MAIN PAPER — CY. CY : CHEMISTRY Duration : Three Hours ‘Maximum Marks :150 Read the following instructions carefully 10, 12, ‘This question paper contains 24 printed pages including pages for rough work, Please check all pages and report discrepancy, if any. Write your registration number, your name and name of the examination centre at the specified locations on the right half of the ORS. Using HB pencil, darken the appropriate bubble under each digit of your registration number and the letters corresponding to your paper code. All the questions in this question paper are of objective type. Questions must be answered on Objective Response Sheet (ORS) by darkening the appropriate bubble (marked A, B, C, D) using HB pencil against the question number on the left hand side of the ORS. Each question has only one correct answer. In case you wish to change an answer, erase the ‘old answer completely. More than one answer bubbled against a question will be treated as a wrong. answer, Questions 1 through 20 are I-mark questions and questions 21 through 8S are 2-mark questions. ‘Questions 71 through 73 is one set of common data questions, questions 74 and 75 is another pair of common data questions. The question pairs (76, 77), (78, 79), (80, 81), (82, 83) and (84, $5) are questions with linked answers. The answer to the second question of the above pairs will depend on the answer to the first question of the pair. Ifthe first question in the linked pair is wrongly answered ‘is un-attempted, then the answer to the second question in the pair will not be evaluated. Un-attempted questions will carry zero marks. NEGATIVE MARKING: For Q.1 to Q.20, 0.25 mark will be deducted for each wrong answer. For Q21 to Q.75, 0.5 mark will be deducted for each wrong answer. For the pairs of questions with linked answers, there will be negative marks only for wrong answer to the first question, i. for Q.76, Q.78, Q.80, Q.82 and Q.84, 0.5 mark will be deducted for each wrong answer. There is no negative marking for Q.77, 0.79, Q.81, Q.83 and Q.85. Calculator without data connectivity is allowed in the examination hall . Charts, graph sheets and tables are NOT allowed in the examination hall Rough work can be done on the question paper itself: Additional blank pages are given at the end of the question paper for rough work. a vasMAIN PAPER CY Some Useful Data Physical Constants: Universal gas constant, R = 8.314JK" mot! = 0.082 L atm K" mot" 6.626 x 10 Js Planck constant, Avogadro number, 6.023 x 10° mot Faraday constant, F = 96485 C mol" Electron charge, e = 1602x10"%C ‘Speed of light, © = 2.998x10°ms" Boltzmann constant, kp = 1.381 x 103K? Electron mass, me = 9.109 x 10°" kg 2. Atomic Numbers: S= 16; Cl= 17; Ti= 22; V = 23; Cr= 24; Mn= 25; Ru= 44; Rh= 45; Re = 75; Os = 76. B 9; Al= 13; Si= 14; P Fe = 26; Co= 27; Ni=28; Cu aq Te2008 MAIN PAPER CY Q.1-Q. 20 Carry one mark each QL The total number of isomers of Co(en);Cl; (en = ethylenediamine) is ws (B)3 os ms Q2 — Metal-metal quadruple bonds are well-known for the metal (A) Ni (B) Co (Fe (D) Re Q3 The reaction of AL,C; with water leads to the formation of (A) methane (B) propyne (C) propene (D) propane Q.4 The correct statement about Cys is (A) Ceo is soluble in benzene (B) Ceo does not react with tert-butyllithium | (C) Ceo is made up of 10 five-membered and 15 six-membered rings. (D) Two adjacent five-membered rings share a common edge Q5 The lattice parameters for a monoclinic crystal are (A)a¢b#c;a=y=90" (Bya=b#c;aF¢BFy (Cha¢bsc;a¢pey (D)a=b=c;a=y=90" Q.6 The magnetic moment of [Ru(H;0).]"