1

Diffusion Mass Transfer

 General Considerations 2
• Mass transfer refers to mass in transit due to a species concentration gradient
in a mixture.
¾ Must have a mixture of two or more species for mass transfer to occur.
¾ The species concentration gradient is the driving potential for transfer.
¾ Mass transfer by diffusion is analogous to heat transfer by conduction.

• Physical Origins of Diffusion:

¾ Transfer is due to random molecular motion.
¾ 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 3
Molar concentration ( kmol/m ) of species i.
3
Ci :
ρi : Density (kg/m3) of species i.

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

ρi = MiCi
J i* : Molar flux ( kmol/s ⋅ m 2 ) of species i due to diffusion.
¾ Transport of i relative to molar average velocity (v*) of mixture.

N i′′ : Absolute molar flux ( kmol/s ⋅ m 2 ) of species i.

¾ Transport of i relative to a fixed reference frame.
ji : Mass flux ( kg/s ⋅ m ) of species i due to diffusion.
2

¾ Transport of i relative to mass-average velocity (v) of mixture.

ni′′: Absolute mass flux ( kg/s ⋅ m 2 ) of species i.

¾ 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 = ρi / ρ ) .
 Property Relations 4

• Mixture Concentration:
C = ∑ Ci Ci → ∑ xi = 1
i xi = i
C
• Mixture Density:
ρ = ∑ ρi ρi → ∑ mi = 1
mi =
i ρ i

• Mixture of Ideal Gases:

pi
Ci = ℜi Universal ideal gas constant
ℜiT
pi i-gas constant
ρi = Ri
RiT
p = ∑ pi
i

Ci pi
xi = =
C p
 5
Molar and Mass Fluxes of Species A due to Diffusion
in a Binary Mixture of Species A and B
• Molar Flux of Species A:
¾ By definition:
J A∗ = C A ( v A − v∗ )
v∗ = x A v A + xB v B

¾ From Fick’s law (mass transfer analog to Fourier’s law):

J A∗ = −CDAB∇x A
Binary diffusion coefficient or mass diffusivity (m2/s)
• Mass Flux of Species A:
¾ By definition:
jA = ρ A ( vA − v )
v = mA v A + mB v B

¾ From Fick’s law:

j A = − ρ DAB∇mA
 Absolute Molar and Mass Fluxes of Species A 6
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 = J∗A + C A ( x A v A + xB v B )
N ′′A = −CDAB∇x A + x A ( N ′′A + N B′′ )

• Mass Flux of Species A:

n′′A = ρ A v A = jA + ρ A v
n′′A = j A + ρ A ( mA v A + mB v B )
n′′A = − ρ DAB∇mA + mA ( n′′A + n′′B )

• Special Case of Stationary Medium:

¾ v = 0 → N ′′A = J A
∗ ∗

¾ v = 0 → n′′A = j A
¾ Achieved to a good approximation for x A (or mA ) << 1
1 and N B′′ (or n′′B ) ≈ 0.
 Conservation of Species 7

• Application to a Control Volume at an Instant of Time:

&
dM
& & &
M A ,in − M A ,out + M A ,g = A &
=M A ,st
dt
&
M &
,in ,A,in ,M
AM out → rate of transport across the control surfaces
M AA,,out
& A, g → rate of generation of A due to homogeneous chemical reactions
M
M A ,g
occurring in the control volume
& A,st → rate of accumulation of A in the control volume
M
M A ,st

• Application in Cartesian Coordinates to a Differential Control Volume for a

Stationary Medium of Constant DAB and C or ρ :
¾ Species Diffusion Equation on a Molar Basis:

∂ 2CA ∂ 2CA ∂ 2C A N & 1 ∂ CA

+ + + A
=
∂ x2 ∂ y2 ∂ z2 DAB DAB ∂ t
¾ Species Diffusion Equation on a Mass Basis:

∂ 2ρ A ∂ 2ρ A ∂ 2ρ A n& A 1 ∂ ρA
+ + + =
∂x 2
∂y 2
∂z 2
DAB DAB ∂ t
 8
• Boundary Conditions (Molar Basis):
¾ 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 (Henry’s 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)

