PAPER : CSIR-UGC-NET/JRF June 2015 1

PAPER : CSIR-UGC-NET/JRF June 2015

CHEMICAL SCIENCES BOOKLET-[A]

Part-B
21. The biological functions of carbonic anhydrase and carboxypeptidase A, respectively, are
(a) interconversion of CO2 and carbonates, and hydrolysis of peptide bond
(b) gene regulation and interconversion of CO2 and carbonates
(c) gene regulation and hydrolysis of peptide bond
(d) interconversion of CO2 and carbonates and gene regulation
22. The Fe–Nporphyrin bond distances in the deoxy and oxy-hemoglobin, respectively, are
(a) ~ 2.1 and 2.0 Å (b) ~ 2.0 and 2.0 Å (c) ~ 2.2 and 2.3 Å (d) ~ 2.3 and 2.5 Å
23. The binding modes of NO in 18 electron compounds [Co(CO)3(NO)] and [Ni(5–Cp) (NO)], respec-
tively, are
(a) linear and bent (b) bent and linear (c) linear and linear (d) bent and bent
24. The role of copper salt as co-catalyst in Wacker process is
(a) oxidation of Pd(0) by Cu(II) (b) oxidation of Pd(0) by Cu(I)
(c) oxidation of Pd(II) by Cu(I) (d) oxidation of Pd(II) by Cu(II)
25. For typical Fischer and Schrock carbenes, consider the following statements
A. Oxidation state of metal is low in Fischer carbene and high in Schrock carbene
B. Auxilliary ligands are -acceptor in Fischer carbene and non--acceptor in Schrock carbene
C. Substituents on carbene carbon are non--donor in Fischer carbene and -donor in Schrock
carbene
D. Carbene carbon is electrophilic in Fischer carbene and nucleophilic in Schrock carbene
The correct statements are
(a) A, B and C (b) A, B and D (c) B, C and D (d) A, C and D
26. The species having the strongest gas phase proton affinity among the following,
(a) N3– (b) NF3 (c) NH3 (d) N(CH3)3
27. Consider the following statements regarding the diffusion current at dropping mercury electrode
A. It does not depend on mercury flow rate
B. It depends on drop time
C. It depends on temperature
[Link]
Correct statement(s) is/are
(a) A only (b) B only (c) A and B (d) B and C
28. Q value for the reaction 13N(n, p)13C is 3.236 MeV. The threshold energy (in MeV) for the reaction
13
C(p, n)13N is
(a) –3.236 (b) –3.485 (c) 3.485 (d) 3.845
29. The Sn NMR chemical shift (approximately in ppm) corresponding to (5–Cp)2Sn (relative to
119

Me4Sn) is
(a) – 4 (b) + 137 (c) + 346 (d) – 2200
30. All forms of phosphorus upon melting, exist as
P P P
(a) n P P (b) P P P P
n
P P P

P P P P
P P P
P P P
P P P P
P P
(c) n P P ` (d) P
P P P P
P P
P P
2 PAPER : CSIR-UGC-NET/JRF June 2015

31. For the oxidation state(s) of sulphur atoms in S2O, consider the following
A. –2 and +4 B. 0 and +2 C. +4 and 0
The correct answer(s) is/(are)
(a) A and B (b) A and C (c) B and C (d) C only
32. The correct set of pseudohalide anions is
(a) CN  , ClO4 , BF4 , PF6 (b) N 3 , NO3 , HSO 4 , AsF6
(c) SCN  , PO34 , H 2 PO4 , N 3 (d) CN  , N 3 , SCN  , NCN 2
33. In transition metal phosphine (MPR3) complexes, the back-bonding involves donation of elec-
trons from
(a) M(t 2g )  PR 3 (*) (b) M(t 2g )  PR 3 ( *)
(c) M(e g )  P(d) (d) PR 3 ()  M(t 2g )
34. The refluxing of RhCl3.3H2O with an excess of PPh3 in ethanol gives a complex A. Complex A and
the valence electron count on rhodium are, respectively,
(a) [RhCl(PPh3)3], 16 (b) [RhCl(PPh3)5], 16 (c) [RhCl(PPh3)3], 18 (d) [RhCl(PPh3)5], 18
35. The -hydrogen elimination will be facile in

M M M
(a) (b) (c) (d) M H
H H H
2 2
36. The reaction  Co  CN 5 H 2 O   X   Co  CN 5 X   H 2O follows a/an
(a) Interchange dissociative (Id) mechanism (b) Dissociative (D) mechanism
(c) Associative (A) mechanism (d) Interchange Associative (Ia) mechanism
37. Correct statement on the effect of addition of aq. HCl on the equilibrium is
OH
HO O
..... Eq. A
O O
O
–
O + CN ..... Eq. B
CN

