Mulungushi University

Colligative properties
By Daka J. J
 Learning outcomes
-Definitions
-Identify the colligative properties of matter
-Perform calculations relating to:
(a) Lowering of vapour pressure
(b) Boiling point elevation
(c) Freezing depression
(d) Use Rauolt’s Law to relate pressure to molar
fractions.
-Calculate using appropriate equations the osmotic
pressure and explain reverse osmosis.
-Identify types of solution in relation to movement of
solvent.
-Evaluate the Van’t Factor for ionic and non ionic
molecules and use it in calculations.
 Colligative properties definitions
- A colligative property is a property of a solution that is dependent on the
ratio between the total number of solute particles (in the solution) to the total
number of solvent particles.
-Colligative properties are not dependent on the chemical nature of the
solution’s components.
-Colligative properties can be linked to several quantities that express the
concentration of a solution, such as:
(i) Molarity
(ii) Normality
(iii) Molality.
The four colligative properties that can be exhibited by a solution are:
 Basic conversions

Mole Fraction and Molality

Several units commonly used to express the concentrations of solution components,
each providing certain benefits for use in different applications. Molarity (M) is a
convenient unit for use in stoichiometric calculations, since it is defined in terms of
the molar amounts of solute species in a unit volume:

M=mol solute/ L solution

Because solution volumes vary with temperature, molar concentrations will

likewise vary.
When expressed as molarity, the concentration of a solution with identical numbers
of solute and solvent species will be different at different temperatures, due to the
contraction/expansion of the solution.
More appropriate for calculations involving many colligative properties are mole-
based concentration units whose values are not dependent on temp

The mole fraction, X, of a component is the ratio of its molar amount to the total
number of moles of all solution components:

Molality is a concentration unit defined as the ratio of the numbers of

moles of solute to the mass of the solvent in kilograms:
 Calculations

(a)
(b)
 Colligative properties

Colligative properties exhibited by solutions

•Boiling point elevation
•Freezing point depression
•Relative lowering of vapour pressure
•Osmotic pressure

In the context of defining a solution, colligative properties help us understand

how the properties of the solution are linked to the concentration of solute in the
solution.
Different Types of Colligative Properties of Solution
There are different types of colligative properties of a solution. These include:
(i) vapour pressure lowering
(ii) boiling point elevation
(iii) freezing point depression
(iv) osmotic pressure.
1. Lowering of Vapour Pressure
In a pure solvent, the entire surface is occupied by the molecules of the solvent. If a
non- volatile solute is added to the solvent, the surface now has both solute and
solvent molecules; thereby fraction of surface covered by solvent molecules gets
reduced. Since the vapour pressure of the solution is solely due to solvent alone, at
the same temperature the vapour pressure of the solution is found to be lower than
that of the pure solvent.
 1. Lowering of Vapour Pressure
If P0 is the vapour pressure of pure solvent and Ps is the vapour pressure of the
solution.
The difference which is termed as lowering in vapour pressure. (Po – Ps)

The ratio which is known as the relative lowering of vapour pressure.

(Po – Ps / Po)

Raoult’s Law acknowledges the ratio as:

The relative lowering in vapour pressure of a dilute solution is equal to the mole
fraction of the solute present in the solution.
Which can be written as:
Where n = moles of solute
N = moles of pure solvent
 1. Lowering of Vapour Pressure

Raoult’s Law Concluded that:

or pressure exerted by mixture = x (Ps)

Calculations on Raoult’s Law (Example 1)

Hexane and heptane were mixed to form an ideal solution. At 100 0C, the vapour
pressure of two liquids( Hexane C6H14 and heptane C7H16) are 190kPa and 45kPa
respectively. What will be the vapour pressure of the solution obtained by mixing
25g of hexane and 35 g of heptane will be:
Soln
No of moles of hexane,n1= 25/86= 0.29
No of moles of heptane, n2=35/100=0.35
Calculations on Raoult’s Law

=0.45
 Calculations on Raoult’s Law (Example 2)

The vapour pressure of a pure liquid at 298K is 4 x 10 4 N/m2. When a non-volatile

solute is dissolved the vapour pressure becomes 3.65 x 10 4 N/m2. Calculate
(a) Relative vapour pressure
(b) Lowering of vapour pressure
(c) Relative lowering of vapour pressure
Tasks required.
Relative vapour pressure =
Lowering of vapour pressure =
Relative lowering of pressure =

(a) Relative vapour pressure = p/po = (3.65 x 104 N/m2)/(4 x 104 N/m2) = 0.9125
 Calculations on Raoult’s Law

(b)Lowering of vapour pressure = po – ps = 4 x 104 N/m2 – 3.65 x 104 N/m2

= 0.35 x 104 N/m2 = 3.5 x 103 N/m2

(c) Relative lowering of pressure = (po – ps)/po = (3.5 x 103 N/m2)/(4 x 104 N/m2)

= 0.0875
 Calculations on Raoult’s Law (Example 3)

