SOLUTIONS AND COLLIGATIUE

PROPERTIES
1.1 Introduction and definition of solution

1.2 Ways of expressing concentration of solution

1.3 Colligative properties

1.4 Lowering of vapour pressure and Raoult's law

1.5 Determination of molecular weight from lowering of vapour pressure

1.6 Boiling point elevation

1.7 Determination of molecular weight from elevation of boiling point

1.8 Freezing point depression

1.9 Determination of molecular weight from depression of freezing point

1.10 Osmosis and osmotic pressure

1.11 Measurement of osmotic pressure by Berkeley and Hartley's method

1.12 Laws of osmotic pressure

1.13 Determination of molecular weight from osmotic pressure

1.14 Abnormal osmotic pressure

1.15 Self-learning (evaluative) Van't Hoff-Avogadro's law

1.1 INTRODUCTION AND DEFINITION OF SOLUTION

Terms, Definitions, Formulae and Theory
A solution may be defined as the homogeneous mixture of two or more non-reacting
substances. The composition of solution varies within limit e.g. solution of sugar in water, NaCl
in water.
(1) Solution : Homogeneous mixture of two or more non-reacting substances is called solution.
(2) Solute : The substance in small amount in solution is called solute.
(3) Solvent: The substance in large amount in solution is called solvent.
e.g. NaCl solution in water, solute - NaCl, solvent ≈ water
(4) Solution containing two components is called binary solution.
Concentration : Amount of solute present in given amount of solvent is called
concentration of solution.
(5) Dilute solution : A solution containing relatively low concentration of solute is called
dilute solution.
(6) Concentrated solution : A solution containing relatively high concentration of solute is
called concentrated solution.
(7) Types of solution : Common solution is the solution in which solute is solid and solvent is
liquid. But by considering three states of matter, there are nine types of solutions.
Types of Solution Example
(1) Gas in gas Air, mixtures of all gases.
(2) Gas in liquid Oxygen in water, CO2 in water.
(3) Gas in solid Adsorption of H2 by palladium.
(4) Liquid in gas Moisture of air, spray in air.
(5) Liquid in liquid Oil in petrol, Alcohol in water.
(6) Liquid in solid Jellies, Jams and Ice cream.
(7) Solid in gas Camphor in air.
(8) Solid in liquid Salt in water, sugar in water.
(9) Solid in solid Metal alloys, solid solution, carbon in iron steel.
Useful Information for MHT-CET 1
1. Solution is homogeneous mixture of two or more substances.
2. If solution contains two substances, solution is called binary solution.
3. In dilute solutions, solute is present in very less amount as compared to solvent.
4. Ideal solution is a solution in which there is no change in volume and enthalpy after
mixing the component.
5. Non-ideal solution is a solution in which there is change in volume and enthalpy on
mixing the components.
Questions As Per Board Pattern
1. Define the following : [1 M each]
(a) Solution, (b) Salute, (c) Solvent, (d) Dilute solution.

2. What is solution? Explain solute and solvent with suitable example. [2 M]

 Multiple Choice Questions
1. Solute is the substance in solution which is..................
(a) present in large amount (b) present in small amount
(c) present in equal amount (d) present in large or in small amount
2. In binary solution, number of components are.................
(a) one (b) two
(c) three (d) four
3. In ideal solution, volume of solution.................after mixing component.
(a) remains same (b) changes
(c) increases (d) increases or decreases
4. In jellies and jams, solute and solvent are.................
(a) solid and liquid (b) solid and gas
(c) liquid and solid (d) liquid and gas

Answer Key

1-b . 2-b 3-a 4-c

1.2 WAYS OF EXPRESSING CONCENTRATION OF SOLUTION
Terms, Definitions, Formulae and Theory
There are several ways of expressing concentration of solution :
(1) Percentage by weight
(2) Mole fraction
(3) Molarity
(4) Molality
(5) Normality.
(1) Percentage by weight: Weight of the solute in gram present in 100 gm of the solution is
termed as percentage by weight.
Mathematically, it is represented as
Weight of solute
% by weight = x 100
Weight of solution
Weight of solute and solvent in above formula should be used in same unit.
 (2) Mole Fraction : Mole fraction of solute is defined as the ratio of the number of
moles of solute to total number of moles of solute and solvent. Mole fraction of solute is
denoted as Xsolute.

Number of moles of solute solute

Xsolute. =
Moles of solute + Moles of solvent
If n1 = moles of solvent
n2 = moles of solute
n2
Xsolute =
n1 + n 2

n1
Xsolute =
n1 + n 2
Mole fraction is unitless. Sum of mole fraction of solute and solvent is always 1.
(3) Molarity : Generally for expression of concentration, molarity is used. The number
of
moles of solute per litre or per dm3 of solution is called molarity.
If n is the number of moles of solute present in 'V dm3 of solution,
Moles of solute
Molarity =
Volume of solution
n
M=
v
Unit of molarity is moles per litre or moles per dm 3.
. . Weight of substance
Number of moles are calculated as n =
Molecular weight
Weight of substance and molecular weight of substance are used in same unit.
(4) Molality : The number of moles of solute per kilogram of solvent is called as
molality.
Moles of solute
Molarity =
Mass of solvent in kg
Molal solution is obtained by dissolving 1 mole of solute in 1 kilogram of solvent.
Unit of molality is mole per kg.
Remember number of moles of solute per kg of solvent (not solution).
 (5) Normality : The number of gram equivalents of solute present per litre of
solution is called normality.

