21. Molar composition of a mixture of P and Q at equilibrium is 3 : 1 (P:Q). A small disturbance in composition results in change of chemical potential of P by 10 J mol^–1. The chemical potential of Q will change (in J mol^–1) by:

(a) 30

(b) 3.3

(c) –30

(d) –3.3

Ans. c

Sol.

22. If the rate constant for a base catalyzed ester hydrolysis reaction is 0.20 L mol^–1 s^–1, half-life (in s) of the ester (Given [ester]_o = [base]_o = 0.05 mol. L^–1) would be closest to

(a) 40

(b) 100

(c) 140

(d) 200

Ans. b

Sol. For A second order reaction

23. For an octahedral Cu²⁺ complex depicting axial EPR spectrum the gemoetry of Cu²⁺ and the orbital containing the unpaired electron are, respectively

(a)

(b)

(c)

(d)

Ans. 1

Sol.

24. For the complex shown below in non functional state, the expected ³¹P(¹H) NMR resonance(s) is/are [³¹P. I = ¹/₂]

(a) one singlet

(b) one doublet

(c) two singlets

(d) two doublets

Ans. 4

Sol.

Correct answer is (d)

25. The correct order of basicity of the following anions is

(a) B > A > C > D

(b) D > B > C > A

(c) C > D > B > A

(d) B > A > D > C

Ans. d

Sol.

The –M strength of –NO₂ group is greater than and hence leads to more delocalisation of e^– decreasing the basicity

Here the bulky nitro group pushes the out of plane making it most basic of all

delocalisation of negative charge makes this comparitively less basic than (c)

So correct order is B > A > D > C

Correct option is (d)

26. Pair of lanthanide ions which shows significant deviation between the experimental and calculated magnetic moments, considerign contribution from the ground state only (given

(a) Gd³⁺ and Lu³⁺

(b) Sm³⁺ and Tb³⁺

(c) Eu³⁺ and Tb³⁺

(d) Sm³⁺ and Eu³⁺

Ans. d

Sol. The calculated magnetic moments are given by formula

In this particular formula only ground state contribution is considered but in case of Sm⁺³ and Eu⁺³ both the ground state and excited states contribution is considered. Hence the magnetic moment calculated is different from the magnetic moment observed.

Correct option is (d)

27. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. b

Sol.

The above reaction is an S_N2 reaction with the inversion of configuration.

Correct option is (b)

28. The hydrogen atomic orbital given by represents

(a) 2p orbital

(b) 3p orbital

(c) 3d orbital

(d) 4d orbital

Ans. 3

Sol.

29. Consider four species A, B, C and D

Oxidation of A with C in an acidic medium gives A, B, C and D are, respectively

(a)

(b)

(c)

(d)

Ans. 3

Sol.

30. The ion having the highest bond order is

(a) NO⁺

(b)

(c)

(d)

Ans. a

Sol.

31. The cell potential (in V) of a Ag/AgCl/KCl electrode connected to the standard hydrogen electrode at 298 K is closed to and assume that the activity of

(a) 0.197

(b) 0.297

(c) 0.340

(d) 0.440

Ans. c

Sol.

32. A cube does not have the symmetry element

(a) C₂

(b) C₃

(c) C₄

(d) C₆

Ans. d

Sol. The cube does not have C₆ symmetry element.

(1) The cube has there 4-fold axes each of which passes through the centre of 2 opposite faces.

(2) It has four 3-fold axes, each of which passes through two opposite vertices.

(3) And has six 2-fold exes, each of which passes through the mid points of 2 opposite edges.

Correct option is (d)

33. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. d

Sol.

Selective deprotection of the –COOt-Bu group takes place in the given conditions

Correct option is (d)

34. The frequency of O – H stretch occurs at ~3600 cm^–1. The O – D stretch frequency (in cm^–1) would be closed to

(a) 3000

(b) 2600

(c) 1800

(d) 900

Ans. b

Sol.

35. Identify from following, the products of K-electron capture by the nucleus:

A. neutron B. neutrino C. positron

Answer is

(a) A only

(b) A and B

(c) C only

(d) B and C

Ans. 2

Sol. Products of K-electron capture by the nucleus are neutron and neutrino.

