CHAPTER SEVEN

DIFFUSION

In a mixture consisting of two or more components, if the concentrations of the

components vary from point to point, then there is a natural tendency for each component to
migrate/move from regions of high concentration to those of low concentration. The process
of transfer of mass as a result of the concentration difference of a component in a mixture or
two phases in contact is called mass transfer.
The operations carried out for separating the components of a mixture, involving the
transfer of material from one homogeneous phase to another, utilising the difference in
vapour pressure, solubility or diffusivity and in which the driving force for transfer is a
concentration difference are called as mass transfer operations.
In case of evaporation of water from a pool of water into a stream of air flowing over the
water surface, molecules of water vapour diffuse through those of the air at the surface into
the main portion of air stream, as a result of which they are carried away with the air flowing.
In this case, mass transfer is a result of a concentration difference or gradient, the diffusing
substance (water) moving from a region of high concentration to a region of low
concentration. Hence, the driving force for mass transfer is a concentration difference just as
a temperature difference in heat transfer.
Fractional distillation (one of the methods of separation) depends on the difference in
vapour pressures of different components at the same temperature (volatility), while gas
absorption depends on the difference in solubility of gases in a selective solvent. Liquid-
liquid extraction and leaching depend on the difference in solubility in a liquid solvent.
Mass transfer operations include separation techniques such as distillation, gas
absorption, liquid extraction, drying, crystallisation, etc.
In mass transfer operations, mass transfer may occur :
(a) In one direction, e.g., gas absorption.
(b) In opposite directions (i.e., in both directions), e.g., distillation.
(c) With simultaneous heat transfer, e.g., drying and crystallisation.
(d) With a simultaneous chemical reaction, e.g., gas absorption accompanied by a
chemical reaction (absorption of CO2 in an aqueous solution of KOH)
(e) With the exchange of one or more components.
(f) Isothermally (i.e., at constant T) and non-isothermally.
The phenomena those must exist in mass transfer operations are :
(a) At least two phases must come in contact with each other.
(b) Materials must flow from one phase to the other.
(c) A part of the total flow of material must occur by molecular diffusion.
(7.1)
Unit Operations – II 7.2 Diffusion

Three states of aggregation of a substance are gas, liquid and solid and due to this
we have six possibilities of the phase contact. Gas-gas (not practically realised), gas-liquid,
gas-solid, liquid-liquid, liquid-solid and solid-solid (no industrial separation operation in this
category is found).
Mass transfer operations have been classified according to the phases in contact as
given in Table 7.1.
Table 7.1
Phases in contact Mass transfer operation
Liquid-vapour (gas) Distillation (Fractionation)
Liquid-gas Gas absorption
Stripping
Humidification
Dehumidification
Liquid-solid Crystallisation
Leaching
Adsorption
Liquid-liquid Extraction
Solid-vapour Sublimation
Solid-gas Adsorption
Solid (wet) gas (usually air) Drying
Hence, distillation, gas absorption, stripping are gas-liquid operations, liquid extraction is
a liquid-liquid operation, crystallisation is a liquid-solid operation and drying is a gas-solid
operation.
As the basic mechanism is the same whether the phase is a gas, liquid or solid, there are
some similarities among the various mass transfer operations and these are given below.
(a) Equilibrium between the phases is attained after a sufficiently long time of phase
contact between them.
(b) Material transfer is caused by the combined effect of molecular diffusion and
turbulence.
(c) There is no resistance to mass transfer at the phase interface (because of the
existence of equilibrium at the interface).
(d) Rate of mass transfer is evaluated by deviation/departure from equilibrium
concentration.
1. Distillation : Distillation is a gas-liquid operation. It is a method of separating the
components of a liquid mixture using thermal energy. The difference in vapour pressures of
different components is responsible for such a separation. It is also called as fractionation or
fractional distillation. (The term fractionation is commonly used in petroleum refineries).
The separation of a crude petroleum into gasoline, kerosene, etc. is a typical example of
distillation.
Unit Operations – II 7.3 Diffusion

Consider a binary liquid mixture. For this, we have : C = 2, P = 2.

∴ F = 2 (phase rule : F = C – P + 2). In this case there are four variables; temperature,
pressure, composition of A in the liquid and vapour phases. If the pressure is fixed, then
according to the phase rule only one variable, e.g., the liquid phase concentration can be
varied and the temperature and vapour phase concentration follow and thus the system is
defined completely. Here the equilibrium data are presented in temperature-composition
diagrams at constant pressure or by plotting vapour phase composition against liquid phase
composition. Such a plot is called the equilibrium curve.
2. Gas absorption : Gas absorption is a gas-liquid operation. It is a method of
separating one or more constituents of a gas mixture by contacting it with a suitable liquid
solvent. The necessary condition is the difference in solubility of the constituents in a given
solvent. The washing of ammonia from a ammonia-air mixture by means of water is a typical
example of gas absorption.
Consider that a gas mixture contains two components and one component is transferred.
Thus, we have C = 3, P = 2 and ∴ F = 3. There are four variables : temperature pressure,
and the concentration of A in liquid and gas phases. If the temperature and pressure are fixed,
one concentration may be chosen as the remaining independent variable that may be varied
and the other concentration follows. A plot of equilibrium concentration in the gas phase v/s
concentration in the liquid phase gives an equilibrium relationship between the phases.
3. Liquid extraction : Liquid extraction is a liquid-liquid operation. It is a method of
separating the constituents of a liquid mixture by treating it with a suitable solvent that
preferentially dissolves one or more of the constituents of the mixture. It is also called as
solvent extraction. It is used as a separation technique only when distillation is ineffective
and difficult. The separation of penicillin from fermentation mixtures is a typical example of
application of liquid extraction.
4. Crystallisation : It is a liquid-solid operation and used to obtain materials in the
form of attractive and uniform crystals of good purity. Crystallisation is the formation of
solid particles within a homogeneous liquid phase.
5. Drying : Drying is a gas-solid operation. In general, it is the removal of moisture of
a substance.
In case of drying, there are two phases and three components. C = 3, P = 2, ∴ F = 3.
The variables are : temperature, pressure, the concentration of water in the solid and the
gas phases. If the temperature and pressure are fixed, one concentration may be taken as the
remaining independent variable and the other concentration follows. These two
concentrations can be plotted as the equilibrium curve.
DIFFUSION
It is the movement of an individual component through a mixture from a region of higher
concentration to a region of lower concentration at fixed temperature and pressure with or
without the help of an external force.
A mixture which is non-uniform initially will be ultimately brought to uniformity
(a mixture is everywhere uniform in the concentration of its constituents) by diffusion since
the concentration gradient which acts as a driving force for diffusion tends to move the
component in such a direction as to equalise concentrations and destroy the gradient. If we
maintain the concentration gradient by constantly supplying the diffusing component to the
Unit Operations – II 7.4 Diffusion

high concentration end and removing it at the low concentration end, then the flow of
diffusing component is continuous. This movement is utilised in mass transfer operations.
When diffusion results from the random movement/motion of the molecules, it is called
molecular diffusion. As the molecular diffusion requires actual migration of molecules, the
rate of mass transfer is higher in gases than liquids and very slow in solids. When the
movement of the molecules occurs with the help of an external force (e.g., mechanical
stirring and convective movement of the fluid), then it is called eddy or turbulent diffusion.
The molecular diffusion is a slow process, whereas the eddy diffusion is a fast process. The
molecular diffusion is the mechanism of a stationary fluid, i.e., a fluid at rest and fluids in
laminar flow. In case of fluids in turbulent flow, the mechanism of mass transfer is by eddy
diffusion. The transfer of material in the presence of a concentration gradient is classified as
molecular transfer and eddy transfer. Molecular transfer of mass occurs in stationary fluids or
fluids in laminar flow whereas eddy transfer occurs in fluids under turbulent conditions.
Role of diffusion in mass transfer :
Diffusion may occur in one phase or in both phases in all the mass transfer operations.
In case of distillation, the more volatile component diffuses through the liquid phase to the
interface between the phases (liquid and vapour phases) and away from the interface into the
vapour phase. The less volatile component diffuses in the opposite direction and passes from
the vapour phase to the liquid phase. In case of gas absorption, the solute gas diffuses
through the gas phase to the interface and then through the liquid phase (liquid solvent
phase) from the interface between the phases. In case of crystallisation, the solid solute
diffuses through the mother liquor (liquid phase) to the crystals and deposit on the solid
surfaces. In case of drying operation, liquid water (moisture) diffuses through the solid
towards the surface of the solid, evaporates and diffuses as a vapour into the gas phase
(drying medium). In case of liquid-liquid extraction, the liquid solute diffuses through the
raffinate phase and then into the extract phase (solvent phase) from the interface between
the phases.
Molecular Diffusion :
Concentrations, velocities and fluxes :
Let us consider two chemical species A and B are placed in two compartments that are
separated by a impermeable partition. Now, assume that the partition is suddenly removed so
that the species A will diffuse into B and the species B will diffuse in A and this will
continue at a constantly decreasing rate until the mixture becomes everywhere uniform in the
concentration of its constituents, i.e., of A and B. The process is one of molecular diffusion
in which the species are diffused in one another as a result of the random motion of
molecules. The rate of diffusion is governed by Fick's law and before dealing with this law,
we will define the above mentioned terms based on the combination of such species. We
make it clear here that by the word solution we mean a mixture of species of the same phase
– gas in gas, liquid in liquid, etc., i.e., one phase - a gaseous, a liquid or a solid mixture.
Concentration :
There are various ways to express the concentration of the various species in a
multicomponent system/mixture. We limit our discussion to mass concentration, molar/
concentration, mass fraction and mole fraction.
Unit Operations – II 7.5 Diffusion

Mass concentration : The mass concentration of a species A in a solution is the mass of

species A per unit volume of the solution (mixture). It is equivalent to the density of A and
denoted by the symbol ρA.
For a binary mixture/solution of A and B,
ρA + ρB = ρ … (7.1)
where ρ is the mass density of the solution.
Molar concentration : The molar concentration of a species A in a solution is the
number of moles of species A per unit volume of the solution.
ρA
CA = M … (7.2)
A
where MA is the molecular weight of component A. The unit of molar concentration in the
SI system is kmol/m3.
Hence, for a binary mixture of A and B, the total molar concentration of the mixture is
given by
C = CA + CB … (7.3)
'
Mass fraction : The mass fraction x of a species A in a solution may be defined as the
A
ratio of the mass concentration of species A to the mass density of the solution.
ρA
x'A = … (7.4)
ρ
Mole fraction : The mole fraction (xA) of a species A in a solution may be defined as the
ratio of the molar concentration of A to the molar concentration of the solution.
CA
xA = C … (7.5)
For a binary system of A and B, we have
x' + x' = 1
A B

and xA + xB = 1
In the gas phase, concentrations are usually expressed in terms of partial pressures.
For an ideal gas A, pAV = nART
nA pA
CA = V = RT … (7.6)
where pA is the partial pressure of species A in the mixture, nA is the number of moles of A in
the mixture, V is the molar volume of the mixture, T is the temperature (absolute), and R is
the univeral gas constant.
xA in terms of pA is given as :
CA pA/RT pA
xA = C = P/RT = P … (7.7)
where P is the total pressure exerted by the gas mixture.
pA pB P
Also, we have C = CA + CB = RT + RT = RT … (7.8)
Unit Operations – II 7.6 Diffusion

Velocities :
In a diffusing mixture, various chemical species are moving at different velocities as they
may have different mobilities. The bulk velocity of the mixture would be some sort of an
average velocity. Let ui be the velocity of the ith species with respect to the stationary
coordinate system. Then, for a mixture of n species, the local mass average velocity u is
defined by
n
∑ ρi ui
i=1
u = n … (7.9)
∑ ρi
i=1
ρu is the local rate at which mass passes through a unit cross-section when it is placed
perpendicular to u.
For a binary system of A and B components, we can write
ρA uA + ρB uB
u = … (7.10)
ρ
The local molar average velocity of the mixture, U, is defined by
n
∑ Ci ui
i=1
U = n … (7.11)
∑ Ci
i=1
Cu is the local rate at which moles pass through a unit cross-section which is placed
perpendicular to U.
For a binary system of A and B, we can write
CAuA + CB uB
U = C … (7.12)
Let us define two diffusion velocities relative to/with respect to the two bulk velocities
(mass and molar average velocities of the mixture).
The mass diffusion velocity of a species is the velocity of that species relative to the local
mass average velocity of the mixture.
Mass diffusion velocity of species i w.r.t. u = ui – u
Mass diffusion velocity of species A w.r.t. u = uA – u.
The molar diffusion velocity of a species is the velocity of species with respect to/relative
to the local molar average velocity of the mixture.
Molar diffusion velocity of species i w.r.t. U = ui – U … (7.13)
Molar diffusion velocity of species A w.r.t. U = uA – U … (7.14)
Mass flow rate : It is the quantity of material flow in mass units per unit time (e.g., kg/s)
Molar flow rate : It is the quantity of material flow in molar units per unit time
(e.g., kmol/s).
Unit Operations – II 7.7 Diffusion

Flux : The mass transfer flux of a given species (vector quantity) is defined as the
amount of that species, in either mass or, molar units, that crosses a unit area per unit time.
We will define four types of fluxes, two with reference to fixed coordinates in space and two
with respect to local mass average velocity and local molar average velocity (w.r.t.
coordinates moving with mass average velocity and molar average velocity).
Mass flux : The mass flux of a species i is defined as the mass of species i that passes
through a unit area per unit time.
The mass flux relative to stationary/fixed coordinates is given by
ni = ρi ui … (7.15)
The mass flux relative to the mass average velocity u is given by
ji = ρi (ui – u) … (7.16)
Molar flux : It is defined as the moles of species i that passes through a unit area per unit
time.
The molar flux relative to stationary coordinates is given by
Ni = Ci ui … (7.17)
The molar flux relative to the molar average velocity U is given by
Ji = Ci (ui – U) … (7.18)
It is true that any one of the above mentioned notation used for the flux is adequate for all
diffusion problems, but each has certain advantages. In process calculations, it is usually
desirable to refer to a coordinate system fixed in an equipment so the flux Ni is used in
engineering. The fluxes ji and Ji are the usual measures of rates of diffusion and are useful in
formulating the equations of change for multicomponent systems.
For a binary system of A and B :
The mass fluxes of A and B relative to stationary coordinates are :
nA = ρA uA … (7.19)
nB = ρB uB … (7.20)
The mass fluxes of A and B relative to mass average velocity are :
jA = ρA (uA – u) … (7.21)
jB = ρB (uB – u) … (7.22)
The molar fluxes of A and B with respect to stationary coordinates are :
NA = CA uA … (7.23)
NB = CB uB … (7.24)
The molar fluxes of A and B relative to molar average velocity U are :
JA = CA (uA – U) … (7.25)
JB = CB (uB – U) … (7.26)
Unit Operations – II 7.8 Diffusion

