CSIR Chemical Sciences Previous Year

PAPER : CSIR-UGC-NET/JRF Dec.
2016 1
PAPER : CSIR-UGC-NET/JRF Dec. 2016

CHEMICAL SCIENCES BOOKLET-[A]
PART-B
21. The HOMO (highest occupied molecular orbital) to LUMO (lowest unoccupied molecular orbital)
electronic transition responsible for the observed colours of halogen molecules (gas) is
(a) *  * (b) *  * (c)   * (d)   *

22. In the hydrolysis of trans-  Co  en  2 Cl  A   , if the leaving group is chloride, the formation of cis
product is the least, when A is
(a) NO 2 (b) NCS (c) Cl (d) OH 

23. The expected number of 19F NMR spectral lines, including satellites, for  XeF5  is [Abun-
dance of 129Xe (I = ½) = 26%]
(a) two (b) twenty one (c) three (d) one
24. The expected H–H–H bond angle in [H3]+ is
(a) 180º (b) 120º (c) 60º (d) 90º
25. The number of bridging ligand(s) and metal-metal bond(s) present in t he complex
 Ru 2  5  Cp   CO   Ph 2PCH 2 PPh 2   (obeys 18-electron rule), respectively, are
 2 2 
(a) 0 and 1 (b) 2 and 1 (c) 3 and 1 (d) 1 and 2
26. The oxidation state of gold in the following complex is
Me Me
Cl Au Au Cl
www.careerendeavour.com
P
Me Me
(a) 0 (b) 1 (c) 2 (d) 3
2
27. The rate of alkene coordination to  PtCl4  is highest for
(a) norbornene (b) ethylene (c) cyclohexene (d) 1-butene
28. The nephelauxetic parameter  is highest for


(a) Br  (b) Cl (c) CN  (d) F
3
29. The 2 Eg  4A 2g transition in the electronic spectrum of  Cr  NH3 6  occurs nearly at
(a) 650 nm (b) 450 nm (c) 350 nm (d) 200 nm
2 PAPER : CSIR-UGC-NET/JRF Dec. 2016
30. In the catalytic hydration of CO2 by carbonic anhydrase, CO2 first interacts with
(a) OH group of the active site of the enzyme and then with zinc
(b) H2O of the active site of the enzyme and then with zinc
(c) zinc of the active site of the enzyme and then with OH group
(d) zinc of the active site of the enzyme and then with H2O
31. For the reaction,
 H 3O  aq   X aq 
HX  aq   H 2 O    

the highest value of  X   aq  , when X  is
(a) OCl (b) F (c) Cl (d) NO 2

32. The correct statement for d.c. polarography is
(a) E1/2 is concentration dependent
(b) Dropping mercury electrode is a macro electrode
(c) Limiting current is equal to diffusion current
(d) A large excess of supporting electrolyte eliminates migration current.
33. Saturation factor in neutron activation analysis is
(A = induced radioactivity;  = neutron flux;  = effective nuclear cross section; N = no. of
target atoms;  = decay constant)
A NA  N
(a) (b) (c) (d)
N  AN A
34. The primary analytical method (not using a reference) is
(a) inductively coupled plasma emission spectrometry
(b) energy dispersive X-ray fluorescence spectrometry
(c) anodic stripping voltammetry
(d) isotopic dilution mass spectrometry
35. The number of inorganic sulphur (or sulphide) atoms present in the metalloprotein active sites of
rubredoxin, 2-iron ferredoxin and 4-iron ferredoxin, respectively, are
(a) 0, 2 and 4 (b) 2, 4 and 3 (c) 0, 4 and 2 (d) 0, 2 and 3
36.
The metal iodide with metallic lustre and high electrical conductivity is
(a) NaI (b) CdI2 (c) LaI2 (d) BiI3
37. The correct order of the bond dissociation energies for the indicated C-H bond in following com-
pounds is
H H H
(A) (B) (C)

(a) C > B > A (b) A > B > C (c) A > C > B (d) C > A > B
PAPER : CSIR-UGC-NET/JRF Dec. 2016 3
38. The correct order of the acidity for the following compounds is
O O
O O
(A) (B) (C)
O
O
(a) B > C > A (b) C > B > A (c) B > A > C (d) C > A > B
39. The correct statement about the following compound is
Me
Me
(a) compound is chiral and has P configuration

(b) compound is chiral and has M configuration
(c) compound is achiral as it possesses C2-axis of symmetry
(d) compound is achiral as it possesses plane of symmetry
40. Methyl groups in the following compound are

Ph
O Me
O Me
Ph
(a) homotopic (b) diastereotopic (c) enantiotopic (d) constitutionally heterotopic
41. Among the structures given below, the most stable conformation for the following compound is
(a) (b) (c) (d)
42. Molecular orbital interactions involved in the first step of the following reaction is
H H Br
+ Br Br
H H Br
(a) C C  *Br  Br (b) n Br   CC (c) C C   Br  Br (d) n Br  C C
43. The major product formed in the dinitration of 4-bromotoluene is
NO2 NO2 NO2
(a) (b) (c) (d)

NO2 O2N NO2 O2N
NO2 Br Br Br
44. The correct order of the rate constants for the following series of reactions (Z = CF3/CH3/OCH3) is
NO2 NO2
Z Br + H N Z N
(a) CF3 > CH3 > OCH3 (b) CF3 > OCH3 > CH3
(c) OCH3 > CF3 > CH3 (d) CH3 > OCH3 > CF3
1
45. H NMR spectrum of a mixture of benzene and acetonitrile shows two singlets of equal integration.
The molar ratio of benzene : acetonitrile is
(a) 1 : 1 (b) 2 : 1 (c) 1 : 2 (d) 6 : 1
46. The compound which shows IR frequencies at both 3314 and 2126 cm–1 is
(a) CH3  CH 2  4 CH 2SH (b) CH 3  CH 2  4 CH 2C  N
(c) CH 3  CH 2  4 CH 2C  C  H (d) CH 3  CH 2  2 C  C  CH 2 2 CH 3
47. Number of signals present in the proton decoupled 13C NMR spectrum of the following compound is
Br
Br
Br
Br
(a) four (b) six (c) eight (d) ten

48. The most stable product formed in the following reaction is
AlCl3
heat
(a) (b) (c) (d)

49. The major product in the following reaction is

O
(i) (CH3)2CuLi
OTBS
(ii) H2O
TBS = Si(CH3)2t-C4H9
HO O O HO
(a) (b) (c) OTBS (d)
OTBS OTBS OTBS
50. The major product formed in the following reaction is

CO2CH3
Zn/Cu, CH2I2
CO2CH3
OCH3
(a) (b)
O
CO2CH3
OMe
(c) (d)
51. www.careerendeavour.com
Correct characteristics of the functional groups of adenine in DNA base pair are
(a) N(3) is a hydrogen bond acceptor and C(6)NH2 is a hydrogen bond donor.
(b) N(1) is a hydrogen bond acceptor and C(6)NH2 is a hydrogen bond donor
(c) Both N(3) and C(6)NH2 are hydrogen bond acceptors
(d) Both N(1) and C(6)NH2 are hydrogen bond acceptors
1
52. H NMR spectrum of an organic compound recorded on a 500 MHz spectrometer showed a quartet
with line positions at 1759, 1753, 1747, 1741 Hz. Chemical shift    and coupling constant (Hz) of
the quartet are
(a) 3.5 ppm, 6 Hz (b) 3.5 ppm, 12 Hz (c) 3.6 ppm, 6 Hz (d) 3.6 ppm, 12 Hz
1
53. The weight of the configuration with two up and three down spins in a system with five spin
2
particles is
(a) 120 (b) 60 (c) 20 (d) 10
54. For a reaction with an activation energy of 49.8 kJ mol–1, the ratio of the rate constants at 600 K and
300 K, (k600/k300), is approximately (R = 8.3 J mol–1 K–1)
(a) ln (10) (b) 10 (c) 10 + e (d) e10
55. Covariance is defined by the relation Cov  x, y   xy  x y . Given the arbitrary constants A, B
and C, Cov  x, y  will be zero only when

2
(a) y  Ax 2 (b) y  Ax 2  B (c) y  Ax  B (d) y  Ax  Bx  C
56. Each void in a two dimensional hexagonal close-packed layer of circles is surrounded by
(a) six circles (b) three circles (c) four circles (d) twelve circles
57. The ionic mobilities of NH 4 and HCO3 are 6  104 V 1s 1 and 5  104 V 1 s 1 , respectively. The
transport numbers of NH 4 and HCO3 are, respectively
(a) 0.545 and 0.455 (b) 0.455 and 0.545 (c) 0.090 and 0.910 (d) 0.910 and 0.090
58. The ionic strength of a solution containing 0.008 M AlCl3 and 0.005 M KCl is
(a) 0.134 M (b) 0.053 M (c) 0.106 M (d) 0.086 M
59. The correct normalized wavefunction for one of the sp2 hybrid orbitals is
1 1 1 1 2 1
(a)  2 s   2 px   2 py (b)  2 s   2 px   2 py
3 3 3 3 3 6
1 1 1 1 1 1
(c)  2s   2 px   2 py (d)  2s   2 px   2 py
3 2 6 3 2 3 6
60. The correct statement in the context of NMR spectroscopy is
(a) static magnetic field is used to induce transition between the spin states
(b) magnetization vector is perpendicular to the applied static magnetic field
(c) the static magnetic field is used to create population difference between the spin states
(d) static magnetic field induces spin-spin coupling.
61. The parameter which always decreases during a spontaneous process at constant S and V, is
(a) U (b) H (c) CP (d) q
62. Triple point pressure of substances A, B, C and D are 0.2, 0.5, 0.8 and 1.2 bar, respectively. The
substance which sublimes under standard conditions on increasing temperature is
(a) A (b) B (c) C (d) D
H #
63. According to the transition state theory, the plot with slope equal to is
R
k k 1 1
(a) ln k vs. T (b) ln   vs. T (c) ln   vs. (d) ln k vs.
T  T  T T
64. The transition that belongs to the Lyman series in the hydrogen-atom spectrum is
(a) 1s  4 s (b) 1s  4 p (c) 2s  4s (d) 2 s  4 p
65. The molecule that possesses S4 symmetry element is
(a) ethylne (b) allene (c) benzene (d) 1, 3-butadiene
66. Vibrations of diatomic molecules are usually modelled by a harmonic potential. If the potential is
given by x2, the correct statement is
(a) force is 2x and force constant is 2 (b) force is –2x and force constant is 2
(c) force is 2x and force constant is –1 (d) force is –2x and force constant is –1
67. When 1×10–5 g of a fatty acid (M = 602.3 g/mol) was placed on water as a surface film, a monomo-
lecular layer of area 100 cm2 was formed on compression. The cross-sectional area (in Å2) of the acid
molecule is
(a) 50 (b) 100 (c) 150 (d) 200
68. Mark-Houwink equation     KM a  is used for the determination of

