Welcome to

Classes
Chemistry

Solutions and Colligative Properties

Wrapping up Henry's Law

What you already know

● Temperature-dependent concentration terms

● Temperature-independent concentration terms
● Types of solutions
● Factors affecting solubility
● Steps involved in dissolution
● Effects of pressure on the solubility of a gas in liquid
(Henry's law)
● Graphical analysis of Henry's isotherm
Wrapping up Henry's Law

What you will learn

● Graphical analysis of Henry's isotherm

● Characteristics of Henry's law constant
● Limitations of Henry's law
● Applications of Henry's law
● Liquid-liquid solutions
● Partial pressure
● Vapour pressure
 Graphical Analysis of Henry’s Isotherm

The solubility of a gas in a liquid at a given temperature is directly proportional

to its partial pressure of the gas present above the solution.

The Henry’s law expression is

given as follows:

Pressure (p)
p = KH × 𝛘
By comparing it with the straight
line equation; Slope = KH
(y = mx + c), we get,
Intercept (c) = 0
Slope (m) = KH
Mole fraction (𝛘)
 Graphical Analysis of Henry’s Isotherm

Compare the intermolecular forces (IMF) between gases A, B and C in the

solvent water.

The Henry’s law expression is given as

follows: A
p = KH × 𝛘

Pressure (p)
B
● Draw a horizontal line parallel to the
x-axis that means at some constant C
partial pressure. From the points
touching the gas A, B and C it is
clear that order of solubility of
gases is:
A<B<C 𝛘A 𝛘B 𝛘C
Mole fraction (𝛘)
 Graphical Analysis of Henry’s Isotherm

● As we already know “like dissolves like” mens polar compounds dissolve in

polar solvents, From the graph clearly C has more solubility means it has
more intermolecular forces.
● For the same partial pressure intermolecular forces is directly related to
solubility. So the order of intermolecular forces is A < B < C.
● From Henry’s law expression p = KH 𝛘. So when p is constant and 𝛘 is
increasing KH must decrease to maintain the same pressure.
● As 𝛘A < 𝛘B < 𝛘C then, KH > K H > KH .
A B C
 Characteristics of Henry's Law Constant (KH)

● According to the relation p = KH 𝛘,

KH has the same units as that of the pressure because there are no units for
mole fraction.
● The different gas-liquid systems have different values of KH.
● KH increases with temperature.
● Its value depends on the intermolecular forces in gas-liquid systems.
● KH decreases with an increase in solubility for the same partial pressure.
 Limitation of Henry's Law

Henry’s law is valid only under the following conditions:

● The pressure of the gas is not too high.
● The temperature is neither too low nor too high. Higher temperature solubility
is less than expected from henry’s law and at lower temperature solubility is
more than expected from henry’s law
● Gas should not have any chemical reaction with the solvent.
● Gas should not undergo dissociation or association in the solvent.
 Henry's law constant for CO2 dissolved in water is
1.67 × 108 Pa at 298 K. Calculate the mole fraction of CO2 in
1 L of soda water when packed under 2.5 atm pressure at 298 K. (1
atm = 101325 Pa)

Solution

Given: KH = 1.67 × 108 Pa We know that, p = KH 𝛘

p = 2.5 atm Substituting the values of p and KH,
1 atm = 101325 Pa 2.5 × 101325 Pa = 1.67 × 108 Pa × 𝛘
Therefore, 2.5 atm = 2.5 × 101325 Pa 𝛘 = 1.517 × 10–3

Therefore, the mole fraction of CO2 in 1 L of soda water when packed under
2.5 atm pressure at 298 K is 1.517 × 10–3.
 If nitrogen gas is bubbled through water at 293 K, how many
millimoles of nitrogen gas would dissolve in 1 L of water? Assume
that nitrogen exerts a partial pressure of 0.987 bar. Given that
Henry's law constant for nitrogen at 293 K is 76.48 kbar.

Solution

● 1 bar = 105 Pa ● 1 atm = 1.01325 × 105 Pa ● 1 atm = 1.01325 bar

Given:
KH = 76.48 kbar = 76480 bar 1000
Number of moles of H2O =
Assume the density of water to be 1 g mL–1 18
1 L of water = 1000 mL = 1000 g = 55.55 moles
 nN
2
⇒ 1 = 76480
⇒ 𝛘 of N2 = n 𝛘 0.987
N + nH O
2 2
Since, nH
1 O
nH O =1+
2
1 2
𝛘 nN
⇒ 𝛘
=1+
nN 2

We know that, p = KH𝛘 ⇒ 76480 = 1 + 55.55

0.987 n
The partial pressure of N2 is given by, N2
0.987 bar = 76480 bar × 𝛘 ⇒ n N = 0.000716 moles
2

0.987 ⇒ n N = 0.716 millimoles

⇒ 𝛘 =
76480 2

Hence, 0.716 millimoles of nitrogen gas would dissolve in 1 L of water.

 Application of Henry’s Law

● To increase the solubility of CO2 in soft drinks and soda water, the bottle
is sealed under high pressure. Therefore, when the bottle opens, the
pressure decreases and the solubility of CO2 also decreases. As a result,
the CO2 comes outside the bottle as shown below.

Bottle is sealed under Fizzes as CO2 comes

high pressure out
Variation of solubility of gas with the pressure
 Application of Henry’s Law
● At high altitudes, the partial pressure of oxygen is less than that at the
ground level because the population density of the oxygen particles is less
at the higher altitudes as compared to that of on the ground level. Low
blood oxygen level causes anoxia.

Low population density of

oxygen particles at higher
altitude

High population density of

oxygen particles at ground
level

Population density of oxygen at different altitudes

 Application of Henry’s Law

● Oxygen diluted with less soluble helium gas is used by sea divers to avoid
bends.
When the sea diver is deep inside the sea, due to high pressure, the
solubility of the gas is more. However, when the diver comes rapidly to the
surface, the dissolved air comes out as the pressure at the surface
suddenly decreases. This forms bubbles in the blood, which are fatal and
can lead to death. Thus, oxygen diluted with less soluble helium gas is
used by sea divers to avoid bends.

What are bends?

Painful effects during the decompression of dissolved air in the blood of
scuba divers are known as bends.
 Application of Henry’s Law

Diver feels comfortable inside the Diver feels uneasiness (bends) due
sea to quick surfacing
Sea divers deep inside the sea and on the surface
 Liquid-Liquid Solutions

Based on miscibility, these liquid-liquid solutions are of the following three types:

Based on miscibility

Completely
Immiscible Partially miscible
miscible
solutions solutions
solutions
 Liquid-Liquid Solutions

Phase

Phase is a physically distinctive form of matter such as a solid, liquid, or gas. The
phase of a matter is characterised by having relatively uniform chemical and
physical properties.

Immiscible solutions

In immiscible solutions, single phase is not observed for any set of compositions.
Examples: Oil in water, water in hexane, etc.
 Liquid-Liquid Solutions

Water Oil Addition of oil to Immiscible

water solution
Oil in water
 Liquid-Liquid Solutions

Partially miscible solutions

In partially miscible solutions, there is a range of compositions over which the

liquids will form a single-phase liquid system.
Examples: Br2 in water, water in butanol, etc.
 Liquid-Liquid Solutions

Water Bromine Addition of Partially miscible

bromine to water solution

Bromine in water
 Liquid-Liquid Solutions

Completely miscible solutions

Single phase is observed for all sets of compositions of the liquids.
Examples: Ink in water, water in ethanol, etc.

Ink

Water

Addition of ink Completely

to the water miscible solution
Ink in water
 Partial Pressure
The pressures of oxygen and nitrogen kept in separate containers are 159 mm
of Hg and 593 mm of Hg respectively. When the contents of both containers are
mixed, the total pressure becomes 752 mm of Hg.

+ =

Beaker: (I) (II) (III)

Oxygen Nitrogen Oxygen + Nitrogen
Pressure: 159 mm of Hg 593 mm of Hg 752 mm of Hg
 Partial Pressure
● In the first beaker, ● In the second beaker,
n RT n N RT
O2 2
p = p =
O2 N2 V
V
● In the third beaker,
n RT Thus,
O2
p = ntotal RT
O2 V ⇒ pO2 + pN = ptotal =
2 V
n N RT
p =
2
⇒ ntotal = nO2 + n N2
N2 V
● If a container is filled with more than one gas, then each gas exerts pressure.
● The pressure exerted by a particular gas within the container is known as its
partial pressure.
 Vapour Pressure

In a liquid-vapour system, the molecules with low energy remain at the surface,
while the molecules with high energy escape from the surface.
Gas particles

Higher energy
molecules escapes from
the surface

Lower energy molecules

remains at the surface
Liquid particles
High energy molecules escaping out of the surface
 Vapour Pressure

Liquid ⇌ Vapour
H2O(l) ⇌ H2O(g)
At equilibrium,
Rate of evaporation = Rate of condensation
Hence, the vapour pressure is the equilibrium constant for the following reaction:
H2O(l) ⇌ H2O(g)
KP = PH O
(g)
2

The pressure exerted by the vapours of a liquid at certain temperature in a closed

system when equilibrium is established between the vapours and the liquid is the
equilibrium vapour pressure or vapour pressure.
 Vapour Pressure

Initial stage Intermediate stage Equilibrium stage

Molecules keep evaporating Few molecules start Rate of evaporation = Rate
condensing back of condensation
 Vapour Pressure

Technically, the pressure exerted by vapours, in thermodynamic equilibrium with

its condensed phase at a given temperature in a closed system is the vapour
pressure.

Condensed phase: Liquid

At t = 0, some liquid (10 g) is taken in a closed conical flask and left for some time.
After some time, the mass of the liquid decreases (less than 10 g). This is because
there is an equilibrium established between the liquid and the vapour phases.
However, the overall mass is the same as some of the molecules in the liquid
phase are converted into the vapour phase.
 Vapour Pressure

Liquid (10 g) at Liquid (< 10 g)

t=0 at t = teq
 Vapour Pressure

Condensed phase: Solid

● All solids materials have vapour pressure.

● However for most of the solids the values of vapour pressure are extremely low
at atmospheric conditions, difficult to measure and can be neglected and these
solids do not directly sublimes at atmospheric temperature and pressure.
● There are few solids which directly sublimes at atmospheric temperature and
pressure, thus shows significant vapour pressure at atmospheric conditions like
dry ice, camphor and iodine.
● The vapour pressure of a vapour-solid system when rate of sublimation becomes
equal to rate of deposition is equilibrium vapour pressure.
 Vapour Pressure
I2(s) I2(g)

I2(g)
I2(s) I2(s)

At equilibrium
Rate of sublimation = Rate of deposition
 Vapour Pressure

Vapour pressure does not depend on the:

● Surface area
● Shape of the container
● Amount of liquid taken

Consider two containers of different surface areas and different volumes. The
number of vapour molecules in each of the containers may be different, but the
volume of the container will also change accordingly so that the number of vapour
molecules (nvap) per unit volume (V) remains constant i.e. their population density
will be the same irrespective of the size and the shape of the container.
 Vapour Pressure

Effect of surface area on population density

Small surface area Large surface area

Both have same population density
 Vapour Pressure

n vap RT
Pvap =
V

Since the ratio of the number of vapour molecules (nvap) to the volume (V) is
constant, the vapour pressure (Pvap) in both containers must also be the same,
provided they are kept at the same temperature.

The vapour pressure of liquid water at 25 oC = 23.8 torr

Welcome to

Classes
Chemistry

Solutions and Colligative Properties

Liquid - Liquid Solutions and Raoult’s Law

What you already know What you will learn

● Characteristics of Henry’s law ● Factors affecting vapour

constant pressure
● Applications of Henry’s law ● Relative humidity
● Partial pressure ● Vapour pressure of
● Limitation of Henry’s Law liquid - liquid solutions
● Liquid - Liquid solutions ● Raoult’s law
● Vapour pressure ● Dalton’s law
 Factors Affecting Vapour Pressure

Vapour pressure depends on the following factors:

1. Surface tension
2. Temperature

Surface tension

● Molecules on the surface of the

liquid have been shown by dark Surface
blue spheres and molecules in
Bulk
the bulk of the liquid have been liquid
shown by light blue spheres .
 Factors Affecting Vapour Pressure

● Any molecule in the bulk of the liquid

Surface
experiences forces in all the
directions and hence, the net vector Bulk
sum of forces acting on the particle liquid

becomes zero.

● However, for the particles on the surface (dark blue spheres), they experience
a force of attraction from the bulk of the liquid only, i.e., from a single direction.
The net force experienced by the particles at the surface per unit length of
the surface is known as surface tension.
 Factors Affecting Vapour Pressure

Effect of surface tension on vapour pressure

Higher the intermolecular forces, higher the surface tension and, lower is
the vapour pressure.
Example
Let us pour some sanitiser and some water on a table. We observe that the
sanitiser evaporates faster than water. Since the intermolecular interactions
between the ethanol molecules are less compared to water molecules, the
surface tension will be less in the case of the sanitiser, and the vapour pressure
will be more. Higher vapour pressure means that the sanitiser will evaporate
faster than water.
 Factors Affecting Vapour Pressure

Sanitiser Water Sanitiser dries

faster than water.
 Factors Affecting Vapour Pressure

Effect of temperature on vapour pressure

Consider two flasks, one at a lower temperature and another at a higher

temperature. As the temperature increases, the average kinetic energy of the
molecules also increases. Thus, at a higher temperature, more molecules from the
liquid have enough kinetic energy to escape from the surface of the liquid into the
vapour state. This increases the number of vapour molecules and the saturated
vapour pressure.
 Factors Affecting Vapour Pressure

The effect of temperature can also be

understood by using thermodynamics as
follows:
Consider the evaporation of a liquid
Liquid ⇌ Vapour
Since for this conversion, i.e., evaporation,
Low temperature High temperature
heat is required, ΔH (or ΔvapH) is positive, particles have low particles have high
or evaporation is always endothermic. average K.E. average K.E.
 Factors Affecting Vapour Pressure

According to Le Chatelier's principle, an

increase in the temperature of a system in a
dynamic equilibrium favours an endothermic
change. So, increasing the temperature
increases the amount of vapour present.
Hence, it increases the saturated vapour
pressure.
Low temperature High temperature
● Saturated vapour pressure is the maximum particles have low particles have high
average K.E. average K.E.
possible vapour pressure at a particular
temperature.
 Factors Affecting Vapour Pressure

● The effect of temperature on the vapour pressure of a liquid can be

measured quantitatively using the Clausius–Clapeyron equation as
follows:

P2 ΔH 1 1
ln
P1
=
R T1
− T2

Where,
ΔH = Enthalpy of vaporization
P1 = Vapour pressure of the liquid at temperature T1
P2 = Vapour pressure of the liquid at temperature T2
 Calculate the vapour pressure of water at 320 K when the aqueous
tension at 300 K is 26.7 torr. (Given: Heat of vaporization of water is
40.65 kJ/mol)

Solution

The vapour pressure of water is known as aqueous tension. So, the vapour
pressure of water at 300 K is 26.7 torr, and the vapour pressure of water at 320 K
needs to be calculated. Let us consider the vapour pressure at 320 K as P2.

