Detailed Solution

CSIR-UGC-NET
CHEMICAL SCIENCES

June 2011 – Dec 2019

CHEMICAL SCIENCES

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SOLUTION
June 2011 – June 2019
280 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011

SOLVED PAPER : CSIR-UGC-NET/JRF June 2011

CHEMICAL SCIENCES BOOKLET-[C]

PART - B

21. Ni 2   Ar 3d8 4s 0 

3d 4s 4p 4d
Geometry Possible hybridisation No. of unpaired electrons
Octahedral sp3d 2 2
Square planar d sp 2 0
Tetrahedral sp3 2

Correct answer: (d)

22. Compound Hybridisation of Ni 2 Number of unpaired electrons

2
 Ni  CN 4  dsp 2 0  diamagnetic 
2
 NiCl4  sp3 2  paramagnetic 

Correct answer: (c)

23. M S C N , M N C S

CN bond stretching CN bond stretching at lower

at higher frequency frequency(wave number)
(wave number)
Correct answer: (b)
24. Charge transfer spectra are possible due to transfer of electron from ligand to metal. This is more
[Link]
probable if the metal is in a high oxidation state or ligand has reducing properties. Intense colour of
ceric ammonium nitrate,  NH 4 2  Ce  NO 3 6  is due to charge transfer from bidentate NO3 to Ce 4
which has C.N = 12.
Correct answer: (b)
25. Structure of above compounds can be represented as

F –
F –
F F F Cl Cl
S B Xe I
F
F F F Cl Cl
F F F

(1 l.p.) (0 l.p.) (2 l.p.) (2 l.p.)

Correct answer: (a)

 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011 281

26. (a) O2 must be removed as it give its own polarogram, due to following reactions,
 H 2 O 2 ; O 2  4H   4e  
O 2  2H   2e    2H 2O
(b) Dropping mercury electrode is the working electrode
(c) Id  C
(d) Residual current need not to be made zero.
Correct answer: (d)
27. Vitamin B12 molecule is built-around a corrin ring containing cobalt (III) atom.
Correct answer: (b)
28. For rotational spectra,   0
Molecule Dipole moment    Rotational spectra
H2 0 No
N2 0 No
CO 0 Yes
CO2 0 No
Correct answer: (c)

29. Ziegler-Natta catalyst is Al  C 2 H 5 3  TiCl4 .

Correct answer: (a)

30. Compound Number of electron in outer shell of central atom

   C H  Fe
5
5 5 2 18

   C H  Co
5
5 5 2 19

   C H  Ru
5
5 5 2 18

   C H  Co
5
5 5 2

18

Oxidation of   5
 C 5 H 5  Co to  5  C 5 H 5  Co  gives an 18 electron compound, so easier to
[Link]
2 2

oxidise.
Correct answer: (b)

CH3
31. H3C CH3
W Cl

H3C CH3 Fe K+ Cl Pt Ru
CH3
Cl
W(CH3)6

(Only 6-bond with metal)

Correct answer: (a)

282 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011

32. O N C
H H
H H H H H H

Bond angle: 104.5º 107º 109.5º

Shape: Bent/angular Pyramidal Tetrahedral
Hybridisation sp3 sp3 sp3

Bond length order: O H < N–H < C–H

Correct answer: (c)

C C C
33.
F F F F F F
Stabilisation via back-bonding. Due to innert pair effect stability of +2 oxidation state increases
down the group.
Correct answer: (b)
34. Isomers of [Ru(bpy)2Cl2] can be represented as

II and III are enantiomers.

Correct answer: (b)
19  e0 Positron
1    e0  particle
1  
35.  19 ; 14 14

[Link]
10 Ne  9 F 6 C  7 N

Correct answer: (b)

36. Kurnakov test is used to distinguish between cisplatin and transplatin, by using thiourea as a reagent.
Cisplatin + Aqueous thiourea deep yellow solution
Crystallisation

yellow needle shape crystal

of tetrakis(thiourea) platinum (II)
chloride

Transplatin + Aqueous thiourea Colourless solution

Crystallisation

white needle shape crystal of

trans-bis(thiourea)diaammine
platinum (II) chloride
Correct answer: (c)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011 283

2 2 2 2 1 1

37.
1  1  
Given electronic configuration of the molecule is 
 2   2  
g 1  1 
u g u u u

Closed shell Valence shell

• Only valence shell is considered while writing term symbol.

2s 1   or – 
Term symbol is,   g or u 

here     1  1 1  0  
1 1
s  1
2 2
Or, 2s  1  3
Reflection under plane containing nuclie = (–) × (+) = (–).
and u×u = g
3 
 term symbol,  g

Correct answer: (b)

dq
38. From Clausius inequality, dS 
T
dq
Or, dS 
0 ... (1)
T
At constant volume, dw = – PdV = 0
Therefore, from first law of thermodynamics,
 dq  du  dw ; dq = du  dw  0
At constant entropy ds = 0,
Therefore, from equation (1), we get
dU s,v
 0
T
or dU s,v  0
Here equality holds only for reversible process.

dU s,v  0
[Link]
For spontaneous process,

or Us,v  0
Correct answer: (c)
k
39. For zero order reaction, A  P

d A 0
  k A  k   A0  k 
dt  
On integration and putting proper limit we get,
 A 0   A   kt ... (1)

 A 0
at t  t 12 and  A  
2
From equation (1), we get
284 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011

 A 0  A 0
  k t 1 2  t1 2 
2 2k
Correct answer: (a)
40. For an aquous solution at 25ºC, the Debye-Hückel limiting law is
log     A Z  Z  µ

log    0.509 Z  Z  µ  A  0.509

Correct answer (c)
41. For an asymmetric top, I x  I y  Iz
Therefore, Total energy (E) = E x  E y  E z

J 2x J 2y J 2y  J 
  
2I x 2I y 2I z  E  2 I 
 
So, above equation will give three rotational constants, Bx , By & Bz .
Correct answer: (c)
42. Q-band (or PQR contour) is obtained for the bending vibration of C2H2 when its linearity is lost.
Correct answer: (c)

43. • The degeneracy associated with the quantum number  M J  (the orientation of the rotation in
space) is partly removed when an electric field is applied on a polar molecule (eg. HCl, NH3,etc)
• This splitting of states by an electric field is called Stark Effect.
• For any linear molecule (eg. AX or BX) in electric field (E), the energy of the state with quantum
number J and MJ is given by,
E  J, M J   hc B  J  J  1  a  J, M J  2 E 2

here energy depends on  2  square of dipole moment  , so large   dipole moment  will cause larger
splitting.
  AX   BX
Correct answer: (b) [Link]
44. For Langmuir adsoption (Monolayer, only), 
1.0
kp 0.9
=1 (zero order)

Coverage()

0.8
1  kp high pressure
0.7
0.6  = kp/(1+kp)
0.5
At lower pressure , kp << 1 0.4
So, that   kp    p  = kp (first order)
0.3
0.2
At high pressure, kp >>1 Low pressure
0.1

  1 (Independent of p) pressure 
As Langmuir assumed that binding at a site has no influence on the properties of neighbouring sites;
this means that enthalpy of adsorption is independent of coverage.
Correct answer: (a)

45.  C  g 
A  s   B  g  

G 0  G 0  product   G 0  reactant 
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011 285


G 0  G 0f  C   G 0f  A  G 0f  B  
 0  0  0  0  In standard state G 0f  0 

 G 0  0
Or, RTnK p  0
Or, nK p  0

Or, Kp  1
Kp = 1 is possible when, partial pressure of B (PB) is equal to partial pressure of C (PC),
i.e. PB  PC  3 atm and Ptotal = PB + PC = 6 atm.
Correct answer: (c)
46. As per B.O. approximation we can consider the two different motions independent if their energy
difference is large. In other words if energy difference of two different motions is large, the coupling
between them will be minimum.
In case of AX the energy difference of vibrational and rotational energy is large compared to
BX. Hence coupling will be stronger in BX.
Correct answer: (a)
47. • The entropy of a compound is related to the number of ways in which the molecules can be
distributed among different energy states; the greater the number; the larger is the degree of
disorder, i.e. larger is the entropy.
• According to Boltzmann distribution, larger, the energy difference w.r.t. ground state lower will
be population in exited state.
n exited
 e / kT , here  = ex  gs
n ground
 ex  Bhc , so higher the value of B, lower will be population in different exited state (i.e.
lower disorder or entropy)

1  h2 
B ,  B 
•
I  82 I 
[Link]
BO 2  B N 2  B D 2  B H 2

Srot for O2 is highest.
Correct answer: (b)
48. True normalised wave function for 1s orbital of H-atom is given by
3
2
1  1   r a0
1s    e and E1s  0.5 atomic unit
  a0 
2
12 1 1.24  1 1
Since, E1s   2
    1.5625    1.6  0.8
2n 2 1 2 2
So, 0.8  0.5
Correct answer: (c)
286 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011

49. A is constant of motion (i.e., does not change with time) if

d 1 ˆ ˆ ˆ
A
If, dt A  i A, H   t  0

 Â  1 ˆ ˆ
If  is time independent  i.e., t  0  then, for  to be constant of motion, A,H  0
  i  

Or, ˆ ˆ 0
A,H
 
ˆ H
Note: If  A, ˆ   0 , then also we can say A is a constant of motion.

Correct answer: (b)
50. Hermitian conjugate or adjoint of an operator  is written as † , and is defined as
† *
 d   d  d
    
 dx   dx  dx
Correct answer: (a)

 T 
51. For ideal gas, Joule-Thomson coefficient   JT    P   0 . So we can not produce cooling or
 H
heating by expansion under isoenthalpic process.
Under the given process,
PV a  constant ... (1)
For ideal gas, PV  nRT ... (2)
Replacing P from equation (2) in (1), we get
TV a 1  constant
a 1
or, TV
1 1  T2V2a 1
a 1
T2  V1 
  
T1  V2 
T  V 
 log  2    a  1 log  1   V  V 
 T1  [Link]
... (3)
 V2 
2 1

Now, in equation (3)

V 
 log  1    ve
 V2 
So far T2  T1  heating 
T2
 log   ve
T1
a must be less than 1. Also expansion causes decrease in pressure of gas, this is possible for a > 0, as
PV a  constant .
Correct answer: (c)
52.  y 2  4x ... (1)
After 1% increase in value of x,
y  4x
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011 287

y  2 x½
y 1 x
100   100
y 2 x
% error in y = ½ ×% error in x.
= ½ × 0.1 = 0.05.

Correct answer: (d)

(3)
(3) (4)
3
Me
53. (4) 1
(2) (1) O
(1) 3 2
(2) 4
H 2
1R-Configuration 1 4R-Configuration
4

Correct answer: (a)

180º
O O
Me Me

54.
H H

Correct answer: (b)

55. Chemical reaction involved in the above transformation can be illustrated as

SH S
BF3.Et2O
O +
SH S

OHBF3 HS

O .......BF3 [Link]

OBF
–H
HS
–H
3 S

HS
SH S
HS
SH S

S
Correct answer: (a)
56. Chemical reaction involved in the above transformation can be illustrated as
O
O OH
[3, 3]
sigmatropic
rearrangement
 H Ortho-allyl phenol
aryl allyl ether
Correct answer: (a)
288 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011

57. Chemical reaction involved in the above transformation can be illustrated as

H
O O O
Na2CO3 I2/KI
O
OH O O O
I H
I
Correct answer: (a)

58. Chemical reaction involved in the above transformation can be illustrated as

OLi O
O

e–(NH3)x NH3 Me
Me Me
Me Me Me Me Me
Me
Correct answer: (d)

59. Chemical reaction involved in the above transformation can be illustrated as

Me Me
H Me Me
H
N2 H H
hv Me Me

Carbene
(Intermediate)

Correct answer: (d)

60. 1, 3-trans-disubstitution = a, e substitution.
At C–1 - equatorial -t-Bu; At C–3 - axial - methyl group.
Larger substituent always prefer equatorial position. Hence, correct conformation can be repre-
sented as
CH3
H3C H
2
[Link]
H3C 1 3
CH 3
Most Stable
Correct answer: (c)
H H

+ +
61. H H
H
H

(A) Homoaromatic character

(A romatised by bypassing the sp3-carbon atom)
(+)

(B) + (C) +

• Delocalisation • Delocalisation
• sp2 - carbons (planar)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011 289

• 4n = 4 (  - electron) • (4n+2) = 2 (  -electron)

n=1 n=0
• Antiaromatic character. • Aromatic character.
Correct answer: (a)

62. Because C–O of anhydride = 1800 –1900 cm–1.

C–O of ketone = 1720 cm–1. C–O of amide = 1600–1700 cm–1.
Correct answer: (d)
63. Because the ease of elimination increasing with increased size and branching in the radical.
Correct answer: (b)
64. Chemical reaction involved in the above transformation can be illustrated as
1
H
5 5 1
Me [1, 5]H shift 4 H Me
4 
1
(Sigmatropic
rearrangement) 3 Me
3 2 2
Correct answer (c)

R R
– R R R R
65. hv R R
LUMO + R R
 R R R R
R R
HOMO
alkene
hv

– HOMO Cycloaddition

HOMO

[Link]
LUMO

Correct answer: (b)

66. Chemical reaction involved in the above transformation can be illustrated as

H H H
R C
BH3 + –
CH2 R C CH2 R C CH2 BH2 R C CH2
H H H BH2
H BH
Syn-addition (H & BH2–Syn
(Markovnikov) addition)
More Stable T.S.

Correct answer: (c)

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67.  max  279 is n–* , which can be differentiated by low  15

Correct answer: (b)

68. Chemical reaction involved in the above transformation can be illustrated as

MeO NO2 MeO NO2 NO2

H H
NaOEt
E1CB

Carbanion
(Stable)

Correct answer: (d)

69. Chemical reaction involved in the above transformation can be illustrated as
O O

H2O2
 HOO 
H 2O 2  NaOH   H 2O
NaOH O Soft Nucleophile 

Me Me
Mechanism:

O O O

+ OOH O
O OH
Me Me Me
Correct answer: (d)

I (+) OR
Solvent

70.
[Link] (ROH)

A 2º Carbocation
(sp2)

I OR
slow (ROH)

B sp2

I OR
NGP ROH
O
O Fast O

C (NGP-Anchimeric
Stable assistance in ionisation)
Correct answer: (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011 291

PART -C
71. Alkali metals in liq. NH3 act as source of electrons and are supposed to be a good one-electron
reducing agents.
 –
  M  NH 3  x    e  NH 3  y 
M   x  y  NH 3 
These solvated electrons can reduce O2 molecule to superoxide ion.

 O 2  yNH 3
 e  NH 3  y   O 2 
These superoxide ions can combine with solvated metal ion to give Alkali metal superoxides.

 M  NH 3 x   O 2 
 MO 2  xNH 3
Correct answer: (a)
4 3
  II     III  
72. H 2 O 2 oxidise, Fe to Fe ,  Fe  CN 6  to  Fe  CN 6  , NH 2 OH to HNO3 ,SO32 to SO24
2 3

   
H 2O 2 reduce KMnO 4 , KIO 4 ,Ce  SO 4 2 [All are stronger O.A. than H2O2)

Note: In the question, only I7 and Ce 4 are in their highest oxidation states, so the only possibility
of reduction by H2O2 exists.
Correct answer: (b)
73. Compound Uses

(A) Na 3 PO 4 Water softener, paint stripper

(B) Ar3 PO4 Plasticizers
(C) Et3 PO4 Insecticides
(D) CaHPO 4 .2H 2 O Toothpaste
Correct answer: (a).
74. (A) Correct, As 4f-electrons are too well shielded to interact, so they are like inert gas-type ion,
like those of alkaline earth metals, that attracts ligands only by overall electrostatic forces.
(B) Correct, Lanthanides, owing to the unavailability of orbitals for bonding, high basicity and
rather large size of Ln+3, form few complexes and mostly with oxygen or oxygen plus
[Link]
nitrogen chelating ligands such as   dietones, hydroxy acids EDTA etc. So, they
rarely show isomerism and also lability of ligands make the isolation of isomers is
difficult.
(C) Incorrect, C.N. more than 8 are common, due to their larger size and smaller chelating ligand
like, NO 3 , SO 42 etc.
2
eg.  Ce  NO3 6  , C • N  12
(D) Correct, As 4f electrons are well shilded from external fields by the overlying 5s and 5p elec-
trons. Thus the magnetic effect of orbital motion is can not be neglected.
Correct answer: (a)
292 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011

O –1/2

75. F
S O
F S
Cl
S • O O –1/2 S S
•
F –1/2 O Cl Cl O
F –1/2 Cl
–1/2 (S2Cl2)
(SO42–) distorted tetrahedral
(SF4) (Because all bonds are
Tetrahedral bent shape around not equivalent, so repulsion
Sea-Saw both s-atom will be different between
different bonds.)

Correct answer: (b)

2
76. For a d5 octahedral complex  Mn  H 2O 6  , all transitions are Laporte forbidden (orbital forbid-
den) as well as spin forbidden. Absorptions associated with doubly forbidden transi-
tions are extremely weak, so it is very lightly coloured.
Correct answer: (d)
77. X-axis as internuclear axis.
N 2  1s2 1s*2  22s *2 2 2 2 2 *2 2 *2 2 2 2 *1 *1
2s  2p x  2p y  2p z ; O 2  1s 1s  2s  2s  2p x  2p y  2p z  2p y  2p z

Correct answer: (a)

78. In the given case ligand in same, so higher the formal oxidation state of the metal, lower will be
LMCT, So, order is MnO 4  CrO 42  VO34
Correct answer: (a)
79. Carboxypeptidase enzyme contains Zn+2 ion and it cleaves (hydrolyses) the carboxy terminal amino
acid from a peptide chain.
Correct answer: (b)
80. g ||  g   g e , gives the evidence that Cu+2 ion is present in tetragonally distorted octahedral field.

[Link]
ground state

3d

octahedral field
Tetragonally disorted
octahedral field
Correct answer: (b).
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011 293

81. Oxidation of metal is easier for electron rich systems, so electron rich metals undergo oxidative
addition and as reduction is easier for electron-deficient metal, so it undergoes reductive elimina-
tion.
Correct answer: (d)

82. Ti  i  Pr  4  TiEt 4  TiMe 4  Ti  CH 2 Ph  4 . This is correct stability order because Ti  CH 2 Ph 4

has no  - elimination but Ti  i  Pr 4 has more  - elimination. More  - elimination less stable.
Correct answer: (c)
1 atm
Ni  4CO 
25ºC
 Ni  CO 4
83. 200 atm
Fe  5CO 
200ºC
Fe  CO 5
Correct answer: (c)

84. Shape Number of lone pair

O C O Linear 4
–
I — I — I Linear 9

N
O O
Angular 6

O N O Linear 4

Correct answer: (b)

85. For, Cu 2  2e 
 Cu, E 0  0.34V

1
0 0.059 1 0.059 635  103
E cell  E cell  log 2  0.34  log
2 Cu  2 63.5 g/mol  0.1 Lit

0.054
 0.34  log10 = 0.31 volt.
2
[Link]
So, when Ecell = 0.31 volt will reach, then deposition of Cu will start.
For Ag   e 
 Ag , E0 = 0.50V
On completion of this reaction,
0.059 1 0.1 103
E cell  E 0cell  log 
[Given :  Ag 
 
1  Ag    108  0.1 ]

1
0.059 3
E cell  0.50  log 0.1 10 = 0.203 volt
1 108  0.1
So, we will have to fix cathode potential above 0.31 volt so that no. Cu is deposited at the cathode.
We can not reduce the potential upto 0.203 V. So, that all Ag+ has been deposited.
Correct answer: (c)
294 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011

OC
OC CO

Ru H
OC CO
OC CO
Ru Ru
OC CO
H

CO
86. OC Ru Ru
CO
OC
OC CO
Ru
OC
CO CO

86-electron cluster H 2 Ru 6  CO 18 displays a distorted octahedral metal geometry..

Here each hydride ligand is connected to 3-Ru atoms.
Correct answer: (d)
87. During hydroformylation the intermediate CH3–CH2–CH2–Co(CO)4 gets transformed to acyl inter-
mediate CH 3CH 2 CH 2 – COCo  CO 3 .
Correct answer: (a)
88. As we move from 2nd row transition element (Zr) to 3rd row transition element (Hf), size should
increase, but due to lanthanide contraction offset the increase, so Zr and Hf have almost similar size.
Correct answer: (a)
89. SnF4 is ionic, here Sn+4 = 5sº, so no quadrupole splitting.
SnCl4 is covalent, and Sn is sp3 hybridised, So there is S-electron density in the molecule.
 quadrupole splitting is possible.
R3SnCl is covalent, and Sn is sp3, so there is S-electron density in the molecule.
 quadrupole splitting is possible.
Correct answer: (c)
[Link]
90.  

 
Cr+2 Co+3 Cr+2 Ru+3

Large reorganisation for Co+3 Reorganisation of Ru+3 less

outer sphere, so inner sphere than CO+2, so, slower tendency to go
much faster inner sphere
+2 +2
HOMO =  (of Cr ) HOMO =  (of Cr )
+3 +3
LUMO =  (of Co ) LUMO =  (of Ru )
Acceleration IS/OS=1010 Acceleration IS/OS=102
Inner sphere mechanism is favorable for totransition only
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011 295

As Cr 2 / Ru 3 has * to * transition which is responsible for its slower acceleration in going from
outer sphere mechanism to inner sphere mechanis.
Correct answer: (b)
91. Both Fe(II)–TPP and Fe(III)–TPP are square planar (because of tetradentate-planar, porphyrine type
ligand), and both Fe(II) and Fe(III) are dsp2–hybridised, so there is s-electron density, which is re-
sponsible for their quadrupole moment and existence of mossbauer spectra.
So both Fe(II)-TPP and Fe(III)-TPP show increase in s-electron density, but Fe(II) has higher
s-electron density. So Fe(II) has isomer higher shift (0.52 mms–1) than Fe(III) (0.45 mms–1).
Correct answer: (b)
1 k
92. As frequency of vibration  2  ;
where k = force constant of bond
µ= reduced mass.
 Ratio of frequency/wave number of Co–D and Co–H bond is,
60  1
Co– D  Co– D 61  1
 
Co2H  Co–H 60  2 2
62
1840
 Co –D  Co– H / 2   1300 cm1
2
Correct answer: (a)
93. Due to Jahn-Teller distortion.
Correct answer: (d)
94. B2 O 3  3H 2O 
 2H 3BO3 (orthoboric acid)
N 2 O 5  H 2 O 
 2HNO3 (Nitric acid)
SO 3  2H 2 O 
 H 2SO 4 (Sulfuric acid)
P4 O10  6H 2 O 
 4H 3 PO 4 (orthphosphoric acid)
Correct answer: (b)
[Link]
235 1 142
95. 92 U  n 
0  56 Ba  91 1
36 Kr  30 n

Energy released per atom (E) =  m  c 2 .

  mu  mn    mBa  mKr  3m n  c 2
2
E   235.0435  1.00866   141  9164  90.9234  3  1.00866  1.67  1027   3  108  J

Therefore, E  per atom   2.8  10 11 J  1 amu  1.67  10 27 kg , c  3  108 m/s 
235
 Energy released from 1 mole disintegration of 92 U  E  Per mole 
 E  per atom   N A  2.8  1011  6.023  1023
 1.68  1013 J  1.68  1010 kJ
Correct answer: (d)
296 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011

k
96. Acetaldehyde (CH3CHO)   product, rate = k[CH3CHO]2.
2
In terms of partial pressure , rate = kPCH 3 CHO

1 1
Integral rate law expression is, P  0  kt
CH3 CHO PCH3CHO

1
Or, t 12  0
k  PCH 3 CHO

0
Since given t = 400 sec and PCH3CHO
 250
1
400 sec   k  105 Torr 1s1
k  250 Torr
0
and PCH 3CHO
 200 Torr

1 1
Then t 12  0
 5
 500 sec
kP CH3 CHO 10  200
Correct answer: (d)

97. From enzyme kinetics, R  k 2  E 0 s 0

k m  s 0
1  km  1 1
   
R  k 2  E 0  S0 k 2  E 0
  
 
Slope Intercept


1 km
slope =
R k2[E0]
[Link]
1
intercept = k [E ]
2 0

1 
[S]0

We know that,
k2 1 1 1
Catalytic efficiency = k     107
m k m
 E 0
Slope   E 0 40  2.5  10 9

k 2  E 0
Correct answer: (c)
98. Given for any H-orbital
Radial function has form r  exp   r  and  -part has form exp  3i .
From the solution of Schrodinger equation for H-atom,
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011 297

1  im
We get  part  e ; where m is integer = 0, 1, 2, 3, ...............
2
1 im
 e . (Here m can be +ve or –ve integer including zero).
2
From given   part , m can be either +3 or –3.
Option (a)  incorrect, for n  4  let n  5 

  3 let   5  this is not possible
m3 

Option (b)  correct,for n =4,   3 , m = –3 (Can be possible solution)
Option (c)  incorrect, for n = 4, l > 3 (let 4), m = 3 (Can not be possible)
Option (d)  incorrect, for n > 4, l = 3, m = –3
for n > 4, l can be upto 4. (So not possible)
Correct answer (b)
2
99. Standard deviation in speed  V2  V

2 2
 rrms  Vavg

3RT 8RT  8  RT  8  RT
   3    3 
M M   M   M

RT RT
 0.67  0.7
M M
Correct answer: (a)

100. Second order perturbation for nth state is given by,

2
  0m H1  0n 
E n   
2
0 0
m n E n  Em
[Link]
Therefore, perturbation for ground state, (i.e., n = 0)
2 2
 10 H '  00   0 0

E 0 
2
     2 H ' 0 
E 00  E10 E 00  E 02
2 2
 V10   V20  22 42
     2   4   6
E 00  E10 E 00  E 02 02 04
Correct answer: (a)

1
101. n A1   6  1   2  1  3   3  1 0    2
6
1
n A2   6  1   2  1  3   3  1 0    2
6
1
nF   6  2    2  1 3    3  0  0    1
6
298 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011

T  2A1  2A 2  E
Correct answer: (a)
102. The direct product of two energy state should transform according to x, y or z axis for electronic
transition.
A1  A1  A1  transform with z axis = allowed
A1  E  E  Transform with x,y axis = allowed
A 2  E  E  Transform with x,y axis = allowed
A1  A 2  A 2  Not transform as per x,y or z = forbidden
Correct answer: (d)
103. 64 Gd   Xe  4f 7 5d1 6s 2 , Gd 2   Xe  4f 7 5d1 6s 0
Removal of electrons takes place from the outermost orbital only.
Correct answer: (d)
104. For 3D
2S + 1 = 3, 2S = 3–1 For term, S, P, D, F
2S = 2, S = 1 Value of L= 0, 1, 2, 3
S = 1, L = 2
J can have values from |L+S| ........... |L–S|
|2+1| ............ |2–1|
3 2 1
Correct answer: (b)

105.

Energy

Delocalisation energy =  2    2   2   4      = 0
Correct answer: (a) [Link]
H
106. We have nk  constant– ... (1)
RT
2.0  104
Given, nk  3.0  ... (2)
T
From (1) and (2),
H 0    2  10 4  R   166 kJ / mol
In equation (2) multiplying both sides by (–RT),
RTnk  3RT  2  104 R ... (3)
G 0  TS0  H 0 ... (4)
From equation (3) and (4)
S0  3R  24.9 JK 1mol 1
Correct answer: (c)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011 299

107. 1  10  RTnP1 Standard state for component 1 is defined at,

P1  1 bar (Standard pressure)
 1  10   R  298  n1
 1  10  n1  0

So, 10 is independent pressure, but  0 is dependent on temperature.

Correct answer: (c)

e2 N A  
108. We have,    Ci Zi2 
0r k BT  i 
2
2e 2 N A
1 C Z i i 1
  Ci Z 
i 2 r
2
i
0 k B T
 i

2 r

30 nm molkg 1 
2  0.03  12  0.03  22  molkg 1   30  nm 1

2  100
1
  molkg 1 
0.18 9
  30 nm 1   nm 1
10 2 10
10
Therefore, Debye-Hückel screning length    
1
nm
9
Correct answer (a)
109. For oxidation reduction half-cell

 Reduced state (R)
Oxdised state  O   ne 

From modified nernst equation (in terms of formal potential E 0 )

RT  R 
 E  E 0'  ln
nF  O
[Link]
0' RT 1
or, EE   ln
nF e 2
RT
or, E  E0   ln  e2 
nF
RT
or, E  E 0    2  ln e  ln e  1
nF
2RT
or , E  E 0'  
nF
Correct answer: (a)

110.  CO 2  g   H 2  g  ;
(i) CO  g   H 2 O  g   k eq  k1 ... (1)
 CO  g   3H 2  g  ;
(ii) CH 4  g   H 2 O  g   k eq  k 2 ... (2)
300 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011

Adding equation (1) and (2)

 CO 2  g   4H 2  g  , k eq  k 1k 2
CH 4  g   2H 2O  g  
Correct answer: (c)

111. The virial expression for a real gas can be written as

PV
 1  BP P  CP P 2  ...... ... (1)
RT
PV B C
 1  V  V  .... ... (2)
RT V V
From equation (2),
RT  BV CV 
P 1   ......... 
V  V V2 
Substitute this ‘P’ in R.H.S. of equation (1),
PV RT  BV CV   B C 
 1  BP  1  2  .........  +  1  V  V  ........ 
RT V  V V   V V 
PV B RT 1
Or,
RT
 1 P
V V
 2
 2 BP BV RT  CP  RT   ......... 
Compare Ist term on R.H.S. of equation (1) and (3)
BV  BP  RT  ; BV  BP  here   RT 
Correct answer: (d)

kT 2 df
112. Average energy per particle E  ... (1)
f dT
AT m
(Where f = single particle, partition function,) here, f 
V
df d AT m

dT dT V
df A ... (2)
  mT m 1
dT V [Link]
Put this value in equation (1), we get
kT 2 A m 1
E   mT  mkT
 AT m  V
 
 V 
Correct answer: (a)
1
113. Optical density (O.D) = Absorbance = log    c ... (1)
T
1 
Solution A: T = 0.5; O.D  log    log 2  0.301
 0.5 
From equation (1),  0.1  1 =0.301  3.01 mol1dm3cm 1
Solution B: O.D  c  3.01  0.5  0.1  0.1505
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011 301

1 1
Solution C: O.D  log  T   log 0.1  1
 
Therefore, optical density order is C > A > B.
Correct answer: (d)
114. In Raman Spectra, Stokes lines are seperated by 4 B cm–1 and have wave number value less than the
incident radiation, but the first Stoke’s line is obsorbed at   6B
 6B  6  2 cm 1  12 cm 1
Therefore, first Stoke line wave number = wave number of incident – 12cm–1 radiation.
  20487 –12  cm 1  20475 cm 1
Correct answer: (b)

115. Given, Tunelling probability , T  e 2kL  e10

1
2
2mE 
where k    and L  barrier length
  

 m k
If mass if halved  m '  2  , then k '  and L'  2L
  2
1
10 2
 T'  e  e 10
2 2

Correct answer: (b)

116. If A †  A , then Hermitian operator..
A†  A , then antihermitian operator..
d
Given, A  x
dx
†
d  d  † d   d † d 
 A    x  A†       x   x      and x †  x 
dx  dx  dx   dx  dx 
So, A is neither Hermitian nor antihermitian.
[Link]
† † †

 A A†    dxd  x  d   d   d 
†
   x       x    x    AB †  B† A † 
  dx    dx   dx   

 d  d 
   x    x   A A†
 dx  dx 
AA † is Hermitian. Clearly it can be shown than A† A is also hermitian.
Correct answer: (c)

kp
117. In Langmuir isotherm, Fractional coverage    
1  kp
Case I: At low pressure, kp < < 1
   kp  directly proportional to pressure 
Case II: At high pressure, kp > > 1
302 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011

kp
  1 ( Independent of pressure)
kp
Correct answer: (b)

1
118. Width of conduction band 
lattice dimension
Correct answer: (b)

119. From Pauli Principle, “When the labels of any two identical fermions are exchanged, the total
wavefunction changes sign”.
As electrons are Fermions, So
 1,2     2,1 ... (1)
Here,  1, 2    1,2   1, 2 
and   2,1    2,1   2,1 [Given,  1,2     2,1 ]
So, far condition (1), to be satisfied we must have
 1, 2     2, 2  ... (2)
The above condition is satisfied only
If  1,2    1   2     2   1
So,   2,1    2   1   1   2   12
Correct answer: (c)
120. Method Polymer Mass
(a) Osmometry (number dependent) Mn
(b) Light scattering (weight dependent) Mw
(c) Sedimentation (viscosity dependent) Mz
Correct answer: (c)

121. C7 H12 O2 . Two important data will differentiate the structure

[Link]
(i) J value cis and trans alkene.
(ii) Position of oxygen in ester.
• In the given data J value of define protons is 16.5 that indicates trans structure.
• One quartet of 2H at 4.1 ppm confirms structure (a).
5.9 ppm
d.t.
H
H2
C O CH3
H3C C
H2
H O q
d.t. 4.1 ppm
7.10 ppm
Correct answer: (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011 303

(B) (C)
(2)
122. (A) (2) (2) (2)
(1)
(2) (3) (2) (2) (3) (4) (5)
(2)
(1) (1)
(1) (1) (3)
(3) (2) (2) (2)
(2) (4)
Three signals Two signals Five signals
Correct answer: (b)

123. Natural ratio of Cl35 and Cl37 is 3:1

M M+2 M+4

Cl35 Cl35 Cl37 Cl37

Cl35 Cl37 Cl35 Cl37

3 3 1 1
× × + × ×
3 1 3 1
9 6 1
Ratio = [Link]
Correct answer: (d)
124. Chemical reaction involved in the above transformation can be illustrated as
OH OH H Cl
OH PCC, CH2Cl2 O
Cr
+ O O
O N
H

OH
OH H
O C O
O

[Link]
Cr
H O O N
O
H

H O O (Vmax = 1765 cm–1)

O
H O

Correct answer: (d)

304 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011

CF3 CF3 CF3

125. F3C CF3 F3C CF3 F3C CF3
H2O –
+ H3 O+
F3C CF3 F3C CF3 F3C CF3
A Aromatised
(stable)
This is more acidic
even than HNO3

H
H H
H2O
+ H3O+ –
4n = 4
n=1
B (Antiaromatic)
(Unstable)
This is not acidic molecule
Me Me Me
Me Me Me Me Me Me
H2O –
+
+ H3O
Me Me Me Me Me Me
C Aromatised
(Stable)
This is acidic in nature

Correct answer: (c) A > C >B.

126. Chemical reaction involved in the above transformation can be illustrated as

[Link]
OH
HC COMe
CH CH COOMe CHO
COOMe 1. CH2(COOMe)2/NaOMe
COOMe
Knoevengel 
reaction

COOMe COOMe
COOMe
COOMe COOMe
COOMe H
H
H
C H  ene reaction
H H

R COOMe
R
COOMe
Correct answer: (d)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011 305

127. For Allylic oxidation of alkene SeO2 is the most important reagent. The oxidation are beleived to
involve an ene reaction between the alkene and the hydrated form of the oxide, followed by [2-3]-
sigmatropic rearrangement of the resulting allylseleninic acid and final hydrolysis of the Se(II) ester
of the allylic alcohol.

H OH
3
Ene reaction –H2O
Se 2
O
OH OH
OH 1
Se O
Se 2
H O OH 1

[2, 3] sigmatropic O Se hydrolysis

rearrangement OH and
OH
HO H
H OH
(B) (A)
Strong electronic repulsion

In the case of endo arrangement there is strong electronic repulsion between  bond and lone pair of
electron on oxygen which makes it less stable as compared to exo in which this repulsion is mini-
mum. Thus major product will be (A).
Correct answer: (c)
128. Chemical reaction involved in the above transformation can be illustrated as

NH2 N2
NaNO2
HCl
COOH C O
(Benzyne)
O
(A)

[Link]
+

(B)
Correct answer: (d)
129. Chemical reaction involved in the above transformation can be illustrated as
OH BuNH2 OH
H C C Cu C C
CuI
OH
I OH Pd(PPh3)4 C C
LiAlH4 OH
+ Cu C C

trans alkene
Correct answer: (c)
306 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011

130. Chemical reaction involved in the above transformation can be illustrated as

O OH
OH
SPh
O
SPh
H SPh H

Correct answer: (b)

131. Chemical reaction involved in the above transformation can be illustrated as
H
HOH2C
O PhCHO Ph O
HO O
OH +
HO H or O
OH
HO CH3 HO
HO
(Stable Ph in equatorial
in 10 membered chair form)

SO3H
(P-TSA)
Correct answer: (d)
132. When papaverine is oxidised with hot conc. permangnate it is broken down into small fragments for
example, veratric acid, metahemipinic acids, pyridine-2, 3, 4-tricarboxylic acid and 6, 7-
dimethoxyisoquinoline-1-carboxylic acid.
MeO MeO COOH MeO COOH
KMnO4
N KOH +
MeO MeO MeO COOH
OMe (I) (II)
metahemipinic acid
Veratric acid
OMe
HO2C
HO2C
N
HO2C +
[Link]
C O HO C 2
N

(III)
COOH
(IV)
OMe
Pyridine-2, 3, 4-tricarboxylic acid
OMe
Papaverinic acid
Correct answer: (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011 307

133. Chemical reaction involved in the above transformation can be illustrated as

O O
O
O2N H2N
NH NH
NH
N O N O
N O O O
HO O HNO3/H2SO4 HO Tin(Sn)
HO

HCl
HO OH OH OH HO OH

Correct answer: (c)

134. Chemical reaction involved in the above transformation can be illustrated as

NO2 + K 2C O 3 NO2 +
O
O
O O
Me OH
[1, 4-addition] H2
10% Pd/C N
NO2 NH2 Et
(X) H

Me Me
N Et N Et

H H
Correct answer: (b)

135. Chemical reaction involved in the above transformation can be illustrated as

O
OH tBuOOH, Ti(O–iPr)4 OH

(+)–diethyl tartrate

Correct answer: (a) [Link]

136. I. Axis of chirality present in the following compound.
(i) Allene (ii) Biphenys (iii) Bipyrroles, (iv) Spiranes (vi) Hemispiranes
II. Plane of chirality present in the following compound
(i) Ansa compound (ii) Paracyclophanes (iii) Transcyclooctene
III. Helical chirality present in

(i) DNA (ii)

Correct answer: (d)

137. Correct answer: (b)
308 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011

138. Chemical reaction involved in the above transformation can be illustrated as

OH
3 O
OH P-TSA
HO 2 H3CH2C C CH2CH3 O O
H4 + (H+)
1 OH 3-Pentanone Et Et
(S)-1, 2-4-Butanetriol
Correct answer: (c)

139. Chemical reaction involved in the above transformation can be illustrated as

O O O
O
1. [Link] N N N
N 
TMEDA 
H Li Li Me
H3C I
Bu
Correct answer: (b)

140. Chemical reaction involved in the above transformation can be illustrated as

O
H O H H
Br Br
O O
1. NBS C O
COOH O O
2. KO tBu H
O
H H
Correct answer: (c)

141. Chemical reaction involved in the above transformation can be illustrated as

O O O

MeMgCl [Link]
Cl

CuCl Me
Me
Ph Ph Ph
Correct answer: (d)

142. Chemical reaction involved in the above transformation can be illustrated as

O
 hv
+ [endo rule] Paterno
Buchi reaction
O O
(X) (83%)

Correct answer: (c)

 SOLVED PAPER : CSIR-UGC-NET/JRF June 2011 309

R
R
CO2Et
143. EtO2C
H EtO2C CO2Et
O pH-8.5
EtOH N
O H3N O
H
(Hantzsch)
(Dihydropyridine)
Correct answer: (d)

KOH
144. EtOH +
Br

B B C

2 : 1
(60%) (30%)

Molecular weight of A = 199 g mol–1

Molecular weight of B = 118 g mol–1
According to the above balanced equation 199 of A will give product = 118 g
118  1.99
Thus 1.99 will gives the product =  1.18 g
199
But the yield is 1.062 g
1.062
Percentage yield =  100  90%
1.18
Since the ratio of B and C is 2 : 1
Therefore, yield of B = 60% and C = 30%
Correct answer: (a)
145. Chemical reaction involved in the above transformation can be illustrated as

[Link]
O CH3MgCl
+ HO
O OH
(A) (C)
(B)
(C8H16O2)
H+ (E1)
LiAlH4

H HO (=1.5 ppm)
H
+
H H
OH
(C)
(C6H12)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011 307

SOLVED PAPER : CSIR-UGC–NET/JRF– Dec. 2011

CHEMICAL SCIENCES BOOKLET - [C]
PART -B
†
21. A†  A (Hermitian) and A  A (Not hermitian)
For option (a),
† †
 d   d   †  d  d 
       i   i and     
 i dx  i  dx    dx  dx 
 d

i dx
It is Hermitian.
† † †
 d2  † d   d   d  d  d2
For option (b),  i 2 
  i        i        i
 dx   dx   dx   dx   dx  dx 2
It is Not Hermitian.
† † †
 d 2   d   d   d  d  d 2
For option (c),  2              2
 dx   dx   dx   dx  dx  dx
It is Hermitian.
For option (d),
† †
x 2   x   x   xx  x 2
It is Hermitian.
Correct answer is (b).

+1 0 –1
22. N  1s 2 2s2 2p3 ml
L  1  0 1  0 term defined as S
3
[Link]
s
2
3
2s  1  2   1  4
2
3 3 3
J   L  S  .....  L  S  0  ..... 0  
2 2 2
4
Therefore, Ground state term = S3 2
Correct answer is (d)
23. Population P  e  E/ kT ...(i)
Therefore at constant temperature lower the energy (E) higher will be population.
 EA  EB

 PA  T1   PB  T1  , PA  T2   PB  T2 
Also higher the energy value, higher will be the change in population ratio when temperature is
308 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011

changed from T2 toT1

PA  T1  PB  T1  PA  T1  PB  T2 
   
PA  T2  PB  T2  PA  T1  PB  T2 
Correct answer is (c).
24. From Heisenberg uncertaintity principle,

h h 1
 E . t    . t    . t 
4 4 4
Or  . t  constant ...(i)
(where t = life time or Relaxation time and   uncertainty in frequency )
  0.1 Hz 1sec   constant ...(ii)

And   Hz  104   constant ...(iii)

From equation (ii) and (iii)
0.1 1  104    103  1000
Correct answer is (c).

25.  CH3COO   aq.  NH 4  aq.  H 2O

CH3COOH  NH 4OH 
weak acid weak base ionised salt
end point

b c

[Link]
When weak base is added to weak acid then salt is formed which is more dissociated w.r.t. weak
acid, so conductance increases upto end point but after the end point only concentration of weak
base increases which remains in almost undissociated form so does not lead to increases in conduc-
tance.
Correct answer is (d).
26. If charge on cation is high then its flocculation value will be low for an anionic sol and if charge on
anion is high then its flocculation value will be low for a cationic Sol. As K2SO4 has low floccu-
lation value than KBr (due to SO 24 has higher are charge than Br  ) ; so sol. A is cationic in nature.
On sol B, CaCl 2 has low flocculation value than NaCl due to higher the change on calcium ion
than sodium ion. So sol B is negatively charged.
Correct answer is (c).

 U   U 
  P
27. dU  TdS  PdV   V   P or  V s
 s
Correct answer is (b).
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011 309

a a
28. 325.6    a  325.6  3
2 2 2
1 1 1 3
325.6  3 325.6  3
d 333    108.5 pm
2 2 2
3 3 3 27
Correct answer is (c)
29. Correct answer is (b)
30.  2CO 2  g   2H 2O   
C2 H 4  g   3O 2  g  
Here n g  n g  product   n g  reactant 
 2  1  3  2

 H  U  n g RT
Or, H  U  n g RT  –2  8.314  300  5000 J  5 k J .
Correct answer is (a).

31.

n = splitting due to spin orbital coupling = E 2  E1 .

Correct answer is (b).

32. [Link]
If k1 and k 2 are rate constant at temperature t1 and t 2 respectively and  is temperature coefficient,
then these are related by the expression
t /10
k 2  k1    [Where, t  t 2  t1 ]
Here, k1  2.66  10 3 s 1 ; k 2  2.2  10 1 s 1

And t1  120k ; t 2  360 k

2.2 101 24
 3
      1.2
2.66 10
Now at temperature 240 K, rate constant  k 3 
12
k 3  2.66  10 3  1.2   0.024 or 2.4  102 s 1 .

Correct answer is (a).

310 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011

33. In potentiometric titration the rate of change in slope of E vs V graph has maximum at the equiva-
lence point
d  dE  d2E
  0  0
dV  dV  dV 2
dE dE
And as can be positive or negative. But will always be greater than zero.
dV dV
Correct answer is (c).

34. Osmotic pressure,   C1RT 1  BC1  ...

Where C1 = concentration of polymer in mol L1 unit and B = constant.
When concentration is expressed in terms of ‘c’  gL1  then, C1  Mc

   MRTc 1  MBc  ....   MRT  BM 2 RTc  ...
c

 Vs c graph will give intercept  c ' = MRT
T
c
c'
 M
RT
Correct answer is (b).

35. Conc. time

(i) 0.1 M t1  1 hr
(ii) 0.08 M t 2  2hr
(iii) 0.067 M t 3  3hr

Above data firts with second order rate law expression for the reaction
 A 
P

1 1 1 1 1 
 
 A t  A t [Link]
  t  k  k  
t   A t  A t


2 1  2 1 
From data (i) and (ii)
1  1 1 
k     2.5 M 1hr 1
 2  1  0.08 0.10 
From data (i) and (iii)
1  1 1  1 1
k     2.5 M hr
 
3  1 0.067 0.1 
As the value of k is constant so it is second order reaction
Correct answer is (c).
36. For 1-D box, the energy is
n 2h2
En  (where L = length of 1-D box)
8mL2
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011 311

n 2h 2
  L  2a 
32ma 2
22 h 2 4h 2
Therefore, E2  
32m a 2 32m a 2

32 h 2 9h 2
and E3  
32m a 2 32m a 2

5h 2
E  E3  E 2 
32 m a 2
Correct answer is (d).
37. At room temperature due to rapid interconversion of axial and equatorial F atoms, all the fluorine
will be equivalent. Hence 19F NMR of PF5 at room temperature will appear as doublet of 5F.
Correct answer is (b).
38. Closo BnHn species has always –2 charge.
Correct answer is (a)
39. BCl3  p  p back bonding

CH3
sp3

B(CH3)3 sp2 B CH3 B-attracts B–CH3 electron (Hyperconjugation).

CH3

Ph sp2

BPh3 sp2 B B and C both are sp2-hybridised. No shifting of electrons (Resonance).

Ph
BCl3  BPh 3  BMe3
Correct answer is (a) [Link]
40. Correct answer is (b)
2 2
41. Energy level for NO, 1s2 1s*  22s *2s  22px  2py
2 2
2pz *1
2px

Number of electrons in antibonding MO = 1

2
Energy level for CO, 1nb 22 12   22 3nb
2

No electron is present in antibonding MO.

So, number of antibonding MO is zero
Correct answer is (a)
42. M = V, x = 6, z = 1
1
i.e.  V  CO 6  = 5  2  6  1  18
Correct answer is (b).
312 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011

43. (A) IE1 for O and S are 1314 and 1000 kJ mol–1.
difference = 1314-1000 = 314
(B) For N and P IE1 are 1402 and 1012.
difference = 1402 – 1012 = 390
(C) For P and As IE1 are 1012 and 947
difference = 1012 - 947 = 165 (less 300 kJ mol–1).
(D) Also for IE1 difference is less than 300 kJ mol–1.
Correct answer is (b)
44. Because main group element follows octet rule.
2  5 1  8
Correct answer is (d).
liq.NH3
45. Na  Na   NH 3  x  e   NH 3  y

1
NH 4 Br   e  NH 3  y 
 NH 3  H 2  y NH 3  Br 
2
Na   NH 3  x  Br  
 NaBr  xNH3
Correct answer is (b).

46. SN x  because it is a giant cross linked molecule and have mobile electrons.
Correct answer is (d)

47. Correct answer is (a)

48. pH = 6.40  – log [H+] = 6.40  [H+] = 3.98×10–7
HIn  H   In 

initial 100 0 0
At end point 80 20 20
 H    In   3.98  107  20
K In  
 H In  80
[Link]
K In  9.95  10 8
Correct answer is (a).
49. Sm3  due to spin-orbital coupling
Correct answer is (d)
3
50.  Co  NH 3 6   highest value of  0

 Highest energy  v  or lowest value of wavelength is absored

Correct answer is (c).
1
51. K.E  mV 2
2
According to question,
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011 313

1
1MeV  M  S12 ...(i)
2
1 2
And 2MeV  M S2 ...(ii)
2
Dividing equation (ii) by (i)
2
 S2 
  2  S2  2 S1
 S1 
Correct answer is (c).
52. Ni  PPh 2 Et  2 Br2 ;   3.20
Number of unpaired electrons = 2.
Thus this complex is tetrahedral. Tetrahedral complexes show only one isomer.
Magnetic moment corresponding to two unpaired electrons = 2.9 B.M. The hesh values 3.20 BM is
due to spin-orbit coupling.
Correct answer is (b)
53. NO  O3  NO 2  O 2
Correct answer is (a)
54. C = O stretching frequency for simple ester 1750-1725 cm–1.
For six membered lactone = 1750 – 1735 cm–1.
For five membered lactone = 1795-1760 cm–1.
Correct answer is (b).

55. Nitromethane is used as a synthetic equivalent for formyl anion.

Correct answer is (b)
56. According to the given product stereochemistry, the product is formed by 6  disrotatory
electrocyclisation

H

[Link]
disrotatory

6 H
electron participate

Correct answer is (a).

57. Chemical reaction involved in the above transformation can be illustrated as

O O

H3C S OH H3C S O + H+
O O

O
OCH3 O H

H2C
H+ H2C H3C CH3
C CH3 C CH3
Acetone
2-methoxy propene
314 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011

OH CH3 O CH3

+ O C
OH CH3 O CH3

Correct answer is (c).

58. IUPAC name of above compound can be written using following keynotes
(1) carboxylic group has to be given highest priority
(2) keeping the chain double bond is parent chain.

2 1
3 COOH
6
H .
5 4 (S)

(S)-3-(prop-2 ynyl) hex-5-enoic acid

Correct answer is (d).

59. In C20H20 due to 20 carbons, there will be 20×1.1% probability of one 13C in the molecule, where
1.1% is natural abundance of 13C with molecular ion, there will be 22% of M + 1 signal. Hence if 260
is 100% and 261 will be 22%.
100
So, ratio  5 :1
22
Correct answer is (b).

I
I2/KI
60. I a
COOH NaHCO3
COONa O
O

Correct answer is (a). [Link]

61. Correct answer is (c).
62. Chemical reaction involved in the above transformation can be illustrated as

O O O
O
Cl – BH Cl Cl SN2
EtO O
EtO EtO
B O EtO EtO
H
Cl
O O

Correct answer is (b).

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011 315

63. Since in case of A the hydrogens present at 1st and 6th position repel each others. Hence planarity of
distorts. While in case of B and C this type of planarity is maintained.
1
H
H
6
Correct answer is (c).
64. Chemical reaction involved in the above transformation can be illustrated as
sp2
Br Br

HBr Br– +
Br Br Br Br B
A
diastereomers
Compound A and B are diastereomers due to difference in absolute configuration at carbon 2 and 3.
Correct answer is (c)
65. Chemical reaction involved in the above transformation can be illustrated as

OMe OMe OMe

NaNH2 NH2
Liq. NH3
Cl
Benzyne NH2

Correct answer is (a)

66. Compound B can be represented in fisher projection as shown below

HO
4
OH HO H
3
H OH
[Link]
OH H
HO OH
HO H 2 OH
OH OH 1
Staggered form Plane is present
(B) Eclipsed form HO
so, it is not optically
active.

Here in fisher projection it contain plane of symmetry passes through mid of C2-C3. Hence, it is
optically inactive.
Correct answer is (c)
316 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011

67. Chemical reaction involved in the above transformation can be illustrated as

CH3 CH3
H Ph H
according to
Ph H3C Ph
Cram's rule
O H OH
H O
H AlH3

Correct answer is (a).

68. Characterization of organic compound can be done as
10
DBE  8  1  9  5  4 .
2
At 6.8 ppm d of 2H 
 Indicates para hetro disubstituted benzene ring.
7.2 ppm d of 2H 
2.5 ppm 3H singlet. – CH3
H3 C OCH3
3.8 ppm 3H singlet – OCH3
Correct answer is (c).
69. Pyrrole > Indole > Pyridine
Pyrrole is cosidered to be   rich centre where in HOMO is at higher energy level where as Pyri-
dine is   sin k centre whose HOMO is at low energy level, and pyridine gives nucleophilic substi-
tution reaction rather then electrophilic substitution reaction.

N N
Pyridine H
Pyrrole
Correct answer is (c)

70. Chemical reaction involved in the above transformation can be illustrated as

[Link]
Li
CH3 CH2 CH2 CH2 CH2 C C CH3 H3C.(H2C)4
Liq. NH3 H
– C
e
H CH3

H3C(H2C)4 H3C(H2C)4
• e –
C C
H H CH3
CH3
radical anion

Correct answer is (c).

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011 317

PART C

71.

EV=0
Ec  Ed
At T = 0K, E f 
2
2.0 eV  1.98 eV
 Ef   1.99 eV
2
For fermi level lies exaclty half any between the bottom or conduction band and the donor level. But
as temperature is increased fermi level drops (i.e., E f decreases).
Correct answer is (d).
72. Correct answer is (a)

73.  CO  g   H 2O  g 
H 2 O  g   C  graphite  

As the number of mole of gaseous product is more than reactant  n g  1 ,

So there is overall increase in entropy
 S0   ve
0
 TS0 will increase with increase in temperature ( A  TS )
Enthalpy of reaction  H 0  is independent of temperature

 H 0  constant   B  H 0 
0
 G  H 0  TS0  const  TS
So with increases of temperature G 0 decreases because S0   Ve ( C  G 0 ).
Correct answer is (d).

74. Correct answer is (c)

75. [Link]
From Roult’s law, Relative lowering of vapour pressure = activity of solute
0
P P P0  P
  ax or,   x x [where a   x x ]
Po Po
0.0400  0.0392 2 0.0008
or,  x  or,  24   x
0.0400 48 0.0400
or,  x  1.02
Correct answer is (d).
O R O R R O
     
76. R O P OR + R' X R O P O R + R' X R' O P OR + RX

Because P–O bond very strong affinity very high not easily break. So, R–O bond break.
So, correct answer is (a)
318 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011

77. Since, we konw that for the entropy of mixing is

Smixing  n total R  x i ln x i
i

 n total R  x1 ln x1  x 2 ln x 2  x 3 ln x 3 

1 1 1 1 2 2 1 1 1 1
  1  1  2  R  ln  ln  ln   4R  ln  ln 
4 4 4 4 4 4 2 4 2 2
 1 1 1
 4R  ln    ln  = 6 R ln 2
 2 2 2
Correct answer is (a).

78. For H –atom, virial theorem,

(i) V = 2E (ii) V = –2T (iii) T = –E
Where,T = total energy
T = kinetic energy
V = potential energy
 V2T
Correct answer is (b).
79.  Vapour
liquid 

dP H vap.

dT Tvap  Vvap.  Vliq. 

dP H vap.
or,   Vvap.  Vliq. 
dT Tvap. Vvap.

 dP 
H vap.    Tvap. Vvap.  8  10  bar K   400  K   200  L mol   640 bar L mol1
3 1 1
or,
 dT 
[Link]
1 bar L  100 J 
 640 100 J mol1
 64 KJ mol1
Correct answer is (d).
80. Higher the charge and smaller size of the central metal cation increases the acidic strength of
hydrated complex because it polarizes O–H band of H2O easily.
3
In Sc  H 2 O 6  , Sc is in +3 oxidation state and has smallest size.

Therefore, in size of dipositive ions increase in the order Ni2+ < Mn2+. Na+ has lowest oxidation
state and largest size.
Correct answer is (b).
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011 319

81. For non-dissociative Langmuir adsorption ,

KP
 A 2 M  s  ,  
A 2  g   M  s  
1  KP
For dissociative Langmuir adsorption
1/ 2
 KP 
 2AM  s  ,  
A 2  g   M  s   1/2
1   KP 
Correct answer is (d).
82.  Fe 2 , E10  0.77V, G1   nFE10   F  0.77
Fe 3  e  ... (i)
0 0
 Fe, E 2  0.44V, G 2  nFE 2  2F  0.44 
Fe 2  2e  ... (ii)
Adding above half cell reactions
Fe 3  3e 
 Fe
0
G 3  G1  G 2  3FE 3  0.77F  0.88 F = 0.11F
1F

0.11
E 03   V  0.036 V  0.04 V
3
Correct answer is (d).
83. Number of radial nodes = n–l–1
For s-function l = 0
Therefore, number of nodes = n–0–1 = n–1
Every function either s, p, d or f have non zero at the origin.
Correct answer is (a)

84. According to “ The variation principle“ If any orbitary wavefunction is used to calculate the
energy, the value calculated is never less the true energy.
 Energy calculated by using an arbitary wavefunction and applying perturbation will always be
greater than or equal to true energy.

  E   E     E
0
0
0
1
0

Correct answer is (c). [Link]

85. For allowed transitions are g  u ,  g   u , g   u
Correct answer is (b)

86. According to the pauli exclusion principle, the wavefunction of fermions (here electrons) must be
antisymmetric  i.e.,  1, 2     2,1  .

For a triples state, spin wavefunctions can be  1   2  or  1   2  or [ 1   2     2   1] ,
which are symmetric in nature. As  total   space  spin . So, for  total to be antisymmetrical w.r.t.
electron exchange,  space must be antisymmetric because for triplet state  spin is symmetric so,
 space g 1 u  2   u 1  g  2 
Correct answer is (c).
320 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011

87. In AX 3 A proton spectra will be a quartet (Intensity ratio 1 : 3 : 3 : 1) at

  4.1, 4.3, 4.5 and 4.7 ppm and X proton spectra will be a doublet (Intensity ratio 1:1)

 J  0.2 ppm
106    100MHz 
or,  0.2  
   100 106 Hz 

106
or,  0.2    20
100 106
Correct answer is (a).
88. 1  P1  2P2  2P3  P4

+ +
+ H
+ H

H H

E C2 v v '
 B2 ,  2  2P1  P2  P3  2P4
1 1 1 1
- -
+ +
E C2 v v '
 B2
1 1 1 1

Both the molecular orbitals belongs to B2.

Correct answer is (c).
1 m1m 2 1
89. Since, r  when,   . When r is same then, r 
r 2 [Link]
m1  m2 
2
 1 2  2
2    
r  H 2  r  D 2    HD    1 2  3
   
8

  r  HD  
2
 H2  D2  11  2  2   1  9
     1
 1  1  2  2   2 
Correct answer is (c).
90. Let one faraday of electricity is withdrawn from the cell
(i) Electrode reaction at anode Ag  s   Cl  a1   AgCl  s   e 

(ii) Electrode reaction at cathode AgCl  s   e   Ag  s   Cl  a 2 

(iii) Migration of K+ ions t  K   a1   t  K   a 2 

(iv) Migration of Cl– ions t  Cl   a 2   t  Cl  a1 

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011 321

The net effect is obtained by adding the above four changes, which gives
Cl   a1   t  K   a1   t  Cl  a 2   Cl  a 2   t  K   a 2   t  Cl  a1 

Or, t  K   a 1   Cl  a1   t  Cl   a1   t  K   a 2   Cl  a 2   t  Cl  a 2 

t  K   a1   t  Cl   a1   t  K   a 2   t  Cl  a 2 
Correct answer is (a).
91. In order to have 10 unit total energy only 2 combinations of selecting particles are possible
(i) One particle with 1 unit energy and 3 particles with 3 unit energy each
Therefore, number of ways possible = 4 C1  3 C3  4 1  4 ways
(Because first particle can be selected in 4 ways next 3 particles from remaing 3-particles can
be selected in only 1 way)
(ii) 2 paticles with 2 unit energy each and 2 particles with 3 unit energy each
Therefore, number of ways possible = (selection of 2 particles out of 4-particles) × (selecting of
2 particles out of remaining 2-particles)  4 C2  2 C 2  6  1  6 ways
Therefore, total number of ways = 4 + 6 = 10 ways.
Correct answer is (d).

92.   HCOOH   HCOO   H 

   

   HCOONa     HCl –  1   Na SO     KCl   1   K SO  

2 2 4
2 2 4

1 1 
 105  426    260   150   308    405 Scm 2 mol1 .
2 2 
Correct answer is (b).
93. Basis set is displacement of vectors of all atoms = 3 N coordinates.

H z
H

[Link]
H
x
H H H
y

C2 E C2 v v '
No. of unshift
10 0 10 0
atoms
Contribution
3 1 1 1
per atom
R.R. 30 0 10 0

Correct answer is (b)

322 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011

94. For data set X i Yi  . When equation is Y = AX + B

Its deviations are taken from the middle period so that X  0 , the value of A and B can be directly
XY Y
written as A  and B
X 2 N
Correct answer is (b).

95. Heavier isotope contains heavier bonding. Heavier the bonding reaction rate slow. But in lighter
isotope bonding is weak, so reaction rate is faster.
Correct answer is (a)

96. When equilibrium reactions are disturbed from their equilibrium condition via either T-Jump or pH-
Jump then measurement of relaxation time leads to the study of reaction rate.
Correct answer is (c).
97. Overall reaction can be obtained by simple addition of mechanism steps,
So , A + B 
 P (overall reaction)
d P
 rate of reaction   k 3  A 2  C ...(1)
dt
As A 2 and C are not appearing in the overall reaction so they are intermediates. As equilibrium is
fast so concentration of  A 2  and [C] can be determined using equilibrium conditions.

K1 
 A2  2
  A 2   K1  A 
i.e., 2 ...(2)
 A
K2 
 C   C   K 2  A  B ...(3)
 A  B
dP 3
From reaction (1), (2) and (3), we get  k 3 K1 K 2  A   B 
dT
Correct answer is (a).
98. 01  e 1  2x e 
[Link]
or, 2143 cm 1  e  2e x e or, 2143 cm 1  e  2  14 cm 1
or e  2171 cm 1
First overtone more number is given by,
02  2e 1  3x e  = 2 e  6 e x e  2  2171  6 14  4258 cm 1
Correct answer is (a).
rate of propagation
99. Kinetic chain length 
rate of initiation

rate of reaction 4  103 mol dm 3s 1

   2000
k i  I  2 103 s 1 103 mol dm 3 
Correct answer is (a).
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011 323

100. For d3 and d8, the lowest transition gives the value of  0 .

Energy

with mixing

4
no mixing T1g (P)
4
P

15B
4
T1g (F)
6Dq 8Dq
4
F
4
T2g

12Dq 10Dq

4
A2g
Correlation of spectra for [CrF6 ]3– (in cm–1)

Observed spectra Predicted

4 4
A2 g  T1g ( P ) 3 34 400 30 700 (12D q + 15B)
4
A2 g  4T1g ( F ) 2 22 700 26 800 (18 D q)
4 4
A2 g  T2g 1 14 900 14 900 (10 D q)

Correct answer is (b).

