i ENTRANCE EXAMINATION, 2015 ENTRANCE EXAMINATION, 2015 Pre-Ph.D./Ph.D, CHEMICAL SCIENCES [ Field of Study Code : CHEP (162) ] Time Allowed : 3 hours Maximum Marks : 70 INSTRUCTIONS FOR CANDIDATES (i) All questions in Part—A are compulsory. (i) In Part—A, each correct answer carries 15 marks and wrong answers carry (05) mark. (iii) The answers for Part—A must be written in the box provided on Page 3. (iv) Answer only 8 questions from Part—B. (*) Answer for Part—B must be done in the space provided along with the question. (vi) If additional space is required, two extra sheets provided at the end of the paper can be utilized for rough work. (vii) Use of calculator is permitted. 187-A i i i i i 1 i i 1 ' 1 1 1 fl I i 1 1 1 i 1 1 1 1 I i i i ' t i i i i 1 I i ' 1 I 1 t 1 I 1 ' 1 I i t I I i ' 1 i i ' 1 i i i Pre-Ph.D./Ph.D. CHEMICAL SCIENCES SUBJECT FIELD OF STUDY CODE NAME OF THE CANDIDATE . REGISTRATION NO. 87 CENTRE OF EXAMINATION. DATE. . (Signature of Candidate) (Signature of Invigilator) (Signature and Seal of Presiding Officer) 187-0/87-AWrite down the answers for the multiple choice answers given in Part—A : Question No. Answer Question No. Answer Al All a2 Al2 a3 A13 At Ald AS Als AG Al6 AT Al7 AS Als as alg Alo A20 /87-A 3 [P.T. 0.(37-AFundamental Constants : . Value Speed of light (c} 299792558 x 108 ms! eee) 1602176 x 10719 ¢ Boltzmann constant (k) 138065 x 10°23 y K-1 Gas constant (R= N,k) 831 JK! mol7! Planck constant (h) 662608 x 10°54 J s Avogadro's constant (NV, ) 602214 x 1074 mol? Electron mass (m,) 911 x 1073! kg Proton mass (m_,) 167 x 1077 kg Neutron mass (m,,) 167 x 10°77 kg Bohr radius (ag = 4ne gh? /m,e2) 53 x107! m 187-A 5 [P.7.0.PART—A Important Note : Each wrong answer carries (-0'5) mark Multiple Choice Questions 1-5*20=30 Al. The coordination number of phosphorus in [PMo, 049°" is (a) (b) (a) aaws A2. The electronic transition of the metal complexes [MnjH0}¢|?* and [NilH0}6]2* would be (a) spin-forbidden, laporte-forbidden and _—_spin-allowed, _laporte-forbidden, respectively (0) both spin-forbidden, laporte-forbidden llowed (c) both spin-allowed, laporte- (@) both spin-allowed, laporte-forbidden 3. Which one of the following pairs of d-electron configuration of high-spin transition metal ions (3d) in an octahedral field undergoes a strong Jahn-Teller distortion? (@ a8, a9 ) a9, a9 ) a4, a9 @ a®, a9 A4. Superoxide dismutase contains the metal ions (a) Cufll) and Fe(tity () Cu(ll) and Zn) () Cully and Co(itt) (d) Cuqtty and Ni(ll) AS. 41 (calculated) for Cr?* in high-spin and low-spin complexes should be (a) 490 BM and 2:83 BM, respectively (b) both 4-90 BM () 1-73 BM and 2:83 BM, respectively (d) 490 BM and 1-73 BM, respectively /87-A 6A6. The complex which obeys the 18-electron rule is (a) Fe(CO), (0) Ni(CO)(PPh3) () CrCO)s (a) CrCsHs)y Az. are (a) (o) (C) (a) closo and arachno nido and closo closo and nido nido and arachno A8. The product of the given reaction is, (c) Ts—-N NH—Ts (a) None of the above Applying the Wade's rule, the structures of BygCgHyo and [BgCoH 1]7”, » respectively A9. In the given coupling reaction, the correct product and name of the reaction is S mol % Pa(PPhs}e dioxane, LiCl, 80“ ao” So @ o» SA Negishi-coupling Negishi-coupling