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Physical Chemistry UNIT 1

Section - A : Straight Objective Type

Number of moles of 200 ml of 3 M AgNO3 = 200 × 3 × 10–3
= 0.6
Number of moles of 300 ml of 2M AgNO3 = 300 × 10–3 × 2
= 0.6
 Total number of Ag + ions = 0.6 + 0.6
= 1.2 moles
Moles of Cl– released by 200 ml of 10 M
= 200 × 10 × 10–3
= 2 moles
1.2 moles of Ag+ will precipitate 1.2 moles of Cl–
The number of moles of NaCl left unprecipitated = 2 – 1.2 = 0.8 moles
Amount of NaCl left unprecipitated = 0.8 × (23 + 35.5)g = 46.8 g
1 ml H2O is equal to 1 g of H2O because density of water is 1 g/ml.
The change in oxidation number of Cr is +3 to +6. Total e– lost are 6. Hence, equivalent weight of
M
Cr2(SO4)3 = .
6

3% solution of H2O2 means
100 ml H2O2 solution — 3g H2O2
1000 ml H2O2 solution — 30g H2O2

234 22.4 L
at NTP

68 g of H2O2 liberates 22.4 L of O2

30 g of H2O2 liberates 9.88 L of O2
30 g of H2O2 = 1000 ml of H2O2 = 9.88 × 103 ml of O2
1 ml of H2O2 = 9.88 ml of O2
 volume strength = 9.88

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MgCO3 + 2 HCl  MgCl2 + CO2 + H2O
MgCl2 + HCl  no reaction
Now, 1 mole of MgCO3  1 mole of CO2
1 mole of CO2  1 mole of MgCO3

4 4
moles of CO2 = moles of MgCO3
44 44
= 0.09
= 0.09 × 84 g of MgCO3
= 7.64 g
 % of MgCO3 in the mixture = 38.2%
% of MgCl2 in the mixture = 61.8%

x
 1000
mol. wt. of KMnO 4 56
 60  N
5 5 .6

158 56
 60 
x 5 5 .6
1000

= 18.96 g

18.96
% purity of KMnO4 =  100  63.2%
30
100 g of solution contain 49 g of H2SO4

49
mol. weight of H2SO 4
 M  100
weight of solution
density

100  NH2SO4  50  12

NH2SO4  6N

6N H2SO4 = 3 M H2SO4

49
3  98  1000
100
d

49
 3  10  d
98
d = 0.6 g/ml

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0.395
Number of moles of KClO4 formed = (molar mass of KClO4 = 138.5)
138.5
= 2.85 × 10–3
Number of moles of KClO3 decomposed to give 2.85 × 10–3 moles of KClO4

4
=  2.85  10 3
3
= 3.8026 × 10–3 moles of KClO3
= 3.8026 × 10–3 × 122.5 g KClO3 = 0.466 g of KClO3
 Amount of KClO3 used in 1st reaction = 1.034 g of KClO3
= 8.44 × 10–3 moles of KClO3
Number of moles of O2 formed by 8.44 × 10–3 moles of KClO3

3
=  8.44  10 3
2
= 0.01266
Volume occupied by 0.01266 moles of O2 = 0.01266 × 22.4 L = 283.6 ml
5 FeC2O4 + 3 MnO4– + 24 H+  5 Fe3+ + 10 CO2 + 3 Mn2+ + 12 H2O
Molecular weight of FeC2O4 = 144 g

1
Number of moles in 1.44 g of FeC2O4 =  1.44 = 0.01 mole
144
From the above balanced equation
5 moles of FeC2O4 are oxidised by 3 moles of KMnO4

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

1000
=  0.006
0.01
= 600 ml
Milli equivalent of NaOH = x
Milli equivalent of Na2CO3 = y

y
x  50  0.2
2
2x + y = 10 × 2 = 20
x + y = 72 × 0.2
x + y = 14.4
 x = 20 – 14.4
= 5.6
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Number of milli equivalent of NaOH in 25 ml = 5.6

5.6  40
 Weight of NaOH in the solution = = 0.224 g
1000
y = 14.4 – 5.6 = 8.8
Number of milli equivalent of Na2CO3 in 25 ml of solution = 8.8

8.8  53
 Weight of Na2CO3 of solution =  0.4664 g
1000

WNaOH 0.224
   0.48
WNa2CO3 0.4664

KMnO
Fe2 
4 Fe3
No. of neutron in 1H2 = 1

4
No. of mole of 1H2  4
1

1 1 1
u= th wt. of C-12 atom = th wt. of O-16 atom = th wt. of C-14 atom
12 16 14
No. of moles of solute does not change on dilution.
Equal volume of gas must have same mole and entities.
Percentage by weight also can be calculated by the empirical formula.

1 5
No. of atom = 5   NA  NA
4 4

x A 1000
m 
xB 18

No. of moles of compound

x
Total no. of mole of solution
For 1 kg solvent

5.2 5.2
x   0.086
55.5  5.2 60.7

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No. of moles of Cl– 423 9

M    1.8
Total volume in litre 5 5
1000  0.8 400

46 23

20a. Answer (3) (AIEEE 2012)

As per Avogadro’s Law v  n (At constant P & T)
Sum of positive and negative charges should be equal.
 3(number of atoms of A) + 6 NB = 2 NC
 NA = 2
NB = 3
NC = 12
Hence A2(BC4)3
100 ml of 1 M Ca(OH)2 = 100 ml of 2 N Ca(OH)2
10 ml of 20 N H2SO4 = 100 ml of 2 N H2SO4
 100 ml of 1 M Ca(OH)2 will neutralize 10 ml of 20 N H2SO4 completely.
Thus, the resulting solution will be neutral.

24a. Answer (2) [JEE (Main)-2016]

Number of equilibrium of acid = Number of equilibrium of base

1
Given V.D. of A = ( V.D)B and molecular mass of B = x = 2 × V.D. of B
6
 Molecular mass of A = 2 × V.D. of A
1
= 2 VB
6
1
= 2  VB 
6
x
=
6
Molecular mass of CH3OH = 12 + 4 + 16 = 32

12
% of C in CH3OH =  100  37.5%
32

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12
% of C in CO2 =  100  27.27%
44

48
% of C in CH3CH CHCOOH =  100  55.8%
86

24
% of C in COOH–COOH =  26.6%
90

 (3) is the correct answer.

100 g of solution contain 40 g solute
1000 g of solution contain 400 g solute
Amount of solute left in solution after precipitation = 400 – 200 = 200 g
Weight of the solution after precipitation = 1000 – 200 = 800 g

200
% concentration of new solution =  100  25%
800

12 g of N in 100 g of compound

100
14 g of N in  14 g of compound
12
= 116.67 g

28a. Answer (2) [JEE(Main)-2016]

8 g sulphur present in 100 gm organic compounds
 32 g sulphur present in 400 gm of organic compound
Hence minimum molecular weight of compound = 400 g/mol

(170 ) ( 58.5 )

68 g of AgNO3 = 0.4 moles

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

21
84  1000  1.25 M
Molarity of the solution =
200

1.25 × 25 = x × 1250
x = 0.025 M

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1
100 × 0.5 + 200 × × 2 N = 600 × x
4
N
x = 0.25
4
20 ml of 0.25 N solution (acidic)  25 ml of 0.2 N acidic solution
10 ml of 0.2 N NaOH will neutralize 10 ml of 0.2 N acidic solution
 15 ml of solution will be left unneutralized
 Nature of solution = acidic.
50
32
The mole fraction of methanol = = 0.59
50 50

32 46

MgCO3  MgO CO 2
84 g 40

40
Weight of MgO =  42  20 g
84

35a. Answer (4) [JEE (Main)-2017]

M2CO3 + 2HCl  2MCl + H2O + CO2
nM2CO3  nCO2
1
 0.01186
MM2CO3
1
MM2CO3 = = 84.3 g/mol
0.01186

A=H B=N
AB3 = HN3 – acid
A3B = NH3 – base
MH2PO4 = M+ and H2PO4–  univalent metal
 Metal chloride = MCl
81.6
The number of atoms of A =  2.2988
35.5
18.4
The number of atoms of B =  1.15
16
 Mole formula = A2.2988 B1.15
= A1.99 B1
= A2B
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Amount of MgCl2 in the sample = 50% of 25 g
= 12.5 g
Molecular mass of MgCl2 = 24 + 35.5 × 2
= 24 + 71
= 95 g
95 g of MgCl2 = 24 g of Mg
12.5 g of MgCl2 = 3.157 g of Mg
Amount of MgSO4 in sample = 50% of 25 = 12.5 g
120 g of MgSO4  24 g of Mg

24
12.5 g of MgSO4 =  12.5 = 2.5 g of Mg
120

Total Mg in sample = 2.5 + 3.157 = 5.657 g

5.657
% of Mg in sample =  100  22.63%
25

The volume of NaOH neutralized by 30 ml of 0.1 N HCl
40 × 0.1 = 0.2 × x
x = 20 ml
The amount of NaOH left unneutralized by 0.1 N HCl
= 120 – 20
= 100 ml

 100 × 0.2 = 40 × NH2SO4

NH2SO4  0.5 N

0 .5
 Molarity of H2SO4 =  0.25 M
2

12
% composition of CH : C  100  92%
13

12 2
% composition of CH2O : C  100  40% H   100  6.7%
12  2  16 30

36
% composition of C3H6O : C  100  62%
36  6  16

36
% composition of C3H4O2 : C   100  50%
36  4  32

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Element Relative Relative Simplest whole

mass mole number ratio
6
C 6 = 0.5 1
12
1
H 1 =1 2
1
So, X = 1, Y = 2
Equation for combustion of CXHY

⎛ Y⎞ Y
C XHY  ⎜ X  ⎟ O2  XCO2  H2 O
⎝ 4⎠ 2
⎛ Y⎞
Oxygen atoms required = 2 ⎜ X  ⎟
⎝ 4⎠
As per information,

⎛ Y⎞
2 ⎜ X  ⎟  2Z
⎝ 4⎠
⎛ 2⎞
 ⎜1  ⎟  Z
⎝ 4⎠
 Z = 1.5
Molecule can be written
CXHYOZ
C1H2O3/2
 C2H4O3

0.26% zinc means 100 g of compound contains 0.26 g of zinc

100
 65.38 g of Zn is present in  65.38
0.26

= 25146

= 2.5146 × 104 g

The molecular mass of M(OH)2 = 171

x + 2(16 + 1) = 171

x = 171 – 34

= 137 g

137
 Equivalent mass of metal is =  68.5 g
2

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6 M = 12 N H2SO4

12 × 1 = 15 × NH2SO4

12
NH2SO 4 
15
= 0.8

 MH2SO4  0.4 M

V.D. of gas = 45 g
Molecular mass of gas = 90 g
90 g of a gas occupies 22.4 L

22.4
22.5 g of a gas occupies  22.5 = 5.6 L
90
0.01 M K2Cr2O7  0.06 N K2Cr2O7
W
0.06 × 50 =  1000
152
= 0.456 g
0.456
 % purity of sample =  38%
1 .2
The weight loss is due to the evolution of O2 gas
2 KClO3  2 KCl + 3O2
∵ 3 × 32 g O2 is obtained by 2 × 122.5 g KClO3

2  122 .5
 0.384 g O2 is obtained by  0.384 = 0.98 g KClO3
3  32

0.98
% of KClO3 decomposed =  100 = 10%
9 .8
Only Na2CO3 reacts with HCl.
M.e. of Na2CO3 = M.e. of HCl

W 1
 1000  100 
53 10
W = 0.53 g Na2CO3
So, weight of NaCl = 1 – 0.53 = 0.47 g

0.47
% of NaCl =  100  47%
1

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(109% of oleum means 109 g of H2SO4 formed when 100 g of oleum is diluted hence amount of water added
= 109 – 100 g = 9 g with water)

80 g 18 g

From above equation,

18 g of water combines with SO3 = 80 g
80
9 g of water combines with SO3 =  9  40
18
 % of SO3 = 40%
5.6 L of gas weighs 4.5 g

4.5
112 L of gas weighs  112
5 .6
= 90 g

12.25
0.5   1000 (x is the basicity)
98
x
500

x=2
 Acid has been neutralized to HPO42–.
The balanced chemical equation is

I2  10 HNO3  2 HIO 3  10 NO 2  4 H2O

1272 1063 g

254 g = 630 g
Thus, HNO3 required for 5 g iodine

630
=  5  12.4 g
254
5 3
AsO34  AsO33  nf  2 ; I  I2 nf  1

1.5  1022 1
n 23
 mole electrons
6.02  10 40

1
I  I2  e
2
1 1
mol mol
80 40

1
wt. of iodine = w = × 254 = 3.2 g
80

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11
2FeS2  O2  Fe2 O3  4 SO2
x mol 2 2x mol
11 x
mol
4

0.21 mol O2 = 1 mol air

11x 1 11x
⇒ mol O2    13.1 x
4 0.21 4

so, mol of air taken = 1.6 × 13.1 x = 21 x

mol of N2 present = 0.79 × 21 x = 16.6 x
mol of air left = 21 x – 2.75 x + 2x = 20.25 x

16.6 x
⇒ %N2   100  81.97%
20.25 x

Aufbau principle violated because ns should be preferentially full filled and only after that np should be filled.
In np the two electrons with same spin will have all the four quantum numbers same, hence 1 is incorrect.
Possible exchanges in 1 = 2
Possible exchanges in 2 = 10
Possible exchanges in 3 = 20
Possible exchanges in 4 = 16

z2
The number of revolution = 6.55 × 1015 ×
n3

12
= 6.55 × 1015 × = 2.43 × 1014
33

t  n3

t1 33 27
= 3 =
t2 4 64

There are 3 complete waves in figure, means it produces 3 waves.