(a) Equilibrium will shift towards right in case of both A and B

[Link]
(b) Equilibrium will shift towards left in case of both A and B
(c) Equilibrium will shift towards right in A and left in case of B
(d) Equilibrium will shift towards right in B and left in case of A.
38. The compound that exhibits sharp bands at 3300 and 2150 cm–1 in the IR spectrum is
(a) 1-butyne (b) 2-butyne (c) butyronitrile (d) butylamine
39. The 1H NMR spectrum of a dilute solution of a mixture of acetone and dichloromethane in CDCl3
exhibits two singlet of 1 : 1 intensity. Molar ratio of acetone to dicholromethane in the solution is
(a) 3 : 1 (b) 1 : 3 (c) 1 : 1 (d) 1 : 2
40. Intense band generally observed for a carbonyl group in the IR spectrum is due to
(a) The force constant of CO bond is large
(b) The force constant of CO bond is small
(c) There is no change in dipole moment for CO bond stretching
(d) The dipole moment change due to CO bond stretching is large.
 PAPER : CSIR-UGC-NET/JRF June 2015 3

41. The compound that gives precipitate on warming with aqueous AgNO3 is
Br Br Br
Br

(a) (b) (c) (d)

N
42. Following reaction goes through
COOAg Br
Br2

(a) free radical intermediate (b) carbanion intermediate

(c) carbocation intermediate (d) carbene intermediate
43. The most stable conformation for the following compound is
Me Me

Me

Me
Me Me Me
Me Me Me
Me
(a) H (b) Me (c) H (d) Me

Me H Me H

44. The major product formed in the following reaction is

O
NaBH4, CeCl3
Me
MeOH, H2O
CHO

OH O OH
Me
(a) Me [Link]
(b)
OH
OH
(c) Me
OH
(d) Me
CHO
O
45. The correct relation between the following compounds is
H H H Cl
· ·
Cl Me Me H
HO
OH
(a) enantiomers (b) diastereomers
(c) homomers (identical) (d) constitutional isomers
46. The correct order of heat of hydrogenation for the following compounds is
Me
Me Me Me Me Me
Me
(I) (II) (III) Me (IV)
(a) I > II > III > IV (b) I > III > II > IV (c) IV > I > III > II (d) IV > II > I > III
4 PAPER : CSIR-UGC-NET/JRF June 2015

47. Among the following, the correct statement(s) about ribose is (are)
(A) on reduction with NaBH4 it gives optically inactive product.
(B) on reaction with methanolic HCl it gives a furanoside
(C) on reaction with Br2–CaCO3–water it gives optically inactive product.
(D) it gives positive Tollen’s test
(a) A, B and D (b) A, B and C (c) B and C (d) D only
48. Biogenetic precursors for the natural product umbelliferone among the following are

HO O O
umbelliferone
(A) L-tryptophan (b) cinnamic acid (c) L-methionine (d) L-phenylalanine
49. Number of signals in the 13C{1H| NMR spectrum of (R)-4-methylpentan-2-ol are
(a) 3 (b) 4 (c) 5 (d) 6
50. The major product formed in the following reaction is
Me Me

EtO2C
NaBH4
0ºC
H MeOH/THF
O

Me Me Me Me Me
Me Me Me

EtO2C EtO2C
HO HO
(a) (b) (c) (d) OH
H OH H
H H
H
H H
OH OH H
51. The major product formed in the following reaction is
heat
Me

Me [Link]
H H H

(a) (b) (c) (d)

H Me H Me H Me
52. The major product formed in the following reaction is
Me
O
O
H2N–NH2HCl
Et3N, CH3CN, rt

Me
Me Me Me Me
O O
HO HO

(a) (b) (c) (d)

Me Me Me Me Me
 PAPER : CSIR-UGC-NET/JRF June 2015 5

53. The magnitude of the stability constants for K+ ion complexes of the following supra-molecular
hosts follows the order,

N N S
H H
O O O O O O

O O O O O O
H
N O S

(A) (B) (C)

(a) B > A > C (b) C > A > B (c) A > B > C (d) C > B > A

54. Antitubercular drug(s) among the following is (are)

(A) Salbutamol (B) Ethambutanol (C) Isoniazid (D) Diazepam
(a) A and B (b) B and C (c) C and D (d) D alone
55. A particle is in a one-dimensional box with a potential V 0 inside the box and infinite outside. An
energy state corresponding to n = 0 (n : quantum number) is not allowed because
(a) the total energy becomes zero
(b) the average momentum becomes zero
(c) the wave function becomes zero everywhere
(d) the potential V0  0
56. An eigenstate of energy satisfie H n  E n  n . In the presence of an extra constant potential V0
(a) both En and  n will change (b) both En and average kinetic energy will change
(c) only En will change, but not  n (d) only  n will change, but not En.
57. The intensity of a light beam decreases by 50% when it passes through a sample of 1.0 cm path
length. The percentage of transmission of the light passing through the same sample, but of 3.0 cm
path length, would be
(a) 50.0 (b) 25.0 (c) 16.67 (d) 12.5
58. The electric-dipole allowed transition among the following is
(a) 3 S  3 D [Link]
(b) S  P 3 3
(c) S  D (d) S  3 1 3 1
F
59. The product C2x  xy ( C2x is the two-fold rotation axis around the x-axis and xy is the xy mirror
plane) is
(a)  xz (b)  yz (c) C2y (d) Cz2
60. The simplest ground-state VB wave function of a diatomic molecule like HCl is written as
   H 1s, 1 Cl  3 pz , 2   B , where B stands for
(a)  H  3 pz , 2  Cl 1s, 1 (b)  H 1s, 2  Cl  3 pz , 1

