SA 15 16 XII XII Chemistry Unit-1 Section-A

Physical Chemistry
UNIT
Section - A : Straight Objective Type

1.
Answer (1)
Number of moles of 200 ml of 3 M AgNO3 = 200 3 103
= 0.6
Number of moles of 300 ml of 2M AgNO3 = 300 103 2
= 0.6
Total number of Ag + ions = 0.6 + 0.6

= 1.2 moles
Moles of Cl released by 200 ml of 10 M

= 200 10 103
= 2 moles
1.2 moles of Ag+ will precipitate 1.2 moles of Cl
The number of moles of NaCl left unprecipitated = 2 1.2 = 0.8 moles
Amount of NaCl left unprecipitated = 0.8 (23 + 35.5)g = 46.8 g
2.
Answer (4)
1 ml H2O is equal to 1 g of H2O because density of water is 1 g/ml.
3.
Answer (4)
The change in oxidation number of Cr is +3 to +6. Total e lost are 6. Hence, equivalent weight of
M
.
Cr2(SO4)3 =
6
4.
Answer (3)
3% solution of H2O2 means
100 ml H2O2 solution 3g H2O2
1000 ml H2O2 solution 30g H2O2
2H2O 2 2H2O O 2
234
22.4 L
at NTP
68 g of H2O2 liberates 22.4 L of O2

30 g of H2O2 liberates 9.88 L of O2
30 g of H2O2 = 1000 ml of H2O2 = 9.88 103 ml of O2
1 ml of H2O2 = 9.88 ml of O2
volume strength = 9.88
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2
5.
Physical Chemistry
Success Achiever (Solutions)
Answer (3)
MgCO3 + 2 HCl MgCl2 + CO2 + H2O
MgCl2 + HCl no reaction
Now, 1 mole of MgCO3 1 mole of CO2
1 mole of CO2 1 mole of MgCO3
4
4
moles of CO2 =
moles of MgCO3
44
44
= 0.09
= 0.09 84 g of MgCO3
= 7.64 g
% of MgCO3 in the mixture = 38.2%

% of MgCl2 in the mixture = 61.8%
6.
Answer (3)
x
1000
mol. wt. of KMnO 4
56
60
N
5 .6
5
158
56
60
5
5
.6
x
1000
= 18.96 g
% purity of KMnO4 =
7.
18.96
100 63.2%
30
Answer (3)
100 g of solution contain 49 g of H2SO4
49
mol. weight of H2SO 4
M
100
weight of solution
density
100 NH2SO4 50 12
NH2SO4 6N
6N H2SO4 = 3 M H2SO4
49
98
3
1000
100
d
49
10 d
98
d = 0.6 g/ml
8.
Answer (1)
Number of moles of KClO4 formed =
0.395
138.5
(molar mass of KClO4 = 138.5)
= 2.85 103
Physical Chemistry
Number of moles of KClO3 decomposed to give 2.85 103 moles of KClO4

4
2.85 10 3
3
= 3.8026 103 moles of KClO3
= 3.8026 103 122.5 g KClO3 = 0.466 g of KClO3
Amount of KClO3 used in 1st reaction = 1.034 g of KClO3

= 8.44 103 moles of KClO3
Number of moles of O2 formed by 8.44 103 moles of KClO3

3
8.44 10 3
2
= 0.01266
Volume occupied by 0.01266 moles of O2 = 0.01266 22.4 L = 283.6 ml

9.
Answer (2)
5 FeC2O4 + 3 MnO4 + 24 H+ 5 Fe3+ + 10 CO2 + 3 Mn2+ + 12 H2O
Molecular weight of FeC2O4 = 144 g
Number of moles in 1.44 g of FeC2O4 =
1
1.44 = 0.01 mole
144
From the above balanced equation

5 moles of FeC2O4 are oxidised by 3 moles of KMnO4
3
0.01 = 0.006 moles
5
0.01 mole of FeC2O4 are oxidised by
Volume of 0.01 M KMnO4 solution required

1000
0.006
0.01
= 600 ml
10. Answer (1)

Milli equivalent of NaOH = x
Milli equivalent of Na2CO3 = y
x
y
50 0.2
2
2x + y = 10 2 = 20
x + y = 72 0.2
x + y = 14.4
x = 20 14.4
= 5.6
Number of milli equivalent of NaOH in 25 ml = 5.6
Weight of NaOH in the solution =
5.6 40
= 0.224 g
1000
y = 14.4 5.6 = 8.8

Number of milli equivalent of Na2CO3 in 25 ml of solution = 8.8
Weight of Na2CO3 of solution =
WNaOH
0.224
0.48
WNa2CO3 0.4664
8.8 53
0.4664 g
1000
Physical Chemistry
11. Answer (1)

KMnO
4
Fe2
Fe3
12. Answer (2)
No. of neutron in 1H2 = 1

2
No. of mole of 1H2
4
1
4
13. Answer (4)

1
1
1
th wt. of C-12 atom =
th wt. of O-16 atom =
th wt. of C-14 atom
12
16
14
u=
14. Answer (3)

No. of moles of solute does not change on dilution.
15. Answer (4)
Equal volume of gas must have same mole and entities.
16. Answer (1)
Percentage by weight also can be calculated by the empirical formula.
17. Answer (1)
No. of atom = 5
1
5
NA NA
4
4
18. Answer (1)

m
18a.
x A 1000
xB
18
Answer (4)
(AIEEE 2011)
No. of moles of compound

Total no. of mole of solution
For 1 kg solvent
5.2
5.2
0.086
55.5 5.2 60.7
19. Answer (2)
No. of moles of Cl
Total volume in litre
423 9
1.8
5
5
20. Answer (4)
1000 0.8 400
46
23
20a.
Answer (3)
(AIEEE 2012)
21. Answer (1)

As per Avogadros Law v n (At constant P & T)
Physical Chemistry
22. Answer (2)

23. Answer (2)
Sum of positive and negative charges should be equal.
3(number of atoms of A) + 6 NB = 2 NC
NA = 2
NB = 3
NC = 12
Hence A2(BC4)3
24. Answer (2)
100 ml of 1 M Ca(OH)2 = 100 ml of 2 N Ca(OH)2
10 ml of 20 N H2SO4 = 100 ml of 2 N H2SO4
100 ml of 1 M Ca(OH)2 will neutralize 10 ml of 20 N H2SO4 completely.
Thus, the resulting solution will be neutral.

25. Answer (2)
1
( V.D)B and molecular mass of B = x = 2 V.D. of B
6
Molecular mass of A = 2 V.D. of A
Given V.D. of A =
= 2
1
VB
6
= 2 VB
=
1
6
x
6
26. Answer (3)

Molecular mass of CH3OH = 12 + 4 + 16 = 32
% of C in CH3OH =
12
100 37.5%
32
% of C in CO2 =
12
100 27.27%
44
% of C in CH3CH
CHCOOH =
% of C in COOHCOOH =
48
100 55.8%
86
24
26.6%
90
(3) is the correct answer.
27. Answer (1)

100 g of solution contain 40 g solute
1000 g of solution contain 400 g solute
Amount of solute left in solution after precipitation = 400 200 = 200 g
Weight of the solution after precipitation = 1000 200 = 800 g
% concentration of new solution =
200
100 25%
800
Physical Chemistry
28. Answer (2)

12 g of N in 100 g of compound
14 g of N in
100
14 g of compound
12
= 116.67 g
29. Answer (1)
AgNO3 NaCl AgCl NaNO3

(170 )
( 58.5 )
68 g of AgNO3 = 0.4 moles

11.7 of NaCl = 0.2 moles
NaCl is limiting reagent
Hence 0.2 moles of AgCl is formed.

30. Answer (4)
21
84 1000 1.25 M
Molarity of the solution =
200
1.25 25 = x 1250
x = 0.025 M
31. Answer (1)
100 0.5 + 200
x
1
2 N = 600 x
4
N
4
= 0.25
20 ml of 0.25 N solution (acidic) 25 ml of 0.2 N acidic solution
10 ml of 0.2 N NaOH will neutralize 10 ml of 0.2 N acidic solution
15 ml of solution will be left unneutralized
Nature of solution = acidic.
32. Answer (4)
The mole fraction of methanol =
50
32
50 50
32 46
= 0.59
33. Answer (1)

34. Answer (4)
35. Answer (2)
MgCO3
MgO CO 2
84 g
Weight of MgO =
40
40
42 20 g
84
Physical Chemistry
36. Answer (4)

A=H
B=N
AB3 = HN3 acid

A3B = NH3 base
37. Answer (4)
MH2PO4 = M+ and H2PO4 univalent metal
Metal chloride = MCl
38. Answer (1)

The number of atoms of A =
81.6
2.2988
35.5
The number of atoms of B =
18.4
1.15
16
Mole formula = A2.2988 B1.15

= A1.99 B1
= A2B
39. Answer (3)

Amount of MgCl2 in the sample = 50% of 25 g
= 12.5 g
Molecular mass of MgCl2 = 24 + 35.5 2
= 24 + 71
= 95 g
95 g of MgCl2 = 24 g of Mg
12.5 g of MgCl2 = 3.157 g of Mg
Amount of MgSO4 in sample = 50% of 25 = 12.5 g
120 g of MgSO4 24 g of Mg
12.5 g of MgSO4 =
24
12.5 = 2.5 g of Mg
120
Total Mg in sample = 2.5 + 3.157 = 5.657 g

% of Mg in sample =
5.657
100 22.63%
25
40. Answer (2)

The volume of NaOH neutralized by 30 ml of 0.1 N HCl
40 0.1 = 0.2 x
x = 20 ml
The amount of NaOH left unneutralized by 0.1 N HCl
= 120 20
= 100 ml
100 0.2 = 40 NH2SO4
NH2SO 4 0.5 N
Molarity of H2SO4 =
0 .5
0.25 M
2
Physical Chemistry
41. Answer (2)

% composition of CH
: C
12
100 92%
13
% composition of CH2O
: C
12
2
100 40% H
100 6.7%
12 2 16
30
% composition of C3H6O
: C
36
100 62%
36 6 16
% composition of C3H4O2 : C
36
100 50%
36 4 32
42. Answer (1)

0.26% zinc means 100 g of compound contains 0.26 g of zinc
65.38 g of Zn is present in
100
65.38
0.26
= 25146
= 2.5146 104 g
43. Answer (4)
The molecular mass of M(OH)2 = 171
x + 2(16 + 1) = 171
x = 171 34
= 137 g
Equivalent mass of metal is =
137
68.5 g
2
44. Answer (4)

45. Answer (1)
6 M = 12 N H2SO4
12 1 = 15 NH2SO4
NH2SO 4
12
15
= 0.8
MH2SO4 0.4 M
46. Answer (3)

47. Answer (1)
V.D. of gas = 45 g
Molecular mass of gas = 90 g
90 g of a gas occupies 22.4 L
22.5 g of a gas occupies
22.4
22.5 = 5.6 L
90
Physical Chemistry
48. Answer (4)

0.01 M K2Cr2O7 0.06 N K2Cr2O7
0.06 50 =
W
1000
152
= 0.456 g
% purity of sample =
0.456
38%
1 .2
49. Answer (1)

The weight loss is due to the evolution of O2 gas
2 KClO3 2 KCl + 3O2
3 32 g O2 is obtained by 2 122.5 g KClO3
0.384 g O2 is obtained by
2 122 .5
0.384
3 32
= 0.98 g KClO3
% of KClO3 decomposed =
0.98
100
9.8
= 10%
50. Answer (3)
Only Na2CO3 reacts with HCl.
M.e. of Na2CO3 = M.e. of HCl
W
1
1000 100
53
10
W = 0.53 g Na2CO3
So, weight of NaCl = 1 0.53 = 0.47 g
% of NaCl =
0.47
100 47%
1
51. Answer (1)

(109% of oleum means 109 g of H2SO4 formed when 100 g of oleum is diluted hence amount of water added
= 109 100 g = 9 g with water)
SO 3 H2O H2SO 4
80 g
18 g
From above equation,

18 g of water combines with SO3 = 80 g
9 g of water combines with SO3 =
80
9 40
18
% of SO3 = 40%
52. Answer (4)

5.6 L of gas weighs 4.5 g
112 L of gas weighs
4.5
112
5 .6
= 90 g
10
Physical Chemistry
53. Answer (1)
0.5
12.25
1000
98
x
500
(x is the basicity)
x=2
Acid has been neutralized to HPO42.
54. Answer (4)

The balanced chemical equation is
I2 10 HNO3
1272
1063 g
2 HIO 3 10 NO 2 4 H2O
254 g = 630 g
Thus, HNO3 required for 5 g iodine
=
630
5 12.4 g
254
55. Answer (4)

5
AsO34 AsO33 nf 2 ; I I2 nf 1
1.5 1022
1
mole electrons
6.02 1023 40
1
I2
2
1
mol
80
e
1
mol
40
wt. of iodine = w
1
80
254
3.2 g
56. Answer (1)
2FeS2
x mol
11
O2 Fe2 O3 4 SO2
2
2x mol
11 x
mol
4
0.21 mol O2 = 1 mol air
11x
1
11x
mol O2
13.1 x
4
0.21
4
so, mol of air taken = 1.6 13.1 x = 21 x

mol of N2 present = 0.79 21 x = 16.6 x
mol of air left = 21 x 2.75 x + 2x = 20.25 x
%N2
16.6 x
100 81.97%
20.25 x
Physical Chemistry
11
57. Answer (1)

