Archive JEE Advanced Solutions Chemistry PDF

Unit 2
CHEMISTRY
Solutions
SECTION - A
Only One Option Correct Type Questions
1. Answer (B)
We will have to take weighted average
54  5  90  56  5  57
= 55.95
100
2. Answer (C)
Centripetal force = Coulombic force of attraction
mV 2 KZe2
=
r r2
KZe2
V2 =
mr
nh
V=
2mr
n 2h 2
V2 =
4  2m 2r 2
KZe2 n 2h 2
 
mr 4  2 m 2r 2
⎛ h2 ⎞ n2 a 0 n 2
 r⎜ 2 2 ⎟

⎝ 4 mKe ⎠ Z Z
hZ
Vn =
2ma0n
1 h2 Z 2 h2
K.E. = mv n2  2 2 2 ; K.E. (for x = 2 and Z = 1) =
2 8 ma0n 32 2ma02
3. Answer (A)
Radial probability function curve for 1s is
r
Here ‘P’ is 4 r 2  r2 dr
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2 Answers and Solutions_Chemistry ARCHIVE - JEE (Advanced)
4. Answer (A)
Molecular orbital diagram for B2 where Hund’s rule is violated.
2p2X
1s 2  * 1s 2 2s 2  * 2s 2
2p0Y
 Bond order = 1 and diamagnetic.

5. Answer (D)
Pyramidal
S
O F
F
6. Answer (D)
F O
Xe  See saw.
F O
7. Answer (C)
Be2 = 1s2*1s22s2*2s2
B2 = 1s2*1s22s2*2s22pz2
C2 = 1s2*1s22s2*2s22pz22px12py1
N2 = 1s2*1s22s2*2s22pz22px22py2
8. Answer (B)
Correction factor in pressure is directly proportional to square of density.
an2
 It is
V2
9. Answer (C)
⎛ a ⎞
⎜ P  V 2 ⎟ V = RT
⎝ ⎠
a
PV + = RT
V
a
PV = RT –
V
⎛ 1⎞
So, plot of (PV) vs ⎜ ⎟ has slope – a.
⎝V⎠
20.1  24.6
 Slope =  – 1.5
3
 a = 1.5 atm L2 mol–2
ARCHIVE - JEE (Advanced) Answers and Solutions_Chemistry 3
10. Answer (B)
Cl2 is considered as standard state of chlorine and enthalpy of formation in standard state is zero (assumed).
11. Answer (C)
Bond energy of C—C is considered to be 100 kcal mol–1 approximately.
12. Answer (D)
H = Bond energy in reactant – Bond energy in product
 225 = (1410 + 330) – (700 + HCC)
 HCC = 1740 – 925 = 815 kJ/mol
13. Answer (C)
C6H12O6(s) + 6O2(g)  6CO2(g) + 6H2O(l)
H° = 6 (–400) + 6(–300) – (–1300)
H° = –2900 kJ/mol
2900
H    16.11 kJ/gm
180
14. Answer (B)
Given conditions are boiling conditions for water due to which
Stotal = 0
Ssystem + Ssurroundings = 0
Ssystem = –Ssurroundings
For process, Ssystem > 0
Ssurroundings < 0
15. Answer (C)
For isothermal change U = 0
 q = – w = PexU
= 3 × (2 – 1)
= 3 L atm
= 3  101.3 J
Heat released from surrounding = –3 × 101.3 J
–3  101.3
So, Ssurrounding   –1.013 JK –1
300
16. Answer (A)
Gº = V·P
 2900  2  10 –6 P
2900  106
 P  Pa
2
PF–1 = 14500 bar
 PF = 14501 bar
17. Answer (D)

(MX) S2 = 4.0 × 10–8
S = 2.0 × 10–4
(MX2) 4S3 = 3.2 × 10–14
S3 = 0.8 × 10–14
S3 = 8 × 10–15
S = 2 × 10–5
(M3X) 27S4 = 2.7 × 10–15
S = 1 × 10–4
 Order is MX > M3X > MX2
18. Answer (B)
( 5) ( 2) (0) ( 3)
H NO3 , NO, N2 , NH4 Cl
19. Answer (A)
H2O2 acting as a reducing agent with KIO4 and H2O2 acting as an oxidising agent with NH2OH.
20. Answer (A)
Oxidation state
H3PO4 P=+5
H4P2O6 P=+4
H3PO3 P=+3
H3PO2 P=+1
H3PO4 > H4P2O6 > H3PO3 > H3PO2
21. Answer (D)
Area covered by particle

Packing efficiency =
Total area
2  r 2
=
a2
2  r 2
=
(2 2 r)2

=
4
22. Answer (B)
1 1
Number of X atoms/ ions per unit cell = 8  6 4
8 2
1
Number of M atoms/ions per unit cell = 1  4  2
4
 Empirical formula of the compound is MX2.
23. Answer (A)
Cation A+ occupies octahedral void formed by anions X–. The maximum radius ratio for a cation to
accommodate a octahedral void without distortion is 0.414. Radius of anion X– is 250 pm.
RA
 0.414
R X
 R A   0.414  250  103.50 104 pm
24. Answer (A)

As the mole fraction of N2 gas is 0.8 and total pressure is 5 atm. Therefore the partial pressure of N2 will be
4 atm.
Now, Pa = KH Ha
n
4 = 1 × 105  (∵ n is much less than 10)
n  10
n = 4 × 10–4 moles
25. Answer (C)
wt. of solute 1000

M 
mol. wt. of solute volume of solution
120 1000
M   2.05
60 1120
1.15
26. Answer (A)
0.1
329
Tf – Tf = 0 – Tf = 4 × 1.86 ×
100
1000
0.1 1000
Tf  4  1.86    0.023
329 100
27. Answer (A)
Tb = 1 × Kb × m
 2 = 1 × 0.76 × m
2
 m=  2.63
0.76
760  PS 18
  2.63 
760 1000
 Ps = 724 mmHg
28. Answer (C)
⎡ W  1000 ⎤
Tf = iK f ⎢ 2 ⎥
⎣ M2  W1 ⎦
⎡ 34.5  1000 ⎤
= 1 2 ⎢
⎣ 46  500 ⎥⎦
=3K
273 (K) – Tf = 3 (K)

 Tf = 270 K
Also, with decrease in temperature, V.P. decreases.
 Graph (C) is correct.
29. Answer (B)
W it

E F
W 10  10 3  t
 0.01 2 
E 96500
t = 19.3 × 104 s
30. Answer (D)
Ag+ and K+ have nearly same ionic mobility
AgNO3 + KCl  AgCl(s) + KNO3
conc. of KCl
31. Answer (D)
0.0591 [Fe2 ]2
Ecell  1.67  log
4 pO2  [H ]4
0.0581 (103 )2
 1.67  log
4 0.1 (103 )4
0.0591 106
 1.67  log
4 1013
0.0591
 1.67  log107
4
0.0591
 1.67   7  1.57
4
32. Answer (D)
H2 (g)  2H  2e –
M4   2e –  M2 
H2 (g)  M4   2H  M2
H 2  M2 
Qx 
M4 
(1)2  M2  M2  , º
  Ecell  Eº 4 – Eº 
/M2 
M 
4 M4  M H /H2
= 0.151 – 0
= 0.151 V
0.059
E  0.151– log10 x
2
0.059
0.092  0.151– log10 x
2
On solving, we get x = 2
33. Answer (A)
Zn | ZnSO4 || CuSO4 | Cu
(aq) (aq)
G =G° + RT In Q
⎛ [Zn2 ] 10 ⎞
G = G° + 2.303 RT log Q ⎜⎜ Q   ⎟
⎝ [Cu2 ] 1 ⎟⎠
G° = – nFE°Cell
= – 2F  1.1
= – 2.2 F
10
G = – 2.2 F + 2.303 RT log
1
G  2.303 RT – 2.2 F
34. Answer (D)

1
log k = – (2000) + 6.0
7
Ea
Comparing this equation with log k = log A – , we get
2.303 RT
log A = 6
 A = 106 s–1
Ea 2000
and – =–
2.303 RT T
Ea = 2000 × 2.303 × 8.314
Ea = 38.3 kJ mol–1
35. Answer (A)
Ea

k  A e RT
Ea
ln k = ln A –
RT
36. Answer (A)
He4
27
13 Al 
2
 30
14 Si  1H1
(X)
He4
27
13 Al 
2
 30
15 P  10 n
(Y)

14 Si 
30 1
1 e
(Z)
37. Answer (D)
The order of reaction with respect to P is one since t3/4 is twice of t1/2. From the given graph the order of
reaction with respect to Q is zero. Therefore, overall order of reaction is one.
38. Answer (B)

r2 ⎛ [M]2 ⎞
⎜ ⎟
r1 ⎝ [M]1 ⎠
8 = (2)
=3
So, order of reaction is 3.
39. Answer (C)
Coagulating power of a electrolyte is dependent on the valency of effective ion and Sb2S3 is negatively charged
sol.
 Answer is Al2(SO4)3.
40. Answer (B)
The adsorption of methylene blue on activated charcoal is physiosorption which is exothermic, multilayer and
does not have energy barrier.
41. Answer (D)
 A solution of CH 3OH and water shows positive deviation from Raoult's law, it means by adding
intermolecular force of attraction decreases and hence surface tension decreases.
 By adding KCl in water, intermolecular force of attraction bit increases, so surface tension increases by
small value.
 By adding surfactant like CH3(CH2)11OSO3–Na+, surface tension decreases rapidly and after forming micelle
it slightly increases.
42. Answer (B)
P4  O2  P4 O6
(air )
(78% N2  21% O2 )
43. Answer (D)
Ba(N3)2  Ba(s) + 3N2 

44. Answer (D)
P4 on disproportionation produces PH3, NaH2PO2 and Na3PO3.
45. Answer (B)
Conc. HNO3 slowly decomposes as
4HNO3  4NO2 + 2H2O + O2
It acquires yellow-brown colour due to the formation of NO2.
46. Answer (A)
P4  8SOCl2  4PCl3  4SO2  2S2Cl2

(White)
47. Answer (C)
Complete
XeF6 Hydrolysis
XeO3 + H2F2
OH–/H2O
–
HXeO4
Slow disproportionation in OH–/H2O
–4
XeO6 + Xe(g) + H2O + O2(g)
48. Answer (B)
The increasing order of atomic radii is
Ga < Al < In < Tl

r
(pm) 135 145 167 170
49. Answer (D)
Haematite Fe2O3 Fe+3
Magnetite Fe3O4 Fe+2 and Fe+3
50. Answer (B)

Ag2 S  4NaCN
2Na[Ag(CN)2 ]  Na2 S
Na 2 S 2  2O 2  Na 26 SO 4
2Na[Ag1(CN)2 ]  Zn  Na2 [Zn(CN)4 ]  2Ag0 
51. Answer (A)
Silver, copper and lead are commonly found in earth's crust as Ag2S (silver glance), CuFeS2 (Copper pyrites)
and PbS (Galena)
52. Answer (C)
In CuF2, copper is in +2 oxidation state
 coloured. In other options copper is in +1 oxidation state therefore colourless.
53. Answer (A)
Complementary colour of blue is (Orange-red)
54. Answer (B)
Zn + 2NaOH  Na2ZnO2 + H2
Iron become passive with conc. HNO3.
Copper liberate NO2 with HNO3
55. Answer (B)
[Ni(CO)4] --------- sp3 hybridization
[Ni(CN)4]–2 --------- dsp2 hybridization
56. Answer (A)

Cr(CO)6
Cr in G.S.
Under the influence
of strong ligand
2 3
d sp hybridization
Diamagnetic  = 0
57. Answer (B)
Cr(H2O)4Cl(NO2)]Cl and [Cr(H2O)4Cl2](NO2) have same molecular formula but they give different ions on ionization.
58. Answer (C)
HOOC CH2 CH2 COOH
N CH2 CH2 N
HOOC CH2 CH2 COOH
59. Answer (B)
Ni2+ is sp3 hybridized and metal ion is connected with weak ligands.
 Ni2+  d 8
two unpaired electrons sp3
 s = 2 (2  2) B.M.
= 8 B.M. = 2.83 B.M.

