60 SOLVED PAPER : CSIR-UGC-NETIJRF Dec. 2014 65, ‘The major product formed in the following reaction is 7 we CS 0 of" 0 Q - ol NH2 ba NH2, Nie Soln. Chemical reaction involved in the above transformation can be illustrated as OMe | Oo mi? OMe Cy t Benzyne NHy Correct answer is (a) C. the con xnds which can exhibit optical activity are © Bory ()AandConly (4) Band Conly Compound B can be represented in fisher projection as shown below oo on ‘Eclipsed form (a) A, Band C (b) Aand Solu. HO. Staggered form ‘B) $0, its not optically Here in fisher pro} ion ir contain plane of symmetry passes through mid of "y Hence, it is optic: inactive. Correct answer is (c)Sola. 63. Soln. 64, Soln, ‘SOLVED PAPER : CSIR-UGC-NETIJRF Dec. 2011 59 ‘Among the following drugs, the anticancer agents is: {a) captopril (©) chloroquine (©) camptothecin (d) ranitidine Correct answer is (c). ‘The reaction that involves the formation of both C-C nd C-O bonds is (@) Diels-Alder reaction (b) Darzen’s glycidic ester condensation (©) aldol reaction (@) Beckmann rearrangement (Chemical reaction involved in the above transformation can be illustrated as ° ° i —BR, ONY gy2 Ss <>, | > >} SN wee - ASO 0. BO. cl ° 0 Correct answer is (b). ‘Among A- , the aromatic compounds are ~S C2 2 @) {B) © (a) A, Band C ()AandBonly — (c) Band Conly (a) Aand C only Since in ease of A the hydrogens present at 1* and 6* position repel each others. Hence planarity of distorts. While in case of B and C this type of planarity is maintained, t In the following Markownikov addition reaction, the products A and B are AY a er (a) homomers (®) enantiomers Correct answer is (¢). (©) diastereomers (d) regioisomers Chemical reaction involved in the above transformation can be illustrated as sp 5 oe eo Se. An Ar Br Br ‘Compound A and B are diastereomers due to differatiasiexabandite configuration at carbon 2 and 3 Correct answer is (€)58 Soln. Soln. 60. ‘SOLVED PAPER : CSIR-UGC-NETIJRF Dec. 2011 TUPAC name of above compound can be wiitten using following keynotes~ (1) carboxylic group has to be given highest priority (2) keeping the chain tripple bond is parent chain. ‘A © ($)-3-(prop-2 enyl) hex-S-yncie acid Correct answer is (b). In the mass spectrum of dodecahedrane (CagH1,), approximate ratio of the peaks at mvz 260 and 261 is: @1si (b) 5:1 (10:1 (20:1 In Cyl, dte to 20 carbons, there will be 201.1% probability of one C in the molecule, where 1.1% is natural abundance of C with molecular ion, there will be 22% of M+ I signal. Hence if 260 is 100% and 261 will be 22% 100 So, ratio > Correet answer is (b)- The reaction en below proceeds through Correct answer is (a).SOLVED PAPER : CSIR-UGC-NETIJRF Dec. 2011 7 56. Inthe following concerted reaction, the product is formed by a q O-- Cp <4 A (b) 4n—disrotatory electrocyclisation (d) 4xx—conrotatory electrocyclisation. According to the given product stercochemistry, the product is formed by 6x—disrotatory clectrocyetisation (2) 6x—disrotatory electrocyclisation (©) 6n—conrotatory clectrocyclisation Soln, 4 A Z Se | iscotatory “E On : Correct answers (2). 57. A suitable reagent combination for carrying out the following conversion is a Me a Oe (a) trimethyl orthoscetate and p- toluenesulfonic acid (b) trimethyl ortho acetate and_ sodium hydroxide {c) 2-methoxypropene and p-toluenesulfonic (d) 2 methoxypropene and sodium hydroxide id Soln. Chemical reaction involved in the above transformation can be illustrated as ° 9 I lo Hye: ‘S—OH ———> HC: S—O 4 Ht i i oO CCH; ——> Ho Scr, sO CH, Non Correct answer is (c). ‘The JUPAC name of the following compound is \ 9008 Ue (2) (R}-3- (prop-2-enyl) hex-S-ynoic acid () (S)-3- (prop-2-enyf) hex (c) (R)-3- (prop-2-enyl) hex-S-enoic acid (A) (S)-3- (prop-2-snyl) hex -ynoie acid envic acid56 Soln, Soln. Soln. Soln. ‘SOLVED PAPER : CSIR-UGC-NETIJRF Dec. 2011 According to question, ‘And 2MeV= ; MS; Dividing equation (i by @ (3) 2. s=v28, Correct answer is (c). Green coloured Ni(PPhEt), Br,, has a magnetic moment of 3.20 B.M. The geometry and the nurn- ‘ber of isomers possible for the complex respectively, are (@) square planar and one (b) tatrahedral and one (©) Square planer and two (@) tetrahedral and two Ni(PPh,Et), Br; 1 =3.20 Number of unpaired electrons = 2. Thos this complex is tetrahedarl. Tetrahedral complexes show only are isomer. ‘Magnetic moment correspondin due to spin-orbit coupling. to two unpaired el Correet answer is (b) The uminescence method for determining NO in environmental samples is based on forma- tion of NO,’ (excited) which is. generally generated by reacting NO with «a 0, (®) 05 9, (07 NO+0;=NO) +0, Correct answer is (2) Jn the IR spectrum, carbonyl absorption band for the following compound appears at (2) 1810 cm” (b) 1770 cm" (©) 1730 ean’ (@ 1690 am" =O stretching frequency for simple ester 1750-1725 car! For six membered lactone = 1750 ~ 1735 em’. For five membered lactone = 179: Correct answer is (b). Among the following compounds, the formyl anion equivalent is (a) acetylene (b) nitromethane —_(c) ethyl chloroformate Nitrom (@) 1, 4-dithiane ane is used as a synthetic equivalent for formyl anion, Correct answer is (b)a 46, Soln. Soln. 48. Soln. 49. Soln. ‘SOLVED PAPER : CSIR-UGC-NETIJRF Dec. 2011 85 ‘The material that exhibits the highest electrical conductivity among the following sulfur- nitrogen compounds is @ SN, ©) SNH SNe (sy), (SN), — because it is a giant cross linked molecule and have mobile electrons. Uranium fluorides. co-precipitate with (a) Cak, (&) ARF Correct answer is (2) (© LiF (@) Mgr, ‘The acid-base indicator (Hin) shows a colour change at pH 6.40 when 20% of it is ionized. ‘The dissociation constant of the indicator is (a) 9.95x10* () 395x10* (©) 45x10" pH =6.40= —log (H']=6.40 => [H"]= 3.98107 Hin == Ht + ir @ 60x10" initial 100 0 0 Atend point 80 2 20 [H°][@] 398x107 20 fA] 80 K,, = 9.9510" Correct answer is (a). The actual magnetic moment shows a large deviation from the spin-only formula in the case of (a) TH" ) v* (c) Ga* Sm" due to spin-orbit coupling, Correct answer is (d) ‘The complex that absorbs light of shortest wavelength is (a) [COR © [co(tt,0),}" © [co(H,), }" ( [co(ox), T (0x=c,0, {Co(NH,),}” — highest vate of 4, 7 —>Highest energy (¥) or lowest value of wavelength is absored Correct answer is (¢). ‘Two a particles having speeds S, and S, have kinetic energies | and 2 MeV respectively: the relationship between S, and S, is (a) 8,28, ()S, =28, (© S, = 25, @s,84 42. Soin. 3 Sota. Soln, 45, Sol. SOLVED PAPER : CSIR-UGC-NETIJRF Dec. 2011 “The correct combination of metal, number of carbonyl ligands and the charge for a metal carbonyl complex [M(CO), ]” that satisfies the 18 electron rule is @M=Ti,x=6, 251 (6) M=V, (QM=Co,x= 42-2 M=V,x=6, z=1 al (@ M=Mo, x ie [V(CO),]=542x6+1= Correct answer is (b). ‘Among the following pairs (1) oxygen-sulfiar (2) nitrogen -phosphorus (3) phosphorus arsenic (4) chlorine iodine ‘Those in which the first ionization energies differ by more than 30013 mole” are : {a) (1) and (3) only (0) (2) and (2) only (¢) (2) and (3) only (@) (3) and (4) only (A)IE, for Oand $ are 1314 and 1000 kJ mot difference = 1314-1000 = 314 (B) For Nand P IE, are 1402 and 1012. difference = 1402 ~ 1012 = 390 (C) For P and As IE, are 1012 and 947 difference = 1012 - 947 = less 300 1 mot! (D) Also for IE, difference is less than 300 KI mot? Correct answer is (b) The stable cyclopentadienyl complex of beryllium is (oy [Be(n?