1

Solutions (4/6)
Mixture is a combination of two or more substances (i.e. components).
Mixtures are of two types –
a) homogeneous mixture in which mixing of components are uniform and
b) heterogeneous mixture in which mixing of components are non-uniform.
Solution is a homogeneous mixture of two or more pure substances.
Solution contains two parts solute and solvent. Solute is present in small amount and solvent
is present in large amount. Ex. In the solution of salt in water, salt is solute and water is
solvent.
Types of solutions – On the basis of physical state of solute and solvent there are nine types
of solutions -
Types of solutions

State of State of Examples

Solute solvent

Solid Liquid Sea water, benzoic acid in benzene, sugar in water

Solid Solid Metal alloys such as brass, bronze.

Solid Gas Iodine in air

Liquid Liquid Gasoline, ethanol in water

Liquid Solid Amalgams of mercury with metals as mercury in silver

liquid Gas Chloroform in nitrogen

Gas Liquid Carbonated water (CO2 in water), oxygen in water

Gas Solid Hydrogen in palladium

Gas Gas Air (O2, N2, Ar and other gases)

Capacity of a solution to dissolve a solute –

Solute + Solvent Dissolution Solution
Crystallization
Saturated solution – Saturated solution contains maximum amount of solute dissolved in
given amount of solvent at a specific temperature.
Supersaturated solution – Supersaturated solution contains solute more than that required to
form a saturated solution
When a tiny crystal of a solute is added to supersaturated solution, the excess solute separates
out and forms saturated solutions.
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Que – Define the terms – a) Saturated solution and b) Supersaturated solution.

Solubility – The solubility of a solute is its amount per unit volume of saturated solution at a
specific temperature. It is expressed in mol L -1 or mol dm-3.
Factors affecting solubility – The extent of dissolution of a substance (solute) depends upon
the following factors –
i) Nature of solute and solvent – Compounds with similar chemical properties dissolve
easily. The substances having same
intermolecular forces are soluble with each other. Polar
solute dissolve in polar solvent easily. Ex. sugar dissolves in water.
Also, nonpolar solute dissolve in nonpolar solvent easily. Ex. cholesterol dissolves in
benzene.
ii) Effect of temperature on solubility –
a) Effect of solubilities of ionic solids with temperature –
Que – What is the effect of temperature on solubility of solids in water? Give example.
Solubility of solid α Temperature.
As temperature increases, solubility increases.
In case of endothermic reaction like KCl dissolve in water, increase in temperature
increases solubility.
In case of exothermic reaction like CaCl2 dissolve in water, increase in temperature
decreases solubility.

