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Tutorial

Tutorial #7
WWWR# 24.1, 24.12, 24.13,
24.15(d), 24.22.

Molecular Mass Transfer
Molecular diffusion
Mass transfer law components:
Molecular concentration:

Mole fraction:
(liquids,solids) , (gases)
c
c
y
c
c
x
A
A
A
A
= =
RT
p
V
n
M
c
A A
A
A
A
= = =

For gases,

Velocity:
mass average velocity,

molar average velocity,

velocity of a particular species relative to mass/molar average is
the diffusion velocity.

P
p
RT P
RT p
y
A A
A
= =

=
=
=
= =
n
i
i i
n
i
i
n
i
i i
1
1
1
v v
v
c
c
n
i
i i
=
=
1
v
V
mol
Flux:
A vector quantity denoting amount of a particular species that
passes per given time through a unit area normal to the vector,
given by Ficks First Law, for basic molecular diffusion

or, in the z-direction,

For a general relation in a non-isothermal, isobaric system,
A AB A
c D V = J
dz
dc
D J
A
AB z A
=
,
dz
dy
cD J
A
AB z A
=
,
Since mass is transferred by two means:
concentration differences
and convection differences from density differences
For binary system with constant V
z
,

Thus,

Rearranging to
) (
, , z z A A z A
V v c J =
dz
dy
cD V v c J
A
AB z z A A z A
= = ) (
, ,
z A
A
AB z A A
V c
dz
dy
cD v c + =
,
As the total velocity,

Or

Which substituted, becomes
) (
1
, , z B B z A A z
v c v c
c
V + =
) (
, , z B B z A A A z A
v c v c y V c + =
) (
, , , z B B z A A A
A
AB z A A
v c v c y
dz
dy
cD v c + + =
Defining molar flux, N as flux relative to a fixed z,

And finally,

Or generalized,
A A A
c v N =
) (
, , , z B z A A
A
AB z A
N N y
dz
dy
cD N + + =
) (
B A A A AB A
y y cD N N N + + V =
Related molecular mass transfer
Defined in terms of chemical potential:

Nernst-Einstein relation

dz
d
RT
D
dz
d
u V v
c AB c
A z z A

= =
,
dz
d
RT
D
c V v c J
c AB
A z z A A z A

= = ) (
, ,
Diffusion Coefficient
Ficks law proportionality/constant

Similar to kinematic viscosity, v, and
thermal diffusivity, o
t
L
L L M t L
M
dz dc
J
D
A
z A
AB
2
3 2
,
)
1
1
)( ( =

=
Gas mass diffusivity
Based on Kinetic Gas Theory

= mean free path length, u = mean speed

Hirschfelders equation:

u D
AA

3
1
*
=
2 / 1
3
2 2 / 3
2 / 3
*
) (
3
2
A A
AA
M
N
P
T
D
k
o t
=
D AB
B A
AB
P
M M
T
D
O
(

+
=
2
2 / 1
2 / 3
1 1
001858 . 0
o
Lennard-Jones parameters o and c from tables,
or from empirical relations
for binary systems, (non-polar,non-reacting)

Extrapolation of diffusivity up to 25
atmospheres

2
B A
AB
o o
o
+
=
B A AB
c c c =
2
1
1
,
1 2
,
2
2 / 3
1
2
2
1
T D
T D
AB AB
T
T
P
P
D D
P T P T
O
O
|
|
.
|

\
|
|
|
.
|

\
|
=
Binary gas-phase Lennard-Jones
collisional integral
With no reliable o or c, we can use the Fuller
correlation,

For binary gas with polar compounds, we
calculate O by

( ) ( ) | |
2
3 / 1 3 / 1
2 / 1
75 . 1 3
1 1
10
B A
B A
AB
v v P
M M
T
D

+
|
|
.
|

\
|
+
=

*
2
196 . 0
0
T
AB
D
o
+ O = O
where

( )
b b
P
B A AB
T V
2 3
2 / 1
10 94 . 1
,

o o o o

= =
AB
T T c k /
*
=
2 / 1
|
.
|

\
|
=
k
c
k
c
k
c
B A AB
( )
b
T
2
3 . 1 1 18 . 1 / o k c + =
( )
) exp( ) exp( ) exp(
* * *
*
0
HT
G
FT
E
DT
C
T
A
B
D
+ + + = O
and

For gas mixtures with several components,

with

( )
2 / 1
B A AB
o o o =
3 / 1
2
3 . 1 1
585 . 1
|
.
|

\
|
+
=
o
o
b
V
n n
D y D y D y
D

+ + +
=
1
'
3 1
'
3 2 1
'
2
mixture 1
/ ... / /
1
n
y y y
y
y
+ + +
=
...
3 2
2
'
2
2
Liquid mass diffusivity
No rigorous theories
Diffusion as molecules or ions
Eyring theory
Hydrodynamic theory
Stokes-Einstein equation

Equating both theories, we get Wilke-Chang eq.
B
AB
r
T
D
t
k
6
=
( )
6 . 0
2 / 1
8
10 4 . 7
A
B B B AB
V
M
T
D u
=

For infinite dilution of non-electrolytes in

water, W-C is simplified to Hayduk-Laudie eq.

