Csir Net JRF: Chemical Sciences Question Papers With Detailed Solutions

CSIR NET JRF
Chemical Sciences
Question Papers with
Detailed Solutions
June 2011 – Dec. 2018

Content
QUESTION PAPERS
1. CSIR UGC NET JRF June 2011.
2. CSIR UGC NET JRF December 2011.
18. CSIR UGC NET JRF December 2019
DETAILED SOLUTIONS
18. CSIR UGC NET JRF December 2019
QUESTION
PAPERS
June 11 - Dec 18
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
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
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
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
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
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
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

1
PART A
1. A boy holds one end of a rope of length l and the other end is fixed to a thin pole of radius r (r << l). Keeping
the rope taut, the boy goes around the pole causing the rope to get wound around the pole. Each round takes
10 s. What is the speed (in units of s–1) with which the boy approaches the pole?
r l 20  l  r 
(a) (b) (c) 20  r  l  (d)
5 5 5
2. The smallest square floor which can be completely paved with tiles of size 8 × 6, without breaking any tile,
needs n tiles. Find n.
(a) 56 (b) 12 (c) 24 (d) 48
3. A 2 m long ladder is to reach a wall of height 1.75 m. The largest possible horizontal distance of the ladder from
the wall could be
(a) slightly less than 1 m (b) slightly more than 1 m
(c) 1 m (d) 1.2 m
4. A rectangular flask of length 11 cm, width 8 cm and height 20 cm has water filled up to height 5 cm. If 21
spherical marbles of radius 1 cm each are dropped in the flask, what would be the rise in water level?
(a) 8.8 cm (b) 10 cm (c) 1 cm (d) 0 cm
5. Contours in the bivariate (weight, height) graph connect regions of approximately equal populations. Which of
the following interpretations is correct?
Population
Short (Height) Tall

Light (Weight) Heavy
Population
ax
M
(a) There is no correlation between height and weight of the population

(b) Heavier individuals are likely to be taller than lighter individuals
(c) Taller and lighter individuals are more in number than taller heavier individuals
(d) There are no individuals of medium weight and medium height
6. A path between points P1 and P10 on a level ground is shown, and positions of a moving object at 1 second
intervals are marked. Which of the following statements is correct?
P1
P2
P6
P5 P7
P3 P4
P8
P10
P9
South Delhi : 28-A/11, Jia Sarai, Near-IIT Hauz Khas, New Delhi-16, Ph : 011-26851008, 26861009
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2
(a) The motion is uniform
(b) The speed between P3 and P4 is greater than that between P5 and P6
(c) The speed of P1 to P2 increases because of downward slope
(d) The section P3 to P4 is covered at the slowest speed
7. A new type can be used for at most 90 km. What is the maximum distance (in km) that can be covered by a
three wheeled vehicle carrying one spare wheel, all four tyres being new?
(a) 180 (b) 90 (c) 120 (d) 270
8. A plate of 5m  2m size with uniform thickness, weighing 20 kg, is perforated with 1000 holes of 5cm  2cm
size. What is the weight of teh plate (in kg) after perforation?
(a) 10 (b) 2 (c) 19.8 (d) 18
9. What is the maximum number of cylindrical pencils of 0.5 cm diameter that can be stood in a square shaped
stand of 5 cm × 5 cm inner cross section?
(a) 99 (b) 121 (c) 100 (d) 105
10. The sum of two numbers is equal to sum of square of 11 and cube of 9. The larger number is (5)2 less than
sqaure of 25. What is the value of the sum of twice of 24 percent of the smaller number and half of the larger
number?
(a) 415 (b) 400 (c) 410 (d) 420
11. What is the volume of soil in an open pit of size 2 m × 2 m × 10 cm?
(a) 40 m3 (b) 0.4 m3 (c) 0 m3 (d) 4.0 m3
12. For which values of A and B is sin A = cot B ?
  
(a) A = B = 0 (b) A = B = (c) A  0, B  (d) A  ,B  0
2 2 2
13. For which one of the following statements is the converse NOT true?
(a) If a patient dies even with excellent medical care, he likely had terminal illness.
(b) If a person gets employed, he has good qualifications.
(c) If an integer is even, it is divisible by two.
(d) If an integer is odd, it is not divisible by two.
14. Four small squares of side x are cut out of a square of side 12 cm to make a tray by folding the edges. What
is the value of x so that the tray has the maximum volume?
(a) 6 cm (b) 2 cm (c) 3 cm (d) 4 cm
15. Two runners A and B start runnign from diametrically opposite points on a circular track in the same direction.
If A runs at a constnat speed of 8 km/h and B at a constant speed of 6 km/h and A catches up with B in 30
minutes what is the length of the track?
(a) 1 km (b) 4 km (c) 3 km (d) 2 km
16. Three-quarters of a circle is shown in the figure; OA and OB are two radii perpendicular to each other. C is a
point on the circle.
O A
C ?
B
What is angle ACB?
(a) Cannot be determined (b) 30°
(c) 60° (d) 45°
3
17. If a plant with green leaves is kept in a dark room with only green light ON, which one of the following would
we observe?
(a) The plant appears brighter than the surroundings
(b) The plant appears darker than the surroundings
(c) We cannot distinguish the plant from the surroundings
(d) It will have above normal photosynthetic activity
18. A person purchases two chains from a jeweller, one weighing 18 g made of 22 carat gold and another weighing
22 g made of 18 carat gold. Which one of the following statements is correct?
2
(a) 22 carat chain contains times more gold than 18 carat chain
11
1
(b) 22 carat cahin contains times more gold than 18 carat chain
11
(c) Both chains contain the same quantity of gold
2
(d) 18 carat chain contains times more gold than 22 carat chain
11
19. Find the missing pattern
21 7 4 20 U G D T O E BH
x A
?
3 5 C E 1 F
A 1 1 x 26 *
(a) 5 15 8 2 (b) 15 5 2 8 (c) 50 10 2 12 (d) 8 6 5 15

+ + × ×
10 6 10 6 5 6 2 10
26 Z Z 26 A 1 Z 26
20. There are small and alrge bacteria of the same species. If S is surface area and V is volume, then which of the
following is correct?
(a) Ssmall  Slarge (b) Vsmall  Vlarge
(c)  S / V small   S / V large (d)  S / V small   S / V large
PART B
21. Among the following nuclear reactions of thermal neutrons, the cross section is highest for
235
(a) 92 U
235
 0 n1  92 U235  0n1 (b) 92 U  0 n1  92 U 236
235
(c) 92 U  0 n1 92 Th 232  2He 4 (d) 92 U
235
 0n1  36Kr 94  56 Ba
140
 2 0 n1
22. Spectrophotometric monitoring is not suitable to determine the end point of titration of
(a) oxalic acid vs potassium permanganate (b) iron(II) vs 1, 10-phenanathroline
(c) cobalt(II) vs eriochrome black T (d) nickel (II) vs dimethylglyoxime
23. The first ionization energy is the lowest for
(a) Br (b) Se (c) P (d) As
24. Among ClO3 , XeO3 and SO3 , species with pyramidal shape is/are?
(a) ClO3 and X e O3 (b) Xe O3 and SO3 (c) ClO3 and SO3 (d) SO3
4
25. The role of BF3 as an industrial plymerization catalyst is to generate
(a) carbanion (b) carbocation (c) organic radical (d) cation radical
26. For the following complexes, the increasing order of magnetic moment (spin only value) is
A.  TiF6 3 B.  CrF6 3 C.  MnF6 3 D.  CoF6 3
(a) D < A < B < C (b) C < A < D < B (c) B  A  D  C (d) A  B  C  D
27. The correct statement for cytochrome c is
(a) It is a non-heme protein
(b) The coordination numer of iron in cytochrome c is five
(c) It is a redox protein and an electron carrier
(d) It can store or carry dioxygen
28. Geometries of SNF3 and XeF2O2, respectively, are
(a) square planar and square planar (b) tetrahedral and tetrahedral
(c) square planar and trigonal bipyramidal (d) tetrahedral and trigonal bipyramidal
29. The IR spectrum of Co(CO)4H shows bands at 1221, 2062, 2043 and 1934 cm–1. The VCo - D (in cm–1)
expected in the spectrum of Co(CO)4D is
(a) 2111 (b) 1396 (c) 2053 (d) 1910
30. In trigonal prismatic ligand field, the most stabilized d orbital is
(a) d z2 (b) d xy (c) d xz (d) d yz
31. The most unstable complex on the basis of electro-neutrality principle among the following is
3 3 3 3
(a)  Al  OH 2 6  (b)  Al  NH3 6  (c)  AlF6  (d)  Al  NCCH 3 6 
32. The band in the electronic spectrum of l2 appearing at 520 nm will undergo maximum blue shift in
(a) water (b) hexane (c) benzene (d) methanol
33. Mismatch among the following is
(a) Sharp transition and fluorescence in lanthanides (b) Broad bands and d-d transitions
(c) Very high spin-orbit coupling and transition elements
(d) Charge transfer and molar absorptivity of the order of 104 L mol–1 cm–1
34. Among the following, the compound that gives base peak at m/z 72 in the El mass spectrum is
O O
O O
(a) (b) (c) (d)
35. The following molecule has

H CO2H
HO2C H
(a) plane of symmetry (b) R configuration (c) S configuration (d) centre of symmetry
36. The following natural product Enterodiol is a
HO
OH
OH
HO
5
(a) terpene (b) steroid (c) lignan (d) alkaloid
37. The correct order of basicity for the following heterocycles is
N
N
N N N
H H H
A B C
(a) A > C > B (b) C > A > B (c) C > B > A (d) B > A > C
38. The kinetic product formed in the following reaction is
OH
conc. H2SO4
OH OH
(a) (b)
SO3H
SO3H
SO3H
OH OH
(c) (d)
HO3S
39. Among the structures given below, the one that corresponds to the most stable conformation of compound A
is
O
O
A
OH
O
(a) O (b) Me O OH
Me O
Me
Me
O
(c) O (d) O
O OH
OH
40. According to Frontier Moleculaor Orbital (FMO) Theory, the Highest Occupied Molecular Orbital (HOMO)
of hexatriene in the following reaction is
hv
6
(a) (b)
(c) (d)
41. The number of signals observed in the proton decoupled 13C NMR spectrum of the following compound is
(a) Five (b) Six (c) Ten (d) Thirteen

42. The correct order of stability of the following carbocations is
MeO
MeO
MeO
(A) (B) (C)

(a) A > C > B (b) B > C > A (c) C > A > B (d) C > B > A
43. An optically pure organic compound has specific rotation of +40°. The optical purity of the sample that exhibits
specific rotation of +32° is
(a) 8% (b) 12% (c) 20% (d) 80%
O O
KOH
MeOH
(a) (b) (c) (d)

O
O O
45. Correct match of the compounds in Column P with the IR stretching frequencies (cm–1) in Column Q is
Column P Column Q
O
I A 1865
II O B 1770
7
O O O
III C 1745
(a) I - B; II - C; III - A (b) I - C; II - A; III - B (c) I - C; II - B; III - A (d) I - A; II - C; III - B

46. The organic compound that displays following data is
1
HNMR (400 MHz):  7.38 (d), 7.25 (d), 1.29 (s) ppm
Br
Br
Br
(a) (b) (c) (d)
Br
47. The molecule with a C2 axis of symmetry among the following is
(a) BH2Cl (b) CH3Cl (c) NH2Cl (d) HOCl
48. The molecule that will show Raman spectrum, but not IR spectrum, among the following is
(a) H2 (b) HCl (c) BrCl (d) CS 2
49. Boron in BCl3 has
(a) sp hybridization (b) sp2 hybridization (c) sp3 hybridization (d) no hybridization
50. The number of degenerate spatial orbitals of a hydrogen-like atom with principal quantum number n = 6 is
(a) 12 (b) 6 (c) 72 (d) 36
51. If  Aˆ , Bˆ   0 and  Aˆ , Cˆ   0 , then which of the following necessarily holds:  Aˆ , Bˆ and Cˆ are operators 
(a)  Bˆ , Cˆ   0   0
(b)  Aˆ , BC   0
(c)  Bˆ , AC   0
(d) Cˆ , AB
  
52. The correct statement among the following is ( Â is a hermitian operator)

(a) The eigenvalues of  A2 can be negative.

(b) The eigenvalues of A2 are always positive

(c) No eigenvalues of  A is an eigenfuncation of A2 .

(d) The eigenvalues of A2 can be complex.
53. If the atoms/ions in the crystal are taken to be hard spheres touching each other in the unit cell, then the fraction
of volume occupied in the body centered cubic structure is
2  3
(a) 3 (b) (c) (d)
6 6 8
54. Repeated measurements of Pb in a lake water sample gave 3.2, 5.2 and 7.2 ppb of Pb. Standard deviation int
eh measurement of Pb is
2
(a) 2 ppb (b) 4 ppb (c) 0 ppb (d) 2 ppb
55. The stability of lyophobic colloids is a consequence of the
(a) electrical double layer at the surface of the particles.
(b) van der Waals force between the particles.
(c) small particle size.
(d) shape of the particles.
8
56. The equivalent conductance at infinite dilution of a strong electrolyte (0) can be obtained from the plot of
1
(a) vs. C (b)  vs. C (c)  vs. C2 (d)  vs.
C
57. The number-average molar mass  M n  for a monodisperse polymer is related to the weight-average molar
mass  M w  by the relation
Mw Mw
(a) M n  (b) M n  (c) M n  2M w (d) M n  M w
3 4
k1 k2
58. For a sequence of consecutive reactions, A   I   P the concentration of I would be, by steady
state approximation.
k1
(a) k1  A (b)  k1  k2   A (c) k1k 2  A (d) k  A
2
59. Enthalpy is equal to

