JEE COMPENDIUM

SOLUTION MANUAL
CHEMISTRY
Module-1
 Atomic Structure Atomic Structure

DPP-1
Q.1 (1)
Q.2 (2) Q.8 (2)
Q.3 (2) When electron falls from n to 1, total possible number
Q.4 (4) of lines = n – 1.
Q.5 (1) Q.9 (3)
Q.6 (2)
h 6.626  1034
The -ray particle constitute electrons. = = = 2.4 ×
Q.7 (3) mv 3.1  1031  3  108  10 100
This is because chargeless particles do not undergo 10–9 cm
any deflection in electric or magnetic field.
Q.8 (2)
Proton is 1837 (approx 1800) times heavier than an DPP-4
1
electron. Penetration power  Q.1 (1)
mass
Q.2 (4)
Q.9 (3)
Q.3 (3)
c 3  10 8
When c     than     1 .5  10 2 m Q.4 (2)
 2  10 6 Q.5 (1)
Q.10 (4) Q.6 (2)
Q.7 (4)
DPP-2 Q.8 (2)
Q.9 (3)
Q.1 (1) Q.10 (1)
Q.2 (4) Q.11 (1)
Q.3 (2) Q.12 (1)
Q.4 (3) Q.13 (2)
Q.5 (2) Q.14 (4)
Q.6 (1) Q.15 (2)
Q.7 (1) Q.16 (4)
Q.8 (2)
Q.9 (4) EXERCISES
Q.10 (2)
JEE MAIN
OBJECTIVE QUESTIONS
DPP-3 Q.1 (4)
e / me 
e / me

3672
Q.1 (3) e / m 2e / 4  1836 me 1
Q.2 (1)
Q.3 (1)
Q.2 (1)
Q.4 (4)
Q.5 (3) Volume of nucleus
Q.6 (2) Volume fraction = Total vol. of atom
Q.7 (2)
( 4 / 3)  (10 13 )3
= = 10–15
10 ( 4 / 3)  (10 8 )3
First Excited level = 2
9
ninth level = 10 Q.3 (3)
8
7 R = R0 A1/3 = 1.3 × 641/3 = 5.2 fm
6 Q.4 (1)
5
4  n2 
r    As Z increases, radius of I orbit decreases.
Total line = 6  Z 
 

C HEMISTRY 1
Atomic Structure

Q.5 (2) Q.10 (1)

x  y + 2He4 hC
y 8O18 + 1H1 I.E. of one sodium atom =

––––––––––––––––––––
Adding both eq. hC
& I.E. of one mole Na atom = NA =
x  2He4 + 8O18 + 1H1 
By conservation of mass 6.62  1034  3  108  6.02  1023
= 494.65 kJ.mol.
X = 4 + 18 + 1 gm 242  10 9
= 23
23 gm  (2 + 10) moles neutrons. Q.11 (3)
12 For photoelectric effect to take place, Elight  W
1 gm  neutrone
23 hc hc
    or   0 .
0
12 46
4.6 gm  × = 2.4 neutrans Q.12 (4)
23 10
Photoelectric effect is a random phenomena. So,
Q.6 (2)
electron It may come out with a kinetic energy less
Given :
than (h – w) as some energy is lost while escaping
P = 1 kW
out.
P = 1 × 103 watt
Q.13 (4)
E = 103 J/S in one sec
v = 880 Hz nhC 80
Power =  40 × =
 E = nhv t 100
 103 x × 6.626 × 10–34 × 880
n  6.62  1034  3  108
 x = 1.71 × 1033 in one sec  n = 2 × 1021
620  109  20
Q.7 (3)
Q.14 (2)
hc We know that, for wave no.
E=

3  1  2
1240
= = 40 1 1 1
31  
 3  2 1
K.E. max = 40 – 12.8
= 27.2 eV Q.15 (2)

1 n2
mv2 = 27.2 × 1.6 × 10–19 r = 0.529 × Å
2 Z

54.4  1.6  10 19 12

V2 = = 0.529 × Å
9.1 10 31 1
V2 = 9.56 × 1012 = 0.529 × 10–10 m
V = 3.09 × 106 m/sec. = 0.529 × 10–8 cm
Q.8 (4) Q.16 (4)

hc r3  0.529  32 Z
E=
 r1  0.529  12 Z
1  r3 = 9r1
E
 Q.17 (1)
E1 4000 2
hc
E2 = 2000  i.e. 1 = 2 K.E. max =   = 8 – 5 = 3eV

Q.9 (3)  V0 = 3 eV
Violet colour has minimum wavelength so maximum
energy.

2 J EE C OMPENDIUM
 Atomic Structure

Q.18 (4)
r=  (b) Potential energy of  orbit of H-atom = – 27.2 × 12 =
Q.19 (2) – 27.2 eV (ii)

12 22 22
E1 (H) = – 13.6 × = – 13.6 eV ; E2 (He+) = – 13.6 × (c) Kinetic energy of  excited state of He+ = 13.6 ×
12 22 32
= – 13.6 eV = 6.04 eV (i)
(d) Ionisation potential of He+ = 13.6 × 22 = 54.4 V (iii)
32
E3 (Li2+) = – 13.6 × = – 13.6 eV ; E4 (Be3+) = – 13.6 × Q.26 (2)
32
S1 : Potential energy of the two opposite charge system
42 decreases with decrease in distance,
= – 13.6 eV
42 S4 : The energy of Ist excited state of He+ ion
 E1(H) = E2(He+) = E3 (Li2+) = E4(Be3+) = – 3.4 Z2 = – 3.4 × 22
– 13.6 eV.
Q.20 (3)
En = – 78.4 kcal/mole = – 78.4 × 4.2 = – 329.28 kJ/mole S2 and S3 are correct statement.

329 .28
=– eV = – 3.4 eV.. (energy of II orbit of H Q.27 (4)
96.5
atom). R 0.529  4
=
Q.21 (1) R' 0.529  9

Z 9R
V = 2.188 × 106 m/s R’ =
n 4
V 2 Z1 / n1
= 2.25 R
Z Li 3/3
Now, V  so, V = – Z /n = = 1 or,,
n H 2 2 1/ 1
Q.28 (1)
VLi2  = VH Z2 (1)2
En = E1 E5 = – 13.6 × = – 0.54 eV
Q.22 (1) n2 (5)2
IE1 + IE2 + IE3 = 19800 Q.29 (4)
IE2 + IE3 = 19800 – 520 hc 1
IE2 + IE3 = 19280  
E E
Q.23 (1)
r1 – r2 = 24 × (r1)H Q.30 (2)
r1 = 0.529 Å
0.529  n12 0.529  n22
– = 24 × 0.529 r3 = 0.529 × (3)2 Å = 9x
1 1

 
2r 2 (9 x )
 n12 – n22 = 24 so,  = = = 6 x.
n 3
So, n1 = 5 and n2 = 1
Q.31 (2)
Q.24 (3) n3
T
Z2 Z2
I.P. = 340 V so, I.E. = 340 eV = 13.6
(1)2
T1 13 12 1
 3 2 
T2 2 1 8
so, Z2 = 25 so, Z = 5 Therefore, (B) is correct option.
Q.32 (4)
Q.25 (3) Is  As it is the ground state
(a) Energy of ground state of He+ = – 13.6 × 22 = – 54.4
eV (iv) Q.33 (2)
Balmer means transition

C HEMISTRY 3
Atomic Structure

to n = 2
1. line  3 to 2
1  1
 RH 1  
2. line  4 to 2 Lymen  4
3. line  5 to 2
4
Lymen = 3 R
Q.34 (2) H

1 1  1 1 
= RH.4   0 
1
4    
x Balmer = RH × 4  4 16 

1 16
RH =
x Balmer = 8  3R
H

1 1 1 
= RH × 9    Lymen 4 / 3RH 1
  9 16   = 1:1
Balmer 4 / 3RH 1
1 1 16  9 
= ×9   Q.37 (3)
 x  144 
(n22  n12 ) = 8
1 1  7  (n2 – n1) (n2 + n1) = 8
= ×9  
 x 144   (n2 – n1) = 8/4
n2 – n 1 = 2
1 7 n2 + n 1 = 4
=
 16 x –––––––––––––––––
 n2 = 3
16 x
= n1 = 1
7
1  1
Q.35 (2) = RH × 4 1  
  9
1
= 109677 × 9 9
  = 32 R
 = 1.01 × 10–6 cm H

6.62  10 34  3  108

Q.38 (1)
E= Li2+ and He+ are single electron species.
1.01 10 8
= 19.66 × 10–18 J Q.39 (3)
Visible lines  Balmer series (5  2, 4  2, 3  2). So,
1 3 lines.
 mv 2 = 19.66 × 10–18
2
Q.40 (4)
18
39.32  10 1 1 
1
= RH × 4   
V2 =
9.1 10 31   9 16 
V2 = 4.32 × 1013
V2 = 43.2 × 1012 1 7
= RH ×
V = 6.57 × 106 m 36

6.62  10 34 1 36 1

debroglie = 31
= × 16  
9.1 10  6.57  10 6  required 7m 9 
= 1.17 × 10–10 m
= 1.17 Å 1 36 1
 × 16  
 required 7m 9 
Q.36 (1)
7m
req. =
64
4 J EE C OMPENDIUM
 Atomic Structure

Q.41 (3) Q.46 (4)

infrared lines = total lines – visible lines – UV lines =
1 V2 200 2
6( 6 – 1)
– 4 – 5 = 15 – 9 = 6. 2 = V1 = 50
= .
1
2
(visible lines = 4 62, 52, 42, 32) Q.47 (1)
(UV lines = 5 61, 51, 41, 31, 21) Mass of  particle = 4 (mass of proton)
Mass of proton = 1840 (mass of e–)
Q.42 (4)
Let
According to energy, E4  1 > E3  1 > E2 1 > E3  2 .
Mass of e– = m
According to energy, Violet > Blue > Green > Red.
 Mass of p+ = 1840 m
 Red line   2 transition.
and mass of  particle = 7360 m
Q.43 (4)
1
For 1st line of Balmer series meV2 = 16 E
2
 1 1   5  5
v1 = RH (3)2    = 9R   = R
 (2)
2
(3)2   36  4 32E
Ve2 
For last line of Pachen series m

 1 1  8E
v 2 = RH (3)2  
5 Vp2 
2  = R so, v 1 – v 2 = 4 R 1840 m
 (3)
2
( ) 

E
–R=
R
. V2 
4 7360 m
Q.48 (2)
Q.44 (2)
h
n n1 n2 2 4 
 Z = Z or = (n = 4 of C5+ mv
Z 1 2 3 6
ion). h
p=

Q.45 (3)
dp d L
1   
mV2 = 6 × 1.6 × 10–19 d d   A 
2
dp h
12  1.6  10 19 = 2
V2 = d 
9.1 10 31
V2 = 2.10 × 1012 h
dp = 2 .
V = 1.44 × 106 m/sec 

6.62  10 34 h h
= 6 31 x . 2 
1.44  10  9.1 10  4
= 0.5 × 10–9
 1
 x . 2 =

1  4
x .
0.25  10 18 
 1
x  
7  1  4 
 10 9  

22 0.25  10 18 4
(5  10 7 )2

0.25  10 9 10–12  4
 =
4 Ans. 0.0199 m
–9
= 0.0625 × 10
= 0.625 Å
C HEMISTRY 5
Atomic Structure

Q.49 (3) Q.60 (1)

34 h
h 6.62  10 Orbital angular momentum =  (  1) = 0.
p . x =  x = = 5.27 × 10– 2
4 4  3.14  1 10 5   = 0 (s orbital).
30
m. Q.61 (1)

Q.50 (1) Magnetic moment = n(n  2) = 24 B.M.

5-fold degenerate  No. of unpaired electron = 4.
All d-orbitals are of same energy.
X26 : 1s2 2s22p63s23p63d64s2.
Q.51 (3) To get 4 unpaired electrons, outermost configuration
will be 3d6.
z  No. of electrons lost = 2 (from 4s2).
 n = 2.
nodal plane
Q.62 (4)
x 10 electrons Neon
Q.63 (4)
26
Fe  1s2 2s2 2p6 3s2 3p6 4s2 3d6
Fe2+  4s0 3d6
z nodal plane

dxz x 6e
–

Px Cl–  3s2 3p6

17

Q.52 (3) 6 e–
y Q.64 (2)

n(n  2)  35
45º
x n=5
dxy
x3+  4sº 3d5
x  4s2 3d6
Q.53 (1)
i.e., 26Fe
As graph is not starting from origin.
 For s-subshell with 1 radial no.
Q.65 (2)
i.e., n –  – 1 = 1
Zn2+ : [Ar] 3d10 (0 unpaired electrons).
 n – 0 – 1 = 1  n = 2
Fe2+ : [Ar] 3d6 (4 unpaired electrons) maximum.
 2s 3+
Ni : [Ar] 3d7 (3 unpaired electrons).
Q.54 (1) +
Cu : [Ar] 3d10 (0 unpaired electrons).
Graph must be in increasing order
Q.66 (4)
Q.55 (4)
d7 : 3 unpaired electrons.
Q.56 (2)
Na+, Co+2, Cr2+, Fe+3 n 3
Total spin = ± =± .
2 2
M. M. () = n(n  2)
Q.67 (1)
we get Na+, Co+2, Cr2+, Fe+3 X23 : 1s2 2s2 2p6 3s2 3p6 3d3 4s2.
Q.57 (2) No. of electron with  = 2 are 3 (3d3).
h Q.68 (2)
O.A.M. = (  1)
2 Cr (Zn = 24)
here l = 0 electronic configuration is : 1s2 2s2 2p6 3s2 3p6 4s1 3d5
OAM = zero
so, no of electron in  = 1 i.e. p subshell is 12 and no of
Q.58 (4)
electron in  = 2 i.e. d subshell is 5.
Spin
Q.59 (3) Q.69 (1)
h
5p, as using (n + l) rule energy of 5p > 4d
Orbital angular momenting = (  1)
2

6 J EE C OMPENDIUM
 Atomic Structure

1s  0 Q.4 (4)
3s  0 } ( = 0 for s)

h V=
2(2  1) ( = 2 for d) T
For 3d =
2 V = 
=h 6 3 × 108 = × 5 × 1013

Q.70 (4) 3
= × 10–5
Cl17– : [Ne] 3s2 3p6. 5
Last electron enters 3p orbital. = 0.6 × 10–5 m
  = 1 and m = 1, 0, –1.
6.6  10 34  3  108
E=  33 × 10–21
Q.71 (3) 0.6  10 5
Number of radial nodes = n –  – 1 = 1, n = 3.
330
No. of photons =
  = 1. 33  10 21

h h = 1022 photons Ans.

Orbital angular momentum =  (  1) = 2 2 .
2 Q.5 (3)
Q.72 (3)  = 58.44 nm
Cl17 : [Ne] 3s2 3p5.
1 107
Unpaired electron is in 3p orbital.  = = cm–1 = 17115.67 cm–1
 58.44
 n = 3,  = 1, m = 1, 0, – 1. req. = 17115.67 – 485.7
Q.73 (3) = 166258.67 cm–1
n no. of e–
hc
3s  = 0  s  E= = hc 

Q.74 (1) = 6.62 × 10–34 × 3 × 108 × 16625867
Zn2+  3d10 4s0 = 3.3 × 108 × 108 × 10–34
30
no. of unpaired e– = 0 = 3.3 × 10–18 J Ans.

JEE-ADVANCED Q.6 (1)

OBJECTIVE QUESTIONS Let absored e– be n1
Q.1 (1) and emitted e– be n2
Hydrogen atom contains 1 proton, 1 electron and no n2hc 47
neutrons. E
2 100

Q.2 (1) n1hc E
Ne contains 10 electrons 1
O2– contain 10 electrons
n21 47
Q.3 (1) 
n1 2 100
hc 6.6  10 34  3  108
E= = 47  5080
854  10 10
 n2

n1 100  4530
For 1 mole

6.626  10 34  1018  3  6.022  10 23 n2

Emole = n1 = 0.527 Ans.
854
Q.7 (2)
6.626 107  3  6.022
=
854
= 0.140 × 107 J/mole 120º

= 1.4 × 103 KJ/mole Ans.

C HEMISTRY 7
Atomic Structure

The photons will strike the metal like only on shaded

1
part and rest photons will escape out. = 2.18 × 106 ×
 Part Qd circular disc where 4
= 5.45 × 105 m/sec Ans.
120 1
photons will strike =  Q.11 (2)
360 3
z2
1 –3.4 = –13.6 × 2
 rd part the disc. n
3
2
n =4
Total energy = 90 J per sec.
1240 nh 2h h
n = 2 (Angular momentum = = = )
Ephaton =
400
= 3.1 eV 2 2 

90 h
Ans.
No. of photons = 
3.1 10 19  1.6
Q.12 (4)
90 1
No. of photo e– ejected =  n13
3.1 1.6  10 19 3 T1 13 1
T2 = 3 = 3 = 8 .
Magnitude of Photocurrent n2 2

90 1
   1.6  10 19  2r  n3
3.1 1.6  10 19 3  T  V  so, T 
  Z2
90 Q.13 (3)
= = 9.78 amp = 10 amp Ans.
3 .1  3
r1 n12 R n1 1 T1 n13 1
Q.8 (4) r2 = n2 = 4R  n2 = 2  T2 = n3 = 8 .
2 2
Stopping potential depends on metal surface or
emitter's properties. Q.14 (1)
z
Q.9 (2) Vel. of e– in n = 2 = 2.18 × 106 ×
n
rH(1s orbit) = 0.529 × 10–10m
= 1.09 × 106 m/s
re = 16 × 0.529 × 10–10 m
Distn travelled in 10–8 sec = 1.09 × 106 ×10–8
= 16 × 0.529 Å = 1.09 ×10–2 m
1 KZe 2 Circum ference = 2r
T. E. = – = 2 ×  × 0.529 × 4 × 10–10
2 r
= 4.23  × 10–10 m
1 9  109  1 1.6  .1.6  10 19  10 19 1.09  10 2
=– ×  revolutions =
2 16  0.529 4.23  10 10
 – 13.6 × 10–20 J  – 1.36 × 10–19 J Ans. = 0.08 × 108 rev
= 8 × 106 rev Ans.
Q.10 (2) Q.15 (1)
r = 0.85 nm
= 8.5 Å V
frev =
2r
n2
8.5 = 0.529
Z 2.18  10 6  7
=
8. 5 2  22  0.529  10 10
n2 = = 0.6556 × 1016 Hz
0.529
n = 16  n = 4
2 = 6556 × 1012 Hz Ans.
Q.16 (2)
z IP = 13.6Z2 = 16 (given).
V = 2.18 × 106 × m/s
n
8 J EE C OMPENDIUM
 Atomic Structure

3 3 = 0.078 × 10–17 × 1023 × 6.02 J/mol

1st excitation potential = 13.6 × × Z2 = 16 × = 12 V. = 0.47 × 106 J/mol
4 4
IP = 13.6Z2 = 16 (given). K. E. = 470 – 430.53
= 39.47 KJ
Q.17 (1) 39.47
Angular momentum J = mvr  = 100
470
J2 = m2v2r2
= 8.38% Ans.
J 1
2
2 J2
=  mv  mr
2
or or K.E. = Q.22 (1)
2 2  2mr 2
c
Q.18 (4)  = a(z – b) = 
= a (29 – b)

 2Ke2 
e 
3  108
eVn  nh  4 2mk 2 e 5
  or = a (29 – b)
In = 2r =
 n2h2 
= . 15.42  10 9
n
  n 3h 3
2 
 42me 2K  or 13.94 × 107 = 1 (29 – b) .............(1)
 
also,

Q.19 (4) 3  108

= a (29 – b)
192000 7.12  10 9
Energy required per atom =
6.022  1023  20.52 × 107 = a(29 – b)
= 31883.09 ×10–23 J ..............(2)
Dividing eq. (1) and (2)
31.88  10 20
= 29  b
1.6  10 19 13.94
=
= 19.92 × 101 20.52 42  b
= 1.992 eV Solving we get
= 2 eV
60
hc b= = 1.27
47
 =
E
20.52  107
1240 a= = 0.5 × 107
= = 623.11 nm ( 42  1.27)
1992
 6231.1 Å Ans.
3  108
 = 0.5 × 107 (z – 1.27)
Q.20 (2) 22.85  10 9
0.01 6  1023 11.45 × 107 = 0.5 × 107 (z – 1.27)
no. of photons =
0. 2 z = 22.9 + 1.27  24 Ans.
= 3 × 1022 Ans. Q.23 (1)
Molecules reacting
Quantum yield = quanta absorbed 150
= Å
volt

Q.21 (3) 150

Energy required per molecule = 450530 J =
100  103
6.62  10 34  3  108
= = 15  10 4
253.7  10 9
= 0.0387 Å
= 0.078 × 10–17 J = 3.88 pm Ans.

C HEMISTRY 9
Atomic Structure

Q.24 (2)  = 1093.6 nm

= 1093.6 × 10–9 m
13.6 Z 2 13.6 ( Z )2  1 
Total energy = = = 3.4 eV 1  1 
n2 ( 4)2 9 = RHZ2  2  2 
1093.6  10  3 n wight 
Now K.E. = 3.4 – 1.4 = 2 eV
Now, Total energy = 2 + 4 = 6 eV i.e. potential = 6 V 9.14  105  1 1 
  
10973000  9 n2 
150
For electron  = so  = 5 Å.
V 1 1
0.083 = – 2
Q.25 (1) 9 n
Number of lines in Balmer series = 2.
1 1
 n = 4 (lines will be 4  2, 3  2). = – 0.083
2
n 9
13 .6
KE of ejected photoelectrons = Ephoton – BEn = 13 – 1
42
= 0.11 – 0.083
= 13 – 0.85 = 12.15 eV. n2
n2 = 35.93
Q.26 (2) n = 6 Ans.

Q.29 (2)
 1 1 
1  
= RHZ2  n 2 n2 
  1 2

A 
n n  1 1
 A1  1 – 2 = 
2 1 1 2 1 1 
RH Z    RH Z   
2
4 9 1 4 
A   4rn2  r 
n  n   n    n  n  1 1  36 4 
 4r2 
 A1     r1   
RH 4  5 3 
1 10–9 × 133.7 =


= n
 0.529  n2 / 1 

0 .529  12
/ 1
  n n4

  10–9 × 133.7 =
1 9 1
5  3
  RH  
= 4 n(n)
1  22 
Using the straight line eq. with zero intercept
RH  15 
10–9 × 133.7 =
y = mx
comparing the eq. we get slope = 4 & line passing
through origin.
1 133.7  15  10 9
RH =
22
Q.27 (3)  RH = 0.01096 × 10+9
For Lymen series = 1.096 × 107 m–1Ans.

1  1   1 
 RHZ2 1  1   Q.30 (4)
  n2  = 109700  16 
 2
1 1 1 
= 109700 × 4  4  16 
1 15   
= 109700 ×
 16
1 1 1 
1 = 109700 × 1  4 
= 102843.75   

 = 9.72 × 10–6 cm 1 3
 = 9.72 × 10–8 m Ans. = 109700 ×
 4
Q.28 (3)  = 1.21 × 10–5

10 J EE C OMPENDIUM
 Atomic Structure

For Hydrogen 3
= RC Z2.
 1 4
3
109700 × = 109700 × 1 1  2 
4  n   1 1  1
3 = RC Z2  2
– 
2  = 4 RC Z .  1 – 2 = 3.
2
2  
1 3
2 =1–
Q.34 (2)
n 4 Shortest wave length of Lyman series of H-atom
n=2
1 1  1 1 
i.e., transition from n = 2 to n = 1 Ans. = =R 2  
 x  (1) ( )2 
Q.31 (2)
1
so, x =
1 1 1 R
= 109700 × 9   
 1 9  For Balmes series

1  1 1 
=
1
= R (1)2  2  
109700  8   (2) (3)2 
= 1.139 × 10–6 cm–1
1 1 5 36 x
= 1.139 × 10–8 m–1 = × so,  = .
 x 36 5
113.9 Å Ans.
Q.35 (3)
Q.32 (4) nh h
Change is angular momentum = = (5 – 2) =
2 2
1 1 1 
= 109677 × 4   
 1 4  3h
.
2
1
= Q.36 (3)
109677  3 Let quantum no. be ‘n’
= 3.03 × 10–6 cm 2.7451 × 104
= 30.3 nm
 1 1 1 1 
1240 = RH × 4  2   – RH × 4  2 
E= = 40.92 eV n    n (n  1)2 
30.3
K. E. = 40.92 eV 1 1 1 
= 40.92 × 1.6 × 10–19 J  2 0 2  
= 27451 = 4RH  n
 n (n  1)2 
1
K. E. = mv2
2 1 27451

(n  1)2 4  109677
2  40.92  1.6  10 19  1031
v2 = (n+ 1)2 = 15.98 = 16
9 .1
 n=3
v2 = 14.38 × 10+12
1  1 1
v = 14.38  1012 = RH(z)2  2  2 
 3 4 
= 3.79 × 106 m/s
= 3.8 × 106 m/s 1 7
= 3.8 × 108 cm/sec Ans. = 109677 × 4 ×
 36  4
= 4.689 × 10–5 cm–1
Q.33 (1)
= 4689 Å Ans.
 1 1  Q.37 (3)

 = RC Z2  2 – 2  . x = 2p
 n1 n2 
 h 
x . p = =  2 p . p =
 1 1   1 1  2 4 2
1 = RC Z2  2 – 2  = RC Z2 , 2 = RC Z2  –
2

1   1 22 

C HEMISTRY 11
Atomic Structure

   1
 2(mV)2 = ; (V)2 = 2  V = . mv2 = eV0
2 4m 2m 2
Q.38 (4) 1
=v  1840  9.1 10 31  3.95  3.95  10 6
2 = V0
h h h 1.6  10 19
then  = or 2 = So,  = .
mV m m V0 = 81640.08 × 10–6 V
= 0.0816 Volts Ans.
Q.39 (2)
y mx v x y mx v x 16 Q.44 (4)
x
= m v . = (0.25m ) (0.75 v ) = .
y y 1 x x 3 hc
 y = 5.33Å. = E1 – E2 = KE2 – KE1


2
Q.40 (2) h h 1 1 h2
 = (mV)2 =   ; mV2 =
For an electron accelerated with potential difference V mV  2 2m 2
h 12 . 3
volt,  = Å.  21 22 
2mqV = V hc h 2 h 2
2mc
 = – .=  2 .
Q.41 (2)  2
2m  2 2
2m 1 h  1  22 

6.64  10 34
debrogli = Q.45 (1)
mv
p mKE 4mp  325
6.64  10 34 = = 26  5.
V= = 1.45 × 104 m/sec  mpKEp = mp  50
10 31
500  10  9.1 10
1/2 mv2 = eV0
Q.46 (1)
1
 9.1 10 31  1.45  108  1.45 hc
2 = V0 debroglie =
1.6  10 19 mv
V0 = 5.97 × 10–4 Volts Ans.
6.62  10 34
= = 0.368×10–64 m = 3.68 ×–65 m
Q.42 (4) 6  1024  3  106
1 Ans.
Velocity of proton = × 3 × 108
10
Q.47 (2)
= 3 × 107 m/sec
KE = – TE
V = 3 × 105 m/sec
 KE = – (–3.4)
h  KE = +3.4 eV
V. x =
4m & for e–

6.62  1034 150 150

Å  , Å =
x = = KE 3.4
4  3.14  9.1 1031  3  105  1840
Å = 6.6 Å
6.62  10 8  = 6.6 × 10–10 m
4  3.14  9.1 1840
Q.48 (1)
 1.05 × 10–13 m Ans.
s orbital is spherical so non-directional.
Q.43 (3)

6.62  10 34 Q.49 (3)

10–10 = The lobes of dxy orbital are at an angle of 45º with X and
m
Y axis. So along the lobes, angular probability
6.62  10 34
distribution is maximum.
V= = 3.95 × 103 m/sec
1840  9.1 10 31  10 10 Q.50 (1)
12 J EE C OMPENDIUM
 Atomic Structure

I : For n = 5, lmin = 0.  Orbital angular Q.54 (4)

Spin quantum number does not comes from Schrodinger
momentum =  (  1)  = 0.(False)
equation.
II : Outermost electronic configuration = 3s1 or 3s2.
1 1
 possible atomic number = 11or 12 (False). s=+ and – have been assigned arbitrarily..
2 2
III : Mn25 = [Ar] 3d5 4s2.  5 unpaired
Q.55 (1)
5 After np orbital, (n + 1) s orbital is filled.
electrons.  Total spin = ±
2
(False). Q.56 (2)
IV : Inert gases have no unpaired electrons. Magnetic moment = 2.83
spin magnetic moment = 0 (True). so, no. of unpaired electrons = 2
so, Ni2+ is the answer.
Q.51 (3)
Q.57 (1)
The lobes of d x 2  y 2 orbital are alligned along X and Cr : 1s2 2s2 2p6 3s2 3p6 4s1 3d5
Y axis. Therefore the probability of finding the n+=3
electron is maximum along x and y-axis. so the combinations are 2p, 3s. So 8 electrons.

JEE-ADVANCED
Q.52 (3) COMPREHENSION/STATEMENT/MATCHING/MCQ
Q.1 (2,4)
(x) = K1. e r / K 2 (r2 – 5K3r + 6K32)
 is quadratic in ‘r’ and is a f() c 3  108
= = = 5 × 1014 sec–1
 it certainly represents  600  10 – 9
3  sheell
s  subshell 12400
E= = 2.07 eV..
An=3 6000
B  ang. nodes = 0 Q.2 (1,3)
Cl=0 Q.3 (1,3)
D  (n + 5)s  8S  8 Ground state binding energy = 13.6 Z2 = 122.4 eV.
(n + 5)p  8P  9
i.e., 6f, 2d, 5g  Z = 3.
h 1st excitation energy = 10.2 Z2 = 91.8 eV.
E  0 i.e., (  1)
2  an 80 eV electron cannot excite it to a higher
r / K 2 state.
F  r = K 1 e (r 2  5r  6)
Q.4 (1,3)
1 2  / 2
= (6  5   ).e
9 3 .a03 / 2 Q.5 (2,3,4)
solving is quadratic z 1
2 – 5 + 6 = 0 V V
n n
2 – 2– 3 + 6 = 0
( – 2) – 3( – 2) = 0 n2
= 3, 2 r  r  n2
z
code is = 300303 Ans.
1
Q.53 (4) P. E.   A V
r
Total number of electrons in an orbital = 2 (2 +1).
The value of  varies from 0 to n – 1. 1
K.E.  r
r
 Total numbers of electrons in any orbit
Q.6 (3,4)
  n 1
=  2 (2  1) .  
1
 0 

C HEMISTRY 13
Atomic Structure

Q.7 (1,3,4)
n1 4
Z (A) = =2
(1) v1 = 2.188 × 106 × m/sec. n2 2
n
v1 (n > 1) = 2.188 × 106 m/sec. n1 8
(B) = =4
1 n2 2
(2) 3.4 × 1.6 × 10–19 = × 9.1 × 10–31 × v2
2
n1 8
2  3 .4  1 .6 (C) = =8
v=  10 12 n2 1
9 .1
= 1.09 × 106 m/sec. n1 6
(3) 2r = n (D)
n2
= =2
3
 n 2   (A) & (D) are correct

2  
Z  = n × 2 × 0.529
0 .529
 Q.10 (1,2,3,4)
In transition froms 3  1 in H
n=1
v1 = 2.18 × 106 m/sec.
1  1 1  8
energy of electron = 6.9 eV  1
(4)
2
mv2
= (1)  2  2 =
v = 1.55 × 106 m/sec.  RH  (1) (3)  9

Q.8 (1,3,4) 1  1 1  8
Binding energy of ground state means energy required (1) B+4 = = (25)  2 =
 RH  (5) (15) 2  9
to more e– from n = 1 to n =  .
Ebinding energy = En=1 to n=  × Z2
 122.4 = 13.6 × Z 2
1  1 1 
 Z2 = 9 (2) He+ = = (4)  2  2 = 4 ×
 RH  (2) (6) 
Z=3
(3) Minimum energy required to excite e– from n = 1 to
1 1  8
 4  36  = 9
n = 2.

e
—
E n=2
1  1 1  8
(3) C+5 = = (6)2   2 =
n=1  RH 2
 (6) (18)  9
e
—

E = 10.2 × Z2
1  1 1  8
 2  2 = ]
E = 10.2 × 32
(4) Li+2 = = (3)2
E = 91.8 eV  RH  (3) (9)  9
(4) Egained – I.E. = kEe–
kEe– = 2.6 eV Q.11 (1,3)
Max. number of different photons emitted is 4 [(4  3
Q.9 (1,4)  1 and 4  2  1) or (4  3  2  1 and 4  1)].
Minimum number of different photons emitted is 1(4 
T1 n13 / Z2 T1 n13 1 and 4  1).
 
T2 n32 / Z22 , T2 n32
Q.12 (1,2,3)

8T1 n13 h h h
 3 = = = 2mqV .
T2 n2 mv 2mKE
When v, KE and V are same, as m increasing, 
n1 decreases. e > p >  (if v, KE and V are same).
 = 2
n2

14 J EE C OMPENDIUM
 Atomic Structure

Q.13 (1,2,3)

Q.14 (1,2,3)
R. N. = 3 – 1 – 1 = 1
1240
E = 310 nm eV  4.0eV r

(KEmax)e = 1.5 eV = qV Peaks = 1 + 1 = 2

V = 1.5 V Q.18 (1,2,3)
n = 4, m = 2
150 150 Value of  = 0 to (n – 1) but m = 2.   = 2 or 3 only
(1) e = Å Å  10Å
V 1.5 Value of s may be +1/2 or – 1/2.
(2) E = KEe + w.f. Q.19 (1,2,3)
3 = 1.5 + w.f. (1) 24Cr : [Ar]3d54s1
wf = 2.5 eV
(2) m = –  to +  through zero.
1240 1240 (3) 47Ag : 1s22s22p63s23p64s23d104p65s14d10.
(3) = nm = nm = 496 nm Since only one unpaired electron is present.
w.f . 2.5
Q.15 (3,4)  23 electrons have spin of one type and 24 of the
opposite type.
1 1
R H  12  2  2  Q.20 (2)
1 / 1 2 3 
 For minimum  of emitted photoelectron, the K.E. of
1 / 2 2 1 1
RH  1  2  2  emitted photoelectron should be maximum
1 2  E0 = 4.5 × 10–19 J E = Energy of one photon
e— K.E.max = E – E0
n=3 (2nd excited state)  E should be maximum
 Power of laser gun should be maximum & number of
e— photons should be minimum
n=2 (1st excited state)
5
E= J = 1.25 × 10–18 J
n=1(ground state) 4 1018
e— K.E.max = (1.25 × 10–18 – 4.5 × 10–19) = 0.8 × 10–18 J
2 1 5
  h
1 x 27
 = 2m(KE)
27
x=
5 6.63 10 34
=
h 2  9.1 1031  0.8 1018
As ,  
me
= 30 Å Ans.
for photons
Q..21 (4)
(mc)1 h / 1 For minimum photocurrent the combination is as
 (mc)  h /  follows
2 2
(a) 2 watt  5 × 1018 photons / sec.
2 5 (b) 3 watt  9 × 1018 photons / sec.
 y
1 27 (c) 5 watt  4 × 1018 photons / sec.
Combination (a) & (b) does not give any photoelectron
E1 hc / 1 2 5 only combination (c) will produce photoelectron.
 = z
E2 hc / 2 1 27  photocurrent = 4 × 1018 × 1.6 × 10–19 Amp.
Q.16 (3, 4) = 0.64Amp. Ans.
Q.17 (2,3)
Q..22 (4)

C HEMISTRY 15
Atomic Structure

For maximum photocurrent the combination is as

follows Q..27 (1)
(a) 2 watt  4 × 1018 photons / sec. Initial
(b) 3 watt  5 × 1018 photons / sec. Potential energy of electron = 0
Kinetic energy of electron = 6 eV
(c) 5 watt  9 × 1018 photons/ sec.
Photoelectrons will be emitted from combination (a), 150
(b) and (c) all (5  potential of electron = 6V,  kinetic
 Photocurrent = (4 +5 +9) × 1018 × 1.6 × 10–19 Amp V
= 2.88 energy of electron = 6eV)
Hydrogen like species is He+ (Z = 2) & electron comes
2.88 18 9
 Ratio = = 4.5 =  Ans.  13.6 (2) 2
0.64 4 2 in 4th shell, in this state energy = eV
Q.23 (4) 42
= – 3.4 eV.
e
—
47.2 n=3  In overall process it emits energy = 6 – (– 3.4) = 9.4
eV
eV. ]
n=2
e
—
Q..28 (2)
E = 1.89 × Z 2
n (n  1) 4  3
 47.2 = 1.89 × Z2 2
=
2
=6 ]
 Z2 = 25
Z=5 Q..29 (2)
1 1 1 1
Q.24 (3) R H  4 2  2   R H Z2  2  2 
1 4  2 8 
1 1
E = 13.6 × Z2  2  2  Q.30 (1)
 n1 n2 
2  rn = n  = 4   n = 4
1 1 
= 13.6 × 52  2  2  eV
z 2 .18  106
 3 4  v = 2.18 × 106 m/s = m/s Ans. ]
n 4
= 26.5 ×10–12 erg
Q.31 (4)
Q.25 (1) Final excited state , n = 4 , E4 = – 0.85 eV
12400 K.E. of electron after colliding with photon of 1 eV =
= Å (1–0.85) eV = 0.15 eV
E

12400 150
= 2
Å = Å = 10 10 Å
13.6  5 0.15
= 36.5 Å
Q.32 (4)
3rd highest energetic photons  (13.6 – 3.4) eV = 10.2
Q.26 (3)
KE = –TE
eV, transition is 2 1
2
Z
= –(–13.6× ) eV hc 1240
n2 = = nm = 121.5 nm
E 10.2
52 For H atom = for Li+2 ion
= + 13.6 × 2 × 1.6 × 10–19 J
1
 1 1 1
13.6 ×1 1  2  = 13.6 × 9  2
 2
 3 6 
= 544 × 10 × 107 erg
–19

= 5.5 × 10–10 erg  2 

16 J EE C OMPENDIUM
 Atomic Structure

 for Li+2 ion transition is 3 6 i.e. transition from

Initial excited state = 3 n = 1 to n = 3, n = 2 to n = 6
Final excited state = 6 n = 3 to n = 9
K.E. of electron in initial excited state of Li+2 = 13.6 ×
Q.38 (1)
32
= 13.6 eV h
32 x, mv =
4

Q.33 (4) h
V, mv =
4
h 1 0.001
x = 4 Me  V = V ´ = 300  10–5 m/ hm
V 100 multiplying by m (mv)2 =
4
s
1 Q.39 (3)
x = 5.8  10–5  = 1.92  10–2 m
300  10 5 Two unpaired electrons present in carbon atom are in
different orbitals. So they have different magnetic
Q.34 (4) quantum number.
The maximum KE of potoelectron is corresponding to
maximum stopping = 22 eV Q.40 (2)
Electronic configuration of Zn2+ ion is 1s2 2s2 2p6 3s2
 Eincident = Ethresold + KEmaxi = 40 eV + 22eV = 62 eV
3p6 3d10 so no electron in 4s orbitals.
12400 Å
incident = 62 = 200 Å
Q.41 (2)

h 1 1  h 3 h
Q.35 (3)
s (s  1) =   1 = =
Circumference = 2r = n 2 22  2 2 2

2r 3nm h
de-broglie –  = = = 1 nm = 10Å 0.866
n 3 2

12.3
Q.42 (A) – u ; (B) – s ; (C) – p ; (D) – t ; (E) – q ; (F) – r
 = Å
V It is factual.
 KE of electron in third orbit = 1.51 eV 
binding energy of third orbit in this atom Q.43 (A) – b , (B) – a, (C) – b, c , (D) – c, d.
1240 eV Å vn Z2 2rn n3
 = of photon required to ionise = 1.51 eV = 821 fn = 2r , fn  3 , T n = v , Tn  2 .
n n n Z
nm
Z2 Z2 n2
En = – 13.6 2 , En  2 , rn  .
Q.36 (1) n n Z
Mass  debrogli 
Q.44 (A) –s, (B)– r, (C)– q, (D)–p
Q.37 (3)
150
A  debroglie = (S)
debrogli h costant 13.6
=
mv z 2.18  10 6
B  Vel. = 2.18 × 106 × (R) = m/s
1 n 3

v
z2
C  Energy = – 13.6 × = – 13.6 × 9
and v 
z costant n2
n n2
D  r = – 0.529 ×
1 z
v P = 0.529 Å
n

C HEMISTRY 17
Atomic Structure

Q.45 (A) – c, (B) – d, (C) – a, (D) – b. Q.5 5

i : For Lyman series,  for second line (3  1) = Q.6 3
No of waves = principal quantum no.
1 1 8R
R(1)2  2
–
2  = 9 (c).
n=3
1 3  Q.7 3
ii : For Balmer series,  for second line (4  2) =
2 a0 n
 1 1  3R  of e- in nth Bohr's orbit =
R(1)2  –
2  = 16 (d). z
 22 4 
n = Bohr's orbit, z = atomic number, a0 = radius of 1st
iii : In a sample of H-atom for 5  2 transition, maximum Bohr's orbit of H-atom.
(5 – 2)(5 – 2  1)
number of spectral lines observed = = Q.8 1
2 Number of radial node is equal to n – l – 1
6 (a).
For p-orbital l = 1.
iv : In a single isolated H-atom for 3  1 transition,
Q.9 3
maximum number of spectral lines observed = 2 (3  2, Maximum three quantum number can be same but
2  1) (b). fourth must be different.
Q.46 (A)-p, (B)-pqs, (C)-pr, (D)-qs Q.10 2
A  R.N. = 3 P One orbital can accommodate only two electrons
B  R.N. = 3 PQR Q.11 (1)
D  A.N. = l QS Principle quantum number also gives information about
the energy of electron in an orbit and also measure the
Q.47 (A) – s ; (B) – s ; (C) – u ; (S) – q ; (E) – p ; (F) – r
average distance of e– from nucleus
It is factual.
Q.12 (3)
NUMERICAL VALUE BASED K and Cs have low ionisation energy. So can be used in
STATEMENTS photo-electric cells as they emit electrons on exposure
Q.1 6 to light
 n 2  n1  n 2  n1  1   5  2  5  2  1  6 Q.13 (2)
2 2 Mass number are always whole number as it the sum of
Q.2 2 protons and neutrons which can never be fractional.
No. of nodal axis in a px orbital are 2. Q.14 (1)
Q.3 3 Energy of 4s < 3d according to (n + 1) rule, which states
For hydrogen that energy increases in value of (n + 1)
Q.15 (1)
1 1 1 
 RZ 2   2 
 1 3  JEE MAIN
PREVIOUS YEAR QUESTIONS
1 8R Q.1 (1)

 9 Z = 37.
for ionic species Rb is in fifth period.
[Kr]5s1 is its configuration.
1 1 1
 RZ 2  2  2  1 1
 3 9  So n = 5, l = 0, m = 0, s = + or –
2 2
1 8 Q.2 (3)
 RZ 2  (En)H = – 13.6 eV
 81
n = 2  E2 = – 3.4 eV
8R 8 Q.3 (3)
 RZ 2 
9 81
h
81  ; where, m is mass and E is kinetic energy of
Z   9;
2
Z=3 2mE
9
the particle.
Q.4 6
At constant temperature, E is constant.
No. of spherical lines produced =
1
 n2  n1  n2  n1  1   5  2  5  2  1  6  
m
2 2

18 J EE C OMPENDIUM
 Atomic Structure

Q.4 (3)
2 0.529  1
The shortest wavelength of hydrogen atom in Lyman =
series is from n1 = 1 to n2 =  1
 = 2 0.529 Aº
1  1 1 
 RZ 2  2  2 
  n1 n2  Q.8 (3)
K.E = h  -h  0, So (B) is not correct.
1 1 1 1 
  R  2  2  Rfor hydrogen}
1 A 1   Q.9 (1)
We have,
1
R = 1  1 1 
A  RZ2  2  2 
The longest wavelength in Paschen series of He+ is   n1 nf 
from n1 = 3 to n2 = 4 Here of n1 = 3 and nf = 
1 1 1 1 1 1 1  12 1  10 –7
 RZ2  2  2   (2)2  2  2   10 –7  12   2    900 nm
2  n1 n2  A 3 4   3   9

4 7 7 So, the correct option A is

36A
= A  16  9  36A  Q.10 (3)
7
Q.5 (4) hc 1
= – mv 2
r = 211. 6 pm = 2.11 Å λ 2
n2 1 1 1 
r = 0.529  Å(Z = 1) mv 2  hc   
Z 2   0 
n2 = 4 n 
In Balmer series, transition of electron occurs from 6.626  1034  3  108 1
 
2
higher orbitals to orbital of n = 2    9  1031  6  105
4000  1010 2
Q.6 (4)   3.35 1019 J    2.1 eV
E = E0 + K.E Q.11 (4)
hc 2r = n
Eincident 

2r 2n 2a 0 n
 = 250 nm  2.5 × 10–7 m    2 a 0
n nZ Z
(6.626 10 –34 )  (3 108 )  = 1.5 a0
Eincident 
2.5  10 –7 n
Eincident = 7.95 × 10–19 J  2 a 0  1.5a 0
Z
7.95  10 –19 n 1.5
Eincident =  ev  5ev    0.75
1.6 10–19 Z 2
KE = Q × V
= e × 0.5V Q.12 Official Ans. by NTA (4)
K.E = 0.5 eV h    KE
E0 = E – KE
 hc 
= 5 – 0.5    KE  
   incident
E 0  4.5eV
 hc 
   KE
Q.7 (2)  incident
2r = n
p2 hc hc
n2 KE =   .......(1)
n = 2 ×0.529× Aº 2m  incident 
z
p 2  1.5
2
2 0.529  n hc
= Aº   .......(2)
Z 2m 
C HEMISTRY 19
Atomic Structure

divide (1) and (2) Q.19 (4)

 Cs has least work function value because of less
(1.5)2 =
 electronegativity thats why it is used in photoelectric
cells.
4 Q.20 (3)
  
9 In the hydrogen spectrum,
Q.13 OfficialAns. by NTA (4) Balmer series lies in visible region.
Q.21 (4)
Shortest wavelength  Max energy (   1)
(Lyman series)
1 1 
 R H (1) 2   0 
1 1 

r 1 1
 RH  RH 
1 1
For Balmer series,
Longest wavelength  Min energy (3  2)
1 1 1
 R H (2) 2  2  2 
1 2 3 

1 94
   R H (4)  36 
1  

Q.14 (4) 1 5R H 9 9
  =  1
Graph of ||2 v/s r, touches r axis at 1 point so it has one 1 9 5R H 5
radial node and since at r = 0, it has some value so it
Q.22 (3)
should be for ‘s’ orbital.
 n –  – 1 = 1 where  = 0  n – 1 = 1 n2
rn = a 0
 n = 2 ‘2s’ orbital Z
Q.15 (2)
P(x) = 4 x2 × [x]2 n2
rn 
Probability will be maximum at a and c Z
Q.16 (3)
R1 ZHe 2
a n2  R  Z  3
r 0 2 Li 2
Z
Q.23 [222]
2
a 0 (2) 4a w, work function of sodium metal
For Li2+ r   0
= 4.41 × 10–19 J
3 3
Q.17 (4) , wavelength of incident light = 300 nm
2 r = n = 3 × 10–7 m
According to Photoelectric effect
n2
2× a = n hc
Z 0 = w + KE

42
2× a = 4 6.63  1034  3  108
1 0 = 4.41 × 10–19 + KE
3  107
 = 8 a0
Q.18 (2) 6.63 × 10–19 = 4.41 × 10–19 + KE
Total no. of electronsin n = 5 are 2n2 i.e., 2  KE = 2.22 × 10–19 J = 222 × 10–21 J

1 50 Q.24 (1)
Thus, electrons having, ms = + = = 25 which is
2 2 2 subshells are associated with n = 4 and m = –2.
equal o no. of orbitals. (d and f subshells)

Q.25 (2)
20 J EE C OMPENDIUM
 Atomic Structure

 2 (probability density) can be zero for 3p orbital other vp 4m p

than infinite distance. It has one radial node. = m =4
v p
Radial nobe n – l – 1
Ans. 4
For 3p
R.N = 3 – 1 – 1
Q.31 n = 4 and ml = –3
R.N = 1
Hence,  value must be 3.
Q.26 (1)
Now, number of radial nodes = n –  – 1
=4–3–1=0
Orbital Angular Radial
Q.32 [3]
Node Node For, n = 5
5d 2 2  = (0, 1, 2, 3, 4)
4f 3 0 If  = 0, m = 0
 = 1, m = {–1, 0, +1}
3p 1 1
 = 2, m = {–2, –1, 0, +1, +2}
2s 0 1  = 3, m = {–3, –2, –1, 0, +1, +2, +3}
 = 4, m = {–4, –3, –2, –1, 0, +1, +2, +3, +4}
Q.27 [181] 5d, 5f and 5g subshell contain one-one orbital having
34 m = +2
hc (6.63  10 )(3  10 )
8

E= = 9 J/ atom
 (663  10 ) Q.33 [9]
hc
 3 10 –19  6.2 1023 = 18.06 ×104 J/mole Energy incident =
= 180.6 kJ/mole 
Q.28 [1.732] 6.63  10 34  3.0 10 8
Z = 29 [Cu element]  eV
Cu  [Ar]4s1 3d10 248  10 9 1.6  10 19
Cu+2  [Ar]3d9 6.63  3 100

248  1.6
3d = 0.05 eV × 100 = 5 eV
Now using
No of unpaired electron = 1 E = + K.E.
Magnetic moment  = n(n  2) BM 5 = 3 + K.E.
K.E. = 2eV = 3.2 × 10–19J
= 1  3 BM = 1.732 BM h
Q.29 (2) for debroglie wavelength  =
mv
1 1 1 2
DB   K.E = mv
m.K.E. mQV 2

 Li3 mp  epV 2KE

so =
= 8.33m p  3e p V m
P
h
hence  =
1 1
= = 0.2 = 2  10–1 2KE  m
25 5
6.63  10 34
Q.30 (4) =
p =  2  3.2  10 19  9.1 10 31
h h 6.63 10 34 66.3 10 10 m
=  
m p v p = m v  7.6 10 25 7.6
= 8.72 × 10–10 m
vp m 910–10 m
= m = 9Å
v p

(m = 4mp)
Q.34 (2)

C HEMISTRY 21
Atomic Structure

Statement-I is false since Bohr’s theory accounts for Q.39 [5]

the stability and spectrum of single electronic species
c 3  108
(eg : He+, Li2+ etc) nm ;   –7  z


Statement II is true. (it is a drawback of Bohrs modul  5  10

called zeeman effect) z
hh
Q.35 (4) = hhh( 
Line spectrum was explained by Bohr’s theory so J
statement-I is correct. Bohr’s model is based on
certainty so contradicts Heisenberg’s uncertaintity 1 2K.E.
= mv2 v =
principle so statement-II is correct. 2 m

Q.36 [58] 2 11.27  10 –20

v= = 5 m/s
9.1 10 –31
h
x ·p =
4 Q.40 (3)
According to Bohr’s model
h
x ·mv = Z 1
4 Vn  m/sVn nVn
n n
v = 5 
0.02
 m/s zVn
100
Q.41 [3155]
h 6.63 10 –34
x =  n2h2
4 mv 4  3.14  9.1 10 31  1000 Kinetic energy in Bohr atom =
= 5.8 m = 58 m 8m2 r 2
For second Bohr orbit n = 2, r2 = (2)2 a0 = 4a0
Q.37 [2]
(2) 2 h 2 h2
According to the question,, work function of metal is
K.E. =  ......(i)
equal to energy of photon. 8  m(4a 0 ) 2 2 322 a 02 m
photon = 400 nm
h2
hc 6.626 10  310
–34 8
Given, K.E. = .....(ii)
photon =  = 4.95 J xma 02
 400 10–9
x = 32
In 10 seconds, the amount of energy provided is 1000 x = 32 
J.
In 1 second, the amount of energy provided is 100 J. Q.42 [2]
nhc
Number of photons emitted per second E=

total energy
= energy of one photon n  6.63  1034  3 108
50 =
795  10 –9
100
Number of photons = 4.95 1019 = 2.02    50  795  109
n= = 2 
6.63  10 –34  3  108
photons
So, 2.02  photons eject 2.02 electrons from Q.43 [4]
the sodium metal. Ele. conf. of Li = 1s2 2s1
z2 9
Q.38 [6]
 E Li n  2   E H  2
 2.2  10 –18  J
h n 4
h
 p 
2meV  hc  9
E     2.2 1018  J

  4
6.6 10 34
 m
2  9.110 –31 1.6 10 –19  40 103 6.63  1034  3  108 9
 2.2  1018  J
 m   4
m x = 6  = 4 × 10–18m = 4
22 J EE C OMPENDIUM
 Atomic Structure

Q.44 (3)
Plot of 2(r) v/s 'r' for 2s orbital of single electron
E = E0 + KE
species.
For minimum energy, E = E0 (i.e. K.E of e– = 0 )
ONE radial node is there
 hc 
E =   = hv
 λ 
= 6.6 × 10–34 × 1.3 × 1015
= 8.58 × 10–19 J
 (r)
2

Q.45 (3)
We know:
hc r
E=

Radial Node  n  l  1
6.63  10 –34  3  108
  2  0 1
300  10 –9
 1 radial Node
 6.63 × 10–19 J  = 0 zero angular Node
Energy of 1 mole of photons
 6.63 × 10–19 × 6.02 × 1023 mol–1 Q.51 (4)
 399 kJ / mol O2–, Mg2+ and Al3+ have 10 electronic so they are iso-
electronic
Q.46 (1)
4d orbital Q.52 [1758]
Angular nodes   
Radial nodes = (n –  –1)   e 
h
and  n 
h
me vn mn vn
Q.47 (300) IfVe = xVn
Given; Work function 6.63  10–19 J then e = n
Planks constant = 6.63  10–34 J
C = 3  108 m/s h h

me ve m n vn
hc
E=
λ h h

(6.63 10 34
)(3 10 )
8 m e  xv n m n v n
(6.63  10–19)J =
 m n 1.6  1027
X 
(6.63  10  34 )(3  10 8 ) m e 9.1 10 31
= (6.63  10 19 ) = 175.82
 176
  300
Q.53 [10]
Q.48 (a) Number of values of n = 1, 2, 3, ..... Number of emission line
(b) Number of values of  = 0 to (n – 1)
n(n  1) 5  (5  1)
(c) Number of values of m = –  to +     10
2 2
Total values = 2  + 1
1 Q.54 (3)
(d) Values of spin =  For n = 3 only 3s, 3p & 3d
2

(e) For  = 5 number of orbitals = 2  + 1 = 11  = 0  = 1  = 2 (possible)
 = 3 (not possible) for n = 3
Q.49 (4)
Option (A), (B) and (C) are correct. Q.55 [4]
Hence option (D) is correct
no. of e  22  3  25
48 3
22 x 
Q.50 (2) no. of n 0  48  22  26

C HEMISTRY 23
Atomic Structure

No. of neutron = 9% of no of e– + no. of e– The number of electrons in the orbitals of sub-shell of n

 a  = 4 are
26 =   25   25
 100  4s 2
a
1= 4p 6
4
a=4 4d 10
4f 14
Q.56 (4) (Total) 32
Orbital is represented by n, l, m.
Q.62 (1)
Q.57 (2)
Greater the value of (n + l) grater is energy. He+ ion:
for same (n + l), greater the value of n greater is the
1 2  1 1
energy  R 1  2  2 
 H  1
n n 2 
Q.58 [270]
n2 1 2  1 1
r  R  2  2  2 
Z   He 
  2 4 
2
rHe = rH ×
n Given (H) =  (He+)
Z
1 1 1 1
 2   R  4  2  2 
 3 
2
2 4 
22
rHe = 0.6 × R(1)  n1 n 2 
2
= 2.7 Å
1 1 1 1
rHe = 270 pm 2
 2  2 2
n1 n 2 1 2

Q.59 (2) On comparing n1 = 1 & n2 = 2

Ans. 1
1 1 1 
For H: = RH × 12  2 2 ...(1)
 l   Q.63 (3)

1 1 1 Li 2  Be3 
He = RH ×22 ×    ...(2)
4 9 r2  x  k 
2 2 4k

32 9K
r3  y  k  =
3 3 4 4
He 9
From (1) & (2)  y 9 3 27
 5   
x 4 4 16
9
He    y=
27
x
5 16

9
He  Q.64 [5]
5
Q.60 (4) p x , p y , p z , d z 2 & d x 2  y2 are axial orbitals.
At node 2s = 0
Q.65 [492]
r
2  0  0
a0 1 1 1 
 R H Z2   
 r0 = 2a0  1 P  9 16 

Q.61 (2) 1 1 1 
 R H Z2   
  2 P  9 25 
24 J EE C OMPENDIUM
 Atomic Structure

60  100J
7 =
  2 P 16  9 25  7 5
 1 P = 16 =
16 16 = 1200JK–1
25  9
Q.71 [1]

25  7 Except (B) all other statements are correct.