Correct option is (b)

36. A liquid of density 1.1 g cm^–3 climbs to a height of 5.0 cm when a apillayr with internal radius of 0.2 mm is dipped into it. The surface tension (in Nm^–1) of the liquid is closed to

(a) 0.05

(b) 0.108

(c) 0.018

(d) 0.005

Ans. a

Sol. The height of the column at equilibrium is given by

37. The most stable vandium species in aqueous medium is

(a) [V(H₂O)₅(OH)]²⁺

(b) [VO(H₂O)₅]²⁺

(c) [VO(H₂O)₅]⁺

(d) [V(H₂O)₄(OH)₂]²⁺

Ans. b

Sol. Vanadium is most stable in +4 oxidation state VO²⁺.

In aquoues solution exist as [VO(H₂O)₅]²⁺

Correct option is (b)

38. The correct match for the drug molecules in Column A with their medicinal use in Column B is

(a) P-(i), Q-(ii), R-(iii)

(b) P-(ii), Q-(i), R-(iii)

(c) P-(iii), Q-(i), R-(ii)

(d) P-(i), Q-(iii), R-(ii)

Ans. a

Sol. (1) Procaine is a local anesthetic drug of amino ester group and is used primarily so reduce pain of intramuscular injection of panicillin, its also used in dentistry

(2) Warfarin sold under the brand name coumadin is used as an anticoagulant.

(3) Cephalerin is an antibiotic that can treat a number of bacterial infections.

Correct option is (a)

39. Correct order of molar extinction coefficient values of the vissible absorption bands for the following species is

(a) [Cr(H₂O)₆]²⁺ > [Mn(H₂O)₆]²⁺ > Chlorophyll > [NiCl₄]²⁺

(b) Chlorophyll > [NiCl₄]²⁺ > [Cr(H₂O)₆]²⁺ > [Mn(H₂O)₆]²⁺

(c) [NiCl₄]²⁺ > Chlorophyll > [Cr(H₂O)₆]²⁺ > [Mn(H₂O)₆]²⁺

(d) Chlorophyll > [Cr(H₂O)₆]²⁺ > [NiCl₄]²⁺ > [Mn(H₂O)₆]²⁺

Ans. b

Sol. In chlorophyll Charge transeter

40. E1cb mechanism is followed in the reaction of

(a) 2-bromopentane with t-BuOK to give pent-2-ene

(b) nitromethane with benzaldehyde in the presence of KOH to give nAtrostyrene

(c) bromobenzne with NaNH₂ to give aniline

(d) p-chloronitrobenzene with NaOMe to give p-nitroanisole

Ans b

Sol. E₁C_b mechanism is followed in the reaction of nitromethane with benzaledehyde

41. The correct match of ¹³C NMR chemical shift values for pyridine is

(a) C2 : 136; C3 : 124; C4 : 150

(b) C2 : 124; C3 : 150; C4 : 136

(c) C2 : 150; C3 : 124; C4 : 136

(d) C2 : 150; C3 : 136; C4 : 124

Ans. c

Sol. Electron rich centre coms in a shielded region and the electron deficient centre comes in deshielded region

Correct option is (c)

42. The Miller index for the plane as shown in the figure and parallel to the c-axis is

(a) 110

(b) 120

(c) 210

(d) 220

Ans. b

Sol. The plane is parallel to c-axis, therefore,

The intercept on X-axis, OA = 4a

The intercept on Y-axis, OB = 2b

Therefore, the millar indices of plane are (120)

Correct option is (b)

43. Consider the entropy changes in a system undergoing transformation, as depicted in the diagram, below

The correct statement among the following is

(a)

(b)

(c)

(d)

Ans. d

Sol. As S is a state function.

44. The magnitude of bond angles in gaseous NF₃, SbF₃ and SbCl₃ follow the order

(a) NF₃ > SbF₃ > SbCl₃

(b) SbCl₃ > SbF₃ > NF₃

(c) SbF₃ > SbCl₃ > NF₃

(d) NF₃ > SbCl₃ > SbF₃

Ans. d

Sol.

(1) According to rule (2) of VSEPR the bond angle α electronegetivity of central

So e^– vity of N > Sb atom.