➢ P1 = 26.7 torr
➢ T1 = 300 K
➢ T2 = 320 K
➢ ΔvapH = 40.65 kJ/mol
➢ P2 = ?
Using the Clausius-Clapeyron equation,

⇒ P2 = 74.04 torr
Therefore, the vapour pressure of water at 320 K is 74.04 torr.
 Vapour Pressure of Liquid-Liquid Solutions

Consider both the liquid solute and the liquid solvent to be volatile in
nature. If the solution consists of a volatile solute and a volatile solvent,
then the vapour consists of components of both the solvent and the solute.

Thus, the composition of the vapour may vary as the mole fraction of the
solute and the solvent varies.

Example: In the given three cases, the constituting liquids are the same.
However, as the mole fraction changes, the composition of the vapour
also changes.
 Vapour Pressure of Liquid-Liquid Solutions

1) 1 mol of liquid A and 1 mol of liquid B. +

1 mol of 1 mol of Solution

liquid A liquid B A+B

2) 1 mol of liquid A and 2 mol of liquid B.

+

1 mol of 2 mol of Solution

liquid A liquid B A+B
 Vapour Pressure of Liquid Solutions

3) 2 mol of liquid A and 1 mol of liquid B. +

2 mol of 1 mol of Solution

liquid A liquid B A+B

As the composition of the vapour changes, the vapour pressure also changes.
Hence, vapour pressure depends on the mole fraction of the constituting liquids
in case both the solvent and solute is volatile.

The partial pressure of each component depends on the mole fraction of the
corresponding component.
 Raoult’s Law

Consider three beakers given below, in the first beaker, there is only pure red
volatile liquid(A); in the second beaker, there is only pure green volatile liquid(B);
in the third beaker, there is a solution of red and green volatile liquids.

Red Green Solution of red

liquid liquid and green
volatile liquids
 Raoult’s Law

The vapour pressure in the first beaker is the vapour pressure of the molecules of
the red volatile liquid in their pure state. This is the vapour pressure of the pure red
liquid denoted as PoA . Similarly, the vapour pressure of the pure green liquid is PoB .

Partial pressure of liquid A and liquid B in terms of their mole fractions is given by
Raoult’s law as:

Partial pressure of A = PA = PA0 χA

Partial pressure of B = PB = PB0 χB

 Raoult’s Law
Where,
χA is the mole fraction of component A in the solution phase
χB is the mole fraction of component B in the solution phase
PoA is the vapour pressure of A in its pure state
PoB is the vapour pressure of B in its pure state

The partial pressure of each component of an ideal mixture of liquids is equal to the
vapour pressure of the pure component multiplied by its mole fraction in the mixture.
Here, ideal solutions are the solutions that obey Raoult's law in all the compositions.

Partial pressure of each component of an ideal mixture of liquids = (Vapour

pressure of the pure component) × ( Mole fraction of the component in the
solution)
 Raoult’s Law
Graphical representation
● As the partial pressure of component A is given by PA = PoAχA, the graph of partial
pressure of component A (PA) versus its mole fraction (χA) must be a straight line.

PoA

pressure (PA)
Vapour

χA = 0 0.2 0.4 0.6 0.8 1

Mole fraction (χ)
 Raoult’s Law
● Comparing the equation for partial pressure with the equation of a straight
line, y = mx + c,
➢ Slope of the line = tan θ = PoA
➢ The intercept is zero.
● Also, when the mole fraction of component A is one (χA = 1), i.e., only
component A is present, then,
PA = PoA(1) = PoA
● If component B is also in the solution and no other component is present,
then the mole fraction of component B can be related to the mole fraction of
component A as,
χB = 1 - χA
● Similar to component A, the partial pressure of component B is given by,
PB = PoBχB
 Raoult’s Law
● Using χB = 1 - χA, the graph of partial pressure of component B versus its mole
fraction can be drawn as follows:

Vapour pressure (P) o

PB

1 0.8 0.6 0.4 0.2 χB = 0

Mole fraction (χ)

 Raoult’s Law

● Here, if χB = 1, then,
PB = PoB

● Now, both the lines can be drawn in the same graph. Since at any point
the sum of the partial pressures of both the components gives the total
pressure, in the same graph, we can draw a line representing the total
vapour pressure of the solution given by the sum of the partial
pressures of both the components (PA and PB).
 Raoult’s Law
Total vapour pressure of solution

Vapour pressure (P) PoA

PoB

χ A= 0 0.2 0.4 0.6 0.8 χ A= 1

χ B= 1 0.8 0.6 0.4 0.2 χ B= 0
Mole fraction (χ)
 Raoult’s Law
Expression for the vapour pressure of a binary liquid-liquid solution

For a binary solution having two components A and B, the total vapour pressure is
given as:
PTotal = PA + PB
Where,
PA and PB are the partial pressures of components A and B, respectively.

From Raoult’s law,

Partial pressure of A = PA = PoAχA
Partial pressure of B = PB = PoBχB
So, PTotal = PoAχA + PoBχB
 Raoult’s Law

We know that, χA + χB = 1 ⇒ χA = 1 - χB

⇒ PTotal = PoA (1 - χB) + PoBχB

⇒ PTotal = PoA + (PoB - PoA)χB

 An equimolar mixture of benzene and toluene is prepared.
The total vapour pressure of the mixture as a function of the
mole fraction of benzene is found to be:
PTotal = 200 + 400 χBenzene. Calculate the value of PoToluene and
PoBenzene. (Take the units of pressure to be atm)

Solution

Given: PTotal = 200 + 400 χBenzene

On comparing this equation with PTotal = PoA + (PoB - PoA) χB,
PoA = PoToluene = 200 atm (Since benzene is more volatile)
PoB - PoA = PoBenzene - PoToluene = 400 atm

⇒ PoBenzene = PoToluene + 400

⇒ PoBenzene = 200 + 400 = 600 atm

Therefore, the values of PoToluene and PoBenzene are 200 atm and 600
atm, respectively.
 Dalton’s Law

Consider a binary solution of two non-reacting liquids A and B. Dalton’s law relates
the partial pressure of a component with the mole fraction of that component in the
vapour phase.

Example:
Assume a binary solution in which the components A and B are in a 100:1 mol ratio
in the solution with PoA = 100 torr and PoB = 1,000 torr. So, B is more volatile than A.
However, A is present in a higher amount than B. So, to get an idea of which will be
present in what amount in the vapour phase, Dalton’s law is used.
 Dalton’s Law
According to Dalton’s law,
PA = yA × PTotal
PB = yB × PTotal
Where, yA = Mole fraction of A in the vapour phase
yB = Mole fraction of B in the vapour phase

Relating Raoult’s law with Dalton’s law

From Raoult's law,
PA = PoAχA
PB = PoBχB
From Dalton’s law,
PA = yA × PTotal
PB = yB × PTotal
 Dalton’s Law
Comparing Raoult's law and Dalton's law,

yA PTotal yB PTotal
From both the
χA = and χB =
equations we have, PA0 PB0

Since χA + χB = 1

1 yA yB
Hence, = +
PTotal 0
PA
0
PB
Two liquids A and B have PoA and PoB in the ratio 1 : 3. The
ratio of the number of moles of A and B in the liquid phase is
1 : 3. What is the mole fraction of A in the vapour phase in
equilibrium with the solution?

a) 0.1 b) 0.2

c) 0.5 d) 1.0
 Solution

We know that the total vapour pressure of the solution is related to the
partial pressure of the components as:
PTotal = PA + PB = PoAχA + PoBχB

χA PoA 0.25 × PoA

Now, yA = =
PTotal 0.25 × PoA + 0.75 × 3PoA

1
yA = = 0.1
1+9

Therefore, option (a) is the correct answer.

Welcome to

Classes
Chemistry

Solutions and Colligative Properties

Introduction to Solutions

What you will learn

● Solution and its characteristics

● Components of a solution
● Identifying solute and solvent
● Measuring concentration of
solutions
 Solutions and its Characteristics

Solutions

When two or more chemically non-reacting substances are mixed and a

homogeneous mixture is formed, it is known as a solution.
Homogeneous mixtures are those solutions where the substances tend to mix
uniformly with each other. A homogeneous mixture is a gaseous, liquid, or solid
mixture that have uniform composition and properties throughout a given
sample. Only single phase is visible.
Examples: Sugar in water, ink in water, etc.
 Solutions
Solutions and
and its
its Characteristics
Characteristics
Sugar in water
● When sugar is dissolved in water, it forms a homogeneous mixture. The
sweetness is the same in all the parts of the solution.
● The composition is the same throughout the sugar solution.

Sugar

Water Addition of Homogeneous

sugar to water solution
 Solutions and its Characteristics

Ink in water

When blue ink is dropped in water, we can observe that after stirring the solution
or leaving it for some time, the blue colour dissolves in all the parts of the water
i.e., uniform composition. Hence, it is a homogeneous mixture.

Ink

Homogeneous
solution

Water Addition of ink

to the water
 Solutions and its Characteristics

Diesel in petrol

We already know from

organic chemistry that
diesel and petrol are
nonpolar.
Petrol Diesel Addition of diesel Homogeneous
to petrol solution

When diesel is added to petrol, as we know that like dissolves like, polar
substances dissolve in polar compounds and nonpolar substances dissolve in
nonpolar compounds, diesel gets dissolved in petrol, forming a uniform
composition. Hence, it is a homogeneous solution.
 Solutions and its Characteristics
Benzene and toluene

Benzene and toluene forms a

homogeneous mixture, because
Benzene and toluene both are
nonpolar.

Toluene Benzene Addition of toluene to Homogeneous

benzene solution
 Solutions and its Characteristics

Heterogeneous mixtures are those mixtures that contain physically distinct parts
and have non-uniform compositions. Suspensions and colloids are examples of
heterogeneous mixtures.
Example: Oil in water
Suspensions: Heterogeneous mixtures in which the solid particles are spread
throughout the liquid without dissolving in it.
Colloids: Appear to be homogeneous but are heterogeneous.
Example: Toothpaste, blood, cream etc.

Toothpaste
 Solutions and its Characteristics

Oil in water

Water Oil Addition of oil Heterogeneous

to water mixture

When both oil and water are mixed, they form two layers. This clearly indicates that it is
a heterogeneous system as the solution is non uniform throughout. Oil is nonpolar and
water is polar. If we mix oil and water and shake them a cloudy suspension is formed.
 Solutions and its Characteristics

Characteristics of solution

● Only a single phase is visible.

● It has uniform composition and properties throughout.
● It is usually transparent and can be coloured as well.
● It does not separate even when it is undisturbed.
 Components of a Solution

Formation of a solution

+ =

Solute Solvent Solution

● Solute and solvent when mixed together form a solution.

 Components of a Solution

Solute Solvent
Present in less amount Present in more amount
Low dielectric constant High dielectric constant
Found in solid, liquid and gaseous Represents the phase of the
state solution

Phase: A phase is a chemically and physically homogeneous quantity of

matter that can be separated from a non homogeneous mixture. The same
physical state but different arrangement of particles gives different phases.
 Components of a Solution

Every molecule has its own dipole. A solvent like water is composed of large
amount of H2O molecules. Each of them have a dipole moment of their own
(Dipoles may be oriented in random ways). When we pass an electric field through
the solution, the dipole of the individual molecules will somehow interact with the
external field and there is some change in electric field value inside. It can be
expressed by dielectric constant.

Dielectric constant: The ratio of the permittivity of the substance to the

permittivity of the free space. It expresses the extent to which a
material can hold electric flux in it.
 Identifying Solute and Solvent

Solute and Solvent

In different phases In same phase

The component
The phase of the The one that
which is more
solvent is the phase of dissociates is the
in amount is
the solution solute
the solvent
 Identifying Solute and Solvent

● If solute and solvent are in different phases, then the phase of the solvent is the
phase of the solution.
For example: If we mix sugar and water, both of them are in different phases.
Thus phase of the solvent i.e., water, is the phase of the solution.
● It is possible to have the same state but different phases.
For example: Amorphous and crystalline solids are in the same state (solid) but
in different phases.
● If they are in the same phase, the component that is more in amount is the
solvent and the one that dissociates is the solute.
For example: If we mix ink with the water, both of them are in the liquid phase
and water being in large amount acts as a solvent here.
 Measuring Concentration of Solutions

Composition of a solution

Composition of a solution can be described by expressing its concentration.

Percentage Concentration Terms

% w/w % w/V % V/V

 Measuring Concentration of Solutions

Mass percentage (% w/w) Mass by volume percentage (% w/V)

Weight in grams of the solute per 100 g of Weight in grams of the solute per 100 mL
the solution. of the solution.

w Weight of solute (g) w Weight of solute (in g)

% = × 100 % = × 100
w Weight of solution (g) V Volume of solution (in mL)

Volume percentage (% V/V)

Volume of solute (in mL)
Volume in mL of the solute per 100 mL % V = × 100
of the solution. V Volume of solution (in mL)
 Measuring Concentration of Solutions

Other concentration terms

Concentration Terms

Strength (S)

Molarity (M)

Normality (N)

Molality (m)

Mole fraction

ppm
 Measuring Concentration of Solutions

Concentration
Formula Unit
term

Weight of solute (in g)

Strength (S) Strength = g L−1
Volume of solution (in L)

Number of moles of solute

Molarity (M) Molarity = mol L−1 or M
Volume of solution (in L)

Number of gram equivalent of solute

Normality (N) Normality = g eqiv. L−1 or N
Volume of solution (in L)
 Measuring Concentration of Solutions

Concentration
Formula Unit
term

Number of moles of solute

Molality (m) Molality = mol kg−1 or m
Weight of solvent (in Kg)

Moles of the component

Mole fraction (𝛘) Mole fraction = -
Total moles in solution

Parts per million Weight of solute

ppm = × 106 -
(ppm) Weight of solution
 4 g of NaOH is added to 500 mL of water. Calculate the
molarity and strength of the solution.