JA and JB are the diffusion flux of components A and B. The various fluxes can be
interrelated as,
nA = ρA uA
= ρA (u + uA – u)
= ρA u + ρA (uA – u)
= ρA u + ji … (7.27)
ρA
We have, xA' = ∴ ρA = xA' ρ
ρ
nA = x'A (ρu) + ji
Since, ∑ ni = ∑ ρi ui = ρv
∴ n = x' ∑ n + j
A A i i … (7.28)
Similarly, NA = CA uA
= CA (U + uA – U)
= CA U + CA (uA – U)
NA = CA U + J A … (7.29)
NA = xA (CU) + JA
∑ Ni = ∑ Ci ui = CU
NA = xA (∑ Ni) + JA … (7.30)
Fick's law of diffusion :
A relation between the flux of the diffusing substance and the concentration gradient
responsible for molecular diffusion-mass transfer was first proposed by FICK in 1855 and is
therefore referred to as Fick's first law of diffusion.
The flux of a diffusing component A (diffusion flux of A) in z direction in a binary mixture
of A and B is proportional to the concentration gradient.
Therefore, the Fick's law of diffusion for species/component A in a binary mixture of A
and B for steady state diffusion in z direction can be expressed as
dCA
JA = – DAB · dz … (7.31)

where JA is the molar flux of A in the z direction relative to the molar average velocity [moles
per unit area per unit time, kmol/(m2.s)].
CA is the molar concentration of A [moles of A per unit volume, kmol/m3]
dCA
dz is the concentration gradient in the z-direction.
DAB is a proportionality constant, known as the molecular diffusivity or diffusion
coefficient for component A diffusing through B, m2/s and z is the distance in the direction of
diffusion, m.
Unit Operations – II 7.9 Diffusion

The negative sign in Equation (7.31) indicates/implies that diffusion occurs in the
direction of decrease in concentration. Thus, the term dCA/dz is –ve and the flux becomes
+ve.
Diffusivity is defined as the ratio of the flux to the corresponding concentration gradient.
The dimensions of the diffusivity are L2/θ and its unit in the SI system is m2/s. The diffusivity
of any component is a measure of its diffusive mobility and is a function of temperature,
pressure, nature, and composition.
Diffusivity increases with decrease in pressure and increases with increase in
temperature.
For a binary system in z direction, dropping the subscript z, we have
JA = CA (uA – U) … (7.32)
Equating Equations (7.31) and (7.32), we get
dCA
JA = CA (uA – U) = – DAB dz
dCA
CA uA = – DAB dz + CAU … (7.33)
According to Equation (7.12), U is given by
1
U = C (CA uA + CB uB)
CA
CA U = C (CA uA + CB uB)
CAU = xA (CA uA + CB uB)
Substituting CAU in Equation (7.33), we get
dCA
CA uA = – DAB dz + xA (CA uA + CB uB)
Using Equation (7.23), the above expression becomes
dCA
NA = – DAB dz + xA (NA + NB)

NA = JA + xA (NA + NB) … (7.34)

Here, JA is the concentration gradient contribution, the diffusion flux and xA (NA + NB) is
the bulk motion contribution, the flux due to bulk flow.
Molecular Diffusion in Gases :
For a diffusion in the z direction and for NA and NB both constant (steady state), we will
derive equations for the flux.
For an ideal gas, we have
CA pA
C = P = yA … (7.35)

where pA is the partial pressure of component A.

and P is the total pressure.
Unit Operations – II 7.10 Diffusion

1. Steady state equimolar counter diffusion : For the steady state diffusion of two
ideal gases A and B with an equal number of moles the gases diffusing counter current to
each other (in opposite directions to each other), the flux equation for A is given by
DAB
NA = RTz (pA1 – pA2) … (7.36)
where NA is the molar flux of A in kmol/(m2.s), DAB is the diffusivity of A in B in m2/s,
z (z2 – z1) is the distance through which diffusion occurs in m and pA1 and pA2 are the partial
pressures of the component A (in Pa) at the beginning and end of the diffusion path
respectively.
We have : NA = JA + xA (NA + NB)
dCA CA
NA = – DAB dz + C (NA + NB) … (7.36 A)
From the ideal gas law, for the component A, we can write :
pA = CA RT
pA
∴ CA = RT
dpA
dCA = RT
P
C = RT … for gas as a whole
Substituting for CA, C and dCA in Equation (7.36 A), we get
DAB dpA pA
NA = – RT dz + P (NA + NB) … (7.37)
For equimolar counter diffusion,
NA = – NB = constant. Therefore, Equation (7.37) reduces to
DAB dpA
NA = – RT dz … (7.38)
If DAB is constant, then the above equation can be integrated. Therefore,
z2 pA2
DAB
NA ⌠
⌡ dz = – RT ⌠⌡ dpA
z1 pA1

– DAB
NA (z2 – z1) = RT (pA2 – pA1)
Let z2 – z1 = z. Rearranging the above equation, we get
DAB
NA = RTz (pA1 – pA2) … (7.39)

Here, the concentration difference is expressed in terms of partial pressure difference.

It can also be expressed in terms of mole fraction or molar concentration.
Unit Operations – II 7.11 Diffusion

2. Steady state diffusion of A through nondiffusing/stagnant B :

Gas absorption and humidification are typical operation of this kind.
For the steady state diffusion of an ideal gas A through a stagnant gas B, the molar flux
of A is given by
DAB P
NA = RTz · p (pA1 – pA2) … (7.40)
B‚ M

where pB, M is the log mean partial pressure of the gas B.

dCA CA
We have : NA = – DAB dz + C (NA + NB)
– DAB dpA pA
NA = RT dz + P (NA + NB)
For the steady state diffusion of A through a nondiffusing B, we have
NA = constant and NB = 0
With this, the above equation reduces to
– DAB dpA pA
NA = RT dz + P · NA
Rearranging, we get
P – pA – DAB dpA
NA  P  = RT dz
 
If DAB is constant, then the above equation can be integrated. Therefore,
z2 pA2
– DAB · P dpA
NA ⌠
⌡ dz = RT
⌠
⌡ P – pA
z1 pA1
DAB P P – pA2
NA = RTz ln P – p  … (7.41)
 A1
According to the Dalton's law of partial pressure, we have
pA1 + pB1 = P
and pA2 + pB2 = P
∴ pB1 = P – pA1
pB2 = P – pA2
∴ pB2 – pB1 = pA1 – pA2
DAB P pB2
∴ NA = RTz ln p 
 B1
DAB P (pB2 – pB1)
NA = RTz (p – p ) ln (pB2/pB1) … (7.41 A)
B2 B1
pB, M is the log mean partial pressure of component B and is given by
pB2 – pB1
pB, M = ln (p /p )
B2 B1
Unit Operations – II 7.12 Diffusion

Replacing (pB2 – pB1) by (pA1 – pA2) since (pB2 – pB1) = (pA1 – pA2) in the numerator of
Equation (7.41 A) and substituting pB, M for (pB2 – pB1)/ln (pB2/pB1), we get
DAB P
NA = RTz · p (pA1 – pA2) … (7.42)
B‚ M
In this case, the flux is proportional to the concentration difference expressed in terms of
partial pressure of A and inversely proportional to the distance z and the concentration of the
stagnant gas (pB, M). Increase in z and pB, M, increases resistance to diffusion and thus, flux
decreases.
Molecular Diffusion in Liquids :
1. Steady-state equimolar counter diffusion :
We have : NA = – NB = constant
The flux equation for steady state equimolar counter diffusion for component A is
given by
DAB DAB  ρ 
NA = z (C A1 – C A2 ) = z Mavg. (xA1 – xA2) … (7.43)

where xA1 – xA2 is the concentration difference of component A in terms of mole fraction.
(ρ/M)avg. = Cavg. = [ρ1/M1 + ρ2/M2]/2 … (7.44)
Cavg. is the total average concentration of A and B in kmol/m3, ρ1 and ρ2 are the average
densities of the solution in kg/m3 at locations 1 and 2 respectively, and M1 and M2 are the
average molecular weights of the solution at locations 1 and 2, respectively in kg/kmol.
2. Steady state diffusion of A through nondiffusing B :
Here, we have : NA = constant, NB = 0
The flux for component A is given by
DAB
NA = z · x (ρ/M) avg. (xA1 – xA2) … (7.45)
B‚ M

where xB‚ M = logarithmic mean mole fraction of B

= (xB2 – xB1)/ln (xB2/xB1)
Diffusion in Solids :
The operations like leaching, drying, etc. involve contact of fluids with solids and
involve diffusion in the solid phase.
Fick's law for the steady state diffusion can be written as
dCA
NA = – DA dz … (7.46)

where NA is the rate of diffusion of A per unit cross-section of solid. DA is the diffusivity of A
through the solid, – dCA/dz is the concentration gradient in the direction of diffusion.
Unit Operations – II 7.13 Diffusion

1. Diffusion through a flat slab of thickness z :

Considering DA constant, integration of Equation (7.46) yields
DA [CA1 – CA2]
NA = z … (7.47)
z = z2 – z1 = thickness of the slab
CA1 and CA2 are the concentrations of A at the opposite sides of the slab.
For other solid shapes, the rate of diffusion is given by
D Aavg. (CA1 – CA2)
W = NA Aavg. = z … (7.48)
Aavg. is the average cross-section available for diffusion.
For the radial diffusion through a solid cylinder of inner and outer radii r1 and r2 and
length L :
2π (r2 – r1) L
Aavg. = ln (r2/r1) , and z = r2 – r1
For the radial diffusion through a spherical shell of inner and outer radii r1 and r2,
Aavg. = 4π r1 r2 and z = r2 – r1
Steady State Equimolar Counter Diffusion :
The diffusion of two components in opposite directions to each other in a stationary
mixture is of importance in distillation of a binary system. If the two components are at the
same temperature and the same total pressure, then no net movement of the mixture will take
place and it will be simply the replacement of the molecules of one component by the
molecules of other component. In a language of diffusion, two components diffuse at the
same molar flow rate in the opposite directions to each other. This overall transfer process is
called as equimolar counter diffusion.
Consider a case of two gases A and B at constant total pressure P in two chambers.
Let us consider that two large chambers containing gases A and B are connected by a
tube in such a way that molecular diffusion at steady state is occurring. The total pressure P
is uniform (constant) throughout.
A B
pA1 pA2
pB1 JA pB2
1 JB 2
x
(a)

P = pA + pB
pA1 P
pB2
pA
p or P
pA2
pB1 pB
0 x
(b)
Fig. 7.1 : Equimolar counter diffusion of gases A and B;
(a) system, (b) concentration profile
Unit Operations – II 7.14 Diffusion

Stirring provided in each chamber keeps the concentration in each chamber uniform.
The partial pressure pA1 > pA2 and pB2 > pB1. The molecules of A diffuse to the right, while
the molecules of B diffuse to the left.
As the temperature and total pressure P is constant throughout, the net moles of A
diffusing to the right must be equal to the net moles of B diffusing to the left. If this is not so,
the total pressure would not remain constant throughout the system. This implies/indicates
that
JA = – JB … (7.49)
JA is the molar flux of component A in the x-direction due to molecular diffusion in
kmol/(m2.s).
Fick's law for component B for constant molar concentration, C, becomes
dCB
JB = – DBA dx … (7.50)
Here the flux is in the x-direction.
According to the Dalton's law, the total pressure is the sum of the partial pressures of
A and B.
∴ P = pA + pB … (7.51)
and we know that : pA ∝ CA … (7.52)
The total molar concentration for the gaseous mixture is given by
C = CA + CB … (7.53)
Differentiating both the sides of Equation (7.53) with respect to x gives
dCA d CB
0 = dx + dx … (7.54)

dCA – dCB
or dx = dx … (7.55)

Therefore, if a gradient exists in the gas A, a gradient also exists in the gas B. The
gradient of B is equal but opposite in sign to that of A.
Fick's law for component A for constant total concentration is
dCA
JA = – DAB dx … (7.56)

Combining Equations (7.49), (7.50) and (7.51),

dCA
JA = – DAB dx

 dCB
= – JB = – – DBA dx  … (7.57)
 
dCA dCB
– DAB dx = DBA dx … (7.58)
Unit Operations – II 7.15 Diffusion

dCA dCB
but dx = – dt … (7.59)
∴ DAB = DBA … (7.60)
This shows that for a binary mixture of A and B, the diffusivity coefficient DAB for A
diffusing in B is the same as DBA, for B diffusing in A.
dCA
We have : JA = – DAB dx … (7.61)
For ideal gases, the molar concentration of A is related to the partial pressure of A by
NA pA
CA = V = RT … (7.62)
dCA 1 dpA
∴ dx = RT dx … (7.63)
DAB dpA
∴ JA = – RT dx … (7.64)
Integrating, we get
DAB (pA1 – pA2)
JA = RT (x – x ) … (7.65)
2 1

DAB (pA1 – pA2)

= RT x , x = x2 – x1 … (7.66)
For species B,
DBA (pB1 – pB2)
JB = RT x … (7.67)

Equations (7.66) and (7.67) are the equations for steady state equimolar counter diffusion.
We know that
dCA dCB
dx = – dx … (7.68)

The gradient of B is equal but opposite in sign to that of A. Since the gradient for B
exists, there must be molar flux of B, as stated by Equation (7.50). Combining of Equations
(7.50), (7.56) and (7.68) gives
JA = – JB … (7.69)
This shows that the rates of diffusion are equal but in opposite directions. Equation (7.69)
is always true in the binary mixtures inspite of any other mechanism for mass transfer may be
occurring. The rates of transfer of the two species by molecular motion (diffusion) are always
equal but in opposite directions. When molecular motion is the only mechanism, the overall
transfer process is called as an equimolar counter diffusion.
Mass Transfer Coefficients :
In many mass transfer operations, the turbulent flow is desired to increase the rate of
mass transfer per unit area. In such cases, the mass transfer rate is expressed in terms of mass
transfer coefficients. In turbulent flow there are three regions of mass transfer but as it is very
Unit Operations – II 7.16 Diffusion

difficult to know the value of a distance in the turbulent region through which diffusion
occurs, it is considered that the entire resistance to mass transfer lies in a laminar sublayer of
thickness z (effective laminar film thickness). The resistance offered by the effective laminar
film thickness is approximately the same as the combined resistance offered by three regions
in turbulent motion. The flux equations for such situations are of the type :
Flux = (Mass transfer coefficient) × (Concentration difference)
As the concentration can be expressed in number of ways, we have a variety of types of
mass transfer coefficients.
Mass transfer coefficient is thus defined as the rate of mass transfer per unit area per
unit concentration difference.
The flux equation obtained for the steady state equimolar counter diffusion components
A and B diffusing at the same molar rates in opposite directions for turbulent motion
becomes
DAB
NA = RTz (pA1 – pA2) … (7.70)
G

DAB
The term RTz is constant for a given situation and it can be termed as the mass transfer
G

film coefficient for the gas and may be denoted by the symbol k'G. With this, Equation (7.70)
becomes

NA = k'G (pA1 – pA2) … (7.71)

The flux equation obtained for the steady state diffusion of A through non-diffusing
(stationary) B for turbulent motion may be written as :
DAB P
NA = RTz p (pA1 – pA2) … (7.72)
G B, M

NA = kG (pA1 – pA2) … (7.73)

DAB P
where, kG = RTz p
G B, M

Similar equations can be written for the liquid phase.

