1

Introduction to Mass Transfer

Mass transfer is the movement of mass from one place to another due to differences in
chemical potential of a compound in the two places.
In a single phase this means transfer of a component from a region where its
concentration is high to a region where its concentration is lower. At equilibrium the
concentration is the same everywhere.
If the transfer is across a phase boundary it can be from a low to a high
concentration. Imagine solutions of salt in oil and water with an equal concentration
of salt in both if you mixed them you would expect a mass transfer of salt into the
water in which it is more soluble. At equilibrium the concentrations will be different
in the two phases.

Examples
1. Dissolution of a crystal

Initially there is a high solute concentration close to the crystal surface and a low
solute concentration in the bulk of the liquid. Through time the concentration in the
bulk rises. Figure 1 shows how the concentration of the bulk solution might change
from the time that the crystals are added. One curve represents the case where the
crystals never completely dissolve. Which curve? Why do they not completely
dissolve? What does the dotted line represent?

Figure 1 Crystal dissolution

2. Evaporation of water into air
Figure 2 shows water evaporating from two shallow trays into a flow of air. Which
tray will dry up first, A or B? What factors affect the rate of drying?


Figure 2 Water evaporation into a flow of air.
Time
Bulk
Concentration
1 cm depth 2 cm depth
A B
0.5 m
2
1.0 m
2
2

3. Gas Phase Catalytic Reaction
Consider a gas phase catalytic reaction in which A reacts to form B. There are three
steps in series (three resistances):
- Mass transfer of A through the boundary layer.
- Chemical reaction on the surface.
- Mass transfer of B through the boundary layer.
Figure 3 illustrates the concentration profiles. Notice that the concentrations where
the reaction takes place (at the surface) are different from the ones you would measure
in the bulk gas.

Figure 3 Concentration profiles for gas phase catalytic reaction
4. Separation of components in a mixture by a Mass Transfer Operation

These operations involve concentration gradients within phases and transfer across
phase boundaries.

Gas / Liquid
- Absorption
- Evaporation
- Distillation

Gas / Solid
- Drying
- Adsorption

Liquid / Solid
- Crystallisation
- Ion exchange

Liquid / Liquid
- Solvent extraction

Measures of Concentration for Gas and Liquid Phases

For ideal gases: P
T
V=RT
And Daltons Law: p
A
=y
A
P
T


p
A
is the partial pressure of A.
Solid non-porous
Catalyst
Bulk
Gas
C
A
C
B
Boundary
Layer
3
y
A
is the mole fraction of A.
V is molar volume, i.e. m
3
per mole of total gas.
V
1
gives molar concentration, c
T
i.e. moles per m
3
.
For a binary ideal gas mixture with components A and B:

RT
p
RT
P y
V
y
c y c
A T A A
T A A
= = = =
And similarly for B.

For liquids: x
i
= c
i
/c
T
x
i
is the mole fraction of component i.
Molecular Diffusion in a Binary Gas Mixture
Transfer of a component within a phase can be by:
- Molecular diffusion: random movement of molecules. This predominates in a
stagnant fluid or in laminar flow.
- Eddy diffusion: transport by natural or forced convection currents or
turbulence.
In this course we only deal with molecular diffusion. Figure 4 shows diffusion from
point 1 to 2 in a single phase.



Figure 4 Diffusion in a single phase
There are two important idealised cases to be considered:

- Transfer of A and B at equal molar rates but in opposite directions. This is
equimolar counterdiffusion of A and B. There is no net flow of material
across any plane.
e.g. Catalytic Reaction, A B
Binary distillation of eg. ethanol and water.

- No transfer of B. Diffusion of A occurs through a stagnant/stationary gas B.
there is a net flow of material in the direction of decreasing c
A
.
e.g. Evaporation of water vapour into air or condensation of water vapour
from air.
Absorption of CO
2
from air using a liquid absorbent.
c
A1
c
A2
distance
Transfer of A
Perhaps transfer of B
4

It is important to grasp the difference between molecular diffusion and bulk flow.
Look at Figure 5a. Initially pure A is separated from pure B by a permeable barrier.
The pressure is the same everywhere. A will diffuse into B, and B will diffuse into A.
Imagine that you stand on either side of the barrier. Face left. Would you feel a wind
on your face? Face right. Would you feel a wind now?
The diffusion of A is exactly balanced by the diffusion of B.

Now look at Figure 5b. Ammonia in air is brought into contact with water. The
ammonia will start to dissolve. Assume that the air does not dissolve and the water
does not evaporate. Stand on the air side of the interface. Face left then right. Would
you feel a wind on your face in either direction? Why?
There is a bulk movement of gas towards the water. The air cannot move so while it
is blown towards the water it must diffuse back at the same rate. For the diffusion of
air to take place the concentration of air must be higher at the interface than in the
bulk gas.

