Mto-I Even 2020

Mass Transfer Operations-I
Dr. A. P. Vyas
EVEN-2020
Introduction to Mass Transfer
Unit Operations: Operations which are concerned
with the problem of changing the compositions
of solutions and mixtures through methods not
necessarily involving chemical reactions.
Separating a substance into its component
parts. Separation may be entirely mechanical or
by density difference.
e.g. Distillation, Absorption, Adsorption,
Extraction, Leaching, Drying, Humidification, etc.
Unit Processes: It is depending upon the type of
reaction involved and the product may be
different than the reactant.
e.g. Halogenation, Amonolysis, Amination,
Sulphation, Sulphonation, Nitration, etc.
Mass Transfer Operations: If the operations
involves changes in composition of solutions,
they are known as the mass transfer operations.
MTO are characterized by transfer of a substance
through another on a molecular scale. It is not a
bulk movement.
MTO is a result of a concentration difference or
concentration gradient.
Classification of MTO
(1) Direct contact of two immiscible phases:
(A) Gas-Gas: Since most of the gases are
completely soluble with each other, this
category is not realized practically.
(B) Gas-Liquid:
(i) Fractional distillation or distillation: All the
components of the system distribute between
the phases at equilibrium.
e.g. Acetic acid and water
Direct contact of two immiscible phases (Contd..)
(B) Gas-Liquid (Contd…):

(ii) Gas Absorption: Both the phases may be solutions, each
containing, however, only one common component (or
group of components) which distributes between the
phases.
e.g. Ammonia & air in water
(iii) Desorption or Stripping: Opposite to Gas Absorption

e.g. Ammonia & Water in air
The difference between (ii) and (iii) is purely in the direction of

solute transfer.
(B) Gas-Liquid (Contd…):

(iv) Humidification: The liquid phase is a pure liquid
containing only one component while the gas contains
two or more components.
e.g. Contact of dry air with liquid water results in evaporation
of some water into the air.
(v) Dehumidification: Opposite to Humidification

e.g. Contact of very moist air with pure liquid water result in
condensation of part of moisture in the air.
The difference between (iv) and (v) is in the direction of
transfer.
(C) Gas-Solid:
(i) Sublimation: If a solid solution is partially vaporized without the
appearance of a liquid phase, the newly formed vapour phase and the
residual solid each contains all the original components, but in different
proportions.
(ii) Drying: If a solid moistened with a volatile liquid is exposed to relatively

dry gas, the liquid leaves the solid and diffuses into the gas, the operation
is known as Drying. The diffusion takes place in direction of solid to gas.
(iii) Adsorption: If the diffusion takes place in opposite direction to drying,

the operation is called Adsorption.
e.g. mixture of water vapour and air is brought into contact with silica gel,
the water vapour diffuses to the solid, which retains it strongly, and the
air is thus dried.
(D) Liquid-Liquid:
(i) Liquid-liquid extraction: Separations involving the
contact of two insoluble liquid phases.
e.g. Acetone - Water solution in Carbon Tetra Chloride
Acetic acid – acetone solution into insoluble mixture
of water and carbon tetra chloride.
(ii) Fractional extraction: Producing two liquid phases
from a single-phase solution by cooling the latter
below its critical solution temperature. The two
phases which form will be of different composition.
(E) Liquid-Solid:
(i) Fractional crystallization: All the constituents are present in both phases at
equilibrium.
(ii) Zone refining: Used to obtain ultrapure metals and semiconductors
(iii) Adductive crystallization: Substance has a crystal lattice which will selectively
entrap long straight-chain molecules and exclude branched molecules.
(iv) Leaching (or solvent extraction): Selective solution of a component from a
solid mixture by a liquid solvent is known as a leaching.
e.g. gold from its ores by cyanide solution, cottonseed oil from the seeds by
hexane.
The diffusion is from solid to the liquid phase.
(v) Adsorption: The diffusion in opposite direction.
(F) Solid-Solid: Due to very slow rate of diffusion within solid phases, there is no
industrial separation operation in this category.
(2) Phases separated by a membrane:
Though rapidly increasing importance, used infrequently.
The membranes operate in different ways, depending
upon the nature of the separation to be made.
They serve to prevent intermingling of two miscible
phases.
They prevent ordinary hydrodynamic flow and
movement of substances through them is by diffusion.
They permit a component separation by selectively
controlling passage of the components from one side to
other.
Phases separated by a membrane: (Contd…)
(A)Gas-Gas:
(i) Gaseous Diffusion or effusion:
- Membrane is microporous
- Gas mixture comprises of different molecular weight components
brought into contact with microporous diaphragm to separate
components based on molecular weight differences.
e.g. Separation of uranium isotopes in form of gaseous uranium
hexafluoride.
(ii) Permeation: Gas transmitted through the non-porous membrane

first dissolves in it and then diffuses through it. Separation takes
place by difference in solubility.
e.g. Helium can be separated from natural gas by selective permeation
through fluorocarbon polymer membranes.
(B) Gas-Liquid:
(i) Permeation:
e.g. A liquid solution of alcohol and water is brought into contact with a suitable
non-porous membrane, in which the alcohol is preferentially dissolves. After
passage through the membrane the alcohol is vaporized on the far side.
(C) Liquid-Liquid:
(ii) Dialysis: The separation of a crystalline substance from a colloid, by contact of
their solution with a liquid solvent with an intervening membrane permeable
only to the solvent and the dissolved crystalline substance, is known as
dialysis.
e.g. aqueous beet sugar solutions containing colloidal material are freed from
latter by contact with water with an intervening semipermeable membrane.
Sugar and water diffuse through the membrane, but larger colloidal particles
can not.
(ii) Fractional dialysis: For separating two crystalline substances in solution makes
use of the difference in membrane permeability for the substances.
(C) Liquid-Liquid:
(iii) Electrodialysis: If an electromotive force is applied across the
membrane to assist in the diffusion of charged particles, the
operation is known as electrodialysis.
(iv) Osmosis: If a solution is separated from the pure solvent by a
membrane which is permeable only to the solvent the
solvent diffuses into the solution, an operation is known as
osmosis.
(v) Reverse Osmosis: By superimposing a pressure to oppose the
osmotic pressure the flow of solvent is reversed, and the
solvent and solute of a solution can be separated by reverse
osmosis.
e.g. desalination of seawater
(3) Direct contact of miscible phases:
(i) Thermal diffusion: Involves the formation of a concentration
difference within single liquid or gaseous phase by imposition of a
temperature gradient upon the fluid, thus making a separation of
the components of solution possible.
e.g. 3He is separated from its mixture with 4He.
(ii) Sweep diffusion: Condensable vapour (e.g. steam) is allowed to
diffuse through a gas mixture. It will carry one component with it.
(iii) Atmolysis: Two zones within the gas phase where concentrations
are different are separated by a screen containing large openings.
(iv) Centrifugation: If a gas mixture is subjected to a very rapid
centrifugation, the components will be separated because of the
slightly different forces acting on the various molecules owing to
their different masses.
(4) Use of surface phenomena:
(i) Foam separation:
(5) Direct and Indirect operations:

Choice of separation method
 Whether to choose MTO or MO?
 Whether to choose MTO or a Chemical Reaction
or a combination of both?
 Choices within MTO
 Separated components must be pure.
 Cost (Most important)
 The simplest operation
 Knowledge of design methods
 Unavailability of design data
 Past history
Molecular Diffusion in Fluids
• The two modes of mass transfer:
- Molecular diffusion
- Convective mass transfer or Eddy diffusion
General molecular transport equation
rate of a transfer= driving force/resistance
Definition of diffusion:
• Diffusion is the movement, under the
influence of physical stimulus, of an individual
component through a mixture.
• Most commonly caused by a concentration
gradient.
• A concentration gradient tends to move the
component in such condition to equalized the
concentration.
Diffusion example:
• Initially, the particles are all
near one corner of the glass.
• If the particles all randomly
move around ("diffuse") in the
water, then the particles will
eventually become distributed
randomly and uniformly, and
organized.
• But diffusion will still continue
to occur, just that there will be
no net flux).
Type of Diffusion
• Thermal diffusion: Diffusion due to a temperature gradient. Usually
negligible unless the temperature gradient is very large.
• Pressure diffusion: Diffusion due to a pressure gradient. Usually negligible
unless the pressure gradient is very large.
• Forced diffusion: Diffusion due to external force field acting on a molecule.
Forced diffusion occurs when an electrical field is imposed on an electrolyte
( for example, in charging an automobile battery)
• Knudsen diffusion: Diffusion phenomena occur in porous solids.
• Fick’s First Law:
* dcA dxA
J AZ  DAB   cDAB
* dz dz
J A is the molar flux of component A in the z direction (In the
direction normal to the diffusion) in kg mol A/s.m2.
D AB
is the molecular diffusivity of the molecule A in B in m2/s
c Ais the concentration of A in kg mol/m3.
z is the distance of diffusion in m
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
flux JA to its concentration gradient.
The negative sign emphasizes that diffusion occurs in the direction of drop of
concentration.
The diffusivity is a characteristic of a constituent and its environment (T, P, C,
whether L, G or S solution and the nature of other constituent)
Fick’s Law of Diffusion
• Molecular diffusion or molecular transport can be defined as the transfer or movement of
individual molecules through a fluid by mean of the random, individual movements of the
molecules.
(2) A
B B B
Schematic diagram of molecular diffusion process
B B
B
B
B
B B
(1) A
• If there are greater number of A molecules near point (1) than at (2), then since molecules
diffuse randomly in both direction, more A molecules will diffuse from (1) to (2) than from (2)
to (1).
• The net diffusion of A is from high to low concentration regions.
Example:
A mixture of He and N2 gas is contained in a pipe at 298 K and 1
atm total pressure which is constant throughout. At one end of
the pipe at point 1 the partial pressure pA1 of He is 0.6 atm and at
the other end 0.2 m pA2 = 0.2 atm. Calculate the flux of He at
steady state if DAB of the He-N2 mixture is 0.687 x 10-4 m2/s.
Assume: ideal gas law applied
Solution:
• Since a total pressure P is constant, the c is constant, where
c is as follows for a gas according to the perfect gas law:
• Where n is kg mol (A+B), V is volume in m3, T is temperature
in K, R is 8314.3 m3.Pa/kg mol.K or R is 82.057 x 10-3 cm3.
atm/g. mol. K, and c is kg mol/m3 of (A+B).
• For steady state the flux J*Az is constant. Also DAB for gas is
constant. Rearranging and integrating.
• Also, from the perfect gas law, pAV=nART, and
• Substituting
• This is the final equation to use, which is in a form easily used for
gases. Partial pressures are pA1 = 0.6 atm = 0.6 x 1.01325 x 105 = 6.04 x
104 Pa and pA2 = 0.2 atm = 0.2 x 1.01325 x 105 = 2.027 x 104 Pa. Then,
using SI units,
• If pressures in atm are used with SI unit,
• Other driving forces (besides concentration differences)

for diffusion also occur because of temperature,
pressure, electrical potential, and other gradients.
• Self study problem:
• A gas of CH4 and He is contained in a tube at 101.32 kPa and 298 K. At
one point the partial pressure of methane is p A1= 60.79 kPa, and at a
point 0.02 m distance away, pA2=20.26. If the total pressure is constant
through the tube, calculate the Flux of methane at steady state for
equimolar counter diffusion.
In a non-uniform solution even containing only two constituents, however,
both constituents must diffuse if uniformity is the ultimate result and these
leads to the use of two fluxes to describe the motion of one constituent.
There are two types of fluxes:

J N
The flux of a constituent relative to the The flux relative to a fixed position in space
average molar velocity of all constituents
More characteristic of the nature of Important in applications to the design of
constituent equipment
Example: A fisherman is most interested in the rate at which a fish swims

upstream against the flowing current to reach his baited hook (analogous to N),
but the velocity of the fish relative to the stream (analogous to J) is more
characteristic of the swimming ability of the fish.
P
I II
If the direction to the right is taken as positive, the flux NA of A relative to the fixed position
P has been positive and the flux NB of B has been negative. For a condition of steady state,
the net flux is
NA + NB = N
The movement of A is made up of two parts:
1. Resulting from the bulk motion N and the fraction xA of N which is A
2. Resulting from diffusion JA C C A
N A  ( N A  N B ) A  DAB
NA = NxA + JA => C z
The counter part of above equation for B is, N  ( N  N ) CB  D CB
B A B BA
C A C C z
Adding these gives,  DAB  DBA B
z z
or JA = -JB. If cA + cB = const, it follows that DAB = DBA at the prevailing conc. and temp.
The Equation of Continuity
Consider the volume element of fluid as shown y
in figure, where a fluid is flowing through the Δx
Δy x + Δx,
element. We shall need a material balance for a
G y + Δy,
component of the fluid applicable to a
differential fluid volume of this type. z + Δz
The mass rate of flow of component A into the Δz
three faces with a common corner at E is E

M A N A, x x y z  N A, y y x z  N A, z z x y 
(x, y, z)
Where, NA,x signifies the x-directed
flux and (NA,x)x its value at location x. x
Similarly the mass rate of flow out of z (An elemental fluid volume)
the three faces with a common
corner at G is

M A N A, x x  x y z  N A, y y  y x z  N A, z z  z x y 
The total component A in the element is Δx Δy ΔzρA, and
its rate of accumulation is therefore Δx Δy Δz ∂ρA/∂Ѳ.
If in addition, A is generated by chemical reaction at the rate RA mol/(volume)(time).
Its production rate is MARAΔx Δy Δz, mass/time.
Since, in general
Then,      
M A N A, x x  x  N A, x x y z  N A, y y  y  N A, y y x z  N A, z z  z  N A, z z x y 
 A
  x y  z  M A R A  x y z

Dividing by Δx Δy Δz and taking the limit as Similarly for component B,
the three distances become zero gives,
 N N B , y N B , z   B
 N N A, y N A, z   A M B  B , x      M B RB
M A  A, x      M A RA  x y z  
 x y z  
The total material balance is obtained by adding those for A Where, ρ = ρA + ρB = the
and B, solution density, since,
M A N A  M B N B x M A N A  M B N B y M A N A  M B N B z  the rate of generation of
   0
x y z  A and B must equal zero.
Now the counterpart of eq. NA = NxA + JA Where, ux is the mass-average velocity such that
in terms of masses and in the x direction ρux = uA,x ρA + uB,x ρB = MANA,x + MBNB,x
is MANA,x = uxρA + MAJA,x
Therefore ,
 M A N A  M B N B x u 
  x  ux
x x x
Hence, equation M A N A  M B N B x M A N A  M B N B y M A N A  M B N B z 
   0
x y z 
Becomes, Equation of continuity or a mass balance, for total substance:
 u u u     
  x  y  z   u x  uy  uz  0
 x  y z  x y z 
If the solution density is constant, it becomes:

 u x u y u z 
     0
 x y z 
Returning to the balance for component A, we see from equation, MANA,x = uxρA + MAJA,x
That, N A, x  A u x J A, x  A u x  2c A
MA  ux  A MA  ux  A  M A DAB 2
x x x x x x x
N N N A, z   A
Equation, M A  A, x  A, y  then  becomes
 M AThe
RA equation of
 x y z  

continuity for substance ‘A’.
 A  A  A  u x u y u z    2u x  2u y  2u z   A
ux  uy  uz   A      M A DAB  2  2  2    M A RA
x y z x y z  x  y  z  
   
For a solution of constant density, above equation to the terms multiplying ρA, Dividing by
MA, we then have:
c A c A c A c A   2c A  2c A  2c A 
ux  uy  uz   DAB  2  2  2   RA
x y z   x y z 
In the special case where the velocity equals zero and there is no chemical reaction, it
reduces to Fick’s second law. This is frequently applicable to diffusion in solids and to
limited situation in fluids.
c A  c
2 2
 c c 
2
 DAB  2A  2A  2A 
  x y z 
In similar fashion, it is possible to derive the equation for a differential energy balance. For a
fluid of constant density, the result is
t t t t   2 t  2t  2 t  Q
ux  u y  uz     2  2  2  
x y z   x y z  C p
Where, α = k/ρCp and Q is the rate of heat generation within the fluid per unit volume
from a chemical reaction.
Steady state molecular diffusion in fluids
(At rest and in Laminar flow)
Applying equation
CA C A
N A  (N A  NB )  DAB
C z
to the case of diffusion only in the z-direction, with NA and NB both constant (steady state),
we can readily separate the variables, and if DAB is constant, it can be integrated
cA2  dc A 1 z2
c A1

N Ac  c A N A  N B  cDAB 
z1
dz
Where, 1 indicates the beginning of the diffusion path (cA high) and 2 the end of the
diffusion path (cB low). Letting z2 – z1 = z, we get
NA c
 A2
1 N c  c A2 N A  N B  z N A cDAB N  N B  c
ln A  or N A  ln A
N A  N B N Ac  c A1 N A  N B  cDAB N A  NB z NA c
 A1
N A  N B  c
Steady state molecular diffusion in Gases
When the ideal gas law can be applied, equation, given below
1 N c  c A2 N A  N B  z
ln A 
N A  N B N Ac  c A1 N A  N B  cDAB
cA pA
can be written in a form more convenient for use with gases. Thus,   yA
c pt
Where, p ̅A = Partial pressure of component A

pt = total pressure
yA = mole fraction
p A concentration
n p
c  t
Further, pt V RT
So, Equation
NA c
 A2
NA 
N A cDAB N  N B  c
ln A
becomes, N A  NB z NA c
 A1
N A  N B  c
 NA   NA 
 p
 t  p    y A2
N A DAB pt  N A  N B  N A DAB pt  N A  N B 
A2
NA  ln or N A  ln
N A  N B RTz  NA  N A  N B RTz  NA 
 N  N  tp  p A1  N  N   y A1
 A B   A B 
This is usually fixed by other considerations, for example if Methane is being cracked on a
catalyst, CH4 ----- C + H2, under circumstances such that CH4 (A) diffuses to the cracking
surface and H2 (B) diffuses back, the reaction stoichiometry fixes the relationship NB = -2NA,
and
NA NA
  1
N A  N B  N A  2 N A 
On other occasions, in the absence of chemical reaction, the ratio can be fixed by enthalpy
considerations.
In the case of purely separational operations, there are two situations which frequently
arise.
1. Steady state diffusion of A through non-diffusing B

2. Steady state equimolal counter-diffusion
1. Steady state diffusion of A through non-diffusing B
For example, if ammonia (A) were being absorbed from air (B) into water. In the gas phase,
since air does not dissolve appreciably in water, and if we neglect the evaporation of water,
only the ammonia diffuses. Thus, NB = 0, NA = const. NA
1
N A  N B 
 NA 
And equation,   pt  p A2
N A DAB pt  N A  N B 
NA  ln
N A  N B RTz  NA 
 N  N  pt  p A1
DAB pt pt  p A2  A B 
Becomes, NA  ln
RTz pt  p A1
Since, pt  p A2  pB 2 , pt  p A1  pB1 , pB 2  pB1  p A1  p A2

then, D p p  p A2 pB 2
N A  AB t A1 ln
RTz pB 2  pB1 pB1
pB 2  pB1
 pB , M DAB pt
If we let, pB 2 Then, NA   p A1  p A2 
ln RTzpB , M
pB1
1. Steady state diffusion of A through non-diffusing B (Contd…)
DAB pt
Equation, N A   p A1  p A2 
RTzpB , M
can be shown graphically as in the figure. Substance A diffuses by virtue if its concentration
gradient,  dp A
dz
Substance B is also diffusing relative to the average
molar velocity at a flux JB, which depends upon  dpB
But like a fish swims upstream at the same dz
Velocity as the water flows down stream, NB = 0
relative to a fixed place In space.
2. Steady state equimolal counter-diffusion
Such diffusion takes place mainly in distillation. NA = -NB = Const. Below equation becomes
indeterminate,  NA 
  pt  p A2
N A DAB pt  N A  N B 
NA  ln
N A  N B RTz  NA 
 N  N  pt  p A1
 A B 
CA C A
N
But at the same time, the equation, A  ( N  N )  D , which
z is for gases, becomes
A B AB
C
This is shown graphically in figure.