(2)P = × 720
16 16
Q.72 [1]
(2)P = 492 nm
 1 1 
× (9)  n 2  
    n  1
–17 –18
Q.66 (2) 1.47 × 10 = 2.18 × 10 2


The spectrum of Black body radiation is explained
using quantization of energy. With increase in 1 1
0.749 = n 2 
 n  1
2
temperature, peak of spectrum shifts to shorter
wavelength or higher frequency. For above graph
 T1 > T2 > T3 > T4 . n = 1 If we take 0.749  0.75 
3
4
Q.67 (4) Q.73 (2)
Z = 55 [Cs]  [Xe] 6s1 A is correct as electrons are ejected when
[Cs+]  [Xe] i.e. upto 5s count e– of s-subshell Incident frequency > Threshold frequency
i.e. ls, 2s, 3s, 4s, 5s  10 electrons R is incorrect as atoms are ionised resulting in transfer
of energy when photons of sufficient energy strike the
Q.68 (2) metal surface.
(A) Ve = 1000 m/s ; h = 6 × 10–34 Js ;
me = 9 × 10–31 kg Q.74 (2)
Both statements (I) and (II) are correct.
h 6  1034
= = = 666.67 × 10–9m
mv 9  1031  1000 Q.75 [0]
Orbital angular Momentum
= 666.67 nm
h
(B) The characteristic of electrons emitted is independent      1
of the material of the electrodes of the cathode ray 2
tube. For s-orbital =   0
(C) The cathode rays start from cathode and move Orbital angular momentum for s – orbital = 0
towards anode.
Q.76 (1)
(D) The nature of the emitted electrons is independent
on the nature of the gas present in cathode ray tube. E1
E3 =
n2
Q.69 (3) E1
Except B and C all statements are correct. =
9
Probability density curves for 1s, 2s and 2p orbitals are Q.77 (3)
given below. The number of radial nodes in an orbital is given as
Probability Probability number of radial nodes =n – l – 1
1s density 2s density Number of radial nodes
Probability 2p
density 7s : n = 7, l = 0 7–0–1=6
7p : n = 7, l = 1 7–1–1=5
r r r 6s : n = 6, l = 0 6–0–1=5
8p : n = 8, l = 1 8–1–1=6
Q.70 [1200] 8d : n = 8, l = 2 8–2–1=5

Heat absorbed Q.78 [7]

Heat capacity 
Change in temperature

C HEMISTRY 25
Atomic Structure

h while energy order of H– is decided by (n + ) rule :

 Electronic configuration of ‘H–’ is - 1s2 its Energy order
2mKE
is decided by n+ rule.
6.6  10 34 H– = 1s22s02p0
= Its 2nd excited state is 2p
2  9  1031  4.5  10 29
and degenery 2p is ‘3’
6.6  10 34 6.6
=   104
9  1030 9 Q.3 (D)
66
=  105 Q.4 (3)
9 s-orbital is non directional so wave function will be
= 7.33 ×10–5 independent of cos .

Q.79 (4) Q.5 (1)

Size of nucleus is of order For 2s orbital no. of radial nodes = n –  – 1 = 1
1.5 × 10–15 m or 1.5 × 10–3 pm
H+ always exists in combined form. There is no relation
between two statements and hence option (4) is the
answer.

(r)
n, ,m
Q.80 (0)
All the given statements A, B, C & D are correct. The
amount of electromagnetic radiation emitted (intensity
of radiation) form a black body and its spectral –ar
o
(frequency) distribution depends only on its
temperature.
Fig. 2.8 Wavelength-intensity relationship.
(Ref : Particle nature of electromagnetic radiation; Q.6 (4)
Planck's quantum theory, ncert chapter structure of For 1s orbital  should be independent of , also it
atom.) does not contain any radial node.
Shows as the temperature increases, maxima of the
curve shifts to shorter wavelength or say higher Q.7 (1,3)
frequency.
13.6  4
JEE-ADVANCED # –3.6 =
n2
PREVIOUS YEAR’S
n=4
#=2
Q.1 6 #m=0
n = 4, Angular nodes =  = 2
m = 1, –1 Radial nodes = (n –  – 1) = 1
Hence can be n  = 4d state
= 3,2,1
i.e. Hf ; Q.8 (C)
2 orbitals n2
Hd ; r = 0.529 ×  r  n2  (I) (T)
z
2 orbitals
nh
Hp ; mvr =  (mrv)  n  (II) (S)
2 orbitals 2

1 z2
Hence total of 6 orbitals, and we want ms = – , that is KE = + 13.6 ×  KE  n–2  (II) (S)
2 n2
only one kind of spin. So, 6 electrons. z2
PE = – 2 × 13.6 ×  PE  n–2  (IV) (P)
n2
Q.2 3
Energy order of orbitals of H is decided by only principle Q.9 (D)
Same as 1 (Section-3)
quantum number (n)

26 J EE C OMPENDIUM
 Atomic Structure

Q.10 (–5246.49)
At d = d0, nucleus-nucleus & electron-electron repulsion
is absent.
Hence potential energy will be calculated for 2 H atoms.
(P.E. due to attraction of proton & electron)

–
e
– r
r e

Kq1q 2  9  10 1.6 10 

9 192

P.E.    4.355 10 21 kJ

r 0.529 10 10
 Bohr radius 

For 1 mol = –4.355 × 10–21 × 6.023 × 1023 = –2623.249 kJ/

mol
For 2 H atoms = –5246.49 kJ/mol

Q.11 30

Q.12 [30]

C HEMISTRY 27
Mole Concept Mole Concept
DPP-1
Q.1 (4)
5
Q.2 (1) 1 mol of x will give = = 2.5 mol
Q.3 (2) 2
Q.4 (2) 1.25
Q.5 (1) But % yield =  100 = 50%
2. 5
Q.6 (2)
Q.7 (3)
Q.8 (2) DPP-3
Q.9 (3)
Q.10 (2) Q.1 (2)
Q.11 (3) Q.2 (2)
Q.12 (2) Q.3 (3)
Q.13 (4) Q.4 (3)
Q.14 (3) Q.5 (1)
Q.15 (1) Q.6 (4)
Q.7 (2)
DPP-2 Q.8 (1)
XB
Q.1 (4) Molality = X  M × 1000
A A
Q.2 (3)
Q.3 (4) mB = 75 m
Q.4 (3) M  1000
Q.5 (4) m = d  1000  M  M
1
C  24 gm , H  4 gm , O  32 gm
M = 30
So, Molecular formula  C 2 H 4 O 2
So, Empirical formula  CH 2 O Q.9 (1)
(Simplest formula). 8
Q.6 (2) 125ml  1
NaOH = 100 mole
Element %(1) At.wt.(2) a/b Ratio
40
X 50 10 5 2
Y 50 20 2.5 1 10
125 
Simplest formula  X 2 Y HCl = 100 = 0.34 mole
Q.7 (3) 36.5
0.1 M AgNO 3 will react with 0.1 M NaCl to form 0.1 M HCl > NaOH
NaNO 3 . But as the volume is doubled, conc. of
Acidic
Q.10 (2)
0 .1
NO 3   0 . 05 M Let, nH2O = nNaCl = n
2
Q.8 (1) Mole of solute n
Same emprical formula m = wt. of solvent (kg) = × 1000
n  18
 same compostion by mass
Q.9 (1) 1
= ×1000 = 55.55 m.
2  56 7 18
Fe2O3 = =
3  16 3 JEE-MAIN
56 7 OBJECTIVE QUESTIONS
FeO = = Q.1 (2)
16 2
mass 46
7 7 mole  = = 2 mole.
 Fe2O3 : FeO = × =3:2 at. wt. 23
3 2
Q.10 (1) Q.2 (3)
In Ca3(PO4)2
28 J EE C OMPENDIUM
 Mole Concept

mole of Ca atom 3 12
= (3) n = × 3 = 0.75
mole of O atom 8 48

8 N
(4) n = = 0.2 × 2 = 0.4
Mole of ‘O’ atom =
3
(mole of Ca atom) NA
Mole of ‘Ca’ atom = 3 Q.9 (4)
Q.3 (A) 4.4 2.24
 (where x is mol. wt of gas)
1 x 22.4
(1) No. of atom of (C4H10) = × 14 Na ; x = 4.4 × 10
58
x = 44 (N2O and CO2 both gases may be possible).
1
(2) No. of atom of (N2) = × 2 Na
28 Q.10 (1)

1 1023
(3) No. of atom of (Ag) = × 2 Na ; No. of atoms = = 2.509 × 10+22
108 3.9854
Q.11 (3)
1
(4) No. of atom of water = × 3 Na Q.12 (2)
18
Hence greatest No. of atom = C4H10 5. 6
mole =
22.4
Q.4 (1) 5.6 1
Let mole of B = x  no. of molecule = × 2Na = × 6.02 × 1023 =
22.4 2
V.D = 25 mole ofA = 100 x
Mol. mass = 50 3.01 × 1023 atoms

80x  40(100  x) Q.13 (2)

 250 =
100
2
100 N = 6.023 × 1023 × = 1.20 × 1022
x=  25 100
4 Q.14 (2)

Q.5 (3) 1
Moles of Mg3(PO4)2 =  0.25 = 3.125 × 10–2
N2 : Ne : N2O : 8
SO3 Q.15 (3)
Ratio of total no. of moleculas = 1
: 1 : 1 : 1 1.12  10 –7
So ratio of total no. of atoms = 2 mole =
22400
: 1 : 3 : 4
1.12  10 –7
Q.6 (1) No. of molecule = × 6.02 × 1023 = 3.01 ×
22400
Mgas 1012
1.17 = M
air
Q.16 (2)
Mgas
1.17 = No. of atoms mole simplest ratio ratio
29 Cr 4.8  10 10 4.8  1010
 8  10 –14
8  10 – 4
1 1
M gas = 29 × 1.17 = 33.9 6  10 23 8  10 – 4
9.6  1010 16  10 –14
O 9.6  1010  16  10 –14 2
6  10 23 8  10 –14
Q.7 (1)
Hence E.F. is CrO2
13.5
mole of SO2Cl2 = = 0.1 mole. Q.17 (1)
135
C H O
Q.8 (3) Mass 24 8 32
10  1 24 8 32
(1) n = = 0.55
18 Moles
12 1 16
(2) n = 0.1 × 5 = 0.5
Ratio 2 8 2
C HEMISTRY 29
Mole Concept

Simple integer ratio 1 4 1 H atoms = 6 mole

by option C
Hence empirical formula is CH4O
Q.25 (1)
Q.18 (2)
3. 4
M.F.M 120 x× = 32
n 100
= n=4
E.F.M 30 x = 941.76.
 M.F = n × CH2O
= 4 × CH2O Q.26 (1)
= C4H8O2 Urea (NH2COH2)
Q.19 (A) M.wt of Urea = 60
28
Simplest ratio Ratio
% of N = × 100 = 46 %.
60
C 75 75/12 = 6.25 6.25/6.25=1 1 Q.27 (2)
H 25 25/1=25 25/6.25=4 4 0.8v + (54.2 – v) × 1 = 49.6
Hence E.F is CH4 & M.F is = n × E.F (n =1, 2, 3.....) 4.6
= 1 × CH4 = CH4. V= = 23 ml
0.2
Q.20 (3) 23  0.8
% ethanol = × 100 = 37.1%
49.6
a Simplest ratio ratio
X Q.28 (1)
30 a / 30 / a / 30  1 2
a 2  103
Y a / 20 / a / 30  3 / 2 3 amount of butter = = 363.6 gm
20 5.5  106
Hence E.F is X2Y3. Q.29 (3)
x y
Q.21 (4) =
x y
Mole fraction of H2O = 1 – 0.25 = 0.75
x C2H5OH n C2H5OH 16.006
 y’ = y + y = × 107.868
16
X C2H5OH  XH2O = n C2H5OH  nH2O or wt. % =

0.25  46 Q.30 (4)

× 100 = 46%.
0.25  46  0.75  18 8.082  12  0.234  7.833  12  0.766
Mavg =
1
Q.22 (2)
E.F of glucose = CH2O Q.31 (2)
E.F of (CH3COOH) = CH2O M2O3 0.30 × (2M + 48) = 48
 M.F = n × E.F (where n =1,2,3.....). 0.6 M = 0.7 × 48
Q.23 (3) M = 7 × 8 = 56

28.9 Q.32 (4)

194 ×
100 Q.33 (2)
= 56.06 g BaCO3  BaO + CO2
56.06 9.85
No. of Nitrogen = =4
14 197
Q.24 (3) mole–mole analysis
132 9.85
CO2 = 132 g = mole = 3 mole mole of BaO
44 197 =
1 1
54
H2O = 54 g = mole = 3 mole
18 9.85 vol
 C atoms = 3 mole Hence
197
=
22.4
(at STP)

30 J EE C OMPENDIUM
 Mole Concept

Q.38 (4)
1120
Vol = = 1.12 Lit. 1
1000
C + O  CO .... (1)
Q.34 (1) 2 2
y
CaC2 + H2O  Ca(OH)2 + C2H2  C2H4
x
Initial mole 0
... (1) 12 32

 x 1
nC2H4 
y
... (2) Final mole 0 – 
32  12  2
From equation (1)
1
mole of CaC2 = mole of C2H4 CO + O2  CO2
2
64  10 3 .... (2)
= mole of C2H4
64 For no solid residue C should be zero in eq. (1)
From equation (2) y x 1
For that –  >0
mole of C2 H 4 mole of polymer 32 12 2
=
n 1 y x
>
10 3 wt of polymer 32 24
= n (28)
n y 32 y
> > 1.33
Wt. of polymer = 28  103 g = 28 Kg x 24 x
Q.35 (1) Q.39 (2)
Use reaction C12H22O11 + 12O2  12CO2 + 11H2O. C2H4 + 3O2  2CO2 + 2H2O
From Gay lussac's law
34 C2H4 & O2 are in 1:3 vol.ratio
In 24 hr. moles of sucrose consumed = × 24.
342 i.e O2 will be 60 ml.
34
 In 24 hr. moles of O2 required = × 24 × 12. Q.40 (2)
342
(according to stoichiometry). (C + S)  CO2 + SO2

34 nCO2
Mass of O2 required = × 24 × 12 × 32 = 916.2 g. nSO2 
342 2
Q.36 (1) Let wt. of C = x
So, wt. of S = 12 – x
2 SO2 + O2  2 SO3
Initial mole 10 15 0 12  x 1  x 
  
Final mole (10 – 2x) (15 – x) 2x 32 2  12 
 Given 2x = 8
x = 5.14 g.
 x=4
 Mole of SO2 left = 10 – 2 × 4 = 2 Q.41 (2)
Mole of O2 left = 15 – 4 = 11 Let mol of Fe undergoing formation of FeO = x
Let mol of Fe undergoing formation of Fe2O3 = 1 – x
Q.37 (4)
1
5 then, Fe + O  FeO
2NH3 + O2  2NO + 3H2O 2 2
2 x x/2 x
from mole-mole analysis
3
nNH3 nO2 2Fe + O 
2 2
=
2 5/2 Fe2O3
3 1 x
6.8 nO2 1–x
4
(1 – x)
2
17 = 5
2 x 3
2 As given,  (1 – x) = 0.65 = Total moles of
24 4
nO2 = 0.5 mole.
oxygen
C HEMISTRY 31
Mole Concept

x = 0.4 = moles of FeO  60 n + 64 n = 620  n = 5

1 x produced CO2 = 2n = 10 mole
= 0.3 = moles of of Fe2O3 CO2 mass produced = 10 × 44 = 440 gram
2
Q.47 (3)
Mole of FeO CO = x ml ; CO2 = y ml, N2 = z ml
 Mole of Fe O
2 3 x + y + z = 200 ....(i)
4 CO + 1/2 O2 = CO2
= x o Contraction = x/2
3
o x
Q.42 (2) CO2 No reaction ; N2 + O2  no reaction
C6H5OH + 7O2  6CO2 + 3H2O() change in volume = x/2 = 40
30ml x = 80 ml
6 × 30 = 180 ml of CO2 is produced 50
x + y = 200 × = 100 ...(ii)
Volume used initially 100
= 30 + 210 = 240 y = 20 ml ; z = 100 ml
(for C6H5OH) (for O2)
Q.48 (1)
change in volume = 240 – 180 = 60 ml
Let volume is V ml
H2SO4 + 2 NaOH  Na2SO4 + 2H2O
Q.43 (3)
mmole 0.2 V 40 x 0.1
NxOy + y H2  yH2O () + x/2 N2(g)
40  0.1
x / 2 10 m. moles of H2SO4 remains = 0.2 V –
= 2
y 30
40 x 0.1
x 2 0.2V  6
= 2 = V = 70 mL
y 3 V  40 55
Q.44 (2)
CaC2 + 2H2O  Ca(OH)2 + C2H2 Q.49 (2)
3BaCl2 + 2Na3PO4  Ba3(PO4)2 + 6 NaCl
100 mole 0.5 0.1
(excess)
64
0.5 0 .1
From mole-mole analysis (L.R is Na3PO4)
3 2
100 nC2H2
= (here n = mole) Now from mole– mole analysis
64 1
mole of Na 3PO 4 mole of Ba 3 PO 4 2
vol. = nC2H2 × 22.4 (at N.T.P) =
2 1
100 0 .1
= × 22.4 = 35 lit. = = mole of Ba3(PO4)2
64
2
Q.45 (2)  mole of Ba3(PO4)2 = 0.05 mol.
C = 84/12 = 7 mole Q.50 (3)
H2 = 12 g = 6 mole 2P + Q  R
O2 = 56/22.4 = 5/2 mole 8 5
12C + 11H2 + 11/2 O2  C12H22O11 8/2 5/1 (L.R is P)
L.R. = O2 from mole-mole analysis
11/2 mole O2 produce 1 mole sucrose
8 nR
5/2 mole O2 will for 5/11 mole sucrose = (here n= mole)
mass of sucrose = 5/11 × (mol. mass) 2 1
= 5/11 × 342 nR = 4 mole of R.
= 155.45 g
Q.46 (3) Q.51 (1)
C2H4O2 + 2O2  2CO2 + 2H2O (1) Explanation : 2 Ag + S  Ag2 S
n mole 2n mole for max. energy 2 × 108 g of Ag reacts with 32 g of sulphur
60 n gram 2n × 32 gram 32 320
 60 n gram 64 n gram 10 g of Ag reacts with × 10 = >1g
216 216
32 J EE C OMPENDIUM
 Mole Concept

It means ‘S’ is limiting reagent balancing O atom

32 g of S reacts to form 216 + 32 = 248 g of Ag2S 3n = 2n + 1
n=1
248
1 g of S reacts to form = = 7.75 g
32 Q.58 (1)
Alternately M1V1 + M2V2 = MR [V1 + V2]
10 1 1 × 500 + 1 × 500 = MR [500 + 500]
neq of Ag = = 0.0925 neq of S = = MR = 1.
108 16
0.0625 (neq = number of equivalents)
Q.59 (3)
Since neq of S is less than neq of Ag
 0.0625 eq of Ag will react with 0.0625 eq of S to 0.10  2  V – 50  0.10  1
0.050 × 2 =
form 0.0625 eq of Ag2S V  50
Hence , amount of Ag2S = neq× Eq. wt. of Ag2S =  V = 100 ml.
0.0626 × 124 = 7.75 g

Q.52 (2) Q.60 (1)

A + 2B  C Both have equal volume = V
5 8
 v  10   d
5 8  
(B is L.R) HCl =  100  HCl
mole; NaOH =
1 2 36.5
From mole–mole analysis
 v  10   1.5 d
8 nC  
=  100  HCl
mole
2 1
40
nC = 4 mole of C.
NaOH mole > HCl mole
Q.53 (1) Basic Solution
Limiting reactant is A
Ideally with 2 moles of A, D formed = 3 moles Q.61 (1)
But yield = 25% Molar fraction & molality is independent of
So, moles of D formed temperature.
= 3 × 0.25 = 0.75 mol
Q.62 (2)
Q.54 (1) 1000 mL solution contain 2 mole of ethanol or 1000 ×
1.025 g solution contain 2 mole of ethanol
Mole of HCl 0.52 wt. of solvent = 1000 × 1.025 – 2 × 46
LR  HCl, so Mole of H2 = = =
2 2
2
0.26 m= × 1000
1000  1.025  2  46
Q.55 (1) 2
(1) L.R.  Al m=
933
× 1000 = 2.143
(2) Mole of AlCl3 = mole of Al = 1.0
(3) Mole of Cl2 used = 1.5
Q.63 (3)
Hence left mole = 3 – 1.5 = 1.5.
6.02  10 22 1
Q.56 (1) Molarity = 23  = 0.2
6.02  10 1/ 2
I2 + 2CI2  ICI + ICI3 Q.64 (2)
Given mass 25.4 gram 14.2 gram
0 0 2 .8
1
0.1 mole 0.2 mole M = 56 × 1000 = M
0 0 100 2
0 0
0.1 0.1 Q.65 (1)
Q.57 (2) 100 gm oleum gives H2SO4 = 112 gm
M2(CO3)n + 2HCl  nCO2 + 2MCln + H2O
C HEMISTRY 33
Mole Concept

Q.72 (2)
112
12.5 gm will give H2SO4 =  12.5 = 14 gm Mole = M  V
100 100  10–3 = 0.8  V
14 V = 0.125
No. of moles of H2SO4 = Q.73 (4)
98
2 4
14 Moles of Cl– in 100 ml of solution =  ×2+
2 58.5 111
Conc. of H ions = 98
+
= 2.85 × 10–3 M
100 6
= 0.2184
53.5
Q.66 (2) 0.2184
Molarity of Cl– = × 1000 = 2.184.
250  0.5  0 100
 NA = 6 × 6.023 × 1023 = 3.76 × 1022
750 Q.74 (4)
Q.67 (4) 400  300  200
Conc. of cation =
m = 0.2 mole / kg 400
weight of solvent = 1000 gram
weight of solute = 0.2 × 98 = 19.6 gram 200  300  400
Conc. of anion =
Total weight of solution = 1000 + 19.6 = 1019.6 ml. 400
 Ratio of the conc. = 1
Q.68 (1)
JEE-ADVANCED
nA
Mole fraction of A i.e. XA = Total moles OBJECTIVE QUESTIONS
Q.1 (1)
H2SO4 A2(SO4)3
nH2O
So XH2O =  
Total moles 32 3 × 32
so total molecular 
XA n
Now  A 1
XH2O nH2O mass = 98 (A2(SO4)3)
3
n A  1000 X A  1000 
and molality =  =
nH2O  18 XH2O  18 1
× 342
3
0.2  1000 
= 13.9 Ans.
0.8  18 114
Q.69 (3) 98
= 0.86
98  10  1.84 114
Molarity = = 18.4 M
Gmm Q.2 (1)
46x + 30(100–x) = 34 × 100
(% w / w )  (d)  10 Let % by mole of NO2 be x.
{ M = Mol. mass of solute } (d in g/ml.)
Q.3 (3)
Q.70 (2) 3  0.5
Weight of KOH = 2.8 gram NaI mass = = 0.015 gm
100
Volume of solution = 100 ml
0.015
2.8  1000 28 No. of moles of NaI = = 1 × 10–4
M= = = 0.5 M 150
56  100 56
No. of I– ions = 10–4 × 6.023 × 1023 = 6.023 × 1019
Q.71 (3)
M Q.4 (3)
Molarity of Cl– = 3 (molarity of FeCl3) = 3  30  =
  79  24  21  x  25  x  26
Mavg = 24.31 =
M 100
.
10 x = 10
34 J EE C OMPENDIUM
 Mole Concept

Q.5 (3) Q.13 (1)

Average atomic mass =
M
P = V  V = 8.533
f i % of I isotope  its atomic mass  % of II isotope  its atomic mass
100
Q.6 (1)
1.71 75.53 x 34.969  24.47 x 36.96
No. of carbon atom in glucose = × 12 Na =
342 100
= 3.6 × 1022 = 35.5 amu.
Q.7 (3)
0.79 × 24 + x + 26 + (21 – x) × 25 = 24.31 Q.14 (3)
x = 0.1  1 mol of C6H12O6 has = 6 NA atoms of C
 % Mg26 = 10%  0.35 mol of C6H12O6 has
= 6 × 0.35 NA atoms of C
Q.8 (2) = 2.1 NA atoms
= 2.1 × 6.022 × 1023 = 1.26 × 1024 carbon atoms
0.15x  5 8 460
Let initial = xg ; = x= g
x 5 100 7 Q.15 (1)
 mol. wt. of CaCl2 = 111 g
0.4x
× 100 = 43.29% 111 g CaCl2 has = NA ions of Ca+2
x 5
N  222
 222g of CaCl2 has A = 2NA ions of Ca+2
Q.9 (3) 111
Also  111 g CaCl2 has = 2NA ions of Cl–
A:B:C  1:3:5
b  x : y = 32 : 84 by mass 2 N A  222
 222 g CaCl2 has = ions of Cl– = 4NA
= 1 : 3 by mole 111
C  x : y = 16 : 5  16 : 70 ions of Cl– .
Q.16 (1)
Q.10 (1)  1.429 gm of O2 gas occupies volume = 1 litre.
32
 y y  32 gm of O2 gas occupies = = 22.4 litre/
CxHy +  x  4  O2  XCO2 + H2O (g) 1429
.
  2 mol.
(g) (g) Q.17 (3)
C4H10 = 80 ml
 y
1  x   CH4 = xml CO = y ml
 4  600
 x + y = 120 ml
 y 700 C4H10  4 CO2 ,
x  
 2  80 ml 320 ml,
CO  CO2
5y y ml y ml
x+7=
4 CH4  CO2
by option (1) x ml x ml
Q.11 (1) total CO2 volume
X Y = 320 + x + y ml
75.8 24.2 = 320 + 120
= 440 ml
75 16
1.01 1.5 × 2 Q.18 (4)
2 3 On balancing the reaction,
Q.12 (2) 13
The weight % of available Cl2 from the given sample of C4H10 + O  4CO2 + 5H2O
2 2
bleaching powder on reaction with dil acids or CO2 is
called available chlorine. Mole of C 4H10 Mole of CO 2
=
1 4 1
CaOCl2  H2SO 4  CaSO 4  H2O  Cl2
Hence mole of CO2 = 4 × mole of C4H10
71 4 × 0.15 = 0.60.
Max. % of available of Cl2 = × 100 = 55.9 %.
127
C HEMISTRY 35
Mole Concept

Q.19 (1)
5
On balacing Na atoms on both sides of reaction, we get Moles of HNO3 =  10
: 254
y = 6x.
 x:y=1:6 5  10
(only A option matches). Mass of HNO3 =  63 = 12.4 g
Q.20 (2) 254
Q.24 (1)
21.2  10 3
Moles of Na2CO3 = = 200 20 g KCl present in 100–20 = 80 g of H2O
106
20
So moles of CO2 = 200 Wt. of KCl in 60 g water =  60  15 gram
& so moles of CaCO3 reqd = 200 80
 wt of CaCO3 reqd = 200 × 100 = 20 kg. Q.25 (2)
Q.21 (4) 2NaCl + Ag2SO4  2AgCl + Na2SO4
CxHy + O2  CO2 + H2O Initially
POAC on c No. of moles of Ag2SO4 = 2 × 2 = 4
500 2.5 No. of moles of NaCl = 4 × 1
x× =1× AgCl formed = 4 moles
22400 22.4
No. of moles of Ag2+ left = 4 × 2 – 4 = 4
x=5 No. of moles of Cl– left = 0
POAC on H No. of moles of Na+ = 4
500 3 No. of moles of SO4–2 = 4
y× =2×
22400 22.4 12
y = 12 Sum of molar conc. = =2M
6
Hence hydrocarbon is C5H12.
Q.26 (2)
Q.22 (2)
2H2 + O2  2H2O
P4 + O2  P4O6 + P4O10
8  16 
31 (g) 32 (g) Given moles    
According to question weight of P is conserved so 2  32 
Let Mole of P4O6 = a 4 0.5
Mole of P4O10 = b So O2 is the limiting reagent
Initial weight of P = Final weight of P. moles used of H2 = 1
31 = [a × 4] × 31 + [b × 4] × 31 So unreacted moles = 6 gm.
4 a + 4b = 1] (1) × 3
Initial weight of oxygen = Final weight of oxygen Q.27 (3)
32 = [ a × 6] × 16 + [a × 10] × 16 2H2 + O2  2H2O
3a + 5b = 1] (2) × 4
4 4 1
12 a + 20 b = 4 mole =
2 32 8
1
12 a + 12 b = 3 So b = 4/2 1/ 8
8 (O2 is L.R.)
2 1
8b=1
From mole–mole analysis
1
Similarly a = 1
8 n
8 = H2O
1 284 1 2
So weight of P4O6 = × 220 = 27.5 P4O10 = =
8 8 1
35.5. nH2O =
4
Q.23 (1)
I2 + 10 H NO3  2 HIO3 + 10NO2 + 4H2O 1
MassH2O = × 18 = 4.5 g.
4
5 Q.28 (1)
Moles of iodine =
254 CaCl2 + NaCl = 10 g
Let weight of CaCl2 = x g
CaCl  CaCO3  CaO
36 J EE C OMPENDIUM
 Mole Concept

1 mol 1 mol 1 mol Q.32 (C)

x x x B2 [H2PtCl6]2  Pt
mol mol mol 12 gm w gm
111 111 111
POAc for Pt
1.62
Mole of CaO =
56 12  2 w
=
x
2  58  410  2 195
1.62
 = or w = 5 gm Ans. ]
111 56
x = 3.21 g Q.33 (1)
3.21
% of CaCl2 = ×100 = 32.1 % Ag + HMO3   AgCI
NaCI
10 21.6
Q.29 (2) 14.35
P4S3 + 8O2 
21.6
P4O10 + 3SO2 mole = 0.2
108
440 g 384 g
Ag Atom remain conseved
(mass)
So No. of mole of Ag = No.
440 of mole of Ag CI
=2 12 So. No. of mole of AgCI = 0.2
220
Weight of AgCI = 28.7
(mole) % Yield =
O2 is limiting reagent
14.35
12 × 100 = 50 %.
28.7
so moles of P4O10 produced =
8
Q.34 (4)
12 100kgimpuresamplehaspure CaCO3 = 95 kg
mass of P4O10 produced = × 284 = 426 g
8 95  200
Q.30 (1)  200 kg impure sample has pure CaCO3 =
100
3 Mg + 2NH3  Mg3 = 190 kg.
N2 + 3H2 CaCO3  CaO + CO2
48 34  100 kg CaCO3 gives CaO = 56 kg.
(mass)
56  190
2 2  190 kg CaCO3 gives CaO = = 106.4 kg.
(mole) 100
Mg is limiting reagent Q.35 (D)
Initially 15 m mole
2 2NH3 + H2SO4 
So moles of Mg3 N2 = (NH4)2 SO4
3
6 m mole
2 200 No. of m moles of H2SO4 neutralised = 15–6 = 9 m mole
mass of Mg3N2 = × 100 = No. of m mole of NH3 required = 2×9 = 18 m mole
3 3
=
Q.31 (3)
18×10–3 mole
Relative no. of atoms C : H : O
From PV = nRT
9 1
: : 0.25 nRT 18  10 3  .0821 273
12 1 VNH3 = = =.4914
3 4 1
P 0.821
Empirical formula mass = 36 + 4 + 16 = 56 litre = 491.4 mL Ans.]

108 Q.36 (B)

n= =2
50 Moles of Na2SO4 = 200 × 0.1 × 10–3
Molecules formula = 2 (Empirical formula) Moles of Na+ = (200 × 0.1 × 10–3 ) × 2 = (2 × 10–2 ) × 2
= 2 (C3H4N) Moles of Na3PO4 = 100 × 0.2 × 10–3
= C6H8N2 Moles of Na+ = (100 × 0.2 × 10–3 ) × 3 = 2 × 10–2 × 3
Total moles of Na+ = 5 × 2 × 10–2 = 10–1
C HEMISTRY 37
Mole Concept

10 1 1 3
M Na  =  1000 = = 0.33 M Ans. ] x – x = 9 [29 – 20 = 9]
300 3 2
Q.37 (C) x = 18
x = 90% [O3]
500 O2 = 10%
Mol. of H2SO4 = 2 × = 1 mol Q.40 (1)
1000
 Mol of H+ = 1 × 2 = 2 CH4 + 2O2  CO2 + 2H2O
but given mol of H+ = 1.5 1 2
x 2x
1.5
 % purity = ×100 = 75 % Ans. x + 2x + 8x = 1
2
11x= 1
and required mol of OH¯ = mol of H+
 1.5 mol 1
x=
1.5 11
 Vol. of NaOH = = 1.5 litre
1 1 2 8
CH4 = , XO = , x N2 =
11 2 11 11
(mol of H+)
Q.41 (B)
1.5
1.5 M H3PO4 150
1.0 ml
H3PO3 + 2NaOH  Na2HPO3 + 2H2O
0.5 0.225 450
135°
n NaOH 450
1.5 L M= V= = 900 ml ]
vol. of NaOH added V(l ) 0 .5
(L)
Q.42 (3)
Slope = tan135° = –1 Ans. ]
Q.38 (1) M1V1  M2 V2
NaH2PO4 + Mg2+ + NH4+  Mg(NH4)PO4. 6H2O M final = V1  V2  Vwater ; 0.25 =
heated
   Mg2P2O7
0.6  250  0.2  750
Since P atoms are conserved , applying POAC for P
250  750  Vwater ; So Vwater = 200 mL.
atoms,
moles of P in NaH2PO4 = moles of P in Mg2P2O7
1 × moles of NaH2PO4 = 2 × moles of Mg2P2O7 Q.43 (2)
( 1 mole of NaH2PO4 contains 1 mole of P and 1 mole
of Mg2P2O7 contains 2 moles of P) Q.44 (3)
V1 ml 0.2 M NaOH, V2 ml 0.1 M CaCl2
wt.of NaH 2 PO 4 wt.of Mg 2 P2 O7
= 2 × (+ve ion) = 0.2 V1 = 0.1 V2 mole
mol.wt.of NaH 2 PO 4 mol.wt.of Mg 2 P2 O7 (–ve ion) = 0.2 V1 + 0.1 ×2V2
= 0.2V1 + 0.2 V2 mole
wt.of NaH 2 PO 4 1.054
=2× . by equation
120 222
40
Wt. of NaH2PO4 = 1.14 g. (+ve) = (–ve) – (–ve) ×
100
Q.39 (2) 60
= (–ve) ×
2O3  3O2 100
2 3
6
 0.2 V1 + 0.1 V2 = 0.2 (V1 + V2) ×
3 10
x x
2  2V1 + V2 = 1.2 V1 + 1.2 V2
 0.8 V1 = 0.2 V2  4V1 = V2
V1 = 200 ml, V2 = 800 ml

38 J EE C OMPENDIUM
 Mole Concept

Q.45 (1) = 0.2 mole of CO2 = 0.4 mole of O-atom.

XB Q.2 (A,B,C)
Molality = X  M × 1000 Mole of NH3 = 1.7 = 0.1
A A
Mole H atom = 0.3
mB = 75 m Total atoms = 0.4  6.02  1023 = 2.408  1023
M  1000 3 1
m = d  1000  M  M %H=  100 = 17.65%
1 17
M = 30 Q.3 (A,B)
M.Wt. = d × volume of 1 mole of gas at STP
Q.46 (4) 28.96
V. D = = 14.48
% by weight  10  d 2
M= Mw 2 So (A) and (B) are correct answer.
Q.4 (C,D)
36.5  10  1.2
= = 12 M 1
36.5 M
(A) V.D. = ;M 
36.5  1000 2 total moles
m= as mole will decrease  V.D. decrease  correct
36.5  (100  36.5)
(B) with reaction moles will decrease  correct
1000 (C) incorrect
= = 15.7 m
63.5 (D) incorrect ]

Q.47 (1) Q.5 (A,B,C)

v.s. = N × 5.6 Let volume of solution = 1000 mL
or 11.2 = N × 5.6 [Ba2+] = 5 M ; [Cl–] = 10 M
or N = 2eq/L [Na+] = 10 M
= 2 × 17 g/L [Cl–] = 10 M
= 34 g/L 1000 ml solution = 1949 g solution
solute  BaCl2, NaCl & Na2X
34g BaCl2 = 5 mole = 1040 g
= 1000 ml × 100 = 3.4% (wt/vol)
NaCl = 588 g ; Na2X = mole of Na2X × 142
Q.48 (4) Solvent = 1949 – (1040 + 588 + 142nNa2X)
Total wt. of NaOH = 30 + 90 = 120 = 321 – 142 n Na2X
Total vol. of solution = 100 + 100 = 200 nNa X
2
mNa2X = 321  142n  1000 = 2
120 1000
M=   15 Na X 2

40 200 nNa
2X
= 0.5
JEE-ADVANCED Q.6 (B,C,D)
COMPREHENSION/STATEMENT/MATCHING/MCQ
Q.1 (B,C) C + O2  CO2
Equal number of present Mass 27 88
10 10 27 88
(A) 10 mole H2O (l) = 10 gm = mole of H2O = Moles
18 18 12 32
mole O-atom C is limiting reagent
(B) 0.15 mole of V2O5 = 5 × 0.15 = 0.75 moles of O-atom 27
Moles of CO2 produced = moles of C = = 2.25
12 12 12
(C) 12 gm O3(g) = mole of O3 =  3 = 0.75  Volume of CO2 at STP = 2.25  22.4 = 50.4 L
48 48
Ratio of C and O in CO2 = 12 : 32 = 3 : 8
mole O-atom
Moles of unreacted O2 = 2.75 – 2.25 = 0.5
12.044 1022  Volume of unreacted O2 at STP = 0.5  22.4 = 11.2 L
(D) 12.044 × 1022 molecules of CO2 = Q.7 (A,C)
6.023 1023
216
mole of CO2 0.5 x n = = mol of Ag
108
C HEMISTRY 39
Mole Concept

n=4 Q.11 (A,B)

M.wt = 58 + [165]n g/mol = 718 g/mol In 5 gm molecules of C14H18N2O5
Q.8 (A,C) No of g-atoms of H = 18 × 5 = 90
Convert all the wt. in mole and use limiting reagent  Mass of hydrogen = 90 g
concept find out the mole produced of NH3. No of g-atoms of C = 14 × 5 = 70
In (A) & (C) it comes equal to 10 moles  Mass of C = 70 × 12 = 840 g
A&C No of g-atoms of O = 5 × 5 = 25
Q.9 (B,C)  Mass of O = 25 × 16 = 400 g

(i) K4Fe(CN)6 + 3H2SO4  2K2SO4 + FeSO4 + 840

6HCN Ratio of mass of C to oxygen = = 2.1
400
1 mole 5 mole total moles of all atoms = 5 × (14 + 18 + 2 + 5)
Limiting 1/1 5/3 = 39 × 5 = 195
reagent
(1–1) (5–3 × 1)2 × 1 1×1 6×1 Q.12 (A,C)
0 mole 2 mole 2 mole 1
mole 6 mole 1.12
CaCl2  CaCO3  CaO =0.02mole
Limiting reagent in step (i) is K4[Fe(CN)6] 56
CaO
(ii) 6HCN + 12H2O  6HCOOH + 6NH3  Moles of CaCl2 = 0.02 Mole
6 mole (excess) 0 0 Mass of CaCl2 = 0.02 × 111 = 2.22 g
0 6 mole 6 mole
2.22
 % of CaCl2 = 4.44 × 100 = 50 %
(iii) (a) 6NH3 + 3H2SO4  3(NH4)2
SO4 Q.13 (B,D)
6 mole 2 mole 0
Limiting 6/6 2/3 3A + 2B 
reagent A3B2
Initial mole 3 3
2 2 2
(6– × 6) (2– × 3) (3 × ) 0
3 3 3 Final mole 0 3–2
2 mole 0 mole 2 mole 1
H2SO 4
(b) 6HCOOH    6CO + 6H2O
6 mole 0 mole 0 mole A3B2 + 2C 
0 mole 6 mole 6 mole A3B2C2
Limiting reagent in step (i) is K4[Fe(CN)6] Initial mole 1 1
(NH4)2SO4 = 2 mol 0
CO gas = 6 mol 1
Q.10 (A,B,C) Final mole 1 – 0
2
(Mw of Na2CO3 = 106, Mw of HCl = 36.5, Mw of NaCl =
58.5) 1
2
106
Moles of Na2CO3 = = 1.0 mol Q.14 (A,B,D)
106 (A) Weight of CaCO3 = (0.22 g CO2)
109 .5  1 mol CO 2   1 mol CaCO 3   100g CaCO3 
Moles of HCl = = 3.0 mol      
36.5  mol CaCO 
 44 g CO 2   mol CO 2   3 
(A) Since for 1 mol of Na2CO3, 2 mol of HCl is required.
So, HCl is in excess (3 – 2) = 1.0 mol 0.22  100
Therefore, Na2CO3 is the limiting quantity. = = 0.5 g CaCO3
44
(B) Weight of NaCl formed = (1.0 mol Na 2CO 3)
 0.22 
 2 mol NaCl   58.5g NaCl  (B) Moles of CaCO3 = moles of Ca =   = 0.005
 
 mol Na CO   mol NaCl  = 1 × 58.5 = 117.0 g  44 
 2 3   
mol
NaCl Weight of Ca = 0.005 × 40 = 0.2 g Ca
(C) 1 mol of Na2CO3 = 1 mol of CO2 = 22.4 L at NTP

40 J EE C OMPENDIUM
 Mole Concept

(D) % of Ca =
0. 2
× 100 = 20% Ca PV 0.05  240  10 12
1 .0 n= = = 7.5×10–13 mole
RT 0.08  200
Hence (C) is wrong.
Q.15 (A,B,C,D) n 7.5  10 13 mole
Silica H2O Impurities Concentration = = = 7.5 × 10–
% in original clay  40 19 100 V 1
– (40 + 19) = 41 13 mole/L

% after partial drying  a 10 100

VCCl2F2
Similarly , VCCl2F2 ( ppt )  1012
– (a + 10) = 90 – a
On heating, only water evaporates from clay, whereas Vall gas
silica and impurities are left as it is. Therefore, % ratio
of silica and impurities remains unchanged, i.e. VCCl2F2
40 41 300   1012
= ,  a = 44.4% 1
a 90  a
% of impurities after partial drying = (90 – a) = (90 – VCCl2F2 = 800 × 10–12
44.4) = 45.6%
PV 0.05  800  10 12
Q.16 (A,C) VCCl2F2 = = = 2.5 × 10–12
Mw of CaCO3 = 100, Mw of Na2CO3 = 106
RT 0.08  200
Mw of HNO3 = 63 g mol–1 mole/L ]
Q.20 (B,D)
Na2CO3 + CaCO3  CaCO3 + 2NaCl
2  1000  2
 4.44
1000 1.09  190
10 Molality of Cl¯ =
(a) moles of CaCO3 = = 0.1 mol
100
moles of Na2CO3 = moles of CaCO3  2 × moles of NaCl
Weight of Na2CO3 = 0.1 × 106 = 10.6 g Q.21 (A,B)
Q.22 (A,B,C,D)
10.6 Assuming 1000 gm of water
% purity Na2CO3 = = 100 = 50%
21.2 wt. of solution = 1000 + 2 × 34 = 1068 gm
(b) wrong
(c) correct
1068
Vol. of solution = = 1000 ml
(D) moles of NaCl = 2 × 0.1 = 0.2 mol 1.068

Q.17 (A,B) moles of H 2 O 2 2

Molarity =
Q.18 (A,B) vol. of solution (in L) 1 = 2M
=
Q.19 (A,C)
volume strength
VCCl3F Molarity =
VCCl3F( ppt )  10
12
11.2
Vall gas  Volume strength = 2 × 11.2 = 22.4 V
Let Vall gas = 1 L 1000 ml of solution contains 68 gm H2O2

VCCl3F 68
 10 12  100 ml   100 = 6.8 gm
240 = 1000
1
VCCl3F  240  10 12 w
%   = 6.8%
v
Let Vall gas = 1L
VCCl3F 1000
240 =  1012 250
1 18
Mole fraction of water = = ]
1000
VCCl3F = 240 × 10–12  2 259
18
Thus mole of CCl3F, PV = nRT
Q.23 (A,B,D)

C HEMISTRY 41
Mole Concept

1 mole of air = 0.8 mole N2 + 0.2 mole O2

10  d  x
(A) Molarity of second solution is = =1M = 0.8 × 28 + 0.2 × 32 = 28.8 g = 22.4 Ltr volume.
M
(B) Volume = 100 + 100 = 200 mL m 22.8
D= = = 1.2857 g/L
V 22.4
200  1
(D) Mass of H2SO4 = × 98 = 19.6 g.
1000 Q.31 (A)
Q.24 (A,B,D) Q.32 (B)
Vml 0.1 M NaCl Q.33 (B)
Vml 0.1 M FeCl2
V  0 .1 Q.34 (B)
[Na+] = = 0.05 M
VV Q.35 (C)
Q.36 (B)
V  0 .1
[Fe2+] = = 0.05 M
VV Q.37 (B)
V  0 . 1  V  0 . 1 2
[Cl–] =
VV
= 0.15 M 20 / 80 0.25
x= = =
20 30
 0.25  0.31
Q.25 (B) 80 98
Q.26 (C) 0.25
 0.45
Q.27 (D)
0.56
Q.38 (C)
x C2H4 C 2H 4 H2O(l) Mass of H2O added
CO CO2 = moles of SO3 in (100g) × 18
Sparking
y CO N2 N2
O2 O2 20
z N2 H2O(Vapour) =2×  18
80
x + y + z = 250 .... (i) = 4.5 × 2 = 9
C2H4 + 3O2  2CO2 + 2H2O (l) Labelling = 100 + 9 = 109%
(2x + y) + z + [(250 – (3x + y/2)] + 20 = 370
1 Q.39 (A)
CO + O2  CO2(g)
2 1000
m of pure subtance =
–x + y/2 + z = 100 ......(iii) M. mass of subs tan ce
2x + y = 200 .... (ii)
 MA = 44, MB = 64
molarity of A is solution is 0.1 M
From (i), (ii) & (iii)
i.e. 0.1 mol of gas A present 1 l solution
x = 50 , y = 100 & z = 100 ]
10 1
Q.28 (C) PV
 n total in solution = 200
11.2 R T = 0.082 
11.2 g of N2  = 0.4 mole 0.821
28
= 0.5 mol.
 air = 0.5 mole  0.5 × 22.4 = 11.2 Ltr air  nA + nB = 0.5
 nB = 0.5 – 0.1 = 0.4 mol
Q.29 (B)
1 mole of air  0.8 mole of N2 = 0.8 × 28 g N2 0.1 103 250 125
 0.2 mole of O2 = 0.2 ×32 g O2  mA = = =
0.4  64 64 32
w O2  100 0.2  32  100
 % w/w O2 = = =
w O2  w N2 0.2  32  0.8  28 Q.40 (C)

22.2% 0.1 44  0.4  64

Mavg = = 60 ]
0 .5
Q.30 (B) Q.41 (B)
Density of air at NTP
42 J EE C OMPENDIUM
 Mole Concept

nRT 0.5  0.0821  500 89  3

V=
P
=
8.21
= 2.5 L % of Y =
89  3  5  27   12 16 × 100
0 .1 4 267  100
 [A] =  = = 44.95%
2 .5 4 594
= 0.04 M ] 5  27
Q.42 (B) % Al =  100 = 22.73
Q.43 (D) 594
Q.44 (C) 12  16
Mass ratio  1 : 2 : 2 %O=  100 = 32.32%
594
1 2 3 Q.47 A-Q, B-R, C-P, D-T
Mole ratio  : : 
5  28 5  28 5  28 (A) N2 + 3H2
2NH3
1:2:2
1 1
Volume ratio  1 : 2 : 2 (mass)
C2H4 = 10 litre, CO = 20 litre, N2 = 20 litre, O2 = 60 litre (1/28) (1/2)
Initial volume = 10 + 20 + 20 + 60 = 110 litre (mole)
C2H4 + 3O2  2CO2 + 2H2O
t=0 10 30  1 
Mass of NH3 =  2   × 17 = 1.214 g
t = end 0 0 20  28 
(B) CaCO3  CaO +
1 CO2
CO + O2  CO2 1g
2 10–2 mole 10–2 mole
t=0 20 10 –2
10 mole
t = end 0 0 20 mass of CaO = 10–2 × 56 = 0.56 g
O2 used = 40 litre, O2 remaining = 20 litre (C) 2H2 + O2 
Total CO2 formed = 40 litre 2H2O
= VO 2  VCO 2  VN 2
1g 1g
Final volume
1/2 1/32 2/32
= 20 + 40 + 20 = 80 litre mole
2
42 Volume contraction = 110 – 80 = 30 litre mass of H2O =  18 = 1.125 g
Ans. 32
43 After passing through KOH, CO2 is absorbed (D) C + 2H2  CH4
1g 1g
 Final volume = VO 2  VN 2 = 20 + 20 = 40 litre
1/12 1/2 1/12
mole
1 2 2
44 Mavg =  28   28   28  28 mass of CH4 = 1.33 g
5 5 5 Q.48 (A - p,q,r,s; (B - p,s; (C - q,r) ; (D - q)
Q.45 A-Q ; B-P, R ; C-P,R ; D-P
(A) Zn(s) + 2HCl (aq)  ZnCl2(s) + H2
16 g CH4 = 1 mole of CH4 = 5 mole of atoms
= 5NA = 6.023 × 1023 × 5 (g)
= 22.4 lit (At STP) Initial mole 2 2 0 0
1 g H2 = 1/2 mole of H2 = 1 mole of atoms final mole (2-1=1) 0 1 1
= 6.023 × 1023 atoms = 11.2 2 1
lit Excess reagent left = × 100 = 50%
22 g CO2 = 1/2 mole of CO2 = 3/2 mole of atoms 2
= 1/2 × 6.023 × 1023 atom Volume of H2 = 22.4 lit.
= 11.2 lit (At STP) Solid product obtained = 1 mole
9 g H2O = 1/2 mole H2O = 3/2 mole of atoms Limiting reagent is HCl.
= 3/2 × 60.03 × 1023 atoms (B) AgNO3(aq) + HCl  AgCl(s)
Q.46 (A) R, (B) P, (C) Q + HNO3(g)

C HEMISTRY 43
Mole Concept

Moles of y = 0.4
170 18.25 1
Initial mole =1  0 Mass of x = 0.6 × 20 = 12
170 36.5 2 Mass of y = 0.4 × 25 = 10
0
1 1 1 1 12x g  y  10 g
1- = 0 120x g  y  = 100 g
2 2 2 2
1 Q.50 (A - p,s); (B - s); (C - p,q); (D - r)
Excess reagent = 1 × 100 = 50%
2 M1V1  M2 V2
1 (A) Molarity of cation = =
V1  V2
Volume of gas = 11.2 lit.
1 0.2  100  0.1 400 0 .6
Solid product = mole = = 0.12
2 500 5
Limiting reagent is HCl. 3(0.2)100  0.1 400 0.6  0.4
Molarity of Cl— = =
(C) CaCO3(s)  CaO(s) + CO2(g) 500 5
= 0.2
100
Initial mole 1 0 0 50  0.4  0
100 (B) Molarity of cation = = 0.2
0 1 1 100
Excess reagent not present 0.4  50  0
Volume of gas = 22.4 lit. at STP Molarity of Cl— = = 0.2
100
Solid product is 1 mole
2(0.2)30  0
(C) Molarity of cation = = 0.12
(D) 2KClO3(s)  2KCl + 3O2(g) 100
Initial mole 2/3 0 0 30  0.2
0 2/3 2 Molarity of SO42– = = 0.06
100
No excess reagent left
(D) 24.5 g H2SO4 in 100 mL solution
Volume of gas = 44.8 lit.
Molarity =
2
Solid product is mole. 25.4
3
98
= 2.5
Q.49 (A) Q; (B) P; (C) S; (D) R 0 .1
(A) 10 mole present in 1000 mL of solution  Concentration of cation = 2 × 2.5 M
400 g in [1000 × 1.2] Concentration of SO42– = 2.5 M.
400 g in 1200 g
solvent = 1200 - 400 = 8000\ Q.51 (A - q,s); (B - p, s); (C - p, q, r); (D - q, r)

1200 solution  800 g solved

800 solution 1200 JEE-ADVANCED
INTEGER TYPE
1200
100 solution =  100 Q.1 [5]
800 Mole of SO42– 4 × 1.25 = 5 g ion.
= 150 gram
Q.2 [78]
(B) 40 g in 100 mL of solution C:O:S=3:2:4
40 in 160 g of solution Hydrogen is = 7.7%
40 g in 160–40 = 120 g solution  100 – 7.7 = 92.3 % contains C,O & S
 3 
(C) 8 × 100 in 1000 g of solvent %C=   92.3 ; %O
800 g in 1000 g of solvent 324

1000 2 4
100g solvent =  100 = 125 =  92.3 ; %S=  92.3
800 9 9
(D) Moles of x = 0.6
44 J EE C OMPENDIUM
 Mole Concept

Ele m e nts % % / Atom ic m a ss Sim ple ra tio Sim ple st w hole no.

