42nd International Chemistry Olympiad Tokyo, July 19-28, 2010

Instructions
• Ensure that your name and student code are written in the spaces provided at the top of each answer sheet. • You have 5 hours to work on the problems. • Use only the pen and the calculator provided. • All results must be written in the appropriate boxes. Anything written elsewhere will not be graded. Use the reverse of the sheets if you need scratch paper. • Write any relevant calculations in the appropriate boxes when necessary. If you provide no working and only the correct result for a complicated calculation, you will receive no marks. • Numerical answers are meaningless without the appropriate units. You will be heavily penalized if units are not given where required. • You must stop work immediately when the STOP command is given. A delay in doing this may lead to your disqualification from the exam. • When you have finished the examination, you must put your papers into the envelope provided, and seal the envelope by yourself. • Do not leave your seat until permitted by the supervisors. • This examination has 22 pages. The answer booklet comprises 17 pages. • The official English version of this examination is available on request only for clarification.

Theoretical Problems

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42nd International Chemistry Olympiad Tokyo, July 19-28, 2010

Constants and Formulae
Avogadro constant: Gas constant: NA = 6.022 x 1023 mol–1 R = 8.314 J K–1 mol–1 Ideal gas equation: Gibbs energy: pV = nRT G = H – TS

Faraday constant: F = 96485 C mol–1

o Δ r G o = −RT log e K = −nFE cell

Planck constant: Speed of light: Zero of the Celsius scale:

h = 6.626 x 10–34 J s c = 2.998 x 108 m s–1 273.15 K

Nernst equation: Energy of a photon: Lambert-Beer law:

E = Eo +

c RT log e ox zF c red

E=

hc

λ

= hν
I0 = εcl I

A = log 10

In equilibrium constant calculations all concentrations are referenced to a standard concentration of 1 mol L-1. Consider all gases ideal throughout the exam.

Theoretical Problems

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91 91.97 200.94 11 22.07 102.94 43 Fe 55.01 14 N 14.09 32 72.26 168.42nd International Chemistry Olympiad Tokyo.33 178.91 140.24 150.82 118.42 107.59 204.38 207.93 167.25 158.93 45 Ni 58.00 42 95.30 20 B 10.94 41 92.91 106.85 44 Co 58.22 101.64 50 P 30.76 127.72 49 Si 28.92 51 Se 78.10 37 3 21 4 22 5 23 6 24 7 25 8 26 9 27 10 28 11 29 12 30 Al 26.99 19 Be 9.38 48 Ga Ge In 81 As 74.05 174.12 140.91 137.91 144.81 13 C 12.96 157.04 238.23 192. 2010 Periodic table with relative atomic masses 1 1 18 2 H 1.08 44.41 114.93 173.00 17 Ne 20.96 74 Mn 54.03 Theoretical Problems 3/32 .69 46 Cu 63.22 195.00 16 F 19.62 88.60 126.97 33 S 32.90 131.80 54 40.93 162.84 186.04 231.98 Fr - Ra - Rf - Db - Sg - Bh - Hs - Mt - Ds - Rg - 57 58 59 60 61 93 62 63 64 65 66 67 68 69 70 71 La 89 Ce 90 Pr 91 Nd Pm Sm Eu 92 94 95 - Gd 96 - Tb 97 - Dy 98 Ho 99 - Er 100 - Tm Yb 101 102 - Lu 103 138.47 55 Sr 56 Y 5771 89103 Zr 72 Nb Mo Ta 105 Tc 75 Ru 76 Rh 77 Pd 78 Ag 79 Cd 80 Sn 82 Sb 83 Te 84 I 85 Xe 86 87.98 31 69.91 73 Cr 52. July 19-28.97 Ac - Th Pa U Np - Pu Am Cm Bk Cf - Es Fm Md No Lr - 232.96 52 Br 79.96 47.95 183.87 112.55 47 Zn 65.2 208.50 164.01 3 2 4 13 5 14 6 15 7 16 8 17 9 He 4.01 15 O 16.29 Cs 87 Ba 88 Hf 104 W 106 Re 107 Os 108 Ir 109 Pt 110 Au 111 Hg Tl Pb Bi Po - At - Rn - 132.90 53 Kr 83.45 35 Ar 39.49 180.21 190.00 10 Li 6.18 18 Na Mg K 39.87 Rb 85.36 151.01 12 24.08 196.71 121.95 36 Ca Sc 38 39 Ti 40 V 50.06 34 Cl 35.

