21. The correct order of acceptor ability of the phosporus ligands is

(a)

(b)

(c)

(d)

Ans. b

Sol. As the electronegativity of X in PX₃ increases, π-acceptor tendency increases,

PF₃ > P(OPh)₃ > PPh₃ > PMe₃

Correct option is (b)

22. In the ³¹P{¹H} NMR spectrum of a diamagnetic complex mer-[M(PR₃)₃Cl₃] (M = transition metal, I = 0) expected number of resonance(s) is

(a) Three

(b) One

(c) Two

(d) Six

Ans. c

Sol.

Correct answer is (c)

23. Consider the species NO, I₂, I^–₂, Cu²⁺ and VO²⁺. The number of paramagnetic species among them and the EPR inactive species, respectively, are

(a)

(b) 4 and I₂

(c) 3 and VO²⁺

(d) 3 and NO, Cu²⁺

Ans. b

Sol. is paramagnetic. Hence, EPR active where as I₂ is diamagnetic and EPR inactive.

Correct answer is (b)

24. Identify the correct statement(s) for H₃B.CO.

(A) sp² hybridized orbital of B accepts the lone pair of CO.

(B) Its v_CO value is more than that for free CO

(C) Formal oxidation state of C is +4 in the compound

Answer is

(a) A and B

(b) B only

(c) A only

(d) A and C

Ans. b

Sol.

In BH₃.CO formation CO interact with vaccant p-orbital, where as electron is donated by antibonding orbital of CO due to which bond order increases and v_CO increases.

Correct option is (b)

25. Match the items of Column-I with those of Column-II

Column-I Column-II

(A) Laser source (I) Electron Capture Detector

(B) Thermometric titration (II) Polarography

(C) Gelatin (III) Heat of reaction

(D) Gas-liquid chromatography (IV) Spectrofluorimetry

Correct Answer is

(a) A-IV, B-III, C-II, D-I

(b) A-I, B-III, C-II, D-IV

(c) A-IV, B-II, C-III, D-I

(d) A-III, B-II, C-IV, D-I

Ans. a

Sol. Thermometric titration is the method in which a titrant is added stepwise to a vessel containing another reactant. The enthalpy change on heat of reaction causes a temperature change which when plotted versus volume of titrant is used to detect the end point.

(i) Electron capture detector is a device for detecting atoms and molecules in a gas and is used in atoms and molecules in a gas and is used in Gas-liquid chromatography.

(ii) The abnormal peak which appears in polographic titration can be supposed by addition of Gelatin.

(iii) In spectrofluorimetry laser may used as source.

Correct answer is (a)

26. Consider compounds PF₅, SbF₅, PH₃ and SbH₃. The strongest acid and the strongest base among these are, respectively.

(a) PF₅ and PH₃

(b) SbF₅ and PH₃

(c) SbF₃ and SbH₃

(d) PF₃ and SbH₃

Ans. b

Sol. SbF₅ is strongest acid and PH₃ is strongest base.

Correct answer is (b)

27. Among SiCl₄, P(O)Cl₃, NF₃, trans-[SnCl₄(py)₂] (py = pyridine), those with zero dipole moment are

(a) SiCl₄ and NF₃

(b) SiCl₄, P(O)Cl₃ and trans-SnCl₄(py)₂

(c) SiCl₄ nad trans-SnCl₄(py)₂

(d) NF₃ and trans-SnCl₄(py)₂

Ans. c

Sol.

28. The standard reduction potentials in acid medium for F₂, Cl₂, Na and Zn are in the order

(a)

(b)

(c)

(d)

Ans. b

Sol. The standard reduction potential in acid follow the order

F₂ > Cl₂ > Zn > Na

Correct answer is (b)

29. The characters of LUMO and CN^– and O₂ respectively, are

(a)

(b)

(c)

(d)

Ans. c

Sol. According to MOT the LUMO of CN^– and O₂ respectively are

Correct answer is (c)

30. The intermediate is decided in the reaction of with in aqueous medium to produce

The mechanism of the reaction is

(a) Interchange dissociateve

(b) Interchange associative

(c) Inner sphere electron transfer

(d) Outer sphere electron transfer

Ans. c

Sol.