60. Answer (B)
Ni+2 + 4Cl–  [NiCl4]–2 (tetrahedral)
Ni+2 + 4CN–  Ni(CN)4–2 (square planar)
Ni+2 + H2O  Ni(H2O)6+2 (octahedral)
61. Answer (C)
[Co(NH3)6]Cl3 d 2sp3 diamagnetic
Na3[Co(OX)3] d 2sp3 diamagnetic
K2[Pt(CN)4] dsp2 diamagnetic
[Zn(H2O)6](NO3)2 sp3d2 diamagnetic
62. Answer (D)
63. Answer (C)
The hybridisation of Ni2+ in paramagnetic complex is sp3 and hence the complex is tetrahedral. The diamagnetic
complex is square planar as the hybridisation of Ni2+ is dsp2.
64. Answer (B)
The electronic configuration of central metal ion in complex ions P, Q and R are
P  [FeF6 ]3 ; Fe3 :

3d
Q = [V(H2O)6]2+; V2+:
3d
R = [Fe(H2O)6]2+; Fe2+
3d
The correct order of spin only magnetic moment is Q < R < P

65. Answer (B)
[NiCl4]2– and Na3[CoF6] are paramagnetic since involve weak field ligand. CsO2 is paramagnetic due to
paramagnetism by O2–.
66. Answer (A)
2
Ni2   6NH3  ⎡⎣Ni NH3 6 ⎤⎦
octahedral
2
Pt 2   4NH3  ⎣⎡Pt NH3 4 ⎦⎤
(square planar )
2
Zn2  4NH3  ⎡⎣ Zn NH3 4 ⎤⎦
tetrahedral
67. Answer (A)

Cu+2 and Hg+2 belong with 2nd group of basic radical.
68. Answer (D)
Upon treatment with ammoniacal H2S, Zn2+ ion gets precipitated as ZnS. Fe3+ ion and Al3+ ions also get
precipitated as hydroxides but not as sulphide.
69. Answer (A)
+ +
Ag Ag with time
S2O32– [Ag(S2O3)2]3– Ag2S2O3 Ag2S
Clear solution white ppt (black ppt)
70. Answer (D)

I & III are stabilized by resonance, hyperconjugation and + inductive effect.
 Order (I) > (III) > (II) > (IV)
71. Answer (A)
COOH COOH OH OH
> > >
CH3 Cl
(+I effect) (–I effect)
72. Answer (B)
OH
CN
Br
2-Bromo-5-hydroxy benzonitrile
73. Answer (D)
H H H H
1 + 5 +
2 4
H3C—C —C—C
3
—CH3 CH3—C—C—C—CH3
HO H CH3 :OH H CH3

More stable resonance
stabilized carbocation
74. Answer (B)
Resonating structures having maximum number of covalent bonds are more contributing. Among charge
separated resonating structures, structures where opposite charge are close enough are more contributing.
75. Answer (D)
Br
CH2—CH2—CH2 —CH3
NH2
CH3—CH2—CC—H CH3—CH2—CC CH 3—CH2—CC—CH2—CH 2—CH2—CH 3
3-octyne
76. Answer (C)
COOH COOH
HNO3/H2SO4
HO HO
NO2
OCH3 HNO3/H2SO4 OCH3
H3C H3C NO2
O O NO2
C HNO3/H2SO4
C
O O
77. Answer (B)
H (sp) H
C=C=C
H H
(sp2) (sp2)
(Allene)
78. Answer (A)
Ozonolysis produces CH3CHO and CH3–CH(CHO)2
79. Answer (B)
As branching increases boiling point decreases, so order of boiling point is III > II > I.
80. Answer (B)
O
Cl
Compounds : CH3–Cl : : Cl
Cl
S P R Q
Relative reactivities 1,00,000 : 200 : 79 : 0.02

towards SN2 reaction
81. Answer (D)

H
H—Br
O O – OH + CH3Br
Br
CH3 CH3
82. Answer (D)
OH O
O2N NO2 NH
HN
,
O O
NO2 (Barbituric acid)
(Picric acid)
O
OH
O–C–CH3
HO O COOH
O ,
H
HO OH
(Ascorbic acid) (Aspirin)
83. Answer (C)
–OCH3 group has +R effect. It increases the stability of the carbocation.
84. Answer (C)
O O O O
 I2 + NaOH
–CO2 C  C 
iodoform reaction
Ph  OH Ph CH3 Ph ONa + CHI3
-keto acid E G
85. Answer (C)
O H O
–
C C

O –H O
H H
O O
Most acidic Stabilized by strong
intramolecular hydrogen
bonding
86. Answer (B)
H
– H :O – CH2 – R
:
CH2
O O O O R
H

–H
CH2 – R
O O
An acetal
87. Answer (C)
CH2OH
|
CH3 — CHO + H — CHO 
OH
Aldol
 HOCH2 — CH2 — CHO 
+ HCHO/OH
Aldol
HOCH2 — CH — CHO
CH2OH CH2OH
| |

+ HCHO/OH
Aldol
HOCH2 — C — CHO 
+ HCHO/OH
Cannizzaro HOCH2 — C — CH2OH
| |
CH2OH CH2OH
 Number of aldol reactions = 3

88. Answer (B)
COOH
O
 -keto acid undergoes easy decarboxylation just by heating through the formation of six membered
transition state.
89. Answer (B)
O OH CN CN
CN 95% H2SO4
CH3 – CH2 – C – CH3 CH3 – CH2 – C – CH3 
CH3 – CH = C – CH3
90. Answer (D)

Carbolic acid (Phenol) is weaker acid than carbonic acid and hence does not liberate CO2 on treatment with
aq. NaHCO3 solution. Benzoic acid, benzenesulphonic acid and salicylic are more acidic than carbonic acid
and hence will liberate CO2 with aq. NaHCO3 solution.
91. Answer (D)
O O– CH3
Cl Cl
CH3
CH3
O
CH3 – MgI
92. Answer (A)
COOH O– O
H C H
HO OH
O O
(I)
(stabilizes by H-bonding)
COOH O O– H
OH O
(II) (stabilizes by H-bonding)
COOH COO–
OH OH
(III) (stabilizes by –I effect)
COOH COO–
OH OH
(IV) (destabilizes of +m effect)
 Acidity order is I > II > III > IV.
93. Answer (A)
O O
C C
H – CH = O, NaOH, 
(crossed aldol condensation)
CH2
OH
OH O O
H H
C=O C=O
H H
OH–,  H+
HO
94. Answer (C)
O
O C
O C
NaOH + Br2 Cl NH
H3C C H3C NH2
NH2
H 3C
95. Answer (A)
More reactive
site for SN2
O O
O
C C Br CH2 Cl
OH
N H N K N CH2 Br
C C
O
O O
96. Answer (C)
OH
HO
NH2 NaNO /HCl N N N N
2 –
Cl
H3C H3C H3C
Brilliant coloured dye
97. Answer (D)
+ –
N2 Cl O H
O H O N N
NaOH
98. Answer (A)
NH2
H2N NH
IV
Resonance with two NH2 groups increases electron density on 'N' of NH
NH
Lesser increase of electron density on = NH due to
only one resonance with one –NH2
CH3 NH2
sp2
N
–
N This LPe is not available as it is involve in aromatic Sextet.
H 'N' is bonded to sp2 C on both sides.
III
N This LPe– is not involve in aromaticity. So more available

H
Also, 'N' is bonded to sp3 C on one side.
II
 IV > I > II > III
99. Answer (B)
–
OH OH O
NaNO2 + HCl aq.NaOH

0°C
+
NH2 N+  NCl– NN
OH O
N=N N=N H
100. Answer (C)
Cellulose is polymer of -D glucose. Hence structure (C) is correct.
101. Answer (A)
CH2OH
5 O
H H CH2OH H
H O
4 1
OH H H OH
O—CH2—CH2—O CH2OH
OH
3 2
H OH -linkage OH H
(a) (b)
Ring (a) is six membered oxygen containing ring.
 Pyranose ring and CH2OH of C—5 and —OR of C—1 are across of one another hence, it is -glycosidic
linkage.
102. Answer (B)

OH
O
OH
HO
HO HO
-D-Glucopyranose, which is cyclic form of an aldohexose.
103. Answer (D)
In natural rubber polar groups are absent and hence it will have only weak van der Waals force of attraction.
104. Answer (A)
ethylene unit
n (i) Polymerisation
(ii) Hydrogenation
Polymer
Propylene unit
So, it is called ethylene-propylene unit.

105. Answer (B)
Detergent will form micelles in aqueous solution at the lowest molar concentration at ambient condition.

SECTION - B
One or More Option(s) Correct Type Questions
1. Answer (B, C)
Compound Number of lone pairs on central atom
BrF5  1
ClF3  2
XeF4  2
SF4  1
2. Answer (A, C)
By MOT, C22– is diamagnetic as it is isoelectronic with N2.
By MOT, O22+ has bond order 3 and O2 has bond order 2. So, bond length of O22+ is shorter than O2.
N2+ and N2– have bond order 2.5
He2+, since has bond order 0.5 it has lower energy than He atoms.
3. Answer (A, B, C)
According to Kinetic theory of gases,
(i) Collisions are always elastic
(ii) Momentum transferred on wall
By one collision along x component = 2 mvx
Fraction of
(iii) molecule
Velocity
4. Answer (C)
V(r)
0
r
As per given conditions atoms have no interaction at long range but repell at short range.
5. Answer (A, C, D)
In a reversible expansion work, process is very slow, isothermal and work done in a state function.
6. Answer (A, B)
Molar conductivity and electromotive force are intensive properties.
7. Answer (A, C)
Entropy is a state function. In this diagram initial state is X and final state is Z.
Therefore, SX  Z = SX  Y + SY  Z
Work is a path function. Therefore WX  Y  Z = WX  Y
8. Answer (A, C, D)
Obviously here T1 > T3 from the graph and T1 = T2 as process curve is isothermal. Uisothermal = 0 and that
for an adiabatic process is negative so option (D) is correct. Now Wisothermal > Wadiabatic also hence answer
is (A, C, D).
9. Answer (A, B, C)
Work against zero external pressure is zero q = 0 due to insulated boundary
So, q = 0
U = 0
T = 0
 T2 = T1
and P2V2 = P1V1
10. Answer (A, B, C)
(A) In free expansion, Pex = 0  w = 0
For isothermal free expansion of an ideal gas,
U = 0  q = 0
 Adiabatic also
(B)
WIsothermal > WAdiabatic

Isothermal
P
Adiabatic
V1 V V2
(C) Area under irreversible P v/s V graph in compression is more than that under P-V graph of reversible
compression.
(P1, V1)
P1 (P1, V2)
Irreversible
P
Reversible
P2 (P2, V2)
V1 V V2
11. Answer (B, C)

A – C (Isochoric process)  wAC = 0 and UAC = qAC
B – C (Isobaric process)  UBC = qBC + wBC
wBC = –P2(V1 – V2) = P2(V2 – V1)
qBC = HBC
∵ (T)A–C = (T)B–C
 UBC = UAC = qAC
HBC = HAC = qBC
∵ T2 > T1
HCA and UCA are negative
HCA = UCA + VP
(–ve)
 HCA < UCA
A – B (Isothermal process)
UAB = HAB = 0
V2
wAB = –nRT1 ln
V1
12. Answer (D)
Solution of weak acid and its salt with strong base behave like buffer.
CH3COOH  CH3COONa
13. Answer (A)
Rate with respect to weak acid
R1 = K[H+]WA[ester]
and rate with respect to strong acid
R2 = K[H+]SA[ester]
R1 [H+ ]WA 1
 = =
R 2 [H+ ]SA 100
[H ]SA 1
 ⎡⎣H ⎤⎦    0.01M  C
WA 100 100
 = 0.01
Ka for weak acid = C2
= 1(0.01)2
= 1 × 10–4
14. Answer (A, B, D)
CaCO3 (s) CaO(s)  CO2 (g)
K  PCO2
K is only dependent on temperature and it is independent of the amount of reactant or product.

H is dependent on temperature according to Kirchoff's equation but independent of addition of catalyst.
15. Answer (B)
The solubility of Ag2CrO4 = ⎡CrO4–2 ⎤

⎣ ⎦
K sp 1.1  10 –12
 ⎡CrO4–2 ⎤ 
⎣ ⎦ 2
  1.1  10 –10 mol L1
⎡ Ag ⎤ (0.1)2
⎣ ⎦
16. Answer (B)
On increasing temperature forward as well as backward reaction rate increases due to which initially %yield of
NH3 is higher at T2 K but equilibrium attain at lower time at T2 K hence its yield at equilibrium is low at T2 K.

Whether reaction is endothermic or exothermic in forward direction increase in temperature cause intake of
heat from surrounding to system in endothermic direction due to which entropy change in system is positive
and S of surrounding is negative.
18. Answer (A, C)
ln K1 T2

ln K 2 T 1
 On increasing temperature, K decreases.
 H° < 0
From graph K > 1  G° < 0
– H S

ln K1 TR R T
 1  2
ln K 2 H S T1

T2R R
( H  T1S) T2 T2

( H  T2 S) T1 T1
–H° + T1S° > –H° + T2S°
 S° < 0
19. Answer (A, D)
aq
MnO4   MnO2
 Mn2
–
MnO4 
acidic

Therefore in aqueous and in acidic mediums 3 and 5 electrons will transfer respecitvely.
Balanced chemical equation is 6I  ClO3  6H2SO4 

 Cl  6HSO4  3I2  3H2O
Here, H2O is produced and I– is oxidized.
21. Answer (B, C)
ASchottky defect are favoured by small difference in sizes of cation and anion.
BIn Frenkel defect cations are dislocated therefore. (True)
CElectron trapped in lattice are called F-centre. (True)
DSchottky defect decrease density.
22. Answer (A)
The formula will be MgAl2O4
Total tetrahedral voids = 8
Total octahedral voids = 4
1
as only one Mg atom is present hence, n =
8
2 1
as there are two Al atoms are present hence, m = =
4 2
1 1
 m, n = ,
2 8
23. Answer (B, C, D)
In CCP, the coordination number for atom in top-most layer is 9.
Benzene and naphthalene form an ideal solution. For an ideal solution, H = 0, Ssystem > 0 and Ssurroundings
= 0 because there is no exchange of heat energy between system and surroundings.
25. Answer (A, B)
Mixture Nature of deviation from Raoult's Law
Carbon tetrachloride + methanol +ve
Carbon disulphide + acetone +ve
Benzene + toluene Ideal solution
Phenol + aniline –ve deviation
26. Answer (A, D)
pL
xM = 1 xM  xM = 0
Pure M xL = 1
Pure L
Point Z represents v.p. of pure liquid L

At xL  1, solution is very dilute, L becomes solvent. Very dilute solution of M in L is nearly ideal and obey
Raoults law (pL = xLpL°)
Also, there is positive deviation indicated by graph above dotted line (expected for ideal solution)
 L-M interaction < L - L & M - M Interactions.
Oxidation of V
E° = 0.96 – (–1.19) = 2.15 V
For Fe,
E° = 0.96 – (–0.04) = 1.0 V
For Au,
E° = 0.96 – 1.4 = – 0.044 V (not feasible)
For Hg
E° = 0.96 – 0.86 = 0.1 V
28. Answer (A, B)
In a galvanic cell, the salt bridge does not participate in the cell reaction, stops diffusion of ions from one
electrode to another and is not necessary for the occurrence of the cell reaction.
2.303 A
t log
m 0.4  102  Α
8  0.693 2.303
  log250
k k
103
 2.303log
4
 2.303  (3  2  0.3010)
30. Answer (A, B)
9
4 Be    84Be  10n
9
4 Be  H  84Be  12H
1
1

 A high activation energy usually implies a slow reaction.
 Rate constant of a reaction increases with increasing temperature due to the increase in greater number
of collisions whose energy exceeds the activation energy.
–E /RT
 k  P Ze a
So, pre-exponential factor (A) = P × Z and it is independent of activation energy or energy of molecules.
32. Answer (B, D)
When N/P ratio is less than one, then proton changes into neutron.
Positron emission : 11 H  10n  01 
Capture : 11 H  0
1 e  10 n  X-rays
33. Answer (A, D)
A exp erimental
Steric factor =
A calculated
Steric factor = 4.5
It means Aexperimental > Acalculated
[This seems that reaction occurs more quickly than particles collide, thus concept of steric factor was
introduced]
34. Answer (A, D)
A  2B + C
P0 – –
P0 – P 2P P
Pt = P0 + 2P
Pt  P0
P=
2
⎡ P0 ⎤ 2P0
Kt  ln ⎢ ⎥  ln
P  P 3P0  Pt
⎢ P0  ⎛⎜ t 0⎞⎥
⎢⎣ ⎝ 2 ⎟⎠ ⎥⎦
Kt  ln 2P0  ln(3P0  Pt )
ln (3P0 – P)t
Time
Rate constant of reaction is independent of initial concentration.

