Lecture week 6 & 7

Knudsen Diffusion
The movement of molecules in a mixture is governed by molecular
velocity as well as collision with other molecules.Collision of the
diffusing molecules with others present in the mixture offers the
resistance to diffusion. If gas diffusion occurs in a very fine pores ,
particularly at a low pressure , the mean free path of the molecules
may be larger than the diameter of the passage . Then collision with
the wall becomes much more frequent than collision with other
molecules.
The rate of diffusional transport of a species is now governed by its
molecular velocity , the diameter of passage and the gradient of
concentration or partial pressure . This is called Knudsen diffusion
and becomes important if the pore size is normally below 50nm. A
simple approach based on kinetic theory of gases yields the following
expression for Knudsen Diffusivity.
 2
Dk= rpvT
3

Where
8𝑅𝑇 1/2
vT=( )
π𝑀

𝐷𝑘 = 9700𝑟𝑝(𝑇/𝑀)0.5
The equation of flux due to Knudsen diffusion is similar to
that of Fick’s Law
𝑑𝐶𝐴 𝐷𝑘 𝑑𝑃𝐴
Jk=-Dk = -
𝑑𝑧 𝑅𝑇 𝑑𝑧
Problem
Estimate the knudsen diffusivity of ethylene
within a 100A pore of a catalyst at 600K.

Solution
2
Dk= rpvT
3
2 8RT 1/2
Dk = rp( )
3 πM

2 −6 8(82.1)(600) 1/2
Dk= ( 10 )( ) = 0.045 centimeter. sq/sec
3 π(28)
Surface Diffusion
Self Diffusion
The molecules of gas or liquid continuously move
from one position to another. As a result of this
continual motion , the molecules in a mixture of
uniform composition also diffuse but the net rate
of transport across any plan over a macroscopic
time scale is zero. Self diffusion refers to the
diffusion of the molecules in a pure substance. ;
the corresponding diffusion coefficient is called
the self diffusion coefficient .
Diffusion in Turbulent Stream
Eddy Diffusion:

As an example of molecular diffusion, let us consider a few

crystals of copper sulphate placed at the bottom of a tall
bottle kept away from any source of disturbance. What we
would observe initially is that the colour will concentrate at
the bottom of the bottle. After a day, it will penetrate a few
centimetres upwards. Ultimately, the solution will become
homogeneous only after a very long time. The movement
of the coloured solution is the result of molecular diffusion
and, as evident, it is extremely slow. In gases molecular
diffusion takes place at a rate of about 10 cm/min, in
liquids its rate is about 0.05 cm/min, and in solids its rate
may be as low as 0.00001 cm/min.
Consider the case of copper sulphate crystals placed at the
bottom of a glass bottle containing water. As the water was
quiescent without any disturbance, the copper sulphate
crystals took unusually long time to get dissolved in water.
If, on the other hand, the contents of the bottle are
vigorously stirred, the copper sulphate crystals will be
completely dissolved within very short time may be within
a minute. Another similar example may be taken from our
daily life with which most of us are well acquainted. When
we add a sugar cube in a cup of tea and leave it as such, the
sugar cube takes very long time to get completely
dissolved. If, on the other hand, the contents of the cup are
vigorously stirred with a spoon, the sugar cube gets
dissolved within a very short time, may be within a minute.
The above examples distinguish two distinct types of
diffusion, molecular diffusion and eddy diffusion or
convective mass transfer.
Eddy diffusion or convective mass transfer occurs in
turbulent fluids and its rate is much faster than that of
molecular diffusion because of high velocity of the
medium that reduces the thickness of the laminar film
at the phase boundary as well as due to random
motion of small lumps of fluid which physically carry
the solute from one position to another.
As in case of convective heat transfer, there may be two
types of convective mass transfer
(i) Forced convection mass transfer
(ii) natural convection or free convection mass transfer.

