GATE-CY 2016 QUESTION PAPER 1

CHEMISTRY-CY
Q.1 – Q.25 : Carry ONE mark each.
1. [CpMoCl2]2 obeys the 18 electron rule. The correct structure of this compound is (atomic number of Mo
= 42)
Cl Cl Cl Cl

Mo Mo Mo Mo
(a) (b)
Cl Cl Cl Cl

Cl

Cl
Cl Cl
Mo Mo
Mo Mo
(c) Cl
(d)
Cl Cl
Cl
2. During oxygen transport by hemerythrin, oxygen is bound as
(a) O2– to one Fe(III) only (b) HO2– to one Fe(III) only
(c) O22– to one Fe(II) and one Fe(III) (d) O22– to two Fe(II)
3. Among the following, the most stable isotope to radioactive decay is
206 210 212 214
(a) 82 Pb (b) 82 Pb (c) 82 Pb (d) 82 Pb
4. At pH 7.2 and 10 Torr oxygen partial pressure, the extent of O2 binding is
(a) high for both haemoglobin and myoglobin
(b) high for haemoglobin and low for myoglobin
(c) high for myoglobin and low for haemoglobin
(d) low for both haemoglobin and myoglobin
5. In the first row high-spin transition metal complexes [M(H2O)6]Cl2 with d5 and d7 metal ions, the d-d
transitions are
(a) spin-forbidden for both
(b) spin-allowed for both
(c) spin-forbidden for d5 and spin-allowed for d7
(d) spin-allowed for d5 and spin-forbidden for d7
6. Among the given boranes and heteroboranes, the example which belongs to ‘closo’ type is
(a) B5H8– (b) [C2B9H11]2– (c) GeC2B9H11 (d) B6H10
7. The reaction of P2O5 with HNO3 and HClO4, respectively, gives
(a) NO2 and ClO2 (b) N2O5 and Cl2O6
(c) N2O3 and Cl2O7 (d) N2O5 and Cl2O7
8. When crystals of sodium chloride are heated in the presence of sodium vapor, they turn yellow. This is
due to the formation of
(a) Schottky defects (b) Frenkel defects
(c) F-centres (d) H-centres
9. One mole of an ideal gas is compressed from 5L to 2L at constant temperature. The change in entropy,
in J K–1, of the gas is ___________________. (R = 8.314 JK–1 mol–1)
GATE-CY 2016 QUESTION PAPER 2

10. The linear momentum of a particle described by the wavefunction e ikx is

(a) kh (b) kh (c) k (d) k 
11. For an elementary bimolecular gas phase reaction, activation energy is 5.5 kJ mol–1. Enthalpy of activa-
tion, in kJ mol–1, at 300K is _________. (R = 8.314 J K–1 mol–1)
12. The titration of a strong acid with a strong base is represented by the plot

pH/V pH/V
(a) (b)
Volume (V) Volume (V)

pH/V pH/V
(c) (d)
Volume (V) Volume (V)
13. Of the following inequalities, the criteria for spontaneity of a chemical reaction is/are
(i)  G T , P  0 (ii)  U  S ,V  0 (iii)  S U ,V  0
(a) (i) only (b) (ii) only (c) (i) and (ii) (d) (i) and (iii)
14. A protein sample consists of an equimolar mixture of ribonuclease (molar mass = 13.7 kg mol–1), hemo-
globin (molar mass = 15.5 kg mol–1), and myoglobin (molar mass = 17.2 kg mol–1). The statement that is
true about the weight-average molar mass  M w  , the number-average molar mass  M n  , and the poly-
dispersity index (PDI) for this sample is
(a) M w  M n  15.5 kg mol 1 and PDI  1 (b) M w  M n  15.5 kg mol 1 and PDI  1
(c) M w  15.5 kg mol 1 > M n and PDI  1 (d) M w  15.5 kg mol 1 < M n and PDI  1

15. The band structure given below represent a

Conduction
Band
Energy

Valence
Band

(a) n-type semiconductor formed by doping Si with B

(b) n-type semiconductor formed by doping Si with P
(c) p-type semiconductor formed by doping Si with P
(d) p-type semiconductor formed by doping Si with B
16. The experimental ionization energies of hydrogen and helium atoms in their ground states are, respec-
tively, 13.6 eV and 24.6 eV. The ground state energy of helium atom, in eV, is
1 1
(a)  13.6   24.6 (b) 4 13.6   24.6 (c)  13.6   24.6 (d) 2 13.6   24.6
2 4
GATE-CY 2016 QUESTION PAPER 3
17. Ring flipping of the compound in the following conformation leads to
CH3
Br
HO

OH OH
CH3 CH3
(a) (b) CH3
(c) (d)
Br Br Br H3C Br
OH OH

18. The total number of lines expected (due to spin-spin coupling of proton with fluorine and deuterium nuclei) in
the 1H NMR spectrum of the following compound is _______________.