(2) According to rule (3) of VSEPR the bond angle and e^– vity of F > Cl

So correct order is NF₃ > SbCl₃ > SbF₃

Correct option is (d)

45. The pair of light source and atomizer resulting highest sensitivity to atomic absorption spectrometric measurement is

(a) Hg lamp; nitric oxide flame

(b) Hg lamp; graphite furnace

(c) Hollow cathode lamp; graphite furnace

(d) Hollow cathode lamp; acetylene-nitric oxide flame

Ans. c

Sol. In atomic absorption spectroscopy, hollow cathode camp is used as radiation source and the best atomizer used is graphite furnace/tube or electro thermal atomizer.

Correct option is (c)

46. In IR spectrum, recorded neat, a compound shows a strong and broad band at 3300 cm^–1. The band becomes sharp and shifts to 3600 cm^–1 when the spectrum is recorded in CCl₄ at high dilution. This proves that the compound has

(a) OH group, which is involved in intramolecular H-bonding

(b) OH group, which is involved in intermolecular H-bonding

(c) a terminal alkyne group

(d) OH group, present in severely sterically hindered environment

Ans. b

Sol. Inpresence of ccl4 the intramolecular hydrogen binding breaks and also the stretching frequesncy increases and is nearly 3300 cm-1

Correct option is (b)

47. Choose the correct satements for oxymyoglobin and cytochrome P₄₅₀ (resting state) from the following :

A. Both contain dianion of protoporphyrin-IX

B. They have same fifth-ligand bonded to metal centre from the protein backbone

C. They contain single active site

D. They contain metal ion in +3 oxidation state

Answer is

(a) A, B and C

(b) A, C and D

(c) A, B and D

(d) B and C only

Ans. b

Sol. A. Both contain dianion of protoporphyrin-IX

B. They have same fifth-ligand bonded to metal centre from the protein backbone

D. They contain metal ion in +3 oxidation state

Correct option is (b)

48. In common galss electrode, alkaline error caused at pH > 10 is least for

(a) 0.01 M NaCl

(b) 1.0 M NaCl

(c) 1.0 M LiCl

(d) 1.0 M KCl

Ans. d

Sol. Alkaline error range At low concentration of H⁺ ions (high pH) contributions of interfering alkali metals (like Li, Na, K) are comparable with the one of hydrogen ions. In this situation, dependence of the potential on pH become non-linear.

In common glass electrode, alkaline error will be least for K⁺ due to larger size.

Correct option is (d)

49. Consider a two-level system in which the excited state, separated from the ground state by energy is doubly degenerate. The fraction of the molecules in the excited state, as

(a)

(b)

(c)

(d) 1

Ans. c

Sol. Consider a 2 level system

50. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. b

Sol.

Anti elimination [E₂ is preffered in this case].

The aligument of hydrozen anti periplanar is parallel to the

Correct option is (b)

51. The value of a physical variable was formed to be 196, 198, 194, 199 and 198 in a set of five independent measurements. The average value and the standard deviation would be closed, respectively to

(a) 198 and 2

(b) 197 and 4

(c) 197 and 2

(d) 198 and 4

Ans. c

Sol.

52. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. a

Sol.

Since radical initiator and heat/ right given therefore allylic bromination takes place.

Correct option is (a)

53. The expected number of V_CO bands in the IR spectra of fac-[Mo(PPh₃)₃(CO)₃] and trans-[Mo(PPh₃)₂(CO)₄] are, respectively

(a) one and one

(b) two and two

(c) two and one

(d) three and one

Ans. c

Sol. fac-[Mo(PPh₃)₃(CO)₃] trans-[Mo(PPh₃)₂(CO)₄]

Correct option is (c)

54. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. c

Sol.

55. The common heptacity observed for coordination of C₆₀ to a metal center is

(a) 2

(b) 4

(c) 5

(d) 6

Ans. a

Sol. Hepticity of C₆₀ to metal centre is 2.

Correct option is (a)

56. TRUE statement for the following transformation is

(a)

(b)

(c)

(d)

Ans. b

Sol.

We know the energy profile diagram

Energy of product - Energy of reactant from reaction coordinate diagram since entropy decreases.

57. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. d

Sol.

