Diffusion Through Solids

Dr. P. A. Joshi
Professor, Department of Chemical Engineering
Faculty of Technology
Dharmsinh Desai University, Nadiad
[email protected]
 Diffusion in Solids
A good number of MTO involve contact of fluid with solids.
The most commonly encountered conventional MTO are
Drying, Leaching, Adsorption, Crystallization and almost all
of the non-conventional membrane operations, such as RO,
Dialysis, Electro-dialysis and Pervaporation. In fluid-solid
non catalytic and catalytic reaction it is very important.
The mechanism of diffusion through solids are highly
complex as compared to the diffusion in fluids and vary for
each one and to a great extent depends on the structure of
the solid. However in some cases Fick’s Law can describe
the operations.

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 Steady State vs. Unsteady State
• Operations involving solids are carried out in
either batch or semi-batch mode
• The reason is lack of fluidity of solids
• Even if continuous operation is carried out,
the diffusion in solid particles is unsteady state
• Under exceptional condition we may assume
the operation to be in steady state

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 Fick’s Law Diffusion
Steady state should prevail, diffusivity should be
independent of concentration and concentration gradient
should be constant to apply Fick’s law. In the absence of
bulk flow (N=NA+NB=0), we have

Where CA1 and CA2 are the concentrations on two sides of

the slab.
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For other solid shapes rate equations are given as

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 Illustration 1
Hydrogen gas at 298 K and 2 atm pressure flows
through a rubber tube having ID 25 mm and OD
50 mm. If the solubility of hydrogen in the
rubber is 5.3X10-2 m3/m3.atm and diffusivity is
1.8X10-10 m2/s calculate the rate of hydrogen loss
per unit length of the tube.

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 Solution

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 Assignment -1
Discuss the applicability of Fick’s law of diffusion
for solids. Calculate the rate of diffusion of
methane through a rubber membrane 1.2 mm
thick at 298 K if the partial pressure of methane
is 0.1atm on one side of the membrane and zero
on the other side. The solubility coefficient is
0.89 cm3 gas (STP)/ cm3 atm and diffusivity is
1.2x10-10 m2/s.

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 Unsteady State Diffusion
Majority of diffusion through solids fall in this category
as the solids lack fluidity and hence the operations
involving solids are in batch or semi batch manner. Even
if continuous operation is carried out the solid particles
exhibit unsteady state diffusion, e.g. continuous dryer
and adsorber.
Where there is no bulk flow and no chemical reaction,
the Fick’s second law can be used with appropriate
boundary conditions. For some simple cases the results
are summarized as
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 Diffusion from a Slab with Sealed Edges
• Slab of thickness 2a and four edges sealed. (Fig. 4.1)
• Diffusion through the two parallel flat sides only on
exposure to a medium.
• Initial concentration through out the slab is CAo
• Ultimate concentration on diffusion for infinite time is
and
gives amount of solute removed
• If diffusion is stopped after time the concentration
profile can be given by curve C and on internal diffusion
level offs to average value
• The quantity gives the solute unremoved
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 Fig.4.1
Unsteady State
Diffusion in slab

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1. The fraction unremoved E can be obtained from Fick’s 2nd
law

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 Fig. 4.2

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 • If only one face, instead of two faces, is exposed then
the length of the diffusional path is doubled and
calculations are made with
• Concentration C may be given as mass solute/volume
or mass solute /mass solid
• It is assumed that diffusivity is constant, initial
concentration in solid is uniformly CAo and the
concentration at the edges is also constant
• The last assumption is true if, there is no resistance to
diffusion in fluid, the quantity of fluid is so large that
there is no change in its concentration and the fluid is
continuously replenished.
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 Illustration-2

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 Assignment-2
A cube with 30 mm sides is impregnated with sugar
with initial concentration of 5.1 gm/100 cm3 and is
exposed to running water. Only one face is made
available for diffusion of sugar and rest of the faces are
sealed. After 63 h, the sugar concentration fell to 2.5
gm/100 cm3. Calculate the diffusivity of sugar and the
time required for the concentration to fall to 1.2
gm/100 cm3. The relation between Ea and Dϴ/a2 is
Dϴ/a2 0.1 0.3 0.5 0.7

Ea 0.65 0.38 0.23 0.14

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 Excersize-1
A 50 mm gel cube containing a uniform boric acid conc. of 50
kg/cu.m. is in a mold with one face open and exposed to running
fresh water stream leading to diffusion of boric acid. If the
diffusivity is 4.7x10*-10 sq.m/s, calculate the time required to
fall the boric acid conc. to 25 kg/cu.m. How long will it take to
bring down the boric acid conc. To 40, 30 and 20 kg/cu.m.? What
will be the conc. of boric acid after 125 h of exposure?
Ans. 280 h
40------44.3 h
30------185 h
20----413 h