101. [Link]
(A) N 3  linear, XeF2  Linear

(B) ClF2  Bent, ICl 2  Linear

(C) ICl4  square planar,  PtCl4 2  square planar

(D) XeO3  Trigonal pyramidal, SO 3  Trigonal planar
Correct answer is (b)

102.  CpFe  CO  NO   2
Step-1: Determine the total valence electron (TVE) = A
A   5  8  2  3  2  18  2  36

Step-2: B   n 18   A , where n = number of metal.

B   2 18   36  36  36  0
324 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011

No metal-metal bond found.

 CpMo  CO 3 
2

Step-1: A   5  6  2  3  2  17   2  34

Step-2: B   n 18   A  2 18  34  36  34  2

Step-3: B/2 = gives the total number of M-M bonds in the complex
B = 2 and B/2 = 2/2 = 1
In this complex, the total number of M-M bonds is one.
Correct answer is (d).

103. N 2  8H   8e  16 ATP 

 2NH 3  H 2  16ADP  16Pi
Correct answer is (d).
104. Correct answer is (a)
H
H H
H B H
B B
105. H H
B
H H
H

s = number of B–H–B bonds = 4

B

t = number of B–B–B or B B bonds = 0

y = number of B–B bonds = 1
x = number of BH2 groups + twice the BH3 groups = 2
Therefore, styx code = 4012
Correct answer is (c)
106. Correct answer is (c)
107.
[Link]
Order of  donor ability NMe3 > NH3 > Py
Order of  CO , Py > NH3 > NMe3
Correct answer is (a)
8
108. A 4  224 He
B 
m  2  4.002603  8.005300  0.000094
There is mass loss. Thus , energy evolve.
Therefore, exothermic
80 40
(B) 36 Kr 
 2 18 Ar
m  2  39.96238  79.81638  0.10838
No mass loss, no energy realsed
Therefore, endothermic.
Correct answer is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011 325

109. Correct answer is (c).

V
110. Frequency shift     ; Where V  relatime velocity of source and observer
c
  frequency of emitted radiation
m
2.2 103    3.48 1018  Hz 
s 
    2.55  107 Hz  25.5 MHz
m
 
3  108  
s 
Correct answer is (b)

111. Na 2 B4 O 7  16Na  8H 2  7SiO 2  4NaBH 4  7Na 2SiO3

Correct answer is (b)
112. Substitution nucleophilic unimolecular conjugate base mechanism.
2 


(i)  Co  NH 3 5 Cl   OH   Co  NH 3 4  NH 2  Cl   H 2O
acid conjugate base

 2
slow step
(ii)  Co  NH 3 4  NH 2  Cl  
rate
  Co  NH 3  4  NH 2   Cl
determining
step

2 2
(iii)  Co  NH 3  4  NH 2    H 2 O 
  Co  NH 3 5  OH  
Correct answer is (b)
113. Correct answer is (a).

114. Energy

Correct answer is (d) [Link]

2
115.  Co*  NH 3 6   HS ;

3
 Co*  NH 3 6  
 Low spin
2 3
 Ru  NH3  6  
 Low spin ;  Ru *  NH 3 6  
 Low spin
Correct answer is (c).
326 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011

 hydrogen
H3C H3C
elimination
116. C CH2 Ti Ti H + C CH2
H3C
H3C
H
Correct answer is (b).
2
117. For Ce4+ ions NO 3 behaves as bidentate ligand. Thus C.N. for  Ce  NO3  6  is 12. and shape
corresponding to C.N. 12 is icosahedron.
Correct answer is (d)

118.

Correct answer is (a).

Non-labile sulfur
S-cys

119. Fe
syc-S S-cys
S-cys
Correct answer is (d).
120. This reaction is supposed to be proceeds through addition elimination mechanism as shown below.

Na OEt OEt
EtOH,  elimination of Cl–
N Cl addition of N N OEt
Cl

Correct answer is (a) [Link]

OEt

121. 60% enantiomeric excess of R-enantiomer gives +90º rotation.

90
Specific rotation of R enantiomer =  100  150º
60
Hence, specific rotation of R-enantiomer = + 150º
specific rotation of S-enantiomer = –150º.
Now, for sample optical rotation = – 135º
135
Enantiomeric excess of S isomer    100  90%
150
Racemic part will be 10% (5% R-isomer, 5% S-isomer)
Total R = 5%, total S = 90 + 5 = 95%
Ratio R : S = 5 : 95 = 1: 19
Correct answer is (a).
122. Correct answer is (d)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011 327

123. Correct answer is (b)

124. Chemical reaction involved in the above transformation can be illustrated as
Br
Br CBr3 Br
Ph3P Ph3P P Br + C Br C
Br Br

C PPh3 Br Br CHO Br
Br Br C PPh3 C PPh3
Br Br Br
H

n-BuLi

n-BuLi Br
Br
(A)
Li Br

Ph N N N
(1, 3 dipolar) N
CuSO4 N
1, 4 isomer
Terminal alkyne sodium ascorbate (B) N
(Click reaction)
Ph
The last step in this reaction includes 1, 3 dipolar cycloaddition reaction also known as click reac-
tion.,
Correct answer is (d).
125. Chemical reaction involved in the above transformation can be illustrated as

OH
Br O OEt

H2C CH OEt [Link]

+ NBS H C CH OEt 2
Br
(A)

O OEt O OEt O OEt

Bu3SnH Bu3SnH

•
• (B)
Correct answer is (a)

126. To solve this question we will calculate the DBE first

number of monovalent atoms number of trivalent atoms
DBE   number of carbons  1  
2 2
328 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011

14
i.e. for C15H14O; DBE = (15 + 1) –  16  7  9
2
DBE = 9 indicates it may contain 2 benzene ring and one carbons group. Now lets look at NMR
data
1
H 2.4 ppm singlet DBE = 9
7.2 ppm doublet 

7.7 ppm doublet 
Two doublets in aromatic region indicates HOMO disubstituted benzene ring at ortho or hetero
disubstituted benzene ring at para position.
Four 13C singlet in aromatic region confirms 4 types of aromatic carbon.

13 C O group.
C singlet at 190 indicates presence of
Hence, compound is p-heterodisubstituted.
7.7ppm
H O
7.2ppm H

2.4ppm
Correct answer is (d).
127. • LiAlH4 reduces COOEt and COOH both group
• BH3, Me2S reduced only COOH group
• LiBH4 reduced only COOEt group.
Chemical reaction involved in the above transformation can be illustrated as

OH OH OH

BH3. Me2S 

OEt O O
O OH O
OEt O
[Link]
HO

OH OH OH

LiBH4 

O OH OH O O
OEt O OH O

Correct answer is (c).

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011 329

128. Chemical reaction involved in the above transformation can be illustrated as

O
O O

H2O2, NaOH
O
O O H
O
O

H
H
Ts Ts
N N
N N O
NH2–NHTs

O H2/Lindlar catalyst
O
O

Correct answer is (d).

129. This problem can be solved using mole concept

CHO

+ (Ph3P)RhCl
(mol. wt. 923)
A(mol. wt. 232) B

1 mole 1 mole

0.05 mole 0.045 mole

[Link]
% yield

The use of catalyst in term of percentage mole can be calculated as

11.6 0.462
mole is used with mole of catalyst is
232 923

0.05 mole 
 0.005 mole
0.0005
% 
  100  1%
0.05
Correct answer is (b)
330 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011

130. Chemical reaction involved in the above transformation can be illustrated as

O HOOC NH2
O O
O 1. NH4Cl, NaCN O
H 2. H3O
BnO O strecker BnO O
synthesis LAH
of amino
acid
NHAc NH2
AcO O HO O
O CH3COOH O

BnO O BnO O
Above shown process is an example of strecker synthesis used in preparation of amino acids.
Correct answer is (c).

131. Chemical reaction involved in the above transformation can be illustrated as

O
LiAlH4
Ph3P = CHCOOEt C OEt Ph OH
Ph CHO Ph Et2O, –78º
(Stablised) (A)
(Trans)
at low temp. double
E-alkene bond will not reduced.
, TsOH
O
O
O
Ph OEt Ph O

Correct answer is (d).

132. Chemical reaction involved in the above transformation can be illustrated as

O
H O
[4+2] cycloaddition
4n,  reaction
[Link]
conrotatory
+ O O

H O
O
Correct answer is (b).
133. Position of classical shift for different hydrogen in this case can be decided by using the concept
of resonance as shown below.
O O
C
H3C H3C D
OCH3 OCH3

H H HB HA

deshielded carbon
HA = 5.7, HB = 6.8; HC = 2.1, HD = 3.9 ppm.
Correct answer is (d).
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011 331

134. Chemical reaction involved in the above transformation can be illustrated as

O O
OMe O OMe O C O C CF3
O O
CF3
+ F3C C O C CF3
H
MeO MeO
NH3 O
NEt3
OMe O C CF3

MeO

O
OMe O C CF3 OMe O OMe O

O3, Me2S OO OH O

MeO MeO MeO

O OH
– H2O

OMe O

MeO

Correct answer is (b)

135. PCC oxidise alcohol into carbonyl compound. Since the medium is acidic in PCC, so some side
reaction may be takes place. To stop this side reaction normally buffer solution like sodium acetate
is used.
Chemical reaction involved in the above transformation can be illustrated as
[Link]
CHO
OH
PCC PCC
H O O
H3C C ONa
A
NaOH (IR = ~ 1720)

PCC OH–
isomerization
O OH O will take place O
H in the presence
of OH –
(IR = ~ 1680)
Correct answer is (a).
332 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011

136. Chemical reaction involved in the above transformation can be illustrated as

O
Norrish-II
OH
(i) hv
(C)
O
O O
Norrish-I
• • H
(ii) •
hv H (A) O
•

hv H

(iii) cis-trans
H isomerisation
(B)
Correcrt answer is (a)

137. Chemical reaction involved in the above transformation can be illustrated as

O O
O OLi
O OLi
LDA(2 eq) Br O CH3
OCH3 O CH3

OH O O OLi O

OH LiAlH4 OCH3 OCH3

(A) (A)
(B)
Correct answer is (a).
[Link]
138. Chemical reaction involved in the above transformation can be illustrated as

O BrMgO Ph Ph Ph
HO Ph
H HO
PhMgBr TsOH Hydroboration
Dehydration BH3.SMe2
(A)
Ph
Ph
O O
PCC m-CPBA
Oxidation Baeyer–Villiger O
oxidation
(B)
Correct answer is (a).
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011 333

139. Chemical reaction involved in the above transformation can be illustrated as


+ O MeOH O
4+2 cycloaddition
O (A) O
OH
O
TsOH

O
O
O O H
(B)
Correct answer is (b).

140. Chemical reaction involved in the above transformation can be illustrated as

Li/liq. NH3 m-CPBA (1 eq.)

t-BuOH (Epoxidation at
OMe (Birch reduction) OMe OMe
e– rich center) O
Correct answer is (b)
141. Chemical reaction involved in the above transformation can be illustrated as

O
Me S
S O Me CH2 O
O Me CH2 Me

CH2I2, Zn/Cu

[Link]
O

Sulphonium ylide cause CH2 group transfer to carbonyl double bond while sulphoxonium group
transfer CH2 group to conjugated double bond on the other hand CH2I2, Zn|Cu causes CH2 group
transfer to isolated double bond commonly known as simmon’s smith reaction.
Correct answer is (a)
334 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011

142. Chemical reaction involved in the above transformation can be illustrated as

H N3 H N N N H N N N

Back side
attack, so PPh3
stereochemistry
will change

H N PPh3 H N PPh3
–N2 H N N N
H 2O PPh3

Cbz-Cl, Et3N

H NH2 H HN C O
O

O
(A)
Hint: Cbz – Cl Cl
H NHCOOBn

Oxymercuration Hg(OAc)2
demercuration NaBH4
OH

N NHCOOBn
COOBn
(B)

Correct answer is (b).

143. Chemical reaction involved in the above transformation can be illustrated as

OEt
[Link]
I O
O Pd(PPh ) 3 4
+ B O
NaOH
NH CH3 O Suzuki coupling N CH3
(A)
OEt H

OH
H3O + H
O
O –H2O N
N CH3 N H

H
(B) CH3
O
O CH3
Correct answer is (c).
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2011 335

144. Chemical reaction involved in the above transformation can be illustrated as

O OMe
N OMe OMe OMe
N N N
NH2 LDA
N N N
shift base
will form
Me I

O OMe This group decides

ozonolysis N
stereochemistry
Me
N
(B) Me

(A)

Correct answer is (a).

145. Chemical reaction involved in the above transformation can be illustrated as

H
O 2 4 O O
1 3 [5, 5]-sigmatropic
5 rearrangement H+

1 3 5
2 4
tautomerism
O

Correct answer is (c).

[Link]
336 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012

SOLVED PAPER : CSIR-UGC-NET/JRF June 2012

CHEMICAL SCIENCES BOOKLET-[C]

Part - B

21. nH 2 O  Cl   Cl  H 2O  n 

If negative end of O  H dipole approaches the Cl ion, then there well be repulsion
+
O H
–
Cl H +

 
ion dipole interaction positive and of O  H  dipole approaches the Cl ion and form  Cl  BO n 
+
– H
Cl O +
H
repulsion
2
Not stabilized. Thus H 2 O does not behave as a base 6H 2 O  Mg 2   Mg  H 2 O  6 
In this reaction Mg 2  behave as lewis acid and H 2 O behave as a ligand or lewis base.
Correct answer is (b).
22. Size of d-orbitals decrease with decrease in size of element. The decreasing order of size is Si > P >
S >Cl
Therefore decreasing order of size of d-orbitals is Si > P > S > Cl
Correct answer is (d).
23. Correct answer is (a).
••
••
••

I –
••

••

••
•••I•  •I• •• -
24. •• ••
 ••I•• or I

[Link]
••
••
••

I
••

Number of lone pair of electrons = 9

Correct answer is (d).

–3/2
–1/2

25. + 3/2
– Selection rule M I  0.  1 .
+1/2
+3/2

+1/2

+ 1/2
–
–1/2
Magnetic field

Correct answer is (d).

 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012 337

26. Correct answer is (c).

14
27. In carbon dating, 6 C undergoes  - ray decay
14
C  14
6 7 N 

Correct answer is (a).

28. Correct answer is (d).
29. Correct answer is (a).
30. Ni  CO  4  L  PMe3 , P  OMe 3 

Ni  CO  4 Total valence electron around

Ni  10  4  2  18 electron
Substitution reactions at coordinatively saturated tetrahedral complexes with a 18 electron count
like Ni  CO  4 or Ni  CO 2  PR 3 2 follows a simple first order kinetics.
CO CO CO
–CO PMe3
Ni Ni Ni
slow
CO OC CO OC fast R3P OC
OC OC
Since rate does not depend upon the concentration and nature of the ligand suggesting a dissociative
mechanism.
Correct answer is (b).

31. Ligand Cl– is both   donor  and  donor 

According to LFT, each ligand is always   donor some ligands like : NH3 which has only one
lone pair of electrons is only   donor. Some ligands like F–, Cl–, OH– etc which hence two or more
lone pair of electrons are   as well as  donors Some ligands like CO, CN  , SH 4 bpy, phen etc
how vacant *  orbitals so these are   donor but   acceptors.
Correct answer is (c).
32. Spin-orbit coupling of d-electrons takes place in which t2g orbitals are unsymmetrically filled.
[Link]
Correct answer is (c).

33. CH3Li  the tendency of organolithium compounds to associate in the solid state as well as in
solution is due to the fact that in a single molecule (LiR), the number of valence electrons is too
low to use all the available Li valence orbitals for 2e–2c bonding. This electron deficiency is
compensated by the formation of multicentre bonds e.g. (2e–4c) bonding.
Li Li C

Li
Li
Li Li Li
Li (2e-4c bonding)
In this structure methyl group of one (LiCH3)4 unit interacts with the Li atoms of neighbouring (Li)4
tetrahedron.
Correct answer is (b).
338 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012

34. Cl
Ph3P Cl Ph3P Cl
+ Cl2
Ir Ir
+3
OC +1 PPh3 OC PPh3
Cl
Since in product metal Ir is present in the higher oxidation state. So, there is less back bonding to
* orbital of CO .

Weaker the CO bond

+
Ir C O

(strong back
bonding)

Strong the CO bond

+3
Ir C O

weak back bonding

Hence,   CO  product    CO  reactant

Correct answer is (a).
35. Nucleophilic attack on olefins under mild conditions
M+
C C C C
[Link]
M+
Nu– can attack easily
So, it requires activation by coordination to metal.
Correct answer is (d).
2 2 2 2
36. In  CrO 4  ,  Mo O 4  ,  WO 4  and  Re O 4  all the metals have same oxidation state but
Cr 6  is of smallest size. Therefore it has strongest tendency to attract electrons. Therefore stron-
gest oxidizing agent.
Correct answer is (b)

37. Al  OH 3  Amphoteric whereas hydroxides of lanthanoids are all base.

Correct answer is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012 339

38.  A  A  is not Hermitian in nature.

†

†
Because for being Hermitian an operator should full till the condition that  OP    OP 
† †
A  A   A †  A    A  A †  . So, it is antihermitian in nature
Correct answer is (d)

39. As we know that, the energy of hydrogen like atom with nuclear charge ‘z’ the energy of orbital with

13.6 Z2 Z2
principal quantum number ‘n’ is E    E n 
n2 n2
Correct answer is (d).

40. The average value of radius r in the 1s state of hydrogen atom is

 1 1
r   1s* rˆ1s d   3/2
rˆ 3/2
e  r /a 0 4r 2dr
0
 a0  a0

4  4 3! 24a 0 3
  r 3e 2r /a 0 dr  4
  a0
a 30 0 3
a0  2  16 2
 
 a0 
Correct answer is (b).
41. The number of irreducible representations is equal to number of classes of symmetry operations in
the group. This is first postulate of Great orthogonality theorem (GOT).
Correct answer is (a).
42. J = 0 to J = 1 appears at 2B = 3.9 cm–1.
Value of rotational constant B = 3.9/2 = 1.95
1
E   J 4   J3  20B  12B  8B  1.95  8  15.6 cm
Correct answer is (d).
43. [Link]
For diatomic simple harmonic oscillator. All the vibrational energy levels are equally spaced and
selected rule v  1 only .
Correct answer is (b).
44. In adsorption of a gas (adsorbate) on a solid surface (adsorbent), adsorbate changes from the more
random state to the less random state.
Adsorbate

Adsorbent

Therefore, adsorption is accompanied by decrease in entropy of the system, i.e. TS is negative.
Also, there is decrease of surface energy which appears as heat.
Therefore, adsorption is accompanied by decrease in enthalpy of the system.
340 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012

Also, G  H  TS
For a spontaneous process, the G should be negative.
Therefore, H should have a sufficiently high negative value.
As T increases, TS becomes positive and also G .
Correct answer is (c).
45. Correct answer is (c)

46. N V N V N V N V
T T T T
N V N V N V N V
T T T T
N V N V N V N V
T T T T
N V N V N V N V
T T T T
Canonical ensemble of replies in thermal contact

Correct answer is (b)

47. If we take a half-cell
1
H   e 1  H2
2
RT 1
E  E0  n
F M H
RT
E  E0 n M H 
F
Then E vs log m graph gives intercept E0. Intercept in the given figure is BB '

[Link]


E C
B
Intercept

A B C

log m
Correct answer is (c)
48. Equilibrium is maintained between reaction and activated complex.
 X # 
A  B  P

Correct answer is (a)

49. We know that Arrhenius equation is
k  A e  Ea /RT ... (1)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012 341

Given: k  5.4  1011 e 50 ... (2)

compare equation (1) and (2), then we get
Ea
  50
RT
 E a  50 RT  50  8.314 J K 1mole1   300K 
 124710 J mole1
Correct answer is (d)
50. In addition polymerization reaction proceeds via free radical chain reaction.
Correct answer is (b)
51. Atoms that are packed in fcc structure. There are 8 atoms in the

corner of a cube. Since a corner of cube is shared by 8 unit cells.

Hence total atoms contribution to a unit cell = 8 × 1/8 = 1 atom.
Atom in a face is shared by two unit cells and there are 6 faces in the cube. Hence atoms = 6×1/2
= 3 atom.
Total number of atoms in fcc = 3 + 1 = 4 atoms.
Correct answer is (c).
52. If the number of close packed spheres be N then the number of tetrahedral voids are 2N.
Since all the tetrahedral holes are occupied. Hence the correct option is CaF2.
Correct answer is (c).

53. Dispersion of a solid in a liquid 

 Sol
Dispersion of a liquid in a gas 
 Aerosol

[Link]
Dispersion of a liquid in a liquid 
 Emulsion.
Correct answer is (b)
100×2
54. For A, RSD = 4
50
100  2
For B, RSD = 2
100
More RSD less precise. Less RSD more precise.
Correct answer is (b)
342 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012

55. Ester is the main functional group.

IUPAC name for ester:

O O
(4)
(3) (1)
Ethyl (S)-2-methyl-4-oxo
(1) cyclohex-2-ene carboxylate (3) (2) (3)
(2) (2)
OEt OEt
H C H (1) C
(4) (4)
O O 'S'

Correct answer is (b).

56. The major product formed in the following reaction is:
NaH, THF
Br

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

Soln. Chemical reaction involved in the above transformation can be illustrated as

Br
NaH, THF
Br

Correct answer is (d).

57. [Link]
Number of signals appears in the broad decoupled 13C NMR spectrum of phenanthrene and an-
thracene can be counted as
3 1 2 4 2
4 2 1 1 3 3 1
2
5 7 3
7 1 3 3 1
6 2 4 2
6 4 Anthracene
Phenanthrene
5
Molecule have axis of symmetry Molecule have axis of symmetry
and plane of symmetry and plane of symmetry
Here identical carbon has given same numeric as they same signal in 13C NMR.
Correct answer is (c).
58. Correct answer is (d)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012 343

59. The molecule has double bond with diastereotopic faces.

OH OH OH
H H

O O

95% H 5% H
(R)-cyclohex-2-enol Diastereomeric pair

Correct answer is (b).

60. It is an electrocyclic reaction. Both the systems 4, 6 are present. In case of 4 electrons, conrotatory
process will occur, but it leads to a trans junction leading to steric strain in the molecule. So, it must
be 6 electron system which will undergo photochemical reaction through distrotatory process.
H

[4n+2] H


disrotation C C
H C C H
H H
cis-junction

Correct answer is (a).

COOH
61.
COOH

[Link]
COOH
The molecule has plane of symmetry. Only in this compound has plane of symmetry. So, this meso
tricarboxylic acid, any given choice.
Correct answer is (b).

62. Chemical reaction involved in the above transformation can be illustrated as

Br Br
Br2
Br
OMe
O O OMe
O O

Correct answer is (b).

344 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012

63.
CH3
CH3
 H
1. CF3COOH O
2. H3O+ H O
H O Now epoxide ring will open in
H trans diaxial from (condition for SN2)
C O

CF3
CF3COOH will attack from bottom. Due
to steric hindrance of –CH3 from top.

axial attack

H2O
CH3 CH3 H3C
OH
H+

H H H OH
O O H
H CH3 OH

H OH
Correct answer is (d).

64. Base
H3CH2C NO2 H 3C CH NO2
Correct answer is (a)
65. Hydrogenolysis  cleavage of the bond between the carbon and heteroatom and addition of hydro-
gen.
The usefulness of benzyloxy carbonyl group in deprotection is the result of the ease by which it can
be removed by hydrogenolysis over a palladium catalyst and the intermediate carbonic acid that
[Link]
loses carbondioxide to give the amine product.
O O

H2
R N O Ph R N O R NH2
Pd-C + CO2
H H H
Correct answer is (b).
Me HO

66. Me
H
H
CO2H
CO2H
H2N tyrosine H2N
Leucine
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012 345

O
H
H2N N
H H2N H
NH
H2N CO2H CO2H
H2N
Arginine
Asparagine
More number of NH2 groups, more basic, the amino acid hence more basic is arginine.
Correct answer is (d).
67. Phosphorescence is in a transfer from triplet state to singlet which can be represented as
T1 
 S0  h
ISC
S1
T1

Phosphorescence
(hv)

S0
Correct answer is (a)

C COOH COOH
OH COOH
68.
OH
C COOH HOOC COOH
O II III IV
I [Link]
In compound I and III, free rotation is not possible. Hence, in II and IV, free rotation between C–C
bond occur. I and III compounds has fixed configuration but in III reactive group are on opposite side
which are not available for cyclization. The only structure I has all the condition suitable for cycliza-
tion to give an hydride.
O O

C C
OH
O
OH
C C
O O
Correct answer is (a).
346 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012

69. Chemical reaction involved in the above transformation can be illustrated as

1. Li, NH3(liq.), BuOH 2. m-CPBA

O
OMe OMe OMe

m-CPBA attacks at more electron rich double bond.

Correct answer is (c).
70. Coupling constant can be calculated as
2.38 2.35

0.03
J J   2.38 – 2.35   400  0.03  400  12 Hz

Correct answer is (d)

Part - C

71. Smaller the inter nuclear distance between two atoms, stronger will be the  - bonds. The increas-
ing or due of inter nuclear distance is Cl – O < S – O < P – O < Si – 0
Therefore strength of p   d  bonding is Cl – O > S –O > P – O > Si – O
Correct answer is (d).
72. Correct answer is (a)
73. Eu 2   4f 7  Half filled  stable; Yb 2   4 f 14  Completly filled  stable
Correct answer is (b).

74. Smaller the size of ln 3 ion, higher will be the partition coefficient.
Correct answer is (d).
75. Correct answer is (d).
76. [Link]
NCl3  4 H 2 O  NH 4 OH  3HOCl ; PCl3  3H 2 O  H 3 PO3  3HCl (two different Acids)
AsCl3  3H 2 O  H 3 AsO3  3H 3 (two different acids)
Correct answer is (c).
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012 347

•• •• •• ••
77.
O N N
H H H F F
H H F
More electronegativity Less electronegativity E.N. of F is greater than
difference between difference between that of N
O and H N and H

Therefore, order of dipole moment is H2O > NH3 > NF3.

Correct answer is (d).
78. Step-I: Calculate T.V.E. (total valency electron)
= 8×3 + 2 ×12 = 48
Step-II: Polyhedral electron count
= T.V. E. – (n×12) = 48–36=12 n = number of the metal atom
Step-III: = P.E.C./2 = 12/2 = 6 = (n + 3) = Archano.
Correct answer is (b).
79. Triplet of carbonyl carbon indicates the each CO is attached with chemically equivalent two Rh
atoms–that means  2  CO complex. Actual structure is:
O

Rh Rh

Rh C
C
O
O

80. Correct answer is (d). [Link]

Triplet
81. Two signals
Doublet
Indicates total three phosphorus atoms in the molecules in two sets – 2P and 1P
2P – doublet, 1P – Triplet
PPh3
That is possible in mer   IrCl3  PPh 3 3 
Cl PPh3
fac   IrCl3  PPh 3 3  will give singlet of 3P.. Ir
Cl Cl
Trans   IrCl  CO  PPh 3  2  will give singlet of 2P..
PPh3
 mer
 Ir  PPh 3 4  will give singlet of 4P..
Correct answer is (a).
348 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012

82.  5 C5 H 5 Ru 2 Cl 1  CO  PPh 3  
T.V.E.  6  6  2  2  2  18
 W 2  CO   Si 1Me3  Cl1  NCMe  
 3 2

Total valence electron = 4 + 6 + 2 + 2 + 4 = 18


 Ir 3Cl33  PPh 3   AsPh 2  
 2 
Total valence elecatron = 6 + 6 + 4 + 2 = 18

 Os 5  N 3  Br22  PMe3   N 1Me 2  
 
Total valence electron = 8 + 3 + 2 + 2 + 1 +1 = 17
Correct answer is (d).
83. For Ni2  ion in free state, the thus having same spin multiplicity an 3F and 3P . In octahedral field,
F splits into 3 A 2g ,
3 3
T2g and 3 T1g terms but 3P does not split but it transforms into 3 T1g  P  . There-
fore or orgel diagram is.

3
T1g(P)
3
3 T1g
P

3
T2g
3
F
Energy
3
1 A 2g

Ligand Field strength

Three electronic transitions are 3 T2g  3A 2g , 3 T1g  3A 2g , 3 T1g  P   3A 2g

Correct answer is (b) [Link]
84. Structure of P4S3.

P
S S
S
P P

Correct answer is (a).

 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012 349

Me O O
OC C CO
OC C Me
85. [Mn(CO)6] + Mn Mn
+ MeLi OC
CO OC CO
OC CO CO

Correct answer is (d).

86. LiH  excess   AlCl3  Li  AlH 4   3HCl
Correct answer is (c).
n!
87. We know that number of microstates 
r! n  r !
For d 5 , r = 5, l = 2
Therefore, n = 2(2l + 1) = 2(2×2+1) = 10
10!
Number of microstates   252  7  62
5!5!
Correct answer is (c).
88. r0  15.3dpm ; r = 14.2 dpm
Rate at any time  Number of atoms
r0 N 0 15.3
 
r N 14.2
2.303  t ½ N 2.303  5730 15.3
t log 0  log = 617 years
0.693 N 0.693 14.2
Correct answer is (d).
89. Because metal carbonyls are stronger bond then break this bond huge amount of energy are required.
But metal-metal bonds are weaker bond. So, reaction is endothermic and enthalpy predominant and
entropy unfavourable.
Correct answer is (b).
90. [Link]
Correct answer is (d).
3
91.  4  10 lit / mol cm
Wt. of sample dissolved in 1 lit solution = 0.1358g
Absorbance of solution 1 lit = 0.441 at 1 cm.
A 0.441
Absorbance (A) =  c i.e. c    0.11025  10 3 M
  1 4  103
gm quantity of compound = conc. × [Link]. = 0.11025×10–3 ×180 = 0.019845 g.
0.019845
w/w % of compound  100  14.60%
0.1358
Correct answer is (b).
350 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012

His (73) His (73)

(101) His (101) His
92. His (77) His (77)
Fe Fe H
d6-system Fe(II) O O H Fe(II) O O
O O
O2
C O C O O
(58)Glu C (58)Glu C O
Fe Fe
O O
Asp (106) His (54) Asp (106) His (54)
His (25) His (25)
(II)Fe (II)Fe
Deoxy hemerythrin Oxy hemerythrin

Correct answer is (a).

93. NAD   Biological reductant


Flovoprotein

cyt.b  cyt.c  cyt.c1  cyt.c oxidase

Correct answer is (c).

94. The total number of fine and hyperfine lines from high spin Mn(II) complex, I = 5/2.
Number of fine lines = Number of unpaired electron in Mn = 5
Number of hyperfine lines = Number of unpaired electron × (2nI + 1)
 5 
Note: n = number of Mn atom = 1, I = Nuclear spin of Mn = 5/2 = 5   2  1  1  5  6  30
 2 
Correct answer is (c).

95.
[Link]
(i) Fe III  High  Spin  d 5  Spherical electronic configuration
t 52g e g2  No quadrupole splitting, singlet signal as shown in  B 

II 6
(ii) Fe  High  Spin  d  axial electronic configuration
t 42g e g2  quadrupole splitting, gives doublet signal as shown in  A 

III 5 0
(iii) Fe  Low  Spin  t 2g eg  Axial electronic configuration quadrupole splitting,
doublet signal as shown in  A 

Correct answer is (b).

2 n x
96. Given that,   sin
 
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012 351

3 /4 2 n x 2 n x
  sin sin
 /4    
2 3 / 4 2 n x n
 sin  a
  / 4  
2 3  /4 2 3  /4 1  cos 2ax 
  dx
  / 4 
 sin 2ax
  / 4 2 
3 /4
2  3 /4 3 / 4 1  3 / 4  sin 2ax  
  1dx   cos 2axdx    x   
2   /4 /4     /4  2a   / 4 

1  3   1  3 2a.  
       sin 2a  sin 
  4 4  2a  4 2  
1   1  3a a   1 1  n n   
    sin  sin       sin    sin 
  4 2a  2 2    2 2a  4  2  

1  1 1  3n n 
    sin  sin  [For ground state n = 1]
   2a  2 2 

1   1  3  
    sin  sin  
  2 2a  2 2 

1  1 
    sin 270º  sin 90º   sin 270º  sin 180º 90º    sin 90º  1
  2 2a 
1  1 
     sin 90º  sin 90º  
  2 2a 
1  1  1  1 
      1  1      1  1 
  2 2a    2 2a 
 

1  1 
  n  2  
[Link]
1  1  1 1
 2    .  
  2  n 2 
  
Correct answer is (b)
4 h 2
97. Particle in a 3D cubic box of length ‘L’ has a energy of .
8mL2
The degeneracy may be calculated by taking the energy formula for 3D cubic box into consideration

n x2
 n y 2  n z2   14h 2

8m 2 8mL2

 n x 2  n y2  n z2  14

n x , n y , n z combination may (1, 2, 3) (1, 3, 2) (2, 1, 3) (2, 3, 1) (3, 1, 2) (3, 2, 1)

352 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012

14h 2
At the energy level there is 6 energy state. So, degeneracy = 6.
8mL2
Correct answer is (c).
98. Energy correction for second order energy
m ŵ n
En2   0 0
m n E n  E m

Generally E 0n  E 0m

So, second order correction to energy is negative.

So, statement (A) and (B) is true.
Correct answer is (b).
99. H2C=CH2
H
H
 
C  C 

H H

The secular determinant will take the form.

 C11 C12    E 
C   0
 21 C22    E
Dividing each element of the above determinant by  and then setting (  E) /   x we get.
x 1
0
1 x
Which on expanding gives.
x2 – 1 = 0
[Link]
The two roots of the above equation are
x = – 1 and + 1
 E E
Thus,  1 or,, 1
 
Which gives E    
E    
Correct answer is (c).

100. For molecule H2 in the excited state 1g 1s . The spin part of triplet state with ms = 0 is propotion to

The three triplet states are  1   2  ms = +1


 1
   1   2    1   2   ms  0
 2
 1   2  ms  1

 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012 353

1
So, triplet state with ms = 0 is  12  1 2 
2
Correct answer is (d).

E 2C4 C2 2 V 2 d X X
101. 5 1 1 1 3
X X
Correct answer is (a).
102. Transition A1 to B1 can be evaluated by direct product A1 × B1 and its transformation.

E C2 V V '
1 1 1 1
A1  B1  X X X X
1 1 1 1
1 1 1 1 = B1

B1 transforms according to x-axis hence transition will be x-axis polarized..

Correct answer is (c).
103. A = 2 – log10 T%
A = 2 – log10 50% = 0.301
A  c   0.301 10 4  0.5   6020 M 1 cm 1
Correct answer is (d).
104. The transitions    ,    ,    etc are allowed only when the spin multiplicity of two
states are same.
Correct answer is (c).

105. [Link]
Given: e  512 cm 1 and e x e  8 cm 1
8
 512cm 1  X e  8 cm 1  Xe 
512

Dissociation energy De  e  512  512  512  8192 cm 1

4x e 48 32
512

Correct answer is (c).

106. q denotes the heat added to the system and ‘w’ is work done by system.
Then, q < 0, w > 0
Correct answer is (b).
354 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012

107. Correct answer is (d).

108. Applying Euler Theorem Maxwell equation we get Maxwell relation.
 V   S 
dG  VdP  SdT ;  T     P 
P T

 S   P 
dA  SdT  PdV ;  V    T 
T V

 T   V 
dH  TdS  VdP  P    S 
;
S P

 T   P 
dU  TdS  PdV ;  V     S 
S V

Correct answer is (b).

1
109. We know that,  vib   hv/ k B T ... (1)
1 e
h  k B T ... (2)

From equation (1) and (2)

1 1 1
 vib   k B T /k B T
 1

1 e 1 e 1
1
e

Correct answer is (d).

110. S  k B n w ... (1)

where w = arrangement.

6! 6  5  4  3  2 1
 W=   60
0!1!2!3! 1 2  3  2  1
[Link]
From equation (1), S  k B ln 60

Correct answer is (c).

111. E cell  E L  E R  E  Cl |AgCl|Ag

E   E
H  |H 2 |Pt L H  |H 2 |Pt
E
Cl |AgCl|Ag R 
Nernst equation for each potential.
 1   1 
 RT RT 
P | P0  2
  RT P | P0  2
RT 
E c e ll  E 0   n a     n 
    n  E0
C l  |A g C l|A g
 
n a   


C l |A g C l|A g F Cl 1 F a   H 1
 
 
F a 
H   2
F Cl 2



E cell 
RT
n
a 
H
  a  2 Cl 2
2
RT  a   2
n
F a    a 
H 1 Cl 1
F  a  1
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012 355

Correct answer is (c).

112. Debye-Hückel equation,  log    A z  z  I

Since, total number of ‘+’ ion per unit volume = n 
total number of ‘–’ ion per unit volume = n 
 n   n e i /kT and n   n e i / kT  i  e 
charge
Since charge density    
volume
z 2n 2 e 2 
   n  n   e   n e  ze / kT
 ne  ze / kT
   kT
Than we expand them and put e  kT condition. Then we apply poission equation to calculate
4
the potential. The equation is  2   
r
Correct answer is (d).

113. Z+
OH + [ML6]
 log  
A B or
 k 
 k  log  
 k0 
log    2A ZA ZB I slope = –2.1
 k0  
I
Slope = 2A ZA ZB (for bivalent complex)
–2.1 = 2×0.509 ×(–1) ×ZB
2.1 2.1
ZB   ZB   ZB  2
2  0.509 1.018
Correct answer is (b).

k 2
1
[Link]
114. k overall  k 2  1 
 k4 
Taking logarithm both sides
1/2
k 
log k over all  log k 2  log  1 
 k4 
1
log k over all  log k 2   log k1  log k 4 
2
1
 Ea overall  E a  2   E a 1  E a  4  
2
Correct answer is (c).

v max S
115. v  Vmax  k 3  E 0 
S  k m
356 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012

k 3  E 0 S v k3
v  
S  k m  E 0 S  S  k m

v v  S v km
 S  k m   k 3   k
 E 0 S   E 0 S  E 0 S 3
v v km v km v
  k   k3 
 E 0  E 0 S 3  E 0 S  E 0
v k3 v
   ... (1)
 E 0 S k m  E 0 k m

v 104 v
Given :  E  s   1.4  1012  ... (2)
0
 E 0
Compare equation (1) and (2)
k3
 1.4 1012 ... (3)
km
1
 104  k m  104
km
Putting the value of km in equation (3), we get
k3
 1.4 108  k 3  1.4  108 , k m  10 4
104
Correct answer is (c)
116. Correct answer is (b)
hc hc 6.626  1034 J sec  3  108 ms 1
117. E   
 E 1.98 10 19 J

 10.039  107 m  1003.9  109 m  1003.9 nm

[Link]
This wavelength lies in the IR region
Correct answer is (b).
118. Given a = 4.04 Å
a 4.04Å
For fcc lattice r    1.428Å
2 2 2  1.44
Correct answer is (b).
119. Correct answer is (a).
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012 357

120.

y
y

x
O y
Intercept slope  m 
x
x

y
For value of slope m 
x

dy y 2  y1 11.3  11.1 0.2

mB     2
dx x 2  x1 4.4  4.3 0.1

dy y 2  y1 11.5  10.9 0.6

mA     6
dx x 2  x1 4.4  4.3 0.1
For different value of y and x, m A  m B and for value of intercept c A  c B .
Correct answer is (c).

O O
121. C C ring H’s are shielded due to resonance.
O Me O Me

O Me O Me
C C
O
O
[Link]
Ring becomes electron rich , proton get shielded; appears at 6.9 ppm.

O OMe O OMe

B
ring H’s are deshielded

C O C O

OMe OMe
Ring becomes electron defficient, proton get deshielded, appears at 7.7 ppm.
C Me appears at 2.1 ppm, C OMe appears at 3.9 ppm.
O O
Correct answer is (a).
358 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012

OAc OAc

AcO O H+ AcO O

122. AcO AcO

OAc O Ac
OAc OAc
H

OAc
AcO
AcO O axial attack
– O
AcO + Br due to anomaric
AcO
effect AcO
OAc
AcO Br

OAc OAc

AcO O AgNO3 AcO O

AcO MeOH AcO
AcO Br AcO

OAc OAc
OAc

AcO O AcO O OMe O

AcO AcO AcO
AcO
O O O AcO
O OMe
C C
CH3 CH3

Correct answer is (b).

123. Chemical reaction involved in the above transformation can be illustrated as
Cl [Link]
N Me
(i) NBS(2 eq), Bz2O, 
(ii) aq. NaOH
N Me
NBS generates Br •
Cl Cl
N CH2 H N
• Br
+ Br
N CH3 N CH3
In benzyl position (C–H) bond is relatively weaker
• •
H2C CH CH2 H H2C CH CH2 H2C C CH2
H
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012 359

Since we have two equation of NBS – Br attacks other –CH3 group also.

Cl Cl

N N
Br Br
+ Br•
H Br
N N

Cl Cl

N N
Br SN2 Br
+ OH
Br OH
N N

–H+ OH–

Cl Cl
N N
SN2 Br
O
O
N N

Correct answer is (d).

124. Chemical reaction involved in the above transformation can be illustrated as

CH3
H

H
H electrocyclic HO
HO reaction
[Link]
CH 3
H

HO

Since there is a trans ring junction, so it is a photochemical conrotatory process.

H
1
H2C CH2
7
H
2 6 1, 7H
shift
HO 3 5 HO
4
desired product
Correct answer is (b).
360 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012

125. Chemical reaction involved in the above transformation can be illustrated as

O O H
N3 N C O N
 N
O
NH2 NH2 N
NH2
isocyanate H
intermediate
Correct answer is (d).

126. Chemical reaction involved in the above transformation can be illustrated as

Br

O OK
(A) OH OH
O
H O
O

Because Br and H are antiperiplanar. So, E2 elimination will take place.

Br Br

+ CO2
(B) O
OH O O
O
Correct answer is (b).
9BBN, H2O2
NaOH
127.
COOMe COOMe
OH (A)
9BBN being a larger group will attack from least hindered side i.e. attack from rear side.

[Link]
COOMe
MsCl
Et N 3

OH O O
(B)
Correct answer is (b).

128. Chemical reaction involved in the above transformation can be illustrated as

CH3 O
NaOH HO
alk. KMnO4 OH Br2
O O
A
O
pinic acid OH
pinonic acid
-pinene
Correct answer is (b).
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012 361

129. (3R, 4S)–3, 4-dimethyl hexa-1, 5-diene

CH3 CH3
H3C CH3
1 1

2 2 [Sigmatropic rearrangement]
3 3
Now we have to find stereochemistry of methyl groups it is E or Z. For this we have to draw cyclic
chair transition state.
Me Me Me
Me Me Me

Reactant Chair transition H

state
(2E, 6Z)–octa-2-6 diene
Correct answer is (c).

130. Chemical reaction involved in the above transformation can be illustrated as

O
O • O
hv •
Norrish-I
Correct answer (c).

131. Chemical reaction involved in the above transformation can be illustrated as

O OH H
Et Et
LiAlH4
rear side
H– attack

(i) Since there is already chiral centre present in reactant. So, it has diastereotopic faces option (a) is
wrong. [Link]
(1) O Si-face (anticlockwise)

Et
(ii) (2) (3)

Since H– is attacking from back side of Si-face. Or we can say attacking from re-face. Option (b) is
right.
(iii) Since reactant has diastereotopic faces. So definitely it is a diastereoselective reduction. Option
(c) is also raight.
Correct answer is (c).
362 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012

132. Chemical reaction involved in the above transformation can be illustrated as

O
Ar
H + – C
O O
O
1. m-CPBA m-CPBA
2. BF3/H2O

O O BF3
BF3

BF3 is a lewis acid. So it will accept lone pair of electron from oxygen atom.
OBF2
O BF3 O BF2 OBF2
–
–F
+

Major
Bond breaking can be of two ways leading to two different cation but cation at benzylic position is
more stable.

OBF2 OBF2
O BF2 O
H
H+
shift

Correct answer is (d).

133. Chemical reaction involved in the above transformation can be illustrated as

H
[Link]
DIBAL
O OH
O O
H

Al H
DIBAL is selective reducing agent for lactones.

OH H
(1)
O OH
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012 363

O OH

(2) H BrMg
OH OH

PCC
(3) OH oxidising agent O
OH O
Correct answre is (a).
134. (i) Acetic acid = 175 ppm
(ii) Acetonitrile = 115 ppm
(iii) Acetone = 205 ppm
(iv) CCl4 = 95 ppm
Correct answer is (a).

135. Chemical reaction involved in the above transformation can be illustrated as

I
OH O
O n-Bu3SnH
PPh3, DEAD
2-iodo phenol AlBN, 
SN2

Correct answer is (a).

136. Chemical reaction involved in the above transformation can be illustrated as

O O O

Br NaOM e Br NaOM e COOM e

This is an example of favorskii type rearrangement

Correct answer is (b).
[Link]
137. Chemical reaction involved in the above transformation can be illustrated as

O CH3 CH3
S O
S CH
H2C 3
CH3
H2C H2C CH3
OH

O O O
H H H

Stabilized ylide will give cyclopropane and Simmon’s Smith reagent will attack at allylic double
bond and form cyclopropane.
Correct answer is (b).
364 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012

138. Chemical reaction involved in the above transformation can be illustrated as

Mechanism:
OH LiAlH4
R
Triple bond is reduced by LiAlH4 when oxygen containing group is attached to triple bond. Since
there is co-ordination between oxygen and metal atom. After co-ordination with oxygen atom hy-
dride ion is transfered leading to formation of trans double bond.
H
H
Al OH
H H O
R R

sharpless epoxidation
LiAlH4 OH
OH L(+1) diethyl tartarate
NaOEt (A)

Sharpless
OH OH
L(+) O
diethyltartarate (B)
Sharpless asymmetric epoxidation occur at the allylic alcohol not on the simple double bond.
Correct answer is (c).

139. Chemical reaction involved in the above transformation can be illustrated as

H B

O
O

[Link]
Addition of B – H bond to the triple bond
HB

n-Bu
O Pd(PPh3)4, K3PO4
B + I n-Bu Suzuki reaction
O

Correct answer is (b)

 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012 365

140. Chemical reaction involved in the above transformation can be illustrated as

H n–BuLi

O N N Ts

+ H2N NH Ts

Li
Li Li N N Ts

N N Ts
N N Li
H n-Bu Li

Li O
OH
+ C
H H

Correct answer is (d).

141. Chemical reaction involved in the above transformation can be illustrated as

O Me2CuLi
Et2O
I
1, 4-addition of Me ion.

O I O
O I

Me
[Link]
Me
Me
(down the plane)
Correct answer is (d).
O
OEt
142. Ph
O
Since we have two functional groups, so first we have to protect one carbonyl group so last two
options can not be the right one.
O
OEt
(CH2OH)2
Ph
PTSA, 
O
Ketonic group is more reactive than ester group. So, it will be protected first.
366 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012

Cp2Ti AlMe 2
O O Cl O O H3O+
OEt OEt
Ph Ph
Tebbe's reagent
O CH2
In this hydrolysis process two reactions will occur. One is deprotection of carbonyl group and an-
other reaction formation of ketone.

O
O
O O
H+ C O H Ph
OEt Ph
Ph
O
CH2 CH2
O O
OH – ••
CH3 CH2
Ph Ph
O O
O O
H2
C O
HO H+ H

Ph
OH2 Ph
Ph
Correct answer is (a).

143. Chemical reaction involved in the above transformation can be illustrated as

Me Me O

H– O Ph H
abstract proton OH PTSA, 
N N N
H
Me

Me
[Link]
Me
H
Ph
Ph OH Ph OH2
3
C PTSA C N O
H H +
1 2 –H
O O
N N
CH3

Ph
Note: (3) position is blocked. So, electrophilic substitution will
be occur at (2) position. N O
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2012 367

144. Chemical reaction involved in the above transformation can be illustrated as

H
O Br
CHBr3 Br Ag+ H
Br
t
KO Bu Br

(Carbene)
H H
OH O

Br Br
–H+

Correct answer is (c).

145. Chemical reaction involved in the above transformation can be illustrated as

OH
H H
H
O + O
N
N (A)
H
H
N
racemic
mixture
N
H
H
O

H OH
N

Correct answer is (b).[Link]

368 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012

SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012

CHEMICAL SCIENCES BOOKLET-[A]

Part-B
21. In ‘g’ nuclear orbital total subshell is nine.

One odd nucleon finding in g-subshell

Total spin = 9/2
 4
Parity   1   1    
Correct answer is (a)
22. PbCl2 and PbSO4 are ionic compounds and insoluble in cold water. Therefore, cannot be used for
deposition of Pb and Pb(Et4) is toxic.
Correct answer is (d)
23. • Beer’s law is subjected to certain real and apparent deviation.
• Real deviations are most usually encountered in relatively concentrated solutions of the ab-
sorbing compound (> 0.01 M). These deviations are due to interactions between the absorbing
species and to attractions of the refractive index of the medium.
• Most common are the apparent deviations. These deviations are due to:
Chemical reasons arising when the absorbing compound dissociates, associates or reacts with a
solvent to produce a product having a different absorption spectrum.
• Strict adherence to Beer’s law is observed only with truly monochromatic radiation.
Correct answer is (b)
24. Since size of Lu3+ is smallest, therefore Lu(OH)3 complex most easily formed with NaOH and
dissolves.
3
Lu  OH 3  3OH    Lu  OH 6 
Correct answer is (d)
25. CO2 has centre of symmetry so on per exclusion principle all the IR active vibration will be
[Link]
Raman inactive. Hence, fundamental vibrational modes common in both IR/ and Raman will be
zero.
Correct answer is (d)

eg
electron transition from
26. [Co(H2O)6] 2+ 5
t2g eg 2 t2g to eg. Therefore, d-d
transition.
t2g

t2
electron transfer from e to t2
[CoCl4]2– e4
t23 therefore, d-d transition.
e

Correct answer is (c)

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012 369

2
27.  Mo 2  S2  6 
2
The structure of  Mo 2  S2  6  cluster is:

S
S S
S
S S S

Mo Mo
S
S
S S S

So, the bridging S22– is two and co-ordination number of Mo is 8.

Correct answer is (a)
28. Duterium D Spin I = 1
Multiplicity = 2nI + 1 = 2×1×1+1=3
Where,n = number of duterium atom
I = spin of duterium atom.
Intensity ratio will be non-pascal.
Hence, 1H NMR of HD will appear as triplet with intensity ratio [Link].
Correct answer is (d)

acac acac
PPh3
PPh3 PPh3
29. acac Ru acac Ru Ru
PPh3 PPh3
PPh3
acac Mirror acac
Trans cis-d cis-l

Correct answer is (b)

O
OH2
O
[Link]
30. H3CC Cu CCH3
O
O
10 Cu–O bonds
O
O CCH3
H3CC
Cu
O O
OH2

Correct answer is (a).

31. Among these elements K is least electronegative and F is most electronegative. Therefore electrone-
gativity difference is highest for the pair K, F.
Correct answer is (b)
370 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012

32. CO32– SO3 XeO3 NO3–

O
O O
O C Xe
S O N
O O O O O
O O
2 2 3 2
sp -hybridization sp -hybridization sp -hybridization sp -hybridization
(Trigonal planar) (Trigonal planar) (Trigonal pyramidal) (Trigonal planar)

CO32 , SO3 and NO3 have planar structure.

Correct answer is (d)

33.
NO
Ni Ni Stable complex
N

20 e– 18e–

Correct answer is (c)

OCH3
34. (OC)5M C
Ph
2 × 5 + M + 2 = 18, M = 18–12 = 6
So, M = Cr, and Re+.
Correct answer is (a)
Fe, Mo, Cu, Zn
Hb & Mb
Metalloenzymes
35. (i) cytochromes
Hemocyanin
[Link]
Nitrogen fixation
Correct answer is (a)

N N
2+ CH2 n N  number of equivalent nitrogen atoms
H2C
36. Cu n Cu  number of Cu atom
CH2
H2C N N I N  spin of one nitrogen
ICu  spin of copper

1 3
mICH   , mI N  1 ; mICu 
2 2
 3 
Multiplicity   2n N I N  1 2n N ICu  1   2  4 1  1  2 1  1   9  4  36
 2 
Correct answer is (d)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012 371

37. Degradation of penicillin G occurs at carbon hetero bond and produces

donor atom

H H H SH
N S
Ph
O
N H2N OH
O
OH O donor atom
O donor atom
Correct answer is (a).
38. B2H6 has D2h point group and S2 axis
CH4 has Td point group and S4 axis
PH5 has D3h point group and S3 axis
SF6 has Oh point group andS6 axis. Hence, SF6 has S6 symmetry element.
Correct answer is (d).
39. Electric dipole allowed transition in d2
For electronic transition selection rule, spin multiplicity S  0 ;    1, J  0,  1
3
F  3 D is allowed transition because S  0,   1
Correct answer is (c)
40. When a hydrogen atom is placed in an electric field along the y-axis. The magnetic moment i.e.
electron density will be oriented along y-axis and therefore the orbital that mixes most with the
ground state 1s orbital is 2py.
Correct answer is (c)
41. Given : for water H vap  41 kJ / mol
H vap
Molar entropy of vaporization, S 
Tb
For water Tb = 373 K (at 1 atm)
41103 J / mol
S   109.9 Jk 1mol 1  110 Jk 1mol1
373
Correct answer is (b). [Link]
42. The eigenvalues of an anti-Hermitian operator are either purely imaginary or equal to zero. If A and
B are non-commuting hermitian operator. So, all eigenvalues are purely imaginary or zero.
Correct answer is (c).

43. The value of  x, p nx   ni p x n 1

 x, p 2x   2ip 2x 1  2ip x
Correct answer is (d)
44. If two arbitrary variables x and y then measure the intensity of correlation coefficient
n  xy  xy 
r
 nx 2   x  2   ny 2   y  2 
  

If xy  x y  xy  x y   r  0
372 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012

They may be related in a non-linear fashion.

Correct answer is (d)

45. Given : Q h  90J and Th  300K

Qc T
Since we know that   1   1 h
Qh Tc

Qc T Q T
1  1  h  c  1 h
Qh Tc Qh Tc

For option (a), we get

60 200 6 2 2 2
    
90 300 9 3 3 3
Correct answer is (a).
46. The relative population in two states with energy E1 and E2 satisfy Boltzmann distribution law,
 E1  E 2 
n 1 g1  k BT
 e ... (1) [where, g1 and g2 are degeneracy]
n2 g2

n1  3 
Given : n   2  exp    E1  E 2  /k BT  ... (2)
2  

g1 3
Compare equation (1) and (2), we get, g  2
2

g2 2
The value of g  3
1

Correct answer is (b).

[Link]
47. Daniel cell consists of two half cells. The half cell on the left contains a zinc metal electrode dipped
in ZnSO4 solution. The half cell on the right consits of copper metal electrode in a solution of CuSO4.
The half cell joined by a salt bridge.
Oxidation half reaction,  Zn 2  aq   2e
Zn  s  

Reduction half cell, Cu 2  aq   2e  

 Cu  s 
__________________________________________
Net Zn  s   Cu 2  aq  
 Zn 2  Cu  s 
Correct answer is (a).
1
48. Quarter life is the time in which the concentration decreases to th of its initial value.
4
Rate law expression for first order reaction is
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012 373

 a 
kt  n   ... (1)
ax
3a
Therefore, Quarter life, x and t  t 1
4 4
So, (1) becomes,

 
 a   a  n4
kt 1  n    n    n 4  t 1 
4 3a  a/4  4 k
a 
 4 
Therefore, correct answer is (b)
49. Due to Kohlrausch’ law at infinite dilution, when dissociation is complete, each ion makes a definite
contribution towards molar conductance of the electrolyte irrespective of the nature of the other ion
with which it is associated and that the molar conductance at infinite dilution for any electrolyte is
given by the sum of the contribution of the two ions. Only hydrochloric acid in water completely
dissociation and contribution with equal ion.
Correct answer is (c).

50. A dilute solution of siliver nitrate is add a slight excess of a dilute solution of sodium iodide, a
negatively charged solution of silver iodide is formed. This is due to the adsorption of iodide ions.

Na+
Na+
Na + – I– –
I I
I– I–
+

Na
+ I– AgI I– Na
I– I–
–
I I
– –
I Na+
Na+
+
Na

This is the electrical property of colloid based on the concept of electrical double layer
[Link]
AgNO3  NaI   AgI   NaNO 3
The ions preferentially adsorbed on the surface of a particle of a colloidal system are called potential
determining ions. The negatively charged surface of AgI particle attracts the positive ions (Na+) and
repels the negative ions (NO3–). The positive Na+ ions tend to form a compact layer in the vicinity of
the potential determining I– ion layer. This is called stern layer. The ion present in the stern layer are
called counter ions.
Correct answer is (a)
374 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012

51. Oe

D0 Eex
Energy 

continum
Og

D0 Dg

Illustration of dissociation

Dissociation energy, Dg  56875  15125  41750

Correct answer is (d)

52. The angle between two planes having Miller Indices  h1k11  &  h 2 k 2 2  is given by

h1h 2  k1k 2  1 2

cos  
h12  k12  12 h 22  k 22   22

11  11  0 1 2 2
cos    
12  12  02 12  12  12 2 3 3
1
cos   0.816 ;   cos  0.816 

  35.27º
Actually all options are incorrect.
53.
[Link]
The molar conductance of anionic surfactant of the type Na+R– in water is plotted against the square
root ofthe normality of the solution. The curve obtained, instead of being the smoothly decreasing
curve characteristic of ionic electrolytes of this type, has a shart break in it, at low concentrations.
This sharp break in the curve accompanied by reduction in the conductance of the solution, indicat-
ing a sharp increase in the mass per unit charge of the material in solution, is interpreted as evidence
for the formation of micelles at that point from the unassociated molecules of surfactant with part of
the charge of the micelle neutralized by associated counter ions. The concentration at which this
phenomenon occurs is called the critical micelle concentration (CMC)
The effect of concentration of electrolyte is given by
log CMC  a log ci  b
For homologous ionic surfactant
log CMC  A  BN
Correct answer is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012 375

54. Chemical reaction involved in the above transformation can be illustrated as

Me Me Me
Ag2O CH Wolf
Ph N2 Ph Ph
rearrangement C O
MeOH or hv
O –N2 O
MeOH

Me OMe Me Me

Ph OH Ph proton
C OH Ph C O
transfer
OMe HOMe
Me OMe

Ph O

Correct answer is (a)

k P–OMe
55. log 
kH

  log k P–OMe  log k H =  log k H    log k P–OMe   pk a H  pk a P OMe = 4.19 - 4.46 = – 0.27
Correct answer is (d)
56. Biosynthetic precursor of cardinene is mevalonic acid.
Correct answer is (b)

O O
HO O
57. squaric acid is acidic
like H2SO4
HO O
O [Link]
O

–H+ –H+ –H+

O O
O O

O O
O O

Sqaric acid ion is

Here Phenyl ring aromatic in nature.
increases
The E.W. tendency

Acidity  E.W. tendency..

376 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012

So, the correct order of acidity is C > A > B.

Correct answer is (c).

58. Chemical reaction involved in the above transformation can be illustrated as

H Ph
H Ph
peperidine N
N O COOEt
O COOEt O
O
Carbanion(stable)

E1CB

Ph
+ H2N + CO2
COOEt

Correct answer is (d)

59. Chemical reaction involved in the above transformation can be illustrated as
F O
DMSO
+ MeO2S N O
K2CO3
MeO2S N

It is an aromatic Ipso nucleophilic substitution reaction in which which N-atom of reagent attacks on
Ipso position leading to formation of desired product.
Correct answer is (b)

60. Chemical reaction involved in the above transformation can be illustrated as

•
O Ph
[Link]
hv
O
•
CH OH
•
• CH
N
3 2 OH
N N Ph
Ph Me Ph Ph Ph Ph
1, 4-biradical N
Ph
Norrish-type-II reaction

Then reaction proceeds through H -transfer..

Correct answer is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012 377

61. Chemical reaction involved in the above transformation can be illustrated as

Ph O
HN H
N
+ H2N OH
S
N O
O
Ph
O
Ph
OH H2N
H2N + OH
H2N
O
O
Gly
OH
Ala
Phe
Since, Edman degradation occur from N–T–AA. So, the sequence is Phe–Ala–Gly.
Correct answer is (a).
62. DMF appears in two forms as shown below
O
O CH3
C CH3
H N C N
CH3 H CH3

Form-1 at higher temperature Form-2 at 293 K

At lower temperature DMF remains in form-2 preferentially
In form-2 methyl groups are chemically non-equivalent and they appears as singlets at 2.8 and 2.6
ppm.
Singlet at 7.8 ppm appears due to olefinic proton of form-2.
Correct answer is (a)
63. [Link]
C = O structure occurs at cm–1.
1750 – 1735cm–1 for aliphatic esters.
1740 – 1715cm–1 if C = O conjugated with aromatic.
1765 – 1762cm–1 if oxygen atom is conjugated with alkene or aromatic.
Example: Phenyl acetate 1765 cm–1
p-nitrophenyl acetate 1761 cm–1.
O
O2N O C
CH3

Correct answer is (d)

378 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012

64. According to CIP Priorities

H3C CH3

CH3
O
1

4
H
View from inside the cavity.
Bridging group always denote, above the plane.
At chiral centre (1) At chiral centre (4)

2 1

3 1 2 3

4 4
(1s) (4s)
Correct answer is (d).

Position 3 is more susceptible for electrophilic attack in the

65. 3 case of indole.

N1
2 So, the major product will be (a)

H
O
O
CH3
H N
CH3 H

POCl3
N N
H 3O +
H
H
Correct answer is (a)
66.
[Link]
[Link] has isolated individual isomers first time. Pasteur separated the left and right crystal sphapes
from each other to form two piles of crystals.

Mirror image crystals

Correct answer is (b)
67. [18] annulene is aromatic compound and shows ring current
• The ring current produces strong induced magnetic field.
• Outer 12 protons appears at 8.9 ppm because they remains in deshielding zone.
Inner six protons appears at – 1.8 ppm because they remains in shielding zone (up-field)
Hence, statement A and C are correct.
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012 379

H H
H H
Outer hydrogen H~9.828 ppm
H H H
H H

H H
H H H Inner hydrogen H~ -1.8 ppm

H H
H H

Correct answer is (d).

HB

CH3 CH3
68. HA

Br1 Br 2
Molecule has a plane of symmetry bisecting HA and HB reflecting Br1/Br2 and CH3/CH3.
• Br1 and Br2 are reflected by plane so they are enantiotopic to each other.
• HA and HB are bisecting by plane. Hence, they are diasterotopic to each other.
Correct answer is (b).