The reagent used here is H₂/Raney Ni. i.e. used for reduction and it reduces NO₂ group and not the COOH group there fore

58. The correct order for the rate of thermal decarboxylation of the following compounds is

(a) C > B > A

(b) C > A > B

(c) A > C > B

(d) B > C > A

Ans. a

Sol.

Thermal decomposition gives a carbanion and more is stability of carbanion more is the rate of decarboxylation.

So, c > b > a

band a are judged on basic of inductive effect.

Correct option is (a)

59. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. d

Sol.

Taking (A) as substrate

Both the compounds can be formed rul the fused ring system is much more stable than the bridged system

Correct option is (d)

60. The titration of 4.4 g of a polymer having carboxylic acid end group requires 11 mL of 0.02M NaOH. The average molar mass (in kg mol^–1) of the polymer is

(a) 40

(b) 20

(c) 15

(d) 10

Ans. b

Sol. The titration of 4.4g of a polymer having A carbonylic acid group requires 11 ml of 0.02 M NaOH the avg molar mass of polymer is

We know that

M = 20 kg (mol)

Correct option is (b)

61. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. c

Sol.

62. FeCr₂O₄ and NiGa₂O₄ have normal and inverse spinel structures, respectively. The correct statement is

(a) Fe(II) and Ni(II) occupy octahedral sites

(b) Fe(II) and Ni(II) occupy tetrahedral and octahedral sites, respectively.

(c) Cr(III) and Ga(III) occupy only octahedral sites

(d) Cr(III) and Ga(III) occupy tetrahedral and octahedral sites, respectively.

Ans. b

Sol. Normal spinal

So, Fe(II) & N(II) will occupy tetrahedral & octahedral sites respectively because, FeCr₂O₄ is normal spinal & NiGa₂O₄ have inverse spinal

Correct option is (b)

63. (C_p – C_v) for a non-ideal gas differs from (C_p – C_v) for a perfect gas by the expression.

(a)

(b)

(c)

(d)

Ans. b

Sol.

Put value in equation 1

64. The correct statement about base hydrolysis of [Co(py)₄Cl₂]⁺ (py = pyridine) is

(a) rate expression is, Rate = k [Co(py)₄Cl₂]⁺[OH^–]

(b) reaction does not depend on hydroxide ion concentration

(c) reaction proceeds through S_N1CB mechanism

(d) intermediate involved in this reaction is [Co(py)₄Cl₂(OH]

Ans. b

Sol. [Co (Py)₄Cl₂]⁺

Because there is no proton, so there will be normal hydrolysis.

reaction does not depend on hydroxide ion concentration.

Correct option is (b)

65. In linear variation method using two orthogonal basis functions, the two roots obtained are andThe correct relation to these with exact ground and first excited state energies, E₀ and E₁, respectively, is

(a)

(b)

(c)

(d)

Ans. d

Sol. When ever a trial wave function is used to find the energy of any state, it is always greater than the energy of a particulare state.

66. Match column I, II and III

The correct match is

(a) A – iii – Y; B – i – Z; C – ii – X

(b) A – iii – Y; B – ii – X; C – i – Z

(c) A – ii – X; B – i – Y; C – iii – Z

(d) A – i – X; B – iii – Z; C – ii – Y

Ans. a

Sol. Carbonic anhydrase Zn Metal Carbonic Acid

67. In spectrofluorimetric determination in solution

(1) absorbance of analyte solution is kept near to 0.05

(2) oxygen is eradicated from solution.

(3) pH of solution is controlled.

(4) wavelength of incident light is always above 400 nm

Correct from the above is

(a) 1, 2 and 4

(b) 2, 3 and 4

(c) 1, 2 and 3

(d) 1, 3 and 4

Ans. c

Sol. In spectroflowrimetric determination, absorbance of analyte solution is kept near to 0.05, oxygen is eradicated from solution and pH is controlled, (1, 2, 3 are correct)

Correct option is (c)

68. The spatial part of the dominant resonance structure of the LiH molecule is (only valance part of the wavefunction is shown).

(a) 2s_Li(r₁) 2s_Li(r₂)

(b) 2s_Li(r₁) 1S_H (r₂) + 2s_Li(r₂) 1S_H(r₁)

(c) 2s_Li(r₁) 1S_H(r₂) – 2s_Li (r₂) 1S_H(r₁)

(d) 1S_H (r₁) 1S_H(r₂)

Ans. d

Sol. only possible combination for the ............... part

69. The intermediate A and the major product B formed in the following reaction are

(a)

(b)

(c)

(d)

Ans. b

Sol.