H 7.7 7.7 6 6

C 30.76 30.76/12 = 2.56 2 2

O 20.51 20.15/16 = 1.28 1 1

S 41.02 41.02/32 = 1.28 1 1

 empirical formula C2H6OS = (1.31 – 0.92) = 0.39 mol

minimum molar mass = 24 + 6 + 16 + 32 = 78 Weight of excess Cr2O3 = 0.39 × 152 = 59.28 g Cr2O3

Q.3 [4] Q.6 [28]

Balanced chemical equation is
1
4nXeF6 +  + F2 + 2NaOH 
2
4nHF + 4nXeF4
O2 + 2NaF + H2O
100 1 Mole 50 × 103
nteflon = 100 n = 2[50 × 103]
n
2NaF + CaO + H2O 
1
 n XeF6 required = × 4n = 4 moles CaF2 + 2 NaOH
n 2× [50 × 103] 50 × 103 Mole
Weight of lime (CaO) = 50 × 103 × 56
Q.4 [11] = 2800 kg.
1 Feed amount of lime = 10,000
2 2 
A + B AB , 100 Kcal
2800
x x/2 x % Utilisation = × 100 = 28%
10, 000
A + 2B2  AB4 , 200 Kcal Q.7 [2]
(1–x) 2(1–x) (1–x) From one mole of initial mixture, some FeO must have
100 x + 200 (1–x) = 140 reacted with oxygen and got converted into Fe2O3.
200 – 100 x = 140 4FeO + O2  2Fe2O3
60
x= = 0.6 3 2
100 Initial moles
5 5
x 1 3 2 x
nB2 used = + 2(1–x) = x 0.6 + 2 (1– 0.6) = 0.3 + 2 Final moles –x +
2 2 5 5 2
x 0.4 = 1.1 mol But, final moles ratio is 2 : 3.
Ans = 1.1  10 = 11
3 
  x
Q.5 [59.28]  5  2
 2 x
=
(Atomic weight ofAl and Cr = 27 and 52, M.wt. of Cr2O3   
3
= 152) 5 2
49.8 g 1
Moles of Al = 27 g Al = 1.84 mol  x=
4
1
1.84  Moles of FeO reacted = x =
= = 0.92 mol of Cr2O3 4
2
1 1
200 g  Moles of O2 required = (x) = = 0.0625
4 16
Moles of Cr2O3 = 152 g Cr O = 1.31 mol
2 3  Mass of O2 required = 0.0625 × 32 = 2 g
Since 2 mol Al is required for 1 mol of Cr2O3. Q.8 [4]
So, Al is the limiting reagent and Cr2O3 is in excess. 112
nCl2 = =5
Moles of Cr2O3 is excess 22 .4

C HEMISTRY 45
Mole Concept

nKOH = 1 × 10 = 10 Q.12 [27]

Let wg water in added to 16 g CH3OH
60%
Cl2 + 2KOH  KCl + KClO + H2O
16  1000 500
5 10 5 × 0.6 5× molality = =
W  32 W
0.6
=3 =3 500 x A  1000 0.25  1000
50% = (1  x )m = W=
3KClO  2KCl + KClO3 W A B 0.75  18
2 1
27 g.
3 3 × 3 × 0.5 3 Q.13 [18]
× 3 × 0.5 10  1.8  98
=1 = 0.5 Molarity = = 18 M
98
80%
4KClO3  3KClO4 + KCl Q.14 [10]
0 .5 % by weight  10  d
0.5 0.8 × = 0.1 Use M =
4 Mw 2
(nKCl)total = 3 + 1 + 0.1 = 4.1 moles  4 moles. M1V1 = M2V2
Q.9 [50] 90  10  0.8 10  10  0.9
×V= × 80
Use POAC for carbon atom. 46 46
C + O2  CO2 + CO V = 10 mL
POAC on ‘C’ atom, 1 (mole of C) = 1 (mole of CO2) + 1 Q.15 [2]
(mole of CO)
Total moles of HCl 52
240 280 Molarity of HCl = = =2
= mole of CO2 + Total volume 23
12 28
Mole of CO2 = 20 – 10 = 10 M

10 Q.16 [4]
Mole % of CO2 = ×100 = 50%.
20
MClx + x AgNO3  xAgCl + M (NO3)x

Q.10 [42] Mole of MCl x Mole of AgNO3


Let x be the mass of CaCO3 hence mass of MgCO3 = 92 1 x
–x
CaCO3 + MgCO3 1
0.1 = (0.5 × 0.8)
x
x 92  x
100 84 0.4
x= =4
CaO + CO2 MgO + CO2 0.1
x 92  x Q.17 [40]
100 84 2
mass of residue = 48 g % CO2 = × 100 = 40%.
2  1 2
x 92  x Q.18 (1)
 × 56 + × 40 = 48 For calculation of molality we need mass of solvent
100 84
and for this purpose we need mass of solution and if
x 92  x 6 we know molarity then from density we can calculate
 + = 
100 84 7 mass of solution.
x = 50
 mass of MgCO3 = 92 – 50 = 42 g. Q.19 (1)
According to law of constant proportion which was
Q.11 [8] given by Joseph Proust, any chemical compound
Balance the equation by any method contains different elements in fixed ratio by mass
4Zn + 10HNO3  4Zn(NO3)2 + 3H2O + NH4NO3 Q.20 (1)
 a+b+c=4+3+1=8 Molality is independent of temperature because it does
not include any volume term so one molal solution
46 J EE C OMPENDIUM
 Mole Concept

prepared at 20°C will retain its molality at 100°C Q.4 (4)

Q.21 (2)
1
mass 1 g of C8H7SO3Na = mole
 NA 206
Number of atoms = mole × NA =
mm
2C8H7SO3Na + Ca2+  (C8H7SO3)2Ca + 2Na+
16 N
16g O2  Number of atoms =  NA  A 1 1
32 2 mole mole
206 412
16 N
16 g O3  Number of atoms =  NA  A
48 3 Q.5 (3)
mass  AB C
A + 2B + 3C 
Number of molecules = moles × NA =  NA 2 3
mm 6.0g ofA, 6.0×1023 atoms of B and 0.036 mol of C yields
Given mass of O2 and O3 are same 4.8 g of compound AB2C3.
So, number of molecules will be different Atomic mass of A = 60amu, Atomic mass of C = 80 amu

Q.22 (1) 6 6.0  1023

Mole ofA= = 0.1 mol, Mole of B = = 1 mol
Average mass is due to existence of isotopes 60 6 1023
So average mass is not the actual mass of atom Mole of C = 0.036 mol
Hence, C is the limiting reagent which is consumed
JEE MAIN completely.
PREVIOUS YEAR'S  AB C
So according to reaction, A + 2B + 3C  2 3
Q.1 (1)
MmixVmix = M1V1 + M2V2 0.036
0.036 mole of C will form = 0.012 mol ofAB2C3.
M1V1  M 2 V2 0.5  750  2  250 3
Mmix=   0.875M
Vmix 1000 Weight
Mole of AB2C3 = Molecular weight
Q.2 ( 3)
Let the mass of O2 = x and that of N2 = 4x 4.8
0.012 
x Molecular weight of AB2 C3
No.of molecules of O 2  ; So, molecular wt. of AB2C3 = 400
32
Atomic mass of A + 2 × Atomic mass of B + 3 Atomic
4x x
No. of molecules of N2 =  mass of C = 400
28 7 60 + 2B + 3 × 80 = 400  Atomic mass of B = 50 amu
x x
Ratio = : or 7: 32 Q.6 ( 3)
32 7
Atomic wt.of sulphur
Q.3 (2) % of sulphur = Mol.wt.of compound  100
Weight of hydrated BaCl2 = 61g
Weight of anhydrous BaCl2 = 52g; 32
Loss in mass = 61 – 52 = 9 g 8  100
Mol. wt.of compound
Assuming BaCl2 . xH2O as hydrate;
Mass of H2O removed = 9g  Mol. wt of compond = 400 g mol–1

9 Q.7 (4)
Moles of H2O removed = = 0.5
18 Combustion of hydrocarbon,
Molecular mass of BaCl2 = 208
 y y
Cx H y   x   O2  xCO2  H2 O
9  4 2
% of H2O in the hydrated BaCl2 = × 100 = 14.75%
61 5 L of alkane requires 25L of oxygen.

 14.75 
18x
 100  y
208  18x 1 L of alkane requires 5 L   x   of oxygen.
 4 
On solving we get, x = 2
y
 The formula of the hydrated salt is BaCl2. 2H2O.  x  5 which is satisfied by propane (C3H8).
4
C HEMISTRY 47
Mole Concept

Q.8 (4) Total weight of person = 75kg

Molar mass of H3AsO4 = 142g mol-1
10
 Number of moles of H3AsO4 in 35.5 g Mass due to 1H is = 75 × = 7.5 kg
100
35.5
  0.25mol
1
H atoms are replaced by 2H atoms.
142 So mass gain by person = 7.5 kg
2H3 AsO4  5H 2S 
Conc.HCl
 As 2S5  8H 2 O
Q.14 ( 3)
2 moles of H3AsO4 gives 1 mole of As2S5 % of chlorine = 3.55
1 mole of H3AsO4 gives 1/2 mole of As2S5 Thus, in 100 g of chlorohydrocarbon, mass of chlorine
0.25 = 3.55g
 0.25 mol of H3AsO4 gives mol of As2S5 = 0.125
2 3.55
mol of As2S5 1 g of chlorohydrocarbone will contain = g of
100

Q.9 (1) Mass

No. of equivalents of acid of moles of chlorine atoms = Atomic mass
= Normality Volume = 0.1 Vacid
1 mole of chlorine contains 6.023 chlorine atoms.
No. of quiivalents of OH– = No. of moles = 0.04
1  mole of chlorine will contain
For neutralisation,
= 1 6.023 
No, of equivalents of acid = No. of equivalents of base
chlorine atoms
0.04
0.1 Vacid = 0.04 ; Vacid = = 0.4 L = 400 mL Q.15 ( 3)
0.1
Decomposition of NaClO3 is given as :
2NaClO3 
Q.10 (1)  2NaCl + 3O2
3NaOH + FeCl3 Fe (OH)3 + 3NaCl (Residue) 0.16 g
100mL 2.14 g
0.16
M=? No. of moles of O2 formed = = 5 
32
2.14
Moles of Fe(OH)3 = = 2  2n 2 1
107 n
aCl O =  5 
Moles of FeCl3 = moles of Fe(OH)3 = 2  3 2 3 300
aClg+ gCl + Na+
No.of moles 1000 2 10 –2
Now  1000  1 mole of AgCl is precipitated from one mole of NaCl.
Volume(mL) 100
1
Mole of AgCl =
300
Q.11 ( 2)
Mass of AgCl = Molar mass of AgCl nAgCl
V  45 (800  V)20 800  29.875
  1
100 100 100 = 143.5    g
300
9V V 5V
 160  = 239  V = 316 mL.
20 5 20 Q.16 ( 4)
(a) 2NH4NO3(s) ggg
Q.12 (2) l. mass l. mass
Given chemical eqn = 80 g mol–1 = 28 g mol–1
M2CO3 + 2CHl  2MCl + H2O + CO2 80 g of NH4NO3 give 28 g of N2
1 gm 0.01186 mol 28
 from the balanced chemical eqn 1 g of NH4NO3 will give = 1 = 0.35 g
80
1 (b) Ba(N3)2(g) a(s) + 3N2(g)
= 0.01186  M = 84.3 gm/mol
M Mol. mass
= 221 g mol–1
Q.13 (3)
Mass in body of a healthy human adult has: 221 g of Ba(N3)2 gives 3 g of N2
Oxygen = 61.4%, carbon = 22.9 %
Hydrogen = 10.0% and Nitrogen = 2.6%

48 J EE C OMPENDIUM
 Mole Concept

3 28 1980
1 g of Ba (N3)2 will give = 1 = 0.38 g g C57H110O6 produces =  445 = 495 g
221 1780
(c) (NH4)2Cr2O7(s) (g) + 4H2O(g) + Cr2O3(s) Q.19 (4)
N1V1 = N2V2
Mol. mass For Na2CO3 (N2) = 2 
= 252 g mol–1
2  0.1  30
N1  = 2  
252 g of (NH4)2Cr2O7 gives 28 g of N2 25
For titration with NaOH
28
1 g of (NH4)2Cr2O7 will give =  1 = 0.111 g N1V1 = N2V2 V1 = 0.2 
252
0.2  30
V1 = = 25 mL
(d) 2NH3(g) g) + 3H2(g) 0.24
Q.20 (3)
Mol. mass n C12H 22O11
= 17 g mol–1 0.1 
2
2 g of NH3 gives 28 g of N2 n C12H22O11  0.2
28 Wt C12H22O11  0.2  342  68.4
1 g of NH3 will give = 2 17 1 = 0.823 g
Q.21 (3)
Volume strength = 11.35 × M = 11.35 (STP)
Q.17 (3)
12x 6 Q.22 (1)
 2NaHCO3 + (COOH)2 COONa)2 + 2H2O+ 2CO2
y 1
0.25 mL
2x  y for C x H y O z 0.25
T = 298.15 K, P = 1 bar, n = = 10–5
25000
 y y
C x H y  g    x   O 2 g   xCO 2 g   H 2O   
 4 2 Weight
No. of moles (n) = Molecular weight
no. of oxygen atom in C x H y Oz  z

no. of oxygen atom required for Cx H y 84105

w = 84 g = 100 = 8.4%
102
 y  y
combustion is  x    2   2x  
 4  2 Q.23 (Bonus)
Eq. of (COOH)2 = Eq. of NaOH
1 y
So z   2x   50 × 0.5 × 2 = 25 × M × 1
2 2
50  2
Mass of NaOH in 50 mL =  40  4g
y 1000
zx
4 Q.24 (4)
CH4
2x 3x
zx 
4 2 1molatom
% by mole of carbon   100
5molatom
3x
x : 2x : = 20%
2
Q.25 (3)
2x : 4x : 3x
5[MA + 2MB] = 125
2:4:3
MA + 2MB = 25 ......(1)
Hence C2H4O3
2MA + 2MB = 30 ......(2)
from eq. (1) & (2)
Q.18 (2)
MA = 5
Wt. of C57H 110 O6 = 2  890 = 1780 g
MB = 10
Wt. of H2O = 110  18 = 1980 g
 1780 g C57H110O6 produces 1980 g H2O

C HEMISTRY 49
Mole Concept

Q.26 (3)
34
N2(g) + 3H2(g)  2NH3(g) % w/w   100  3.4%
(1) 0.5 mol 2 mol 1000
(LR)
(2) 1 mol 3 mol (completion) Q.31 (2)
(3) 2 mol 5 mol n eq .CaCO3  N eq Ca(HCO3 ) 2  n eq Mg(HCO3 ) 2
(LR)
(4) 1.25 mol 4 mol W 0.81 0.73
Or, 2  2 2
(LR) 100 162 146
 Ans. (3)  w  1.0
Q.27 (3) 1.0
 Hardmess   106  10000ppm
C3H8(g ) + 5O2(g) 3CO2(g) + 4H2O (  ) 100
Each lg of C3H8 requires 3.63 g of O2 Correct option : (2)
P4(s) + 5O2g P4O10(s)
Each lg of P4 requires 1.29 g of O2 Q.32 [100.00 to 100.00]
4Fe(s) + 3O2(g) 2Fe2O3(s) 10–3 molar MgSO4  10–3 moles of MgSO4 present in 1
Each lg of Fe requires 0.428 g of O2 L solutions.
2Mg(s) + O2(g) 2MgO(s) n CaCO3  n MgSO4
Each lg of Mg requires 0.66 g of O2 therefore least
amount of O2 is required in option (3). 103  100
ppm(in termof CaCO3 )  106
1000
Q.28 (2)
ppm(in termof CaCO3 )  100 ppm
 Y Y
C x H y   X   O 2 –  xCO2  H 2 O
 4 2
Q.33 [10]
25 y 25
 25  X  10.3103
  M 2 M ppm = 106 = 10 ppm
M 2  0.5 1030

25 Q.34 (1)
C x 2 Except (c) all postulates were given by Dalton.
M
25
H y 1 Q.35 (3)
M
35  3  37  1
C2y H y  24 y gm C  y gm H Average molar mass =  35.5
4
or  35Cl : 37Cl = 3 : 1
24 :1ratio by mass
Q.36 [47]
Q.29 (4) Mole fraction of glucose in aqueous solution
= 0.1
 y y
CxHy +  x 
Mass percentage of water in it
 O2  xCO2 + H2O
 4 2 0.9 18
 
=   100
 y  0.9  18  0.1180 
10  x 
4 
10 10x = 47.37  47

 y Q.37 (25.00)
By given data, 10  x 
4 
= 55 .......(1) Mass of 6.023 × 1022 molecules of a substance

= 10 g
10x= 40 .......(2)
Mass of 6.023 × 10 23 molecules of the substance
 x = 4, y = 6  C4H6
= 100 g
Q.30 (2)
Volume strength = 11.2 × molarity = 11.2 5
 molarity = 1 M Molar mass of the substance = = 2.5 × 10–2
100  2
 strength = 34 g/L = 25 ×10–3
50 J EE C OMPENDIUM
 Mole Concept

Q.38 [100] Q.43 (2)

Molarity of H2O2 solution = 8.9 M 2.64
Volume strength of H2O2 solution n co2 = = 0.06 nc = 0.06
44
= 8.9 × 11.2 =100 V
Weight of carbon = 0.06  12 = 0.72 gram
Q.39 [3400] 1.08
nH2O = = 0.06
N2 (g) + 3H2(g)  18
 2NH3(g)
nH = 0.06  2 = 0.12
2.8  103 Weight of H2 = 0.12 gram
Number of moles of N2 =  100
28  Weight of oxygen in CxHyOz
= 1.8  0.72 – 0.12
1000 = 0.96 gram
Number of moles of H2 =  500
2 0.96
Number of moles of NH3 produced = 200 % weight of oxygen =  100
1.8
Mass of NH3 produced = 200 × 17 = 3400 gm
= 53.3 %
Q.40 [10]
Q.44 [243  10–2]
Equivalent of Na2CO3. x H2O = N1V1 = 0.1 
Ph – NH2
1
Moles of Na2CO3. xH2O = (0.01) O
2
||
1  Ph NH C CH 3

|
|
Mass of Na2CO3.xH2O =  0.01 x) = 1.43
2  (C6H7N) Acetanilide (C8H9NO)
1.43 = 0.53 + 0.09x 1.86 g
Molar mass = 93 Molar mass = 135 * 93
0.9 g aniline produces 135 g acetanilide
0.9 = 0.09x, x = = 10
0.09
135  1.86
1.86 g aniline produces = 2.70 g
93
Q.41 [5]
* At 90% efficiency of reaction it produces
Ratio of mass% of C : H = 4 : 1 = 12 : 3
Ratio of mass% of C : O = 3 : 4 = 12 : 16 2.70  90
= = 2.43 g
Thus, 100
Element Mass ratio Mole ratio Ans. 243  10–2
C 12 12/12 = 1
H 3 3/1 = 3 Q.45 [8]
O 16 16/16 = 1  y y
CxHy +  x   O2 
 X CO2 c   H2O(  )
Thus, empirical formula = CH3O  4 2
As organic compound ‘X’ is saturated acyclic Volume-Volume V 6V 4V
compound thus, its molecular formula will be Analysis
(CH3O)2 = C2H6O2
VCx H y VCO2
5 
C2H6O2 + O2  2CO2 + 3H2O 1 x
2
v 4v
1 mole 5/2 mole  x=4
1 x
5
2 moles 2  moles VCx H y
2 VO2

= 5 moles 1 y
x
Q.42 [129.3478gm] 4
Mass of Na+ in 50ml = 70  50 = 3500 mg
23000mg of Na+ is present in 85000 mg NaNO3 V 6V

85000 1 x y
 3500 mg Na+ will be present in  35000 4
23000
= 129347.8mg y
= 129.3478 gm. x =6
4
C HEMISTRY 51
Mole Concept

y 0.140
4 =6 Mole of Ph – CoCl = = 10–3 mol
4 140
y
=8 Mole of , that should be obtained
4
y=8
by mol-mol analysis = 10–3 mol.
Formula C4H8
Theoritical mass of product = 10–3 × 273 = 273 × 10–3g
Observed mass of product = 210 × 10–3g
Q.46 [18]
C2H6 ® 3H2O 210  10 –3
%yield of product = × 100 =76.9%=77
0.1 0.3 = 0.3 × 6 × 1023 = 18 × 1022 273  10 –3
mol mol
No. of molecules = 0.3 × 6.023 × 1023 Q.49 [1]
= 18.069 × 1022 PV = nRT
20 N
Q.47 [16] 1.0 ×  × 0.083273
H2 1000 6.023  10 23
 Number of Cl2 molecules, N = 5.3 × 1020
C 
64% C 3H4O + H 2O
(HO)H 2C CHO Hence, Number of Cl-atoms = 1.06 × 1021
1 × 1021
x x 7.8
mol  0.64  Q.50 [80]
74 74 56
x = 16.10
; 16.00

Q.48[77] 2 4

1 mole 1 mole
O O 78gm 123gm
C–N(C6 H5)2 123
3.9gm × 3.9 = 6.15gm
Cl + C H NHC H 78
6 5 6 5
But actual amount of nitrobenzene formed is
1 mole 1 mole 1 4.92 gm and hence.
mole 4.92
= 140.5 gm = 169 gm = 273 gm Percentage yield = × 100 = 80%
6.15
169
0.140 gm  0.140 Q.51 [525]
140.5 3Pb(NO3)2 +Cr2 (SO4)3 3PbSO4 +2Cr(NO3)3
L.R. = 0.168 gm < 0.388 gm 35ml 20 ml
excess 0.15 M 0.12 M
Theoretical amount of given product formed = 5.25 m.mol = 2.4 m.mol 5.25 m.mol
273 = 5.25 × 10–3 mol
= 0.140 0.272gm therefore moles of PbSO4 formed = 5.25 × 10–3
140.5 = 525 × 10–5
But its actual amount formed is 0.210 gm.
Hence, the percentage yield of product. Q.52 (3)
0.210 H3PO3 + 2NaOH  Na2HPO3+ 2H2O
= 100 77.20 77 50 ml 1M
0.272
OR 1M V=?
n NaoH 2
O O
 n 
Ph N 3PO3 1
C–Cl
0.388g Ph
1 V 2
  VNaOH  100ml
50  1 1
0.140g 0.210g H3PO2 + 2NaOH  NaH2PO3+ H2O

52 J EE C OMPENDIUM
 Mole Concept

100 ml 1M
58
2M V=? 1 g of H2O is produced by g butane.
90
n 1 1 V 1
 n
NaoH
   VNaOH  200ml 58
H 3 PO3 1 2  100 1 72gof H2O is produced by
90
 72 = 46.4 g of butane.

The amount of butane required is 46.4 g = 464 g

Q.53 (3)
44 gm CO2 have 12 gm carbon Q.58 [68]
12 Br– + Ag NO gBr
So, 420 gm CO2   420
44 atomic mass of Br  m1 100
1260 % of Br = molecular mass of AgBr  m(mass of o.c.)
 gmcarbon
11
 114.545 gram carbon 80  0.2397 100
188  0.15 = 68
114.545
So, % of carbon =  100
750
; 15.3% Q.59 [4]
18 gm H2O  2 gm H2 Let moler added a
2 Ag+(aq) + 2NH3(aq) g (NH3)2(aq)]
210 gm  x 210
18 a
= 23.33 gm H2 t=0 0.80
2
23.33
So, % H   100  3.11% a
750 t=0 5  10–8 –1.6 0.8
 3% 2
0.8
Q.54 (3) 2

a
8 
Zeros preceeding to first non-zero digit are not 5 10   1.6 
significant.  2 
a
Q.55 (1)
Given that solution is equimolar so, Q.60 [2]
x y 106 8
 y  x Mole of Na =
40 106 40 23
Also x + y = 4
 6.02 1023
106 146 4  40 Number of atoms = = 2.09 
x+ x = 4  x = 4 x = 23
40 40 146
x = 1.095  Q.61 [19]
C3H8(g) + 5O2(g) CO2(g) + 4H2O
Q.56 [226]
No. of moles of NaOH 100 1000
t=0 mol mol 0 0
44 32
0.5  250 1
=   0.125 t= mol 6.81 mol 9.08 mol
1000 8
Mole fraction of CO2 in the final reaction mixture
1 500 1 (heterogeneous),
No. of moles of HCl =  = 0.5
1000 2 n
CO 2 6.81
No. of moles of HCl unreacted = 0.5 – 0.125 = 0.375 X CO2 = n =
O 2  CO 2  n H 2 O 19.9  6.81  9.08
n
No. of molecules of HCl left unreacted
= 0.375   = 0.19 = 19 

Q.57 [464] Q.62 [78]

13 C6 H 6 
Methylation
 C 6 H 5CH 3
C4H10 + O 2 CO2 + 5H2O
2 1 mole of benzene gives 1 mol of toluene
58 g of butatne produces 90 g of H2O 78 g of benzene gives 92 g of toluene.
C HEMISTRY 53
Mole Concept

C6H12O6  Glucose
10
(Wtheoretical   mass of C 72
78
We know : mass of glucose  180
Wactual  9.2 
% yield = W 100 =   78 100 = 78%
10  92  mass of C
Given : %C = 10.8 = mass of solution  100
theoretical

Q.63 [40]
10.8  250
Mass of bromine = 80 = mass of C  Mass of C = 27 g
Molar mass of AgBr = 108 + 80 = 188 100
Weight of o.c = 29  mass of glucose = 67.5 gm
Weight of AgBr = 1.88 g  moles of glucose = 0.375 moles
Mass of solvent = 250 – 67.5 gm = 182.5 gm
Molar mass of Br  weight of AgBr
% Br = Molar mass of AgBr  weight of o.c. 0.375
 Molality = = 2.055  2.06
0.1825
80 1.88 100 Q.70 [3]
= 188  2 = 40%
CH3CH2MgBr + CH3OH 
 CH3 – CH3(g)
Q.64 [7]
2.24 ml
Q.65 [3]
Q.66 [46] 2.24
Mole of ethane =
N2 (g) 3H2 (g) 2NH3 (g) 22400
56 L excess 20 lit = 10–4 mole
Used N2 = 10 lit, unused N2 = 46 L Mass of ethane = 10–4 × 30
= 3 × 10–3 gm
Q.67 (3) = 3 mg
So2Cl2 + 2H2O  H2SO4 + 2HCl Q.71 [8]
a mole a mole 2a mole Mass of mixture = 10 g = H2 + He
Volume of container = 0.0125m3
(1) H 2SO 4  2NaOH  Na 2SO 4  2H 2 O = 12.5 l
a mole 2a mole P = 6 bar = 5.922 atm
Total mole of NaOH required = 4a = 16 T = 27°C = 300 K
a = 16 PV = nRT
Total mole (n) =
Q.68 [24] PV 5.922 12.5 101.33

 dsolution  1 gm/ml RT 8.314  300
Volume of solution = 2L = 2000 ml  1 l-atm = 101.33 J
Mass of solution = 2000 gm = 3.01  3 mol
mass of solute Let mass of H2 in mixture = x gm
ppm   106 Mass of He = (10 - x) gm
mass of solution
x
mass of Mg Mole of H2 =
48   106 2
2000
10  x
48 × 2 × 10–3 = mass of Mg Mole of He =
4
48  2  10 3
Mole of Mg = x 10  x
24 Total mole =  3
2 4
= 4 × 10–3 mol
No. of Mg-atoms 2x + 10 - x = 12
= mole × NA X = 2 gm
= 4 × 10–3 × 6.02 × 1023 Mass of H2 = 2g
= 24.08 × 1020 Mass of He = 10 - x
= x × 1020 = 8 gm
x = 24 Q.72 (3)
% of Iron in hemoglobin = 0.34%
Q.69 (2) Given mass of hemoglobin = 3.3g

54 J EE C OMPENDIUM
 Mole Concept

0.34 = 0.4 = 0.2

Mass of Iron in hemoglobin = 3.3 × 0.4 0.2
100
L.R. = 0.1
= 0.01122 gm 1 2
mass L.R. × NaOH
No. of Iron atoms =  NA
GAM
Q.76 [6]
0.01122
=  6.023 1023 1.344
 6  105
56 Mole of H2 gas =
22400
= 1.206 ×1020 No. of H.atoms per molecule of H2 = 2
 1.21 × 1020 Moles of alcoholic hydrogens = 6 × 10–5 × 2
Q.73 (2) 1.84 103
x + y + 3z  n×
92
= 2 × 6 × 10–5
xyz3
12  92
n 1 1 n= 6
0.05 184
% mass 10 20 Q.77 (3)
30 4HNO3(l) + 3KCl(s)  Cl2(g) + NOCl(g)
Limiting reagent = Z + 2H2O(g) + 3KNO3
1 4 110
Moles of product formed =  0.05 Moles of HNO3 = 
3 3 101
mass = 110
0.05
= Moles 4 110
3 Mass of HNO3 =   63
Amount = Moles × Molecular mass 3 101
Molecular mass =
0.05
= × (10 + 20 + 3 × 30) 39×1+14×1+16 ×3
3 = 91.485 g
0.05 = 39 + 14 + 48
 × 120 = 2 g
3
Q.74 (3) = 39 + 62 = 101
110
N 2 (g)  3H 2 (g)  2NH 3 (g) Moles =
101
W2  20g 5
Q.78 (3)
20 Mass of C15H30=V×d=1000×0.756 g/ml =756 gm
n 5/2
28 75.6 75.6g
Moles of C15H30    3.6 moles of
Stoichiometric Amount 180  30 210g
20 / 28 20 5/2 5
N2   H2   45
1 28 3 6 C15 H 30  O2  15CO 2  g   15H 2 O
2
 N2 is the limiting reagent
45
20 Moles 3.6  3.6 15  3.6 15  3.6
 n(NH3) = 2 × n(N2) = 2 × = 1.42 2
28
45
,Q.75 [25] Mass O2 mass 
 3.6  32  2592g of O2
H2SO4 + 2NaOH  2
Na2SO4 + 2H2O (mole ×mol. cot.) CO2 mass=15×44×3.6=2376 g of CO2
M = 0.2 M = 0.1
Moles = 0.1 Q. 79 [5418]
V=2L V=2L Molar massof C7H5N3O6 is 84 + 5 + 42 + 96 = 227
V=4L 681
n C 7 H 5 N 3O 6   3 moles
0.1 227
n=M×V n=M×V m= × 1000
4
681
= 0.2 × 2 = 0.1 × 2 m = 25 Ans. nN   3  9 moles of N
227
C HEMISTRY 55
Mole Concept

No. of N atoms = 9 × 6.02 × 1023 6.5

= 5418 × 1021  
2
= 5418
L.R.)
Q.80 [25] n CO2
n O2 
 75×1  1
% of glycine =   ×100 = 0.3
 GMM  6.5
= n CO2
2
 75×100  3
GMM =   = 25×10 6.5
 0.3  Mass of CO2 = gm
Q.81 (4) 2
Q.85 (2)
y y Q.86 (1)
CxHy + (x + ) O2  xCO2 + H2O
4 2 Q.87 (2)
120 g mass = 330 g 270 g For
330 270 7.5
moles = =7.5 moles = =15 % Hydrogen = Relation atomicities
44 18 116
Moles of CO2 = moles of ‘C’ 60
 so mass of carbon = n × Atomic mass % Oxygen = 
116
= 7.5 × 12
= 90 gram 48.5 51.7
Carbon =  
116 16
90
% of carbon in organic compound =  100 = 75% 41.8
120 Empirical formula CH2O;Weight = 30 g; C= = 3.5
12
% of Hydrogen in organic compound =
30
 100  C2H4O2 (B) CH2O relate to this formula.
120
= 25 % Q. 88 (4)

Q.82 (C) C 74% 74 6.16

 6.16 5
Given HCl by mass = 35% = 0.35 12 1.23
10  d N 17.3% 17.3 1.23
M 100  1.23 1
molecular weight 14 1.23
H 8.7% 8.7 8.7
10  0.35 1.46  8.7 7
M=  100 1 1.23
36.5
= 14 M Emperical formula = C5NH7
Emperical weight = 81
Q. 83 [225]
CH4 + 2O2 CO3 + 2H2O 162
Multiplying factor = 2
moles = 2.25 Mass = 81 81
81 Molecular formula = C10N2H14
Moles =
18
Q.89 (3)

4CO + Fe3O4  3Fe + 4CO2
So, 225 moles of CH4 are required to produce. 81
According to equation
g fo water after complete combustion.
1 mole (232 g) of Fe3O4 is reacting with
4 mole (112 g) of CO and
Q. 84 [143]
3 mole (168 g) of Fe and 4 mole (176 g) of CO2 with
CH4 + 202(g) CO2(g) + H2O
produce.
Mass 100 208 Moles 
According to question
100 208 4.640 × 103 g of Fe3O4 and 2.52 × 103 g of CO is reacting.
oles Mass = 143
16 32 Since
gram 232 g Fe3O4 needs 112 g CO to react

56 J EE C OMPENDIUM
 Mole Concept

8KMnO4 + 3Na2S2O3 + H2O ’! 8MnO2 + 3Na2SO4 +

112
1 g Fe3O4 needs 232 g CO to react 3K2SO4 + 2KOH
No. of sulphur containing products is 3 + 3 = 6
Q.4 [2992]
112
So 4.64 × 10 g Fe3O4 needs 232 ×4.640 ×103 CO to  NH 4 2 SO4  Ca  OH 2  CaSO4 .2H 2O 2NH3
3

1584g gypsum(M 172) 24mole

react 12mol 12mol
= 2.24 × 103 g CO to react
 That means Fe3O4 is limiting reagent (L.R) NiCl2 .6H 2 O  6NH3   Ni  NH3 6  Cl2  6H 2 O
 232 g Fe3O4 produce 168 g Fe 952g 4mol 24mol  M 232 
4mol
168
1 g Fe3O4 produce 232 g Fe Total mass = 12 × 172 + 4 × 232 = 2992 g

Q.5 [2.98 or 2.99]

168
4.640 × 10 Fe3O4 produce 232 ×4.640 × 103 Fe
3
n
Xurea = 0.05 =
n  50
= 3360 g
 Hence option (C) is correct. 19n = 50
n = 2.6315
Q.90 (2) (2.6315  60  900)
Vsol = = 881.5789 ml
0.02585× 0.112 1.2
 Result should be of three
0.5702 2.6315  1000
significant figures. Molarity = = 2.9849
881.5789
0 .0 0 3 2 0 0 9 6 Molarity = 2.98M

0 .5 7 0 2
Q.6 [6.15]
 0.005613749....
2Al+3H2SO4 Al2(SO4)3+3H2
Hint:- Least number of significant figure
5.4
Moles of Al takes   0.2
JEE-ADVANCED 27
PREVIOUS YEAR'S
50  5.0
Q.1 [8] moles of H2SO4 taken   0.25
Given 3.2 M solution 1000
 moles of solute = 3.2 mol 0.2 0.25
Consider 1 L Solution. As  , H 2SO4 is limiting reagent
2 3
 volume of solvent = 1 L
3
Psolvent = 0.4 g.mL–1 Now, moles of H2 formed   0.25  0.25
 msolvent = P × V = 400 g 3
3.2 mol nRT
 molality = 0.4 kg = 8 molal  Volume of H2 gas formed =
P
Q.2 [9] 0.25  0.082  300
  6.15L
Given, molality = Molarity 1
And assuming no volume change in forming solution
Density of solvent = 1 gml–1 Q.7 [2.38]
And density of solution (given) = 2 gml–1
Implies, solvent and solute are present in equal P 4  3NaOH  3H 2 O  PH 3  3NaH 2 PO 2
1.24g
qualities or
0.01mole

1 As NaOH is present in excess. So, amount of phosphine

M solute formed is 0.01 mole (as P4 is limiting)
  solute  0.1  
M solute
9 2PH 3  3CuSO 4  Cu 3 P2  3H 2SO 4
1 1
 msolvent 0.01mole
M solvent M solute
3  0.01
Q.3 [6] Amount of CuSO4 required = mole
2

C HEMISTRY 57
Mole Concept

Mass of CuSO4 (in g) required

0.03
= × (63 + 32 + 16 × 4)
2
0.03
= ×159
2
= 2.38g

Q.8 (2,3)
(1) If empirical formula of 3 is P3Q4, then molecular
formula is (P3Q4)n
3M p 40 2
  
3M p  4M Q 100 5
15Mp = 6Mp + 8MQ
9Mp = 8MQ
 For P3Q5, % Of
 3M P  8M Q
P 100  100  34.78%
 3M  5M  23M Q
 P Q 

(2) If empirical formula of compound 3 is P3Q2, we have

3M P 2

3M P  2M Q 5
15MP = 6MP + 4MQ
9MP = 4MQ
If MP = 20
180
MQ   45
4
(3) If empirical formula of 2 is PQ
MP 4 44.44
 M  M  9  100
P Q

9MP = 5MP + 4MQ

5MP = 4MQ

If empirical formula is assumed as P5Q4,

 5M P 
% of P   5M  4M  100  50
 P Q 

Hence P5Q4 is the empirical formula of compund

(4) If empirical formula of I is P2Q, we have
 2M P 
% of P   2M  M  100  50
 P Q 
4MP=20MP+MQ
2MP=MQ

Hence, atomic weight of P and Q cannot be 70 and 35

respectively.
Hence (B,C) are correct

58 J EE C OMPENDIUM
 Gaseous State Current
Gaseous
Electricity
State

DPP-1
Q.4 (4)
Q.1 (3)
1
P 1 12 r
P = CRT; T = = = 12 K. M
RC 1 1
Q.2 (2)
n = const. Q.5 (1)
no of molecules = const 3 3
KE  RT  PV
same number of molecules 2 2
2 E 2
Q.3 (4) P  for unit volume (V = 1)  P  E
3 V 3
Boyle’s Law
1 Q.6 (1)
V  (Mass & Temperature constant)
P 1
rg  .rH
5 2
Q.4 (1)
2
Q.5 (1) Mg  rH 
Q.6 (3)  2   (5 )  25 ; M g  2  25  50
2
M H2  rg 
Q.7 (2)
Q.8 (2)
Q.9 (2) Q.7 (3)
Q.10 (1) Q.8 (1)
Q.9 (2)
Q.10 (1)
DPP-2 Q.11 (1)
Q.12 (1)
Q.1 (3)
Q.13 (1)
( Vrms )1 T1 M2 Q.14 (2)
( Vrms )2 = M1 T2 Q.15 (1)
Q.2 (2)
DPP-3
u1 T1  M2
u2 = T2M1 Q.1 (1)

Q.3 (4)  2
 P  an 
 V 2 
(V–nb) = nRT..
rA 16 w A 2 
Given r = ; w =
B 3 B 3 Q.2 (3)
Value of constant a is greater than other for NH 3 that’ss
rA nA MB
we have r = n MA why NH 3 can be most easily liquefiedz
B B
Q.3 (3)
16 w A MB MB Q.4 (2)
= M w Q.5 (2)
3 A B MA
Q.6 (1)
3/2 3/2 Q.7 (4)
16 2  MB   MB  Q.8 (4)
    
3  M A
= =8
3   MA  Q.9 (4)
Q.10 (1)
MB
M =4 4   (2  10 8 )3  6  10 23
A Required % = × × 100.
3 22400
8 = 0.09 %
mole ratio =
3
C HEMISTRY 59
Current Electricity
Gaseous State

EXERCISES
JEE-MAIN
PA  MMA   ART
OBJECTIVE QUESTIONS
Q.1 (3) PB  MMB  BRT

V1 T1 PA 1 / 2MMB 3
=
V2 T2 PB × MMB =
1.5
Q.2 (4)
n,T  const PA
PV = const PB = 4 Ans.
Q.3 (4)
n  constant Q.9 (2)
v  fixed
 P & T const P
 .
Q.4 (2) T
V = 2 litre Q.10 (A)
P,T,V  const
v1 T1
v2 = T2 nSO2 nO2

1
2 273 WO2 = WSO2
 = 2
4 T (inK)
Q.11 (C)
 T = 546 K  T = 273°C P,n  const
Q.5 (A)
Two flask initally at 27º and 0.5 atm, have same volume V1 T1
and 0.7 mole thus each flask has 0.35 mole V2 = T2
Let n mole of gas are diffuse from II to I on heating the
flask at 127ºC 10 Lt 273
 V =
Mole in I flask = 0.35 + n, Mole in II flask = 0.35 – n 2 373
If new pressure of flask is P then sV2 = 13.66 Lt.
for I flask P × V = (0.35 + n) × R × 300 ; for II flask P × V
= (0.35 – n) × R × 400 n = 0.5 Q.12 (4)
mole in I flask = 0.40mole in II flask = 0.30
0.5 × 2V = 0.7 × 0.0821 × 300 (initially)V = 17.24 Lt. pH2 nH 2 30 15
P × 17.24 = 0.30 × 0.0821 × 400 (finally) P = 0.57 atm. p C2H6 = n = = .
C2H6 2 1
Q.6 (1)
15 75 Q.13 (4)
= M
30 B Weight of H2 = 20 g in 100 g mixture ; Weight of O2 = 80
g
150
MB = 150. (V.D.)B = = 75. 20 80 5
2  Moles of H2 = = 10 ;  Moles of O2 = =
2 32 2
Q.7 (4)
R is depend upon unit of measurement 5 25
 Total moles = 10 + =
Q.8 (3) 2 2
10
 PH2 = PT x mole fraction of H2 = 1 x
'
= 0.8 bar
25 / 2
Q.14 (B)
A B Since A and A2 are two states in gaseous phase having
3 3
0.5 dm 1 dm their wt ratio 50% i.e. 1 : 1
PV = nRT
96 1 96 1 1
moles of A =  = 1Moles of A2 =  
W 2 48 2 96 2
PV = RT
T
MM Total mole = 3/2
 P× Mm = RT P = nRT/V.

60 J EE C OMPENDIUM
 Current
Gaseous
Electricity
State

Q.15 (1) Q.23 (1)

P = XPT mA = 2 mB
uA = 2 u B
P1 3 / 10 PT P1 2.7 nA = nB
P2 = 2 / 9 PT = P2 = 2 vA = vB
2.7 1
P2 – P2
2
P1 – P2 PA VA mAnAuA
 P × 100 = 2 ×100 =
3
1 P2 PB VB 1
m B n B u B2
3
26 %
Partial pressure of O2 is changed by about 26% Q.24 (A)
3 N
  R  150
Q.16 (C) 2 32 x N1
K.EO = 3 N' =  K.EO2 = N'2 =
Initial N2 + 3H2  2NH3 2
  R  300 2 x
2 32
1 3
final – – 2 1
2
4 2
ratio =  .
2 1 N  N' Therefore, (A) option is correct.
Q.17 (2)
20 30 32
× = . Q.25 (B)
60 V 64
3 8.314  300
Q.18 (3) Average KE = × = 6.21 × 10–21 J/
2 6.023  1023
1
r molecule.
M
So NH3 diffuses with faster rate. Q.26 (D)
3
Q.19 (2) K.E. = nRT
T
2
r1 t2 M2 Q.27 (2)
= =
r2 5 2 v T

Q.28 (1)
Q.20 (2)
K.E. = 3/2 nRT
rx dy 3 dy n 1 T1 = n 2 T2
 
ry = dx 1 dx 0.4  400
T1 =
0.3
dy 9
= 32 = Ans. T1 = 533 K
dx 1
Q.21 (1) Q.29 (3)
rN 2 MM H2 3RT 5  104
 Urms = =
rH 2 MM N2 M 10  104

2 1 3RT1
= = M
28 14 1 T1
= 3RT2 = 4  T
1 : 14 : 7 2
M
Q.22 (4) T2 = 4T1
T2 = 4 times T1
C3H6O  CO2
3  nC3H6O = nCO2 Q.30 (B)

C HEMISTRY 61
Current Electricity
Gaseous State

xml n-butane
3RT1 y ml isobutane
5  104 M 13 13
4 = 3RT2 Volume of O2 = x  +y
10  10 2 2
M Q.36 (1)
T1 = 4 T 2 8a
If T1 is 4 times TC =
27Rb
by heating the gas, pressure is made four times.
a
TB =
Q.31 (B) Rb
Ti = 2TB
3RT 3PV 3  1.2  105 TC < T B < T i
Urms = = =
M M 4
= 300 ms Q.37 (D)
8a 
Q.32 (B)  TC =
27Rb 
CxHy + O2  CO2 + H2O It sould be z.
x  nCxHy = nCO2 (POAC on C)
Q.38 (3)
x  500 = 2500 (x = 5) Factual question
y  nCx Hy = 2  nH2O (POAC on H)
Q.39 (3)
y  500 = 2  3000 y = 12
Factual question
Formula = C5H12
Q.40 (3)
Q.33 (A)
y Ease of liquification  a
CxHy + O2  x CO2 + + H 2O
2
Q.41 (2)
357  21
15 ml ml 75ml Boiling point  a
100

 y y 75 Q.42 (1)
 x    15 = 75 x + = (P) (V – nb) = nRT
 4 4 15
nRT
y y P=
x+ =5 x+ =5 V  nb
4 4
y Q.43 (3)
3+ = 5 15 x + 15x + 282 = 327 PV = Pb + RT
4
y=8 x=3 PV Pb
Formula = C3H8 =1+
RT RT
Q.34 (2) Q.44 (1)
 y y  a 
CxHy +  x   O2  xCO2 + H2O  P   (V) = RT
 4  2 T
 V2 
y
x 7 y 3 y 3 a
4 = = = PV + = RT
T
4 4x 4 x 1 V
x
PV
Q.35 (2) RT
13 a
2 2 
C4H10 + O 4 CO2 + 5 H2O =1–
VRT

62 J EE C OMPENDIUM
 Current
Gaseous
Electricity
State

Q.45 (1) Q.7 (B)

4 3 PM
4× r × NA = 24 =
3 RT
JEE-ADVANCED
OBJECTIVE QUESTIONS Q.8 (B)
Q.1 (D) 76  13.6 = x  13.6 + 1  13.6 + 3.4  20 + 6.8  30 + 13.6
nR  15
P= T 76  13.6 = x  13.6 + 13.6 + 13.6  5 + 13.6  15 + 13.6 
V 15
P, T, Plot is linear 76 = x + 1 + 5 + 30
nR x = 40 cm
Slope =
V Q.9 (B)
V1  V2 thus slope will be different ]
P1 P2

Q.2 (1) n1RT1 n 2 RT2
Pi = x atm n, V  const
0.4 P1 T1 1 M1 0.5  M 2
Pf = x + x =
100 P2 = T2 2 3
x T M1 2  0 .5 1
Ti = T   Tf = T + 1
0.4 T 1 M2 = = ]
x x 3 3
100
T = 250 K
Q.10 (C)
PV = nRT (P and T constant)
Q.3 (C)
Vn (W is constant)
V1 V
 2 W
T1 T2 V (Heavier gas)
M
3 2.7
 1
320 T2 V
T2 = 288 K = 15°C
M
1 1 1
Q.4 (C) V1 : V2 : V3 = : : = 5 : 2 : 40 Ans.]
PV  T 32 80 4

Q.11 (D)
Q.5 (C) nRT 4 0.0821 273
PV = nRT P(atm) = =  = 2 atm
V 40 1.12
1 Ptorr = 2 × 760 = 1520 torr.]
PV = RT
T
M
Q.6 (C) Q.12 (B)
Max capacity of balloon = 600 ml
P1V1 = P2V2 H2
500  1 = 600  P2
5 H2O
P2 =  760 mm = 633 mm
6 T1 = T
Height above which balloon will burst = (760 – 633)  P1 = 830 – 30 = 800 mm
100 cm P1 = 2
= 127  100 cm T2 = 0.9 T
= 127 m

C HEMISTRY 63
Current Electricity
Gaseous State

P1 P2 800 P2 PA MA dA RT P 1
 or    =   A  =2
T1 T2 T 0.9 T PB MB dB RT PB 3
 P2 = 720 mm
 Ptotal at 2nd temp. = 720 + 45 = 745 mm Ans. ]
PA 6
  ]
PB 1
Q.13 (D)
PM = dRT Q.18 (D)
N2  2N
dRT 1.34  0.0821 273 1 .4 1
Mmix = = = 30 at t = 0 = 0
P 1 28 20

Mmix = X N 2  28  X O 2  32 = 30 at t = tf
1
– x 2x
20
X N 2 = 0.5 1 3
but, x = 30% of =
20 200
X O 2 = 0.5
 Total pressure = 1 atm 1 1 1
Final number of mole = – x + 2x = +x= +
then partial pressure of O2 = 0.5 atm. ] 20 20 20
3 13
Q.14 (D) =
200 200
n O2 PO2 13 0.0821  1800
= P P = × = 1.92 atm.
ncyclopropa ne 200 5
cyclopropa ne
Q.19 (A)
H2 +1/2O2 H2O(l)
Q.15 (C) a b 0
Let initial pressure of the bulb (A) is P a–2b 0 b
Reaction is studied at constant P &T
Now PAVB =PfVf a+b = 40 a–2b = 10
P × 100 = (P ×0.4) × (x + 100) a = 30 ml b = 10ml
1000 mole fraction of H2 = volume fraction of H2 =30/40 =
x=  100 = 150 cm3 ] 0.75.
0 .4
Q.20 (C)
Q.16 (C)
n r( He ) n ( He ) 16
r  M SO 64 r  = . 1 ]
 mix  = 2

2 m r( CH 4 ) n ( CH ) 4
=
M av  Mav = 16
4
 rSO 2  M av 1
  Q.21 (A)
Let the initial moles be one rH 2 4 2 22 2
2NH3  N2 + 3H2   
1–2x x 3x rHe 2 1 2 2
Total mass 17 1
 16 = x= rHe 32 2 2
Mav =
Total moles 1  2x 32  
rO2 4 1 ]
 1 
2  Q.22 (B)
 32 
% diss. = ×100 = 6.25% ]
1 rmixture 32 20  60
Q.17 (C) rO2 = M
=
311
dA = 2dB M = 2.16
3MA = MB V.D. = 4.32
 PM = d RT

64 J EE C OMPENDIUM
 Current
Gaseous
Electricity
State

Q.23 (D) Q.32 (C)

It is factual question
t mix rO2 Mmix
t O2 = rmix = 32 Q.33 (B)
It is factual question
234 Mmix
=
224 32 Q.34 (A,C)
(A) UM.P.S. 
80  32  x  20 (B) T 
Mmix =
100 Q.35 (A)
1
Q.24 (B) 
N*
of container is rigid then N* will not change  = l ]
Q.36 (A)
H2 gas will be having longest mean-free path.
rHCl 17 x 17
 200  x =  x = 81.13 cm Q.37 (B)
rNH3 = 36.5 36.5
 y y
CxHy +  x   O2  XCO2 + H2O
Q.25 (C)  4 2
Let both gases meet at nth row 7.5ml 36ml
 y
36 – 7.5  x   + 7.5 x = 28.5
 4

 y
36 – 7.5 15   + 7.5 x = 28.5
 4
rNO2 y=4
x 179
x=2
rC6H10Br = 12  x = 44 = 2
So formula = C2H4
x = 24 – 2x Q.38 (4)
3x= 24 (Pr +3 ) (3 × 3 –1)
x=8=n–1
 1
n = 9th Row  Pr   × 8 = 8 × 1
Q.26 (C)  3
1 1 2
r Pr = 1 – =
M
3 3
Q.27 (B)
Q.28 (C) 2
P= × 30
Since for both N2 and C4H8, T M is same. 3
= 20 atm
dN
Therefore the value of for both gases in all range
N Q.39 (C)
of velocities will be same. ]
Q.40 (D)
Q.29 (B)
Q.30 (A) Q.41 (B)
Transtational K. E. =3/2 nRT PV real
Z = PV 
3 ideal
×2×2×300 = 1800 cal
2 Q.42 (C)
Q.31 (D) High T, low P
Charles law is applicable
Q.43 (B)
C HEMISTRY 65
Current Electricity
Gaseous State

 – Slope of isotherm below critical point < 0. (d) at T < 500 K, P > 50 atm corresponds to 'd' substance
Slope of isotherm above critical point < 0. - liquid
Slope of isotherm at critical point = 0. So, Answer (D)
JEE-ADVANCED
COMPREHENSION/STATEMENT/MATCHING/MCQ
Q.1 (A,B,D)
(A) V = KT
logV = logK + log T

So slope of isotherm at critical point is maximum.