The vapour pressure of a solution containing 13 × 10 -3 kg of solute in 0.1 kg of

water at 298 K is 27.371 mm Hg.
Calculate the molar mass of the solute. Given that the vapour pressure of water at
298 K is 28.065 mm Hg.
Given data
mass of solute W2 = 13 × 10-3 kg
mass of solvent (water) = W1 = 0.1 kg
vapour pressure of pure solvent (water) = P0 = 28.065 mm of Hg
vapour pressure of solution = Ps = 27.371 mm of Hg
temperature = T = 298 K
Molecular mass of solvent (water) = M1 = 18 g mol-1
Task: Molecular mass of solute = M2 =?
Calculations on Raoult’s Law (Example 3)

= )(

= )(

= )(

=
2. Elevation in Boiling Point

The boiling point of a liquid is the temperature at which the vapour pressure is
equal to atmospheric pressure.
We know that on the addition of a non-volatile liquid to a pure solvent, the vapour
pressure of a solution decrease.
Therefore to make vapour pressure equal to atmospheric pressure we have to
increase the temperature of the solution.
The difference in the boiling point of the solution and the boiling point of the pure
solvent is termed as elevation in boiling point.

If is the boiling point of the pure solvent and is the boiling point of the solution
then elevation in boiling point is given as
∆Tb =T0b-Tb
 2. Elevation in Boiling Point

Experimental results show that there is a relation between elevation in boiling

point and molality ‘m’ of the solute present in solution
∆Tb ∝ m
∆Tb = kb x m
Where,
kb = molal elevation constant

Substituting the value of ‘m’ in the above relation we get

∆Tb = 1000 x kb x m2 / M2 x m1

Where, m2 = mass of solvent in g, m1 = mass of solvent in kg, M2 = molar mass of

 2. Elevation in Boiling Point - Calculations

The molal elevation constant for water is 0.513 o C kg mol–1. When 0.2mol of sugar
is dissolved in 250g of water.
Calculate the temperature at which the solution boils under atmospheric pressure.

∆Tb = moles of sugar x 1000 / weight of water in gram

∆Tb = 0.2 x 1000 / 250
∆Tb = 0.8
⇒ T0b-Tb = 0.8
For pure water, T0b =100oC
⇒ Tb= 0.8 + 100
=100.80 0C
 2. Elevation in Boiling Point - Calculations
0.64 g of adrenaline in 36.0 g of CCl4 produces a b.p elevation of 0.49 °C. What
is adrenaline's molecular weight?
Solution
Determine number of moles of adrenaline in solution:
ΔT = i Kb m
0.49 °C = (1) (4.95 °C kg mol¯1) (x / 0.0360 kg)
0.49 °C = (137.5 °C mol¯1) (x)
x = 0.0035636 mol

M = m/n
0.64 g / 0.0035636 mol = 180 g/mol
3. Depression in Freezing Point
The freezing point of a substance may be defined as the temperature at which the
vapour pressure of the substance in its liquid phase is equal to its vapour pressure in
the solid phase.
According to Raoult’s law when a non-volatile solid is added to the solvent its
vapour pressure decreases and now it would become equal to that of solid solvent at
a lower temperature.
The difference between the freezing point of the pure solvent and its solution is
called depression in freezing point.
If T0f is the freezing point of the pure solvent and T f is the freezing point when non-
volatile solute is dissolved in it then depression in freezing point is given as:
∆Tf =T0f -Tf
Just like elevation in boiling point, depression in freezing point is also directly
related to molality ‘m’.
3. Depression in Freezing Point
Therefore: m’ = mol solute/mass solvent in Kg.
∆Tf = 1000 x kf x m2 / M2 x m1

Where,

kf = molal depression constant

m2 = mass of solute in g

M1 = mass of solvent in kg

M2 = molar mass of solute

ΔT = i K m’
Van’t Hoff Factor (i)
When the solute undergoes dissociation or association in solution,
the number of particles in solution increases or decreases and thus,
colligative properties changes accordingly. The extent of dissociation or
association of the solute in a solution can be expressed by a factor called
Van’t Hoff.
 3. Depression in Freezing Point-Van’t Factor
A solution of CaCl2 was prepared by dissolving 0.0169g in 1 Kg of distilled water
in ( molar mass of Ca2+= 41g mol–1 and Cl= 35.5gmol–1). The molal depression
constant of water is 2kg mol–1. The depression in freezing point of the solution is:
Solution:
Van’t Hoff factor(i) of CaCl2 is 3
Kf = 2 kg mol–1
Given,
Mass of CaCl2 (m2) = 0.0169g
Molar mass of CaCl2( M2) =112g
Weight of water(m1) =1000g
∆Tf = i x 1000X Kf x m2 / M2 x m1
= 3 x 1000 x 2 x 0.0169 / 112 x 1000g
= 9× 10-4
A 1.00 M solution of acetic acid (CH3COOH) in benzene has a freezing point
depression of 2.6 K. Calculate the value for i and suggest an explanation for its
value.

Solution

The freezing point depression equation is:

ΔT = i Kf m’

The only value we do not know is i:

2.6 K = (x) (5.10 K m¯1 ) (1.00m)

x = 0.51
Here's an explanation: If i = 1, then one item dissolving yields one item in solution.
If i = 2, then one item dissolving yields two items in solution.