Solution

Step 1: Calculation of the molarity

Let us assume that the volume of the solution is V.

Given mass of NaOH

Moles of NaOH =
Molar mass of NaOH
4
Thus, moles of NaOH = = 0.1 mol
40
 Moles of NaOH = 0.1 mol Step 2: Calculation of the strength
Volume of solution = 500 mL = 0.5 L
Weight of solute (in g)
Strength =
No. of moles of a solute Volume of solution (in L)
Molarity (M) =
Volume of solution (in L)
4g
0.1 Thus, strength (S) = = 8 g L−1
Thus, Molarity (M) = = 0.2 M 0.5 L
0.5 L

Hence, the strength and molarity of the given solution is 8 g L−1 and 0.2 M
respectively.
 A sample of H2SO4 (density = 1.4 g mL−1) is labelled as 49%
w/w. Calculate its molality.

Solution

Step 1:
Take 1 L (1000 mL) of the given solution. (Given, d = 1.4 g mL−1)
1 L (1000 mL) solution weighs 1,400 g

Step 2: Step 3:
49 686 g
Weight of H2SO4 = × 1400 g = 686 g Number of moles of solute =
100 98 g mol−1
Weight of water = 1400 g − 686 g = 714 g = 7 moles
Step 4:

No. of moles of solute

Molality (m) =
Weight of solvent (in Kg)

7 × 1000
Molality (m) = = 9.8 m
714

Hence, molality of the given solution is 9.8 m.

 The density of a 15% (w/w) urea solution is found to be
1.1 g mL−1. Find the molarity, molality, mole fraction of the
solute, and strength of the solution in g L−1.

Solution

Step 1:
15 % (w/w) urea solution contains 15 g urea in 100 g of the solution. So, there is
150 g urea in 1000 g of the solution (i.e., in 850 g of the solvent).

Step 2:
Number of moles of solute
Molality (m) =
Mass of solvent (in Kg) 2.5
Molality (m) = = 2.94 m
150 g 0.85
Number of moles of urea = = 2.5 moles
60 g mol−1
Step 3:

Number of moles of urea

Mole fraction of urea =
Number of moles of urea + Number of moles of water

150 g
Number of moles of urea = = 2.5 moles
60 g mol−1

850 g
Number of moles of water = −1 = 47.22 moles
18 g mol

2.5
Therefore, mole fraction of urea = = 0.0502
2.5 + 47.22
 Step 4:
Step 5:
Density of solution = 1.1 g mL−1
Weight of solution (g)
We know that Strength =
Volume of solution (L)
Mass of solution
Density = 150 g
Volume of solution Strength =
0.909 L
1000 g
Volume of solution = = 909.1 mL Strength = 165.01 g L−1
1.1 g mL−1
Number of moles of solute
Molarity =
Volume of solution (in L)
2.5
Molarity = = 2.75 M
0.909

Hence, molarity, molality, mole fraction of the urea, and strength of the given
solution are 2.75 M, 2.94 m, 0.0502 and 165.01 g L−1 respectively.
Welcome to

Classes
Chemistry

Solutions and Colligative Properties

 Ideal and Non-Ideal Solutions

What you already know

What you will learn

● Factors affecting vapour
pressure
● Interactions in liquid—liquid
● Relative humidity
solutions
● Vapour pressure of liquid-liquid
● Ideal solutions
solutions
● Non-ideal solutions
● Raoult's law
● Vapour pressure and boiling
● Binary liquid-liquid solution
point
● Relating Raoult's law with
Dalton's law
 Two liquids A and B have PA and PB in the ratio 1 : 3 and the ratio of the
number of moles of A and B in liquid phase is 1 : 3. The mole fraction
of A in vapour phase in equilibrium with the solution is equal to:

(a) 0.1 (b) 0.2

(c) 0.5 (d) 1.0

Solution

Step 1: Analysing the parameters given in the question

It is given that the vapour pressure of pure components A (PoA) and B (PoB) is in the
ratio 1 : 3
Let us assume that PoA = P
Hence, PoB = 3P
Also, the number of moles of A(n(l)A) and B(n(l)B) in the liquid phase is in the ratio 1 : 3.
That means, n(l)A = n and n(l)B = 3n

Step 2: Finding mole fractions of A and B in the liquid phase

Let 𝛘A and 𝛘B be the mole fractions of A and B, respectively, in the liquid phase.
Step 3: Finding the mole fraction of A in the vapour phase
Let yA and yB be the mole fractions of A and B, respectively, in the vapour phase.
According to Dalton’s law of partial pressures, PA = yA × PTotal and PB = yB × PTotal
From Raoult’s law, PTotal = PA + PB = 𝛘APoA + 𝛘BPoB
Hence,

The mole fraction of A in the vapour phase in equilibrium with the solution = 0.1
Hence, option (a) is the correct answer.
 Interactions in Liquid–Liquid Solutions
When the solute A (liquid) dissolves in the solvent
B (liquid), the extent of dissolution depends on the
following:
● A—A interaction (solute—solute interactions)
● B—B interaction (solvent—solvent interactions)
● A—B interaction (solute—solvent interactions)
Representation of A—A, B—B, and A—B
interactions A—A B—B A—B
Red balls represent solute A, and blue balls
represent solvent B.

Classification of solution on the basis of liquid-liquid interactions

(1) Ideal solution (2) Non-ideal solution
 Ideal Solutions

● The solutions that obey Raoult’s law over the entire range of component
concentration are known as ideal solutions.
● For ideal solutions, the solute—solvent (A—B) interaction is equal to the
solute—solute (A—A) and solvent—solvent (B—B) interactions.
● The enthalpy of mixing pure components to form an ideal solution is zero, i.e.,
∆mixH = 0. This means no heat energy is released or absorbed when the
components are mixed, since the interactions between the particles before
and after mixing are the same.
 Ideal Solutions

● For ideal solutions, ∆mixV = 0. The volume of solution is equal to the sum of the
volumes of the two components.
● For ideal solutions, ∆mixS > 0. Mixing of two pure components is always
accompanied with an increase in entropy.
● For ideal solutions, ∆mixG < 0, indicating that the process of mixing is
spontaneous.

Examples:
Solutions of n-hexane and n-heptane, bromoethane and chloroethane,
benzene and toluene are some examples of ideal solutions.
 Ideal Solutions

Graphical interpretation of an ideal solution

The plot of vapour pressure and mole fraction of an ideal solution at a constant
temperature is given in which PA and PB represent the partial pressures of
components A and B. The plot of PA or PB versus the mole fractions 𝛘A and 𝛘B for a
solution gives a straight line. The total vapour pressure of the solution (PTotal) for
any given composition is equal to the sum of the partial vapour pressures of A and
B.
For ideal solutions, PTotal = PA+ PB = 𝛘APoA + 𝛘BPoB
 Ideal Solutions

P
T = P
A + P
Vapour pressure B

o
PA
o
PB PA PB

𝛘A = 1 Mole fraction 𝛘A = 0
𝛘B = 0 𝛘A 𝛘B = 1
𝛘B
 Ideal Solutions

The ideality of a solution implies that a molecule of component A

will have the same tendency to escape into the vapour phase
whether it is surrounded entirely by other molecule of its own
type (i.e., A), entirely by component B, or partly by the molecules
of component A and partly by B.
 Non-Ideal Solutions

● The solutions that do not obey Raoult’s law over the entire range of
concentration are known as non-ideal solutions.
● The vapour pressure of such solutions is either higher or lower than that
predicted by Raoult’s law.
● Non-ideal solutions can show positive or negative deviations from Raoult’s law.
The cause for these deviations lies in the nature of interactions at the molecular
level.

Positive deviation from Raoult’s law

● When the vapour pressure of a solution is higher than that predicted from
Raoult’s law, then the solution exhibits a positive deviation from Raoult’s law.
 Non-Ideal Solutions

● In case of a positive deviation from Raoult’s law, A—B interactions are weaker
than those between A—A and B—B, i.e., the intermolecular attractive forces
between the solute—solvent molecules are weaker than those between the
solute—solute and solvent—solvent molecules. This means that in such
solutions, the molecules of A (or B) will find it easier to escape in the solution
than in a pure state. This causes an increase in the vapour pressure of A and B
in solution. An increase in PA and PB has resulted in an increase in the total
vapour pressure over the solution (PTotal).
● For solutions with a positive deviation

PTotal = PA + PB > 𝛘APoA + 𝛘BPoB

 Non-Ideal Solutions
Vapour pressure
of the solution

Here, the plot of vapour pressure PT

and mole fraction of a solution with
a positive deviation from Raoult’s
law is given where the dotted lines

Vapour pressure
o
represent the vapour pressure
PA o
according to Raoult’s law, and the PB
PA PB
solid curves represent a positive
deviation of the solution from
Raoult’s law. Mole fraction 𝛘A = 0
𝛘A = 1
𝛘B = 0 𝛘A 𝛘B = 1
𝛘B
 Non-Ideal Solutions

● Solutions with positive deviation from Raoult’s law are characterised by a

positive enthalpy of mixing (∆mixH > 0). The amount of energy released in
the A—B interaction is very less when compared to the energy required to
break A—A and B—B interactions.
● Solutions with a positive deviation from Raoult’s law are characterised by
a positive volume of mixing (∆mixV > 0). Because of the weak attractions
between A and B, the resulting solution obtained on mixing experiences
expansion.
 Non-Ideal Solutions

● Positive deviations are also accompanied by an increase in entropy (∆mixS >

0). Entropy always increases when two pure components are mixed together
to form a mixture.
● Positive deviation is also accompanied by a decrease in the Gibbs free
energy, ∆mixG < 0, indicating that the process is spontaneous.
Examples for solutions with positive deviations:
Ethanol and acetone, CS2 and acetone, water and ethanol.
 Non-Ideal Solutions

Negative deviation from Raoult’s law

● When the vapour pressure of a solution is lower than that predicted from
Raoult’s law, the solution exhibits a negative deviation from Raoult’s law.
● In negative deviations from Raoult’s law, the intermolecular attractive forces
between A—A and B—B are weaker than those between A—B.
● The escaping tendency of molecules for each component (i.e., A and B)
decreases and consequently, the vapour pressure decreases, resulting in a
negative deviation from Raoult’s law. The decrease in PA and PB results in a
corresponding decrease in PTotal.
● For solutions with a negative deviation, PTotal= PA + PB < 𝛘APoA + 𝛘BPoB
 Non-Ideal Solutions

Vapour pressure
of the solution
Here, the plot of vapour pressure
and mole fraction of a solution PT
with negative deviation from
Raoult’s law is given where the

Vapour pressure
dotted lines represent vapour o PB
PA o
pressure according to Raoult’s PA PB
law, and solid curves represent
negative deviation of solution
from Raoult’s law. 𝛘A = 1 Mole fraction 𝛘A = 0
𝛘B = 0 𝛘A 𝛘B = 1
𝛘B
 Non-Ideal Solutions

● Negative deviations are accompanied with a negative enthalpy of mixing

(∆mixH < 0). Since A—B attractions are stronger than A—A and B—B, energy is
released, when A and B are mixed.
● Due to stronger A—B interactions, negative deviations are accompanied by a
decrease in the volume of mixing (∆mixV < 0).
● Negative deviations are also accompanied by an increase in entropy (∆mixS >
0) and decrease in Gibbs free energy (∆mixG < 0).
● Examples for solutions with negative deviations:
Phenol and aniline, CHCl3 and acetone.
 Interactions in Liquid–Liquid Solutions

The major points to be noted for ideal and non-ideal solutions are given as follow:

Ideal Non-ideal solution

Solution Positive deviation Negative deviation

Follow Raoult’s law at all

Do not follow Raoult's Do not follow Raoult's
temperature &
law law
concentration
PT > 𝛘APoA + 𝛘BPoB PT < 𝛘APoA + 𝛘BPoB
PT = 𝛘APoA + 𝛘BPoB
A—A = B—B = A—B A—A and B—B > A—B A—A and B—B < A—B

Benzene + Toluene Water + Ethanol CHCl3 and acetone

An equimolar mixture of benzene and toluene is prepared. The total
vapour pressure of this mixture as a function of the mole fraction of
benzene is found to be PTotal= 200 + 400 𝛘B.
(a) Calculate the composition of vapour of this mixture (assume that
the number of moles going into the vapour phase is negligible in
comparison to the number of moles present in the liquid phase).
(b) If the vapours above the liquid in part (a) are collected and
condensed into a new liquid, calculate the composition of vapours of
this new liquid.
 Solution

Step 1: Analysing the question

Given PTotal = 200 + 400 𝛘B … (1)
Since prepared solution is a mixture of benzene and toluene, we can write,
PTotal = PT + PB = 𝛘TPoT + 𝛘BPoB … (2)
Where, PT and PB are the partial pressure of toluene and benzene in the
solution, respectively.
PoT and PoB are the vapour pressures of pure toluene and benzene,
respectively.
𝛘T and 𝛘B are mole fractions of toluene and benzene in liquid phase,
respectively.
We know, that, 𝛘T + 𝛘B = 1
i.e., 𝛘T = 1 - 𝛘B.
Substituting 𝛘T in equation (2), we obtain:
PTotal = (1 - 𝛘B)PoT + 𝛘BPoB
PTotal = PoT -𝛘BPoT + 𝛘BPoB
PTotal = PoT +(PoB - PoT)𝛘B … (3)
From (1) and (3),
200 + 400 𝛘B = PoT + 𝛘B(PoB - PoT)
Hence, PoT = 200 mm of Hg, and PoB - PoT = 400 mm of Hg
∴ PoB = 600 mm of Hg
Step 2: Solving part (a)
Since equimolar mixture of benzene and toluene is prepared, the mole
fractions in liquid phase for benzene 𝛘B) and toluene (𝛘T) is given as follows:
𝛘B = 𝛘T = ½
PTotal over the solution phase is given as:
Let, yT and yB be the mole fractions of toluene and benzene in the vapour
phase.
We know, that, PT = 𝛘TPoT = yTPTotal (from Raoult’s law and Dalton’s law of
partial pressures)
Similarly, PB = 𝛘BPoB = yBPTotal (from Raoult’s law and Dalton’s law of partial
pressures)

