Mass Transport Described by Diffusion Coefficient

In your second year course CL 203: Transport Phenomena, you studied concentration
distribution in solids where mass transport is described by diffusion coefficient. Well quickly
review this mass transport and then move on to convective mass transport, one of the main
topics of the present course, CL 319.
Transport of hydrogen in metals (Cusslers book): Hydrogen diffusion in metals makes them
brittle so they break easily. We wish to study hydrogen diffusion under different conditions.
We have two options available:
1. saturate metals with hydrogen and determine ductility their ductility as a function of
average hydrogen concentration,
2. expose metal surface to a certain hydrogen concentration and describe its transport
in the metal by a diffusion coefficient, .
If we were to select option 2, set-up a differential equation for hydrogen transport through a
metal shown below. (Recall shell mass balances learnt in CL 203) You need not solve this
equation now.
Gas with hydrogen
Hydrogen concentration at
surface =
hickness

Hint: Consider a thin slice of thickness

slice.

and write mass balance for hydrogen across this

ydro en accumulation
in

ydro en in
minus
hydro en out
both by diffusion

Now, write above equation mathematically usin Ficks law of diffusion.

Adolf Ficks experiments to establish his law of diffusion: Fick placed sodium chloride
crystals at the bottom of a glass cylinder on the top of which was a large volume of water as
shown. He conducted two experiments as shown. Calculate the steady state profiles in
these two experiments. He verified his proposed law by comparing these profiles with
predictions.

Experiment 1:

Experiment 2:

In the above two examples, mass transport is by molecular diffusion and the exact space
over which concentration (of H2 or salt) is known. Now, contrast these examples with the
ones discussed below.

Mass Transport by Convection

Dissolution of sugar crystals

Whats the difference between a) dissolution of su ar
crystals placed in glass of water without stirring and
b) dissolution of sugar crystals in an agitated glass of water?

Not drawn to scale

Assume that the crystals dont break durin a itation. Discuss time for dissolution,
concentration distribution.

oxygen

oxygen

Dissolution of oxygen in water

Imagine a closed glass vessel partially filled with water.
The remaining space at the top of the vessel contains pure oxygen gas.

water

water

Think of two possibilities: a) oxygen dissolution when the water is unstirred

and b) oxy en dissolution when it the water is stirred at a rate which doesnt
change the gas volume during agitation. Discuss mass transfer of oxygen into water in both
cases.

Drying of wet cloth

A wet cloth from which water is squeezed thoroughly is dried in a) quiescent air and b)
moving air. Discuss drying rates for a and b.
a

Moving air

Compare the examples for mass transport by diffusion and convection.

Mass transfer is also critical in many chemical processes such as

a) Removal of carbon dioxide and sulphur dioxide from flue gas for pollution abatement
and reduction of greenhouse gases, removal of H2S from natural gas because H2S is
a poison to catalyst which transforms natural gas into synthesis gas (CO + H2).
b) Production of antibiotics and other pharmaceuticals where oxygen is to be supplied
to microbes; and in purification of dilute streams of antibiotics.
c) Oxidation of ammonia to NO at high temperatures where reactions are fast and the
process is limited by the supply of ammonia to the Platinum catalyst.
d) Crystallization where growth of small nuclei that are generated from the mother liquor
due to high supersaturation in it is determined by mass transfer rates.
e) The list could go on and on
What you will study in this course will enable you to analyze mass transfer occurring in
several situations including those described above, design equipment for the mass transfer.

Learning Objectives

We are interested in describing and quantifying mass transfer across interfaces between two
phases as seen in previous examples. The transfer could be from liquid to gas, gas to liquid,
liquid to solid, solid to liquid, gas to solid and solid to gas.
Mass transfer across an interface into a well-mixed solution is proportional to the difference
between the concentration of transferring species at the interface and its concentration in the
bulk solution. The transfer is also proportional to the interfacial area. Thus,
Rate of mass transfer =

interfacial area concentration difference

Here , the proportionality constant is called a mass transfer co-efficient. In chemical

engineering analyses, one is interested in fluxes as in heat transfer flux. Mass transfer flux
is obtained by dividing both sides of the above equation with interfacial area. Expressing the
flux in usual symbols gives,
(1)
Where
is the mass transfer flux,
and
interface and in the bulk, respectively.

are concentrations of the species at the

Mass transfer can also occur from bulk of well-mixed solution to interface between that
solution and another phase. For this transfer,
(2)
If ammonia is transferred from its dilute mixture with other gases into water, to describe
ammonia transfer from gas phase to the interface between gas and liquid phases, we use
the equation 2. To find mass transfer rates from the interface into water phase, we use
equation 1.
Lets analy e the mass transfer rates in the previous examples studied.

