July 2014, 17

Chemistry: The flavor of life 18

Problem 7. Applied thermodynamics

46th IChO Preparatory Problems, Hanoi, Vietnam, July 2014, 19

3. In an experiment, NiO powder and CO gas were placed in a closed container

Chemistry: The flavor of life 20