H
D

Cl F

19. The compound in ‘R’ configuration is [GATE 2016]

C2H5 CH3 H3C CH3
(a) (b)
H H H3C H
H3C CH3 H CH3
(c) (d)
H CH3 C2H5 H

20. The most suitable reagent for performing the following transformation, is
O CH3 O CH3

N3 NH2

(a) LiAlH4 (b) H2, Pd/C (c) PPh3, H2O (d) Li, Liq. NH3
21. The major product obtained in the following reaction, is
hv
acetophenone
(as sensitizer)

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

cis-trans mixture
22. The Favourable transition state leading to the formation of the product in the following reaction, is
B(Chx)2
O O OH
(i) PhCHO, –78ºC

(ii) H2O2, NaOH Ph Ph

Ph
CH3
CH3
Chx = cyclohexyl
GATE-CY 2016 QUESTION PAPER 4

Chx
Chx B
O Ph
O O Chx
H B
H
(a) (b) Ph
H3C
H O
Ph Chx Ph
CH3
Chx
Chx
B
O O O
Chx Ph Ph B
H
(c) Ph (d)
H3C
H O
H Chx Ph
CH3
23. The major product of the following reaction is,

(CH3CO)2O
BF3.Et2O, 0ºC
O
O
O O
CH3 H3C
CH3 CH3 CH3
H3C
(a) (b) O (c) O (d)
O
O O O
O
24. The major product obtained in the following reaction, is
(i) LiNH2 (2equiv.)/liq. NH3
H C C CH2OH
(ii) C2H5Br(1 equiv.)
(ii) H3O+
(a) H3CH2C C C CH2OH (b) H C C CH2OCH2CH3
(c) H3CH2C C C CH2NH2 (d) H C C CH2NH CH2CH3

25. The major product formed in the following reaction, is

O

(i) CH3I
N(C2H5)2
(ii) NaHCO3/MeOH, warm

O OCH3
H3C
N(C2H5)2 N(C2H5)2
(a) (b)

O O
CH2 CH3
N
(c) (d)
C2H5
GATE-CY 2016 QUESTION PAPER 5
Q.26 – Q.55 : Carry TWO marks each.
26. The Larmor frequency of 1H at 1 Tesla (T) is 42.57 MHz. If the magnetogyric ratios for 1H and 13C are 26.75
× 107 rad T–1 s–1 and 6.72×107 rad T–1 s–1, respectively, the Larmor frequency of 13C, in MHz, at 1 Tesla will
be _____________

27. At 1 bar and 298K, for the process A  s   A    , the G is 200 J mol–1 and Vm is –2×10–6 m3 mol–1.
The minimum pressure, in bar, at which the process becomes spontaneous at 298K is ____________. (1 bar
= 105 Pa).

28.  B, is first order in both the directions. The forward and reverse rate constants are
The reaction, A 

4.2  104 s 1 and 1.04  103 s 1 , respectively. The relaxation time for this reaction, in seconds, in a tempera-
ture jump experiment is _____________
29. Adsorption of CO on charcoal at 273K follows Langmuir isotherm. A plot of P(kPa)/V(cm3) versus P
(kPa) is linear with a slope of 0.01 y-intercept of 0.5. The equilibrium constant, K (kPa–1), for the
adsorption is _____________.
30. For the following reaction,
5 1 1
 
k1 10 L mol s 1
k 2 10s
A  B 
k 104 s1
 I  P
1

if steady state approximation can be applied on [I], the observed rate constant of product formation, in L
mol–1 s–1, will be ______________