Dissolution of sugar crystals with agitation (solid to liquid)

At any given instant of time, ,

is _____________________________________________

and is ________________________________________________, and interfacial area is

_______
Sugar dissolves faster at lower temperature or higher temperature? Why?

Dissolution of oxygen in water with agitation (gas to liquid)

Write and interfacial and bulk concentrations and interfacial area
is ______________________________________________________________
is _______________________________________________________________

Write a mass balance equation to determine how oxygen concentration in water changes
with time.
How can the rate of mass transfer be raised?

Evaporation of water from wet cloth into air (liquid to gas)

For this case,
is ______________________________________________________________
is _______________________________________________________________
Why does a spread out cloth dry faster than a crumpled cloth?

Why do clothes dry faster in summer than in winter?

Summary of driving forces for mass transfer between two phases

Mass transfer
direction
Solid to liquid
Gas to liquid
Liquid to gas
Solid to gas
(sublimation)

Interfacial area
We discussed the drivin forces so far. heres more to them which will be covered later
durin discussion on units of mass transfer coefficient. Lets turn our attention to interfacial
area. For fluid-fluid interfaces, this area can be tricky; for fluid-solid interfaces it is welldefined. Consider the following examples for interfacial areas.
1. Sublimation of a naphthalene ball into air. If you assume that the ball is spherical,
interfacial area is ___________ (even if you dont assume spherical shape, area can
be defined)
2. Dissolution of a drug in stomach. If the drug is assumed to be a thin disk, area for
mass transfer is ___________
3. Drying of a wet towel. If the towel is rectangular, interfacial area is ____________

4. Transfer of CO2 from flue gas into amine solutions in a cylindrical tower. Gas flows
upward in the tower as liquid moves down through it. The tower is packed with
material such as small glass pieces. What is the interfacial area?

Amine solution
with no CO2

Flue gas
containing CO2

Gas with
traces of CO2

Amine solution
with absorbed
CO2

5. In petroleum refineries, the crude oil is distilled into fractions in two distillation towers
(if you dont know how distillation looks or operates, its ok; well discuss these in
detail in later part of the course). The fraction exiting the bottom of the second tower
contains many hydrocarbons which can be converted into fuels. Unfortunately these
are present along with asphaltenes (tar). Their separation by distillation is not
possible. These hydrocarbons are separated from the asphaltenes by contacting
them with liquid propane in a tower shown below; hydrocarbons dissolved in propane
while asphlatenes dont. What is the interfacial area?

Heavy phase is mixture of

asphaltenes and hydrocarbons
Light phase is liquid propane.
Propane is immiscible with
asphaltenes; hydrocarbons partition
between propane and asphaltenes

Taken from
http://modularprocess.com/liquid-liquidextraction/extraction-column-types/rdc/

In examples such as 4 and 5, it is difficult to estimate the interfacial area; it cannot be usually
measured through experiments. The trick is to lump the area with mass transfer co-efficient
as
and estimate it. This parameter is called volumetric mass transfer coefficient.
Of course, manufacturers provide interfacial area of packings as in example 4, in units of
m2/m3. Here volume refers to the volume of the column. We shall analyze in detail, later,
design of absorption towers that use packings for effective mass transfer.

Mass transfer coefficient

A gas contains 5% ammonia. Ammonia is being absorbed into water. The gas phase mass
transfer coefficient which characterizes mass transport of ammonia from bulk gas to the
interface between gas phase and water phase is reported as 1.6 x 10-4 g mol NH3/(s cm2).
The liquid phase mass transfer coefficient which characterizes mass transport of ammonia
from the interface into bulk water is reported as 2.9 x 10-3 cm/s.

Write the flux equation for transfer of ammonia from bulk gas phase to the interface (Hint:
how would you like to express the driving force)

Write the flux equation for transfer of ammonia from the interface to the bulk water

Another study reports mass transfer coefficient for the liquid phase as 2.2 x 10-3 mol(s cm2).
Write the flux equation for this coefficient.

What do you observe from the three flux equations.

Summary of fluxes when different driving forces are used

Driving force

Flux equation

Units of mass transfer

Coefficient

Pressure
Concentration
Mole fraction
Note that the units could change if pressure is given in mm Hg, bar, atm, kPa etc.
Sometimes, mass fraction also could be used instead of mole fraction.
How do we convert a given mass transfer units from one driving force to another?
Lets say we are iven mass transfer units in cm/s ( ). However, we would like to use
, what is the relation between
and ?