(a) number-average molar mass
(b) weight-average molar mass
(c) viscosity-average molar mass
(d) z-average molar mass
69. Many properties of nanoparticles are significantly different than the corresponding bulk materials
due to
(a) smaller band gap of nanoparticles compared to bulk
(b) higher heterogeneity of the nanoparticle solutions
(c) larger ratio of surface area to volume of the nanoparticles compared to the bulk
(d) smaller ratio of surface area to volume of the nanoparticles compared to the bulk
70. The correct match for the following is
Column-A Column-B
 i  camphor  A  structural protein
 ii  insulin  B  hormone
 iii  keratin  C  enzyme
 D  steroid
 E  terpene
(a) (i)-(A); (ii)-(C); (iii)-(E) (b) (i)-(E); (ii)-(B); (iii)-(A)
(c) (i)-(D); (ii)-(C); (iii)-(A) (d) (i)-(E); (ii)-(B); (iii)-(D)
PART-C
71. Consider the following statements for K C8:
(A) It is paramagnetic, (B) It has eclipsed layer structure, (C) Its electrical conductivity is greater
than that of graphite. The correct answer is
(a) A and B (b) A and C (c) B and C (d) A, B and C
72. Among the following, choose the correct products that are formed in the reaction of S2Cl2 with
ammonia in CCl4:
NH4Cl(A), S4N4(B), S8(C), and S3N3Cl3(D).
(a) A, B and C (b) A, B and D (c) B, C and D (d) A, C and D
73. For [Ce(NO3)4(OPPh3)2], from the following
A. Its aqueous solution is yellow-orange in colour
B. Coordination number of Ce is ten
C. It shows metal to ligand charge transfer
D. It is diamagnetic in nature
The correct answer is

(a) A and B (b) A and C (c) A, B and D (d) B, C and D
74. Consider the following statements, I and II:
I: [Rh(CO)2I2]– catalytically converts CH3I and CO to CH3COI
II: [Rh(CO)2I2]– is diamagnetic in nature
The correct from the following is
(a) I and II are correct and II is an explanation of I
(b) I and II are correct and II is not an explanation of I
(c) I is correct and II is incorrect
(d) I and II are incorrect
75. In a direct isotopic dilution method for determination of phosphate, 2 mg of 32PO43– (specific
activity 3100 disintegration s–1 mg–1) was added to 1g of a sample solution. The 30 mg of
phosphate isolated from it has an overall activity of 3000 disintegration s–1. The % mass of PO43–
in the sample is
(a) 30 (b) 6 (c) 9 (d) 15
76. Consider the following statements for [FeO4]4–.
A. It is paramagnetic
B. It has Td symmetry
C. Adopts distorted square planar geometry
D. Shows approximately D2d symmetry
(a) A, B and C (b) A, C and D (c) A and D (d) A and B
77. The geometry of [ReH9]2– is
(a) monocapped square antiprism (b) monocapped cube
(c) tricapped trigonal prism (d) heptagonal bipyramid
78. The reaction between PI3, PSCl3 and zinc powder gives P3I5 as one of the products. The solution
state 3IP NMR spectrum of P3I5 shows a doublet (  98) and a triplet (  102). The correct structure
of P3I5 is
I I
I I P
P P I I
I P I I I
(a) P P (b) I P P
I
(c) P P
(d) P P I
I
I I
I I I I
79. Some molecules and their properties in liquid ammonia are given in columns A and B respectively.
Match column A with column B
Column A Column B
(A) Cl 2 (i) Weak acid
(B)S8 (ii)Strong acid
(C) CH 3CO 2 H (iii) Disproportionation
(D) Urea (iv)Solvolysis and disproportionation
The correct match is

(a) (A) – (i); (B) – (ii); (C) – (iii); (D) – (iv)
(b) (A) – (ii); (B) – (iii); (C) – (iv); (D) – (i)
(c) (A) – (iii); (B) – (iv); (C) – (i); (D) – (ii)
(d) (A) – (iv); (B) – (iii); (C) – (ii); (D) – (i)
80. The spectroscopic ground state term symbols for the octahedral aqua complexes of Mn(II), Cr(III)
and Cu(II), respectively, are
(a) 2H, 4F and 2D (b) 6S, 4F and 2D
2 2 2
(c) H, H and D (d) 6S, 4F and 2P
81. From the following transformations,
A. Epoxidation of alkene
B. Diol dehydrase reaction
C. Conversion of ribonucleotide-to-deoxyribonucleotide
D. 1, 2-carbon shift in organic substrates
those promoted by coenzyme B12 are
(a) A and B (b) B, C and D (c) A, B and D (d) A, B and C
82. Match the items in column A with the appropriate items in column B
Column A Column B
(A) Metallothioneins (i) cis-[Pd(NH3)2Cl2]
(B) Plastocyanin (ii) Cysteine rich protein
(iii) Electron transfer
(D) Chemotherapy (iv) Iron transport
(v) Iron storage
(vi) Carboplatin
(a) (A) – (ii); (B) – (iii); (C) – (v); (D) – (iv)
(b) (A) – (ii); (B) – (iii); (C) – (iv); (D) – (i)
(c) (A) – (ii); (B) – (iii); (C) – (v); (D) – (vi)
(d) (A) – (iii); (B) – (v); (C) – (vi); (D) – (ii)
2
83. For OH– catalysed SN1 conjugate base mechanism of  Co  NH 3 5 Cl  , the species obtained in
the first step of the reaction is/are
2 
(a)  Co  NH 3 5  OH    Cl (b)  Co  NH 3  4  NH 2  Cl   H 2 O
2 
(c)  Co  NH 3  4  NH 2    Cl (d)  Co  NH 3 5 Cl  OH   only
84. Match the species in column X with their properties in column Y
Column-X Column-Y
(1) Heme A (i) oxo-bridged, Mn4 cluster
(2) Water splitting enzyme (ii) tetragonal elongation
2
(3)  Mn  H 2 O 6  (iii) Predominantly   * , electronic transitions
2
(4)  Cr  H 2 O 6  (iv) d  d spin-forbidden transitions
(v) tetragonal compression
(a) (1)-(iii), (2)-(i), (3)-(v), (4)-(ii) (b) (1)-(iii), (2)-(i), (3)-(iv), (4)-(ii)
(c) (1)-(v), (2)-(iii), (3)-(iv), (4)-(ii) (d) (1)-(iii), (2)-(i), (3)-(iv), (4)-(v)
85. According to isolobal analogy, the right set of fragments that might replace Co(CO)3 in
 Co 4  CO 12  is
(a) CH, BH and Mn(CO)5 (b) P, CH and Ni  5 -C5 H 5 

(c) Fe(CO)4, CH2 and SiCH3 (d) BH, SiCH3 and P
According to Wade’s rules, the correct structural types of  Co   -C5 H5  B4 H 8  and
5
86.
 Mn  2  B3 H8   CO   are
 4
(a) closo and nido (b) nido and arachno (c) closo and arachno(d) nido and nido
2
87. The correct geometry of  Rh 6 C  CO 15  is
(a) octahedron (b) pentagonal pyramid (c) trigonal prism (d) monocapped square
pyramid
88. The final product(s) of the reaction of arachno borane, B4H10 with NMe3 is/are
 
(a)  BH 3.NMe3  and  B3H 7 .NMe3  (b)  BH 2  NMe3 2   B3 H8 
 
(c)  B4 H10 .NMe3  (d)  B4 H10 .NMe3  and  BH 2  NMe3 2   B3 H8 
89. Product A in the following reaction is
H H
H H H
+ CD3H + A
Co H Co
Me3P CD3 PMe3
H
CD3
H
CD3
(a) D2C CD 2 (b) D3 C CD 3 (c) (d) H2C CD 2
90. Treatment of Fe(CO)5 with 1, 3-butadiene gives B that shows two signals in its 1H NMR spectrum.
B on treatment with HCl yields C which shows four signals in its 1H NMR spectrum. The compound
C is
Cl H
OC OC
OC Cl OC
Cl
Fe Fe
(a) Fe (b) OC (c) Fe (d) OC
OC CO OC CO
CO H
91. In the following redox reaction with an equilibrium constant K = 2.0 × 108,
2 3 3 2
  Ru  NH 3     Fe  H 2 O  
 Ru  NH 3 6    Fe  H 2 O  6    6  6
–1 –1 3 –1 –1
the self exchange rates for oxidant and reductant are 5.0 M s and 4.0×10 M s , respectively. The
approximate rate constant (M–1s–1) for the reaction is
(a) 3.16×106 (b) 2.0×106 (c) 6.32×106 (d) 3.16×104
92. The correct statement for a Fischer carbene complex is
(a) the carbene carbon is electrophilic in nature
(b) metal exists in high oxidation state
(c) metal fragment and carbene are in the triplet states
(d) CO ligands destabilize the complex
93. The acidic solution containing trimethylamine (A), dimethylamine (B) and methyl amine (C) (pKa of
cations 9.8, 10.8 and 10.6, respectively) was loaded on a cation exchange column. The order of their
elution with a gradient of increasing pH > 7 is
(a) A < C < B (b) B < C < A (c) B < A < C (d) C < B < A
94. For complex A, deuteration of NH protons does not alter the EPR spectrum. The number of hyper-
 63 3
fine lines expected in the EPR  I  Cu   spectrum of A is
 2 
O O
63
Cu
N N
H H
(a) 20 (b) 12 (c) 60 (d) 36
95. The numbers of triangular faces in square antiprism, icosahedron and tricapped trigonal prism (capped
on square faces), respectively, are
(a) 8, 20 and 14 (b) 8, 20 and 12 (c) 10, 12 and 14 (d) 10, 12 and 12
96. Number of lines in the 19F NMR spectrum of F2C(Br)–C(Br)Cl2 at –120ºC assuming it a mixture of
static conformations given below, are
Br Br Br
Cl Cl Br Cl Cl Br
F F F F F F
Br Cl Cl
(a) one (b) two (c) four (d) five
97. The correct statement for the reactants A, B to give products C, D is

OSO2Ph OH
O O
(A) (C)
H2O
O O
PhO2SO HO
(B) (D)
(a) A gives C and B gives D (b) A gives D and B gives C
(c) A and B give identical amounts of C and D (d) A and B give D
O O
(i) t-BuLi
(ii) ICH2CH2Cl
N
Cl
O O
O O
(a) (b)
Cl N
N
I
O O
O O
(c) (d)
I N
N
I
N
CHO
(i) S , NaOMe
(ii)
CHO
O
OH O
O O
(a) (b)
O OH
O OH
O O
(c) (d)
O OH
100. The compound that exhibits following spectral data is

1
H NMR :  8.0  d, J  12.3 Hz, 1H  , 7.7  d, J  8.0 Hz, 2H  ,
6.8  d, J  8.0 Hz, 2H  , 5.8  d, J  12.3 Hz, 1H  , 3.8  s, 3H  , 3.0  s, 6H  ppm