* corresponds to the presence of (A) four unpaired electrons (B) three unpaired electrons (C) two unpaired electrons (D) zero unpaired electrons Q7 The compound that is NOT aromatic is “ ® @ 8 © ©) C w va2008 MAIN PAPER CY. Q.8 The order of stability for the following cyclic olefins is irmeey wien (QOu< Wl<1 Bultio> BsHy > Bothy (B) Bally = Bullio> BsHy = Bots (©) Biols > BSH,> Belo > Balls (D) Belly > ByHio> Bul, > Bots NaCl is crystallised by slow evaporation ofits aqueous solution at room temperature, The correct statement is (A) The crystals will be non-stoichiometric (B) The crystals should have Frenkel defects (C) The percentage of defects in the crystals will depend on the concentration of the solution and its, rate of evaporation (D) The nature of defects will depend upon the concentration of the solution and its rate of evaporation CaTiO has a perovskite crystal structure. The coordination number of titanium in CaTiO; is as (6 ©3 12 IECIE; were to be stereochemically rigid, its '"F NMR spectrum (I for "F =") would be (assume that Cl is not NMR active) (A) a doublet and a triplet (B) a singlet (C)a doublet and a singlet (D) two singlets ‘The point group of NSF, is (A) Dig (B) Cy, (Dy O)CyQ31 Q32 Q33 Q34 Q35 Q36 MAIN PAPER CY When NiO is heated with a small amount of Li,O in air at 1200 °C, a non-stoichiometric compound Li,Niq.)0 is formed. This compound is (A) an n-type semiconductor containing only Ni'* (B) an n-type semiconductor containing Ni'* and Ni"* (©) ap-type semiconductor containing Ni™* and Ni** (D) p-type semiconductor containing only Ni™* White phosphorus, Py, belongs to the (A) closo system (B) nido system (©) arachno system (D) hypho system ‘Among the compounds Fe,O,, NiFe:0, and MnO, (A) NiFe,O, and Mn;O, are normal spinels (B) Fe;0, and MnO, are normal spinels (C) Fe,O, and MnO, are inverse spinels (D) FexO, and NiFe:0. are inverse spinels ‘The number of M-M bonds in Ir(CO))2 are (A) four (B) six (Oecight (D) zero Schrock carbenes are (A) triplets and nucleophilic (B) triplets and electrophilic (©) singlets and nucleophilic (D) singlets and electrophilic ‘The INCORRECT statement about linear dimethylpolysiloxane, {(CH,):SiO]p, is (A) itis extremely hydrophilic (8) itis prepared by a KOH catalysed ring-opening reaction of [MesSiO]. (©)it has a very low glass transition temperature (D) it can be reinforced to give silicon elastomers a2008 MAIN PAPER CY Q.37 Match the entries a-d with their corresponding structures p-s. OO are << b _atropisomeric system q os — : ae Me OMe (in Sa, (A) acs; b-r; e-q; d-p (B) a-p;_b-s; e-g; dr (C) a-q; b-p; e-s; dor ()a-s; b- 3 d-q Q.38 The reaction between X and ¥ to give Z proceeds via (A) 4x-conrotatory opening of X followed by endo Diels-Alder cycloaddition (B) 4x-cisrotatory opening of X followed by endo Diels-Alder cycloaddition (©) 4r-conrotatory opening of X followed by exo Diels-Alder cycloaddition (D) 4x-disrotatory opening of X followed by exo Diels-Alder cycloaddition ae om2008 MAIN PAPER CY 0.39 The major products Py and P,, respectively, in the following