CHAPTER: SOLUTION

 Various types of concentrations: -

1) Molarity(M)
𝑛𝑠𝑜𝑙𝑢𝑡𝑒 𝑊𝑒𝑖𝑔ℎ𝑡 1
𝑠𝑜𝑙𝑢𝑡𝑒(𝑔𝑚)
M= M= ×
𝑉𝑜𝑙𝑢𝑚𝑒𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛(𝑙) 𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡𝑠𝑜𝑙𝑢𝑡𝑒(𝑔𝑚) 𝑣𝑜𝑙𝑢𝑚𝑒𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛(𝑙)
 Important Technique: -
1. X % of solute (w/w) or by weight
X gram of solute in 100 grams of solution.
2. X % of solute (w/v) or by volume
X gram of solute in 100 ml of solution.
 Equation of dilution: - Mi Vi = Mf Vf
 Numerical on molarity: -
1. An aqueous solution of 5% urea (w/w) is having density of solution 1.6gm/ml, calculate
molarity and what volume of this solution is equivalent to 10ml of 2M of it? (molecular
weighturea = 60gm)
Sol. 5% urea (w/w) means 5 grams of urea in 100gm of solution
(𝑔𝑚)
𝑊𝑒𝑖𝑔ℎ𝑡𝑢𝑟𝑒𝑎 1 mass of solution
M= (𝑔𝑚) × Density of solution =
𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡𝑢𝑟𝑒𝑎 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛(𝑙) volume of solution
5𝑔𝑚 1 1.6gm 100𝑔𝑚
M= × =
60𝑔𝑚 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛(𝑙) 𝑚𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
100
5𝑔𝑚 1 1.6
M= ×
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛(𝑙)
Volume of solution = (𝑙)
60𝑔𝑚 1000
M = 1.3 molar or moles/l
Objective shortcut: -
If x% solute (w/w) and density of solution is given then:
10 × X × density of solution 10 × 5 × 1.6
M= = = 1.3 molar
molecular weightsolute 60
Further: - MiVi = MfVf = 1.3 × Vi = 2M × 10ml
Vi = 15.3 ml
2. 200 grams of ethylene glycol (molecular weight = 62gm) is dissolved in 220gm of water
forming solution having density of solution = 1.2gm/ml. Calculate molarity?
𝑊𝑒𝑖𝑔ℎ𝑡𝐸𝑡ℎ𝑦𝑙𝑒𝑛𝑒 𝑔𝑙𝑦𝑐𝑜𝑙 1
Sol. M = ×
𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡𝐸𝑡ℎ𝑦𝑙𝑒𝑛𝑒 𝑔𝑙𝑦𝑐𝑜𝑙 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑙)
200𝑔𝑚 1 1.2𝑔𝑚 420gm
M= × Density of solution = =
62𝑔𝑚 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑙) 𝑚𝑙 volume of solution
420
1.2
M = (9.2) molar or moles/l Volume of solution = 𝑙
1000
Volume of solution = 0.35l
3. Calculate molarity of water whose density is 1gm/ml (molecular 𝑤𝑒𝑖𝑔ℎ𝑡𝐻 𝑜 = 18gm). 2
1 gram 1 1000
Sol. MH o
= × 1 l = = 55.55 mole/l
2 18 gram 18
1000

1
4. If density of methanol is 0.793kg/l, what will be its volume needed for making 2.5l of its
0.25 molar solution (molecular weightmethanol = 32grams).
Sol. Weightmethanol = 793grams
V(l) = 1l
(𝑔𝑚)
𝑊𝑒𝑖𝑔ℎ𝑡𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙 1 793𝑔𝑚 1
Molaritymethanol = × = × = 24.78mole/l
𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑣𝑜𝑙𝑢𝑚𝑒 (𝑙) 32𝑔𝑚 1𝑙
Equation of dilution: - MiVi = MfVf = 24.78 × Vi = 0.25M × 2.5l
Vi = 0.025l
2) Molality (m)
(𝑔𝑚)
𝑛𝑠𝑜𝑙𝑢𝑡𝑒 𝑊𝑒𝑖𝑔ℎ𝑡𝑠𝑜𝑙𝑢𝑡𝑒 1
m= (𝑘𝑔) => (𝑔𝑚) × (𝑘𝑔)
𝑊𝑒𝑖𝑔ℎ𝑡𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡𝑠𝑜𝑙𝑢𝑡𝑒 𝑊𝑒𝑖𝑔ℎ𝑡𝑠𝑜𝑙𝑣𝑒𝑛𝑡
 Numerical on molality: -
1. An aqueous solution of 10% glucose (w/v) is having density of solution = 1.5gm/ml,
Calculate molality (m) (molecular weightglucose = 180gm).
1.5𝑔𝑚 𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
Sol. 10% glucose (w/v) Density of solution = =
𝑚𝑙 100𝑚𝑙
10 gm of glucose in 100ml of solution Weight of solution = 150gm
(𝑔𝑚)
𝑊𝑒𝑖𝑔ℎ𝑡𝑔𝑙𝑢𝑐𝑜𝑠𝑒 1 10𝑔𝑚 1
m= × (𝑘𝑔) => × 140 = m = 0.39moles/kg
𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡𝑔𝑙𝑢𝑐𝑜𝑠𝑒 𝑊𝑒𝑖𝑔ℎ𝑡𝑠𝑜𝑙𝑣𝑒𝑛𝑡 180𝑔𝑚 𝑘𝑔
1000
2. Why molality (m) is preferred over Molarity (M)?
Sol. Since Molarity is a volume dependent term which changes with change in temperature
due to which molality is preferred which is independent of volume and do not change with
change in temperature.
3. Out of 1 molal and 1 molar aqueous solution of same substance which is having more
concentration and why?
Sol. Since in 1 molal solution; solvent content (dilution) is more than 1 molar solution that is
why concentration content in 1 molar is more than 1 molal.
 Objective shortcut between Molarity (M) and Molality(m): -
1000M
m = 1000 density of solution−M × molecular weight
solute
3) Mole fraction (x): -
Solution
xA + xB = 1
A B
𝑛𝐴 𝑛𝐵
𝑥𝐴 = , 𝑥𝐵 =
𝑛𝐴 +𝑛𝐵 𝑛𝐴 +𝑛𝐵
 Numerical on Mole fraction (x): -
1. An aqueous solution of 30 % Urea is (w/w). Calculate Mole fraction of each component.
(molecular weighturea = 60gm, molecular weightH2O = 18gm)?
30 70
Sol. murea = 30gm , nurea = , mwater = 70gm , nwater =
60 18

2
 𝑛𝑢𝑟𝑒𝑎
xurea = xwater = 1 – xurea
𝑛𝑢𝑟𝑒𝑎 +𝑛𝑤𝑎𝑡𝑒𝑟
30
60
xurea = 30 70 = 0.11 xwater = 1 – 0.11 = 0.89
+
60 18
2. An aqueous solution of H2So4 is having mole fraction of water is 0.85. Calculate molality
(m).
𝑥𝑠𝑜𝑙𝑢𝑡𝑒 × 1000
Sol. XH + 𝑋𝐻 =1 m = (1−𝑥
2 So4 2 𝑜 𝑠𝑜𝑙𝑢𝑡𝑒 ) × 𝑚𝑜𝑙𝑤𝑡𝑠𝑜𝑙𝑣𝑒𝑛𝑡