1
b) Solubilities of gases in liquids – Solubility of gas α
temp .
Solubility of gases in water decreases with increase in temperature.
When gases dissolves in water gas molecules in liquid phase are condensed.
Condensation is an exothermic process, hence solubility of gases in liquid decreases as
temperature increases.
Que – How does solubility of gas in water varies with temperature.
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iii) Effect of pressure on solubility – Pressure do not on solids and liquids because they are
incompressible.
Pressure affects the solubility of gases in liquids. Solubility of gases in liquids increases with
increase in pressure.
Henrys law – Solubility of gas in a liquid is directly proportional to the pressure of the gas
above the solution at constant temperature.
If ‘S’ is the solubility of a gas in liquid in mol/dm3 and
‘P’ is the pressure of the gas in bar over the solution.
S
Then, S α P i.e S = KHP where KH is Henrys constant and KH ¿
P
Henrys law constant (KH) – Solubility of gas in mol/dm3 at 1 bar pressure at a particular
temperature is called Henrys law constant. Its unit is moles dm⸺3 bar⸺1.
Problem -1) The solubility of N2 gas in water at 250C and 1 bar is 6.85×10−4 mol/L.
Calculate a) Henry’s law constant b) molarity of N2 gas dissolved in water under atmospheric
conditions when partial pressure of N2 in atmosphere is 0.75 bar.
−4 3
S
Ans. – a) KH = =¿ 6.85× 10 mol/dm = 6.85 ×10−4 mol /L / ¯¿
P 1 ¯¿ ¿
b) S = KH P = ¿ ¿ = 5.138 ×10−4 mol /L
Problem – 2) The Henry’s law constant of methyl bromide (CH3Br) is 0.159 mol/L/bar at
250C. What is the solubility of methyl bromide in water at 250C and at pressure of 130 mm
Hg.
1
Ans. – Since, P = 130 mm Hg × = 0.171 atm ×1.013 ¯¿ atom = 0.173 bar
760 mm Hg/atom
Here, KH = 0.159 mol/L/bar
According to Henry’s law, S = KH P = ¿ = 0.271 M .
Problem – 3) Henry’s constant for CH3Br (g) is 0.159 mol dm-3bar-1 at 250C. Calculate its
solubility in water at 250C, if its partial pressure is 0.164 bar.
Ans. – Given – KH = 0.159 mol dm-3bar-1, P = 0.164 bar
Formula : S = KH P = 0.159 × 0.164 = 0.02 mol dm-3.
Problem – 4) Henry’s constant for solubility of methane in benzene is 3.25×10−2 mol L-1
atm-1 at constant temperature. Calculate solubility of methane at 1 bar pressure and at same
temperature.
Ans. - Given – KH 3.25×10−2 mol L-1 atm-1, P = 1 bar
−2
3.25× 10
KH = 3.25×10−2 mol L-1 atm-1 = = 3.21×10−2 mol L-1 bar-1
1.013
S = KH P = 3.21×10−2 mol L-1 bar-1 × 1 bar = 3.21 mol L-1.
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Problem – 5) For a gas, the Henry’s constant is 1.25×10−3 mol dm-3 atm-1 at 250C. Calculate
the solubility of the given gas at 2.5 atm and 250C.
Ans. – Given – KH = 1.25×10−3 mol dm-3 atm-1, P = 2.5 atm, S = ?
By using Henry’s law S = KH P = 1.25×10−3 mol dm-3 atm-1 ×2.5 atm = 3.125×10−3 mol dm-3
Problem – 6) The solubility of dissolved oxygen to 170C is 2.6×10−3 mol dm-3 at 2 atm. Find
its solubility at 8.4 atm and 270C.
Ans. – Solubility of O2 = S1 = 2.6×10−3 mol dm-3, Solubility of O2 = S2 = ?
Initial pressure of O2 = P1 = 2 atm, Final pressure of O2 = P2 = 8.4 atm
(i) By Henry’s law S1 = KH P1
S 1 2.6 ×10−3
KH = = = 1.3 ×10−3 mol dm-3 atm-1
P1 2
(ii) By Henry’s law S2 = KH P2 = 1.3 ×10−3 × 8.4 = 10.92 ×10−3=1.092 ×10−2 mol
dm-3
Solubility of O2 = 1.092 ×10−2 mol dm-3
Problem – 7) Henry’s law constant for the solubility of methane in benzene is 4.27 ×10−5
mm-1 Hg mol dm-3 at constant temperature. Calculate the solubility of methane at 7600 mm
Hg pressure at same temperature.
Ans. – Given Henry’s law constant, KH = 4.27 ×10−5 mm-1 Hg mol dm-3,
Pressure of the gas = P = 760 mm Hg
KH = 4.27 ×10−5 ×760 = 3245× 10−5 atm-1 mol dm-3 = 3.245 × 10−2 atm-1 mol dm-3
760
P = 760 mm Hg = atm = 1 atm
760
By Henry’s law, S = KH P = 3.245 × 10−2 atm-1 mol dm-3× 1 atm = 3.245 × 10−2 mol dm-3
Problem – 8) The solubility of ethane at 250C is 0.92×10−3 g dm-3 at 1000 mm Hg pressure.
Calculate henry’s law constant.
Ans. – Solubility of ethane = S = 0.92×10−3 g dm-3, Pressure of ethane = P = 1000 mm Hg
Molar mass of ethane (C2H6) = 30 g/mol, Henry’s law constant, KH = ?
0.92 −3 −5
S = 0.92×10−3 g dm-3 = ×10 =0.3067 × 10 mol dm-3
30
1000
P = 1000 mm Hg = atm = 1.316 atm.
760
S 3.067 ×10−5
By Henry’s law, KH = = = 2.22 ×10−5 mol dm-3 atm-1
P 1.316
Problem – 9) The solubility of nitrogen at 300C is 2.5 ×10−3 g dm-3 at 760 m pressure. What
will be its solubility in mol dm-3 at 20, 000 mm and same temperature.
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Ans. – Initial solubility of N2 = S1 = 2.5 ×10−3 g dm-3, Initial pressure = P1 = 760 mm

