MASS TRANSFER OPERATION-I (2150501)

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.

Molecular diffusion takes place because of random movement of individual molecules.

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 is called as molecular diffusion.

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.

There are two mass transfer mechanisms of interest –

Molecular scale mass diffusion (conduction).

Bulk mass transport (convection).

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 :

1. Distillation : Separation of miscible liquids.

2. Absorption : Soluble vapour absorbed in liquid.
3. Desorption-Stripping : Solute moving from liquid to gas.
4. Dehumidification : Pure liquid condensed from inert gas.
5. Evapouration : Liquid converted to gas.

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 MASS TRANSFER OPERATION-I (2150501)
Semester – V (CHEM)
CHAPTER: 2
Chapter Name: Molecular Diffusion in Fluids
6. Liquid extractions : Impurities removal from liquid using other liquid
7. Crystallization: Formation of crystals
8. Membrane separations: To remove impurities from solution
9. Adsorption : Surface phenomena
10. Leaching: To remove impurities from solid
11. Drying: to remove moisture

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.

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 MASS TRANSFER OPERATION-I (2150501)
Semester – V (CHEM)
CHAPTER: 2
Chapter Name: Molecular Diffusion in Fluids
Next consider what happens when the partition c-c is removed.
The molecules will move around in all directions in a random manner. But since most of the A-molecules are to
the left of c-c, more of the A-molecules will travel from the L.H.S. and to the R.H.S. than in the opposite
direction.
This is the molecular diffusion often A in the direction of decreasing concentration (i.e. from the region of high
concentration to the region of low concentration).
At the same time there is also a net diffusion of B from the R.H.S. to the L.H_S. This diffusion continues until
the concentrations of A and B is uniform throughout.
The rate of diffusion is much greater in gases than in liquids while, diffusion becomes extremely slow process
in solids for same difference in concentration.

MOLECULAR DIFFUSION VERSUS EDDY/TURBULENT DIFFUSION

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.

Now consider Fig.

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 MASS TRANSFER OPERATION-I (2150501)
Semester – V (CHEM)
CHAPTER: 2
Chapter Name: Molecular Diffusion in Fluids
If we place a simple paddle type agitator rotating in the same tank as shown in Fig. at 22 rpm will bring
complete uniformity in about 1 min.
The mechanical agitation has produced rapid movement of relatively large chunks or eddies of fluid
characteristic of turbulent motion, which has carried the salt with them.
This method of solute transfer is called as eddy or turbulent diffusion.

MOLAR FLUX
Rate of diffusion are most conveniently expressed in terms of molecular flux-

It may be described by two terms :

(a) Molar flux (N): It is defined w.r.t. fixed locations in space.

(b) Molar flux (J): It is defined w.r.t. the relative velocity of all components.

MOLECULAR DIFFUSION IN FLUIDS AND DIFFUSION COEFFICIENT OR

DIFFUSIVITY

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

This is FICK’S FIRST LAW OF DIFFUSION in Z-direction.

where:
JAZ = molar flux of A in Z-direction relative to the molar average velocity, (mole/m2 sec.).

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 MASS TRANSFER OPERATION-I (2150501)
Semester – V (CHEM)
CHAPTER: 2
Chapter Name: Molecular Diffusion in Fluids

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-

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 MASS TRANSFER OPERATION-I (2150501)
Semester – V (CHEM)
CHAPTER: 2
Chapter Name: Molecular Diffusion in Fluids

Relation Among Molar Fluxes

For a binary system containing A and B,
For component A,
NA = JA + yA.N
For component B,
NB = JB + yB.N
Add both equations,
NA + NB = (JA + yA.N) + (JB + yB.N)

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

This leads to the conclusion that diffusivity of A in B is equal to diffusivity of B in A.

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 MASS TRANSFER OPERATION-I (2150501)
Semester – V (CHEM)
CHAPTER: 2
Chapter Name: Molecular Diffusion in Fluids

Diffusivity in gases-

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 MASS TRANSFER OPERATION-I (2150501)
Semester – V (CHEM)
CHAPTER: 2
Chapter Name: Molecular Diffusion in Fluids

The diffusion coefficient or diffusivity of liquids may be estimated by Wilke-Chang correlation-

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 MASS TRANSFER OPERATION-I (2150501)
Semester – V (CHEM)
CHAPTER: 2
Chapter Name: Molecular Diffusion in Fluids

YB2 + YA2 =1
YB2 = 1 - YA2
and,
YB1 + YA1 =1
YB1 = 1 – YA1
Put these values in above equation of YB,lm

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 MASS TRANSFER OPERATION-I (2150501)
Semester – V (CHEM)
CHAPTER: 2
Chapter Name: Molecular Diffusion in Fluids
We get,

Substitute value of from above equation into equation of NA ,

This is the equation of molar flux for steady-state diffusion of one gas through a second stagnant gas.

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 MASS TRANSFER OPERATION-I (2150501)
Semester – V (CHEM)
CHAPTER: 2
Chapter Name: Molecular Diffusion in Fluids

So equation becomes,

Prepared By: Mr. Dhiraj Tatar

 MASS TRANSFER OPERATION-I (2150501)
Semester – V (CHEM)
CHAPTER: 2
Chapter Name: Molecular Diffusion in Fluids

Prepared By: Mr. Dhiraj Tatar

 MASS TRANSFER OPERATION-I (2150501)
Semester – V (CHEM)
CHAPTER: 2
Chapter Name: Molecular Diffusion in Fluids

SOLVED NUMERICALS
QUESTION

Solution-

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 MASS TRANSFER OPERATION-I (2150501)
Semester – V (CHEM)
CHAPTER: 2
Chapter Name: Molecular Diffusion in Fluids

QUESTION

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 MASS TRANSFER OPERATION-I (2150501)
Semester – V (CHEM)
CHAPTER: 2
Chapter Name: Molecular Diffusion in Fluids
Solution-

QUESTION

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 MASS TRANSFER OPERATION-I (2150501)
Semester – V (CHEM)
CHAPTER: 2
Chapter Name: Molecular Diffusion in Fluids
Solution-

QUESTION

Solution-

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 MASS TRANSFER OPERATION-I (2150501)
Semester – V (CHEM)
CHAPTER: 2
Chapter Name: Molecular Diffusion in Fluids
QUESTION

Solution-

Prepared By: Mr. Dhiraj Tatar