molecules are little (hard) spheres moving

around with their thermal velocity and

occasionally bumping into each other
d
d d
12
1 2
2
,
=
+
( )

RT
pd M M
12
3
3 2
12
2
1 2
1 2
2 1 1
,
/
,
/
= +
|
\

|
.
|
t A
d
1
d
2
( )

T
p
M M
12
8
175
1
1 3
2
1 3
2
1 2
1 2
316 10
1 1
,
.
/ /
/
. =
+
+
|
\

|
.
|

u u
empirical modification:
diffusion volume s liquid volume, m
3
mol
-1
Diffusivities in Gases
Gases, empirical equation
( )

T
p
M M
12
8
175
1
1 3
2
1 3
2
1 2
1 2
316 10
1 1
,
.
/ /
/
. =
+
+
|
\

|
.
|

u u
H
2
N
2
CO
2
NH
3
H
2
O
7.07 17.9 26.9 14.9 12.7
u
i
10
6
m mol
3 1
diffusion volume s liquid volume, m
3
mol
-1
Gases, example
N
2
(1) CO
2
(2)
T = 300 K
p = 10
5
Pa
( ) ( )
| |

12
8
175
5 6
1 3
6
1 3
2
3 3
1 2
5
316 10
300
10 17 9 10 26 9 10
10
28
10
44
175 10
,
.
/ /
/
.
. .
.
=
+
+

(
=

m s
2 1

1 2 ,
0 1
x
1

1 2 ,
does not depend
on composition
binary: multicomponent:

i j i j
binary
, ,
=
also does not
depend on
composition
1 2
3

1 2 ,

13 ,

2 3 ,
mole fraction
composition
triangle
Gases - Multicomponent
Dilute Species in a Liquid
d
1
1
1 3
=
|
\

|
.
|
u
A
/
u
1

RT
d
12
2 1
3
,
=
t q A
this constant varies with the
size ratio of the species:
d d
1 2
>>
d d
1 2
=
3t
2t
1t
0 2 4
d
d
1
2
1 2 9
2
2
1 2
2 , 1
s m 10
2

~
q t
=
d d
RT

A
Ideal Binary
5
2
1
0.5
0
1

1 2 ,
D
12 ,
D
12 12
9
10
, ,
,

m s
2 1
25
o
C
hexane (1) -
hexadecane (2)
D
12 12 , ,
~
logarithmic interpolation:
larger in the mobile fluid
x
1
MS and Fick diffusivities
almost equal
( ) ( )

x
x
x
x
12 12
1
12
1
1
1
2
2
, , ,
=
= =
Non-ideal Binary
25
o
C

1 2 ,
ethanol (1) - water (2)
5
2
1
0.5
0
1
x
1
D
12 ,
D
12 12 , ,
>
interpolation roughly
logarithmic for
MS and Fick diffusivities
differ
only at
x x
1 2
1 1 = = and is
D
12 12 , ,
=
D
12 12
9
10
, ,
,

m s
2 1
Very Non-ideal
5
2
1
0.5
0
1
x
1

1 2 ,
D
12 ,
25
o
C
acetone (1) - water (2)
factor of 4 difference
between MS and Fick
diffusivities
interpolation very roughly
logarithmic for
D
12 12
9
10
, ,
,

m s
2 1
( ) ( ) ( )

i j i j
x
x
i j
x
x
i j
x
x
i
i
j
j
k
k
, , , ,
=
=
=
= 1
1
1
1 2
3

1 2 ,

13 ,

2 3 ,
mole fraction
composition
triangle
for lack of better...
logarithmic
scale
if only binary data
are available:
( )( )
| |

i k
x
j k
x
k k
, ,
/
= = 1 1
1 2
Ternary - Interpolation
5
2
1

i j ,
10 m s
-9 2 1
1
3 2
mole fraction composition triangle

1 2 ,

13 ,

2 3 ,
Toluene, Chloro- & Bromo-benzene