What is the relation between

Now, try to convert

Do the conversion of

and

given in above problem to

into

1. Water evaporates from pond near IIT Guest House into air that is roughly 50%
saturated with water vapour. Mass transfer coefficient for the evaporation is 1.8
cm/s. If the average daily temperature during summer months (April and May) is 35
o
C, at what rate does the water level decrease? Will the pond dry up by the end of
May? Vapour pressure of water at 35 oC is 42 mm Hg.
2. Pure oxygen is being bubbled into a tank containing 5 liters of water. Average
diameter of the bubbles in water is 2-cm. Experiments indicate that the total bubble
volume is 1.5 liters (fraction of bubbles volume to total fluid volume). How long will it
take to attain 50% saturation starting with pure water. Mass transfer coefficient of
oxygen in water is 1.6 x 10-3 cm/s.

Measurements of mass transfer coefficients by experiments

Wetted Wall Column
A popular way of measuring mass transfer coefficient in liquids is by a wetted column shown
below.
Pure
Pure water
water
Almost
pure air
z

Air with soluble gas such

as NH3

Air flows into the column at

velocity, (cm/s); column height is
(cm); water film thickness is
(cm); diameter is (cm),
concentration of gas in inlet water is
0; concentration in outlet water is
(mol/cm3)

Water with absorbed gas

Air having a soluble gas such as ammonia is sent up a column along the walls of which
water flows down in a thin film. The film thickness can be controlled by changing the flow
rate of water. As water flows down it absorbs the soluble gas. By measuring concentration
10

of gas in water, mass transfer coefficient of the gas in water is calculated. It is assumed
reasonably that the air is well mixed up to the interface with water. We wish to develop
equations for calculating the coefficient by writing a mass balance for the soluble gas in a
thin slice across the column at some height. Then this equation is integrated with
appropriate boundary conditions to give the final result.
Write the mass balance equation of the gas in water in a thin section z and then integrate it.

If the mass transfer coefficient obtained by an experiment described above, deviates from
reported values significantly, what could have gone wrong? Mention three possible reasons.
1.
2.
3.

Sublimation of naphthalene
A naphthalene ball having a mass of 0.6 g (1-cm in diameter) is hung in quiescent air at 25
o
C. Vapour pressure of naphthalene at 25 oC is 0.087 mm Hg. Its mass after 42 days is
0.57 g. What is the mass transfer coefficient in appropriate units?

11

Homework 1

1. (Ch 8, Prob 4) A disk of radioactively tagged benzoic acid 1-cm in diameter is

spinning at 20 rpm in 94 cm3 of initially pure water. We find that the solution contains
benzoic acid at 7.3 x 10-4 g/cm3 after 10 hours 4 minutes and 3.43 x 10-3 g/cm3 after a
long time (i.e. at saturation). (a) What is the mass transfer coefficient?, (b)How long
will it take to reach 14% saturation?
2. (Ch 8, Prob. 5) As part of the manufacture of electronic circuits, silicon wafers are
partially coated with 5400-Angstrom thick polymerized organic film called photoresist.
The density of this polymer is 0.96 g/cm3. After the wafers are etched, the
photoresist must be removed. To do so, the wafers are placed in groups of twenty in
an inert boat which in turn is immersed in a strong organic solvent. The solubility
of the photoresist in the solvent is 2.23 x 10-3 g/cm3. If the photoresist dissolves in 10
minutes, what is the mass transfer coefficient?
3. A wet T-shirt is hung in air at 25 oC for drying. The total surface area of the shirt is
0.6 m2. The relative humidity of air is 50%. The following time versus weight data
are collected. What is the mass transfer coefficient?
Time,pm
Weight, g

3:15
661

3:20
640

12

3:48
580

4:00
553

Lets now solve the sublimation problem of naphthalene ball with a diffusion coefficient
instead of a mass transfer coefficient. For this purpose, write mass balance of naphthalene
in a thin shell around the ball as shown below. We will solve this problem as a pseudo
steady state because naphthalene sublimation is very slow and diffusion ensures that its
concentration profile develops before more naphthalene sublimates. Our goal is to relate
mass transfer coefficient to diffusion coefficient.

The above derived relation is exact for a simple case such as solid sphere suspended in
quiescent fluid.
Experiments made to estimate mass transfer coefficient showed that it varied with flow rate
of air, size of the naphthalene ball, and other physical properties such as density and
viscosity. How do we organize data collected from several sets of these experiments to
generate an equation to predict the coefficient as a function of all changed variables? We
would like to use this equation for any other solid either suspended in any quiescent fluid or
moving fluid.
----------------------------------------------------------------------------------------------------------------------Lets di ress a bit and o over boundary layer theory, which might have come across in
courses such as Transport Phenomena and Heat Transfer.

