IIT JEE

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INDIA’S FIRST NOTES WITH MOST
IMPORTANT SUBTOPICS MARKED
ACCORDING TO JEE MAINS
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SAMPLE PROBLEMS FOR

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UNDERSTANDING WHICH ARE

HIGHLY EXPECTED IN JEE MAINS
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EXAM
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 Chapter - 1
SOLUTIONS
1.1 Introduction
When several non reacting substances are mixed, then there are three possible types of mixtures :

(a) Coarse mixture (Sand + Salt and Sugar + Salt)

(b) Colloidal dispersion (Gum + water and fine clay + water)

(c) True Solution (Salt + water)

In the coarse mixture there exists heterogeneity where as in true solutions there is complete
homogeneity, In colloidal dispersions the heterogeneity is not readily apparent and it is not homogeneous.

Distinction between Solute and Solvent

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I. Phase Method: Let there be a substance ‘A’ in solid phase and ‘B’ in liquid phase then if the
phase of the resulting mixture is
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(a) Solid, then Solute = B and Solvent = A.

(b) Liquid, then Solute = A and Solvent = B.

II. Amount Method: According to this method, the substance which is in larger proportion by mass
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is solvent while the one in lesser proportion is solute.

Example: a solid mixture of A and B. If WA > WB then solute is B and solvent is A.

In the solutions of solids in liquids, where the liquid is usually present in large excess over the
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solid, there is no ambiguity, here liquid is solvent and solid is solute.

However, when we deal with solubility of liquid.

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Example: Acetone + water, here the one which is in larger quantity is solvent.

Saturated, Unsaturated And Super Saturated Solutions

Saturated Solution: A solution, which contains as much solute as it can hold at a given temperature
is said to be a saturated solution.

Unsaturated Solution: A solution which contains less solute than the amount of solute it can hold
then it is called unsaturated solution.

Super Saturated: A solution which contains more solute than the amount it can hold at a particular
temperature is called a super saturated solution.

Factors Influencing Solubility

The extent to which a substance will dissolve in another varies greatly with the substance, and
depends on nature of solute, solvent, temperature, and pressure.

[1]
Solutions

1. The effect of pressure on solubility is small unless gases are involved.

2. The effect of temperature however is very pronounced. The direction in which the solubility of
a substance in a solvent, changes with temperature depends on heat of solution.
(a) If the dissolution is exothermic then the solubility decreases with increase in temperature.
(b) If the dissolution is endothermic then the solubility increases with increase in temperature.
3. In general, the compounds with similar character are more readily soluble in each other. While
those with entirely different chemical characteristics will be very much insoluble.
Hence with these two extreme ends, a considerable number of intermediate stages are possible,
which we call as mutual solubilities, e.g.
(i) When ethyl alcohol and water are mixed, the two dissolve in each other in all proportions and
hence there is no saturation limit. Such substances are completely miscible.
(ii) When water and mercury are mixed they do not dissolve in each other at all and hence are
called completely immiscible.
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(iii) Between these two extreme pairs we have liquid pairs as ether + water, phenol + water
which dissolve in each other to a limited extent only. Liquid pairs of these kinds are called
partially miscible.
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Types of Binary Solutions (Table-1)

[Link]. Solute Solvent Example of solution

1. Solid Solid Alloy (Brass)
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2. Liquid Solid Hydrated salts butter

3. Gas Solid H2/Ni adsorption
4. Solid Liquid Sugar in water
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5. Liquid Liquid Alcohol in water

6. Gas Liquid Cold Drinks
7. Solid Gas Dust, Smoke
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8. Liquid Gas Fog

9. Gas Gas Air

Expressing concentration of Solutions

Concentration of a solution is defined as the amount of solute dissolved in a known amount of the
solvent or the solution.

The concentration of a solution can be expressed in various ways as follows:

1. Percentage of Solution:

[2]
Solutions

The formula for calculating percentage concentration is:

Mass of the component in the solution

Mass % of a compound (w/w %) =  100
Total mass of solution
Mass of the component in the solution
Mass / volume % of a component (w/v %) = 100
Total volume of the solution (in ml)
Volume of the component
Volume percentage of a component (v/v %) = 100
Total volume of the solution
2. Strength: Strength of a solution is defined as the amount of solute present in one litre of solution.
So, it is expressed in gm L–1.

Mass of solute (in gm)

 Strength of a solution =
Volume of the solution in litres
3. Molarity (M): Molarity of a solution is defined as the no. of moles of solute dissolved in one litre
of solution.
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No. of moles of solute

 Molarity of a solution (M) =
Volume of solution in litres
Mass of solute (w)
No. of moles of solute (n) =
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Molar mass of solute

Also, M1V2 = M2V2 Dilution formula

4. Molality (m): Molality of a solution is defined as the no. of moles of solute dissolved in 1 kg of
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solvent.

No. of moles of solute

 Molality of a solution (m) =
Mass of solvent in kg
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5. Mole Fraction (x): Mole fraction is being calculator for both solute and solvent in a solution.
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It is defined as the no. of moles of a component upon total no. of moles of all the components
present in the solution.

n2
 Mole fraction of solute (n2 ) 
n1  n2

n1
and mole fraction of solvent (n1 )  n  n
1 2

Where, n2 and n2 are the no. of molar of solvent and solute respectively.

Also, n1  n2  1

 n1  1  n 2 and n2  1  n1

6. Normality (N): Normality of a solution is defined as no. of gram equivalent of solute per litre of
solution.

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Solutions

No. of gm. equivalents of solute

  Normality of a solution (N) =
Volume of solution in litres
Mass of solute
 No. of gram equivalents of solute =
Equivalent mass (or wt.) of solute
Molar mass of solute
 Equivalent mass (or wt.) of solute =
n - factor
 n - factor = basicity of an acid or acidity of a base or No. of electrons involved during the
reaction by a salt or an oxidising agent or a reducing agent.

 Basicity of an acid = No. of H+ ions liberated by an acid during reactions.

Example: HCl (nf = 1), H2SO4 (nf = 2), H3PO4 (nf = 3), CH3COOH (nf = 1), etc.

Acidity of a Base = No. of OH– ions liberated by a base during the reaction.

Example: NaOH (nf = 1), Ca(OH)2 (nf = 2), Al(OH)3, (n = 3), etc.
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No. of electrons involved during the reaction by a salt

Example: NaCl (nf = 1), CaCl2 (nf = 2), Al2(SO4)3 (nf = 6), Fe2O3 (nf = 6), SnCl4 (nf = 4), etc.
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 Normality equation: N1V1  N 2 V2

 Normality (N) = Molarity (M) × nf

N
 N  M  n f and M 
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nf

 Milliequivalent (meq.) = N × V ml
meq. of an acid = meq. of a base
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N1 V1  N 2 V2
Also, N 3  (V1  V2 ) (here V1 + V2 = V3)
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Illustration 1: A solution contains 25% water, 25% ethanol and 50% acetic acid by weight. Find out the
mole fraction of each component.

Solution: Let us consider that total mass of the solution is 100 g

Mass of water = 25 g
Mass of ethanol = 25 g
Mass of acetic acid = 50 g

25
Moles of water = = 1.388
18

25
Moles of ethanol = = 0.543
46

50
Moles of acetic acid = = 0.833
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Solutions

1.388
Mole fraction of water = 1.388  0.543  0.833 = 0.502
0.543
Mole fraction of ethanol = 1.388  0.543  0.833 = 0.196

0.833
Mole fraction of acetic acid = 1.388  0.543  0.833 = 0.301

Illustration 2: Find out the mass of sodium bromate and molarity of solution necessary to prepare 85.5 ml
of 0.672 N solution where the half cell reaction are
(i) BrO3– + 6H+ + 6e– — Br– + 3H2O
(ii) BrO3– + 12H+ 10e– — Br2 + 6H2O

Solution: For equation (i)

Molecular weight 151

Equivalent weight of NaBrO3 = = = 25.167
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Mass of NaBrO3 is solution = N  V in litre  Equivalent weight

85.5
= 0.672   25.167 = 1.446 g
1000
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Normality 0.672
Molarity = No. of electrons accepted = = 0.112
12
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For equation (ii)

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Mol. wt. 151
Equivalent weight of NaBrO3 =  = 15.1
10 10

85.5
Mass of NaBrO3 in solution = 0.672  15.1 = 0.867 g
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1000

Normality 0.672
Molarity = No. of electrons accepted  10 = 0.0672
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SAMPLE PROBLEMS 1.1 (MCQ)

Problem 1: The volume of 95% H2SO4 (density = 1.85 g cm–3) needed to prepare 100 cm3 of 15%
solution of H2SO4 (density = 1.10 g cm–3) will be
(a) 5 cc (b) 7.5 cc
(c) 9.4 cc (d) 12.4 cc

95 1
Solution: (c) Molarity of 95% H2SO4    1000  17.93M
98 100 / 1.85
Molarity of 15%
15 1
H2SO4   1000  1.68 M
98 100 /1.10
M1V1  M 2 V2
(95% H2SO4 ) (15% H2SO4 )
17.93  V1  1.68  100 or V1  9.4 cm3

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Solutions

Problem 2: An X molal solution of a compound in benzene has mole fraction of solute equal to 0.2. The
value of X is
(a) 14 (b) 3.2
(c) 1.4 (d) 2.0

Solution: (b) x1 =0.2,  x2 = 0.8

n2 n1
i.e., n  n  0.2 and n  n  0.8
1 2 1 2
n2 0.2 1
Dividing n  0.8  4
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If n1 =1000 g = 1000/78 mol = 12.8 mol,

12.8
n2   3.2, i.e., molality = 3.2
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Alternatively, mole fraction of solute = 0.2

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moles of solute = 0.2 mole, solvent = 1 – 0.2 = 0.8 mole

Mass of solvent = 0.8 × 78 g = 62.4 g.
0.2
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Hence, moles of solute in 1000 g of solvent  1000 = 3.2

62.4
Problem 3: The normality of mixture obtained by mixing 100 ml of 0.2 M H2SO4 with 100 ml of 0.2 M
NaOH is
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(a) 0.2 (b) 0.01

(c) 0.1 (d) 0.3

Solution: (c) 100 ml of 0.2 M H2SO4 = 100 × 0.2 millimoles

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= 20 millimoles = 40 milli eq.

100 ml of 0.2 M NaOH = 100 × 0.2 millimoles
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= 20 millimoles = 20 milli eq.