O
COB COB
69. O OH
NH CH3 NH
OTBDMS OTBDMS

Ester group
The hydrolysis of ester is faster in alkaline medium. So, the correct answer will be K2CO3, MeOH.
Correct answer is (c). [Link]
70. (i) Synthesis of Malachite green
NMe2

H2SO4
CHO + 2 NMe2 CH

NMe2

Malachite (Toxic)
(ii) Friedel-Craft’s acylation of anisole with Ac2O/AlCl3.
380 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012

O CH3 O CH3
O O
AlCl3
+ H3C C O C CH3

COCH3
In this reaction using reagent as well as product is toxic.
(iii) Jones oxidation of benzyl alcohol to benzoic acid.
H2C OH COOH

Acetone/H2SO4/CrO3

In this reaction using reagent is hazardous for body.

(iv) Diels-Alder reaction of Furan and Maleic acid in water.
O
O

OH H2 O
O + COOH
OH
COOH
O
endo
Diels-Alder reaction is the case of Green synthesis.
Correct answer is (d)

Part-C
 2
71. Recoil energy R 
2Mc2

536 E 2
Recoil energy R  eV
M

6 536E 2
[Link]
2.5  10 
139  931.5
2.5 139  931.5  106
E   24.57  103 eV
536
Correct answer is (d).
72. As the -accepting abilities of phosphine increases vC–O stretching frequency of the complex
increases. So, the order of -accepting abilities among the given phosphine is:
PF3 > PCl3 > PClPh2 > PMe3.
i.e. A > B > C > D.
So, the correct combination for vC–O stretching is:
A  2090 C  1977
B  2040 D  1945
Correct answer is (a).
73. Correct answer is (c).
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012 381

74. CH 3COOH  C5 H 5 N :  CH 3COO   C5H 5 NH   solvocation 

CH 3COOH  H 2SO 4  CH3COOH 2  HSO 4  solvent anion 
HClO 4  H 2SO 4  ClO 4  H 3SO 4  solventcation   weak acid

SbF5  2HF  SbF6   H2 F   strong acid 
Correct answer is (c)
75. C2B4H8
(BH)2B4H8; B2H2B4H8
4
Or, 4H
B6 H10    B6 H 6   nido borane
Correct answer is (b)


76.   B  OH  
B  OH 3  OH    4
reversible reaction

In presence of ethylene glycol, B(OH)4– is consumed as shown below and boric acid behaves as
strong acid.
–
H2C OH HO H2C O HO CH2
OH OH
–H2O
+ B B +
HO H2C O HO CH2
H2C OH OH OH

H2C O O CH2
–H2O
B
H2C O O CH2
Correct answer is (b).
77. In Be 2C3 ; Be+ = In tetrahedral voids
[Link]
+
Be =
C3– – =

C3 = In FCC arrangement (Lattice point at corner + at each face centre)

Therefore, coordination number of Be+ = 4
And coordination number of C3  8
Correct answer is (d)
382 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012

H
H H all 5H proton gives on signal in
1
Mo H NMR at 5.48
78. H3C CO
NH CO H H

H3C

Since, the molecule is C2–symmetric. So, two CO’s will give two absorption band in IR spectrum
Correct answer is (a)
79. The structure of cluster [Co3(CH)(CO)9]
CO
OC CO
Co
OC CO
C
OC Co Co CO

OC H CO

So, the number of M–M bond = 3 and bridging ligand = 1 CH

Correct answer is (a)
80. The electronic configuration of Gd3+ and Lu3+ are 4f7 and 4f14, for this ions total angular momentum
is zero i.e. there is no orbital contribution. Therefore, calculated and observed values of magnetic
moment are closest for this pair.
Correct answer is (a)
81. Correct answer is (d)
82. Co3O4 is a normal spinel. In normal spinel the Co2+ ions occupy tetrahedral voids and Co3+ ions
occupy octahedral voids. Therefore, spinel structure of Co3O4 is (Co2+)t(2Co3+)oO4.
Correct answer is (a).
83. In trigonal bipyramidal complexes, the two ligands lie on z-axis and the three in xy plane somewhere
in between the axes. In xy plane, there are four electrons and on z-axis there is only one electron in
2 2 2 2 1
d orbital (Electronic Configuration, d xz  d yz  d xy  d x 2  y 2  d z 2 )
z2

Correct answer is (a)

[Link]
84. So, it creat chiral environment across the catalyst.
Correct answer is (b).
85. [Rh(CO)2I2]– Hydroformylation.
[Pd(PPh3)4]  Heck coupling (It is a catalyst for Heck coupling)

Ru
Ts
N NH  Asymmetry hydrogen transfer.

Correct answer is (a).

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012 383

86. The weight of Pt-gauze as electrode increases by 16–14.5 = 1.5 g because 1.5 g of Cu is deposited on
Pt-gauze. Therefore, weight of Cu in 2.0 gram brass is 1.5g.
1.5
Therefore, percentage weight of Cu in brass =  100  75
2.0
Correct answer is (d)
87. Trans effect of Cl– > NH3 Anti-tumour agent is cis-[Pt(NH3)2Cl]
The precursor of this complex is [PtCl4]2–
2– –
Cl Cl + NH3 Cl NH3
+ NH3 Cl NH3
Pt Pt Pt
Cl Cl Cl Cl Cl NH3

Correct answer is (a).

88. When Fe(NO3)3.9H2O is dissolved in water, the complex ion [Fe(H2O)6]3+ is formed.
+Cl–
[Fe(H2O)5Cl]2+
+PO43–
[Fe(H2O)5(PO4)]
[Fe(H2O)6]3+
SCN– [Fe(H2O)5(SCN)]2+

F–
[Fe(H2O)5F]2+
Correct answer is (a).
89. [Rh(CO)2I2]–  16e– and a better coordinate for O.A.
[Ir(PPh3)2(CO)Cl]  16e– species (Vaska’s complex) O.A. is possible.
[Cp2Ti(Me)(Cl)]  16e– system O.A. is not possible because metal in high oxidation
state.
[CpRh(CO)2]  18e– species as such O.A. is not possible but after the dissociation of
ligand CO’ O.A. is possible.
Correct answer is (d)

[Link]
CO
90. PPh 3

Ph3P Rh
PPh3
H
18 electron species in excess PPh3 it becomes 20 electron species but the active catalyst is 16 elec-
tron species. So, in presence of excess PPh3. The rate of hydroformylation will be decreases.
Correct answer is (b).
384 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012

1 1 1 1 15 1 19 1
91. H 15 H
H I ; N I ; F I
2 2 2
N

2 F
H P
15 F
1 N 1
H H

Four H1 are equivalent. Two nitrogen are equivalent.

Two fluorine are equivalent. One 2H is separate.

Multiplicity =  2  4  1  1 1  1  1 
 2  2   1 2   2  1 2  1  1  = 5  3  3  2  90
 2  2  2  2 
4H1 2N15 2F 1H
Correct answer is (d)
92. The rate of water exchange in [Cu(H2O)6]2+ is fastest due to Jahn-Teller distortion. For other three
complexes of 3d-series dipositive metal cation. The rate of water exchange decreases with increase
in effective nuclear charge and decrease in size.
Correct answer is (a)
93. Because zinc is a Lewis acid and hence,
H H
–H+
Zn2+ O Zn O Zn(OH)
H H
So, correct option is (b)
However, oxidase are enzyme that catalyse the reduction of O2  H2O or H2O2.
 2H 2 O     4H   outside 
O 2  g   4e   8H   inside  
Correct answer is (b)
94. Free heme (i.e. without globular protein chain) it foms-oxodimer) i.e.

O
(III) Fe Fe (III)
[Link]
-oxo-dimer (hematin).

Which is unable to bind O2.

Correct answer is (b)
95. Since SnCl2 will behaves as a carbene and it insert into the M–M bond. So, it is a kind of insertion
reaction.
Cl
SnCl2
(OC)4Co Co(CO)4 Co(CO)4 Sn Co(CO)4
insertion
Cl

Re(CO)5 CH3
H3C Cl
Re(CO)5 Sn Re(CO)5
Sn Metathesis
CH3
H3 C Cl

Re(CO)5
Correct answer is (a).
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012 385

ZM N 0a 3
96. We have,   M
N 0a 3 Z
3

M
1.33 g cm 6.023 10
3 23

mole 1 500 1010 cm  = 25
4
Correct answer is (c)
97. Smaller the volume the greater will be possibility of collisions and therefore the activation energy
will decrease.
Correct answer is (c).
98. In many electron atom, there is strong electron-electron i.e. inter-electron repulsion. Due to inter-
electron repulsion, the orbital angular momentum (l1, l2) as well as spin angular momenta (s1, s2) are
coupled together to give total orbital angular momentum (L) and spin (S).
Correct answer is (a)

volume occupied by particles

99. Packing fraction =
total volume of the unit cell
 No. of particles per unit cell    Volume of 1 particle 
=
Total volume of the unit cell
For simple cubic lattice,
Number of particles per unit cell = 1
4 3
Volume of one particle =r
3
where, r = radius of one particle and a = unit cell edge length.
Then the total volume of the unit cell = a3.
4
1 r3
3 4 r3
Packing fraction =   3.14   0.52 [ for SCC, a  2r ]
a3 3  2r 
3

[Link]
Correct answer is (c)
100. C5H5N
z H

H C H
x C C

y C C
H N H
C2V point group
• Reducible represented by 3N coordinates as basis sets.
E C 2 V  v '
R.R. 33 3 3 11
1 1 1
n A1  33  3  3  11  11 ; n A2  33  3  3  11  4 ; n B1  33  3  3  11  7
4 4 4
1
n B2  33  3  3  11  11
4
386 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012

R.R.  11A1  4A 2  7B1  11B2

Rotational = A2 + B1 + B2.
Transitional = A1 + B1 + B2
Vibrational = 10A1 + 3A2 + 5B1 + 9B2 = 27
Out of 27 3A2 are IR inactive.
So, total IR active 10A1 + 5B1 + 9B2
Total = 24 vibrations.
Correct answer is (c).

+2 +1 0 –1 –2 +1 0 –1 +2 +1 0 –1 –2 +1 0 –1
101.

Total arrangement = 15

Correct answer is (b).

[Link]
102.  2A
A 2 
1 0
1  2
Total moles at equilibrium = 1 
2
 2 
P2  X P  X2
2 1   2
 KP  A  A  A P    4 P
PA 2 XA2 P XA2  1  
  
1  2 
1  

4 2 P
 KP   K P  K p  2  4 2 P
1  2
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012 387

1
2
2
 KP 
 KP    K P  4P    
 K P  4P 
Correct answer is (b)
103. Correct answer is (a)
ZRT
104. P ... (1)
V

 dP   d ZRT  R  d  I  II 
      T Z
 dT V  dT V  V V  dT 

 dP  R   dZ  
  dT   V T  dT   Z ... (2)
 V   V 

 dU   dP   R  dZ  
  dV   T  dT   P  T  V  T dT   Z   P [from equation (2)]
 T  V   V 

RT 2  dZ  ZRT RT 2  dZ 
    P    PP
V  dT V V V  dT V
||
P

 dU  RT 2  dZ 
     
 dV T V  dT  V
Correct answer is (c).
105. For hamonic oscillator, the ground state wave function is,
1
4 x 2
  2
0    e ... (1)

Given :  0  exp  Ax 2  ... (2)

[Link]
Compare equation (1) and (2), we get

  mk 
So, A    2A    
2   
1 1
mk m2k 2
1
 2A  A   A  k 2 
 2
Correct answer is (c)

106. Combining two real wave function 1 and 2 constructed functions  1  2  and i  1  2  repre-
sent the same state because if these two function multiplied by any constant, no effect on the state
and on the energy because multiply only in the eigenvalue, no effect on the energy and no affect on
the wavefunction. If we use any eigenfunction which given eigenvalue. If multiply by any constant
not change in the eigenfunction and no change in the energy of the state. Energy is same, so state is
same only change in eigenvalue.
Correct answer is (c)
388 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012

107. We know that, selection rule for allowed reflection for BCC and FCC lattice is
BCC h + k + l should be even
FCC h, k, l all either even or odd.
Therefore, A is FCC and B is BCC
Correct answer is (a)
108. At low pressure Langmuir Hinshelwood mechanism follows first order kinetics.
2.303 P0 2.303 102
 k log10  log10 4  0.4606 min 1
t Pt 10 10
Correct answer is (b).

N i M i N1M1  N 2 M 2  N 3M 3
109. We know that, Mn  
N i N1  N 2  N 3
10  1000  50  2000  40  4000
 = 2700
10  50  40
Ni M i 2 N1M12  N 2 M 22  N3M 32
Mm  
N i M i N1M1  N 2 M 2  N3M 3
2 2 2
10  1000   50   2000   40   4000  85  107
 
10  1000  50  2000  40  4000 270000
M m 850
 P.D.I.  
M n 729
Correct answer is (c)

110.  2Fe 2  Sn 4

2Fe 3  Sn 2 

Fe 3  e  
 Fe 2  2 ... 1
Sn 2 
 Sn 4  2e  ...  2 
[Link]
2Fe3  2e   Sn 2 
 2Fe2  Sn 4  2e

Since, we know that at room temperature, equilibrium constant

nE0 nE 0
log K eq  
0.0591 0.06
E0  E 0right  E 0left  E0  0.75  0.15  E 0  0.60

2  0.60
log K eq 
0.06
log K eq  20  K eq  1020
Correct answer is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012 389

111. Radioactive process follows first order kinetics and rate law expression is,
N t  N 0 exp  t  (for concentration with increasing time)

And N t  N 0 exp  t  (for concentration increasing with increasing time)

Here, Since bacterial colony is growing i.e. concentration is increasing with increasing time.
Correct answer is (c)
112.
#
We have, H  Ea  n g  1 RT   ... (1)

Here, n #g  1  Bimolecular reaction 

 H  105 kJ mole 1   1  1 2.5 kJ mole1

 105  5  kJ mole1  100 kJ mole 1

Correct answer is (d).
113. Rotational partition function
Zrot  2  Z 'even Zeven  Z 'odd Zodd  ... (i)

For H2 molecule,

1
spin ‘i’ equal to .
2

i i 1
So, Z 'even  and Z 'odd 
2i  1 2i  1

Zeven    2J  1 eBhcJ J1 and Zodd    2J  1 eBhcJ J1

J 0,2,4..... J 1,3,5.....

 1/ 2  1 3
 ortho Z'odd  
 1  2 4
H2  i   
 2  para Z '
 even [Link]
1/ 2 1
2

4

Put the value Z 'even Zeven Z 'odd Zodd in equation (i)

1 hcBJ  J 1 hcBJ  J 1 

   2J  1 e  3   2J  1 e 
4  J 0,2,4...... J 1,3,5....... 

Correct answer is (d).

2n e2 
114. From Debye-Hückel limiting law, charge density    
k BT

 2 4  4  2ne 2 
According to Poission equation of electrostatics            k T 
 r  r  B 
390 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012

8ne 2   2 1  2  
 2    2 r 
r k BT  r r r 

 2 8n e 2 
The equation may be written as  2   k 2   where, k  
 k BT 

ze  kr ze e  kr
The solution of this equation is equal to   e = , the term is total potential in
r r r r
Debye-Hückel it means electrical potential.

e  kr ze ze ze k ze ze
Expand term   1  kr     
r r r r r r r r r  1k 
 I  II 
Potential due to Potential on the ion
the given ion itself due to its ionic atmosphere

Correct answer is (c).

115. Given : e  300 cm 1 and X e  0.0025

Fundamental mode = e 1  2X e 

First overtone = 2e 1  3X e 

Fundamental  300 1  2  0.0025  = 300 (1–0.0025) = 300×0.995 = 298.5

First overtone = 2×300 (1–3×0.0025) = 600(1–0.0075) = 595.5

Correct answer is (b).
116. Langmuir isotherm is given as
kP   
    kP  kP    kP 1     kP   
1  kP 1  

P  
[Link]
1    1  0.95 
= 21.1
k  1    0.9 1  0.95 
Correct answer is (b).
1
117. The energy of a harmonic oscillator in its ground state is 
2
According to Virial Theorem for SHO
Every contribution is equal for kinetic energy operator and potential energy operator.

E  KV
E  KK  K  V 
E  2K  E  

K
2
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012 391

   
 2  2K  K  4 
 
  
Energy only possible if k  and V  energy contribution is equal for K and V.
2 4 4
Correct answer is (a)

hcR H  z2 
118. Energy of a hydrogen in a state is    13.6 2  ... (1)
n2  n 
Degeneracy gn = n2. (for hydrogen atom)

h cR H
If spin include = 2n2 Given : 
25

Compare with equation (1), n 2  25 Degeneracy = 25

Correct answer is (c)

119. H11  ES11 H12  ES12

S11  1; S22  1; S12  S12  0
H 21  ES21 H 22  ES22
H11  1 H 1  0 , H12  H 21  1 H 2   2 H 1  2.0 , H 22  2 H 2  3.0

0  E 2  0  2
 2  0 3  E   3E  E  4  0
 
E 2  3E  4  0; E 2  4E  E  4  0; E  E  4   1 E  4   0
 E  1 E  4   0;
E  4 1
Ground state is lower energy = –1.
Correct answer is (a).
120. Polar molecule AB  A  B has the form C A  A  C B  B
[Link]
C 2A  C 2B  1 for normalization.
Probability on atom B find the electron = 90%
C B 2  90%  0.9  CB 2  0.9
C B 2  0.9 and CA2  0.1
CB  0.9  0.95  CA  0.1  0.32
CA  0.32  C B  0.95
Correct answer is (d)
392 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012

OH OH OH
4 3
– – 162
121. – – – – 116
+
2
133
1 – – C O m-directing 122
C O ortho para directing C
171
OH
HO O OH

• Positions-3 is most shielded because of ortho-to OH and meta to COOH. So, it will appear at 116
ppm.
• Position-1 is shielded because it is para-to OH. It will upper 122 ppm.
If we compare position 2 and 4 position 4 is deshielded due to directly attached OH and it will appear
at 162 ppm.
• Position is normal and appear at 133 ppm.
Correct answer is (b)
122. All of the compounds given 1-4 will give same number of signals and their multiplicity in their
NMR spectrum.
The key parameter to assign the correct structure will be chemical shift of aromatic protons.
• The most shielded singlet 1H signal in aromatic region is at 6.5 ppm is possible.
• In structure 4 only. Because Ortho to OH , Ortho to OMe Meta to COMe
O
HO C
Me
singlet 6.5 ppm
H OMe

Correct answer is (d)

123. • Optically purity also known as enantiomeric excess a compound of 90% B.E. shows 135º specific
rotation.
135
So, its 100% optically pure isomer will show  100  150º specific rot.
90
[Link] 120
• At one hour the specific rotation reduced to 120º. So, E.E, or optical purity =  100  80%
150
150
• At three hours optical purity is 40%. So, specific rotation =  40  60º
100
The over all relation of optical purity, composition and specific rotation can be summarized in the
table.
Optical purity % dext. 10 levo. sp. rot.
100% 100% 0% 150º
90% 95% 5% 135º
80% 90% 10% 120º

40% 70% 30% 60º

Correct answer is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012 393

124. Chemical reaction involved in the above transformation can be illustrated as

Me
3 3, 3 sigmatropic
2 C C
rearrangement H
1O O Ph
2 3
1
Ph Me

PhNEt2
Me Me
Ac2 O
C C C C C C

OAc Ph OH Ph

3, 3 sigmatropic belong to 4n+2 system and 4n+2 system undergo photochemical reaction under
thermal condition with retention in configuration takes place. So, the stereochemistry of –Me and –
Ph group maintain.
Correct answer is (a).
125. Chemical reaction involved in the above transformation can be illustrated as
H
Ph
H Ph
Ph
 
COOH
Con dis
COOH H COOH
H
4n 4n + 2
Correct answer is (c).
126. This reaction is believed to proceed through deprotonation, 3,3, sigmatropic rearrangement and keto-
enol tautomerism.
Chemical reaction involved in the above transformation can be illustrated as

[Link]
OH O
KH, THF 1

3 O
2 1

3 2

 3, 3, sigmatropic
rearrangement

keto-enol H3O+
O OH

O
Correct answer is (c).
394 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012

127. Chemical reaction involved in the above transformation can be illustrated as

Ph Ph Ph
N Et3N C N C N
Cl NO2 NO2
Cl Cl NO2

1, 3 dipolar

Ph NO2

C N
Ph N
Cl NO2 Base
Cl
+
COOEt
COOEt
NO2
H NO2 NO2
Ph N
Ph N Ph N
+
H3O Cl

COOEt COOEt COOEt

Now, the 1, 3 dipolar species will undergo cycloaddition reaction as shown below.
Correct answer is (a).
128. Chemical reaction involved in the above transformation can be illustrated as

O
OH

C H OH CH
Me Me
+ MeHN N

N N
OH

[Link]
N
Me
3
Me

H
CH C Me
OH  N 2
3, 3 sigmatropic
N Me N
3
In Mannich reaction this type intermediate form 2 OH
Me
iminium ion
Me Me
CH N –H+ CH N

N N
O
Me OH

Correct answer is (a)

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012 395

129. Chemical reaction involved in the above transformation can be illustrated as

COOH HOOC O
HOOC O
3
2 COOH
3 Claisen oxidation COOH
rearrangement decarboxydation
1 O
1 2
OH COOH OH O
O O

COOH COOH

OH O
keto form
So, this reaction is Claisen rearrangement and oxidative decarboxylation.
Correct answer is (a)

CH3
H NHCH3
ephedrine
130. H OH
Ph

alkaloid secondary
alcohol

HO
Phenolic part alkaloid

O
N CH
3 squalene

HO
[Link]
Morphine acyclic triterpene polyene

-amyrin triterpene and secondary alcohol.

HO
-amyrin

Correct answer is (a).

396 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012

OH O
Ph CHO Ph
131. + B
Me Me
The above case belong to aldol condensation. In aldol condensation two types enolate are formed as
intermediate
(i) Z enolate (ii) E enolate
The formation of a particular enolate depends upon the carbonyl compound. For example.

O O O

Base

E enolate
O O O

Z enolate
Z enolate give syn product. E enolate give anti product.

In the product the stereochemistry of –OH and CH3 is syn. So, Z enolate participate in reaction.
1
O
H H OH
OH 2
3
NaBH4 (Re face attack) NaBH4
H3C H3C
H3C

Re face (Si face attack)

1 [Link]
O Nu OH
Ph 2 3 Ph
Nu
H H
Re face attack
Me Si Face Me Si Face
1
O O OLi
3 2 Ph
Ph LDA Ph

Si Face
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012 397

O
OH O
Ph O–Li+
H Ph
+
Me Me Me

The enolate is Z. So, syn product will be form and Re face of carbonyl compound and Si face of
enolate.
Correct answer is (c)

132. Chemical reaction involved in the above transformation can be illustrated as

N i-PrMgCl N

O O MgCl
Grignard reagent
The Grignard reagent give monosubstitution with Wein-Reb amide.
O
N N O
OMe
N + C
O MgCl
Me O
Wein-Reb amide
Correct answer is (a).
133. Correct answer is (a).
134. Chemical reaction involved in the above transformation can be illustrated as

H O HO O O O
Ca2+
2 O H
H OH H OH H OH
Br2/H2O CaCO3 H2O2/Fe3+ H OH
H OH H OH H OH
Mild oxidising H OH
H OH agent
[Link]
H OH H OH
CH2OH
CH2OH CH2OH CH2OH
(Ruff degradations)
Correct answer is (a).

H CH3 H Me B
H H MeA H MeA
CH3 5 6 1 2 2
135. CH3 H MeB H H
A CH3 A
4 3 H H
2
cis Total = 1 Gauche

MeB is gauche with MeA. MeB is also gauche with C2–C3 and C5–C6 bond. Hence, total 3 Gauche.
So, it has 2 more Gauche interation. So, Total energy 2×0.9 = 1.8 kcal/mol.
Correct answer is (b).
398 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012

136. Chemical reaction involved in the above transformation can be illustrated as

Cu  acac 
N 2 CH – COOEt 
2
 : CH – COOEt 
(A)

COOEt COOEt
:CHCOOEt
H2, 10% Pd/C
MeO MeO
MeO (B)
The formation of product B takes place via hydrogenolysis by H2, 10%, Pd/C. Hydrogenolysis of
cyclopropane takes place via H2, 10% Pd/C and least hindered bond will break.
Correct answer is (a)
137. Chemical reaction involved in the above transformation can be illustrated as
Me
Me O
Chair form
O

LiAlH4, Et2O, –20ºC

O H
LiAlH4 provides a smaller attacking
Ac2O, Py Me OH species. So, in the above existing
H3C O C CH3
structure axial attack takes place

Flliping H3C

1,3, a,e  1, 3 trans

Me
Me
Me
O C CH3 H3C
Me2CuLi
Equatorial attack O

Correct answer is (c). [Link]

138. Iodoform reaction, NaOH  I2 
 NaOI  HI

Ph C CH3 + 3NaOI Ph C CI3 + 3NaOH

O O

Ph C CI3 + NaOH Ph C ONa + CHI3

O O

1 mole of acetophenone = 1 mole of iodoform

mol. wt. = 120 mol. wt. = 394
120 g acetophenone will give 394g iodoform.
394
12 g acetophenone will give  12  39.4 g
120
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012 399

39.4  75
If yield is 75% then 12 g acetophenone will give  29.5 g iodoform
100
Correct answer is (d)
139. Step (A) is O.A. because the oxidation state of the metal is increased by two units.
Ph

L2Pd(O) PhI
L2Pd
I

+2
Step(B) is transmetallation because the ligand is transferring from one metal to another metal.
Step(C) is reductive elimination because the oxidation state of the metal is increased by two units.
Ph
RE
L2Pd Ph + L2Pd(0)

+2
Correct answer is (a).

140. Chemical reaction involved in the above transformation can be illustrated as

OH OH

CHO
CHCl3, NaOH

Reimer-Tiemman reaction

H2O2 + NaOH O O OH

O O
OH OH

C H
[Link]
OH
O H OH
C
O O H
+ O O H

OH

OH O
OH OH OH
O O
OH C
H O C H O
H
HCOOH +

Second step is an example of Dakin reaction.

Correct answer is (b).
400 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012

141. Chemical reaction involved in the above transformation can be illustrated as

O
B D D
Ph
O
Ph C C D O
Syn Addition D B

O
+
H3O

Ph D I Ph Ph D
Ph
Pd(OAc)2 B(OH)2
D D
(A) PPh3, Et3N
Suzuki Coupling

The structure A also be can written as Ph .

D Ph
Correct answer is (a).

142. Chemical reaction involved in the above transformation can be illustrated as

O O

(i) CH2N2Et2O
(ii) Me MgCl, Et2O
O (iii) H3O+ Me

Mechanism:
Step-I:

[Link]
This 'H' in between two
carbonyl hence more acidic.

O O

H
H2C N2 CH2N2
+ H3C N2
Et2O
O O
O O

+ N2
+ H3C N2
O OMe
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012 401

O
ClMgO Me HO Me
MeMgCl, Et2O H+/H2O
Step-II:
OMe OMe OMe
Note: Grignard reagent give 1, 2 addition not 1, 4.

Step-III:

OH2 Me
OH O Me
Me Me

H+/H2O H2O

O CH3 O CH3 O Me Me O
Product

Correct answer is (a).

143. Chemical reaction involved in the above transformation can be illustrated as
H O NNHPh
NNHPh
NNHPh NNHPh
H OH
H OH O
HO H
HO H NH2NHPh NH2NHPh NH2NHPh
HO H
HO H H OH
H OH
H OH
H OH H OH
H OH
H OH
H OH CH2OH
CH2OH
CH2OH Ozazone of D-glucose
CH2OH
D-glucose

NNHPh NNHPh
NNHPh NNHPh
O
[Link]
O
HO H HO H O NNHPh
NH2NHPh NH2NHPh NH2NHPh HO H
HO H HO H HO H

H OH H OH H OH H OH

H OH H OH H OH H OH

CH2OH CH2OH CH2OH CH2OH

(A)
So, the osazone (A) could be obtained from D-glucose and D-mannose.
Correct answer is (a).
402 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2012

144. Chemical reaction involved in the above transformation can be illustrated as

O

(i) Li. liq. NH3, t-BuOH

(ii) H3O+
N (iii) KOH, MeOH Me
Mechanism:
Step-I:

(i) Li. liq. NH3, t-BuOH

N N
H
Step-II:
+
H H H
+
H , H2 O H 3 O+ H 2O H + , H2 O

N N O NH O O O
NH2
H H
Step-III:

KOH, MeOH
O O O O O
O O O
H
O

H+
KOH
MeOH O
HO
O
H
[Link]
Correct answer is (b).
145. Correct answer is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013 403

SOLVED PAPER : CSIR-UGC-NET/JRF June 2013

CHEMICAL SCIENCES BOOKLET-[C]

Part-B

21. First ionization potential of Ne – 2080

First ionization potential of Na – 495
1585 eV

Ionisation Energy = Difference in ionization potential of Neon and Sodium (Ne–Na)

So, 1585 eV is the largest difference in given pairs. The reason being as we move down the group
number of electrons and proton increases simultaneously with addition of new energy shells so
increase in distance from Nucleus to electron is more pronounced as that of increases in electron and
proton resultantly Zeff (effective nuclear charge) decreases and first ionization potential also decreases
down the group.
Correct answer is (d)
22. Uranocene U(C8H8)2 is the most notable cyclo octatetraenidl
of f-block elements and first organouranium compounds.
 K 2  C8H8 
2K  C8 H8 
U C8H82–
2K 2  C8H8   UCl4 
 U  C8H8 2  4KCl
Correct answer is (a)

23. Isolated sp2 hybridisation

But when olefin attach to metal the hybridization of olefin carbon change sp2 
 sp3

sp2 sp3
M M
[Link]
Correct answer is (c).
24. [(-tropylium) Mo(Co)3]+1

x zero-oxidation state
+1 oxidation state

1  x  0  1  x  11  0
Mo in zero oxidation state.
Correct answer is (c)
404 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013

25. Trans effect Cl– has larger trans effect than NH3.

–2 –1 –
Cl Cl Cl Cl Cl NH3
+NH3 +NH3
Pt Pt Pt
–Cl –Cl
Cl Cl Cl NH3 Cl NH3
cis
Correct answer is (a)

26. The electronic transition responsible for the colour of the transition metal ions is d   d * which
is in according to LFT.

character of metal orbitals

antibonding

t2g has -symmetry

a1g, t1u, eg

eg
character of LGO's
t1u
a1g
Correct answer is (b)
27. Total valency electron = 12 + 18 = 30 (A) [ (OPh) in bridging donate 3 electron]
B = (n×18–A) = 36–30 = 6
Metal-metal bond = B/2 = 6/2 = 3
Correct answer is (c)
28.
[Link]
The mulliken symbols for the spectroscopic states arising from free ion term F are
T1g  T2g  A 2g
Correct answer is (c)
29. Nitrous acid (N2O) which is commonly known as laughing gas used as a propellent in whipping
cream. So, also known as whippits or nangs.
Correct answer is (a)

30. The Flame proof fabrices contain urea and phosphoric acid ( H 2 NC  O  NH 2 .H3 PO 4 )
Correct answer is (c)
31. BiCl3 is not readily hydrolysed by water to give BiOCl.
BiCl3  H 2 O 
 BiOCl  2HCl

But BiOCl redissolve in conc. HCl to produce BiCl3 after evaporation. It has quasi molecular struc-
ture. PCl3 is easily hydrolysed by water.
Correct answer is (d)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013 405

32. The coordination geometry of copper(II) in coper(I) protein plastocyanin is distorted tetrahedral.
Correct answer is (d)
33. Nitrogenase enzyme cofactor contains Fe, Mo also known as Iron-molebdenum cofactor.
Correct answer is (a)

CH3 CH3
OC CO O C O C
CH3
Mn insertion OC Mn +CO OC Mn CO

34. OC CO OC CO OC CO
CO CO CO
Insertion reaction

Correct answer is (d)

35. If the system has an even number of unpaired electrons then zero field splitting within the ground
state may result in the EPR transitions being undetectable and only one EPR signal is observed.
Since Ni(II) octahedral complex has two unpaired electrons, therefore, number EPR signals is one
Correct answer is (a)
36. For an element the favourable characteristics both the target and the product in neutron activation is
high neutron cross-section area of the target and long half-life of the product.
Correct answer is (a)
37. From given, we observe that, on reducing the concentration to half of its initial value. The half -life
becomes double.
concentration = ½

Concentration : 1.0, 0.5, 0.33, 0.25 mol dm –3

Time : 0, 1, 2 3 seconds
t½=1 t½=2
1 1
t1  k
2 ak a  t½
Since, order of reaction is 2
Correct answer is (a).

38. n  2 
 n 1
[Link]
n 2h 2 22 h 2 12 h 2
Energy of 1-D box, E n   
 (Difference)
8m2 8m2 8m2
3h 2 h2 6
So, E   6 unit  given     2 units ... (i)
8m 2 8m 2 3

n  3 
 n2  Difference 
For, 32 h 2 22 h 2 h2

  E  5 
8m2 8m2 8m 2
E  5  2  10 unit From equation (i)
Correct answer is (d)
406 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013

1 3
39.  1  2 ... 1
4 4
  c11  c 2 2 ...  2 
From equation (1) and (2), we get
1 3
c1  and c2  (since probability)
4 4
Probability corresponiding E1 equal to c12 .

1 1
c1   c12 
4 4
Correct answer is (c)

40. 1s2
L = 0, S = 0
J  L  S ....... L  S  0

L=0 term defined as S 2s 1

ZJ
1 1
S=  0 2s + 1 = 2×0+1=1
2 2
Term symbol, 1
S0
Correct answer is (c)
41. Number of classes = E, 2C6 , 2C3 , C 2 , 3d , 3 v
1 1 1 1 1 1
Total operation = 1 + 1 + 1 + 1 + 1 + 1 = 6
Order = 1 + 2 + 2 + 1 + 3 + 3 = 12
Correct answer is (c)

42. [Link]
Molecule contains two IR absorbtion lines and one Raman line. So, molecule contains centre of
symmetry and follow the mutual exclusion principle. Because in this type of molecule if IR band is
present then Raman band absent. The common band or line is always zero. e.g. CO2 type molecule.
Correct answer is (b)
–½
43. I½
+½
E    B0
e h eh
  mI  g N  N 
2mc 2 4mc
  mI g n  N  E   m I g N  N B0 for m I
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013 407

 1 1 
for  E mI      g N  N B0 
 2 2 
 E  difference 
 1 1
for  E mI      g N  N B0 
 2 2 

E  g N  N B0
Correct answer is (a)
44. NaCl – HCl – NaOH

Mix neutralized by NaOH

 NaCl  H 2 O
NaOH  HCl 
For component C = N – E = 3–1 = 2
Or total ion = Na+, OH–, H+, Cl– and total N = 4
Equation, (1) Electroneutality
 NaCl  H 2 O
(2) NaOH  HCl 
C = N– E = 4–2 = 2
Correct answer is (b)
45. At the triple point pressure the liquid phase of a pure substance exist.
Correct answer is (c)
46. According to transition state theory, for activated complex, one of its vibrational degree of freedom
is being converted into translational degree of freedom.
Therefore, required vibration degree of freedom = (3N–6)–1 = 3N–7.
Correct answer is (c)
47. Given : total particles = 6 (N) and states {1, 2, 3}
n1 = 1, n2 = 2, n3 = 3
N 6 6  5  4  3  2 1
So, possible arrangements = n n n    60
1 2 3 12 3 2  3  2 1
[Link]
Correct answer is (c)

48. 0 ... (1)

m   m b c
If the concentration four times increased.
 m '   0m  b 4c   m '   0m  2b c ... (2)
From equation (1) and (2), we get
 m   m '   0m  b c   0m  2b c

m  m '  b c
Correct answer is (b)
408 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013

49. For atom recombination, there is a relatively small amount of rearrangement of energy among the
various defracts in the activated complex. Consequently, S# is expected to have a small negative
value. Such process occurs with zero activation energy and negative enthalpy change. e.g. dimeriza-
tion of nitric oxide.

Ea =0

Energy
H = –ve
N2O4

Reaction concentration
Correct answer is (b)
50. In the Lindemann mechanism, unimolecular reaction at low concentration or pressure second order
reaction.
Correct answer is (d)
51. The aggregation of surfactant molecules is defined as micelles.
Correct answer is (a)

52.
1 2

1
Z  8   1 1  2
8
Consider one particle at origin and second one at body center (0, 0, 0), (½, ½, ½)
Correct answer is (b)
a 4
53. d  4
2 2 2 2
h  k 1 00
Correct answer is (c)
54. The value of correlation coefficient lie between –1 to +1.
[Link]
The value found –0.99 near by –1 mean strongly correlate if value out side of –1 to +1 almost on
correlated.
Correct answer is (a)

OH
H 4 6
Ph configuration at the chiral centre at C–2
55. 2 is S geometry at the double bond is E.
1 3 5 7
Therefore, IUPAC name is (2S, 3E)-7-phenylhept-3-en-2-ol.
Correct answer is (d)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013 409

56. Chemical reaction involved in the above transformation can be illustrated as

OH
O OH

O CH3 O CH3 O CH3

H+/H2O OH
H2O
OH OH OH

OH O H
O
O
+ +
H3C OH OH OH H3C OH
More stabilization of reaction intermediate, enhances the rate of hydrolysis.
Correct answer is (b)

H2
57. O CH2 P
10% Pd/C
The above case belong to hydrogenolys is. Bond cleavage by the more electronegative atom in the
presence of catalyst is known as hydrogenolysis.
Hydrogenolysis
C Z C H
Z = High electronegative
Chemical reaction involved in the above transformation can be illustrated as
H2
O CH2 OH + CH3
Pd/c
Cyclohexanol + Toluene
Correct answer is (a)
58. Vicinal dibromides may be dibrominated by treating them with reducing agents like, Iodide ion or
zinc. Debromination using sodium iodide is found to be an anti-elimination.
I

R
[Link]
1 Br
Br R2 R1 R3
slow R3 R1
fast
I + Br + IBr2–
R3 R2
R4 Bridged R4 R2
R4 Br
Anti-periplanar intermediate
This iodine induced reduction is essentially the reverse of a halogenation. Application of the prin-
ciple of microscope reversibility suggest that the reaction proceeds through a bridged intermediate
as shown above.
Out of four options only (b) and (c) are vicinal and out of (b) and (c) only in (c) the two Br are anti
thus the correct answer is (c)
410 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013

Br
Br
Br
Br

Br Br
Br vicinal anti
vicinal syn Br Br
Geminal Br
(a) (b) Br (c) (d) 1, 4 dibromide
Br
Br
Br Br Br

empty antibonding orbial

Br

Br cyclohexene
I
Correct answer is (c)
NH2 O O
H H
N H H F
S
N N2 4 5
O N 2 1
6
59. HO O O N O N
O OH
H H
Amoxicilin (anti-bacterial agent) Uracil 5-fluorouracil

The 5-fluorauracel is anticanceragent.

Correct answer is (d)
60. Chemical reaction involved in the above transformation can be illustrated as

Me Me
O
[Link]
CH3CO3H O

Bayer-Villiger oxidation O
(According to migrating aptitude)
3ºC > 2ºC
migrating aptitude order

Me Me
Me OH
OH
O LiAlH4
OH OH
O

LiAlH4 is a reducing agent and it reduces ester group into alcohol.

Here lactone i.e. cyclic ester is converted into corresponding alcohol.
Correct answer is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013 411

61. The biosynthetic precursor for the steroids is Mevalonic acid.

OH
HO2C
OH
Mevalonic acid
Correct answer is (c)

N CN
62. CN N 2 • + N2
AlBN CN
4Bu 3SnCl  NaBH 4 
 4Bu 3SnH  NaBCl 4
•
• H SnBu3 + Bu3Sn
CN CN
H SnBu3
• • •
Br SnBu3 • H2C H2C
CH2

O OEt O OEt O OEt O OEt

Two groups at position1, 2

will prefer anti-configuration H2SO4, CrO3
to avoid steric repulsion

H HSO4

O O O O Et O OEt
OH
H

CrO3
O OH O O

Correct answer is (b) [Link]

63. Homomorphic ligands: Ligands are called homomorphic, if they are indistinguishable when consid-
ered in isolation. Here HA and HB are thus homomorphic.
Two homomorphic ligands are homotopic, if substitution of first one and then the other by an atom
or a group, which is not already attached to the ligend centre, gives identical product, else hetero-
topic. Since substitution of HA and HB by D gives different products, thus HA and HB are heterotopic.

Ph N Ph Ph N Ph

D H H D
COOH COOH
R S
412 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013

Also, two heterotopic ligands are enantiotopic if replacement of first one and then the other by a
different achiral ligand gives rise to two enantiomers.
Correct answer is (c)

H3C C O

64. (It decreases the

If increases the electron density)
electron density

O
Normal ester gives 1735–1750 but due to phenyl group some extend frequency of C group
upto 1765 cm–1.
Correct answer is (b)

65. Chemical reaction involved in the above transformation can be illustrated as

Br NHMe Br NHMe N Me
aryne
H
H
NH2 NH2

N N N

Me Me Me
H2N H

Correct answer is (d).

66. [Link]
The Terpene Lupeol contains 30 carbons, dividing by 5 (5 carbons in one Isoprene) we get 6.

Isoprene
Hence, lupeal contains 5 isoprene unit.
Correct answer is (c)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013 413

COOH

H
NH2
67. The structure of Amino acid Histidine is N NH

Imidazole ring

Correct answer is (d)

68. The Gauche conformations of n-Butane are non-superimposable mirror image of each other, thus
Gauche conformation is chiral.
Me Me

Me

H
Mirror Me H
If contains neither plane nor centre of symmetry.
A C2 axis passes through the mid-point of C2–C3 bond and bisecting the dihedral angle
between the two methyls.
Correct answer is (b).

69. Chemical reaction involved in the above transformation can be illustrated as

O Me O
H

hv

Mechanism:

[Link]
H 
 • 
O Me O CH2 OH CH2
H H
   • 
 Y-H transfer


H
O OH

-bond cleaves

The above reaction takes place via Norish type-II mechanism.

Correct answer is (d)
414 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013

70. A degenerate rearrangement is a reaction process in which no overall change in structure occurs
and the product is structurally identical to the starting material. An example is the
homotropilidene rearrangement.

20ºC

Homotropilidene
other examples of this rearrangement are bullvalene, semibullvalene, Barbaralane etc.
Correct answer is (a)
PART-C

C  1  34500 
71. kt  n  0   k  n  
 Ct  75 min  21500 

 k  6.3049  103 min 1

0.693 0.693
 t1    110 min
2 k 6.3049  103 min 1
Correct answer is (b)

Me +4 Cl
72. Ti
Cl Cl
In the first complex titanium in high oxidation state +4. So, react faster with  -donor ligand.
Correct order NMe3 > PMe3 > CO.
Where as in the second complex
THF
OC CO
Mo
OC CO
CO [Link]
Mo in low oxidation state. So, reactivity order is CO > PMe3 > NMe3
Correct answer is (c)

73.

Correct answer is (a)

 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013 415

129
74. I, 57Fe and 121Sb
Mössbauer nuclei and they fulfill all the properties for that 57Co is unstable nuclei which is used as
 -source in the Mössbauer spectro photometer for 57Fe study..
Correct answer is (d)
75. Co(II), Zn(II) and Be(II) form tetrahedral complexes with Cl– or OH–.
Be(II) has no d-orbitals, therefore it form tetrahedral complexes.
Co(II) and Zn(II) form tetrahedral complexes with halides and OH–.
Correct answer is (c)

2
 CoCl4 
2
  Co  H 2 O    4Cl
 6H 2O 
76.  6
 blue   Light pink 
Correct answer is (a)

His (73)
(101) His
77. His (77)
Fe
d6-system Fe(II) O O H
O

C O
(58)Glu C
Fe
O
Asp (106) His (54)
His (25)
(II)Fe

Deoxy hemerythrine

In Hemerythrin, one iron centre is pentacoordinated and is hexacoordinated. And iron exist at
peractive site found in mariene invertebrates.
Correct answer is (b)
 1
78. For systems with more than one unpaired electrons  s   , the ground state can be split in the
 2
absence of external magnetic field due to local site symmetry-the zero field splitting. For odd
electrons systems, this results in pairs of energy levels known as Kramer’s doublets. Since Cr(III)
[Link]
has three unpaired electrons, therefore number of Kramer’s doublets in tetragonally distorted
Cr(III) complex in zero field splitting is 2.
Correct answer is (b)

79.  Bu 4 N 2 Re 2 Cl8

Cl
–2
Cl
Cl Cl
2[Bu4N]+ + [Re2Cl8]–2 Cl
Re Re
Cl
Cl Cl
416 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013

*
*
ABMO
*
[LUMO]

HOMO


BMO


* transition
Correct answer is (b)
80. Ce(SO4)2 and KMnO4 gives one electron on reduction with hydrazine in acidic medium and HNO2
and I2 gives two electron and four electron on reduction with hydrazine in acidic medium.
Correct answer is (a)
81. HClO4 behave as an acid in H2SO4. Because HClO4 contain higher dissociation constant than that of
H2SO4.
HClO4 pKa value –9, H2SO4 pKa value –3, HNO3 pKa value –1, CH3COOH pKa value 4.7.
pKa value of HClO4 > pKa value of H2SO4.
Correct answer is (c)

2 H O
82. (A) N2O3: HNO2  HNO2  N 2O3
O
O
N N
– O

N–N bond
2 H O
(B) N2O4: HNO3  HNO2  N2O4
O
O
N N

O [Link]
O

N–N bond
Correct answer is (c)
83. This follows electron transfer (radical) process
•
Br
•
n BuLi

Hence, formation of 4-membered transition state model.

Li Bu #
Li
Br
+ nBuBr

Correct answer is (d)

 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013 417

84. Cyclobutadiene is
which is antiaromatic and unstable due to this reasons it dimerizes, but when it attached with metal
such as

Fe(CO)5 + + 2CO
Fe
OC CO
OC
The back  -bonding occurs from metal to cyclobutadienes due to this it gain electro from the metal
and converted, into cyclobutadiene anion which aromatic and hence stables.
Correct answer is (c)
85. Increasing   acidity
NEt3 < C2H4 < C2F4 < CO
Where,NEt3 = Neither  -donor nor  -acceptor
C2H4 < C2F4 < CO = Increasing order of  -acceptor ability (on the bases of LFT)
Correct answer is (d)

86. [VCl6]–4 Oh V(II) d3

3 electron unpaired

e1g
a1g 2 electron unpaired
Cr
e2g

[Co(NO2)6]–3 Oh Co(III) d6
No unpaired electron

[Ni(EDTA)]–2
[Link]
8
Ni(II) 3d square planar no unpaired electron
More unpaired electron in [VCl6]–4. So, it contain highest magnetic moment.
s  3  3  2   15 B.M.
Correct answer is (a)

87. OC CO
CO
Ir
OC CO
OC Ir Ir CO
OC CO
Ir
CO
OC CO
418 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013

A = TVE = 60
B = (n × 18)–TVE = 72–60 = 12
Metal metal bond = B/2 = 12/2 = 6
Correct answer is (b)
88. Intensity of C  4
A 2g  2 E g  is lowest, since it is spin forbidden.
Correct answer is (b)
89. As we move from Nb–Ta and Mo–W there is introduction of electron into f-orbital. As the shielding
power of f-orbital is very less. Therefore, as we move from La–Lu in 4f series the size decreases, this
is termed as Lanthanide contraction. This leads to slight increase in size of 5d metal than 4d. Due to
this size of d and 5d metals are nearly similar. Hence Nb–Ta and Mo–W have similar covalent radii.
Correct answer is (a)

90. obs  s  
obs  s only if   0 {completely quinched}
+3 +2 +1 0 –1 –2 –3
Nd(III) = f 3 L0

+3 +2 +1 0 –1 –2 –3
Gd (III) = f 7 L=0

+3 +2 +1 0 –1 –2 –3
9
Py(III) = f L0

L  m So,   will be zero only for Gd (III) f 7.

Correct answer is (a).

91. From spectro chemical series order, Br   Cl  NCS

Order of  t
2
[Link]
2 2
 Co  NCS   CoCl4    CO  Br4  
 4
Correct answer is (a)
92. If S and P have   0 , then titrant shows parallely and after end point goes increasingly with respect
to substate.
Correct answer is (c)
 3
93.  Cr  EDTA   and  Ru  bipy 3  are octahedral and have no plane of symmetry. Therefore these

are chiral complex.  PtCl  diene   is square planar and has plane of symmetry. Therefore, it is
achiral.
Correct answer is (b)
94. Correct answer is (c)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013 419

Low
95. temperature -quartz -tridymite -cristobalite

573ºC 120–160ºC 200–275ºC

1710ºC
-quartz -tridymite -cristobalite Liquid SiO2
High 870ºC 1470ºC
temperature

Correct answer is (b)

96. For (c), r  k  AB B2 
Since, rate is given by slow step.
Therefore, this mechanism is consistent with the given rate law.
Correct answer is (c)
97. When chain machism exceeds the chain termination, it result in uncontrolled step, chain reaction
that ultimately results in explosion.
1n
For nth order, t 1   A0 
2

1 2.5  32
Therefore, for n = 2.5, t 1   A 0  i.e. t 1   A 0
2 2

2
k1k 3  A 
Rate law expression is, r 
k 2  A  k3

1
For low ‘P’ k 2  A   
 3
2
 r  k1k 3  A 

and for high P, k 2  A   k 3

 r  k1k 3  A  /k 2
k1

A  A  
 A*  A and A * 
k3
P
k
[Link]
2

2 2
 
 A*    r  k1  A  k1k 3  A 
 r  k  A *
   A*    r 
3      k 2  A  k3
 k3  k 2  A   k3
Correct answer is (a)
98. As we know for the particle in 1-D box
n 2h 2
En 
8m2
Variation principle says.

E approx  E actual

L 
 approx  x   x   L  x 
2 
420 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013

at x  0   0
 boundarycondition
at x  L   0

L 
Also at x    0 node means given wave function represent n  2 one node
2 

n 2h 2 h2
E  E 
So, approx 8mL2 approx 2mL2
22 h 2
E2  E2 E 
approx approx 8mL2
Correct answer is (b)

1 N
99. Covariance, A    x i  x  yi  y 
N i 1

x y xi  x y1  y
1 1 1  0  1 1  2  1
0 2 00  0 1  2  1
1 3 1 0  1 3 2 1
6
x 0 and y  2
3
1
A
3
 x1  x  y1  y    x 2  x  y2  y    x3  x  y3  y 
1 1 2
  1 1   0  0   11  1  1 
3 3 3

Correlation coefficient,
  x  x  y  y   i i

[Link]
 x  x  y  y i
2
i
2

xi  x yi  y
1 1
0 0
1 1
2 2 2 2 2
 x  x  x  x  x
i 1 2  x    x 3  x    1  0 2  12  2
2 2 2 2 2
 y  y   y  y  y
i 1 2  y    y 3  y    1  0 2  12  2

  x i  x  yi  y   2 (from covarience)
2
B 1
2 2
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013 421

Correct answer is (a)

100. In r 2  1  r   2  r  e r
Where, 1  r = represent one radial node i.e. 1  r
 2  r = represent one radial node i.e.  2  r
i.e. total 2 nodes
We know that, radial node = n– l –1 = 2
For option (c), n = 5, l = 2
Radial node = 5 – 2–1 = 2
Correct answer is (c)

2
101. Operator  x,  x, p  

 x, p 2   2ip n n 1
 x, 2ip   2i 2  2   because  x, p x   nip x

2
   p  x , p      p, 2ix   2ih  p, x   2i  i   2i 
2 2

Correct answer is (c)

L
102. 0  x 3 *d

L 2 nx 3 2 nx
 0 sin x sin dx
 L  L

 2nx 
2 L 3 2 nx  2 1  cos 2  x 3  1  cos 
 0 x sin sin     2 L  L 
dx
L 0
L L  2  2

 
 L 3  L
2 x 1 L 3 2nx   x4 
 dx  x cos dx 2 1 2 1 L4 L3
L  0 2 2 0 L      
[Link]
 ||  L 2  4  L2 4 4
0
 0 
Correct answer is (c)

103.

dimension 1 means parallel to the h double prime

mulliken symbol
A or B antisymmetric w.r.t. inversion
2-Antisymmetric [Link] subsidary axis.
a symmetric w.r. to
principle axis.

So, A"2u mulliken symbol.

Correct answer is (b)
422 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013

x
C2(z)
104.
x x
C2(x)

x C2(y)

The structure has three C2 axis perpendicular to each other. If C2(z) is P-axis. Then there is two
vertical plane also.
C 2  2C2  2 v  D 2 d point group

Correct answer is (c)

105. Ground state term  6 D
2s + 1 = 6
5
2s = 5  s  i.e. five unpaired electrons
2
For D, term L = 2

4d5 5s0 not possible

+2 +1 0 –1 –2
L=0
4d 5s

4d4 5s1
[Link]
+2 +1 0 –1 0
L = 2 i.e. D term
4d 5s 5p

4d3 5s1 5p1

+2 +1 0 0 +1
L = 4 i.e. G term (not possible)

4d3 5s2
+2 +1 0 –1 –2 0
L = +3 i.e. F term (not possible)
Correct answer is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013 423

106. Selection rule, M L  0, 1 (for Zeeman Effect) ML

+2
+1
1D
2 0
1
-2

+1

1P1 0
(9 lines)
-1

No field
 
Field

Correct answer is (a)

107. 1 2

4 3
 H11  ES11 H12  ES12 H13  ES13 H14  ES14 
 
 H 21  ES21 H 22  ES22 H 23  ES23 H 24  ES24 
 H31  ES31 H 32  ES32 H 33  ES33 H34  ES34 
 
 H 41  ES41 H 42  ES42 H 43  ES43 H 44  ES44 
H11  H 22  H 33  H 44    coulomb integral

H12  H 21  H14  H 41  H 23  H32  H 34  H 43    (exchange integral)

H13  H 31  H 24  H 42   0

[Link]
S11  S22  S33.....  S44  1 
  overlap integral
S12  S21  S32  S31.....  0 
  E  0  
  E  0 

 0  E  
 
  0    E
Correct answer is (c)

108.  CH3COONa  H 2O

CH3COOH  NaOH 
120×0.05 40×0.05
t=0 6 2 0 0
t=t 4 0 2 2
Therefore, we have acidic buffer
424 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013

pH  pK a  log
salt   pK  log  2   pK  log  1   pK  log 2  pK  0.3010
 a   a   a a
 acid  4  2
Correct answer is ( )
109. Degree of freedom F = C–P+2
Component C = N–E
Only one phase exist i.e. gaseous phase.
C = N–E = 4–2 = 2
Therefore, F = 2 – 1 +2 = 3
Correct answer is (b)
110. With reference to bulk colloid are thermdonynamically unstable but kinetically stable because inter-
facial surface tension form thermodynamically unstable colloid and kinetically stable colloid formed
on electrical double layer
Correct answer is (b)
111. Ax type mean X split with A and A split with X.
Two doublets.

4.72 4.6 1.12 1.0

Difference in chemical shift
AX
measured from centre of multiplex

Centre Centre
4.66 1.06

AX  4.66  1.06  3.6 ppm

[Link]
Coupling constant JAX is separation between peaks of a multiplet.
So, J  4.72  4.6  1.12  1.0
AX

 0.12ppm
 0.12 100  12Hz
Correct answer is (a)
112. k BT  1

n J g j  /k BT 2 2
 e  e  2e 2
ni gi 1
Correct answer is (a)

113.  dq  0 is not true.

Cyclic integral of state function(exact differential) is zero but q is path function (inexact differen-
tial). So cyclic integral of q is not zero.
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013 425

 dw  0 is not true as in the case above.

Heat cannot be converted completely into work in cyclic process because it is the violation of carnot
cycle or carnot engine. Work can be completely converted into heat. (Second law statement)
Correct answer is (d)

114.  Na   Cl

NaCl 
0.01 0.01 0.01
1 1 1 2 2 1
I  m i z i2 =   m1z12  m 2 z 22    0.01 1  0.01 1    0.01  0.01  0.01
2 2   2  2

 2Na   SO42

Na 2SO 4 
0.01 2  0.01 0.01

1 2 2 1 1
I 2  0.01 1  0.01 2     0.02  0.04    0.06   0.03
2  2 2
Correct answer is (b).

100
100 
115. W  for boson particle 
100
100
100 
 S  k B nW  k B n
100

 k B n100100  n 100 
k B 100n100  100n100  100   102 k B
Correct answer is (b)

116.  R
O  ne 
[Link]
RT  R 
Nernst equation, E  E0  n
nF  O 

 RT  R 
E  E0  n
nF O 

n
 R    nF E  E 0    n
 O   nF E  E 0 
O  RT    R  RT  

nF 
O   nF E  E 0  O  e RT E  E 0 

 R  RT  
n  

R 
Correct answer is (b)
426 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013

117. From Bragg’s equation, we have 2d sin   n


 2d sin    (for first order reflection)  d
2 sin 
Then for spacing 2d, we have
  sin 
 2  2d  sin     sin    
4d 4   / 2sin   2

 sin  
   sin 1  
 2 
Correct answer is (c)
118. In molecular orbital treatment of H2, two electrons with opposite spins are assigned to the lowest
molecular orbital   . Thus, the spatial wave function of H2 is
1
 
spatial    1    2  = 2 1  S 1s  H a  1  1s Hb  1 1s  Ha   2   1s Hb   2 
  
Opening out the above expression, we get

1 
 spatial  1 1s Ha   2   1s Ha  1 1s Hb   2  1sHb  1 1s Ha   2   1s Hb  1 1sHb   2 
2 1  S  1s Ha 
In the above expression, the various terms represent the structuers as described below.
First and fourth terms: The terms are 1s H a  1 1s  H a   2  and 1s  H b  1 1s  H b   2  . These con-
figuration assign both the electrons either to atom Ha or Hb and hence they represent ionic structures.

Second and third terms: The terms are 1s  Ha  1 1s H b   2  and 1s  H b  1 1s  H a   2  . These con-
figuration assign one electron to each of the atom and hence they represent covalent structures.
Since the coefficients of all the tems are identical, it follows that MO treatment gives equal
weightage to the ionic and covalent structures. It is expected that the MO function will be poor at
large internuclear separations since the dissociation products will be an equal mixture of ions and
[Link]
atom. In actual practice we get two hydrogen atoms. On the other hand, for very short internuclear
distances one expects that there will also be some chance of finding both electrons in the same
atomic orbital. Thus, MO treatment does take into account this fact, but perhaps gives more weightage
to this fact than what actually exists in the molecule.
Correct answer is (d)
119. A, T = 0.50, c = 0.1m, b = 1cm
B, A = 0.01761, c = 0.1m, b = 1cm
For solution (a),
Ab = –log T = – log(0.5) = 0.3010
Therefore, abs of simultaneous solution of (A) and (B) = 0.3010 + 0.1761 = 0.4771
Therefore, required transmittance = 10  Ab = 100.4771  33.3%
Correct answer is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013 427

120.    KM aV
0.050  5  105 M1/2
V

2 5 1/2
 5  10  5  10 M V
3 1/2
 10  M V  M V  106 g/mol

Correct answer is (d)

121. Chemical reaction involved in the above transformation can be illustrated as

O CH3
CH3
MeMgBr H3PO4 OH2
HO H H2PO4

H2
C HA

HB
By loss of HA By loss of HB
Hoffmann product Sytzeff's product
less stable more stable
Minor Major

c b a
d
Five distinct carbon atoms, thus five signals in proton
e c decoupled 13C NMR spectrum.
e d
Plane of symmetry

c b a
d Eight distinct carbon atoms, thus eight signals in proton
e h decoupled NMR spectrum.

f g
Correct answer is (d)
[Link]
122. Chemical reaction involved in the above transformation can be illustrated as
OH O

OH MnO2 OH

MnO2 (Manganese dioxide) specifically oxidizes allylic and benzylic hydroxyl groups. MnO2 does
not attack carbon-carbon double bonds, triple bonds and saturated hydroxyl group.

O H2C CH2 O O
OH OH
OH OH
P-TSA
428 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013

PCC and Jones reagent oxidizes both primary and secondary alcohols, so cannot be used in first step,
also Jones reagent oxidises primary OH into COOH thus PCC will be used in final step.

O O O O H
PCC
OH O
Pyridinium
chlorochromate
Therefore, correct sequence of steps is
(i) MnO2 (ii) (CH2OH)2/p-HSA (iii) PCC
Correct answer is (a).
123. This is an example of Cram’s rule having chelation.
Chemical reaction involved in the above transformation can be illustrated as

MgBr Co-ordination between Mg and oxygen

O
H Me Me
OH

PhH2C H CH2Ph
H H
Cram's rule

Mg

Me Me
H H
OH
PhH2C H PhH2C H

Reagent attacks away from CH2Ph bulky group.

Therefore, major product is Cram’s product.
[Link]
OH

Ph
Me
(A)
Correct answer is (a)

124. Chemical reaction involved in the above transformation can be illustrated as

Here epoxidation takes place ,  unsaturated double bond and we konw that H2O2/NaOH is the
best reagent for epoxidation at ,  unsaturated double bond. This is due to nucleophilic nature of
attacking spaces.

HO OH + NaOH O OH
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013 429

OH
Front attack
O
O O O O
OOH

Major
Correct answer is (d)

125. Chemical reaction involved in the above transformation can be illustrated as

Li, Liq. NH3, t-BuOH 10% aq. H2SO4

Birch Reduction
MeO MeO O
Me
H OH2 OH2

Intramolecular
proton exchange
H

MeO MeO
H O H2O
H H OH
H

HO O

Correct answer is (d)

126. [Link]
The compound which have maximum charge separation, have highest dipole moment.

Aromatic Aromatic
This compound is aromatic in nature, and have maximum charge separation. So, it have highest
dipole moment.
Correct answer is (b)
430 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013

127.

HOOC H

For homo annular diene,

Basic value = 253
Ring residue = +20
1 exodouble bond = +5
 max  278 nm
Close to 275 nm.
Correct answer is (c)


128. + P
NO2 TiCl3, HCl

D.A.R TiCl3, HCl

+
4+2
NO2 NO2 O
Diels-Alder reaction is ortho-para directive.
Correct answer is (a)
129. To count the number of signal pass the c2-axis, then count number of carbon on each side of c2-axis
as

OH
e b e b
e c a OH f c
a
g d
b c b i b
d c c
[Link]
d
h
e e
HO
a c J g OH
b e i f
c2 one
c2 2c2 axis 5 signal c2 10 signal
only one c2

Group on either side of c2 axis will give same signal.