0.15 ×1000
0.15 0.85 m = (1−0.15) = 9.8molal
×18𝑔𝑚
4) P.P.M (Part Per Million): -
𝑚𝑎𝑠𝑠𝑠𝑜𝑙𝑢𝑡𝑒 ×106 𝑃𝑃𝑀 ×10−3
*PPM = *m or M =
𝑚𝑎𝑠𝑠𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑚𝑜𝑙𝑤𝑡𝑠𝑜𝑙𝑢𝑡𝑒
6
*PPM = mass fraction(solute) × 10
*PPM = % of solute × 104
 Numerical on PPM: -
1. A solution of Carcinogen contains 15 P.P.M CHCl3 (Molwt = 119.5gm) by mass. Calculate
(i) percentage of CHCl3 (2) molality (m).
𝑃𝑃𝑀 ×10−3 15 ×10−3
Sol. (i) PPM = % of CHCl3 × 104 (ii) m = = = 12.5 × 10-5molal
𝑀𝑜𝑙𝑤𝑡𝐶𝐻𝐶𝑙3 119.5
15
15
% = % 𝑜𝑓 𝐶𝐻𝐶𝑙3
104
5) Normality (N):-
(𝑔𝑚)
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑔𝑚 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠𝑜𝑙𝑢𝑡𝑒 𝑊𝑡𝑠𝑜𝑙𝑢𝑡𝑒 1
N= (𝑙) => (𝑔𝑚) × (𝑙)
𝑉𝑜𝑙𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑤𝑡𝑠𝑜𝑙𝑢𝑡𝑒 𝑉𝑜𝑙𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
(𝑔𝑚)
𝑀𝑜𝑙𝑤𝑡𝑠𝑜𝑙𝑢𝑡𝑒
𝑛𝑓
𝒏𝒇
Acid Base Salt
nf => Number of replacable nf => Number of OH- ions or (Acidity) nf => Total charge on
H+ ions or (Basicity) particular ion.
Eg:- NaOH => nf => 1 Ca2+𝐶𝑙21−
H3Po2 H3Po3 H3Po4 HCL Ca(OH)2 => nf => 2 nf = 2
o o o nf=>1 A𝑙23+ (So4)2−
3
P P P nf = 6
H O-H H O-H O-H O-H
H O-H O-H
nf =>1 nf =>2 nf=>3

3
  Relation between N and M: -
𝑊𝑡𝑠𝑜𝑙𝑢𝑡𝑒 1
N= 𝑀𝑜𝑙𝑤𝑡 × (𝑙) N = nf × M
𝑣𝑜𝑙𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑛𝑓

 Numerical on Normality (N): -

1. 20% aqueous solution of CaCl2 (w/w) is having densitysolution => 1.6gm/ml. Calculate
Normality (N). (𝑀𝑜𝑙𝑤𝑡𝐶𝑎𝐶𝑙2 => 111gm)
1.6𝑔𝑚 100𝑔𝑚
Sol. 20gm of Ca2+Cl2 in 100gm of solution Densitysolution =
𝑚𝑙
=
𝑣𝑜𝑙𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
(𝑔𝑚)
𝑊𝑡𝐶𝑎𝐶𝑙 1 100
2
N= (𝑔𝑚) × (𝑙) Volsolution = 1.6 𝑙
𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑤𝑡𝐶𝑎𝐶𝑙 𝑉𝑜𝑙𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 1000
2
20𝑔𝑚 1
N= 111 × (𝑙)
2
𝑉𝑜𝑙𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
10×𝑥×𝑑𝑒𝑛𝑠𝑖𝑡𝑦𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
=>5.8N Shortcut: N =
𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑤𝑡𝑠𝑜𝑙𝑢𝑡𝑒
10×20×1.6
N= 111 = 5.8N
2

 Special cases: - N = nf × M

Acid1 Acid2 Base1 Base2 Acid Base

N1 N2 N1 N2 N1 N2
V1 V2 V1 V2 V1 V2

𝑁1 𝑉1 +𝑁2 𝑉2 𝑁1 𝑉1 +𝑁2 𝑉2
Acid(N) = Base (N) = (1) Salt (Acidic)
𝑉1 +𝑉2 𝑉1 +𝑉2
N1V1 > N2V2
𝑁1 𝑉1 −𝑁2 𝑉2
N=
𝑉1 +𝑉2
(2) Salt (Basic)
N1V1 < N2V2
𝑁2 𝑉2 −𝑁1 𝑉1
N=
𝑉1 +𝑉2
(3) Salt (neutral)
(N1V1 = N2V2)
2. 30ml of 0.1M H2So4, 20 ml of 0.2M HCL and 20ml of 0.1ml Ca(OH)2 are mixed. Find
Resultant Normality?
Sol. H2So4 HCL Ca(OH)2
M1 = 0.1 M2 = 0.2 M3 = 0.1
N1 = 0.1×2 => 0.2 N2 = 0.2×1 =>0.2 N3 = 0.2
V1 = 30ml V2 = 20ml V3 = 20ml
N1V1+N2V2 => 6+4 =>10 > N3V3 = 4

4
 𝑁1 𝑉1 +𝑁2 𝑉2 −𝑁3 𝑉3 10−4 6
N (salt) => => => 𝑛𝑜𝑟𝑚𝑎𝑙
𝑉1 +𝑉2 +𝑉3 70 70

 RAOULT’S LAW: -
“According to this law, vapour pressure of any component in a solutionis equal to
vapour pressure of that component at pure state multiply by mole fraction of that
component.”
 Raoult’s law: -
A B
PAo PBo

Mixed
Solution
PA = 𝑃𝐴𝑜 . 𝑥𝐴, 𝑃𝐵 = 𝑃𝐵𝑜 . 𝑥𝐵
 Case 1: Raoult’s law for volatile solute:
Psolution = PA + PB
Psolution = 𝑃𝐴𝑜 𝑥𝐴 + 𝑃𝐵𝑜 𝑥𝐵

𝑥𝐴 + 𝑥𝐵 = 1

Psolution = 𝑃𝐴𝑜 . 𝑥𝐴 + 𝑃𝐵𝑜 (1 − 𝑥𝐴 )

Graph (Raoult’s law for volatile solute)

PA PB

𝑥𝐵 = 1
PA = 𝑃𝐴𝑜 . 𝑥𝐴 𝑥𝐴 = 1 Mole fraction PB = 𝑃𝐵𝑜 . 𝑥𝐵
𝑥𝐵 = 0 𝑥𝐴 = 0
 Numericals on Raoult’s law: -
1. Benzene (Molwt = 78gm) and Toluene (Molwt = 92gm) are two liquid components
exerting pressure of 20mm and 30mm respectively. Calculate vapour pressure of solution
in following cases: (1) 25gm benzene mixed with 35gm Toluene. (2) equal weights of both
are mixed (3) equal molecules of both are mixed?
Sol. (1) Psolution = 𝑃𝐵𝑜 . 𝑥𝐵 + 𝑃𝑇𝑜 . 𝑥𝑇

5
 25 35
𝑛 𝑛
Psolution = 𝑃𝐵𝑜 . 𝐵 + 𝑃𝑇𝑜 . 𝑇 = 20 × 78
25 35 + 30 × 92
35 25 = 20×0.457+30× 0.54
𝑛𝐵 +𝑛𝑇 𝑛𝑇 +𝑛𝐵 + +
78 92 92 78
= 25.34mm
(2) Psolution = 𝑃𝐵𝑜 . 𝑥𝐵 + 𝑃𝑇𝑜 . 𝑥𝑇
WB = WT = W 𝑤 𝑤
𝑛 𝑛
Psolution = 𝑃𝐵𝑜 . 𝐵 + 𝑃𝑇𝑜 . 𝑇 = 20 × 𝑤 𝑤
78
+ 30 × 92
𝑤 𝑤 = 24.4mm
𝑛𝐵 +𝑛𝑇 𝑛𝑇 +𝑛𝐵 + +
78 92 92 78
𝑜 𝑜
(3) Psolution = 𝑃𝐵 . 𝑥𝐵 + 𝑃𝑇 . 𝑥𝑇
𝑛 𝑛 𝑛 𝑛
Psolution = 𝑃𝐵𝑜 . 𝐵 + 𝑃𝑇𝑜 . 𝑇 = 20 × + 30 × = 25mm
𝑛𝐵 +𝑛𝑇 𝑛𝑇 +𝑛𝐵 𝑛+𝑛 𝑛+𝑛
2. Two liquids X and Y form Ideal solution. Vapour pressure of solution containing 3 moles
of X and 1 mole of Y is 550mm and when 4 moles of X and 1 mole of Y are mixed,
Vapour pressure becomes 560mm. Calculate vapour pressure of pure X and Y?
𝑛 𝑛
Sol. Psolution = 𝑃𝑋𝑜 . 𝑋 + 𝑃𝑌𝑜 . 𝑌
𝑛𝑋 +𝑛𝑌 𝑛𝑌 +𝑛𝑋
3 1
550 = 𝑃𝑋𝑜 × + 𝑃𝑌𝑜 ×
3+1 1+3
𝑜 4 𝑜 1
560 = 𝑃𝑋 × + 𝑃𝑌 ×
4+1 1+4
𝑜 𝑜
𝑃𝑋 = 600𝑚𝑚 𝑃𝑌 = 400𝑚𝑚
3. For an expression: P = 120 − 80𝑥𝐵 . Calculate 𝑃𝐴𝑜 and 𝑃𝐵𝑜 ?
Sol. P = 120 − 80xB
For pure A, xB = 0 For pure B, xB = 1
=> PAo = 120mm => PBo = 120 − 80(1) => 40mm
 Dalton’s law (To find mole fraction in vapour phase): -
PA Po
A . 𝑥A
𝑥A′ (V. P) = =>
Psolution Psolution
1
𝑥B′ (V. P)
= 1 − 𝑥A(V.P)
 Numerical on Dalton’s law: -
1. The vapour pressure of pure liquids A and B are 450mm and 700mm respectively. Find
composition in both liquids phase and vapour phase if vapour pressure of solution is
600mm.
Sol. Psolution = 𝑃𝐴𝑜 . 𝑥𝐴 + 𝑃𝐵𝑜 . (1 − 𝑥𝐴 )
600mm = 450.xA + 700 (1 - xA)
600 = 450.xA + 700 – 700xA
-100 = -250xA
2 3
xA(L.P) = , xB(L.P)=
5 5
2
′ 𝑃𝐴𝑜 .𝑥𝐴 450×
5 ′ 1
𝑥𝐴(𝑉.𝑃) = = = 0.3 𝑥𝐵(𝑉.𝑃) = 1 − 𝑥𝐴(𝑉.𝑃) = 0.7
𝑃𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 600

