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4. Answer (3)
3% solution of H2O2 means
100 ml H2O2 solution — 3g H2O2
1000 ml H2O2 solution — 30g H2O2
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5. 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 5 .6
158 56
60
x 5 5 .6
1000
= 18.96 g
18.96
% purity of KMnO4 = 100 63.2%
30
7. 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
3 98 1000
100
d
49
3 10 d
98
d = 0.6 g/ml
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Success Achiever (Solutions) Physical Chemistry 3
8. Answer (1)
0.395
Number of moles of KClO4 formed = (molar mass of KClO4 = 138.5)
138.5
= 2.85 × 10–3
Number of moles of KClO3 decomposed to give 2.85 × 10–3 moles of KClO4
4
= 2.85 10 3
3
= 3.8026 × 10–3 moles of KClO3
= 3.8026 × 10–3 × 122.5 g KClO3 = 0.466 g of KClO3
Amount of KClO3 used in 1st reaction = 1.034 g of KClO3
= 8.44 × 10–3 moles of KClO3
Number of moles of O2 formed by 8.44 × 10–3 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
1
Number of moles in 1.44 g of FeC2O4 = 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 mole of FeC2O4 are oxidised by 0.01 = 0.006 moles
5
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
y
x 50 0.2
2
2x + y = 10 × 2 = 20
x + y = 72 × 0.2
x + y = 14.4
x = 20 – 14.4
= 5.6
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4 Physical Chemistry Success Achiever (Solutions)
5.6 40
Weight of NaOH in the solution = = 0.224 g
1000
y = 14.4 – 5.6 = 8.8
Number of milli equivalent of Na2CO3 in 25 ml of solution = 8.8
8.8 53
Weight of Na2CO3 of solution = 0.4664 g
1000
WNaOH 0.224
0.48
WNa2CO3 0.4664
4
No. of mole of 1H2 4
1
13. Answer (4)
1 1 1
u= th wt. of C-12 atom = th wt. of O-16 atom = th wt. of C-14 atom
12 16 14
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)
1 5
No. of atom = 5 NA NA
4 4
18. Answer (1)
x A 1000
m
xB 18
5.2 5.2
x 0.086
55.5 5.2 60.7
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19. Answer (2)
1
Given V.D. of A = ( V.D)B and molecular mass of B = x = 2 × V.D. of B
6
Molecular mass of A = 2 × V.D. of A
1
= 2 VB
6
1
= 2 VB
6
x
=
6
26. Answer (3)
Molecular mass of CH3OH = 12 + 4 + 16 = 32
12
% of C in CH3OH = 100 37.5%
32
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12
% of C in CO2 = 100 27.27%
44
48
% of C in CH3CH CHCOOH = 100 55.8%
86
24
% of C in COOH–COOH = 26.6%
90
200
% concentration of new solution = 100 25%
800
100
14 g of N in 14 g of compound
12
= 116.67 g
21
84 1000 1.25 M
Molarity of the solution =
200
1.25 × 25 = x × 1250
x = 0.025 M
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31. Answer (1)
1
100 × 0.5 + 200 × × 2 N = 600 × x
4
N
x = 0.25
4
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)
50
32
The mole fraction of methanol = = 0.59
50 50
32 46
33. Answer (1)
34. Answer (4)
35. Answer (2)
MgCO3 MgO CO 2
84 g 40
40
Weight of MgO = 42 20 g
84
24
12.5 g of MgSO4 = 12.5 = 2.5 g of Mg
120
5.657
% of Mg in sample = 100 22.63%
25
NH2SO4 0.5 N
0 .5
Molarity of H2SO4 = 0.25 M
2
41. Answer (2)
12
% composition of CH : C 100 92%
13
12 2
% composition of CH2O : C 100 40% H 100 6.7%
12 2 16 30
36
% composition of C3H6O : C 100 62%
36 6 16
36
% composition of C3H4O2 : C 100 50%
36 4 32
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Success Achiever (Solutions) Physical Chemistry 9
⎛ Y⎞ Y
C XHY ⎜ X ⎟ O2 XCO2 H2 O
⎝ 4⎠ 2
⎛ Y⎞
Oxygen atoms required = 2 ⎜ X ⎟
⎝ 4⎠
As per information,
⎛ Y⎞
2 ⎜ X ⎟ 2Z
⎝ 4⎠
⎛ 2⎞
⎜1 ⎟ Z
⎝ 4⎠
Z = 1.5
Molecule can be written
CXHYOZ
C1H2O3/2
C2H4O3
100
65.38 g of Zn is present in 65.38
0.26
= 25146
= 2.5146 × 104 g
x + 2(16 + 1) = 171
x = 171 – 34
= 137 g
137
Equivalent mass of metal is = 68.5 g
2
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10 Physical Chemistry Success Achiever (Solutions)
12 × 1 = 15 × NH2SO4
12
NH2SO 4
15
= 0.8
MH2SO4 0.4 M
22.4
22.5 g of a gas occupies 22.5 = 5.6 L
90
48. Answer (4)
0.01 M K2Cr2O7 0.06 N K2Cr2O7
W
0.06 × 50 = 1000
152
= 0.456 g
0.456
% purity of sample = 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
2 122 .5
0.384 g O2 is obtained by 0.384 = 0.98 g KClO3
3 32
0.98
% of KClO3 decomposed = 100 = 10%
9 .8
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
0.47
% of NaCl = 100 47%
1
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Success Achiever (Solutions) Physical Chemistry 11
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)
4.5
112 L of gas weighs 112
5 .6
= 90 g
53. Answer (1)
12.25
0.5 1000 (x is the basicity)
98
x
500
x=2
Acid has been neutralized to HPO42–.
54. Answer (4)
The balanced chemical equation is
254 g = 630 g
Thus, HNO3 required for 5 g iodine
630
= 5 12.4 g
254
55. Answer (4)
5 3
AsO34 AsO33 nf 2 ; I I2 nf 1
1.5 1022 1
n 23
mole electrons
6.02 10 40
1
I I2 e
2
1 1
mol mol
80 40
1
wt. of iodine = w = × 254 = 3.2 g
80
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11
2FeS2 O2 Fe2 O3 4 SO2
x mol 2 2x mol
11 x
mol
4
11x 1 11x
⇒ mol O2 13.1 x
4 0.21 4
16.6 x
⇒ %N2 100 81.97%
20.25 x
z2
The number of revolution = 6.55 × 1015 ×
n3
12
= 6.55 × 1015 × = 2.43 × 1014
33
t n3
t1 33 27
= 3 =
t2 4 64
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Success Achiever (Solutions) Physical Chemistry 13
y 2x – 0
=
4y 3 x – 0
8x – 40 = 3x – 0
5x = 30
5x
0 =
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.
n (n – 1)
= K, where n = number of unpaired electrons having similar spin
2
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
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h h h
orbital angular momentum = l (l 1) = 2 (2 1) = 6
2 2 2
72. Answer (4)
4s 3d
1 6
s = 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)
p 2 4mp 2 ev 2 2
2 mp .ev 1
e4 Z2
I.E.