Gram equivalent of solute

Normality =
Volume of solution in litre
If 40 gm of NaOH is dissolved in 1 litre of H2O, IN solution of NaOH is formed.
4 gm of NaOH in 1 litre of H 2O = 0.1 N NaOH

Useful Information for MHT-CET

1. Concentration of solutions can be expressed in different ways.
2. In case of molality, number of moles of solute per 1 kilogram of solvent.
3. Molarity is number of moles of solute per litre of solution.
4. Normality is common unit for measurement of concentration. Normality is number of
gram equivalents of solute per litre of solution.
5. Gram equivalent of solute is calculated as,
Weight of substance in gram
Gram equivalent =
Equivalent weight or substance
6. Percentage and mole fraction depend on amount of solute and solvent.
Questions As Per Board Pat tern
1, Define (March 2008) [1M each]
(a) Mole fraction, (b) Molarity, (c) Molality.
2. Explain the ways of expressing concentration of solution. [2M]

Multiple Choice Questions

1. 0.2 gm of NaOH is dissolved in a litre of its solution. Normality of solution is...............
(a) 0.2 N (b) 0.02 N
(c) 0.005 N (d) 0.05 N
2. A gaseous mixture contains 5.6 gm of N2 and 3.2 gm of O2. Mole fraction of N2 in mixture
is ...............
2 1
(a) (b)
3 3
3
(c) (d) 3
2
3. Which one of the following methods of expressing concentration of solution is
independent of temperature ?
 (a) molarity (b) molality
(c) normality (d) formality
4. The weight of NaCl required to make 250 ml of 0.1 M solution is...............
(a) 1.462 gm (b) 14.63 gm
(c) 0.1462 gm (d) 0.01462 gm
5. Molarity of 4% NaOH solution is ..............
(a) 1 (b) 0.1
(c) 0.01 (d) 0.5
6. When solution contains 1 gm equivalent of substance in one litre of solution then solution
is called ...............
(a) centinormal solution (b) normal solution
(c) decinormal solution (d) molar solution
7. Molality is defined as number of moles of solute per...............
(a) kg of solution (b) kg of solvent
(c) lit. of solution (d) lit. of solvent
Answer Key
1-b 2-a 3-c 4-a
5-a 6-c 7-c
1.3 COLLIGATIVE PROPERTIES
Terms, Definitions, Formulae and Theory
The properties which depend only on number of molecules of solute and not on the nature of
solute are called colligative properties.
• Colligative properties are shown by dilute solution containing non-volatile solute.
• Following are colligative properties of solution :
(1) Lowering of vapour pressure.
(2) Elevation of boiling point.
(3) Depression of freezing point.
(4) Osmotic pressure.
Useful Information for MHT-CET
1. Colligative properties depend only upon number of molecules and not on nature of solute.
2. For study of colligative properties, solute should be non-volatile.
3. Solute is considered as it does not undergo association or dissociation.
4. For study of colligative properties, solution should be dilute.
Questions As Per Board Pattern
1. Give names of different colligative properties of solution. [2M]
2. Define : (a) Colligative properties, (b) Dilute solution, (c) Non-volatile. [3M]
Multiple Choice Questions
1. Which one of the following is not a colligative property ?
(a) osmotic pressure (b) elevation of boiling point
(c) lowering of vapour pressure (d) pressure
2. Colligative properties of solution are independent of nature of solute but depend
on ..............
(a) number of solvent molecules
(b) number of solute molecules
(c) number of solute and solvent molecules
(d) number of water molecules
Answer Key

1-d 2-b
1.4 LOWERING OF VAPOUR PRESSURE AND RAOULT'S LAW
Terms, Definitions, Formulae and Theory
Every liquid exerts a vapour pressure in the space above it. The value of vapour pressure
depends upon nature of liquid and the temperature.
Vapour Pressure and Nature of Liquid : If liquid containing liquid is placed under a bell jar,
at certain constant temperature, some molecules in the surface layer of liquid evaporate and
pass into free space above. However, some molecules return to the surface layer of liquid.

Fig. 1.1: Evaporation and Condensation

At initial, rate of evaporation is higher than condensation. After some time both rates
become equal. Under this condition, vapours become saturated at that temperature. This
pressure exerted by vapours on the surface of liquid is called vapour pressure of the liquid at
that temperature.
Effect of temperature : It is found that as temperature increases, vapour pressure of the
liquid increases. As temperature decreases, vapour pressure also decreases. When vapour
pressure of liquid is equal to atmospheric liquid then liquid starts to boil.
Lowering of vapour pressure : When a non-volatile solute is dissolved in liquid, vapour
pressure of the resulting solution is lowered. It is because on the surface of solution, solute
molecules take place of solvent molecules. Hence, rate of evaporation decreases. Therefore,
vapour pressure decreases.
Relative lowering of vapour pressure : It is the ratio of the lowering of vapour pressure of
pure solvent to vapour pressure of pure solvent.
Po -Ps
Thus, relative lowering of vapour pressure of pure solvent = —------
Po
It is not dependent on the nature of solute, solvent and temperatur. It depends only on
concentration of solute.
Raoult's law and relative lowering of vapour pressure (Statement) : The relative lowering
of vapour pressure of pure solvent is equal to the mole fraction of the" solute in the solution. If n↑
arid n2 are moles of solvent and solute respectively, then according to Raoult's law,

po - ps n2
=
po n1 + n 2
 Since, n 2 is very small in dilute solution, n 2 at denominator is negligible as compared to
number of moles of solvent nv

po - ps n 2
Hence, =
po n1

If W2 = Weight of solute
M2 = Molecular weight of solute
W2 = Weight of solvent
M 1 = Molecular weight of solvent

W1 W2
then n1 = and n2 =
M1 M2

W2
po - ps n 2 M 2
 = =
po n1 W1
M1

p o - p s W2 xM1
=
po M 2 xW1

From this equation molecular weight of solute (M2) can be calculated.