(c)  Cl 1s, 2  Cl  3 p z , 1 (d)  Cl 1s, 2  H  3 pz , 1

61. Heat capacity of a species is independent of temperature if it is
(a) tetratomic (b) triatomic (c) diatomic (d) monatomic
6 PAPER : CSIR-UGC-NET/JRF June 2015

62.  PCl3  g   Cl 2  g  , xenon gas is added at constant volume.

In a chemical reaction : PCl5  g  
The equilibrium
(a) will shift towards the reactant
(b) will shift towards the products
(c) will not change the amount of reactant and products
(d) will increase both reactant and products
63. The temperature-dependence of a reaction is given by k  AT 2 exp  E 0 / RT 

The activation energy  E a  of the reaction is given by

1
(a) E 0  RT (b) E0 (c) E0  2RT (d) 2E 0  RT
2
64. For a reaction, 2A  B  3Z , if the rate of consumption of A is 2  104 mol dm 3s 1 the rate of
formation of Z (in mol dm–3 s–1) will be
4
(a) 3  104 (b) 2  104  10 4 (c) (d) 4  104
3
65. Dominant contribution to the escaping tendency of a charged particle with uniform concentration in
a phase, depends on
(a) chemical potential of that phase (b) electric potential of the phase
(c) thermal energy of that phase (d) gravitational potential of that phase
66. The intrinsic viscosity depends on the molar mass as    KMa
The empirical constants K and a are dependent on
(a) solvent only (b) polymer only
(c) polymer solvent pair (d) polymer-polymer interaction
67. The correct G for the cell reaction involving steps
Zn  s   Zn 2  aq   2e 

Cu 2  aq   2e   Cu  s  is

a Zn2 0
a Zn 2 a Zn s  a Zn2
[Link]
0 0 0
(a) G  RT ln G  RT ln G  RT ln G  RT ln
a Cu2 (b) a Cu  s  (c) a Cu 2 (d) a Cu 2

68. The lowest energy-state of an atom with electronic configuration ns1np1 has the term symbol
(a) 3 P1 (b) 1 P1 (c) 3 P2 (d) 3 P0
69. Energy of interaction of colloidal particles as a function of distance of separation can be identified as
(1) vander Waals, (2) double layer, (3) vander Waals and double layer. The correct order of interac-
tions in the figure corresponding to curves (a) , (b) and (c), respectively, is

(b)
E (a)

(a) 1, 2, 3 (b) 2, 3, 1 (c) 3, 1, 2 (d) 1, 3, 2

 PAPER : CSIR-UGC-NET/JRF June 2015 7

70. The packing factor (PF) and number of atomic sites per unit cell (N) of an FCC crystal system are
(a) PF = 0.52 and N = 3 (b) PF = 0.74 and N = 3
(c) PF = 0.52 and N = 4 (d) PF = 0.74 and N = 4

PART-C
71. Differential pulse polarography (DPP) is more sensitive than D.C. Polarography (DCP). Consider
following reasons for it
(A) non-faradic current is less in DPP in comparison to DCP
(B) non-faradic current is more in DPP in comparison to DCP
(c) polarogram of DPP is of different shape than that of DCP
Correct reason(s) is/are
(a) A and C (b) B and C (c) B only (d) A only
72. Considering the following parameters with reference to the fluorescence of a solution:
(A) molar absorptivity of fluorescent molecule
(B) intensity of light source used excitation
(C) dissolved oxygen
The correct answer for the enhancement of fluorescence with the increase in these parameters is/are
(a) A and B (b) B and C (c) A and C (d) C only
73. The geometric cross section of 125Sn (in barn) is nearly
(a) 1.33 (b) 1.53 (c) 1.73 (d) 1.93
74. Match column A (coupling reactions) with column B (reagents)
Column-A Column-B
(1) Suzuki coupling (I) H2C CHCO2CH3
(2) Heck coupling (II) RB(OH)2
(3) Sonagashira coupling (III) PhCO(CH2)3Znl
(4) Negeshi coupling (IV) CH CR
(V) SnR4
The correct match is
(a) 1-II, 2-I, 3-IV, 4-III(b) 1-I, 2-V, 3-III, 4-IV
(c) 1-IV, 2-III, 3-II, 4-I(d) 1-II, 2-III, 3-IV, 4-V
75. The oxoacid of phosphorus having P atoms in +4, +3, and +4 oxidation states respectively, is
(a) H5P3O10 (b) H5P3O7 (c) H5P3O8 (d) H5P3O9
[Link]
76. The geometries of [Br3]+ and [I5]+, respectively, are
(a) trigonal and tetrahedral (b) tetrahedral and trigonal bipyramidal
(c) tetrahedral and tetrahedral (d) linear and trigonal pyramidal
77. According to Wade’s theory the anion [B12H12]2– adopts
(a) closo-structure (b) arachno-structure (c) hypo-structure (d) nido-structure
78. Considering the inert pair effect on lead, the most probable structure of PbR2[R =2. 6-C6H3(2, 6–
Pr2C6H3)2] is
R R
R
R
(a) Pb Pb (b) Pb Pb
R R R
R

