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Advanced Mass Transfer

1-Fundamentals
Saeed GUL, Dr.Techn, M.Sc. Engg.
Associate Professor and Chairman

Department of Chemical Engineering,


University of Engineering & Technology Peshawar, PAKISTAN

Introduction on of Mass Transfer


The term mass transfer is used to denote the transference of a
component in a mixture from a region where its concentration
is high to a region where the concentration is lower.
Mass transfer process can take place in a gas or vapour or in a
liquid, and it can result from the random velocities of the
molecules (molecular diffusion) or from the circulating or eddy
currents present in a turbulent fluid (eddy diffusion).
Fractional distillation depends on differences in volatility, gas
absorption on differences in solubility of the gases in a
selective absorbent and, similarly, liquid- liquid extraction is
based on the selectivity of an immiscible liquid solvent for one
of the constituents.
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

Cont.
The mass transfer rate dependent on both the driving force
(concentration difference) and the mass transfer resistance.
Example:

A simple example of a mass transfer process is that occurring in


a box consisting of two compartments, each containing a
different gas, initially separated by an impermeable partition.
When the partition is removed the gases start to mix and the
mixing process continues at a constantly decreasing rate until
eventually (theoretically after the elapse of an infinite time) the
whole system acquires a uniform composition. The process is
one of molecular diffusion in which the mixing is attributable
solely to the random motion of the molecules.
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

Mass Transfer in a Single Phase (Binary Diffusion)


The rate of diffusion is governed by Fick's Law, first proposed by
Fick in 1855 which expresses the mass transfer rate as a linear
function of the molar concentration gradient.
In a mixture of two gases A and B, assumed ideal, Fick's Law for
steady state diffusion may be written as:

Where NA is the molar flux of A (moles per unit area per unit
time)
CA is the concentration of A (moles of A per unit volume),
DAB is known as the diffusivity or diffusion coefficient for A in B,
and y is distance in the direction of transfer.
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

Mass Transfer in a Single Phase (Binary Diffusion)


Fick's law of diffusion
Diffusion occurs in response to a
concentration gradient expressed as the
change in concentration due to a change in
position, . The local rule for movement or
flux J is given by Fick's law of diffusion:

in which the flux NA [cm-2 s-1] is proportional to the diffusivity [cm2/s]


and the negative gradient of concentration, [cm-3 cm-1] or [cm-4].
The negative sign indicates that J is positive when movement is down
the gradient, i.e., the negative sign cancels the negative gradient
along the direction of positive flux.
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

Mass Transfer in a Single Phase (Binary Diffusion)


An equation of exactly the same form may be written for B:

where DBA is the diffusivity of B in A.


As for an ideal gas mixture, at constant pressure
(CA + CB) = constant
so
The condition for the pressure or molar concentration to
remain constant in such a system is that there should be no net
transference of molecules. The process is then referred to as
one of equimolecular counter diffusion
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

Mass Transfer in a Single Phase (Binary Diffusion)


This relation is satisfied only if DBA = DAB

If circulating currents or eddies are present, then the molecular


mechanism will be reinforced and the total mass transfer rate
may be written as:

Whereas D is a physical property of the system and a function


only of its composition, pressure and temperature, ED, which is
known as the eddy diffusivity, is dependent on the flow pattern
and varies with position.
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

Mass Transfer in a Single Phase (Binary Diffusion)


As the pressure P increases, the molecules become closer
together and the mean free path is shorter and consequently
the diffusivity is reduced, with D for a gas becoming
approximately inversely proportional to the pressure.

When diffusion is occurring in the small pores of a catalyst


particle the effects of collision with the walls of the pores may
be important even at moderate pressures.
Where the main resistance to diffusion arises from collisions of
molecules with the walls, the process is referred to Knudsen
diffusion, with a Knudsen diffusivity DKn which is proportional
to the product uml, where l is a linear dimension of the
containing vessel.
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

Mass Transfer in a Single Phase (Binary Diffusion)

Each resistance to mass transfer is proportional to the


reciprocal of the appropriate diffusivity and thus, when both
molecular and Knudsen diffusion must be considered together,
the effective diffusivity De is obtained by summing the
resistances as:
In liquids, the effective mean path of the molecules is so small
that the effects of Knudsen type diffusion need not be
considered.