-C.H,},] ) [Be(n’ -C,H,)(n"-C.H,)] (©) [Be(w'- CHA ("-CH,)] @ [Bel CyH,)(n? CH.) } Because main group element follows octet rule. 24541=8 Correct answer is (4). ‘The reaction between NH,Br and Na metal in liquid ammonia (solvent) results in the products (@) NaBr,HBr—(®) NaBr,H, (©) H,, HBr (@ HBr, H, Na—S™5 Na’ (NH,), +¢° (NH), +2°(NHL) one +H, +y NH, HBr Na’ (NH,} +Be—+NaBr+ xNH, Correct ansiver is (b)-37, Soln. 40, Soin, 41 Soln. athe YE NMR spectum of PF the mber of signal an mpi, at oom temperate are @) one, singlet (Jone, doublet —_() two, doublet _(d) two singlet Se At room temperature due to rapid interconversion of axial and equatorial F atoms, all the fluorine will be equivalent. Hence "F NMR of PF, at room temperature will appear as doublet of F. Correct answer is (b). ‘The correct statement regarding closo-{B,H.} species is : (a) it always has -2 charge (b) it always has +2 charge (6) itis a neutral species (d) it is more reactive than nido arachno-, and hypo-boranes Closo B,H, species has always -2 charge. Correct” answer is (a) Lewis acidity of BCl,,BPh, ad BMe, with respect to pyridine follows the order (a) BCI, > BPh, > BMe, (®) BMe, > BPh, > BCI, (©) BPh, > BMe, > BCI, (@) BCI, > BMe, > BPh, BCI, + pr—pr back bonding oy BICH)s sp? Box, Cy e (ae BPhy sp? > Band C both are sp’-hybridised. No shifling of electrons. Ph BPh, > BMe, > BCI, Correct answer is (c) Beattracts B-CH; electron Superoxide dismutase contains the metal ions ‘@) Zn (I) and Ni) (&) Cu() and Zn (c) Ni(II) and Co(HiD) (@ Cu (1 and Fe( ttt Correct answer is (b) ‘The number of antibonding electrons in NO and CO according to MO theory are respectively. (@)1,0 2,2 (3,2 2,3 Energy level for NO, 03,64, 63, 6%, 03,, 73, x1) Number of electrons in antibonding MO = 1 Energy level tor CO, o},, 08 x? = x? a, No electron is present in antibonding MO. Correct answer is (a)eq 5 SOLVED PAPER ; CSIR-UGC-NETIIRE Dec. 201 = ‘The concentration of a reactant undergoing decomposition was 0.1, 0.08 and 0.067 mol L* after 4.0, 2.0 and 3.0 hr respectively. The order of the reaction is @o 1 2 @3 Soln, Cone. @ | 01M (| 008M |, =2hr Gi 0067M |, =3r a time =the Above data firts with second order rate law expression for the reaction = AP 1 oo = et a(ak fa), 1A), From data (i) and (i) k eo \- SM ‘ht (21)\008 “o.10) From data (i) and (i) As the value of k is constant so it is second order reaction Correct answer is (¢). 36. Aparticleis constrained in a one dimensional box of length 2a with potential V(x) =a; x<-a,x>a and V(x)=0: axa. Energy difference between levels n= 3 and n= 2 is oes oe a 32ma” es Sina Soln. For 1-D box. the energy is (where L = length of I-D box) and Correct answer is (d),SOLVED PAPER : CSIR-UGC-NETIJRF Dec. 2011 51 Here, .66x10°St; ky =2.2x10tst And => g=12 ‘Now at temperature 240 K, rate constant (k;) k= 2.66107 (1.2) =0.024 or 2.4x102s"t Correct answer is (b). 33. Fora potentiometric titration, in the curve of emf (E) vs volume (V) of the titrant added, the equivg- lence point is indicated by a (a) (E/4V|=0,|PE/av"|=0 (ME /aV}=0,|°E av" >0 (¢) |SE/aV| > 0,|@?E/av?|=0 (@ ME /av|>0,{0°E/dv']>0 Soln. In potentiometric titration the rate of change in slope of E vs V graph has maximum at the equiva- lence point E And as 37 can be positive or negative. But [25] will always he greater than zero. Correct answer is (c). 34. The osmotic pressure (x) ofa polymer sample at different concentrations (c) was measured at TUK), we Aplot of (/c) versus ¢ gave a straight line with slope (m) and intercept (c'). The number average molecular weight of the ploymer is (R= gas constant), Rt c oz Om (ORT (8) mT Soln. Osmotic pressure, x=C,RT(I+BC, +...) Where C, = concentration of polymer in mol [: unit and B = constant. ‘When concentration is expressed in terms of ‘c’ (gL'") then, C x=MRTe(1+MBe+. = se graph will give intercept (c')= MRT Ma RT Correct answer is (b).50 ‘SOLVED PAPER : CSIR-UGC-NETIJRF Dec. 2011 ‘The symmetry point group of ethane in its staggered conformation is @ Gy @D OP» @s, Soin, Correct answer is (b) For the reaction C,H, (z)+30,(g)-> 2CO, (g)+2H,O(), the value of AH—AU (in kJ) at 300 K and 1 baris @50 @00 (2.5 Sol. CyH,(g) +30,(g)——>2C0, (g)+28,0(¢) @so Here An, = En, (product)~En, (reactant) =2-(l43)=2 . | AH =aU+An,RT Or, AH-AU= 40,87 Correct answer is (a). 2x 8314x300 =—5000 J =-5kI. 3h. The sodium D lines are due to *Py +” Sy(SE,) and *Py -¥ Sy(AB,) transitions. The splitting due to spin-orbit coupling in *p state of the sodium atom is AE, +A, AE,—AE, (a) AE, +AE, (b) AE, - 4B, © ae @ aoe Solu TT | ar AE. | n= splitting due to spin orbital coupling = |AE, — AE,| Correct answer is (b). he rate constant of a unimolecular reaction was 2.66x10" sand 2.2x197 sat T=120K and 360 K respectivel ‘The rate constant (in s+ units ) at 240 K would be fa) 2410" (h) 24407 (c) 4.810" (a) 18x10" Soin, Ifk, and k, are rate e nt at temperature {, and t, respectively and 4 is temperature coefficient then these are related by the expression ne (Where, At aca |ic] ‘SOLVED PAPER : CSIR-UGC-NETIJRF Dec. 2011 Soln. CH,COOH + NH,OH —»CH,COO™ (aq.)+NH;(aq.)