N(CH3)2
CO2CH3
(H3C)2N CO2CH3
(a) (b)
O O
CH3 CH3
N N
(c) (d)
CH3 CH3
H3CO H3CO

Ph
N Ph
O O
B
BH3
OH H
H HO
(a) , by Re face attack (b) , by Re face attack
H OH
HO H
(c) , by Si face attack (d) , by Si face attack

OAc
(i) PBr , H O 3 2
O (ii) Zn, AcOH
AcO OMe
AcO (iii) NIS, CH3OH
OAc
NIS : N-iodosuccinimide
OAc
I
I
O O
AcO OMe AcO
(a) AcO (b) AcO
OAc OCH3
I
AcO OCH3
O O
AcO
(c) AcO (d) AcO
AcO
I OAc OMe

H3CS
(i) CH3I
(ii) t-BuOK
O
H3CS H3CS
H3CS
(a) (b) (c) (d)

O O O
O

Cl PCy3
Ru
Cl Ph C2H5O2C CO2C2H5
CO2C2H5 PCy3
(A) (B)
CO2C2H5
CO2C2H5
H
C2H5O2C
CO2C2H5 CO2C2H5
(a) A = B=
CO2C2H5 CO2C2H5
CO2C2H5
H
C2H5O2C
CO2C2H5 CO2C2H5
(b) A = B=
CO2C2H5 CO2C2H5
H
CO2C2H5
CO2C2H5
(c) A = B= H CO2C2H5
CO2C2H5
C2H5O2C CO2C2H5
H
CO2C2H5
CO2C2H5
(d) A = B= H CO2C2H5
CO2C2H5
C2H5O2C CO2C2H5
105. Correct sequence of reagents for the following conversion is

Br Br
Br
N Br
N OH
OH O
(a) (i) K2CO3, (ii) HC  CCOCH 3 , (iii) Br2, (iv) NaBH4
(b) (i) NaBH4, (ii) HC  CCOCH 3 , (iii) Br2, (iv) K2CO3
(c) (i) HC  CCOCH 3 , (ii) K2CO3 , (iii) Br2, (iv) NaBH4
(d) (i) Br2, (ii) HC  CCOCH 3 , (iii) K2CO3, (iv) NaBH4
O
O
S N TESO
N + NaHMDS
O N N
Ph OHC
TES : Triethylsilyl
OMe
OTES
O
(a)
OMe
OTES
(b) O
OMe
OTES OTES
(c) (d)
O O
OMe OMe
107. For the four reactions given below, the rates of the reactions will vary as
O
(1) O2N N O2N O N
O
(2) H N H O N
O2N O2N
H2O
OTs OH
(3)
H H
H2O
OTs OH
(4)
(a) 1 > 2 and 3 > 4 (b) 2 > 1 and 3 > 4 (c) 2 > 1 and 4 > 3 (d) 1 > 2 and 4 > 3
(i) L-proline, acetone, DMSO
CHO
(ii) Me4NBH(OAc)3,
AcOH, CH3CN, –40ºC
(a) (b) (c) (d)

OH OH OH OH OH OH OH OH
The correct sequence of pericyclic reactions involved in the following transformation is
(i) SeO2 (cat.)
t-BuOOH CHO
(ii) PCC
(a) (i) ene reaction, (ii) [2, 3]-sigmatropic shift, (iii) [3, 3]-sigmatropic shift
(b) (i) ene reaction, (ii) [3, 3]-sigmatropic shift, (iii) [1, 3]-sigmatropic shift
(c) (i) [2, 3]-sigmatropic shift, (ii) ene reaction, (iii) [1, 3]-sigmatropic shift,
(d) (i) [1, 3]-sigmatropic shift, (ii) [2, 3]-sigmatropic shift, (iii) [3, 3]-sigmatropic shift
110. The intermediate that leads to the product in the following transformation is
OCH3
Tl(NO3)3
CH3OH
OCH3
H H
OCH3 OCH3
(a) H (b) Tl(NO3)2 (c)
Tl(NO3)2 H
H
OCH3
(c) Tl(NO3)2 (d) ONO2
H
111. Product(s) of the following reaction is (are) [*-indicates isotopically labelled carbon]
*
OH BF3 .OEt2
N
H
(a) (b) *
N
N
H
H
* *
*
+
(c) * (d) +
N N N N
H H H H
The major product formed in the following reaction is
OMe
MeO
ZnCl2, Pd2(dba)3, PPh3
+
THF, r.t.
NMe2
Br N N Li
O
(dba = dibenzylidene acetone)
OMe
OMe
MeO
N
NMe2
(a) N (b) NMe2
Br N
N O
O
N OMe
MeO
MeO
(c) (d)
NMe2 Br N N
Br N
O
O
1. TMSCN, ZnI2 (cat.)
2.(i) LDA, THF, –78ºC to r.t.
(ii) i-Pr-I
PhCHO
3. (i) H+, H2O
(ii) aq. NaOH
OTMS OH O
(a) Ph (b) Ph (c) Ph (d) Ph

(i) Hg(OAc)2
(ii) NaBr
(iii) O2, NaBH4
NHCbz
OH
OH
(a) N (b) N (c) N (d) N
Cbz Cbz Cbz Cbz

115. Correct match for the products of the reactions in Column-A with the properties in Column-B is
Column-A Column-B
(i) + 2K (P) aromatic
(ii) + H2SO4 (Q) antiaromatic
heat
(iii) (R) non-aromatic
heat
(iv) + 2K (S) homoaromatic
(a) (i)-P, (ii)-S, (iii)-R, (iv)-Q (b) (i)-P, (ii)-R, (iii)-Q, (iv)-S
(c) (i)-Q, (ii)-R, (iii)-S, (iv)-P (d) (i)-S, (ii)-Q, (iii)-R, (iv)-P
116. The correct starting compound A in the following reaction is

EtO2C
CH3C(OEt)3
(A) BnO
cat. CH3CH2CO2H
heat
OH OH
(a) BnO (b) BnO
OH OH
(c) BnO (d) BnO

N
N NaNO2-HCl
pH = 5-6
NH2
N N N N
N N N N N N
(a) N (b) N (c) Cl (d)

N
N
(i) hv
(ii) H3O+
ONO
O
(a) OH (b) OH
(c) OH (d) OH
CHO

H+
O
OH
(a) (b) (c) (d)
O O
OMe
OMe
Cl Cl
O
O O O
O O
Ph O
O NC CN (1 equiv.)
OAc
CH2Cl2–H2O
OMe
OMe
OMe
OMe
O
O
O HO O
O O O
O OAc
(a) Ph O (b)
O
OAc
OH
OMe
OMe
OMe
OMe
OH
O
Ph O O
O OMe
OAc
O
(c) (d) O
O
Ph O O
HO
OAc
OMe
121. A constant of motion of hydrogen atom in the presence of spin-orbit coupling is

(a)  (b) s (c)   s (d)   s
122. The orbital degeneracy of the level of a one-electron atomic system with Z = 5 and energy  –13.6
eV, is
(a) 1 (b) 5 (c) 25 (d) 36
123. If we write a normalized wavefunction   Â , then  is also normalized when

(a) Â is hermitian (b) Â is anti-hermitian
(c) Â is unitary (d) Â is any linear operator
124. The ground state of a certain system with energy 0 is subjected to a perturbation V, yielding a first-
order correction 1 . If E0 is the true ground-state energy of the perturbed system, the inequality that
always holds is
(a) 1  0 (b) 1  E 0 (c) 0  1  E 0 (d) 0  1  E 0
125. The spatial part of an excited stat e b 3  u of hydrogen molecule is proportional to
1 g 1 1u  2   1g  2 1 u 1  . Using LCAO–MO expansion of 1g and 1u in terms of 1s-atomic
orbitals, one can infer that this wavefunction has
(a) only ionic parts (b) only covalent parts
(c) both ionic and covalent parts (d) neither ionic nor covalent parts
126. The highest molecular orbitals for an excited electronic configuration of the oxygen molecule are
1 1
1g  3u  . A possible molecular term symbol for oxygen with this electronic configuration is
(a) 1  (b) 3  (c) 1  (d) 1 
127. For H2O molecule, the electronic transition from the ground state to an excited state of B1 symmetry
is
C2 v E C2  v  'v
A 1 1 1 1 1z, z , x , y 2 2 2
A2 1 1 1 1 xy
B1 1 1 1 1 x, xz
B2 1 1 1 1 y, yz
(a) not allowed (b) allowed with x polarisation

(c) allowed with y polarisation (d) allowed with z polarisation
128. The pair of symmetry points groups that are associated with only polar molecules is
(a) C2 v , Dh (b) C3v , C2 h (c) D2 h , Td (d) C2 v , Cv
129. The rotational constant and the fundamental vibrational frequency of HBr are, respectively, 10 cm–1
and 2000 cm–1. The corresponding values for DBr approximately are
(a) 20 cm–1 and 2000 cm–1 (b) 10 cm–1 and 1410 cm–1
–1 –1
(c) 5 cm and 2000 cm (d) 5 cm–1 and 1410 cm–1
130. Among the following, both microwave and rotational Raman active molecule is
(a) CH4 (b) N2O (c) C2H4 (d) CO2
131. In a 200 MHz NMR spectrometer, a molecule shows two doublets separated by 2 ppm. The observed
coupling constant is 10 Hz. The separation between these two signals and the coupling constant in a
600 MHz spectrometer will be, respectively
(a) 600 Hz and 30 Hz (b) 1200 Hz and 30 Hz
(c) 600 Hz and 10 Hz (d) 1200 Hz and 10 Hz
132. The equation of state for one mole of a gas is given by P V  b   RT , where b and R are constants.
 H 
The value of  P  is
 T
RT
(a) V  b (b) b (c) 0 (d) b
P
133. The volume change in a phase transition is zero. From this, we may infer that the phase boundary is
represented by
P P P P
(a) (b) (c) (d)
T T T T
 T 
134. The partial derivative  V  is equal to
 P
 P   P   P   P 
(a)   S  (b)   S  (c)   S  (d)   S 
 T  V  n  H
135. If the energies of a bare proton aligned along and against an external static magnetic field  Bz  are
 Bz  Bz
 and  , respectively, then the ratio of probabilities of finding the proton along and
2 2
against the magnetic field is
(a) e  Bz /4 kBT (b) e  Bz /2 kBT (c) e Bz / 2 kBT (d) e  Bz / kBT
136. Partition function of a one-dimensional oscillator having equispaced energy levels with energy spac-
ing equal to kBT and zero ground state energy is
1 e 1
(a) e (b)  e  1 (c)  e  1 (d)  e  1
137. A reaction goes through the following elementary steps


k1
A  B   2C  fast 
k 
1
k2
A  C  D  slow 
Assuming that steady approximation can be applied to C, on doubling the concentration of A, the
rate of production of D will increase by (assuming k2  A  k1 C  )
(a) 2 times (b) 4 times (c) 8 times (d) 2 2 times
138. The rate of an acid-catalyzed reaction in aqueous solution follows rate equation
r  k  X   Y 2    H  
If k16 and k4 are rate constants for the reaction at ionic strength of 16 molL–1 and 4 molL–1, respec-
k4
tively, ln k , in terms of Debye-Hückel constant (B = 0.51), is
16
(a) 4B (b) 8B (c) 10B (d) 12B

