DIFFUSION

CHEMICAL ENGINEERING REVIEW

Engr. Ronnie V. Flores

CHEMICAL ENGINEERING SERIES: DIFFUSION

PRINCIPLES OF DIFFUSION
MASS TRANSFER

Is the net movement of a component in a mixture from one location to another location
where the component exists at a different concentration
The transfer takes place between the two phases across an interface
Mass transfer occurs by two basic mechanisms: (1) molecular diffusion and (2) eddy
diffusion

MOLECULAR DIFFUSION

Transfer or movement of individual molecules through a fluid by means of the random,

individual movements of the molecules
In a binary mixture, molecular diffusion occurs because of one or more different potentials or
driving forces
1. Concentration gradient (ORDINARY DIFFFUSION)
2. Pressure gradient (PRESSURE DIFFUSION)
3. Temperature (THERMAL DIFFUSION)
4. External force fields (FORCED DIFFUSION) as in centrifuge
5. Activity gradient as in reverse osmosis
Molecular diffusion occurs in solids and in fluids that are stagnant or in laminar or turbulent
motion

EDDY (TURBULENT) DIFFUSION

Takes place in fluid phases by physical mixing and by the eddies of turbulent flow

FICKS LAW OF DIFFUSION AT STEADY STATE

Ficks Law of Diffusion

Gives the rate of mass transfer by molecular diffusion perpendicular to an relative to a

stationary surface which is at fixed distance from the interface

Ficks First Law of Molecular Diffusion is proportionality between a flux and a gradient. For a
binary mixture of A and B

=
=

ENGR. RONNIE V. FLORES

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CHEMICAL ENGINEERING SERIES: DIFFUSION

and

where:

is the molar flux of A by ordinary molecular

diffusion relative to the molar average velocity
of the mixture in the positive z direction
mutual diffusion coefficient of A and B
concentration gradient of A, which is negative in
the direction of ordinary molecular diffusion
moles of A diffusing per unit time
cross sectional area
concentration of A
distance of diffusion

Ficks Law of diffusion is based on the following observations:

1. Mass transfer by ordinary molecular diffusion occurs because of a concentration difference
or gradient; that is, a species diffuses in the direction of decreasing concentration
2. The mass transfer rate is proportional to the area normal to the direction of mass transfer
and not to the volume of the mixture. Thus, the rate can be expressed as a flux
3. Mass transfer stops when the concentration is uniform
PREDICTION OF DIFFUSIVITY
For Gases:
1. Chapman and Enskog Equation
1.8583 107 3/2 1
1 1/2
=
(
+
)
2 ,

Where:
diffusivity, m2/s
- temperature, K
absolute pressure, atm
, - molecular weights of A and B, in kg/kmol
- average collision diameter,
, - collision integral based on the Lennard-Jones potential
and , can be obtained from Appendix 19 (Unit Operations, by McCabe and Smith)

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CHEMICAL ENGINEERING SERIES: DIFFUSION

2. Fuller Method (Geankoplis)

=

1 107 1.75
1
1 1/2
(
+
)
[( )1/3 + ( )1/3 ]2

Where:
- sum of structural volume increments (table 6.2-2, Geankoplis)
3. Schmidt Number
=

For liquids:
1. Stokes-Einstein Equation
=

7.32 1016

Where:
- diffusivity, cm2/s
- absolute temperature, K
- molecular radius, cm
- viscosity, cP
2. Wilke-Chang Equation
= 7.4 108

( )1/2
0.6

Where:
- molar volume of solute as liquid at its normal boiling point, cm3/mol
- association parameter for solvent (water = 2.6; methanol = 1.9; ethanol = 1.5;
benzene = 1.0; heptanes = 1.0)
3. Nernst Equation (for dilute solutions of completely ionized univalent electrolytes
2
=
1
1
( 0 + 0 ) 2
+
Where:
- Faraday constant, 96,500 coul/gequiv
- gas constant, 8.314 J/Kgmol
0+ , 0 - limiting (zero concentration) ionic conductances, A/cm2(V/cm)(gequiv/cm3),
Table 17.1 Unit Operations by McCabe and Smith

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CHEMICAL ENGINEERING SERIES: DIFFUSION