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(KE)1 1 –  0 2x – 0
= =
(KE)2 2 – 0 3 x – 0

y 2x – 0
=
4y 3 x – 0

8x – 40 = 3x – 0
5x = 30
5x
0 =
3
Increase in photocurrent implies higher number of emitted electrons per second. Increase in frequency increases
the kinetic energy of emitted electrons only.
We know that 2rn = n
2rn 2.n2a0
= =
n n
= 2na0 = 8a0 (... n = 4)
Number of subshell = 2l + 1
... Each subshell contain 2 electrons.

Hence total number of electrons = 2 (2l + 1)

h
x . p 
4
h
0 . p 
4
h
p 
4 . 0
p 
Number of peaks = n – l
n
Exchange energy = nC2 .K = K
2 n–2

n (n – 1)
= K, where n = number of unpaired electrons having similar spin
2
Cu(29) = 1s2 2s2 2p6 3s2 3p6 4s2 3d9 (expected)
= 1s2 2s2 2p6 3s2 3p6 4s1 3d10 (Real)
Expected exchanges for 4s2 3d9 = 16
Real exchanges for 4s1 3d10 = 20

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The difference between energies of adjacent energy levels decreases as we move away from nucleus. Thus
in H-atoms.
(E2 – E1) > (E3 – E2) > (E4 – E3) ..................
For d orbital l = 2

h h h
orbital angular momentum = l (l  1) = 2 (2  1) = 6
2 2 2

4s 3d

1 6
s = 6 × = =3
2 2
Spin multiplicity = 2s + 1 = 2 × 3 + 1 = 7
Last electron is filled in 3d orbital.
Energy of unfilled orbital is decided by (n+l) rule
e– is excited to 3rd shell.
Work function of metal depend on ionisation energy.

p 2  4mp  2  ev 2 2
 
 2  mp .ev 1

Spin quantum number have no relation with probability.
All orbital in s orbital have zero orbital angular momentum.
In representation of , sign of wave function are shown.
1
n
⎞
4⎛
sin ⎜ ⎟
2
⎝ ⎠

e4 Z2
I.E.  
802h2n2
where  is reduced mass.

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Cu, Pf, Pd have abnormal E.C. in which Aufbau principle is voilated.
Cr have 3d5 electronic configuration.
Energy in H atom
RHhC R hC
– 2 =– H
n 9

n=3

3s 3p 3d

1 3 5
Total degeneracy = 1 + 3 + 5 = 9
dxy orbital lies in xy plane.
s orbital does not have angular nodes, only p and d orbitals have angular nodes.
Number of nodal planes l
for 4d, n = 4, l = 2
Number of nodal planes = 2
Spectrum depends on electronic environment of an atom.
Visible region belongs to Balmer series. Since the electron transition is from 5th energy level to 3rd energy level.
So no line obtained in Balmer series.
1s2 2s2 2p6 3s2 3p6
l = 0 for s subshell hence total number of electrons having l = 0 is 6.
After filling np level electron enters into (n + 1) s level.
Since 1s is lowest energy level hence it can absorb photon only but cannot emit it.

⎡ ⎤
1 ⎢ 1 1⎥ ⎡1 1 ⎤ R34

 max = RZ2 ⎢ 2 2 ⎥ = R (2)2 ⎢ – ⎥ = = 3R
⎣ n1 n2 ⎦ ⎣1 4 ⎦ 4

1
max =
3R

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h
=
mv
v=

h
Hence,  =
m
h
2 =
m

h
=
m
We know that,

nh
mvr =
2

nh
v=
2mr
frequency (number of revolutions per sec)

velocity
=
circumference
v
=
2 r

nh
= 2mr
2r

nh
= s–1
4  2mr 2

1
2p contains 6 electrons out of which only 3 electrons have spin – .
2

l varies from 0 to n – 1 and number of electrons in any energy level = 2 (2l + 1).

98a. Answer (4) [JEE (Main)-2016]

Number of orbitals associated with a shell
= n2
= 52 = 25

Number of orbitals = n2 = 52 = 25

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For n = 3, l  2.
Thus m cannot have value of 3.
Sc (21) = 1s2 2s2 2p6 3s2 3p6 4s2 3d1
Outermost electron lies in 4s.
Therefore

1
n = 4, l = 0, m = 0, s = ±
2

101a. Answer (1) [JEE (Main)-2014]

37  1s22s22p63s23p63d104s24p65s1
So last electron enters 5s orbital

1
Hence n = 5, l = 0, ml = 0, ms  
2

h
x.p 
4

h
x.m v 
4

h
v.mv 
4
h
(v)2 =
4m

h
v =
4m

h mh 1 mh
p = mv = m = =
4m 4 2 

m1 m2 m2 m
  
m1  m2 2m 2

RH
 Rydberg's constant 
2

n2
rn  0.53 Å
Z

L      1 

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Fact
Follow Schrodinger's wave equation.
From the data
Ionic radius of an element depend on the charge reside on that ion, effective nuclear charge and group to which
it belong.
If IE2 is 7 to 14 times of IE1, then that element will belong with Ist group.
IInd successive ionisation energy is always greater than Ist ionisation energy and difference between these two
differ for element to element.
Ga : 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p1
Ga belong with 13th group, 4th period and p block.
Ionisation energy  Electron affinity
Electronegativity =
2
van der Waal radius is larger than metallic radius because in metallic radius, atoms are closer to each other
because metallic bond is stronger than van der Waal bond.
In process of ionisation, energy have to be supplied to remove the outermost electron.
1. Electron affinity of noble gases is negative (means endothermic).
2. Addition of e– to anion is always endothermic.
3. The process of ionisation is endothermic.
Fact
IE1 of Be is more than I.E.1 of B.
I.E.  E.A.
E.N. 
2
Shielding power is s > p > d > f
Cu belong with XI group.
Fact

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Element Electronegativity
F 4.0
O 3.5
Cl 3.2
N 3.0
Charge per unit area is same
Mosley equation is as

  k(Z  b)
where b is screening constant.
Addition of e– in N is an endothermic process.
Fact
Gallium have smaller size than aluminium.

1
For isoelectronic species, size  .
Atomic number

130b. Answer (3) [JEE (Main)-2015]

Radius of N3–, O2– and F– follow order
N3– > O2– > F–
As per inequality only option (3) is correct
that is 1.71 Å, 1.40 Å and 1

130c. Answer (3) [JEE (Main)-2017]

Mg2+, Na+, O2– and F– all have 10 electrons each.

Energy have to be absorbed to increase the energy of the E.C. and decrease the stability.
With respect to oxygen valency along period generally increase.
Al2O3, SiO2, P4O10, SO3, Cl2O7
Polar bond is present between two atoms which have different electronegativity. If electronegativity is different,
then I.E. and E.A. should be different.
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Electronegativity of an atom depend on the electronic configuration, hybridisation and effective nuclear force.
Electron affinity of silicon is higher than carbon because of small size and high electron density of carbon.
Na + e–  Na– it is exothermic process while all other are endothermic process.
107 — Unnilseptium.
Technetium.
15th group element = P
16th group element = O
On basis of valency common formula P4O10.
Gallium have smaller size than aluminium this is called scandide contraction.
O > N > B > Be.
Take example of Al and O whose formula is Al2O3.
Mg < C (graphite) < B < Al
He is inert and has weakest van der Waal's forces.

146b. Answer (2) [JEE (Main)-2016]

ClF3, XeOF2 and XeF3 are sp3d hybridised with 2 lone pairs hence all have T-shape.

Bond order of C O is 3.5.
5
Bond order = = 1.67,
3
1
Charge per atom = – = – 0.33
3

O 2  O 2  O 2–  O 2–2
2 .5 2 1 .5 1

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149a. Answer (4) (AIEEE 2009)

Higher is the bond order, shorter is the bond length.

Bond order of O22 is 3.0.

sp3 hybridised carbon atom contains 75% p-character.
N  N, N  O+, C = C.

In KO2, O 2– contains one unpaired electron.

O

P—Cl
Cl Cl
H

54°44'
C H

H H
Due to intramolecular hydrogen bonding.
Its dipole moment is 3 D.
Due to see-saw shape.
14 carbon atoms are sp2 hybridised and 4 carbon atoms are sp3.

.. ..
O
H H

 obs
Percentage ionic character =  × 100
th

Fact.

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F F

F
F

Structure of I3–

I

Number of lone pairs in I3 is 9.

Due to pentagonal bipyramidal shape.

163a. Answer (1) (AIEEE 2011)

Hybridisation of iodine is sp 3d 3
So, structure is pentagonal bipyramid.

CH=CH2

Smaller halogen atom more possibility of back bonding.

F Cl

P F
F
Cl
Fact.
168. Answer (4 )
Larger anion, easier polarisation.

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Larger ionic radius, more ionic mobility (drift velocity per unit electric field).
ClF3 is T-shaped and other are pyramidal.
Cl F Cl F

P F , P Cl
Cl Cl
Cl F
>0  =0
Low heat of sublimation of metal, lower bond energy of non metal element, high lattice energy and high electron
affinity of non metal favour ionic bond formation.
Fact.
All peroxides are polar.
O 2–2 contains zero unpaired electrons.
O
||
P
O O
O
4- bonds O=P—O P=O
O O
P
||
O
1
Polarising power of cation 
Size of cation
Peroxide are diamagnetic

179a. Answer (1, 2) [JEE (Main)-2013]

The electronic configuration of the given diatomic molecules is
2 2 2 2 2 2
C2 : 1s *1s 2s *2s 2px 2py
2 2 2 2 2 2 2
N2 : 1s  *1s 2s  * 2s 2p 2p 2pz
x y

2 2 2 2 2 2 2 1 1
O2 : 1s  *1s 2s  * 2s 2pz 2p 2p  * 2p  * 2py
x y x

2 2
S2 : 1s  *1s 22s  *22s 22pz 2p
2 2
2p  *22p  *22py
x y x

 *22pz 3s
2 2
 *3s 2
3p 2 2  *13px  *13py
z 3p x 3p y

So, C2 and N2 are diamagnetic.

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179b. Answer (4) [JEE (Main)-2017]

CO has 14 electrons (even)  it is diamagnetic
NO has 15e–(odd)  it is paramagnetic and has 1 unpaired electron in 2p molecular orbital.
B 2 has 10e – (even) but still paramagnetic and has two unpaired electrons in 2p x and 2p y
(s-p mixing).
O2 has 16 e– (even) but still paramagnetic and has two unpaired electrons in *2px and *2py molecular
orbitals.

Cl

B
Cl Cl
Due to more negative charge on F–

181a. Answer (4) [JEE (Main)-2015]

H-bond is one of the dipole-dipole interaction and dependent on inverse cube of distance between the
molecules.

In Ar, London forces exist
When Z 7, sp mixing take place

BCl3  H2O  H3BO3  3HCl

In valence cell of S is 10e– are present.
Compound Bond angle
OF2 102
H2O 104.5
CH4 109.25
BCl3 120
Fact
O2[AsF6]   O2 + [AsF6] –
( 2.5 )

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190a. Answer (4) [JEE (Main)-2018]

Electronic configuration Bond order
2–1
He2  *  0.5
1s2 1s1 2
2–1
H2–  *  0.5
1s2 1s1 2
2–2
H2–
2  * 0
1s2 1s2 2
2–0
He22  1
1s2 2
Molecule having zero bond order will not be a viable molecule.

It is sp hybridised.
NO contains 15 electrons.
Both bond moments lie in same direction.
In pyrolle lone pair of N is resonance stabilised.
It is sp3 hybridised and tetrahedral.

195b. Answer (1) [JEE(Main)-2016]

In CH4, bond angle is highest


N
Fact.
LiH contains 76% (approx.) ionic character.
In aqueous medium movement of ion becomes easier.
Factual

In NO2 , there are no l.p – b.p repulsions and bond angle of O — N — O is 180º.

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201a. Answer (4) [JEE(Main)-2016]

Molecule/ion Hybridization

NO2– sp2

NO3– sp2

NO2 sp2

NO2 sp

In (3) there is maximum charge separation.
3 2 1 1
NH4  N2 H4  NH2 OH  N2 O
(1), (2) and (3) are unstable.
PV = nRT
He 1 × 2 = n1 × R × 300 …(i)
H2 1 × 2 = n2 × R × 300 …(ii)
Divide equation (i) by (ii)
n1
1
n2

n1 = n2
In vessel B, number of atoms will be 2 times that present in vessel A. Because H2 is diatomic while He is
monoatomic.
At constant pressure (parallel to V axis)
V1 > V 2 > V 3
Since V  T hence T1 > T2 > T3.

V
= constant
T

Charle’s law.
Molecular weight of C2H6 = 30 gm
Molecular weight of H2 = 2 gm
Since H2 is lighter hence it diffuses faster into balloon containing C2H6 hence balloon will be enlarged.

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W
PV = RT
M

200 0 .5
0.821   0.0821  400
1000 M

M = 100
Molecular weight of C2F4 = 2 × 12 + 4 × 19 = 100.

1
P
V
 (3) is not correct representation.
b = 4Vm
where Vm is volume of a gas molecule.

2 2 2 2
1 2 3 4 30
Vrms  =  7 .5 .
4 4

⎛ ⎞
⎜ P  a ⎟( V  b)  RT
⎜ 2⎟
⎝ V ⎠

If a and b are small they can be neglected

PV = RT
Which is equation of ideal gas.