139. For two reactions,
X  g   Y  g  
Z g 1
M  g   N  g  
Pg 2
According to the collision theory, the ratio of squares of pre-exponential factors of reactions 2 (A2)
2
 A2 
and 1(A1) at the same temperature,   , is
 A1 
Species Mass  g / mol  Diameter  nm 

X 5 0.3
Y 20 0.5
M 10 0.4
N 10 0.4
(a) 4/5 (b) 5/5 (c) 5/3 (d) 3/5

140. If the specific conductances of a sparingly soluble (1 : 1) salt (MW = 200 g mol–1) in its saturated
aqueous solution at 25ºC and that of water are 1.5×10–3 ohm–1 dm–1 and 1.5×10–5 ohm–1 dm–1, respec-
tively, and the ionic conductances for its cation and anion at infinite dilution are 0.485 and 1.0 ohm–
1
dm2 mol–1, respectively, the solubility (in g L–1) of the salt in water at 25º C is
(a) 1×10–6 (b) 1×10–3 (c) 2×10–1 (d) 2×10–4
141. Given, www.careerendeavour.com

 Zn  NH   2e, E  1.03 V
(i) Zn  4NH  3
2
3 4
0
 Zn 2   2e,
(ii) Zn  E 0  0.763V
2
The formation constant of the complex Zn  NH 3 4 is approximately
 2.303RT 
  0.0591
 F 
(a) 1 105 (b) 1 10 7
(c) 1109 (d) 1 1012
142. The molar conductivity    vs. concentration (c) plot of sodium dodecylsulfate in water is expected
to look like
   
(a) (b) (c) (d)
c c c c
143. The sin 2  values obtained from X-ray powder diffraction pattern of a solid are 2x, 4x, 6x, 8x where
x is equal to 0.06. The wavelength of X-ray used to obtain this pattern is 1.54Å. The unit cell and the
unit cell length, respectively are
(a) BCC, 3.146Å (b) FCC, 3.146Å (c) SCC, 6.281 Å (d) BCC, 1.544Å
144. Distribution of molar masses in a typical polymer sample is shown below
Molecular weight
The A, B and C represent

(a) M w , M v and M n , respectively (b) M n , M v and M w , respectively
(c) M v , M w and M n , respectively (d) M n , M w and M v , respectively
145. Two bound stationary states, 1 and 2, of a one-electron atom, with E 2  E1 (E is the total energy)
obey the following statement about their kinetic energy (T) and potential energy (V)
(a) T2 > T1; V2 > V1 (b) T2 > T1 ; V2 < V1
(c) T2 < T1 ; V2 > V1 (d) T2 = T1 ; V2 > V1
SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016 25
SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016

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 
 8  5 1
23.  XeF5    7 sp3d 3 hybridization
2
F –
••
F F
Xe
F•• F
Pentagonal Planar
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.
26 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016
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
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
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.
28. According to Nephelauxetic series
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.
30. In carbonic anhydrase OH group first attack on CO2 and then CO2 intract with Zn.

31. Due to more acidity of HCl it will undergo more ionization. Hence, concentration of  Cl  aq will be
maximum.
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
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
34. Primary analytical method is isotopic dilution mass spectrometry (not using a reference).
35. Ruberdoxin cysteine 2-iron ferredoxin Fe2S2

S (Cys)
(Cys)
Fe Fe Fe
S S (Cys)
S (Cys) S
cysteine cysteine
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)
36. LaI2 exists as La 3  2I   e  

The electron present is responsible for metallic cluster and high electrical conductivity.
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.
38. • Cyclic  -diketones are more acidic than open chain  -diketones
• As the ring decreases, acidity increases
O O
(B) > (A) > (C)
Least acidic
Me
Me
39. (chiral)
P-configuration
Helical chirality, P-configurations. Since, clockwise path from front side.

Correct option is (a) www.careerendeavour.com
Ph
O Me
C2 symmetry
40.
O Me
Ph
Homotopic
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)
H H H H
Br
Br Br
42. + Br Br
-HOMO *
H H LUMO H H Br
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
45. C6H6
6H
: www.careerendeavour.com
CH –CN
3H
3
1 equivalent : 2 equivalent
6H 6H
1 : 1 (Integration ratio)
3314 cm–1
46. H3C(H2C)4H2CC C H
2126 cm–1
C C 2126 cm–1
C C–H 3314 cm–1
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.

AlCl3 –H Rearrangement
48.
endo exo
AlCl3
Rearrangement
Rearrangement

O O
49.
OTBS OTBS
attack from less
Top hindered side
H3C CuLi
Me
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.
H
N  
N H O
51. 6
5
 
N 4 N H N
1
N
3 2
(Adenine) O
(Thymine)
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).
53.  total spin ½ particle

5 5 4 3
Weight of configuration = 5 C3    10
32 32
54.
 k  E T  T 
ln  2   a  2 1  www.careerendeavour.com
 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
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

56. From figure it is clear that each void is surrounded by three circles.

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
58. AlCl3  Al3  3Cl1

0.008 0 0
0 0.008 0.024
KCl  K   Cl  www.careerendeavour.com
0.005 0 0
0 0.005 0.005
1 1
I
2
  2 2 2
C1Z12  C2 Z 22  C3 Z32  C4 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
59. For normalised wave function, c12  c22  c32  1

1 1 1
   1
3 2 6
60. In NMR spectroscopy the static magnetic field is used to create population difference between the
spin states
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.
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 www.careerendeavour.com
Same explanation as above
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
64. For allowed transition,   1 and for Lyman Series Transition is from higher level to n = 1
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

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
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) www.careerendeavour.com
68. In equation,    kM a
  represents intrinsic viscosity

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.
70. Camphor  Terpene
Insulin  Hormone
Keratin  Structural Protein
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
72. CCl4 or C6H6

6S2 Cl2  16NH 3   S4 N 4  S8  12NH 4 Cl
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

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.
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
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
mA  2  30  60 mg
Out of 1g amount of PO4–3 in 60 mg.
3 60
So, % PO4   100  6%
1000
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
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.
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 
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 
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
L   | M L | 2  D
1
S  , 2S  1  2
2
Ground state term  2 D
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
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 .
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  
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

2
87.  Rh 6 C  CO 15 
 
TVE = 9×6 + 4 + 15×2 + 2 = 54 + 4 + 2 + 30 = 90
Hence, it has trigonal prism geometry.
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

H
CO Cl
H
OC
Fe(CO)5 + HCl
90. OC Fe Fe H
OC
CO CO H
(B) H
(C)
H H
Compound (C) has show four 1H NMR signal
1/ 2 1/ 2
91. k12   k11 K k 22 f    5  4 103  2 108 1.0   20  105  2.0  106
92. Fischer carbene carbon is electrophilic in nature due to strong  -acceptor ligands
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.
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
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
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
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
SN2  less hindered

OSO2Ph O
OH2
O PhO2SO
97.
O
(A) (B)
H2O O
OH HO
O (D)
(C)
Me
O I
Li
I O O
O Cl
O O t-BuLi
98. Me
H2C CH2
N
N +
N
+ –
I Cl
O O O
N
S
C H N C
H
H S +
99. H
NaOMe S N
O
OH
OH
S
+ H
O H O
transfer O
OH N
N S N SO
O
OH

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
Backside
O HO H H
HO
H
101. RS RL RS RL
Si-face
(Backside)
OAc OAc OAc
102. O 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

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
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
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

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
O O
107. O2N N H N
More stable Less stable
–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.

H H H
OTs OH
H2O
More stable
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
O
2
O Se 3
O Se O 1 O
H OH Se O
O
H O
O 2
1 3
109.
www.careerendeavour.com [3, 3] S.T.R.

OH
CHO PCC

OMe
OMe
110. MeOH OMe
Tl(NO2)2
Tl(NO2)2
Tl Tl(NO2)2 ring
O2N Me control
OMe
MeOH
OMe OMe
* * *
OBF3
H
111.
N N N
H
H H
*
*
N N
H H

112. Coupling reaction
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

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
115. (i) + 2K
10 e– system (Aromatic)
(ii) + H 2SO 4 H
H
Homoaromatic
H
heat
(iii)
H Non-aromatic
heat
(iv) + 2K
Anti-aromatic
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)

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)

118. Barton reaction :
hv -H abstract
 
•  •
ONO NO O OH

H N
H
O
H3 O+
OH
OH
O
N
OH
+
+H
ring –
119. HO HO
expension O

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
 
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
Z2 25
122. E  13.6 2
  13.6  2  13.6  n  5
n n
Therefore, orbital degeneracy = n2 = 25.
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
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  
 
 www.careerendeavour.com
  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  

 
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
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
A1 1 1 1 1
B1 1 1 1 1
127.
A1  B1  1 1 1 1  x polarised

128. The polar point group are
Cnv , Cn , C1 , Cs
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
www.careerendeavour.com  1410 cm 1
1
 BPBr   5 cm and v 
2 2
130. N2O is microwave and rotational Raman active molecule.
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
 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
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    www.careerendeavour.com
  90º
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
 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
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
136. Since, zero point energy = 0

1
 q E / kT [Given : E  k BT ]
1 e
1 1 1 1 e
 q
1 e www.careerendeavour.com

 kT / kT
 
1  e 1 1  1 e  1
 q
e 1
e e
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)
2 k 1  C   k 2  A
 k2  A  k1 C 
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 
#
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  www.careerendeavour.com
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
5  20 10  10
µ1   4 and µ2  5
25 20
2
 A2  4
   
 A1  5
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 
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
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
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
Mn
Mv
Mw
144. Weight Mz
fraction
Molecular weight
Correct order is Mn < Mv < Mw < Mz.