28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)
Properties of binary mixtures

If A and B are ideal gases in a mixture, the ideal gas law is given by

where nA and nB are the number of moles of A and B and n is


the total number of moles in a volume V, and PA , PB and P are
the respective partial pressures and the total pressure.

28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

10

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

Properties of binary mixtures

where CA and CB are mass concentrations and MA and MB


molecular weights, and CA, CB, CT are, the molar concentrations of
A and B respectively, and the total molar concentration of the
mixture.
From Dalton's Law of partial pressures:

28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

11

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

Properties of binary mixtures


where XA and XB are the mole fractions of A and B. Thus for a
system at constant pressure P and constant molar
concentration CT.

The mass transfer rates NA and NB can be expressed in terms of


partial pressure gradients rather than concentration gradients.
Furthermore, NA and NB can be expressed in terms of gradients
of mole fraction.
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

12

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

Properties of binary mixtures

28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

13

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

Equimolecular Counter Diffusion


When the mass transfer rates of the two components are equal
and opposite, the process is said to be one of equimolecular
counter diffusion.
In binary distillation applications in which the molar heats of
vaporization for species A and B are approximately equal, both
species are diffusing, but at equal rates in opposite directions.

Another example, consider diffusion that occurs in a tube


connecting two tanks containing a binary gas mixture of species
A and B. If both tanks as well as the connecting tube are at a
uniform pressure and temperature, the total molar
concentration would be uniform throughout the tanks and the
connecting tube.
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

14

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

Equimolecular Counter Diffusion


In the case of Equimolecular counter diffusion, the differential
forms of equation for NA may be simply integrated, for
constant temperature and pressure, to give respectively
Integrated form
Differential form

Similar equations apply to NB which is equal to -NA, and suffixes


1 and 2 represent the values of quantities at positions y1 and y2
respectively.
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

15

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)
Equimolecular Counter Diffusion

may be written as:


where hD = D/(y2 y1) is a mass transfer coefficient with the
driving force expressed as a difference in molar concentration;
its dimensions are those of velocity (LT-1).
Similarly:
may be written as:
where k'G = D/[RT(y2 y1] is a mass transfer coefficient with the
driving force expressed as a difference in partial pressure. It
should be noted that its dimensions here, NM-1L-1T, are different
from those of hD
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

16

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)
Equimolecular Counter Diffusion

may be written as:


where kx = DCT/(y1 y2) is a mass transfer coefficient with the
driving force in the form of a difference in mole fraction. The
dimensions here are NL-2T-1
It is always important to use the form of mass transfer coefficient
corresponding to the appropriate driving force.
The mass transfer coefficient is a diffusion rate constant that
relates the mass transfer rate, and concentration gradient as
driving force
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

17

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

Mass transfer through a stationary second component


(Stefans diffusion)
In several important processes, one component in a gaseous
mixture will be transported relative to a fixed plane, such as a
liquid interface, and the other will undergo no net movement.
In gas absorption a soluble gas A is transferred to the liquid
surface where it dissolves, whereas the insoluble gas B
undergoes no net movement with respect to the interface.

In evaporation from a free surface, the vapour moves away


from the surface but the air has no net movement.
The mass transfer process therefore differs from equimolecular
counter diffusion and called Stefans diffusion
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

18

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

Mass transfer through a stationary second component


For the absorption of a soluble gas
A from a mixture with an insoluble
gas B, the respective diffusion rates
are given by:
Mass transfer through a
stationary gas B

Since the total mass transfer rate of B is zero, there must be a


"bulk flow" of the system towards the liquid surface exactly to
counterbalance the diffusional flux away from the surface, as
shown in Figure where:
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

19

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

Mass transfer through a stationary second component


(Stefans diffusion)
The corresponding bulk flow of A must be CA/CB times that of B,
since bulk flow implies that the gas moves en masse.
Thus:
Therefore the total flux of A, N'A, is given by:

The above equation is known as Stefan's Law.