31. The chelate rings made by macrocyclic ligand in vitamin B₁₂ are

(a) One five-membered and three six-membered

(b) Two five-membered and two six-membered

(c) Three five-membered and one six-membered

(d) Four six-membered

Ans. a

Sol.

Correct answer is (a)

32. For magnesium complex of EDTA^2–, the number of N-donor and O-donor centers, are respectively

(a) Two and four

(b) two and two

(c) two and six

(d) two and eight

Ans. a

Sol.

Correct answer is (a)

33. The correct set of electronic configurations for metal ions in octahedral coordination geometry for strong Jahn-Teller distrotion is

(a)

(b)

(c)

(d)

Ans. a

Sol. For strong Jahn-Teller distortion e_g orbital must be assymetrical filled.

Correct answer is (a)

34. The order of relative rate of cyclization of following bromocarboxylates to generate corresponding lactones is

(a) B > A > C

(b) A > C > B

(c) B > C > A

(d) C > B > A

Ans. c

Sol. The rate of cyclization is a function of ring size and the relative order is 5 > 6 > 4

Thus, order of lactonization will be B > C > A

Correct option is (c)

35. Oxidation of A with HNO₃/H₂O provides the product(s) which is (are)

(a) Optically inactive as it is recemic mixture

(b) Optically inactive as it is meso

(c) Optically active as it is a single diastereomer

(d) Optically active as it s a single enantiomer

Ans. b

Sol.

Correct answer is (b)

36. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. d

Sol.

Nucleophilic attack is more facile at 2-and 4-position of pyridine ring. Here, Cl-atom is present at 2-position as leaving group.

Correct answer is (d)

37. The order of reactivity of the following dienes towards Diels-alder reaction is –

(a) B > A > C

(b) A > C > B

(c) B > C > A

(d) C > B > A

Ans. a

Sol. The diene must be capable of achieveing s-cis conformation for the Diels-Addler reaction.

Correct answer is (a)

38. Among the following, the optically active compound is

(a)

(b)

(c)

(d)

Ans. d

Sol.

Correct answer is (d)

39. Among the following reaction(s) which provide(s) 1-butanes as the major product is (are)

(a) A alone

(b) A and B

(c) A and C

(d) C and D

Ans. c

Sol. A and C gives 1-butene, B and D gives 2-butene.

Correct answer is (c)

40. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. a

Sol. Alkaline hydrolysis of trichloro alkane gives corresponding carboxylic acid

Correct answer is (a)

41. Among the following, the compound that will have highest rate for nucleophilic substitution through S_N1 mechanism is

(a)

(b)

(c)

(d)

Ans. d

Sol.

Correct answer is (d)

42. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. b

Sol. Mixed anhydride as acylating agent

Correct answer is (b)

43. The mechanism of acid catalyzed hydrolysis of benzonitrile involes

(a)

(b)

(c)

(d)

Ans. b

Sol.

Correct answer is (b)

44. In the energy profile diagram of the reaction given below, the species A would correspond to the position.

(a) I

(b) II

(c) III

(d) IV

Ans. b

Sol.

Correct answer is (b)

45. Following reaction is an example of

(a) Alder-Ene reaction

(b) Michael addition

(c) Sigmatropic Rearrangement

(d) Wagner-Meerwein Rearrangement

Ans. a

Sol.

Presence of Lewis acid Mg(ClO₄)₂ makes the reaction more favourable.

Correct option is (a)

46. In IR spectra, the stretching frequency (in cm^–1) of the carbonyl group of the following compound is in the order

(a) B > A > C

(b) A > C > B

(c) B > C > A

(d) C > B > A

Ans. c

Sol.