(a) TS  PV   ui ni (b) TS   ui ni (c)  ui ni (d) PV   ui ni
60. The structure of ribonucleoside uridine is
O O
NH NH
(a) HO (b) HO
N O N O
O O
OH OH OH
NH NH
(c) HO (d) HO
O N O O N O
O O
OH OH OH
PART C
61. The peak area of differential thermal analysis curve is proportional to one or more of the following:
A. mass loss
B. mass of the sample
C. heat of decomposition/phase change
(a) A only (b) B only (c) A and C (d) B and C
62. To determine the bond parameters at 25°C, electron diffraction is generally unsuitable for both
(a) O3 and NO2 (b) Sulfur and dry ice (c) NO2 and sulfur (d) O3 and dry ice
9
63. Match lanthanides in Column I with their properties in Column II
Column I Column II
A. Lu (i) Reagent in oxidation state IV
B. Eu (ii) Ml2 of metallic lustre
C. Ce (iii) Diamagentic M(III)
D. Tb (iv) Pink in oxidation state III
Correct match is
(a) A-(iii), B-(ii); C-(i); D-(iv) (b) A-(ii), B-(iii); C-(iv); D-(i)
(c) A-(iv), B-(ii); C-(i); D-(iii) (d) A-(iii), B-(ii); C-(iv); D-(i)
64. Among the following species isolobal to CH2 are
A. CpCr(CO)2 B. CpCu C. Ni(CO)2 D. Cr(CO)4
E. Fe(CO)4
(a) A, C and E (b) B, C and D (c) B, C and E (d) A, B and D
65. Choose the incorrect statement for the phosphomolybdate anino, [PMO12O40]3–.
(a) It has a Keggin structure.
(b) Phosphorus is in +5 oxidation state.
(c) It is extremely basic.
(d) It forms crystalline precipitates with [R4N]+ (R = bulky alkyl or aryl group)
66. Consider the following statement(s) for actinides (An):
A. Oxidation states greater than +3 are more frequent in An compared to lathanides (Ln)
B. Some An(III) ions show d-d transitions
C. UO22+ and PuO22+ are stable
D. Some of actinides do not have radioactive isotopes
(a) A and C (b) B and D (c) A, B and C (d) B, C and D
67. According to Bent’s rule, for p-block elements, the correct combination of geometry around the central atom
and position of more electro-negative substituent is
(a) Trigonal bipyramidal and axial (b) Triogonal bipyramidal and equatorial
(c) Square pyramidal and axial (d) Square pyramidal and basal
68. Allred-Rochow electronegativity of an element is
A. directly proportional to the effective nuclear charge
B. directly proportional to the covalent radius
C. inversely proportional to the square of the covalent radius
D. directly proportional to the square of the effective nuclear charge
(a) A and B (b) A and C (c) B and C (d) A and D
69. Br2 with propanone forms a charge transfer complex and l2 forms triiodide anion with I–. This implies that
(a) both Br2 and I2 act as bases (b) both Br2 and I2 act as acids
(c) Br2 acts as an acid and I2 acts as a base (d) Br2 acts as a base and I2 acts an an acid
70. In the complex [Pd(L-L)(Me)(Ph)], the bisphosphine (L-L) that does not allow reductive elimination of PhMe,
is
10
Ph Ph
P Ph
P
P Ph
(a) (b)
P
(c) MeO (d)
MeO P
P P
Ph Ph Ph Ph
71. In the reaction given below, the bisphosphine (P-P) that is in effective for transfer hydrogenation reaction is
4CH3CN
CpRu(P–P) + N BF4 CD2Cl2
CpRu(P–P)(CH3CN)]+BF4- + N
Ph Ph
(a) Diphenylphosphinomethane (b) 1, 2-Diphenylphosphinoethane
(c) 1, 3-Diphenylphosphinopropane (d) 1, 4-Diphyenylphosphinobutane
6
72. For high spin and low spin d octahedral complexes (ML6), the generally observed spin allowed transitions,
respectively, are
(a) two and one (b) one and two (c) zero and one (d) two and two
73. The reactions given below,
A. Cl2 + 2H2O  HOCl + H3O+ + Cl–
B. Cl2 + 2NH3  NH2Cl + NH4 + Cl–
are examples of
(a) disproportionation only (b) disproportionation (A) and solvation (B)
(c) solvation (A) and disproportionation (B) (d) solvalysis as well as disproportionation
74. According to Wade’s rules, the cluster type and geometry of [Sn9]4-, respectively, are
(a) closo and tricapped trigonal prismatic (b) nido and monocapped square-antiprismatic
(c) arachno and heptagonal bipyramidal (d) closo and monocapped square antiprismatic
75. Assuming 1 J PH  1 J PB , the expected 31P NMR spectrum of H3P: 11BCl3 [for 11B, I = 3/2] is
11
(a) (b)
(c) (d)
76. The geometry around Cu and its spin state for K3CuF6 and KCuL2, [H2L = H2NCONHCONH2], respectively
are:
(a) (octahedral, high-spin) and (square planar, low-spin)
(b) (octahedral, low-spin) and (square planar, low-spin)
(c) (trigonal prismatic, high-spin) and (tetrahedral, high-spin)
(d) (trigonal prismatic, low-spin) and (tetrahedral, high-spin)
77. The active site structure for oxy-hemerythrin is:
O HO
(His)N N(His)
O
(a) Fe(III) Fe(III)
(His)N O O
N(His)
O O
C
Glu
Asp
O HO
(His)N N(His)
O
(b) Fe(II) Fe(III)
(His)N O O
N(His)
O O
C
Glu
Asp
O
H O N(His)
(His)N O
(c) (His)N Fe(III) Fe(III)
(His)N O O
N(His)
O O
C
Glu
Asp
12
O
H O N(His)
(His)N O
(d) (His)N Fe(II) Fe(III)
(His)N O O
N(His)
O O
C
Glu
Asp
78. Consider the following statements with respect to the base hydrolysis of [CoCl(NH3)5]2+ to [Co(NH3)5(OH)]2+.
A. One of the ammonia ligands acts as a Bronsted acid.
B. The entering group is water.
C. A heptacoordinated Co3+ species is an intermediate.
The correct statement(s) is/are
(a) A and B (b) A and C (c) B and C (d) C only
79. The number of inorganic sulfides in cubane like ferredoxin and their removal method, respectively, are
(a) eight and washing with an acid (b) four and washing with a base
(c) eight and washing with a base (d) four and washing with an acid
80. Considering the ambidentate behaviour of thiocyanante ion, the most stable structure among the following is
(a) PH P (b) PH P
Pd Pd
NCS SCN SCN NCS
(c) PH PH (d) PH P
Pd Pd
SCN NCS NCS SCN
81. Major product of the following reaction is
O
1. LDA, TBDMSCl
2. CO2Me
heat
then H2O
13
(a) HO2C (b) HO2C

CO2Me CO2Me
CO2Me CO2Me
(c) HO2C (d) HO2C
82. Major product in the following reaction is
1. NH2OH
2. AcCl
(a) CN (b) CN
(c) CN (d) CN
83. Major products A and B of the following reaction sequence are

O
1. TsNHNH2, AcOH H2, Pd/CaCO3

O A B
2. base Pb(OAc)2
O O
O
(a) A = B= (b) A = B=
O
O O O
O
(c) A = B= (d) A = B=
14
CH2Cl2/MeLi
N
H
Cl
Cl
(a) (b) (c) (d)
N N N
N
Cl
85. Major products A and B of the following reaction sequence are
CO2H l2 DBU
A B
NaHCO3
(a) A = O B= O
O O
H H
(b) A = O B= O
O O
H H
(c) A = O B= O
O O
H H
(d) A = O B= O
O O
H H
2-
O 1.
BnO 2Li+
S Cu
CN
2. NH4Cl/H2O
15
S
(a) (b)
BnO OH
BnO OH
OH OH
(c) BnO (d) BnO
S
87. Correct sequence of reagents (i)-(iii) required for the conversion of A to B is
N NH N
O
H2N COOH
(A) (B)
A. Thionyl chloride, B. 4-Chloropyridine C. Piperidine
(a) A, B and C (b) A, C and B (c) B, A and C (d) C, A and B
88. The following reaction involves
O O
Rh2(OAc)4 (cat)
O N2 O
(a) [1, 2] sigmatropic rearrangement (b) [2, 3] sigmatropic rearrangement

(c) [3, 3] sigmatropic rearrangement (d) C-H insertion reaction
89. Correct sequence of steps involved in the following transformation is
O
SOPh
KOH
O OH
(a) Michael addition, aldol condensation, syn-elimination, keto-enol tautomerism

(b) aldol condensation, electrocyclic ring closing, syn-elimination, dehydrogenation
(c) Michael addition, Claisen condensation, anti-elimination, keto-enol tautomerism
(d) Robinson annulation, dehydrogenation, anti-elimination
90. The major products A and B in the following reaction sequence are
O
NEt2 AcOH
A B
heat H2O
16
O O
NEt2
(a) A = B=
COOH
O O NEt2
NEt2
(b) A = B=
O
O O
COOH
(c) A = B=
NEt2
O O
O
(d) A = B=
NEt2
NEt2
91. The major product formed in the following reaction sequence is

1. H2O2, AcOH
2. HNO3, H2SO4
3. PCl3
N
NO2 Cl
NO2 Cl
(a) (b) (c) (d)
N N N N
92. The number of optically active steroisomers possible for
CH3–CH(OH)–CH(OH)–CH(OH)–CH3 is
(a) two (b) four (c) six (d) eight
1
93. The correct match of the circled protons in Column P with H NMR chemical shift ( ppm) in Column Q is
P Q
I H A 6.72
Br
17
O
H
II B 16.4
H
III C –0.61
(a) I-A; II-B; III-C (b) I-B; II-A; III-C (c) I-B; II-C; III-A (d) I-C; II-B; III-A
1. MeOH/H+
2. TBDMSCl (1 equiv)
O OH Et N
3
HO
3. PDC
4. AcOH/H O
HO 2
OH O
O OH
TBDMSO
(a) TBDMSO OH (b)
OH O
H H
O OTBDMS O OH
O O
(c) (d)
O TBDMSO
95. For the successful synthesis of peptide linkage leading to the product A, the side chain of the amino acid D
should have
H O
peptide N CO2Me
SPh + XH pH = 7
NH2
(B)
HX H2N CO2Me
H O H O
peptide N peptide N
N CO2Me X
H
18
(a) XH = – OH (b) XH = –(CH2)4NH (c) X H = – p – (C6H4)OH (d) XH = –SH
SiMe3 1. H2SO4 Ti(PrO)4
2. TBAF (+)-DET
OTBDMS A B
t-BuOOH
OH CH2Cl2-20°C
(a) A = OH B = OH
O
(b) A = OH B= OH
O
O
(c) A = B=
OH OH
O
(d) A = B=
OH OH
97. The intermediate A and the major product B in the following reaction are
OMe
Br
1. LDA (1 equiv.)
[A] B
2. MeO2C CO2Me
OMe OMe
CO2Me
(a) A = B=
CO2Me CO2Me
CO2Me
OMe OMe
CO2Me
(b) A = B=
CO2Me
CO2Me
CO2Me
OMe CO2Me OMe

CO2Me
(c) A = CO2Me
B=
CO2Me
19
OMe CO2Me OMe
CO2Me CO2Me
(d) A = B=
CO2Me
98. The correct intermediate which leads to the product in the following reaction is
O O
NaNO2
OH OH
HBr
NH2 Br
O
O
(a) OH (b)
Br N2 O
O O
(c) (d)
O N
N
99. In the following transformation, the mode of electrocyclization A and the major product B are
H
cat. OsO4
heat NMO
B
A
H
H OH
(a) A = (4n) e–, dis B=
H OH
H OH
(b) A = (4n + 2) e–, dis B =
H OH
H OH
(c) A = (4n) e–, con B =
H OH
20
H OH
(d) A = (4n + 2) e–, con B =
H OH
O
B H Br
O
n-Bu A B
then H2O (Ph3P)2PdCl2
KOH
(a) A = n-Bu B = n-Bu

B(OH)2
(b) A = n-Bu B = n-Bu

B(OH)2
n-Bu B(OH)2 n-Bu

(c) A = B=
n-Bu B(OH)2 n-Bu
(d) A = B=
101. The correct statement about the symmetry of the eigenfunctions of a quantum of 1-D harmonic oscillator is
(a) All the eigenfunctions are only even functions, because the potential is an even function.
(b) All the eigenfunction are only odd functions, although the potential is an even function.
(c) The eigenfunctions have no odd-even symmetry.
(d) All the eigenfunctions are either odd or even functions, because the potential is an even function.
102. The correct statement about the difference of second and first excited state energies (E) of a particle in 1-D,
2-D square and 3-D cubic boxes with same length for each, is
(a) E (1 – D box) = E (2 – D box) = DE (3 – D box)
(b) E (1 – D box) > E (2 – D box) > DE (3 – D box)
(c) E (1 – D box) > E (2 – D box) = DE (3 – D box)
(d) E (1 – D box) < E (2 – D box) < DE (3 – D box)
103. A one-dimensional quantum harmonic oscillator is perturbed by a potential x3. The first order correction to
the energy for the ground state (E(1)) is
(a) E(1) > 0 but < 1 (b) E(1) < 0 (c) E(1) = 0 (d) E(1) > 2
104. The normal mode of ethylene represented, by the figure below, is
H H
H H
(a) only IR active (b) only Raman active

(c) both IR and Raman active (d) neither IR nor Raman active
105. The pair that contains a spherical top and a symmetric top, among the following, is
(a) CH 4 , CH 2Cl2 (b) CH 2 Cl2 , CH 3Cl (c) CH 3Cl , CH 4 (d) CH 4 , C  CH 3 4
21
106. A part of the character table of a point group (of order 4) is given below.
E X1 X2 X3
1 1 1 1 1
2 1 1 1 1
3 1 1 1 1
4 ? ? ? ?
The four characters of 4 are, respectively

(a) 1, 1, –1, –1 (b) 2, 0, 0, 1 (c) 1, i, i, 1 (d) 1, –i, i, –1
107. The electronic transition energy from 1  2 in propenyl radical is 4.8 eV. Within the frame work of Huckel
theory, the transitions energy from 1  3 would be
(a) 2.4 eV (b) 4.8 eV (c) 9.6 eV (d) 14.4 eV
108. The g-factors of 1H and 13C are 5.6 and 1.4 respectively. For the same value of the magnetic field strength, if
the 1H resonates at 600 MHz, the 13C would resonate at
(a) 2400 MHz (b) 600 MHz (c) 150 MHz (d) 38 MHz
3
109. The term symbol for the ground state of a metal ion is P2. The residual entropy of a crystal of a salt of this metal
ion at 0 K is
(a) kB ln 1 (b) kB ln 3 (c) kB ln 5 (d) kB ln 7
110. In stretching of a rubber band,
dG = V dp – SdT + f dL
Which of the following relations in true?
S f   S   f 
(a)       (b)      
 L  p ,T  T  p , L  L  p ,T  V  p , L
S V   S   f 
(c)       (d)      
 L  p ,T  T  p , L  L  p,T  p T , L
111. Four distinguishable molecules are distributed in energy levels E1 and E2 with degeneracy of 2 and 3, respectively.
Number of microstates, with 3 molecules in energy level E1 and one in energy level E2, is
(a) 4 (b) 12 (c) 96 (d) 192
112. One mole of an ideal gas undergoes a cyclic process (ABCDA) starting from point A through 4 reversible steps
as shown in the figure. Total work done in the process is
V2 B C
Volume
V1 A D
T1 Temperature T2
V2 V2 V2
(a) R T1  T2  (b) R T1  T2  (c) R T1  T2  ln V2 (d) R T2  T1  ln
V1 V1 V1 V1
113. If the specific conductance of an electrolyte solution is 0.2 –1 cm–1 and cell constant is 0.25 cm–1, the conduc-
tance of the solution is
22
(a) 1.25  –1 (b) 1.0  –1 (c) 0.8  –1 (d) 2.0  –1
114. The predicted electromotive force (emf) of the electrochemical cell
Fe  s  / Fe 2  aq   0.01 M  | Cd 2  aq   0.01 M  / Cd  s  is
E 
0
Fe2  / Fe 
 0.447 V and E 0
Cd 2 / Cd 
 0.403 V 
(a) –0.850 V (b) +0.044 V (c) +0.0850 V (d) –0.044 V
115. A polymer has the following molar mass distribution
Number of molecules Molar mass (g.mol1 )

