Models for Mass Transfer at a Fluid-Fluid Interface

~Of greater interest in separation process is mass transfer across an interface

between a gas and a liquid or between two liquid phases.
~Such interface exist in absorption, distillation, extraction, and stripping.
~At fluid-fluid interfaces, turbulence may persist to the interface.
~The following theoretical models have been developed to describe mass transfer
from a fluid to such an interface.
Film Theory
Penetration Theory
Surface Renewal Theory
Film-Penetration Theory
Film Theory
Figure 3.18 (a)
Nernst postulated that the entire resistance to mass transfer in a given turbulent phase is
in a thin, stagnant region of that phase at the interface, called a film, as shown in Figure
3.18 (a). This film is similar to the laminar sublayer that forms when a fluid flows in the
turbulent regime parallel to a flat plate.
pure component A
nonvotatile
~no resistance to mass transfer in the gas phase
due to pure A in the gas
~at the gas-liquid interface, equilibrium obeys the
Henrys law, c
Ai
=H
A
p
A
~in the thin, stagnant liquid film of thickness o,
molecular diffusion only occurs with a driving
force of c
Ai
-c
Ab
~the film is assumed to be very thin, all of the
diffusing A passes through the film and into the
bulk liquid
~the bulk flow of A is neglected, the concentration
is linear as in Figure 3.18 (a)
) (

) (

A A
AB
A A
AB
A b i b i
x x
cD
c c
D
J = =
diffusion flux
total flux
) (

) (

A A
AB
A A
AB
A b i b i
x x
cD
c c
D
N = =
~the liquid phase is dilute in A
~the bulk-flow effect is neglected
) (
) 1 ( 1
1
ln

A A
LM A
AB
A
A
AB
A b i
i
b
x x
x
cD
x
x
cD
N

=
|
|
.
|

\
|

=
~the bulk-flow effect is not neglected
| |
LM B
A A
A A
LM A
) (
) 1 /( ) 1 ( ln
) 1 ( x
x x
x x
x
i b
b i
=


=

AB
D
k
c
=
n
c
D k
AB

experimental: n=0.5~0.75
theory: n=2/3(based on boundary layer)
Example 3.17
Sulfur dioxide is absorbed from air into water in a packed absorption tower. At a certain
location in the tower, the mass transfer flux is 0.0270 kmol SO
2
/m
2
-h and the liquid-
phase mole fraction are 0.0025 and 0.0003, respectively at the two-phase interface and in
the bulk liquid. If the diffusivity of SO
2
in water is 1.710
-5
cm
2
/s, determine the mass
transfer coefficient, k
c
, and the film thickness.
Example 3.18
Sulfur dioxide is absorbed from air into water in a packed absorption tower. At a certain
location in the tower, the mass transfer flux is 0.0270 kmol SO
2
/m
2
-h and the liquid-
phase mole fraction are 0.0025 and 0.0003, respectively at the two-phase interface and in
the bulk liquid. If the diffusivity of SO
2
in water is 1.710
-5
cm
2
/s, determine the contact
time for Higbies penetration theory.
Example 3.19
For the conditions of Example 3.17, estimate the fractional rate of surface renewal, s, for
Danckwerts theory and determine the residence time and probability distributions.
Penetration Theory
Higbie provided a penetration theory for mass transfer from a fluid-fluid interface
into a bulk liquid stream, as shown in Figure 18 (b).
Figure 3.18 (b)
~the stagnant-film concept is replaced by Boussinesq eddies.
(1)move from the bulk to the interface
(2)stay at the interface for a short, fixed period of time
during which they remain static so that molecular
diffusion takes place in a direction normal to the
interface
(3)leave the interface to mix with the bulk stream
~when an eddy moves to the interface, it replaces another
static eddy.
~the eddies are intermittently static and moving
2
A
2
AB
A
z
c
D
t
c
c
c
=
c
c
B.C
c
A
=c
Ab
at t=0 for 0szs
c
A
=c
Ai
at z=0 for t>0
c
A
=c
Ab
at z= for t>0
|
|
.
|