Final pressure = P2 = 20, 000 mm, Final solubility = S2 = ?
Molar mass of N2 = 28 g/mol
2.5 −3 −5
S1 = 2.5×10−3 g dm-3 = ×10 =8.93 ×10 mol dm-3
28
760
P1 = atm = 1 atm
760
20000
P2 = atm = 26.32 atm
760
By Henry’s law, S1 = KH P1
S 1 8.93 ×10−5
KH = = = 8.93 ×10−5 mol dm-3 atm-1
P1 1
S2 = KH P2 = 8.93 ×10−5 × 26.32 = 2.35 ×10−3 mol dm-3
Alternative method - S1 = KH P1 and S2 = KH P2
S 2 K H P2 P 2
Since, = =
S 1 K H P1 P 1
P2 −5 20 , 000
Hence, S2 = S1× =8.93 ×10 × = 2.35 ×10−3 mol dm-3
P1 760
Problem -10) Fish generally needs O2 concentration in water at least 3.8 mg/L for survival.
What partial pressure of O2 above the water is needed for the survival of fish? Given the
solubility of O2 in water at O0C and 1 atm partial pressure is 2.2×10−3mol/L
S 2.2× 10−3 mol /L
Ans. – KH = = = 2.17 ×10−3 mol L-1 bar-1
P ¯
1.013 ¿ ¿
−3
3.8× 10
Required concentration of O2 = 3.8 mg/L = = 1.18×10−4 mol/L
32
−4
S 1.18× 10
Pressure needed = P = = = 0.054377 atm.
K H 2.17 ×10−3
Vapor pressure of solutions of liquids in liquids –
Consider a binary solution of two volatile liquids A1 and A2. When the solution is placed in a
closed container, both the liquids vaporize. An equilibrium is reached between vapor and
liquid phase. The partial pressure of the components is related to their mole fractions in the
solution.
Raoult’s law –
Que – State and explain Raoult’s law for volatile components.
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Ans. - Statement – The partial vapor pressure of any volatile component of a solution is
equal to the vapor pressure of pure component multiplied by its mole fraction in the solution.
Consider a binary solution of two volatile liquids A1 and A2, with partial vapor pressure P1
and P2 and mole fractions x1 and x2.
Then according to Raoult’s law, P1 = P10 x1 and P2 = P20 x2
Where P10 and P20 are the vapor pressures of pure liquids A1 and A2 respectively.
According to Daltons law of partial pressures, Total pressure (P) = P1 + P2
From the above equations P = P10 x1 and P2 = P20 x2
For binary solution x1 + x2 = 1 Hence x1 = 1 – x2
Put this value in the above equation we get, P = P10 (1 – x2) + P20 x2
P = P10 - P10 x2 + P20 x2
P = (P20 - P10) x2 + P10
As P10 and P20 are constants, plot of P versus x2 is a straight line.

I) For P1o versus x2 straight line, P = P10 at x2 = 0 and P = P20 at x1 = 1

II) For P1 versus x1 straight line, P1 = 0 at x1 = 0 and P1 = P10 at x1 = 1
III) For P2 versus x2 straight line, P2 = 0 at x2 = 0 and P2 = P20 at x2 = 1
Problem – The vapour pressures of pure liquids A and B are 450 mm Hg and 700 mm Hg
respectively at 350 K. Find the composition of liquid and vapour if total vapour pressure is
600 mm.
Ans. – i) Composition of A and B in the solution are x1 and x2
Here P1o = 450 mm Hg, P20 = 700 mm Hg and P = 600 mm Hg
Hence, 600 mm Hg = (700 mm Hg – 450 mm Hg) x2 + 450 mm Hg = 250 x2 + 450
600 – 450 = 250 x2
150 = 250 x2
Or x2 = 250/150 = 0.6
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Since, x1 = 1 – x2 = 1 – 0.6 = 0.4

ii) Composition of A and B in vapour are y1 and y2 respectively.
P1 = y1 P and P2 = y2 P
Then according to Raoult’s law P1 = P10 x1 and P2 = P20 x2
P 1 P 01 x 1 450 mm Hg× 0.4
Hence, y1 = = = = 0.3
P P 600 mm Hg
y2 = 1 – y1 = 1 – 0.3 = 0.7
Ideal solution and Non-ideal solution –
Ideal solution –
a) Ideal solution obey Raoult’s law for entire range of concentrations.

