Mehran University of Engineering and

Technology, Jamshoro

ASSIGNMENT
Name: UZAIR AHMED
Roll No: 21CH060
Subject: Transport Phenomena
Submitted To: Dr.Masroor Abro
Department: Chemical Engineering
1. Introduction to Mass Transfer Coefficient
The mass transfer coefficient (k) is a key parameter used to quantify the rate of
mass transfer across a phase boundary in chemical engineering operations such as
absorption, extraction, distillation, and drying.

It is defined in the context of Fick’s law, which describes the diffusion-driven

transport of a species due to a concentration gradient:

This equation relates the mass flux to the driving force for mass transfer (the
concentration difference) and the mass transfer coefficient, which captures the
ease with which species A is transported through the phase boundary.

2. Interfacial Mass Transfer

Interfacial mass transfer occurs when a species moves from one phase to another
(e.g., from a gas to a liquid, or liquid to solid). The steps typically involved are:

a. Transport to the Interface (Bulk Phase)

 In the bulk phase, species A is carried mainly by convection toward the

phase boundary, where molecular diffusion becomes dominant.
b. Diffusion Across the Interface

 Near the interface, a thin stagnant layer or boundary film forms. In this
film, mass transfer occurs by molecular diffusion only.

c. Transfer into the Second Phase

 After crossing the interface, the solute diffuses away from the boundary
layer into the bulk of the second phase.

This process is often rate-limited by diffusion through the stagnant film near
the interface, making the mass transfer coefficient critically dependent on film
behavior.

1. Film Theory
Film Theory: Overview

Film theory assumes a stationary film of thickness δ\deltaδ exists next to the
interface. Within this film, mass transfer is solely by steady-state diffusion.

The film concept of mass transfer was alreadt discussed briefly briefly in the
section on mass transfer coefficienl.The concentration profile in turbulent flow
when the solute is dissolving from the surface and is diffusing to the main stream.
The concentration of the solute decreases as the distance from the wall increases.
Three regions can be visualized in the flowing stream. In the stagnant layer of fluid
immediately adjacent to the solid surface, most of the mass transfer occurs by
moleculardiffusion; this layer is known as diffusional sub-layer. No eddies are
present in this layer. A large concentration drop occurs across the viscous sub-layer
as is clear from the figure. Major portion of the fluid cross section is the turbulent
core in which the mass transfer is mainly due to eddy transport. The 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 of mass transfer
C D AB
should
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.
C D AB
Then the quantity will represent film coefficient of mass transfer which is
z
related to k, or k, as given by Eq (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 first

approximation for highly turbulent fluids near solid surfaces, where the existence
of a thin stagnant layer is a reality.

Governing Equation:

2-Strengths of Film Theory:

 Simple and Intuitive: Provides a straightforward model for predicting mass

transfer in systems with low turbulence.

 Foundational Model: Forms the basis for more complex theories (e.g.,
penetration and surface renewal theories).

 Useful for Laminar Flow: Applies well to systems with stable flow and low
Reynolds numbers.

3-Limitations of Film Theory:

 Oversimplifies Reality: Assumes a flat, constant-thickness film, which is

rarely the case in real systems.

 Neglects Turbulence: Does not account for eddies or mixing near the
interface.

 Steady-State Assumption: Fails to model time-dependent behavior of real

diffusion processes.

 No Surface Renewal: Ignores the renewal or displacement of fluid elements

at the interface.
4-Assumptions in Film Theory for Mass Transfer Coefficient Prediction

To derive the mass transfer coefficient using film theory, the following
assumptions are made:

1. Stagnant Film Exists: A thin, unmixed layer (film) of fluid exists near the
interface through which diffusion occurs.

2. Steady-State Diffusion: The concentration profile does not change with

time within the film.

3. No Convection in the Film: Only molecular diffusion occurs in the film

region; no bulk motion.

4. Instantaneous Equilibrium at Interface: The concentration at the interface

is in equilibrium with the other phase.

5. Linear Concentration Gradient: Assumes a linear drop in concentration

from the bulk to the interface.
Higbie’s Penetration Theory:
Overview of Higbie’s Theory

Proposed by R. Higbie (1935), this theory assumes that fluid elements randomly
reach the interface and stay in contact with it for a finite and equal amount of
time, during which unsteady-state diffusion occurs.