MOLECULAR DIFFUSION IN GASES

1. EQUIMOLAR COUNTER-DIFFUSION

=
=

Where:
- diffusion flux relative to the moving fluid
2. GENERAL CASE FOR DIFFUSION OF GASES A AND B PLUS CONVECTION
In terms of velocity of diffusion of A to the right
=
If the whole fluid is moving in bulk or convective to the right
= +
= +
= +

Let = total convective flux of the whole stream, relative to the stationary point, then
= = +
=

= +

( + )

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CHEMICAL ENGINEERING SERIES: DIFFUSION

( + )
+

For equimolar counter-diffusion,

=
=

=
=

3. SPECIAL CASE FOR A DIFFUSING THROUGH STAGNANT, NON-DIFFUSING B

In this case,
= 0
=
(1

) =

(
) =

[
]=

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CHEMICAL ENGINEERING SERIES: DIFFUSION

(
)=

=
(
)

MOLECULAR DIFFUSION IN LIQUIDS

4. EQUIMOLAR COUNTER-DIFFUSION
=

1 1 2
= ( ) = ( + )

2 1 2
Where:
- average total concentration of liquids A and B, mol/vol
- mol fraction of A

5. DIFFUSION OF A THROUGH A NON-DIFFUSING B

=

( + )
+

= 0
=

=
+

(1 +

) =

=
=
(1 + ) =

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CHEMICAL ENGINEERING SERIES: DIFFUSION

2

=
1

(2 1 ) = ln
=

1 +

1 + 2
1 + 1

1 + 2
=
ln
(2 1 ) 1 + 1

(1 1 ) (2 2 )

ln 1 1
2
2

For dilute solution,

=

(0 1 ) (0 2 )
0
ln 0 1
2

2 1

ln 2
1

ln

2
2 1
=
1

1 + 2
=
ln
(2 1 ) 1 + 1

2
=
ln
(2 1 ) 1

2 1
=
(
)
(2 1 )

For dilute solutions,

= 1
=

( 1 )
=
(2 1 ) 2

( 1 )
=
(2 1 ) 2

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CHEMICAL ENGINEERING SERIES: DIFFUSION

(2 1 )
(2 1 )

=
=
(2 1 )
(2 1 )

MOLECULAR DIFFUSION IN SOLIDS

=

6. DIFFUSION EQUATIONS USING GAS SOLUBILITY IN A SOLID SURFACE

=

Where: is the molar volume of gas at STP, 22.4 m3/kmol; solubility of solute
gas in a solid

7. DIFFUSION IN SOLIDS USING PERMEABILITY EQUATIONS

=
Where: - solute gas permeability, or the volume of solute gas at STP diffusing per
second per unit cross sectional area through a solid under a pressure difference of 1
atm pressure

8. DIFFUSION IN POROUS SOLIDS THAT DEPENDS ON STRUCTURE

(1 2 )
=

(2 1 )

Where: - open void fraction; tortousity (factor that corrects for

the path longer than the (2 1 )

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CHEMICAL ENGINEERING SERIES: DIFFUSION

MASS TRANSFER COEFFICIENTS

MASS TRANSFER COEFFICIENT
It is defined as the rate of mass transfer per unit area per unit concentration difference
and is usually based on equal molal flows

=

=

( )
1

= [
](
)=
2 1

Sherwood Number
Reynolds Number
Graetz Number
Schmidt Number
Peclet Number

=
=

MASS TRANSFER WITH FLOW INSIDE PIPES

-

Prediction of the internal mass-transfer resistance for separation processes using

hollow-fiber membranes
= 1.621/3

For turbulent flow mass transfer to pipe walls

0.14
= 0.023 0.8 1/3 (
)

FLOW NORMAL TO CYLINDERS

= 0.61 1/2 1/3

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CHEMICAL ENGINEERING SERIES: DIFFUSION

FLOW NORMAL TO TUBE BUNDLE

= 1.28 0.4 0.33

FLOW PAST SINGLE SPHERES

-

For Re up to 1,000 (using modified Frssling equation)

= 2.0 + 0.6 1/2 1/3

For low reynolds number and high Peclet number

1/2

= (4.0 + 1.21 2/3 )

MASS TRANSFER IN PACKED BEDS

= 1.17 0.585 1/3

MASS TRANSFER TO DROPS AND BUBBLES

= 1.13 1/2 1/2

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