\
|
=

c b i
i
t D
z
c c
c c
AB A A
A A
2
erf
) ( ) ( 2
A A
AB
A A A b i c
c
b i
c c k
t
D
c c N =
t
=
unsteady-state diffusion
t
c
=contact time of the static
eddy at the interface during
one cycle.
average mass transfer flux
c
c
t
D
k
t
=
AB
5 . 0
AB
D k
c

~the penetration theory is most useful when mass transfer involves bubbles or droplets or flow
over random packing.
~for bubbles, the contact time, t
c
, of the liquid surrounding the bubble is taken as the ratio of
bubble diameter to bubble rise velocity.
~for a liquid spray, where no circulation of liquid occurs inside the droplets, the contact time is
the total time for the droplets to fall through the gas.
~for a packed tower, where the liquid flows as a film over particles of random packing, mixing
can be assumed to occur each time the liquid film passes from one piece of packing to another.
Surface Renewal Theory
The penetration theory is not satisfying because the assumption of a constant contact time
for all eddies that temporarily reside at the surface is not reasonable, especially for
stirred tanks contactors with random packing, and bubble and spray columns where the
bubbles and droplets over a wide range of sizes.
Danckwerts suggested an improvement to the penetration theory that involves the
replacement of the constant eddy contact time with the assumption of a residence-time
distribution, wherein the probability of an eddy at the surface being replaced by a fresh
eddy is independent of the age of the surface eddy.
t t F t d / } { d } { = |
|{t}dt=the probability that a given surface eddy will have a residence time t.
}

= |
0
1 d } { t t
F(t) is the fraction of eddies with
a contact time of less than t.
The instantaneous mass transfer rate for an eddy with an age t in flux form as
) (
A A
AB
A b i t
c c
t
D
N
t
=
The integrated average rate is
t N t N
t
d } { ) (
0
A avg A
}

| =
st
s t

= | e } {
) ( ) (
A A AB avg A b i
c c s D N = s D k
c AB
=
5 . 0
AB
D k
c

~The more reasonable surface renewal theory predicts the same dependency on molecular
diffusivity as the penetration theory.
~Unfortunately, s, the fractional rate of surface renewal, is as elusive a parameter as the
constant contact time, t
c
.
t t
e t F
/
1 } {

= me sidenceti averagere = t
ewal urfaceren rateofs fractional / 1 = = t s
Film-Penetration Theory
Toor and Marchello combined feature of the film, penetration, and surface renewal theories
to develop a film-penetration model. Their theory assumes that the entire resistance to mass
transfer resides in a film of fixed thickness o. Eddies move to and from the bulk fluid and
this film. Age distributions for time spent in the film are of the Higbie or Danckwerts type.
2
A
2
AB
A
z
c
D
t
c
c
c
=
c
c
B.C
c
A
=c
Ab
at t=0 for 0szs
c
A
=c
Ai
at z=0 for t>0
c
A
=c
Ab
at z=o for t>0
For small t, the solution is
(
(

|
|
.
|

\
|
+
|
.
|

\
|
t
=

=1 n AB
2 2
2 / 1
AB
A A A

exp 2 1 ) (
t D
n
t
D
c c N
b i t
For large t, the solution is
(

|
.
|

\
|
t +
|
.
|

\
|
=

=1 n
2
AB 2 2 AB
A A A

exp 2 1

) (
t D
n
D
c c N
b i t
( )
(
(

|
|
.
|

\
|
+ =

=1 AB
2 / 1
AB A A avg A
2 exp 2 1 ) (
n
b i
D
s
n sD c c N
(
(
(
(

t +
+
|
.
|

\
|
=

=1
2
AB
2 2
AB
A A avg A

1
1
2 1

) (
n
b i
s
D
n
D
c c N
0 . 1 ~ 5 . 0
AB
D k
c

surface renewal theory
film theory
s is high
s is low
Two-Film Theory and Overall Mass Transfer Coefficients
Whitman suggested an extension of the film theory to two fluid films in series.
~Each film presents a resistance to mass transfer, but concentration in the two fluid at
the interface are in equilibrium.
~There is no additional interfacial resistance to mass transfer.
~This concept has found extensive application in modeling of steady-state gas-liquid and
liquid-liquid separation processes, when the fluid phases are in laminar or turbulent
flow.
~The assumption of equilibrium at the interface is satisfactory unless mass transfer rates
are very high or surfactants accumulate at the interface.
L b i
L
L
G i b
G
G
c c
D
c c
D
N ) (