Steady – state diffusion in multi-component mixtures:
Diffusivity of gases:
The diffusivity or diffusion coefficient, D is a property of depend upon temperature,
pressure, and the nature of the components.
Expressions for estimating D in absence of experimental data are based on consideration of
kinetic theory of gases.
The Wilke-Lee modification of the Hirschfelder-Bird-Sportz method is recommended for the
mixtures of non-polar gases or of a polar with non-polar gas.
The diffusivities of gases at standard atmospheric pressure, 101.3 kN/m 2 is listed in table
below for ready reference. Detail list may be available in “The Chemical Engineer’s
Handbook”.
The values of r and ε, such as those listed in table 2.2, can be calculated from other
properties of gases, such as viscosity. If necessary they can be estimated for each
component empirically.
r = 1.18 ν1/3 and ε/k = 1.21 Tb
Where,
ν = Molal volume of liquid at normal boiling point, m3/kmol (estimated from table 2.3)
Tb = normal boiling point in K.
In using table 2.3, the contribution for the constituent atoms are added together.
Thus for toluene, C7H8, ν = 7(0.0148) + 8(0.0037) – 0.015 = 0.1182.
Diffusion through air, when the constituents of the air remain in fixed proportions, is
handled as if the air were a single substance.
Estimate the diffusivity of ethanol vapour, C2H5OH, (A), through air (B) at 1 std atm pressure,
0°C.
Solution:
T = 273 K, pt = 101.3 kN/m2, MA = 46.07, MB = 29. From table 2.2 for air, εB/k = 78.6 and rB =
0.3711 nm. Values for ethanol will be estimated from equations: r = 1.18 ν1/3 & ε/k = 1.21 Tb
From table 2.3, νA = 0148) + 6(0.0037) + 0.0074 = 0.0592.
Therefore, rA = 1.18 ν1/3 = 1.18 (0.0592)1/3 = 0.46 nm.
The normal boiling point is Tb,A = 351.4K and εA/k = 1.21425 (351.4)
(78.6) = 425
rAB = (0.46 + 0.3711)/2 = 0.416 and εAB/k = = 170.7
1 1
kT/εAB = 273/170.7 = 1.599   0.237
MA MB
From Figure 2.5, f(kT/εAB) = 0.595
3
4  
10 1 . 084  0 . 249 ( 0 . 237 )( 273 )( 0 . 237 ) 
2
   1 . 05  10 5 m2
D AB  3 2
(101 . 3  10 )( 0 . 416 ) ( 0 . 595 ) s
Molecular diffusion in Liquids:
C C
The integration of equation N A  ( N A  N B ) A  DAB A
C z
to put it in the form of equation NA c
 A2
NA 
N A cDAB N  N B  c
ln A
N A  NB z NA c
 A1
N A  N B  c
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.
Hence, the above equation may be written as, NA

 x A2
NA 
N A DAB   
ln
N A  N B 
 
N A  N B z  M  avg NA
 x A1
N A  N B 
Where, ρ and M are the solution density and

molecular weight, respectively.
Diffusivity of Liquids: For dilute solutions of nonelctrolytes, the empirical correlation of Wilke
and Chang is recommended.
Diffusivity of Liquids: The diffusivity in concentrated solutions differs from that in dilute
solutions because of changes in viscosity with concentration and also because of changes in
the degree of nonideality of the solution.
Where, D°AB is the diffusivity of A at infinite dilution in B and D°BA the diffusivity of B at infinite
dilution in A.
The activity coefficient ϒA can typically be obtained from vapour-liquid equilibrium data as
the ratio (at ordinary pressures) of the real to ideal partial pressures of A in the vapour in
equilibrium with a liquid of concentration xA:
The derivative (d log ϒA / d log xA) can be obtained graphically as the slope of a graph of log ϒA
vs. log xA.
Diffusivity of Liquids:
Mass Transfer Coefficients
 The mechanism of eddy diffusion is not well understood. But it is well understood in case
of molecular diffusion.
 Hence, rate of mass transfer for turbulent region should also be described in the same
manner as for laminar region.
 Hence, DABc/z, which is a characteristic of molecular diffusion, is replaced by F, a mass
transfer coefficient. NA c
 A2
 For Binary solutions,
NA 
NA
F ln A
N  N B  c
Where, cA2/c = mole fraction concentration N A  NB NA c
 A1
xA = mole fraction for liquids N A  N B  c
yA = mole fraction for gases
F = Local Mass Transfer Coefficient (MTC) defined for a particular location on the
phase-boundary surface.
NA (Flux at the interface, or boundary) is positive when cA1 is at the beginning of the
transfer path and cA2 at the end.
Case: Liquid evaporates into flowingc A gas, cA of vapour in the gas varies1 fromS cA1 at liq. Surface
to the value at z = Z. Take cA2 = and it is defined as, cA 
ux S 
0
u x c A dS
ux
Where, ux(z) = velocity distribution in gas across the duct
=bulk-average velocity (volumetric rate/duct c.s.)
Value of F depends upon the nature of the fluid motion, which may vary along the
surface, an average value Fav is sometimes used with constant cA1 and cA2, which takes
into account these variations in F.
For multicomponent systems, NA + NB is replaced by i 1 N
n
, where
i n is the number of
components.
The two situations, (i) equimolar counter diffusion and (ii) Transfer of A through
nontransferring B, occur so frequently that special mass- transfer coefficients are
usually used for them. These are defined by equations of the form,
Flux = (coefficient)(Concentration difference)
Since the concentration may be defined in various ways, the flux may be written in
different ways,
Mass Transfer Coefficients In Laminar Flow
Figure shows a liquid falling in a thin film in laminar
flow down a vertical flat surface while being
exposed to a gas A, which dissolves in liquid. The
liquid contains a uniform concentration cA0 of A at
the top. At the liquid surface, the concentration of
the dissolved gas is cA,i, in equilibrium with the
pressure of A in the gas phase. Since, cA,i > cA0, gas
dissolves in the liquid.
The problem is to obtain the mass-transfer

coefficient kL, with which the amount of gas
dissolved after the liquid falls the distance L can
be calculated.
The problem is solved by simultaneous solution of

the equation of continuity for component A with
the equations describing the liquid motion, the
Navier –stokes equation.
Assumptions:
c A c A   2 c A  2c A2.17
c A c A ------Equation  2c A 
ux  uy  uz   DAB  2  2  2   RA
x y z   x y z 
Film Theory
The oldest theory giving meaning of MTC.
When a fluid flows turbulently past a solid surface,

with mass transfer occurring from surface to the fluid,
the concentration – distance relation is as shown by
the full curve in figure, the shape of which is
controlled by the continuously varying ratio of ED to D.
Postulation: The concentration will follow the broken

curve of the figure, such that the entire concentration
difference, cA1 – cA2 is attributed to molecular diffusion
within an “effective” film of thickness zF.
The concentration gradient in the film is the

characteristic of steady state.
Conclusion: If this theory were to have useful application, the film would have to be very
thin, so that the quantity of large solute within the film would be small relative to the
amount passing through it, or the concentration gradient would have to be set up quickly.
Prediction: F and k- type MTCs for different solutes being transferred under the same fluid –
flow conditions are directly proportional to the D’s for the solutes.
Mass Transfer at Fluid Surfaces
Because the velocity of a fluid surface, as in contact with gas and liquid, is not zero, a
number of theories have been developed to replace the film theory.
Penetration Theory (Higbie’s theory): In many situations the
time of exposure of a fluid to mass transfer is short, so that
the concentration gradient of the film theory, characteristic of
the steady state, would not have time to develop.
Higbie’s theory describes the contact of two fluids.
Fig. (a):
1. Gas bubble rises through a liquid in which gas will absorb.
2. A liquid particle, b, is in contact with gas for
time ϴ required for the bubble to rise a
distance equal to its diameter.
3. Liquid particle slips along with a surface of
the bubble.
Fig. (b):
1. Eddy b rising from the turbulent depth of the
liquid and remaining exposed for a time
ϴ to the action of the gas.
2. cA0 = Initial concentration of dissolved gas in
the eddy. (Internally eddy is considered stagnant).
3. cA,i = Concentration of gas, when eddy exposed at the surface, in the liquid at the gas –
liquid surface. It is also taken as the equilibrium solubility of the gas in liquid.
4. During time ϴ, the liquid particle is subject to unsteady state diffusion or penetration of
solute in the z- direction. As an approximation, following equation may be applied:
c A  2c A
 DAB
 z 2
Surface – Renewal Theories (Danckwerts’s Theory):
Comparison: Higbie’s theory with its constant time of exposure of the eddies of fluid at the
surface is a special case of what may be a more realistic picture, where the eddies are
exposed for varying length of time.
Hence, the liquid – gas interface is then a mosaic of surface elements of different exposure –
time histories.
Since, the rate of solute penetration depends upon exposure time, the average rate for a unit
surface area must be determined by summing up individual values.
Assumption: The chance of a surface element’s being replaced by another is quite

independent of how long it has been in the surface.
If s is the fractional rate of replacement of elements, Danckwerts found,

 
and
N A,av  c A,i  c A0therefore
DAB s k L,av  DAB s
Danckwerts pointed out that all theories of this sort, derived with the original boundary
conditions on equation c A will lead
 2c A to kL,av proportional to , regardless
DAB0.5
 DAB
 z 2
the nature of the surface-renewal rate s which may apply.
Combination of Film - Surface – Renewal Theory (Dobbin’s Theory):
Dobbin’s , concerned with the rate of absorption of oxygen into flowing streams and rivers,
pointed out that
(i) The film theory k L assumes
DAB  a time exposure of the surface elements sufficiently long for
the concentration profile within the film to be characteristic of steady state.
(ii) The penetration and surface-renewal theories k L  Dassume
AB 
0.5 the surface elements to be
essentially infinitely deep, the diffusing solute never reaching the region of constant
concentration below.
(iii) The observed dependence,k L  DAB n
, with n dependent upon circumstances, might be
explained by allowing for a finite depth of the surface
elements or eddies.
Accordingly, Dobbins replaced the third boundary condition
by cA = cA0 for z = zb, where zb is finite. With Danckwerts’
rate of renewal of the surface elements, he obtained
szb2
k L ,av  DAB s coth
DAB
For rapid penetration (DAB is large), the rate of surface small
(s small), or for thin surface elements, the MTC takes on
Character described by the film theory.
For slow penetration or rapid renewal it follows k L ,av  DAB s
Consequently, k L  DAB n
, where n may be between 0.5 to 1.0
Surface – Stretch Theory (Lightfoot and his coworker’s Theory):
It is an extension of penetration-surface-renewal concepts to situations where the interfacial
surface through which mass transfer occurs changes periodically with time.
System: Liquid drop such as ethyl acetate rising through a denser liquid
such as water, with mass transfer of a solute such as acetic acid from the
water to the drop.
What happens: Such a drop, if relatively large, wobbles and oscillates,
changing its shape as shown in figure. If the central portion of the drop is
thoroughly turbulent, the mass transfer resistance of the drop resides in a
surface layer of varying thickness.
Similar situations occur while drops and bubbles form at nozzles and when
liquid surfaces are wavy or rippled.
For these cases, theory leads to, A / Ar  DAB / r
k 
L , av  /r

0
A / Ar 2 d
Where,
A = time-dependent interface surface
Ar = reference value of A, defined for each situation
ϴr = Const., with dimensions of time, defined for each situation; e.g. for
drop formation ϴr might be drop formation time.
Interphase Mass Transfer
Equilibrium: It is convenient to consider the equilibrium characteristics of a particular
operation and then to generalize the result for others.
Equilibrium is the e quality of chemical potential, not of the concentration.
e.g. Ammonia and air in water.

Interphase Mass Transfer
Equilibrium: Following principles are common to all systems involving the distribution of
substances between two insoluble phases.
1. At a fixed set of conditions, referring to temperature and pressure, there exists a set of
equilibrium relationships which can be shown graphically in the form of an equilibrium –
distribution curve for each distributed substance by plotting the equilibrium
concentrations of the substance in the two phases against each other.
2. For a system in equilibrium, there is no net diffusion of the components between the
phases.
3. For a system not in equilibrium, diffusion of the components between the phases will
occur so as to bring the system to a condition of equilibrium. If sufficient time is available,
equilibrium concentration s will eventually prevail.
Diffusion between phases
Departure from equilibrium provides the driving force for
diffusion. Hence, let us study the rate of diffusion in
terms of the driving forces.
Many of mass transfer operations are carried out in

steady-flow fashion, with continuous and invariant flow of
the contacted phases and under circumstances such that
concentrations at any position in the equipment used do
not change with time. e.g. Wetted wall tower.
Let us consider the system: Ammonia (Substance A) and

Air entered from the bottom. Liquid water as an
absorbent entering from the top.
Gas mixture changes its composition from high to low

concentration as it flows upward while water dissolves
ammonia and leaves as aqueous ammonia at bottom.
Under Steady state conditions, concentration at any point
in the apparatus do not change with passage of time.
(Local Two-Phase Mass Transfer, Two Resistance Theory)
Assumption: No chemical Reaction occurs.
Figure shows the condition at the middle of
the absorber.
Solute is diffusing in to the gas phase from
liquid phase giving concentration gradient in
the direction of mass transfer in each phase.
yAG = Concentration of solute A (in mole
fraction) in bulk gas phase
yAi = Concentration of solute A (in mole
fraction) at the interface in gas phase.
xAi = Concentration of solute A (in mole
fraction) at the interface in liquid phase
xAL = Concentration of solute A (in mole
fraction) in bulk liquid phase
Bulk concentrations yAG & xAL are not equilibrium values, otherwise no diffusion can take
place. Also, they cannot be used to calculate MTC as they are differently related to the
chemical potential, which is the real driving force of mass transfer.
Another assumption says only diffusional resistances residing inside fluids and no resistance
to solute transfer across interface. As a result the concentrations yAi and xAi are equilibrium
(Local Two-Phase Mass Transfer, Two Resistance Theory)
The various concentrations are shown graphically
with equilibrium concentrations as coordinates.
P: Two bulk phase conc.
M: Two interface conc.
For steady state, The rate at which A reaches to
the interface, at the same rate will diffuse into
the bulk liquid. Hence, no accumulation or
depletion of A at interface.
Let’s write the flux of A in terms of k-type MTC.
Hence, ky and kx are local MTC.
At steady state,
NA = ky(yA,G – yA,i) = kx(xA,i – xA,L) ---------- (5.1)
Rearrangement gives,
-------------- (5.2)
If the MTCs are known, interfacial concentrations

and hence, the flux NA can be determined either
graphically or analytically by the algebraic
equation for equilibrium distribution curve,
yA,I = f(xA,i) ------------------------------------ (5.3)
(Local Overall Mass Transfer Coefficients)
Experimentally, rate of mass transfer can be
determined in bulk but not at interface as it is a very
small area for sampling. In fact, it is also difficult to
determine the rate of mass transfer between yA,G to
yA,i as it is a very small area.
Consider the equilibrium distribution curve at fixed T
and P. In this case, yA* is the good measure of xA,L as
xA* on the same basis as yA,G. The entire two-phase
mass transfer effect can then be measured in terms
of overall mass transfer coefficient, Ky
-------- (5.4)
Where, yA,G – yA* = driving force
Now, from the geometry of the figure,
--- (5.5)
Where, m’ = slope of the chord CM.
Similarly, NA = Kx(xA* - xA,L) => (xA* - xA,L) = NA/Kx
Now, substituting for the concentration differences
the equivalents (flux/coefficient) as given by eq. 5.1
and 5.4, we can derive
N A N A mN A 1 1 m
      (5.6) or Overall resis tan ce    (5.7)
Ky ky kx K y k y kx
This shows the relationship between the individual
phase transfer coefficients and the overall coefficient
takes the form of addition of resistances, (hence,
“two-resistance” theory).
Similarly, another overall coefficient, Kx can be
derived as below:
 
N A  K x x *A  x A, L     (5.8)
y A ,G  y A , i
 
x*A  x A, L  x *A  x A,i  x A,i  x A, L 
m
 x A,i  x A, L 
N N N 1 1 1
 A A  A       (5.9)
K x k y m k x K x k y m k x
Where, m” = slope of the chord MD.