42nd International Chemistry Olympiad Tokyo.2990 g 2.2990 g 2. this difference was attributed to the presence of argon in atmospheric nitrogen. July 19-28. as shown in Tables 1 and 2.3001 g 2. Lord Rayleigh reported that the mass of chemically prepared nitrogen was different from that of nitrogen extracted from the atmosphere. The masses of gases were measured by using a glass vessel with a known volume under atmospheric pressure (1.3102 g 2. Table 1. Mass of Atmospheric Nitrogen in the Vessel O2 was removed by hot copper (1892) O2 was removed by hot iron (1893) O2 was removed by ferrous hydrate (1894) Mean a) 2. 2010 Problem 1 8% of the total 1a 1b 1c 1d 1e 1f 1g 1h 1i Task 1 2 4 2 1 1 1 3 2 1 17 In 1894. Mass of Chemical Nitrogen in the Vessel From nitric oxide From nitrous oxide From ammonium nitrite purified at a red heat From urea From ammonium nitrite purified in the cold Mean Table 2.2987 g 2.3102 g Calculate the volume V [m3] of the vessel used by Rayleigh from the mean mass of chemical nitrogen. which must have been pure nitrogen.3100 g 2.3103 g 2.013 × 105 Pa). Later.2987 g 2. Assume that the measurements were carried out at a temperature of 15.2985 g 2. V= m3 Theoretical Problems 4/32 .0 °C.

42nd International Chemistry Olympiad Tokyo. near the wellknown D1 and D2 lines of sodium. by assuming that argon and nitrogen were the only constituents. and rare earths. Spectral lines around 588 nm c) Calculate the energy E [J] of a photon with the wavelength of the D3 line of helium shown in Figure 1. which was first observed in the spectrum of solar prominence during a total eclipse in 1868. x= Ramsay and Clève discovered helium in cleveite (a mineral consisting of uranium oxide and oxides of lead. E= Theoretical Problems 5/32 J . Use the mean masses of the atmospheric and chemical nitrogen for the calculation. an impure variety of uraninite) independently and virtually simultaneously in 1895. thorium. The gas extracted from the rock showed a unique spectroscopic line at around 588 nm (indicated by D3 in Figure 1). July 19-28. 2010 b) Estimate the mole fraction x of argon in Rayleigh's atmospheric nitrogen. 587 588 589 590 nm D3 He D2 Na D1 Figure 1.

2 3. d) Identify the transition relevant to the D3 line of helium among the transitions [A] to [E] indicated in Figure 2. The arrows indicate the "allowed" transitions according to the spectroscopic principle.6 3.4 3.0 1s Figure 2. Energy diagram of atomic orbitals of helium when an electron resides in the 1s orbital. 2010 Figure 2 shows an energy diagram of the atomic orbitals of helium. Mark one on the answer sheet: e) Which equation explains the occurance of helium in cleveite among [A] to [D] below? Mark one on the answer sheet: [A] [C] [D] 238 U → 234Th + α U → 240Np + β– U + n → 95Y + 139I + 2n [B] UHe2 → U + 2He 240 235 Theoretical Problems 6/32 . 3p 3d 3.4 E / 10–18 J 3.42nd International Chemistry Olympiad Tokyo.0 [ B] [ A] 3.2 3. July 19-28.6 3s [D] [C] 2s [ E] 2p 3.0 0.

which is exactly 5/3 (1. γ = Cp / CV.01) for a monoatomic gas. where f and λ are the frequency and wavelength of the sound. g) Calculate the molar mass M [kg mol–1] of this gas.42nd International Chemistry Olympiad Tokyo. The density ρ of the gas for these conditions was measured to be 0. absolute temperature.005 kg m–3. M= kg mol–1 Theoretical Problems 7/32 .850 ± 0. and R. [A] ArF2 → Ar + F2 [B] ArXe → Ar + Xe [C] [D] 40 K → 40Ar + ε/β+ (electron capture / positron emission) I → 126Ar + β– 126 One of the strongest evidences for the monoatomicity of argon and helium is the ratio of the heat capacity under constant pressure to that at constant volume. July 19-28. f) Which equation explains the occurance of argon in rocks among [A] to [D] below? Mark one on the answer sheet. T. and M denote the molar gas constant.116 m at a frequency of f = 3520 Hz (Hz = s–1) and temperature of 15. vs = f λ = γ RT M For an unknown gas sample.0 °C and under atmospheric pressure (1. respectively. and molar mass.013 × 105 Pa). 2010 Argon is also found in minerals such as malacon. The ratio was derived from the measurement of speed of sound vs by using the following equation. the wavelength of the sound was measured to be λ = 0.67 ± 0.