Figure 5 Illustration of counter-diffusion and movement of one species
We will use J to represent diffusional flux and N to represent the total movement of a
species by diffusion and bulk movement.
Ficks 1st Law
The basic law describing molecular diffusion is Ficks 1
st
Law:
dx
dc
D J =
J is the molar flux, mol/m
2
s
D is diffusivity, m
2
/s
c

is concentration, mol/m
3

x is distance, m

Note that it is convenient to work in molar terms.
In a mixture of A and B, the diffusion of A is given by:
dx
dc
D J
A
AB A
=
And for B:
dx
dc
D J
B
BA B
=

For a constant pressure ideal gas system, c
A
+ c
B
= c
T
= constant.
Hence:
dx
dc
dx
dc
B A
=
And if the pressure is the same everywhere there is not net transfer of molecules so
J
A
= -J
B
.
Ammonia
in air
A B
Water
(a) (b)
5
And hence D
AB
= D
BA.
From now on we will use D to represent both D
AB
and D
BA
.

For an ideal gas:
dx
dy
Dc
dx
dp
RT
D
dx
dc
D J
A
T
A A
A
= = =

Equimolar Counterdiffusion

Figure 6 Equimolar counterdiffusion in a single phase binary system

The fluxes of A and B are equal and opposite
J
A
= - J
B
=
dx
dc
D
A


} }
=
2
1
0
A
A
c
c
A
x
A
dc D dx J

Integrate to give: ( ) ( )
2 1 2 1 A A
T
A A A
y y
x
Dc
c c
x
D
J = =
or for an ideal gas: ( ) ( )
2 1 2 1 A A
T
A A A
y y
RTx
DP
p p
RTx
D
J = =
Since there is no bulk flow with equimolar counterdiffusion, N = J for any species.

( )
2 1 A A A A
c c
x
D
J N = =

( )
2 1 A A B B
c c
x
D
J N = =
Figure 7 shows the concentration profiles for A and B. Note that they are linear.
Concentration
Distance, x
c
A1
x
x c
A2
x 0
Transfer
of A
Transfer
of B
6

Figure 7 Concentration profiles for equimolar counterdiffusion
Summary of fluxes
A B A + B

Diffusion, J
dx
dc
D
A

dx
dc
D
A
0

Bulk Flow 0 0 0

Total, N
dy
dc
D
A

dy
dc
D
A
0


Diffusion Through A Stationary Gas

Again:
dx
dc
D J J
A
B A
= =

But the total movement of B, N
B
= 0 since B is stationary.

So J
B
must be opposed by a bulk flow of B =
dx
dc
D
A

N
B
= diffusional flux of B + bulk flow of B 0 = + =
dx
dc
D
dx
dc
D
A A

Accompanying a bulk flow of B =
dx
dc
D
A

there must be a proportional bulk flow of A =
dx
dc
c
c
D
A
B
A


N
A
= diffusional flux of A + bulk flow of A
dx
dc
c
c
D
dx
dc
c
c
D
dx
dc
D
A
B
T A
B
A A
= =

The ratio c
T
/c
B
is called the drift factor (>1) ( 1 for systems dilute in A, for
which c
B
~ c
T
)

C
T
C
A1
C
B2
C
A2
C
B1
0
0 x
7
Stefans Law,
dx
dc
c
c
D N
A
B
T
A
=
Integrating,
} }

=
2
1
0
A
A
c
c A T
A
x
T
A
c c
dc
dx
Dc
N


integrate to give:
|
|
.
|

\
|

=
|
|
.
|

\
|

=
1
2
1
2
1
1
ln ln
A
A T
A T
A T T
A
y
y
x
Dc
c c
c c
x
Dc
N

or for an ideal gas:
|
|
.
|

\
|

=
|
|
.
|

\
|

=
1
2
1
2
1
1
ln ln
A
A T
A T
A T T
A
y
y
RTx
DP
p p
p p
RTx
DP
N



Figure 8 shows the concentration profiles for A and B. Note that they are non-linear.