The flux equation for the equimolar counter diffusion for the liquid phase is
DAB
NA = z (CA1 – CA2) = k'L (CA1 – CA2) … (7.74)
L

where zL is the effective laminar film thickness and k'L is the mass transfer film coefficient
for the liquid or the liquid film mass transfer coefficient/individual mass transfer coefficient
for the liquid phase.
Mass transfer film coefficient may be defined as the rate of mass transfer from the
bulk of one phase to an interface of unit area for a unit driving force.
Unit Operations – II 7.17 Diffusion

The flux equations for transfer of A through non-transferring B (i.e., diffusion of A

through non-diffusing B) in terms of the driving force expressed in terms of concentration
and molefraction are :
NA = ky (yA1 – yA2), NA = kC (CA1 – CA2) for gases … (7.75)
NA = kx (xA1 – xA2), NA = kL (CA1 – CA2) for liquids … (7.76)
Similar equations for equimolecular counter diffusion are :
' '
NA = ky (yA1 – yA2), NA = kc (CA1 – CA2) for gases … (7.77)
' '
NA = kx (xA1 – xA2), NA = kc (CA1 – CA2) for liquids … (7.78)
In two film concepts, z is the effective thickness of the film.
Relation between film coefficients :
' P ' pB, M '
Gases : kc RT = kc C = kc RT = k'G P = ky = kv yB, m = kG pB, M = kG yB, M · P
pB, M = (pB1 – pB2)/ln (pB1 / pB2) , yB, M = (yB1 – yB2)/ln (yB1 / yB2),
' '
Liquids : kL' C = k'L ρ/M = kc C = kx = kx xB, M = kL xB, M C
Overall Mass Transfer Coefficient :
The overall mass transfer coefficients are measured on the basis of the gas phase or the
liquid phase driving force.
The flux equation in terms of the overall mass transfer coefficient and the overall driving
force for diffusion of A through non-diffusion B is given by
*
NA = KG (pA – pA) … (7.79)
*
KG is the overall gas phase mass transfer coefficient in kmol/(m2⋅s) and (pA – pA) is the
overall driving force for the gas phase in terms of partial pressure.
*
pA is the partial pressure of solute A over the solution having a composition of the bulk
liquid of CA. (Partial pressure of A in the gas phase that would be in equilibrium with CA, the
concentration of A in the bulk liquid phase.)
The flux can also be written as :
*
NA = Ky (yA – yA) … (7.80)
Similarly,
*
NA = KL (CA – CA) … (7.81)
where KL is the overall liquid phase mass transfer coefficient and is based on the
*
concentration difference driving force for the liquid phase. CA is the concentration of solute
A in the liquid phase that would be in equilibrium with pA, partial pressure of A in the bulk
gas phase.
Mass transfer (film) coefficients in terms of the driving force in each phase are given by
NA = kG (pA – pAi) = kL (CAi – CA) … (7.82)
The overall driving force for the gas phase is
* *
pA – pA = (pA – pAi) + (pAi – pA ) … (7.83)
Unit Operations – II 7.18 Diffusion

For a state of equilibrium according to the Henry's law, we have :

* *
pA = H CA, pAi = H CAi and pA = H CA
With this, Equation (7.83) becomes
*
pA – pA = (pA – pAi) + H (CAi – CA) … (7.83 A)
From Equations (7.81), (7.82) and (7.83), we have
* NA NA NA
pA – pA = K , pA – pAi = k , CAi – CA = k
G G L
*
Substituting for (pA – pA), etc., Equation (7.83 A) becomes
1 1 H
KG = kG + kL … (7.84)
1
Here K is the total resistance, the resistance in both the phases, based on the overall gas
G
phase driving force. It is equal to the sum of the gas film resistance (1/kG) and the liquid film
resistance k .
H
 L
The overall driving force for the liquid phase :
* *
CA – CA = (CA – CAi) + (CAi – CA)
Adopting the same procedure as for the gas phase, we get
* pA – pAi
CA – CA = H + (CAi – CA)
1 1 1
and KL = H kG + kL … (7.85)
CAi is the concentration of A at an interface between the phases.
Controlling Film Concept :
1 1 H
We have : KG = kG + kL … (7.86)
H
If H is very small, H –~ 0 (a case with a highly soluble gas), the liquid film resistance k
L
1
is negligible compared to k and the total resistance equals the gas film resistance (i.e., a gas
G
film offers entire resistance to transfer). Such a transfer process is called gas film (gas phase)
controlling as the resistance to transfer lies entirely in the gas film.
1 1
∴ KG = kG
or KG –~ kG
The overall mass transfer coefficients in such cases are based on the gas film coefficients
only. A typical example of this kind is absorption of ammonia in water.
We have :
1 1 1
KL = H kG + kL … (7.87)
Unit Operations – II 7.19 Diffusion

If H is very large, H >>1 (a case with a insoluble gas, i.e., a gas having low solubility),
1
the gas film resistance H k is negligible and the total resistance equals the liquid film
G
1
resistance k and the transfer process in such cases is considered to be liquid film
L
controlling. A typical example of this kind is absorption of CO2 in water.
1 1
KL ≈ kL
∴ KL ≈ kL
The overall mass transfer coefficients in such cases are based on the liquid film
coefficients only.
For absorption of a moderately soluble gas obeying Henry's law either KG or KL can be
used for mass transfer calculations. The absorption of sulphur dioxide in water is an example
of this type.
Interphase Mass Transfer :
In most important industrial applications of mass transfer, the material is transferred
across a phase boundary (an interface). For example, in distillation, the vapour and liquid are
brought into contact in a fractionating column and the more volatile component is transferred
from the liquid to vapour, while the less volatile component is transferred from the vapour to
liquid. In gas absorption, the solute gas is transferred from the gas to the liquid. In both of
these examples, one phase is liquid and the other is gas.
Phase : It is a homogeneous and physically distinct part of a system which is bounded by
a surface and, therefore, can be separated from the other parts of the system, e.g., water is
one phase, but ice is another phase. Phases may be liquid, solid or gaseous.
Interphase mass transfer : It is the process of mass transfer from the bulk of one phase
to the interphase surface, and then from the interphase to the bulk of another phase.
In the absorption of ammonia by water from an ammonia-air mixture, the solute
ammonia may diffuse through the gas phase and then pass through the interface between the
phases, and finally diffuse through the adjacent immiscible water phase (liquid phase).
In each phase, mass transfer occurs owing to the concentration gradient existing in that
phase and a state of equilibrium is assumed to exist at the interface between the two fluid
phases.
Interface
Gas
pA Liquid
Concentration of A

CAi

pAi

CA

Distance
Fig. 7.2
Unit Operations – II 7.20 Diffusion

In absorption of a solute gas A in a liquid solvent from a gas mixture, as shown in

Fig. 7.2, mass transfer occurs in the gas phase from pA to pAi (at the interface) and in the
liquid phase from CAi (at the interface) to CA. Equilibrium exists at the interface (between
the phases) and due to this there is no resistance to mass transfer at the interface and pAi and
CAi are related through the equilibrium relationship :
pAi = H CAi … (7.88)
where H is the Henry's law constant for the system under consideration.
Equilibrium :
In mass transfer operations usually there are two phases which are brought in contact for
the transfer of constituent material(s) from one phase to another or in both the phases. If two
phases come to a state of equilibrium, then the net transfer of material ceases. The
equilibrium relationship between the phases involved is of basic importance in all the mass
transfer calculations. The equilibrium relationships can be expressed by an equation or can
be shown graphically.
For gas absorption operation, the relationship between the equilibrium concentrations of
solute in a gas phase and a liquid phase at constant temperature and pressure is the desired
equilibrium relationship between the two phases. Now we will obtain the equilibrium
relationship for absorption of ammonia in water from an ammonia-air mixture. Consider that
a definite amount of liquid water along with a gaseous mixture of ammonia and air is placed
in a closed container which is maintained at constant temperature and pressure. As the
ammonia is very soluble in water, some of the ammonia molecules will transfer from the gas
phase to the liquid phase, crossing the interface separating the two phases. Some of the
ammonia molecules return back into the gas, at a rate proportional to the ammonia
concentration in the liquid. As more and more ammonia enters the liquid, its concentration in
that phase increases and due to this the rate at which ammonia returns back to the gas phase
increases. This will continues and ultimately a stage will reach at which the rate with which
ammonia enters the liquid phase becomes exactly equal to the rate with which it leaves the
liquid phase and also at the same time ammonia concentration throughout each phase
becomes uniform through the mechanism of diffusion, at this stage, a dynamic equilibrium is
now said to exist between the phases. In a state of equilibrium, the net transfer of ammonia
ceases even though the ammonia molecules continue to transfer to and fro from one phase to
another. The concentrations of ammonia within each phase do not change with time. Then
these concentrations of ammonia in these two phases are its equilibrium concentrations.
If we further inject additional ammonia into the container, equilibrium will be disturbed,
the system will try to attain a state of equilibrium and finally we get a new set of equilibrium
concentrations. These equilibrium values of concentrations are higher than those previous
obtained. In this way we can obtain the complete relationship between the equilibrium
concentrations in both phases at constant temperature and pressure. If we express the
equilibrium concentrations of ammonia (A) in both the phases in terms of its mole fractions
xA and yA in the liquid phase and the gas phase, respectively and plot the values of yA (as an
ordinate) against the corresponding values of xA (as an abscissa), we obtain a curve as shown
in Fig. 7.3. Such a curve is called an equilibrium distribution curve. This curve changes only
Unit Operations – II 7.21 Diffusion

by changing the conditions imposed on the system such as temperature and pressure. One
should note here that at equilibrium, the concentrations of ammonia in the two phases are not
equal but it is the chemical potential of ammonia which is the same in both the phases and it
is this equality of chemical potentials and not of concentrations, because of which the net
transfer of the solute ammonia ceases.
Mole fraction of A in gas
(yA)

Mole fraction of A in liquid

(xA)

Fig. 7.3 : Equilibrium-distribution curve at constant temperature

Mechanism of Mass Transfer :
The mechanism of mass transfer across a phase boundary (an interface) can be explained
by the various theories such as :
(i) Whitman's two-film theory
(ii) Higbie's penetration theory
(iii) Danckwert's surface renewal theory
(iv) Toor and Marchello's film penetration theory.
The Two-film Theory :
Salient features of Whitman's two film theory are :
(i) Resistance to transfer in each phase is regarded as lying in a thin film close to the
interface (i.e., in two fictitious films one on each side close to the interface).
(ii) The transfer in these films is by a steady state process of molecular diffusion.
(iii) The concentration gradient is assumed to be linear in these films and it is zero
outside the films, i.e., zero in the bulk fluid.
Interface (gas-liquid)
Gas
yA
of diffusing solute A

Liquid film
Concentration

xAi

yAi

Gas xA
film
Distance
Fig. 7.4
Unit Operations – II 7.22 Diffusion

(iv) The theory assumes that the turbulence in the bulk fluid vanishes at the interface of
the films.
(v) The film capacity is negligible, i.e., the time taken for a concentration gradient to
establish is small compared to the time of transfer.
Consider a solute gas (A) diffusing from a gas phase into a liquid phase. There must be a
concentration gradient in the direction of mass transfer within each phase. This is shown in
Fig. 7.4 graphically in terms of distance through the phases.
The concentration of A in the bulk of gas phase is yA molefraction, and it falls to yAi at
the interface. The concentration of A in the liquid phase falls from xAi at the interface
between the phases to xA in the bulk liquid. The bulk concentrations yA and xA are not in
equilibrium because otherwise the solute will not be diffused from the gas to the liquid
phase.
Whitman assumed that the resistance to transfer of A lies in two hypothetical films, one
on each side of the interface, in which the transfer is entirely by molecular diffusion. There is
no resistance to transfer across the interface and as a result the concentrations
yAi and xAi are the equilibrium values.
For steady state mass transfer, the rate of transfer of A to the interface must be equal to
the rate at which A is transferred from the interface to the bulk of liquid phase so that there is
no accumulation or depletion of A at the interface.
Therefore, we can write the mass transfer flux of A or rate of transfer of A in terms of
mass transfer coefficients and concentration changes occurring in the phases involved.
NA = ky (yA – yAi)
= kx (xAi – xA) … (7.89)
The differences in y's and x's are the driving forces for mass transfer.
Rearranging Equation (7.89), we get
kx yA – yAi
ky = xAi – xA … (7.90)
yA – yAi kx
xA – xAi = – ky … (7.91)
Fig. 7.5 shows typical values of the concentrations of the bulk phases (P) and at the
interface (Q).

yA P
Equilibrium curve yAi = f(xAi)
of solute A in gas
Concentration

yAi Q – kx
Slope =
ky
yA*

xA xAi
Concentration
of solute A in liquid
Fig. 7.5
Unit Operations – II 7.23 Diffusion

In experimental determinations of the rate of transfer of the solute A, it is possible to

measure only the bulk concentrations of the solute A and to measure the interface
concentrations is ordinarily impossible. The equilibrium-distribution curve shown in Fig. 7.5
*
is unique at fixed T and P, so yA in equilibrium with xA is a good measure of xA. Therefore,
the entire two phase mass transfer effects can be measured in terms of overall mass transfer
coefficient, Ky, i.e., the rate of mass transfer can also be set equal to the overall coefficient Ky
* *
( )
times the driving force yA – yA , where yA is the composition of the solute A in the gas
phase which is in equilibrium with xA.
*
NA = Ky (y A – yA ) … (7.92)
* *
1 yA – yA (yA – yAi) + (yAi – yA)
Ky = NA = NA
*
1 yA – yAi yAi – yA
Ky = NA + NA
*
1 1 yAi – yA
Ky = ky + kx (xAi – xA)
1 1 m
Ky = ky + kx … (7.93)

*
where, m = slope = (y
Ai – yA ) / (xAi – xA)
1/Ky is the overall resistance to mass transfer and 1/ky and m/kx are the resistances in the
liquid and gas films. The resistances in two phases are added to get an overall resistance and
hence it is also called as two resistance theory.
*
On the similar line, xA is a measure of yA and it can be easily shown that
1 1 1
Kx = m ky + kx … (7.94)

The Penetration Theory :

The penetration theory was proposed by Higbie. The main features of this theory are :
1. As the time of exposure of fluid for mass transfer generally being short,
development/establishment of the concentration gradient of the film theory (the
characteristic of a steady state) is not possible.
2. The transfer is largly because of fresh material brought to the interface by the eddies.
3. A process of unsteady state transfer occurs for a fixed period at the freshly exposed
surface.
4. Each fluid element (eddy) resides for the same length of time period at the surface.
According to this theory, the mass transfer coefficient is proportional to the square
root of the diffusivity.
Unit Operations – II 7.24 Diffusion

Surface Renewal Theory :