31. The correct set of infra-red spectral bands (in cm–1) for the  CO stretching mode of the given carbonyl
complex is

Rh
CO OC

Rh Rh
O
C

(a) 1827, 1783, 1766 (b) 1973, 1827, 1794

(c) 1833, 1775, 1650 (d) 1960, 1918
19
32. The F NMR spectrum of ClF3 when measured at –60ºC will be observed as a
(a) singlet (b) doublet
(c) doublet and triplet (d) doublet of doublet and a doublet of triplet
33. Among the given platinum(II) complexes, the one that is thermally the most unstable is
Ph3P CH2C(CH3)3 Ph3P

(a) Pt (b) Pt
Ph3P CH2C(CH3)3 Ph3P

H
Ph3P
Ph3P CH2CH2CH2CH3
Pt Pt
(c) (d)
CH2CH2CH2CH3 Ph3P
Ph3P
H
GATE-CY 2016 QUESTION PAPER 6

34. T he shapes of X eF5+ and XeF5– , respectively, are

(a) pentagonal planar and square pyramidal
(b) pentagonal planar and trigonal bipyramidal
(c) square pyramidal and pentagonal bipyramidal
(d) square pyramidal and pentagonal planar
35. Sodium salt of pseudohalogens, X, Y and Z form colorless solutions in water. Solution of X decolorizes
I3– solution with brisk effervescence. Solution of Y gives an intense red colour on reaction with Fe3+
solution. Solution of Z gives an intese blue color on reaction with a solution containing Fe3+ and Fe2+ ions.
The pseudohalogens X, Y and Z respectivley are
(a) CN  , N 3 and CNS (b) N 3 , CNS and CN 
(c) N 3 , CN  , and CNS (d) N 3 , CNS , and CNO 

36. On reacting 1.55g of a diol with an excess of methylmagnesium iodide, 1.12L (corrected to STP) of
methane gas is liberated. The molecular mass  g mol  of the diol is _____________
37. The structure of the compound having the following characteristics spectral data, is IR : 1690 cm–1.
1
H-NMR : 1.30 (3H, t, J = 7.2 Hz); 2.41 (2H, q, J = 7.2 Hz); 2.32 (3H, s); 7.44 (1H, t, J = 7.0 Hz);
7.57 (1H, dt, J = 7.0, 3.0 Hz); 7.77 (1H, t, J = 3.0 Hz); 7.90 (1H, dt, J = 7.0, 3.0 Hz); EI mass : m/z 119
(100%); 57 (80%)
O O
O O
CH2CH3 CH3
CH2CH3 CH3
(a) (b) (c) (d)
CH3 CH2CH3
CH3 CH2CH3

38. The major products X and Y formed in the following formed in the following synthetic scheme, are

(i)
N
, cat. H+
O
H
benzene (solvent) (H3C)2S CH2
(X) (Y)
(ii)
O
+
(iii) H , H2O
(iv) aq. NaOH, heat

O O O
O

(a) X = Y= (b) X = Y=

O O O O
(c) X = Y= (d) X = Y=
GATE-CY 2016 QUESTION PAPER 7
39. The major product S and T formed in the following synthetic schemem, are
O O
O
P
(i) EtO OEt , NaH
OEt D-(–)-diethyl tartrate
(S) (T)
(ii) LiAlH4 t-BuOOH, Ti(OiPr)4

HO HO HO HO
O O

(a) (b)
S= T= S= T=

OH OH OH OH
O O

(c) (d)
S= T= S= T=

40. Among the following, the transformation(s) that can be accomplished using umpolung concept is(are)
O
OEt (i)

H3C O O
(ii)
H
O
H3CH2C H (iii)

OTr O
(iv)
(Tr = trityl)
(a) (i) and (iii) (b) (ii) and (iv) (c) (ii) only (d) (i) and (ii)
41. A disaccharide does NOT give a positive test for Tollen’s reagent. Upon acidic hydrolysis, it gives an
equimolar mixture of two different monosaccharides, both of which can be oxidized by bromine water.
This disaccharide is
OH

O HO OH
HO
HO O O
(a) (b) HO OH
OH HO
O HO
OH
OH O
OH O
HO
OH
OH
GATE-CY 2016 QUESTION PAPER 8

OH OH

O O
HO HO
HO HO
OH OH
O O
HO HO
(c) HO (d) HO
HO
O O

OH
OH OH

42. The major products M and N in the following reaction sequence are
O H
H3C CH3
LiPPh2 CH3I
(M) (N) + + LiI
PPh2
H3CO O
CH3
OLi H H3C CH3
H3C
(a) M = N=
H3CO CH3
PPh2 H3CO H