6
 2. Hexane (86gm) and Heptane (100gm) are liquid components weighing 40gm and 50gm
each exerting vapour pressure of 25mm and 35mm respectively. Calculate composition
in vapour phase.
40

𝑜
25× 40 8650
′ 𝑃𝐻𝑒𝑥 . 𝑥𝐻𝑒𝑥 +
Sol. 𝑥𝐻𝑒𝑥𝑎𝑛𝑒(𝑉.𝑃) = 𝑜
𝑃 . 𝑜
𝑥𝐻𝑒𝑥 +𝑃𝐻𝑒𝑝𝑡 . 𝑥𝐻𝑒𝑝𝑡
= 40
86 100
50 = 0.4
𝐻𝑒𝑥
25× 40 8650 + 35× 5010040
+ +
86 100 100 86
′ 1
𝑥𝐻𝑒𝑝𝑡𝑎𝑛𝑒(𝑉.𝑃) = 1 − 𝑥𝐻𝑒𝑥(𝑉.𝑃) => 1 – 0.4 => 0.6
 Case 2: Raoult’s law for non-volatile solute:
𝑜
𝑜 𝑃𝑠𝑜𝑙𝑣𝑒𝑛𝑡 −𝑃𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
Psolution = 𝑃𝑠𝑜𝑙𝑣𝑒𝑛𝑡 . 𝑥𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑜 = 𝑥𝑠𝑜𝑙𝑢𝑡𝑒
𝑃𝑠𝑜𝑙𝑣𝑒𝑛𝑡
Psolution o
= 𝑥𝑠𝑜𝑙𝑣𝑒𝑛𝑡 Psolvent − Psolution => lowering in V. P
Po
solvent
𝑜
𝑃𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑃𝑠𝑜𝑙𝑣𝑒𝑛𝑡 −𝑃𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
1− 𝑜 = 1 − 𝑥𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑜 => 𝑅𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑙𝑜𝑤𝑒𝑟𝑖𝑛𝑔 𝑖𝑛 𝑉. 𝑃
𝑃𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑃𝑠𝑜𝑙𝑣𝑒𝑛𝑡
𝑚𝑜𝑙𝑒𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛𝑠𝑜𝑙𝑢𝑡𝑒
 Special Cases:
Po
solvent −Psolution
𝑜
𝑃𝑠𝑜𝑙𝑣𝑒𝑛𝑡 −𝑃𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑛𝑠𝑜𝑙𝑢𝑡𝑒
(A) = 𝑥𝑠𝑜𝑙𝑢𝑡𝑒 If solute is 5% or less: - =
Po
solvent
𝑜
𝑃𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑛𝑠𝑜𝑙𝑣𝑒𝑛𝑡
𝑜
𝑃𝑠𝑜𝑙𝑣𝑒𝑛𝑡 −𝑃𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑛𝑠𝑜𝑙𝑢𝑡𝑒
𝑜 =
𝑃𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑛𝑠𝑜𝑙𝑢𝑡𝑒 +𝑛𝑠𝑜𝑙𝑣𝑒𝑛𝑡
(B) Role of molality (m) in relative lowering of vapour pressure: -
Po
solvent −Psolution 𝑛𝑠𝑜𝑙𝑢𝑡𝑒 Po
solvent −Psolution 𝑚
= => = 1000𝑔𝑚
Po
solvent 𝑛𝑠𝑜𝑙𝑢𝑡𝑒 +𝑛𝑠𝑜𝑙𝑣𝑒𝑛𝑡 Po
solvent 𝑚+ (𝑔𝑚)
𝑀𝑜𝑙𝑤𝑡
𝑠𝑜𝑙𝑣𝑒𝑛𝑡

 Numerical on Raoult’s law: -

1. A 2% aqueous solution of non-volatile solute exert pressure of 1.004bar at normal boiling
point of solvent. Calculate molecular weight of solute?
Sol. 2gm of solute in 98 gm of water.
𝑜
Psolution => 1.004bar ; 𝑃𝑠𝑜𝑙𝑣𝑒𝑛𝑡 = 1𝑎𝑡𝑚 or 1.013bar
2
𝑜
𝑃𝑠𝑜𝑙𝑣𝑒𝑛𝑡 −𝑃𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑛𝑠𝑜𝑙𝑢𝑡𝑒 1.013−1.004 𝑀𝑜𝑙𝑤𝑡𝑠𝑜𝑙𝑢𝑡𝑒
𝑜 = <=> = 98
𝑃𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑛𝑠𝑜𝑙𝑣𝑒𝑛𝑡 1.013
18
Molwtsolute = 41.35gm/mole
2. The vapour pressure of water is 12.3k Pa. Calculate vapour pressure of 1 molal aqueous
solution in it?
Po
solvent −Psolution 𝑚
Sol. Po
= 1000𝑔𝑚
solvent 𝑚+ (𝑔𝑚)
𝑀𝑜𝑙𝑤𝑡
𝑠𝑜𝑙𝑣𝑒𝑛𝑡
12.3−𝑃𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 1
= 1000
12.3 1+
18
Psolution = 12.08KPa
7
 3. Calculate the mass of non-volatile solute (molwt = 40gm) which should be dissolved in
114gm of octane (molwt = 114gm) to reduce its vapour pressure by 20%?
Po
solvent −Psolution 𝑛𝑠𝑜𝑙𝑢𝑡𝑒
Sol. Po
=
𝑛𝑠𝑜𝑙𝑢𝑡𝑒 +𝑛𝑠𝑜𝑙𝑣𝑒𝑛𝑡
solvent
𝑚
100−80 40
= 𝑚 114
100 +
40 114
m = 10gm
4. 30gm of non-volatile solute is dissolved in 90gm of water such that vapour pressure of
solution is 2.8kpa. Further when 18gm of water is added; new vapour pressure become
2.9kpa. Calculate molecular weight of solute and vapour pressure of solvent?
Po
solvent −Psolution 𝑛𝑠𝑜𝑙𝑢𝑡𝑒
Sol. Po
=
𝑛𝑠𝑜𝑙𝑢𝑡𝑒 +𝑛𝑠𝑜𝑙𝑣𝑒𝑛𝑡
solvent
30 30
Po
solvent − 2.8 𝑀 Po
solvent −2.9 𝑀
= 30 90 (i) = 30 108 (ii)
Po
solvent + Po
solvent +
𝑀 18 𝑀 18
𝑜
𝑃𝑠𝑜𝑙𝑣𝑒𝑛𝑡 = 3.53KPa 𝑚𝑜𝑙𝑤𝑡𝑠𝑜𝑙𝑢𝑡𝑒 = 23gm
5. Why do gases tends to be less soluble when temperature is increased?
Sol. Gas + solvent Solution + heat
Since it is an exothermic process therefore when temperature increase; reaction shifts in
backward direction in according to lechatlier’s principle therefore solubility of a gas decreases.
 Henry’s law: -
“According to the this law the solubility of a gas in a given solvent depends upon partial
pressure of a gas in equilibrium with solution”.
 Henry’s law: -
𝑛𝑔𝑎𝑠
*Pgas ∝ Solubilitygas *𝑃𝑔𝑎𝑠 = 𝐾𝐻 .
𝑛𝑔𝑎𝑠 + 𝑛𝑠𝑜𝑙𝑣𝑒𝑛𝑡
*Pgas ∝ 𝑥𝑔𝑎𝑠 Since gas (solute) is very less therefore ignored
𝑛𝑔𝑎𝑠
*[𝑃𝑔𝑎𝑠 = 𝐾𝐻 . 𝑥𝑔𝑎𝑠 ] *[𝑃𝑔𝑎𝑠 = 𝐾𝐻 . ]
𝑛𝑠𝑜𝑙𝑣𝑒𝑛𝑡
Henry’s constant
 Numerical on Henry’s law: -
1. If N2 gas is bubbled in 1l of water at 298 K; how many millimoles of it would exert
pressure of 0.987 bar (KH of N2 is 76.48K bar)
𝑛
Sol. 𝑃𝑁2 = 𝐾𝐻(𝑁2 ) × 𝑛 𝑁2𝑜
𝐻2
𝑛𝑁2
0.987 = 76.48 × 103 𝑏𝑎𝑟 × 1000 𝑚𝑖𝑙𝑙𝑖𝑚𝑜𝑙𝑒𝑠𝑁2 => 𝑛𝑁2 × 1000 =0.716millimoles
18

