MASS TRANSFER AND ITS

APPLICATIONS
 Mass transfer – transfer of material from
one homogeneous phase to another.
 Based on differences in vapor pressure,
solubility, diffusivity.
 Driving force for transfer is a concentration
difference.
 Mass transfer operations – gas absorption,
distillation, extraction, leaching, adsorption,
crystallization, membrane separations, etc..
PRINCIPLES OF DIFFUSION
 Diffusion– is the movement, under the
influence of a physical stimulus, of an
individual component through a mixture.

 Common cause of diffusion: concentration

gradient

 Example: Removal of ammonia by gas

absorption.
 Fick’s Law of Diffusion:

dc A
J A   DV
db
 JA = molar flux of comp. A (kg mol/m2.h)
 Dv = volumetric diffusivity (m2/h)

 cA = concentration (kg mol/m3)

 b = distance in direction of diffusion (m)

Mass Transfer Theories

 Turbulent flow is desired in most mass-

transfer operations:
1. to increase the rate of transfer per unit
area
2. to help disperse one fluid in another
3. to create more interfacial area

 Masstransfer to a fluid interface is often

unsteady-state type.
MASS TRANSFER THEORIES

Mass transfer coefficient, k

 Is defined as rate of mass transfer per unit area per
unit conc. difference.

 kc is molar flux divided by conc. difference

 kc has a unit of velocity in cm/s, m/s

 Concentration, c in moles/volume
MASS TRANSFER THEORIES
Mass transfer coefficient, k

 ky in mol/area.time (mol/m2.s)
 y or x are mole fractions in the vapor or liquid phase.
Gas phase coefficient, kg
 MASS TRANSFER THEORIES
There are three types of theories in mass transfer
coefficients.
1) Film theories
2) Penetration theories
3) Surface –renewal theories
Film Theory
The simplest conceptualization of the gas-liquid transfer process
is attributed to Nernst (1904).
Nernst postulated that near the interface there exists a stagnant
film . This stagnant film is hypothetical since we really don't
know the details of the velocity profile near the interface.

• Basic concept – the resistance to diffusion can be considered

equivalent to that in stagnant film of a certain thickness

• Often used as a basis for complex problems of

multicomponent diffusion or diffusion plus chemical reaction.
a) Mass transfer occurs by molecular diffusion through a
fluid layer at phase boundary (solid wall). Beyond this
film, concentration is homogeneous and is CAb.
b) Mass transfer through the film occurs at steady state.
c) Flux is low and mass transfer occurs at low
concentration. Hence,
Integrating Equation (3.55) for the following boundary
conditions: CA=CAi when Z=0 CA=CAb when Z=δ We have
now:
In this film transport is governed essentially by
molecular diffusion. Therefore, Fick's law
describes flux through the film.

C mg
J  D (typical units )
X 2
cm sec
If the thickness of the stagnant film is given by
dn then the gradient can be approximated by:

C Cb Ci

X dn

Cb and Ci are concentrations in the bulk and at

the interface, respectively.
At steady-state if there are no reactions in the
stagnant film there will be no accumulation in
the film (Assume that D = constant) -- therefore
the gradient must be linear and the
approximation is appropriate.
And:

(Cb  Ci )
J  D
dn
Calculation of Ci is done by assuming that
equilibrium (Henry's Law) is attained instantly at
the interface. (i.e., use Henry's law based on the
bulk concentration of the other bulk phase.) Of
course this assumes that the other phase doesn't
have a "film". This problem will be addressed
later. So for the moment:

Cg (if the film side is liquid and the

Ci  opposite side is the gas phase).
Hc
A problem with the model is that the effective
diffusion coefficient is seldom constant since
some turbulence does enter the film area. So the
concentration profile in the film looks more like:
Penetration and Surface Renewal Models

Most of the industrial processes of mass transfer is unsteady state

process. In such cases, the contact time between phases is too short to
achieve a stationary state. This non stationary phenomenon is not
generally taken into account by the film model.