13

Turbulent
region

The problem is find how a sharp-edged plate inserted into a smooth flow disturbs it. The
plate perturbs the flow near its leading edge. The region from this edge to the point where
the flow attains 99% (fixed arbitrarily) of its free-stream velocity is called boundary layer.
The thickness of this layer changes along the flow direction. Refer to the figure below to
understand the boundary layer clearly.

Boundary
layer
Laminar
region

Equations of continuity and momentum written in the boundary layer with suitable and
reasonable modifications with relevant boundary conditions, gives the following result for
boundary layer thickness, :

Please refer to Cusslers book for the above derivation. If a plate made of sparin ly soluble
solid, such as benzoic acid, is placed in the smooth flow, a concentration boundary layer
develops. That is the region from the plate to the point where the concentration equals 99%
bulk concentration.
It can be derived that the thickness of concentration boundary layer,

(see Cussler for

complete derivation) is:

The mass transfer coefficient can be shown to be equal to:

This is the result we are seeking. The mass transfer coefficient characterizes the rate of
dissolution of benzoic acid into the flowing liquid. The prediction agrees with experiments for
a flat plate closely. A similar relation can be derived for heat transfer coefficient also.
A quick check of the above equation reveals that all terms are dimensionless, that is they
dont have any units. he first term on the L S is called Sherwood Number
.
mass transfer coefficient x characteristic len th
diffusivity
14

The characteristic length in the above derivation is length of the plate; for dissolution of a
sphere it is the diameter; for flow through a packed bed, it is the nominal size of the packing.
What is the first term on the RHS?

The second term on the RHS is the Schmidt number,

It signifies the ratio of

momentum transport to mass transport. It is high for liquids and low for gases.
We now return to the question raised earlier on organization of collected data for mass
transfer of sphere into flowing fluid. Inspired by the relation generated by boundary layer
theory, the data is organized such that
. This kind of organization helps us
predict mass transfer coefficient without conducting experiments and gain some insight into
the mass transfer process.
Do you recollect a correlation similar to

in heat transfer?

Write it:

he next few pa es reproduced from Cusslers book shows several correlations for mass
transfer coefficient.

15

Physical situation
Liquid in a packed tower

Basic equation

Key variables
packing area per bed volume
nominal packing size

nominal packing size

Gas in a packed tower

The classic result, widely quoted;

probably less successful than above.

nominal packing size

Based on older measurements of

HTUs; is of order one.

packing area per bed volume

nominal packing size

Probably the best available

correlation for gases.

nominal packing size

bed void fraction

Pure gas bubbles in a stirred

tank

Remarks
Probably the best available
correlation for liquids; tends to give
lower values than other correlations.

bubble diameter
stirrer power per volume

Again, the most widely quoted

classical result.
Note that does not depend on
bubble size

Pure gas bubbles in an

unstirred tank

bubble diameter
is density difference between
gas and liquid

For small swarm of bubbles rising in

a liquid.

Large liquid drops rising in

unstirred solution

bubble diameter
is density difference between
bubbles and surrounding fluid

Drops 0.3-cm diameter or larger.

Small liquid drops rising in

unstirred solution
Falling films

16

drop diameter
drop velocity

These small drops behave like rigid

spheres

position along film

average film velocity

Frequently embroidered and

embellished.

Physical situation
Membrane

Basic equation

Key variables
membrane thickness

Laminar flow along flat plate

Remarks
Often applied where membrane is
hypothetical
Solid theoretical foundation, which is
unusual.

plate length
bulk velocity

Turbulent flow through

horizontal slit

Mass transfer here is identical with

that in a pipe of equal wetted
perimeter.
Same as slit because only wall
regime is involved.

average velocity in slit

(slit width)

Turbulent flow through circular

tube

average velocity in tube

pipe diameter

Laminar flow through circular

tube

pipe diameter
pipe length
average velocity in tube

Flow outside and parallel to a

capillary bed

area/wetted diameter
superficial velocity

Flow outside and

perpendicular to a capillary
bed
Forced convection around a
solid sphere
Free convection around a
solid sphere

Very strong theory and experiment.

Not reliable because of channelling in

bed.

capillary diameter
velocity approaching bed

Reliable if capillaries are evenly

spaced

sphere diameter
velocity approaching sphere

Very difficult to reach

experimentally.

sphere diameter
g = acceleration due to gravity

For a 1-cm sphere in water, free

convection is important when
-9
3
10 g/cm .

Packed beds

particle diameter
superficial velocity

The superficial velocity is that which

would exist without packing.