1 1
145. T1  V1  T2   V2
2 2
E1  E2
V1 V2
T1  V1  T2  V2    V1  V2 and T1  T2
2 2
PAPER : CSIR-UGC-NET/JRF June 2017 1
PAPER : CSIR-UGC-NET/JRF June 2017

PART-B
21. Which one of the following pairs has two magic numbers for closed nuclear shells ?
(a) 8, 10 (b) 10, 20 (c) 50, 82 (d) 82, 130
22. Identify the correct statement(s) for phosphorimetric measurement from the following :
A. It is done after a time delay when fluorescence, if present becomes negligible
B. Immobilization of analytic increases phosphorescence
C. Phosphorescence decreases in the presence of heavy atoms
(a) A only (b) A and B (c) A and C (d) B and C
23. Choose the isoelectronic pair among the following :
A. [V(CO)6 ]
B. [Cu(5  C5H 5 ) (CO)]
C. [Co(CO)4 ]
D. [IrCl(CO) (PPh 3 )2 ]
(a) A and B (b) B and C (c) C and D (d) A and D
24. An organometallic fragment that is isolobal to CH3+ is
(a) [Fe(CO)5 ] (b) [Mn(CO)5 ] (c) [Cr(CO)5 ] (d) [Ni(CO)3 ]+
25. The calculated and observed magnetic moments (in B.M.) of aqua complex of a lanthanide ion are 0
and ~3.5, respectively. The lanthanide ion is
(a) Pm3+ (b) Pr3+ (c) Eu3+ (d) Sm3+
26. The compound that gives a basic solution in HF is :
(a) AsF5 (b) PF5 (c) BF3 (d) BrF3
–
27. Based on VSEPR theory, the predicted shapes of [XeF5] and BrF5 respectively, are
(a) pentagonal planar and square pyramidal
(b) square pyramidal and trigonal bipyramidal
(c) trigonal bipyramidal and square pyramidal
(d) square pyramidal and pentagonal planar
28. Both potassium and sulfuric acid form intercalation compounds with graphite. The graphite layers
are
(a) reduced in both the cases
(b) oxidized in both the cases
(c) oxidized in the case of potassium and reduced in the case of sulphuric acid
(d) reduced in the case of potassium and oxidized in the case of sulphuric acid
29. The resonance Raman stretching frequencies (in cm–1) of the bound O2 species in oxy-hemerthyrin
and oxy-hemoglobin, respectively, are
(a) ~850 and 1100 (b) ~750 and 850 (c) ~850 and 850 (d) ~1100 and 850
30. CdS, HgS and BiI3, are coloured due to
(a) L  M charge transfer transitions
(b) d  d electronic transitions
(c) M  L charge transfer transitions
(d) combination of L  M charge transfer and d  d electronic transitions
2 PAPER : CSIR-UGC-NET/JRF June 2017
31. The relative rates of water exchange for the hydrated complexes of (1) Ni2+, (2) V2+ and (3) Cr3+
ions follows the trend
(a) (1) > (2) > (3) (b) (1) < (2) < (3) (c) (1) > (2) < (3) (d) (1) < (2) > (3)
32. Consider the following sulfur donor atom bearing bidentate ligand where X and name of ligands are
given in following columns :
S
X
S
X Ligand name
A. NR2 I. Dithiocarbonate
B. OR II. Dithiocarbamate
–
C. O III. Xanthate
D. SR IV. Thioxanthate
Correct match of entries given in two columns is
(a) A-II, B-III, C-I, D-IV (b) A-III, B-II, C-IV, D-I
(c) A-I, B-II, C-III, D-IV (d) A-IV, B-I, C-II, D-III
33. In vitro reaction of an excess of O2 with free heme B in aqueous medium the end product is
(a) hematin (b) [ O 2 Fe(III) -protoporphyrin-IX]
(c) heme B(O2) (d) oxoferrylprotoporphyrin-IX cation radical
13
34. C NMR spectrum of DMSO-d6 gives a signal at  39.7 ppm as a
(a) singlet (b) triplet (c) quintet (d) septet
35. Following reaction is an example of
1.
2. t-BuOK
S S
(a) Ramberg-Backlund reaction (b) [2, 3]-sigmatropic shift
(c) [3, 3]-sigmatropic shift (d) Pummerer rearrangement
36. Among the following, the synthetic equivalent of acetyl anion is
O www.careerendeavour.com
S
(a) (b) CH 3CN (c) (d) CH 3CH 2 NO 2
H3 C Cl S
37. Following reaction is an example of
S NC CN
S
heat
+
S
S NC CN CN
CN
NC CN
(a) [3 + 2] cycloaddition (b) [4 + 2] cycloaddition
(c) [6 + 2] cycloaddition (d) [8 + 2] cycloaddition
38. The major product of the following reaction is

O
H+
O
(a) (b) (c) (d)
39. The most stable conformation of 2-fluoroethanol is

OH OH
H OH F OH
F H H H
(a) F (b) (c) H (d)

H H H H H H H H
H H H F
40. The IUPAC name of the following compound is
H
(a) 9-borabicyclo[3.3.1]nonane (b) 1-borabicyclo[3.3.1]nonane

(c) 9-borabicyclo[3.3.0]octane (d) 1-borabicyclo[3.3.0]octane
41. The correct match of natural products in Column-I with their biosynthetic precursors in Column-II
is
Column-I
Column-II
Me
A. OH I. L-Lysine
Me Me
B. N II. L-Ornithine
H
N
III.Farnesyl
IV. Geranyl pyrophosphate

(a) A-IV, B-I (b) A-IV, B-II (c) A-III, B-I (d) A-III, B-II
42. The correct order of pKa values for the following species is
(a) PhNH 3+  i-Pr2 NH 2+  Ph 2 NH2+ (b) Ph 2 NH 2+  PhNH3+  i-Pr2 NH2+
(c) i-Pr2 NH 2+  Ph 2 NH 2+  PhNH3+ (d) PhNH 3+  Ph 2 NH 2+  i-Pr2 NH2+
43. Among the following, the natural product that is a steroid and contains an ,  -unsaturated ketone is
(a) estrone (b) prostaglandin (c) cortisone (d) morphine
Li, liq. NH3
(a) (b) (c) (d)

N N N N
H
45. The major product formed in the sodium ethoxide mediated reaction between benzophenone and
ethyl chloroacetate is
Ph
Cl Ph O Ph
Ph EtO Cl
COOEt COOEt COOEt
(a) (b) Ph (c) Ph (d) Ph
O
O Cl Ph OH
NBS (2 equiv)
hv, CCl4
www.careerendeavour.com reflux
Br Br
Br
Br Br
Br
(a) (b) (c) (d)
Br Br
47. Consider a particle in its ground state confined to a one-dimensional box in the interval (0, 8). The
probability of finding it between 4.0  2 and 4.0  2 is close to ( is sufficiently small so that the
wavefunction can be taken as a constant in this interval).
  
(a) (b) (c) (d) 
4 3 2
d d2
48. Which of the functions below is a common eigenfunction of and operators ?
dx dx 2
(a) cos x (b) kx (c) eix (d) e  x 2
49. A one-component system with the associated phase diagram (see the figure) is not possible because
B C
Phase 
Phase 
Pressure
Phase  D
O
Phase 
A
Temperature
(a) OB has a negative slops (b) OC has a positive slope

(c) Both OB and OC are linear (d) OB, OC and OD cannot all coexist, given OA
50. A phase transition process is always
(a) isothermal – isoentropic (b) isochoric – isothermal
(c) isobaric – isochoric (d) isothermal – isobaric
51. The correct statement for any cyclic thermodynamic process is
(a)  dq  0 (b)  dw  0 (c)  dU  0 (d)  Vdq  0
52. Metallic silver crystallizes in face-centred-cubic lattice structure with a unit cell of length 40 nm.
The first order diffraction angle of X-ray beam from (2, 1, 0) plane of silver is 30º. The wavelength
of X-ray used is close to
(a) 11 nm (b) 18 nm (c) 25 nm (d) 32 nm
53. If the pre-exponential factor in Arrhenius equation is 1.6  1012 s 1 , the value of the rate constant at
extremely high temperature will be close to
(a) 1.6  1012 s 1 (b) 4.2  1012 s 1 (c) 2.4  109 s 1 (d) 1.2  106 s 1
In kinetic study of a chemical reaction, slopes are drawn at different times in the plot of concentra-
tion of reactants versus time. The magnitude of slopes with increase of time
(a) remains unchanged (b) increases
(c) decreases (d) increases and decreases periodically
55. The electrochemical cell potential (E), after the reactants and products reach equilibrium, is (E0 is
the standard cell potential and n is the number of electrons involved)
(a) E  E 0  nF /RT (b) E  E 0  RT /nF (c) E  E 0 (d) E  0
3
56. For the electronic configuration 1s 2 2 s 2 2 p 4 , two of the possible term symbols are 1 S and p . The
remaining term is
(a) 1 D (b) 1F (c) 3 D (d) 3 F
57. The v = 0 to 1 vibration-rotation spectrum of a diatomic molecule exhibits transitions for

R  0  , R 1 , P 1 and P  2  lines at 2241, 2254, 2216 and 2203 cm–1, respectively. From this data,
we can conclude that the molecule
(a) has rigid rotation and harmonic vibration (b) has anharmonic vibration
(c) has rotational-vibrational interaction (d) is affected by nuclear spin-statistics
58. Consider aqueous solutions of two compounds A and B of identical concentrations. The surface
tension of the solution of A is smaller than that of pure water while for B it is greater than that of pure
water under identical conditions. From this one infers that
(a) surface concentration of A is smaller than its bulk concentration
(b) surface concentration of B is larger than its bulk concentration
(c) surface concentration of A is larger than that of B
(d) surface concentration of A is smaller than that of B
59. For a monodisperse polymer, the number-average molar mass  M n  and weight-average molar mass
 M  are related according to

w
(a) M w  M n (b) M w  M n (c) M w  M n (d) M w  log M n
60. An intense purple colour (Plasmon band) is exhibited by a colloid consisting of spherical
(a) silver particles of 10 mm diameter (b) silicon particles of 5 mm diameter
(c) gold particles of 5 nm diameter (d) iron particles of 3 mm diameter
PART-C
61. Choose the correct statement for magnitude of threshold energy of an endoergic nuclear reaction
between stationary nucleus and a moving projectile.
(a) It is greater than ‘ Q ’ of nuclear reaction.
(b) It has to be more than kinetic energy of a projectile.
(c) It is less than ‘ Q ’ of nuclear reaction.
(d) It has to be equal to kinetic energy of a projectile.
62. Identify correct statements from the following:
A. Area of differential thermal analysis peak is proportional to amount of sample.
B. Area of differential thermogravimetric analysis curve is proportional to mass loss.
C. Phase transition cannot be studied with differential scanning calorimetry.
D. Simulatneous determination of two metal ions is possible with thermogravimetric analysis.
Answer is
(a) A, B and C (b) A, B and D (c) B, C and D (d) A, C and D
63. Consider following statements for fission of 235 U with thermal neutrons.
A. The % of nuclei undergoing unsymmetrical fission is maximum.
B. In each fission, one thermal neutron is produced.
C. Magnitude of energy released per fission is of the order 200 MeV
Correct statement(s) is/are
(a) A and B (b) A and C (c) B and C (d) C only
64. Addition of two electrons to the bismuth cluster Bi35 results in a change of structure type from
(a) closo to nido (b) nido to arachno (c) closo to arachno (d) arachno to hypho
65. Reaction of Na  Mn  CO 5  with H 2 C  CHCH 2 Cl gives A along with NaCl. Photolysis of com-
pound A results in compound B together with elimination of CO. the correct structural formulations
of compounds A and B are respectively,
CO CO CO CO
CO CO CO
CO
OC Mn CO OC Mn OC Mn CO OC Mn CO
(a) OC CO (b) OC OC
A B A B
CO CO CO CO
CO CO CO
CO CO CO
Mn Mn OC Mn OC Mn CO Mn Mn
(c) CO CO (d) OC CO
CO CO CO CO
A B A B
66. A copper(II) complex having distorted octahedral geometry shows an absorption band at 625 nm.
Given spin-orbit coupling of the complex as –625 cm–1, the  eff (in B.M.) is
(a) 1.73 (b) 1.81 (c) 1.63 (d) 1.93
67. Match items in column A with items in column B:
Column A Column B
+ 
I: SbF5  BrF3   BrF2   SbF6  A. Lewis acid behaviour of BrF3
II:  BrF2 SbF6   Ag  BrF4  
B. Lewis base behaviour of BrF3
Ag SbF6   2BrF3