Aufbau principle violated because ns should be preferentially full filled and only after that np should be filled.
In np the two electrons with same spin will have all the four quantum numbers same, hence 1 is incorrect.
58. Answer (3)
Possible exchanges in 1 = 2
59. Answer (2)
The number of revolution = 6.55 1015
= 6.55 1015
z2
n3
12
33
= 2.43 1014
60. Answer (4)

t n3
t1
27
33
= 3 =
t2
64
4
61. Answer (2)
Cr(24) = 1s2 2s2 2p6 3s2 3p6 4s1 3d5
Number of unpaired electrons = 6.
62. Answer (2)
There are 3 complete waves in figure, means it produces 3 waves.
63. Answer (2)
2x 0
1 0
(KE)1
=
=
3 x 0
2 0
(KE)2
y
2x 0
=
4y
3 x 0
8x 40 = 3x 0
5x = 30
0 =
5x
3
64. Answer (3)

Increase in photocurrent implies higher number of emitted electrons per second. Increase in frequency increases
the kinetic energy of emitted electrons only.
65. Answer (4)
We know that
2rn = n
2rn
2.n2a0
=
n
n
= 2na0 = 8a0
(... n = 4)
66. Answer (2)

Number of subshell = 2l + 1
... Each subshell contain 2 electrons.
Hence total number of electrons = 2 (2l + 1)
12
Physical Chemistry
67. Answer (4)

h
4
h
0 . p
4
h
p
4 . 0
p
x . p
68. Answer (1)

Number of peaks = n l
69. Answer (1)
Exchange energy = nC2 .K =
=
n
2 n2
n (n 1)
K,
2
where n = number of unpaired electrons having similar spin
Cu(29) = 1s2 2s2 2p6 3s2 3p6 4s2 3d9 (expected)

= 1s2 2s2 2p6 3s2 3p6 4s1 3d10 (Real)
Expected exchanges for 4s2 3d9 = 16
Real exchanges for 4s1 3d10 = 20
70. Answer (1)
The difference between energies of adjacent energy levels decreases as we move away from nucleus. Thus
in H-atoms.
(E2 E1) > (E3 E2) > (E4 E3) ..................
71. Answer (2)
For d orbital l = 2
orbital angular momentum =
l (l 1)
h
=
2
2 (2 1)
h
=
2
h
2
72. Answer (4)

4s
3d
s = 6
1
6
=
=3
2
2
Spin multiplicity = 2s + 1 = 2 3 + 1 = 7
73. Answer (3)
Last electron is filled in 3d orbital.
74. Answer (3)
Energy of unfilled orbital is decided by (n+l) rule
75. Answer (3)
e is excited to 3rd shell.
76. Answer (4)
Work function of metal depend on ionisation energy.
77. Answer (3)
2 4mp 2 ev
2 mp .ev
2 2
1
Physical Chemistry
13
78. Answer (4)

Spin quantum number have no relation with probability.
79. Answer (3)
All orbital in s orbital have zero orbital angular momentum.
80. Answer (2)
In representation of , sign of wave function are shown.
81. Answer (3)
n
sin4
2
82. Answer (1)

I.E.
e4 Z2
802h2n2
where is reduced mass.

83. Answer (4)
Cu, Pf, Pd have abnormal E.C. in which Aufbau principle is voilated.
84. Answer (1)
Cr have 3d5 electronic configuration.
85. Answer (3)
Energy in H atom
RHhC
R hC
= H
9
n2
n=3
3s
3p
3d
1
3
5
Total degeneracy = 1 + 3 + 5 = 9
86. Answer (3)
dxy orbital lies in xy plane.
87. Answer (1)
s orbital does not have angular nodes, only p and d orbitals have angular nodes.
88. Answer (3)
Number of nodal planes l
for 4d, n = 4, l = 2
Number of nodal planes = 2
89. Answer (3)
Spectrum depends on electronic environment of an atom.
14
Physical Chemistry
90. Answer (3)

Visible region belongs to Balmer series. Since the electron transition is from 5th energy level to 3rd energy level.
So no line obtained in Balmer series.
91. Answer (2)
1s2 2s2 2p6 3s2 3p6
l = 0 for s subshell hence total number of electrons having l = 0 is 6.
92. Answer (2)
After filling np level electron enters into (n + 1) s level.
93. Answer (1)
Since 1s is lowest energy level hence it can absorb photon only but cannot emit it.
94. Answer (2)
1
max
max =
1
1
1 1
R34
= RZ2 2
= 3R
2 = R (2)2 =
1 4
n
n
4
2
1
1
3R
95. Answer (2)

h
mv
v=
Hence, =
h
m
2 =
h
m
h
m
96. Answer (3)

We know that,
mvr =
v=
nh
2
nh
2mr
frequency (number of revolutions per sec)

=
velocity
circumference
v
2 r
nh
2
mr
=
2r
=
nh
4 2mr 2
s1
Physical Chemistry
15
97. Answer (4)
2p contains 6 electrons out of which only 3 electrons have spin
1
.
2
98. Answer (4)

l varies from 0 to n 1 and number of electrons in any energy level = 2 (2l + 1).
99. Answer (2)
Number of orbitals = n2 = 52 = 25
100. Answer (4)
For n = 3, l 2.
Thus m cannot have value of 3.
101. Answer (2)
Sc (21) = 1s2 2s2 2p6 3s2 3p6 4s2 3d1
Outermost electron lies in 4s.
Therefore
n = 4, l = 0, m = 0, s =
1
2
101a. Answer (1)
[JEE (Main)-2014]
37 1s22s22p63s23p63d104s24p65s1
So last electron enters 5s orbital
Hence n = 5, l = 0, ml = 0, ms
1
2
102. Answer (1)

x.p
h
4
x.m v
h
4
v.mv
h
4
(v)2 =
v =
h
4m
h
4m
p = mv = m
h
=
4m
mh
1 mh
=
4
2
16
Physical Chemistry
103. Answer (1)
m1 m2
m2 m
m1 m2 2m 2
Rydberg's constant
RH
2
104. Answer (3)
rn 0.53
n2
105. Answer (1)

L 1
106. Answer (3)
Fact
107. Answer (2)
Follow Schrodinger's wave equation.
108. Answer (2)
From the data
109. Answer (4)
Ionic radius of an element depend on the charge reside on that ion, effective nuclear charge and group to which
it belong.
110. Answer (3)
If IE2 is 7 to 14 times of IE1, then that element will belong with Ist group.
111. Answer (2)
IInd successive ionisation energy is always greater than Ist ionisation energy and difference between these two
differ for element to element.
112. Answer (1)
Ga : 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p1
Ga belong with 13th group, 4th period and p block.
113. Answer (1)
Electronegativity =
Ionisation energy Electron affinity

2
114. Answer (1)

van der Waal radius is larger than metallic radius because in metallic radius, atoms are closer to each other
because metallic bond is stronger than van der Waal bond.
115. Answer (3)
In process of ionisation, energy have to be supplied to remove the outermost electron.
116. Answer (4)
1.
Electron affinity of noble gases is negative (means endothermic).
2.
Addition of e to anion is always endothermic.
3.
The process of ionisation is endothermic.
117. Answer (4)

Fact
118. Answer (3)
IE1 of Be is more than I.E.1 of B.
119. Answer (4)
I.E. E.A.
E.N.
2
Physical Chemistry
17
120. Answer (1)

Shielding power is s > p > d > f
121. Answer (3)
Cu belong with XI group.
122. Answer (1)
Fact
123. Answer (3)
Element
Electronegativity
4.0
3.5
Cl
3.2
3.0
124. Answer (3)

Charge per unit area is same
125. Answer (2)
Mosley equation is as
k(Z b)
where b is screening constant.
126. Answer (3)
Addition of e in N is an endothermic process.
127. Answer (1)
Fact
128. Answer (2)
129. Answer (2)
Gallium have smaller size than aluminium.
130. Answer (2)
For isoelectronic species, size
1
.
Atomic number
130a. Answer (2)

130b. Answer (3)
Radius of N3, O2 and F follow order
(AIEEE 2012)
[JEE (Main)-2015]
N3 > O2 > F
As per inequality only option (3) is correct
that is 1.71 , 1.40 and 1
131. Answer (3)
Energy have to be absorbed to increase the energy of the E.C. and decrease the stability.
132. Answer (2)
With respect to oxygen valency along period generally increase.
Al2O3, SiO2, P4O10, SO3, Cl2O7
133. Answer (4)
Polar bond is present between two atoms which have different electronegativity. If electronegativity is different,
then I.E. and E.A. should be different.
18
Physical Chemistry
134. Answer (4)

Electronegativity of an atom depend on the electronic configuration, hybridisation and effective nuclear force.
135. Answer (3)
Electron affinity of silicon is higher than carbon because of small size and high electron density of carbon.
136. Answer (2)
Na + e Na it is exothermic process while all other are endothermic process.
137. Answer (1)
107 Unnilseptium.
138. Answer (2)
Technetium.
139. Answer (1)
15th group element = P
16th group element = O
On basis of valency common formula P4O10.
140. Answer (3)
Gallium have smaller size than aluminium this is called scandide contraction.
141. Answer (2)
O > N > B > Be.
142. Answer (2)
Take example of Al and O whose formula is Al2O3.
143. Answer (4)
Mg < C (graphite) < B < Al
144. Answer (4)
He is inert and has weakest van der Waal's forces.
145. Answer (3)
146. Answer (3)
All are linear except BH2 (V-shape).
146a. Answer (2)
(AIEEE 2012)
147. Answer (2)
Bond order of C O is 3.5.

148. Answer (4)
Bond order =
5
= 1.67,
3
Charge per atom =
1
= 0.33
3
149. Answer (4)

O 2 O 2 O 2 O 22
2 .5
1 .5
149a. Answer (4)
Physical Chemistry
19
(AIEEE 2009)
Higher is the bond order, shorter is the bond length.

Bond order of O22 is 3.0.
150. Answer (3)
sp3 hybridised carbon atom contains 75% p-character.
151. Answer (4)
N N, N O+, C = C.
152. Answer (1)
In KO2, O 2 contains one unpaired electron.
153. Answer (1)
O
PCl
Cl Cl
154. Answer (2)
H
5444'
H
H
H
155. Answer (3)
Due to intramolecular hydrogen bonding.

156. Answer (2)
Its dipole moment is 3 D.
157. Answer (2)
Due to see-saw shape.
158. Answer (3)
14 carbon atoms are sp2 hybridised and 4 carbon atoms are sp3.
159. Answer (2)
..
..
160. Answer (2)

obs
100
Percentage ionic character =
th
161. Answer (3)

Fact.
20
Physical Chemistry
162. Answer (3)
O 14 lone pairs (12 on fluorine and 2 on oxygen).
F
163. Answer (2)
Due to pentagonal bipyramidal shape.
163a. Answer (1)
(AIEEE 2011)
Hybridisation of iodine is sp 3d 3
So, structure is pentagonal bipyramid.
164. Answer (1)
CH=CH2
165. Answer (1)

Smaller halogen atom more possibility of back bonding.
166. Answer (1)
Cl
F
Cl
167. Answer (2)
Fact.
168. Answer (4 )
Larger anion, easier polarisation.
169. Answer (3)
Smaller ionic radius, larger hydration radius.
170. Answer (1)
Larger ionic radius, more ionic mobility (drift velocity per unit electric field).
171. Answer (2)
ClF3 is T-shaped and other are pyramidal.
172. Answer (2)
Cl
F
P
Cl
Cl
>0
Cl
F
F
P
Cl
Cl
F
=0
173. Answer (3)

Low heat of sublimation of metal, lower bond energy of non metal element, high lattice energy and high electron
affinity of non metal favour ionic bond formation.
174. Answer (3)
Fact.
175. Answer (2)
All peroxides are polar.
Physical Chemistry
21
176. Answer (2)

O 22 contains zero unpaired electrons.
177. Answer (3)
O
4- bonds O=PO
O
O
||
P
O
O
P=O
O
P
||
O
178. Answer (4)

1
Polarising power of cation
Size of cation
179. Answer (4)
Peroxide are diamagnetic
179a. Answer (1, 2)
[JEE (Main)-2013]
The electronic configuration of the given diatomic molecules is

2
2
2
2
2
2
C2 : 1s *1s 2s *2s 2px 2py
2
2
2
2
2
2
2
N2 : 1s *1s 2s * 2s 2p 2p 2pz
x
O2 :
2
2
1s
*1s
2
2
2s
* 2s
22pz 22p
S2 :
2
2
1s
*1s
2
22s *2s
2
2p
2
z 2p
2
2p
*12p *12py
y
2
2p
*22p
2
*2p
y
2
2
2
*22pz 3s
*3s
3p
2 2 *13px *13py
z 3p x 3p y
So, C2 and N2 are diamagnetic.