213a. Answer (2) (AIEEE 2011)

Both a and b for Cl is more than C2H6.

If thermal energy >> molecular attraction then molecules will be largely separated and will be present in
gaseous state.

Force between two layers of liquid known as viscous force.

At low temperature and high pressure molecules of gas come closer and hence it favour liquefaction of gas.

2a
Ti 
Rb

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a
TB 
Rb

8a
TC 
27Rb

Ti
2
TB

Ti 2 54
   6.75
TC 8 8
27

TC 8
  0.296
TB 27

TB
 3.375
TC

TC
Hence T is least.
B

At high temperature gas approaches ideal behaviour and curve starts becoming flat.
Gas cannot be liquefied at a temperature higher than critical temperature and a pressure lower than critical
pressure.
3O2  2O3
Let x lit oxygen converted to ozone.

2
Volume of ozone produced = x
3
Volume of oxygen remaining = 1 – x

2
1 x  x  0.8 litre
3

x
1  0 .8
3

x
 1  0 . 8  0 .2
3
x = 0.6 litre

2
Volume of ozone =  0.6  0.4 litre
3
Volume of oxygen remaining = 1 – x = 1 – 0.6 = 0.4 litre.
Since volume are equal hence mole fraction of both will be 0.5.

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v 100
r=   10
t 10

x 100
(1)   2 .5
t 40

x 25
(2)   2 .5
t 10

x 100
(3)   10
t 10

x 5
(4)   2 .5
t 2
In option (3) rate of diffusion of O2 is same as that of rate of diffusion of H2 which is never possible because
H2 is lighter and O2 is heavier hence rate or diffusion of H2 will be faster and that of O2 will be slower.
Collision frequency  (pressure)2
Hence at 5 atm, collision frequency will be 25z.

8a
Tc 
27Rb

a
Vc = 3b and Pc  2 .
27b
At high temperature, a and b both negligible hence PV = RT.

224a. Answer (2) [JEE (Main)-2014]

PV
Compressibility factor (Z) 
RT
(For one mole of real gas)
van der Waal equation

a
(P  )(V  b)  RT
V2

At low pressure

V b  V

⎛ a ⎞
⎜⎝ P  2 ⎟⎠ V  RT
V

a
PV   RT
V

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a
PV  RT 
V

PV a
 1
RT VRT

a
So, Z  1
VRT

224b. Answer (2) [JEE (Main)-2016]

a
At high pressure can be neglected
V2

⎛ a ⎞
⎜ p + 2 ⎟ (Vm  b) = RT
⎝ Vm⎠

p(Vm – b) = RT

pb
Z = 1+
RT

At critical temperature density of liquid and gas phase become equal hence meniscus will disappear.

rA vA / t MB
 
rB vB / t MA

2 MB

1 MA

1 MA

2 MB

MA 1

MB 4

Pwet gas = Pdry gas + aqueous tension
Pdry gas = Pwet gas – aqueous tension.
PVm = RT

RT
Vm =
P
Vm will be maximum at higher temperature and lower pressure.

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At Boyle’s temperature, a real gas behave like ideal.
Vm, real > V m, ideal  Z > 1  repulsive forces are dominant this is only possible when gas is highly
compressed, for this experimental temperature should be more than Tc.
Z < 1  Intermolecular force of attraction is dominant, so liquefaction is possible.
‘a’ is large when force of attraction is large.

2a
Ti 
Rb
When temperature Texp < Ti, cooling occurs.
When Texp < Tc, repulsive forces do not develop.

2a 2  27
Ti    304.2  2053.3 K  1780.3C
Rb 8

8
Tc   33  9.8 K  263.2C
27
So, for liquefaction temperature must be maintained below –264°C.
2
⎛n⎞
Pressure correction  ⎜ ⎟
⎝v⎠
and P  n, so pressure correction increases with pressure.
PV = K
 log P + log V = log K
 log P = log K – log V (y = c + mx)
On comparing, m = –1 = tan 
  = tan–1(–1) = 135°
P1V1 P2 V2

T1 T2
PV = constant

1
d
V
At sea level pressure is more hence volume less and density more.

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Postulate of kinetic theory of gases.
3
KE = KT
2
T = constant
hence KE = constant
Postulate of kinetic theory of gases.
Due to viscous force (frictional force) liquid comes to rest.
At constant pressure the volume of a given sample of an ideal gas varies with temperature as follows
⎛ t ⎞
Vt  V0 ⎜1  ⎟
⎝ 273 ⎠
V = kT
log V = log T + log k
y = mx + c
m=1 c = log k
 graph (2) is correct.
Reciprocal of viscosity is called fluidity.
The film of a soap bubble has small thickness and there is air both inside and outside the film.

⎛ V⎞
P1  ⎜ ⎟
PV P1V ⎝ 2⎠
n  
RT1 RT1 RT2
P P1 P1 2PT2
⇒   or P1 
T1 T1 2T2 2T2  T1
P1V1 = P2V2
g(h1 + 10) × V = g × 10 × 8V. [∵ P = gh]
 h1 = 70 m
1
2x + y = 50 H2 + O  H 2O
2 2
5
15 mL O2 is in excess C 2H2 + O  2CO2 + H2O
x
2 2 2x

1
CO O2  CO2
y 2 y

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If during neutralisation acid/base or both are weak than it is possible.
For non spontaneity
G > 0
H – TS > 0
If H = +ve and S = –ve
Then, G = H – T (–S)
G = + H + TS
G = +ve
G > 0
When rod cools, energy is given to surrounding hence entropy of universe increase and entropy of rod
decreases.

⎛ E ⎞
For Ideal gas, ⎜ ⎟ = 0.
⎝ P ⎠ T

When T  0 Randomness is zero S = 0.
H = (Bond energy of Reactants) – (Bond energy of product)
= (BEH—H + BEO = O) – (2 × BEOH + BEO—O)
= (x + y) — (2w + z)
= x + y – 2w – z
Density is an intensive property as it does not depend upon amount of substance.
ng = (1 + 3) – 2 = 4 – 2
ng = 2
ng > 0
 H > E

9
C2H5SH + O 2  2CO 2  3H2 O  SO 2
2 ( g) (l) ( g)
( g)

At 298K, H2O will be in liquid state and CO2 and SO2 will be in gaseous state.
Entropy is a state function i.e. change in entropy depends upon the initial and final states of the system, not
on how that change is brought about.

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An increase in number of moles of gaseous phase shows more increase in entropy.
A reversible process is carried out infinitesimally slowly so that all changes occurring in the direct process
can be exactly reversed and the system remains almost in a state of equilibrium with the surrounding at every
state of the process.

C + 2H2  CH4 Ho = – 74.8 kJ mol–1

In order to calculate average energy for C—H bond formation we should know the following data. C(graphite) 
C(g), Ho = enthalpy of sublimation of carbon.

H2  2H Ho = Bond dissociation energy of H2.

( g) ( g)

If a gas was to expand by a certain volume reversibly, then it would do a certain amount of work on the
surrounding. If it was to expand irreversibly it would have to do the same amount of work on the surrounding
to expand in volume, but it would also have to do work against frictional forces. Therefore amount of work has
greater modulus but –ve sign.
WIrreversible > WReversible
(Tf)Irreversible > (Tf)Reversible

1
C O 2  CO 2
2
(s) ( g) ( g)

1 1
ng = 1 – =
2 2

1
H – U = ng RT = × R × 298 = 149R
2

268a. Answer (4) [JEE (Main)-2018]

15
C6H6 (l)  O2 (g)  6CO2 (g)  3H2O(l)
2
15 3
n g  6  
2 2
H = U + ngRT

⎛ 3⎞ 3
= 3263.9  ⎜  ⎟  8.314  298  10
⎝ 2⎠
= –3263.9 + (–3.71)
= –3267.6 kJ mol–1

As no heat can enter or leave the system work is done at the cost of internal energy which falls and so does
the temperature (joule Thomson effect).

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Bond energy of O—H bond = 109 kcal/mol means that when 1 mole of O—H bonds are formed, 109 kcal energy
is released (because dissociation of bond absorb energy). Formation of one mole of water is equivalent to
formation of 2 moles of O—H bond (H—O—H).
Hence energy released = 2 × 109 = 218 kcal.

270a. Answer (1) (AIEEE 2009)

I. H2O(l)  H+(aq) + OH–(aq); H = 57.32 kJ

1
II. H2(g) + O (g)  H2O(l); H = –286.20 kJ
2 2
Adding I & II we get,

1
H2(g) + O (g)  H+(aq) + OH–(aq)
2 2
H = 57.32 – 286.2
= –228.88 kJ

G = H – TS
The process would be
Reversible if G = – ve
Irreversible if G = +ve
Equilibrium if G = 0
Given H = – 25000 cal and S = 90 cal
at 300K, G = H – TS
= – 25000 – 300 × 90 = – 52000
G is –ve (reversible).

271a. Answer (2) [JEE(Main)-2016]

G = H – TS
If H and S are both positive, then G may be negative at high temperature hence reaction becomes
spontaneous at high temperature

For expansion against vacuum work done PdV = 0.
For expansion of an ideal gas the change in internal energy E = 0 as there is no force of attraction amongst
gas molecules or no work has to be done to overcome the intermolecular force. Under adiabatic condition no
heat enters or leaves this further confirms E = 0.
H = E + PV
H = 0 + 0 = 0
 H = 0
These are well known criterion of spontaneity.

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H – G 276.5 – 76.5 200 2

S = = = =
T 300 300 3

At equilibrium G = 0

H 276.5  3
Teq = = = 414.75 K
S 2

Adiabatic curve is more steeper.
At low temperature system is spontaneous.
Enthalpy change is path independent.
In Bomb calorimeter reaction is carried out at constant volume, V = 0 hence heat measured is E.
Variation of heat of reaction with temperature is known as Kirchhoff’s equation.
CH4 + 2O2   CO2 + 2H2O, H = x

3
CH3OH + O   CO2 + 2H2O, H = y
2 2

1
CH4 + O   CH3OH H = –ve
2 2
H = x – y = –ve
x–y<0
y > x
For endothermic reaction the minimum value of activation energy is equal to H.
Formation of oxides of Nitrogen is in general endothermic.
Since heat of neutralisation of strong acid and strong base is equal to formation of water.
NaOH + HCl  NaCl + H2O + q
where q = heat of neutralisation
Na+ + OH– + H+ + Cl–  Na+ + Cl– + H2O + q
H+ + OH–  H2O + q
G = H – TS
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Qrev – Wrev
S = =
T T

P1
nRT ln
S = P2
T

P1
S = nR ln P
2

Fact.
Factual
P1V1 = P2V2

3  2.5
P2   15 bar
0.5
W = –Pext V = –15 × (–2.0) = 30 dm3 bar

288a. Answer (2) [JEE(Main)-2016]



2H2O2(l) 
 2H2O(l) + O2(g)
w = – Pext (4V)

= – nO2 RT

= – 124.5 kJ
work done by O2(g) = 124.5 kJ

228
P–H bond energy =  76 kcal / mol1
3

H H
P P
H H
4(P – H) + (P – P) = 355
or 4 × 76 + (P – P) = 355
 (P – P) .E = 51 kcal/mol–1

R
Cp – Cv = R  Cv 
 1

nR
∫ dW  nC ∫ dT    1 T  T 
v 2 1

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For occurrence of a reaction,
(rH – TrS) < 0
 rH < TrS

283
 T  103
87
 T > 3253 K (2980°C)

291a. Answer (4) [JEE (Main)-2016]

G° = H° – TS°
= – 29.8 + 298 × 0.1
= – 29.8 + 29.8 = 0
Apply relation between G° and Keq

K eq  1

 2NO (g)

2NO(g) + O2(g)  2

 G 
°
reaction ⎣ 
= ⎡⎢ G° ⎤
⎥product
formation ⎦

– ⎡⎢ G  ° ⎤
⎣ formation ⎥
⎦reactant

⇒ –RT ln K P = 2×  G°  – 2  G ° 
NO 2 NO

⇒  G °   2  G °   RT ln K P
NO 2 NO

2×86600 – R  298  ln K P
⇒ G  °
NO 2
=
2

2

= 0.5 ⎡⎣ 2×86,600 – R  298  ln1.6×1012 ⎤⎦

Amount of heat released
3.6
=  (393.5)  103 J
12
= 1.18 × 105 J

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293a. Answer (1) [JEE (Main)-2014]

C2H5OH(l) + 3O2(g)  2CO2(g) + 3H2O(l)
Bomb calorimeter gives U of the reaction
So, as per question
U = –1364.47 kJ mol–1
ng = –1
H = U + ngRT

1  8.314  298
 1364.47 
1000
= –1366.93 kJ mol–1

= rG + 0

kf
K  1
kb

fH H+(aq) = 0 , others are not in standard state.

Let B.EC–H = x, B.EC–C = y
4x = 360 …(1)
6x + y = 620
 y = (620 – 540) = 80
Number of eqs. of KOH = 1
For maximum heat, there must be complete neutralisation.
 Number of eqs. of H2SO4 = (0.5 × 2) V
 V = (0.5 × 2) V
 V = V

57.1 kJ
t 
mc

S = 2.303nR log 10
= 2.303 × 2 × 8.314
= 38.29 JK–1

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298a. Answer (2) (AIEEE 2011)

V2
S  nRln
V1
100
S  2.303  2  8.314 log
10
S = 38.3 J/mole/K

H2O(l), 10C 
S

 H2O(l),0C  H2O(s),0C
1 S2

S = S1 + S2

273 ⎛ 1440 ⎞
= 2  2  2.303 log 2⎜ ⎟
283 ⎝ 273 ⎠
= –11.84 cal K–1

fHC2H6(g) = Eqn. (3) × 3 + Eqn. (2) × 2 – Eqn. (1)

= 312 + 342 – 681.8
= –27.8

1
Wirr = 2(70  20)  101 = –2416 cal
4.18

Wirr  Pext. (Vf  Vi )

E remains constant, as it is a state function.