Correct option is (b)

70. The correct order of the reactions involved in the following transformation is

(a) Michael addition, Quasi – Favorskii rearrangement, Aldol condensation

(b) Quasi – Favorskii rearrangement, Michael addition, Aldol condensation

(c) Michael addition, Aldol condensation, Quasi – Favorskii rearrangement

(d) Aldol condensation, Quasi – Favorskii rearrangement, Michael addition

Ans. c

Sol.

71. The species for which the shapes (geometry) can be predicted by VSEPR theory is/are

(1) [PtCl₄]^2– (2) [TeCl₆]^2– (3) PF₃ and SF₆

(a) 1 and 3

(b) 2 and 3

(c) 3 only

(d) 1 and 2

Ans. c

Sol. In VSEPR theory both bond pair and lone pair repulsion are considered.

The shape of transition metal complexes are explained on the basis of Kepert rule considering only ligand-ligand repulsion. So, shape of [PtCl₄]^2– can not predicted by VSEPR theory.

In case of [TeCl₆]^2–, the lone pair present on Te is stereochemically inactive and not participate in hybridisation [TeCl₆]^2– is perfect octahedral geometry. So, no predicted by VSEPR theory.

Correct option is (c)

72. The molar residual entropy (in J K^–1) of solid OCS would be closest to

(a) 0

(b) 2.9

(c) 5.8

(d) 8.7

Ans. c

Sol. Type of arrangement of OCS

Here R = 8.314 JK^–1, W = 2

Entropy = 5.76 JK^–1

Correct option is (c)

73. Consider the gas phase reaction at the given temperature. When 2.0 moles of A(g) are reacted with 2.0 moles of B(g), 0.8 moles of C(g) are formed at equilibrium at a total pressure of 2.0 bar. The value of the equilibrium constant, K_P of this reaction at the given temperature is closest to

(a) 0.3

(b) 0.9

(c) 2.4

(d) 19.1

Ans. c

Sol.

74. The main product of nucleophillic attack of H^– on the complex ion given below is

(a)

(b)

(c)

(d)

Ans. b

Sol.

Priorityorder of attack Open acyclic even > Cyclic > Odd system.

Correct option is (b)

75. The correct absolute configuration of the following compounds is

(a) I: M; II : R

(b) I : M; II : S

(c) I : P; II : R

(d) I : P; II : S

Ans. a

Sol.

Along chiral plane considering pilot atom,

II – R

I

using helical chirality, making upward to downwards roration will be anticlockwise (M)

I : M

Correct option is (a)

76. The correct order of metal – carbon distance is

(a)

(b)

(c)

(d)

Ans. d

Sol.

The metal carbon distance can be calculated by central metal atom

Fe(n⁵–Cp)₂ has Fe⁺² = 3d⁶4s⁰

Co(n⁵–Cp)₂ has Co⁺² = 3d⁷4s⁰

Ni(n⁵–Cp)₂ has Ni⁺² = 3d⁸4s⁰

The more the number of unpaired e^– more is the bond length between metal carbon bond correct is order is Ni(n⁵–Cp)₂ > Co(n⁵–Cp)₂ > Fe(n⁵–Cp)₂

Correct option is (d)

77. Product A and B formed in the following transformation of alkylidenecarbenes are

(a)

(b)

(c)

(d)

Ans. a

Sol.

Reactivity order Gxialh > eq. H

78. The correct match of spin-only magnetic moment for the complexes cis-[Fe(phen)₂(NCS-N)₂] (A) and [Fe(phen)₃]Cl₂ (B) at 300 K is (phen = 1,10-phenanthroline)

(a) 4.89 BM for both A and B

(b) 0 BM for both A and B

(c) 4.89 BM for A and 0 BM for B

(d) 0 BM for A and 4.89 BM for B

Ans. c

Sol. Spin Cross over phenom

In this compound some ligands are weak and some are strong, soit shows S.C.

