Fick’s Law for Binary

Systems

9 MassTransfer.key - January 10, 2014

 SHR §3.1.1

Molar Fluxes in Binary Systems

• A
species “A” in mixture of A & B.

NA = cxA vA Here we have assumed 1-D. • NA
molar flux of A.

We could use vectors for
N = NA + NB fluxes & velocities...
• vA
velocity of A.

• xA
mole fraction of A.

N NA + NB • c
mixture molar concentration.

vM = = = xA v A + xB v B • N
total molar flux.

c c
• vM
mixture molar-averaged velocity.
• JA - molar diffusive flux of A relative to a
J A = NA cxA vM molar averaged velocity. (motion of A
molar diffusive molar convective relative to the mixture motion)

flux of A
flux of A
• Diffusive fluxes are only defined relative
(relative to vM) (carried by vM) to a convective and total flux!

• Diffusive and convective fluxes are NOT
independent (they must sum to NA).
Fick’s “Law” JA = cDAB rxA
dxA
• Fick’s law is a MODEL for JA (has limitations!)
JA = cDAB
• DAB = DBA
dz
dxA
• JA = -JB
NA = cxA vM cDAB
• For C > 2 components, everything changes! dz
(graduate school, anyone?) dxA
= xA N cDAB
dz
Often we know something about xA(z) dxB
NB = x B N cDAB
and vM. Fick’s law lets us get NA. dz
10 MassTransfer.key - January 10, 2014
 “Mixture Velocities”
Motorcycle: um = 50 If there are nm motorcycles and nt trucks
Dump Truck: ut = 30 on the road, what is the average velocity?

#
nm v m + nt u t ut = v# + vt,di↵ what if
Number averaged: v# = # nm=nt?
nm + nt um = v# + vm,di↵

nm mm vm + nt mt ut ut = v + vt,di↵ what if
Mass averaged: v = nm=nt and
nm mm + nt mt um = v + vm,di↵ mt≫mm?

NA NA
Molar flux
NA = cA vM +JA vA = =
(analogous to number flux) cA cxA
= xA cvM +JA vA,di↵ = JA/cA
= xA N +JA N NA + NB
vM = =
c c
Fick’s Law gives us a relationship between JA & xA.
11 MassTransfer.key - January 10, 2014
 SHR §3.3.1

Steady-State Diffusion in Binary Systems

dxA
NA = xA (NA + NB ) +JA JA = cDAB
| {z } dz
N
If there is no “bulk flow” (N = 0) then
nA = xA (nA + nB ) +AJA dxA
| {z } NA = cDAB
n dz
Be careful with areas!
dcA
(flux vs. flow rate)
= DAB (if c is constant)
dz
Planar system with constant NA (or nA):
✓ ◆ Note: in cylindrical & spherical
c A2 c A 1
NA = DAB coordinates, constant nA does
z2 z1 cA
1
cA
2
not imply constant NA.

Concentric cylinders with constant nA: Spherical shell with constant nA:
✓ ◆ ✓ ◆
c A2 c A1 c A2 c A1
nA = 2⇡LDAB nA = 4⇡r1 r2 DAB
ln (r2/r1 ) cA
1
r 2 r1

cA
2
12 MassTransfer.key - January 10, 2014
The Molar Balance Equations (Again)
Ni = ci vM + Ji = xi N + Ji
Integral Forms
Z Z Z
In terms of “total” d
ci dV = Ni · a dS + Si dV
species fluxes: dt V S V
Z Z Z Z
In terms of “convective” and d
ci dV = xi cvM · a dS Ji · a dS + Si dV
“diffusive” species fluxes: dt V S S V

Differential Forms
In terms of “total” @ci
species fluxes:
= r · Ni + Si
@t
In terms of “convective” and @ci
= r · (ci vM ) r · J i + Si
“diffusive” species fluxes: @t

For a binary system of “A” and “B”: JA = cDAB rxA

13 MassTransfer.key - January 10, 2014

 SHR §3.1.3

Fick’s Law Example: Equimolar Counter-diffusion

Assume:
Find flux through the tube. xA = x0A z=0
• T, p are constant

• No reaction
xA = xL
A z=L
• 1-D domain z=[0,L]
Equimolar counter-diffusion: for
• Compositions are known at every mole of A that moves to the
domain boundaries z = 0, z = L. z=0 z=L left, a mole of B moves to the right.

Total flux must be zero (closed pseudo-

vM = 0 no reaction
Zsteady state Z Z Z
system, constant T, p).
d
Therefore, N = cvM = 0 so vM = 0. ci dV = xi cvM · a dS Ji · a dS + Si dV
dt V S S V

Break the surfaceZintegral into pieces:

NA = xA N + JA
dxA Tube sides: JA · a dS = 0
S Z
= JA = cDAB
dz Tube face at z=0: a = ẑ 0
JA · a dS = Ac JA
Z S
NA dz = cDAB dxA L
Tube face at z=L: a = ẑ JA · a dS = Ac JA
Z L Z xLA S
NA dz = cDAB dxA ∴ Tube mole
L
Ac J A 0
Ac J A =0
0 x0A
Z L Z xL
A
balance gives: 0
JA L
= JA
NA dz = cDAB dxA
0 x0A Note: we could have done this integral balance on
any segment of the tube and arrived at the same
cDAB L conclusion regarding JA. Therefore, it must be
NA = xA x0A
L constant! Since JA = NA, NA is also constant!

14 MassTransfer.key - January 10, 2014

 We previously showed:

• NA = JA (no bulk flow/convection)

z=0 z=L
• NA is constant (so JA is constant)

What is the species mole fraction profile through the tube?

dxA
JA = cDAB =α
dz
↵
dxA = dz
cDA B
Z xA Z z
↵
dxA = dZ
x0A cDA B 0
↵
xA x0A = z
cDA B

Note: to determine α, we can use xA (L) = xL

A

z
xA = x0A + xL
A x0A
L

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 “Bulb” Balances

Find the composition in each NA =
cDAB L
xA x0A
bulb as a function of time. L

Pseudo-steady state:
z=0 z=L
The tube is at steady state (adjusts to the Z Z vM = 0
Z Z no reaction
slowly changing bulb compositions quickly). d
ci dV = xi cvM · a dS Ji · a dS + Si dV
dt V S S V

Mole balance on A relating

to steady-state conditions: For the dx0A dx0A Ac DAB L
cx0A V0 + cxL 1 “left” bulb: cV0 dt = NA0 Ac V0 = xA x0A
A VL = cxA (V0 + VL ) dt L
| {z } | {z } L
at time t at t=1 We need to eliminate xA
1
xL
A = xA (1 + /VL )
V0 x0A V0/VL
dx0A Ac DAB ⇥ 1 0
⇤
0.5 = xA xA (1 + /VL )
V 0
dt V0 L ✓ ◆
Dab = 0.01 A c V 0
0.4
D
ab
= 0.001 = DAB x1 A x 0
A
⌘
V0 L
1 +
VL
0.3 Dab =0.0001
Dab = 1e−05
“Geometry factor”
x0A

0.2
Separate
& solve...
x0A = x1
A + x 0
A,0 x1
A exp( DAB t)
0.1
⌧⌘ t
0
0 2000 4000 6000
2
8000 10000 A nice way to determine DAB experimentally!
(s/m )
16 MassTransfer.key - January 10, 2014
 SHR §3.1.4

Example: Evaporation from a Beaker

(Unimolecular Diffusion)
Benzene (A)
& air (B) Determine xA(z). NA = x A N + J A

What do we know about NA & NB?

NA = x A NA + J A (1-xA) accounts for “bulk flow.”

In very dilute systems (xA→0),
JA this effect is small relative to JA.
=
DAB=0.0905 cm2/s 1 xA
Z z Z xA
cDAB dxA NA dxA
NA = dz =
1 xA dz cDAB z0 x0A 1 xA
✓ ◆
cDAB 1 xA
NA = ln
z z0 1 x0A
or 
NA (z z0 )
xA = 1 (1 x0A ) exp
cDAB
Note: from xA(z) and NA you 1. Estimate gas-phase composition of benzene at the
can determine anything else vapor-liquid interface (from equilibrium thermo).

about the system (e.g. JA(z)).
2. Determine NA from xA at z=0.

3. Determine xA(z).
17 MassTransfer.key - January 10, 2014
 The Log-Mean
✓ ◆
cDAB 1 xA
NA = ln
z z0 1 x0A

(1 xA2 ) (1 xA1 )
(1 xA )LM = (xB )LM = h i
1 x A2
ln 1 xA
1
Log-mean of xA at
the two ends of
x A1 x A2
=
the diffusion path. ln [(1 xA2 )/(1 xA )]
1

This makes things look a bit “cleaner” and allows

cDAB xA us to express NA in terms of ΔxA.

NA =
(1 xA )LM z You will see this used more when we start
dealing with Mass-Transfer Coefficients (soon)...

18 MassTransfer.key - January 10, 2014

Comments on Fick’s 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.

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