Dr.

Nagi Osman Mohammed (2021)

Lecture NO(2)
Diffusion
2.1 Definition
The term diffusion (mass transfer) is used to denote the transference of a component in a
mixture from a region where its concentration is high to a region where the concentration
is lower. Diffusion process can take place in a gas or vapors or in a liquid, and it can result
from the random velocities of the molecules (molecular diffusion) or from the circulating
or eddy currents present in a turbulent fluid (eddy diffusion).
2.2 Diffusion depends on:
1. Driving force (ΔC), moles per unit volume (kmol/m3).
2. The distance in the direction of transfer (Δz), meter (m).
3. Diffusivity coefficient, unit area per unit time (m2/s).

Dr.Nagi Osman Mohammed (2021)

Dr.Nagi Osman Mohammed (2021)

2.3 Models of Diffusion

Two mathematical models have been more or less successful in explaining the mechanism
of diffusion. The one proposed by Adolf Fick, uses a diffusion coefficient while the other
model uses a mass transfer coefficient. Both the models were verified by a simple
experiment shown in Figure1.1.

Figure1.1 Verification of diffusion law.

Tank 1 containing carbon dioxide is connected by a long connecting line to tank 2

containing air[Figure1.1(a)]. Both tanks of equal volume were sufficiently large. These
were kept at constant temperature and pressure. On opening the valve the diffusion
proceed, and the concentration of carbon dioxide in tank 2 was measured at a regular
interval of time. The concentration of carbon dioxide in tank 2 thus measured was found
to vary linearly with time as shown in Figure1.1(b). Similar observation was made
elsewhere (Cussler 1997) for different system. In Fick’s model, the results were correlated
as

Dr.Nagi Osman Mohammed (2021)

Dr.Nagi Osman Mohammed (2021)

Where, the proportionality constant D is the diffusion coefficient. A discussion on Fick’s

law has been taken up in Section 2.3. The other model assumed the carbon dioxide flux to
be proportional to the gas concentration.
Carbon dioxide flux = k (carbon dioxide concentration difference)
Where, the proportionality constant k is the mass transfer coefficient. This is a type of
reversible rate constant. Fick’s model is commonly used in basic sciences to describe
diffusion. In the mass transfer coefficient model, on the other hand the coefficient, k takes
care of several parameters which cannot be directly measured. Mass transfer coefficient
leads to the development of correlations commonly used in chemical engineering, chemical
kinetics and medicine. Both the models have striking similarity with Ohm’s law. The
diffusion coefficient is analogous to the reciprocal of resistivity while mass transfer
coefficient is analogous to the reciprocal of resistance. Both the models have some
demerits also. For instance, the flux may not be proportional to the concentration
difference if the capillary is very thin or if the gases react. The model based on diffusion
coefficient gives results of more fundamental value than those obtained using the model
based on mass transfer coefficient. The diffusion model has distributed parameters for the
dependent variable, i.e. the concentration is allowed to vary with all independent variables
like position and time.
2.4 Fick’s Law
Based on his diffusion model (Section 2.2) and series of experiments conducted by
Graham (Graham 1850) and himself, Adolf Eugen Fick proposed the basic law of
diffusion known as Fick’s law (Fick 1885) which is the foundation of all subsequent

works on molecular diffusion. According to Fick’s Law for one-dimensional steady-

state molecular diffusion, the molar flux of a component in a frame of reference moving

Dr.Nagi Osman Mohammed (2021)

Dr.Nagi Osman Mohammed (2021)

with the molar average velocity is proportional to the concentration gradient of the
component. If A diffuses in a binary mixture of A and B, then according to Fick’s law
The rate of diffusion is governed by Fick's Law, first proposed by Fick in 1855 which
expresses the mass transfer rate as a linear function of the molar concentration gradient.
In a mixture of two gases A and B, assumed ideal, Fick's Law for steady state diffusion
may be written as:

Where:

[ ]

[ ].

The negative sign in Eq. (2.2) indicates that diffusion takes place in the direction of
decreasing concentration. It is interesting to note that Eq. (2.2) is similar to other basic
laws of transport, namely Fourier’s law of heat conduction and Newton’s law of viscosity.
In case of heat conduction, the heat flux is proportional to the temperature gradient, i.e.

Where, is the flux of heat in the z-direction in which the temperature decreases,
= a is the thermal diffusivity, L2/θ and [ ] is the gradient of concentration of
heat.

Dr.Nagi Osman Mohammed (2021)

Dr.Nagi Osman Mohammed (2021)

According to Newton’s law of viscosity, the shear stress or momentum flux in a

viscous fluid in laminar motion is proportional to the velocity gradient from a faster
moving layer to an adjacent slower moving layer, i.e.

Where, ux is the velocity in the direction normal to the direction of momentum

transfer, is the gradient of concentration of momentum, ( ) = n is the
kinematic viscosity or momentum diffusivity, L2/ θ and is the flux of momentum
in the z-direction.
Fick’s law for one-dimensional diffusional mass transport in three different co-ordinates
can be represented as
(i) For one dimensional diffusion in Cartesian co-ordinates [Eq. (2.2)]

(ii) For radial diffusion in Cylindrical co-ordinates

(iii) For radial diffusion in Spherical co-ordinates

2.5 Diffusion with bulk of mass in motion:

Although the original form of Fick’s law as given in Eq. (2.2) defines molar flux, JA with
respect to a frame of reference moving with the molar average velocity, molar flux NA
with respect to stationary frame of reference has been found to be more useful for
practical purposes. NA can be derived from JA in the following way:
From Eq. (1.17) for a binary system,

And from Eq. (1.21),

Combining Eqs. (2.3) and (2.4), we get

Dr.Nagi Osman Mohammed (2021)

Dr.Nagi Osman Mohammed (2021)

Therefore, from Eqs. (1.23) and (2.2)

Substituting the expression for U from Eq. (2. 5), we obtain

[ ]

[ ]

[ ]
Equation (2.6) gives the molar flux of A in a binary mixture of A and B with respect to a
stationary frame of reference. The molar flux, NA may be considered to consist of two

parts, the part [ ] due to

diffusion. In dilute solutions, bulk motion becomes negligible and the molar flux reduces
to

Total diffusion equation (2.6) in the form of concentration (normally used for liquids)
The total diffusion equation can be written in other forms:
a. Partial pressure for gases.
b. Mole fraction for gases and liquids.

a. Total diffusion equation in the partial pressure form:

If A and B are ideal gases in a mixture, the ideal gas law may be applied to each gas
separately and to the mixture:

Dr.Nagi Osman Mohammed (2021)

Dr.Nagi Osman Mohammed (2021)

Total diffusion equation (2.8) in the form of partial pressure (normally used for gases)

b. Total diffusion equation in the mole fraction form:

Then:

Total diffusion equation (2.9) in the form of mole fraction (used for gases and liquids)
If the gas mixture is ideal , the mutual diffusivities of A and B are equal .
The flux of B in the mixture can be written following Eq (2.6)

[ ]

( )[ ]

Noting that

We get the result

Dr.Nagi Osman Mohammed (2021)