2. Air is a mixture of 20% O2 and 79% N2 exerting total pressure of 10 atm. Find their
7
composition if K H(N2) => 6.5 × 10
7
mm and K H(o2) => 3.3 × 107 mm).
6.5×10 mm
79
Sol. 𝑃𝑁2 = 100 × 10 × 760𝑚𝑚 = 𝐾𝐻(𝑁2 ) × 𝑥𝑁2 𝑥𝑁2 = 9.2 × 10-5

8
 20
𝑃𝑂2 = × 10 × 760𝑚𝑚 = 𝐾𝐻(𝑜2) × 𝑥𝑜2 𝑥𝑜2 = 4.6 × 10-5
100
3.3×107mm
3. H2S is a toxic gas with rotten egg smell. If solubility of H2S in water at S.T.P is 0.195m.
Calculate KH?
𝑛 𝑠
Sol. 𝑃𝐻2 𝑆 = 𝐾𝐻 . 𝐻 2 𝑛𝑤𝑎𝑡𝑒𝑟
𝑚
𝑃𝐻2 𝑆 = 𝐾𝐻 . 1000
18
0.195
760mm = KH ×
55.5
KH = 217142.85
 Significance of KH (Henry’s constant): -
1. KH is a gas dependent term that is different gases have different values of KH.
2. At a particular pressure, KH is inversely proportional to solubility.
1
KH ∝
𝑆𝑜𝑙𝑢𝑏𝑖𝑙𝑖𝑡𝑦
 Applications of Henry’s Law: -
(i) To increase the solubility of CO2 in soft drinks and soda water, the bottle is sealed
under high pressure.
(ii) To minimize the painful effects accompanying the decompression of deep-sea divers,
oxygen diluted with less soluble helium gas is used as breathing gas.
(iii) In lungs, where oxygen is present in air with high partial pressure, haemoglobin
combines with oxygen to form oxyhaemoglobin. In tissues where partial pressures
of oxygen is low, oxyhaemoglobin releases oxygen for utilization of cellular
activities.
 Raoult’s Law as a special case of henry’s Law: -
“According to Raoult’s law, the vapour pressure of a volatile component in a given
solution is directly proportional to its mole fraction”.
𝑃1 = 𝑃1𝑜 𝑥1
In a solution of gas in liquid, the gas is volatile component and its solubility is given by
Henry’s law.
𝑃 = 𝐾𝐻 𝑥
In both the cases, partial pressure of volatile component is directly proportional to its
mole fraction in solution. Only the proportionality constant KH differs from 𝑃1𝑜 . Thus
Raoult’s law is a special case of Henry’s law.
 Question: -
1. At the same temperature, hydrogen is more soluble in water than helium. Which of
them will have a higher value of KH and why?

9
Sol. As 𝑃𝐴 = 𝐾𝐻 𝑥𝐴 . Thus, at constant temperature, for the same partial pressure of different
gases, 𝑥𝐴 ∝ 1⁄𝐾 . In other words, solubility is inversely proportional to Henry’s constant of the
𝐻
gas. Higher the value of KH lower is the solubility of the gas.
As H2 is more soluble than helium, H2 will have lower value KH than that of helium.
 Colligative properties: -
‘’Those properties of solution which depends upon amount of solute rather than nature
are known as colligative properties.
 Four types: -
1) Elevation in boiling point: - (∆𝑻𝒃 )
To b => Boiling point of solvent

Solute is added

Ts b = Boiling point of solution

∆Tb = TS b − To b = k b × m
k b => ebullioscopic constant or molal elevation constant
*Kb is defined as elevation in boiling point when molality is one.
k b = ∆Tb when m = 1
*Kb is a solvent dependent term.
𝐴𝑞𝑢𝑒𝑜𝑢𝑠𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 𝑆𝑜𝑙𝑣𝑒𝑛𝑡 => 𝑤𝑎𝑡𝑒𝑟
𝑇𝑜 𝑏 => 1000 𝐶 𝑜𝑟 373𝑘

 Formula for ebullioscopic constant: -

M. R. To2 b
Kb =
1000∆HV
M = molwtsolvent
∆HV
𝑻𝒐 𝒃 => 373k(Aqueoussolution ) LV =
M
∆HV => enthalpy of vapourization (J/mole)
LV => Latent heat of vapourization (J/gm)
R => 8.314 J/mole
R =>
8.314
KJ/mole R. To 2b
1000 Kb =
R => 2 Cal/mole 1000 LV

10
 y-axis Graph
V.P

1atm

∆𝑇𝑏

x-axis
𝑇𝑜 𝑏 𝑇𝑠 𝑏
T
 Numerical: -
1. A solution containing 0.5126g naphthalene (mol. mass = 128) in 50.0g of carbon tetra
chloride yields a boiling point elevation of 0.4020 C while a solution of 0.6216g of an
unknown solute in the same weight of the same solvent gives a boiling point elevation of
0.6470 C. Find the molecular mass of the unknown solute.
Sol. ∆𝑇𝑏 = 𝑘𝑏 . 𝑚
0.5126 1
0.402=kb × × 50
128
1000
0.6216 1
0.647=kb × × 50
M
1000
M = 96.45gm/mole
2. On dissolving 3.24g of Sulphur in 40g of benzene, boiling point of solution was higher
than that of benzene by 0.81 k. kb value for benzene is 2.53k kg/mole. What is the
molecular formula of Sulphur (At massSulphur = 32).
Sol. ∆Tb = k b × m
3.24 1
0.81 = 2.53 × × 40
32×𝑥
1000
204.93
0.81 = 𝑆𝑥 = 𝑆8
32×x
6.405
0.81 =
𝑥
6.405
𝑥= = 7.9 𝑜𝑟 8
0.81
2) Depression in freezing point: - (∆𝐓𝐟 )
To f => Freezing point of solvent
Solute is added
Ts f => Freezing point of solution

