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IIT JAM 2011 : Chemistry

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A A 2011 CY 2011 CY Test Paper Code: CY Time: 3 Hours Maximum Marks: 300 INSTRUCTIONS 1. This question-cum-answer booklet has 38 pages and has 44 questions. Please ensure that the copy of the question-cum-answer booklet you have received contains all the questions. 2. Write your Registration Number, Name and the name of the Test Centre in the appropriate space provided on the right side. 3. Write the answers to the objective questions against each Question No. in the Answer Table for Objective Questions, provided on Page No. 7. Do not write anything else on this page. 4. Each objective question has 4 choices for its answer: (A), (B), (C) and (D). Only ONE of them is the correct answer. There will be negative marking for wrong answers to objective questions. The following marking scheme for objective questions shall be used: (a) For each correct answer, you will be awarded 3 (Three) marks. (b) For each wrong answer, you will be awarded -1 (Negative one) mark. (c) Multiple answers to a question will be treated as a wrong answer. (d) For each un-attempted question, you will be awarded 0 (Zero) mark. (e) Negative marks for objective part will be carried over to total marks. 5. Answer the subjective question only in the space provided after each question. 6. Do not write more than one answer for the same question. In case you attempt a subjective question more than once, please cancel the answer(s) you consider wrong. Otherwise, the answer appearing last only will be evaluated. 7. All answers must be written in blue/black/blueblack ink only. Sketch pen, pencil or ink of any other colour should not be used. 8. All rough work should be done in the space provided and scored out finally. 9. No supplementary sheets will be provided to the candidates. 10. Clip board, log tables, slide rule, calculator, cellular phone and electronic gadgets in any form are NOT allowed. 11. The question-cum-answer booklet must be returned in its entirety to the Invigilator before leaving the examination hall. Do not remove any page from this booklet. 12. Refer to special instructions/useful data on the reverse. CY- i / 38 READ INSTRUCTIONS ON THE LEFT SIDE OF THIS PAGE CAREFULLY REGISTRATION NUMBER Name: Test Centre: Do not write your Registration Number or Name anywhere else in this question-cum-answer booklet. I have read all the instructions and shall abide by them. ... Signature of the Candidate I have verified the information filled by the Candidate above. ... Signature of the Invigilator A CY- ii / 38 A Q.1 IMPORTANT NOTE FOR CANDIDATES Questions 1-30 (objective questions) carry three marks each and questions 31-44 (subjective questions) carry fifteen marks each. Write the answers to the objective questions in the Answer Table for Objective Questions provided on page 7 only. The pair of semimetals in the following is (A) Al, Si Q.2 (C) Sb, Te (D) Ca, B The most probable oxidation states for both Cr and Mo are (A) +2, +3, +4 Q.3 (B) Ge, As (B) +2, +3, +5 (C) +2, +3, +6 (D) +3, +4, +5 The correct order of acidic character is (A) Al2O3 > MgO > SiO2 > P4O10 (C) P4O10 > SiO2 > Al2O3 > MgO Q.4 (B) P4O10 > Al2O3 > MgO > SiO2 (D) SiO2 > P4O10 > Al2O3 > MgO The pair of amphoteric oxides is (A) VO, Cr2O3 Q.5 (B) V2O3, Cr2O3 In the structure of B4O5(OH)4 (C) VO2, Cr2O3 (D) V2O5, CrO3 2 (A) all four B atoms are trigonal planar (B) one B atom is tetrahedral and the other three are trigonal planar (C) three B atoms are tetrahedral and one is trigonal planar (D) two B atoms are tetrahedral and the other two are trigonal planar Q.6 The pH of an aqueous solution of Al3+ is likely to be (A) neutral Q.7 (B) acidic (C) slightly basic (D) highly basic Hydrolysis of (CH3)2SiCl2 and CH3SiCl3 leads to (A) linear chain and cross-linked silicones, respectively (B) cross-linked and linear chain silicones, respectively (C) linear chain silicones only (D) cross-linked silicones only Q.8 The oxide that has the inverse spinel structure is (A) FeCr2O4 (B) MnCr2O4 (C) CoAl2O4 CY- 1 / 38 (D) Fe2CoO4 A Q.9 The transition metal monoxide that shows metallic conductivity is (A) NiO (C) TiO Q.10 (B) MnO (D) CoO The metal that is extracted by the reduction method is (A) Al Q.11 (B) Au (B) Ca(II) (C) Ba(II) (B) KFe[Cr(CN)6] (D) Fe[Cr(CN)6] +X Am + 243 97 Bk 1 (B) 0 n (C) 2 1 1H (D) 4 2 He Based on the principle of equipartition of energy, the molar heat capacity of CO2 at constant volume Cv,m is (A) 3.5R (B) 6R (C) 6.5R (D) 9R One mole of a van der Waals gas undergoes reversible isothermal transformation from an initial volume V1 to a final volume V2. The expression for the work done is (A) RT ln 1 V2 b 1 + a V1 b V1 V2 1 V b 1 (D) RT ln 2 a V1 b V1 V2 V2 + a (V2 V1 ) V1 (C) RT ln Q.17 (C) KCr[Fe(CN)6] In the following equation X is 1 (A) 2 0 n Q.16 (D) Sr(II) Addition of an aqueous solution of Fe(II) to potassium hexacyanochromate(III) produces a brick-red colored complex, which turns dark green at 100 C. The dark green complex is 241 95 Q.15 (D) glycerol In ammonical buffer, oxine (8-hydroxyquinoline) forms yellow precipitate with (A) Fe4[Cr(CN)6]3 Q.14 (C) ethylene glycol (B) methanol (A) Mg(II) Q.13 (D) Mg The most viscous liquid is (A) water Q.12 (C) Hg (B) RT ln P2 P1 The scalar product of two vectors u and v, where u = 2i + 3j 5k and v = i + j + 3k, is (A) -10 (B) 2i + 3j 15k CY- 2 / 38 (C) 3i + 4j 2k (D) 10 A Q.18 The minimum concentration of silver ions that is required to start the precipitation of Ag2S (Ksp = 1 10 51) in a 0.1 M solution of S2 is (A) 1 10 49 M Q.19 (B) 1 10 50 M (C) 1 10 26 M (D) 1 10 25 M Identify the correct statement regarding Einstein s photoelectric effect (A) The number of electrons ejected depends on the wavelength of incident radiation. (B) Electron ejection can occur at any wavelength of incident radiation. (C) The number of electrons ejected at a given incident wavelength depends on the intensity of the radiation. (D) The kinetic energy of the ejected electrons is independent of the wavelength of incident radiation. Q.20 The hydrolysis constant (Kh) of NH4Cl is 5.6 10 10. The concentration of H3O+ in a 0.1 M solution of NH4Cl at equilibrium is (A) 5.6 10 11 (C) 5.6 10 10 Q.21 (B) 5.6 10 10 (D) 2.8 10 5 The acid dissociation constant (Ka) for HCOOH, CH3COOH, CH2ClCOOH and HCN at 25 C are 1.8 10 4, 1.8 10 5, 1.4 10 3 and 4.8 10 10, respectively. The acid that gives highest pH at the equivalence point when 0.2 M solution of each acid is titrated with a 0.2 M solution of sodium