Spinning disc

disc diameter
disc rotation (radians/time)

Valid for Reynolds number between

100 to 20,000

diffusion coefficient;
is kinematic viscosity.

and

are Reynolds numbers;

is Schmidt number;

17

is Grashof number;

is Sherwood number;

is fluid density,

Another example to show organization of data is dissolution of a spinning disk.

Spinning disk

Solute from
dissolving disc

Flow

See Cusslers book for detailed mathematical modellin of solute dissolution in movin fluid
from a spinning disk. The model involves solving fluid mechanics (velocities) and mass
balance equations simultaneously. The equations are not shown here. The final equation
for the flux of solute is

This equation can also be arranged in the form

. Here the mass transfer
coefficient is derived from theory. The plot scanned from the text book shows excellent
agreement between theory and measurements. Such agreement can be found for fluid-solid
interfaces but rarely for fluid-fluid interfaces. The accuracy of correlations for fluid-fluid
interfaces is typically about 30%; larger errors are also possible. For solid-fluid interfaces,
the accuracies are typically 10% or even better. They are useful in preliminary design of
experiments and pilot plants; for design of full scale equipment, experiments are necessary.

18

Huang et al. (1981) reported mass transfer studies with liquid spinning discs in the journal
Chemical Engineering Science. In one such study, a microporous polymer disc is
completely wet by a solute; this disc is then placed in a solvent and rotated at a certain
speed. The solvent does not wet the polymer. In other words, only the solute in the pores of
the disc is transferred into the solvent; the solvent is not transferred into the pores. One
such solute-solvent system is heptanoic acid and water.
Table below shows the experimental data collected. How do you proceed to organize this
data to present a correlation? Radius of the disc = 0.794 cm, kinematic viscosity of
heptanoic acid,
3.69 x 10-3 cm2/s, Solubility of heptanoic acid = 3.45 x 10-3 g/cc; Volume
of vessel = 15 cm3.
Speed,
3.1

2.72

10.7

17.1

27.2

, rad/s

Time, , min
0
3
15
0
3
115
0
3
15
0
3
5
8
15
0
2
15

Concentration,
0
1.11
3.78
0
1.50
5.34
0
2.02
6.97
0
2.32
3.65
5.34
8.70
0
2.28
10.23

19

x 10-4 g/cc

A wetted wall column is used to study mass transfer of oxygen into water. In one
experiment, a 5-cm column absorbs oxygen so the water leaving it is 10% saturated.
Entering water has no oxygen in it. The film thickness is 0.07 cm and the liquid velocity is 3
cm/s. What is the mass transfer coefficient? How closely does it match with correlation
given in the above Table?

20

Homework 2
1. (Ch 8, Prob 11) Air at 100 oC and 2 atm is passed through a bed of 1-cm in diameter
composed of iodine spheres 0.07-cm in diameter. The air flows at a rate of 2 cm/s,
based on the empty cross section of bed. The area per volume of the bed of spheres
is 80 cm2/cm3, and the vapour pressure of iodine is 45 mm Hg. How much iodine will
evaporate from a bed 13 centimetre long, assuming a bed porosity of 40%? Bed
porosity is the fraction of bed volume not occupied by the spheres.
2. A 500-gallon tank 8 feet deep is to be saturated with oxygen using a small sparger 2
inches in diameter with a flow of 1 ft3/min. The sparger produces 0.3-cm bubbles
that rise through the tank at 10 cm/s; other properties of the fluid in the tank are
essentially those of water. How long does it take it to reach 50% saturation? Useful
correlations are as follows: within the bubbles, Sherwood is two; outside the bubbles,
one good correlation is given by P. H. Calderbank [In: Mixing, ed. V. Uhl. New York:
Academic Press (1967)]:
3. A microorganism is being grown in a shaker flask at 37 oC. The volume of water in
the flask is 100 ml. Air is supplied through a porous stopper. The air bubble is 0.3cm in diameter. The microorganism consumes oxygen at the rate of 6.3 x 10-6
kmol/s. What is the concentration of oxygen in the solution as a percent of its
saturation?

21

Theories for interfacial mass transfer

Two-film theory (Lewis and Whitman, Industrial and Engineering Chemistry Research, 1924)
This theory supposes that for interfacial mass transfer of a species from one phase to
another, where both phases are well-mixed two films or unstirred layers exist one on each
side of the interface. All the mass transfer resistance exists is in this film or layer. Beyond
these films, the concentration of transferring species is uniform. Such hypothetical films was
first suggested by Nernst in 1904.
For clarity lets consider an example. Oxy en is diffusin from air into water; this example
was alluded to earlier (see page 1). Below Figure shows two film theory for this system.