According to this theory (proposed by Danckwerts) :
1. The eddies of the fluid at the surface are exposed to varying lengths of time.
2. On the basis of exposure-time histories, an age distribution for the surface elements is
calculated.
3. The mass transfer coefficient is proportional to the square root of the diffusivity
regardless of the nature of the surface renewal rate.
Counter current and Cocurrent Mass Transfer :
Mass transfer processes that involve two fluid streams are frequently carried out
continuously by passing the fluid streams either in a counter current or a cocurrent fashion in
a column or device. The average driving force for a given situation will be larger in the
countercurrent operation than in the cocurrent operation and because of which a smaller size
equipment is needed for a given set of flow conditions for the countercurrent operation and
thus, the counter current flow is more common.
Examples of counter current mass transfer processes are :
(i) Distillation in packed column : In this case, a vapour stream (thermally created) is
moving up against the downward flow of a liquid reflux. At steady state, a state of
dynamic equilibrium is set up. The more volatile component under the action of a
concentration gradient is transferred from the liquid phase to the interface and then
from the interface into the vapour phase. The less volatile component is transferred
in the opposite direction and passes through the vapour into the liquid. Here
equimolar counter diffusion takes place since the molar latent heats of vaporisation
of two components are essentially the same.
(ii) Absorption in packed column : In this case, a solute gas together with a carrier
gas moves up against the downward flow of a liquid (solvent). The solute gas
diffuses through the gas phase to the interface where it dissolves and is then
transferred into the bulk of the liquid.
(iii) Liquid-liquid extraction in packed/spray column : In this case, both the streams
are liquid. The lighter liquid rises through the denser one. The solute diffuses from
the raffinate phase to the interface and away from the interface into the extract
phase.
Examples of Cocurrent Flow :
The cocurrent flow of gas and liquid streams usually in the downward direction through a
packed column is used for – catalytic chemical reaction between components of fluids,
diffusional operation when a gas to be dissolved in a liquid is a pure substance and for
diffusional operation accompanying a chemical reaction, e.g., in the absorption of hydrogen
sulfide in a sodium hydroxide solution. The cocurrent flow produces a separation effect
equivalent to that obtained with only one theoretical stage so used for such cases only. With
cocurrent flow there is no flooding and there is no upper limit for permissible phase flow
rates. The cocurrent flow is rarely used in the absence of a chemical reaction.
Analogies among Heat, Mass and Momentum Transfer :
Depending upon the fluid flow conditions, the mechanism of transfer process can be
classified as molecular transport (characteristic of stream line flow) and combined molecular
and eddy transfer (characteristic of total flow regime). There are similarities in governing
Unit Operations – II 7.25 Diffusion

equations for molecular transport as well as for turbulent transport and we can say that we
have analogies among these transport processes. A great deal of effort has been taken in
developing analogies (similarities) among these three transport processes for turbulent
transfer.
General Molecular Transport Equation :
The molecular transport of momentum, heat and mass is characterised by the same
general equation of the type :
Driving force
Rate of a transfer process = Resistance … (7.95)
Molecular transport or molecular diffusion equations for momentum, heat and
mass transfer :
These equations are applicable to laminar flow as molecular transport is a characteristic
of laminar/stream line flow.
Newton's law for momentum transport, i.e., Newton's equation for molecular diffusion
of momentum for constant density is
– µ d (ux ρ)
τzx = dz … (7.96)
ρ
d (ux ρ)
τzx = – ν dz … (7.97)

where τzx is the momentum transferred per unit time per unit area, where the momentum has
the units of (kg.m)/s. [It is also called as the momentum flux], µ is viscosity and ρ is the
density of fluid. ν is the kinematic viscosity and also called as the diffusivity of momentum
and has the units of m2/s.
Fourier's law for heat transport, i.e., Fourier's equation for molecular diffusion of heat
for constant ρ and Cp is
qz d (ρ CpT)
A = – α dz … (7.98)

qz
where A is the heat transferred per unit time per unit area and is called as heat flux and has
the units of W/m2 [J/(m2.s)]. α is the thermal diffusivity or diffusivity of heat in m2/s.
Fick's law of molecular mass transport or Fick's equation for molecular diffusion of mass
for constant total concentration in a fluid is
dCA
JAz = – DAB dz

d(ρA/MA)
= – DAB dz … (7.99)

where JAz is the molar flux of component A in the z direction due to molecular diffusion in
kmol A/(m2.s), DAB is the molecular diffusivity of molecule A in B or mass diffusivity in
m2/s. CA is the molar concentration of A in kmol/m3.
Unit Operations – II 7.26 Diffusion

These three equation states, respectively, that (a) the momentum transport occurs
because of a gradient in momentum concentration, (b) the energy transport occurs because of
a gradient in energy concentration, and (c) the mass transport occurs because of a gradient in
mass concentration.
Turbulent diffusion equations for momentum, heat and mass transfer :
For combined molecular and eddy transfer, the relations for momentum, heat and mass
are :
For turbulent momentum transfer for constant density, we have
d(ux ρ)
τzx = – (µ/ρ + εM) dz … (7.100)

d (ρ ux)
τzx = – (ν + εM) dz … (7.101)

For turbulent heat transfer for constant ρ and Cp, we have

qz d(ρ Cp T)
A = – (α + εH) dz … (7.102)

For turbulent mass transfer for constant total molar concentration, we have
dCA
JAz = – (DAB + εD) dz … (7.103)

In the above equations, εm is the turbulent or eddy diffusivity of momentum in m2/s, εH is

the turbulent or eddy diffusivity of heat or eddy thermal diffusivity in m2/s and εM is the
turbulent or eddy diffusivity of mass in m2/s. Again, these equations are quite similar or
analogous to each other.
Equations (7.97), (7.98) and (7.99) for momentum, heat and mass transfer are similar to
each other and to the general molecular transport Equation (7.95). All these equations have a
flux on the left hand side which is momentum, heat or mass transferred per unit time per unit
area and a diffusivity of momentum, heat and mass (i.e., transport properties, ν, α and DAB)
all in m2/s, and a derivative of the concentration of a property with respect to the distance on
the right hand side. In all the above cases, the flux is proportional to the driving force. These
three molecular transport equations are mathematically identical. Thus, we say that we have
an analogy or similarity among them. Even though there is a mathematical analogy among
them, the actual physical mechanisms occurring is totally different.
The mass diffusivity DAB, the kinematic viscosity, ν and thermal diffusivity, α are
analogous as seen from the above equations.
The similarity in nature of transfer of these three processes are referred to as analogy.
Considering similarities between the governing equations of heat, mass and momentum
transfer, it is to be expected that the correlations for heat transfer coefficients and mass
transfer coefficients would also be similar. Various quantitative relations are available to
describe the analogical behaviour. The simplest and oldest is due to Reynolds.
Unit Operations – II 7.27 Diffusion

The Reynolds Analogy :

Reynolds was first to note similarities in transport processes and relates turbulent
momentum and heat transfer.
The basic assumption of the Reynolds analogy is that the ratio of two molecular
diffusivities equals to that of two eddy diffusivities.
ν εM
= NPr = … (7.104)
α εH
For turbulent flow conditions, the Reynolds analogy equations are :
The statement of Reynolds analogy between heat and momentum transfer is :
h h f
= C G = NSt = 2 … (7.105)
Cp u ρ p

The statement of Reynolds analogy between mass and momentum transfer is :

'
kc f
u = 2 … (7.106)

Therefore, the complete Reynolds analogy is

'
h kc f
= u = 2 … (7.107)
Cp u ρ
f
NSt = NStm = 2 … (7.108)

where f is the Fanning friction factor (a measure of skin friction), u is the average velocity of
'
fluid, kc is the convective mass transfer coefficient, h is the convective heat transfer
coefficient.
Equation (7.107) agrees well with the experimental data (correlates data) for gases in
turbulent flow if the Schmidt and Prandtl numbers are about unity and only the skin friction
is present in a flow past a flat plate or inside pipe. The equations do not correlate the data for
liquids in turbulent flow nor for any fluids in laminar flow, i.e., in such cases the analogy is
not valid.
Although the Reynolds analogy is of limited utility, the significant conclusion that may
be drawn is the mechanisms for momentum, heat and mass are identical at NPr = NSc = 1.0.
If a measure of the skin friction, i.e., the fanning friction factor is known, the analogy
may be used to find the heat transfer coefficient from the mass transfer coefficient and
vice-versa.
Unit Operations – II 7.28 Diffusion

SOLVED EXAMPLES
Example 7.1 : A large tank filled with a mixture of gases A and B at 101 kPa and 298 K
(25 oC) is connected to another large tank filled with a mixture of A and B of different
compositions of A and B at 101 kPa and 298 K (25 oC). The tanks are connected by a tube of
inner diameter of 50 mm and is 150 mm long. Calculate the steady state rate of transport of
A through the tube when the concentration of A in one tank is 90 mole % and in the other is
5 mole % assuming uniformity in the composition in each tank and transfer takes by
molecular diffusion. The diffusivity of A in B is 4.3 × 10–3 m2/s.
90
Solution : Mole fraction of A in tank–1 = xA1 = 100 = 0.90

5
Mole fraction of A in tank–2 = xA2 = 100 = 0.05

DAB = 4.3 × 10–3 m2/s

z = 150 mm = 0.15 m = length of diffusion path
π π
Area = 4 D2 = 4 × (0.05)2 = 1.963 × 10–3 m2

pA1 = xA1 . P = 0.9 × 101 = 90.9 kPa

pA2 = xA2 . P = 0.05 × 101 = 5.05 kPa
R = 8.31451 m3. kPa/(kmol.K)
DAB (pA1 – pA2)
Rate of transport of A = NA · A = RTz × A

4.3 × 10–3 × (90.9 – 5.05) × 1.963 × 10–3

=
8.31451 × 298 × 0.15
= 1.95 × 10–6 kmol/s … Ans.
Example 7.2 : In an oxygen-nitrogen gas mixture at 101.3 kPa and 298 K, the
concentrations of oxygen at two planes 2 mm apart are 20 and 10% by volume respectively.
Calculate the flux of diffusion of oxygen for the cases where :
(i) nitrogen is non-diffusing
(ii) there is equimolar counter diffusion of the two gases. Diffusivity of O2 in N2 is
1.81 × 10–5 m2/s.
Solution : 1. For the diffusion of A through a non-diffusing B, the flux is given by
DAB P
NA = RTz p (pA1 – pA2) … (1)
B, M

Total pressure, P = 101.3 kPa

For an ideal gas, volume % = mole %. Therefore, mole % of O2 = volume % of O2
Unit Operations – II 7.29 Diffusion

20
∴ xA1 = 100 = 0.20

10
xA2 = 100 = 0.10

Partial pressure of A = Molefraction of A × Total pressure

pA1 = xA1 P = 0.20 × 101.3 = 20.26 kPa
pA2 = xA2 P = 0.10 × 101.3 = 10.13 kPa
We have, P = pA1 + pB1
∴ pB1 = 101.3 – 20.26 = 81.04 kPa
pB2 = 101.3 – 10.13 = 91.17 kPa
pB, M = (pB2 – pB1) / ln (pB2 / pB1)
= (91.17 – 81.04) / ln (91.17 / 81.04) = 86 kPa
z = 2 mm = 2 × 10–3 m, DAB = 1.81 × 10–5 m2/s
R = 8.31451 [Link] / (kmol.K), T = 298 K
Substituting the values, Equation (1) gives
1.81 × 10–5 [20.26 – 10.13] × 101.3
NA =
8.31451 × 298 × 2 × 10–3 × 86
= 4.356 × 10–5 kmol/(m2.s) … Ans.
2. The flux for the equimolar counter diffusion is given by
DAB
NA = RTz (pA1 – pA2)

1.81 × 10–5 × (20.26 – 10.13)

=
8.31451 × 298 × 2 × 10–3
= 3.7 × 10–5 kmol/(m2.s) … Ans.
Example 7.3 : Methane diffuses at steady state through a tube containing helium.
At point 1, the partial pressure of methane is 55 kPa and at point 2 it is 15 kPa. The points
1 and 2 are 30 mm apart. The total pressure is 101.3 kPa and temperature is 298 K (25 oC).
Calculate the flux of CH4 at steady state for equimolar counter diffusion. The diffusivity of
methane at the prevailing conditions is 6.75 × 10–5 m2/s.
Solution : The flux for the equimolar counter diffusion is given by
DAB
NA = RTz (pA1 – pA2)

where, DAB = 6.75 × 10–5 m2/s, R = 8.31451 [Link]/(kmol.K)

T = 298 K , z = 30 mm = 0.03 m
Unit Operations – II 7.30 Diffusion

pA1 = 55 kPa, pA2 = 15 kPa

6.75 × 10–5 (55 – 15)
NA =
8.31451 × 298 × 0.03
= 3.63 × 10–5 kmol / (m2.s) … Ans.
Example 7.4 : Ammonia gas (A) diffuses through a non-diffusing nitrogen gas (B) under
steady state conditions. The partial pressure of A at location 1 is 1.5 × 104 Pa and that at
location 2 is 5 × 103 Pa (Pascal). The locations 1 and 2 are 0.15 m apart. The total pressure
is 1.103 × 105 Pa and temperature is 298 K. Calculate the flux of diffusion of ammonia. Also
calculate the flux of diffusion for equimolar counter diffusion considering that nitrogen is
also diffusing. The diffusivity of ammonia at the prevailing conditions is 2.30 × 10–5 m2/s.
Solution : 1. The flux equation for the diffusion of A through a non-diffusing B is
given by
DAB P
NA = RTz p (pA1 – pA2)
B, M

where DAB = 2.30 × 10–5 m2/s

P = 1.103 × 105 Pa
pA1 = 1.5 × 104 Pa
pA2 = 5 × 103 Pa
pB1 = P – pA1 = 1.103 × 105 – 1.5 × 104 = 8.63 × 104 Pa
pB2 = P – pA2 = 1.103 × 105 – 5 × 103 = 9.63 × 104 Pa
pB2 – pB1
pB, M = ln (p / p )
B2 B1

(9.63 × 104 – 8.63 × 104)

=
ln (9.63 × 104/8.63 × 104)
= 9.121 × 104 Pa
T = 298 K, z = 0.15 m
R = 8.31451 m3. kPa/(kmol.K) = 8314.51 [Link] / (kmol.K)
2.30 × 10–5 × 1.103 × 105 (1.5 × 104 – 5 × 103)
NA =
8314.51 × 298 × 0.15 × 9.121 × 104
= 7.484 × 10–7 kmol/(m2.s) … Ans.
2. The flux equation for the equimolar counter diffusion is given by
DAB
NA = RTz (pA1 – pA2)
2.30 × 10–5 (1.5 × 104 – 5 × 103)
=
8314.51 × 298 × 0.15
= 6.19 × 10–7 kmol/(m2.s) … Ans.
Unit Operations – II 7.31 Diffusion

Example 7.5 : Hydrochloric acid (A) at 283 K diffuses through a thin film of water (B).
The film is 4 mm thick. The concentration of A at location 1, on one boundary of the film, is
12 weight % (density ρ1 = 1060.7 kg/m3) and at location 2, on the other boundary, is
4 weight % (density ρ2 = 1020.15 kg/m3). The diffusivity of HCl in water is 2.5 × 10–9 m2/s.
Calculate the flux of diffusion of A assuming water to be stagnant (i.e., non-diffusing).
Solution : Molecular weight of HCl = 36.5, Molecular weight of H2O = 18
At location 1 : Mole fraction of HCl (A)
12/36.5
xA1 = 12/36.5 + (100 – 12)/18

= 0.063
We have : xA1 + xB1 = 1
∴ xB1 = 1 – 0.063
= 0.937
Average molecular weight at location-1 is
100
M1 = 12/36.5 + (100 – 12)/18

= 19.166 kg/kmol
OR : In 100 kg of HCl – water mixture, there are 12 kg of HCl and 100 – 12 = 88 kg of H2O
at location-1 (as at location-1, HCl concentration is 12 weight %).
12 88
moles of HCl = 36.5 = 0.3287 kmol, moles of H2O = 18 = 4.8888 kmol