Hence, the composition of vapour of this mixture is given as: yT = 0.25 and yB =
0.75.
Step 3: Solving part (b)
In part (a), we already found the composition of the vapour phase as: yT = ¼ and
yB = ¾ . These vapours of toluene and benzene are collected, and condensed
into a new liquid. So the vapour phase composition will be the same, as the new
liquid phase composition. Let 𝛘T’ and 𝛘B’ be the mole fractions of toluene and
benzene in the new liquid.
Hence, 𝛘T’ = yT = ¼ and 𝛘B’ = yB = ¾ .
Now, PTotal over the solution phase is given as:

Ptotal = 𝛘T’ PTo + 𝛘B’ PBo Ptotal = ¼ × 200 + ¾ × 600

Ptotal = 500 mm of Hg
 Let, yT’ and yB’be the mole fractions of toluene and benzene in the vapour phase.
Also, PT = 𝛘T’PoT = yT’PTotal

Similarly, PB = 𝛘BPoB = yB’PTotal

Hence, the composition of vapours of new mixture is given as: yT’ = 0.1 and yB’ =
0.9.
 Vapour Pressure and Boiling Point

● Vapour pressure of a liquid can

affect its boiling point. Gas
particles

● Consider a beaker filled with Liquid

particles
some liquid. The high energy
molecules of liquid state (i.e., the
fastest moving particle of liquid
The high energy
state) will easily escape from the molecules escape
surface of liquid to the vapour the surface.
phase.
 Vapour Pressure and Boiling Point

For a better understanding, let us

analyse the liquid surface in more
detail. Atmospheric pressure is
Patm
exerted on the surface of the liquid, as
a result of the collision of atmospheric
particles (like O2, N2) with the liquid
surface. At the same time, the liquid
particles will try to escape to the Pvap
vapour phase, and these vapours will
exert a pressure against the
atmospheric pressure (Patm).
 Vapour Pressure and Boiling Point

When the vapour pressure increases, it pushes the air molecules above the
surface, making it easier for the liquid molecules to spread (expand) and form
vapour. On heating the liquid under constant pressure, say, under the
atmospheric pressure, it will start boiling at a temperature, at which, its total
vapour pressure becomes equal to the atmospheric pressure. This temperature is
the boiling point of liquid.
Vapour Pressure and Boiling Point

Vapour pressure = Atmospheric pressure

Boiling point
 Vapour Pressure and Boiling Point

Some important points to be noted regarding vapour pressure and boiling point
are as follows:
● When a beaker containing liquid is kept inside a vacuum, the liquid will boil
even at room temperature, as there is no atmospheric pressure acting
against vapour pressure of liquid.
● At a lower atmospheric pressure, any liquid will boil at a lower temperature.
● If a liquid has a high vapour pressure at a particular temperature, it means
that its molecules can escape easily from the surface. The liquid with the
higher vapour pressure at a particular temperature is the one with the lower
boiling point.
 Vapour Pressure and Boiling Point

● Due to the presence of extensive hydrogen bonds in water, a higher

amount of energy has to be supplied to water molecules, so that they
break the hydrogen bonds between the molecules and escape to the
vapour phase. Hence, water has a higher boiling point of 100 oC.
● On the contrary, a liquid with weak intermolecular attractions has a higher
vapour pressure, and will boil at a lower temperature.
Welcome to

Classes
Chemistry

Solutions and Colligative Properties

Depression in Freezing Point and Osmotic Pressure

What you already know What you will learn

● Characteristics of Kb ● Depression in freezing point

● Elevation of boiling point ● Osmosis and osmotic pressure
● Ostwald-Walker method ● Types of solutions
● Question based on ● Reverse osmosis
Ostwald-Walker method
 Depression in Freezing Point

Freezing point: It is the temperature at which the vapour pressure of the

substance in its liquid phase is equal to its vapour pressure in the solid phase.

For a better understanding of the meaning of freezing point, an illustration is

given as follow:
Ice cubes are enclosed in a container. Since, the melting point of ice is 0 oC at
1 atm. Thus, the ice cubes can melt at any temperature above it . At freezing
point, the vapour pressure of the substance in its liquid phase is equal to its
vapour pressure in the solid phase. i.e., V.P.1 = V.P.2, where V.P.1 is the vapour
pressure of the solid phase (ice) and V.P.2 is the vapour pressure of the liquid
phase (water).
Depression in Freezing Point

V.P.1
Solid phase
Liquid phase
V.P.2
 Depression in Freezing Point

Triple point of water

At the triple point, water can exist in three phases, namely, solid, liquid, and
vapour simultaneously. Hence, there can be three forms of equilibria given as
follows:

● Solid ⇌ Vapour
● Liquid ⇌ Vapour
● Solid ⇌ Liquid

Each equilibrium involves two phases. The pressure-temperature (case A) plot for
the water system is given.
 Depression in Freezing Point

Pressure vs Temperature (phase diagram) plot for water

● The point A in the P−T plot is known as a triple point, and all the three
phases (solid, liquid, and vapour) coexist at this point.
● Curve AD represents fusion curve, the equilibrium between ice (solid) and
water (liquid).
● Curve AB represents vapourisation curve, the equilibrium between liquid
water and its vapour (gas).
● Curve AC represents sublimation curve, the equilibrium between ice (solid)
and its vapour (gas).
Depression in Freezing Point

Case A
 Depression in Freezing Point

Depression in freezing point

On the addition of a non-volatile solid to a pure liquid, the freezing point of the
solution becomes lower than that of the pure liquid, that means, the freezing point
of the solution is lowered.
Reason for depression in freezing point
Consider a beaker filled with water. Some non-volatile solute particles are added to
water to form a solution. In the process of freezing, only pure water molecules will
convert into the solid phase to form ice. The non-volatile solute particles do not
enter the solid phase. During freezing, a solid - liquid equilibrium is established.
Since we have ice in its pure form (i.e., devoid of solute particles), the rate of
melting of ice to water is not affected by solute particles.
 Depression in Freezing Point

However, the rate of freezing is affected by solute particles as some of the solute
particles in liquid state will hinder the process of freezing (the solute particles
cannot solidify to form ice). Thus, solute particles decrease the rate of freezing
resulting in a lowering of the freezing point.

Graphical representation

● We know that freezing point is the temperature at which the vapour pressure
of a substance in its liquid phase is equal to the vapour pressure of the
substance in its solid phase.
 Depression in Freezing Point
Graphical representation

lvent
id s o
Liqu

Vapour pressure
e nt l u tion
s olv S o
e n
z
Fro

ΔTf

o
Tf Tf
Temperature in K
 Depression in Freezing Point

● From the graph, it can be observed that the pure solvent freezes at a
temperature Tfo. We know that when a non-volatile solute is added to the
solvent, its vapour pressure decreases (it can be observed from the graph, that
the freezing curve for pure liquid solvent is above the curve for the solution)
and now, it would become equal to that of the solid/frozen solvent at a lower
temperature (Tf ). Thus, the freezing point of the solvent decreases.
● The depression in the freezing point on the addition of non-volatile solute is
given as:
ΔTf = Tf − Tfo
Where, Tfo is the freezing point of the pure liquid, and Tf is the freezing point of
the solution.
 Depression in Freezing Point

Entropy perspective of depression in freezing point

The entropy of a pure substance (solvent) is always less than the entropy of an
impure substance (solution). The freezing of both the solution and the pure solvent
will result in the formation of solid ice (containing pure solvent). The entropy of the
solid is given as Ssolid. Change in entropy when the pure solvent is solidified is given
as:
ΔSsolvent = Ssolid − Ssolvent
Change in entropy when the solution is solidified is given as:
ΔSsolution = Ssolid − Ssolution

Since, Ssolution > Ssolvent , we can say that ΔSsolution > ΔSsolvent.
 Depression in Freezing Point

ΔHfusion
ΔSfusion is related to ΔHfusion ΔSfusion
= Tf
as:
● ∆Hfusion is the enthalpy of fusion of the solvent. Since both the pure solvent and
the solution freezes to form 1 mole of solid, the enthalpy of fusion, ΔHfusion, is
the same in both the cases.
ΔHfusion of solution ΔHfusion of solvent
ΔSfusion = ΔSfusion of solvent =
of Tf Tfo
solution
We know ΔSfusion of solution > ΔSfusion of solvent

Thus, the freezing point of pure solvent (Tfo) is higher than that of the solution (Tf).
 Depression in Freezing Point

Depression in freezing point and molality

Similar to the elevation of boiling point, depression in freezing point (ΔTf) for a dilute
solution (ideal solution) is directly proportional to the molality (m) of the solution.
ΔTf ∝ m
ΔTf = Kf m
Where, Kf is the freezing point depression constant or cryoscopic constant or molal
depression constant.
 Depression in Freezing Point

For a better understanding about the relation of ΔTf and molality (m), an
experiment is given as follow:
Suppose three beakers A, B and C are filled with pure water, 1 m sugar solution,
and 2 m sugar solution, respectively. From the experiment, the freezing point of
pure water is obtained as 0 oC, that of 1 m sugar solution as −1.86 oC and that of
2 m sugar solution as −3.72 oC. Thus, it can be observed that when the molality
of the solution is doubled, ΔTf is also doubled. Thus, ΔTf is directly proportional
to the molality of the solution.
 Depression in Freezing Point

A B C
Water 1 m sugar 2 m sugar
solution solution
Freezing Point 0 oC −1.86 oC −3.72 oC

A B C
Illustration to understand the relation between ΔTf and molality (m)
 Depression in Freezing Point

Since ΔTf = Kf m follows the equation of the straight line, y = mx + c, the plot
between ΔTf and molality is a straight line with a slope Kf . The graph is given as
follow:

ΔTf
(Depression in
freezing point) Slope = Kf

m (molality)
 Depression in Freezing Point

Since the depression in freezing point is only dependent on the

solute concentration and not on its nature, freezing point is a
colligative property.

Characteristics of Kf

● Cryoscopic constant is the depression in freezing point when the

molality of the solution is unity.
We know that, ΔTf = Kf m. When m = 1 molal, ΔTf = Kf .
● Unit of cryoscopic constant is K kg mol−1.
● Kf is dependent on the nature of solvent.
● Kf value is independent of the nature of the solute.
 Depression in Freezing Point
Kf can be calculated as follows:
● In terms of the molar enthalpy of fusion of solvent, ΔHfus.

RTfo 2 M
Kf =
1000 × ΔHfus

Where,
Kf is the cryoscopic constant,
Tfo is the freezing point of the pure solvent (K),
M is the molar mass of the solvent (g mol−1),
ΔHfus is the molar enthalpy of fusion of the solvent (J mol−1),
R is the universal gas constant.
 Depression in Freezing Point
Kf can be calculated as follows:
● In terms of latent heat of fusion of solvent, Lfus

RTfo 2
Kf =
1000 × Lfus

Where,
Kf is the cryoscopic constant,
Tfo is the freezing point of the pure solvent (K),
Lfus is latent heat of fusion of the solvent (in J g−1),
R is the universal gas constant.
 Depression in Freezing Point

Applications of depression in freezing point

(1) Salting of roads in winter

Roads are salted in the winter to reduce the freezing point of water, so that the
removal of ice from roads and footpaths becomes easy. Water normally freezes at
0 oC. On adding salt (i.e., a solute), the freezing point of water is reduced to, say
around, −3 oC (this value is taken for understanding purposes). Thus, the ice
formed will melt at any temperature above −3 oC. Hence, the snow on the road
can be easily removed as it will start to melt when the temperature is above −3 oC.
(2) Adding salt to ice-cream to soften it
It is difficult to chew ice-cube. Hence, salt is added to the ice-cream to lower its
freezing point, so that its softness is maintained.
 Diffusion and Osmosis

Diffusion

The spontaneous flow of particles from a region of higher concentration to a

region of lower concentration is known as diffusion.
Illustration of diffusion in the liquid state
Adding a drop of ink into a glass of water is an example of diffusion. The ink
diffuses in the water because of the random motion of water and ink
molecules. Here, the intermixing of the blue-coloured ink with water takes
place, and gradually, the water turns homogeneously blue.
 Diffusion and Osmosis

Illustration of diffusion in the liquid state

 Diffusion and Osmosis
Illustration of diffusion in the gaseous state
A cuboidal container with a partition in the middle and one part of this
container is filled with gas molecules. Once the partition is removed, the gas
molecules will diffuse from the region of higher concentration to a region of
lower concentration, and spread uniformly.

Illustration of diffusion in gaseous state

 Diffusion and Osmosis

Semipermeable membrane (SPM)

● A membrane, which allows only solvent particles to pass through it is known

as a semipermeable membrane.
● The submicroscopic holes or pores present in the membrane are designed
in such a way that only solvent particles can be passed through these pores.
● The transfer of bigger solute molecules through SPM is hindered.
 Diffusion and Osmosis
Illustration of SPM:
Blue coloured particles represent solvent
molecules and the red coloured particles
represent the solute molecules in the figure
shown. Since the solvent molecules are
smaller than the solute molecules, they can
pass through the holes in SPM. The solute
particles being bigger in size, cannot pass
through the holes in SPM.