change is zero, △mix H = 0

b) During the formation of ideal solution, neither heat is evolved or absorbed i.e. enthalpy

c) During the formation of ideal solution, volume does not change on mixing △mix V = 0 and
volume of solution is equal to sum of two liquid components.
d) In ideal solution solute-solute, solvent-solvent and solute-solvent molecular interactions
are comparable.
e) The vapor pressure of ideal solution always lies between vapor pressure of pure
components. Example – solution of benzene and toluene.
Non-ideal solution –
a) Non ideal solution do not obey Raoult’s law over entire range of concentrations.
b) The vapor pressure of non-ideal solutions is higher or lower than those of pure
components.
c) Non ideal solution shows two types of deviations from Raoult’s law –
i) Positive deviation from Raoult’s law –
Those solutions in which solute-solvent interactions are weaker than those between solute-
solute molecules and solvent-solvent shows positive deviations.
The vapor pressure of such solutions is higher than those of pure components.
Ex. Solution of ethanol and acetone, carbon disuphide and acetone.
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ii) Negative deviation from Raoults law –

Those solutions in which the interaction between solute-solvent molecules is stronger than
solute-solute or solvent-solvent interaction shows negative deviations.
The vapor pressure of such solutions is lower than those of pure components.
Ex. Solutions of phenol and aniline, chloroform and acetone.

Colligative properties – The physical properties of the solutions that depend upon the
number of solute particles and not on the nature of solute particles are called colligative
properties. These are –
1. Vapour pressure lowering
2. Boliling point elevation
3. Freezing point depression
4. Osmotic pressure
Colligative properties depends upon number of solute particles, as solute particles increases
colligative properties increases.
Types of colligative properties –
i) Vapor pressure lowering – Vapor pressure is the pressure exerted by vapours of liquid
when it is in equilibrium with the liquid at constant temperature. Vapor pressure of liquid
increases with increase in temperature.
a) In case of pure solvent its surface area is completely occupied by volatile solvent
molecules hence its vapor pressure is larger. All surface particles can undergo evaporation.
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b) In case of solution containing non-volatile solute its surface area is not completely
available for evaporation because partly it is occupied by non-volatile solute. Hence rate of
evaporation of solution will be less as compared to that of pure solvent and vapor pressure of
solution is lower than that of pure solvent.
If P10 is vapor pressure of pure solvent, P1 is the vapor pressure of solution containing non
volatile solute (i.e. P10 > P1). Then lowering of vapor pressure (△P) = P10 – P1
Raoult’s law for solutions of non-volatile solutes –
Que – State and explain Raoult’s for solutions of non volatile solutes.
Que – Derive the equation of Raoult’s law for binary solution containing non volatile
solute.
Que – Using Raoult’s law, how will you show that △P = P10 x2? Where x2 is the mole
fraction of solute in the solution and P10 is the vapour pressure of pure solvent.
Statement – The vapour pressure of solvent over the solution is equal to the vapour pressure
of pure solvent multiplied by its mole fraction in the solution. Thus, P1 = P10 x1
For binary solution containing solute x1 = 1 – x2 and hence P1 = P10 (1 - x2)
P1 = P10 – P10 x2
or (P10 – P1) = P10x2

Hence, △P = P10 x2 where △P = P10 – P1 = lowering of vapor pressure. Hence,

△P
0 = x2
P1

The above equation shows that △P depends upon x2 i.e. number of solute particles.
Thus △P the lowering of vapour is a colligative property.
Problem – An aqueous solution is made by dissolving 20 g of non volatile solute (molar
mass = 60 g/mol) in 90 g of water at 303 K. If the vapour pressure of pure water at 303 K is
32.8 mm Hg, what would be the vapour pressure of the solution.
Ans. – Given : Vapour pressure of pure water = P10 = 32.8 mm Hg
Mass of non volatile solute = 20 g, Molar mass of non volatile solute = 60 g/mol
Vapour pressure of solution (P1) = ?
90
Number of moles of water = = 5 mol
18
20
Number of moles of non volatile solute = = 0.333 mol
60
5
Mole fraction of water = x1 = = 0.938
5+0.333
Vapour pressure of solution, P1 = P10 x1 = 32.8 × 0.938 = 30.77 mm Hg
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Relative lowering of vapor pressure – The ration of vapor pressure of lowering of solvent
from solution to the vapor pressure of pure solvent is called relative lowering of vapor
pressure.

But △P = P10 x2
△ P P 01−P1
Relative lowering of vapor pressure = 0 = 0
P1 P1

△ P P 01−P1 △P
Hence, 0 = 0 = x2 or 0 = x2
P1 P1 P1
0
△ P P 1−P1 △P
0
= 0
=x 2 or 0 =x 2 (where x2 = mole fraction of solute)
P1 P1 P1

Hence relative lowering of vapor pressure is equal to mole fraction of solute.

