INTRODUCTION

Solution

Going by the definition, a binary solution is nothing but a homogeneous mixture of two
substances. These two substances or components are the solute and the solvent. The
solute is the substance that gets dissolved. It is present in a smaller quantity. On the other
hand, the solvent is the substance that dissolves the solute. It is present in a comparatively
larger quantity.There are different types of solutions.

Colligative Properties of Liquids

Colligative properties are those properties of a liquid which depend on the number of
solute particles and not on the concentration of the solution. These properties are studied
in liquids.Non-colligative propertties depend on the identity of the dissolved species and
the solvent.

There are four colligative properties namely- relative lowering of vapour pressure,
elevation of boiling point, depression of freezing point and osmosis and osmotic pressures.
Related to these properties, the following deductions can be made:

1) Relative Lowering of Vapour Pressure

Vapour Pressure of liquid solutions is the amount of pressure that the vapours exert on the
liquid solvent when they are in equilibrium and a certain temperature.

The law states that the partial pressure is directly proportional to the mole fraction of the
solute component. So, according to Raoult’s Law, the partial pressure of A will be

PA ∝ xA

PA = P0A xA -------------(1)

In a pure liquid, the surface of the liquid is occupied by the molecules of the liquid.
Suppose a non-volatile solute is now added to this pure liquid. Since the solute
molecules are non-volatile, the vapour above the solution consists of only solvent (pure
liquid) molecules. After adding the solute, the vapour pressure of the solution is found
to be lower than that of the pure liquid at a given temperature.
This lowering in vapour pressure is due to the fact that after the solute was added to the
pure liquid (solvent), the liquid surface now had molecules of both, the pure liquid and
the solute. The number of solvent molecules escaping into vapour phase gets reduced
and as a result the pressure exerted by the vapour phase is also reduced. This is known
as relative lowering of vapour pressure. This decrease in vapour pressure depends on the
amount of non-volatile solute added in the solution irrespective of its nature and hence it
is one of the colligative properties.

PA = P0A xA (From equation 1)

PA =P0A (1-XB) or XB=(P0A-PA)/P0A

2) Elevation of Boiling Point

The vapour pressure of a solute tends to decrease as a non-volatile solute is added in a

solvent. The boiling point of such solution is always greater than the pure solvent in which
it is added. This happens because the pressure of vapour is in direct proportion to the
temperature of the solution.

If the solution is to be boiled, the temperature of such a solution has to be raised. This
phenomenon comes to be identified as the elevation of boiling point. The solute particles
in the solvent, along with the vapour pressure, together play a role in this phenomenon.

Formula: ΔT = Kbm

where ΔT= change in temperature

m = the molality, which is the moles of solute per kilograms of solvent
Kb = the molal boiling point constant (for water, Kb = 0.5121C/m)

3) Depression of Freezing Point

Decreasing the vapor pressure of a solution results in decreasing the freezing of the
solution as well. The freezing point of a solution can be identified as a point at which the
vapor pressure of a given substance is equal in the liquid and vapor state. As per the law,
the freezing point for a given dilute solution also stays directly proportional to molality of
the solute, same as the boiling elevation point.

Formula: ΔT = Kfm

ΔT= change in temperature

m = the molality, which is the moles of solute per kilograms of solvent
Kf = the molal freezing point constant (for water, Kf = -1.86 C/m)

4) Osmosis and Osmotic Pressure

Raw mangoes shriveling when placed in salt water or wilted flowers reviving when
placed in fresh water. This happens due to a process called osmosis. Osmosis is the flow
of solvent molecules from pure solvent to the solution through a membrane. The flow
continues until equilibrium is reached.

The process of osmosis occurs through a membrane that looks continuous but contains
small pores that allow small solvent molecules like water to pass through, but not bigger
solute molecules. Such membranes are called semipermeable membranes (SPM).

The flow of solvent towards the solution side across the semipermeable membrane can be
stopped by applying extra pressure on the solution. This pressure is known as the osmotic
pressure of the solution.

Few important things to note –

 During osmosis, the solvent flows from the dilute (lower concentration) to
concentrated (high concentration) side across the semipermeable membrane.

 Osmotic pressure depends on the concentration of the solution.

The osmotic pressure of a solution is the excess pressure applied to the solution to prevent
osmosis. It is also a colligative property and depends on the number of solute molecules
and not their identity.

For dilute solutions, osmotic pressure is directly proportional to the molarity (M) of the
solution at a given temperature (T).
Π = M R T = (n/V) R T or ΠV=nRT

where, Π – osmotic pressure, C – molarity, R – gas constant, T – temperature, V – a

volume of solution in liters, n – the number of moles of solute.

Abnormal Molar Masses

In chemistry, when the molar masses are calculated and if they are higher or lower
than the expected value are known as abnormal molar masses. These are calculated
using the colligative properties. Colligative properties include; elevation of boiling
point, lowering relatively of vapor pressure, freezing point depression, and ease of
osmotic pressure. The name in itself has abnormal in it which suggests the
abnormality of how the molar masses are being calculated, using the Van’t Hoff
factor.

Introduction to Abnormal Molar Masses

To understand the abnormal molar masses, first, we need to understand the total
number of particles left either after the association or dissociation of the solute
molecules present in a solution or a solvent. To study and understand more about more
about the abnormalities, Dutch chemist Van’t Hoff, discovered (i), which is known as
the Van’t Hoff’s factor.

This factor represents the extension of dissociation or association of a solute. This

factor alone accounts for all the abnormalities in the molar mass.

Association of the Solute Particles

In a solution, some solute molecules start to associate with each other. Thus, now there
is less number of these particles inside a solution. The colligative properties will vary
with a number of solute particles in the solution. As a result, they will now, start to
decrease with the number of solute particles being less.

The molecular mass of the solute is inversely proportional to its colligative properties.
Thus a decrease in colligative properties will lead to an increase in the molecular
masses.

Example: acetic acid or ethanoic acid associate in the solution, when dissolved in
benzene, dimerizes, because the number of particles and hydrogen bondings are
reduced. This happens usually with the solvents which have low dielectric constants.
This experiment increases the molar mass more than the expected value achieved
theoretically.

Dissociation of Solute Particles

Contrary to the association, some solute particles will dissociate into more ions or
particles when they are dissolved in the solution. Thus, this will increase the number
of solute particles in the solution and thereby the colligative properties of the solution.

Now, the molar mass being inversely proportional to the colligative properties will
reduce the molar mass in the solution. This will result in the lower number of molar
mass than the expected value. Thus the molar mass will be abnormal molar mass.

Example: The weak electrolytes are dissolved in the water, ions are formed.
Hydrofluoric acid will dissociate into fluorine anion and hydrogen cation.

Van’t Hoff factor

To understand the concept of abnormalities, Van’t Hoff introduced a factor called

Van’t Hoff factor. This factor is used to sort out the dissociation and association
problem while calculating the molar mass of the solute. The factor is denoted by ‘i’
and is obtained when the normal mass or the expected value is divided by the
abnormal mass.

Mathematically, the factor is represented by,

 i = Normal molar mass/Abnormal molar mass or

i = observed or expected colligative properties/ calculated colligative properties or

i = Total moles in the particles after dissociation or association/total moles in the

particles before dissociation or
association

How to calculate i?

Firstly, we will write whether the solute is being dissociated or associated.

For association, α= ni−1(n–1)

where n is the no. of particles being associated and α is the degree of association. The
equation is derived as follows:

nα → αn

Initial moles: 1 mol and 0 mol

Moles at equilibrium: 1 – α and α/n

Therefore, total moles = 1 – α + α/n

Thus, i= 1 – α + α/n

For solute which depicts the association, the Van’t Hoff factor will always be less than
1. For dissociation, i = 1 + (n – 1)α. Here, α (alpha) will be the degree of dissociation
and n will be a number of dissociated particles.

For solutes depicting dissociation, Van’t Hoff factor will always be greater than 1. For
particles, that shows neither association or dissociation, the Van’t Hoff factor is
considered as 1. Thus, after the inclusion of Van’t Hoff’s factor, the equation of the
colligative properties will be,
 Boiling point elevation, ∆Tb = i x Kb x m

 Relative Lowering of vapour pressure, i XB=(P0A-PA)/P0A

 Freezing point depression, ∆Tf = i x kf × m

 Osmotic pressure, Π =i M R T