802h2n2
where is reduced mass.
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Success Achiever (Solutions) Physical Chemistry 15
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
– 2 =– H
n 9
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.
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 ⎢ 1 1⎥ ⎡1 1 ⎤ R34
–
max = RZ2 ⎢ 2 2 ⎥ = R (2)2 ⎢ – ⎥ = = 3R
⎣ n1 n2 ⎦ ⎣1 4 ⎦ 4
1
max =
3R
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16 Physical Chemistry Success Achiever (Solutions)
h
Hence, =
m
h
2 =
m
h
=
m
96. Answer (3)
We know that,
nh
mvr =
2
nh
v=
2mr
frequency (number of revolutions per sec)
velocity
=
circumference
v
=
2 r
nh
= 2mr
2r
nh
= s–1
4 2mr 2
97. Answer (4)
1
2p contains 6 electrons out of which only 3 electrons have spin – .
2
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Success Achiever (Solutions) Physical Chemistry 17
1
n = 4, l = 0, m = 0, s = ±
2
1
Hence n = 5, l = 0, ml = 0, ms
2
h
x.m v
4
h
v.mv
4
h
(v)2 =
4m
h
v =
4m
h mh 1 mh
p = mv = m = =
4m 4 2
103. Answer (1)
m1 m2 m2 m
m1 m2 2m 2
RH
Rydberg's constant
2
104. Answer (3)
n2
rn 0.53 Å
Z
105. Answer (1)
L 1
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Success Achiever (Solutions) Physical Chemistry 19
123. Answer (3)
Element Electronegativity
F 4.0
O 3.5
Cl 3.2
N 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)
1
For isoelectronic species, size .
Atomic number
O 2 O 2 O 2– O 2–2
2 .5 2 1 .5 1
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Success Achiever (Solutions) Physical Chemistry 21
P—Cl
Cl Cl
154. Answer (3)
H
54°44'
C 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)
.. ..
O
H H
160. Answer (2)
obs
Percentage ionic character = × 100
th
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22 Physical Chemistry Success Achiever (Solutions)
F F
Structure of I3–
–
I
CH=CH2
F Cl
P F
F
Cl
167. Answer (2)
Fact.
168. Answer (4 )
Larger anion, easier polarisation.
169. Answer (3)
Smaller ionic radius, larger hydration radius.
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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 Cl F
P F , P Cl
Cl Cl
Cl F
>0 =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.
176. Answer (2)
O 2–2 contains zero unpaired electrons.
177. Answer (3)
O
||
P
O O
O
4- bonds O=P—O P=O
O O
P
||
O
178. Answer (4)
1
Polarising power of cation
Size of cation
179. Answer (4)
Peroxide are diamagnetic
2 2 2 2 2 2 2 1 1
O2 : 1s *1s 2s * 2s 2pz 2p 2p * 2p * 2py
x y x
2 2
S2 : 1s *1s 22s *22s 22pz 2p
2 2
2p *22p *22py
x y x
*22pz 3s
2 2
*3s 2
3p 2 2 *13px *13py
z 3p x 3p y
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B
Cl Cl
181. Answer (1)
Due to more negative charge on F–
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Success Achiever (Solutions) Physical Chemistry 25
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 180º.
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26 Physical Chemistry Success Achiever (Solutions)
NO2– sp2
NO3– sp2
NO2 sp2
NO2 sp
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
Charle’s 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.
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Success Achiever (Solutions) Physical Chemistry 27
209. Answer (3)
W
PV = RT
M
200 0 .5
0.821 0.0821 400
1000 M
M = 100
Molecular weight of C2F4 = 2 × 12 + 4 × 19 = 100.
210. Answer (3)
1
P
V
(3) is not correct representation.
211. Answer (3)
b = 4Vm
where Vm is volume of a gas molecule.
212. Answer (1)
2 2 2 2
1 2 3 4 30
Vrms = 7 .5 .
4 4
⎛ ⎞
⎜ P a ⎟( V b) RT
⎜ 2⎟
⎝ V ⎠
At low temperature and high pressure molecules of gas come closer and hence it favour liquefaction of gas.
2a
Ti
Rb
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28 Physical Chemistry Success Achiever (Solutions)
a
TB
Rb
8a
TC
27Rb
Ti
2
TB
Ti 2 54
6.75
TC 8 8
27
TC 8
0.296
TB 27
TB
3.375
TC
TC
Hence T is least.
B
2
Volume of ozone produced = x
3
Volume of oxygen remaining = 1 – x
2
1 x x 0.8 litre
3
x
1 0 .8
3
x
1 0 . 8 0 .2
3
x = 0.6 litre
2
Volume of ozone = 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.
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Success Achiever (Solutions) Physical Chemistry 29
221. Answer (3)
v 100
r= 10
t 10
x 100
(1) 2 .5
t 40
x 25
(2) 2 .5
t 10
x 100
(3) 10
t 10
x 5
(4) 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)
8a
Tc
27Rb
a
Vc = 3b and Pc 2 .
27b
224. Answer (4)
At high temperature, a and b both negligible hence PV = RT.
PV
Compressibility factor (Z)
RT
(For one mole of real gas)
van der Waal equation
a
(P )(V b) RT
V2
At low pressure
V b V
⎛ a ⎞
⎜⎝ P 2 ⎟⎠ V RT
V
a
PV RT
V
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30 Physical Chemistry Success Achiever (Solutions)
a
PV RT
V
PV a
1
RT VRT
a
So, Z 1
VRT
a
At high pressure can be neglected
V2
⎛ a ⎞
⎜ p + 2 ⎟ (Vm b) = RT
⎝ Vm⎠
p(Vm – b) = RT
pb
Z = 1+
RT
rA vA / t MB
rB vB / t MA
2 MB
1 MA
1 MA
2 MB
MA 1
MB 4
RT
Vm =
P
Vm will be maximum at higher temperature and lower pressure.
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229. Answer (2)
At Boyle’s 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)
2a
Ti
Rb
234. Answer (4)
When temperature Texp < Ti, cooling occurs.
235. Answer (3)
When Texp < Tc, repulsive forces do not develop.