Eq. 5.7 and 5.9 gives the relationship between mass transfer resistances:
What is the importance of slope m’ and m”?
If the m’ is very small (i.e. equilibrium-distribution
curve is flat almost parallel to x-axis), then at
equilibrium only a small concentration of A in gas will
provide a very large concentration in the liquid
(solute A is highly soluble in liquid). The term m’/kx in
eq. 5.7 will be negligible and 1/ky will provide
maximum resistance. Hence, the rate of mass transfer
will be gas-phase controlled. i.e. 1/Ky ≈ 1/ky --- (5.12)
Or, ------------------- (5.13)
Hence, to increase the rate of mass transfer, gas-
phase resistance must be decreased.
Similarly, if m” is very large (i.e. equilibrium-

distribution curve is vertical almost parallel to y-axis),
Then, solute A is relatively insoluble in liquid and eq. 5.9 becomes, 1/Kx ≈ 1/kx --- (5.14)
Or, ------------------- (5.15). Hence, to increase the rate of mass transfer, liquid-
phase resistance must be decreased (here, kx and ky are nearly equal).
In case where kx and ky are not equal, then relative size of ratio kx/ky and of m’ (or m”)
determine the location of controlling mass transfer resistance.
General equation for k-type MTC for all types of mass
transfer operations:
E and R = different Phases
I and j = conc. In phase E and R, respectively.
Where, f is the equilibrium distribution function.

(Local Coefficients – General case)
When to use F- type MTC?
When we deal with the situations which do not involve either diffusion of only one substance
or equimolar counter diffusion or if mass transfer rates are large, the F-type MTC should be
used.
Thus, in a situation shown in fig. 5.2 to 5.4, the mass transfer flux is
Where, FG and FL = Gas and liquid phase coefficients for substance A, respectively
Eq. 5.20 can be re-written as.

Material Balances
(Steady State Cocurrent Processes)
Both phases (E and R) are insoluble. Single substance A diffuses from phase R to E
Other constituents of phases and solvent for diffusing solvent are considered not to diffuse.
R1 is consisting of nondiffusing solvent Rs mole/time and diffusing solute A whose conc. is x1
mole fraction.
solvent
solvent
A
A is diffuses to the phase E with the flow phase R through the equipment. And the total
quantity of R falls to R2 mol/time at the exit. But the flow rate of Rs remains constant.
x1 > x2, y1 < y2, Es,Entry = Es,Exit, Rs,Entry = Rs,Exit
Material Balances
Material balance for substance A across envelope-I:
R1x1 + E1y1 = R2x2 + E2y2 --------- (5.29)
R1x1 – R2x2 = E2y2 – E1y1 --------- (5.30) But, R1x1 = Rs(x1/(1-x1) = RsX1 (5.31)
Where, X1 = mole ratio conc. of A at the
entrance, mol A/ mol non-A
The other terms can be similarly described and eq. 5.30

becomes, Rs (X1 – X2)= Es (Y2 – Y1) --------- (5.32) => (Y1 – Y2)/(X1 – X2) = - Rs/Es
Which is a straight line equation with Y and X coordinates with (–Rs/Es) as a slope passing
through the two points (X1,Y1) and (X2,Y2), respectively.
Material Balances
Material balance for substance A across envelope-II:
R1x1 + E1y1 = Rx + Ey
R1x1 – Rx = Ey – E1y1 But, R1X1 = Rs(x1/(1-x1) = RsX1 (5.31)
Where, X1 = mole ratio conc. of A at the entrance, mol A/
mol non-A
The other terms can be similarly described and we may

write, Rs (X1 – X)= Es (Y – Y1) --------- (5.33) => (Y1 – Y)/(X1 – X) = - Rs/Es
Which is a straight line equation with Y and X coordinates with (–Rs/Es) as a slope passing
through the two points (X1,Y1) and (X,Y), respectively.
Material Balances
Equilibrium relationship of X and Y as they represent the concentration in two phases:
Line QP = Operating line (Refer eq. 5.32 and 5.33), If an equilibrium established between
two phases, the corresponding
equilibrium composition Xe and Ye
Interface composition at entrance and the represented by extension of line PQ to
distance KM and MP represent, respectively the intersection point T on equilibrium
the driving force in phase E and R curve. Diffusion rate at T is zero.
Interface composition at exit and the
line LQ represent the driving forces
Driving force line

Material Balances
If the diffusion is in opposite direction, i.e. from phase E to phase R, the operating line will fall
on opposite side of equilibrium curve. (Fig. 5.8)
Operating lines in fig 5.7 and 5.8 are straight lines because they are depend upon the
units of conc. of the material balance. Here it is expressed in mole-ratio conc. based on
unchanging quantities of Es and Rs. If the conc. expressed in mole fraction units such as
partial pressure, the operating curve would be of as shown in fig 5.9
Material Balances
(Steady State Countercurrent Processes)
Material balance for substance A across envelope-I:
R1x1 + E2y2 = R2x2 + E1y1 --------- (5.34)
Rs (X1 – X2)= Es (Y1 – Y2) --------- (5.35) But, R1x1 = Rs(x1/(1-x1) = RsX1 (5.31) => (Y1 –
Y2)/(X1 – X2) = Rs/Es Where, X1 = mole ratio conc. of A at
the entrance, mol A/ mol non-A
Which is a straight line equation with Y and X coordinates with (Rs/Es) as a slope passing
through the two points (X1,Y1) and (X2,Y2), respectively.
Material balance for substance A across envelope-II:
R1x1 + Ey = Rx + E1y1 ----- (5.36) and R1x1 – Rx = E1y1 – Ey => Ey – Rx = E1y1 – R1x1 ----- (5.38)
Rs (X1 – X)= Es (Y1 – Y) --------- (5.37)

Material Balances
(Steady State Countercurrent Processes)
If partial pressure is used in place of
mol fraction to express conc., the
operating line will be curved.
In countercurrent, the average driving force for a given situation will be larger, resulting in
either smaller equipment for a given set of flow conditions or smaller flows for a given size
of equipment.
Stages
Continuous cocurrent processes
Stage: A stage is defined as any device or combination of devices in which two insoluble
phases are brought into intimate contact, where mass transfer occurs between the phases
tending to bring them to equilibrium, and where the phases are then mechanically
separated. A process carried out in this manner is a single stage process.
An Equilibrium, ideal or theoretical stage: It is one where the time of contact between
phases is sufficient for the effluents indeed to be in equilibrium. (and although in principle
this cannot be attained)
Continuous Cocurrent Process: Fig 5.6 is a single stage process. If the stage is an ideal one,
or the effluent composition would be at point T in Fig 5.7 or 5.8.
Stage Efficiency: It is defined as the fractional approach to equilibrium which a real stage
produces.
i.e (Actual solute transfer/ solute transferred if equilibrium attained) = QP/TP (Fig. 5.7)
Murphree Stage Efficiency: The fractional approach of one leaving stream to equilibrium
with the actual concentration in the other leaving stream.
(Refer fig. 5.7 for conc. in phase E to R)
Stages
Continuous cocurrent processes
Murphree stage efficiency is an arbitrary
because in case of true cocurrent
operation, it is not possible to achieve
concentration in phase E higher than Ye and
in phase R less than Xe.
Also, two Murphree stage efficiency are not
equal for a given stage and they can be
related only when the equilibrium relation
is a straight line.
Thus for a straight equilibrium line of slope
m = (Y2* -Y2)/(X2 – X2*) , it can be shown
That,
Here, S = mEs/Rs = Stripping Factor

A = Rs/mEs = Absorption Factor
Stages
Batch processes
 The batch operation is a single stage process.
 Even when no in- or out-flow is there, the conc. changes
in the reactor with time.
 When initially phases come in contact they are not in
equilibrium, but with time they may achieve equilibrium.
Rs (X1 – X)= Es (Y – Y1) --------- (5.33)
=> (Y1 – Y)/(X1 – X) = - Rs/Es
Composition X and Y coexist at any point
of time after start of operation.
Cascades
Cascade: A group of stages interconnected so that the various streams flow from one to the
other is called Cascades.
Purpose: It is used to increase the extent of mass transfer over and above which can be
achieved using single stage operation.
Fractional Overall Stage Efficiency of a cascade: It is defined as the number of equilibrium

stages to which the cascade is equivalent divided by the number of real stages.
Two or more stages connected so that the flow is cocurrent between stages will be like one
equilibrium stage, although the overall stage efficiency thereby be increased.
For effects greater than one equilibrium stage, they can be connected for cross flow or
countercurrent flow.
Cascades
Cross Flow Cascades
There may be different flow rate of Phase E For

each stage and each stage may have different
Murphree stage efficiency.
Cross flow is used sometimes in adsorption,

leaching, extraction, and drying operations but
rarely in others.
The material balance is simply a repetition of that for a single stage operations and the
construction on the distribution diagram is obvious.
Cascades
Countercurrent Cascades
These are the most efficient arrangements, requiring the fewest stages for a given change
of composition and ratio of flow rates and therefore, they are the most frequently used.
yNp
YNp
xn+1
Xn+1
Each stage is identical in its action to the

cocurrent process of Fig. 5.6; yet the
cascade as a whole has the characteristics
of the countercurrent process of Fig 5.10.
In special case where both, operating line and equilibrium curve are straight, analytical solution to be
developed:
Cascades
These are the most efficient arrangements, requiring the fewest stages for a given change
of composition and ratio of flow rates and therefore, they are the most frequently used.
If solute transfer from E to R, the operating
If equilibrium line and
line construction falls above the equilibrium
cascade operating line
curve.
touch, the stages become
pinched and infinite
For most cases, the number of stages are
relation between required to bring about
no. stages, desired composition
compositions and change.
flow ratio must be
determined
graphically.
By substitution and rearrangement, eq. 5.41, becomes

----- (5.42)
Cascades
Cascades
The equations derived from eq. 5.49 are known as Kremser-Brown-Souders (or simply
Kremser) equations. They are later plotted in Fig. 5.16 which becomes very convenient
for quick solutions.
Cascades
Cascades
Cascades
Equipment for Gas-Liquid Operations
Gas Dispersed
Purpose: The purpose of equipment for gas-liquid operations is to provide intimate contact
of two fluid in order to permit interphase diffusion of the constituents.
The rate of mass transfer is directly depend upon

(i) the interfacial surface exposed between the phases
(ii) the nature and degree of dispersion of one fluid in the other.
The equipment can be broadly classified according whether its principal action is to,
(iii) disperse of gas
(iv) disperse of liquid
(v) Dispersion of both phases
Gas Dispersed Equipment:

(1) Sparged Vessels (Bubble columns):
- A sparger is a device for introducing a stream of gas in the form of small bubbles in
the liquid.
- The purpose of sparging may be contacting the sparged gas with the liquid.
- Sparging can also provide gentle agitation.
- If the vessel diameter is small, the sparger located at the bottom of the vessel.
- For vessel diameter greater than 0.3 metre, it is better to use several orifices for gas
distribution.
Gas Dispersed
Sparged Columns
Gas Dispersed
Factors affecting the design of Sparged Column (Bubble Tower):
1. Gas-bubble diameter
2. Rising Velocity (Terminal Velocity) of single bubble
3. Group of Gas bubble
4. Gas Hold up
5. Specific interfacial area
6. Mass Transfer
7. Power
(2) Mechanically Agitated Vessels:

- Mechanical agitation of a liquid, usually by rotating device, is specially suitable for
dispersing solids, liquids or gases in to liquids, and it is used for many mass transfer
operations.
- Mechanical agitation can be done using various stirring equipments, like
- Impellers, propellers, agitators, etc.
- Vortex formation and prevention are very important factors
Gas Dispersed
(a) Marine type propellers:

Operated at high speed,
useful for low-viscosity
liquids
(b) Turbines: Flat blade used
for MTO, Curved blade
useful for fragile pulp,
crystals, etc., Pitched blade
is used for blending liquids,
Gas Dispersed
Typical flow patterns and vortex formations for single
phase Newtonian liquids of moderate viscosity are
shown in fig.6.4.
Vortex formation can be avoided by the following

means:
(1) In an Open tank with gas-liquid surfaces:
- Operation in laminar flow with slow mass transfer
- Installation of Baffles
- Off centre of impeller on a shaft
(2) In closed tanks, operated full, with no gas-liquid
surface:
- Baffles should be used.
Gas Dispersed
(3) Mechanical Agitation (Gas-Liquid contacts):
Factors affecting the operation:

(i) Impellers: Open and disk flat-blade
turbines are useful
(ii) Gas flow: High gas flow creates
blocking of gas bubbles below impeller
(iii) Impeller power: Presence of gas in
vessel reduces the power requirement
due to low viscosity of contents.
(iv) Bubble diameter, Gas holdup and
Interfacial area
(v) Mass Transfer Coefficients
(vi) Multistage absorption
Gas Dispersed
(4) Tray Towers: Tray towers are vertical cylinders in
which the liquid and gas are contacted in stepwise
fashion on trays or plates (refer fig. 6.8, sieve trays).
The overall effect is a multiple countercurrent contact of
gas and liquid, whereas , individual tray shows cross
current contact of gas and liquid.
Each tray of the tower is a stage as fluid are brought to
intimate contact, diffusion occurs and fluid are
separated.
The number of equilibrium stages in a column is depend
upon difficulty of the separation to be carried out and
determined by material balance and equilibrium
considerations.
Gas Dispersed
Operating characteristics of a sieve tray:
Flooding: Due to high pressure drop across trays. As
the Pressure difference increased due to the
increased flow rate of gas or liquid the level in the
downspout will rise further to permit the liquid to
enter the lower tray. Ultimately the liquid level may
reach that on the tray above. As a result, ultimately
tower gets flooded and tray efficiency decreases.
Priming: When liquid-gas combination tend to
create foam on the tray, which carries the liquid with
it to the upper tray (entrainment condition). As a
result liquid recirculates between trays and increase
the liquid load.
Coning: If liquid rates are too low, the gas rising from
the openings of tray push away the liquid and
resulted into poor gas-liquid contact.
Weeping: If the gas rate is too low, much of the liquid will rain down the openings and will not
use the complete flow over the tray benefit.
Dumping: At very low gas rates, none of the liquid reaches to the downspouts.
Gas Dispersed
General characteristics of tray tower:
Shall and Trays: The tower may be made of any number of materials , depending upon the
corrosion conditions expected. In order to cleaning, the towers are facilitated by manways or
hand holes, depending upon the size of tower.
Tray spacing: It is chosen on the basis of cost of construction, maintenance and other
entrainment conditions. (please refer Table 6.1 of W. E. Trebyl book on Mass Transfer
Operations).
Tower diameter: It must be large to handle the gas-liquid rates within the region of
satisfactory operation (please refer Fig. 6.9 of R. E. Treybal book on Mass Transfer
Operations).
Downspouts (or downcomers): It allows the liquid to travel from one tray to another by
providing disengagement of gas from liquids, so that the clear liquid enters the tray below.
Weirs: The depth of liquid on tray required for gas contacting is maintained by an overflow
(outlet) weir, which may or may not be a continuation of downspout plate.
Liquid flow: several of schemes commonly used for directing the
liquid flow on trays are shown in Fig. 6.11. Reverse flow or cross flow
can be used for small towers. Radial- or split flow can be used for
large-diameter towers. Cascade design is used for very large
diameter towers.
Gas Dispersed
Bubble cap tray:
Gas Dispersed
Sieve (perforated) tray:
Gas Dispersed
Tray efficiency: It is the fractional approach to an equilibrium stage which attained by a real
tray. Since, it is different from stage to stage, it is good to measure local, or
point efficiency, efficiency of mass transfer at a particular place on tray
surface.
Point Efficiency: --- (6.47)
Where,
EOG = (Change in conc. which actually occurs)/ (Change in
conc. Would occur if equilibrium established)
In EOG, ‘O’ emphasizes that EOG is a measure of the overall
resistance to mass transfer for both phases and ‘G’
Signifies that gas conc. are used.

yn,local = Conc. of gas leaving tray n and entering to tray (n-1).
yn+1,local = Conc. of gas leaving tray (n+1) and entering to tray
n.
y*local = Conc. in equilibrium with xlocal (which is assumed
constant in vertical direction).
of one tray of multi-tray tower

Gas Dispersed
Murphree Tray Efficiency: The bulk-average concentrations of all local pencils of gas of Fig.
6.21 are yn+1 and yn. The Murphree efficiency of the entire tray is then, .
----- (6.54)
Where, y*n is the value in equilibrium with leaving
liquid conc. xn.
In case of liquid completely back mixed, everywhere uniform conc. xn, In this case, eq. (6.54)
reverts to eq. (6.47) and EMG = EOG.
Entrainment: A further correction is required for the damage done by entrainment.