20 milli eq. NaOH neutralize 20 milli eq. of H2SO4
H2SO4 left = 20 milli eq.
Volume after mixing = 200 ml
20
 Normality =  0.1N
200
Problem 4: A 500 mL sample of the effluent from a water softener required 6 drops of standard soap
solution to produce a permanent lather. The soap solution had been calibrated against an
artificial hard water solution containing 0.136 g of CaCl2 per litre. On the average it required
28 drops of standard soap solution to lather 500 mL of the artificial sample. Then the hardness
of effluent sample in terms of ppm of CaCO3 is
(a) 123 ppm (b) 26 ppm
(c) 0.123 ppm (d) 38 ppm

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Solution: (b) Harness of effluent sample is th of the hardness of CaCl2 solution
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Hardness of CaCl2 solution can be calculated as follows:
111 parts of CaCl 2 = 100 parts of CaCO 3 (Mol. wt. of CaCl 2 = 111,
[Link]. of CaCO3 = 100)
100
0.136 parts of CaCl2 =  0.136  0.123 parts of CaCO3
111
0.136g of CaCl2 in 1000 g of water = 0.123 g of CaCO3
 In 106 parts it will be = 123
i.e., Hardness of CaCl2 in terms of CaCO3 = 123 ppm
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Hardness of effluent sample =  123  26 ppm
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Problem 5: 250 mL of 6 M HCl and 630 mL of 3 M HCl were mixed together. The volume of water to
be added so that the molarity of the final solution is 3 M will be
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(a) 250 mL (b) 1150 mL

(c) 500 mL (d) 975 mL

Solution: (a) M1V1 + M2V2 = M3(V1 + V2)

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6 × 250 + 3 × 650 = M3 (250 + 650)

or 1500 + 1950 = 900 M3 or M3 = 3450/900 M
i.e., Molarity of solution after mixing = 3450/900 M
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M1V1  M2 V2

Again applying (Before dilution ) (Before dilution )

3450
 900  3  V2  1150 mL
900
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Volume of water to be added = 1150 – 900 = 250 mL

Problem 6: The molality and molarity of a sulphuric acid solution are 94.5 and 11.5 respectively. The
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density of the solution is

(a) 1.15 g L–1 (b) 1.25 g L–1
(c) 1.35 g L–1 (d) 1.45 g L–1

Solution: (b) Molarity 11.5 means 11.5 moles of H2SO4 are present in 1 L of the solution. Suppose the
density of the solution is d g mL –1, then 1 L, i.e., 1000 mL of solution has
mass = 1000 d g. Thus, 1000 d of the solution contain H2SO4 = 11.5 moles = 11.5 × 98
g = 1127 g
1000 M
M
1000d  MM1
1000  11.5
94.5 
1000d  (11.5  98)

1248.7
d  1.2487 gL1
1000
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Solutions

Problem 7: One litre of N/2 HCl solution is heated in a beaker. When volume of the solution was
reduced to 600 mL, 3.25 g of HCl was found to have been lost. The normality of the new
solution is
(a) 0.585 N (b) 0.685 N
(c) 0.785 N (d) 0.883 N

N 1
Solution: (b) 1 L of HCl contains HCl = × 36.5 g = 18.25 g
2 2
HCl now present = 18.25 – 3.25 = 15 g
Now volume = 600 ml = 0.600 L

15 1
Normality = mol   0.685N
36.5 0.600L

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Problem 8: 5 g of NaOH is added to 250 mL of NaOH solution (density = 1.05 g/cm3). The density
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of the new solution is formed to be 1.06 g/cm3. The molarity of the new solution will be
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(a) 0.46 M (b) 0.56 M

(c) 0.66 M (d) 0.76 M
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M
Solution: (d) 250 ml of NaOH  2.5 g NaOH
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WNaOH = 5.25 + 2.5 = 7.5 g
Mass of solution = 250 × 1.05 = 262.5 g
262.5
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Volume of solution = ml
1.06
7.5  1000  1.06
M  0.76 M
40  262.5
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Problem 9: 250 mL of 0.10 M K2SO4 solution is mixed with 250 mL of 0.20 M KCl solution. The
concentration of K+ ions in the resulting solution is
(a) 0.30 M (b) 0.15 M
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(c) 0.20 M (d) 0.40 M

Solution: (c) No. of moles of K+ in 250 ml of 0.1 M K2SO4

0.1 2
  250  0.05 mole
1000
No. of moles of K+ in 250 ml of 0.2 M KCl
0.2
  250  0.05 mole
1000
Total volume of the solution after mixing = 500 ml = 0.5 L
0.1 mole
Molar conc. of K+ in the final solution =  0.2 M
0.500 L
Problem 10: You are given one litre each of 0.5 M HCl and 0.2 M HCl. The ratio in which they should be
mixed so as to give maximum volume of 0.4 M HCl should be
(a) 3 : 2 (b) 2 : 3
(c) 2 : 1 (d) 3 : 1
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Solutions

Solution: (c) Suppose V lire of 0.5 HCl is mixed with 1 litre of 0.2 M HCl to prepare 0.4 M HCl. Then
M1V1 + M2V2 = M3 (V1 +V2) gives
0.5 × V + 0.2 × 1 = 0.4 (V + 1)
or 0.5V + 0.2 = 0.4V + 0.4 or 0.1 V = 0.2
or V = 2 L
Thus, 2 L of 0.5 HCl is needed which is not available.
Again, suppose V litre of 0.2 M HCl is mixed with 1 litre of 0.5 M HCl to prepare 0.4 M
HCl. Then
M1V1 = M2V2 = M4 (V1 + V2)
0.2 × v = 0.5 × 1 = 0.4 (V +1)
or 0.2 V +0.5 = 0.4 V + 0.4 or 0.2V = 0.1
or V = 0.5 L
Thus, 0.5 L of 0.2 M HCl should be added to 1 litre of 0.5 M HCl to obtain 0.4 M HCl.
Volume of the 0.4 M HCl solution obtained =1.5 L
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Then, ratio in which 0.5 HCl and 0.2 M HCl should be mixed = 1 L : 0.5 L = 2 : 1
Alternatively, suppose x L of 0.5 M HCl are mixed with y L of 0.2 M HCl to make
0.4 M HCl. Then,
M1V1 + M2V2 = M3(V1 + V2)
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i.e., 0.5 x + 0.2 y =0.4 (x + y)

x 2
or 0.1 x +0.2 y or 
y 1
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Thus, 0.5 M HCl and 0.2 M HCl should be mixed in the ratio of 2 : 1. As maximum
amount available is 1 L of each, thus means 1 L of 0.5 M HCl should be mixed with 0.5
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L of 0.2 M HCl. Volume of 0.4 M HCl obtained = 1.5 L.

1.2 Solubility of Gases In Liquids

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Gases dissolve in liquids to form true solutions, the degree of solubility depends on the nature of the
gas, the nature of the solvent, the pressure and the temperature. Gases like nitrogen, hydrogen and
helium dissolve to a slight extent, while gases like hydrogen chloride and ammonia are very soluble.
The large solubility of HCl and ammonia is accounted by the chemical reaction of these gases with
the solvent to form hydrochloric acid, and ammonium hydroxide respectively.

Under the same pressure and temperature:

(a) N2, CO2 are more soluble in CH3OH than in H2O.

(b) H2S and NH3, are more soluble in H2O than in C2H5OH.

From this it is quite clear that chemical similarity between solute and solvent leads to higher solubility.
e.g., Hydrocarbons vapours (non polar) are more soluble in other hydrocarbons (non polar) and
other organic solvents than they do in water. HCl vapours (polar) more soluble in H2O (polar) than in
CS2 (non polar).

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Solutions

Factors Influencing Solubility of Gases in Liquids

The solubility depends upon

(i) Nature of solute or solvent (ii) Temperature (iii) Pressure (In case of gases)

1. Nature of Gas and Nature of Solvent: The solubility of gas in a given solvent varies considerably
with nature of the gas. Generally speaking, the gases which are easily liquified, are more soluble
in common solvents.

Thus, CO2 is more soluble than H2 and O2 in water or in any other solvent.

The gases which are capable of forming ions in aqueous solutions, are much more soluble in
water than in other solvents, e.g., Hydrogen chloride is highly soluble in water but not in benzene,
because HCl dissociates into H+ +Cl– in water: Similarly NH3 is highly soluble in H2O than in
benzene.

The solubility of gases is generally expressed in terms of absorption co-efficient (a). This is
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defined as the volume of the gas reduced to STP dissolved by a unit volume of a solvent at the
temperature of the experiment and under a pressure of one atmosphere of the gas.
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The absorption co-efficient of few gases at 20ºC in different solvents.

H2 N2 O2 CO 2

Solvent
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H2O 0.017 0.015 0.028 0.88

C2H5OH 0.080 0.130 0.130 3.00
C 6H 6 0.066 0.104 0.105 —
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2. Effects of Temperature: It has been found that under constant pressure the solubility of a gas
diminishes with rise in temperature. The absorption coefficient of a few gases at different
temperatures are
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Temperature CO 2 O2 N2

0 1.713 0.0484 0.0239

10 1.194 0.0380 0.0196
20 0.878 0.0380 0.0196
30 0.665 0.0260 0.0138
40 0.530 0.0231 0.0118

3. Effects of Pressure on solubility of gases in liquids: The effect of pressure on the solubility
of a given gas in a particular liquid at constant temperature can be obtained by carefully observing
the process in reverse direction, viz., the gas as a solute which vapourizes to establish a vapour
pressure above the solution.

Henry’s Law: It states that at constant temperature the solubility of a gas in a liquid is directly
proportional to the pressure of the gas above it.

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Solutions

When several gases are dissolved simultaneously in a solvent, the solubility of each gas from a
mixture of gases is directly proportional to the partial pressure of the gas mixture. The proportionality
constant will however be different for each gas.

The strict applicability of Henry’s law is limited to the lower pressure and at high pressures the law
becomes less exact.

Generally, higher the temperature and lower the pressure, the more closely is the law obeyed. This
law is not valid when the gas reacts with the solvent, or when the dissolved gas ionizes.

Solubility of Partially Miscible Liquids

These are pairs of liquids which dissolve in each other to a limited extent only.

There are four types of such partially miscible liquid -liquid systems.

Case-1: Those in which partial miscibility increases with increase in temperature

Example: C6H5OH + H2O, C6H5NH2 + H2O

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C6H5NH2 + hexane, CH3OH + CS2

cyclohexane + CH3OH

Case-2: Those in which partial miscibility decreases with increase in temperature

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Example: (C2H5)2NH + H2O, (C2H5)3N + H2O

Case-3 : Those in which partial miscibility increase both on increasing the temperature as well as
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decreasing the temperature, in certain ranges

Example: H2O + Nicotine, and H2O + -picoline

Case-4: Those in which complete miscibility cannot be attained.

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Example: ether + H2O

Nernst Distribution Law

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H3BO3 is soluble in both water and amyl alcohol. But when a solution of H3BO3 in amylalcohol is
shaken with water, it is found that H3BO3 distributes itself in such a way that the ratio of the
concentration of H3BO3 in water and alcohol is a constant at a particular temperature.

Similarly iodine is soluble in H2O and CCl4 and the distribution of iodine in H2O and CCl4 remains
constant at a particular temperature.

This is also one of the direct consequences of thermodynamic requirement for equilibrium.

Let a substance ‘X’ be miscible in two immiscible pairs of solvents A and B. Then

aA
 Cons tan t  K
aB

aA
This equation a = Constant = K is a mathematical representation of Nernst distribution law..
B

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Solutions

It states that a substance will distribute itself between two solvents until at equilibrium the ratio of the
activities of the substances in two layers is a constant at any given temperature.

Assuming the solution to be dilute or when solute behaves ideally the activity becomes equal to
concentration C and hence, we have

cB
K
cA

where K = distribution or partition co-efficient of solute between two solvents.

K depends upon:

(i) Nature of solute.

(ii) Nature of liquids involved.

(iii) The temperature at which the liquids are maintained.

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(iv) The magnitude depends upon the manner in which the constant is represented CA/CB or CB/CA.