236. Answer (3)
2a 2 27
Ti 304.2 2053.3 K 1780.3C
Rb 8
237. Answer (2)
8
Tc 33 9.8 K 263.2C
27
So, for liquefaction temperature must be maintained below –264°C.
238. Answer (1)
2
⎛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
= tan–1(–1) = 135°
241. Answer (4)
P1V1 P2 V2
T1 T2
242. Answer (1)
PV = constant
1
d
V
At sea level pressure is more hence volume less and density more.
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⎛ V⎞
P1 ⎜ ⎟
PV P1V ⎝ 2⎠
n
RT1 RT1 RT2
P P1 P1 2PT2
⇒ or P1
T1 T1 2T2 2T2 T1
252. Answer (3)
P1V1 = P2V2
g(h1 + 10) × V = g × 10 × 8V. [∵ P = gh]
h1 = 70 m
253. Answer (1)
1
2x + y = 50 H2 + O H 2O
2 2
5
15 mL O2 is in excess C 2H2 + O 2CO2 + H2O
x
2 2 2x
1
CO O2 CO2
y 2 y
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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
9
C2H5SH + 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.
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.
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In order to calculate average energy for C—H bond formation we should know the following data. C(graphite)
C(g), Ho = enthalpy of sublimation of carbon.
1
C O 2 CO 2
2
(s) ( g) ( g)
1 1
ng = 1 – =
2 2
1
H – U = ng RT = × R × 298 = 149R
2
15
C6H6 (l) O2 (g) 6CO2 (g) 3H2O(l)
2
15 3
n g 6
2 2
H = U + ngRT
⎛ 3⎞ 3
= 3263.9 ⎜ ⎟ 8.314 298 10
⎝ 2⎠
= –3263.9 + (–3.71)
= –3267.6 kJ mol–1
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270. Answer (2)
Bond energy of O—H bond = 109 kcal/mol means that when 1 mole of O—H 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 O—H bond (H—O—H).
Hence energy released = 2 × 109 = 218 kcal.
1
II. H2(g) + O (g) H2O(l); H = –286.20 kJ
2 2
Adding I & II we get,
1
H2(g) + O (g) H+(aq) + OH–(aq)
2 2
H = 57.32 – 286.2
= –228.88 kJ
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At equilibrium G = 0
H 276.5 3
Teq = = = 414.75 K
S 2
3
CH3OH + O CO2 + 2H2O, H = y
2 2
1
CH4 + O CH3OH H = –ve
2 2
H = x – y = –ve
x–y<0
y > x
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
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285. Answer (3)
Qrev – Wrev
S = =
T T
P1
nRT ln
S = P2
T
P1
S = nR ln P
2
3 2.5
P2 15 bar
0.5
W = –Pext V = –15 × (–2.0) = 30 dm3 bar
2H2O2(l)
2H2O(l) + O2(g)
w = – Pext (4V)
= – nO2 RT
= – 124.5 kJ
work done by O2(g) = 124.5 kJ
228
P–H bond energy = 76 kcal / mol1
3
H H
P P
H H
4(P – H) + (P – P) = 355
or 4 × 76 + (P – P) = 355
(P – P) .E = 51 kcal/mol–1
290. Answer (1)
R
Cp – Cv = R Cv
1
nR
∫ dW nC ∫ dT 1 T T
v 2 1
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283
T 103
87
T > 3253 K (2980°C)
K eq 1
G
°
reaction ⎣
= ⎡⎢ G° ⎤
⎥product
formation ⎦
– ⎡⎢ G ° ⎤
⎣ formation ⎥
⎦reactant
⇒ –RT ln K P = 2× G° – 2 G °
NO 2 NO
⇒ G ° 2 G ° RT ln K P
NO 2 NO
2×86600 – R 298 ln K P
⇒ G °
NO 2
=
2
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1 8.314 298
1364.47
1000
= –1366.93 kJ mol–1
= rG + 0
kf
K 1
kb
57.1 kJ
t
mc
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H2O(l), 10C
S
H2O(l),0C H2O(s),0C
1 S2
S = S1 + S2
273 ⎛ 1440 ⎞
= 2 2 2.303 log 2⎜ ⎟
283 ⎝ 273 ⎠
= –11.84 cal K–1
300. Answer (3)
1
Wirr = 2(70 20) 101 = –2416 cal
4.18
302. Answer (3)
4763.9 ⎞
K = 5.88 × 10–2 exp ⎛⎜ –
⎝ 8.314 573 ⎟⎠
ln 2
⇒ t1 35 s
2
K
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305. Answer (3)
⎛ E⎞
S nF ⎜ 2 96500 1.5 104 = 28.95 JK–1 mol–1
⎝ T ⎟⎠ P
1
H2(g) + S (g) H2S(g) K1 ...(I)
2 2
H2(g) + Br2(g) 2HBr(g) K2 ...(II)
1
Br2(g) + H2S(g) 2HBr(g) + S (g) K ...(III)
2 2
(III) = (II) – (I)
K2
K= K
1
1
HgO(s) Hg(g) + O (g)
2 2
Total pressure at equilibrium = P
Molar ratio of Hg : O2 = 2 : 1
2 1
PHg = P PO2 = P
3 3
1/ 2
KP = PHg × PO2 1/ 2 ⎛2 ⎞ ⎛1 ⎞
= ⎜ P⎟ ⎜ P⎟
⎝3 ⎠ ⎝3 ⎠
2
KP = P3/2
33 / 2
311. Answer (1)
1–
pN2O4 = × 0.5 atm
1
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2
pNO2 = × 0.5 atm
1
pN2 O
2
KP =
p N2 O 4
2
4 2 (0.5)2 (1 ) 2
2= =
(1 )2 (1 – ) 0.5 1 – 2
1 – 2 = 2
22 = 1
1
2 =
2
= 0.707
= 71%
312. Answer (3)
CO Cl2 COCl2
0.1 0 .1 0.3
0.5 0.5 0.5
0.3
0.5
KC = = 15
0.1 0.1
5 5
KP = KC (RT ) ng
KP 1
= (RT)–1 =
KC RT
1
SO2 (g) O (g) SO3 (g)
2 2
KP = KC(RT)x
⎛ 1⎞ 3 1
= 1 ⎜⎝ 1 ⎟⎠ 1
2 2 2
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315. Answer (2)
AgCl(s) Ag+(aq) + Cl–(aq) ...(i)
Ag+ + 2NH3 [Ag (NH3)2]+ ...(ii)
Due to removal of Ag+ through reaction (ii), equilibrium (i) shifts in forward direction.