180. Answer (3)
Cl
B
Cl
Cl
181. Answer (1)
Due to more negative charge on F
181a. Answer (4)
[JEE (Main)-2015]
H-bond is one of the dipole-dipole interaction and dependent on inverse cube of distance between the
molecules.
182. Answer (1)
In Ar, London forces exist
183. Answer (1)
When Z 7, sp mixing take place
184. Answer (3)
PCl5 exist as PCl4 PCl6 [PCl4] [PCl6]
185. Answer (2)
BCl3 H2O H3BO3 3HCl
186. Answer (3)
In valence cell of S is 10e are present.
22
Physical Chemistry
187. Answer (1)

Compound
OF2
H2O
CH4
BCl3
Bond angle
102
104.5
109.25
120
188. Answer (1)

Fact
189. Answer (2)
190. Answer (2)
O2[AsF6] O2 + [AsF6]
( 2.5 )
191. Answer (2)

It is sp hybridised.
192. Answer (2)
NO contains 15 electrons.
193. Answer (2)
Both bond moments lie in same direction.
194. Answer (4)
In pyrolle lone pair of N is resonance stabilised.
195. Answer (4)
It is sp3 hybridised and tetrahedral.
195a. Answer (2)
(AIEEE 2012)
196. Answer (1)
N
197. Answer (1)
Fact.
198. Answer (1)
LiH contains 76% (approx.) ionic character.
199. Answer (2)
In aqueous medium movement of ion becomes easier.
200. Answer (4)
Factual
201. Answer (1)
In NO2 , there are no l.p b.p repulsions and bond angle of O N O is 180.
202. Answer (3)
In (3) there is maximum charge separation.
203. Answer (3)
3
NH4 N2 H4 NH2 OH N2O

204. Answer (4)
(1), (2) and (3) are unstable.
Physical Chemistry
23
205. Answer (3)

PV = nRT
He 1 2 = n1 R 300
(i)
H2
(ii)
1 2 = n2 R 300
Divide equation (i) by (ii)
n1
n2
n1 = n2
In vessel B, number of atoms will be 2 times that present in vessel A. Because H2 is diatomic while He is
monoatomic.
206. Answer (3)
At constant pressure (parallel to V axis)
V1 > V 2 > V 3
Since V T hence T1 > T2 > T3.
207. Answer (2)
V
= constant
T
Charles law.
208. Answer (1)
Molecular weight of C2H6 = 30 gm
Molecular weight of H2 = 2 gm
Since H2 is lighter hence it diffuses faster into balloon containing C2H6 hence balloon will be enlarged.
209. Answer (3)
PV =
W
RT
M
0.821
200
0 .5
0.0821 400
1000
M
M = 100
Molecular weight of C2F4 = 2 12 + 4 19 = 100.
210. Answer (3)
1
V
(3) is not correct representation.
211. Answer (3)

b = 4Vm
where Vm is volume of a gas molecule.
212. Answer (1)
Vrms
1 2 3 4
4
30
7 .5 .
4
24
Physical Chemistry
213. Answer (1)
P a ( V b) RT
2
V
If a and b are small they can be neglected

PV = RT
Which is equation of ideal gas.
213a. Answer (2)
(AIEEE 2011)
Both a and b for Cl is more than C2H6.

214. Answer (2)
If thermal energy >> molecular attraction then molecules will be largely separated and will be present in
gaseous state.
215. Answer (1)
Force between two layers of liquid known as viscous force.
216. Answer (1)
At low temperature and high pressure molecules of gas come closer and hence it favour liquefaction of gas.
217. Answer (3)
Ti
2a
Rb
TB
a
Rb
TC
8a
27Rb
Ti
Ti
TB
TC
2
54
6.75
8
8
27
TC
8
0.296
TB 27
TB
3.375
TC
TC
Hence T is least.
B
218. Answer (2)

At high temperature gas approaches ideal behaviour and curve starts becoming flat.
219. Answer (3)
Gas cannot be liquefied at a temperature higher than critical temperature and a pressure lower than critical
pressure.
Physical Chemistry
25
220. Answer (1)

3O2 2O3
Let x lit oxygen converted to ozone.
Volume of ozone produced =
2
x
3
Volume of oxygen remaining = 1 x

1 x
1
2
x 0.8 litre
3
x
0 .8
3
x
1 0 . 8 0 .2
3
x = 0.6 litre
Volume of ozone =
2
0.6 0.4 litre
3
Volume of oxygen remaining = 1 x = 1 0.6 = 0.4 litre.

Since volume are equal hence mole fraction of both will be 0.5.
221. Answer (3)
r=
v 100
10
t
10
(1)
x 100
2 .5
t
40
(2)
x 25
2 .5
t 10
(3)
x 100
10
t
10
(4)
x 5
2 .5
t 2
In option (3) rate of diffusion of O2 is same as that of rate of diffusion of H2 which is never possible because
H2 is lighter and O2 is heavier hence rate or diffusion of H2 will be faster and that of O2 will be slower.
222. Answer (3)
Collision frequency (pressure)2
Hence at 5 atm, collision frequency will be 25z.
223. Answer (2)
Tc
8a
27Rb
Vc = 3b and Pc
a
27b
26
Physical Chemistry
224. Answer (4)

At high temperature, a and b both negligible hence PV = RT.
224a. Answer (2)
[JEE (Main)-2014]
Compressibility factor (Z)
PV
RT
(For one mole of real gas)

van der Waal equation
(P
a
)(V b) RT
V2
At low pressure
V b V
P 2 V RT
V
PV
a
RT
V
PV RT
a
V
PV
a
1
RT
VRT
So, Z 1
a
VRT
225. Answer (3)

At critical temperature density of liquid and gas phase become equal hence meniscus will disappear.
226. Answer (2)
rA
rB
vA / t
vB / t
MA
MA
MA
MB
MB
MB
MA
MB
1
4
227. Answer (1)

Pwet gas = Pdry gas + aqueous tension
Pdry gas = Pwet gas aqueous tension.
Physical Chemistry
27
228. Answer (3)

PVm = RT
RT
P
Vm will be maximum at higher temperature and lower pressure.
Vm =
229. Answer (2)

At Boyles temperature, a real gas behave like ideal.
230. Answer (4)
Vm, real > V m, ideal Z > 1 repulsive forces are dominant this is only possible when gas is highly
compressed, for this experimental temperature should be more than Tc.
231. Answer (1)
Z < 1 Intermolecular force of attraction is dominant, so liquefaction is possible.
232. Answer (1)
a is large when force of attraction is large.
233. Answer (3)
Ti
2a
Rb
234. Answer (4)

When temperature Texp < Ti, cooling occurs.
235. Answer (3)
When Texp < Tc, repulsive forces do not develop.
236. Answer (3)
Ti
2a 2 27
304.2 2053.3 K 1780.3C

Rb
8
237. Answer (2)
Tc
8
33 9.8 K 263.2C
27
So, for liquefaction temperature must be maintained below 264C.

238. Answer (1)
n
Pressure correction
v
and P n, so pressure correction increases with pressure.

239. Answer (4)
PV = K
log P + log V = log K
log P = log K log V
(y = c + mx)
240. Answer (2)

On comparing, m = 1 = tan
= tan1(1) = 135
28
Physical Chemistry
241. Answer (4)
P1V1
P V
2 2
T1
T2
242. Answer (1)
PV = constant
1
V
At sea level pressure is more hence volume less and density more.
d
243. Answer (4)

Postulate of kinetic theory of gases.
244. Answer (2)
KE =
3
KT
2
T = constant
hence KE = constant
245. Answer (3)
Postulate of kinetic theory of gases.
246. Answer (2)
Due to viscous force (frictional force) liquid comes to rest.
247. Answer (1)
At constant pressure the volume of a given sample of an ideal gas varies with temperature as follows
t
Vt V0 1
273
248. Answer (2)
V = kT
log V = log T + log k
y = mx + c
m=1
c = log k
graph (2) is correct.
249. Answer (1)

Reciprocal of viscosity is called fluidity.
250. Answer (2)
The film of a soap bubble has small thickness and there is air both inside and outside the film.
251. Answer (1)
PV P1V
n
RT1 RT1
V
P1
2
RT2
2PT2
P P1 P1
or P1
T1 T1 2T2
2T2 T1
252. Answer (3)

P1V1 = P2V2
g(h1 + 10) V = g 10 8V.
[ P = gh]
h1 = 70 m
Physical Chemistry
29
253. Answer (1)

H2 +
2x + y = 50
15 mL O2 is in excess
C 2H2 +
x
1
O H2O
2 2
5
O 2CO2 + H2O
2 2
2x
CO
y
1
O2 CO2
2
y
254. Answer (4)

If during neutralisation acid/base or both are weak than it is possible.
255. Answer (3)
For non spontaneity
G > 0
H TS > 0
If H = +ve and S = ve
Then, G = H T (S)
G = + H + TS
G = +ve
G > 0
256. Answer (3)
When rod cools, energy is given to surrounding hence entropy of universe increase and entropy of rod
decreases.
257. Answer (3)
E
For Ideal gas, = 0.
P T
258. Answer (4)
When T 0 Randomness is zero S = 0.

259. Answer (2)
H = (Bond energy of Reactants) (Bond energy of product)
= (BEHH + BEO = O) (2 BEOH + BEOO)
= (x + y) (2w + z)
= x + y 2w z
260. Answer (3)
Density is an intensive property as it does not depend upon amount of substance.
261. Answer (3)
ng = (1 + 3) 2 = 4 2
ng = 2
ng > 0
H > E
262. Answer (2)

C2H5SH +
9
O 2 2CO 2 3H2 O SO 2
2
( g)
(l)
( g)
( g)
At 298K, H2O will be in liquid state and CO2 and SO2 will be in gaseous state.
30
Physical Chemistry
263. Answer (2)

Entropy is a state function i.e. change in entropy depends upon the initial and final states of the system, not
on how that change is brought about.
264. Answer (2)
An increase in number of moles of gaseous phase shows more increase in entropy.
265. Answer (2)
A reversible process is carried out infinitesimally slowly so that all changes occurring in the direct process
can be exactly reversed and the system remains almost in a state of equilibrium with the surrounding at every
state of the process.
266. Answer (1)
C + 2H2 CH4 Ho = 74.8 kJ mol1
In order to calculate average energy for CH bond formation we should know the following data. C(graphite)
C(g), Ho = enthalpy of sublimation of carbon.
H2 2H Ho = Bond dissociation energy of H2.

( g)
( g)
267. Answer (1)

If a gas was to expand by a certain volume reversibly, then it would do a certain amount of work on the
surrounding. If it was to expand irreversibly it would have to do the same amount of work on the surrounding
to expand in volume, but it would also have to do work against frictional forces. Therefore amount of work has
greater modulus but ve sign.
WIrreversible > WReversible
(Tf)Irreversible > (Tf)Reversible
268. Answer (1)
1
C O 2 CO 2
2
(s)
( g)
( g)
1
1
ng = 1
=
2
2
H U = ng RT =
1
R 298 = 149R
2
269. Answer (4)

As no heat can enter or leave the system work is done at the cost of internal energy which falls and so does
the temperature (joule Thomson effect).
270. Answer (2)
Bond energy of OH bond = 109 kcal/mol means that when 1 mole of OH bonds are formed, 109 kcal energy
is released (because dissociation of bond absorb energy). Formation of one mole of water is equivalent to
formation of 2 moles of OH bond (HOH).
Hence energy released = 2 109 = 218 kcal.
270a. Answer (1)
I.
H2O(l)
(AIEEE 2009)
H+(aq)
OH(aq);
H = 57.32 kJ
1
O (g) H2O(l); H = 286.20 kJ
2 2
Adding I & II we get,
II.
H2(g) +
1
O (g) H+(aq) + OH(aq)
2 2
H = 57.32 286.2
= 228.88 kJ
H2(g) +
Physical Chemistry
31
271. Answer (1)

G = H TS
The process would be
Reversible if G = ve
Irreversible if G = +ve
Equilibrium if G = 0
H = 25000 cal and S = 90 cal
Given
at 300K, G = H TS
= 25000 300 90 = 52000
G is ve (reversible).
272. Answer (1)
For expansion against vacuum work done PdV = 0.
For expansion of an ideal gas the change in internal energy E = 0 as there is no force of attraction amongst
gas molecules or no work has to be done to overcome the intermolecular force. Under adiabatic condition no
heat enters or leaves this further confirms E = 0.
H = E + PV
H = 0 + 0 = 0
H = 0
273. Answer (4)

These are well known criterion of spontaneity.
274. Answer (2)
H G
276.5 76.5
200
=
=
= 0.667
T
300
300
At equilibrium G = 0
S =
H
276.5
=
= 414.5 K
S
0.667
275. Answer (1)
Teq =
Adiabatic curve is more steeper.

276. Answer (4)
At low temperature system is spontaneous.
277. Answer (4)
Enthalpy change is path independent.
278. Answer (3)
In Bomb calorimeter reaction is carried out at constant volume, V = 0 hence heat measured is E.
279. Answer (3)
Variation of heat of reaction with temperature is known as Kirchhoffs equation.
280. Answer (2)
CH4 + 2O2 CO2 + 2H2O,
CH3OH +
CH4 +
3
O CO2 + 2H2O,
2 2
1
O CH3OH
2 2
H = x
H = y
H = ve
H = x y = ve
xy<0
y > x
32
Physical Chemistry
281. Answer (4)

For endothermic reaction the minimum value of activation energy is equal to H.
282. Answer (2)
Formation of oxides of Nitrogen is in general endothermic.
283. Answer (1)
Since heat of neutralisation of strong acid and strong base is equal to formation of water.
NaOH + HCl NaCl + H2O + q
where q = heat of neutralisation
Na+ + OH + H+ + Cl Na+ + Cl + H2O + q
H+ + OH H2O + q
284. Answer (4)
G = H TS
285. Answer (3)
Qrev
Wrev
=
S =
T
T
P1
nRT ln
P2
S =
T
P1
S = nR ln P
2
286. Answer (3)
Fact.
287. Answer (2)
Factual
288. Answer (2)
P1V1 = P2V2
3 2.5
15 bar
0.5
W = Pext V = 15 (2.0) = 30 dm3 bar
289. Answer (2)
P2
228
76 kcal / mol1
PH bond energy =
3
H
H
P P
H
H
4(P H) + (P P) = 355
or 4 76 + (P P) = 355
(P P) .E = 51 kcal/mol1
290. Answer (1)
Cv
Cp Cv = R
R
1
dW n C dT 1 T T
v
nR
291. Answer (4)

For occurrence of a reaction,
(rH TrS) < 0
rH < TrS
283
103
87
T > 3253 K (2980C)

Physical Chemistry
33
292. Answer (3)

rG = 2(394) + (237) (1234) = 209 kJ
292a. Answer (4)
[JEE (Main)-2015]
2NO (g)

2NO(g) + O2(g)
2
reaction
= G
formation
product
reactant
formation
RT ln K P = 2 G
NO 2
NO 2
NO 2
2 G
NO
2 G
NO
RT ln K P
286600 R 298 ln K P
2
286600 R 298 ln1.61012