Thus the bulk flow enhances the mass transfer rate by a factor
CT/CB, known as the drift factor
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

20

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

Mass transfer through a stationary second component


Fluxes of components of a gas mixture

28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

21

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

Mass transfer through a stationary second component


As:
On integration:
By definition, CBm, the logarithmic mean of CB1 and CB2 is given by:

Thus, substituting for In (CB2/CB1) :

28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

22

Mass transfer through a stationary second component


In terms of partial pressures:
Similarly, in terms of mole fractions:
This can be simplified when the concentration
of the diffusing component A is small.
Under these conditions CA is small compared with CT, and the
equation becomes:

28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

23

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

Mass transfer through a stationary second component

For small values of CA, CT CAi CT and only the first term in the
series is significant

The above equation is identical to equation for equimolecular


counterdiffusion, Thus, the effects of bulk flow can be
neglected at low concentrations

28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

24

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

Mass transfer through a stationary second component

The above equation can be written in terms of a mass transfer


coefficient hD to give:
Where
Similarly, working in terms of partial pressure difference as the
driving force, the equation can be written:

Where
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

25

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

Mass transfer through a stationary second component


Using mole fractions as the driving force, the equation becomes:

Where

It may be noted that all the transfer coefficients here are greater
than those for equimolecular counter diffusion by the factor
(CT/CBm)(= P/PBm), which is an integrated form of the drift factor.
When the concentration CA of the gas being transferred is low,
CT/CBm then approaches unity and the two sets of coefficients
become identical.
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

26

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

Mass transfer through a stationary second component

Example 10.1
Ammonia gas is diffusing at a constant rate through a layer of
stagnant air 1 mm thick. Conditions are such that the gas
contains 50 per cent by volume ammonia at one boundary of
the stagnant layer. The ammonia diffusing to the other
boundary is quickly absorbed and the concentration is negligible
at that plane. The temperature is 295 K and the pressure
atmospheric, and under these conditions the diffusivity of
ammonia in air is 1.8 x 10-5 m2/s. Estimate the rate of diffusion
of ammonia through the layer.

28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

27

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

Mass transfer through a stationary second component

Solution:
If the subscripts 1 and 2 refer to the two sides of the stagnant
layer and the subscripts A and B refer to ammonia and air
respectively, then the rate of diffusion through a stagnant layer is
given by:
In this case, x = 0.001 m, D = 1.8 x 10-5 m2/s, R = 8314 J/kmol K,
T = 295 K and P = 101.3 kN/m2 and hence:

28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

28

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

Mass transfer through a stationary second component

Thus, substituting in equation


gives:

28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

29

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

Mass transfer velocities


It is convenient to express mass transfer rates in terms of
velocities for the species under consideration where:
which, in the S.I system, has the units
(kmol/m2s)/(kmol/m3) = m/s.
For diffusion according to Fick's Law:
and

Since NB = -NA, then:


As a result of the diffusional process, there is no net overall
molecular flux arising from diffusion in a binary mixture, the two
components being transferred at equal and opposite rates.
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

30

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

Mass transfer velocities


If the physical constraints placed upon the system result in a bulk
flow, the velocities of the molecular species relative to one
another remain the same, but in order to obtain the velocity
relative to a fixed point in the equipment, it is necessary to add
the bulk flow velocity.