Total moles of the mixture = 0.3287 + 4.8888 = 5.2175 kmol

Moles of HCl 0.3287
∴ xA1 = Total moles = 5.2175 = 0.063

M1 = kg of mixture / kmol of mixture

100
= 5.2175 = 19.166 kg/kmol

At location–2, the molefraction of HCl is

4/36.5
xA2 = (4/36.5) + (100 – 4)/18

0.1096
= 0.1096 + 5.3333 = 0.0201

xB2 = 1 – 0.0201
= 0.9799
Unit Operations – II 7.32 Diffusion

Average molecular weight at location-2 is

100
M2 = 4/36.5 + 96/18
= 18.3728 kg/kmol
ρ1/M1 + ρ2/M2
Cavg = 2
(1060.7/19.166) + (1020.15/18.3728)
= 2
= 55.4336 kmol/m 3

xB, M = (xB2 – xB1) / ln (xB2 / xB1)

= (0.9799 – 0.937) / ln (0.9799/0.937)
= 0.958
z = 4 mm = 0.004 m
The flux equation for the diffusion A through a non-diffusing B is given by
DAB Cavg
NA = x . z (xA1 – xA2)
B, M

2.5 × 10–9 × 55.4336 (0.063 – 0.0201)

=
0.958 × 0.004
Flux of HCl = 1.55 × 10–6 kmol/(m2.s) … Ans.
Example 7.6 : Calculate the rate of diffusion of acetic acid (A) across a film of non-
diffusing water (B) which is 1 mm thick at 290 K if the concentrations of acetic acid on the
opposite sides of the film are 9% and 3% respectively. The densities of 9% and 3% solutions
are 1012 kg/m3 and 1003.2 kg/m3 respectively. The diffusivity of acetic acid in water is
0.95 × 10–9 m2/s.
Solution : DAB = 0.95 × 10–9 m2/s, z = 1 mm = 1 × 10–3 m
At location 1, on one side of the film :
ρ1 = 1012 kg/m2, Acetic acid = 9% by weight
Mol. Wt. of acetic acid (CH3COOH) = 60, Mol. Wt. of water (H2O) = 18.
In 100 kg mixture there are 9 kg of acetic acid and 91 kg of water
moles of A 9/60
∴ xA1 = Total moles = 9/60 + (100 – 9)/18

0.15
= 0.15 + 5.05

0.15
= 5.2 = 0.0288

kg of solution 100
M1 = Average molecular weight of solution = kmol of solution = 5.2 = 19.21 kg/kmol
Since xA1 + xB1 = 1
xB1 = 1 – 0.0288 = 0.9712
Unit Operations – II 7.33 Diffusion

At location-2, on the other / opposite side of the film :

Weight % of acetic acid = 3%, ρ2 = 100.3 kg/m3
3/60
∴ xA2 = 3/60 + (100 – 3)/18 = 0.0092
and xB2 = 1 – 0.0092 = 0.9908
100
M2 = 3/60 + (100 – 3)/18 = 18.40
ρ1/M1 + ρ2/M2
Cavg. = 2
(1012/19.21) + (1003.2/18.40)
= 2
= 53.6 kmol/m 3

xB, M = (xB2 – xB1)/ ln (xB2 /xB1)

= (0.9908 – 0.9712)/ ln (0.9908/0.9712)
= 0.980
The flux of acetic acid is
DAB . Cavg
NA = z.x (xA1 – xA2)
B, M

0.95 × 10–9
= (0.0288 – 0.0092)
1 × 10–3 × 0.98
= 1.018 × 10–6 kmol/(m2.s) … Ans.
Example 7.7 : Hydrogen gas at 202.6 kPa (2 atm) and 298 K (25oC) flows through a
pipe made of unvulcanised neoprene rubber with i.d. and o.d. 25 and 50 mm, respectively.
The diffusivity of hydrogen through rubber is 1.8 × 10–6 cm2/s. Calculate the rate of loss of
hydrogen by diffusion per meter length of the pipe.
The solubility of hydrogen is 0.053 cm3 (NTP)/cm3·atm.
Solution : Consider 1 m of the pipe,
o.d. – i.d. 50 – 25
z = r2 – r1 = 2 = 2 = 12.5 mm = 0.0125 m
DA = 1.8 × 10–6 cm2/s = 1.8 × 10–10 m2/s
L = 1m
2πL (r2 – r1) 2π (1) (0.0125)
Aavg. = ln (r /r ) = ln (0.025/0.0125)
2 1

= 0.1133 m2
At 202.6 kPa (2 atm) hydrogen pressure, the solubility is
2
= 0.053 × 1 = 0.106 cm3 (NTP)/cm3
= 0.106 m3 (NTP)/m3
Unit Operations – II 7.34 Diffusion

0.106
∴ CA1 at the inner surface of the pipe = 22.4 × 1 = 4.73 × 10–3 kmol H2/m3

At the outer surface, CA2 = 0

The rate of loss of hydrogen per 1 m length of the pipe is
w = NA · Aavg. = DA · Aavg. [CA1 – CA2]/z
= 1.8 × 10–10 × 0.1133 (4.73 × 10–3 – 0)/0.0125
= 7.72 × 10–2 kmol H2/s per m … Ans.
Some Important Definitions :
1. Gram mole : It is defined as the mass in grams of a substance that is numerically
equal to its molecular weight.
In this book, gram mole and kilogram mole are specified as mol and kmol respectively.
2. Weight fraction : It is the ratio of the weight of the individual component to
the total weight of the system. It is denoted by the symbol x'.

For two component system : x'A + x'B = 1.0.

Weight % of A = Weight fraction of A × 100
3. Mole fraction : It is the ratio of the moles of the individual component to the total
moles of the system. It is denoted by the symbol x.
For a binary system of A and B : xA + xB = 1.0.
Mole % of A = mole fraction of A × 100.
4. More volatile component : It is the component with a lower boiling point or with a
higher vapour pressure at a given temperature (in a binary system). It is also called as the
lighter component.
In case of distillation, the compositions of vapour and liquid phases are expressed in
terms of mole fraction of the more volatile component.
5. Less volatile component : In a binary system, it is the component with a higher
boiling point or with a lower vapour pressure at a given temperature. It is also called as the
heavier component.
6. Vapour pressure : The vapour pressure of a liquid is defined as the absolute
pressure at which the liquid and its vapour are in equilibrium at a given temperature.
7. Partial pressure : The partial pressure of a component gas that is present in a
mixture of gases in the pressure that would be exerted by that component if it alone were
present in the same volume and at the same temperature as the mixture.
8. Ideal gas law : The ideal gas law is given by
PV = nRT
if P is in kPa, V in m3, n in kmol and T in K then R will be in m3·kPa/(kmol·K).
R (universal gas constant) = 8.31451 m3 · kPa/(kmol·K)
Unit Operations – II 7.35 Diffusion

9. Dalton's law : Mathematically, Dalton's law is given by

P = pA + pB + pC + …
where P is the total pressure exerted by a gas mixture and pA, pB, pC … are the partial
pressures of component gases A, B, C, …. present in the mixture.
10. Raoult's law : It states that the equilibrium partial pressure of component A is equal
to the product of the vapour pressure and the mole fraction of A in the liquid phase.
0
∴ pA = pA · xA
pA is also related to yA by the following equation
pA = yA · P
yA is the mole fraction of A in the gas phase.
11. Henry's law : Mathematically Henry's law is given as,
pA = H xA
where H is the Henry's law constant.
Henry's law expresses the relationship between the concentration of a gas dissolved in a
liquid and the equilibrium partial pressure of the gas above the liquid surface.
12. Gibb's phase rule : It is the relationship that governs all heterogeneous equilibria. It
is given by
F = C–P+2
where C = number of components
P = number of phases
F is the number of degrees of freedom or number of intensive variables (temperature,
pressure, composition) that must be specified so that remaining variables will be fixed
automatically and the system will be defined completely.
EXERCISES
1. Give the mathematical statement of Fick's law of diffusion and give the meaning of
each terms involved in it.
2. Define :
(i) Mass fraction,
(ii) Mole fraction,
(iii) Molar concentration,
(iv) Mass average velocity, and
(v) Molar average velocity.
3. Define : Mass flux and Molar flux and give the expressions for Mass and Molar
fluxes relative to the mass average velocity and molar average velocity.
 CHAPTER NINE

GAS ABSORPTION

In gas absorption, a gas phase contacts a liquid phase and mass is transferred from the
gas phase to the liquid phase (liquid solvent).
Gas absorption refers to an operation in which a gas mixture is contacted with a liquid
to preferentially dissolve one or more soluble components of the gas mixture in the liquid.
This unit operation is also termed as scrubbing. The differences in solubility of gases in a
given solvent are utilised to effect such a separation. Gas absorption is the second most
important mass transfer operation encountered in the chemical industry and is used for the
recovery or removal of the solute gas.
In absorption, the soluble component of a gas mixture is called as the solute gas, the
insoluble component is called as the inert gas or carrier gas and the liquid used for absorption
purpose is called as the solvent or absorbent. Under a given set of operating conditions, the
volatility of the solvent used is very low, so it is essentially immiscible in the gas phase. A
typical example of gas absorption is the removal of ammonia from a mixture of ammonia
and air using water as a solvent. Here, since ammonia is soluble in water, air is almost
insoluble and water does not vapourise to an appreciable extent in the gas mixture at ambient
temperature, the only transfer is of ammonia from the gas phase to the liquid phase.
The reverse of absorption is called desorption or stripping. It is an operation in which a
dissolved gas from a solution (a liquid) is removed from the liquid by contacting it with an
inert gas (i.e., a stripping medium). Therefore, the removal of sulfur dioxide from flue gases
by alkaline solutions is an example of absorption, whereas the removal of the volatile
components of oil by steam is an example of stripping.
The absorption may be a purely physical phenomenon - physical absorption, e.g.,
absorption of ammonia from a mixture of ammonia and air by water or it may be
accompanied by a chemical reaction (the transfer of a solute component to the liquid phase
and then reaction of this solute with a constituent of the liquid), e.g., absorption of NO2 in
water to produce nitric acid. Gas absorption is exothermic in nature, so this operation
demands a cooling provision and is normally carried out at low temperatures (since the
solubility of a solute gas in a given solvent is high at low temperatures).

(9.1)
Unit Operations – II 9.2 Gas Absorption

Comparison of gas absorption and distillation :

Absorption Distillation
1. Gas absorption deals with the 1. Distillation deals with the separation of
separation of the constituents of a gas the constituents of a liquid mixture.
mixture.
2. In gas absorption, the constituents of a 2. In distillation, the constituents of a liquid
gas mixture are separated by using mixture are separated by using thermal
liquid solvent. energy.
3. Liquid solvent used in gas absorption is 3. Liquid in distillation operation is at its
below its boiling point. bubble point.
4. In gas absorption, a gas phase contacts 4. In distillation, a vapour phase contacts a
a liquid phase and mass (solute) is liquid phase and mass is transferred both
transferred from the gas phase to liquid from the liquid phase to the vapour phase
phase (i.e., mass transfer takes place in and from the vapour phase to the liquid
one direction). It is a case of steady phase (i.e., mass transfer takes place in
state diffusion of A through a non- both the directions simultaneously). It is a
diffusing B. case of steady state equimolar counter
diffusion.
5. Gas absorption does not yield a pure 5. Distillation yields almost pure product in
product. It needs further processing for a single processing step.
the recovery of the solute/solvent
(usually by distillation).
6. In gas absorption, heat effects are 6. In distillation, heat effects are attributed
attributed to the heat of solution of the to the latent heats of vaporisation and
dissolved gas. condensation.
7. Gas in absorption operation is well 7. Vapour in distillation is always at its dew
below its dew point. point.
8. Example – the removal of SO2 from 8. Example – separation of petroleum crude
flue gases by alkaline solutions. into gasoline, kerosene, fuel oil, etc.
9. Packed towers are widely used for 9. Plate towers are widely used for
absorption operation. distillation operation.
10. The difference in solubility of gases in 10. The difference in vapour pressures
a given solvent is responsible to effect (volatilities) of different components at
the separation by absorption. the same temperature solution is
responsible to effect the separation by
distillation.
Though both the gas absorption and distillation operations can be carried out in plate or
packed columns, packed columns are very common for absorption.
Condition of Equilibrium : Liquid-Gas :
The degree to which a gas is absorbed from a gaseous mixture by a liquid solvent is
determined by its partial pressure. Each dissolved gas exerts a definite partial pressure at a
given temperature and concentration. The gas is said to be slightly soluble when the partial
pressure exerted by the dissolved gas from the solution is higher, while it is said to be more
Unit Operations – II 9.3 Gas Absorption

soluble when the partial pressure exerted by the dissolved gas from the solution of given
concentration is lower. Thus, oxygen is slightly soluble, while ammonia is highly soluble in
water. With water as a solvent, ammonia is very soluble gas, sulphur dioxide is moderately
soluble gas and oxygen is slightly soluble gas.
A given quantity of liquid will dissolve any amount of a slightly or more soluble gas
depending upon the partial pressure of the dissolved gas in the gas phase in contact with the
liquid. A slightly soluble (insoluble gas) gas requires a higher partial pressure of the gas in
contact with the liquid to yield the solution of a desired concentration, while a very soluble
gas requires very low partial pressure to give the solution of the same concentration.
Equilibrium condition will be reached when the partial pressure of solute gas in the gas
phase is equal to its partial pressure from the liquid phase. The equilibrium condition thus
fixes the upper limit for operation of an absorption unit.
The solubility of a gas (the concentration of a dissolved gas in the liquid at a given
temperature and pressure) is not substantially affected by the total pressure over the system
but gets influenced by the temperature. Generally, the solubility of a gas in a given solvent
decreases with increase in temperature.
In a majority of cases, the gas absorption results with the evolution of heat and solubility
falls off if provisions are not made to remove the heat evolved. Usually adequate cooling
arrangements are provided to keep the temperature sufficiently low to achieve a good rate of
absorption.
For dilute solutions of most gases, the equilibrium relationship is given by Henry's law :
pA = H · xA … (9.1)
where pA is partial pressure of the solute gas A in the gas phase
xA is mole fraction of the solute gas A in the liquid phase (the
concentration of A in terms of mole fraction)
H is the Henry's law constant.
Please refer to Equilibrium - Chapter 7 for Equilibrium in gas absorption.
Selection criteria for solvent in gas absorption :
While selecting a particular solvent for absorption operation, the following properties of
the solvent are considered :
1. Gas solubility :
The solubility of a solute gas in a solvent should be high, i.e., the solvent should have a
high capacity for dissolving the desired solute gas so that the less amount of the solvent will
be required for a given absorption duty. In general, for good solubility, a solvent of chemical
nature similar to that of the solute to be absorbed must be searched out and used.
The solvent selected should have a high solubility for the solute to be absorbed.
2. Volatility :
As the gas leaving an absorption unit is generally saturated with the solvent, there will be
a loss of the solvent with the gas leaving the unit operation. Hence, to minimise the solvent
loss (in the gas leaving), the solvent should be less volatile, i.e., it should have a low vapour
pressure under given operating conditions.
Unit Operations – II 9.4 Gas Absorption

3. Corrosive nature :
The solvent should not be corrosive (as far as possible) towards common materials of
construction so that the construction material for an absorption equipment will not be too
expensive.
4. Viscosity :
The solvent should have a low viscosity for rapid absorption rates, low pumping cost and
better heat transfer. The solvent should be non-viscous.
5. Cost and availability :
The solvent should be cheap and readily available. Losses are less costly with the cheap
solvent.
6. Miscellaneous :
The solvent should be non-toxic, non-flammable, non-foaming, and chemically stable
from a handling and storage point of view.
Material balances – One Component Transferred :
Consider a packed column as shown in Fig. 9.1. Let V1, V2 and V be the molal flow rates
of the total gas at the inlet (rich gas), outlet (lean gas) and at an arbitrary section in the
column, respectively. Let y1, y2 and y be the mole fractions of the solute gas at the respective
stations.
x2, X2, L2 V2, y2, Y2
L' V'

L, x V, y

x1, L1, X1 V1, Y1, y1

Fig. 9.1 : Material balance diagram for Absorption tower
Let L1, L2 and L be the molal flow rates of the liquid (as a whole) at the outlet, inlet and
at an arbitrary sections, respectively and x1, x2 and x be the mole fractions of the solute gas in
the liquid at the respective stations. Also let V' and L' be the molal flow rates of the inert
(insoluble) gas and the non-volatile solvent (solute free solvent), respectively through the
column.
The overall material balance over the control surface 'A' of Fig. 9.1 gives
V1 + L = L1 + V … (9.2)
Material balance of the solute component over the control surface A of Fig. 9.1 :
V1 y1 + L x = L1 x1 + V y … (9.3)
Unit Operations – II 9.5 Gas Absorption

The overall material balance over the entire column is

V1 + L2 = V2 + L1 … (9.4)
The material balance of the solute over the entire column is
V1 y1 + L2 x2 = L1 x1 + V2 y2 … (9.5)
where y is the mole fraction of the solute in the gas phase
and (1 – y) is the mole fraction of the inert gas in the gas phase
Therefore, V' = V (1 – y) = V1 (1 – y1) = V2 (1 – y2) … (9.6)
Similarly, (1 – x) be the mole fraction of the solute free solvent in the liquid phase.
∴ L' = L (1 – x) = L1 (1 – x1) = L2 (1 – x2) … (9.7)
Equation (9.3) becomes
 y1   x1 
V' 1 – y  + L' 1 – x = L' 1 – x  + V' 1 – x
x y
… (9.8)
 1    1  
 y1 y   x1 x 
∴ V' 1 – y – 1 – y = L' 1 – x – 1 – x … (9.9)
 1   1 
Let Y and X be the mole ratio defined as :
y
Y = 1–y

= moles solute per mole of solute-free gas (inert gas)

x
X = 1 – x moles solute per mole of solute-free solvent.

