CL319 Autumn 2015 Friday, 18 September 2015

Mass Transfer

Topic 5 > 5.5 Mass transfer with chemical reaction (contd..)

5.5.4 Mass transfer with chemical reaction - Surface renewal theories:

We may briefly take a look at what the surface renewal theories (Higbie and Danckwerts) have
to say about the effect of chemical reaction on mass transfer. To keep the discussion short and
simple, we recall the comparison earlier drawn between the two theories, and note that in
general, we may relate the mass transfer coefficient to diffusivity as:
DA
kc0 = . (5.23)
t ch
where tch is some characteristic time - the two theories differ only slightly in the magnitude they
have for this time. On the other hand, typical experimental values of the mass transfer coefficient
and diffusivities suggest that t ch O(0.1s) . Also, we note that, from the theory-neutral
formulation of the Hatta number, its definition in terms of the surface renewal theory parameters
can be written as
M = kcBbt ch .(5.24)
the interpretation being that M is the ratio of time available to time required (by the reaction to
proceed to a significant extent).

With the same assumptions about the non-volatility of B and a second order rate expression for
the reaction, the surface renewal theories have the concentration profile in an element t sec old
at the interface given by the solution of the following equations (after non-dimensionalization;
note that tb is used to non-dimensionalize time to and DAtb to non-dimensionalize
distance; the latter comes from the characteristic penetration depth in pure diffusion):
a 2 a
= Mab
2
(5.25)
DA b 2 b M
= ab
DB 2 q
with
t = 0, ,a = ab ;b = 1
b
t > 0, = 0,a = 1; =0

t > 0, ,a = ab ;b = 1

Thus the ratio of diffusivities occurs as an additional dimensionless group in this case.

It may be shown (see Prob. set 6) that M q leads to the pseudo-first order regime here also,
viz., b 1 and the concentration of B is unaffected in the liquid element by the reaction since its

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CL319 Autumn 2015 Friday, 18 September 2015
supply is so much in excess of requirement. Thus we have only the first equation in (5.29) with
b=1.

If in addition, M 1 , we can drop the reaction term from the RHS and we have the same
equation as we had for physical mass transfer. That is, the reaction is so slow in this case that, in
the time available at the interface, it occurs to a negligible extent, the solute accumulating just as
if the reaction were not there. Thus the mass transfer rate in this case is identical to that in
physical mass transfer for the same bulk concentration of A. We may assess the effect of
reaction by a balance on the reactant A in the bulk liquid (which in this case is the liquid pool
from where the surface elements originate, equal in volume to the difference between total liquid
volume and the volume of the surface elements); for a batch absorber in (quasi) steady state,

Rate of absorption of A = Rate of consumption of A by chemical reaction.

kc0 '(cA* cAb ) = kcAb cBb

which is the same equation we wrote for the slow reaction regime in the Film theory. The ration
of the film to bulk volumes that made DSR possible is replaced here by the ratio of the volume of
the elements which contain the concentration gradient to the bulk volume, and its smallness
again makes a DSR possible.

Thus the slow reaction regime is identically treated in the two theoretical frameworks.

For the next regime of transition to Fast reaction, we need to solve:

t = 0, ,a = ab 0
a 2 a
= Ma with t > 0, = 0,a = 1; (5.26)
2
t > 0, ,a = ab
This can be solved using the Danckwerts method (refer BSL), as:

a = M aPD e Mt dt + aPD e M
0

where aPD is the solution to the pure diffusion problem with the same conditions (this is easily
verified by substitution). One can therefore solve the model for the instantaneous concentration
profile, and hence the instantaneous flux at the interface, and average it over the life of the
surface elements to obtain the average flux. The Danckwerts surface renewal theory provides a
particularly elegant way of solving this problem by Laplace transformation where, because of the
nature of the age distribution function employed, the average flux is directly obtained without the
need for inversion. This solution gives:
E = 1+ M ..(5.27)

Higbies theory (using the Danckwerts method above) gives a more complex expression, as
follows:

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 Slow-to-Fast Transition regime- Enhancement factors