reaction sequence are @°0 A He/ Ni fonoee ae iGo ey (A) 9 enue arte A me i i (B) See rs OQ OH coal a i © n-O QO OH wee due ow Ane @) a esl f ned wee Me Me 40. The products ¥ and Z-are formed, respectively, from X via ° oe : ct 4 x (in Zz D (A) hy, conrotatory opening, and A, disrotatory opening (B) hy, disrotatory opening and A, conrotatory opening (©)A,conrotatory opening and hy, disrotatory opening (D) A, disrotatory opening and hy, conrotatory opening, a Toa2008 MAIN PAPER CY Q441_o-Bromophenol is readily prepared from phenol using the following conditions (A)i) (CH,CO);0; it) Bry; iii) HCL-H0, 4 (B) i) H:S0,, 100°C fi) Bry iti) HO", 100°C (©) N-Bromosuccinimide, dibenzoyl peroxide, CCly, A (D) Bry/FeBry Q.42._ The major product of the following reaction is ‘Pr T(O-Pr)., L-(+)-iethy| tartarate ee oH "BuOOH, CHzCl,, 20°C “ B) és °: ase Pr oH © ©) of ‘Pr Q.43 The photochemical reaction of 2-methylpropane with F: gives 2-fluoro-2-methyipropane and 1- ‘uoro-2-methylpropane in 14:86 ratio. The corresponding ratio of the bromo products in the above reaction using Br; is most likely to be (A) 14:86 (B) 50:50 ©r9 (D)99:1 Q44 The major product P of the following reactions is O° QO eS 2 ) a =~" On On ‘ i) MeN (excess) iy H0° “) © ° on wasp 9 my “om © © ° ° MeOH HO wv TiaPn [MAIN PAPER CY Q45__ The reagent X in the following reaction is, cb A, ap Ho. PhgP,PhCO2H, Xp THE (A) 8) HO;CN=NCO;H E10,CHC=CH-CO;Et © ©) — OrerO Q.46 The major product of the following reactions is . 4 i) Hol OAc) HzO, THE oon i) NaBHs, OH? heat (A) 8) wot wn woh nay © ° @) Hier anee Arr yo Q.47 The major product of the following reaction is C. Ho, PtO2 (cat.) CO;CHy ACOH, room temperature @ ®) © ) oa ‘ore ar Tae48. Q49 Qs0 Qs MAIN PAPER CY In the following compound, the hydroxy group that is most readily methylated with CH:N3 is q Pp HO OH ce HO. 07 SO HO’ s “Ap @q Or ()s ‘The most appropriate sequence of reactions for carrying out the following transformation is O—C (A) i) OvHOs; fi) excess SOCIy/pyridine; ili) excess NHs; iv) LiAIH (B) 1) OYMe,S; ii) excess SOCl/pyridine; ii) LiAIHy: iv) excess NH; (©) i) OYHLOs; ii) excess SOClypyridine; iii) LiAIHa; iv) excess NHy (D) i)O,MesS; ii) excess SOClypyridine; iii) excess NHs; iv) LiAIHy ‘The number of optically active stereoisomers possible for 1,3-cyclohexanediol in its chair conformation is ays (B)3 (2 1 ‘The major product of the following reactions is Me i) BHy-THF il) Haz, NaOH (A) ®) Me Me OH OH © @) OH : ° OF Tae2008 Qs2 Q53 Qs4 Q55 [MAIN PAPER CY In the following reaction, we HCN OH =» Xx+¥ ‘CH,OH D-Giyceraldehyde (2 diastereomers) ‘The absolute configurations of the chiral centres in X and ¥ are (A) 25,3R and 2R,3R (B) 2R,3R and 28,38 (©) 28,38 and 22,38 (D) 28,3R and 25,3R ‘The IR stretching frequencies (cm) for the compound X are as follows: 3300-3500 (s, br); 3000 (mm); 2225 (8); 1680 (s). sisy : NC "OH os ‘The correct assignment of the absorption bands is Mie ai a te na Voor = 3300-3500; Vicw) = 3000; Vien = 2225; Vico) = 1680 ®) pou = 3000; Vicry = 3300-2500; View = 2225; Vico) = 1680 oO ‘Voor = 3300-3500; Vien = 3000; Von) = 1680; Vico) = 2225 @) ‘oe Voor = 3000; Vicx) = 3300-3500; Vion = 1680; Veco) = 2225 ‘The T, point group has 24 elements and 5 classes. Given that it has two 3-dimensional irreducible representations, the number of one