35. Answer (B, D)
At high temperature, sufficient activation energy for chemical adsorption is provided.
Hadsorption for chemical lies between 200-400 kJ/mole. Chemisorption of H2 on glass is an endothermic process.
36. Answer (A, D)
Lyophobic colloids carry either +ve or –ve charge. In order to acquire stability the colloidal particles attract
oppositely charged ions forming a diffused layer. A potential is developed between fixed layer and diffused layer
called zeta potential. Higher the value of zeta potential higher will be the stability of lyophobic colloid.
37. Answer (A, C)
Under mild conditions of temperatures extent of physisorption decreases with increasing temperature so
graph (I) is correct. As initial temperature provided meets the necessary activation energy needed for chemical
bond formation for chemisorption so graph (II) is also correct. Finally graph (IV) is correct for chemisorption
as plot is now of potential energy vs distance of molecule from surface. Hence, answer is (A, C).
Reaction on metal surface
M  M  e 
O2  e 
 O2
This is an example of chemisorption.
39. Answer (A, C)
Adsorption is an exothermic process and is accompanied by decrease is entropy,
H  0, S  0
sys sys
More is critical temperature (Tc), more are intermolecular forces of attraction.

 More is extent of adsorption.
40. Answer (B, C)
Ca(OH)2 and Na2CO3 is used to remove hardness of water. Ca(OH)2 is used in Clarke's method.
In ice water molecules are excessively H-bonded giving a cage-like structure which is lighter than water. Primary
amines are more basic than tertiary amines in aqueous solution mainly due to H-bonding with water molecules.
Dimerisation of acetic acid in benzene is due to intermolecular H-bonding.
42. Answer (C, D)
Fe3+ is reduced to Fe2+ by H2O2 and Na2O2 in acidic medium.
43. Answer (A, B)

44. Answer (A, B)
Small bases (NH3 and 1º amine) are able to break the bond of bridged hydrogen in a unsymmetrical manner.
 s O O O O
N  N—O , N—N , N—N
O O O


Property-wise graphite is softer than diamond. However both electrical and thermal conductivity of graphite is
higher than that of diamond. Bond order (C–C) in graphite is 1.5 and higher than C–C bond order in diamond.
Hence, answer is (B, C, D).
47. Answer (A, C, D)
 
O O
O O O O
Ozone is diamagnetic in nature and both the O – O bond length are equal. It has a bent structure.
Dilute solution of Na in liquid ammonia is paramagnetic
K O2  KO2
(excess)
O2– is paramagnetic due to unpaired electron in antibonding orbital
3Cu  8HNO3  3Cu(NO3 )2  2NO  4H2O

(diluted)
NO is paramagnetic due to unpaired electrons on "N".

49. Answer (B, D)


H3BO3  H2 O
B(OH)4  H
CH2 OH CH2 O O CH2

B(OH)4 + B
CH2 OH CH2 O O CH2
OH
B
HO OH
In boric acid, planar H3BO3 units are joined by hydrogen bonds to give layered structure.
50. Answer (B)
(CH3)2 SiCl2 form linear polymer on hydrolysis and (CH3)3 SiCl is a chain terminator.
51. Answer (B, C)
HClO HClO2 HClO3 HClO4
Cl O 0 1 2 3
lone pair on Cl 3 2 1 0
Hybridization sp3 sp3 sp3 sp3
HClO4 is strongest acid
Borax formula is Na2[B4O5(OH)4].8H2O
[B4O5(OH)4]2– has following structure
O H
(–)
B(I)
OO O
H
(IV) O
H B (–) B(II) B(III)
O O
O O H
B(I) and B(II) are sp3 hybridized
B(III) and B(IV) are sp2 hybridized.
53. Answer (B, D)
P4O10 is dehydrating agent and dehydrate HNO3.
PO
2HNO3 ⎯⎯⎯⎯
4 10
→ N2O5
N2O5 is dia magnetic

N2O5
NO2+ + NO3–
Na  Na+ + e–
NO2+ + e–  NO2
(brown)
54. Answer (B, C)
The colours arise from the absorption of light on promoting an electron from the ground state to higher state.
On descending the group, the energy levels become closer and gap between HOMO – LUMO decreases.
HOMO is *
LUMO is *
(A) HClO4 > H2O Acidic character
ClO4– < OH– Conjugate Base
Strong acids have weak conjugate base
(B) Both HCIO4 and HClO central atom is sp3 hybridised
(D) HClO4 > HClO Acidic strength
 H+ + ClO4
HClO4 
 H+ + ClO 
HClO 
O
–
O O O
CI O CI O CI CI O–
– O
O O O O O
O O– O
In ClO4 , nagative charge is dispersed on four oxygen, so better resonance stabilised.
56. Answer (A, C)

ZnO, Al2O3, PbO, PbO2, Cr2O3, BeO, SnO and SnO2 are amphoteric oxides.
NO is neutral oxide
CrO is basic oxide
B2O3 is acidic oxide
H e– H e
– H
B – B It has two 3c-2e bonds.
e– e
H H H
Cl Cl Cl
2AlCl3  Al Al No 3c-2e bond
Cl Cl Cl
CH3 CH3 CH3
Al Al Has two 3c-2e bonds.
CH3 CH3 CH3
Also, BCl3 is stronger lewis acid than AlCl3.
58. Answer (B, C)
NH4NO3 on heating at 250°C decomposes to nitrous oxide and water
NH4NO3  N2O + H2O
Nitrous oxide above 600°C decomposes to dinitrogen and dioxygen gas
2N2O  2N2 + O2
Ammonium dichromate on heating decomposes to give dinitrogen and chromium (III) oxide

(NH4)2Cr2O7  N2 + Cr2O3 + 4H2O
Barium azide on heating around 180°C decomposes to give dinitrogen gas and barium
Ba(N3)2  3N2 + Ba
Magnesium nitride decomposes above 700°C to give magnesium and dinitrogen gas
Mg3N2  3Mg + N2
So, below 300°C only (NH4)2Cr2O7 and Ba(N3)2 can provide N2 gas only heating.
Basic character of oxide decreases as we move down the group.
 Bi2O5 is more basic than N2O5
- Covalent nature depends on the electronegativity difference between bonded atoms.
 NF3 is more covalent than BiF3
- Boiling point of NH3 is more (due to H-bonding) than PH3
- P–P single bond is stronger than N–N single bond (as in N, due to smaller size of atoms lone pair-
lone pair repulsion will be more)
12001300C
SnO2  Sn  CO
if after contain Fe and Cu as impurity.
61. Answer (C, D)
Al2O3 and MgCO3.CaCO3 are separately reduced by electrolytic reduction.

Cu2S  2Cu2O  6Cu  SO2
Since, CuSO4 as well as CuO both on heating produces Cu2O as shown below so, they also produce Cu on
heating with Cu2S.
 1
2CuO  Cu2O  O2
2
 1
CuSO4  CuO  SO2  O2
2
In electrolytic refining of blister Cu, acidified CuSO4 is used as electrolyte, pure Cu deposits at Cathode and
impurities sattle as anode mud.
Extraction of Cu from copper pyrite (CuFeS2) involves following steps:
Step 1: Pulverisation or crushing of copper pyrite ore.
Step 2: Concentration of the ore by froth-flotation method.
Step 3: Self-reduction during partial roasting.
CuFeS2 + O2  Cu2S + FeS + SO2
Cu2S + O2  Cu2O + SO2
2Cu2O + Cu2S  6Cu + SO2

(blister copper )
FeS + O2  FeO + SO2
FeO + SiO2 ⎯⎯
→ FeSiO3
(flux) (slag)
Step 4: Refining of blister copper : Refining is done by electrolytic refining method.

Cr2+ is a reducing agent and Mn3+ is an oxidizing agent and both have electronic configuration d4.
E  0.41 V E  1.51 V
Cr 3  /Cr 2 Mn3  /Mn2
Above E° values explains reducing nature of Cr2+ and oxidizing behaviour of Mn3+.
66. Answer (B, D)
(A) Manganese show pale purple colour in flame test.
H2S
(B) Cu2 
HCl
 CuS 
Black ppt.
(C) Both Cu+2 and Mn+2 form precipitate with H2S in basic medium.
(D) ECu2 /Cu  0.34
EMn2  /Mn  1.18 V
67. Answer (C, D)

Cl
en
Cl
(C) en Pt en &
Cl
en
Cl
Cl NH3 Cl NH3
(D) Pt & Pt
NH3 Cl Cl NH3
68. Answer (B, D)
The pair of complex ions [Co(NH3)4Cl2]+ and [Pt(NH3)2(H2O)Cl]+ show geometrical isomerism. The pair of
complexes [Pt(NH3)3(NO3)]Cl and [Pt(NH3)3Cl]Br show ionisation isomerism. The other pairs given do not have
same type of isomerism.
(X) = CoCl26H2O, or, [Co(H2O)6]Cl2 (Pink)
2+
Co = [Ar]
3d
H2O is weak field ligand, therefore No pairing of electron
 Number of unpaired electron, n = 3
 s  n(n  2) B.M.
= 15 B.M.
= 3.87 B.M.
[Co(H2O)6 ]2   6NH3(aq)

2
[Co(NH3 )6 ]  6H2O
O2 will oxidise [Co(NH3)6]2+ to [Co(NH3)6]3+, therefore shift in forward.
 Y = [Co(NH3)6]3+Cl3 [1 : 3 complex]
Co(III) = [Ar]
3d
NH3 is strong field ligand
 Forces electrons to pair up.
 n=0
 = 0 B.M.
[Co(NH3)6]3+ = [Ar]
3d 4s 4p
2 3
d sp
Also, [Co(H2O)6] + 4Cl
2+ –
[CoCl4]2–(aq) + 6H2O; H = +ve
(X) (Z)
(Pink) Blue
At 0°C, equilibrium shifts in backward, therefore pink colour.
70. Answer (B, C)
(A) Valence shell electrons in iron in compound Fe(CO)5.
Fe(26) – 1s2, 2s2, 2p6, 3s2, 3p6, 3d8 (after pairing of electrons)
3d 4s 4p
3
dsp Hybridization
Valence = 2 + 6 + 8 = 16
Electrons (3rd shell)
Valence shell electrons in nickel in compound Ni(CO)4
Ni(28) - 1s2, 2s2, 3s2, 3p6 ,3d10
3d
3
sp Hybridization
Valence electrons (3rd shell) = 2 + 6 + 10 = 18

(B) Both complexes are formed in low spin condition due to strong field ligand 'CO'.
(C) Metal carbon bond strengthens when complex is formed in lower oxidation number of metal. Since in lower
oxidation number; number of electrons in d-subshell are higher, so it can donate more electrons in ABMO
of ligands and increases the double bond character between metal and carbon.
(D) In higher oxidation number, metal may have less number of electrons in d-orbitals, which decreases the
extent of synergic bonding.
(A) [Co(en)(NH3)3(H2O)]3+
3+ 3+
OH2 NH 3
CH 2 H2N NH 3 CH 2 NH 2 OH2
Co Co
CH 2 NH 2 NH 3 CH 2 NH 2 NH 3
NH 3 NH 3
(B) [Co(CN)2(NH3)3(H2O)]1+
1+ 1+ 1+
OH2 NH 3 CN
NC NH 3 NC OH2 H 3N OH 2
Co Co Co
NC NH 3 NC NH 3 H 3N NH 3
NH 3 NH 3 CN
(C) Co3+ = [Ar]3d6

in presence of en and NH3 it form low spin complex.
(D) [Co(en)(NH3)4]3+ has larger gap between eg and t2g than [Co(en)(NH3)3(H2O)]3+. So [Co(en)(NH3)3(H2O)3+
absorb longer wavelength than [Co(en)(NH3)4]3+.

2Na S O
Na2S2O3 + AgX  Ag2S2O3 
2 2 3
 Na2[Ag(S2O3)3]
[X = Cl and Br]
2[Excess KI] + 2K3[Fe(CN)6] 2K4[Fe(CN)6] + I2
ZnSO4
I2 + K2Zn3[Fe(CN)6]2
Brown-yellow (white ppt)
filtrate
+2 2– +
Zn + 4NaOH [Zn(OH)4] + 4Na
Soluble
2Na2S2O3 + I2 Na2S4O6 + 2NaI

colourless solution
So, answer is (A, C, D).