316. Answer (1)
At 25°C pKb for NH3 = 4.7 (in aqueous solution)
[NH4Cl] = 0.1 M
[NH3] = 0.01 M
for basic buffer
[conjugate acid B] 0 .1
pOH = pKb + log = 4.7 + log = 4.7 + log 10 = 5.7
[ weak base BOH] 0.01
pH + pOH = 14
pH = 14 – 5.7 = 8.3
1 1
pH = 7 +
2
pK a – pK b = 7 + 3.2 – 3.4 = 6.9
2
1 0
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
IP = × 10–8 which is greater than KSP.
8
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According to this equation the concentration of CrO4–2 ions will be half of concentration of Ag+ ions.
[ CO32 ] = 10–4 M
K sp 5.1 109
[Ba2+] = = = 5.1 × 10–5 M
[CO32 ] 104
[50 1]
Final concentration of [SO4– –] = = 0.1 M
[500]
Ksp of BaSO4,
[Ba2+][SO42–] = 1 × 10–10
10 10
[Ba2+][0.1] = = 10–9 M
0.1
Concentration of Ba2+ in final solution = 10–9 M
Concentration of Ba2+ in the original solution.
M1V1 = M2V2
M1 (500 – 50) = 10–9 (500)
M1 = 1.11 × 10–9 M
So, option (3) is correct.
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324. Answer (2)
The pH of Buffer is given by
[Salt]
pH = pKa + log10
[ 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 5 5 0
2SO 2 O2 2SO 3
60 3
at equilibrium 5 – 5 5 – 1 .5
100
5–3 3 .5
2
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3
⎡4⎤
[C]3 ⎢2⎥
⎣ ⎦
Q= = = 16
[ A ] [B] 1 2
2 2
B + C, G° = 2494.2 J
2A
1 1
Now A = , B = 2 and C =
2 2
1
⎛ ⎞
CB ⎜⎝ 2 ⎟⎠
2
Now QC = = =4
A 2 ⎛ 1⎞
2
⎜ ⎟
⎝2⎠
10 –2
Ca(OH)2 = M = 10–2 N
2
= 10–1 equivalent in 100 ml = 1 milliequivalent
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.
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
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0.03 0 0.04
Now [ Ag(CN)2 ] – Ag 2CN– (left from KCN)
0.03 – a a 0.04 a
0.03 0.04
(0.04)2 a
KC = 4 × 10–19 =
0.03
a = 7.5 × 10–18
335. Answer (1)
Initial 0 .2 0 .6 0
N2 3H2 2NH3
At equilibrium 0.2 – a 0.6 – 3a 2a
0.8 40 0.8 40 1
Total mixture is 0.8, 40% of its reacts i.e. 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
0.64 4
Ratio of final to initial mole = = 0.8 =
0 .8 5
336. Answer (2)
1 0 0
NH4HS NH 3 + H2S
( s) ( g) (g)
1– x x x
Total mole of gaseous substances = 2x
1
x H2S = x NH3 =
2
P
pH2S = pNH3 =
2
p2
KP = pNH3 × pH2S = = 64
4
p2 = 256
p = 16 atm.
X(g) Y(g)
XY(s)
P P
2P = 10 bar, KP = P2 = 25
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0.01
Hence [CH3COONa] = M
2
pKa log C
pH = 7 + +
2 2
log 0.005
= 7 + 2.37 + = 8.22
2
339. Answer (4)
B + A– + H2O BOH + HA
C (1 – h) C (1 – h) Ch Ch
mol / L mol / L mol / L mol / L
h2 Kw
Kh = , Kh =
(1 – h) 2 (1 – h) 2
1 10 –14 h2
=
5 10 – 7 5 10 – 7 (1 – h)2
1 10 –7 h
–7 =
5 10 1– h
5h = 1 – h
1
h =
6
h = 0.166
h = 16.6%
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340. Answer (3)
C = 0.1
HA H + A –
C (1 – ) C C
pH = – log10 [H+]
2 = – log10 C
2 = – log10 0.1
log10 0.1 = –2
0.1 = 10–2
10 –2
= = 10–1 = 0.1
10 –1
[HI] 2
K=
[H2 ] [I2 ]
At the initial number of moles of H2 and I2 were same therefore at equilibrium [H2] = [I2]
[HI] 2
47.6 = K =
[I2 ] 2
A B C D
Initially : 1 1 1 1 [D]eq = 1.818 M
Q=1
Q < keq
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A B C D
Equilibrium : 1–x 1–x 1+x 1+x
(1 x)2
102
(1 x)2
1 x
= 10
1 x
1 + x = 10 – 10x
11x = 9
9
x= = 0.818
11
So, equilibrium concentration of 'D' = 1.818 M.
PPCl3 PCl2
PCl5(g) PCl3(g) + Cl2(g) KP =
PPCl5
PCO PCl2
COCl2(g) CO(g) + Cl2(g) KP =
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.
346. Answer (1)
t0 1 0
N2 O 4 2 NO 2
t eq 1 – x 2x
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
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= 2 milliequivalent of HCl
4 2 0
NH4 OH HCl NH4 Cl H2O
4–2 0 2
2
[NH4 Cl] 2
pOH = pKb + log [NH OH] = 4.74 + log = 4.74
4 2
pH = 14 – 4.74 = 9.26
348. Answer (4)
[Ag(H2O)2]+(aq) + NH3(aq) [Ag(NH3)(aq) (H2O)]+ + H2O(I) ...(1)
K1 = 2.0 × 103
[Ag(NH3) (H2O)]+ + NH3(aq) [Ag(NH3)2]+(aq) + H2O(aq) ...(2)
K2 = 8.3 × 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 4–2
H2SO4
Since pH of both is same, H+ concentration has to be equated.
Hence 0.1M 0.05 M H2SO4
350. Answer (2)
AgCl Ag+ + Cl–
KSP = S2
S= K SP = 1.5 10 –10
Kw 1 10 –14
Kn = K = = 2 × 10–10
a 5 10 – 5
0.02
ASC– + H2O HASC OH –
x x
0.02 – x
0.02
[HASC][OH– ] x.x x2
Kn = – = =
[ ASC ] 0.02 – x 0.02
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x2
2 × 10–10 =
0.02
x = 2 × 10–6
[OH–] = 2 × 10–6
1 10 –14
[H+] = = 5 × 10–9
2 10 – 6
10 –2
Number of OH– in 250 ml =
4
= 0.25 × 10–2 = 2.5 × 10–3
1
Soluble mole of Ca(OH)2 = × 2.5 × 10–3 = 1.25 × 10–3
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.