Solvent particles can pass through a semipermeable membrane,

but solute particles cannot pass through a semipermeable
membrane.
 Diffusion and Osmosis

Osmosis

● The spontaneous flow of the solvent particles from the solvent side to the
solution side through a semipermeable membrane (SPM) is known as
osmosis.
● In other words, the spontaneous flow of the solvent particles from a solution
of lower concentration to a solution of higher concentration through a
semipermeable membrane is known as osmosis.
● The flow will continue till an equilibrium is attained. Equilibrium implies that
the concentration of both the solvent and the solution must be the equal on
both the sides.
 Diffusion and Osmosis

Osmotic pressure (π)

Illustration of osmotic pressure: A thistle funnel filled with a solution is placed

inside a container, which is filled with solvent. The mouth of the funnel is covered
with a semipermeable membrane. The level of solution rises in the thistle funnel
due to the osmosis of the solvent. ⍴gh is the pressure (i.e., osmotic pressure, π)
exerted by the solution to prevent the inward flow of the solvent into the solution.
When the level of solution in the thistle funnel is showing no further rise, we can
say that no more solvent is entering the solution side (i.e., osmosis has stopped).
Diffusion and Osmosis

Solvent

Solution
Semipermeable
membrane
 Diffusion and Osmosis

● The flow of the solvent from the solvent side to the solution side across a
semipermeable membrane can be stopped if some extra pressure is applied
on the solution side.
● Osmotic pressure is the external pressure which must be applied on the side of
the solution with the higher concentration to stop the process of osmosis.
● Alternatively, osmotic pressure can be also interpreted as the equilibrium
hydrostatic pressure developed by the solution column when it is separated
from the solvent by a semipermeable membrane.
 Diffusion and Osmosis
● Formula for osmotic pressure is given as follows:
π = ⍴gh
Where, π is the osmotic pressure,
⍴ is the density of the solution,
g is the acceleration due to gravity,
h is the equilibrium height.

Some cases of osmotic pressure are discussed below:

Case A:
When solution 1 of concentration C1 is in contact with the pure solvent.
● The external pressure applied on the solution side to prevent osmosis is
given by,
Pext = π1
 Diffusion and Osmosis

Pext

Solution 1 Solvent

C1 SPM

Pext = π1
 Diffusion and Osmosis

Case B:
When solution 2 of concentration C2 is in contact with the pure solvent.
● The external pressure applied on the solution side to prevent osmosis is given
by,
Pext = π2
 Diffusion and Osmosis

Pext

Solution 2 Solvent

C2 SPM
Pext = π2
 Diffusion and Osmosis

Case C:
When solution 1 of concentration C1 is in contact with solution 2 of
concentration C2 and C1 > C2.
● The external pressure applied on the solution 1 (of C1 concentration) side to
prevent osmosis is given by,
Pext = π1 − π2.
 Diffusion and Osmosis
Pext

Solution 1 Solution 2

C1 SPM C2
C1 >
C2= π − π
Pext 1 2
 Diffusion and Osmosis

Osmotic pressure as colligative property

● Osmotic pressure is a colligative property as it depends on the number of

solute molecules and not on their identity or nature.
● The osmotic pressure has been found to depend on concentration of the
solution and temperature.

For dilute solutions, it has been found experimentally that osmotic pressure is
proportional to the molarity, C of the solution at a given temperature T.
Thus,
π ∝ C (molarity) and π ∝ T
 Diffusion and Osmosis

Hence,
π = CRT
Where, π = Osmotic pressure, C = Concentration (mol L−1), R = Universal gas
constant (L atm mol−1 K−1) and T = Temperature (K)

Concentration can be expressed as C = n/V, where n is the number of moles of

the solute and V is the volume of the solution. Substituting C = n/V in the
equation for osmotic pressure,

This equation can be related to the ideal gas equation, PV = nRT

 Diffusion and Osmosis

Graphical representation of osmotic pressure

The equation, π = CRT follows the

equation of a straight line (y = mx + c).
When a graph is plotted between π
osmotic pressure (π) and the molar (Osmotic
concentration of the solute (C) at a pressure) Slope = RT
constant temperature T, we obtain a
straight line with slope RT as shown:

C (Concentration of
solute )
 Types of Solutions
Solutions are classified on the basis of osmotic pressure as follows:
● Hypotonic solutions
● Hypertonic solutions
● Isotonic solutions

Hypotonic solutions and hypertonic solutions

● Consider two solutions (solution 1 and solution 2) of osmotic pressures π1 and

π2, respectively. Consider π2 > π1.
● The solution with the lower osmotic pressure is known as a hypotonic solution.
Here, solution 1 is a hypotonic solution.
● The solution with the higher osmotic pressure is known as a hypertonic
solution. Here, solution 2 is a hypertonic solution.
 Types of Solutions

Isotonic solution

● Two solutions having the same osmotic pressure at a given temperature

are known as isotonic solutions.
● When such solutions are separated by a semipermeable membrane, no
osmosis occurs between them.
 Types of Solutions

Illustration of hypotonic, hypertonic, and isotonic solutions

The white shell of an egg is carefully removed so that a semipermeable
membrane is obtained on the egg.
● When this egg is placed in a solution of low concentration like corn
syrup/vinegar/any solute, then the water flows into the egg and the egg
swells. This solution is known as a hypotonic solution as shown in case A.
● When this egg is placed in a solution with equal concentration like water, no
net loss or gain of water occurs. This solution is known as an isotonic
solution, as shown in case B.
● When this egg is placed in a solution with higher concentration like boric
acid, water will flow out of the egg, and the egg will shrink. Such a solution is
known as a hypertonic solution as in case C.
 Types of Solutions

Hypotonic Isotonic Hypertonic

Solution Solution Solution

Net water gain No net Net water loss

Cell Swells loss or gain Cell Shrinks
Case A Case B Case C
 Reverse Osmosis

● The direction of osmosis can be reversed if a pressure larger than the

osmotic pressure is applied to the solution side.
● If the pressure applied on the solution side is more than osmotic pressure of
the solution, the solvent particles move from the solution to the solvent side
through the semipermeable membrane. This phenomenon is known as
reverse osmosis.
Welcome to

Classes
Chemistry

Solution and Colligative Properties

Colligative Properties Part I

What you already know

● Interaction in liquid-liquid
What you will learn
solutions
● Ideal solutions and non-ideal ● Colligative properties
solutions ● Relative lowering of vapour
● Positive and negative deviation pressure
from Raoult’s law ● Elevation in boiling point
● Practice questions
● Vapour pressure and boiling
point
 Colligative Properties

Colligative properties are properties that do not depend on the nature of the
solute particles but only on the number of the solute particles present in a
solution.

The types of colligative properties that we are going to discuss are:

 Colligative Properties

Relative lowering ΔP
of vapour pressure = χB
P0A

Elevation in boiling
ΔTb = Kbm
point
Colligative
properties
Depression in
ΔTf = Kfm
freezing point

Osmotic pressure π = CRT

 Relative Lowering of Vapour Pressure

When a non-volatile solute is present in a volatile solvent, the vapour pressure of

the solvent decreases. This is known as the lowering of vapour pressure. The
ratio of the lowering of vapour pressure to the vapour pressure of the pure solvent
is known as the relative lowering of vapour pressure (RLVP).
 Relative Lowering of Vapour Pressure

Consider two flasks having a pure solvent, A.

Both the flasks are connected to each other
through a manometer. Now, since both the
flasks have the same solvent in the same
amount, they must also have the same vapour
P1 = P2
pressure, i.e., P1 = P2 = PoA (since both are
Pure solvent Pure solvent A
pure solvent A, so the vapour pressure must
A
be pure vapour pressure). Both flasks have same
vapour pressure
 Relative Lowering of Vapour Pressure

Now, when a non-volatile solute is added to

the flask I, it results in the liquid to rise in the
manometer on the left side, indicating the
decrease in the vapour pressure, i.e., P1 < P2.

This decrease in pressure on adding the P1 < P2

non-volatile solute is due to the coverage of I II
the surface of the solvent by the solute Solution Pure
(non-volatile solvent A
particles, which results in the decrease in the
solute in
number of solvent particles that are able to solvent A)
make up to the vapour phase. Thus, the
Flask I have lower vapour pressure
vapour pressure decreases. than flask II
 Relative Lowering of Vapour Pressure
Example:
Consider two beakers with one having only a volatile solvent (blue balls) and the
other having a non-volatile solute (red balls) and a volatile solvent (blue balls). In the
case of the solvent that contains the non-volatile solute, the solute particles (red
balls) will cover some of the surface area and will, therefore, result in the decrease in
the vapour pressure.

Solute particles occupies

some of the surface area
causing decrease in
vapour pressure
Pure solvent Solvent containing non
volatile solute
 Relative Lowering of Vapour Pressure

Mathematical form of relative lowering of vapour pressure

Consider that a volatile solvent A and a non-volatile solute B form a solution. The
vapour pressure of pure solvent A = PoA
And the vapour pressure of pure non-volatile solute B = PoB = 0 (Since the solute is
non-volatile and will, therefore, not form vapours)

Now, from Raoult’s law, the total pressure of the solution (denoted by Ps) is given as
follows:
Ps = PoAχA + PoBχB
Here, χA is the mole fraction of component A (solvent) and
χB is the mole fraction of component B (solute).
 Relative Lowering of Vapour Pressure

Mathematical form of relative lowering of vapour pressure

Since PoB = 0, Ps = PoAχA + PoBχB = PoAχA

Now, the lowering of vapour pressure is defined as follows:
ΔP = Vapour pressure of the solvent - Vapour pressure of the solution

i.e., ΔP = PoA - Ps
Where, PoA is the pure state vapour pressure of the solvent and PS is the vapour
pressure of solution
 Relative Lowering of Vapour Pressure

Mathematical form of relative lowering of vapour pressure

Formula for the relative lowering of vapour pressure (RLVP)

As we stated earlier, the relative lowering of vapour pressure is the lowering
of vapour pressure per unit vapour pressure of the pure solvent. So, the
relative lowering of vapour pressure is given as follows:
 Relative Lowering of Vapour Pressure

Mathematical form of relative lowering of vapour pressure

 Relative Lowering of Vapour Pressure

Mathematical form of relative lowering of vapour pressure

For dilute solutions, the number of solute particles is much less than that of
the solvent particles, i.e., nA >> nB

Since according to the given derived formula, the relative lowering of vapour
pressure is dependent only on the solute concentration and not on its nature. Hence,
it is a colligative property.
 Relative Lowering of Vapour Pressure

Graphical representation

The relative lowering of a vapour pressure can be represented graphically

against mole fraction of the solute (χB) as follows:

RLVP

χB = 0 χB = 1
χB (mole fraction of the solute)
 Relative Lowering of Vapour Pressure

Graphical representation

If the mole fraction of the solute is 1, i.e., only the molecules of the non-volatile
solute are present, there will be no vapour pressure and hence, lowering of the
vapour pressure = ΔP = PoA - PS = PoA
So, the relative lowering of the vapour pressure is given as follows:

If the mole fraction of the solute is 0, i.e., there are no molecules of the
non-volatile solute (it is pure solvent), the vapour pressure must be equal to pure
state pressure of the solvent, i.e., PoA, and there is no lowering in the vapour
pressure.
 Relative Lowering of Vapour Pressure

Graphical representation

As the mole fraction of solute χB increases, the relative lowering of vapour

pressure also increases.

Alternate formula for RLVP (When the solution is not dilute)

If the solute is not very dilute, then nB cannot be neglected as compared to nA
and the following formula derived must be used.
Relative Lowering of Vapour Pressure
 Elevation in Boiling Point

Boiling point: It is the temperature at which the vapour pressure of the liquid
becomes equal to the atmospheric pressure.

Atmospheric pressure
(downwards)

Vapour pressure
(upwards)
 Elevation in Boiling Point

100 oC 100.52 oC 101.04 oC

I II III
Water 1 mol non-volatile 2 mol non-volatile
solute in water solute in water

Consider three beakers. One beaker is filled with a solvent, the second is filled
with a solution that has 1 mol of a non-volatile solute, and the third is filled with a
solution having 2 mol of a non-volatile solute.
 Elevation in Boiling Point

Now, to boil the liquids, they need to be heated such that their vapour pressure
becomes equal to the atmospheric pressure.

Since the non-volatile solute decreases the vapour pressure of the solution, a
highest temperature is required in the third case, followed by the second case,
and least in the first case in order to make the vapour pressure equal to the
atmospheric pressure.

Therefore, more the amount of solute, more the relative lowering of vapour
pressure and higher the boiling point.
 Elevation in Boiling Point

Let a non-volatile solute B be added to the pure liquid A. After the addition of
B, the vapour pressure of the solution will decrease, and thus the boiling point
of the solution becomes higher than that of the pure liquid. So, the boiling
point is elevated.

Let Tob be the boiling point of the pure liquid and Tb be the boiling point of the
solution.

Then, the elevation in the boiling point = Tb - Tob

 Elevation in Boiling Point
Boiling point of Boiling point of
pure solvent solution
Graphical representation
1 atm
The graphical representation of the
re
vapour pressure vs temperature in K Pu ent
lv

Vapour pressure
so
n
For the pure solvent, the vapour io
l ut
So
pressure is equal to the atmospheric
ΔTb
pressure (1 atm) at Tob. However, for the
solution, a high temperature (Tb) is
required to equalise its vapour pressure
to the atmospheric pressure (1 atm). Tbo Tb
Temperature (K)
 Elevation in Boiling Point

Expression for elevation in the boiling point

The elevation in the boiling point is given by ΔTb = Tb - Tob

Experimentally, it is found that the elevation in the boiling point is directly
proportional to the molality.
i.e., ΔTb ∝ m (molality)
ΔTb = Kbm
Here, the proportionality constant, Kb, is known as the boiling-point elevation
constant, molal elevation constant, or ebullioscopic constant.
If molality m = 1, then ΔTb = Kb. This means that the ebullioscopic constant is the
elevation in the boiling point for 1 molal solution.
 Elevation in Boiling Point

The elevation in the boiling point is dependent on the

solute concentration and not its nature.
 Elevation in Boiling Point

Graphical representation of elevation in the boiling point vs molality

When the graph is plotted ΔTb vs m, a straight line passing through the origin
with slope Kb is obtained.

ΔTb
(Elevation in B.P.)
Slope = Kb

m (molality)
 Elevation in Boiling Point

Characteristics of Kb

1. The unit of ebullioscopic constant is K kg mol-1 since it is the ratio of the

change in temperature to the molality.

2. Kb is the property of the solvent and is independent of the nature of the

solute.

3. Kb is given by the following expression:

 Elevation in Boiling Point

Here, Tb is the boiling point of the pure solvent (K)

M is the molar mass of the solvent (g)

ΔHvap is the molar enthalpy of vaporization of the solvent (Unit: J mol-1)

Lvap is the latent heat of vaporization of the solvent (Unit: J g-1 )

 The relative lowering in the vapour pressure of 1 kg of an aqueous
solution containing 50 g of a non-volatile solute is 0.02. Calculate
the molality of the solution and the molar mass of the solute.