1
W2 xM1
M2 = x Relative lowering of W,vapour pressure
W1

Useful Information for MHT-C ET ]

1. Vapour pressure of liquid depends upon nature of liquid and temperature.
2. Lowering of vapour pressure of pure solvent is due to non-volatile solute.
3. Relative lowering of vapour pressure is a mere number. It is independent of nature of
solute, solvent and temperature.
4. Relative lowering of vapour pressure of pure solvent depends upon concentration of
solute.
5. According to Raoult's law, relative lowering of vapour pressure is equal to mole fraction
of solute in solution.
6. For Raoult's law, solution should be dilute containing non-volatile solute.
7. As mole fraction of solute increases, vapour pressure of solution decreases.
8. Decrease in vapour pressure of pure solvent is due to acquiring surface of liquid by some
molecules of non-volatile solute. Therefore, rate of evaporation decreases, which
decreases vapour pressure.
 Questions As Per Board Pattern
1. Define : [1 M each]
(a) Vapour pressure.
(b) Raoult's lazv for vapour pressure.
(c) Relative loiuering of vapour pressure.
(d) Boiling point.
2. Define Raoult's law and derive expression of it for vapour pressure. [4M]
3. Vapour pressure of pure solvent decreases by adding non-volatile solute. Explain. [4M]

Multiple Choice Questions

1. Raoult's law gives relationship between relative lowering of vapour pressure and

(a) mole fraction of solvent (b) mole fraction of solute

(c) temperature (d) nature of solute
2. Relative lowering of vapour pressure of pure solvent is.................
(a) ratio of lowering of vapour pressure of pure solvent to vapour pressure of pure
solvent.
(b) ratio of vapour pressure of solvent to lowering of vapour pressure of solvent.
(c) ratio of pressure of solvent to vapour pressure of solute.
(d) ratio of vapour pressure of solute to solvent.
3. Which one of the following is correct equation of Raoult's law for vapour pressure ?

ps - p o n1 p o - ps n1
(a) = (b) =
ps n1 + n 2 po n1 + n 2
po - ps n2 po - ps n2
(c) = (d) =
po n1 + n 2 ps n1 + n 2

4. Relative lowering of vapour pressure of pure solvent depends upon................

(a) nature of solvent (b) nature of solute
(c) temperature (d) concentration of solute
Answer Key
1-b 2-a 3-c 4-d
1.5 DETERMINATION OF MOLECULAR WEIGHT FROM
LOWERING OF VAPOUR PRESSURE
Terms, Definitions, Formulae and Theory
Molecular weight of solute can be determined by Ostwald and Walker's method. In this
method a current of dry air is passed through a bulb A containing the solution. Then air is
further passed through bulb B containing pure solvent as shown in Fig. 1.2.
 Fig. 1.2 : Ostwald and Walker's method
When the dry air passes through the solution in bulb A, the air becomes saturated upto the
vapour pressure of solution (P s). The loss in weight of bulb A is determined by weighing bulb
before and after the air has passed through.
Therefore, loss in weight of bulb A  Ps,
As air is already saturated to vapour pressure of the solution and enters the bulb of pure
solvent (B), it takes up little more vapour, because vapour pressure of solvent is greater than
solution. The air becomes saturated upto vapour pressure of pure solvent (P o ). The loss in weight
of bulb B is proportional to the difference in vapour pressures of solvent and solution.
Therefore, loss in weight of bulb BPO - P s.
(Loss of weight of bulb A + Loss of weight of bulb B)  Po.
Loss in weight of bulb B (solvent) P 0 -P s
Thus, =
Loss of weight of bulb A + Loss of weight of bulb B Po
If water is the solvent then air coming out from bulb B is passed through weighed tube
containing fused CaCl 2 . Increase in weight of CaCl 2 tube is equal to vapour pressure of solvent
(Po)
 By using Raoult's law,
Po - Ps M2 W2
=
Po M2 W2

Useful Information for MHT-CET

1. Weight of bulbs A and B are taken before passing air through them.
2. Air should be dry before passing.
3. Temperature of air should be maintained.
4. If solvent is water then after passing air through bulbs A and B, it is passed through
the tube containing fused CaCl2. Increase in weight of tube is equal to vapour pressure of
solvent.
5. It is dynamic process.
6. Temperature of solvent and solution is kept constant by thermostat.
 5. Loss of weight of bulb B is equal to difference between vapour pressure of pure
solvent and solution (Po - Ps).
6. Loss of weight of bulb A is related to vapour pressure of solution (P s).
Unsolved Problems
1. Vapour pressure of pure water is 3.16 x 10 3 Nm-2, while vapour pressure of solution
containing 5.3 x 10 -3 kg of solute per 0.1 kg of water is 3.11 x 10 3 Nm -2 at same
temperature. Calculate molar mass of solute.
2. Vapour pressure of pure water is 18.15 torr at 298 K and that of solution containing
9.47 x 10" 3 kg of sugar in 0.1 kg of water at the same temperature is 18.06 torr. Calculate
molecular mass of sugar.
Answers
1. 60.3 2. 344.2