Stille-coupling 187-A See eeeeee ree Kumada-coupling [P.1.0,lowing molecule are A10. The absolute configurations of two chiral centres in the foll 1 COOH OH (a) AR), 318) (b) AR), SR) () 2S), 3(S) (a) 2S), 3(R) 11. In allene, hybridization of the central and terminal carbons, respectively are (a) sp? and sp* () sp? and sp? (c) sp and sp? (4) sp? and sp 12. Match List—I (Rearrangement) and List—II (Intermediate of the rearrangement) and select the correct answer using codes given below List List—I1 (Rearrangement) (intermediate of the ® rearrangement) A. Favorskii rearrangement 1. Ketene B. Wolff rearrangement 2. Carbocation C. Schmidt rearrangement 3. Cyclopropanone D. Wagner-Meerwein rearrangement 4. Isocyanate Codes : @ aA B oc oD 3 1 2 4 A B oc op 3 91 4 2 MA B Cc Dp 204 1 3 @aA B oc Dp 392 4 1 (87-A 8Al3. Ala, Als. Al6. /87-A In the given reaction, the final step is (a) (b) (o} (a) CH CHa iy Natt (i) Bui 7 — a) Sa i) (a) HS ale} oH Ph Br (3, 3] sigmatropic rearrangement Ph (2, 3] sigmatropic rearrangement (1, 3] sigmatropic rearrangement electrocyclic ring opening reaction TH NMR spectra of (CH3)90, CHF and RCOOH show chemical shift (8) in ppm at (a) (b) to} (a) 3-27, 4:30 and 10-80 respectively 430, 327 and 10:80 respectively 3-27, 108 and 4:30 respectively 10°80, 4:30 and 3:27 respectively A dye solution of concentration 26 uM shows the optical density of 0:5 in a 1 cm quartz cell at 400. nm. The molar extinction coefficient of the dye is given by (a) (b) (c) (a) 1923077 M7! mm7! 50 M7! cm? 13000 M~! mm~? Cannot be calculated If the rate constants for decomposition NOs, q+ 30 are 3-46x 107° and 487x107 at 25°C and 65°C, respectively, then the activation energy is given by (given R = 1-987 cal mol~! K~}) fa) (b) (c} (a) 26-8 kcal mol! 24-8 keal mol! 23-5 kcal mol”! 48-2 kcal mol! 9 [P.T.0.AIT. Als. Al9. /87-A Which of the following statements explains why the speed of some chemical reactions is increased when the surface area of the reactant is increased? (a) This change increases the density of the reactant particles (b) This change increases the concentration of the reactant (c) This change exposes more reactant particles to a possible collision (@) This change alters the electrical conductivity of the reactant particles ‘The energy of a 355 nm photon can be converted to the wave number equal to (a) 21171 em=! (6) 21269 cm) (21160 cm~! (a) 21169 cm"! ‘The heat absorbed by 2-5 mole of a gas in expanding it from 31 L to 47 Lat 25 °Cis (a) 2678.5 fo) 2578.5 () 3578 (a) 2587 5 Given standard electrode potentials Fe2+ +20 — Fe, E°=()0-440V, Fe3* 4 3¢ 7 : Se Fe E° =()0-360 V. The standard electrode * potential (69) for Fe* +e pe2* ig (a) -0-476V fo) -0-404,V @ +0 404.V (@ +0-771V 10PART—B 5x8 Answer any eight questions (Descriptive) BL. Green crystals of [Ni(Ph jEtP)) Br] have a magnetic moment of 3:20 BM and red crystals of [Ni(PhEtP)>Br5] do not have any magnetic moment. Suggest the structures for the green and red compounds and offer an explanation for the magnetic moment. /87-A ll [P.T.O,/87-AB2. The following thermolysis of the dimer [{q5-C /87-A gas per mole of dimolybdenum complex and generates a m>-CsHg)Mo(CO}g}o : (a) o) ‘SH5)Mo(CO}3]5 releases 2 moles of CO stable product Sketch the structures of the reactant and the product, What is the oxidation state of Mo in each compound and what is the d-electron count of Mo in each? 13 [P.T.0./87-A 14B3. Sn** +2e > Sn?