4763.9 ⎞
K = 5.88 × 10–2 exp ⎛⎜ –
⎝ 8.314  573 ⎟⎠

ln 2
⇒ t1   35 s
2
K

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⎛ E⎞
S  nF ⎜  2  96500  1.5  104 = 28.95 JK–1 mol–1
⎝  T ⎟⎠ P

1st I.E. is for gaseous atoms only.
In free expansion, W.D = 0.
Fact.

1
H2(g) + S (g) H2S(g) K1 ...(I)
2 2
H2(g) + Br2(g) 2HBr(g) K2 ...(II)

1
Br2(g) + H2S(g) 2HBr(g) + S (g) K ...(III)
2 2
(III) = (II) – (I)

K2
K= K
1

309a. Answer (3) (AIEEE 2012)

1
HgO(s) Hg(g) + O (g)
2 2
Total pressure at equilibrium = P
Molar ratio of Hg : O2 = 2 : 1

2 1
PHg = P PO2 = P
3 3

1/ 2

KP = PHg × PO2   1/ 2 ⎛2 ⎞ ⎛1 ⎞
= ⎜ P⎟ ⎜ P⎟
⎝3 ⎠ ⎝3 ⎠

2
KP = P3/2
33 / 2

N2O 4 (g) 2NO 2 ( g) KP  2

1–  2 at equilibrium

P at equilibrium = 0.5 atm

1– 
pN2O4 = × 0.5 atm
1 
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2
pNO2 = × 0.5 atm
1 

pN2 O
2
KP =
p N2 O 4

2
4 2 (0.5)2 (1   ) 2
2=  =
(1   )2 (1 –  )  0.5 1 – 2

1 – 2 = 2
22 = 1

1
2 =
2
 = 0.707
  = 71%

CO  Cl2 COCl2
0.1 0 .1 0.3
0.5 0.5 0.5

0.3
0.5
KC = = 15
0.1 0.1

5 5

More the value of equillibrium constant less is the stability of the oxide of nitrogen.

KP = KC (RT ) ng

CO(g) + Cl2(g) COCl2(g)

ng = np – nr = 1 – 2 = – 1

KP 1
= (RT)–1 =
KC RT

314a. Answer (2) [JEE (Main)-2014]

1
SO2 (g)  O (g)  SO3 (g)
2 2
KP = KC(RT)x

x = ng = no. of gaseous moles in product – no. of gaseous moles in reactant

⎛ 1⎞ 3 1
= 1  ⎜⎝ 1  ⎟⎠  1  
2 2 2

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AgCl(s) Ag+(aq) + Cl–(aq) ...(i)
Ag+ + 2NH3 [Ag (NH3)2]+ ...(ii)
Due to removal of Ag+ through reaction (ii), equilibrium (i) shifts in forward direction.
At 25°C pKb for NH3 = 4.7 (in aqueous solution)
[NH4Cl] = 0.1 M
[NH3] = 0.01 M
for basic buffer

[conjugate acid B] 0 .1
pOH = pKb + log = 4.7 + log = 4.7 + log 10 = 5.7
[ weak base BOH] 0.01
pH + pOH = 14
pH = 14 – 5.7 = 8.3

316a. Answer (4) [JEE (Main)-2017]

1 1
pH = 7 +
2
 pK a – pK b  = 7 +  3.2 – 3.4 = 6.9
2

1 0
N2O 4 (g) 2NO 2 (g)
1 – 0.2 0 .4
Total moles at equilibrium = 1.2
at t = 0, PV = nRT
1 × V = 1 × RT1
V = RT1
at equilibrium
P2V = n2RT2

1.2 1.2 1.2  600

P2 = RT2 = RT × RT2 = = 2.4 atm
V 1 300
Fact.
Solution will be neutral hence pH = 7.
[Sr2+] [Cl–]2
(IP)  KSP
2
⎛1 –2 ⎞ ⎛ 1 –3 ⎞
IP = ⎜  10 ⎟ ⎜  10 ⎟
⎝2 ⎠ ⎝2 ⎠

1
 IP = × 10–8 which is greater than KSP.
8
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pH = 13
[H+] = 10–13 mole ion/lit
1 mole ion have = 6 × 1023 ions
1 × 10–13 mole ion have = 6 × 1023 × 1 × 10–13
= 6 × 1010 ions per litre
Hence number of ions in 1 ml solution = 6 × 107.
Aqueous solution of FeCl3 is acidic, as on hydrolysis it produces H+ ions according to following equation
Fe+3 + H2O [Fe(OH)2]+2 + H+
This is known as cationic hydrolysis.

Ag2CrO4 2 Ag+ + CrO4–2

According to this equation the concentration of CrO4–2 ions will be half of concentration of Ag+ ions.

323a. Answer (1) (AIEEE 2009)

[ CO32 ] = 10–4 M

Ksp [BaCO3] = [Ba2+] [ CO32 ]

K sp 5.1 109
 [Ba2+] = = = 5.1 × 10–5 M
[CO32 ] 104

323b. Answer (3) [JEE (Main)-2018]

[50  1]
Final concentration of [SO4– –] = = 0.1 M

Ksp of BaSO4,
[Ba2+][SO42–] = 1 × 10–10

10 10
[Ba2+][0.1] = = 10–9 M
0.1
Concentration of Ba2+ in final solution = 10–9 M
Concentration of Ba2+ in the original solution.
M1V1 = M2V2
M1 (500 – 50) = 10–9 (500)
M1 = 1.11 × 10–9 M
So, option (3) is correct.

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The pH of Buffer is given by

[Salt]
pH = pKa + log10
[ Acid]

pKa = 4.76
[Acid] = 10 ml of 1.0 M
[Salt] = 20 ml of 0.5 M
But total volume is made up 100 ml
[Acid] = 0.1 M
[Salt] = 0.1 M
[Acid] = [Salt]
pH = pKa
Hence pH of Buffer solution will be 4.76.
Each reaction has a definite value of the rate constant at a particular temperature i.e. KP is constant at constant
temperature.
Backward reaction is dissociation reaction and hence endothermic. The forward reaction will therefore be
exothermic. Further it is acccompanied by decrease in number of gaseous moles. Hence its equilibrium will
be affected by temperature and pressure.

t0 5 5 0
2SO 2  O2 2SO 3
60 3
at equilibrium 5 – 5 5 – 1 .5
100
5–3  3 .5
2

t0 1 mole 1 mole

P4 (s)  6Cl2 (g) 4PCl 3 ( g)
at equilibrium 1 – x 1 – 6x 4x
1 – x  1 – 6x

The reaction in which value of K is more goes fastest to completion.
On doubling the volume, pressure decreases and the reaction shifts in the direction of increasing number of
moles.

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3
⎡4⎤
[C]3 ⎢2⎥
⎣ ⎦
Q= = = 16
[ A ] [B] 1 2

2 2

Given KC = 20 here QC < KC rxn will be forward.

Thus to have Q = KC. The concentration of C must increase i.e. reaction should proceed from left to right.

331a. Answer (2) [JEE (Main)-2015]



 B + C, G° = 2494.2 J
2A 

As we know G° = –2.303 RT logKC

 2494.2 = –2.303 × 8.314 × 300 log KC
 –0.434 = log KC
 KC = anti log (–0.434)
 KC = 0.367

1 1
Now  A  = , B = 2 and C =
2 2

1
⎛ ⎞
 CB  ⎜⎝ 2 ⎟⎠
 2
Now QC = = =4
 A 2 ⎛ 1⎞
2

⎜ ⎟
⎝2⎠

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

pH = 12
pOH = 2
[OH–] = 10–2 M

10 –2
Ca(OH)2 = M = 10–2 N
2
= 10–1 equivalent in 100 ml = 1 milliequivalent
K for the reaction is given by K = [CO2]
Because concentration of solids taken to be unity. Since [CaCO3] and [CaO] do not figure in the expression
there will be no effect of addition of CaCO3.

0 .1 0.03 0 0 0
2KCN  AgNO 3  Ag(CN)2–  KNO 3  K 
0.1 — 0.06 0 0.03 0.03 0.03

[Ag(CN)2]– = 0.03

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0.03 0 0.04

Now [ Ag(CN)2 ] – Ag  2CN– (left from KCN)
0.03 – a a 0.04  a
 0.03  0.04

(0.04)2  a
KC = 4 × 10–19 =
0.03
a = 7.5 × 10–18

Initial 0 .2 0 .6 0
N2  3H2 2NH3
At equilibrium 0.2 – a 0.6 – 3a 2a

0.8  40 0.8  40 1
Total mixture is 0.8, 40% of its reacts i.e. reacts to give  mole of NH3 or NH3 formed
100 100 2
is 0.16 mole
2a = 0.16
a = 0.08
Initial mole = 0.8
Final mole = (0.2 – 0.08) + (0.6 – 0.24) + 0.16
= 0.12 + 0.36 + 0.16 = 0.64

0.64 4
Ratio of final to initial mole = = 0.8 =
0 .8 5

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

1
x H2S = x NH3 =
2

P
pH2S = pNH3 =
2

p2
KP = pNH3 × pH2S = = 64
4
p2 = 256
p = 16 atm.

336a. Answer (3) [JEE (Main)-2016]



 X(g)  Y(g)
XY(s) 
P P

2P = 10 bar, KP = P2 = 25

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CuS Cu+2 + S–2
Ksp [CuS] = S2 = 10–31
S = 3.16 × 10–16
Ag2S 2Ag+ + S–2
KSP (Ag2S) = (2S)2 × S = 4S3 = 10–44
S = 1.36 × 10–15 = 13.6 × 10–16
HgS Hg+2 + S–2
KSP (HgS) = S2 = 10–54
S = 1 × 10–27
At 50% neutralisation
[CH3COOH] = [CH3COONa]
pKa = 14 – pKb = 4.74
pH = pKa = 4.74
At complete neutralisation CH3COONa solution is alkaline due to hydrolysis and concentration is halved due
to dilution by equal volume NaOH.

0.01
Hence [CH3COONa] = M
2
pKa log C
pH = 7 + +
2 2
log 0.005
= 7 + 2.37 + = 8.22
2

Weak acid Weak base Salt

HA + BOH  BA + H2O

B + A– + H2O   BOH + HA
C (1 – h) C (1 – h) Ch Ch
mol / L mol / L mol / L mol / L
h2 Kw
Kh = , Kh =
(1 – h) 2 (1 – h) 2
1  10 –14 h2
=
5  10 – 7  5  10 – 7 (1 – h)2

1 10 –7 h
–7 =
5  10 1– h
5h = 1 – h
1
h =
6
h = 0.166
 h = 16.6%

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C = 0.1

HA H + A –
C (1 –  ) C C

pH = – log10 [H+]
2 = – log10 C
2 = – log10 0.1
log10 0.1 = –2
0.1  = 10–2

10 –2
= = 10–1 = 0.1
10 –1

340a. Answer (2) (AIEEE 2012)

... n = 0 for H + I 2HI
g 2 2

hence this reaction will be not influenced by changing volume.

A & C are weak base and it salt with strong base hence will form basic buffer.
At the half neutralisation point of an acid pH = pKa.
H2 + I2 2HI

[HI] 2
K=
[H2 ] [I2 ]

At the initial number of moles of H2 and I2 were same therefore at equilibrium [H2] = [I2]

[HI] 2
47.6 = K =
[I2 ] 2

[I2]2 < [HI]2
[I2] < [HI]

344a. Answer (2) [JEE(Main)-2016]

A  B  C  D
Initially : 1 1 1 1 [D]eq = 1.818 M
Q=1
Q < keq

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 Equilibrium is forward shifted.

A  B  C  D
Equilibrium : 1–x 1–x 1+x 1+x

(1  x)2
 102
(1  x)2

1 x
 = 10
1 x
 1 + x = 10 – 10x
 11x = 9

9
 x= = 0.818
11
So, equilibrium concentration of 'D' = 1.818 M.

