702 15 July 2012 ss see cca nw eemEAEY ‘roa even 17" National and the 5" International Chemistry Olympiad Summer 2012 Kish Island, Iran Analytical Chemistry and Instrumental Analysis Do NOT Write here 5" International Olympiad Summer 2012 Do NOT Write here Name: Time: 90 minutes ‘Question Points: | Signat total score ‘Surname: No. foreach question | _ Signature (out of 100) 1 | z a | Subject title: 7 7 2 6 |_| Gote Date of Exam: Important Note: Please write your personal information only in the appropriate boxes provided on this page. Do not write on any other page.Analytical Chemistry page 3 Nol. What is the largest value of Ksp for a metal sulfide, MS,), that allows [OH'] to be taken as 1.00 x 107M? For H28 : Ky = 1.02 « 107, Ky = 1.10 « 107% No 2. Find the pH of 0.10 M ammonium bicarbonate. NH," : pKa= 9.244 No3. 1- When the high-temperature superconductor yttrium barium copper oxide is heated under flowing Ha, the solid remaining at 1000°C ixture of Y203, BaO and Cu, The starting material has the formula YBaxCusO,z.. in which the oxygen stoichiometry varies between Tand 6.5 (x= 0 to 0.5), a YBa,Cu,O,_,(s) + (3.5 — JH,(g) 1°" ™M 666.19 — 16.00% Y,0,(s) + 2BaO(s) + 3Cu(s) + (3.5 — x)H,O(g) essa sean ae ‘YBa,Cu,0,, a) When 34.397 mg of YBayCusQj;.4) were subjected to this analysis, 31.661 mg of solid remained after heating to 1000°C. Find the value of x in YBaxCujO(7.). 'b) Suppuse that the uncertainty in each mass in part (A) is 40.002 mg. the value of x. ind the uncertainty in No 4. A 3.000 g Cu wire was immersed into a 100 mL solution initially containing [Fe*"]=0.020 M and [Fe*"}=0.010 M. Calculate a) The equilibrium concentration of all species. b) Theoretical potential of Cu wire. ©) The change in Cu wire weight. Erqaticu = 0.34 V , B resi) rere = 0.77 V Fw(Cu)= 63.55 g/mol , R=8.314 Jmol K, F-96485 CAnalytical Chemistry page 11 — eee No 5. Low concentrations of Ni near the detection limit gave the following signal in a atomic emission measurement: 175, 104, 164, 193, 131, 19, 155, 133, 151, 176, Ten measurements of a blank had a signal of 45. A sample containing 1.00 4M Ni gave a signal of 1797. Estimate the detection limit for Ni No6. In the preceding example, methane gave a sharp spike in 42 s, whereas benzene required 251 s. The open tubular chromatography column has an inner diameter of 250 yum and is coated on the inside with a layer of stationary phase 1.0 pm thick, Estimate the partition coefficient for benzene between stationary and mobile phases and state what fraction of the time benzene spends in the mobile phase.ET 14 July 2012 602 17" National and the 5" International Chemistry Olympiad Summer: 2012 Kish Island, [ran Inorganic Chemistry Tand IT Time: 90 minutes Do NOT Write here | 5" International Olympiad Summer 2012 Do NOT Write here ‘Question Points oe Total score First Name: No. for each question = (out of 100) 1 2 . Surname: i | 3 Important Note: Please write your personal information only in the appropriate boxes provided on this page. Do not write on any other page. [Date of Exam:Inorganic Chemistry Page 3 L- forms. C is not solubk be C+2K > D+B: C+4KOH > D+E a. Metal A forms several modifications (Crystal phases) . Transi be shown in the form of the scheme below, where unit cell parameters and densities are indicated: ° eA PE pg OS yg HONE 2.86 ? 293; A (unit cell parameters) 7.93 761 8.23 2 g/em> — (Densities) At heating of A in the flow of gas B at 150°Cand 15 atm yellow volatile liquid C water and decomposes at 300°C, Chemical properties of C can lustrated by the following reactions: 2H,0; C+1, > F +B. Determine metal A and unknown compounds, marked as "2", if a,B,8 are modifications with body-centered cubic cell (one atom in the center of cube and eight —in the corners). Which cell does 7 -modification possess? Find all compounds, if it is known that E and D are salts, and molecule B, in a contrast to isoelectronic molecule G,, has dipole moment p=0.04% 107? Gm 602.10" °C). Describe the structure of molecule B by the method of, molecular orbitals and determine the charges on atoms, if the distance between nuclei is 1.128A. What is the structure of the molecule C (indicate hybridization and oxidation states of all atoms, electronic configuration and the quantity of unpaired electrons of central atom, geometrical shape of the molecule)? What is dipole moment of molecule cr 2-Complexes of the [Co (en)s|°* have two enantiomeric forms. Please sketch the absolute 3. configurations and show a mechanism for racemization of enantiomeric forms. en=ethylene diamine Consider a trigonal bipyramid structure for the following complex, write the orbital ing pattern and electronic configuration for central atom, vanadium (Z: This compound has Jahn-Teller distortion. Explain and draw the true structure ( considering bonds length) of the complex after Jahn-Teller distortion. 