III: KF  BrF3  K +   BrF4  C. Self ionisation
+ 
IV: 2BrF3   BrF2    BrF4  D. Neutralisation

(a) I-(A); II-(B); III-(C); IV-(D) (b) I-(B); II-(D); III-(C); IV-(A)
(c) I-(C); II-(D); III-(B); IV-(A) (d) I-(B); II-(D); III-(A); IV-(C)
68.
Mössbauer spectrum of complex  Fe 1, 10  phenanthroline  2  NCS  2  shows two lines at 300 K,
four lines at 186 K, and again two lines at 77 K. This can be attributed to
A. change in the coordination mode of NCS
B. change in the spin-state of iron
C. cis-trans isomerisation
D. change in metal-ligand bond distances
The correct statements are
(a) A and B (b) B and C (c) A and C (d) B and D
69.  R 3Ge 2 on photolysis gives a radical which shows ESR spectrum. The ESR signals carrying the
73
signature of Ge  I  9/2  are in terms of
(a) Nine lines (b) Ten lines (c) Two lines (d) One line
+
70. Mass fragment of  IrCl in mass spectrometry shows three mass peaks at m/z = 226, 228, and 230.
Given that natural abundances of 191Ir, 193 Ir, 35 Cl and 37 Cl are 37%, 63%, 76%, and 24% respec-
tively, the intensities of the mass peaks are in the order
(a) 49.5 : 100 : 26.6 (b) 100: 49.5: 26.6 (c) 26.6: 100: 49.5 (d) 26.6: 49.5: 100
71. The 31
P  1 H NMR spectrum of 2,2,6,6-N 4 P4 Cl4  NMe2  4 is expected to show
(a) two triplets (b) two doublets
(c) one doublet and one triplet (d) one quartet and one doublet
2
72. The number of bonding molecular orbitals and the number of available skeletal electrons in  B6 H 6  ,
respectively, are
(a) 7 and 14 (b) 6 and 12 (c) 18 and 12 (d) 11 and 14
73. The compound N 2 F2 has two isomers. Choose the correct option from the following:
(a) both isomers possess  v plane
(b) both isomers possess h plane
(c) one isomer has h plane while the other has a  v plane
(d) none of them have a h plane
74. Consider the following statements for metallothioneins:

A. the contain about 30% cysteine residues
B. they prefer to bind soft metal ions such as Cd(II), Hg(II) and Zn(II)
C. they are involved in electron transfer reactions
D. they are low molecular weight proteins
Correct statements are
(a) A, B and C (b) A, B and D (c) A, C and D (d) B and C
75. Consider the following statements for deoxy-hemerythrin and deoxy-hemocyanin:
A. they are involved in O2 transport in biological systems
B. they contain two metal ions in their active site
C. active site metal centres are bridged by amino acid residues
D. they prefer to bind only one O2 per active site
(a) A, B and D (b) A, C and D (c) B, C and D (d) A and C
3 3
76. Consider the following statements for octahedral complexes, (a)  CrF6  , (b)  Cr  ox 3  and (c)
3+
 Cr  en 3  :
A. their dd transitions are at 14900, 17500, and 21800 cm–1, respectively
B. their spin-only magnetic moments are same
C. two of them have optical isomers
D. all of them show Jahn-Teller distortion
(a) A, B, and C (b) A, C, and D (c) B, C, and D (d) B and D

77. Addition of NaBH 4 to  5  Cp  Fe  6  C 6 H 6   will give

  (b)    Cp  Fe  H     C 6 H 6  
5 6
(a)  5  Cp Fe  H  2 
(c)    Cp  Fe    C6 H 6   (d)    Cp  Fe    C6 H 7  

5 6 5 6
78. The  eff of  Fe  S2 CNEt 2 3  changes with temperature with the involvement of two electronic
states. The states are
(a) low spin 2 T2g and high-spin 6 A1g . (b) low spin 1 A1g and high-spin 3 T2g
(c) low spin 2 E g and high-spin 6 A1g . (d) low spin 2 T2g and high-spin 4 T1g .
79. Match the items in the three columns.
Absorption max
Complex (column 1) Color (column 2)
( max , nm) (column 3)
A.  Ni  H 2O  6   NO3  2 I. Blue X. 675
B.  Ni  NH3 6   NO3  2 II. Green Y. 565
C.  Ni  en 3   NO3  2 III. Violet Z. 615

(a) A-II-X; B-I-Z; C-III-Y (b) A-I-X; B-II-Y; C-III-Z
(c) A-III-Y; B-I-Z; C-II-X (d) A-I-X; B-II-Z; C-III-Y
80. Identify the product in the reaction between
Ph3P CO
Ir
2
Cl PPh3 and CH 3 I going at room temperature via SN mechanism
CH3 CH3 CH3 CH3
Ph3P CO Ph3P I Ph3P I Ph3P CO
Ir Ir Ir Ir
(a)
Cl
I
(b)
PPh3 Cl
CO
PPh
(c)
OC
Cl
PPh
(d)
Ph P
3 3 3
I
Cl
81. The major products A and B formed in the following reactions sequence are
Ph3P
CBr4 i. n-BuLi (2 equiv.)
CHO Zn THF, -78 ºC
Ph A B
ii. CO2
iii. H3O+
Br CO2H
(a) A = Ph B=
Br Ph
Br CO2H
(b) A = Ph B = Ph
(c) A = Ph B = Ph
Br CO2H
Br CO2H
(d) A = Ph B = Ph
Br CO2H
82. The intermediate A and product B formed in the following reaction sequence are
O
SH N
n-Bu3SnD
AlBN
CO2H A B
DCC, DMAP C6H6, reflux
H C6H6, reflux
O O
(a) A = B=
S D
H N H
O
O
(b) A = B= D
S
H N H
O
D O
O
O
(c) A = B=
O N
H H
S
O
(d) A = B= D
O N
H H
S
83. The major products A and B formed in the following reaction sequence are
1. N
O O
H
A
AlCl3
CH Cl
B
O 2. CH2N2Et2O 2 2
MeO2C
MeO2C
(a) A = N B= O N
O
MeO2C
MeO2C
(b) A = N B= O N
O
MeO2C
H H
(c) A = MeO2C N B=
O O N
MeO2C
(d) A = MeO C N B= O
2 N
O
O
O O i NaH 0 ºC F3C OH
A B
t-BuO CO2Me CH2Cl2
ii Br THF, RT
O
O O O
(a) A = t-BuO B=
CO2Me CO2Me
HO O
O
O O O
t-BuO
(b) A = t-BuO B=
CO2Me CO2Me
O
O
O O
(c) A = t-BuO B = HO2C CO2H

CO2Me
O
O
O O O O
t-BuO O
(d) A = B=
Br
CO2Me CO2Me
OH

H
1. NaH, CS2, Mel
2. n-dodecane heat
H
OH
H H H
H
(a) (b) (c) (d)

H H H
86. The correct combination of reagents to effect the following reaction is

HO
CHO
OH OH
(a) A. POCl3 , pyridine; B. AgOAc ; C. LiAlH 4

(b) A. NaBH 4 ; B. Ph 3 P, DEAD, PhCO2 H
(c) A. Ph 3 P, DEAD, PhCO2 H ; B. LiAlH 4
(d) A. PCC ; B. L-selectride
CO2Et i. O3
Ph
AlCl3 ii. NaBH4
A B
CH2Cl2, 0 ºC iii. H3O+
OH
Ph Ph
(a) A = B=
H H
CO2Et
O O
H Ph
Ph
HO
(b) A = B= H H
H CO2Et O
O
OH
Ph Ph
(c) A = B=
H H
CO2Et
O O
OH Ph
(d) A = CO2Et B=
O O
Ph
88. The correct combination of reagents A and B to effect following transformations are
H OH
B A
H OH
OH H
OH H
(a) A  cat. OsO 4 , NMO; B = i. I 2 , PhCO2 Ag, ii. aq. NaOH

(b) A  alkaline KMnO4 ; B = i. I2 , PhCO2 Ag, H 2 O, ii. aq. NaOH
(c) A = I2 , PhCO 2 Ag, ii. aq. NaOH; B = cat. OsO 4 , TMEDA, NMO
(d) A = i. m-CPBA, ii. aq. NaOH; B = alkaline KMnO 4
(i-PrO)4Ti
L-(+)-DET t-BuSH
O t-BuOOH NaOH
OH A B
CH2Cl2, -20 ºC
Mol. Sieves 4 Å
OH
O
(a) A = O B= O
OH OH
SBu-t
OH
O
(b) A = O
OH
B= O
OH
SBu-t
OH
O
(c) A = O B= O
OH SBu-t
OH
OH
O
(d) A = O
OH
B= O
SBu-t
OH
OMe
DDQ
O (1 equiv.) Phl(OAc)2
A B
www.careerendeavour.com MeOH
OH O
(a) A = B=
OMe
OH O
(b) A = B=
OMe
O
OH O
(c) A = B=
OMe
O O
(d) A = B=
OAc
91. The specific rotation  D for (S)–(+)–2–butanol is 10º mL/g dm. The observed optical rotation
  obs  of a sample composed of a mixture of (R)- and (S)-2-butanol is –0.45º. If the cell path length
is 0.6 dm and the concentration of 2-butanol in the sample is 0.15 g/mL, the percentages of (R) and
(S) enantiomers in the sample are
(a) (R) = 25%, (S) = 75% (b) (R) = 40%, (S) = 60%
(c) (R) = 60%, (S) = 40% (d) (R) = 75%, (S) = 25%
1. i. Mg, ii. CO2, iii. H3O+
2. (COCl)2
CH2Br 3. Et3N
Cl
Cl
(a) (b) O (c) O (d)