γ = i) Which is this gas among [A] to [D]? Mark one on the answer sheet: [A] HCl [B] HF [C] Ne [D] Ar Theoretical Problems 8/32 . July 19-28.42nd International Chemistry Olympiad Tokyo. 2010 h) Calculate the heat capacity ratio γ for this gas sample.

ions in a unit cell and the coordination numbers of Na+ and Cl.42nd International Chemistry Olympiad Tokyo. 2010 Problem 2 2a 4 2b 4 2c 4 2d 3 2e 5 Task 2 20 6% of the total Crystal structure of alkali metal halide In crystals of ionic compounds. Calculate the density [kg m-3] of the sodium chloride crystal.ions in sodium chloride crystal. July 19-28. cations are generally arranged in the interstices of the closest packed lattice of anions.ions form a face-centered cubic lattice. Density of NaCl crystal (kg m-3): Theoretical Problems 9/32 .ions in the crystal of sodium chloride are 0. The structure of an ionic crystal such as sodium chloride becomes stable when the cations are in contact with the nearest anions. Give the numbers of Na+ and Cl. both Na+ and Cl.102 nm and 0.181 nm. respectively. Na+: Na+: Cl-: Cl-: Number of ions Coordination number b) The ionic radii of Na+ and Cl. a) In the crystal of sodium chloride.

c) The figure below shows the Born-Haber cycle of NaCl. 2010 Born-Haber cycle and lattice enthalpy In ionic inorganic compounds such as sodium chloride. the heat of lattice formation from gaseous ions is very high. the lattice formation enthalpy is estimated from enthalpy data by using a Born-Haber cycle. The labels “g” and “s” represent “gas” and “solid” states respectively. July 19-28. Show chemical equations in the A and F steps. Therefore. Na+ (g) + Cl (g) + eD: Dissociation of Cl2 (g) E: Electron gain by Cl (g) C: Ionization of Na (g) B: Sublimation of Na (s) F: Dissociation of NaCl (s) A: Formation of NaCl (s) from elemental substances. NaCl (s) A: F: d) Calculate the enthalpy of the lattice formation of NaCl [kJ mol-1] by using the following enthalpy data of the respective steps in the above Born-Haber cycle. and the contribution of the change in entropy is small. Formation of NaCl (s) –411 kJ mol-1 Sublimation of Na (s) 109 kJ mol-1 Ionization of Na (g) 496 kJ mol-1 Dissociation of Cl2 (g) 242 kJ mol-1 Electron gain by Cl (g) –349 kJ mol-1 Lattice formation enthalpy of NaCl (kJ mol-1): Theoretical Problems 10/32 .42nd International Chemistry Olympiad Tokyo.

e) The total chemical reaction in the ammonia-soda process is represented as follows: 2NaCl + CaCO3 → Na2CO3 + CaCl2 This reaction between sodium chloride and calcium carbonate does not proceed directly. medicaments. July 19-28. The process comprises the following five reactions involving ammonia: CaCO3 Δ [ A ] + [ B ] → NaCl + NH3 + [ B ] + H2O →[ C ] + [ D ] Δ 2 [ C ] → Na2CO3 + H2O + [ B ] [ A ] + H2O → [ E ] [ E ] + 2 [ D ] → CaCl2 + 2H2O + 2NH3 where Δrepresents applying heat treatment.42nd International Chemistry Olympiad Tokyo. 2010 Synthesis of sodium carbonate by the ammonia-soda process (Solvay process) Sodium carbonate (anhydrous soda ash) is a raw material in the manufacture of glass. etc. A: B: C: D: E: Theoretical Problems 11/32 . alkaline detergents. Insert the chemical formulas of the appropriate compounds in the blank spaces [ A ]–[ E ] in the above reactions.