The flux of A has been given as Stefan's Law


28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

31

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

General case for gas-phase mass transfer in a binary mixture


Whatever the physical constraints placed on the system, the
diffusional process causes the two components to be
transferred at equal and opposite rates and the values of the
diffusional velocities UDA and UDB are always applicable.
It is the bulk flow velocity uF which changes with imposed
conditions and which gives rise to differences in overall mass
transfer rates.
In equimolecular counterdiffusipn, uF is zero,
In the absorption of a soluble gas A from a mixture the bulk
velocity must be equal and opposite to the diffusional velocity
of B as this latter component undergoes no net transfer.
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

32

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

General case for gas-phase mass transfer in a binary mixture


In genera], for any component:
Total transfer = Transfer by diffusion + Transfer by bulk flow
For component A:
Total transfer (moles/area time) = N'A
Diffusional transfer according to Fick's Law

Transfer by bulk flow


Thus for A:
and for B:

28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

33

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

General case for gas-phase mass transfer in a binary mixture


Substituting:

Similarly for B:
For equimolecular counterdiffusion NA = NB and equation 3
above reduces to Fick's Law. For a system in which B undergoes
no net transfer, NB = 0 and equation 3 is identical to Stefan's
Law
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

34

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

General case for gas-phase mass transfer in a binary mixture


For the general case: fN'A = -N'B
If in a distillation column, for example the molar latent heat of
A is f times that of B, the condensation of 1 mole of A (taken
as the less volatile component) will result in the vaporization
of f moles of B and the mass transfer rate of B will be f times
that of A in the opposite direction

Substituting into equation (

becomes:
Thus:
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

35

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

General case for gas-phase mass transfer in a binary mixture


If xA changes from xAl to XA2 as y goes from y1 to y2

then:
Thus:
Or:

28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

36

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

Diffusion as a mass flux


Fick's Law of diffusion is normally expressed in molar units or:

where XA is the mole fraction of component A.


The corresponding equation for component B indicates that
there is an equal and opposite molar flux of that component. If
each side of equation is multiplied by the molecular weight of A,
MA , then:
where JA is a flux in mass per unit area and unit time (kg/m2 s in
S.I units), and CA is a concentration in mass terms, (kg/m3 )
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

37

Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

Diffusion as a mass flux


Similarly, for component B:
Although the sum of the molar concentrations is constant in an
ideal gas at constant pressure, the sum of the mass concentrations
is not constant, and dcA /dy and dcB /dy are not equal and
opposite,
Thus:
Or:
and:

Thus, the diffusional process does not give rise to equal and
opposite mass fluxes.
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

38

Quiz # 1
Ammonia is absorbed in water from a mixture with air
using a column operating at 1 bar and 295 K. The
resistance to transfer may be regarded as lying entirely
within the gas phase. At a point in the column, the partial
pressure of the ammonia is 7.0 kN/m2. The back pressure
at the water interface is negligible and the resistance to
transfer may be regarded as lying in a stationary gas film
1 mm thick. If the diffusivity of ammonia in air is 236 x
10-5 m2/s, what is the transfer rate per unit area at that
point in the column? How would the rate of transfer be
affected if the ammonia air mixture were compressed to
double the pressure?

28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

39

Mass Transfer in a Single Phase


(Diffusion in Liquids)

The diffusion of solution in a liquid is governed by the same


equations as for the gas phase.
The diffusion coefficient D is about two orders of magnitude
smaller for a liquid than for a gas.
The diffusion coefficient is a much more complex function of
the molecular properties.

For an ideal gas, the total molar concentration CT is constant


at a given total pressure P and temperature T.
This approximation holds quite well for real gases and
vapors, except at high pressures.