SAMPLE PROBLEMS 1.2 (MCQ)

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Problem 1: If N2 gas is bubbled through water a 293 K, how many millimoles of N2 gas would dissolve
in 1 L of water. Assume that N2 exerts a partial pressure of 0.987 bar. Given that Henry’s
law constant for N2 at 293 is 76.48 K bar.
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(a) 0.716 (b) 716

(c) 7.16 (d) 71.6
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Solution: (a) The solubility of gas is related to its mole fraction in a aqueous solution. The mole
fraction of the gas in its solution is calculated by applying Henry’s law. Thus,
pN 0.987 bar
 1.29  105
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χ N2  2 
K H 76480 bar
As 1 L water contains 55.5 mol of it, therefore,
n mol n
χ N2    1.29  105
n mol  55.5 mol 55.5
Thus, n = 1.29 × 10–5 × 55.5 ml
= 7.16 × 10–4 mol
4 1000 mmol
= 7.16 10 mol  =0.716 mmol
1 mol
Problem 2: Henry’s law constant for oxygen dissolve in water is 4.34 × 104 atm at 25°C. If the partial
pressure of oxygen to air is 0.4 atm. Calculate the concentration (in mole per litre) of the
dissolved oxygen in water in equilibrium with air at 25°C.
(a) 5.11 × 10–3 M (b) 5.11 × 10–4 M
(c) 5.11 × 10–2 M (d) 5.11 × 10–1 M

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Solutions

Solution: (b) Given:

Henry’s law constant KH = 4.34 × 104 atm
According to Henry’s law,

p  KHχ

n O2
pO2  K H 
n O2  n H2 O
n O2
0.4  4.34  104 
55.56  n O2
 n O  n H2 O
2

55.56  0.4
 n O2   5.1110 4
4.34  104
Since 5.11 × 10–4 mol are present in 1000 ml of solution, therefore, molarity is
5.11 × 10–4 M
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Problem 3: Henry’s law constant for the solubility of N2 gas to water at 298 K is 1.0 × 105 atm. The
mole fraction of N2 in air is 0.6. The number of moles of N2 from air dissolved in 10 moles
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of water at 298 K and 5 atm pressure is
(a) 3 × 10–1 (b) 3 × 10–2
(c) 3 × 10–4 (d) 3 × 10–3

 
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Solution: (c) Partial pressure of N2 in air pN 2  Ptotal  χ N2 (in air) = 5 × 0.6

pN2 (in air)  K H  χ N2 (in H2O)

ka

5 × 0.6 =1.0 × 105 × χ N2 (in H2 O)

n N2
3  105 
n N2  10
lp

 n N2  n H 2 O
n N2
  3 105
10
 nN2  3  10 4

Problem 4: For a solution of acetone in chloroform, Henry’s law constant is 150 torr at a temperature of
300 K. (a) Calculate the vapour pressure of acetone when the mole fraction is 0.12. (b)
Assuming that Henry’s law is applicable over sufficient range of composition to make the
calculation valid, calculate the composition at which Henry’s law pressure of chloroform is
equal to Henry’s law pressure of acetone at 300 K. (Henry’s law constant for
chloroform is 175 torr).
(a) 18, 0.103 (b) 10, 0.103
(c) 14, 0.103 (d) 15, 0.403

[ 13 ]
Solutions

Solution: (a) The given values are

K H  150 torr; χ acetone  0.12
Using Henry’s law equation
P  K H χ , on substituting all values
P = (150 torr) (0.12) = 18.0 torr
(b) Here P = 18.0 torr, and KH = 175.0 torr
P 18.0 torr
 χ acetone    0.103
K H 175.0 torr
Problem 5: Henry’s law constant for oxygen and nitrogen dissolved in water at 298 K are 2.0 × 109 Pa
and 5.0 × 109 Pa, respectively. A sample of water at a temperature just above 273 K was
equilibrated with air (20% oxygen and 80% nitrogen) at 1 atm. The dissolved gas was
separated from a sample of this water and then dried. Determine the composition
of this gas.
(a) Percentage of O2 is 38.27, Percentage of N2 is 61.73
(b) Percentage of O2 is 36.27, Percentage of N2 is 60.73
JE

(c) Percentage of O2 is 35.27, Percentage of N2 is 59.73

(d) Percentage of O2 is 30.27, Percentage of N2 is 55.73
Solution: (a) The given values are:
K H(O2 )  2  109 Pa; K H( N2 )  5  109 Pa
ES

Partial pressure of oxygen

pO2 = 0.2 atm = 20265 Pa
Partial pressure of nitrogen; [1 atm = 101325 Pa]
an

pN2 =0.8 atm = 81080 Pa

Using Henry’s law equation
p
χ
ka

KH
 Amount fraction of O2 in water
pO 2 20265
χ O2    10.13 104
lp
9
K H (O2 ) 2  10
Amount fraction of N2 in water
pO 2 81060
χ N2    16.212  10 6
K H( N 2 ) 5  109
Amount of dissolved oxygen 10.13  106
   0.62
Amount of dissolved nitrogen 16.212  106
0.62
Hence, percent of O2 = 100  38.27%
1.62
Percent of N2 = 100 – 38.27 = 61.73%

Problem 6: Which of the following gases are highly soluble in water

(a) HCl (b) SO2
(c) NH3 (d) H2

Solution: (c) Conceptual

[ 14 ]
Solutions

Problem 7: Henry’s law can be applied for which of the following gases for solubility in water
(a) H2 (b) HCl
(c) SO2 (d) NH3

Solution: (d) As it is highly soluble.

Problem 8: It takes larger time to cook food on hills than in plains. This is because
(a) high pressure on hills
(b) low pressure on hills
(c) boiling point decreases on going up the hills
(d) none of these

Solution: (c) At hills atm pressure is low so boiling point is also low.

Problem 9: Which of the following will have maximum intermolecular hydrogen bonding?
(a) H2O (b) CH3OH
(c) H2S (d) PH 3

Solution: (a) 1 molecule of H2O forms H-bond with 4 other H2O molecule.
JE

Problem 10: The melting points of most of the solid substances increase with an increase of pressure
acting on them. However, ice melts at lower temperature than its usual melting point when
the pressure increases. This is because
ES

(a) ice is less dense than H2O (b) pressure generates heat
(c) the bonds break on pressure (d) ice is not a true solid

Solution: (a) Conceptual

an

1.3 The Vapour Pressure of Binary Ideal solution Containing Volatile liquids
In a liquid, the molecules are always in the state of random motion, due to collision of molecules with
each other and with walls of container. This leads to the molecules acquiring certain kinetic energy. The
ka

molecules of the liquid which possess high kinetic energy have a tendency to change to vapour state.

The minimum energy which the molecules of a liquid should acquire to transform from liquid state to
vapour state is termed as escape energy. Lesser the escape energy, greater is the volatility of
lp

a liquid from liquid surface.

When a liquid is placed in a closed container then due to evaporation, vapours of liquid are produced
which ultimately leads to an equilibrium state due to the tendency of the vapours to convert back to
liquid.

Vapour Pressure
A(g)
The pressure exerted by the vapours of the liquid which are in
equilibrium with the liquid phase at the given temperature is called A(l) A(g)
equilibrium
vapour pressure. A(l)
A(l) A(g) (Rate of evaporation = Rate of condensation)

The vapour pressure of liquid depends upon

(i) Nature of the liquid
(ii) Temperature

[ 15 ]
Solutions

Nature of Liquid: When the intermolecular forces of attractions are stronger then the vapour
pressure will be low because less number of molecules can leave the liquid

Temperature: Higher the temperature, greater would be the vapour pressure. This is because
when temperature is raised, kinetic energy of the molecules increase and therefore, the number of
molecules leaving surface of liquid, is large.

Vapour Pressure
A(l) A(g)

The Clausius Clapeyron equation gives the relationship for

vapour pressure of liquid with temperature

P2 H  T2 – T1 
i.e. log P  2.303 R  T T  . Temperature
1  1 2 
Vapour Pressure of Solution
Let two volatile liquids A and B dissolve in each other to form an ideal A(g) B(g)

solution. Then the vapours above the solution will contain the vapours of A
JE

and B. A (l) B (l)

An ideal solution is one in which the activity of each constituent is equal to its mole fraction throughout
complete range of concentration.
ES

Hence, applying Dalton’s law of partial pressure the vapour pressure of the solution will be
vapour pressure of solution =Psolution = PA + PB

Where, PA and PB are the partial vapour pressures of A and B.

an

Solution being dilute (Condition for ideality) Raoult’s law can be applied.

Raoult’s law for binary solutions state that “the vapour pressure of any volatile constituent of
ka

a binary solution at any given temperature is equal to the product of the vapour pressure of
pure constituent and its mole fraction.”

PA = PA0  A PBº
lp

ºB
+ PB
A
PB = PA0  B = P Aº
PS
B
º

0 0
PA and PB are vapour pressure of pure A and B respectively P Aº
B
P
=

A and B are mole fraction of A and B respectively.

PB

Hence,
Vapour
Ps = PA0  A  PB0  B Pressure P
A =
Hence, P
A º


Ps = PA0 (1 χ B )  PB0 χ B [A + B = 1]

A = 1 B A = 0
Ps = PA0  ( PB0  PA0 ) χ B
B = 0 B = 1
Increasing
This equation is of the form y = mx + c Mole fraction

Where y = Ps, c = PA0 , x = B, and m = ( PB0  PA0 )

[ 16 ]
Solutions

The value of m (slope) may be (+ve) or (–ve).

Depending upon whether PB0  PA0 (m = +ve) or PB0  PA0 (m = –ve).
Hence a plot of a graph of Ps vs B will be a straight line with an intercept on y-axis.
Note: Formation of a true ideal solution is rare and largely exceptional. However, a large number of
solution are obtained which are found to be nearly ideal.

Ideal Solution
A few binary miscible liquid systems which obey Raoult’s law throughout the complete range of
concentration, are:
(1) Ethylene dibromide and Propylene dibromide.
(2) Chlorobenzene and Bromobenzene.
(3) Benzene and Ethylene dichloride.
(4) CCl4 + SnCl4.
(5) CH3OH + C2H5OH.
JE

(6) n-Hexane + n-Heptane.

(7) Benzene + Toluene.
Such systems are called nearly ideal or ideal solutions.
ES

Such solutions obey Raoult’s law and comply to the equation Ps = PA0 . χ A  PB0 . χ B .

To comply to this condition for ideality the two liquids A and B should fulfill the under mentioned
conditions:
an

1. The attractive forces between the particles A and B (i.e., A–B interactions) should be equal to
the attractive forces between A and A (i.e., A–A interaction) and between B and B (i.e., B–B
interaction)
ka

2. Such an interaction can be equal if the structure and polarity are almost same. e.g., CH3–OH and
C2H5–O–H.
lp

In such solutions:

(i) Vmix = 0 (ii) S mix > 0 (iii) H mix = 0.

Non Ideal Solutions

There are certain liquid pair systems which deviate from the Raoult’s law to a greater or lesser
extent depending upon the nature of the liquids and the temperature.

