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Semester – V (CHEM)
CHAPTER: 2
Chapter Name: Molecular Diffusion in Fluids
When the composition of a fluid mixture varies from one point to another, each component of the mixture will
tend to flow in the direction that will reduce the difference in local concentration.
If the bulk fluid is stationary or moving in laminar motion in a direction normal to the direction of concentration
gradient, the process reducing the concentration difference is known as molecular diffusion.
It is a very slow process and quite different from bulk transport by eddies which phenomenon is much faster as
it takes place in a turbulent fluid.
Molecular transport of mass, heat and momentum occurs in gases, liquids and solids.
It is the basic physical mechanism underlying many important unit operations.
Molecular transport occurs in any homogenous material, it may be gas, liquid or solid.
When a system contains two or more components whose concentrations vary from point to
point, there is a tendency for mass to be transferred to minimize the concentration differences.
The factors affecting mass transfer includes vapour pressure, solubility and diffusivity.
In unit operations, mainly concerned with the transfer of mass between three phases : solid,
liquid and gaseous :
MOLECULAR DIFFUSION
Definition : The mass transfer of the species from region of higher concentration to region of lower concentration
is accomplished by the actual migration of molecules. This phenomenon is called as molecular diffusion.
Molecular diffusion or molecular transport can be defined as the transfer or movement of individual molecules
through a fluid by means of random, individual movements of the molecules.
The molecules travel only in straight lines and in the process, may collide with other molecules in their path.
The molecules then change direction (still in a straight line) after the collision.
This is sometimes referred to as a random-walk process as shown in the Fig. as follows.
Now consider a container with a mixture of two components A and B at constant pressure P and constant
temperature T as shown in the figure below. A fictitious partition c-c separates the container into two sections.
The L.H.S. contains more molecules of component A than the R.H.S., and the reverse is true for the B.
Molecular diffusion is a slow process and with rapid mixing which can be brought about by mechanical stirring
and convective movement of fluids. Consider a tank as shown in Fig. Here a 0.75 m — deep layer of pure water
has been carefully placed over the brine solution without disturbing the brine solution in any way.
If the contents of the tank are left completely undisturbed by molecular diffusion, the salt will completely
permeate the liquid, ultimately coming everywhere to one-half its concentration in the original brine.
But this process is very slow, and it is estimated that the salt concentration at the top surface will be only 87.5%
of its final value after 10 years and will reach 99% of its final value only after 28 years.
MOLAR FLUX
Rate of diffusion are most conveniently expressed in terms of molecular flux-
(b) Molar flux (J): It is defined w.r.t. the relative velocity of all components.
The diffusivity, DAB. of component A in solution in B which is a measure of its diffusive mobility is defined as
the ratio of its flux JA, to the concentration gradient
Fick’s Law
An empirical relation for the diffusional molar flux, first postulated by Fick and accordingly, often referred to
as Fick's first law, defines the diffusion of component A in an isothermal, isobaric system. For diffusion in only
the Z direction, the Fick’s rate equation is
So, total flux for component A will be addition of flux due to internal molecules or fixed positions and due to
their velocity-
N = JA + JB + yA.N + yB.N
N = JA + JB + (yA+ yB)N
N = JA + JB + N
N - N = JA + JB
JA + JB = 0
JA = - JB
Diffusivity in gases-
YB2 + YA2 =1
YB2 = 1 - YA2
and,
YB1 + YA1 =1
YB1 = 1 – YA1
Put these values in above equation of YB,lm
This is the equation of molar flux for steady-state diffusion of one gas through a second stagnant gas.
So equation becomes,
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