OLi H H3C H
H3C
(b) M = N=
H3CO CH3
PPh2 H3CO CH3

OLi H H3C CH3

H3C
(c) M = N=
H3CO CH3
PPh2 H3CO H

OLi H3C H
H3C H
(d) M = N=
H3CO CH3
PPh2 H3CO CH3
43. The major products P and Q in the following reaction sequence, are
Me3SiO
CN OAc (i) , 110ºC (i) PhMgBr(1 equiv.)
+ (P) (Q)
(ii) excess NaOMe (ii) dil. H2SO4, heat
in MeOH

(a) P = Q= (b) P = Q=
O O Ph O O
O O Ph

Ph O Ph
O
(c) P = Q= (d) P = Q=
O O O O
GATE-CY 2016 QUESTION PAPER 9
44. The major product formed in the following reaction, is
PhBr(1 equiv.)
Cat. Pd(PPh3)4
KOAc, DMF
O CH3

Ph
Ph Ph
Ph
(a) (b) (c) (d)
O CH3 O CH3 O CH3
O CH3
45. The following synthetic transformation can be achieved using
O
O

NH

Reagents:
(p) (i) NH2OH/H+, (ii) H2SO4
(q) NH3/H+
(r) (i) NH2OH/H+, (ii) NaOH
(a) p only (b) p and q (c) q and r (d) r only
46. Consider a two-state system at thermal equilibrium with equal degeneracy where the excited state is
higher in energy than the ground state by 0.1 eV. The ratio of the population of the excited state to that of
the ground state, at a temperature for which kBT = 0.05 eV, is __________
47. Of the vibrational modes given below, the IR active mode(s) is(are)

(i) O C O (ii) O C O (iii) O C O

(a) (ii) only (b) (iii) only (c) (i) and (ii) (d) (ii) and (iii)
48. A system is described by the following real wavefunction.

I III

 x

II
The probability (P) of finding the particle in a region dx around points I, II and III in the figure obeys the
trend
(a) P(I) > P(II) > P(III) (b) P(II) > P(III) > P(I)
(c) P(II) > P(I) > P(III) (d) P(III) > P(I) > P(II)
GATE-CY 2016 QUESTION PAPER 10
49. The temperature-composition (T-x) phase diagram of the two-component system made of X and Y is
given below. At a temperature of 288K and starting at the point P, Y is added until the composition
reaches S. Which of the following statements is NOTR TRUE?

T
Liquid
Q R S
288K P

Solid X + Y

0 0.4 1.0

mole fraction of Y

(a) At P, the solid and liquid are present in almost equal proportions
(b) At Q, the system is all liquid
(c) At S, the system has more solid than liquid
(d) At R, the liquid is pure X
50. For a system subjected to only P-V work, entropy is given by

 
G
(I)  T
P
 G 
(II) P
T
A
(III)  V  T
(IV)  T
A
 
V
(a) I and II (b) I and IV (c) I only (d) II only
51. According to Irving-Williams series, the number of d electrons for the first row transition metal (M) ion
having the highest overall stability cosntant log for [M(EDTA)]2– is ______________
52. The magnitude of the difference in the crystal field stabilization energies, in 0 (irnoring pairing energy), of
[Fe(H2O)6]2+ and [Fe(CN)6]4– is _________________
53. The calculated and observed magnetic moments differ considerably for an aqua complex of a Lanthanide
(III) ion as a result of low lying states of high J. The ion, among the follwing, is
(a) Ce3+ (b) Pr3+ (c) Eu3+ (d) Yb3+
3
54. In the electronic spectra of  CrF6  , absorption bands observed at 670, 440 and 290 nm are, respectively,,
due to the transitions.
(a) 4 A 2g  4 T1g  P  , 4 A 2g  4T1g  F  and 4 A 2g  4T2g
(b) 4 A 2g  4T1g  P  , 4 A 2g  4T2g and 4 A 2g  4T1g  F 
(c) 4 A 2g  4T1g  F  , 4 A 2g  4T1g  P  and 4 A 2g  4 T2g
(d) 4 A 2g  4T2g , 4 A 2g  4T1g  F  and 4 A 2g  4 T1g  P 
55. Amongst the following, the group that is bound to the metal ion in coenzyme B12 is
(a) methyl (b) cyanide (c) adenosyl (d) hydroxyl

***** END OF THE QUESTION PAPER *****