PPCl3  PCl2
PCl5(g) PCl3(g) + Cl2(g) KP =
PPCl5

PCO  PCl2
COCl2(g) CO(g) + Cl2(g) KP =
PCOCl2

If CO is introduced, the dissociation of COCl2 will decrease and PCl2 will decrease. This will favour dissociation
of PCl5 because both reactions are attained in same vessel.

t0 1 0
N2 O 4 2 NO 2
t  eq 1 – x 2x

Total moles at equilibrium = 1 – x + 2x = 1 + x

2x = 50% of 1 + x
2x = 0.5 (1 + x)
2x = 0.5 + 0.5 x
x = 0.33

[NO2 ]2 0.66  0.66 0.66  0.66

KC = = =
[N2O 4 ] 1 – 0.33 0.66

KC = 0.66
40 ml of 0.1 M ammonia solution = 40 × 0.1
= 4 milliequivalent ammonia solution
20 ml of 0.1 M HCl = 20 × 0.1

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= 2 milliequivalent of HCl
4 2 0
NH4 OH  HCl  NH4 Cl  H2O
4–2 0 2
2

[NH4 Cl] 2
pOH = pKb + log [NH OH] = 4.74 + log = 4.74
4 2
pH = 14 – 4.74 = 9.26
[Ag(H2O)2]+(aq) + NH3(aq) [Ag(NH3)(aq) (H2O)]+ + H2O(I) ...(1)
K1 = 2.0 × 103
[Ag(NH3) (H2O)]+ + NH3(aq) [Ag(NH3)2]+(aq) + H2O(aq) ...(2)
K2 = 8.3 × 103
adding (1) and (2)
[Ag(H2O)2]+(aq) + 2NH3(aq) [Ag(NH3)2]+(aq) + 2H2O(I) : K
On addition of reactions equilibrium constants are multiplied
K = K1K2 = 2 × 103 × 8.3 × 103 = 16.6 × 106
HCl ionises as
HCl  
 H+ + Cl–

 2H+ + SO 4–2
H2SO4  
Since pH of both is same, H+ concentration has to be equated.
Hence 0.1M  0.05 M H2SO4
AgCl Ag+ + Cl–
KSP = S2

S= K SP = 1.5  10 –10

S = 1.225 × 10–5 g-molecule/litre

= 1.225 × 10–5 × 143.5 g/litre
= 17.58 × 10–4 g/litre

Kw 1  10 –14
Kn = K = = 2 × 10–10
a 5  10 – 5

0.02
ASC– + H2O HASC  OH –
x x
0.02 – x
 0.02

[HASC][OH– ] x.x x2
Kn = – = =
[ ASC ] 0.02 – x 0.02

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x2
2 × 10–10 =
0.02
x = 2 × 10–6
[OH–] = 2 × 10–6

1  10 –14
[H+] = = 5 × 10–9
2  10 – 6

pH + pOH = 14
12 + pOH = 14
pOH = 2
[OH–] = 10–2 mole/litre

10 –2
Number of OH– in 250 ml =
4
= 0.25 × 10–2 = 2.5 × 10–3
1
Soluble mole of Ca(OH)2 = × 2.5 × 10–3 = 1.25 × 10–3
2

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

1 mole 0 0

NH2 COONH 4 2NH3  CO 2
1–  2 
Total number of moles = 1 –  + 2 +  = 1 + 2
Average molar mass = 2 × 16 = 32

(1 –  )  78  (2  17)    44
32 =
1  2

78 – 78  34  44 78

32 = =
1  2 1  2

32 + 64 = 78
 = 0.71875 = 0.72
[Ag2O](s) = [Ag](s) = 1
KP = p O 2

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1
pH = pKW (for pure H2O)
2

1
pH = × 13.26 = 6.63
2

Value of KSP of AgI is lower than that of AgCl.

CO (Carbon monoxide) is a lewis base. The C atom tends to donate a pair of e–.

Ans-(4) BCl3 and AlCl3

SiCl4 can accept lone pair of electron in d-orbital of silicon hence it can act as Lewis acid.

* Although the most suitable answer is (4). However, both option (4) & (2) can be considered as correct
e.g. hydrolysis of SiCl4
Cl Cl
H
Si + H2O Si O
Cl Cl Cl H
Cl
Cl Cl

Cl
Cl Si OH + HCl
Cl
Hence option (2), AlCl3 and SiCl4 is also correct.

0.1435
Moles of AgCl formed =  103 mole
143.5

eq. of H2SO4 present = 2 × 10–3 – 10–3 = 10–3

= 5 × 10–4 moles

1000
 Strength of H2SO4 = 5  10 4  98   2.45 gL1
20

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54 Physical Chemistry Success Achiever (Solutions)

1
H2 O  H2  O2
2
1 0 0

1  
2

∑ n  1
2

2 1    2 
XH2O  ; XH2  ; XO2 
2   2   2  

PH2  PO1/22
KP 
PH2O

1
1
⎛ 2 ⎞ ⎛  ⎞2
⎜⎝ ⎟  P  ⎜⎝ ⎟  P2 3/2 P1/2
2  ⎠ 2  ⎠
⇒ KP  
2 1  1  2  1/2
P
 2  

1 3
N2  H2  NH3 , n  1
2 2

H 2 ⎡⎣S2 ⎤⎦
k1k 2 
H2S

 0.12  S2 
1021  ⇒  S2    10 20
0.1

362a. Answer (2) [JEE (Main)-2018]

In presence of external H+,


  2
 2H  S , K a 1  K a2  K eq
H2S 

H 2 S2 
  1 10 7  1.2  1013
H2S
0.22 S2 
 1.2  10 20
0.1
[S2–] = 3 × 10–20

NH4Cl is the salt of weaker base and strong acid, so will be acidic. NaCl neutral and NaCN will be basic as
this is the salt of strong base and weak acid HCN.

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363a. Answer (2) [JEE (Main)-2018]

CH3COOK + H2O  CH3COOH + KOH
Basic
FeCl3 – Acidic solution
Al(CN)3 – Salt of weak acid and weak base
Pb(CH3COO)2 – Salt of weak acid and weak base
CH3COOK is salt of weak acid and strong base.
Hence solution of CH3COOK is basic.

Ksp = 22  33  S2+3 = 108(S)5

HCO3  H 


 H2CO3

and HCO3 


  2
 H  CO3

s1 K a1 s1 10 4 103
 ⇒  
s2 K a2 s2 4  10 10 2

Ksp = 10–11 = [Mg2+][OH–]2 = 0.1[OH–]2
 [OH–] = 10–5 (Minimum conc. for precipitation)
 pH = 9
In water, solubility will be maximum as in other cases, there is common-ion effect. In 0.05 M AgNO3, it will
be least.
Q < K  Reaction goes forward

⎛ 11.45  103 ⎞
Kc = ⎜  103 mole/L
⎜ 8.314  298 ⎟⎟
⎝ ⎠
= 4.6 × 10–3 M

1
K p =
(K p )2
1
=
(4  103 )2
106
=
16
= 6.25 × 104 atm

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56 Physical Chemistry Success Achiever (Solutions)

Volume occupied by diamond is less.
As ‘K’ is increasing on increase of ‘T’.

Hº Sº
log K  
2.303 RT R

374a. Answer (1) [JEE (Main)-2018]

H
⎛A ⎞ 
Equilibrium constant K  ⎜ f ⎟ e RT
⎝ Ab ⎠

⎛A ⎞ H ⎛ 1 ⎞
ln K  ln ⎜ f ⎟  R ⎜⎝ T ⎟⎠
⎝ Ab ⎠
y= C+ m x
Comparing with equation of straight line,

H
Slope =
R
Since, reaction is exothermic, H° = –ve, therefore, slope = +ve.
ln K
A

B 1
(0, 0) T(K)

Hence, option (1) is correct.

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

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The sum of oxidation number of all the carbon atoms = 5(–1) + 0 + 3 = –2.
O–H
(+3)C = O
(0)
(–1) (–1)
(–1) (–1)
(–1)
6 2  3  4
H
 Cr 3   Fe 3   C O 2
K 2 Cr 2 O 7  Fe C 2 O 4 
(nf  6 ) (nf 3 )

Inverse of nf ratio is the mole ratio

3 K2Cr2O7 + 6 FeC2O4  Cr3+ + Fe3+ + CO2
∵ 6 mole FeC2O4 required 3 mole of K2Cr2O7

3 1
 1 mole FeC2O4 required 1  mole of K2Cr2O7
6 2

8 e
N2H4   (N2H4 ) 8 ( y )
2 x  4  8
x  2

+2 –2 0
Cu S Cu + SO2

+2 e

–6 e
So, 1 mole of CuS loses 4 mole of electrons.
M
Equivalent weight of CuS =
4
0 –3
N2  N H3
One mole of N2 loses 6 mole of electrons and one mole of NH3 gains 3 mole of electrons. Hence, equivalent
M1 M2
weight of N2 and NH3 will be and respectively. If an element is present in its lowest oxidation state
6 3
then it behaves as reducing agent only. So, NH3 acts as reducing agent only.
If an element is present in its highest oxidation state then it behaves as oxidising agent only and if an element
is present in its lowest oxidation state then it behaves as reducing agent only. S has highest oxidation state
+6 and lowest oxidation state –2. So, H2SO4 acts as oxidising agent only and H2S acts as reducing agent
only.
The structure of K3CrO8 is
O O
Cr – +
O O—O K
– O
O
+ –
K O+
K
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In the reaction, only two chlorine atom change its oxidation number (–1) to zero.

2
So, n-factor for HCl =  0 .5
4

M 36.5
Equivalent weight of HCl =   73
0 .5 0.5

Balanced reaction is
3 Cl2 + 6 OH–  5 Cl– + ClO3– + 3H2O
Cu2+, Sn4+ and Fe3+ are placed below hydrogen in electrochemical series. So, it is reduced by hydrogen but
Al3+ is placed above hydrogen in electrochemical series.
Less electronegative halogen does not displace more electronegative halogen from the salt but I2 displaces
chlorine and bromine from oxysalt because in this case, displacement of halogen is done by reduction.

2+ –1 +3 +4
Fe S 2 Fe2O3 + SO2

–1 e

–2 × 5e

M
Total 11 mole of electrons are lost by 1 mole of FeS2. Hence, equivalent weight of FeS2 = .
11
Equivalents of KMnO4 = 0.5 × 5 (nf = 5) = 2.5
In 4th option,
Equivalents of FeSO4 = 2.5 × 1 (nf = 1) = 2.5
M
Br2  Br–, equivalent mass of Br2 =
2
M
Br2  BrO3– equivalent mass of Br2 =
10
M M 6M
Net equivalent mass of Br2 =  
2 10 10
10 5
 n-factor of Br2 = 
6 3

O O
– (+5) (0) (0) (+5) –
O —S—S—S—S—O
O O
In which, two sulphur atoms have (+5) oxidation number and two sulphur atoms have zero oxidation number.

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393a. Answer (4) [JEE(Main)-2016]

Fluorine is most electronegative element and it does not show positive oxidation state.

Silver can’t displace Cu from CuCl2 because Ag is placed below than Cu in electrochemical series.
Electrolysis makes a non-spontaneous change spontaneous.
Factual
Factual
Here energy evolved (–G) is converted in electrical energy.
Factual
Electrochemical series is the arrangement of increasing order of standard reduction potentials.
Oxidation potential of Li is highest and of H is zero.

= 0.41 – (–0.74)
= 1.15 V

H2(g) Temperature = 298 K

1 atm

Pt(s)
1 M HCl
This is schematic diagram of S.H.E.
This is as per the law of conservation of mass and law of conservation of charge.
As oxidation potential of metalloids must be less than metals and greater than non-metals.
Oxidation potential under standard conditions will be positive and constant irrespective of concentration.

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6 2  4
H
 Cr 3   Sn Cl 4
K 2 Cr2 O 7  Sn Cl 2 
( nf  6 ) (nf  2 )

Inverse of nf ratio is the mole ratio

H
 Cr 3   SnCl 4
K 2Cr2 O 7  3SnCl 2 

∵ 3 mole SnCl2 will be oxidised by 1 mole K2Cr2O7

1
 1 mole SnCl2 will be oxidised by  1 mole K Cr O
3 2 2 7

1
So, mole of K2Cr2O7 required = mole
3
Na2 B4 O7
2 × 1 + 4x – 14 = 0
4x = +12
x = +3
In H2SO4, S has highest oxidation number i.e. +6 and in SO2, S has oxidation number +4 which lies in
between range of S (–2 to +6).
+1 –2 +2 2+ +4
Cu2 S Cu + SO2

+2 e

–6 e
M
Total 8 e– are lost by one molecule of Cu2S. So, equivalent weight of Cu2S = .
8
1 2
CH3  CH  CH2
4 4
 CO2 , n  4   4   8
CH4 

Total 4 alternate corners, 4 alternate edges and 2 alternate faces are present in a cubic unit cell.

1 1
Number of ‘A’ atoms = 4 
8 2

1
Number of ‘B’ atoms = 4 1
4
1
Number of ‘C’ atoms = 2 1
2
Hence, formula of unit cell = A1/2BC and simplest formula of compound is AB2C2.
Orthorhombic crystal system has simple, body centred, end centred and face centred unit cell.

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Only Ba forms body centred structure, Ca and Sr forms face centred structure while Be forms hexagonal close
packed structure.

NM (2) (20 g mol1 )

= = = 9.11 × 105 gm–3 = 0.91 g cm–3
  
3
a3NA 2  452  1012 m / 3 6.023  1023 mol1

In Fe3O4, O2– ions form the ccp lattice, one Fe2+ is present in octahedral void. While Fe3+ ions are equally
distributed in between octahedral and tetrahedral voids. So, only 12.5% tetrahedral voids are occupied.

ZA
d
V(in cm 3 )  N0

For F.C.C., Z = 4, then

4  27 4  27
d 8 3 23 = = 2.8 g/c.c
 24
( 4  10 )  6.023  10 64  10  6.023  10 23

All the correct statements.

1
Number of ‘A’ atoms = 8 1
8

1
Number of ‘B’ atoms = 6  3
2

1
Number of ‘C’ atoms =  12  1  4
4
After passing tetrad axis, 2 face atoms and 1 body atom is removed. Now,
1
Number of ‘A’ atoms = 8 1
8

1 1
Number of ‘B’ atoms = 6 2  2
2 2
Number of ‘C’ atoms = 4 – 1 = 3
Hence, formula of unit cell is AB2C3.

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426a. Answer (1) (AIEEE 2011)

8
ZA 
8
5
ZB 
2
So formula of compound is AB5/2
i.e., A2B5

In Frenkel defect, ions occupy the interstial site like interstitial defect and create a vacancy in the lattice site
like vacancy defect. So, it is the combination of vacancy as well as interstitial defect.

