Chapter 15

Mass transfer with chemical

reactions
(Material presented in this chapter are based on those in Chapter 16, Diu-
sion mass transfer in uid systems second edition by EL Cussler and Chapter
14, Fundamental of heat and mass transfer, second edition by Incropera
and DeWitt)
The liquid-phase mass transport across interface depends on the diusion
of the solute in the liquid phase. The diusion of the solute depends on the
chemical reaction, if any involving the solute in the interface. There are
several examples in which simultaneous mass transport between two phases
and chemical reactions are involved. For example, several polymerization
reactions occur in emulsions, which consist of two liquid phases. One of the
reactants is usually in a phase in which the reaction does not occur. Thus,
the reactant has to cross the interface and react in another phase.
Chemical reaction under certain conditions strongly inuence the diu-
sion. This inuence depends on whether the reaction is homogeneous or
heterogeneous. In this chapter, mass transport during homogeneous chemi-
cal reactions will be characterized. The expressions for the coecient with
chemical reactions will be compared with those without chemical reactions.
191
192 CHAPTER 15. MASS TRANSFER WITH CHEMICAL REACTIONS
15.1 Mass diusion with homogeneous reac-
tion
Consider the system where a solute species present in the gaseous phase that
transports into the liquid phase, maintained at a certain concentration where
the solute gets converted into products via an irreversible reaction (Fig. 15.1)
Figure 15.1: Mass transfer with chemical reaction
A Products (15.1)
If the transport in the interface in the liquid-phase follows lm theory, then
the model that describes the simultaneous transport and reaction is given by
the following dierential balance
D
d
2
C
A
dx
2
+

N
A
= 0 (15.2)
15.1. MASS DIFFUSION WITH HOMOGENEOUS REACTION 193
where, C
A
is the concentration of the species A, D is the mass diusivity of
the species in the liquid-phase,

N
A
is the rate of formation of the species A
per unit volume, and x is the distance in the interface.
If the reaction (Eq. 15.1) were to be a rst order reaction, then the model
(Eq. 15.2) can be written as
D
d
2
C
A
dx
2
k
rxn
C
A
= 0 (15.3)
where, k
rxn
is the reaction rate constant. One boundary condition is the in-
terface concentration at the contact point between the gas and liquid. There
are two possible second boundary conditions for this model at the other end
of the interface. If the bulk concentration of the speices is known then the
constant boundary conditions at the edge of the interface can be used. If the
bulk concentration is unknown, then somewhere just outside the interface,
the bulk concentration should remain constant, that is, the ux or concen-
tration gradient of the solute must be zero at the interface.
15.1.1 No ux boundary condition
The solution of the model (Eq. 15.3) subject to the boundary conditions
C
A
(x = 0) = C
Ai
;
dC
A
dx
|
x=L
= 0 (15.4)
is given by
C
A
(x) = C
Ai
(cosh(mx) tanh(mL) sinh(mx)) (15.5)
where, m =
_
krxn
D
. The concentration at the end of the interface, that is, at
x = L is
C
A
(L) = C
Ai
cosh
2
2(mL) sinh
(
mL)
cosh(mL)
=
C
Ai
cosh(mL)
(15.6)
and the ux at the gas-liquid contact point is given by
N

A
(x = 0) = DC
Ai
mtanh(mL) (15.7)
If the mass transport ux across the interface is dened as N

A
= k
L
(C
Ai

C
A
(L)) then using Eqs (15.6) and (15.7), the eective mass transport coe-
cient across the interface can be found.
194 CHAPTER 15. MASS TRANSFER WITH CHEMICAL REACTIONS
15.1.2 Constant boundary condition
The solution of the model (Eq. 15.3) subject to the boundary conditions
C
A
(x = 0) = C
Ai
; C
A
x = L = C
Ab
(15.8)
is given by
C
A
C
Ai
=
sinh
__
krxn
D
(L x)
_
sinh
_
krxn
D
L
_ (15.9)
The ux at x = 0 is given by
j
A
= D
dC
A
dx
|
x=0
= C
Ai
_
Dk
rxn
coth
_
k
rxn
L
2
D
(15.10)
If the mass transport ux across the interface is dened as N

A
= k
L
(C
Ai

C
A
(L)) then, the eective mass transport coecient across the interface is
given by
k
L
=
_
Dk
rxn
coth
_
k
rxn
L
2
D
(15.11)
Supposing the k
L0
is the mass transfer coecient when no chemical re-
action occurs, then according to the lm theory (section 14.1), k
L0
=
D
L
,
using which the ratio of mass transfer coecients with and without reaction
is given by
k
L
k
L
0
=

Dk
rxn
k
2
L0
coth
_
Dk
rxn
k
2
L0
_
(15.12)
The solution in both rst and second cases shows that the concentration
does not follow a linear prole as in the case observed during pure mass
transport.
15.2 Mass transfer with second order reac-
tions
Consider the case where one solute gets transported to the second phase,
which reacts with another reactant in the second phase. Assume the reaction
to be rst order with respect to both components. If species A and B are
15.2. MASS TRANSFER WITH SECOND ORDER REACTIONS 195
the reactants to form a certain product via the chemical reaction A + B
Products, the model describing mass transport in the interface is given by
D
A
d
2
C
A
dx
2
k
rxn
C
A
C
B
= 0 (15.13)
D
B
d
2
C
B
dx
2
k
rxn
C
A
C
B
= 0 (15.14)
subject to the boundary conditions, z = 0, C
A
= C
Ai
,
dC
B
dz
= 0 and z =
L, C
A
= 0, C
B
= C
Bi
. Equations (15.14) when solved can provide an expres-
sion for the mass transfer coecient.
196 CHAPTER 15. MASS TRANSFER WITH CHEMICAL REACTIONS