3.

2 THEORIES OF MASS TRANSFER

In most of the practical applications of mass transtfer, material is transferred across a phase boundary.
The rate of mass transtfer between the two phases depends on the physical properties of the phases, the
concentration difference. the interfacial area and the degree of turbulence. A number of theories have
been proposed to explain the mechanism of mass transfer at the phase boundary. Some of them are
reviewed in the following sections.

Film Theory
The film concept of mass transfer was alreaay aiscussea Drietly in the section on mass transfer coefficienl.
The concentration profile in turbulent tlow when the solute is
dissolving from the surface and is
diffusing to the main stream is shoWn in
Fig J.L. 1ne concentration of the solute decreases as the
distance from the wall increases. Three regions can be visualized in the flowing stream. In the stagnant
the solid surface, most of the mass transfer occurs by molecular
layer of fluid immediately adjacent to
diffusion; this layer is known as diffusional sub-layer. No eddies are present in this layer. A large
of the
concentration drop occurs across the viscous sub-layer as is clear from the figure. Major portion
The
fluid cross section is the turbulent core in which the mass transfer is mainly due to eddy transport.
contribution of molecular diffusion to mass transport is insignilicant compared to that of eddy transport.
In between the diffusional sub-layer and the turbulent core, is the buffer zone, where the mass transter
by both molecular diffusion and eddy diffusion are significant.
It can be seen that the concentration profile from Caadjacent to the solid surface to Cain the average
bulk composition is very steep in the diffusional sub-layer and thereafter the concentration levels off

rapidly. The exact shape of the concentration-distance relation curve is dependent on the relative
magnitudes of eddy diffusivity and molecular diffusivity at that point. The film concept of mass transfer
proposed by Nermst (1904) assumes that the principal resistance to overall transfer process lies in the
region near the wall. In the film theory of mass transfer, the entire concentration change from Ca to CAb
is assumed to be confined within an effective film of thickness Z. It is a fictitious length offering the
same resistance to molecular diffusion as that encountered in the combined processes of molecular
diffusion and eddy diffusion. It is also assumed that within this film, the change in concentration with
distance is linear as in steady-state equimolar counter diffusion. We have seen that if the concept of film
coefficient of heat transfer is extended to represent the convective transport of mass, the film coefficient
CDAB
of mass transfer should be Z
In the treatment of interphase mass transfer, it is assumed that a film of stagnant fluid similar to that
existing near a solid boundary is present at the fluid-fluid interface within which, the mechanism of
mass transfer is molecular diffusion. Then the quantity CDAB will represent film coefficient of mass
Z
transfer which is related to k, or k, as given by Eq (3.19)

kyB,M CDAB
A=K
Z
k .(3.19)

The film theory is simple to comprehend and easy to apply. It suggests that the mass transfer
coefficient is directly proportional to the diffusion coefficient DaB. This linear dependency of the mass
transfer coefficient on the diffusivity 1s the main limitation of the film theory. The experimental data.
predicts a dependency of (DAR where n ranges from 0.5 to 0.75. Using the Chilton-Colburn analogy.
discussed later in this chapter, it is seen that k, o« DAB which is in better agreement with experimental

data. These observations suggest that the film thickness Z should be a function of DaR. Even though the
film model cannot be used effectively for prediction and correlation, it is useful because of its mathematical
simplicity for predicting and analysing the effects of such complicating factors as the simultaneous
chemical reaction at the interface and the influence of high solute concentration and fluxes. Also, it is
a useful model for membranes as they satisfy the film assumptions, and is reasonably good as a tirst
approximation for highly turbulent fluids near solid surfaces, where the existence of a thin stagnant
layer is a reality.