Figure 8 Concentration profiles for diffusion of A through stagnant B
Summary of fluxes
A B A + B

Diffusion, J
dx
dc
D
A

dx
dc
D
A
0

Bulk Flow
dx
dc
c
c
D
A
B
A

dx
dc
D
A

dx
dc
c
c
D
A
B
T


Total, N
dx
dc
c
c
D
A
B
T
0
dx
dc
c
c
D
A
B
T



Example
A layer of benzene (C
6
H
6
) 5 mm deep lies at the bottom of an open cylindrical tank 5m
in diameter. The tank temperature is 295K and atmospheric pressure is 101.3 kN/m
2
. At
this temperature, the diffusivity of benzene in air is 8 x 10
-6
m
2
/s and the saturated
vapour pressure of benzene is 13.3 kPa. If diffusion of benzene may be assumed to take
C
T
C
A1
C
B2
C
A2
C
B1
0
0 x
8
place through a stagnant gas film, 3mm thick, how long will it take for the benzene to
evaporate?

The density of liquid benzene is 880 kg/m
3
at 295K.

At the point of contact, the gas and liquid will be assumed to be in equilibrium and so
the benzene partial pressure will equal its vapour pressure, i.e.13.3 kPa On the other
side of the stagnant gas film the partial pressure of the benzene will be zero.

This is a case of diffusion of A (benzene) through stagnant B (air). It is probably
simplest to use the form:

|
|
.
|

\
|

=
1
2
ln
A T
A T T
A
p p
p p
RTx
DP
N or
|
|
.
|

\
|

=
1
2
ln
Bz T
Bz T T
Bz
p p
p p
RTx
DP
N

p
T
= 101.3 kN/m
2

p
Bz1
= 13.3 kN/m
2

p
Bz2
= 0.0 kN/m
2

5
6
Bz
10 x 1.55
3 . 13 3 . 101
0 3 . 101
ln
0.003 x 295 x 8.314
10 x 8
N

=
|
.
|

\
|

|
|
.
|

\
|
= kmol/m
2
s

The area for mass transfer is the area of the tank = x 2.5
2
.
The rate of transfer is N
Bz
x Area = 3.04 x 10
-4
kmol/s

The mass of benzene initially in the tank (from area, depth and density) is 86.4 kg
(i.e. 1.107 kmol).

The time taken for this to evaporate will be: 1.107/3.04 x 10
-4
= 3640 s

Alternatively the mass transfer rate can be found from:


|
|
.
|

\
|

=
1
2
ln
Bz T
Bz T T
Bz
c c
c c
x
Dc
N
c
T
= n
T
/V = P
T
/ RT =
295 x 314 . 8
3 . 101
= 0.0413 kmol/m
3

c
Bz1
=
295 x 314 . 8
3 . 13
= 0.0054 kmol/m
3

c
Bz2
= 0.0 kmol/m
3


N
Bz
= |
.
|

\
|

|
|
.
|

\
|

0054 . 0 0413 . 0
0 0413 . 0
ln
0.003
0413 . 0 10 x 8
6
x
= 1.55 x 10
-5
kmol/m
2
s as before.

Experimental Determination of Vapour Diffusivities
The following method was developed by Winkelmann, see C&R vol 1 p581.
9

Figure 9 Winkelmanns method for determination of vapour diffusivities

The partial pressure of vaporising component, A, just above the liquid surface will
equal its saturated vapour pressure; and it will be zero at the top of the vertical tube,
where A is diluted and carried off by the gas phase component B.

The gas stream flow is selected to ensure sufficient dilution of A so that c
A
can be
taken to be zero, but without causing eddy currents in the vertical tube.

While in the previous example we were dealing with diffusion over a fixed distance
(3mm), in this case the distance, L, increases as vaporisation proceeds.

If c
A
*
is the concentration of A in the vapour corresponding to its saturated vapour
pressure p
A
*
then:
|
|
.
|

\
|

=
|
|
.
|

\
|

=
*
1
2
0
ln ln
A T
T T
A T
A T T
A
c c
c
L
Dc
c c
c c
x
Dc
N

Since the rate of diffusion must also equal the rate at which material is lost from the
liquid phase:
|
|
.
|

\
|

= |
.
|

\
|
=
*
0
ln
A T
T T L
A
c c
c
L
Dc
dt
dL
M
N


M = molar mass of A

If we take the diffusion distance at t = 0 to be L
0
, this integrates to:
t
c c
c MDc
L L
A T
T
L
T
|
|
.
|

\
|

=
*
2
0
2
ln
2

In principle we should be able to plot (L
2
L
0
2
) against t, to get a straight line,
through the origin. The gradient would allow us to determine D.

While L
0
is difficult to determine accurately, (L L
0
) is easier to find and the
equation above can be organised as follows:

( )( ) t
c c
c MDc
L L L L L
A T
T
L
T
|
|
.
|

\
|

= +
*
0 0 0
ln
2
2

|
|
.
|

\
|

+
|
|
.
|

\
|

*
0
*
0
0
ln
2
2
ln
2
A T
T
L
T
A T
T
L
T
c c
c MDc
L
c c
c MDc
L L
L L
t


Distance, L, over
which diffusion
occurs
Gas
Stream, B
Liquid, A
10

A plot of
0
L - L
t
against ( L L
0
) will give a straight line with a gradient:
|
|
.
|

\
|

*
ln
2
1
A T
T
L
T
c c
c MDc

from which D can be found. (see example in C&R vol 1 p582 the algebra in the
equations is different but the numbers still work.)

Prediction of Vapour Diffusivities

If experimental values of diffusivity are not known, various theoretical models (based
on the kinetic theory of gases) can estimate diffusivity. For example, a method due to
Gilliland based on the Stefan-Maxwell hard sphere model:

( ) B A
B A T
AB
M M
V V P
T
D
1 1 10 x 3 . 4
2
3 / 1 3 / 1
5 . 1 4
+
+
=



D
AB
= diffusivity for system A/B (m
2
/s)
P
T
= total pressure (N/m
2
)
T = absolute temperature (K)
M
A
,M
B
= molecular masses (kg/kmol) of A and B
V
A
,V
B
= molar volumes (m
3
/kmol) of liquid A and B at their boiling
points

If the molar volumes are not known, they can be built up from tables of contributions
associated with the atoms within its structure. See C&R vol 1 p585.

If the diffusivity of a mixture is known at one condition, the above equation can be
used to estimate its value at other conditions. For example if the diffusivity of
benzene in air is 8 x 10
-6
m
2
/s at 295K and 101.3 kPa, find D
Bz
at
350K and 101.3 kPa (10.34 x 10
-6
m
2
/s)
295K and 200 kPa (4.052 x 10
-6
m
2
/s)

Combining the above equation with, for example, the equation for diffusion through a
stationary gas,
|
|
.
|

\
|

=
1
2
ln
A T
A T T
A
p p
p p
RTx
DP
N
we can predict how mass transfer rates will be affected by changes in temperature and
pressure.
Diffusion in the Liquid Phase
Liquid phase diffusion is governed by essentially the same laws as for gas phase
diffusion, but:
11
- In the gas phase the average distance between molecular collisions >> molecular
size.
- In the liquid phase the average distance between molecular collisions < molecular
size.
- Diffusivities in liquid phase are very much less than those in gas phase.
- Liquid phase diffusivities are much more dependent on concentration than those
in gas phase.
- In the liquid phase, D
AB
= D
BA
.

For dilute systems with diffusion of A through stagnant B, the bulk flow will be small
so:

dx
dc
D J N
A
AB A A
= = which on integration becomes:

( )
2 1 A A
AB
A
c c
x
D
N |
.
|

\
|
=

Guidance to estimation of liquid phase diffusivities is provided in C&R vol 1, p597
and in Sinnott, p332.
Mass Transfer In The Vicinity Of A Phase Boundary
Figure 10 shows schematically what might be happening near a phase boundary. If it
helps, think of phase 1 as Coke and phase 2 as air. A represents CO
2
coming out of
the Coke into air. Molecular diffusion (a slow process) predominates in the laminar
sub-layer. Eddy diffusion (a fast process) predominates in the turbulent bulk.

Figure 10 Laminar and turbulent regions near an interface
A simpler picture is to assume that all of the mass transfer resistance within a phase
lies in a thin stagnant film through which the transfer mechanism is molecular
diffusion. This is illustrated in Figure 11.
1 2 3
1 = Laminar sub-layer
2 = Buffer layer
3 = Turbulent bulk
Phase 1
Liquid?
Phase 2
Gas?
Flux of A
Interphase
boundary
12

Figure 11 Simplified picture for mass transfer at an interface: linear
gradient
For equimolar counterdiffusion through the boundary layer
( )
Ao Ai A
c c
L
D
N =
or ( )
Ao Ai D A
c c h N =
where h
D
= D/L = the film mass transfer coefficient with units m
3
/m
2
s (or m/s)

For mass transfer through stagnant B in the boundary layer

Figure 12 Simplified picture for mass transfer at an interface: non-linear
gradient

|
|
.
|

\
|

=
Ai T
Ao T T
A
c c
c c
L
Dc
N ln
or ( )
Ao Ai D A
c c h N =
where
|
|
.
|

\
|

=
Ai T
Ao T
Ao Ai
T
D
c c
c c
c c
c
L
D
h ln
) (
= the film mass transfer coefficient.
Show that for dilute systems this simplifies to h
D
= D/L, the same as for equimolar
counterdiffusion. (Hint: divide the terms inside the log by c
T
and remember that
ln(1 - x ) = -x if x is a small number.)

c
A0
c
Ai
L
c
Ai
c
Ao
L
13
Mass Transfer across a Phase Boundary

The Whitman two-film theory models the mass transfer across a phase boundary by
assuming a stagnant film in each phase as shown in Figure 13.