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 move away from interface to get mixed with bulkstream thus according to
this theory, a fluid element whose initial concentration is the same as the
concentration of the bulk stream ace. (CA), A proc wA exposed to the second fluid
phase, equilibrium is established instantaneously at the interface is replaced by
fresh one and moves to and gets mixed with the bulk stream. Th the eddies
aementnsteady-state molecular diffusion occurs for a fixed time of exposure, after
which the fluid elema Thus the eddies are alternately static and moving. In Higbie's
experiments, a slug-like bubble of carbon dioxide was allowed to rise through a
column of water. 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 took place during this period by unsteady state
molecular diffusion. The depth of the liquid element is assumedto be infinite in
comparison with the depth of penetration of the solute. The concentration-time-
distance history in the liquid which was exposed to diffusion of a soluble gas can
be plotted as shown in Fig. 3.3. In the figure, the percentage saturation of the
liquid is plotted against 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 penetrationtheory. The rate of diffusion is governed by Fick's second law.

where t is the exposure time for the fluid element. For bubbles, the contact time of
the liquid surrounding the bubble is assumed to be the ratio of bubble diameter to
bubble rise velocity. For liquid spray, contact time is the time taken by the droplets
to fall through the gas. The depth of penetration is defined as the distance at which
the concentration change is one percent of the final value. Molar flux under
thicondition is
compare this with the folowing experission for mass flux written in terms of mass
transfer coefficent.

Thus, according to the penetration theory,

which predicts that the mass transfer coefficient is proportional to the square root
of the diffusion coefficient. If the dependeney of kL, to DAB is written as KL o«
DnAB. the penetration theory sets the value 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.

Expression for mass transfer coefficient:

This theory is useful in systems with moderate turbulence, such as gas-liquid

absorption in agitated tanks.
2-Strengths of Higbie’s Theory

 Accounts for Unsteady-State Diffusion: More realistic than film theory for
dynamic systems.

 More Applicable to Turbulent Flow: Handles systems where elements are

constantly replaced at the interface.

 Foundation for Further Models: Basis for the more advanced surface
renewal theory.

3-Limitations of Higbie’s Theory

 Assumes Equal Contact Time: All fluid elements have the same exposure
time, which isn’t true in real systems.

 Ignores Renewal Frequency: Doesn't consider how frequently the interface

is refreshed.

 No Surface Renewal Distribution: Lacks randomness in contact times

(improved in surface renewal theory).

 Mathematically Idealized: Real systems often deviate from this idealized

unsteady behavior.

4-Assumptions in Higbie’s Penetration Theory

The theory makes the following simplifying assumptions:

1. Unsteady-State Diffusion: Mass transfer occurs due to time-dependent

diffusion into a semi-infinite medium.

2. Constant Contact Time (tct_c): Every fluid element at the interface

remains in contact for the same finite time.

3. Fresh Fluid Elements Replace Old Ones: At the end of the contact time,
each fluid element is replaced with a new one.
4. No Bulk Convection During Exposure: Only molecular diffusion occurs
during the contact period.

5. Instantaneous Equilibrium at Interface: The interface is assumed to be at

equilibrium throughout.

6. Negligible Mass Transfer Resistance at Interface: The resistance is

primarily in the contacting phase (not across the interface).
3. Surface Renewal Theory
Overview of the Theory

Proposed by Danckwerts in 1951, the Surface Renewal Theory improves upon

Higbie’s model by allowing fluid elements to have varying contact times at the
interface. It introduces a probabilistic model to describe how often the surface is
refreshed.

Penetration theory with constant exposure time fails to represent the mass transfer
occurring in devIcessuch 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

Here ∅ 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

Which relates KL and DAB as,

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.

Mass transfer coefficient equation:

Where:

 D = molecular diffusivity (m²/s)

 s = surface renewal rate (1/s), representing the fraction of the surface

renewed per unit time

2-Strengths of Surface Renewal Theory

 Realistic Contact Times: Unlike Higbie’s theory, it allows fluid elements to

have a distribution of contact times.

 More Accurate for Turbulent Systems: Especially in agitated or bubbling

systems where the interface is frequently renewed.

 Bridges Theory and Reality: Offers a closer approximation to experimental

observations in industrial processes.

3-Limitations of Surface Renewal Theory

 Difficult to Measure sss: The renewal rate is not easy to calculate directly
and often must be estimated empirically.

 Complex Mathematics: The model involves more complex integrals when

applied rigorously.

 Still Idealized: Assumes renewal happens randomly and uniformly, which

may not always match chaotic flow conditions.
4- Assumptions in Surface Renewal Theory

The Surface Renewal Theory is based on the following assumptions:

1. Unsteady-State Diffusion: Solute diffuses into fluid elements for a finite

time.

2. Random Surface Renewal: Each fluid element at the interface is randomly

replaced by a fresh element at a certain rate sss.

3. No Bulk Motion in Diffusion Zone: Only molecular diffusion occurs

within the fluid elements.

4. Instantaneous Interfacial Equilibrium: The interface is assumed to always

be at equilibrium.

5. Semi-Infinite Medium: Diffusion occurs into a semi-infinite region during

the contact time.

6. Turbulent System: Assumes the system is turbulent enough to allow

random, frequent surface renewal.

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