(As in 1 mole of a gas mixture, there will be y moles of the solute gas and (1 – y) moles
of the inert gas (insoluble gas).
Equation (9.9) is the equation of the operating line for absorption operation in terms of
mole fraction and is a curve on x - y co-ordinates.
Equation (9.9) in terms of mole ratio is :
V' [Y1 – Y] = L' [X1 – X] … (9.10)
Equation (9.10) is the equation of the operating line for absorption operation. It is a
straight line on x - y co-ordinates with a slope equal to L'/V' and passes through point
(X1, Y1). The line also passes through point (X2, Y2).
Material balance of the solute gas component over the entire tower/column in terms of
L', V' and mole ratios is :
V' [Y1 – Y2] = L' [X1 – X2] … (9.11)
If the solvent used is pure/fresh, x2 = 0 and X2 = 0, then the above equation becomes
V' [Y1 – Y2] = L' (X1) … (9.12)
Minimum Liquid Gas Ratio : Refer to Fig. 9.2.
Unit Operations – II 9.6 Gas Absorption

Consider that the values of the terms V', Y1, Y2 and X2 are fixed by a process requirement
and the value of L' is decreased through the absorption tower. The operating line on X, Y
coordinates passes through the point (X2, Y2) and has a slope equal to L'/V'. As the liquid
flow rate is decreased, the slope of the operating line decreases (operating line shifts toward
the equilibrium curve) and the exist liquid composition (with respect to the solute) increases
from X' to X" as indicated by line AC. A reduction in the liquid flow rate reduces the
1 1
driving force for mass transfer and absorption becomes more and more difficult. Further
reduction in the liquid flow rate leads to a situation wherein the upper end of the operating
line touches the equilibrium curve as indicated by line AD and the exist liquid composition is
then in equilibrium with the inlet gas. Thus, the driving force for mass transfer becomes zero
at the bottom of the tower, required time of contact for the desired concentration change
becomes infinite, and an infinitely tall tower is required. The value of L'/V' corresponding to
this situation (corresponding to the line AD) represents a minimum liquid-gas ratio. If tower
is to operate practically, the liquid flow rate should be greater than that corresponding to the
minimum L'/V' ratio.
Low values of L'/V' ratio result into taller tower and hence there is an increase in the
fixed cost but the recovery cost of the solute will be low (due to small quantities of liquid).
High values of L'/V' ratio result into small tower due to favourable driving force, and hence,
there is a decrease in the fixed cost but the recovery cost of the solute will be higher.
Therefore, while selecting L'/V' ratio, a balance must be made between the fixed and the
recovery costs. In general, the operating liquid flow rate for the absorber is usually 1.1 to 1.5
times the minimum.

B C D
Y1
Operating
line for
Y minimum
L'/V' ratio
)
/V'

moles
(L'

solute Equilibrium
moles curve
inert
gas

Y2 A
X'1 X''1 X1
X2 moles X
solute
moles
solvent
Fig. 9.2 : Minimum liquid-gas ratio for absorption
Pressure drop in packed columns :
In packed columns operated in a counter current fashion, the liquid fed at the top flows
downward under the influence of gravity/gravitational force and the gas fed at the bottom of
the column is moved upward by a fluid moving machinery such as a blower or fan. So as to
Unit Operations – II 9.7 Gas Absorption

maintain the upward flow of gas, pressure at the top must be less than at the bottom. In
packed columns since the same channels are available for liquid downflow and gas upflow,
the gas pressure drop is a function of both the phase flow rates and further its knowledge is
must as it is a important factor in the design of packed towers.
In randomly packed towers, the dependency of a gas pressure drop on the gas and liquid
flow rates is similar to that shown in Fig. 9.3 wherein the pressure drop per unit height of
packed bed is plotted against the superficial gas mass velocity (mass flow rate per unit empty
tower cross-section) on logarithmic co-ordinates.
In case of dry packing (L = 0), the relationship between pressure drop and gas mass
velocity is represented by a straight line A indicating that the pressure drop is proportional to
(V/A)1.8 – 2 which is consistent with a usual law of fluid friction in turbulent flow. For wet
packing, the relationship is indicated by a straight line B similar to the line A (for dry
packing) but for a given velocity, the pressure drop will be more than that for dry packing.
If in addition to gas flow, liquid flows down the tower at a fixed gas velocity, the pressure
drop increases with increased liquid flow rate (see lines C and D) as most of the free space in
the packed bed gets occupied by the liquid, i.e., the free cross-section available for the gas
flow becomes smaller and smaller as liquid flow increases.
D C
B
Y Y A
Pressure drop

X X Dry
packing
uid igh
Liq ow te
rate
ra
H

Wet
uid

packing
Liq
L

Gas mass velocity

(Log - Log co-ordinates)

Fig. 9.3 : Pressure drop characteristics of packed column (logarithmic axes)

With liquid flowing down the tower at low and moderate gas velocities, the pressure drop
is proportional to 1.8 th power of the gas velocity but is greater than that for wet packing as
liquid flow occupies part of the free cross-section available for the gas flow. Upto point 'X'
the amount of liquid held in packings is constant. At point 'X', the gas flow begins to impede
the downflow of liquid and the local accumulation of liquid appears here and there in
packings.
As the gas velocity increases further (beyond X upto Y), the liquid hold up progressively
increases due to which the free area for the gas flow becomes smaller and the pressure drop
rises much more quickly (pressure drop is proportional to 2.5 th power of the gas mass
velocity over the X-Y section). At gas flow rates beyond Y, the pressure drop rises very
steeply for a given liquid flow rate. Point X is called as the loading point and point Y is
called as the flooding point. At a given liquid flow rate at point Y, a layer of liquid may
Unit Operations – II 9.8 Gas Absorption

appear at the top of packings or inversion of phases may occur (the liquid becomes the
continuous phase and the gas becomes the dispersed phase) and the entrainment of liquid by
the gas leaving the top of the tower increases rapidly and tower is then said to be flooded.
The gas velocity corresponding to the flooding conditions is called as the flooding velocity.
The point at which the liquid hold up in the column starts to increase, as indicated by a
change in the slope of the pressure drop line, it is called the loading point.
From this point onward the present drop increases more rapidly with increase in gas
velocity.
If tower is to operate practically, the operating gas mass velocity must be lower than the
flooding velocity. For safe operations, the packed towers are designed using gas velocities of
about 50 to 70 per cent of the flooding velocity at the expected liquid rate. This value
corresponds to the one somewhere below the loading point and thus, ensures stable operating
conditions.
Gas Absorption Equipments :
Various gas absorption equipments used are :
1. Mechanically agitated vessels.
2. Packed Columns/towers.
3. Plate Columns.
1. Mechanically agitated vessel :
Gas in

Gas in

Turbine
agitator

Baffle
Turbine (4 Nos)
agitator Vessel

Baffle
(4 Nos)
Sparger
Vessel

Sparger

Fig. 9.4 : Standard mechanically agitated Fig. 9.5 : Multiple impeller for deep
vessel vessels
Unit Operations – II 9.9 Gas Absorption

It is usually used in a small scale industry. This unit gives performance equivalent to one
theoretical stage. It consists of a baffled vessel usually incorporating an open or disc flat
blade turbine type agitator as it maintains very large discharge velocities normal to the gas
flow. Solvent liquid with a depth equal to the vessel diameter is taken in the vessel and gas is
introduced below the impeller through a ring shaped sparger under agitation. Adequate free
board is provided over the liquid level for the gas hold up during gas flow and ultimately the
unabsorbed gas leaves the top of the vessel. For a high absorption capacity, the operation is
carried out at low temperature and for maintaining it, a cooling coil is incorporated in the
vessel. The diameter of sparger is equal to or slightly less than that of the impeller and is
arranged with holes (3 to 6.5 mm in diameter) on top.
Deep vessels with usually two impellers are used when the time of contact required is
relatively large, wherein a large interfacial area is maintained by redispersing the gas bubble
coalesced.
2. Packed Columns/Towers :
Packed columns are most frequently used for gas absorption (and are used to a limited
extent for distillation) wherein the liquid is dispersed in the form of film and the gas flows as
a continuous phase. These are continuous contact equipments generally operated in a counter
current fashion.
Liquid in

Liquid
distributor Gas out

Packings

Gas in Perforated
support plate

Liquid out
Fig. 9.6 : Packed tower / Column for absorption
A packed column consists of a vertical cylindrical shell constructed out of metal, plastic,
ceramic, etc. and filled with suitable packings which offer a large interfacial area for gas-
liquid contact for mass transfer between the phases. A bed of the packing rests on a support
plate which offers very low resistance to gas flow. It is provided with a gas inlet and
distributing space at the bottom, a liquid inlet and a liquid distributor at the top and gas and
liquid outlets at the top and bottom. A liquid solvent is introduced from the top through the
liquid distributor (which distributes the liquid on the packing), which irrigates/wets the
Unit Operations – II 9.10 Gas Absorption

surface of packing uniformly, liquid trickles down the bed, and finally the liquid enriched in
the solute to be absorbed called a strong liquor (solute + solvent) leaves the bottom of the
column. The liquid flow rate should be sufficient for good wetting of packing. A solute-
containing gas (rich gas) is introduced from the bottom of the tower and rise upward through
the interstices/open spaces in the packing counter current to the flow of the liquid. The lean
gas (dilute gas) leaves the column from the top of the tower. In case of tall columns/towers,
liquid redistributors are used to redistribute the liquid to avoid channeling of the same (flow
the liquid along the wall).
Advantages of packed columns :
(i) Minimum structure (ii) low pressure drop (iii) low liquid hold-up (iv) handle
corrosive liquids and liquids that tends to foam (v) low initial investment and (vi) high liquid
to gas ratios.
Disadvantages of packed columns :
(i) Relatively inflexible (ii) can not operate over wide ranges of either vapour or liquid
rates per unit cross section (iii) distribution of liquid is difficult (iv) can not handle dirty
fluids that tend to deposit a sediment on packings (v) can not be used where large
temperature changes are occurred.
Packed columns are well suited for :
1. Small diameters
2. Handling highly corrosive fluids.
3. Handling liquids that tend to foam.
4. Operations where it is important to have a low pressure drop and low liquid hold up.
Tower Packings :
Many types of packings are in use ranging from simple to complex geometric shapes.
Packings are made of ceramics, metals and plastics and vary in size from 6 to 75 mm.
Characteristics of a Tower Packing :
1. It should provide a large interfacial area for phase contacting., i.e., it should have a
large wetted surface area per unit volume of packed space for high efficiencies.
2. It should provide a large void volume or empty space in the packed bed so that
reasonable throughputs of the phases are handled without excessive pressure drop.
3. It should possess good wetting characteristic.
4. It should have a high corrosion resistance.
5. It should be relatively cheap/inexpensive.
6. It should have a low bulk density so that the weight of the entire packed bed is low
which thereby reduces serious support problems.
7. It should possess enough structural strength.
8. It should be chemically inert to the fluids handled in the tower.
Unit Operations – II 9.11 Gas Absorption

Types of packings :
In order to obtain the efficient gas-liquid contact, many different types of packings are
available ranging from simple to complex geometrical shapes but are generally classified as
random packings and regular packings. If the packings are simply dumped into the tower
during installation and fall in a random fashion (the individual pieces are not arranged in any
particular pattern), they are called random packings. The packings arranged in a particular
pattern are called stacked packings.

