aggregated

porous
fibrous
membrane
catalyst
scale of
heterogeneity
scale of
the phase
<<
Two ways of looking at porous media:
N S
Non-structured Structured
etcetera
filter
expected to be equal when:
Two Ways
Species: 1 a small one (water)
2 a large one (protein)
The matrix M is solid phase that
can resist stresses, and
can transmit support forces
membrane support
Our Species
Driving Forces
dz
dp
V
dz
d
dz
a d
RT F
2 2
2
2
ln

|
= Fz

dz
dp
V
dz
d
F x F x F
|
= + = Fz
2 2 1 1
dz
dp
V
dz
d
dz
a d
RT F
1 1
1
1
ln

|
= Fz
on the components separately
on the mixture as a whole
internal forces cancel
N
mol of i
N
mol of mixture
2 2 1 1
z z z x x + =
with
2 2 1 1
V x V x V + =
u
i

v
i

u
i

v
i

w u v
i i i
= +
diffusive velocity
slipping past the matrix
viscous velocity
transport by convection
whole (overall) velocity
1
2
3
Three Velocities
F v
V
= ,
viscous friction coefficient
,
q
V
cB
=
hydraulic permeability
B
d
pore
=
2
32
( )
B
d
sphere
=

2
2
2
170
1
c
c
( )
B
d
fibre
=

2 2
2
80
1
c
c
Viscous Flow and Friction
void fraction
complications in channels of colloidal dimensions:
surface adsorption
changes diameters
particles cause
increased friction
Complications
Viscous Selectivity
viscous velocity of a centerline
species higher than average
v
v
v
i
v
i
o
i
> 1
viscous velocity of adsorbing
species lower than average
o
i
< 1
v v
i i
= o
v v v
i i i i i i
= = =

c c o c o 1
volume balance
viscous selectivity
Transport Equations
( )
1 , 1 2 1 2 , 1 2 1
u u u x F
M
, + , =
( )
2 , 2 1 2 2 , 1 1 2
u u u x F
M
, + , =
F v
V
= , v v
1 1
= o v v
2 2
= o
Structured model
w u v
1 1 1
= + w u v
2 2 2
= +
diffusive
viscous
whole
Non-structured model
( )
1 , 1 2 1 2 , 1 2 1
w w w x F
M
+ =
( )
2 , 2 1 2 1 , 2 1 2
w w w x F
M
+ =
whole velocities in one go

(ksi)
,
(zeta)
Mason Equations
( )
M M V
M M M
x x
x
, 2 2 2 , 1 1 1
2 1 , 2 2 , 1 2 , 2 , 1 1
2 , 1 2 , 1
, o + , o + ,
o o , , + , , o
+ , =
( )
M M V
M M M
x x
x
, 2 2 2 , 1 1 1
1 2 , 1 2 , 1 1 , 2 , 1 2
2 , 1 1 , 2
, o + , o + ,
o o , , + , , o
+ , =
| |( )
|
|
.
|

\
|
, o + , o + ,
o o , + , + , , , + ,
, =
M M V
M M M V
M M
x x
x x x x
. 2 2 2 , 1 1 1
2 1 , 1 1 2 , 1 2 1 , 2 , 1 2 , 1
2
1
, 2 , 2
| |( )
|
|
.
|

\
|
, o + , o + ,
o o , + , + , , , + ,
, =
M M V
M M M V
M M
x x
x x x x
, 2 2 2 , 1 1 1
1 2 , 2 2 2 , 1 2 1 , 1 , 2 2 , 1
2
2
, 1 , 1
Approaches identical when:
Non-structured Structured
w
1
d
p
v
1

u
1
Structured Non-structured
= V
dp
dz
u
M
,
1 1 ,
= V
dp
dz
v
V
,
1
= V
dp
dz
w
M

1 1 ,
w u v
1 1 1
= + | |
, ,
1
1
1
1
1
, , M V M
= +


Single Liquid Permeant
Permeant - Matrix Coefficient
a rough estimate
d
1
d
p
t
u
1
u
d
at wall
1
1
2
=
t
q
t =
d
dp
dz
pore
4
=

(
(
V
dp
dz
V
d d
u
pore
at wall
4
2
1
1
q
pore
wall at
pore
wall at
M
d
d
d d
V
2
1
1
, 1
4 8 q ~
q
= ,
Friction Coefficients vs Pore Diameter
permeant-permeant
permeant-matrix
viscous
,
V pore
d
2
1
, 1

,
pore M
d
0
2 , 1 pore
d ,
2 , 1
,
M , 1
,
,
V
ln,
lnd
p
Wide Pores
write N- equations per mol of mixture:
( ) v x v v x x F x
M , 1 1 2 , 1 2 1 1 1
+ =
( ) v x v v x x F x
M , 2 2 1 , 2 2 1 2 2
+ =
summing the equations:
( ) v v x x F
V M M
, + =
, 2 2 , 1 1
identical to viscous flow through a tube
Wide pores:
w v
w v
1
2

Two similar Permeants

o o
1 2
1 = =
M M M
, = , = ,
, 2 , 1
M V
M
, + ,
,
+ , =
2
2 , 1 2 , 1
M V
V
M M
, + ,
,
, =
, 1
M V
V
M M
, + ,
,
, =
, 2
2 , 1 2 , 1
, >
viscous flow makes the N-coefficient
larger than the S-coefficient
M M , 1 , 1
, <
Permeants similar, with slipping
M V
M
, + ,
,
+ , =
2
1 , 2 1 , 2
viscous flow makes the N-coefficient
smaller than the S-coefficient
Dilute Solute, no Slipping
= ,
M , 1
M , 2 2 , 1 2 , 1
, + , =
M , 2 2 1 , 2 1 , 2
, o + , =
,
1,M V
=
( )( )
2 2 , 1 , 2 , 2
1 o , + , =
M M
Protein (2) dilute, no slipping of water (1)
w v v
1 1
= =