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Other mechanisms for mass transport Other mechanisms for mass transport
E ti f h f t Equation of change of entropy.

Flux expressions for heat and mass p
Concentration diffusion and driving forces
M ll S f i Maxwell-Stefan equations
Mass transfer across selectively permeable y p
membranes
Diff i i di Diffusion in porous media
Luis Moreno - Transport Phenomena
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1
The equation of change of entropy The equation of change of entropy
ilib i h d i f Non-equilibrium thermodynamics use four
postulates
quasi-equilibrium postulate. gradients not too large
Linearity postulate Fluxes linearly force dependent Linearity postulate. Fluxes linearly force dependent
Curies postulates. No coupling of fluxes and force if
diff i t i l d i dd b difference in tensorial order is an odd number.
Onsagers reciprocal relations. The matrix fluxes-
forces is symmetric
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2
Fluxes and Forces
D i i V l it T t C t ti Driving
Forces /
Fluxes
Velocity
gradient
Temperature
gradients
Concentration,
pressures, external
forces Fluxes forces
Momentum Newtons ()
Energy Fourier (k) Dufour effect (D
A
T
)
T
Mass Soret effect Fick (D
ab
)
D
A
T
(
ab
)
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3
The flux expressions for heat and mass The flux expressions for heat and mass
The fluxes vectors
|
|
V = d
cRTa
) T ln( a q
N
0
00
) h (
|
= |
|

V d ) T ln( a q
1
00
cRTa
N
N ,... 2 , 1 for d
cRTa
) T ln( a j
N
1
0 a
= o

V =
|
= |
| o
o|
o o
Diffusional driving forces: d
|
Concentration pressure forced diffusion
1

|
| o
Concentration-, pressure-, forced-diffusion
a = phenomenological coefficients
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4
Mass transport Mass transport
N
Generalised Fick equation
N ,... 2 , 1 for d D ) T ln( D j
N
1
T
a
= o V =
|
= |
o| o o

1 = |
T
D
T
D
o
o|
D
Multicomponent thermal diffusion
Multicomponent Fick diffusivities | p
|o o|
= D D
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5
|o o|
Mass transport p
Four contributions to mass flux vector
Concentration diffusion term (activity coefficient)
Pressure diffusion term (pressure gradient) Pressure diffusion term (pressure gradient)
Forced diffusion (external forces)
Thermal diffusion (proportional to the thermal e a d us o (p opo o a o e e a
gradient)
Solving the generalised Fick equation for the
driving forces the Maxwell-Stefan equations are driving forces, the Maxwell-Stefan equations are
obtained
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6
Generalized Maxwel-Stefan equations Generalized Maxwel-Stefan equations
D
D
x x
T
T
|
|
|
( ) T ln
D
D
D
x x
d V
|
|
.
|
\
|
=
|
|
o
o
o = |
o|
| o
o

. \

| o
|
o|
( ) N 3 2 1
j
j
x x
= o
|
|
|
|
o
| o
( ) N ... 3 , 2 , 1
D
= o
|
|
.
\

| o
o = |
o|
is the multicomponent Maxwell-

St f diff i iti
o|
D
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7
Stefan diffusivities
Heat Transport Heat Transport
Heat flux vector Heat flux vector
N
+ V =
o
j
M
H
) T ln( k q
N
1
|
|
|
| | o
= o
o
j
j D
x cRTx
M
T
A
N N
1
|
|
.
|
\
|

+
|
|
o
o
o|
= o
|
= |
o
| o
j
j
D
D
x cRTx
A
1 1
. \
o = |
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8
Heat Transport Heat Transport
Heat flux vector consist of three terms: Heat flux vector consist of three terms:
heat conduction term. Containing the thermal
conductivity conductivity
heat diffusion term. Containing the partial molar
enthalpies and the mass fluxes enthalpies and the mass fluxes
Dufour term. Containing the thermal diffusion
coefficients and the mass fluxes Dufour term is coefficients and the mass fluxes. Dufour term is
usually small)
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9
Relationships between diffusivities Relationships between diffusivities
Multicomponent Maxwell-Stefan diffusivities as
function of the Multicomponent Fick p
diffusivities
( )
|
o o
adjB D
x x
( )
( )
|
o =
|
o o
|
| o
o|
e e
=
adjB
x x
D
( )
o =
|
o | o
e e adjB
Matrix B contains the Multicomponent Fick
diffusivities (sum of two terms)
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10
( )
Mass transport Useful cases Mass transport. Useful cases
Multicomponent diffusion in gases or liquids p g q
( ) ( ) a ln x v v
x x
T
N
V =
|
| o
( ) ( ) a ln x v v
D
p , T
1
(
V
o o | o
o = |
= |
o|
( ) g g p
cRT
1
N
1
(
e + V e |
= |
| | o o o | o