50 5000
75 6000
The calculated number average molar mass  M n  of the polymer is

(a) 5200 (b) 5600 (c) 5800 (d) 6000
116. The separation of the (123) planes of an orthorhombic unit cell is 3.12 nm. The separation of (246) and (369)
planes are, respectively,
(a) 1.56 nm and 1.04 nm (b) 1.04 nm and 1.56 nm
(c) 3.12 nm and 1.50 nm (d) 1.04 nm and 3.12 nm
117. The slope and intercept obtained from (1/Rate) against (1/substrate concentration) of an enzyme catalyzed
reaction are 300 and 2 × 105, respectively. The Michaelis-Menten constants of the enzyme in this reaction is
(a) 5 × 106 M (b) 5 × M–6 M (c) 1.5 × 103 M (d) 1.5 × 10–3 M
118. The pressure inside (Pin) a spherical cavity with a radius r formed in a liquid with surface tension  is related to
the external pressure (Pout) as
2 
(a) Pin  Pout  2  (b) Pin  Pout  (c) Pin  Pout   (d) Pin  Pout 
r r r r
119. Reaction between A and B is carried out for different initial concentrations and the corresponding half-life times
are measured. The data listed in the table:
Entry  A0   M   B 0  M  t1/2  sec 

1 500 10 60
2 500 20 60
3 10 500 60
4 20 500 30
The rate can be represented as

2 2 2
(a) k  A B  (b) k  A (c) k  A  B  (d) k  A B 
120. The plot of the rate constant vs. ionic strength of the reaction A2  B  follows the line (refer to the figure)
23
I
II
log k
III
IV
(a) I (b) II (c) III (d) IV
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UGC ACADEMY LEADING INSTITUE FOR CSIR-JRF/NET, GATE & JAM

CHEMISTRY –CSIR-NET -PAPER JUNE -2018- BOOKLET (A )
PART-A
1. A and B move clockwise around a circle, starting from a common point O. a takes 9 minutes to complete
a round but restarts after a delay of 1 minutes. B takes 13 minutes to complete the round but restarts after
a delay of 2 minutes. How many minutes after began would they meet again at O ?
1. 30 2. 29 3. 31 4. 28
2. Fourteen of the students in a class are girls. Eight students in the class wear blue shirts. Two are neither
girls nor wear blue shirts. Five students who wear blue shirts are girls. How many students are there in
the class ?
1. 19 2. 29 3. 17 4. 24
3. A stick of length L is broken into two pieces at random. What is the average length of the smaller piece ?
1. L/6 2. L/4 3. L/3 4. L/2
1
4. A long – distance runner finds a water station after completing th of the total distance. After covering
7
1
another th of the total distance he gets medical – acid. Another runner joins him 4 km after the medical
6
1
– acid station. The second runner stops 4 km before the completion of run, covering of the total
2
distance. What is the total distance ?
1. 21 km 2. 30 km 3. 42 km 4. 50 km
5. Movement of a car with respect to time is given below :
The average speed of the car is

1. 30.42 2. 20.43 3. 10.43 4. 21.43
6. A fuel station sold diesel costing rs 15000 to 150 persons on a day. If the lower limit of sale to a person is
rs 50, what is the maximum amount in rupees for which one person could have purchased diesel on that
day ?
1. 7450 2. 7500 3. 7550 4. 7600
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7. The area of the triangle formed by joining the points (2017, 2017), (2027, 2027) and (2037, 2017) is
1. 2017 2. 100 3. 100 10 4. 100 20
8. If Sangeeta’s daughter is my daughter’s mother, then how am I related to Sangeeta ?

1. Son is only possibility
2. Son – in – law is the only possibility
3. Daughter is the only possibility
4. Son – in – law or daughter.
9. Four males M 1 , M 2 , M 3 , M 4 and four females F1 , F2 , F3 and F4 are sitting around a round table facing
away from the table as shown in the figure below. If each one moves three positions to his/her right and
then one position to the left, then in which direction does F4 face ?
1. East 2. North – East 3. North – West 4. North
10. Prob. Murthy likes to let her students choose who their partners will be; however, no pair of students may
work together for more than seven class periods in a row. Alice and Bob have worked together for seven
class periods in a row. Calvin and Denny have worked together for three class periods in a row. Calvin
does not want to work with Alice. Who should be assigned to work with Bob ?
1. Calvin 2. Alice 3. Denny 4. None
11. In a group of 44 players, 26 play hockey, 24 play football and 24 play cricket. Eight of them play both
hockey and football, 12 play both football and cricket, and 5 play all the three games. How many play
both hockey and cricket ?
1. 10 2. 15 3. None 4. 7
12. It is given that
Suppose for two real numbers x and y, (xy)* = (x)*(y)*. Then which of the following I necessarily true ?
1. x > 0 and y > 0
2. {x > 0 and y  0} or {x > 0 and y > 0}
3. {x  0 and y  0} or {x  0 and y  0}
4. {x  0} or { y  0} or {x  0 and y  0}
13. Number of time a research paper is viewed and cited is shown in the plot. In which month was the
percentage increase in citation more than the double of the percentage increase in view ?
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1. February 2. April 3. May 4. June
14. Which of the following options is the best choice for the missing number ? 1.1, 0.25, 0.3, 0.2, 0.5, 0.6,
0.3,_, 0.9, 0.4, 1.0, 1.2
1. 1.05 2. 0.85 3. 0.75 4. 0.65
15. Consider a number 54 expressed in a base different from ten. What is the base of this number system if
its equivalent value in the decimal system is 49 ?
1. 1 2. 3 3. 6 4. 9
16. Which of the option is appropriate for the blank space ?
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17. In the diagram, what is the ratio of the total shaded area (of the circle and semi – circle) to the total area
of the square and the rectangle ?
5 6 5 
1.  2.  3.  4.
6 5 12 4
18. Two students are solving the same problem independently. If the probability that the first one solves the
3 4
problem is and the probability that the second solves the problem is , what is the probability that at
5 5
least one of them solves the problem ?
17 19 21 23
1. 2. 3. 4.
25 25 25 25
19. A ball is dropped from a height of 100 m. the ball after each bounce rises vertically by half its previous
height (this means at the first bounce it rises by 50 m, by 25 m at the second bounce and so on). What is
the vertical distance travelled by the ball between the first and the fifth bounces ?
355 365 375 385
1. m 2. m 3. m 4. m
2 2 2 2
20. Three semi – circles are drawn inside a big circle as shown in the figure. If the radius of the two identical
1
smaller semi circles is th of that of the big circle and the radius of the bigger semi – circle is twice that
4
of the small semi – circle, what proportion of the big circle’s area is shaded ?
11 12 13 13
1. 2. 3. 4.
12 16 16 14
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PART-B
21. Dinuclear anion [ I 2 (OH )2 O8 ]4 has two bridging oxo groups. The geometry around each iodine is
1. Octahedral 2. Monocapped octahedral
3. Square pyamidal 4. Pentagonal bipyramidal
22. Using a double beam UV – visible spectrophotometer, Beer’s law fails for K2Cr2O7 Solution when
1. Intensity of light source is changed
2. Detector is not a photomultiplier tube
3. Cuvette of 2 cm size is used
4. pH is not kept same in all measurements.
23. Trivalent lanthanide ion having isotropic magnetic susceptibility is –

1. Eu 3 2. Gd 3 3. Yb3 4. Lu 3
24. The structure of CaB6 is close to that of –

1. Cesium chloride 2. Nickel arsenide
3. Rock salt 4. Zinc blende
25. The correct of C – O bond length is –

1. H3 B.CO [Mn(CO)6 ]  [Cr (CO)6 ] [V (CO)6 ]
2. [V (CO)6 ] [Cr (CO)6 ] [Mn(CO)6 ]  H3 B.CO
3. [Mn(CO)6 ]  H3 B.CO [V (CO)6 ] [Cr (CO)6 ]
4. [Cr (CO)6 ]  [V (CO)6 ]  H3 B.CO [Mn(CO)6 ]
26. Among the elements Zn, Ga, Ge as As, the one with the lowest first ionization energy is –
1. As 2. Zn 3. Ga 4. Ge
27. The total degeneracy of the ground term of Co11 (high spin) in octahedral geometry is –
1. 18 2. 12 3. 28 4. 9
28. For the following reaction
The structure of the intermediate is
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29. High spin complex of a 3d metal ion M has a magnetic moment of 2.9 B.M. in octahedral coordination
environment and 4.1 B.M. in tetrahedral environment. The M ion is
1. Co 2. Ni 3. Cu 4. Co
30. For electronic spectra of K2CrO4 (A) and K2MoO4 (B) the correct combination is –
1. Transition is d – d and λmax for A < B
2. Transition is LMCT and λmax for A < B
3. Transition is LMCT and λmax for A > B
4. Transition is MLCT and λmax for A > B
31. Removal of an electron form NO molecule results in

A. An increase in the v(NO) in the IR spectrum
B. An EPR active species
C. Electrons in HOMOs being closer to the oxygen than to nitrogen 2p orbital’s
D. Electrons in HOMOs being closer to the nitrogen than to oxygen 2p orbital’s
1. A only
2. A and C
3. B and D
4. A, B, and C
32. Consider the nature of solvents in column I and the corresponding λmax for I2 in various solvents given in
column II. (for I2 vapor λmax is 520 nm). Match column I with column II
1. (a) – (i); (b) – (ii); (c) – (iii); (d) – (iv) 2. (a) – (iii); (b) – (iv); (c) – (ii); (d) – (i)
3. (a) – (i); (b) – (iii); (c) – (iv); (d) – (ii) 4. (a) – (iv); (b) – (iii); (c) – (ii); (d) – (i)
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33. For the catalytic activity of Cu and Zn containing enzyme, superoxide dismutase, what is /are the correct
statement (S) ?
(A) Cu and Zn both are essential
(B) Only Cu is essential
(C) Zu is essential and Cu may be replaced by any other divalent metal atom
(D) Zn may be replaced by any other divalent metal atom
1. (A) only 2. (C) Only 3. (D) Only 4. (B) and (D)
34. Mass spectrum of a compound shows an [M+2] ion peak that is about 4% of M+. this indicates that the
compound has one
1. Fluorine 2. Sulfur 3. Bromine 4. Chlorine
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36. For the following compounds, the correct order of reactivity towards nucleophilic acyl substitution is
1. Acetyl chloride < methyl acetate < acetic anhydride < acetamide
2. Acetamide < methyl acetate < acetic anhydride < acetyl chloride
3. Acetamide < acetic anhydride < acetyl chloride < methyl acetate
4. Methyl acetate < acetamide < acetic anhydride < acetyl chloride
37. The major product formed in the following reaction is –
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39. The major product in the following reaction is –
41. Number of signals observed in the 13C NMR spectrum of the following compound is –
1. 4 2. 5 3. 6 4. 8
42. The structure of the product formed during the reaction of amino acid with ninhydrin is –
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43. The correct order of rate of sololysis in 80% ethanol at 25°C is –
1. B > C > A 2. A > B > C 3. C > B > A 4. C > A > B
44. IUPAC nomenclature of following propellane is –
1. Tricyclo [1.1.1.02.4] pentane

3. Tricyclo [1.1.11.3.01.5] pentane
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45. The correct statement about following species is –
(a) Both A and B are aromatic

(b) A is aromatic and B is antiaromatic
(c) A is nonaromatic and B is antiaromatic
(d) A is aromatic and B is homoaromatic
46. The correct statement about the following compounds is –
1. A is more stable than B

2. B is more stable than A
3. A and B are equally stable
4. A and B are both locked conformations
47. In the pure Raman rotational spectrum of 16

O2 , whose electronic ground state is 3  g , transitions to/from
1. Even J levels are missing
2. Odd J levels are missing
3. All J levels appear
4. None of the J levels appear
48. Elementary steps of a reaction are as follows

k1
A  B 2C
k1
2C  D
If steady state approximation is applicable to C, the rate of product formation in the reaction is
1. Proportional to [A][B]
2. Proportional to [A]2 [B]2
3. Proportional to [A]1/2 [B]1/2
4. Independent of [A][B]
49. The term symbol for the ground state of B2 is

1. 1 g 2. 1 g 3. 3
 g 4. 3
 g
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2
A Gaussian distribution has the functional form f ( x)  e ( x b)
2
/2 d 2
50. . The variance of such
2a 2
distribution is
1. a 2. a2 3. b 4. b2
51. The change in entropy for a reversible adiabatic process is

1. Maximum 2. Minimum 3. Zero 4. Positive
52. The standard cell potential for the reaction Zn(S)  Cu 2 (aq) Zn2 (aq)  Cu( S ) is +1.10 V. the
Gibb’s free energy change during the reaction is
(F = 96500 coulomb mol-1)
1. – 21.2 KJ mol-1
2. + 212 KJ mol-1
3. – 212 KJ mol-1
4. – 212 KJ mol-1
53. If the unit of the rate constant of a reaction is L3mol-3S-1, the order of the reaction is
1. 1 2. 2 3. 3 4. 4
54. The lowest energy state of a 1s12s1 electronic configuration, according to hund’s rule, is
1. 3 S0 2. 1 S0 3. 3 S1 4. 1 S1
55. The commutator of with the Hamiltonian is

 2  i 
1. 0 2. i 3. px 4. px
2m m
56. A 5 g/L polymer solution is prepared with a polymer whose molar mass is 25 kg. the osmotic pressure (in
atm) of this solution at 25°C is
(consider RT 2500 J mol-1)
1. 0.002 2. 0.05 3. 0.005 4. 0.008
57. If all the lattice points of an FCC structure are occupied by uniform hard spheres that touch each other,
the fraction of volume occupied is
 2  3  2
1. 2. 3. 4.
6 6 6 6
58. Origin of the colligative properties of a dilute solution is

1. Volatility of solute molecule
2. Interaction of solute – solvent molecules
3. Zero enthalpy of mixing
4. Entropy of mixing
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59. The graph that represents the Langmuir adsorption Isotherm is
60. Correct match for the coenzymes is Column A with their function in Column B is
1. P – i; Q – ii, R – iii 2. P – iii; Q – i, R – ii

3. P – iii; Q – ii, R – i 4. P – ii; Q – i, R – iii
PART-C
61. One of the product formed in the bis(η3 – allyl) nickel complex catalyzed cyclo – dimerization of
butadiene in the presence of PR3 is compound A given below. Identify its precursor.
62. The transformation are given in Column I and reagent in Column II. Match the items of Column I with
those of Column II
Column I Column II
(a) [MnO4]- → [MnO4]2- (i) H2SO4
+
(b) Me3 CH → [Me3 C] (ii) Na in liquid NH3
(c) Ag + Au → [AuF4] (iii) [H2SO4F]+ (super acid)
(d) H3PO4] → [P(OH)4]+ (iv) Liquid BrF3
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1. (a) – (i); (b) – (ii); (c) – (iii); (d) – (iv)

2. (a) – (ii); (b) – (iii); (c) – (iv); (d) – (i)
3. (a) – (iii); (b) – (ii); (c) – (i); (d) – (iv)
4. (a) – (iii); (b) – (i); (c) – (iv); (d) – (ii)
63. Consider the following statements for the oxygenation of hemocyanine:

(A) Oxidation state of both copper atoms changes by two
(B) It becomes intense blue from colorless
(C) Dioxygen is reduced to O22 .
(D) The    2 :  2 bond forms between each oxygen and copper atoms.
The correct statements are:
1. (A) and (C) 2. (B) and (C) 3. (A),(B) and (C) 4. (B),(C) and (D)
64. The correct increasing order of C – C bond length in the following molecules (A – D)
[ PtCl3 (C2 H 4 )] ( A), [ Pt ( PPh3 )2 (C2 H 4 )] (B),[ Pt ( PPh3 ) 2{C2 (C H 4 )}] (C)
1. (C) < (A) < (B) 2. (A) < (B) < (C) 3. (B) < (C) < (A) 4. (C) < (B) < (A)
65. Which of the following are NOT closo clusters ?