O
O O
O
93. Following reaction involves

O
OH CHO
H N N
N
p-TSA N
C6H6, reflux
(a) Claisen followed by Mannich reaction (b) aza-Cope followed by Mannich reaction
(c) Claisen followed by aza-aldol reaction (d) aza-Cope followed by aza-aldol reaction
94. The intermediate A and the major product B formed in the following reaction is
Pd(OAc)2
I Ph3P
Ag CO
[A]
2
B
3
PdLn
H H
(a) A = B=
H PdLn
(b) A = B=
PdLn
H H
(c) A = B=
PdLn
H
(d) A = B=

O O
i. Bu2BOTf
N Et3N
ii. PhCHO
iii. LiOH, H2O2
H2O
O OH O OH O OH O OH
(a) HO Ph (b) HO Ph (c) HO Ph (d) HO Ph

COOMe O 175 ºC
N +
Me OTBDMS toluene
Ph (sealed tube)
O OTBDMS O OTBDMS
Me Me
(a) MeOOC N (b) MeOOC N
Ph Ph
O OTBDMS O OTBDMS
Me Me
(c) N COOMe (d) N COOMe
Ph
Ph
97. The most stable conformation for the following compound is

HO
OH
OH HO
OH
(a) (b)
OH
OH OH
HO OH
• •
(c) (d)
H
H H H
98. The correct structure of the compound based on the following characteristic spectral data is
IR: 1736 cm–1
1H NMR:  3.59 (s, 3H), 3.32 (t, 2H), 2.25 (t, 2H), 1.85-1.75 (m, 2H), 1.73-1.62 (m, 2H)
13
C NMR:  174.0, 51.0, 32.9, 32.9, 32.8, 31.0, 23.0
O O
(a) Br (b) Br
OEt O
O Br O
(c) (d)
Br OMe OMe
99. The major product formed in the reaction of D-glucose with ZnCl2 in MeOH is a methyl
glucopyranoside (A or B). The structure of this product and the molecular orbital interaction present
between ring-oxygen and the anomeric C-O bond responsible for its stability, respectively, are
HO HO
O O
HO HO
OMe
HO HO
OH
OH OMe
A B
(a) A and n   (b) A and n   (c) B and n   (d) B and n  
100. Among the following correct statement for nucleic acids is
(a) Uracil is present in DNA
(b) Uracil is present in RNA
(c) Phosphorylation in RNA is at 2’ and 5’ positions
(d) Normally three hydrogen bonds stabilize A-T base pair
101. The figure below depicts an adsorption isotherm of O2 on charcoal at 90 K.
200
v(cm3/g)
100
0 200 400
P/torr
At a pressure 25 torr, only 10% of charcoal sites are occupied by O2. Therefore, the ratio of adsorp-
tion to desorption rate constants (in torr–1) is close to
(a) 0.003 (b) 0.004 (c) 0.006 (d) 0.015
102. Polonium is the only metal known to exist in a simple cubic lattice form. The density of polonium at
0ºC is measured to be 10.00 g/cm3. The atomic radius of polonium would then be (assume the mass
of a polonium atom = 2.7 × 10–22 g)
(a) 1.1 Å (b) 1.9 Å (c) 1.5 Å (d) 2.3 Å
103. The specific conductance of a solution is 0.176  1cm 1 . If the cell constant is 0.255 cm–1, the
conductance   1  of that solution is

(a) 1.449 (b) 0.690 (c) 0.045 (d) 0.431
104. Photochemical decomposition of HI takes place with the following mechanism

HI + hv (I a )   H+I
k1
H + HI  H 2  I
k2
I + I + M   I2  M
Considering hydrogen (H) and iodine (I) atoms as intermediates, the rate of removal of HI is
(a) I a /2 (b) Ia (c) 2Ia (d) I 2a
105. In an enzyme-catalysed reaction

k k2

1 
E + S  ES   E+P
k1
k2  3.42  104 s 1 . If  E 0  1  10 mol dm , the magnitude of maximum velocity and turn over
2 3
number using Michaelis-Menten kinetics are

(a) 3.42  102 mol dm 3s 1 ; 3.42  104 s 1 (b) 3.42  106 mol dm 3s 1 ; 3.42  10 4 s 1
(c) 3.42  104 mol dm 3s 1 ; 3.42  106 s 1 (d) 3.42  104 mol dm 3s 1 ; 3.42  102 s 1
106. Arrhenius equations for two chemical reactions are: k1  A1e  E1 / RT , k2  A2 e  E2 / RT . If E1  E2 , then at
a given temperature T,
k1 A1 k 2 A2
(a) k  A (b) k  A (c) k1k2  A1 A2 (d) k1  k2  A1  A2
2 2 1 1
107. The fugacity of a real gas is less than the pressure (P) of an ideal gas at the same temperature (T) only
when (Tb is the Boyle temperature of the real gas)
(a) high P, T  Tb (b) low P, T  Tb (c) high P, T  Tb (d) low P, T  Tb
1
108. For the reaction H 2 O  g   H 2  g   O 2  g  , the equilibrium constant K p depends on the degree
2
of dissociation     1 and total pressure P as
(a) K p   2 P www.careerendeavour.com
(b) K   Pp
3/2 1/2
(c) K   P (d) K p
1/2 3/2
p  P 2
109. The minimum work required by an engine to transfer 5 J of heat from a reservoir at 100 K to one at
300 K is
(a) 5 J (b) 10 J (c) 15 J (d) 20 J
110. The correct relation involving symmetry operations
(a) S 42  S2 (b)   xz    yz   C2  x 
(c) S 43  C43 (d) S 63  S2
111. A polydisperse polymer sample has ten molecules of molar mass 20,000 g mol–1 and fifteen mol-
ecules of molar mass 10,000 g mol–1. The number-average molar mass  g mol1   M n  of the sample
is
(a) 13,000 (b) 14,000 (c) 15,000 (d) 16,000
112. Consider a system of three particles which can occupy energy levels with energy 0,  and 2, such
1
that the total energy E  4 . Cases A, B and C correspond to spin fermions, spin 0 bosons, and
2
classically distinguishable particles, respectively. The correct ordering of entropy is
(a) S A  S B  SC (b) S B  S A  SC (c) SC  S B  S A (d) SC  S A  S B
113. For a point group, an incomplete character table is given below with one irreducible representation
missing
E 2C3 3 v
A1 1 1 1
   
E 2 1 0
The Mulliken symbol and characters of the missing representation are
(a) A1 1  1 1 (b) B1 1  1  1 (c) A2 1 1  1 (d) B2 1  1 1
114. Given below is a specific vibrational mode of BCl3 with  and denoting movements of the
respective atoms above and below the plane of the molecule respectively. The irreducible represen-
tation of the vibrational mode and its IR / Raman activity are
D3h E 2C3 3C2 b 2 S3 3v

A1 1 1 1 1 1 1 x2  y 2 , z2
A2 1 1 1 1 1 1 Rz
E 2 1 0 2 1 0  x, y  x 2
 y 2 , xy 
A1 1 1 1 1 1 1
A2 1 1 1 1 1 1 z
E  2 1 0 2 1 0  Rx , Ry   xz , yz 
Cl
B
Cl Cl
(a) A2 ; neither IR nor Raman active (b) E  ; both IR and Raman active
(c) A1 ; Raman active (d) A2 ; IR active
115. The first excited state  2

P1/ 2  of fluorine lies at an energy of 400 cm–1 above the ground state  2
P3/2  .
The fraction of Fluorine atoms in the first excited state at k BT  420 cm 1 is close to
1 1 1 1
(a) (b) (c) (d)
1 e 2e 1  4e 1  2e
116. The two limiting wavefunctions of the ground state of H +2 molecular ion, as the internuclear separa-
tion R goes to (i)  (infinity) and (ii) 0 (zero) are (1s a , 1sb are 1s-orbital wave functions of hydrogen
atoms a and b in H +2 , and 1s He is the wave function of the 1s orbital of He  )
(a) (i) 1sa  r  ; (ii) 1sb  r  (b) (i) 1sb  r  ; (ii) 1sa  r 
(c) (i) 1sa  r1 1sb  r2  ; (ii) 1s He  r1 1s He  r2  (d) (i) 1sa  r   1s b  r  ; (ii) 1s He  r 
117. For a certain magnetic field strength, a free proton spin transition occurs at 700 MHz. Keeping the
magnetic field strength constant the 14

N nucleus will resonate at g  p   5.6 and g  N   0.4
14

(a) 700 MHz (b) 400 MHz (c) 200 MHz (d) 50 MHz
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 most likely reason for the Stokes shift is
(a) large change in molecular geometry in the excited state
(b) increase in dipole moment of the molecule in the excited state
(c) decrease in polarizability of the molecule in the excited state
(d) lowered interaction of the excited molecule with polar solvent
119. The un-normalized radial wave function of a certain hydrogen atom eigenstate is  6r  r 2  exp  r /3 .
A possible angular part of the eigenstate is
(a) 5 cos 3   3cos  (b) 3cos 2   1 (c) cos  (d) 1
120. Given a trial wave function  t  C11  C2 2 , and the Hamiltonian matrix elements,  1* H 1dv  0 ,
* *
  H  dv  2.5 ,   H  dv  12.0 , the variationally determined ground state energy is
1 2 2 2
(a) –0.52 (b) –0.50 (c) 12.50 (d) 12.52

20 SOLVED PAPER : CSIR-UGC-NET/JRF June 2017
SOLVED PAPER : CSIR-UGC-NET/JRF June 2017

PART–B
21. 2, 8, 20, 28, 50, 82 and 126 are magic number.
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.
23. The species having same number of electrons are called isoelectronic.
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 
24. Two fragments are isolobal if the number, symmetry properties, approximate energy and shape of
their frontier molecular orbitals and the number of electrons in them are similar not identical but
similar.
CH 3  4  3  1  6 ;  Cr  CO 5   6  10  16
+3 +2 +1 0 –1 –2 –3
25. Eu 3  f 6
L = 6–3 = 3 J = |L–S| = 0
S=3
Hence, µ  g J  J  1  0
 
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)
SOLVED PAPER : CSIR-UGC-NET/JRF June 2017 21
F –
••
F F
27. [XeF5]– Xe
F •• F
Shape = Pentagonal planar
F
F F
[BrF5] Br
F •• F
Shape = square pyramidal


28. K  graphite   graphite K 

H2SO4  graphite   graphite HSO4
29. In oxyhemerythrin  O O  850 cm1
In oxyhemoglobin  O O  1100 cm 1
30. In CdS, HgS and BiI3 colour is due to LMCT as 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 3 d   2.00
3
Ni 2 d   2.00
8
32. NR2  Dithiocarbamate

OR  Xanthate
O–  Dithiocarbonate
SR  Thioxanthate
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
34. S
D3C CD3
13
C NMR n = 3; I = 1 (for D)
Multiplicity = 2nI + 1 = 2×3×1 + 1 = 6 + 1 = 7 (septet)
35. [2, 3] S.T.R.

