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lecture 4

The document discusses molecular diffusion in solids, emphasizing its slow rate and importance in various processes such as leaching, drying, and catalytic reactions. It outlines diffusion mechanisms, including Fick's law and diffusion in porous solids, providing equations for different geometries like slabs, cylinders, and spheres. Additionally, it relates concentration to solubility and permeability, with examples illustrating calculations for gas diffusion through membranes and porous materials.

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0% found this document useful (0 votes)
2 views15 pages

lecture 4

The document discusses molecular diffusion in solids, emphasizing its slow rate and importance in various processes such as leaching, drying, and catalytic reactions. It outlines diffusion mechanisms, including Fick's law and diffusion in porous solids, providing equations for different geometries like slabs, cylinders, and spheres. Additionally, it relates concentration to solubility and permeability, with examples illustrating calculations for gas diffusion through membranes and porous materials.

Uploaded by

tanyesabe8005
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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MOLECULAR DIFFUSION

IN SOLIDS
 Diffusion in solids are occurring at a very slow rate.
Mass transfer in solids are very important
especially in chemical and biological processing.

 Examples:
 Leaching of metal ores
 Drying of timber, and foods
 Diffusion and catalytic reaction in solid catalysts
 Separation of fluids by membranes
 Treatment of metal at high temperature by gases.
 Diffusion in solids occur in two different ways:

 Diffusion following Fick’s law (does not depend


on the structure of the solid)

 Diffusion in porous solids where the actual


structure and void channels are important
1. Diffusion in solids following Fick’s Law

NA = -cDAB dxA cA (NA + NB)


+
dz c
Bulk term is set to zero in solids

Therefore, the following equation will be used to describe the process:

dCA
NA = -DAB
dz

Note: DAB does not equal to DBA in solids!


Case 1: Diffusion through a slab
Integrate the equation for steady-state diffusion through a solid slab

DAB (CA1 - CA2)


NA =
z2 - z1

where NA and DAB are taken as constants.

CA1

CA2
z2-z1
Case 2: Diffusion through a cylinder wall
For steady-state diffusion through a cylinder wall of inner radius r1 and outer radius r2
and length L in the radial direction outward, we get

Mass transfer per Mass transfer per time


area per time
nA dCA
NA = = -DAB
2πrL dr

Area of mass transfer


CA2
CA1
r
2πL DAB(CA1 - CA2)
NA = r2 r1
ln(r2 / r1)
Case 3: Diffusion through a spherical shell
For steady-state diffusion through a spherical shell of inner radius r1 and outer radius
r2 in the radial direction outward, we get

Mass transfer per Mass transfer per time


area per time
nA dCA
NA = = -DAB
4 π r2 dr

Area of mass transfer

4πr1r2 DAB(CA1 - CA2)


NA = CA2
CA1
(r2 - r1) r
r2 r1
Relating the concentration and solubility
The solubility of a solute gas in a solid is usually expressed by the notation S.

Unit used in general is the following:

m3 solute at STP
m3 solid . atm partial pressure of solute

Relationship between concentration and solubility:

S pA
CA = kmol solute /m3 solid where pA is in atm
22.414

D AB S ( p A1 − p A 2 )
NA = kgmol / s.m 2
22 .414 ( z 2 − z1 ) STP of 0oC and 1 atm
Example 8

Diffusion of H2 through Neoprene membrane:


The gas hydrogen at 17oC and 0.010 atm partial pressure is
diffusing through a membrane on vulcanized neoprene
rubber 0.5 mm thick. The pressure of H2 on the other side
of neoprene is zero. Calculate the steady-state flux,
assuming that the only resistance to diffusion is in the
membrane. The solubility S of H2 gas in neoprene at 17oC is
0.051 m3 (at STP of 0oC and 1 atm)/m3 solid. atm and the
diffusivity DAB is 1.03 x 10-10 m2/s at 17oC.

c A1 − c A 2
N A = D AB
S pA1
CA1 = kmol solute /m3 solid
22.414
z 2 − z1
Tutorial (Q6)

A flat plug 30 mm thick having an area of 4.0 x 10-4 m2


and made of vulcanized rubber is used for closing an
opening in a container. The gas CO2 at 25°C and 2.0
atm pressure is inside the container. Calculate the total
leakage or diffusion of CO2 through the plug to the
outside in kg mol CO2/s at steady state. Assume that
the partial pressure of CO2 outside is zero. The
solubility of the CO2 gas is 0.90 m3 gas per m3 rubber
per atm pressure of CO2. The diffusivity is 0.11 x 10-9
m2/s.
Relating the concentration and permeability
The permeability of a solute gas (A) in a solid is usually expressed by the notation
PM. in m3 solute at STP (0oC and 1 atm) diffusing per second per m2 cross-sectional
area through a solid 1 m thick under a pressure difference of 1 atm.

Unit used in general is the following:

m3 solute at STP . 1 m thick solid

s . m2 cross-sectional area . atm pressure difference

Relationship between concentration and permeability:

PM = DAB S where DAB is in m2/s and S is in m3/m3.atm

PM ( p A1 − p A 2 )
NA = kgmol / s.m 2
22 .414 ( z 2 − z1 )
Example 9

Diffusion through a packaging film using permeability:


A polythene film 0.00015 m (0.15 mm) thick is being considered for use
in packaging a pharmaceutical product at 30oC. If the partial pressure
of O2 outside the package is 0.21 atm and inside it is 0.01 atm, calculate
the diffusion flux of O2 at steady state. Assume that the resistances to
diffusion outside the film and inside are negligible compared to the
resistance of the film. Permeability of O2 in polythene at 303 K is 4.17 x
10-12 m3 solute (STP)/(s.m2.atm.m).
Would you prefer nylon to polythene? Permeability of O2 in nylon at
303 K is 0.029 x 10-12 m3 solute (STP)/(s.m2.atm.m). Support your
answer.

PM ( p A1 − p A 2 )
NA = kgmol / s.m 2

22 .414 ( z 2 − z1 )
2. Diffusion in porous solids that depends on
structure
Case 1: Diffusion of liquid in porous solids
For diffusion of salt in water at steady state:

( c A1 − c A 2 )
N A = D AB
NA  ( z 2 − z1 )

ε : open void fraction


DAB: diffusivity of salt in water
 : vary from 1.5 to 5 for inert-type solid

z1 z z2
Example 10

A sintered solid of silica 2.0 mm thick is porous, with


a void fraction of 0.30 and a tortuosity of 4.0. The
pores are filled with water at 298K. At one face, the
concentration of KCl is held at 0.10 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 KCl at steady
state. 3
0.1 kgmol/m 0
0.3 ( c A1 − c A 2 )
N A = D AB
 ( z 2 − z1 ) 2 x 10
-3 m
4.0
Case 2: Diffusion of gases in porous solids

( p A1 − p A 2 )
N A = D AB
NA RT ( z 2 − z1 )

z1 z z2

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