Correct answer is (c).
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013 431

130.  value and J values of corresponding H’s are illustrated below as

O CH3 2.4(3H, s)
 7.8
(2H, d) H H
J = 8Hz

 6.8 H H
(2H, d)  1.25
O
CH2 CH3 (3H, t)
J = 8Hz
J=7.2Hz

 4.10
(2H, quartet)
J=7.2Hz
Correct answer is (a).

131. Chemical reaction involved in the above transformation can be illustrated as

OH
OH
KMnO4/OH– CrO3 O
COOH
[O]
cleavage of C–C
-Pinene bond (A)
O

A contains H3C C group and will give positive haloform test.

Correct answer is (c)
132. Structure of guanosine is
O
(1)
N
HN
[Link]
N
H2N N
R
Because at position (1) electron density is easily available for donation to the electrophilic reagent.
Hence, electrophilic methyl will joined there .
Chemical reaction involved in the above transformation can be illustrated as
O O
Me

N N I
HN HN
+ H3C I
N H2N N N
H2N N
R
R
Correct answer is (a)
432 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013

133. [4+2] cycloaddition reaction is thermal allowed. So, the above reaction takes place via 4+2 Mecha-
nism in thermal condition. Chemical reaction involved in the above transformation can be illustrated
as
CN
CN
 [Ring opening]
Electrocyclic
reaction
CN O CN O
H
[4+2]
+ 
D.A.R
H
O
O
Correct answer is (c)

134. Chemical reaction involved in the above transformation can be illustrated as

O
O CH3 H
H H H HO N OH
Ph O N OH + N
H
O O
O O Ph
Ph

CH3 O
H N OH
+ CO2 + 2 N
H
O
Ph

[Link]
Phe leu
Correct answer is (b)

The ketonic group can be resolved by the formation

of diastereomeric ketal which can be prepared by diethyl
135. tartarate (optically active) molecule.
CH3
(+)
–
Correct answer is (c)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013 433

136. Chemical reaction involved in the above transformation can be illustrated as

O
H2 O
CH2 H OEt CH2 C OEt C
C
OEt
C OEt
COOEt
NO2 NO2 NO2
O

O O
OH Zn/AcOH
COOEt COOEt
N COOEt NH2 treating NO2 with reducing NO2
H metals in acidic medium
gives amine.

–H2O
COOEt
N
H
(An indole)
Aromatic compound

Correct answer is (a)

137. Suppose initially we had 100 moles of
OH OH OH
OH NO2 NH2
HNO3 Sn/HCl
+

100 moles 25% of 100 moles 90% of 25 moles

NO2
=25 moles =22.5 moles
70% of 100 moles
=70 moles Ac2O
[Link]
OH
OH OH NHAc

Ac2O
90% of 22.5 moles
=20.25 moles
NHAc NH2 20 moles
90% of 63 moles 90% of 70 moles overall yield = 20%
= 56.7 moles =63 moles
57 moles
overall yield = 57%
Correct answer is (a)
434 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013

138. x

In general staggered conformation is stable but in case of F  CH 2  CH 2  F Gauche conforamtion

is stable due to Gauche effect i.e. hyper conjugation.
F F
H F
CH *C–F So,
H H
H H
stable due to Gauche effect
Correct answer is (d)
139. When there is a choice ketone, prefers to react with a 1, 2-diol to form five-membered ring, while
aldehydes prefer to react across a 1, 3-diol to form a six membered ring and Chemical reaction
involved in the above transformation can be illustrated as
O OH
H P-TSA
Ph C + HO
OH
H H3C SO3H

O O
Ph
O* + O* OH
OH
P Ph Q

[Link]
HO HO
O O O O

Ph Ph
more stable less stable
and formed not formed
In P, both Ph and O* are syn. Here all the ring substituents are equatorial thus more stable. Whereas
in Q, Ph and O* are anti and Ph is in axial position. Thus a very large syn diaxial or 1, 3-diaxial
repulsions results thus Q is very less stable and is not formed. Therefore, P is the actual product A.
Correction answer is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013 435

140. Chemical reaction involved in the above transformation can be illustrated as

H OTs
H
OTs
KH/THF

OH O O
O
Correct answer is (d)
141. Chemical reaction involved in the above transformation can be illustrated as

S
SMe
OH
O C O C
H Na Me I
S S

Xanthate ester

On heating this xanthate ester syn elimination results.

This is Pyrolytic syn elimination known as chugaev reaction which can be better shown as

SH

H + C O
O
S
C SMe
SMe 2-Menthene

Correct answer is (a)

N2
O O O O O O O
hv [Link]
  
–CO
142. 
Insertion of Carbene in C—H

Correct answer is (b)

143. Conformational preference is seen in the phtotolysis of cyclodecanone where transannular hydrogen
abstraction takes place for te E-carbon, i.e. a 1, 7-hydrogen transfer to form the cyclodecanol.
OH OH
O
hv •
O O
Et2O •
H H
H H
H and OH trans to each other. Because trans decalin is more stable than cis-decalin.
Correct answer is (d)
436 SOLVED PAPER : CSIR-UGC-NET/JRF June 2013

144. Chemical reaction involved in the above transformation can be illustrated as

hv
hv
transoid 4n Dis

cisoid
COOEt
O3, Me2S OHC Ph3P CHCOOEt

Ozonolysis Wittig reaction

OHC COOEt
Ph3P = CHCOOEt form E alkene.
Correct answer is (a)

145. H
H
hv
4n Dis

H
H

H
H

4n+2 Dis

Correct answer is (d) [Link]

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013 437

SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013

CHEMICAL SCIENCES BOOKLET-[C]

Part-B
21. L-DOPA is used for Parkinson’s disease.
Correct answer is (b)

22. O

O CH3
p-nitrophenoxy group will be strong electron withdrawing group for carbonyl so, C = O
stretching frequency will increase from normal ester to 1770 cm–1.

N
O O

Correct answer is (d)

23. Chemical reaction involved in the above transformation can be illustrated as

Li(NH3) isomerisation Reduction

t-BuOH

H H
Correct answer is (d)

24. Chemical reaction involved in the above transformation can be illustrated as

OMe OMe O OMe O
O O
1. 
+ 2. H2SO4/ OH
NH2 N Me N
OMe [Link]
H OMe H OMe
OMe O OMe
H
H
H2SO4 

N N
OMe OMe
Correct answer is (c)
25. The structure of estrone is
O

It contains one ketone and

one hydroxyl group.

HO estrone
Correct answer is (c)
438 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013

1 1
CH3 CH3
1 1
26. H3C H H3C 2 2 H
2
2 H1 NMR signal 3
3 3 13C NMR signal
H CH3 H 2 2 CH3
2 1 1
CH3 CH3
1
1
1
H NMR: Singlet 12H, singlet 2H
13
C NMR : CH3 signal, CH signal, C signal.
Correct answer is (a)

27.
Lowest energy barriers
This bond has low energy barrier
(cyclopentadienyl anion and tropylium cation)

Among all options, option (c) has gain aromaticity in both the rings. Therefore, the lowest energy
barries for cis-trans isomerisation is option (c)

E-alkene
28.
2 4 6
HO 3 5
OH
1
Cl H

z-alkene
(2Z, 4E)-3-chloro-2, 4-diene-1, 6-diol.
Correct answer is (b)
29. Chemical reaction involved in the above transformation can be illustrated as

Cl
[Link]
Cl Cl

N N N
MeOH
Cl
NaOMe
MeO N Cl MeO N MeO N OMe
OMe

Correct answer is (c)

30. Constituent amino acid present in above dipeptide can be shown as
COOH
COOH
(3)
H(1) (3)
(4) N NH2
H2N (2) COOH Asp
(2) H2N
(1) H COOH
R O (4) S O

Correct answer is (a).

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013 439

31. This reaction is an example of Robinson annulation. In this reaction we required a base and for the
synthesis of optically active compound (A) we will have to use chiral base among all the option only
protein is naturally occuring base.
H
OH
N
O
H
(Optically active base)
The correct answer is (a)

OH O O
32.
H Cr O

O
T.S.-cis
T.S.-trans Ea' > Ea
So, cis oxidised faster then
Ea
Ea' trans isomer
P.E.
H H cis
H
trans
OH
R.C.
Cis O
H O O H

OH O
O
Trans
‘A’ undergoes acylation faster while as ‘B’ undergoes oxidation faster.
Correct answer is (c).

33. HA
HA
N HB
[Link]
Ph
N
Ph
HB

(I)
(II)
Ph Ph
N N

HB HA HB HA
+Z, –HA +Z, –HB +Z, –HA +Z, –HB

Ph Ph
Ph N Ph N
N N
Z HA Z HA
HB Z HB Z

Enantiomer Diastereomer

Correct answer is (b)

440 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013

34. Chemical reaction involved in the above transformation can be illustrated as

4 4
4 3 5
3 3 H 5
5 3
 6
2 6
2 O 1 3, 3-sigmatropic 7 2 O 7 8 6 CHO
1 2 O 1 7
3 1 8
8

Correct answer is (c)

35.
1, 3, 5-hexatriene
+ + – – + + HOMO
n=2 3 m(s)
– – + + – –

+ + + – – –
n=1 2 c2(s)
– – – + + +

+ + + + + +
n=0 1 m(s)
– – – – – –
[Here nodes are represented by dot(•)]

There are two node present in the highest occupied molecular orbital HOMO of 1, 3, 5 hexatrine.
Correct answer is (b)
36. Kinetic isotope effect is seen in slow step. In case of E2-reaction, ‘H’ or ‘D’ is involved.
Correct answer is (b) [Link]
37. Correct answer is (b)

38.  
  Re 2 Cl4  PMe 2 Ph  
  4
CML

1  2M  4

 2M  5

Total valence electron  14  5  9  2M  2  7  14

M  Number of valence electron present in the metal
Nb  Na 8 1
Bond order    3.5
2 2
Correct answer is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013 441

39. +3 –3 +4–2 –2 +3 –3 +4 –4 +1 –1
FeCl3.6H2O + SOCl2 FeCl3 (s) + SO2(g) + HCl(g)
Correct answer is (d)
40. Wilson’s disease is caused by excess accomulation of Cu in the body.
Correct answer is (c)
41. Correct answer is (d)
42. HCo(CO)4, HCo(CO)3PBu3 and HRh(CO)(PPh3)3. These all are the catalyst for hydroformylation
process.
Correct answer is (d)
43. Correct answer is (b)
44. Correct answer is (b)
45. H3CoRu3(CO)12
3+9+8×3 + 12×2 = 60 electron.
Correct answer is (b)

2 3 3
46.  Fe  H 2O     Fe  H 2O     Al  H 2 O  
 6  6  6
Reference – Shriver Atkin ([Link]. 123  Bronsted acid base concept)
Correct answer is (c)
47. Large difference between the size of Li and Cs. So, it is difficult to get a solid solution of these two
metals.
Correct answer is (c)


48. More than 8 electrons in the valence shell of P in  PF6  .
Correct answer is (c)

49. Co 2  t 52g eg2 µ  3.89 B.M.

Cr 2  t 42g eg2 µ  4.9 B.M.

Mr 2  t 32g e1g µ  4.9 B.M.

[Link]
Fe2  t 42g e2g µ  4.9 B.M.
Correct answer is (a)

50. Number of valence electrons in I3 central atom are 8 while in I3 are 10 and hence the geometries
are tetrahedral and trigonal bipyramidal.
Correct answer is (c)


51. ClF3  SbF5   ClF2  SbF6 
 
SbF5 is a very strong F– acceptor and leads to the formation of ionic compound.
Correct answer is (c)
442 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013

52.

60
Bond order  3 bond order  bonding energy
2
High bond energy and HOMO-LUMO gap.
Correct answer is (d)
53. H3PO3 is a dibasic and reducing in nature.
Correct answer is (a)
54. Maxwell square,

S H P

U H

V A T

dU  TdS  PdV
Differentiate w.r.t. dV at constant ‘S’
 U   S   V 
 V   T  V   P  V 
 S  S  S

 S  because entropy is constant.

 V   0
S

 U   U 
  V   0  P   V    P
 S
Correct answer is (a)
[Link]
 S

55. Correct answer is (b)

56. K  A e  E a /kT  Arrhenius equation 

Ea
ln K  ln A  Slope = –Ea/R
RT Intercept = lnA
lnk
 E  1 
ln K    a     ln A
 k  T  (1/T)
y  mx  c
Clearly lnk decreases linearly as 1/T increases.
Correct answer is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013 443

57. 2d sin   n
a
 2
2 2 2
sin    for first order reflection n  1
h k 
 h 2  k 2   2 2.29Å 1  1  0 1
 sin     0.5  = sin 30º   30º
2a 2  3.28Å 2
Correct answer is (a)
58. For radial node = n–l–1= 5-2-1=2
Angular node = l =2
Correct answer is (b)
59. Correct answer is (b)
60. Li  1s 2 2 s1 2 p 0
Li   1s1 2 s 0 2 p 0  hydrogen like 
Be   1s 2 2 s 0 2 p 0
H   1s 2 2 s 0 2 p 0
Li has one electron in 2s and no electron in 2p hence the energies of 2s and 2p orbitals will be
different.
Li++ has only one electron in 1s1 hence will have no screening effect therefore, 2s and 2p will
have same energies.
Correct answer is (b)
61. If a homonuclear diatomic molecule is oriented the z-axis, then linear combination of pz orbitals of
two atoms form  -orbitals.
The molecular orbitals formed by linear combination of px or py orbitals of two atoms is  .
Correct answer is (c)
62. kp changes only by change in temperature.
Correct answer is (b)
63. When we plot  vs P graph it increasing gradually and multilayered is formed. No monolayer is
formed.
Correct answer is (d)

64.
1 [Link]
1
M  8   1 1  2 ; X  6   3
8 2
Therefore, formula = M2X3
Correct answer is (d)
65. In case of Frenkel defect, ions are not missing from the lattice. They just displace into interstitial
sites. Also, no extra ion come from outside into the lattice. Therefore, density remains same.
Correct answer is (c).
2 2
2 *
66. B2  1s 1s 22s *2s 12px 12p y
64
B.O.  1
2
If an electron is added to B2, then will go bonding to   orbital .
74 3
B.O. becomes    1.5
2 2
Correct answer is (b)
444 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013

67. Correct answer is (b)

68. Anode : 4OH  
 2H 2O  O   4e 

Cathode: 2H   2e 
 H2 
Correct answer is (b)

69.  Zn 2  2e 
Zn   oxidation 
Cu 2  2e  
 Cu  reduction 
E 0  1.07V , E 0  0.34, E  Eright  Eleft

1.07  E reduction  E reduction

potential potential
right left

1.07  0.34  E  1.07  0.34   E  0.73V   E

Zn2 |Zn Zn 2 |Zn Zn2 |Zn

 E  0.73
Zn2 |Zn
Correct answer is (d)
70. In this reaction, the first step is chain initiation step, in which the bromine molecule acquires energy
as a result of collision with another bromine molecule to dissociate into two Br atoms.
Correct answer is (b)
Part-C

71.
1 1
For two non-equivalent  -electrons  ,   
If we consider the
following arrangement
mL H –1 mL +1 –1
L = 0  L = 0 
S=1 S=0 H –1 +1 –1

[Link]
2S + 1 = 3 2S + 1 = 1 L= 2  0
term 3 term 1 S=1 term 3
2S + 1 = 3
3
 is not possible.
Correct answer is (d)

1 1
72. V  x, y   k x x 2  k y y2  V  x   V  y 
2 2

2  d 2 d2 
      x, y    V  x   V  y    x, y   E  x, y  
2m  dx 2 dy 2 

2  2
  x, y     x    y     x   V  x  V  y   E  x, y 
2m x 2
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013 445

 2 
 2  x   x   x
   
x     
2   x 2 y 2 
     V  x   V  y    x, y   E  x, y   
 2m    x    y    x    y 
 

2  1  2 1 2 
  2
  x   2
  y   V  x  V  y    x, y   E  x, y  
2m    x  x   y  y 

2
2 1  2 2 1    y 
  2m   x  x 2   x   V  x   E  2m   y  y 2

2
Px2 Py  Px2   Py2 
 E = K.E. + P.E.   V  x   V  y     V  x      V  y  
2m 2m  2m   2m 

 E  Ex  Ey
Correct answer is (c)

V V V
73. V x, y, z   x y z 2 ... (i)
x y z
1 1 1
V x   k x x 2  V y   ky y2  V z   kz z2
2 2 2
V 2  k x x V 2  k y y V 2  k z z
  kx x    ky y    kz z
x 2 y 2 z 2
Put these value in equation (i)
xk x x  y.k y y  z.k z z  2T
[Link]
k x x  k y y  k z z 2  2T
2 2

2 V  2T  V  T
Correct answer is (a)
74. Particle in a box hamiltonian as zeroth order hamiltonian and potential vi from a/2 to a.
a a
2 n x 2 n x 2 n x
 sin V1 sin dx   V1 sin 2 dx
a a a a a a
a /2 a /2

a cos 2n x
2 n x 1
V1  sin 2 dx n x a
 a a  sin 2 
a /2 a 2
446 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013

cos 2n x a a
2
a 1 dx 2 1 cos 2n x 
 V1 a  V1    1dx   dx 
a  2 a 2
 a /2 a /2
a 
a /2

a
2 1 a a  2n x  
 V1   x a /2  sin a  
a 2  2n a /2 

2 1  a a 
  V1    a    sin 2n  sin n 
a 2  2  2n 
Since, sin n  0 , sin 2n  0
2 1 a a
  V1    0  0
a 2  2 2n 
2 1 a V
  V1     1
a 2 2 2
n2h2
V1
 E 
(Perturb part)
2
8 a 2
Correct answer is (d)


1
75.  e  r / a0  P  r  dr    1s 1*s d  d  4 r 2 
3/2  
 a0 0


1 1
P  r  dr   e r / a0 e r / a0 4 r 2 dr
0  a03/2  a03/2
2 2
P  r  dr  4 r 2 1s dr  P  r  dr  4 r 2 1s dr

1
P  r  dr  4 r 2 e2r / a0 dr
 [Link]
dP  r 
Most probable distance, 0
dr
dP  r  4 d 2 2r / a0
 dr
 3
a0 dr
r e 0  
4  2r 2 2 r / a0 2 r / a0 
  e  e 2r   0
a03  a0 
4  r  r r
  2r r 2 r / a0   1  0  1  0   1
a03  a0  a0 a0
r
 1  r  a0
a0
Correct answer is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013 447

76. L  Lx iˆ  L y ˆj  Lz kˆ
 L  mvr  P
and r  xiˆ  yjˆ  zkˆ ; P  px iˆ  p y ˆj  p z kˆ
 
L rP
 iˆ ˆj kˆ  ˆ
   
  i ypz  zp y  ˆj  xp z  p x z   kˆ xp y  p x y
x y z
p
 x py 
ˆ  ˆ ˆ
p z   i ypz  zp y  j  zpx  xpz   k xp y  ypx 
  
L  Lx iˆ  L y ˆj  Lz kˆ = iˆ ypz  zp y  ˆj  zp x  xp z   kˆ xp y  ypx 
Lx  yp z  zp y , Ly  zpx  xpz , Lz  zpx  xp z

 
px  i ; pz  i
x z
         i   
Ly  z  i   x  i   i  z  x    i  z  x 
 x   z   x z  i  x z 

i2       
   z  x   z  x 
i  x z  i  x z 
Correct answer is (b)
77. Since rotational partition function is given by
k BT h
q where, B 
 hcB 8 2 Ic

k BT 8 2 IkT
 q  I
 hc 2
h  h2 q

8 Ic
[Link]
Hence, two factor should be considered
(i) I  µ (ii)   symmetry number 
In present case, H  C  C  H has smallest µ (reduced mass) also having   2 .
Therefore, H  C  C  H will have lowest rotational partition function.
Correct answer is (b)

78. Since, K  and Cl are isoelectric, some of the peaks are missing entirely. The scattering intensities
for X-rays are directly related to the number of electrons in the atom. Light atoms scatter X-rays
weakly, while heavy atoms scatter X-rays more effectively.
Correct answer is (a)

79.  Zn 2  2 Fe 2
Zn  2 Fe 3 
Nernst equation,
448 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013

 Zn 2   Fe2 
0.0591
Ecell  E0  log  
2

2  Fe 3 
 
2
 E0 
0.0591 0.010.001
 Ecell log
2 0.012
0.0591
 1.71  E0  log104
2
0.0591
 1.71  E0    4  log10
2
0.0591
 1.71  E0  4  1.71  E0  0.1182
2
 E0  1.5918
G   RT ln Keq  – nFE0  2.303  8.314  298  log Keq

 – nFE0  2.303  8.314  298  log Keq

 2  96500 1.5918  2.303  8.314  298  log Keq

307217.4
log K eq   53.84  Keq  1054
5705.8
Correct answer is (b)
80. Diffusion coefficient D
D = µkT/ez
which measures the mobility of the ion due to its thermal energy.
Diffusion is the process which involves the migration of a component in solution down a gradient of
its own concentration.
Diffusion coefficient in water of sucrose is smallest because its mobility is very low. It contains high
[Link]
concentration of ion. So, migration of component in solution very small.
Correct answer is (d)
81. We know that, for FCC atomic radius is given by
a 4Å
r   1.414Å
2 2 2  1.414
Correct answer is (b)
82. From Arrhenius, equation, we have
 k  E  1 1  E  T T 
ln  2   a     a  2 1 
 k1  R  T1 T2  R  T1T2 

RT1T2  k  2calk 1mole 1  500k  510k

Ea  ln  2   ln  3  55 kcal mole1
 T2  T1   k1   510  500  k
Correct answer is (c)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013 449

a
83. r  kPNO PHb
2
From experiment I, on doubling pressure of NO rate becomes 4 times
Therefore, a = 2
From experiment II, on doubling pressure of H2 rate becomes almost double.
Therefore, b = 1
2 1
 r  kPNO PH 2
Correct answer is (b)
1+

84.
2 3
Huckel determinant
c11 c12 c13 E  
c 21 c 22 c 23  0   E  0
c31 c32 c3   E

E
Let x  ... (i)


x 1 1 x 1 1 1 1 x
1 x 1  0  x 1 x 1 1 x  1 1 1  0
1 1 x

2
 
 x x  1  1 x  1  11  x   0
3
x3  x  x  1  1  x  x  3x  2  0
 x  2 x  12  0   x  2  x  1 x  1  0  x  2,1,1

[Link]
For x  2 , so from equation (i)
 E
 2  E    2 

For x  1 , so from equation (i)
E
1  E    

Again, for x  1 , so from equtaion (i)
E
1  E    

450 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013

Single electron excitation in

cyclopropenium cation
-
- -
-  

+2
+2 +2


E    2          2      3
Correct answer is (c)

85. F atomic mass = 19.0 amu.

H atomic mass = 1 amu
H–F bond length = 2.0Å
m1m2 2
I  µr 2 , I r
m1  m2
2
19  1 amu  19
I  2.0 Å  2.0 Å  amu  2.0  2.0  Å 2
20amu 2

19  1.67  1027 kg  4
  1010  1010 m 2
20
76  1.67  1047
 kgm2  6.4  1047 kgm 2
20
Correct answer is (b)

86. x1  15.8, x2  15.4, x3  15.6, x4  16

n = 4.
[Link]
15.8  15.4  15.6  16
x  15.7
4

  x1  x 
2
 x1  x 2   x2  x    x3  x 2   x4  x 2
 
n 4


15.8  15.7 2  15.4  15.7 2  15.6  15.7 2  16  15.7 2
4


 0.12   0.32   0.12   0.32 
 0.01  0.09  0.01  0.09
4 4

0.02  0.18 0.2

   0.05
4 4
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013 451

2
Variance (closest) =  2   0.05   0.05
Correct answer is (b)
87. If direct product of ground and excited state transforms according to the x, y and z axis then the
transition will be allowed.
Au × Bg = 1×1, 1×–1, –1×1, –1×–1
= 1 –1 –1 1
= Bu
and Bu transforms as per x-axis. Hence, Bg to Au transition will be x-polarized.
Correct answer is (b)

88. CP  C V  nR
300  C V  10  8.314
CV  300  83.14  216.86  217J / K
Correct answer is (b)
89. dG  VdP  SdT ... (i)
In an isobaric – isothermal process
dP  0 and dT  0
dG = 0 or G = constant
Thus Gibb’s function is that physical quantity which remains constant in reversible isobaric process
From equation (i)
G  G  P, T 

 G   G 
dG    dP    dT ... (ii)
 P T  T  P
From equation (i) and (ii)
 G   G 
 P   V;  T   S
 T  P
And since dG is a perfect differential
  G    G 
[Link]
 V   S 
  T     P 
T  P T P  T  P ;
 
 P  T
Correct answer is (c)
90. The chemical potentials are thus the rate of change of free energy per mole at constant temperature
and constant pressure.
n
dG  SdT  VdP   µi dn i and constant temperature dT = 0 and constant pressure dP = 0
i 1

n  dG 
dG   µi dn i and µi   
i 0  dn i  T,P
Correct answer is (d)
452 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013

91. Work done in reversible expansion process for an ideal gas

W   PdV
nRT
P
V
If gas expand from volume Vi to Vf if process is isothermal then we may integrate it from Vi to Vf.
Vf
dv V
 W   nRT   W  nRT  nVVf
V i
Vi

Vf V
 W   nRT n  W  2.303nRT log f
Vi Vi
Correct answer is (a)
92. 
NaCl  

   ... (i)
Na  Cl


NaI  

   ... (ii)
Na  I


RbI  

   ... (iii)
Rb I
Add (i) and (iii) substract (ii)
                12.7  9.1  10.8
Na  Cl Rb I Na  I

     21.8  10.8
Cl Rb

RbCl  11.0 mSm 2 mol
Correct answer is (d)
93. Number of energy levels (gi) = 2
Number of molecules (Ni) = 4
The number of ways of distribution = giN i  24  16
(since, it is not given either particles are distinguisable or indistinguishable, therefore, we will con-
sider it as distinguishable) [Link]
Correct answer is (c)

ZM 4M
94.  FCC   ... (i)
NVFCC NVFCC

ZM 4M 2M
 BCC    ... (ii)
NVBCC NVFCC NVBCC
4M
 i   FCC NVFCC 2VBCC
 
 ii   BCC 2M VFCC
NVBCC
Correct answer is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013 453

95. Gyromagnetic ratio = 2.7×108 T–1S–1 = 2.7×108/2×3.14 Hz T–1

= 42.5 × 106 Hz T–1 = 42.5 MHz T–1.
Frequency at 12.6 T = 42.5 × 12.6 MHz = 536 MHz.
Correct answer is (c)

speed of source × frequency 2.2  103 m /s  3.48  1018 Hz

96. Doppler shift  
speed of light 3  108 m /s
 2.552  107  25.5 MHz
Correct answer is (c)
97. Order of ligand is spectro chemical series
SCN  Cl  F  CN 
From above it is clear that CN will produce highest energy difference, followed by F , Cl ,
SCN  . As colour of complex is complementary colour of absorbed light.
2
Thus  Co  CN  4  absorbs orange colour radiation which complementary colour is blue therefore
2
colour of  Co  CN  4  is blue.
The other combination according to energy are mismatched. Hence, only option (c) is correct.
Correct answer is (c)

98. (A) N3P3Cl5F = only one isomer

F Cl
P
N N
Cl Cl
P P
N Cl
Cl

(B) N3P3Cl3F3 = three isomer

F
[Link]
Cl F Cl F Cl
P P P
N N N N N N
Cl F F Cl F Cl
P P P P P P
N Cl N Cl N F
F Cl Cl

(C) N3P3Cl3F4 = three isomer

F Cl F Cl F F
P P P
N N N N N N
Cl Cl F F Cl F
P P P P P P
N Cl N Cl N Cl
Cl Cl Cl
454 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013

(D) N3P3Cl2F4 = three isomer

F Cl Cl F Cl F
P P P
N N N N N N
Cl Cl F Cl F F
P P P P P P
N Cl N F N Cl
Cl Cl F

(E) N3P3ClF4 = one isomer

Cl F
P
N N
F F
P P
N F
F

Correct answer is (b)

99. Relative acidic strength of xenon fluorides follows order
XeF6 > XeO3 > F2 > XeOF4 > XeF4 > XeO2F2 > XeF2
This order depends upon
(i) number of lone pair (ii) number of ‘F’ atoms
Correct answer is (a)

100.

450ºC 620ºC

C2B10H12 is show three isomeric derivative which is depend on the temperature.

Correct answer is (a)
[Link]
101. Styx rule
(BH)pHq B5H 9
s : number of BHB unit 
t : number of BBB unit  BH 5 H 4
y : number of BB unit
x : excess hydrogen attached to B alone.  
Hydrogen balance p q
sx q
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013 455

orbital balance
t s  p sx  4
Electron balance t s 5
q 4
p sf  y x t  y  5
3
2 2
q s t y x
p  f  y 2 3 0 2
2
H 3 2 1 1
H B H
4 1 2 0  more symmetry
H B B H

H
H B B
H H
Correct answer is (d)
102. Chemical reactions between analyte and matrix that prevent the atomization of the analyte. One
common one is that Sulfate or phosphates anions will form non-volatile salts with Fe+3, so its signal
decreases. Can be treated in two ways 1. Releasing agents - can add to metal to prevent formation of
interference complexs. This this example EDTA or 8- hydroxyquinoline.
Correct answer is (b)
103. Limiting current (id)
DnF
Current density

id  Cº

Limiting current proportional to cocentration
id1  C10 ... (i) id

id 2  C02 ... (ii)

Electrode Potential
id1  27.15  9.15  18µA
C10  3.0  1.0  2mM
id 2  13.65 µA [Link]
(i) divided by (ii)
id1 C10 18µA 2mM
 0  
id 2 C2 13.65µA C 02
27.30 mM
C02   1.510 mM
18
Correct answer is (d)

104. SO 2  ClF 
 SO 2 ClF
ClF  SO3 
 ClOSO 2 F
Correct answer is (d)
456 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013

OC CO
105. OC
(CO)3 Co
Ir
O CO
OC
(OC)3Ir Ir(CO)3 Co Co
OC CO
Ir C Co C
(CO)3 O
O OC CO
No bridging
3-bridging CO's

Correct answer is (d)

Na 2
106. Fe3  CO 12   Fe  CO  4 
8 + 8 + 2 = 18 electron
2
 Fe  CO   is isoelectronic with Ni  CO 4
 4
Correct answer is (b)
107. (i) Ozone is diamagnetic in nature
(ii) It is non toxic even at 1ppm level
(iii) It is not destroyed by no radial in atmosphere

NO  O 3 
 NO 2  O 2 
(iv) It absorbs radiations in wave length region 290-320 nm
Correct answer is (a)

0 
 
108. (a)  H  Co5  CO 15   H is encapsulated in this clusters
 
+2 +2
(b) [(H)2.Os6(CO)18] [Link]
(c) [(H)2.Os5(CO)16]
Correct answer is (a)
109. AlF3 has octahedral arrangement in 3-dimethyl structure which causes high methyl point of AlF3 in
comparison to AlCl3, AlBr3 and AlI3. AlCl3 dimer has layered structure.
Correct answer is (c)
110. Catalase is a tetramer of four polypeptide chains covering 500 amino acids.
 H 2O  O  Fe  IV   E 0
It works as H2O2  Fe  III   E 

H2O2  O  Fe  IV   E  
 H 2O  Fe  III   E  O2
The colour arises as Fe(III) changes into Fe(IV).
Correct answer is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013 457

O O
111. 4 H H
5
3 NH2 NH2
2 6
N N
1
Z Z
+
NAD
Therefore, the 4-position of the pyridine ring is reactive position in the biological reaction.
Correct answer is (c)
+
112.
CPh3
Fe CH3 Fe D
OC CO D OC CO
CH3 CH3

5 + 8 + 4 + 1 = 18 electron
Correct answer is (d)
113. In case of (c) the chances of conversion of haptacity from 5  3 is more due to partial bond
fixation.
Correct answer is (c)
114. CH  4  1  5 e 
Co  CO 3  9  6  15 e 
But, CH 2  4  2  6e 
O
Ni  CO 2  10  4  14 e  i.e. CH 2   Ni  CO  2
and so on ............
Correct answer is (a)
115. Mn 2  3d5  t 32g e2g  high spin octahedral
CFSE in Oh field = (–0.4×3 + 0.6×2) = 0
[Link]
Cr 3  3d3  t 32g e0g  octahedral 
CFSE in octahedral field. = –0.4×3  0 =    0.4  3 0  1.20
Correct answer is (d)
116.   Xe 4f 6 5d 0 6s2 ; Sm 3 
Sm    Xe 4f 5 5d 0 6s
+3 +2 +1 0 –1 –2 –3
5 5
S  2s  1  2   1  6
2 2
L  3  2  1  1  5
01 23 4 5
SPDFGH
458 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013

J  L  S ............ L  S
5 5
 5 .............. 5 
2 2
15 5

2 2
6 6
H15/2 H5/2
Ground state term, 6 H5/2

Eu  Xe 4f 7 5d 0 6s2 ; Eu 3  Xe 4f 6 5d 6 6s

+3 +2 +1 0 –1 –2 –3
6 6
S  2S  1  2   1  7
2 2
L  3  2  10  1  2 = 3
01 23
SPDF
J  L  S .......... L  S
 3  3 ...... 3  3
6 0
7 7
F6 F0
Ground state term 7 F0
Correct answer is (b)
CH 3 Li
117.
Li

Li
CH3

CH3 Li [Link]
The diagram clearly indicates the four centered-two electron interaction (4c-2e). This takes place in
L i 4(CH3)4. The sp3 hybrid orbital is of carbon while the three s-orbitals are of three surrounding
lithium atoms.
Correct answer is (c)
118. In tetragonal elongation In tetragonal compression

Correct answer is (b)

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013 459

119. Ph Ph
P Cl
Rh
P CO
Ph Ph
IR band at 1985 cm–1 indicates terminal CO. Both P atoms are non-equivalent. Each P atom will
show doublet of doublet with (1JPRh and 2JPP).
Correct answer is (a)
120. Pt  S  d  d bonding in weaker than that of Pt-P bonding. When Pt-S and Pt-P bond are trans to
each other then Pt-S become weaker therefore in such a situation SCN ligand tends to form bonding
through M atoms of ligand as M do not form d  p bonding. Hence, the most probable structure
will be
H3N NCS PPh3
Pt Pt
SCN NH3
Ph3P

Correct answer is (c)

121. Chemical reaction involved in the above transformation can be illustrated as

H Hg(OAc)2
Ph Ph
OAc R C C Hg
2 H2SO4, H2O 2 H
Hg
O O H2O OH

+H –Hg+
R C CH2 Hg R C CH2 Hg R C CH2 R C CH3
from H2SO4
O OH OH O
[R = COPh]
H
Ph Ph N Bn
[Link]
BnNH Ph N Bn
2 2
2 2 Ph
N
O O O OH O
Ph

Correct answer is (d)

460 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013

122. Chemical reaction involved in the above transformation can be illustrated as

H O
O O H2 N NHTs N N N N Ts
Ts
H2O2, NaOH –H2O
O O O

Ts
N
N
H2, Pd/CaCO3
guinoline
(lindlar's catalyst)

O O
O
since lindlar's catalyst convert
alkyne
Correct into cisisalkene
answer (b)

O
H H
123. SePh SePh
H2 O2 heat
O O O
O
SO2 SO2 S
O

H O
heat heat
[4+2]
cycloaddition
H O

Correct answer is (d)

[Link]
124. Chemical reaction involved in the above transformation can be illustrated as

OH O O
NaBH4 Li/Liq. NH3
CeCl3.7H2O
Luche reagent

H2, (Ph3P)3RhCl
Wilkinson cat.

Correct answer is (a)

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013 461

60 80
125. % yield =   100  48%
100 100
Therefore option (b) and (d) are not possible.
O
(3) OH
H (4) (S)-glutamic acid
H2N (2) OH
(1)
O
Since, the reaction is not happen at the stereocentre, therefore stereochemistry of the reactant will
preserved in the product.
(3) H
(2)
N
(1) Ph
N (5)
H
(4)
H
Correct answer is (a)

6.95 ppm, s
126.
H
3.9 ppm, s 4.6 ppm, s
H3CO
OH 5.3 ppm, br, s

H H 6.9 ppm, d
7.0 ppm, d 8.0 Hz
8.0 Hz H
7.3 ppm, t
8.0 Hz

Correct answer is (b)

127. O
5
[Link]
3
H3C 4 CH 3
32 2 1 O 51
O
OMe  = 52 is due to attachment of carbon to O.
C-5 CH3 is due to attachment of carbon to carbonyl group.
C-4 is aliphatic carbonyl centre so above 200
C-1 is ester carbonyl group so below 200.
Correct answer is (d)

128. Chemical reaction involved in the above transformation can be illustrated as

CHCl3/NaOH
H CCl3 CCl2 CCl2
N OH Cl carbene
(intermediate)
H
462 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013

Cl
Cl
Cl
ring
N expansion N
H
Correct answer is (d)
129. Chemical reaction involved in the above transformation can be illustrated as

H2SO4
H
O O HO
H
O O O
H
O O O
H CH3

HO HO
O O
O O

This is a dienone-phenol type rearrangement.

Correct answer is (b)

130. Chemical reaction involved in the above transformation can be illustrated as

O O
m-CPBA Ac2O/ Deoxygenation
+
O OAc
N N N N

O O

Correct answer is (d)

[Link]
131. Chemical reaction involved in the above transformation can be illustrated as

H
BH2 OH
BH3, THF; H2O2/NaOH H2O2/NaOH
hydroboration 2 oxidation

OPPh3 OH
PPh3 K2CO3
MeOH
N N COOEt
EtOOC

Correct answer is (a)

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013 463

132. Chemical reaction involved in the above transformation can be illustrated as

O O
H
H H H
OH CH2I2, Zn-Cu, CH2Cl2 OH PCC, DCM OH
Simmon-Smith O H
OH OH OH
reaction
H H H
OH O
H H
PCC
O DCM O

H H
Correct answer is (a)

133. Chemical reaction involved in the above transformation can be illustrated as

O O Ph O
SOCl2 Ph [2+2] Ph
Ph Ph
OH Cl • O
Ph Ph H2C CH OEt
Ph H NF3 EtO
(favoured)
Correct answer is (b)
134. 2, 4-dinotrofluorobenzene is said to be Sanger reagent and it will react with N-terminal aminoacid.
The DNB-derivative of glycene indicates that, glycene is present at the N-terminal side in the pep-
tide.
i.e.
H2N Gly Ala Phe Ser COOH

O2N F

NO2

O2N NH Gly Ala Phe Ser COOH

NO2 H2O
[Link]
H
O2N N Gly + H2N Ala Phe Ser COOH

NO2
Correct answer is (c)
135. Correct answer is (c)
464 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013

136. Chemical reaction involved in the above transformation can be illustrated as

CN N N CN 
• + N2

NC NC
H •
• + n-Bu3SnH + n-Bu3Sn

H H
Br
nBu3Sn• •
COOEt COOEt
O O
H H
H CN H

• H
COOEt COOEt
O O
H H
H H
Correct answer is (d)

137. Chemical reaction involved in the above transformation can be illustrated as

TsNHNH2
O N N Ts N N
H H
Bu H Bu
O
O
+ NMe2 CHO
H NMe2
DMF

Correct answer is (a) [Link]

138. Chemical reaction involved in the above transformation can be illustrated as
OH OH

BnO SiMe3 BnO

SiMe3
O H O
H
O OH
O
m-CPBA H
BnO O BnO
H O Ar O
H
Correct answer is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013 465

139. Chemical reaction involved in the above transformation can be illustrated as

H
H Me
Me H

8 disrotatory 6 disrotatory
H hv(photochemical) H (thermal)
H Me
H

Correct answer is (b)

140. Chemical reaction involved in the above transformation can be illustrated as

H
H H
H
 
6Disrotatory 6Disrotatory
; H
H H

H
Correct answer is (d)
141. % ee = 90
100  90 10
  5 (100% diastereoselectivity)
2 2
Hence, one diastereomer will be (90 + 5) = 95% and another will be 5%
In case of diastereomer both of stereocentre are changed.
Correct answer is (d)

142. Chemical reaction involved in the above transformation can be illustrated as

O H
Br t-Bu
[Link]
Br
OH Br
O OH O O

Correct answer is (b)

466 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2013

143. Chemical reaction involved in the above transformation can be illustrated as

O O O H
H
hv KOH, MeOH
+ [2+2] cycloaddition
OAc
O H CH O H CH OMe
3 3

H O
O O O O
O H H H
H
CH3COOH
H+
H
O O H O O H

Correct answer is (a)

O

144. The reagent Ph H protects 1, 3diol

O OH
O

Ph O OH
OH
and NaIO4 can cleave diol i.e.
O OH OH
O (i) NaIO4 O
(ii) NaBH4 OH
Ph O OH Ph O
OH
Correct answer is (a)

145.
[Link]
Chemical reaction involved in the above transformation can be illustrated as

(A)  prefer H

•
 O
Norrish type-II •
 Ph OH
(B)   two '' hydrogen are possible but • OH
• C
(not preffer H preffer only A H which is proximity with Ph
not proximimity O
with Ph
C group
O
C group

Ph
O
O
Ph
Correct answer is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014 467

SOLVED PAPER : CSIR-UGC-NET/JRF June 2014

CHEMICAL SCIENCES BOOKLET-[C]

Part-B

21. OH OH OH
NO 2

NO 2
NO 2

O O
O
NO 2

NO 2
NO 2

In case of the first operate resonance as well as more inductive effect, so less basic.
In case of ortho and para resonance as well as inductive effect both operate. Thus, electron withdrawl
will be more in the case of ortho and para substituted nitro phenol.
Thus, conjugate base of ortho and para will be less basic.
Meta substituted phenoxide (II) will be most basic.
Now, in between I and III, since H-bonding (intramolecular) occurs in the case of I, it is less acidic as
compared to para, thus it will be more basic as compared to III.  II > I > III.
Correct answer is (a).
O
P2O5
C
22.
O
O
Mechanism: [Link]
P2O5 is a dehydrating agent. Reacts with 1, 4-dicarbonyl compound to form substituted furan.
This reaction is known as Paal Knorr synthesis.
Correct answer is (a)

2 1 O
3
II I
I 6 IV
III
4
23. 5 III
III
(5S, 6R)
Correct answer is (c)
24. In Biphenyl system chirality is due to presence of plane that is why it comes under planar chirality.
Since, the given molecule possesses a chiral plane. Thus it is optically active.
Correct answer is (a)
468 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014

25. • Trans-Decalin is more stable about 2.7 kcal/mole as compared with cis-decalin.
• Trans-Decalin has a unique and rigid conformation ring fliping is not possible as it would
other wise afford a highly strained system with one ring attached to other by two axial bond.
• Cis-Decalin exists as an equilibrium between two enantiomeric all chair conformation. So, flip
into one other.
H

Flip
No Flipping

H
Trans-Decalin

H
Flipping
H

Cis-Decalin H Cis-Decalin

Correct answer is (a)

26. Ni++ is tested by dmg.

Ni   2dmg  
  Ni  dmg  2   Tschugaeff test 
 Red 
The structure of complex is
H
O O O
Me Me
Me C N C N N C
II
Ni
Me C N C N N C
Me Me
OH
dmg O O
[Link]
H Hydrogen bond
Therefore,
Ni – N bonds  4
Ni – O 
 Zero
Hydrogen bonds  two
Correct answer is (a)
27. Correct answer is (b)
28. N 2  8H   8e  16 ATP 
 2NH 3  H 2  16ADP  16Pi
Correct answer is (b)
29. Particles that are always to emit during positron emission
1
 0 n1  10e  v
P1   antineutrino 
Correct answer is (c)
30. Toxicity of cadmium and mercury in the body is being reversed by cysteine amino acid.
Correct answer is (d)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014 469

Et. Ph 2 .P
31. NiBr2 
78º/CS
A 
  B
2
Re d Green
 
µ  0 BM µ  3.2 BM

n = unpaired n  0 µ  n  n  2 n = near about two.
electrons

Ni++ = 3d84s04p0 =
3d 4s 4p
Hence, (A) will be square planar.
For (A), Ni++ =
dsp2 hybridisation

For (B), Ni++ =

3d 4s 4p
sp3 hybridisation
Hence, (B) will be tetrahedral.
Br
Br PEtPh2
Therefore, NiBr 2 EtPh2P
2 Ni Ni
Br
Ph2EtP Br Ph2EtP
PEtPh2
Square planar Tetrahedral
(A) (B)
(A) and (B) are polytopal isomers.
Correct answer is (a)
32. (I) SCl2 b.p. = 2 l. p. = 2 Stearic number (S) = 4
(II) I3 b.p. =2 l.p. = 3 S=5

(III) I3 b.p. = 2 l.p. = 2 S=4

(IV) ClF2 b.p. = 2 [Link]

l.p. = 3 S=5
Shapes of species are

SCl2 I3 I3
ClF2
•• I •• F
••

••
••

••

S I I I Cl
Cl
••

Cl •• •• ••
I I F
Angular Linear Angular Linear

Correct answer is (b)

33. Ozone is a diamagnetic gas which is of dark blue coloured due to absorption of red light.
   557 and 602 nm 
Ozone depliction discovered by J.C. Farman over Halley Bay in Antarctica.
470 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014

Ozone also show strong absorption in   255 UV which is good for earth and living beings as this
‘UV-b’ is most dangerous
  255  UV  b
Correct answer is (c)
2 2
34. In  AgL4  and  AgL6  , Ag2+ has d9 configuration, hence have unpaired electron. Hence para-
magnetic.
 AgL4 3  Ag 3 has d8 configuration and dsp2 hybridization (square planar so pairing of electron).
Hence, diamagnetic in nature.
Correct answer is (a)
35. Chromium is extracted from chromite ore:
fusion
(I) 4FeCr2O4  8Na 2CO3  7O2 
1100ºC

 8Na 2CrO4  2Fe2O3  8CO2

(II) 2Na 2CrO4  H 2SO4 

 Na 2SO4  Na 2Cr2O7  H 2O

(III) Na 2Cr2O7  2C 
 Cr2O7  Na 2CO3  CO

(IV) Cr2O3  2Al   Al2O3  2Cr

Correct answer is (a)
36.   
221 298K
 5  C5H5 1  C5H5 Fe  CO   
 2   
 5  C5H5 5  C5H5 Fe 
  
Correct answer (b)

37.  CoL6 3  red colour  absorbs green radiations.

V
B
G
3 Y
 CoL '6   green colour  absorbs red radiations. O
R
Energy of green radiations > enegy of red radiations.
Therefore, L will be stronger ligand and than L ' . Thus, L and L ' are NH3 and H2O respectively..
Correct answer is (a)
2 –2
38.  Ni 2  CO 6  OC CO
 
2x  0  2 [Link]
OC Ni N CO
OC CO
2
x  M–M bond =1
2
x  1
Correct answer is (c)
39. SbPh5 is square pyramidal while PPh5 is trigonal bipyramidal.
Ph Ph
Ph
Ph Ph
P Ph
Sb
Ph Ph Ph
Ph
This is due to size of central atom. ‘Sb’ is bigger than ‘P’, therefore favour square planar while small
sized ‘P’ favour trigonal bipyramidal.
Correct answer is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014 471

40. Most commonly the metal in the complexes in their low oxidation state with d8 or d10 configuration
undergo oxidative addition.
Cl H H
+H2O
PPh3 Ir Ph3P PPh3 Ir Ph3P
(+1)
OC OC Cl (+3)
(16 electron)
0
PhBr
Pd  PPh 3 4 
2PPh
 Pd  PPh 3  2  PhBr 

18 electron  3

Correct answer is (c)

41. Correct answer is (a)

42. (pKa = 9.9) H3N COOH (pKa = 2.0)

COOH (pKa = 3.9)

It is aspartic acid (amino acid) which contains ionizable side chain.
When pH = 5; since both COOH group have pKa = 2.0, pKa = 3.9. It will be deprotonated form.
Thus the predominant species that would exist at pH = 5 is

H3N COO

COO
Correct answer is (b)

t-Bu
t-Bu
t-Bu t-Bu
43. hv
[2+2) cycloadition
t-Bu H
t-Bu
Correct answer is (a).
44. [Link]
PCl5 is a polar solvent which will dissolve only in polar solvent.
Therefore, since benzene and carbon tetrachloride both are non-polar solvent. Thus, PCl5 will not
dissolve in it
Correct answer is (c)
472 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014

H
Me
H
AcOH Me
Ph H
OTs Me
OTs
45. Me H Me H
Me
H
Neighbouring group
participatation

+
H H
Me Me

Me H
OAc H Me
OAc

In the presence of neighbouring phenyl group (OTs) depart.

Correct answer is (a)
46. Since N is a electronegative element, thus it decreases the electron density in the ring and thus the
ring is less prone to be attacked by the electrophile in electrophilic aromatic substitution reaction.
Hence, pyridine (I) will be least reactive in which the electronegative element N is present in the
same ring.
Since in structure (I) N is outside the ring and thus it increases the electrophilicity of the ring
by donating electron pair through its lone pair.
Thus it will be most prone to electrophilic attack.
Correct order will be I > III > II
Correct option is (d)
47. Tˆx , pˆ x 
 
 2  2 
  2
,  i 
 2m x x 

2  2    2 2 
  i    
 i    
2m x 2
[Link]
x  x 2m x 2 
 i   i 2   
2 2
 
2m x 2 x 2 m x x x
2i  3 i 2  3
 
2m x 3 2m x3
i3  3 i3  3
   0  zero 
2m x3 2m x 3
Correct answer is (c)
Me
48. NaI
?
DMF
Br
Trans
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014 473

I– strong nucleophile and polar solvent (aprotic) favour SN2 mechanism.

• Since, SN2 mechanism proceed via inversion of configuration.
• Thus, the product formed will have confirmation opposite to that of reactant i.e.
Me Me
NaI
DMF
Br I
Correct answer is (c)
49. When Si is doped with group V elements like P, then at each P centre there is extra electron which
constitute a donor band that lies close to empty conduction band.
VB = Valence band, CB
DB = Donor band, DB

CB = Conduction band VB
Correct answer is (b)

50.
H
H
H
C H

H Plane and axes

C3V
Correct answer is (b)
c    A 0    A t 
51. A  ln  0   k f  ln    ln     kt
 A   A 
 ct  [Link]
 t   0 
y  mx  c
Therefore, straight line with negative slope and intercept = 0
Correct answer is (b)
52. Kinetic chain length describes the number of chain propagation steps in between the chain initiation
step and the chain termination step.
Mathematically it is defined as
rate of product formation
Kinetic chain length = rate of initial step
Correct answer is (a)
53. The triclinic crystal with parameters a  b  c and       90º is least symmetric.
Therefore, no axis of symmetry
Correct answer is (d)
54. Correct answer is (c)
474 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014

55. Steady state approximation for consecutive reactions

k1 k2
P   Q  R
is applied when first step is slow and second step is fast.
Correct answer is (d)

56. W  PV W  P V2  V1 

A – B Work
A I I  B
AI
Work, P = 5 atm
V = 1 to 1
W = 5(1–1) = 5(0) = 0
I  B,
P=1
V  V2  V1  5  1  4
W  PV  1  4   4
Correct answer is (d)

 30 300
57.     60º
c 0.01 5 5
Correct answer is (b)
58. If two phases  ,   of a species are in equilibrium then temperature, pressure and chemical poten-
tial for both phases are in same type.
T  T ; P  P ; µ  µ
Correct answer is (c)

59. S  k B nW
S  k B nW  arrangement 
S  k B nW
S / k B  nW
[Link]
W  eS / kB
Correct answer is (a)
1
60. H NMR chemical shift of these species can be explained on the basis of ring current leads to
deshielding effect.
When these species are placed in magnetic field, the  -electrons in the aromatic ring system
are induced to circulate around the ring. Thus, hydrogen corresponds to these ring are said to be
deshielded by the diamagnetic anisotropy of the ring.
Since, in cylopentadiene ring 4 e  are there and also it is not aromatic, thus, its proton are
least deshielded compared to rest two ring. Thus  value is lowest among three.
Since, benzene and tropylium cation both are aromatic and contains 6 e , but since in the
case of tropylium cation positive charge is there. Thus, its proton are more deshielded as compared
to benzene. Thus,  value will be in order..
III > II > I
Correct answer is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014 475

O O O
OEt
(i) Ph3 C–Na+ C C
61. OEt OEt
(ii) H3O+ O C
C O OEt
OEt
O
O O
–EtO– C OEt
C C + EtOH
H3O+ C OEt
O
Correct answer is (c)

1 2 1 1
2 2
62. 3
1 4
3 2 6
3 6
4 5
5 6
3 5
5 4
4 (2Z, 4Z)-2, 4 hexadiene
6
(4E)-1, 4-hexadiene (4Z)-1, 4-hexadiene

(2E, 4E)-2, 4-hexadiene

Now, for better overlap in Diels-Alder reaction, the diene must be in cisoid fashion. Thus, favourable
configuration is (2E-4E)-2, 4 hexadiene.
Correct answer is (c)

Ph CN Ph •
63. NH
X Y
H

Ph C Ph C Ph •
X N
[Link]
Y NH N
Y
Thus, X and Y are tautomers.
Also, it is clear from the structure of X and Y that Yis more basic than X.
Correct answer is (d).

3
2
O (i) heat OH
64. 
S [2, 3] sigmatropic shift O (ii) (EtO)3P
1 S1 2
Ph
Ph
(ii) (EtO)3P

Correct answer is (d)

65. Atorvastatin is a cholesterol lowering drug.
Correct answer is (a)
476 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014

66. A maximum five ‘d’ orbitals can form bonding with each other
M M  bonds 1
 bonds 2
 bonds 2
Firstly reported in 2007 in chromium complexes.
Ar Cr Cr Ar
Ar = Substituted aromatic rings.
Correct answer is (c)
67. For np2 configurations (microstates)
L M S

1
(I) l = +1 0 –1 D 2 1 0
2
(II) P 1 3 1
1
(III) S 0 1 0
3
(IV) D 1 3 1
The configuration (IV) violets the Pauli’s Principle, Hence term symbol 3D is not possible.
Correct answer is (d)
68. The formula for ionisation energy is
13.6  z 2 eV
I.E.  | z  atomic number, n  shell number
n2 atom
This is for one electron ‘H’ atom like system
Hence, for Li++ = 1s1 (one electron system)
13.6  32 13.6 12
I.E.   13.6  9 . For ‘H’ atom, I.E. = I.E.   13.6  x
12 12
Therefore, I.E. of Li++ = 9x
Correct answer is (c)

3RT T
69. rms 
M
 rms  [Link]
M
... (i)
Given, T = 2T, m = m/2
From equation (i), we get
2T 4T
rms   rms 
M /2 M
T
 rms  2 (Two time increase)
M
Correct answer is (b)
70. According to Kohlrausch law molar conductance of strong electrolyte decreases linearly with
square root of concentration while that of weak electrolyte decreases exponentially. Hence, (c) is a
strong electrolyte while D is a weak electrolyte.
Correct answer is (c)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014 477

PART-C

3+
O
71. 2+
(H2N)5Ru N C NH2 + [Cr(H2O)6]
Labile
Inert
–H2O

+5
O Cr(H2O)5
(H2N)5Ru N C
NH2

Electron exchange

+5
+2 +3
(H2N)5Ru N C O Cr(H2O)5

NH2
Successor complex

In the successor complex inert ruthenium bridged to inert chromium.

Correct answer is (a)
72. (Phen) is an  -acceptor ligands hence there is mixing of donor and acceptor orbital having similar
symmetry this leads to fast transfer of electron leading to enhance rate of reaction.
3 2
 Fe  phen 3   Fe  phen 3 
   
 
t 52g eg0 t 62g eg0

*5*0 *6e0g
*6 2
Electron transfer takes place from  Fe  *5 Fe3    
Correct answer is (a)
73. [Re2(Me2PPh)4Cl4] – (M)
[Link]
*


82 6
M=  B.O.   3
2 2


*


8 1 7
M+ =  B.O.  2  2  3.5

478 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014

*


8
M+2 =  B.O.  4
2


Correct answer is (a)

74. Correct answer is (c)
•• F
b
F
a Cl F
75. F Cl c2 axis and plane
F •• F
b
19
F  2F doublet
19
F 1F triplet
T shaped structure
Correct answer is (a)
F
76. F
S
••

F
F
Correct answer is (d)
Cl
77. +
Si -
Cl Cl + RMgX
Cl
RLi
R3Al
[Link]
+
In all case there is electrostatic interaction between Si and R
Cl

Si R SiCl3
XMgR
Cl
Cl Cl
Correct answer is (d)
3
78.  V  H 2 O 6 
  V 3 
 3d 2  t 22g eg 0

eg eg eg
hv hv

t2g t2g t2g

3
T1g one electron transfer two electron transfer
3 3 3
T1g + T2g A2g
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014 479

Two transitions.
V1  3T1g  F  
 3T2g  F  ; V2  3T1g  F 
 3T1g  P 
3
A2g
3
T 1g (P)
3
P
3
T 2g
3
F

3
T1g

Correct answer is (a)

79. HNO3
As H3AsO4 Arsenic acid (V)
Hot. and conc.

H2SO4 H2SO4
[H3AsO3] As4O6
Arseneous acid (III)
The reason is that HNO3 is better oxidising agent than H2SO4 also acts as dehydrating agent.
Correct answer is (d)
80. [Fe5(CO)15C)]
Total valency electron = 8×5 + 15×2 + 4 = 74
PEC = TEC – n × 12
PEC = 74–5×12 = 74–60 = 14
PEC 14
 7
2 2
7=n+2 where, n = number of metal in electron.
= 5 + 2 = (n + 2) Nido

81.
Correct answer is (a)
Correct answer is (a) [Link]
82. Correct answer is (d)
83. In thermogravimetric analysis (TGA) use of dynamic innert atmosphere is decrease decomposition
with respect to temperature.
Correct answer is (a)
84. Correct answer is (a)
480 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014

OH2

OH2
85. equatorial bond short
H2O OH2 H2O OH2

Ni Cu

H2O OH2
H2O OH2
OH2

OH2
eg eg

Ni2+ Cu2+

t2g t2g
Symmetrical electronic There is large electron density at z-axis
environment so all bond So, on z-axis increases
length same

Correct answer is (c)

O
N 124º (bent NO)
Cl CO Cl CO
NO
Ir Ir
BF4– BF4
86. Ph3P PPh3 Ph3P PPh3

16 electron 18 electron
Terminal NO = 1672 cm–1
Bridging NO = 1505 cm–1
Correct answer is (a)
87. The electronegativities of elements are
Ca Al As S
1.0 1.5 2.0 2.5
Correct answer is (b)
88.
[Link]
s and p both form  -bonding with complex and  -bonding capacity of sulphur is greater than
phosphorus due to smaller size of d-orbital of sulphur. Hence, in presence of sulphur trans to phos-
phorus donor atom phosphorus-metal bond will be weak hence they do not lie trans to each other in
the complex. As nitrogen does not involment in  -bonding with complex hence when nitrogen atom
is trans to phosphorus, phosphorus become able to form efficient  -bond with metal hence become
stable thats why P and N are trans to each other
Me
Me
SCN N
Pd
NCS
Ph
P

Ph
Correct answer is (c)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014 481

89. Correct answer is (a)

90. H CO2
H+ O

Zn O
His119 C
His94
H O
His96
H H O
O
Zn
His119
Zn His94
His119
His94 His96
His96

HCO3–
O
H
O O O
H2 O H
O O Zn
His119
His94
Zn His96
His119
His94
His96

Correct answer is (a)

91. Correct answer is (d)
92. Sm 4f 6 5s0 6s2
7 0
Eu 4f 5s 6s2
Sm can accept one electron and become half field. So, it is better oxidant.
Correct answer is (b)
93. The movement of iron atom and imidazole side chain of histidine toward the porphyrin plane results
in breaking of some of the salt bridges. The breaking of these salt bridges reduces the strain in
hemoglobin molecule. Therefore, the oxyform of hemoglobin is called relaxed state (i.e., R state).
The T form of deoxyhemoglobin discourages the addition of first dioxygen molecule.
The bonding of one dioxygen molecule to a subunit of hemoglobin reduces the steric hin-
drance in the other subunits (due to breaking of salt bridges) and therefore encourages the third as
well as fourth subunits. This is called cooperative mechanism.

94.
Correct answer is (a)
Total electron [Link]
Co(CO)3 15 electron not isolobal
R2Si 6 electron
Mn(CO)5 17 electron isolobal
CH3 7 electron
Fe(CO)4 16 electron isolobal
O 6 electron
Mn(CO)5 17 electron isolobal
RS 7 electron
Correct answer is (c)
95. As positive charge increases the size decreases while with increase in negative charge increase the
size. This is due to increase in Zeff in former case while decrease in Zeff in later case.
Hence, order of size is S2  S  S2  S4
Correct answer is (c)
482 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014

H
96. H H
Br C
C • C
C C C
n-Bu3SnH, AlBN •
benzene reflux
Homolytic cleavage
H H H
H

H C•

nBu3SnH
AIBN
H H H
Product
Correct answer is (a).

H
N
N Ts N Ts N
O N N
97.
H H
H2N NHTs Bu Bu

CO2H  Li
(i) O C O

(ii) H+

Correct answer is (c)

Bu4N+Br– H H
Br
anhyd. CF3COOH
98. CH2Cl2
H+ Br
Correct answer is (b) [Link]
Ph Ph Ph
O O N N N HO N N N O N N N

CF3COOH
99. + Ph N N N

Intermediate
O
Ph
N –N2

Product
Correct answer is (d)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014 483

100. O a
d
e Me
Me c b O

167
143
O a
d
e Me
Me c b O
52
19
125
Correct answer is (d)
O NH2
101. O
C
C MeO Cl
OH (A) (B)
Et3N

Since less basic group are better leaving group. Thus, Cl will be a better leaving group as com-
pared to methoxy group.
Thus, formation of A takes place according to following mechanism.