28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

40

Mass Transfer in a Single Phase


(Diffusion in Liquids)

For a mixture of ethanol and water for example, the mass


density will range from about 790 to 1000 kg/m3 whereas the
molar density will range from about 17 to 56 kmol/m3.
For this reason the diffusion equations are frequently written
in the form of a mass flux JA (mass/area x time) and the
concentration gradients in terms of mass concentrations, such
as cA .
Thus, for component A, the mass flux is given by:

where is mass density (now taken as constant), and A is the


mass fraction of A in the liquid.
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

41

Mass Transfer in a Single Phase


(Diffusion in Liquids)

For component B:

Thus, the diffusional process in a liquid gives rise to a situation


where the components are being transferred at approximately
equal and opposite mass (rather than molar) rates.
Liquid phase diffusivities are strongly dependent on the
concentration of the diffusing component which is in strong
contrast to gas phase diffusivities which are substantially
independent of concentration.
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

42

Mass Transfer in a Single Phase


(Diffusion in Liquids)

Values of liquid phase diffusivities which are normally quoted


apply to very dilute concentrations of the diffusing
component, the only condition under which analytical
solutions can be produced for the diffusion equations.
For this reason, only dilute solutions are considered here, and
in these circumstances no serious error is involved in using
Fick's law expressed in molar units.
The molar flux is given by:
where D is now the liquid phase diffusivity and CA is the molar
concentration in the liquid phase.
On integration:
D/(y2 y1) is the liquid phase mass transfer coefficient.
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

43

Mass Transfer across a Phase Boundary


In many important applications of mass transfer, material is
transferred across a phase boundary

In distillation a vapor and liquid are brought into contact in


the fractionating column
In gas absorption, the soluble gas diffuses to the surface,
dissolves in the liquid, and then passes into the bulk of the
liquid
In liquid -liquid extraction however, a solute is transferred
from one liquid solvent to another across a phase boundary
These processes is characterized by a transference of material
across an interface.
Because no material accumulates there, the rate of transfer
on each side of the interface must be the same
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

44

Mass Transfer across a Phase Boundary


The mass transfer rate between two fluid phases depend on
the physical properties of the two phases, the concentration
difference, the interfacial area, and the degree of turbulence.
Mass transfer equipment is therefore designed to give a large
area of contact between the phases and to promote
turbulence in each of the fluids.

In most industrial equipment, the flow pattern is so complex


that it is not capable of expression in mathematical terms, and
the interfacial area is not known precisely
A number of mechanisms (models) have been suggested to
represent conditions in the region of the phase boundary
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

45

Mass Transfer across a Phase Boundary


Models for Mass Transfer at a Fluid-fluid Interface
Theoretical models have been developed to describe mass
transfer between a fluid and an interface
The two-film theory
The Penetration Theory
Surface Renewal Theory

28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

46

Mass Transfer across a Phase Boundary


Models for Mass Transfer at a Fluid-fluid Interface

The two-film theory


The two-film theory of WHITMAN was the first serious attempt
to represent conditions occurring when material is transferred
from one fluid stream to another
Although it does not closely reproduce the conditions in most
practical equipment, the theory gives expressions which can be
applied to the experimental data which are generally available,
and for that reason it is still extensively used.
In this approach, it is assumed that turbulence dies out at the
interface and that a laminar layer exists in each of the two fluids.

Outside the laminar layer, turbulent eddies supplement the


action caused by the random movement of the molecules, and
the resistance to transfer becomes progressively smaller.
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

47

Mass Transfer across a Phase Boundary


Models for Mass Transfer at a Fluid-fluid Interface

The two-film theory


AGC and DHF
indicate the
hypothetical
concentration
distributions
L1 and L2:
thicknesses of
the two films

For equimolecular counterdiffusion the concentration gradient is


therefore linear close to the interface, and gradually becomes
less at greater distances as shown in Figure by the full lines ABC
and DEF
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

48

Mass Transfer across a Phase Boundary


Models for Mass Transfer at a Fluid-fluid Interface

The two-film theory


Equilibrium is assumed to exist at the interface and therefore the
relative positions of the points C and D are determined by the
equilibrium relation between the phases.
Integrated form of Ficks law

Can be written in terms of


two film theory

Because material does not accumulate at


the interface, the two rates of transfer
must be the same and:
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

