MASS TRANSFER: DIFFUSION

Mass Transfer: Diffusion Page 1 of 4

Franz Adrian L. Sy
Notes
MASS TRANSFER


Mass Transfer involves the separation of the components of mixtures
through the transfer of material from one homogeneous phase to another


Mass Transfer by Diffusion


FICKS LAW

Molecular diffusion the transfer or movement of individual
molecules through a fluid by means of the random, individual
movements of the molecules

In molecular mass transfer, one or more of the components of the
medium is moving.

Ficks Law the basic relation for molecular diffusion of mass; relates
the flux of a components to its concentration gradient (E 5-189)

dz
dC
D J
A
AB Az
=
*

The above equation applies for diffusion of molecules when the
whole bulk fluid is not moving but is stationary.


EFFECT OF
PROCESS
CONDITIONS
ON MOLECULAR
DIFFUSIVITY

Molecular diffusivity a measure of how fast two species diffuse into
each other in molecular diffusion
- Liquids: P 2-454 (for 1 atm and various temperatures)
- Gases: P 2-456 (for 1 atm and 25C)

- For gases, D
AB
is generally proportional to 1/P and T
1.75
(Fuller et al.):
( ) ( )
2
75 . 1
1
75 . 1
T P D T P D
AB AB
= (E 5-204)

- For liquids, D
AB
is proportional to 1/
B
and T (Wilke & Chang).
( ) ( )
2 1
T D T D
B AB B AB
= (E 5-218)


MOLECULAR
DIFFUSION IN
GASES

General case of diffusion plus convective mass transfer

m A A A
v C J N + =
*
(E 5-190)
Where: N
A
= total flux of A relative to a stationary point
J
A
*
= diffusion flux relative to the moving fluid
C
A
v
m
= convective flux of A relative to a stationary point
v
m
= molar average velocity of the whole fluid relative to
a stationary point

JAz
*
= molar flux (kmol/m
2
-s)
DAB = molecular diffusivity of
molecule A in B (m
2
/s)
CA = concentration of A (kmol/m
3
)
z = distance of diffusion (m)
MASS TRANSFER: DIFFUSION


Mass Transfer: Diffusion Page 2 of 4
Franz Adrian L. Sy
Notes

The above equation may also be written as:
( )
B A
A A
AB A
N N
C
C
dz
dC
D N + + =


- The term C
A
v
m
accounts for conveyance, which is the amount of
component A carried by the net flow in the direction of diffusion.


EQUIMOLAR
COUNTER-
DIFFUSION

Equimolar counterdiffusion the net moles of A diffusing to the right
must equal the net moles of B to the left, due to the condition of
constant total pressure.

For equimolar counterdiffusion,
B A
N N = . Thus: (E 5-197)
z
C
D N
A
AB A
A
A
=
z RT
P D
N
A AB
A
A
A
=
z RT
x P D
N
A AB
A
A
A
=

- For gases, D
AB
= D
BA
.


UNIMOLECULAR
DIFFUSION

Unimolecular diffusion substance A diffuses through stagnant or
nondiffusing B at steady state, and one boundary at the end of the
diffusion path is impermeable to component B

Examples of unimolecular diffusion:
Evaporation of pure benzene at the bottom of a narrow tube, with a
large amount of nondiffusing air passed over the top
Absorption of NH
3
vapor which is in air by water

For unimolecular diffusion, 0 =
B
N . Thus: (E 5-198)
|
|
.
|

\
|

A
=
1
2
ln
A
A AB
A
P P
P P
z RT
P D
N
|
|
.
|

\
|

A
=
1
2
1
1
ln
A
A AB
A
x
x
z RT
P D
N
BM
A AB
A
P
P
z RT
P D
N
A
A
=
BM
A AB
A
x
x
z RT
P D
N
A
A
=
- Since N
B
= 0, D
BA
= 0.