O O O
O O
C C O C OMe
C C
OH O MeO Cl
(A)
Et3N

O NH2

N
H
(B)

Correct answer is (a)

102. [Link]
The biosynthesis of isopentenyl pyrophosphate from acetyl CoA consumes three molecule of
ATP and two molecule of NADPH.
Correct answer is (c)

HO
103. O hv OH •
•

O OH
C
OH • OH •
tautomerisation
•
•
• •

Correct answer is (d)

484 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014

104.
O O
C OMe C OMe

BnO BnO
O O
O
N NH2NH2 NH NHNH2
BnO OMe
O O C
NH

H
O O

–H 
NH NH2
BnO BnO

Correct answer is (a)

O O
105. C C O
OH iso-amyl nitrite –CO2
–N2
NH2 N N N
O O Benzyne
Benzene diazonium
2-carboxylate
Now two molecule of benzene combines to form biphenyl (dimerises)

Biphenyl
This benzyne has m/z value [Link]
Correct answer is (a)

)3 B
Et2Zn CH3
106. attack from Pd(PPh3)4
H Zn H
H same side

Correct answer is (d)

 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014 485

107. Total probability = PT = 1

Probability of occupying first three levels = P0 + P1 + P2
PT = P0 + P1 + P2 + probability of finding an oscillator in energy levels in n  3
1 = 0.952 + Pn 3  1  0.952  0.048
Correct answer is (b)
Isoxazoline NH
108. N O OH
PhMCO H 2, raney Ni MeOH, H2O
NO2 C N O O OH
Et3N AcOH
+

Correct answer is (a)

O
109.
C OCH3 O

C OCH3
OH
O
This reaction is acyloin condensation.
The acyloin condensation of diesters favours intramolecular cyclisation over intermolecular
polymerisation.
The mechanism of acyloin condensation consist of 4 steps, which is as follows.
(i) Oxidative ionization of two sodium atoms on the double bond of two ester molecules

O ONa
C
• C• OCH3
OCH3 Na
OCH3 Na
C C
• • OCH3
O ONa

(ii) Intramolecular free radical coupling, followed by alkoxy elimination in both side, producing a 1,
2 diketone.
[Link]
ONa O
OCH3
C• OCH3 C O

C
• OCH3 C
OCH3 O
ONa O

(iii) Oxidative ionization of two sodium atoms on both diketone double bonds. The sodium enodiokete
is formed.
486 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014

•
Na
O ONa ONa
•
•
O ONa ONa
•
Na

ONa OH OH
H2O tautomerisation
(IV)
–2NaOH
ONa OH O

Note : Here along with Na, xylene TMsCl has been used to improve the yield of the product. This is
because by removing the alkoxide ion formed, thereby preventing the base catalyzed side reaction.
Correct answer is (a)
O
110. IR frequency indicates towards a C N group ( ~ = 2210 cm–1) and a carbonyl group C (~ = 1724)
  1.4  t , J  7.1 Hz , 3H    a  CH 3 – CH 2
  1.4  t , 3H 

  4.4  q, J  7.1Hz, 2 H    b  CH 3 – CH 2 – O – EWG

(Further deshielded due to the presence of
electron with drawing group)

Thus the required structure will be

 = 127
O  = 168

 = 118 O  = 62

CN  = 16
=1
[Link]
25
 = 119

Correct answer is (c).

Ph
111. Ph Ph O
N N COOCH3 H3COOC N
 C OCH3

H3COOC [4+2]
H3COOC COOCH3 cycloaddition
Ph Ph
4 electron system
Product
Ph Ph
Correct answer is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014 487

A B
112. O O
O O
Rose Bengal is a dye used for catalytic purpose.
It is [4+2] cycloaddition reaction, which is favourable in photochemical condition.

O O KOOC N N COOK
O O
AcOH
[4+2] cycloaddition O O
O2 Rose Bengal, hv
Note : H2/Pd will lead to the formation of dihydroxy compound
OH

O H2/Pd
O

OH
Thus, it will not be the suitable reagent for above reaction sequence
Correct answer is (b)

H Li I CH2 CH2 I I
BuLi
+ H2C CH2 + LiI
113. N N
N

O O O
Ortho lithiation
Correct answer is (d)
114. For cubic box energy,
h2
Enx n y nz 
8m 2 
n 2x  n 2y  n z2  ... (i)
For cubic box, lowest energy,
3h 2 (2,2,2)
Enx ny nz  12h2 (g=1)
8m 2
[Link]
2
8ml
If energy is twice,
3h 2 11h2 (3,1,1),(1,1,3),(1,3,1)
E n x n y nz  2 (g=3)
8m 2 8ml 2

6h 2 9h2 (2,2,1),(2,1,2),(1,2,2) (g=3)

Enx ny nz  ... (ii) 8ml
2

8m 2
From equation (i) and (ii), we get 6h2 (1,1,2),(1,2,1),(2,1,1)
8ml
2
(g=3)
n 2x  n 2y  n z2 6
It follow if 3h2 (1,1,1)
8ml 2 (g=1)
n x  1, n y  1 and n z  2
0 l
Or, n x  2, n y  1 and n z  1
so, its give three degeneracy of levels.
Correct answer is (a)
488 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014

115.

NaNH2
(a)
O O

(b) O O
From (a),

Br CH2CH2Br Br NaNH2 Br
CH2
C
H2
O O O O
(P)
From (b),

Br CH2CH2 Br Br NaNH2 Br

O O O O
(Q)
Thus, P and Q are the required product.
Correct answer is (a)

MeOOC
116. COOMe MeOOC
C H
Heat O +
O [4+2] C [4+2]
O
COOMe
H
Correct answer is (a) [Link]
SeO2
117. (A)
dioxane reflux
SeO2 is most commonly used for allylic oxidation. First formation of allylic alcohol takes place,
which can be oxidized easily to  ,   unsaturated carbonyl compound if desired.
The oxidation are belived to involve an ene reaction, between the alkene and the hyrated
form of the dioxide, followed by a [2, 3]-sigmatropic rearrangement of the resulting allyl selenic
acid and final hydrolysisof Se(II) ester to the allylic alcohol. Further, oxidation of the alcohol gives
the  ,   unsaturated carbonyl compound. A notable application of this reaction is in the oxidation
of 1, 1 dimethyl alkene to the corresponding E allylic alcohols or aldehydes by selective attack on the
E-methyl group.
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014 489

–H 2O 2
ene 1 3
reaction
H Se 1
Se O OH Se 2
O O
O HO

further H 2O [2. 3]-sigmatropic

oxidation rearrangement
CHO OH HO Se O

Aq. NaCN O–Na+ MnO2

MnO2
CHO CH C O

Cyanohydrin CN CN
Me2NH

i-PrOH
C O
N Me

Me
The aldehyde formed reacts with cyanide to give cyanohydrin. Oxidation of the cyanohydrin with
manganese dioxide gives the acyl nitrile. Which then reacts with the alcohol solvent to give the
ester.
Correct answer is (d)
118. According to the pauli exclusion principle the wavefunction of fermions (here electrons) must be
antisymmetric  i.e.,  1, 2     2,1  .
For a triplet state, spin wavefunctions can be  1   2  or  1   2  or [ 1   2     2   1] ,
which are symmetric in nature. As  total   space  spin . So, for  total to be antisymmetrical w.r.t.
[Link]
electron exchange,  space the spatial part of wavefunction is symmetrical so the spin part will be
1
antisymmetric   1   2    1   2  
2
Correct answer is (d)

 NO 2
NO  O2   add Ar  g  
119. g g  g
(1) Phase only (gas phase) all are gases
P=1
(2) Component
C = N–E
C = 4–1 = 3
(3) F = C–P+2
F = 3–1+2 = 4
Correct answer is (c)
490 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014

TsCl
120. pyridine
OH OTs
OTs OTs
Correct answer is (b)
1/4 1/4
     x 2 /2   2
121.     e x  e  x /2
dx
 
1/2 1/2
     x2    2

    x e dx      x e  x dx
    

n is odd. So, total integration is zero.

 n   x 2
 x e dx  0 if n is odd
 2

 x n e   x dx  0 if n is even.
Correct answer is (a)
122. HO
CHO
H OH H OH OH
OH OH
HO H HO H HO O
HO CHO
H OH H OH O HO
OH OH H OH H HO OH
CH2OH CH2OH

Thus, this nothing but    D  glucose. (cyclic form of    D  glucose).

Now, methylation with MeOH in the presence of acid leads to the formation of mono-methylated
   D  glucose.

Ph CH OHMe
H
OMe
OH [Link]
OH Ph OMe
HO O HO O HO
MeOH/H+ H+
HO HO O O
reflux, 24h PhCH(OMe)2(1 eq) HO
HO OH HO OMe
HO
OMe
Ph O
O O
HO
HO OMe
Product
Correct answer is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014 491

123. Natural abundance of Cl35 is 100% while C37 is 32.5. While natural abundance of 79Br is 100 while
81
Br is 98.0.
Thus, relative intensities of isotope peaks for various combination of bromine and chlorine will be
as follows.
M M+2 M+4
Br 100 97.7 –
Cl 100 32.6 –
Br2 100 199.0 95.4
Since in given problem M, M+2, M+4 peak is in ratio 1 : 2 : 1.
Thus, two Br atom is present in compound A
OH OH2 Br

HBr Br
–H2O
Br
Br
Br Br Br
Benzyl cation (A)
Correct answer is (c)
124. Correct answer is (a)
125. When the variational term are increased the energy come closer to ground state energy. So, the
2
energy of two even function x  x  a  and x 2  x  a  correspond to the energy E2 come closer to E0.
Because the system are very complicated and not solve easily.
Correct answer is (b)

126. NaX  H 2O 
 HX  NaOH  ka HX  2.5 105
C 0 0
C 1    C C

C 2
Kb   K b  C 2
1     1
Kb K
  
C KaC
[Link]
14
K CK  0.01 10
 OH    C  C    2  106
  KaC Ka 2.5  10 5

pOH   log10 OH     log10  2  106   5.698

pH  14  5.698  8.301  8.3
Correct answer is (c)
127. For hydrogen atom.
Virial Theorem.
2 T  V
2 kinetic energy   potential energy
[Link] energy = –13.598
 potential energy  2 kinetic energy
492 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014

 potential energy  2  13.598

potential energy  27.196
kinetic energy  13.598
Correct answer is (a)
128. c12  c 22  2c1c 2s  1
2 2
 0.8   0.4   2  0.4  0.8  s  1
0.64  0.16  0.64s  1
0.64s  1  0.80
0.64s  0.20
0.20
s
0.64
5
s  0.31
16
Correct answer is (b)

129.  2Fe  s   3CO2  g 

Fe 2 O3  s   3CO  g   K1  0.05 1
 2CO  g   O2  g 
2CO 2  g   K 2  2  10 12 2
Equation (1) × (2)
Equation (2) × (3)
Adding both
 4Fe  s   6CO2  g 
2Fe2O3  6CO   K1 2
 6CO  3O 2  g 
6CO 2  g    K 2 2
 4Fe  s   3O 2
2Fe2O3 

K  K12  K 32
2 [Link]
3

  0.05   2  1012  36 36
 0.05  0.05  8 10  0.4  0.05  10  0.020  10 36  2  10 38
Correct answer is (b)
130. Molar internal energy of combution =
M 50  4  2.5 50  10 50 10 10 5000
z        1000 kJ = – 1000 kJ
m 0.5 0.5 0.5 5
Note : Energy of combution has always a negative sign.
Correct answer is (b)

N A kT Q #
131. A is given by A   A  BC  non-linear transition state 
h Q A Q BC
3 3 2
N kT  q rot   q trans   q vib 
 A . 3  3 2 2
h  q   q trans   q rot   q vib  
 trans  
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014 493

N A kT  q rot  q vib  10 1  6 107

 3
 6  1023  1013
h  q trans  1030

Correct answer is (b)

a
132. d hk 
h 2  k 2  2
4.242
 d110   3Å
11 0
Correct answer is (d)
1 1
133. A= corners + face centres  8   6   1  3  4
8 2
And B = 4 (Full 1 contribution in tetrahadral void)
Correct answer is (a)
134. CD3 (ID = 1)
(2nI + 1) = (2×3 × 1 + 1) = 7
Correct answer is (d)
135. The moment of inertia of CO2.

mB
O C O

mA R m
A

I  2m A R 2
2
I  2  2.5 1027 kg  120 pm 
I  2  2.5  10 27 kg  120  120  10 12  10 12 mtr 2
I  5  14400  10 51 kg mtr 2
I  72000  10 51 kg mtr 2 [Link]
I  7.2  10 47 kg mtr 2
Correct answer is (d*)

f
136. f  ... (i)
kf
1
f  ... (ii)
k f  k IC  k ISC
Given, k IC  k ISC  1.2 108 sec 1 and f  5 109 sec
1
Therefore, (ii)  5  109 sec 

k f  1.2  108 sec 1 
1
k f  1.2 108 sec1 
5 109 sec
494 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014

10
kf   101  109 sec 1  1.2  108 sec 1
5
 2  108 sec 1  1.2  108 sec1  0.8  108 sec 1


9 8
 1
Therefore, (i)  f  f  k f  5  10 sec  0.8  10 sec  0.4 
Correct answer is (c)

e 2 NA
137. 
 0  r k BT
 
ci z i2 (Debye-Hückel length)

Debye-Hückel screening lengths

1  k T
 20 r B 2
 e N A c i z i
1
 0

1 1 1
  4 2   25 5   81 9
  
Correct answer is (b)
138. In simple Hückel molecular orbital theory only distinguishes between cis-butadiene and cyclobutadiene
on the bases of energy correction. In cyclobutadiene delocalization energy is zero and cis butadiene
is 0.472
Correct answer is (c)

kp 
139.  or kp 
1  kp 1 
1   1  0.6 
k     0.05
p  1    30 bar  1  0.6 

Correct answer is (a)
140. n = 10, variance = 0.04, µ = 8
[Link]
Standard deviation,   variance  0.04  0.20
 0.2
Coefficient of variation =   0.025
µ 8
In percentage (coefficient of variation) = 0.025×100% = 2.5%
Correct answer is (c)

1 1 
141. Lineweaver-Burk plot  r vs s 
  
km
Slope  r , rmax  k 2  E 0
max

1
and Intercept = r TON (Turn Over Number) = k2
max
Given, Intercept = 5000 M–1 s
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014 495

1
  500 M 1s
rmax
1
 rmax 
5000 M 1s
1
 k 2   E 0 
5000 M 1s
1
 TON 1109 M 
5000 M 1s
1 106 10
 TON  3 9
  105  2 105
5 10 10 5 5
Correct answer is (d)
142. E×E = 2×2 (–1) (–1) 0×0
= 4 1 0
1 1
n A1   4  2  0  1  n A 2   4  2  0  1  n E  1 8  2  10  1
6 6 6
Therefore, E × E = A1 + A2 + E
Correct answer is (a)
143. The product of C2  x  C2  y  is C2(z)
z

x
y
2
H
1 O 2 c2(x) H c2(y)
2 O 1
H H O
H H

c2(z)

1 O 2 2 O 1
H H H
H

c2  x  c2  y   c2  z  [Link]
Correct answer is (c)
144. (I) Cell A and B

Fe  OH  2  s   2e  
 Fe  s   2OH  E0  0.877V
Al3  3e  
 Al E0  1.66V

E0  E0right  E 0left
 –0.87   1.66   0.79V

G  nFE  E   ve 
G   ve  spontaneous 
Fe reduced.
(II) A and C
496 SOLVED PAPER : CSIR-UGC-NET/JRF June 2014

Fe  OH  2  s   2e  
 Fe  s   2OH   aq  E 0  0.877
AgBr  e  
 Ag  s   Br   aq  E 0  0.071

E0  E0right  E 0left
 0.071   0.877   0.948

G   nFE 0 E 0
  ve  (Reaction spontaneous)
G   ve
In this cell Fe carried negative reduction potential goes to left hand side of the half cell and in this
half cell oxidation occur.
Fe oxidised
Note : In electrochemical series (Al+3, Al) stay below to (Fe+2, Fe) and (AgBr(s), Br– : Ag) stay
above. So, (Al+3, Al) reduced and (AgBr, Br–.Ag) oxidised by (Fe+2, Fe).
Correct answer is (b)
O
A BrCN
145. (B)
N N
Me Me
Catalytic hydrogenating works in the case of alkene and alkyne. Thus, H2|Pd will not work here.
Therefore, NaBH4 reduces aldehyde and ketones to corresponding alcohol.
Therefore, reduction of amide to amine can be beautifully done by LiAlH4, but it does not follow the
same pattern as observed for ester and acids.

O O Li OAlH3Li H
Li H AlH3 H
H
N N N N N
Me Me Me Me Me

Br CN Br
Br N
N N CN
CN
Me Me
Correct answer is (a) [Link]
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014 497

SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014

CHEMICAL SCIENCES BOOKLET-[A]

PART – B
21. HF exist as H2F2 and it act as fluoride donar if strong fluoride acceptor is present like SbF5, AsF5.
Therefore, the reaction will be
HF 2 moles  H2F2.
H 2 F2  SbF5   H 2 F  SbF6 
 Lewis base   Lewis acid 
SbF5 act as Lewis acids as it has vacant ‘d’ orbital of suitable energy.
Correct answer is (d)
22. A  -bond involves the overlapping of eight lobes by facewise overlapping. This can take place by
‘d’-orbitals and ‘f’ orbitals.
In ‘d’ orbitals following two possibilities are
Case-I : d x2  y 2  d x2  y2 
  -bond
Case-II : d xy  d xy 
  -bond.
x y x x x

y y y y y
y y
Case : I z Case : II

dxy dxy
d x2  y2 d x2  y2
Both cases are reported in many examples like.
Case-I is reported in dimeric copper acetate (II)
Case-II is reported in Re 2 Cl8
z z

[Link]
Cu Re

Y Cu X Y Re X

d x2  y 2 — d x2  y2 dxy — dxy

Hence, options (a) and (c) are correct.

23. All the ions are isoelectronic. Therefore, the size depends upon effective nuclear charge.
1
Size of isoelectronic ions  z .
eff

F O 2 Na  Mg 2 
Atomic number 9 8 11 12
498 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014

Number of electrons 10 10 10 10
Hence, the order of size will be
2
O F Na  Mg 2

Since, atomic number increases.
Therefore, zeff increases
Therefore, size decreases.
Correct answer is (c)

CH2 Me
24.
CH3
CH2 Me
Et
N
H3C N
N Mg
N
Fe (II) N N
Me
N N Me
H3C
CH3
MeO O
RO2C O
HEME Chlorophyl
O
OH Total 10 -electron in microcyclic ring
OH O

Total 11 -electron in microcyclic ring

NH2
O O NH2

O
H2N
NH2
O N N
CN
Co
H
[Link]
O N N

H2N
O

O NH2
N
HN
N
HO
O
O
P
O
O
O
HO
Vitamin B12
Total -electron is 5

Correct answer is (a )
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014 499

25. The retention of ion in exchanges column depends upon the size of ion. Smaller the size of cation,
stronger will be its binding ability. In cation exchanger column the aqueous solution of ion is passed
where binding ability depends upon hydrated radii.
K+(aq) Na+(aq) Li+(aq)
Since, size of hydrated ion increases
Therefore, binding ability decreases
Ag+(aq) show polarization effect, hence, has high binding ability.
Correct answer is (a)
26. Mercury can be easily oxidised to Hg(I) above +0.4 versus SCE(Standard Chemical Potential). This
property restricts the use of Mercury as anode. This is the limitation of DME (Droping Mercury
Electrode). DME can be applied over the range + 2.4 to –3.0 V with reference to SCE. Above +0.4V
mercury dissolves, gives an anode wave and begins to oxidise to mercurous ion.
Correct answer is (a)
27. Fe  II   3d 6 4 s 0 ; Fe  III   3d 5 4s 0 ; Fe  IV   3d 4 4 s 0
Isomer shift in Mössbauer spectra depend on the s-electron density and d-electron density increase
the s-electron density decrease the isomer shift increase the d-electron density increase the isomer
shift.
So, so correct order, Fe (II) > Fe (III) > Fe (IV).
Correct answer is (a)
28.  x  C6 H 6  Ru  y  C6 H 6  
 
x  4, y  6
 4  C6 H 6  Ru  6  C6 H 6  
 
Total electron = 4 + 8 + 6 = 18 electron. (Diamagnetic complex)
Example : 57 Fe  3d 6 4 s 2
Correct answer is (c)
29. h
Ni  CO  4  PPh 3    Ni  CO 3  PPh 3    CO
18e 
Since Ni(CO)4 follows 18 electron rule. So, it follow substitution via dissociation mechanism i.e.
CO [Link]
Step-1 : Ni  CO  4  Ni  CO 3 (slow)
18 e  16e 
CO
Step-2 : Ni  CO 3  PPh 3  Ni  CO 3  PPh 3 
16 e 
So, the rate of reaction depends upon the concentration of Ni(CO)4 only because this step is slowest
step.
Correct answer is (b)

CO2(CO)8 H2
H3C C CH2 + CO + H2 H3C C CH2 CHO
30. H
(butanal)
Hydroformylation.
Correct answer is (b)
500 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014

31. N  1s 2 2s2 2p3

l = +1 0 –1

1 1 1 3
S   
2 2 2 2
L = +1 + 0 – 1 = 0
Correct answer is (d)
*32. Correct answer is (a)
33. CO 4  CO 12
TVE = 36 + 24 = 60
PEC = TVE – (n×12) = 60–48 = 12
PEC 12
  6  42 (n + 2 = Nido)
2 2
Correct answer is (b)

34. Rh  PPh 3 3 Cl is a Wilkinson catalyst in hydrogenation step one PPh3 loss due to steric factor and

form Rh  PPh 3 2 Cl
PPh3
Cl Rh and shape is T-shaped
Ph3
Correct answer is (a)
2– 2– –
Cl Cl Cl
Cl +NO2– NO2 NO2
+ NH3
35. Pt Pt Pt
Cl Cl Cl Cl H3N Cl

Trans effect NO 2  Cl  NH3

Correct answer is (a)

36. [Link]
(His)
(His)
(His)
(His) (His)
Fe
N N
O O
(II)
(His) N Cu (II) Cu N (His) O
Glu C O H
O
N N AsP C O O
(His) (His)
Oxyhemocyanin O Fe O
(3, 3-histidine amino acids) Oxyhemerythrin
(His) (His) (2, 3-histidine amino acids)

Correct answer is (b)

37. In 1956, in Japan minamata disater had been broken out in coastal area. This is a neurological
syndrome caused by mercury pollution. The Hg ++ get converted into MeHg + by carbonic
blomethylation. Which form strong bonding with thiol(–SH) group of protein having cysteine amino
acid. Hence, A, B and C are correct.
Correct answer is (d)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014 501

38. H O1
C
2
H OH
3
H OH
4
H OH
5 CH2OH

Both 3rd and 4th carbon have same configuration which is R

Correct answer is (c)

39. For antiaromaticity, there are 4n e  and there must be delocalization. Since boron is electron defi-
cient, it has vaccant p-orbital and thus electron can be delocalized.
In the given compound I species has 4n e  .
Thus it is antiaromatic.
H
B

Correct answer is (a)

1
40. Acidity  Ka  pK
a

Thus, the hydrogen which will be more acidic, will have lower pKa.
O Me
H H CN
N N
–
BF4 H
O N H2N NH2 N
BF4–
(I) Me (II) Me (III)

It is clear from above that III will generate as unstable anion which is vinyl anion. thus it will less
[Link]
acidic and thus having highest pKa value among three.
Now, between I and II, II will have lower pKa value because the conjugate base obtained after re-
moval of hydrogen from II will be more stabilized.
O O O N N
C C
N N
BF4– BF4–
O N O N O N H2N NH2 H2N NH2
Me Me Me
Thus the order will be III > I > II.
Correct answer is (c)
502 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014

H N N
N
H
N N N
41. N N
(I) (II) (III) (IV)
sp3 hydridized N is less electronegative than sp2 hybridized nitrogen. That is why sp3 hydridized.
Nitrogen will be more basic as compared to sp2 hydrized nitrogen.
Hence, II and III will be more basic as compared to I and IV.
• Since III contains 3 nitrogen, it will be more basic as compared to II.
• Imidazale is more basic than pyridine. This is because protonation of N of imidazole that does
not takes part in resonance does not break up the aromatic ring. Thus, its confugated acid will be
more stable as comapred to corresponding conjugate acid of pyridine, which eliminates the aro-
maticity in pyridine.
Correct answer is (c)
42. The most stable conformation of neomenthol is
H3C OH

CH3

CH3
which can be also written as
OH

Thus, option (b) is correct.

O
H
O Me 2 H 4 R HO H
H Et
Et H LiAlH4
43. Et 6 4 * 2
* attack from 3 3 1
5 S
Me [Link]
(R)
(S) Me back side

According to Cram’s rule formation of S alcohol at 2 indicates 3rd will have R configuration.
Thus, option (a) is correct.
F
Br

44. ?
O

F F
Mg

Br MgBr
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014 503

O
O
[4+2] Diels
Alder reaction

Correct answer is (c)

Br H O
O O CH OMe O OMe O OMe C H

45. Br CH OMe H –MeOH

Correct answer is (c)

O
OCH2OCH3 OCH2OCH3 C OCH2OCH3 OCH2OCH3
Li COO H3O+ COOH
46. sec BuLi O

H3C H3C H3C H3C

Correct answer is (c)
47. This is known as Birch reduction. When electron withdrawing group substituted aromatic ring are
subjected to Birch reduction, they are found mainly on the reduced position of product. Birch reduc-
tion reduces alkyne to trans alkene. Thus.
H H
COOH
COOH C COOH C
C (i) Na, NH3(i), EtOH C H3O+ C
C
(ii) H3O+ H

Correct option is (a)

48. Electrophilic aromatic substitution is benzothiophene will occur preferably at 3-position. But in
[Link]
excess of reagent substitution also takes place at 2-position.
Br Br Br Br Br
Br
S S H S
Br
H
Br
Br
Br S
S

Correct answer is (c)

49. Me Me Me ••
O O
It will produce a mixture of product, becuse during the reaction caurse C–C  bond rotation can
takes place
504 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014

Correct answer is (c)

50. M. F. = C4H6O2
IR = 1770 cm–1
 value for 13C NMR = 178, 68, 28, 22 ppm. From 13C  value it is clear that there are 4 types of
carbon IR value indicates towards ester functional group  value at 28 and 22 shows that in the
structure two carbon are nearly at similar environment.
O
 value at 178 ppm indicates C
carbon and 68 ppm indicates C–O carbon.
All this observation will be well explained and satisfied by
O O
 = 68 ppm
 value = 178

 value = 22 ppm  value = 28 ppm

Correct answer is (c)

51. O O O
+
O CH3 O CH3 OH
O CH3 –CO

O O
+, 177] [F2+, 122]
[M+, 222] [F1

 2
daughter ion  F2 , 149  149  149
For mass of metastable =  =  125.4
parent ion  F1 , 177  177

Correct answer is (b)

52. 13
C NMR [Link]
D (I = 1)
Number of time (2NI + 1) = 2×3×1 + 1 = 7 line (non pascal)
[Link]
Correct answer is (d)
53. Abetic acid is a resin acid having molecular formula C20H30O2.

C OH
O Abietic acid
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014 505

Its biosynthetic raute is given as follows

Mevalonic acid  geranyl-geranyl pyro phosphate  abietic acid.
Correct answer is (b)
54. This artificial sweetner is aspartame
COOH
COOH
H H2N COOH
N OH +
COOH H2N
H2N H
O Ph
O
Ph L-aspartic acid L-Phenylalanine

Its IUPAC name is L-a aspartyl L-phenyl alanine.

Thus aspartame is a methyl ester of the dipeptide of the natural amino acid. L-aspartic acid and L-
phenyl alanine.
Correct answer is (c)
55. Homonuclear diatomic molecules does not have any permanent dipole moment. So, it will not show
rotational spectra.
On the other hand, vibration does not make any changes in the permanent dipole moment of the
homonuclear diatomic molecule. So, it will not show vibrational spectra. But the homonuclear di-
atomic molecules shows rotational Raman and electronic spectra and with the help of both, we can
calculate the bond length.
Correct answer is (c)
56. For a heteronuclear diatomic molecule having non-zero component of orbit angular momentum
along the molecular axis, the energy levels of the vibrational rotational spectra will be
Evib rot  Evib  Erot
2
 1  1 (in units of m–1)
 BJ  J  1   v   e  xe  v   e
 2  2
Consdering the transtition from v  0  v  1
J  1 will correspond to P branch
J  0 will correspond to Q branch
[Link]
J  1 will correspond to R branch.
Correct answer is (d)
57. Length = L
x  L
1/ 2
P  min   p 2

h
x  p x 
4
h h
L  p x   px 
4 4 L
2
 h 
p 2   h2 h2 2
4 L 
E x    
2m 2m 16 2 L2 2m 32 2 L2 m 8mL2
Correct answer is (b)
506 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014

58. Method-I:
As per the Maxwell’s distribution.
3/2
dN  M   Mc 2 
F V    4   c 2 exp    dc
N  2 kT   2kT 
dN
F V   M
N
dN
So, higher the value of molar mass higher is the value of
N
M Ne  M Ar  M Kr
So, Ne will have lower curve and Kr will have higher.
Method-II: Maxima in the curve corresponds to most probable speed of the gas.
2 RT
CM . P. 
M
As M Ne  M Ar  M Kr . So, C M .P. Ne  C M . P. Ar  C M .P.Kr
So, curve C corresponds to Ne. B to Ar and A to Kr.
Correct answer is (c)
0 RT
59. Ecell  Ecell  ln Q ... (1)
nF
At equilibrium Q = K (equilibrium constant) and Ecell  0

0 RT
So, Ecell  ln K ... (2)
nF
Sn 4  2e  
 Sn 2 E 0  0.15  Reduction potential of cathode 

Sn 2  2e  
 Sn E 0  0.14V  Reduction potential of anode 
0 red red
Ecell  Ecathode  Eanode  0.15   0.14   0.29V
0
[Link]
Putting value of Ecell in equation (2)

0 RT
Ecell  ln K
nF
RT
0.29V  ln K
nF
RT
n  2,  25.7  103V
F
25.7  103
0.29  ln K
2
0.29  2
 ln K
25.7 103
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014 507

ln k  22.6
Correct answer is (a)

60. The fractional coverage for dissociative adsorption is

1/ 2


 kp 
1/ 2
1   kp 
1/ 2
If P is small, then    kp 

   p1/2
Correct answer is (c)

61. H
S P

U G

V A T
dH  TdS  VdP
 H 
 S   T
 P
Correct answer is (d).
62. As we know, according to Euler theorem
For equation, df  Mdx  Ndy ... (i)
f is exact differential only when
 M   N 
   
 y  x  x  y
Given exact differential

df 
1 x [Link]
dx  2 dy ... (ii)
y y
From equation (i) and equation (ii), we get
1 x
M and N   2 (Its follows Euler’s theorem)
y y

 M    1  1
     2 ... (iii)
 y  x  y y  x y

 N    x  1
And     2 
 2 ... (iv)
 x  y  x y  y y
From equation (iii) and (iv)
 M   N 
   
 y  x  x  y
508 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014

Hence, both sides are equal.

Correct answer is (d)

63. The angular momentum operator Lˆz  i has eigenfunction of the form exp im  , where ‘m’ is

the magnetic quantum number.
Comparing with the eignfunction given in the question, we get
A=m
The value of m will be from  to  .
Since, l will be a positive integer i.e. 0, 1, 2, 3, ......................
Therefore, m will be 0,  1,  2,..........
Correct answer is (b)
64. X-ray diffraction give structural information only for crystalline solids.
Correct answer is (d)

65. A  B  AB H
AB  C  D E0
H is the enthalpy change for the reaction and E0 is the activation energy for the second reaction.
So, the activation energy of the overall reaction is E0  H
Correct answer is (c)

hc 6.6 1034 J .s  3 108 m.s 1

66. I .E  
 24 109 m
6.6
I .E   1017 J
8
6.6  1017 1019
I .E    0.5156  102  51.56 eV
8 1.6
Correct answer is (c)
67. [Link]
Variance = (Difference between molar mass and weight molar mass) × molar mass
= (16–3) × 13 = 3×13 = 39
Here molar mass represented xi and weighted molar mass fi. In this question data set and there

frequency is not given. All the final values are given. So, variance =  E  x 2  – E  x 
Correct answer is (a)
1 km 1 1
68.    Line weaver equation 
v vmax  S 0 rmax

km km
Slope = r  k  E   40 s  given 
max 2 0

k2 1 1
Catalytic efficiency =    104 L mol 1 sec 1
km 40s  E 0 40sec 2.5  106 M
Correct answer is (d)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014 509

69. Number average molecular weight is determined by osmometry.

Correct answer is (b)

NaOH  CH3COOH 
 CH3COONa  H 2O
70. Initial milli moles 0.02×10  0.2 0.02 10  0.2
After reaction 0 0 0.2

0.2
 CH 3COONa    0.01  10 2
20
pH of CH3COONa can be calculated by hydrolysis of CH3COONa.

 CH 3COOH  OH 
CH 3COO   H 2O 

1/2
  k C 
 OH   C   w 
 
 ka 
1 1 1
log OH    log k w  log c  log k a
2 2 2
1 1 1
pOH   log k w  log k c  log k a
2 2 2

1 1 1 1
  log1014  log102  pk a  7  1   4.75  7  1  2.37  5.63
2 2 2 2

pH  14  pOH  14  6.37  7.63 = 14  5.63  8.37

Correct answer is (b)
PART – C
71. Limitations of Beer’s law are
Solution must be dilute, radiation must be monochromatic, temperature should not vary largely.
[Link]
Analyte molecule should not undergo any kind of association or dissociation.
Refractive index of medium should not change.
Correct answer is (a)
72. For ICP-OES and ICP_MS argon is most suitable gas to generate plasma
A number of gases cane be used to produce plasma, like Ar, Ne, N2, O2, H2, air and mixture of gases.
The physical properties of the gases play a decisive role in this regard. Such important properties are
ionization and dissociation energy, thermal conductivity, atomic weight and chemical reactivity.
Argon belongs to the group of inert gases. It means that it does not react with the material during
production of plasma. Its atomic weight - the highest among all plasma gases and it generates high
kinetic energy of the plasma beam. Due to its low ionization potential argon is excellently suitable
for generating the plasma beam. However, argon has a low thermal conductivity and a low thermal
capacity which limits its application is some specific areas only.
Correct answer (a)
510 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014

2 22 2
73. Cross section =  r  r
7
1/3
Now, radius of nucleus = R0  A

Where, R0  constant  1.4×1013 cm

Since, 1 barn = 10–24 cm2.
Radius = 1.4×10–13 ×(125)1/3 = 1.4×10–13 ×53×1/3 = 1.4×10–13× cm
22 2 22
Now, cross section =
7 7
 
5 1.4  10 13  5   1.4  1.4  25  10 26 cm 2

= 22×0.2×1.4×25×10 cm2 = 154×10–26 cm2 = 1.54×10–24 cm2 = 1.54 barn.

–26

Correct answer is (b)

H2 CH2 +
C + Cl
NH2 H2C NH2 H2 H2
74. CH2 H2C N N CH2
Cl N H2C N Cl
CH2
Co Co H2C Co CH2
CH2 H2C
Cl NH NH Cl N N NH
NH NH2
H2C Cl
CH2 CH2 C
H2 CH2 CH2
cis-d cis-l
Trans optically inactive
Correct answer is (c)

75. 100

Mb
80 7.6 7.2 6.8
pH
% saturation

60
[Link]
Hb
40

20

0 40 80 120
Po2 (mm Hg)

Correct answer is (a)

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014 511

76. Oxyhemocyanin stables as oxygen carrier.

Carbonic anhydrase
Carbonic anhydrase converts CO2 to H2CO3.
carbonic
CO 2  H 2O   H   HCO 3
 H 2CO3 
anhydrase

cytochrome P450 oxidizes alkene to epoxide.

O
cyt. P450

Carboxy peptidase A catalyzes the hydrolysis of C-terminal peptide bond.

H O H H H
O O O
N C C NH C C + H 2O NH C C + NH3 C C
H
R O O O
R1 R1 R1
Correct answer is (a)

H3Al H

Br Br
Fe Fe Fe Fe
77. CO CO H
OC OC OC Br
CO OC
CO
(A) (B)

So, in the product (B) it shows two signals in 1H NMR one for 5H of Cp ring and one for Fe H
proton with intensity ratio 5 : 1.
Correct answer is (a)

78. [IrCl(CO)(PPh 3 )2 ] is a 16 electron complex called as Vaska complex. Only show oxidative addi-
tion in the presence of
Cl Cl
Ph3P H
Ph3P Ir PPh3 + H2 Ir

[Link]
Ph3P H
CO CO
16 electron stable complex 18 electron stable complex
Correct answer is (c)
79.

OC Cr CO
CO

1

H NMR 400 MHz,  CD3  2 CO 
 ppm   5.61  5.6H 
13
C NMR 101 MHz : CDCl3  ;  ppm  234.54, 95.13
Benzene shows a peak at ~ 7.2 ppm when benzene attach to metal decrease the chemical shift due to
discruten of ring current.
Correct answer is (a)
512 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014

80.
eg

[Mn(H2O)6]2+, Mn2+ 3d5

t2g

Ground state term for d5 is 6S which transform into 6 A1g in octahedral field.

eg eg
hv

t2g t2g

There is spin change during electron transition. Therefore, transition is spin disallowed.
Correct answer is (a)
81. PCl3 + PhLi PPh3 + 3LiCl
(A)

Ph3P H3C I Ph3P CH3 I

(B)

Ph3P CH2 H BuLi Ph3P CH2 or Ph3P CH2

(B)
Correct answer is (c)

82. The reaction is as follows

Ph 2SiCl 2  2H 2 O  Ph 2Si  OH 2  2HCl
1 : 2 Diphenyl disilanol
Diphenyl A
dichloro silane

[Link]
Now, (A) undergo condensation polymerisation to yield (B), which is an inorganic silicon, polymer,
as follows

Ph Ph Ph Ph Ph Ph
–H2O
HO Si OH + H O Si OH HO Si O Si OH O Si O Si O
further
Ph Ph Ph Ph reactions Ph Ph
at both
ends (B) Linear chain polymer
Correct answer is (c)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014 513


83. The C 2 B9 H12 is potta carborane anion.

C 2 B9 H12 follow wade rule as
C BH
(4e–) (4e–)

isoelectronic

Now, B11H14 is equivalent to B11H15 neutral borane which follows the formula BnHn–4, which is the
general formula of nidoborane.

B11H14  B11H15  Bn H n  4  Nido
Correct answer is (b).
84. It is a kind of insertion reaction of M–H (metalhydride bond between CO)
* * O
Cp Cp
Th H C O Th H
Cp Cp
* *
Correct answer is (d)
H3C CH3
85. Dipivaloylmethane, H3C CH3 form chelats with lanthanides
CH3 CH3
Correct answer is (b)
86. 2 
 Co  NH 3  Cl    Co  NH 3   NH 2  Cl   H 2O
 OH  
 5   4 
 2
 Co  NH 3  4  NH 2  Cl 
 Co  NH 3  4  NH 2    Cl 

2 2
 Co  NH 3   NH 2  
 4   OH  
 Co  NH 3 5 OH 
2 2
Base hydrolysis of  Co  NH 3 5 Cl  depends on the concentration of both  Co  NH3 5 Cl 
[Link]

and base. In this reaction OH abstract proton from coordinated NH3.
3
The base hydrolysis of  Co  CN 6  is independent of base because it has no ionizable proton.
Correct answer is (a)
87. Diborane reacts with ammonia as
H3N H
B2H6 + NH3 B BH4
H3N H
(X)
(A) (B)
Here NH3 show unsymmetrical cleavage.
H H
H
B B BH2 + BH4
H H H
514 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014

‘Y’ is actually [A + B]. In ‘Y’ ‘B’ part gives quintet and ‘A’ part gives triplet by ‘B’ and ‘H’ coupling.
Correct answer is (a)
88. The reaction of XeF6 with NaNO3 takes place as
XeF6  NaNO 3   XeOF4  NaF  F  NO 2
Correct answer is (a)

89.  MnF6 3 , Mn 3  3d 4  t 32g eg1

 HS

µ  4  4  2   24  4.9

d4
+2 +1 0 –1
s2  2s  1  2  2  1  5
L2D
Ground state term symbol  5 D
Correct answer is (a)
90. 6+
NH3
H3N NH3
Co
NH3 HO NH3
H OH
H3N O
Co Co
O 6Br–
H3N H OH
NH3 HO
NH3
Co
H3N NH3
NH3

It is first inorganic optically active compound discovered by Werner.

Number of Co–O bonds = 12
Number of Co–N bonds = 12
Correct answer is (a)
[Link]
91.  CrCl6 3 Cr 3  3d3
µs  3  3  2   3.87 B.M.

µLS  n  n  2   L  L  1 B.M.

–1 –2
d3

ml +2 +1 0
L=3

µLS  3  3  2   3  3  1  15  12  27  5.20 B.M.

Correct answer is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014 515

92. Complex (A) HM (CO)5

M = Mn [7 electron]
CO
OC CO
–
Mn
1 + 7 + 10 = 18 e OC CO
H [1H NMR = –7.5 ppm]

Complex (B)  5C5 H 5  M '  CO  

 3 2

 5  C5 H 5  Cr  CO   M '  Cr  6e

 3 2

10 + 12 + 12 + 2 (M–M) bond = 36 electron.

5
OC
OC
Cr Cr
OC
CO
CO CO

5
1H NMR = 4.10 ppm

Correct answer is (a)

93. The crown ether binds metal cation in their cavity. They are selective as they have fixed ring size.
Crown ether Metal cation
crown-4 Li+
crown-5 Na+
crown-6 K+
crown-7 Rb+
crown-8 Cs+
Therefore, 12-crown-4 is best suited for Li+ cation. After then as the size increases binding capacity
decreases.
Correct answer is (a)
94. In the formation of SF6 the following atomic orbitals are involved.
[Link]
S= 6F =
3s 3p 2p
The 3s, 3p of ‘s’ and 2 pz of ‘F’ are mixed to give ten MO’s. Calculations indicate that four of
orbitals will be bonding and four of orbitals will be bonding and four will be antibonding. The
remaining two will be non-bonding.
There are 12 electrons to be filled in ten MO’s. The first two can enter 1a and the next six
can in it. The remaining four fill the non-bonding pair of orbitals. Thus it gives 1a2 1t 6 e4 as
configuration.
This gives the molecular diagram of SF6 as
516 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014

1S SF6 6F
2a1

2t1

3p t

1e
e

a
3s

1t1

1a1
Therefore answer will be (a)
95. Gel permeation chromatography is a size exclusion chromatography, that separates analytes on the
basis of size. So, the size difference in fatty acids and low molecular weight peptides is greater so
they can be separated by using gel permeation chromatography.
Correct answer is (c)

HO O HO
HO O O O
O Me2C(OMe)2, TsOH(cat.) BH3, THF
96.
O O
HO
Me O O
OH Me O
O
O H3O+
O

O
[Link]
HO O

Correct answer is (c)

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014 517

O O O
97. O O O O
C
N N C N
Bu2BOTf, i-Pr2NEt Ph H
O O O
Me Me Me

Ph Ph Ph
HO Me O
O
O HO
O
Ph N
Ph N
O Me
Me O
Me
Ph
Ph

Two stereogenic centre present in the molecule direct the stereochemistry.

Correct answer is (a)

Br
98. Br Br
Br Br
Br
Note : Bromination in hydrocarbon solvent gives crystalline trans isomer.

Br Br Br NMe 2 SN 2
Me2 NH inversion
NMe 2
SN 2 Me2 NH NMe 2
inversion
NMe 2

Correct answer is (c)

[Link]
N N
N H N
H H
H

O O

99. MeO MeO O

Me O

O CF3COO

Correct answer is (b)

518 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014

100. Hofmann Lofflar freytag reaction

Cl
MeN
Me Me
H
(i) H3O+, hv
(ii) NaOH
H
•Cl
Cl Cl MeHN H
•
MeN MeN  H • MeN H Cl
 Me H • Me CH2 Me
Me Me Me CH 2
 H H
H H NaOH
H3O+ 
hv
-hydrogen
H H H H

Me Me
Cl HN N
CH2 Me Me
H H
H+
–H+

H H
Note : Five membered ring is more stable over six membered in free radical mechanism.
Correct answer is (a)

O I O
H
O P I2, PhI(OAc)2 O P free radical
101. MeO N OPh
CH2Cl2, r.t.
MeO N OPh cation formation
H OPh H OPh
MeO MeO
O H O
O P O P
+ I2 MeO N OPh MeO N OPh
H2 OPh OPh
–H+ MeO MeO

[Link]
OPh
O
I
O PO P OPh
MeO N OPh N
H OPh O
MeO
MeO
MeO
Correct answer is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014 519

O O O O O
Br PdCl2, O2
102. LDA
acid, DMF, H2O O
O (A)
H O O
O OH2
– H2O NaOEt

(B)

Correct answer is (a)

Boc Boc
Boc N
Me3Si N Co2(CO)8, CH2Cl2 N SmI2
O O H
103. O O THF, EtOH OH
Me3N O
[Pauson khand reaction] Me3Si Me3Si
Correct answer is (a)

O
O
P Cl
O Cl P Cl O
Cl
C Cl C Pyridine
Ts N H Ts N O
104. (A) H H
H
P Cl
O
Cl
C
C C Ts N
H H
Ts N Ts N

O O O
H C
C C
N OEt N OEt N OEt
(B) BuOH
N [Link]
PPh N PPh
3
EtO N
PPh 3
COOEt C 3
COOEt
O
O

O O N OH

O
N OBu N O PPh3
C C BuO
O O

O O
H2SO4 OH2
(C)
COOH + t-BuOH COH C
O

Correct answer is (d)

520 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014

105. Trimethyl silyl chloride is used as a protecting group for alcohol functionality selectively.
O
NH2 NH2 H2N
O NH2
Me3SiCl 
H2N COOH MeOH H2N C Deprotection
OH OSiMe3 OMe
OH
O

C Cl
H O O
N H2N
NH NH
–H
O
–H
(B) OH (A) OH

Correct answer is (a)

106. Mechanism-I :

O N N Br COOEt N
Me N H Me H Me Me
NC H
H COOEt
N N N N
NC H
R R R R

O
N N
Me O
Me
COOEt H Me
EtOOC
NC H N
N N CN
R R
R EtOOC
EtOOC N R
[Link]
CN
CN

Mechanism-II:

Br
COOEt
N N NC H N N

Me Me Me H Me

H
N N N N
R R R R
EtOOC EtOOC

CN CN
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014 521

O
N
Me O
Me
H EtOOC Me
N CN
N
EtOOC R
EtOOC R
N R
CN
CN
Correct answer is (a)
107. H NC CN
C CN

C NC CN CN
CN C CN
C [2+ 2] NC ring opening
C cycloaddition CN
NC CN

NMe2 NMe2
NMe2
Correct answer is (c).

108. O
N SPh O
N SPh C C Et
Bu4NF EtO O

N SiMe3 N

CO2Me CO2Me
O
O

C
N Et
PhS PhS N
Et
[Link]
H

Intramolecular
[4+2]
N cycloaddition reaction N
(A)
(B) COOMe CO2Me
Correct answer is (a)
522 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014

O O
O O C CH2CH3 O C CH CH3
109. OH
C
LDA, THF, –70ºC
OMOM Et Cl
OMOM OMOM
O O
O
Me
O
O SiMe3 Me Si Me
O C CHCH3
O SiMe3  O C CHCH3 Cl
O C
OMOM OMOM
CH OMOM O
O O
CH3

O O

H3 O+ C CH 2N2 C
HO OMOM MeO OMOM
CH O o-methylation CH O
CH3 O–H insertion of : CH2 CH3

Correct answer is (d)

110. PPh3 + I I Ph3P I

OH O PPh3 I

Ph3P I I
+ O PPh3
N N N
BOC BOC BOC

I
Cl
[Link]
Cl

Br
CN
Zn, Pd(dppf)Cl2 NC
N Cu(cat.)
Note : Reactivity order of halogen (I > Br > Cl)
BOC
N
BOC

Correct answer is (a)

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014 523

H O OH
111. H
Me DiBAL-H ClCH2COOH
Me Me Diethyl azodicarboxylate, PPh
Me Reduction of C = O 3
to C–OH
H Me H
Me
O
OH O C CH2Cl
H H

LiAlH4
Reduction
H H

Correct answer is (b)

112. ‘’ is called reaction constant.
First reaction is benzoylation of aniline. The slow, rate limiting step of this reaction is found to
be initial attack by the electron pair of of the nitrogen atom. This develops positive charge at the
reaction centre. The reaction is thus accelerated by electron donating substituents. This leads to
a sufficient negative ‘’ value which will –2.69. Now base catalyzed hydrolysis of ethyl ben-
zoates in which the slow rate limiting step in this reaction is attended by the development of –
ve charge adjacent to the reaction centre in the transition state leading to the intermediate in
which the reaction is accelerated by electronic withdrawing and retarded by electron donating
substitutents. Thus ‘’ value can be regarded as a measures susceptibility of a reaction to the
electron donating or withdrawing effect exerted by a substituent. The sign of ‘’ value is of
diagnostic value, –ve value indicates the development of positive charge at the reaction centre
during formation of the T.S. in the rate limiting step.
On the other hand + value indicates development of –ve charge at that centre. Thus in the
base catalyzed hydrolysis in which –ve charge develops at reaction centre ‘’ value will be
positive which is +2.09
Correct answer is (b)
113. From 1H NMR it is clear that there is no methyl group present, because no value corresponding 
[Link]
value is there for three hydrogen.
Now, since the product is racemic, then it will be 3
Hb Hb

Ha Ha For Ha ; 2.67, singlet

Hb; 5.60, singlet
HOOC COOH
Correct answer is (c)
524 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014

114. Step-1 : (nBu3Sn)2 2nBu3Sn

(free radical)
Step-2:
O O
O SnBu3 O cyclisation
I
O O
Bu3Sn I

O O
nBu3Sn
+ nBu3Sn nBu3Sn–SnBu3n

I
5-iodooxacan-2-one

Correct answer is (b)

115.

OH
OH
C H
OH O CH OMe OPMB
–H+
HO C + HO C HO
C C
Me Me Me
OMe
DIBAL-H does not effect triple bond. At low temperature esters and loctones are reduced directly to
aldehydes or lactols.
OMe OMe
OH2
OPMB

[Link]
OH O
HO C
C
C O O Me
C
Me
C
C
Me
Correct answer is (a)
116. • From IR at 3400 (broad) confirms presence of –OH.
• J = 18 Hz indicates the presence of trans geometry of H’s. Thus, possibility of 2nd option ruled
out.
•  value 3.8 (3 H,s) indicates –OMe group. Thus possibility of 4th option ruled out.
•  value at 6.8 (1 H,s) rules out 3rd option.
Hence, option ‘(a)’ is correct structure.
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014 525

(6.75 (1H, d)

H H (6.28, 1H, d, J = 18Hz)

6.90 (1H, d) H Me (1.85, 3H, d, J = 6Hz)

H 6.0 (1H, dq, J = 18.6 Hz)

HO H
IR or 3400
OMe 6.8 (1H, s)
(5.0, 1 H, s, exchangable)

3.8 (3H, s)

Correct answer is (a)

OH OH2 O Ph
117. S
SPh
SHPh mCPBA
O PTSA O O
O

O O O O

O O O

O S Ph O S Ph O O S Ph O
H2C C C OEt C
Li OEt
LDA H
O O O

O O O
Correct answer is (d)
118. With zinc and acetic acid debromination takes place selectively for the bromine, which is adjacent to
carbonyl group.
[Link]
Br Ph Se
Br Br
Zn, AcOH PhSeNa

O Me O O Me O O
Me O
Ph
heat Se mCPBA

O H
Me O Me O O
O

Correct answer is (a)

526 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014

O O
119. H
C CH3NH–CH2COOH CH CH2COOH
H N H
CH3 Transfer
Et3N, DMF
N N
Ts Ts
O
Me
Me O Me
C
OH COOH N N
N H
COOH
CH C
N Et3N H
CH3 H
N N N N

Ts Ts Ts Ts

The product have hydrogen in cis ring junction becuause both the hydrogen’s are in same direction
in the preceding compound.
Correct answer is (d)

120. O O O
O

LDA, THF Cl CH2 CH2 CH2 I

Cl
OEt OEt OEt
OEt
Me (A)
BrMgO Me
Cl Cl MeMgBr, Et2O

O OEt
(B)

Correct answer is (c)

121. [Link]
2NO(g)  Cl 2 (g)  Non-linear T.S.  2NOCl
T 3/ 2 1 7/ 2
A 3/ 2 3/ 2 ; A  7/ 2  A  T
T TT T T
Correct answer is (d)
122. 
k1
A  A  
 A*  A  fast 
k 1

k2
A *  p  slow
r  k2  A * ... (i)
2
SSA on A*, k1  A  k 1  A * A  k 2  A *
2
k H  A
 A * 
k 1  A   k 2
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014 527

2
k1k2  A
Therefore, (i), r  ... (ii)
k 2  k 1  A
2
k1k2  A 2
At low P, r  r  k1  A ... (iii)
k2
2
k1k 2  A k1k2
At high P, r r  A ... (iv)
k 1  A k 1
According to question,
k1k2
Therefore, equation (iv), r   A  k  A
k 1

k1k 2 k k
i.e. k   2   ... (v)
k 1 k1 k1

k1k 2
k  k  1
 k2
1
k 1  A 
The first order rate constant from equation (i),

k1k2  A k1k 2  A / k 1  A k1k2 / k 1

k' k  
 k2  k1  A  k 2  k  1  A  1
k2
k 1  A  k 1  A 
k
In question it is given that first order rate constant becomes  at  A   A1/2 and for that,
2
k2
1
k1  A1/ 2
k
i.e.  A1/[Link]
2
 2 ... (vi)
k 1
Therefore, from equation (v) and (vi),
k k
  A1/ 2   k1  
k1  A1/ 2
Correct answer is (a)
e  hv /2 kT
123. For vibrational partition function qvib  ... (i)
1  e  hv / kT
hv
For condition     . So, from equation (i), we get
 k 

e  /2T
qvib  ... (ii)
1  e  /T
528 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014

Case-(i) : T is very low so that  / T  1 . Then e /T is negligible compared with unity in the
denominator of equation (ii), we get

qvib  e  /2T (at low temperature)

Case-II : T is very high so that  /T  1 . Then the exponential in the denominator can be expand as
series retaining only the first two terms.

e /T  1   / T  .......
T  /2T
qvib 
e

Correct answer is (b)
1 1
124. Neglecting zero point energy, q  1  e  h / kT   
 1  e 1   h  kT 
N i 1  / kT 1  / kT 1 1
 Probability =
N q
 e  e
q
 1 
e  h / kT  1  e 1  e 1  e2  e  1
1  e1  
Correct answer is (d)
L
125. 2 n x  L 2 n x
 sin  x  sin dx
0
L L  2 L L

 L L
Dirac-delta condition,   x    0 ; x 
 2 2
L
The value of x 
2
Between the 0  L
L
So, direct put the value of x  in the wavefunction and n = 1, no integration.
2
2
sin
L 2
sin
L [Link]
L L2 L L2
2   2   
sin sin =  sin  1
L 2 2 L  2 
Correct answer is (d)

126. S   S x  iS y
S   S x  iS y
 S z , S    S z , S x  iLy    S z , S x   i  S z , S y 
 iS y  i  iS x   iS y  i 2 S x 

 iS y  S x   iS y  S x   S 
Correct answer is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014 529

127. Since for transition probability we have, T  e2  L

2 2mV0  E  2m V0  E 


L where,  
T e 
Transmission probability is maximum if L is minimum. and V is minimum.
Correct answer is (b)
128. For a multicomponent open system
G   ni µi
i
Differentiating above equation
dG   µi dni    dµi  ni ... (i)
i i
But by the fundamental equation,
dG   SdT  VdP   µi dni ... (ii)
i
Substracting equation (i) and equation (ii)
 ni dµi   SdT  VdP  Gibb's Duhem equation 
i
If T and P are constant,
 ni dµi  0 ni  xi
i

 xi dµi  0
i

xi dµ1  x2 dµ2  0 ... (A)

Gibb’s-Duhem equation involving partial molar volume, we have
V   niVi
i

dV   dniVi   ni dvi ... (iii)

[Link]
i i

Taking V  f T , P, ni  , we have

 dV   dV   dV 
dV    dT       dni  J  1
 dT  P,nJ  dP T , nJ  dni T , P,nJ S
At constant T and P we have
 dV 
dV     dni  J  1
i  dni T , P ,n S
J

dV   vi di ... (iv)
i
Substracting equation (iii) and (iv)
 ni dvi  0
i
530 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014

For a binary solution, we have

n1dv1  n2 dv2  0

 ni dvi  0  ni  xi    xi dvi  0
i
i

x1dv1  x2 dv2  0 ... (B)

For a binary mixture relation (A) and (B) are correct.
Correct answer is (a)
129. For a heteronuclear diatomic molecule, the energy levels of the virbrational rotational spectra will be
2
 1  1
Evib rot  BJ  J  1   v   e  xe  v   e (in units of m–1)
 2  2
h
Where, B  is the rotational constant of the molecule.
8 2 Ic
h
 B 2 2
8 µr c
where ‘r’ is the bond length of the molecule.
If the bond length of the heteronuclear diatomic molecule is greater for upper vibrational state, the
wave number corresponding to the P-branch lines will be ,
Evib  rot  e 1  2 xe    2 B  J '  B  B '    J ' 1
where, J ' = rotational quantum number of upper vibrational state,
B ' = rotational constant of upper vibrational state.
Gap between two successive P-branch lines is proportional to  4 B  2 B '
As bond length r increases, B ' decreases and gap between successive absorption line of branches
increases non-linearly.
Correct answer is (a)
130. Selection rule for EPR, M S  1 ; M I  0
Correct answer is (b)

131. G  nRT ln
P2 [Link]
P
 G2  G1  nRT ln 2
P1 P1
P2 P2 P2
And µ  RT ln  µ2  µ1  nRT ln  µ2  µ1  nRT ln
P1 P1 P1
If initial state is standard state than,
P
µT , P   µ0T   RT ln ... (i)
P0
P
G  T , P   G0T   nRT ln ... (ii)
P0
Equation (i) shows that the chemical potential varies with natural logrithm.
µ vs P may be represented as
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014 531

P
µ vs P for ideal gas
However measurement on the real gas shows that the relation between µ and P is not show exact at
very-2 low gas pressure all gas appear ideal behaviour at moderate pressure region. The pressure is
lower than expected because real gas molecule attract each other and the measured pressure is lower
than ideal.
At very high P the pressure is higher than expected because gas molecule become. So, densely
packed that they begin to repel each other. So, the real behaviour or actual behaviour of chemical
potential vs the real pressure may be show that here is attractive palt clominate.
Repulsive part dominate
µ at high pressure
t
ar
ep
ctiv Dominate at low pressure
tra
at

P
µ vs P for ideal gas
Correct answer is (b)
132. H 2 
 2H D0 H 2 ... (1)

H 2 
 H  H D0  H 2 ... (2)

 H  e
H  IH ... (3)

 H 2  e
H 2  IH 2 ... (4)
Now, adding (2) and (4)
H 2  H 2 
 H   H  H 2  e D0 H 2  IH 2 ... (5)
Subtracting (3) from (5)
H 2  H 2  H  [Link]
 H   H  H 2  e  H   e D0 H 2  IH 2  IH

H 2 
 2H D0 H 2  IH 2  IH ... (6)
From (6) and (1)

D0 H 2  D0 H 2  IH  IH 2
Correct answer is (b)

v' C 2v E C2  v  v '
133. ;
Number of unshift atoms 10 0 0 10
H H Contribution per atom 3 1 1 1
H H
Reducible representation 30 0 10 0
v
532 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014

C2v E C2  v  v '
A1 1 1 1 1 z, x 2 , y 2 , z
E C2  v  v ' A2 1 1 1 1 Rz , xy
R.R 30 0 0 10 ; B1 1 1 1 1 x, R y , xz
B2 1 1 1 1 y, Rx , y z

1 40
nA1  30  0  10  0   10
4 4
1 20
nA2  30  10   5
4 4
1 40  20 20
nB1  30  0  10  0   5
4 4 4
1 20  20
nB2  30  10   10
4 4
R.R  10 A1  5 A2  5B1  10 B2
Rotational = A2  B1  B2
Translational = A1  B1  B2
Vibrational = Total – (Rotational + vibrational) = 10A1 + 5A2 + 5B1 + 10B2 – A2 – A1 –2B1 –2B2
= 9A1 + 3B1 + 8B2
Correct answer is (d)
134.
z

xy xy z
 z
 xy  S4z   xy  C4z   xy  C4     C4  E  C4
Correct answer is (a)
135. d = 160 pm
d a r
 
2 2 2 1
[Link]
 ad 2
3
 
V  a3  d 2   2 2d 3
3
 2  1.44  160  1010 cm 

 11583488  103 cm3

 1.1583488  1023 cm3
1.158  1023 cm3 contains 4 atoms
4
Therefore, 1 cm3 contains atoms  3.45  1023 atoms
1.158  1023
Correct answer is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014 533

136. G  nFE  G   ve for spontaneous 

G  2746.06  103 joule / mole
2746.06 103  26  96500  E
2746.06 1000 2746060
E E ; E  1.09 volt
26  96500 2509000
Correct option is (b)
1 1
137. kt  
ax a
1 1
Or, kt  
 A0  x  A0
1 1 k  A0 t  1
 kt  
 A0  x  A0  A0
 A0
  A0  x
kt  A0  1

 A0
x   A0 
kt  A0  1

 1   kt  A0  1  1  kt  A0 
  A0 1     A0     A0  
 kt  A0  1  kt  A0  1   1  kt  A 0 

x kt  A0
Therefore, fraction of group condensed  A  1  kt A
 0  0
Correct answer is (c)
138. [Ne] 2 p1 3 p1
2s  1  3; [Link]
2s  2; s 1
For, D, L = 2
J  L  s .......... L  s  2  1 ...... 2  1  3, 2,1

Levels for 3D are 3 D3 , 3D 2 , 3D1

Correct answer is (c)
139. Ground state wave function : N0 e
First excited state wave function : N1  2    e /2
The variational wave function N 2  3    e  will be good approximation for the first excited state
wave function. Since, the energy calculated from the variational wave function will be greater than
or equal to that of exact energy.
Therefore, E  E1
Correct answer is (c)
534 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014

0 0 – –
n 4
140. The number of microstate = r n  r = 2 4  2 0 – 0 –
0 – – 0
4 4  3  2 1
 6 – 0 0 –
2 2 2 2
There are 4 given states and number of particles 2 possible distribution. – 0 – 0
– – 0 0
Correct answer is (d)
141. Ionic part of the ground state valence bond wave function of H2 molecule if
12
1sa 1sa  Ha Hb 1sb 1sb 

Atomic spin of hydrogen atoms a and b.