+H,O weak acid weak base —_fonised salt end point { t i 7 Conductan ‘Volume of weak base ——> 49 ‘When weak base is added to. weak acid then salt is formed which is more dissocited [Link], week acid, 80 conductance increases upto end point but after the end point only concentration of weak base increases which remains in almost undissociated form so does not lead to increases in conductance. Correct answer is (d). (@) Sol Ais negatively charged and Sol B is positively charged (b) Both the sols are negatively charged. (©) Sot Ais positively charged and sol B is negatively charved (€) Both the sols are positively charged. Sok anion is high then its flocculation value will be low for a cation Floccalation value of K,SO,_ismuch less than that of KBr for Sol A. Floccultion value of CaCl, is mnuch less than that of NaC\ for Sol B. Which of the following statements is correct ? \fcharge on cation is high then its flocculation value will be low for an anionic sof and if ehaege on lation value than KBr (due to SO} has higher are charge than Br ) ; so sol. A is cationic in nature. On sol B, CaCl, bas low flocculation value than NaCl due to higher the change on calciuan ion than sodium ion. So sol B is negatively charged. Correct answer is (c). For a system of constant composition, the pressure (P) is given by ) (F) © & \ -P oor {2 Sola. dU=TdS-PdV => ( wv, Correct answer is (b)- ‘The value of d,,, in a cubic crystal is 325.6 pm. The value of (@) 325.6 pm. (0) 976.8 pm (6) 108.5 pm a a Soin. 325 = rears = ean 325.605 Correct answer is (c)Soln. Soln. ‘SOLVED PAPER : CSIRUGC-NETIURF Dec. 2011 , and Py denotethe populations oftwo merpystates B, and Ey, and E, >Ey Theconeet statment when the temperature T, >T, is (a) %(T) > PalT.)oPa (Te) a /Pade, (8) P(E) Pol) a (%!Pa)y (Pa Pads, (6) Py (ty) Pa (Ta) (Pa Pods, ( Pa (T)E, p(T) wee Me Me Me’ Mo c Aromatised (Stable) This is acidic in nature (pk, = 13) Correct answer: (¢) A> C>B. 126. The major product formed in the reaction sequence is: 20 1. CH{COOMe}, (citron!) Me tt @) ®) oy ro @ a aw . ‘OMe Ay 680M Soln, Chemical reaction involved in the above transformation can be illustrated as, MP coon PSST ane oom = _S00ME [Link] WOME Kaoevengel ° 1 | reaction Correct answer: (d)36 14, Solu. ‘SOLVED PAPER: CSIR-UGC-NETIJRF June 2011 ‘The major compound X formed in the following reactinn exhibited a strong absorption atv... 1765 cm in the IR spectrum. The structure of X is: OH 1H _PCC, CHCl, 9 9 ° ona I A go : @§ T W)\A © @ ° ‘Chemical reaction involved in the above transformation can be illustrated as Soln. Correct answer: (d) ‘The correct order of acidity of the following compound AC is: C Me ST A Te FC CF) Mer Me A B c (@B>Caa (@)C>B>A (QA>C>B (A>B>C OF crs + 1,0" —— Fs Aromatised (able) “This is more azide ‘even than HNO) (pk, =9.)Soln. C,H,,0,. Two important data will differentiate the structure (BJ value cis and trans alkene. Position of oxygen in ester. + In the given data J value of define protons is 16.5 that indicates trans structure. + One quartet of 2H at 4.1 ppm confirms structure (a). 5.9 ppm H & ct HC aa He q 441 ppm 7.10 ppm Correet answer: (a) 122, Inthe broadband decoupled "C NMR spectrum, the number of'signals appearing for the bieyelooctane A-C, respectively, are “ @) (a) Five, four and eight (8) Thre, two and five (c) Five, four and five a ‘wo and eight @ ¥ ae a son. a OO @ 2) ‘Taree siguals Two signals Five a Correct answer: (b) 123. In the mass spectrum of dichlorobenzene the ratio of the peaks at mz 146, 148 and 150. is (ay itt 33:1 (giz (9-01 Soin, Natural ratio of CP* and CP” is 3:1 M M2 Meg ce a eg? crs cers 3 3 1 3 ies U 9 6 1 Ratio = [Link] Correct answer: (4)M Sola. 120, Soln. ‘SOLVED PAPER : CSIR-UGC-NETIJRF June 2011 For aH, molecule, the ground state wavefunction is (1,2) = $(1,2)6(12) Where @ refers to the space part and cr to the spin part. Given that ¢(1,2)= (2,1), the form of o{1,2) would be {@) a(1) B(2) © a(2)80) © «()6(2)-2(2)8) © a(1)B(2)+<(2)B0) From Pauli Principle, “When the labels of any two identical fermions are exchanged, the total wavefunction changes si As electrons are Fermions, So wG2)=-¥@.) () Here, w(1,2)=6(4.2)0(12) and w(2.1)=9(2,1)6(2,1) [Given, 6(1.2)=4(2,1)) So, far condition (1), to be satisfied we must have: a(1,2)=+0(24) 2) ‘The above condition is satisfied only if @(.2)=a¢(1)8(2)-a(2)8(0) $0, 6(2,1)= 4(2)B(t)-a(1)B(2)=-o,, Correct answer: (¢) ‘There are s methods like: (1) Osmometry (2) Light scattering 3) Sedimentation. Corvect relation between mean molar masses and experimental method is: () M, 2 G),M, © (2),M, © (I) | types of mean molar masses for polymer and they are dependent on experimental ©) M, 2 (2),M, 2 @),M, © (1) () M, 2. M, = (2), M, 2 (3) @ M, 2 @,M, 2 3),M, (2) Method Polymer Mass fa) Osmometry number ‘Gependent) (b) Light scattering (weight dependent) / {e) Sedi Ez! dependent) =z Ly Correct answer: (¢) An organic compound (C,H,,0,) exhibited the following data in the 1H NMR spectrum. 87,10(1H, dt, =16 and 7.2Hz), 5.90 (1H, dt, J =16 and 2 Hz), 41(2H.9,3 Hz),2.10(2H, m),1.25@H, (,J =7.2Hz), 0.90 GH. t, J= 7.2 Hz) ppm The compound, among the choices given below, is: Lo Q @) I © XO 8 yt 9 ° a @ DP116. Soln, ug. Soln. 3 a + ‘An operator Ais defined as A. X. Which one of the following statements is true’ x g (@) Ais a Hermitian operator. (©) Both AA' and A'A are Hermitian. If A’=A, then Hermitian operator. ‘At =A; then antihermitian operator. 2 ae (b) A! is an antihermitian operator. @) AA! is Hermitian, but ATA is antihermitian. a - Given, A= tx So, A is neither Hermitian nor antihermitian, wotfemken]-( AA’ is Hermitian. Clearly it can be shown than A'A is also hemnitia, Correct answer: (¢} Isothermal which has fractional coverage. linearly. dependent on pressure at low pressures but at ‘most indepenent at high pressure is called (a) BET isotherm (b) Langmuir isotherm (©) Freundlich isotherm (@) Temkin isotherm Jn Langnnar isotherm, Fractional coverage (0) = o +k Case I: At low pressure, kp << 1 8 kp (directly proportional i pressure) Case TI: At high pressure, kp >> 1 8 2 1 (Independent of pressure) Correct answer: (b) A one-dimensional crystal of lattice dimension ‘a’ is metallic. Ifthe structure is distorted in such a a ‘way that the lattice dimension is enhanced to “2a”. — (a) The electronic structure remains unchagned. (b) The width of conduction band decreases and a band wap is generated (c) The width of conduction band increases (2) The width ofthe conduction band remains unchanged. Width of conduction band ° = Correct answver: (b)2 SOLVED PAPER : CSIR-UGC-NETIURF June 2011 113. Observe the following aqueous solutions of same compound. All the measurements are made at same wavelength and same temperature, Solution A: The transmittance of 0.1 ‘mol dor? using 1 cm cell is 0.5. Solution B: The optical density 0.5 mol dar? is measured using 1mm cell. Solution C: The transmittance of this solution is 0.1. a [mre = 0-1 MBER The optical density of these solutions follow the order. (log 20 1.3010; log 30 = 1.4771, log 50 = 1.6990 (ASBOC Q)B>C2A— @BYASC — @C>A>B Soin, Optical density (.D) = Absorbance = be{ #)-« ot () Solution A: T=0.5; OD ~loe{ g} +920 301 From equation (1), €*0-1x1=0.301 =>. Solution B: OD =e Cl=3.01x0.5x0. (a Solution C: OD =ve( 4) ‘Therefore, optical density order is C> A> B. “orrect answer: (8) 4 ‘The rotational constant of “N, is 2 car, The wave number of