Questions As Per Board Pattern

1. Define vapour pressure. Vapour pressure of solution is less than vapour pressure of pure
solvent. Explain. [2M]
2. Describe Ostzvald-Walker's method for measurement of lowering of vapour pressure.
[4M]
3. Write a short note on Raoult's law for lowering of vapour pressure. [2M]
4. How from lowering of vapour pressure, molecular weight of solute is calculated ? [3M]
M u l t i p l e Ch o i c e Q u e s t i o n s
1. Which one of the following is not colligative property ?
(a) vapour pressure (b) elevation of b.p.
(c) depression of freezing point (d) osmotic pressure
2. Relative lowering of vapour pressure is equal to...............
(a) ratio of number of solute molecules to number of solvent molecules
(b) ratio of number of solute molecules to total number of molecules of solution
(c) ratio of number of solvent molecules to number of solute molecules
(d) ratio of total number of molecules of solution to number of molecules of solute
3. Vapour pressure of solution is...............
(a) directly proportional to mole fraction of solvent
(b) inversely proportional to mole fraction of solvent
(c) directly proportional to mole fraction of solute
(d) inversely proportional to mole fraction of solute
 4. Pressure cooker reduces cooking time because..............
(a) heat is uniformly distributed
(b) high pressure makes food soft
(c) boiling point inside the cooker is increased
(d) a large flame is used
Answer Key
1-a 2-b 3-a 4-c
1.6 BOILING POINT ELEVATION
Terms, Definitions, Formulae and Theory
Boiling Point: The temperature at which vapour pressure of liquid is equal to atmospheric
pressure is called boiling point of the liquid.
It is found that if in pure liquid, non-volatile solute is added, boiling point of solution is
increased than pure solvent. Increase in boiling point of solution is called elevation of boiling
point.
Raoult's Law for Elevation in Boiling Point:
(1) Equimolar quantities of different solutes when dissolved in equal weights of same
solvent, elevate the boiling point to same extent.
(2) The elevation of the boiling point of the solvent is directly proportional to the
molality of the solution.
 ∆Tb  m
where ∆Tb is elevation of boiling point and m is molality
If Kb is molal elevation constant, then ∆T b = Kbm
Let us suppose elevation of boiling point of solvent is ∆T b when W2 solute of molecular
weight M2 is dissolved in Wj of solvent. Molality of the solution is given by
W2 �1000
m=
W1 �M 2
1000W2 �K b
Thus, DTb =
W1 �M 2
1000W2 K b
 M2 =
W1 �DTb

Molecular weight of solute is calculated from above equation if elevation of boiling point is
known from known weight of solute in given weight of solvent.
 Useful Information for MHT-CET
1. Boiling point elevation and lowering in vapour pressure of solvent are related to each
other. It is found that boiling point of pure solvent is less than solution with non
volatile solute. It is because vapour pressure of pure solvent is higher, hence it boils at
low temperature. But vapour pressure of solution is lower, hence it boils at high
temperature.
2. Elevation of boiling point is due to non-volatile solute.
3. Molal elevation in boiling point of a solvent is constant for different solute in same
solvent.
4. According to Raoult's law, elevation of boiling point of solvent depends upon molality
of solute.
5. Boiling point of liquid changes by change in pressure. If pressure increases, boiling point
increases.
6. If pressure on surface of liquid decreases, boiling point decreases.
7. Molal elevation constant is also known as ebullioscopic constant.
 Unsolved Problems
1. A solution of 5.6 gm glucose in 1000 gm of water is prepared. Calculate boiling point of
solution if Kb of water is 0.52 K. (Molecular weight of glucose = 180).
2. A solution containing 2.44 gm of solute in 75 gm of water boiled at 100.413°C. Calculate
molecular weight of solute. (Kb for water = 0.52).
Answer s
1. 373.0161 K. 2. 40.96
Questions As Per Board Pattern
1. Boiling point of solution is greater than pure solvent. Explain. [2M]
2. Define Ebullioscopic constant and explain how it is used to determine molecular weight
of solute. [4M]
3. Define Raoult's law for elevation in boiling point. Derive expression for elevation in
boiling point by using this law. [3M]
M u lt ip le Ch o ice Q u est io n s
1. Elevation of boiling point of solvent is directly proportional to.................
(a) normality of solution
(b) mole fraction of solute
(c) molality of the solution
(d) molarity of solution
2. Elevation in boiling point for 1 molal solution is called.................
(a) molal lowering of vapour pressure
(b) molal elevation of boiling point
(c) molal depression of freezing point
(d) molal elevation of freezing point
3. Among the following equimolar aqueous solutions identify the one having highest
boiling point ............ (March 2008)
(a) urea (b) sucrose
(c) sodium chloride (d) sodium sulphate
Answer Key
1-c 2-b 3-d
1.7 DETERMINATION OF MOLECULAR WEIGHT FROM ELEVATION
OF BOILING POINT
Terms, Definitions, Formulae and Theory
Landsberger and Walker's Method [Ebullioscopic Method]:
This method is useful for the determination of elevation of boiling point of solvent and
solution. This process consists of following apparatus. The apparatus consists of boiling tube.
This tube has a bulb with a hole H in the side and is graduated in ml. The tube is fitted with
sensitive thermometer and a glass tube with the bulb blown at the end with many holes. This
rose head ensures uniform heating of liquid in the boiling tube. The solvent or solution is heated
by passing vapours of solvent through rose-head tube. Latent heat of vapours is absorbed by
solvent and temperature increases upto boiling point. Arrangement of apparatus is as shown in
Fig. 1.3.

In actual experiment, 6 to 8 x 10 -3 dm3 of solvent is placed in the boiling point tube and the
vapour is passed through it. In the beginning, vapour is condensed and heat is absorbed by
solvent. After some time it begins to boil. The constant temperature recorded on thermometer is
boiling point of solvent (T o). Excess of vapours is escaped from hole. Now supply of solvent
vapour is cut off temporarily and weighed amount of substance under test is dropped into the
solvent in the boiling point tube. Solvent vapours is again passed and boiling point of the
solution is determined as before (Ts).
Immediately after this temperature recorded, the thermometer and rose head are carefully
raised out of the solution and the volume of the solution (V s) is noted. This difference in these
two temperatures is elevation of boiling point (T s - To). By knowing density of solvent (d), mass
of solvent is calculated. To calculate the molecular weight of solute, following formula is used.
1000K b W2
M2 =
DTb W1
 W1 = Vs x d (weight of solvent)

1000K b W2
 M2 =
DTb �Vs �d

Useful Information for MHT-CET

1. Elevation of boiling point is determined from Landsberger and Walker's method. This
method is also known as Ebullioscopic method.
2. In this method, boiling point of pure solvent is measured by using sensitive
thermometer. Solvent is heated with steam of pure solvent.
3. Boiling point of solution is measured by same method. In this method, sensitive
thermometer is used. Solution or solvent is heated by steam.
1000 �W2 K b
M2 =
DTb W1

where W1 = Weight of solvent = Volume x Density.