Entrainment represents a form of back-mixing, which acts to destroy the conc. changes
produced by the trays. It can be shown that the Murphree stage efficiency corrected for
entrainment is
------- (6.60)
Overall Tray Efficiency: Another method of describing the performance of a tray tower is
through the overall tray efficiency.
---- (6.65)
Liquid Dispersed
Venturi Scrubbers: Wetted wall towers: Spray Towers & Spray Chambers:
e.g. Absorption of SO2

from furnace gases
with lime/ slurry of e.g. Absorption of HCl
limestone. in industry
Liquid Dispersed
Packed Towers: Packed towers used for continuous
contact of liquid and gas in both counter-current
and cocurrent flow, are vertical columns which
have been filled with packing or devices of large
surface. The liquid distributed over and trickles
down through, the packed bed, exposing a large
surface to contact the gas.
Characteristics of packing:
1. Provide large interfacial surface between gas
and liquid. The specific packing surface ap in
any event is almost always larger than the
interfacial liquid-gas surface. e.g. lumps of coke
2. Possess desirable fluid-flow characteristic. i.e.
large fractional void volume ϵ, or fraction of
empty space, in the packed bad should be
large.
3. Be chemically inert to fluids being processed.
4. Have structural strength to permit easy
handling and installation.
5. Represent low cost.
Liquid Dispersed
Random Packing: Such packings are simply dumped into the tower allowing to fall randomly.
Earlier such readily material like broken stone, gravel or lumps of coke were used. They were
inexpensive but having small surface and poor fluid-flow characteristic. Now they are
manufactured from various materials like plastic, ceramic, wood, chemical stoneware,
porcelain, metals, carbon, etc.
During installation the packings are poured into tower to fall at random, and in order to
prevent breakage of ceramic or carbon packings, the tower may first be filled with water
to reduce the velocity of fall.
Generally the random
packings offer larger specific
surface and high gas-pressure
drop, in the smaller sizes, but
they cost less per unit volume
in the larger sizes.
As a rough guide, packing

sizes of 25-49 mm or more
are used for gas rates of 0.25
m3/s and 50 mm or larger for
gas rates of 1 m3/s.
Liquid Dispersed
Regular Packing: They are available in great variety. Regular packings offer the advantage of
(i) low pressure drop for gas, (ii) greater possible fluid flow rates (iii) more costly installtion
compared to random packing.
Stacked raschig rings are
economically practical only
in very large sizes.
Wood grids, or hurdles, are

inexpensive and used where
large void volumes required.
Knitted or woven wire screen

provide large interfacial
surface and a very low
pressure drop. Highly useful
for vacuum distillation.
Liquid Dispersed
Tower shells: These may be of wood, metal, chemical stoneware, acid-proof brick, glass,
plastic, plastic- or glass- lined metal, or other material depending upon the corrosion
conditions. For ease of construction and strength they are usually circular in cross section.
Packing Supports:
1. Packing supports must provide sufficient passage (free area for flow) for gas and liquid to
pass through it with minimum resistance.
2. Support must be strong enough to carry the weight of reasonable height of packing.
3. Specially designed supports are preferred.
4. It can be made of different materials including metals, expanded metals, ceramics, and
plastics.
Liquid Dispersed
Random Packing Size and Liquid Redistribution: Packing density, i.e. no. of packing pieces
per unit volume, in tower is less near the wall of a tower and hence the liquid distributed
more near the wall considering the less resistance and gas flows from the centre. As a result,
channeling occurs.
How to avoid channeling?
1. Keep the diameter of individual packing piece smaller than at least one-eighth (1/8) of
the tower diameter.
2. If possible keep the ratio dp/T =1:15. Where, dp is the packing diameter and T is the
tower diameter.
3. Provide redistribution of the liquid at intervals varying from 3 to 10 times the tower
diameter, but at least every 6 to 7 m.
Packing Restrainers:
4. They are necessary when the gas velocity is high.
5. They are generally desirable to guard the against lifting of packing due to sudden gas
surge.
6. Heavy screens or bars may be used.
7. For heavy ceramic packing, heavy bar plates resting freely on the top of the packing may
be used.
8. For plastics and other light weight packings, the restrainer is attached to the tower shell.
Liquid Dispersed
Entrainment Eliminators (mist eliminators): In case of high gas velocity, the gas leaving at
the top of the tower may carry liquid droplets, mostly in form of mist, with it. This can be
removed by mist eliminators, through which the gas must pass, installed at the top of the
tower above liquid inlet.
It is a layer of mesh (of wire, Teflon, PE, or other material) knitted with 98-99% voids,
roughly 100 mm thick, will collect mist particles/ droplets.
Counter current flow of liquid and gas through packing: For most random packing, the
pressure drop suffered by the gas is influenced by the gas and liquid flow rates in a manner
shown in fig. 6.33.
At a fixed gas velocity, the gas pressure drop increases with increased liquid rate, may be
due to less area available for gas flow as liquid hold up increases.
Region below A in fig. 6.33: The liquid hold up is constant with changing gas velocity,
although it increases with liquid rate.
Region between A and B: The liquid holdup increases rapidly with gas rate, the free area
becomes smaller for gas flow, and pressure drop rises more rapidly. This is known as
loading.
At B: As the gas rate is increased to B at fixed liquid rate, one of a number of changes occur:
(i) A layer of liquid, through which the gas bubbles , may appear at the top of the packing
(ii) Liquid may fill the tower so that there is a change from gas-continuous liquid-dispersed
to liquid-continuous gas-dispersed (Inversion)
(iii) Slugs of foam may rise rapidly upward through the packing.
Liquid Dispersed
Counter current flow of liquid and gas through packing (contd…):
At the same time, entrainment of liquid by the effluent gas increases rapidly, and the tower is
flooded.
The gas pressure drop then increases rapidly.
The change in the conditions from A to B is gradual, and initial loading and flooding are
determined by the change in slope of the pressure-drop curves rather than any visual effects.
Trickle bed reactor: When catalyst is used as
packing with cocurrent flow of gas and liquid, the
arrangement is called Trickle bed reactor.
Axial dispersion: It is the spreading of the residence
time in unidirectional flow owing to the departure
from purely plug flow, the fluid particle move
forward but at different speeds.
Back mixing: It is the backward flow in a direction
opposite to that of the net flow, caused by frictional
drag of one fluid upon the other, spray of liquid into
the gas (entrainment)and the like.
Points for choice between two main towers
Points Packed Towers Tray Towers
Gas pressure Require small pressure drop.
drop Useful for vacuum distillation.
Liquid holup Provide smaller liquid holdup
Useful for batch distillation
Liquid/gas ratio High values are best handled. Very low values are best handled.
Liquid cooling Not easy to do as in Tray tower. Cooling coils are more readily built.
Liquid can be removed from the tower,
pass through the coolers and returned
Side streams Difficult to get the side streams. Easy to get the side streams.
Foaming Systems Not preferred. More suitable as operate with less
bubbling of gas through the liquid.
Corrosion Less costly for corrosive systems Less preferred.
Solids present Neither type of tower is suitable unless the solids are removed as a pre-
treatment.
Cleaning Frequent Cleaning is difficult Frequent cleaning is easy
Large temp. Fragile packings are not suitable Good.
fluctuations Metal packings are good
Points for choice between two main towers
Points Packed Towers Tray Towers
Floor loading Plastic packed towers are lighter Tray towers are lighter than ceramic or
in weight than Tray towers metal packed towers.
Floor loading should be designed for accidental complete filling of the
tower with liquid.
Cost If there is no overriding considerations, cost is the major factor to be
taken into consideration.
Gas Absorption
Gas Absorption: It is an operation in which a gas mixture is contacted with a liquid to dissolve
one or more components of the gas and to provide a solution of them in the liquid. e.g. Coke
oven gas in washed with water to remove ammonia and again with to remove benzene and
toluene vapours.
• Here mass transfer takes place from gas to the liquid.

• When mass transfer occurs in opposite direction, i.e. from liquid to gas, the operation is
known as desorption or stripping.
• Generally, these operations are used for solute recovery or solute removal.
Gas Absorption
Equilibrium Solubility of Gases in Liquids
Why to study equilibrium solubility of gases in liquids?
The rate at which a gaseous constituent of a mixture dissolves in an absorbent liquid
depends upon the departure from equilibrium which exists. Hence, it is necessary to study
equilibrium solubility of gases in liquids.
Two component systems:
 What is gas solubility? If a quantity of a single gas
and relatively nonvolatile liquid are brought to
equilibrium, the resulting conc. of dissolved gas in
liquid is said to be the gas solubility at the
prevailing temp. and pressure.
 Different gases and liquids yield separate solubility
curves, which must determined experimentally for
each system.
 If the equilibrium pressure of a gas at a given
liquid conc. is high (curve B), the gas is insoluble in
liquid, while if it is low (curve C), the solubility is
high.
 Generally, solubility of gas decreases with increase
in temp. (Curve A and E for NH3)
 At boiling pt. of solvent, the gas solubility will be
zero, if vapour pressure of solvent is less than that
of gas or vapour solute.
Gas Absorption
Two component systems: If a mixture of gases is brought into contact with a liquid, under
certain conditions the equilibrium solubilities of each gas will be independent of the others,
provided that the equilibrium is described in terms of the partial pressures in the gas
mixture. e.g. Ammonia-air in water. Air is insoluble in water but it will not affect much the
solubility of ammonia in water.
Ideal liquid solutions: When the liquid phase is considered an ideal, equilibrium partial
pressure of gas from the solution can be calculated without experimentation.
There are four significant characteristics of an ideal solution:

1. The average intermolecular forces of attraction and repulsion in the solution are
unchanged on mixing the constituents.
2. The volume of the solution varies linearly with composition.
3. There is neither absorption nor evolution of heat in mixing the constituents. For gases
dissolving in liquids, this criterion should not include the heat of condensation of gas to
the liquid state.
4. The total vapour pressure of the solution varies linearly with composition expressed as
mole fractions.
In reality there is no ideal solutions and actual mixtures only approach ideality as a limit.
Gas Absorption
Ideal liquid solutions (contd..):
Requirement for ideality: The molecules of the constituents be similar in size, structure and
chemical nature. e.g. Solutions of optical isomers of organic compound. i.e., adjacent or
nearly adjacent members of a homologous series of organic compounds (solutions of
benzene in toluene, of ethyl and propyl alcohols, or of the paraffin hydrocarbon gases in
paraffin oils).
When the gas mixture is in equilibrium with an ideal liquid solution also follows the ideal gas
law (Raoult’s law): The partial pressure of a solute gas A equals the product of its vapour
pressure p at the same temperature and its mole fraction in the solution x.
------- (8.1)
Since, the nature of solvent is not affecting the ideality, it can be said that solubility of a
particular gas in ideal solution in any solvent is always the same.
For total pressures in excess of those for which the ideal-gas law applies, Raoult’s law can
frequently be used with fugacities substituted for the pressure terms.
Gas Absorption
Ideal liquid solutions (contd..):
Gas Absorption
Nonideal liquid solutions: As can be seen from Fig. 8.1, the line D (calculated partial
pressure for ammonia in equilibrium with water solution at 10°C) does not represent the
solubility data. On the other hand, line E is presenting the data very well fit up to 0.06 mole
fractions in liquid. The equation for such line is given by Henry’s law.
------- (8.2)
Where, m = constant, which must be established experimentally.
This equation is valid for wide range of data and chemicals with equilibrium pressure to 5 X
105 N/m2 to the low solubility systems to pressures as high as 34 N/m 2.
Gas Absorption
Choice of solvent for absorption: There are two purpose of absorption operation:
(i) to produce a specific solution, then the solvent is specified by the nature of the product.
(ii) to remove some constituent from the gas, some choice is frequently possible.
Water is the cheapest and the most plentiful solvent (Universal solvent).
Followings are the properties to be considered in selection of solvent for absorption:
1. Gas solubility: The gas solubility should be high, thus increasing the rate of absorption
and decreasing the quantity of the solvent required. Generally, the solvent of similar
chemical nature to the solute to be absorbed gives good solubility.
2. Volatility: The solvent should have low vapour pressure since the
gas leaving the absorber is mostly saturated with the solvent and
much may thereby be lost. A second less volatile liquid can be
used to recover the evaporated portion of the first.
3. Corrosiveness: The materials required for the equipment should
not be unusual or expensive.
4. Cost: Should be inexpensive and easily available.
5. Viscosity: Low viscosity preferred for reasons of (i) rapid
absorption rate, (ii) improved flooding characteristics in tower
(iii) low pressure drops on pumping (iv) good h.t. characteristics
6. Miscellaneous: nontoxic, nonflammable, chemically stable and
have low freezing point.
Gas Absorption
One Component Transferred; Material Balances
Countercurrent Flow: Fig. 8.4 shows a countercurrent tower with an arrangement to bring
about liquid-gas contact. The gas stream at any point in the tower consists of G total
mol/(area of tower cross section)(time), made up of diffusing solute A of mole fraction y,
partial pressure , or mole ratio Y, and nondiffusing, essentially insoluble gas Gs mol/(area)
(time). The relationship between these is,
--- (8.5) -- (8.6)
Similarly, the liquid stream consists of L total mol/(area)(time),

containing x mole fraction soluble gas, or mole ratio X, and essentially
nonvolatile solvent Ls mol/(area)(time).
--- (8.7) --- (8.8)
Since the solvent gas and solvent liquid are unchanged quantity
passing through the tower, it is convenient to express the material
balance in solvent term. A solute balance about Envelope-I is:
--- (8.9)
This is the straight line equation with Ls/Gs slope of
operating line.
Gas Absorption
One Component Transferred; Material Balances
Countercurrent Flow: Fig. 8.5 represents eq. 8.9. If the conc. In in mole fraction or partial
pressure, in place of mol ratio, the operating line will be curved (Fig. 8.6) and eq. 8.10 is used.
Eq. 8.9 and 8.10 and fig. 8.4 to 8.8 are for packed towers with 1 indication at the bottom and 2
at the top. For tray towers, considering the number of tray, eq. 8.9 becomes, when applied to
an entire tower:
Gas Absorption
Minimum Liquid Gas Ratio for Absorbers
In the design of absorbers, the quantity of gas to be treated G or Gs, the terminal conc. Y1
and Y2, and the composition of the entering liquid X2 are generally fixed by process
requirements, but the quantity of the liquid to be used is subject to choice. The operating
line must pass through point D and must end at the ordinate Y1. In this case, DE is the
operating line and exit liquid composition will be X1.
Line DF: Less liq. used, driving force for diffusion is less, absorption is more difficult, high
contact time between liquid and gas is needed, absorption tower must be tall.
Line DM: At P, diffusional driving force is zero, infinite time of contact needed for desired
conc. change, infinitely tall tower needed. This then represents limiting liquid - gas ratio.
The minimum liquid gas ratio is then
corresponds to an exit liquid
concentration in equilibrium with the
entering gas. (Fig. 8.7(b))
For strippers, an operating line which

anywhere touches the equilibrium curve
represents a maximum ratio of liquid to
gas and a maximum exit gas
concentration.
Gas Absorption
Minimum Liquid Gas Ratio for Absorbers
Cocurrent flow:
 Negative operating line slope, -Ls/Gs and no limit on this ratio but an infinitely tall tower
would produce an exit liquid and gas in equilibrium as at (Xe, Ye).
 Cocurrent flow may be used when an exceptionally tall tower is built in two sections (Fig.
8.9) with the second section operated in cocurrent flow to save on the large diameter gas
pipe connecting the two.
 It may also be used if the gas to be dissolved in liquid is a pure substance, where there is no
advantage of countercurrent operation, or if a rapid irreversible chemical reaction with
dissolved solute occurs in the liquid, where only one equivalent theoretical stage is needed.
SOLVE THE
PROBLEM
8.2 AT
HOME.
Gas Absorption
Countercurrent Multistage Operations: One Component Transferred
Tray towers and similar devices brings stepwise contact of the liquid and gas and are therefore
multistage cascades. Liquid and gas are brought into intimate contact and separated on each
tray. Hence, each tray is a stage.
Theoretical or ideal tray: It is
where the average composition of
all the gas leaving the tray is in
equilibrium with the average
composition of all the liquid
leaving the tray.
How to calculate the no. of
theoretical/ideal trays to bring
about a given change in liquid and
gas composition can be
determined graphically as shown
in Fig. 8.12.
Nearer to equilibrium curve means
more no. of stages required and
touching the equilibrium curve
means minimum Ls/Gs and infinite
no. of trays needed.
Gas Absorption
The Absorption Factor A: It is defined as the ratio of the slope of the operating line to that of
the equilibrium curve. (A = L/mG). Reciprocal of A is called stripping factor, S.
If A is less than 1: Infinite no. of trays required and absorption of solute is limited.
If A is greater than 1: Any degree of absorption is possible if sufficient no. of trays provided.
For a fixed degree of absorption from a fixed amount of gas, as A increases beyond unity, the
Absorbed solute is dissolved in more and
more liquid and becomes less valuable. At
the same time, the no. of trays decreases and
so equipment cost decreases.
Such opposing cost tendencies means, there

will be a value of A or of L/G for which the
most economical operation results.
As a thumb rule, it is found that the most

economical A will be in the range of 1.25 to
2.0
Solve problem 8.3 at home.

Gas Absorption
Real Trays and Tray Efficiency: For a given absorber or stripper, corrected methods for
estimating the Murphree tray efficiency for entrainment (EMGE) permit estimation of the tray
efficiency as a function of composition and temperature as they vary from one end of the
tower to the other.
Generally, it is sufficient to make such calculations at three or four locations and then proceed
as in fig. 8.16. The broken line drawn between equilibrium curve and operating line at a
fractional vertical distance from the operating line equal to the prevailing Murphree Gas
Efficiency. Thus the value of EMGE for the bottom tray is the
ratio of the lengths of lines, AB/AC. Since the broken line then
represents the real effluent compositions from the trays, it is
used instead of the equilibrium curve to complete the tray
construction, which now provides the number of real trays.
Analytical calculation: When Murphree efficiency is constant
for all trays, and under conditions such that the operating line
and equilibrium curves are straight (Henry’s law, isothermal
operation, dilute solutions), the overall tray efficiency can be
computed and the number of real trays can be determined
analytically:
Gas Absorption
Continuous Contact Equipment
 Packed towers and spray towers operate on continuous basis.
 The composition of liquid and gases change continuously with the height of the packing and
hence every point on an operating line represents condition found somewhere in tower.
 In tray towers, only isolated points on the operating line corresponding to trays have
significance.
Height Equivalent to an Equilibrium Stage (Theoretical Plate) (HETP):

 Simple and the oldest method for designing packed towers ignoring the differences
between stagewise and continuous contact.
 In this method the number of theoretical trays or plates required for a given change in
concentration is computed by the methods of the previous section.
 This is then multiplied by a quantity, the height equivalent to a theoretical tray or plate
(HETP) to give the required height of packing to do the same job.
 The HETP must be an experimentally determined quantity characteristic for each packing.
 HETP varies with the type and size of the packing, flow rates of each fluid, for every system
with concentration.
 HETP methods requires enormous amount of experimental data to permit utilization of the
method.
 HETP method fail to consider the different action of tray and packed tower.
 Now, this method is abandoned.
Gas Absorption
Absorption of one component: Consider a packed tower of unit cross section (fig. 8.17).
S = The total interfacial surface of mass transfer, as a result of spreading of the liquid in a film
over packing, per unit cross section.
= a Z, where a = surface per unit volume of packing
and Z = packed volume per unit tower cross section or height.
In the differential volume dZ, the interface surface is
dS = a dZ ------------------------------------ (8.17)
Gy = The quantity of solute A in the gas passing the differential section of
the tower under consideration, mol/(area)(time).
Since, NB = 0, NA/(NA + NB) = 1, application of eq. 5.20 provides eq. 8.18,
Both G and y vary from one end of the tower to the other, but Gs, the
solvent gas which is essentially insoluble, remains unchanged. Therefore,
Gas Absorption
Substitute eq. 8.19 into eq. 8.18, rearranging and integrating,
d (Gy) G dy G dy Z y1 G dy
dZ  but d (Gy)   dZ  Hence, Z   dZ     (8.20)
1  yi 1  y 1  yi 0 y2 1  yi
a FG ln FG a (1  y ) ln FG a (1  y ) ln
1 y 1 y 1 y
The value of y can be found out using eq. (5.21) with NA/ΣN = 1; FL FL a
1 yi  1 x  FG  1 x  FG a
         (8.21)
1 y  1 xi   1 xi 
Now take, y – yi = (1 – y) – (1 – yi) ----- (8.22)
Now, the numerator and denominator of eq. (8.20) can be multiplied respectively by right- and
left- side of eq. (8.22).
y1 G dy [(1  y )  (1  yi )] (1  y )  (1  yi ) y1 G dy (1  y )iM
Z  but  (1  y )iM  Z     (8.23)
y2 1  yi 1  yi y 2 F a (1  y )( y  y )
( y  yi ) FG a (1  y ) ln ln G i
1 y 1 y
Let us define, height of gas transfer units (HtG) as, (8.24)
Substitute eq. (8.24) in eq. (8.23),
------ (8.25)
where NtG = = Number of gas transfer units