2
= 0.5 286,600 R 298 ln1.61012

293. Answer (2)
Amount of heat released
3.6
(393.5) 103 J
12
= 1.18 105 J
=
293a. Answer (1)

C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O(l)
Bomb calorimeter gives U of the reaction
So, as per question
U = 1364.47 kJ mol1
ng = 1
H = U + ngRT
[JEE (Main)-2014]
1 8.314 298
1000
1
= 1366.93 kJ mol
1364.47
294. Answer (4)

rG = rG + 2.303RT log Q
0 = rG + 2.303RT log K
= rG + 2.303RT log 1
= rG + 0
K 1
kf
kb
295. Answer (1)

fH H+(aq) = 0 , others are not in standard state.
34
Physical Chemistry
296. Answer (2)

Let B.ECH = x, B.ECC = y
4x = 360
(1)
6x + y = 620
y = (620 540) = 80
297. Answer (3)
Number of eqs. of KOH = 1
For maximum heat, there must be complete neutralisation.
Number of eqs. of H2SO4 = (0.5 2) V
V = (0.5 2) V
V = V
t
57.1 kJ
mc
298. Answer (2)

S = 2.303nR log 10
= 2.303 2 8.314
= 38.29 JK1
298a. Answer (2)
S nRln
(AIEEE 2011)
V2
V1
S 2.303 2 8.314 log
100
10
S = 38.3 J/mole/K
299. Answer (2)

H2O(l), 10C
H2O(l),0C
H2O(s),0C
S
S2
S = S1 + S2
= 2 2 2.303 log
273
1440
2
283
273
= 11.84 cal K1
300. Answer (3)
C2H6 (g) 2C(g) 6H(g)
(1)
rH = (99.8 6 + 83)
C(graph) C(g); 171kcal
(2)
H2 (g) 2H(g);
(3)
104 kcal
2C(graph) 3H2 (g) C2H6 (g)

Here, rH = fHC2H6(g) = ?
fHC2H6(g) = Eqn. (3) 3 + Eqn. (2) 2 Eqn. (1)
= 312 + 342 681.8

= 27.8
301. Answer (4)
Wirr = 2(70 20) 101
1
= 2416 cal
4.18
Physical Chemistry
35
302. Answer (3)

Wirr Pext. (Vf Vi )
303. Answer (4)

E remains constant, as it is a state function.
304. Answer (1)
4763.9
K = 5.88 102 exp
8.314 573
t1
2
ln 2
35 s
K
305. Answer (3)
E
S nF
2 96500 1.5 104 = 28.95 JK1 mol1
T P
306. Answer (2)
1st I.E. is for gaseous atoms only.
307. Answer (3)
In free expansion, W.D = 0.
308. Answer (1)
Fact.
309. Answer (3)
H2(g) +
1
S (g)
2 2
H2S(g)
H2(g) + Br2(g)
2HBr(g)
Br2(g) + H2S(g)
2HBr(g) +
1
S (g)
2 2
K1
...(I)
K2
...(II)
...(III)
(III) = (II) (I)

K2
K= K
1
309a. Answer (3)
(AIEEE 2012)
310. Answer (1)

HgO(s)
Hg(g) +
1
O (g)
2 2
Total pressure at equilibrium = P

Molar ratio of Hg : O2 = 2 : 1
PHg =
2
P
3
PO2 =
KP = PHg PO2
KP =
2
3
3/2
1/ 2
1
P
3
2 1
= P P
3 3
1/ 2
P3/2
36
Physical Chemistry
311. Answer (1)
N2O 4 (g)
1
2NO 2 ( g)
2
KP 2
at equilibrium
P at equilibrium = 0.5 atm
1
0.5 atm
1
2
=
0.5 atm
1
pN2O4 =
pNO2
KP =
2=
pN2 O
pN2O 4
4 2
(1 )2
2
(0.5)2 (1 )
=
1 2
(1 ) 0.5
1 2 = 2
22 = 1
2 =
1
2
= 0.707
= 71%
312. Answer (3)
COCl2
0.3
0.5
CO Cl2
0.1
0 .1
0.5
0.5
0.3
0.5
KC =
= 15
0.1 0.1
5
5
313. Answer (4)
More the value of equillibrium constant less is the stability of the oxide of nitrogen.
314. Answer (1)
KP = KC (RT ) ng
CO(g) + Cl2(g)
COCl2(g)
ng = np nr = 1 2 = 1
KP
1
= (RT)1 =
KC
RT
314a. Answer (2)
[JEE (Main)-2014]
1
O (g) SO3 (g)
2 2
KP = KC(RT)x
SO2 (g)
x = ng = no. of gaseous moles in product no. of gaseous moles in reactant

1
3 1
= 1 1 1
2
2 2
Physical Chemistry
37
315. Answer (2)

Ag+(aq) + Cl(aq)
AgCl(s)
Ag+
...(i)
(NH3)2]+
+ 2NH3
[Ag
...(ii)
+
Due to removal of Ag through reaction (ii), equilibrium (i) shifts in forward direction.
316. Answer (1)
At 25C pKb for NH3 = 4.7 (in aqueous solution)
[NH4Cl] = 0.1 M
[NH3] = 0.01 M
for basic buffer
[conjugate acid B]
pOH = pKb + log
[ weak base BOH]
= 4.7 + log
0 .1
0.01
= 4.7 + log 10 = 5.7

pH + pOH = 14
pH = 14 5.7 = 8.3
317. Answer (2)
0
1
N2O 4 (g)
2NO 2 (g)
1 0.2
0 .4
Total moles at equilibrium = 1.2
at t = 0, PV = nRT
1 V = 1 RT1
V = RT1
at equilibrium
P2V = n2RT2
1.2
1.2
P2 =
RT2 = RT RT2
V
1
=
1.2 600
= 2.4 atm
300
318. Answer (2)

Fact.
319. Answer (3)
Solution will be neutral hence pH = 7.
320. Answer (2)
[Sr2+] [Cl]2
(IP) KSP
1
2 1
3
IP = 10 10
2
2
1
108 which is greater than KSP.
8
321. Answer (4)
pH = 13
[H+] = 1013 mole ion/lit
1 mole ion have = 6 1023 ions
1 1013 mole ion have = 6 1023 1 1013
= 6 1010 ions per litre
Hence number of ions in 1 ml solution = 6 107.
IP =
38
Physical Chemistry
322. Answer (4)

Aqueous solution of FeCl3 is acidic, as on hydrolysis it produces H+ ions according to following equation
Fe+3 + H2O
[Fe(OH)2]+2 + H+
This is known as cationic hydrolysis.

323. Answer (2)
Ag2CrO4
2 Ag+ + CrO42
According to this equation the concentration of CrO42 ions will be half of concentration of Ag+ ions.
KSP = [Ag+]2 [ CrO42 ] = (1.5 104)2 (7.5 105)
= 1.6875 1012 = 16.875 1013
323a. Answer (1)
(AIEEE 2009)
[ CO32 ] = 104 M
Ksp [BaCO3] = [Ba2+] [ CO32 ]
[Ba2+] =
K sp
[CO32 ]
5.1 109
104
= 5.1 105 M
324. Answer (2)

The pH of Buffer is given by
pH = pKa + log10
[Salt]
[ Acid]
pKa = 4.76
[Acid] = 10 ml of 1.0 M
[Salt] = 20 ml of 0.5 M
But total volume is made up 100 ml
[Acid] = 0.1 M
[Salt] = 0.1 M
[Acid] = [Salt]
pH = pKa
Hence pH of Buffer solution will be 4.76.
325. Answer (4)
Each reaction has a definite value of the rate constant at a particular temperature i.e. KP is constant at constant
temperature.
326. Answer (1)
Backward reaction is dissociation reaction and hence endothermic. The forward reaction will therefore be
exothermic. Further it is acccompanied by decrease in number of gaseous moles. Hence its equilibrium will
be affected by temperature and pressure.
327. Answer (3)
t0
O2
2SO 2
60
5
5 1 .5
at equilibrium 5
100
53
3 .5
0
2SO 3
3
2
Total = 2 + 3.5 + 3 = 8.5
Physical Chemistry
39
328. Answer (3)
t0
1 mole
1 mole
P4 (s) 6Cl2 (g)
at equilibrium 1 x
1 6x
1 x 1 6x
4PCl 3 ( g)
4x
329. Answer (1)

The reaction in which value of K is more goes fastest to completion.
330. Answer (3)
On doubling the volume, pressure decreases and the reaction shifts in the direction of increasing number of
moles.
331. Answer (1)
3
4
2
[C]3

Q=
=
= 16
[ A ] [B]
1 2
2 2
Given KC = 20
here QC < KC
rxn will be forward.
Thus to have Q = KC. The concentration of C must increase i.e. reaction should proceed from left to right.
331a. Answer (2)
[JEE (Main)-2015]

2A
B + C, G = 2494.2 J
As we know G = 2.303 RT logKC

2494.2 = 2.303 8.314 300 log KC
0.434 = log KC
KC = anti log (0.434)
KC = 0.367
1
1
Now A = , B = 2 and C =
2
2
Now QC =
CB
A 2
1
2
2
= 2 =4
1

2
as QC > KC, hence reaction will shift in backward direction.

332. Answer (1)
pH = 12
pOH = 2
[OH] = 102 M
10 2
M = 102 N
2
= 101 equivalent in 100 ml = 1 milliequivalent
Ca(OH)2 =
333. Answer (4)

K for the reaction is given by K = [CO2]
Because concentration of solids taken to be unity. Since [CaCO3] and [CaO] do not figure in the expression
there will be no effect of addition of CaCO3.
40
Physical Chemistry
334. Answer (2)
0 .1
0.03
0
0
0
2KCN AgNO 3 Ag(CN)2 KNO 3 K

0.1 0.06
0
0.03
0.03
0.03
[Ag(CN)2] = 0.03
0
0.04
Ag 2CN (left from KCN)

a
0.04 a
0.04
0.03
Now [ Ag(CN)2 ]
0.03 a
0.03
KC = 4 1019 =
(0.04)2 a
0.03
a = 7.5 1018
335. Answer (1)
Initial
0 .2
0 .6
N2
3H2
At equilibrium 0.2 a 0.6 3a
Total mixture is 0.8, 40% of its reacts i.e.
0
2NH3
2a
0.8 40
0.8 40 1
reacts to give
mole of NH3 or NH3 formed
100
100
2
is 0.16 mole
2a = 0.16
a = 0.08
Initial mole = 0.8
Final mole = (0.2 0.08) + (0.6 0.24) + 0.16
= 0.12 + 0.36 + 0.16 = 0.64
Ratio of final to initial mole =
0.64
4
= 0.8 =
0 .8
5
336. Answer (2)

1
NH4HS
( s)
1 x
0
0
NH 3 + H2S
(g)
( g)
x
x
Total mole of gaseous substances = 2x

x H2S = x NH3 =
1
2
pH2S = pNH3 =
P
2
KP = pNH3 pH2S =
p2
= 64
4
p2 = 256
p = 16 atm.
Physical Chemistry
41
337. Answer (4)

Cu+2 + S2
CuS
Ksp [CuS] = S2 = 1031

S = 3.16 1016
2Ag+ + S2
Ag2S
KSP (Ag2S) = (2S)2 S = 4S3 = 1044

S = 1.36 1015 = 13.6 1016
Hg+2 + S2
HgS
KSP (HgS) = S2 = 1054

S = 1 1027
338. Answer (2)
At 50% neutralisation
[CH3COOH] = [CH3COONa]
pKa = 14 pKb = 4.74
pH = pKa = 4.74
At complete neutralisation CH3COONa solution is alkaline due to hydrolysis and concentration is halved due
to dilution by equal volume NaOH.
Hence
[CH3COONa] =
0.01
M
2
pH = 7 +
pKa
log C
+
2
2
= 7 + 2.37 +
log 0.005
= 8.22
2
339. Answer (4)
Weak acid Weak base

+
BOH
HA
Salt
BA + H2O
A
B
+
+ H2O BOH + HA
C (1 h)
C (1 h)
Ch
Ch
mol / L
mol / L
mol / L mol / L
Kh =
1 10 14
5 10 7 5 10 7
1 10 7
5 10
h2
(1 h)
, Kh =
Kw
(1 h) 2
h2
(1 h)2
h
1 h
5h = 1 h
1
6
h = 0.166
h =
h = 16.6%
42
Physical Chemistry
340. Answer (3)

C = 0.1
H + A
C C
HA
C (1 )
pH = log10 [H+]
2 = log10 C
2 = log10 0.1
log10 0.1 = 2
0.1 = 102
=
10 2
10 1
= 101 = 0.1
340a. Answer (2)
(AIEEE 2012)
341. Answer (1)

... n = 0 for H + I
g
2
2
2HI
hence this reaction will be not influenced by changing volume.