Correct order is B > C > A

Correct option is (c)

47. The uncertainty in the position of a moving electron is 100 pm. The uncertainty in its speed is closest to (m_e = 9.11×10^–31 kg; h = 6.63×10^–34 J.s)

(a)

(b)

(c)

(d)

Ans. b

Sol. Accroding to Heisenberg's uncertainty principle,

Correct answer is (b)

48. The spectrum of sodium atom has a closely separated dublet at 16956.2 and 16973.4 cm^–1. The higher energy transition is due to

(a)

(b)

(c)

(d)

Ans. a

Sol. The correct involed in the transition are 3s and 3p. The erergy of 3s is lower than that of 3p. The 3p orbital energy level gets split into two further energy level i.e. 3p^1/2 and 3p^3/2, out of which 3p^3/2 is of higher than 3p^1/2. Therefore, in emission spectrum the large value of transition should be because of transition between 3p^3/2 – 3s^1/2. (We have used before orbital because we are denoting the orbital which is involed in transition. In question instead of 3p^3/2 they have written 3p^3/2 – 2s^t/2. They are mentioning spin multiplicity rather than orbital).

Correct answer is (a)

49. N₂O molecule belongs to the point group

(a)

(b)

(c)

(d)

Ans. b

Sol.

Correct answer is (b)

50. For a closed system in the absence of non-PV work, the correct statement is

(a) dU = TdS – PdV

(b) dG = VdP + SdT

(c) dU = TdS + PdV

(d) dU = VdP – SdT

Ans. a

Sol. For the closed system the correct statement is dU = TdS – PdV (Maxwell equation)

Correct answer is (a)

51. The volume change in a certain phase transition is 2.0 mL mol^–1 at the transition point. From this, we may conclude that the transition is most likely to

(a) first order phase transition

(b) second order phase transition

(c) third order phase transition

(d) phase transition

Ans. a

Sol. Condition of first order phase transition is

Correct answer is (a)

52. Root mean square speed of the molecules of a perfect gas is proportional to

(a) 1/T^1/2

(b) T

(c) T^1/2

(d) 1/T

Ans. c

Sol.

Correct answer is (c)

53. For a second-order reaction, the straight line among the following plots is

(a) [X] versus time

(b) 1/[X] versus time

(c) log[X] versus 1/time

(d) log[X] versus time

Ans. b

Sol. For second order reaction

Correct answer is (b)

54. The activation energy of a reaction reduces by 12 kcal mol^–1 in the presence of an enzyme at 300 K. Assuming pseudo-first order kinetics, calculate the factor by which the reaction rate is increased. [Given: R = 2 cal K^–1mol^–1]

(a) 2 × 10^–9

(b) 1.02

(c) 8.7 × 10⁶

(d) 5 × 10⁸

Ans. d

Sol. (where un = uncatalysed reaction, c = catalysed reaction)

Correct answer is (d)

55. The correct statement among the following is

(a) Salt bridge is required for the mixing of the solution in the two half cells.

(b) Salt bridge allows current to flow between the half cells without mixing the solutions

(c) Salt bridge enhances the rate of the reaction

(d) Salt bridge consists of a non-electrolyte in a gel.

Ans. b

Sol. Correct Statement: Salt bridge allows current to flow between the half cells with out mixing the solution.

Correct answer is (b)

56. The standard free energy of the reaction

(a) 7 kJ mol^–1

(b) 70 J mol^–1

(c) 70 kJ mol^–1

(d) 7 J mol^–1

Ans. c

Sol. The given cel, can written as

Correct answer is (c)

57. The internal pressure of a liquid drop (radius = 10^–6 m) is greater than the external pressure by 1.5 × 10⁵ Nm^–2. The surface tension (mN m^–1) of the liquid is closest to

(a) 150

(b) 125

(c) 100

(d) 75

Ans. d

Sol.

Correct answer is (d)

58. In a cubic crystal, the (1 1 1) and (222) reflections are observed, but not the (001) reflection. The Bravais lattice is

(a) body centred cubic

(b) face centred cubic

(c) simple cubic

(d) side centred cubic

Ans. b

Sol.

Correct answer is (b)

59. The dispersity of a polymeric sample is

(a)

(b)

(c)

(d)

Ans. a

Sol. The polydispersity can be expressed in terms of the normalised standard deviation.