354. Answer (1)
1 mole 0 0
NH2 COONH 4 2NH3 CO 2
1– 2
Total number of moles = 1 – + 2 + = 1 + 2
Average molar mass = 2 × 16 = 32
(1 – ) 78 (2 17) 44
32 =
1 2
32 + 64 = 78
= 0.71875 = 0.72
355. Answer (1)
[Ag2O](s) = [Ag](s) = 1
KP = p O 2
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356. Answer (4)
1
pH = pKW (for pure H2O)
2
1
pH = × 13.26 = 6.63
2
CO (Carbon monoxide) is a lewis base. The C atom tends to donate a pair of e–.
SiCl4 can accept lone pair of electron in d-orbital of silicon hence it can act as Lewis acid.
* Although the most suitable answer is (4). However, both option (4) & (2) can be considered as correct
answers.
e.g. hydrolysis of SiCl4
Cl Cl
H
Si + H2O Si O
Cl Cl Cl H
Cl
Cl Cl
Cl
Cl Si OH + HCl
Cl
Hence option (2), AlCl3 and SiCl4 is also correct.
0.1435
Moles of AgCl formed = 103 mole
143.5
= 5 × 10–4 moles
1000
Strength of H2SO4 = 5 10 4 98 2.45 gL1
20
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1
H2 O H2 O2
2
1 0 0
1
2
∑ n 1
2
2 1 2
XH2O ; XH2 ; XO2
2 2 2
PH2 PO1/22
KP
PH2O
1
1
⎛ 2 ⎞ ⎛ ⎞2
⎜⎝ ⎟ P ⎜⎝ ⎟ P2 3/2 P1/2
2 ⎠ 2 ⎠
⇒ KP
2 1 1 2 1/2
P
2
1 3
N2 H2 NH3 , n 1
2 2
362. Answer (3)
H 2 ⎡⎣S2 ⎤⎦
k1k 2
H2S
0.12 S2
1021 ⇒ S2 10 20
0.1
2
2H S , K a 1 K a2 K eq
H2S
H 2 S2
1 10 7 1.2 1013
H2S
0.22 S2
1.2 10 20
0.1
[S2–] = 3 × 10–20
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HCO3 H
H2CO3
s1 K a1 s1 10 4 103
⇒
s2 K a2 s2 4 10 10 2
⎛ 11.45 103 ⎞
Kc = ⎜ 103 mole/L
⎜ 8.314 298 ⎟⎟
⎝ ⎠
= 4.6 × 10–3 M
371. Answer (3)
1
K p =
(K p )2
1
=
(4 103 )2
106
=
16
= 6.25 × 104 atm
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Hº Sº
log K
2.303 RT R
H
⎛A ⎞
Equilibrium constant K ⎜ f ⎟ e RT
⎝ Ab ⎠
⎛A ⎞ H ⎛ 1 ⎞
ln K ln ⎜ f ⎟ R ⎜⎝ T ⎟⎠
⎝ Ab ⎠
y= C+ m x
Comparing with equation of straight line,
H
Slope =
R
Since, reaction is exothermic, H° = –ve, therefore, slope = +ve.
ln K
A
B 1
(0, 0) T(K)
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379. Answer (1)
The sum of oxidation number of all the carbon atoms = 5(–1) + 0 + 3 = –2.
O–H
(+3)C = O
(0)
(–1) (–1)
(–1) (–1)
(–1)
380. Answer (4)
6 2 3 4
H
Cr 3 Fe 3 C O 2
K 2 Cr 2 O 7 Fe C 2 O 4
(nf 6 ) (nf 3 )
3 1
1 mole FeC2O4 required 1 mole of K2Cr2O7
6 2
381. Answer (2)
–
8 e
N2H4 (N2H4 ) 8 ( y )
2 x 4 8
x 2
2
So, n-factor for HCl = 0 .5
4
M 36.5
Equivalent weight of HCl = 73
0 .5 0.5
2+ –1 +3 +4
Fe S 2 Fe2O3 + SO2
–
–1 e
–
–2 × 5e
M
Total 11 mole of electrons are lost by 1 mole of FeS2. Hence, equivalent weight of FeS2 = .
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)
M
Br2 Br–, equivalent mass of Br2 =
2
M
Br2 BrO3– equivalent mass of Br2 =
10
M M 6M
Net equivalent mass of Br2 =
2 10 10
10 5
n-factor of Br2 =
6 3
393. Answer (2)
O O
– (+5) (0) (0) (+5) –
O —S—S—S—S—O
O O
In which, two sulphur atoms have (+5) oxidation number and two sulphur atoms have zero oxidation number.
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= 0.41 – (–0.74)
= 1.15 V
Pt(s)
1 M HCl
This is schematic diagram of S.H.E.
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.
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1
So, mole of K2Cr2O7 required = 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 2+ +4
Cu2 S Cu + SO2
–
+2 e
–
–6 e
M
Total 8 e– are lost by one molecule of Cu2S. So, equivalent weight of Cu2S = .
8
411. Answer (3)
1 2
CH3 CH CH2
412. Answer (3)
4 4
CO2 , n 4 4 8
CH4
1 1
Number of ‘A’ atoms = 4
8 2
1
Number of ‘B’ atoms = 4 1
4
1
Number of ‘C’ atoms = 2 1
2
Hence, formula of unit cell = A1/2BC and simplest formula of compound is AB2C2.
414. Answer (2)
Orthorhombic crystal system has simple, body centred, end centred and face centred unit cell.
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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)
ZA
d
V(in cm 3 ) N0
4 27 4 27
d 8 3 23 = = 2.8 g/c.c
24
( 4 10 ) 6.023 10 64 10 6.023 10 23
1
Number of ‘A’ atoms = 8 1
8
1
Number of ‘B’ atoms = 6 3
2
1
Number of ‘C’ atoms = 12 1 4
4
After passing tetrad axis, 2 face atoms and 1 body atom is removed. Now,
1
Number of ‘A’ atoms = 8 1
8
1 1
Number of ‘B’ atoms = 6 2 2
2 2
Number of ‘C’ atoms = 4 – 1 = 3
Hence, formula of unit cell is AB2C3.
426. Answer (2)
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62 Physical Chemistry Success Achiever (Solutions)
3a
r r– (a = cell edge length, r+ + r– = inter ionic distance)
2
3 3.5
r r–
2
r+ + r– = 3.031 Å
—
Cl –
Cl
— Cl
Cl
2rCl 2rCs 3 a
3a
rCl rCs
2
In a cubic crystal, 9 plane of symmetry, 13 axis of symmetry and 1 centre of symmetry is present.
Factual type.