Figure 13 Mass transfer through two stagnant films at an interface
Assumptions in the theory are:
- There is a discrete interface between the phases, and all material transferring
must pass through it.
- Mass transfer resistance is confined to a thin layer of fluid on each side of the
interface.
- There is no resistance to mass transfer at the interface itself.
- The phases are in equilibrium at the interface. (The two concentrations, c
Ai1

and c
Ai2
, will be related by some phase equilibrium or solubility relationship.)
- The system is at steady state. (Flux of A to the interface through phase 1
equals its flux away through the interface through phase 2.)

Flux through the film in phase 1 = flux through the film in phase 2
N
A
= h
D1
(c
Ao1
- c
Ai1
) = h
D2
(c
Ai2
- c
Ao2
)
( )
2 2
1
2
1 1 Ao Ai
D
D
Ao Ai
c c
h
h
c c =
On a graph of c
A1
versus c
A2
, this equation will give a straight line which will pass
through c
Ao1
, c
Ao2
and have a gradient of
1
2
D
D
h
h
. We can then find the interface
concentrations (remembering that they are in equilibrium) using Figure 14.
L
2
c
Ai2
c
Ai1
c
Ao1
c
Ao2
L
1
14

Figure 14 Graphical determination of interface concentrations

Figure 15 shows the concentrations if h
D2
is much larger than h
D1
. There is a low
concentration difference in phase 2 (c
Ai2
~ c
Ao2
) and a large concentration difference
in phase 1. A large h value means a small resistance and so a small driving force is
necessary to give the flux.

Figure 15 Graphical determination of interface concentrations with a small
resistance in phase 2
Figure 16 shows the concentrations if h
D2
is much smaller than h
D1
. There is a large
concentration difference in phase 2 and a small concentration difference in phase 1.
c
A1
Equilibrium
Line
c
Ao1
c
Ai1
c
Ai2
c
Ao2 c
A2
Bulk
Conditions
Interface
Conditions
c
A1
Equilibrium
Line
c
Ao1
c
Ai1
c
Ai2
c
Ao2 c
A2
Bulk
Conditions
Interface
Conditions
15

Figure 16 Graphical determination of interface concentrations with a small
resistance in phase 1
Overall Mass Transfer Coefficients

Up until now we have used film mass transfer coefficients:
N
A
= h
D1
(c
Ao1
- c
Ai1
) = h
D2
(c
Ai2
- c
Ao2
)
Because the interfacial concentrations, c
Ai1
and c
Ai2
, cannot readily be measured or
estimated, it is convenient to define overall mass transfer coefficients K
1
, K
2
, such
that:
N
A
= K
1
(c
Ao1
- c
Ae1
)
N
A
= K
2
(c
Ae2
- c
Ao2
)

K
1
= overall mass transfer coefficient based on phase 1
K
2
= overall mass transfer coefficient based on phase 2
c
Ae1
= phase 1 composition that would be in equilibrium with c
Ao2
in phase 2
c
Ae2
= phase 2 composition that would be in equilibrium with c
Ao1
in phase 1
Figure 17 shows the driving forces.

Figure 17 Mass transfer driving forces for overall coefficients
For a straight equilibrium line, i.e Henrys Law:

c
A1
Equilibrium
Line
c
Ao1
c
Ai1
c
Ai2
c
Ao2 c
A2
Bulk
Conditions
Interface
Conditions
c
A1
Equilibrium
Line
c
Ao1
c
Ao2
c
A2
Bulk
Conditions
c
Ae1
c
Ae2
Phase 2
driving force
P
h
a
s
e

1

d
r
i
v
i
n
g

f
o
r
c
e
16
c
Ai1
= H c
Ai2
and c
Ae1
= H c
Ao2
and c
Ao1
= H c
Ae2


Using film coefficients: N
A
= h
D1
(c
Ao1
- c
Ai1
) = h
D2
(c
Ai2
- c
Ao2
)

Using overall coefficients: N
A
= K
1
(c
Ao1
- c
Ae1
) = K
2
(c
Ae2
- c
Ao2
)

Hence: K
1
(c
Ao1
- c
Ae1
) = h
D1
(c
Ao1
- c
Ai1
)


1 1
1 1
1 1
1 1
Ai Ao
Ae Ao
D
c c
c c
h K

=
Adding and subtracting c
Ai1
:

1 1
1 1
1 1 1
1 1
1 1 1
1 1 1 1
1 1
1 1 1 1
Ai Ao
Ai Ao
D Ai Ao
Ae Ai
D Ai Ao
Ai Ai Ae Ao
D
c c
c c
h c c
c c
h c c
c c c c
h K

+
=

also:
2 2
1 1
2 1
1 1
Ao Ai
Ai Ao
D D
c c
c c
h h

=
combining these:
1 2 2
1 1
2 1
1 1 1
D Ao Ai
Ae Ai
D
h c c
c c
h K
+

=
But: ) (
2 2 1 1 Ao Ai Ae Ai
c c H c c =
So:
2 1 1
1 1
D D
h
H
h K
+ =
Similarly:
2 1 2
1 1 1
D D
h Hh K
+ =
and:
2 1
1
K
H
K
=

If h
D1
>> h
D2
or H is large (fairly insoluble gas) K
2
~ h
D2


If h
D1
<< h
D2
or H is small (very soluble gas) K
1
~ h
D1


Example
Propionic acid (molar mass 74 kg/kmol) is removed from aqueous solution by
liquid/liquid extraction with ethyl butyrate. At a particular point in the process, the
concentration of propionic acid in the aqueous phase is 3% by mass while that in the
organic phase is 0.4% by mass. The propionic acid transfer rate is 1.2x10
-6
kmol/m
2
s.

The process is operated at 20
o
C and the densities of the aqueous and organic phases at
this temperature are 998 kg/m
3
and 879 kg/m
3
respectively.

It may be assumed that the resistance to mass transfer lies solely in a pair of liquid
films at the liquid/liquid interface and that 60% of this resistance lies in the aqueous
phase.

For dilute solutions, the equilibrium distribution of propionic acid between water and
ethyl butyrate is given by:
17
c
A1
= 4.98 c
A2


where c
A1
and c
A2
are the concentrations (kmol/m
3
) of propionic acid in the aqueous
and organic phases respectively.

a) Find the overall mass transfer coefficients K
1
and K
2
, based on the aqueous and
organic phases respectively.
b) Find the film mass transfer coefficients, h
D1
and h
D2
.
c) Find the interfacial concentration of propionic acid in each phase.

First we need to work out the molar concentration of propionic acid in the bulk of
each phase.
Molar concentration of acid in the aqueous phase =
74
998 x 03 . 0
= 0.405 kmol/m
3

Molar concentration of acid in the organic phase =
74
879 x 0.004
= 0.0475 kmol/m
3


Using the equilibrium relationship we can find c
Ae1
and c
Ae2


c
Ae1
= 4.98 x 0.0475 = 0.237 kmol/m
3

0.405 = 4.98 x c
Ae2
c
Ae2
= 0.0813 kmol/m
3


Now N
A
= K
1
(c
Ao1
- c
Ae1
)

K
1
= 1.2 x 10
-6
/(0.405 0.237) = 7.1 x 10
-6
m
3
/m
2
s


and: N
A
= K
2
( c
Ae2
- c
Ao2
)

K
2
= 1.2 x 10
-6
/(0.0813 0.0475) = 3.55 x 10
-5
m
3
/m
2
s


And
2 1 1
1 1
D D
h
H
h K
+ =
i.e. Total resistance = Aqueous phase resistance + Organic phase resistance
Since 60% of the resistance is in the aqueous phase, then
1 1
1
100
60 1
K h
D
=
so h
D1
= 1.19 x 10
-6
m
3
/m
2
s
and:
1 2
1
100
40
K h
H
D
=
so h
D2
= 8.9 x 10
-5
m
3
/m
2
s

Finally we can obtain the interfacial concentrations using:
N
A
= h
D1
(c
Ao1
- c
Ai1
)
1.2 x 10
-6
= 1.19 x 10
-5
(0.405 c
Ai1
)
c
Ai1
= 0.304 kmol/m
3


Similarly we could use N
A
= h
D2
(c
Ai2
- c
Ao2
) to find c
Ai2
. Alternatively we can use
the equilibrium relationship:
c
Ai1
= 4.98 c
Ai2

18
c
Ai2
= 0.062 kmol/m
3

Correlations for Film Mass Transfer Coefficients

Mechanisms of mass transfer are very similar to those of convective heat transfer.