the COD of service water is kept below 1 mg L-1.00 × 10-2 L of the solution was used for the titration. such as organic compounds. An example of the operation is presented below.00 × 10-3 mol L-1 potassium permanganate solution. 2010 Problem 3 3a 3b 3c 3d 2 3 1 3 Task 3 9 7% of the total The chemical oxygen demand (COD) refers to the amount of oxidizable substance. in a sample solution. lakes. 3. July 19-28.00-L sample solution was acidified with a sufficient amount of sulfuric acid. b) Calculate the amount of O2 (mg) that will oxidize the same number of moles of oxidizable substance as 1.25 × 10-2 mol L-1 disodium oxalate (Na2C2O4 or NaOOC-COONa) standard solution was added.00 × 10-3 mol L-1 potassium permanganate does. 1. To the sample solution.00 × 10-3 L of 5. ****************************************************** Analytical Operation A 1. and marshes.00 × 10-1 L of 5. and it is used as an indication of water quality in seas. and the mixture was stirred well.00 × 10-3 mol L-1 potassium permanganate solution was added. For example. 1. Theoretical Problems 12/32 . Further. and the mixture was heated for 30 min. The COD (mg L-1) is represented by mass of O2 (mg) which accepts the same amount of electrons which would be accepted by the strong oxidizing agent when 1 L of a sample solution is treated with it. Oxalate ions that remained unreacted were titrated with 5.42nd International Chemistry Olympiad Tokyo. and chloride ions were removed by the addition of silver nitrate solution.00 × 10-1 L of 1. ****************************************************** a) Give the equation of the redox reaction of potassium permanganate and disodium oxalate.

select the most appropriate reason for the removal of chloride ions: [A] Some of the chloride ions react with potassium permanganate. [B] Some of the chloride ions react with disodium oxalate. d) Calculate the COD (mg L-1) of the sample solution described in the analytical operation above. Theoretical Problems 13/32 . [C] Some of the chloride ions react with organic compounds in the sample solution. resulting in an error in COD.42nd International Chemistry Olympiad Tokyo. July 19-28. [D] A color is developed during titration. 2010 c) From the following choices. resulting in an error in COD. resulting in an error in COD. resulting in an error in COD.

and the half-reaction at the anode is LiC6 → 6C + Li+ + e-.→ LiCoO2. 2010 Problem 4 4a 4b 4c 4d 2 3 2 1 Task 4 8 6% of the total The rechargeable lithium ion battery has been developed in Japan. Assume that the half-reaction at the cathode is CoO2 + Li+ + e. Calculate the mass of the anode in the completely charged state and that in completely discharged state if 10.00 g of graphite (C) are present initially. a) Write the total reaction equation of the battery and calculate the value of the standard Gibbs energy of the reaction [kJ mol-1].42nd International Chemistry Olympiad Tokyo.00 g of LiCoO2 and 10. Total reaction equation: The standard Gibbs energy of the reaction: b) The battery cell is constructed using LiCoO2 and graphite (C) as the electrode materials.70 V. The standard electromotive force of the battery is 3. In the completely charged state: In the completely discharged state: Theoretical Problems 14/32 . July 19-28.

Give the chemical formula of the gas generated if water is present in the electrolyte. Theoretical Problems 15/32 . d) Because an aqueous solution cannot be used as an electrolyte. In comparison. July 19-28. the energy density of lead-acid batteries used for vehicles is about 200 kJ kg-1. an organic solution is used in the lithium ion battery cell.0% of the total mass of the battery cell. Assume that the correct ratio for complete reaction between the cathode and anode materials is used and the sum of the mass of electrodes is 50. 2010 c) Calculate the maximum energy generated per mass of the lithium ion battery cell [kJ kg-1].42nd International Chemistry Olympiad Tokyo.