More realistic models of the process have been proposed by Higbie

(1935, penetration model) and by Danckwerts ( 1951, surface renewal
model). In these models bulk fluid packets (eddies) work their way to the
interface from the bulk solution. While at the interface they attempt to
equilibrate with the other phase under non-steady state conditions. No
film concepts need be invoked. The concentration profile in each eddy (
packet) is determined by the molecular diffusion dominated advective-
diffusion equation:
 Basic assumptions of the penetration theory are as follows:
1) Unsteady state mass transfer occurs to a liquid element so long it
is in contact with the bubbles or other phase
2) Equilibrium exists at gas-liquid interface
3) Each of liquid elements stays in contact with the gas for same
period of time

C 2
 C
D
t X 2

Assumption: no advection within the eddy

The solution to this governing equation depends, of
course, on boundary conditions. In the Higbie
penetration model it is assumed that the eddy does not
remain at the surface long enough to affect
concentration at the bottom of the eddy ( z = zb). In
other words the eddy behaves as a semi-infinite slab.
Where C (@ z = zb ) = Cb. Also C (@ z = 0) = Ci .
The boundary conditions are:
t = 0, Z > 0 : c = cAb
and t > 0, Z = 0 : c = cAi.
Solving the equation with these boundary conditions and
then solving for the gradient at z = 0 to get the flux at z = 0
and then finding the average flux over the time the eddy
spends on the surface yields the following:

D  = average time at surface (a

J 2 Ci Cb  constant for a given mixing level).


The average mass transfer coefficient during a time interval tc is then

obtained by integrating Equation (3.61) as
For the mass transfer in liquid phase, Danckwert (1951) modified the Higbie’s
penetration theory with the surface renewal model. He stated that a portion of the
mass transfer surface is replaced with a new surface by the motion of eddies near the
surface and proposed the following assumptions:
1) The liquid elements at the interface are being randomly swapped by fresh
elements from bulk
2) At any moment, each of the liquid elements at the surface has the same probability
of being substituted by fresh element
3) Unsteady state mass transfer takes place to an element during its stay at the
interface.

J  Ci Cb  Ds

s = surface renewal rate (again, a function of

mixing level in bulk phase).
Comparison of the models:
Higbie and Danckwert's models both predict that
J is proportional to D0.5 where the Nernst film
model predicts that J is proportional to D. Actual
observations show that J is proportional to
something in between, D0.5 -1 . There are more
complicated models which may fit the
experimental data better, but we don't need to
invoke them at this time.
 Mass transfer coefficients
To simplify calculations we usually define a mass
transfer coefficient for either the liquid or gas
phase as kl or kg (dimensions = L/t).

D
k l,g  2 (Higbie)

k l,g  Ds (Danckwerts)

D
k l,g  (Nernst)
dn
Boundary Layer Theory
• Mass transfer often take place in a thin boundary
layer near a surface where the fluid is in laminar
flow.
• The coefficient, kc depends on 2/3 power of
diffusivity and decreases with increasing distance
along the surface in the direction of flow
• Boundary layer theory can be used to estimate kc
for some situations,
• but exact prediction of kc cannot be made when the
boundary layer become turbulent.
When δ=δ(x)u=Uα and when δ=δm(x)-> u=0.99Uα distance over which solute
concentration drops by 99% of (CAi-CAb).

where, x is the distance of a point from the leading edge of the plate; kL,x is the
local mass transfer coefficient.

where, l is the length of the plate.

 Two film model
In many cases with gas-liquid transfer we have
transfer considerations from both sides of the
interface. For example, if we invoke the Nernst
film model we get the Lewis-Whitman (1923)
two-film model as described below.
The same assumptions apply to the two films as
apply in the single Nernst film model. The
problem, of course, is that we will now have
difficulty in finding interface concentrations, Cgi
or Cli. We can assume that equilibrium will be
attained at the interface (gas solubilization
reactions occur rather fast), however, so that:

Cgi
Cli 
Hc
A steady-state flux balance (okay for thin films)
through each film can now be performed. The
fluxes are given by:

J = kl(Cl -Cli)
and
J = kg(Cgi-Cg)
If the Whitman film model is used:

Dl,g
kl,g  (m/sec)
dl,g

(Note the Higbie or Danckwerts models can be

used without upsetting the conceptualization)
Unfortunately, concentrations at the interface
cannot be measured so overall mass transfer
coefficients are defined. These coefficients
are based on the difference between the bulk
concentration in one phase and the
concentration that would be in equilibrium
with the bulk concentration in the other phase.
 Define:

 *
J  K l Cl  Cl 
*
J  K g Cg  Cg 
Kl = overall mass transfer coefficient based on
liquid-phase concentration.

