Dr LQ Qwabe, Physical Chemistry II, 2023

Module unit objectives

At the end of this module unit, you must be able to:

• Define colligative properties and distinguish different types of colligative properties

• Perform calculations in relation to each colligative property

• Distinguish between a colloidal solution and true solution

• Describe a micelle and its formation mechanism

Physical Chemistry 2, Colligative properties

 Colligative properties

Colligative properties of solutions are properties that depend on the concentration of a solute
molecules but not on the chemical identity of the solute.

Before we deal with these properties let us deal with ways of expressing concentration, which are:

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
• Molarity =
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑖𝑛 𝐿

Example: A 0.500 mol sample of solute dissolved in 1 L gives a solution that 0.500mol/1L or
0.500 mol. L-1 or mol.dm-3.

Physical Chemistry 2, Colligative properties

 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
• Mass percentage of solute = × 100
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

Example: A 2.50 g sample of KCl dissolved 97.5 g of solvent (water) will give a 2.50% of
KCl in that solution (note that the total solution is 100 g).

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
• Molality =
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑖𝑛 𝑘𝑔

• Example: A 0.500 mol sample of solute dissolved in 3000 g of solvent will give a solution
with a molality of 0.500/0.3 kg = 1.7 mol/kg of molal

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝐴
• Mole fraction =
𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

Physical Chemistry 2, Colligative properties

Example 1: A solution made of 1 mol of solute and 3 mols of the solvent gives a total number of 4
moles. The mole fraction of the solute is therefore ¼ = 0.25 or 25%. This applies to all solutes in
the solution individually.

Example 2: An aqueous solution is 0.120 m glucose, C6H12O6, What are the mole fractions of each component in the

solution?

Solution:

n C6H12O6 = 0.120 mol

nH2O = 1000𝑔ൗ18.02 = 55.49 𝑚𝑜𝑙

𝑋C H O = 0.120ൗ(0.120+55.49) = 0.00216 and 𝑋H O = 55.49Τ

55.61 = 0.998
6 12 6 2

Physical Chemistry 2, Colligative properties

Homework exercises:

1. A solution that is 0.150 mole fraction glucose, C6H12O6, and 0.850 mole fraction water. What
is the molality of the solution?

2. An aqueous solution is 0.273 m KCl. What is the molar concentration of KCl? The density of
the solution is 1.011 × 103 g/L

Physical Chemistry 2, Colligative properties

Now that we have dealt with concentration expressions let us dela with colligative properties.

There are four colligative properties:

• Vapour pressure lowering

• Boiling point elevation
• Freezing point depression
• Osmotic pressure

• These properties are of great importance to many natural phenomenon and technological
applications.

Physical Chemistry 2, Colligative properties

 Vapour-pressure lowering

Vapour pressure is defined as the tendency of a substance to change into its vapour state.

The vapour pressure of a volatile solvent can be lowered by addition of a nonvolatile solute and
that phenomenon is called vapour-pressure lowering.

Vapour-pressure-lowering is a colligative propery that is equal to the vapour- pressure of the pure
solvent minus the vapour pressure of the solution.

For example, the vapour-pressure of water at 20 °C is 17.54 mmHg but a solution containing
0.0100 mole fraction ethylene glycol has a vapour-pressure of 17.36 mm Hg, thus the vapour-
pressure lowering is ΔP = 17.54-17.35 = 0.18 mm Hg

Physical Chemistry 2, Colligative properties

Raoult’s law shows that the partial vapour-pressure of a solvent over a solution of a non-electrolyte
solute depends on the mole fraction of the solvent in the solution.

Hence according to Raoult’s law , the partial pressure of a solvent, 𝑃𝐴 , over a solution is equal to
the vapour-pressure of the pure solvent, 𝑃𝐴0 , times the mole fraction of solvent, 𝑋𝐴 , in the solution,
𝑃𝐴 = 𝑋𝐴 𝑃𝐴0 .

In general, Raoult’s law holds for dilute solutions (where 𝑋𝐴 is close to 1). If the solvent and solute
are chemically similar Raoult’s law may hold for all mole fractions (see diagram below).