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433. Answer (3)
1 1
Number of O2– ions = 8 6 4
8 2
= 80 2
So, a = 80 pm (a = cell edge length)
In NaCl type structure,
a 80
r r 40 pm
2 2
a 361
r= 127.6 pm
2 2 2 2
By ABC,
a
2a2 = 16r2
1 2 C B
r2 a
8
1
r a
2 2
a
Distance of closest approach = 2r =
2
670.3
r+ = pm – 181 pm = 154 pm
2
436. Answer (3)
Factual type.
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a
x
2
3
⎛ a ⎞ a3
⎜
Volume of fcc unit cell = ⎜ ⎟
⎟
⎝ 2⎠ 2 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
r 2.165 Å
4 4
r = 216.5 pm
4
edge length = r
3
4
4.29 = r
3
4.29
r= 3 1.86 Å
4
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444. Answer (1)
rNa
From r 0.75
K
rNa
Putting the value of rNa in 0.55 then we get
rCl –
0.75 rK
0.55
rCl–
rK 0.55
0.733
rCl– 0.75
(Side for unit cell for KCl = 2(rK rCl– ) , Side for unit cell for NaCl = 2(rNa rCl– ))
10 5
Number of cation vacancies = 2 6.023 10 23 = 1.2046 × 1017
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
⎝ 2 8 ⎠ 2
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3
V2 = Vhexagonal = a2c
2
(because a = b c, = = 90°, = 120°)
V1 2
V2 3
98 1000 1.6
N= 32
49 100
459. Answer (2)
9.1 × 10–31 kg = 1 e–
1
1 kg = e
31
9.1 10
∵ 6.023 × 1023 e– = 1 mole
1 1 1
e
31 23 31
9.1 10 6.023 10 9.1 10
Number of moles (n) = 0.018 × 108 = 1.8 × 106 moles
n
Molarity = v
2
1.8 106
M=
0.5
M = 3.6 × 106 M.
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460. Answer (4)
According to Raoults law for non-volatile solution.
PB P ⎡ A solute ⎤
xA ⎢ ⎥
PB ⎣B solvent ⎦
Mass
1000 NVml …(i) (N = 0.5 N, V = 100 ml)
Eq mass
⎛ g ⎞ 1000
5 ⎜⎜ ⎟⎟
⎝ Eq mass ⎠ w
g
1000 w 5 …(ii)
Eq mass
⎡N 0.5 N ⎤
w × 5 = 0.5 × 100 ⎢ ⎥
⎣ V 100 ml ⎦
w = 10 g.
(mass of solvent )
a3Na
M=
N
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⎛ i1n1 i2n 2 ⎞
⎜ ⎟
or = ⎜ v v ⎟RT .
⎝ 1 2 ⎠
472. Answer (4)
18
pº –ps nsolute 180 18
ps nsolvent 178.2 17.82
18
760 – ps 18
ps 1782
PB P in A ⎡ A solute ⎤
…(i) ⎢ ⎥
PB in A nB ⎣B solvent ⎦
∵ solution is concentrated
P°B = 760 mm-Hg P = 750 mm-Hg
5.85
nA = = 0.1 mole
58.5
180
nB = = 10 moles
18
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for AB A B
1
i=1+
1 0.1(1 )
(dilute solution)
76 10
100
1+=
76
= 0.315.
3
Al 2 (SO 4 ) 4 2Al 3SO 4 2
2 moles
1 mole 3 moles
nsolute
molality = w 1000
solvent
⎡ w ⎤
⎢d v ⎥
⎢ ⎥
n ⎢ w 250 1⎥
3= 1000 ⎢ w 250 g ⎥
250 1
⎢ ⎥
⎣ ⎦
3
n= mole
4
3 2 3 3
mole of Al2SO4 producing = mole
4 1 4 2
3 23 23
number of Al3+ ions = 6.023 10 9.03 10 ions.
2
i1 = 1 + 2
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i1 = 1 + 1
i1 = 2
for CH3COOH, = 50% i.e. = 0.5
1
CH3 COOH (CH3 COOH)2
1
2
2
i2 = 1 Total value of
2
i2 = 1 – 0.25 i = i1 + i 2
i2 = 0.75 i = 2 + 0.75
i = 2.75
477. Answer (1)
478. Answer (3)
479. Answer (3)
Addition of acid in to water is exothermic and H < 0 then solution will be non ideal showing negative deviation.
Solvent is the component which have same physical state as that solution.
484. Answer (3)
3
For AlCl3 Al 3Cl
1 3
i1 = 1 + 3 ( = 100%)
i1 = 4
NaCl Na Cl
1
i=1+ ( = 100%)
i=2
1 = i1RT
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2 = i2cRT
1 i1
2 i2
1 4
2 2
1 : 2 = 2 : 1.
485. Answer (1)
1000 1000
m 55.56
18 1000
489. Answer (3)
PB P ⎡ A solute ⎤
xA …(i) ⎢ ⎥
PB ⎣B solvent ⎦
xA ⎛ 1 ⎞
3 = x 55.55 x A ⎜1 ⎟ 1
B ⎝ 0.054 ⎠
xA 1
= 0.054 xA
xB 19.5
xA
xB …(i) xA = 0.05
0.054
∵ xA + xB = 1 P°B – P = xA × P°B
P°B – P = 0.05 × 760 = 38.97 mm-Hg.
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P°A – PS nB
as we know =
PS nA
185 – 183 WB MA
⇒ = ×
183 MB WA
2 1.2 58
⇒ = ×
183 MB 100
1.2 58
⇒ MB = × ×183
2 100
= 63.68 g / mole
g
NV 1000(NaHSO 3 )
(NaOH) eq mass
g
0.1 1 100 1000
104
PB P ⎡ A solute ⎤
xA ⎢ ⎥
PB ⎣B solvent ⎦
1.04
PB P
104
PB 36 (dilute solution)
18
PB P 0.01
PB 2
0.01
(P°B – P) = 1 (atm)
2
P P
B = 0.005 atm
(lowering of vapour pressure)
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492. Answer (2)
RT0 2
Kb
1000 Hv
2
2 (373)
Kb
9.72 3
1000 10
18
Kb = 0.52° mole/kg
Tb = Kb × m
Tb = 0.52 × 0.1 = 0.052°.
493. Answer (2)
1
C 6H5 COOH C H COOH
1
n 6 5
1
n
i = 1
n
⎛ 1⎞ ⎡ 100%⎤
i = 1 ⎜ 1 ⎟ ⎢ ⎥
⎝ n⎠ ⎣ ⇒ 1 ⎦
⎛ 1⎞
i = 1 ⎜1 ⎟ …(i)
⎝ n ⎠
Tf (obserbed)
i=
Tf (calculated)
Tf
i …(ii)
Kfm
12.2 1000
m=
122 100
m = 1 molal
0.93
i=
1.86 1
1
i=
2
Putting the value of ‘i’ in equation (i)
⎛ 1⎞
i 1 ⎜1 ⎟
⎝ n⎠
1 ⎛ 1⎞
1 ⎜1 ⎟
2 ⎝ n ⎠
n = 2.