the energy is conserved as shown in Figure 1.0 Kinetic energy of photoelectron (eV) 3. eV is a unit of energy and 1. Theoretical Problems 16/32 .6 × 10-19 J.42nd International Chemistry Olympiad Tokyo. No photoelectrons are detected above 6.0 5.2 eV. absorbs short-wavelength light.0 4. The energy of the incident light is 21.0 eV. In this event. Kinetic energy of photoelectron X+ hν IE Intensity (arb. the atom is ionized to generate an ion X+ and the electron (called a photoelectron) is ejected at the same time. A photoelectron spectrum is a plot of the number of photoelectrons as a function of the kinetic energy of the photoelectrons. July 19-28. the photoelectron is ejected and an H2+ ion with a variety of vibrational states is produced.2 eV. Schematic diagram of photoelectron spectroscopy. that is.2 eV X 6. Figure 2. for example. H2.0 Figure 1.) Photoelectron spectrum of H 2 h ν = 21. 2010 Problem 5 7% of the total 5a-1 5a-2 5b 5c 5d 5e 5f Task 5 1 1 2 2 3 4 5 18 When an atom X absorbs radiation with a photon energy greater than the ionization energy of the atom. Photoelectron spectrum of H2.0 eV is equal to 1. Photon energy (hν) = ionization energy (IE) of X + kinetic energy of photoelectron. Figure 2 shows a typical photoelectron spectrum when H2 in the lowest vibrational level is irradiated by monochromatic light of 21. When a molecule.

a-2) a-1) & a-2) ΔEA1 (eV) = ΔEA2 (eV) = b) H The electronic energy levels E n of a hydrogen atom are given by the equation H En = − Ry n2 (n = 1. Here n is a principal quantum number. Calculate the ionization energy EB (eV) of the hydrogen atom to the first decimal place. 2. 3Λ ) . v and v ion denote the vibrational quantum numbers of H2 and H2+. 2010 a-1) Determine the energy difference ΔEA1 (eV) between H2 (v = 0) and H2+ (v ion = 0) to the first decimal place. and Ry is a constant with dimensions of energy. July 19-28. The energy from n = 1 to n = 2 of the hydrogen atom is 10. Determine the energy difference ΔEA2 (eV) between H2+ (v ion = 0) and H2+ (v ion = 3) to the first decimal place. Theoretical Problems 17/32 .2 eV. respectively.42nd International Chemistry Olympiad Tokyo.

July 19-28. then use 15. determine the bond energy ED (eV) of H2+ to the first decimal place. 2010 c) The energy threshold for the generation of two electronically excited hydrogen atoms H* (n = 2) from H2 (v = 0) has been derived to be 24. Determine the bond energy EC (eV) of H2 to the first decimal place.0 eV and 5.42nd International Chemistry Olympiad Tokyo. EC (eV) = d) Considering an energy cycle. respectively.9 eV by an experiment. → 2 If you don’t have the values for EB and EC.0 eV for EB and EC.0 eV and 5. ED (eV) = e) Calculate the threshold energy EE (eV) of the following dissociative ionization reaction to the first decimal place: + H ⎯⎯ H* (n = 2) + H + e. If you don’t have the values for EB and EC. - EE (eV) = Theoretical Problems 18/32 .0 eV for EB and EC. then use 15. respectively..

u (m/s) = Theoretical Problems 19/32 . 21.42nd International Chemistry Olympiad Tokyo. then use 5. If you don’t have the value for EC.0 eV for EC. H2 is assumed to be at rest. July 19-28. the following dissociation process occurs at the same time. 2010 f) When H2 absorbs monochromatic light of 21.2 eV.2 eV H ⎯⎯ ⎯ ⎯⎯→ H (n = 1) + H (n = 1) 2 Two hydrogen atoms move in opposite directions with the same speed. Calculate the speed u (m s-1) of the hydrogen atoms generated in the above reaction.

