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Ficks Law for Binary

Systems
9 MassTransfer.key - January 10, 2014
Molar Fluxes in Binary Systems
N = N
A
+N
B
v
M
=
N
c
=
N
A
+N
B
c
= x
A
v
A
+x
B
v
B
Ficks law is a MODEL for J
A
(has limitations!)
D
AB
= D
BA

J
A
= -J
B

For C > 2 components, everything changes!
(graduate school, anyone?)
A species A in mixture of A & B.
N
A
molar ux of A.
v
A
velocity of A.

x
A
mole fraction of A.

c mixture molar concentration.
N total molar ux.
v
M
mixture molar-averaged velocity.

J
A
- molar diffusive ux of A relative to a
molar averaged velocity. (motion of A
relative to the mixture motion)
Diffusive uxes are only dened relative
to a convective and total ux!
Diffusive and convective uxes are NOT
independent (they must sum to N
A
).
N
A
= cx
A
v
A
molar convective
ux of A
(carried by v
M
)
molar diffusive
ux of A
(relative to v
M
)
J
A
= N
A
cx
A
v
M
J
A
= cD
AB
x
A
Ficks Law
J
A
= cD
AB
dx
A
dz
N
A
= cx
A
v
M
cD
AB
dx
A
dz
= x
A
N cD
AB
dx
A
dz
N
B
= x
B
N cD
AB
dx
B
dz
Here we have assumed 1-D.
We could use vectors for
uxes & velocities...
Often we know something about x
A
(z)
and v
M
. Ficks law lets us get N
A
.
SHR 3.1.1
10 MassTransfer.key - January 10, 2014
Mixture Velocities
Motorcycle:
Dump Truck:
u
m
= 50
u
t
= 30
If there are n
m
motorcycles and n
t
trucks
on the road, what is the average velocity?
Number averaged:
Mass averaged: v =
n
m
m
m
v
m
+n
t
m
t
u
t
n
m
m
m
+n
t
m
t
v
#
=
n
m
v
m
+n
t
u
t
n
m
+n
t
u
t
= v
#
+v
#
t,di
u
m
= v
#
+v
#
m,di
u
t
= v +v
t,di
u
m
= v +v
m,di
N
A
= c
A
v
M
+J
A
= x
A
cv
M
+J
A
= x
A
N +J
A
Molar ux
(analogous to number ux)
what if
n
m
=n
t
?
what if
n
m
=n
t
and
m
t
!m
m
?
v
A
=
N
A
c
A
=
N
A
cx
A
v
M
=
N
c
=
N
A
+N
B
c
v
A,di
=
J
A
/c
A
Ficks Law gives us a relationship between J
A
& x
A
.
11 MassTransfer.key - January 10, 2014
Steady-State Diffusion in Binary Systems
SHR 3.3.1
Be careful with areas!
(ux vs. ow rate)
If there is no bulk ow (N

= 0) then
N
A
= cD
AB
dx
A
dz
= D
AB
dc
A
dz
(if c is constant)
Planar system with constant N
A
(or n
A
):
Concentric cylinders with constant n
A
:
N
A
= x
A
(N
A
+N
B
)
| {z }
N
+J
A
Note: in cylindrical & spherical
coordinates, constant nA does
not imply constant NA.
n
A
= 2LD
AB

c
A
2
c
A
1
ln (
r
2
/r
1
)

Spherical shell with constant n


A
:
N
A
= D
AB

c
A
2
c
A
1
z
2
z
1

c
A
2
c
A
1
c
A
1
c
A
2
n
A
= 4r
1
r
2
D
AB

c
A
2
c
A
1
r
2
r
1

J
A
= cD
AB
dx
A
dz
n
A
= x
A
(n
A
+n
B
)
| {z }
n
+AJ
A
12 MassTransfer.key - January 10, 2014
The Molar Balance Equations (Again)
c
i
t
= N
i
+S
i
c
i
t
= (c
i
v
M
) J
i
+ S
i
J
A
= cD
AB
x
A
For a binary system of A and B:
Integral Forms
Differential Forms
In terms of total
species uxes:
In terms of convective and
diffusive species uxes:
In terms of total
species uxes:
In terms of convective and
diffusive species uxes:
N
i
= c
i
v
M
+J
i
= x
i
N+J
i
d
dt
Z
V
c
i
dV =
Z
S
N
i
adS +
Z
V
S
i
dV
d
dt
Z
V
c
i
dV =
Z
S
x
i
cv
M
adS
Z
S
J
i
adS +
Z
V
S
i
dV
13 MassTransfer.key - January 10, 2014
Ficks Law Example: Equimolar Counter-diffusion
Assume:

T, p are constant

No reaction

1-D domain z=[0,L]