74. Answer (C, D)
Only group II cations precipitate as sulphide with H2S in acidic medium that is (Cu2+, Pb2+) and (Hg2+, Bi3+)
75. Answer (A or A, C)
S2– SO42–
Cu2+ CuS (ppt) CuSO4 (Soluble)
Ba2+ BaS (Soluble) BaSO4 (ppt)

Pb(OAc)2 PbS (ppt) PbSO4 (ppt)
Na2[Fe(CN)5NO] Na4[Fe(CN)5(NOS)] ______
Colour (not a ppt)
76. Answer (B, C)

H
C H
H
C
sp C C C O
2
C
H sp
2
H
H
All atoms lie in one Planar

plane in all conformation
H
H
C C C is nonplanar
H
H
H
H
C C H
H C C
H H
Non-planar in many conformations due to rotation along.
C2 — C3 bond.
77. Answer (B, C)
The compound is antiaromatic and hence unstable at room temperature. The other compound
–
O O
+
is also unstable at room temperature due to partial positive charge at carbonyl C-atom
78. Answer (A)

In hyperconjugation   p (empty) electron delocalization for tert-butyl carbocation and   * electron
delocalization for 2-butene will take place.
79. Answer (A, B)
IUPAC name
Cl
1
2
(A) 1-chloro-4-methylbenzene
3
4
CH3
CH3
1
2
(B) 4-chlorotoluene
3
4
Cl
80. Answer (B, D)
X H3C CH3
H3C CH3
X C
C
H H H HY
Y
When X = H & Y = C2H5
H3C CH3
H C
2
C C2H5
H 1 H
2, 2- dimethyl butane
When X = CH3 and Y = CH3
H3C CH3
C2
4CH3
C CH3
H 3 H 1
2, 2-dimethyl butane
81. Answer (D)
CH3
CH2 1 equiv. HBr
H2C H
+
H3C 
 Br
–
Br
(Major)

Br
+
NaOEt
–
AlCl3 + 1, 2 H +
Shift
Cl
+
H +
BF3 1, 2 H– +
+
O–H Shift
H
83. Answer (B, D)

HC
3 H
(i) C=C
H CH 3
Trans
Br2 /CHCl3
CH 3 CH
3
H Br Br H
+
H Br Br H
CH 3 CH
3
Meso (M and N)
CH3 CH3
(ii) C=C
H Cis H
Br2
CH3 CH3
H Br Br H
+
Br H H Br
CH3 CH3
O P
Pair of enantiomers
Cis anti Racemic
M and N are meso (identical)
O and P are pair of enantiomers
(B) Bromination proceeds through anti addition.
(D) (M and O) and (N and P) are two pairs of diastereomer.
84. Answer (A, D)
Given compound has three stereocentre with symmetrical substituents. It will form six stereoisomers out of
which 2 will be meso and one dl pair of cis and one dl pair of trans.
With reference to structure (M), if the chiral carbon bearing the methyl group is C–1 and that bearing the
chlorine is C–2, then
Structure Configuration of C–1, C–2

respectively
M S, R
N R, R
O S, R
P R, S
Q R, R
Now from the above configurations we learn that
(A) M and N are diastereomers i.e., non-mirror image stereoisomers.
(B) M and O are surely identical as their configurations are same.
(C) M and P are also enantiomers due to opposite configurations.
But M and Q are again not identical but diastereomeric.
Hence answer is (A, B, C).
86. Answer (B, D)
H Br H Br
H2/Ni
(A) *
(Optically active)
H Br H Br
H2/Ni
(B)
(Optically inactive)
H Br H Br
H2C H2/Ni
H3C
CH3 CH3
(C)
CH3 CH3
(Optically active)
Br H Br H
H2/Ni
(D) H2C CH3 H3C CH3
(Optically inactive)

When medium is highly polar and protic I & III will follow SN1.
Hence, (A) is correct.
Option (B) is correct as
Nu–
Br Nu
SN2
Inversion in case of SN2.

(D) I & II will follow SN2 when medium is polar aprotic and nucleophile is strong in high concentration.
(C) is incorrect for both SN1 and SN2 conditions.
(A) & (C) is usual product. Formation of (B) is justified as
O O
Br Br Br Br Br
89. Answer (B)
OH OH
Br Br
aqueous
Br2 (3.0 equivalents)
SO3H Br
90. Answer (B, D)
OH OH O
CHO
CHCl3
– +
OH
CH3 CH3 H3C CHCl2

(S) (Q)
(Major product) (Minor product)
O–H
(I) (III)
(II)
(I), (II) and (III) are probable positions as per electronic effect of OH group where electrophile can attack
and due to steric hindrance at (II) and (III) positions bulky electrophiles are not preferred like I only preferred
at position I, Bromine at positions II and I while chlorine at all three positions.
92. Answer (B)
O H
O
+
,H Radical, initiator, O2
High pressure, heat
'T' 'U'
93. Answer (B, C)
CH3 CH3
H3C – C – H H3C – C – O – O – H OH
O
(i) O2 H3O+
+ CH3 – C – CH3
(P)
H H
OH O O O
CH
CHCl3
+
NaOH
(P) (Q)
CH = O
(Major)
(R)
(i) NaOH (Minor)
(ii) PhCH2 – Br
O – CH2 – Ph
CH = O
(S)
 Q is steam volatile due to intramolecular hydrogen bonding but (R) is a high melting solid.
 Since, Q contains a phenotic group, it forms dark brown solution with 1% aqueous FeCl3 solution.
O – CH2 – Ph O – CH2 – Ph NO2

NO2
CH = O
H+ CH = N – NH NO2
 + H2N – NH NO2
2, 4 DNP (yellow precipitate)
 Since, (S) does not contain free phenolic group, therefore it will not form violet colour with FeCl3 solution.
94. Answer (B)
Me OH
The correct structure of X is
Me OH Me Br Me I
PBr3 NaI
Et2O(SN2) acetone(SN2 ) NaN3, HCONMe2
(SN2)
Me N3
enantiomerically pure
Enantiomerically pure product after several substitution reactions, is only possible when each reaction must
stereospecific in nature which confirms pathway used is SN2 in nature.
95. Answer (A, B, C, D)
X (CH2)4 X
When x = –COO Me and Y = H2/Ni will give diol. Diol will form polyester with dicarboxylic acid.
In B, C and D diamine is obtained which will give polyamide with dicarboxylic acid.
96. Answer (B, D)
C6H5COOH + NaOH  C6H5COONa + H2O
C6H5COOH + NaHCO3  C6H5COONa + CO2 + H2O
C6H5CH2 – OH + NaOH  No reaction
C6H5CH2OH + NaHCO3  No reaction
C6H5CH2COOH + NaOH  C6H5CH2 – COONa + H2O
C6H5CH2COOH + NaHCO3  C6H5CH2COONa + CO2 + H2O
C6H5CH2OH + NaOH  No reaction
C6H5CH2OH + NaHCO3  No reaction
97. Answer (A, C)
O
OCOCH3
CH2OH CH2
O LiAlH4 OH Excess (CH3CO)2O OCOCH3
H3C H3C H3C

T Optically W
inactive (Molecular formula
(U) C10H18O4)
CHO
+
CrO3 /H
CHO
H3C
V
No effervescence
Hence answer is (A, C).
98. Answer (A, B, C, D)
AlCl3
(i) Cl AlCl4 (P)
(AROMATIC)
Na
NaH
(ii) (Q) + H2
(AROMATIC)
(NH4)2CO3
R
(iii) 100–115ºC
O O

(NH4)2CO3 2NH3 + CO2 + H2O
 IMPE
+ NH3
O O O O NH2 O NH2 OH
H
H H H H
N N N
 IMPE
–2H2O
HO OH O OH
(R) AROMATIC
HCl
(iv) O OH Cl (S)
(AROMATIC)
99. Answer (C)

O
Reaction I : C Br2 (1.0 mol)

CHBr3 + CH3COONa
CH3 CH3 aqueous NaOH
(1.0 mol)
O O
Br2 (1.0 mol)
Reaction II : C CH3COOH
C
CH3 CH3 CH3 CH2Br
(1.0 mol)
100. Answer (A)

CH3 CH3
CH3 O OH
O H O O O +
O
KOH, H2O H
CH3
O
O O

+
(Minor) (Major)
All aldehydes gives Tollen's test as shown below
O
R – CH = O + [Ag(NH3)2 ]+ R – C – O– + Ag+ NH+4
(Silver mirror)
-hydroxy ketones are oxidised to 1, 2 diketones and Ag+ is reduced to Ag.

OH O O O
+
[Ag(NH3)2] +
Ph – CH – C – Ph Ph – C – C – Ph + Ag+ NH4
102. Answer (B, C)
O O
(i) O3/CH2Cl2
CH3 CH3 C–H+H–C–H
(ii) Zn/H2O
Undergoes
Cannizzaro's
reaction
CH2 O O
O3/CH2Cl2
C C + H–C–H
Zn/H2O
CH3 CH3
Undergoes
Haloform reaction
O O
O3/CH2Cl2
CH3 C – H + CH3 – C – H
Zn/H2O
CH3 CH3 Undergoes

Cannizzaro's reaction
CH3
CH3 O CH3 CH3
O3/CH2Cl2
C +
Zn/H2O
CH3 O
CH3
CH3 Undergoes
Haloform reaction
H
H
C
H O Me Me
(A) Me C C Me Conc.H2SO4
+ 3H2O
O C H 
H H H
H Me
C O
H C
Me
Me
|
C H Me Me
H C
C Heated iron tube
(B) 873K
C C
Me C Me
Me
|
H
O
||
C—Me
|
Br2/NaOH
(Haloform reaction)
Me
(C) Me—C C
|| ||
O O
O
O Na
C
|
C C—O Na
Na O || ||
O O
3H3O+
COOH
Soda lime

(decarboxylation)
COOH
COOH
CHO CH3
Zn/Hg,HCl
(D) (Clemmensen reduction)
OHC CHO CH3 CH3
104. Answer (A)
H
+
NH2 N
O O
H O
O
+ CH3COO–
NH2 CH2Cl2
O
H
N
O
+ CH3COOH
105. Answer (C)

H H
O O
O
C O C O C O
NaNO2
(Inversion)
H aq. HCl
– H
NH2 0°C +
Cl N2 H
(Diazotisation)
H
O
O
C O C O
(Inversion)
H OH2
OH H
(Retention Product)
(Major)
106. Answer (A)

+ –
N  NCl OH
N=N
NH2 , NaOH OH
NaNO2, HCl
0°C
(V) (W)
107. Answer (A)
O OH
H NH
(1) O3 H NH3
(2) Zn, H2O
O OH
–2H2O
108. Answer (B)
O O
NH2 NH – C – CH3 NH – C – CH3
Ac2O KBrO3/HBr
pyridine
acetamilide
Br
(major)
+ –
NH2 N  NCl Br
H3O+ NaNO2/HCl Cu
273 – 278 K HBr
(diazotisation)
Br Br Br
109. Answer (D)
NH 2 NH 2 NH2 NH2
Conc. HNO3 NO 2
+ +
Conc. H2SO 4
NO 2
NO 2
51% 47% 2%
(P) (Q) (R)
O O
NH2 NH – C – CH 3 NH – C – CH 3
NO2 Ac 2O, Pyridine NO2 Br2 NO 2
CH3COOH
(R) Br
+
H3 O
+ –
N2 Cl NH2
NO2 EtOH
NO 2 NaNO2, HCl
NO 2
 273-278 K
Br Br Br
(S)
Br
NO2 Sn/HCl
NH2 Br 2
NH2
H2 O (excess) Br Br
Br Br Br
(S)
NaNO2 , HCl
Br Br
+ –
H 3PO 2 N2 Cl
Br Br Br Br
Br Br
110. Answer (B, C)
No hemiacetal linkage is free in X. Therefore it is non-reducing. While Y having hemiacetal linkage would be
reducing sugar.
CH2OH CH2OH
O O
O HOH2C H H
H H H HOH2C H H
O O OH
HO OH H CH2OH O H OH
H OH H H
H HO H
H OH HO H HO
-Glucosidic linkage -Glucosidic linkage
111. Answer (A)
CHO CHO
H OH HO H
HO H H OH
H OH HO H
H OH HO H
CH2OH Mirror CH2OH
D-(+)-glucose L-(–)-glucose
112. Answer (B, C)

Invert sugar is an equimolar mixture of D-(+) glucose and D(–) glucose.
+
H +
C12H22O11 + H2O C6H12O6 + H2O C6H12O6
(+) sucrose D(+)-glucose D(+)-glucose
(+52°) (–92°)
Invert sugar
92  52
 Specific rotation of invert sugar =  20
2
 D-glucose on oxidation with Br2-water produces gluconic acid and not saccharic acid
113. Answer (D)
Structure of -L-Glucopyranose is
H
O
HO CH 2OH H
H H OH OH
OH H

SECTION - C
Linked Comprehension Type Questions
C1. 1. Answer (B)
S1 state is 2s
In 2s, one radial node is present.
2. Answer (C)
Energy in S1 state
–13.6  32 9
E  – 13.6 eV
22 4
E( H1 ) = –13.6 eV [Ground state]

1
So, energy = 2.25 × energy of e– in ground state in 1H1

3. Answer (B)
S2 state is 3p orbital.
Orbital angular momentum of 3p is 1.
C2. 1. Answer (C)
x 40

24 – x 10
x
2
24 – x
x = 16
2. Answer (D)
Increased collision frequency of X with the inert gas as compared to that of y with the inert gas. Therefore,
the experimental value of d is found to be smaller than the estimate obtained using Graham's law.
C3. 1. Answer (C)
2. Answer (B)
K L
Pressure
N M
Volume
As PV product increases temperature increases as PV product decreases temperature decreases.