[{Co(η5-C5H5)}2(C2B6H8)] (A), [B4C2H8] (B), [B10H13{Au(PPh3)}] (C), [C2B8H10] (D)
1. (C) and (D) 2. (A) and (B) 3. (A) and (C) 4. (B) and (C)
66. Identify the pair of molecules which are isoelecronic as well as isostructural from the following :
[Pd(PPh3)4] (A), [V(CO)6] (B), [Cr(CO)6] (C), [Rh(PPh3)3Cl] (D), [η5-C5H5)Ni(NO)] (E), Ni(CO)4 (F)
1. B and C 2. A and F 3. A and D 4. C and E
67. For the following reaction, correct statement (S) is/are
(A) Oxidation state of iridium increases from I to II

(B) It is β – hydride elimination reaction
(C) (I) and (II) both are diamagnetic
(D) It is migratory insertion reaction
1. (A) only
2. (A) and (C)
3. (C) and (D)
4. (B),(C), and (D)
68. The reaction of [(η5 – C5H5(Fe(CO)2]- with CH3I gives compound A. The 1H NMR spectrum of A shows
two singlets in an integrated intensity ratio of 3:5. Compound A upon reaction with PPh 3 gives
compound B. The 1H NMR spectrum of B shows 3 sets of signals in an integrated intensity ratio of
3:5:15. Compounds A and B respectively, are
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69. Identify the correct statements about the electro negativity of groups given below:
(A) CF3 group has greater value than that of NF2.
(B) NH2 group has lower value than that of NF2
(C) OH group has greater value than that of NF2
(D) CH3 and C2H5 groups have almost similar values
Correct answer is
1. A, B and D 2. B and C 3. B, C and D 4. B and D
70. Height equivalent to theoretical plate (HETP) in gas – liquid chromatography depends significantly in
which of the following ?
(A) Temperature of column (B) Velocity of carrier gas
(C) Packing of column (D) Column material
Correct answer is
1. A, B and C 2. C and D 3. B, C and D 4. A and C
71. A binary fluoride (Z) of xenon combines with two moles of NaF to give a product which on hearting to
100°C affords compounds A. the alkaline hydrolysis of A gives perxenate salt. Z and A are, respectively,
1. XeF2 and XeF4 2. XeF4 and XeF6 3. XeF6 and XeF4 4. XeF6 and XeF6
72. Match fluorescence colours given in column A with lanthanide ions given in Column B
Column A Column B
(i) Pink (a) Sm(III)
(ii) Red (b) Tb(III)
(iii) Green (c) Eu(III)
(iv) Blue (d) Tm(III)
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Correct match is –
1. (i) – (a); (ii) – (c); (iii) – (b); (iv) – (d)
2. (i) – (d); (ii) – (c); (iii) – (b); (iv) – (a)
3. (i) – (a); (ii) – (b); (iii) – (c); (iv) – (d)
4. (i) – (c); (ii) – (b); (iii) – (d); (iv) – (a)
73. Choose the correct set of statements for cis – platin.

(A) It can be prepared from K2[PtCl4].
(B) It can be prepared from [Pt(NH3)4Cl2.
(C) In its preparation, the observed trans effect for Cl- is greater than that of NH3.
(D) In blood it stays in equilibrium with cis-[Pt(NH3)2Cl(H2O)]+.
(E) In DNA strand, it binds to two adjacent cytosine bases.
The correct set is
1. A, C and D 2. A, C, D and E 3. B, C and D 4. B, C, D and E
74. In fission of 235U atom the energy released is 200 MeV. In one day fission of 1 kg 235U will give power
(in M W) approximately
1. 550 2. 650 3. 950 4. 1250
75. The structures of [Re2Cl8]2- (A) and [Os2Cl8]2- (B) are made up of two MCl4 units. For these structures,
which statement is correct ?
1. (A) and (B) both have MCl4 units eclipsed.
2. (A) and (B) both have MCl4 units staggered.
3. (A) has both MCl4 units staggered and (B) has both MCl4 units eclipsed.
4. (A) has both MCl4 units eclipsed and (B) has both MCl4 units staggered.
76. For the Wacker process, pick the correct statement (s) from the following:
(A) Pd(II) is reduced to Pd(0) by Cu(i)
(B) Pd(0) is oxidized to Pd(II) by Cu(II)
(C) Cu(II) promotes the reductive elimination
correct answer is
1. A and C 2. B and C 3. A and B 4. B Only
77. Consider following statements:
I: AsCl5 is thermally less stable than PCl5.
II: Size of As is more than that of P.
choose correct answer from the following
1. Statements I and II are true and II is the correct explanation of I.
2. Statements I and II are true but II is not the correct explanation of I.
3. Statement I is true and statement II is false.
4. Both the statements I and II are false.
78. Consider the following statements for Be2Cl4 (I), B2Cl4 (II) and Ga2CL4 (III):
(A) There is an M – M (M = Be, B, Ga) bond in all.
(B) The oxidation state of Be, B and Ga is +2.
(C) The geometry around the central atom is planar for all.
(D) The geometry around the central atom is planar in I and II only.
The correct statement(s) is/are
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1. A, B and C 2. A and B 3. D only 4. B, C and D
79. Consider the following statements :

(A) Cr2+ is easier to oxidize than V2+ in the gas phase
(B) Cr2+(aq) is a more powerful reducing agent than V2+(aq).
(C) The rate of water exchange for Cr2+(aq) is much faster than for V2+(aq).
1. A and B 2. A and C 3. B and C 4. A, B and C
80. Consider the statements A – D regarding equation I – III :

(I) [Fe(CN)6]3- + [Co(CN)5]3- → [Fe(CN)6]4- + [Co(CN)5]2-
(II) [Co(bipy)3]2+ + [Co*(bipy)3]3+ → [Co(bipy)3]3- + [Co*(bipy)3]2+
(III) [Co(NH3)5F]2+ + [Cr(H2O)6]2+ → [Co(NH3)5(H2O)2+]2+ + [Cr(H2O)5F]2+
(A) Marcus equation is applicable to I and II.
(B) Marcus equation is applicable to II only.
(C) Equation I and II involve inner sphere electron transfer.
(D) Equation I and III involve inner sphere electron transfer.
The correct statements are :
1. A and B 2. B and C 3. B and D 4. C and D
81. The major formed in the following oxidation reaction is
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84. The major product A and B formed in the following reaction sequence are
85. Structure of the intermediate A and the final product B in the following reaction sequence are
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86. Mechanism of the following transformation involves
1. A [2+2] cycloaddition followed by ‘con’ rotatory electrocyclic ring opening

2. A [4+2] cycloaddition followed by ‘con’ roratory elecrocyclic ring opening
3. A [4+2] cycloaddition followed by cope rearrangement
4. A [2+2] cycloaddition followed by ‘dis’ rotatory elecrocyclic ring opening
87. The correct statement about solvolysis using NaOAc/AcOH of following compounds is
1. A reacts faster than B to give trans – 1,2 – diacetoxycyclohexane

2. B reacts faster than A to give trans – 1,2 – diacetoxycyclohexane
3. A reacts faster than B to give cis – 1,2 – diacetoxycyclohexane
4. B reacts faster than A to give cis – 1,2 – diacetoxycyclohexane
88. The structure of the intermediate A and the major product B formed in the following reaction are
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89. A compound shows following spectral data:

1
H NMR: δ 7.9 (d,J = 8 Hz, 2H), 6.6 (d, J = 8 Hz, 2H), 4.3 (q, J = 6 Hz, 2H), 4.0 (br s, 2H, D2O
exchangeable), 1.4 (t, J = 6 Hz, 3H) mass: m/z 165, 137, 120, 92
The correct structure of the compound is
90. The major allylic alcohol A and the ester B formed in the following reaction sequence are
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92. Reaction of D – glucose with following reagents produces

Reagents: 1. Acetone, H+; 2. PDC; 3. (EtO)2P(O)CH2CO2Et, NaH
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93. For the following thermal [2+2] cycloaddition reaction, the correct statement about Transition state (TS)
and preference for endo product formation is
1. Ts : 2 s   2 s ; Me  i  Pr  t  Bu 2. Ts : 2 s   2 a ; t  Bu  i  Pr  Me
3. Ts : 2 a   2 s ; Me  i  Pr  t  Bu 4. Ts : 2 s   2 s ; t  Bu  i  Pr  Me
95. The major products formed in the following photochemical reaction are
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96. Irradiation of either cis – or trans – stilbene at 313 nm results in the formation of a mixture of 93% cis
and 7% trans olefin because.
1. Trans – stilbene is more stable than cis – stilbene.
2. The extinction coefficient of trans – stilbene is greater than cis – stilbene at exciting wavelength
3. The transition state structures of cis and trans – stilbenes are different
4. The triplet excited states of cis – and trans – stilbenes are at different energy levels.
97. The major heterocyclic compound formed in the following reaction is –
98. The major product A and B formed in the following reaction sequence are –
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99. The correct order of rates for the following reactions is
1. K1 > K2 and K3 > K4 2. K1 > K2 and K4 > K3

3. K2 > K1 and K3 > K4 4. K2 > K1 and K4 and K3
100. The correct match of protons in Column A with the 1H NMR chemical shift in Column B for the product
of the following reaction is
1. P – ii; Q – i; R – iii; S – iv 2. P – i; Q – ii; R – iv; S – iiii

3. P – iv; Q – i; R – iii; S – ii 4. P – ii; Q – iv; R – i; S – iii
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101. Which of these is not a suitable unnormalized wave function for the excited 1s ‘2s’ electron
configuration of the helium atom ?
1. [1s (1)2 s (2)  2 s(1)1s(2)][  (1)  (2)]
2. [1s(1)2 s(2)  2 s(1)1s(2)][ (1)  (2)   (1) (2)]
3. [1s(1)2 s(2)  2 s(1)1s(2)][ (1)  (2)   (1) (2)]
4. [1s (1)2 s(2)  2 s(1)1s(2)][ (1)  (2)]
102. Two opposite sides (in the y – direction) of a square box of side L are slightly stretched. Consider the
following four statements:
A. The point group changes from D4h to D2h.
B. The (1,2) and (2,1) energy levels remain doubly degenerate
C. Both the energy levels are lowered and the energy of the (1,2) level higher than that of the (2,1)
level.
D. Both the energy levels are lowered and the energy of the (1,2) level lower than that of the (2,1) level.
The two correct statements are :
1. A and B 2. A and C 3. B and C 4. A and D
103. Consider a model system of five non – interacting fermions in a single 3 – dimensional harmonic
 1  2 2 
2
oscillator. The Hamiltonian of a single particle is H  
2m 
p x  p y  p z  
1 2
 
x  y 2  z 2 where m
 2
  
is the mass of the particle, ω is the angular frequency, Px , Py and Pz are the momentum operators. The
ground state energy of the system of non – interacting fermions is
21 15 5 25
1.  2.  3.  4. 
2 2 2 2
104. A particle is in a state ϕ = ψ1 + 3ψ2, where ψ1 and ψ2 are eigenfunctions of the Hamiltonian of the
particle with eigenvalues E1 and E2, respectively. The average energy of the particle in the state ϕ is
1. ( E1  9 E2 ) /10 2. ( E1  3E2 ) 3. ( E1  9 E2 ) /14 4. ( E1  3E2 ) /10
105. Which of the following statements on ground state perturbation theory, involving the zeroth order energy
E0(0) , first order energy correction E0(1) and second order energy correction E0(2) , is false ?
1. E0(1) is the average value of perturbation operator with respect to the ground state of the zeroth order
Hamiltonian.
2. E0(1) is necessarily negative.
3. E0(2) is necessarily negative.
4. E0(0) + E0(1) is an upper bound to the exact ground state energy.
106. Difference between activation energies of the reverse and forward steps of a reversible reaction is
9:21RT. If the pre-exponential factor of the forward reaction is double that of the reverse reaction at the
same temperature, the equilibrium constant for the reaction at that temperature will be (In10 = 2.303)
1. 1 × 104 2. 2 × 104 3. 1 × 10-4 4. 2 × 10-4
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107. For an enzyme – substrate reaction,

k1
E  S ES
k1
,
1 1
The slope and the intercept of the plot between and are 102 s and 102 M 1s, respectively. If
r [S ]
k1
E0 106 M and  1000, the value of K1 will be close to (in units of M 1 s 1 ) [r is the rate of the
k2
reaction and E0 is the initial concentration of the enzyme)
1. 1 × 1011 2. 1 × 104 3. 1 × 108 4. 1 × 106
108. Translation partition function of a D2 molecule confined in a 100 cm3 vessel at 25°C is
(h  6.626  1034 J .s, K 1.3811023 JK 1 )
1. 3.8  10 22 2. 5.8  10 24 3. 7.8  10 26 4. 9.8  10 28
109. The volume (cm3) of CO adsorbed in charcoal (273 K) at two different pressures is given below
P(kPa) 40 80
3
V(cm ) 25 40
Assuming Langmuir isotherm, the maximum possible volume (cm3) CO that can be adsorbed is
1. 50 2. 100 3. 150 4. 200
110. The number of lines in EPR spectrum of CD3 (ID = 1) is

1. 3 2. 5 3. 7 4. 9
111. A symmetric top molecule, among the following, is

1. Ethylene 2. allene 3. butatriene 4. hexatriene
112. The allowed electronic transition in fluorine molecule is

1. g  g 2. g  g 3. g  u 4.  g  u
113. Assuming harmonic approximation, the energy change for the reaction HCl + D2 → DCl + HD in cm-1 is
(the vibrational frequency data in cm-1 is given in the table below),
HCl D2 DCl HD
2885 2990 1990 3627
1. -258 2. +258 3. -129 4. +129
114. The transition moment integral for a rotational transition between J = 1; Mj = 0 and J = 2; Mj = 0 states
for a diatomic molecule along the z axis is proportional to
 
 cos  (3cos   1)d  cos  (3cos   1) sin  d
2 2 2 2
1. 2.
0 0
 
 cos  (3cos   1) sin  d  cos  (3cos   1) sin d
2 2 2
3. 4.
0 0
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115. One of the correct normalized sp2 hybridorbitals is