incident radiation in a Raman spec- \ trometer is 20487 cm. What is the wave mumber of first scattered Stokes line (in crt!) of #N,? (a) 20479 (b) 20975 (c) 20499 (a) 20495, » and have wave number value less than the incident radiation, but the first Stoke's line is obsorbed at 7-63 6B=6x2em™ =12 cm" ‘Therefore. first Stoke line wave number = wave mumber of incident — 12enr? radiation. = (20487-12) em" = 20475 em Correct answer: (b) 5. For a certain particle encountering a barrier, the tunneling probability is approximately ¢”. If the mass js halved and width of the barrier (rectangular) doubled, approximate value of the tunneling probability will be @ er oem @e" Soln. Given, Tunelling probability 2m whore k={ 2" and = Rarer Feng f m* k Us iPhaed |= 5 then Kp and L'= Correet answer: (b)iit Soln. SOLVED PAPER : CSIR-UGC-NET/JRF June 2011 an ‘The virial expansion for a real gas can be written in either of the following for : a SY St BPtGP +. er Gr =14B,V+G,V +. If By =aB,, the valueof a would be (a PvIRT RIV fry (@Rr ‘The virial expression fora real gas can be written as Pv - +BPHC Pt @) ” PV 14 Be RE VV ‘From equation (2), P (eer Ge. : ) RT ~-Q) Vv Substitute this ‘P* in RELS. of equation (1), ews RT PV _| BRT 2 Yai Be ByRT + pe lB RT C, (RT) J+ ‘Compare Ist term on RHS. of equation (1) and (3) B, =B,(RT); By=aB, — (herew=RT) Correct answer: (d) 148, Or, A certain system of noninteracting particles has the single-particle pation has the single-particle partition function f=A- where A is some constant. The average energy per particle will _ (a) mx () Act (©) xP liam . @aTIA =_kE af Average ener gta (l erage energy per parle B= (y {Where f = single particle, partition function.) here, afd ar aT Vv > eae “2 dv Vv Put this value in equation 1), we get K A 7 = |mT™" = mk) (i)ert-ae (*] Correct answer: (a)30 SOLVED PAPER : CSIR-UGC-NETIJRF June 2011 ‘Therefore, Debye-Hiickel screning length (x Correct answer (a) 109, If the ratio of composition of oxidized and reduced species in electrochemical cell, is given as (@ B-EY + () E-EP RT E-E* =-— Q oF Sola. For oxidation reduction half-cell {[Graisd state (0} 40" = Rested sate) From modified nernst equation (in terms Of formal potential E°) 2RT E-B === or A Correct answer: (2) 110, Ifthe equilibrium constants for the reactions J and 2 1. CO(g)+H,0(g)—==CO,(g)Ha(g) 2. CHy(g)+H,0(g}==CO(g)+3H,(g) are k, and k, the equilibrium constant for the reaction CH, (g)+28,0(g)—==CO, (2)+4H, (8) is (a) ky +k; () kk © kk @k/k, Soln, (i) CO(y)+H,0(g)—==CO. (g) +H, (8); 0) ky aks ~-Q) CH, (2) +2H,0(2) Correct answer: (©)107. Soln, 108. Soln, SOLVED PAPER : CSIR-UGC-NET/JRF June 2011, 29 Ait =-(2x10'xR)=-166 13 / mol In equation (2) multiplying both sides by (-RT), -R¥tak =-3RT-2x10R @) AG® = ~TAS* +A" (4) From equation (3) and (4) AS? =3R=24.9 Tktmol*, Correct answer: (€) : ‘The chemical potential of component in asolution of binary mixture is jy =p +R In, , when p, is the partial pressure of component | vapour phase. The standard state y,° iss (7 (2) Independent of temperature and pressure (b) Depends on temperature and pressure both (©) Depends on temperature only (@) Depends on pressure only °+RTénP, Standard state for component 1 is defined at, P,=1bar (Standard pressure) by =Ho +(Rx 298) Ent > eH [ ai=9] So, p? is independent pressure, but 1° is dependent on temperature. Correct answer: (c) Debey-Huckel sereening length (x) is a measure of size of diffuse ion cloud around an ion, pro- vided feetNa $30 nen foot t Yegkst U™ ) at 298K, which of the following values of x" is true for a 0.03 ‘molal solution for Na,SO, in water (c,=100)? 10 9 1ov2, @5™ © = (©) —=am @ nm roy We have,28 Soln. 104. Soin. Soln. 106, Soin. ‘SOLVED PAPER : CSIR-UGC-NETIJRF June 2011 AXE ‘ansform with xy axis = allowed w/ a A, xE=E= Transform with xy axis = allowed AXA, ‘Not transform as per x,y or z.= forbidden Correct answer: (@) ‘The electronic configuration for gadalonium (Gd) is [Xe] 4f”5d"6s, where as that of Gd** is: (a) [Ke]4£*Sa6s" _ (b) [Xe] 466s? © [Xe]f*sa'es! uGd=[Xe]4f"sa'6s', Gd? =[Xe]4f7sa6s? ‘Removal of electrons takes place from the outermost orbital only. Correct answer: (4) The possible J values for ’D term symbol are @ [Xe]4f7 5a" (a2 ()3 @4 @s For *D 2841=3,28=31 For term, S, P, D, F 28=2,S=1 Value of = 0, 1, 2, 3 L=2 J can have values from |L+8| iL-S} HI eae) 3 1 Correct answer: (b) ‘The energy levels for eyclobutadiene are +28, a, a and o-28. The delocalization energy in this molecule is: (ao (b) 48 (©) 8B @ 4a +28 ,(BMo) Delocalisation energy = [2 +28)+20)}—4(« +8) =0 Correct answer: (a) The variation of equilibrium constant (K) of a certain reaction with temperature (T) is 2.0x10* gen R=83 Jk"'mol™!, the values of AH? and AS? are. (a) 166 kJ mol" and 24.9 Jk" mol" (c) -166 kJ mol" and 24.9 Jc! mot! Ink=3.04 (b) 166 kJ mot"! and -24.9 Jk" mol (@) -166 KS mot! and 24.9 Tk mol We natafnk = constant 1 fe havalink = constant- 5 cu) 20x10 Given, & Fr 2) on From (1) and (2),‘SOLVED PAPER:: CSIR-UGC-NETIURF June 2011 ar ‘Bt Le 100. The unperturbed energy levels of a system are €= 0, €)=2 and a ‘The second order correc- y tion to energy. for the ground state in pressure of the perturbation V for which Vio = 3 Vig =4 and Vj. =6 hasbeen found to be . {a) 6 (bo (+6 (d)-8 Soln. Second order perturbation for n* state is given by, way LAE ‘Therefore, perturbation for ground state, (Le., n= 0) eo Let] Correct answer: (a) 101. Given the character table of the point group C,,. Its irreducible components are (EL2A,+2A, (D)IELA+A, — (©) 3A, +3A, (4) E42, Soln. EL (6x1) +(21%3) + (x10)] 2H (Ost) +(2e3)+(-n0)]=2 a =F (6=2)+(2x-1%3) + (340%0)] T=2A,+2A, +E Correct answer: (a) 102, Refer to the character table of the point group C,, given above. Find wh tion is forbidden 7 (a) a—a, (b) ae (c) a,e—e (d) a, —>a, The direct product of two energy state should transform according to x, ¥ or 7 axis for electe transition, Ah of the following transt- Soln, A.A, =A, = tansform with z axis = allowed26 98, Soln. Soln. ‘SOLVED PAPER : CSIR-UGC-NETIJRF June 2011 — 1 1 : =-—_-x lopex[E], ~ 40x2.5xi07 Correct answer: (c) A hydrogenic orbital with radial function of the form 1 exp[~r] and §—patt asexp[—3i 6] corre- sponds to (@) n>4,0>3,m=3 () n=4,0=3,m=-3 (0) n=4,6>3,m=3 (@) n>4,¢=3,m=-3 Given for any H-orbital Radial function has form 1" exp{-Br] and $-part has form exp{-3id]. From the solution of Schrodinger equation for H-atom, 1 We get @ part = =e"; where mis integer =0, 1, 2,3, Fagt” Here m can be ve or—ve integer including zero). From given @—part, m can be either +3 6r—3. Option (a) > incorrect, for n> (let n= 3) 6 H(le €=5) in is not