PV product increases (K  L, N  K)
PV product decreases (M  N, L  M)
Isochoric process are (L  M, N  K)
C4. 1. Answer (A)

Exp-I
Energy released = 5.7 kJ
Heat absorber by temperature rise = 200 × 4.2 × 5.7 = 2 × 42 × 57 = 4.788 kJ
Calorimetric constant = 5.7 – 4.788 = 0.912 J
Exp-II
Q = 200 × 4.2 × 5.6 = 4.704 kJ
Net energy = 4.704 + 0.912 = 5.616 kJ
Per mole of neutralization energy released = 56.16 kJ
Dissociation energy = 57 – 56.16 = 0.84 kJ  1 kJ
2. Answer (B)
Buffer is formed
⎡CH3COO  ⎤
pH  pK a  log ⎣ ⎦
⎡⎣CH3COOH⎤⎦
As per given question concentration of CH3COO– and CH3COOH is equal.
pH = pKa = –log2 + 5
= 4.7
C5. 1. Answer (B)
X2(g)

2X(g)
Initial mole: 1 0
⎛ βeqbm ⎞
1− eqbm
⎝⎜ ⎟
Moles at equilibrium :
2 ⎠
βeqbm
1− βeqbm
2 ×P P
Partial pressure :
⎛ βeqbm ⎞ ⎛ βeqbm ⎞
⎜⎝1 + 1+
2 ⎠
⎟ ⎝⎜ 2 ⎠
⎟
(Px )2 β2eqbmP
 Kp = =
Px2 ⎛ β2eqbm ⎞
⎜⎝1 − ⎟
4 ⎠
4β2eqbm × P
 Kp =
(4 − β 2
eqbm )
Since P = 2 bar
8β2eqbm
So, K p =
(4 − β 2
eqbm )
2. Answer (C)
Since, G°, is positive
It means Kp < 1.
Kp = –2.303 RT log Kp
So, eqbm = 0.7
8 × (0.7)2
Kp = >1
4 − (0.7)2
Hence, eqbm  0.7
C6. 1. Answer (C)
25  N  45  0.25
N  48  0.25
25
 N = 0.48 M
0.48
 M  0.24 M
2
2. Answer (A)
Oxoacid is HOCl. The anhydride of oxoacid is Cl2O.
C7. 1. Answer (B)
1 1
The number of effective atom in a unit cell = 12   2   3 1 = 6
6 2 ⎛ no of atoms in ⎞
corner  ⎛⎜ Face ⎞⎟ ⎜ hexagonal primitive ⎟
⎝ Centre ⎠ ⎜ unit cell ⎟
⎝ ⎠
2. Answer (A)
Volume of HCP unit cell = Base area × height
⎛ 3 2 ⎞⎟ 2 ⎞⎟
= ⎜6  a  4r
⎜
⎝ 4 ⎟
⎠ 3 ⎟⎠
3 ⎛ 2 ⎞⎟
= 6 2r 2  ⎜⎜ 4r
4 ⎝ 3 ⎟⎠
= 24 2 r 3
3. Answer (D)
4 3
r 6
Packing fraction =
3
Base area  Height
4 3
6 r
3
=
⎛ ⎞
⎜ 6  3 a 2 ⎟  4r 2
⎜ 4 ⎟ 3
⎝ ⎠
= 0.74
% of empty space = (1 – 0.74) × 100 = 26%
C8. 1. Answer (B)
Cell reaction M 
 M
(1 M) (0.05 M)
Apply Nernst equation,
0.059 0.05
E  Eº – log
1 1
0.059
E–
1

log 5  10 –2 
0.059
E– ⎡ –2   log5 ⎤⎦
1 ⎣
2. Answer (C)
E1 log0.05

E2 log0.0025
E1 log5  10 –2

E2 log25  10 –4
E1 70(given)
70 –1.3 1
 
E2 –2.6 2
C9. 1. Answer (B)
0.059 0.001
0.059   log 2
2 (M )
0.001
log 2
[M 2 ]
0.001
 100 Ksp = 4 × (10–5)3 = 4 × 10–15
[M 2  ]
[M2+] = 10–5
2. Answer (D)
G = –nFE = –2 × 96500 × 0.059
= –11387 joule mol–1
 –11.4 kJ mol–1
C10. 1. Answer (A)
Cl2  2NaOH(dil.) 

cold
 NaOCl NaCl  H2O
(P)
hot
3Cl2  6NaOH(conc.)   NaClO3  5NaCl  3H2O
(Q)
(P) and (Q) are salts of HOCl and HClO3 respectively.

2. Answer (A)
Charcoal
SO2  Cl2 
Catalyst
SO2Cl2
(R)
10SO2Cl2  P4  4PCl5  10SO2

(R) (S)
PCl5  4H2O  H3PO4  5HCl

(S) (T)
C11. 1. Answer (C)
2. Answer (A)
Solutions of C11 (Q.1 & Q.2)
[MnO ]
2KClO3 
2
 2KCl  3O2
(W )
5O2  P4  P4O10
(X)
P4 O10  4HNO3  2N2O5  4HPO3

(Y) (Z)
C12. 1. Answer (A)

Partial roasting of chalcopyrite
O2 / 
CuFeS2   Cu2S  FeO
2. Answer (D)
FeO  SiO2  FeSiO3
gauge flux slag
3. Answer (C)
Cu2S + Cu2O  6Cu + SO2
C13. 1. Answer (B)
2. Answer (A)
3. Answer (C)
Solution of C13 (Q.1 to Q.3)
Cu  Ag  Cu2  Ag
Ag  NaCl  AgCl

White ppt
AgCl  NH3 [Ag(NH3 )2 ] Cl
Cu2  NH3  Cu(NH3 )24

(Blue)
M - Cu
N - Solution of AgNO3
O - AgCl
C14. 1. Answer (B)
Ni+2 + HCl  [NiCl4]–2
Ni+2 + KCN  [Ni(CN)4]–2
2. Answer (D)

OH
Zn2  OH  Zn(OH)2   [Zn(OH)4 ]2
white ppt Soluble
C15. 1. Answer (D)

N(CH3)2 N(CH3)2
Cl–
+
(CH3)2N S N(CH3)2
+3
+ H2S + + 6 Fe 6Fe2  NH4  4H 
N
Methylene blue
NH2 NH2
2. Answer (C)
Fe 3  [Fe(CN)6 ]4 

 Fe4 [Fe(CN)6 ]3
Prussian blue ppt.
3. Answer (B)
Fe 3  [Fe(CN)6 ]3 

 Fe[Fe(CN)6 ]
Brown colouration
C16. 1. Answer (A)

Lead salts give white precipitate of PbCl2 with dil. HCl which is soluble in hot water.
2. Answer (D)
The filtrate on treatment with ammonical H2S gives a precipitate which dissolves in aqueous NaOH
containing H2O2 giving a coloured solution. It contains Cr3+ ion.
Cr 3  3NH4 OH  Cr(OH)3   3NH

4
(Green)
2Cr(OH)3  3H2O2  4NaOH  2Na2CrO4  8H2O

(yellow colour )
C17. 1 Answer (D)

2. Answer (B)
Solution of C17 (Q.1 & Q.2)
O (i) NaBH4 OH
H3C 2+ + H3C + H3C
Hg /H3O (ii) dil H
H3C C – C C–H H3C C – C H3C C – C – H
H3C H3C CH3 H3C CH3

H3C H H3C H 
–H   H
C – C – CH3 H3C C – C
H3C CH3 H3C CH3
(i) O3
H3C CH3 CH3
(ii) Zn–H2O
C C 2 C O
H3C CH3 CH3
C18. 1. Answer (A)
NaNH2 – + CH3 CH2 I
H C Na C
+ – (1 eq) + –
HO Na O Na O
CH3 I
CH3
H2
CH3 O
O Lindlar's
H H catalyst
2. Answer (C)
1. NaNH2 (2 eq ) O
2. OH
Br
H +
3. H3O (mild)
4. H2, Pd/C
5. CrO3
C19. 1. Answer (C)
OH
Pd-BaSO4 i. B2H6
C8H6
H2 ii. H2O2, NaOH, H2O
X
2. Answer (D)
O
H2O
C8H6
HgSO4
H2SO4
i. Et MgBr, H2O
+
ii. H , Heat
Y
C20. 1. Answer (B)
2. Answer (A)
3. Answer (D)
O OH
Ph – C – CH3 + PhCH2MgBr Ph – C – CH2 – Ph
CH3 H
Conc. H2SO4 dehydration
Ph – C = CHPh Ph CH3
or
CH3 H Ph
I
Ozonolysis
O
Ph – C = O + Ph – C – H
CH3 J
K
Cannizzaro's
KOH reaction
Aldol followed
KOH
by dehydration
PhCH2OH + PhCOOK
O
H3C L
Ph Ph
H
M
C21. 1. Answer (B)

2. Answer (A)
3. Answer (B)
Me Me Me
(i) MeMgBr H2SO4 (i) O3
(ii) H3O
+ OH (ii) Zn-H2O
O Me Me Me Me Me
P Q
– Me
(i) OH/H2O O
O
(ii) H , 
+
C
O Me
Me Me Me Me
S R
C22. 1. Answer (B)
2. Answer (A)
3. Answer (D)
CH3 O
H3C
1. K2CO3 C
C H
2. H H C H
H3C C H3C
H C
(Q) CH2
(P) O 3. H + O OH
(R)
HCN
OH
H3C CN
CH O
C C H3C
H3C CH
Hydrolysis
C OH
H2C HO H3C
O H CH2
 OH
(S)
OH
H3C
C O
H3C
H2C O
C23. 1. Answer (C)
2. Answer (A)
CHO CH = CH–COOH
(CH3CO)2O (i) H2, Pd/C

CH3COONa (ii) SOCl2
(iii) Anhyd. AlCl3
O
C24. 1. Answer (B)
H COOH COOH
H OH
C dil. alk. KMnO4
H OH
C
COOH
H COOH
(S)
(P)
H COOH
COOH COOH
C dil. alk. KMnO4 H OH HO H
C HO H + H OH
HOOC H COOH COOH
(Q) (T) (U)
2. Answer (A)
O
H COOH
C H2/Ni
O

C
HOOC H
(Q) O
(V)
O O
O+ AlCl3 Zn(Hg) H3PO3

anhydrous HCl
HO HO
O O O O
(V) (W)
C25. 1. Answer (A)
O O
NH2
KMnO4/H +
C OH NH3 C NH2 Br2/NaOH
 C OH  C NH2 (Hoffman bromamide)
NH2
O O
(P) (Q) (R)
2. Answer (B)
C
Br – C
C=O
O
O O O
CH2
C – NH2 C C C
 CH3
–NH3
N–H N–C
C=O
C – NH2 C C
(Q) (S)
O (Phthalimide) O O O
CH2
+
H3O
CH3
O
O C – OH
C – C – C – OH+
NH2 C – OH
(alanine)
(T) O
C26. 1. Answer (B)

2. Answer (C)
– +
O OMgBr
C(CH3)3 C – OEt CH3MgBr (excess)/(C2H5)2O C(CH3)3 CH3–C–CH3
(P)
H2O
H H
O O–H
C(CH3)3 C(CH3)2 H2SO4/ C(CH3)3 CH3–C–CH3
0°C
(Q)
–H2O (dehydration)
CH3
CH3
C(CH3)3 C(CH3)2 C(CH3)3
(alkylation)
(R)
O
CH3–C–Cl/AlCl3
(Acylation)
CH3
CH3
C(CH3)3
COCH3
(S)
C27. 1. Answer (C)
CHO O—H
COOH
Ac2O Br Moist
CO/HCl Br2/Na2 CO3
AlCl3 AcONa COOH KOH
(anhy.) D
(X) (473 K) (Y)
CuCl
2. Answer (A)
O
CO/HCl – C– H AC2O/NaOAC – CH = CH – COOH
AlCl3/CuCl
(X)
H2/Pd–C
– CH 2 – CH 2 – COOH
H3PO4
O
(Z)
C28. 1. Answer (A)
CH2–CH2 O
(C11H12O2) dibasic acid OH OH O
oxidation C C (CH2)2 O
P, Organic acid (P must have O
multiple bond) O
dacron
dibasic acid must be terephthalic acid i.e.
COOH
to give dacron, compound must have benzene based structure
COOH
Ozonolysis
C11H12O2 ketone + oxidized products of benzene.
COOH
Possible structure of P is (C11H12O2)
COOH COOH
O
oxidation
+
COOH
(P)
COOH
ozonolysis
O
+ oxidized product
ketone
(P)
O O Me
COOH COOH C–Cl C–Me H–C–OH
H 2/Pd-C SOCl2 MeMgBr, CdCl2 NaBH 4
(P) (Q)
Me Me
–
CH–OH CH–Cl Me–CH Mg+2 Cl– Me–CH–COOMgCl Me–CH–COOH
+
HCl Mg, Et2O CO2 H 3O
(Q) (R)
2. Answer (B)
 –
COOH COOH CONH 2 NH2 N C NH CH3
H2 /Pd-C NH3 / Br2 /NaOH CHCl3/KOH H2 /Pd-C

SECTION - D
Matrix-Match Type Questions
1. Answer A(q); B(s); C(p, q, r), D(p, q, r)
2. Answer (D)
1s orbital is nondirectional so  will not depend upon cos.
Hence, 'D' is incorrect.
3. Answer (D)
For H-like species only D is correct, because
in (A), 1s orbital has no radial node.
In (B) for 3dz2 , xy plane is not nodal plane.
In (C), 2pz orbital has no radial node.