1 3
2
S S S S
1
I 2
t-BuOK H
H C C
36.
acetyl anion
H3C CH NO2 H3C CH NO2
Base
H www.careerendeavour.com
Nitroethane
Hence, nitroethane anion is synthetic equivalent of acetyl anion.

S
S

37.
[8+2]
S
S cyclo-addition
CN
NC CN CN
NC CN
NC CN

O OH
HO
38.
H+ ring Ring
O
expansion Contraction
H
O
F H
39. Most stable due to intramolecular hydrogen bonding
H H
H
9 H
B
8 1
7 2
40.
9-borabicyclo [3, 3, 1] nonane
5 4
6 3
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
Gernyl pyrophosphate is the biosynthetic precursor of (+)–menthol.

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)
OH
OH
O
H
43.
Cortisone
H H
H H
Li, liq. NH3

(Birch reduction)
44.
N N
H
• •
e– +H+ e–
N www.careerendeavour.com
N N
H
H+
N N
H
H
O CO2Et O
O Ph
+ Cl CO2Et
Ph Ph Cl CO2Et
45. Ph
Ph Ph
Darzen's glycidic ester
synthesis
hv •
46. NBS + HBr Br2 2Br
(Limited supply)
H H Br
•
• Br Br
+ Br
–Br • + Br•
– HBr
Br Below the •
Br Br Br
plane attack •
•
+ Br
Trans-1, 2-dibromoacenaphthene

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   www.careerendeavour.com
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 
1   
 sin 2     
4 2 4
d ix
48. e  i eix therefore, eigen function
dx
d 2 ix 2 ix
e  i e therefore, eigen function
dx 2
49. In one component system 4 phases carnot simultaneously exist at single point.
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
51. For any cyclic process cyclic integral of state function is zero.
So,  dU  0 as U is a state function
a 40 1
52. 2 sin   n  2    1 
2 2 2
h k  5 2
  18 nm

 a
53. k  Ae RT at very high temperature T  

 a A
k Ae 
R  k  A e 0  k    k  A
e0
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
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

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
58. Greater the surface tension, the greater the surface concentration.
M
59. P.D.I. = M  1 (for monodisperse)
n
 Mw  Mn
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.
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
62. Correct statement are
• Area of different thermal analysis peak is proportional to amount of sample
• 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)
64. Bi35  5  5  3  22
Hence, (4n + 2), closo
On addition of 2 electron it become (4n + 4), nido
65. Na  Mn  CO 5   CH 2  CH  CH 2  Cl 
Mechanism:
CO CO
OC CO OC CO
– Mn NaCl –CO Mn
[Mn(CO)5] + CH2 = CH – CH2 – Cl CO + CO
OC hv OC
(A) upon heating 1 allyl converted into 3

(B)
allylwith evolution of
CO gas
  
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
 
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
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*)
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
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
www.careerendeavour.com 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
Me2N (a) Cl
P
NMe2
N
N P
Cl (b)
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 
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 
73. N2F2 has two isomers,
F
N N N N
F F F
1C2 + 2v 1C2 + 1h

74. Metallothioneins are cystein rich, low molecular weight protein. Due to soft sulfur centre they prefer
to bind.
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.
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.
+ H 
77.  
Fe 5  C5 H5  
5

 C6 H 7 

H
NaBH4
Fe Fe

 Fe 5  C6 H 6 5  C5 H5 
  
78. In  Fe  S2CNEt 2 3  oxidation state of Fe = +3
Fe3+ (low spin) ; Fe3+ (high spin)
2
T2g 6
A1g
 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 absorption 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
Mechanism:
CH3 CH3
••
Ph3P CO Ph3P CO Ph3P CO
CH3I
Ir Ir Ir
Cl PPh3 Cl PPh3 Cl PPh3
I
I
H
+
CHO Ph3P, CBr4, Zn 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
HS N O
82. DCC, DMAP
COOH + C
C6H6, reflux O
H H •
Bu3Sn
S
Bu3SnD, AlBN
+ D
–CO2
Bu3SnS
H
CH2N2
HO2C N
83. O O + N methylation
O H O
H
AlCl3
MeO2C ene reaction
EtO2C N
O
O
N
O O O O
O O
84.
t- BuO t- BuO t-BuO
Na+H– CO2Me
Br CO2Me
H
O
O
O O
H O H O O O
H H+
HO t-Bu O
OH2
CO2Me H CO2Me
HO O CO2Me O
O CO2Me
O O

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
OH
CHO CHO
Ph3P, DEAD, PhCO2H LiAlH4

86.
OH O C Ph OH
O
Ph HO
87. Ph Ph
(4+2) O3/NaBH4
+ Cycloaddition
EtO2C CO2Et HO CO2Et
OH OH
Ph
Ph H
H3O+
H H
H H
O O
O O
OH
(i) I2, PhCO2Ag, H2O (woodward reagent) KMnO4/OH–
88. (ii) Aq. NaOH OH
OH
OH
O H O
O L–(+)–DET O OH O
89. OH O O
epoxidation
below the plane Product (A) above the
plane attack
OH
OH t-Bu-S
O t-Bu-SH , NaOH O
S-tBu
O
Product (B) OH
OMe
O OH OAc
DDQ
1 equiv. + Ph I
90.
Deprotection of OAc
–OH group OAc
I
O O Ph
–PhI
–OAc –OAc
OMe
MeOH

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
 0.45
 T   www.careerendeavour.com
  C 0.6  0.15
 –5º
 mixt 5º
ee    100  50% excess of R
 pure 10º
50
R  50   75%
2
S  25%
(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
OH 3 2
93. N [3,3] S.T.R. N
Aza-cope reagent O H
1
H N O
1
C N 3 N
H 2 OH
O
N (Mannich reaction)
N
94.  Pd  PPh 3 4
Pd  OAc  2  PPh 3 
Active form is Pd  PPh 3 2 or PdL2 (where L = PPh3)

This reaction is an example of intramolecule Heck reaction
(1) Oxidative Addition : www.careerendeavour.com
I
L2
I Pd
4 PdL2
3 1
2
(2) Olefin insertion (Syn addition):
L2 PdL2
I
H H
Pd 4 H
4
Olefinic insertion H  elimination
3 1 SYN addition 3 SYN
2 1
2
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
H2O2
HO Ph (Hydrolysis)
Me
O
CO2Me
CO2Me
175ºC
N
N OTBDMS
96.
Ph
Ph N CO2Me
Ph
(1, 3-Dipole)
O
OTBDMS
1, 3-Dipolar
Me
Cyclo-addition
CO2Me
N
Ph
Hydrogen bonding
H H
O O
OH
97. OH
Highly unstable due to 1, 3- Twist boat
diaxial interaction, steric
hinderance and Gauche
interaction

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 
99. Anomeric effect present in compound (B)
OH n
••
HO
O 
interaction
HO
OH
OMe
100. In case of RNA-uracil is present. Inspite of thymine-DNA
 1 0.1 1
101. k     0.0044
1   P 1  0.1 25
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) www.careerendeavour.com

103. k  G
A
0.176 176
0.176  G  0.255  0.255  G  255  G
0.6901  1  G
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
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

k1
106.  e  E1 / RT ... (1)
A1
k2
 e E2 / RT ... (2)
A2
 2   k2  A1  e E1 E2 / RT
1 A2 k1
k2 A1 A k
1  1  1
k1 A2 A2 k2
107. Fugacity of gas is less than P when attractive forces are dominant. It happens at low P and when
T < T 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
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
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 
110. S63  C63   3  C '2  a  S 2
10  20000  15  10000
111. Mn   14, 000
10  15
112.   no. of arrangements Cclassical   no. of arrangements  Afermions   no. of arrangements bosons
B
 SC  S A  S B
113. Character table of C3V points group and complete table is
E 2C3 3 v
A1 1 1 1
A2 1 1 1
E 2 1 0
114. The given vibrational is not symmetric w.r.t.  h
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
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    1sa  r   1s b  r 
He  : r  0  1s He  r 
vp g  p 700 MHz 5.6 700 MHz  0.4

117.     vN   50 MHz
vN g N  vN 0.4 5.6
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.  2
From radial part 6r  r exp  3
Minimum power of r1  1
So,   1
Corresponding   1 possible angular part of eigen state is cos 
For cos  ,   1
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

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PAPER : CSIR-UGC-NET/JRF Dec.

PAPER : CSIR-UGC-NET/JRF Dec. 2016

28. The nephelauxetic parameter  is highest for

(a) OCl (b) F (c) Cl (d) NO 2

(A) (B) (C)

(a) compound is chiral and has P configuration

40. Methyl groups in the following compound are

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

43. The major product formed in the dinitration of 4-bromotoluene is

NO2 NO2 NO2

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

(a) four (b) six (c) eight (d) ten

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

49. The major product in the following reaction is

50. The major product formed in the following reaction is

and C, Cov  x, y  will be zero only when

68. Mark-Houwink equation     KM a  is used for the determination of

The correct answer is

The correct match is

(a) CH, BH and Mn(CO)5 (b) P, CH and Ni  5 -C5 H 5 

97. The correct statement for the reactants A, B to give products C, D is

100. The compound that exhibits following spectral data is

6.8  d, J  8.0 Hz, 2H  , 5.8  d, J  12.3 Hz, 1H  , 3.8  s, 3H  , 3.0  s, 6H  ppm

101. The major product in the following reaction is

102. The major product formed in the following reaction is

103. The major product formed in the following reaction is

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

104. The major product formed in the following reaction is

105. Correct sequence of reagents for the following conversion is

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

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

114. The major product formed in the following reaction is

Cbz Cbz Cbz Cbz

(i) + 2K (P) aromatic

116. The correct starting compound A in the following reaction is

(c) BnO (d) BnO

117. The major product formed in the following reaction is

(a) N (b) N (c) Cl (d)

118. The major product formed in the following reaction is

119. The major product formed in the following reaction is

121. A constant of motion of hydrogen atom in the presence of spin-orbit coupling is

123. If we write a normalized wavefunction   Â , then  is also normalized when

(a) not allowed (b) allowed with x polarisation

137. A reaction goes through the following elementary steps

(a) 4B (b) 8B (c) 10B (d) 12B

Species Mass  g / mol  Diameter  nm 

(a) 4/5 (b) 5/5 (c) 5/3 (d) 3/5

141. Given, www.careerendeavour.com

The A, B and C represent

SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2016

Hence, total number of signal is 3.

25. T.V.E. = 8×2 + 5×2 + 2×2 + 4 = 34 = A

1  e tirr    saturation factor

35. Ruberdoxin cysteine 2-iron ferredoxin Fe2S2

36. LaI2 exists as La 3  2I   e  

Helical chirality, P-configurations. Since, clockwise path from front side.

Correct option is (a)

Ortho NO2 NO2

ortho, para When m-directing group is meta to the