Relation between relative lowering of vapor pressure and molar mass of solute –
Que – Derive the relationship between relative lowering of vapor pressure and molar mass
of non volatile solute.
Ans. - Consider a solution is prepared by dissolving W1 g of solvent and W2 g of solute.
If M1 is the molar mass of solvent and M2 is the molar mass of solute.
If n1 is the number of moles of solvent and n2 are the number of moles of solute.
W1 W2
Then n1 = ∧¿ n2 =
M1 M2
n2
But x2 =
n1 +n2
For a dilute solution, n1 > > n2 Hence, n1 + n2 = n1
n2
So, mole fraction of solute (x2) is x2 =
n1

△ P P 01−P1
Relative lowering of vapor pressure = 0 = 0 = x2
P1 P1
△ P n2
Hence the above equation becomes 0 =
P1 n1
W2
△ P n2 M 2
0 = =
P1 n1 W 1
M1
W2
0
P −P1 M 2
1
or 0 =
P1 W1
M1
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0
W 2 × M 1 × P1
Hence M2 =
W 1× △ P
Problem – 1) A solution is prepared by dissolving 394 g of a non-volatile solute in 622 g of
water. The vapour pressure of solution is found to be 30.74 mm Hg at 30 0C. If vapour
pressure of water at 30 0C is 31.8 mm Hg, what is the molar mass of solute?
0
P 1−P1 W2 M1
Ans. - 0 =
P 1
M2 W 1

Since, W2 = 394 g, W1 = 622 g, M1 = 18 g/mol, P1 = 30.74 mm Hg, P10= 31.8 mm Hg.

Substitute these values in above equation, we get
−1
31.8 mm Hg−30.74 mm Hg 394 g ×18 g mol
=
31.8 mm Hg M 2 × 622 g
−1 −1
11.4 g mol 11.4 g mol
0.033 = Hence, M2 = = 342 g/mol
M2 0.033
Problem – 2) The vapour pressure of pure benzene (molar mass 78 g/mol) at a certain
temperature is 640 mm Hg. A non-volatile solute of mass 2.315 g is added to 40 g of
benzene. The vapour pressure of the solution is 600 mm Hg. What is the molar mass of
solute?
Ans. - P10= 640 mm Hg, P1 = 600 mm Hg, W1 = 49 g, W2 = 2.315 g
0
P 1−P1 W2 M1
0 =
P1 M2 W 1

640 mm Hg−600 mm Hg 2.315 g−78 g/mol

Then, =
640 mm Hg M 2 × 40 g
2.315 g−78 g/mol × 640 mm Hg
M2 = = 72.23 g mol
40 mm Hg × 40 g
Problem – 3) The vapour pressure of water at 200C is 17 mm Hg. What is the vapour
pressure of solution containing 2.8 g urea in 50 g of water?
Ans. – Given : Vapour pressure of pure water = P10 = 17 mm Hg, Mass of urea (W2) = 2.8 g
Molar mass of water (W1) = 50 g, Vapour pressure of the solution (P1) = ?
Molar mass of urea (NH2CONH2) = 14 + 2 + 12 + 16 + 14 + 2 = 60 g/mol
Molar mass of water = 18 g/mol
0
P 1−P1 W2 M1
0 =
P 1
M2 W 1

17−P1 2.8× 18
=
17 50× 60
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17−P1
= 0.0168
17
17 – P1 = 0.0168 × 17 = 0.2856
P1 = 16.71 mm Hg

point of solvent containing non volatile solute and pure solvent at a given pressure. △Tb = Tb
ii) Boiling point elevation (△Tb) – Elevation in boiling point is a difference between boiling

– Tb0
If Tb0 is the boiling point of pure solvent and Tb is the boiling point of solution. Then, △Tb =
Tb – Tb0 and Tb > Tb0
Boiling point elevation as a consequence of vapor pressure lowering – If a graph of vapor
pressure versus temperature is plotted, vapor pressure temperature curve of solution is always
below the vapor pressure temperature curve of pure solvent. The difference between two
vapor pressures increases as temperature and vapor increases.

△P = x2 P10. The intersection of the solution curve at pressure of 760 mm is the boiling point

observed that boiling point of solution (Tb) is higher than that of pure solvent (Tb0). △Tb α
of solution. The intersection of solvent curve is the boiling point of pure solvent. It is

△P △ Tb = Tb - Tb0
Boiling point elevation and concentration of solute –
For dilute solution elevation in boiling point is directly proportional to molality of the
solution.
Then, △Tb α m i.e. △Tb = Kb m
where m is the molality of solution, and Kb is the molal elevation constant called
ebullioscopic constant.