8a
– TC = 27 Rb A is correct
TC  a
Larger value of T C It means less decreases in
temperature is required to liquifly the gas. Gas will liquify V
at higher temperature. So, easier'll be liquification. (B) log = log K
 – When gas is below critical temperature. It is 'liquid' T
so vander waal equation of state is not valid.
So, Answer (B).

Q.44 (C)
It is factual question B is correct

Q.45 (D)
a 1
TC  (C) log V + log = log K C is not correct
b T
Q.46 (C)
4 3 (D) V = KT
VC = 3 × N × r × 0.44 TV = KT2
3
Q.47 (D)
It is factual question

Q.48 (D) D is correct

It is factual question

Q.49 (C)
If Z > 1 positive deviation Q.2 (B,C,D)
Z < 1 negative deviation (B) PV = nRT

Q.50 (D) nRT

P=
V

lnP = ln nRT – ln V
Slope = –1
Intercept value = ln (nRT)
1
= ln 1 × 0.0821 ×
0.0821
(a) at T = 500 K, P = 40 atm corresponds to 'a' substance =0
- gas (C) PM = d RT
(b) at T = 300 K, P = 50 atm corresponds to 'b' substance
- liquid P RT 1 1
(c) at T < 300 K, P > 20 atm corresponds to 'c' substance = = = = 0.01
d M M 100
- liquid
66 J EE C OMPENDIUM
 Current
Gaseous
Electricity
State

(D) PV2 = nRT V

 3x 
PT = 1  
slope = nRT = 1 = tan 45° ]
Q.3 (A, B)  2 
Suppose the cylinder will burst at T2K
3
T2 
P2T1 14 .9  300 =1+ ×0.2
P1 (V1 = V2) = 12
= 372.5 K 2
Q.4 (A, C) PT = 1.3 atm
V = 8.21 L P = 0.3 atmor 76 × 0.3 cm of Hg or
n=2 760 × 0.3 mm of Hg ]
T = 300 K
(A) P = 6 atm Q.9 (A,B)
He SO2 X
nR Mol.r Mass
(B) P  KT  K = 4 64 256
V
4
Q.5 (A, B) n He  64  44
   
n SO 2  4 
(A) ,
B 1
P
4
A n SO2 256  2 
  
T nX 64  1 
PT
1
nR  nHe : n SO 2 : nX = 44 : 1 :  16 × 44 : 16 : 1
K=
V
( 2) 4
n = chang ; V = must change to maintain  4096 : 16 : 1
n = const; V constant 6
Q.6 (A, D)  n He   64 
  
(B)    4 
I II  n SO 2   
300 K 400 K
6
mole H2 mole H2  n SO 2   256 
16.42 8.211     
 
 nX   64 
nRT
(A) I. P. = 3 atm by P =
V  nHe : n SO 2 : nX = (4)6 . (2)6 : 26 : 1
(B) Pressure just after openin doesn’t changes  262144 : 64 : 1
(D) Pressure becomes same after some time (C) 512 : 8 : 1 is not possible composition.
Q.7 (B, C) Q.10 (B,D)
2  10 8
At point A T   1
A R 2 R r
M
2  10 10
At point D T  
D 2R R Q.11 (B, D)
Pressure at B
rA 16 w A 2
TB P Given r = ; w =
 B B 3 B 3
TA PA
rA nA MB
300 we have r = n
PB   75 R B B MA
(B / R)
16 w A MB MB
Q.8 (B,D) = M w MA
3 A B

C HEMISTRY 67
Current Electricity
Gaseous State

3/2 3/2
Q.17 (A,B,D)
16 2  MB   MB  (B) H2O is not present in gaseous form
=      =8
3 3  MA   MA  (C) At critical point
PC VC 3
MB 8 ZC = 
M =4
A
mole ratio =
3 RTC 8 (for any gas)
300
Q.12 (A,B,D) (D) T/M for SO2 =
64
Volume = V Volume = V 600
T/M for O2 =
Flask-A Flask-B 32
Mass = m gm 400 K Mass = m gm 800 K since T/M for both gases are different, so graph for
both gases will be different]

H2 gas He gas Q.18 (A,B,C,D)

N2(g) should not satisfy ideal gas conditions as:

H2 =  He (Given) (A) Find P × Vm = 9.6 × 0.821
 RT = 0.0821 × 96
 P (Vm) = RT
(A) (Urms)A = (Urms)B  It is a wrong condition
(B) P(Vm) = 0.821 × 40
TA T
as  B RT = 0.0821 × 400
mA mB  P (Vm) = RT
 Wrong
3 3 m  (C) P(Vm) = 0.310 × 0.821 = 25.45 l atm
(B) (K.E.) H 2 = R (n. T) = R   400  RT = 0.0821 × 324 = 26.6 l atm
2 2 2   P(Vm) RT
3 m  Wrong
3 
(K.E.) He = R (n. T) = R  800  (D) P(Vm) = 0.0324 × 0.0821 = 0.0266 (l atm)
2 2 4  RT = 0.0821 × 324 = 26.6 l atm
 Difference is quite large
 (K.E.) H 2 = (K.E.) He  (D) is a incorrect condition

 
Z1 (H 2 ) Q.19 (A,B,C,D)
(C)
Z1 (He) = 2   2 400  N * ,  N H 2  N He Q.20 (A,D)
RT 
 ( Z1 ) H 2  ( Z1 ) He as V is same] P= 
V   TV 2
Q.13 (B,C,D) 
Q.14 (B, C) 1
PV V    
Clearly from the diagram
   1   
T2 T1 T2 MB RT V   RT V  V 
2
RT 2 V
(vMPS)B > (vMPS)A  M  M  T  M
PV   P 2    
B A 1 A
hence if T1 > T2. MA is necessarily greater than MB  1   2  ......    2 
Q.15 (A, B, C) RT  V V   RT V 
With increase in temperature, most probable velocity
increases & fraction of molecules with velocity equal PV    1 2
to M.P. velocity decreases. Total no. of molecules   1        .......
remain same. RT  RT 2  V V 2
comparing with virial equation.
Q.16 (A, B, D)
K.E. is a function of temperature. If temperature is  
B = – and TB =
constant, K.E. will be constant.
RT 2 R
68 J EE C OMPENDIUM
 Current
Gaseous
Electricity
State

Q.21 (A,B,C) Q.29 (B)

(A) When attractive force dominate then actual molar
volume is less then 22.4 litre.
nRT 10R  900
Ptotal = = = 450 R
(B) Compressibility factor at critical condition is same V 20
for different gases.
(C) The real gas do not behave as an ideal gas at critical 2
 ( PH 2 ) I = × 450 R = 90 R Ans. ]
condition] 10
Q.22 (B, D) Q.30 (A)
2
a 64 a n1 2
PC = TC 2 = 2 2 Ratio of moles in two container =
27b 2
27  27 R b n2 3
TC2 64 a 2 (KE) I =
27 b 2
VC = 3b = 
PC 2
27  27 R b 2
a  7 3 
n H 2,1  2 R  n Ne ,1  2 R  n CH 4,1  12R  ×
8a 27 R 2 TC2
TC = 27 Rb a = 900
64 PC
( K E ) I I
Q.23 (A, C, D)
 7 3 
= n H 2, 2  R  n Ne, 2  R  n CH 4, 2  12R  ×
Q.24 (A, B)  2 2 
incorrect
1200
(A) at boyle’s temperture a real gas behave as ideal
=
irresp. of pressur
(B) At critical condn a real gas behave as ideal. 3 7 3 
 n H 2,1  R  n Ne,1  R  n CH 4,1  12R  ×
Q.25 (A, B, C, D)
2 2 2 
Factual Question 1200

Q.26 (A,C)
(KE ) I 900  2 1
 = = Ans. ]
Q.27 (B, D) ( KE ) II 1200  3 2
Initially P = 760 mm of Hg = 1 atm
 PA (initial) = 1 atm Q.31 (B)
2 A  3B + 2C Pev/2 = nCT
100 T = 500 K
1–0.20.30.2
PTotal = 1.3 atm = 98.8 cm Hg
P
Total Pressure inaeared by 0.3 atm 1 atm
diffenence in Hg level = 98.8 – 76 n = 2 moles
= 22.8 cm
=228 mm v(lit)
Q.28 (B) P = 1 atm
Pressure in each container is same on solving
n1RT1 n 2 RT2
1 e 0
= C= = 0.001
V1 V2 500  2
Q.32 (D)
n1  V1   T2  1 4 2 P. ev/2 = nCT
   
n 2  V2   T1  = 2 3 = 3
= nC
T
P=
ev / 2
3 3
 n2 = n1 = ×10 = 15 mole Ans. ] nC
2 2 Slope =
ev/2
C = 0.001 & V = 2L
C HEMISTRY 69
Current Electricity
Gaseous State

n=2
1 1 1
 4
P=
2
e1 4 2 2 2 2
1000
Z11y  2 2 Z11x  2 2 A
Q.33 (A)
V = 2001 P = 1 atm T = 200 K at earth Q.37 (D)
200 1 (I) Z = 1  Ideal behaviour.
n= = (II) Z > 1  On applying pressure, volume decreases.
200  T R
(III) Z < 1  Gas can easily liquefied.
1 (VI) At low P, Z  1 means gas is approaching
P. e100 = × C × 821
R to ideal behaviour.

10 Q.38 (B)
On solving P =
e100 Z=
PVm
>1
RT
Q.34 (D)
Z = z 2 u N* PVm 1 22.4
=
RT RT
1
N*  At same pressure = 1 atm.
V
1 Vm 1 22.4
1 >
RT RT
x  =A
A
V  Vm > 22.4 L at STP for real gas.
For, Vm = 22.4 L of real gas, we have to increase
1 A
y = the pressure.
2V 2
Ratio = 2 : 1 Q.39 (D)
None of these On moving from region (II) to region (I), pressure tends
to zero. So, Z  1.
Q.35 (C)
Q.40 (B)
(N*)2
Total no. of colusons per unit volume 
V TH 2 TCH 4 TSO 2
: : 
Ratio = 1 : 2 M H2 M CH 4 M SO 2
Q.36 (A)
H2  2H 200 400 1600 20 40
: :  10 : :
nx n x/4 1 2 16 64 4 8
 He  
ny nH x /1 4  10 : 5 : 5  2 : 1 : 1 ]

Vx 1 Q.41 (A)

Vy 2 
u av 8RT 1
=
Nxx 1 1 Z1 = M
×
Z1
 2 
Nxy 4 4
 1 T   1 T 
x      
Z M  : Z M  :
 y = 2 (because H2 become H)  1 H2  1  CH 4

Uavgx (T / M)x T /4 1  1 T 
     
Uavgy (T / M)y 2T / 1 2 2 Z M 
 1 SO 2
2 2
 N     
z11x
 x    Uavex     x  = 1 200 1 400
Z11y  Ny 

 Uavg    y
  

 18
 : 17
 :
10 2 10 16
70 J EE C OMPENDIUM
 Current
Gaseous
Electricity
State

(ii) if T>TB , it will behave more like ideal gas, shape

1 1600 would be like A.
  1 : 5 :1]
5 1017
64 (iii) B will show real gas behavious but A will show
more likely a ideal gas behavous at T > TA
Q.42 (C)
Q.48 (B)
Trans Rotational CV Total kinetic energy
b = 4 Vm
5R 5R 4
H2 3 2 T × 32 b = 4×NA ×  r3
2 2 H2 3
CH4 3 3 3R 3R TCH × 4  V1 = V–nb
4  nb = V–V1
SO2 3 3 3R 3R TSO 2 × 2
V – V1 4  3 v – V1  
b = 4×NA ×  r3 r =  
16 nNA 
Ratio is 3
h
5 1/3
 × 32 × 200 : 3 × 4× 400 : 3 ×2 × 1600  8  3(V – V1 ) 
2 diamatery = 2r   
 10 : 3 : 6 ]  16 nNA 
Q.43 (C)
 3 (V – V1 ) 
dN 1 N d 
  U avg  A  2  nNA 
dt 4 V
Q.49 (C)
Nt t After transferring contents
dN 1 A
   U avg dt
N 04 V n H 2O ( g ) 
0.1
N0 = 0.05
2
1 A
 U avg t
 0.4  246.3  1
Nt = N0 e 4 V Ans. ] n N2 (g)    = 2
 24.63  2
Q.44 (A)
(2  0.05) R  300
1 A  P(first vessel) = = 0.205 atm
U avg   t =0.7 246.3
4 V Ans. ]
4  2  0.7 Q.50 (C)
t= = 1.4 ×105 sec.
4 103 10 2 10 6
0.1 0.0821 300
Ans. ] PH 2O   = 5 × 10–3 atm
Q.45 (B) 2 246.3
Uavg will double therefore
PH 2O 5 10 3  760
t 1.4 10 5 R.H. = 100  100 = 25 %
time = = = 7 × 104 sec. Ans.] aq.T 15.2
2 2 Q.51 (B)
Q.46 (A) P1 = 70 + 20 = 90 cm of Hg,
P2 = (70 + 5) cm of Hg  90 × 20 = 75 × (5 + x) x = 19
P
A cm.
B
PA Q.52 (C)
V
P1 = 75 cm of Hg, V1 = 24 × A
At critical temperture gaseous behave as ideal
T > TA & TB > T
T A < T < T B. 0.4  10
P2 = 75 + 10 + = 100 cm of Hg
Q.47 (C) 13 .6
(i) B is behaving like real gas at T K from graph
 Pressure correction term can not be hegligibel
C HEMISTRY 71
Current Electricity
Gaseous State

Patm (C) PV = nRT

P2
x
 75 × 24 = 100 × x log P + log V = log K
x = 18 cm
(D) PV = nRT
Q.53 (A)
K
Case  Case  V=
P1 = (P0 + h)P2 = (P0 – h) P
P1V1 = P2V2
K2
Now in both the cases, the gas is the same and V2 =
temperature is also constant, hence boyles law can be P2
applied.
y
1 A (P0 + h) = 2 A (P0 – h)
h(1   2 )
P0 = (    ) cm of Hg column.
2 1
x
Q.54 A-r; B-s; C-p; D-q
1
(A) v / sP
V2 y2 x

y Q.55 (A) - s ; (B) - q, s ; (C) - r ; (D) - p

(A) PV = nRT
At constant temperature
PV = K (T = constant)
x Higher the value of PV, higher the temperature.
So, T3 > T2 > T1
PV = nRT
Since, P1 = P2 = P3
K2 So, V  T  V3 > V2 > V1
P2 =
V2 PM
d=
RT
Since, P1 = P2 = P3
X2 y 1
d  d1 > d2 > d3
y = mx T
(B) PV = nRT (B) From Graph,
V3 > V2 > V1 and T1 = T2 = T3
y Higher the volume, lesser the pressure because
temperature is same for all.
P 1 > P2 > P3
PM
x d=
RT
Since, T1 = T2 = T3
V nR
= =K So,d  P  d1 > d2 > d3
T P (C) From the graph,
V = KT P3 > P2 > P1 and T 1 = T2 = T3
K Higher the pressure, lesser the volume because
temperature is same for all.
V =  1 

V1 > V2 > V3
T
72 J EE C OMPENDIUM
 Current
Gaseous
Electricity
State

PM (D) From Dalton's law of partial pressure at constant

d= temperature.
RT
P = P1 + P2 + .......
Since,T1 = T2 = T3
(E) Vander Waal's equation (real gas equation)
So,d  P  d3 > d2 > d1
(D) From the graph,  a 
 P   (V – b) = RT (For 1 mole)
d3 > d2 > d1and P 1 = P2 = P3  V2 
PM 1
d= d  R
RT T (F) = K (Boltzmann constant)
N
So,T1> T2 > T3
(G) Molar volume = 22.4 L at STP
PV = nRT
(I) Constant temperature P – V curve is called isotherm.
Since,P1 = P2 = P3
(J) Graph between V and T at constant pressure called
VT
isobar.
So,V1 > V2 > V3
Q.56 (A) - q, r ; (B) - p,s ; (C) - q,r ; (D) - p,s
Q.58 (A)Q,R (B) P,Q (C) Q,R,T (D) (D) P,S or P,Q,S]
(A) At low pressure, b is negligible in comparison to
(D) Assuming only translational kinetic energy
Vm.
Ans. P,S
  Assuming translational, rotational as well as vibrational
P  a 
 Vm2  (Vm) = RT
T K.E. Ans. P,Q,S ]
 

PVm a JEE-ADVANCED
 = Z = 1 – V RT < 1 INTEGER TYPE
RT m
Q.1 [2]
So, gas is more compressible than ideal gas.
P1T2 1 273 1
a P1T2  P2T1 or P2 or P2  
(B) At high pressure, V 2 is negligible in comparison T1 546 2
m
to P. hence x = 2
P (Vm – b) = RT
Q.2 [2]
PVm Rb
 =Z=1+ < 1.
RT RT
Q.3 [4]
So, gas is less compressible than ideal gas.
(C) Low density of gas means pressure is low so, at 16
PHe  X He PTotal  = 4 atm
a 4
low pressure Z = 1 – V RT < 1 and gas is more Q.4 [6]
m
compressible than ideal gas.
(D) At 0ºC H2 and He have a  0. Q.5 [5]
Pb
So, Z = 1 + and gas is less compressible than Q.6 [5]
RT H – 14.3%, C = 85.7%
ideal gas.  Emperical formula is CH-2
Q.57 (A-w), (B-u), (C-v),(D-p), (E-x), (F-y),(G-r),(H-q),(-s), (3n)
(J-t). (CH2--)n + O 2 
 nCO 2  nH 2O
2
(A) PV = K (Boyle's law)
P1V1 = P2V2 = P3V3 3n
(B) From charle's law 1 mL reacts with mL
2
V V1 V2
V  T  =K T = T 3n
T 1 2 10 mL reacts with  10
2
(C) From Graham's law
3n
1 PM  .10 75
r and d =  d  M. 2
M RT
150
1 n 5
So, r  . 30
d

C HEMISTRY 73
Current Electricity
Gaseous State

Q.7 [6 atm]
4 3
V C* : C : C = 1 : : = 1 : 1.128 : 1.225
P1V1  P2 V2 or 2  V  P2  P2  8atm  2
4 Note : As no option correspond to mean square speed,
Total increase = 8-2 = 6 atm it is understood as misprint. It should be root means
square speed. So, ans is (3)
Q.8 [4]

1 r1 M2 Q.2 (2)
Graham’s Law r  ,  In low pressure region, vanderwaal equation becomes.
M r2 M1
a
Z = 1 – RTV
Q.9 [8] m
Q.3 (3)
Q.10 [9] At high pressure, real gas particles can be easily
compressed.
nRT an 2
P   10  1  9
V  nb v 2 Q.4 (3)
At high pressure and low temperature, molecules do
Q.11 (1) have a volume and also exert intermolecular attractions.
Vn
K.E.  n Q.5 (1)
 a 
K.E.1 n1 V1 1
 For 1 mole of gas,  P  2  (V–b) = RT
T
 V 
K.E.2 = n 2 V2 = 2
a a
At very high pressure, P > > 2 so, is negligible.
Q.12 (3) V V2
2 × M. Mass = V. D. P(V – b) = RT  PV – pb = RT
no. of moles remain same pb
 average mol. mass remains constant. ] 
RT
Q.13 (4)
Average translational kinetci energy of 1 mol gas is Q.6 (1)
depend only on temperature not on molecular mass] Instantaneous dipole-induced dipole forces or loosely
van der Waals’ forces are responsible for the
Q.14 (1) liquefaction of xenon.
For Helium compressibility factor Z > 1
value of "a" is very small for He. Q.7 (1)
a: Vander Waal constant ] 3RT
urms =
M
Q.15 (1)
For case I, i.e., at temperature 2T and for N2 molecules
JEE MAIN 3RT
PREVIOUS YEAR'S u=
28
Q.1 (3)
For case II, i.e.,at temperature 2T and for N atoms :
2RT
C* = most probable speed = 3R  2T u 1 1
M u     u  2u
14 u 4 2
8RT
C = average speed = M Q.8 (3)

3RT
C = Mean square speed corrected as rms =
M Pi Pf
C* < C <C
P,T1 V,T2

74 J EE C OMPENDIUM
 Current
Gaseous
Electricity
State

Pi (V) Pi (V) Pf (V) Pf (V) 4R

   On solving x 
RT1 RT1 RT1 RT2 2R
Q.13 (2)
2Pi 1 1  Z = PV/nRT
 Pf   
T1  T1 T2  ZnRT
P
V
2Pi  T1T2 
Pf    Z
T1  T1  T2  at constant T and mol P 
V
2Pi T2 PA ZA VB  3   1  3
Pf        
T1  T2 PB A B VA  2   2  2
Q.9 (2) 2PA = 3PB
Mass  RT 
Density = ; PV = RT  V   Q.14 (1)
Volume  P 
8a
MP Tc =
So, d = 27Rb
RT
Now, d1= x, p1= 4, M1= 28, d2= 2x, p2= 2, M2= ? a
Greater value of  higher is Tc'
d1 M1P1 RT2 M1P1 b
So, d  RT  M P  M P ( T1 = T2)
2 1 2 2 2 2
Gas a
b
M1P1d 2 2x  28  4
 p d  2  x 1.3
2 1 Ar = 0.406
3.2
Q.10 (2) 0.2
Real gases show ideal behaviour at high temperature Ne = 0.118
1.7
and low pressure.
5.1
Q.11 (4) Kr = 5.1
1
PM
For an ideal gas, d = 4.1
RT Xe = 0.82
Molar mass of NH3 = 14 + 3 = 17 g mol–1 5
Molar mass of HCl = 1 + 35.5 = 36.5 g mol–1  Tc has order : Kr > Xe > Ar > Ne
 Ans. Is (1)
PNH3 M NH3
d NH3 
RTNH3 Q.15 (3)

PHCl M HCl Z
d HCl 
RTHCl
b
Dividing eqn. (i) by (ii), we get Slope = RT

d NH3 PNH3 M NH3 RTHCl

 
d HCl RTNH3 PHCl M HCl
P
M NH3
= (  T and P are same) As b slope
M HCl Hence, Xe, will have highest slope
17
= = 0.465 Q.16 (3)
36.5  Gas A and C have same value of ‘b’but different
Q.12 (4) value of ‘a’ so gas having higher value of ‘a’ have
PV = nRT more force of attraction so molecules will be more closer
200 × 10 = (0.5 × x)R × 1000 hence occupy less volume.

C HEMISTRY 75
Current Electricity
Gaseous State

 Gas B and D have same value of ‘a’ but different 4

V2 = (12)
3
value of ‘b’ so gas having lesser value of ‘b’ will be
3
more compressible.
so option 3 is correct. P1V1 48  10 3  (3)3
P2 = 
V2 (12)3
Q.17 (4)
2RT 2RT 48  10 3
Vmp  = = 7.5 × 10–4 = 750 × 10–6 bar
Þ Vmp  64
M M
For N2, O2 H2
Q.24 (4)
300 400 300 Pressure due to 1 mole of H2 gas = 2 atm
   Pressure due to 1 mol of H2 + 1 mol of
28 32 2
He + 1 mol of O2 = 6 atm.
Vmp of N2(300K) < Vmp of O2(400K) < Vmp of H2(300K)
Q.25 [70oC]
Q.18 (4)
CRMS > CAvg > CMPS P1 P2
T1 = T2
Q.19 (2)
Among given intermolecular forces, ionic interactions 35 40
= T
are strongest forces. Thus, correct order is ion-ion > 300 2
ion-dipole > dipole-dipole
40  300
T2 =
Q.20 (3) 35
Ethyl acetate is polar molecular so dipole-dipole = 342.86 K
interaction will be present in it. = 69.85oC
 70o C
Q.21 (3)
Edge length, a = 300 pm, Q.26 [1]
density, d = 6.17 g cm–3 P(V – b) = RT
For bcc, Z = 2 PV – Pb = RT
Z M PV
–
Pb
=1
Density, d = a 3  N RT RT
A
Pb
2 M 2M z=1+
6.17 = 6.02 1023 (300 1010 )3  6.02  2.7 RT
dz b
M = 50 g/mol =0+
dp RT
Mass 200g
Number of moles = Molar mass  50g / mol = 4 mol b xb
= =
RT RT
umber of molecules = 4 NA x=1
Q.22 (1) Q.27 [5]
PM = dRT
 4.75 
d 
1    0.0826  323
= 
nRT 26 
T V= 5L
d  P P  740 
 
 760 
Q.23 [750]
At constant temperature and number of moles, Q.28 [150]
P1V1 = P2V2
Total moles of gases, n = n CH 4  n CO2
4
P1 = 48 × 10–3 bar ; V1 = (3)
3
6.4 8.8
3 =   0.6
16 44

76 J EE C OMPENDIUM
 Current
Gaseous
Electricity
State

nRT 0.6 8.314 300 8.2  10 3

Now, P =  P V =  RT
V 10 103 M
= 1.49652 × 105 Pa = 149.652 kPa From equations (i) and (ii)
150 kPa
3.47 14.2103 8.2 103  3.47
Q.29 [927]  P = 
P1 = 3 Pa = 3 bar and T1 = 300 K P 8.2 103 14.2 103
Maximum pressure that can withstand by cylinder
= 12 Pa = 12 bar Q.34 [1655]
Pv = nRT
P1 P2 3 12
  
T1 T2 300 T2 11
2 × 106 × 2 × 10–3 = × 8.3 × T
44
300 12 T = 1927.7 K
 C
3 T = 1654.7°C

Q.30 [84] Q.35 [2]

Total moles = n1 + nII H2 + O2
As TI = 300 K TII = 60 K on mixing 
Heat lost by I is gained by II 40% by mass
nICm (nIICm ( Let mass of mixture = 100 gm
Mass of H2 = 40 gm
2.8 0.2
C m (300 – T)  C m (T – 60) Mass of O2 = 60 gm
28 28
Loosing gaining 40
Mole of H2 = = 20 mol
2
14(300 – T) = T – 60 60 15
T = 284 K Mole of O2 = mol = mol
32 8
Let final P = P
Partial pressure of H2
N t RT n
PV = nt RT, P = H2
V   Ptotal
n
H2  n O2
 2.8  0.2  8.31Jmol K  284K
–1 –1
bar
P=   10 –5
 28  3  10 –3
m 3
Pa 
20
 2.2
15
= 84.28 bar 20 
 84 bar = 84 8

 20  8 
Q.31 (4)    2.2
 160  15 
an 2
= atm (as it is in pressure correction) 160  2.2
V2 
175
V2 (dm3 ) 2
a = atm  atm 
352
 2.011  2 bar
n2 (mol) 2
175
Unit of a = atm dm6 mol–2

Q.32 (1) Q.36 [25]

For an ideal gas, PV = nRT p = 99 bar z = 2 b = ?
So PV = constant (at constant T) = 99  0.987 atm
Vander wall equation –
Q.33 (2) a
Initial mass of gas = 29 – 14.8 = 14.2 kg (P + ) (V – b) = RT for 1 mole
v2
Mass of gas used = 29 – 23 = 6 kg
Gas left = 14.2 – 6 = 8.2 kg 
At high p   Can be neglect
2
14.2  103
PV = nRT V  RT
T (i) But b  can not be neglected
M P (V – b) = RT
C HEMISTRY 77
Current Electricity
Gaseous State

P V – Pb = RT
E abe K 2.215  10 18
PV pb RT  1  1
13.6  1.602  1019
= 2.0166
  E req E req
RT RT RT
 Q.40 [80]
Pb PNe = Ptotal × XNe
Z= 1  20 = 25 × XNe
RT
20 4
2=
Pb
1  X Ne   
RT 25 5

pb  200 
RT
=2–1=1   4
  20  
99  0.987  b =8.3  298 200 x
   5
b = 0.253 = 25.3  10 – 2  20 32 
Ans.: 25 (nearest integer)
10 4
 
x 5
10 
Q.37 [1] 32
Normality of Acid - Base mixture solutions  400 = 320 + x
N A VA  N B VB  x = 80
NMIX = VA  VB
Q.41 [32]
At constant volume and mole
M A n A vA  M B n B vB
VA  VB P1 P2
=
T1 T2
0.1  2 100  0.1 1 50
= 30 P
100  50 = 2
300 318
20  5 15
=   0.1N  30 
150 150 P2 =    318  31.8  32
Ans: 1x 10–1, Ans (1)  300 

Q.42 [45]
Q.38 (2) Wgas
PA= PA0 × XA = Ptotal × YA (PV)gas = ( MM )RTTgas
gas

 PA0 × 0.2 = 0.8 × 0.5 WH 2

(PV) H2 = ( RT
PA0 = 2atm MM H2 ) H2

Q.39 [2] According to question (PV)gas =  PV H 2

h 3 0.2
 ( )300  ( )200
2mK M gas 2

h2 3  300  2
K M gas 
2m 2 0.2  200
Mgas = 45
h2 43.9 1068
K 
2m 2 2  9.1  10 31 10.89 10 20
K = 2.215 × 10–18 Q.43 [9960]
Eabs = Ereq + K nRT
VH2  g  
P

78 J EE C OMPENDIUM
 Current
Gaseous
Electricity
State

2
   0.0831 300
 
2
 24.9L T3
1
T2
 Volume of H2(g) adsorbed on 2.5 g Pt=24.9 L P3
24.9 P T1
 Volume of H2(g)adsorbed on 1 g Pt   9.96L (atm) P2
2.5
We know 1L=1000 ml P1
So 9.96 L  9960 ml. d (g cm )
–3

Q.44 (D)
Weight of liquid = 135 – 40 = 95g Q.48 [22]
Press . of moist = 4 atm
mass 95
Volume of liquid = = =100ml Press. of gas = 4-v.p of H2O
density 0.95 = 4 – 0.4
Volume of vessel = 100 ml = 3.6
PV = nRT When volume is doubled  P = P/2
100 3.6
0.82   nRT   1.8
1000 2
100 Total Press. = 1.8 + v.p of H2O
0.82  = 1.8 + 0.4 = 2.2 atm
1000 1
n 
0.0821 250 250
JEE-ADVANCED
mass of ideal gas 40.5–40 0.5 g PREVIOUS YEAR'S
Given mass Q.1 [5]
We know, n 
M.mass h
1 0.5 = 2m (KE) KE  T
 
250 M Mass
M Mass = 0.5×250  He mNe KENe 20  1000
= 125 g  Ne = mHe KEHe
=
4  200
= 5.

Q.45 [29]
Q.2 (C)
V=
nRT 0.90× 0.82×300× 760
= 29.21 K  L  V at constant P
P 18×32 Hence T(Heating)
Q. 46 [4]
100
1.5  4.16  0.83  300
M
M = 3.99
Q.47 (B)
PM = dRT
Where P = Pressure of an ideal gas; d = density of ideal
gas
R = Universal gas constant; T = Temperature
P density
on plotting a vertical line, where to put density
is constant L  M  P at constant V
P Temperature P3 > P2 > P1 Hence T(Cooling)
from there T3 > T2 > T1 M  N  V at constant P
Hence T(Cooling)
N  K  P at constant V
Hence T(Heating)
Q.3 (B)
C HEMISTRY 79
Current Electricity
Gaseous State

LM Hence Z > 1 at all pressures.

MK This means , repulsive tendencies will be dominant when
Both are having constant volume therefore these pro- interatomic distance are small.
cesses are isochoric. This means, interatomic potential is never negative but
Q.4 (C) becomes positive at small interatomic distances.
According to Grham’s law, if all conditions are identical, Hence answer is (C)
Q.8 [4 times]
1
r Given diffusion coefficient is proportional to mean free
M path (λ) and mean speed (Vmean)
As in this question, all conditions are identical for X And absolute T is increased by 4 times
and Y, it will be followed
1
And average K E  T  mV 2  T
rx My 2
Hence 
ry Mx When T increased by 4 times  Vmean increases by 2
times (i)
d 40 Also mean free path, λ =

24 – d 10 KT T
 
d 2 d P 2
P
=2 Increasing T 4 times and P 2 times,
24 – d
λ increases 2 times (ii)
d = 48 – 2d
from (i) and (ii) implies, diffusion coefficient increases
3d = 48
4 times
d = 16 cm.
Q.5 (D) Q.9 [2.22]
The general formula of mean free path () is P1 = 5 P2 = 1
v1 = 1 v2 = 3
RT
 (d = diameter of molecule, p = T1 = 400 T2 = 300
2d2N A P
5 3
pressure inside the vessel). n1  n2 
400R 300R
 d & p are same for both gases, ideally their  are
Let volume be (v + x) v = (3 – x) 15 – 5x = 4 + 4x
same. Hence it must be the higher drift speed of X due
to which it is seeing more collisions per second, with PA PB

the inert gas in comparison to gas Y. So X see TA TB
comparably more resistance from noble gas than Y and
hence covers lesser distance than that predicted by n b1  R nb  R
Graham's Law.  2
v b1 v b2
Q.6 [9]
Initial moles of gases = 1 5 3
 
92 U 
238
 206
82 Pb  8 42 He  6 1e 400  4  x  300R  3  x 
Inital moles 1 moles
11
Moles after 8 mole  5 (3 – x) = 4 + 4x x
decompostion 9
Total gaseous moles after decompostion = 8 + 1 = 9 11  20 
v  1 x  1     2.22
moles 9  9 
Pf nf Q.10 [1,2,3]
Ratio of pressures P  n  9 3RT
i i Urms =
Q.7 (C) M
P(V–b) = RT 3
Eavg = kT
 PV – Pb = RT 2
PV Pb Q.11 (B)
  1 Graph represents symmetrical distribution of speed and
RT RT
hence, the most probable and the average speed should
Pb be same. But the root mean square speed must be
Z = 1  greater than the average speed.
RT
80 J EE C OMPENDIUM
 Redox Reaction and Equivalent Concepts

Redox Reaction and Equivalent Concepts

DPP-1
Q.1 (3) Q.13 (3)

Q.2 (4) Q.14 (3)

Q.15 (3)
Q.3 (1) Let the oxidation state of sulphur in Na2S4O6 is x.
1 × 2 + 4 × x + (–2) × 6 = 0
Q.4 (1) 2 + 4x – 12 = 0
NC–H 4x – 10 = 0
4x = 10
Q.5 (3) 10
x= = 2.5
+1 4
O – Cl
Ca
Cl
–1 DPP-2
Bleaching powder
Q.1 (2)
1  1
 Average oxidation state = =0
2 Q.2 (4)

Q.6  Q.3 (3)

Q.4 (4)
Q.7 (3)
The oxidation state of iodine in HIO4 is + 7 as
Q.5 (3)
1 + x + 4 (–2) = 0
x=+7
Q.6 (2)
The oxidation state of iodine in H3IO5 is +7 as
3 + x + 5 (–2) = 0
x=+7
The oxidation state of iodine in H5IO6 is + 7 as
5 + x + 6 (–2) = 0
x=+7
by cross multiply
Cr2O72–+6Fe2++14H+  2Cr3+ + 6Fe3+ + 7H2O
Q.8 (2)
Q.7 (1)
Q.9 (2)
An amalgam is a homogeneous mixture  5e 
 8H  MnO 
 Mn2  4H2O  2 ...(1)
4 
 Oxidation state of sodium and mercury in sodium
amalgam is 0. C O 2
–2
4  
 2CO2  2e  5 ..... (2)
10e  16H  2MnO  2Mn 2  8H2O ..(3)
  
Q.10 (3) 4

5C 2 O 4–2   10CO 2  10e  ..... (4)

Q.11 (1) ________________________________
–2 sp
2 1 6H   2M n O 
4  5C 2 O 4  
–2
 2M n  2  1 0C O 2  8H 2O
S sp3 Compare this equation with
– –
O–S–O  z
4  yC 2O 4  zH 
xMnO –2
 xMn 2  2yCO2  H2O
O +6 2
so x = 2, y = 5, z = 16
Q.12 (2)

Q.8 (1)

C HEMISTRY 81
Redox Reaction and Equivalent Concepts

Apply N1V1 = N2V2

Q.9 (1)
M1 x n 1 x v 1 = M2 x n 2 x v 2
N2  NH3 (v.f. = valence factor) (Acid) (Base)
O.N. = 0 O.N. = –3  v2 = 40 ml
v.f. = 6
Q.8 (2)
28 100 ml mixture
Eq. wt. =
6 NaOH + Na2SO4
eq. of H2SO4 = eq. of NaOH
Q.10 (1) 0.5 x 10 x 2 = M × v × n-factor
7 5 10 = M × 100 × 1
Mn O4–  Mn O3– – 2e –
M  0.1
moles = 0.1 × 0.1
= 0.01
DPP-3 mass = .01 × 40
mass  0.4 gm
Q.1 (3)

Q.2 (4) Q.9 (3)

BaCl2 + Al2(SO4)3 BaSO4+ AlCl3
MnO4 + C2O4  Mn + CO2
– 2– 2+

Initial meq. 30 × 0.2 40 × 0.3 0 0 O.N. = +7 +3 +2 +4

=6 = 12 0 0
After rexmeq. 6 – 6 12–6 6 6 vf1 = +5
vf2 = +2
So meq.of BaSO4 = 6
& Eq. of BaSO4 = 6 × 10–3 n1vf1 = n2vf2
1 × 5 = n2 × 2
 233  Wt.
 eq.w t  2  & Eq. = eq.Wt. n2 
5
 
2
W t.  2
= 6 × 10–3 = Q.10 (3)
233
0.1914 25  0.12
Q.3 (3) 0.1 M NaOH H 2 C2 O 4 Equivalents of acid = 
E 1000
v=?? + 20 ml = Equivalents of base
0.05 m  E = 63.8 g
eq. of NaOH = eq. of H2C2O4  (3)
0.1 × V × 1 = 0.05 × 20 × 2
V  20 ml Q.11 (4)
v.f.1 = 5
Q.4 (4)
MnO4– + FeC2O4  Mn2+ + Fe3+ + CO2
ZnS + HNO3  Zn(NO3)2 + H2SO4 + +7 +2
+2 +3 +3 +4
NO2
(+2) (–2) (+5) (+2) (+6) v.f.2 = 1+2 = 3
(+4)
n1vf1 = n2vf2
Q.6 (1) n×5=1×3
6e  Cr2O7–2  14H  2Cr 3  7H2 O n1 
3
5
5
Xn  X O3–   5 – n  e
According to question
6 × 10–3 × 6 = (5 – n) × 9 × 10–3
So n = 1

Q.7 (3)

82 J EE C OMPENDIUM
 Redox Reaction and Equivalent Concepts

EXERCISES-I
JEE MAIN The O.N. of P in P2O5 is 2x + 5 (–2) = 0 or x = +5
OBJECTIVE QUESTIONS The O.N. of P in H4P2O7 is 4 (+1) + 2 (x) +7 (–2) =
Q.1 (2) 0
Q.2 (4) 2x = 10 or x = +5
H2 S2 O 7 Since there is no change in O.N. of P, hence the above
+2 + 2x + (–14) = 0 reaction is neither oxidation nor reduction.
x = +6 Q.12 (1)
Q.3 (3) In KI3 1 + 3 × (a) = 0
Q.4 (4) 1
H2SO3 = +4 a=–
3
SO2 = + 4
H2SO4 = +6 or KI3 is KI + I2
H2S = – 2  I has two oxidation no. –1 and 0 respectively..
Q.5 (1) However factually speaking oxidation number of I in
K2Cr2O7 KI3 is on average of two values – 1 and 0.
+2 + 2x + (–14) = 0 1  2  ( 0 ) 1
Average O.N. =  .
2x = 12 3 3
x=+6 Q.13 (1)
KMnO4 Q.14 (2)
+ 1 + x + (–8) = 0 Q.15 (2)
x=7 Q.16 (3)
Q.6 (4) Q.17 (1)
F2O Q.18 (3)
Q.7 (3) Valency factor ratio is inversely related to molar ratio.
Q.8 (1) (V.f.)HI : (V.f.)HNO3 = 1 : 3 = 2 : 6  Molar ratio = 6
Cr2O72– + 14H+ + 6e–  2Cr3+ + 7H2O :2
Q.19 (1)
(H2O2  O2 + 2H+ + 2e–) × 3
MnO4– + C2O42– + H+  Mn2+ + CO2 + H2O
_
__________________________________________ V.f. = 5 V.f. = 2
 Balanced equation : 2MnO4– + 5C2O42– + 16H+
Cr2O72– + 8H+ + 3H2O2  2Cr3+ + 7H2O + 3O2
 2Mn2+ + 10CO2 + 8H2O
The reaction practically occurs with this
stoichiometry. Q.20 (1)
Q.9 (1) Q.21 (1)
In the above reaction C 2O4–2 acts as a reductant Q.22 (2)
because it is oxidised to CO2 as : In this +2  +5 (Oxidation)
C2O4–2  2CO2 + 2e¯(oxidation) Hence Nitric oxide act as reducing agent
C2O4–2 reduces MnO4¯ to Mn+2 ion in solution. Q.23 (1)
Q.10 (3) Q.24 (1)
Let the O.N.of Co be x Balance reaction is
O.N. of NH3 is zero 2KMnO4 + 5H2O2 + 3H2SO4  2MnSO4 + 5O2
O.N. of Cl is –1 + 8H2O + K2SO4
O.N. of Br is –1  Sum of stoichiometric coefficients = 2 + 5 + 3 +
Hence, x + 6 (0) – 1 x 2 –1 = 0 2 + 5 + 8 + 1 = 26
 x=+3 Q.25 (1)
so, the oxidation number of cobalt in the given 2MnO + 5PbO 2 + 10 HNO 3  2HMnO 4 + 5
complex compound is +3. Pb(NO3)2 + 4 H2O
Q.11 (3)
In the reaction P2O5  H4P2O7

C HEMISTRY 83
Redox Reaction and Equivalent Concepts
Q.26 (4)
Q.27 (4) V = 50 ml
n factor of K2C2O4. 3H2C2O4.4H2O
Q.28 (4)
for redox titration = 8
Q.29 (3)
for acid base titration = 6
Q.30 (1)  for acid base titration normality of
(NH4)2 Cr2 O7  Cr2O3 + N2 + 4H2O
O.S. of N= – 3 O.S. of Cr = +3 0.1
K2C2O4.3H2C2O4.4H2O = ×6N
O.S. of Cr = +6 O.S. of N = 0 8
Q.31 (1) Eq. of acid = Eq. of base
Q.32 (4)
0.1 50 1 Vml
Q.33 (2) 6  
Q.34 (1) 8  1000 8 1000
Q.35 (3) Vml = 30 ml Ans. ]
Fe(CO)5
O.S. = O JEE-ADVANCED
Q.36 (2) OBJECTIVE QUESTIONS
Q.37 (3) Q.1 (D)
n factor for Mn+3 = 1/2 Q.2 (D)
Q.38 (1) Na2S4O6 O.S = 2.5
Q.39 (1)
n.F. = 3 Q.3 (B)
2x + (–8) + 0 + 0 = – 2
equivalent wt. of FeC2O4 = M/3
x = +3
Q.40 (1)
Q.4 (B)
Q.5 (B)
Q.6 (A)
 (V.f.) BrO3– = 5 CO3O4 COx = +2
 Eq wt = M/5 COy = +3
Q.41 (1) 2x +3y –8 = 0
In this reaction H2SO4 is providing only 1 H+ therefore,
98 Q.7 (A)
its n-factor = 1 and equivalent mass = . Q.8 (B)
1 Na2W4O13. 10 H2O
Q.42 (1)
+2 + 4x + (–26) + 0 = 0
Given Emetal = 2 × 8 = 16
x=+6
Weight oxide Q.9 (A)
Weight metal = ?
Q.10 (C)
eqmetal = eqoxide – 1/2= oxidation state of oxygen, so it will form
w metal w oxide w oxide superoxide
24 3
=  w = = =
16 16  8 metal 16 2
Q.11 (A)
1.5
Fe0.93 O
Q.43 (4)
Eq. of NaH2PO3 + Eq. of NaHCO3 = Eq. of NaOH 0.93 x + (–2) = 0

20  0.1 40  0.1 x
200
1  1  x 93
1000 1000
x = 6 × 10–3 Q.12 (A)
Q.44 (2) In the above reaction C 2O4–2 acts as a reductant
Redox titration because it is oxidised to CO2 as :
Eq. of K2C2O4.3H2C2O4.4H2O = Eq. of KMnO4 C2O4–2  2CO2 + 2e(oxidation)
C2O4–2 reduces MnO4¯ to Mn+2 ion in solution.
0.1 V 20  0.05  5

1000 1000 Q.13 (C)

84 J EE C OMPENDIUM
 Redox Reaction and Equivalent Concepts

Q.14 (D) Q.21 (C)

CrO4–2    Cr2O7–2
x + (–8) = – 2 2x + (–14) = –2 AS2S3 + 28H+ + NO3–  NO + 14 H2O + ASO4–
x = +6 x = +6 5 + SO 2–
4
no. change occur in oxidation state.
Q.15 (A) M
Equivalent wt. of AS2S3 =
Q.16 (B) 28
HNO3  NH3 Q.22 (D)
Q.17 (1) If we assume XeF = 100
2MnO + 5PbO2  2HMnO4 + 5 Pb(NO3)2 Xe = 53.3 %
+ 10 HNO3 + 4 H 2O F = 100 – 53.3 = 46.70
] F = = = 6.1 6
formula = XeF6

Q.18 (B) Q.23 (D)

Balanced reaction Acidic MnO4–  M+2 n.F =
5
Basic MnO 4 –  MnO 4 –2
O. No. O. No. n.F. = 1
+3 –3
6e¯ + C6H5NO2 + 6H+  C6H5NH2 + 2H2O Neutral MnO4–  MnO2 n.F.
=3
 To produce 93 gm (or 1 mole) aniline absorbed
Equivalent wt. of in acidic basic : neutral
number of moles of electron in above reaction = 6
23.8 : 120 : 40
 To produce 18.6 gm (or 1 mole) aniline absorbed
3 : 15 : 5
number of moles of electron in above reaction
Q.24 (D)
6 Equivalent wt. = Molecular weight
=  18.6  1.2 Ans. Due to non ionization of Mohr’s salt
93
Q.25 (A)
Q.19 (C)
K4Fe(CN)6 + FeCl3 KFe [Fe(CN)6] + 3KCl
200 n=3 n=3
O.N. of. Fe in wustite is = = 2.15
93 K4Fe(CN)6 + FeCl2  K2Fe[Fe(CN)6] + 2KCl
It is an intermediate value in between Fe (II) & Fe n =2 n=2
(III)
Let % of Fe (III) be a, then (MV) K 4Fe(CN )6  (MV) FeCl3
2 x (100 – a) + 3 x a = 2.15 x100 10 × M1 = M2 × 10
a = 15.05
 % of Fe (III) = 15.05% (MV) K 4Fe( CN )6  (MV) FeCl2
10 × M1 = 0.5 × 20
Q.20 (A)
O2 + FeS2  FeO + SO2 M FeCl3 = 1 M Ans.
Oxidation half reaction :
S22–  2s4+ + 10e¯ .... (i) Q.26 (A)
Reduction half reaction : S  S2O32– + S–2
4e¯ + O2  2O2– .....(ii)
So, on doing 2 × (i) + 5 (ii) 2 2
n-factor of S = 1
 2S22– + 5O2  4s4+ + 10 O2– 22
2FeS2 + 5O2  4SO2 + 2FeO
 Since one molecule of FeS2 liberates 10 electrons Atomic weight 32
E= = ]
So 2 moles of FeS2 required to liberate 20 mole e¯. V / F / n  factor 1

C HEMISTRY 85
Redox Reaction and Equivalent Concepts

Q.27 (C) Q.34 (D)

Let Z undergoes change in oxidation number from n1
(NH4)3 PO4  
4  NO3¯ + PH3
KMnO
16 ml to n2 (n2 > n1) as a result of reaction with KMnO4.
–3 +5 +5 –3  meq of Z = meq of KMnO4
+24 – 8 = 16 0.1 × 25 × (n2 – n1) = 0.04 × 25 × 5
50 × 0.2 M  n2 – n1 = 2
n–factor of KMnO4 in acidic medium = 5 Hence, the oxidation number of Z increases by 2.
n-factor of (NH4)3PO4 = 16  change = (Z2+  Z4+).
Eq. of (NH4)3PO4 = Eq. of KMnO4
Q.35 (A)
0.2  50 N  16
 16 = CI– + MnO4–  Mn+2 + CI2
1000 1000
N= 10 Ans. ] Eq of Cl2 = Eq of KMnO4
 10 
Q.28 (B) 2 [mole of CI2] = 5  158 
 
m eq of KMnO4 = 0.1 × 5 × V = 0.5 V
& m eq K2Cr2O7 = 0.1 × 6 × V = 0.6 V 50
mole of CI2 = = 0.15823 mole
2  158
So, K2Cr2O7 will oxidise more Fe2+
volume of CI2 at STP = 0.15823 × 22.4 = 3.54 L
Q.29 (B) Q.36 (B)
Q.37 (B)
 Mn 2
M nO 4–  Fe(NH 4 ) 2 SO 4 
Q.38 (C)
n.F. = 5e KMnO4 + FeS2 + CuS  Cu+2 + Fe+3 + SO2
x=+7 x=+2
n= 11 n = 6
Eq. wt of KMnO4 = M/5 Eq. of KMnO4 = Eq. of FeS2 + Eq. of CuS

Q.30 (A) N  V MVFeS2 MVCuS

m. eq. of H2SO4 = m. eq. of Na2CO3
 n  n
1000 1000 1000
V 0.125
0.1 × = 2 N  20 10  1 20  1 6
1000 106   11 
V = 23.6 mL
1000 1000 1000
Q.31 (D) 110  120 230
Milli equivalents of FeC2O4 = 0.1 × 3 × 25 = 7.5 N=   11.5 N Ans.
From choice (D), milli equivalents of KMnO4 = 0.1 20 20
× 5 × 15 = 7.5
 m. eq. of FeC2O4 = m. eq. of KMnO4
Q.39 (B)
Q.32 (B) 2 moles of Cu2+ = 1 mole of 2 = 2 moles of hypo.
1.68 × 10–3 × 6 = 3.36 × 10–3 × x so moles of hypo used = 20 × 10–3 × 0.1 = 2 moles
x=3 = moles of copper hence
So, oxidation number of A increases by 3.
2  10 3  63.5
% of copper = × 10% = 63.5%
 New oxidation number of A = –n + 3 = 3 – n. 0 .2
Q.40 (1)
Q.33 (A) Likewise in Br3O8, each of the two terminal bnromine
Equivalent of KMnO4 = Eq. of H2C2OH stoms are present in +6 oxidation state and the middle
0.0162 × V × 5 = .022 bromine is present in +4 oxidation state. Once again
× 2 × 25 the average, that is different from reality, is + 16/3.
0.022  2  25
V= =
.0162
13.6 ml