Gas Absorption
Eq. (8.25) can be further simplified by substituting the arithmetic average for the logarithmic
average (1 - y)iM,
Which involves a little error. NtG then becomes,
y1 dy 1 1  y2 dy
N tG    ln (8.27), where, can be obtained by graphical integration.
y2 y  yi 2 y  y1 y  yi
For dilute solutions, the second term on the right of eq. (8.27) is negligible, FG a ≈ ky a, and yi
can be obtained by plotting a line of slope (-kx a/ky a) from points (x, y) on the operating line to
intersection with the equilibrium curve.
Gas Absorption
The above relationships all have their counterparts in terms of liquid concentrations, derived in
exactly the same way,
Solve the Problem 8.6 at home

Gas Absorption
Overall coefficients and transfer units (m = dyi/dxi = const.): For the cases where the
equilibrium distribution curve is straight and the ratio of MTCs is constant, it is convenient to
express in terms of overall MTCs. The expressions for the height packing can then e written as,
-- (8.33) --- (8.38)
---- (8.34) -- (8.39)
-- (8.35) -- (8.40)
-- (8.36) (8.41)
(8.37) (8.42)
NtoG & HtoG = Number of an overall gas transfer units and Height of an overall gas transfer
units (used when the principal mass transfer resistance lies within the gas)
NtoL & HtoL = Number of an overall liquid transfer units and Height of an overall liquid transfer
units (used when the principal mass transfer resistance lies within the liquid)
Gas Absorption
Topics “Dilute Solutions” and “Dilute Solutions, Henry’s law” are in self study.
Graphical construction of transfer units:
Line KB has been drawn so as to be everywhere vertically halfway between operating line and
equilibrium curve.
CFD (corresponding to one transfer unit) has been constructed by drawing the horizontal line
CEF so that CE = EF and continuing vertically to D.
Since, GE = EH, and if the operating line is straight,

DF = 2(GE) = GH, the step CFD corresponding to one
transfer unit. yD
yG
For computing NtOL, the line KB would be drawn
horizontally halfway between yF
(yG – YH) =
equilibrium curve and operating line driving force for
and would bisect the vertical composition
change (yD – yF) yH
portions of step.
Gas Absorption
Overall heights of transfer units: When overall number of transfer units are appropriate, the
overall heights of transfer units can be synthesized from those for the individual phases
through the relationships developed like in eq. (5.25(a)), with m’ = m” = m = const. can be
written,
-- (5.25(a))
Where,
-- (8.52)
Whereas, by definition of the heights of transfer units,
If the mass-transfer resistance is essentially all in the gas, yi ≈ y*, and
For dilute solution, concentration ratio of eq. 8.54 can be dropped.

Gas Absorption
Overall heights of transfer units: In similar fashion, eq. 5.26 (a) yields,
Where,
And if the mass transfer resistance is essentially all in the liquid,
The concentration ratio of eq. 8.56 can be dropped for dilute solutions.
Self study:
Solve Problem: 8.7 at home.
Absorption with Chemical Reaction.
Liquid – Liquid Extraction (Solvent Extraction)
Liquid Extraction: It is the separation of the constituents of a liquid solution by contact with
another insoluble liquid. Example of stage-wise contact, it
Acetic acid Ethyl acetate Water can be carried out in batch or
Feed: Solution which is continuous fashion.
to be extracted.
Solvent: The liquid with Shaking well/
which the feed is agitation
After settling,
contacted. due to density Acetic acid +
Extract: The solvent-rich and solubility Ethyl acetate
product of the Extract + little water
difference….
operation Raffi
Little Acetic
Raffinate: The residual nate
acid + little
liquid from which solute
Ethyl acetate
has been removed.
+ water
Double solvent or Fractional extraction: Two solvents are used to separate the components of
a feed. e.g. p- and o- nitrobenzoic acids are separated by distributing them between the
insoluble liquids chloroform and water. The chloroform preferentially dissolves the para isomer
and the water the ortho isomer.
https://www.khanacademy.org/test-prep/mcat/chemical-processes/separations-purificatio
ns/v/extractions
Fields of Usefulness: Applications of extraction fall in several categories:
 Those where extraction is in direct competition with other separation methods
 Those where it seems uniquely qualified.
(i) In competition with other mass transfer operations:
 Relative cost is an important factor because distillation and evaporation gives relatively
pure product whereas the products from extraction needs to be separated by further
processing.
 Extraction is an attractive alternative to distillation under high vacuum at very low
temperatures to avoid thermal decomposition.
 Many a time, extraction is better option against crystallization.
(ii) As a substitute for chemical methods:
 Chemical methods consume reagents and frequently lead to expensive disposal
problems for chemical by-products. Liquid extraction, incurs no chemical consumption
or by-product production and hence can be less costly.
(iii) For separations not now possible by other methods:
 For nearly boiling point chemicals are difficult to separate by distillation, there
extraction is the best option.
 Many pharmaceutical products are produced in mixtures are so complex that only
liquid extraction is a feasible separation device.
Liquid Equilibria
Notation Scheme:
Liquid Equilibria
Notation Scheme:
Liquid Equilibria
Equilateral -Triangular Coordinates: It is widely used to describe graphically the concentrations
in ternary systems.
Property of an equilateral triangle: Sum of the perpendicular distances from any point within
the triangle to the three sides equals the altitude of the triangle. Therefore, the altitude
represents the 100% composition and the distances to the three sides the percentages or
fractions of the three components.
Liquid Equilibria
Equilateral -Triangular Coordinates:
 In fig. 10.1, each apex of the triangle represents one or more pure components, as marked.
 The perpendicular distance from any point such as K to the base AB represents the
percentage of C in the mixture at K, the distance to the base AC the percentage of B, and
that to the base CB the percentage of A. Thus xK = 0.4.
 Any point on a side of the triangle represents a binary mixture.
 Point D, for example, is a binary containing 80% A, 20% B. All points on the line DC represent
mixtures containing the same ratio of A to B and can be considered as mixtures originally at
D to which C has been added.
 If R kg of mixture at point R is added to E kg of a mixture at E, the new mixture is shown on
the straight line RE at point M, such that
 Alternatively, the composition

corresponding to point M can be
computed by material balances.
 Similarly, if a mixture at M has
removed from it a mixture of
composition E, the new mixture is on
the straight line EM extended in the
direction away from E and located at
R, so that eq. 10.1 applies.
Liquid Equilibria
The Mixture Rule:
Liquid Equilibria
Equilateral -Triangular Coordinates: The following are the major kind of systems occur in liquid
extraction:
(A) System of three liquids-One Pair Partially Soluble: This is the most common type of
system in extraction, and typical examples are water (A)- Chloroform (B) – acetone (C) and
Benzene (A) – water (B) – Acetic acid (C). The triangular coordinates are used as isotherms,
or diagrams at constant temperature.
Liquid C is completely soluble in A and B, but A and B dissolve only to a limited extent in each
other to give rise to the saturated liquid solutions at L (A-rich) and at K(B-rich).
Liquid Equilibria
extraction:
(A) System of three liquids-One Pair Partially Soluble: The more insoluble the liquids A and B,
the nearer the apexes of the triangle will point L and K be located.
 Take a binary mixture J, anywhere between L and K, will separate into two insoluble liquid
phases of composition L and K, the relative amounts of the phases depending upon the
position J, according to the principle of eq. 10.1
 LRPEK = binodal solubility curve indicating change in composition of A & B upon addition of
C.
 Any mixture outside this region creates homogeneous solution of one liquid phase.
 Any ternary mixture under the curve, e.g. M, will for, two insoluble saturated equilibrium
compositions such as R (A-rich) and E (B-rich).
The line RE joining this
equilibrium composition is a tie
line, which must pass through
point M representing the
mixture as a whole.
There are infinite number of tie
lines in the two phase region.
They are rarely parallel and
change their slope slowly in one
direction.
Liquid Equilibria
extraction:
(A) System of three liquids-One Pair Partially Soluble:
 Solutropic system: In a relatively few systems the direction of tie line slope changes, and one
tie line will be horizontal. Such systems are said to be solutropic.
 Plait point, P: The last of the tie lines and the point where A-rich and B-rich solubility curves
merge, is generally not at the maximum value of C on the solubility curve.
 The % of C in solution E is more than in solution R and hence, the distribution of C favours B-
rich phase. This is shown on distribution diagram, where point (E,R) lies above the diagonal y
= x. The ratio y*/x, distribution coefficient, is greater than unity.
 The concentration of C at the ends of tie line, when plotted against each other, gives
distribution curve.
If the slope of tie line is in
opposite direction, with C
favouring A at equilibrium, the
distribution curve lies below the
diagonal.
The distribution curve may be
used for interpolating the tie
line.
Liquid Equilibria
(A) System of three liquids-One Pair Partially Soluble:
Temperature effect: It is as shown in fig. 10.4(a), where temp. is plotted vertically and the
isotherm triangles are seen to be sections through prism.
With increase in temperature, the solubility of A and B increases and above point P (i.e. above
some temp. t4, the critical solution temp.) they dissolve completely.
The increased solubility at high temp. influences the ternary equilibria considerably and this is
best shown by projection of isotherms onto base triangle.
That will decrease the area of heterogeneity and also change the slope of tie lines.
The liquid extraction must be
carried out below temp. t4.
Effect of Pressure:
Except at very high pressures, the
influence of pressure on the liquid
equilibrium is so small that it can
generally be ignored.
Liquid Equilibria
(B) System of three liquids-Two Pair Partially Soluble: It can be explained by the system
Chlorobenzene (A)-water (B) – methyl ethyl ketone (C), where A and C are completely
soluble, while the pairs A-B and B-C show only limited solubility.
 At the prevailing temp., points K and J represent the mutual solubilities of A and B and
points H and L those of B and C.
 Curves KRH (A-rich) and JEL (B-rich) are the ternary solubility curves, and mixtures outside
the band between these curves form homogeneous single phase liquid solutions.
 Mixtures such as M, inside the heterogeneous area, form two liquid phases at equilibrium
at E and R, joined on the diagram by a tie line.
 The corresponding curve is shown in fig. 10.5(b).
Liquid Equilibria
(B) System of three liquids-Two Pair Partially Soluble:
Effect of Temperature:
 Increased temperature generally increases the solubilities and at the same time influences
the slope of the tie lines.
 Above the critical solution temperature of the binary B-C at t3, the system is similar to the
first type discussed.
Liquid Equilibria
(C) System of two partially liquids and one solid: Such system exists when solid does not form
compounds such as hydrates with the liquid, the isotherms will be like as shown in fig. 10.7
Example, naphthalene (C) – aniline (A) – isooctane (B).
 Solid C dissolves in liquid A to form a saturated solution at K and in liquid B to give the
saturated solution at L.
 A and B are soluble only to the extent shown at H and J. Mixtures in the regions AKDH and
BLGJ are homogeneous liquid solutions.
 The curves KD and GL show the effect of adding A and B upon the solubilities of the solid.
 In the region HDGJ two liquid phases
form: if C is added to the insoluble
liquids H and J to give a mixture M, the
equilibrium liquid phases will be R and
E, joined by a tie line.
 All mixtures in the region CDG consist
of three phases, solid C, and saturated
liquid solutions at D and G.
 Liq. Extraction operation are confined
to the region of the two liquid phases,
which is that corresponding to the
distribution curve shown in fig. 10.7(b)
Liquid Equilibria
Other Coordinates:
 The coordinate scales of equilateral triangles are necessarily always the same and in order
to be able to expand one concentration scale relative to the other, rectangular coordinates
can be used.
 In fig. 10.9(a), concentration of B is plotted as abscissa against concentration of C (x and y)
as ordinate.
 Unequal scales can be used in order to expand the plot as desired.
 Eq. 10.1 applies for mixtures on Fig. 10.1(a), regardless of any inequality of the scales.
 ---- (10.1)
Liquid Equilibria
Other Coordinates:
 Another rectangular coordinate system involves
plotting as abscissa the weight fraction C on a B-free
basis, X and Y in the A- and B-rich phases, respectively,
against N, the B-concentration on a B-free basis, as
ordinate, as shown in upper part of fig. 10.10.
 This has been plotted for a system of two partly
miscible pairs (fig. 10.5)
 In extraction, the two phases are produced by addition
of solvent and in distillation, it is done by addition of
heat. So heat and solvent are analogous to each other.
 Tie line such as QS can be projected to X, Y coordinates
to produce a solvent –free distribution graph similar
to those of distillation.
 The mixture rule on these coordinates is
Where, M’ and N’ are the B-free weights of these

mixtures.
(Multicomponent system – Self study)
Liquid Equilibria
Choice of Solvent: It is not possible that any solvent can possess all the properties of ideal
solvent. Followings are the criteria to be taken care while selecting solvent for extraction:
1. Selectivity: The effectiveness of solvent B for separating a solution of A and C into its
components is measured by comparing he ratio of C to A in the B-rich phase to that in the
A-rich phase at equilibrium. The ratio of the ratios, the separation factor, or selectivity, β. If
E and R are the equilibrium phases,
-- (10.3)
For extraction, it should be greater than unity. At plait point it is equals to unity.
2. Distribution Coefficient: This is the ratio y*/x at equilibrium. Larger the value of
distribution coefficient, less the solvent required for extraction.
3. Recoverability: Solvent must be easily recoverable at lower cost from the solute or mixture.
For that another mass transfer operation can be used like distillation.
4. Density: A density difference between extract and raffinate phase is must, for both stage-
wise and continuous –contact equipment operation. The larger the difference the better.
5. Interfacial Tension: The larger the interfacial tension (is good), the more readily
coalescence of emulsions will occur but the more difficult the dispersion of one liquid in
the other will be. It is zero at plait point.
6. Chemical Reactivity: The solvent must be chemically stable and inert towards the other
components of the system and material of construction.
Liquid Equilibria
Choice of Solvent: It is not possible that any solvent can possess all the properties of ideal
solvent. Followings are the criteria to be taken care while selecting solvent for extraction:
7. Insolubility of Solvent: More the insolubility of solvent with anyone component, more the
easy the separation is. (Only those A-C mixtures between D and A can be separated by use
of the solvents B or B’, since mixtures richer in C will not form two liquid phases with the
solvents.
8. Viscosity, vapour pressure, and freezing

point: These should be low for ease in
handling and storage.
9. Miscellaneous: The solvent should be
nontoxic, nonflammable, and of low
cost.
Equipment and Flowsheets
Stage-wise contact: Extraction in stage type equipment is depending upon the type of the
system and extent of separation desired.
Each stage is a theoretical or equilibrium stage, where extract and raffinate solutions are in
equilibrium with each other.
Each stage must include facilities for contacting insoluble liquids and separating the product
streams.
A combination of mixer and settler can therefore constitute a stage. It may also be arranged in
cascade. Counter current operation may be carried out in a tower.
Single –stage extraction:
 Feed of mass F (if Batch) or F mass / time (if continuous) contains substances A and C at xF
weight fraction C.
 This is contacted with mass S1 (or mass /time) of a solvent, principally B, containing ys
weight fraction of C, to give equilibrium extract E1 (mass / time) and raffinate R1 (mass /
time)
 Solvent recovery then involve separate removal of solvent B from each product stream.
 M1 = adding S to F produces in the extraction stage a mixture, M1, which forms the
equilibrium phases E1 and R1 by joining tie line through M1.
 Total M.B.: --- (10.4)
 C-balance: -------- (10.5)
From eq. 10.5, xM1 can be computed.
The operation can be followed in either of the phase diagram as shown.
If the solvent is pure B (ys = 0), it will be plotted at the B apex, but it has been recovered
from the previous extraction and therefore contains a little A and C as well, as shown by the
location S.
 Alternatively, the amount of solvent required to get location for M1, on FS line,
----- (10.6) and the extract and raffinate can be computed by the
mixture rule or by the material balance for C: --- (10.7) and hence,
---- (10.8) and R1 can be determined

through eq. 10.4.
 For extraction, two insoluble phase must form, hence, point M1 must lie within
heterogeneous liquid area.
 The minimum amount of solvent is found by locating M1 at D, which can give infinite
amount of extract at G
 The maximum amount of solvent is found by locating M1 at K, which will give infinite
amount of raffinate at L (where, L represents the raffinate with the lowest possible C
concentration.)
 Calculations for systems of two insoluble liquid pairs, or with a distributed solute which is a
solid, are made in exactly the same manner, and eq. 10.4 to 10.8 all apply.
 All calculations can also be made on solvent free basis. (Upper part of fig. 10.13)
If solvent S is pure B, its N value is infinite and the line FS is then
vertical. Products E1 and R1 lie on a tie line through M1
representing the entire mixture in the extractor. Material balances
for use with this diagram must be made on a B-free basis. Thus,
---- (10.9)
Where the primes indicate B-free weight (The feed is normally B-
free, and F = F’). A balance for C is
-- (10.10)
And for B ---- (10.11)
(generally, NF = 0 since the feed contains no B). The coordinates of
M1’ can be calculated, point M1 located on line FS, the tie line
located and the B-free weights E1’ and R1’, computed:
----- (10.12)
And R1’ is obtained through eq. 10.9 . The total weights of the
saturated extract and raffinate are then,
--- (10.13)
Single –stage extraction: If the solvent is pure B (i.e. Ns = ꚙ), these equations still valid with
the simplifications that S’ = 0, Ys = 0, S’Ns = B and F’ = M1’.
Minimum and maximum amounts of solvent correspond to

putting M1 at D and K on the figure.
Eq. 10.9 and 10.10 leads to,
----- (10.14)
When the equilibrium extract and raffinate are located on the

lower diagram of fig. 10.13, eq. 10.14 is seen to be that of the
operating line shown, of slope, -R1’/E1’.
Multistage Crosscurrent Extraction: This is an extension of single-stage extraction, wherein
raffinate is successively contacted with fresh solvent, and may be done continuously or in
batch. (Fig. 10.14, three stage extraction).
 A single final raffinate results, and the extracts can be combined to provide the composited
extract.
 Calculations are shown on triangular and on solvent-free coordinates.
 All the material balances for a single-stage can be applied to each stage separately, except
the feed to any stage is the raffinate from the preceding stage.
 Thus for any stage n:
Continuous Countercurrent Multistage Extraction:
 Extract and raffinate streams flow from stage to stage in countercurrent and provide two
final products, raffinate RN and extract E1.
P
 For a given degree of separation, this type of operation requires less stages for a given
amount of solvent, or less solvent for a fixed number of stages, than the crosscurrent
methods.
 A total material balance about the entire plant is: -- (10.22)
 Point M can be located on line FS through a balance for substance C:
 Eq. 10.22 indicates that M must lie on RN E1 , as shown in fig. 10.19. Rearrangement of eq.
P
10.22 provides, RN – S = F – E1 = ΔR ----- (10.25), where ΔR, a difference point, is the

P
net flow outward at the last stage NP.

