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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
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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
– Curie’s 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.
– Onsager’s reciprocal relations. The matrix fluxes-
forces is symmetric
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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 (µ)
Energy Fourier (k) Dufour effect (D
A
T
)
T
Mass Soret effect Fick (D
ab
)
D
A
T
(
ab
)
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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 (
|
= |
|
¿
µ
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
µ µ
µ ÷ V ÷ =
|
= |
| o
o|
o o ¿
– Diffusional driving forces: d
|
Concentration pressure forced diffusion
1
µ µ
|
| o
– Concentration-, pressure-, forced-diffusion
– a = phenomenological coefficients
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Mass transport Mass transport
N
• Generalised Fick equation
N ,... 2 , 1 for d D ) T ln( D j
N
1
T
a
= o µ ÷ 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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|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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Generalized Maxwel-Stefan equations Generalized Maxwel-Stefan equations
D
D
x x
T
T
|
|

|
( ) T ln
D
D
D
x x
d ÷ V ·
|
|
.
|

\
|
µ
÷
µ
÷ =
|
|
o
o
o = |
o|
| o
o
¿
. \
µ µ
| o
|
o|
( ) N 3 2 1
j
j
x x
= o
|
|
|

|
÷
|
o
| o
¿
( ) N ... 3 , 2 , 1
D
= o
|
|
.

\
µ µ
| o
o = |
o|
¿
• is the multicomponent Maxwell-
St f diff i iti
o|
D
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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
|
|
.
|

\
|
µ
÷
µ µ
+
|
|
o
o
o|
= o
|
= |
o
| o
¿¿
j
j
D
D
x cRTx
A
1 1
. \
o = |
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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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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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( )
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
(
¸
(

¸

µ e + µ ÷ 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
|
|
.

\
µ µ
| o
o = |
= |
o|
¿
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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 µe ÷
V e ÷ | + V · ÷ =
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( ) ] T ln k g g
T B A B A
V + e µe
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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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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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
|
.

\
µ
+
z=L
dp
z=L
z=0
o
R g
dz
dp
O µ ÷ ~ µ ÷ =
O
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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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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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+ ¬ | > 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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