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 TYPES OF SOLID DIFFUSION
The structure of the solid and its interaction with the diffusing
substance have a profound influence on how diffusion occurs
and on the rate of transport.
1. Diffusion through Polymers
2. Diffusion through Crystalline Solids
3. Diffusion in Porous Solids
(a) diffusion at constant total pressure
(b) Hydrodynamic flow of gases
In many respects, diffusion of solutes through certain types of
polymeric solids is more like diffusion of solute through liquid
solutions than any of the other solid-diffusion phenomena. This is
true for permanent gases.

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 TYPES OF SOLID DIFFUSION
1. Diffusion
through Polymers
In many respects, diffusion of solutes through certain
types of polymeric solids is more like diffusion through
liquid solutions than any of the other solid-diffusion
phenomena at least for the permanent gases as
solutes.
• Imagine two bodies of a gas (e.g., H2) at different
pressures separated by a polymeric membrane (e.g.,
polyethylene)
• The gas dissolves in the solid at the faces exposed to
the gas to an extent usually describable by Henry's law,
concentration directly proportional to pressure
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• The gas then diffuses from the high to the low-
pressure side in a manner usually described as
activated (the polymeric chains are in a state of
constant thermal motion, and the diffusing
molecules jump from one position to another over
a potential barrier)
• A successful jump requires that a hole or passage
of sufficient size be available and this in turn
depends on the thermal motion of the polymer
chains
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 TYPES OF SOLID DIFFUSION
The term "activated" refers to the temperature dependence of
the diffusivity, which follows an Arrhenius-type expression

where HD is the energy of activation and Do is a constant

• For simple gases, DA is usually reasonably independent of
concentration
• It may, however, be a strong function of pressure of molding
the polymer
• For the permanent gases, diffusivities may be of the order of
10-10 m2/s
• For large molecules, the size and shape of the diffusing
molecules determine the hole size required.
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• Solvents sometimes diffuse by plasticizing the
polymers, and consequently the rate may be very much
higher for good solvents (e.g., benzene or methyl ethyl
ketone in polymeric rubbers) than for the permanent
gases
• Such diffusivities are frequently strongly dependent
upon solute concentration in the solid
• With certain oxygenated polymers, e.g., cellulose
acetate, such solutes as water, ammonia, and alcohols
form hydrogen bonds with the polymer and move from
one set of bonding sites to another
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 TYPES OF SOLID DIFFUSION
• In this case, diffusional characteristics is described in terms
of a quantity P, known as the permeability.
• Since at the two faces of a membrane the equilibrium
solubility of the gas in the polymer is directly proportional to
the pressure, eqn can be written as:

• where VA = diffusional flux, m3 gas (STP) / m2• s

• D A = diffusivity of A, m2/ s
• p A = partial pressure of diffusing gas, N/sq.m.
• SA solubility coefficient or Henry's law constant, m3 gas (STP)/
(m3 solid). N/sq.m/m
• z = thickness of polymeric membrane, m

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 TYPES OF SOLID DIFFUSION
• Permeability is then defined as
P=DA.SA
where P = permeability, m3 gas (STP)/m2 • s .
(N/sq.m./m)
Commercial application:
• Separating hydrogen from waste refinery gases in
shell-and-tube devices which resemble in part the
common heat exchanger
• However, in this use the polymeric-fiber tubes are
only 0.03 mm OD, and there are 50 million of them in
a shell roughly 0.4 m in diameter
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 Illustration-3

p = (l.l X 10 - 6)(0.01184) = 0.13 x 10 -7 cm) (STP)/cm2• s . (cmHg/cm)

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 Assignment-2
Hydrogen is diffusing through a 1.5 mm thick
membrane at 300 K. The partial pressure of
hydrogen on one side of the membrane is 0.066
atm and on the other side there is just air. If the
solubility coefficient of hydrogen in the membrane
material is 0.9 m3/m3.atm and diffusivity is 1.1X10-
10
m2/s calculate the permeability of the membrane
and volumetric rate of diffusion of hydrogen
through the membrane.

