Some solute particles undergo association or dissociation in solution which

causes a change in their colligative property as well as in their molar mass.

Colligative properties are properties that are dependent on the ratio of the
number of solute to solvent particles present in the solution. The extent to
which particles undergo association or dissociation is calculated through
the Van't Hoff factor.

This factor is named after Jacobus Henricus Van't Hoff, the Dutch physical
chemist, who earned the first Nobel Prize in chemistry. It is important to
remember that the calculated value for electrolytic solutions of the Van't
Hoff factor is typically lower than the expected value (due to the pairing of
ions). The higher the charge on the ions, the higher the deviation.

Here, you will learn about van't Hoff factor, how to calculate van't hoff
factor, and abnormal molar mass.

Abnormal Molecular Mass

Do You Know What Abnormal Molar Mass Is?

The molar mass calculated through the colligative properties is sometimes

different from that of experimentally determined molar mass is known as
abnormal molar mass. This abnormal molar mass is due to the solute
particles that undergo association or dissociation.

There are four types of colligative properties by which molar mass can be
calculated-

Relative Lowering of Vapour Pressure

The phenomenon where the addition of a non-volatile solute to a solvent
leads to the vapour pressure getting lower is called relative lowering of
vapour pressure. The relation between the pressure of the solution, the
vapour pressure of the pure solvent and the mole fraction of the solute was
discovered by a French Chemist.

He observed that it is mainly the concentration of the solute particles which

was responsible for the lowering of vapour pressure.

As per the laws devised by scientists,

Decrement in Vapour Pressure = Vapour Pressure of Pure Solvent –

Vapour Pressure of Solvent.

This equation is used to determine the ultimate molar mass of a solute.

Elevation in Boiling Point

The vapour pressure of a solute decreases as a non-volatile solute is added
to a solvent. The boiling point of such a solution is always greater than the
pure solvent that it is added to. This is because the pressure of vapour is in
direct proportion to the temperature of the solution. For the solution to
boil, the solution’s temperature has to be raised. This phenomenon is called
the elevation of boiling point.

Formula: ΔT = iKbm

(ΔT= change in temperature, i = the Van’t Hoff factor, m = the molality, Kb =

the molal boiling point constant)

Depression in Freezing Point

Decreasing the vapour pressure of a solution results in a decrease of the
freezing point of the solution. The freezing point of a solution can be
identified as a point at which the vapour pressure of the substance is equal
in the liquid and vapour state.

As per the law, the freezing point for a given dilute solution stays directly
proportional to the molality of the solute.
Formula: ΔT = iKfm

(ΔT= change in temperature, i = the Van’t Hoff factor, m = the molality, Kf =

the molal freezing point constant)

Osmotic Pressure
Osmosis is the flow of solvent molecules from the pure solvent to the
solution through a membrane. This flow does not stop until equilibrium is
reached. This process occurs through a membrane that contains small
pores that allow small solvent molecules like water to pass through. Such
membranes are called semipermeable membranes (SPM).

The solvent’s flow across the semipermeable membrane to the solution

side can be stopped by applying extra pressure on the solution. This
pressure is known as the osmotic pressure of the solution.

Thus, the osmotic pressure of a solution is the excess pressure applied to

the solution to prevent osmosis.

Osmotic pressure depends on the concentration of the solution, and when

it comes to dilute solutions, this pressure is directly proportional to the
molarity of the solution at a certain temperature.

Π = C R T = (n2/V) R T

(Π is osmotic pressure, C is molarity, R is gas constant, T is temperature, V

is a volume of solution in litres, n is the number of moles of solute).

Van't Hoff explained that solute dissociates into ions when solutes are
dissolved in a solvent. The dissociation of solute molecules into ions results
in an increase in the number of particles and thus affects the colligative
properties, as the colligative properties depend only on the number of
solute particles.

Some compounds tend to be associated in the aqueous state and the

amount of ions/molecules found in the solution is smaller than the total
number of molecules for those molecules. Thus, for those substances that
dissociate in solution, the molar mass measured will always be less than the
real mass, and the real mass will always be less than the molar mass
observed for those substances that associate in solution.

It is Possible to Describe the Abnormality in Molecular Mass as

Follows:

1. A rise in the number of particles results from the dissociation of

solute molecules into several ions. This, in essence, increases the
solution's colligative properties.

2. Since the molar mass is inversely proportional to the colligative

properties, it tends to have a lower value than predicted.

3. The total number of particles in the solution decreases as solvent

particles interact with each other, contributing to a decrease in
colligative properties.

4. The molar mass values obtained are higher than expected in this case

What is the Van't Hoff Factor?

The Van't Hoff factor denoted by the symbol ‘i’ measures the extent of
association or dissociation of solute in a solution.

Let’s see How to calculate Van’t Hoff factor-

Van’t Hoff Factor Formula -

i=

ObservedColligativePropertyNormalorColligativePropertyObserved
ColligativePropertyNormalorColligativeProperty
i=

NormalMolarMassObservedorMolarMassNormalMolarMassObserved
orMolarMass
i=

ActualNumberofParticlesObservedNumberofParticlesActualNumbero
fParticlesObservedNumberofParticles
These three formulas show the Van't Hoff Equation.

Van't Hoff Law for Dissociated Solutes

When 1 mole of NaCl is dissolved in 1 Kg of water, if all NaCl molecules
dissociate in water, the resulting solution would contain 1 mole of Cl-ions
and 1 mole of Na+ ions (a total of 2 moles of ions in the solution). But we
consider only 1 mol of NaCl to be present in the solution when measuring
the molar mass using the colligative properties.

So how to calculate Van’t Hoff factor-

i=

ObservedColligativePropertyNormalOrColligativePropertyObserved
ColligativePropertyNormalOrColligativeProperty
i=

2121
=2
So in case, the dissociation value is greater than 1- the number of solutes
increases, colligative properties increase, and decreases in the molar mass
of the solute. Hence colligative property is inversely proportional to the
molar mass of the solute.
This shows the relation between the van't hoff factor and degree of
dissociation.

Van't Hoff Law for Associated Solutes

Example- A solution of acetic acid in benzene. Dimerization of acetic acid in
benzene occurs. So 2 molecules of acetic acid combine to form one.
2CH COOH + benzene(CH COOH)
3 3 2

i=

1212
= 0.5
The value of ‘i’ is smaller than 1, so the quantity of solute decreases, thus
the colligative property, and hence the mass of solute increases.

Did You Know?

Osmotic pressure is one of the colligative properties which plays a major
role in a biological cell. An important factor that affects cells is osmotic
pressure. Osmoregulation is an organism's homeostasis process for
osmotic pressure to achieve equilibrium.

• Hypertonicity is the presence of a solution that causes the shrinkage

of cells.

• The presence of a solution that causes cells to swell is hypotonicity.

• Isotonicity is the presence of a solution that does not cause any

change in the volume of cells.

If the cell within accumulates water when a biological cell is in a hypotonic

environment, water flows into the cell via the cell membrane, allowing it to
expand. The cell wall limits expansion in plant cells, resulting in pressure
from within on the cell wall called turgor