Physical Chemistry 2, Colligative properties

 Raoult’s law for ideal and non-ideal solutions

𝑷𝟎𝑨 Non-ideal solution

follows Raoult’s law
Vapour-pressure of for dilute solutions
solvent

Type the label of the photo here

Mole faction of solvent

Physical Chemistry 2, Colligative properties

If Raout’s law holds for and that the solute is nonvolatile, we express the vapour-pressure lowering
as:
∆𝑃 = 𝑃𝐴0 − 𝑃𝐴
Substituting in Raoult’s law,
∆𝑃 = 𝑃𝐴0 − 𝑃𝐴0 𝑋𝐴 = 𝑃𝐴0 1 − 𝑋𝐴

The sum of the mole fractions of components in a solution must equal 1, i.e., 𝑋𝐴 + 𝑋𝐵 + ⋯ . . = 1
hence 𝑋𝐵 = 1 − 𝑋𝐴 and therefore the vapour-lowering is given by:

∆𝑃 = 𝑃𝐴0 𝑋𝐵

Physical Chemistry 2, Colligative properties

A solution of two substances that follows Raoult’s law for all values of mole fraction is called an
ideal solution.

Ideal solutions occur when the two substances, A and B forming a solution are chemically similar
so that the intermolecular forces between two A or B molecules are the same as those between A
and B molecules.

The solute in this case does not have to be non-volatile (both solute and solvent can have
significant vapour pressures).

The total vapour-pressure above that solution equals to the sum of partial vapour pressures as
described by Raoult’s law:
𝑃 = 𝑃𝐴0 𝑋𝐴 + 𝑃𝐵0 𝑋𝐵
Physical Chemistry 2, Colligative properties
Suppose a solution of benzene and toluene is made of 0.70 mole fraction benzene and 0.30 mole
fraction toluene. If the vapour pressures of pure benzene and toluene are 75 mmHg and 22 mmHg
respectively, we can find the total vapour-pressure above that solution as

𝑃 = 75 𝑚𝑚𝐻𝑔 × 0.70 + 22 𝑚𝑚𝐻𝑔 × 0.30 = 59 𝑚𝑚𝐻𝑔

It is evident that the vapour is rich in benzene than toluene because it is more volatile by virtue of
its higher vapour pressure.

To find the mole fraction of each component in the vapour phase we must find individual partial
vapour pressures hence,

𝑃 𝑏𝑒𝑛𝑧𝑒𝑛𝑒 = 0.7 × 75 𝑚𝑚𝐻𝑔 = 53 𝑚𝑚𝐻𝑔

Physical Chemistry 2, Colligative properties

 𝑃 𝑡𝑜𝑙𝑢𝑒𝑛𝑒 = 0.3 × 22 𝑚𝑚𝐻𝑔 = 6.6 𝑚𝑚 𝐻𝑔

The mole fraction of benzene in the vapour phase is therefore:

𝑃(𝑏𝑒𝑛𝑧𝑒𝑛𝑒) 53 𝑚𝑚𝐻𝑔
𝑋 𝑏𝑒𝑛𝑧𝑒𝑛𝑒 = = = 0.9
𝑇𝑜𝑡𝑎𝑙 𝑣𝑎𝑝𝑜𝑢𝑟 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 59 𝑚𝑚𝐻𝑔

To find the mole fraction of toluene we can use the same approach, or we can find it as a
difference, 1-0.9 = 0.1, because the mole fractions must be equal to zero.

Physical Chemistry 2, Colligative properties

 Boiling Point Elevation and Freezing Point Depression

The next colligative properties we will now deal with are boiling point elevation and freezing
depression.

The boiling point of a substance is temperature at which its vapour- pressure is equal to 1 atm
(atmospheric pressure).

The boiling point elevation, ∆𝑇𝑏 , is a colligative property of a solution equal to the boiling point of
the solution minus the boiling point of the pure solvent. This colligative property is proportional to
the to the molar concentration, 𝑐𝑚 , of the solution (dilute solution), i.e.

∆𝑇𝑏 = 𝐾𝑏 𝑐𝑚
Where 𝐾𝑚 is the boiling-point-elevation constant and depends only on the solvent

Physical Chemistry 2, Colligative properties

Benzene has a boiling point of 80.2 °C and a boiling-point-elevation constant of 2.61 °C/m. A
solution of 0.100 m solution of a nonvolatile solute in a benzene solution has boiling point elevation
of 2.61°C/m × 0.100m = 0.261 °C.

This means that such a solution will boil at 0.261 °C above the boiling point of benzene, i.e. 80.2
°C + 0.261 °C = 80.46 °C ≈ 80.5 °C

The freeing point depression, ∆𝑇𝑓 , on the other hand is a colligative property of a solution equal to
the freezing point of the pure solvent minus the freezing point of the solution. Thus,

∆𝑇𝑓 = 𝐾𝑓 𝑐𝑚
Where 𝐾𝑓 is the freezing-point-depression constant and depends only on the solvent.

Physical Chemistry 2, Colligative properties

Example
A aqueous solution is 0.222 m in glucose. What are the boiling and freezing points of the solution?
Solution:

∆𝑇𝑏 = 𝐾𝑏 𝑐𝑚 = 0.512 ℃ൗ𝑚 × 0.0222 𝑚 = 0.0114 ℃

∆𝑇𝑓 = 𝐾𝑓 𝑐𝑚 = 1.86 ℃ൗ𝑚 × 0.0222 𝑚 = 0.0413 ℃

The boiling and freezing points are 100°C + 0.0114 °C = 100.01 °C and 0.00 °C-0.0413 °C = -
0.041°C respectively

(Boiling and freezing point constants are obtainable from prescribed or recommended textbooks)
Physical Chemistry 2, Colligative properties
Class exercise

A solution is prepared by dissolving 0.131 g of a substance in 25.4 g of water. The molality of the
solution is determined by freezing point depression to be 0.056 m. What is the molecular mass of
the substance?

Work on this exercise as a group of two or three !!!

Physical Chemistry 2, Colligative properties

 Osmotic pressure

Osmosis is the process of solvent flow through a semipermeable membrane to equalize the
concentration of the solute on both sides of the membrane.

If solutions of the same concentrations exist on both sides of the membrane, the solvent will
migrate in both directions. If one side has a higher concentration, then the solvent will migrate
towards a more concentrated solution.

Osmotic pressure, 𝜋, is colligative property of a solution equal to the pressure that, when applied to
the solution, just stops the osmosis.

Physical Chemistry 2, Colligative properties

The osmotic pressure, 𝜋, of a solution is related to the molar concentration of solute, M:

𝜋 = 𝑀𝑅𝑇
R is the universal gas constant and T is absolute.

The equation is similar to the ideal gas equation 𝑃𝑉 = 𝑛𝑅𝑇. If we modify the ideal gas equation
by replacing 𝑛Τ𝑉 with M we get 𝑃 = 𝑀𝑅𝑇 similar to the osmotic pressure equation.

Physical Chemistry 2, Colligative properties

Example
The formula for low-molecular-mass starch is (C6H10O5)n, where n averages 2.00 × 102. When
0.798 g of starch is dissolved in 100.0 mL of water solution, what is the osmotic pressure in mm Hg
at 25 °C?
Solution:
The molecular mass of starch ((C6H10O5)2000 is = 32400 g/mol
n (C6H10O5)2000 = 0.798Τ32400 = 2.46 × 10−5 mol
−5
M (C6H10O5)2000 = 2.46 ×10 ൗ0.1𝑜𝑜0 = 2.46 × 10−4 mol.dm-3

𝑚𝑜𝑙 𝑎𝑡𝑚
𝜋 = 𝑀𝑅𝑇 = 2.46 × 10−5
× 0.0821𝐿. × 298 𝐾 = 6.02 × 10−3 𝑎𝑡𝑚
𝐿 𝐾𝑚𝑜𝑙
𝜋 in mm Hg = 6.02 × 10−3 𝑎𝑡𝑚 × 760 𝑚𝑚 𝐻𝑔 = 4.58 𝑚𝑚 𝐻𝑔

Physical Chemistry 2, Colligative properties

 Colligative properties of ionic solutions

Colligative properties of ionic solution depends on the total ionic concentration rather than the
concentration of the ionic substance.

A typical example is that the freezing point depression a solution of NaCl with a molality of 0.100 m
is twice that of a solution of glucose with the same concentration.

This is because NaCl dissociates to produce two ions, Na+ and Cl- whereas glucose does not
hence the equation for the freezing-point depression for ionic solutions is:

∆𝑇𝑓 = 𝑖𝐾𝑓 𝑐𝑚

Physical Chemistry 2, Colligative properties

Where 𝑖 is the number of ions resulting from each formula unit and 𝑐𝑚 is the molality computed
based on the formula of the ionic compound.

The equation for other colligative properties are modified in similar manner to account for the factor
𝑖, hence,

∆𝑃 = 𝑖𝑃𝐴0 𝑋𝐵

∆𝑇𝑏 = 𝑖𝐾𝑏 𝑐𝑚

𝜋 = 𝑖𝑀𝑅𝑇

Physical Chemistry 2, Colligative properties

Example:
Estimate the freezing point of 0.010 m aqueous solution of aluminum sulfate, Al2(SO4)3.

Solution:
Since Al2(SO4)3 dissociates according to the equation, Al2(SO4)3 → 2Al3+ + 3SO42-
𝑖 = 5 hence,
∆𝑇𝑓 = 𝑖𝐾𝑓 𝑐𝑚 = 5 × 1.86 ℃ൗ𝑚 × 0.01 𝑚 = 0.093 ℃

The estimated freezing point of the solution is 0.00 °C-0.093 °C = - 0.093 °C

Physical Chemistry 2, Colligative properties

 Colloids

A colloid is a dispersion of one substance (dispersed phase) through out another substance or
solution (continuous phase).

In colloids the dispersed phase particles are larger than in a normal solution, ranging between 1 ×
103 pm and 2 × 105 pm in size.

While a colloid may appear to be homogeneous it is different from a true solution because it
scatters light, a phenomenon called the Tyndall effect.

Colloids are characterized according to the state (solid, liquid or gas) of the dispersed phase and of
the continuous phase.

Physical Chemistry 2, Colligative properties

Fog and smoke are aerosols which are either liquid or gas dispersed through out a gas.

An emulsion consists of liquid droplets dispersed through out another liquid (butterfat
dispersed though out homogenized milk).
A sol consists of solid particles dispersed in a liquid phase.
Colloids in which a continuous phase is water have two major classes:

• Hydrophilic colloids which are colloids in which there is a strong attraction between the dispersed
phase and the continuous phase (water).

• Hydrophobic colloids which are colloids in there is poor attraction between the dispersed phase and
the continuous phase (water).

Physical Chemistry 2, Colligative properties

Hydrophobic colloids are generally unstable whereas hydroplic colloids are stable. The dispersed
phase particles ted to aggregate over time in to larger particles.

Hydrophobic sols tend to when a solid crystallizes rapidly from a chemical reaction of
supersaturated solution.

When crystallization occurs rapidly many centers of crystallization called nuclei form at the same
time. These centers attract ions to them as a result very small crystals form, but they do not
precipitate out because of random solvent thermal agitation.

The process in which the dispersed phase particle of a colloid is made to aggregate and separate
from the continuous phase is called coagulation.

Physical Chemistry 2, Colligative properties

When molecules or ions that both the hydrophobic and hydrophilic ends are dispersed in water, at
a certain concertation they tend to associate for form colloid-sized particles called micelles.

A micelle is a colloid-sized particle formed in water by association of molecules or ions that each
have a hydrophobic end and a hydrophilic end.

In this association the hydrophobic ends tend to point inward and hydrophilic ends point outward in
the water phase. This type of a colloid is called association colloid.

Soaps and other detergents form part of association colloid.

Physical Chemistry 2, Colligative properties