 According to eq. 10.25, (RN – S = F – E1 = ΔR ----- (10.25),) E1F and RN S must intersect at ΔR
P P
(Refer Fig. 10.19). This intersection in some cases may be located on right side.
 A material balance for stages s through Np is
 So that the difference in flow rates at a location between any two adjacent stages is
constant, ΔR. Line EsRs-1 extended must therefore pass through ΔR , as shown in the figure.
 The graphical construction is as follows:  After location of points F, S, M, E1, RN and
P
ΔR , a tile line from E1 provides R1 since

extract and raffinate from the first
theoretical stage are in equilibrium.
 A line from ΔR through R1 when extended
provides E2, a tie line from E2 provides R2,
etc.
 The lowest possible value of xN is that
P
given by the A-rich end of tie line which,

when extended, passes through S.
 If the amount of solvent is increased, point M representing overall plant balance will move
towards S (Fig. 10.19) and point ΔR moves away to the left.
 At an amount of solvent such that line E1F and SRN are parallel, point ΔR will be at infinite
P
distance.
 Still higher amount of solvent will cause these lines to intersect on the right hand side of the
diagram with ΔR nearer B for increasing quantities.
 If a line from ΔR coincide with a tie line, an infinite number of stages will be required to reach
this condition.
 The maximum amount of solvent for
which this occurs corresponds to the
minimum solvent/feed ratio which can be
used for the specified products.
 The procedure for determining the
minimum amount of solvent is indicated
in Fig. 10.20
 All tie lines below that marked JK are extended to line SRN , to give intersections with line
P
SRN as shown.
P
 The intersection farthest from S (if on the LHS of diagram) or nearest S (if on the RHS of
diagram) represents the difference point for minimum solvent, as at point ΔRm.
 The actual position of ΔR must be farther from S (if on LHS) or nearer to S (if on RHS) for a
finite number of stages.
 The larger the amount of solvent, the less the number of stages.
 The tile line which when extended passes through F, that is tie line JK, will locate ΔRm for
minimum solvent.  When the number of stages is very large,
the construction indicated in Fig. 10.21
may be more convenient.
 A few lines drawn at random from point ΔR to intersect the two branches of the solubility
curve as shown. (Remember, the intersection may not indicate streams between two actual
adjacent stages).
 The C concentrations xs and ys+1 corresponding to these are plotted on x, y coordinates as
shown to provide an operating curve.
 Tie line data provide the equilibrium curve y* vs. x, and the theoretical stages stepped off in
the manner used for absorption.
 Fig. 10.22 shows the construction for solvent-free coordinates.
 The B-free material balance for entire plant is
---- (10.28)
Where, F = F’ because the feed is B-free.
 M’ is therefore on the line FS at XM calculated by a C balance.
------- (10.29)
 If pure B is used as solvent, S’ = 0, S’Ys = 0, F’ = M’, XM = XF, and
point M is vertically above F.
 Line E1RN must pass through M. Then
P
------- (10.30)
 The balance stages s through NP is
------ (10.31)
 Where, ΔR‘ is the difference in solvent-free flow, out minus in, at
stage NP, and the constant difference in solvent-free flows of
the streams between any two adjacent stages.
 Line EsRs-1 extended, where s is any stage, must therefore pass
through ΔR on the graph.
The graphical construction is then as follows:
 After locating points F, S, M, E1, RN and ΔR, a tie line from E1
P
provides R1, line ΔRR1 extended locates E2, etc.

 A ‘C’ balance, stages s through NP, following eq. 10.30 is,
---- (10.32)
A ‘B’ balance is,
--- (10.33)
(10.34)
The ratio of flows can be obtained from the ratio of

line lengths EsΔR/Rs-1ΔR on the upper part of fig. 10.22 or as the
slope of cord from (Xs-1, Ys) to XΔR on the 45°diagonal of the
lower diagram, as shown. The difference point coordinates are,
As the solvent/feed ratio is increased, ΔR moves lower (Fig.10.22),

and minimum solvent is determined by the lowest point of
intersection of all extended tie lines with the line SRN .
P
Continuous Countercurrent Extraction with Reflux:
 The feed to be separated is introduced at an appropriate place into the cascade, through
which extract and raffinate liquids are passing counter currently.
 The concentration of solute C is increased in the extract-enriching section by counter current
contact with a raffinate liquid rich in C.
 This is provided by removing the solvent from extract E1 to produce the solvent-free stream
E’, part of which is removed as extract product PE’ and part returned as reflux R0.
 C stripped from the raffinate by counter current contact with solvent.
 For the stages in the raffinate stripping section, eq. 10.31 to10.34 can be applied.
 In the extract enriching section, an A + C balance about the solvent preparator is,
--- (10.39)
 Let ΔE = Net rate of flow outward from this section, then for A + C content,
(10.40)
 and for its C content, XΔE = XPE ---- (10.41) , while for its B content --- (10.42)
 The point ΔE is plotted on Fig. 10.28, which is drawn for a system of two partly miscible
component pairs. For all stages through e, an A + C balance is
---- (10.43)
or ---- (10.44)
A ‘C’ balance is ----------- (10.45)
And A ‘B’ balance is ----------- (10.46)
 Since e is any stage in this section, lines radiating from
point ΔE cut the solubility curves of Fig. 10.28 at points
representing extract and raffinate flowing between any
two adjacent stages.
 ΔE therefore a difference point, constant for all stages in
this section, whose coordinates mean
 Alternating tie lines and lines from ΔE then establish the

stages, starting with stage 1 and continuing to the feed
stage.
 Fig. 10.28 also shows the raffinate-stripping stages,
developed as before for countercurrent extraction.
 Solving eq. 10.43 with 10.45 and 10.46 produces
the internal reflux ratio at any stage,
 This can be calculated from line lengths on the

upper diagram of fig. 10.28 or from the slope of a
chord on the lower diagram, as shown.
 The external reflux ratio is,
---- (10.48)
 Which can be used to locate ΔE for any specified

reflux ratio.
 Material balance for entire plant, for A+C is,
---- (10.49)
 If eq. 10.30 and 10.40 are used, this becomes
--- (10.50)
Where, normally F = F’.
(10.30)
(10.40)
 Point F must lie on line joining the two difference
points , and the optimum location of the feed
stage is represented by the tie line which crosses
line ΔRFΔE, as shown.
 Higher the location of ΔE (and the lower ΔR), larger
the reflux ratio and smaller the no. of stages.
 When, R0/PE’ is infinite (infinite reflux ratio or total
reflux), NΔE=ꚙ and minimum number of
theoretical stages results.
 In that case, the capacity of the plant falls to zero,
feed must be stopped and solvent BE is
recirculated to become S.
 See the Fig. 10.29 on N, X, Y coordinates.
 Corresponding XY diagram uses the 45° diagonal
as operating line for both sections of cascade.
 An infinity of stages is required if a line radiating from either
ΔE or ΔR coincides with a tie line, and the greatest reflux ratio
for which this occurs is the minimum reflux ratio. (Fig. 10.30)
 Tie lines to the left of J are extended to intersect line SRN +1
P
and those to the right of J are extended to line PE’E1.

 Points ΔEm and ΔRm for minimum reflux ratio are found by
selecting the intersections farthest from N=0, consistent with
the requirement that ΔE, ΔR, and F must always lie on the
same straight line.
 Self Study: Economic balances
Stage Efficiency:
Stage Type Extractors
Major two types of stage-type equipment are used:
1. Single stage mixer-settlers and multi stage cascades constructed from them.
2. Sieve tray, multi stage towers.
3. A mixer-settler is a single stage device, generally consisting of two parts,

(i) a mixer for contacting the two liquid phases to bring about mass transfer
(ii) a settler for their mechanical separation.
Operation may be continuous or batch wise.
There are two types of mixers: (1) Flow mixers and (2) Mixing vessels
Flow mixers (or line mixers): These are devices of very small volume placed in a pipeline, such as
series of orifices or mixing nozzles through which the two liquids to be contacted are
pumped cocurrently. Mechanical energy loss due to pressure drop used to disperse liquid
with each other.
These devices are useful only for continuous operation and limited applications.
Disadvantage: Degree of dispersion depends upon the flow rate and specific interfacial area
reduces rapidly downstream from the mixer, while the holding time is very less, mass
transfer can be expected to be poor.
Agitated Vessels: They are discussed in Chapter-6 earlier. Impellers, turbines and other means
of agitation are used in agitators.
Emulsions and Dispersions:
 Dispersion takes place of one liquid into other in form of small bubbles having diameter
varying from 0.1 to 1 mm. Too small bubbles can cause difficulty in settling.
 Generally liquid flowing at lower rate will disperse in other.
 Generally, emulsion should be avoided for better separation. Emulsion creates third layer in
during settling between extract and raffinate. That causes difficulty in clear settling and
separation.
 To break an emulsion created, both sedimentation and coalescence of both dispersed phase
must occur.
Settlers:
In continuous extraction, the dispersion issuing from the mixer must be passed to a settler or
decanter, where at least the primary break occurs.
Typical gravity settlers arrangements are shown in Fig. 10.40.
Settlers: Fig. 10.40(a): Simple design,
Inlet “Picket-fence” baffle design prevents entering
dispersion from disturbing inside settled liquid,
At larger flow rates, the dispersion-band thickness
increases and unsettled dispersion issues from
the outlet, must be avoided.
Design methods are empirical and arbitrary. Three
approaches to the design:
(a) Provision of sufficient residence time based on
lab observation of settling
(b) Estimation of the rate of flow to produce
suitable dispersion-band thickness
(c) Calculation of the time to settle individual drops
through a clear liquid and below the dispersion
band.
In absence of any experimental data, an empirical
equation below is used for first hand settler
calculation:
TS = 8.4 (qC + qD)0.5 ----- (10.72)
Which is developed on a typical settling rate of
dispersed phase and L/D ratio of settler is 4.
Mixer-Settler cascades: Fig. 10.41 shows the counter current mixer-settler extraction cascade.
 Many such designs are possible (Refer Fig. 10.42) to reduce inter-stage piping and related
costs
 The mixing vessels are immersed in a circular settling tanks, heavy liquid flows by gravity,
light liquid by air lift and recycling of settled light liquid to the mixer is accomplished by
overflow.
Mixer-Settler cascades: Fig. 10.43 shows the Box Extractors designed to permit dispensing
with immediate piping.
The mixers and settlers are rectangular in cross section and are arranged in alternate positions
for adjacent stages.
Sieve Tray (Perforated Plate) Towers (Fig. 10.44):
These multistage, countercurrent towers are very effective, both
with respect to liquid handling capacity and extraction
efficiency, particularly for systems of low interfacial tension
which do not require mechanical agitation for good
dispersion.
Their mass transfer effectiveness results because
(1) Axial mixing of the continuous phase is confined to the
region between trays and does not spread throughout the
tower fro stage to stage and
(2) The dispersed-phase droplets coalesce and are formed again
at each tray, destroying the tendency to establish
concentration gradients within the drops which persist for
the entire tower height.
The arrangements of the tower is similar to the tray tower as
discussed earlier in Chapter-6, except the weirs are not
provided.
The figures is a self explanatory for equipment working
discussion.
Sieve Tray (Perforated Plate) Towers :
Stage efficiency calculation is shown graphically below having the same procedure as
discussed earlier using material balance and Murphree stage efficiency.
Differential (Continuous Contact) Extractors:
In countercurrent flow, the flow is produced due to difference in densities of the liquids and /
or due to the force of gravity, wherein the extractor is a vertical tower where the light
liquid is entering from the bottom and heavy liquid from the top.
Alternatively, a larger centrifugal force can be generated by rotating the extractor rapidly, in
which case the counter flow is radial with respect to the axis of revolution.
Spray Towers:
 The simplest of the differential-contact devices.
 It consists of am empty shell with provisions of introducing and removing liquids at
extreme ends.
 Due to empty space in tower, axial mixing is dominating.
 Horizontal baffles are used to reduce axial mixing.
 Nor much recommended for extraction.
Packed Towers:
 Random packing filled in tower serves to reduce axial mixing.
 Fig. 10.51 is for light liquid dispersed.
 The most of the void space in the packing is filled with continuous heavy liquid, which
flows downward.
 Rest of the void space occupied by droplets of the light liquid, mostly at the lower
distributor.
 Such light liquid droplets rise through the heavy liquid and coalesce (combined) at the top
into the bulk layer, forming an interface.
Packed Towers (contd..):
 To maintain the interface in this position, the pressure of liquid in the
tower at the bottom must be balanced by a corresponding pressure in
the bottom outlet pipe, as set by the control valve.
 If the pressure drop through the valve is reduced, the weight of the
contents of the tower adjusts to a lower value, the light liquid becomes
continuous, the heavy liquid dispersed, and the interface falls to below
the light liquid distributor.
 The interface positions are best regulated by a liquid level control
instrument activating the bottom outlet valve.
 The valve just above the interface is for periodic removal of scum and
dust particles which accumulates at the interface.
 Choice of packing and arrangement of dispersed phase distributor is
important.
 To avoid the channeling problem (If the dispersed phase is in form of
flow in place of droplets) and low interfacial area problem due to
channeling, the packing material should be wetted by the continuous
phase.
 The packing should be sufficiently small, not greater than 1/8 th of the
tower diameter.
Fig. 10.51 Packed extraction
tower, light liquid dispersed.
Packed Towers (contd..):
 Axial mixing is less severe than in spray towers.
 But mass transfer rates are poor.
 For low interfacial tension systems, sieve-tray towers should be used.
 For high interfacial tension systems, mechanically agitated extractors
should be used.
Mechanically Agitated (Counter Current Extractors):
 In liquid extractors, where density differences are likely to be 1/10 th
as large or less, good dispersion of systems of high interfacial
tension is impossible in such towers, and mass transfer rates are
very poor.
 For such systems, dispersion is best brought about by mechanical
agitation of the liquids, whereupon good mass transfer rates are
developed.
 Mixco Lightnin CMContactor (Oldshue-Rushton Extractor) uses flat
blade disk turbine impellers to disperse and mix the liquids and
horizontal compartmenting plates to reduce axial mixing.
Fig. 10.52 Mixico Lightnin

CMContactor (Mixing
Equipment Co.)
Rotating-Disk Contactor (RDC):
 Somewhat similar to earlier device, except the vertical baffles are
omitted and agitation results from rotating disks, which usually turn at
much higher speeds than turbine-type impellers.
Scheibel Extractor:
Turbine type impellers surrounded by
the doughnut type baffles which are
supported by vertical tie rods.
SELF STUDY:
1. Karr Reciprocating –Plate
Extractor
2. Trebyl Extractor
3. Graesser Extractor
4. Pulsed Columns
5. Centrifugal Extractors
Fig. 10.53 Rotating-Disk

Contactor (RDC) (General
American Transportation Corp.)
LEACHING
Leaching:
1. Leaching is the preferential solution of one or more constituents of a solid mixture by
contact with a liquid solvent.
2. It is the percolation of the liquid through a fixed bed of the solid.
3. Leaching of alkali from wood ashes is known as Lixiviation.
4. It is also termed as Solid – liquid extraction as separation using mass transfer operation or
mechanical methods is involved.
5. When the solvent is used at its boiling temperature, it is termed as Decoction.
6. When the soluble material is largely on the surface of an insoluble solid and is merely
washed off by the solvent, the operation is sometimes called Elutriation or Elution.
Applications of leaching:
7. In metallurgical industries to separate minerals from mixtures of solids. e.g. copper is
separated from its ore by leaching with H2SO4, gold is separated using sodium cyanide
solution, etc.
8. Many naturally occurring organic products are separated from their original structure by
leaching. e.g. sugar is leached from sugar beets with hot water.
9. Many pharmaceutical products are similarly recovered from plant roots and leaves.
10. Preparation of Tea and Coffee.
11. Washing off of the chemical precipitates.
LEACHING
Preparation of the solids: The success of a leaching and the technique to be used will very
frequently depend upon any prior treatment which may be given the solid.
1. In most of the metallurgical materials, small particles of the soluble material are
completely surrounded by a matrix of insoluble matter. The solvent must then diffuse into
the mass and the resulting solution must diffuse out, before separation can result.
2. Crushing and grinding can help a lot in above situation increasing the surface area.
3. When the soluble substance is more or less uniformly distributed throughout the solid or
even in solid solution, the leaching action may provide channels for the passage of fresh
solvent and fine grinding is not needed.
4. Vegetable and animal bodies are cellular in structure and the natural products to be
leached from them are found inside the cells. Osmotic passage of the solute through cell
walls is not a practical solution. Hence, they are cut into thin, wedge shaped slices called
cossettes before leaching in order to reduce the time required for solvent water to reach
the individual plant cells.
5. Sometimes, in pharmaceutical industry, the plant is dried and that way the cell walls are
ruptured and release the solute for direct action by the solvent.
6. Cells less than 5 mm size are largely ruptured by the flaking process and the oils are then
readily contacted by the solvent.
7. When the solute is adsorbed upon the surface of solid particles or merely dissolved in
adhering solution, no grinding or crushing is necessary and the particles can be washed
directly.
LEACHING
Temperature of leaching:
1. Higher the temperature, higher the solubility of solute in the solvent, higher the ultimate
concentration of leach liquor.
2. At high temperature, the viscosity of liquid is low and the diffusivities are higher leading
towards higher rate of leaching.
3. However, in some products, like sugar beet, too high temperature may lead to leaching of
excessive amounts of undesirable solutes or chemical deterioration of solids.
Methods of operation and equipment:

4. Leaching operations are carried out under batch and semi-batch (unsteady state) as well as
completely continuous (steady-state) conditions.
5. In each category, both stagewise and continuous contact types of equipment are to be
found.
6. Two major handling techniques are: (i) spraying or trickling the liquid over the solid and
(ii) immersing the solid completely in the liquid.
7. The choice of equipment to be used in any case depends upon the physical form of the
solids and the difficulties and cost of handling them.
LEACHING
Unsteady State Operations
Followings are the methods/techniques applied,
1. Solids and liquids are contacted in purely batchwise fashion.
2. Batch of the solid is contacted with a continually flowing stream of the liquid (semi batch
method).
3. Coarse solids are usually treated in fixed beds by percolation methods.
4. Finely divided solids, which can be kept in suspension more readily, can be dispersed
throughout the liquid with the help of some sort of agitator.
In-Place (In situ) leaching:

5. This operation is also known as solution mining.
6. It refers to the percolation leaching of minerals in place at the mine, by circulation of the
solvent over and through the ore body.
7. It is used regularly in the removal of salt from deposits below the earth’s surface by
solution of the salt in water which is pumped down to the deposit.
8. It has been applied to the leaching of low-grade copper ores containing as little as 0.2%
copper and to ores as deep as 335 m below the surface.
9. In the solution mining of uranium, the ore must be oxidized in place in order to solubilize it
in carbonate solutions.
LEACHING
Heap leaching:
1. Low-grade ores whose mineral values do not deserve the expense of crushing or grinding
can be leached in the form of run-of-mine lumps built into huge piles upon impermeable
ground.
2. The leach liquor is pumped over the ore and collected as it drains from the heap.
3. Copper has been leached from pyritic ores in this manner in heaps containing as much as
2.2 x 107 tons of ore, using over 20,000 m3 (5 x 106 gal) of leach liquor per day.
4. It may require up to 7 or more years to reduce the copper content of such heaps from 2 to
0.3 %.
Percolation Tanks:
5. Solids of intermediate size can conveniently be leached by percolation methods in open
tanks.
6. The construction of these tanks varied greatly, depending upon the nature of the solid and
liquid to be handled and the size of the operation, but they are relatively inexpensive.
7. Small tanks are made of wood, if it is not chemically attacked by the leach liquid.
8. The solid particles to be leached rest upon a false bottom, which in the simplest
construction consists of a grating of wooden strips arranged parallel to each other and
sufficiently close to support the liquid.
9. These again rest upon similar strips arranged at right angles, 150 mm or more apart, so
that the leach liquor flows to a collection pipe leading from the bottom of the tank.
LEACHING
Percolation Tanks:
6. For supporting fine particles, the wood grating may be further covered by a coconut
matting and a tightly stretched canvas filter cloth, held in place by tying a rope into groove
around the periphery of the false bottom.
7. Small tanks may also be made entirely of metal, with perforated false bottoms upon which
a filter cloth is placed, as I the leaching of pharmaceutical products from plants.
8. Very large tanks made up of reinforced concrete and lined with lead or bituminous mastic.
9. Small tanks may be provided with side doors near the bottom for washing away the
leached solid, while very large tanks are usually emptied by excavating from the top.
10. Tanks should be filled with uniform particle size solids, so that the percentage of voids will
be largest and minimum pressure drop required for the low of leaching liquid.
11. After the tank is filled with solid, a batch of solvent sufficient to immerse the solid
completely may be pumped into the tank and the entire mass allowed to steep or soak for
a prescribed period of time.
12. During this period the batch of liquid may or may not be circulated over the solid by
pumping.
13. The liquid is then drained from the solid by withdrawing it through the false bottom of the
tank.
14. This entire operation represents a single stage.
15. Repetition of this process will dissolve all solute.
16. The only solute then retained is that dissolved in the solution wetting the drained solid.
LEACHING
Percolation Tanks:
17. This can be washed out by filling the tank with fresh solvent and repeating the operation as
many times as necessary.
18. An alternative method is continuously to admit liquid into the tank and continuously to
withdraw the resulting solution, with or without recirculation of a portion of the total flow.
19. Such an operation may be equivalent to many stages.
Countercurrent Multiple Contact; The Shank System:

 Leaching and washing of the leached solute from the percolation tanks by the cross current
methods result in weak solutions of the solute.
 The strongest solution will result if a counter current scheme is used wherein the final
withdrawn solution is taken from the contact with the freshest solid and the fresh solvent
is added to solid from the which the most solute has already been leached or washed out.
 In order to avoid moving the solids physically from tank to tank in such a process the
arrangement (fig. 13.2) shown schematically for a system of six tanks is used.
 This is known as Shanks system, operated in the following manner:
1. Assume that the system is in operation for some time (fig. 13.2(a)).
2. Tank 6 is empty, tanks 1 to 5 are filled with solid, tank 5 most recently and tank 1 for the
longest time.
3. Tanks 1 to 5 are also filled with leach liquid, and the most concentrated is in tank 5 since it
is in contact with the freshest solid. Fresh solvent has just been added to tank 1.
LEACHING
Countercurrent Multiple Contact; The Shank System (contd..):
4. Withdraw the concentrated solution from tank 5, transfer the liquid from tank 4 to tank 5,
from 3 to 4, from 2 to 3. and from 1 to 2.
5. Add fresh solid to tank 6.
6. (Fig. 13.2(b)), Discard the spent solid from tank 1.
7. Transfer the liquid from tank 5 to tank 6, from 4 to 5, from 3 to 4 and from 2 to 3.
8. Add fresh solvent to tank 2.
9. The circumstances are now the same as they were at the start in Fig. 13.2(a), except that
the tank numbers are each advanced by one.
10. Continue the operation in the same manner as before.
11. The tanks need not be operated in circle
but better to place in row. It is called
extraction battery. That enable
addition/deletion of the tanks in the
system easily.
12. The tanks may be placed at progressively
decreasing level to avoid the additional
cost of pumping.
13. Main application is in metallurgical
industries, tannins recovery from bark
and woods, etc.
LEACHING
Percolation in Closed Vessels (Diffusers):
 When the pressure drop for flow of liquid is too high for gravity flow, closed vessels must
be used and the liquid is pumped through the bed of solid. Such vessels are sometimes
called diffuser.
 Closed vessels are also useful to prevent evaporation losses when
the solvent is very volatile or when the temperatures above the
normal boiling point of the solvent are desired.
 Designs may vary considerably, depending upon the application.
 Design like Fig. 13.3 can be used in case of leaching sugar from
sugar-beet slices, or cossettes.
 They are arranged in a battery containing up to 16 vessels and the
beets are leached with hot water in fashion of Shanks system.
 Heaters are placed between the diffusers to maintain a solution
temperature of 70°C to 78°C.
 In this manner 95 to 98% of the sugar, in beets containing initially
about 18%, can be leached to form a solution of 12%
concentration.
 Countercurrent continuous equipment is also used in the sugar
beet industry.
Fig. 13.3 Sugar beet diffuser

LEACHING
Filter Press Leaching:
 Finely divided solids, too fine for treatment by percolation in relatively deep percolation
tanks, can be filtered and leached in the filter press by pumping the solvent through the
press cake. This is common practice in washing mother liquor from precipitates which have
been filtered.
Agitated Vessels:
 Channeling of solvent can be avoided by stirring the
liquid and solid in leaching vessels.
 For coarse solids, agitated vessels are used (Fig. 13.4(a)
vertical and Fig. 13.4 (b) horizontal).
 Closed cylindrical vessels are arranged vertically and re
fitted with power driven paddles or stirrers on vertical
shaft as well as false bottoms for drainage of the leach
solution at the end of the operation.
 Fig. 13.4 (c), horizontal drum is the extraction vessel and
solid and liquid are tumbled about
inside by rotation of the drum on
rollers.
 Used for leaching of vegetable oil
from seeds.
Fig. 13.4 Agitated batch leaching vessels
LEACHING
Agitated Vessels (Contd..):
 Pachuca tank is used to leach finely divided solids
suspended in leaching solvents.
 Highly used in metallurgical industry.
 These tanks are constructed of wood, metal or
concrete and may be lined with inert metal depending
upon the nature of the leaching liquid.
 Agitation is accomplished by an air lift.
 The standard mechanical agitator with turbine
impeller used to keep finely divided solids suspended
in liquid.
 After completion of leaching, agitation stopped and
solid is allowed to settle, and the clear supernatant
liquid is decanted by siphoning over the top of the
tank or using withdrawal discharge pipes.
 In case of sludge formation, agitation and settling with
several batches of wash solvent is necessary to
recover last traces of solute.
 The solids may be filtered and wash in the filter.
Fig. 13.5 Pachuca Tank

LEACHING
Batch Settling:
 When dilute solution is allowed to settle in a measuring cylinder, fine particles/
suspended solids will start getting settled under no interruption condition and after
some time a clear demarcation is visible between clear liquid layer and settled solid layer.
 In case of concentrated liquid, the condition is little different and hindered settling is
observed.
Zone A: Clear liquid
Zone B: Solid concentration is uniform at w0.
Zone C: Transition zone between B and D, which may not always be
clearly defined.
Zone D: Compression Zone, wherein the particles settled by resting
upon each other and liquid will squeezed out of this zone due to
such compression effect. Hence, high solid concentration.
If the settling continues with high amount of solids, the zone B may
disappear slowly.
LEACHING
Batch Settling:
 The rate of settling is followed by plotting the height of the line of demarcation between
zones A and B against time (Fig. 13.7).
 The broken curve represents the position of the upper level of Zone D.
 The top of zone B settles at constant rate (curve of Z vs. time straight) until the zone B
disappears and all the solids are in the compression zone.
 The rate of settling of the compression zone to its ultimate height Zꚙ
is then relatively slow and is not constant.
 The appearance of curves is also depend upon the type of slurry,
initial height, concentration of slurry, extent of flocculation and
stirring, if any given during settling.
 Flocculation: If the finely divided solid particles are all similarly
electrically charged, they repel each other and remain dispersed. If
the charge is neutralized by addition of an electrolyte (flocculating
agent) to the mixture, the particles may form aggregates, or flocs.
Since the flocs are of larger size, they settle more rapidly. Slurries and
suspensions encountered in chemical operations are usually
flocculated.
Basically, coagulation is a process of addition of coagulant to destabilize a
stabilized charged particle. Flocculation is a mixing technique that promotes
agglomeration and assists in the settling of particles.
The product of the mixing intensity and mixing time is used to
describe flocculation processes.
LEACHING
Batch Settling (contd..):
Stirring:
 Under very slow stirring, eddy currents are not formed within the liquid, changes the
settling characteristics largely.
 As the floc structure changes, the solid concentration in zone B is not uniform at the
initial value and zone D may not be clearly defined.
 The ultimate height of the settled slurry may be only a fraction of
that obtained without stirring.
 The ultimate concentration of solids in the settled mass is greater.
 The zones of constant and falling rate settling are still observed, but
at different rates.
LEACHING
Batch Settling (contd..):
Concentration:
 The rate of settling is difficult with increase in solid concentration as effective density and
viscosity of the medium also increases through which the particles settled.
 Fig. 13.8 shows the effect of increasing concentration of the same substance in medium
are settled in columns of the same height.
 This study is successful only for slurry which are not at one or more concentrations and
incompressible.
Height: Fig. 13.9 shows the settling curves for he same slurry at different initial heights.
The initial constant settling rate is independent of
height and minimum value of Z0 is exceeded (Zꚙ/Z0
will be constant).
 The constant settling lines terminate on
a line OA starting from the origin.
 Any line like OB will be cut so that line
OC/line OB = Z0/Z0’.
 It means the time for a slurry to settle
to a fixed fractional height Z/Z0 is
proportional to the initial height Z0.
LEACHING
Percolation vs. Agitation:
 If a solid in the form of large lumps is to be leached, a decision must frequently be made
whether to crush it to coarse lumps and leach by percolation or whether to grind it fine
and leach by agitation and settling. No general answer is available but following
considerations are important:
1. Fine grinding is more costly but provides more rapid and possibly more thorough leaching.
2. It has the disadvantage that the weight of liquid associated with settled solid may be as
great as the weight of the solid, or more so that considerable amount of solvent is used in
washing the leached solute and the resulting solution is dilute.
3. Coarsely ground particles leach more slowly and possibly less thoroughly but on draining
may retain relatively little solution, require less washing and thus provide a more
concentrated final solution.
4. For more fibrous solids, leaching is generally more efficient in a thoroughly agitated vessel
than by percolation, probably because the large amount of static liquid holdup makes
important amount of solute unavailable.
LEACHING
Steady State Continuous Operations
It can be divided into two major categories:
1. Stage-wise operations: It is sometimes assembled in multiple units to produce multistage
effects
2. Continuous contact operations: It may provide the equivalent of many stages in a single
device.
Leaching during Grinding:

 Many solids require grinding in order to make the soluble portions accessible to the
leaching solvents.
 Some of the leaching may be accomplished using wet grinding.
 50-75% of the soluble gold may be dissolved by grinding the ore in the presence of cyanide
solution.
Agitated Vessels:
 Finely ground solids can be continuously leached in agitation tanks or vessels.
 Continuous flow of liquid and solid into and out of the tank must be arranged so that no
accumulation in the tank.
 Such arrangements are single-stage in their action and liquid and solid tending to come to
equilibrium within the vessel.
 Mechanically agitated vessels are most useful.
 Pachuca tanks are used in metallurgical industry.
LEACHING
Agitated Vessels (contd…):
Dorr Agitator: It is extensively used in metallurgical and chemical industry for continuous
leaching and washing of finely divided solids.
 It consists of a flat bottomed tank provided with a central tube
that acts as an air-lift and also serves as shaft and carries a set
of arms both at the top and the bottom.
 The upper arm in the form of launders. The launders are
having a number of perforations for distribution of suspension
they receive.
 The lower arms (arms attached to the centre tube and also
acting as a shaft)are provided with the scrapper blades set at
an angle so that they carry the settled solids towards the
centre of the tank bottom from where they are lifted by the air
lift through the central tube and discharged into the revolving
launders.
 The launders then distribute the suspension evenly over the
entire surface of the liquid in the tank . The lower arms are
usually hinged and provided with the arrangements for lifting
them from the bottom of the whenever the power
interruption is there, so that they may not be blocked in the
settled solids that would otherwise prevent them from starting
again.
LEACHING
Thickeners:
 Thickeners are mechanical devices designed especially
for continuously increasing the ratio of solid to liquid in
a dilute suspension of finely sized particles by settling
and decanting, producing a clear liquid and a thickened
sludge as two separate products.
 Thickeners may be used before any ordinary filter in
order to reduce filtering costs.
 Thickeners are also used to wash leached solids and
chemical precipitates free of adhering solution in a
continuous muti-stage countercurrent arrangement.
 A thin slurry of liquid and suspended solids fed from the
top of the tank.
 The settled solids from the liquid fills the tank and gently
directed towards discharge cone at the bottom using
plow blades, which are rotating slowly at about 3 to 4
RPM. (diameter varies from 1 to 180 m)
 Sludge is discharged from the bottom using diaphragm
pump and clear liquid overflows into launders about the
periphery of the tank
 It can handle granular as well as flocculent solids.
LEACHING
Thickeners (contd..):
 In order to reduce the ground-area requirement, several thickeners operating in parallel and
superimposed as in Fig. 13.12 may be used. Such a device delivers a single sludge product.
 The liquid content of the
sludge is greatly dependent
upon the nature of the solids
and liquid and upon the time
allowed for settling.
 In typical cases the liquid
content of the sludge might
be in the range of 15 – 75%
liquid.
 The less liquid retained, the
more efficient the leaching or
washing process being carried
on.
LEACHING
Continuous Countercurrent Decantation (CCD):
 Leaching equipment such as agitators or grinding mills may discharge their effluent into a
cascade of thickeners for continuous countercurrent washing of finely divided solids free of
adhering solute.
 The same type of cascade can also
be used to wash the solids formed
during chemical reactions , as in
manufacture of phosphoric acid,
by treatment of phosphate rock or
sulfuric acid.
 Solid and solution enter to
leaching agitator from second
thickener and concentrated
solution decanted from the
solids by the first thickener.
 The sludge is passed through the
cascade to be washed by the
solvent in countercurrent
fashion and washed
solids discharged at the right.
 Agitators may be replaced
by grinding mills, if needed.
LEACHING
Continuous Settling:
 The concentrations existing at various levels in continuous thickener under steady state
operation is different than batch settling.
 The four clear zones found in thickener are shown by solid curves in the fig. 13.14.
 The feed slurry is diluted as it entered from the feed well of the thickener and bulk of the
liquid passes upward to overflow into the launder about the thickener periphery.
 The solid concentration in the top zone is negligible if the overflow is clear.
 The solids and remainder of the feed liquid move downward through the lower three zones
and leave in the thickened underflow.
 The solids conc. In the settling zone is much lower than that in the feed, because of the
dilution, but rises rapidly in the compression zone immediately below.
 In the bottom zone, the action of the rake disturbs arched structure which may form by the
solids, the weight of the solids passes
out the liquid, and the conc. rises to the
value in underflow.
 If the feed rate to the thickener
increased, the conc. of the solids in the
settling zone rises and reaches a
maximum value not related to feed
conc. when the settling capacity of this
zone exceeded.
LEACHING
Continuous Settling:
 The excess solids which cannot settle, overflow with the liquid (broken curve in Fig. 13.14).
 The conc. of solids in underflow sludge for a given rate and concentration of feed can be
increased by reducing the rate of withdrawal of sludge.
 This increases the depth of compression zone and detention time of the solids within
thickener. (Care should be taken so that solids must not appear in overflow with increase in
height of compression zone).
 Let, Flux of solids during settling, Gs = cV, (determined from the slopes of the curve like in
Fig. 13.8) which is to be plotted against c.
 Where, V = Initial settling velocities for slurries of the solid
 c = Initial uniform concentration of slurry of the solid
 The tangent of smallest negative slope is drawn to the curve from point (Gs = 0, c = cU)
Where, cU = desired underflow conc. , to intersect the
ordinate at GSL (the limiting solid flux).
The minimum required thickener cross section for handling
W mass/time of solids is then, A = W/GSL --------------- (13.7)
Conc. cL is that at the point of compression and cS that in the
settling zone.
LEACHING
Hydro Cyclone (Hydroclones):
 Hydrocyclones used as liquid-solid separators in place of thickeners in countercurrent
washing of solids in a slurry.
Continuous Leaching of Coarse Solids:
 Machines used for mechanical separation are used for leaching.
 Except Classifiers, which are
mainly developed for
metallurgical industry, the
equipments were principally
developed for the special
solid handling problems
arising in the leaching of
sugar beets and of
vegetable seeds such as
cotton seed, soybeans, etc.
LEACHING
Continuous Leaching of Coarse Solids:
1. Classifiers:
 Coarse solids can be leached, or washed free of adhering solution or solute, in machinery
used for classification of particle size.
 The solids are introduced into a tank, made with a sloping bottom and partly filled with the
solvent.
 The rakes, which are given a reciprocating and circular lifting motion by the driving
mechanism, rake the solids upward along the bottom of the tank and out of the liquid.
 In the upper part of the tank the solids are discharged and discharged.
 The liquid overflows at the deep end of the tank.
 The solute concentration in
the liquid is reasonably
uniform throughout the tank
as a result of the agitation by
the rakes, so that the
apparatus produces a single-
stage action.
 Cascade of classifiers can also
be created for continuous
multi-stage countercurrent
action.
LEACHING
Leaching of Vegetable Seeds:
 Cottonseeds, soybeans, linseeds (flaxseeds), peanuts, rice bran, castor beans, and many
other similar products are leached or extracted with organic solvents for removing the
vegetable oils they contain.
 Preparation of seeds includes dehulling, precooking, adjustment of moisture content, and
rolling or flaking.
 Sometimes a portion of the oil is first removed mechanically by expelling or expression.
 Leaching solvents are generally petroleum naphtha, hexane, chlorinated hydrocarbons
(leaves too toxic residue for leached meal to be used for animal feed).
 The oil-solvent solution, which generally contains a small amount of finely divided,
suspended solids, is called miscella and the leached solids marc.
 The various leaching devices are usually called extractors in this industry.
 The Rotocel is a modification of the Shanks system wherein the leaching tanks are
continuously moved, permitting continuous introduction and discharge of solids.
LEACHING
Leaching of Vegetable Seeds:
 A circular rotor, containing 18 cells, each fitted with a hinged screen bottom for supporting
the solids, slowly revolves above a stationary compartmented tank.
 As the rotor revolves, each cell passes in turn under a special device for feeding the prepared
seeds and then under a series of sprays by which each is periodically wetted with solvent for
leaching.
 After nearly one revolution, the leached contents each cell are automatically dumped into
one of the lower stationary compartments, from which they are continuously conveyed
away.
 The solvent from each spray percolates
downward through the solid and the
supporting screen into the appropriate
compartment of the lower tank, from
which it is continuously pumped to the
next spray.
 The leaching is countercurrent and the
strongest solution is taken from the
freshest seeds.
 The entire machine is enclosed in a vapour
tight housing to prevent the loss of solvent
vapours.
LEACHING
LEACHING
French Stationary-Basket Extractor:
 It is a variant of Rotocell. The flakes are contained in stationary, compartmented beds filled
by a rotating spout to feed the solids and are leached with solvent and miscella
countercurrently.
Kennedy Extractor: (Fig. 13.19)
 Used for leaching tannins from tanbark, oilseed and other chemical leaching operations.
 The solids are leached in a series of tubs and are pushed from one to the next in the cascade
by paddles, while the solvent flows in countercurrent.
 Perforations in the paddles permit drainage of the solids between stages, and the solids are
scraped from each paddle as shown.
 As many tubs may be placed in a cascade as are required.
LEACHING
Bollman Extractor (Fig. 13.20) :
 It is a basket type machine.
 Solids are conveyed in perforated baskets attached
to a chain conveyor, down on the right and up on
the left in figure.
 As they move downward, they are leached in
parallel flow by a dilute solvent-oil solution (half
miscella) pumped from the bottom of the vessel
and sprayed over the basket, collects at the
bottom as the final strong solution of the oil (full
miscella), and is removed.
 On the upward side, the solids are leached
countercurrently by a spray of fresh solvent to
provide half miscella.
 A short drainage time is provided before the
baskets are dumped at the top.
 There are many variants of this device, e.g. the
horizontal arrangement of Fig. 13.21
LEACHING
LEACHING
LEACHING
LEACHING
Vegetable oil production process showing the use of Bollman extractor
LEACHING
Horizontal Filter(Fig. 13.22) :
 The filter in the form of circular wheel, is divided into a number of sectors and revolves in
the horizontal plane.
 Prepared seeds are slurried with solvent which has already been used for leaching, and the
slurry is sent to the filter.
 The first filtrate is passed again through the filter cake to remove finely divided solids
(polishing) before being discharged as miscella.
 The principle is much the same as Rotocel.
 Horizontal moving screen-type belts are also used for conveying the solids during leaching.
 The recovery of solvent from both the miscella and the leached seeds or beans is important.
 The filtered miscella is passed to an evaporator