Solution

Step 1: Calculating the number of moles of the solvent

Mass of the solvent = Mass of the solution - Mass of the solute
Therefore,
⇒ Mass of the solvent water = 1000 - 50 = 950 g
Step 2: Calculating the molar mass of the solute
As given,
Relative lowering of vapour pressure = χB = 0.02

On reversing this equation, we get,

⇒ nA = 49nB

⇒ MB = 46.42 g
Step 3: Calculating the molality

Molality (m) = 1.13 mol kg-1

Therefore, the molar mass of the solute is 46.42 g and molality of the
solution is 1.13 mol kg-1.
Calculate the weight of urea that must be dissolved in 400 g of
water such that the final solution has a vapour pressure 2%
less than the vapour pressure of pure water.

(a) 17.2 g (b) 27.2 g

(c) 37.2 g (d) 47.2 g

 Solution

Step 1: Calculating the RLVP

Since the % relative change the in vapour pressure is 2%.

Step 2: Calculating the number of moles of the solvent

As given,
Mass of water = 400 g
Step 3: Calculation of weight of urea to be taken
Since the molecular formula of urea is NH2CONH2,
Molar mass of urea = 2 × Molar mass of N + 4 × Molar mass of H + Molar mass
of C + Molar mass of O
= (2 × 14) + (4 × 1) + 12 + 16 = 60 g
Now, the relative lowering of vapour pressure is given by,
On Reversing the above equation, we get:
Therefore, the weight of urea that needs to be taken is 27.2 g.
Thus, option (b) is the correct answer.
 Calculate the molal elevation constant of water, given that 0.1
molal aqueous solution of a substance boils at 100.052 oC.

Solution

Step 1: Calculating the elevation in the boiling point

Since Tb and Tob are in degree celsius
As we know, ΔTb = (Tb + 273) K - (Tob + 273) K = Tb - Tob
And Tb = 100.052 oC;
Tob = 100 oC
So, the elevation in the boiling point is given as follows:
ΔTb = Tb - Tob
⇒ ΔTb = 100.052 - 100 K
⇒ ΔTb = 0.052 K
Step 2: Calculating the ebullioscopic constant
As we know, ΔTb = Kbm
⇒ 0.052 = Kb × 0.1

Therefore, the value of the ebullioscopic constant is 0.52 K kg mol-1.

 The boiling point of benzene is 353.23 K. When 1.80 g of a
non-volatile solute was dissolved in 90 g of benzene, the
boiling point rose to 354.11 K. Calculate the molar mass of the
solute. (Kb for benzene is 2.53 K kg mol-1) .

Solution

Step 1: Calculating the elevation in the boiling point

As the elevation in the boiling point is given by ΔTb = Tb - Tob
⇒ ΔTb = 354.11 - 353.23 K
⇒ ΔTb = 0.88 K
Step 2: Calculating the molality
Since the elevation in the boiling point is given by ΔTb = Kbm,
⇒ 0.88 = 2.53 × m
⇒ m = 0.3478 mol kg-1

Step 3: Calculating the number of moles of the solute

Now, the molality of the solution (m), in terms of number of moles of
the solute, can be expressed as follows:

⇒ n = 0.0313 mol

Step 4: Calculation of molar mass of solute

Molar mass of the solute = 57.5 g mol-1

Therefore, the correct answer is 57.5 g mol-1.

 The boiling point of pure water is 100 oC. Calculate the boiling point
of an aqueous solution containing 0.6 g of urea (molar mass = 60 g
mol-1) in 100 g of water. (Kb for water is 0.52 K kg mol-1).

Solution

Step 1: Calculating the molality

Since the molality of the solute is given as follows,
⇒ Molality = 0.1 m

Step 2: Calculating the elevation in the boiling point

The elevation in the boiling point is given by ΔTb = Kbm
⇒ ΔTb = 0.52 × 0.1
⇒ ΔTb = 0.052 K
Step 3: Calculating the boiling point of the solution
⇒ ΔTb = Tb - Tob
⇒ 0.052 = Tb - 100
⇒ Tb = 100.052 oC

Therefore, the boiling point of the solution is 100.052 oC.

Welcome to

Classes
Chemistry

Solutions and Colligative Properties

Colligative Properties Continued

What you already know

● Colligative properties
What you will learn
● Relative lowering of vapour
pressure and its graphical ● Characteristics of Kb
representation ● Elevation of boiling point
● Elevation in boiling point and its ● Ostwald-Walker method
graphical representation ● Question based on
● Characteristics of ebullioscopic Ostwald-Walker method
constant
● Practice questions
 Characteristics of Ebullioscopic Constant (Kb)
● Kb is the property of the solvent and it is independent of the nature of solute.
● The unit of the ebullioscopic constant (Kb) is K kg mol−1.
● The formula of the elevation of boiling point in terms of the heat of vaporisation
is given as follows:

Where,
Kb = Ebullioscopic constant
R = Gas constant (in J K−1 mol−1)
Tb = Boiling point of the pure solvent (in K)
M = Molar mass of solvent (in g mol−1)
ΔHvap = Molar enthalpy of vaporisation of the solvent (in J mol−1)
 Characteristics of Ebullioscopic Constant (Kb)

● The formula of the elevation of boiling point in terms of the latent heat of
vaporisation is given as follows:

Where,
Kb = Ebullioscopic constant
R = Gas constant (in J K−1−1 mol−1)
Tb = Boiling point of the pure solvent (in K)
Lvap = Latent heat of vaporisation of the solvent (in J g−1)
 Elevation of boiling point

Justification of the elevation in boiling point by entropy

A solution is made by dissolving a non-volatile solute in a volatile solvent. So,

when the solution is heated, vapours are formed only from the solvent.

Let us consider two cases

Case I: A pure solvent is vaporised from its liquid state.
Case II: The solution prepared by dissolving non-volatile solute is vaporised from
its liquid state.

The entropy of a pure substance (solvent) is always less than the

entropy of an impure substance (solution).
 Elevation of boiling point

Thus, in both the cases vapours contains only solvent molecules. We know that a
solution always has a greater entropy as compared to a pure solvent as there is
more randomness in solution. Therefore, the liquid form of the pure solvent (case
I) has less entropy as compared to solution. However, both have the same
entropy in the final state, as final state has only solvent particles. Thus, in the first
case, there is a high entropy change between the initial state and the final state
as compared to the second case.
 Elevation of boiling point

Vapour is always pure solvent

Svapour

ΔSvapour, solution
ΔSvapour, solvent

Ssolution
More entropy more
Ssolvent randomness

Case I Case II
Case I has higher entropy change than case II
 Elevation of boiling point

First case (Solvent) Second case (Solution)

Entropy change is given as: Entropy change is given as:

Where: Where:
ΔSo = Entropy change of pure solvent ΔSS = Entropy change of solution
Tbo = Boiling point of pure solvent TbS = Boiling point of solution
 Elevation of boiling point

The entropy change of a pure solvent (ΔSo) is greater as compared to the

entropy change of a solution (ΔSS). Since ΔHvap is the same, the value of Tbo
should be less than TbS.

Conclusion: When a non-volatile solute is added to a solvent, there is an

elevation in the boiling point of the solution, which is always greater than that of
the pure solvent.
 Ostwald-Walker Method

● It is a dynamic method to measure the pressure of a solution and a solvent.

● In this method, dry air is passed through the solution, solvent, and
drying/dehydrating agent. The dry air carries vapours with it. The amount of
vapours carried over is proportional to the vapour pressure over the liquid.
There is a corresponding change in the weight.
I. Amount of vapours carried over from the solvent ∝ Saturated vapour
pressure of the solvent (P∘); The weight of the solvent decreases.
II. Amount of vapours carried over from the solution ∝ Saturated vapour
pressure of the solution (Ps).
 Ostwald-Walker Method

III. Dry air passed first through the solvent carries vapours proportional to P∘. If
passed through the solution next, it condenses the vapours in the solution
and carries only the ones proportional to Ps.
IV. When most of the air is passed through a dehydrating agent, the weight of
the dehydrating agent increases because of the absorption of the moisture
present in the air.
 Ostwald-Walker Method

Case 1

Dry air is passed through a pure solvent (i.e., water) and then through a dehydrating
agent, for example, anhydrous CaCl2.
Dry air
Anhydrous CaCl2
(dehydrating
agent)
Po

Solvent
 Ostwald-Walker Method

● When the solvent is poured into a flask, there is an equilibrium between the
liquid and vapour phases of the solvent. When dry air passes through the pure
solvent, the dry air takes away the vapour molecules that are present over the
solvent and air becomes moist.
● The moist air is passed through anhydrous CaCl2, which absorbs moisture from
the moist air. As moisture is absorbed by anhydrous CaCl2, its weight
increases. The gain in the weight of the dehydrating agent is directly
proportional to the vapour pressure of the pure solvent.
Thus,

Gain in weight of the dehydrating agent ∝ Po

 Ostwald-Walker Method

● As the vapours are absorbed by the dry air, there is a disturbance in the
equilibrium between the liquid and vapour phases of the solvent, and to
maintain this equilibrium, solvent evaporates. This leads to a decrease in the
mass of the solvent. The loss in the weight of the solvent is directly
proportional to the vapour pressure of the solvent.
Thus,

Loss in weight of the solvent container ∝ Po

 Ostwald-Walker Method

Case 2

Dry air is passed through a pure solvent, followed by a solution with a non-volatile
solute, and then through the dehydrating agent.

Dry air
Anhydrous CaCl2
(dehydrating
Po agent)
Ps

Solvent Solution
 Ostwald-Walker Method

● When dry air is passed through the pure solvent, it absorbs the water vapour,
followed by which is made to pass through the solution. The solution also has
vapours, but these vapours are less in amount (population density is less) as
compared to the vapours of the pure solvent because a non-volatile solute is
present in it.
● As the solvent vapours are absorbed by the dry air, the equilibrium is
disturbed. To maintain the equilibrium, evaporation of the solvent takes place
and this leads to a decrease in the weight of the solvent. Therefore, the loss of
the weight of the solvent container is directly proportional to the vapour
pressure of the solvent.
Thus,

Loss in weight of the solvent container ∝ Po

 Ostwald-Walker Method

● The air coming from solvent is more humid as compared to the solution
because vapour pressure of solvent is greater than solution. Thus, as the moist
air is passed through the solution, some weight of the moist air is lost to
maintain the pressure of the solvent. Hence, the weight gain of the solution is
proportional to the difference between the vapour pressure of the pure solvent
and solution. Therefore,
Gain in weight of the solution ∝ Po − PS

● The moist air is passed through the dehydrating agent and the moisture is
absorbed by this dehydrating agent. Thus, the gain in the weight of the
dehydrating agent is directly proportional to the vapour pressure of the
solution. Therefore,
Gain in weight of the dehydrating agent ∝ PS
 Ostwald-Walker Method

According to Raoult’s law, the vapour pressure of a solution that has a

non-volatile solute is less than the vapour pressure of a pure solvent.
PS < Po

Case 3

Dry air is passed through two flasks of a pure solvent and then through the
dehydrating agent.
 Ostwald-Walker Method

Dry air

Anhydrous CaCl2
(dehydrating
Po agent)

Solvent
 Ostwald-Walker Method

● When dry air passes through a pure solvent, it takes away the vapour molecules
that are present over the solvent and becomes moist. This moist air is passed
through the same solvent again, which has the same vapour pressure as
previous. The moist air passes through anhydrous CaCl2, which absorbs the
moisture from the moist air. Therefore, the gain in the weight of the dehydrating
agent is directly proportional to the vapour pressure of the solvent. Thus,

Gain in weight of the dehydrating agent ∝ Po

● Thus, the loss in the weight of the solvent container is also directly proportional
to the vapour pressure of the solvent. Therefore,

Loss in weight of the solvent container ∝ Po

 Ostwald-Walker Method
Case 4

Dry air is passed through a solution, followed by a pure solvent, and then through
the dehydrating agent.

Dry air
Anhydrous CaCl2
(dehydrating
agent)

Solution Solvent
 Ostwald-Walker Method

As we know, the solution has less population density as compared to the solvent.
As the dry air is passed through the solution, it absorbs some vapours and then this
moist vapour passes through the solvent that has more vapour pressure as
compared to solution. Due to this, the moist air absorbs more water vapours and
the air that is more humid is passed through the dehydrating agent, where the
moisture is absorbed by the dehydrating agent. Therefore,
● The loss in the weight of the solution container is directly proportional to the
vapour pressure of the solution. Thus,
Loss in weight of the solution container ∝ PS
 Ostwald-Walker Method

● The loss in the weight of the solvent container is directly proportional to the
difference between the vapour pressure of the pure solvent and solution.
Thus,
Loss in weight of the solvent container ∝ Po − PS

● The gain in the weight of the dehydrating agent is directly proportional to the
pure solvent.
Thus,
Gain in weight of the dehydrating agent ∝ Po
 Ostwald-Walker Method

Case 5

Dry air is passed through two identical solution containers and then through the
dehydrating agent.

Dry air
Anhydrous CaCl2
(dehydrating agent)
Ps

Solution
 Ostwald-Walker Method

● When dry air passes through the solvent, it takes away the vapour molecules
that are present over the solution and becomes moist air. This moist air is passed
through the same solution container again, it has the same vapour pressure as
previous. The moist air passes through anhydrous CaCl2 which absorbs the
moisture from the moist air. Therefore, the gain in the weight of the dehydrating
agent is directly proportional to the vapour pressure of the solution. Thus,
Gain in weight of the dehydrating agent ∝ PS

● The loss in the weight of the solution is directly proportional to the vapour
pressure of the solution. Therefore,
Loss in weight of the solution ∝ PS
 Dry air is passed through a solution of 5 g of a solute in 80 g of
water, and then it is passed through pure water. The loss in the
weight of the solution is 2.50 g and the loss in the weight of pure
water is 0.04 g. What is the molecular weight of the solute?

Solution

In this case, the dry gas first passes through the solution and then through the
solvent. Thus, it is similar to case 4 of the Ostwald-Walker method.