hydroxide is (A) HCOOH (C) CH2ClCOOH Q.22 (B) CH3COOH (D) HCN For an ideal gas undergoing reversible Carnot Cycle, the plot of enthalpy (H) versus entropy (S) is (B) (A) H H S S (C) (D) H H S S CY- 3 / 38 A Q.23 Hybridizations of the atoms indicated with the asterisk (*) in the following compounds sequentially are O Ph CH2 * Ph O Ph O O * Ph O * O Ph HC CH Ph Ph (A) sp2, sp2, sp3, sp2 Q.24 Ph (B) sp2, sp3, sp3, sp2 (C) sp3, sp3, sp3, sp2 * O (D) sp2, sp2, sp3, sp3 The Cahn-Ingold-Prelog (CIP) priorities of the groups and the absolute configuration (R/S) of the following compound are OH CH2 (H3C)2HC CH3 (A) CH2OH > CH(CH3)2 > CH=CH2 > CH3 and S (B) CH2OH > CH=CH2 > CH(CH3)2 > CH3 and S (C) CH2OH > CH=CH2 > CH(CH3)2 > CH3 and R (D) CH2OH > CH(CH3)2 > CH=CH2 > CH3 and R Q.25 The optically active stereoisomer of the following compound is CH3 HO OH H3C CH3 CH3 (A) (B) OH OH CH3 OH CH3 OH (C) (D) CH3 HO HO CH3 OH OH CY- 4 / 38 A Q.26 The correct relationship within each pair of the natural products is (A) camphor terpene; insulin protein; nicotine alkaloids; streptomycin carbohydrate (B) camphor terpene; insulin carbohydrate; nicotine alkaloid; streptomycin lipid (C) camphor alkaloid; insulin protein; nicotine terpene; streptomycin carbohydrate (D) camphor carbohydrate; insulin protein; nicotine alkaloid; streptomycin terpene Q.27 The correct sequence of relationships between the compounds of the following pairs i-iv is (ii) (i) COOH NH2 H H CH2CH3 CH3 H NH2 Br COOH CH3 Br H CH3 H Br Br H CH3 (iii) Ph CH3 HO H H H2N H HO CH3 NH2 H CH2CH3 CH2CH3 CH3 (iv) H Cl Cl H H Br Br H Ph CH3 CH2CH3 (A) identical, enantiomers, diastereomers and structural isomers (B) enantiomers, identical, structural isomers and diastereomers (C) enantiomers, identical, diastereomers and structural isomers (D) identical, identical, diastereomers and structural isomers Q.28 The INCORRECT statement in the following is (A) the nucleobase pairs are aligned perpendicular to the helical axis in DNA (B) RNA contains uracil and thymine, but DNA contains only thymine (C) all naturally occurring amino acids with the exception of glycine are chiral (D) all enzymes are proteins, but all proteins are not necessarily enzymes CY- 5 / 38 A Q.29 The products P and Q in the following reactions, respectively, are Cl CH3 AgNO3 NaNH2 P Q Cl (B) (A) Cl CH2 CH2 and and Cl CH2 (C) (D) Cl CH3 CH3 and and Cl CH2 Q.30 The major product in the following reaction is O H2NCONHNH2 (1 equiv), HCl, 100 0C O (1 equiv) CHO (1 equiv) (A) (B) O O N C NHNH2 O (C) CH N C NHNH2 (D) O O N NH C NH2 O CY- 6 / 38 CH N NH C NH2 A Answer Table for Objective Questions Write the Code of your chosen answer only in the Answer column against each Question Number. Do not write anything else on this page. Question Answer Number Do not write in this column Question Answer Number 01 16 02 17 03 18 04 19 05 20 06 21 07 22 08 23 09 24 10 25 11 26 12 27 13 28 14 29 15 Do not write in this column 30 FOR EVALUATION ONLY Number of Correct Answers Marks (+) Number of Incorrect Answers Marks ( ) Total Marks in Question 1-30 CY- 7 / 38 ( ) A Q.31 (a) In the following reactions, identify X, Y and Z. Na2SO3 + S AgBr boiling water excess X X + Cl2 + H2O X (colorless solid) Y (soluble complex) boiling water Z + HCl (b) Draw the structures of S4N4H4 