for removal of solvent, sometimes followed by
final stripping in a tray column, to produce
solvent-free oil.
 The wet seeds are steamed to remove residual
solvent and air-cooled.
 Vented gas from condensers may be sent to an
absorber to be scrubbed with petroleum white
oil, and the resulting solvent-white-oil solution
stripped to recover any solvent.
LEACHING
Methods of Calculations
The methods of calculation are very similar to those used for liquid extraction.
Calculations needed for the followings:
1. To calculate the amount of soluble substance leached from a solid
2. Knowing the initial solute content of the solid
3. The number and amount of washings with leaching solvent
4. The concentration of solute in the leaching solvent, if any
5. The method, batch or continuous countercurrent.
Alternatively, it may be necessary to compute the number of washings, or the number of stages,
required to reduce the solute content of the solid to some specified value., knowing the amount
and solute concentration of the leaching solvent.
Stage Efficiency :
 Consider a simple batch of where the solid is leached with excess solvent to dissolve all the
soluble solids and no preferential adsorption of solvent or solute by the solid.
 If enough time of contact between solid and solvent is permitted, all the solute will be
dissolved in a solution of solute in the solvent.
 The insoluble phases are separated physically by settling, filtration, or drainage and the
entire operation constitutes one stage.
 If the mechanical separation of liquid and solid were perfect, there would be no solute
associated with the solids leaving the operation and complete separation of solute and
insoluble solid would be completed in one stage.
 This would be an equilibrium stage, of 100% efficiency.
LEACHING
Stage Efficiency (contd..) :
 In practice, stage efficiencies are much less than this:
(1) The solute may be incompletely dissolved due to insufficient contact time
(2) Most certainly it will be impractical to make liquid – solid mechanical separation perfect, and
the solids leaving the stage will always retain some liquid and its associated dissolved solute.
(3) When the solute is adsorbed by the solid, even though equilibrium between the liquid and
solid phases is obtained, imperfect settling or draining will result in lowered stage efficiency.
Practical Equilibrium: In practice, it is easy to make calculations graphically:
 Consider three component system: A= Pure solvent, B=insoluble carrier solid C= soluble
solute.
 Triangular coordinates (Ternary diagram) can be used. But rectangular coordinates are
preferred due to frequent crowding of construction in one corner of the diagram in Ternary
diagram.
 N = The conc. of insoluble solid B (it may be wet with liquid solution or not) in any mixture or
slurry. [mass B/mass (A + C)] {for pure solvent A, N = 0, x = 0}
 Solute C compositions will be expressed as weight fractions on a B-free basis
 x = wt. fraction C in the effluent solution from a stage (B-free basis)
 y = wt. fraction C in the solid or slurry (B-free basis) (it includes all solute C associated with
the mixture, including that dissolved in adhering solution as well as undissolved or adsorbed
solute)
 If the solid is dry, like before leaching begin, N = Wt. of (insoluble/soluble substance) and y =
1.0
LEACHING
Practical Equilibrium:
 Consider the case of a mixture of insoluble solid from which all the solute has been leached,
suspended in a solution of the solute in a solvent, as represented by point M1 on the figure.
 x = concentration of clear solution, NM1 = Insoluble solid / solution ratio.
 R1 = Clear liquid which can be drawn off from a batch settling tank after settling of mixture.
 Remaining sludge will consists of the insoluble solid suspended in a small amount of solution
 The composition of the solution in the sludge will be the same as that of the clear liquid
withdrawn, so that y* = x.
 NE1 = Conc. of solid B in sludge (depend upon the time ϴ1 allowed for settling) so that point
E1 represents the slurry.
 E1R1 = tie line joining the points
 If therepresenting two effluent
above conditions streams,
maintained clear situation,
in actual liquid andpoint
slurry.E &
1
R1 can be taken as an equilibrium condition for that leaching.
 If the less time allowed for settling, say ϴ1’ , the sludge will be
less concentrated in insoluble solids and may be represented by
point E1’
 N = Maximum value of the sludge corresponding to its ultimate
settled height with sufficient time for settling.
 Since the concentration of insoluble solid in a sludge settled for
a fixed time depends upon the initial concentration in the slurry,
Fig. 13.23 Concentrations in a mixture M2 settled for time ϴ1 result in a sludge corresponding
leaching and washing
LEACHING
Practical Equilibrium:
 If solid does not settle enough to give clear solution, if too much solution withdrawn from
the settled sludge so that a small amount of solid is carried with it, or if solid B dissolves to a
small extent in the solution, the withdrawn solution will be represented by point like R2,
somewhat above the lower axis of the graph.
 Similar interpretations can be made for compositions obtained when wet solids are filtered
or drained of solution rather than settled, or when continuously thickened.
 The settling or thickening characteristics of a slurry depend upon the viscosity and relative
density of the liquid in which the solid is suspended.
 Since it is depending upon the solution compositions, it is possible to obtain experimental
data showing the variation of compositions of thickened solids with composition of solution
and to plot them on the diagram as practical equilibrium
conditions.
Fig. 13.23 Concentrations in

leaching and washing
LEACHING
Types of Equilibrium Curves:
(A) Solute C is infinitely soluble in solvent A:
 x and y may have values over the entire range from 0 to 1.0
 e.g. Soybean oil (C) – Soybean meal (B) – Hexane (A), where (C)
and (A) are infinitely soluble.
 Curve DFE represents the separated solid under conditions
actually to be expected in practice.
 Curve GHJ, the composition of withdrawn solution, lies above
the N = 0 axis, and in this case, therefore, either solid B is partly
soluble in the solvent or an incompletely settled liquid has been
withdrawn.
 The tie lines such as line FH are not vertical, and this will result
(i) If insufficient time of contact with leaching solvent to dissolve
all solute is permitted
(ii) If preferential adsorption of the solute occurs, or
(iii) If the solute is soluble in the solid B and distributes unequally
between liquid and solid phases at equilibrium.
The data may be projected upon a plot of x vs. y as in the manner
of liquid adsorption.
Fig. 13.24 (a)

LEACHING
(B) No adsorption of solute occurs:
 Since, no adsorption of solute occurs, the withdrawn solution
and solution associated with the solid have the same
composition and tie lines are vertical.
 As a result the xy curve is identical with the 45° line and
distribution coefficient m, defined as y*/x = 1.
 Line KL is horizontal, indicating that the solids are settled or
drained to the same extent at all solute concentrations.
 It is possible to regulate operation of continuous thickeners so
that this will occur and the conditions are known as constant
underflow.
 The solution in this case contains no substance B, either
dissolved or suspended.
Fig. 13.24 (b)

LEACHING
(C) Solute C has a limited solubility xS in solvent A:
 Since, Solute C has a limited solubility xS in solvent A, no clear
solution stronger than xS can be obtained, so that the tie lines
joining slurry and saturated solution must converge, as shown.
 In this case any mixture M to the right of line PS will settle to
give a clear saturated solution S and a slurry U whose
composition depends on the position of M.
 Point T represents the composition of the pure solid solute after
drainage or settling of saturated solution.
 Since tie lines to the left of PS are shown vertical, no adsorption
occurs and overflow liquids are clear.
Fig. 13.24 (c)

LEACHING
Single Stage Leaching:
 The circle represents the entire mixing, leaching or washing and separation stage.
 Weights of the various streams are expressed as mass for a batch operation or mass/ time
[or mass/(area)(time)] for continuous flow.
 Since for most purposes the solid B is insoluble in the solvent and a clear liquid leach
solution is obtained, the B discharged in the leached solids will be taken as the same as that
in the solids to be leached.
 By definition of N, B = NFF = E1N1 -------- (13.8)
 A solute (C) balance gives, FyF + R0x0 = E1y1 + R1x1 -------------- (13.9)
 and a solvent (A) balance gives, F(1 – yF) + R0(1 – x0) = E1(1-y1) + R1(1 – x1) --- (13.10)
 a “solution” (solute + solvent) balance gives F + R0 = E1 + R1 = M1 -------- (13.11)
 Mixing the solids to be leached and leaching solvent produces a mixture B-free mass M1 such
that,
 ---- (13.12)

 ----- (13.13)
 These relations can be shown on the

coordinate
Fig. 13.25 system
Single-stage of or
leaching Fig. 13.26)
washing
LEACHING
Single Stage Leaching:
 Point F represents the solids to be leached and R0 the leaching solvent.
 Point M1, representing the overall mixture, must fall on the straight line joining R0 and F, (just
as did in Liquid Extraction).
 Points E1 and R1, representing the effluent streams, are located at opposite ends of the tie
line through M1, and their compositions can be read from the diagram.
 Weight of E1 and R1 can be calculated from the eq. (13.8) and (13.11), respectively.
 Modification to allow for the presence of B in the liquid withdrawn, necessitating an
equilibrium diagram of the type shown in Fig. 13.24(a), is readily made by analogy with the
corresponding problem in liquidextraction.
In case of insufficient separation due to less contact and
settling time, the effluent streams can be represented by
points E1’ and R1’ and a stage efficiency (yF – y1’)/(yF – y1)
can be described to this cause.
 If the equilibrium curve was obtained under conditions of
contact time corresponding to the actual leaching, the tie
line E1R1 will give the effluent composition directly.
Multi Stage Crosscurrent Leaching:
 Fresh solvent comes in contact with the leached solids
and additional solute can be dissolved or washed away
Fig. 13.26 Single-stage leaching or washing
from the insoluble material.

LEACHING
Multi Stage Countercurrent Leaching (Continuous):
 It is assumed that B is insoluble and is not lost in the clear solution.
 A solvent balance for the entire plant is F + RN +1 = R1 + EN = M ---- (13.14)
P P
 And a “solution” (A + C) balance, FyF + RN +1xN +1 = R1x1 + EN yN = MyM -----(13.15)

P P P P
 M represents the hypothetical B-free mixture obtained by mixing solids to be leached and
leaching solvent. (Refer Fig. 13.29 for operating diagram of the plant).
 The coordinates of point M are,
 -- (13.16)
 -- (13.17)
LEACHING
 The EN and R1, representing the effluents from the
P
cascade, must lie on a line passing through M, and EN P
will be on the practical equilibrium curve.

 Eq. (13.14) can be rearranged to read,
F - R1 = ENP - RN +1 = ΔR ---- (13.18)
P
 Similarly a solution balance about any number of stages,

such as first three, written as,
F - R1 = E3 – R4 = ΔR ---- (13.19)
 ΔR represents the constant difference in flow E – R
(usually a negative quantity) between each stage.
 In Fig. 13.29 it can be represented by the intersection of
lines FR1 and EN RN +1 extended.
P P
 Effluents from each stage are joined by practical tie line.

 E1 is found at the end of the tie line through R1.
 A line from E1 to ΔR provides R2, and so forth.
 Alternatively, the stage constructions may be made on
the x,y coordinates after first locating the operating line.
 This can be done by drawing random lines from point ΔR
and projecting their intersections with the equilibrium
diagram to the lower curve in usual manner.
 The usual staircase construction then establishes the
End of
Mass Transfer Operations-I
Dr. A. P. Vyas
EVEN-2020
Thank you for your attention
Do well
All the best

Mto-I Even 2020

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Mass Transfer Operations-I

(B) Gas-Liquid (Contd…):

(iii) Desorption or Stripping: Opposite to Gas Absorption

The difference between (ii) and (iii) is purely in the direction of

(B) Gas-Liquid (Contd…):

(v) Dehumidification: Opposite to Humidification

(ii) Drying: If a solid moistened with a volatile liquid is exposed to relatively

(iii) Adsorption: If the diffusion takes place in opposite direction to drying,

(ii) Permeation: Gas transmitted through the non-porous membrane

(5) Direct and Indirect operations:

• Other driving forces (besides concentration differences)

There are two types of fluxes:

Example: A fisherman is most interested in the rate at which a fish swims

If the solution density is constant, it becomes:

Where, p ̅A = Partial pressure of component A

1. Steady state diffusion of A through non-diffusing B

Since, pt  p A2  pB 2 , pt  p A1  pB1 , pB 2  pB1  p A1  p A2

This is shown graphically in figure.

r = 1.18 ν1/3 and ε/k = 1.21 Tb

Hence, the above equation may be written as, NA

Where, ρ and M are the solution density and

The problem is to obtain the mass-transfer

The problem is solved by simultaneous solution of

When a fluid flows turbulently past a solid surface,

Postulation: The concentration will follow the broken

The concentration gradient in the film is the

Higbie’s theory describes the contact of two fluids.

Assumption: The chance of a surface element’s being replaced by another is quite

If s is the fractional rate of replacement of elements, Danckwerts found,

e.g. Ammonia and air in water.

Many of mass transfer operations are carried out in

Let us consider the system: Ammonia (Substance A) and

Gas mixture changes its composition from high to low

If the MTCs are known, interfacial concentrations

Where, m” = slope of the chord MD.

Similarly, if m” is very large (i.e. equilibrium-

Where, f is the equilibrium distribution function.

Eq. 5.20 can be re-written as.

The other terms can be similarly described and eq. 5.30

The other terms can be similarly described and we may

Driving force line

Rs (X1 – X)= Es (Y1 – Y) --------- (5.37)

Here, S = mEs/Rs = Stripping Factor

Fractional Overall Stage Efficiency of a cascade: It is defined as the number of equilibrium

There may be different flow rate of Phase E For

Cross flow is used sometimes in adsorption,

Each stage is identical in its action to the

By substitution and rearrangement, eq. 5.41, becomes

The rate of mass transfer is directly depend upon

Gas Dispersed Equipment:

(2) Mechanically Agitated Vessels:

(a) Marine type propellers:

Vortex formation can be avoided by the following

Factors affecting the operation:

Signifies that gas conc. are used.

of one tray of multi-tray tower

Entrainment: A further correction is required for the damage done by entrainment.

e.g. Absorption of SO2

As a rough guide, packing

Wood grids, or hurdles, are

Knitted or woven wire screen

• Here mass transfer takes place from gas to the liquid.

There are four significant characteristics of an ideal solution: