Diffusion Mass Transfer

Chapter 14
Sections 14.1 through 14.7

General Considerations

General Considerations
Mass transfer refers to mass in transit due to a species concentration gradient
in a mixture.
Must have a mixture of two or more species for mass transfer to occur.
The species concentration gradient is the driving potential for transfer.
Mass transfer by diffusion is analogous to heat transfer by conduction.
Physical Origins of Diffusion:
Transfer is due to random molecular motion.
Consider two species A and B at the same T and p,
but initially separated by a partition.
Diffusion in the direction of decreasing
concentration dictates net transport of
A molecules to the right and B molecules
to the left.
In time, uniform concentrations of A and
B are achieved.

Definitions

Ci :

Definitions
Molar concentration kmol/m of species i.
3

i : Mass density (kg/m3) of species i.

Mi : Molecular weight (kg/kmol) of species i.
i MiCi

J i* : Molar flux kmol/s m 2 of species i due to diffusion.

Transport of i relative to molar average velocity (v*) of mixture.
N i : Absolute molar flux kmol/s m 2 of species i.
Transport of i relative to a fixed reference frame.
ji :

Mass flux kg/s m of species i due to diffusion.

Transport of i relative to mass-average velocity (v) of mixture.

ni:

Absolute mass flux kg/s m 2 of species i.

Transport of i relative to a fixed reference frame.

xi :

Mole fraction of species i xi Ci / C .

mi :

Mass fraction of species i mi i / .

Property Relations

Property Relations
Mixture Concentration:
C Ci xi 1
i

Mixture Density:

i mi 1
i

Mixture of Ideal Gases:

p
Ci i
iT

pi
RiT

p pi
i

xi

Ci pi

C
p

Diffusion Fluxes

Molar and Mass Fluxes of Species A due to Diffusion

in a Binary Mixture of Species A and B
Molar Flux of Species A:
By definition:
J A C A v A v
v x A v A xB v B

From Ficks law (mass transfer analog to Fouriers law):

J A CDABx A
Binary diffusion coefficient or mass diffusivity (m2/s)

Mass Flux of Species A:

By definition:
jA A vA v
v = mA v A mB v B
From Ficks law:
j A DABmA

Absolute Fluxes

Absolute Molar and Mass Fluxes of Species A

in a Binary Mixture of Species A and B
Molar Flux of Species A:
N A C A v A J A C A v
N A JA C A x A v A xB v B
N A CDABx A x A N A N B
Mass Flux of Species A:
nA A v A jA A v
nA j A A mA v A mB v B
nA DABmA mA nA nB
Special Case of Stationary Medium:
v 0 N A J A
v 0 nA j A
Achieved to a good approximation for x A (or mA ) = 1 and N B (or nB ) 0.

Conservation of Species

Conservation of Species
Application to a Control Volume at an Instant of Time:
g

M A,in M A,out M A, g
g

g
dM A
M A,st
dt

M A,in , M A,out rate of transport across the control surfaces

g

M A, g rate of generation of A due to homogeneous chemical reactions

occurring in the control volume
g
M A, st rate of accumulation of A in the control volume
Application in Cartesian Coordinates to a Differential Control Volume for a
Stationary Medium of Constant DAB and C or :
Species Diffusion Equation on a Molar Basis:
g

CA CA CA N A
1 C A

x 2
y 2
z 2 DAB DAB t
2

Species Diffusion Equation on a Mass Basis:

2 A 2 A 2 A ng A
1 A

x 2
y 2
z 2 DAB DAB t

Conservation of Species (cont)

Boundary Conditions (Molar Basis):

Consider a Gas (A) / Liquid (B) or
Gas (A) / Solid (B) Interface.
Known surface concentration:
x A 0 x A, s
For weakly soluble conditions of a gas A in liquid B,
p
x A, s A
(Henrys law)
H
H Henry's constant (Table A.9)
For gas A in a uniform solid B,
C A 0 Sp A

S solubility kmol/m3 bar (Table A.10)

Heterogeneous (surface) reactions (Catalysis)

g
dx
N A 0 N A CDAB A
dx x 0

Special Cases

Special Cases for One-Dimensional , Steady-State Diffusion

in a Stationary Medium
Diffusion without Homogeneous Chemical Reactions
For Cartesian coordinates, the molar form of the species diffusion equation is
d 2 xA
0
dx 2