4. Answer (D)
For H-atom,
3 ⎛ Zr ⎞
⎛ Z ⎞ 2 ⎜ a ⎟
1s-orbital   ⎜ ⎟ e ⎝ 0 ⎠
⎝ a0 ⎠
3
Also, E4  E2 
16
2
E6  E2 
9
27
Hence, (E6  E2 )   E 4  E2
32
5. Answer A(p, r, t), B(s, t), C(p, q), D(p, q, s)
Electronic configuration as
2p1x
B2 ⇒ 1s2 * 1s2 2s2 * 2s2
2p1y
 It is paramagnetic, as highest occupied orbital is partially filled and it is of bonding nature, therefore it will
readily undergo reduction.
When Zeff is less like B and N, then energy difference between 2s and 2pz is very small. Due to their same
symmetry mixing of s and p orbital take place.
Similarly in N2 b.o. is 3, it is diamagnetic, Neither it will undergo oxidation nor reduction.
O2 and O2 are paramagnetic.
6. Answer (C)
P. d – d ( bonding)
Q. p – d ( bonding)
R. p – d ( antibonding)
S. d – d ( antibonding)
7. Answer : A(p, r, s), B(r, s), C(t), D(p, q, t)

Phase is the part which is physically and chemically uniform throughout. During phase transition from solid to
liquid or gas, S = +ve.
In 2H 
 H2, S is –ve because no. of entities decreases.
8. Answer A(R, T), B(P, Q, S), C(P, Q, S), D(P, Q, S, T)
(A)  R, T

H2O( )
H2O(S)
It is at equilibrium at 273 K and 1 atm

So Ssys is negative
As it is equilibrium process so G = 0
(B)  P, Q, S
Expansion of 1 mole of an ideal gas in vacuum under isolated condition
Hence, w = 0
and qp = CpdT (∵ dT = 0)
 q=0
U = CvdT (∵ dT = 0)
U = 0
(C)  P, Q, S
Mixing of two ideal gases at constant temperature
Hence, T = 0
 q=0
U = 0
also w = 0 (U = q + w)
(D)  P, Q, S, T
Reversible heating and cooling of gas follows same path also initial and final position is same.
q0 ⎫
Hence, ⎬ Path same
w  0⎭
U  0 ⎫
⎬ State function
G  0 ⎭
9. Answer (D)
20  0.1– 10  0.1 1
(P) CH3 COOH  
old 30 30
⎡ CH COO – ⎤ = 1
⎣ 3 ⎦ old 30
Buffer with [Salt] = [Acid]
pH does not change on dilution (P)  (1)
20× 0.1 2
(Q) [ CH 3COO– ] old = =
40 40
2
[ CH 3COO– ] new = 80
–
 CH3 COOH+ OH–
CH 3COO + H2O 
c x x
x 2 [OH– ]old
2
[OH– ]new
2
Kh = = =
c 2 / 40 2 / 80
– 2
 [OH ] new = [OH ]old
– 2
[OH– ]old
 [OH– ]new =
2
 [H+ ]new = 2[H+ ]old

(Q)  (5)
20 × 0.1 2
(R) [NH+4 ]old = =
40 40
2
[NH +4 ]new =
80
NH+4 + H2 O
NH4 OH + H+
c y y
y 2 [H+ ]old
2
[H+ ]2
Kh = = = new
c  2 / 40   2 / 80 
+ [H+old ]2
 [Hnew ]2 =
2
+ [H+ ]old
[Hnew ]=
2
(R)  (4)
–
(S) For a saturated solution, [OH ] = 3 2K sp
irrespective of volume of solution. [H+] remains constant.

(S)  (1)
10. Answer (A)

(P)
Conductivity
(C2H5)3N
+
Firstly it decreases due to nutrilization of CH3COOH and replacement of H+ by (C2H5)3NH but thereafter buffer
+
formation takes place and [H+] becomes constant and (C2H5)3NH increases hence conductivity increases but
+
after equivalence point (C2H5)3N is not ionized due to much higher concentration of (C2H5)3N in solution.
(Q)
Conductivity
VKI
AgNO 3 + KI 
 AgI(S) + KNO 3
Initially only Ag+ is replaced by K+ hence conductivity remain the same thereafter equivalence point [K+]
increases hence conducitity increases.
(R)
Conductivity
VCH3COOH
Initially conducitity decreases due to replacement of OH– by CH3COO– and then almost constant due to
buffer formation
(S)
Conductivity
VNaOH
Decreases due to removal of H+ by Na+ then increases due to OH–.

11. Answer (D)
+3 +2
(P) Fe + e Fe ºG1 = – 1F × 0.77
+2
Fe + 2e Fe ºG2 = + 2F × 0.77
+3
Fe + 3e Fe ºG3 = – 3F × EºFe+3/Fe
ºG 3 = ºG 1 + ºG2
– 3F × EºFe+3 /Fe = – 0.77 F + 0.88 F
– 3EºFe+3 /Fe = 0.11 (V)
0.11 (V)
EºFe+3 /Fe = – = – 0.036 (V)
3
+
(Q) 2H2O O2 + 4H + 4e Eº = – 1.23 V
–
4e + O2 + 2H2O OH Eº = + 0.40 V
+ –
4 H2O 4H + 4OH Eº = – 0.83 V
2+
(R) Cu + 2e Cu Eº = + 0.34 V
2+
2Cu Cu + 2eu Eº = – 0.52 V
2+ +
Cu + Cu 2Cu Eº = – 0.18 V
+3
(S) Cr + 3e Cr ºG1 = + 3 × F × 0.74
+2
Cr Cr + 2e ºG2 = + 2 × F ×0.91
+3 +2
Cr + e Cr
EºCr+3 /Cr+2 = – 0.4 V
12. Answer A(p, s), B(q, s), C(r, t), D(q, t)
3Cu  8HNO3 

 3Cu(NO3 )2  2NO  4H2O
(dil.)
Cu  4HNO3 
 Cu(NO3 )2  2NO2  2H2O
(conc.)
4Zn  10HNO3 

 4Zn(NO3 )2  N2O  5H2 O
(dil.)
Zn  4HNO3 
 Zn(NO3 )2  2NO2  2H2O
(conc.)
13. Answer : A(p, s), B(p, q, r, t), C(p, q), D(p)

CH3
CH3
Polymerise Si
(A) (CH3)2SiCl2 + H2O Si—OH O O
OH CH3 CH3
n
(B) 6XeF4  12H2 O  4Xe  2XeO3  24HF  3O 2
(C) Cl2  H2 O  HCl  HOCl
(D) VCl5  H2 O  VOCl3  HCl
Note : Vanadium in (+V) oxidation state from only fluoride. Existence of VCl5 is doubtful.
14. Answer (D)

Warm
(P) 2PbO2 + 2H2 SO 4   2PbSO 4 + 2H2 O + O2
(Q) Na2 S2 O3 + 5H2 O + 4Cl2 

 2NaHSO 4 + 8HCl
(R) N 2H 4 + 2I2  N 2 + 4HI
(S) XeF2 + 2NO 

 Xe + 2NOF
15. Answer : A(p); B(q); C(p, r), D(p, s)

16. Answer A(P, Q, S), B(T), C(Q, R), D(R)
Siderite  FeCO3
Malachite  CuCO3
Cu(OH)2
Bauxite  Al2O3·xH2O or
AlOx(OH)3 – 2x 0 < x < 1
Calamine  ZnCO3
Argentite  Ag2S
17. Answer (B)

Hint : Magnetic character Isomerism
P. [Cr(NH3)4Cl2]Cl Paramagnetic cis/trans
Q. [Ti(H2O)5Cl](NO3)2 Paramagnetic ionization
R. [Pt(en)(NH3)Cl]NO3 Diamagnetic ionization
S. [Co(NH3)4(NO3)2]NO3 Diamagnetic cis/trans
18. Answer (C)
1. [FeF6]4–
3d 4s 4p
Fe+2
High spin complex because F– is weak field ligand.

sp3d2
2. [Ti(H2O)3Cl3]
Ti
3+
d2 sp3
2 3
d sp
3. [Cr(NH3)6]3+
2 3
Cr3+ d sp
2 3
d sp
4. [FeCl4]2–
Fe+2 : 3d6, Cl– is weak field ligand.
3d 4s 4p
sp 3
5. Ni(CO)4
Ni0 – 3d84s2, CO is strong field ligand
Ni
3
sp
6. [Ni(CN)4]2–
+2
Ni
2
dsp
CN– is strong field ligand.
19. Answer (A)
NaOEt
(P) Cl
(Q) ONa + Et-Br OEt
(1) Hg(OAc)2 OH
(R)
(2) NaBH4
(1) BH3
(S) (2) H2O2/NaOH
OH
20. Answer (B)
(P) ONa + Br + OH
with 3° halide, elimination predominates.
(Q) OMe + HBr Br + MeOH
(R) Br + NaOMe
(S) ONa + MeBr OMe

P  1, 4; Q  2; R  4; S  3.
21. Answer : A(r, s); B(p, q); C(p, q, r), D(p)
22. Answer A(p, q, s, t), B(p, s, t), C(p), D(r)
(A) CH3CH2CH2CN will give negative test with alkaline CHCl3. It will give mentioned reaction with other reagents.
(B) Esters will be reduced by catalytic hydrogenation, DIBAL-H and it will be hydrolyzed by alkaline hydrolysis.
(C) Alkenes are only reduced by catalytic hydrogenation.
(D) Primary amines will give +ve carbyl amine test with NaOH and CHCl3.
 
O
NaOH
CH3 CH2CH2CH2 — NH2 
CHCl
 CH3 CH2CH2CH2 — N  C
3
Carbyl amine
23. Answer : A(p, q), B(p, q, s, t), C(r, s), D(p)
NCl
SN2
Br
O
(A)
O E2
(B) OH ZnCl2/HCl Cl [Nucleophilic substitution]

El
im
ina
tio
no
rd
eh
(RCO)2O yd
ro
ge
na
O tio
n
C CHO
O R
HO NCl
C
NCl H
O
OH
C
(C) H
O
OH O O
C
R C O C R H
O
O R
Br s
Nu
Nu
(D) (SNAr)
NO2 Mechanism NO2
24. Answer : A(r, s), B(t), C(p, q), D(r)
(A) NN + O—H

Cl–
OH
N=N O
H
N=N O
 Coupling reaction and electrophilic substitution reaction.
OH OH OH OH2
+H
(B) CH3 — C — C — CH3 CH3 — C — C — CH3
CH3 CH3 CH3 CH3
O CH3 OH
CH3
CH3 — C — C — CH3 CH3 — C — C
CH3
CH3 CH3
Carbocation intermediate
O OH
O H3O
+
LiAlH4 H
(C) C Nucleophilic addition
C H C H
CH3
CH3 CH3
Racemic mixture
Nucleophilic
H Base S substitution S
(D)
S Cl Cl
B
25. Answer : A(r, s, t), B(p, s, t), C(r, s), D(q, r)
O O
H CH2 H2C
O O O O
OH Nucleophilic addition
A.
Carbanion
O OH O
Dehydration HO – H
–H2O
O Cl
Cl O O
B. CH3MgBr Nucleophilic
CH3 substitution CH3
Carbanion
Nucleophilic
addition
H
..
.O
. O H H
18 18
H–O H–O O  H–O O
–H
Nucleophilic +H
C.
addition H
Dehydration
18
O

+H Electrophilic
D. OH Dehydration substitution
H
Me Me
26. Answer (A)
O
O
(1) C6H5CH2 – C – O CH3 C6H5CH2 + CO2 + CH3 – O
O CH3 CH3
O
(3) C6H5CH2 – C – O C CH3 CO2 + C6H5CH2 + CH3 – C – O
CH2 – C6H5 CH2 – C6H5
O
C O CH3 O CH3
(4) C6H5 O C – CH3 C6H5 – C – O + O – C – CH3

CH3 CH3
O O
C O C
(2) C6H5 O CH3 C6H5 O + CH3 – O
27. Answer (D)
h
Br2 Br + Br
CH3 CH2
+ Br + HBr
CH2 CH2 – Br
+ Br2 + Br
28. Answer (C)

– +
COO Na
NaOH
C CH3 Br2 + CHBr3
O
H2O/H+
COOH
It is haloform reaction
29. Answer (C)
O
CH3 – C
O
CH3 – C
CH = O CH = CH – COOH
O
CH3 COOK
Cinnamic acid
It exists in two geometrical forms.
C –H C –H
H – C – COOH HOC – C – H
Trans O
isomer Cis isomer
It is basic example of Perkin's reaction.
30. Answer (D)
Ph Ph O O
Me Ph
I2/NaOH
(P) HO + H2SO4 Me Me C – OH
Ph HO Me Ph Me Ph
O
Ph
NaOBr
Me C – OH
Ph
P  1, 5
Ph Ph O Ph
H [Ag(NH3)2]OH
(Q) H2N OH + HNO2 Me Me COOH
Ph Me Ph H Ph
Ph
Fehling
Me COOH
Solution
Ph
Q  2, 3
Ph Ph O
Ph
(R) HO OH + H2SO4 Ph
Me Me Me Me
NaOBr I2/NaOH
Ph Ph
Me COOH Me COOH
Ph Ph
R  1, 5
Ph Ph
Ph
(S) Ph OH + AgNO3 Ph CHO
Br Me Me
Fehling [Ag(NH3)2]OH
solution
Ph Ph
Ph COOH Ph COOH
Me Me
S  2, 3
31. Answer (C)
NO2
Scheme I (S)
CH3
NO2
Scheme II (R)
Scheme III H – C  C – H (P)

OH
Scheme IV
OH

SECTION - E
Integer Answer Type Questions
1. Answer (3)
25.2  25.25  25
Average titre value = = 25.15
3
Siginificant figure is 3.
2. Answer (4)
6.023 × 1023 × 1.380 × 10–23 = 8.312
It has four significant figure.
3. Answer (8)
w 2  1000
m
m2  w 1
1 mL solvent having mass 0.4 g.
1000 mL solvent having mass 400 g
1000 mL solution contain 3.2 × 80 g solute = 256 g
256  1000
 m 8
80  400
4. Answer (4)
Energy of incident photon should be higher than work function to slow photoelectric effect
6.62  1034  3  108

Energy of photon =  4.14 eV
300  109  1.6  1019
5. Answer (9)
3s 3p 3d
Out of 18 electrons present in 3rd shells.
1
Will have s  
2
6. Answer (5)
3RTNe
MNe
He MNe VNe MNe
 
Ne MHe VHe 3RTHe
MHe
MHe
TNe
MNe
MNe MNe TNe
 
THe MHe THe
MHe
MHe
205  1000

4  200
He  5Ne
7. Answer (6)
|ml| = 1
means ml can be +1 and –1
1
So, for n = 4 six orbitals are possible and bear six electrons with s  –
2
8. Answer (3)
Ground state configuration:
–
H:
1s 2s 2p
in second excited state, electron will jump from 1s to 2p, so degeneracy of second excited state of H– is 3.
9. Answer (4)
In CuSO4.5H2O, one molecule of water is H-bonded and other four molecules are bonded to metal centre.
10. Answer (0)
Fa
Feq Feq
Feq Feq
Br
Presence of lone pair will distort all the bond angles and none of the bond angle is exactly equal to 90º
FaBrFeq = 84°
FeqBrFeq = 89°
11. Answer (4)
Cl – Be – Cl N3–
Hybridization sp Hybridisation sp
Structure linear structure linear