20/32 Theoretical Problems . If there are stereoisomers. B. B. Note that any wrong isomers will be penalized. no coloration was observed in C. July 19-28. in which a piece of sodium is added to the neat samples in the case of the liquid samples and to the concentrated solution of the samples in an aprotic solvent in the case of the solid ones. It was found that the saturated alcohol(s) obtained from C has no stereogenic carbons. give all structural formulas. and C in test tubes and the evolution of hydrogen gas was observed only in the case of C. (1)At room temperature. A was oxidized when (2)aqueous potassium permanganate was added to it and the mixture was heated. a) Among all the isomeric organic compounds of C8H10O having a benzene ring. All have C8H10O and contain a benzene ring. while only two kinds of such isomers can be obtained from D. b) Among all the isomeric organic compounds of C8H10O having a benzene ring. When an iron(III) chloride aqueous solution was added to C and D. 2010 Problem 6 6a 6b 6c 6d Task 6 5 4 6 11 26 6 % of the total Read the description of four kinds of isomeric organic compounds of A. Hydrogenation of the benzene ring in C and D using a catalyst gave saturated alcohol(s). it is possible to obtain four kinds of monochlorinated structural isomers from B. and D.42nd International Chemistry Olympiad Tokyo. Answer the questions that follow. C. Let’s imagine that (3)a hydrogen atom in the benzene ring is replaced by a chlorine atom. a piece of sodium metal was added to A. whereas D was colored. give the structural formulas of all the isomers that do NOT yield hydrogen gas in the underlined procedure (1). the acidification of the heated mixture and its isolation afforded benzoic acid. but the one(s) from D has stereogenic carbon(s). give the structural formulas of all the isomers that yield benzoic acid in the underlined procedure (2).

d) A Give the structural formulas of A. July 19-28. 2010 c) Among all the isomeric organic compounds of C8H10O having a benzene ring. When several isomers can be considered. C.42nd International Chemistry Olympiad Tokyo. give the structural formulas of all the isomers that could yield four different monochlorinated structural isomers when the underlined transformation in (3) is performed. and D. B. give the structural formulas of all of them. B C D Theoretical Problems 21/32 .

dehydration and aromatization from E produce quinazoline derivative 2. Studies on tetrodotoxin (1) have been performed from the beginning in the 20th century. HO H H N N H HO H O– O OH O H H H OH OH H2N tetrodotoxin (1) a) The guanidine group in tetrodotoxin exhibits strong basicity. Finally. NHR1 H2N A NHR2 B C B C b) Many derivatization reactions were performed in structure studies of tetrodotoxin. Treatment of tetrodotoxin (1) with ethanolic potassium hydroxide upon heating afforded quinazoline derivative 2.42nd International Chemistry Olympiad Tokyo. are highly prized as foods in Japan. Draw structures of the postulated intermediates D. E. First. A retroaldol reaction of D cleaves a carbon-carbon bond to provide intermediates E and F. The reaction mechanism can be described as follows. The guanidinium ion resulting from protonation on the guanidine group is stabilized by the existence of the following resonance. July 19-28. which provided an insight into the nature of the fundamental skeleton of tetrodotoxin. Since the viscera (especially ovaries and livers) of the fish contain a potent toxin (tetrodotoxin). 2010 Problem 7 7a 7b 7c 7d Task 7 4 9 6 5 24 7% of the total Certain varieties of puffer fish. Draw two resonance structures B and C. and F. food poisoning often results from its ingestion. Theoretical Problems 22/32 . its chemical structure was elucidated in 1964. tetrodotoxin is hydrolyzed into carboxylate 3. Fugu in Japanese. Then the hydroxyl group highlighted with a frame is eliminated by the base to give intermediate D.

it is proposed that tetrodotoxin may be biologically synthesized from L-arginine and isopentenyl diphosphate. Among the carbons included in tetrodotoxin. 2010 H2N HO H H N N H HO O– O OH O H H 1 H H OH H2O base H2N HO H H N N H HO H COO– OH HO OH H H 3 H OH OH OH OH H HN H2N N H HO H OH OH OH OH OH COO– 3 dehydration (-H2O) N H2N N OH 2 OH base dehydration & aromatization base intermediate E F retro-aldol reaction base intermediate D D E F c) Although biosynthesis of tetrodotoxin still remains to be clarified. NH2 H2N N H L-arginine COO– NH2 –O O O P O P O O– O– tetrodotoxin (1) isopentenyl diphosphate H 2N HO H H N N H HO H O– O OH O H H H OH OH Theoretical Problems 23/32 . July 19-28. circle all the carbons that are expected to be of L-arginine origin.42nd International Chemistry Olympiad Tokyo.