Compositions are known at


domain boundaries z = 0, z = L.
z = 0 z = L
Equimolar counter-diffusion: for
every mole of A that moves to the
left, a mole of B moves to the right.
x
A
= x
0
A
z = 0
x
A
= x
L
A
z = L
Total ux must be zero (closed
system, constant T, p).
Therefore, N = cv
M
= 0 so v
M
= 0.
N
A
= x
A
N +J
A
= J
A
= cD
AB
dx
A
dz
pseudo-
steady state
vM = 0 no reaction
a = z
a = z
Tube sides:
Tube face at z=0:
Tube face at z=L:
Z
S
J
A
adS = 0
Note: we could have done this integral balance on
any segment of the tube and arrived at the same
conclusion regarding JA. Therefore, it must be
constant! Since JA = NA, NA is also constant!
Break the surface integral into pieces:
" Tube mole
balance gives:
N
A
dz = cD
AB
dx
A
Z
L
0
N
A
dz =
Z
x
L
A
x
0
A
cD
AB
dx
A
Find ux through the tube.
N
A
Z
L
0
dz = cD
AB
Z
x
L
A
x
0
A
dx
A
N
A
=
cD
AB
L

x
L
A
x
0
A

A
c
J
L
A
A
c
J
0
A
= 0
J
0
A
= J
L
A
Z
S
J
A
adS = A
c
J
L
A
Z
S
J
A
adS = A
c
J
0
A
SHR 3.1.3
d
dt
Z
V
c
i
dV =
Z
S
x
i
cv
M
adS
Z
S
J
i
adS +
Z
V
S
i
dV
14 MassTransfer.key - January 10, 2014
z = 0 z = L
We previously showed:
N
A
= J
A
(no bulk ow/convection)
N
A
is constant (so J
A
is constant)
What is the species mole fraction prole through the tube?
J
A
= cD
AB
dx
A
dz
= !
dx
A
=

cD
A
B
dz
Z
x
A
x
0
A
dx
A
=

cD
A
B
Z
z
0
dZ
x
A
x
0
A
=

cD
A
B
z
Note: to determine !, we can use x
A
(L) = x
L
A
x
A
= x
0
A
+

x
L
A
x
0
A

z
L
15 MassTransfer.key - January 10, 2014
Bulb Balances
z = 0 z = L
N
A
=
cD
AB
L

x
L
A
x
0
A

Find the composition in each


bulb as a function of time.
Pseudo-steady state:
The tube is at steady state (adjusts to the
slowly changing bulb compositions quickly).
For the
left bulb:
vM = 0 no reaction
V
0
dx
0
A
dt
=
A
c
D
AB
L

x
L
A
x
0
A

Mole balance on A relating


to steady-state conditions:
cx
0
A
V
0
+cx
L
A
V
L
| {z }
at time t
= cx

A
(V
0
+V
L
)
| {z }
at t=
x
L
A
= x

A
(1 +
V
0
/V
L
) x
0
A
V
0
/V
L
dx
0
A
dt
=
A
c
D
AB
V
0
L

A
x
0
A

(1 +
V
0
/V
L
)

= D
AB

A
x
0
A

We need to eliminate x
L
A

A
c
V
0
L

1 +
V
0
V
L

Geometry factor
x
0
A
= x

A
+

x
0
A,0
x

exp(D
AB
t)
Separate
& solve...
A nice way to determine D
AB
experimentally!
d
dt
Z
V
c
i
dV =
Z
S
x
i
cv
M
adS
Z
S
J
i
adS +
Z
V
S
i
dV
0 2000 4000 6000 8000 10000
0
0.1
0.2
0.3
0.4
0.5
(s/m
2
)
x
A 0


D
ab
= 0.01
D
ab
= 0.001
D
ab
=0.0001
D
ab
= 1e05
t
cV
0
dx
0
A
dt
= N
0
A
A
c
16 MassTransfer.key - January 10, 2014
Example: Evaporation from a Beaker
(Unimolecular Diffusion)
Benzene (A)
& air (B)
Determine x
A
(z).
What do we know about N
A
& N
B
?
N
A
= x
A
N +J
A
N
A
= x
A
N
A
+ J
A
=
J
A
1 x
A
N
A
=
cD
AB
1 x
A
dx
A
dz
(1-xA) accounts for bulk ow.
In very dilute systems (xA!0),
this effect is small relative to JA.
N
A
=
cD
AB
z z
0
ln

1 x
A
1 x
0
A

or
1. Estimate gas-phase composition of benzene at the
vapor-liquid interface (from equilibrium thermo).
2. Determine N
A
from x
A
at z=0.
3. Determine x
A
(z).
SHR 3.1.4
N
A
cD
AB
Z
z
z
0
dz =
Z
x
A
x
0
A
dx
A
1 x
A
x
A
= 1 (1 x
0
A
) exp

N
A
(z z
0
)
cD
AB

DAB=0.0905 cm
2
/s
Note: from x
A
(z) and N
A
you
can determine anything else
about the system (e.g. J
A
(z)).
17 MassTransfer.key - January 10, 2014
The Log-Mean
N
A
=
cD
AB
z z
0
ln

1 x
A
1 x
0
A

(1 x
A
)
LM
= (x
B
)
LM
=
(1 x
A
2
) (1 x
A
1
)
ln
h
1x
A
2
1x
A
1
i
=
x
A
1
x
A
2
ln [
(1x
A
2
)
/(1x
A
1
)]
N
A
=
cD
AB
(1 x
A
)
LM
x
A
z
This makes things look a bit cleaner and allows
us to express N
A
in terms of !x
A
.
You will see this used more when we start
dealing with Mass-Transfer Coefcients (soon)...
Log-mean of x
A
at
the two ends of
the diffusion path.
18 MassTransfer.key - January 10, 2014
Comments on Ficks Law
In this class, we typically assume that the total molar
concentration, c, is constant.
This is usually reasonable for isothermal, isobaric systems or for liquid
systems.
We have only considered binary systems.
For multicomponent systems, things become considerably more complex.
Other driving forces:
other species can cause strange diffusion (push a species against its
gradient) for C > 2 components.
pressure gradients (centrifugation)
thermal gradients (Soret effect)
In general, the chemical potential is the correct driving force for diffusion.
19 MassTransfer.key - January 10, 2014