1 1 1
1.  2 s   2 px   2 p y
3 3 3
1 3 3
2. 2 s   2 px  2 py
2 8 8
1 3
3. 2 s   2 px
3 8
1 2
4.  2 s   2 px
3 3
116. At 300 K, the thermal expansion coefficient and the isothermal compressibility of liquid water are 2 × 10-
5  U 
bar-1, respectively.   (in Kbar) for water at 320 K and 1 bar will be
 V T
1. 2.4 2. 1.2 3. 0.6 4. 12.0
117. In the phase diagram of water, the solid – liquid boundary has a negative slope. The reason for this
unusual behavior can be traced to decrease in
1. Density of the system on melting
2. Volume of the system on melting
3. Entropy of the system on melting
4. Enthalpy of the system on melting
118. The standard cell potential of cell, Pt H 2 ( g ) HBr (aq) AgBr (s) Ag (s), was measured over a range of
temperature , and the data was fitted as E 0 (Volt )  0.01  1104 (T  298)  2 106 (T  298) 2 the
standard reaction entropy (JK-1 mol-1) and enthalpy (KJmol-1) at 298 K are
1. – 9.65 and – 3.85 2. – 3.84 and – 9.65 3. – 18.3 and – 7.68 4. – 7.68 and – 18.3
119. The (002) plane of an elemental FCC crystal diffract X – rays (λ = 0.154 nm) at Bragg angle 90°. The
density of the crystal is 4×104 kg m-3. The atomic weight of the elemental solid is
1. 22 2. 44 3. 88 4. 66
120. A solution of Fe3 is titrated potentiometrically using Ce3 solution at 25°C. the emf (in V) of the redox
system thus formed when, (i) 50% of Fe3 and (ii) 80% of Fe3 are titrated, would respectively be
(Given EFe0
3
/ Fe2
 0.77V , log10 2  0.301)
1. 0.734 and 0.77 2. 0.77 and 0.385 3. 0.77 and 0.734 4. 0.385 and 0.367
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1
CSIR-UGC-NET/JRF | GATE CHEMISTRY

CSIR-UGC-NET CHEMICAL SCIENCES DEC. 2018
[BOOKLET CODE -A ]
PART - A
1. A mineral contains a cubic and spherical cavity. The length of the side of the cube is the same as the
diameter of the sphere. If the cubic cavity is half filled with a liquid and the spherical cavity is completely
filled with liquid, what is the approximate ratio of the volume of the liquid in the cubic cavity to that in the
spherical cavity?
(a) 2 : 1 (b) 1 : 1 (c) 1 : 2 (d) 1 : 4
2. Out of 6 unbiased coins, 5 are tossed independently and they all result in heads. If the 6th is now independently
tossed, the probability of getting head is
(a) 1. (b) 0. (c) 1/2. (d) 1/6.
3. What could the fourth figure in the sequence be?
(a) (b) (c) (d)
4. The average age of A, B and C, whose ages are integers x, y and z respectively.  x  y  z  is 30. If the age
of B is exactly 5 more than that of A, what is the minimum possible vlaue of z?
(a) 31 (b) 33 (c) 35 (d) 37
5. Percentage-wise distribution of all science students in a university is given in the pie-diagram. The bar chart
shows the distribution of physics students in different sub-areas, where a student takes one and only one sub-
area. What percentage of the total science students is girls studying quantum mechanics?
Astro- 150 Girls
Physics
250 Boys
Physics
Quantum 160
Earth 20% Mechanics 190
Sciences 15% Maths
15%
Optics 170
20% 330
30%
Biology Chemistry
Others 100
250
(a) 10 (b) 1 (c) 0.2 (d) 2

South Delhi : 28-A/11, Jia Sarai, Near-IIT Metro Station, New Delhi-16, Ph : 011-26851008, 26861009
2
6. What is the total number of parallelograms in the given diagram?
(a) 27 (b) 24 (c) 22 (d) 14

7. Election results of a city, which contains 3 segments (A, B and C) are given in the Table. Percentage votes
obtained by parties X, Y and Z are also shown. Which party won the election?
Segment Total Voters % of voting X Y Z

A 2, 00, 000 60 30 30 40
B 2,50, 000 70 40 30 30
C 3, 00, 000 80 30 40 30
(a) Y (b) X (c) Z (d) It was a tie between X and Y

8. The diagram shows the dimensions (in cm) of a zircon crystal having a square prism and two identical square
pyramids. What is the volume of this crystal (in cm3)?
0.3
1
1
3
3 3
1 1
0.3
(a) 3.2 (b) 3.6 (c) 6.4 (d) 7.2

9. A boy throws a ball with a speed v at a vehicle that is approaching him with a speed V. After bouncing from the
vehicle, the ball hits the boy with a speed
(a) v (b) v + V (c) v + 2V (d) v + 4V
10. Four friends were sharing a pizza. They decided that the oldest friend will get an extra piece of pizza. Bahu is
two months older than Kattappa, who in turn is three months younger than Bhalla. Devsena is one month older
than Kattappa. Who should get the extra piece of pizza?
(a) Bahu (b) Devsena (c) Bhalla (d) Kattapa
11. A funnel is connected to a cylindrical vessel of cross-sectional area A as shown, to make an interconnected
system of vessels. Water is poured in the cylinder such that the height of water in the funnel is l as shown. If the
level of water in the cylindrical vessel is pushed down by a distance x << l, the level of water in the funnel:
Area A
l 45º
Ax
(a) remains unchanged (b) rises by
 l2
3
 l2 A2 x
(c) rises by (d) rises by 2 4
Ax  l
12. Marks (out of 30) of seven students in an examination are 4, 15, 6, 7, 5, a and b, where a (> 0) is a multiple
of 4 and b is a prime. What is the maximum possible value of the difference between the maximum and
minimum marks?
(a) 25 (b) 26 (c) 27 (d) 29
13. Two persons A and B start walking in opposite directions from a point. A travels twice as fast as B. The speed
at which B travels is 1 km/h. If A travels 2 km and turns back and starts walking towards B, at what distanec
from the starting point will A cross B?
(a) 2 km (b) 4 km (c) 6 km (d) 8 km
14. A person wanted to travel from Charbag to Alambag with an average speed of 60 km/h by car. The distance
between Charbag and Alambag is 2 km. Due to heavy traffic, he could travel at 30 km/h for the first kilometre
of his journey. What should his speed be for the remaining journey to achieve his average speed target of 60
km/h?
(a) Cannot achieve his target with any finite speed
(b) 60 km/h
(c) 90 km/h
(d) 120 km/h
15. The average rainfall over a given place during the three-year period of 2003-2005 was 65 cm. During the
three-year period 2002-2004 the average rainfall was 63 cm. The actual rainfall during 2005 was 60 cm. What
was the rainfall in 2002?
(a) 55 cm (b) 60 cm (c) 54 cm (d) 53 cm
16. In a four consecutive day schedule, four pilots flew flights each on a different day. Mr. A was scheduled to work
on Monday, but he traded with Ms. B who was originally scheduled to work on Wednesday. Ms. C traded
with Mr. D, who was originally scheduled to work on Thursday. After all the switching was done, who worked
on Tuesday?
(a) Mr. A (b) Mr. D (c) Ms. B (d) Ms. C
17. After 6g of carbon is completely burnt in an atomosphere of 40g of oxygen, the percentage oxygen left is:
(a) 80 (b) 60 (c) 40 (d) 20
18. What fraction of the equilateral triangle shown below with three identical sectors of a circle is shaded?
  2 3
(a) 1  (b) (c) 1  (d) 1 
2 3 2 3 3 2
19. How many different vegetables can be made from cauliflower, tomatoes, onions, potatoes and carrots?
(a) 16 (b) 28 (c) 31 (d) 32
20. A bottle of perfume is opened and a person at a distance of 10 m gets the smell after 10 seconds. The time
taken for a person 20 m away to get the smell is about
4
(a) 20s (b) 40s (c) 14s (d) 80s
PART - B
21. The correct order of acceptor ability of the phosphorus ligands is
(a) PMe3  PPh 3  P  OPh 3  PF3 (b) PF3  P  OPh 3  PPh 3  PMe3
(c) PF3  PMe3  PPh 3  P  OPh 3 (d) P  OPh 3  PF3  PMe3  PPh 3
22. In the 31P{1H} NMR spectrum of a diamagnetic complex mer-[M(PR3)3Cl3] (M = transition metal, I = 0)
expected number of resonance(s) is
(a) Three (b) One (c) Two (d) Six
23. Consider the species NO, I2, I2 , Cu2+ and VO2+. The number of paramagnetic species among them and the
EPR inactive species, respectively, are
(a) 4 and I2 (b) 4 and I2 (c) 3 and VO2+, Cu2+ (d) 3 and NO, Cu2+
24. Identify the correct statement(s) for H3B.CO.

(A) sp2 hybridized orbital of B accepts the lone pair of CO.
(B) Its CO value is more than that for free CO
(C) Formal oxidation state of C is +4 in the compound
Answer is
(a) A and B (b) B only (c) A only (d) A and C
25. Match the items of Column-I with those of Column-II.
Column-I Column-II
(A) Laser source (I) Electron Capture Detector
(B) Thermometric titration (II) Polarography
(C) Gelatin (III) Heat of reaction
(D) Gas-liquid chromatography (IV) Spectrofluorimetry
Correct answer is
(a) A-IV, B-III, C-II, D-I (b) A-I, B-III, C-II, D-IV
(c) A-IV, B-II, C-III, D-I (d) A-III, B-II, C-IV, D-I
26. Consider compounds PF5, SbF5, PH3 and SbH3. The strongest acid and the strongest base among these are,
respectively.
(a) PF5 and PH3 (b) SbF5 and PH3 (c) SbF5 and SbH3 (d) PF5 and SbH3
27. Among SiCl4, P(O)Cl3, NF3, trans-[SnCl4(py)2] (py = pyridine), those with zero dipole moment are
(a) SiCl4 and NF3 (b) SiCl4, P(O)Cl3 and trans-SnCl4(py)2
(c) SiCl4 and trans-SnCl4(py)2 (d) NF3 and trans-SnCl4(py)2
28. The standard reduction potentials in acid medium for F2, Cl2, Na and Zn are in the order
(a) F2 > Cl2 > Na > Zn (b) F2 > Cl2 > Zn > Na
(c) Na > Zn > Cl2 > F2 (d) Cl2 > F2 > Zn > Na
29. The characters of LUMO and CN– and O2 respectively, are
(a) g and u (b) u and u (c) g and  u (d) u and g
2 2
30. The intermediate  Fe  SCN  H 2 O 5  is detected in the reaction of Co  NCS  NH 3 5  with
2 2 3
 Fe  H 2 O 6  in aqueous medium to produce Co  H 2 O 6  and  Fe  H 2 O 6 
5
The mechanism of the reaction is
(a) Interchange dissociative (b) Interchange associative
(c) Inner sphere electron transfer (d) Outer sphere electron transfer
31. The chelate rings made by macrocyclic ligand in vitamin B12 are
(a) One five-membered and three six-membered
(b) Two five-membered and two six-membered
(c) Three five-membered and one six-membered
(d) Four six-membered
32. For magnesium complex of EDTA2–, the number of N-donor and O-donor centers, are respectively,
(a) two and four (b) two and two (c) two and six (d) two and eight
33. The correct set of electronic configurations for metal ions in octahedral coordination geometry for strong
Jahn-Teller distortion is
(a) t 62g e1g , t 32g e1g , t 62g e3g (b) t12g , t 32g e g2 , t 62g , e1g
(c) t 32g , t 32g e1g , t 32g eg2 (d) t 32g eg2 , t 62g eg2 , t 62g e3g
34. The order of relative rate of cyclization of following bromocarboxylates to generate corresponding lactones
is
O O O
Br
Br O O Br O
(A) (B) (C)
(a) B > A > C (b) A > C > B (c) B > C > A (d) C > B > A
35. Oxidation of A with HNO3/H2O provides the product(s), which is (are)
OH
HO CHO
(A) OH
(a) Optically inactive as it is racemic mixture
(b) Optically inactive as it is meso
(c) Optically active as it is a single diastereomer
(d) Optically active as it is a single enantiomer
Br
MeNH2
(P)
heat
Cl N
NH
H Br
N
(a) (b) (c) (d)

Cl N N N N
H Cl N H
Cl N
6
37. The order of reactivity of the following dienes towards Diels-Alder reaction is
t-Bu t-Bu
t-Bu
(A) (B) (C)
t-Bu
38. Among the following, the optically active compound is
(a) (b) (c) (d)
39. Among the following, reaction(s) which provide(s) 1-butene as the major product is (are)
t-BuOK t-BuOK
(A) Br
(B)
Br
AgOH
H2SO4
(C) I N (D)
OH
(a) A alone (b) A and B (c) A and C (d) C and D

OH
aq. NaHCO3
CCl3
OH Cl O
CO2H
(a) CO2H (b) CO2H (c) CO2H (d)
41. Among the following, the compound that will have highest rate for nucleophilic substitution through SN1
mechanism is
NO2 NO2
O O
(a) (b)
O O
NO2 NO2
O O
(c) (d)
O O
7
OH
O O
O O
Pyridine
NH2
O OH O OH
O O O
(a) (b) (c) (d)

HN HN O
NH2 O NH2 O
43. The mechanism of acid catalyzed hydrolysis of benzonitrile involves
Ph C N
(a) (b) Ph C N H (c) Ph C N H (d) Ph C N H
••
O H •• ••
O O OH
H H
H H H
44. In the energy profile diagram of the reaction given below, the species A would correspond to the position
COCH3
CH3COCl
anhyd. AlCl3
H COCH3
(A)
8
I
III
E II
IV
Reaction co-ordinate
(a) I (b) II (c) III (d) IV

CO2Et
Mg(ClO4)2 EtO2C
(a) Alder-Ene reaction (b) Michael addition

(c) Sigmatropic Rearrangement (d) Wagner-Meerwein Rearrangement
46. In IR spectra, the stretching frequency (in cm–1) of the carbonyl group of the following compounds is in
the order
O O O
O O O
(A) (B) (C)