Draw a structure of the postulated intermediate G showing the stereochemistry.42nd International Chemistry Olympiad Tokyo. 2010 d) In the 1990s. an alternative biosynthetic pathway of tetrodotoxin was proposed. HO O O OH HN NH2 NH2 G ( C6H11N3O3) O O –O P O P O O– O– isopentenyl diphosphate tetrodotoxin (1) 2-deoxy-3-oxo-D-pentose HO OH O CHO G Theoretical Problems 24/32 . July 19-28. Condensation between 2-deoxy-3-oxo-D-pentose and guanidine provides intermediate G with cyclic guanidine moiety (molecular formula C6H11N3O3). Tetrodotoxin may be biologically synthesized from intermediate G and isopentenyl diphosphate.

p.6 sample was prepared by polycondensation between an equimolar mixture of adipic acid (hexanedioic acid) and hexamethylenediamine (hexane-1. we add the suffixes of “A” or “B” such as NA0.42nd International Chemistry Olympiad Tokyo. N0 = NA0 + NB0 and N = NA + NB.e. NA or NB.(1) by polycondensation (often called “condensation polymerization”).N) / N0 (≦ 1). NB0. n HOOC-R1-COOH + n HO-R2-OH → HO-[COR1CO-OR2O]n-H + (2n-1)H2O (1) X can be estimated from the consumption of functional groups (here.e. i. as p = (N0 .2pAr) (2) a) Some nylon-6. it is not always an integer but a value with decimal figures. pA is identical to p and eq. For each functional group of the dicarboxylic acid molecules (A) and diol molecules (B). 2010 Problem 8 8a-1 2 8a-2 4 8a-3 3 8b-1 4 8b-2 7 Task 8 20 6% of the total The esterification reaction between bi-functional molecules gives one of the typical linear chain polymers as shown in eq.6diamine). July 19-28. respectively.(2).6 sample. where N0 and N denote the total numbers of functional groups before and after the polymerization. Let us define the degree of reaction. If r = 1. i. the average degree of polymerization.(2) becomes the same to the Carothers equation. where r = NA0 / NB0 (≦ 1) and pA = (NA0 – NA) / NA0. X (note that X = 2n in the present instance). The control of polymerization conditions and procedures determines the length of polymer strands.. X = (1 + r) / (1 + r .. [Caution: what are the end groups when polycondensation was started from the equimolar mixture?] Theoretical Problems 25/32 . respectively. X is expressed by pA and r as shown in eq. Because X (and also n ) is an averaged number. When the initial feed is unbalanced such as NA0 ≦ NB0. a-1) Show the chemical structure of this nylon-6. -COOH and -OH).

25 (g mol-1). July 19-28. ≒ p= b) The low-molecular-weight polyester (oligoester) is prepared from the mixture of 36. use 52.4-diol (Bdiol).6 sample of M = 5507. the oligoester with X = 11. give its X value to the second decimal place.50 instead.6 sample carries an average molecular weight. M. Under the condition of pA→1. If you get no numerical answer in a-2).25 (g mol-1) to the fifth decimal place.42nd International Chemistry Olympiad Tokyo.54 (g) of adipic acid (hexanedioic acid) and an unknown amount [W (g)] of butane-1.00. Calculation procedures must be shown by suitable equation(s) (otherwise. 2010 a-2) When this nylon-6. of 5507.00 carrying Bdiol units in both chain ends is obtained. no score will be provided): X= a-3) Give the p value necessary to prepare this nylon-6. Theoretical Problems 26/32 . b-1) Show the precise chemical structure of this oligoester of X = 11.

July 19-28. W (g). 2010 b-2) Calculate the unknown amount. no score will be provided): W= (g) Theoretical Problems 27/32 . Calculation procedures must be shown by suitable equation(s) (otherwise. to the first decimal place.42nd International Chemistry Olympiad Tokyo.

which is a cyclic oligosaccharide of six α(1 → 4) linked α-Dglucopyranoside units. Left: view through the hole. Right: side view. Also. α αCyD αCyD Figure 1. draw a stereostructure of the open chain form of D-glucose. can be topologically represented as toroids (Figure 1). 2010 Problem 9 9a 9b 9c 9d 9e 9f Task 9 4 2 8 4 8 8 34 7% of the total α-Cyclodextrin (αCyD). α-Dglucopyranoside units in αCyD are usually in the most stable chair conformation. July 19-28. Space filling model of αCyD. Chain form: Absolute configuration at C-2: Absolute configuration at C-5: Theoretical Problems 28/32 .42nd International Chemistry Olympiad Tokyo. a) Give the absolute configuration (R or S) at stereogenic carbons C-2 and C-5 of Dglucose.

add four OH groups and four H atoms to complete the α-D-glucopyranose formula. 2010 b) Choose the most stable conformation from the four incomplete α-D-glucopyranose formulas given in the answer box and enclose it in a box.42nd International Chemistry Olympiad Tokyo. Also. July 19-28. H OH O O H OH O H OH Theoretical Problems 29/32 .

