Molecular diffusion in Liquids

Diffusion coefficient in liquids is slower than in

gases (10
5
times lower).
The flux in liquid is lower around 100 times
than in gases.
D
AB
is composition dependent and it is slower
than in the gases.

1
Equations for diffusion in liquids
2
| |
A A
A AB A B
dC C
N D N N
dz C
= + +
Equimolar counter diffusion (N
A
= - N
B
)
( )
( )
1 2
2 1
AB A A
A
D C C
N
z z

( )
( )
1 2
2 1
AB avg A A
A
D C x x
N
z z

( )
1 2
1 2
2
M M
avg
C

+
=
D
AB
is a function of composition, therefore it
must be calculated based on the average
values between point 1 and 2
Equations for diffusion in liquids
3
Diffusion of solute (A) through stagnant solvent (B) (N
B
= 0)
( )
1 2
2 1
AB avg
A A
A
BLM
D C
x x
N
z z x
| |

=
|

\ .
2
1
2 1
ln( )
B
B
B B
BLM
x
x
x x
x

=
Example
An ethanol (A)-water (B) solution in the form of
a stagnant film 2.0 mm thick at 293 K is in
contact at one surface with an organic solvent in
which ethanol is soluble and water is insoluble.
Hence, N
B
=0. At point 1 the concentration of
enthanol is 16.8 wt% and the solution density is

1
= 972.8kg/m
3
. At point 2 the concentration of
ethanol is 6.8 wt% and
2
= 988.1 kg/m
3
. The
diffusivity of ethanol is 0.740e-9 m
2
/s. Calculate
the steady-state flux N
A
.
4
Solution
5
M
A
= 46.05, M
B
=18
16.8
46.05
1
16.8 83.2
46.05 18
0.073
A
x = =
+
2
0.0277
A
x =
x
B1
= 0.9268, x
B2
= 0.9723
1
16.8 83.2
46.05 18
100
20.07 M = =
+
2
18.75 M =
Solution cont.
6
972.8 988.1
20.07 18.75
50.6
2
avg
C
+
= =
Kg mol/m
3

x
BLM
= 0.949
( )
9
0.740 10 50.6 0.0732 0.0277
2 / 1000 0.949
A
N

| |
=
|
\ .
N
A
= 8.99e-7 kg mol/s. m
2

Liquid Diffusivity, D
AB

D
AB
= f(T,P,C).
Effect of pressure is insignificant compared to
temperature and concentration.
D
AB
D
BA

Several eqns to estimate the liquid diffusivity
are available, however not all of them can give
an accurate prediction.
Successful equations are developed for dilute
mixtures.
7
Equations for D
AB

8
D
AB
for dilute solution
1. Wilke and Chang (1955)
( )
1
2 13
0.6
1.17 10
B B
AB
A
M T
D
V

=
AB
D =
Diffusion coefficient in dilute solution, m
2
/s
M
B
= Molecular weight of the solvent
V
A
= Molar volume of solute at normal boiling point, m
3
/kgmol

B
= Association factor for solvent
Solvent
Non-polar 1
Water 2.6
Methanol 1.9
Ethanol 1.5
= viscosity of solution, cP
Error is within 11% when water is
the solvent, and 27% for organic
solvent.
Error can reach up to 200% when
water is the solvent

Equations for D
AB

9
D
AB
for concentrated solution
1. Vignes (1966)
( ) ( )
ln
1
ln
B A
x x
A
AB AB BA
A
D D D
x

(
c
= +
(
c

A
= Activity coefficient of solute
2. Leffler and Cullinan (1970)
( ) ( )
ln
1
ln
B A
x x
A
AB mix AB B BA A
A
D D D
x

(
c
= +
(
c