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y = mx + c
m=1 (tan = 1, = 45°) log m
496. Answer (4)
Solute solvent interaction is equal to solute-solute and solvent-solvent interaction.
497. Answer (4)
For dilute solution
nA
xA ~ n (nA + nB ~ nB)
B
PB P in A
ix A .
PB nB
P A x A
x A
( vapour phase )
P A x A PB x B
50 0.5
xA =
50 0.5 100 0.5
25
xA =
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.
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502. Answer (2)
Partial pressure of water
R.H 100
Saturated partial pressure of water
503. Answer (2)
Fact
504. Answer (3)
P XA PA0 XBPB0
505. Answer (3)
2A
A2
3A
A3
1 0
1
1 3
2
2
⇒ i 1 ⇒ i 1
2 3
1 2 1
1 0.5 1 0.33
2 3 3
CH3COOH2
2CH3 COOH
1–
2
i 1–
2
0.527 = 1 –
2
= 0.473
2
= 0.946
% association = 94.6%
8.314 383.7 92
2
RTb2 M1
Kb ⇒ Hv = 34 kJ mol–1
1000Hv 1000 3.32 103
507 Answer (2)
i = 5 for K4[Fe(CN)6) and i = 5 for Mohr salt.
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i CRT
WC6 H6 0.8 78
0.2 1000
m 3.2
0.8 78
510. Answer (4)
6
Cr 2 O72 2Cr O24
3+ E0 = ? 2+ E0 = – 0.439 V
Fe (1)
Fe (2)
Fe
0
E = – 0.036 V
(3)
0.0591 1
E = 0.80 – log
1 2x
513. Answer (2)
AgNO3 will react with copper.
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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
E= – log Q
nF
2H+
H2
PH2
Q=
[H ]2
518. Answer (4)
519. Answer (4)
Fact.
520. Answer (2)
Only H2O is electrolysed.
521. Answer (4)
Change in oxidation number of N is 6
22.4
Veqv = = 3.73 L
6
522. Answer (1)
2H2O + 2e– H2 + 2OH– ...(i)
2H2O O2 + 4H+ + 4e– ...(ii)
2x
From (i) 1 mol of H2 = 22.4 LH2 is obtained by 2 units xL of H2 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
2e– +
nf 2
n=2
1
Net charge = = 1.25 F
0 .8
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i.e. E° = E0 – E0
OH– /Fe(OH)3 /Fe Fe2 /Fe
0.75V
Eocell = EFe
o
2
/ Fe
o
– E Cr 3
/ Cr
WAg WMg
=
E Ag EMg
M 0.01
K= = (C1 – 2C2 + C3) ×
1000 1000
C A C
Here A = B
C B C
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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)
0.0591
E = Eo – 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
0.250 35 60
The quantity of electricity passed = F = 5.44 × 10–3 F
96500
5.44 10 –3
Molarity of NaOH = 1.36 10 –2
0.4L
G
=
H
3
CH3OH(l) + O (g) CO2(g) + 2H2O(l)
2 2
Greaction = Gproducts – Greactant
= [–394.4 – 2 × 237.2] – [–166.2]
= –702.6 kJ
G
We know, efficiency of a fuel cell, 100
H
–702.6
= 100
–726
97%
M C 2
= ,K=
1–
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c 48.15
x (degree of ionisation) = = 0.1232
0 390.7
l
Now, R
a
l R
50 1.4 10 2
a
l
50 1.4 10 2
a
l
R
a
1 1 l
R a
1 1
= 50 1.4 10 2 = 70 10 2 = 2.5 × 10–3 S cm–1
280 280
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539. Answer (3)
dE S
=
dT nF
E > 0, Q < 1.
1
H e –
H2
2
0.059 PH2 2
E0 log
1 [H ]
0.059 21/2
E log
1 1
Therefore E is negative.
Fact.
1
H2O O + 2e–, H2O2 O2 + 2e–
2 2
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electrolys is 1
NaH Na H2 (g)
2
( cathode) anode
1
At cathode : H2O + e– H + OH–
2 2
0.0591 [Cu 2 ]1
E1 – E2 = log
2 [Cu 2 ] 2
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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
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.
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⎛ 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
1
0.059
⇒ E Eo
1
log PCl2 2
–w max = G = –nFE = (–1) (–1.14) × 96500 × 10–3
=110 kJ mol–1
563. Answer (4)
2 × 1.6 × 10–19C is carried by 1 molecule of Zn2+
1
2 × 10–5 C is carried by = 2 10 5
2 1.6 1019
1 1
moles
1.6 1014 N0
1
1.6 6.023 1014 1023
= 10–10
564. Answer (2)
1000 sp.conduc tance
0 (BaSO4 )
conc.(Normality)
1000 8 10 –5
Normality =
400
Normality
Molarity = 10 –4 M
2
Ksp = S2 = 10–8 M2
565. Answer (3)
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+ –
Ag Ag + e ; E°Ag/Ag+ = –0.80V
– –
AgI+e Ag + I ; E°I– / AgI/Ag+ = –0.15V
Ag + I–
+
AgI E°Cell = –0.95V
0.0591
ECell = log k sp
1
–0.95
log K sp
0.0591
Ksp = 8.42 × 10–17
567. Answer (2)
0.059 ⎛ D ⎞
Ecell 0.003 log ⎜ ⎟ 0 at equilibrium
2 ⎝ H ⎠
⎛ D ⎞
0.006 0.059log ⎜ ⎟
⎝ H ⎠
⎛ D ⎞ D
0.102 log ⎜ ⎟ ⇒ 100.102 1.2
⎝ H ⎠ H
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)
2.303 ⎛ a ⎞
k= log ⎜⎜ ⎟⎟
t ⎝a– x ⎠
at time (t/2) seconds
0.6932 2.303 ⎛ a ⎞
log ⎜⎜ ⎟⎟
t ( t / 2) ⎝a– x ⎠
0.6932 ⎛ a ⎞
log ⎜⎜ ⎟⎟
2 2.303 ⎝a– x ⎠
⎛ a ⎞
log ⎜⎜ ⎟⎟ 0.15
⎝a– x ⎠
⎛ a ⎞
⎜⎜ ⎟⎟ 1.413
⎝a– x ⎠
a = 1.413a – 1.413x
0.413a = 1.413x
x 0.413
a 1.413
0.413
% fraction of element decayed = 100 = 29%
1.413
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86 Physical Chemistry Success Achiever (Solutions)
1
t 1/ 2 & where n is order of reaction
n –1
a
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
ln 2
t1/2 =
k
2.303 0.301
k=
6.93
2.303 ⎛ a ⎞
log ⎜
⎝ a – 0.99a ⎟⎠
Also, t =
k
2.303 ⎛ 1 ⎞
t = 2.303 0.301 6.93 log ⎜⎝ 0.01⎟⎠ = 46.05 minutes
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Success Achiever (Solutions) Physical Chemistry 87
d[C]
Or, k[A]x [B]y
dt
y
⎡ 1⎤
⇒ 1 ⎢ ⎥
⎣2⎦
⇒ y0
1 x
⎡ 1⎤ ⎡ 1⎤
⇒ ⎢2⎥ ⎢2⎥
⎣ ⎦ ⎣ ⎦
⇒ x 1
d[C]
Hence = k[A]1[B]0 .