R R
R R
(c) R Pb Pb (d) Pb Pb
R R R
8 PAPER : CSIR-UGC-NET/JRF June 2015

79. The reaction of SbCl3 with 3 equivalents of EtMgBr yields compound X. Two equivalents of SbI3
react with one equivalent of X to give Y. In the solid state, Y has a 1D-polymeric structure in which
each Sb is in a square pyramidal environment. Compounds X and Y respectively, are
(a) SbEt 3 and Sb  Et  I 2  n (b) Sb  Et 2  Cl and Sb  Et 2  Cl  n

(c) SbEt 3 and SbEt 2 Br2 n (d) Sb  Et  Br2 and SbEt  I  Br   n

80. Match the complexes given in column I with the electronic transitions (mainly responsible for their
colours) listed in column II
Column-I Column-II
(I) Fe(II)–protoporphyrin IX (A)   *
(II) [Mn(H2O)6]Cl2 (B) spin allowed d  d
(III)  Co  H 2 O 6  Cl 2 (C) spin forbidden d  d
(D) M  L charge transfer
The correct answe is
(a) I-A, II-C and III-B (b) I-D, II-B and III-C
(c) I-A, II-C and III-D (d) I-A, II-B and III-C

81. The following statements are given regardng the agostic interaction C H Ir observed in
[Ir(Ph3P)3Cl].
(A) Upfield shift of C–H proton in 1H NMR spectrum
(B) Increased acid character of C–H
(C)  CH in IR spectrum shifts to higher wavenumber
The correct answer is/are
(a) A and C (b) B and C (c) A and B (d) C only

Amongst the following (A)  Mn    Cp   CO 3  , (B)  Os    Cp  2  , (C)  Ru    Cp 2  and

5 5 5
82.

(D)  Fe    Cp  2  , the compounds with most shielded and deshielded Cp protons respectively, are
5

(a) D and A (b) D and B (c) C and A (d) C and B

83. [Link]
Tot al number of vert ices in metal clusters  Ru 6  C  CO 17  , Os 5  C  CO 15  and

 Ru 5  C  CO 16  are 6, 5 and 5, respectively. The predicted structures of these complexes, respec-
tively are
(a) closo, nido and nido (b) closo, nido and arachno
(c) arachno, closo and nido (d) arachno, nido and closo
84. Among t he complexes, (A) K 4  Cr  CN 6  , K 4  Fe  CN  6  , (C) K 3 Co  CN  6  and

K 4  Mn  CN  6  , Jahn-Teller distortion is expected in

(a) A, B and C (b) B, C and D (c) A and D (d) B and C
 PAPER : CSIR-UGC-NET/JRF June 2015 9

85. The reductive elimination of Ar–R (coupled product) from A is facile when
Ph Ph
P Ar
(A) Pd
P R
Ph
Ph
(a) R = CH3 (b) R = CH2Ph (c) R = CH2COPh (d) R = CH2CF3
86. The total number of metal ions and the number of coordinated imidazole units of histidine in the
active site of oxy-hemocyanin, respectively, are
(a) 2Cu2+ and 6 (b) 2Fe2+ and 5 (c) 2Cu+ and 6 (d) Fe2+ and 3
87. Match the action of H2O2 in aqueous medium given in column A with the oxidation/reduction listed
in column B
A : action of H2O2 B : type of reaction
3 4
(I) Oxidation in acid (A)  Fe  CN 6    Fe  CN  6 
4 3
(II) Oxidation in base (B)  Fe  CN 6    Fe  CN  6 

(III) Reduction in acid (C) MnO 4  Mn 2 

(IV) Reduction in base (D) Mn 2   Mn 4 
The correct answer is
(a) I-A, II-B, III-C, IV-D (b) I-B, II-D, III-C, IV-A
(c) I-C, II-D, III-B, IV-A (d) I-D, II-A, III-C, IV-B
88. The reduced form of a metal ion M in a complex is NMR active. On oxidation, the complex gives an
EPR signal with g||  2.2 and g   2.0 . Mossbauer spectroscopy cannot characteristic the metal
complex. The M is
(a) Zn (b) Sn (c) Cu (d) Fe
89. The least probable product from A on reductive elimination is
Ph Ph
P CH3
[Link]
P CH
M
3
Ph Ph
(A)
CH3
(a) H C CH3 (b) CH4 (c) H C CH3 (d)
3 3 H3C CH3
90. Water plays different roles in the following reactions.