342. Answer (3)
A & C are weak base and it salt with strong base hence will form basic buffer.
343. Answer (3)
At the half neutralisation point of an acid pH = pKa.
344. Answer (3)
H2 + I2
2HI
[HI] 2
K=
[H2 ] [I2 ]
At the initial number of moles of H2 and I2 were same therefore at equilibrium [H2] = [I2]
47.6 = K =
[HI] 2
[I2 ] 2
[I2]2 47.6 = [HI]2

[I2]2 < [HI]2
[I2] < [HI]
345. Answer (3)
PCl5(g)
COCl2(g)
PCl3(g) + Cl2(g)
KP =
CO(g) + Cl2(g)
KP =
PPCl3 PCl2
PPCl5
PCO PCl2
PCOCl2
If CO is introduced, the dissociation of COCl2 will decrease and PCl2 will decrease. This will favour dissociation
of PCl5 because both reactions are attained in same vessel.
Physical Chemistry
43
346. Answer (1)
t0
1
N2 O 4
t eq 1 x
0
2 NO 2
2x
Total moles at equilibrium = 1 x + 2x = 1 + x

2x = 50% of 1 + x
2x = 0.5 (1 + x)
2x = 0.5 + 0.5 x
x = 0.33
KC =
0.66 0.66
[NO2 ]2
0.66 0.66
=
=
1 0.33
[N2O 4 ]
0.66
KC = 0.66
347. Answer (3)
40 ml of 0.1 M ammonia solution = 40 0.1
= 4 milliequivalent ammonia solution
20 ml of 0.1 M HCl = 20 0.1
= 2 milliequivalent of HCl
4
2
0
NH4 OH HCl NH4 Cl H2O
42
0
2
2
[NH4 Cl]
2
pOH = PKb + log [NH OH] = 4.74 + log
= 4.74
2
4
pH = 14 4.74 = 9.26
348. Answer (4)
[Ag(H2O)2]+(aq) + NH3(aq)
K1 = 2.0
...(1)
[Ag(NH3)2]+(aq) + H2O(aq)
...(2)
103
[Ag(NH3) (H2O)]+ + NH3(aq)

K2 = 8.3
[Ag(NH3)(aq) (H2O)]+ + H2O(I)
103
adding (1) and (2)

[Ag(H2O)2]+(aq) + 2NH3(aq)
[Ag(NH3)2]+(aq) + 2H2O(I) : K
On addition of reactions equilibrium constants are multiplied

K = K1K2 = 2 103 8.3 103 = 16.6 106
349. Answer (4)
HCl ionises as
HCl
H+ + Cl
2H+ + SO 42
H2SO4
Since pH of both is same, H+ concentration has to be equated.

Hence 0.1M 0.05 M H2SO4
44
Physical Chemistry
350. Answer (2)

Ag+ + Cl
AgCl
KSP = S2
1.5 10 10
K SP =
= 1.225 105 g-molecule/litre

= 1.225 105 143.5 g/litre
= 17.58 104 g/litre
351. Answer (2)

Kw
1 10 14
Kn = K =
= 2 1010
5 10 5
a
0.02
ASC + H2O
0.02 x
0.02
HASC OH
x
[HASC][OH ]
Kn =
[ ASC ]
2 1010 =
x.x
x2
=
0.02 x
0.02
x2
0.02
x = 2 106
[OH] = 2 106
[H+]
1 10 14
2 10 6
= 5 109
352. Answer (3)

pH + pOH = 14
12 + pOH = 14
pOH = 2
[OH] = 102 mole/litre
Number of OH in 250 ml =
10 2
4
= 0.25 102 = 2.5 103

Soluble mole of Ca(OH)2
1
2.5 103 = 1.25 103
2
353. Answer (2)

A + B
2C + D + Heat
2 moles
3 moles
Reaction is exothermic.
Reaction involved increase in volume (number of moles). So it is most favoured at low temperature and low
pressure.
Physical Chemistry
45
354. Answer (1)

1 mole
NH2 COONH 4
1
0
0
2NH3 CO 2
Total number of moles = 1 + 2 + = 1 + 2

Average molar mass = 2 16 = 32
32 =
(1 ) 78 (2 17) 44
1 2
32 =
78 78 34 44
78
=
1 2
1 2
32 + 64 = 78
= 0.71875 = 0.72
355. Answer (1)
[Ag2O](s) = [Ag](s) = 1
KP = p O 2
356. Answer (4)
pH =
1
pKW (for pure H2O)
2
pH =
1
13.26 = 6.63
2
357. Answer (2)

Value of KSP of AgI is lower than that of AgCl.
358. Answer (1)
CO (Carbon monoxide) is a lewis base. The C atom tends to donate a pair of e.
359. Answer (2)
Moles of AgCl formed =
0.1435
103 mole
143.5
= eq. of HCl present

Total eq. of mixture = 20 0.1 103 = 2 103
eq. of H2SO4 present = 2 103 103 = 103
= 5 104 moles
Strength of H2SO4 = 5 10 4 98
1000
2.45 gL1
20
46
Physical Chemistry
360. Answer (2)

1
O2
2
0
H2 O H2
1
n 1
2 1
2
; XH2
; XO2
2
2
2
XH2O
KP
PH2 PO1/22
PH2O
2
2
P
P2
3/2 P1/2
2
2
KP
2 1
1 2 1/2
P
2
361. Answer (1)
1
3
N H NH3 , n 1
2 2 2 2
362. Answer (3)
k1k 2
H 2 S2
1021
H2S
0.12 S2
0.1
S2 10 20
363. Answer (4)

NH4Cl is the salt of weaker base and strong acid, so will be acidic. NaCl neutral and NaCN will be basic as
this is the salt of strong base and weak acid HCN.
364. Answer (2)
Ksp = 22 33 S2+3 = 108(S)5
365. Answer (1)

HCO3 H
H2CO3
2

and HCO3
H CO3
366. Answer (4)

K a1
s1
s2
K a2
s1
s2
10 4
4 10 10
103
2
Physical Chemistry
47
367. Answer (3)

Ksp = 1011 = [Mg2+][OH]2 = 0.1[OH]2
[OH] = 105 (Minimum conc. for precipitation)
pH = 9
368. Answer (3)
In water, solubility will be maximum as in other cases, there is common-ion effect. In 0.05 M AgNO3, it will
be least.
369. Answer (1)
Q < K Reaction goes forward
370. Answer (1)
11.45 103
Kc =
103 mole/L
8.314 298
= 4.6 103 M
371. Answer (3)
K p =
1
(K p )2
1
(4 103 )2
106
16
= 6.25 104 atm

372. Answer (2)
Volume occupied by diamond is less.
373. Answer (2)
As K is increasing on increase of T.
374. Answer (1)
log K
H
S
2.303 RT
R
375. Answer (3)

Apply mass balance
376. Answer (4)
In the expression of Q, all activity terms are taken at unit pressure or unit concentration.
377. Answer (3)
Weaker acid has stronger conjugate base.
378. Answer (3)
In benzaldehyde, 5 carbon atoms have 1 oxidation number, 1 carbon atom has zero oxidation number and
1 carbon atom has +1 oxidation number.
H
(+1)C = O
(0)
(1)
(1)
(1)
(1)
(1)
48
Physical Chemistry
379. Answer (1)

The sum of oxidation number of all the carbon atoms = 5(1) + 0 + 3 = 2.
OH
(+3)C = O
(0)
(1)
(1)
(1)
(1)
(1)
380. Answer (4)

6
2 3
H
K 2 Cr 2 O 7 Fe C 2 O 4
Cr 3 Fe 3 C O 2
(nf 6 )
(nf 3 )
Inverse of nf ratio is the mole ratio

3 K2Cr2O7 + 6 FeC2O4 Cr3+ + Fe3+ + CO2
6 mole FeC2O4 required 3 mole of K2Cr2O7
1 mole FeC2O4 required
3
1
1
mole of K2Cr2O7
6
2
381. Answer (2)
8 e
N2H4
(N2H4 ) 8 ( y )
2 x 4 8
x 2
382. Answer (3)

+2
Cu S
Cu + SO2
+2 e
6 e
So, 1 mole of CuS loses 4 mole of electrons.

Equivalent weight of CuS =
M
4
383. Answer (4)

0
N2 N H3
One mole of N2 loses 6 mole of electrons and one mole of NH3 gains 3 mole of electrons. Hence, equivalent
M1
M2
and
respectively. If an element is present in its lowest oxidation state
6
3
then it behaves as reducing agent only. So, NH3 acts as reducing agent only.
weight of N2 and NH3 will be
384. Answer (2)

If an element is present in its highest oxidation state then it behaves as oxidising agent only and if an element
is present in its lowest oxidation state then it behaves as reducing agent only. S has highest oxidation state
+6 and lowest oxidation state 2. So, H2SO4 acts as oxidising agent only and H2S acts as reducing agent
only.
Physical Chemistry
49
385. Answer (1)

The structure of K3CrO8 is
O
+
K
O
Cr
O
OO K
O+
K
386. Answer (2)

In the reaction, only two chlorine atom change its oxidation number (1) to zero.
So, n-factor for HCl =
2
0 .5
4
M
36.5
73
0 .5
0.5
Equivalent weight of HCl =

387. Answer (2)
Balanced reaction is
3 Cl2 + 6 OH 5 Cl + ClO3 + 3H2O

388. Answer (4)
Cu2+, Sn4+ and Fe3+ are placed below hydrogen in electrochemical series. So, it is reduced by hydrogen but
Al3+ is placed above hydrogen in electrochemical series.
389. Answer (3)
Less electronegative halogen does not displace more electronegative halogen from the salt but I2 displaces
chlorine and bromine from oxysalt because in this case, displacement of halogen is done by reduction.
390. Answer (4)
2+
+3
Fe S 2
+4
Fe2O3 + SO2
1 e
2 5e
Total 11 mole of electrons are lost by 1 mole of FeS2. Hence, equivalent weight of FeS2 =
M
.
11
391. Answer (4)

Equivalents of KMnO4 = 0.5 5 (nf = 5) = 2.5
In 4th option,
Equivalents of FeSO4 = 2.5 1 (nf = 1) = 2.5
392. Answer (4)
Br2 Br, equivalent mass of Br2 =
M
2
Br2 BrO3 equivalent mass of Br2 =

Net equivalent mass of Br2 =
n-factor of Br2 =
M
10
M M 6M
2 10 10
10 5
6
3
50
Physical Chemistry
393. Answer (2)

O
(+5) (0)
(0)
O
(+5)
O SSSSO
O
In which, two sulphur atoms have (+5) oxidation number and two sulphur atoms have zero oxidation number.
394. Answer (3)
Silver cant displace Cu from CuCl2 because Ag is placed below than Cu in electrochemical series.
395. Answer (3)
Electrolysis makes a non-spontaneous change spontaneous.
396. Answer (2)
Factual
397. Answer (1)
Factual
398. Answer (4)
Here energy evolved (G) is converted in electrical energy.
399. Answer (1)
Factual
400. Answer (4)
Electrochemical series is the arrangement of increasing order of standard reduction potentials.
401. Answer (1)
Oxidation potential of Li is highest and of H is zero.
402. Answer (3)
Eocell = EoC EoA

= 0.41 (0.74)
= 1.15 V
EoCu2 /Cu EoZn2 /Zn Cu will work as cathode.
403. Answer (4)
H2(g)
1 atm
Temperature = 298 K
Pt(s)
This is schematic diagram of S.H.E.
1 M HCl
404. Answer (1)

This is as per the law of conservation of mass and law of conservation of charge.
405. Answer (3)
As oxidation potential of metalloids must be less than metals and greater than non-metals.
406. Answer (3)
Oxidation potential under standard conditions will be positive and constant irrespective of concentration.
Physical Chemistry
51
407. Answer (4)

6
H
K 2 Cr2 O 7 Sn Cl 2
Cr 3 Sn Cl 4
( nf 6 )
(nf 2 )
Inverse of nf ratio is the mole ratio
H
K 2Cr2 O 7 3SnCl 2
Cr 3 SnCl 4
3 mole SnCl2 will be oxidised by 1 mole K2Cr2O7
1 mole SnCl2 will be oxidised by
So, mole of K2Cr2O7 required =
1
1 mole K Cr O
2
2 7
3
1
mole
3
408. Answer (1)

Na2 B4 O7
2 1 + 4x 14 = 0
4x = +12
x = +3
409. Answer (3)
In H2SO4, S has highest oxidation number i.e. +6 and in SO2, S has oxidation number +4 which lies in
between range of S (2 to +6).
410. Answer (4)
+1
+2 2+
Cu2 S
+4
Cu + SO2
+2 e
6 e
Total 8 e are lost by one molecule of Cu2S. So, equivalent weight of Cu2S =
M
.
8
411. Answer (3)

1
CH3 CH CH2
412. Answer (3)
4
CH4
CO2 , n 4 4 8
413. Answer (2)

Total 4 alternate corners, 4 alternate edges and 2 alternate faces are present in a cubic unit cell.
Number of A atoms =
1
1
4
8
2
Number of B atoms =
1
4 1
4
Number of C atoms =
1
2 1
2
Hence, formula of unit cell = A1/2BC and simplest formula of compound is AB2C2.
52
Physical Chemistry
414. Answer (2)

Orthorhombic crystal system has simple, body centred, end centred and face centred unit cell.
415. Answer (4)
416. Answer (4)
Only Ba forms body centred structure, Ca and Sr forms face centred structure while Be forms hexagonal close
packed structure.
417. Answer (3)
=
NM
a3NA
(2) (20 g mol1)
2 452 1012 m / 3
6.023 1023 mol1
= 9.11 105 gm3 = 0.91 g cm3
418. Answer (3)

419. Answer (2)
In Fe3O4, O2 ions form the ccp lattice, one Fe2+ is present in octahedral void. While Fe3+ ions are equally
distributed in between octahedral and tetrahedral voids. So, only 12.5% tetrahedral voids are occupied.
420. Answer (1)
421. Answer (1)
422. Answer (3)
d
ZA
V(in cm 3 ) N0
For F.C.C., Z = 4, then

d
4 27
( 4 10
8 3
) 6.023 10
23
4 27
64 10
24
6.023 10 23
= 2.8 g/c.c
423. Answer (4)

All the correct statements.
424. Answer (1)
425. Answer (1)
Number of A atoms =
1
8 1
8
Number of B atoms =
1
6 3
2
Number of C atoms =
1
12 1 4
4
After passing tetrad axis, 2 face atoms and 1 body atom is removed. Now,
Number of A atoms =
1
8 1
8
Number of B atoms =
1
1
6 2 2
2
2
Number of C atoms = 4 1 = 3
Hence, formula of unit cell is AB2C3.
Physical Chemistry
53
426. Answer (2)

426a. Answer (1)
ZA
(AIEEE 2011)
8
8
5
2
So formula of compound is AB5/2
ZB
i.e., A2B5
427. Answer (3)
In Frenkel defect, ions occupy the interstial site like interstitial defect and create a vacancy in the lattice site
like vacancy defect. So, it is the combination of vacancy as well as interstitial defect.
428. Answer (2)
429. Answer (1)
In case of BCC structure,
3a
2
r r
(a = cell edge length, r+ + r = inter ionic distance)
3 3.5
2
r+ + r = 3.031
r r
429a. Answer (3)

Cl
Cl
[JEE (Main)-2014]
Cl
Cl
+
Cs
Cl
Cl
Cl
Cl
2rCl 2rCs 3 a
rCl rCs
3a
2
430. Answer (3)

431. Answer (4)
In a cubic crystal, 9 plane of symmetry, 13 axis of symmetry and 1 centre of symmetry is present.
432. Answer (3)
Factual type.
433. Answer (3)
Number of O2 ions =
1
1
8 6 4
8
2
Number of metal ions =
(12.5% T.V )
( 50% O.V.)
Hence, formula of metal oxide is M3O4.