Scheibels equation eliminates u
B
,

589 . 0 14 . 1 5
10 26 . 13

=
A B AB
V D
3 / 1
A
B AB
V
K
T
D
=

(
(

|
|
.
|

\
|
+ =

3 / 2
8
3
1 ) 10 2 . 8 (
A
B
V
V
K
As diffusivity changes with temperature,
extrapolation of D
AB
is by

For diffusion of univalent salt in dilute solution,
we use the Nernst equation
n
c
c
ABT
ABT
T T
T T
D
D
|
|
.
|

\
|

=
1
2
) (
) (
2
1
F
RT
D
AB
) / 1 / 1 (
2
0 0
+
+
=

Pore diffusivity
Diffusion of molecules within pores of porous
solids
Knudsen diffusion for gases in cylindrical pores
Pore diameter smaller than mean free path, and
density of gas is low
Knudsen number

From Kinetic Theory of Gases,

pore
d
Kn

=
A
AA
M
NT u
D
t
k 8
3 3
*
= =
But if Kn >1, then

If both Knudsen and molecular diffusion exist, then

with

For non-cylindrical pores, we estimate

A
pore
A
pore pore
KA
M
T
d
M
NT
d
u
d
D 4850
8
3 3
= = =
t
k
KA AB
A
Ae
D D
y
D
1 1 1
+

=
o
A
B
N
N
+ =1 o
Ae Ae
D D
2 '
c =
Example 6
Types of porous diffusion. Shaded areas represent nonporous solids
Hindered diffusion for solute in solvent-filled
pores
A general model is

F
1
and F
2
are correction factors, function of pore
diameter,

F
1
is the stearic partition coefficient

) ( ) (
2 1
F F D D
o
AB Ae
=
pore
s
d
d
=
2
2
1
2
( )
( ) (1 )
pore s
pore
d d
F
d
t

t

= =
F
2
is the hydrodynamic hindrance factor, one
equation is by Renkin,

5 3
2
95 . 0 09 . 2 104 . 2 1 ) ( + = F
Example 7
Convective Mass Transfer
Mass transfer between moving fluid with
surface or another fluid
Forced convection
Free/natural convection
Rate equation analogy to Newtons cooling
equation
A c A
c k N A =
Example 8
Differential Equations
Conservation of mass in a control volume:

Or,
in out + accumulation reaction = 0
( )
}}} }}
=
c
c
+
. . . .
0
v c s c
dV
t
dA n v
For in out,
in x-dir,

in y-dir,

in z-dir,

For accumulation,

x x A x x x A
z y n z y n A A A A
A + , ,
y y A y y y A
z x n z x n A A A A
A + , ,
z z A z z z A
y x n y x n A A A A
A + , ,
z y x
t
A
A A A
c
c
For reaction at rate r
A
,

Summing the terms and divide by AxAyAz,

with control volume approaching 0,

z y x r
A
A A A
, , , , , ,
0
A x x x A x x A y y y A y y A z z z A z z
A
A
n n n n n n
r
x y z t

+A +A +A

c
+ + + =
A A A c
, , ,
0
A
A x A y A z A
n n n r
x y z t
c c c c
+ + + =
c c c c
We have the continuity equation for
component A, written as general form:

For binary system,

but
and
0 =
c
c
+ V
A
A
A
r
t

n
( )
( )
( )
n n 0
A B
A B A B
r r
t
c +
V + + + =
c
v v v n n = + = +
B B A A B A
B A
r r =
So by conservation of mass,

Written as substantial derivative,

For species A,

0 =
c
c
+ V
t

v
0 = V + v

Dt
D
0 = V +
A A
A
r
Dt
D
j
e
In molar terms,

For the mixture,

And for stoichiometric reaction,

0 =
c
c
+ V
A
A
A
R
t
c
N
( )
( )
0 ) ( = +
c
+ c
+ + V
B A
B A
B A
R R
t
c c
N N
0 ) ( = +
c
c
+ V
B A
R R
t
c
cV