=
△Tb K
Kb =
m mol /kg
Unit of molal elevation constant or ebullioscopic constant is K kg/mol or 0C kg/mol
Ebullioscopic constant (Kb) – If m = 1, △Tb = Kb
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Ebullioscopic constant is the elevation in boiling point is produced by 1 molal solution.

Que – Define the term ebullioscopic constant. What is its unit.
Relation between elevation in boiling point and molar mass of solute –
Que – Derive the relationship between elevation in boiling point and molar mass of solute.
Ans. – Consider a solution is prepared by dissolving W1 g of solvent and W2 g of solute. If M2
is the molar mass of solute and number of moles of solute (n2) = W2/M2.
W1 g W1
Mass of solvent = W1 g = = kg
1000 g /kg 1000
number of moles of solute W 2 / M 2 mol
If molality of solution, m = = Hence, m
mass of solvent ∈kg W 1 /1000 kg
1000W 2
= mol kg-1
M2W1

Since, △Tb = Kb m Then, △Tb = Kb

1000W 2 1000 K b W 2
Hence, M2 =
M2 W1 △Tb W1
Problem – 1) The normal boiling point of ethyl acetate is 77.06 0C. A solution of 50 g of a
non-volatile solute in 150 g of ethyl acetate boils at 84.27 0C. Evaluate the molar mass of
solute if Kb for ethyl acetate is 2.77 0C kg/mol.
1000 K b W 2
Ans. - M2 = Since, W2 = 50 g, W1 = 150 g
∆ T bW 1

△Tb = Tb - T b = 84.27 0C – 77.06 0C = 7.21 0C = 7.21 K

0

Kb = 2.77 0C kg/mol = 2.77 K kg/mol

Substitute these values in above equation we get,
1000 g /Kg ×2.77 K Kg/mol × 50 g
M2 = = 128 g/mol
7.21 K ×150 g
Problem – 2) 3.795 g of sulphur is dissolved in 100 g of carbon disulfide. This solution boils
at 319.81 K. What is the molecular formula of sulphur in solution? The boiling point of the
solvent is 319.45 K.
(Given that Kb for CS2 = 2.42 H Kg/mol and atomic mass of S = 32u)
1000 K b W 2
Ans. - M2 = Since, W1 = 100 g, W2 = 3.795 g
∆ T bW 1

△Tb = Tb - T b = 319.81 K – 319.45 K = 0.36 K

0

1000 g /Kg ×2.42 K kg /mol ×3.795 g

M2 = = 255.10 g/mol
0.36 K ×100 g
Atomic mass of S = 32 u
 14

molar mass of S 2.55.1

Therefore, number of atoms in a molecule of S = = = 7.92 = 8
atomic mass of S 32
Hence, molecular formula is S8 in CS2.
Que – What is the effect on the boiling point of water if 1 mole of methyl alcohol is added
to 1 dm3 of water? why?
Ans. – The boiling point of water depends on its vapour pressure, higher the vapour pressure
lower is the boiling point. If 1 mole of volatile methyl alcohol is added to 1 dm3 of
water its vapour pressure is increases by decreasing the boiling point of water.
iii) Depression in freezing point (△Tf) –
Freezing point of a liquid is the temperature at which liquid phase and solid phase are in
equilibrium and two phases have same vapor pressure.
Depression in freezing point is defined as the difference between freezing point of pure
solvent and freezing point of solution. If Tf0 is the freezing point of pure solvent and Tf is the
freezing point of solution.
Then, △Tf = Tf0 - Tf Here, Tf0 > Tf
Freezing point depression as a consequence of vapor pressure lowering -
If a graph of vapor pressure versus temperature is plotted, three curve are observed. Vapor
pressure curve of solution lie below the curve of solvent. The curve AB and CD intersect at
point B where solid and liquid phases of pure solvent are in equilibrium. The temperature
corresponding to B is the freezing point of solvent (Tf0). At point E equilibrium is formed. At
this point vapor pressure of solvent and solution becomes equal. The temperature
corresponding to E is the freezing point of solution (Tf). Freezing point of solution Tf is lower
than that of pure solvent Tf0.