49

Mass Transfer across a Phase Boundary


Models for Mass Transfer at a Fluid-fluid Interface

The Penetration Theory


The penetration theory was propounded in 1935 by HlGBlE
He was investigating whether or not a resistance to transfer
existed at the interface when a pure gas was absorbed in a
liquid.
In his experiments, a slug-like bubble of carbon dioxide was
allowed rise through a vertical column of water in a 3 mm
diameter glass tube.
As the bubble rose, the displaced liquid ran back as a thin film
between the bubble and the tube,
Higbie assumed that each element of surface in this liquid was
exposed to the gas for the time taken for the gas bubble to
pass it; that is for the time given by the quotient of the bubble
length and its velocity.
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

50

Mass Transfer across a Phase Boundary


Models for Mass Transfer at a Fluid-fluid Interface

The Penetration Theory


It was further supposed
that during this short
period, which varied
between 0.01 and 0.1 s
in the experiments,
absorption took place as
the result of unsteady
state molecular diffusion
Penetration of solute into a solvent
into the liquid, and, for
the purposes of calculation, the liquid was regarded as infinite
in depth because the time of exposure was so short.
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

51

Mass Transfer across a Phase Boundary


Models for Mass Transfer at a Fluid-fluid Interface

Regular Surface Renewal Theory


Dankwerts surface renewal theory (1951), represents an
extansion to penetration theory.
Higbie always presupposed that the contact time between the
phases was the same at all positions in the apparatus.
Dankwerts went on to suggest that fluid elements which
come into contact with each other, have different residence
times which can be described by a residence time spectrum.
One has to imagine that mass exchange between two
different materials in the fluid phase takes place in individual
fluid cells.
28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

52

Mass Transfer across a Phase Boundary


Models for Mass Transfer at a Fluid-fluid Interface

Regular Surface Renewal Theory


After a certain amount of time an element can be dislodged
from the contact area and be replaced by another one.
It has been successfully applied in the absorption of gases
from agitated liquids.
However the fraction of time for surface renewal is equally as
unknown as the contact time in penetration theory, so both
theories are useful for the understanding of mass transfer
processes, often neither is applicable for the calculation of the
quantities involved in mass transfer

28 November 2015

Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan

53

Phase Equilibria
A limit to mass transfer is reached if the two phases come to
equilibrium and the net transfer of material ceases.

For a practical process, which must have a reasonable


production rate, equilibrium must be avoided, as the rate of
mass transfer at any point is proportional to the driving force,
which is the departure from equilibrium at that point.
To evaluate driving forces, a knowledge of equilibria between
phases is therefore of basic importance.
Several kinds of equilibria are important in mass transfer.

In nearly all situations two phases are involved, and all


combinations are found except two solid phases.
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Phase Equilibria
More specifically, there are three important criteria for different
phases to be in equilibrium with each other:
The temperature of the two phases is the same at
equilibrium.
The partial pressure of every component in the two phases is
the same at equilibrium.
The Gibbs free energy' of every component in the two phases
is the same at equilibrium.

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Single-Component Phase Equilibrium


If there is only a single component in a mixture, there is only a
single possible temperature (at a given pressure) for which phase
equilibrium is possible.
For example, water at standard pressure (1 atm) can only remain in
equilibrium at 100C.
Below this temperature, all of the water condenses, and above it,
all of the water vaporizes into steam.
At a given temperature, the unique atmospheric pressure at which a
pure liquid boils is called its vapor pressure.
If the atmospheric pressure is higher than the vapor pressure, the
liquid will not boil.
Vapor pressure is strongly temperature-dependent. Water at 100C
has a vapor pressure of 1 atmosphere, which explains why water on
Earth (which has an atmosphere of about 1 atm) boils at 100C.
Water at a temperature of 20C(a typical room temperature) will
only boil at pressures under 0.023 atm, which is its vapor pressure
at that temperature.
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Multiple-Component Phase Equilibrium:


Phase Diagrams
In general, chemical engineers are not dealing with single
components; instead they deal with equilibrium of mixtures.
When a mixture begins to boil, the vapor does not, in general,
have the same composition as the liquid. Instead, the substance
with the lower boiling temperature (or higher vapor pressure)
will have a vapor concentration higher than that with the higher
boiling temperature, though both will be present in the vapor.
A similar argument applies when a vapor mixture condenses.
The concentrations of the vapor and liquid when the overall
concentration and one of the temperature or pressure are fixed
can easily be read off of a phase diagram.
In order to read and understand a phase diagram, it is necessary
to understand the concepts of bubble point and dew point for a
mixture.
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Bubble Point and Dew Point


To predict the phase behavior of a mixture, the limits of phase
changes should be examine, and then utilize the laws of
thermodynamics to determine what happens in between those
limits. The limits in the case of gas-liquid phase changes are called
the bubble point and the dew point.
The bubble point is the point at which the first drop of a liquid
mixture begins to vaporize.
The dew point is the point at which the first drop of a gaseous
mixture begins to condense.
If you are able to plot both the bubble and the dew points on the
same graph, you come up with what is called a Pxy or a Txy
diagram, depending on whether it is graphed at constant
temperature or constant pressure.
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Pxy Diagram
what causes a liquid
to vaporize?
Increasing the temperature
Decreasing the pressure
the two lines intersect at two
ends These intersections are
the pure-component vapor
pressures

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Pxy Diagram
Composition of each component in a 2-phase mixture,

overall composition and the


vapor pressure.
start on the x-axis at the
overall composition
go up to the pressure

Then from this point, go


left until you reach the
bubble-point
go to the right until reach
the dew-point curve to find
the vapor composition
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Txy Diagram

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Txy Diagram

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VLE phase diagram summary


To summarize, here's the information you can directly garner
from a phase diagram. Many of these can be used for all
types of phase diagrams, not just VLE.
You can use it to tell you what phase(s) you are in at a given
composition, temperature, and/or pressure.
You can use it to tell you what the composition of each phase
will be, if you're in a multiphase region.
You can use it to tell you how much of the original solution is
in each phase, if you're in a multiphase region.

You can use it to gather some properties of the pure materials


from the endpoints (though these are usually the best-known
of all the mixture properties).
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Mass Transfer in a Single Phase


(Binary Diffusion in Gas Mixtures)

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Qualitative Analysis of Concentration Profiles


and Mass Transfer

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hypothetical concentration profiles near a gasliquid interface


Mass transfer can only occur along a negative concentration gradient

Case:-1
Here the concentrations in both
the gas and liquid phase diminish
in the positive direction, causing
solute to transfer from the gas to
the liquid phase.
The fact that the interfacial liquid
mole fraction is higher than the
gas
concentration
is
no
impediment.
It is merely an indication of high
gas solubility, a perfectly normal
and acceptable phenomenon.
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Case:- 2
The gas-phase concentration here
increases in the positive direction
so that no transfer of solute from
gas to liquid can take place.
Neither can there be any transfer in
the opposite sense, because the
liquid concentration rises in the
negative direction.
Such profiles arise only in cases
when solute is generated by
chemical reaction at the gas
liquid interface. The product
solute then diffuses from the
interface into the bulk fluids.
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Case:- 3
This case involves decreasing
concentrations in both phases,
but the decrease is in the
negative direction.
Solute will therefore desorb from
the liquid into the gas phase.
Gas solubility is low because
the interfacial concentrations
are nearly identical.

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Case 4:The flat liquid-phase


profile indicates that the liquid
phase is well
stirred and shows no mass
transfer resistance. Because the
gas phase concentration
diminishes in the negative
direction, the transfer will be
from
liquid to gas.

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Case 5:What was stated for Case 4


applies here as well, but the transfer
this time is from the gas. This follows
from the fact that gas-phase
concentration decreases in the positive
direction.
The question is now asked whether the
results would still be the same if
the gas-phase profiles had in each case
been located above the liquid-phase
counterparts. The answer is yes; transfer
would still take place as indicated
before. The only change would be in the
equilibrium solubility of the gas,
which would now be lower than before.
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