(i) 2H 2 O  Ca  Ca 2   2OH   H 2 (ii) nH 2 O  Cl   Cl  H 2 O  n 
2
(iii) 6H 2 O  Mg 2   Mg  H 2 O  6  (iv) 2H 2 O  2F2  4HF  O 2
The correct role of water in each reaction is,
(a) (i) oxidant, (ii) acid, (iii) base and (iv) reductant
(b) (i) oxidant, (ii) base, (iii) acid and (iv) reductant
(c) (i) acid, (ii) oxidant, (iii) reductant and (iv) base
(d) (i) base, (ii) reductant, (iii) oxidant and (iv) base
10 PAPER : CSIR-UGC-NET/JRF June 2015

91. With respect to  and  bonding in Pt in the structure given below, which of the following
represent the correct bonding.
Ph
Ph3P C
Pt 1.32Å
Ph3P C
Ph

(a) M     L    and M     L  *  (b) L     M    and L     M   

(c) L     M    and L     M    (d) L     M    and M     L  * 

92. The complex  Fe  phen 2  NCS  2   phen  1,10  phenanthroline  shows spin cross-over behaviour
CFSE and µeff at 250 and 150K, respectively are
(a) 0.4 0 , 4.90 BM and 2.40 , 0.00 BM (b) 2.4 0 , 2.90 BM and 0.4 0 , 1.77 BM
(c) 2.40 , 0.00 BM and 0.4 0 , 4.90 BM (d) 1.2 0 , 4.90 BM and 2.40 , 0.00 BM
93. Consider the following statements with respect to uranium
(A) UO2+ disproportionates more easily than UO22+
(B) U3O8 is its most stable oxide of U
(C) Coordination number of U in  UO 2  NO 3  2  H 2 O 2   4H 2 O is six.
(D) UO22+ is linear
The correct set of statements is
(a) A, B and D (b) A, C and D (c) B, C and D (d) A, B and C
Et

(R3P)2Ni(1, 5-cyclooctadiene) Et Et
94. 2 Et Et , CO2

Et O O
For the above conversion, which of the following statements are correct?
[Link]
(A) CO2 combines with Ni(PR3)2 (1, 5-cyclooctadiene)
(B) Insertion of CO2 occurs
(C) Insertion of Et Et takes place
The correct answer is
(a) A and B (b) B and C (c) C and A (d) A, B and C
95. Consider the following statements for  NH 4 2 Ce  NO 3 6   Z 
(A) Coordination number of Ce is 12
(B) Z is paramagnetic
(C) Z is an oxidising agent
(D) Reaction of Ph3PO with Z gives a complex having coordination number 10 for Ce.
The correct statements are
(a) A, B and C (b) B, A and D (c) B, C and D (d) A, C and D
 PAPER : CSIR-UGC-NET/JRF June 2015 11

96. The major prouct formed in the following reaction sequence is

HO2C

O 1. (i) SOCl2, (ii) NaN3, MeOH

?
2. t-BuOK
3. H3O+

O
O

NH
(a) NH (b)
HO2C H
H
HO2C

HO2C
H H
N HO2C N
O O
(c) (d)

H H
97. The major proucts A and B in the following reaction sequence are
R

R=OH R=Me
(A) NaNH2
(B)
NaNH2
NH3(l) NH3(l)

Br
OH Me Me

(a) A = B= +
NH2 NH2
NH2 (1 : 1)
[Link]
OH Me

(b) A = B=
NH2
NH2

OH OH Me Me

(c) A = + B= +
NH2 NH2

NH2 (1 : 1) NH2 (1 : 1)
12 PAPER : CSIR-UGC-NET/JRF June 2015

OH Me

(d) A = B=
NH2 NH2

98. The major product formed in the following reaction is

AcO
p-TsNH-NH2

O NaBH3CN

AcO AcO AcO

(a) (b) (c) (d)

99. The major products A and B in the reactions sequence are

O O aq. KOH aq. KOH
r.t.
(A) reflux (B)
H2N + CO2Et
EtO2C
CO2H CO2H

(a) A = CO2Et
B=
CO2H
N N
H H
CO2H CO2H

(b) A = CO2Et
B=
N
H [Link]
N
H
CO2Et CO2H

(c) A = CO2H
B=
N N
H H
CO2Et

(d) A = CO2H
B=
N N
H H
100. The major products formed in the following reaction are
0.5 equiv. PhC(Me)2OOH
1.0 equiv. Ti(OiPr)4
OH 1.2 equiv. (–)–DIPT
OMe CH2Cl2, –20ºC
 PAPER : CSIR-UGC-NET/JRF June 2015 13

(a) A= B=
OH OH
OMe OMe
O

(b) A= B=
OH OH
OMe OMe
O

(c) A= B=
OH OH
OMe OMe
O

(d) A= B=
OH OH
OMe OMe
101. The correct statement about hte following reaction is
O

NH2
Br2
NaOH
N F
(a) The product is 2-fluoropyridin-3-amine and reaction involves nitrene intermediate
(b) The product is 2-fluoropyridin-3-amine and reaction involves radical intermediate
(c) The product is 2-hydroxynicotinamide and reaction involves benzyne-like intermediate
(d) The product is 2-hydroxynicotinamide and reaction involves addition-elimation mechanism