According to this case,

● Loss in weight of the solution container ∝ PS = k PS
● Loss in weight of the solvent container ∝ Po − PS = k (Po − PS)
Given,
Loss in mass of the solution = 2.5 g
Loss in weight of the solvent = 0.04 g
By taking their ratio,

By Raoult's law,
PS = PAo 𝜒A + PBo 𝜒B
However, for a non-volatile solute,
PS = PAo 𝜒A
 Po 𝜒solvent
Po (1 − 𝜒solvent )

𝜒solvent
𝜒solute

62.5 ×
 Dry air was passed through a solution of 2.5 g of a non-volatile
solute in 100 g of water and then through pure water. The loss in
the weight of the former was 1.25 g and that of the latter was 0.05
g. Calculate the following:
(i) Molecular weight of the solute
(ii) Mole fraction of the solute

Solution

In this case, the dry gas first passes through the solution (former) and then through
the solvent (latter). Thus, it is similar to case 4 of the Ostwald-Walker method.
According to this case,
● Loss in weight of the solution container ∝ PS = k PS
● Loss in weight of the solvent container ∝ Po − PS = k (Po − PS)
Given,
Loss in mass of the solution = 1.25 g
Loss in weight of the solvent = 0.05 g
(i) Calculation for molecular weight of the solute
Loss in mass of solution 1.25 g k PS
= =
Loss in weight of solvent 0.05 g k (Po − PS)

PS
25 =
(Po − PS)

By Raoult's law,
PS = PAo 𝜒A + PBo 𝜒B
However, for a non-volatile solute,
PS = PAo 𝜒A
 PS PS 𝜒solvent
25 = =
(Po − PS) Po(1 − 𝜒solvent )

𝜒solvent
25 = 𝜒
solute
(ii) Calculation for the mole fraction of the solute
By the equation, we get,

𝜒solute =
Welcome to

Classes
Chemistry

Solutions and
Colligative Properties
Abnormal Colligative Properties and
van't Hoff Factor

What you already know What you will learn

● Depression in freezing point ● Abnormal colligative properties
● Osmosis and osmotic pressure ● Corrected colligative properties
● Types of solutions ● van’t Hoff factor (i)
● Reverse osmosis ● Degree of dissociation
● Degree of association
 Calculate osmotic pressure of 0.1 M aqueous solution of urea
at 300 K?

Solution

Given,
C = Concentration of aqueous solution = 0.1 M or 0.1 mol L−1,
R = Gas constant = 0.0821 L atm mol−1 K−1, T = Temperature (K) = 300 K
The formula to compute the osmotic pressure:
π = CRT
So, π = 0.1 mol L−1 × 0.0821 L atm mol−1 K−1 × 300 K
π = 2.463 atm
Hence, osmotic pressure of 0.1 M aqueous solution of urea at 300 K is
2.463 atm.
 A red coloured aqueous solution is brought into contact with
pure water through a semipermeable membrane. What will
be the colour of the aqueous solution after osmosis has
occurred ?

Solution

Osmosis is a process in which only the solvent moves and not the solute. So
that means the colour of the solution is due to the solute and now if the solvent
(water) moves to the solution part, then the solution will become dilute and the
colour of the solution will change from red to faded red whereas the solvent
colour will remain the same.
 A solution of urea is isotonic with a 12 g L−1 glucose solution.
The concentration of urea solution is:

(a) 4 g L−1 (b) 12 g L−1

(c) 16 g L−1 (d) 1 g L−1

Solution

Isotonic solution: Two solutions having same osmotic pressure, π1 = π2

As we know, π = CRT
C1RT = C2RT
C1 = Concentration of glucose solution and C2 = Concentration of urea solution
C1 = C2
Now, Strength
Concentration of glucose (C1) =
Molecular mass

12 g L−1 2
Concentration of glucose (C1) = = mol L−1
180 g mol−1 30

Strength
Concentration of urea (C2) =
60
Strength 2
= mol L−1
60 30
Concentration of urea solution is: 4 g L−1
Hence, option (a) is the correct answer.
 Abnormal Colligative Properties
Colligative Properties

● Relative lowering in vapour pressure ● Elevation in boiling point

Δp1 ΔTb = Kb × m
o
= 𝛘2
p 1

● Depression in freezing point ● Osmotic pressure

ΔTf = Kf × m π = CRT

While computing the values of colligative properties theoretically, it was found that
these values are different from the values which are connected to the real world. This
difference in the values was then known as the abnormal nature in colligative
properties.
 Abnormal Colligative Properties
Why was there an abnormality?

● Let’s understand through an example,

Let's consider two beakers, one beaker containing one mole of non-volatile
solution of AB and another beaker containing one mole of non-volatile solution
of XY. Consider XY dissociates into X+ and Y− but AB does not undergo
dissociation. Due to the dissociation of XY the number of particles of XY in the
solution seemingly becomes double as that of AB and as we know that increase
in the number of particles, increases the elevation in boiling point in XY. So,
here comes the abnormality.
● AB and XY solutions were supposed to have equal elevation in boiling point but
XY solution has more than AB solution because of the dissociation.
 Abnormal Colligative Properties
1 mol non-volatile
solute AB
373.15 K 373.67 K

Solvent
B
A
 Abnormal Colligative Properties
1 mol non-volatile
solute XY
373.15 K 374.13 K

Solvent
Y−
+
X
 Abnormal Colligative Properties

Let us take another situation,

Let's consider 2 beakers, one beaker containing one mole of non-volatile solution
of M and another beaker containing one mole of non-volatile solution of N.
The elevation in boiling point of N is less than of the same for M as N undergoes
association to form N2, but M does not undergo any change.
Now, due to that association, the number of particles of solute has reduced. Due
to this association, the calculated and observed value of elevation in boiling points
are different.
 Abnormal Colligative Properties

1 mol non-volatile
solute M
373.15 K 373.67 K

Solvent M
 Abnormal Colligative Properties

1 mol non-volatile
solute N
373.15 K 373.41 K

Solute N
associates in
Solvent N N solvent
 Abnormal Colligative Properties

Colligative properties depend upon the number of solute particles in the solution.
● Abnormality in colligative properties occurs when the electrolytic solutes can
either dissociate or associate in the solvent.
● This leads to an increase or decrease in the number of solute particles.
● Actual value of colligative properties is different from the theoretical value.

To remove the error cause, we multiply colligative property with ’i’ which is
known as van't Hoff factor.
 Abnormal Colligative Properties

Dissociation of solute

Let’s take a case, when 1 mol of KCl is present in an aqueous solution but as KCl
dissociates into one mole of K+ and one mole of Cl−, so due to that there are 2 moles
of solute particles in the solution.
So ,
Number of molecules (actual)
i=
Number of molecules (expected)

2 moles (K+ , Cl− )

i= =2
1 mole
 Abnormal Colligative Properties
Note
● Colligative properties depend upon the number of solute particles which actually
depend on association and dissociation of solute in solvent.
● Association or dissociation both will cause abnormal colligative property which can
be corrected by introducing van't Hoff factor (i).
Moles of particles in solution after association or dissociation
● van’t Hoff factor (i) =
Moles of solute dissolved
● van’t Hoff factor (i) for electrolytic solution is not equal to 1
■ If it is association, i < 1 ■ If it is dissociation, i > 1
● van’t Hoff factor (i) for non-electrolytic solutions is equal to 1 as they do not
undergo association or dissociation.
Examples: Urea, glucose and sucrose etc.
 Considering the van't Hoff factor (i) = no. of ions in the
respective formula units, what is the van’t Hoff factor for the
following chemical species ? (Assuming 100% dissociation)

(a) NaCl (b) Urea

(c) Al2(SO4)3 (d) NaOH

Solution
(a) For NaCl: As NaCl dissociates into (c) For Al2(SO4)3: van’t Hoff factor (i) = 5
Na+ and Cl−, As Al2(SO4)3 dissociates into two Al3+
So, van’t Hoff factor (i) = 2. and three SO42− .
(b) For Urea: van’t Hoff factor (i) = 1 (d) For NaOH: van’t Hoff factor (i) = 2
As there is no association and As NaOH dissociates into Na+ and
dissociation. OH−.
 Which of the following will give the maximum value of van’t
Hoff factor (i) in an aqueous solution?

(a) 1 mole of sugar (b) 1 mole of urea

(c) 1 mole of Al2(SO4)3 (d) 1 mole of NaCl
Solution
The substance which can dissociate into the most number of ions will have the
highest van’t Hoff factor (i) value so let’s check for each option,
(a) For sugar, van’t Hoff factor (i) = 1, as there is no association and dissociation.
(b) For urea, van’t Hoff factor (i) = 1, as there is no association and dissociation.
(c) For Al2(SO4)3, van’t Hoff factor (i) = 5, as it dissociates into 2Al3+ and 3SO42−.
(d) For NaCl, van’t Hoff factor (i) = 2, as NaCl dissociates into Na+ and Cl− .
Hence, option (c) is the correct answer.
 Corrected Colligative Properties

● Relative lowering in vapour pressure ● Elevation in boiling point

Δp1 ΔTb = i × Kb × m
= i × 𝛘2
po1

● Depression in freezing point ● Osmotic pressure

ΔTf = i × Kf × m π = i × CRT
 van't Hoff factor (i)

Formulae

Experimental CP (observed)
i=
Calculated CP (expected)

Normal or Theoretical Molar mass

i=
Abnormal or Observed Molar mass

No. of moles after association or dissociation

i=
No. of moles before association or dissociation
 van't Hoff factor (i)
Dissociation:
Let’s have 12 chalk pieces of 36 g, then break each chalk into two piece, now
you have 24 pieces of chalk of the same mass that is 36 g. Now if you take 12
chalk pieces from those 24 chalk pieces, the mass of 12 chalk pieces will be 18 g
only. The mass of one dozen chalk pieces decreases from 36 g to 18 g. In the
similar way, dissociation decreases the molar mass.
Association:
Suppose we are having a cello chair each having mass 100 g, so a dozen mass
(Mass of 12 chairs) is 1200 g. As, we glued two chairs and now they are looking
like one chair only, so the number of such chairs will be 6 only but the mass
remains 1200 g (Association). So, we can conclude that in the association dozen
mass increases.
 van't Hoff factor (i)

When any solute undergoes association or dissociation, the total mass of them
does not change although the number of solute particles in the solvent
changes. But upon association or dissociation molar mass does change
although total mass does not. Molar mass changes because in these
conditions molar mass depends upon the smallest unit of solute which exists in
the solution which is definitely affected by the association or dissociation.
 Degree of Dissociation (𝛼)

Definition: Degree of Dissociation (𝛼) is a measure of the extent of dissociation.

Suppose C is the concentration of a solute An in 1 L of solution, which dissociates
as:

An ⇌ nA i = 1 + 𝛼 (n − 1)
(i − 1)
Initial conc. C 0 𝛼=
(n − 1)
Equilibrium conc. C − C𝛼 n𝛼C
Hence for dissociation,
No. of moles after association or dissociation i = 1 + 𝛼 (n − 1)
i=
No. of moles before association or dissociation
C − C𝛼 + n𝛼C
i=
C
 Degree of Dissociation (𝛼)
Examples

(1) For NaCl (100% ionised), (3) For K4[Fe(CN)6] (75% ionised),
𝛼=1 𝛼 = 0.75
i = 1 + 𝛼 (n − 1) i = 1 + 𝛼 (n − 1)
= 1 + 1 (2 − 1) = 1 + 0.75 (5 − 1)
van’t Hoff factor (i) = 2 van’t Hoff factor (i) = 4

(2) For BaCl2 (100% ionised), (4) If K4[Fe(CN)6] is 100% ionised

𝛼=1 van’t Hoff factor (i) = 5, as it will
i = 1 + 𝛼 (n − 1) dissociate into four K+ and one
= 1 + 1 (3 − 1)
[Fe(CN)6]4−.
van’t Hoff factor (i) = 3
 Degree of Dissociation (𝛼)
Examples

Suppose C is the concentration of a solute HA in 1 L of solution, which dissociates as:

HA ⇌ H+ + A−
Let it be 50% dissociated, so 𝛼 = 0.5
HA ⇌ H+ + A−
Initial conc. C 0 0
Equilibrium conc. C − 0.5C 0.5C 0.5C

Total number of moles of particles after dissociation = (1 − 0.5 + 0.5 + 0.5) C = 1.5 C

No. of moles after association or dissociation 1.5 C

i= = = 1.5
No. of moles before association or dissociation C
 Degree of Dissociation (𝛼)

Effect of dissociation

● Number of solute particles increases.

● Colligative property (CP) increases.
● Molar mass (MM) of solute decreases.
● Observed molecular mass is less than expected molecular mass.
 Degree of Association (β)
Association

The degree of association (β) is the measure of the extent of association.

● Some organic solutes undergo an association in a non-aqueous solution.
● Acetic acid dimerizes in benzene, 2CH3COOH ⇌ (CH3COOH)2
Formula:
● Suppose C is the concentration of B in 1 L solution that combines to form
associated molecules Bn.
nB ⇌ Bn
Initial conc. C 0
Cβ
Equilibrium conc. C − Cβ
n
 Degree of Association (β)

No. of moles after association or dissociation

i=
No. of moles before association or dissociation
Cβ
Total number of effective moles after dissociation = C − Cβ +
n
Cβ
C − Cβ +
n
i=
C
β 1
i= 1−β+
n
⇒ i =1 + β −1
n
n
⇒ β = (i − 1) (1 − n)
 Degree of Association (β)

Effect of association

● Number of solute particles decreases.

● Colligative property (CP) decreases.
● Molar mass (MM) of solute increases.
● Hence, observed molar mass is more than expected molar mass.
Welcome to

Classes
Chemistry

Solutions and Colligative Properties

A Deeper Dive into the Solution

What you already know What you will learn

● Solution and its ● Concentration terms

characteristics ● Types of solution
● Components of a solution ● Solubility
● Identifying solute and solvent ● Factors affecting solubility
● Measuring concentration of ● Evaporation
solutions ● Partial pressure
● Henry’s law
 Concentration Term
It can be classified into two types, which are given as follows:

Concentration terms

Temperature-dependent Temperature-independent

All volume-dependent concentration terms are dependent on the

temperature. Thus, as the temperature changes (increases or
decreases), the concentration term also changes accordingly.
 Concentration Term
Temperature-dependent concentration terms

Concentration
Formula Unit
term

Weight of solute (in g)

Strength (S) Strength = g L−1
Volume of solution (in L)

Number of moles of solute

Molarity (M) Molarity = mol L−1
Volume of solution (in L)
 Concentration Term
Concentration
Formula Unit
term

Number of gram equivalent of solute

Normality (N) Normality = Eq. L−1
Volume of solution (in L)

w w Weight of solute (in g) g mL−1

% % = × 100
V V Volume of solution (in mL)

V Volume of solute (in mL)

V % = × 100
% V Volume of solution (in mL) -
V
 Concentration Term

Temperature-independent concentration terms

The concentration terms that do not dependent on the temperature are given
as follows:

Concentration Formula Unit

term
Number of moles of solute
Molality (m) Molality = mol kg−1
Weight of solvent (in kg)
 Concentration Term

Concentration
Formula Unit
term

Moles of component
Mole fraction (𝛘) Mole fraction = -
Total moles

Parts per million Weight of solute

ppm = × 106 -
(ppm) Weight of solution

w w Weight of solute
% % = × 100 -
w w Weight of solution
 Types of Solution
One or more components present in the solution other than solvent are known
as solutes.