11
 ∆Tf = TO f − Ts f = k f . m

k f = molal depression constant or Cryo Scopic constant

K f = ∆Tf when m = 1
𝐴𝑞𝑢𝑒𝑜𝑢𝑠𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑇𝑜 𝑓 = 𝑂𝑜 𝐶 𝑜𝑟 273𝑘 𝑀. 𝑅. 𝑇𝑜 2𝑓 𝑅. 𝑇𝑂 2𝑓
(𝑤𝑎𝑡𝑒𝑟)
𝑘𝑓 = =
M = molwt of solvent 1000∆𝐻𝑓 1000𝐿𝑓
8.314
R = 8.314j/mole or kj/mole
1000
∆Hf => enthalpy of fusion (J/mole)
𝐿𝑓 => 𝑙𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑓𝑢𝑠𝑖𝑜𝑛

∆Hf
J/gm
M
Graph
y-axis
V.P

∆𝑇𝑓

x-axis
𝑇𝑠 𝑓 𝑇𝑜 𝑓 T

 Numerical on depression in freezing point: -

1. A solution of urea in water has a boiling point of 100.128oC. Calculate the freezing point
of the same solution. Molal constant for water kf and kb 1.86oC, 0.512oC respectively.
Sol. Ts b => 100.128o C
To b => 100o C
Ts f =>?
To f => 0o C
Ts b −To b =kb .m
To f −Ts f =kf .m

12
 100.128−100=0.512×𝑚
Ts f = -0.465oC
0−𝑇𝑠 𝑓 =1.86×𝑚

2. How many grams of sucrose (M wt = 342) should be dissolved in 100g water in order to
produce a solution with 105.0oC difference between the freezing point and boiling point?
(kf = 1.86o C/m, kb = 0.51o C/m)
Sol. Wsucrose = ? WH 2 o = 100gm
𝑇𝑠 𝑏 − 𝑇𝑠 𝑓 => 105
[To b + k b . m] − [To f − k f . m] = 105
𝑇𝑜 𝑏 − 𝑇𝑜 𝑓 + 𝑚 [𝑘𝑏 + 𝑘𝑓 ] = 105
𝑊 1
100-0+ × 100 [0.51+1.86]=105 W=72gm
342
1000

3. A 5% solution (by mass) of cane sugar in water has freezing point 271k. Calculate the
freezing point of a 5% glucose in water if freezing point of pure water is 273.15k.
5 1
273.15−271=kf × × 95
342
Sol. 5
1000
1
273.15−Ts f =kf × × 95
180
1000
𝑇𝑠 𝑓 = 269𝐾
4. Two element A and B form compounds having molecular formula AB2 and AB4. When
dissolved in 20g of benzene(C6H6), 1g of AB2 lowers the freezing point by 2.3k whereas
1.0g of AB4 lowers it by 1.3k. The molal depression constant for benzene is 5.1k kg mol-1.
Calculate atomic masses of A and B.
Sol. AB2 AB4
∆𝑇𝑓 = 𝑘𝑓 × 𝑚 ∆𝑇𝑓 = 𝑘𝑓 × 𝑚
1 1 1 1
2.3 = 5.1 × × 20 1.3 = 5.1 × × 20
MAB 2 MAB 4
1000 1000
𝑀𝐴𝐵 2 = 𝐴 + 2𝐵 𝑀𝐴𝐵 4 = 𝐴 + 4𝐵
A=25.59gm
B=42.64gm
5. Latent heat fusion of ice is 1436.3cal mol-1. Calculate the molal depression constant of
water.
1M RT2O 18×2×(273K)2
Sol. Kf = 1000∆ =
1000×1436.3cal mol−1
= 1.87K kg mol-1
fus H

 Osmosis: -
*“Osmosis is defined as the flow of solvent molecules from lower concentration solution
towards high concentration solution through semi permeable membrane is known as
osmosis”.
*The minimum amount of pressure that must be applied towards high concentration
solution so that the flow of solvent stops is known as osmotic pressure.
13
 *When pressure more than osmotic pressure is applied so that the flow of solvent is
reversed is known as reverse osmosis.

𝜋 =CRT(k)

Molarity 0.0821 Latm

𝑛
𝑉(𝑙)
 Isotonic solution: -
“Two solution are said to be isotonic if they have same osmotic pressure at a particular
temperature T(kelvin)”.
(𝜋1 = 𝜋2) T(k)  C1RT = C2RT  C1 = C2
 Numerical on osmosis: -
1. 5% aqueous solution of glucose is isotonic with 10% aqueous solution of unknown
substance (Find its molecular weight).
Sol. 5% Glucose isotonic with 10% X (It means 5gm of glucose in 100ml of solution isotonic
with 10gm of X in 100ml of solution).
5 1 10 1
𝐶𝐺𝑙𝑢𝑐𝑜𝑠𝑒 = 𝐶𝑋  × 100 = × 100  MX = 360gm
180 𝑀𝑋
1000 1000

2. 100cm3 of 1.8% of glucose is mixed with 100cm3 of 3.42% cane sugar. Calculate the
resultant osmotic pressure at 27o C.
Sol. 1.8gm glucose 3.42gm of cane sugar

100cm3 100cm3
Mix
1.8 3.42
nglucose +ncane sugar +
180 342
πres = (l) ×R×T= 200 × 0.0821 × 300K = 2.46atm
VTotal 1000

 Biological importance of osmosis: -

1) Plants absorb water from the soil through their roots due to osmosis because
concentration of cell sap inside root hair cells is higher than that of the water present in
the soil.
2)
(i) A 0.9% solution of pure Nacl is isotonic with human red blood cells(RBC). Therefore,
in this solution, RBC neither swell nor undergo plasmolysis.
(ii) A pure Nacl solution with concentration less than 0.9% is called hypotonic solution.
On placing RBC in this solution, they will swell and even burst.

14
 (iii)
A pure Nacl solution with concentration more than 0.9% is called hypertonic
solution. On placing RBC’s in this solution, they shrink due to plasmolysis.
3) For the determination of molecular masses of proteins, polymers and other
macromolecules, it is considered to be one of the most suitable methods because of the
following reason: -
(i) The changes observed in these properties are very small. On the other hand,
osmotic pressure can be easily measured in terms of mm.
(ii) Elevation in boiling point method for biomolecules such as proteins is not suitable
because these molecules are not stable at higher temperature whereas the
advantages of the osmotic pressure is that it can be measured at room
temperature.
(iii) The osmotic pressure method has the advantage that it uses molarities instead of
molalities.
 Numerical on osmotic pressure: -
1. The osmotic pressure of a urea solution is 500mm of Hg at 10o C. The solution is diluted
and its temperature is raised to 30o C. Its is now found that osmotic pressure of the
solution is reduced to 100mm of Hg. Determine the extent of dilution of the solution.
Sol. ∧= CRT
500mm
𝜋1 =C1 .R283K 500=𝐶1
= × 0.94
𝜋2 =C2 .R303K 100=𝐶2
100mm
C1 1 5 𝑉
= × = 5.3 Therefore: 2 = 0.188
C2 0.94 1 𝑉1

 Vanthoff’s factor(i)
Electrolyte
Dissociate Associate
+ −
𝐾 𝐶𝑙 (𝑛 = 2) Dimer
𝑁𝑎2 (𝑆𝑜4 ) (𝑛 = 3) 2A (A)2
1
𝐴𝑙. 𝐶𝑙3 (𝑛 = 4) n=
2
𝐾4 [𝐹𝑒(𝐶𝑁)6 ] (𝑛 = 5) Trimer
1
n=
3
Tetramer
1
n=
4
i = 1 + (n-1)∝ Degree of dissociation or association

15
  Numerical: -
1. Calculate Vanthoff’s factor (i) in following cases.
Sol. (i) 50% dissociation of K2So4
50
i = 1+(3-1) =2
100
(ii) 30% association of No2
1 30
i = 1+ ( − 1) = 0.85
2 100
 Definition of i: -
“(i) is define as ratio of calculated molecular mass and observed or abnormal molecular
mass”. M c
i=
Mo
 Abnormal molecular mass: -
“Defined as molecular mass of electrolytic solute (Mo) when it is dissolved in a solvent to
form solution such that it either dissociate or associate”.