102. The major product formed in the following reaction is

Pd(OAc)2
OAc PPh3, Et3N
[Link]
CH CN 3
N Ph
H

Ph
Ph H
N

(a) N (b)
H

Ph HO
H
N

(c) (d) N Ph

H Ac
14 PAPER : CSIR-UGC-NET/JRF June 2015

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

Me Me
BrPh3P
KH
(A) (B)
THF n-BuLi, 0ºC
HO Me 18-crown-6, rt

Me Me
(a) A = Me CHO B = Me
Me Me
Me Me
Me CHO B = Me
(b) A =
Me Me

Me Me
(c) A = Me CHO B = Me
Me Me
Me Me
Me CHO B = Me
(d) A =
Me Me
104. The major products A and B formed in the following reactions are
O
1. PdCl2, CuCl
(i) Li, NH3(i) O2, DMF-H2O
(A) (B)
(ii) allyl bromide 2. ethanolic KOH

O
O O
OH

(a) A= B= O (b) A= B=

[Link]
H Me

O
O O
O
Me
(c) A= A= B= O
B= OH (d)
H

105. An organic compounds shows following spectral data:

IR  cm 1  :1680
1
H NMR  CDCl3  : 7.66  m, 1H  , 7.60 (m, 1H), 7.10  m, 1H  , 2.50  s,3H 
13
C NMR  CDCl3  : 190, 144, 134, 132, 128, 28 m/z (EI) : 126 (M+, 100%), 128 (M++2, 4.9%)
The structure of the compound is
 PAPER : CSIR-UGC-NET/JRF June 2015 15

OAc

(a) (b) (c) CO2Me (d)

O O S
O S O
106. The correct set of reagents to effect the following transformation is
O O
CO2Me

(a) (I) (i) NaOMe, MeI; (ii) NaCl, wet DMSO, 160ºC; (II) (i) LDA, –78ºC, TMSCl; (ii) t-BuCl,
TiCl4, 50ºC
(b) (I) (i) NaOMe, MeI; (ii) aq. NaOH then HCl, heat; (II) (i) Et3N, TMSCl, rt; (ii) t-BuCl, TiCl4,
50ºC
(c) (i) LDA, t-BuCl, (ii) LDA, MeI; (iii) aq. NaOH then HCl, heat
(d) (I) (i) NaCl, wet DMSO, 160ºC; (ii) NaH, t-BuCl; (II) (i) morpholine, H+ ; (ii) MeI then H3O+.
107. The correct structures of the intermediates [A] and [B] in the following reactions are

POCl3 Ph NH2
[A] [B]
N O N N Ph
H
H

(a) A = Cl B= Cl Cl
N OP(O)Cl2 N P
Cl
H H O

(b) A = B= Cl
N O N Cl
P(O)Cl2 [Link]
P(O)Cl 2

(c) A = Cl B=
N OP(O)Cl2
N Cl
H

A= B= Cl Cl
(d) N O N P
Cl
P(O)Cl2 H O
108. The correct reagent combination A and the major product B in the following reaction sequence are
O O O H2N-NH2
A
EtO2C EtO2C
B
16 PAPER : CSIR-UGC-NET/JRF June 2015

N N
(a) A : LiHMDS, AcCl B = EtO2C N (b) A : n-BuLi, AcCl B = EtO2C N
H H
OH OH
OH OH
(c) A : LiHMDS, AcOEt B = (d) A : n-BuLi, AcOEt B =
N N
N N
109. The major product of the following reaction sequence is
Br I NHAc OH

CO2Me
Pd(OAc)2 Pd(OAc)2
N
PPh3, Et3N PPh3, Et3N
Ts
CO2Me CO2Me
OH
(a) AcHN (b) AcHN

N N
Ts Ts

OH
CO2Me CO2Me

NHAc NHAc
(c) (d)
N N
Ts Ts
110. The major product formed in the following reaction is
[Link]
O
Me
Cp
Ti Al
O
Cp Cl Me
pyridine, toluene, –40ºC
H
O

COOEt
PhMe2Si
O O

PhMe2Si H PhMe2Si H
(a) (b)
EtOOC EtOOC
O O
 PAPER : CSIR-UGC-NET/JRF June 2015 17

O O

PhMe2Si H PhMe2Si H
(c) (d)
EtOOC EtOOC
O O
111. The major products A and B in the following synthetic sequence are
O

(i) PhMgBr, CuI NaOEt

Me (A) (B)
(ii) H3 O+ Br2

O O

Me CH2Br
(a) A = B=
Ph Ph

O O

Me CH2Br
(b) A = B=
Ph Ph

O O
Br
Me Me
(c) A = B=
Ph Ph

O O
Br

(d) A = [Link]
Me
B=
Me

Ph Ph
112. The major product formed in the following reaction is
O
hv, acetone

Me
O

Me Me
(a) (b) (c) (d)
O O
O
18 PAPER : CSIR-UGC-NET/JRF June 2015

113. The hydrocarbon among the following having conformationally locked chair-boat-chair form is
H H H H

(a) (b)
H H H H
H H H H

(c) (d)
H H H H
114. The major product formed in the following reaction sequence is
O
(i) (Boc)2O, pyridine
HO
(ii) TBSCl, Imidazole
NH2
(iii) LiAlH(OtBu)3
EtOH, –78ºC
OH OH