Set-A Set-B

(i) Ether + Acetone (i) CH3 OH + CH3COOH

(ii) CCl4 + CH3OH (ii) H2O + HNO3
(iii) C6H6 + acetone (iii) H2O + HCl
(iv) H2O + C2H5OH (iv) H2O + H2SO4
(v) n-Hexane + Ethyl alcohols (v) CHCl3 + CH3COOCH3

Set A exhibits positive deviation while set B exemplify negative deviation.

[ 17 ]
Solutions

Positive Deviation Solution

Here the A Sets of solution show a relationship where the vapour pressure of the solution observed
is greater than the vapour pressure of solution under ideal conditions
Ps PBº
i.e., Ps (obs) > Ps(ideal)
or Pi
Ps > Pi where Pi = PA0 χ A  PB0 χ B

B
P
i.e., Ps > PA0 χ A  PB0 χ B PAº

(i) B
P
Such solutions are said to have a +ve deviation from
Vapour
ideality. The graph obtained resembles as given below Pressure P
A

The reasons for such a +ve deviation could be linked PB

(i )
to the fact that after mixing the interactions between
the liquid A and B is less than the interaction between
A–A particle and B–B particles. A = 1 B A = 0
B = 0 B = 1
JE

This leads to a less escape energy for the molecules of Increasing

A and B liquids in the solution. Molefraction of B

This also some times leads to an increase in volume of solution after mixing,
ES

Vmix > 0. Vmix = Vobs – Vactual Smix > 0

Negative Deviation
The B set of solutions show a relationship where the vapour pressure of solution observed is lesser
an

than the vapour pressure of the solution under ideal conditions, i.e.

Ps(obs) < Psolution (ideal)

Ps < Pi.
ka

 Ps < PA0 χ A  PB0 χ B

Here this equation is due to the fact that when interactions increase the escape kinetic energy
lp

required, increases, leading to a lowering of vapour pressures such that PA < PA0 χ A and PB < PB0 χ B
Hence the sum.
PB º
PA + PB < PA0 χ A  PB0 χB ide a
l)
Ps ( )
obs
 Ps < Pi Ps (
P Aº
When the interactions between liquid A particles and
(i )
B
P

liquid B particles increases

P

Vapour
Pressure
A–B interaction > A–A interaction and B–B interactions.
P
Hmix < 0  Hmix = –ve. and also P A (i)
A

Vmix < 0  Vmix = –ve

A = 1 B A = 0
Smix > 0. B = 0 B = 1
Increasing
The graph corresponds to the one given. Molefraction of B

[ 18 ]
Solutions

Vapour Phase Composition

To obtain the relationship between the composition of solutions and the composition of
the vapour above it.
Let A and B be the mole fraction of components A and B in the vapour phase above the liquid
solution consisting of A and B mole fractions of A and B respectively.
Then according to gas law
PB A P PA 
n A 
P(s)
 B and P   A  P  n  n   A  ,
(s)  S A B 
0 0
PB χ B P χ
   B  0 B B0 = Vapour phase composition of B.
P(s) PA χ A  PB χ B

PA0 χ A PA0 χ A
and A  = Vapour phase composition of A.
P(s) PA0 χ A  PB0 χ B

Generally the distillate composition is the vapour phase composition.

JE

Azeotropic Mixtures
The study of the vapour pressure curves of completely miscible liquid mixture is of great help in
ES

separating the constituents of the liquid mixtures by distillation.

Azeotropic mixture are those completely miscible liquid mixtures which distil over unchanged in
composition and boil at constant temperature.
an

The separation by fractional distillation is possible only when the vapour phase has a composition
different from that of the boiling mixture. Thus azeotropes can not be separated by frictional distillation.
When a plot of the boiling point temperature versus composition of solution is done then we get.
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I For Ideal Solution

TAº Vap
our
lp
nA  nB
A B
T Tb(a)
Liq u
id
Vapour Phase
Vapour TBº
Pressure
Liquid Phase
a n n
A A B B
(b) (a) (a)
B = 1
A = 1 Molefraction Distillate
richer in B
Residue from
distillation Mixture composition
of a a richer in A

Graph for boiling point vs composition for ideal solution:

Point 1: Mixture composition (a) taken richer in a component (A).
Point 2: Mixture composition (a) boils at Tb(a) temperature.
Point 3: Distillate (a) of (a) is the mixture composition richer in component B.
Point 4: ‘b’ is residue during distillation of mixture composition ‘a’.
Hence, such solution can be successfully separated into pure A and pure B.
Successive distillation of a’ give a” and then finally pure B. as distillate.

[ 19 ]
Solutions

II For non Ideal Solutions

A) +Deviation solution or (–ve boiling azeotropes)
When temperature versus composition graphs are drawn for +ve deviation solution we get

TAº Vap
ou r
Liquid
V TBº
T Tb(a)
Vapour L
Pressure e)
D
es i du
e (R

b a a
c c B = 1
A = 1 d
Molefraction
(Graph for boiling point vs composition for non-ideal solution showing +ve deviation)

Point 1: Here when mixture composition ‘a’ is boiled, then the distillate (a) becomes
more rich in ‘B’ but, successive distillation of a will finally lead to compositions
JE

(‘d’) where vapour phase and liquid phase compositions are same. Hence d(D)
is a solution which cannot be separated into pure A and B. Hence, it is a –ve
boiling azeotropic mixture. But the residue ‘b’ becomes richer in ‘A’.
ES

Point 2: When mixture composition ‘c’ is boiled then distillate is (c) richer in ‘A’ but
successive distillation makes it to composition d(D), i.e., –ve boiling azeotropic
mixture.
The distillate is ‘e’ richer in (B) component:
an

Table for Minimum Boiling Azeotropic Mixtures

Component A [Link] Component B B.P. B. pt of % of B
Azeoropic mixture
ka

H2O 100ºC CHCl3 61.2ºC 56.12 97%

H2O 100ºC C2H5OH 78.3º 78.13 96%
H2O 100ºC C 6H 6 80.2ºC 69.25 91%
lp

H2O 100ºC C3H7OH 97.2ºC 87.7 97%

Chloroform 61.2ºC CH3OH 64.7ºC 53.43 13.6%
B) –ve Deviation solutions (+ve Boiling azeotropic)
When temperature versus composition are drawn for the solutions showing –ve deviation the
graph obtained is

D
V V

TB º
L
T Aº L

a a b c c
A = 1 d e B = 1
Molefraction

(Graph of Boiling point VS composition for non-ideal solutions –ve deviation)

[ 20 ]
Solutions

Point 1: When mixture composition ‘a’ is taken, then on boiling:

(i) Distillate a is obtained which is richer in component A.

(ii) Residue is ‘b’
Successive distillation of ‘b’ leads to azeotropic solution D. (+ve boiling azeotropic
mixture).
(iii) Successive distillation of a will lead to pure (A)

Point 2: When mixture composition c is taken and boiled:

(i) Distillate is c which is richer in component B and successive distillation of

distillates lead to solution becoming pure ‘B’.

(ii) The residue of ‘c’ is ‘e’ successive distillation of ‘e’ makes the residue richer in
‘D’ which is +ve boiling azeotropic mixtures.

Table for Maximum Boiling Azeotropic Mixture

JE

A [Link] of A B [Link] B B. pt of % of B
in ºC in ºC Azeoropic mix

HCl –20º H2O 100 108.5 79.96

ES

HNO3 86º H2O 100 120.5 32

CHCl3 61.2 Acetone 56.5 64.7ºC 20

an

CHCl3 61.2 CH3COOC 2H5 57 64.8 23

Ratio of Distillate to Residue Compositions

ka

The relative proportions of the two liquids in the distillate can be calculated on the basis that the
number of moles of each component present in the vapour phase is proportional to its vapour pressure.
If nA and nB are the number of moles of the components A and B in the vapour phase, then
lp

nA/nB = p ºA / p Bº (1)

If wA and wB represent the actual masses of the two components in the distillate and MA and MB
their respective molecular masses, then Eq. (1) may be written as,

wA n A M A po M wA po M
  Ao A   Ao A
wB n B M B pB M B wB pB M B

Thus, the masses of the liquids in the distillate will be in the ratio of their vapour pressures and molar
masses.

Illustration 1: 4.45 g of pure sulphuric acid is added to 82.20 g water. The density of the solution was found
to be 1.029 g/ml. Calculate (a) weight percent (b) mole fraction (c) mole percent (d) molality
(e) molarity and (f) normality of sulphuric acid solution.

[ 21 ]
Solutions

Solution: Mass of H2SO4 = 4.450 g

Mass of water = 82.20 g
Mass of solution = 86.65 g
Density of solution = 1.029 g/ml
4.45
(a) Weight percent of H2SO4 in solution = 100 = 5.14
86.65

4.45
(b) Moles of H2SO4 = = 0.0454
98

82.20
Moles of H2O = = 5.566
18
Total no. of moles = 0.0454 + 4.566 = 4.6114
0.0454
Mole fraction of H2SO4 = = 0.0098
4.6114
Mole fraction of water = 1 – 0.0098 = 0.9902
JE

(c) Mole percent

Moles of solute
Mole percent of solute =  100
Total moles in solution
= Mole fraction of solute  100 = 0.0098  100 = 0.98
ES

Mole percent of solvent = Mole fraction of solvent  100

= 0.9902  100 = 99.02
(d) Molality
an

Moles of solute
Molality = Mass of solvent in g  1000

0.0454
= 1000 = 0.552.
82.2 ´
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(e) Molarity
Moles of solute
Molarity =
lp

Volume of solution in litres

Mass of solution in g 86.65

Volume of Solution = Density of solution = 1.029  1000 litre

0.0454  1000  1.029

Molarity = = 0.539
86.65
(f) Normality
No. of equivalent s of solute dissolved
Normality =
No. of litres of solution made
4.45
Equivalent of H2SO4 =
49
86.65
Volume of solution = 1.029  1000

4.45  1000  1.029

Normality = 49  86.65 = 1.078

[ 22 ]
Solutions

Illustration 2: The vapour pressures of ethanol and methanol are 44.6 mm and 88.0 Hg, respectively. An
ideal solution is formed at the same temperature by mixing 60 g of eathanal with 40 g of
methanol. Calculate the total vapour pressure of the solution and the mole fraction of methanol
in the vapour.