14 ppm are 0. K: Theoretical Problems 30/32 . the inclusion complexation can be given by the following equilibrium.41 and 0.42nd International Chemistry Olympiad Tokyo. The doublet peak at 5.14 ppm is from H-1 of αCyD complexed with BTAD.59. K for the inclusion complexation of αCyD/BTAD. the relative peak areas of the doublets at 5. respectively. while the doublet at 5. Expanded 1H NMR spectra (signals from H-1 of αCyD) of solutions containing 5. Calculate. G + H k1 k-1 HG (1) where k1 and k-1 are the rate constant for the forward and backward reaction. the concentration equilibrium constant. 2010 αCyD in water is able to host hydrophobic molecules.0 ×10-2 mol L-1 BTAD.06 and 5.06 ppm is from H-1 of free αCyD. When the host/guest (H/G) stoichiometry is 1/1. to 2 significant figures. (Note that the spectra given in Figure 2 were measured in the complexation equilibrium state. Figure 2 shows a part of 1H NMR spectra (signals from H-1 of αCyD) showing the chemical shift change in the presence of varying amounts of 1. respectively. The complexation of a guest to αCyD causes a chemical shift change in 1H NMR spectra.0 x10-3 mol L-1/5. July 19-28.0×10-3 mol L-1 αCyD and 0-3.) BTAD Figure 2. c) In the spectrum of 5.0 x10-3 mol L-1 αCyD/BTAD.10-bis(trimethylammonium)decane diiodide (BTAD).

HTAB Figure 3.740 ppm and 0. d) The signal of HTAB in αCyD/HTAB solutions appears as one triplet. K of αCyD/HTAB > K of αCyD/BTAD d. only one signal of the guest is observed at the weighted average of the chemical shifts of the free guest and the shift of the guest included in αCyD. a. The H-6 signals from free HTAB and HTAB complexed with αCyD are triplets at 0. respectively. Choose the rational interpretation(s) just from these spectra. Figure 3 shows a part of 1H NMR spectra (H-6 signal of HTAB) in αCyD/HTAB solutions. The signal appears as one triplet (not two triplets). 2010 Complexation of αCyD with hexyltrimethylammonium bromide (HTAB) appears in NMR spectra in a way different from the αCyD/BTAD complexation.0×10 mol L HTAB and 0-3. which shifts depending on the concentration of αCyD.0×10-2 mol L-1 αCyD.860 ppm. July 19-28. Expanded 1H NMR spectra (H-6 signal of HTAB) of solutions containing -2 -1 1. which shifts depending on the concentration of αCyD from the position of free HTAB to the position of αCyD/HTAB in proportion to the fraction of the complex in the solution.42nd International Chemistry Olympiad Tokyo. k1 of αCyD/HTAB > k1 of αCyD/BTAD b. hint: When a guest molecule move in and out of αCyD rapidly and repeatedly. k1 of αCyD/HTAB < k1 of αCyD/BTAD c. K of αCyD/HTAB < K of αCyD/BTAD Theoretical Problems 31/32 .

to 2 significant figures.0 ºC and 60. K for the complexation of αCyD/HTAB. Calculate. the enthalpy change. 2010 e) The signals of HTAB in 1.0 x10-2 mol L-1 αCyD/HTAB are positioned at 0.42nd International Chemistry Olympiad Tokyo. Calculate. K: f) At 40.0 ºC. July 19-28.) ΔSº: ΔHº: Theoretical Problems 32/32 . and the entropy change.09 × 102 respectively. K for the complexation of αCyD/HTAB are 3.815 ppm.12 × 102 and 2. (Ignore the temperature dependence of ΔHº and ΔSº. ΔSº [J K-1 mol-1].0 x10-2 mol L-1/1. ΔHº [kJ mol-1]. to 2 significant figures.

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