Liquid film

Gas film
Air-water
interface

Few points are worth noting and remembering/understanding.

The gas film is on the gas-side next to the interface; the liquid film is on the liquid-side next
to the interface.
For oxygen transfer in gas phase,
For oxygen transfer in liquid phase,
The interface does not offer any resistance to mass transfer; hence, it is always at
equilibrium. The implication of these statements is that the concentrations at the interface
on its either side are related. Please note that the concentrations are expressed as and .

22

They could also be written as and or any other combination of , and . It is customary
to write gas phase concentrations in ; liquid phase concentrations are expressed as or .
What would be the relation between and for transfer of oxygen in water? (Recall
solubility of sparingly soluble gases in liquids)

On the other hand, if a highly soluble gas such as hydrogen chloride in being absorbed into
water from a gas mixture, we need to know the equilibrium relation to find the interfacial
concentrations. One could use information such as given below charts.

What is the concentration in the liquid at

the interface if temperature and HCl partial
pressure are:
a) 30 oC, 0.01 mbar
b) 70 oC, 0.1 mbar
c) 50 oC, 1 mbar

Taken from: http://www.qvf.com/qvf-processsystems/mineral-acids/absorption-of-hydrogenchloride

At the interface, can the concentration on liquid-side be greater than the concentration on
gas-side if transfer happens from gas to liquid?

The flux of oxygen can also be written in terms of the diffusion coefficient and thickness of
the liquid film, :

Comparing this equation with the one written in terms of mass transfer coefficient gives,

23

A similar relation between mass transfer coefficient on gas-side and diffusion coefficient of
oxygen in air can also be written easily.
The thickness of the films is known apriori. One might wonder, if the film theory cannot
predict mass transfer coefficient, of what use is it?
As Cussler notes, the theory provides an insight into mass transfer process and also as we
will see later, it is useful in analysis of mass transfer processes involving chemical reaction.
This theory also shows that Sherwood number equals one,

Recall that Sherwood number appears in all correlations shown above. The film thickness is
also a function of flow and physical properties such as density, viscosity. Therefore,
other system variables
Mass transfer into a rapidly flowing liquid is faster because the film thickness is reduceda
film theory interpretation of increase in mass transfer with flow.
For the cases shown below, draw films and concentration profiles next to the diagrams.
Describe the physical significance of the variables you indicate in the diagram.

Naphthalene ball
sublimating in air

Sugar crystal
dissolving in water

Dispersion of an aqueous solution containing

a protein in an immiscible organic24solution. The
protein transfers from aqueous phase into the
organic phase.

O2
H2O
Pure O2 dissolving into water
The agitation does not disturb the
interface.
What is the difference between the concentration profiles drawn for above oxygen transport
to that drawn in the explanation of two film theory?
We shall return to film theory when overall mass transfer coefficient is discussed. Now lets
analy e i bies penetration theory

Penetration Theory (Higbie, AIChE J, 1935)

Higbie suggested a model for his theory of mass transfer in a paper in 1935. Figure below
captures the model.

Flowing liquid

Short time

long time

Taken from Cusslers book

A sparingly soluble pure gas is in contact with a flowing liquid. As the liquid move down, the
gas dissolves in the liquid and diffuses through it. The mass transport in the direction is by
diffusion and in the direction is by convection. This is a reasonable assumption for a
sparingly soluble gas.

25

The math is a little bit daunting. Those interested can read further and those who detest
math can assume that the final equation is correct and learn from the conclusions drawn by
solving the model equations.
We start by writing mass balance equation in a control volume

Mass accumulation in the volume = (Mass diffusing in at minus mass diffusing out at
) + (Mass flowing in at minus mass flowing out at
).
Written mathematically the above statement gives,
+

Convection

Diffusion

For steady state proble, LHS = 0, If diffusive flux, is described by Ficks law, both sides
are divided
and a limit is taken that the volume goes to zero and
is assumed to be
, the above equation simplifies to:

This differential equation is subjected to the following conditions:

is the thickness of the liquid film; for short times it can be assumed to be . That is, for
certain time, the dissolving and diffusing gas does not see the end of the film. After long
time, of course, the profile reaches the other end. Our analysis is for short times, therefore,
the last condition can be replaced by
.
The solution of this differential equation can be obtained by defining a new variable in terms
of and ,
, where
.
Detailed derivation of further solution of the equation is not given. Please check out the
book for the details. The concentration profile is given by,

The flux at the interface,

is

The interfacial flux averaged over

is given by

26

Double integration of the flux gives

Comparing this with the flux written with a mass transfer coefficient,
quantity

. The

is contact time. This time is also unknown apriori as was the film thickness

in the film theory. This theory suggests that the mass transfer coefficient varies with
instead of as su ested by the film theory. Which of them is ri ht? We dont know.
However, they tend to bracket the experimentally observed results.
The equation obtained for mass transfer coefficient can be rearranged in terms of
dimensionless numbers recognizing the fact that average velocity is two-thirds of maximum
velocity. The rearrangement gives,

This is of the form

Recall that the correlations generated from experiments look similar to the above equation.