dimensional irreducible representations is (i (B)6 (2 (D)3 ‘The total number of ways in which two nonidentical spin / particles can be oriented relative toa constant magnetic field is at (B)2 ©3 (D4Q56 Qs7 Qs8 Q59 Q.60 Qe Q62 Q63 MAIN PAPERC¥ Approximately one hydrogen atom per cubic meter is present in interstellar space. ‘Assuming that the H-atom has a diameter of 10" m, the mean free path (m) approximately te (A) 10"° (B) 10" (©) 10" (D) 10" {ee Mavefinction ofa diatomic molecule has the form y = 0.89 cyan + 0.45 @ sae The chance that both electrons of the bond will be found on the same atom in 100 inspections of the molrenla approximately is a7 (B)20 (4s (D) 60 For the reaction given below, the relaxation time is 10° s, Given that 10% of A remains at equilibrium, the value of &; (3") is hy A= =s ky (A) 9x 10° (B) 10% Ow (D) 9x 10% ‘The minimum number of electrons needed to form a chemical bond between two atoms is @ @)2 (3 (4 ‘The ground state electronic energy (Hartree) of a helium atom, neglecting the inter-clectron repulsion, is (A)- 10 (B)-05 (©)-20 @)-40 Article is confined toa one-dimensional box of length 1 mm. Ifthe length is changed by 107 m, the % change in the ground state energy is (A)2x 10% (B)2x 10? (©)2x 107 (0 certain molecule can be treated as having only a doubly degenerate state lying at 360 cm above the nondegenerate ground state. The approximate temperature (K) at which 15% ofthe trolecete, will be in the upper state is (A) 500 (B) 150 (€) 200 (D) 300 A box of volume V contains one mole of an ideal gas. The probability that all N particles will be found occupying one half ofthe volume leaving the other half empty is @in (B)2N mars (Dy (12) " 15a65 2.66 Q67 Q.68 Q09 Q70 MAIN PAPER CY According to the Debye-Hiickel limiting law, the mean activity coefficient of 5 x 10% mol kg" aqueous solution of CaCl, at 25 °C is (the Debye-Hiickel constant °A* can be taken to be 0.509) (A) 0.63 (B)o72 (©)0.80 (D091 ‘The operation of the commutator (x, d/dx] on a function f(x) is equal to (Ayo (B) fix) (C) -fix) (D) x dfidx Ifa gas obeys the equation of state P (V —nb) = aRTT, the ratio (Cy_Cy)/ (Cy-C)ies is (aye @<1 ou. (D)(1-b) Physisorbed particles undergo desorption at 27 °C with an activation energy of 16.628 kJ mol, Assuming first-order process and a frequency factor of10" Hz, the average residence time (in seconds) of the particles on the surface is (A)8x 10" (B)8x 10" (©)2x 10” (D) 1x10 ‘The rotational constants for CO in the ground and the first excited vibrational states are 1.9 and 1.6 em’, respectively. The % change in the internuclear distance due to vibrational excitation is (ayo (B)30 (16 (yo ‘The mechanism of enzyme (E) catalysed reaction of a substrate (S) to yield product (P) is k ets pg te pep; [5] __ kik [S}-KiKIPI (E, ky ka dt Ky [S}k [P+ Ifa small amount of S is converted to P, the maximum rate for the reaction will be observed for (A) (ki +a) >> [ST (B) (ki +k) << ky [S] 0 (©) (ka + ks) = (ki +k) () ka << ky The lowest energy state of the (1s)" (2s)' (3s)! configuration of Be is (A) 'So (B)'D; ©’s: o'r, a2008 (MAIN PAPER CY Common Data Questions ‘Common Data for Questions 71, 72 and 73: An electron accelerated through a potential difference of @ volts impinges on a nickel surface, whose (100) planes have a spacing d = 351.8 x 10"* m (351.8 