and N4S4F4. CY- 8 / 38 (9) (6) A CY- 9 / 38 A Q.32 (a) The magnetic moment of [Fe(phen)2(NCS)2] varies with temperature. The magnetic moments at 200 K and 50 K are 4.9 BM and 0 BM, respectively. Write the delectron configurations of Fe at both temperatures and give reason for the observed change in the magnetic moment. (phen = 1,10-phenanthroline) (6) (b) PCl5 exists as a discrete covalent molecule in the gaseous state, but is ionic in the solid state. Draw the structures of PCl5 in gaseous and solid states. CY-10 / 38 (9) A CY-11 / 38 A Q.33 In the following equilibrium and reactions, identify species B to E. Write the balanced chemical equation for the conversion of C to E. A dil. HCl pH > 6 oxide of Cr solid no d-electrons B yellow color tetrahedral B + diphenylcarbazide C + HCl C strong oxidizing agent D (violet color) E (greenish yellow gas) (15) CY-12 / 38 A CY-13 / 38 A Q.34 (a) Identify species A and C in the following. Write the balanced chemical equation for the conversion of A to A3+. A + aquaregia A3+ + IB + I-(excess) A3+ + NO B (black precipitate) C (orange color) Hint: C on dilution with water gives B (9) (b) Draw the structures of X and Y in the following reactions (i) Borazine + HCl X (ii) Borazine + Br2 Y (6) CY-14 / 38 A CY-15 / 38 A Q.35 (a) The molar conductances at infinite dilution for BaCl2, KCl, K2SO4 and Cl are 280, 150, 300 and 76 1 m2 mol 1, respectively. Calculate the transport number of Ba2+ in BaSO4 solution at infinite dilution. (9) (b) If 4 moles of a MX2 salt in 1 kg of water raises the boiling point of water by 3.2 K, calculate the degree of dissociation of MX2 in the solution. (For water, Kb = 0.5 K kg mol-1) (6) CY-16 / 38 A CY-17 / 38 A Q.36 (a) For the reaction R P, the plot of ln[R] versus time (t) gives a straight line with a negative slope. The half life for the reaction is 3 minutes. (ln 2 = 0.693, ln 0.1 = 2.303) (i) Derive the expression for t1 / 2 . (ii) Calculate the slope of the straight line. (iii) Calculate the time required for the concentration of R to decrease to 10% of its initial value. (9) (b) Shown below is the Jablonski diagram that describes various photophysical processes. The solid arrows represent radiative transitions and the wavy arrow represents a non-radiative transition. (b) Z Absorption S1 T1 (a) X (c) Y S0 (i) Name the photophysical pathways X, Y and Z. (ii) Which of the radiative decays is faster? CY-18 / 38 (6) A CY-19 / 38 A Q.37 (a) (i) Given that G = nFE, derive the expression for the temperature dependence of the cell potential (E) in terms of the change in entropy ( S). (ii) For a cell reaction, E (at 25 C) = 1.26 V, n = 2 and S = 96.5 J K 1 mol 1. Calculate E at 85 C by assuming S to be independent of temperature. (F = 96500 C mol 1) (9) Temperature ( C) (b) The phase diagram for the lead-antimony system at a certain pressure is given below. Liquid 631 327 Region I M 246 Region II 0 Mole fraction of Lead 1 (i) Identify the phases and components in region I and region II. (ii) Calculate the number of degrees of freedom (variance) at point M. CY-20 / 38 (6) A CY-21 / 38 A Q.38 (a) One mole of an ideal gas initially at 300 K and at a pressure of 10 atm undergoes adiabatic expansion (i) reversibly and (ii) irreversibly against a constant external pressure of 2 atm until