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DEFINITION OF MASS FLUXES

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

Local Mass Average Velocity

n
∑ ρi vi
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 vi = ∑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

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

v JA = ρA (vA _ v v )

dxA
M JA = _ cDAB 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 = ρA (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
m JA + w A ∑ni
Nc Nc
i =1
(5-182 ChE HB)
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

N A ≠ _ 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
NA + NB

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

1. UNIMOLECULAR DIFFUSION (UMD)


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

dxA
N A = _ cDAB + x A (N A + N B ) NB = 0
dz
dxA
N A = _ cDAB + xANA
dz

dx z x d xA
N A (1 x A ) = cDAB A
_ _
 N A ∫z 2 d z = _ c DA B∫x 2
dz 1 1 1_ x
A

cDAB 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

dxA
N A = _ cDAB + x A (N A + N B ) N = NA + NB = 0
dz

dxA
N A = _ cDAB
dz

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

Important!

For EMD: DAB = DBA

For UMD: There is no such thing as DBA!

I. DIFFUSION
Eq. 5-189 IN
ChEGASES
HB

CaseP1 UMD
c=
RT
2
PDAB 1_ x A2 B
NA = _
ln _
RT( z 2 z 1 ) 1 x A1 1
A

A,C

Case 2 EMD

Eq. 5-190 ChE HB

P
c=
RT

_P x A 2 _ x A1
NA = D
R T A B 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''


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

Fuller-Schettler-Giddings Correlation

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

Σ 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 = ( ) = 1
M av 2

Case 2 EMD

_ x A 2 _ x A1
N A = c avD A B
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


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