1
 Unsolved Problems
1. The boiling point of pure water is 373 K. Calculate ∆T b and boiling point of aqueous
solution of urea containing 6 x 10-4 kg in 0.1 kg of water. Kb for water is 0.52 and molar
mass of urea is 60.
2. A solution containing 3.5 x 10 -3 kg of substance in 0.125 kg of water boils at 373.52 K.
Calculate the molar mass of the solute. K b for water is 0.52 K kg mol.
3. The boiling point of 6% solution of glucose in water boils at 373.104 K. Calculate the
Ebullioscopic constant (Kb) for water. Molecular weight of glucose = 180.
4. Boiling point of water is 373 K. Calculate elevation in boiling point and boiling point of
solution containing 18% glucose in water.
(Kb for water is 0.52 K kg mol"1)
Answers
1. ∆Tb = 0.052 K, B.P. of solution = 373.052 K 2. Mol. wt. of solute = 28
3. 0.52 K kg mor1 4. ∆Tb = 0.52, B.P. of solution = 373.52 K
Questions As Per Board Pattern
1. Define : (i) Boiling point, (ii) Ebullioscopic constant. [1 Mark each]
2. Describe Landsberger - Walker's method for determination of molecular weight of
solute. (March 2008) [4 M]
3. Draw heat labelled diagram of Landsberger - Walker's method for determination of
boiling point. [2M]
Multiple Choice Questions
1. Landsberger-Walker's method is used for determination of molecular weight by

(a) lowering of vapour pressure (b) elevation in boiling point

(c) depression in freezing point (d) osmotic pressure
2. Boiling point of solvent is always...............that of solution.
(a) greater than (b) equal to
(c) lower than (d) equal to solvent
 3. Elevation of boiling point of solvent is directly proportional to ............... of the
solution.
(a) normality (b) molarity
(c) mole fraction (d) molality
4. In Landsberger-Walker's method for measurement of elevation boiling point,...............
thermometer is used.
(a) Beckmann's (b) sensitive
(c) alcohol (d) coloured
5. When NaCl is dissolved in water, its boiling point................
(a) remains constant (b) increases
(c) decreases (d) increases or decreases
Answer Key
l-b 2-c 3-d 4-b
5-b
1.8 FREEZING POINT DEPRESSION
Terms, Definitions, Formulae and Theory
The temperature at which vapour pressure of liquid and its solid form are equal is called as
freezing point. Freezing point of pure solvent is decreased when solute is dissolved.
Raoult's law for depression in freezing point:
(1) Equal molal solution of different solute depress the freezing point of solvent to same
extent.
(2) The depression of freezing point of solvent is directly proportional to the molality of
the solution.
∆Tf  m
∆Tf = Kf m
where Kf is known as molal depression constant of the solvent.
Let us suppose depression of freezing point of solvent be ∆T f when W2 solute is dissolved in
W1 solvent. M, and Mj are molecular weights of solute and solvent respectively. Molality is

1000 �W2
m=
W1 �M 2

1000 �W2 K f
DTf =
W1 �M 2
 1000 �W2 �K f
 M2 =
W1 �DTf

Molecular weight of solvent is calculated by using this equation.

Depression of freezing point is determined by using Beckmann's method (cryoscopic
method). Temperature is measured in this method by Beckmann's thermometer. Beckmann's
thermometer has least count of 0.01°C.
NaCl and CaCl 2 are used to clear snow on the road, because by dissolving these
solutes, freezing point of water is depressed below zero degree. Therefore snow gets melt.
Useful information for MHT-CET
1. Freezing point is the temperature at which vapour pressure of solid state and liquid
is
same.
2. Depression in freezing point is directly proportional to the molal concentration
of
solute, hence it is colligative property.
3. Molal depression constant is decreasing in freezing point by 1 molal solution.
4. Molal depression constant of freezing point for organic solvent is larger.
5. Molal depression of freezing point is independent of nature of solute.
 Unsolved Problems
1. An aqueous solution containing 0.26 gm of solute dissolved in 25 gm of water freezes at
- 0.43°C. Calculate molecular weight of solute. (Kf = 1.86).
2. 0.36 gm of substance dissolved in 25.5 gm of benzene lowered freezing point by 0.42.
Calculate molecular weight of solute (Kf per kg of benzene = 5.12).
3. 2 gm of substance dissolved in 100 gm of benzene produces depression of 1°C in freezing
point of solvent. Calculate the molecular weight of solute. (K f = 5).
Answers
1. 44.98 2. 173 3. 100
Questions As Per Board Pattern
1. Write a short note on depression of freezing point. [2M]
2. Describe Beckmann's method for determination of molecular weight by depression in
freezing point. [4M]
3. Explain hoiu molecular weight of solute is determined by depression in freezing point.
[4M]

Multiple Choice Questions

1. Which one of the following will have maximum depression in freezing point ?
(a) 1M sucrose (b) 2 M sucrose
(c) 3 M sucrose (d) 4 M sucrose
2. For measurement of depression in freezing point, which one of the following methods is
used ?
(a) Landsberger - Walker's method
(b) Beckmann's method
(c) Berkeley and Hartley's method
(d) Ostwald - Walker's method
3. Freezing point is the temperature at which the liquid and solid state of substance have
the same ...............
(a) vapour pressure , (b) partial pressure
(c) osmotic pressure (d) total pressure
Answer Key
1-d . 2-b 3-a
1.9 DETERMINATION OF MOLECULAR WEIGHT FROM DEPRESSION
OF FREEZING POINT
Terms, Definitions, Formulae and Theory
Determination of Freezing Point by Beckmann's Method (Cryoscopic Method)
In this method, supercooled liquid is stirred vigorously, crystallised immediately to form
solid. The temperature is called freezing point.
The apparatus consists of freezing tube having side tube at upper part. Side tube is used for
adding accurately weighed solute. This tube is fitted with a cork carrying stirrer and
Beckmann's thermometer. Freezing tube is surrounded by thin outer jacket which is useful for
uniform cooling. Whole apparatus is dipped in freezing mixture, whose temperature is below
the freezing point of solvent. The arrangement of the apparatus is as shown in Fig. 1.4.