Freezing point depression and concentration of solute –

For a dilute solution, the freezing point depression (△Tf) is directly proportional to molality
of the solution (m).
△Tf α m △Tf ¿ Kf m
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△Tf
Hence, Kf = Where Kf is the freezing point depression constant or cryoscopic constant.
m
If m = 1 molal, Then △Tf ¿ Kf
Thus, cryoscopic constant is the depression in freezing point produced by 1 molal solution.
Unit – Unit of molal elevation constant or ebullioscopic constant is K kg/mol or 0C kg/mol.
Que – Define the term cryoscopic constant. What is its unit.
Cryoscopic constant (Kf) – The depression in freezing point produced by dissolving 1 mole
of solute in 1000 g of solvent (one molal solution) is called cryoscopic constant.
Relation between freezing point depression and molal mass of solute –
Que – Obtain the relationship between freezing point depression of a solution containing
nonvolatile-nonelectrolyte solute and its molar mass.
Ans. - Consider a solution is prepared by dissolving W1 g of solvent and W2 g of solute. If M2
is the molar mass of solute and number of moles of solute (n2) = W2/M2.
W1 g W1
Mass of solvent = W1 g = = kg
1000 g /kg 1000
number of moles of solute W 2 / M 2 mol
If molality of solution, m = = Hence, m
mass of solvent ∈kg W 1 /1000 kg
1000W 2
= mol kg-1
M2W1

From the equation △Tf ¿ Kf m,

Then the above equation becomes △Tf ¿ Kf

W2 W2
×1000 Hence, M2 ¿ Kf
M2 W 1 △ Tf W1
×1000
Problem – The freezing point of pure benzene is 278.4 K. calculate the freezing point of the
solution when 4 g of a solute having molecular weight 100 g/mol is added to 200 g of
benzene (Kf for benzene = 5.12 K kg/mol)
Ans. – Given : T 0f =278.4 K , W2 = 4 g, M2 = 100 g/mol, W1 = 200 g, Kf 5.12 K kg/mol, Tf = ?

Hence, △Tf ¿
1000 K f W 2 1000 K f W 2 1000× 5.12× 4
M2 = = = 1.024 K
∆ Tf W1 M 2W 1 100 ×200

Now, , △Tf ¿ T f −T f = 278.4 K – 1.024 K = 277.376 K

0

Hence, freezing point of solution is 277.376 K

iv) Osmotic pressure ( π ¿ – Osmotic pressure is the term used for determination of molar
mass of solute.
Semipermeable membrane – Semipermeable membrane is the membrane which allows
solvent molecules to pass through it but not solute particles.
 16

Osmosis – The net spontaneous flow of solvent molecule in to the solution or from a solution
of lower concentration to higher concentration through semipermeable membrane is called
osmosis. Osmosis can takes place because vapor pressure of solvent is greater than solution.

Que – Define the term osmosis.

Osmotic pressure – Osmosis can be demonstrated by following experiment.

i) Apparatus consists of long Thistle tube. The mouth of thistle tube is closed by
semipermeable membrane.
ii) Sucrose solution is filled in thistle tube and immersed a solvent like water. There occurs a
net flow of solvent molecules into the solution through the semipermeable membrane.
iii) As a result, the original volume of solution increases and the liquid level of the solution
rises. This increase the hydrostatic pressure.
iv) At a certain stage this rising level stops indicating an equilibrium between the rates of
flow of solvent molecule from solvent to solution and from solution to solvent.
v) The hydrostatic pressure at this stage represents osmotic pressure in the thistle tube.
vi) Hydrostatic pressure is equal to hρg, where h is the height of liquid column in the tube, ρ
is the density solution and g is the acceleration due to gravity.
Osmotic pressure (π) –
The excess mechanical pressure which is applied on the side of solution to stop the flow of
solvent molecule in to the solution through semipermeable membrane is called osmotic
pressure. It is denoted by π .
Or The hydrostatic pressure that stops osmosis is called osmotic pressure.
Que - Define the term osmotic pressure.
 17