Therefore, polydispersity

Correct answer is (a)

60. The keto-hexose among the following is

(a) Xylose

(b) Galactose

(c) Fructose

(d) Mannose

Ans. c

Sol.

Among given compound fructose is the only one which contains a ketone functional group and having six carbon stom, thus ketohexose.

Correct answer is (c)

61. The product for the reaction given below is

(a)

(b)

(c)

(d)

Ans. b

Sol.

Correct answer is (b)

62. The ¹³P {¹H} NMR spectrum of cis-[Pt(PEt₃)₂Cl₂] (¹⁹⁵Pt(33.8% abundance) I = ½ its other isotopes are NMR inactive; ³¹P : I = ½) is comprised with satellite peaks of a

(a) triplet

(b) singlet

(c) doublet

(d) quartlet

Ans. b

Sol.

Overall the ³¹P NMR signal will be singlet signal with 33.8% doublet satellite as given below.

The ³¹P {¹H} NMR spectrum is comperised with satellite peak of a singlet signal.

Correct answer is (b)

63. The correct order of intensity of the d-d transitions in the complexes of a 3d-transition metal ion M²⁺ is

(a) cis–[M(H₂O)₄Cl₂] > trans – [M(H₂O)₄Cl₂] > [M(H₂O)₆]²⁺

(b) [M(H₂O)₆]²⁺ > cis – [M(H₂O)₄Cl₂] > trans – [M(H₂O)₄Cl₂]

(c) trans – [M(H₂O)₄Cl₂] > cis – [M(H₂O)₄Cl₂] > [M(H₂O)₆]²⁺

(d) [M(H₂O)₆]²⁺ > cis – [M(H₂O)₄Cl₂] ≈ trans – [M(H₂O)₄Cl₂]

Ans. a

Sol. The correct order or intensity of d-d transitions in the complexes follows order

Correct answer is (a)

64. The reaction of decaborane B₁₀H₁₄ with acetylene in the presence of Et₂S gives

(a) C₂B₁₀H₁₂

(b) C₂B₈H₁₀

(c) C₂B₁₀H₁₄

(d) C₂B₉H₁₁

Ans. a

Sol.

Correct answer is (a)

65. In compound N₃P₃F₆, the geometry around nitrogen and phosphorus, respectively are

(a) pyramidal and tetrahedral

(b) planar and tetrahedral

(c) pyramidal and planar

(d) planar and trigonal bipyramidal

Ans. b

Sol.

Correct answer is (b)

66. The number of 2c-2e bonds ('x') of a molecule is related to 'N' (valence electrons) and 'n' (skeletal atoms) by x = (8n – N)/2. For P₄S₃, the values of x, N and n, respectively, are

(a) 7, 38, 9

(b) 7, 24, 9

(c) 9, 38, 7

(d) 9, 24, 7

Ans. c

Sol.

Valence electron (N)

Correct answer is (c)

67. Match the following complxes with their ν_CO stretching frequency

The correct match is

(a) A-I, B-IV, C-II, D-III

(b) A-III, B-II, C-I, D-IV

(c) A-IV, B-III, C-I, D-II

(d) A-I, B-II, C-III, D-IV

Ans. b

Sol. Complex:

tendency of spectator ligand is Therefore, PF₃ reduce more electron density from the metal in complex to pyridine consequently. As the electron density on metal decreases, M–C bond strength decreases, C–O bond strength increases. Hence, v_CO increases.

Correct answer is (b)

68. The and [Fe(CN)₆]^4– (B) and (C) and [Cr(CO)₆] (D) are compared below. The pair with correct order is

(a) A > B; C > D

(b) A > B; C < D

(c) A < B; C > D

(d) A < B; C < D

Ans. b

Sol.

Correct answer is (b)

69. Consider the following statements for [FeO₄]^2–

(A) It is stable in the pH range 0–14

(B) It is stable in strongly basic medium only

(C) It is a very strong oxidizing agent

(D) The isomer shift in its Mossbauer spectrum is more negative compared to that of FeCl₃.

The correct statements are

(a) A, C and D

(b) B, C and D

(c) B and C

(d) C and D

Ans. b

Sol.