427a. Answer (3) [JEE (Main)-2018]

In Frenkel defect, cation is dislocated from its normal lattice site to an interstitial site.

In case of BCC structure,

3a
r  r–  (a = cell edge length, r+ + r– = inter ionic distance)
2

3  3.5
r  r– 
2

r+ + r– = 3.031 Å

429a. Answer (3) [JEE (Main)-2014]

Cl
– Cl

Cl –
Cl
+
Cs

Cl –
Cl
— Cl
Cl

2rCl  2rCs  3 a

3a
rCl  rCs 
2

In a cubic crystal, 9 plane of symmetry, 13 axis of symmetry and 1 centre of symmetry is present.

Factual type.

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1 1
Number of O2– ions = 8  6  4
8 2

Number of metal ions = 1  2 3

(12.5% T.V ) ( 50% O.V.)

Hence, formula of metal oxide is M3O4.

The length of face diagonal = a 2

= 80 2
So, a = 80 pm (a = cell edge length)
In NaCl type structure,
a 80
r  r    40 pm
2 2

a 361
r=   127.6 pm
2 2 2 2

In FCC, one of the face is like A

By ABC,
a
2a2 = 16r2

1 2 C B
 r2  a
8

1
 r a
2 2

a
Distance of closest approach = 2r =
2

2 (r+ + r–) = 670.3 pm

670.3
r+ = pm – 181 pm = 154 pm
2

Factual type.

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437a. Answer (1) [JEE(Main)-2016]

CrO2 is strongly attracted towards magnetic field so it is ferromagnetic.

For fcc,

ax 2 (x = cell edge length)

a
x
2

3
⎛ a ⎞ a3

Volume of fcc unit cell = ⎜ ⎟
⎟ 
⎝ 2⎠ 2 2

The length of body diagonal is a 3 . Two tetrahedral voids are present on each body diagonal at the distance

a 3
.
2
The simplest unit of hcp structure is hexagon. Other statements are correct.
For bcc,

a 3 5 3
r   2.165 Å
4 4
r = 216.5 pm

Edge length of BCC is 4.29 Å.

In BCC,

4
edge length = r
3

4
4.29 = r
3

4.29
r= 3  1.86 Å
4

Total 4 body diagonals are present in a cube. 1 middle tetrahedral void is present on each body diagonal is
common for all. So, total number of tetrahedral voids are 9.

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rNa 
From r  0.75
K

rNa  0.75 rK  …(i)

rNa 
Putting the value of rNa in  0.55 then we get
rCl –

0.75 rK 
 0.55
rCl–

rK  0.55
  0.733
rCl– 0.75

2(rK   rCl– ) 2(0.733  1)

So, 2(r   r – )  2(0.55  1)  1.118
Na Cl

(Side for unit cell for KCl = 2(rK   rCl– ) , Side for unit cell for NaCl = 2(rNa  rCl– ))

Triclinic is the most irregular system. The cell dimensions of this system are a  b  c and      
90°.
All statements are correct for fluorite structure.
1 mole AlCl3 develops 2 mole of cation vacancies in the doping in NaCl.

10 5
Number of cation vacancies = 2   6.023  10 23 = 1.2046 × 1017
100
In this defect, some Fe2+ ions are converted into Fe3+ ions. Due to charge balance number of Fe atoms
decrease. Hence, it is found as Fe0.95O not FeO.
Both Al3+ ions are present in octahedral voids. Other statements are correct.
In the unit cell of NaCl, Na+ ions are present in octahedral voids and Cl– ions are present on ccp lattice. When
one body diagonal plane is placed in the unit cell, then 4 corner ions, 2 edge ions, 2 face ions and 1 body
ions are removed. Now,

⎛1 ⎞ 1
Number of Na+ ions = 4  ⎜  2  1⎟  2
⎝4 ⎠ 2

⎛1 1 ⎞ 1
Number of Cl– ions = 4  ⎜  2   4 ⎟  2
⎝ 2 8 ⎠ 2

37.46 a13 a 37.46

 3 ⇒ 1 3  1.103
27.94 a2 a2 27.94

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Fact
Volume of any lattice is
V = abc(1 – cos2– cos2– cos2– 2cos cos cos)1/2
V1 = Vtetragonal = a2c
(because a = b  c,  =  =  = 90°)

3
V2 = Vhexagonal = a2c 
2
(because a = b  c,  =  = 90°,  = 120°)

V1 2
 
V2 3

MnO2 has rutile structure.
No. of T-voids = 2 × no. of atoms
No. of O-voids = no. of atoms.
Reverse osmosis involves moment of solvent particles through semipermeable membrane from concentrated
solution to dilute solution.
For isotonic solution C1 = C2 (at constant temperature).

98 1000  1.6
N=   32
49 100
9.1 × 10–31 kg = 1 e–

1 
 1 kg = e
31
9.1 10
∵ 6.023 × 1023 e– = 1 mole

1  1 1
 e  
31 23 31
9.1 10 6.023  10 9.1 10
 Number of moles (n) = 0.018 × 108 = 1.8 × 106 moles

n
 Molarity = v
2

1.8 106
M=
0.5
M = 3.6 × 106 M.

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According to Raoults law for non-volatile solution.

PB  P ⎡ A  solute ⎤
  xA ⎢ ⎥
PB ⎣B  solvent ⎦

PB  P loss in weight of solvent

PB gain in weight of CaCl2 .

Because in positive deviation solvent-solvent interaction is greater than solute-solvent interaction.
Elevation in boiling point is inversely proportional to molecular length of solute.
meq of HCl = meq of NaOH

Mass
 1000  NVml …(i) (N = 0.5 N, V = 100 ml)
Eq mass

mass of HCl  1000

∵ molality = M.m  mass of solvent (g)

⎛ g ⎞ 1000
5  ⎜⎜ ⎟⎟ 
⎝ Eq mass ⎠ w

g
  1000  w  5 …(ii)
Eq mass

from eq. (ii) to (i)

⎡N  0.5 N ⎤
 w × 5 = 0.5 × 100 ⎢ ⎥
⎣ V  100 ml ⎦

w = 10 g.
(mass of solvent )

a3Na
M=
N

(1.984 gcm3 )(630  1010 cm)3 (6.023  1023 mol1 )

=
4
= 74.7 g mol–1

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nRT
Osmotic pressure () =
v
i1n1RT i2n 2RT
 1 = and 2 =
v v
  = 1 + 2
⎛ i1n1RT ⎞ ⎛ i2n2RT ⎞
 = ⎜⎜ v ⎟⎟  ⎜⎜ v ⎟⎟
⎝ ⎠ ⎝ ⎠
and v1 + v2 = v
⎛ i1n1  i2n 2 ⎞
 = ⎜⎜ v
⎟RT

⎝ ⎠
T ⎡ ini in2 ⎤
⎢  ⎥
v ⎣v v ⎦

⎛ i1n1  i2n 2 ⎞
⎜ ⎟
or  = ⎜ v  v ⎟RT .
⎝ 1 2 ⎠

472a. Answer (2) [JEE(Main)-2016]

18
pº –ps nsolute 180 18
  
ps nsolvent 178.2 17.82
18

760 – ps 18
 
ps 1782

or, 1800 ps = 760 × 1782

ps = 752.4 torr

PB  P in A ⎡ A  solute ⎤
 …(i) ⎢ ⎥
PB in A  nB ⎣B  solvent ⎦

∵ solution is concentrated
P°B = 760 mm-Hg P = 750 mm-Hg
5.85
nA = = 0.1 mole
58.5

180
nB = = 10 moles
18
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 
for AB  A  B
1   

 i=1+

760  750 0.1(1   )

760 (1   )0.1  10

1 0.1(1   )
 (dilute solution)
76 10

100
1+=
76

 = 0.315.

Solution will be ideal and for ideal solution Hmix. = 0.

3
Al 2 (SO 4 ) 4  2Al  3SO 4 2
2 moles
1 mole 3 moles

nsolute
molality = w  1000
solvent
⎡ w ⎤
⎢d  v ⎥
⎢ ⎥
n ⎢ w  250  1⎥
3=  1000 ⎢ w  250 g ⎥
250  1
⎢ ⎥
⎣ ⎦
3
n= mole
4

∵ 1 mole of Al2SO4 producing 2 moles of Al3+

3 2 3 3
 mole of Al2SO4 producing  = mole
4 1 4 2

3 23 23
 number of Al3+ ions =  6.023  10  9.03  10 ions.
2

For MgCl2,  = 50% i.e. 0.5
2 
MgCl2  Mg  2Cl
1   2

 i1 = 1 + 2

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i1 = 1 + 1
i1 = 2
for CH3COOH,  = 50% i.e. = 0.5

1
CH3 COOH  (CH3 COOH)2
1 
2

2

i2 = 1  Total value of
2

i2 = 1 – 0.25 i = i1 + i 2
i2 = 0.75 i = 2 + 0.75
i = 2.75
Addition of acid in to water is exothermic and H < 0 then solution will be non ideal showing negative deviation.

479a. Answer (1) (AIEEE 2009)

Ethanol has H-Bonding, n-heptane tries to break the H-bonds of ethanol, hence, V.P. increases. Such a
solution shows positive deviation from Raoult's Law.

At –56.6°C, solid and liquid are in the same phase.

Vapour pressure does not changes with enthalpy.

Solvent is the component which have same physical state as that solution.

3 
For AlCl3  Al  3Cl
1   3

 i1 = 1 + 3 ( = 100%)
i1 = 4

 
NaCl  Na  Cl
1   

i=1+ ( = 100%)
i=2
 1 = i1RT

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2 = i2cRT
1 i1

2 i2

1 4

2 2
 1 : 2 = 2 : 1.

485a. Answer (4) [JEE (Main)-2018]

The solution which shows maximum freezing point must have minimum number of solute particles.
(1) [Co(H2O)6]Cl3  [Co(H2O)6]3+ + 3Cl–, i = 4
(2) [Co(H2O)5Cl]Cl2  H2O  [Co(H2O)5Cl]2+ + 2Cl–, i = 3
(3) [Co(H2O)4Cl2]Cl  2H2O  [Co(H2O)4Cl2]+ + Cl–, i = 2
(4) [Co(H2O)3Cl3]  3H2O  [Co(H2O)3Cl3], i = 1
So, solution of 1 molal [Co(H2O)3Cl3]  3H2O will have minimum number of particles in aqueous state.
Hence, option (4) is correct.

When benzoic acid dissolved in benzene it gets dimerises and molecular mass of its diemer is 244 amu.

Hvap = Lv × M.m = 540 × 18 = 9720 cal/mole.

1000 1000
m   55.56
18 1000

PB  P ⎡ A  solute ⎤
 xA …(i) ⎢ ⎥
PB ⎣B  solvent ⎦

From Eqn (i)

xA xA
m = x  55.55 xA  1
B 0.054

xA ⎛ 1 ⎞
3 = x  55.55 x A ⎜1  ⎟ 1
B ⎝ 0.054 ⎠

xA 1
= 0.054 xA 
xB 19.5

xA
 xB  …(i) xA = 0.05
0.054
∵ xA + xB = 1 P°B – P = xA × P°B
P°B – P = 0.05 × 760 = 38.97 mm-Hg.

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Vapour pressure of pure acetone P°A = 185 torr

Vapour pressure of solution, PS = 183 torr
Molar mass of solvent, MA = 58 g/mole

P°A – PS nB
as we know =
PS nA

185 – 183 WB MA
⇒ = ×
183 MB WA

2 1.2 58
⇒ = ×
183 MB 100

1.2 58
⇒ MB = × ×183
2 100

= 63.68 g / mole

SO2 + NaOH  NaHSO3
meq. of NaOH = meq of NaHSO3

g
NV   1000(NaHSO 3 )
(NaOH) eq mass

g
0.1 1 100   1000
104

3 3

 For the calculation of lowering of vapour pressure

PB  P ⎡ A  solute ⎤
 xA ⎢ ⎥
PB ⎣B  solvent ⎦

1.04
PB  P
 104
 PB 36 (dilute solution)
18

PB  P 0.01
 
PB 2

0.01
 (P°B – P) =  1 (atm)
2

P  P
B = 0.005 atm
(lowering of vapour pressure)

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RT0 2
Kb 
1000 Hv

2
2  (373)
Kb 
 9.72 3
1000   10
18
Kb = 0.52° mole/kg
 Tb = Kb × m
Tb = 0.52 × 0.1 = 0.052°.
1
C 6H5 COOH  C H COOH
1 
n 6 5
1

n

 i = 1  
n

⎛ 1⎞ ⎡  100%⎤
i = 1  ⎜ 1  ⎟ ⎢ ⎥
⎝ n⎠ ⎣ ⇒ 1 ⎦

⎛ 1⎞
 i = 1  ⎜1  ⎟ …(i)
⎝ n ⎠

Tf (obserbed)
i=
Tf (calculated)

Tf
 i …(ii)
Kfm

12.2  1000
m=
122  100
m = 1 molal

0.93
 i=
1.86  1

1
i=
2
Putting the value of ‘i’ in equation (i)

⎛ 1⎞
i  1  ⎜1  ⎟
⎝ n⎠

1 ⎛ 1⎞
 1  ⎜1  ⎟
2 ⎝ n ⎠
n = 2.
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494a. Answer (2) [JEE(Main)-2016]

For MX2 salt
Van’t Hoff factor = 1 + 2 = 2
 = 0.5

Tb = Kbm
 logTb = logKb + logm log  Tb

y = mx + c
 m=1 (tan = 1,   = 45°) log m
Solute solvent interaction is equal to solute-solute and solvent-solvent interaction.
For dilute solution

nA
xA ~ n (nA + nB ~ nB)
B

PB  P in A
   ix A .
PB nB

For isotonic solution
A = B
 CART = CBRT
CA = CB.