(1)

Plane wall with known surface concentrations:

x A x x A, s ,2 x A,s ,1 x x A, s ,1
L
dx A DAB C A,s ,1 C A,s ,2

N A, x J A, x CDAB

dx
L
N A, x AN A, x
Rm ,diff

DAB A
C A,s ,1 C A,s ,2
L

L
DAB A

Results for cylindrical and spherical shells

Table 14.1

Special Cases (cont)

Planar medium with a first-order catalytic surface:

Assuming depletion of species A at the catalytic surface (x = 0),

g

N A, x 0 N A k1 C A 0
Reaction rate constant (m/s)
DAB

dx A
dx

x 0

k1 x A 0

Special Cases (cont)

Assuming knowledge of the concentration at a distance x=L from the surface,

x A L x A, L
Solution to the species diffusion equation (1) yields a linear distribution for x A x :

x A x 1 xk1 / DAB

x A, L
1 Lk1 / DAB

Hence, at the surface,

xA 0
1

x A, L
1 Lk1 / DAB

dx
N A 0 CDAB A
dx

x 0

Limiting Cases:
Process is reaction limited:
k1 0
xA 0
1
xA L

k1Cx A, L

1 Lk1 / DAB

Lk / D = 1
1

AB

N A 0 k1Cx A, L

Special Cases (cont)

Process is diffusion limited:

xA 0 0

k1

Equimolar counterdiffusion:

Lk / D ? 1
1

AB

CDAB x A, L
N A 0
L

Occurs in an ideal gas mixture if p and T, and hence C, are uniform.

N A, x N B, x
N A, x DAB

C A,0 C A, L DAB p A,0 p A, L

L
T
L

Special Cases (cont)

Diffusion with Homogeneous Chemical Reactions

For Cartesian coordinates, the molar form of the species diffusion equation is
g
d 2C A
DAB
NA 0
dx 2
For a first-order reaction that results in consumption of species A,
g

N A k1C A
and the general solution to the diffusion equation is
C A x C1e mx C2e mx

m k1 / DAB

1/ 2

Consider diffusion and homogeneous reaction of gas A in a liquid (B) container

with an impermeable bottom:

Special Cases (cont)

Boundary conditions
C A 0 C A ,0
Solution

dC A
dx

0
x L

C A x C A,0 cosh mx tanh ml sinh mx

N A, x 0 DABC A,0 m tanh ml

Column Evaporation

Evaporation in a Column: A Nonstationary Medium

Special Features:
Evaporation of A from the liquid interface x A,0 x A,sat ( v ) x A, L
Insolubility of species B in the liquid. Hence downward motion by diffusion
must be balanced by upward bulk motion (advection) such that the absolute
flux is everywhere zero.
N B, x 0
Upward transport of A by diffusion is therefore augmented by advection.

Column Evaporation (cont)

Solution:
1 x A 1 x A, L

1 A,0 1 x A,0
N A, x

x/L

CDAB 1 x A, L
1n

L
1

x
A,0

Transient Diffusion

One-Dimensional, Transient Diffusion in a Stationary Medium

without Homogeneous Chemical Reactions
Species Diffusion Equation in Cartesian coordinates
2C A C A
DAB

x 2
t
Initial and Boundary Conditions for a Plane Wall with Symmetrical Surface Conditions
C A x, 0 C A,i
C A L, t C A, s
C A
x

0
x 0

Nondimensionalization
C C A, s
A
C A ,i C A , s
x x
L

tm

DABt
Fom
L2

Mass transfer Fourier number

Transient Diffusion (cont)

Species Diffusion Equation

2

x2 Fom
Initial and Boundary Conditions

x , 0 1

1, Fom 0

x

x 0

Analogous to transient heat transfer by conduction in a plane wall with symmetrical

surface conditions for which Bi , and hence Ts T .
Hence, the corresponding one-term approximate solution for conduction may be
applied to the diffusion problem by making the substitutions

Fo Fom
Table 14.2 summarizes analogy between heat and mass transfer variables.