• It is stable in strongly basic medium

• Power oxdizing agent

• The isomer shift of its Mossbauer spectrum is more negative compared to that of FeCl₃.

Correct answer is (d)

70.

The isomers A and B undergo base hydrolysis by forming a trigonal bipyramidal intermediate. The correct statement is

(a) A reacts faster than B and both results in a mixture of products

(b) B reacts faster than A and both results in a mixture of products

(c) A reacts faster than B and B results in a mixture of products

(d) B reacts faster than A and A results in a mixture of products.

Ans. c

Sol.

A react faster than B and B resuslt in a mixture of product.

Correct option is (c)

71. B₂H₆ reacts with

(A) water to give boric acid and H₂O₂ (B) oxygen to give B₂O₃ and H₂

(C) water to give boric acid and H₂O (D) oxygen to give B₂O₃ and H₂O

Correct statements from the above are

(a) A and B

(b) A and D

(c) B and C

(d) B and D

Ans. d

Sol.

Correct answer is (d)

72. The ligand that binds strongly to the nickel center in (2, 2'-bipyridine) Ni(0) complex is

(a)

(b)

(c)

(d)

Ans. a

Sol. The ligand which have strong electron withdrawing group have strong tendency. So, binds strongly

Correct option is (a)

73. Match the items given in Column-I with those given in Column-II

Column-I Column-II

(A) Magic number (I) Nuclear fission

(B) Liquid drop model of nucleus (II) Q-value

(C) Actinides (III) Radioactivity

(D) Threshold energy (IV) Shell model of nucleus

The correct match is

(a) A-IV, B-I, C-III, D-II

(b) A-II, B-I, C-III, D-IV

(c) A-III, B-IV, C-I, D-II

(d) A-IV, B-III, C-I, D-II

Ans. a

Sol. Magic number shell model of nucleus

Liquid drop model of nucleus nuclear fission

Actinides radioactivity

Correct answer is (a)

74. The cluster type and geometry of the species [Rh₉P(CO)₂₁]^2– are

(a) closo, tricapped trigonal prism

(b) arachno, trigonal prism

(c) nido, capped square antiprism

(d) nido, bicapped, trigonal prism

Ans.

Sol.

75. Hydroformylation of 1-propene with [HRh(CO)L₂] leads to linear and branched formylated products. The linear hydroformylated product is formed with highest selectivity when 'L' in the rhodium complex is

(a)

(b)

(c)

(d)

Ans. c

Sol.

The linear and branches formylated product is depends upon natural bite angle of biphosphines. As the natural bite angle increases selectivity for linear product increases.

Correct option is (c)

76. The hydrocarbon having an analogous structures to that of P₄O₆ is

(a)

(b)

(c)

(d)

Ans. a

Sol.

77. Match the items given below in the three columns:

Correct matches:

(a) A-III-Z, B-I-Y, C-II-X

(b) A-II-Y, B-I-X, C-III-Z

(c) A-III-Y, B-I-Z, C-II-X

(d) A-I-X, B-II-Y, C-III-Z

Ans. a

Sol.

78. A solid sample of Na[Fe(EDTA)(H₂O)_s] (X) showed 5.6% weight loss at 120ºC in a thermogravimetric experiment. Identify the complex left after this weight loss.

(a) Na[FE(EDTA)(H₂O)]

(b) Na[Fe(EDTA)]

(c) Na[Fe(EDTA)(H₂O)₂]

(d) Na[Fe(EDTA)(H₂O)₃]

Ans. b

Sol. n can either be 1 or 2

Molecular mass of the complex (when n = 1)

22.98 + 55.845 + 292.24 + 18.01 = 389.075 g/mol

Molecular mass after 9.6% weight loss = 367.295 which is molecular

79. Consider the two sets of molecules.

The slowest ligand exchange rate in Set A and Set B are, respectively

(a)

(b)

(c)

(d)

Ans. b

Sol. As the oxidation state increases and size of central decreases ligand exchange rate decreases.