i) Isotonic solution – Two or more solutions having same osmotic pressures are called
isotonic solutions. Example - 0.1 M urea and 0.1 M sucrose are the isotonic solutions since
they have same osmotic pressure. Isotonic solutions have same molar concentrations.
ii) Hypertonic solutions and hypotonic solutions – If two solutions have different osmotic
pressure, then the more concentrated solution with higher osmotic pressure is called
hypertonic solution and the more dilute solution with lower osmotic pressure is called
hypotonic solution.
Ex. If osmotic pressure of sucrose solution is higher than that of urea solution, the sucrose
solution is said to be hypertonic solution to urea solution, and the urea solution is said to be
hypotonic solution to sucrose solution.
Que – Define the terms – a) Isotonic solution, b) Hypertonic solution and c) Hypotonic
solution.
Osmotic pressure and concentration of solution –
Que – Derive the equation : π=CRT
Ans. - For very dilute solution osmotic pressure ( π ¿ is given as,
n2 RT n
π V = n2RT or π = or π=CRT where C = 2
V V
Where n2 is the number of moles of non-volatile solute,
R is the gas constant 0.082 atm dm3K-1mol-1 and V is the volume of solution in dm3.
Molar mass of solute from osmotic pressure –
n2 RT
π= since number of moles of solute (n2) = W2/M2.
V
W 2 RT W RT
Then, π=¿ or M2 = 2
M 2V πV
Que – Derive an expression to calculate molar mass of non-volatile solute by osmotic
pressure measurement.
Reverse osmosis – The direction of osmosis can be reversed by applying pressure larger than
the osmotic pressure. The pure solvent then flows from solution into the pure solvent through
semipermeable membrane. This phenomenon is called reverse osmosis.
Fresh water and salty water are separated by a semipermeable membrane. When pressure
larger than the osmotic pressure of solution is applied to solution, pure water from salty water
passes into fresh water through membrane.
 18

Colligative properties of electrolytes - Electrolytes are the substances which when

dissolved in water gives two or more ions due to dissociation. Non electrolyte substances do
not dissociate into ions in aqueous solution. Electrolytes dissolves in aqueous solution
produces ions hence number of ions (i.e. particles) increases. Hence colligative properties of
electrolyte solutions are higher than non electrolyte solutions.
For electrolytic solutions dissociation of solutes – i) NaCl → Na+ + Cl⸺, Two particles are
formed.
ii) K2SO4 → 2 K+ + SO42⸺ Three particles are formed.
iii) AlCl3 → Al3+ + 3 Cl⸺ Four particles are formed.
iv) Na2SO4 → 2 Na+ + SO42⸺ Three particles are formed.
Colligative property of 0.1 M NaCl is twice than that of 0.1 M sucrose solution as sodium
chloride dissociates into ions while sucrose is not dissociated in an aqueous solution.
Van’t Hoff factor (i) – Van’t Hoff factor is the ration of colligative property of electrolytic
solution to colligative property of non electrolytic solution of same concentration.
coligative property of electrolytic solution (∆ T ¿¿ f )
i = colligative property of nonelectroltic solutionof same concentration = ¿=
¿ ( ∆T ¿¿ f )¿
¿
(∆ T ¿¿ b) (∆ P) (π )
¿ =
( ∆T ¿¿ b)=¿ ¿ ( ∆ P)0 ( π )0
Or i =
actual moles of particles∈ solutionafter dissociation formula mass of substance M therotical
= =
moles of formulaunits dissolved∈solution observed molar mass of substance M observed
1) i = 1 for non-electrolytic solution (no association and no dissociation in the solution)
2) i > 1 for electrolytic solution undergoes dissociation and i < 1 for electrolytic solution
undergoes association
Modification of expressions of colligative property –

△P = i P10 X2 = i
W2M1
i)
M2 W 1
 19

△Tb = i Kb m = i
W2 Kb
ii) ×1000
M2 W 1

△Tf = i Kf m = i
W2 Kf
iii) ×1000
M2 W 1

W 2 RT
iv) π = i MRT = i
M 2V
Relation between Van’t Hoff factor (i) and degree of dissociation (α) –
Consider an electrolyte AxBy which dissociates into its ion as – AxBy → x Ay+ + y Bx+
Initial moles 1 0 0
Moles at equilibrium (1 – α) xα yα
If α is the degree of dissociation of electrolyte, then moles of cations are xα and anions are yα
at equilibrium. Initial moles are 1 mol of electrolyte is dissolved hence (1 – α) remains
unionized at equilibrium.
Total moles after dissociation (mt) = (1 – α) + xα + yα = 1 + α (x + y – 1)
mt = 1 + α (n – 1) ….. (I)
where n = x + y = moles of ions obtained from dissociation of 1 mole of electrolyte.
actual moles of particles∈ solutionafter dissociation mt 1+ α (n−1)
Van’t Hoff (i) = = =
moles of formulaunits dissolved∈solution 1 1
i−1
Hence i = 1 + α (n – 1) Degree of dissociation (α) =
n−1
Que – What is Van’t Hoff factor. How is it related to degree of dissociation?