86 J EE C OMPENDIUM
 Redox Reaction and Equivalent Concepts

O O O 0.02  100  5 2x 2x
+6 +4 +6 = y  1 = y 2x = y
O Br Br Br O 0.05  100  2
O O
O Q.7 (A,C)
Structure of Br3O6 (Tribromoctaoxide)
M.wt
(A) 6 M1V1 = M2V2 [  For K2Cr2O7 , Eq . wt. = ]
JEE-ADVANCED 6
COMPREHENSION/STATEMENT/MATCHING/MCQ (C) N1V1 = N2V2
Q.1 (C,D) (B) and (D) are not possible.
In (C) option, Cl goes from +5 to +7 and –1, while in Q.8 (A,B,C,D)
(D) option, Cl goes from 0 to +1 and –1. equivalent of oxidising agent = equivalents of reducing
agent.
Q.2 (A,B,C) EqMnO  = Eq 2
4 Fe
Cr oxidises from +3 to +6 while I reduces from +5
nMnO  × 5 = n 2 × 1
to –1. One I atom gain 6 electron. 4 Fe
Q.3 (B,C) Eq Cr 2
2O 7
= EqFe2
S undergoes increase in oxidation number from +2 to
+2.5, while I undergoes decrease in oxidation number n Cr 2 × 6 = nFe2 × 1
2O 7
from 0 to –1.
EqMnO  = EqCu S
4 2
Q.4 (A,B,C)
nMnO  × 5 = nCu S × 8
(A) Oxidation state of K is +1 in both reactant and 4 2

product. Eq Cr 2
2O 7
= EqCu2S
In (B), oxidation state of Cr(+6) does not change.
In (C), oxidation states of Ca and C and O do not n Cr O 2  × 6 = nCu S × 8
2 7 2
change.
Q.9 (A,B,C,D)
In (D), the H 2O2 which disproportionates is both
For HCl N = M
oxidising and a reducing agent.
V1  1  V2  0.25
Final molarity = = 0.75
Q.5 (A,C,D) ( V1  V2 )
1 3  3 0.75 (V1 + V2) = V1 + V2 × 0.25
4H2O + Cu P  3Cu2+ + H3PO4 + 11e
1e– + 5H+] 0.75 V1 + 0.75 V2 = V1 + V2 × 0.25
3
0.5 V2 = 0.25 V1
×6
6e– + 14H+ + Cr2O72–  2Cr3+ + 7H2O] × 111 V1
V2 = 2 (All options are possible)
------------------------------------------------------------
------------------------
Q.10 (A,C,D)
6Cu3P + 124H+ + 11Cr2O72–  18Cu2+ + 6H3PO4 milli equivalent of KMnO4 = 25 × 0.2 = 5 meq.
+ 22Cr3+ + 53H2O (A) Fe2+  Fe3+
milli equivalent of FeSO4 = 25 × 0.2 × 1 = 0.2 × 25 =
Q.6 (A,B) 5 (same)
m.eq. of KMnO4 = m.eq. of KHC2O4
(B) H3AsO3  H3AsO4
x
0.02 × 100 × 5 = × 2 × 1000 milli equivalent of H3AsO3 = 2 × 50 × 0.1 = 10 (not
M
same)
....(1)
m eq. of Ca(OH)2 = m. eq of KHC2O4 (C) H2O2  2H+ + O2
y milli equivalent of H2O2 = 25 × 0.1 × 2 = 5 (same)
0.05 × 100 × 2 = × 1 × 1000 (M = Mol. wt. of (D) Sn2+  Sn4+
M
KHC2O4) ....(2) milli equivalent of SnCl2 = 25 × 0.1 × 2 = 5 (same)
Divide (1) and (2)
Q.11 (A,B,D)
Cu2S + I2  Cu+2 +
SO4–2 + I– .....(1)
C HEMISTRY 87
Redox Reaction and Equivalent Concepts

(nf = 10) (nf = 2)

CuS + I2  Cu+2 +
SO4–2 + I– .....(2) No. of equivalents of H2O2 = 6 × 10–3 eq.
(nf = 8) (nf = 2)
I2 + S2O3–2  I– + Wt of H2O2 present in 25 ml of solution = 6 × 10–3 ×
S4 O 6 –2 .....(3) 17
(nf = 2) (nf = 1) ( Eq. wt H2O2 = 17) = 0.102 g
(nf = 2) Statement (A) is correct.
In reaction (1) :
0.102  1000
Meq of Cu2S = Meq of I2 Wt of H2O2 in 1L of the solution = =
0.5 × 10 × V = 250 × 1 × 2 25
V = 100 ml (of Cu2S) 4.08 g
In reaction (2) : Statement (C) is wrong.
Meq of CuS = Meq of I2 4.08
0.5 × 8 × VCuS = 250 × 1 × 2 molarity of H2O2 solution = = 0.12 M
34
VCuS = 125 ml
Statement (B) is correct.
mol.wt 254 2H2O2 
eQ.wt of I2 = = = 127 2H2O + O2
nf 2
2 mol
1 mol
Q.12 (A,C,D) 0.12 mol
Na2SO4 + Ba(NO3)2  BaSO4  + 2 0.06 mol
NaNO3 Volume of O2 at NTP = 0.06 × 22.4 lit = 1.344 lit
4 × 10–3 V × 4 × 10–3 ppt. 2 × 4 V × 10– Statement (D) is correct.
3
Comprehension # 1 (Q. No. 15 to 17)
0 0 Q.15 (C)
Q.16 (C)
8V  10 3
M=  10 3 Q.17 (B)
5V Comprehension # 2(Q. No. 18 to 25)
Q.18 (B)
8 8 Q.19 (A)
=  M Na   M NO   M
5 3 5 Q 20 (B)
Q.21 (A)
Q.13 (A,D)
Q.22 (C)
1 mole Na2C2O4  1 mole CaC2O4 [from reaction
Q.23 (A)
(i)]
Q.24 (A)
1 mole CaC2O4  1 mole H2C2O4 [from reaction
Q.25 (B)
(ii)]
1 mole H2C2O4  2 mole CO2 [from reaction (iii)] Sol.18 Na2 [Fe(CN)5 No]
+2 + x + (–5) + (+1) = 0
 n CO2 = 2
x=+2
Sol.22 K 2O  K 2O2  KO2  KO3
3RT 3PV
Urms =  –2 –1 –1/2 –1/3
M nM
For CO2 gas
Sol.23 Because F2 gain and get reduced, so act as oxidising
3RT 3PV agent.
Urms = 
M CO 2 2M CO 2
Sol.25 FeSO4. 7H2O
Q.14 (A,B,D) x + (–2) = 0
No. of equivalents of S2O32– = 20 × 0.3 × 10–3 = 6 × x = +2
10–3 eq.
No. of equivalents of I2 produced = 6 × 10–3 eq. Comprehension # 3 (Q. No. 26 to 28)

88 J EE C OMPENDIUM
 Redox Reaction and Equivalent Concepts

Q.26 (C) 0.0549

Q. 27 (B) Moles of BaCrO4 in 10 ml =
Q.28 (C) 253
Sol.26 10 e– + 2MnO4–  2Mn2+ ; v.f. = 10
0.0549
M Moles of BaCrO4 in 250 ml =  25
 Eq. mass of Ba(MnO4)2 (Ba(MnO4)2 = 253
10
0.0549
Sol.27 Fe0.9 O + K2Cr2O7  Fe+3 + Cr+3 Moles of BaCrO4 = moles of Cr =  25
253
 2 
n factor of Fe0.9 O = 0.9  3   = 0.7
 0 .9  0.0549
wt. of Cr =  25  52  0.282 g
M
253
10M
 Eq mass = =
0.7 7 0.282
Sol.28 n factor is 2 for CaC2O4 % of Cr by wt. =  100 = 2.82 %
10
M 128 Q.34 (A)
Eq. weight = = = 64.
2 2 H
2BaCl2 + Cr2O7–2  2BaCrO4
Comprehension #4 (Q. No. 29to 32)
Q.29 (D) 0.0549
Moles of BaCrO4 =
Q.30 (B) 253
Q.31 (B)
Q.32 (C) 0.0549
FeCr2O4 Fe0.95O Moles of Cr2O7–2 =
253  2
x mol y mol
MnO4¯ + Fe+2  Mn+2 + Fe+3 Step–I
FeCr2O4  Fe + CrO4
+3 2– Cr2O7–2 + Fe+2  Cr+3 + Fe+3 Step–II
(nf = 7)
Total millieq of Fe+2 = 1.19
Fe0.95O  Fe +n millieq of Fe+2 in step–II = millieq of Cr2O7–2 =
(nf = 0.85)
0.0549
K4[Fe(CN)6] + Fe+3  KFe [Fe(CN)6] + K+  6 = 0.65
(nf = 3) (nf =3) 253  2
K4[Fe(CN)6] + Fe+2  K2Fe [Fe(CN)6] + 2K+ Total millieq of Fe+2 = millieq of Fe+2 in step I +
(nf =2) (nf =2) millieq of Fe+2 in step II
m moles of K4[Fe(CN)6] 1.19 = I step + 0.65
reacted with Fe+3 = 10 ×1 – 0.7 = 9.3 millieq of Fe+2 in step-I
= m moles of Fe+3 equivalent of Fe+2 = 5.44 × 10–4
x + 0.95 y = 9.3 × 10–3
7x + 0.85 y = 0.0482 Q.35 (C)
x = 6.5319 × 10–3 Moles of BaCrO4 in 250 ml solution = moles of BaCl2
y = 2.9138 × 10–3 0.0549
=  25
w Fe0.95O = 0.2016 gm 253  2
w FeCr2O4 = 1.463 0.0549
wt. of BaCl2 =  25  208  1.125
253
Comprehension # 5 (Q. No. 33 to 35)
Q.33 (B) Comprehension # 6 (Q. No. 36 to 38)
Q.36 (C)
wt. of steel sample = 10 g in 250 ml of solution
Q. 37 (D)

BaCl2 + Cr2O7–2 
H 2BaCrO4 Q.38 (B)
Sol.36 Let V mL of H2O2 is taken
0.0549 g

C HEMISTRY 89
Redox Reaction and Equivalent Concepts

20
Normality = (B) Eq of H3PO4 = 4.9 × 3 = 0.15
5 .6 98
meq of H2O2 = meq of 2 liberated = meq of Na2S2O3
Millimoles of O-atoms = (Millimoles of H3PO4) × 4
20
Vx = 200 x 0.1  V = 5.6 mL  4.9 
5.6 =  1000  × 4 = 200
 98 
P is in + 5 oxidation state (Max = +5)
Sol.37 meq of H2O2 = meq of K2Cr2O7
It will not react with an oxidising agent as P is already
20 x in max O.S.
5.6 × = x 6 x 1000
5.6 294
4 .5
20 x 294 (C) Eq of H2C2O4 = × 2 = 0.1.
x = 6 x 1000 = 0.98 90
Millimoles of O-atoms = (Millimoles of H2C2O4) ×
Mass of K2Cr2O7 needed is 0.98 g
 4.5 
4=  1000  × 4 = 200
 90 
Sol.38 1000 mL H2O2  liberates 20 L O2 at STP C is in + 3 oxidation state (Max = + 4).
20 It may react with an oxidising agent and C may get
 1 mL H2O2  x 1000 mL O2
1000 oxidised from + 3 to + 4.
 5.6  20 × 5.6 mL of O2 = 112 mL of O2 (D) Na2CO3 is itself basic in nature, so it will not react
with a base.
Comprehension # 7 (Q. No. 39 to 41) Millimoles of O-atoms = (Millimoles of Na2CO3) ×
Q.39 (BC)
 5.3 
Q40 (A) 3=  1000  × 3 = 150.
Q.41 (A)  106 
Sol.39 I2  I– (Reduction) C is in + 4 oxidation state (Max = + 4).
(O.A.) It will not react with an oxidising agent as C is already
–2 –2
in max oxidation state.
S2O3  S 4O6
2  2.5 (ox ida tion
) Q.43 (A) p,q; (B) r,s; (C) r, s ; (D) p,q]
(R.A.) (A) Container–I reacts with container–II
n factor of KI = 6
+6e- KMnO4 K2Cr2O7
1×5=x×6 1×6=x×6
Sol.41
Cr2O7-2 Cr2O3 5
x= x=1
equivalent wt of (NH4)2 Cr2O7 = M/6 6
(B) n factor of Cu2S = 8
KMnO4 K2Cr2O7
Q.42 (A) – p,s ; (B) – q,r ; (C) – p,q,s ; (D) – r 1×5=x=8 1×6=x×8
(A) Eq. of base = N × VL = 0.5 × 0.2 = 0.1 5 6 3
x= x= =
4 .1 8 8 4
Eq. of H2SO3 = × 2 = 0.1
82 (C) n factor of K2C2O4· 3H2C2O4· 3H2O = 8
Millimoles of O-atoms = (Millimoles of H2SO3) × 3 KMnO4 K2Cr2O7
 4.1  5 3
=  1000   3 = 150 x= x=
 82  8 4
S is in + 4 oxidation state (Max = + 6)
(D) n factor of NH4SCN = 6
It may react with an oxidising agent and it may get KMnO4 K2Cr2O7
oxidised from + 4 to + 6.

90 J EE C OMPENDIUM
 Redox Reaction and Equivalent Concepts

 To produce 93 gm (or 1 mole) aniline absorbed

5 number of moles of electron in above reaction = 6
x= x=1  To produce 18.6 gm (or 1 mole) aniline absorbed
6
number of moles of electron in above reaction

6
NUMERICAL VALUE BASED =  18.6  1.2
Q.1 [3] 93
 10 x = 1.2 ×10 = 12
N2H4  ( Y )  10e 
( Y contains all N atoms) Q.5 [7]
Fe+2  Fe3+ + e¯
 N22   ( 2N) x  10e  Cr2 6+  Cr+6 + 6e–
– 4 = 2x – 10 -------------------------
x = +3 FeCr2O4  Fe2O3 K2CrO4 + 7e–
 oxidation state of N in Y is + 3
Q.6 [30]
Q.2 [16] Redox titration
Eq. of K2C2O4.3H2C2O4.4H2O = Eq. of KMnO4
2×(–3e¯)
0.1 V 20  0.05  5

(+6)
CrCl3 + H2O2 Na 2CrO 4 + 2H 2O 1000 1000
(–4)
2×(+1e¯) V = 50 ml
n factor of K2C2O4. 3H2C2O4.4H2O
for redox titration = 8
(balanced skelton) 2CrCl3 + 3H2O2 + 10NaOH  for acid base titration = 6
2Na2CrO4 + 6H2O + 6NaCl + 2H2O  for acid base titration normality of

______________________________________________________________________ 0 .1
K2C2O4.3H2C2O4.4H2O = ×6N
2CrCl3 + 3H2O2 + 10NaOH  2Na2CrO4 + 6NaCl 8
+ 8H2O
Eq. of acid = Eq. of base
 a=2 b=3 and c = 10
0.1 50 1 Vml
6  
8  1000 8 1000
Q.3 [10]
Vml = 30 ml Ans.
(NH4)3 PO4  
 NO3¯ + PH3
KMnO 4
16 ml Q.7 [6]
–3 +5 +5 –3 Eq. of NaH2PO3 + Eq. of NaHCO3 = Eq. of NaOH
+24 – 8 = 16 20  0.1 40  0.1
50 × 0.2 M 1  1
1000 1000
n–factor of KMnO4 in acidic medium = 5
= 6 × 10–3
n-factor of (NH4)3PO4 = 16
x = 6 Ans. ]
Eq. of (NH4)3PO4 = Eq. of KMnO4

0.2  50 N  16 Q.8 [6]

 16 = 2BrO3¯ + 10 Br¯ + 12 HCl  6Br2 + 6H2O + 12
1000 1000
Cl¯
N = 10 Ans.
21 2
Q.4 [12] Mol of Br2 = = 21 m mol
2
Balanced reaction
O. No. O. No. 5
+3 –3 No. of eq. of Br2 produced in 1st Reaction = 21 ×
6e¯ + C6H5NO2 + 6H  C6H5NH2 + 2H2O 3
+

C HEMISTRY 91
Redox Reaction and Equivalent Concepts

= 35 meq.
8
10 V.F. of Fe = .
3
 70 × M × = 35
12 Atomic mass 56
EFe = = = 21.
V.F. 8/3
6
M=
10 Q.15 [10]
x=6 Ans. meqCa(OH)2 = meq H3PO4
0.05 × V × 2 = 10 × 0.1 × 1
Q.9 [90] V = 10 mL
milli equivalent of H 3PO 4 = milli equivalent of
Ba(OH)2 Q.16 [68]
120 × 1.5 × 3 = V × 3 × 2 85 = Emetal + EOH–
So, V = 90 mL or 85 = Emetal + 17
or Emetal = 68
Q.10 [2] Q.17 [12]
meq of Na2SO3 = meq of salt 40 g, O  60 g metal
25 × 0.1 × 2 = 50 × 0.1 × x  x=1  8 g, O  12 g metal (E)
So, oxidation number of metal decreases by 1.
 New oxidation number of metal = 3 – 1 = Q.18 [32]
v.f. of SO2 = 1 (6 – 4) = 2
2.
M 64
 Eq. wt. = = = 32
2 2
Q.11 [2]

Ni(CO)4  Ni + 4CO Q.19 [16]
Valency factor of K2C2O4 . 3H2C2O4. 4H2O is 2 +
5CO + 2O5  2 + 5CO2
3(2) = 8
2S2O32– + 2  2– + S4O62– (as we now that KMnO4 oxidises only C2O42– to CO2)
so moles of 2 produced = 4 moles w
so moles of hypo used = 8 moles = (4 M) (2 litres). Now equivalent of K 2C 2O 4. 3H 2C2O 4 . 4H 2O =
equivalent of MnO4–
Q.12 [4] 5.08 1
×8=1×5×V×
Mg – 2 e–  Mg2+ 508 1000
so V = 16 mL Ans.
equivalents = moles × n-factor
=2×2=4 Q.20 (3)

Q.13 [1] Q.21 (1) n-factor of KMnO 4 is different in different

22400 mL volume contains = 1 mole gas conditions.
1 1
 224 mL volume contains =  224 = JEE MAIN
22400 100 PREVIOUS YEAR'S QUESTIONS
mole CO2 Q.1 (3)
Eq of CO2 = Eq of HCl 6 1 1 –2 6  2 1 1 1
(a) XeF6  H 2 O 
 XeOF4  2HF
1 20 No change in oxidation numbers, hence, no redox
×2= ×N
100 1000 reaction occurs.
N=1N 6 1 1 –2 6  2 1 1 1
(b) XeF6  2H2O 
 XeO2 F2  4HF
Q.14 [21] No change in oxidation numbers, hence, no redox
0 8 / 3
reaction occurs.
3 Fe + 4H2O  Fe3O 4 + 4H2
3Fe + 4H2O  Fe3O4 + 8H+ + 8e–

92 J EE C OMPENDIUM
 Redox Reaction and Equivalent Concepts

Decrease in O. No.
(Reduction)
Q.9 [3]
0
4 + 4H + e  MnO 4 + MnO2 + 2H2O
2MnO 2–
+4–1 +1–1 +6–1 + – –

(c) XeF 4 + O 2 F2  XeF 6+ O 2 +

(Oxidation) Oxidation state of Mn in MnO 4– = +7
Increase in O. No.
Oxidation state of Mn in MnO 2– = +4
Hence, it is a redox reaction.
Difference = 3
+2 –1 +5 –1 +2 –1 +5 –1
(d) XeF + PF [XeF] + PF –
2 5 6
Q.10 [1]
No change in oxidation numbers, hence, no redox
MnO4– + CrO4–2  Mn+2 + CO2
reaction occurs.
O. No. of C in C2O4–2 = +3
O. No. of C in CO2 = +4
Q.2 (4)
Change in O. No. of C = 1
Fact based.
Q.3 [19.00]
2Fe2+ + H2O2  2Fe3+ + 2OH– Q.11 (1)
2MnO4– + 6H+ + 5H2O2  2Mn2+ + 8H2O + 5O2 2KMnO 4 + 16HCl  2MnCl 2 + 2KCl + 8H 2O +
 x + y + x' + y' + z' = 19 Cl2(gas)
KMnO 4 oxidise HCl to Cl 2 that's why for acidic
Q.4 [10.00] medium HCl is not used in permaganate titration.
Phosphinic acid is H3PO2
NaOH + H3PO2  NaH2PO2 + H2O Q.12 [4]
milliequivalents of NaOH = milliequivalents of
H3PO2 7 4

V × 0.1 = 10 × 0.1 3MnO42  4H   2MnO4  MnO2  2H 2O

(A) (B)
V = 10 mL

Q.5 [6 ] 25 Mn
4
  Ar  4s 2 3d5  [Ar]4s03d3

Cr2 O 2- + 2OH– 2Cr O 2-

n  n  2
+ H2O
7 4 =
Cr O 2-
4
x + (–2 × 4) = –2  3  3  2   15  3.87
x=6
= 4 BM
Q.6 [0]
Q.13 [1]
Chromate salt MnO4– + CrO4–2  Mn+2 + CO2
CrO42  O no. of Cr=+6 O. No. of C in C2O4–2 = +3
O. No. of C in CO2 = +4
Dichromate salt
Change in O. No. of C = 1
CrO42  O no. of Cr=+6
Q.14 (1)
Difference in O. No =6–6=0
2KMnO 4 + 16HCl  2MnCl 2 + 2KCl + 8H 2O +
Q.7 [30] Cl2(gas)
N1V1 = N 2V2 KMnO 4 oxidise HCl to Cl 2 that's why for acidic
0.01 × 5 × V1 = 0.05 × 1 × 20 medium HCl is not used in permaganate titration.
V1 = 20 ml used
 Volume left = 50 – 20 = 30 ml Q.15 (1)
In acidic medium
Q.8 [6]
2KMnO4 + 5H2C2O4 + 3H2SO4 + K2SO4 + 2MnSO4 + 2MnO 4  10I   16H   2Mn 2   5I2  8H 2 O
10 CO2 + 8H2O In neutral/faintly alkaline solution
Mn2+ has 5 unpaired electrons therefore the magnetic
2MnO 4  I   H 2 O  2MnO 2  2OH   IO3
moment is 35 BM
C HEMISTRY 93
Redox Reaction and Equivalent Concepts

(+6)
Q.16 (3)
Q.25 (3)
Sodium have lowest oxidation potential in alkali metals. (A) Oxidation state of zinc is changing from 0 to +2.
Hence it is weakest reducing agent among alkali metals. (B) Zinc is displacing Au from complex.

Q.17 (3) JEE-ADVANCED

PREVIOUS YEAR’S
Q.1 (ABD)
+1 –1 –1
 O
HOCl + H2 O2  H3 O + Cl + O2 6 –  ClO3–  6H2SO4  Cl–  6HSO4–  3 2  3H2O
(O.A) (R.A) Hence, I– is oxidised to I2
Oxidise
Reduce Coefficient of HSO4– = 6
and H2O is one of the product.
Hence (A), (B), (D)
Q.18 (4) Q.2 (B)
Ce+4 and Tb+4 act as oxidising agent. Correct order :
H 3 PO 4 > H 4 P2 O6 > H 3PO3 > H 3 PO 2
Q.19 [12]  5  4  3  1
HBrO3 (Bromic acid)
Ox. State of Br = +5 Q.3 [1.87 or 1.88]
HBrO4 (per bromic acid) Fe + 2HCl  FeCl2 + H2
OX. State of Br = +7 x mole x mole
Sum of Ox. State = 12 Fe+2 + MnO4–
x 12.5ml
0.03 M
Q.20 [5]
nf = 1 nf = 5
KMnO4  Kl  H  
 Mn 2  I 2  H 2 O
x 12.5  0.03  5
Hence the change in O.S. of Mn is (5). 
10 1000
Q.21 [6] x = 0.01875 (x = 1.88 or 1.87)
O wt of Fe = 1.05g
= =

Chromyl chloride is Cl – Cr – Cl 1.05

% Fe =  100 = 18.75
5.6
O

Q.4 [18.75]
Hence the O.S. of Cr is +6

Q.22 (4) Q.5 [1.58]

[BF4]– 3.74
Covalency = No. of Bonds = 4 Number of moles of Cu(NO3)2 =  0.02
187
Oxidation state = +3 for Boron

Q.23 [10]
Fe(CO)5 O.S. of Fe = 0
VO2+ O.S. of V = +4
WO3 O.S. of W = +6
Sum of oxidation state of metals = 10

Q.24 [6]
Ammonium-phosphomolybdate is
(NH4)3PQ4 · 12 MoO3
MoO3


94 J EE C OMPENDIUM
 Chemical Equilibrium

Chemical Equilibrium

DPP-1
Q.1 (1) Q.6 (2)
We know, For the reaction,
Kp = Kc (RT)n n = 1
In the reaction,  Kp = Kc (RT)n =Kc RT
n = 2 – (1 + 3) = – 2
 Kp = (RT)–2 × Kc
Kp 1.8  103 atm
 Kc  
RT 0.082 L atm K –1 mol–1  700K
1
= 2 2 Kc = 3.13 × 10–5
R T
Q.7 (3)
Q.2 (3)
Q.8 (4)
 C
A + B  Q.9 (4)
Q.10 (1)
K
 C Q.11 (3)
 A  B Q.12 (4)
Q.13 (2)
mol L1 Q.14 (1)
 
1
  mol L1 = mol–1 L
mol L1  mol L1
Q.3 (2)
DPP-2
 3C(g)+D(s)
2A(g) 
Q.1 (1)
PCl5 dissociation a closed container
For this reaction, ng = 3 – 2 = 1 PCl5 (g) PCl3 (g) + Cl2 (g)
 Kp = Kc(RT)1 1 0 0
Kp 1 –   
or K C  Total mole = 1 –  +  + 
RT
 1+
Q.4 (2)
N2(g) + 3H2(g)  2NH3(g) 
KPCl3 (mole fraction) =
Kp = 1.44 × 10–5 1 

From Kp  KC RT 
ng P
  
 (partial pressure) PPCl3   
ng = np – nR 1  
=2–4=–2
4 2 ·P
KP Q.2 (4) KP =  const.
KC  1  2
(RT ) ng
4  (0.15) 2  4 4  (0.25) 2  P
or, 
1.44  10 –5
1  (0.15) 2 1  (0.25) 2
KC 
(0.082  773)–2 P = 1.38 atm
Q.5 (4)
Q.3 (1)
2KCN + AgNO   Ag(CN) 2  + KNO3 + K +
-

0.1 0
0.03 0 8.5
[NH3 ] 
(0.1-0.06) 0 (0.03)
0 (0.03) (0.03)
= 1 mole/litre
17  0.5
 Ag(CN) 2   Ag + +
-
2CN Q.4 (3)
2NO2
a 0.04(left from KCN)
0.03 N2O4  
(0.03-a) a (0.04 + a)
 
0.04  0.04 t=0 1 0
t = eq. 1 – 1/3 2 × 1/3 [33% = 1/3]
 0.04  a
2
nT = 2/3 + 2/3 = 4/3
 Kc = 4  10 -19
=
0.03 2/3
a = 7.5  10-18 x=
4/3
= 1/2

C HEMISTRY 95
Chemical Equilibrium

Q.9 (3)
1/ 2  1/ 2  P12
Kp1   2C
2A  B  ; K=x
1/ 2  P1
1 
1  A  B  C ; K= x
K p1  P1 2
2
1 1
N2O4   A 
 C  K


2NO2
2
B ;
x
t=0 1 0
Q.10 (3)
t = eq. 1 – 1/2 2 × 1/2 [50% = 1/2]
= 1/2 1 A(g) B(g) + C(g)
nT = 3/2 At equi. (1)  
1 2 1 1 2 Total = 1 + 
x =  = & xNO2   2 
2 3 3 3 3
 
2

 P
2 2
  P22  1   
K p1  3 3 Kp = 1  
1 .P
 P2 1 
3

4 3 4 2
× = P Kp = P
9 1 3 2 1 2
4 1 P
K p2  P2  1
3
 2
Kp
[  K p1  K p 2 ]
 Kp = 2 (Kp + P)
P1 4P2 Q.11 (1)
= Q.12 (2)
2 3
Q.13 (3)
P1 8 Q.14 (4)
 P  3 Q.15 (1)
2
Q.16 (1) Highest value of K C means does reactions
Q.5 (2) maximum approaches completion
Q.6 (3)
CO2 + C = 2CO DPP-3
·5 – x 2x
Total pressure at equilibrium Q.1 (2)
·5 + 2x – x = ·5 + x = ·8
K f 2.38  10 –4
x = ·3 KC  
K b 8.15  10 –5
 6 2
k= = 2.92
·5 ·3
Q.7 (1) Q.2 (1)
2 CO2  2CO + O2 Q.3 (2)
2 0 0
2–·8 ·8 ·4 Q.4 (1)
Q.8 (2) Q.5 (2)
H2(g) + I2(g) 2HI(g) Q.6 (1)
Q.7 (4)
K2 H 1 1
log K =  –  Q.8 (1)
1 2.303R  T1 T2  Q.9 (4)
Q.10 (3)
50 H  1 1 
log =  623 – 721
66.9 2.303R  
After calculation negative value of H is obtained.

96 J EE C OMPENDIUM
 Chemical Equilibrium

EXERCISES

JEE-MAIN Q.4 (4)

A B
OBJECTIVE QUESTIONS
The rate transformation of A to B just equal to rate of
Q.1 (1) transformation of B to A in the system.
A+B C+D
3n n 0 0 t=0
Q.5 (1) The rate of reaction directly propotional to
(3n–x) (n–x) x x t = teq.
molarities of the reactant.
(n–x) = x n = 2x
n
x= Q.6 (1) Given : Equilibrium constant, K C = 2.5
2
Q.2 (2) We know :
Given :- 1 mole of N2O4 Kf
 2.5
Initial temp. = 300 K Kb
Final temp. = 600 K Kf= 2.5×3.2×10–2 = 8×10–2
N2O4 decomposes
N2O4(g) 2NO2(g) Q.7 (3)
1 0 Given : K1 and K2 are rate constants of forward &
1–0.2 0.4 backward reaction.
 0.8  As we know
as we know Kf
PV = nRT  KC
Kb
P P K
 2 KC  1
n1 T1 n2 T2 K2
Q.8 (1)
1 P2
 K1 bx
1  300 1.2  600 A B Kc = =
K2 ax
P2= 2.4 atm

Q.3 (2) K1a  K 2b

Given :- Volume = 20.0 lit a - xb + x x = K K
1 2
0.50 mole of each gas that is H2 + I2 Therefore, (1) option is correct.
Now, H 2 + I2 2HI Q.9 (2)
intially 0.5 0.5 0 C2H5OH () + CH3COOH () CH3COOC2H5 ()
at eq. 0.5–x 0.5–x 2x
+ H2O ().
[HI]2 a a 0
Keq = 0
[H2 ] [I2 ]
a 0.33a a – 0.33a
0.33a 0.33a
(2x)2
49 = (as Keq = 49) (0.33a)  (0.33a)
(0.5  x)2 KC =
(0.67a)  (0.67a)
= KC = 1/4.
Q.10 (1)
2x
7= Given :- N2O4 2NO2
0.5  x
(g) (g)
2x = 3.5 – 7x conc. of N2O4 = 4.8 × 10–2 mol/lit
9x = 3.5 NO2 = 1.2 × 10–2 mol/lit
x = 0.39
2x x .39 KC 
1.2  10   3  10
–2 2
–3
conc. of [HI] = –
20 10

10
= 0.039 
4.8  10 
–2

C HEMISTRY 97
Chemical Equilibrium

Q.11 (2)
(1 / 5)
Given : N2(g) + O2 (g) 2NO(g) KC 
2 25
KC = 4 × 10–4  2   a–1 K = ....(1)
5  5  C 4(a  1)
1 1    
Now, No (g) N2(g) + O2(g)
2 2 as KC = 0.25 ....(2)
from (1) & (2)
K'C =?
25
1 1 .25 =
4(a  1)
K'C = [K ]1 / 2  (4  10  4 )1 / 2
C  4(a – 1) = 100
a – 1 = 25
1  a = 26
 50
2  102 Q.15 (2)
Given :- Reaction
Q.12 (2) Given : PCl5(g) CO(g) + H2O(g)
PCl3(g)+Cl2(g) CO2(g) + H 2 KC = 3
0.01 0.01 0.01 (g) (g)
[PCl3 ]  [Cl2 ] 0.01  0.01 (g) (g)
Kc    0.01 2 mole 5 mole
1 [0.01] 0.01
2 mole
2HI(g) H2(g)+I2(g) At eq. 2–x 5–x
0.01 0.01 0.01 x 2+x
0.01  0.01 [CO2 ] [H2 ]
Kc  1
2 (0.01)2 KC = [H O] [CO ]
2 2
N2(g) + 3H2(g) 2 NH3(g)
0.01 0.01 0.01 (x).(2  x)
3=
(5  x) (2  x)
(0.01)2 1
Kc  3
  10– 4 3[10 – 7x + x2] = 2x + x2
3 (0.01)(0.01) 10– 4 2x2 – 23x + 30 = 0
Extent of reaction KC (iii) > (ii) > (i)  3
x   (x – 10) = 0
 2
Q.13 (1)
Given 3A(g) + B(g) 2C(g) 3
at equ. 2 mole 2 mole 2 mole x x  10
2
2 2 2
 3
conc. of H2 =  2   /2
concn v v v
 2
KC = 9.0(given)
2  1.5 3.5
2 2  
[C] [2 / V] 2 2
KC = 3 
[A] [B] [2 / V]3 [2 / V] Now,  1.75

V2 PH2S  0.17
q=
4
v2 = 36  v = 6L Kp = [PNH3 ] [PH2S ]  .67 × .17= 0.114
Q.14 (3)
Given :- reaction
Q.16 (2)
A(g) + 2B(g) C(g)
Given 1 mole N2 , 3 mole H2
a 4 0
total pressure = 4 atm
(at equill.) a–x 4–2x x
reaction N2(g) + 3 H2(g) 2 NH3(g)
as x = 1
A(g) = a – 1, B(g)=2, C(g)=1 initially 1 3
at equilibrium 1–x 3–3x 2x
a–1 2 1 Ptotal = 1 – x +3 – 3x + 2x
[A] = [B] = , [C]=
5 5 5 = 4 – 2x ....(1)
98 J EE C OMPENDIUM
 Chemical Equilibrium

an given in question Now PC = 3x

Ptotal fall to 3 atm
1
 Ptotal = 3 ....(2) =3×
from (1) & (2) 16

1 3
3 = 4 – 2x  x    0.1875
2 16

1 3 1
PN2 = ; PH2 = 3 – ; PNH3 (eq.)=2 × Q.19 (1)
2 2 2 2H2O (g) + 2Cl2 (g) 2HCl (g) + O2 (g)
3 Kp = 0.03 T = 477oC = 700 K
 1 Kp = KC(RT)1
2
KP  0.03 
(PNH )2 (1)2
KC =
RT
=  0.082  700 
 
3
Kp  
(PN )(PH )3 1 3
3 KC = 5.23 × 10–4
2 2 
2  2 
Q.20 (2)
1 Using KP = KC (RT)ng

0.5  (1.5)3 KP
KP for dissociation of NH3  (0.5) × (1.5)3 so, log K = ng log RT
T
C
Q.17 (2) so, ng = –1.
Q.21 (4)
2 4 2 4 2 1
KP = 0.667 atm = atm = . P = . Given :- N2O4(g) 2NO2 (g)
3 1 2 1 2 2 Kp = KC ......(1)
4 2 4 Kp = KC RT ng
so, = 32 = 1 – 2
1 2 3 ng = 2 – 1
 1
1 1
so, 2 =  = KP = KC × RT
4 2 RT = 1
Q.18 (2)
1
A(g) + 2B(g) 3C(g) Kp = 2×10–3 T=
1 2 0 R
At eq. 1–x 2–2x 3x 1
 12.19 K
0.082
[C]3 (3x)3
Kp   T = 12.19 K
[B]2 [A] (2  2x)2 (1  x) Q.22 (3)

(3x)3 1
Kp  Given :- CO(g) + O (g) CO2(g)
4(1  x)3
.....(1) 2 2

as kp = 2 × 10–3 1 
ng = 1 –   1
2 × 10–3 × 4 = d  2 
(3x)3 1
2×10 ×4 =–3
3 ng = 
(1  x) 2
as we know
3x
2 × 10–1 =
(1  x) Kp
Kp = KC RT ng  T)–1/2
= (RT)
.2 (1 – x) = 3x Kc
.2 = 3x + .2x Q.23 (1)
0.2 1 Given :- 2NO2 2NO+ O2 Ke = 1.8×10–6
x=  (g) (g) (g)
3.2 16
T = 184ºC
C HEMISTRY 99
Chemical Equilibrium

= (184 + 273)K  475 K

1
R = 0.083 J K–1 mol–1  K 3  k1  K3 = K1 K2
K2
Now, ng = 3 – 2  1
Q.27 (1)
Kp = KC RT ng
N2O4 2NO2 M mix
KP
Kp = KC (RT)1  K = (RT)1 (1   ) 92  2  46
C =
1 
KP 1– 2
KC = 0.0821 × 457 92
Mmix =
1 
KP
KC > 1  KP > Kc D 46
= = (1 + ). Therefore, (1) option is
d 46 /(1   )
Q.24 (2)
Given :- Reaction as correct.
H2(g) + CO2(g) H2O(g) + CO(g) Q.28 (2)
Here K P = KC
D – d  D 
initally 0.25 0.25 0 0 =  ;  =  – 1 ;
at eq. 0.25–x 0.25x x x  d  d 

[CO] [H2O] x2 D

KC = [H ] [CO ]    =  + 1.
2 2 (0.25 – x)2 d

x2 D–d D–d
 0.16 – 2 [as KP = KC = 0.16] = ; = ;
(0.25 – x) (n – 1)d d

x2 D
(0.25 – x)
= 0.4  =   – 1.
d
x = 0.1 – 0.4 x
The point at which  = 0.
0 .1 1
x= 
1.4 14
(1 / 14)
% mole of CO = × 100
total mole
total mole = 0.5 mole
(1 / 14)
% mole of CO=  100
0.5 D  D
= 14.28%  d – 1 = 0 ; So,  d  = 1.
   

Q.25 (3)
Q.29 (3)
Given: H2(g) + I2(g) 2HI(g) Kp = 0.5
Dd
ng x=
Kp= KC (RT) d

now, D
x= –1
ng = 2 – 2 = 0 d
 Kp=KC D
KC = 50 =x+1
d
Q.30 (4)
Q.26 (3) Given - Reaction :
Rewrite the equation as 2HI(g) H2(g) + I2(g)
CO(g)+3H2 (g) CH4(g)+H2O(g) ; 1/K2 1 0 0
CH4(g)+2H2O (g) CO2(g) + 4H2(g) ; K3
 
1– (where a is degree
CO(g)+H2O(g) CO2(g)+H2(g) ; k1  

100 J EE C OMPENDIUM
 Chemical Equilibrium

C C  of dissociation)  3
C(1–) Total no. of moles = 1 –  + +
2 2  2
2  1 –  + 2
as K C= K p = 2  1+
4(1– )
Apply Mass conservation
 wt. of NH3 at t=0 =wt. of mixture of equil.
Kp 
2(1– ) 1 × [14 + 3] = (1 + ) 2 × U.
17 = (1 + ) × 2 × 6

2 Kp  17
1–  –1=
12
1 1
1 1 5 5
= 2 K  –1  =  % of  = × 100  41.66
 p  2 Kp 12 12

1 1
= 1 + 2 Kp Q.34 (1)
 Given: A(g) + B(g) C(g) + D(g)
1 1 0 0
1 2 Kp  1 2 Kp 1– 1–  
=  =
 2 Kp 2 Kp  1 [C][D]
K
Q.31 (2) [B][A]
2
KP = P  2P. 2
1 2 K
KP 1   2
so,   .
P

Q.32 (1) K 
Given - V.D of N2O4 = 30 1– 
N2O4 2NO2 1 1
1 0 
 K
1– 22
Total mole = 1 + 2 –   1 + 
1 1 K
Mass conservation 
wt. of N2O4 at t = 0 = wt. of mixture.  K
1 × (92) = (1 + ) 2 × 30 Now,
92
 =1+ K
60 
32 8 1 K
= 
60 15 Q.35 (1)
8 Given :
% = × 100 = 53.3%
15 A(g) B(g) + C(g) + D(g)
Q.33 (3) initially 1 0 0 0
Given :- Vapour density = 6 at eq. 1–x x x x
Reaction - Total mole = 1 + 2x
2NH 3(g) H 2(g) + Apply mass conservation
3H2(g) Wt. of A at t=0 = wt of mixture at eq.
initally t = 0 1 0 1 ×Mwt. = [1+2x] 2×50
0 Mwt. =(1+0.2)×100 (as x = 0.1)
 Mwt. = 120
At eq. 1–
2
Q.36 (3)
3 Given: N2O4 dissociated
2 N2O4 2NO2

C HEMISTRY 101
Chemical Equilibrium

1 0 Q.42 (2) On adding inert gas at constant pressure effect on

at eq. (1–x) 2x equilibrium will be similar to as if volume of container
Total mole = 1 – x + 2x has been increased.
=1+x
Mass conservation Q.43 (2) For any physical equilibrium on increasing pressure
wt. of N2O4 at t=0 = wt. of NO2 at eq. equilibrium shifts in the direction of higher density.
1 × 92 = (1+x)×82
92 Q.44 (3)
1 = x Solubility of gas is directly proportional to the
82
pressure of gas above liquid.
10
x%= %  12.2%
82 Q.45 (1) SO2Cl2(g) SO2(g) + Cl2(g)
Q.37 (3) Volume of container is constant
so no effect of addition of inert gas.
Given: PCl5 PCl3 + Cl2
initially 1 0 0 Q.46 (4)
at eq. 1–x x x Exothermic
Total mole = 1 – x + x + x  low yield at high temperature
=1+x ng < 0
apply mass conservation,  low yield at low pressure
1 ×208.5 = (1+x)×(2×57.9)
Q.47 (1)
208.5 2C(s) + O2(g) 2CO(g)
=1+x
115.8 ng = 2 – 1  1
 1 + x = 1.80 ng > 0
x = 0.80  so on increasing the pressure equilibrium shifted
left (or backward direction)
Q.38 (2) as pressure increases volume decreases.

D Q.48 (2)
We know that d = 1  (n  1)  PCl5(g) PCl3(g) + Cl2(g)
CO(g) + Cl2(g) COCl2(g)
where n is number of mole of gases produced from
Ni will react will CO hence concentration fo CO. will
one mole of a gas reduees
 Second equilibrium shifted backward which
increase the concn of Cl2 thus first equilibrium also
K2 Ho  1  1 
Q.39 (1) log =   shifted backward.
K1 2.303R  T1 T2 

K2 597.4  10 3  1  1  JEE-ADVANCED
log =   OBJECTIVE QUESTIONS
0.0118 2.303  8.314  1300 1200 
Q.1 (A)
log K2 = – 2 + log (0.0118) = – 3.928  K2 = 1.18 X2 + Y2 2XY
× 10-4
Therefore, (1) option is correct. 1 2
x x 2x 2x = 0.6  x = 0.3
Q.40 (1) 3 3
2SO2(g) + O2(g) 2SO3(g)
Hº=–198 Kj 1 2
[x2] = - 0.3 [y2] = - 0.3
Exothermic reaction 3 3
favourable at low temperature ng < 0 Therefore, (A) option is correct.
 favourable at high pressure
Q.2 (A) Since both concentration varies exponential. So
Q.41 (4) On adding any reactant equilibrium shifts in forward both rates are similar variation with time.
direction, so amount of product increases.

102 J EE C OMPENDIUM
 Chemical Equilibrium

 n =1+
3
2 
~1
Reactant
Rate & product
] 
1- 2x 1- ~
1
2
Time
4
   2 
Q.3 (D)  P   P
KP = 
2  1 
Ni+2 + 6NH3  [Ni (NH3)]+6 = 8P35
P2

Kf = 6 × 108
t =0 0.01 mole 0.1 mole 0 Q.7 (1) 2NH3  N3 + 3H2
100 80 80
Ni(NH )  (0.1)
6
80  (80)3
Ni NH  = Ni 0.4
3 6
K =
c 2 6 2 6 = 6 × 108 . [Ni+2] =
3 KP =
100
4 × 10–8.
Q.4 (A) N2(g) + 3H2(g)  2NH3  N2 + 3H2
2NH3(g) 80 + 3x = 128
1 3 100 80 80
1 x 3  3x x = 16
P P 100 80 – p 80
4  2x 4  2x 100 – 2x 80 – p + x 80 + 3x
2x 68 96 – p 128
P
4  2x (96  p)  (128)3 (80) 4
KP = 
(68) 2 100
4x 2  (u ) 2 64 x 2
KP = = (96 – p) = 9 = Partial pressure of N2
1 33 P 2 27 P 2
Q.8 (B)
3P. 3.K P
x= 2O3(g) 3O2(g) Kp = 4 × 1014
8
Q.5 (C) pO >> pO
2 3
2NH3(g) N2(g) + 3H2(g) p 3o 2
Kp = p 2 p O + PO = 8
o3 2 3

 Po  3 Po   PO ~
3
 8 atm.
  2
2(1   )  2(1   )  83
 14
Kp = 4 × 10 = p2O = 11.3 × 10-7 Therefore, (B)
1   
2 2
pO 3
3

 Po option is correct.

1   
Q.9 (3) G = G° + RT ln Q
 3 G – G° = RT ln Q
1- G – G° = –ve {ln Q < 1}
2 2
so G < G° Ans. (3)
 1 and 1 +  ~
1- ~ 1
27 Q.10 (4) D(l) + A(g) B(g) + C(g)
 27 × 10-8 P2o = Po2 × 4
16
 = 2 × 10-2
lnK =45°
Q.6 (A)
2AB4(g) A2(g) + 4B2(g)
1
K
T
C HEMISTRY 103
Chemical Equilibrium

G° = H° – TS° direction

(4) No effect on equilibrium as Qc remain same as
–RTlnKeq = H° – TS°
Keq
 H S  H
ln Keq =  m=– =1 Q.14 (B) A(g) + 2B(g)  C(g) + D(g) + E(g) Keq = 2
RT R R t=0 10 20
10  x 20  2 x x x x
 H 1 S t=t
ln Keq =   H° = – R 2 2 2 2 2
R T R
x3
S 2=
(10  x )(20  2 x ) 2
Y = mX + C C= >0
R
x3 x
Srxn > 0 8= 3  2 =  20 – 2x = x
Q.11 (B) (10  x ) 10  x
(I) N2O4 2NO2 Kc = 4
40 20
at point — A 20 20 = 3x x=
3 20 10 3
Pr oduct  [B] = = M
Q = Re ac tan t  = 0 2 6 3
So, Q have minimum value at point A.
Q.15 (B) Given :
(II) at point [N2O4] = [No2] = 0.1m
1
No2 2 0.1 0.1 2H2(g)+O2 2H2O(g) K
Q = N O  = = 0.1 1
2 4 0. 1

Q < Kc 2CO2 2CO(g) + 2()O2 K2

So, reaction proceeds left to right K2
(III) Kc = Q at point [D & F]. 2H2(g) + 2CO(g) 2H2O(g) + 2CO(g) K
1

Q.12 (B) H2(g) + CO2(g) H2O(g)+CO(g)

A (g)  2B(g) K2
at equilibrium 2 atm 1 atm  K= K1
12 K = 2.58
KP = = 0.5 atm
2
on doubling volume: A (g)  2B(g) P0
Q.16 (D)
new partial pressure 1 atm 0.5 atm P0 = 0.4 = mol fraction of solute
at new equilibrium 1 – x 0.5 + 2x
1  1 

(0.5  2 x ) 2 0.4 =
3 1  4  
= 0.5
1 x
2 1 
x  0.08 
so partial pressure of A = 0.92 atm 5 4
8 + 2 = 5 + 5
endo =1
Q.13 (C) CaCO3(s) CaO(s) + CO2(g) so 100 % dissociation Ans.
(1) as temperature dcreases  reaction moves
forward so extent of dissociation increases. Q.17 (B)
1 1
(2) P decreases by V increases Qc  i.e. Q > Keq SO3(g) SO2(g) + O (g)
V 2 2
reaction moves backward i.e. CO2 used.
(3) If inert gas add at constant pressure 0.9  0.082  1000
Mmix = =60
Volume decreases  Qc < Keq reaction moves forward 1.23

104 J EE C OMPENDIUM
 Chemical Equilibrium

 CuSO4 . 5H2O(s) CuSO4 . 3H2O(s) + 2H2O(g)

1-  KP = 2.25 × 10 -4
2
KP = p 2 H2O = 2.25 × 10-4

.Mso2  .Mo  (1   )Mso3
2 2
p H O = 1.5 × 10-2
Mmix =  2

1
2 22.8 PH O
Vapour Pr = = 3 × 10-2 R.H. = 2 × 100 = 50%
760 V.P.
 80  20 Therefore, (B) option is correct.
1+ = =
2 60 2 60 Q.22 (C)
(1) H > 0 so reaction will move in forward direction
2 with increasing in temperature.
=
3 (2) Reaction will move in forward direction with
decrease in pressure since gaseous moles are more
Q.18 (B) On decreasing pressure reaction will move
in products.
forward and  will increase so answer is (B). (3) BaCO3(s) will not impact equilibrium since active
mass of pure solid is 1.
Q.19 (D) (4) At constant pressure addition of inert gas will
CaCO3 CaO(s) + CO2(g) decrease the partial pressure of CO2 and reaction will
move forward.
Kp = (PCO2 )

(PCO2 ) is equal to equilibrium constant which only Q.23 (A)

Q.24 (B) N2 + 3H2  2NH3 H = –ve
change with canging only KP Yield of NH3 will be low (i.e. reaction will move in
But equilibrium constant only depends on temperature backward direction) at high temperature and high
so. volume. ]

Q.20 (B) Q.25 (D)

P1 = 15 atm; T1 = 300 K. As we know
Equilibrium temperature is 300ºC that is 573 K.  KP2 
  H  1 1 
So first of all we have to calculate pressure of NH3 at ln  K  – 
 = R T T
573 K.  p1   1 2 

P1 P2 15 P2 H  1 1 
T1 = T2 = 300 = 573 ln 4 =  – 
8.314  298 313 
P2 = 28.65 atm at 300ºC. H° = 71.6 kJ
1 3 Q.26 (A)
NH3 (g) N2(g) + H2(g). 2A2B(g) 2A2(g) + B2(g) KP = P
2 2
t=0 28.65 atm 0 0 4(1 – ) 4 2  n = 4 + 2
x 3
t = teq. [28.65–x] atm x 2
2 2  4   2 
  p   p
But according to question.  4  2   4  2 
KP = 2 =P
 4(1 –  ) 
x 3   P
Ptotal = 28.65 – x + + x  4  2 
2 2
= 28.65 = x = 40.11.  23 = (1 – )2 (4 + 2)
x = 11.46. 23 = (1 + 2 – 2) (4 + 2)
23 = 4 + 2 + 42 + 23 – 8 – 42
11.46
Degree of dissociation of NH3 = = 0.4. 2
28.65 =
3
Q.21 (B)

C HEMISTRY 105
Chemical Equilibrium

Q.27 (D) On increasing temperature though reaction Q.9 (A,C)

equilibrium shifts in the backward direction but for rate Given :
of reaction to be higher, higher temperature is required NH2COONH4 (s) 2NH3 9 + CO2(g)
and particle 500ºC is found to be optimum temperautre. 2x x
(2x)2(x) = 2.92×10–5
Q.28 (C) 2.92
x3 =  10–5
H2(g) 2H(g) 4
reaction is endothermic Ptotal = 3x = 0.0582
H>0  High temperature Q.10 (C,D)
ng>0 low pressure Q.11 (B,C)
Q.29 (B) Exothermic  low temp
 forward reaction favoured
H2O() H2O(g)
High temp backward
KP = (PH2O )
When neon is added at constant pressure, we have to Q.12 (C,D)
increase volume of the container. So more water will As given :
evaporate to mantain equilibrium. HgO(s)+4I–(aq)+H2O() HgI42–(aq)+2OH– (aq),
[HgI24 ] [OH ]2
K=
JEE-ADVANCED [I ]4
COMPREHENSION/STATEMENT/MATCHING/MCQ as, OH  HgI2– 


H2O()  OH 
Q.1 (A,C)
AB A+ + B¯ Q.13 (B,D)
K1 G = Hº + ST .....(1)
y y–x G = RT n k .....(2)
AB + B¯ AB2– K2 from (1) & (2)
y–x x Hº S
nk = 
x RT R
 K1 = (y – x)y K2 = y  x slope of the line equal to Hº/R
Q.14 (A,C)
k1 y As given :
 k = (y – x)2 H2O(s) H2O()
2 x
At OºC density of H2O (s) < H2O ()
As P  & V 
Q.2 (A,C)
 formation of more H2O (s)
Q.3 (A,B)
and increase in melting point of H2O (s)
kc 1 Q.15 (C,D)
log k = log Introduction of inet gas at constant Pressure will in-
p (RT )
crease  & volume  the Pressure of gases of equi-
 kp = kc (RT)  n = 1
Q.4 (A,B,C) librium
From given reactions.  equilibrium shifted forward
Q.16 (C,D)
1 NaNO3 (s) NaNO2(s) + O2(g)
(i) = – (iii); (i) = – (iv);
2 H > 0 endothermic
High temperature
1
(iii) = – (ii)  forward reaction favoured
2 1000 pressure
Q.5 (C,D) High pressure  Reverse reaction
Q.6 (B,C) Q.17 (A,C,D)
Q.7 (A,C,D) (A) As reaction is endothermic therefore it will go in
Q.8 (C,D) Addition of solids have no effect on equilibrium the forward direction hence moles of CaO will increase.
and temperature favours endothermic direction while (B) With the increase or decrease of volume particle
increasing pressure will shift equilibrium in backward pressure of the gases will remain same.
direction as ng is +ve. (C) Due to the addition of inert gas at constant pressure

106 J EE C OMPENDIUM
 Chemical Equilibrium

reaction will proceed in the direct in which more number

of gaseous moles are formed.
Q.26  
(B,C,D) From KP = PNH3 ( g) 2 (PCO2 ( g) )
and since reaction is exothermic.
Q.18 (B,C,D) Q.27 (B)
CO2(g) + C(s) 2CO(g)
PPCl3 ( g)  PCl2 ( g) t = 00.1 t = teq. 0.1 – x 2x
According to KP = PPCl5 ( g) =

(0.1  x )44  ( 2 x  28 )
(nPCl3 ( g) )eq.  (nCl2 ( g) )eq. = 36
0 .1  x
V  (nPCl5 ( g) )eq.
1
and on adding inert gas at constant pressure effect on  x=
30
equilibrium will be similar to as if volume of container
has been increased. 1 2
Q.19 (A,D) Total moles = 0.1 + =
30 15
For endothermic reaction, Hº is positive so, if T2 > Q.28 (A)
T1 then K2 > K1.
For exothermic reaction, Hº is negative so, if T2 > 1
Moles of CO2 at eq. = 0.1 – x =
T1 then K2 < K1. 15
Q.20 (C,D)
As few moles of CO(g) are introduced into the vessel 2 1
Moles of CO at eq. = 2x = =
second equilibrium shifts backward, decreasing the 30 15
concentration of Cl2. So, first equilibrium will go for- 0 . 082 x 900
ward. PCO2 = = 6 atm
15 x 0 . 82

1 0.082
Q.21 (A,B,C,D,E) PCO = x x 900 = 6 atm
15 0.82
H2(g) + 2(g) 2HI (g)
(A) For changing pressure volume has to be changed, 6x6
though number of moles of HI(g) do not get changed  KP = = 6 atm
6
but its concentration will get changed. Q.29 (B)
(B) Temperature change will change KP and hence nC = 0.1
concentration.
C(s) + CO2 (g) 2CO (g)
(C) Volume change will change concentration, not the
t=0 0.1 n
number of moles.
t = teq. – n – 0.1 0.2
(D) Same equilibrium will be attained from either
direction. 0.2 x 0.082 x 900
PCO = = 18 atm
(E) Catalyst does not change equilibrium 0.82
concentrations. (18)2
KP = 6 = P ; PCO2 = 54 atm
Q.22 (B,D) CO 2

(A) Backward shifting will take place.

