Dec-23

Mass Transfer and diffusion

Diffusion
Definition:
The movement of particles from a region of
higher concentration to a region of
lower concentration down the
concentration gradient.

High concentration Low concentration

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 Dec-23

Diffusion cont…

The dye is very concentrated when it

enters the water.
The dye diffuses through the water to lower
concentrated areas until equilibrium is
reached

Diffusion in liquid state The dye is

very
concentrat
ed when it
enters the
water.

: food
coloring
: Water
molecules

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Diffusion in liquid state

The dye diffuses through the water to
lower concentrated areas until
equilibrium is reached

: food
coloring
: Water
molecules

Diffusion in gaseous state

: Perfume
molecules
: Air
molecules
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Diffusion mass transfer

Mass transfer occurs by two basic
mechanisms:
(1) Molecular diffusion by random and
spontaneous microscopic movement of
individual molecules in a gas, liquid, or solid as
a result of thermal motion; and
(2) Eddy (turbulent) diffusion by random
macroscopic fluid motion.

Molecular diffusion
In a binary mixture, molecular diffusion occurs
because of one or more different potentials or
driving forces, including differences (gradients) of
concentration (ordinary diffusion), pressure
(pressure diffusion), temperature (thermal
diffusion), and external force fields (forced
diffusion) that act unequally on the different
chemical species present.
The rate at which a solute moves at any point in
any direction must therefore depends on the
concentration gradient at that point and in that direction.

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Molecular diffusion Cont....

Rates will be most conveniently describes in

terms of a molar flux or mol/(area)(time)

How do we quantify the rate of diffusion?

moles (or mass) diffusing mol kg

J ≡ Flux ≡ = or 2
(surface area )(time) 2
cm s m s

The area being measured in a direction

normal to the diffusion.

Molecular diffusion Cont....

The diffusivity, or diffusion coefficient, DAB of

a constituent A in solution in B, which is a
measure of its diffusive mobility is then
defined as the ratio of its concentration gradient.
Diffusion coefficient/diffusivity

Molar
flux N A = − D AB
dC A

dZ

Concentration gradient
Matter transport is down the concentration gradient
Which is Fick’s law written for the Z direction. 10

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Molecular diffusion Cont....

The negative sign emphasizes that diffusion

occurs in the direction of a drop in
concentration.
The diffusivity is a characteristics of a
constituent and its environment
(temperature, pressure, concentration,
whether in liquid, gas, or solid solution and
the nature of the other constituents).

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Molecular diffusion Cont....

Example:- a box which is separated into two
parts by partition P into
section I water(A) is placed and
in section II ethanol (B)
Density of the liquids are different
Partition- indicates that the depths of the
liquids in each section are the same
Imagine partition carefully removed thus
allowing diffusion of both liquids to occur
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Molecular diffusion Cont....

When diffusion stops, the concentration will
be uniform through out each constituents.

It is clearly indicates that water has diffused

to the right and ethanol to the left
If the direction to the right is taken as
positive flux NA of A relative to the fixed
position P has been positive and flux NB of B
has been negative

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Molecular diffusion Cont....

For a condition of steady state

The net flux is
NA + NB = N
The movement of A is made up of two
parts :
Bulk motion N & the fraction XA of N which is A &
that resulting from diffusion JA
NA = NXA + JA For B,
CA dCA NB = NXB + JB
NA =[NA + NB ] −DAB
C dZ
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or JA = -JB. If CA + CB = const., it follows that DAB

= DBA at the prevailing concentration and
temperature.
All above as considered diffusion in only one
direction, but in general concentration gradients,
velocities, and diffusion fluxes exist in all directions

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Steady state molecular diffusion

for fluids
Applying this eq. to the case of diffusion in Z
direction with NA and NB both constant
(steady state) and if DAB is constant
It can be integrated

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Cont...
Where:- 1= begining of diffusion path (CA high)
2= end of the diffusion path (CA low)
Letting Z2-Z1=Z

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Molecular diffusion in gases

When the ideal gas law applied, this eq. can
be written as in the form of

Also
So that the eq. becames

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Steady state diffusion of A through

nondiffusing B
Example: if ammonia (A) were absorbed
from air (B) into water
In the gas phase air does not dissolve
appreciably in water, and if we neglect the
evaporation of water , only the ammonia
diffuses.
Thus: NB=0, NA =constant

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Cont....
The eq. becomes

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Cont....

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Example:
Oxygen (A) is diffusing through carbon
monoxide (B) under steady-state conditions,
with the carbon monoxide nondiffusing. The
total pressure is 1×105 N/m2, and the
temperature 0oC. The partial pressure of
oxygen at two planes 2.0mm apart is,
respectively, 13,000 and 6500 N/ m2. The
diffusivity for the mixture is 1.87×10-5 m2/s.
Calculate the rate of diffusion of oxygen in
kmol/s through each meter of the two
planes.
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Cont’d….

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.Molecular diffusion in liquid

The integration of the above eq. requires the
assumption that DAB and c are constant.

This is satisfactory for binary gas mixtures

but not in the case of liquids, where both may
vary considerably with concentration.

Nevertheless, in view of our very meager

knowledge of the D's, it is customary to use
together with an average c and the best
average DAB available. 24

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where p and M are the solution density and

molecular weight, respectively.

As for gases, the value of N A/(N A + NB)

must be established by the circumstances
prevailing.
For the most commonly occurring cases,
we have, as for gases:
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Cont’d..
I. Steady state diffusion of A through
nondiffusing B. N A = canst, N B = 0,

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Cont’d….

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Cont’d….

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Diffusivity of Liquids
.
The dimensions for diffusivity in liquids are
the same as those for gases, length2/time.

Unlike the case for gases, however, the

diffusivity varies appreciably with
concentration.

For dilute solutions of nonelectrolytes, the

empirical correlation of Wilke and Chang is
recommended.
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Cont’d..

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DIFFUSION IN SOLIDS
It was indicated that certain of the diffusional
operations such as leaching, drying, and
adsorption and membrane operations such as
dialysis, reverse osmosis, and the like involve
contact of fluids with solids.

In these cases, some of the diffusion occurs in

the solid phase and may proceed according to
any of several mechanisms.
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While in none of these is the mechanism

as simple as in the diffusion through
solutions of gases and liquids nevertheless
with some exceptions it is usually possible
to describe the transfer of diffusing
substance by means of the same basic law
used for fluids, Fick's law.

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FICK'S-LAW DIFFUSION
When the concentration gradient remains
unchanged with passage of time, so that the
rate of diffusion is constant, Fick's law can be
applied when the diffusivity is independent
of concentration and there is no bulk flow.

Thus N A' the rate of diffusion of substance A

per unit cross section of solid, is proportional
to the concentration gradient in the
direction of diffusion, - dcA/dz,

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where DA is the diffusivity of A through the solid. If

DA is constant, integration for diffusion through a
flat slab of thickness z results in

which parallels the expressions obtained for fluids

in a similar situation. Here C Al and CA2 are the
concentrations at opposite sides of the slab. For
other solid shapes, the rate is given by
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with appropriate values of the average cross section

for diffusion S av to be applied. Thus, for radial
diffusion through a solid cylinder of inner and
outer radii al and a2 respectively, and of length l,

and
For radial diffusion through a spherical shell of
inner and outer radii a l and a2,
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