possible m=3 Option (b) > correct,iorn=4, ¢=3,m=—3 (Can be possible solution) Option (c) + incorrect, _forn= 4, 1>3 (let 4), m=3 (Can not be possible) Option {d) > incorrect, forn> 4,1=3,m=—3 forn>4, Lean be upto 4. (So not possible) Correct answer (b) For an assembly of molecules (molar mass = M) at temperature T, the standard deviation of ‘Maxweller’s speed is approximately [Rt I i) ane (ore oi = Standard deviation in spead = |[¥°)—(VP Correct answer: (a)‘SOLVED PAPER : CSIR-UGC-NETIJRF June 2011, 25 96. The decomposition of gaseous acetaldehyde at T(K) follows second order kinetics. The halflife of this reaction is 400 s when the intial pressure is 250 Toor. What will be the rate constant (in Toor" s~ +) and half-life (in s) respectively, ifthe initial pressure of the acetaldehyde is 200 Torr at the same temperature? . (@) 10%and 500, (6) 10F and 400 (©) 10+ and 400 (a) 10 and 500 Soln, Acetaldchyde (CH,CHO) —> product, rate = k{CH,CHOP. In terms of partial pressure , rate = KPZ,ax0 Since given t = 400 sec and Piy,cag = 250 400 sec=—4 ek =10 Tors kx 250 Tor and [Link] = 200 Torr r J = = 500s Then "EPR ge 107x200 Correct answer: (4) 97. For an enzyme catalyzed reaction, a Lineweaver- Burk plot gave the following data slope = 40s intercept = 4 (mmol dar? 5". Ifthe initial concentration of enzyme is 2.510 mol dm, what is the catalytic efficiency (in dm? mot" ¢) of the reaction? (a 1° (b) 106 ow (4) 10% Soln. SEL From enzyme kinetics, : Keb w(ele arse Sea 94 Soin. SOLVED PAPER : CSIR-UGC-NETIJRF June 2011 1840 con ND = Ee =13000n" v2 Correct answer: (a) For the complexes ca) NiO), [oin(Ht,0),F” © [cr(H,0),]" @) [ri(H,0),}", the ideat octahedral geometry will not be observed in @Aand@) Cami) (Bony. (@) ©) only Due to Jahn-Teller distortion Correct answer: (d) Among the following, the number of anhydrides of acids are CO, No, N,O, B,0,,N,O,, SO, and PO, (3 ws (5 6 B,0, +3H,O—>2H,80, (orthoboric acid) N,O, +0 —>2HNO, (Nitric acid) SO, +2H,0—+H.S0, (Sulfuric acid) P,0,, +6H,0—> 48,20, {(orthphosphoric acid) Correct answer: (b) For a given nuclear fission reaction of U U4 hn ae MKe4 abn the amount of energy (in kS/mol) released during this process is (given ™U = 235.0439 amu, "Ba = 141.9164 amu, “Kr = 90.9234 amu, neutron = 1.00866 amu) (a) 3.1210" (b) 2.8810" (©) 1.0«10° BU 4 jn (Bay Eke (@ 1.68%10", Ener: leased per atom (E) = (Am)c* -[la,+0,)- +m, +3m,)]e° = [(235.0435 +1.00866)— (141-9164 490.9234 + 3 1.00866) ]}x1.67%10" x{3x10*) J ‘Therefore S(peranom)=2810%5 E> Tama =1.67%10%Kg,¢=5410 mis] Eneryy released from } mole disintegration RU = E(Per mote) =E(per atom) Ny =2.8%10"" x6,023 x10" =1.68x10" J =1,68%10" 1d Correct answer: (d)90. Soln. a Soln. Soln. 23 Consider two redox pairs (1) Ce(yRuGit) (2) CrVCo(h) “The rate of acceleration in going fiom a outer-sphere to a inner-sphere mechanism is lower for (1) relative to 2). Its correct explanation is: ~— Oe (a) HOMO/LUMO are o” and a" respectively. (b) HOMO/LUMO are o” and x” respectively. (©) HOMO/LUMO are x” and o” respectively. (4) HOMO/LUMO are nx" and x” respectively. o ve HL ce? os cm? Lange reorganisation for Co"? Reorganisation of Ru" less cute sphere, so iner sphere than CO. s, slower tendency o 20 such faster inner sphere HOMO= o* (of CF) HOMO = * (of Ce) LUMO « 9* (0fCo") LUMO = nine (of Ru?) Acceleration IS0S=10!° ‘Acceleration IS10S-10? Inner sphere mechanism s favorable for s* to 6* transition only ASCr?/ Ru” has g” to n° transition which is responsible for its slower accelera ‘outer sphere mechanism to inner sphere mechanis. Correet aise (By going from ‘The correct value of isomer shift (in Mossbater spectra) and its explanation for Fe({I)~TP! Fe(lil)-TPP respéctively from the following are: (TPP = tetraphenylporphyrinate) (A) 0.52 mms" (B) 0.45mms" (C) Increase in s electron density (D) Decrease in s electron density (a) (A) and (DJ; (B) and (C) (b) (A) and (C); (B) and (C) (©) (B) and (D); (A) and (D) (4) (B) and (D); (A) and (C) Both Fe(Il)-TPP and Fe(ITI)-TPP are scare planar (because of p ligand), and both Fe(II) and Fe(III) are dsp*-hybridised, so there is s-electeon density, which is re= sponsible for their quadrupole moment and existence of mossbaue spectry. So both Fe(I)-TPP and Fe(IIl)-TPP show increase in electron density, but Fe({I) has higher s-elactron density. So Fe(II) has isomer higher shift (0.52 mms) than Fe({I1) (0.45 mms Correct answer: (b) identate-planar, porphyrine type In IR spectrum of [Co(CN),H] the Co-H stretch is observed at 1840 cm, The (Co-1) stretch in {co(CN),H] will appear at nearly (a) 1300 cmt (6) 1400 cnr! (d) 1600 vib = ‘As frequency of vation f Where k = force constant of bond reduced mass. Ratio of frequency/wave number of Co-D and Co-H bond isSola. Soin. Soln. 89, Soln. ‘SOLVED PAPER : CSIR-UGC-NET/JRF June 2011 86-electron cluster H,Ru,(CO),, displays a distorted octahedral metal geometry. Here each hydride ligand is connected to 3-Ru atoms. Correct answer: (4) In the hydroformylation reaction, the intermediate CH,CH,CH,Co(CO),: (a) Forms are acyl intermediate CH,CH,CH,COCo(CO), (0) Forms an adduct with an olefin reactant. (©) Reacis with H, (@) Eliminates propane During hydroformylation the intermediate CH,-CH,-CH,-Co(CO), gets transformed to acyl inter- medinte CH , Statement I: The sizes of Zr and Hf are similar Statement Il: Size of His affected by lanthanide contraction. (a) Statement [ and I] are vorrect anid tl is correct explanation of I, {(b) Statement [ and II are correct but IL is not a correct explanation of I. () Statement | is correct and II is incorrect {d) Statements I and II both are incorrect. As we move trom 2 row transition element (Zr) to 3" row transition element (11). increase, but due to lanthanide contraction ofiet the increase, so Zr and Hf have almost Correct answer: (a) ize should ilar size. Consider the compounds, (A) SnF,, (B) SnCI, and (C) R,SnCL The nuclaer quadrupole spliting are observed for. @) (4), (B) and (C) (b) (A) and (B) only (6) (B) and (C) only (4) (A) and (C) only SnF, is ionic. here Sn'*= 5s", so no quadrupole spitting SnCl, is covalent. and Sn is sp' hybridised, So there is $-electron density in the molecule, => quadrupole splitting is possible. R,SnClis covalent, and Sn is sp’, so there is S-electron density in the molecule = quadrupole splitting is possible Correct answer: (¢)aq SOLVED PAPER : CSIR-UGC-NETIIRF June 2011 a S4. The molecule with highest number of lone-pairs and has @ linear shape based on VSEPR theory is: (9.00, OG (© NO; (@ Not Soln. = Shape Number of lone pair Linear 4 Linear 9 ‘Angular 6 Linear 4 85. Given, Ag'+e>Ag, Ey =0.50V a Cu™ +264 Cu, ‘A 100 ml sokution