DIFFUSION WITH A HOMOGENEOUS CHEMICAL REACTION

we consider the system shown in Fig. 1. Here gas A dissolves in liquid B in a beaker
and diffuses isothermally into the liquid phase. As it diffuses, A also undergoes an
irreversible first-order homogeneous reaction: A + B AB. An example of such a
system is the absorption of CO, by a concentrated aqueous solution of NaOH.

Fig:1 Absorption of A by B with a homogeneous reaction in the liquid phase

We treat this as a binary solution of A and B, ignoring the small amount of AB that is
present (the pseudobinay assumption). Then the mass balance on species A over a
thickness z of the liquid phase becomes

-Eq-1
in which k1''' is a first-order rate constant for the chemical decomposition of A, and S
is the cross-sectional area of the liquid. The product k1'''cA represents the moles of A
consumed by the reaction per unit volume per unit time. Division of Eq.1 by Sz and
taking the limit as Z 0 gives

-Eq-2
If the concentration of A is small, then we may to a good approximation write this
following eq. As

-Eq-3
 Since the total molar concentration c is virtually uniform throughout the liquid.
Combining the last two equations gives,

-Eq-4
This is to be solved with the following boundary conditions:
B.C. I: at z = 0, CA=CAO -Eq-5
B.C. 2: at z = L, NAZ = 0 (or dcA/dz = 0) -Eq-6
The first boundary condition asserts that the concentration of A at the surface in the
liquid remains at a fixed value CAO. The second states that no A diffuses through the
bottom of the container at z = L.

If Eq. 18.4 is multiplied by L2/CAODAB then it can be written in dimensionless

variables in the form of

-Eq-7
where r = CA/CAO is a dimensionless concentration, = z/L is a dimensionless length,
K 1' ' ' L 2
and = D AB is a dimensionless group, known as the Thiele modulus.' This

group represents the relative influence of the chemical reaction k1'''CAO and diffusion
CA0DAB/L2. Equation 18.7 is to be solved with the dimensionless boundary conditions
that at = 0, r = 1, and at = 1, dr/dc = 0. The general solution is

-Eq-8
When the constants of integration are evaluated, we get

-Eq-9
Then reverting to the original notation

-Eq-10
The concentration profile thus obtained is plotted in Fig. 18.1.
Once we have the complete concentration profile, we may evaluate other quantities, such
as the average concentration in the liquid phase
 -Eq-11
Also, the molar flux at the plane z = 0 can be found to be

-Eq-12
This result shows how the chemical reaction influences the rate of absorption of gas A
by liquid B.
The reader may wonder how the solubility C A0 and the diffusivity DAB can
be determined experimentally if there is a chemical reaction taking place. First, k1'''
can be measured in a separate experiment in a well-stirred vessel. Then, in principle,
CA0 and DAB can be obtained from the measured absorption rates for various liquid
depths L.

Example 1:

Estimate the effect of chemical reaction rate on the rate of gas absorption in an agitated tank.
Consider a system in which the dissolved gas A undergoes an irreversible first order reaction
with the liquid B; that is, A disappears within the liquid phase at a rate proportional to the
local concentration of A. An example of such a system is the absorption of SO, or H2S in
aqueous NaOH solutions.

Solution:-

Fig :2 Gas Absorption Apparatus.

An exact analysis of this situation is not possible because of the complexity of the gas-
absorption process. However, a useful semiquantitative understanding can be obtained by the
analysis of a relatively simple model. The model we use involves the following assumptions:

a. Each gas bubble is surrounded by a stagnant liquid film of thickness , which is small
relative to the bubble diameter.
b. A quasi-steady concentration profile is quickly established in the liquid film after the
bubble is formed.
c. The gas A is only sparingly soluble in the liquid, so that we can neglect the convection
term in Eq. 1.
d. The liquid outside the stagnant film is at a concentration cA which changes so slowly
with respect to time that it can be considered constant.

The differential equation describing the diffusion with chemical reaction is the same as that in
Eq. 18.4, but the boundary conditions are now
BC :1 at z=0, cA= cAO Eq-13
BC:2 at z = cA=cA -Eq-14

The concentration CA0 is the interfacial concentration of A in the liquid phase, which is
assumed to be at equilibrium with the gas phase at the interface, and CA, is the concentration
of A in the main body of the liquid. The solution of Eq. 18.4 with these boundary conditions
is

:Eq-15

Fig:3 Predicted concentration profile in the liquid film near a bubble.

Next we use assumption (d) above and equate the amount of A entering the main body of
liquid at z = over the total bubble surface S in the tank to the amount of A consumed in the
bulk of the liquid by chemical reaction:

Eq-16
Substitution of cA from Eq.15 into Eq. 16 gives an expression for B:
 -Eq-17

Fig: 4 Gas absorption accompanied by an irreversible first-order reaction.

When this result is substituted into Eq.15, we obtain an expression for cA/cAO in terms of ,
and V/s.
From this expression for the concentration profile we can then get the total rate of absorption
with chemical reaction from NAZ = -DAB(dcA/dz) evaluated at z = 0, thus:

-Eq 18
The result is plotted in Fig.4.
It is seen here that the dimensionless absorption rate per unit area of interface, N increases
with for all finite values of V/S. At very low values of that is, for very slow reactions N
approaches zero. For this limiting situation the liquid is nearly saturated with dissolved gas,
and the "driving force" for absorption is very small. At large values of the dimensionless
surface mass flux N increases rapidly with and becomes very nearly independent of V/S.
Under the latter circumstances, the reaction is so rapid that almost all of the dissolving gas is
consumed within the film. Then B is very nearly zero, and the bulk of the liquid plays no
significant role. In the limit as becomes very large, N approaches .