Correct answer is (b)

80. Consider following statements for Eu³⁺

(A) The positions of sharp bands in UV-vis spectra of its complexes depend heavily on the ligand environment

(B) Its ground state term symbol is ⁷F₀

(C) The observed magnetic moment is due to populated higher J level

(D) At 2 K its magnetic moment approaches to zero

The set of correct statements is

(a) A, C and D

(b) B, C and D

(c) A, B and D

(d) A, B and C

Ans. b

Sol.

Hecnce, ⁷F₀

Since, J = 0 hence should be zero but due to population of higher J level But as temperature decreases population is excited J level decreases hence magnetic moment approaches to calculated value i.e. zero.

Correct option is (b)

81. The major product formed in th following reaction is

(a)

(b)

(c)

(d)

Ans. a

Sol.

Correct answer is (a)

82. Structure of the compound displaying following characteristics spectral data

IR : 1720 cm^–1

¹H NMR : 6.2(br s, 1H), 5.5(br, s, 1H), 4.2(q, 2H), 2.0(s, 3H), 1.1(t, 3H) is

(a)

(b)

(c)

(d)

Ans. b

Sol. IR value at 1720 cm^–1 indicates the

Correct answer is (b)

83. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans.

Sol. Kulnkovich Reaction (Cyclopropanation):

Correct answer is (a)

84. The intermediate(s) involved in the following reaction is(are)

(a) Only I

(b) Only II

(c) I and II only

(d) I and III only

Ans. c

Sol. Aqueous Ag₂O gives OH^– ions and Ag⁺ ions reaction mixture

Correct answer is (c)

85. Correct sequence of reagents to be used for the following conversion is

(a) (I) NaH, 1-fluoronaphthalene; (II) NaBH₄; (III) (i) (CH₂O)_n, Me₂NH.HCl; (ii) 5 N NaOH

(b) (I) NaBH₄; (II) NaH, 1-fluoronaphthalene; (III) (i) (CH₂O)_n, Me₂NH.HCl (ii) 5 N NaOH

(c) (I) (i) (CH₂O)_n, Me₂NH.HCl; (ii) 5N NaOH; (II) NaBH₄; (III) NaH, 1-fluoronaphthalene

(d) (I) (i) (CH₂O)_n, Me₂NH.HCl; (ii) 5N NaOH; (II) NaH, 1-fluoronaphthalene; (III) NaBH₄.

Ans. c

Sol.

Correct answer is (c)

86. The major products (A) and (B) formed in the following reactions are

(a)

(b)

(c)

(d)

Ans. a

Sol. Presence of Lewis acid favoured the Michael 1, 4-addition reaction in enones.

Correct answer is (a)

87. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. a

Sol.

Correct answer is (a)

88. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. d

Sol.

Correct answer is (d)

89. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. d

Sol.

Correct answer is (d)

90. The major product formed in the following photochemical reaction is

(a)

(b)

(c)

(d)

Ans. c

Sol. Correct answer is (c)

91. Correct sequence of reagents to be used for the following conversion is

(a) (I) LDA, EtBr; (II) EtLi; (III) H₃O⁺

(b) (I) EtLi, (II) LDA, EtBr; (III) H₃O⁺

(c) (I) H₃O⁺; (II) EtLi; (III) LDA, EtBr

(d) (I) EtLi; (II) H₃O⁺; (III) LDA, EtBr

Ans. a

Sol.

Correct answer is (a)

92. Both, 1-chloro-1-phenylpropan-2-one and 1-chloro-3-phenylpropan-2-one give sam product (A) when heated in presence of NaOMe. The product (A) is

(a) methyl 3-phenylpropanoate

(b) methyl 2-phenylpropanoate

(c) methyl 2-methoxy-2-phenylacetate

(d) 1-methoxy-3-phenylpropan-2-one

Ans. a

Sol.

Correct answer is (a)

93. The major product formed in the following reaction sequence is

(a)

(b)

(c)

(d)

Ans. c

Sol.

Hydrolysis in presence of Cu(II), salt helps to remove

Correct answer is (c)

94. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. c

Sol.