..
+ O
O=N O ..
O O
..
..
..
..
Hybridisation sp Hybridisation sp2

Structure linear Structure Trigonal planar
..
S ..
..
–
[Cl –..I – Cl]
..
Cl Cl 3 3
Hybridisation sp Hybridisation sp d
Structure Angular Structure linear
.. – ..
[I –..I – I]
.. F –..Xe – F
..
3 3
Hybridisation sp d Hybridisation sp d
Structure linear Structure linear
 
NNO
Hybridisation sp
Structure linear

Only BeCl2, N3–, N2O and NO2 are linear with sp-hybridisation.
12. Answer (6)
H2 12s Diamagnetic
He2 12s 1*s1 Paramagnetic
Li2 12s 1*s 2 22s Diamagnetic
Be2 12s 1*s 2 22s 2*s 2 Diamagnetic
B2 12s 1*s 2 22s 2*s 2 12 px  12 py Paramagnetic
C2 12s 1*s 2 22s 2*s 2 22 px  22 py Diamagnetic
N2 12s 1*s 2 22s 2*s 2 22 px  22 py 22 pz Diamagnetic
O2 12s 1*s 2 22s 2*s2 22 pz 22 px  22 py 2* p1  2* p1 Paramagnetic
x y
F2 12s 1*s2 22s 2* s2 22 pz 22 px  22 py , 2* p2  2* p2 Diamagnetic
x y
13. Answer (6)

Br
Br Br
Te It has one lone pair
Br Br
Br
Br It has two lone pairs

F
F
F
SN It has no lone pair
F
F
F
F
Xe It has three lone pairs
F
14. Answer (4)
3RT
Urms( X ) 
M
2RT
Vmp( Y ) 
M
Equating both, we get
3R(400) 2R(60)

40 X
X=4
15. Answer (7)

1 atm PT = 1 atm
1 atm vapour pressure of compound = 0.68 atm
⇒ PHe = 0.32
PHeV = nHeRT
0.1 0.082  273

V= = 7 litre
0.32
16. Answer (4)
Diffusion coefficient 
Here  = mean free path
 = mean speed
T
since  
P
and   T
T T
 Diffusion coefficient 
P
As per question, 'T' is increased four times and 'P' is increased two times.
Hence, diffusion coefficient becomes four times.
17. Answer (2.22)
From figure - 1,
5 1 5
nA = 
R  400 400 R
1 3 3 1
nB =  
R  300 300 R 100 R
From figure. 2,
After the system attains equilibrium,
PA = PB and TA = TB = T
n A RT nBRT
 
VA VB
5 1
 
400 R.VA 100 R.VB
VA 5 4
  ⇒ VB  VA
VB 4 5
4
∵ VA + VB = 4 m3  VA + VA  4
5
20
 VA = = 2.22 m3
9
18. Answer (9)
q = heat capacity × T
1.125 kJ for 3.5 g
for 1 mole = 9 kJ
19. Answer (2)
Solid line path work done (Ws) is isothermal beacuse PV is constant at each point & dash line path work
done (Wd) is isobaric.
V2
Total work done on solid line path (Ws) = 2.303nRT log
V1
V2
= 2.303PV log
V1
5.5
= 2.303 × 2log
0.5
 4.6 l atm
Total work done on dash line path (Wd) = 4 × 1.5 + 1 × 1 + 0.5 × 2.5
= 8.255 l atm.
Wd 8.25
  2 (closest integer)
Ws 4.6
20. Answer (8)
pK a 4 2
pH = 7   log C = 7   8
2 2 2
21. Answer (3)
In basic medium, red litmus paper turn blue
(1) CN  H2 O

HCN  OH

(2) CO32  H2 O


HCO3  OH

(3) CN  H2O

HCN  OH

22. Answer (6)

H2SO4, H3PO3, H2CO3, H2CrO4 and H2SO3 and H2S2O7 will behave as dibasic acid.
23. Answer (7)
 Ag  Cl
AgCl 
x xy
K sp1 = 1.6 × 10–10 = x(x + y) ...(i)
 Cu  Cl
CuCl 
y yx
K sp2  1 10 –6  y(x  y) ...(ii)

From equation (i) and (ii),
K sp1 x
 1.6  10 –4  ...(iii)
K sp2 y
 x = 1.6 × 10–4 y
 K sp1  1.6  10 –10  1.6  10 –4 y(1.6  10 –4 y  y)
 10–6 = y2(1.6 × 10–4 + 1)

 y = 10–3  x = 1.6 × 10–7
 [Ag+] = x = 1.6 × 10–7
24. Answer (4.47)
AB(s) A  (aq)  B  (aq)

s s x
B   H3 HB
s x 10
Ka of HB = 1 × 10–8
⎡H ⎤ ⎡B ⎤  s  x   103

Ka  ⎣ ⎦ ⎣ ⎦ 
HB x
sx
 105 s  x  x  105
x
Ksp = [A+] [B–] = s(s–x) = 2 × 10–10
Sx = 2 × 10–5 s2–sx = 2 × 10–10
s2 = 2 × 10–10 + 2 × 10–5
s2 = 2 × 10–5
s  20  103  4.47  103

25. Answer (–14.60)
1
(i) 2Cu(s)  O2 (g)  Cu2O(s), G  –78 kJ / mole
2
1
(ii) H2 (g)  O2 (g)  H2O(g), G  –178 kJ / mole
2
(i) – (ii)
2Cu(s)  H2O(g)  Cu2O(s)  H2 (g), G  100 kJ
G  G  RT ln K  0
⎛ pH ⎞
 105  8  1250 ln ⎜ 2 ⎟0
⎜ pH O ⎟
⎝ 2 ⎠
⎛ pH ⎞
10 4 ln ⎜ 2 ⎟  105  0
⎜ pH O ⎟
⎝ 2 ⎠
ln pH2 – ln pH2O  –10
–2
Now, pH2O  XH2O  PTotal  0.01 1  10
 ln pH2  2 ln10  –10
ln pH2  4.6  –10
ln pH2  –14.60
26. Answer (2)
F will only exhibit –1 oxidation state except zero.
and Na will exhibit +1 oxidation state.
27. Answer (5)
⎡Br2  2Br – ⎤ 5 –
⎢ ⎥  5 ⎡⎣Br2  2Br  10e ⎤⎦
⎢⎣2 e ⎥⎦
Br2 + 5Br2  10NaBr + 2NaBrO3 + 6CO2 + 6Na2CO3
3Br2 + 3Na2CO3  5NaBr + NaBrO3 + 3CO2
28. Answer (8)
1.25  29.2  1000
Molarity of HCl =  10(M)
100  1 36.5
V × 10 = 200 × 0.4
V = 8 mL
29. Answer (7)
K2Cr2O7 + I– + H+  I2
CuSO4 + I–  I2
H2O2 + I–  I2
Cl2 + I–  I2
O3 + I–  I2
FeCl3 + I–  I2
HNO3 + I–  I2
30. Answer (6)
3S2O3– + 8MnO4–  6SO42– + 8MnO2
 8 moles of MnO4– form 6 moles of SO42–
31. Answer (126.00)
From POAC,
m moles of MnCl2 = m moles of KMnO4 = x((let)
and, meq of KMnO4 = meq of oxalic acid
⎛ 225 ⎞
x5  ⎜ ⎟2
⎝ 90 ⎠
x=1
 m moles of MnCl2 = 1
mg of MnCl2 = (55 + 71) = 126 mg
32. Answer (7)
4 3
Volume of 1 Ag atom = r
3
4 3 108
 r  cm3
3 6.023  1023  10.5
 r = 1.6 × 10–8 cm
r = 1.6 × 10–10 m
 Number of Ag atoms in 10–12 m2

r2 × n = 10–12 m2
10 –12
n
3.14  (1.6  10 –10 )2
10  107
n
8
n = 1.25 × 107
 The value of x = 7
33. Answer (8)
Truncated octahedron contain 14 faces out of that eight are hexagonal and six are square.
34. Answer (2)
a = 4  10–8 cm (a = edge length)
d=8g cm–3 (density)
ZM
d M = molecular mass (g/mol)
NA a3
Z  number of atom in 1 unit cell
3
dNA a 8  6  1023  64  10–24
M   76.8 g/mol
Z 4
Mole of solid in 256 g = 3.33 moles
No. of atom = 3.33  NA = 20  1023 = 2  1024
35. Answer (3.00)
MX has NaCl type structure.
From instructions, it is clear that in MX ionic solid.
Cation M - undergoes CCP
anion X - occupies all octahedral voids
(i) No. of anions left = 1
(ii) No. of anions added = 3
No. of cations left = 1
(iii) No. of cations left = 0
(iv) No. of cations added = 1
No. of anions left = 3
Final no. of cations in an unit cell = 1
Final no. of anions in an unit cell = 3
3
 ratio = = 3.00
1
36. Answer (2)
 = 0.5
2

MX2
M  2X 
(1 )  2
1      2
i
1
i = 1 + 2
i = 1 + 2 × 0.5 = 2
37. Answer (9)
0.1 1000
Molality (m) = ...(i)
0.9  MWsolvent
0.1 2  1000
Molarity (M) = ...(ii)
 0.9  MWsolvent  0.1 MWsolute 
Equating (i) & (ii),
0.1 1000 0.1 2  1000

0.9  MWsolvent  0.9  MWsolvent  0.1 MWsolute 
MWsolute
So, 9
MWsolvent
38. Answer (19.00)
P°A = 20 Torr
1
For equimolar binary solution : xA = xB =
2
PA° + PB°
 = 45
2
 P°B = 70 Torr
If mole fractions are xA & xB
P°B + (P°A – P°B)xA = 22.5
 70 + (20 – 70)xA = 22.5
47.5 2.5
 xA = and xB =
50 50
x A 47.5
= = 19.00
xB 2.5
39. Answer (0.05)
When NaCl as solute is used
For solvent X For solvent Y
2 = 2Kb m 1 = 2 × Kb m
Kb
 =2
K b
When solute S is used then molality in both solvent is equal.
For solvent X For solvent Y
a 0.7
i = 1– i = 1– = 0.65
2 2
⎛ a⎞
Tb = ⎜ 1 – ⎟ K b m Tb = (0.65)Kbm
⎝ 2⎠
⎛ a⎞
1– ⎟ × 2
Tb ⎜⎝ 2⎠
3= =
Tb 0.65
 3
1– = × 0.65
2 2
 3
= 1 – × 0.65
2 2
 = 0.05
40. Answer (4)

X  Y; rG° = – 193 kJ mol–1
M+  M3+ + 2e– E° = – 0.25 V
Hence G° for oxidation will be
G° = – nFE°
= –2× 96500 × (–0.25)
= 48250 J = 48.25 kJ
48.25 kJ energy oxidises one mole M+
193
 193 kJ energy oxidises mole M  4 mole M
48.25
41. Answer (3)
1  HX 2  HY
(m )HX (m )HY
1  o
2  o
m m
K a1  C112 K a2  C2 22
2 2
(m )HX (m )HY
 0.01 o 2
 0.1 o 2
( m ) ( m )
2
K a1 2
0.01(m )HX ⎛ ( ) ⎞
  2
 0.1⎜ m HX ⎟
K a2 0.1(m )HY ⎝ (m )HY ⎠
2
⎛ 1⎞
 0.1⎜ ⎟
⎝ 10 ⎠
= 10–3
K a1
pK a (HX)  pK a (HY)   log   log10 3
K a2
=3
42. Answer (6)
⎛ l ⎞ 120
  C ⎜ ⎟  5  107 
A
⎝ ⎠ 1
= 6 × 10–5 S cm–1
  1000 6  105  1000

M  
M 15  104
 M = 40 S cm2 mol–1
[H+] = C = 10–4
10 4 1
 
15  10 4 15
M
  º
M

 M = 40 × 15 = 600 = 6 × 102 S cm–1 mol–1
43. Answer (10.00)
Cell reaction :
Mg(s)  Cu2 (1 M)  Cu(s)  Mg2 (xM)
2.303T
Ecell  Ecell  log x
F/R
2.303  300
2.67  2.70  log x
11500  2
2.303  3
0.03  log x
115  2
0.03  115  2
log x  1
2.303  3
x = 10.00
44. Answer (–11.62)
A  A n  ne –
B2n  2ne –  B
2A  B2n  2A n  B
H° = 2G°, Ecell = 0
G° = H° – TS°
G
 G° = TS°  S 
T
– RT ln K [A n ]2 22
S   – R ln 2n  – 8.3  ln
T [B ] 1
 S° = – 11.62 JK–1 mol–1
45. Answer (8)
238 214
92 U 
 82 Pb  X24 He  y01 e
24 = 4x; x = 6
10 = 2x – y
y=2
 x+y=8
46. Answer (0)
For zero order reaction,
dx
k
dt
From 1 to 0.75 (M),
0.25
5
0.05
From 0.75 to 0.40,
0.35
5
0.07
From 0.40 to 0.10,

0.30
5
0.06
It mean order of this reaction is zero.
47. Answer (3)
142
92 U235  54 Xe + 38
90
Sr +3 10n
48. Answer (8)
63
29 Cu  11H  610 n  ( 24 He)  211H  X(52
26 Fe)
Fe belongs to group-8.
49. Answer (9)
2.303 1
t1/8  log10 ...(i)
k 18
2.303 1
t1/10  log10 ...(ii)
k 1 10
[t1/8 ] log8
 10   10  3  0.3  10  9
[t1/10 ] log10
50. Answer (9)
238 206 4 0
92 U  82 Pb  8 2He  6 – 
Now, number of moles in gas phase = 1 + 8 = 9 mole

At constant temperature and pressure
PF nF 9
  9
Pin nin 1
51. Answer (8)
8H  5 Fe(H2O)2 (OX)2   MnO4  Mn2  5 Fe(H2O)2 (OX)2   4H2O