As the names imply, in forced convection mass transfer

turbulence is created in the medium by external agencies
such as pump, blower, stirrer, etc. In natural convection
mass transfer, on the other hand, turbulence in the
medium is generated mainly due to variation in local
conditions such as variation in solute concentration in the
solution which causes variation in local density
For instance, when a solid gets dissolved in a liquid,
the liquid adjacent to the solid surface becomes
saturated almost immediately and as a result,
becomes heavier than the bulk of liquid. If this
phenomenon takes place at the bottom of the
container, then the heavier fluid remains at the
bottom and natural convection will not take place. If,
on the other hand, dissolution takes place at a certain
height above the bottom of the container, then the
heavier fluid being above the lighter fluid, natural
convection starts. The influence of natural convection
on mass transfer may be considerable, particularly in
the absence of forced convection.
Consider a sugar cube suspended in a glass of
water .Sugar dissolves, the concentration of the
liquid near the surface increases and its density
increases as a result . But the density of the liquid
of the liquid below the sugar cube is less. Thus, a
density difference is created . This causes a
motion in the medium in the form of free
convection currents and thereby enhances the rate
of mass transfer. However , if the sugar cube rests
at the bottom , the density of the liquid at the
bottom will be more than that at top. No buoyancy
force comes into play in this case and there is no
free convection mass tranfer.
For more complex situation such as dissolution
of solid in a mechanically stirred vessel , the
absorption of a gas in a liquid flowing down the
packing in a tower or in a liquid in agitated tank,
the theoretical calculation of mass transfer rate
becomes very difficult. So the concept of mass
transfer gas been introduced with a view to
developing a simple and practically useful
approach to the solution of such problem.
Mass transfer Coefficient
Rate of mass transfer ∞ concentration(driving force)
Rate of mass transfer ∞ area of contact between the
phases

WA is the rate of mass transfer

∆ CA is the concentration driving force between the points
a is the area of contact between the phases

then,
WA ∞ a ∆ CA
WA = kc a ∆ CA
kc = mass transfer coefficient
Since ,

Rate (WA)= NA * a

therefore
NA * a = kc a ∆ CA
NA = kc ∆ CA
kc = NA /∆ CA (molar flux/ concentration driving force)

The inverse of mass transfer coefficient is the

mass transfer resistance
Turbulent or Eddy Diffusion
Wetted Wall Column
Theories of Mass Transfer at phase
Boundary
• Several theories have been proposed with the
objective of explaining the mechanism of
interphase mass transfer and develop
quantitative relations for the same.
1) Two Film theory
2) The Penetration theory
3) Surface Renewal theory
4) Boundary Layer theory
Two Film Theory
In their theory, Lewis and Whitman assumed the
existence of an imaginary film on each side of
the interface (phase boundary). Mass was
visualized as being transferred by steady-state
molecular diffusion through these films each
having such thickness that its resistance to
molecular diffusion is equal to the total
resistance due to both molecular and eddy
diffusion actually offered by the respective
phase.
• When a fluid flows in turbulent motion past a
solid surface with mass transfer taking place
from solid to fluid, the concentration profile is
shown by the continuous line in Figure
 According to the two-film theory, the
concentration profile will be as shown by the
broken line.The basic assumptions of this theory
are:
(i) Mass transfer takes place only by molecular
diffusion through the two imaginary films on
both sides of the interface. Beyond these films,
the fluids are well mixed so that its
concentration is same as that of the bulk fluid.
(ii) Mass transfer through the films is by steady-state
diffusion.
(iii) Bulk flow through the films being very small, the
fluxes within the films can be represented by the
equation.

(iv) The interface itself does not offer any resistance to

mass transfer so that the diffusing component passes on
from one side of the interface to the other side without
any resistance and its concentrations on the two sides of
the interface are in equilibrium.
The mass transfer flux is constant at the film and given as

Comparing with above equation we get

Penetration Theory
In this theory, it has been assumed that the
principal mechanism of interphase mass transfer
involves motion of turbulent eddies from the
core of the fluid to the interface, followed by a
short interval of unsteady-state molecular
diffusion into the other fluid before these eddies
are displaced from the surface by subsequent
eddies.
Higbie further assumed that all eddies that reach the
interface have the same exposure time and the
diffusing molecules cannot reach the depth ze of the
eddies due to slow diffusion and short exposure.
According to this theory, in most cases the time of
exposure of fluid elements to mass transfer is too
short for steady-state concentration gradient to
develop, which is the characteristic of the two-film
theory.
Higbie considered a gas bubble to rise through a
liquid which absorbs the gas. A particle or eddy (
e) of the liquid, initially at the top of the bubble
is in contact with the gas for a time is required
by the bubble to raise a distance equal to its
diameter. The liquid particle then slips along the
surface of the bubble.
He shows an eddy (e) rising from the turbulent
core of the liquid and remaining exposed to the
action of the gas for a time i. In this theory, the
time of exposure has been taken to be the same
for all eddies or particles of the liquid.
Initially, the concentration of the dissolved gas in an
eddy is uniform at cA0 and internally the eddy may
be considered stagnant. When the eddy is exposed
to the gas at the interface, the concentration in the
liquid at the gas-liquid surface becomes cAi which
may be taken as the equilibrium solubility of the gas
in the liquid. During the time i, the liquid particle is
subjected to unsteady-state diffusion of solute in the
z-direction. Therefore as an approximation, the
situation may be represented by Fick’s second law
for unidirectional diffusion.
The average mass flux over the time tc is given by
Fick’s Second Law of Diffusion