Ionic part : 1sa 1 1sa   2   1sa  2  1sa  1

1sa 1 1sa  1

1sa  2  1sa   2 

Covalent : 1sa 1 1sb   2   1sa  2  1sb  1

1sa (1) 1sa  (1)

1sa (2) 1sa  (2)
Correct answer is (a)
 g /kT
142. Partition function is given by q   g j e
j

 j / kT
 q  g 0  g1e 1 / kT  g 2e  2 / kT  .....g j e
When T  
 q  g0  g1e 0  g 2 e0  .......  g j e 0
 g 0  g1  g 2  ......  g j
[Link]
q gj
j

Correct answer is (c)

 
143. Since, log  k   2 AZ A Z B I
 kc 
1 2 30 102
 0.3  2   1 n  10  n  1
 30 101  n3
2 10
Correct answer is (c)
q1 q2 q3
+
144. H2C CH CH2 (where, q is charge on carbon atom)
1 2 3
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014 535

 E
1 0

E  0
E
  E  0  1 1 0

0  E
 E
0 1

 E
Let x ... (i)


x 1 0
 1 x 1  0  x3  2 x  0
0 1 x

2
 x  x 2  2  0  x  x 2   2    0  x  x  2  x  2   0


Three roots, x   2, x  0, x  2
Then from equation (i), putting the values of x we get,

E1    2  ; E2   ; E3    2 
The secular equations are
c1 x  c2  0 ; c1  c2 x  c3  0 ; c2  c3 x  0

For x   2 , we will have from above equation,

 2c1  c2  0 ... (ii)

c1  2c2  c3  0 ... (iii)

c2  2 c3  0 ... (iv)
[Link]
c2 c
Equation from (ii) and (iii), c1  ; c3  2
2 2
Using the normalization criteria
c12  c22  c32  1
2 2
 c2  2 c  1
We get, 
 2
  c2     2   1  c2  
 2 2
Thus, the first wave function is given by
1 1 1
 1   2 pz 1   2 pz  2    2 pz  3 (bonding)
2 2 2

x  0 and x  2
536 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2014

1 1
2   2 pz 1   2 pz  3 (non bonding)
2 2
1 1 1
 3   2 pz 1   2 pz  2    2 pz  3 (antibonding)
2 2 2
2 2 2
2 1 1 2  1  2 1 1
q1  2c11  2    ; q2  2c12  2   1 ; q3  2c13  2   
2 2  2 2 2
Correct option is (c)
145. A = Monolayer
B = Multilayer without condensation
C = Multilayer with capillary condensation
Therefore, correction answer is (b)

[Link]
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015 537

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

CHEMICAL SCIENCES BOOKLET-[A]

Part-B

21. The carbonic anhydrase enzyme that catalyst the rapid interconversion of carbon-di-oxide and water
to bicarbonate and protons (and vice versa).
carbonic
CO 2  H 2 O 
anhydrase
 H 2 CO3  in tissue high CO 2 concentration 
HCO3  H  
 H 2CO3 
 CO 2  H 2O  in lungs and nephronse of kidney 
R O R O
H
N O H3N
N O + H2O N + O
H H
O R' O R'
Polypeptide (n-residues) Polypeptide (n-1residues) Amino acid
Where, R ' = Arg, Lys, and Ornithine
Correct option is (a)

Deoxy form
Fe+2 (high spin) oxy form
Fe+2 (low spin)
22. 2.1Å 2Å

N N N N

N N N N

protein protein
tense form [Link]
relax form
(out of cavity) (enter the cavity)

Correct answer is (a)

23. [Co(CO)3 (NO)]

9  6 + 3 = 18 electron

[Ni( 5 – Cp) (NO)]

10  5 + 3 = 18 electron
In both complexes NO donating three electron. So, NO is in linear form.
Note : When NO in bent form donating 1 electron.
Correct option is (c)
538 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015

24.  PdCl4 2  C 2H 4  H 2O 

 CH 3CHO  Pd  2HCl  2Cl 
Pd(II) Pd(0)
oxidation

2
 PdCl 4   2CuCl
Pd  2CuCl 2  2Cl  
Pd[0] Cu(II) Pd(II) Cu(I)
reduction

1
2CuCl2  O2  2HCl   2CuCl2  H 2O
2
Correct option is (a)
25. Correct option is (b)
26. Gas phase proton affinities
N 3  308 kJ / mole
NF3  604 kJ / mole
NH 3  872 kJ / mole
N  CH 3 3  974 kJ / mole
Proton affinity decide the energy release when a molecule/ion accept a proton. Higher the value of
gas phase proton affinities more will be basicity. Hence, N 3 is most basic.
Correct option is (a)
27. According to Ilrovic equation,
id avg  607 n O1/2 m 2/3 t1/6 cM0
(1) So diffusion current depends on m t which is mass flow rate of mercury. So, option (a) is wrong.
(2) Diffusion current also depends on ‘t’ which is drop time.
(3) Though temperature is not directly involved in the equation but changing temperature will change
concentration Cº as well as mt so idavg also depends on temperature.
Correct option is (d)

28. Threshold energy = Q 

[Link]
Total mass of reactant 14
 3.236   3.485
mass of target nuclei 13
Correct option is (c)
29. Correct option is (d)
30. All the allotropic phosphorous forms changes into white P4 discrete units. Which has structure
P

P P

P
Correct option is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015 539

31. The structure of S2O show resonance as

0 +2
+2 +2
0 S –2 S –2
–2 O
S S
O –2
OS = 0 +2 –2 OS = –2 +4 –2
(I) (II)
Hence, the probable O.S. of ‘S’ are (0 and +2) from structure ‘I’ and (–2 and +4) from structure II.
Correct option is (a)
32. There are many anions which show similar properties like halide ions, they are called pseudo halide
and their dimers are called pseudo halogens.
Pseudo halides are CN  , N 3 , SCN  , NCN 2  , CNO  , NCO  , SeCN  etc.
Correct option is (d)
33. The bonding in phosphine ligands, like that of carbonyls having two components. The primary com-
ponent is sigma donation of the phosphine lone pair to on empty orbital on the metal. The second
component is back donation from filled metal orbital to an empty orbital on the phosphine ligand.
This empty phosphorous orbital has been described as being either a d-orbital or an antibonding
sigma orbital  *  .
-backbond
-bond
••
M PR3
M • PR3
• empty
filled filled *-orbital
empty
d or p-orbital -orbital d-orbital (red colour)
PR3

LnM LnM(PR3) PR3



[Link]
M 
PR3

M t2g PR3

So, in transition metal phosphine (M–PR3) complexes, the back bonding involves donation of elec-
trons from
 PR 3  * 
M  t 2g  
Correct option is (a)
540 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015

34. The refluxing of RhCl3.3H2O with an excess of PPh3 in boiling ethanol gives a RhCl(PPh3)3–
chlorotris (triphenyl phosphine) rhodium (I) is known as wilkinson catalyst.
boiling ethanol
RhCl3  3H 2 O  excess PPh 3   RhCl  PPh 3 3  Ph 3P  O  2HCl  2H 2O
A
 
oxidized solvent

PPh3 serves as the reducing agent.

PPh3
Cl
Rh
PPh3
Ph3P
It is a square planer 16-electron complex. Valence electron counting on rhodium metal centre.
(i) there is no overall charge on complex
(ii) there is one anionic ligand (Cl– )
(iii) Rh metal atom must have +1 charge to compensate for the one negatively charged ligand.
So, the oxidation state of Rh is +1.
Now, we can do our electron counting.
Rh (+1) d9 (9 electron)
3PPh3 6 electron
–
Cl 1 electron
____________________________________
Total 16 electron
____________________________________
Correct option is (a)
35. -hydrogen elimination mechanism.
empty orbital agostic interaction
H H #

M M


M H
H
H2C CH2
M
[Link]
Since C–H,  bond pair electron donate to the metal for this elimination. Therefore, as the donor
ability of the  -electron pair increases rate of  -elimination increases.
Electron donor ability at  bond is
C
3
H (sp ) >C 2
H (sp ) >C H (sp)

So, more facile  -elimination occur in option (a)

Correct option is (a)
36. Correct option is (*)
37. In first, examples is an esterification in forward direction and an ester hydrolysis in the backward
direction. Ester hydrolysis is catalysed by acid or base but esterfication by acid only.
The equilibrium will shift towards right in HCl.
In second example is cyanohydrin formation from a ketone. In HCl solution (at pH less than 12). The
oxyanion will be protonated and the reaction driven over to the right.
Correct option is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015 541

38. C C H 3300 cm–1

C C 2150 cm–1
H C C CH2 CH3

3300 cm–1 2150 cm–1

Correct option is (a)

C
H3C CH3 + CH2Cl2
39. Acetone Dichloromethane

6 proton 2 proton
6×1=6 2×1=2 (1:1 intensity)

Both acetone and CH2Cl2 have equal intensity (1:1) for equalization. Dichloromethane multiply by
(3)
6×1 = 6 2×3 = 6
Ratio = 1 : 3
Correct option is (b)
40. Intensity in IR spectrum is due to change polarity and change in dipole moment and expressed in
term of transition moment between two levels.
Transition moment, Rv   v ' µ v " d (transition moment in the form of dipole moment)
2
Intensity, I    v ' µ v " (intensity in the form of dipole moment)
Correct option is (d)
41. Those compound gives precipitate on warming with aqueous AgNO3. Which is more stable
Br
NO3
aq. AgNO3
+ AgBr

[Link]
Aromatic
more stable

Correct option is (c)

42. A free radical has been generated at bridgehead position via the Hunsdieker reaction to show that a
free radical need not be planar.
Correct option is (a)
43. The most stable conformation for the following compound is
Me Me
Me Me
Me Me
steric
Me
H Me hinderence

Me H (1, 3 allylic strain occurs)

(more stable) free from allylic (less stable)
(A) 1, 3 strain (B)
542 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015

(B) is less stable due to the presence of Eclipsing interaction between allylic substituent result in
allylic 1, 3 strain.
Correct option is (a)

O OCeCl3 OCeCl3
NaBH4, CeCl3 + NaBH4
44. Me Me Me
MeOH, H2O
CHO CHO H CHO

OH
H
NaBH4 Na + H B H Me MeOH, H2O
CHO
H

Correct option is (d)

180º
45. H H H Cl

S
· ·
Cl Me Me S H
HO
R R
OH
So, these two molecule are homomers (identical)
Correct option is (c)
46. Trans alkene is more stable than cis alkene. More the number of  -hydrogen, lesser will be heat
of hydrogenation.
Correct option is (b)

O
47.
C H CH2OH
H OH H OH
NaBH4
H OH H OH Plane of symmetry is present.
Hence, optically inactive
[Link]
H OH H OH
CH2OH CH OH 2

Ribose

O
C H
OH
H OH O OH
HCl O HCl
H OH
MeOH MeOH HO
HO
H OH
HO OH
CH2OH HO OH
furanoside
(Open chain)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015 543

CHO
CHO
H OH
Br2–CaCO3 H OH
H OH
H2O H OH
+ CO2
H OH
CH2OH
CH2OH
Optically active

Yes, ribose gives positive Tollen’s test.

Correct option is (a)
48. Umbelliferone is a phenylpso and as such is synthesized form L-phenylalanine. Which is pro-
duced via the Shikimate path way. Phenylalanine is lysated into cinnamic acid. Followed by
hydrolyzed 4-hydroxylate to yield 4-coumaric acid.
Correct option is (b)
49. (R)-4-methylpentan-2-ol are
OH CH3
H

2 4 5
1 3

OH CH3
5 High deshielded region (higher value)

2 4 CH3
1 3 6
So, total number of signal in 13C{1H| NMR spectrum is 6.
Correct option is (d)

50. steric hinderence

H
H H
H
C Me Me
C H Me Me
H
EtO2C EtO2C EtO2C
NaBH4
[Link]
H OMe
O
0ºC OH
H MeOH/THF H H
O H H
H

Correct option is (d)

51. The major product formed in the following reaction is
Me
Ene reaction

CH2 H
Correct option is (a)
544 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015

Me Me Me Me
52. O H O O O
OH OH2
O
H2N NH2 H N NH2
NH NH2
N NH2 H
H

Me
Me H
NH Me Me Me
HO N NH O NH O
O N N N NH
H NEt3 Et 3N
Base

Me Me Me
N
HO N HO HO

+ H NEt3

Correct option is (c)

53. The crown ether form complex with metal cation of I-st group. This depend upon
(i) size of cavity
(ii) complexation ability.
K+ is best filled in crown-6 and ‘N’ is good donar than O and S therefore the order of hosts will be
A>B>C
Correct option is (c)
54. (B) Ethanbutanol and (C) isoniazid are the first line drugs, they are active against mycobacterium
turbercli.
Correct option is (b)
55. If n = 0, then function becomes not acceptable.
Correct option is (c)
56. H n  En n
[Link]
H n   En  V0  n
In presence of extra potential function will remain same but correction term will be introduced into
energy in accordance with perturbation theory.

Correct option is (c)

57. – log T1  cx1 ... (1)
– log T2  cx2 ... (2)
Substituting (2) from (1)
log T2 x2 3  50 

log T1 x1
 log T2   log 
1   3  log1  log 2  3   0.3010 
 100 
1 1
T2  1030.3010  30.3010
 0.9030
10 10
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015 545

1 1
   0.125  100  12.5%
7.99 8
Correct option is (d)
58. For allowed transition selection rule is
S  0   1
3 3
In S  P
S  0   1
Correct option is (b)
 Cx
59.  x, y , z  
xy
 x, y ,  z  
2
  x,  y , z 

 C2x   xy   xz
Correct option is (a)
60. HCl is a ionic compound in valency bond theory

H
 H   Cl 
HCl 
1s
1s 3 pz
Cl
3pz
   H 1s 1  Cl  3 pz  2   Cl  3 pz 1  H 1s  2 
Correct option is (b)
61. For a monatomic species only translational degree of motion is occur. No vibrational degree of
freeom. So, heat capacity is independent of temperarure.
Correct option is (d)
62. Addition of neutral gas xenon at constant volume will increase total pressure. But partial pressure of
gases PCl 5, PCl3 and Cl2 will remain same.
n PCl5
For example, PPCl5  as neither n PCl5 is changing nor V so PPCl5 will remain same.
V
[Link]
So, there will be no effect on equilibrium.
Correct option is (c)
E 
 0 
63. k  AT e2  RT 

E0
ln k  ln A  2 ln T 
RT
d 2 E
ln k  0   0 2
dT T RT
d E 2 E E
But, ln k  a 2   0 2  a 2
dT RT T RT RT
2 E 
Ea  RT 2   0 2   Ea  2 RT  E0
 T RT 
Correct option is (c)
546 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015

3
64. Rate of formation of Z =  rate of consumption of A
2
3
=  2  104  3  104
2
Correct option is (a)

65. µzi '  µzi "   zi F

Electrochemical Chemical Electrical

part potential potential part

For a electron, µe '  µe "  F zi  1

If  is negative µe '  µe "
• Escaping tendency of charge species more
If the negative electrical potential is an applied to an electrode electrochemical potential is larger
then chemical potential. So, it means that tendency of an electron suffering from the electrode is in
hence tendency of oxidation reaction is increase if the positive potential is applied then the tendency
of electron to escape. It means the reduction of electron is increased.
Correct option is (b)
66. Correct option is (c)

Zn  s   Zn 2  aq   2e 
Cu 2   aq   2e   Cu  s 
67. Zn  Cu 2 
 Zn 2  Cu
G  G 0  RTnQ

0 RT
E cell  E cell log Q ... (i)
nF
Equation (i) is multiplied by –nF.
0
 nFE cell  nFE cell
[Link]
 RT log Q

 Zn 2   Cu  s    Zn 2 
G  G  RT log  2  
0
 Q
Cu   Zn  s    Cu 2 

a Zn2
 G 0  RT ln
a Cu 2
Correct option is (d)
68. ns1 np1
L=1
3
S=1 hence, 2S + 1 = 3 P
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015 547

For J value, if orbital is less than half filled than

J  L  S  1  1  0
3
Hence, P0, correct option is (d).
69. The attractive energy due to vander waals interaction is inversely proportional to the sixth power of

the interatomic distance r i.e. Ga  
r6
E

The electrostatic energy of repulsion, Gel is

4 r 0 r 2 d2e  kh
Gel 
2R  h

Correct option is (b)

1 1
70. Z  8  6  1 3  4
8 2
3 3
400  r  400  r 
And % P.F.   Z     4  3.14     0.74
3 a 3  2 2r 
Correct option is (d)
[Link]
PART-C
71. The residual current in case of DCP is non-faradic current which should be minimum to get the
accurate result. This problem of non-faradic current is overcome by use of DPP in which non-faradic
current is less than DCP. That is why DPP is more sensitive than DCP.
Though the polarograph is different in both cases but it has nothing to do with sensitivity.
Correct option is (d)
72. Increase of intensity of light used increases fluorescence as the fluorescence life-time increases.
Molar absorptivity increases absorbance which further enhances fluorescence.
Correct option is (a)
22 2
73. Cross-section =  r 2  r ... (1)
7
1/3 1/3
r  R0  A   1.4  10 13 cm  125   7  10 13 m
Therefore, from (1),
548 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015

22
Cross-section   49 10 26 cm 2  154  10 26 cm 2
7
22
  49 10 26 cm 2  154  10 26 cm 2
7
 1.54 barn  1 barn  10 24 cm 2 
Correct option is (b)
74. For Suzuki coupling boron is required.
For Heck coupling alkene is required
For Sonagashira coupling terminal alkyne is required
For Negeshi coupling organo zinc is required.
Correct option is (a)
4  3  4 11
75. The average of oxidation states is 
3 3
H5 P3O10 5  3x  20  0
3x  15  x  5

H5 P3O7 5  3x  14  0
x  3

H5 P3O8 5  3x  16  0
11
x
3

H5 P3O9 5  3x  18  0
13
x
3
Correct option is (c)

76. Br3  Br  Br2

[Link]
S
7  2 1
 4  sp 3

2
Therefore, geometry = tetrahedral
•• I
[I5+]
I ••I•• I I (trigonal bipyramidal, sp3d hybridisation)
I I I I
••
I
Correct option is (b)
2
77. B12 H12  Bn H n2 
Therefore, it is closo structure
Correct option is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015 549

78. Due to IPE ns2 electron-pair become inactive. In Pb

Pb =
ns np
npz
(n=6)
Therefore, the structure must be
ns npz
R
R
Pb Pb
R
R
ns
npz

Correct option is (a)

79. SbCl3  3EtMgBr 
 SbEt 3  3MgBrCl

2SbEt 3  SbI3  Sb  Et  I 2  n  SbEt 2 I

Correct option is (a)

80. Fe  II  protoporphyrin    * transition

 Mn  H 2 O   Cl2  Mn 2  d 5  high spin  spin forbidden  d  d  transition.

eg eg
hv

t2g t2g
S=5/2 S=3/2

S  1 . Hence, not allowed.

[Link]
 Co  H 2 O 6  Cl2  Co 2   d 7  high spin  (d–d)

eg eg
hv

t2g t2g
S=3/2

S  0 , hence allowed
Correct option is (a)
550 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015

Cl
81. (Ph3P)2Ir
P 2
H

agostic interaction

Due to this agostic interaction C–H bond becomes weak and hydrogen flanked in between M and C.
As proton come in contact with metal becomes shielded and upfield shift in 1H NMR. Since v  k ,
bond strength of C–H bond decreases, in IR spectrum shift to lower wave number.
Correct option is (c)
82. Here, Cp is cyclopentadienyl ligand is one of the most common and popular ligands in organometal-
lic chemistry.

6 electron donor

It is an anionic ligand that normally coordinates in an n5 mode as a 6 electron donor.

Now, 18-electron rule apply on the complexes
(A)  Mn    Cp   CO 3 
5

Mn(II) d5 (5 electron)
Cp 6 electron
3CO 6 electron
____________________________________________________
Total 17 electron


(B)  Os   Cp 2 
5

Os (II) d6 (6 electron)
2Cp 12 electron
________________________________________________
Total 18 electron

(C)  Ru    Cp 2 
5 [Link]
Ru (II) d6 (6 electron)
2Cp 12 electron
_______________________________________________
Total 18 electron

(D)  Fe    Cp  2 
5

Fe (II) d6 (6 electron)
2 Cp 12 electron
______________________________________________
Total 18 electron
 Mn  5  Cp   CO   does not follow 18-electron rule. So, this complex is most deshielded com-
 3

pound whne we going 3d to 4d and 4d to 5d series in the transition element the shielding effect
decrease because of the electron density or the distance between metal to ligand, increases. So,
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015 551

 Fe  5  Cp   is more shielded than other..

 2

Thus, the compound D is most shielded and compound A is most deshielded.

Correct option is (a)
83.  Ru 6  C  CO 17 
TEC = 8×6 + 4 +17×2 = 86
PEC = 86–6×12 = 14
PEC 14
 7
2 2
Therefore, 7 = 6 + 1 = (n + 1) closo
Os5  C  CO 15 
 
TEC = 8×5 + 4 + 15×2 = 74
PEC = 74–12×5
14
PEC = 74–60 =  7   5  2    n  2  .Therefore, nido
2
 Ru 5  C  CO 16 
TEC  8  5  4  16  2
TEC = 76
PEC = 76–60 = 16
PEC 16
  8   5  3   n  3 Arachno
2 2
Correct option is (b)
84. K 4  Cr  CN 6   Cr 2  d 4  low spin 
For a compound to show Jahn-Teller Distortion eg or t2g set should be electronically degenerate.

eg

(1) Cr2+ d4 (low spin) [Link]

t2g
Electronically degenerate hence show John Teller Distortion.
(2) K 4  Fe  CN 6   Fe 2   low spin   d 6  low spin 

eg

t2g
Electronically non-degenerate hence, no Jahn-Teller Distortion.
(3) K 3  Co  CN 6   Co 3  low spin  d 6  low spin 
Same as above hence, no Jahn-Teller Distrotion.
552 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015

(4) K 4  Mn  CN 6   Mn 2  low spin 

eg

t2g
electronically degenerate
Hence, complex will show Jahn-Teller Distortion.
Correct option is (c)

Ph Ph
85. P Ar
Pd
P R
Ph
Ph
For reductive elimination, the eliminating group should be electron releasing group and also the
eliminating product should be neutral.
So, only Me group is electron releasing group among all the given option.
Correct option is (a)
86. Oxy-hemocyanin are proteins that transport oxygen throughout the bodies of some invertebrate ani-
mals. These metalloprotein contain two copper atoms that reversibly bind a single oxygen molecule
(O2).
H
NH N

N O

Cu2+ O Cu2+
N N
N

[Link]
N
NH
H HN

Oxy-hemocyanin
The total of six coordinated imidazole units of histidine present in the active site of oxy-hemocyanine.
Correct option is (a)
3 4
87. (I) 2  Fe  CN 6   H 2 O 2  OH   2  Fe  CN 6   2H 2O  O 2
(alkaline medium ) Reduction
4 3
(II) 2  Fe  CN 6   2H   H 2 O 2 
 2  Fe  CN 6   2H 2O
(acidic medium) Oxidation
(III) 2MnO 4  6H   5H 2 O 2 
 2Mn 2   8H 2O  5O 2
(acidic medium) Reduction
Correct option is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015 553

88. Correct option is (c)

P CH3
89. (1) M reductive elimination CH3
H3C
P CH3

CH3
P CH3 P R.E. P
M  elimination M H M + CH4
(2)
P H P CH3 P
CH3

CH3 H3C

P Olefin insertion P CH3 R.E. P H3C CH3

(3) M H M M+
insertion into
P CH3 M–H bond P CH3 P CH3

H3C
CH3 CH3
H CH3
P Olefin insertion P -elimination P
(4) M CH3 M M +
insertion into H
P H M–H bond P P H H 3C
CH3
difficult then
M–H bond

All the product is possible but possibility (4) is least probable.

Correct option is (c)

90. +1 –2 0 –2 +1 0
H2O + Ca ++
Ca + 2OH + H2

Oxidant
Reduction

H 2 O  Cl   Cl  H 2 O n 

[Link]
Where,Cl = Base, H2O = Acid

OH2
++
H2O OH2

6H2O + Mg++ Mg

H2O OH2
OH2

Base(ligand)
554 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015

+1 -2 0 +1 -1 0
2H2O + 2F2 4HF + O2
same oxidation state
Reductant
Oxidation
Correct option is (a)
91. Step-2 (-bond formed)
 (empty)
M
 (filled)
Step-1 (-bond formed)

Correct option is (d)

92.  Fe  Phen 2  NCS  2 

Fe 2  d 6 complex
At high temperature high spin and at low temperature low spin behaviour at 250 K.

eg

t2g

CFSE = –1.6 0  1.20  0.4 0

µ  n  n  2   4  4  2   4.90 BM at 150 K

eg
[Link]
t2g

CFSE = 0.4  6 0  2.4 0

µ=0
Correct option is (a)
93. 2UO 2  aq   4H   aq  
 U 4  UO 22  aq   2H 2O E  0.56
UO 2 undergo disproportional than UO 22 

2
• UO 22  is linear  O  U  O 

•  UO 2  NO 3 2  H 2 O  2  , co-ordination number = 8
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015 555

• U 3O8 is stable at high temperature.

Correct option is (a)

Et
94. Et Et
O Et Et
[2+2+2]
C
cycloaddition
O reaction Et O O
Et Et
The preparation of tetraethyl pyrone via [2 + 2 + 2] cycloaddition of dynes and CO2. The reaction
employs catalytic amounts of Ni(0), PR3 ligand, CO2 (1 atm).
Correct option is (b)
95.  NH 4 2 Ce  NO3 6   Z 
(1) NO 3 behaves as bidentate ligand. Hence, C.N = 12
(2) Ce4+ has no unpaired electron hence dimagnetic not paramagnetic.
(3) Ce4+ has higher oxidation state hence behave as oxidising agent.
Me2 CO
(4)  NH 4  2  Ce  NO 3  6  
Ph3PO
 Ce  NO 3 4  Ph 3 PO 2  C.N.  10

OPPh3 = mono dentate ligand; NO 3 = bidentate

Correct option is (d)

O O O
96.
C SOCl2 C NaN3 Na+ + N3– C
HO Cl N3
O O O

O C N H
O C N O C N
t
Curtius reaction BuOK H3O+
O O O
[Link]
Base
H OH–
(enolate ion)
H COOH group goes to back side and CH3
group goes to above side

H3C
H COOH HOOC
COOH H
N N
+ HN H3O+ rotate
H3O O C O
C
O H H
Correct option is (c)
556 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015

Me Me Me Me

NaNH3
97. +
NH2
50%
Br NH2 NH2
50%

OH O O O O O

NaNH2 NH3(l) H+
NH 3(l) work up
NH2 NH2
NH 2
Br Br H H [A]

Correct option is (a)

98. AcO AcO AcO

p-TsNHNH2, AcOH H
NaBH3CN H
O N TS N
N N
H
H

AcO AcO
heat N –N2
N
H

Correct option is (c)

O CO2Et O CO2Et
O O aq. KOH
[Link]
99. CH H
r.t.
H2N + CO Et 2
EtO2C N C CO2Et N CO2Et
H
O O

C OEt OH2 CO2Et

COOH C OEt
aq. KOH KOH H H3O+
reflux

N N CO2H N C OEt H N CO2Et

H H H H
(B) (A) O
Correct option is (c)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015 557

0.5 equiv. PhC(Me)2OOH

1.0 equiv. Ti(OiPr)4 OH
100. OMe
OH
+ (A)
1.2 equiv. (–)–DIPT
OMe CH2Cl2, –20ºC

OH
OMe
(B)

Correct option is (a)

Hofmann rearrangement
101.
O O O O
Br Br
NH2 NaOH NH Br Br N NaOH N
Br2 H OH
N F N F N F N F

–Br
O
H
NH2 N CO2H N C O
–CO2 H2O N

N F N F N F N F
isocyanate acyl nitrene
2-fluoropyridin-3-amine
intermediate

Correct option is (a)

102. (OAc)2Pd
(OAc)2Pd Pd(II)

[Link]
OAc
OAc Pd(OAc) oxidation to Pd(II)
2
Pd(0)
N Ph
N Ph H N Ph
H H H
Ph
H
Pd(0)
N

Correct option is (b)

558 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015

2 2
103. Me 1 3 Me Me
Me
KH MeO Me
THF O
18-crown-6, rt Me OHC
HO 1 3 Me Me
2 3, 3-S.T. shift 1
eclipsed form
1, 2-e,e-trans
(6-M.C.T.S)

Me O Ph3P Me
Me C Me CHO
H
ClPh3P
Me Me
H staggered form
0ºC n-BuLi more stable
non-stabilized phosphorous ylide
form z-alkene

Me O Me
PPh3
Me Me

Me
Me
z-alkene

Correct option is (b)

Br
O
104.
• Li •
O O O

[Link]
O
HO 3
+
O

O O O O O
(i) PdCl2, CuCl
O2, DMF, –H2O O Ethanolic KOH O
(base)
(A)

O O O
O OH
H3O+ H3 O+ ethanol
H O
KOH
H

Correct option is (d)

 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015 559

105. 7.10 (m, 1H)

H H (7.66 (m,1H)
132
128

144 2.50 (s, 3H)

134
190 CH3
H 13
S C NMR (28)
7.60 (m, 1H)
O
IR–1680 cm–1

Correct option is (d)

O O O O

CO2Me CO2Me COMe

NaOMe Me I NaCl
106. MeI Me wet DMSO
160ºC

O O O O O
C O Me Me Me
–CO2 H+ LDA, –78ºC
Me
TMSCl

O OSMT O SiMe3 O
Me Me
TMS Cl SN1 reaction
t-BuCl,
TiCl4, 5ºC

Correct option is (a)

O
O O
107.
N O
+
Cl
[Link]
P
N O
P
Cl
P
Cl N O
Cl Cl Cl
H H Cl Cl H Cl
(A)

H2N Ph
Cl
N N Ph N N Ph N Cl
H H H (B)

Correct option is (c)

560 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015

O OLi O O O
LiHMDS
108. EtO2C EtO2C + Cl C CH3 EtO
O C CH3
H3C C Cl O

N NH 1, 3-H-shift N N H2N NH2

–2H2O
EtO2C EtO2C
(B)
H
Correct option is (a)
NHAc
Br OH
I NHAc Br
Pd(OAc)2 CO2Me
CO2Me
CO2Me PPh3.Et3
109. Pd(OAc)2 OH NHAc
N N
PPh3, Et3N
Ts (Heck reaction)
Ts (Heck reaction) N
Ts
Correct option is (d)

110. O O
O
O H2C
Tebbe reagent (4+2) cycloaddition

H Olifination H H
PhMe2Si
O COOEt O

EtOOC
COOEt PhMe2Si O
PhMe2Si

This above two steps are taken from “Total synthesis of Azadiractin”.
Correct option is (c)
[Link]
O
O PhMgBr O Me
EtO H C
H3O+ CH3
111. H
NaOEt
Me • •
O Ph OEt Ph
Me (A) (A)
Michael addition O

Me
A=
Ph
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015 561

O O
Isomerise C NaOEt C Br2
to gain the stability Ph CH2 Base Ph CH2
H

O O
O
O
C CH2Br CH2Br
Br Br C
Ph
Ph CH2Br Ph
Ph
(B)
Correct option is (a)
CH3
CH3
112. CH3 O CH3 O CH3 O O
6 •
hv, acetone hv, acetone hv, acetone 1 5 4
• • • 6
2
• •
5 4 3
3 O 1
H H 2

Correct option is (a)

H H H H
4 1
113.
3 2
H
5 6 H H
H
Correct option is (d)

O O TBSCl
O
114.
(Bn)3Si Cl
HO HO HO
O O
NH2 NH C O NHBoc
O O O
[Link]
O

(Boc) 2

Li O
O L
H
H LiAlH(OtB)3 *
OH BocN TBSO
BTSO attack from
BTSO H NHBoc
(Anticrames) above side S
NHBoc H
Correct option is (c)
562 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015

O Me Me
115. O O
N2 C O
OTIPS
hv OTIPS
[2+2]
–N2 hv
ketene
Me Me Me Me Me Me

H 5
HO OTIPS O OTIPS O 4 OTIPS
tautomerization [1, 5] H-shift hv
H 3
or aromatization 80ºC 2 [1, 3] C–C
1
Cl CH2 CH2 Cl sigmatropic
(solvent)

Correct option is (d)

116. Ph3P CHCO2Me Ph3P CHCO2Me
Stabilized phosphorous ylide to form (E alkene)
O O H
O PPh3 wittig reaction
AcO N C AcO N C CO2Me
H + CH CO2Me H H
H

NH N O
AcO O H
C H
CO2Me CH2OH
–AcO
N N
LiAlH4

[Link]
MeO2C MeO2C

Correct option is (b)

 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015 563

NBS •
* AlBN * *
117. CCl4 +
heat 1 • 2

All are in same

proportion * •*

•
3 4
Br
Br Br Br Br
*
* *
+ + +
*
(A) (C) (A) (B)

So, A : B : C = 2 : 1 : 1.
Correct option is (c)

118.
CO2Me

(i) CuI CO2Me CuI

N2
(ii) SeO2
N2

H H
Me
[Link]
Me
HC SeO
CO Me 2
2 CO 2 M e CO 2 Me
H [2, 3] sigm atrop ic H
rearrangem ent

HO

Correct option is (a)

119.
Br Br
Br2 NaOEt, EtOH

O O O
564 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015

Br

Br
KOH, EtOH COOH

O OH
O OH

Correct option is (b)

120. A gives racemic mixture of C and B gives optically pure C.

NMe2
N3 N3
Br
Br NMe2 N Me2N
(A) Me2 racemic
mixture
OR
N3
N3

NMe2
N
Me2

NMe2
N3 – N3

Br Br NMe2 Br NMe2 NMe2

(B) (Optically pure)
Correct option is (b)

121. + [Link]
–
180º
– +

-BMO

+ – – +
180º
– + + –

-ABMO
If the sign is changed it is called ‘  ’ otherwise ‘  ’.
Correct option is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015 565

122. E 8C3 3C2 6 S4 6 d

IRR 15 0 1 1 3

nA1  1, nE  1, nT2  3
nA2  0, nT1  1
IRR = A1 + E + T1 + 3T2
Translation = T2
Rotational = T1
Therefore, normal modes of vibration = A1 + E + 2T2.
Now, IR active modes = T2
Correct option is (d)
123. Symmetric rotor is CH3Cl

H
H H
IB = IC
C

IA Cl

Symmetric tops, I B  I C  I A where, I A  0

The moment of inertia about the C–Cl bond axis is now not negligible because it involves the rota-
tion of three compartively massive hydrogen atoms off this axis such a molecule spinning about this
axis can be imagined as a top and called symmetric top.
Correct option is (b)

e
124.    B0    g
2m

  gB0    g

[Link]
1 g1 1 0.4
  
2 g 2 700MHz 5.6
0.4
1  700MHz   50 MHz
5.6
Correct option is (d)
566 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015

125. The ground state energies of the atomic molecule can be estimated by infrared spectroscopy.

D0 Eex
Energy 

continum

D0 Dg

Illustration of dissociation

 continuum limit  D0"  Eex cm 1 ( D '0 and D "0 are dissociation energies)
Correct option is (b)
126. Be  1s2 2s1 3s1

2s 3s

1 1
S  1
2 2
 Multiplicity  2S  1  2  1  1  3
L = 0 + 0 = 0  S – term

J   L  S  —  L  S    0  1 —  0  1  1  1  1
[Link]
Hence, terms is 3S1.
Correct option is (a)
127. In quantum mechanics, a slater determinant is an expression that describe the wave function of a
multifermionic system that satisfies antisymmetry requirements and consequantly the Pauli prin-
ciple by changing sign upon exchange of two electrons. Slater determinants is a means of ensuring
the antisymmetry of a wave function through the use of matrices. A Slater determinant always corre-
sponds to a particular spin state is not true.
Correct option is (c)

n2h2
128. Energy in 1-D box
8m 2
4h2
E2 – first excited state energy n = 2 
8m 2
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015 567

h2
E1 – ground state energy n  1 
8m 2
Difference, E2  E1
4h 2 h2 3h 2
 
8m 2 8m 2 8m2

Energy in 2-D box,

n 2
x  n 2y  h 2
8m2
5h 2
E2 – first excited state any (2, 1) (1, 2) 
8m 2
2h2
E1 – ground state energy (1, 1) 
8m 2
Difference, E2  E1

5h 2 2h 2 3h 2
 
8m 2 8m 2 8m2

3D-box energy 
n 2
x  n y2  nz2  h 2
8m 2
 4  1  1 h 2 6h 2
E2 – first excited state energy (2, 1, 1) (1, 2, 1) (1, 1, 2)  
8m 2 8 m 2
1  1  1 h 2 3h 2
E1 – ground state energy (1, 1, 1)  
8m 2 8 m 2
6h 2 3h 2 3h 2
Difference, E2  E1   
8m 2 8m 2 8m 2
Correct option is (b)

129. [Link]
One dimensional simple harmonic oscillator
1/ 4
  2 /2
 0  x   e  x
 
  1/ 4 1/ 4
    x 2 /2   2
*
x    x dx     e x  e   x / 2 dx
  
  
1/ 2  
  2 2
    x1 e   x dx  x n e  x dx
    

In the above equation, n = 1 if n is odd, integral value is zero

Therefore, the vlaue = 0

  1/ 4 1/ 4
    x2 / 2      2
 i x     e   x / 2 dx
*
px    px  dx     e
  
   
568 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015

1/ 2 
  2 /2    x2 /2
   i    e   x e dx
  
x
1/ 2 
  2 /2  2  x    x 2 / 2
    i   e   x  2 e dx
    
1/2  
    x2 n  x 2
       i   x e dx  xe dx  0 if n = odd
   

1/ 2
 
      i   0  0
 
Hence, px  0
Correct option is (c)
130.  x,  x, p x  ... (1)

     
 x, px   xpx  px x  x  i    i  x
 x   x 
     
 ix  i  x      xi  i x  i   i 
x  x  x x

 x, p x   i 
From equation (1), we get
 x, i  xi  ix  xi  xi  0
Correct option is (d)
131.  CO 2  g   4H 2  g 
CH 4  g   2H 2 O  g   K1 1
Co  g   H 2 O  g   CO 2  g   H 2  g 
 K2 2

[Link]
Equation (1) substracting from equation (2)

 CO 2  g   4H 2  g 
CH 4  g   2H 2 O  g  
CO  g   H 2 O  g   CO2  g   H 2  g 

 CO  g   3H 2  g 
CH 4  g   H 2 O  g    K1 / K 2 
 K1 
and the equilibrium constant  K 
 2
Correct option is (c)
132. Correct option is (*)
133. For a multicomponent open system, we have
G   ni µi
i

Differentiating the above equation, we get

 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015 569

dG   µi dni    dµi  ni
i i

But, by the fundamental equation,

dG   SdT  Vdp   µi dni

i

Subtracting the two equations, we get

 n dµ
i
i i   SdT  Vdp

Where,µi = Chemical potential

ni = number of moles
I = components
Correct option is (b)

D D #
134.
A–B + E E
C C
Linear Non-linear
A B
non-linear
transition state

A A 
N A k BT q#

N A k BT
 3 1
 qt3 qr qv11 
non  linear

h q A B qCDE h  qt qr qv   qt qr qv3 
3
linear non  linear

N A k BT qv7

h qt3 qr  linear 

0 7
N A k BT T  T
  A 3/2  A  T 3/ 2
h T 3/ 2 T T T

 A  T 1.5 [Link]
Correct option is (d)
k 
135. log    2 AZ A Z B I
 k0 

Given, 2 AZ A Z B I  4  0.51 I

 Z A Z B  2

Correct option is (b)

2
   1/ 2 
136. kP      kP  
 1  1
570 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015

1/ 2

 
 kP 
1/ 2
1   kP 
1/ 2
At low P, 1   kP 
1/ 2 ½
    kP      H 2 
Correct option is (c)
137. G   nFEcell
Gibb’s-Helmholtz equation,
   G  
G  H  T   ... (1)
 T  P
G  nFE
Therefore, we get
   G    F 
    nF   ... (2)
 T  P  T  P
From equation (1) and (2), we get
 E 
nFE  H  nFT   ... (3)
 T  P
Rearranging we have,
  E  
H  nF  E  T  T  
  P 
But, G  H  T S ... (4)
H  G
S 
T
From equation (3) and equation(4), we get
 E 
T S  nFT  
 T  P
 E  [Link]
 E  S
S  nF      
 T  P  T  P nF

S
Temperature dependence =
nF
Correct option is (c)
138. f  AVe BT
... (1)
 nf 
Since, average energy  NkT 2  
 T V

2  nf 
Therefore, average energy per particle  kT   ... (2)
 T V
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015 571

 nf   nA   nV   ne 

BT

From equation (1), we get,  T    T    T    T   0  0  B

 V  V  V  V
From equation (2), average energy per particle = kT 2  B   BkT 2
Correct option is (b)
139. Since Boltzmann formulation deals with whole system containing N number of particles
fN
Therefore, fN should be replaced by . {Since on incorporating condition of indistinguishability
N!
1
total number of arrangements changes by }
N!
Correct option is (b)
2
140. Rate of reaction, r  k2 C2 H 5  ... (1)
SSA on C2H5, Rate of formation of C2H5 = Rate of dissociation of C2H5
2 2
2k1 I a  2k 1 C2 H 5   2k2 C2 H 5 
2
k1 I a   k1  k2  C2 H 5 
2 k1 I a
C2 H 5  
k 1  k 2
Therefore, from equation (1),
k2 k1 I a
r
k 1  k 2  r  I a
Correct option is (a)

141. When a strong alkali e.g. sodium hydroxide is added to a solution of a strong acid, e.g. hydrochloric
acid, the reaction.
H 
 Cl    M   OH    M   Cl   H 2 O

[Link]
• During the reaction highly conducting H  are replaced by M  which has much lower conduc-
tance , so addition of alkali to acid solution is accompanied by a decrease of conductance.

• When neutralisation is complete then the further addition of alkali results in an increase of
conductance, since the sodium ion and hydroxyl ion are no longer used up in the chemical reac-
tion.
572 SOLVED PAPER : CSIR-UGC-NET/JRF June 2015

• At the neutral point the conductance of the system will have a minimum value.
Correct option is (c)

1 1
142. kav   p  1
1 p kav
1
 p  1 0.9
10
1
p  1  1  0.02  0.98
50
1
p  1  1  0.01  0.99
100
Correct option is (c)
143. Lyophobic colloids are thermodynamically unstable but they are kinetically stable does or does not
occur depend on the balance of attractive and repulsive force. For stabilisation to occur, the repul-
sive forces must dominate.
Correct option is (d)
144. Four sets of measurements are 1.71 105 , 1.77  105 , 1.79  105 and 1.73  105

1.71  1.77  1.79  1.73 105  1.75 105

Therefore, average value (Mean value) 
4
2 2
1.71  1.75 1010  1.77  1.75 1010
2 2 2
  xi  µ   1.79  1.75  1010  1.73  1.75  1010
Standard deviation,  
N 4

 0.0010 1010  0.0316  105

which is in range of 0.030  10 5  0.039  10 5
Correct option is (c)
145. 2d sin   n
a [Link]
2 sin   n  
h2  k 2  2
a
2 sin 30º  2 1Å
3

3 3
a   2  2  1.732  3.464
sin 30º 1
Correct option is (d)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015 573

SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015

CHEMICAL SCIENCES BOOKLET-[A]

PART B
21. Cytochrome P450 function as monooxygenase and catalyses the insertion of oxygen in substrate
R R R O R
cyt P-450
R R R R
Myoglobin is found in tissue and store the oxygen in tissue transported by Haemoglobin.
Correct option is (a)
22. In deoxyhaemocyanin Cu is in Cu(I) state i.e. have d10s0 configuration therefore it colourless and
diamagnetic. Diamagnetism is due absence of unpaired electrons and colourless is due to no d-d
transition as all the orbitals are filled.

His His

N N

His-N Cu(I) (I) Cu N-His

N N

His His

Cu(I) d10
Correct option is (b)
23. CrO 24   MnO 24   FeO 24 
All have +6 oxidation state but due to smaller size on going from Cr to Fe. Fe has very high charge
[Link]
density. Hence, it has very high tendency to accept electron. Hence, strongest oxidising agent.
Correct option is (a)
24. Number of unpaired electrons
3
(A)  CoF6   d 6  high spin   t 2g
4
eg2 4
3
(B)  IrCl6   d 6  low spin   t 2g
6
e g0 0
2
(C)  Fe  H 2 O 6   d 6  high spin   t 2g
4 2
eg 4
Since, A and C has same number of unpaired electron. Hence, they have same magnetic moment. As
A and C are 3d-block metal with weak ligand. Hence, they are high spin while Ir being 5d-metal is
low spin. Because 5d has greater splitting power than 3d.
Correct option is (c)
574 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015

25.  w  5 -C5 H 5     Cl  CO  
 2 2

TVE  A    6  5  3  4   2  36
B  n 18  A  2 18  36  0

B 0
Hence, number of M–M =  0
2 2
Correct option is (d)
2
26.  Mn  H 2 O 6   d5  H.S 

As all the levels are electronically non-degenerate. Hence, No Jahn-Teller distortion. Therefore, all
the Mn-O bond length will be equal.
Correct option is (a)

27.

Fe Fe O Fe O
H3C CO H3C C OC C
CO Intermediate PMe3
CH3
cH3

Example of migratory insertion reaction in which alkyl group insert to CO. A new ligand create acycl
[Link]
a vaccancy is created which is occupied by new ligand.
Correct option is (b)
2 3

oxidising agent
 Fe  Phen 3   
  Fe  phen 3   e

28.
 Re d   Blue 
2
In presence of oxidising agent like K 2 Cr2 O 7 ,  Fe  phen 3  changes it colours from red to blue
hence, they are used in redox titration.
Correct option is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015 575

8 2
29. XeF2 ; S = stearic number = 5
2
Therefore, G = Geometry = trigonal bipyramidal (TBP)

••
F

Xe

••
••

Hence, the shape = linear Xe

F
8 2
XeO 2 F2 s  5 Geometry = TBP
2
Hence, the shape = see – saw

O F
F
O
Xe Xe
••

O O
F
F
Correct option is (c)
30. Correct option is (d)
31. Coulometry is based on Faraday’s law of electrolysis
Correct option is (a)
32. Acidic strength of Borane depends upon
(i)  number of Boron atoms
(ii)  decapping [Link]
Hence, the correct order of acidity is B5 H9  B6 H10  B10 H14
Therefore, correct option is (a)
33. In IF7 and Fe(CO)5, the rearrangement is so fast that axial and equatorial ligands can not be differen-
tial by spectroscopy). The molecules in which rearrangement leads to configuration which are chemi-
cally equivalent are called fluxional molecule.
Correct option is (b)
576 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015

12 
34. The structure of Si6O18  is

Hence, the number of linked tetrahedrals = 6

The size of ring = 12
Therefore, correct option is (b)
35. The structure of C3O2 (carbon suboxide) is
   
O

C

C

C

O (Linear)
4 and 4
Correct option is (a)
36. The Eu and Yb donate two electrons in their metallic bonding unlike other lanthanoids which donate
three electrons.
2 7
 
2
This is due to Eu 4f and Yb 4f
14
 
stable configurations

 Ln 3  3e 
Ln 
 kernel 

 Eu 2  2e 
Eu 

 4f  half filled stable kernel

7

 Yb [Link]
Yb  2
 2e 

 4f  full filled stable kernel

14

Hence, they show abnormally larger sizes than other lanthanoids.

Eu = 1.99Å, Yb = 1.94Å
Correct option is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015 577

(C) (D)
37.
H CH3
Br Br
H3C CH3 H3C H
Br H Br
H

Br H H Br
Br H
H Br
CH3 CH3
CH3 CH3

CH3 CH3
Br H H Br
H Br Br H
CH3 CH3
mirror image
non-superimposable

Enantiomers

Correct option is (d)

O
O Cl
38. O
Cl
[Link]
Cl O
O
Me S Me Me S Me Me S Me
O Cl
Cl +
CO2 + CO Cl

Cl
Me
OH
Me S Me Cl
O S Me

Cl
Correct option is (d)
578 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015

H Br Br O
NaOEt
Br Br
39. Br Br NaOMe OMe
O O MeO O
O
Correct option is (c)

Ph

H2C Ph H2C Ph H2C

O N O O
BnO N N2
HC
Rh2(OAc)4
HC
N2 CH
40. N2
DCM, reflux
O
O O O
Ph carbene formation
H2C
O
O
CH2 Ph rearrangement
CH

O
O
insertion

Correct option is (b)

41. Correct option is (a)

180ºC
42.
O Cope-Syn-elimination
O N N

(A)

[Link]
160ºC
H syn-elimination
O N
N O

(B)
Correct option is (c)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015 579

HO O
HO
OH O OH O OH O OH
O HO HO H+ O
HO H+
43. HO Acetone
HO OH HO OH
D-mannose OH O O
OH

Correct option is (c)

44.

H hv
con-rotation
H

(4+2)

Correct option is (a)

45. O O O
MeOH hv MeOH
hv N2
carbene C CO2Me
N2 N2
O

Correct option is (a)

NO2
( = 7.75 ppm)
46. (J = 8.82 Hz) ( = 7.58 ppm)
(Meta ortho coupling) H H (J = 2.4 Hz)
(Metacoupling)

(Ortho-coupling)
( = 6.70 ppm) [Link]
H OCH ( = 3.80 ppm) 3

(J = 8.8 Hz)
NH2
( = 6.50 ppm)

Correct option is (b)

O O

47. (P) O 
 1770 cm–1 (Q) O 
 1800 cm–1

(R) O 
 1750 cm–1

Correct option is (a)

580 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015

a
H
h
48. (diastereotopic c g H
different methyl) H b H i
H a
H
fH H
d b
F H e CH3 H
H3C H3C
(environment different) e
I j c
H (environment different) H3C H H
d
GH
HJ

Correct option is (d)

H2C CH2
49.
Cl Cl
35
Cl–natural abundance –3
37
Cl – natural abundance – 1
35 35 37 37
Cl – Cl Cl Cl
35 37 35 37
Cl – Cl Cl Cl
3 3 3 1  3 1 1 1
9 : 6 : 1
Correct option is (b)
CF3 O
50. CF3 O CF3 O
H
MeO

N C OMe N CO2Me N CO2Me

Cl H O Cl H Cl H

Correct option is (d)

[Link]
H

CO2Me H 150ºC
H
intramolecular
51. (4+2) cycloaddition
H
MeO2C H CO2Me

Correct option is (a)

OEt O OEt
H+
52. H3C C OEt H3C C OEt
–EtOH
OEt
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015 581

OEt OEt OEt

OH O C OEt O C CH2 1 O C CH2

OEt 2 3
CH3 H
1 2
H3C C OEt H+ E2 200ºC
CO2Et
3 [3, 3]
sigmatropic shift

Correct option is (c)

1
53. ct vs t straight line is observed for ‘0’ order and c vs t straight line is observed for second order..
t
Correct option is (c)
2  0  0  0  1 1 1
54. cos       6.43
4  0 1 0  0 1 5
Correct option is (d)

55. d  B
 Rate of formation of B – Rate of deformation of B
dt
2
= 2k1  A   2k 1  B  k 2  B
Correct option is (b)
1 k 1
56.  v v  = reduce mass
2  
v2 µ1 µ1 1
  
v1 µ2 2µ1 2

1 1
 v2  v1  times the original frequency..
2 2
Correct option is (b)

57. [Link]
Standard deviation in speed  V  V 2 2

2 2 3RT 8RT  8  RT  8  RT RT
 c  rrms  Vavg    3   3   0.67
M M  M  M M

RT
 c  0.7
M
c  T
Correct option is (b)
58. H  U  ngRT
U  H  ngRT

Fe 2CO3  s   3C  s  
 2Fe  s   3CO  g 
582 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015

ng  3  0

ng  3  only  gaseous atom

U  H  3RT
Correct option is (a)
59. Psystem > Psurrounding

Psurrounding

Psystem

Process of expansion takes place. Work is done by the system on the surrounding.
Correct option is (b)
60.  Aˆ  Bˆ  Aˆ  Bˆ   Aˆ  Aˆ  Bˆ   Bˆ  Aˆ  Bˆ 
 Aˆ 2  AB
ˆ ˆ  BA
ˆ ˆ  Bˆ 2
ˆ ˆ  BA
 Aˆ 2  Bˆ 2 only if AB ˆˆ
Correct option is (d)
3h 2 9h 2
61. Given, energy = 3 × E0 = 3× 
8m 2 8m 2
Therefore, degeneracy = 3 (221, 212, 121) (for 3-D box)
Correct option is (a)
62. According to Gibbs-Helmholtz equation
 G 
G  H  T  
 T  P
G
G or H

[Link]
H
Temperature
At absolute zero, i.e. when T = 0, G  H . H of a reaction is equal to the slope of the plot of
 G / T  versus 1/T
Correct option is (d)

63. kp   kp  kp  
1
kp
 kp   1  kp    
1  kp
Correct option is (c)
64. K  Kohlrausch’s constant is specified for uni-univalent electrolyte (stoichiometry) and strong elec-
trolyte (specific identify).
Correct option is (d)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015 583

N i M i Ni M i2
65. Mn  M w    N 1N i M i2
N N i M i
Correct option is (b)
66.  2 Na   SO42
0.1M Na2 SO4 
2  0.1 0.1
1 1 1
I  m1 z12  m2 z22    0.2  0.4    0.6  0.3
2 2 2
 Mg 2  SO42
MgSO4 
let conc. m m m
Ionic strength = 0.3

1
I  m1 z12  m2 z22 
2
1
0.3   m  4  m  4
2
8m
0.3   8m  0.6
2

0.6
m  0.075 M
8
Correct option is (c)

67.   c1 2 s  c2 2 pz is normalized
2 1 2 1
 c12  c22  1 & c1  , c2 
2 2
1 1
 c1   , c2  
2 2
Correct option is (a) [Link]
68. The Mo configuration of N2 and N2+ are
N 2  KK 2s 2 *2 2 2 2
2s 2p x 2p y  2p z

82
B.O.  3
2
N 2  KK  2s 2 *2 2 2 1
2s 2p x 2p y  2p z

72
B.O.   2.5
2

N2 N2
Bond order decreases
Correct option is (c)
584 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015

69. The stability (formation constant for complexation of cryptate complex depends upon)
(1) size of cavity
(2) size of metal cation

cryptand suitable cation

crypt  211 Li 
crypt  221 Na 
crypt  222 K
Hence, k+ ion will form most stable complex with cryptand-222.
Correct option is (a)

70. (P)  Ibuprofen


CO2H

OH
(Q)  Oil of Wintergreen

CO2Me

CO2H
(R)  Aspirin

OCOCH3
(b) P-Z, Q-X, R-Y
Correct option is (b)

PART ‘C’
71. In oxyhaemoglobin Fe is in +3 oxidation state and O2 is in in O2–
[Link]
O v  1560 cm
2 O O
1

O2  vO O  1100 cm 1
O22  vO O  750 cm 1

As oxygen accept electron in  * orbital. Hence, bond order get reduced and frequency decreases.
Since, after binding to Fe in Hb bond between O–O become weaker comparison to free O–O bond in
O2.
Therefore, Force constant k decreases and v  k
Stretching frequency would decrease
 1100 cm 1 is correct option.
Correct option is (d)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015 585

72. Hb  it functions as O2 transfer and contain Fe as active centre.

Cytochrome.b  it functions as electron transfer and contain Fe
Vitamin B12  it is responsible for group transfer reaction and contain cobalt.
Haemocyanin  it is a non-haem, non-iron, copper containing protein and function as O2 transport
system.
Correct option is (a)
73. Inductively coupled plasma atomic spectroscopy (ICP-AES) is an analytic technique used for detec-
tion for trace metals and it is better than AAS for simultaneous determination of metal ions. Hence,
option (d) is correct.
In Atomic Absorption Spectroscopy mercury lamp is not suitable source but hollow cathode
lamp (HCl) are the most common radiation source in Atomic Absorption Spectroscopy and atomiz-
ers most commonly used are flame and electro thermal (graphite). Solid sample is used in determi-
nation.
Correct option is (a)
74. The reaction which involve evolution of  radiation are called radioactive capture reaction.
23
Na  10 n 
 24 Na  
Correct option is (b)
75. Fluorescence intensity is typically directly proportional (linear) to concentration. There are however
factor that affect this linear relationship. When concentration is too high, light can not pass through
the sample to cause excitation, thus very high concentration can have very low Fluorescence and
thus calibration curves become non-linear.
Correct option is (c)

Re(6d)
76.
Mn(3d)

E1 E2

O(2p) [Link]
O(2p)

E2 > E1 hence, energy required for transfer of electron from oxygen to Re falls in UV region. Hence,
Re O 4 colourless while in MnO 4 due to less energy difference it falls in visible region. Hence,
MnO 4 coloured. Also as both Mn and Fe have +7 oxidation stae i.e. they have no d-electron hence.
no d-d transition and colour arises due to LMCT.
Correct option is (c)
586 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015

Hc
Hs Hs
77.
Ha
Ha
Mn
OC
CO
CO

Hc = central proton
Ha = is anti with respect to Hc
Hs = syn with respect to Hc
Ha, Hs, Hc environment are different new intensity ratio 2 : 2 : 1. When allyl is non-fluxional.
Correct option is (c)

78.
species stearic number b.p. .p
7  4 1
BrF4 6 4 2
2
86
XeF6 7 6 1
2
563
SbCl36 7 6 1
2

Hence, correct option is (c)

Note: The lone pair of SbCl36 is stereochemically inactive and that of XeF6 is boderline of
stereochemically active and stereochemically inactive condition.
Correct option is (c)
79. NMe2 Cl NMe2 Cl NMe2
Me2N N N
N
[Link]
P P P P
P P
Cl Me N Cl
2 Cl NMe 2
Cl
N N N N N N
P P P
Cl NMe2 Cl NMe2 Cl NMe2

Correct option is (b)

80. C2B5H7 C  BH
 BH 2 B5 H 7  B7 H 9  B7 H 72  closo 
B H 
n n
-2

Correct option is (b)

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015 587

3–
Ox +
81. O Cl
O O O O

Ox Co Cr

O O O O

O
Ox Cl

(A) No plane of symmetry (optically active) (B) Optically inactive or achiral

or chiral There is plane of symmetry bisecting both the
chlorides and divide the molecule in equal
half reflecting each other

O
C
–
CH2
O C CH2
O
O N CH2

Cr No plane of plane of symmetry

CH2 (optically active or chiral)
O N
O
CH2
O C CH2
O
(C)
Thus, A and C are chiral and B is achiral. Hence, correct option is (d)
82. Mössbauer spectrum of a complex gives information about
(1) oxidation state and spin state of metal
[Link]
(2) types of ligands co-ordinate to metal define by quardurpole splitting on the behalf of electronic
environment of ligand symmetry.
(3) Also information about geometry of metal
Correct option is (c)
83. Structure of Uranocane

U –2 = C8H82–

Cyclooctatetraenide

Hence, oxidation state of U = +4

Thus in uranocene U is in +4 oxidation state and have cyclooctatetraenide ligand.
Correct option is (a)
588 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015

 H 3 PO4
84. V  CO 6    V  CO  6 

H 3 PO4
Co  CO 4     HCo  CO 4 
Correct option is (a)
3 3
85.  Co  CN 5 Cl   OH  
  Co  CN 5  OH    Cl 
The reaction proceed through dissociative pathway and rate is dependent only concentration of sub-
strates. As substate do not have acidic hydrogen. Hence, it does not undergo SN1CB mechanism.
3 2  3
slow
 Co  CN 5 Cl    Co  CN 5   Cl  
OH
  Co  CN 5 OH 
Correct option is (a)

(III) (II)
86. [Co(NH3)5Cl] 2+
+ [Cr(H2O)6] 2+
[(NH3)5Co Cl Cr(H2O)5]4+

Labile due to d7(HS)

(III)
[Co(NH3)5] 2+
+ [Cr(H2O)5Cl] 3+
[(NH3)5Co Cl Cr(H2O)5]4+
(II)
H3O+
d3 (inert)
2+ +
[Co(H2O)6] + NH4 inert due to stable (d3 state)

Correct option is (a)

Cl
Cl H
87. B B H BH H
ClN NCl NaBH HN NH NH NH
4 HCl
BCl3 + NH4Cl
[Link]
ClB BCl HB BH BH BH
N N Cl NH Cl
Cl H
(A) (B) (C) H
Correct option is (a)
88. Number of electron involving in metal cluster = T.V.E – 12
T.V.E in Ru(CO)3 = 8 + 6 = 14 (T.V.E = total valence electron)
Hence, number of electron provided for cluster bonding = 14–12 = 2
Correct option is (d)
89. Tanabe-Sugano are useful in interpretation of spectra of both high spin and low spin complexes of
d2-d8 metal cation.
In Tanabe-Sugano, the energy of excited sate (expressed as E/B) are plotted against ligand field
strength (expressed as   0 / B  .
Zero energy is taken for the lowest term and also two form of same symmetry never cross each other
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015 589

and they bent for apart from each other due to repulsion.
4
T1
30
4
T1
20
4
E/B 4P T2

10

F 0
4
0/B
Correct option is (c)

90.  
(a) There is no good agreement between the calculated  g  g J  J  1 B.M . and experimental
magnetic moments for Eu3+ and Sm3+ ions because of low value (~300 cm–1) of spin orbit coupling
constant. Therefore, the ground state and the first excited states become equally populated, due to
the thermal motion become equally populated due to thermal motion. Hence, the observed magnetic
moment of Eu3+ at room temperature is higher than that calculated from spin-orbit coupling.
(b) Lanthanide oxides are predominantly basic in nature.
(c) The Sm(II) ion has 4f6 configuration. Thus, in Sm(II) 4f subshell is not half filled.
(d) Since the chemical properties of the tripositive lanthanide ions (due to their similar size) they can
not be separated easily by chemical method. Instead they can be separated by ion exchange chroma-
tography.
Correct option is (a)

91.

hv
Mo Mo Mo
OC CO OC OC
OC OC OC
18 electron
[Link]
16 electron
therefore, ' allyl converted into 
intermediate
3 allyl

Correct option is (b)

I
92. I2 
(CO)5Mn–Mn(CO)5 (CO)5MnI + CO (OC)4Mn Mn(CO)4
120ºC
(A) I (B)

(CO)4MnI(py)
(C)
N

Correct option is (a)

590 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015

O
93.
C OC
Fe Fe
CO C

Terminal CO = 2120 – 1850 cm–1

 2 .CO  1850  1750 cm -1
In this complex M–M bond order = 1 and two types of CO’s terminal as well as  2 -bridging. So,
 C O band lies in both range.
Correct option is (a)
94. Correct option is (a)

95.  CrF6 3  d 3

Orgel diagram for d3.

4
T1g (P)

4
P
v3 4
T 1g (F)

v2
4 4
F T 2g(–0.2)  o
v1
[Link]
A (–1.2)  4
2g o

= ground state = 4F
First excited state = 4P
4
 4T2g   0 
A 2g 
v1  14900 cm –1 ; v2  22700 cm 1; v3  34400 cm 1
Since, 4 T1g  P  and 4 T1g  F  have no fix energy therefore, they will not provide accurate value of

0 . Thus, energy difference between 4 A2 g 4 T2 g  14900 cm 1 will be correspond to  0 .

