Diffusivity in Solids and its Applications

• In many processes such as drying, adsorption and

membrane separations require the contact of gases or
liquids with solids.
• Diffusion occurs in these cases in the solid phase and the
diffusion mechanism is not as simple as in the case of
gases or liquids.
• It is possible to describe by the Fick’s law used in the case
of fluids.
• If the diffusivity is independent of concentration and there
is no bulk flow, the steady state molar flux (NA) in the Z
direction is given by Fick’s law
Fick’s Law

where DA is the diffusivity of A through the solid.

Integration of the above Equation gives diffusion through a
flat slab of thickness z.

where CA1 and CA2 are the concentrations at two opposite

sides of the slab. This is similar expression for diffusion
obtained for fluids under identical situation.
For other solid shapes the general Equation for rate of diffusion (w) is

where Sav is the average cross section for diffusion

 Mechanism of diffusion in solids and its application

• The diffusion of solutes through the solids plays an

important role in many processes such as heterogeneous
catalytic reactions.
• The structure of solid and interaction with the solutes are
important for the rate of diffusion.
 Diffusion in porous solids
The solid sometimes may act as porous barrier or as porous
catalyst pellets and is normally surrounded by a single
body of fluid.
The inward or outward movement of the solutes through
the pores of the solid is mainly by diffusion.
This movement may occur inside the pore or at the surface of
the adsorbed solute.
 Diffusion inside pore
At low pressure the mean free path of the molecules may be
larger than the diameter of the passage when the diffusion
occurs inside the fine pores of the solid.
Between every two consecutive collisions, a gas molecule
travels a straight path. The average distance of all the paths of
a molecule is the mean free path.
The collision with the pore wall becomes important compared
to collision among molecules.
The diffusion of this kind is known as “Knudsen diffusion". To
quantify Kundsen diffusivity a simple Equation based on
kinetic theory of gases was proposed as follows:
rp radius of passage and v is the average velocity of the gas
molecules due to their thermal energy.
Here T is the temperature in K and M is the molecular weight.
The flux due to Knudsen diffusion is similar to Fick’s law
Example Problem 2.1: A test tube, 1.5 cm in diameter and 18
cm long, has 0.4 gm camphor (C10H16O) in it. How long will it
take for camphor to disappear?
The pressure is atmospheric and temperature is 20 0C. The
sublimation pressure of camphor at this temperature is
97.5 mm Hg; diffusivity of camphor can be estimated by
using Fuller’s Equation
Where, T in K; P in bar, MA, MB are molecular weights of A
and B, respectively. A is camphor (C10H16O) and B is air
νA, νB are atomic diffusion volume in m3.
m3 ; 20.1 m3.
Contd.
Contd.
Example 2.2: A mixture of He and N2 gas is contained in a pipe
at 250C and 1 atm. total pressure which is constant through
out. At one end of the pipe, partial pressure of He is 0.6 atm.
and at the other end (0.2 m) it is 0.2 atm
Calculate the steady state flux of He if DAB of He-N2 mixture
can be estimated by using Fuller’s Equation with
m3 m3
Solution
MeOH (A) is separated from aqueous solution by
distillation. At a section of column, vapor phase contains
0.76 mole fraction MeOH and liquid phase has 0.6 mole
fraction. Temperature of the section is 71.20C and total
pressure is 1 atm. throughout 1 mm thick vapor film. If
molar latent heat of vaporization of MeOH is 8787 K Cal/K
mol and that of water (B) is 10039 K Cal/K mol at the given
temperature. Calculate MeOH and water vapor flux.
Given: If mole fraction of MeOH in liquid is 0.6, equilibrium
vapor will be 0.825. Vapor phase diffusivity of MeOH, DAB =
1.816×10-5 m2/s.
Soln
Contd