Physical Chemistry 2 Van’t Hoff Factor

Colligative Properties of Electrolytes

VAN’T HOFF FACTOR

Introduction
Some chemical substances undergo dissociation or association in solution when used as solutes.
This results in a change in their molar mass and other colligative properties. This can be explained by
Van't Hoff Factor. It was named after Jacobus Henricus Van't Hoff, Jr., a Dutch physical chemist.
Abnormal Mass
The molar mass of a compound is defined as the mass of a sample divided by the amount of
substance in that sample, measured in moles.
When the molecular mass of a solute is calculated from the colligative properties of the solution (in which
that solute has been dissolved), it is occasionally discovered to differ from experimentally obtained values.
This is known as the solute's abnormal molar mass. The reason for this is that some solutes dissociate into
ions or larger molecules when dissolved in solutions.
Colligative Properties
Colligative properties are those properties of solutions that depend on the ratio of the number of
solute particles to the number of solvent molecules in a solution and not on the nature of the chemical
species present.
Colligative properties include the following four main properties:

• Vapor pressure lowering

Raoult’s Law:
p = p⋆AxA
• Boiling point elevation
ΔTb = i × Kb × m
• Freezing point depression
ΔTf = i × Kf × molality
• Osmotic pressure
Π = iMRT
What is Van’t Hoff Factor?
Van't Hoff factor is the measure of the effect of solute on various colligative properties of solutions.
Colligative properties such as relative vapor pressure reduction, osmotic pressure, boiling point elevation,
and freezing point depression are proportional to the amount of solute in the solution. The Van't Hoff factor
is the ratio between the actual concentration of particles produced when a substance is dissolved, and the
concentration calculated from its mass. It is denoted by 'i'.
If we dissolve 1 mole of sugar in 1 liter of water, its colligative properties will not change; however,
if we dissolve 1 mole of salt in 1 L of water, its colligative properties will change because 1 mole of NaCl
will dissociate into 1 mole Na+ and 1 mole Cl-. As a result, theoretical and experimental data for NaCl
solutions will differ. In this case, the Van't Hoff factor is required to correct or measure the change in the
colligative properties of the solution. Various formulae of calculating Van't Hoff factor are given below:
Physical Chemistry 2 Van’t Hoff Factor
Colligative Properties of Electrolytes

Van't Hoff Factor Formula

Van’t Hoff Factor for Dissociated Solutes:

Let's understand it by using NaCl solution. 1 mole of sodium chloride dissolved in 1 L water and
gives 1 mole of sodium and 1 mole of chloride ions. At time 0, when dissociation did not start-

At time t, when dissociation is completed-

On keeping the values from equation in the above formula-

For dissociation, in absence of association, the value of i is greater than 1.

Van't Hoff Factor for Associated Solutes

Let's understand it by using the example of the solution of acetic acid in benzene. Dimerization of
acetic acid takes place in benzene. So, if we take 2 molecules of acetic acid in benzene then it becomes 1.

Thus, at t=0, when association did not start, 2 moles of acetic acid is present. While at time t, when
association is completed, 1 mole of acetic acid is present. As we know Van't Hoff factor-
Physical Chemistry 2 Van’t Hoff Factor
Colligative Properties of Electrolytes

On keeping the values-

For association, the value of i is smaller than 1.

Van't Hoff Factor for Associated solutes and Dissociated solutes can be
summarized in tabulated form as follows:

Quantity of Solute Colligative Molar Mass of Van’t Hoff

Property Solute Factor (i)
Dissociation Increases Increases Decreases i>1
Association Decreases Decreases Increases i<1

Practice Problems

1. Calculate Van't Hoff factor (i) for an aqueous solution of K3[Fe(CN)6] having a degree of
dissociation (α) equal to 0.778.

2. When 9.12 g of HCl was dissolved in 190 g of water, the freezing point of the solution was -
4.65℃. What is the value of the Van't Hoff factor for HCl?

3. Using the Van't Hoff factors in the table below, calculate the mass of solute required to make
each aqueous solution.
Van't Hoff factors at 0.05 m concentration in aqueous solution
Solute Expected Measured
Nonelectrolyte 1 1
NaCl 2 1.9
MgSO4 2 1.3
MgCl2 3 2.7
K2SO4 3 2.6
FeCl3 4 3.4
Calculate the mass of solute required to make 261 mL of a magnesium sulfate solution that has an
osmotic pressure of 3.91 atm at 307 K.

4. The osmotic pressure of 0.01 M solution of CaCl2 and 0.01 M sucrose solution at 298.15 K are
0.605 atm and 0.224 atm respectively. Calculate the Van’t Hoff factor of CaCl2.