Film Theory
p
CL319 M
Autumn 2015 Friday, 18 September 2015
E = p
tanh M

Higbies Surface Renewal Theory

" r p #
4M 1 4M 4M 4M .(5.28)
E = p + erf + exp
4 M 2

Danckwerts Surface Renewal Theory

but the expressions from the three theories give numerical values which are close in any case.
They are compared, in the region 1E< =Hap<1 +
5Min the figure below:

Before proceeding further, we may mention in passing an important application of the equation
for enhancement factor provided by the Danckwerts theory, eq. (5.27). Using this in the
expression for the volumetric rate of absorption RA and rearranging terms, we get
2
RA
( ) + '2 DA ( kcBb )
2
c
*
= k 0
c ' ..(5.29)
A

which shows that, from data collected on the absorption rate for different values of ( kcBb ) (either
through the use of a catalyst to change k or through variation in cBb ), one can obtain both the
volumetric mass transfer coefficient and interfacial area from a plot of the LHS vs. ( kcBb ) . This is
the only way of determining both of these quantities simultaneously from the same set of data.

Proceeding further on the scale of increasing Hatta number, we note from eq. (5.27) that
E M for Ha>3 with the error in the approximation being about 15% or less. This is the same
result as given by Film theory. Physically, this convergence can be understood as follows. The
reaction, in the surface element, has the effect of decreasing accumulation in general, and, if fast
enough, will reduce it to zero, resulting in a steady state profile within the surface element. For
large enough values of the Hatta number, this steady state is achieved soon enough in the
lifetime of the surface element that, to a good approximation, the entire lifetime may be regarded

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CL319 Autumn 2015 Friday, 18 September 2015
as being spent in such a steady state. A steady state formulation of eq. (5.26) and comparison
with the film theory formulation for the fast reaction regime shows that the theories become
identical for this case. Essentially, the finite field of the film theory can be replaced by an infinite
field for fast reaction (since the flux goes to zero within the film), while the unsteady state nature
of the process in the surface element can be replaced by a steady state process, thus
eliminating the differences between the theories.

Thus, the theoretical predictions are identical for slow and fast reaction, and nearly so for the
transition (to fast reaction) regime.

Let us now consider even faster reactions, those for which we can no longer assume pseudo-
first order kinetics. Clearly, the full set of equations (5.25) needs to be solved in this case, and
we may expect an additional group, the ratio of diffusivities of A and B, to come into play.
Physically, we expect concentration profiles of B to develop and become more pronounced as a
function of time. For fast enough reactions, the reaction becomes confined to a region
1 < < 2 with A diffusing through B-free medium in the region 0 < < 1 and B diffusing
through A-free medium in the region 2 < < 1 . The difference from the film theory picture here
is that 1 and 2 are functions of time now, and the reaction zone thins down during the life of
the surface element. In the limit as the Hatta number increases, the zone becomes a plane with
1 and 2 coinciding, right at the start of the life of the element. This reaction plane then moves
in the direction of positive with time. Since A and B cannot co-exist in this case, this is the
Instantaneous reaction regime in the framework of the surface renewal theories. The equations
have to be formulated differently for this case, and the details can be seen in the references. See
also the NPTEL course (http://nptel.ac.in) on reaction engineering by A.K. Suresh, S.M.
Mahajani and Ganesh Vishwanathan, Lectures 25 and 26.

While the results for Enhancement factor ( E ) in the instantaneous regime are implicit and in
general not very easy to evaluate, an approximation that applies for large values of E is useful,
1
the error being of the order of . This approximation is:
2E

DA
E = (1+ q ) (5.30)
DB
which shows that, under these conditions, the predictions of the film and surface renewal
theories differ by the square root of the ratio of diffusivities.

Using eq. (5.30) for E in eq. (5.21) and (5.22) gives an approximate way for calculating
enhancement factors in the regime of transition to instantaneous regime, in the framework of the
surface renewal theories. In general, surface renewal theory expressions are to be preferred
over the film theory expressions for this transition and the instantaneous reaction regimes.

The discussion of mass transfer with chemical reaction is now complete.