is 1080 mg with respect to Ag’ and 635 mg with respect to Cu. If O.1mg Ag" let in the solution is considered to be the complete deposition of Ag”, the cathode potential, so at no copper is deposited during the process, is (@) 0.16 084¥ (031¥ (0.16 Soln. For, Cu +2e—sCu, E,=034V 0059, 1 2 Tow =0534 og 10=0.31 volt ‘So, when Eat 0.31 volt will reach, then deposition of Cu will start, For Ag’ +e—>Ag, E,=0.50V On completion of this reaction, 27 Oix10" wen : [g"]= M (Given: (8e = Te5s07 a 50-0959 jog 0.1x107 = 9.203 voit 1 8 t08x0.1 So, we will have to fix cathode potential above 0.31 volt so that no. Cu is deposited at the eathode. We ‘an uot reduce the potential upto 0.203 V. So, that all Ag’ has been deposited. Correct answer: (c) Inthe H,Ru,(CO),, cluster, containing 8-coordinated Ru centers, the hydrogen atoms are (2) Both terminal (b) One terminal and the other brid; () Both bridging between two Ru centers (d) Both bridging between three Ru ging, ters20 SOLVED PAPER : CSIR-UGC-NETIJRF June 2011 80. In the EPR spectrum of tetragonal Cu(II) complex, when gJ>g>g, the unpaired electron re- sides in the orbital @ dy 42 a? @4a, Soln. gil>g-L>ge , gives the evidence that Cu ion is present in tetragonally distorted octahedral field. tty <— ground sate “addy “hth a, octahedral field te ‘Texagonally disorted ott ld Correct answer: (b)- ‘The oxidative addition and reductive elimination steps are favoured by (a) Electron rich metal centres. (b) Electron deficient metal centers (c) Election deficient and clectron rich metal centers respectively. (@) Electron rich and electron deficient metal centers respectively. Soln, Oxidation of metal is easier for clect tron rich systems, $0 electron rich metals undergo oxidative addition and as reduction is easier for electron-debcient metal, so it undergoes reductive elimina- Correct answer: (2) $2. Identify the order according to increasing stability of the following organometallic compounds, TiMe, T(CH,Ph),, TWi-Pd), and TEL, (Me = methyl, Ph = phenyl, iPr = isopropyl, Et = ethyl) (a) Ti(CH,Ph), Cr0 > Vor (©) MnO; > Cry < VOT (¢) MnO; Vor In the given case ligand in same, so higher the formal oxidation state of the metal, lower will be LMCT, So, orderis MnO; [M(NH,), ] +[e(NH,}y] ‘These solvated electrons can reduce O, molecule to superoxide ion [e(n,)y] +0, +0; + yn, ‘These superoxide ions can combine with solvated metal ion to give Alkali metal superoxides, [M(ou,),] +0; —>M0, + xn Correct answer: (a) HO, reduces (a) [Fe(cn),P KIO, (©) Ce(S0,), (0) sor (a)Aand Bonly —()BandConly — (c)CandDonly (a) Band D only ray fr HO, oxidise, Fee toFe" | Fe(CN), | rs | Fe [Link] to HNO,,SOF to H,O, reduce KMn0,, KIO, ,Ce(SO, Note: In the question, only 1” and Ce** are in their highest oxidation states, so the only possibility of reduction by H,O, exists Correct answer: (b)16 SOLVED PAPER : CSIR-UGC-NETIIRF June 2011 Soln. Chemical reaction involved in the above transformation can be illustrated as “sabe Correct answer: (8) 69. The suitable reagent for the following conversion is: a oe (a) m-CPBA (b) HOJAcOH —(¢)"BUOHMHCL_——(@) HO NaOH Soln. Chemical reaction involved in the above transformation can be illustrated as ° 0, +Na0H—> HOO™ + HO sotto) { wow” Co Me Me ° 3 ° ~) Bon ae a Cah Correct answer: (d) 70, The rel Mechanism: ¢ rates of solvolysis of iodides A-C are (Be CPA @B>A (a)65. Soln. 66. Soln. 67 Son, ‘SOLVED PAPER : CSIR-UGC-NET/JRF June 2011 15 The concerted photochemical reaction between two olefins leading to a cyclobutane ring is: (a) ,2,+ .2, cycloaddition (© 625% 02, cycloaddition (®) 2, + .2, cycloaddition @ 42, + 42, cycloaddition RR RUR 7 LUMO + | —?}f ke 4%, ‘Cjeloadiition K Correct answer: (b) Addition of BH, to a carbon-carbon double bond is: (@) anti-Markovinikov syn addition (b) anti-Markovnikov anti addition (6) Markovnikov syn addition (@) Matkovnikov anti addition Chemical reaction involved in the above transformation. can be illustrated as t 8H) —> R—-C—ch 4 BH2 - Syn-addition (& BHy-Syn (Markovnikov) addition) Correct answer: (c) The absorption at Lge 279 nm (¢=15) in the UV spectrum of ace eis due to (a) x—7" transition (b) n—x' transition (©) ¢—a" transition (4) xc" transition 7h = 279 is ton , which can be differentiated by low ¢ (15) Correct answer: (b) The reaction given below is an example of Meo,_W0, (3) E,-elimination (c) synelimination (b) E,-elimination (@) E,CB-elimination14 Soln. o Soln ‘SOLVED PAPER : CSIR-UGC-NETIJRF June 2011 Or e-Q,, (A) Homoaromatic character (Aromatised by bypassing the sp!-carbon atom) @ of) ‘oA= + Delocalisation + sp? carbons (planar) + 4n= 4 (x- electron) + (Ant2) = 2 (x-electron) nel n=0 + Antisromatic character. + Antiaromatic character. Correct answer: (a) + Delocalisation ‘The order of carbonyl stretching frequency in the IR spectra of ketone; amide and anhydride is: (a) Anhydride > amide > ketone (b) Ketone > amide > anhydride (c) Amide > anhydride > ketone (d) Anhydride > ketone > amide Because ve. of anhydride = 1800 1900 emt Veo Of Ketone = 1720 cnr". Veg of amide = 1600-1700 ent, Correct answer: (4) In the mass spectrum of the compound given below, during the o.~ cleavage, the order of preferen- tial loss of groups is Me. ‘OH ee Cott, (a) Me>CH,> Et (0) CH, >Et>Me (6)Et>Me>CH, (a) Et> CH, > Me Because the ease of elimination increasing with increased size and branching in the radical. Correct answer: (b) The reaction given b ow is an example of Onn = > Me Me (a) 1, 3-sigmatropic hydrogen shift (b) 1, 3-sigmatropic methyl shift (©) 1, S-sigmatropic hydrogen shift (6) 1, S-sigmatropic methyl shift. Chemical reaction involved in the above transformation can be illustrated as # 5 ‘Cy = i) " awe tf ee | Correct answerSola, 60, Soin. ol ‘SOLVED PAPER : CSIR-UGC-NETIJRF June 2011, 2 & 2 Oe, £4 Ny Me Me Me = = Me" Correct answer: (d) 13 ‘The intermediate involved in the reaction a below is: (a) Free radical a carbocation (© Carbanion (A) Carbene Chemical reaction involved in the above transformation can be illustrated as Moon co Correct answer: (d) In the most stable conformation of trans-I--butyl-3-methyleyefohexane, the substituents at C-1 and C-3, respectively, are (2) Axial and equatorial (b) Equatorial and equatorial (c) Equatorial and axial (@) Axial and axial. 