54
Physical Chemistry
434. Answer (2)

The length of face diagonal = a 2
= 80 2
So, a = 80 pm (a = cell edge length)
In NaCl type structure,
r r
a 80
40 pm
2
2
434a. Answer (1)

r=
a
2 2
(AIEEE 2009)
361
2 2
127.6 pm
435. Answer (4)

Body diagonal of cube =
3 a = (1.732) (387 pm)
= 670.3 pm
2 (r+ + r) = 670.3 pm
670.3
pm 181 pm = 154 pm
2
436. Answer (3)
r+ =
Factual type.
437. Answer (2)
438. Answer (1)
For fcc,
ax 2
(x = cell edge length)
a
2
3
a
a3
Volume of fcc unit cell =
2 2
2
439. Answer (2)
The length of body diagonal is a 3 . Two tetrahedral voids are present on each body diagonal at the distance
a 3
.
2
440. Answer (3)
The simplest unit of hcp structure is hexagon. Other statements are correct.
441. Answer (4)
For bcc,
a 3 5 3
2.165
4
4
r = 216.5 pm
r
441a. Answer (3)
(AIEEE 2012)
Physical Chemistry
55
441b. Answer (1)

[JEE (Main)-2015]
Edge length of BCC is 4.29 .
In BCC,
4
r
edge length =
3
4
4.29 =
r
3
4.29
r=
3 1.86
4
442. Answer (2)
443. Answer (3)
Total 4 body diagonals are present in a cube. 1 middle tetrahedral void is present on each body diagonal is
common for all. So, total number of tetrahedral voids are 9.
444. Answer (1)
rNa
0.75
From r
K
rNa 0.75 rK
Putting the value of rNa in
0.75 rK
rCl
rK
rCl
0.55
(i)
rNa
rCl
0.55 then we get
0.55
0.733
0.75
2(rK rCl ) 2(0.733 1)

So, 2(r r ) 2(0.55 1) 1.118
Na
Cl
(Side for unit cell for KCl = 2(rK rCl ) , Side for unit cell for NaCl = 2(rNa rCl ))
445. Answer (2)

Triclinic is the most irregular system. The cell dimensions of this system are a b c and 90.
446. Answer (4)
All statements are correct for fluorite structure.
447. Answer (4)
1 mole AlCl3 develops 2 mole of cation vacancies in the doping in NaCl.
10 5
6.023 10 23 = 1.2046 1017
Number of cation vacancies = 2
100
448. Answer (3)
In this defect, some Fe2+ ions are converted into Fe3+ ions. Due to charge balance number of Fe atoms
decrease. Hence, it is found as Fe0.95O not FeO.
449. Answer (2)
Both Al3+ ions are present in octahedral voids. Other statements are correct.
450. Answer (3)
In the unit cell of NaCl, Na+ ions are present in octahedral voids and Cl ions are present on ccp lattice. When
one body diagonal plane is placed in the unit cell, then 4 corner ions, 2 edge ions, 2 face ions and 1 body
ions are removed. Now,
1
1
Number of Na+ ions = 4 2 1 2

4
2
1
1
1
Number of Cl ions = 4 2 4 2
8
2
2
Hence, simplest formula is NaCl.

56
Physical Chemistry
451. Answer (2)

a
37.46 a13
37.46
3 1 3
1.103
27.94 a2
a2
27.94
452. Answer (3)

Fact
453. Answer (2)
Volume of any lattice is
V = abc(1 cos2 cos2 cos2 2cos cos cos)1/2
V1 = Vtetragonal = a2c
(because a = b c, = = = 90)
V2 = Vhexagonal = a2c
3
2
(because a = b c, = = 90, = 120)
V1
2
V2
3
454. Answer (1)

MnO2 has rutile structure.
455. Answer (1)
No. of T-voids = 2 no. of atoms
No. of O-voids = no. of atoms.
456. Answer (4)
Reverse osmosis involves moment of solvent particles through semipermeable membrane from concentrated
solution to dilute solution.
457. Answer (3)
For isotonic solution C1 = C2 (at constant temperature).
458. Answer (1)
N=
98 1000 1.6
32
49
100
459. Answer (2)

9.1 1031 kg = 1 e
1
1 kg =
6.023 1023 e = 1 mole
9.1 10
1
9.1 10
31
31
1
6.023 10
23
1
9.1 10
31
Number of moles (n) = 0.01 108 = 106 moles
Physical Chemistry
57
n
Molarity = v
2
6
10
M=
0.5
M = 2 106 M.
460. Answer (4)
According to Raoults law for non-volatile solution.
PB P
PB
A solute
B solvent
xA
and in Ostwald Walker process
PB P
PB
loss in weight of solvent

gain in weight of CaCl2 .
461. Answer (1)

Because in positive deviation solvent-solvent interaction is greater than solute-solvent interaction.
462. Answer (4)
463. Answer (1)
Elevation in boiling point is inversely proportional to molecular length of solute.
464. Answer (4)
465. Answer (2)
meq of HCl = meq of NaOH
Mass
1000 NVml
Eq mass
(i)
(N = 0.5 N, V = 100 ml)
mass of HCl 1000

molality = M.m mass of solvent (g)
1000
g

5
w
Eq mass
g
1000 w 5
Eq mass
(ii)
from eq. (ii) to (i)
w 5 = 0.5 100
w
(mass of solvent )
N 0.5 N
V 100 ml
= 10 g.
58
Physical Chemistry
466. Answer (3)

M=
a3Na
N
(1.984 gcm3 )(630 10 10 cm)3 (6.023 1023 mol1)

4
= 74.7 g mol1
467. Answer (1)
468. Answer (2)
469. Answer (3)
470. Answer (3)
471. Answer (1)
Osmotic pressure () =
i1n1RT
1 =
= 1 + 2
nRT
v
and 2 =
i2n 2RT
v
i1n1RT i2n 2RT

= v v
and v1 + v2 = v
i1n1 i2n 2
RT
=
T ini in2

v v
v
or
i1n1 i2n 2
= v v RT .
1
2
472. Answer (4)

473. Answer (2)
PB P
PB
in A
(i)
in A nB
A solute
B solvent
solution is concentrated
PB = 760 mm-Hg
nA =
5.85
= 0.1 mole
58.5
nB =
180
= 10 moles
18
P = 750 mm-Hg
Physical Chemistry
59
AB A B
for
i=1+
from equation (i)
760 750
0.1(1 )
760
(1 )0.1 10
1
0.1(1 )
76
10
1+=
(dilute solution)
100
76
= 0.315.
474. Answer (3)
Solution will be ideal and for ideal solution Hmix. = 0.
475. Answer (3)
Al 2 (SO 4 ) 4 2Al
1 mole
2 moles
3SO 4 2
3 moles
nsolute
1000
molality = w
solvent
3=
n
1000
250 1
n=
3
mole
4
d v
w 250 1
w 250 g
According to above equation
1 mole of Al2SO4 producing 2 moles of Al3+
3
2 3
3
mole of Al2SO4 producing =
mole
4
1 4
2
number of Al3+ ions =
3
23
23
6.023 10 9.03 10 ions.
2
476. Answer (2)

For MgCl2, = 50% i.e. 0.5
MgCl2 Mg
1
2Cl
i1 = 1 + 2
i1 = 1 + 1
i1 = 2
60
Physical Chemistry
for CH3COOH, = 50% i.e. = 0.5

CH3 COOH
1
1
(CH3 COOH)2
2
2
i2 = 1 0.25
i2 = 0.75
i2 = 1
Total value of
i = i1 + i 2
i = 2 + 0.75
i = 2.75
477. Answer (1)

478. Answer (3)
479. Answer (2)
Addition of acid in to water is exothermic and H > 0 then solution will be non ideal showing positive deviation.
479a. Answer (1)
(AIEEE 2009)
Ethanol has H-Bonding, n-heptane tries to break the H-bonds of ethanol, hence, V.P. increases. Such a
solution shows positive deviation from Raoult's Law.
480. Answer (3)
At 56.6C, solid and liquid are in the same phase.
481. Answer (1)
Vapour pressure does not changes with enthalpy.
482. Answer (2)
483. Answer (3)
Solvent is the component which have same physical state as that solution.
484. Answer (3)
For AlCl3 Al
i1 = 1 + 3
3Cl
( = 100%)
i1 = 4
NaCl Na Cl
1
i=1+
( = 100%)
i=2
1 = i1RT
2 = i2cRT
i
1
2 i2
1
4
2
1 : 2 = 2 : 1.
485. Answer (1)

486. Answer (2)
When benzoic acid dissolved in benzene it gets dimerises and molecular mass of its diemer is 244 amu.
487. Answer (1)
Hvap = Lv M.m = 540 18 = 9720 cal/mole.
Physical Chemistry
61
488. Answer (1)

m
1000 1000
55.56
18
1000
489. Answer (3)

PB P
xA
PB
(i)
From Eqn (i)

xA
m = x 55.55
xA
xA
3 = x 55.55
B
xA
x = 0.054
xA
xB
xA + xB = 1
0.054
xA
0.054
x A 1
1
0.054
xA
A solute
B solvent
(i)
1
19.5
xA = 0.05
PB P = xA PB
PB P = 0.05 760 = 38.97 mm-Hg.
489a. Answer (2)
[JEE (Main)-2015]
Vapour pressure of pure acetone PA = 185 torr

Vapour pressure of solution, PS = 183 torr
Molar mass of solvent, MA = 58 g/mole
PA PS nB
=
PS
nA
185 183 WB MA
183
MB WA
as we know
2
1.2 58
=
183 MB 100
MB =
1.2 58
183
2 100
= 63.68 g / mole
490. Answer (3)
491. Answer (1)
SO2 + NaOH NaHSO3
meq. of NaOH = meq of NaHSO3
NV
(NaOH)
g
1000(NaHSO 3 )
eq mass
g
1000
104
gNaHSO 1.04 g (mass of NaHSO )
3
3
For the calculation of lowering of vapour pressure
0.1 1 100
PB P
PB
xA
A solute
B solvent
62
Physical Chemistry
1.04
104
36
PB
18
PB P 0.01
PB
3
PB P
(dilute solution)
0.01
1 (atm)
2
PB P
= 0.005 atm
(PB P) =
(lowering of vapour pressure)
492. Answer (2)

Kb
RT0 2
1000 Hv
2 (373)
9.72
3
1000
10
18
Kb = 0.52 mole/kg
Kb
Tb = Kb m
Tb = 0.52 0.1 = 0.052.
493. Answer (2)

C 6H5 COOH
1
1
C H COOH
n 6 5
1
i = 1
100%
i = 1 1
n
i = 1 1
n
Tf (obserbed)
i=
(i)
Tf (calculated)
Tf
Kfm
(ii)
12.2 1000
122 100
m = 1 molal
m=
0.93
1.86 1
1
i=
2
Putting the value of i in equation (i)
i=
i 1 1
n
1
1
1 1
2
n
n = 2.
Physical Chemistry
63
494. Answer (2)

495. Answer (3)
log Tb
log m
Tb = Kbm
logTb = logKb + logm

y = mx + c
(tan = 1, = 45)
m=1
496. Answer (4)

Solute solvent interaction is equal to solute-solute and solvent-solvent interaction.
497. Answer (4)
For dilute solution
nA
xA ~ n
B
(nA + nB ~ nB)
PB P in A
ix A .
PB
nB
498. Answer (2)

For isotonic solution
A = B
CART = CBRT
CA = CB.
499. Answer (2)

x A
( vapour phase )
P A x A
P A x A PB x B
xA =
50 0.5
50 0.5 100 0.5
xA =
25
75
xA = 0.33.
500. Answer (1)

Volume strength of H2O2 = 5.6 normality
volume strength = 5.6 4.5 = 25.2.
501. Answer (3)

The solution which flow into the blood stream are of the same osmotic pressure as that of blood otherwise
due to difference in osmotic pressure blood cells may swell and burst.
502. Answer (2)
R.H
Partial pressure of water

100
Saturated partial pressure of water
64
Physical Chemistry
503. Answer (2)

Fact
504. Answer (3)
P XAPA0 XBPB0
505. Answer (3)

2A
A2
1
0
1
2
2
1
1 0.5
2
506. Answer (2)
i 1
Kb

3A
A3
1
3
2
3
2 1
1 0.33
3 3
i 1
RTb2 M1
8.314 383.7 92
Hv
1000Hv
1000 3.32 103
2
= 34 kJ mol1
507 Answer (2)
i = 5 for K4[Fe(CN)6) and i = 5 for Mohr salt.
507a. Answer (3)
(AIEEE 2010)
Tf = i Kfm
i for Na2SO4 is 3(100% ionisation)
Tf = 3 1.86
0.01
1
Tf = 0.0558 K
507b. Answer (1)
[JEE (Main)-2014]
i CRT
C2H5OH 1 0.500 R T 0.5 RT

Mg3 (PO4 )2 5 0.100 R T 0.5 RT
KBr 2 0.250 R T 0.5 RT
Na3PO4 4 0.125 RT 0.5 RT

508. Answer (4)
509. Answer (2)
0.2 mol I2 and 0.8 mol C6H6
WC6 H6 0.8 78
m
0.2 1000
3.2
0.8 78
Physical Chemistry
65
510. Answer (4)