Surface Renewal Theory (Danckwerts, Industrial and Engineering Chemistry Research

1951)
Imagine a stirred vessel containing water into which oxygen is sparged (injected through
small holes in a ring placed in the vessel). The water at the surface of a oxygen bubble is
continuously replaced with water from the bulk. Some water spends very little time at the
surface and some very large time. That is, there is a distribution of times that water spends
at the surface of the bubble. Penetration theory assumes that all water spends certain same
time with the bubble.
The key in deriving relation between mass transfer coefficient and diffusion coefficient in
surface renewal theory is to get the distribution of ages.
The derivation is not difficult but out of scope of this course. The final relation is

where is average residence time of bubbles. Comparison with penetration theory shows
that there is no significant change in the relation. An unknown is replaced with an
unknown . Two points are worth mentioning: First,
as in penetration theory;
second surface renewal theory is a more realistic physical situation than penetration theory.
he unstirred layer thickness in film theory the time in penetration theory and average
residence time, , in renewal theory are all unknown. Nevertheless they provide a simple
way in which to think about mass transfer.
27

Overall Mass Transfer Coefficient

Ram: I completed studies on finding mass transfer coefficient in gas phase of the gas
component, A, to be absorbed from a gas mixture.
Shyam: I determined the mass transfer coefficient of A in liquid phase into which its
absorbed.
Ram: Your value is far lower than mine. This comparison indicates that the mass transfer
process is controlled by liquid phase and not gas phase. In other words, mass transfer in
gas phase is way faster than liquid phase.
Shyam: But, A is highly soluble in the liquid. So, the liquid can absorb large volumes of A.
Ram: You are right. However, solubility is an equilibrium property. Mass transfer
coefficients characterize the rate at which equilibrium is approached. Hence, I maintain that
liquid phase controls the process.
Shyam: If I recollect correctly, interfacial equilibrium is discussed in two film theory. Does it
equilibrium affect mass transfer at all?
Ram: Why dont we start from basics write equations and then conclude.
Shyam: Lets do it.

Film in Phase 1

Film in Phase 2
Interface
between
two phases

Mass flux from bulk of phase 1 to the interface in terms of mass transfer coefficient,

28

is:

Mass flux from the interface to bulk of phase 2 in terms of mass transfer coefficient,

is:

Relate the interfacial concentrations throu h enrys law:

Now find the equation for mass flux in terms of bulk concentrations,
final equation should not have interfacial concentrations,
and .

and

. The

What is the overall mass transfer coefficient?

Could we now resolve Ram and Shyams ar ument?

How do we interpret the concentration driving force that multiplies with overall mass transfer
coefficient?

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Example for Cusslers book

Jasome is a valuable material in the perfume industry, used in making soaps and cosmetics.
Suppose we are recovering this material from a water suspension of jasmine flowers by an
extraction with benzene. The aqueous phase is continuous; mass transfer coefficient in the
benzene drops is 3.0 x 10-4 cm/s; the mass transfer coefficient in the aqueous phase is 2.4 x
10-3 cm/s. Jasmone is about 170 times more soluble in benzene than in the suspension.
What is the overall mass transfer coefficient?

30

Below problem is adapted from Qin et al. (Journal of Membrane Science, 50, 51-55, 1990)
Fermenter of a wine making industry produces acidic wine due to its unsuccessful
operations. A major contaminant in the produced wine is acetic acid. Note that the
concentration of acetic acid is very low. This acid is to be removed by flowing the acidic
wine through a hollow fiber membrane; the acid transfers through the membrane surface into
an aqueous solution of NaOH flowing on the other side of the membrane. NaOH reacts fast
with acetic acid that diffuses through the membrane. A wine with known concentration of
acetic acid flows from a reservoir through the membrane and back into the reservoir. NaOH
solution flows from another reservoir on the outside of the membrane and back into the
reservoir. The concentration of acid in the wine reservoir is measured with time. What is the
overall mass transfer coefficient? Use the Tabulated concentration of acetic acid in the feed
solution. The numerical values of membrane area and volume of feed solution are same.
Time, min
C/Co