3-trans-disubstitution = a, e substitution, At C-1- equatorial t-Bu; "At C-3- axial - methyl group 7 Larger substituent always prefer equatorial position. Hence, correct conformation cas be repre sented as Ch Hc. ry Hae 7 CH3 Most Stable Correct answer: (6) Among the carbocations given below OG A wa ® (a) Ais homoaromatic, B is antiaromatic and C is aromatic. (b) A ts aromatic, B is antiaromatic and C is homoaromatic. (c) Ais antiaromatic, B is aromatic and C is harmoaromatic (4) A is homoaromatic, B is aromatic and C is antiaromatic.2 Soln. Sola. Soln. Sal, SOLVED PAPER: CSIR-UGC-NETIJRF June 2011 ‘Chemical reaction involved in the above transformation can be illustrated as ps s. ( , BE; BLO o* = Cx) Losi = ] x3 Correct answer: (a) ‘Thermolysis of allyl phenyl ether generates (a) o-allylphenol only (b) o- and p-allylphenols (0) o-, mand p-allyiphenols @ mvallylphenol only Chemical reaction involved in the above transformation can be illustrated as ; ee CL-OC, ° — * OO allyl ether Ortho-allyl phenol Correct answer: (a) “The major produet formed in the reaction given below is: KI Cymer Teo Chemical reaction involved in the above transformation can be illustrated as cone OH Ze eo o a & Correct answer: (a) The most suitable reagent for the following transformation is: wef Yo ——e ed haart aa (a) LiAiH, {h) NHNH/KOH — (c) NaBH/CeCl,—_(@) Lifiq. NH, Chemical reaction involved in the above transformation can be illustrated as=.) ‘SOLVED PAPER : CSIR-UGC-NETIJRF June 2014 it 52. Ify=4x ‘and 0.1% error is incurred for x, the percentage error involed in y will be (@o4 (6) 0.025 (or (@ 0.05 Soln, vod ~() After 1% increase in value of x, =%x0.1=0.05. Correct answer: (€) 33. ‘The configuration at the two stereocentres in the. compound given below are Me, “4 9 4 (a) IR, 4R (b) IR, 4S (c} 18, 4R (d) IS, 48, @ o ° Me Sole. ~~ & a @ {R-Configuration cA 4R-Con guration Correct answer: (a) 54. The two compounds given below are 9 te we Me Me and A ih o é ii q H H (a) Enantiomers_(b) Identical (©) Diastereomers (a) Regioisomers. Soln. Both the compounds are po: mn isomers oF regioisomers. Correet answer: (@) A suitable catalyst for bringing out the transformation given below is O- L— OO (a) BFE. (b) NaOEt (6) Tungsten iarap (d) Dibenzoyl peroxide0 Sola, Soln, ‘SOLVED PAPER: CSIR-UGC-NETIIRF June 2011 If A is time independent (i= a 4} then, for A to be constant of motion, Saat o (apo Note: If [A,8 ]=0, then also we can say Ais a constant of motion, Correct answer: (b) ‘The hermitian conjugate of operator dds, called (4/ dx), is actually equal to (@) a/dx () ddx (©) i(@/ax) @-W@iax) ‘Hermitian conjugate or adjoint ofan operator A is written as At, and is defined as (dy _(ay_i¢ (la) -4 Correct answer: (a) [An ideal gas expands by following an equation PV* = constant. In which case does one expect heating? ()3>a>2 ()2>a>1 (@0 0, as PV =constant Correct answer: (c)47. Soln. 48. Soln. Soln, At room temperature, which molecule has the maximum rotational entropy? @H, @)0, (Db, @N, ‘The entropy of a compound is related to the number of ways in which the molecules can be distributed among different energy states; the greater the number; the larger is the degree of disorder, ic. larger is the entropy. According to Boltzmann distribution, larger, the energy difference w.r.t. ground state lower will be population in exited state. Beet Pernt + €_= Bho, so higher the value of B, lower will be population in different exited state (ie. lower disorder or eatropy) fees aed, [-»-25] => Ba =0 (ce) A= fH) Ais constant of motion (i., does not change with time) if wor La it). (%)-0 WaSOLVED PAPER : CSIR-UGC-NETIIRF June 2011 Soln, For Langmuir adsoption (Monolayer, only), kp 2 T+kp z Atlower pressure , kp << 1 i Sotht @=kp >Oxp At high pressure, kp >> O=1 (Independent of p) ‘As Langmuir assumed that binding at a site has no influence on the properties of neighbouring sites; ‘this means that enthalpy of adsorption is independent of coverage. ‘Correct answer: (a) 45. In. a chemical reaction AG)+B(g)==C(s) (2 9 1 (6 Sola, A(s)+B(g)==C(g) IC =0-(0+0)=0 {im standard state aG§ = 0] AG =0 On -RTEnK, Or, fa, = On {Kel K, = Lis possible when, partial pressure of B (P,) is equal to partial pressure of C (P.), ie P= Pp =3atm and P= P,+P,=6 atm. Correct answer: (¢) 36. Amolecule, AX, ational energy of 1000 cnt’ and rotational energy of 10 em, Another molecule. BX, has a vibrational energy of 400 env" and rotational energy of 40 enr!, Which one of the following statements about the coupling of vibrational and rotational motion is true? (a) The coupling is stronger in BX. (b) The coupling is stronger in AX. {c) Magnitude of coupling is same in both AX and BX, (4) There is no coupling in both AX and BX Soln, As per B.O. approximation we can consider the two different motions independent if their energy difference is lage. In other words if energy difference of two different motions is large, the coupling, etween them will be minimum Incase of AX the energy difference of vibrational and rotational energy is large compared to BX. Hence coupling will be stronger in BX. Correct answer: (3)| ‘SOLVED PAPER : CSIR-UGC-NETHRF June 2011 1.) The microwave spectrum of a molecule yields three rotational constants. The molecule is (a) Prolate symmetric top (b) Spherical top (©) Asymmetric top Soin, Soln, Soln, 441 (@ Oblate symmetric top For an asymmetric top, J, #1, #1, ‘Therefore, Total energy (B)= E, +E, +E, So, above equation will give three rotational constants, B,,B, & B, Correct answer: (@) ‘The Q band in the vibrational spectrum of acetylene is observed in the (® C-C stretching made (b) C-H symmetric stretching mode (c) Bending mode (@ C-H amtisymnmetric stretching mode. Q-band (or PQR contour) is obtained for the bending vibration of C,H, when its linearity is lost. Correct answer: (€) ‘The Stark splitting for a given ficld is larger for a molecule AX following is tre? (i isthe dipole moment) as compared to BX. Which one of the fa) Hax =Hox, ©) Bax > Pax (©) Bax $ Hex: @P ‘The degeneracy associated with the quantum number (M,} (the orientation of the rotation in space) is partly removed when an electric field is applied on a polar molecule (eg. HCI, NH,ete) This splitting of states by an electric field is called Stark Effect. For any linear molecule (eg. AX or BX) in electric field (E), the energy of the state with quantum number J and M, is given by, E(,M,) =he BxJ(J-+1)-+a(.M, 10 here energy depends on 7 (square of dipole moment), so large 1t(dipole moment) will cause larger splitting, Hac Hs Correct answer: (b) The adsoprtion ofa gas on a solid surface exhibits the following isotherm. Which one of the follow- ing statements is true? oe sé (a} Heat of adsoprtion is independent of coverage (b) Adsorption is multilayer {c) Heat of adsorption varies monotonically with coverage (a) Heat of adsorption varies exponentially with coverage.Sola. ‘SOLVED PAPER : CSIR-UGC-NETIJRF June 2011 On, as-a0 -() ‘At constant volume, dw=-PdV=0 Therefore, ftom frst law of