6
Cr 2 O72 2Cr O24
511. Answer (2)

G1 = 2Fx1, G2 = + x2F, G3 = FE
G3 = G1 G2 = ( 2Fx1) (x2F) = FE
E = (x2 2x1) V
511a. Answer (2)
Fe
E0 = ?
3+
(1)
(AIEEE 2009)
Fe
2+
E0 = 0.439 V
(2)
Fe
E = 0.036 V
(3)
G01 + G02 = G03
n1E01 n2E02 = n3E03
E0 + 2 0.439 = +3 0.036
E0 = +0.77 V
512. Answer (3)

Ksp = 4x3, (x is solubility of Ag2CrO4)
[Ag+] = 2x
E = 0.80
0.0591
1
log
1
2x
513. Answer (2)

AgNO3 will react with copper.
514. Answer (3)
Standard free energies of reactant and product are same.
Go = 0
515. Answer (4)
516. Answer (4)
Value of n is not given
517. Answer (4)
2.303 RT
log Q
nF
H2
2H+
E=
Q=
PH2
[H ]2
518. Answer (4)
519. Answer (4)
Fact.
520. Answer (2)
Only H2O is electrolysed.
66
Physical Chemistry
521. Answer (4)

Change in oxidation number of N is 6
Veqv =
22.4
= 3.73 L
6
522. Answer (1)

2H2O + 2e H2 + 2OH
...(i)
2H2O O2 + 4H+ + 4e
...(ii)
From (i) 1 mol of H2 = 22.4 LH2 is obtained by 2 units xL of H2
2x
units costing Rs.x
22.4
hence, 1 units costs = Rs. 11.2

from (ii) : 22.4 L at NTP costs = 4 units
= 4 11.2
xL costs = 2x
523. Answer (3)
NO2
NO
nf 2
2e +
n=2
gram Eq = n mole = 2 0.5 = 1
1 Eq nitrogen benzene require 1F
Net charge =
1
= 1.25 F
0 .8
524. Answer (2)

It is 2.26V.
525. Answer (1)
The cell can be formed as Fe|Fe3+; OH|Fe(OH)3(s)|Fe
The electrode reactions can be written as
Fe(s) Fe3+ + 3e
Fe(OH)3(s) + 3e Fe(s) + 3OH
Overall reaction is i.e., by adding
i.e. E = E0
OH /Fe(OH)3 /Fe
E0
OH /Fe(OH)3 /Fe
E =
E0
Fe2 /Fe
can be calculated if we know E and E can be calculated as follows
0.0591
0.0591 (36.4)
log10 36.4
0.3
3
0.75V
EOH/Fe(OH)3 /Fe = 0.75 0.036 = 0.786V

526. Answer (3)
Larger cation, more ionic mobility.
Physical Chemistry
67
527. Answer (2)

o
Eocell = EFe
E oCr 3 / Cr
2
/ Fe
528. Answer (2)

Li has maximum reducing power.
529. Answer (3)
WAg
WMg
E Ag
EMg
530. Answer (3)
BaSO4 = (C1 2C2 + C3)

M
0.01
= (C1 2C2 + C3)
1000
1000
K=
530a. Answer (3)
[JEE (Main)-2014]
According to Debye Huckle onsager equation,
C A C
Here A = B
C B C
531. Answer (2)

Pb(s) + CaC2O4(s) PbC2O4(s) + Ca+2 + 2e
532. Answer (2)
Temperature coefficient becomes minimum.
533. Answer (3)
Example : Pt | Sn+2, Sn+4
534. Answer (1)
E = Eo
0.0591
log [H+]2 = Eo + 0.0591 pH
2
E1 E2 = 0.0591 [(pH)1 (pH)2]

535. Answer (2)
After electrolysis aqueous NaCl is converted into aqueous NaOH
The quantity of electricity passed =
0.250 35 60
F = 5.44 103 F
96500
The number of equivalents of OH ion formed = 5.44 103

Molarity of NaOH =
5.44 10 3
1.36 10 2
0.4L
POH = log (1.36 102) = 1.87

pH = 12.13
536. Answer (3)
=
G
H
68
Physical Chemistry
536a. Answer (3)
(AIEEE 2009)
CH3OH(l) +
3
O (g) CO2(g) + 2H2O(l)
2 2
Greaction = Gproducts Greactant

= [394.4 2 237.2] [166.2]
= 702.6 kJ
G
100
H
We know, efficiency of a fuel cell,
702.6
100
726
97%
537. Answer (2)

M
C 2
=
,K=
1
538 Answer (2)
CHCOOH + H2O
CH3COO + H3O
c
48.15
0.1232
x (degree of ionisation) = =
390.7
0
Ka(ionisation constant) =
cx2
1.0283 10 3 (0.1232)2
=
= 1.78 105
(1 x)
(1 0.1232)
Current = conductance potential difference

Equivalent conductance c =
97.1 (ohmcm2equiv1) =
1000 conduc tance cell constant

normality
1000 conduc tance 0.50cm1

0.1(equivalent cm 3 ) 1.50
conductance = 0.02913 ohm1

current = 0.02913 5 = 0.1456A
538a. Answer (1)
[JEE (Main)-2014]
For 0.2 M solution

R = 50
= 1.4 S m1 = 1.4 102 S cm1
1
1
cm
1.4 10 2
Now, R
l
a
l R
50 1.4 10 2
a
Physical Chemistry
69
For 0.5 M solution

R = 280
=?
l
50 1.4 10 2
a
l
a
1 1 l

R a
1
1
50 1.4 10 2 =
70 10 2 = 2.5 103 S cm1
280
280
Now, m
1000
2.5 10 3 1000
=
= 5 S cm2 mol1 = 5 104 S m2 mol1
M
0.5
539. Answer (3)
dE
S
=
dT
nF
540. Answer (3)
Order of deposition, Br > OH > N O3 > F
541. Answer (1)
E > 0, Q < 1.
541a. Answer (4)
(AIEEE 2011)
1
H2
H e
2
Apply Nernst equation
1
PH 2
0.059
E0
log 2
1
[H ]
E
0.059
21/2
log
1
1
Therefore E is negative.
542. Answer (4)
E = Z 96500
543. Answer (1)
Fact.
544. Answer (3)
Electrons released from Fe move towards impurity.
545. Answer (1)
546. Answer (2)
Cell is used for prepation of NaOH.
70
Physical Chemistry
547. Answer (4)

1 Eq of H2O will evolve 11.2 L H2 and 5.6 L O2 at NTP.
548. Answer (3)
No relation with reactions.
549. Answer (2)
H2O
1
O + 2e, H2O2 O2 + 2e
2 2
550. Answer (1)

wq
551. Answer (3)
electrolys is
NaH
Na
( cathode)
1
H2 (g)
2
anode
551a. Answer (2)
[JEE (Main)-2014]
On electrolysis only in case of Ca2+ salt aqueous solution H2 gas discharge at Cathode.
Case of Cr
At cathode : Cr3+ + 2e Cr
So, Cr is deposited.
Case of Ag
At cathode : Ag+ + e Ag
So, Ag is deposited.
Case of Cu
At cathode : Cu2+ + 2e Cu
Case of Ca2+
At cathode : H2O + e
1
H + OH
2 2
552. Answer (1)

w=
E
it
96500
553. Answer (4)

E1 E2 =
0.0591
[Cu 2 ]1
log
2
[Cu 2 ] 2
554. Answer (2)

Go = nF Eocell = 2 96500 1.10 J
555. Answer (4)
1
+
H2

H +e
2
K = [H+] = C1
E = E 0.0591 logC1
Physical Chemistry
71
E decreases if C1 increases
1

Cl
Cl2 e
2
1
1
K
[Cl ] C2
E = E + 0.0591 logC2
E increases if C2 increases
+
Ag

Ag + e
K = C3
E = E 0.0591logC3
E decreases if C3 increases
556. Answer (2)
557. Answer (4)
For spontaneous cell reaction, E > 0.
557a. Answer (3)
(AIEEE 2012)
558. Answer (1)
G3 = G1 + G2
n3E3 = n1E1 n2E2
+3E3 = 2 1.26 1 0.336
E3 = 0.728 V
559. Answer (2)
Cu does not react with dilute H2SO4.
560. Answer (2)
w=
E
it
96500
127
1
10 =
i 60 60
96500
i = 2.11 A
561. Answer (2)
It requires no gaseous reactant.
562. Answer (1)
Eo = +0.22 1.36 = 1.14 V
E Eo
0.059
log PCl2
1
w max = G = nFE = (1) (1.14) 96500 103

=110 kJ mol1
72
Physical Chemistry
563. Answer (4)

2 1.6 1019C is carried by 1 molecule of Zn2+
2 105 C is carried by =
1
2 105
2 1.6 1019
1
1
moles
14
N0
1.6 10
1
1.6 6.023 1014 1023
= 1010
564. Answer (2)

0 (BaSO4 )
Normality =
Molarity =
1000 sp.conduc tance

conc.(Normality)
1000 8 10 5
400
Normality
10 4 M
2
Ksp = S2 = 108 M2
565. Answer (3)
Ecell ECu2 /Cu ECr3 /Cr

= 0.34 ( 0.74) = +1.08 V
566. Answer (4)
E
Cu /Cu
0.5208 V
+
Ag + e ; EAg/Ag+ = 0.80V
Ag
AgI+e
Ag + I ;
+
Ag + I
AgI
EI / AgI/Ag+ = 0.15V
ECell = 0.95V
K = [Ag+] [I] = Ksp

ECell =
0.0591
log k sp
1
0.95
log K sp
0.0591
Ksp = 8.42 1017

567. Answer (2)
Ecell 0.003
D
0.059
log 0 at equilibrium
H
2
D
0.006 0.059log
H
D
D
0.102 log 100.102 1.2
H
H
Physical Chemistry
73
568. Answer (3)

569. Answer (3)
570. Answer (1)
The fraction of collision with sufficient energy i.e., e E a / RT becomes unity only at Ea = 0.
571. Answer (4)
k=
a
2.303
log
t
a x
at time (t/2) seconds
a
0.6932 2.303
log
t
( t / 2)
a x
a
0.6932
log
2 2.303
a x
a
0.15
log
a x
a
1.413
a x
a = 1.413a 1.413x
0.413a = 1.413x
x 0.413
a 1.413
% fraction of element decayed =
0.413
100
1.413
= 29%
572. Answer (1)
t 1/ 2 &
1
a
n 1
where n is order of reaction
for zero order reaction n = 0

t1/2 & a
573. Answer (4)
On decreasing the volume of vessel the to half conc. of A and B are increased by factor of
2 times
rate will be increased by a factor of 4 times
574. Answer (2)

For the completion of 75% reaction 2 half life requires
2 t1/2 = 50
t1/2 = 25 mins
74
Physical Chemistry
574a. Answer (2)

t1/2 =
ln 2
k
k=
(AIEEE 2009)
2.303 0.301
6.93
a
2.303
log
k
a 0.99a
Also, t =
1
2.303
t = 2.303 0.301 6.93 log 0.01 = 46.05 minutes
575. Answer (3)

Rate = k[0.1]m [0.2]n = 2 103
(i)
(ii)
(iii)
k[0.1] [0.4] = 4 10
k[0.2] [0.2] = 2 10
dividing equation (i) by (ii)
1 1
2 2
n=1
dividing equation (i) by (iii)

1
2

m=0
Rate = k[A]0 [B]
575a. Answer (4)
[JEE (Main)-2014]
2A B C D
Rate of Reaction =
1 d[A]
d[B]
d[C] d[D]
2 dt
dt
dt
dt
Let rate of Reaction = k[A]x[B]y

Or,
d[C]
k[A]x [B]y
dt
Now from table,

1.2 103 = k [0.1]x[0.1]y
...(i)
1.2 103 = k [0.1]x[0.2]y
...(ii)
2.4 103 = k [0.2]x[0.1]y
...(iii)
Dividing equation (i) by (ii)
1.2 10 3 k[0.1]x [0.1]y
1.2 10 3 k[0.1]x [0.2]y
1
1
2
y0
Physical Chemistry
75
Now Dividing equation (i) by (iii)
1.2 10 3 k[0.1]x [0.1]y
2.4 10 3 k[0.2]x [0.1]y
1
1
2 2

x 1
Hence
d[C]
dt
k[A]1[B]0 .
576. Answer (3)

Temperature cofficient is the ratio of rate constant when the temperature differ by 10
75
32 K
65
16 K
55
8K
45
4K
35
2K
25 K
Since the value of rate constant will be increased by 32 times therefore the rate will be increased by 32 times.
577. Answer (1)
t1/2 a
t1/2 = ka
log t1/2 = log k + log a
y = c + mx
m=1
= 45
578. Answer (3)

k = A e Ea / RT
when Ea = 0
The k = A, it means rate constant is independent of temperature
k rate constant at 330 K will be 4.5 105 sec1
579. Answer (1)

k=
x
10
for zero order reaction =
= 10
t
1
In second case k =
20
= 10
2
30
= 10
3
Since rate constant (k) is equal in each case therefore reaction follows the zero order mechanism.
In third case k =
580. Answer (1)

k1
Value of k1 is the least, therefore the conversion A
B is the slowest and rate determing step of the
reaction.
76
Physical Chemistry
581. Answer (4)

r1 = k[A]
1st order reaction
r2 = k[A]2
2nd order reaction
r3 = k[A]3
3rd order reaction
When the rate constant k is same for three reaction it is clear that
r1 = r2 = r3 when [A] = 1
r1 > r2 > r3 when [A] < 1
r1 < r2 < r3 when [A] > 1
582. Answer (3)
Energy
Ea
H
R
z
Reaction progress
It is clear from the graph that Ea should be greater than H.