pm). Q.71 The de-Broglie wavelength of the electron is 2 / pm = (a/ @)"?. The value of ‘ain volts is (A) 15x10" (B) 15x 10° (©)6.63 x 10° (D)2.5 x 10" Q.72__ The condition for observing diffraction from the nickel surface is (A) a>> 2d (B)As24 (O Asad (D) Azad Q.73. The minimum value of ¢ (V) for the electron to diffract from the (100) planes is (A) 3000 (8) 300 (C30 (D3 Common Data for Questions 74 and 75: An iron complex [FeL}”* (L = neutral monodentate ligand) catalyses the oxidation of (CH);S by perbenzoic acid. Q74 The formation of the organic product in the above reaction can be monitored by (A) gas chromatography (B) cyclic voltammetry (©) electron spin resonance (D) fluorescence spectroscopy Q.75 The oxidation state of the metal ion in the catalyst can be detected by (A) atomic absorption spectroscopy (B) Massbauer spectroscopy (COHPLC (D) gas chromatography w 1782008 MAIN PAPER cy Linked Answer Questions: Q.76 to Q.85 carry two marks each Linked Answer Questions 76 and 77: In the reaction, HCN (PPha)srncr —CH X+Y Q.76 Compound X is (A) (B) PPhs PhsP—Rh—ci Hye © (D) a Q.77 _Rh(PPh;)sCl reacts very fast with a gaseous mixture of Hy and C3H, to immediately give Z. The structure of Z is Oy) ¥ @) pee C-CHs PN Rh wore © ©) (PPh;),RhCI(n7-C2H,) PPhs2008 MAIN PAPER CY Linked Answer Questions 78 and 79: ‘The reaction of PCL, with methanol inthe presence of triethylamine affords compound X. El mass pen of X shows a parent ion peak at m/z = 124. Microanalysis of X shows that it contains C, H, O and The 'H NMR spectrum of X shows a doublet at 4.0 ppm. The separation between the two nec eft doublet is approximately 15 Hz (I for 'H and "'P = ¥), Q78 Compound X is (A) (CH,O);P (B) (CH;O),P(0) (©)(CH,0),P(0 KOH) ()(CH.O)PH 2.79 Upon heating, compound X is converted to ¥, which has the same molecular formula as that of X. The 'H NMR spectrum of ¥ shows two doublets centered at 3.0 ppm (separation of twe lines 2) Hz) and 4.0 ppm (separation of two lines ~ 15 Hz) respectively. Compound ¥ is (A) (CH,O):P(OKOH) (8) (CH,0);P (©) (CH.O)(CH,)P(O) (D) (CHO)(CHy)P(OH), Linked Answer Questions 80 and 81: For butyrophenone (PhCOCH:CH:CH;), 2.80 the most probable fragmentation observed in the electron impact ionization (El) mass spectrometry (a) ®) © () Je i +e + A Ph’ CHs on H,C7 ~CHs, Q.81 _ photoirradiation leads to the following set of products. (A) a (B) 6 pry + eer Me JX © @) z 9 JL + HyC-CHy JL Pho ~cHy, + wr 182008 MAIN PAPER CY Linked Answer Questions 82 and 83: In the following reaction, oN i hy Sie °e Q82 the reactive intermediate I and the product P are a @) carbene and 7 radical and. ASS 4 © @) carbene and ANH radical and eee) Q.83__ the product P shows ‘m’ and ‘n’ number of signals in 'H and "C NMR spectra, respectively. The values of ‘m’ and ‘n’ are (A) m=3andn=2 (B) m=2andn=3 (©) m=2andn=2 () m= and n=3 Linked Answer Questions 84 and 85: The infrared spectrum of a diatomic molecule exhibits transitions at 2144, 4262 and, 6354 em" corresponding to ex: jons from the ground state to the first, second and, third vibration states respectively. Q.84 The fundamental transition (em") of the diatomic molecule is at (ay 2157 (B) 2170 (E2183 (D) 2196 Q.85__ The anharmonicity constant (cm) of the diatomic molecule is (A) 0.018 (B) 0.012, (©)0.006 (D) 0.003 END OF THE QUESTION PAPER wr Toa