(a) TBSO (b) BocO

NHBoc NHTBS
OH OH

(c) TBSO (d) BocO

NHBoc NHTBS
115. The major product in the following reaction sequence is
O
N2 Me
OTIPS
hv, Me
vycor filter
ClCH2CH2Cl, 80ºC
Me Me
[Link]
Me Me
H
HO OTIPS O OTIPS

H
(a) (b)

Me Me Me Me

HO OTIPS HO OTIPS

(c) (d)
 PAPER : CSIR-UGC-NET/JRF June 2015 19

116. Structures of A and B in the following synthetic sequence are

O
(i) Ph3P CHCO2Me (i) LiAlH4
AcO N CHO (A) (B)
H (ii) heat (ii) H3O+

CO2Me
(a) A = N
B=
N
OAc
O O

H H

(b) A = CO2Me
B= CH2OH
N N

O O
H H
(c) A = AcO N B = AcO N
H H
HOH2C HOH2C

H H

(d) A = N CO2Me
B=
N CH2OH

O O
117. In the following reaction, the ratio of A : B : C is (*indicates labelled carbon)
Br Br Br
NBS *
* AlBN *
+ +
CCl4
heat [Link]
*
(A) (B) (C)
(a) 1 : 1 : 1 (b) 1 : 2 : 1 (c) 2 : 1 : 1 (d) 3 : 2 : 1
118. Structure of the major product in the following synthetic sequence is
CO2Me

(i) CuI
(ii) SeO2
N2

H OH H
Me Me
(a) HO (b)
H CO2Me H CO2Me
20 PAPER : CSIR-UGC-NET/JRF June 2015

OH H HO H
Me Me
(c) (d)
H CO2Me H CO2Me
119. Major product formed in the following synthetic sequence on the monoterpene pulegone is
(i) Br2
(ii) NaOEt, EtOH
(iii) KOH, EtOH
O

COOH

CO2H O
(a) (b) (c) (d)
HO

OEt
120. Optically pure isomers A and B were heated with NaN3 in DMF. The correct statement from the
following is
NMe2 NMe2 NMe2 NMe2

Br Br N3 N3
(A) (B) (C) (D)
(a) A gives optially pure D and B gives optically pure C
(b) A gives racemic mixture of C and B gives optically pure C
(c) A gives optically pure C and B gives racemic C
(d) A gives optically pure D and B gives racemic D
121. A molecular orbital of a diatomic molecule changes sign when it is rotated by 180º around the
molecular axis. This orbital is
(a)  (b)  (c)  (d) 
122. [Link]
IR active normal modes of methane belong to the irreducible representation:

Td E 8C3 3C2 6S 4 6 d
A1 1 1 1 1 1 x2  y 2  z 2
A2 1 1 1 1 1
E 2 1 2 0 0 2 z 2  x2  y 2 , x 2  y 2
T1 3 0 1 1 1 Rx , Ry , Rz
T2 3 0 1 1 1 x, y , z , xy, yz , zx

(a) E  A1 (b) E  A2 (c) T1 (d) T2

123. The symmetric rotor among the following is
(a) CH4 (b) CH3Cl (c) CH2Cl2 (d) CCl4
 PAPER : CSIR-UGC-NET/JRF June 2015 21

124. The nuclear g-factors of 1H and 14N are 5.6 and 0.40 respectively. If the magnetic field in an NMR
spectrometer is set such that the proton resonates at 700 MHz, the 14N nucleus would resonate at
(a) 1750 MHz (b) 700 MHz (c) 125 MHz (d) 50 MHz
125. The spectroscopic technique, by which the ground state dissociation energies of diatomic molecules
can be estimated, is
(a) microwave spectroscopy (b) infrared spectroscopy
(c) UV-visible absorption spectroscopy (d) X-ray spectroscopy
126. The term symbol for the first excited state of Be with the electronic configuration 1s2 2s1 3s1 is
(a) 3S1 (b) 3S0 (c) 1S0 (d) 2S1/2
127. Which of the following statement is INCORRECT?
(a) A Slater determinant is an antisymmetrized wavefunction
(b) Electronic wavefunction should be represented by Slater determinants
(c) A Slater determinant always corresponds to a particular spin state
(d) A Slater determinant obeys the Pauli exclusion principle
128. Compare the difference of energies of the first excited and ground states of a particle confined in (i)
a 1-d box  1  , (ii) a 2-d square box   2  and (iii) a 3-d cubic box  3  . Assume the length of each
of the boxes is the same. The correct relation between the energy differences 1 ,  2 and 3 for the
three states is
(a) 1   2  3 (b) 1   2  3 (c) 3   2  1 (d) 3  1   2