(n  0.1) (0.082 ) (900 )
(B) Forward shifting will take place.  = 54
(C) Backward shifting will take place. 0.82
(D) Forward shifting will take place. n = 0.7
Q.30 (B)
Q.23 (A,B,C,D) Addition of inert gas at constant volume ng
has no effect on equilibrium concentrations. As we know, KP = KC (RT)
ng = 2 – 2  0
Q.24 (A,C) Addition of solids have no effect on equilibrium  49 × (.0802 × 700)0
and temperature favours endothermic direction while KP  49
increasing pressure will shift equilibrium in backward
direction as ng is +ve. Q.31 (C)
H2 + I2  2HI
Q.25 (A,B,C) Addition of inert gas at constant volume has 0.5 0.5
no effect on equilibrium concentrations. 0.5–x 0.5–x 2x

C HEMISTRY 107
Chemical Equilibrium

for SrCl2 2H2O PH2O = (KP)1/4

Total number of moles
0.5 – x + 0.5 – x + 2x = 1 (5×10–12)1/4 =1.49×10–3
for Na2HPO4 7H2O
1 × 0.0821 × 700
P= PH2O = (2.43×10–13)1/5 = 3×10–3
7
for Na2SO4
P = 8.21 atm
Q.32 (B) PH2O = (1.02×10–27)1/10 = 2×10–3
from above question Q.37 (B)
2
4x Na2SO4 10H2O will release moisture
KC =
(0.5  x)2 when PH O < 2×10–3
2

2 V.PH2 o  6  10–3 atm

 2x 
 
 7 
PH2O 2  10–3
 0.5 – x  0.5 – x  = 49
   Relative humidity = VP = = 33.33%
 7  7  H2O 6  10 –3
if relative humidity < 33.33%
2x  PH2O < 2×10–3
 7  x = 0.388
0.5 – x it will releases the moles
remaining I2= 0.5–0.388 = 0.112
Q.33 (A)
At equilibrium mole of HI =2x Q.38 (A)
= 2×0.388 above 33.33%
from previous question
(2  0.388)  0.082  700
PHI  Q.39 (B)
7
H 230
= 6.38 Slope = 2.3 R =  = –50
PHI < Ptotal 2.3  2
PHI <8.21 only case PHI=6.385 Q.40 (B)

20 –1 Hº Sº
Q.34 (A) PCl3(g) + Cl2(g) PCl5(g) ; KC = M Using equation, logK =  2.3RT  2.3 R
3
t = teq x 0.1+x 0.1–x
Q.41 (B)
20 (0.1  x )
 K2  Hº  1 1 
3 (0.1  x ) x Using equation, log K  2.30 R  T  T 
1  1 2
On solving x = 0.05]
Q.42 (C)
Given as :
H2(g) + I2(g) 2 HI(g)
2 initally 1 3
PNO 2
Q.35 (B) N2O4 2NO2 K= =1 At equilbrium 1–x/2 3–x/2 x
PN 2O4 addition of 2 mole H2’

PN 2O4 = 40 atm x x
At 60 atm 3– –
2 2
PNO = 20 atm x x
2 3– – x+x
2 2
and reaction will backward so PN 2O4 will be more =3–x
than 40. ] 3–x 2x

(x)2
Q.36 (A) Best drying agent reduces the moisture more
 x  x = (2x)2
effectively means reduces the  1 –  3  
2  2 (3  x)(3  x)

PH2O to the minimum

108 J EE C OMPENDIUM
 Chemical Equilibrium

3 Q.49 [(A)  P,R,S; (B)  P,Q,R,S; (C)  P,Q,R,S ; (D)  Q]

 2x=3  x  As we know
2
x=1.5 Kp
Q.43 (C) = (RT)ng
Kc
(2x)2 9 KP & KC ratio depend on T & ng
KC=  4 if we take T=0°C than
(3  x)(3  x)  9 
  (RT) > 1
4
Kp
KC=KP because ng =0
(A) if ng < 0 < 1  KP < KC
K C=K P=4 Kc
Q.44 (B)
Given : Kp
if ng > 0 > 1  KP > KC
2SO2(g) + O2(g) 2SO3(g) Kc
2 1.5
if we take T=0°C than
2  2x 1.5 – x 2x P, R, S
conc. =
5 5 5 (B) Addition of inert gas at const pressure means
SO2  SO3 (nf of SO2=2) pressure of equilibrium gases will decrease
m.eq of KMnO4 = m.eq of SO2 equilibrium shift where mole of gases are high due
0.4×5 = (2.2x)×2 to the conc of reactant means equilibrium shifted
2 = 2(1–x)×2 to forward
 ng > 0
1 But pressure is constant  volume 
 1-x = 1/2  x=
2  conc. of reactants 
P, Q, R, S
1 1
[SO2]= ; [O2] = (C) K°P always dimensonless P, Q, R,S
5 5 (D) T forward shift  H > 0
1
[SO3] = NUMERICAL VALUE BASED
5
KC = 5 Q.1 [2]
Q.2 [7]
Q.45 (A) q, s; (B) p ;(C) p ;(D) r Q.3 [3]
(A) ng = 2 – 4 = – 2 and KP = KC (RT)ng [PCl3 ][Cl2 ] (1.59) 2
(B) ng = 2 – 1 = 1 and KP = KC (RT)ng Q.4 [2] K c  [PCl5 ]

1.26
2.00

(C) ng = 2 – 1 = 1 and KP = KC (RT)ng

Cl2 n PCl3  P 
n 1
(D) KP is not defined.
Q.5 [1] K p   
 n 
n
PCl5
Q.46 [Ap; Bq; Cs; Dr]
1
Kp = KC (RT)ng 2 3
 2   
2 6
Q.47 (A – r) ; (B – r) ; (C – q) ; (D – p)
(A) ng is +ve so as P is increased, backward shifting 1 atm
will take place. Total pressure even after shifting will Q.6 [3]
remain same.
(B) ng is –ve so as V is increased, backward shifting Q.7 [0] G0  2.303RT logKp
will take place. But Pfinal < Pinitial.
If Kp  1 , G0  0
(C) No change but Pfinal < Pinitial as volume has increased.
(D) Forward shifting will take place and Pfinal < Pinitial.
Q.8 [2]
Q.9 [2]
Q.48 [A–p,t ; B–q, r; C–q,s]
0.1
Molar conc. of H 2S  mol L-1  0.25 mol L-1
(A)ng = 0
(B) ng = – 1 0.4
(C) ng = 2 Suppose degree of dissociation of H2S =  then
2H 2S  2H 2  S2
C HEMISTRY 109
Chemical Equilibrium

0.25 M equilibrium, the equilibrium tends to shift in adirection

in which volume decreases, i.e., in the forward direction.
0.25
0.25(1  ), 0.25 , 
2 Q.4 (2)
 0.125  0.125 A + B C + D
[H 2 ]2 [S2 ] t=0 1 1 1
KC =
[H 2S]2 1

(0.25) 2 (0.125) teq 1–x 1–x 1+x 1+x

10-6 
[0.25(1  2)]2
Neglecting in comparison to 1 we get (1  x)2
 = 100
6(0.25) 2 (0.125) (1– x)2
10   0.02
(0.25) 2 1 x
% age dissociation = 0.02 × 100 = 2%  = 10
1– x
 1 + x = 10 – 10x
Q.10 [7] As NaCl is salt of strong base + strong acid, it
does not undergo salt hydrolysis  11x = 9
9
Q.11 (1)  x=
11
Q.12 (1)
Q.13 (3) 9
 [D] = 1 +
Q.14 (4) 11
Q.15 (4)  [D] = 1.818
Q.5 (1)
JEE MAIN
1
PREVIOUS YEAR’S According to Boyle’s law : Pressure  i.e.,
Volume
Q.1 (4)
when volume of the container is increased, the
1  SO3(g)
For the reaction, SO2(g) + O 2 (g)  pressure decreases, To undo the effect of decreased
2 pressure. the reaction will move in a direction where
Using formula, Kp = Kc (RT)ng pressure increases i.e., towards the greater moles of
Where, ng = no. of products(g) – no. of reactants(g) gaseous substances. This is in accordance with Le
Chatelier’s principle.
 1 1
= 1 – 1   = – = x
 2 2 Q.6 (4)
Q.2 (1)
CO + 
Cl2  COCl2
 X + Y
X Y(s)  (g) (g)
Initial moles 2 3 0
Kp = (px) (py) At equil. 1 2 1
1
Px = xx PTotal = 10 = 5 bar 1
2
Kc =
COCl2   5  5 = 2.5
1  COCl2   1   2  2
Similarly, Py = 10 = 5 bar   
2  5  5 
Now, Kp = 5  Q.7 (1)
A 2(g) 
 2A (g)
Q.3 (3)
Ice  Water
+ Heat  Pressure at t = 0 1 atm 0
More volume More volume 20 20
On increasing the pressure on this system in At eqm. 1– = 0.8 atm 2 = 0.4 atm
100 100

110 J EE C OMPENDIUM
 Chemical Equilibrium

(p A ) 2 (0.4) 2 D  s  
Cg  E g

 k P2  x atm 2
Equilibrium constant, Kp = p = = 0.2 P1  P 2 P
A2 0.8 2

G° = – 2.303 RT log KP = –2.303  log k P1  P1  P1  P2 

0.2
k P2  P2  P1  P2 
= – 19.147 × 320 (log2–1)
k P1  k P 2   P1  P2 
= – 19.147 × 320 (0.301–1) 2

= 4282.64 J mol–1
x + y = (P1 + P2)2
Q.8 (4) P1  P2  2. x  y
2NO2(g) g) ; H = –ve 2  P1  P2   x  y
According to Le-Chatelier’s principle, when inert gas
is added at constant pressure, the total volume PTotal  PB  PC  PE  2  P1  P2   2 x  y
increases which leads to decrease in molar Q.13 (1)
concentration of reactant and product. Thus, the A  2B   2C  D
reaction moves towards backward direction and
Initial conc. a 1.5a 0 0
decomposition of N2O4 increases. Addition of inert at eq. a–x 1.5 (a – 2x) 2x x
gas at constant volume does not affect equilibrium. at eq. a – x = 1.5 a – 2x
On increasing the pressure, the reaction moves a – 1.5 a = –2x + x
towards forward direction (lesser moles) a = 2x
On lowering temperature, the reaction moves to
forward direction as it is an exothermic reaction. kC 
 2x 2 x 
4x 2 .x
4
 a  x 1.5a  2x 2  x  x 2
Q.9 (4)
From thermodynamics
Q.14 (4)
H S
Ink =   H 3 O   OH –
2H 2 O 
RT R
for exothermic reaction, Kw = 10–14
H = – ve G° = – 2.303 RT log K = – 2.303 RT log 10–14
H = + 2.303 8.314 14
slope =   ve
R = 79881.3 ~ 80000 J/mol = 80 kJ mol–1
So from graph, line should be A & B.
Q.15 (1)
Q.10 (3) Gº = – RT Ink
if K < 1  Gº > 0

1
A 2 (g)  B2 (g) 
K
 2AB(g) .......(1)
Q.16 (3)

6AB(g) 
K 2
 3A 2 (g)  3B2 (g) .......(2)
 SO2(g)
S(s) + O2(g)  K1 = 1052 ....(1)
Reaction (2) = –3 × reaction (1)
3  2SO3(g) K2 = 10129
2S(s) +3O2(g)  ....(2)
 1  3
 K2     K 2  K1
 1
K  2SO3 (g)
2SO2(g) + O2(g)  K3 = x
Q.11 (4) multiplying equation (1) by 2 ;
 3   2SO2 (g) K’1 = 10104 ....(3)
2S(s) + 2O2 (g) 
Gº = 120  T  0  Substracting (3) from (2) ; we get
8
Then T = 320 K 2SO2(g) + O2(g)   2SO3(g) ;
Hence T > 320 K Y formed (129–104)
Keq = 10 = 1025
T < 320 K X formed
Q.17 (4)
Q.12 (2) n g
K p  K c (RT)
A  s  

 Bg   Cg  k P1  x atm 2
when, n g = 0, Kp = Kc
P P  P
For, 2C(s) + O2(g) CO(g)
1 1 2

C HEMISTRY 111
Chemical Equilibrium

n g = 2 – 1 = 1 Q.23 [5]
Q.18 (2)  2Cl
Cl2 
At equilibrium, Moles at eq x x
rate of forward reaction = Rate of backward reaction
1 1
Q.19 (2) Peq
2 2
 Given reaction is endothermic
 On decreasing temperature backward reaction will PCl2
be favoured. On adding N2, pressure is increased at Kp = P
CL2
constant T, and volume would also be constant so no
change is observed. 2
Q.20 (1) 1
 
n g 2 1
K p  K C (RT) P = 1 = = 0.5
2
= KC (RT)1–3/2 2
= KC (RT)–1/2
= 5  10–1
 KC = Kp (RT)1/2
x=5
Q.21 (1)
Q.24 [2]
N2(g) + 3H2(g)  2NH3 (g) KC rG0 = – 2.303 RT log Kp
1
2NH3(g) + N2(g)  3H2 (g) r G0 25200 25200
KC log Kp =    3.3
2.303RT 2.303  8.3  400 7646
For Kp = 10 –3.3 = 0.501 × 10–3 = 0.501 × 10–4
1 Kp 5.01 104
 1 N 2 (g)  3 H 2 (g)
NH3 (g)  Kc = 
 RT 
n g
2 2 K1/2
C (8.3  400) 1
1  1 Kc = 5.01 × 8.3 ×400 × 10– 4
1/2
 1/2

KC (64) 8 16633.2 × 10– 4
166.33 × 10– 2
Q.22 [7]

AB2 (g)  A(g) + 2B(g) Q.25 [354] N2O4(g)  2NO2(g); ng = 2 – 1 = 1
Initial 1 0 0 Now, Kp = Kc . (RT)ng
At eq (1–x) x 2x or, 600.1 = 20.4 × (0.0831 × T)1
T = 353.99 K = 354K
n 1 0.82  300
Pi = RT   0.98 ~ 1.0 Q.26 [875]
v 25 2SO2(g) + O2(g)  SO3(g)
Total = ( 1– x) x + 2x = (1+2x) Initial 250 m bar 750 m bar
1  2x 0
peq =  1  1  2x  1.9 Final – 250 m bar –125 m bar 250 m bar
1
 
1 + 2x = 1.9

0.9 0 625 m bar 250 m
x= bar
2
Final total pressure = 625 + 250 = 875 m bar
0.9 2  0.96 2  0.9
 
x.(2x)2 Q.27 [16]
Kp =  2 2 2
(1  x) 1
0.9
 M (s)  1 O 2(g)
A (s) 
2 2
3
As only O2 is present in gaseous state.
 0.9 
  So, Kp = (PO2 )1/2
Kp =  2   0.6627  6.6 10 –1 ~ 7 101
0.55 PO2 = KP2 = 42 = 16

112 J EE C OMPENDIUM
 Chemical Equilibrium

Q.28 [1400] At equilibrium 1– x 1– x 1+ x 1+ x

 PCl +
PCl5  Cl2 (1  x) 2
 100  1  x 
3
Kc =
Initial conc. 3 0 0 (1 – x) 2 1 x
At eqm. 3– x x x
x x
xx 9 = 11x 
Kc = (3  x) = 1.844
[D] = 1 + x = 1.818 

x2 5.1
= 1.844 Q.33 [6] Moles of NH4HS = = 0.1 mol
3 x 51
x2 = 5.532 – 1.844x  NH 3(g )  H 2 S(g )
NH 4 HS(s) 
x2 + 1.844x – 5.532 = 0
Initial moles 0.1 0 0
1.844  (1.844) 2  4(1)( 5.532) at time t 0.1 – 0.02 0.02 0.02
x
2 = 0.08
x = 1.604 Since number of moles of NH3 and H2S is same, their
[PCl5] = 3 – x = 3 – 1.604 = 1.396 = 1396  partial pressure will also be same in this case.

Q.29 [25] nRT 0.020.082  300

P=   0.246 atm
 2C V 2
A  B 
Kp =  PNH3   PH 2S 
[C]2
Keq =
[A][B] Kp = 0.246 


A + B 


 2C
initial conc. Q.34 [2742]
at equilibrium 1– x 1– x 1+ 2x
1 1
HI  H2 + l2
1  2x 
2
2 2
K eq   100
1  x 1  x  initial 1 0 0
 0.4   0.4 
 1  2x   2   2 
2
1  2x after reaction 1–0.4
   100 ; = 100 = 10    
 1 x  1 x
1/2 1/2
1 + 2x = 10(1 –x)  0.4   0.4 
1 + 2x = 10 –10x x = 9     (0.2)1/2 (0.2)1/2
Keq=  2   2  =
0.6 0.6
9
x = = 0.75
12 0.2 1
[C] = (1 + 2 × 0.75) Keq= 
0.6 3
(1 + 1.5) = 2.5
G° = –nRT ln Keq
Q.30 [2] 1
= –1 ln  
Kp = Kc(RT) n g  3
47.9 = Kc (0.083 c = 2 G° = 2735 J mol –1

= 2742 Ans.
Q.31 [172] Q.35 [125]
2 NOCl (g)  2NO(g)
 + Cl 2
(pSO3 ) 2 (43) 2
Kp = (p ) 2 (p )  (g)
 45
2
SO2 O2 (0.53) Initial 2M 0 0
= 1.72 or 172  at eg (2 – 0.4) 0.4 M 0.2
M
Q.32 [182]
0.4 0.2  0.16  0.2  1 101
2

 C +
B  KC =
A + D
1.6 1.6 1.6 8
2

Initial conc. 1 1 1 1
C HEMISTRY 113
Chemical Equilibrium

= 0.125 × 10–1 = 125 × 10 – 4 1/ 2

 1 
= 125  15 
 2  10 
Q.36 (1) = (5 × 10–16)1/2
PCl5  PCl3 (g) + Cl 2 (g)  5  108
t=0 5 0 0 = 2.23 × 10–8
t = eq 5-n n n = x × 10–8
x2
Total moles = 5 - n + n + n
Q.39 [4]
=5+n
N2 (g) + 3H2 (g) 2NH3(g), K1 = 4 × 105 ...(i)
PV = nRT N2 (g) + O2 (g) 2NO(g), K2 = 1.6 × 1012 ..(ii)
nAr = 4
1
PV 6×100 H2 (g) + O (g) H2O(g), K3 = 1.0 × 10–13 ...(iii)
n= = 2 2
RT 0.082× 610 (ii) + 3×(iii) – (i)
PTotal= 6 5
PAr= 2 atm 2NH3 (g) +  2NO(g) + 3H O(g)
O (g) 
2 2 2

For 4 moles  2 atm

1.6  1012  1013 
3
5+n=8 k 2  k 33
n=3 keq = =
k1 4  105
3 3 1.6
PPCl PCl2 ( × 6)( × 6) = × 10–32 = 4 × 10–33
Kp = 3
= 12 12 4
PPCl 2
5 ( × 6)
12

27 9  H 2  g   1 O 2  g 
Q.40 [2] H 2 O  g  
= = = 2.25 2
12 4
P0
Q.37 [710] P0[1–] P 0 Partial pr. at eq.
2
N2O4 (g)  2NO2(g)
1– 2  
P0 1   = 1 ...(i)
 2
4 2 p 4   0.5   1
2
1
kp   
1  1   0.5 
2
0.75
 P  P 
1/ 2
H2 O2
Kp 
4 PH2 O
kp 
3
G° = – 2.3 RTlogKp
P0 
1/ 2
= – 2.3 × 8.31 × 300 × log (1.33)
 P0   
= – 710. 4 J mol–1  710 J mol–1  2  = 2×10–3
= 710 P0 1   

Q.38 [2] since  is negligible w.r.t 1 so P0 = 1 and 1 –  1

Cu(S) + 2Aq+(aq)  Cu2+(aq) + 2Ag(s)
K = 2 × 1015  
= 2×10–3
Cu2+(aq) + 2Ag(s)  Cu(s) + 2Ag+(aq) 2
1 1 3/2 = 23/2 × 10–3
K'  
K 2  1015  =23/2×2/3 × 10–3×2/3
 = 2 × 10–2 %  = 2%
1 2 1
Cu (aq)  Ag(s)  Cu(s)  Ag  (aq)
2 2
Q.41 [6]
K ''  (K ')1/ 2 Gº = – RT ln Keq

114 J EE C OMPENDIUM
 Chemical Equilibrium

Q.45 [12]
Kf
and Keq = K
b
x(g)  y(g) + z(g) k p1 = 3
Initial moles n – –
103 at equilibrium n – n n n
 Keq = 2 = 10
10
 
2
 G = – RT ln 10 
  p1 
 – (8.3 × 300 × 2.3) = – 5.7 kJ mole–1  6 kJ mole–1 1  
(nearest integer)
k p1 = 1 
p1
Ans = 6 1 

Q.42 [3] The yield of SO3 at equilibrium will be due to:  2  p1

3=
B. Increasing pressure 1  2
C. Adding more SO2 A(g)  2B(g) k p2 = 1
D. Adding more O2
Initial mole n –
at equilibrium x – n 2 n ptotal = p2
Q.43 [1]

 2
2
1  SO3 g  
SO 2 g   O 2 g     p2 
2 1  
k p2 = 1 
KP = 2 × 1012 at 300K p2
1 
K P  K C   RT 
n g

2 × 1012 = KC × (0.082 × 300)–1/2 4 2  p 2

1=
KC = 9.92 × 1012 1  2
KC = 0.992 × 1013
Ans. 1 k p1 p1
k p2 = 4p
2

Q.44 [6]
Gº = – RTnK 3 p1
= 4p  p1 : p2 = 12 : 1
 nFE ocell = – RT × 2.303 (log10K) 1 2

x = 12
E oCell Q.46 [1,4]
×n = log K ...(1)
0.06
PCI5 (g)  PCI3 (g) + CI2 (g)
 Pd  s  , E o n  0.83
Pd 2  aq.  2 e   (Case 1 : At constant P – volume will increase so
cat,red
reaction will shift in forward direction then answer
 PdCl 24  ,  aq   2e  .E o
Pd  s   4Cl   aq.  will be A
Anode,Oxid n

= 0.65 Case 2 : At constant volume no change in active mass

so reaction will not shift in any derection then answer
 PdCl42–(aq.)
Net Reaction  Pd2+ (aq.) + 4Cl–(aq.) 
will be D.
E ocell  E ocat,redn  E oAnode,Oxidn
Q.47 [1]
E ocell  0.83 – 0.65  2HI
H2 + I2 
E ocell  0.18 ...(2) at initial 4.5 4.5 0
Also n = 2 ...(3) at equilibrium 3 3 3
Using equation (1), (2) & (3)  HI   32  1
2

k eq 
logK = 6
 H 2  I2  3  3
C HEMISTRY 115
Chemical Equilibrium

Q.48 (3) A, B and D statements are correct. Q.3 (8.92 or 8.93)

 FES(s)
The equilibrium is possible when there is no exchange
Fe+2(aq) + S–2(aq)
of matter between system and surroundings.
At equilibrium state the forward and backward 0.03 M 0.1M
processes occur with same rate (speed) (0.03 – x)(0.1 – x)
When equilirbium is attained, the value of all its  y  0.07
Kc >> 10  0.03 – x  0  y
parameters became constant. 3
The solubility is function of solubility product. the
value of which is constant at a given temperature.  x = 0.03

1
JEE-ADVANCED Kc = 1.6 × 1017 =
PREVIOUS YEAR’S
y  0.07

Q.1 (B) 1017

y= = 8.928 × 10–17 = Y × 10–17
1.6  0.07
 2   g 
X 2  g  
y = 8.93

1 
2 Q.4 [0.25]

K eq. 
 B
 
2
 A
  
   22 K1000 
10
 10 and K 2000 
100
 100
 1     1 1
  
2   2

KP 


2
2 G1000
0
 RTnk eq 1000  1000  n10
1 1 Now, G 0   RTnk
2 2 4 2000  eq 
2000  n100
2000

1
2 = 0.25

Q.5 [5]
8 2
KP 
42
Q.2 (C)

G 0     ve

 RT ln K P  G 0     ve
KP < 1
Also β cant be 0.7 otherwise KP will have to be (+)ve

116 J EE C OMPENDIUM
 Ionic Equilibrium
Ionic Equilibrium
DPP-1 DPP-2
Q.1 (3) Q.1 (4)
For conjugate acid-base K w increases with increase in temperature
pka + pkb = 14
Q.2 (1)
pka = 14 – 9.26 = 4.74
1 1
1 1 pH = 7 + pKa – pKb
pH = pk a – logc 2 2
2 2
1 1
4.74 log10 –3 pH = 7 + ×5.76 – × 5.25
pH = – 2 2
2 2
1
3log10 pH = 7 + × 0.51
 2.37   3.87 2
2 pH = 7.255
pOH = 14 – pH = 14 – 3.87 = 10.13
Q.3 (2)
Q.2 (2) 
Alkaline, CH 3 COONa  H 2 O 
C = 0.005 M
pH = 5 CH 3 COOH  NaOH
Weak acid Strong base
[H+] = 10–5
And [H+] = c[from ostwald dilution law]
Q.4 (1)
H  10 –5
    0.2  10 –2 pH  pK a  log
[Salt]
  log 2  10 5  log
10  1
4.
C 0.005 [Acid] 50  2
Q.5 (1)
Q.3 (3) M of HCl = 25 × 0.5 = 12.5
eq
M of NaOH = 10 × 0.5 = 5
H 2 PO4  H   HPO 2  action.
eq
Conjugate acid
 4
M of HCl remaining 12.5 – 5 = 7.5
eq
[H+] = = 0.15
pH = – log 0.15
Q.4 (1) = 0.8239
2
 2C 0 . 01  0 . 01 
K ;   1  K   2C    1 Q.6 (2)
1  100  100  [Salt]= 0.1 M, [Acid]= 0.1 M
 1  10 8 . [Salt]
K a  1 . 8  10 5 ; pH  logK a  log [Acid]

Q.5 (2) 0 .1
Q.6 (1)  log1 .8  10  5  log  log 1 . 8  10 5
0 .1
Q.7 (2)
pH  4 .7 .
Q.8 (2)
Q.9 (2)
Q.7 (4)
Q.10 (2)
NaClO4 is a salt of strong acid HClO 4 . So it is a strong
Q.11 (3)
Q.12 (2) acid salt.
Q.13 (2)
Q.8 (3)
Q.14 (2)
Salt of weak acid & weak base
Q.15 (1) [H+] =
pH = [pK + pK – pK ]
w a b
= [14 + 4.8 – 4.78]
pH = 7.01

C HEMISTRY 117
Ionic Equilibrium

Q.9 (2) Q.6 (3)

12 Q.7 (3)
For pure water [H  ]  [OH  ] ,  K w  10 s Q.8 (3)
Q.10 (4) Q.9 (4)
(1) HCI. NaOH Q.10 (3)
No. of mili eq. = × 100 = 10 × 100 = 10
EXERCISES
So solution is Neutral
(2) × 55 = 5.5 × 45 = 4.5 JEE-MAIN
[H+] = = 10–2 M,pH = 2 OBJECTIVE QUESTIONS
(3) × 10 = 1 × 90 = 9Basic Q.1 (4)
(4) × 75 = 15 × 25 = 5 HCl (aq) + CH COOH (aq)  Cl– (aq) + CH
3 3
+
[H+] = 0.1 M, pH = 1 COOH (aq).
2
Q.11 (1) Acid-1 base-2 base-1
Q.12 (4) acid-2
Q.13 (1) Q.2 (1)
Q.14 (2) NH – + H+ 
Q.15 (2) 2
Q.3 (3)
Amphiprotic : can accept and
DPP-3 Release H+
Q.1 (2) Only H PO – & HCO –
2 4 3
Q.4 (4)
K  Mg(OH)
sp 2 = 10–12 Fact based
Mg Cl2 = 0.01 M Q.5 (1)
For a precipitating form [OH–] = in pure water.
Kionic Product > Ksolubility Product So as temperature increases K decreases [OH–]
w
At limiting pH consider that kip = ksp decreases.
Ksp = [Mg+2] [OH–]2 Q.6 (2)
10–12 = 0.01 [OH–]2 [H+] = = 5.5 × 10–2 M.
[OH–]2 = 10–10 ,  pH = 2 – 0.74 = 1.26
[OH–] = 10–5 Q.7 (2)
POH = – log10 (10–5) In this solution, source of OH– is water
POH = 5  C = [OH–]
PH = 14 - 5 = 9  = = 1.8 × 10–11 M
limiting pH = 9 % ionisation = 1.8 × 10–9 M
Q.8 (4)
Q.2 (1) [H+] = 10–2 ; [H+] = 10–6
Ag2CrO4 2Ag+ + CrO 4–2
1 2
= 104
2S S Q.9 (2)
Ksp = [2S]2[S] (1) At 25ºC, [H+] in a solution of 10–8 M HCl > 10–7 M.
(2) [H+] = 10–8 M.
1.1 10 –12
K sp
S3   (3) [OH–] = 4 × 10–6 M [H+] = 2.5 × 10–9 M.
4 4 (4) [H+] = 10–9 M.
S = 6.43 × 10–5
Q.3 (4) Q.10 (3)
AX 2A3+ + 3X2– [H+] = 0.016 M
2
2y 3y
3
[H+] [OH–] = 10–14  [OH–] = = 6.25 × 10–13 M
K = (2y)2 (3y)3 Q.11 (1)
sp
K = 108y5 Inital Final
sp
pH = 12 pH = 11
Q.4 (4) [H+] = 10–12 M [H+] = 10–11 M
Calculate the solubility ‘s’ for each option, –
[OH ] = 10 M–2 [OH–] = 10–3 M
Higher the value of ‘s’ Higher the solubility. Inital No. of mole of OH = 10–2 Final No. of mole of
–

OH– = 10–3
Q.5 (1)

118 J EE C OMPENDIUM
 Ionic Equilibrium

So no. of mole of OH– removed = [.01 – 0.001] = Q.24 (4)

0.009 Salt of weak acid & strong
Q.12 (3) As V, effect of water dominates so pH become Base
7. CH COONa CH COO– + Na+
3 3
Q.13 (3) CH COO– + H OCH COOH + OH–
3 2 3
CH COOH (aq) H+ (aq) + CH COO– (aq) Basic Solution
3 3
t = 0 0.01
t = eq 0.01 – xx x Q.25 (4) Factual
[H+] = x + 0.01  0.01 M Q.26 (2) Solution of HCl & NH Cl will be acidic, solution of
4
 K = 1.69 × 10–5 = NaCl neutral whereas solution of NaCN will be basic.
a
 [CH COO–] = 1.69 × 10–5 M Q.27 (1) NaCl + HCl : Not the Buffer
3
So, degree of dissociation of CH COOH = = 1.69 × 10– and Solution is acidic due to HCl.
3
3 pH < 7.
Q.14 (4) Q.28 (4) m. equivalent of KOH = 8
RNH + H O RNH + + OH– m. equivalent of HCOOH = 16
2 2 3 Remaining m. eq. (HCOOH) = 8
0.01 – XX X+10–4
= 2 × 10–6 (Neglect x) Formed m. eq. (HCOOK) = 8
x2 + 10–4 x – 2 × 10–8 = 0 Acidic Buffer
x = 10–4 pH = pKa = 4 – log2
[OH–] = x + 10–4 = 2 × 10–4 = 3.7
pOH = 10.3
Q.15 (3)
Q.29 (2) CH COOH + OH–  CH COO– + H O
3 3 2
 salt  t = 0 20 20
pH = pKa + log  
 acid  t = eq – – 20
50% ionised [Salt] = [Acid] So, [CH COO–] = = 0.1 M
3
pH = pKa = 4.5 pOH = 9.5 pH = 7 + pK + log C = 7 + 2.37 + log 10–1 = 7 + 2.37 –
a
Q.16 (1) 0.5 = 8.87
Q.17 (4) As concentration of solution decreases, degree of Q.30 (3) pH = 8.7 pOH = 5.3
dissociation of weak electrolyte increases. Basic Buffer
Q.18 (3) pOH = pK + log
b
HF  H+ + F–  = 4
pK = pK + pK [For conjugate Acid-Base] If volume of salt = V ml
w a b
 pK = 14 – 10.87 = 3.17  = 4
a
K = 6.76 × 10–4 Q.31 (4) Factual
a
Q.19 (3) Ostwald dilution law is valid for weak acid and
CH COOH is the weak acid. Q.32 (1) pH = pKa + log
3
Q.20 (3)  5.5 = 5 + log
NaCl Solution : pH is the, pH of water. = 3.16
As T , Kw , & [H+]  Suppose x m. mole NaOH was added
pH at 25°C <7 Acid + Base Salt
Q.21 (2) 10x 10
Volume of resulting solution = 100 ml 10 - x 0 10 + x
[H+] = = 10–3 = 3.16 x = 5.2 m.mole
pH = 3. NaoH (mass) = × 40 = 0.208 g
Q.22 (3) Q.33 (1) HCOOH + KOH HCOOK + H O
2
HCI NaOH milimole 20 – 10
N = 0.4 N = 0.2 10 – 10
V = 50 ml V = 50 ml pH = pK + log = 3.74 + log pH = 3.74
a
No. of milieq = 0.4 × 50= 200.2 × 50 = 10
[H+] = 0.1 M, pH = 1 Q.34 (2)
Q.23 (2) CH COOH + NaOH CH COONa + H O
3 3 2
% Hydrolysis does not time t = 0 40 mmole 20 mmole
depend on the conc. in case time t = t 20 mmole –20 mmole
of “Weak acid + weak base : Salt”
C HEMISTRY 119
Ionic Equilibrium

pH = pK + log pH = pK [H+] = K = 1.8 × 10– (3) solubility of AgCl in 0.01 M NaCl = s = (4)
3
a a a
5M solubility of AgCl in 0.05 M AgNO = s =
3 4
So s > s > s > s
1 3 2 4
Q.35 (2) Q.45 (1)
For ppt Q > K K (Ba CrO ) = 2.4 × 10–10 M2
sp sp SP 4
CaF Ca2++2F– [CrO –2] = 6 × 10–4 K (BaCrO ) = [Ba+2] [CrO –2] 2.4
2 4 SP 4 4
Q = (Ca2+) (F–)2 × 10–10
sp
(1) Q = 12.5 × 10–14
sp
 [Ba+] × 6 × 10–4 = 2.4 × 10–10
(2) Q = 12.5 × 10–10 [Ba+] = 4 × 10–7 M
sp
(3) Q = 12.5 × 10–13 Q.46 (1)
sp
(4) Q = 12.5 × 10–15 pH = 4 [H+] = 10–4 M [OH–] = 10–10 M
sp
Only (2) option will get precipitate. Al (OH) Al+3 + 3 OH–
Q.36 (4) WA Vs SB end point > 7 Phenolphthalein 3
K (Al (OH) ) = [Al+3] [OH–]3
Q.37 (1) Same as problem Number = 28 sp 3
[Al3+] [OH–]3 = 1 × 10–33
Q.38 (3) pH = pK + log 6 = 5 + log 1 = log
a [Al3+] (10–10)3 = 1 × 10–33 [Al+3] = 10–3 M
= 10
Q.47 (4) Higher the concentration of H+ , higher is the
Q.39 (1)
solubility of Fe(OH) .
MX M4+ + 4X–S 4S 3
4
K = [S][4S]4 solubility of Fe(OH) is maximum in 0.1 M H SO
3 2 4
sp Q.48 (4) MnS(s) Mn2+ (aq) + S2– (aq) ;
1/5 2– +
 K sp  S (aq) + 2H (aq) H2S (aq)
K = 256S5 S =  
sp  256  Q.49 (1) order of solubility : Complex formation > Pure water
Q.40 (4) (1) Li Na (AlF ) 3Li+ + 3Na+ + 2[AlF ]3– > Common ion effect.
3 3 6 2 6
3s 3s 2s AgBr form complex [Ag (NH ) ]+ in NH so solubility
3 3 2 8 3 2 3
K = (3s) (3s) (2s) = 2916 s . is maximum in NH (aq).
sp 3

Q.41 (2) Q.50 (1)

K of Mg (OH) = 2.56 × 10–13 pH of 0.1 M H S solution can be derived by :
sp 2 2
3=2.56 × 10–13 s
H S H+ + HS– ; K = 1 ×10–7
4s = 4 × 10–5 M 2 1
1 1
 [H+] = C = C = = = = 10–4  pH = 4
K of Al (OH)3 = K = 4.32 × 10–34
sp sp JEE-ADVANCED
27 s 4 = 4.32 × 10–34s = 2 × 10–9 M = = 2 × 104 OBJECTIVE QUESTIONS
2 2 Q.1 (4)
Q.42 (3) HC O – (aq) + PO 3–(aq)  HPO 2–(aq) + C O 2–
2 4 4 4 2 4
NaF Na++F– (aq)
0.10.1 0.1 Acid-1 base-2 base-1 acid-
CaF Ca2++2F– 2
2
(2x + 0.1) 0.1 Q.2 (3) Factual.
K = x (0.1)2 = 3.4 × 10–11 x = 3.4 × 10–9
sp Q.3 (D)
Q.43 (3) K w 50ºC H  1 1 
log K   
Na CO 2Na+ + CO 2– 2.303  323 298 

=
2 3 3 w 25 ºC
2 × 0.010.01
Ag CO 2 Ag+ + CO 2– 5.474 H 25
2 3 3  log  
2 x (x + 0.01) 0.01 1.08 2.303  8.314 323  290
K = 4x2 (0.01) (H)ionization of H2O = 51.963 KJ/mol
sp
K = 4s3 = 4 × 10–12 = 4x2 (0.01) x = 10–5  (H)Neutralization = – 51.963 KJ/mol
sp

Q.44 (3) Let K of AgCI = x Q.4 (4)

sp
(1) solubility of AgCl in pure water = s = (2) solubility (1) HCINaOH
1
of AgCl in 0.01 M CaCl = s = No. of mili eq. = × 100 = 10 × 100 = 10
2 2

120 J EE C OMPENDIUM
 Ionic Equilibrium

So solution is Neutral Ionic product = Kw = (2x) (x) = 10–14

(2) × 55 = 5.5 × 45 = 4.5  2x2 = 10–14  x = –8
50 × 10
[H+] = = 10–2 M,pH = 2
Q.9 (B)
(3) × 10 = 1 × 90 = 9Basic
HA  H+ + A–
(4) × 75 = 15 × 25 = 5
[H+] = 0.1 M, pH = 1 1–x x x
Q.5 (C) x = 1%
2Ag(s) + 2I– + 2H2O 2Ag(s) + H2(g) + 2OH– [H+] = 0.01
pH = 2
[H2 ][OH ]2 Q.10 (A)
K eq  ..............(1)
[I ]2 h = .03 C = 0.1 M
For H2(s) K = Ch2 = 9 × 10–5
h
PV = nRT, K = = 9 × 10–5 K = = 1.11 × 10–10 1 ×
h a
10 –10
P = CRT
Q.11 (A)
P 0. 6
C=  = 0.0245 Weak acid + Strong base : Salt
RT 0.082  298
CN– + H O HCN + OH–
From eqn(1) 2
–xXX
1.2  10 2  0.12 X can be neglected
[OH–]2 = X = 3.1 × 10–4
0.0245
[OH–] = 0.0699 % Hydrolysis = × 100
= 2.48 %
1.2  10 2  0.12 Q.12 (A) Order of basic strength O2– > S2– > Se2– > Te2–
[OH–]2 = = 1.650
0 .6
Q.6 (1) Q.13 (A) pH of amphioprotic salts and weak acid-weak base
M of HCl = 25 × 0.5 = 12.5 salt is independent of its concentration.
eq
M of NaOH = 10 × 0.5 = 5
eq
M of HCl remaining 12.5 – 5 = 7.5
eq Q.14 (C)
[H+] = = 0.15
pH = – log 0.15 C6H5NH2 +H+  C6H5NH3+
= 0.8239 t=0 5 2.5teq2.5–2.5
pOH = pKa = 14 – 8 = 6
Q.7 (D)  pKa = 6
Fe3+ + H2O Fe(OH)2+ + H+ Now for the solution of [C6H5NH3+] = 0.01 M
1 0.05 0.05 0.05 0.05 1 1 6 1
conc at eqn pH = 7 – pKa – log C = 7 – – log (0.01) = 5
V V V V 2 2 2 2
Q.15 (A)
0.05 / V 2 Na3PO4  3Na+ + PO43–
we have Keq = 6.5 × 10–3 =
1  0.05 / V  PO43– + H2O HPO42– +OH–
Kw 10 14
100 K '3  
 V= K 3 4.5  10 13
19  13
0.05 0.1 (1–1) 0.1 1(1–)0.11 + 0.1 12 + 0.1 123
 (H+) = = 0.1235
V
HPO43– + H2O H2PO42– + OH–
PH = – log(H+) = 0.908

Q.8 (B) Kw 10 14

K '2  
HCl  H+ + Cl– K 2 6.3  10 8
(x + x) (x) 0.1 (1–2) 0.1 12(1–)0.112 + 0.1 1 + 0.1 123
H 2O H+ + OH–
(x + x) (x) H2PO4– +H2O H3PO4+ OH–

C HEMISTRY 121
Ionic Equilibrium

[C6H5COO ]
K 10 14 pH = pK a + log  4.5 = 4.2 + log
K1'  w  [C6H5COOH]
K1 7.1 10 3
 V2  V2
0.1 12(1–3) 0.1  12 3 0.1 1 2 3  
 V  V = 2
 1 1
+ 0.1 1 + 0.1 12
Now 1 – 2 1  volume of C6H5COONa required = V2 = 200 ml
1 – 3 1 volume of C6H5COOH required = V1 = 100 ml.
or [OH–] ~ 0.1 1 Q.21 (B)
For the buffer solution of NH3 & NH4+
' [OH ][HPO 24 ] 0.11  0.11
We have K 3  = 0.1(1  1) =
[NH3 ]
[PO 34 ] pH = pKa + log [NH  ]  8.26 = 9.26 + log
4
0.022
0.1 12 = 0.022 – 0.022 1 (500  0.01)
0.1 12 + 0.022 1 – 0.022 = 0 m. moles of NH4
1 = 3.73 × 10–2 M  m. moles of NH4+ = 50 moles of (NH4)2 SO4
required = 0.025.
[OH–] = 0.1 3.73 ×10–2 M
Q.22 (C)
[OH ][H2PO 4 ]
K '2  Q (AgBr) = [Ag+] [Br–]
[HPO 24 ] sp
Q =
sp
As, [OH—] [HPO42–] = 2 × 10–16
Q <K
sp sp
We have, [H2PO4–] = K21 = 1.587 × 10–7 M No precipitation
[Ag+] = = 10–7 M
' [OH ][H3PO 4 ]
So, K1 
[H2PO 4 ]
Q.23 (A)
14 7 CH3COONa+HCI 
 NaCI + CH3COOH
10 1.587  10
[H3PO4] =  = 6 ×10–18 M
7.1 10 3 3.73  10 2 t= 0 20 m eq. 20 meq.teq.––20 meq.
Q.16 (A) 20
Ag CO 2Ag+ + CO 2– [CH3COOH] = = 0.1 M
2 3 3 200
2ss
Here [Ag+] = 2 s = 2 × 10–4 Ms = 1 × 10–4 1 1
pH = [pKa – log C]= [5 – log2 + 1]
 K = 4 s3 = 4 (1 × 10–4 )3 = 4 × 10–12 2 2
SP
1
Q.17 (D) HgSO Hg2+ + SO 2–SS = [6 – log2] = 3 – log 2
4 4 2
Ksp = S2
Q.24 (C)
6.4 × 10–5 =S2
meq. of acid = meq of base  20 × M = 20 × 0.2 = 4
S = 8 × 10–3 mole/L
Molarity of HA = 0.2 M
S = 8 × 10–3 × 103 mole/m3
S = 8 mole/m3 HA +OH  A– + H2O
5 2m. mole
Q.18 (C) Mole of NaOH is required for 1 lit solution = x 3– 2 m. mole
 Mole of NaOH is required for 100 ml of solution =
[A  ] 2
0.1x  pH = pKa + log 5.8 = pKa + log  3  pKa
Now, 0.1x = 1 × V , V = 0.1x lt = 100x ml. [HA ]  
= 5.98
Q.19 (C) K = 5 × 10–10pK = 10 log 5 = 9.3 Q.25 (D)
a a
pH = pK + log
b CH3COOH + OH–  CH3COO– + H2O
9 = 9.3 + log – 0.3 = log
0.3 = log  = 2 V = 2 ml 1 2
ml Difference in pH between & stages of
3 3
Q.20 (C)

122 J EE C OMPENDIUM
 Ionic Equilibrium

POH = 9.16
  2 / 3 
neutralisation = pK a  log   –
  1/ 3  Q.29 (B) (A) pH of NaHCO3 is independent of dilution.
(C) pH of buffer solution is approximately ramains
  1/ 3 
pK a  log   = 2 log 2. constant with dilution.
  2 / 3  (D) pH of salt of WA & WB is independent of dilution.
Q.26 (B)
m. moles of HA taken = 27 × 0.1 = 2.7 Q.30 (C)
–  A– +H2O
CaF2(s) Ca2+ + 2F– s2s
HA +OH
4s = Ksp = 4 × 10–11  s = 2.15 × 10–4 M
3

t=0 2.71.2 So, amount of F– in 20000 lt of water = 2s × 20000 = 8.6

t eq 1.5 –1.2 mol.
[A  ]  1 .2  Q.31 (C)
pH = pKa + log 5 = pKa + log  1.5  [Fe3+] [OH–]3  Ksp
[HA ]  
[OH–]  3.7 pOH  3.7 pH  10.3.
4 Q.32 (B)
= pKa + log
5 Ca(OH)2 Ca2+ + 2OH–
 pKa = 5.1  Ka = 8 × 10–6. 1.48
Q.27 (B) t=0 = 0.02 00 teq00.020.04
74
m. moles of HCl = 0.1 × 20 = 2
m. moles of CH3COOH = 0.1 × 20 = 2 so, pOH = 2 – log 4 = 1.4
After titration of HCl by NaOH so pH = 12.6

2 1 Q.33 (D)
[CH3COOH] = = M
40 20 CH3COOH + NaOH  CH3COONa + H2O
1 1 1 Initially
 pH = (pKa – log C) = [5 – log 2 – log ( )] = no. of milli moles 20.10
2 2 20
3. After r × n 1.900 0.1
Q.28 (B) [Salt]
BOH + HCl  BCI + H2O (PH )1 = PKa + log
[ Acid]
Initially 4 0.16 × V 0
no. of milli moles 0.1
= PKa + log
After R×n 004 1.9
1.9
 0.16 × V = 4 Similarly (PH )2 = PKa + log
0.1
4 (1.9)2
 Concentration of BCl =
25  40 = pH = (PH)2 – (PH) = log = 2.558
(0.1)2
4 Q.34 (A)
= 6.15 × 10–2 M Ksp(AgCl) = 2.8 × 10–10
65
AgCl Ag+ + Cl–
1
[pk 2  pk b  log C] = 5.23
–10
 pH = 2.8 × 10 = (s + 0.1)s
2 s = 2.8 × 10–9
 pkb = 4.75
Q.35 (A) S2– + Zn2+  ZnS (s)
Now,
BCl + NaOH  BOH + NaCl m.moles 0.40.20.2-so in solution,
Initially 41.800 0 .2
no. of milli moles [S2–] = = 0.01 M
20
After R×n 4–1.801.81.8
= 2,2 = 0 =1.8 K sp 4  1024
 [Zn2+] = 2 = = 4 × 10–22 M
The mixture is buffer of BOH and BCl [S ] 0.01
[BCl]  mass of Zn2+ remain unprecipitated in 20 ml of
 POH = pkb + log
[BOH] 4  1024
solution = × 20 × 65 = 5.2 × 10–22 gm.
2 .2 1000
= 4.75 + log
1 .8
C HEMISTRY 123
Ionic Equilibrium

Q.36 (A)  PH = 11.22

m.moles of Ag+ in 100 ml of saturated solution of AgCl
Q.41 (C) If x be the concentration of AgCl in the solution,
= K sp × 100 = 1.4 × 10–3
then [Cl–] = x
Now Ag + +SCN – From the Ksp for AgCl, we derive
 AgSCN (s)
1.7  10 10
K sp
–
m.moles of SCN = m.moles of Ag + [Ag+] =  =
[Cl ] x
1 × 10–5 × V = 1.4 × 10–3  volume = 140 mL.
Q.37 (A) If we answer that the majority of the dissolved Ag +
goes into solution as Ag(NH3)2+ then Ag(NH3)2+ then
Cd2+ + H2S  CdS  + 2H+ Ag(NH3)2+ = x
m.moles 0.10.2 Since two molecules of NH3 are required for every
Total m.moles of H+ in solution after the reaction = 0.2 Ag(NH3)2+ ion formed, we have [NH3] = 0.2 – 2x
+ 0.8 = 1
 1.7  10 10 
1 [ Ag ][NH3 ]2  0.2  2x 2
 [H+] = = 0.01 M  pH = 2.  x 
 Kinst = =  
100 [ Ag(NH3 )2 ]
Q.38 (A) x
2Ag+ (aq) + H2S(g)  Ag2S (s) + 2H+ (aq) ;K = 6 × 10–8
 x = [Ag(NH3)2+] = 9.6 × 10–3 M, which is the
= 1029
solubility of AgCl in 0.2 M NH3
moles of H2S dissolved = 1.5 × 10–4
Q.42 (3)
 moles of Ag+ precipitated = 3 × 10–4
H A H+ + HA–
2
3  10 4
3  10 4  10–5 =
 Ksp(AgBrO3) =  0.25   0.25  = 1.44 × 10–6
   HA– H+ + A2–
Q.39 (B) 5 × 10–10 =
H A 2H+ + A–
2
K = 5 × 10–10 × 10–5
overall
= 5 × 10–15
Q.40 (A)
BOH + HCl  BCl + H2O JEE-ADVANCED
a a COMPREHENSION/STATEMENT/MATCHING/MCQ
a 6 Q.1 (B, D)
4 4
pKa (H3O+) = –1.74 = pKb of OH–
3 a pKa + pKb = 14 only for conjugate acid base pair.
= 24 × = 18 meq Now, = 6 m eq  = 1.8 × 10–9 or1.8 × 10–7 % for H2O.
4 4
[salt ] Q.2 (A, B, C)
POH + log a = 24 m eq
[basic ] pK = – logK = – log 1 × 10–12 = 12.
w w
K = [H+][OH–] = 10–12 .
4 w+
[H ] = [OH–]
= PKb + log = 14 -9.24 = 4.76
43  [H+]2 = 10–12 ; [H+] = 10–6 ; pH = – log[H+] = – log
10–6 = 6.
 PKb = 5.237 H O is neutral because [H+] = [OH–] at 373 K even
Now, BCl + NaOH  BOH + NaCl
2
when pH = 6.
6–6 6 – 6 66 (D) is not correct at 373 K. Water cannot become
=0 =0=6=6 acidic.
Total BOH = 6 + 18 = 24 m eq
24 Q.3 (B, C)
(BOH) = M (A) pH of 10–8 m sol. of HCl is 6.97
50
(consider the H+ from H2O also)
1 – H+
POH = [Pkb – logC] (B) H2PO4– HPO42–
2
(C) Kw = [H+] [OH–]
1 24 On temp [H+] [OH–]
= [5.237 – log ] = 2.774 both  Kw 
2 50

124 J EE C OMPENDIUM
 Ionic Equilibrium

(D) HA + NaOH  NaA + H2O x + y = 0.01

C C/2 C–C/2
0.1 y 0.01
Also, K CH3cOOH  10 5 = 
salt 0.01  y 0.1
pH = pKa + log
acid x 0.01
Q.4 (B, C) x  0. 1 0.01 0.1
 K Cl2HCOOH   1.25 ×
[Salt] 0.09  0.01 0.08
(B) is correct because pH = pKa + log [Base] for
10–2
acidic buffer. Q.9 (A,B,C)
If [Salt] increases, pH of acidic buffer will increase. MW of ClCH2COOH = 44.5
[Salt] 9.45
pOH = pKb + log for basic buffer.. No. of Moles of acid = = 0.1
[ Acid] 94.5
If [Salt] increases, pOH will increase, pH will decrease  [acid] = 0.1 × 2 = 0.2 M
as pH = 14 – pOH. ClCH2COOH ClCH2COO– + H+
Therefore (C) is correct but (D) is wrong. 0.2(1 – ) 0.1  10–2 = 0.2 

[Salt] 10 2  105
(A) is not correct pH = pKa + log = = 0.05
[ Acid] 2
If [Salt] increase, pH will increase. Q.10 (A, C, D)
Q.5 (B, C, D) (A) In 0.6 m M HCOOH solution
(B), (C) and (D) are the mixtures of conjugate acid-
[H ]2 [H ]2
base pairs. Ka =  8 × 10–4 =
C  [H ] 6  10  4  [H ]
Q.6 (A, B)  [H+] = 4 × 10–4 M.
(A) is buffer because it contains weak acid and its salt So solution in (A), (C) & (D) are SOHYDRIC.
and they will also show common ion effect.
(B) is also a buffer because it contains a weak acid and Q.11 (A, B)
its salt. They will not show common ion effect.
Total [H + ] = K a1C1  K a 2C2 =
(C) is not buffer solution because they contains strong
acids and its salt. They will not show common ion
 0.5   0.1 
effect.  3.6  10 4   100    8  10 4   400 
(D) is not a buffer solution because it contains strong  500   500 
acids and its salt. They will not show common ion  [H+] = 10–2 M.
effect.
K a [HN3 ] 3.6  104  0.5
For HN3, [N3–] = =  100 =
Q.7 (A, D) [H ] 0.01 500
(A) [H+] = 10–2 and [OH–] = 10–2 3.6 × 10–3 M.
H+ + OH–  H2O Ka [HOCN]
For HOCN, [OCN – ] = =
This leads complete neutralisation [H ]
2  12
so, pH = 7 = 8  104  0.1 400
2 = 6.4 × 10–3 M.
0.01 500
(D) [H+] = 10–5 and [OH–] = 10–5
Q.12 (A, C)
[H+] + [OH–]  H2O As Ka of acid increases, K b of its conjugate base
This leads complete neutralisation decreases.
59 Q.13 (B, C) On the basis of ostwald dilution law, number of
so, pH = 7 = H+ ions will increase but increase in volume will be
2
more. Therefore, [H+] decreases, pH increases.
Q.8 (A,B,C)
Q.14 (B, C, D)
HCl H+ + Cl–
Let BA be this salt BA  B+ + A–
0.09 – 0.09 0.090.09
A– does not undergo hydrolysis because HA is strong
Cl2HCCOOH Cl2COO– + H+
acid. B+ undergoes hydroysis
0.1 – yy y + 0.09 + x
h = h = degree of hydrolysis where K = Hydroly-
We have, y + 0.09 + x = 10–1 = 0.10 h
sis constant = .