Fig. 1.4
Process : A weighed quantity of solvent is placed in freezing tube. The apparatus is
arranged as shown in Fig. 1.4. The solvent is allowed to cool upto 0.5°C below its normal
freezing point, without stirring. Then it is stirred vigorously. Stirring causes crystallization
and temperature rises owing to latent heat set free. The constant temperature is recorded. This
is freezing point of solvent.
The freezing tube is then taken out from freezing mixture. Solvent is allowed to melt,
accurate weight of solute is mixed in the solvent. Again freezing tube is fitted in freezing
mixture. Freezing point of solution is measured as before. Difference between both freezing
points is depression in freezing point of solvent. The molecular weight of solute can be
determined by using following formula

1000 �W2 �K f
M2 =
DTf �W1
 Useful information for MHT-CET
1. This method is also called as cryoscopic method. By this method accurate freezing
point of solvent and solute are measured by Beckmann's thermometer. Beckmann's
thermometer is very accurate and measures accurate temperature.
2. Freezing point of solvent is always greater than freezing point of solution.
3. Solute should be non-volatile for good result.
4. In freezing mixture, generally ice and NaCl is used.
 Unsolved Problems
1. Molal depression constant of benzene is 5.12 K. A solution containing 1 x 10-3 kg of solute
in 0.1 kg of benzene freezes at 5.1 K. What is molar mass of solute. (Freezing point of
pure benzene = 5.5 K).
2. A solution containing 25.6 gm of sulphur dissolved in 1000 gm of naphthalene whose
melting point is 80.1°C gave freezing point lowering of 0.68 oC. Calculate molecular
weight and molecular formula for sulphur.
Answers
1. 128
2. Molecular weight = 256, Molecular formula = S 8.
Questions As Per Board Pattern )
1. Describe method for determination of freezing point of solution and solvent. [3M]
2. Draw neat labelled diagram of cryoscopic method. [2M]
3. Describe why Beckmann's thermometer is used in cryoscopic method. [4M]
4. How lowering of freezing point is useful to calculate molecular weight of solute ? [3M]

Multiple Choice Questions

1. Which one of the following thermometers is used in cryoscopic method for measurement
of temperature ?
(a) 1/10 thermometer (b) alcohol thermometer
(c) sensitive thermometer (d) Beckmann's thermometer
2. Beckmann's method (cryoscopic method) is used to measure.................
(a) lowering of vapour pressure (b) elevation of boiling point
(c) depression in freezing point (d) osmotic pressure
3. Correct equation for determination of molecular weight by depression in freezing point
is ..................

1000 �W2 �K f 1000 �W1 �K f

(a) M 2 = (b) M 2 =
DTf �W1 DTf �W2
1000 �W2 �K f 1000 �W2 �K f
(c) M 2 = (d) M 2 =
DTf DTf �W1

Answer Key
1-d 2-c 3-a
1.10 OSMOSIS AND OSMOTIC PRESSURE
Terms, Definitions, Formulae and Theory
Osmosis : The process of passing solvent molecule through semi-permeable membrane from
solvent to solution or from dilute solution to concentrated solution is known as osmosis.
Osmosis is unidirectional flow of solvent molecules. Osmosis always takes place from dilute
solution to concentrated solution. Absorption of water from soil in plants takes place by osmosis,
water in body of animals passes by osmosis through cell wall. Water absorbed by plants reaches
to top by osmosis.
Semi-permeable membrane : The natural or artificial membrane having very small pores
and allow to pass only solvent molecules is called semi-permeable membrane.
e.g. Cell wall, pig bladder, egg membrane etc. are natural semi-permeable membrane. These
are weak. Strong semi-permeable membranes are prepared artificially e.g. K 4Fe(CN) 6
impregnated in porcelain pot.
Useful Information for MHT-CET
1. Phenomenon of osmosis was first studied by Abbe-Nollet in 1748.
1. When membrane permits the solvent molecules to come out through membrane called
exo-osmosis. For example, when grapes are put in concentrated solution of NaCl, the
grapes shrink.
2. When membrane permits the solvent molecule to enter inside through membrane called
endo-osmosis. For example, if we keep grapes in pure water, the grapes swell.
3. Osmotic pressure depends on number of molecules of solute and not on their nature
Osmotic pressure is hydrostatic pressure which stops osmosis.
4. Hypotonic solution : The solution having lower osmotic pressure than other solution ii
called hypotonic solution.
5. Hypertonic solution : The solution having higher osmotic pressvire than other solution ii
called hypertonic solution.
6. Isotonic solutions : The solutions having same osmotic pressures are called isotonii
solutions.
Saline solution is isotonic with blood. 0.09% solution of NaCl is isotonic with blood.
• Semi-permeable membrane is having very small pores and allow to pass only solven
molecules.
Examples of natural semi-permeable membrane are cell wall, pig's bladder, animal an
vegetable membrane, natural membranes are not strong.