129. The correct statement about both the average value of position  x  and momentum  p  of a 1-
d harmonic oscillator wavefunction is
(a) x  0 and p  0 (b) x  0 but p  0

(c) x  0 and p  0 (d) x  0 but p  0

130. The value of the commutator  x,  x, p x  is
(a) ix (b) i (c) i (d) 0
131.  CO 2  g   4H 2  g  and
The equilibrium constants for the reactions CH 4  g   2H 2 O  g  
[Link]
 CO 2  g   H 2  g  are K and K , respectively. The equilibrium constant for
CO  g   H 2 O  g   1 2

 CO  g   3H 2  g  is
the reaction CH 4  g   H 2 O  g  
(a) K1  K 2 (b) K1  K 2 (c) K1 / K 2 (d) K 2  K1
132. Consider the progress of a system along the path shown in the figure S  B  C  for one mole of an
ideal gas is then given by
A(T1, V1)

Adiabatic
process
P

C(T3, V1) B(T2, V2)

V
T1 T3 V2 V1
(a) R ln T (b) R ln T (c) R ln V (d) R ln V
3 1 1 2
22 PAPER : CSIR-UGC-NET/JRF June 2015

133. A thermodynamic equation that relates the chemical potential to the composition of a mixture is
known as
(a) Gibb’s-Helmholtz equation (b) Gibbs-Duhem equation
(c) Joule-Thomson equation (d) Debye-Huckel equation
134. According to transition state theory, the temperature-dependence of pre-exponential factor (A) for a
reaction between a linear and a non-linear molecule, that forms products through a non-linear tran-
sition state, is given by
(a) T (b) T 2 (c) T–2 (d) T–1.5
135. For a given ionic strength, (I) rate of reaction is given by
k 1/ 2
log  4  0.51 I  . Which of the following reactions follows the above equation?
k0

(a) S2 O82   I  (b) Co  NH 3 5 Br 2  OH 

(c) CH 3COOC 2 H 5  OH  (d) H   Br   H 2 O 2

136. For a reaction on a surface

H H
H2 + S S S S
H H H
slow
S S S + H
S
At low pressure of H2, the rate is proportional to
1/ 2 1/ 2
(a)  H 2  (b) 1/  H 2  (c)  H 2  (d) 1 /  H 2 
137. The temperature-dependence of an electrochemical cell potential is
G H S S
(a) (b) (c) (d)
nFT nF nF nFT
138. The single-particle partition function (f) for a certain system has the form f  AVe BT . The average
energy per particle will then be (k is the Boltzmann constant)
(a) BkT [Link]
(b) BkT 2 (c) kT / B (d) kT / B2
139. The indistinguishability correction in the Boltzmann formulation is incorporated i the following way
: (N = total number of particles, f = single-particl partition function)
(a) replace by f/N! (b) replace fN by fN/N!
(c) replace f by f/ln(N!) (d) replace by fN by fN/ln(N!)
140. In a photochemical reaction, radicals are formed according to the equation
 2C 2 H 5
C4 H10  h 
k2
C2 H 5  C 2 H 5   C2 H6  C2 H4
If I is the intensity of light absorbed, the rate of the overall reaction is proportional to
1/ 2
(a) I (b) I1/2 (c) I  C4 H10  (d) I1/ 2  C 4 H10 
 PAPER : CSIR-UGC-NET/JRF June 2015 23

141. Conductometric titration of a strong acid with a strong alkali (MOH) shows linear fall of conduc-
tance up to neutralization point because of
(a) formation of water
(b) increase in alkali concentration
(c) faster moving H+ being replaced by slower moving M+.
(d) neutralization of acid.
142. Find the probability of the link in polymers where average values of links are (A) 10, (B) 50 and (C)
100
(a) (A) 0.99, (B) 0.98, (C) 0.90 (b) (A) 0.98, (B) 0.90, (C) 0.99
(c) (A) 0.90, (B) 0.98, (C) 0.99 (d) (A) 0.90, (B) 0.99, (C) 0.98
143. The stability of lyophobic colloid is the consequence of
(a) van der waals attraction among the solute-solvent adducts
(b) Brownian motion of the colloidal particles
(c) insolubility of colloidal particles in solvent
(d) electrostatic repulsion among double-layered colloidal particles
144. In a conductometric experiment for estimation of acid dissociation constant of acetic acid, the fol-
lowing values were obtained in four sets of measurements.
1.71 10 5 , 1.77  10 5 , 1.79  10 5 and 1.73  105
The standard deviation of the data would be in the range of
(a) 0.010  105  0.019  105 (b) 0.020  105  0.029  105
(c) 0.030  105  0.039  105 (d) 0.040  105  0.049  105
145. Silver crystallizes in face-centered cubic structure. The 2nd order diffraction angle of a beam of X-ray
   1Å  of (111) plane of the crystal is 30º. Therefore, the unit cell length of the crystal would be
(a) a = 3.151Å (b) a = 3.273 Å (c) a = 3.034Å (d) a = 3.464 Å

[Link]