C HEMISTRY 125
Ionic Equilibrium

h  greater the hydrolysis constant greater the so it is a buffer solution.

h(degree of hydrolysis).
h  greater the K lesser the h.
b (B) H2CO3 + OH–  HCO3– + H2O
Hydrolysis is endothermic, K increases with tempera- moles 1.5 2–0.51.5
h
ture and h also increase with temperature. HCO3– + OH–  CO32– + H2O
h  V = volume of salt solution hence h increases
moles 1.5 0.5– –0.5
with dilution. K =
h so it is a buffer solution.
Both K and K change with temperature, hence K
w b h
changes with temperature. (C) NH4OH + H+  NH4+ + H2O
Hence, statement(B) is correct. h increases if K de- moles 541 –4
b
creases, statement(C) correct. so it is a buffer solution.
It is found that as temperature increase, K and K Q.18 (A, B, C)
w b
increase but increase in K is greater than increase in (A) CH3COOH/CH3COONa
w
K.
b (B) CH3COONaHCl  CH3COOH + NaCl CH3COONa
Hence, h increases with increase in temperature. or h / CH3COOH (Buffer)
decrease in temperature., hence statement. (C) NH3/NH4Cl (Buffer)
(D) is correct. (D) NH3 + NaOH (not Buffer)
(D) is not correct from explanation of (B).
Q.19 (A,B)
Q.15 (A, B, C) (A) A buffer solution is a solution which contains weak
At eq. point pH = 4.5 acid and its conjugate base. it is acidic buffer.
pOH = 9.5 (B) Basic buffer contains weak base and its conjugate
pOH = 1/2 [Pkb + pkw + hc ] acid.
9.5 = 1/2 [5.6 + 14 + hc]  C = 0.25 (C) is wrong because it does not show change in pH on
(C) Total volume be (100 + V) adding small amount of acid or base.
0.25 × (100 + V) = 0.5 × C V = 100 ml (D) is wrong ; all the above statements are not correct.
(D) 100 M = 0.5 V
100 × M = 0.5 × 100 Q.20 (A, C) Sodium acetate and acetic acid solution and
M = 0.5 ammonia and ammonium chloride solution are the ex-
100 ml _________ 0.5 mole amples of acidic buffer.
100 ml _________ 0.055 mole of base Q.21 (C, D)
wt. Higher the Ka of acid lower is the pH of acid for same
0.05 = wt. = 2.25 gm concentration.
45
2.25 Q.22 (A, D)
% of base = ×100 90%
2.5 Hn  H+ + n–
Q.16 (A, D)

[H ]
[H3 AsO4 ] 10 8 1 [H ] [n ] [ n ] K n 10 9
 =
Kn =     9.6 100.6 = 4
(A) =  4 = 25000 [H n] [H n] [H ] 10
[H2AsO4 ] K1 2.5  10
 [H3AsO4] << [H3AsO4–].  % of [n–] in solution =
4
 100 = 80%
5
[H2 AsO4  ] [H ] 10 8 1 so pink colour will be visible.
(B) 2 = = =
[HAsO4 ] K2 5  10 8 5
Q.23 (B,C,D)
3 Initial decrement is due to consumption of free OH–
[ AsO4 ] K3 2  10 13 1
(C) = = = ions, then slow decrement in pH is due to basic buffer
[HAsO4 2
] [H ] 10 8 50000
solution and minimum slope will be there when there is
 [AsO43–] << [HAsO42–]. best buffer action ([salt] / [base] = 1)

Q.17 (A, B, C) Q.24 (B, C)

BOH + HCl  BCl + H2O
(A) H2CO3 +OH–  HCO3– + H2O 100 m 0.5 V 20 M
moles 1.5 1 100 M – 0.5 V 0 = 80 M 14–a
0.5 –1
126 J EE C OMPENDIUM
 Ionic Equilibrium

pH = 1 pH = 3
salt [H+]1 = 10–1 [H+]2 = 10–3
pOH = pKb + log
base
[H ]1
20 M = 100
5 = pKb + log [H ]2
80 M
 pkb = 5 – log 0.25  pkb = 5.6 1
pH = (pKw + pKa– pKb)
 Kb = 2.5 × 10–6 2
greater than 10–6 pH is independent of dilution with in a limit since no
Q.25 (A, B, C,D) concentration term in pH expression.
Factual
11.85
Q.33 (A) Mole of Potash Alum =
Q.26 (C, D) In AgNO3 solution, the solubility of AgCN will 474
decrease as compared to pure water because of
common ion effect of Ag+ ion. = 0.025
In NH3 solution and buffer of pH = 5, the solubility of Mole [Al3+] = 0.025
AgCN will increase due to complex formation in case Mole [K+] = 0.025
of NH3 solution and hydrolysis of CN– ions in case of If none of the Ion Hydrolysed
buffer of pH = 5. [H+] = 10–7
Q.34 (A)
Q.27 (A,B)
Al3+ + H2O Kw
Al(OH)2+ + H+
Ksp = 1.1 × 10–11 = (1.4 × 10–4)x + y xx . yy
so we have x + y = 3 (by comparing values) Ka
C-x x x
1.1 10 11 110
so, xx . yy = = =4 0.025
1.4  1.4  1.4  10 12 1.96  1.4 C= × 1000 = 0.25
100
Hence x = 1, y = 2 or y = 1 , x = 2
Q.28 (B,D) x2
Facutal  = 1.4 × 10–5 x2 = 1.4 × 0.25 × 10–5
0.25  x
Q.29 (C, D)
Given graph is plotted for the titration of weak diprotic x = 1.87 × 10–3
acid with base. Q.35 (C)
Q.30 (A, B, D) SO42– + H2O HSO4– + OH–
Kw
[Ag+] ion required to precipitate Cl– ion = = = 2 × 10–9
Ka
mol/L.
[Ag+] ion required to precipitate I— ion = = = 8 × 10–15 0.5-x x x
mol/L.
Since [Ag+] ion conc. required to precipitate AgI is less x2 10–14
than the [Ag+] ion conc. required to precipitate AgCl, = (Neglect x)
0.5  x 1.25  10–2
AgI precipitates first.
Hence choices (A),(B) and (D) are correct while (C) is [OH–] = x = 6.32 × 10–7
incorrect. 10–14
Q.31 (A, B) H 2SO 4 is a strong acid and it completely [H+] = = 1.58 × 10–8
6.25  10–7
dissociated in H 2O. Hence its K a1 and K a2 are Q.36 (A)
determined in CH3COOH.
Also H2SO4 is neutral while HSO4– because the – ve Al3+ + SO42– + H2O Kw
Al(OH)2+ + HSO4–
charge has more affinity towards H+ ion. Hence choices K a.Kb
(A) and (B) are correct while (C) is incorrect. As H2SO4 0.25-x 0.5-x x x
is completely dissociated in water so a 0.01 M H2SO4 is
Kw 1.4  10 5
completely dissociated and its [H+] ion conc. will be = = 1.12 × 10–3
equal to 0.02 M. K a.K b 1.25  10  2
Hence choice (D) will be incorrect.
x2
 = 1.12 × 10–3
Q.32 (A, B, C) (0.25  x)(0.5)  x
[A2–] = K a2 = 10–5 x = [HSO4–] = 0.0114

C HEMISTRY 127
Ionic Equilibrium

= 7  105 [F–]  10–5 = 7 [F–]

[H ][SO24 ] Here [F–] + [HF] = 2s
 = Ka = 1.25 × 10–2
[HSO4 ] s
 [F–] =
 4
[H ][0.5  0.0114]
 = 1.25 × 10–2
[0.0114] s
2
Ksp = s   = 2.048  10–9
[H+] = 2.92 × 10–4 10–2 4
[H+] = 2.92 × 10–4  s = 3.2  10–3 mol/L
Q.37 (C)
From the Graph 19 ml Q.43 [A–S, B–S, C-Q]
Q.38 (C)
From the Graph pH 8.5 25
200  1.225  2
(A) [H+] = 100
Q.39 (C) 98
1.2 0.222  19 = 1.25
=
Mol. mass 1000 800
[OH–] = 0.525 × × 3 = 1.26
Mol. mass = 284.5 1000
Q.40 (A)
For SrF2 in pure water Remaining [OH–] = 10–2
4s13 = Ksp pOH = 2
For SrF2 in 0.1 M NaF solution pH = 12
s2 (0.1)2 = Ksp Indicator having range 11.4 to 13.
 4s13 = s2 (0.01)
0.8
256 (B) pH = 11 – log2 + log
 4s13 = s1 × (0.01) 0.1
106 = 11 + 2 log 2
 s1 = 8 × 10–4 M = 11.6
 Ksp = 4s13 = 2.048 × 10–9 Indicator having range 11.4 to 13.
(C) HCl m.eq = 5
Q.41 (C) NaOH m.eq = 13
[Sr2+]i = 0.0011 = 11  10–4 M 
[Sr2+]f = 2  10–4 M Remaining NaOH = 8
 [Sr2+] precipitated = (11 – 2)  10–4 M m.eq of HA = 10
= 9  10–4 M Ha + OH–  A– + H2O
[F–] needed for this precipitation = 2  9  10–4 = 18 10 8
 10 M
–4
2 08
Also, [Sr2+]f [F–]2f = Ksp = 2.048  10–9
But, [Sr2+]f = 2  10–4 M
[A – ]
 [F–]f = 3.2  10–3 M pH= PKa+log
 Total [F–] needed = 3.2  10–3 + 18 10–4 = 5  10–3 [HA]
M = 5 + log 4
 5.6
5  10 3  42 Indcator having range 4.6 to 6.4
 NaF needed for 100 ml solution =
10
Q.44 (A – p, q, r, s);(B – p, r) ;(C – r) ; (D – p, q, s)
= 0.021 g
(A) [H+] in HCl solution = 10–5 M
Q.42 (B)
[H+] in H2S solution = K a  C = 10–4 M
SrF2  Sr2+ + 2F– so [H+] in HCl solution < [H+] in H2S solution
s 2s
F– will react with H+ to produce HF & [OH–] in HCl solution > [OH–] in H2S solution
F– + H + HF & degree of dissociation of water in HCl solution >
degree of dissociation of water in H2S solution
1 [HF] 7
K= K =   = pH of HCl solution > pH of H2S solution.
a [H ][F ] 10 5 (B) At pH = 4.74 in CH3COOH solution, [CH3COO–] =
 [HF] = 7  105 [F–] [H+] ( [H+] = 10–5 ; pH=5) [CH3COOH]

128 J EE C OMPENDIUM
 Ionic Equilibrium

1 = 11 – 3 log 2 =11 – 0.9

 degree of dissociation of CH3COOH = = 10.1
2
At pH = 9.26 i.e. pOH = 4.74 in NH4OH solution, (D) CO(OH)3 CO3+ + 3OH–
[NH4+] = [NH4OH] S 3S
 degree of dissociation of CH3COOH = degree of 27S4 = 27 × 10–44
dissociation of NH4OH S = 10–11 &
degree of dissociation of water in CH3COOH solution [OH–] = [10–11 + x] : x from water
> degree of dissociation of water in NH4OH solution. [H+] = x & x (10–11 + x) = 10–14
 pH 7
(C) [H+] in CH3COOH solution = 1.8  10 5  0.1 =
–3 Q.46 (A – p, q); (B – q, r); (C – p, q, s) ; (D – r, s)
1.8 × 10 M
(A) H2C2O4 + OH–  HC2O4– + H 2O
[H +] in HCOOH solution = 1.8  10  4  1 =
m.moles5025 25–25
1.8 × 10 M
–2 Buffer solution pH = pKa1
so, degree of dissociation of CH3COOH = degree (B) H2C2O4 + OH–  HC2O4– + H 2O
dissociation of HCOOH. m.moles5050–– 50
(D) [H+] in HA1 solution = 10 5  0.1 = 10–3 M pK a1  pK a2 13
Amphiprotic, pH = = = 6.5.
2 2
[H+] in HA2 solution = 10 6  0.01 = 10–4 M
(C) H2C2O4 + OH–  HC2O4– + H 2O
so [OH–] in solution of HA1 < [OH–] in solution of
HA2 m.moles5075–2550
pH in solution of HA1 < pH in solution of HA2 HC2O4–+ OH–  C2O42– + H 2O
& degree of dissociation of water HA1 < degree of
dissociation of water HA2. m.moles502525–25
Buffer solution pH = pKa2.
Q.45 [A–P, B-Q, C–S, D–R] (D) H2C2O4 + OH–  HC2O4– + H 2O
10  0.03 m.moles50 100
(A) [OH–] = = 6 × 10–4
500
–50 50
0.08  5
–
[OH ] = = 8 × 10–4 –
HC2O4 + OH –  C2O4 2–
+ H 2O
500
m.moles50 50
Remaining [H+] = 2 × 10–4
pH = 4 – log 2 = 3.7
–– 50
0.5  10 Salt hydrolysis, pH > 7.
(B) [RNH3Cl] = = 0.1
50
[KOH] = 0.1 Q.47 (A – s); (B – p, q); (C – q, s) ; (D – q, r)
RNH3Cl + KOH RNH2 + KCl + H2O (A) For AgBr, Ksp = [Ag+] [Br–]
–
0.1 0.1 0.1 0.1 so on increase in [Br ], solubility of AgBr
decreases.
RNH2 + H2O RNH3+ + OH– (B) For AgCN, Ksp = [Ag+] [CN–]
Kb
–
0.1–x xx CN undergoes hydrolysis so solubility in water
is more than expectation.
x2
Kw In acidic solution, CN – gets protonated so
K x = 10
–5
= Kb =
0.1  x solubility of AgCN increases.
AgCN forms complex Ag(CN)2– with excess of CN–
x = 10–3 pOH = 3 ; pH = 11 .
(C) For Fe(OH)3, Ksp = [Fe3+] [OH–]3.
(C)Buffer : HCO3– / CO32– –
In acidic solution OH decreases so solubility
Salt increases.
pH = pKa + log Solubility decreases in presence of OH–.
Acid
(D) For Zn(OH)2, Ksp = [Zn2+] [OH–]2
4
= 11 – log 4 + log Zn(OH)2 is amphoteric in nature so its solubility
8 increases in both acidic as will as strongly basic
= 11 – log 4 – log 2 solution.
C HEMISTRY 129
Ionic Equilibrium

JEE-ADVANCED
INTEGER TYPE Salt   Salt 
log Acid  1 = log 
Q.1 [7] NaOH + HCl   NaCl + H2O
  
 Acid 
NaCl is a salt of strong base and strong acid, hence it
gives the neutral solution with pH = 7. Salt 
 Acid  = Antilog 1 = 10
Q.2  M+ + OH–
[9] MOH 
[Salt] : [Acid] = 10 : 1
 10
[OH ] K sp  110 = 10–5
Q.2 (4)
pH = 9. pH of a salt of a weak acid and a weak bas is given by :
Q.3 [7] 1 1
pH = 7 + (pKa – pKb) = 7 + (3.2 – 3.4) = 6.9
2 2
Q.4 [6] s  K sp  36 = 6 M

Q.5 [3] CH3COONH4, NH4CN, HCN + NaCN Q.3 (2)

Q.6 [4]  Pb 2   2Cl –
PbCl 2 
Q.7 [9] s 2s (s = solubility of PbCl2)
Q.8 [0] G0 = - 2.303RT logKC Ksp = [Pb2+] [Cl–2]
Q.9 [2] Phenolphthalein is used for titration of solution of 3.2 s s)2 = 4s3 s
(i) strong acid and strong base and
n
(ii) weak acid and strong base PbCl 2
Solubility =
Volume(in L)
Q.10 5 [(i) to (v)]
(i) to(v) are correct 0.1 1
Q.11 [31] s=  = 2 
278 V
[C6H5COO ]
pH = pKa + log 0.1 103
[C6H5COOH] 
V = 0.1798 L
278 2
 V2  V2
 4.5 = 4.2 + log  V   V1 = 2
Q.4 (1)
 1 [H2S] = 0.10 M
 volume of C6H5COONa required = V2 = 62 mL [HCl] = 0.20 M  [H+] = 0.2 M
volume of C6H5COOH required = V1 = 31 mL.
 HS– + H+
(1) H2S  K1 = 1.0 × 10–7
Q.12 (1)
Q.13 (1)
 S2– + H+
(2) HS  K2 = 1.2 × 10–13
Q.14 (2)
Q.15 (1) So,
Q.16 (1)  S2– + 2H+
H2S  K = K1 × K2 = 1.2 × 10–20
JEE MAIN 2
PREVIOUS YEAR'S S–2   H + 
   
Ka = 
Q.1 (4)  H 2 S
HA  
2
S–2   H + 
H  A  –20    
K a      10–5; 1.2×10 =
 HA   H 2 S
1.2  1020  [H 2S] 1.2  1020  101
Salt  [S2–] = =
[H  ]2 4  102
 
pH = pKa + log Acid
= 3 × 10–20 M
All the [H+] will come from strong acid [HCl] only.
Salt 
 
6 = –log [10–5] + log Acid

130 J EE C OMPENDIUM
 Ionic Equilibrium

Q.5 (1) Q.11 (1)

CH3COOK + H2O  CH3COOH + KOH Initially, we have only NaOH solution in a flask so, its
Weak acid Strong base pH value is highest as it is a base. When 0.1 M HCl
Hence nature of solution is basic. solution is added to NaOH solution, pH value will
Q.6 (4) decrease until it becomes 7 due to neutralisation. Then
L.A are those which can accept pair of electrons pH value decreases further as more HCl is added in
excess.
Cl Q.12 (2)
AlCl 3 For the salt of strong acid and weak base
Al Six electrons around
Cl aluminium make it lewis acid K w C
Cl [H+]=
K b
Cl
BCl 3 1014  2  102
B [H+] =
Six electrons around 105
Cl Cl boron make it lewis acid
1
–log[H+] = 6 – log20
2
Cl  pH = 5.35
SiCl 4 Si can expand its vocalency due Q.13 (4)
Si due availability of d-orbitals but
Zr3  PO 4 4 (S)  3Zr 4  (aq.)  4PO 4 (aq.)
3–

Cl Cl due to its small size it can’t be

Cl surrounded by six chloride ion 3S M 4S M
4 3
P K sp  [Zr ] [PO 4 ]  (3S) .(4S) 4  6912 S7
3– 4 3

PH 3 Not a lewis acid

1/ 7
H H H  K sp 
S   
 6912 
Q.7 (1)
Ca(OH)2 + Na2SO4  CaSO4 + 2NaOH Correct option : (4)
100 m mol 14 m mole – – Q.14 (4)
– – 14 m mol 28 m mol  Al 3  3OH 
Al  OH  3 
wCaSO4 = 14 × 10–3 ×136 = 1.9 gm
S S 3S
28
[OH–] =  0.28M 3S 0.2 [OH–]3 = [0.2]3
100 S× (0.2)3 = Ksp = 2.4 × 10–24
S = 3 × 10–22 M
Q.8 (1) Q.15 (2)
Rain water is weakly acid due to presence of H2CO3, Temperature plays a significant role on pH
HNO3, acid in rain water. measurements. As the temperature rises, molecular
Q.9 (2) vibrations increase which results in greater ability of
H 2SO4  2NH 4OH   NH 4  2 SO 4  2H 2 O water to ionise and form more hydrogen ions. As a
2m.m 6m.m 2m.m result, the pH will drop. So assertion is incorrect.
 2m.m
The dissociation of water molecules into ions is bond
4 breaking and is therefore an endothermic process. So
pOH  4.7  log 5 reason is also incorrect.
2

pH = 14 – 5 = 9 Q.16 [10.60 to 10.60]

9.8
Q.10 (3) M H2SO4   103
98  100
2
K sp =  Ag +  CO3–2  4
    MNaOH   103
–12 2
8 × 10 = (2S' + 0.1) S' 40 100
or S' = 8 × 10–10 M
40 103  10 103  2 20
= = 103
50 50
C HEMISTRY 131
Ionic Equilibrium

2
[OH–] = ×10–3
5 0.1 2
pOH = 3.397 4 × 10–7 =  0.1 2
1 
pH = 10.603
 = 2 × 10–3
Q.17 [5.22 to 5.24] [H+] = 0.1  = 2 × 10–4 ; pH = 3.7
m mole of acetic acid in 20 mL = 2 = 37 × 10–1
m mole of HCl in 20 mL = 2
m mole of NaOH = 2.5 Q.22 (3) Ksp value of CuS is very low = 10–36 (3.6 × 10–36) due
CH3COOH + NaOH (remaining)  CH3COONa + to low Ksp value Cu+2 ion gets precipitated very quickly
water even with very low concentration of S–2 ion.
2 3/2 0 0
0.5 0 3/2  Cu+2 + S2–
CuS(s) 
3/ 2 Ksp = [Cu+2] [S–2]
pH = pKa + log
2
 
K
Cu+2 + S–2(s)   CuS(s)
eq
= 4.75 + log 3 = 4.75 + 0.4771 = 5.2271  5.23
= 4.74 + 0.48 = 5.22
1 1
Q.18 (2) Keq = K 
sp 3.6  1036
Q = [Pb2+][Cl–]2
2
300  0.134 100  0.4  1036
 =
 400 
=
400 3.6

3  0.134 Due to high value of K (equilibrium constant) CuS

=  (0.1) 2 precipitated quickly.
4
= 0.105 × 10–2
Q.23 [02.00]
= 1.005 × 10–3
 A (aq)  2B (aq)
AB2 
2
Q  Ksp s 2s
3 –11
Ksp = 4s = 3.2 × 10
Q.19 (4)  s3 = 8 × 10–12
Cr(OH)3  Cr+3 + 3OH– s = 2 × 10–4
s 3s Q.24 [7]
ksp = s. (3s)3 For salt of weak acid and weak base
 6 × 10–31 = 27.s4
1
1/4 pH = 7 +  p K b  p K a 
 6 31 
 s    10  2
 27 
1
–
[OH ] = 3s =7+
2
5.23  4.75
1/4
 6 
 3   10 31  = (18 × 10–31)1/4M .48
 27  =7+
2
Q.20 (1) For titration between HCl and NaOH, pH at = 7.24 ~ 7
equivalence point is found to be 7.
Q.25 [1] H2SO3 [Dibasic acid]
Q.21 [37]
C = 0.588 M
At 30 bar pressure mass of CO2 in 1 kg water = 44 gm
 pH of solution is due to First dissociation only
At 3 bar pressure mass of CO2 in 1 kg water = 4.4 gm
since Ka1 >> Ka2
Moles of CO2 in 1 kg water = 0.1
 First dissociation of H2SO3
H 2CO3  H 
  HCO3
0.1(1 ) 0.1 0.1 H2SO3 (aq)  H+(aq) + HSO 3 (aq) : Ka1 =
1.7×10 –2
[H  ][HCO 3 ] at eq. c–x x x
Ka1 =
[H 2 CO3 ]

132 J EE C OMPENDIUM
 Ionic Equilibrium

Q.29 [1]
1.7  H    H SO 3 
 K a1    Ba 2 
Ba(OH) 2   2OH 
100  H 2 SO 3 
Initially 0.0005 M – –
2 After time t 0 0.005 M 0.005  M
1.7 x
  = 0.01 M
100 (0.58  x)
[OH–] = 0.01
 1.7 × 0.588 – 1.7x = 100 x2 Kw = [OH+][OH–]
 100x2 + 1.7x – 1 = 0 –14
 H +O  = K w  10 =10–12
1.7  (1.7)  4  100  1
2
 3  [OH – ] 0.01
 H    x   0.09186
2  100  H +O  = 1 
Therefore pH of sol. is : pH = – log [H+]  3 
 pH = –log (0.09186) = 1.036 ; 1
Q.26 [2] HA   H+ + A– Q.30 [2]
Zn(OH)2 n+2 + 2OH–
Initial conc. 0.01M 0.1M 0
S S 2S ~ 0.1(for 0.1 MNaOH)
Eq.conc. (0.01 – x) (0.1 + x) x
Ksp = S.(2S)2
[conc. of H+ from 0.01M weak acid is very very 2 × 10–20 = S × (0.1) 2
less compare to H+ from 0.1 M HCl]
 (0.01M 0.1M) ~ 0.1 M 2 × 10–20 = S × 10– 2
 
[x ][A ] 0.1  x 21020
Now, Ka =  2  10 6  S=
[HA] 0.01 102
x = 2 × 10–7 S = 2 × 10–18
 x=2
x 2  10 7
Now, =   2  10 5
0.01 0.01 Q.31 [3]
[NH4+] = 0.0504 M, V = 5.0 mL
[NH3] = 0.0210 M, V = 2.0 mL
[CB]
K b  NH 3 
Q.27 [10] pH = pKa + log
[WA]  NH 4  OH – 
  NH  
[CB]
Kb =
 NH3   4
5.74 = 4.74 + log
1
(1.810 –5 )  0.0210  2
1 = log[CB]  [CB] = antilog1  
[CB] = 10 M 0.0504  5
Q.32 [6021]
Q.28 [64] In pure water, M. Moles of HCl = M1V1 = 50 
Ksp = S2 = (8 × 10–4)2 M. Moles of NaOH = M2V2 = 1 
= 64 × 10–8 M. Moles of H+ left = 
In 0.01 M H2SO4
0.02 20
H2SO4(aq)  2H+(aq) + SO42–(aq.) [H+] = 80 103  80 = [0.25]
0.01 0.02 0.01
CdSO4(s) Cd2+(aq) + SO42–(aq) pH = – log [H+] = – log [0.25]
x x (x + 0.01) = – log 10–1 – log 2.5 = 1 – 0.3979 = 0.6021
Ksp = x (x + 0.01) (x + 0.01 0.01 M) = 6021 
= (8.0 × 10–4)
= 64 × 10–8 Q.33 (4) Water act as a lewis base not lewis acid
So, x (0.01) = 64 × 10–8
x = 64 × 10–6 M Q.34 (1)
Bi 2S3  2Bi 3+ + 3S2–
2s 3s
ksp = (2s) (3s)3
2

= 108 (s)5
C HEMISTRY 133
Ionic Equilibrium

x = 282
1.08×10 –73
s  =
5
Q.40 [27]
108 Ka of Butyric acid  2 × 10–5PKa = 4.7
 s = 10–15 pKa = – log Ka = – log (2 × 10–5) = 4.7
 2A 3  3X 2 pH of 0.2 M solution
Q.35 [3] A2X3(s)  (aq ) aq
1 1 1 1
Solubility = sM 2s 3s pH = pKa – log C = (4.7) – log (0.2)
2 2 2 2
Ksp (2s) 2 (3s)3 = 1.1  10–23
= 2.35 + 0.35 = 2.7
108 s5 = 1.1  10–23
pH = 27 × 10–1
mol mol Q.41 [0]
s  10–5 M = 10–5 = 0.01 Solubility of CaF2 = 2.34 × 10–3 g/100 ml
L m3
Now = 2.34 × 10–2 g/1000 ml

k k n caF22.34  102
  m   m   =
78
= 3 × 10–4 mole
m s
 Solubility of CaF2 = 3 × 10–4 mole/litre
   1 0 5
  m  = 3  10–3 S–m2/mol
0 .0 1 Ksp of CaF2 = 4S3 = 4 × (3 × 10–4)3
Q.36 [11] = 108 × 10–12
0.001M NaOH Q.42 (3)
NaOH  a+ + OH– Vsolution = l litre
0.001 0 0 PH = 8.26  POH = 14 = 8.26 = 5.74
[NH3] = 0.2 M = [Base]
0 0.001 0.001
PKb (NH3) = 4.74
pOH = –log[OH] = –log[10–3] = 3
For basic buffer :
pH + pOH = 14, pH = 14 – 3 = 11
Salt 
Q.37 (2)  
POH = PKb + log Base
pka = – log ka = – log ( 1.3 × 10– 5) = 4.89
 NH 4Cl 
[Salt] 5.74 = 4.74 + log
pH  pK a  log 0.2
[Acid]
1 = log [NH4Cl] - log (0.2)
[CH 3 CH 2 COO  ] log [NH4Cl] = 1 + (– .699)
4 = 4.89 + log log [NH4Cl] = 0.301
[CH 3 CH 2 COOH]
[NH4Cl] = antilog 0.301 = 1.995 ~ 2M
[CH 3 CH 2 COO  ] Vsolution = 1l
log  0.89 Moles of NH4Cl = 2 ×1 = 2 mol
[CH 3 CH 2 COOH] Mass of NH4Cl = 2 × GMM
= 2 × 53.5
[CH 3 CH 2 COO  ]
 anti log(– 0.89)  0.13 = 107.0gm
[CH 3 CH 2 COOH] Q.43 [5]
Q.38 (4) Solubility of AgCl will be maximum in, Deionized  pH = 12
water because there is no common ion effect. Hence  [H+] = 10–12M
option (D) is correct.  [OH–] = 10–2 M
 [Ca(OH)2] = 5 × 10–3M
Q.39 [282]
PbS 2+
Pb + S
2–
milli moles of Ca  OH 2
ksp = s 2
s  Solubility 5 × 10–3 =
100mL
ksp = solubility product
milli moles of Ca(OH)2 = 5 × 10–1
s  k sp Ans. = 5

 8 1028  Given Ksp = 8 × 10–28

Q.44 (9079)
 8  1014  2 2  1014 In resultant solution
= 2.82 × 10–14 = 282 × 10–16 mol/L = x × 10–16

134 J EE C OMPENDIUM
 Ionic Equilibrium

n NH3 = 0.1 – 0.02 = 0.08 1

pH = 7 + (pKa + log C)
2
n NH4Cl = n NH = 0.01 + 0.02 = 0.12
4
1
=7+ [5 + log (2 × 0.005))
 NH 4  2
pOH = pKb + log
 NH3  1 1
=7+ [5 – 2 log 10] = 7 + × 3 = 8.5 = 85 × 10–1
2 2
0.12
= 4.745 + log
0.08 Q.49 [44]
3  CO2  g   H 2  g 
CO  g   H 2O  g  
= 4.745 + log
2 Intial 1 1
= 4.745 + 0.477 – 0.301 Final 1–0.4 1–0.4 0.4 0.4
pOH = 4.921
0.16
pH = 14 – pH  Equilibrium constant 
0.36
= 9.079
 0.44
Q.45 (2)
 KC×102 = 44
[H+] = 1000
pH = –log[H+] = – log103 Q.50 (1)
=–3 H 2 PO 4  HPo 42  H 
acid Conjugatebase

Q.46 (3) Kw increase with increase in temperature as

Assume : Mass of solvent  Mass of solution dissociation of water increases with increase in
Case I :- temperature.
When weak monoprotic acid is titrated against strong
W1 1000 base, at half neutralization point, the solution becomes
0.25   acidic buffer and its pH is given by
62 500
[Salt]
Case II :- pH = pKa + log
[Acid]
W2 1000
0.25    pH  pK a  0 as [salt] = [acid]
62 250

W1 2 Q.51 [458]

W2 1 CH3COOH + NaOH CH3COONa + H 2O
5 2 – –

Q.47 [10]
Buffer of HOAc and NaOAc 3 0 2

2
0.1 pH  pK a  log  
pH = pKa + log 3
0.01
pH = 4.76 + 0.30 – 0.48
5 = pKa + 1 = 4.76 – 0.18
pKa = 4 = 4.58
Ka = 10–4
Q.52 [5]
x = 10
 1.25 
Q.48 [85]  Ba 2    
 50 
Concentration of calcium lactate = 0.005 M,:
 0.5 
concentration of lactate ion = (2 × 0.005) M.  F    
 50 
Calcium lactate is a salt of weak acid + strong base
2 1.25  0.5  0.5
 Salt hydrolysis will take place. Q sp   Ba 2   F –  
50  50  50

C HEMISTRY 135
Ionic Equilibrium

K sp  0.5 106 1
 Molarity of NaOH solution   0.11M
Qsp 9
5
K sp Q.3 [2.30 TO 3.00]
B+HA –– BH++A–
Q.53 [233] 0.1M, V ml
BaSO 4  Ba 2  (aq)  SO 42  (aq) 0.1Vmmol 0.1 V m mol 0.1V0.1V
s s  0.1
0.1V
  BH     0.5M
K 2SO4  K (aq)  SO42 (aq) 2V
0.10.1 0.1 0.1
pH at eq. pt=6 to 6.28
K SP =  Ba 2+  SO 42-  1
1 × 10–10 = S(S + 0.1)
pH  7   pK b  log 0.05
2
 0.1 S So pKb = 2.30–2.80
S = 10–9 M = 233 × 10–9 gL–1 Possible
Solution 2
Q.54 (2) at V=6 ml rxn is complete
A2B3  2A3+ + 3B2– SoV=3ml is half of eq. pt
C – – at which pH=11
   pOH=(14–11) =pKb+log 1
C (1 – ) 2C 3C pKb=3
]
 2C   3C 
2 3

 108C  4 5 Q.4 [0.20]

Keq =
C(1  ) For ppt, [Zn+2] [S–2]=Ksp
1.25  10 22
S2  
1
K eq  Keq  5
 5     4 
0.05
108C4  108C  = 2.5×10–21 M
Q.55 [9000]  2H++S–2
H2S 
The concentration of H+ or say HCl in both the given
2
solution is 10–1 and 10–2 mole L–1 respectively.  H    2.5  1021
For the given amount of HCl the cencentration KNet=10 –21 
0.1
depends over dilution hence
2 1
C1 V2  H   
= 25
C2 V1
2 1
10–1 V2  H    M  0.2M
= 5
10–2 1L
Q.5 [10.02]
1V2 = 10 L = 10000 mL First acid base reaction between H2CO3 and NaOH takes
V = 10000 – 1000 mL = 9000 mL place

JEE-ADVANCED H 2 CO3  NaOH 

 NaHCO3  H2 O
0.01 mole 0.01 mole – –
–
PREVIOUS YEAR’S – 0.01 mole

Q.1 [4.47] In the final solution, we have 0.01 mole Na2CO3 and
0.02 moles of NaHCO3.
 H    103 
Here, we have a buffer of NaHCO3 and Na2CO3
S  K sp     1  2 1010  8  1
 Ka  [Salt]
   10   pH  pK a 2  log
[Acid]

 2  105  4.47  103  0.01 

 
 10.32  log 
Q.2 [0.11] 0.1 
No. of eq. of oxalic acid = No. of eq. of NaOH  0.02 
 
5.00  0.10 9.0  M  0.1 
or 2  1
1000 1000

136 J EE C OMPENDIUM
 Ionic Equilibrium

1
 10.32  log
2
= 10.32 – log2
= 10.32 – 0.3
= 10.02
 pH = 10.02

Q.6 [6]
 H   HSO 42 (Ka1 is verylarg e)
H 2SO 4 
1M 1M
 H  SO42 
HSO 
4

Ka 2  1.2  10 2

SO 24   coming from Na2SO4 = 1.8× 10–2

SO 24   H   1.8  102  1

  Ka 2
 HSO 4  1

 Rather than dissociation of HSO 4 into H +

and SO 24  ions, association between already present
H+ and SO 24  will take place.
Assuming ‘x’ mol/L of SO 24  and H+ combines to form
HSO 4
 [ SO 24  ] = 1.8 × 10–2 – x

 H    1  x  1 
  assuming x  1
 HSO 4   1  x  1


1.8 10 2
 x 1
 1.2  10 2
1
 x = 0.6 × 10–2
[ SO 24  ] = 1.2×10–2 M
 Pb 2   aq   SO 42   aq 
PbSO 4  s  
If solubility of PbSO4 = sM
 [Pb2+] = s
SO 24    s  1.2  10 2  1.2  10 2
(assuming s << 1.2 × 10–2)
 s × 1.2 × 10 = 1.6 × 10–8
–2

1.6
s  10 6  1.33  10 6
1.2
On comparing with X × 10–Y
Y=6
Q.7 (B)

C HEMISTRY 137
Thermodynamics

Thermodynamics
w = + 965.87 Cal
For isothermal process  w = –q
DPP-1
 q = – 965.87 Cal
Q.6 (3)
Q.1 (3)
During reversible process, the internal equilibrium Q.7 (2)
is disturbed only infinitesimally small and in the limit, Q.8 (2)
it is not disturbed at all. Thus system and surroundings Q.9 (1)
remain in equilibrium Q.10 (1)
Q.11 (2)
Q.2 (4) Q.12 (4)
Hint: For isothermal process involving ideal gas
Q.3 (3) T = E = H = 0
The properties, which do not depend on the amount
of substance, are called intensive property. e.g.,
surface tension, viscosity etc. DPP-3
Q.4 (1)
Q.5 (4) Q.1
Q.6 (2) ( 4)
Q.7 (4) E = nCVT
Q.8 (2)
9
24   CV  15
22.4
DPP-2
CP – CV = R
Q.1 (4)
Q.2 (1)
Process is isothermal reversible expansion, hence
Q.3 (4)
U = 0  V2 
 q=–w S = 2.303 nR log  V 
 1
As q = + 208 J
Hence w = – 208 J S  9.2 calK –1

Q.2 (2)
We know that Q.4 (4)
In irreversible process For equilibrium condition, G = H – T S
W = – PextV =O
H 170kJ
Pext  100 K Pa  105 Pa  T= 
  S 170J / k
 V1  1 dm  0.001 m 
3 3

  170  1000J
 V2  1 m
3 T= = 1000 k
 170J / k
w = – 105 (1 – 0.001)N × m for spontaneity of reaction, G < O
w = – 99900 Joule H
H – TS < O T> = 1000 k
Q.3 (4) S
Q.4 (1) T > 1000 k  T = 1200 k
Q.5 (3)  out of given option in equation
For isothermal process E = 0 and w = – 2.303 nRT
P1 Q.5 (2)
log10 P Due to randomness of particles is reduced since,
2
entropy decreases
2
w = – 2.303 × 1 × 2 × 300 × log Q.6 (1)
10
CO2(s)  CO2(g)
w = + 2.303 × 600 × log 5
Solid  gas  endothermic Reacton H + type
w = + 2.303 × 600 × 0.699
138 J EE C OMPENDIUM
 Thermodynamics

Also, Gas is more random state than solid  So Q.6 (3)

S = +ve Q.7 (3)
Q.8 (4)
Q.7 (1) Q.9 (3)
H2O () 
186·5J/mol
 H2O(g) Q.10 (1)
B.P. of Hvap = 186·5 J/mole DPP-5
Q.1 (3)
qp H 186·5
H2O() S = = = = 0·5 1
7 B.P 373k 373 H2 O 
 H2  O .......(1)
= 373 k s = 0·5 J/k 2 2
9
Q.8 (2) For decomposition of mole of water require
18
for endothermic reaction  H = + ve
enthalpy = 142.5 kJ
Also given, S = + ve
Means 285 kJ/mole
G = H – TS
for formation
(+ ve) – (+ ve)
for feasibility  G < 0 1
H2  O   H2 O ....... (2)
means TS > H  0 2 2
Q.9 (4) H = – 285 kJ/mole
Q.10 (1)
Q.2 (1)
DPP-4 Hess's law states that enthalpy changes during and
process are independent of path. So, this law is used
Q.1 (4) in calculating enthalpy.
At equilibrium
H° = TS° Q.3 (3)
 491.1 103 N2(g) + 2O2(g)  2NO2(g) + X kJ
T ...(1)
198
H1 = – X kJ
2480.3 K = T
2NO(g) + O2(g)  2NO2(g) + Y kJ
G° = H° – TS°
...(2)
As H° and S° are positive so for –ve G°
H2 = – Y kJ
temperature should be greater than 2480.3k
Enthalpy of formation of NO
Q.2 (3) 1 1
N 2  O2  NO(g) ; H3
G = H – TS 2 2
For, H < 0 and S > 0, G = –ve (always) ...(3)
spontaneous at all temperatures. Clearly,

Q.3 (3) 1  1
Reaction (3) = (Reaction (1)) –   (Reaction)
2 2
H2O() 
H2O(g)
H1 1
 H   E   n gRT H3   H 2
2 2
1  8.314
40.66   E   373 X  Y  Y  X
1000    
2  2 2
E  37.56 kJmol1 Q.4 (3)
Q.5 (1)
Q.4 (2) Q.6 (4)
Q.7 (1)
G   RT ln K P ; K P   2 X  X  4 X 3
2
Q.8 (2)
G   RT ln  4 X 
3 Q.9 (3)
Q.10 (4)
G    RT ln 4  3RT ln X
Q.5 (1)

C HEMISTRY 139
Thermodynamics

DPP-5 EXERCISES
Q.1 (3)
CH4 + 2O2CO2 + 2H2O
3.2 gm CH4 JEE-MAIN
3.2 OBJECTIVE QUESTIONS
= 0.2 mole Q.1 (3)
16
for 1 mole CH4– 880 kJ/ mole Boiling point, pH & density are intensive properties.
0.2 mole CH4– 880 × 0.2 = – 176 Entropy is an extensive property.
Heat evolved –176 kJ
Q.2 (2)
Q.2 (4 ) V2 V2
W = – nRT ln = – P1V1 ln
P(yellow)
5
+ O2(g) 
1
P O (s); H1 = +9.91 kJ V1 V1 L atm
2 2 2 5
= – 100 ln 10
5 1 = – 2.303 × 100 × 101.355 –23 kJ
P(red) + O2(g)  P O (s); H2 = –8.78 kJ
2 2 2 5 = q  + 23 kJ
Rearranging, we get Q.3 (3)
w = – n Cv (T2 – T1)
5
P(yellow) + O (g)  P2O5(g); H = –9.91 kJ T2 = 150 K
2 2 Q.4 (3)
5 d(G) = (V)dP – (S)dT
P2O5  P(red) + O (g); H = +8.78 kJ 310 310
2 2
Adding these two equations, we get
 P is constant,  298 d(G ) = –  298(S)dT
P(yellow)  P(red) ; (–9.91 + 8.78) kJ = –1.13 kJ  –(G°310 – G°298) = S° [310 – 298] = 24 KJ/
mol
Q.3 (3) Q.5 (2)
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) ; H
H is 890 kJ for 1 mole CH4 q
CP =
We know, 24 L means 1 mol n T
T = 0
1
2.4 L means×2.4 mol = 0.1 CP = 
24 Q.6 (3)
 H = 890 kJ × 0.1 = 89 kJ q = 0 (For adiabatic)
Q.4 (1)
Q.5 (1) T1V1r 1 = T2Vr–1
Q.6 (2)
Q.7 (3) 5
1 1
 5 3
Q.8 (2) T2 = 400   = 400 × 3 2 / 3 = 100 K
Q.9 (3)  408  (2 )
Q.10 (2)
5
H = nCp,m T = –5 × × 2 × 300 = – 7500 Cal
2
DPP-6
3
Q.1 (3) Q.2 (4) Q.3 (3) Q.4 (1) Q.5 (1) U = w - nCv.m T = – 5 × × 2 × 300 = – 4500 Cal
Q.6 (2) Q.7 (3) Q.8 (2) Q.9 (3) Q.10 (2)
2
Q.7 (2)
Q.8 (2)
H = E + n RT
Given
H = – 651 x 103 cal. , R = 2 cal,
T = 290 K and n = 6 + 6 – 6 = 6
E = – 651 × 103 – 6 × 2 × 290
= – 654480 cal = – 654.5 Kcal
140 J EE C OMPENDIUM
 Thermodynamics

Q.9 (1)
H 
T = = 750 K]
Q.10 (2) S
Q.11 (2) Q.21 (1)
Q.12 (4) H = – 3600 cal
ng = 0 G = H – TS
H = U
G = – 600 cal
U = – 185 kJ/Mole
For three moles = – 185 × 3 = – 555 Q.22 (3)
Q.13 (4) H = (435 + 240 – 2 × 430) = – 185 kJ mol–1
C2H4 + HCl  C2H5Cl
2  187  (131  223) 20
ng = – 1 S =  kJ mol 1
HCl is limiting reagent 1000 1000
U = H – ngRT
G = H – TS
= – 185 + (1 × 8.314 × 10–3 × 300)
= – 69.8 kJ 300  20
For two mole of HCl = – 69.8 × 2 = –139.6 kJ = – 185 –
Q.14 (2) 1000
W = –100J , q = 150 J = – 185 – 6 = –191 kJ mol–1 ]
q = E – W Q.23 (1)
150 = E – (–100) Gº = – RT ln k
= 150 – 100 Q.24 (4)
E = 50 J Hº= Hfº(products) –  Hfº(Reactants)
Q.15 (1)
= [H f ( H 2 O )  H f ( CO ) ]  [H f ( CO 2 )  H f ( H 2 ) ]
0 0 0 0
W = – PV
= – 1.5 (1– 0.5)
Hº = [–241.8 – 110.5] – [–393.5 + 0]
= – 0.75 atm-litre = – 0.75 × 101 Joule
= – 352.3 + 393.5 = + 41.2 KJ
q = 200 J
Q.25 (4)
q = E – W
200 = E – (– 0.75 × 101) rH= 0 ;
If all the reactants & products have zero f H.
E = 124.25 Joule
Q.26 (2)
Q.16 (2)
H2 + O2 H2O (l)
U = q + w
H – H + 0 = 0 H20(g) H20 (l)
= – 200 + 300 = 100 J]
Q.17 (2) X = X1 + – 2X3 – X4
Q.27 (1)
H f 6025 H+ = 1 Mole ; OH– = 0.75 Mole
Sf = =
T 273 H = 0.75 (–57)
= 22.1 JK–1 mol–1 3
Q.18 (3) Hear enolved = 57
4
T2 Q.28 (2)
S = nCv ln Q.29 (3)
T1 Q.30 (4)
– 25 = (4x +y ) – (3x + 84 + 103)
3 573 x + y = 162
=2× R ln y = 57.85
2 473
Q.31 (4)
Q.19 (3) Q.32 (2)
Q.33 (3)
300  30
Svap = + = – 30 J/mol.K Q.34 (3)
300 Q.35 (1)
Scond = – 30 J/mol-K Q.36 (4)
Q.20 (2) Q.37 (2)
At Eq. G° = 0 Q.38 (2)
H ° = TS° Q.39 (3)
Q.40 (1)

C HEMISTRY 141
Thermodynamics

Q.41 (3)
Q.42 (4) Q.6 (A)
Q.43 (2) w = zero
Q.44 (2) Since the area of both triangle is equal. Also work done
Q.45 (1) in one is positive while in other is negative.
Q.46 (2) Q.7 (C)
Q.47 (1) W = – Pext [V2 – V1]
Q.48 (1) W1 = – 2 [16 – 4] × 100 = – 2400 J
W2 = – [32 – 16] = – 16 × 100 = – 1600 J
JEE-ADVANCED ---------------
OBJECTIVE QUESTIONS – 4000
Q.1 (C) ---------------
Work done in the cyclic process q = – W = 4000 J
= Area bounded (ABCA) Q.8 (B)
1 For adiabatic expansion against vacuum.
=
2
× AC × AB q = 0 w = 0,  Pext = 0
1 U = q + w
=
2
× 2V1 × 3P1 = 3P1V1 U = 0
 nCvmT = 0 T = 0
Q.2 (A) T1 = T 2 ]
Q.9 (D)
1
Magnitude of work = A = P1 V1 + × P1 ×6 V1
2  T2 T1 
nCv (T2 – T1) = – Pext ×nR   
II
 P2 P1 
2P1
= 4 P1 V1 = 4 nRT1 P I III 9
P1 T2 = T
IV 7 1
V1 2V1 8V1
5 9 
= 4 × 1 × 2 × 300 V
w=2× × R  T1  T1 
2 7 
= 2400 cal = 500 R
Q.3 (C)
Q.10 (D)
Equation of process
U 4.48
log P  2.38 2.10  2.38  0.28  7 Cv =
nT
, n= = 0.2
   22.4
log V  1.10 1.30  1.10 0.20 5
12
 (log P – 2.38) × 5 = –7 (log V – 1.1) = = 4 cal
0.2  15
 5 log P + 7 log V = 19.60 CP = Cv + R = 4 + 2 = 6 cal
 log P5 + log V7 = 19.60 Q.11 (C)
P5V7 = antilog (19.60) = constant Total cubes = n
or PV1.4 = constant
9
  = 1.4 – diatomic & adiabatic Moles of H2O = n × = 0.5 n
Q.4 (A) 18
Heat released by liquid = Heat absorbed by ice
22
|w| =  ab =  7  5 = 110 bar lit. = 11000 J = 111 500
7 n × 0.5 × 6 = × 75.6 × 20 × 10–3
18
kJ
3n = 42
Final Answer = –11
n = 14
Q.5 (B) Q.12 (A)
dP P
=  
dV  V  P1V1T1 P 2 , V 2 , T2
 increases slope decreases]
142 J EE C OMPENDIUM
 Thermodynamics

As container is insulated
q=0  T2   273 
  = 18 ln 
Scooling = + nCpln  
q1+ q2 = 0   373 
n1Cm (T –T1) + n2 Cm (T – T2) = 0
 T1 

n 1T1  n 2 T2 P V  P V T T
 1 1 2 2 1 2
 80 18
Sfusion =
T=
n1  n 2  P1V1T2  P2 V2T1  273