2 
1 d[H ] d[MnO4 ]
Rate   
8 dt dt
rate of [H ] decay
Hence, 8
rate of [MnO4 ] decay
52. Answer (8500.00)
A(g) + B(g) AB(g)
Eab – Eaf = 2RT
Af
=4
Ab
Kf
K=
Kb
–E a f /RT
Kf = Afe
K b = A b e –Eab /RT
Kf A (E –E )/RT
= f e ab af
Kb Ab
 K = 4e2RT/RT
K = 4e2
G° = – RT In K
= – RT (2 + ln 4)
= – 2500 (2 + 2 × 0.7)
= – 8500 J mol–1
Absolute value is 8500.00.
53. Answer (4)
Cl Cl Cl
Al Al
Cl Cl Cl
54. Answer (3)
Be3Al2Si6O18
55. Answer (5)
Structure of S4O62– is
O O
0
+5
O–S–S–S–S–O
O O
 Difference in oxidation state is +5 – 0 = +5.
56. Answer (5)
O2, SO2, H2O, H2SO4 and P4O10 convert PCl5 to POCl3.
57. Answer (8)
..
O
..
.. .. ..
N – N =O..
O
..
..
Number of lone pair = 8

58. Answer (6)
3B2H6 + 18CH3OH  6B(OCH3)3 + 18H2
59. Answer (5.00)
N2O 3 N2O5
O O O O
O
N—N N N
O O O
P4O 6 P4O7 H4P2O5

O O O
P O P P O P P P
HO O OH
O OO O O OO O H H
P O P P O P
H5P3O10 H2S2O3 H2S2O5

O O O S O O
P P P S S S
HO O O OH HO O HO OH
OH OH OH OH O
60. Answer (6.47)

2PbS + 3O2  2PbO + 2SO2
2PbO + PbS  3Pb + SO2
3 moles of O2 produce 3 moles of lead
96 kg of oxygen produce 621 kg of lead.
621
1 kg of oxygen produce = 6.468 = 6.47 kg
96
61. Answer (6)
KOH
MnO2 
fuse
 MnO24
Oxidation state = 6.
62. Answer (3)
Rh Cl(CO)(PPh3)(NH3)] is a square planar complex with four different ligands and hence it will have three
geometrical isomers
a b a b a c
Rh Rh Rh
d c c d d b
63. Answer (6)
Applying equation,
N1V1 = N2V2
0.1 × V = 2 × 0.01 × 30
2  30  10
V 6
100  1
64. Answer (8)
I
O O–C=O
C CH2 CH2
I
II O N
CH2
Co
II CH2
III O N
C CH2 CH2
O O–C=O
IV
So, bond angles are
(1) NI CoOI
(2) NI CoOII
(3) NI CoOIII
(4) NI CoOIV
(5) NII CoOI
(6) NII CoOII
(7) NII CoOIII
(8) NII CoOIV
So, total asked bond angles are 8.
65. Answer (4)
F F
F
F F F
Xe S Si B
F F F F F F F
F F
F 2–
Cl
F F NH3 NH3
Br Cu Fe
F F NH3 NH3 Cl Cl
Cl
2–
Cl 2–
Cl Cl
Co Pt
Cl Cl Cl Cl
Cl
66. Answer (1)
Given Tf = 0.0558°C
as we know, Tf = i × Kf × m
 0.0558 = i × 1.86 × 0.01
 i3
Therefore, the complex will be [Co(NH3)5Cl]Cl2.
Hence, number of chloride in co-ordination sphere is 1.
67. Answer (4)
Fe(26)  [Ar]18 3d64s2
Fe3+  [Ar]18 3d54s0
SCN– is weak field ligand hence pairing will not occur.
3+
 Fe
Unpaired electrons = 5
Magnetic moment  5(5  2) B.M.  35 B.M.  5.92 B.M.

CN– is strong field ligand hence pairing will take place.
3+
 Fe
Unpaired electrons = 1
Magnetic moment  1(1  2) B.M.  3 B.M.  1.732

Difference = 5.92 – 1.732 = 4.188
Hence answer is (4).
68. Answer (3)
Et3P CO
O
– +2 –
CH3 – C Fe Br
Et3P CO
69. Answer (6)
Cl N
N N N Cl
Co Co
N N N Cl
Cl N
Cl O
O O O Cl
Cr Cr
O O O Cl
Cl O
NH3 NH3
NC CN NC NH3
Fe Fe
NC CN NC CN
NH3 CN
NH3 NH3
NH2 NH2 NH2 Cl
Co Co
NH2 NH2 NH2 NH2
Cl NH2
OH2 OH2
H3N NH3 H3N Cl
Co Co
H3N NH3 H3N NH3
Cl NH3
H2O OH
H2O OH H2O OH2
Fe Fe
H2O OH H2O OH2
H2O OH
(All the six complexes will show cis-trans isomerism)
70. Answer (5)
– –
Cl Cl
O O NH2 O
Co Co
NH2 NH2 O NH2
Cl Cl
– –
O NH2
NH2 Cl O Cl
Co Co
NH2 Cl O Cl
O NH2
–
O
H2N Cl
Co
O Cl
NH2
71. Answer (1)
H atom :
NO2 Monomer :
2p2x  * 2p2x
O2– (Superoxide) : 1s2, *1s2, 2s2, *2s2, 2pz2,
2p2y  * 2p1y
One unpaired electron is present in either *2px or *2py. So, it is paramagnetic in nature.
Dimeric sulphur in vapor phase : It is similar as O2 in vapor state, paramagnetic in nature.
Mn3O4 : It is combined form of MnO and Mn2O3
Mn+2 has 5 unpaired electrons (d5 electronic configuration)
Mn+3 has 4 unpaired electrons (d4 electronic configuration)
So, it is paramagnetic in nature.
(NH4)2[FeCl4] : Consist [Fe+2Cl4]–2 ion.
[FeCl4]–2 : Tetrahedral, sp3 Hybridized, has configuration eg3, t2g3. (Paramagnetic in nature)
(NH4)2[NiCl4] : Consist [Ni+2Cl4]–2 ion.
[NiCl4]–2 : Tetrahedral, sp3 Hybridized, has configuration eg4, t2g3. (Paramagnetic in nature)
K2MnO4 : Mn+6 is present in compound which has one unpaired electron in 3d subshell. Mn+6 - [Ar]3d1
Paramagnetic in nature.
K2CrO4 : Cr+6 is present in compound which has zero unpaired electron, diamagnetic in nature.
72. Answer (2992)
12(NH4)2SO4 + 12Ca(OH)2 + 4NiCl2  6H2O

12CaSO4  2H2O + 4[Ni(NH3)6]Cl2 + 24H2O
952
nNiCl 2  6H2O = = 4 mol
238
Mass = 12  MCaSO4 2H2O  4M[Ni(NH3 )6 ]Cl2
= (12 × 172) + (4 × 232)

= 2992 g
73. Answer (7)
Black sulphides are
PbS, CuS, HgS, NiS, CoS, Bi2S3 and Ag2S
MnS is buff
SnS2 is yellow
74. Answer (7)
, , ,
d, l d, l, meso
75. Answer (5)

Index of hydrogen deficiency in the compound C4H6 is 2. Therefore either bicyclic compound or cycloalkenes
are possible as cyclic isomers.
 Possible isomers are
, , , ,
76. Answer (6)
H3C CH2CH3
It contains 6 alpha hydrogen atoms.

 6 contributing structures are possible.
77. Answer (9)
OH O
NaOH
–H2O
O O O O
II III IV V
O O O
III VI VII
O O
VIII IX
78. Answer (5)
, , , and are aromatic.

+
and are non-aromatic while and + are antiaromatic compounds.
79. Answer (4)
Aqueous dilute
OH
+
H H KMnO4 (excess)
Heat
HO OH
HO
(P) OH
80. Answer (5)
Br
3-bromo-3-cyclopentylhexane
Alc. KOH
+ +
(E + Z) (E + Z)
1 + 2 + 2
Total =5
Note : Dehydrobromination of alkyl bromides in the presence of alc. KOH follows E2 mechanism. Hence no
rearrangement in alkylchain is possible
81. Answer (8)
Cl2
Cl
Cl Cl
* * *
Cl
Two + Four + One + One
Stereoisomers Stereoisomers
 Total Number = 8
82. Answer (3)
Following conformers are stable with non-zero dipole moment
CH3 CH3 CH3
Br Cl CH3 Br Cl CH3
Br Cl Br Cl Br Cl
CH3 Cl Br
83. Answer (2)
Possible stereoisomer are
and
84. Answer (5)

CH3 CH2 Br CH3 CH3
H H H H H * Br Br * H
Br2 (1 mole)
H H 300 ºC
H H + H H H H
H Br H * Br H * Br H * Br
*
CH3 CH3 CH3 CH3
(enantiomerically pure) Chiral Achiral Chiral
(1) (1)
CH3 CH3 CH3
H H H H H H
H * Br H H H H
H * Br Br Br H * Br
CH3 CH3 CH2 Br
Chiral Achiral Chiral
(2) (1)
85. Answer (7.00)
HO OH
HO OH
Only three streocentre are present.
 Total isomer = 23 = 8
But one is optically inactive.
OH
OH
HO
OH
86. Answer (3)
1. O3 OH
2. Zn–H2O O O O
O O O
H
+ H3O+
OH
–H2O
+ +
O O O O
On dehydration, this alcohol
will give three products.
87. Answer (4)
Carboxylic acids and aromatic alcohols dissolves in aqueous NaOH.
COOH OH OH COOH
, , ,
N
H3C CH3
will be soluble in aqueous NaOH.
88. Answer (2)
O O O O O
+
OH
H3O OH *
O
OH (–H2O, –CO2)
O O O O O
O
HOOC (i) O3
HOOC (ii) H2O2
O (P)
So, final product (P) has two carboxylic acid
 Heating causes evaporation of water and due to which concentration of acid increases and in concentrated
acidic medium decarboxylation as well as dehydration will take place.
89. Answer (5)
O
1 2 3 4
(I) CH3 CH2 CH2 CH2 C CH3
5 6
(II) CH3 CH2 CH2 C CH2 CH3

CH3 O
(III) CH3 CH2 CH C CH3

It has chiral centre
CH3 O
(IV) CH3 CH C CH3
CH3
CH3 O
(V) CH3 CH C CH2 CH3

O
(VI) CH3 CH CH2 C CH3
CH3
Only (III) form diastereomers on addition reaction so, desired ketones as per addition reaction is 5.
90. Answer (4)
CHO
CO, HCl
(Gatterman Koch Reaction)
Anhyd AlCl3/CuCl
OH
CHCl2 CH CHO
H2O OH
100°C –H2O
COCl CHO
H2
(Rosenmund Reduction)
Pd–BaSO4
COOMe CHO
DIBAL–H
Toluene, –78°C H2O
91. Answer (495.00)
O COOH CONH 2 NH2 NH2

Br Br
NaOBr NH 3 Br 2 KOH
+
H 3O D D
Acetophenone A B C
10 moles (60%) (50%) (50%) Br
D
(100%)
60 50 50
Yield of D in moles = 10     1.5 moles
100 100 100
Amount of D = 1.5 × 330 = 495.00
92. Answer (2)
H3N CH2 CH2 CH2 CH2 O

CH C Basic site (Carboxylate ion will
H2N O also behave as proton acceptor)
Basic site
93. Answer (6)
A decapeptide will have (9) peptide linkage
Mass of hydrolyzed product is (796 + 162) gm/mole
0.47  958
Number of glycine molecule = 6
75
94. Answer (4)
When any group in R 1 and R 2 is basic group then amino acid is positively charged at pH = 7.0.
So, answers are peptide IV, VI, VIII and IX.
95. Answer (8)
Given
CHO
CH2
CHOH
CHOH
CHOH has D configuration
CH2OH
CH2OH
O
HO H OH C* are chiral carbon atoms. Hence total stereoisomers are 8.

* *
* H
HO H
96. Answer (4)
According to question C – Terminal must be alanine and N – Terminal do have chiral carbon means its should
not be glycine so possible sequence is
Val Phe Gly Ala
Val Gly Phe Ala
Phe Val Gly Ala
Phe Gly Val Ala
So, answer is (4).
97. Answer (1)
On hydrolysis only glycine is formed as natural amino acid.
98. Answer (6)
Structure of melamine is
H2N N NH2
N N
NH2
So, melamine has six lone pair of electrons.


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Unit 2

 Bond order = 1 and diamagnetic.

17. Answer (D)

Area covered by particle

 R A   0.414  250  103.50 104 pm

24. Answer (A)

wt. of solute 1000

273 (K) – Tf = 3 (K)

H2 (g)  2H  2e –

H2 (g)  M4   2H  M2

34. Answer (D)

37. Answer (D)

38. Answer (B)

So, order of reaction is 3.

39. Answer (C)

40. Answer (B)

42. Answer (B)

43. Answer (D)

Ba(N3)2  Ba(s) + 3N2 

46. Answer (A)

P4  8SOCl2  4PCl3  4SO2  2S2Cl2

48. Answer (B)

The increasing order of atomic radii is

Ga < Al < In < Tl

49. Answer (D)

Haematite Fe2O3 Fe+3

Magnetite Fe3O4 Fe+2 and Fe+3

50. Answer (B)

2Na[Ag1(CN)2 ]  Zn  Na2 [Zn(CN)4 ]  2Ag0 

51. Answer (A)

52. Answer (C)

In CuF2, copper is in +2 oxidation state

 coloured. In other options copper is in +1 oxidation state therefore colourless.

53. Answer (A)

Complementary colour of blue is (Orange-red)

54. Answer (B)

Iron become passive with conc. HNO3.

Copper liberate NO2 with HNO3

55. Answer (B)

[Ni(CO)4] --------- sp3 hybridization

[Ni(CN)4]–2 --------- dsp2 hybridization

56. Answer (A)

two unpaired electrons sp3

= 8 B.M. = 2.83 B.M.

P  [FeF6 ]3 ; Fe3 :

The correct order of spin only magnetic moment is Q < R < P

67. Answer (A)

70. Answer (D)

> > >

72. Answer (B)

73. Answer (D)

HO H CH3 :OH H CH3

74. Answer (B)

75. Answer (D)

76. Answer (C)

OCH3 HNO3/H2SO4 OCH3

H3C H3C NO2

77. Answer (B)

Ozonolysis produces CH3CHO and CH3–CH(CHO)2

79. Answer (B)

80. Answer (B)

Relative reactivities 1,00,000 : 200 : 79 : 0.02