= [Fe(Phen)₃]Cl₂ low spin complex

Fe²⁺ Low spin t_2g6 e_g^o

unpaired electron is zero

spin only magnetic moment zero for (B)

Correct option is (c)

79. The Hückel molecular orbital of benzene that is degenerate with the molecular orbital

(a)

(b)

(c)

(d)

Ans. a

Sol.

Nodel Plane = 1

So, these are degene rate wave function

Correct option is (a)

80. The major products A and B in the following reaction sequence are

(a)

(b)

(c)

(d)

Ans. b

Sol.

Correct option is (b)

81. The structure of the compound, which displays the following spectral data is

IR = 1690, 1100 cm^–1

(a)

(b)

(c)

(d)

Ans. c

Sol.

82. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. a

Sol.

83. In the pure rotational microwave spectrum of a XY molecule, the adjacent lines are separated by 4 cm^–1. If the molejcule is irradiated by a radiation of 30,000 cm^–1, the first Stokes line (in cm^–1) appears at

(a) 29988

(b) 30012

(c) 30004

(d) 29996

Ans. a

Sol. In Rotational Spectra

lines are seperated by 2B

84. Choose the equilibria from the following that are NOT favoured to go to right:

(a) A and B

(b) A and C

(c) B and C

(d) B and D

Ans. d

Sol.

is exothermie, as predickeed by hard soft rule.

The bond issociation energies measured from these molecules in gas phase are

Be–F 632 Hg–F 268

Be–I 289 Hg–I 145

Therefore, it is not large Hg-I bond energy that ............ that the reaction is .............. but the especially strrong bond between Be & F which is an example of hard intereaction. In fact an Hg atom foms only a weak bond to any other atom.

Using hard - soft acid base theory

So it is no favoured in forward direction.

Correct option is (d)

85. Consider the following statements:

(A) The highest oxidation state of Group 18 elements is more readily shown in their oxides than in fluorides.

(B) Fe can exist in –2 formal oxidation state also.

(C) Mn, Tc and Re easily form M(II) compounds.

The correct statement(s) is/are

(a) A and B

(b) A and C

(c) B and C

(d) C only

Ans. a

Sol. Down the group higher oxidation state is more stable thats why statement C is incorrect

Fe Can exist in – 2 formal oxidation state [Fe(CO)₄]^2–

On the basis of excitation theory statement is correct

Correct option is (a)

86. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. a

Sol.

87. The rate constant of a second order reaction If the initial concentration of the reactant is a₀ and the concentration of the product at time t is x, then a linear function of t with the slope k₂a₀ is

(a)

(b)

(c)

(d)

Ans. c

Sol.

88. Match the items in Column I with those of Column II.

Column I (species) Column II (structure/properties)

A. NaH i. polymeric chain

B. BeH₂ ii. interstitial hydride

C. HfH_2.10 iii. tricapped trigonal prismatic

D. [TcH₉]^2– iv. saline hydride

The correct match is

(a) A-iv, B-ii, C-iii, D-i

(b) A-i, B-iv, C-ii, D-iii

(c) A-iv, B-i, C-ii, D-iii

(d) A-iv, B-i, C-iii, D-ii

Ans. c

Sol. [TcH₉]^2– Tricapped trigonal presimatic any hydride with MH_x, x = fractional is interstitial hydride

& NaH is a saline hydride, saline hydride are compounds formed between hydrogen & the most active metal especially with the alkali & alkaline each metals.

Correct option is (c)

89. The oxidation of NO to NO₂ occurs via the mechanism given below.

in the presence of large excess of O₂ can be written as

(a) 2k₁(NO)²

(b) 2k₁k₂(NO)²(O₂)

(c)

(d) 2k₂(NO)²

Ans. a

Sol.

90. The major product of the following reaction is

(a)

(b)

(c)

(d)

Ans. b

Sol.

91. TRUE statement regarding Hammett reaction constant for the following transformations given in equations A and B is

(a) for A and B is same and positive

(b) for A and B is same and negative

(c) for A is larger positive value than for B

(d) for A is negative and for B is positive

Ans. c

Sol.

The Hammett reaction constant ρ measures the sensitivity of the reaction to electronic effect.

• A positive value means more electrons in transition state than in starting material.

• A negative value means fewer electrons in the transition state in the starting material.