47. The uncertainty in the position of a moving electron is 100 pm. The uncertainty in its speed is closest to
(me = 9.11×10–31 kg ; h = 6.63×10 –34 J.s)
(a) 6.0×10 2 m.s–1 (b) 6.0×10 5 m.s–1 (c) 6.0×10 8 m.s–1 (d) 6.0×10 11 m.s–1
48. The spectrum of sodium atom has a closely separated doublet at 16956.2 and 16973.4 cm–1. The higher
energy transition is due to
(a) 2 P3/2  2S1/2 (b) 2 P1/2  2S1/2 (c) 2 P3/2  2 P1/2 (d) 2 S1/2  2 P3/2
49. N2O molecule belongs to the point group
(a) Dh (b) Cv (c) C2v (d) S2
50. For a closed system in the absence of non-PV work, the correct statement is
(a) dU  TdS  PdV (b) dG  VdP  SdT
(c) dU  TdS  PdV (d) dU  VdP  SdT
51. The volume change in a certain phase transition is 2.0 mL mol–1 at the transition point. From this, we may
conclude that the transition is most likely to
9
(a) first order phase transition (b) second order phase transition
(c) third order phase transition (d)  phase transition
52. Root mean square speed of the molecules of a perfect gas is proportional to
(a) 1/T1/2 (b) T (c) T1/2 (d) 1/T
53. For a second-order reaction, the straight line among the following plots is
(a) [X] versus time (b) 1/[X] versus time
(c) log[X] versus 1/time (d) log[X] versus time
54. The activation energy of a reaction reduces by 12 kcal mol –1 in the presence of an enzyme at 300 K.
Assuming pseudo-first order kinetics, calculate the factor by which the reaction rate is increased. [Given:
R = 2 cal K–1mol–1]
(a) 2×10 –9 (b) 1.02 (c) 8.7×10 6 (d) 5×10 8
55. The correct statement among the following is
(a) Salt bridge is required for the mixing of the solutions in the two half cells.
(b) Salt bridge allows current to flow between the half cells without mixing the solutions
(c) Salt bridge enhances the rate of the reaction
(d) Salt bridge consists of a non-electrolyte in a gel.
56. The standard free energy of the reaction
AgBr  s   Ag   aq   Br   aq 
is closest to
 E  AgBr / Ag, Br   0.07 V, E  Ag / Ag   0.80 V; F  96500 C mol 

0  0  1
(a) 7 kJ mol–1 (b) 70 J mol–1 (c) 70 kJ mol–1 (d) 7 J mol–1

57. The internal pressure of a liquid drop (radius = 10–6 m) is greater than the external pressure by 1.5×105
Nm–2. The surface tension (mN m–1) of the liquid is closest to
(a) 150 (b) 125 (c) 100 (d) 75
58. In a cubic crystal, the (1 1 1) and (222) reflections are observed, but not the (001) reflection. The
Bravais lattice is
(a) body centred cubic (b) face centred cubic
(c) simple cubic (d) side centred cubic
59. The dispersity of a polymeric sample is
2
M2 M M2 M
(a) 2 (b) M 2 (c) (d) 2
M M M
60. The keto-hexose among the following is
(a) Xylose (b) Galactose (c) Fructose (d) Mannose
PART - C
61. The product for the reaction given below is
CH3
IrCl(COE)(PMe3)3
+
COE = Cyclooctene O
10
O O
Cl Cl
Me3P CH2 C CH3 Me3P CH2 C CH3
(a) Ir (b) Ir
H PMe3 Cl PMe3
PMe3 PMe3
O O
Cl H2 H H2
Me3P C C CH3 Me3P C C CH3
(c) Ir (d) Ir
Cl PMe3 Cl PMe3
PMe3 PMe3
62. The 31P {1H} NMR spectrum of cis-[Pt(PEt3)2Cl2] (195Pt (33.8% abundance) I = ½; its other isotopes are
NMR inactive; 31P : I = ½) is comprised with satellite peaks of a
(a) triplet (b) singlet (c) doublet (d) quartlet
63. The correct order of intensity of the d-d transitions in the complexes of a 3d-transition metal ion M2+ is
2
(a) cis   M  H 2 O 4 Cl2   trans   M  H 2 O 4 Cl2    M  H 2 O 6 
2
(b)  M  H 2 O 6   cis   M  H 2 O 4 Cl 2   trans   M  H 2O 4 Cl 2 
2
(c) trans   M  H 2 O 4 Cl2   cis   M  H 2 O 4 Cl 2    M  H 2 O 6 
2
(d)  M  H 2 O 6   cis   M  H 2 O 4 Cl 2   trans   M  H 2O 4 Cl 2 
64. The reaction of decaborane B10H14 with acetylene in the presence of Et2S gives
(a) C2B10H12 (b) C2B8H10 (c) C2B10H14 (d) C2B9H11
65. In compound N3P3F6, the geometry around nitrogen and phosphorus, respectively, are
(a) pyramidal and tetrahedral (b) planar and tetrahedral
(c) pyramidal and planar (d) planar and trigonal bipyramidal
66. The number of 2c-2e bonds (‘x’) of a molecule is related to ‘N’ (valence electrons) and ‘n’ (skeletal atoms) by
x = (8n–N)/2. For P4S3, the values of x, N and n, respectively, are
(a) 7, 38, 9 (b) 7, 24, 9 (c) 9, 38, 7 (d) 9, 24, 7
67. Match the following complexes with their CO stretching frequency
Complex  
 CO cm 1 values
 A  Mo  PF3 3  CO 3 (I) 1835, 1934
 B  Mo P  OMe 33  CO 3  II  1888, 1977

 C  Mo  PPh 3 3  CO 3  III  2055, 2090
 D  Mo  pyridine 3  CO 3  IV  1746, 1888
(a) A-I, B-IV, C-II, D-III (b) A-III, B-II, C-I, D-IV
(c) A-IV, B-III, C-I, D-II (d) A-I, B-II, C-III, D-IV
11
3 4
68. The  CN in  Fe  CN 6  (A) and  Fe  CN 6  (B) and  CO in  Cr  CO 3  NH3 3  (C) and
Cr  CO 6  (D) are compared below. The pair with correct order is
(a) A > B ; C > D (b) A > B ; C < D (c) A < B ; C > D (d) A < B ; C < D
69. Consider the following statements for [FeO4]2–
(A) It is stable in the pH range 0-14
(B) It is stable in strongly basic medium only
(C) It is a very strong oxidizing agent
(D) The isomer shift in its Mossbauer spectrum is more negative compared to that of FeCl3.
(a) A, C and D (b) B, C and D (c) B and C (d) C and D
2+ 2+
N N
NH2 NH2
H2N Co H2N Co
70. Cl NH3
H2N H2N
NH3 Cl
(A) (B)
The isomers A and B undergo base hydrolysis by forming a trigonal bipyramidal intermediate. The correct
statement is
(a) A reacts faster than B and both results in a mixture of products
(b) B reacts faster than A and both results in a mixture of products
(c) A reacts fastser than B and B results ini a mixture of products
(d) B reacts faster than A and A resutls in a mixture of products.
71. B2H6 reacts with
(A) water to give boric acid and H2 (B) oxygen to give B2O3 and H2
(C) water to give boric acid and H2O (D) oxygen to give B2O3 and H2O
Correct statements from the above are
(a) A and B (b) A and D (c) B and C (d) B and D
72. The ligand that binds strongly to the nickel center in (2, 2’-bipyridine) Ni(0) complex is
O
(a) O (b) OAc (c) OMe (d) CH3
O
73. Match the items given in Column-I with those given in Column-II
Column-I Column-II
(A) Magic number (I) Nuclear fission
(B) Liquid drop model of nucleus (II) Q-value
(C) Actinides (III) Radioactivity
(D) Threshold energy (IV) Shell model of nucleus
(a) A-IV, B-I, C-III, D-II (b) A-II, B-I, C-III, D-IV
(c) A-III, B-IV, C-I, D-II (d) A-IV, B-III, C-I, D-II
12
2
74. The cluster type and geometry of the species  Rh 9 P  CO 21  are
(a) closo, tricapped trigonal prism (b) arachno, trigonal prism
(c) nido, capped square antiprism (d) nido, bicapped trigonal prism
75. Hydroformylation of 1-propene with [HRh(CO)L2] leads to linear and branched formylated products. The
linear hydroformylated product is formed with highest selectivity when ‘L’ in the rhodium complex is
PPh2 PPh2
PPh2
(a) (b) (c) (d)
PPh2
Fe
PPh2
O
PPh2 PPh2 PPh2
76. The hydrocarbon having an analogous structure to that of P4O6 is

(a)  CH 4 µ  CH 2 6  (b)  CH 6 µ  CH 2 4 
(c)  CH 2 4 µ  CH 6  (d)  CH 2 4 µ  CH 4 
77. Match the items given below in the three columns:

Metalloprotein Species coordinated to metal Resonance Raman O–O
centre(s) stretching frequency (cm–1 )
(A) Oxymyoglobin (I) 2 2
 : O
2 (X) 844
2
(B) Oxyhemocyanin (II) HO2– (Y) 803
(C) Oxyhemerythrin (III) O 2– (Z) 1105
Correct matches:
(a) A-III-Z, B-I-Y, C-II-X (b) A-II-Y, B-I-X, C-III-Z
(c) A-III-Y, B-I-Z, C-II-X (d) A-I-X, B-II-Y, C-III-Z
78. A solid sample of Na[Fe(EDTA)(H2O)s] (X) showed 5.6% weight loss at 120ºC in a thermogravimetric
experiment. Identify the complex left after this weight loss.
(a) Na  Fe  EDTA  H 2 O   (b) Na  Fe  EDTA  
(c) Na  Fe  EDTA  H 2 O 2  (d) Na  Fe  EDTA  H 2 O 3 
79. Consider the two sets of molecules.

3  2
Set A:  AlF6  ,  PF6  , SF6  and SiF6 
2 2 2 2
Set B :  Ba  H 2 O 6  , Ca  H 2 O 6  ,  Mg  H 2 O 6  , Sr  H 2O 6 
The slowest ligand exchange rate in Set A and Set B are, respectively
3 2 2
(a)  AlF6  and Sr  H 2 O 6  (b) SF6  and  Mg  H 2 O 6 
2 2  2
(c) SiF6  and Ca  H 2 O 6  (d)  PF6  and  Ca  H 2 O 6 
13
80. Consider following statements for Eu3+
(A) The positions of sharp bands in UV-vis spectra of its complexes depend heavily on the ligand environment
(B) Its ground state term symbol is 7F0.
(C) The observed magnetic moment is due to populated higher J level
(D) At 2 K its magnetic moment approaches to zero
The set of correct statements is
(a) A, C and D (b) B, C and D (c) A, B and D (d) A, B and C
SiMe3 (i) n-Bu NF

4
NMe3 (ii) MeO2C

CO2Me
CO2Me CO2Me
(a) (b)
CO2Me CO2Me
CO2Me CO2Me
(c) (d)
CO2Me CO2Me
82. Structure of the compound displaying following characteristics spectral data

IR : 1720 cm–1
1
H NMR : 6.2 (br s, 1H), 5.5(br, s, 1H), 4.2 (q, 2H), 2.0 (s, 3H), 1.1 (t, 3H) is
O
O
(a) (b)
O
O
O
(c) (d) O
O O
14
(i-PrO)4Ti
O + MgCl
(2 equiv.) 20ºC
CHO
OH
(a) (b)
OH
(c) (d)
84. The intermediate(s) involved in the following reaction is(are)

MeO MeO
I2, Ag2O
dioxane, H2O
CHO
MeO MeO MeO

I OH
OH
(I) (II) OH (III) I
(a) Only I (b) Only II (c) I and II only (d) I and III only
85. Correct sequence of reagents to be used for the following conversion is
O NMe2
S
O
(a) (I) NaH, 1-fluoronaphthalene; (II) NaBH4; (III) (i) (CH2O)n, Me2NH.HCl; (ii) 5 N NaOH
(b) (I) NaBH4; (II) NaH, 1-fluoronaphthalene; (III) (i) (CH2O)n, Me2NH.HCl (ii) 5 N NaOH
15
(c) (I) (i) (CH2O)n, Me2NH.HCl; (ii) 5N NaOH; (II) NaBH4; (III) NaH, 1-fluoronaphthalene
(d) (I) (i) (CH2O)n, Me2NH.HCl; (ii) 5 N NaOH; (II) NaH, 1-fluoronaphthalene; (III) NaBH4.
86. The major products (A) and (B) formed in the following reactions are
O O
Cl
SiMe3
(B) (A)
InBr3(cat.) InCl3 (cat.)
Me3SiCl (excess)
O O
(a) A = B=
O
HO
(b) A = B=
O O
(c) A = B=
HO O
(d) A = B=
O (i) I2, Pyridine

(ii) Pd(PPh3)4
H2C = CHSnBu3
(iii) NaBH4, CeCl3.7H2O
OH OH OH OH
(a) (b) (c) (d)
16
(i) SmI2
(ii) H2C=CHCO2Me
O O
O O OMe
(a) (b)
(c) (d)
O
O
O
Pd(OAc)2, n-Bu4NCl
+ KOAc, PPh3
MeO
OMe
(a) O (b)
MeO
MeO OMe
OMe
17
O
O
(c) (d)
MeO
MeO OMe
OMe
90. The major product formed in the following photochemical reaction is

O
hv
(a) (b)
O
O
(c) (d)
91. Correct sequence of reagents to be used for the following conversion is
18
OMe Et
Et
O O
(a) (I) LDA, EtBr; (II) EtLi; (III) H3O+ (b) (I) EtLi; (II) LDA, EtBr; (III) H3O+
(c) (I) H3O+; (II) EtLi; (III) LDA, EtBr (d) (I) EtLi; (II) H3O+; (III) LDA, EtBr
92. Both, 1-chloro-1-phenylpropan-2-one and 1-chloro-3-phenylpropan-2-one give same product (A) when
heated in presence of NaOMe. The product (A) is
(a) methyl 3-phenylpropanoate (b) methyl 2-phenylpropanoate
(c) methyl 2-methoxy-2-phenylacetate (d) 1-methoxy-3-phenylpropan-2-one
O
(i) LDA, H2C=CHCH2Br, –78ºC
N (ii) Cu(OAc)2
CN
CN CN
(a) (b)
O
O
O
N
(c) (d)
O
CH3COCl
AlCl3
Cl
Cl
O
Cl O
Cl
(a) (b) (c) (d)
O O
19
95. The structures of products (A) and (B) formed in the Edman degradation of the dipeptide are
O
H
N
PhNCS
H2N OH (A) + (B)
DIPEA
O
N
O OH
(a) A = Ph S B = H2N
N
H O
N
HN
O
O
(b) A = Ph S B=
N N
H S
Ph
N
HN
O
O
(c) A = Ph S B=
N N
H S
Ph
N
O OH
(d) A = Ph S B = H2N
N
H O
96. Partial spectroscopic data is given below for an organic compound
(I) 4 signals between  120-150 ppm in 13C NMR spectrum
(II) 2 doublets between  6.8-8.5 ppm in 1H NMR spectrum
(III) an absorption band at 1724 cm–1 in IR spectrum
The structure of the compound is
O
O
O
(a) (b)
O
20
O
O
(c) (d)
O
OMe
O
SPh (i) m-CPBA (1 equiv.)

