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CSIR-NET JUNE 2011 1. According to crystal field theory, Ni2+ can have two unpaired electrons in (A) Octahedral geometry only (B) Square-planar geometry only (C) Tetrahedral geometry only (D) Both octahedral and tetrahedral geo...
CSIR-NET JUNE 2011 1. According to crystal field theory, Ni2+ can have two unpaired electrons in (A) Octahedral geometry only (B) Square-planar geometry only (C) Tetrahedral geometry only (D) Both octahedral and tetrahedral geometry. 2. [Ni(CN)4]2– and [NiCl4]2– complex ions are (A) Both diamagnetic (B) Both paramagnetic (C) Diamagnetic and paramagnetic respectively (D) Antiferromagnetic and diamagnetic respectively 3. Which of the following spectroscopic techniques will be useful to distinguish between M-SCN and M-NCS binding modes? (A) NMR (B) IR (C) EPR (D) Mass 4. Which of the following compound show a charge-transfer band? (A) Lanthanum nitrate (B) Ceric ammonium nitrate (C) Manganese (II) acetate (D) Copper (II) sulphate pentahydrate 5. Among SF4 , BF4− , XeF4 and ICl−4 the number of species having two lone pair of electrons on the central atom according to VSEPR theory is: (A) 2 (B) 3 (C) 4 (D) 0 6. The FALSE statement for a polarographic measurement procedure is: (A) O2 is removed (B) Dropping mercury electrode is working electrode. (C) Id is proportional to concentration of electroactive species. (D) Residual current is made zero by adding supporting electrolyte. 7. The ligand system present in vitamin B12 is: (A) Porphyrin (B) Corrin (C) Phthalocyanine (D) Crown ether 8. Which one of the following exhibits rotational spectra? (A) H2 (B) N2 (C) CO (D) CO2 9. In Ziegler-Natta catalysis the commonly used catalyst system is: (A) TiCl4 , Al ( C2 H5 )3 ( ) (B) − Cp 2 TiCl2 , Al ( OEt )3 5 (C) VO ( acac )2 , Al2 ( CH3 )6 (D) TiCl 4 , BF3 10. Oxidation occurs very easily in case of ( 5 ) (A) − C5 H 5 2 Fe (B) − C5 H 5 5 ( ) 2 Co (C) ( −C H ) (D) ( −C H ) Co + 5 5 5 5 2 Ru 5 5 2 11. Complex in which organic ligand is having only − bond with metal is: (A) W ( CH3 )6 ( (B) − C5 H 5 Fe 5 ) 2 (C) K PtCl3 ( C2 H 4 ) (D) ( −C H ) 6 6 6 2 Ru 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2011 12. In the molecules H2O, NH3 and CH4. (A) The bond angles are same (B) The bond distances are same. (C) The hybridizations are same (D) The shapes are same. 13. The correct order of stability of difluorides is: (A) GeF2 > SiF2 > CF2 (B) CF2 > SiF2 > GeF2 (C) SiF2 > GeF2 > CF2 (D) CF2 > GeF2 > SiF2 14. The number of possible isomers for Ru ( bpy )2 Cl2 is (bpy = 2,2’–bipyridine) (A) 2 (B) 3 (C) 4 (D) 5 15. The species 19Ne and 14C emit a positron and − particle respectively. The resulting species formed are respectively (A) 19Na and 14B (B) 19F and 14N 19 14 (C) Na and N (D) 19F and 14B 16. Cis and trans complex of the type [PtA2X2] are distinguished by (A) Chromyl chloride test (B) Carbylamine test (C) Ring test (D) Kurnakov test 17. The term symbol of a molecule with electronic configuration (1 ) (1 ) ( 2 ) ( 2 ) (1 ) (1 ) is: 2 2 2 2 1 1 g u g u u u (A) 1 g+ (B) 3 g− (C) 1 g− (D) 3 g+ 18. A process is carried out at constant volume and at constant entropy. It will be spontaneous if: (A) G 0 (B) H 0 (C) U 0 (D) A 0 19. The half life of a zero order reaction ( A → P ) is given by (k = rate constant): (A) t 1 = A 0 2.303 A 0 (B) t 1 = (C) t1 = (D) t 1 = 1 2 2k 2 k 2 k 2 k A 0 20. For an aqueous solution at 25ºC, the Debye-Huckel limiting law is given by (A) log = +0.509 Z+ Z− (B) log = 0.509 Z+ Z− (C) log = −0.509 Z+ Z− (D) log = −0.509 Z+ Z− 2 21. The microwave spectrum of a molecule yields three rotational constants. The molecule is (A) Prolate symmetric top (B) Spherical top (C) Asymmetric top (D) Oblate symmetric top 22. The Q band in the vibrational spectrum of acetylene is observed in the (A) C–C stretching mode (B) C-H symmetric stretching mode (C) Bending mode (D) C-H antisymmetric stretching mode. 23. The Stark splitting for a given field is larger for a molecule AX as compared to BX. Which one of the following is true? ( is the dipole moment) (A) AX = BX (B) AX > BX (C) AX < BX (D) BX = 2AX 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2011 24. The adsorption of a gas on a solid surface exhibits the following isotherm. Which one of the following statements is true? coverage pressure (A) Heat of adsorption is independent of coverage (B) Adsorption is multilayer (C) Heat of adsorption varies monotonically with coverage (D) Heat of adsorption varies exponentially with coverage 25. In a chemical reaction, A ( s ) + B ( g ) C ( g ) , the total pressure at equilibrium is 6 atm. The value of equilibrium constant is: (A) 1/2 (B) 9 (C) 1 (D) 36 26. A molecule, AX, has a vibrational energy of 1000 cm–1 and rotational energy of 10 cm–1. Another molecule, BX, has a vibrational energy of 400 cm–1 and rotational energy of 40 cm–1. 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. (D) There is no coupling in both AX and BX 27. At room temperature, which molecule has the maximum rotational entropy? (A) H2 (B) O2 (C) D2 (D) N2 3 1 2 −r/a 0 28. The normalized hydrogen atom 1s wavefunction is given by 1s = e where a0 = 1 and energy is – 0.5 au. If we use a normalized wavefunction of the above form with 1 average value of energy of the ground state of hydrogen atom is: (A) Greater than – 0.5 au (B) Equal to – 0.5 au (C) Less than – 0.5 au (D) Equal to times – 0.5 au 29. A constant of motion is defined by the equation: (a) [H, A] = 0 (B) = 0 (C) A = f(H) (D) A† = A 30. The Hermitian conjugate of operator d/dx, called ( d / dx ) , is equal to † (A) −d / dx (B) d/dx (C) i(d/dx) (D) –i(d/dx) 31. An ideal gas expands by following an equation PVa = constant. In which case does one expect heating? 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2011 (A) 3 > a > 2 (B) 2 > a > 1 (C) 0 < a < 1 (D) –1 < a < 0 32. If y2 = 4x and 0.1% error is incurred for x, the percentage error involed in y will be (A) 0.4 (B) 0.025 (C) 0.1 (D) 0.05 33. The configuration at the two stereo centres in the compound given below are (A) 1R, 4R (B) 1R, 4S (C) 1S, 4R (D) 1S, 4S 34. The two compounds given below are (A) Enantiomers (B) Identical (C) Diastereomers (D) Regioisomers. 35. A suitable catalyst for bringing out the transformation given below is: (A) BF3.Et2O (B) NaOEt (C) Tungsten lamp (D) Dibenzoyl peroxide 36. Thermolysis of allyl phenyl ether generates (A) o-allylphenol only (B) o- and p-allylphenols (D) o-, m- and p-allylphenols (D) m-allylphenol only 37. The major product formed in the reaction given below is: 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2011 (A) (B) (C) (D) 38. The most suitable reagent for the following transformation is: (A) LiAlH4 (B) NH2NH2 /KOH (C) NaBH4 /CeCl3 (D) Li/liq. NH3 39. The intermediate involved in the reaction given below is: (A) Free radical (B) Carbocation (C) Carbanion (D) Carbene 40. In the most stable conformation of trans-1-t-butyl-3-methylcyclohexane, the substituents at C–1 and C–3, respectively, are (A) Axial and equatorial (B) Equatorial and equatorial (C) Equatorial and axial (D) Axial and axial. 41. Among the carbocations given below (A) A is homoaromatic, B is antiaromatic and C is aromatic. (B) A is aromatic, B is antiaromatic and C is homoaromatic. 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2011 (C) A is antiaromatic, B is aromatic and C is homoaromatic. (D) A is homoaromatic, B is aromatic and C is antiaromatic. 42. 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 43. In the mass spectrum of the compound given below, during the − cleavage , the order of preferential loss of groups is (A) Me > C3H7 > Et (B) C3H7 > Et > Me (C) Et > Me > C3H7 (D) Et > C3H7 > Me 44. The reaction given below is an example of (A) 1, 3-sigmatropic hydrogen shift (B) 1, 3-sigmatropic methyl shift (C) 1, 5-sigmatropic hydrogen shift (D) 1, 5-sigmatropic methyl shift. 45. The concerted photochemical reaction between two olefins leading to a cyclobutane ring is: (A) 2s + 2a cycloaddition (B) 2s + 2s cycloaddition (C) 2s + 2s cycloaddition (D) 2s + 2s cycloaddition 46. Addition of BH3 to a carbon-carbon double bond is: (A) anti-Markovinikov syn addition (B) anti-Markovnikov anti addition (C) Markovnikov syn addition (D) Markovnikov anti addition. 47. The absorption at max 279 nm ( = 15) in the UV spectrum of is due to (A) − * transition (B) n − * transition (C) − * transition (D) − * tranition 48. The reaction given below is an example of (A) E2-elimination (B) E1-elimination (C) syn-elimination (D) E1cb-elimination 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2011 49. The suitable reagent for the following conversion is: (A) m–CPBA (B) H2O2 /AcOH (C) tBuOH/HCl (D) H2O2 /NaOH 50. The relative rates of solvolysis of iodides A-C are (A) C > A > B (B) C > B > A (C) B > C > A (D) B > A > C 51. Alkali metal superoxides are obtained by the reaction of (A) Oxygen with alkali metals in liquid ammonia. (B) Water with alkali metals in liquid ammonia (C) H2O2 with alkali metals. (D) H2O2 with alkali metals in liquid ammonia. 52. H2O2 reduces 3− A. Fe ( CN )6 B. KIO 4 C. Ce (SO4 )2 D. SO32− (A) A and B only (B) B and C only (C) C and D only (D) B and D only 53. Match List-I (compounds) with List-II (application) and select the correct answer using the codes given below the lists. List -I List-II (A) Trisodium phosphate (i) Plasticizer (B) Triarylphosphates (ii) Water softener (C) Triethylphosphate (iii) Toothpaste (D) Calcium hydrogen (iv) Insecticides phosphate (A) (A)-ii (B)-i (C)-iv (D)-iii (B) (A)-i (B)-ii (C)-iv (D)-iii (C) (A)-ii (B)-iii (C)-iv (D)-i (D) (A)-iii (B)-i (C)-ii (D)-iv 54. Among the following statements, identify the correct ones for complexes of lanthanide(III) ion. (A) Metal-ligand bond is significantly ionic. (B) Complexes rarely show isomerism. (C) The coordination number is not more than 8. (D) The magnetic moments are not accounted even approximately by spin only value for majority of lanthanides. 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2011 (A) A, B and D only (B) A, B and C only (C) B and C only (D) A and D only. 55. According to VSEPR theory, the molecule/ion having ideal tetrahedral shape is: (A) SF4 (B) SO24− (C) S2Cl2 (D) SO2Cl2 56. The complex [Mn(H2O)6]2+ has very light pink colour. The best reason for it is (A) The complex does not have a charge transfer transition. (B) d-d transitions here are orbital forbidden but spin allowed. (C) d-d transitions here are orbital allowed but spin forbidden. (D) d-d transitions here are both orbital forbidden and spin forbidden. 57. The highest occupied MO in N2 and O+2 respectively are (take x-axis as internuclear axis) (A) 2p x , * 2p y (B) 2p y , 2pz (C) * 2px , 2p x (D) * 2p y , * 2pz 58. The correct order of LMCT energies is: (A) MnO−4 CrO42− VO34− (B) MnO−4 CrO42− VO34− (C) MnO−4 CrO42− VO34− (D) MnO−4 CrO42− VO34− 59. Carboxypeptidase contains: (A) Zn(II) and hydrolyses CO2. (B) Zn(II) and hydrolyses peptide bonds. (C) Mg(II) and hydrolyses CO2. (D) Mg(II) and hydrolyses peptide bonds. 60. In the EPR spectrum of tetragonal Cu(II) complex, when g g ⊥ g e the unpaired electron resides in the orbital. (A) dxy (B) d x 2 − y2 (C) d z 2 (D) d xy 61. The oxidative addition and reductive elimination steps are favoured by (A) Electron rich metal centres. (B) Electron deficient metal centres (C) Electron deficient and electron rich metal centres respectively. (D) Electron rich and electron deficient metal centres respectively 62. Identify the order according to increasing stability of the following organometallic compounds, TiMe4 ,Ti ( CH 2 Ph )4 ,Ti ( i − Pr )4 and TiEt 4. (Me = methyl, Ph = phenyl, i-Pr = isopropyl, Et = ethyl) (A) Ti ( CH2 Ph )4 Ti ( i − Pr )4 TiEt TiMe4 (B) TiEt 4 TiMe4 Ti ( i − Pr )4 Ti ( CH2 Ph )4 (C) Ti ( i − Pr )4 TiEt 4 TiMe4 Ti ( CH2 Ph )4 (D) TiMe4 Ti ( i − Pr )4 TiEt 4 Ti ( CH2 Ph )4 63. Among the metals, Mn, Fe, Co and Ni, the ones those would react in its native form directly with CO giving metal carbonyl compounds are: (A) Co and Mn (B) Mn and Fe (C) Fe and Ni (D) Ni and Co 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2011 64. The molecule with highest number of lone-pairs and has a linear shape based on VSEPR theory is: (A) CO2 (B) I3I (C) NO−2 (D) NO+2 65. Given Ag + + e → Ag, E0 = 0.50 V Cu 2+ + 2e → Cu, E0 = 0.34 V A 100 ml solution is 1080 mg with respect to Ag+ and 635 mg with respect to Cu2+. If 0.1mg Ag+ left in the solution is considered to be the complete deposition of Ag+, the cathode potential, so that no copper is deposited during the process, is: (A) 0.16 V (B) 0.84 V (C) 0.31 V (D) – 0.16 V 66. In the H2Ru6(CO)18 cluster, containing 8-coordinated Ru centres, the hydrogen atoms are (A) Both terminal (B) One terminal and the other bridging (C) Both bridging between two Ru centres (D) Both bridging between three Ru centres. 67. In the hydroformylation reaction, the intermediate CH3CH2CH2Co(CO)4: (A) Forms are acyl intermediate CH3CH2CH2Co(CO)3 (B) Forms an adduct with an olefin reactant (C) Reacts with H2 (D) Eliminates propane. 68. Statement I: The sizes of Zr and Hf are similar Statement II: Size of Hf is affected by lanthanide contraction. (A) Statement I and II are correct and II is correct explanation of I. (B) Statement I and II are correct but II is not a correct explanation of I. (C) Statement I is correct and II is incorrect (D) Statements I and II both are incorrect. 69. Consider the compounds, (A) SnF4, (B) SnCl4, and (C) R3SnCl. The nuclear quadrupole splitting are observed for. (A) (A), (B) and (C) (B) (A) and (B) only (C) (B) an d (C) only (D) (A) and (C) only 70. Consider two redox pairs (1) Cr(II)/Ru(III) (2) Cr(II)/Co(III) The rate of acceleration in going from a outer-sphere to a inner-sphere mechanism is lower for (1) relative to (2). Its correct explanation is: (A) HOMO/LUMO are * and * respectively (B) HOMO/LUMO are * and * respectively (C) HOMO/LUMO are * and * respectively (D) HOMO/LUMO are * and * respectively 71. The correct value of isomer shift (in Mossbauer spectra) and its explanation for Fe(II)–TPP and Fe(III)–TPP respectively from the following are: (TPP = tetraphenylporphyrinate) (A) 0.52 mms–1 (B) 0.45mms–1 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2011 (C) Increase in s electron density (D) Decrease in s electron density. (A) (A) and (D); (B) and (C) (B) (A) and (C); (B) and (C) (C) (B) and (D); (A) and (D) (D) (B) and (D); (A) and (C) 3− 72. In IR spectrum of Co ( CN )5 H the Co–H stretch is observed at 1840 cm–1. The (Co–D) 3− stretch in Co ( CN )5 D will appear at nearly (A) 1300 cm–1 (B) 1400 cm–1 (C) 1500 cm–1 (D) 1600 cm–1 73. For the complexes 2+ 2+ 3+ 3+ (A) Ni ( H 2O )6 (B) Mn ( H 2O )6 (C) Cr ( H 2O )6 (D) Ti ( H 2O )6 , the ideal octahedral geometry will not be observed in (A) (A) and (D) (B) (C) and (D) (C) (B) only (D) (D) only 74. Among the following, the number of anhydrides of acids are CO, NO, N2O, B2O3, N2O5, SO3 and P4O10. (A) 3 (B) 4 (C) 5 (D) 6 75. For a given nuclear fission reaction of 235U 92 U + 0 n ⎯⎯ → 142 56 Ba + 36 Kr + 30 n 235 1 91 1 the amount of energy (in kJ/mol) released during this process is (given 235U = 235.0439 amu, 142 Ba = 141.9164 amu, 91Kr = 90.9234 amu, neutron = 1.00866 amu) (A) 3.12 1012 (B) 2.8 1011 (C) 1.0 109 (D) 1.68 1010 76. The decomposition of gaseous acetaldehyde at T(K) follows second order kinetics. The half-life of this reaction is 400 s when the initial pressure is 250 Torr. What will be the rate constant (in Torr –1 s–1) and half-life (in s) respectively, if the initial pressure of the acetaldehyde is 200 Torr at the same temperature? (A) 105 and 500 (B) 10–5 and 400 (C) 10–4 and 400 (D) 10–5 and 500 77. For an enzyme catalysed reaction, a Lineweaver-Burk plot gave the following data: slope = 40 s intercept = 4 (mmol dm–3 s–1)–1. If the initial concentration of enzyme is 2.5 10−9 mol dm–3, what is the catalytic efficiency (in dm–3 mol–1 s–1) of the reaction? (A) 105 (B) 106 (C) 107 (D) 104 78. A hydrogenic orbital with radial function of the form r exp −r and − par as exp −3i corresponds to (A) n 4, 3, m = 3 (B) n = 4, = 3, m = −3 (C) n = 4, 3, m = 3 (D) n 4, = 3, m = −3 79. For an assembly of molecules (molar mass = M) at temperature T, the standard deviation of Maxwell’s speed is approximately 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2011 RT RT (A) 0.7 (B) 1.4 M M M M (C) 0.7 (D) 1.4 RT RT 80. The unperturbed energy levels of a system are 0 = 0,1 = 2 and 0 = 0,2 = 4.The second order correction to energy for the ground state in pressure of the perturbation V for which V10 = 2, V20 = 4 and V12 = 6 has been found to be (A) –6 (B) 0 (C) +6 (D) –8 81. Given the character table of the point group C3V E 2C3 3 v A1 1 1 1 z A2 1 1 –1 E 2 –1 0 (X,Y) Consider the reducible representation, E 2C3 3 v 6 3 0 Its irreducible components are (A) E + 2A1 + 2A2 (B) 2E + A1 + A2 (C) 3A1 + 3A2 (D) E2 + 2A1 82. Refer to the character table of the point group C3V given above. Find which of the following transition is forbidden (A) a1 ⎯ → a1 (B) a1 ⎯→e (C) a 2 ⎯ →e (D) a1 ⎯ →a2 83. The electronic configuration for gadolinium (GD) [Xe]4f75d16s2, where as that of Gd2+ is: (A) [Xe]4f 5 5d6s2 (B) [X]4f 6 6s2 (C) [Xe]4f 65d16s1 (D) [Xe]4f 75d1 84. The possible J values for 3D term symbol are (A) 2 (B) 3 (C) 4 (D) 5 85. The energy levels for cyclobutadiene are + 2, , and − 2. The delocalization energy in this molecule is: (A) 0 (B) −4 (C) −8 (D) 4 86. The variation of equilibrium constant (K) of a certain reaction with temperature (T) is 2.0 104 In k = 3.0 + given R = 8.3 Jk–1mol–1, the values of H 0 and S0 are. T (A) 166 kJ mol–1 and 24.9 Jk–1 mol–1 (B) 166 kJ mol–1 and –24.9 Jk–1 mol–1 –1 –1 –1 (C) –166 kJ mol and 24.9 Jk mol (D) –166 kJ mol–1 and 24.9 Jk–1 mol–1 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2011 87. The chemical potential of component 1 in a solution of binary mixture is 1 = 10 + RT in p1, when p1 is the partial pressure of component 1 vapour phase. The standard state 10 is: (A) Independent of temperature and pressure (B) Depends on temperature and pressure both (C) Depends on temperature only (D) Depends on pressure only 88. Debey-Hückel screening length ( k −1 ) is a measure of size of diffuse ion cloud around an ion, ( ) −1 2e 2 N A provided 30 nm molkg −1 at 298K, which of the following values of −1 is true 0 k BT for a 0.03 molal solution for Na2SO4 in water (r 100 ) ? 10 9 (A) nm (B) nm 9 10 10 2 9 (C) nm (D) nm 9 10 2 89. If the ratio of composition of oxidized and reduced species in electrochemical cell, is given as O = e2 , the correct potential difference will be R 2RT 2RT (A) E − E 0' = + (B) E − E 0' = − nF nF RT RT (C) E − E 0' = (D) E − E 0' = − nF nF 90. If the equilibrium constants for the reactions 1 and 2 (1) CO ( g ) + H 2O ( g ) CO2 (g) + H 2 (g) (2) CH 4 ( g ) + H 2O ( g ) CO(g) + 3H 2 (g) are k1 and k2, the equilibrium constant for the reaction CH 4 ( g ) + 2H 2O ( g ) CO2 (g) + 4H 2 (g) is: (A) k1 + k2 (B) k1 – k2 (C) k1k2 (D) k1/k2 91. The virial expansion for a real gas can be written in either of the following forms: PV = 1 + BP P + CP P 2 +..... RT = 1 + BV V + CV V2 +..... If BV = VP, the value of would be (A) PV/RT (B) RT/PV (C) PV (D) RT 92. A certain system of noninteracting particles has the single-particle partition has the single- m particle partition function f = A T where A is some constant. The average energy per particle V will be (A) mT (B) AT (C) T/m (D) T/A 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2011 93. 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 dm–3 using 1 cm cell is 0.5. Solution B: The optical density 0.5 mol dm–3 is measured using 1 mm cell. Solution C: The transmittance of this solution is 0.1. The optical density of these solutions follow the order. (log 20 = 1.3010; log 30 = 1.4771, log 50 = 1.6990 (A) A > B > C (B) B > C > A (C) B > A > C (D) C > A > B 94. The rotational constant of 14N2 is 2 cm–1. The wave number of incident radiation in a Raman spectrometer is 20487 cm–1. What is the wave number of first scattered Stokes line (in cm–1) of 14 N2? (A) 20479 (B) 20475 (C) 20499 (D) 20495 95. For a certain particle encountering a barrier, the tunnelling probability is approximately e–10. If the mass is halved and width of the barrier (rectangular) doubled, approximate value of the tunnelling probability will be (A) e −10/ 2 (B) e −10 2 (C) e −20 2 (D) e −10 96. An operator A is defined as A = − d + x. Which one of the following statements is true? dx (A) A is a Hermitian operator. (B) A† is an antihermitian operator (C) Both AA † and A † A are Hermitian (D) AA † is Hermitian, but A † A is antihermitian 97. Isothermal which has fractional coverage, linearly, dependent on pressure at low pressures but almost independent at high pressure is called (A) BET isotherm (B) Langmuir isotherm (C) Freundlich isotherm (D) Temkin isotherm 98. A one-dimensional crystal of lattice dimension ‘a’ is metallic. If the structure is distorted in such a way that the lattice dimension is enhanced to ‘2a’. (A) The electronic structure remains unchanged. (B) The width of conduction band decreases and a band gap is generated. (C) The width of conduction band increases (D) The width of the conduction band remains unchanged. 99. For a H2 molecule, the ground state wavefunction is (1, 2 ) = (1, 2 ) (1, 2 ) where refers to the space part and to the spin part. Given that (1, 2 ) = ( 2,1) , the form of (1, 2 ) would be (A) (1) ( 2 ) (B) ( 2 ) (1) (C) (1) ( 2 ) − ( 2 ) (1) (D) (1) ( 2 ) + ( 2 ) (1) 100. There are several types of mean molar masses for polymer and they are dependent on experimental methods like: (1) Osmometry (2) Light scattering (3) Sedimentation. Correct relation between mean molar masses and experimental method is: 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2011 (A) Mn ( 3) , M w ( 2 ) M z (1) (B) M n ( 2 ) , M w ( 3) M z (1) (C) Mn (1) , M w ( 2 ) M z ( 3) (D) M n (1) , M w ( 3) M z ( 2 ) 101. An organic compound (C7H12O2) exhibited the following data in the 1H NMR spectrum. 7.10(1 H, d t, J = 16 and 7.2Hz), 5.90 (1H, d t,J = 16 and 2 Hz), 4.1(2H, q,J = 7.2Hz), 2.10(2H, m), 1.25(3H, t, J = 7.2Hz), 0.90 (3H, t, J = 7.2 Hz) ppm, The compound, among the choices given below, is: (A) (B) (C) (D) 102. In the broad band decoupled 13C NMR spectrum, the number of signals appearing for the bicyclooctane A–C, respectively, are (A) Five, four and eight (B) Three, two and five (C) Five, four and five (D) Three, two and eight 103. In the mass spectrum of dichlorobenzene the ratio of the peaks at m/z 146, 148 and 150, is: (A) 1:1:1 (B) 3:3:1 (C) 1:2:1 (D) 9:6:1 104. The major compound X formed in the following reaction exhibited a strong absorption at v max 1765 cm–1 in the IR spectrum. The structure of X is: (A) (B) 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2011 (C) (D) 105. The correct order of acidity of the following compound A–C is: (A) B > C > A (B) C > B > A (C) A > C > B (D) A > B > C 106. The major product formed in the reaction sequence is: (A) (B) (C) (D) 107. For the following allylic oxidation reaction, the appropriate statement, among the choices given below, is: 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2011 (A) Suitable reagent is KMnO4 and the major product is A. (B) Suitable reagent is KMnO4 and the major product is B. (C) Suitable reagent is SeO2 and the major product is A. (D) Suitable reagent is SeO2 and the major product is B 108. The intermediate A and the major product B in the following conversion are (A) A is carbocation and B is (B) A is carbanion and B is (C) A is a free radical and B is (D) A is a benzyne and B is 109. The major product formed in the following reaction is: (A) (B) 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2011 (C) (D) 110. The major product formed in the following reaction is (A) (B) (C) (D) 111. The major product formed in the reaction of glucose with benzaldehyde and p-TSA is: (A) (B) (C) (D) 112. Papaverine on oxidation with potassium permanganate gives a ketone, which on fusion with potassium hydroxide give 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2011 (A) (B) (C) (D) 113. The major product formed on nitration (HNO3/H2SO4) of uridine followed by reduction with tin and HCl is: (A) (B) (C) (D) 114. In the following reaction sequence, the correct structures for the major products X and Y are (A) (B) (C) 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2011 (D) 115. The major product formed in the following reaction is: (A) (B) (C) (D) 116. Match the following: Column I Column II A. (i) Chiral centre B. (ii) Chiral axis 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2011 C. (iii) Chiral plane (iv) Helical chirality (A) (A)-iii (B)-ii (C)-iv (B) (A)-iv (B)-iii (C)-ii (C) (A)-ii (B)-iv (C)-iii (D) (A)-ii (B)-iii (C)-iv 117. The gauche interaction values for Me/Me, Me/Br and Br/Br are 3.3, 0.8 and 3.0 kJ/mol, respectively. Among the following, the most stable conformation of 2, 3-dibromobutane is: (A) (B) (C) (D) 118. The major product formed in the reaction of (S)-1, 2, 4-butanetriol with 3-pentanone in the presence of a catalytic amount of p-TSA is: (A) (B) (C) (D) 119. The major product formed in the following reaction is 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2011 (A) (B) (C) (D) 120. The major product formed in the following transformation is: (A) (B) (C) (D) 121. The major product formed in the following transformation is: (A) (B) (C) (D) 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2011 122. The structures of the major products X and Y in the following transformation are (A) (B) (C) (D) 123. Match the following: Column I Column II A. Pyrrole i. Pictet-Spengler B. 1, 4-dihydropyridine ii. Chichibabin C. Is quinoline iii. Paal-Knorr iv. Hantzsch (A) (A)-i (B)-ii (C)-iii (B) (A)-ii (B)-iii (C)-iv (C) (A)-iv (B)-i (C)-ii (D) (A)-iii (B)-iv (C)-i 124. Consider the following reaction: 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2011 In an experiment, 1.99 g of bromide A on reaction with ethanolic potassium hydroxide gave 1.062 g of a mixture of the olefins B and C. If the ratio of olefins B : C formed is 2 : 1, the yields for their formation, respectively, are (A) 60 and 30% (B) 50 and 25% (C) 66 and 33% (D) 54 and 27% 125. An organic compound A =(C8H16O2) on treatment with an excess of methyl magnesium chloride generated two alcohols B and C, whereas reaction of A with lithium aluminium hydride generated only a single alcohol C. Compound B on treatment with an acid yielded an olefin (C6H12), which exhibited only a singlet at 1.6 ppm in the 1H NMR spectrum. The compound A is (A) (B) (C) (D) 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 1. Identify which of the following operators is not Hermitian? d d2 (A) (B) i 2 i dx dx 2 d (C) 2 (D) x2 dx 2. The term symbol for the ground state of nitrogen atoms is (A) 3P0 (B) 4P3/2 (C) 1P1 (D) 4S3/2 3. PA and PB denote the populations of two energy states EA and EB, and EA > EB The correct statement when the temperature T1 > T2 is (A) PA ( T1 ) PB ( T1 ) , PA ( T2 ) PB ( T2 ) and ( PA / PB )T1 ( PA / PB ) T2 (B) PA ( T1 ) PB ( T1 ) , PA ( T2 ) PB ( T2 ) and ( PA / PB )T1 ( PA / PB ) T2 (C) PA ( T1 ) PB ( T1 ) , PA ( T2 ) PB ( T2 ) and ( PA / PB )T1 ( PA / PB ) T2 (D) PA ( T1 ) PB ( T1 ) , PA ( T2 ) PB ( T2 ) and ( PA / PB )T1 ( PA / PB ) T2 4. The uncertainty in the NMR frequency of a compound in liquid state (relaxation time =1s) is 0.1 Hz. The uncertainty in the frequency (in Hz) of same compound in solid state (relaxation time 10–4 ) is (A) 10–4 (B) 100 (C) 1000 (D) 10–3 5. Which one of the following conductometric titrations will show a linear increase of the conductance with volume of the titrant added up to the break point and an almost constant conductance afterwards. (A) A strong acid with a strong base (B) A strong acid with a weak base (C) A weak acid with a strong base (D) A weak acid a weak base. 6. Flocculation value of K2SO4 is much less than that of KBr for Sol A. Floccultion value of CaCl2 is much less than that of NaCl for Sol B. Which of the following statements is correct ? (A) Sol A is negatively charged and Sol B is positively charged (B) Both the sols are negatively charged. (C) Sol A is positively charged and sol B is negatively charged (D) Both the sols are positively charged. 7. For a system of constant composition, the pressure (P) is given by. U U (A) − (B) − S V V S V U (C) (D) S T V T 8. The value of d111 in a cubic crystal is 325.6 pm. The value of d333 is (A) 325.6 pm (B) 976.8 pm (C) 108.5 pm (D) 625.6 pm 9. The symmetry point group of ethane in its staggered conformation is (A) C3v (B) D3d (C) D3h (D) S6 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 10. For the reaction C2 H4 ( g ) + 3O2 ( g ) → 2CO2 ( g ) + 2H 2O ( ) , the value of H − U (in kJ) at 300 K and 1 bar is (A) –5.0 (B) 0.0 (C) 2.5 (D) 5.0 11. The sodium D lines are due to 2 P1 →2 S 1 ( E1 ) and 2 P3 →2 S 1 ( E 2 ) transitions. The 2 2 2 2 splitting due to spin-orbit coupling in 2P state of the sodium atom is (A) E 2 + E1 (B) E 2 − E1 E 2 + E1 E 2 − E1 (C) (D) 2 2 12. The rate constant of a unimolecular reaction was 2.66 10−3 s −1 and 2.2 10−1 s −1 at T=120K and 360 K respectively. The rate constant (in s–1 units) at 240 K would be (A) 2.4 10−2 (B) 2.4 10−1 −2 (C) 4.8 10 (D) 1.8 10−3 13. For a potentiometric titration, in the curve of emf (E) vs volume (V) of the titrant added, the equivalence point is indicated by (A) dE / dV = 0, d 2 E / dV 2 = 0 (B) dE / dV = 0, d 2 E / dV 2 0 (C) dE / dV 0, d 2 E / dV 2 0 (D) dE / dV 0, d 2 E / dV 2 0 14. The osmotic pressure () of a polymer sample at different concentrations (c) was measured at T(K). A plot of ( / c) versus c gave a straight line with slope (m) and intercept (c'). The number average molecular weight of the polymer is (R = gas constant). Rt c' (A) (B) c' RT (C) RT (D) mRT 15. The concentration of a reactant undergoing decomposition was 0.1, 0.08 and 0.067 mol L−1 after 1.0, 2.0 and 3.0 hr respectively. The order of the reaction is (A) 0 (B) 1 (C) 2 (D) 3 16. A particle is constrained in a one dimensional box of length 2a with potential V ( x ) =; x −a, x a and V ( x ) = 0; −a x a. Energy difference between levels n = 3 and n = 2 is 5h 2 9h 2 (A) (B) 8ma 2 8ma 2 9h 2 5h 2 (C) (D) 32ma 2 32ma 2 17. In the 19F NMR spectrum of PF5, the number of signals and multiplicity, at room temperature are (A) one, singlet (B) one, doublet (C) two, doublet (D) two singlet 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 18. The correct statement regarding closo-BnHn species is : (A) it always has –2 charge (B) it always has +2 charge (C) it is a neutral species (D) it is more reactive than nido arachno-, and hypo-boranes 19. Lewis acidity of BCl3, BPh3 and BMe3 with respect to pyridine follows the order (A) BCl3 > BPh3 > BMe3 (B) BMe3 > BPh3 > BCl3 (C) BPh3 > BMe3 > BCl3 (D) BCl3 > BMe3 > BPh3 20. Superoxide dismutase contains the metal ions (A) Zn (II) and Ni(II) (B) Cu(II) and Zn(II) (C) Ni (II) and Co(III) (D) Cu (II) and Fe(III) 21. The number of antibonding electrons in NO and CO according to MO theory are respectively. (A) 1, 0 (B) 2, 2 (C) 3, 2 (D) 2, 3 22. The correct combination of metal, number of carbonyl ligands and the charge for a metal z− carbonyl complex M ( CO )x that satisfies the 18 electron rule is (A) M = Ti, x = 6, z =1 (B) M = V, x = 6, z =1 (C) M = Co, x = 4, z=2 (D) M = Mo, x = 5, z = 1 23. Among the following pairs (1) oxygen-sulfur (2) nitrogen -phosphorus (3) phosphorus arsenic (4) chlorine- iodine Those in which the first ionization energies differ by more than 300 kJ/mol−1 are : (A) (1) and (3) only q (B) (1) and (2) only (C) (2) and (3) only (D) (3) and (4) only 24. The stable cyclopentadienyl complex of beryllium is (A) Be ( 2 − C5 H5 ) (B) Be ( 2 − C5 H5 )( 3 − C5H5 ) 2 (C) Be ( 1 − C5H5 )( 3 − C5H5 ) (D) Be ( 1 − C5 H5 )( 5 − C5H5 ) 25. The reaction between NH4Br and Na metal in liquid ammonia (solvent) results in the products (A) NaBr,HBr (B) NaBr,H2 (C) H2, HBr (D) HBr, H2 26. The material that exhibits the highest electrical conductivity among the following sulfur- nitrogen compounds is (A) S4N4 (B) S7NH (C) S2N2 (D) (SN)x 27. Uranium fluorides co-precipitate with (A) CaF2 (B) AgF (C) LiF (D) MgF2 28. 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) 9.95 10−8 (B) 3.95 10−6 −8 (C) 4.5 10 (D) 6.0 10−8 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 29. The actual magnetic moment shows a large deviation from the spin-only formula in the case of (A) Ti3+ (B) V3+ (C) Gd3+ (D) Sm3+ 30. The complex that absorbs light of shortest wavelength is 3+ (A) CoF6 (B) Co ( H 2O )6 3− ( OX = C O ) 3+ 3− (C) Co ( NH3 )6 (D) Co ( OX )3 2 4 −2 31. Two particles having speeds S1 and S2 have kinetic energies 1 and 2 MeV respectively; the relationship between S1 and S2 is: (A) S1 = 2S2 (B) S2 = S21 (C) S2 = 2S1 (D) S1 = 2S2 32. Green coloured Ni(PPh2Et)2 Br2, has a magnetic moment of 3.20 B.M. The geometry and the number of isomers possible for the complex respectively, are (A) square planar and one (B) tetrahedral and one (C) Square planer and two (D) tetrahedral and two 33. The chemiluminescence method for determining NO in environmental samples is based on formation of NO2* (excited) which is generally generated by reacting NO with (A) O2 (B) O−2 (C) O3 (D) O2 2− 34. In the IR spectrum, carbonyl absorption band for the following compound appears at (A) 1810 cm–1 (B) 1770 cm–1 (C) 1730 cm–1 (D) 1690 cm–1 35. Among the following compounds, the formyl anion equivalent is (A) acetylene (B) nitromethane (C) ethyl chloroformate (D) 1, 4-dithiane 36. In the following concerted reaction, the product is formed by a (A) 6 − disrotatory electrocyclization (B) 4 −disrotatory electrocyclisation (C) 6 − conrotatory electrocyclization (D) 4 −conrotatory electrocyclisation. 37. A suitable reagent combination for carrying out the following conversion is (A) trimethyl orthoacetate and p- toluenesulfonic acid (B) trimethyl ortho acetate and sodium hydroxide 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 (C) 2-methoxypropene and p-toluenesulfonic acid (D) 2- methoxypropene and sodium hydroxide 38. The IUPAC name of the following compound is (A) (R)-3- (prop-2-enyl) hex-5-ynoic acid (B) (S)-3- (prop-2-enyl) hex-5-ynoic acid (C) (R)-3- (prop-2-enyl) hex-5-enoic acid (D) (S)-3- (prop-2-ynyl) hex-5-enoic acid 39. In the mass spectrum of dodecahedrane (C20H20), approximate ratio of the peaks at m/z 260 and 261 is: (A) 1 : 1 (B) 5 : 1 (C) 10 : 1 (D) 20 : 1 40. The reaction given below proceeds through (A) (B) (C) (D) 41. Among the following drugs, the anticancer agents is: (A) captopril (B) chloroquine (C) camptothecin (D) ranitidine 42. The reaction that involves the formation of both C-C and C-O bonds is (A) Diels-Alder reaction (B) Darzen’s glycidic ester condensation (C) aldol reaction (D) Beckmann rearrangement 43. Among A-C, the aromatic compounds are (A) A, B and C (B) A and B only (C) B and C only (D) A and C only 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 44. In the following Markownikov addition reaction, the products A and B are (A) homomers (B) enantiomers (C) diastereomers (D) regioisomers 45. The major product formed in the following reaction is (A) (B) (C) (D) 46. Among A-C, the compounds which can exhibit optical activity are (A) A, B and C (B) A and B only (C) A and C only (D) B and C only 47. The major product formed in the following reaction is (A) (B) 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 (C) (D) 48. An organic compound (MF : C8H10O) exhibited the following 1H NMR spectral data : 2.5 (3H,s), 3.8 (3H, s), 6.8 (2 H, d, J=8Hz), 7.2 (2 H, d, J=8 Hz) ppm. The compound among the choices, is (A) 4-ethylphenol (B) 2-ethylphenol (C) 4-methylanisole (D) 4-methylbenzyl alcohol 49. With respect to electrophilic aromatic substitution, reactivity order of pyrrole, pyridine and indole is (A) indole > pyrrole > pyridine (B) pyrrole > pyridine > indole (C) pyrrole > indole > pyridine (D) indole > pyridine > pyrrole 50. The most appropriate reagent suitable for the conversion of 2-octyne into trans-2-octene is (A) zinc and acetic acid (B) 10% Pd/C (C) lithium in liquid ammonia (D) hydrazine hydrate 51. Consider a n-type semiconductor whose Ev = 0, Ec = 2.0eV and Ed = 1.98eV. The correct statement among the following is (A) Ef = 1eV and is independent of T (B) Ef = 1.99 eV and remains independent of T (C) Ef = 1.99 eV and increases towards 2.0 eV with increase of T (D) Ef = 1.99 eV and decreases with increase of T. 52. Reaction of Fe(CO)5 with OH– leads to complex A which on oxidation with MnO2 gives B. Compounds A and B respectively are − − (A) HFe ( CO )4 and Fe3 ( CO )12 (B) Fe ( CO )5 ( OH ) and Fe2 ( CO )9 2− − (C) Fe ( CO )4 and Mn 2 ( CO )10 (D) HFe ( CO )4 and Fe2O3 53. For the reaction H 2O ( g ) + C ( graphite ) CO ( g ) + H 2O ( g ) , the variation of energy parameter G o , H o and T So of the reaction over a large temperature range is shown below. The correct identification of the curves is given by (A) A → G o , B → H o , C → TSo (B) A → H o , B → G o , C → TSo (C) A → G o , B → TSo , C → H o (D) A → TSo , B → H o , C → G o 54. A Sodalite cage in zeolites is (A) a truncated tetrahedron (B) an icosahedron 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 (C) a truncated octahedron (D) a dodecahedron 55. Two moles of a non-volatile solute is dissolved in 48 mol of water and the resultant solution has a vapour pressure of 0.0392 bar at 300 K. If the vapour pressure of pure water at 300 K is 0.0400 bar, the activity coefficient of water in the solution is: (A) 0.96 (B) 0.98 (C) 1.00 (D) 1.02 56. The final product (s) of the reaction P(OR)3 + R’X is/are (A) R 'PO ( OR )2 and RX (B) R ' PO ( OR )2 X (C) R ' RPO2 ( OR ) X (D) ROR 'and P ( OR )2 X 57. 1 mol of CO2,1 mol of N2 and 2 mol of O2 were mixed at 300 K. The entropy mixing is (A) 6 R n2 (B) 8R n2 (C) 8 R n2 (D) 16R n2 300 58. For the eigenstates of the hydrogen atom, which of the following relations between the expectation value of kinetic energy (T) and potential (V) holds true? (A) T = V (B) 2 T = − V (C) 2 T = V (D) T = −2 V dP 59. For the liquid at 1 bar and 400 K is 8 10−3 bar K–1. vapour equilibrium of a substance dT If the molar volume in the vapour form is 200 L mol–1 and the molar volume in the liquid form is negligible, the molar enthalpy of vaporisation is (1.0bar L = 100J) (A) 640 kJ mol–1 (B) 100 kJ mol–1 (C) 80 kJ mol–1 (D) 64 kJ mol–1 60. The correct order of acidity among the following species is + 2+ 2+ 3+ (A) Na ( H 2O )6 Ni ( H 2O )6 Mn ( H 2O )6 Sc ( H 2O )6 3+ 2+ 2+ + (B) Sc ( H 2O )6 Ni ( H 2O )6 Mn ( H 2O )6 Na ( H 2O )6 2+ 2+ 3+ + (C) Mn ( H 2O )6 Ni ( H 2O )6 Sc ( H 2O )6 Na ( H 2O )6 3+ + 2+ 2+ (D) Sc ( H 2O )6 Na ( H 2O )6 Ni ( H 2O )6 Mn ( H 2O )6 Kp 61. The Langmuir adsorption isotherm is given by = , where P is the pressure of the 1 + Kp adsorabate gas. The Langmuir adsorption isotherm for a diatomic gas A2 undergoing dissociative adsorption is: Kp 2Kp (A) = (B) = 1 + Kp 1 + 2Kp ( Kp ) ( Kp ) 2 1/2 (C) = (D) = 1 + ( Kp ) 1 + ( Kp ) 2 1/2 62. The standard electrode potentials (E0) of Fe3+/Fe2+ and Fe2+/Fe electrodes are +0.77V and 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 -0.44V respectively at 300 K. The Eo of Fe3+/Fe electrode at the same temperature is (A) 1.21 V (B) 0.33 V (C) -0.11V (D) -0.04 V 63. Which of the following is true for the radial part of the hydrogen atom wavefunctions R n ( r ) (n principal quantum number) and the nodes associated with them? (A) The radial part of only s function is non-zero at the origin and has (n – 1) nodes. (B) The radial part of s function is zero at the origin and has n number of nodes. (C) All radial functions have values of zero at the origin and have (n –1) nodes. (D) The radial parts of all s functions are zero at the origin and have no nodes. 64. For non-degenerate perturbation theory for ground state, with E (0) (1) 0 as zeroth order energy E 0 as the first-order perturbation correction and E0 as the exact energy, which of the following is true? (A) ( E (0) 0 + E 0 ) is always equal to E0 (1) (B) ( E (0) 0 + E0 ) E0 (1) (C) ( E (0) 0 + E0 ) E0 (1) 0 ( E0 + E0 ) (D) E (0) (0) (1) 65. Observe the following electronic transition of a diatomic molecule. (A) 1 g+ →3 g+ (B) 1 +u →1 g+ (C) 1 u →1 g+ (D) 1 g →1 g+ The allowed transitions are (A) (A) and (C) only (B) (B) and (D) only (C) (A), (B) and (C) only (D) (A), (C) and (D) only 66. An excited triplet state wave function of hydrogen molecule with the electronic configuration 1g 1u has the following space part (A) g (1) u ( 2 ) (B) g (1) u ( 2 ) + u (1) g ( 2 ) (C) g (1) u ( 2 ) − u (1) g ( 2 ) (D) g (1) g ( 2 ) + u (1) u ( 2 ) 67. The NMR spectrum of AX3 exhibits lines at = 2.1 and 2.3 ppm (for X type protons) and = 4.1, 4.3, 4.5 and 4.7 ppm (for A type protons), measured from TMS with an instrument operating at 100 MHz. The chemical shift (in ppm) of A and X protons and coupling constant (in (Hz) are respectively (A) 4.4, 2.2 and 20 (B) 2.2, 4.4 and 10 (C) 2.2, 4.4 and 5 (D) 4.3, 2.1 and 20 68. The character table of the C2v point group is given below: C2V E C2 V 'V A1 1 1 1 1 A2 1 1 –1 –1 B1 1 –1 1 –1 B2 1 –1 –1 1 The two functions 1 = p1 + 2p 2 + 2P3 + P4 and 2 = 2p1 − p 2 − P3 + 2P4 (where pk is the p- orbital on the kth atom of cis-butadiene and v is the molecular plane) belong to (A) A1 and A2 respectively (B) Both A2 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 (C) Both B2 (D) B1 and B2 respectively 69. If r denotes the characteristic temperature of rotation then the magnitude of r ( H2 ) r ( D2 ) / r ( HD ) (assume the bond lengths to be the same for all the molecules) is 2 (A) 2/3 (B) 3/2 (C) 8/9 (D) 9/8 70. The overall reaction for the passage of 1.0 faraday of charge in the following cell Ag ( s ) − AgCl ( s ) KCl ( a1 ) KCl ( a 2 ) AgCl ( s ) − Ag ( s ) is given by (t denotes the transport numbers) (A) t + KCl ( a1 ) → t + KCl ( a 2 ) (B) t + KCl ( a 2 ) → t + KCl ( a1 ) (C) t − KCl ( a1 ) → t − KCl ( a 2 ) (D) t − KCl ( a 2 ) → t − KCl ( a1 ) 71. A system consisting of 4 identical and distinguishable particle, each possessing three available states of 1,2 and 3 units, has 10 units of energy. The number of ways, W, in which these conditions are satisfied is (A) 2 (B) 4 (C) 6 (D) 10 72. The molar conductivities at infinite dilution 0m for Na2SO4, K2SO4, KCl, HCl and HCOONa at 300 K are 260, 308, 150, 426 and 105 S cm–1 mol–2 respectively. Hence 0m for formic acid in the same unit and at the same temperature is (A) 381 (B) 405 (C) 429 (D) 531 73. If the displacement vectors of all atoms in cis- butadiene are taken as the basis vectors the characters of the reducible representation of E, C2, v (molecular plane) and 'v are (A) 30, 10, 30, 0 (B) 30, 0, 10, 0 (C) 30, 20, 0, 0 (D) 30, 0, 20, 0 74. In least square fitting of a date set {XiYi} to the equation Y A.X = , the regression coefficient (A) is estimated by (A) Yi2 / Xi2 (B) Xi Yi / Xi2 (C) X Y / Y i i i 2 (D) X / Y 2 i i 2 75. At any temperature for the following reaction (D and T are deuterium and tritium respectively) correct statement is: (A) HCl + F → HF + Cl, (B) DCl + F → DF + Cl, (C) TCl + F → TF + Cl (A) (A) is fastest (B) (B) is fastest (C) (C) is fastest (D) All the above reactions have the same rate constant. 76. An example of a relaxation method of measuring rates is: (A) Spectroscopic monitoring of product concentration. (B) Stopped flow technique (C) Temperature jump experiments. (D) Measurement of spectral line widths. 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 77. The overall rate of the following complex reaction, K1 2A A2 (fast equilibrium) A+B K2 C (fast equilibrium) A2 + C ⎯⎯→ P + 2A k3 (slow) by steady state approximation would be (A) K1K2k3[A]3[B] (B) K2K1k3[A][B]3 2 (C) K1K2k3[A][B] (D) K1K2k3[A][B] 78. The vibrational energy levels, '' = 0 and ' = 1of a diatomic molecule are separated by 2143cm–1. Its anharmonicity ( e x e ) is 14 cm–1. The values of e ( in cm −1 ) and first overtone (cm–1) of this molecule are respectively. (A) 2143 and 4286 (B) 2157 and 4286 (C) 2157 and 4314 (D) 2171 and 4258 79. The addition polymerization of M (monomer) involves the following stages: (I = initiator, R = free radical) I ⎯⎯ k1 →R (initiation) R + M ⎯⎯ k2 → RM RM + M → RM 2 and so on RM n + M n R ⎯⎯ k3 → R − Mn − Mn ' − R The rate constant for free radical formation is 2 10−3 s −1. The initial concentration of initiator is 10–3 mol dm–3. The overall rate of the reaction is 4 10−3 mol dm −3s −1. Assuming steady state approximation for free radical, the kinetic chain length is: (A) 2000 (B) 8 109 (C) 20 (D) 200 80. The electronic spectrum of [CrF6]3– shows three bands at 14, 900 cm–1, 22400 cm–1 and 34,800 cm–1. The value of 0 in this case is: (A) 5,500 cm–1 (B) 14,900 cm–1 –1 (C) 22,400 cm (D) 34,800 cm–1 81. Among the following pairs, those in which both species have similar structures are: (B) ICl4 , PtCl4 (C) ClF2 , ICl 2 − 2− + − (A) N3− , XeF2 (D) XeO3, SO3 (A) (A) and (B) only (B) (A) and (C) only (C) (A), (B) and (C) only (D) (B), (C) and (D) only 82. The number of metal-metal bonds in the dimers, CpFe ( CO )( NO ) 2 and CpMo ( CO )3 2 respectively, are (A) two and two (B) two and three (C) one and two (D) zero and one 83. The reduction of nitrogen to ammonia, carried out by the enzyme nitrogenase, needs, (A) 2 electrons (B) 4 electrons (C) 6 electrons (D) 8 elecrons 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 84. In the titration of 50 mL of 0.1 M HCl with 0.1 M NaOH using methyl orange as an indicator, the end point (color change) occurs as pH reaches 4.0. The titration error is: (A) – 0.2% (B) – 84.7% (C) + 0.2% (D) + 84.2% 85. The styx code of B4H10 is: (A) 4120 (B) 4220 (C) 4012 (D) 3203 86. Match list I (compounds) with list II (structures), and select the correct answer using the codes given below. List-I List-II (A) XeO 4 (i) square planar (B) BrF4− (ii) tetrahedral (C) SeCl 4 (iii) distorted tetrahedral (A) (A–ii) (B–iii) (C–i) (B) (A–iii) (B–i) (C–ii) (C) (A–ii) (B–i) (C–iii) (D) (A–i) (B–ii) (C–iii) 87. In the trans-PtCl2L(CO) complex, the CO stretching frequency for L = NH3, pyridine, NMe3 decrease in the order. (A) pyridine > NH3 > NMe3 (B) NH3 > pyridine > NMe3 (C) NMe3 > NH3 > Pyridine (D) pyridine > NMe3 > NH3 88. For the nuclear reactions. (A) 84 Be ⎯⎯→ 224 He (B) 80 36 Kr ⎯⎯ → 218 40 Ar (Given masses: 8 Be = 8.005300, 4 He = 4.002603 and 80 36 Kr = 79.81638, 40 18 Ar = 39.96238 ) The correct statement is: (A) (A) and (B) are both spontaneous fission processes. (B) (A) is spontaneous fission but (B) is not. (C) (B) is spontaneous fission but (A) is not (D) Both (A) and (B) are not spontaneous fission processes. 89. A metal ion that replace manganese (II) ion in mangano-proteins without changing its function, is (A) Fe (II) (B) Zn (II) (C) Mg (II) (D) Cu (II) 90. In 57Fe* Mossbauer experiment, source of 14.4 keV (equivalent to 3.48 1012 MHz) is moved towards absorber at a velocity of 2.2 mm s–1. The shift in frequency of the source for this sample is: (A) 35.5 MHz (B) 25.5 MHz (C) 20.2 MHz (D) 15.5 MHz 91. Bayer’s process involves. (A) Synthesis of B2H6 from NaBH4 (B) Synthesis of NaBH4 from borax (C) Synthesis of NaBH4 from B2H6 (D) Synthesis of B3N3H6 from B2H6 2+ 92. A true statement about base hydrolysis of Co ( NH3 )5 Cl is (A) It is a first order reaction 2+ (B) The rate determining step involves the dissociation of chloride in Co ( NH3 )4 ( NH2 ) Cl . (C) The rate is independent of the concentration of the base 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 2+ (D) The rate determining step involves the abstraction of a proton from Co ( NH3 )5 Cl 93. The catalyst involved in carrying out the metathesis of 1-butene to give ethylene and 3-hexene is: (A) (B) Na2PdCl4 (C) Co2(CO)8,H2 (D) RhCl(PPh3)3 94. The correct order of d-orbital splitting in a trigonal bipyramidal geometry is: (A) d z2 d xz d x 2 − y2 ,d xy (B) d xz ,d yz d x 2 − y2 ,d xy d z2 (C) d x 2 − y2 , d xy d z2 , d xy , d yz (D) d z2 d x 2 − y2 d xy d xz , d yz 95. For the following outer sphere electron transfer reactions. 2+ 3+ 3+ 2+ Co ( NH3 )6 + Co* ( NH3 )6 → Co ( NH3 )6 + Co* ( NH3 )6 2+ 3+ 3+ 2+ Ru ( NH3 )6 + Ru * ( NH3 )6 → Ru ( NH3 )6 + Ru * ( NH3 )6 the rate constants are 10–6 M–1 s–1 and 8.2 102 M −1s −2 respectively. This difference in the rate constants is due to (A) A change from high spin to low spin in Co* and high spin to low spin in Ru. (B) A change from high spin to low spin in Co* and low spin to high spin Ru*. (C) A change from low spin to high spin in Co* and the low spin state remains unchanged in Ru. (D) A change from low spin to high spin in Co* and high spin to low spin in Ru*. 96. The greater stability of ( ( CH ) 3 3 C − CH 2 − ) Ti ( A ) compared to that of 4 ( ( CH )3 2 CH − CH 2 − ) Ti ( B ) is due to 4 (A) Hyperconjugation present in complex (A) (B) − hydride elimination is not possible in complex (A) (C) Steric protection of titanium from reactive species in complex (A) (D) The stronger nature of Ti–C bond in complex (A). 2− 97. The coordination number and geometry of cerium in Ce ( NO3 )6 are respectively, (A) 6 and octahedron (B) 6 and trigonal prism (C) 8 and cubic (D) 12 and icosahedron 98. A compound A having the composition FeC9H8O3 shows one signal at 2.5 ppm and another one around 5.0 ppm in its 1H NMR spectrum The IR spectrum of this compound shows two bands around and 1680 cm–1. The compound follows the 18-electron rule of the following statements for A, the correct one is/are (A) It has 5−Cp group. (B) It has a terminal CO ligand. (C) It has a CH3 ligand (D) It has Fe–H bond. (A) (A) and (B) only (B) (C) only (C) (A) and (C) only (D) (B) and (D) only. 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 99. In bacterial rubredoxin, the number of iron atoms, sulfur bridges and cysteine ligands are Fe atom sulfer bridge cysteine (A) 4 4 4 (B) 2 2 4 (C) 2 2 2 (D) 1 0 4 100. In the following reaction, the product formed and the mechanism involved are (A) A is and is formed by addition-elimination mechanism. (B) A is and is formed by benzyne mechanism. (C) A is and is formed by benzyne mechanism. (D) A is and is formed by SN2 displacement. 101. An optically active compound enriched with R-enantiomer (60% ee) exhibited D + 90o. If the D value of the sample is –135º, the ratio of R and S enantiomers would be (A) R:S = 1:19 (B) R:S = 19:1 (C) R:S = 1:9 (D) R:S = 9:1 102. Match the amino acids with their structures: (i) (A) tryptophan (ii) (B) histidine 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 (iii) (C) asparagine (D) serine (E) glutamic acid (A) (i)-A (ii)-E (iii)-(C) (B) (i)-(C) (ii)-(D) (iii)-(B) (C) (i)-(A) (ii)-(B) (iii)-(D) (D) (i)-(C) (ii)-(A) (iii)-(B) 103. Statement I. U(VI) is more stable than Nd(VI). Statement II. The valence electrons in U are in 5f, 6d and 7s orbitals. (A) Statements I and II are correct and Statement II is correct explanation of I. (B) Statements I and II are correct but Statement II is not an explanation for Statement I. (C) Statements I is correct and Statement II is incorrect. (D) Statements I and II both are incorrect. 104. The major products A and B in the following reaction sequence are (A) A = B= (B) A = B= (C) A = B= (D) A = B= 105. The major products A and B in the following reaction sequence are (A) 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 (B) (C) (D) 106. An organic compound having molecular formula C15H14O exhibited the following 1H and 13 C NMR spectral data. 1 H NMR : 2.4(s). 7.2(d, J = 8 Hz), 7.7 (d, J = 8Hz) 13 C NMR : 21.0, 129.0, 130.0, 136.0, 141.0, 190.0, (A) (B) (C) (D) 107. Identify appropriate reagents A and B in the following reactions. (A) A = LiAlH4 B = BH3.Me2S (B) A = BH3.Me2S B = LiAlH4 (C) A = LiBH4 B = BH3.Me2S (D) A = BH3.Me2S B = LiBH4 108. The correct sequence of the reagents to be employed in the following transformation is: (A) (A) m – CPBA; (B) TsNHNH2; (C) AcOH; (D) H2,Pd/BaSO4 (B) (A) H2O2, NaOH; (B) TsNH2NH2; (C) AcOH; (D) H2,Pd/C (C) (A) m – CPBA; (B) TsNHNH2; (C) NaOH; (D) H2, Pd/C (D) (A) H2O2, NaOH; (B) TsNHNH2; (C) AcOH; (D) H2, Lindlar’s catalyst 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 109. Reaction of 11.6 g of the aldehyde A with 462 mg of Wilkinson’s catalyst provided 9.2g of alkene B. The mol % of the catalyst used and the yield of the reaction, approximately are (A) 1.0 mol%; and 80% (B) 1.0 mol %; and 90% (C) 0.1 mol%; and 90% (D) 0.2 mol %; and 80% 110. The major products A and B in the following reaction sequence are (A) (B) (C) (D) 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 111. The major products A and B in the following reaction sequence are (A) (B) (C) (D) 112. The major products A and B in the following reaction sequence are (A) (B) (C) 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 (D) 113. Appropriate 1H NMR chemical shifts () for the protons A-D for the following compound are (A) A– 6.8; B –5.7; C–3.9; D –2.1ppm (B) A– 6.8; B–5.7; C–2.1; D –3.9 ppm (C) A–5.7; B–6.8; C–3.9; D –2.1 ppm (D) A– 5.7; B – 6.8; C–2.1; D –3.9 ppm 114. The major product formed in the following reaction sequence is: (A) (B) (C) (D) 115. Citronellol A on oxidation with pyridinium chlorochromate (PCC) followed by treatment with aq. sodium hydroxide gives the product B (IR : 1680 cm–1); whereas oxidation with PCC in the presence of sodium acetate gives product C (IR: 1720 cm–1). Compound B and C are 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 (A) (B) (C) (D) 116. Match the following starting compounds with corresponding products in photochemical reactions: (i) (A) (ii) (B) (ii) (C) (D) (E) 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 (A) (i) – (E) (ii)–(A) (iii)–(B) (B) (i)–(A) (ii)–(C) (iii)–(b) (C) (i)–(D) (ii)–(C) (iii)–(A) (D) (i)–(E) (ii)–(A) (iii)–(D) 117. The major products A and B in the following reaction sequence are (A) (B) (C) (D) 118. The major products A and B of the following reaction sequence are 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 (A) (B) (C) (D) 119. The major products A and B in the following reaction sequence are (A) (B) 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 (C) (D) 120. The major products A and B in the following reaction sequence are (A) (B) (C) 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 (D) 121. The correct reagents for effecting the following reactions are (A) (B) (C) (D) 122. The major product A and B of the following reaction sequence are 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 (A) (B) (C) (D) 123. The major products A and B in the following synthetic sequence are (A) (B) 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 (C) (D) 124. The major products A and B in the following synthetic strategy are (A) (B) (C) (D) 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET DECEMBER 2011 125. The product formed and the process involved in the following reaction are (A) [3,3]-sigmatropic rearrangement (B) [1,3]-sigmatropic rearrangement (C) [5,5]-sigmatropic rearrangement (D) [1,5]-sigmatropic rearrangement 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2012 1. In the reaction (A) and (B), − → Cl ( H 2O )n nH 2 O + Cl − ⎯⎯...(A) 2+ 6H 2 O + Mg 2+ ⎯⎯→ Mg ( H 2O )6 ...(B) water behaves as (A) An acid in both (A) and (B) (B) An acid in (A) and a base in (B) (C) A base in (A) an acid in (B) (D) A base in both (A) and (B) 2. The size of the d orbitals in Si, P, S and Cl follows the order. (A) Cl > S > P > Si (B) Cl > P > S > Si (C) P > S > Si > Cl ` (D) Si > P > S > Cl 3. The correct structure of basic beryllium nitrate is: (A) (B) (C) (D) 4. The total number of lone pairs of electrons in I3− is: (A) Zero (B) Three (C) Six (D) Nine 5. If Mössbauer spectrum of Fe(CO)5 is recorded in the presence of a magnetic field, the original spectrum with two lines changes into the one with (A) Three lines (B) Four lines (C) Five lines (D) Six lines 6. The spectrophotometric response for the titration of a mixture of Fe3+ and Cu2+ ions against EDTA is given below. c d Mixture a b Volume of EDTA 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2012 The correct statement is: (A) Volume ab = Fe3+ and volume cd = Cu 2+ (B) Volume ab = Cu 2+ and volume cd = Fe3+ (C) Volume ab = Fe3+ and volume ab = excess EDTA (D) Volume ab Cu 2+ and volume cd = excess EDTA 7. In ‘carbon-dating’ application of radioisotopes, 14C emits (A) − particle (B) − particle (C) − radiation (D) Positron. 8. The actual base pairs present in the double helical structure of DNA containing adenine (A), thymine (T), cytosine (C) and guanine (G), are (A) AG and CT (B) AC and GT (C) AG and AC (D) AT and GC 9. The oxidation state of iron in met-haemoglobin is (A) Three (B) Two (C) Four (D) Zero 10. The reactions of |Ni(CO)4 with the ligand (L = PMe3 or P (OMe)3)L yields Ni(CO)3L. The reaction is (A) Associative (B) Dissociative (C) Interchange (Ia) (D) Interchange (Id) 11. As a ligand Cl– is: (A) Only a −donor (B) Only a −donor (C) Both a −donor and a − donor (D) A −donor and a − acceptor 12. The correct d-electron configuration showing spin-orbit coupling is 4 2 6 0 4 0 3 2 (A) t 2g eg (B) t 2g eg (C) t 2g eg (D) t 2g eg 13. The correct statement for the aggregating nature of alkyl lithium (RLi) reagent is: (A) The carbanion nucleophilicity increases with aggregation. (B) The observed aggregation arises from its electron deficient nature. (C) Carbanion nucleophilicity does not depend on aggregation. (D) The extent of aggregation is maximum in polar dative solvents. 14. For the reaction, trans- IrCl ( CO )( PPh 3 )2 + Cl2 → trans − IrCl3 ( CO )( Phh 3 )2 , the correct observation (A) vCO ( p r oduct ) vCO ( reac tan t ) (B) vCO ( p r oduct ) vCO ( reac tan t ) (C) vCO ( p r oduct ) = vCO ( reac tan t ) (D) vCO ( p r oduct ) = vCO ( freeCo ) 15. The nucleophilic attack on olefins under mild conditions: (A) Is always facile (B) Is more facile than electrophilic attack on olefins (C) Is facile for electron-rich olefins (D) Requires activation by coordination to metal. 28 B-7/1, ASAP CHEMTIME, Jia Sarai, Near IIT Delhi, New Delhi – 110016 Website: www.chemtime.co.in, Email: [email protected] Ph. No. 9971494539, 8595764714 CSIR-NET JUNE 2012 16. Among the following the strongest oxidizing agent is: (A) [WO4]2– (B) [CrO4]2– (C) [MoO4]2– (D) [ReO4]2– 17. The least basic among the following is: (A) Al(OH)3 (B) La(OH)3 (C) Ce(OH)3 (D) Lu(OH)3 18. For any operator A and its abjoint A†,the INCORRECT statement is: (A) AA† is Hermitian (B) AA† + A†A + is Hermitian (C) A+A† is Hermitian (D) A−A† is Hermitian. 19. For hydrogen-like atom with a nucl