Penetration Theory
The penetration theory was proposed by Higbie (1935). Instead of the stagnant film at the interface as
proposed in the film theory, Higbie suggested that eddies move from the bulk of the fluid stream to the
interface at definite intervals, they stay at the interface for a short but fixed period of time. During this
fixed time of exposure, the solute diffuses into the eddy by molecular diffusion, after which the eddies
70 Mass Transfer: Theory and Applicalio
C away from the interface to pet mixed with the bulk stream. Thus according to this
eamtheory,
(Cah). a when

of the bulk strea

fluid
concentration (CA), wA
element whose initial concentration is the same as the
instantaneously at the interfac
ace. A proc
exposed to the second fluid phase, equilibrium is established after which the fluid elema
molecular diffusion for a fixed time of exposure, stream. Th
occurs ement
nsteady-state with the bulk Thus the
the eddies
eddies aare
is
replaced byfresh one and moves to and gets mixed
alternately static and moving.
In Higbie's experiments, a slug-like bubble of carbon t
100
dioxide was allowed to rise through a column of water. 5000
It was assumed that the length of time each element of
the surface in the liquid is exposed to the gas was equal
to the time taken by the gas bubble to
pass it. Absorption 1000
took place during this period by unsteady state molecular
diffusion. The depth ofthe liquid element is assumedto 100
be infinite in comparison with the depth of t Exposure time
penetration 10
of the solute. The concentration-time-distance history
in the liquid which was exposed to diffusion of a soluble Distance from surface
gas can be plotted as shown in Fig. 3.3. In the figure,
the percentage saturation of the Fig. 3.3: Solute penetration as function of
liquid is plotted against exposure time
the distance for different
exposure times on arbitrary
units.
The concentration profile
is such that at any time, the effective
depth of liquid which contains an
appreciable concentration of solute can be specified, and hence the theory is known as
theory. The rate of diffusion is governed by Fick's second law penetration
(see Eq. (2.122):
OCA DAB oCA
a2 .3.37)
The following boundary conditions are applicable:
CA=CAb at t = 0, for all z
CA=CAi at z =0, for t>0
CACAb as z , for allr
The solution of Eq. (3.37) can be written as

CACAb=1
CAi-CAb -erf
where t is the exposure time for the fluid element.
For
2 DAB ...(3.38)

the bubble is assumed to be the ratio of bubbles, the contact time of

bubble diameter to surroundine
the liquid
contact time is the time taken by the
droplets to fall bubble rise
as the distance at which the through the gas. The velocity.For liquid spray,
liquid spray, tne
spray,
the

concentratio change is one depth penetration

of on is defined
this condition is percent of the final value.
The 1molar flux under

Camnare this with the

NA=2AC -CAA)
following expression tor mass flux ..(3.39)

NA k(CAi -CAb) written in term

coefficient
Thus, according to the penetration theory,
..(340)

k 2A
Tt N
. (3.41)
.
 Convective Transport and Interphase Mass Transfer 71

which predicts that the mass transfer coefficient is proportional to the square root of the diffusion
coefficient. If the dependeney of k, to DAR is written as k, D'iR. the penetration theory sets the value
o«

of n to be 0.5, which is generally the lower limit of the observed range of values of n. The penetration
theory is most useful when mass transfer involves bubbles or droplets and for flow over random
packing.
Surface Renewal Theory
Penetrat1on theory with constant exposure time fails to represent the mass transfer occurring in devIces
such as stirred tanks, the bubble and spray columns where bubbles and droplets of varying sizes are
present. Danckwerts (1951) suggested an improvement of the penetration theory by assuming a residence
time distribution in the place of the constant exposure time. He suggested that liquid surface elements
will not be exposed to the gas for a constant duration; instead, a random distribution of ages is more
probable for the fluid elements at the interface. That is, the interface will be made up of surface
elements of different exposure-time histories. The probability of any element of surface getting destroyed
and mixed with the bulk of the fluid is independent of the age of the element. Since the rate of solute
penetration depends on the exposure time, an average rate should be determined by summing up the
individual values. Indicating the fractional rate of replacement of elements by s, the surface-age
distribution function is shown to be
= seST. ...(3.42)
Here o represents the probability that any element of area is exposed for time t before being replaced
by fresh fluid from the bulk. The rate of absorption is
N= DABs (Cai-Cab ) ..(3.43)
which relates k and DAB as

kL=DABS ..(3.44)
For the mass transfer coefficient, the surface renewal theory also predicts the same dependency on
molecular diffusivity as the penetration theory. The numerical value of s is difficult to estimate, although
we know that it will increase as the fluid becomes more turbulent. In packed column, s will be of the
same order of magnitude as the ratio of the velocity of the liquid flowing over the packing to the length
of packing.