2.3.

MOLECULAR DIFFUSION IN SOLIDS

 Application :
- Leaching of food
- Drying of timber
- Separation of fluids by membrane

 Classification :
1. Diffusion in solid following Fick’s Law
2. Diffusion in porous solid
2.3.1 Diffusion in solid following Fick’s law

 Not depend on actual solid’s structure

 The fluid is dissolved in solid to form more/less

homogeneus solution

 Diffusion coefficient/diffusivity is not depend on

pressure of gases outside the solid

𝐷𝐴𝐵 𝑑𝑐𝐴 𝐷𝐴𝐵 𝑐𝐴1 −𝑐𝐴2

𝑁𝐴 = − =
𝑑𝑧 𝑧2 − 𝑧1

𝐷𝐴𝐵 ≠ 𝐷𝐵𝐴
 For the case of diffusion radially through a
cylinder wall with inner radius 𝑟1 and outer 𝑟2
and length L 𝑁 𝑑𝑐
𝐴 𝐴
= −𝐷𝐴𝐵
2𝜋𝑟𝐿 𝑑𝑟
2𝜋𝐿
𝑁𝐴 = 𝐷𝐴𝐵 𝑐𝐴1 − 𝑐𝐴2
𝑙𝑛 𝑟2 𝑟1

 To convert solubility,(S)into concentration, 𝑐𝐴

𝑚3 𝑆𝑇𝑃
𝑆 3 . 𝑎𝑡𝑚 𝑆𝑝𝐴 𝑘𝑔 𝑚𝑜𝑙 𝐴
𝑐𝐴 = 𝑚 𝑠𝑜𝑙𝑖𝑑 𝑝𝐴 𝑎𝑡𝑚 =
3
22.414 𝑚 (𝑆𝑇𝑃)/𝑘𝑔𝑚𝑜𝑙𝐴 22.414 𝑚3 𝑠𝑜𝑙𝑖𝑑
In the case where permeability 𝑃𝑀 is known
(instead of solubility or concentration):
𝐷𝐴𝐵 𝑆 𝑝𝐴1 − 𝑝𝐴2 𝑃𝑀 (𝑝𝐴1 − 𝑝𝐴2 )
𝑁𝐴 = = 𝑘𝑔𝑚𝑜𝑙 𝑠. 𝑚2
22.414 (𝑧2 − 𝑧1 ) 22.414 (𝑧2 − 𝑧1 )

𝑚3 𝑆𝑇𝑃
Where: 𝑃𝑀 = 𝐷𝐴𝐵 𝑆
𝑠. 𝑚2 𝐶. 𝑆. 𝑎𝑡𝑚 𝑚

Ex: Diffusion through polyethene

film for packaging of
pharmaceutical product
2.3.2 Diffusion in porous solids that depend on
structure
i. Diffusion of liquids in porous solid
 Porous solids that have pores/interconnected voids

 For dilute solution at steady state, the void fill with liquid:
𝜀 𝐷𝐴𝐵 𝑐𝐴1 − 𝑐𝐴2
𝑁𝐴 =
𝜏 𝑧2 − 𝑧1
 For inert-type of solid
𝜏 = 1.5 𝑡𝑜 5 𝜀
𝐷𝐴 𝑒𝑓𝑓 = 𝐷𝐴𝐵 𝑚2 𝑠
𝜏
https://www.youtube.com/watch?v=zqKotT2zUpM
EXAMPLE 2.3.1 (TREYBAL, ILLUSTRATION 4.3)

Calculate the rate of diffusion of carbon dioxide,

𝐶𝑂2 , through a membrane of vulcanized rubber 1
mm thick at 250 𝐶 if the partial pressure of 𝐶𝑂2 is
1 cmHg on one side and zero on the other.
Calculate also the permeability of the membrane
for 𝐶𝑂2 . At 250 𝐶, the solubility coefficient is 0.9
𝑐𝑚3 gas (STP)/𝑐𝑚3 atm. The diffusivity is 1.1 x
−10 𝑚2
10 𝑠.
ii. Diffusion of gas in porous solid
- The void fill with gas

- When diffusion occurs only by Fickian-types

of diffusion:
𝜀𝐷𝐴𝐵 𝑐𝐴1 − 𝑐𝐴2 𝜀𝐷𝐴𝐵 𝑝𝐴1 − 𝑝𝐴2
𝑁𝐴 = =
𝜏 𝑧2 − 𝑧1 𝜏 𝑅𝑇 𝑧2 − 𝑧1
EXAMPLE 2.3.2