) (
) (

) (
A A
AB
A A
AB
A
= =
c g
c
i b b i i
b
k
N
k
N H
k
N
H p H p c c c c
c c
A A A
A
A A A A A A A
*
A
A
*
A
+ =
+ = + =

) ( ) ( ) (
A
*
A A A A A A b L b i c i b g
c c K c c k p p k N = = =
c g L
k k
H
K
1 1
A
+ =
c g
b i
g
i i b
b
k H
N
k
N
H
c
H
c
k
N
p p p p
p p
A
A A
A
A
A
A
A *
A A A A
*
A A
+ =
+ = + =

) ( ) ( ) (
*
A A A A A A A
p p K c c k p p k N
b G b i c i b g
= = =
c g G
k H k K
A
1 1 1
+ =
x y y
x y x
k
K
k K
k k K K
A
A
1 1
1 1 1
+ =
+ =
c
A
*p
Ab

p
A
*c
Ab

Liquid phase:
|
.
|

\
|
= =
M
k c k k
L
c c x

Gas phase:
c k
RT
P
k P k k
g c g c g y
) ( ) ( = = =
SI American Engineering
k
c
m/s ft/h
k
g
kmol/s-m
2
-kPa lbmol/h-ft
2
-atm
k
y
, k
x
kmol/s-m
2
lbmol/h-ft
2
Taking into account the effect of bulk flow
LM B LM A
'
LM B LM A
'
) ( ) 1 (
) ( ) 1 (
y
k
y
k
k
x
k
x
k
k
=

=
=

=
Case of Large Driving Forces for Mass Transfer
) ( ) ( ) ( ) (
A
*
A
*
A A A A A A A b x b y b i x i b y
x x K y y K x x k y y k N = = = =
x
x
y
b i
i
x y i b
i
y y
i b y
i i b
i b y
b
y
k
m
k
x x
y y
k k y y
y y
k k
y y k
y y y y
y y k
y y
K
+ =
|
|
.
|

\
|

+ =
|
|
.
|

\
|

+ =

+
=

=
1
1 1 1 1
) (
) ( ) (
) (
1
A A
*
A A
A A
*
A A
A A
*
A A A A
A A
*
A A
In a similar manner,
y y x
i b
i
y x b i
i
x x
b i x
b i i
b i x
b
x
m k k
y y
x x
k k x x
x x
k k
x x k
x x x x
x x k
x x
K
1 1
1 1 1 1
) (
) ( ) (
) (
1
A A
A
*
A
A A
A
*
A
A A
A A A
*
A
A A
A
*
A
+ =
|
|
.
|

\
|

+ =
|
|
.
|

\
|

+ =

+
=

=
|
|
.
|

\
|

=
b i
i
x
x x
y y
m
A A
*
A A
|
|
.
|

\
|

=
i
i b
y
x x
y y
m
A
*
A
A A
Example 3.20
Sulfur dioxide (A) is absorbed into water in a packed column. At a certain location, the bulk
conditions are 50 C, 2 atm, y
Ab
=0.085, and x
Ab
=0.001. Equilibrium data for SO
2
between air
and water at 50 C are
p
SO
2
, atm c
SO
2
, lbmol/ft
3

0.0382 0.00193
0.0606 0.00290
0.1092 0.00483
0.1700 0.00676
Experimental values of the mass transfer coefficient are as follows.
Liquid phase: k
c
=0.18 m/h
Gas phase: k
g
=0.040 kmol/h-m
2
-kPa
Using mole fraction-driving forces, compute the mass transfer flux by:
(a) Assuming an average Henrys law constant and a negligible bulk-flow effect
(b) Utilizing the actual curved equilibrium line and assuming a negligible bulk-flow effect
(c) Utilizing the actual curved equilibrium line and taking into account the bulk-flow effect
(d) Determine the relative magnitude of the two resistance and the values of the mole fractions
at the interface from the results of part (c)