Solution: Mol. mass of ethyl alcohol (C2H3OH) = 46

60
Number of moles of ethyl alcohol =  1.304
46
Mol. mass of methyl alcohol (CH3OH) = 32
40
Number of moles of methyl alcohol =  1.25
32
1.304
Mole fraction of ethyl alcohol, χ A   0.5107 mm Hg
1.304  1.25

1.25
Mole fraction of methyl alcohol, χ B   0.4893 mm Hg
1.304  1.25
JE

Partial pressure of ethyl alcohol = χ A PA0  0.5107  44.0  22.46 mm Hg

Partial pressure of ethyl alcohol = χ B PB0  0.4893  88.0  43.05 mm Hg

ES

Total vapour pressure of solution = 22.47 +43.05 = 65.52 mm Hg

43.05
Mole fraction of CH3OH in vapour phase =  0.6870
65.52
an
Illustration 3: Two liquids A and B form ideal solution, A 300 K, the vapour pressure of a solution containing
1 mol of A and 3 mol of B is 500 mm of Hg. At the same temperature, if one more mole of
B is added to the solution, the vapour pressure of the solution increases by 10 mm of Hg.
Determine vapour pressures of A and B in their pure states.
ka

Solution: Let the vapour pressure of pure A be = pA0 , and the vapour pressure of pure B be = pB0
Total vapour pressure of solution (1 mol A = 3 mol B)
lp

= χ B pB0  χ B pB0 [ χ A is mole fraction of A and χ B is mole fraction of B],

1 0 3 0
500  pA  pB
4 4
or 2000  pA0  3 pB0 ...(i)
Total vapour pressure of solution (1 mol A + 4 mol B),
1 4
 p 0A  pB0
5 5
2250  pA0  4 pB0 ...(ii)
Solving equations (i) and (ii), we get:

pB0 = 550 mm of Hg = Vapour pressure of pure B

p 0A = 330 mm of Hg = Vapour pressure of pure A

[ 23 ]
Solutions

Illustration 4: Heptane and octane form an ideal solution. At 373 K, the vapour pressure of the two liquids
are 105.0 kPa and 46.0kPa, respectively. What will be the vapour pressure, of the mixture of
25 g of heptane and 35 g of octane?

Solution: Mw of heptane, C7H10, MwA = 100

Mw of octane, C9H18, MwB = 114
W 25 35
nA  A   0.25; nB   0.3
MwA 100 114
0.25 0.3
χA   0.45; χB   0.55
0.25  0.30 0.25  0.30
P = pA0 χ A  pBχ B

= 105.0 × 0.45 + 46.0 × 0.55 = 47.25 + 25.30

= 72.55 kPa

Illustration 5: Two liquids A and B form an ideal solution such that p 0A  700 mm and pB0  300 mm . A
JE

small amount of solution is vapourized and the vapour condensed (at equilibrium). The
condensate has equilibrium vapour pressure of 500 mm (at same temperature). Find the
composition of the original solution.
ES

Solution: Pt  PA  PB

Pt  PA0 χ A  PB0 χ B  700χ A  300(1  χ A ) ...(i)

P 700χ A 7χ A
an

χ 0A  A  
Pt 300  400χ A 3  4χ A
P 300χ B 300(1  χ A ) 3  3χ A
χ 0B  B   
Pt 300  400χ A 300  400χ A 3  4χ A
ka

Putting value in equation (i),

 7χ A   3  3χ A 
500  700    300  
 3  4χ A   3  4χ A 
lp

 χ A  0.3, χ B  0.7

Illustration 6: Assuming ideal behaviour, calculate the pressure 1.0 molal solution of a non-volatile molecular
solute in water at 30°C. the vapour pressure of water at 30°C is 0.222 atm.

m
Solution: solute 
m  55.56
1
  0.0177
1  55.56
 Psolution  PA0 χ A  0.222  0.0177  0.218 atm

Illustration 7: 100 g of water contains 1.0 g urea and 2.0 g sucrose at 298 K. The vapour pressure of water
at 298 is 0.3 atm. Calculate the vapour pressure of the solution. (Molecular weight of urea =
60; Molecular weight of sucrose = 342).

[ 24 ]
Solutions

Solution: The given values are:

WH2O  100 g ; M H2O  18 g mol 1

Wurea  10 g ; Mwurea  60 g mol1

Wsucrose  2 ; Mwsucrose  342 g mol1

PH02O  0.3 atm
n solvent
solvent 
n solvent  n solute
100 5.556
   0.97
18 5.729
 100   2 10 
   
 18   342 60 
According to Raoult’s law,
pA  pA0 χ A
Vapour pressure of solution = 0.3 × 0.97 = 0.29 atm
JE

Illustration 8: Benzene and toluene form nearly ideal solution. At 298K, the vapour pressure of pure benzene
is 150 torr and of pure toluene is 50 torr. Calculate the vapour pressure of the solution,
containing equal weights of two substances at this temperature?
ES

Solution: Let the weights of benzene and toluene in the solution is = W g

W
χ  78  0.541
Mole fraction of benzene, b W W

an

78 92
Mole fraction of toluene χ t  1  0.541  0.459
According to Raoult’s law pA  pA0 χ A
ka

Partial pressure of benzene pB  Pb0  χ b  150  0.541  81.15 torr

 Partial pressure of toluene, pt  Pt 0  χ t  50  0.459  22.95 torr
Total vapour pressure of solution = pb  pt
= 81.15 +22.95 =104.1 torr
lp

Illustration 9: An aqueous solution containing 28% by weight of a liquid A (molecular mass = 140) has a
vapour pressure of 0.200 bar at 37°C. Calculate the vapour pressure of pure liquid (vapour
pressure of water at 37°C = 0.100 bar).

Solution: The given values are

Wliquid = 28g, Mw1 = 140
WH2 O  72g; MwH2 O  18

pH0 2O  0.10 bar; p total  0.2 bar

28
χ  140  0.048
Mole fraction of liquid, t 28 72

140 18
Mole fraction of water, χ H2 O  1  0.048  0.952

[ 25 ]
Solutions

According to Raoult’s law

p total  pl0 χ l  pH2O χ H2O

0.2  pl0  0.048  0.1 0.952

0 0.2  0.1 0.952

or pl   2.18 bar
0.048
Therefore, the vapour pressure of pure liquid is 2.18 bar.

Illustration 10:The vapour pressure of chloroform CHCl3, and dichloromethane (CH2Cl2) at 298 K is 200
mm Hg and 415 mm Hg, respectively. Calculate
(a) The vapour pressure of the solution prepared by mixing 25.5 g of CHCl3 and 40 g of
CH2Cl2 at 298 K.
(b) Mole fractions of each component in vapour phase.

Solution: Molar mass of CH2Cl2 = 85 g mol–1

JE

Molar mass of CHCl3 = 119.5 g mol–1

40 g
Moles of CH2Cl2 = 85g mol-1  0.47 mol
ES

25.5 g
Moles of CHCl3 = 119.5 mol-1  0.213 mol
Total number of moles = 0.47 + 0.213 = 0.683 mol
0.47 mol
χ CH2Cl2   0.688
an

0.683 mol
χ CHCl3  1.00  0.688  0.312
0 0 0
ptotal  pCHCl  ( pCH  pCHCl )χ CH2 Cl2
ka
3 2Cl 2 3

= 200 + (415 – 200) × 0.688

= 347.9 mm Hg
To calculate the mole fraction of component in vapour phase.
lp

p
χ vi  i
pT
 pCH 2Cl2  0.688  415 mm Hg = 285.5 mm Hg
285.5
χ CH2Cl2V   0.82
347.9
62.4
χ CHCl3V   0.18
347.9
Illustration 11:Certain liquid X boils at 33.5º C at 1 atm. At what temperature will it boil at 750 mm. Latent
heat of vaporization is 88.4 cal/g, R = 1.987 cal. and Mol. wt. of X is 74.

Solution: We known,
P
2  Hv  T  T 
2 1
log P  2.302 R  T T 
1  1 2 
P1 = 760 mm

[ 26 ]
Solutions

P2 = 750 mm
Hv = 88.4  74
T1 = 33.5 + 273 = 306.5
T2 = ?

750 88.4  74  T2  306.5 

log 760  2.303  1.987  306.5  T 
 2 

T2 = 305.9 K
= (305.9 – 273)º C = 32.9ºC

Illustration 12: Solutions of two volatile liquids A and B obey Raoult’s law. At certain temperature T, it is
found that when the total pressure above a given solution is 400 mm Hg the mole fraction of
A in the vapour phase is 0.45 and in the liquid it is 0.65. Find out the vapour pressure of two
pure liquids at temp. T.

Solution Total Pressure = 400 mm

JE

xA = 0.65 YA = 0.45 PºA = ?

xB = 0.35 YB = 0.55 PºB = ?
We know P = PºA xA + Pº[Link]
ES

400 = PºA × 0.65 + PºB × 0.35

Also we know
PA Pº A .x A
YA = 
an

P P

0.65 PA0
0.45 =
400
ka

400 0.45
PºA = = 277 mm
0.65
lp

Now,
400 = 277  0.65 + PºB  0.35

400  180
PºB = = 630 mm
0.35

Illustration 13: At 30ºC A and B have vapour pressures of 119.6 and 36.7 mm respectively. What are the
partial pressures of each of these components and the total pressure over a solution consisting
of equal weights of these two components at 30ºC. What is the composition of the vapour in
equilibrium with the solution at this temperature. Comment on the results. [mol. wt. of A = 78
and mol. wt. of B = 92].

Solution: Say the amount taken is 92 g for each liquid.

92
Moles of A = = 1.18
78
92
Moles of B = =1
92

[ 27 ]
Solutions

1.18
xA = = 0.541
2.18
1
xB = = 0.459
2.18
PA = 0.541  119.5 = 64.7 mm
PB = 0.459  36.7 = 16.8 mm
Total pressure = 64.8 + 16.8 = 81.5
Composition of vapour
64.7
xA in vapour phase = = 0.793
81.5
xB in vapour phase = 1 – 0.793 = 0.207.
This indicates that the vapour is always richer in the more volatile liquid.

Illustration 14: Aniline-water mixture boils at 98ºC at a pressure of 1 atm. At this temperature the vapour
pressure of water is 707 mm. If the system is distilled in steam what fraction of total weight
of the distillate will be aniline
JE

Solution: MA = 93 P 0A = ? WA = ?
MW = 18 P0W = 707 mm WW = ?
We know
ES

P = P 0A + P 0W
760 = P0A + 707
P0A = 53 mm
We know
an

WA PA0 . M A 53  93 4929
WW = 0
PW . M W = 707  18 = 12726
WA 4929
ka

xA = W  W = 4929  12726 = 0.279

A W

% of A = 0.279  100 = 27.9 %.

Illustration 15: The vapour pressure of 2.1% aqueous solution of a non-electrolyte is 755 mm at 100ºC.
lp

Find out the mol. wt. of solute.

Solution: Vapour pressure of pure water at 100ºC = 760 mm

Vapour pressure of solution at 100ºC = 755 mm
Mass of solute = 2.1 g
Mass of water = 100 – 2.1 = 97.9 g
2 .1
Moles of solute = (m = mol. wt. of solute)
m
97.9
Moles of water =
18
We know

P0  Ps Wsolute  M solvent

Ps M solute  Wsolvent

[ 28 ]
Solutions

760  755 2.1 18


755 M solute  97.9
2.1 18  755
M solute   58.3
97.9  5
Illustration16: A very small amount of a non-volatile solute (non-electrolyte) is dissolved in 56.8 ml of
benzene (density 0.889 g cm–3). At room temperature, vapour pressure of this solution is
98.88 mm Hg while that of benzene is 100 mm Hg. Find the molality of this solution. If the
freezing temperature of this solution is 0.73 degree lower than that of benzene what is the
value of cryoscopic constant of benzene.

Solution: We know for a very dilute solution.