¾ Heterogeneous (surface) reactions (Catalysis)

& '' − C D d x A
N 'A' , x (0) = N A AB
dx x =0
 9
Special Cases for One-Dimensional , Steady-State Diffusion
in a Stationary Medium
• Diffusion without Homogeneous Chemical Reactions
¾ For Cartesian coordinates, the molar form of the species diffusion equation is
d 2 xA (1)
=0
dx 2

¾ 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
DAB A
N A, x = AN ′′A, x =
L
( C A,s ,1 − C A, s ,2 )

Rm ,diff = L
DAB A
Results for cylindrical and spherical shells Table 14.1
 10
¾ Planar medium with a first-order catalytic surface:

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

& '' = −k '' C (o )

N 'A' , x (0) = N A 1 A
Reaction rate constant (m/s)
dx A
− DAB = − k1′′ x A ( 0 )
dx x =0
 11
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 k1′′Cx A, L
N A′′ ( 0 ) = −CDAB A =−
dx x=0 (
1 + Lk1′′ / DAB )
Limiting Cases:
– Process is reaction limited: – Process is diffusion limited:

k ′′ → 0
1 (
Lk1′′ / DAB <<11 ) k1′′ → ∞ ( Lk ′′ / D ) >>11
1 AB

xA ( 0 ) CDAB x A, L
≈1 N A′′ ( 0 ) ≈ − k1′′Cx A, L xA ( 0 ) ≈ 0 N A′′ ( 0 ) ≈ −
xA ( L ) L
 12
¾ Equimolar counterdiffusion:

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

N ′′A, x = − N B′′, x

C A,0 − C A, L DAB p A,0 − p A, L

N ′′A, x = DAB =
L ℜT L
 13
• Diffusion with Homogeneous Chemical Reactions
For Cartesian coordinates, the molar form of the species diffusion equation is
∂ 2C A &
DAB + NA = 0
∂x 2

For a first-order reaction that results in consumption of species A,

& = −k C
N A 1 A

and the general solution to the diffusion equation is

C A ( x ) = C1e mx + C2e − mx m = ( k1 / DAB )
1/ 2
 14
Consider diffusion and homogeneous reaction of gas A in a liquid (B) container
with an impermeable bottom:

Boundary conditions
dC A
C A ( 0 ) = C A ,0 =0
dx x=L

Solution

C A ( x ) = C A,0 ( cosh mx − tanh ml sinh mx )

N ′′A, x ( 0 ) = DABC A,0 m tanh ml

 15
Evaporation in a Column: A Nonstationary Medium

¾ 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.

 16

¾ Solution:

x/L
1 − x A  1 − x A, L 
= 
1 − A ,0  1 − x A ,0 

CDAB  1 − x A, L 
N ′′A, x = 1n  
L  1 − x A,0 
 17
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
=0
∂x x =0

• Non dimensional form

C − C A, s
γ∗ ≡ A
C A ,i − C A , s
DABt
x∗ ≡ x tm∗ ≡ ≡ Fom
L L2
Mass transfer Fourier number
 18
¾ Species Diffusion Equation
∂ 2γ ∗ ∂γ ∗
=
∂x∗2 ∂Fom

¾ Initial and Boundary Conditions

γ ∗ ( x∗ , 0 ) = 1

γ ∗ (1, Fom ) = 0

∂γ ∗
=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
θ∗ ↔ γ ∗
Fo ↔ Fom

• Table 14.2 summarizes analogy between heat and mass transfer variables.
 19
N ′′A = C A v A = J A∗ + C A v∗ (
J *A = C A v A − v * )

N ′′A = J∗A + C A ( x A v A + xB v B ) v* = x A v A + xB v B

J *A = −CD AB ∇x A

(C A v A + C B v B ) = Cv *
CA
(C A v A + C B v B ) = C A Cv *
C C
x A (C A v A + C B v B ) = C A v *
1442443
N ´´ + N ' '
A B

N ′′A = −CDAB∇x A + x A ( N ′′A + N B′′ )