For convective heat transfer in pipes we frequently used the Colburn equation for film
heat transfer coefficients:
Nu = 0.023 Re
0.8
Pr
0.33


Or its alternative forms:
j
h
= StPr
0.67
= 0.023 Re
-0.2


where St is the Stanton number (for heat transfer)
St = Nu/(Re Pr) = h/(c
p
u)

For mass transfer from a liquid flowing down the inside of a tube into a gas passing
upwards, Gilliland and Sherwood proposed:

Sh = 0.023 Re
0.83
Sc
0.44

Sherwood Number, Sh =
|
|
.
|

\
|
|
.
|

\
|
T
BM D
c
c
D
d h
where c
BM
is the mean value of C
B
. For
equimolar counterdiffusion and dilute systems, Sherwood Number, Sh = |
.
|

\
|
D
d h
D
.
Schmidt Number, Sc =
|
|
.
|

\
|
D

A very closely related form is:
j
d
= StSc
0.67
= 0.023 Re
-0.2


where St is the Stanton number (for mass transfer)
St = Sh/(Re Sc) = (h
D
/u) (c
BM
/c
T
)

There is a mistake on the SI sheet. It gives Nu in the definition of St for mass transfer instead Sh.

Comparing the j
d
and j
h
factor expressions we see that mass transfer coefficients can
be estimated in terms of heat transfer coefficients and vice versa:
67 . 0
Pr
|
.
|

\
|
|
|
.
|

\
|
|
|
.
|

\
|
=
Sc c
c
c
h
h
BM
T
p
D

C&R vol 1, Section 10.8. p646 gives similar experimental correlations for other
important geometries, e.g:

- Plane surfaces
- Single particles
- Fixed beds of particles
- Fluidised beds of particles
19
Laboratory Determination of Liquid-Liquid Mass Transfer
Effects

Effects of parameters such as liquid density, viscosity, temperature and suspended
solids concentration on liquid-liquid mass transfer can be investigated using a Lewis
Cell shown in Figure 18.

Figure 18 Lewis cell for finding liquid-liquid mass transfer coefficients

Constant flows of feed solution (containing solute A) and extracting solvent are
established so that the system reaches steady state.

Ideally each phase should be perfectly mixed (so that the exit stream has the same
concentration as the liquid in the cell) but the interface should remain flat and smooth
so that the area is well-defined. The stirrers are surrounded by wire mesh to reduce
turbulence and avoid vortex formation. Flat disc stirrers may be useful.

Example
A Lewis cell, Figure 19, is being used in a laboratory study of the transfer of acetone
from an aqueous solution (phase 1) to liquid chloroform (phase 2). The apparatus is
maintained under steady state conditions at 25
o
C. The cell is a vertical cylinder with
an internal diameter of 15cm.

Figure 19 Lewis cell extracting acetone from water into chloroform
Interface
Lean solvent Rich solvent
(Extract)
Feed
Solution
Raffinate
Phase 1
Phase 2
Stirrer
Aqueous Feed
(1)
Aqueous Raffinate
(2)
Chloroform Feed (3) Chloroform Extract (4)
20

The aqueous feed enters at 24 ml/min and the chloroform enters at 60 ml/min. The
acetone concentration in the fresh aqueous feed is 2.2 mass%, while that in the
chloroform extract is 0.18 mass%. The chloroform feed to the cell contains no
acetone.

It may be assumed that neither solvent is soluble in the other and that the small
quantities of acetone transferred have no significant effect on the volumetric flow or
density of either phase. The densities of the aqueous and organic phases at 25
o
C are
997 kg/m
3
and 1482 kg/m
3
respectively. The molar mass of acetone is 58.1 kg/kmol.

The equilibrium relationship for the distribution of acetone at low concentration
between water and chloroform at 25
o
C is:
c
A1
= 2.07 c
A2

a) Find the acetone concentration in the aqueous raffinate (kmol/m
3
). In liquid-liquid
extraction, raffinate is the stream that has been refined.
b) Find the overall mass transfer coefficients, K
1
and K
2
.

Chloroform phase flow = 1.482 x 10
-3
kg/s
Aqueous phase flow = 0.399 x 10
-3
kg/s

Material balance on acetone:
Acetone in (2) + acetone in (4) = acetone in (1) + acetone in (3)
Acetone in (2) = 8.78 x 10
-6
+ 0 - 2.67 x 10
-6
= 6.11 x 10
-6
kg/s

Mass % acetone in (2) = 1.53%
Molar concentration of acetone in (2) =
58.1
997 x 0.0153
= 0.263 kmol/m
3


Stream Acetone
(kg/s)
Acetone
(mass%)
Acetone
(kmol/m
3
)
(1) 8.78x10
-6
2.20 0.378
(2) 6.11x10
-6
1.53 0.263=c
Ao1
(3) 0.0 0.00 0.000
(4) 2.67x10
-6
0.18 0.046=c
Ao2


b) Acetone transferred = 4.6 x 10
-8
kmol/s
Interfacial area =
2
15 . 0
4
t
= 0.01767 m
2

Flux of acetone, N
A
= 4.6 x 10
-8
/0.01767 = 2.60 x 10
-6
kmol/m
2
s

N
A
= K
1
(c
Ao1
- c
Ae1
)
K
1
= 1.55 x 10
-5
m
3
/m
2
s

N
A
= K
2
(c
Ae2
- c
Ao2
)
K
2
= 3.21 x 10
-5
m
3
/m
2
s

21
Alternatives to Film Theory for Interfacial Mass Transfer
See C&R vol 1, Section 10.5.2 p602.

These broadly involve two new concepts:
- Surface Renewal at the interface by interchange of fluid elements between
interface and bulk.
- Penetration of transferring species into these elements while at the interface.