Kg = overall mass transfer coefficient based on gas-

phase concentration.
Kg,l have dimensions of L/t.

Cl* = liquid phase concentration that would be in

equilibrium with the bulk gas concentration.
= Cg/Hc (typical dimensions are moles/m3).

Cg* = gas phase concentration that would be in

equilibrium with the bulk liquid concentration.
= HcCl (typical dimensions are moles/m3).
Expand the liquid-phase overall flux equation to
include the interface liquid concentration.

   
J  K l   C l C li   C li Cl 
*
    
Then substitute
Cgi * Cg
Cli  and Cl 
Hc Hc

to get:

J  Kl Cl Cli Cgi Cg  / Hc

In the steady-state, fluxes through all films must
be equal. Let all these fluxes be equal to J.

On an individual film basis:

J
 Cl Cli  
kl
and

 
Cgi Cg 
J
kg
Since all J’s are equal:

 J J 
J  Kl   
 k l H c k g 
 
 This can be arranged to give:

1 1 1
 
Kl k l H c  k g

A similar manipulation starting with the overall flux

equation based on gas phase concentration will give:

1 Hc 1
 
K g kl k g
These last two equations can be viewed as
"resistance" expressions where 1/Kg or 1/Kl
represent total resistance to mass transfer based
on gas or liquid phase concentration,
respectively.
In fact, the total resistance to transfer is made up of
three series resistances: liquid film, interface and
gas film. But we assume instant equilibrium at
the interface so there is no transfer limitation here.
It should be noted that model selection
(penetration, surface renewal or film) does not
influence the outcome of this analysis.
Single film control
It is possible that one of the films exhibits
relatively high resistance and therefore dominates
the overall resistance to transfer. This, of course,
depends on the relative magnitudes of kl, kg and
Hc. So the solubility of the gas and the
hydrodynamic conditions which establish the film
thickness or renewal rate (in either phase)
determine if a film controls.
In general, highly soluble gases (low Hc) have
transfer rates controlled by gas film (or renewal
rate) and vice versa. For example, oxygen (slightly
soluble) transfer is usually controlled by liquid
film. Ammonia (highly soluble) transfer is usually
controlled by gas phase film.
 APPLICATIONS

Transfer of gas across a gas-liquid interface can

be accomplished by bubbles or by creating
large surfaces (interfaces). The following are
some common applications of gas transfer in
treatment process.
 Absorption
Gas absorption: It is a mass transfer operation in which one or more gas solutes
is removed by dissolution in a liquid. The inert gas in the gas mixture is called
“carrier gas”. In the absorption process of ammonia from air-ammonia mixture by
water, air is carrier gas, ammonia is „solute” and water is absorbent. An intimate
contact between solute gas and absorbent liquid is achieved in a suitable absorption
equipment, namely, tray tower, packed column, spray tower, venture scrubber, etc.
Desorption or stripping operation is the reverse of absorption.

Absorption operation is of two types;

•physical
•and chemical.
𝐴𝑏𝑠𝑜𝑟𝑏𝑒𝑛𝑡
𝑆𝑜𝑙𝑢𝑡𝑒+𝐶𝑎𝑟𝑟𝑖𝑒𝑟 𝑔𝑎𝑠 𝑆𝑜𝑙𝑢𝑡𝑒 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 𝑖𝑛 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑛𝑡+𝐶𝑎𝑟𝑟𝑖𝑒𝑟 𝑔𝑎𝑠

For the determination of driving force in any mass transfer operation, the solubility of a species
in a solvent, i.e., equilibrium distribution between phases is important. With the increase in
temperature, solubility of a gas in liquid decreases.
Hence, absorption is done at lower temperature. On the contrary, desorption is done at higher
temperature.
Selection of solvent for absorption and stripping
Few criteria for the selection of an absorbent are as follows:

(A) Gas Solubility: High solubility of a gas in the solvent is preferred, utilizing low
quantity of solvent. Absorbent should not dissolve carrier gas. Similar chemical nature of
solute and absorbent (solvent) gives a good solubility. If chemical reaction takes place
between solute and solvent, rate of absorption is extremely high. But the reaction should be
reversible to recover solvent during desorption.