A sintered solid of silica 3.0 mm thick is porous

with a void fraction 𝜀 of 0.4 and a tourtosity Ƭ of
0.5. The pores are filled with water at 298 K. At
one face the concentration of KCI is held at 0.20
g mol/liter, and fresh water flows rapidly past the
other face. Neglecting any other resistance but
that in the porous solid, calculate the diffusion of
KCI at steady state.
PROBLEM 6.5-3 (PAGE 456)

The gas hydrogen is diffusing through a sheet of

vulcanized rubber 20 mm thick at 25 C. The
partial pressure of hydrogen is 1.5 atm inside
and 0 at outside. Using data from table 6.5-1.
Calculate :
a. Diffusivity from the permeability and solubility

b. The flux at steady state.

 2.4. INTRODUCTION TO CONVECTIVE MASS
TRANSFER
 More rapid mass transfer

 The fluid need to be flowing by another immiscible

fluid or solid surface

 Exampe: Fluid is flowing in a pipe with wall made of

benzoic acid.

 Concentration profile in turbulence mass transfer from

a surface to a fluid
2.5 TYPE OF MASS TRANSFER COEFFICIENT
 General equation for turbulent mass transfer
with constant c:
∗ 𝑑𝑐𝐴
𝐽 𝐴 = − 𝐷𝐴𝐵 + 𝜀𝑀
𝑑𝑧
 After integrating with point 1 and 2
𝐷𝐴𝐵 + 𝜀𝑀
𝐽 ∗𝐴1 = 𝑐𝐴1 − 𝑐𝐴2
𝑧2 − 𝑧1
 Distance is not known and the cross sectional
area is vary, hence: 𝐽 ∗𝐴1 =𝑘′𝑐 𝑐𝐴1 − 𝑐𝐴2
𝐷𝐴𝐵 + 𝜀𝑀
 Where: 𝑘′𝑐 =
𝑧2 − 𝑧1
2.5.1. Mass transfer coefficient for equimolar
counterdiffusion
𝑁𝐴 = −𝑁𝐵
Hence : 𝑁𝐴 = 𝑘′𝑐 𝑐𝐴1 − 𝑐𝐴2

 For gas :
𝑵𝑨 = 𝒌′𝒄 𝒄𝑨𝟏 − 𝒄𝑨𝟐 = 𝒌′𝑮 𝒑𝑨𝟏 − 𝒑𝑨𝟐 = 𝒌′𝒚 𝒚𝑨𝟏 − 𝒚𝑨𝟐
 For liquid :
𝑵𝑨 = 𝒌′𝒄 𝒄𝑨𝟏 − 𝒄𝑨𝟐 = 𝒌′𝑳 𝒄𝑨𝟏 − 𝒄𝑨𝟐 = 𝒌′𝒙 𝒙𝑨𝟏 − 𝒙𝑨𝟐
𝑘′𝑦
Where : 𝑘′𝑐 =
𝑐
2.5.2. Mass transfer coefficient for A diffusing through
stagnant, nondiffusing B

𝑁𝐵 = 0
𝑘′𝑐
𝑁𝐴 = 𝑐𝐴1 − 𝑐𝐴2 = 𝑘𝑐 𝑐𝐴1 − 𝑐𝐴2 y
𝑥𝐵𝑀
𝑥𝐵2 − 𝑥𝐵1 𝑦𝐵2 − 𝑦𝐵1
Where: 𝑥𝐵𝑀 = 𝑦𝐵𝑀 = 𝑥
𝑙𝑛 𝑥𝐵2 𝑥𝐵1 ln( 𝐵2 𝑥𝐵1 )
 Gases: 𝑵𝑨 = 𝒌𝒄 𝒄𝑨𝟏 − 𝒄𝑨𝟐 = 𝒌𝑮 𝒑𝑨𝟏 − 𝒑𝑨𝟐 = 𝒌𝒚 𝒚𝑨𝟏 − 𝒚𝑨𝟐