* £°=0-15V FeS* +e > Fe? £°=0-77V Write the balanced equation for the reaction expected with given standard potentials, Calculate the equilibrium constant for the expected reaction at 25 °C. /87-A 15 [P.7.0,/87-AB4. (a) Reduction of Coffll) in [Co(NH,)Cl]?* complex by Cr(l) in [Cr(Hi,0)¢]?* is 10'° times faster than the reduction of (Co(NHg)¢]°*. Explain in detail. () Permanganate solutions are intrinsically unstable in acidic solutions and decomposition is catalyzed by sunlight. Comment with detailed equations. (87-A 17 [P.T.O./87-ABS. An organic compound gives amine ‘B’ (CgH) 4N)). Amine B on reaction with excess of Mel followed by heating having molecular formula CgH7N,, on reduction with Ho /Ni with AgOH provides unsaturated compound ‘€’ with molecular formula CgH,7N) Further, reaction of compound C with Mel and subsequent heating with AgOH gives a stable diene ‘D’ (CgHjo) and amine ‘EB’, Compound ‘D’ on oxidative ozonolysis gives pyruvic acid, acetic acid and formic acid. Identify all the products and explain the formation of compound D starting from compound B. 187-8 19 [P.1.0./87-A 20B6. Elucidate the molecular structure from the following spectroscopic data 187-A Molecular formula : C3H,0 UV : No A above 220 nm 3350, 3090-3015, 2990-2870, 1650, 1025 IR ¢m~ NMR : 64-04, doublet of triplet, 2H, J=4-8 and 1-4 Hz 84-40, singlet, 1H 85-10, doublet of multiplet, 1H, J=9:6 and 1-4 Hz 85:25, doublet of multiplet, 1H, J= 17-4 and 1-4 Hz 85-94, doublet of quintet IH, J= 17-4, 96 and 4:8 Hz a. [P.7.0./87-A 22B7. (a) Draw only the y;, V2, W3 and w4 MOs of 1,3-butadiene () Write the products and sketch the mechanism for the following reactions 0 Ly ee » . Hf /87-A 23 [P.T.O./87-A 24BB. Write an arrow formalism econ for the following reactions (a) (o) 187-A HO NaOH 0” NaOH, io” “~~ i 25 [P-7.0.187-8 26B9. (a) Can we apply the steady-state approximation in the following reaction and under which condition? ky k, A—151—25B (b) What is the statement of first law of thermodynamics? Give the correct mathematical equation for work done in isothermal reversible expansion of an ideal gas. /s7-A 7 {P.7.0/87-A 28B10. (a) Starting from the uncertainty principle, ApAx > a show that for a free particle the uncertainty in energy and time is given by AEAt > i (@) Calculate the wavelength associated with a person of weight 70 kg who walks with a speed of 10 km/h. (Planck’s constant is given by 6-63x 10734 J-s) 187-A 292 [P-T.0./87-A 30B11. (a) In the pure rotational spectrum of CO, vo_,, = 3-84235 cm“. Calculate the internuclear distance of the molecule if ugg = 11-38365x 10-27 kg (b) What are meant by Stokes and antiStokes lines in Raman Spectra? /87-A 31 [P.7.0.187A 32B12. (a) Define fluorescence and phosfluorescence. Draw the Jablonski diagram for different electronic transitions showing the fluorescence and phosth luorescence (b) Deduce the Brage’s equation for incoming X-ray beam falling on a crystal /87-A 33 [P.T.0,ake 187-A caSPACE FOR ROUGH WORK /87-A 35 [P:T.0.SPACE FOR ROUGH WORK se7A 36 E15—450%2