( ) ) N 2 1 ( T ln
D
D
x x
cRT
T
T
N
1
= o V
|
|
|
|

|
o
| o
= |
( ) ) N ,....... 2 , 1 ( T ln
D
1
= o V
|
|
.
\

| o
o = |
= |
o|

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11
Mass transport. Useful cases Mass transport. Useful cases
Multicomponent diffusion in Gases at low p
density
Activity is replaced by the mole fraction Activity is replaced by the mole fraction
The Multicomponent Maxwell-Stefan diffusivities
may be replaced by the Binary diffusivities may be replaced by the Binary diffusivities
Binary diffusion in gases or liquids (k
T
is the
thermal diffusion ratio) thermal diffusion ratio)
( ) ( ) | | p
1
a ln x [ D c j
*
V e | + V = ( ) ( ) | |
( ) ] T ln k g g
p
cRT
a ln x [ D c j
A A
A A p , T A A AB A
V + e e
V e | + V =
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12
( ) ] T ln k g g
T B A B A
V + e e
Thermal diffusion and the Clusius-Dickel
column
Thermal diffusion
Mixture of ideal gases A Mixture of ideal gases A
and B
Constant temperatures Constant temperatures
T
1
and T
2
for the bulbs
G Ai i h d
0
d
dT k
d
dx
T A
= +
Gas A is enriched at one
end and depleted and the
h
dz T dz
other
At steady state
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13
y
Thermal diffusion and the Clusius-Dickel
column
Integrating T
T
T
2 A 1 A
dT
T
) T ( k
x x
2
1
=
}
2
T
T
ln ) T ( k
T
1
=
Aplication
1
m T
T
ln ) T ( k =
Aplication
Clusius-Dickel column
Heated
wall a T
2
Cooled
wall at T
1
The upward stream will
be richer in one of the
1
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14
components
Pressure diffusion and the ultra centrifuge g
A and B in diffusion cell. The centrifugal force
tends to separate A and B p
O
A A A A
dp 1 V x M dx
|
|
|
+
R
O z
A
dz M RT dz
|
.
\

+
z=L
dp
z=L
z=0
o
R g
dz
dp
O ~ =
O
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15
Pressure diffusion and the ultra centrifuge g
W i i i f A d B d b i Writing expressions for A and B and subtracting
g dx dx
( ) dz V M V M
RT
g
x
dx
V
x
dx
V
B A A B
B
B
A
A
A
B
=
O
Integrating
B A
Integrating
V M V M x
l V
x
l V
B A A B B A

x g
RT x
ln V
x
ln V
B A A B
0 B
B
A
0 A
A
B O
=
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16
Application of the generalised Maxwell-
Stefan equations
C t if ti f Centrifugation of
Proteins.
dx ln
1 v
x
p p p
|
|
|
|
c
+ =
dr x ln
1 v
D
p
pr
PW
|
|
.
\
c
+ =
( )
dr
dp
cRT
1
p p
e |
dr cRT
+ | > e r to v ) fract volume ( ) fract mass ( if
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17
+ | > e r to v ) fract volume ( ) fract mass ( if
pr p p
M S equations Proteins Centrifugation M-S equations. Proteins Centrifugation
Initially, first term is negligible and proteins
emigrate then in the r-direction. g
At steady state, there is equilibrium between
the pressure diffusion and diffusion caused the pressure diffusion and diffusion caused
by the concentration gradient.
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18

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Other mechanisms for mass transport Other mechanisms for mass transport

E ti f h f t Equation of change of entropy.

is the multicomponent Maxwell-

Luis Moreno - Transport Phenomena

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