583. Answer (3)
CH3COOC2H5 H2O CH3 COOH C2H5 OH

( excess)
rate law = k[CH3COOC2H5 ]

order of reaction = 1
molecularity = 1 + 1 = 2
584. Answer (2)
Since the half life of first order reaction is independent of initial conc.
585. Answer (2)
CH3COOC2H5 + NaOH CH3COONa + C2H5OH
Rate = k[CH3COOC2H5 ] [OH ]
Order of reaction is 2
586. Answer (4)

At intersection of two curve the concentration of A and B are equal (i.e., half of the reactant converted into
products) therefore it represent the half life of A.
587. Answer (2)
Rate = k[A][B]2 since [A] is taken in excess therefore its concentration remain almost constant
Rate = k[B]2 k [A] = k
Order of reaction = 2
588. Answer (2)

Positive catalyst increases the rate of chemical reaction by lowering of activation energy of system.
Physical Chemistry
77
589. Answer (2)

k = A e Ea / RT
ln k = ln A
Ea
RT
y = c + mx
slope of graph =
Ea
R
590. Answer (1)

A (g)
2 B (g) C (g)
t 0 PA 90
t t 90 x
After time t
0
2x
0
x
90 + 2x = 180
x = 45
k=
2.303
90
log
10 60
90 45
0.6932
10 60
= 1.155 103 s1
591. Answer (1)
592. Answer (3)
Heat of the reaction H = Ea f Eab
H = x
and the activation energy of reverse reaction is also x.

593. Answer (2)
Rate = k[NO2] 2
Rate of reaction is independent of concentration of CO.
594. Answer (2)
Rate of reaction = [A]a
[A]I = 2.2 M
[A]II =
2 .2
= 1.1 M
2
r1 = 2.4 M s1
r2 = 0.6 or
2 .4
4
On reducing the conc. of A to half the rate of reaction is decreased by 4 times.

595. Answer (2)
596. Answer (1)
Rate constant depends only on temperature.
596a. Answer (1)
(AIEEE 2012)
597. Answer (1)

78
Physical Chemistry
598. Answer (3)

Rate = k[ester] [H+ ]
K H2SO 4 K [H ]H2SO 4
KHCl = K[H+] HCl

Since [H+] is obtained from H2SO4 is more than HCl therefore K H2SO4 K HCl .
599. Answer (3)
Since concentration of increases time to time but not linearly.
600. Answer (1)
d [I ]
1 d [I ]
2
2 dt
dt
d [I ] 0.5 0.46
0.004 M min 1
dt
10
d [I2 ]
0.002 M min 1
dt
601. Answer (2)

Rate = k[A]
8.75 105 = k(0.5)
k = 17.5 105 s1
= 1.75 104 s1
602. Answer (4)
Since the concentration of H2O2. If (first order reaction) decreases with the time as (at = a0 e kt ) therefore graph
(4) is correct.
603. Answer (2)
t = 144 = 1.44 100
= 1.44 t1/2,
=
tav =
N
N
e = 0 0 e e
N
N
t
N=
N0
e
604. Answer (4)

t=
2.303
a
2.303
log
2
=
k
a 0.99a
k
t=
2.303 2
k
1
t = 2.303 2 = 4.604 tav = 4.6
k
Physical Chemistry
79
605. Answer (2)

Ea
K 2Ea K 2Ea
K 2 K a
1.0 10 2 60 3.0 10 2 70
1.0 10 2 3.0 10 2
= 67.5 kJ mol1
606. Answer (3)

Rate = k[A]x [B] y
R = k[A]x [B]y
(i)
R
= k[2A]x [2B]y
2
(ii)
R
= k[2A]x [B]y
4
(iii)
Dividing equation (ii) by (iii)

2 = [2] y
y=1
dividing equation (i) and (iii)
1
4=
2
x = 2
607. Answer (2)

CA 2, CB 4
608. Answer (3)
t1/ 2
1
a
n 1
t1/2 an 1 = constant
n=2
609. Answer (3)

t1/2 =
t =
0.6932
k
2.303
100 2.303
log
log1000
k
0 .1
k
6.909
k
t = 10 t1/2
80
Physical Chemistry
609a. Answer (2)

t1/2 =
ln 2
k
k =
(AIEEE 2009)
2.303 0.301
6.93
Also, t
a
2.303
log
k
a 0.99a
1
2.303
6.93 log
2.303 0.301
0.01
= 46.05 minutes
610. Answer (3)
k2
e(E1 E 2 ) / RT
k1
E1 E 2
2
2 .5
3
RT
2 10 400
k2
e 2 .5
k1
k 2 e 2 .5 k 1
611. Answer (1)
At very high conc. of NH3
1 + k2 [NH3 ]
rate =
k2 NH3
k 1[NH3 ]
constant
k 2 [NH3 ]
This follows the zero order kinetics therefore rate is independent of conc. of NH3 .
612. Answer (3)
A (g)
2 B (g) C (g)
initial pressure
P
0
After reaction P P
0
2P
0
P
total pressure after the reaction

P0 P + 2P + P = Pt
2P = Pt P0
Pt P0
P =
2
Physical Chemistry
81
P0
2.303
log
=
P0 P
t
2.303
P0
log
t
0 P P0
P t
2 P0
2.303
log
=
3 P0 P
t
t
613. Answer (2)

After the expiry of 40 mins the reactant A decomposes to 75% therefore
A (g)
B (g)
Initial pressure
400
0
3
3
After t 40 mins 4001
400
4
4
C (g)
0
3
400
4
total pressure of reaction mixture

3
3
3
= 400 1 400 400
4
4
4
= 400 400
3
4
= 400 + 300
= 700 mm of Hg
614. Answer (1)
Let N0 and N be the number of atoms of the radioactive substance present at the start and after 5 minutes
respectively rate of disintegration at the start = N0 = 275 and the rate of disintegration after 5 minute = N
= 270 dividing both,
Or,
N0
1.76
N
We know that
N0 475
N
270
N
2.303
log10 0
t
N
2.303
log10 1.76 = 0.113 minute1
5
Half life period =
0.693 0.693
6.1 minute
0.113
82
Physical Chemistry
615. Answer (4)

7500 0.012 0.35
100
100
Weight of radioactive potassium =
= 0.0315 g
Activity =
Activity =
0.693
Weight
t1/2
Atomic weight Avogadros number
0.693
1.3 109 365 24 60
0.0315
6.023 1023
40
= 4.81 105 dpm

616. Answer (2)
% of y =
k1
100
k1 k 2
2.5 10 3
2.5 10 3 1.25 10 2
100
2.5 10 3 10 2
1.50 10 2
25
1.50
= 16.66%
% z = 100 16.66 = 83.34%
617. Answer (2)
K1
Bicyclohexane
K2
Cyclohexene
Methyl cyclopentene
K1
Percentage of cyclohexene = K K 100
1
2
1.26 104
1.26 104 3.8 10 5
100
= 77%
% of methy cyclopentene = 23%
618. Answer (2)
kf = 4 104
kb = 2 104
keq =
kf
4 10 4
2 10 8
4
kb
2 10
Physical Chemistry
83
619. Answer (1)

k 500 A e Ea / R 500
(i)
k 400 A e (Ea 20 ) / 400 R
(ii)
from equation (i) and (ii) we get
Ea
(E 20)
a
500 R
400 R
4 Ea = 5 Ea + 100
Ea = 100 kJ mol 1
620. Answer (4)
Rate = k[N2O5 ]
2.4 105 = 3 105 [N2O5 ]
[N2O5 ] =
2.4
0 .8
3
621. Answer (1)

The rate constant of the decay is
0.693 0.693
t1/2
22
If K 1 and K2 are the rate constants of the reactions leading to

0.693
K1 + K2 =
22
222th
and Fr223, respectively we have
K1
2
K 2 98
On solving for K1 and K2 we get

K2 = 0.030871y1
K1 = 0.000631y1
622. Answer (4)
t t1
2
N
ln N
. 0
ln 2
N0 24 N 48 g
0
623. Answer (4)
0.693
4.5 109
t
2.303
4 1
log
t
4
2.303 4.5 109

10
log 3
0.693
2
2.303 4.5 109
0.1
0.693
= 1.445 109 years

84
Physical Chemistry
624. Answer (4)

Rate = k[A]n
r1 = k[A]n
8r1 = k 4n.[A]n
2n = 3 n = 1.5
625. Answer (3)
X is intermediate.
626. Answer (2)
Ea
K1E1 K 2E2 102 60 3 102 70
K1 K 2
102 3 102
= 67.5 kJ mol1
627. Answer (4)
Apply
x
ap
. At high P, 1 + bp bp.
m 1+ bp
628. Answer (3)

Based on definition of peptization.
629. Answer (3)
Size of clay particles is greater than 100 nm.
630. Answer (4)
The size of crystalline particles are very small as compare to diameter of pores of membrane.
631. Answer (2)
Fluorescein and Eosin are examples.
632. Answer (1)
633. Answer (3)
634. Answer (3)
635. Answer (3)
Higher the critical temperature higher the adsorption of gas.
636. Answer (4)
637. Answer (4)
Catalyst decreases activation energy hence rate constant increases.
K Ae
Ea
RT
A
Ea
e RT
As Ea decreases, K increases
Hence rate of reaction increases.
Physical Chemistry
85
638. Answer (4)

639. Answer (2)
Colloids of metal and their sulphides are prepared by special methods not by simple mixing.
640. Answer (3)
Lyophilic colloids not easily coagutated and are highly stable.
641. Answer (3)
Kraft temp. = Temp. above which micell is formed.
642. Answer (2)
643. Answer (3)
Brownian motion is zig-zag motion responsible for stabilisation of colloids and it prevent the colloidal particle
to settle down.
644. Answer (2)
2Au(sol) + 3HCOOH + 6HCl
2AuCl3 + 3HCHO + 3H2O
645. Answer (2)

Cellulose is a polymer having very large particle size.
646. Answer (3)
Fauzasite is natural, Na56[(AlO2)56(SiO2)136] 250 H2O.
647. Answer (2)
Chemisorption is irreversible.
648. Answer (3)
KI
KI
AgNO3 AgI
[AgI] I
649. Answer (2)

For adsorption, S < 0, H < 0, G < 0.
649a. Answer (3)
(AIEEE 2009)
Physisorption is an exothermic process with H 20 kJ/mol

650. Answer (3)
More contact with catalyst, faster rate of hydrogenation.
651. Answer (4)
In Bergious process Fe2O3 is used as catalyst.
652. Answer (1)
Brownian movement is independent to nature of solute.
653. Answer (2)
Due to very high difference between refractive indices of dispersed phase and dispersion medium.
654. Answer (1)
Proteins in acidic medium is positively charged and in basic medium, negatively charged. Au and CdS are
negatively charged.
86
Physical Chemistry
655. Answer (4)

Z=
4
D
656. Answer (1)

Ferric hydroxide is positively charged colloid.
657. Answer (1)
Gold numbers
Potato starch = 25
Gum Arabic = 0.15
Haemoglobin = 0.03
Gelatin = 0.001
658. Answer (4)
Both emulsions show different properties in given tests.
659. Answer (2)
It can describe only physisorption.
660. Answer (2)
It is an example of induced catalysis.
661. Answer (1)
Micelle formation takes place only above a certain temperature, hence, H = +ve
662. Answer (1)
Fact
663. Answer (4)
Fact
664. Answer (1)
Fact


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SA 15 16 XII XII Chemistry Unit-1 Section-A

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Physical Chemistry

Section - A : Straight Objective Type

Total number of Ag + ions = 0.6 + 0.6

Moles of Cl released by 200 ml of 10 M

68 g of H2O2 liberates 22.4 L of O2

volume strength = 9.88

Success Achiever (Solutions)

% of MgCO3 in the mixture = 38.2%

(molar mass of KClO4 = 138.5)

Success Achiever (Solutions)

Number of moles of KClO3 decomposed to give 2.85 103 moles of KClO4

= 3.8026 103 122.5 g KClO3 = 0.466 g of KClO3

Amount of KClO3 used in 1st reaction = 1.034 g of KClO3

Number of moles of O2 formed by 8.44 103 moles of KClO3

Volume occupied by 0.01266 moles of O2 = 0.01266 22.4 L = 283.6 ml

From the above balanced equation

0.01 mole of FeC2O4 are oxidised by

Volume of 0.01 M KMnO4 solution required

10. Answer (1)

Number of milli equivalent of NaOH in 25 ml = 5.6

Weight of NaOH in the solution =

y = 14.4 5.6 = 8.8

Weight of Na2CO3 of solution =

Success Achiever (Solutions)

11. Answer (1)

No. of neutron in 1H2 = 1

13. Answer (4)

14. Answer (3)

18. Answer (1)

No. of moles of compound

19. Answer (2)

20. Answer (4)

1000 0.8 400

21. Answer (1)

Success Achiever (Solutions)

22. Answer (2)

100 ml of 1 M Ca(OH)2 will neutralize 10 ml of 20 N H2SO4 completely.

Thus, the resulting solution will be neutral.

26. Answer (3)

(3) is the correct answer.

27. Answer (1)

Success Achiever (Solutions)

28. Answer (2)

AgNO3 NaCl AgCl NaNO3

68 g of AgNO3 = 0.4 moles

NaCl is limiting reagent

Hence 0.2 moles of AgCl is formed.

15 ml of solution will be left unneutralized

Nature of solution = acidic.

32. Answer (4)

The mole fraction of methanol =

33. Answer (1)

Success Achiever (Solutions)

36. Answer (4)

AB3 = HN3 acid

Metal chloride = MCl

38. Answer (1)

The number of atoms of B =

Mole formula = A2.2988 B1.15

39. Answer (3)

Total Mg in sample = 2.5 + 3.157 = 5.657 g

40. Answer (2)

100 0.2 = 40 NH2SO4

Success Achiever (Solutions)