the final pressure becomes equal to the external pressure. Calculate Ssystem for (i) and (ii). For (ii), express the final answer in terms of R. Given: Molar heat capacity at constant volume Cv,m = 3R/2 (9) (b) For the following equilibrium at 300 C, N2O4 (g) 2NO2 (g) Calculate Kp when N2O4 is 30% dissociated and the total pressure is 2 bar. CY-22 / 38 (6) A CY-23 / 38 A Q.39 (a) The Maxwell probability distribution of molecular speeds for a gas is 3/ 2 mv 2 m F (v)dv = 4 v 2 exp dv 2kT 2 kT where v is the speed, m the mass of a gas molecule and k the Boltzmann constant. (i) Use F (v) to show that the most probable speed vmp is given by the expression 1/ 2 2 RT v mp = M (ii) Use R = 8 J K 1 mol 1 in the above expression to calculate the v mp for CH4(g) at 127 C. (9) (b) The wavefunction of a quantum state of hydrogen atom with principal quantum number n = 2 is 1 2lm (r , , ) = 32 a0 1 3/ 2 r 2 a 0 r exp 2a 0 (i) Identify the values of quantum numbers l and m and hence the atomic orbital. (ii) Find where the radial node of the wavefunction occurs. CY-24 / 38 (6) A CY-25 / 38 A Q.40 (a) Write the possible substitution products in the following reactions. Indicate the type/s of mechanism/s (SN1/SN2/SN2 ) that is/are operative in each reaction. i) ii) Br Br CN , DMF CH3OH ? ? (9) (b) Write the elimination products A to C in the following reaction. Identify the major product. OH H3PO4, H A B C (6) CY-26 / 38 A CY-27 / 38 A Q.41 (a) Write the structures of A to C in the following reaction sequence. H3C-CH=CH2 HCl, AlCl3 A CH3COCl, AlCl3 B (major product) 1. CF3COOOH, CH2Cl2 2. NaOH, 3. H3O C (9) (b) Write the structures of D and E in the reactions given below. H3C CH3 1. Br2, FeBr3 1. HNO3, H2SO4 2. SnCl2, HCl 3. (CH3CO)2O D (major product) 2. KOH, H2O, E 3. NaNO2, HCl 4. H3PO2 (6) CY-28 / 38 A CY-29 / 38 A Q.42 (a) Write the structures of A to C in the following reaction sequence. 1. NaNH2 CH3 m-ClC6H4COOOH, benzene A CH3 2. H3O B C 3. NaNO2, HCl (9) (b) Write the structures of D and E in the following reaction. OH NH2 Ph O Br2, OH H2O, D (intermediate) E (stable product) (6) CY-30 / 38 A CY-31 / 38 A Q.43 Write the structures of the products A to E in the following reaction sequence. N(CH3)2 Li, NH3 (liq) A H3O t-BuOH B isomerization CH3 C CH3 (H3C)3SiO D H3O E CY-32 / 38 (15) A CY-33 / 38 A Q.44 Oxanamide O, a tranquilizer, is synthesized according to the following reaction Scheme. Write the missing structures and reagent/s K to O. C8H16 K: Reagent/s 2 L (C4H8O and gives positive test with Tollen's reagent) NaOH, (-H2O) (Z) M Ag2O, NaOH (oxidation) N 1. SOCl2 2. NH3 3. CF3COOOH O (an epoxy amide) (15) CY-34 / 38 A CY-35 / 38 A SPACE FOR ROUGH WORK CY-36 / 38 A SPACE FOR ROUGH WORK CY-37 / 38 A SPACE FOR ROUGH WORK CY-38 / 38 A CY-iii / 38 A 2011 CY Objective Part (Question Number 1 30) Total Marks Signature Subjective Part Question Number 31 Question Number 38 Marks 32 39 33 40 34 41 35 42 36 43 37 44 Total Marks in Subjective Part Total (Objective Part) : Total (Subjective Part) : Grand Total : Total Marks (in words) : Signature of Examiner(s) : Signature of Head Examiner(s) : Signature of Scrutinizer : Signature of Chief Scrutinizer : Signature of Coordinating Head Examiner : CY-iv / 38 Marks

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