What about i = 0.5?

Think of it in the reverse fashion to i = 2 and one item (like a molecule) into solution
yielded two items (the dissociated molecule) in solution. This is the reverse.
When one item goes into solution, only one-half is present in the solution.

Sort of a reverse dissociation - call it an association.

4. Osmotic Pressure
When a semipermeable membrane is placed between a solution and solvent, it is
observed that solvent molecules enter the solution through the semipermeable
membrane and the volume of the solution increases.

The semi-permeable membrane allows only solvent molecules to pass through it

but prevents the passage of bigger molecules like solute.

This phenomenon of the spontaneous flow of solvent molecules through a

semipermeable membrane from a pure solvent to a solution or from a dilute to a
concentrated solution is called osmosis.

The flow of solvent molecules through the semipermeable membrane can be

stopped if some extra pressure is applied from the solution side.
This pressure that just stops the flow of solvent is called osmotic pressure of the
solution
Osmotic Pressure

P =hg

P =hg is osmotic pressure, while

extra applied to reverse is what
we refer to as reverse osmosis.
 Osmotic Pressure
Osmotic pressure is a colligative property as it depends on the number of solute
present and not on the nature of the solute. Experimentally it was proved that
osmotic pressure () is directly proportional to molarity(C) and temperature(T).

Mathematically, = iCRT where R is the gas constant.

⇒ = i() RT

i = Van’t factor, V is the volume of solution in litres and n 2 is moles of solute

If m2 is the weight of solute and M2 molar mass of solute, then n2= m2/M2

=i
Thus by knowing the values of ,w2, T and V we can calculate the molar mass of
the solute.
Different Solutions

Isotonic solution: Two solutions having the same osmotic pressure at a given
temperature are known as an isotonic solution.
When such solutions are separated by a semi-permeable membrane than there is
no osmosis.
Hypotonic solution: A hypotonic solution has a lower osmotic pressure than that of
the surrounding i.e, the concentration of solute particles is less than that of the
surrounding.
If the hypotonic solution is separated by semipermeable membrane then water
moves out of the hypotonic solution.
Hypertonic solution: A hypertonic solution has a higher osmotic pressure than
that of the surrounding i.e, the concentration of solute particles is more than that
of the surrounding.
If the hypertonic solution is separated by semipermeable membrane then water
moves inside the hypertonic solution.
 Osmotic Pressure-Calculations
Example 1
300 cm3 of an aqueous solution contains 1.56g of a polymer. The osmotic pressure
of such solution at 27oC is found to be 2.57 ✕ 10-3 bar. Calculate the molar mass of
the polymer

Solution:
Weight of polymer( W2) = 1.56g
Osmotic pressure () = 2.57 ✕ 10-3 bar
volume (V) = 300 cm3 = 0.3L
R = 0.083 L.bar.K-1.mol-1.
=
M2 = W2 RT / V
= 1.56 x 0.083 x 300 / 0.3 x 2.57 x 10-3
= 50381 g mol–1
Example 2
58.5g of table salt is dissolved in one litre of water. At a temperature of 27 oC, what
would be the osmotic pressure in atm of this solution?

Soln
M = 58.5g, n = 58.5/58.5g/mol = 1.0 mol
R = 0.0821 atm.L. mol-1.K-1.
i=2
= iCRT
= 2 x 1 x 0.0821 x 300

= 49.26 atm
Example 3
The osmotic pressure of a potassium chloride solution (at 300K) is 50 atmospheres.
What is the molar concentration of potassium chloride in this solution?

π = iCRT

C = π/(iRT)
KCl dissociates into two ions

C = (50 atm)/(2)*(0.0821 atm.L.mol-1.K-1)*(300K)

C = 50/49.26 M = 1.015 M
 Example 4

A solution is prepared by dissolving 35.0 g of hemoglobin in enough water to make

up 1.00 L in volume. The osmotic pressure of the solution is found to be 10.0
mmHg at 25.0 °C. (Use R = 0.0821 atm.L.mol-1.K-1)
Calculate the molar mass of hemoglobin.

Soln
Change pressure (10.0 mmHg / 760.0 mmHg atm¯1)
= iCRT

(1) (x) (0.0821 L atm mol¯1 K¯1) (298 K) = 0.013157894 atm

x = 0.013157894 atm/0.0821 x 298

x = 0.00053807 M
Determine moles of solute:

M = moles / liters of solution

0.00053807 mol L¯1 = x / 1.00 L

x = 0.00053807 mol

Calculate the molar mass:

molar mass = g / mol
x = 35.0 g / 0.00053807 mol
x = 65,047 g/mol
QUIZ 2
Question
B- is a base when put in water undergoes the following
ionization.
B- (aq) + H2O (l) BH (aq) + OH-(aq).
If 0.0056M of B- undergoes 10% ionization in water, what
is;
(i)Concentration of hydroxide in water, [3]

(ii)What is the pH of the solution, [4]

(iii)The Kb for B-? [3]