2+ (an) ee N+ Inorganic Chemistry Page 10 Give a brief answer for the followings. (a) Write the term symbol of the ground state arising from an free ion with 34° configuration, (b) Determine the irreducible representations for the terms arising from the splitting ofa gas ion °F state by an octahedral ligand field. type of level__Irreducible representations spanned _ s ag Sw ft tg ay thy thay nares +t, +t He aig beg the tog (c) Octahedral Mn‘? complexes are much less intensely colored than those of Cr* why? (d) Predict the order of the energy of charge-transfer band for the ions vo; ,Croy?, MnO; (e) How will the d orbitals split in a trigo: field model, determine the relative energies of the or! 1 bipyramid enviromment? Using erystal Is. 5- Reaction provided below gives two products, A and B. (a) How is it possible to increase product A over B. (b) How might to enhance product B. ub > a Ss PS701 15 July 2012 smueanéuise 17" National and the 5" International Chemistry Olympiad Summer: 2012 Kish, Iran Organic Chemistry I, I, IM and organic spectroscopy Time: 90 minutes Do NOT Write here 5" International Olympiad Summer 2012 Do NOT Write here aia] Fs en ee No. for each question i 2 3 4 5 6 7 8 9 0 Important Note: Please write your personal information only in the appropriate boxes provided on this page. Do not write on any other page. Name: Surname: Subject title: Date of Exam:Organic Chemistry page 3 No 1. Give the correct structures and clearly show stereochemistry of each compounds (Athrough D) in the following sequence of reactions: Br,, NaOH CHa) OOH: soa, Nit, 10 : —~- a —“+s —4 “cn, L_____. p@n,n) PO heat No2. Give the expected major product(s) in the following reaction 0 CHMet LO | ae es No 3. Give the expected major products in the following reaction. OMe ° HOH, H° (catalyst) Home + bes i eo ev ou o 20°C, 15 min No4, Write the mechanism for each step and identify the compounds produced in each step in the following reactions: NaNH, RCOOH Lil —— > A 7 ele -BUOH Compound A (C,H,): 5y (ppm) 5.35 2H, s), 1.00 (4H, 8). ‘Compound B (C,H,0): 8,,(ppm) 3.00 (2H, s), 0.90 2H, d, J=3 Hz), 0.70 (2H, d, J=3 Hz). Compound C (C,H,O): 8, (ppm) 3.02 (4H, t, J=5 Hz), 1.00 2H, quin, J=5 Hz),Organic Chemistry page 7 No 5. Show the product(s) and the stereochemistry of the product(s) for each reaction with (R) and (S) or (E) and (Z) notations. PhCH, H oe Br, HCH PhCH, 1 KMn0, .H,0, KOH : ») = ——_——? Ph = Phenyl dilute, cold H ” aH PhCH. Tscl NaN, ° or 2 H EN ethanol (absolute) nicl No6. i Write the structures of the reagents and the products (A-L) for the following reaction sequences: | ea OOO a H H,0° 1) NaBH, / THF BEGeIys bo | 2 HO 6 r 7 | HH K L ee ——s oe Me ( ‘COOMe [ Jeon HOCH No7. How could you carry out the following transformations. Show the necessary reagents and all the steps for this transformation? 9 tI PhCH,CH,CH=CH, =—§ ———> PhCH,CH,CH,CHOrganic Chemistry page 10 No8. Deduce structure for compound A with molecular formula CigHO according to the attached spectra. Interpret each spectrum as much as possible. “ye IR Spectrum ‘te fin) L 1. 4000 3000 72000 708 200" 00 V ten") +00] cn 705 gear Gof = a Gok g ” 40k 2 Ms 146 Es) Wet CyqHoO 40 80 «120 «160 «200 240280 mie ee "3G NMR Spectrum re (4000 Mz, CDC, soliton) DEPT chid crab cut | 200 160 120 80 40 0 S8ippm) HNMR Spectaum {too Wie, 606, sou) expan on = 2625 ppm 1210 pe so 75 om aan Ts L L 1 a L . 1 1 L 1 L 1 10 9 8 zy 6 5 4 3 1Organic Chemistry page 12 No 9. Write the structures of the compounds A-D formed in the following reaction sequence: ° t 2 -NHCCH, (CH),CcL HCI,H,O Cl, (2 mole) 1) NaNO2, HCI a al EE as Se oe AICI, ee 2) CuBr r. F I 0) ( 2HI(g) and its reverse were assumed to be elementary bimolecular reactions. However, it is suggested the following mechanism for the reaction provides a better explanation of the experimental results: (1) Tage + ky ky Q)1+1+H,>HI+HI ky Obtain the expre: Under what conditions does this rate low reduce to the one for the o1 mechanism? (18 points) mechanism, ally accepted 6- The excess Gibbs energy of solutions of methyleyclohexane (MCH) and tetrahydrofuran (THE) at 303.15Kwas found to the expression GP =RTx (1x) | 0.4857 0.1077(2x — 1) +0.01912x—1)? } ‘Where x is the mole fraction of MCH. Calculate the Gibbs energy of mixing when a mixture of 1.00 mole of MCH and 3.00 mal THF is prepared. (16 points)