(ii) Ac2O
(iii) aq. Na2CO3
O O
O SPh
(a) (b)
OAc O
O O
(c) (d)
98. The major products (A) and (B) in the following reaction sequence are
(+)-DET, (i-PrO)4Ti PhSH
Bu OH (A) NaOH (B)
t-BuOOH
OH
O
(a) A = Bu OH B = Bu SPh
OH
OH
O
(b) A = Bu OH B = Bu SPh
OH
SPh
O
(c) A = Bu OH B = Bu OH
OH
SPh
O
(d) A = Bu OH B = Bu OH
OH
99. The compound P undergoes a pericyclic reaction under photochemical conditions to give compound Q. In
compound Q, the relative stereochemistry and 1H NMR chemical shift values of methyl groups (in  ppm),
respectively, are
21
Me Me
(a) cis; –5 (b) trans; 17 (c) cis; 17 (d) trans; –5

O
Cl3CCOCl m-CPBA
(A) (B)
Zn–Cu
O
O O O
(a) A = B= O
Cl
Cl Cl
Cl
O O O O
(b) A = B= O
Cl
Cl Cl
Cl
Cl Cl
O O Cl
Cl
(c) A = B= O
O
O
Cl Cl
O O Cl
Cl
(d) A = B= O
O
O
101. Arrange the following molecules in order of increasing fundamental vibrational frequencies
(a) O22  O2  O2  O2 (b) O2  O 2  O 2  O 22
(c) O22  O2  O2  O2 (d) O2  O2  O 2  O 22
22
102. One of the Huckel molecular orbitals of 1, 3-butadiene is
  0.601  0.37 2  0.373  0.60 4
The energy of this orbital in terms of the coulomb    and resonance   integrals is
(a)   1.62 (b)   0.62 (c)   0.62 (d)   1.62
103. A molecule AB2 shows the following IR and Raman spectra

 cm 1  IR Raman
2215 vs, PR s, depol.
1250 vs, PR vs, pol.
560 s, PQR 
The structure of the molecule is

(a) Linear symmetruical  Dh  (b) Bent symmetrical  C2v 
(c) Linear asymmetrical  Cv  (d) Bent asymmetrical  Cs 
104. For a one-dimensional (x) harmonic oscillator perturbed by an x3 potential, the sum of the first order and
second order corrections to the ground state energy is
(a) < 0 (b) 0 (c) > 0 (d)  0
105. Difference of average values of position <x> for states n = 1 and n = 2 of a particle confined in a one-
dimensional (x) box of length L is
(a) L/4 (b) L/2 (c) L/3 (d) 0
106. The hermitian operator among the following is
d2 d
(a) i 2 (b) i (c) ix (d) i
dx dx
107. The translational partition function for Ar confined to a volume of 1 L at 300K, having thermal wavelength of
1.60×10–11 m, is closest to
(a) 24.4×1029 (b) 2.44×1029 (c) 0.244×1029 (d) 244×1029
108. Consider a phase transition between two incompressible phases. The correct statement among the following is
(a) The transition is independent of pressure
(b) The transition is independent of temperature
(c) The entropy of such transition is always zero
(d) The enthalpy of such transition is always non-zero
109. The third and fourth lines in the rotational Raman spectrum of CO are separated by 8 cm–1. The CO bond
length is given by
h 3h h 5h
(a) (b) (c) (d)
16 2 µc 32 2 µc 32 2 µc 32 2 µc
110. Conductivities of water and a saturated solution of a sparingly soluble salt AB2 are 7 and 21 µS m–1, respectively.
0 2 1 0 2 1
Given, A2  12.72 mS m mol and B  7.64 mS m mol , the solubility of AB2, in mol m–3, is
(a) 5.0×10–4 (b) 5.0×10–3 (c) 5.0×10–5 (d) 5.0×10–6
23
111. The equilibrium constant of the following reaction:
 2 Sn 2  aq 
Sn  s   Sn 4  aq  
at 300K is close to
 Given : E 0 4 2  0.15V and E 0 2  0.15V , R  8.314 JK 1mol 1; 
 Sn / Sn Sn / Sn 
 F  96485 Cmol 1 
 
(a) 106.08 (b) 108.08 (c) 1010.08 (d) 1012.08
112. Langmuir adsorption isotherm for the dissociative adsorption of D2 (p = partial pressure of D2 and k = ratio of
rate constants for adsorption and desorption) is
1/2 1/2
kp k  kp   p 
(a)   (b)   (c)   1/2 (d)    
1  kp 1  kp 1   kp   1  kp 
113. Entropy of a perfect gas is
(a) independent of V (b) proportional to V
(c) proportional to lnV (d) proportional to V2
114. The contour and root mean square length (in nm) of a polymer chain modelled as a random coil, with N
= 1000 and l = 150 pm, are closest to
(a) 1.50 and 47.4 (b) 15.0 and 4.74
(c) 150 and 47.4 (d) 150 and 4.74
115. The free energy  A  A  0   of a system with 10 non-interacting spins (S = 1) is
(a) k BT ln  3 (b) 10k BT ln  3 (c) k BT ln  0.3 (d) 10k BT ln  0.3
Table-1:
D2 h E C2  z  C 2  y  C 2  x  i   xy    xz    yz 
Ag 1 1 1 1 1 1 1 1 x2 , y2 , z 2
B1g 1 1 1 1 1 1 1 1 Rz , xy
B2 g 1 1 1 1 1 1 1 1 Ry , xz
B3 g 1 1 1 1 1 1 1 1 Rx , yz
Au 1 1 1 1 1 1 1 1
B1u 1 1 1 1 1 1 1 1 x
B2u 1 1 1 1 1 1 1 1 y
B3u 1 1 1 1 1 1 1 1 z
116. The  u -orbital of ethylene, when placed in the xy-plane with the C = C bond aligned to the x-axis, transforms
according to the irreducible representation (Use Table-1)
(a) au (b) b1u (c) b2u (d) b3u
24
117. The b1u  b2 g transition in ethylene is

(a) not allowed (b) allowed by to x-polarized light
(c) allowed by y-polarized light (d) allowed by z-polarized light
(Use Table-1)
118. A metal crystallizes with cubic close-packed structure. The sin 2  values of Bragg reflections of Miller Planes
(200) and (111) are 0.18 and 0.14, respectively. The unit cell length is
  
(a) (b) (c) (d) 0.4
2 0.2 0.4
119. kuni is the effective first-order rate constant of the following unimolecular reaction
k

1
A  M  A*  M
k1
k2
A*  P
The slope and intercept of the plot of 1/ kuni vs. 1/[M] are 4×106 and 8×10111, respectively. The value of
k1 / k2 is
(a) 2×105 (b) 0.5×105 (c) 32×105 (d) 2×10–5
120. The decomposition mechanism of ozone is
k

1
O3  O2  O
k 1
k2
O3  O   2O2
If k1 O2   k2 O3  , then the order of the reaction with respect to ozone is
(a) zero (b) one (c) two (d) complex
DETAILED
SOLUTIONS
June 11- Dec 18
PAPER : CSIR-UGC-NET/JRF Dec. 2016

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 
26. The oxidation state of gold in the following complex is
Me Me
Cl Au Au Cl
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
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
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
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)


O
(i) (CH3)2CuLi
OTBS
(ii) H2O
TBS = Si(CH3)2t-C4H9
HO O O HO
(a) (b) (c) OTBS (d)
OTBS OTBS OTBS

CO2CH3
Zn/Cu, CH2I2
CO2CH3
OCH3
(a) (b)
O
CO2CH3
OMe
(c) (d)
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).
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

(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

(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
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
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
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.
Correct option is (c)
22. Phosphorescence has been observed form a wide variety of compounds and is differentiated from
fluorescence by long lived emission of light after extinction of the excitation source i.e. it done after
fluorescence, if parsists.
Phosphorescence increases when heavy atoms like iodine silver and lead etc. are added.
Phosphorescence increases, when analyte used become immobile.
Hence, both (A) and (B) are correct.
Correct option is (b)
23. 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

Correct option is (a)

28. K  graphite   graphite K 

H2SO4  graphite   graphite HSO4
Correct option is (d)
29. In oxyhemerythrin  O O  850 cm1
In oxyhemoglobin  O O  1100 cm 1
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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SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017 21
SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017

PART–B
21. The cross-section    can be interpreted as the effective ‘target area’ that a nucleus interacts with an
incident neutron. Larger the effective area, greater the probability for reaction
In reaction, 92 U 235  10 n 
 36 Kr 94  56 Ba140  2 10 n , one neutron react with 92 U 235 to give two neu-
tron, which have more tendency to react with other radioactive nuclei. Thus, increases effective area
for reaction.
22. (a) Oxalic acid versus potassium permanganate:
 pink-purple  max  525 nm 
End-point is colorless 
(b) Iron (II) versus 1, 10-phenanthroline:
 Reddish-orange  max  512 nm 
End-point is colorless 
(d) Nickel (II) versus Dimethylglyoxime :
End-point is colorless  Red  max  445 nm 


(c) Cobalt (II) versus Eriochrome Black-T:
End-point is Blue-green  Blue


 pH  8  max  660 nm   max  600 nm 
Free EBT 
 Co  II  +EBT complex
Since, color change at end-point is not significant for option(c) which is requirement of the spectro-
photometric titration. Therefore, color monitoring method is not suitable in this case.
• Generally, ionisation energy increases on moving from left to right in a period in periodic table.
• Ionisation energy decreases as we move down in given group
• Ionisation energy will be more for full filled and half filled orbital.
7  6  3  1 26
24. ClO3    3  1  4  sp3 Tetrahedral
8 8
••
Cl = Pyramidal shape
O O
O
8  6  3 26
XeO3    3  1  4  sp3  Tetrahedral 
8 8
22 SOLVED PAPER : CSIR-UGC-NET/JRF Dec. 2017
••
Xe = Pyramidal shape
O O
O
6  6  3 24
SO3    3  sp 2  Trigonal planar 
8 8
O
S
O O
25. n + BF3 n BF3
H2O + BF3 H+ + HOBF3

cation formation  carbocation
3 eg
26. (A)  TiF6 
Ti  3d 2 4s 2 d1
Ti3  3d1 4s0 t2g
1 unpaired electron eg
(B) CrF63 d3
Cr  3d 5 4s1 t2g
3 3 0
Cr  3d 4s 3 unpaired electron
eg
3
(C)  MnF6  d4
Mn  3d 5 4s2 t2g
3 4
Mn  3d 4 unpaired electron
eg
(D) CoF63 d6
Co  3d 7 4s2
t2g
Co3  3d 6 4s0
4 unpaired electron
Hence, A < B < C = D
27. Cytochrome-C shows redox reaction and it is an essential component of electron transport chain,
whereas it is carriers of one electron and does not bind oxygen
6  5  7  3 32
28. SNF3    4  sp3  Td
8 8
8  6  2  7  2 34
XeO 2 F2    4  1  5  sp3d  TBP
8 8
N F
O
S
••
Xe
F F O
F F
Tetrahedral Trigonal bipyramidal
1  Co  H µCo  D 1934 1934

29. v     2   Co  D   1367.7  1396
µ  Co  D µCo H  Co D 2
30. In trigonal prismatic ligand field, energy of ‘d’ orbital is
d yz  d xz  d 2  d 2 2  d xy
z x y
Hence, the most stablized ‘d’ orbital is d xy

31. According to electroneutrality principle, each atom in any stable substance has a charge close to
zero. This means if central atom has more positive charge then it would be stabilized by ligand
having high negative charge density i.e. more electronegative donor atom.
3
In case of  Al  NH3 6  , nitrogen is sp3 hybridized hence it is least electronegative hence
least stable complex.
Electronic absorption band of I2 vapours appears at 520 nm i.e.  max of I2  gas   520 nm
32.
If solution is prepared with a solvent that able to form a charge transfer complex (CTC) like aromatic
solvents, ethers, alcohols etc. This absorption band shifted towards UV range i.e. blue shift. More
the donation of electrons from solvent to the * (LUMO) of I2 more will be the blue shift.
Here, option(d) methanol has highest electron donating capacity (i.e. most basic)
 max I2  Hexane   523nm Red shift
 max I2  Benzene   502nm Blue shift
 max I2  Methanol   440 nm Blue shift
 max I2  Water   460 nm Blue shift

Note: Methanol has low ionization potential (10.85 eV) than water (12.59 eV), therefore methanol
is better electron donar than water.
33. Spin-orbit coupling is larger for the heavier atoms (Inner transition) and very small for lighter atoms.
H
H H
•O •O •O
 M.C.
 +
34. 
m/z = 72
(4) COOH (1)
H
(R) Configuration
35.
HOOC (3) H (2)

HO
36. OH
OH
HO
Enterodiol is a lignan, formed by the action of intestinal bacteria on lignan precursors found in
plants.
Pyrrole Pyrazole Imidazole

37.
N
N
N N N
Weak
Base
H H H
H+ H+ H+ H
H
N N
Stronger NH
conjugate N N N N
acid
H H H H
H
pKa = –4.5 pKa = 2.5 pKa = 7.1
pK a  basicity
Lesser is the availability of lone pair for donation, lesser is the basic behaviour.
O O O O
H2O O O
S
S S
38. OH OH2
HO HO O
H
O O
S SO3H
H HO3S H
O
OH O H OH

39. Hydrogen bonding and no 1, 3-diaxial interaction
H
O
O
Me O

40. HOMO of hexatriene in hv condition is  4 . In  4 molecular orbital has three nodes.
No. of nodes
5. 6
4. 5
LUMO
LUMO
4
3.
HOMO
2. 3 HOMO
1. 2
0 1 hv

a a
c b c
b
e
d d
e
41.
c b c
a a
13
C NMR 
 Total 5-signal
MeO MeO +
MeO
Carbocation stabilized Carbocation stabilized

through (8 hydrogen) through (6 hydrogen) Carbocation stabilized
42. hyperconjugation hyperconjugation and allylic through (6 hydrogen)
double bond hyperconjugation and
np-vacant orbital
resonance stabilization
Order of stability of carbocation C > B > A

T
   of sample 32
43. Optical purity  T
 100   100  80%
   of pure enantiomer 40
O
O O O
KOH, MeOH
44.
Intramolecular
H H
Aldol reaction
OH H
OH OH
E1cB
O H O
O OH

O O
O O O
45. (I) (II) O (III)
Cyclic Ketone Cyclic Ester Anhydride
IR = 1745 cm–1 IR = 1770 cm–1 IR = 1865 cm–1
(C) (B) (A)
Br
Br a a
H H  = 7.38 (d)
Plane of symmetry
46. b b
H H  = 7.25 (d)
H H
C C singlet 1.29 ppm
c H H
H C H
H Hc
H
c
Cl
Once C2 passing through ‘B’ and ‘Cl’ atoms, two hydrogen interchange their position but
47. B remain same molecule.
H H

