DEFINITION OF MASS FLUXES

Let vi = velocity of the ith species relative to stationary coordinate axis

Local Mass Average Velocity

n
∑ ρi v i
v m = i = 1n
∑ ρi
i =1

Local Molar Average Velocity

n
∑ci v i
v M = i = 1n
∑ci
i =1

Local Volume Average Velocity

n Vi n _
v v = ∑ρi v i = ∑ρi v i M i 1 V i
i =1 M i i =1

Vi partial molar volume of component i

Mi molecular weight of component i

Forms of FICK’s First Law

dc A
v JA = _ D AB flux relative to the volume average velocity
dz

v JA = ρA (v A _ v v )

dx A
M JA = _ cD AB flux relative to the molar average velocity
dz
 M JA = cA (v A _ vM )

dw A
m JA = _ ρD AB flux relative to the mass average velocity
dz

m JA = ρ A ( v A _ vm )

N A = c A ( v A _ 0) = c A v A flux relative to stationary coordinate

Relationship between N and J

Nc
Nc Nc m J A + w A ∑ ni (5-182 ChE HB)
i =1
N A = v J A +c A ∑ N i V i = M J A + x A ∑ N i =
i =1 i =1 MA

DIFFUSION IN BINARY SYSTEMS

STEADY-STATE DIFFUSION

NA ≠ _ NB ≠ 0

NA _
x A2
cD NA N + NB
N A = _AB ln A (5-191 ChE HB)
z 2 z1 N A + N B NA _
x A1
N A + NB

Limiting cases: (1) unimolecular diffusion; (2) equimolar counterdiffusion

1. UNIMOLECULAR DIFFUSION (UMD)

- diffusion of A through a stagnant, non-diffusing B

dx A
N A = _ cD AB + x A (N A + N B ) NB = 0
dz
 dx A
N A = _ cD AB + xANA
dz

dx A z x dx A
N A (1 _ x A ) = _ cD AB  N A ∫z 2 dz = _ cD AB ∫x 2
dz 1 1 1_ x A

cD AB 1_ x A2
NA = ln (5.189 ChE HB)
z 2 _ z1 1 _ x A1

2. EQUIMOLAR COUNTERDIFFUSION (EMD)

- the molar fluxes of A and B are equal but opposite in direction
- NA = -NB

dx A
N A = _ cD AB + x A (N A + N B ) N = N A + NB = 0
dz

dx A
N A = _ cD AB
dz

x A 2 _ x A1
N A = _ cD AB
z 2 _ z1 (5-190 ChE HB)

Important!

For EMD: DAB = DBA

For UMD: There is no such thing as DBA!

I. DIFFUSION IN GASES

Case 1
Eq. 5-189 UMD
ChE HB

P 2
c=
RT
B
1
PD AB 1_ x A 2
NA = ln A
RT( z 2 _ z 1 ) 1 _ x A1
 A,C

Case 2 EMD

Eq. 5-190 ChE HB

P
c=
RT

P x _x
NA =_ D AB A 2 _ A1
RT z 2 z1

Diffusivity or Diffusion Coefficient Of Solute A In Gases (B)

1. Experimental data

Table 2-371 pp. 2-328 to 2-329 ChE HB

Diffusion of pairs of gases and vapors (1atm)

Table 6.2-1 p. 395 Geankoplis

Diffusion coefficients of Gases at 1 atm pressure

2. Prediction using correlations

Table 5-14 ChE HB

Error Correction of DAB:

Chapman-Enskog 7.3% D AB ' P' D AB '' P''

Wilke-Lee 7.0% =
T'1.75 T''1.75
Fuller-Schettler-Giddings 5.4%
 Fuller-Schettler-Giddings Correlation

0.001T1.75M AB 1 / 2
D AB = (5-196 ChE HB / 6.2-45 Geankoplis)
P[(∑ V ) A1 / 3 + (∑ V )B1 / 3 ]2

V atomic diffusion volumes

(Table 5-16 ChE HB / Table 6.2-2 Geankoplis )
MAB = MA-1 + MB-1
T absolute temperature
P pressure in atmosphere
DAB diffusivity (cm2/s in ChE HB; m3/s in Geankoplis)

II. DIFFUSION IN LIQUIDS

Case 1 UMD (diffusion of A through nondiffusing B)

c a D AB 1_ x A 2
NA = ln
z 2 _ z1 1 _ x A1

ρ1 ρ
+ 2
ρ M M2
c av = ( )av = 1
M 2

Case 2 EMD

x A 2 _ x A1
N A = _ c av D AB
z 2 _ z1

Diffusivity of solute A in liquids

For liquids D AB ≠ DBA

1. Experimental data

Table 2-372 ChE HB Diffusivities at 25oC (cm2/s)

Table 6.3-1 p. 401 Geankoplis

D' μ' D' ' μ''

=
T' T' '
2. Correlation

Wilke-Chang
_8
7.4 × 10 (Φ B M B )1 / 2 T
D AB = (5-208 ChE HB /
μ B VA 0.6
6.3-9 Geankoplis)

MB molecular weight of solvent B

B association parameter of the solvent (p. 5-50 ChE HB)
T temperature in kelvins
B viscosity of solvent B, cP
VA molar volume of solute at the boiling point, cm3/gmol
Table 6.3-2 Geankoplis (m3/kgmol)