 Liquid:𝑵𝑨 = 𝒌𝒄 𝒄𝑨𝟏 − 𝒄𝑨𝟐 = 𝒌𝑳 𝒄𝑨𝟏 − 𝒄𝑨𝟐 = 𝒌𝒙 𝒙𝑨𝟏 − 𝒙𝑨𝟐

𝑘′𝑐 𝑘𝑥
Where : =
𝑥𝐵𝑀 𝑐
7.2-1
A large volume of pure gas B at 2 atm pressure is
flowing over a surface from which pure A is
vaporizing. The liquid A completely wets the
surface, which is blotting paper. Hence, the
partial pressure of A at the surface is the vapour
pressure of A at 298 K, which is 0.2 atm. The
𝑘 ′ 𝑦 has been estimated to be 6.78 x
10−5 𝑘𝑔 𝑚𝑜𝑙 𝑠.𝑚2.𝑚𝑜𝑙.𝑓𝑟𝑎𝑐. Calculate 𝑁𝐴 , the
vaporization rate, and also the value of 𝑘𝑦 and 𝑘𝐺
EXAMPLE 2.5.1
A large volume of pure gas B at 2 atm pressure is
flowing over a surface from which pure A is
vaporizing. The liquid A completely wets the
surface, which is blotting paper. Hence, the
partial pressure of A at the surface is the vapour
pressure of A at 293 K, which is 0.1 atm. The
𝑘′𝑦 has been estimated to be 6.78 x
10−5 𝑘𝑔 𝑚𝑜𝑙 𝑠.𝑚2.𝑚𝑜𝑙.𝑓𝑟𝑎𝑐. Calculate 𝑁𝐴 , the
vaporization rate, and also the value of 𝑘𝑦 and 𝑘𝐺
2.5.3. Mass transfer coefficients for general case
of A and B diffusing and convective flow using
film theory
 Mass transfer occurs through a thin film next to the
wall of thickness 𝛿𝑓 and by molecular diffusion
𝐷𝐴𝐵
′
𝑘𝑐=
𝛿𝑓
𝑁𝐴
𝑁𝐴 (𝑁𝐴 +𝑁𝐵 )− 𝑥𝐴2
 𝑁𝐴 = 𝑘 ′ 𝑐. 𝐶 𝑙𝑛 𝑁𝐴
𝑁𝐴 +𝑁𝐵 (𝑁𝐴 +𝑁𝐵 )− 𝑥𝐴1

 For 𝑁𝐵 = 0

𝑘′𝑐
𝑁𝐴 = 𝑐𝐴1 − 𝑐𝐴2 = 𝑘𝑐 𝑐𝐴1 − 𝑐𝐴2
𝑥𝐵𝑀
2.5.4. Mass transfer coefficients under high flux
conditions
 Affected by high fluxes and diffusion-induced
convection
 For A diffusing through stagnant, non diffusing
B:
𝑘 0 𝑐. 𝑐 (𝑥𝐴1 − 𝑥𝐴2 )
𝑁𝐴 =
1 − 𝑥𝐴1
𝑘 0 𝑐 = (1 − 𝑥𝐴1 )𝑘𝑐
 For 𝑁𝐵 = 0
𝑘′𝑐
 𝑁𝐴 = 𝑐𝐴1 − 𝑐𝐴2 = 𝑘𝑐 𝑐𝐴1 − 𝑐𝐴2
𝑥𝐵𝑀

𝑘𝑐 1 𝑘𝑥
 For Film theory, = =
𝑘′𝑐 𝑥𝐵𝑀 𝑘′𝑥

𝑘0𝑐 1 − 𝑥𝐴1 𝑘0𝑥

Hence = =
𝑘′𝑐 𝑥𝐵𝑀 𝑘′𝑥
EXAMPLE 2.5.2
Toluene A is evaporating from wetted porous slab
by having inert pure air at 1 atm flowing parallel
to the flat surface. At certain point the mass
transfer coefficient k’x for very low fluxes has
been estimated as 0.5 lb mol/hr. 𝑓𝑡 2 . The gas
composition at the interface at this point is 𝑥𝐴1 =
𝑘𝑐
0.75. Calculate the flux NA and the ratios ′ and
𝑘 𝑐
𝑘0𝑐
to correct for high flux
𝑘′𝑐
REFERENCES

1. Geankoplis, C.J. (2014). Transport Processes

and Separation Process Principle, 4th Edition.
New York: Prentice Hall

2. Treybal, E. (1990). Mass Transfer Operations,

4th Edition. New York: McGraw-Hill