Pall ring Cross partition ring Intalox saddle

Super intalox packing Intalox saddle

Lessing ring Raschig ring

Fig. 9.7 : Tower Packings
In case of randomly packed installations for obtaining the high and uniform voidage and
preventing breakage, a tower is first filled with liquid (usually water) and packings are then
dumped into it. Most common random packings used in industrial towers are Raschig rings,
Pall rings, Hy-pak, Berl saddles, Intalox saddles, Super intalox saddles, etc. As Pall rings,
Unit Operations – II 9.12 Gas Absorption

and Intalox saddles permit a more economical tower design they are replacing older Raschig
rings and Berl saddles. Pall rings are made out of metal or plastic (poly propylene) and have
the same general form as Raschig rings with height equal to diameter, however portions of
the original cylinder wall are cut with the projections bent inward leaving holes in the wall.
They are generally available in sizes ranging from 16 to 50 mm (5/8 to 2 in).
Berl saddles and Intalox saddles are available in range 6 to 50 mm and are formed out of
plastic or ceramics. They provide more gas-liquid contacting area than the Raschig rings.
Raschig rings are hollow cylinders with their length equal to outside diameter and
usually formed out of ceramic, carbon and metal. They are generally available in a size
ranging from 6 to 100 mm 4 to 4 in . They are simple in construction and relatively cheap
1
 
as compared to other packings. When a single web is added to the inside of the Raschig ring,
the packing is called Lessing ring and when a cross web is added to the Raschig ring, then
the packing formed is called cross partition ring. Added webs provide additional active
surface. They are normally available in a size ranging from 75 to 150 mm (3 to 6 in) and
usually used as stacked packings. Stacked packings offer lower pressure drops for the gas
than random packings for equivalent phase flow rates.
Channeling in Packed Columns :
The tendency of the liquid to segregate towards the walls of a packed column and to flow
along the walls (a region of the greatest void space) is termed as channeling, which leads to
low mass transfer efficiencies. Thus, with a good initial liquid distribution in randomly
packed columns, channeling can be minimised by providing a tower diameter to packing size
ratio greater than 8, i.e., the diameter of the tower should be at least eight times the packing
size (or the packing size smaller than at least one-eighth of the tower diameter).
In packed columns, the region of greatest void space is the region near the wall of the
column since the packing material cannot nest tightly with the plane wall as it does with
itself. It is a natural tendency for the fluid to move toward the region of greatest void space
during its flow.
Height Equivalent to an Equilibrium stage (Theoretical Plate) :
The height equivalent to a theoretical plate (HETP) is the height of a section of packing
that will give the same separation as that achieved with one theoretical plate. The HETP is
determined experimentally and is characteristic of each packing. It depends upon the type
and size of the packing, flow rates of fluids and concentration. The height of a packed
column (i.e., the height of packing) required to effect a given degree separation is calculated
by multiplying the number of theoretical plates required to achieve the same degree of
separation by HETP.
Liquid distribution :
For maximum active surface area, the packing should be wetted completely by the
descending liquid and this can be achieved by its proper distribution. For efficient column
operation, uniform distribution of the liquid at the top of the packed bed is essential. A liquid
distributor is a device that spreads the liquid uniformly across the top of the packing. Several
types of liquid distributors used are : (1) Perforated pipe distributor; (2) Orifice-type
distributor; (3) Trough-type distributor; and (4) Weir-riser distributor.
Unit Operations – II 9.13 Gas Absorption

Support Plate :

Orifice type distributor

Welding ring support plate

Gas

Gas riser

Liquid Liquid
Cap type / Gas injection type
Trough type distributor Support plate

Perforated pipe distributor Wire mesh support

(a) Liquid distributor (b) Support plate for packed towers
Fig. 9.8 : Liquid distributors and support plate
In packed columns, the packing support must be sufficiently strong as it carries the
weight of the entire packed bed and at the same time it must have a large free area for
passage of the gas and liquid phases so as to offer a very low resistance to flow of the phases.
Relative merits of plate and packed towers/columns :
The selection of a particular kind of contactor-plate or packed tower for a given mass
transfer operation, generally rests on the cost and profit considerations but in many cases the
choice can be made on the basis of quantitative analysis of relative merits and demerits of the
plate or packed tower. For selecting the right type of contactor for a given mass transfer duty,
the following merits and demerits should be considered.
1. Plate columns operate over a wide range of liquid flow rates without flooding.
Unit Operations – II 9.14 Gas Absorption

2. Plate columns by repeatedly mixing and separation provide a more positive contact
between fluid phases, whereas packed columns may lead to backmixing or by
passing.
3. Because of the difficulties arising in the dispersion of liquid in a packed tower, a
plate tower is more reliable and needs less safety factors at low liquid to gas mass
velocity ratios.
4. Side streams are very easily taken out from plate towers.
5. For plate towers, design information is generally more readily available and it is
more reliable than it for packed towers.
6. Whenever liquid mixtures containing dispersed solids are to be handled, plate towers
should be preferred as cleaning of the plate is very easy.
7. Whenever intermediate cooling arrangement is required to remove the heat of a
solution or reaction, plate towers are preferred. Cooling coils are easily incorporated
in plate towers.
8. For a given duty, the total weight of a dry plate tower is normally less than the weight
of a packed tower but weight of both towers is approximately the same if the liquid
holdup in the plate tower during the operation is taken into account.
9. For a column diameter more than 1200 mm, packed towers are seldom designed and
for a column diameter less than 600 mm, packings are cheaper than plates.
10. For liquids having tendency to foam, packed towers are usually preferred.
11. High values of liquid-gas ratio are best handled in packed towers.
12. Liquid hold-up is considerably low in packed towers so they are used in cases where
liquid deterioration might occur with high temperatures (i.e., used for handling heat-
sensitive liquids).
13. The pressure drop through a packed tower is usually low which makes the packed
tower particularly desirable for vacuum distillation operations.
14. Packed towers may be more economical than plate towers when highly corrosive
fluids are to be handled because of corrosion resistant ceramic/plastic packings.
15. Plate towers are often preferred when large temperature changes are involved, as in
distillation, thermal expansion or contraction of the equipment component may crush
the packing.
Packed columns and plate columns are the commonly used equipments for gas-liquid
operations such as distillation and gas absorption. They are also used for liquid extraction.
Comparison of packed column and plate column :
Packed columns are differential contactors wherein mass transfer occurs throughout the
length of the contactor and equilibrium is not reached at any point between the phases in
contact, whereas plate columns are stagewise contactors wherein mass transfer occurs
intermittently/stagewise and equilibrium is established between the phases at a number of
discrete stages. In packed columns, packings are used as gas-liquid contacting devices,
Unit Operations – II 9.15 Gas Absorption

whereas in plate columns, plates are used as gas-liquid containing devices. Design of a
packed column mainly involves the calculation of the height of transfer unit and number of
transfer units required to effect a given separation, whereas the design of a plate column
involves the calculation of the number of theoretical stages required to effect a given
separation Constructionwise-packed columns are simple in construction, whereas plate
columns are complex in construction. Raschig rings, pall rings, berl saddles, intalox saddles
are the various types of packings used in packed columns, whereas bubble cap plate, sieve
plate and valve plate are the various types of plates used in plate columns.
The selection of a particular type of equipment for gas-liquid operation in a particular
situation will depend upon many factors such as : efficiency, capacity, pressure drop,
corrosion, hold up, cost, etc.
SOLVED EXAMPLES
Example 9.1 : Ammonia from a ammonia-air mixture is to be absorbed in an absorption
tower using water as a solvent. Data for the absorption system is as follows :
Air flow rate – 200 kg/h
Liquid phase compositions :
At the top of packing – 0.000013 kg NH3/kg H2O
At the bottom of packing – 0.0006 kg NH3/kg H2O
Gas phase compositions :
At the bottom of packing – 0.0084 kg NH3/kg inert gas
At the top of packing – 0.0044 kg NH3/kg inert gas.
Calculate flow rate of water entering the absorption tower.
Solution : Basis : 200 kg/h of air flow to the absorption tower.
Gas out Liquid in

Air - 200 kg/h

Gas in Liquid (solvent + solute)

Fig. Ex. 9.1

'
X1 = NH3 composition at the bottom (in the liquid leaving the tower)
= 0.0006 kg NH3/kg H2O
X2' = NH3 composition at the top (in the solvent entering the tower)
= 0.000013 kg NH3/kg H2O
Y1 = NH3 composition in the inlet gas to the tower
= 0.0084 kg NH3/kg air
Unit Operations – II 9.16 Gas Absorption

Y2 = NH3 composition in the outlet gas from the tower

= 0.0044 kg NH3/kg air
L' = Mass flow rate of solute free solvent in kg/h
V' = Mass flow rate of solute free gas or air in kg/h
For an absorption tower, the overall material balance is
V' [Y1 – Y2] = L' [X1 – X2]
200 [0.0084 – 0.0044] = L' [0.0006 – 0.000013]
L' = 1362.86 kg/h
Mass flow rate of water (solute free) = 1362.86 kg/h … Ans.
Example 9.2 : Gas containing 2 % by volume solute A is fed to an absorption tower at a
rate of 0.35 m3/s at 299 K (26o C) and 106.658 kPa pressure, and 95 % of the original solute
is removed by absorbing it in a solvent B. Solvent containing 0.005 mole fraction of solute
enters the tower at the top and the exit liquid streams from the absorption tower contains
0.12 mole A per mole B. Find out the flow rate of the solvent entering the absorption tower
on solute-free basis.
Solution : Basis : 0.35 m3/s of gas entering the tower.
P = pressure = 106.658 kPa
T = 299 K
Assume that the ideal gas law holds good.
PV = nRT
where R = 8.31451 (m3 · kPa)/ (kmol · K)
n = molal flow rate of gas in kmol/s
V = volumetric flow rate of gas = 0.35 m3/s
Gas out L'
Liquid in
V' X2, x2

2% A
3
0.35 m /s V', y1, Y1
X1, L'

Fig. Ex. 9.2

PV 106.658 × 0.35
n = RT = = 0.015 kmol/s = 15 mol/s
8.31451 × 299
Solute A in the inlet gas = 2 %
y1 = Mole fraction of A in the gas
2
= 100 = 0.02
Mole fraction of inert gas in the inlet gas = 1 – y1
= 1 – 0.02 = 0.98
Unit Operations – II 9.17 Gas Absorption

Moles solute
∴ Y1 = Moles inert gas (solute free gas)
= Mole ratio at the inlet
y1 0.02
Y1 = 1 – y = 1 – 0.02 = 0.020408
1

V' = Molal flow rate of solute free gas (inert gas)

= 15 (1 – y1) = 15 (1 – 0.02) = 14.7 mol/s
Solute A in the inlet
gas per second = 15 × 0.02 = 0.3 mol
95% of the solute is absorbed, i.e., 5% of the solute leaves the tower with the inert gas.
Unabsorbed solute appearing in the gas leaving the tower
= 0.05 × 0.3 = 0.0015 mol/s
Balance of inert gases :
Inert gas leaving the tower = Inert gas entering the tower
= 14.7 mol/s
Y2 = mole ratio at the outlet (gas phase)
moles solute
= moles inert gas
0.015
= 14.7 = 0.0010204
x2 = mole fraction of solute A in the liquid entering tower
= 0.005
moles solute A x2
X2 = mole solute free solvent B = 1 – x
2

∴ X2 = mole ratio at the liquid inlet

0.005
= 1 – 0.005 = 0.005025
moles solute A in exit liquid
X1 = 0.12 moles solute free solvent

L' = molal form rate of solute free solvent to the tower in mol/s
Material balance of solute over tower :
V' [Y1 – Y2] = L' [X1 – X2]
∴ 14.7 [0.020408 – 0.0010204] = L' [0.12 – 0.005025]
∴ L' = 2.48 mol/s … Ans.
Example 9.3 : 1000 m3/h of a gas mixture containing 10 mole % solute and rest inert
enters an absorber at 300 K temperature and 106.658 kPa pressure. 90% of the original
solute is removed. Solute-free water used for absorption contains 5 mole % solute when it
leaves the absorber from the bottom. Calculate the solvent flow rate to the absorber.
Unit Operations – II 9.18 Gas Absorption

Solution : Basis : 1000 m3/h of gas mixture.

Molal flow rate of gas, n, is given by
PV
n = RT
where, R = 8.31451 (m3·kPa) / (kmol·K)
P = 106.658 kPa
T = 300 K, V = 1000 m3/h
(106.658) × 1000
n = = 42.76 kmol/h
8.31451 × 300
10
Mole fraction of solute in the gas mixture = y1 = 100 = 0.10
moles solute y1
Y1 = moles inert gas = 1 – y
1

0.10
= 1 – 0.10 = 0.111
Solute in the gas entering = 0.10 × 42.76 = 4.276 kmol/h
V' = Inert gas at the inlet = 42.76 – 4.276 = 38.484 kmol/h
Given : 90% of the solute is absorbed. Therefore,
Amount of solute absorbed = 0.90 × 4.276 = 3.848 kmol/h
moles solute in gas outlet
At the outlet : Y2 = moles inert gas at outlet
0.428
= 38.484 = 0.0111
For solute-free solvent :
X2 = 0
Given : Solvent leaving the absorption tower contains 5 mole % solute. Therefore,
5
x1 = mole fraction of solute in the solvent leaving the absorption tower = 100 = 0.05.
moles solute
At the exit : X1 = moles solute free solvent
x1 0.05
= 1 – x = 1 – 0.05 = 0.0526
1

Material balance for solute over absorber :

V' (Y1 – Y2) = L' (X1 – X2)
38.484 (0.111 – 0.0111) = L' (0.0526 – 0)
L' = 73.09 kmol/h
Molar flow rate of solute
free water (solvent) = 73.09 kmol/h … Ans.
to the absorption tower
Unit Operations – II 9.19 Gas Absorption

Example 9.4 : Benzene is to be recovered from cool gas by scrubbing it with wash oil as
an absorbent. The coal gas contains 2 % by volume of benzene and is to be fed at a rate of
855 m3/h and 95 % removal of benzene is required. The operating temperature and pressure
are 299.7 K (26.7o C) and 106.658 kPa. The wash oil has an average molecular weight of
260 and contains 0.005 mole fraction benzene as it enters the absorber. Calculate the
minimum circulation rate of the wash oil. The equilibrium relationship at the given
conditions is given by
Y X
1 + Y = 0.125 1 + X
where, Y – moles benzene/mole dry coal gas.
X – moles benzene/mole benzene free wash oil.
Solution : Basis : 855 m3/h of coal gas.
Assuming ideal gas behaviour, the molal flow rate of coal gas is given by
PV
n = RT

where V is the volumetric flow rate of coal gas.

P = 106.658 kPa,
T = 299.7 K, V = 855 m3/h
m3·kPa
R = 8.31451 kmol·K
(106.658) × 855
n =
8.31451 × 299.7
= 36.59 kmol/h
Molal flow rate of the gas at the inlet = V1 = n = 36.59 kmol/h
y1 = mole fraction of benzene in the coal gas
= 2/100 = 0.02
V' = V1 (1 – y1)
= 36.59 (1 – 0.02) = 35.86 kmol/h
Molal flow rate of benzene-free coal gas = 35.86 kmol/h
moles benzene
At the inlet : Y1 = moles dry coal gas
y1 0.02
= 1 – y = 1 – 0.02
1
= 0.0204 kmol benzene/kmol benzene-free gas
95% of benzene is removed by absorption.
At the outlet : Y2 = (1 – 0.95) Y1
= 0.05 Y1 = 0.05 × 0.0204
moles benzene
= 0.00102 moles benzene free gas
Unit Operations – II 9.20 Gas Absorption

Benzene in the coal gas inlet = 0.02 × 36.59 = 0.7318 kmol/h

Benzene removed by wash oil = 0.95 × 0.7318 = 0.6952 kmol/h
Benzene in the coal gas leaving the absorber = 0.7318 – 0.6952 = 0.0366 kmol/h
0.0366
Y2 = 35.86
= 0.00102 kmol benzene/kmol benzene-free gas
x2 = mole fraction of benzene in the wash oil (solvent inlet) = 0.005
x2
∴ X2 = 1 – x
2

0.005 moles benzene

= 1 – 0.005 = 0.00503 moles benzene-free oil

When L' (mole flow rate of benzene-free wash oil) is minimum, from the equilibrium
relationship, we can write
Y1 X1
1 + Y1 = 0.125 1 + X1
Substituting for Y1 yields
0.0204 X1
1 + 0.0204 = 0.125 1 + X1
Solving X1 = 0.1904
Material balance of benzene :
'
V' (Y1 – Y2) = Lmin (X1 – X2)
'
35.86 (0.0204 – 0.00102) = Lmin (0.1904 – 0.00503)
'
Solving, we get Lmin = 3.75 kmol/h
Flow rate (minimum) of benzene-free wash oil = 3.75 × 260 = 975 kg/h … Ans.
Example 9.5 : Benzene is to be recovered from coal gas by scrubbing it with wash oil as
an absorbent (solvent). Absorber handles 900 m3/h of coal containing 2% by volume
benzene. Coal gas enters at a temperature of 300 K (27o C) and 107.324 kPa pressure. 95%
of the benzene should be recovered by the solvent. The solvent enters at 300 K (30o C)
containing 0.005 mole fraction of benzene and has an average molecular weight of 260.
Calculate the circulation rate of oil (solvent) per hour if the column is to be operated at
1.5 times the minimum oil circulation rate.
The equilibrium relationship is :
Y X
1 + Y = 0.125 1 + X
where, Y is mole ratio of benzene to benzene-free coal gas
X is mole ratio of benzene to benzene-free solvent.
Unit Operations – II 9.21 Gas Absorption