So, for A is larger positive (+2.6) value than for B(+0.5)

Correct option is (c)

92. For the reaction which follows the harpoon mechanism, the reactive cross section is closest to

Ionization energy of K = 422.5 kJ mol^–1, electron affinity of Br₂ = 250 kJ mol^–1 and N_A = 6 × 10²³ mol^–1)

(a) 50 × 10^–18 m²

(b) 2 × 10^–18 m²

(c) 64 × 10^–18 m²

(d) 16 × 10^–18 m²

Ans. b

Sol. Reaction cross section

93. In a polymer of N monomer units, the root mean square separation between the two ends is proportional to

(a)

(b) N

(c)

(d) N²

Ans. a

Sol. The not mean square separation between the two ends in a polymer of N monomer units is

94. The reaction that gives (E)-2-methylhex-3-ene as the major product is

(a)

(b)

(c)

(d)

Ans. d

Sol.

95. Complex(es) which has/have unpaired electron(s) that is equal to that of iron center in oxymyoglobin is/are

A. [Fe(ox)₃]^3– B. [Fe(CN)₆]^3– C. [NiCl₄]^2– D. [Cu(NH₃)₄]²⁺

(Given: ox = oxalato)

Correct answer is

(a) A and B

(b) B and D

(c) C only

(d) C and D

Ans. a

Sol. In oxymyeglobin Fe is in +3 oxidation state

96. In Mössbauer spectrum of a sample containing iron recorded in the presence of a static magnetic field, the number of possible allowed transition(s) is

(a) Two

(b) Four

(c) Six

(d) Eight

Ans. c

Sol. In G.S. energy level

97. In the electronic spectrum of [IrBr₆]^2–, the number of charge transfer band(s) and their origin are, respectively

(a)

(b)

(c)

(d)

Ans. c

Sol. [IrBr₆]^2– give, the oxidation state of control metal has Ir⁴. The change transfer takes from ligand to metal charge transfer.

There are 2 bands one from P orbital of ligand to t_2g and one from ligand P-orbital to e_g of the metal.

Correct option is (c)

98. The intermediate A and the major product B formed in the following reaction are

(a)

(b)

(c)

(d)

Ans. b

Sol.

Correct answer is (b)

99. The electrolyte solution that has the smallest Debye-length at 298 K is

(a) 0.01 M NaCl

(b) 0.01 M Na₂SO₄

(c) 0.01 M CuCl₂

(d) 0.01 M LaCl₃

Ans. d

Sol.

100. The reducible representation, in the table is equal to the following superposition of the irreducible representations of C_2v point group.

(a)

(b)

(c)

(d)

Ans. b

Sol. Using Stand area reduction formula

101. In trans 1,2-dichloroethylene, the IR inactive mode is

(a) C–Cl symmetric stretch

(b) C–Cl asymmetric stretch

(c) C–H asymmetric stretch

(d) In phase out of plane C–Cl bend

Ans. a

Sol.

IR Inactive mode C–Cl symmetric streching

Correct option is (a)

102. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. b

Sol.

The above reaction is intramolecular mc-murry coupling reaction

Correct option is (b)

103. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. a

Sol.

Correct answer is (a)

104. 1.0 mol of a perfect monatomic gas is put through the cycle shown in the figure. The total work (in J) done during the cycle is

(use 1L-bar = 100 J, R = 8.3 J K^–1 mol^–1 = 0.083 L-bar K^–1 mol^–1, ln 2 = 0.7)

(a) 930

(b) –4183

(c) 8831

(d) –5113

Ans. b

Sol.

105. For the electrochemical cell Ag|AgCl|MCl(0.01M)|MCl(0.02M)|AgCl|Ag, the junction potential is the highest when M⁺ is

(a) H⁺

(b) Li⁺

(c) Na⁺

(d) K⁺

Ans. a

Sol.

The solution in which the difference between t₊ and t_– is maximum, has highest LJP.

Since, anion is common for all solution. Therefore, the difference is divided by the transport number of cation in solution. Since, is maximum.

Hence, liquid junction potential is maximum where H⁺ is used.

Correct option is (a)

106. The major products A and B formed in the following reactions are

(a)

(b)

(c)

(d)

Ans. a

Sol.