J
Artificial semi-permeable membranes are parchment filter paper, copper ferricyanid
Cu2[Fe(CN)6] deposited in the pores of porous porcelain vessel which is strong artificial sem -
permeable membrane.
 Questions As Per Board Pattern
1. Define : (a) Osmosis, (b) Osmotic pressure, (c) Semi-permeable membrane. [1 Mark each]
2. Write short note on Osmosis. [2M]
3. What we hypertonic solutions ? [2M]
4. What do you mean by endosmosis and exo-osmosis ? Explain with suitable example.
[2M]
Multiple Choice Questions
1. Unidirectional flow of solvent molecules through semi-permeable membrane is called

(a) osmotic pressure (b) osmosis

(c) endo-osmosis (d) exo-osmosis
2. When grapes are kept in concentrated solution of sodium chloride.................
(a) grapes will swell and burst (b) grapes will shrink
(c) grapes will remain as it is (d) may swell or shrink
3. Saline given to human is ................
(a) hypertonic with blood (b) hypotonic with blood
(c) isotonic with blood (d) may or may not be hypertonic with blood
4. Osmotic pressure is colligative property because it depends upon.................
(a) number of solvent molecules
(b) number of solute molecules
(c) number of solvent and solute molecules
(d) temperature
Answer Key
1-b 2-b 3-c 4-b
1.11 MEASUREMENT OF OSMOTIC PRESSURE BY BERKELEY
AND HARTLEY'S METHOD
Terms, Definitions, Formulae and Theory
Berkeley and Hartley employed the technique by applying external pressure on solution
just enough to prevent osmosis. This pressure is called osmotic pressure.
Construction of apparatus : The osmometer used by Berkeley and Hartley is shown in
Fig. 1.5.
 Fig. 1.5
Porcelain tube with copper ferrocyanide membrane deposited in its walls is enclosed in
metallic jacket. Central tube is fitted with reservoir of pure solvent at one end and capillary
tube at the other. Mechanical pressure can be applied on the solution.
In the centre, porcelain tube is filled with pure solvent. In jacket, solution is filled up. The
level of the solvent is marked in capillary tube, solvent will try to pass into solution. Pressure is
applied on solution to stop osmosis. Pressure applied is measured.
It is quick and accurate method. Concentration of solution does not change, hence correct
osmotic pressure is measured.
Useful Information for MHT-CET
1. Berkeley and Hartley's method is quick and accurate for measurement of osmotic
pressure.
2. In the central polcelain tube solvent is filled up. Osmosis take place from central tube to
outer jacket.
3. In outer jacket solution is filled up. Osmosis is stopped by applying external pressure on
solvent. This pressure is osmotic pressure of that solution.
4. Temperature of atmosphere is kept constant during measurement of osmotic pressure.
5. Semi-permeable membrane used is artificial prepared from porcelain tube with copper-
ferrocynide. It has high strength. Hence, osmotic pressure of concentrated solution can
be measured.
Questions As Per Board Pattern
1. Write a short note on osmotic pressure. [2M]
2. Write a short note on semi-permeable membrane. [2M]
3. Describe method of measurement of osmotic pressure by Berkeley and Hartley's
method. [4M]
 Multiple Choice Questions
1. The solution of lower concentration and hence lower osmotic pressure than other is
called ............... solution.
(a) hypertonic (b) hypotonic
(c) isotonic (d) isoelectric
2. Osmosis was first studied by...............
(a) Berkeley (b) Hartley
(c) Abee Nollet (d) Vant-Hoff
3. Osmotic pressure is...............property.
(a) extensive (b) intensive
(c) colligative (d) thermodynamic
4. Berkeley and Hartley's method is used to determine...............
(a) boiling point
(b) lowering point of vapour pressure
(c) osmotic pressure
(d) freezing point
Answer Key
1-b 2-c 3-c 4-c
1.12 LAWS OF OSMOTIC PRESSURE
Terms, Definitions, Formulae and Theory
It was studied by Van't Hoff that there is similarities between osmotic pressure of solution
and pressure of gases.
(a) Van't Hoff-Boyle's Law : At constant temperature, osmotic pressure of dilute solution is
directly proportional to concentration. Concentration is reciprocal of volume.
1
π  C but C =
v
1
π 
v
1
π = constant x
v
πV = constant

Thus, product of osmotic pressure and volume is constant at constant temperature.

 (b) Van't Hoff-Charle's Law : At constant concentration, the osmotic pressure of dilute
solution varies directly proportional to temperature.
π T
p
π = KT or = Constant
T
(c) Van't Hoff equation for dilute solution : According to Van't Hoff-Boyle's law,
1
π  ...(1)
v
According to Van't Hoff-Charle's law,
π  T ...(2)
By combining equations (1) and (2),
T
π
v

πV = RT for 1 mole of solution.

For n moles,
πV = nRT

n
π= RT
v
n
But = mole per volume = C
v
π = CRT

Useful Information for MHT-CET

(1) Units of R, π and V
R = 0.082 lit. atm. K-1 mol-1
π = atm.
V = litre. .
SI units
R = 8.314 JK-1mol-1
π = kPa (kilopascal)
= kNm -2 (kilo newton metre-2)
V = dm3
OR
R = 8.314 J K-1 mor-1
π = Pa orNm - 2
V = m3
 Unsolved Problems
1. Osmotic pressure of glucose solution is 1.7 x 10 5 Pa at 298 K. What will be its osmotic
pressure at 373 K ?
2. 105 ml of sucrose solution have osmotic pressure 2.5 x 10 5 Pa. What will be its osmotic
pressure when volume of solution is increased upto 150 ml ? Temperature remains same.
Answers
1. 2.128 x 105 Nm-2 or Pa 2. 1.75 x 105 Pa
 Questions As Per Board Pattern
1. Define Van't Hoff's-Boyle 's law and derive expression for the law. (March 2008) [2 M]
2. Define Van't Hoff's Charle's law and derive expression for the law.
[2M]
3. Derive general osmotic pressure equation for solution by using Van't Hoff-Charle's and
Van't Hoff-Boyle's law. .
[2M]
Multiple Choice Questions
1: Which one of the following is equation for Van't Hoff-Boyle's law ?
p
(a) π = constant (b) = constant
T
(c) πV = constant (d) π1 V1 = π 1V2
2. What will be osmotic pressure of given solution having πV = 125 x 10 5 if volume of
solution is 50 dm3 ?
(a) 5xl0 5 Pa (b) 50xl0 5 Pa
(c) 25xl0 5 Pa (d) 2.5 x 105 Pa
3. Which one of the following is correct equation for Van't Hoff-Charle's law ?
(a) πV = constant (b) πV = RT

p
(c) = constant (d) πV = nRT
T
Answer Key

1-c 2-d 3-c

1.13 DETERMINATION OF MOLECULAR WEIGHT
FROM OSMOTIC PRESSURE
Terms, Definitions, Formulae and Theory
According to Van't Hoff solution equation,
πV = nRT

n = Moles of solute
V = Volume of solution

n
π= RT
v
Weight of solute WB
n = =
Wg Molecular weight of solute MB
 where, WB = Weight of solute
Mg = Molecular weight of solute