0
1

10
0.987

20
0.974

31

40
0.948

80
0.900

120
0.852

Homework 3
1. (Ch 13, Prob 1) As part of a study of O2 absorption in water in a small packed tower,
you find that the outlet concentration of O2 is 1.1 x 10-3 molar. The partial pressure of
O2 in the tower is about 0.21 atm; the total area in the tower is 1.37 m2; the liquid flow
is 1.62 liters per minute.
1.8 x 10-5 cm2/s. Find (a) the film or unstirred layer
thickness and (b) the contact time
2. (Ch 13, Prob 4) Ether and water are contacted in the Lewis cell shown below. An
iodine-like solute is originally present in both phases at 3 x 10-3 M. However, it is 700
times more soluble in ether than in water. Diffusion coefficient in both phases is 10-5
cm2/s. Resistance to mass transfer in ether is across a 10-2 centimeter film;
resistance to mass transfer in water involves a surface renewal time of 10 seconds.
What is the concentration in the ether after 20 minutes?
3. A packed tower is being used to remove ammonia from a gas stream containing only
3% of that gas. The 50-cm diameter tower contains packing of 1-cm nominal
diameter. The gas flow is 0.93 kg/s at 30 oC and 1100 mm Hg pressure. The liquid
with essentially water-like properties flows through the tower at 6.7 kg/s. The Henrys
law constant under these conditions is
. Find overall mass transfer
coefficient and determine which resistance, gas-side or liquid-side, controls the mass
transfer process.

32

Key Points on Convective Mass Transfer

Rate of mass transfer is the product of mass transfer coefficient, , interfacial area, ,
and concentration difference,
Remember: the concentrations are on the same side of interface. For example, if
transfer of a sparingly gas is being described in liquid side, then
is the
concentration term in enrys law on the liquid side. Think about this a bit clearly.
Imagine transfer from liquid to gas, liquid to liquid and ask yourself what is .
Pay attention to interfacial area. It is easy to describe if mass transfer happens in
fluid-solid interfaces with well described geometry for solids. For fluid-fluid cases, it
cannot be measured easily.
Many times the interfacial area is combined with mass transfer coefficient and the
product
is measured experimentally.
Units of mass transfer coefficient can be potentially confusing. They depend on the
units of concentration used in flux equation. Refer to below Table for clarity. Units of
concentration can be mol/cm3, g/cm3, kmol/m3 etc; pressure can be expressed in mm
Hg, bar, atm, kPa etc; time can be is s, min, h.

Driving force

Flux equation

Pressure

Units of mass transfer

Coefficient
mol/(cm2 mm Hg s)

Concentration
Mole fraction

cm/s
mol/(cm2 s)

You should be comfortable in being able to convert from one units of mass transfer
coefficient to another.
Mass transfer coefficients can be experimentally measured. Wetted wall columns
offer known interfacial area to measure mass transfer coefficients.
The dependence of mass transfer coefficients on physical properties such density,
viscosity, diffusivity and flow properties such as velocity are captured in
dimensionless correlations.
A typical correlation relates Sherwood number with Reynolds number and Schmidt
number. Please refer to the Table in the notes for definitions of these numbers.
The origin on these correlations is probably in boundary layer theory, which derives
relates the above dimensionless numbers from sound theoretical equations.
Remember that the correlations for fluid-fluid interfaces are only
accurate.
They can be used for preliminary estimates and designs; experiments with your own
physical system may not be avoidable.
Two film theory for mass transfer supposes that the entire resistance to mass
transfer lies in two films, one on each side of the interface. The bulk regions of the
two fluids are well-mixed. At the interface, equilibrium is established. This theory
relates mass transfer coefficient and diffusion coefficient as

, is film or

unstirred layer thickness. his quantity is unknown apriori. Hence cannot be

predicted from ; however, this theory helps us understand mass transfer process
but it is invoked in processes involving mass transfer and chemical reaction.

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Higbie developed a penetration theory for mass transfer according to which

a ain here the contact time , is not known. This theory can be used to estimate
mass transfer coefficients if contact time is known reasonably.
Danckwerts improved upon the penetration theory and considered realistic
distribution of contact times to derive what is called surface renewal theory. Mass
transfer coefficient by this theory is given by

where

is surface renewal time.

is unknown beforehand to predict .

Mass transfer rates between two phases are usually described by overall mass
transfer coefficient, which is a somewhat weighted average of individual mass
transfer coefficients.
This overall coefficient determines the controlling resistance to mass transfer. Check
the equation or overall coefficient to see how solubility alters the controlling
resistance.

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