6.1.3.

Fick’s Law of Diffusion

The rate equation for mass diffusion is known as Fick.s
law, and for the transfer of species A in a binary mixture
of A and B, it may be expressed in vector form as;
jA = -ρDAB………………………………………..6.12
jA* = -CDAB…………………………………………….6.13
The quantity jA (kg/sm2) is diffusive mass flux of species
A.
It is the amount of A that is transferred by
diffusion per unit time and per unit area
perpendicular to the direction of transfer, and
it is proportional to the mixture mass density, ρ= ρ

A+ ρ B (kg/m3), and to the gradient in the species

mass fraction, XA = ρ A/ ρ.
 Cont…
The species flux may also be evaluated on a molar basis,
where J*A (kmol/s m2) is the diffusive molar flux of species
A. It is proportional to the total molar concentration of the
mixture, C = CA + CB (kmol/m3), and to the gradient in the
species mole fraction, YA = CA/C.
 6.1.4. Mass Diffusivity
To predicting the mass diffusivity DAB for the
binary mixture of two gases, A and B. Assuming
ideal gas behavior, kinetic theory may be used
to show that;

…………………6.14
Where, c is the mean electron velocity, and
mfp is the electron mean free path, which is
defined as the average distance traveled by an
electron before it collides with either an
imperfection in the material.
 Cont….
c increases with increasing temperature and
decreasing molecular weight,
Therefore the mass diffusivity increases with

increasing temperature and decreasing

molecular weight.
Because of λmfp is inversely proportional to gas
pressure, the mass diffusivity decreases with
increasing pressure.
 6.2. Mass Transfer in Non stationary Media
6.2.1. Absolute and Diffusive Species Fluxes
The diffusion of a species always involves the movement
of molecules or atoms from one location to another.
The molecular scale motion results in bulk motion.
To obtain an expression for the absolute mass flux,
consider species A in a binary mixture of A and B. The
absolute mass flux n’’A is related to the species absolute
velocity vA by;
n’’A = ρAvA………………………………..6.15
A value of vA associated with any point in the mixture,
and it is interpreted as the average velocity of all the A
particles in a small volume element about the point.
 Cont…
An average, or aggregate, velocity associated with the
particles of species B, in which case
n’’B = ρBvB………………………………………………..…6.16
A mass-average velocity for the mixture may then be
obtained from the requirement that;
ρv = n’’ = n’’A + n’’B = ρAvA + ρBvB………………..6.17
and Giving
V = XAvA + XBvB………………………………….6.18
The mass flux of species A relative to the mixture
mass-average velocity as;
jA = ρA(vA - v)……………………………………….…6.19
 Cont…
Whereas n’’A is the absolute flux of species A, jA is the
relative or diffusive flux of the species and the quantity
given by Fick’s law, Equation 6.12. It represents the
motion of the species relative to the average motion of
the mixture. It follows from Equations 6.15 and 6.19 that;
n’’A = jA +ρAv……………………………………6.20
This expression delineates the two contributions to the
absolute flux of species A:
A contribution due to diffusion (i.e., due to the
motion of A relative to the mass-average motion of
the mixture) and
A contribution due to advection (i.e., due to motion
of A with the mass average motion of the mixture).
 Cont….
Substituting from Equations 6.12 and 6.17, we obtain;

………………….6.21
If the second term on the right-hand side of Equation 6.21
is zero, mass transfer of species A occurs purely by
diffusion and
The situation is analogous to heat transfer purely by

conduction. We will later identify special situations for

which this occurs.
The foregoing considerations may be extended to species B.
The mass flux of B relative to the mixture mass-average velocity
(the diffusive flux) is;
jB = ρB(vB - v)………………………6.22
Where, jB = -ρDBAmB…………………….6.23
 Cont….
It follows from Equations 6.17, 6.19, and 6.22 that the
diffusive fluxes in a binary mixture are related by;
jA + jB = 0…………………………………………..6.24
If Equations 6.12 and 6.23 are substituted into
Equation 6.24, and it is recognized that;
mA = -mB,

 since mA + mB = 1

 For a binary mixture, it follows that;

DBA = DAB………………………………………..6.25
Cont….
Hence, as in Equation 6.21, the absolute flux of
species B may be expressed as;
……………………………….6.26