107. Thye order of a surface catalyzed unimolecular reaction, at very low and very high pressures of the reactant, would be, respectively

(a) 0, 0

(b) 1, 0

(c) 0, 1

(d) 1, 1

Ans. b

Sol.

So the above equation shows that reaction is a first order reaction

108. The compound that shows peaks in the EI mass spectrum at m/z 121, 105, 77, 44 is

(a)

(b)

(c)

(d)

Ans. b

Sol.

Correct answer is (b)

109. The rate-determining step in the catalytic synthesis of acetic acid by Monsanto process is

(a) oxidative addition of CH₃I to [RhI₂(CO)₂]^–

(b) migration of CH₃ group to CO of [RhI₃(CO)₂(CH₃)]^–

(c) loss of CH₃COI from [RhI₃(CO)₂(COCH₃)]^–

(d) coordination of CO to [RhI₃CO(COCH₃)]^–

Ans. a

Sol.

Monsanto process.

Oxidative addition step is slowest step & thus will be RDS

110. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. b

Sol.

111. The function, which is NOT an eigenfunction of the indicated operator, is

(a)

(b)

(c)

(d)

Ans. b

Sol.

Thus this combination does not follow eigen volume equation

Correct option is (b)

112. Among SO₂(OH)F, CH₃CO₂H, LiF and H₂O, the compound(s) which behave(s) as a base in liquid HF is/are

(a) CH₃CO₂H and LiF only

(b) LiF only

(c) SO₂(OH)F and LiF only

(d) CH₃CO₂H, LiF and H₂O

Ans. d

Sol.

CH₃CO₂H, LiF and H₂O in liquid Hf gives so behave as base

Correct option is (d)

113. The correct statements for dithionite and dithionate anions from the following are

(A) both have S–S bond (B) both are dianionic

(C) oxidation state of sulphur is +3 and +5, respectively

(D) sulphur in dithionate has lone pair of electrons

(a) A, B and C

(b) A, B and D

(c) B, C and D

(d) A and B only

Ans. a

Sol. Dithionite Dithionate

(A) Both have S–S bonds

(B) Both are diemionic

(C) Oxidation state of sulfur is +3 and +5 respectively

These statements are correct, the fourth statement is

(D) sulfur in dithionate has lone pair of e^– which is not correct.

Correct option is (a)

114. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. c

Sol.

Correct answer is (c)

115. Match the items in column I with those of column II

Column I Column II

A. Conductometric titration i. Voltage

B. Amperometric titrations ii. Resistance

C. pH metric titration iii.

D. Differential pulse polarography iv. I_d

Correct match is

(a) A-ii; B-iv; C-i; D-iii

(b) A-iii; B-i; C-ii; D-iv

(c) A-iii; B-ii; C-iv; D-i

(d) A-i; B-iii; C-iv; D-ii

Ans. a

Sol. In Column-1, when we plot graph, then we get all the terms present in Column-2 on y-axis.

1. Amperometric titration (Titrant reducible)

Conductometric titration Resistance

Amperometric titration Id

pH metric titration Voltage

Differential Pulse Polarography

Correct option is (a)

116. The major product formed in the following reaction is

(a)

(b)

(c)

(d)

Ans. b

Sol.

Correct answer is (b)

117. X-rays of 173 pm wavelength are reflected by the (111) plane of a cubic primitive crystal at 30º. The unit cell length (in pm) is closest to

(a) 173

(b) 300

(c) 346

(d) 600

Ans. b

Sol.

118. The major product A and the byproducts B formed in the following reaction are

(a)

(b)

(c)

(d)

Ans. a

Sol.

Correct answer is (a)

119. The cluster types of [Fe₅(CO)₁₄N]^– and [Co₆(CO)₁₃N]^– are, respectively,

(a) nido-, nido-

(b) nido-, closo-

(c) closo-, nido-

(d) closo-, closo-

Ans. c

Sol.

TVE = 8 + 5 + 14 × 2 + 5 + 1

= 40 + 28+ 6 = 74

(Nitrogen is present in intensitial .........& will donate del is volume e^–)

Here n = 5 So nido

Correct option is (c)

120. The degeneracy of the state having energy for a particle in a 3-D cubic box of length L is

(a) 4

(b) 3

(c) 2

(d) 1

Ans. a

Sol.

Possible combinations,

Correct option is (a)