Non-electrolyte
Mc = Mo eg: - urea, glucose
i=1 Sucrose

Electrolyte
Dissociate Associate
Mc > Mo Mc < Mo
Mc Mc
>1 <1
Mo Mo
i>1 i<1
∆𝑇𝑏 = 𝑇𝑠 𝑏 − 𝑇𝑜 𝑏 => 𝑖𝑘𝑏 . 𝑚
∆𝑇𝑓 = 𝑇𝑜 𝑓 − 𝑇𝑠 𝑓 => 𝑖𝑘𝑓 . 𝑚
π = iCRT
Po −Ps
= i × xsolute
Po
 Numerical: -
1. 0.5g KCL was dissolved in 100g water and the solution originally at 20o C, froze at -0.24oC.
Calculate the percentage ionization of salt kf per 1000g of water = 1.86oC.
Sol. TO f − Ts f = i k f m
0.5 1
0oC -0.24oC 1.86 74.5
× 100 α = 0.92
1000

i = 1 + (n - 1)𝛼 𝛼 % = 𝛼 × 100 =92%

2
16
 2. 2g of benzoic acid dissolved in 25g of benzene, depression in freezing point equal to 1.62k.
Molal depression constant (kf) of benzene is 4.9k kg/mol. What is the percentage
association of the acid if it forms dimer in the solution?
Sol. ∆Tf = i . k f . m
2 1
1.62k = i × 4.9 × × 25
122
1000
1
i = 1 + (n – 1) α = 1 + ( − 1)𝛼 α = 0.992
2
1
α% = α × 100 =99.2%
2
3. 0.6ml of acetic acid (𝐶𝐻3 𝐶𝑜𝑜− 𝐻+ ) having a density of 1.06g/ml is dissolved in 1l of
water. The depression in freezing point observed for this strength of the acid was
0.0205oC. Calculate the Vanthoff’s factor and the dissociation constant of the acid. kf for
water =1.86k kg mol-1.
𝑀𝑎𝑠𝑠𝑠𝑜𝑙𝑢𝑡𝑒
Sol. ∆Tf = i . k . m 1.06 =
0.6
0.6 × 1.062 1
0.0205 = i × 1.86 × × msolute = 1.06 × 0.6gm
60 1𝑘𝑔
1.04 = i = 1+(2-1)α
α = 0.04
Cα2
𝑘= = 1.76 × 10-5
1−α
4. Phenol associates in benzene to a certain extent to form dimer. A solution containing 2.0
× 10-2kg of phenol in 1kg of benzene has its freezing point decreased by 0.69k. Calculate
the degree of association of phenol (kf for benzene = 5.12k kg/mol).
Sol. ∆Tf = i . k . m
2×10−2 ×1000 1
0.69 = i x 5.12 x ×
94 1𝑘𝑔
1
i = 1 + ( – 1) α
2
α = 0.734
5. A decimolar solution of potassium ferrocyanide k4[fe (CN)6] is 50% dissociated at 300k.
Calculate the osmotic pressure of the solution. [R = 0.0821 atm]
Sol. 𝜋 = 𝑖. 𝐶. 𝑅. 𝑇
50 1
π = [1 + (5 − 1) ]× × 0.081 × 300k
100 10
π = 7.4atm
6. Calculate the depression in the freezing point of water when 10g of 𝐶𝐻3 𝐶𝐻2 𝐶𝐻𝐶𝑙𝐶𝑂𝑂𝐻
is added to 250g of water. Ka = 1.4 x 10-3, kf = 1.86k kg/mol.
Sol. ∆Tf = ikm
10 1 10
∆𝑇𝑓 = [1 + (𝑛 − 1)𝛼]. kf . m × 250 => × 4 =>0.326
122.5 122.5
1000

17
 𝐶α2 0.326𝛼 2
Ka = 1.4 × 10-3= => α = 0.065
1−𝛼 1−𝛼
∆𝑇𝑓 = [1 + (2 − 1)0.065] × 1.86 × 0.326 = 0.65𝑜
7. 19.5g of CH2FCOOH is dissolved in 500g of water. The depression in the freezing point
observed is 1.0oC. Calculate the Vanthoff’s factor and dissociation constant of
Fluoroacetic acid. Kf for water is 1.86k kg/mol.
Sol. ∆Tf = ikm
19.5 1
1oC = [1+(2-1) α] 1.86 × × 500
78
1000
19.5 1
1 = [1+α] 1.86 × ×
78 0.5
36.27
1 = [1+𝛼]
39
α = 0.0753 ; i = 1 +α = 1.0753
𝐶𝛼 2
ka = = 3.07×10-3
1−𝛼
8. Determine the osmotic pressure of a solution prepared by dissolving 25mg of k2So4 in 2
litres of water at 25oC, assuming that it is completely dissociated.
Sol. π = iCRT
100 0.025 1
π = [1 + (3 − 1) ] × × 0.0821 × 298k
100 174 2
0.025 1
π=3× × × 0.0821 × 298k
174 2
π = 5.27 × 10−3 𝑎𝑡𝑚
 If concentration is same : -
∆Tf = To f − Ts f αi
1
* Ts f α
i
∆Tb = Ts b − To b αi
∗ Ts b αi
*𝜋𝛼𝑖
1
∗ Ps α
i
 Arrange in 𝑻𝒔𝒇 order: -
1. 1M urea => i = 1
2. 1M CaCl2 => i = 3
3. 1M Ba3(Po4)2 => i = 5
4. 1M AlCl3 => i = 4
1
Ts f α
i
3 < 4 < 2 < 1
𝑇𝑠 𝑓

18
 Arrange in osmotic pressure order: - (i × C)
𝑔𝑚 1
1. 30 𝑙 of urea(60) 1 ×
2
= 0.5
𝑔𝑚
2. 58.5 𝑙 of NaCl(58.5) 2 × 1=2
𝑔𝑚 1
3. 55.5 𝑙 of CaCl2 (111) 3 ×
2
= 1.5
𝑔𝑚
4. 180 𝑙 of glucose(180) 1 × 1=1
𝛑αi×C
1 < 4 < 3 < 2
 Ideal solution: -
(1) “Those solutions which obey Raoult’s law under all conditions of temperature and
pressure are known as ideal solution”.
(2) Here the magnitude of interactions of solute – solute, solvent – solvent, and solute –
solvent comes out to be same.
(3) Graph for ideal solution is same as Raoult’s law for volatile solute.

PA PB

𝑥𝐴 = 1 𝑥𝐵 = 1
𝑥𝐵 = 0 𝑥𝐴 = 0

(4) Here neither heat is evolved nor absorbed i.e. ∆𝐻 mixing = 0 and ∆𝑉mixing = 0.
For example: - Benzene + Toulene
Hexane + Heptane
 Non-ideal solution: -
Two types: -
1. Non ideal showing +ve deviation from Raoult’s law: -
*Here vapour pressure of each component as well as solution is found to be more than
expected from Raoult’s law.
PA > PAo 𝑥𝐴 PB > PBo 𝑥𝐵
𝑃𝑆 > 𝑃𝐴𝑜 𝑥𝐴 + 𝑃𝐵𝑜 𝑥𝐵

19
 𝑃𝑆 > 𝑃𝐴𝑜 𝑥𝐴 + 𝑃𝐵𝑜 𝑥𝐵

𝑃𝐵𝑜

𝑃𝐴𝑜
PA PB

xA = 1 xA = 0
xB = 0 xB = 1
*Here the magnitude of interaction for solute – solute, solvent – solvent is found to be
more than solute – solvent.
For example: - Alcohol + water
C2H5 O H O
H- - - - O C2 H 5 H- - - - -O H
H H

Strong H – bonding Strong H – bonding

Since the magnitude of interaction for ethanol – ethanol, water – water is found to be
more than ethanol – water. It represents non ideal showing +ve deviation from Raoult’s
law.
 Question for above concept
a) What role the interaction plays when we mix alcohol with H2o.
*Whenever this solution is formed ∆𝐻𝑚𝑖𝑥𝑖𝑛𝑔 > 𝑂
i.e. heat is absorbed (endothermic) so Solution become little cooler
*Whenever this solution is formed ∆𝑉𝑚𝑖𝑥𝑖𝑛𝑔 > 𝑂
*These solutions are also called min boiling azeotropes (azeotropes are liquid mixtures
which distills without any changes in their composition) because there vapour pressure
is found to be more than expected from raoult’s law.
For example: - Alcohol + water
2. Non ideal solution show -ve deviation: -
*Here vapour pressure of each component as well as solution is found to be less than
expected from Raoult’s law.
PA < 𝑃𝐴𝑜 𝑥𝐴 𝑃𝐵 < 𝑃𝐵𝑜 𝑥𝐵 𝑃𝑆 < 𝑃𝐴𝑜 𝑥𝐴 + 𝑃𝐵𝑜 𝑥𝐵