Based on the number of components

Binary solution Ternary solution Quaternary solution

It has only one solute in the It has two solutes in the It has three solutes in
solution solution the solution
(One solute + One solvent) (Two solute + One (Three solute + One
solvent) solvent)
Sugar in water Sugar + Salt solution in Lime juice + Salt + Sugar
water solution in water
 Types of Solution

Analogy
Consider that we are making the lime solution. When only lime juice is
added in water, it has only one solute in the water and it is known as a
binary solution (one solute + one solvent). After adding sugar to the
solution, the solution has two solutes (lime juice + sugar) and it is known as
a ternary solution (two solutes + one solvent). Again, on the addition of salt
in the solution, it has three solutes (lime juice + sugar + salt) and it is known
as a quaternary solution (three solutes + one solvent).
 Types of Solution

Binary solution Ternary solution Quaternary

(Water + lime) (Lime water + sugar) solution
(Lime water +
sugar + salt)
Making of lemonade
 Types of Solution

Based on phase of solute and solvent

There are total nine combinations of solute and solvent on the basis of the phases:

Type of Solute Solvent

Examples
solutions phase phase
● In a CNG cylinder, propane, ethane,
Gaseous
Gas Gas etc., are dissolved in methane.
solution
● Mixture of O2 and N2 gases
 Types of Solution

Solute Solvent
Type of solutions Examples
phase phase
● CHCl3 mixed with N2
Liquid Gas gas
Gaseous
● Water in oxygen
solution
● Camphor in nitrogen
Solid Gas gas
● Iodine vapours in air
 Types of Solution

Type of Solute Solvent

Examples
solutions phase phase
● Oxygen dissolved in water
Gas Liquid
● CO2 dissolved in water
● Acetic acid dissolved in
Liquid Liquid Liquid water
solution ● Ethanol dissolved in water

● Sugar in water
Solid Liquid
● Salt in water
 Types of Solution

Type of Solute Solvent

Examples
solutions phase phase
● Air trapped in ice
Gas Solid
● H2 adsorbed on palladium
● Water molecules in the
Solid Liquid Solid CuSO4 lattice
solution ● Sodium amalgam

● Tin in Copper
Solid Solid
● Copper in gold
 Types of Solution

Based on amount of solute dissolved

Based on the amount

of the solute dissolved

Unsaturated Saturated Supersaturated

 Types of Solution

1. Unsaturated solution: A solution that contains less amount of solute than

the maximum amount of solute, which can be dissolved at that
temperature and pressure, is known as an unsaturated solution. In an
unsaturated solution, no precipitation is observed.
Example: Suppose a maximum of 15 g of sugar can be dissolved in water
and if the water has less than 15 g of sugar, then it is an unsaturated
solution.

2. Saturated solution: A solution that contains the maximum amount of

solute, which is capable of dissolving or no more solute can be dissolved
at the same temperature and pressure, is known as a saturated solution.
 Types of Solution
In a saturated solution, there is no precipitation. It is just a boundary between
the precipitation and dissolution (take place or not).
Example: Suppose a maximum of 15 g of sugar can be dissolved in water and if
the water has 15 g of sugar, then it is a saturated solution.

3. Supersaturated solution: A solution that contains more amount of solute

than the maximum amount of solute, which can be dissolved at a given
temperature and pressure, is known as a supersaturated solution. In a
supersaturated solution, precipitation takes place.
Example: Suppose a maximum of 15 g of sugar can be dissolved in water
and if the water has more than 15 g of sugar, then it is a supersaturated
solution.
 Solubility

● The solubility of a substance is the maximum amount of that substance

which can be dissolved in a specified amount of solvent at a particular
temperature and pressure.
● It depends upon the nature of solute and solvent as well as temperature
and pressure.
 Factors-Affecting Solubility

There are three major factors that affect the solubility of any substance.

Nature of Temperature of Pressure of the

the solvent and the system
the solute system
 Factors-Affecting Solubility

Nature of the solvent and solute

Every solid does not dissolve in a given solvent. It is observed that polar
solutes dissolve in polar solvents and nonpolar solutes dissolve in nonpolar
solvents. In general, a solute dissolves in a solvent if the intermolecular
interactions are similar in the two (like dissolves like).

Example:
In the case of water, there is a hydrogen bonding between the hydrogens of
one water molecule and oxygen of another water molecule.
 Factors-Affecting Solubility

Due to this hydrogen bonding, water is liquid in nature. In the given structure,
the dotted green line represents the hydrogen bonding.

Hydrogen bonding in water

 Factors-Affecting Solubility

Effect of temperature

Solution (solute + solvent) reaches the stage when the two processes
(dissolution and crystallisation) occur at the same rate. Under such conditions,
the number of solute particles going into solution will be equal to the solute
particles separating out and a state of dynamic equilibrium is reached.
Solute + Solvent ⇌ Solution … (1)
The solubility of a solid in a solvent is significantly affected by temperature
changes. Consider the equilibrium represented by equation (1) that follows Le
Chatelier's principle.
 Factors-Affecting Solubility
According to Le Chatelier's principle,
● In general, if the dissolution process is endothermic (ΔsolH > 0), then the
solubility increases with the rise in temperature.
● If the dissolution process is exothermic (ΔsolH < 0), then the solubility
decreases with an increase in temperature.

Steps involved in dissolution

Step 1: It involves the separation of solvent molecules (∆H1) because every
solvent has an attraction force between the solvent molecules. If any solute is
added to it, then there should be some distancing between the solvent
molecules for dissolving the solute into it.
 Factors-Affecting Solubility

Step 2: It involves the separation of solute molecules (∆H2) because every

solute has an attraction force between the solute molecules. If it is added
to solvent, then there should be some distancing between the solute
molecules to get dissolved in the solvent.
Step 3: Here, the solute and solvent molecules mix (∆H3). When the solute
is dissolved in the solvent, there is an attraction between the solute and
solvent molecules, leading to stability or releasing the energy.

Dissolution can be an exothermic or an endothermic process

depending upon all the three steps in which the first two steps
requires energy, but in the third step, energy is released.
 Factors-Affecting Solubility

Example:
If a soda bottle is put in both cold and hot water, it is observed that the
soda in the cold environment has more taste (more amount of dissolved
CO2) as compared to the soda in the hot environment because dissolving
CO2 in water is an exothermic reaction. Furthermore, as the temperature
increases, the solubility of the CO2 in water decreases. Due to this, the
soda loses its taste in the hot environment sooner as compared to the
cold environment.
 Evaporation
● Let us take an example in which a cup of water is left in open air. With
passage of time, the level of water decreases. This happens due to the
evaporation of water.
● As all the water molecules do not have the same magnitude of speed. In
this way, some molecules have very high speed, but some have very
low speed, and most of the molecules have an average speed.
● When the molecules of liquid collide, they transfer energy to each other
based on how they collide with each other. On an average, only a
fraction of the molecules in a liquid have enough heat energy to escape
from the liquid. This process is known as evaporation.
 Evaporation
● However, some molecules of water also come back into the liquid
phase from the vapour phase. This process is known as condensation.
Thus, evaporation continues until an equilibrium is reached, where the
rate of evaporation becomes equal to rate of condensation.

Vapour particles
After some
time
Liquid particles

The high energy molecules

escape the surface.

Evaporation of water
 Evaporation
Definition: Evaporation is a type of vapourisation that occurs on the
surface of a liquid as it changes into the gaseous phase. The surrounding
gas must not be saturated with the evaporating substance.
Example: Some water is spilled on the floor and there are two cases:

Case I Case II
In this case, an inverted bucket is put In this case, the spilled water is in an
on the spilled water. open environment.
 Evaporation
Case I Case II
Here, when the water evaporates, a Here, when the water evaporates
very little area (inside the bucket) is there is a huge surrounding in
in the equilibrium with the water. contact with the spilled water. Thus,
Thus, the surrounding is saturated it takes a lot of time to get saturated
very soon with water vapour. with the water vapours.
An equilibrium will not be
An equilibrium will be established
established quickly and it will take a
quickly and the rate of evaporation
lot of time for the rate of evaporation
will be equal to the rate of
to become equal to the rate of
condensation.
condensation.
 Evaporation

Case I Case II
Less water will evaporate. More water will evaporate.
 Factors-Affecting Solubility

Effect of pressure

Pressure does not have any significant effect on the solubility of solids in liquids.
It is so because solids and liquids are highly incompressible and practically
remain unaffected by the changes in pressure. Pressure has an effect only when
gases are involved, i.e., mainly in gas-liquid solutions.

Analogy
Suppose we have a beaker in which a frictionless piston is fitted and the beaker
contains the dissolved CO2 in it. Some CO2 molecules have high energy. Due to
this, some CO2 molecules escapes from the solution and at the same time,
some CO2 molecules come back into the water. Thus, there is an equilibrium
between the process of evaporation and condensation.
 Factors-Affecting Solubility
However, as we apply more pressure on the piston, the CO2 will get
compressed. Due to this, more CO2 molecules will go into the solution and the
solubility of the CO2 increases.

On increasing
pressure the
CO2(g) particles solubility of gas
particles in the
Dissolved CO2 particles
liquid increases.

Effect of pressure on the solubility of CO2 gas in the liquid

 Factors-Affecting Solubility

Example:
Let us take two beakers. The
first beaker has soda and the
second has water. As we add
some drops of methyl red
indicator in both the beakers,
the first beaker (that has soda)
has a red colour (pH < 4.4) and Soda Water (pH < 4.4) (pH > 6.2)
the second beaker has a
yellow colour (pH > 6.2). Addition of methyl red
indicator
 Factors-Affecting Solubility
Now, some coloured soda solution is taken in a syringe and then close its nozzle. If
we pull the syringe up, then the colour of the solution changes from red to yellow.
This means that the amount of CO2 dissolved in the soda water decreases.
However, when we press the syringe again, the colour of the solution changes
back to red. This means that the amount of CO2 dissolved in the soda water
increases.

Soda coloured Water coloured

solution solution Decrease in dissolved Increase in dissolved
CO2(g) in the soda CO2(g) in the soda
 Factors-Affecting Solubility
Conclusion
By the given examples, we can conclude that at equilibrium:
Rate of dissolution of gas = Rate of escape of gas from liquid

Case I

If the pressure increases, the equilibrium gets disturbed. Due to the increase in
the pressure, more gas molecules enter into the solution phase to restore the
equilibrium. This means that an increase in the pressure increases the
solubility, increasing the population density of the gas molecules in solution.
 Factors-Affecting Solubility
On increasing pressure the solubility of gas particles in the liquid increases.

Gas particles

Liquid

Effect of increase in pressure on the solubility of gas in the

liquid
 Factors-Affecting Solubility

Case II

If the pressure decreases then the equilibrium gets disturbed. Due to the
decrease in the pressure, more gas molecules escape into the vapour
phase to restore the equilibrium. This means that a decrease in the
pressure decreases the solubility, decreasing the population density of
the gas molecules in liquid.
 Factors-Affecting Solubility

On decreasing pressure the solubility of gas particles in the liquid decreases.

Gas particles
Liquid
Effect of decrease in pressure on the solubility of gas in the
liquid
 Partial Pressure

Definition: If a container is filled with more than one gas and each gas
exerts pressure, then the pressure of the individual gas exerted within the
container is known as its partial pressure.

Analogy
Let us assume that the pressure in the oxygen gas container is 159 mm of
Hg and in the nitrogen container is 593 mm of Hg. When both the gases
are mixed, the pressure of this container is 752 mm of Hg. Thus, we can
say that the pressure of the mixture is due to the pressure of both the
oxygen and nitrogen gases.
 Partial Pressure

+ =

Oxygen Nitrogen Oxygen + Nitrogen

Pressure: 159 mm of Hg 593 mm of Hg 752 mm of Hg

Analogy for partial pressure

 Henry’s Law
Henry was the first to give a quantitative relation between the pressure and
the solubility of a gas in a solvent known as Henry’s law.
● The law states that at a constant temperature, the solubility of a gas in
a liquid is directly proportional to the partial pressure of the gas
present above the surface of the liquid or the solution.
● The mathematical expression for Henry’s law is given as follows:
p = KH × 𝛘
Where, KH is the Henry’s law constant.
p = Partial pressure of the gas present above the solution
𝛘 = Mole fraction of the gas in the solution
 Henry’s Law

At constant
Gas particles Temp.

Liquid
On increasing pressure, more gas
particles dissolve in the liquid
Illustration of Henry’s law
 Henry’s Law

Graphical analysis

The Henry’s law expression is

given as follows:

Pressure (p)
p = KH × 𝛘
By comparing it with the straight
line equation; Slope = KH
(y = mx + c), we get,
Intercept (c) = 0
Slope (m) = KH
Mole fraction (𝛘)
 Henry’s Law

Graph at different temperatures:

Let us assume that T1 > T2 > T3, T1

Pressure (p)
temperature T1 has the highest slope,
and T3 has the lowest. Thus, for the T2
fixed value of the partial pressure, as
T3
the temperature increases, the slope of
the graph also increases.

Mole fraction (𝛘)

 Henry’s Law

However, to maintain the fixed value of the partial pressure of any gas, the
mole fraction of the gas in the solution decreases. This indicates that the
solubility of the gas also decreases as the temperature increases. This
occurs only in case of exothermic reactions.

By graph: T1 > T2 > T3

Conclusion: KH > K H > KH or 𝛘1 < 𝛘2 < 𝛘3
1 2 3