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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!
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
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
Z
V
S
i
dV
d
dt
Z
V
c
i
dV =
Z
S
x
i
cv
M
Z
S
J
i
Z
V
S
i
dV
13 MassTransfer.key - January 10, 2014
Ficks Law Example: Equimolar Counter-diffusion
Assume:

T, p are constant

No reaction

## 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-
vM = 0 no reaction
a = z
a = z
Tube sides:
Tube face at z=0:
Tube face at z=L:
Z
S
J
A
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
c
J
L
A
Z
S
J
A
c
J
0
A
SHR 3.1.3
d
dt
Z
V
c
i
dV =
Z
S
x
i
cv
M
Z
S
J
i
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.
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

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
Z
S
J
i
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
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