Surface Renewal
As shown in Figure 20, fluid elements in Phase 2 are brought to the interface by
eddies. Elements are in contact with Phase 1 for a short interval of time and then mix
back into the bulk.

An element coming from the bulk will contain a uniform concentration of transferring
species (c
Ao2
). On reaching the interface, the side of the element at the interface will
rapidly reach equilibrium (c
Ai2
) with the interfacial concentration of Phase 1. While
the element is at the surface, A will penetrate further into the element, thus
transferring A into Phase 2.


Figure 20 Surface renewal fluid elements move to and from the interface
Penetration
If the fluid element is considered as an infinitely thick slab, the concentration of A
(c
A
) within it will vary with time (t) and position (x) according to the unsteady state
diffusion equation:
2
2
dx
c d
D
dt
dc
A A
=
with boundary conditions:
c
A
= c
Ao
at t = 0 for all x
c
A
= c
Ai
at x = 0 for all t > 0
c
A
= c
Ao
at x = for all t

The solution to this equation develops with time as shown in Figure 21.
Phase1 Phase 2
Fluid
Element
x
1
2
3
Transfer of A
22

Figure 21 Developing profile in an infinitely thick slab
Solution of the above equation at any point in time, t, gives the flux through the
interface (i.e. x=0) into the element at any time t,
t
D
c c N
Ao Ai x t A
t
) ( ) (
0 ,
=
=


Regular Surface Renewal
In the original formulation of the surface renewal or penetration concepts, Higbie
postulated that all fluid elements spend the same time, u, at the surface, so that total
transfer per unit area

} }
= =
u u
t t
0
2 / 1
0
1
) ( ) (
t
D
c c
t
D
c c
Ao Ai Ao Ai

t
u D
c c
Ao Ai
) ( 2 =
Dividing this by the time, u, gives the average flux,
tu
D
c c N
Ao Ai A
) ( 2 =
Note that:
- The driving force is (c
Ai
c
Ao
) as expected.
- The rate is proportional to D
0.5
rather than D as in all our earlier treatment.
- The rate increases with decreasing u, e.g. through increased agitation, as we
would expect

Random Surface Renewal
In 1951 Dankwerts proposed that instead of all fluid elements spending the same time
at the interface, any element would be replaced randomly irrespective of the time
already spent at the interface.

If the rate of production of fresh surface per unit total area of surface is s, then:
Ds c c N
Ao Ai A
) ( =
Note that:
- The driving force is (c
Ai
c
Ao
) as expected.
- The rate is again proportional to D
0.5
rather than D.
- The rate increases with increasing s, e.g. through increased agitation, as we would
expect.
c
Ai
c
Ao
c
A
x
Increasing Time
23
Comparisons Between Heat and Mass Transfer
Heat and mass transfer are closely related phenomena. Table 1 brings together some
obvious comparisons. If you think of others, please let me know.
Table 1 Properties of heat and mass transfer
Mass Transfer Heat Transfer
Transfer is proportional to a
gradient
dx
dc
i


dx
dT

Diffusion and conduction
Ficks Law:
dx
dc
D J =
Fouriers Law:
dx
dT
k Q
f
=
Film coefficients N
A
= h
D1
(c
Ao1
- c
Ai1
) Q = hA(T
1
T
2
)
At interface

c
A1
in equilibrium with c
A2
T
1
= T
2

Total resistance is sum of
individual resistances
2 1 1
1 1
D D
h
H
h K
+ =
2 1
1 1 1
h h U
+ =
Correlations for film
coefficients
Sh = 0.023 Re
0.83
Sc
0.44


Nu = 0.023 Re
0.8
Pr
0.33



Bibliography
1. "C&R vol. 1" refers to Chemical Engineering, J.M.Coulson, J.F.Richardson et al.,
vol. 1, 6
th
ed., Butterworth, 1999

2. "Sinnott" refers to Chemical Engineering, R.K.Sinnott vol 6, 3
rd
ed., Butterworth,
1999