Correct answer is (c)

95. The structures of products (A) and (B) formed in the Edman degradation of the dipeptide are

(a)

(b)

(c)

(d)

Ans. d

Sol. Edman degradation method is used for N-terminal analysis of protein (Polypeptide). Since, this method can label and cleave the peptide from N-terminal and forms corresponding phenylthiohydonation derivative of amino acid.

Correct answer is (d)

96. Partial spectroscopic data is given below for an organic compound

(I) 4 signals between ppm in ¹³C NMR spectrum

(II) 2 doublets betwen ppm in ¹H NMR spectrum

(III) an absorption band at 1724 cm^–1 in IR spectrum

The structure of the compound is

(a)

(b)

(c)

(d)

Ans. b

Sol. IR absorption at 1724 cm^–1 indicates the conjugated ester.

¹³C NMR and ¹H NMR data shows the 1, 4-disubstitution.

IR = 1724 cm^–1 due to resonance effect of aromatic ring.

Correct answer is (b)

97. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. d

Sol. Pummerer Rearrangement:

Correct answer is (d)

98. The major products (A) and (B) in the following reaction sequence are

(a)

(b)

(c)

(d)

Ans. b

Sol. Payne rearrangement after asymetric epoxidation:

Correct answer is (b)

99. The compound P undergoes a pericyclic reaction under photochemical conditions to give compound Q. In compound Q, the relative stereochemistry and ¹H NMR chemical shift values of methyl groups respectively, are

(a) cis; –5

(b) trans; 17

(c) cis; 17

(d) trans; –5

Ans. d

Sol.

Correct answer is (d)

100. The major products A and B in the following raction sequence are

(a)

(b)

(c)

(d)

Ans. d

Sol.

Carbon (a) migrates, not carbon (b) because of two electron withdrawing Cl atoms which cannot stabilize the positive charge in TS.

Correct option is (d)

101. Arrange the following molecules in order of increasing fundamental vibrational frequencies

(a)

(b)

(c)

(d)

Ans. a

Sol. As bond order increases, stretching frequency increases

Correct answer is (a)

102. One of the Huckel molecular orbitals of 1, 3-butadiene is

The energy of this orbital in terms of the coulomb and resonance integrals is

(a)

(b)

(c)

(d)

Ans. b

Sol. Given wave function corresponds to one node.

Correct answer is (b)

103. A molecule AB₂ shows the following IR and Raman spectra

The structure of the molecule is

(a) Linear symmetrical

(b) Bent symmetrical (C_2v)

(c) Linear asymmetrical

(d) Bent asymmetrical (C_s)

Ans. c

Sol. Since, 2PR and 1PQR band Linear molecule

Since, two of the vibrations are active in both IR and RAMAN assymetric.

Hence, linear assymetric

Correct answer is (c)

104. For a one-dimensional (x) harmonic oscillator perturbed by an x³ potential, the sum of the first order and second order corrections to the ground state energy is

(a) < 0

(b) 0

(c) 0

(d) > 0

Ans. a

Sol. For 1-D harmonic oscillator, wavefunction of the particle in the ground state, will have even parity (defined parity). Therefore, first order correction to ground state energy due to a perturbing potential x³ (odd function) will be equal to zero.

For any potential system, the second order correction to ground state energy due to perturbation is always negative.

So, sum of the corrections will be < 0

Correct answer is (a)

105. Difference of average values of position <x> for states n = 1 and n = 2 of a particle confined in a one-dimensional (x) box of length L is

(a) L/4

(b) L/2

(c) L/3

(d) 0

Ans. d

Sol. For a 1-D box of length 'L', the average value of kposition <x> will be same for all states.

So, different in <x> for n = 1 and n = 2 states, will be zero.

Correct answer is (d)

106. The hermitian operator among the following is

(a)

(b)

(c)

(d)

Ans. b

Sol.

Correct answer is (b)

107. The translational partition function for Ar confined to a volume of 1 L at 300K, having thermal wavelength of 1.60 × 10^–11 m, is closest to

(a) 24.4 × 10²⁹

(b) 2.44 × 10²⁹

(c) 0.244 × 10²⁹

(d) 244 × 10²⁹

Ans. b

Sol.