Consider diffusion at the front and rear surfaces of an incremental planar

volume. Fick's 2nd law of diffusion describes the rate of accumulation (or
depletion) of concentration within the volume as proportional to the local
curvature of the concentration gradient. The local rule for accumulation is
given by Fick's 2nd law of diffusion:

.
 in which the accumulation, dC/dt [cm-3 s-1], is proportional to the
diffusivity [cm2/s] and the 2nd derivative (or curvature) of the
concentration, [cm-3 cm-2] or [cm-5]. The accumulation is positive when
the curvature is positive, i.e., when the concentration gradient is more
negative on the front end of the planar volume and less negative on the
rear end so that more flux is driven into the volume at the front end than
is driven out of the volume at the rear end.
Surface Renewal theory
The penetration theory was modified by
Danckwerts who proposed the surface renewal
theory(Danckwerts 1951). According to this
theory, the main drawback of the penetration
theory is the assumption that all the liquid
elements or eddies are exposed to the gas for the
same length of time. In a turbulent fluid it is
highly probable that some of the eddies are
swept away while still young; others continue to
be in contact with the gas.
As a result, there is a distribution of the eddies
present at the interface into different ‘age groups’
depending upon their contact time with the gas.
Danckwert assumed random replacement of the
eddies by fresh eddies from the bulk of the liquid. At
any time, each of the eddies at the interface has
equal chance of being replaced by fresh eddies. He
further assumed that unsteady-state mass transfer
occurs to the eddies during their stay at the
interface. Accordingly, he introduced a fractional
rate of surface renewal (s),
where s is the fraction of the surface area
renewed in unit time. He introduced a surface
area distribution function and showed the same
to be equal to sesi. According to this theory, the
mass transfer coefficient works out to be
The Boundary layer theory
• The theories of interphase mass transfer
discussed so far are all based on some selected
models of mass transfer at the phase boundary
without considering the hydrodynamic
conditions which largely affect the nature and
rate of convective mass transfer. As a result,
none of these theories represents a generalized
picture of interphase mass transfer although
they fit well in some specific cases. The
boundary layer theory
on the other hand, gives a much more realistic
picture of the mechanism of mass transfer at a
phase boundary. The concept of boundary layer
originated in the study of fluid dynamics by
Prandtl and was later extended to studies of
heat and mass transfer. Let us consider flow of a
fluid past a wide flat plate at zero angle of
incidence as shown in Figure
• The fluid velocity is zero at the surface of the
plate but increases as the distance from the plate
in the z-direction increases till at sufficiently
large distance when the influence of the solid
plate disappears and the liquid attains its free
stream velocity u0. The region above the solid
plate where the velocity of the fluid changes
from zero to the free-stream velocity, i.e. the
velocity of fully developed flow, is called the
hydrodynamic boundary layer or velocity
boundary layer or momentum boundary layer.
Interphase Mass Transfer
Almost all industrial mass transfer operation
however involve transfer of material from one
phase to another. For instance, in operations
such as gas absorption, liquid extraction,
distillation, drying, crystallization, leaching, etc.,
the diffusing molecules have to travel from the
bulk of one phase to the phase boundary or
interface, cross the interface and then enter into
the bulk of the other phase. In these cases, mass
transfer occurs in both the phases on the two
sides of the interface.
Only in some limited cases, mass transfer takes
place in a single phase. Almost all industrial mass
transfer operations however involve transfer of
material from one phase to another. For instance, in
operations such as gas absorption, liquid extraction,
distillation, drying, crystallization, leaching, etc., the
diffusing molecules have to travel from the bulk of
one phase to the phase boundary or interface, cross
the interface and then enter into the bulk of the
other phase. In these cases, mass transfer occurs in
both the phases on the two sides of the
interface.Only in some limited cases, mass transfer
takes place in a single phase.
• During interphase transfer in fluid systems, both
molecular and eddy diffusion are encountered in
each of the two phases. Transfer in the bulk of
both fluids is usually by eddy diffusion due to
the turbulence created there to enhance the rate
of transfer. On the other hand, thin layers of
fluids on both sides of the interface flow in
laminar motion through which transfer is by
molecular diffusion.
• Figure shows the steady-state transfer of a solute A
from gas phase to liquid phase as in gas absorption.
As figure indicates most of the concentration drops
in both the phases are limited within narrow
laminar regions on both sides of the interface PQ.
These laminar layers offer maximum resistance to
mass transfer, and thus control the overall rate of
transfer. A design engineer should therefore create
conditions so that the thicknesses of these laminar
layers are kept at minimum and their resistances
reduced to the extent possible.
Equilibrium Between Phases
Equilibrium between two phases in contact means a
state in which there is no net transfer of the solute from
one phase to the other. At equilibrium the chemical
potentials of two phases are equal.