P A x A
x A 
( vapour phase )
P A x A  PB x B

50  0.5
 xA =
50  0.5  100  0.5

25
xA =
75
 xA = 0.33.
Volume strength of H2O2 = 5.6 × normality
 volume strength = 5.6 × 4.5 = 25.2.
The solution which flow into the blood stream are of the same osmotic pressure as that of blood otherwise
due to difference in osmotic pressure blood cells may swell and burst.

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Partial pressure of water
R.H   100
Saturated partial pressure of water
Fact
P  XA PA0  XBPB0

2A 
 A2 
3A 
 A3
1 0 
 1 
1  3
2
 2
⇒ i  1 ⇒ i  1
2 3
1 2 1
 1   0.5  1    0.33
2 3 3

505a. Answer (2) [JEE (Main)-2017]

0.2 / 60
0.45 = i(5.12)  1000
20
 i = 0.527

  CH3COOH2


2CH3 COOH 
1–  
2

 i  1–
2

 0.527 = 1 –
2

 = 0.473
2
  = 0.946
 % association = 94.6%

8.314   383.7  92
2
RTb2 M1
Kb  ⇒ Hv  = 34 kJ mol–1
1000Hv 1000  3.32  103
i = 5 for K4[Fe(CN)6) and i = 5 for Mohr salt.

507a. Answer (3) (AIEEE 2010)

Tf = i Kfm
i for Na2SO4 is 3(100% ionisation)
0.01
Tf = 3 × 1.86 ×
1
Tf = 0.0558 K

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  i CRT

Na3PO4  4  0.125  RT  0.5 RT

0.2 mol I2 and 0.8 mol C6H6

WC6 H6  0.8  78

0.2  1000
m  3.2
0.8  78

6
Cr 2 O72   2Cr O24

G1 = – 2Fx1, G2 = + x2F, G3 = – FE°
G3 = – G1 – G2 = – (– 2Fx1) – (x2F) = – FE°
E° = (x2 – 2x1) V

511a. Answer (2) (AIEEE 2009)

3+ E0 = ? 2+ E0 = – 0.439 V
Fe (1)
Fe (2)
Fe
0
E = – 0.036 V
(3)

G01 + G02 = G03

 – n1E01 – n2E02 = – n3E03
 – E0 + 2 × 0.439 = +3 × 0.036
 E0 = +0.77 V

Ksp = 4x3, (x is solubility of Ag2CrO4)
[Ag+] = 2x

0.0591 1
E = 0.80 – log
1 2x
AgNO3 will react with copper.

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Standard free energies of reactant and product are same.
Go = 0
Value of ‘n’ is not given

2.303 RT
E= – log Q
nF
2H+ 
 H2

PH2
Q=
[H ]2
Fact.
Only H2O is electrolysed.
Change in oxidation number of N is 6

22.4
 Veqv = = 3.73 L
6
2H2O + 2e–  H2 + 2OH– ...(i)
2H2O  O2 + 4H+ + 4e– ...(ii)

2x
From (i) 1 mol of H2 = 22.4 LH2 is obtained by 2 units xL of H2  units costing Rs.x
22.4
hence, 1 units costs = Rs. 11.2
from (ii) : 22.4 L at NTP costs = 4 units
= 4 × 11.2
xL costs = 2x

NO2 NO

2e– +  
nf 2

n=2

gram Eq = n × mole = 2 × 0.5 = 1

1 Eq nitrogen benzene require 1F

1
 Net charge = = 1.25 F
0 .8
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It is 2.26V.
The cell can be formed as Fe|Fe3+; OH–|Fe(OH)3(s)|Fe
The electrode reactions can be written as
Fe(s)  Fe3+ + 3e–
Fe(OH)3(s) + 3e–  Fe(s) + 3OH–
Overall reaction is i.e., by adding

i.e. E° = E0 – E0
OH– /Fe(OH)3 /Fe Fe2  /Fe

OH– /Fe(OH)3 /Fe

0.0591 0.0591 (–36.4)

E° = log10 –36.4 
0.3 3

 0.75V

EOH–/Fe(OH)3 /Fe = –0.75 – 0.036 = –0.786V

Larger cation, more ionic mobility.

Eocell = EFe
o
2
/ Fe
o
– E Cr 3
/ Cr

Li has maximum reducing power.

WAg WMg
=
E Ag EMg

BaSO4 = (C1 – 2C2 + C3)

M 0.01
K= = (C1 – 2C2 + C3) ×
1000 1000

530a. Answer (3) [JEE (Main)-2014]

According to Debye Huckle onsager equation,

C    A C
Here A = B

 C     B C

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Pb(s) + CaC2O4(s)  PbC2O4(s) + Ca+2 + 2e–
Temperature coefficient becomes minimum.
Example : Pt | Sn+2, Sn+4

0.0591
E = Eo – log [H+]2 = Eo + 0.0591 × pH
2
E1 – E2 = 0.0591 [(pH)1 – (pH)2]
After electrolysis aqueous NaCl is converted into aqueous NaOH

0.250  35  60
The quantity of electricity passed = F = 5.44 × 10–3 F
96500

The number of equivalents of OH– ion formed = 5.44 × 10–3

5.44  10 –3
 Molarity of NaOH =  1.36  10 –2
0.4L

 pH = 12.13

G
=
H

536a. Answer (3) (AIEEE 2009)

3
CH3OH(l) + O (g)  CO2(g) + 2H2O(l)
2 2
Greaction = Gproducts – Greactant
= [–394.4 – 2 × 237.2] – [–166.2]
= –702.6 kJ

G
We know, efficiency of a fuel cell,    100
H

–702.6
=  100
–726

 97%

M C 2
= ,K=
 1– 

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– +
CHCOOH + H2O CH3COO + H3O

c 48.15
x (degree of ionisation) =  =  0.1232
0 390.7

cx2 1.0283  10 –3  (0.1232)2

Ka(ionisation constant) = = = 1.78 × 10–5
(1– x) (1– 0.1232)

1000  conduc tance  cell constant

Equivalent conductance c = normality

1000  conduc tance  0.50cm –1

97.1 (ohm–cm2equiv–1) =
0.1(equivalent cm –3 )  1.50

 conductance = 0.02913 ohm–1

 current = 0.02913 × 5 = 0.1456A

538a. Answer (1) [JEE (Main)-2014]

For 0.2 M solution
R = 50 
 = 1.4 S m–1 = 1.4 × 10–2 S cm–1
1 1
    cm
 1.4  10 2

l
Now, R  
a

l R
   50  1.4  10 2
a 

For 0.5 M solution

R = 280 
=?

l
 50  1.4  10 2
a
l
 R
a

1 1 l
  
 R a

1 1
  =  50  1.4  10 2 =  70  10 2 = 2.5 × 10–3 S cm–1
280 280

  1000 2.5  10 3  1000

Now, m  = = 5 S cm2 mol–1 = 5 × 10–4 S m2 mol–1
M 0.5

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dE S
=
dT nF

E > 0, Q < 1.

1
H  e – 
 H2
2

Apply Nernst equation

1

0.059 PH2 2
E0 log 
1 [H ]

0.059 21/2
E log
1 1

Therefore E is negative.

E = Z × 96500

Fact.

No relation with reactions.

1
H2O  O + 2e–, H2O2  O2 + 2e–
2 2

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B2H6 + 3O2  B2O3 + 3H2O

27.66 of B2H6 = 1 mole of B2H6 which requires three moles of oxygen (O2) for complete burning
6H2O  6H2+ 3O2 (On electrolysis)
Number of faradays = 12 = Amount of charge
12 × 96500 = i × t
12 × 96500 = 100 × t
12  96500
t second
100
12  96500
t hour
100  3600
t = 3.2 hours

wq

electrolys is 1
NaH    Na  H2 (g)
2
( cathode) anode

551a. Answer (2) [JEE (Main)-2014]

On electrolysis only in case of Ca2+ salt aqueous solution H2 gas discharge at Cathode.
Case of Cr
At cathode : Cr3+ + 2e–  Cr
So, Cr is deposited.
Case of Ag
At cathode : Ag+ + e–  Ag
So, Ag is deposited.
Case of Cu
At cathode : Cu2+ + 2e–  Cu
Case of Ca2+

1
At cathode : H2O + e–  H + OH–
2 2

E
w= ×i×t
96500

0.0591 [Cu 2 ]1
E1 – E2 = log
2 [Cu  2 ] 2

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Go = – nF Eocell = – 2 × 96500 × 1.10 J

1
H2 

 +
 H +e

2
K = [H+] = C1
E = E° – 0.0591 logC1
E decreases if C1 increases
1
Cl– 
  Cl2  e

2
1 1
K 

[Cl ] C2
E = E° + 0.0591 logC2
E increases if C2 increases


Ag   +
 Ag + e

K = C3
E = E° – 0.0591logC3
E decreases if C3 increases
For spontaneous cell reaction, E > 0.

2 7

2

4

G3 = G°1 + G°2

–n3E°3 = – n1E°1 – n2E°2
+3E°3 = 2 × 1.26 – 1 × 0.336
E°3 = 0.728 V

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Cu does not react with dilute H2SO4.
E
w= ×it
96500

⎛ 127 ⎞
⎜ ⎟
⎝ 1 ⎠
10 = × i × 60 × 60
96500
i = 2.11 A
It requires no gaseous reactant.
Eo = +0.22 – 1.36 = –1.14 V

1
0.059
⇒ E  Eo 
1

log PCl2 2
–w max = G = –nFE = (–1) (–1.14) × 96500 × 10–3
=110 kJ mol–1
2 × 1.6 × 10–19C is carried by 1 molecule of Zn2+

1
 2 × 10–5 C is carried by =  2  10 5
2  1.6  1019

1 1
  moles
1.6  1014 N0

1

1.6  6.023  1014  1023
= 10–10
1000 sp.conduc tance
0 (BaSO4 ) 
conc.(Normality)

1000  8  10 –5
Normality =
400
Normality
Molarity =  10 –4 M
2
Ksp = S2 = 10–8 M2

Eºcell  EºCu2 /Cu – EºCr3 /Cr = 0.34 – (– 0.74) = +1.08 V

E  0.5208 V
Cu /Cu

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+ –
Ag Ag + e ; E°Ag/Ag+ = –0.80V
– –
AgI+e Ag + I ; E°I– / AgI/Ag+ = –0.15V
Ag + I–
+
AgI E°Cell = –0.95V

K = [Ag+] [I–] = Ksp

0.0591
ECell = log k sp
1
–0.95
 log K sp
0.0591
Ksp = 8.42 × 10–17

0.059 ⎛  D  ⎞
Ecell  0.003  log ⎜  ⎟  0 at equilibrium
2 ⎝ H  ⎠

⎛  D  ⎞
0.006  0.059log ⎜  ⎟
⎝ H  ⎠

⎛ D   ⎞ D
0.102  log ⎜  ⎟ ⇒   100.102  1.2
⎝ H  ⎠ H 

The fraction of collision with sufficient energy i.e., e – E a / RT becomes unity only at Ea = 0.

2.303 ⎛ a ⎞
k= log ⎜⎜ ⎟⎟
t ⎝a– x ⎠
at time (t/2) seconds

0.6932 2.303 ⎛ a ⎞
 log ⎜⎜ ⎟⎟
t ( t / 2) ⎝a– x ⎠

0.6932 ⎛ a ⎞
 log ⎜⎜ ⎟⎟
2  2.303 ⎝a– x ⎠

⎛ a ⎞
log ⎜⎜ ⎟⎟  0.15
⎝a– x ⎠

⎛ a ⎞
⎜⎜ ⎟⎟  1.413
⎝a– x ⎠
a = 1.413a – 1.413x
0.413a = 1.413x
x 0.413

a 1.413
0.413
% fraction of element decayed =  100 = 29%
1.413

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1
t 1/ 2 & where n is order of reaction
n –1
a
for zero order reaction n = 0
t1/2 & a
On decreasing the volume of vessel the to half conc. of A and B are increased by factor of
2 times
 rate will be increased by a factor of 4 times

573a. Answer (1) [JEE(Main)-2016]

Rate = k[A] [B]

For the completion of 75% reaction 2 half life requires
 2 t1/2 = 50
t1/2 = 25 mins

574a. Answer (2) (AIEEE 2009)

ln 2
t1/2 =
k
2.303  0.301
 k=
6.93

2.303 ⎛ a ⎞
log ⎜
⎝ a – 0.99a ⎟⎠
Also, t =
k

2.303 ⎛ 1 ⎞
 t = 2.303  0.301  6.93 log ⎜⎝ 0.01⎟⎠ = 46.05 minutes

Rate = k[0.1]m [0.2]n = 2 × 10–3 …(i)
m n –3
k[0.1] [0.4] = 4 × 10 …(ii)
m n –3
k[0.2] [0.2] = 2 × 10 …(iii)
dividing equation (i) by (ii)
n
1 ⎡ 1⎤
 n=1
2 ⎢⎣ 2 ⎥⎦

dividing equation (i) by (iii)

m
⎡ 1⎤
⎢2⎥ 1 m=0
⎣ ⎦
 Rate = k[A]0 [B]

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2A  B  C  D

1 d[A] d[B] d[C] d[D]

Rate of Reaction =   
2 dt dt dt dt

d[C]
Or,  k[A]x [B]y
dt

1.2  10 3 k[0.1]x [0.1]y

⇒ 
1.2  10 3 k[0.1]x [0.2]y

y
⎡ 1⎤
⇒ 1 ⎢ ⎥
⎣2⎦

⇒ y0

1.2  10 3 k[0.1]x [0.1]y

⇒ 
2.4  10 3 k[0.2]x [0.1]y

1 x
⎡ 1⎤ ⎡ 1⎤
⇒ ⎢2⎥  ⎢2⎥
⎣ ⎦ ⎣ ⎦

⇒ x 1

d[C]
Hence = k[A]1[B]0 .
dt

Temperature cofficient is the ratio of rate constant when the temperature differ by 10°
75 32 K
65 16 K
55 8K
45 4K
35 2K
25° K
Since the value of rate constant will be increased by 32 times therefore the rate will be increased by 32 times.