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 TYPES OF SOLID DIFFUSION
2. Diffusion through Crystalline Solids
The mechanisms of diffusion vary greatly depending upon the
crystalline structure and the nature of the solute. For crystals
with lattices of cubic symmetry, the diffusivity is isotropic, but
not so for noncubic crystals. Particularly, but not necessarily, in
metals the principal mechanisms are the following
1. Inlerstitial mechanism. Interstitial sites are places between the
atoms of a crystal lattice. Small diffusing solute atoms may pass
from an interstitial site to the next when the matrix atoms of the
crystal lattice move apart temporarily to provide the necessary
space. Carbon diffuses through alfa- and gama-iron in this
manner.
2. Vacancy mechanism. If lattice sites are unoccupied (vacancies),
an atom in an adjacent site may jump into such a vacancy.
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 TYPES OF SOLID DIFFUSION

3. Interstilialcy mechanism. In this case a large atom occupying

an interstitial site pushes one of its lattice neighbors into an
interstitial position and moves into the vacancy thus produced
4. Crowd-ion mechanism. An extra atom in a chain of close-packed
atoms can displace several atoms in the line from their
equilibrium position. Thus producing a diffusion flux.
5. Diffusion along grain boundaries. The diffusivity in a single-
crystal meta) is always substantially smaller than that for a multi
crystalline sample because the latter has diffusion along the
grain boundaries (crystal interfaces) and dislocations.

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 TYPES OF SOLID DIFFUSION
3. Diffusion in Porous Solids
The solid may be in the form of a porous barrier or membrane
separating two bodies of fluid, as in the case of gaseous
diffusion.
• Here the solute movement may be by diffusion from one fluid
body to the other by virtue of a concentration gradient, or it
may be hydrodynamic as a result of a pressure difference.
• Alternatively, in the case of adsorbents, catalyst pellets solids
to be dried, ore particles to be leached, and the like, the solid
is normally completely surrounded by a single body of fluid
and inward and outward movement of solute through the
pores of the solid is solely by diffusion.

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• Diffusive movement may be within the fluid filling the pores
or may also involve surface diffusion of adsorbed solute.
• The pores of the solid may be interconnected (accessible to
fluid from both ends of the pores), dead-end (connected to
the outside of the solid only from one end), or isolated
(inaccessible to external fluid).
• The pores in most solids are neither straight nor of constant
diameter.
• Catalyst particles manufactured by pressing powders
containing micropores into pellets, with macropores
surrounding the powder particles of a different order of
magnitude in size, are said to be bidisperse
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 TYPES OF SOLID DIFFUSION

3(a) Diffusion at constant total pressure

• Imagine the pores of a solid to be all of the same length and
diameter, filled with a binary solution at constant pressure,
with a concentration gradient of the components over the
length of the pores.
• Then within the solution filling the pores, Eq. (2.26) for gases
or Eq. (2.40) for liquids would apply.
• The fluxes NA and NB would be based upon the cross-sectional
area of the pores, and the distance would be the length of the
pores l.

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• The ratio of fluxes NA/(NA + NB) would, as usual depend upon
non-diffusional matters, fixed perhaps because in leaching of
a solute A the solvent B would be non-diffusing, or fixed by
the stoichiometry of a catalyzed reaction on the surface of the
pores.
• Since the length of the various pores and their cross-sectional
area are not constant, it is more practical to base the flux
upon the gross external surface of the membrane, pellet.
• or whatever the nature of the solid, and the length upon
some arbitrary but readily measured distance z such as
membrane thickness, pellet radius, and the like

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 TYPES OF SOLID DIFFUSION
• Since the fluxes will be smaller than the true values based on
true fluid cross section and length, an effective diffusivity
DAB, eff , smaller than the true DAB must be used, ordinarily
determined by experiment
• For the same type of processes in a given solid, presumably
the ratio DAB / DAB, eff, will be constant, and once measured it
can be applied to all solutes. DAB, eff like DAB varies inversely
as Pt and approximately directly as T3/2
• When NB = 0, Eqs. (4.1) to (4.13) would be expected to apply
with DAB, eff replacing DA

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 Illustration-4

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 Illustration-4 Cont…..

(Treybal chapter 4)

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 Excersize-1
Porous alumina spheres of 15mm dia were
impregneted with an aq. Sol. Of KCl containing
250kg/cu.m.of solution. The spheres on immersing in
running pure water at 298 K, lost 75% of KCl in 220
minutes. The diffusivity of KCl is 18.45x10*-10 sq.m/s. If
instead of KCl, the spheres were impregneted with aq.
sol. of K2CrO4 having conc. Of 280 kg/cu.m, what
would be the time required to leach out 75% of K2CrO4
The diffusivity of K2CrO4 = 11.5x10*-10 sq.m/s.
(Ans.5.58hr) How much reduction in solute
concentration would have taken place in 3hrs?
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 TYPES OF SOLID DIFFUSION
• In steady-state diffusion of gases, there are two types of diffusive
movement, depending on the ratio of pore diameter d to the mean
free path of the gas molecules .
• If the ratio d /  is greater than approximately 20, ordinary
molecular diffusion predominates and