The absolute molar fluxes of species A and B may be

expressed as;
N’’A = CAvA and N’’B = CBvB……..6.27
A molar-average velocity for the mixture, v*, is
obtained from the requirement that;
N’’ = N’’A + N’’B = Cv* = CAvA + CBvB…………6.28
Giving
v* = xAvA + xBvB………………………………..6.29
Cont….
Equation 6.27 provides the absolute molar flux of
species A and B.
The molar flux of A relative to the mixture molar
average velocity J*A, termed the diffusive flux,
obtained from Equation 6.13 or from the expression;
J*A = CA(vA - v*)………………………6.30
To determine an expression similar in form to
Equation 6.21, we combine Equations 6.27 and 6.30 to
obtain;
N’’A = J*A + CA v*……………………6.31
Or, from Equations 6.13 and 6.28,
………………6.32
Cont….
Note that Equation 6.32 represents the absolute
molar flux as the sum of a diffusive flux and an
advective flux.
Again, if the second term on the right-hand side is
zero, mass transfer is purely by diffusion and is
analogous to heat conduction, when formulated in
molar quantities instead of mass quantities.
For the binary mixture, it also follows that;
J*A + J*B = 0………………………6.33
 6.3. Conservation of Species for a
Stationary Medium
6.3.1. Conservation of Species for a
Control Volume
The law of conservation of species plays an
important role in the analysis of mass transfer.
problems.
The rate at which the
The rate at which the The rate at which this
species mass is
mass species enters + generated within the
- species mass leaves
to a control volume, the control volume
control volume

The rate of increase

= of the species mass
stored within the
control volume.
Cont….
For any species A may enter and leave the
control volume due to both fluid motion and
diffusion across the control surface.
The conservation equation may then be
expressed on a rate basis as;
……………6.41

Species generation exists when chemical

reactions occur in the system.
 6.3.2. The Mass Diffusion Equation
Mass, or species, diffusion equation that is
analogous to the heat equation.
We consider a medium that is a binary mixture of
species A and B for which the stationary medium
approximation holds.
That is, mass transfer may be approximated as
occurring only by diffusion because advection is
negligible.
The resulting equation could be solved for the
species concentration distribution, which could be
used with Fick’s law to determine the species
diffusion rate at any point in the medium
 Cont…
Allowing for concentration gradients in each of the x, y,
and z coordinate directions, we first define a differential
control volume, dx dy dz, within the medium.
The concentration gradients, diffusion must result in the
transport of species A through the control surfaces.

………6.42a
 Cont….

Differential
control volume,
dx dy dz, for
species diffusion
analysis in
Cartesian
coordinates.

…………….. 6.42b

………………6.42c
 Cont…
The rate at which species A is generated within
the control volume due to such reactions may
be expressed as;
………………….6.43
Where nA is the rate of increase of the mass of species A
per unit volume of the mixture (kg/s m3).
Finally, these processes may change the mass of
species A stored within the control volume, and the
rate of change is;

………………………………6.44
 Cont….
With mass inflow rates determined by n’’A,x, n’’A,y, and
n’’A,zand the outflow rates determined by Equations 6.42,
Equations 6.42 through 6.44 may be substituted into
Equation 6.41 to obtain;

………………………6.45
Then, substituting the x, y, and z components of
Equation n’’A = jA = DABmA (stationary medium
approximation is appropriate, the diffusive mass and
molar fluxes), we obtain;

 ……6.46a
Cont…
In terms of the molar concentration, a similar
derivation yields;
…6.47a

In subsequent treatments of species diffusion

phenomena, we shall work with simplified versions of
the foregoing equations. In particular, if DAB and ρ are
constant, Equation 14.46a may be expressed as;

……………..6.46b
 Cont…

Similarly, if DAB and C are constant, Equation
6.47a may be expressed as;
……………………6.47b


The species diffusion equations may also be expressed in
cylindrical and spherical coordinates.

These alternative forms can be inferred from the
analogous expressions for heat transfer, equation and in
terms of the molar concentration are:
Cont…
Cylindrical Coordinates:

Spherical Coordinates:
 THE END
THANK YOU FOR
YOUR ATTENTION!!!