dt
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88 Physical Chemistry Success Achiever (Solutions)
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 s–1
579. Answer (1)
x 10
k= for zero order reaction = = 10
t 1
20
In second case k = = 10
2
30
In third case k = = 10
3
Since rate constant (k) is equal in each case therefore reaction follows the zero order mechanism.
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.
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)
Ea
Energy
P
H
R z
Reaction progress
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Success Achiever (Solutions) Physical Chemistry 89
583. Answer (3)
k = A e –Ea / RT
Ea
ln k = ln A –
RT
y = c + mx
Ea
slope of graph = –
R
590. Answer (1)
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90 Physical Chemistry Success Achiever (Solutions)
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 r1 = 2.4 M s–1
2 .2 2 .4
[A]II = = 1.1 M r2 = 0.6 or
2 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.
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Success Achiever (Solutions) Physical Chemistry 91
599. Answer (3)
Since concentration of increases time to time but not linearly.
600. Answer (1)
1 d [I– ] d [I ]
– 2
2 dt dt
1
= 1.44 t1/2, tav =
1
=
1
N N ·
e = 0 ⇒ 0 e e
t
N N
N0
N=
e
604. Answer (4)
2.303 a 2.303
t= log = 2
k a 0.99a k
2.303 2
t=
k
⎛ 1⎞
t = 2.303 2 · ⎜ ⎟ = 4.604 tav = 4.6
⎝k ⎠
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92 Physical Chemistry Success Achiever (Solutions)
2.303 ⎛ 1 ⎞
t = 2.303 0.301 6.93 log ⎜⎝ 0.01⎟⎠
= 46.05 minutes
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Success Achiever (Solutions) Physical Chemistry 93
610. Answer (3)
k2
e(E1 – E 2 ) / RT
k1
E1 – E 2 2
2 .5
RT 2 10 3 400
–
k2
e 2 .5
k1
k 2 e 2 .5 k 1
1 + k2 [NH3 ] k2 NH3
k 1[NH3 ]
rate = constant
k 2 [NH3 ]
This follows the zero order kinetics therefore rate is independent of conc. of NH3 .
P0 – P + 2P + P = Pt
2P = Pt – P0
⎛ Pt – P0 ⎞ 2.303 ⎛ P0 ⎞ P0 2.303 ⎛ 2 P0 ⎞
P = ⎜ ⎟ = log ⎜ ⎟ = 2.303 log = log ⎜ ⎟
⎝ 2 ⎠ t ⎜ 0 ⎟ t ⎡ 0 ⎛ P – P0 ⎞⎤ t ⎜ 3 P0 – P ⎟
⎝ P –P ⎠ ⎝ t ⎠
⎢P – ⎜⎜ t ⎟⎥
⎟⎥
⎢⎣ ⎝ 2 ⎠⎦
⎛ 3⎞ 3 3 3
= 400 ⎜1– ⎟ 400 400 = 400 400 = 400 + 300 = 700 mm of Hg
⎝ 4⎠ 4 4 4
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94 Physical Chemistry Success Achiever (Solutions)
N0
Or, 1.76
N
2.303 N
We know that log10 0
t N
2.303
log10 1.76 = 0.113 minute–1
5
0.693 0.693
Half life period = 6.1 minute
0.113
615. Answer (4)
7500 0.012 0.35
Weight of radioactive potassium = = 0.0315 g
100 100
0.693 Weight
Activity = t1/2 Atomic weight Avogadro’s number
0.693 0.0315
Activity = 9
6.023 1023 = 4.81 105 dpm
1.3 10 365 24 60 40
616. Answer (2)
K1 1.26 104
Percentage of cyclohexene = 100 = 100 = 77%
K1 K 2 1.26 104 3.8 10 5
% of methy cyclopentene = 23%
618. Answer (2)
kf = 4 × 10–4
kb = 2 × 104
kf 4 10 –4
keq = 2 10 – 8
kb 2 10 4
619. Answer (1)
Ea (E – 20)
– – a
500 R 400 R
– 4 Ea = – 5 Ea + 100
Ea = 100 kJ mol –1
–Ea /RT
k2 = Ae 2
1
k2
e RT Ea1 – Ea2
k1 =
k Ea – Ea2 10 103
ln 2 = 1 = 4
k1 RT 8.314 300
2.4
[N2O5 ] = 0 .8
3
0.693 0.693
K
t1/2 22
If K 1 and K2 are the rate constants of the reactions leading to 222th and Fr223, respectively we have
0.693
K1 + K2 =
22
K1 2
K 2 98
K2 = 0.03087–1y–1
K1 = 0.00063–1y–1
⎡ ⎛ N ⎞⎤
⎢ ln ⎜ N ⎟⎥
⎠ ⎥ ⇒ N0 24 ⇒ N 48 g
t t1
2
.⎢ ⎝ 0
⎣⎢ ln 2 ⎦⎥ N
0
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96 Physical Chemistry Success Achiever (Solutions)
0.693 2.303 4 1
9
log
4.5 10 t 4
= 67.5 kJ mol–1
627. Answer (4)
x ap
Apply . At high P, 1 + bp bp.
m 1+ bp
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Success Achiever (Solutions) Physical Chemistry 97
636. Answer (4)
637. Answer (4)
Catalyst decreases activation energy hence rate constant increases.
Ea
–
K Ae RT
A
K Ea
e RT
As Ea decreases, K increases
Hence rate of reaction increases.
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)
2AuCl3 + 3HCHO + 3H2O
2Au(sol) + 3HCOOH + 6HCl
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.
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98 Physical Chemistry Success Achiever (Solutions)
4
Z=
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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