NPTEL Chemical Mass Transfer Operation 1

MODULE 4: ABSORPTION

LECTURE NO. 6

4.9. Absorption with chemical reaction

Operations in which one or more components of a gas phase are
absorbed into a liquid phase are common throughout the chemical process
industries and frequently serve to achieve desired reactions among components
in the two phases (Lee & Tsui, 1999). Such operations are often called reactive
absorption because of the combination of reaction and absorptive mass
transport. There are a number of cases in which a gas, on absorption, reacts
chemically with a component of the liquid phase. In such processes, the
conditions in gas phase are similar to those of an entirely physical absorption
process, but in the liquid phase, there is a liquid film followed by a reaction zone.
As an example, in the absorption of carbon dioxide by caustic soda, the carbon
dioxide reacts directly with the caustic soda. An advantage of absorption plus
reaction is the increase in the mass-transfer coefficient. This may be due to a
greater effective interfacial area. The process hydrodynamics can also be directly
involved via correlations for the hold-up, pressure drop, and mass transfer
coefficients, etc.

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NPTEL Chemical Mass Transfer Operation 1

4.9.1. Absorption-Reaction Model

The fundamental relations governing simultaneous diffusion and chemical
reaction of a dissolved species have been reviewed by Danckwerts (1970). For
one-dimensional diffusion of a single species (A) with diffusivity independent of
concentration

DA

2 C A C A

v A rA
t
x 2

(4.47)

The reaction rate term r, is generally a function of solute concentration and

of one or more liquid reactant concentrations. If these reactant concentrations
vary appreciably, continuity equations for each reactant must be solved
simultaneously with Equation (4.47) to obtain the solute concentration profile. An
increase in the rate of absorption caused by reaction is a result of a
concentration drop in the bulk liquid phase.

dC
J A k L (C A* C A0 ) D A A
dx x 0

(4.48)

As per film model, the concentration gradient at the interface becomes steeper
while the mass transfer coefficient kL remains unchanged.

4.9.2 Absorption accompanied by irreversible first-order reaction

The bulk concentration becomes zero when the absorption process is
accompanied by a fast irreversible first-order reaction. Then as per film theory
the following balance can be written:

2C A
DA
k1C A
x 2

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(4.49)

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NPTEL Chemical Mass Transfer Operation 1

The reaction rate term r = k1CA for an irreversible reaction. k1 is the rate constant.
The Equation (4.49) can be solved by incorporating boundary conditions:

C A C A*

at x 0
at x

CA 0

(4.50)
(4.51)

The absorption rate RA can be estimated from the concentration profile

dC
RA DA A
dx x0

(4.52)

By introducing the solution of Equations (4.49-4.51) one can get

RA

M
tanh M

k L C A*

(4.53)

Where

k1 D A
k L2

(4.54)

This can be interpreted as ratio of diffusion time ( D A / k L2 ) to reaction time (1/k1).

When M 1 , then tanh M 1 and Equation (4.7) can be written as

R A k L C A* M C A* (k1 DA )

(4.55)

The Equation (4.55) indicates that the absorption rate is independent of the mass
transfer coefficient and therefore the hydrodynamic conditions prevailing at the
interface. The Equation (4.55) can be used to estimate the interfacial area (Si) in
gas-liquid reactor as

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NPTEL Chemical Mass Transfer Operation 1

Si

n A0U
RA

(4.56)

where n A0 is the initial molar flow and U is the overall gas phase conversion.
Therefore the specific interfacial area (the interfacial area per unit volume of
liquid (VL) in the reactor) can be expressed as

n A0U
VL C A* (k1 D A )

(4.57)

As per Danckwerts surface renewal theory, the absorption rate can be derived
as

R A k L C A* 1 M C A* (k1 DA k L2 )

(4.58)

The ratio of specific absorption rate (RA) to the k LC A* is called enhancement

factor of absorption from the diffusion regime. The Equation (4.58) also forms the
basis for the calculation of absorption rate referred to as the liquid volume (VL):

R A a aC A* (k1 DA k L2 )

(4.59)

Example Problem 4.3. In a batch catalytic reactor, chlorination with toluene is

carried out. It is found from the reaction that the film mass transfer coefficient (k L)
is 5 10-4 cm/s, the specific interfacial area is 3.6 cm-1. The liquid holdup (L) of
the reactor was 0.74. The reaction is first order and the equilibrium constant (k 1)
of the reaction is 3.5 10-4 s-1. The overall gas phase conversion is 80%. The
initial molar concentration of the gas phase was 1.2 10-7 mol/cm3. Find out the
enhancement factor of the absorption and the rate of absorption for this reaction.
The diffusivity of the chlorine is 3.74 10-5 cm2/s.

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NPTEL Chemical Mass Transfer Operation 1

Solution4.3:
The parameter M from Equation (4.54) is equal to

k1 DCl2
k L2

3.5 10 4 3.74 10 5

0.05239
(5 10 4 ) 2

Therefore the enhancement factor can be found from the Equation (4.58) as
R A /( k L C A* ) 1 M 1.025

The chlorine concentration as a function of physical solubility can be calculated

from the relation:
0

CL
*

CL

kLa
0.839
k L a k L L

Therefore the absorption rate (RAa) can be calculated from the Equation (4.59)
as
0

R A a aC A* (k1 DCl2 k L2 ) 3.6 (C L / 0.839) (3.5 10 4 3.74 10 5 (5 10 4 ) 2 )

=2.64 10-10 mol/cm3s.

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