• If, however, the pore diameter and the gas pressure are such that
the molecular mean free path is relatively large, d/ less than
about 0.2, the rate of diffusion is governed by the collisions of the
gas molecules with the pore walls and follows Knudsen's law.
• Since molecular collisions are unimportant under these conditions,
each gas diffuses independently
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 TYPES OF SOLID DIFFUSION
• In a straight circular pore of diameter d and length I, Knudsen law
gives,

• where uA is the mean molecular velocity of A. Since the kinetic

theory of gases provides

where DK,A is the Knudsen diffusion coefficient

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 TYPES OF SOLID DIFFUSION
• Since normally d is not constant and the true l is unknown, I is ordinarily
replaced by z, the membrane thickness, and D K,A by D KA, eff the effective
Knudsen diffusivity, which is determined by experiment.
• D KA, eff is independent of pressure and varies as (T /M) 1/2.
• For binary gas mixtures

• In addition, for a given solid, DAB, eff / DKA, eff = DAB / DKA
• The mean free path of A can be estimated from the corelation

• In the range d /  from roughly 0.2 to 20, a transition range, both molecular
and Knudsen diffusion have influence, and the flux is given by
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 Knudsen Diffusion

Conditions under which molecular diffusion prevails (DKA,eff » DAB,eff)

this equation reverts to the general equation for molecular
diffusion in gases
When Knudsen diffusion prevails (DAB,eff >> DKA,eff )
or open-ended pores, eqn

applies throughout the transition range for solids whose pore

diameters are of the order of 10 m or less
Knudsen diffusion is not known in case of liquids
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 Illustration-5

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 Solution

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 Illustration-5 Cont…..
(Treybal chapter 4)

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 TYPES OF SOLID DIFFUSION

Surface diffusion is a phenomenon accompanying adsorption of

solutes onto the surface of the pores of the solid. It is an
activated diffusion [see Eq. (4.14)], involving the jumping of
adsorbed molecules from one adsorption site to another
• It can be described by a two-dimensional analog of Fick's law,
with surface concentration expressed, for example, as mol/area
instead of mol/ volume.
• Surface diffusivities are typically of the order of 10 - 7 to 10 - 9
m2/s at ordinary temperatures for physically adsorbed gases
• For liquid solutions in adsorbent resin particles, surface
diffusivities may be of the order of 10 - 12 m2/s

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 Hydrodynamic Flow in Solids
3 (b) Hydrodynamic flow of gases:
If there is a difference in absolute pressure across a porous solid, a
hydrodynamic flow of gas through the solid will occur.
• Consider a solid consisting of uniform straight capillary tubes of
diameter d and length I reaching from the high- to low-pressure side.
• At ordinary pressures, the flow of gas in the capillaries may be either
laminar or turbulent, depending upon whether the Reynolds number
d u / . is below or above 2100.
• For present purposes, where velocities are small, flow will be laminar.
• For a single gas, this can be described by Poiseuille's law for a
compressible fluid obeying the ideal gas law

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• For a single gas, this can be described by Poiseuille's law for a
compressible fluid obeying the ideal gas law

where + Pt
This assumes that the entire pressure difference is the result of
friction in the pores and ignores entrance and exit losses and
kinetic-energy effects, which is satisfactory for present purposes.

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 TYPES OF SOLID DIFFUSION
Since the pores are neither straight nor of constant diameter,
just as with diffusive flow it is best to base N A on the external
cross section of the solid and rewrite Eq. for N A as

If conditions of pore diameter and pressure occur for which

Knudsen flow prevails (d /  < 0.2), the flow will be described by
Knudsen's law
There will be of course a range of conditions for a transition from
hydrodynamic to Knudsen flow.
If the gas is a mixture with different compositions and different
total pressure on either side of the porous solid, the flow may be
a combination of hydrodynamic, Knudsen, and diffusive
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 Illustration-6

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 Solution

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 Excersize
A gas mixture containing 80% O2 and 20% N2 by volume is
diffusing through a 25mm unglazed porcelain membrane at 1
atm and 293 K. Calculate the molar fluxes of O2 and N2 .
DAB = 20.39x10*-6 sq.m./s and DAB, eff =1.42x10*-6 sq.m./s

DK,AB= 4.2x10*-5 sq.m./s and DK,AB, eff = 2.9x10*-6 sq.m./s at

the given conditions.
Hint: NA/NB= -(MB/MA)*0.5 ; (DAB, eff / DK,AB, eff )= 0.48

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 Assignments-3 & 4
Problem 4.1
Problem 4.2
Mass Transfer Operations-R E Treybal, 3rd Ed.

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 THANK YOU

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