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MODULE 2: DIFFUSION


LECTURE NO. 5

2.5 Measurement of liquid-phase diffusion coefficient
There are few methods of determination of liquid-phase diffusivities. The most
commonly used method is Diaphragm cell method.

2.5.1 Diaphragm cell method
Diaphragm cell contains two compartments as shown in Figure 2.8. These are
separated by diaphragm. Let the area of the diaphragm is a and porosity is .
Effective area for diffusion = a
thickness diaphragm
path diffusion of length average
= t (2.49)
where is tortuosity. As the solute concentration is very low, bulk flow term can
be taken as zero. Hence,











Figure 2.8: Diaphragm cell

Stir bar
Diaphragm
Rotating
magnet
Feed/sampling
Feed/sampling
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t l
C C
D
dZ
dC
D N
A A
AB
A
AB A
) 2 (
1

= = (2.50)
A
A
N a
dt
dC
V c =
1
1
(2.51)
and
A
A
N a
dt
dC
V c =
2
2
(2.52)
Adding Equations (2.51) and (2.52) and substituting N
A
from Equation (2.50) we
have,
(

2 1
2 1 2 1
1 1 ) ( ) (
V V l
C C D a
dt
C C d
A A AB A A
t
c
(2.53)
Boundary conditions
t=0, C
A1
=C
A1,0
; C
A2
=C
A2,0
t=t
f
, C
A1
=C
A1,f
; C
A2
=C
A2,f
Therefore,
|
|
.
|

\
|

+ =

f A f A
A A
f
AB
C C
C C
V V t a
l
D
, 2 , 1
0 , 2 0 , 1
1
2 1
ln
1 1
c
t
(2.54)

2.5.2 Semi-empirical Equation: Wilke-Chang Equation

6 . 0
5 . 0 16
0
) ( 10 173 . 1
A B
B
AB
T M
D
v

= m
2
/s (2.55)
where,
0
AB
D is diffusivity of solute A in solvent B, m
2
/s, is association factor [for
H
2
O=2.26; MeOH=1.9; EtOH=1.5; non-associated solvent=1.0]; M
B
is molecular
weight of B; T is absolute temperature in K;
B
is solution viscosity, kg/m.s;
A
is
solute molar volume at normal boiling point, m
3
/kmol [
A
=0.0756 m
3
/kmol for H
2
O
as solvent].

2.5.3 Stokes-Einstein Equation
Liquid diffusivity varies linearly with absolute temperature and inversely
proportional to viscosity of the medium. Hence,
nt Consta
T
D
AB
=

(2.56)