(B) Volatility: Low volatility or low vapor pressure of the solvent enhances the adsorption
operation as solvent loss with carrier gas is very small. Sometimes, a second less volatile
solvent is used to recover the first solvent.

(C) Viscosity: For better absorption, a solvent of low viscosity is required. In mechanically
agitated absorber, greater amount of power is required for high viscous solvent and flooding
is also caused at lower liquid and gas flow rates.

(D) Corrosiveness: Non-corrosive or less corrosive solvent reduces equipment construction

cost as well as maintenance cost.

(E) Cost: The solvent should be cheap so that losses will be insignificant and should be
easily available.

(F) Toxicity and Hazard: The solvent should be non-toxic, non-flammable, non-hazardous
and should be chemically stable.
Two common gas absorption equipments are packed tower and plate tower. The gas
and the liquid phases come in contact in several discrete stages. Thus, a stage wise
contact is there in a plate column. But in packed tower, the up-flowing gas remains in
contact with down-flowing liquid throughout the packing, at every point of the tower.
Therefore, packed tower is known as “continuous differential contact equipment
Steps for the design of packed tower

(A) Selection of solvent

(B) Selection of packing
(C) Calculation of minimum solvent flow rate as well as actual solvent
flow rate
(D) Column diameter
(E) Height of column
(F) Design of solvent distributors and redistributors (if needed)
(G) Design of gas distributor, packing support, shell, nozzles, column
support

(a) Equilibrium data; (b) gas and liquid flow rates; (c) solute
concentration in two terminals; (d) individual and overall volumetric
mass transfer coefficients should be known for the design of a packed
absorption tower.
Packing Materials:
Packing materials are utilized to provide large interfacial area of contact between two
phases. These are made from either of ceramics, metals or plastics. A number of
packing materials with various size, shape and performance are available. These are
classified into three types, namely, dumped or random, structured and grid.

A) Dumped or random packing materials: Dumped or random packing materials are classified into three
categories as first generation (1907 to mid 1950); second generation (mid 1950 to mid 1970) and third
generation (mid 1970 to till date). The first generation random packing materials are of three categories, such
as, (a) Raschig rings; (b) Lessing rings and modified Raschig rings and (c) Berl saddles. These are shown in
Figure 4.1.
The packing materials have following characteristics:

(a) Cost: The cost of the packing materials should be very low.
(b) Surface area: A large interfacial area of contact is always recommended. In that
case, pressure drop will be more.
(c) Void volume: A high void volume is needed to maintain low pressure drop.
(d) Fouling resistance: Packing materials should not trap suspended solids present in
liquid. Bigger packing materials generally give low fouling resistance.
(e) Mechanical strength: Good mechanical strength is desired for choosing packing
materials as this will not break or deform during filling or operation.
(f) Uniform flow of streams: Stack of packing materials should have uniform void
spaces through which both the streams (gas and liquid) can flow uniformly. Non-
uniform flow of streams leads to stagnant liquid pool which in turn gives low mass
transfer.
The second generation random packing materials are mainly (a) Intalox
saddle and modification; (b) Pall ring and modification. Intalox saddle is
the modified version of Berl saddle and offers less friction resistance due
to particular shape (two saddles will never nest). Pall rings are modified
version of Raschig rings.
The third generation random packing materials:
(B) Structured packing materials: These materials are used
widely as packing materials in packed tower due to low gas
pressure drop and improved efficiency. Corrugated metal sheet
structured packing and Wire mesh structured packing
materials are widely used in the industries. These include
Mellapak, Flexipak, Gempak, Montz and MaxPak.