P0  Ps Wsolute  M solvent

P0 M solute  Wsolvent

P0  Ps m  78

P0 1000
JE

1000  (P0  Ps )
m
78  P0
ES

1000  (100  98.88)

  0.1435
78  100
Further we know,
Tf = Kf  m
an

T f 0.73
Kf = = = 5.087 K kg. mol–1.
m 0.1435

Illustration 17: Dry air was passed through a solution (obtained by dissolving 50 g of solute in 100 g water)
ka

and then through pure water. The loss in weight of pure water is found to be 0.05 g. The wet
air was then passed through concentrated H2SO4. In the process H2SO4 gained 2 g. Find out
the molecular weight of the solute.
lp

Solution: Loss in weight from pure water = 0.05 g

Loss in weight from solution = 2 – 0.05 = 1.95 g
Total loss in weight = 2.0 g
We know,
Loss in weight from solution  Ps
Total loss in weight P
Also we know,
w 50
P  PS m 2.0  1.95 m
= w W; = 50 100
P  2.0 
m M m 18

1 50  18
=
40 900  100m

m = 351

[ 29 ]
Solutions

SAMPLE PROBLEMS 1.3 (MCQ)

Problem 1: The vapour pressure of water at 293 K is 17.51 mm. The lowering of vapour pressure of
sugar is 0.0614 mm. The relative lowering of vapour pressure will be
(a) 0.00351 (b) 0.00311
(c) 0.00355 (d) 0.00358

Solution: (a) Here we are given that

Vapour pressure of water (P0) = 17.51 mm
Lowering of vapour pressure (P0 – Ps) = 0.0614
Relative lowering of vapour pressure
P 0  Ps 0.0614
  0.00351
P0 17.51
Problem 2: The vapour pressure of a 5% aqueous solution of a non-volatile organic substance at 373 K
is 745 mm. Calculate the molecular mass of the solute.
JE

(a) 48 (b) 47
(c) 58 (d) 57
ES

Solution: (a) 5% aqueous solution of the solute implies that 5 g of the solute are present in 100 g of the
solution, i.e.,
Weight of solute (W2) = 5 g
Weight of solute = 100 g
an

Weight of solvent (W1) =100 – 5 = 95 g

Further as the solution is aqueous, it means that the solvent is water and we know that
vapour pressure of pure water at 373 K = 760 mm.
ka

Vapour pressure of the solution at 373 K (Ps) = 745 mm (given)

Molecular mass of solvent (water), Mw1 = 18
Molecular mass of solute Mw2 = To be calculated
lp

Using the formula for dilute solution, viz

P 0  Ps n2 W2 / Mw2
 
P0 n1 W1 / Mw1

760  745 5 / Mw2 5  18

We get,  
760 95 /18 95  Mw2
5  18  760
or Mw2   48
15  95
Problem 3: Two liquids A and B an ideal solution. What will be the vapour pressure at 27°C of a solution
having 1.5 mol of A and 4.5 mol of B? The vapour pressure of A and B at 27°C is 0.116 atm
and 0.140 atm, respectively. Then total vapour pressure at this condition will be
(a) 0.132 (b) 0.133
(c) 0.029 (d) 0.134

[ 30 ]
Solutions

Solution: (d) nA = 1.5 nB = 4.5

1.5 1.5 1
χA   
1.5  4.5 6.0 4
1 3
χ B  1 
4 4
1 3
P  PA0 χ A  PB0 χ B  0.116   0.14 
4 4
P = 0.029 + 0.105 = 0.134 atm

Problem 4: At 298 K, the vapour pressure of water is 23.75 mm Hg. Calculate the vapour pressure at
the same temperature over 5% aqueous solution of urea, [CO(NH2)2].
(a) 23.375 (b) 20.375
(c) 22.375 (d) 21.375

Solution: (a) Applying raoult’s law

P 0  Ps n1 W1  M 2
 
P0 n2 M 1  W2
JE

Substituting the values, we get

23.75  Ps 5 18
 
23.75 60 95
ES

5 18
23.75  Ps    23.75
60 95
or 23.75  Ps  0.375  Ps  23.375 mm
an

Problem 5: Liquids A and B form an ideal mixture, in which the mole fraction of A is 0.25. At temperature
T, a small quantity of the vapour in equilibrium with the liquid is collected and condensed.
This process is repeated for a second time with the first condensed. This process is repeated
ka

for a second time with the first condensate. The second condensate now contains 0.645
mole fraction of A. Calculate the ratio ( PA0 PB0 ) . What will be the mole fraction of B in the
third condensate?
lp

(a) 0.101 (b) 0.104

(c) 0.102 (d) 0.103

Solution: (a) Mole fraction of A (χ A )  0.25

Mole fraction of B (χ B )  0.75

After the condensation

Partial pressure of A ( pA )  PA0 χ A  PA0  0.25

Partial pressure of B ( pB )  PB0  0.75

PA PA0 0.25
  
PB PB0 0.75
After second condensation
Mole fraction of A (χ A )  0.645

[ 31 ]
Solutions

Mole fraction of B ( (χ B )  1  0.645  0.355

Ratio of partial pressures
PA0  P 0  0.25 0.645
  A0   
PA  PB  0.75 0.345
 P 0  0.645 0.75
 A0   
 PB  0.345 0.25
PA0
  2.33
PB0
After third condensation
PA00  PA0  0.25 0.25
 00
  0   (2.33)3   4.242
PB  PB  0.75 0.75
 Mole fraction of B
PA00 1
 00 00
  0.101 = Mole fraction of B
PB  PB 3.42
JE

Example 6: The boiling points of bromine (Br2) and iodine monochloride (IC1) are 58.8ºC and 97.4ºC
respectively. The boiling point of IC1 is higher than that of Br2 because
(a) IC1 is polar and Br2 is non-polar.
(b) the vapour pressure of IC1 is higher than of Br2 at room temperature.
ES

(c) IC1 is ionic, while Br2 is molecular compound.

(d) both (a) and (c).

Solution: (a) Conceptual

an

Example 7. The correct relationship between the boiling points of very dilute solutions of AlCl3 (t1) and
CaCl2 (t2) having the same molar concentrations
(a) t1 = t2 (b) t2 > t1
(c) t1 > t2 (d) t2  t1
ka

Solution: (c) Conceptual

Problem 8. If a thin slice of sugar beet is placed in concentrated solution of NaCl then
lp

(a) sugar beet loses water from its cell

(b) sugar beet will absorb water from solutions
(c) sugar beet will neither absorb nor lose water
(d) sugar beet will dissolve in water

Solution: (a) Conceptual

Problem 9: 2N HCl solution will have same molar concentration as a
(a) 4.0 N H2SO4 (b) 0.5 N H2SO4
(c) 1N N2SO4 (d) 2N H2SO4

Solution: (a) Conceptual

Problem 10. The solution having lower osmotic pressure when compared to another is called
(a) Isotonic solution (b) Hypertonic
(c) Hypotonic (d) None of these

Solution:. (c) Conceptual

[ 32 ]
Solutions

1.4 Colligative Properties of Solution

Solutions of Non Volatile Solute and Volatile Solvent

Colligative Properties
The properties which depend entirely upon the number of particles of solute in a given volume of
solvent and not on the chemical nature of the solute molecule are defined as Colligative properties.

Here, we shall consider four properties of solution containing non volatile solutes.

(i) Lowering in vapour pressure.

(ii) Elevation in boiling point.
(iii) Depression in freezing point.
(iv) Osmotic pressure.
It is convenient to subdivide the solutions in the
JE

A. Solutions of non electrolytes

B. Solutions of electrolytes

A. Solutions of Non Electrolyte

ES

Lowering in Vapour pressure: When a non volatile solute is present in the solution, the vapour
pressure of the solution will be less than vapour pressure of pure solvent.

Let there be a solution of solute B. in solvent A

an
Only 'A' Particles

Since ‘B’ is non volatile it won’t go to the vapour phase Solvent (A)
hence, the vapours above solution will be only due to
Solute (non volatile) (B)
volatile solvent ‘A’. Since,
ka

PA  PA0A
 PA < PA0 so, vapour pressure is lowered.
lp

For a binary system A +B = 1.

Substituting the value of A
 PA = PA0 (1–B)

PA = PA0 – PA0 B

 PA0 B = PA0 – P = P (Lowering in vapour pressure)

P = PA0 B
 P B
 Lowering in vapour pressure is directly proportional to the mole fraction of solute.
The relative lowering in vapour pressure is equal to the mole fraction of solute.

ΔP
= B
PA0

[ 33 ]
Solutions

Hence,

(a) Lowering in vapour pressure is directly proportional to the mole fraction of solute in the
solution.

(b) Relative lowering in vapour pressure is equal to the mole fraction of solute.

1. Calculation of molecular mass of solute (B) in solvent (A)

nB
P = PA0 B = PA0
nA  nB
 
 W /M 
B B
= PA0  W WB


A

 M A M B 
WB WA WB
But when the solution is dilute then M <<< M and hence, M can be neglected in the
B A B
denominator
 0   W M 
0 WB  M A  P   B A
 P = PA  or MB =
JE

WA  M B  P   WA 
   

2. The relative lowering in vapour pressure is determined by Ostwald And Walker Method. In
this method a stream of dry air is passed successively through a set of weighed bulbs containing
ES

the solution and then through a set of merged bulbs containing pure solvent and finally
through weighed U-shaped tubes containing anhydrous CaCl2.
an
ka

(a) Let the loss in weight of solution bulbs be = w1 gm.

(b) Loss in weight of solvent bulbs = w2 gm.
(c) Loss in weight of solution bulbs (w1)  vapour pressure of solution.
lp

(d) Loss in weight of solvent bulbs (w2)  vapour pressure of solvent – vapour pressure of
solution.
 Ps  w1 and (P0 – Ps)  w2
P 0  Ps w2
 0

P w1  w 2

Loss in weight of solvent bulbs

= Total loss in weight of solution bulbs and solvent bulbs

= XB, i.e., mole fraction of solute

Elevation in Boiling Point

When a liquid is heated then due to rise in temperature the liquid vapourises and the vapour pressure
increases. When the vapour pressure of the liquid becomes equal to the atmospheric pressure, the
liquid begins to boil. The temperature at which the equilibrium vapour pressure of the liquid becomes
equal to the atmospheric pressure is called boiling point.

[ 34 ]
Solutions

When a non volatile solute is added to the solvent the vapour pressure of the solvent in the solution
decreases. Consequently the solution has to be heated to a higher temperature to have its vapour
pressure equal to atmospheric pressure.