WB RT
 p= �
MB V

WB RT
 MB =
pV

Useful information for MHT-CET

For accurate molecular weight:
1. Solute should be non-volatile.
2. The solution should be dilute.
3. There should be no association or dissociation of solute molecules.
4. If two solutions have same concentrations then osmotic pressure of both solutions is same
called isotonic or isomotic solutions.
5. It may be noted that 0.85% solution of NaCl is isotonic with blood. Saline and injection
to be injected to human body must be isotonic with solution present in the body cells.
6. The osmotic pressure of blood is 8 atm. If blood cells are put in water, it enters in cell and
cell swells up. If excess of water enters in cell, cell bursts out. If blood cells are kept in
concentrated solution of NaCl, cells shrink. Therefore, injections are mixed with saline
before injected into the veins.
 Unsolved Problems
1. Experiment shows that 10 gm of cane sugar (mol. wt. - 342) in 1 x 10-3 m3 of solution
produces an osmotic pressure of 6.68 x 10 4 N/m2 at 273 K. Calculate the value of R in
SI unit.
2. Calculate osmotic pressure of 5% glucose solution at 18°C. (R = 0.082 lit. arm.).
3. Find the osmotic pressure of solution obtained by 3.4% solution of urea (mol. wt. = 60)
at 20°C (R = 0.0821 lit. atm.).
Answers
1. 8.37J mol -1K-1 2. 6.57 atm.
3. 13.63 atm.
Questions As Per Board Pattern
1. Discuss the relation between osmotic pressure and molecular weight of solute. [2M]
2. Define and explain Van't Hoff's equation for solutions. [2M]
3. Injections are mixed with saline before injected into the veins. Give reasons. [2M]

Multiple Choice Questions

1. Solutions having similar osmotic pressures are known as.................
(a) hypertonic solutions (b) hypotonic solutions
(c) isotonic solutions (d) hypertonic or hypotonic solutions
2. In equation πV - nRT, n means......................
(a) normality (b) number of moles of solvent
(c) number of moles of solute and solvent
(d) number of moles of solute

Answer Key

1-c 2-d

1.14 ABNORMAL OSMOTIC PRESSURE

Terms, Definitions, Formulae and Theory
Osmotic pressures of salt, acids, bases are much higher than those calculated from their
molecular weight.
On the other hand, osmotic pressures of colloidal solutions are much lower than calculated. It
is due to dissociation or association of solute molecules.
 Dissociation : Electrolytes undergo dissociation or ionisation in solution. Thus, number of
solute particles become more than normal particles. Since, osmotic pressure increases.
Association : In case of some solute, when dissolved in solvent undergoes association.
Aggregation of two or more molecules of solute takes place in association. Thus, number of solute
particles decreases. Therefore, osmotic pressure is less than calculated.
Van't Hoff factor : Ratio of actual observed osmotic pressure to normal calculated osmotic
pressure under same conditions of temperature and concentration is known as Van't Hoff factor.
It is denoted by T.

i = Actual value of osmotic pressure

Normal or calculated osmotic pressure
As osmotic pressure depends on number of particles,
i = Actual number of particles
Expected number of particles
If i > 1, then dissociation of solute, i <
1, then association of solute, i = 1,
no association or dissociation.

Useful Information for MHT-CET

1. The osmotic pressure of solution depends upon the number of solute particles in solution.
p(obs)
2. Van't Hoff's factor (i) =
p(cal)

3. Van't Hoff's factor depends upon dissociation or association.

4. A solution depends upon number of solute particles because of the colligative properties.
1.15 SELF-LEARNING - VAN'T HOFF AVOGADROS LAW

Terms, Definitions, Formulae and Theory

Equimolar quantities of different solute dissolved in equal volume of solvent (equimolar
solutions) exert equal osmotic pressure, under identical conditions of temperature and pressure.
Equal volumes of different solutions at same temperature and pressure having same osmotic
pressure contain equal number of solute particles.

Questions As Per Board Pattern

1. What is abnormal osmotic pressure ? How it is observed ? [2M]
2. Define and explain : (i) Van't Hoff-Boyle's law, (ii) Van't Hoff-Charle's law,
(Hi) Van't Hoff equation for solution. [2 Marks each]
3. What is Van't Hoff factor ? How it is related to association or dissociation of solute ?
 Multiple Choice Questions
1. Relation between osmotic pressure and concentration of solution is given by...............
(a) Van't Hoff-Charle's law (b) Van't Hoff-Boyle's law
(c) Van't Hoff-Avogadro's law (d) Van't Hoff factor
2. Solutions having same osmotic pressure are known as...............
(a) isotonic (b) hypertonic
(c) hypotonic (d) normal
3. Normal state of solute is represented when value of Van't Hoff factor i is................
(a) zero (b) less than one
(c) one (d) greater than one
4. Van't Hoff equation for solutions in terms of concentration is................
(a) πV = RT (b) πV = CRT
(c) πV = nRT (d) π = CRT
5. The movement of solvent molecules through semi-permeable membrane is called

(a) diffusion (b) osmosis

(c) cataphorasis (d) electrosmosis
6. The osmotic pressure of 0.2% aqueous solution of non-volatile solute is 821 mm of Hg at
27°C. The molecular weight of solute is...............
(a) 46 . (b) 60
(c) 92 (d) 120
Answer Key
1-b 2- a 3-c 4-d
5-b 6-a