20
 𝑃𝐵𝑜
𝑃𝑆 < 𝑃𝐴𝑜 𝑥𝐴 + 𝑃𝐵𝑜 𝑥𝐵

PAo
PA PB

xA = 1 xA = 0
xB = 0 xB = 1
*Here the magnitude of interactions solute – solute and solvent – solvent are found to
be less thansolvent – solute.
*Whenever this solution is formed ∆𝐻𝑚𝑖𝑥 < 𝑂,
i.e. heat is evolved. So, the solution become little warmer and ∆𝑉𝑚𝑖𝑥 < 𝑂.
*It is also known as max boiling azeotropes ( azeotropes are liquid mixtures which distills
without any changes in their composition) because their vapour pressure is found to be
less than expected from Raoult’s law.
For example: - Chloroform and Acetone.
 Two types of solid solutions: -
(i) Substitutional solid solution: -
Here two salt substances are mixed with each other in such a way that the atoms of one
solid substance easily replaces that of another and a substitutional solid solution is
formed
For example: - Brass, bronge
(ii) Interstitial solid solution: -
When two solid substances are mixed with each other such that atoms of one salt.
Substance easily fits into interstitial site of larger size solid substances such that interstitial
solid solution is formed.
For example: - Tungsten Carbide, Manganese Hydride.
 Miscellaneous questions: -
a) Equimolal solutions of NaCl and BaCl2 are prepared in water. Freezing point of NaCl is
found to be -2oC. What freezing point do you expect for BaCl2 solution?
Sol. i for NaCl = 2, i for BaCl2 = 3.
(∆T )NaCl 2 3
Hence, (∆T f)BaCl = or (∆Tf )BaCl2 = 2 × 2 = 3o so that Tf for BaCl2 = -3oC.
f 2 3
b) Why is freezing point depression of 0.1 M sodium chloride solution nearly twice that of
0.1 M glucose solution?
21
Sol. NaCl, being an electrolyte, dissociates almost completely to give Na+ and Cl- ions whereas
glucose, being non electrolyte, does not dissociate. Hence, the number of particles in 0.1 M NaCl
solution is nearly double than in 0.1 M glucose solution. Freezing point depression, being a
colligative property, is therefore, nearly twice for NaCl solution than for glucose solution of same
molarity.
c) Explain why equimolar aqueous solutions of sodium chloride and sodium sulphate are
not isotonic?
Sol. NaCl dissociates to give 2 ions (Na+ and Cl-). Na2SO4 dissociates to give 3 ions (2Na+ and
𝑆𝑂42− ). Thus, equimolar solutions of NaCl and Na2SO4 have different concentrations of ions in
the solution. As osmotic pressure depends upon concentrations of particles in the solution, they
have different osmotic pressures.
d) Suggest the most important type of intermolecular interaction in the following pairs:
(i) n-hexane and n-octane (ii) I2 and CCl4 (iii) NaClO4 and water (iv) methanol and acetone
(v) acetonitrile (CH3CN) and acetone (C3H6O).
Sol. (i) Both are non-polar. Hence, intermolecular interactions in them will be London
dispersion forces.
(ii) Same as (i)
(iii) NaClO4 gives Na+ and CIO-4 ions in the solution while water is a polar molecule. Hence,
Intermolecular interactions in them will be ion-dipole interactions.
(iv) Both are polar molecules. Hence, intermolecular interactions in them will be dipole-
dipole interactions.
(v) Same as (iv).
e) Based on solute-solvent interactions, arrange the following in order of increase solubility
in n-octane and explain. Cyclohexane, KCl, CH3OH, CH3CN
Sol. (i) Cyclohexane and n-octane both are non-polar. Hence, they mix completely in all
Proportions.
(ii) KCl is an ionic compound while n-octane is non-polar. Hence, KCl will not dissolved at
all in n-octane.
(iii) CH3OH and CH3CN both are polar but CH3CN is less polar than CH3OH. As the solvent
is non-polar, CH3CN will dissolve more than CH3OH in n-octane.
Thus, the order of solubility will be KCl < CH3OH < CH3CN < Cyclohexane.
f) Amongst the following compounds, identify which are insoluble, partially soluble and
highly soluble in water (i) phenol, (ii) toluene, (iii) formic acid, (iv) ethylene glycol,
(v) chloroform, (vi) pentanol.
Sol. (i) Partially soluble because phenol has polar –OH group but aromatic phenyl, C6H5- group.
(ii) Insoluble because toluene is non-polar while water is polar.
(iii) Highly soluble because formic acid can form hydrogen bonds with water.
22
 (iv) Highly soluble because ethylene glycol can form hydrogen bonds with water.
(v) Insoluble because chloroform is an organic liquid.
(vi) Partially soluble because –OH group is polar but the larger hydrocarbon part (C5H11) is
non-polar.
g) Why is the vapour pressure of an aqueous solution of glucose lower than that of water?
Sol. It is because in glucose solution, the surface of liquid consists of both solute and solvent
molecules, therefore, the fraction of surface covered by the solvent molecules gets reduced.
Hence, escaping tendency of solvent molecules into vapours also gets reduced, thus, vapour
pressure of glucose solution decreases.
h) How does sprinkling of salt help in clearing snow covered roads in hilly areas? Explain the
phenomenon involved in the process.
Sol. When salt is spread over snow covered roads, snow starts melting from the surface
because of the depression in freezing point of water and it helps in clearing the roads.
i) Explain why on addition of 1 mole of NaCl to 1 litre of water, the boiling point of water
increases, while addition of 1 mole of methyl alcohol to one litre of water decrease its
boiling point.
Sol. NaCl is a non-volatile solute, therefore, it lowers the vapour pressure of water which
results in increase in the boiling point.
Methyl alcohol is more volatile than water, therefore, it increases total vapour pressure over
the solution which results in decrease in boiling point.
j) The depression in freezing point of water observed for same amount of acetic acid,
trichloroacetic acid and trifluoroacetic acid increase in the order given above. Explain
briefly.
Sol. It is because trifluoroacetic acid is stronger acid than trichloroacetic acid, whereas acetic
acid is the weakest acid. Stronger acid produces more number of ions, therefore, has more ∆𝑇𝑓 .
 M.C.Q for competitive exam: -
1. The mole fraction of a gas dissolved in a solvent is given by Henry’s law. If the Henry’s law
constant for a gas in water at 298K is 5.55 × 107 Torr and the partial pressure of the gas is
200 Torr, then what is the amount of the gas dissolved in 1.0kg of water?
(a) 2.0 × 10-4 mol (b) 2.5 × 10-5mol (c) 3.7 × 10-6mol (d) 1.2 × 10-8mol
2. The solubility of a gas in water at 300K under a pressure of 100 atmospheres is 4 × 10-3kg
L-1. Therefore, the mass of the gas in kg dissolved in 250ml of water under a pressure of
250 atmospheres at 300K is
(a) 2.5 × 10-3 (b) 2.0 × 10-3 (c) 1.25 × 10-3 (d) 5.0 × 10-3 (e) 3 × 10-3
3. The amount of solute (molar mass 60g mol-1) that must be added to 180g of water so that
the vapour pressure of water is lowered by 10% is