Correct option is (b)

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015 591

OMe
2
96. MeO MeO 1 3
2 H
3
O
HO KH O 1 110ºC
Diglyme [3, 3] sigmatropic
110ºC rearrangement

OMe OMe
H+

H tautomerism H
O HO

Correct option is (c)

97. 2
3
1
O O3 1 O
[3, 3] STR
2
1 (Cope rearrangement)
2
1 3
2
OEt OEt 3

H OEt

OH [3. 3] STR
ene reaction
O
Claisen rearrangement

OEt

[Link]
OEt

Correct option is (b)

98.
N3 N3
NaN3
OH
O OH
OH
OH OH
OH
O=PPh3 H PPh3
N N
•• PPh3 MeCN, N2
NH PPh3
O
OH
OH
OH OH

Correct option is (b)

592 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015

H H
H
99. intramolecular Ru
(2+2) cyclo addition H2C HC Ph
N Ru N
Ph Ru Ph N
O O
H H O
H
LiAlH4 – Ru CH2 Ru (2+2)
N N cycloaddition
N
O (A) O

Correct option is (c)

100. Correct option is (d)

101. CHO COOH COO ½ Ca2+

CHO
HO H HO H HO H
Br2, H2O Ca(OH)2 H2O2 H OH
H OH H OH H OH
Fe2(SO4)3 H OH
H OH H OH H OH
CH2OH
CH2OH CH2OH CH2OH
D-erythrose
KCN, HCN (A)

C N C N H C NH CHO
H OH HO H HO H HO H
H2, Pd/BaSO4 +
HO H + HO H HO H H /H2O HO H
H OH H OH H OH H OH
H OH H OH H OH H OH
CH2OH
[Link]
CH2OH CH2OH CH2OH
D-mannose
H2, Pd/BaSO4

H C NH CHO
H OH H OH
H+/H2O
HO H HO H
H OH H OH
H OH H OH
CH2OH CH2OH
D-glucose

Correct option is (b)

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015 593

:PPh 3
102. Br PPh 3 PPh 3 PPh 3
Br Br Br Br
NaH (A)
H
Now, stablized phosphorous ylide forms Z-alkene from aldehyde.
O O PPh3
PPh3
Br
H

Br Br O
OH OH OH

Correct option is (d)

O
O O O
Me3SI
103. NaH
NaH Me S CH2 H Me S CH2
DMSO
Me Me
Me
O
O
SH Me2
•
Me S CH2 H2C
O H2C O O O
Me2S O Li e
Liq. NH3

(A) (A)
Me Me Me Me
•
H3C O H2C O H H2C OH
e– NH3
NH3

(B)
Me Me Me

Correct option is (a)

[Link]
H
B
104. H
H
BH2 B
BH (A)

H
(i)

(ii)
CO2Me
(B) CO2Me
I
Pd(dppf)Cl2
AsPh3, Cs2CO3
DMF, H2O
Suzuki coupling reaction

Correct option is (a)

594 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015

O O OH
105. MeO MeO MeO
t-BuOK(2.2 eq) NaBH4, MeOH
Me–I (2.5 eq)
THF
OH H+ O
O C CH3 O C CH3
Ac-Cl/py
MeO Et3Si–H MeO CF3COOH MeO
Et3Si–H, DCM

(B) (A)
Ortho/meta reduction

MeO
Birch reduction
Li, t-BuOH, liq. NH 3,
THF, –40ºC

Correct option is (d)

H
Ph
106.
Se Se Ph Se Ph
Cl
AcO
AcO AcO H H H
H
H2 O2, MeOH NaOAc
Se Ph Se Ph
syn-elimination
O
H H H
H

Correct option is (d)

H
I H
107. Pd(OAc)2
[Link]
PPh , Ag CO
3 2 3

CN CN
Intramolecular Heck-coupling reaction.
Correct option is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015 595

108. O
–H2O
H C H + Me2NH H2C NMe2

Me I
+ H2C NMe2
CH2 NMe2 CH2 NMe3
N N N
(A)
Me Me Me

NaCN –NMe3
CN CH2
N
N
Me
Me CN

Correct option is (b)

H H
H Cl H Cl H
NH2 N N N•
109.
H
t-BuO Cl H2SO4 hv
E E E   E
5ºC Cl•  
(A)
(A)
H H H H
N Cl Cl • -H transfer
NH2 NaOH H N Cl• N
E H H
(S) E E E
(B)

Correct option is (c)

O OLi
[Link]
CO Me2 CO Me 2
OH OLi
110. Me
[Link] aq. NaOH, then H3O + Me–Li(2.5 eq)

O N N N
N

Ph Ph Ph Ph
O O H

Me OH
H2O Me H3O+

N N

Ph Ph

Correct option is (c)

596 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015

Br
111. H Br H
SN1
H2O
H H
H H H H H
Locked conformation (3º-carbocation)
bottom face is strically hindered.
So, H2O attack from top face
OH
H OH H

HH H
H

Correct option is (d)

112. A concerted [1, 3] sigmatropic shift.
H OAc
D
3 300ºC OAc
1 1 [1, 3]-C shift
H
2 D
H H

[1, 3]-allyl shift under thermally condition occurs antrafacially and hence stereochemistry changes
(inversion in configuration occurs)
Hence, stereochemistry of (D) and (OAc) will become same/cis.
Correct option is (c)

OH O C Ph

113. [Link]
OH OH
PhCOOH, DCC PDC, DCM
DMAP, DCM oxidation of alcohol
Selective esterfication
H of less hindered 1º-alcohol H O
by DCC (A)
O C Ph

H
CH2 O
alumina
O
(-elimination)

H
(A)
H (B)

Correct option is (a)

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015 597

114. Li
O O
HgCl2
B B
O O
Li-CH(OMe)SPh
CH OMe

SPh

OMe
O
CHO
H2O2 CH B
O

Correct option is (d)

115.

hv
electrocyclic
ring chain

Correct option is (b)

116. O
O
OH O O Cl
Cl

O
NaH
+
Cl
(A)
[Link]
O
O
O
O

OH
H
O N H2N
H3O+

(B)

Correct option is (c)

598 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015

P(O)Ph2 H H
117. H CH3 CH3
NaBH3 Ph Ph
CeCl3, MeOH, –78ºC P anti-cram's P
H
O O Ph OH Ph
O O
Ce PO(Ph)2
Chelations

OH

Correct option is (c)

118. O

H2N NH NH2
H
O N
H O
NH O N N
O
H2N N N C
H
HN
t-BuOH H2N

t-BuOH, heat

(B) N
N
H
t-BuOK

Correct option is (b)

119. t-BuO N O
O O O
Br H t-BuONa O
CO2Et CO2Et CO2Et
NaOEt CO2Et

[Link]
Br
(A)
O
O
Zn/HCl
O
N CO2Et H3O+ N
H2N CO2Et CO2Et

Correct option is (c)

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015 599

120. H+
OMe OMe
O
(i) THF, heat O CF3COOH O
OMe
Me (4+2) Me Me
cycloaddition
TMSO O TMSO O
CO2Me CO2Me

Correct option is (c)

1
121. qv   hv / k BT for loose vibration
1 e
1 k BT
qv  
hv hv
11
k BT
Correct option is (d)

2 2 6 1
122. For 1s 2 s 2 p 3 p 

+1 0 –1
1
s
2

1
2s  1  2   1  2
2

J    s ............   s
 1  ½ ........... 1  ½
3 1

2 2

Term symbol 2 P3/2 2

P½ [Link]
Correct option is (b)

n
123. sin   h 2  k 2  2
2a
n
sin 1  1 0 1
2a
n
sin  2  111
2a
sin 1
2 1.414
    0.816  0.82
sin  2
3 1.732
Correct option is (c)
600 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015

124. Stability of lyophobic dispersions is determined by inter-particle electric double layer repulsion
and intra-particle vander waals attraction
Correct option is (a)
125. The second order correction to nth state
2
2 m vn
En   En  Em
mn

2
 2  2 v 1
 E1 
E1  E2
Correct option is (c)
 B0
126. Frequency f 
2
 H B0
For 1H,  f H   ... (i)
2
 C B0
For 13C,  fC   ... (ii)
2
Equation (i) divided by equation (ii),
fH  H 42.4 27  107
  
fC  C fC 6.75  107
42.4 MHz  6.75
 fC   10.6 MHz
27
Correct answer is (a)
127. First titration:
10 mL of HCl + HNO3 with NaOH
Reaction,
HNO3 + HCl + NaOH  NaCl + NaNO3 + H2O
Suppose in 10 ml aliquots n1 mole of HCl are present, and n2 moles of HNO3 are present.
[Link]
(Numberof moles of HCl = number of moles of NaOH + no. of moles of HNO3)
n2 + n1 = 0.1 V1
Second titration:
HCl  AgNO 3   AgCl   HNO 3
Number of moles of HCl = number of moles of AgNO3
n1 = 0.1V2
Number of moles of HNO3 only = n2 = (n2 + n1) – n2 = 0.1V1 – 0.1 V2 = 0.1(V1–V2)
0.1 V1  V2 
So, (V1–V2) will give number of moles of HNO3. So, from it we will get conc. =
10
Correct option is (a)
128. Reaction-1:
1
Cl 2  e  
 Cl  E 0  1.35V
2
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015 601

Reaction-2:
0.06
 Ag   Cl
AgCl  E0  log k sp
n
0.06
E0  log1010  0.6
1
Reaction-3: On reversing reaction-2
 AgCl
Ag   Cl  E 0  0.6
On adding reaction (1) and reaction (3), we get
1
Cl2  Ag   e  
 AgCl  s 
2
n1E1  n 2 E 2 11.35   1 0.6 
E3    1.95V
n3 1
Correct option is (d)

1
H 2  H   aq   e 
2
AgCl  e  
 Ag  Cl
129.
1
 Ag  s   H   aq   Cl  aq 
H 2  g   AgCl  s  
2

 E 
S  nF  
 T  P
As entropy of reaction decreases because gaseous is being consumed. So, S  0
 S 
 0 E 0cell decreases with increase in temperature.
 T 
Correct option is (b)

h [Link]
1
130. B B where, I = moment of inertia
8 2 Ic I
 I for ClC  CF is highest
Therefore, B would be smallest for ClC  CF
Correct option is (c)
131. Cl H Cl Cl

C C C C

H Cl H H
Trans-1, 2-dichloroethylene cis-1, 2-dichloroethylene
dipolemoment dipolemoment
microwave inactive microwave active
602 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015

These two compound are distinguish on the behalf of dipolemoment by microwave spectroscopy
without any calculation.
Correct option is (a)
132. C2  valence electron  12
 C2   12s  1*2s  22s  2*2s  24 p

2pz

2p

pz

2s 2s

2s

K 1s K
1s

1s
[Link]
However, in not included in valence shell.

Correct option is (d)

133. rmax  S  2 103 1106
r   103 s 1
 S   km 6
110  110 6

Correct option is (b)

ka kb
134. A  A  A*  A,
 A*  P
'
ka

2
ka kb  A
 r  r  kobs  A
k a'  A  kb
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015 603

 ka kb  kobs  ka  A
 ' at high P
with kobs  ka
k  A at low P 2  ka  1  ka  2 atm 1s 1
 a
Correct option is (b)
135. c2  2c2  2 v  1 h  D2 h
Correct option is (d)

136. Entropy and heat capacity

Since, entropy change in partition function is compensated by change in total energy and in heat
capacity differentiation with respect to temperature lead to cancellation of constant shift in energy.
Correct option is (d)

137. n2  hv 
 exp   
n1  kT 
n2 ½ n1 1
    given 
n1 n1 2

1  hv  1 hv
  exp     n    
2  kT  2 kT
hv hv
 T  T 
k B n 2 k B n 2
Correct option is (b)
138. Raman active vibrations transform according to quadratic functions of x, y and z which are Ag and
Bg.
Correct option is (a)
3
139. F  3D
Since, for allowed transition (atomic), S  0, L  0,  1
Correct option is (b) [Link]
140. Average end-to-end distance = 106  103
Correct option is (d)

P2
141. G  nRT n
P1
V1
G  nRT n
V2
1
G  1 R  300  n
4
G  600 Rn2
Correct option is (c)
604 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2015

142. At triple point vapour pressure of solid A and liquid A are same. So,
1800 1400
10   8
T T
400
2
T
T  200K
Correct option is (a)
143. Option (a), (b) and (c) talks about the processes which are spontaneous processes.
Option (a) and (c) can be seen through phase diagram of water and (b) is free expansion which is
spontaneous.
Option (d) talks about an equilibrium process.
 ice
water  0ºC
1 atm
So, this is a non-spontaneous process.
Correct option is (d)
144. In radial part of wave function highest power of r denote the value of  .
Here,   1 and radial node = 1  3 p
Correct option is (b)
145.   c1 0  c2 1

c12 3c22 7
Therefore, c12  c22  1 and  
2 2 6
3

 c12  c22  1   2
c12 3c22 7
   ... (1)
2 2 6
3c12 3c22 3
   ... (2)
2 2 2
[Link]
On solving equation (1) and (2), we get
1
c12 
3
Correct option is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016 605

SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016

CHEMICAL SCIENCES BOOKLET-[A]

[SOLUTIONS]

PART - B

21. (A) Cu TVE = 5 + 11 + 2 = 18 electron

CO

(B) Mn TVE = 5 + 7 + 4 = 16 electron

CO
OC

(C) Cr TVE = 5 + 6 + 6 = 17 electron

CO
OC CO

(D) V TVE = 5 + 5 + 8 = 18 electron

OC CO
OC CO
Correct option is (d)
+ +

[Link]
-hydride
H
22. Rh elimination Rh
 CH2
R3P H2C CH2 R3P
H H2C

Correct option is (c)

n  or n 
 II 
23.  Ni L6  has absorption bonds at 8500, 15400, 26000 cm–1.
 

n  or n 
 II 1 
 Ni L6  at 10750, 17500 and 28200 cm–1
 
as for first complex absorptions bands are at low energy i.e. it has weak splitting therefore, it has
weak ligand and for IInd complex high energy absorption bands corresponds to strong ligand.
Thus, L is weak and L1 is strong ligand.
Correct option is (d)
606 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016

24. Number of microstate in 3F is calculated as (2S + 1) (2L + 1)

For F, L = 3
Hence, (3) (2×3+1) = 21
Correct option is (b)

25. B-H = 4e fragment isolobal fragment should have 14 electron.

Cp  Co  5  9  14
Correct option is (d)
26. TVE = 18 + 16 + 22 + 8 = 64 = A
B = (n × 18)–A = (4×18)–64 = 72–64 = 8

B 8
Number of metal-metal bond =  4
2 2
Correct option is (b)

27. B2  1s2  1s

*2 2
 2s  *2 1 1 * * *
2s  2p x  2p y   2 p z   2p x   2p y   2p z

* = gerade while  = ungerade

– + +
+ – –

* (u)
(gerade) (ungerade)

Centre of symmetry No centre of symmetry

Correct option is (b)

28.  TeF5 


6  5 1
2
[Link]
6 sp d 3 2

Number of lone pair = 1

Structure is square pyramidal

F
–
F F

Te

F •• F

Correct option is (b)

 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016 607

29. Structure of P4S3 is

P

S S
S
P P

P
Number of P-S bond = 6
Number of P-P bond = 3
Correct option is (a)

30. In acidic medium dichromate changes into Cr+++ and in titration S2O32 changes into S4O 62
(tetrathionate).

H+
2– H+ +++ S2O32– S4O62–
Cr2O7 Cr
2x = +4 4x = +10
2x = +12 2x = +6
2x = +5

Valency factor z1 = 6 z2 = 1

Now, milliequivalent of Cr2O72– = milli equivalent of S2O32–

Z1M1V1 = Z2M2V2

6  0.1 25  1 x  25  x  0.6
Correct option is (c)
31. Decomposition temperature of CaCO3 in thermogravimetric analysis will be highest in dynamic
atomosphere due to the presence of 1 : 1 mixture of O2 and CO.
Correct option is (c)

32. 56 Ba
131
 0
1e  [Link]
 55Cs131
 Xe
 01e
54
131

Correct option is (a)

33. POCl3   POCl 2  Cl 
POCl6  Cl  
 POCl 4
liq. POCl3 
(i) Et 3 N    OPCl 2  NEt 3   Cl 

POCl6  Cl  
 POCl 4  Cl 
concentration is not enhanced 
POCl3
(ii) KCl   K   Cl
The Cl– ion produced in this reaction increases the concentration of Cl– and it is not consumed by
POCl3.
(iii) FeCl3  OPCl3   POCl 2  CeCl 4
(iv) SbCl6  OPCl 3  POCl 2  SbCl 6
Correct option is (b)
608 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016

34. Absence of globin chain following reaction is occur

II II II III III
P Fe O 2 
 PFe O2  Fe P 
 P  Fe  O  O  Fe  P
IV II III III
P Fe

 2P Fe  O 
 P Fe  O  Fe  P
 Haematin 

Correct option is (a)


35.  UO 2  MO3  
 3

O –
O O
O N U N O
O O
O O O
N

Co-ordinate number is 8 and geometry is hexagonal bipyramidal.

Correct option is (a)
36. Chelate effect is predominately due to entropy change
3 3
 Co  NH3     Co  en  
 3en   6NH 3
 6  3

N
Co–NH3 Co en
N
H nearly same but entropy change is more.
Correct option is (b)
[Link]
 H •
O NO hv O
37.
Barton reaction -H transfer
• 
– NO 


NO
OH • OH
•
NO

Correct option is (d)

 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016 609

H NO2 O
H O
NaOH O TiCl3, H2O
38. N
Nef reaction
NO2
O
OH OH
Correct option is (b)

N n-BuLi (2.1 eq) N

N Ts N Ts N N Li
H (Shapiro reaction)
39. Li
Li
H n-BuLi

n-BuLi
Li
CHO
–NMe2 O

Me2N H

Correct option is (a)

N N
N N
N N
40. triple bond between N atoms
IR : 2150 cm–1

Correct option is (c)

41.  = 0.74 ppm [Link]

H C
3
a
CH
b
 = 1.33 ppm
3

O H

C H
H H
H
H H
myrtenal
Anisotropic effect of  electrons differentiate the chemical environment of Mea and Meb. Mea is slightly
shielded as compare to Meb.

Correct option is (b)

610 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016

N
O Ph
N
OH
42. (A) (B) (C)

OH O O
Flavonoid Terpenoid Alkaloid
Correct option is (c)

H Cl
43.

– + H
+ H – + Cl –
+ + Cl
– + 


HOMO LUMO Carbocation
Correct option is (a)
O
CH3
O
Ph O H2, 10%, Pd/C
44. Ph O N EtOH
HO
+ 2 + CO2
C C H NHBoc hydrogenolysis NH2
H2 NHBoc
O

Correct option is (a)

45. n - π* :
* [Link]
E *
n-orbital is more stablized than * orbital on
n E increasing the polarity of the solvent, E increases.
less polar So,  decreases .............. (Hypsochromic shift)
solvent
n
more polar
solvent

*

E *
E On increasing the polarity of solvent, * orbital is more stabilizes

 the  orbital. Hence, E decreases.  increases (Bathochromic
less polar
solvent more polar shift)
solvent

Correct option is (a)

 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016 611

(axial attack)
H
O O
Ph O Ph O
46. O LiAlH4 (1 eq) O
THF, 0ºC

O OMe OH OMe
Correct option is (a)

OH OH
47. replace Ha
Ha Hb X Hb
with 'X'
OH OH

(P)
replace Hb Diastereoisomer

with 'X'

OH

Ha X

OH

(Q)

[Link]
(P) and (Q) are diastereoisomers. Hence, Ha and Hb are diastereotopic.
Correct option is (b)

Ph Ph Ph
Ph
NaNH2 H NaNH2
48. Ph H Ph CNa Ph
Ph
Ph (X) Ph Ph (Y) Ph
anti-aromatic
Correct option is (b)
H3C O H O

49. View H View H

CH3 CH3
H H3C
(X) (Y)
612 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016

CH3 H
O O

 = 180º
H H H CH3

CH3 CH3
 = 60º
Anti (X) Gauche (Y)

In (Y) Gauche interaction, destabilies the conformation

Correct option is (d)
X
G X = CH3
50. X X = CN
X = Ph
– Ph A = 12.60
– Me A = 7.50
–C  N A = 0.71

As the value ‘A’ increases. Steric crowding increases with the substitutents. Therefore, prefer at
equatorial position. The magnitude of ‘A values’ dependent on the steric hinderence.
The correct order is Ph > CH3 > CN
Correct option is (d)
51. Higher the pKa value lower will be the acidity.
O O

Base
N H N

(X) (X)
O O
CN [Link]
CN
NC NC
CN
Base
CN
H
NC NC
(Y) CN Aromatic CN
Most acidic proton

H H

Base

Aromatic
(Z)
But due to annelation effect the proton will be less acidic. Hence, higher pKa value.
Correct option is (c)
 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016 613

 
Con-rotation Dis-rotation
52.
(4n) (4n+2)

Correct option is (c)

53. 2s and 2pz orbitals are eigen functions of L2 and Lz.
Lz 2s  Lz  200  0 200
Lz 2pz  Lz  210  0  210

L2 2s  L2 200  0  200

L2 2p z  L2 210  2 2 210

3
L2 2p x  L2 R 21 sin  cos 
4

3
L2 2p y  L2 R 21 sin  sin 
4

3
L2 2p y  Lz R 21 sin  cos  Not eigen function
4

Since, Lz  will change cos  to sin 


3
L2 2p y  L z R 21 sin  sin 
4
Therefore, not eigen functions.
3
 2 2 R 21 sin  cos 
4[Link]
3
 2 2 R 21 sin  sin 
4
Correct option is (c)
614 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016

T 2T

54. M 2M

(I) (II)

T
Average speed, 
M
So, it will be same in both. But average kinetic energy  T .
So, it will be double is second case.
Correct option is (c)
+2 +1 0 -1 -2
55. d6 =

L  M L  5  3  2  D
S = 2 2S + 1 = 5
Hence, lowest energy form = 5D
Correct option is (b)
n
R1  c1  R  c 
56.     log  1   n log  1 
R2  c2   R2   c2 
log R1  log R2
 n
log c1  log c2
Correct option is (a)

57. Given rate is in accordance with the rate of NO 2 F 

 NO2  F
Correct option is (c)
Cl H

C C C
[Link]
58.
H Cl
This molecule is chiral
Therefore, no plane, only one C2.
Correct option is (a)

59. ˆ B
If  and B̂ commute i.e.  A, ˆ  = 0, then they have same set of eigen functions.

p2 2  2
Here, T  
2m 2m x 2
1 2
 V kx , H  T  V
2
 ˆ ˆ
 H, ˆ ˆ
 T   0 &  H, V   0
 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016 615

ˆ ˆ
 T,
 V  0
Correct option is (d)

E
E V
60.
–Ve (end point) –Ve (end point)

V V
At end point,
dE d2E
It shows,  0 & 0
dV dV 2
Correct option is (b)

61. NaOH   HCl  CH 3COOH 

First NaOH will react with HCl will use NaOH is completely titrated during this process conduc-
tance will decrease due to less of OH– ions.

Volume

Conductance

Second after that, as NaOH is completely consume. So, simple addition of mixture of HCl and
CH3COOH will only increase the conductance.

Vol. of

[Link]
acidic

Conductance

Correct option is (d)

 H   V 
62.  P   T  T   V
 T  P

 H 
It shows  P  has a dimension of volume.
 T

Correct option is (b)

616 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016

63. Angle between (1 0 0) and (0 1 0)

000
cos      90º
1 1
And angle between (100) and (011)
000
cos      90º
1 2
Correct option is (a)
64. The standard electrode potential E0 at a fixed temperature and in a given medium is dependent on the
electrode reaction and the electrode composition.
Correct option is (d)
65. In a titration, the percentage uncertainties in the measured aliquot volume and the measured titre
1/2

volume are  x and  y respectively. The percentage error in concentration of aliquot is x 2  y 2  .

Correct option is (d)

66. From Maxwell equation,
dU  TdS  PdV ... (i)
Divide the equation by  dV T at constant T

 U   S   V 
 V   T  V   P  V 
 T  T  T

 U   S 
 V   T  V   P
 T  T

 U   P 
 V   T  T  from thermodynamic relation
 T  V

 U   P 
 V   T  T   P
 T  [Link]
V
... (ii)

Ideal gas, PV = RT
RT
P put this value in equation (ii)
V
 U    RT   RT R T R
 V   T  T V   P Note :  
 T  V T V V T V

 U  R  RT 
   T  P  PV  RT, V  
 V T V  P 
TR TR
 P  P  PP 0
V RT/P
Correct option is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016 617

67. H2  excited state  11g *1

1u

 
L0 
1 1
S   1  2S  1  3
2 2
g  u  u  3u
For half filled
Correct option is (d)
68. When river water containing colloidal clay flows into the sea. The salt water induces flocculation
and coagulation, and is a major cause of silting in estuaries.
Correct option is (b)
69. Pt – complex used as anticoncern drug
Au – complex used as antiarthritis agent
Gd – complex used in MRI as contrast agent due to their strong paramagnetic behaviour
Li – complex used in Mariac depression
Correct option is (c)

70. pH = 10 highly basic. So, there will be over all negative charge
Correct option is (a)

PART - C

71. [Cr(bipyridyl)3]3+ d3 = 4F (ground state term)

4 4
A2g T2g
4
T1g

[Link]
As phosphorescence is spin-forbidden transition and also occurs when electron comes from excited
to ground state. Hence, transition 4 A 2g  2 E g is responsible for the phosphorescence.
Correct option is (c)
72. Structure of CoF2 =
O
 
C
F F

due to more space requirement for double bond the bond angle F–C–O will be higher that of F–C–F
and also C–O bond order is larger than C-F hence, C–O bond length will be smaller than C–F.
Correct option is (c)
618 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016

XeF2 [Xe2F3]+ . [AsF6]–

excess AsF4
XeF4 [XeF4]
73. Liq. BrF3
XeF6
[XeF5]+ . [AsF6]–
Separation of XeF4 from a mixture involves preferential complexation of XeF2 and XeF6 and XeF4 is
then removed in vacuo.
Correct option is (c)
N2 O4
74. (A) NOCl  Sn   NO   Cl (NO+ is not major product)

(B) NOCl  AgNO3 

 AgCl  N 2O 4 (Neutralization reaction)
BrF3
(C) NOCl   NO   BrF4

 NO  SbCl6
(D) NOCl  SbCl5 
Correct option is (b)
75. For orbital contribution the t2g set should be unsymmetrically filled
2 6 3
 Cu  H 2O 6  
 t 2g eg 
 No contribution
 
2 6 2
 Ni  H 2O 6  
 t 2g eg 
 No contribution
 
2
 Co  H 2O 6 
   t 52g eg2 
  Orbital contribution
2
   t 32g e1g 
 Cr  H 2 O 6    No contribution
Correct option is (c)
76.  K   BrF4
KF  BrF3 
 2
 2  BrF2   SnF6 
SnF4  2BrF3 

[Link]
 BrF2  SbF6 
SbF5  BrF3 


This only KF increases the concentration of BrF4 in BrF3.

Correct option is (a)
77. In KMnO4 all the electrons are paired. However, its paramagnetic susceptibility of the order of 10–6
cm3 mol–1 is due to the temperature independent paramagnetism.
Correct option is (d)
*
78. As the electron goes to e1g (dxz, dyz), orbital of metallocene bond length increases as they are anologous
eg set orbital of an octahedral complex.
Fe(Cp)2 e*1g
a1g
e2g
 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016 619

Co(Cp)2

Ni(Cp)2

*
Thus, in Ni(Cp)2 there are highest number of electrons in e1g . Hence, it has highest M–C bond
length.
Ni  Cp 2  Co  Cp  2  Fe  Cp 2
Correct option is (b)
79. Milimoles of each ion are 0.25 in solution.
On titrating with 0.1MEDTA each ion will take 2.5 ml of EDTA..
So, total EDTA used = 2.5 + 2.5 = 5
Correct option is (b)
80. Neutron incident on 10B = 1016 m2 sec–1
t  3  107 sec

dV 3
3% fraction disappears i.e. 
N 100

Cross-section   = ?

dN

[Link]
  dx
N

 dN  1 3
     16 7
 1025 m 2  1000  1028 m 2
 N  ndx 100  10  3  10

   1000 barn

Correct option is (a)

620 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016

H H

81. H H

H Ru H
CO
CO
Ru OC
H H CO CO

CO

Therefore, total protons 8, but in  4 -mode COT attached to the four carbon and all 4 protons show
different environment at –140ºC because fluxonial behaviour slow down and hence, 4 signals will
be observed.
Correct option is (c)
82. Lande’s splitting factor g is calculated as
J  J  1  S  S  1  L  L  1
g  1
2J  J  1
+3 +2 +1 0 –1 –2 –3

Ce3+ = f 1
L=3
S=½
J = |L–S| for orbital less then half filled
J = |3–½| = 5/2
5 / 2  5 / 2  1  1 / 2 1/ 2  1  3  3  1
g  1
2  5 / 2  5 / 2  1
g = 6/7
+3 +2 +1 0 –1 –2 –3

Pr3+ = f 3 [Link]
L=3+2=5
S=1
J = |5–1| = 4
4  4  1  11  1  5  5  1 4
g  1 
2  4  4  1 5
Correct option is (d)
83. The complexes having T ground state have orbital contribution to magnetic moment however for
complex having A or E ground state some time µeff is slightly greater than µspin is due to mixing of
first excited state T (having same spin multiplicity to ground state) mixes with A or E due to spin
coupling and there µeff is calculated by
  
µeff  µspin 1  
  
 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016 621

hv
Cu(II) – 2D

2 2
Eg T2g
No orbital contribution

  
Hence, higher value of µ = µspin  1  
  
Correct option is ( a)

84. The structure of  Al  BH 4 3  is

H H
H H
B Al B
H H H H
H H

B
H H

Thus, number of 3c–2e– bond is equal = 6

Correct option is (c)
85. C2 B3H5   B  H 2 B3H 5  B5H 7
Each B–H unit give 2 electron. For cage bonding.
Hence, 5(B–H) = 5×2 = 10 electron. Each hydrogen one electron,
Hence, 2H = 2×1 = 2 electron
_________________________________
= 12 electrons

[Link]
C2 B4 H 6   BH  2 B4 H 6  B6 H8 B5 H 9
6  B  H   6  2  12 e  5  B  H   5  2  10
2H  2 1  2 e 4H  4  1  4
 14 electron 14 e

Correct option is (b)

622 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016

O
O O

V
86.
O O

For vanadium, I = 7/2. So, 2NI + 1 = 2(1) (7/2) + 1 = 8

So, in EPR spectrum it has two g values and it has two patterns of 8 lines each.
Correct option is (a)
87. BH 3 part of the molecule Ph3P. 11BH3
1
H NMR spectrum = (2N1I + 1) × (2N2I + 1) = (2×1×3/2 + 1) × (2×1 × ½ + 1) = 4×2 = 8
11
B spectrum = (2N1I + 1) × (2N2I + 1) = (2×3×½ + 1) × (2×1 × ½ + 1) = 4×2 = 8
Correct option is (a)
57 57
88. Fe* can be prepared by electron capture process from radioactive 27 CO .

57 electron 57 * I = 5/2
27 CO 26 Fe
electron unstable
capture 85%
I = 3/2 (used as a source)
15%
14.4 keV
57 136 keV
I=½ 26 Fe
Correct option is (c)
89. Structure of m-porphyrine complex can be shown as

A B A
N [Link]
N
B M B
N N
A B A

Here, (A) represents = five membered ring

(B) represents = six membered ring
Thus, these are four 5-membered ring and four-6-membered ring.
Correct option is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016 623

90. cis-platin modifies the DNA structure by binding to N-7 nitrogen atom of guanine base.

 cis   Pt  NH3  Cl  H 2O    Cl
cis   Pt  NH 3  2 Cl2   H 2O   2 
 H 2O

 cis   Pt  NH 3  2 Cl   N  DNA  
 
 Cl

cis   Pt  NH 3  2  H 2O   N  DNA  
 cis   Pt  NH 3 2   DNA

Correct option is (a)

91. During fluxional axial ligands are exchanged with equatorial ligand. Hence,
2
CO
5 OC

Fe CO
1
4 OC

CO
3

O
C2 5 2
2 CO CO
5
CO
CO
1
CO 1
1
OC Fe OC Fe CO OC Fe
4
3
CO 3
CO 4 3C
O 4 CO CO

TBP SP TBP

Correct option is (a)

Et
KOH K+NEt2
92. H N
Et [Link]
S
S
S K I2/aq. solution C S NEt2
Et2N C S
C
Et2Cl + CK Et2N S
Et2N S S

[CpMo(CO)3]2
Et4tds
Mo
OC
S
CO C
NEt2

Correct option is (a)

624 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016

93. Cr  CO 6

O Li OMe
Li C6H5 Me3O+BF4
(OC)5Cr C O (OC)5Cr C (OC)5Cr C
C6H5 C6H5

Correct option is (a)

94. TVE = 10 + 12 + 12 = 34 = A
B = (n × 18) – A
B = (2×18)–34 = 36–34 = 2
2
Number of metal-metal bond = 1
2
TVE = 10 + 12 + 8 = 30 = A
B = (n×18)–A = 36–30 = 6
B 6
Number of metal-metal bond   3
2 2
Correct option is (c)

O
95.
O W C C + Ph C C Me

O [Link]
O
W C
3 W C 3

C C Me

Correct option is (b)

NH2 H
N
5% Pd(OAc)2
96. + Me3Si CH2OH SiMe3
PPh3
I n-Bu4NCl, Na2CO3
CH2OH
Correct option is (d)
 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016 625

Al
O
97. HO CH2 CH2 OH , TsOH Cp2 Ti Cl
O
Tebbe reagent
O

COMe C OMe
O O

O
H3O+
O O O
O

O O Me C OMe
CH3
O H 2C H H 2C :OH2 CH2
H

Correct option is (c)

O O O Li O O O
98.
N O Na+ HMDS N O N O
SN2 TsO
TsO
O
O
Bulky group, Anti attack
w.r.t. this group
O O

SN2
N O

[Link]
O

Correct option is (a)

99. O H
NBS aq. Na + OH –
Br
B romonium ion
formed from less
O Br
O H hindered side

O OH –
Me 2 CuLi Br
Me

SN2

Correct option is (a)

626 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016

O
+ –
KH
H

H
100. K+H–
O O O

O
O

HCl
O O O
OH
H

Cl
HO H O O
H+ Cl

Correct option is (a)

H NH
H N N H
OH
101. conc. H2SO4
H+ O
Dehydration
N O N O N
H H H

[Link]
Ph Ph O
O NH

Ph C Ph H2O, H+
O O
TiCl4, Zn
O N N
(Mc-murry coupling H H
N
H reaction)

Correct option is (b)

NH2 CO2Me
N3 CO2Me
Ph3P H
102. OHC reduction of azide
C

O
 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016 627

CO2Me CO2Me CO2Me

NH NH NaBH3CN NH

O H
H

Correct option is (a)

O OH OH
H H H

103. NaBH4, CeCl3 H2, [Ir(COD)(py)P(Cy)3]PF6

MeOH, 0ºC
O
H OH H O C Ph H
H H

LiAlH4 PPh3, PhCOOH

DEAD
Mitsunobu reaction
H H

Correct option is (a)

O
CH2 CH2
Br Zn BrZn H CH2
104. BrZn
Br Br
Br

O ZnBr Br OH Br
[Link]
work-up

(A)

TBDMS-Cl
Py, DMAP
OTBDMS OTBDMS
Br
OTBDMS

Pd(OAc)2
PPh3 H
K2CO3, CH3CN Br
CH2

CH2
Correct option is (a)
628 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016

O O O P(OPh)2
105. C OH P(OPh)2 C N N N

N N N OH
O

Curtius O P(OPh)2
rearrangement
C N N N
C N N2
OH
O

O
t-BuOH
t
N C O N C O Bu
(A) H
Isocynate (Boc)

NHBoc

Correct option is (a)


O CH 3 O
106. (P) Et hv
 Et + CH 2 = CH 2
(i) n *

(ii) -H transfer
[Link]
(iii) -cleavage
(Norrish type-II)

O
Ph + CO
(Q) Ph hv Ph
Ph
(i) n*
(ii) -cleavage
–CO
Norrish type (I)

O O O

hv
(R) + O
(2+2)
O O
cycloaddition
followed by
O Diels-Alder O O
reaction
 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016 629

hv O
(S) + 3
O2
Sensitizer O
(4+2) cycloaddition
or Diels-Alder reaction

Correct option is (c)

O OH OH

107. (P) H+

Nazarov cyclization
O O H H

Tautomerization

I I I
I
Et NaHCO3 Et
Et
HO O
(Q) HO
I

Et
O
Halocyclizations

OH O
O OH
OH
H+, hv hv
(R) electrocyclization Tautomerization
[Link] 3 2 1 [1, 3] allylic
rearrangement
1

H
m-Bu3SnH
(S) Br AIBN •
toulene, 80ºC
radical cyclization
Correct option is (b)
630 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016

O O
O O

108. O
NaH(1 equi)
O
heat
H
NMe3I Me3N
NMe3I
O
O

O O
NMe3 +

Correct option is (a)

OH OH
109. OEt OEt
HCl/H2O
H lactonization
Cl O Cl O

H H
O O O O

H
E1CB
Cl H

Correct option is (b)

[Link] CO2Et
EtO2C CO2Et
O CO2Et
OH OEt
110. EtO P4O10 EtO O
N H heat N H
H H
O O N OH

CO2Et
CO2Et H H
HO CO2Et O CO2Et
HCl ethanol
H
–H2O
N N O H
H

Correct option is (a)

 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016 631

CO2Et CO2Et
Cu(acac)2
111. N I Ph Ts N Ts N
Cheletropic
Ts
CO2Et reaction (A) CO2Et
Diethyl maleate (4n system)
CO2Et
EtO2C
CO2Et EtO2C

Ts N 1, 3-dipolar con-rotatory
cycloaddition Ts N CO2Et ring opening
reaction CO2Et
CO2Et
EtO2C (B)

Correct option is (a)

O
OH
112. HO CH2I2 cat RuCl3.H2O
Me Me
Me
Zn-Cu NaIO4 HO
Simmons-Smith reaction H H H H

Correct option is (d)

O–Li+ O–Li+
O
SN 2
113. O
ring opening
of epoxide PPh3
HC PPh3
HC PPh3 (A)

OH
[Link]
BuCHO
–78ºC– r.t.
(wittig reaction)

(B)
Non-stabilized phosphorus ylide gives Z-alkene

Correct option is (c)

13
114. C NMR DEPT-135 shows positive CH3 and CH and negative CH2 signals.

Odd number of Hs H
H H C1, C2, C3, C5, negative peak
So, positive peak
5 1 OH
4 2
H2C 3 C4 positive peak
H H H H
632 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016

130.4 ppm 31.9 ppm

OH

114.7 ppm
30.2 ppm 61.8 ppm

Correct option is (a)

115. 6.9 (d, J = 8Hz, 2H); 7.8 (d, J = 8Hz, 2H)
Confirms the para-substitution pattern.
Since, J = 8Hz, δ value in aromatic region, 2 doublets of 4Hs.
O
13
C NMR  value =197 pm (for ketone)
carbonyl carbon, in ester have ppm
in 13C NMR. So, option (b) and (c) ruled out
IR : 1690 cm–1 (for ketone)
MeO
Correct option is (a)

Ph hv
heat H
+ S
intramolecular
116. (4+2) cycloaddition O (2+2) cycloaddition
O S
(A) (B)
Ph
Correct option is (c)

H S-BuLi
CH2
CH2
[Link]
S-BuLi NH
O
NH H
117. (i) S-BuLi (2 equivalent) –78ºC EtO
(ii) (2 equivalent) –78ºC
N
N S
S S
S

H
O
N
NH NH

N N
N
Correct option is (c)
 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016 633

Ph

O
O
O N S
Ph
118. H Ha Me
Hb +
KHMDS K HMDS

O O
O
H Ha = less hindered proton

Me Me OH Me
HO
HO

O O No, 1-3 diaxial O 1-3 diaxial interaction

interaction less stable
(more stable)

Correct option is (c)

H H
O O O
F3CCOOOH
epoxidation as well O
119.
as Bayer-Villiger
H oxidation
H
Correct option is (c)

H H CO2Et CO2Et OH
H Ph
H
120. Ph Ph
CO2Et Ph H CO2Et
OH OH HO
(DHQ)2-PHAL

Syn-hydroxylation below the plane

Correct option is (d)

121. [Link]
V
Single-particle translational partition function  f  

, where  = de-Broglie wavelength 3

n
 f   3 (Given : f     )
n = –3
Correct option is (d)
634 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016

122. Since, only heat is given to system  only number of particles in given states would change under
the criterion of Boltzmann-Equilibrium.

I II III IV V

Boltzmann equilibruim is followed on providing heat

number of particles in ground state would decrease in
components to I, which is followed in II only

Correct option is (a)

123. A 90º pulse width or pulse duration is the amount of time the pulse of energy is applied to the
particular sample in order to flip all the spins into the X-Y plane.
The approximate field width of excitation is given by the formula, RFfield = 1/(4*90º pulse dura-
tion in sec).
RFfield is frequency due associated field strength = 2.5×10–4 ×42.57 MHz = 10642.5 Hz
Here, 42.57 MHz/T is gyromagnetic ratio for proton
Now, 1064.5 Hz = 1/(4*pulse duration in sec.)
Pulse duration = 1/(1064.5*4) sec. = 1/42570 sec. = 23.5×10–6 sec.
Correct option is (a)
124. Under the selection rule, M j  0,  1

+1

J=1 0
[Link]
–1
 3 lines
 transition is originating from J = 0
J=0 0
without with
magnetic magnetic
field field

Correct option is (a)

 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016 635

125. H melt  3 kJ mol1  3000 Jmol1

At T = 300 K

 A 
A  s   B
dP 
s l  tan
dT 3
dP H
Using Claypeyron equation, 
dT TV C
A
l g
 H H 3000 
tan   V   cot  
3 TV    300 3 O
T  tan 
 3


V  10 cot
3
Correct option is (c)
126. BC is an adiabatic compression
Correct option is (b)
127. C4  1 h  C4h
Correct option is (b)

13h2 (2,3) (3,2)

128. E = 8ml 2 g=2

(1,3) (3,1)
2
10h g=2
E = 8ml 2

8h 2 (2,2)
E= g=1
8ml 2

E=
5h
2
[Link]
(1,2) (2,1)
g=2
(1, 2)
g=1
8ml 2 n=2
2 (1,1) (2, 1)
2h g=1
E = 8ml 2 g=1

Degeneracy in 2-D box

2 2 2
h 2  n 2x n y   h  n x  n y   h  n x  4n y 
2 2 2 2
E    2
8m  2x  2y  8m  4a a 2  8m  4a 2 

Now for first excited state, n x  2, n y  1

h2  4  4  h 2  2 
 E   
8m  4a 2  8m  a 2 
Also for first excited state
636 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016

nx  1, n y  2
2 2
h 2  nx  4n y  h 2 1  16  h 2 17 h 2  4.25 
E      
8m  4a 2  8m  4a 2  8m 4a 2 8m  a 2 

h2  2 
So, minimum energy =  , g 1
8m  a 2 
Correct option is (a)

z2
129. I E  13.6  13.6  4
He n2
K.E + P.E. = –54.4 eV ... (i)
From Virial Theorem,
2 T  V

2 kinetic energy   potential energy

1
Also, K.E. =  P.E.
2
1
Therefore, from (i),  P.E.+P.E.  54.4
2
P.E.
 54.4 and P.E .  108.8 eV
2
Correct option is (d)
130. From column ‘3’ and column ‘4’
In front of ‘E’ irreducible representation, it is clear that there is a pair of I.R active modes which are
degenerate.
Degeneracy of ‘E’ = 2
Correct option is (d)
131. 0 , 1 , 2 ,........ are the wavefunctions of a harmonic oscillator in ground state, first excited state,
[Link]
second excited state respectively.
We know that for a harmonic oscillator 0 , 2 , 4 , 6 ........ will have even parity and
1 , 3 , 5 , 7 ,......... will have odd parity..

So,  0  a10  a22  a34

   
EVEN EVEN EVEN EVEN
PARITY PARITY PARITY PARITY

 1  b10  b24  b36

   
EVEN EVEN EVEN EVEN
PARITY PARITY PARITY PARITY

 2  c11  c24
  
MIXED ODD EVEN
PARITY PARITY PARITY
 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016 637

 3  d13  d 25
  
ODD ODD ODD
PARITY PARITY PARITY

Since, the dipole operator is linear, therefore electric dipole transition is forbidden if the initial and
final state have same parity.
Since,  0 and  1 have same parity..

So,  0   1 transition is FORBIDDEN.

Correct option is (a)

132. U  f  T, V 

 U   U 
dU    dT    dV
 T  V  V T

 U   U   U   V 
 T    T    V   T 
 P  V  T  P

 U   V 
 T   CV    T 
 P  P
1  V   V 
Now,        V
V  T  P  T P

 U 
   CV  V
 T P
Correct option is (d)
1
133. nA1  6 11  0  2  3 1  2
6
1
nA2 
6 [Link]
6  0 – 6  0
1
nE   2  6  0  0  2
6
Correct option is (b)
134. Entropy of activation for bimolecular reaction is negative. Therefore, (d) is incorrect
Here, positive salt effect. Therefore, (c) is incorrect
Increase of Dielectric constant increases rate constant.
Correct option is (b)
135. If experimental rate is greater than maximum rate using collision theory then impact parameter must
be greater than sum of radii of reactants.
Correct option is (c)
638 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016

136. For a 3rd order reaction,

1 1 1
k3t    
2   a  x 2 a 2 
 
For half-life time,
a
t  t½ , a  x 
2
1 4 1 3
 k3t½  2
 2 2
2 a a  2a
Correct option is (a)

a a
137. d   h 2  k 2  2
h2  k 2   2 d
Correct option is (b)

1 1 1
138.    1
 k p
1
Slope =
k
Greater the slope, lesser will be  .
Therefore,  for A will be least
Correct option is (d)
139. Correct option is (d)
140. For any bound state particle has equal and opposite value of momentum.
Correct option is (d)
141. A  1  a  1 and H  2  b  2 ,  2 H  b  2
a = eigen value
†
[Link]
†
1 A  A 1  a 1 *
 a  1  a 1  a  real 
Now,  1  A, H   1   1 AH  HA  1   1 AH  1   1 H a 1

 a   1 H  1   1 H  1   0
Similarly,
ˆ H    HA
 2  A, H   2   2 A ˆ   b  A b  Aˆ  0
2 2 2 2 2 2 2

Correct option is (d)

 SOLVED PAPER : CSIR-UGC-NET/JRF JUNE 2016 639

142. In FlorySchulz distribution

2
Pk  Mo 1  p  p k 1
Therefore, mole fraction of polymer with a chain length k is
2
P Mo 1  p  p k 1
yk  k   1  p  p k 1
M Mo 1  p 
Correct option is (c)
143. Correct option is (c)

e2 N A
144. 
 0 r k BT
 c z 
2
i 0 (Debye-Hückel length)

Debye-Hückel screening length

1 kT
  20 r B 2
 e N Aci zi

1 TA
 ... (i)
kA CA

1 TB
 ... (ii)
kB CB

1 1

k A k B only if TA  2TB ; C A  2C B put this value in equation (i)

1 2TB TB
 
kA 2CB CB

1 TB
 from equation (ii)
kB CB [Link]
Equation (i) = equation (ii)
Correct option is (a)
145. log    2.303A Z  Z  I

For same concentration of electrolyte Z Z  I will be smallest for NaCl and largest for LaCl3.
As negative sign is there so slope of NaCl will be least negative and slope of LaCl3 will be most
negative.
Correct option is (b)
640 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016

SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016

CHEMICAL SCIENCES BOOKLET-[A]

PART–B
 
21. In halogen molecules, the    transitions are responsible for their colours as evident from the
following figure
*

* *
p5 p5

 

Correct option is (a)

22. The -donor ligands such as Cl , Br  , I , N-bonded NCS etc stabilize the TBP intermediate and
favour the stereochemical change. The trans-forms tendency to isomers in the order
A  NO 2  Cl  NCS  OH 
Correct option is (a)

 8  5 1
23.  XeF5    7 sp3d 3 hybridization
2

F –
••
F F
Xe

F•• F
Pentagonal Planar

[Link]
as 74% Xe are NMR inactive hence a singlet of five fluorine and due to 26% nuclei a doublet of
satellite.

Satellite signal

Hence, total number of signal is 3.

Correct option is (c)

H+ H

24.  H3   H H + H+ H H
H H
Each bond angle is 60º.
Correct option is (c)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016 641

25. T.V.E. = 8×2 + 5×2 + 2×2 + 4 = 34 = A

B = (n×18) – A = 36–34 = 2
B 2
Number of M-M bonds =  1
2 2
Ph H2
C Ph
P P
Ph Ph

Co

Ru Ru
Co
3 - bridging, 1-M-M bonds
Correct option is (c)
26. Oxidation state of gold in this complex is 2
Me Me
X
P
II
Au
II II
Cl Au Au Cl
II
Au [House Craft Page 1104-1106]
P
X
Me Me
AuII in +2 oxidating state
Correct option is (c)
27. When the norbornene is strained molecule because the hyberdization is sp2 when the metal attached
with norbornene back  -bonding takes place and due to this back  -bonding the hyberdization
changes to sp2–sp3 and hence relief to strain.
Correct option is (a)
28. According to Nephelauxetic series
[Link]
F  H 2 O  NH 3  en  NCS  Cl  ~ CN   Br 
The highest value of  is for F
Correct option is (d)
3
29. The 2 Eg  4A 2g transition in the electronic spectrum of  Cr  NH3 6  occurs nearly at 650 nm.
Correct option is (a)
30. In carbonic anhydrase OH group first attack on CO2 and then CO2 intract with Zn.
Correct option is (a)

31. Due to more acidity of HCl it will undergo more ionization. Hence, concentration of  Cl  aq will be
maximum.
Correct option is (c)
642 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016

32. In d.c polarography supporting electrolyte is taken in excess, so that all migration current is carried
by suporting electrolyte. Thus electroactive species remain free from migration current
1. E1/2 does not depend on concentration of electroactive species.
2. DME is a micro electrode.
3. limiting current is sum of diffusion current and residual current
il = id + ir
Correct option is (d)
33. Saturation factor in neutron activation analysis.
 t 
Activity equation, A  N 1  e irr 

1  e tirr    saturation factor

 
A
Saturation Factor 
N
Where, A = number of decays per second
N = number of atoms of the target isotopes
 = activation cross section
  neutron flux
 =decay constant
tirr = irradiation time
Correct option is (a)
34. Primary analytical method is isotopic dilution mass spectrometry (not using a reference).
Correct option is (d)

35. Ruberdoxin cysteine 2-iron ferredoxin Fe2S2

S (Cys)
(Cys)
Fe Fe Fe
S S (Cys)
S (Cys) S
cysteine cysteine

[Link]
cysteine
4-iron ferredoxin
(Cys) S Fe S

SH Fe Fe S (Cys)
Number of inorganic sulfur (sulfide) which do no belong to
protein chain in ruberdoxin, 2-ferredoxin and 4-ferredoxin
are 0, 2, 4 respectively

S Fe S (Cys)

Fe S

S (Cys)
Correct option is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016 643

36. LaI2 exists as La 3  2I   e  

The electron present is responsible for metallic cluster and high electrical conductivity.
Correct option is (c)

H H H

37.
sp2 sp3 sp
(A) (B) (C)
More s % character, stronger will be the bond.
More strong bond required more bond dissociation energy. So, the correct order of bond dissociation
energy, C > B > A.
Correct option is (d)

38. • Cyclic  -diketones are more acidic than open chain  -diketones
• As the ring decreases, acidity increases
O O
(B) > (A) > (C)
Least acidic
Correct option is (c)

Me
Me

39. (chiral)

P-configuration

Helical chirality, P-configurations. Since, clockwise path from front side.

Correct option is (a) [Link]
Ph
O Me
C2 symmetry
40.
O Me
Ph
Homotopic
Correct option is (a)

41.

All three methyl groups on same side (above). But in option(a) : 1, 3-diaxial interaction occurs.
So, it is less stable conformation. It undergoes ring flipping to give more stable conformation as
shown in option (c)
Correct option is (c)
644 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016

H H H H
Br
Br Br
42. + Br Br
-HOMO *
H H LUMO H H Br

Correct option is (a)

Me Me m-director Me

Ortho NO2 NO2

43. nitration

NO2

Br Br Br

ortho, para When m-directing group is meta to the

director ortho, para directing group, then incoming
electrophiles goes ortho to the m-directing
group.

Correct option is (b)

NO2 NO2

Br

44. Z Br + H N Z
NH

z = more electron withdrawing group, stabalize the carbanion,

more will be rate constant.
Electron Withdrawing Effect : CF3 > CH3 > OMe
Correct option is (a)
45. C6H6 : [Link]
CH –CN 3
6H 3H
1 equivalent : 2 equivalent
6H 6H
1 : 1 (Integration ratio)
Correct option is (c)
3314 cm–1

46. H3C(H2C)4H2CC C H

2126 cm–1

C C 2126 cm–1
C C–H 3314 cm–1
Correct option is (c)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016 645

4 3 Br
2
1 1
2
47. Br 3 4

4 3 Br
2 1
1
2
Br 3 4

Molecule have plane of symmetry. So, in 13C NMR four signal.

Correct option is (a)

AlCl3 –H Rearrangement
48.
endo exo
AlCl3
Rearrangement
Rearrangement

Correct option is (a)

O O
49.
OTBS OTBS
attack from less
Top hindered side

H3C CuLi
Me
Correct option is (b)

[Link]
Conjugated double bond

50. CO2CH3
CO2CH3
Zn/Cu, CH2I2

Isolated double bond

Simmons Smith reaction.

Simmons Smith reagent reacts on isolated double bond, to form a cyclopropane.
Correct option is (d)
646 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016

H
N  
N H O
51. 6
5
 
N 4 N H N
1
N
3 2
(Adenine) O
(Thymine)

Correct option is (b)

52. J J J

500 MHz

TMS
1759 1753 1747 1741 Hz

1759+1753+1747+1741 1750 Hz
Chemical Shift δ    3.5 ppm
4 500 MHz
Coupling Constant J  1747 –1741  6 Hz or difference between any two adjacent peaks (coupling
constant is not change in Hertz).
Correct option is (a)

53.  total spin ½ particle

5 5 4 3
Weight of configuration = 5 C3    10
32 32
Correct option is (d)

54.
 k  E T  T 
ln  2   a  2 1  [Link]
 k1  R  T1T2 

 k600  49.8 1000 J mole1   600  300  K 

ln      10
 k300  8.3 J mole 1K 1  300 K  600 K 

k600
  e10
k300
Correct option is (d)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016 647

55. Covariance shows the tendency in the linear relationship between the variables.

If y  f  x   x n (where n > 1), then cov  x, y    ve

If y  f  x   x n (where n < 0), then cov  x, y   ve

If y  f  x   x , then cov  x, y   0

For options (a), (b) and (d), y  x 2  cov  x, y    ve

For option (c), y  x cov  x, y   0

Correct option is (c)
56. From figure it is clear that each void is surrounded by three circles.

Correct option is (b)

u
57. t 
u  u
u   6  10 4 u   5  10 4

6 104 6
t  4 4
  0.545
6 10  5 10 11
t   1  t   1  0.545  0.455
Correct option is (a)

58. AlCl3  Al3  3Cl1

0.008 0 0
0 0.008 0.024
KCl  K   Cl  [Link]
0.005 0 0
0 0.005 0.005
1 1
I
2
  2 2 2
C1Z12  C 2 Z 22  C3 Z32  C 4 Z 42   0.008  3   0.024 1  0.005 1  0.005 1
2
2

1
I  0.072  0.024  0.005  0.005  0.053
2
Correct option is (b)

59. For normalised wave function, c12  c22  c32  1

1 1 1
   1
3 2 6
Correct option is (c)
648 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016

60. In NMR spectroscopy the static magnetic field is used to create population difference between the
spin states
Correct option is (c)
61. dU  TdS  PdV
dq
We know that, dS 
T
dU  PdV
dS 
T
dU  PdV  TdS  0 ... (1)
If S & V are constant, then equation (1) becomes
 dU S,V  0
Criteria of spontaniety.
Correct option is (a)

62. Standard condition means 1 bar pressure

For A

s l
p1

p 0.2 vap

T
So at 1 bar transition will be solid  liquid. So number sublimation
For B

s l
p1

p 0.5

T [Link]
Same explanation as above
Correct option is (d)
H #
k T   #/R
63. k  B e RT e S
 h 

k  k B  S # / R  H # / RT
  e e
T  h  
#
k   k B  S # / R  H  1 
ln    ln   e    
T   h   R T 
y  c  mx
Correct option is (c)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016 649

64. For allowed transition,   1 and for Lyman Series Transition is from higher level to n = 1
Correct option is (b)

H1 H2 H2 H1 H4 H3
65. C C C
C4
C C C
Rotation Reflection
C C C
H4 H3 H4 H3 H2 H1

Equivalent

Correct option is (b)

2
66. Given: V  x
v 
Force     x 2  2 x
x x
1 2
 V kx  x 2  given 
2
1
 k  1  k  2  force constant
2
Correct option is (b)
67. Total surface Area = Number of molecules × Area covered by 1 mole (A1)

105
100 cm 2   6.023  1023  A1
602.3
100 cm2 × 10–16 = A1
A1 = 100 Å2
Correct option is (b) [Link]
68. In equation,    kM a

  represents intrinsic viscosity

Correct option is (c)
69. Many properties of nano-particles are significantly different than the corresponding bulk material
because large ratio of surface area to volume of nono-particles in compare to the bulk.
Correct option is (c)
70. Camphor  Terpene
Insulin  Hormone
Keratin  Structural Protein
Correct option is (b)
650 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016

PART – C
 
71. 8C (graphite)  K  (am)  e  (am)   K (am)   C8 (s)

Due to the presence of unpaired electrons in  band of graphite it is paramagnetic and its electrical
conductance increases. It has eclipsed layer structure
Correct option is (d)

72. CCl4 or C6H6

6S2 Cl2  16NH 3   S4 N 4  S8  12NH 4 Cl
Correct option is (a)

73. Ce  NO3  4  OPPh 3 2

Ce 4   4f 0  No f  f Transition
N D unpaired electrons.
It is diamagnetic and its colur is due to LMCT. Its C.N. = 10
Correct option is (c)

74. Statement I   Rh  CO  2 I 2 
Converts CH3–I and CO into CH3COI

Statement   Rh  CO  2 I 2  is diamagnetic in nature.
I and II are correct but II is not correct explanation of I.
Correct explanation : Monsanto process occurs via oxidative reaction, migratory insertion and re-
ductive elimination reaction for that the starting compound must be square planar.
Correct option is (b)

75. In 30mg sample the overall activity is 3000 s–1. So, mass of 12
PO42 is
3000 30
3100×m = 3000 m  
3100 31

[Link]
mA mB
nA  nB RAB  molar mass  molar mass  R AB

RAB = Ratio of A and B in sample mA  mB  mAB

30
Out of 30 mg mg in B
31
 30 
So,  30   is A
 3 
 1 30
Mass of A = 30 1    30 
 31  11
30
30 
mass of A 31  30
RAB  
mass of B 30
31
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016 651

mA  2  30  60 mg
Out of 1g amount of PO4–3 in 60 mg.
3 60
So, % PO4   100  6%
1000
Correct option is (b)

76. FeO 44  Jahn-Teller distorted away from the ideal tetrahedral towards a flatterred structure

Fe4+
it is paramagnetic due to unpaired electron D2d symmetry
Correct option is (c)

77.  Re H9 2  Tricapped trigonal prismatic

2
H

3 1
7 H H
H 9
Re H
8H
H H
4 6

H
5
Atoms 1 to 6 are the prism atoms, 7 to 9 are H-atom are equatorial hydrogen.
Correct option is (a) & (c)

Correct structure is
I
78.
[Link]
b
I a P a I
P P

I c2 I

One c2 axis and one plane of symmetry exist in this molecules.

So, two types of phoshphorous atoms

For a P   2NI  1   2 1 1  1  2  doublet 

 
 2 

For b P   2NI  1   2  2  1  1  3  triplet 

 2 
Correct option is (c)
652 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016

79. Cl2  solvolysis and disproportionation of Cl2 in NH3

Cl 2  2NH 3  NH 2 Cl  NH 4  Cl 
S8  undergoes disproportionation in liquid NH3
5S8  16NH 3  4S4 N   4S62  12NH 4
CH3COOH acts as strong acid in NH3
CH 3COOH  NH 3  CH 3COO   NH 4
Molecules that do not behave as acid in water, may behave as weak acids in NH3.
H 2 NCONH 2  NH 3  NH 4  NH 2 CONH 
Correct option is (d)
2
80.  Mn  H 2 O 6   H 2 O is a weak ligand, No pairing occurs.

Mn2+
+2 +1 0 –1 –2
S  5, 2S  1  6
L  0  5 Term
 Ground state term  6S

Cr3+ 1
+2 +1 0 –1 –2
L  3  F Term
3 3
S 2S  1  2   1  4
2 2
Ground state term  4 F

Cu2+
+2 +1 0 –1 –2
[Link]
L   | M L | 2  D
1
S  , 2S  1  2
2
Ground state term  2 D
Correct option is (b)
81. Co-enzyme B12 catalyses dehydration, 1, 2-carbon shift reaction.
Hence, correct option is (b)
82. Metallothionines  Cystein rich protein
Plastocyanin  Electron Transfer
Ferritin  Iron storage
Chemotherapy  Carboplatin
Correct option is (c)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016 653

2 
83.  CO  NH 3 5 Cl   OH   CO  NH 3  4  NH 2  Cl   H 2O ... (i)
 2
 CO  NH 3 4  NH 2  Cl    CO  NH 3 4  NH 2    Cl  ... (ii)
2 2
 CO  NH 3  4  NH 2    HOH   CO  NH 3 5  OH  
Correct option (b)

84. Heme A  Iron porphyrin  Colour due to    water splitting enzyme contains transition
0 × 0 bridged Mn 4 cluster
eg
2t Spin forbidden
Mn(H 2O)6 3d5 transitions
t2g
2
 Cr  H 2 O 6   t 32g eg1  Tetragonal elongation .
Correct option is (b)

85. Co  CO 3

9 + 6 = 15 (for 18 electron require 3 electron)

P  BH 2
(for 8 electron require 3 electron)
5 3 2  5

CH  BH 2 (for 8 electron require 3 electron)

4 1  5 3 2  5
 
Ni 5  C5 H5 (for 18 electron require 3 electron)
10  5  15

Co  CO 3  P  CH  Ni 5  C5 H5  
[Link]
Correct option is (b)

86.  
 Co 5  C5 H5 B4 H8 
 

Co 5  C5H 5 
  BH 
14 4

 BHB4 H8    B5 H5 4   BnHn 4  nido


 Mn 2  B3H8  CO   ;    BH 2 
 Mn  CO  4  
 4
7  8  15 5

 B3H8BH 2    B4 H10    B4 H4 6   BnHn 6  Arachno

Correct option is (b)
654 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016

2
87.  Rh 6C  CO 15 
 
TVE = 9×6 + 4 + 15×2 + 2 = 54 + 4 + 2 + 30 = 90
Hence, it has trigonal prism geometry.
Correct option is (c)
88. B4 H10  NMe3  Me3 NB3 H 7  Me3 NBH3
Correct option (a)

H2C CH2 –PMe3 -H elimination

89.

