Unit Operations – Molecular Diffusion of Gases

Molecular diffusion is the movement of one gas through another by

thermal random motion.

Graham's Law of Diffusion

Thomas Graham studied the rate of diffusion of various gases and

gave this law. It states that under similar conditions of temperature and
pressure, the rates of diffusion of gases are inversely proportional to the
square roots of their densities.

It can be represented as:

The rates of diffusion of two gases when compared with each other can be
given as:

Molecular mass is twice the vapour density, substituting this in the

equation, we have,

where M1 and M2 are the molecular masses of the two gases. Thus, the
rate of diffusion of gases is inversely proportional to the square root of
their molecular masses.

Graham's law is useful in:

• Separation of gases having different densities by diffusion.
• Determining the densities and molecular masses of unknown gases
by comparing their rates of diffusion with known gases.
• Separating the isotopes of some of the elements.

Sample problems:
1. An unknown gas diffuses four times as quickly as oxygen. Calculate the
molecular mass of the gas.

Let the rate of diffusion of oxygen be r (O2) = r1

The rate of diffusion of the unknown gas r (x) = 4r

Molecular mass of O, M (O2) = 32

Molecular mass of unknown gas M (x) = M

From Graham's Law of diffusion,

or

Squaring on both sides,

M(x) = 2 g/mol

2. What is the molecular weight of a gas which diffuses 1/50 as fast as

hydrogen?

Solution:

Set rate1 = other gas = 1/50 (r2)

Set rate2 = H2 = r2

The molecular weight of H2 = 2.02

The molecular weight of the other gas = x.

[(1 / 50) r2] / [r2] = √(2.02 / x)

x = 5050 g/mol

3. Equal volumes of two gases A and B diffuse through a porous pot in 20

and 10 seconds respectively. If molar mass of A be 80, find the molar
mass of 'B'.
Sol.

R1/R2 = √ (M2/M1) , V1 = V2

(V1/t1) / (V2/t2) = √ (M2/M1)

t2/t1 = √ (M2/M1)

10/20 = √ (M2/80)

1/2 = √ (M2/80) 1/4 = (M2/80)

M2 = 20 g/mol