Relationship for elevation in Boiling points

Consider the graph of vapour pressure

1 atm A D E
versus temperature in Kelvin scale. Pº
Vapour
Pressure
Here, Triangle ADB and ACE are similar P1 T Bº = Boiling point
nt B temperature
l ve 1
So tion- 2
Hence, P2 lu -
i on C
So lu t
AD AB So

AE AC TBº T1 T2

TB
T1 – T 0 P 0 – P1 Temperature

T2 – T 0 P 0 – P2
JE

 T 1 – T 0  P0 – P1
 TB  P
Also,
P  B
ES

 TB  B
nB
TB 
nA  nB
an

nB
TB  [Dilute solutions]
nA

B W
A M
TB  M  W
ka

B A
WB
  TB  Kb
MB WA
lp

WB
When, M = 1 mole and WA = mass of solvent in kilogram (kg)
B

  TB  K b  m m = molality of solution KB = Ebullioscopic constant

 TB  K B [when concentration is kept constant]. Hence, elevation in boiling point depends

upon
KB, i.e., nature of solvent

ΔTB  m [When solvent taken is same]

KB is defined as the elevation in boiling point of a solvent when 1-gm mole of a non-volatile solute is
dissolved in 1000 gm of solvent.
2
RTb
Kb = lv = latent heat of vapourization per gram of the solvent.
1000 lv

[ 35 ]
Solutions

RTb2 M 0
Also Kb = where M0 = molecular weight of solvent.
1000H v

Kb W solute Kb WB
ΔTB   1000 ΔTB   1000
M soluteW solvent MB  WA

WB = Wsolute = Mass of solute taken

MB = Msolute = Molecular weight of solute

WA = Wsolvent = Mass of solvent taken in grams

Kb WB
 Msolute   1000
TB  WA
TB (1) K B (1)
Also TB ( 2) = K B ( 2 ) when concentration is same but solvent different

TB (1) m1
JE

TB ( 2) = m2 when solvent is same but concentration different

TB (1) Mo(2) 1

=  TB  Mo when solvent same and amount of solute is same
ES

TB ( 2) Mo(1) (1)

Depression in Freezing Point

When a solvent is cooled, a temperature is eventually reached at which solid begins to separate from
an

the solution. The temperature at which this separation begins is called freezing point of solvent.

At freezing point liquid and solid are in equilibrium.

F.P.
ka

Liquid Solid

At the freezing point, the vapour pressure of liquid and solid will be same.
lp

Addition of a non-volatile solute, decreases the vapour pressure of pure liquid. Therefore, for a solid
to have the same vapour pressure as the solution, the temperature would lower down. This phenomenon
is called depression in freezing point.

Relationship for Depression in Freezing Point.

Here again.
Tf p Tf  P
p  molality or P  XB
Tf  molality Tf  XB

nB
 Tf  n for dilute solutions
A

WB
 Tf = Kf M W when WA is in kilogram
B A

[ 36 ]
Solutions

 T f  K f m
K f = molal depression constant

K f is defined as the depression in freezing point of a solvent when 1-gm mole of a non-volatile
solute is dissolved in 1000 gm of solvent, i.e.
RT f2 RT f2 M 0
Kf  also Kf 
1000 l f 1000 H f
where T f = freezing point
T f = latent heat of fusion per gram
Also
RT f  w solute
T f  1000
M solute  W solvent
Hence molecular weight of solute
K f  W solute
JE

M solvent  1000
T f  W solvent

Since, T f = Kf m  T f  Kf [When concentration is same but different solvents are taken]

ES

T f  m [when solvent is same but different concentration are taken]

Osmotic Pressure
an

Osmosis
1. The phenomenon of osmosis, first observed by Abbe Nollet, may be defined as a process in
which pure solvent molecules pass through a semipermeable membrane from a solution of low
ka

concentration to a solution of higher concentration.

(a) Exosmosis is the outward flow of water from a cell containing an aqueous solution through
a semipermeable membrane, e.g., grape in NaCl solution.
lp

(b) Endosmosis is the inward flow of water into a cell containing an aqueous solution through a
semipermeable membrane, e.g., grape in water.

2. The most frequently used semipermeable membrane in laboratory is that of copper ferrocyanide,
Cu2[Fe(CN)6] because it is very strong and can withstand very high pressure. Remember that
semipermeable membrane of Cu2[Fe(CN)6] does not work in non-aqueous solution because it
gets dissolved in non-aqueous solvents. Other synthetic semipermeable membrane is that of
calcium phosphate. Natural semipermeable membranes are parchment paper, cell walls, pig’s
bladder, skin surrounding white of an egg, membrane surrounding RBCs, etc.

When a solution (say of sugar) is separated from the pure solvent (water in present case) by
means of a semipermeable membrane (a membrane which allows only the solvent molecules but
not the solute molecules to pass through it), the pure solvent passes through the membrane and
goes to solution (osmosis) till the hydrostatic pressure of the liquid column exactly balances the

[ 37 ]
Solutions

tendency of water to pass inward through the semipermeable membrane. The hydrostatic pressure
set up as a result of osmosis is a measure of the osmotic pressure of the solution. For instance,
if the solution of density d rises to height h, then osmotic pressure is expressed as
 = h × d × g, where, g is the acceleration due to gravity.
The osmotic pressure may be defined as the excess pressure which must be applied to a solution
in order to prevent flow of solvent into the solution through the semipermeable membrane.
Osmotic pressure may also be defined in several other ways.
(i) Osmotic pressure is the excess pressure which must be applied to a given solution in order
to increase its vapour pressure until it becomes equal to that of the solution.
(ii) Osmotic pressure is the negative pressure produced when a solution is separated from the
solvent by a semipermeable membrane.
(iii) Osmotic pressure is the hydrostatic pressure produced when a solution is separated from
the solvent by a semipermeable membrane.
JE

Laws of Osmotic Pressure

The different laws of osmotic pressure are:
1. Boyle-Vant Hoff law 2. Charles-Vant Hoff law
ES

3. Avogadro-Vant Hoff law 4. Vant Hoff theory of osmotic pressure

Vant Hoff Theory of Dilute solution:
Vant Hoff gave an idea that dilute solution behave like ideal gases and gas laws obeyed by ideal gas
an

are also obeyed by dilute solution .

We know that
1
V (Boyle - van’t Hoff Law)
ka


VT (Charles Van’t Hoff law)
Vn (Avogadro - Van’t Hoff law)
n T
 V
lp


nRT
 V= R = solution constant (0.0821 it atm K–1 mol–1)

n
 = RT
T
V
 = CRT
Hence, at a given temperature
C

Important relations concerning osmotic pressure, P or 

n
(i) V = n RT or V = n ST or = ST or = CST
V
where = Osmotic pressure in atmospheres
n = Number of moles of the solute present in V litres of the solution
C = Concentration of the solution in moles per litre
T = Temperature in K
R or S = 0.0821 l atm deg–1 mole–1

[ 38 ]
Solutions

w  w 
(ii) V = M ST  n  M 
0  0 

wST
M0 = (M0 = Molecular weight of solute)
V
where w = Wt. of solute in g dissolved in V l of solution
m = Molecular wt. of the solute

(iii)  = h d g

where h = Height, d = density, g = Gravitational acceleration.

(iv) In isotonic solutions, since osmotic pressure, p is equal, their concentration (C) must also
be equal, i.e.
n1 n2 w1 w
 ;  2
V1 V2 m1V1 m2 V2

(v) If a number of solutes are present in the solutions and 1, 2, 3, etc., are their individual osmotic
pressures, then
JE

Total osmotic pressure = 1 + 2 + 3 + .....

Reverse osmosis
ES

If a pressure higher than osmotic pressure is applied on the solution, the solvent will flow from the
solution into the pure solvent through the semipermeable membrane. Since, here the flow of solvent
is in the reverse direction to that observed in the usual osmosis, the process is called reverse osmosis.
It is used in the desalination of sea water to obtain pure water.
an

Isotonic Solutions
A pair of solutions having the same osmotic pressure are known as isosmotic or isotonic solutions.
ka

Isotonic solutions have the same concentration. 0.85% NaCl solutions is found to be isotonic with
blood, while 0.9% NaCl solution isotonic with human RBCs. A solution having lower or higher osmotic
pressure than the other is to be hypotonic or hypertonic respectively in respect to other solution.
lp

(i) When placed in water or hypotonic solutions, cell swell and burst (haemolysis).

(ii) When placed in hypertonic solutions, the fluid from the plant cells comes out and thus the cells
contract in size (plasmolysis). When excess of fertilizers (like urea) are applied, plasmolysis
takes place and plants dry up (wilt).

Osmolarity
Osmolarity is the term used by physiologists to discuss the osmotic behaviour of solutes which either
dissociate or associate in solution. Mathematically,

Osmolarity = Molarity × No. of particles produced per formula unit of the solute

B. Solution of Electrolytes
Abnormal Behaviour of Solutions: Since the colligative properties of solutions, viz. lowering
of vapour pressure, elevation in boiling point, depression in freezing point and osmotic pressure,

[ 39 ]
Solutions

depend solely on the number of solute particles present in solution and not on their nature,
colligative properties of the solutes which undergo dissociation (electrolytes) in solution would be
higher than expected for the normal substances (non-electrolytes). For example, one mole of a
solute like glucose, cane sugar, urea, etc. when dissolved in 1000 g of water depresses the
freezing point of water by 1.86ºC. However, solution of one mole of NaCl or BaCl2 in 1000 g of
water depress the freezing point of water by 3.72ºC (2 × 1.86) and 5.58ºC
(3 × 1.86) respectively because each molecule of NaCl and BaCl2 dissociates to give 2 (Na+ &
Cl–) and three (Ba2+ and 2Cl–) ions respectively and each ion behaves as a particle in itself.
Thus, among the 0.1 M solution of the various substances like can sugar, NaCl, BaCl2, Al2(SO4)3,
etc. the colligative effect will be maximum in Al2(SO4)3 solution giving 5 ions per molecule.

Similarly, there are certain substances which associate when dissolved in a particular solvent.
Hence, the molecular weight of such substances as determined with the help of colligative
properties will be more than the theoretically calculated value from the molecular formula. For
example, the observed molecular weight of acetic acid when dissolved in benzene is found to be
118 which is nearly double the value (60) calculated from its molecular formula, CH3COOH.
JE

This is due to the fact that acetic acid, in benzene, does not exist as CH3COOH but as a dimer,
i.e., (CH3COOH)2.

Vant’f Hoff Factor, i.

ES

To account for the above anomalies, Van’t Hoff introduced a factor ‘i’ in the Van’t Hoff equation
( V = RT) of osmotic pressure. The modified equation may thus be written as V = iRT

The factor ‘i’ was defined by the expression:

an

Observed osmotic pressure

i = Normal osmotic pressure
ka

The experimental value of i can be obtained by dividing the observed osmotic pressure of the
solution under study with that of the solution of a normal substance (say sucrose) of the same
concentration (molarity) as that of the substance under study.
lp

Now since osmotic pressure behaves like other colligative properties, the factor i can also be
applied to other colligative properties. Thus, in general,

Actual number of particles

i = No. of particles when no ionisation /associati on

Observed colligativ e property (experimen tal)

i= Normal colligativ e property (calculate d)

Now, since molecular weight of a solute is inversely proportional to the colligative property, the
factor i may also be defined in the following way

Normal molecular wt. (calculated value)

i = Observed molecular wt. (experimental value)

Evidently for a normal substance (which neither dissociates nor associates in solution), the factor
i is always unity.