DIFFUSION
WITH A CHANGE
IN PATH
LENGTH

- Occurs when the liquid level for unimolecular diffusion drops slowly
over time

dt
dz
M P
P
RTz
P D
N
A
A
BM
A AB
A

=
A
=

Rearranging and integrating, the equation becomes:
( )
(

A
=
A
A
F
A AB
BM
F
M
z z
P P D
RTP
t

2
0
2
2
1



MASS TRANSFER: DIFFUSION


Mass Transfer: Diffusion Page 3 of 4
Franz Adrian L. Sy
Notes
DIFFUSION
THROUGH A
VARYING
CROSS-
SECTIONAL
AREA

- Occurs when the cross-sectional area through which the diffusion
takes place varies with the distance z. In this case, N
A
is defined as:
A N N
A A
=
Where:
A
N

= amount of A diffusing per unit time (kmol/s)

Since
A
N is constant, N
A
is inversely proportional to the cross-sectional
area for diffusion; i.e.
2 2 1 1
A N A N
A A
= .

- For diffusion from a sphere

( )
2
4 1 r
N
dr P P
dP
RT
D
N
A
A
A AB
A
t
=

=

Rearranging and integrating, and taking r
2
to be a large distance
away, the equation becomes:

BM
A AB
A
P
P
RTr
P D
N
A
=
1
1


- For diffusion through a conduit of nonuniform cross-sectional area
(such as a frustum), the area should be expressed as a function of
diffusion length z, and the Ficks Law equation will be integrated
including this function.


MOLECULAR
DIFFUSION IN
LIQUIDS

The rate of molecular diffusion in liquids is considerably slower than
in gases.

Equimolar counterdiffusion (E 5-197)

z
C
D N
A
AB A
A
A
=
z
x
C D N
A
ave AB A
A
A
=

Where:
|
|
.
|

\
|
+ =
2
2
1
1
2
1
M M
C
ave



Unimolecular diffusion (E 5-198)

z
x
x
C D
N
A
BM
ave AB
A
A
A
=


ESTIMATION OF
MOLECULAR
DIFFUSIVITY

Diffusivity estimation for gases
- Chapman-Enskog
D AB
AB
AB
P
M T
D
O
=
2
2 1 2 3
001858 . 0
o
(E 5-202)
Relevant tables/equations: E 5-213a, T 5-11


MASS TRANSFER: DIFFUSION


Mass Transfer: Diffusion Page 4 of 4
Franz Adrian L. Sy
Notes


Where:
AB
= effective collision diameter

D
= collision integral, function of
AB
kT c

AB
= Lennard-Jones force constant for common gases

- Fuller-Schettler-Giddings
( ) ( ) | |
2
3 1 3 1
2 1 75 . 1
001 . 0
B A
AB
AB
P
M T
D

+
=
u u
(E 5-204)
Relevant tables/equations: T 5-12
Where: = atomic diffusion volume

Diffusivity estimation for liquids
- Wilke-Chang
( )
6 . 0
2 1 8
10 4 . 7
A B
B B
AB
V
T M
D

= (E 5-218)
Where: = association paramenter for solvent (2.26 for water)
V
A
= molar volume of solute as liquid at its normal
boiling point


MASS-
TRANSFER
COEFFICIENTS

Relationships between N
A
and mass-transfer coefficients
General: ( )
i c A
C C k N =
'

Gases Liquids
( )
i G A
P P k N =
'
( ) C C k N
i L A
=
'
(E 5-261)

( )
i G A
y y k N = ( ) x x k N
i L A
= (E 5-262)
( )
*
y y K N
G A
= ( ) x x K N
L A
=
*
(E 5-266)

Where: subscript i refers to the gas-liquid interface
subcripts G and L refer to gas and liquid phase
small k refers to the film mass-transfer coefficient
capital k refers to the overall mass-transfer coefficient
y* = vapor composition in equilibrium with x
x* = liquid composition in equilibrium with y

Relationships between k
G
, k
L
, K
G
, and K
L


L G G
k
m
k K
+ =
1 1

G L L
mk k K
1 1 1
+ =

(E 5-268) (E 5-270)
The slope m is the slope of the equilibrium curve, and may be
obtained from Henrys Law at dilute concentrations.

For systems which are not dilute, i.e. when the solute concentrations in
the gas and/or liquid phases are large, Equations 5-274 to 5-282
must be used instead.