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t1/2  a
t1/2 = ka
log t1/2 = log k + log a
y = c + mx
m=1
  = 45°

k = A e –Ea / RT
when Ea = 0
The k = A, it means rate constant is independent of temperature
 k rate constant at 330 K will be 4.5 × 105 s–1
x 10
k= for zero order reaction = = 10
t 1
20
In second case k = = 10
2
30
In third case k = = 10
3
Since rate constant (k) is equal in each case therefore reaction follows the zero order mechanism.
k1
Value of k1 is the least, therefore the conversion A  B is the slowest and rate determing step of the
reaction.
r1 = k[A] – 1st order reaction
r2 = k[A]2 – 2nd order reaction
r3 = k[A]3 – 3rd order reaction
When the rate constant k is same for three reaction it is clear that
r1 = r2 = r3 when [A] = 1
r1 > r2 > r3 when [A] < 1
r1 < r2 < r3 when [A] > 1

Ea
Energy
P
H
R z
Reaction progress

It is clear from the graph that Ea should be greater than H.

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( excess)

rate law = k[CH3COOC2H5 ]

order of reaction = 1
molecularity = 1 + 1 = 2
Since the half life of first order reaction is independent of initial conc.
CH3COOC2H5 + NaOH  CH3COONa + C2H5OH
Rate = k[CH3COOC2H5 ] [OH– ]
 Order of reaction is 2
At intersection of two curve the concentration of A and B are equal (i.e., half of the reactant converted into
products) therefore it represent the half life of A.
Rate = k[A][B]2 since [A] is taken in excess therefore its concentration remain almost constant
 Rate = k[B]2 k × [A] = k
 Order of reaction = 2
Positive catalyst increases the rate of chemical reaction by lowering of activation energy of system.

k = A e –Ea / RT

Ea
ln k = ln A –
RT
y = c + mx

Ea
slope of graph = –
R

A (g)  2 B (g)  C (g)

t  0 PA  90 0 0
tt 90 – x 2x x

After time t 90 + 2x = 180

x = 45
2.303 90
k= log
10×60 90 – 45
0.6932
= 10×60
= 1.155 × 10–3 s–1

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590a. Answer (1) [JEE (Main)-2018]

Assume the order of reaction with respect to acetaldehyde is x.
Condition-1 :
Rate = k[CH3CHO]x
1 = k[363 × 0.95]x
1 = k[344.85]x ...(i)
Condition-2 :
0.5 = k[363 × 0.67]x
0.5 = k[243.21]x ...(ii)
Divide equation (i) by (ii),
x
1 ⎛ 344.85 ⎞
⎜ ⎟ ⇒ 2  (1.414)x
0.5 ⎝ 243.21 ⎠
 x=2

Heat of the reaction H = Ea f – Eab

 H = x
and the activation energy of reverse reaction is also x.
Rate = k[NO2] 2
Rate of reaction is independent of concentration of CO.
Rate of reaction = [A]a
[A]I = 2.2 M r1 = 2.4 M s–1
2 .2 2 .4
[A]II = = 1.1 M r2 = 0.6 or
2 4
On reducing the conc. of A to half the rate of reaction is decreased by 4 times.
Rate constant depends only on temperature.

596a. Answer (1) (AIEEE 2012)

Rate = k[ester] [H+ ]
K H2SO 4  K [H  ]H2SO 4
KHCl = K[H+] HCl
Since [H+] is obtained from H2SO4 is more than HCl therefore K H2SO4  K HCl .

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Since concentration of increases time to time but not linearly.

1 d [I– ] d [I ]
–  2
2 dt dt

d [I– ] 0.5 – 0.46

  0.004 M min –1
dt 10
d [I2 ]
 0.002 M min –1
dt

600a. Answer (1) [JEE(Main)-2016]

0.693
Rate = K[H2O2] =  0.05
25
1 0.693
Rate of formation of H2O2 =   0.05 = 6.93 × 10–4 mol min–1
2 25

Rate = k[A]
8.75 × 10–5 = k(0.5)
k = 17.5 × 10–5 s–1 = 1.75 × 10–4 s–1
Since the concentration of H2O2. If (first order reaction) decreases with the time as (at = a0 e –kt ) therefore graph
(4) is correct.
t = 144 = 1.44 × 100

1
= 1.44 t1/2, tav =

1
=

1
N N ·
e = 0 ⇒ 0 e  e
t
N N
N0
 N=
e

2.303 a 2.303
t= log = 2
k a  0.99a k

2.303  2
t=
k

⎛ 1⎞
t = 2.303  2 · ⎜ ⎟ = 4.604 tav = 4.6
⎝k ⎠

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K 2Ea  K 2Ea 1.0  10 2  60  3.0  10 2  70

Ea  = = 67.5 kJ mol–1
K 2  K a 1.0  10 2  3.0  10 2
Rate = k[A]x [B] y
R = k[A]x [B]y …(i)
R
= k[2A]x [2B]y …(ii)
2
R
= k[2A]x [B]y …(iii)
4
Dividing equation (ii) by (iii)
2 =  y
y=1
dividing equation (i) and (iii)
x
⎛ 1⎞
4 = ⎜ ⎟ x = –2
⎝2⎠
CA  2, CB  4
1
t1/ 2  n –1
a
t1/2 × an – 1 = constant
 n=2
0.6932
t1/2 =
k
2.303 100 2.303
t = log  log1000
k 0 .1 k
6.909
=
k
 t = 10 t1/2

609a. Answer (2) (AIEEE 2009)

ln 2
t1/2 =
k
2.303  0.301
 k =
6.93
2.303 ⎛ a ⎞
log ⎜
⎝ a – 0.99a ⎟⎠
Also, t =
k

2.303 ⎛ 1 ⎞
 t = 2.303  0.301  6.93 log ⎜⎝ 0.01⎟⎠

= 46.05 minutes

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k2
 e(E1 – E 2 ) / RT
k1

E1 – E 2 2
  2 .5
RT 2 10 3  400

k2
 e 2 .5
k1

k 2  e 2 .5 k 1

At very high conc. of NH3

1 + k2 [NH3 ] k2 NH3

k 1[NH3 ]
rate =  constant
k 2 [NH3 ]

This follows the zero order kinetics therefore rate is independent of conc. of NH3 .

A (g)  2 B (g)  C (g)

initial pressure P0 0 0
0
After reaction P – P 2P P

total pressure after the reaction

P0 – P + 2P + P = Pt

 2P = Pt – P0

⎛ Pt – P0 ⎞ 2.303 ⎛ P0 ⎞ P0 2.303 ⎛ 2 P0 ⎞
P = ⎜ ⎟ = log ⎜ ⎟ = 2.303 log = log ⎜ ⎟
⎝ 2 ⎠ t ⎜ 0 ⎟ t ⎡ 0 ⎛ P – P0 ⎞⎤ t ⎜ 3 P0 – P ⎟
⎝ P –P ⎠ ⎝ t ⎠
⎢P – ⎜⎜ t ⎟⎥
⎟⎥
⎢⎣ ⎝ 2 ⎠⎦

After the expiry of 40 mins the reactant A decomposes to 75% therefore

A (g)  B (g)  C (g)

Initial pressure 400 0 0
⎛ 3⎞ 3 3
After t  40 mins 400⎜1– ⎟ 400  400 
⎝ 4⎠ 4 4

 total pressure of reaction mixture

⎛ 3⎞ 3 3 3
= 400 ⎜1– ⎟  400   400  = 400  400  = 400 + 300 = 700 mm of Hg
⎝ 4⎠ 4 4 4

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Let N0 and N be the number of atoms of the radioactive substance present at the start and after 5 minutes
respectively rate of disintegration at the start = N0 = 275 and the rate of disintegration after 5 minute = N
N0 475
= 270 dividing both, 
N 270

N0
Or,  1.76
N
2.303 N
We know that   log10 0
t N
2.303
 log10 1.76 = 0.113 minute–1
5
0.693 0.693
Half life period =   6.1 minute
 0.113
7500  0.012 0.35
Weight of radioactive potassium =  = 0.0315 g
100 100
0.693 Weight

Activity = t1/2 Atomic weight  Avogadro’s number

0.693 0.0315
Activity = 9
  6.023  1023 = 4.81  105 dpm
1.3  10  365  24  60 40

k1 2.5 10 –3 2.5 10 –3 10 2 25

% of y =  100 = 100 = –2 = = 16.66%
k1  k 2 –3
2.5 10  1.25 10 –2 1 . 50  10 1 .50

% z = 100 – 16.66 = 83.34%

K1
Cyclohexene
Bicyclohexane
K2
Methyl cyclopentene

K1 1.26  104
Percentage of cyclohexene =  100 =  100 = 77%
K1  K 2 1.26  104  3.8  10 5
 % of methy cyclopentene = 23%
kf = 4 × 10–4
kb = 2 × 104

kf 4 10 –4
keq =   2 10 – 8
kb 2 10 4

k 400  A e –(Ea – 20 ) / 400 R …(ii)

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from equation (i) and (ii) we get

Ea (E – 20)
– – a
500 R 400 R
– 4 Ea = – 5 Ea + 100
Ea = 100 kJ mol –1

619a. Answer (2) [JEE (Main)-2017]

–Ea /RT
k1 = Ae 1

–Ea /RT
k2 = Ae 2

1
k2
e RT Ea1 – Ea2 
k1 =

k Ea – Ea2 10  103
ln 2 = 1 = 4
k1 RT 8.314  300

Rate = k[N2O5 ]

2.4
[N2O5 ] =  0 .8
3

The rate constant of the decay is

0.693 0.693
K 
t1/2 22

If K 1 and K2 are the rate constants of the reactions leading to 222th and Fr223, respectively we have
0.693
K1 + K2 =
22

K1 2

K 2 98

On solving for K1 and K2 we get

K2 = 0.03087–1y–1

K1 = 0.00063–1y–1

⎡ ⎛ N ⎞⎤
⎢ ln ⎜ N ⎟⎥
⎠ ⎥ ⇒ N0  24 ⇒ N  48 g
 
t  t1
2
.⎢ ⎝ 0
⎣⎢ ln 2 ⎦⎥ N
0

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0.693 2.303 4 1
9
 log
4.5  10 t 4

t log 3
0.693 2

=  0.1
0.693

= 1.445  109 years

Rate = k[A]n
r1 = k[A]n
8r1 = k 4n.[A]n
 2n = 3  n = 1.5
X is intermediate.

K1E1  K 2E2 102  60  3  102  70

Ea  
K1  K 2 102  3  102

= 67.5 kJ mol–1

x ap
Apply  . At high P, 1 + bp  bp.
m 1+ bp

Based on definition of peptization.
Size of clay particles is greater than 100 nm.
The size of crystalline particles are very small as compare to diameter of pores of membrane.
Fluorescein and Eosin are examples.
Higher the critical temperature higher the adsorption of gas.

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Catalyst decreases activation energy hence rate constant increases.

Ea

K  Ae RT

A
K Ea

e RT

As Ea decreases, K increases
Hence rate of reaction increases.
Colloids of metal and their sulphides are prepared by special methods not by simple mixing.
Lyophilic colloids not easily coagutated and are highly stable.
Kraft temp. = Temp. above which micell is formed.
Brownian motion is zig-zag motion responsible for stabilisation of colloids and it prevent the colloidal particle
to settle down.
2AuCl3 + 3HCHO + 3H2O 
 2Au(sol) + 3HCOOH + 6HCl
Cellulose is a polymer having very large particle size.
Fauzasite is natural, Na56[(AlO2)56(SiO2)136]  250 H2O.
Chemisorption is irreversible.
KI KI
AgNO3  AgI  [AgI] I—
For adsorption, S < 0, H < 0, G < 0.

649a. Answer (3) (AIEEE 2009)

Physisorption is an exothermic process with H  –20 kJ/mol

More contact with catalyst, faster rate of hydrogenation.

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In Bergious process Fe2O3 is used as catalyst.
Brownian movement is independent to nature of solute.
Due to very high difference between refractive indices of dispersed phase and dispersion medium.

653a. Answer (4) [JEE (Main)-2017]

For Tyndall effect refractive index of dispersion phase and dispersion medium must differ significantly.
Secondly, size of dispersed phase should not differ much from wavelength used.

Proteins in acidic medium is positively charged and in basic medium, negatively charged. Au and CdS are
negatively charged.

4 
Z=
D
Ferric hydroxide is positively charged colloid.
Gold numbers
Potato starch = 25
Gum Arabic = 0.15
Haemoglobin = 0.03
Gelatin = 0.001
Both emulsions show different properties in given tests.
It can describe only physisorption.