23
 (a) 30g (b) 60g (c) 120g (d) 12g (e) 24g
4. At 80oC, the vapour pressure of pure liquid ‘A’ is 520mm Hg and that of pure liquid ‘B’ is
1000mm Hg. If a mixture solution of ‘A’ and ‘B’ boils at 80oC and 1atm pressure, then
amount of ‘A’ mixture is (1 atm = 760mm Hg)
(a) 48 mol percent (b) 50 mol percent (c) 52 mol percent (d) 34 mol percent
5. Two liquids X and Y form an ideal solution. The mixture has a vapour pressure of 400mm
at 300K when mixed in the molar ratio of 1 : 1 and a vapour pressure of 350mm when
mixed in the molar ratio of 1 : 2 at the same temperature. The vapour pressure of the two
pure liquids X and Y respectively are
(a) 250mm, 550mm (b) 350mm, 450mm (c) 350mm, 700mm (d) 500mm, 500mm
(e) 550mm, 250mm
6. Two liquids X and Y forms an ideal solution. At 300K, vapour pressure of the solution
containing 1 mol of X and 3 mol of Y is 550mm Hg. At the same temperature if 1 mol of Y
further added to this solution, vapour pressure of the solution increase by 10mm Hg.
Vapour pressure (in mm Hg) of X and Y in their pure states will be respectively
(a) 200 and 300 (b) 300 and 400 (c) 400 and 600 (d) 500 and 600
7. If two substances A and B have PAo : PBo = 1 : 2 and have mole fraction in solution 1 : 2,
then mole fraction of A in vapours is
(a) 0.33 (b) 0.25 (c) 0.52 (d) 0.2
8. The relative lowering of vapour pressure of an aqueous solution containing non-volatile
solute is 0.0125. The molality of the solution is
(a) 0.70 (b) 0.50 (c) 0.60 (d) 0.80 (e) 0.40
9. An ideal solution is formed by mixing two volatile liquids A and B. XA and XB are the mole
fractions of A and B respectively in the solution and YA and YB are the mole fractions of A
and B respectively in the vapour phase. A plot of 1/YA along y-axis against 1/XA along x-
axis gives a straight line. What is the slope of the straight line?
(a) PBo/PAo (b) PAo/PBo (c) PBo- PAo (d) PAo- PBo
10. 1 mole of liquid A and 2 moles of liquid B make a solution having a total vapour pressure
of 38 torr. The vapour pressures of pure A and B are 45 torr and 36 torr respectively. The
described solution
(a) is an ideal solution (b) shows negative deviation (c) is a minimum boiling azeotrope
(d) has volume greater than the sum of individual volumes
11. The empirical formula of a non-electrolyte is CH2O. A solution containing 3g L-1 of the
Compound exerts the same osmotic pressure as that of 0.05 M glucose solution. The
Molecular formula of the compound is
(a) CH2O (b) C2H4O2 (c) C4H8O4 (d) C3H6O3
12. A 5.25% solution of a substance is isotonic with a 1.5% solution of urea (molar mass = 60g
24
 Mol-1) in the same solvent. If densities of both the solutions are assumed to be equal to
1.0g cm-3 molar mass of the substance will be
(a) 210.0g mol-1 (b) 90.0g mol-1 (c) 115.0g mol-1 (d) 105.0g mol-1
13. A solution containing 1.8g of a compound (empirical formula CH2O) in 40g of water is
observed to freeze at – 0.465o C. The molecular formula of the compound is (Kf of water
=1.86kg K mol-1)
(a) C2H4O2 (b) C3H6 (c) C4H8O4 (d) C5H10O5 (e) C6H12O6
14. A solution of urea (mol. mass 56g mol-1) boils at 100.18oC at the atmospheric pressure. If
Kf and Kb for water are 1.86 and 0.512K kg mol-1 respectively, the above solution will
Freeze at
(a) -6.54oC (b) -0.654oC (c) 6.54oC (d) 0.654oC
15. In 100g of naphthalene, 2.423g of S was dissolved. Melting point of naphthalene = 80.1oC.
∆𝑇𝑓 = 0.661𝑜 𝐶. 𝐿𝑓 = 35.7𝑐𝑎𝑙/𝑔 of naphthalene. Molecular formula of Sulphur added is
(a) S2 (b) S4 (c) S6 (d) S8
16. Kf for water is 1.86K kg mol-1. If your automobile radiator holds 1.0 kg of water, how many
Grams of ethylene glycol (𝐶2 𝐻6 𝑂2 ) must you add to get the freezing point of the solution
Lowered to -2.8oC?
(a) 27g (b) 72g (c) 93g (d) 39g
17. When mercuric iodide is added to the aqueous solution of potassium iodide
(a) freezing point raised (b) freezing point is lowered (c) freezing point does not change
(d) boiling point does not changes
18. A solution containing 50g of ethylene glycol in 200 g of water is cooled to -9.3oC. The
amount of ice that will separate out will be (Kf = 1.86 Km-1)
(a) 18.71g (b) 28.71g (c) 38.71g (d) 48.71g
19. Which of the following aqueous solution has the highest boiling point?
(a) 0.1 M KNO3 (b) 0.1 M Na3PO4 (c) 0.1 M BaCl2 (d) 0.1 M K2SO4
20. Which one of the following electrolytes has the same value of van’t Hoff factor (i) as that
of Al2(SO4)3 (if all are 100% ionized)
(a) K2SO4 (b) K3[Fe(CN)6] (c) Al(NO3)3 (d) K4[Fe(CN)6]
21. 1g of a monobasic acid in 100 g of water lowers the freezing point by 0.168o. If 0.2g of the
Same acid requires 15 ml of N/10 alkali for complete neutralization, the degree of
dissociation of the acid is (Kf for water = 1.86K kg mol-1)
(a) 9.8% (b) 19.6% (c) 4.9% (d) 1.68%
22. The freezing point (in oC) of a solution containing 0.1g of K3[Fe(CN)6] (Mol. Wt. 329) in
100g of water (Kf = 1.86K kg mol-1) is
(a) -2.3 x 10-2 (b) -5.7 x 10-2 (c) -5.7 x 10-3 (d) -1.2 x 10-2

25
23. The freezing point depression constant for water is -1.86oC m-1. If 5.00g Na2SO4 is dissolved
In 45.0g H2O, the freezing point changed by -3.82oC. Calculate the vant’ Hoff factor for
Na2SO4
(a) 0.381 (b) 2.05 (c) 2.63 (d) 3.11
24. A 0.1 molal aqueous solution of a weak acid is 30% ionized. If Kf for water is 1.86o C/m,
the freezing point of the solution will be
(a) -1.18oC (b) -0.54oC (C) -0.36oC (d) -0.24oC
25. A 0.004 M solution of Na2SO4 is isotonic with a 0.010 M solution of glucose at the
temperature. The apparent degree of dissociation of Na2SO4 is
(a) 25% (b) 50% (c) 75% (d) 85%
26. van’t Hoff factors x, y and z for association, dissociation and no change of solute in the
Solution respectively are in order:
(a) x < y < z (b) x > z > y (c) x < z < y (d) x > y > z
27. For week monobasic acid, if pKa = 4, then at a concentration of 0.01 M of the acid solution,
the van’t Hoff factor is
(a) 1.01 (b) 1.02 (c) 1.10 (d) 1.20
28. The pH of 1 M solution of a weak monobasic acid (HA) is 2. Then, the van’t Hoff factor is
(a) 1.01 (b) 1.02 (c) 1.10 (d) 1.20
29. One molal solution of a complex of cobalt chloride with NH3 in water showed an elevation
in boiling point equal to 2.08o. Assuming that the complex is completely ionized in the
solution, the complex is (Kb for water = 0.52 K kg mol-1)
(a) [Co(NH3)6] Cl3 (b) [Co(NH3)5Cl] Cl2 (c) [Co(NH3)4Cl2] Cl (d) None of these
30. Depression in freezing point of 0.01 m aqueous acetic acid solution is found to be 0.02046
K. One molal urea solution freezes at -1.86oC. Assuming molarity equal to molality. pH of
acetic acid solution is
(a) 2 (b) 3 (c) 3.2 (d) 4.2
 Answers:
1. (a) 2. (a) 3. (b) 4. (b) 5. (e) 6. (c) 7. (d) 8. (a) 9. (a) 10. (b) 11. (b) 12. (a) 13. (e) 14. (b)
15. (d) 16. (c) 17. (a) 18. (c) 19. (b) 20. (d) 21. (b) 22. (a) 23. (c) 24. (d) 25. (c) 26. (c) 27. (c)
28. (a) 29. (a) 30. (b)

26