[ 40 ]
Solutions

When the Van’t Hoff factor is included then the colligative properties get modified as follows

(a) Relative Lowering in Vapour Pressure

0
P  PS P0  Ps inB
0 = i  XB  0

P P inB  nA
Where i = van’t Hoff factor
XB = mole fraction of solute for dilute solution

P 0  PS nB
0 =i n
P A

nB = number of moles of solute

nA = number of mole of solvent

P 0  PS B W A M
 0 =i M W
P B A
JE

Where, WB = Amount of solute dissolved

WA = Amount of solvent taken

ES

MB = Molecular mass of solute

MA = Molecular mass of solvent

(b) Elevation in Boiling point

an

TB = iKb m

WB
TB = iKb  M  W ( gms) 1000
B A
ka

(c) Depression in Freezing Point

Tf = iKf m.
lp

WB
Tf = iKf  M  W ( gms) 1000
B A

(d) Osmotic Pressure

v = inRT

 = iCRT

Relationship between Van’t Hoff factor for Dissociation and

association
1. Dissociation: Degree of dissociations : It is defined as the number of moles dissociated
over the initial concentration taken.
Total number of particles at equilibriu m
Van’t Hoff Factor :
Initial concentrat ion

[ 41 ]
Solutions

Let c moles per litre of an electrolyte AxBy be taken and let it dissociate as
AxBy xAY+ + yBx–
Initial conc c o o
.. yC moles of Bcx– is formed
c o o
 Ax By xAy+ + yBx–
(C – C) xC yC

(C  C )  x C   y C 
i=
C

1    x  y
 i= = 1 + [(x + y)–1]
1
JE

Let x + y = n = number of particles formed after dissociation

 i = 1 + (n – 1)
ES

i 1
=
n 1

2. Association: Degree of Association : It may be defined as the number of molecules associated

over initial concentration
an

number of moles associated

=
Initial concentrat ion
ka

Total number of moles of particles at equilibriu m

i=
Initial concentrat ion

Let n molecules of an electrolyte A undergo association

lp

nA An
Let the initial concentration of A = C
The degree of association = 

C
when C moles of A associate then moles of An are formed
n
C
C  C 
C n
number of moles of equilibrium (C – C) i=
n C

If C = 1

1  
n
i= 1

1  i 1
i = 1 +  n 1  = 1
  1
n
[ 42 ]
Solutions

Illustration 1: Calculate the freezing point of an aqueous solution of non-electrolyte having an osmotic
pressure of 2.0 atmosphere at 300 K. [Given Kf = 1.86 K kg mole–1 and S = 0.0821 litre atm
K–1mol–1]

Solution: We know
 = CST
Given
 = 2.0 atm
T = 300 K
S = 0.0821 litre atm K–1 mol–1
C=?
2.0 = C  0.0821  300

2.0
C= = 0.0812 mol litre–1
0.0821 300
Since solution is very dilute molality may be taken as equal to molarity
JE

Tf = Kf  m
Tf = 1.86  0.0812
= 0.151
ES

F.P. = –0.151ºC

Illustration 2: A tube of uniform bore (a = 1 cm2) is closed at one end with semipermeable membrane. A 5%
(w/v) solution of glucose is filled in the tube and it is dipped in pure water at 27ºC, so that
equilibrium is attained. Find out
an

(a) Osmotic pressure of the solution

(b) Height developed in vertical column
[Given density of the final sucrose solution is 2g/cc]
ka

Solution: We know,
v = nRT
lp

w
v = . RT
T
M
w = 5g, v = 100 ml or 0.1 litre, M = 180, R = 0.0821, T = 300 K
5
0.1  =  0.0821  300
180
5  0.0821 300
= = 6.84 atm.
180  0.1
Further,
 = 6.84 atm = 6.84  1.01  105 Nm–2
d = 2 g/ml = 2  103 kg m–3
g = 9.81 m sec–2
we know
 = hdg
 6.84  1.01105
h = dg =
2  103  9.81
= 35.22 meters
[ 43 ]
Solutions

Illustration 3: Boiling point of an aqueous solution is found to be 100.5ºC. Find out the osmotic pressure of
this solution. [Given K b = 0.5 K kg mol–1]

Solution: B.P. of water = 100ºC

Tb = 100.5 – 100 = 0.5
We know
Tb = Kb  m
0.5 = 0.5  m
m =1
Since, solution is dilute molality = molarity
We know,
 = CRT
 = 1  0.0821  300
= 24.63 atm
JE

Illustration 4: The boiling point of pure benzene is 80ºC. The boiling point of a solution containing 1g of a
substance dissolved in 83.4 g of benzene is 80.175ºC. If the latent heat of vaporization of
benzene is 94 cal per g. Calculate the [Link]., of solute.
ES

Solution: Latent heat of vaporization = 94 cal per g

Boiling point of benzene = 80ºC = 353 K
We know,
[Link] 2 1.98  353  353
= 2.624 K Kg mol–1
an

Kb = =
1000lv 1000  94
Further we know,
1000Kb  w
ka

Msolute =
Tb  W
Tb = (80.175 – 80) = 0.175ºC
lp
1000  2.624  1
Msolute = = 179.78
0.175  83.4

Illustration 5: 100 g of Sucrose solution in water is cooled to 272.5 K. Find out the weight of ice that will
separate at this temperature. Assume that the solution started freezing at –38ºC.
[K f = 1.86 K Kg mol–1]

Solution: Mass of solution = 100 g

Say mass of solute is w g and mass of solvent Wg
w = 100 – W
Tf = 38º
Molecular weight of sucrose = 342

1000 1.86 100 w

m=  W
38

W = 93.47 g
[ 44 ]
Solutions

When the solution is cooled to –0.5ºC let the mass of water left unfrozen = W1g
Tf = 0.5

1000  K f  w
m = ΔTf  w

[w = 100 – 93.47 = 6.53 g]

1000  1.86  6.53

342 = 0.5  W1

W1 = 71.028 g
Hence, amount of water separated out = 22.43 g.

SAMPLE PROBLEMS 1.4 (MCQ)

Problem 1: A solution containing 6 g of a solute dissolved in 250 cm3 of water gave an osmotic pressure
of 4.5 atm at 27°C. Calculate the boiling point of the solution. The molal elevation constant
of water is 0.52°C per 1000 g.
JE

(a) 100.095 (b) 0.095

(c) 0.094 (d) 0.092

Solution: (a) Van’t Hoff equation for osmotic pressure is

ES

πV  nRT
4.5 × 0.25 = n × 0.0821 × 300
4.5  0.25
or n   0.0457 mol
an

0.0821 300
i.e., 0.0457 mol of the solute is present in 250 ml of solution.
0.0457
Molality of the solution m   1000 = 0.1128
250
ka

ΔTb  K b m  0.52  0.1128  0.095C

Boiling point of solution
lp

Tb s  Tb0  Δ Tb  1 0 0  0 .0 9 5  1 0 0.0 9 5  C

Problem 2: A mixture which contains 0.550 of camphor and 0.090 g of an organic solute melts at 161°C.
The solute contains 93.75% C and 6.25% H by weight. What is the molecular formula of
compound? Kf for camphor is 37.5°C mol–1 kg. The melting point of camphor is 209°C.
(a) C10H8 (b) C10H10
(c) C10H12 (d) C10H22

Solution: (a) Given,

ΔT  209  161  48C
W2 = 0.09 g (organic solute)
W1 = 0.55 g (camphor)
Kf = 37.5°C mol–1 kg
1000  K f  W2
ΔT 
Mw2  W1

[ 45 ]
Solutions

1000  37.5  0.09

48 
Mw2  0.55
 Mw2  127.84
% No. of moles Mole ratio
93.75 7.8125
C = 93.75  7.8125  1.25
12 6.25
6.25 6.25
H = 6.25  6.25 1
1 6.25
 Empirical formula is C5H4 and empirical formula weight = 64

127.84
 Molecular formula is (C5H4)n and n  2
64
 Molecular formula of solute is (C5H4)2= C10H8
JE
Problem 3: If the boiling point of an aqueous solution 100.1°C, what is its freezing point? Given Lf = 80,.
Lv = 540 cal g–1 respectively for H2O.
(a) 0.36°C (b) 0.46°C
(c) 0.56° (d) 0.76°
ES

Solution: ΔT f  K f  m

ΔTb Kb RTb2 1000 L f

  
an

ΔT f K f 1000Lv RT f2
2
ΔTb Tb  L f
 2
ΔT f Tf  Lv
ka

Tbs  100  273  373K

Tb0  273 K
ΔTb  100.1 100  0.1C
lp

0.1 (373)2  80

ΔT f (273) 2  540
ΔT f  0.36C
Tf  0.36C

Problem 4: 0.5 g KCl was dissolved in 100 g water, and in solution, originally at 20°C, freezes at
– 0.24°C. Calculate the percentage dissociation of salt. (Kf for water is 1.84 K kg mol–1).
(a) 92% (b) 90%
(c) 85% (d) 80%

Solution: (a) Calculate the (theoretical) molecular mass of KCl

= 39 + 35.5 = 74.5
ΔTf  K f  m
1.84  0.5
0.24  i   1000
74.5  100

[ 46 ]
Solutions

i = 1.92
Now, KCl dissociates as KCl K  Cl
Total moles 1 0 0
Mole after dissociation 1–  
Total number of moles after dissociation = 1 –  +  +  = 1 + 
1 α
i
1
or  + i – 1 = 1.92 – 1 = 0.92
Percentage dissociation = 0.92 × 100 = 92%

Problem 5: Calculate the Van’t Hoff factor when 0.1 mole NH4Cl dissolved in 1 L of water. The degree
of dissociation of NH4Cl is 0.8 and its degree of hydrolysis is 0.1.
(a) 7.68 (b) 2.68
(c) 1.68 (d) 0.68

Solution: (b) Given,

Degree of dissociation () = 0.8
JE

Degree of hydrolysis (h) = 0.1

Considering, ionsiation of NH4Cl;
NH 4 Cl NH 4  Cl 
ES

Initial 0.1 0 0
At equilibrium – 0.08 + 0.08 + 0.08
–––––––––––––––––––––––––––––––
0.02 0.08 0.08
an

Considering hydrolysis of NH 4 ion

NH 4  H2O NH 4OH + H
ka

Initial 0.08 0 0
– 0.008 + 0.008 + 0.008
––––––––––––––––––––––––––––––––––––––––––––––––
lp
At equilibrium 0.072 0.008 0.008
Total number at equilibrium
i
Initial moles
n NH4 Cl  n NH  n Cl  n NH 4 OH  H 
i  4

0.1

0.02  0.072  0.08  0.008  0.008 0.188

   1.88
0.1 0.1

Problem 6: Each salt undergoes 90% dissociation which of the following will have the highest building
point?
(a) Decinormal Al2(SO4)3
(b) Decinormal BaCl2
(c) Decinormal Na2SO4
(d) A solution obtained by mixing equal volume of (b) and (c) and filtering

[ 47 ]
 Solutions

Solution: (a) Al2(SO4)3 can furnish maximum no. of ions.

Problem 7: The ratio of the value of any colligative property for KCl solution to that of sugar solution is:
(a) 1 (b) 2
(c) 0.5 (d) 4

obs. C.P. 1    x  y (KCl) 2

Solution: (b) i   
cal. C.P. 1 1
Problem 8:. Which of the following aqueous solution will have highest boiling point?
(a) 1 g NaCl solution (b) 1 g KCl solution
(c) 1 g urea solution (d) all will have same boiling point

Solution (a) Elevation in boiling point depends upon number of solute particle only.

Problem 9:. When HgI2 is added to an aqueous solution of KI there will be

(a) increase in boiling point (b) decrease in freezing point
(c) increase in vapour pressure (d) both (a) and (b)
JE

Solution: (c) Conceptual

Problem 10:. That solvent is better to be used during ebullioscopic measurements where the solvent has
(a) high Kb value
ES

(b) low Kb value

(c) where K b and Kf values are equal for solvent
(d) none of these

Solution: (a) Conceptual

an
ka
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