thermodynamics, dq=du—dw dg=du [> aw=0} At constant entropy ds = 0, ‘Therefore, from equation (1), we get Here equality holds only for reversible process. For spontaneous process, 8, <0 o au,, <0 Correct answer: (0) The halt life of a zero order reaction (A> P) is given by (k = rate constant): [a 2.303 fal Oty OTA On integration and putting proper limit we get, {a}, fal a) at anafa]-2b From equation (1), we get a Bhiiu oy Correct answer: (a) For an aqueous solution at 25°C, . the Debye-Huckel limiting law is given by (a) logy, = 0.509122. | fir (b) logy, =0.509|Z,Z_|ue fc) logy, = -0.809]Z.Z | yu (@) logy, =-0.509|Z,Z_|p For ' sofution at 25°C. the Debye-Hiickel limiting law is log iz, Zu S02. Z1yR [vd = 8.509] Correct answer (c)Som, Sotn, Soln, ‘SOLVED PAPER : CSIR-UGC-NETIJRF June 2011, Ne tits y Bp Maem) ey ‘Correct answer: (b) Cis and trans complexes of the type [PtA,X,] are distinguished by (a) Charomy chloride test () Carbytamine test (©) Kurmakov test, (© Ring test Kurnakov test is used to distinguish between cisplatin and transplatin, by using thiourea as a reagent. Cisplatin + Aqueous thiourea ———> deep yellow solution |Crystallisation yellow needle shape crystal of tetrakis(hioucea) patie (U) chloride ‘Transplatin + Aqueous thiourea——»> Colourless solution [eomstinine ‘white needle shape erystat of trans-bis(thioures)iaamatine platinum (U1) chloride Correct answer: (9) The term symbol of a molecule with electronic —_canfiguration (10,) (10, ¥ (26, (20,Y (on, (Ix) is @ yy, oy ©'X, Given electronic configuration of the molecule is ( ead ( + Only valence shell is considered while writing term symbol, Tenn symbolis. “Wi here a Le(-)=0 = Reflection under plane containing nucli and wxu=g term symbol, “Y. Correct answer: (b) pontaneous if A process is cared dat at constant volume and at constant entropy twill fa) aG <0 () AH <0 ) au <0 Marco aq _ From Clausius inequality, 4S:4 ‘SOLVED PAPER : CSIR-UGC-NETIIRE June 2011 in the molecules H,0, NH, and CH, (a) The bond angles are same (b) The bond distances are same. (©) The hybridizations are same (@) The shapes are same. 4 , tee of Sele AN, AH rH W WH Woon Bond angle: 104.5" 107 109.9" ‘Shape: Bent/angular Pyramidal ‘Tetrahedral Hybridisation » x - Bond length onder: O-H < N-H < C-H Correct answer: (c) ‘The correct order of stability of difluorides is: (a) GeF, > Sif, > CR, (b) CR, > SiR, > Gek, (c) SiF, > GeF, (@ Ck, > Gek, > Si, EN soln Ne) a Se ef — Stabilisation via back-bonding. Due to innet pair effect stability of +2 oxidation state increases down the group, Correet answer: (b) M4. The number of possible isomers for [ Ru(bpy), Cl} is (opy= 2,2*-bipyridine) (a)? 3 4 @s Soln. Isomers of (Ru(bpy),Cl} can be represented as e Q) _ pH Li Lo ON bey Ru py RY VIN j IN a [3 a @ 3) a % on wy, a {Optical inactive) cis form eisform IL snd Il] are enantiomers. Correet answer: (b} The specie: “Ne and "C emit a positron and f— particle respectively. The resulting species rectively 688) Fang 4N (6) Naand4N @) ¥F and *Bqe SOLVED PAPER : CSIR-UGC-NET/JRF June 2011 29. In Ziegler-Natta catalysis the commonly used catalyst system is: (a) TiCl,,Al(C,H,), ) (nb ©), TiC!,, Al(OEt), (©) VOfacac), . Al, (CH), (@) TiC1,, BF, Sola. Ziegler-Natta catalyst is Al(C,H,),+TiCl, Correct answer: (a) 30. Oxidation occurs very easily in case of (a) (n°-C,H,), Fe () (n°-CH,), Co (o) (n° CoH), Ru Soln. Compound (n°-C,H,), Fe (a (n° - CH), Co" Number of clectron in outer shell of central atom 8 (n° ~ C,H), Co 9 (n’ - CH), Ru 18, (a ~C,8,), Co 18 Oxidation of (n'—C,H,), Coo (x oxidise. Correct answer: (b) Co” gives an 18 electron compound, so easier to Complex in which organic ligand is having only ¢—bond with metal is (=) W(CH)), @) (1° ~CsH,), Fe (©) K[Ptct, (CH,)] (a (n? C,H), Ru Hy Sala, teow | cts Z\\ cH Hy” by CHa is W(CHy)g (Only 6-bond with metal) (u'=C,H,), Fe (a'=cyH,), Ru Correct answer: (a)= (ea SOLVED PAPER: CSIR-UGC-NETURFJunez0H 2 — Soln. Charge transfer spectra are possible due to transfer of electron from ligand to metal. This is more probable ifthe metal is ina high oxidation state or ligand has reducing properties. Intense colour of ceric ammonium nitrate, (NH,),[Ce(NO,), ] is due to charge transfer from bidentate NOS to Cet which has C.N = 12. Correct answer: (b) 25, Among SE,,BE/,XeF, and ICI; the number of species having two lone pair of electrons on the cen- tral atom according to VSEPR theory is: @2 3 4 @o Soln. Soln. Soln. 28. Soin. Structure of above compounds can be represented as, c KR | KF [> a B Xt “I >>4 eo NE la Ng (lp) lp) Qip) Qip) Correct answer: (a) ‘The FALSE statement for a polarographic measurement procedure is: (a) 0, is removed (8) Dropping mercury electrode is working electrode, (c) 1, is proportionaal to concentation of electroactive species. (@) Residual current is made zero by adding supporting electrolyte, (a) , must be removed as it give its own polarogram, due to following reactions, 0, #28" +2" ==2H,0,; O, +4H" +4e°==2H,0 {b) Dropping mercury electrode is the working electrode (ac (@) Residual current need not to be made zero. Correct answer: (8) ‘The ligand system present in vitamin B,, is: (2) Porphyrin (6) Corrin (6) Phthalocyanine (d) Crown ether Vitamin B,_ molecule is built-around a corrin ring containing cobalt (IN) atom. Correct answer: (b) Which one of the following exhibits rotational spectra? (a) A, (b) y (©)CO (co, For rotational spectra, p #0 Molecule Dipole moment(:) Rotational spectra H No XN, uso No co peo Yes co. n=0 No‘SOLVED PAPER : CSIR-UGC-NETIJRF June 2011, SOLVED PAPER : CSIR-UGC-NET/JRF June 2014 CHEMICAL SCIENCES BOOKLET-{C] - PART-B 1 According to crystal field theory, NF” can have two unpaired electrons in (a) Octahedral geometry only (b) Square-planar geometry only . (©) Tetrahedral geometry only (@ Both octahedral and tetrahedral geometry. wear PET CC 3d 4s 4p 4d ‘Geometry _| Possible hybridisation Ostahedral pe | Square planar | ip “Tetrahedral| Correct answer: (4) [NWCCN), Fane [NCI] compe ions are (a) Bogh diamagnetic (b) Both param: (c) Djamagnetic and paramagnetic respectively (4) Antiferromagnetic and diamagnetic respectively Soln, [Compound | Hybrid [ Hybridisation ation of Ni* | Number of unpaired electrons [NWCN), J O(diamagnetic) | [ica ye oom Correct answer: (¢) 23, Which of the following spectroscopic teghniques will be use iguish between M-SCN and MENCS binding modes? : (ay NMR IR () EPR (ly Ma Soln etching CN bond stretching at lower at higher frequency frequeney(wave number) (wave number) Correct answer: (6) (2) writ of ine towing compound stow argent a) Lanthanum nitrate (b) Cerie ammenisn fo) Manganese (11) acetate 14) Connor 1