Co H2C Co Co D3C Co
Me3P CD3 PMe3 or CD3 H2C CD3 CD3
– 18 e–
CD3 CH2 CD3 18 e H2C CD3 H
18 electron
CD3

D3C CD3H +
+ R.E. reaction
PMe3
H2C D3C Co
Co
PMe3
CH2 PMe3

Correct option is (c)

H
CO Cl
H
OC
Fe(CO)5 + HCl
90. OC Fe Fe H
OC
CO CO H
(B) H
(C)
H H
[Link]
Compound (C) has show four 1H NMR signal
Correct option is (b)
1/ 2 1/ 2
91. k12   k11 K k 22f    5  4 103  2 108 1.0   20  105  2.0  106
Correct option is (b)
92. Fischer carbene carbon is electrophilic in nature due to strong  -acceptor ligands
Correct option is (a)
93. (A) trimethylamine  pKa 9.8
(B) dimethylamine  pKa 10.8
(C) methyl amine  pKa 10.6
pH > 7 is a basic pH and amine with lower pKa value will give the proton easily, and will elute at last.
Correct option is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016 655

94. Number of hyperfine line (due to Cu and nitrogen)

 2NICu  1  2NI N  1
 3 
 2  1 1  2  2 1  1
 2 
4  5  20
Correct option is (a)
95. Number of triangular anti-prism are 8, in icosahedron it is 20 and in tricapped trigonal prism capped
on square faces) it is 14
On capping to square faces

4 new ages are generated and

4 triangular faces. Hence,
total faces become 4×3+2=14

Correct option is (a)

Br
96. Cl Cl

F F
Br
Both fluorine in same environment.
1 
So, form doublet  2NIF  1   2 1  1 = 2
 2 

Br Br
Br Cl Br Cl

F F F F
[Link]
Cl Cl
Both are mirror image to each other but flourine
in different environment

 1 
 2  2   1  3 triplet
 2 
So, total number of line = 2+ 3 = 5
Correct option is (d)
656 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016

SN2  less hindered

OSO2Ph O
OH2
O PhO2SO
97.
O
(A) (B)
H2O O

OH HO

O (D)
(C)

Correct option is (c)

Me
O I
Li
I O O
O Cl
O O t-BuLi
98. Me
H2C CH2
N
N +
N
+ –
I Cl

Correct option is (c)

O O O
N
S
C H N C
H
H S +
99. H
NaOMe S N

O
[Link]
OH
OH
S
+ H
O H O
transfer O
OH N
N S N SO
O

OH

Correct option is (b)

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016 657

7.7 ppm 8.0 ppm

100. H O H
6.8 ppm
H CH3
N

H CH3
H3CO H 3.0 ppm (s, 6H)
5.8 ppm
3.8 ppm(s, 3H) H 7.7 ppm

6.8 ppm

O O

CH3 CH3
N N

CH3 CH3
H3CO H3CO
(More stable structure)

Spectral data confirms the Para-pattern, so option (a) and (b) ruled out. Options (c) and (d) may be
correct but in option (d), the methyl are non-equivalent due to resonating structure, exhibit different
signal. But in option (c), two methyl group are chemical equivalent and exhibits a singlet of 6-Hs
Correct option is (c)
Backside

O HO H H
HO
H
101. RS RL RS RL

Si-face
(Backside)

Correct option is (d)

OAc OAc
102. [Link]
O
OAc
O
O PBr3 + H2O
AcO AcO AcO
AcO AcO AcO
axial attack
OAc OAc OAc
OAc OAc Br
OAc Br OAc
I O
NIS O O Zn, AcOH
AcO AcO AcO
AcO AcO AcO
axial attack
OAc
CH3OH OAc Br
I Zn
O
AcO
AcO

OCH3

Correct option is (b)

658 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016

H2 C H Me
t-BuO–K+
S H3C I S S
H3C Me H2C
103.

O O O
Me
H3CS S
H2 C

O
O

Correct option is (b)

Cl PCy3
Ru
Ph CO2C2H5 C2H5O2C CO2C2H5
104. CO2C2H5 Cl PCy3
CO2C2H5
CO2C2H5 Grubb's catalyst [4+2]
cycloaddition reaction

CO2C2H5
H
C2H5O2C
CO2C2H5

CO2C2H5

[Link]
Correct option is (a)

Br
Br
Br
(i) K2CO3 Br
N Br N O N C Br
1, 3-dipolar
105. O cycloaddition
N O
O OH O
H H3C C C CH (iii) Br2
(ii)
Br Br
Br Br
(iv) NaBH4
N OH N O
O O

Correct option is (a)

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016 659

106. This is Julia Olefinations reactions, under the given set of reaction E-alkene is formed. The detail
mechanism is shown below.

O O
O O
S N TESO S N
N + NaHMDS N
O N N O N N
Ph OHC
Ph
TES : Triethylsilyl H
OMe OMe
C
O

TESO

O
O
OTES
S N
N
CH O
O N N
O Ph
OMe
OMe E-alkene
TESO

Correct option is (b)

O O

107. O2N N H N

More stable Less stable

[Link]
–R effect of this group, increase stability of intermediate.
In that case electron withdrawing group increase the rate of reaction.

O2N O2N O2N

OTs OTs OH
H2O

Less stable

EWG containing carbocation intermediate decrease the stability.

660 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016

H H H
OTs OH
H2O

More stable

Correct option is (d)

O
108. DMSO
+ N COOH N COOH
N CO2H
Acetone H H H
L-protein
+

H H
O OH N
OH OH O O B (OAc)2
O HOOC
O
CH3

Correct option is (a)

O
2
O Se 3
O Se O 1 O
H OH Se O
O
H O
O 2
1 3
109.

[Link] [3, 3] S.T.R.

OH
CHO PCC

Correct option is (a)

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016 661

OMe

OMe
110. MeOH OMe
Tl(NO2)2
Tl(NO2)2
Tl Tl(NO2)2 ring
O2N Me control
OMe
MeOH

OMe OMe

Correct option is (b)

* * *
OBF3
H
111.
N N N
H
H H
*

*
N N

H H

Correct option is (c)

112. Coupling reaction
Correct option is (a)
[Link]
SiMe 3 OSiMe3
O O
LDA
113. Ph C H + Me3Si CN Ph C H Ph C

CN CN i
O OSiMe3 Pr I
Hydrolysis
Ph Ph C iPr

CN

Correct option is (d)

662 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016

Hg(OAc)
Br
114.
Hg OAc HgBr
NHCbz 5-membered N N
ring formed
easily Cbz Cbz
NaBH4
O O
OH O O OBr
N N N

Cbz Cbz H Cbz H

Correct option is (d)

115. (i) + 2K

10 e– system (Aromatic)

(ii) + H 2SO 4 H

H
Homoaromatic
H

heat
(iii)
H Non-aromatic

heat
(iv) + 2K

[Link]
Anti-aromatic
Correct option is (a)

H
OEt
OEt Me
OEt
OEt O O OEt
C
H3C OEt BuO BuO
116. H3C C OEt
3
EtO OH
2
BuO 1O
H EtO2C OEt
[3, 3] STR
BuO
BuO 1 3
2
(Product)

Correct option is (b)

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016 663

N N
117. x
N Less stable N N
N resonating
N N
structure

+ve charge comes on both 'N' atom

(Less stable resonating structure) Positive charge comes on one nitrogen atom
(More stabilized resonating structure)

Correct option is (b)

118. Barton reaction :

hv -H abstract
 
•  •
ONO NO O OH

H N
H

O
H3 O+
OH
OH
O
N
OH

Correct option is (a)

+
+H
[Link]
ring –
119. HO HO
expension O

Correct option is (b)

120. DDQ used for deprotection of benzylether through one electron oxident process. As the number of –
OMe increases on the aryl ring, reactivity towards deprotection increases. So,
O

removed to give Alcohol.

OMe
Correct option is (d)
664 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016

 
121. Hˆ  Hˆ 0  a L  S
For constant of motion C, we must have
C , Hˆ   0
 
      
Here,  L  S , Hˆ   0 and  L  S   0   S , Hˆ  ,  L, S , Hˆ   0
Correct option is (c)

Z2 25
122. E  13.6 2
  13.6  2  13.6  n  5
n n
Therefore, orbital degeneracy = n2 = 25.
Correct option is (c)

123.    Aˆ is normalised

†
   Aˆ   Aˆ  d  1
†
  A† A d  1    † d  1

Therefore,  will be normalised if A† A = 1

 A is unitary
Correct option is (c)
124. According to Perturbation theory, “The energy of perturbed system is equal or greater than the stan-
dard system”.
Correct option is (*)

125. 1 g 1 1 u  2   1 g  2  1 u 1

  
   1s H a  1  1s  Hb  1  1s H a   2    1s  H b   2  
 

 [Link]
  1s H a   2   1s  H b   2    1s  H a  1  1s  Hb  1 
 

 2  1s H a   2  1s  Hb  1  1s H a  1 1s  Hb   2  

 
Correct option is (b)
1 1
126. The arrangements for  1 g   3 u  configurations are

(I) mL u
0

g g
mL +1 -1
S = 1, 2S + 1 = 3
L  1   Term
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016 665

Spectroscopic Term  3 

(II) mL u
0

g g
mL +1 -1

L  1   Term
S  0, 2S  1  1
Spectroscopic Term  1S
Thus one of possible moleculer term symbol is 1
Correct option is (a)

A1 1 1 1 1
B1 1 1 1 1
127.
A1  B1  1 1 1 1  x polarised

Correct option is (b)

128. The polar point group are
Cnv , Cn , C1 , Cs
Correct option is (d)

129. BHBr  10 cm 1 , vHBr  2000 cm 1

H HBr vHBr  1 2000 cm 1 

BPBr  and vHBr   B  and v  
2 2  µ µ 

10 cm 1 2000 cm 1
[Link]  1410 cm 1
1
 BPBr   5 cm and v 
2 2
Correct option is (d)
130. N2O is microwave and rotational Raman active molecule.
Correct option is (b)
131. 200 MHz 600 MHz
J coupling constant = 10 Hz
Difference in terms of  -value remains constant.
So, at 600 MHz, 2ppm = 1200 Hz . Hence, correct option is (d)
132. dH  TdS  UdP
S H P

U G

V A T
666 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016

 H   S 
 P   T  P   V
 T  T

 S   V   H   V 
Now  P     T  . So,  P   T  T   U
 T  P  T  P
This is T.E.S. II
Now for given gas
P  V  b   RT  PV  Pb  RT
Constant P on differentiating with respect to T
 V   V  R  H  R
P  0  R       P   T P  V
 T  P  T  P P  T
now from equation

RT TR TR
P  V  b   RT  Vb  V    V  V  b  V  b
 P Vb
P
RT

 H 
So  P   b
 T
Correct option is (b)
133. According to Clapyeron equation
dP H

dT T V
if V  0 (because change in volume is zero)
dP H dP
 ; 
dT T(0) dT
dP
represents the slope of phase diagram.
dT
When tan    [Link]
  90º
Correct option is (a)

S P

134.
V T

 V   S 
 T     P  ... (1)
 P  T
Now, according to reciprocal theorem of partial derivatives
 V   S 
 T     T / V 
 P  P
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016 667

 S  1
  
 P T  P / S T
Putting these values in equuation (1), we get
1 1  P   T 
      
 V / T P  P / S T  S T  V  P

 T   P 
Or,  V     S 
 P  T
Correct option is (a)
kTBz kTBz
135. Ealong   E ground 
2 2
 Ealong / kT  Ealong / kT
n e n e
   &   
 N  along q  N  ground q
Rate of probability of finding the proton along end against magnetic field

n
  E / kT E / kT
 N  a log e along e along e  Bz / 2kT
    Bz    Bz /2 kT  e Bz /2kT e  Bz / kT  e Bz / kT
n q e / 2kT e
  Ealong
 N  along e / kT
q
Correct option is (d)

136. Since, zero point energy = 0

1
 q E / kT [Given : E  k BT ]
1 e
1 1 1 1 e
 q
1 e [Link]

 kT / kT
 
1  e 1 1  1 e  1
 q
e 1
e e
Correct option is (c)
137. Rate of production of D
r  k2  AC  ... (1)
SSA on ‘C’,
2
2k1  A B   2k1  C   k2  AC   C   2k1 C   k2  A

2k1  A B 
C   ... (2)
2k 1 C   k 2  A

 k2  A  k1 C 
668 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016

1/2
 k 
  2   C    1   A1/2  B 1/2
 k1 
1/2
 k 
 1  r  k2  1   A3/2  B 1/2 ... (3)
 k1 
Correct option is (d)
#
138.   XYH   Product
X   Y 2  H  
 
k  X   Y 2  H 

k0   #
XYH
 

k  2 2 2 2
log     B I  1   2    1   0  
 k0   

  B I 1  4  1

 6B I ... (1)

k 
log    6 B I1 ... (2)
 k0 1

k 
log    6 B I 2 ... (3)
 k0 2
Here, I1 = 16 and I2 = 4
 k2 
1   2   log    6 B  I 2  I1 
k
 1

k 
 log  4   6 B  4  16   6 B  2  4  12 B
 k16  [Link]
Correct option is (d)
2
139. Pre-exponential factor in collision Theory, A 
µ
2 1/2
A2   2   µ1 
   
A1   1   µ2 
4
A22   2   µ1 
     ... (1)
A12   1   µ2 

Here, 1   2  0.4

A22 µ1
(1)  2  µ ... (2)
A1 2
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016 669

5  20 10  10
µ1   4 and µ2  5
25 20
2
 A2  4
   
 A1  5
Correct option is (a)

140. K salt  K solution  K water  1.5  10 3  1.5 10 5  ohm 1dm 1

K salt  1.5  0.99  10 3
K salt
Solubility(s)  
salt

s
1.5  0.99 10  ohm
3 1
dm 1
 0.485  1 ohm 1dm 2 mol1
1.485 mol mol
s  103  s  1 103
1.485 dm 3 dm 3
s  1 10 3  200 gm/dm 3  s  2  10 1 gm/L  1dm 3
 1L 
Correct option is (c)
2
141. (1) Zn  4NH 3  Zn  NH 3  4  2e  E 0  1.03V
(2) Zn  Zn 2   2e E 0  0.763V
on reversing 2nd reaction and adding it to reaction 1
2
Anode Zn  4NH 3  Zn  NH 3  4  2e 

Cathode Zn 2  2e   Zn
2 2
Zn  4NH 3  Zn  NH3  4
Equilibrium constant of above cell reaction is formation constant
E 0cell  E red
0 cathode
 E 0red anode
[Link]
But values in equation given are of oxidation potential
so E 0red cathode  0.763
E 0red anode  1.03
E 0cell  0.763  1.03
E 0cell  0.267

0 0.0591
Now, E cell  log K eq
n
0.0591 0.267  2
0.267  log K eq   log K eq  9.03  log K eq
2 0.0591
K eq  109.03  K eq  109
Correct option is (c)
670 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016

142. The molar conductance of anionic surfactant of the type Na+R– (sodium dodecylsulfate in water) in
water is plotted against the square root ofthe normality of the solution. The curve obtained, instead
of being the smoothly decreasing curve characteristic of ionic electrolytes of this type, has a shart
break in it, at low concentrations. This sharp break in the curve accompanied by reduction in the
conductance of the solution, indicating a sharp increase in the mass per unit charge of the material in
solution, is interpreted as evidence for the formation of micelles at that point from the unassociated
molecules of surfactant with part of the charge of the micelle neutralized by associated counter ions.
The concentration at which this phenomenon occurs is called the critical micelle concentration (CMC)

y


CMC
 x
The effect of concentration of electrolyte is given by
log CMC  a log ci  b
For homologous ionic surfactant
log CMC  A  BN
Correct answer is (d)

143. sin 2  at 2x, 4x, 6x, 8x

 B.C.C
2 7 1.54
x 2
 a   3.14 Å
4a 2 x 2  0.06
Correct option is (a)

Mn
Mv
Mw
[Link]
144. Weight Mz
fraction

Molecular weight

Correct order is Mn < Mv < Mw < Mz.

Correct option is (b)
1 1
145. T1  V1  T2   V2
2 2
E1  E2
V1 V2
T1  V1  T2  V2    V1  V2 and T1  T2
2 2
Correct option is (c)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2017 671

SOLVED PAPER : CSIR-UGC-NET/JRF June 2017

CHEMICAL SCIENCES BOOKLET-[A]

PART–B
21. 2, 8, 20, 28, 50, 82 and 126 are magic number.
Correct option is (c)
22. Phosphorescence has been observed form a wide variety of compounds and is differentiated from
fluorescence by long lived emission of light after extinction of the excitation source i.e. it done after
fluorescence, if parsists.
Phosphorescence increases when heavy atoms like iodine silver and lead etc. are added.
Phosphorescence increases, when analyte used become immobile.
Hence, both (A) and (B) are correct.
Correct option is (b)

23. A   V  CO 6   5  12  17 e 

 
B   Cu 5  C5 H5  CO    11  5  2  18 e 
 

C   Co  CO 4   9  8  1  18 e 

D   IrCl  CO   PPh 3  2   9  1  2  4  16 e 
Correct option is (b)

24. CH 3  4  3  1  6
 Cr  CO 5   6  10  16
Correct option is (c)

+3 +2 +1 0 –1 –2 –3

25. Eu 3  f 6
[Link]
L = 6–3 = 3 J = |L–S| = 0
S=3

Hence, µ  g J  J  1  0
Correct option is (c)
26.   AsF6    H 2 F
AsF5  2HF 
 
  PF6    H 2 F
PF5  2HF 

  BF4    H 2 F

BF3  2HF 
 
  BrF2    HF2 
BrF3  HF 
BrF3 acts as base as it donate F– in HF. Hence, correct option is (d)
672 SOLVED PAPER : CSIR-UGC-NET/JRF June 2017

F –
••
F F
27. [XeF5]– Xe

F •• F

Shape = Pentagonal planar

F
F F

[BrF5]
F •• F

Shape = square pyramidal

Correct option is (a)

28. K  graphite   graphite K 

H2SO4  graphite   graphite HSO4
Correct option is (d)

29. In oxyhemerythrin  O O  850 cm1

In oxyhemoglobin  O O  1100 cm 1
Correct option is (a)
30. In CdS, HgS and BiI3 colour is due to LMCT Cd2+ and Hg2+ has d10 configuration. Hence, no d-d
transition. Also, no MLCT as ligand is not  -acceptor. Hence, correct option is (a).
31. Change in CFSE on going for Oh to five coordinate intermediate for ions is as follows.

 
V 2 d 3  2.00

Cr  d  [Link]
3 3
2.00

Ni  d   2.00
2 8

Correct option is (a)

32. Correct option is (a)

II II II III III
33. PFe + O2 PFeO2 + PFe PFe — O — Fe — P

II
III III IV
PFe
PFe—O—FeP 2PFe = O
Hematin

Correct option is (a)

 SOLVED PAPER : CSIR-UGC-NET/JRF June 2017 673

34. S
D3C CD3
13
C NMR n = 3; I = 1 (for D)
Multiplicity = 2nI + 1 = 2×3×1 + 1 = 6 + 1 = 7 (septate)

[2, 3] S.T.R.
1 3
2
S S S S
1
35.
I 2
t-BuOK H

Correct option is (b)

H C C
36.
acetyl anion
H3C CH NO2 H3C CH NO2
Base
Nitroethane
H

Hence, nitroethane anion is synthetic equivalent of acetyl anion.

Correct option is (d)

S
S

37.
[8+2]
S
S cyclo-addition
CN
NC CN CN
NC CN
NC [Link]
CN

Correct option is (d)

O OH
HO

H+ Ring
O
38. Contraction

Correct option is (d)

674 SOLVED PAPER : CSIR-UGC-NET/JRF June 2017

H
O
F H
39. Most stable due to intramolecular hydrogen bonding
H H
H
Correct option is (b)

H
9
B
1
7 8
40. 2
9-borabicyclo [3, 3, 1] nonane
6 5 3
4

Correct option is (a)

N
H
41.
N
Anabasine

It is a pyridine and piperidine alkaloid found in the tree tobacco plant. Its principal industrial use is
an insecticide.
Lysine serves as the precursor of piperidine ring of anabasine.

OPP
[Link]

Gernyl pyrophosphate is the biosynthetic precursor of (+)–menthol.

Correct option is (a)
42. Basicity order for their conjugate base is
i
Pr2 NH  PhNH 2  Ph 2 NH
Hence, pKa value for their conjugate acid
i
Pr NH 2  PhNH3  Ph 2 NH 2

pK a
Hence, correct option is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2017 675

OH

OH
O

H
43.
Cortisone
H H

Correct option is (c)

H H

Li, liq. NH3

(Birch reduction)
44.
N N
H
• •
–
e +H+ e–

N N N
H

H+

N N
H
H
Correct option is (b)
[Link] O
O O CO2Et Ph
+ Cl CO2Et
Ph Ph Cl CO2Et
45. Ph
Ph Ph
Darzen's glycidic ester
synthesis
Correct option is (c)
676 SOLVED PAPER : CSIR-UGC-NET/JRF June 2017

hv •
46. NBS + HBr Br2 2Br
(Limited supply)

H Br
•

• Br Br
+ Br
–Br •

Br Below the •
Br Br Br
plane attack •

•
+ Br

Trans-1, 2-dibromoacenaphthene

Correct option is (b)

47. The probability of finding the particle lies between x to x + dx is given by
2
p  x  dx    x   dx
x  4, dx  

2  2  n x  2  n x  
Pr   dx   sin   sin    dx
        

2  n x  2 2  n x  2 2  1   4 
 sin 2    sin    sin  
        8  8 
[Link]
1   
 sin 2     
4 2 4

Correct option is (a)

d ix
48. e  i eix therefore, eigen function
dx
d 2 ix 2 ix
e  i e therefore, eigen function
dx 2
Correct option is (c)
49. In one component system 4 phases carnot simultaneously exist at single point.
Correct option is (d)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2017 677

50. (i) Phase transition cannot be isoentropic

 liquid
solid 
So, entropy is going to change during phase transition
(ii) Phase transition cannot be isochoric as
 gas or
solid   gas
liquid 
Volume is going to change
(iii) Volume is going to change
As phase transition takes place at constant temperature and pressure
Correct option is (d)
51. For any cyclic process cyclic integral of state function is zero.
So,  dU  0 as U is a state function
Correct option is (c)
a 40 1
52. 2 sin   n  2    1 
2 2 2
h k  5 2
  18 nm
Correct option is (b)

 a
53. k  Ae RT at very high temperature T  

 a A
k Ae 
R  k  A e 0  k    k  A
e0
Correct option is (a)
54. As the time increases slope will decreases.
So, correct option is (c)

55. At equilibrium E is zero, because G is zero at equilibrium.

G  nFE
if G  0
So, E=0
Correct option is (d) [Link]
56. 1s2, 2s2, 2p4
6!
Number of microstate for P4 = 4! 6  4  !  15

s = 1×1 = 1  3 p  3  3  9
1

Thus, remaining microstate are 5 which comes from 1D = 1×5 = 5

Correct option is (a)
57. Since, due to vibrational-rotational interaction P and R lines are obtained and molecule behave as a
diatomic vibrating rotor.
2
 1  1
E  BJ  J  1     e     e xe
 2  2
Correct option is (c)
58. Greater the surface tension, the greater the surface concentration.
Correct option is (d)
678 SOLVED PAPER : CSIR-UGC-NET/JRF June 2017

M
59. P.D.I. = M  1 (for monodisperse)
n

 Mw  Mn
Correct option is (b)
60. Intermediate colours been understood and correlated to the formation of intermediate nanostructures
before the formation of the final gold nanoparticles. Specifically, TEM images have shown that after
few seconds of citrate addition, gold nanowires 5 to 8 nm are formed, which are responsible for the
dark purple colour. Beyond a certain threshold, the nanowires disintegrate into nanoparticles, and
the solution turns ruby-blue.
Correct option is (c)

PART–C
61. We have the relation between threshold energy and ‘Q’ of a reaction, as

 M  MA 
KTh  Q  a 
 MA 
Here, Ma = mass of moving projectile or bombarding particle
MA = mass of stationary nucleus
Also, for endoergic reaction, Q > 0
Therefore, magnitude of threshold energy

 M MA    Ma  M A  
KTh  Q  a      1
 MA    MA  

 KTh  Q
Correct option is (a)

62. Correct statement are

• Area of different thermal analysis peak is proportional to amount of sample
[Link]
• In the thermogravimetric analysis area of curve is proportional to mass loss
• In thermogravimetric analysis two metal ion simultaneously determine.
63. In fission of U235 with thermal neutrons
(1) On the average, each fission of a U235 nucleus produces about 2.5 free neutrons
(2) Each fission produce 200 MeV energy
(3) Fission always occure in assymmetric fashion, it means number of nuclei undergoing unsym-
metrical fission is maximum.
Hence, correct statement is (1) and (3)
Correct option is (b)
64. Bi35  5  5  3  22
Hence, (4n + 2), closo
On addition of 2 electron it become (4n + 4), nido
Correct option is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2017 679

65. Na  Mn  CO 5   CH 2  CH  CH 2  Cl 

CO CO
OC CO OC CO
Mn –CO Mn
OC CO + NaCl OC CO
hv

(A) (B)

  
66. µeff = µspin  1  
  

1 1 107
   107 cm  cm 1
 625 625
For Cu2+  Term is 2D, hence,   2 ,   625 cm 1

 2   625 cm 1   2  625  625 

µeff = 1.73 1   625   1.73  1  
 7 1 
 10  cm   107 

 2  625  625 
 1.73 1    1.731  0.078  1.731.078
 107 

µeff  1.864
Correct option is (b)

 
67.   BrF2   SbF6   Lewis base behaviour of BrF3
SbF5  BrF3 

 BrF2 SbF6   Ag  BrF4   Ag SbF6   2BrF3  Neutralization


KF  BrF3  K    BrF4   Lewis acid behaviour of BrF3
 
2BrF3   BrF2    BrF4   self ionization
Correct option is (d) [Link]
68.  Fe 1,10-phenanthroline  2  NCS 2 

HS
300K

186K

77K Low spin

–4 –2 0 2 4

• Since NCS is ambidentate ligand therefore change in co-ordinate mode

• Change in the spin-state of iron at high temperature
Correct option is (a)
680 SOLVED PAPER : CSIR-UGC-NET/JRF June 2017

h
69.  R 3Ge 2   2R 3Ge• in R 3 Ge• radical
9
multiplicity = (2NI + 1) = 2×1× + 1 = 10 lines
2
73  9
Ge  I  
 2
Correct option is (b)
191 193 35 37
70. Ir : Ir  Cl : Cl
37% : 63%  76% : 24%
Natural abundance x y a b

 3.7 x  6.3 y 1  7.6a  2.4b 1

 3.7  7.6 xa  6.3  7.6 ya  3.7  2.4 xb  6.3  2.4 yb
xa ya xb yb
 28.12  47.88  8.88  15.12
M M 2 M 2 M 4
 28.12M  56.76  M  2   15.12  M  4 

 28.12 1.76 M  56.76  1.76  M  2  15.12  1.76  M  4 

 49.49 M  100  M  2   26.6  M  4 

 49.5M  100  M  2   26.6  M  4 

M :M  2:M 4
49.5 : 100 : 26.6
Correct option is (a)

Me2N (a) Cl
P
NMe2
N
Cl (b)
N
[Link]
P
Cl
P
71. N
Me2N N
P (b)
NMe2
Cl

 1 
31
Pa 1 H   2NI  1   2  2   1  3  triplet 
 2 

 1 
Pb 1 H   2NI  1   2  2   1  3  triplet 
31

 2 
Correct option is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2017 681

72.  B6 H 6 2 has 6 + 1 = 7 binding molecular orbital

 B6 H 6 2 B  H  2  6  12 e 
for 2 negative charge, hence 12 e   2 e  14 e 
Correct option is (a)
73. N2F2 has two isomers,
F

N N N N

F F F
1C2 + 2v 1C2 + 1h

Correct option is (c)

74. Metallothioneins are cystein rich, low molecular weight protein. Due to soft sulfur centre they prefer
to bind.
Correct option is (b)
75. Both deoxyhemerythrin and deoxy hemocyanin are O2 transport protein in biological system. Both
contain two metal ion at active site and they bind only O2 per active site.
Correct option is (a)
76. As the strength of ligand increases energy for d-d transition increases.
Strength of ligand order is F   OX 2  en .
All complex have same number of unpaired electron. Hence, all have same spin only magnetic
moment.
3 3
76.  Cr  ox 3  and  Cr  en 3  will show optical isomer. As t2g level is electronically non-degener--
   
ate. Hence, there will be no Jahn-Teller distortion.
Correct option is (a)

+ [Link]
H 
77.  5 5 
  
Fe   C5 H5   C6 H 7 
H
NaBH4
Fe Fe


 
 Fe 5  C6 H 6 5  C5H 5 
  
Correct option is (d)
682 SOLVED PAPER : CSIR-UGC-NET/JRF June 2017

78. In  Fe  S2 CNEt 2 3  oxidation state of Fe = +3

Fe3+ (low spin)

2
T2g

Fe3+ (high spin)

6
A1g

Correct option is (a)

  A   Ni H2O    NO3   B  Ni NH3   NO3   C  Ni en    NO3 
6 2  6 2  3 2
79. 
 increases

0
Thus, order for energy absorition is 675 (A) < 615 (B) < 565 (C)
Complementary colour of blue  Orange, green  Red, Violet  Yellow
Energy order for absorbed light is, yellow > orange > red
Thus, A absorbs red hence it is green
B absorbs orange hence it is blue
C absorbs yellow hence it is violet
Thus, correct option is (a)
CH3
Ph3P CO Ph3P CO
CH3I (polar)
Ir Ir
80. Cl SN2 Cl
PPh3 PPh3
anti addition I
Correct option is (a)

CHO
[Link]
Ph3P, CBr4, Zn
H
Br n–Bu–Li
+
81. Ph Corey-Fuchs reaction Ph Ph
Br Br

Ph (ii) CO2 Ph (i) n–Bu–Li+

COOH (iii) H3O+ Li

Correct option is (a)

 SOLVED PAPER : CSIR-UGC-NET/JRF June 2017 683

HS N O

82. DCC, DMAP

COOH + C
C6H6, reflux O

H H •
Bu3Sn
S

Bu3SnD, AlBN
D

Correct option is (d)

CH2N2
HO2C N
83. O O + N methylation
O H O
H
AlCl3
MeO2C ene reaction
EtO2C N
O
O
N

Correct option is (d)

O O O O
O O
84. t- BuO t- BuO t-BuO
Na+H– CO2Me
[Link]
Br CO2Me
H
O
O
O O
H O H O O O
H H+
HO t-Bu O
OH2
CO2Me H CO2M
HO O CO2Me O e
O CO2Me
O O

Correct option is (a)

684 SOLVED PAPER : CSIR-UGC-NET/JRF June 2017

SMe
S C S
C
H H S O H
OH O
NaH Me–I H Pyrolytic
85. syn-elimination
H H H H
H CH3
H

H
H

Correct option is (c)

OH
CHO CHO

Ph3P, DEAD, PhCO2H LiAlH4

86.

OH O C Ph OH
O

Correct option is (c)

Ph HO
Ph Ph
(4+2) O3/NaBH4
87. + Cycloaddition
EtO2C CO2Et HO CO2Et
[Link]
H
OH

HO Ph
H3O+
H H
H H

O O
O O

Correct option is (a)

OH
(i) I2, PhCO2Ag, H2O (woodward reagent) KMnO4/OH–
88. (ii) Aq. NaOH OH
OH
OH
Correct option is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2017 685

O
89. O L–(+)–DET O
OH OH
epoxidation
below the plane Product (A)
OH
OH t-Bu-S
O t-Bu-SH , NaOH O
S-tBu
O
Product (B) OH

Correct option is (c)

OMe

O OH OAc
DDQ
90. 1 equiv. + Ph I
Deprotection of OAc
–OH group OAc

I
O O OAc

OMe
MeOH

Correct option is (b)

91.  D for S–(+)–2-butanol = 10º mL/g dm
 obs for mixture of R and S 2-butanol = – 0.45º
If l = 0.6 dm; C = 0.15 g/mL

 T 

 [Link]
0.45
  C 0.6  0.15
 –5º

 mixt 5º
ee    100  50% excess of R
 pure 10º

50
R  50   75%
2
S  25%
Correct option is (d)
686 SOLVED PAPER : CSIR-UGC-NET/JRF June 2017

(i) Mg (ii) CO2 (COCl)2

92.
+
(iii) H3O
Br MgBr C O C O
H
OH Cl

(2+2) Et3N
addition

C
O C
O

Correct option is (d)

OH 3 2
N [3,3] S.T.R. N
Aza-cope reagent O H
1
93. N O
1
C N 3 N
H 2 OH
O
(Mannich reaction)

Correct option is (b)

94. Pd  OAc  2  PPh 3 
[Link]
 Pd  PPh 3 4

Active form is Pd  PPh 3 2

This reaction is an example of intramolecule Heck reaction
(1) Oxidative Addition :
I
Ln
I Pd
4 Pd(PPh3)2

3 1

2
(2) Olefin insertion (Syn addition):
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2017 687

OAc PdL2
H
Pd H 4 H
4
Olefinic insertion H  elimination
3 1 SYN addition 3 SYN
2 1
2 H

Correct option is (a)

1
O O O OBBu2 O O OH
1
2 PhCHO
N N N Ph
95. Bu2BOTf 2
Me
Et3N

z-enolatesyn
O OH LiOH, H2O2
H2 O2
HO Ph (Hydrolysis)

Me

Correct option is (b)

O
CO2Me
CO2Me
175ºC
96. N [Link]
N

Ph
Ph N CO2Me

Ph
(1, 3-Dipole)
O
OTBDMS
1, 3-Dipolar
Me
Cyclo-addition

CO2Me
N

Ph

Correct option is (c)

688 SOLVED PAPER : CSIR-UGC-NET/JRF June 2017

Hydrogen bonding

H H
O O
OH

97. OH
Highly unstable due to 1, 3- Twist boat
diaxial interaction, steric
hinderance and Gauche
interaction

Correct option is (c)

O
98.
Br O Me
 3.59  s, 3H  suggest option (c) and (d)
 3.32, t , 2 H 
 only possible in option (c)
2.25, t , 2 H 
Correct option is (c)
99. Anomeric effect present in compound (B)
OH n
••
HO
O 
interaction
HO
OH
OMe
Correct option is (c)
100. In case of RNA-uracil is present. Inspite of thymine-DNA
Correct option is (b) [Link]
 1 0.1 1
101. k     0.0044
1   P 1  0.1 25
Correct option is (b)

Zm
102. 
a3
1/3 1/3
 Zm  1 2.7 1022 g 
a   3   3 103 cm  3 Å
    10 gcm 
a
And r  1.5 Å
2
Correct option is (c)
 SOLVED PAPER : CSIR-UGC-NET/JRF June 2017 689


103. k  G
A
0.176 176
0.176  G  0.255  0.255  G  255  G

0.6901  1  G
Correct option is (b)

104. Rate of removal of HI = k1  H  HI   I 0 ... (1)

•
SSA on H •  I a  k1  H   HI 

Therefore, (1)  r  I a
Correct option is (c)

105.  max  k2  E 0  3.42 10 4  1 10 2  3.42  10 2 mol dm 3 sec 1

And T.O.N. = k2  3.42 104 s 1

Correct option is (a)
k1
106.  e  E1 / RT ... (1)
A1
k2
 e E2 / RT ... (2)
A2

 2  k2 A1
  e 1 2 
E  E / RT

1 A2 k1

k2 A1 A k
1  1  1
k1 A2 A2 k2
Correct option is (a)
107. [Link]
Fugacity of gas is less than P when attractive forces are deminant. It happens at low P and when T <
Tb.
Correct option is (b)

108.  H 2  g   1 O2  g 
H 2O  g  
2
P '
P ' 1    P '
2
1/2
 
P '   P '  1/2
 2   
kP    P '1/2
P ' 1    1     2 
P
PT  P 1     P 
2
690 SOLVED PAPER : CSIR-UGC-NET/JRF June 2017

P P   PT
PT  P  P   PT  P   PT  P  1    P 
2 2  2  
1  
 2
 3/2 PT1/2
kP 
2 1      1/2  
1    1 so 1    1 and 1   1
  2
 2
 3/2 PT1/2
kP  so k P   3/2 PT
2
Correct option is (b)
109. The given engine is working as refrigerator as it is transfering heat from sink (lower temperature) to
source (higher temperature). So, efficiency of refrigerator/coefficient of performance
T1 100 100 1 output q 1 5
'     '  ' c      10 J
T2  T1 300  100 200 2 input  2 
Correct option is (b)
110. S63  C63   3  C '2  a  S 2
Correct option is (d)
10  20000  15  10000
111. Mn   14, 000
10  15
Correct option is (b)

112.   no. of arrangements Cclassical   no. of arrangements  Afermions   no. of arrangements bosons
B

 SC  S A  S B
Correct option is (d)
113. Character table of C3V points group and complete table is
E 2C3 3 v
A1 1
A2 1
1
1
1
1
[Link]
E 2 1 0
Correct option is (c)
114. The given vibrational is not symmetric w.r.t.  h
Correct option is (d)

115. N2 g 2 e   E2 g 2 e    E2  E1   N 2 g 2 N g 2 e  E2 
     N 2  NP2  
N g1 e   E1  g 2 e  E2 g1  g 2 e    E2  E1  N1 g1 gi e   E2 
400

2e 420 1 1
 400
 400

 1  2e
42 e 420 2 e 420

Correct option is (d)

 SOLVED PAPER : CSIR-UGC-NET/JRF June 2017 691

u u

116. H2 H 2+
1s 1s 1s 1s
a b a b
g g

2 He  1s
2
; He  1s1

H 2 : r    1s a  r   1s b  r 

He  : r  0  1s He  r 

Correct option is (d)

vp g  p 700 MHz 5.6 700 MHz  0.4

117.     vN   50 MHz
vN g N  vN 0.4 5.6
Correct option is (d)

118. The first electronic absorption band maximum of a polar and relatively rigid aromatic molecule
appears at 310 nm but its fluorescence maximum in acetonitrile solution appears with a large stokes
shift at 450 nm. The reason for stokes shift increasing dipole moment of the molecule in the excited
state.
Correct option (b)
r

119. From radial part 6r  r  2
 exp 3

Minimum power of r1  1
So,   1
Corresponding   1 possible angular part of eigen state is cos 
For cos  ,   1
Correct option is (c) [Link]
H11  ES11 H12  ES12
120. 0
H 21  ES21 H 22  ES22

0E 2.5
0
2.5 12  E

 E 12  E   6.25  0

12 E  E 2  6.25  0
E 2  12 E  6.25  0
The root of this equation is E  0.50
 E  0.50
Correct option is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017 21

SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017

CHEMICAL SCIENCES BOOKLET-[A]

PART–B
21. The cross-section    can be interpreted as the effective ‘target area’ that a nucleus interacts with an
incident neutron. Larger the effective area, greater the probability for reaction
In reaction, 92 U 235  10 n 
 36 Kr 94  56 Ba140  2 10 n , one neutron react with 92 U 235 to give two neu-
tron, which have more tendency to react with other radioactive nuclei. Thus, increases effective area
for reaction.
Correct option is (d)
22. (a) Oxalic acid versus potassium permanganate:
 pink-purple  max  525 nm 
End-point is colorless 
(b) Iron (II) versus 1, 10-phenanthroline:
 Reddish-orange  max  512 nm 
End-point is colorless 
(d) Nickel (II) versus Dimethylglyoxime :

End-point is colorless  Red  max  445 nm 


(c) Cobalt (II) versus Eriochrome Black-T:

End-point is Blue-green  Blue


 pH  8  max  660 nm   max  600 nm 
Free EBT 
 Co  II  +EBT complex

Since, color change at end-point is not significant for option(c) which is requirement of the spectro-
photometric titration. Therefore, color monitoring method is not suitable in this case.
Correct option is (c)
23. [Link]
• Generally, ionisation energy increases on moving from left to right in a period in periodic table.
• Ionisation energy decreases as we move down in given group
• Ionisation energy will be more for full filled and half filled orbital.
Correct option is (b)

7  6  3  1 26
24. ClO3    3  1  4  sp3 Tetrahedral
8 8

••

Cl = Pyramidal shape
O O
O
8  6  3 26
XeO3    3  1  4  sp3  Tetrahedral 
8 8
22 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017

••

Xe = Pyramidal shape
O O
O
6  6  3 24
SO3    3  sp 2  Trigonal planar 
8 8
O

S
O O
Correct option is (a)

25. n + BF3 n BF3

H2O + BF3 H+ + HOBF3

cation formation  carbocation
Correct option is (b)

3 eg
26. (A)  TiF6 
Ti  3d 2 4s 2 d1
Ti3  3d1 4s0 t2g
1 unpaired electron eg

(B) CrF63 d3
Cr  3d 5 4s1 t2g
3 3 0
Cr  3d 4s 3 unpaired electron

[Link]
eg
3
(C)  MnF6  d4
Mn  3d 5 4s2 t2g
3 4
Mn  3d 4 unpaired electron

eg
(D) CoF63 d6
Co  3d 7 4s2
t2g
Co3  3d 6 4s0
4 unpaired electron
Hence, A < B < C = D
Correct option is (d)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017 23

27. Cytochrome-C shows redox reaction and it is an essential component of electron transport chain,
whereas it is carriers of one electron and does not bind oxygen
Correct option is (c)
6  5  7  3 32
28. SNF3    4  sp3  Td
8 8
8  6  2  7  2 34
XeO 2 F2    4  1  5  sp3d  TBP
8 8
N F
O
S
••

Xe
F F O
F F
Tetrahedral Trigonal bipyramidal
Correct option is (d)

1  Co  H µCo  D 1934 1934

29. v     2   Co  D   1367.7  1396
µ  Co  D µCo H  Co D 2
Correct option is (b)
30. In trigonal prismatic ligand field, energy of ‘d’ orbital is
d yz  d xz  d 2  d 2 2  d xy
z x y

Hence, the most stablized ‘d’ orbital is d xy

Correct option is (b)
31. According to electroneutrality principle, each atom in any stable substance has a charge close to
zero. This means if central atom has more positive charge then it would be stabilized by ligand
having high negative charge density i.e. more electronegative donor atom.
3
In case of  Al  NH3 6  , nitrogen is sp3 hybridized hence it is least electronegative hence
least stable complex.
Correct option is (b)

Electronic absorption band of I2 vapours appears at 520 nm i.e.  max of I2  gas   520 nm
32.
[Link]
If solution is prepared with a solvent that able to form a charge transfer complex (CTC) like aromatic
solvents, ethers, alcohols etc. This absorption band shifted towards UV range i.e. blue shift. More
the donation of electrons from solvent to the * (LUMO) of I2 more will be the blue shift.
Here, option(d) methanol has highest electron donating capacity (i.e. most basic)

 max I2  Hexane   523nm Red shift

 max I2  Benzene   502nm Blue shift

 max I2  Methanol   440 nm Blue shift

 max I2  Water   460 nm Blue shift

Note: Methanol has low ionization potential (10.85 eV) than water (12.59 eV), therefore methanol
is better electron donar than water.
Correct option is (d)
24 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017

33. Spin-orbit coupling is larger for the heavier atoms (Inner transition) and very small for lighter atoms.
Correct option is (c)
H
H H
•O •O •O
 M.C.
 +
34. 

m/z = 72
Correct option is (a)
(4) COOH (1)
H
(R) Configuration
35.
HOOC (3) H (2)

Correct option is (b)

HO
36. OH

OH

HO
Enterodiol is a lignan, formed by the action of intestinal bacteria on lignan precursors found in
plants.
Correct option is (c)

Pyrrole Pyrazole Imidazole

37.
N

N
N N N
[Link]
Weak
Base
H H H

H+ H+ H+ H
H
N N

Stronger NH
conjugate N N N N
acid
H H H H
H

pKa = –4.5 pKa = 2.5 pKa = 7.1

pK a  basicity
Lesser is the availability of lone pair for donation, lesser is the basic behaviour.
Correct option is (c)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017 25

O O O O
H2O O O
S
S S
38. OH OH2
HO HO O
H
O O
S SO3H
H HO3S H
O
OH O H OH

Correct option is (d)

39. Hydrogen bonding and no 1, 3-diaxial interaction

H
O

O
Me O

Correct option is (a)

40. HOMO of hexatriene in hv condition is  4 . In  4 molecular orbital has three nodes.
No. of nodes
5. 6

4. 5
LUMO

LUMO
4
3.
[Link]
HOMO

2. 3 HOMO

1. 2

0 1 hv

Correct option is (d)
26 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017

a a

c b c
b
e
d d
e
41.
c b c

a a

13
C NMR 
 Total 5-signal
Correct option is (a)

MeO MeO +
MeO

Carbocation stabilized Carbocation stabilized

through (8 hydrogen) through (6 hydrogen) Carbocation stabilized
42. hyperconjugation hyperconjugation and allylic through (6 hydrogen)
double bond hyperconjugation and
np-vacant orbital
resonance stabilization

Order of stability of carbocation C > B > A

Correct option is (d)
T
   of sample 32
43. Optical purity  T
 100   100  80%
   of pure enantiomer 40

Correct option is (d)

O
[Link]
O O O
KOH, MeOH
44.
Intramolecular
H H
Aldol reaction
OH H

OH OH

E1cB

O H O
O OH

Correct option is (c)

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017 27

O O
O O O
45. (I) (II) O (III)
Cyclic Ketone Cyclic Ester Anhydride
IR = 1745 cm–1 IR = 1770 cm–1 IR = 1865 cm–1
(C) (B) (A)
Correct option is (c)
Br
Br a a
H H  = 7.38 (d)
Plane of symmetry
46. b b
H H  = 7.25 (d)
H H
C C singlet 1.29 ppm
c H H
H C H
H Hc
H
c
Correct option is (a)

Cl
Once C2 passing through ‘B’ and ‘Cl’ atoms, two hydrogen interchange their position but
47. B remain same molecule.
H H

Correct option is (a)

48. H2 a homo diatomic molecule will have not change in dipole moment. Thus, it will be IR inactive but
since H2 having polarisability in a Raman spectra. Thus, it will be Raman active.
Correct option is (a)
Cl
[Link]
sp2 [hybridisation]
B
49. Cl Cl
2
(3 + 3×7)/8 = 3 sp
Correct option is (b)
50. Orbital degeneracy = n2 = 62 = 36
Correct option is (d)
ˆ ˆ ˆ ˆ ˆ ˆ ˆ ˆ ˆ
 A, ˆ B
  A, ˆ C
ˆ   0 &  A, ˆ   0
51.  BC    A, B C  B  A, C   0      
Correct option is (b)
 ikx
52. e.g. Let Aˆ  pˆ x which is a Hermitian operator and   e be operand
2
 
Aˆ  Aˆ e ikx    k  ; Aˆ 2   2 2 e ikx    2 k 2 e ikx
x
Therefore, eigen value is positive.
Correct option is (b)
28 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017

3 3
4 r 4  3 3  a 3
53. Packing fraction = Z      2  3.14      r  
3 a 3  4  8  4 
Correct option is (d)
 3.2  5.2  7.2 
54. x   ppb  5.2 ppb
 3 
2 2 2
 xL  x   3.2  5.2    5.2  5.2    7.2  5.2 
s  N 1

3 1
ppb

22  0  22 8
 ppb  ppb  2 ppb
2 2
Correct option is (a)
55. The stability of lyophobic colloids is a consequence of electrical double layer at the surface of the
particles
Correct option is (a)
56. For strong electrolyte,  0 can be obtained from the plot of  vs c
Correct option is (b)
Mw
57. P.D.I.= =1 for Monodisperse sample
Mn
 Mw  Mn
Correct option is (d)
58. Rate of formation of I = Rate of deformation of I
k
 k1  A  k2  I    I   1  A
k2
Correct option is (d)
59. G  ui ni
G  H  TS
H  G  TS
H  ui ni  TS
Correct option is (b)
[Link]
O

NH

N O
O
60. HO

OH OH
Uridine is glycosylated pyrimidine-analog containing uracil attached to ribose ring (ribofuranose)
via a ,  N1  glycosidic bond
Correct option is (b)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017 29

PART–B
61. The peak area of differential thermal analysis is propportional to
(i) mass of the sample
(ii) heat of decompositional phase change
Correct option is (d)
62. Electron diffraction is used to get the bond parameters of gaseous samples.
Correct option is (b)
63. (a) Lu(III) = [Xe] 4f145d06s0, hence diamagnetic
(b) EuI2 has metallic lustre
(c) Ce(IV) used as oxidising agent
(d) Tb(III)-f8 has pink colour
Correct option is (a)
64. Number of valence electron in CH2 = 6
Hence, fragment having 16 electron will be isolobal to this fragment.

A  CpCr  CO  2  5  6  4  15

B  CpCu  5  11  16

C  Ni  CO  2  10  4  14

D  Cr  CO  4  6  8  14 ; E  Fe  CO  4  8  8  16
Correct option is (c)

65.  PMo12O40 3 is less basic. It is slightly less basic than ClO 4

Correct option is (c)

66. (A) Due to more expansion of 5f orbital actinoids has more tendency to release electron hence have
more tendency to show oxidation state greater than +3 compared to Lanthanoids
(B) Actinoids (III) show either f-d or f-f transition, but no d-d transition
(C) UO 22 and PuO 22 are stable
[Link]
(D) All the actinoids have radioactive isotopes
Correct option is (a)
67. According to Bent’s Rule, ‘more electro negative element occupy axial position in trigonal bipyramidal
geometry.
Correct option is (a)
68. According to Allred-Rochow, electronegativity can be given as
0.3590 Zeff
 AR   0.744 where, r = covalent radius.
r2
Correct option is (b)
69. In I3 , there is intraction between * of I2 and non-bonding electron of I–. In case propanone and Br2,
there in interaction between * of Br2 and non-bonding electron of propanone.
Thus, both I2 and Br2 behave as acid.
Correct option is (b)
30 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017

70. According to reductive elimination reaction mechanism cis-complex can give the product but
trans-complex is not suitable for reaction and does not give reductive elimination product. Since,
ligand given in option (d) forms a trans-complex with Pd(II) due to the presence of flexible
methylene (–CH2–) groups. Therefore, reductive elimination not occured.

Me

P Pd P P P
Ph Ph Ph Ph
Pd
Ph Ph Ph Ph Ph
Me Ph
(trans)
(cis)
Actually formed but does not give reaction This can give the reaction but not formed

Correct option is (d)

71. As the chelate ring size increases (in case of (d)), the energy of LUMO of complex cation
CpRu(P–P)+ (which formed after H– transfer) decreases and makes the complex cation better H–
acceptor and therefore decreasing the rate of H– transfer from CpRu(P–P)H.
+

Ph Ph CH3CN Ph Ph
P P P P + H–
Ph Ru Ph No reaction Ph Ru Ph
Cp H Cp NCCH3
(d) Low energy LUMO
High steric crowding due to so, better H– acceptor
large chelating ring
Correct option is (d)
72. [Link]
For d 6  high spin  there is one spin allowed transition from 5 T2g  5E g
In case of d6 low spin commonly two spin allowed transitions are observed.
1
 1T1g
A1g 
1
 1T2g
A1g 
there are additional spin allowed transitions at higher energy but they are marked by allowed transi-
tions. Hence, are not observed
Correct option is (b)
73.  HOCl  H3O   Cl
A  Cl2  2H 2O 
B  Cl 2  2NH 3   NH 2 Cl  NH 4  Cl
Above both reactions are example of solvolysis as well as disproportionation
Correct option is (d)
74. Sn 94  9  4  4  40 , thus it follow 4n + 4. Hence, it has nido structure
Correct option is (b)*
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017 31

75. H 3 P  11BCl3
31  1 
P NMR   2 NI H  1 for 3H   2  3   1  4  quartet   1: 3 : 3 :1
 2 
31  3 
P NMR   2 NI B  1 for B   2   1  1  4  quartet   [Link]
 2 
3H

1 3 3 1
B B B B

1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

Intensity ratio : 1 : 1 : 1 : 1 : 3 : 3 : 3 : 3 : 3 : 3 : 3 : 3 : 1 : 1 : 1 : 1
Correct option is (c)
3
76. K 3CuF6  3k   CuF6  , oxidation state of Cu3+ = 3d8

Thus, Cu3+ d8  Oh 

KCuL2  oxidation state of Cu = 1 + x–4 = 0  x  3

 
Cu 3 d8
Hence, square planar low spin
O H H O –
C N N C

K+ HN [Link]
Cu NH

C N N C

O H H O
Correct option is (a)
77. In oxyhemerythrin, both the Fe are present as Fe(III) and there is presence of hydrogen bonding and
dioxygen bind to only one Fe.
Correct option is (c)
78. Mechanism of base hydrolysis can be given as
2 
 Co  Cl   NH 3    Co  Cl   NH3   NH 2  
 OH  
 5  4 

slow 2
 Co  Cl   NH 3 4  NH 2   
RDS
  Co  NH3 4  NH 2   Cl
intermediate  C.N.5 
2
fast 2
 Co  NH3   NH 2    H 2O  Co  NH 3   OH  
 4   5 
Correct option is (a)
32 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017

79. Cubane like ferredoxin is Fe4S4

It has four inorganic sulfide which can be removed by treatment with acid.
8H 
Fe 4S4   Fe84  4H 2S
Correct option is (d)

Ph Ph
Ph Ph Ph Ph
P 76º P P 85º P P 89º P
Ph Ph Pd Ph Ph Ph
Ph Pd Pd
80.
NCS SCN NCS SCN
SCN NCS
Small P–Pd–P angle, less Increase in P–Pd–P angle,increase in steric hindrance. No P–Pd–P bond angle, further increase
steric hindrance effective effective  bonding from the P atom, the S atom of SCN– with increase in size of chelate ring and
 Pd–SCN– bonding ligand can form  bond but due to steric hindrance SCN– hence steric hindrance increases. No effective
binds through N atom.  bonding from P, the S atom of SCN– can
form the  bond but steric hindrance favours
the Pd-N bonding
Correct option is (a)

O Li O OTBDMS

O N O O
H
H Li TBDMS Cl MeO2C heat
81. LDA (4+2)
+ cycloaddition

OTBDMS

2
O1
CO2Me CO2Me 3
H2O O 1
CO2Me
2
HOOC [3,3]
TBDMSO sigmatropic
3

[Link]
Correct option is (c)

82.
H2N OH Ac–Cl
NH OH

O OH N OH

CN CN Backmann
fragmentation

N OAc
H
Correct option is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017 33

Base H N Ts Ts N
O OH N N

AcOH TsNHNH2
83. O O O
O

O H2, Pd/CaCO3 O
Pd(OAc)2
(Lindlar catalyst)
Product (B) Product (A)
Correct option is (c)

H
H Cl
(Carbene)
C
••

C
Li+Me– H Cl
Cl
H Cl
C C
••

H
84. Cl
Carbene insertion –LiCl
N Me–Li+ N N N
H Li Li (Product)

Correct option is (c)

O O
OH
C I2 I
NaHCO3
I
85. O H O
O

[Link]
I I H DBU

DBU
O O O
Base
O O O
H H
*DBU = [1, 8-Diazabicycle [5.4.0] undec-7-ene]
Product (B) Product (A)

Correct option is (b)

CN 2–
O Cu S OH
86. BnO NH4Cl/H2O
BnO

Correct option is (d)

34 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017

Cl
O
S
87. N Cl Cl
OH O
OH HN C HN C
H2N C
O O Cl
Cl

N N

N N
H
N
H Cl
N N C
H

HN N C N O
H
O

Correct option is (c)

O O
Rh2(OAc)4(cat.)
+ N2
••
88. N2
••
O O
••

O O
[2, 3 STR]
2
O1 O

1 3
2

Correct option is (b)

O O
S Ph [Link]
S Ph
O
SOPh
H
89. KOH Michael
H addition H
O O
O OH O
PhOS Intramolecular SOPh SOPh
Aldol
Reaction KOH
KOH
O O O
O O
OH H
Ph O
S H
H
syn elimination keto enol
Tautomerism
O O OH
OH

Correct option is (a)

 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017 35

O O O O
•• NEt2
NEt2 NEt2 NEt2
C
90. OH2

Product (A) H+ –NEt2

O O O
O
O H3O+ O
OH2

OH OH
Product (B)

Correct option is (a)

NO2 NO2
H NO2

H2O2/AcOH O N O
HNO3/H2SO4
91. N N N N N

O : PCl3
O O

Correct option is (b)

92. The number of optically active stereoisomer are two

CH3 CH3

H OH HO H

H OH HO H

HO H H OH

CH3
[Link]
CH 3

Optically active
Correct option is (a)
36 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017

O
H
H
93. (I) H (II) (III)

O
Br
 = 6.72 ppm
4n = 12 e– 4n+2 = 14 e–
in delocalization vinylic proton with EWG in delocalization
Therefore,anti-aromatic inner proton will Therefore, aromatic inner proton will be
be highly deshielded i.e. paratropic highly shielded i.e. diatropic anisotropy
anisotropy  = 16.4 ppm  = – 0.61

Correct option is (b)

O O OH2 O
OH MeOH O OMe
HO + HO MeOH/H+ HO
H HO
94.
HO HO HO
HO

O O OMe
O OMe TBDMS-Cl
OH TBDMSO TBDMSO
HO (1eq.) Et3N
PDC
AcOH/H2O HO
O
O
Correct option is (b)
H O

Peptide N CO2Me
SPh HS
NH2
95.
[Link]
H O H O
H2N CO2Me
SH
Peptide N N
NH Peptide
S

CO2Me
Correct option is (d)

SiMe3 SiMe3
H2SO4 TBAF
OTBDMS OTBDMS OH
96. Deprotection
OH OH2 of (–OH)
Anti-elimination
Ti(Pro)4, (+)–DET
t-BuOOH, CH2Cl2, –20ºC
OH
O
Correct option is (a)
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017 37

OMe OMe OMe

Br
LDA CO2Me
97.
1 equivalent
CO2Me CO2Me
H
(A)
CO2Me

O O OMe
OMe OMe

C H3O+ C O
OMe OMe
workup C
CO2Me CO2Me OMe
(B) C
O OMe

Correct option is (a)

O
O O O
NaNO 2 NGP HBr
OH
OH OH
98. O
NH2 N2 Br
Br Br
Correct option is (c)

H
H H
OH
heat cat. OsO4
99. 6 e– NMO
OH
H H
H
[Link] (cis-hydroxylation from
less hindered face)

Correct option is (b)

O Br
B H
O (Ph3)2PdCl2, KOH
100. n Bu n-Bu n-Bu
then H2O
B(OH)2

Correct option is (b)

101. Eigen functions are even for even values of vibrational quantum number (n) and odd for odd values
of n.
Correct option is (d)
38 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017

 h2   h2 
102. In 1-D box, E  5  2  and in 2-D box
E  3  2 
 8m   8m 

 h2 
And in 3-D box, E  3  2 
 8m 
Correct option is (c)

103. For odd power of perturbed potential, E 1 is always ‘0’

Correct option is (c)
104. Only Raman active, (symmetric vibration, change in dipole moment is zero during vibration)
Correct option is (b)

105. Spherical top molecule  CH 4  Perfect geometry

I a  I b  Ic
Symmetrical top molecule  CH 3Cl  Ia  0, I b  Ic
Correct option is (c)
106. According to GOT theorem, any two IR must be orthogonal to each other.
Correct option is (a)
3 =  – 2 
2 = 
107.
1 =  + 2 
E1 3  2 E1 2  2  4.8  9.6 eV
Correct option is (c)
108. E  g  B0  h  g  B0
  g
 H gH 600 MHz 5.6 600
    C   150 MHz
 C gC C
Correct option is (c)
[Link]
1.4 4

3
109. P2
Degeneracy = (2×2+1) = 5
S  k B nqe
For electron ground state, qe  ge
S  k B ng e  k B n5
Correct option is (c)
110. dG  VdP  SdT  fdL ... (1)
Differentiating equation w.r.t. T at constant P, L
 G 
 T    S
  P, L
Similarly differentiating equation (1), w.r.t. L at constant P and T
 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017 39

 G 
    F
 T , P
Since, G is a stable function,
   G      G  
        
 L  T  P , L  T , P  T  L T , P  P , L
 S   F 
Or,     
 L T , P  T  P , L
Correct option is (a)
111. For distinguishable particles,
n
g1ni g 0 0 g1n1 23 31 8
W  N i W  4    4    4   3  24  4  96
ni ; n0 n1 3 1 3 2
Correct option is (c)

B C
V2

112.
Volume

V1
A D

T1 T2

wtotal  wAB  wBC  wCD  wDA

Process AB is isothermal,
V 
 wAB   nRT1n  2 
[Link]
 V1 
Process BC is isochoric,
 wBC  0
Process CD is isothermal,
V  V 
 wCD   nRT2n  1   nRT2n  2 
 V2   V1 
Process DA is isochoric

V  V 
 wDA  0  wtotal   nRT1n  2   nRT2n  2 
 V1   V1 
V 
 nR T2  T1  n  2 
 V1 
Correct option is (d)
40 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017

 A 0.2
113. R  G k ; G   0.8  1
A  0.25
Correct option is (c)
0.0591  0.01 
114.
0

Ecell  Eright 0
 Eleft   2
log  
 0.01 
Ecell  0.403  0.447 ; Ecell  0.044V
Correct option is (b)
N1M1  N 2 M 2 50  500  75  6000
115. Mn    5600
N1  N 2 50  75
Correct option is (b)

d123 3.12 d 3.12

116. d 246    1.56 nm ; d 369  123   1.04 nm
2 2 3 3
Correct option is (a)
km
117. slope   300 ... (1)
rmax
1
Intercept   2  105 ...(2)
rmax

1  k  1.5 103

m
 2
Correct option is (d)

118. For a bubble, surface tension counteracts internal pressure

2
 Pint  Pout 
r
2
[Link]
 Pint  Pout 
r
Correct option is (b)
119. From entry (1) and (2), order [Link], B = 1
And from entry (3) and (4), order [Link]. A = 2
Correct option is (c)

120. A2  B   product

Slope = 2 AZ A Z B  2 A  2  1  4 A   ve  salt effect 
Thus, plot having negative slope
Correct option is (d)