48. H2 a homo diatomic molecule will have not change in dipole moment. Thus, it will be IR inactive but
since H2 having polarisability in a Raman spectra. Thus, it will be Raman active.
Cl
sp2 [hybridisation]
B
49. Cl Cl
2
(3 + 3×7)/8 = 3 sp
50. Orbital degeneracy = n2 = 62 = 36
ˆ ˆ ˆ ˆ ˆ ˆ ˆ ˆ ˆ
 A, ˆ B
  A, ˆ C
ˆ   0 &  A, ˆ   0
51.  BC    A, B C  B  A, C   0      
 ikx
52. e.g. Let Aˆ  pˆ x which is a Hermitian operator and   e be operand
2
 
Aˆ  Aˆ e ikx    k  ; Aˆ 2   2 2 e ikx    2 k 2 e ikx
x
Therefore, eigen value is positive.
3 3
4 r 4  3 3  a 3
53. Packing fraction = Z      2  3.14      r  
3 a 3  4  8  4 
 3.2  5.2  7.2 
54. x   ppb  5.2 ppb
 3 
2 2 2
 xL  x   3.2  5.2    5.2  5.2    7.2  5.2 
s  N 1

3 1
ppb
22  0  22 8
 ppb  ppb  2 ppb
2 2
55. The stability of lyophobic colloids is a consequence of electrical double layer at the surface of the
particles
56. For strong electrolyte,  0 can be obtained from the plot of  vs c
Mw
57. P.D.I.= =1 for Monodisperse sample
Mn
 Mw  Mn
58. Rate of formation of I = Rate of deformation of I
k
 k1  A  k2  I    I   1  A
k2
59. G  ui ni
G  H  TS
H  G  TS
H  ui ni  TS
O
NH
N O
O
60. HO
OH OH
Uridine is glycosylated pyrimidine-analog containing uracil attached to ribose ring (ribofuranose)
via a ,  N1  glycosidic bond
PART–B
61. The peak area of differential thermal analysis is propportional to
(i) mass of the sample
(ii) heat of decompositional phase change
62. Electron diffraction is used to get the bond parameters of gaseous samples.
63. (a) Lu(III) = [Xe] 4f145d06s0, hence diamagnetic
(b) EuI2 has metallic lustre
(c) Ce(IV) used as oxidising agent
(d) Tb(III)-f8 has pink colour
64. Number of valence electron in CH2 = 6
Hence, fragment having 16 electron will be isolobal to this fragment.
A  CpCr  CO  2  5  6  4  15
B  CpCu  5  11  16
C  Ni  CO  2  10  4  14
D  Cr  CO  4  6  8  14 ; E  Fe  CO  4  8  8  16
65.  PMo12O40 3 is less basic. It is slightly less basic than ClO 4

66. (A) Due to more expansion of 5f orbital actinoids has more tendency to release electron hence have
more tendency to show oxidation state greater than +3 compared to Lanthanoids
(B) Actinoids (III) show either f-d or f-f transition, but no d-d transition
(C) UO 22 and PuO 22 are stable
(D) All the actinoids have radioactive isotopes
67. According to Bent’s Rule, ‘more electro negative element occupy axial position in trigonal bipyramidal
geometry.
68. According to Allred-Rochow, electronegativity can be given as
0.3590 Zeff
 AR   0.744 where, r = covalent radius.
r2
69. In I3 , there is intraction between * of I2 and non-bonding electron of I–. In case propanone and Br2,
there in interaction between * of Br2 and non-bonding electron of propanone.
Thus, both I2 and Br2 behave as acid.
70. According to reductive elimination reaction mechanism cis-complex can give the product but
trans-complex is not suitable for reaction and does not give reductive elimination product. Since,
ligand given in option (d) forms a trans-complex with Pd(II) due to the presence of flexible
methylene (–CH2–) groups. Therefore, reductive elimination not occured.
Me
P Pd P P P
Ph Ph Ph Ph
Pd
Ph Ph Ph Ph Ph
Me Ph
(trans)
(cis)
Actually formed but does not give reaction This can give the reaction but not formed

71. As the chelate ring size increases (in case of (d)), the energy of LUMO of complex cation
CpRu(P–P)+ (which formed after H– transfer) decreases and makes the complex cation better H–
acceptor and therefore decreasing the rate of H– transfer from CpRu(P–P)H.
+
Ph Ph CH3CN Ph Ph
P P P P + H–
Ph Ru Ph No reaction Ph Ru Ph
Cp H Cp NCCH3
(d) Low energy LUMO
High steric crowding due to so, better H– acceptor
large chelating ring
For d 6  high spin  there is one spin allowed transition from 5 T2g  5E g
In case of d6 low spin commonly two spin allowed transitions are observed.
1
 1T1g
A1g 
1
 1T2g
A1g 
there are additional spin allowed transitions at higher energy but they are marked by allowed transi-
tions. Hence, are not observed
73.  HOCl  H3O   Cl
A  Cl2  2H 2O 
B  Cl 2  2NH 3   NH 2 Cl  NH 4  Cl
Above both reactions are example of solvolysis as well as disproportionation
74. Sn 94  9  4  4  40 , thus it follow 4n + 4. Hence, it has nido structure
Correct option is (b)*
75. H 3 P  11BCl3
31  1 
P NMR   2 NI H  1 for 3H   2  3   1  4  quartet   1: 3 : 3 :1
 2 
31  3 
P NMR   2 NI B  1 for B   2   1  1  4  quartet   1:1:1:1
 2 
3H
1 3 3 1
B B B B
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
Intensity ratio : 1 : 1 : 1 : 1 : 3 : 3 : 3 : 3 : 3 : 3 : 3 : 3 : 1 : 1 : 1 : 1
3
76. K 3CuF6  3k   CuF6  , oxidation state of Cu3+ = 3d8
Thus, Cu3+ d8  Oh 
KCuL2  oxidation state of Cu = 1 + x–4 = 0  x  3

 
Cu 3 d8
Hence, square planar low spin
O H H O –
C N N C
K+ HN www.careerendeavour.com
Cu NH
C N N C
O H H O
77. In oxyhemerythrin, both the Fe are present as Fe(III) and there is presence of hydrogen bonding and
dioxygen bind to only one Fe.
78. Mechanism of base hydrolysis can be given as
2 
 Co  Cl   NH 3    Co  Cl   NH3   NH 2  
 OH  
 5  4 

slow 2
 Co  Cl   NH 3 4  NH 2   
RDS
  Co  NH3 4  NH 2   Cl
intermediate  C.N.5 
2
fast 2
 Co  NH3   NH 2    H 2O  Co  NH 3   OH  
 4   5 
79. Cubane like ferredoxin is Fe4S4

It has four inorganic sulfide which can be removed by treatment with acid.
8H 
Fe 4S4   Fe84  4H 2S
Ph Ph
Ph Ph Ph Ph
P 76º P P 85º P P 89º P
Ph Ph Pd Ph Ph Ph
Ph Pd Pd
80.
NCS SCN NCS SCN
SCN NCS
Small P–Pd–P angle, less Increase in P–Pd–P angle,increase in steric hindrance. No P–Pd–P bond angle, further increase
steric hindrance effective effective  bonding from the P atom, the S atom of SCN– with increase in size of chelate ring and
 Pd–SCN– bonding ligand can form  bond but due to steric hindrance SCN– hence steric hindrance increases. No effective
binds through N atom.  bonding from P, the S atom of SCN– can
form the  bond but steric hindrance favours
the Pd-N bonding
O Li O OTBDMS
O N O O
H
H Li TBDMS Cl MeO2C heat
81. LDA (4+2)
+ cycloaddition
OTBDMS
2
O1
CO2Me CO2Me 3
H2O O 1
CO2Me
2
HOOC [3,3]
TBDMSO sigmatropic
3
82.
H2N OH Ac–Cl
NH OH
O OH N OH
CN CN Backmann
fragmentation
N OAc
H
Base H N Ts Ts N
O OH N N
AcOH TsNHNH2
83. O O O
O
O H2, Pd/CaCO3 O
Pd(OAc)2
(Lindlar catalyst)
Product (B) Product (A)
H
H Cl
(Carbene)
C
••
C
Li+Me– H Cl
Cl
H Cl
C C
••
H
84. Cl
Carbene insertion –LiCl
N Me–Li+ N N N
H Li Li (Product)
O O
OH
C I2 I
NaHCO3
I
85. O H O
O
I I H DBU
DBU
O O O
Base
O O O
H H
*DBU = [1, 8-Diazabicycle [5.4.0] undec-7-ene]
Product (B) Product (A)
CN 2–
O Cu S OH
86. BnO NH4Cl/H2O
BnO

Cl
O
S
87. N Cl Cl
OH O
OH HN C HN C
H2N C
O O Cl
Cl
N N
N N
H
N
H Cl
N N C
H
HN N C N O
H
O

O O
Rh2(OAc)4(cat.)
+ N2
••
88. N2
••
O O
••
O O
[2, 3 STR]
2
O1 O
1 3
2
O O
S Ph www.careerendeavour.com
S Ph
O
SOPh
H
89. KOH Michael
H addition H
O O
O OH O
PhOS Intramolecular SOPh SOPh
Aldol
Reaction KOH
KOH
O O O
O O
OH H
Ph O
S H
H
syn elimination keto enol
Tautomerism
O O OH
OH

O O O O
•• NEt2
NEt2 NEt2 NEt2
C
90. OH2
Product (A) H+ –NEt2

O O O
O
O H3O+ O
OH2
OH OH
Product (B)
NO2 NO2
H NO2
H2O2/AcOH O N O
HNO3/H2SO4
91. N N N N N
O : PCl3
O O

92. The number of optically active stereoisomer are two
CH3 CH3
H OH HO H
H OH HO H
HO H H OH
CH3
CH 3
Optically active
O
H
H
93. (I) H (II) (III)
O
Br
 = 6.72 ppm
4n = 12 e– 4n+2 = 14 e–
in delocalization vinylic proton with EWG in delocalization
Therefore,anti-aromatic inner proton will Therefore, aromatic inner proton will be
be highly deshielded i.e. paratropic highly shielded i.e. diatropic anisotropy
anisotropy  = 16.4 ppm  = – 0.61
O O OH2 O
OH MeOH O OMe
HO + HO MeOH/H+ HO
H HO
94.
HO HO HO
HO
O O OMe
O OMe TBDMS-Cl
OH TBDMSO TBDMSO
HO (1eq.) Et3N
PDC
AcOH/H2O HO
O
O
H O
Peptide N CO2Me
SPh HS
NH2
95.
H O H O
H2N CO2Me
SH
Peptide N N
NH Peptide
S
CO2Me
SiMe3 SiMe3
H2SO4 TBAF
OTBDMS OTBDMS OH
96. Deprotection
OH OH2 of (–OH)
Anti-elimination
Ti(Pro)4, (+)–DET
t-BuOOH, CH2Cl2, –20ºC
OH
O
OMe OMe OMe
Br
LDA CO2Me
97.
1 equivalent
CO2Me CO2Me
H
(A)
CO2Me
O O OMe
OMe OMe
C H3O+ C O
OMe OMe
workup C
CO2Me CO2Me OMe
(B) C
O OMe

O
O O O
NaNO 2 NGP HBr
OH
OH OH
98. O
NH2 N2 Br
Br Br
H
H H
OH
heat cat. OsO4
99. 6 e– NMO
OH
H H
H
www.careerendeavour.com (cis-hydroxylation from
less hindered face)

O Br
B H
O (Ph3)2PdCl2, KOH
100. n Bu n-Bu n-Bu
then H2O
B(OH)2

101. Eigen functions are even for even values of vibrational quantum number (n) and odd for odd values
of n.
 h2   h2 
102. In 1-D box, E  5  2  and in 2-D box
E  3  2 
 8m   8m 
 h2 
And in 3-D box, E  3  2 
 8m 
103. For odd power of perturbed potential, E 1 is always ‘0’

104. Only Raman active, (symmetric vibration, change in dipole moment is zero during vibration)
105. Spherical top molecule  CH 4  Perfect geometry

I a  I b  Ic
Symmetrical top molecule  CH 3Cl  Ia  0, I b  Ic
106. According to GOT theorem, any two IR must be orthogonal to each other.
3 =  – 2 
2 = 
107.
1 =  + 2 
E1 3  2 E1 2  2  4.8  9.6 eV
108. E  g  B0  h  g  B0
  g
 H gH 600 MHz 5.6 600
    C   150 MHz
 C gC C
1.4 4
3
109. P2
Degeneracy = (2×2+1) = 5
S  k B nqe
For electron ground state, qe  ge
S  k B ng e  k B n5
110. dG  VdP  SdT  fdL ... (1)
Differentiating equation w.r.t. T at constant P, L
 G 
 T    S
  P, L
Similarly differentiating equation (1), w.r.t. L at constant P and T
 G 
    F
 T , P
Since, G is a stable function,
   G      G  
        
 L  T  P , L  T , P  T  L T , P  P , L
 S   F 
Or,     
 L T , P  T  P , L
111. For distinguishable particles,
n
g1ni g 0 0 g1n1 23 31 8
W  N i W  4    4    4   3  24  4  96
ni ; n0 n1 3 1 3 2
B C
V2
112.
Volume
V1
A D
T1 T2
wtotal  wAB  wBC  wCD  wDA

Process AB is isothermal,
V 
 wAB   nRT1n  2 
 V1 
Process BC is isochoric,
 wBC  0
Process CD is isothermal,
V  V 
 wCD   nRT2n  1   nRT2n  2 
 V2   V1 
Process DA is isochoric
V  V 
 wDA  0  wtotal   nRT1n  2   nRT2n  2 
 V1   V1 
V 
 nR T2  T1  n  2 
 V1 
 A 0.2
113. R  G k ; G   0.8  1
A  0.25
0.0591  0.01 
114.
0

Ecell  Eright 0
 Eleft   2
log  
 0.01 
Ecell  0.403  0.447 ; Ecell  0.044V
N1M1  N 2 M 2 50  500  75  6000
115. Mn    5600
N1  N 2 50  75
d123 3.12 d 3.12

116. d 246    1.56 nm ; d 369  123   1.04 nm
2 2 3 3
km
117. slope   300 ... (1)
rmax
1
Intercept   2  105 ...(2)
rmax
1  k  1.5 103

m
 2
118. For a bubble, surface tension counteracts internal pressure

2
 Pint  Pout 
r
2
 Pint  Pout 
r
119. From entry (1) and (2), order w.r.to, B = 1
And from entry (3) and (4), order w.r.to. A = 2
120. A2  B   product

Slope = 2 AZ A Z B  2 A  2  1  4 A   ve  salt effect 
Thus, plot having negative slope

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CSIR NET JRF

June 2011 – Dec. 2018

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

PAPER : CSIR-UGC-NET/JRF June 2017

37. Following reaction is an example of

38. The major product of the following reaction is

39. The most stable conformation of 2-fluoroethanol is

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

(a) 9-borabicyclo[3.3.1]nonane (b) 1-borabicyclo[3.3.1]nonane

IV. Geranyl pyrophosphate