Solution : Basis : 900 m3/h

Assuming ideal gas behaviour, the molal flow rate of coal gas is given by
PV
n = RT
where V is the volumetric flow rate of coal gas.
P = 107.324 kPa
(m3 · kPa)
R = 8.31451 (kmol · K)
T = 300 K
V = 900 m3/h
(107·324) × 900
n = = 38.72 kmol/h
8.31451 × 300
Molal flow rate of coal gas = V1 = n = 38.72 kmol/h
molal flow rate of benzene-free
V' = coal gas (inert/dry gas) = 0.98 × 38.72 = 37.95 kmol/h
y1 = mole fraction of benzene in the coal gas
2
= 100 = 0.02
V' = (1 – y1) V1 = (1 – 0.02) 38.72 = 37.95 kmol/h
moles benzene
At the inlet : Y1 = moles benzene free coal gas
y1 0.02
= 1 – y = 1 – 0.02 = 0.0204
1

95% of the benzene is recovered by absorption

At the outlet : Y2 = (1 – 0.95) Y1
Y2 = 0.05 × 0.0204
moles benzene
= 0.00102 moles benzene-free coal gas
x2 = mole fraction of benzene in the solvent (wash oil) at inlet
= 0.005
x2 0.005
At the inlet : X2 = 1 – x = 1 – 0.005 = 0.005025
2
moles benzene
X2 = moles benzene-free coal gas = 0.005025
Let X1 = mole ratio of benzene to benzene-free wash oil at the exit.
When L' (molal flow rate of benzene-free wash oil/solvent) is minimum, from the
equilibrium relationship, we can write
Y1 X1
1 + Y1 = 0.125 1 + X1
Unit Operations – II 9.22 Gas Absorption

Substituting for Y1 gives

0.0204 X1
1 + 0.0204 = 0.125 1 + X1
Solving, we get
X1 = 0.1904
Material balance of benzene over absorber :
'
V' (Y1 – Y2) = Lmin (X1 – X2)
'
37.95 (0.0204 – 0.00102) = Lmin (0.1904 – 0.005025)
'
Lmin = 3.97 kmol/h
'
Minimum flow rate of benzene-free wash oil (solvent) : Lmin
'
Given : L'actual = 1.5 Lmin . Therefore,
L'actual = 1.5 × 3.97 = 5.96 kmol/h
Actual flow rate of
benzene-free solvent = 5.96 × 260 = 1549.6 kg/h … Ans.
(i.e., circulation rate of wash oil)
Example 9.6 : Benzene is to be recovered from coal gas by scrubbing it with wash oil as
an absorbent. 1000 m3/h of coal gas containing 2% by volume benzene enters a column at a
temperature of 300 K (27o C) and 106.658 kPa pressure. 95% of benzene should be
recovered by the solvent. The solvent (wash oil) enters at 300 K (27o C) containing
0.005 mole fraction of benzene and has an average molecular weight of 260. Calculate the
circulation rate of solvent per hour if the column is to be operated at 1.5 times the minimum
solute free solvent flow to the absorber.
Assume that the wash oil-benzene obeys Raoult's law and the vapour pressure of benzene
at 300 K (27o C) is 13.33 kPa.
Solution : Basis : 1000 m3/h of coal gas.
Assuming ideal gas behaviour, the molar flow rate of coal gas can be calculated by
PV
n = RT

where P = 106.658 kPa

T = 300 K
V = Volumetric flow rate = 1000 m3/h
(m3·kPa)
R = 8.31451 (kmol·K)

(106.658) × 1000
n = = 42.76 kmol/h
8.31451 × 300
Unit Operations – II 9.23 Gas Absorption

Molal flow rate of coal gas = V1 = n = 42.76 kmol/h

2
y1 = mole fraction of benzene in the coal gas at inlet = 100 = 0.02

V' = molal flow rate of dry coal gas to the absorber.

= V1 (1 – y1)
= 42.76 (1 – 0.02) = 41.90 kmol/h
Y1 = mole ratio of benzene to dry coal gas at inlet to the absorber
y1 0.02
= 1 – y = 1 – 0.02 = 0.0204
1

95% of benzene is removed by absorption.

moles benzene
∴ Y2 = (1 – 0.95) Y1 = 0.05 × 0.024 = 0.00120 moles dry coal gas

x2 = mole fraction of benzene in the wash oil at inlet

= 0.005
moles benzene
∴ X2 = moles benzene free wash oil

x2 0.005
= 1 – x = 1 – 0.005 = 0.005025
2

At a total pressure of 106.658 kPa and a temperature of 300 K, the equilibrium

relationship is given by
p* = po x
p* po
y = P = P x
 
13.33
y = 106.658 x

y = 0.125 x
Y X
∴ 1 + Y = 0.125 1 + X
y
[as Y = 1 – y

y 1
1+Y = 1–y + 1 = 1–y

Y y
∴ 1+Y = 1 = y]
(1 – y) × (1 – y)
Unit Operations – II 9.24 Gas Absorption

'
when Lmin, molal flow rate of benzene-free wash oil that is minimum, from the
equilibrium relationship, we have
Y1 X1
1 + Y1 = 0.125 1 + X1
Substituting for Y1, we get
0.0204 X1
1 + 0.0204 = 0.125 1 + X1
∴ X1 = 0.1904
Material balance of benzene over absorber :
'
V' (Y1 – Y2) = Lmin (X1 – X2)
'
41.90 (0.00204 – 0.00102) = Lmin (0.1904 – 0.005025)
'
Lmin = 4.38 kmol/h
'
Actual benzene-free wash oil flow rate = 1.5 × Lmin = 1.5 × 4.38
= 6.57 kmol/h
Mass flow rate of benzene-free wash oil = 6.57 × Avg. Mol. Wt. of wash oil
= 6.57 × 260 = 1708.2 kg/h … Ans.
Example 9.7 : A packed tower is designed to recover 98% CO2 from a gas mixture
containing 10% CO2 and 90% by volume air using water. A relation y' = 14 x' can be used
for equilibrium conditions where,
kg CO2 kg CO2
y' is kg dry air and x' is kg water
The water to gas rate is kept 30% more than the minimum value. Calculate the actual
mole ratio of water to solute-free gas.
Solution : The gas mixture contains 10% CO2 and 90% air by volume (i.e., by mole).
Therefore,
10
y1 = mole fraction of CO2 in the mixture = 100 = 0.1

moles CO2 y1 0.1

∴ Y1 = moles dry air = 1 – y = 1 – 0.1 = 0.1111
1

98% CO2 is absorbed. Therefore,

Y2 = (1 – 0.98) Y1 = 0.02 × 0.1111 = 0.0022
For pure water as a solvent
X2 = 0
∴ x2 = 0
Unit Operations – II 9.25 Gas Absorption

The equilibrium relationship is

y' = 14 x'
Y/44 X/44
1/29 = 1/18
0.66 Y = 14 (0.409 X)
Y = 8.676 X
For a minimum liquid rate,
0.1111
X1 = Y1/8.676 = 8.676 = 0.0128
Material balance of CO2 :
'
V' (Y1 – Y2) = Lmin (X1 – X2)
Since X2 = 0, we get
'
Lmin Y1 – Y2
= X1
V'
'
Lmin 0.1111 – 0.0022
V' = 0.0128 = 8.5

L' 
 L' 
V' = 1.3  V' 
min
   
= 1.3 × 8.5 = 11.05
Actual mole ratio of water to solute-free gas = 11.05 … Ans.
Example 9.8 : An air-ammonia mixture containing 5% ammonia by volume is absorbed
in water in a packed column operated at 293 K (20o C) and 101.325 kPa pressure so as to
recover 98 % ammonia. If the inert gas mass velocity to the column is 1200 kg/(m2·h),
calculate the mass velocity of water to this column if the column is operated at 1.25 times the
minimum liquid rate to the column. Also calculate the composition of liquid leaving the
column corresponding to this condition.
The equilibrium relationship is : y = 1.154 x, where x and y are mole fractions.
Solution : Basis : 1200 kg/(m2·h) of inert gas to the column.
Mol. Wt. of air = 29
V' = inert gas (air) to the column = 1200/29 = 41.38 kmol/(m2·h)
mole fraction of ammonia 5
y1 = at inlet to the column = 100 = 0.05

moles ammonia y1 0.05

At the inlet : Y1 = moles air = 1 – y = 1 – 0.05
1

Y1 = 0.0526
Unit Operations – II 9.26 Gas Absorption

98% of ammonia is absorbed. Therefore,

moles ammonia
At the outlet : Y2 = moles air = (1 – 0.98) Y1

= (1 – 0.98) × 0.0526 = 0.001

The equilibrium relationship is
y = 1.154 x
Y X
∴ 1 + Y = 1.154 1 + X
At inlet to the column since water is pure, X2 = 0
At minimum liquid rate :
Y1 X1
1 + Y1 = 1.154 1 + X1
Substituting for Y1 gives
0.0526 X1
1 + 0.0526 = 1.154 1 + X1
X1 = 0.0453
Material balance of ammonia over column :
'
V' (Y1 – Y2) = Lmin (X1 – X2)
'
41.38 (0.0526 – 0.001) = Lmin (0.0453 – 0)
'
∴ Lmin = 41.73 kmol/(m2·h)
' '
Lactual = 1.25 Lmin

= 1.25 × 41.73 = 58.9 kmol/(m2·h)

Actual mass velocity of water to the column
= 58.9 × 18 = 938.92 kg/(m2·h)

Let X'1 be the liquid composition corresponding to this condition.

Hence, 41.38 (0.0526 – 0.001) = 58.9 X1'

Solving X1' = 0.0363

Composition of liquid leaving the column in terms of mole ratio = 0.0363 … Ans.
Unit Operations – II 9.27 Gas Absorption

Example 9.9 : A mixture of acetone vapour and air containing 5% acetone by volume is
to be freed of its acetone content by scrubbing it with water in an absorber. The flow rate of
the gas mixture 700 m3/h of acetone-free air measured at N.T.P. and water flow rate is
1500 kg/h. The absorber operates at an average temperature of 293 K (20 oC) and a
pressure of 101 kPa. 98% of the acetone is absorbed.
The equilibrium relationship for the acetone vapour-water system is : – Y* = 1.68 X.
where Y* = kg mole acetone/kg mole dry air
X = kg mole acetone/kg mole water.
Calculate the quantity of acetone absorbed per hour and the mean driving force for
absorption.
∆Y 1 – ∆Y 2
Hint : ∆Ylm =
ln (∆Y1/∆Y2)
∆Y1 and ∆Y2 are the driving forces at the top and bottom of the tower. ∆Y = Y – Y*
Solution : Flow rate of acetone-free air
= 700 m3/h N.T.P.
= 700/22.4 = 31.25 kmol/h
[Since 1 kmol of an ideal gas occupies a volume of 22.4 m3]
Flow rate of acetone-free water
= 1500 kg/h
= 1500/18 = 83.33 kmol/h
The mole fraction of acetone in the mixture is
y1 = 5/100 = 0.05
0.05
Y1 = y1/(1 – y1) = 1 – 0.05 = 0.0526

Given : 98% of the acetone is scrubbed. Therefore, we can write

Y2 = (1 – 0.98) Y1 = 0.02 Y1 = 0.02 × 0.0526
Y2 = 0.00105
Water entering the absorber is pure and therefore,
X2 = 0.0
Let us obtain X1.
Solute material balance over absorber :
V' (Y1 – Y2) = L' (X1 – X2)
Unit Operations – II 9.28 Gas Absorption

V'
X1 = (Y1 – Y2)
L'
31.25
= 83.33 (0.0526 – 0.00505) = 0.0193

Let us obtain the quantity of acetone absorbed.

Mol. Wt. of acetone = 58
Quantity of acetone absorbed = V' (Y1 – Y2)
= 31.25 (0.0526 – 0.00105)
= 1.611 kmol/h
= 1.611 × 58 = 93.44 kg/h … Ans.
The driving force for the absorption process at the bottom of the tower is
*
∆Y1 = Y1 – Y1 = Y1 – 1.68 X1
= 0.0526 – 1.68 × 0.0193 = 0.0202
At the top of the tower :
*
∆Y2 = Y2 – Y2 = Y2 – 1.68 X2
= 0.00105 – 1.68 × 0
= 0.00105
The mean driving force is
∆Y1 – ∆Y2
∆Ylm =
ln (∆Y1 / ∆Y2)
0.0202 – 0.00105
= 0.0202
ln 0.00105

= 0.0065 kg mol acetone/kg mol dry air … Ans.

Example 9.10 : For the data of Example 9.10, estimate the number of transfer units
(NTU) and the height of column required if the height of transfer unit (HTU) is 2 m.
Height of column = NTU × HTU
Y1 – Y2 Y1 – Y2
and NTU = * * =
(Y1 – Y1 ) – (Y2 – Y2 ) ∆Ylm
* *
ln (Y1 – Y1 ) / (Y2 – Y2 )
Solution : Y1 = 0.0526 , Y2 = 0.00105
The equilibrium relationship is
Y* = 1.68 X
Unit Operations – II 9.29 Gas Absorption

*
∴ Y1 = 1.68 X1 = 1.68 × 0.0193 = 0.0324
*
Y2 = 1.68 X2 = 1.68 × 0 = 0.0
(0.0526 – 0.00105)
NTU = (0.0526 – 0.0324) – (0.00105 – 0)
ln (0.0526 – 0.0324) / (0.00105)
= 7.95 ≈ 8
Height of packed column = NTU × HTU = 8 × 2 = 16 m … Ans.

EXERCISES
1. Fill in the blanks :
(a) In gas absorption, mass transfer takes place from the ...... phase to the liquid phase.
Ans. gas
(b) ....... used for gas absorption should be less volatile to avoid its loss in a lean gas.
Ans. Solvent
(c) ............. are continuous gas-liquid contactors and ................. are stage-wise
contactors. Ans. Packed columns, plate columns
(d) Operating velocity in packed columns should be 50 to 70% of the .......... velocity.
Ans. flooding
(e) Packing size should not be more than 1/8th of the column ............. Ans. diameter
(f) Absorption of NO2 in water to produce nitric acid is an example of absorption with
............ Ans. chemical reaction.
(g) The tendency of the liquid to segregate towards the walls and to flow along the
walls is termed as ................ Ans. channeling
2. Define gas absorption. What for it is carried out industrially ? Give suitable
examples.
3. What factors should be considered while selecting solvent for gas absorption ?
4. State the desirable characteristics of packings.
5. List various types of packings used in industry and state their materials of
construction.
6. Explain briefly the hydrodynamics / press drop characteristics of a packed column.
7. Compare plate and packed columns for merits and demerits.
8. Draw a neat sketch of packed column and write its construction and functioning.
9. What do you mean by HETP ? State the factors on which HETP depends.