Correct answer is (b)

108. Consider a phase transition between two incompressible phases. the correct statement among the following is

(a) The transition is independent of pressure

(b) The transition is independent of temperature

(c) The entropy of such transition is always zero

(d) The enthalpy of such transition is always non-zero

Ans. a

Sol. Since, the given phases are in comprssible. Therefore, the effect of pressure is zero on this phase transistor.

Correct answer is (a)

109. The third and fourth lines in the rotational Raman spectrum of CO are separated by 8 cm^–1. The CO bond length is given by

(a)

(b)

(c)

(d)

Ans. a

Sol.

Correct answer is (a)

110. Conductivities of water and a saturated solution of a sparingly soluble salt AB₂ are 7 and 21 m^–1, respectively. Given, and the solubility of AB₂, in mol m^–3, is

(a) 5.0 × 10^–4

(b) 5.0 × 10^–3

(c) 5.0 × 10^–5

(d) 5.0 × 10^–6

Ans. a

Sol.

Correct answer is (a)

111. The equilibrium constant of the following reaction:

(a) 10^6.08

(b) 10^8.08

(c) 10^10.08

(d) 10^12.08

Ans. c

Sol.

Correct answer is (c)

112. Langmuir adsorption isotherm for the dissociative adsorption of D₂(p = partial pressure of D₂ and k = ratio of rate constants for adsorption and desorption) is

(a)

(b)

(c)

(d)

Ans. c

Sol.

Correct answer is (c)

113. Entropy of a perfect gas is

(a) independent of V

(b) proportional to V

(c) proportional to ln V

(d) proportional to V²

Ans. c

Sol.

Therefore, entropy is proportional to

Correct answer is (c)

114. The contour and root mean square length (in nm) of a polymer chain modelled as a random coil, with N = 1000 and l = 150 pm, are closest to

(a) 1.50 and 47.4

(b) 15.0 and 4.74

(c) 150 and 47.4

(d) 150 and 4.74

Ans. d

Sol. Contour

And root mean square length

Correct answer is (d)

115. The free energy [A – A(0)] of a system with 10 non-interacting spins (S = 1) is

(a)

(b)

(c)

(d)

Ans. b

Sol.

Correct answer is (b)

Table-1:

116. The of ethylene, when placed in the xy plane with the C = C bond aligned to the x-axis transforms according to the irreducible representation (Use Table-1)

(a) a_u

(b) b_1u

(c) b_2u

(d) b_3u

Ans. b

Sol. If ethylene molecule is in xy plane (As in english version)

117. The transition in ethylene is

(a) not allowed

(b) allowed by to x-polarized light

(c) allowed by y-polarized light

(d) allowed by z-polarized light

(Use Table-1)

Ans. d

Sol.

Correct answer is (d)

118. A metal crystallizes with cubic close-packed structure. The values of Bragg reflections of Miller Planes (200) and (111) are 0.18 and 0.14, respectively. The unit cell length is

(a)

(b)

(c)

(d)

Ans. c

Sol.

Correct answer is (c)

119. k_uni is the effective first-order rate constant of the following unimolecular reaction

The slope and intercept of the plot of 1/k_uni vs. 1/[M] are 4 × 10⁶ and 8 × 10¹¹, respectively. The value of k_–1/k₂ is

(a) 2 × 10⁵

(b) 0.5 × 10⁵

(c) 32 × 10⁵

(d) 2 × 10^–5

Ans. a

Sol. ... (i)

Applying Steady state approximation on A^*

Rate of formation of A^* = rate of deformation of A^*

On substituting the value of [A^*] in equation (i)

Correct option is (a)

120. The decomposition mechanism of ozone is

If then the order of the reaction with respect to ozone is

(a) zero

(b) one

(c) two

(d) complex

Ans. b

Sol. r = k₂[O₃][O] ... (i)

Applying SSA on O gives

Rate of consumption of [O] = Rate of formation of [O]

On substituting the value of [O] in equation (i)

Hence, order with respect to ozone is 1.

Correct option is (b)