  80 540   273 
=  18    18 ln 
373 
Q.13 (D)
  273 373  
209
U = 100 – = 50 cal
4.18  80 540 373 
= –18    ln 
U = nCvdT  273 373 273 
5  36.95 cal /°
Cv, m = R Q.19 (C)
2
0.40 = aT13 + bT1  0.40 = a × (1000) + b ×
20 10
ndT =
R  0.4 = 1000a + 10 b
...(1)
q = nCmdT
0.92 = aT23 + bT2  0.92 = a × 8000 + 20b
100R ...(2)
Cm = = 5R On solving
20
0.12 = 6000 a ; a = 2 × 10–5
Q.14 (B) –5
0.40 = 2 × 10 × 1000 + b × 10
He has no vibrational and rotational degree of freedom
 b = 0.038
because of its monoatomicity so for a monoatomic
gas so heat capacity is independent of temperature.]
aT 3  bT a[T23  T13 ]
Q.15 (B)
Heat released to cool 500 g water from 20°C to 0°C,
Sm =  T ·dT 
3
+ b[T2 – T1]

q = ms T
= 500 × 4.18 × 20 = 41800 J = 41.8 kJ 2  10 5  (8000  0)
Number of moles of water (ice) that will melt to ab-   b(20)
3
sorb 41.8 kJ
41.8
7 2  10 5  8000
=
6.02   0.038  (20)
Number of cubes of ice that will melt = 7
3
Q.16 ( B)  0.053 + 0.76  0.813 J/K-mol
2A2(g) + 5B2(g)  2A2B5 (g); H = –50160 J Q.20 (D)
n = 2– (5 + 2) = – 5 mol.
Tc  Th
H = E + (n) RT Cv(Th – T) = Cv(T–Tc)T = ;
– 50160 = E + (n) RT 2
E = – 50160 – (–5) (8.314) (300)
T2 C v ·dt
Q.17
= – 50160 + 12471 = –37689 J
(B)
 S = T 1 T
U =q+w
= (40 × 200) + (–2 × 10 × 100) T T
= 6000 J Ans. ScCvln & ShCvln
Tc Th
Q.18 (B)

 H vap  540 18 Tc  Th  Tc  Th 

Scondensation = = Total S = Cvln + Cvln
T 373 2Tc 2Th

C HEMISTRY 143
Thermodynamics

Tc  Th 2 log KC = –
1
= Cvln 9
4Tc ·Th
Q.21 (B) C eq2 1 C eq 1

300 log
A eq2 9
log
A eq =–
18
=
=1–
500 5.56 × 10–2 (at equilibrium [C]eq= [D]eq [A]eq
= 1 – 0.6 – 0.4 = [B]eq)
W Q.29 (B)
%  = 40 = 100 CH3 – CH = CH2 + H2 CH3 – CH2 – CH3;
q
H1 = (BEC=C + BEH–H) – (2BEC–H + BEC–C)
40 CH2
w=  2 = 0.8 Kcal + H2 CH3 – CH2 – CH3
100 CH2 CH2
Q.22 (D) H2 = (BEC–C + BEH–H) – (2 × BEC–H)
H2 – H1 = 2BEC–C – BEC=C
V2
S = nR ln Q.30 (D)
V1 CaO(S) + 3C(S)CaC2 + CO
V2 = 40 r = – 14 – 26 + 152 = 112 per mole
V1 = 20 for 1.28 Kg = 112 20 = 2240 Kcal
S = 2 × 2 ln 2 Q.31 (A)
= 4 ln 2 = 2.77 cal. HCl = NaOH = = 510–Mole
Q.23 (C) q = 4.2 3 = 1.26 KJ.
per mole
P1 KJ = 2.5 102 KJ/Mole
S (system) = nR ln
P2 = 10 × 8 × ln 2 = 80 × 0.7 Q.32 (D)
C – E bond has highest bond energy ; it means that the
= 56 covalent bond C – E will be strongest. Smaller is the
q irr w irr size of atom, stronger is the covalent bond.]
Ssurr = –  Q.33 (D)
T T
 58 g isobutane provides energy
Q.24 (C) = 2658 kJ
Gº = 2 × Gº NH 3 – Gº N 2 – (Gº H 2 × 3)  11.2 × 103 g isobutane provides energy
= 2 × (–16.66) – 0 – 0 2658  11.2  103
= kJ = 513268.9 KJ
= – 33.32 KJ 58
Q.25 (A) The daily requirement of energy = 15000 kJ
Gº = – 2.303 RT log Kp 513268.9
 cylinder will last = = 34 days
KP = P = 10–5.44 15000
Q.26 (D) Q.34 (C)
G = Gº + 2.303 RT log Q HA BOH

0.022 H+ A– + B+ OH–  H2O + BA

Q=
1 3 3 – 56.1 = ionH – 57.3
1.5  = 1.2 = 0.8
= – 60.5 kJ/Mol
Q.35 (C)
Q.27 (C)
C (graphite) (diamond) ; H1 –H2
Gº = – 2.303 RT log Keq H1 – H2 = (6g º Mole)
= – RT ln KP = 0.95
Q.28 (A) Q.36 (A)
Gº = 2.303 RT log KC N2(g) + 3Cl2 (g) 2NCl3(g) ; rH
460.6 = – 2.303 × 2 × 900 log KC above eqn can become

144 J EE C OMPENDIUM
 Thermodynamics

Q.50 (B)
2 Rxn + Rxn – 3 Rxn
f H (NCl3,g) = rH
= [–2H1 +H2 – 3H3] JEE-ADVANCED
= – H1 + – H3 COMPREHENSION/MATCHING/MCQ
Q.37 (C) Q.1 (A) (C) (D)
By Rxn .....1 – Rxn .....2 Q.2 (A) (B) (C)
4 AuBr4+4 HCl HA4Cl4 + 4HBr Q.3 (A) (B)
H = – 28 + 36.8 = 8.8 Kcal/mol
Q.4 (B) (D)
But H = 0.44 Kcal
Q.5 (A) (B) (D)
= = 0.05
% dissociation = 5% (a) y = mx + C
Q.38 (A) 10 = m × 300 + C
By 15 = m × 600 + C
Eq ....2 – Eq....1 ---------------------
t – 2–butene 1 – butene 5 = 300 m
H2 –H1 > 0
By 1
Eq ....6 – Eq....7 m= , c=5
60
t – 2 – butene 1– butene
H2 – H1 > 0 1
H = – 647 + 649.8 = 2.8 V=
60
T+5 w=–  PV
H2 – H1 = 2.8 and
9H1+5H2= 0 300R
H2 = 1.0 and H2 =1.8 P = 60 R –
V
Q.39 (D)
H2 + O2 OH(g) ; 42 ....(1)
 300R 
15
H2(g) +O2(g) H2O(g) ; –242 ....(2)
H2(g) 2H(g) ; 436 ....(3)
w=–   60R 
10
V 
dV = – 1496.52 J
O2(g) 2O(g) ; 495 ....(4)
(b) U = q + w or q = U – w
(a) Eq——3 + Eq ——4 Eq 2
U = CvT = 374.13
242 + 436 + = 925.5 ; True
(b) Eqn 3 + Eqn 4 – Eqn 1 q = 374.13 + 1496.525 = 5237.82 J
H = –42+, false 5
(c) H2  2H ;rH = 2fH (H,g) (c) H = × R × 300
2
fH(H,g) = = 218 ; False
(d) First reaction is rH = fH(OH,g) (d) S = + ve
= 42 ; True
Q.40 (C) Q.6 (A),(B),(C)
+ 3H2
rH = fH (cyclohexane) fH(Benzene)  G < 0 for spontaneous
= – 156 – 49 (D) Assumed to zero not unity
rH = 3(– 19) + R.E
R.E = – 156 – 49 + (3 119) = 152 KJ/ Mole Q.7 (C)
Q.41 (B) 35000
Q.42 (A) Svaporisation{1 atm 350 K} = = 100 J/K
Q.43 (B) 350
Q.44 (D)
Svaporisation{0.5 atm 350 K} = 100 J/K mole + RT ln
Q.45 (B)
Q.46 (C) P1
Q.47 (C)
P2 = 100 J + RT ln 2
Q.48 (A)
Q.49 (D)

C HEMISTRY 145
Thermodynamics

1
Svaporisation{2 atm 350 K} = 100 J + RT ln  ] or 521 kJ/Mole
2
Q.13 (C), (D)
Q.8 (B),(C),(D) Enthalpy of formation : follow the definition

Q.9 (A),(B),(C) Q.14 (A) (C) (D)

Pwhite < Pred (Stability)
C (diamond) ;  fH  0
 Exothermic
Q.15 (A) (D)
Q.10 (A) (C) (D) 3A (l)  A3(l) at 300 K.
PT = constant  PV1/2 = constant
3A (l)  A3 (l)
P2 V2  P1V1
W=
x 1
nR (T2  T1 ) 3A(g)  A3(g)
=
x 1 Enthalpy for trimerization of liquid
H = –100 ×103 + 3 × 25 × 103 – 50 × 103
2  R (300) H = –75 × 103 J/mol or – 775 kJ/mol
=
1/ 2 3  25  103 50  103
= 1200 R S = – 400 + 
300 400
3 = –400 –125 + 250 = –275 J / K.mole
U = nCv,m T = 2 × R (300 – 600) = – 900 R
2 G = – 75 × 103 + 300 × 275
Q = U – q = – 900 R – 1200 R = – 2100 R = 7500 J or 7.5 kJ / mol]
]
Q.16 (A) (B) (C)
Q.11 (A),(C)  nRT2 nRT1 
3UO2 +O2 U3O8 nCv,m [T2 –T1] = – Pext   
 P2 P1 
– 76.01 = – 853.5 – (3   fH(UO2)
 853.5  76.01 3  RT2 R  250 
R [T2 – 250] = – 3  
  fH =
3 2  3 1 
= – 259.16 Kcal /Mole
2
T2 – 250 = – T + 500
3 2
Q.12 (A), (C)
 2
1 T2 1 
3 
= 750
UF(g) U(g) + F2(g)
2 

 rH =  fH (U,g) –  fH(UF,g)
,g) 5
T2   = 750
= 128 – 22 = 106 3
or T2 = 450 K

1 3
W = U = 2 × R × 200  600 R
 rH = E U–F – 2 EF–F = 106 2

1 5
H = 2 × R × 200  1000 R
 E U–F = 106 +  37 2
2
= 124.5 Kcal /Mole

146 J EE C OMPENDIUM
 Thermodynamics

Q.17 (A), (B), (C), (D)

Sol.25 I2(s) I2(g)
Solid liquid
 H2 –  H1 =  Cp (T2 –T1)
Endothermic ;  H > 0
50
 H2 – 6.096 = (0.031 – 0.055) 1000  254
Q.18 (A) (B) (D)
G = H – TS
 H2 = – 0.3048 + 6.092
(i) Combustion is spontaneous reaction so H is –
= 5.78
ve as H > TS
(ii) G is – ve for vaporisation above boiling point as
TS > H Comprehension # 02 (Q. No. 26to 29)
(iii) G is +ve for fusion at 0°C as H = +ve and S Ans. 26. B; 27. A; 28. A; 29. C
= –ve
(iv) G is –ve as S = +ve & H = +ve but TS > H Comprehension # 3 ( Q. No. 30to 33)
Ans. 30. A, 31. B; 32. B; 33. A
Q.19 (A), (C), (D)
Sol.30 1 True 2 True 3 True 4 True 5 False

Q.20 (C),(D)
H
Arrhenius equation ; K = Ae–Ea/RT
Kirchaff’s Equation ;
H C H 360
d (  rH) =  r CpdT Sol.31 EC–H = = 90
4
H
Comprehension # 01 (Q. No. 21 to 25)
Ans. 21. (A) ; 22. (B); 23. (B); 24. (A); 25 (A)
H H
Sol.21 Stable state had zero standard molar enthalpy
H C C H 620 = 90  6 + EC–C
Sol.22 N2 + O2 2NO ;  rH > O
H H
N2 + 2O2 2NO2 ;  rH > O  EC–C = 80
Endothermic reactions are favourable High tem-
perature.
Sol.23 (diamond) +O2 CO2 ; – 94.3 Sol.32 To Keep the temp. constant  H
(Amorphous) + O2 CO2; – 97.6 overall = 0
(diamond) (amorphous) ; Let x mole O2 and y mole steam
 rH  rH = –94.3 +97.6  110  2x = 132 y
=3.3 KCal / Mole
x no2
1
for 6g C  Mole C
 y =n = 0.6
steam
2
3.3 no2 1
 rH =  = = 1.666
2
= 1.65 KCal nsteam 0.6

Sol.24 H2O (l) H2O(g) Sol. 33 H2O (s) H2O (l) ; 1.44 KCal
 18  0.62778 =  fH(H2O, g) –  fH(H2O,l)
1.44
=  fH(H2O, g) + 68.3 For 27 g  27 = 2.16
18
  fH(H2O, g) = – 68.3 + 11.3
= –57.0 KCal

C HEMISTRY 147
Thermodynamics

Comprehension # 4 (Q. No. 34 to 36) –w is work done by the system

Ans. 34. A; 35. D; 36. B U = q + w
Sol.34 Acetic acid ; weak acid (Less than 13.7) =5+4=9
And HF is the exceptional case having langer value
for Heat of neupralization than 13.7
Q.3 [0]

Sol.35 (i) True CH 4(g )  2O 2(g )  CO 2(g )  2H 2 O (g )

(ii) Due to cont. volume it measure  U
n g  (3  3)  0
(iii)  ng = 0   H =  U
(iv) False (due to involvement of R.E)
Q.4 [4]
P V³ = constant  (P/P’) x (V/V’) ³ = 1  (P/P’) =
Sol.36 Case I ; H+ = 0.1  100  2 = 20 m.eq. (V’/V) ³
OH– = 0.1  100  2 = 20 m.eq.  (P/P’) =(d/d’) ³ (Since V  1/d)
Case II ; H+ = 50  0.1  2 = 10 m.eq.  (d’/d) = (1/32) –³ = (1/32)–1.4 = 128 = 32x
OH– = 100  0.1 = 10 m.eq. x=4
 2 HII =  HI
HI = 274 cal ;  HII = 137 Q.5 [8]
TI = TII (Because amount of substasace in case I w  Pdv
is double than case II)
 1  2.5  2.0 
Q.37 A  (P,R), B  (Q,S), C  (Q,S), D  (Q,S) =–0.5 litre-atm
If ng > 0 : S > 0
0.5  1.987  4.184
  50.63J
0.0821
Q.38 A  (P,S), B (Q), C  (R)
Kircaff’s equation
 work is carried out of constant P and thus
irreversible
d(  rH) =  rCpdt from 1st law of thermodynamics
  H =  U +  ngRT
T q  U  w
q rev 58.63  U  50.63
 s=
T U  8 joule

Q.39 (A) S, (B) P, (C) Q, (D) R

Q.6 [2]
Q.40 (A) P, S, R, (B) P, R, (C) P, (D) Q, R, S H fusion  6.025 1000 J mol–1
6025
Q.41 (A) P,Q (B) P,T (C) R,S (D) Q  J / g 1  334.72Jg 1
18
NUMERICAL VALUE BASED/STATEMENTS
H fusion 334.72
Q.1 [6] Sfusion    2Jk 1g 1
Tf 167K
H = U + (PV)
 H = 40 + (P2V2 – P1V1) = 40 + (5 x 6 – 2.5 x
4) = 40 +20 = 60 = 10x Q.7 [5]
x=6  = 1.4
5 7
CV  R CP  R
Q.2 [9] 2 2
q = U – w H  85 Joule at constant pressure

148 J EE C OMPENDIUM
 Thermodynamics

85 140  2 40 Hf 
12
 6Kcal
T   
nCp 7n  R n 2

40 Q.14 [6]
Now, w   nRT   n  2   80J
n H  E  nRT
q P  H  U    W  , 3.6
n  6
U  H  W  85  80  5J 2 103  300

Q.8 [2] Q.15 [7]

Reversible work is maximum work
Since G = H - TS
w  2.303nRT But at equilibrium, G = 0 = H - TS
 v 2   16  8.314  300  log 25 3 H 2000
log 2.303
10    2.01 10 2kJ
joule  S =   7 J / mole / K
 v1  32 5 T 286

Q.16 [8]
Q.9 [0] Theoretical heat of formation of NO2 142KJ/mol
Pext  0, w   pext ( v2 v1 )  0(v2  v1 )  0 1
As temp is not given, assume it as constant and
N 2  O 2 
 O  NO
2
therefore  E=0
1
E  q  w  0  q  0  0, H  0 H (Theoretical) =  946  498  222  607
2
= 142 kJ / mol
Q.10 [9]
In isothermal reversible process Q.17 [3]
S = qrev/T
1
q = W = 2.303RT log(V2/V1) N2(g) + O2 ( g ) 
 N 2O ( g ) H = 30 kJ
= 2.303  8.314  300 log 3 = 2740.6 J mol-1 2
. . . . (i)
q 2740.6
Ssystem  rev   9.135 JK 1mol 1  9 1 1
T 300 N 2 ( g )  O2 ( g ) 
 NO ( g ) H =
2 2
90 kJ . . . . (ii)
Q.11 [1]
By eq [4  (ii) – 2  (i) ]
 L  0.075  40  3Cal  4NO H = 300 kJ
2N2O + O2 
 P  0.125  40  5Cal 3  102 kJ x=3

Q.18 [4]
P 5
  1.66 gas is mono atomic eA – A = a;eA – B = a ; eB – B = 0.5a
L 3 1 1
Also, A2  B2 
 AB;
2 2
Q.12 [1] H = -100 kJ mol-1
Heat of neutralisation of a strong acid by strong 1
 H = [eA – B] + [e +e ]
base is -13.7 Kcal 2 A–A B– B
1 mole of H2SO4 furnishes 2 moles of H+ 1
= a + [a  0.5a]
2
Q.13 [6]  100 = 0.25 a
H  12Kcal  a = 400 kJ mol-1 = 4  102
 X=4

C HEMISTRY 149
Thermodynamics
 Resonance Energy = 142 – 134 = 8 kJ /
mol.
Q.5 (3)
Q.19 [6] C (s) + O2 (g)  CO2 (g) ; H = – 393.5 kJ/
x 100   10  x 150   x  6 mol.
1
CO (g) + O2 (g)  CO2 (g) ; H = –
Q.20 (3) 2
283.5 kJ/mol.
Absolute entropies of ions are relative to H+ (aq)
1
C (s) + O (g)  CO (g) ; H = –
Q.21 (4) 2 2
393.5 + 283.5 kJ/mol = –110 kJ/mol.
Q.22 (4) Q.6 (2 )
For an isothermal expansion of an ideal gas at constant
Q.23 (3) pressure, H = nCPT = 0; S = nRln(Vf/Vi ) > 0

Q.24 (1) Q.7 (2)

Total enthalpy change involves the the following steps
JEE-MAIN :
PREVIOUS YEAR’S 1. Enthalpy change during conversion of 1 mole water
Q.1 (1) at 5°C to 1 mol of water at 0°C
C2H5OH() + 3O2(g)  2CO2(g) + 3H2O() 2. Enthalpy change during conversion of water at
0°C to ice at 0° C
U = – 1364.47 KJ/mol.
3 . Enthalpy change during conversion of 0°C ice into
H = U + ng RT
– 5°C ice.
ng = – 1
Total H = CP H2O(l ) T + Hfreezing + CP H2O( s )
  1 8.314  298 
H = – 1364.47 +   = 75.3 
 1000 
kJ mol–1
= – 1364.47 – 2.4776 = – 1366.94 KJ/mol.
Q.8 (3)
Q.2 (4) From A to B;
2Gºf(NO ) – [2Gºf(NO) + Gºf(O )] = Gºr = – RTn Kp q = + 5 J, w = – 8 J (work done by the system)
2 2
According to first law of thermodynamics,
2Gºf(NO ) – [2 × 86,600 + 0] = – RTn Kp
2 U = q + w = 5 – 8 = – 3J
From B to A; U = + 3J
Gºf (NO ) = 0.5[2 × 86,600 – R (298) n(1.6 × 1012)]
2 (As internal energy is state function and does not
depend on path)
q = – 3 J (heat evolved), w = U – q = + 3 – (–3) = +
Q. 3 (3)
6 J)
G = H – TS
Thus, 6 J work will be done by the surrounding on the
= – 29.8 – 298 × (– 0.1)
gas.
= – 29.8 + 29.8  0
G = RT log KC
Q.9 (3)
0 = –2.303 × 8.314 × 298 log KC From 1st law :
0 = – 5705.84 log KC U = q + w
log KC = 0 For adiabatic process:
KC = antilog 0.0 = 1 q=0
KC = 1 U = w
Work involve in adiabatic process is at the expense
Q. 4 (4) of change in internal energy of the system.
G = H – TS
According to the above reaction if H > 0 and S > 0 Q.10 (2)
then the process is spontaneous at high temperature From the first law of thermodynamics,
and non spontaneous at low temperature. U = q + w

150 J EE C OMPENDIUM
 Thermodynamics
Now, for state A UAB = qAB + wAB  W1  nRT1 nV  nRT1 nV1
= 2 – 5 = – 3 kJ mol–1
W2  nRT2 nV  nRT2 nV2
For state A C, UABC = UAB + UBC
= – 3 – 5 = – 8 kJ mol–1 Slope of W2 > Slope of W1
As nRT2 > nRT1(T2 > T1)
UCBA = UABC C = – (– 8) = + 8 kJ mol –1
 The intercept of W2 is more negative than that of
As, internal energy is a state function, thus,
W1 because V2 > V1.
UCBA = UCA= + 8 kJ mol –1 and, UCA = qCA + WCA
8 = qCA + 3 qCA = 8 – 3 = + 5 kJ mol–1
Q.15 (4)
Q.11 (2)
H = U + ngRT S1 S2 S3 S4

H will be equal to U if , ng is zero, i.e., moles H 2 O(s)  H 2 O()  H 2 O()  H 2 O(g)  H 2 O(g)
gaseous reactants and products are equal. 1 kg 1 kg 1 kg 1 kg 1 kg
(a) 2NO2(g) N2O4(g) ; ng = 1 – 2 = – 1 at 273 K at 273 K at 373 K at 373 K
(b) 2HI(g) H2(g) + I2(g) ; ng = (1+ 1) – 2 = 0 at 383 K
(c) 2SO2(g) O2(g) +  2SO3(g) ; ng = 2 – (2 + 1) = –
1 s = s1 + s2 +s3 +s4
(d) N2(g) H2(g) 3(g) ; ng = 2 – (1 + 3) = – 2 334 373 2491 383
  4.2n   2n
273 273 373 373
Q. 12 (1)
 9.267 kJ Kg 1K 1
S(l)  S(g)
(f G° = 100.7 (f G° = 103
Q.16 (3)
kcal mol–1) kcal mol–1)
G = H – S
G° for this transformation is : For a spontaneous reaction, G = – ve thus, H < S
G° = 103 – 100.7 = 2.3 kcal mol–1 = 2.3 cal
H 200
mol –1 T, T
G° = – RT ln KP S 40
2.3 logKP  log KP = – 1 Thus, T should be greater than 5 K.
KP KPps = 0.1 atm
Q.17 (4)
N2(g) + 3H2 (g)  2NH3(g)
Q.13 (3)
N2(g) + 3H2  2NH3(g)
C6H6(l) + 15/2O2(g)  6CO2(g) + 3H2O(l)
ng = 6 – 7.5 = – 1.5 (change in gaseous mole) S  2SNH3   SN2  3SH2 
U or E = – 3263.9 kJ
there is decrease in number of moles of NH3 entropy
H = U + ngRT
is decreasing.
ng = – 1.5
R = 8.314 JK–1 mol–1 Q.18 (1)
T = 298 K G° = H° – TS°
So, H = –3263.9 +(–1.5) 8.314 × 10–3 × 298 G° = A – BT
= – 3267.6 kJ In endothermic reaction H = +ve. Hence, A = +ve
H = Heat at constant pressure
H/E = Heat at constant volume Q.19 (3)
R = gas cosntant In order to be spontaneous Gº should be –ve
G° = H° – TS°
Q.14 (1) 0 = 491.1 × 103 – T × 198
Let the gas is expanded form V1 to V at T1 and from V2 491100
to V at T2. T= = 2480
198
At T1 If temp is above 2480 K, the reaction will be
V spontaneous.
W1  nR T1  n  nR T   nV   nV1 
V1
Q.20 (1)
Similarly at T2
W2  nRT2 (nV  nV2 ) Q.21 (1)

C HEMISTRY 151
Thermodynamics
CP does not changes with change in pressure = –9 bar lit
= – 900 J
Q.22 (3) = –0.9 kJ
(A) q + w = U  definite quantity
(B) q  Path function Q.30 [–192.50]
(C) w  Path function C2H6(g) + 3.5O2(g)  2CO2(g) + 3H2O(I)
(D) H – TS = G  state function From the given data
2 × (–286) + 3 × (–393.5) – (–1560) = –572 – 1180.5
Q.23 (4) + 1560 = –192.50kJ/mol.

T2 1000 Q.31 [–2.70 to –2.70]


H  n Cp,m dT  3 
T1

300
(23  0.01T)dT H = U +  ngRT  (R  2cal k –1 mol 1 )
= 2.1 × 103 + 2(2) (300)
= 2100 + 1200
0.01
 3[ 23(1000 – 300)  (10002 – 3002 )] = 3300 cal
2 G = H – TS = 3300 – (300)(20) = 3300 – 6000 =
– 2700 cals = –2.7 kcal
 61950 J  62kJ
Correct option : (4) Q.32 (3)
dq
Q.24 (3) S  
T
For cyclic process : U = 0  q = – w
For isothermal process : U = 0  q = – w
T
ncdT
ST  
For adiabatic process : q = 0  U = W O
T
For isochoric process : w = 0  U = q
Q.33 [6.25 to 6.25]
Q.25 (2) U = nCvT
G = H – TS 5000 = 4 × CV ( (500 – 300)
for spontaneous process at all temp. G < 0 and it is Cv = 6.25 JK–1 mol–1
possible when H < 0 and S > 0.
Q.34 (1)
Q.26 (1) Pext = 0
U = q + w w = – Pext V
q = –2kJ, W = 10 kJ =0
U = 8kJ
Q.35 (2)
Q.27 (3) For 1 mole of ideal gas.
C7H16(  ) + 11O2(g)  7CO2(g) + 8H2O (  )  Both internal energy (U) and Enthalpy (H) depends
ng = np – nr = 7 – 11 = – 4 on temperature
 Compressibility factor Z = 1
 H= U + ngRT T
 H – U = – 4 RT  CP, m – CV,m = R
and dU = CV, mdT
Q.28 (4)
Q.36 (189494)
I2(s)  I2(g) : H1= 24 cal/g at 200º C
H2O(l)  H2O(g)
H2 H1 + CP rxn(T2–T1)
Hvap = U + ngRT
H2 H1 + CP (product) – CP(reactant) (T2–T1)
U = Hvap – RT
= 24 + (0.031 – 0.055) × 50
= 41,000–8.314 × 373 J mol–1
= 24 – 1.2
= 37898.878
= 22.8 cal/g
For 5 moles, U = 37898.878 × 5 J
= 189494 J
Q.29 (3)
W = –Pext (V2–V1)
Q.37 (–326400)
= – 1 bar × (10 – 1)lit
C2H5OH (l) +3O2(g)  2CO2 (g) + 3 H2O(l)

152 J EE C OMPENDIUM
 Thermodynamics
H = – 327 kcal; ng = – 1 1 8.314  298
H = U + ngRT = –744.24 + 
2 1000
U = – 327 + 2 × 10–3 × 300
= –744.24 + 1.24
= – 326.4 kcal
= – 326400 cal  –743 kJ/mole

Q.42 [673.4]
Q.38 [309.16 ]

S(g) + 6F(g) 
 SF6(g) Na(s) 
 Na (g) , H = 426.4 kJ / mole

H R = H f (SF6) – H f (S) – 6H f (F)

o o o o
1
Br ( )  
 Br (g) , H = 325kJ / mole
= (–1100) –(275) –6 (80) = – 1855 2 2
H R = –1855 = 0 – 6 (H So  F )
o
 
Na (g)  Br(g)  NaBr(s) , H   774.8kJ / mole
1855 kJ 1
H So  F = = 309.16 Na (s)  Br2 ()  NaBr(s) , H  ?
6 mole 2
 H = 426.4 – 325 – 774.8
Q.39 [200 K] = –673.4 kJ/mole
For spontaneous reaction G < 0
H – TS < 0 Q.43 [1380]
80,000 – (T) (2T) < 0 rG° = –RTlnKeq
2T2 > 80,000 = –R × 300 × 2 × 2.3
T2 > 40,000 = –1380 R
T > 200 K
 Ans. 200 K Q.44 [150.72]

Q.40 [15]
o
Go = G m  C6 H 6
 o
–3 G m C2 H 6
For isothermal expansion at constant pressure heat
= –1.4  – 3  2.4  105
105
gained by the system
= – 8.6  10 Joule
5
So
–2.303RT log10 k = –8.6  105
Q = – W (U = 0)
–2.303  8.314  298 log10 k = –8.6  105
 W = – PV
log10k = 150.72
 Q = + Pex (V2 – V1)

nRT nRT Q.45 [230]

V2 = P V1 = P1 3CaO + 2Al Al2O3 + 3Ca
2
H 0f  H 0f  Al2 O3   3H 0f (CaO)
1 1 = – 1675 – 3 (– 635)
 Q = Pex × n× R × T  P  P 
 2 1  H 0f  1675  3( 635)

 1 1  H 0f = 230kJ
Q = 4 . 3 × 5 × 8.314 × 293   
 1.3 2.1 
Q.46 [1]
Q = 15. 345 kJ Mol –1 (For five mole)
(A) Water 0 C ice; S = –ve
Q.41 [743] (B) Water 10  C
 ice; S = –ve
(C) N2(g) + 3H2(g) 2NH3(g); S = –ve
3
NH 2 CN(S) + O (g) 
 N 2 (g) + CO 2 (g) + (D) Adsorption; S = –ve
2 2
(E) NaCl(s) Na+(aq) + Cl–(aq); S = +ve
3 1
H2O ( ) ng = (1 + 1) – = Q.47 [31]
2 2
100 C,1bar
H = U + ng RT H 2 O(l )   H 2 O(g)
vap H = vap U + ngRT

C HEMISTRY 153
Thermodynamics
ng RT = 1 – 0 = 1
vap H – vap U = ngRT E = Internal energy change = ?
= 1 J/mol = J/mol So from equation (i)
41 = E + 1 × 8.3 × 10– 3 × 373
Q.48 [50] E = 41 – 3 = 38 kJ mol–1
q = 150 joules, W = – 200 joules
According to first law of thermodynamics,
Q.54 [964]
U = q + W = 150 + (– 200) = – 50 joule
FeO(s) + C(graphite)  Fe(s) + CO(g)
Q.49 [101] H°f (kJ/mol) – 266.3 0 0 –110.5
Enthalpy of fusion of a solid S(Jmol–1K –1 ) 57.49 5.74 27.28 197.6
Solid  Liquid ; H = 2.8 kJ mol–1 .... (i)
Enthalpy of vaporisation of a liquid H°(reaction) = (H°f(Fe) + H°f(CO) – H°f(FeO) + H°f(C))
Liquid Gas ; kJ mol–1 .... (i) = (0 – 110.5) – (– 266.3 + 0)
Add equation, (i) and (ii) = – 110.5 + 266.3 = 155.8 kJ/mol
Solid  Liquid ; H1 = 2.8 kJ mol–1 H°(reaction) = S°Fe + S°CO) – S°FeO + S°C)
Liquid  Gas ; H2 = 98.2 kJ mol–1 = (27.28 + 197.6) – 57.49 + 5.74)
Solid  Gas ; H = H2 + H2 = 161.65 J/mol-K
= 2.8 + 98.2 = 101 kJ mol–1
H 155.8 103 J / mol
Tmin. = = 
Q.50 [26] S 161.65J / mol  K
PV = nRT 1m3 = 1000 L
Volume = 4 L
Q.55 [82]
1 at m  4 L = n (CH4 )  0.083 L at m K–1 Millimoles of HCl = 200 m mol
mol–1  Millimoles of NaOH = 300 m mol
NaOH + HCl aCl
40  12
14103 1000 1 mol 1 mol 1 mol 1 mol
=
2 .4
0.083300 Hence, NaOH is the limiting reagent.
CH4(molar mass = 16) Energy evolved by 30 mmol = 30 kJ
weight of CH4 gas = kJ
Q = msT = 1713 J
4103 100016 1713 = 500 T
0.083300
1713
= 25.7  gram T = 500  4.18 = 0.8196 °C or  °C

Q.51 [21]
Heat of combustion per mol for Q.56 [5]
12 g = – 4.48 × 102 kJ.  N 2 O4(g)
2NO 2(g) 
2.48  10 2
G = H – TS
Heat of combustion for 1g graphite =
12 = – 57.8 kJ/mol – (– 176  kJ/mol)
= – 20.66 kJ  – 21 kJ = – 57.8 kJ/mol + 52.448 kJ/mol = – 5.35 kJ/mol

Q.52 [336] Q.57 [300]

G = – 49.4 kJ/mol G° = H° – TS° = 0 at equilibrium
H = 51.4 kJ/mol – 165 × 103 – T × (–505) = 0
G = H – TS T = 300 K
– 49400 = 51400 – 300 S = 300

100800 Q.58 (3)

S =  336 J k 1mol 1
300 Hr = (HC) reactant – (HC) product
= 3 [HC(C2H2,g)] – [HC (C6H6,)]
Q.53 [38] = 3 × (– 1300) – (–3268)
= – 3900 + 3268 = – 632 kJ/mole

H2O() 
H2O(g)
Hvap = 41 kj mol–1 Q.59 [38]
H = E + ng RT .......(i) T = 373 K

154 J EE C OMPENDIUM
 Thermodynamics
Given weight of water = 36 gm w = + 5J
36 U = – 200 + 5 = – 195J
Moles of water = = 2 moles
18
Given – vapH° = 41.1 kJ/mol Q.65 [117]
U = H – nR A/q  For 17 g (1 mole NH3) enthalpy change for
 vapourisation = 23.4 kJ mol–1
kJ mol–1 So for 85 (g) (5 mole NH3)
Value will be = 23.4 × 5 = 117 kJ
Q.60 (2)
(A) For spontaneous process  G T,P  0 (II) Q.66 [600]

(D) For exothermic process  H  0 1

(I) Mg(s)  O 2 (g)  MgO (s)
2
(B) For isothermal process  T  0 (III)
H = U + ngRT
For isobaric process  P  0
1
(C) H r   B.E  Re actants    B.E  Products  (IV) – 601.70 × 103 = U –  8.3  300
2
– 601.70kJ = U – 1.245 kJ
Q.61 [0] U = – 600.455 kJ
In case of free expansion, w = – (Pext   V)
Q.67 (3)
Pext = 0  w = 0 Given
First law of thermodynamics;   = q = w
H comb (C 2 H 6 ,g) = – 1560 kJ / mole
 = 0
 Hcomb (C) = – 394 kJ / mole
q = –w = 0
Amount of heat absorbed = 0  Hcomb H 2(g) = – 286.0 kJ / mole
7
Q.62 [51] (i) C2H6(g)+ O2(g)  2CO2(g) +3H2O ()c Ho = – 1560 kJ/
2
Pt(s) |H2(g)| H+(aq)||Ag+(aq)|Ag(s)
mole
E 0cell = + 0.5332 V.. Ag+ + e– g
(ii) C(s) + O2(g)  CO2 (g), H ocomb =–394 kJ / mole
fG0 = –nF E 0
cell
1
= – 1  (iii) H2 (g) + O (g)  H2O (g), Hocomb = – 286 kJ / mole
  kJ/mol. 2 2
= 51 kJ/mol. 2C(s) + 3H2(g)  C2H6(g) H orxn = H of (C2H6,g)

Q.63 [8630] H of = HoC (reactant) – HoC (Product)

n = 5; T = 300; V1 = 10L & V2 = 20 L. = (–394) × 2 + (–286) × 3 – (–1560)
v2  20  = –788 – 858 + 1560
W = –nRTln v = –5 by   = – 1646 + 1560
1  10 
= – 86.0 kJ / mol
= – 5 
J Q.68 [747]

Q.64 [195]  3O 2  g 

2O3  g  
2.2 1 t=0 (mole) 1 0
N 2 O moles = 
4.4 20 teq(mole) 1–0.5
H = nCpT = 1/2 × 100 (–40) = – 200 J 3
H = qp + w    0.5  0.75Mole
2
w = – Pext. DV
(=0.5)
(167.75 - 217.1) Total final moles = 1.25, Ptotal=1atm
W = -1 ×101.3J
1000 Partial pressure =mole fraction ×total pressure

C HEMISTRY 155
Thermodynamics

3
 0.75  Q.74 (1)
 1
 Po2 3
 1.25  H = U + PV
kp    1.35
 Po3 2  0.5 
1
2

 Q.75 [54]
 1.25  HNO3 + NaOH  NaNO3 + H2O
600 ml 400 ml
We know 
0.2M 0.1 M
G=–RT ln Kp mili moles of HNO3 = 600 × 0.2 = 120 m mol
G=–8.3×300 ln 1.35 mili moles of NaOH = 400 × 0.1 = 40 m mol
= –747 J mol = 747 HNO3 + NaOH  NaNO3 + H2O
120 40
Q.69 [2] 80 0 40
Cp,m = Cv,m + R After the reaction
 Cv,m = 20.785 – 8.314 = 12.471 Jk–1 ml–1  40 m moles = 40 × 10–3 moles are reacting
U = nCv,mT Enthalpy change for reaction
5000 25 rH = 40 × 10–3 × 57 × 103 J
 n   2 = 2280 J
12.471 200 12.471
C = Specific heat of water
M = mass of solution
Q.70 [2]
= density × volume
Ionisation energy of CH3COOH = 57.3 – 55.3 = 2 kJ
= 1 gm/ml × 1000 ml
= 1000 gm
Q.71 [200]
q = mcT  q = rH
C(s) + O2(g)  CO2(g) H = – x kJ/mol
2280 = 1000 × 4.2 × T
Q = C T = 20 × 2 = 40 kJ
T = 54.286 × 10–2k = 54.286 × 10–2 °C  54 × 10–
40kJ heat is released from 2.4 g C 2
°C
40  12
 For 1 mole C, Q = = 200 kJ/mol Q.76 (4)
2.4
Q = E = H = 200 kJ (ng = 0) 1
 x = 200 C(s) + O (g)  CO(g); H = –100KJ/mole
2 2
Q.72 [57] C(s) + O2(g)  CO2(g); H = –100KJ/mole
60 600  60
H2F2(g)   H2(g) + F2(g) Mass of carbon = (0.6× 103) = = 360
U = -59.6 kJ/mol, ng = 2 - 1 = 1 100 100
T = 27°C = 300 K gram
H = U + ngRT 360  60
= - 59.6 + 1 × 8.314 × 300 × 10–3 60% of carbon   216 gram
100
= - 59.6 + (8.314 × 0.3)
= - 57.10 kJ/mol 1
 - 57KJ/mol (1) C(s) + O CO(g); H = –100KJ/mole
2 2
Q.73 [35]  216  216
At constant volume  U   H = –100 × = –
 12  12
Heat capacity change in temp. 1800KJ/mole
u (kJ/Mol.) = No.of moles of gas (2) C(s) + O2 CO2(g); H = –400KJ/mole
T = 298.5 –298 = 0.45 K  144  144
Heat capacity (CV) = 2.5 kJ/K   H = –400 × = – 4800
 12  12
u = 9 KJ
KJ
2.5KJ / k  0.45k
9kJ = No . of moles of gase Total heat released = 1800 + 4800 = 6600 KJ

No. of moles of gas = 0.125 mol Q.77 (2)

Mass of gas = 280 x 0.125 = 33 gram Only (B) and (C) are correct
Ans: 35 (B) G = H – TS

156 J EE C OMPENDIUM
 Thermodynamics
At constant T 1  2  Isobaric process
G = H – TS 2  3  Isochoric process
(A) First law is given by 3  1  Isothermal process
U = Q + W
W = W12 + W23 + W31
If we apply constant P and recersible work.
U = Q – PV
   V2   
=  P  V2  V1   0  P1V1 ln  V   
(C) By definition of entropy change
dq rev    1  
dS =
T
At constant T    20   
=  1  40  20   0   1 20ln  40   
q rev     
S =
T = – 20 + 20 ln 2
(D) H = U + PV = – 20 + 20 × 2.3 × 0.3
For ideal gas
= – 6.2 bar L
H = U + nRT
At constant T |W| = 6.2 bar l = 620 J
H = U + nRT
Q.82 [499]
Q.78 [610] 2H2O(g)  2H2(g) + O2(g) +(242 × 2) kJ
–1
1 mol
Cl  Cl g   Clg   Claq. H2(g) + O2(g)  2OH
2 2 g  +78 kJ mol–1
H2(g)  2H +436 kJ mol–1
Hº=
1
× 240 + (– 350) + (–380) 2H2O  2H + 2OH +998 kJ mol–1
2
= – 610 ans. 1
H2O  H + OH 998 × = +499 kJ mol–1
2

Q.79 [12] Q.83 [1006]

millimole of NaOH = 0.24 × 25 (Bomb calorimeter  const volume
 millimole of acid = 0.24 × 25 Heat released
 mass of acid = 0.24 × 25 × 24.2 mg By combustion of 1 mole
for pure acid,
20  0.5
w C2H6 (U) =  × 30 = –1000 kJ
V= ; (d = 1.21 kg / L = 1.21 g / ml) 0.3
d
C2H6(g) + 7/2 O2(g)  2CO2(g) + 3H2O(l)
0.24  25  24.2 ng = 2 – (2 + 7/2) = - (7/2)
V= × 10–3
1.12 H = U + nRT
= 120 × 10-3 ml = –1000 –7/2 × 8.3 × 300 kJ
= 12 × 10-2 ml = –1000 – 6.225
= –1006 kJ
Q.80 [2] So heat released = 1006 kJ mol-1
G = H – TS
A : G (J mol–1) = –25 × 103 + 80 × 300 : –ve Q.84 [4]
B : G (J mol–1) = –22 × 103 – 40 × 300 : –ve Molar heat capacity, molarity, Eocell and molar mass are
C : G (J mol–1) = 25 × 103 + 300 × 50 : +ve intensive properties.
D : G (J mol–1) = 22 × 103 – 20 × 300 : +ve
Processes C and D are non-spontaneous. Q.85 [4]
(D) C (s) + O2(g)  CO2 (g)
Above reaction is combustion of Carbon and hence
Q.81 [620]
exothermic

C HEMISTRY 157
Thermodynamics
(E) Dissolution of Ammonium chloride in water is
–k
endothermic process. – 200 =
2
Q.86 [4] k= 400 = B.E. of A2 (in kJ/mol)
Fe2O3 + 2Al  2Fe + Al2O3
Q.92 [1411]
1 : 2
C2H4(g)3O2(g)  2CO2(g) + 2H2O(l )
H 0reaction  1700  (840) U = –1406 kJ mol–1
= –860 kJ H = U + ngRT
Mass ratio of Fe2O3 and Al
 1406 
 2   8.3  300
= 160 : 54 1000
= 2.96 in 214 gm mixture = –1406 – 4.98
Hº 860  –1411 kJ mol–1
   4 kJ/gram The minimum value of TS at equalibrium = H
1gm mixture 214
TS = –1411 kJ

Q.87 [1070] Q.93 [2]

H fus At point a : Slope = –ve
Melting point = dG = –ve
S
 spontaneous
Q.88 [130] At point b : Slope = 0
As per the quetion dG = 0
 equilibrium
300103 – Ea
600 R = Ae 300 R At point c: Slope = +ve
Ae
dG = +ve
103 Ea  non-spontaneous
 
2 300
Q.94 [10]
 Ea = 150 × 103J mol–1
Gº = Hº – TSº
 Ea = 150 kJ mol–1
 Activation energy of catalysed backward reaction 298(10)
= –54.07 –
= Ea – H 1000
= 150 – 20 = 130 kJ mol–1 = – 57.05 kJ/mole
Gº = –2.303 RT logKeq
Q.89 (2) – 57.05 × 1000 = –2.303 × 8.314 × 298 logKeq
Isotopes of hydrogen have almost same chemical –57.05 ×1000 = –5705 logKeq
properties, but rate will be differetn due to difference 10 = logKeq
in bond dissociation enthalpy.
Q.95 (3)
Q.90 [1] (A) 2CO (g) + O2(g)  2CO2 (g) H1 = –x kJ mol–1
For adiabatic system, heat will not escape and
temperature of system will rise. (B) C (graphite) + O2(g)  CO2(g) H 2 = –ykJmol–
For diathermic container, heat will escape the 1

container and hence temperature of container will Multiply eq - B by (2) and subtract eq. (A) from it
remain same. 2C(graphite) + O2 (g)  2CO (g) Ho = x – 2y
1 x  2y
Q.91 [400] C (graphite) + O2  CO Ho =
2 2
A2 + B2  2AB, H fº  –200 kJ mol –1

k Q.96 [03]
B.E. of A2 : B2 : AB = k : :k For isothermal process Q = – W
2
The W for isothermal reversible process is
H fº  [(BE of A 2 )  (B.E.of B2 ) – 2B.E.ofAB]
V2
W = –nRT In
 k  3k V1
=  k  – 2k   – 2k
 2  2

158 J EE C OMPENDIUM
 Thermodynamics

V2 q = 0, w = 0, U = 0, G = 0, Ssys = 0
ΔSsurrounding = –nR In
V1
Comprehension # 1 (Q. No. 4 to 5)
3 Q.4 (A)
= –1×8.314× 2.303× log
2 Let the heat capacity of insulated beaker be C.
= – 3.37 JK–1 Mass of aqueous content in expt. 1 = (100 + 100) × 1
= 200 g
 –3JK –1
 Total heat capacity = (C + 200 × 4.2) J/K
Note : - The given process is mentioned as isothermal Moles of acid, base neutralised in expt. 1 = 0.1 × 1 =
reversible process hence the Ssurrounding is calculated 0.1
accordingly. Heat released in expt. 1 = 0.1 × 57 = 5.7 KJ
5.7 × 1000 = (C + 200 × 4.2) × T.
JEE-ADVANCED
5.7 × 1000 = (C + 200 + 4.2) × 5.7
PREVIOUS YEAR’S (C + 200 × 4.2) = 1000
Q.1 (B) In second experiment,
For H2O()  H2O(g) at T = 100ºC, 1atm
equilibrium exists. G = 0, H – TS = 0 nCH3COOH  0.2, nNaOH  0.1
H = TS > 0 for system, since evaporation is Total mass of aqueous content = 200 g
endothermic Total heat capacity = (C + 200 × 4.2) = 1000
qsurr Heat released = 1000 × 5.6 = 5600 J.
 (S)system > 0, also (S)surrounding = T Overall, only 0.1 mol of CH 3 COOH undergo
surr
neutralization.
Heat gained by system = heat lost by surroundings
 qsurr. < 0  (S)surr. < 0 5600
 H neutralization of CH 3COOH = = –
0.1
Q.2 (A) (B) (C) 56000 J/mol
Since the vessel is thermally insulated so = – 56 KJ/mol.
q=0  Hionization of CH3COOH = 57 – 56 = 1 KJ/
pext = 0 , so w = 0 mol
so U = 0 (ideal gas)
Hence T = 0 Q.5 (B)
T = 0 Final solution contain 0.1 mole of CH3COOH and
T2 = T1 CH3COONa each.
P2V2 = P1V1 Hence it is a buffer solution.
The process is however adiabatic irriversible.
So we cannot apply P2V2 = P1V1 [CH3COO ]
pH = pKa + log
Hence ans is (A) , (B), (C) [CH3COOH]

Q.3 [(A-R,T) (B-P,Q,S) (C-P,Q,S) (D-P,Q,S,T)] 0.1

= 5–log 2 + log = 4.7
(A) H2O(  )  H2O(s) at 273 K. & 1 atm 0.1
H = – ve = q
Q.6 (C)
Ssys < 0, G = 0.
w  0 (as water expands on freezing), U
 Process is done against const. External P, process
will be irreversible.
 0
 Pext V2  V1 
(B) Free expansion of ideal gas.  “Ssure = =
T
q=0 w = 0 U = 0 Ssys > 0G < 0
3   2  1  101.3
(C) Mixing of equal volume of ideal gases at  1.013 J / K
300
constant pressure & temp in an isolated container
q = 0, w = 0, U = 0, Ssys > 0
Q.7 C)
G < 0
dG = VdP – SdT
At 298 K, SdT = 0
(D) H 2 (g) 300 K 
Re versible
Heating,1atm
 600 K  dG = VdP


Re versible
Cooling,1atm
 300 K.

C HEMISTRY 159
Thermodynamics

P P
(wrong)
qBC = HAC = nCP (T2 – T1)
 dG   VdP  G  G  V  P  1
#
WBC = – P2(V1 – V2) B
1 1
(correct)
[ Solids involved  V almost constant] # nCP (T1–T2) < nCV(T1 – T2) C (correct)
rG = [G°diamond + Vd (P – 1)] – [G°graphite +Vg(P – 1)] HCA < UCA
0 = 2.9 ×103 + (P – 1) 105 (–2 ×10–6) # D (wrong)
 P = 14501 bat
Q.11 (A,B)
Q.8 (A, B) Enthalpy of formation is defined as enthalpy change
for formation of 1 mole of substance from its ele-
H ments, present in their natural most stable form.
SSurr 
TSurr
Q.12 (A, B, C)
For endothermic, if Tsurr. increases, Ssurr will increases. For 1 mole Vander Waal's gas
For exothermic, if Tsurr. increases, Ssurr. will decreases.
RT a
P  2
Vb V
Q.9 (A, C, D)
If Pext=P, means process is reversible. For Vanderwaal
gas, expression is correct for all reversible process.
P
(P1,V1,T1 ) Q.13 [935.00]
reversible isothermal SnO2(S)+C(S)  Sn(S)+CO2(g)
reversible adiabatic Hºrxn=[–394]–[–581] =187 kJ/mole
(A)
Sºrxn=[52+210]–[56+6]
= 200J/k–mole
V2 V
Hº 187  1000
T   935K
Area under curve in reversible isothermal is more. So, Sº 200
more work will be done by gas.
(B) T1 = T2  U = nCVT = 0
In reversible adiabatic expansion, T2 < T1 Question Stem for Question Nos. 14 and 16
T= – ve  U = – ve Q.14 [166.28]
(C) In Free expansion, Pext = 0  W = 0
If carried out isothermally (U = 0)  q = 0 P
Gº = – RT In   = Hº – TSº
(Adiabatic) ; From I law 1
If carried out adiabatically (q = 0)  U = 0
(isothermal) ; From I law P H º Sº
In  =– 
P 1 RT R
(P1, V1) H º  4
Slope = – = 104 ×  
R  2
(D)
(P2, V2) Hº = 2 × 104 × R
= 166.28 kJ/mole
V
During irreversible compression, maximum work is Q.15 [141.33 or 141.34]
done on the gas (corresponding to shaded area)
104
Q.10 (B, C) From the plot when, = 10  T = 1000 K
AC  Isochoric
T
AB  Isothermal
BC  Isobaric
 P2 
In   =–3
# qAC = UBC = nCV (T2 – T1) 1
 V2  Substituting in equation
WAB = nRT1 ln  V  A
 1

160 J EE C OMPENDIUM
 Thermodynamics

 P2  H º Sº
In    –  disorder increases and hence, entropy increases.
1 RT R (D) For [Ni(H2O)6]2+ + 3en  [Ni(en)3]+3+6H2O,
Entropy increases when bidentate ligands replace
We get, monodentate ligands due to increase in the number
of molecules on the product side.
2  104  R Sº
–3= –  Hence, (B,C,D) are correct.
R  1000 R
Sº = 17R Q.20 [0.31]
Sº = 17 × 8.314 J/K-mol
Sº = 141.34 J/K-mol Q.21 [300]

Q.16 (A, B, D) Q.22 [7]

From state I to II (Reversible isothermal expansion)
P decreases, V increases, T constant Q.23 [8]
H constant & S increases.
From state II to III (Reversible adiabatic expansion)
P decreases, V increases, T decreases
H decreases, S constant
 Plots (A), (B), (D) are correct while (C) is wrong
as from II to III, H is decreasing.

Q.17 [10]

Q.18 {90.39}
2Hg(g) + O2(g) 2HgO(s)
Heat capacity of calorimeter = 20 kJ K–1
Rise in temperature = 14.8 K
Heat evolved = 20 × 14.8 = 296 kJ
H° = U° + ngRT
= –296 – 3 × 8.3 × 298 × 10–3
 –303.42 kJ
H° = Hf° (HgO(s)) – Hf° (Hg(g))
–303.42 = Hf° (HgO(s)) – 2 × 61.32
Hf° (HgO(s)) = –303.42 + 122.64 = –180.78 kJ
|Hf° (HgO(s))| = 90.39 kJ mol–1

Q.19 (B, C, D)
(A) M(s) + 2H+ (aq)  H2 (g) + M2+(aq)
dE cell R
if 
dT F
dE R
S  nF  2F    2R
dT F
2.303RT 0.01 2.303RT
(B) E cell  log 
F 0.1 F
dE cell 2.303R

dT F
dE
 S  nF 0
dT
It is an entropy driven process.
(C) It is correct
During racemisation of optically active compound,

C HEMISTRY 161