1/23/2019

Diffusion
Asra Nafees

Steady State Molecular Diffusion through a constant

area in Binary Gas Mixture

• flux equation cannot be used directly

• flux equation expresses flux in terms of concentration
gradient
• concentration gradient is not an easily measurable
quantity
• concentration can be measured rather.

1
 1/23/2019

Binary Mixture of A & B

Assumptions:

• Area through which diffusion occurs is constant

• The gas mixture is ideal
• Temperature is uniform
• Diffusion occurs at steady state(variables &
parameters do not change with time)

 through a constant area the flux does not change with

position in steady state
 through a variable area the flux changes with position
even when the system is at steady state

2
 1/23/2019

Diffusion of A through non Diffusing B:

Stagnant diffusion (Mass transfer through a stationary second

component):

In gas absorption a soluble gas A is transferred to the liquid surface

where it
dissolves, whereas the insoluble gas B undergoes no net movement
with respect to the interface. The mass transfer process therefore:
N A = P A /P ( NA + NB) - D AB / RT dPA/ dz
Since stagnant diffusion layer: NB = 0

Since diffusion is through constant area at steady state therefore NA = constant

Diffusion occurs from a point z= 0 ( partial pressure of A is pA = PA0) to the point z= l (PA =
P AL)

Since total pressure in the medium is uniform

3
 1/23/2019

Rearranging,

where,

Considering diffusion of A from point z=0 to any point z=z where the partial
pressure of A is pA

4
1/23/2019

5
 1/23/2019

Example 2.4

6
1/23/2019

7
 1/23/2019

• Equimolar Counter Diffusion:

When the mass transfer rates of the two components are

equal and opposite the process is said to be
equimolecular counter diffusion

• If the distillation column is perfectly insulated against

the heat loss then amount of vaporization is equal to
amount of condensation and at the interface, and
consequently throughout the liquid and vapor phases,
equimolecular counter diffusion is taking place (NB =
- NA)
• NA + NB = 0

8
 1/23/2019

Non-equimolar Counter Diffusion of A & B

• Examples where the molecules of A & B diffuses at

different molar rates

• O2 diffuses through a gas film to reach the surface of

the hot char particle and the product is carbon mono
oxide

• For each mole of O2 diffusing towards the particle, two

moles f CO diffuse in the opposite direction.

• Therefore NA = - NB/2

9
 1/23/2019

• Molecular Diffusion in liquids:

• Diffusion in liquids is very slow being about ten
thousand times slower than diffusion in gases
• Example:
• the diffusivity of ammonia in air at 0°C and 1 atm
is 1.98 # 10-5 m2/s while its diffusivity in water at
5°C and solute concentration of 3.5 kmol/m3 is
only 1.24 􀀀 10-9 m2/s

Flux Equation:

• NA = (NA + NB) CA/C – DAB dCA/dz

10
 1/23/2019

• flux equation is similar for both liquids and gases

• the total molar concentration varies from one point to
another

For diffusion of A through non diffusing B

For equimolar counter diffusion of A & B

Estimation of rate of diffusion of a liquid through a

stagnant layer of another liquid):
Example:
Calculate the rate of diffusion of trichloroacetic acid
across nondiffusing methanol solution 2mm thick at
20°C when the concentrations of the acid on the two
opposite sides of the methanol film are 6% and 2% by
weight of acid. The densities of 6% and 2% acid
solutions are 1012 kg/m3 and 1003 kg/m3 respectively.
The diffusivity at infinite dilution of trichloroacetic acid
in methanol at 20°C is 1.862 * 10-9 m2/s

11
 1/23/2019

T = 293 K, z = 2 mm = 0.002 m, DAB = 1.862 # 10-9 m2/s,

MA = 163.5, MB = 32, Density of 6% acid = 1012 kg/m3,

Density of 2% acid = 1003 kg/m3

For 6% acid, xA1 = = 0.01234 mol fraction.
xB1 = (1 - 0.01234) = 0.9876 mol fraction.

For 2% acid, xA2 = = 0.00397 mol fraction.

xB2 = (1 - 0.00397) = 0.9960 mol fraction.

xBM = = 0.9918

For 6% acid, M = 33.62 kg/kmol,

= = 30.10 kmol/m3
For 2% acid, M = 32.57 kg/kmol,
ρ /M= 30.79 kmol/m3
( ρ /M)av = 30.445 kmol/m3
where, M represents the molecular weight of the mixture.

Substituting the values

NA = 1.862 * 10-9 /0.002 * 0.9918
(30.445) *(0.01234 - 0.00397)
= 2.392 # 10-7
The rate of diffusion of trichloroacetic acid = 2.392 *10-7 kmol/ s$m2

Diffusion in Solids

• Diffusion in drying & adsorption involve diffusion

through solid phase

Classification of diffusion in solids

Structure sensitive diffusion
• porous solids permit flow of fluid through their
interstices and capillaries
Structure insensitive diffusion
• the diffusing substance dissolves in the solid to
form solid solution

12
 1/23/2019

• If diffusivity is independent of concentration and there

is no bulk flow, the rate of diffusion NA of component
A per unit cross section of the solid is given by
• NA = -DA (dCA/dz)
where, DA is the diffusivity of A through the solid and
(dCA/dz) is the concentration gradient of the solute in the
direction of diffusion.
• If DA is constant equation may be integrated for steady-
state diffusion through a flat slab of thickness z to give
NA = -DA (CA1- CA2) /z
where, CA1 and CA2 are the concentrations of the solute
at the two faces of the slab.

• For other solid shapes the rate is given by:

W = NA Sav
DA Sav (CA1 – CA 2)/z

For solid cylinder of inner & outer radius r1 & r2

Sav = 2 π l (r2-r1)/( ln r2/r1) & z = r2- r1

For a spherical shell of inner & outer radius r1 & r2

Sav = 4 π r1 r2 & z = r2-r1

13
 1/23/2019

• If CO2 is diffusing through a rubber or any other

polymer , the diffusivity will be independent of partial
pressures on the surface but rather the concentration
depends on the solubility of CO2 in the polymer.

• Concentration of the solute in the solid can be defined

by:

• CA = Solubility * partial pressure of the gas

Volume at S.T.P
• Flux = DAB (CA1 – CA2)
l

• Example:

CO2 is diffusing through a polyvinyl alcohol membrane

of 200 micron thickness at 700 ̊C & 10 kPa partial
pressure. The pressure of CO2 on the sweep side of
membrane is assumed as zero. The solubility of CO2 in
the PV alcohol membrane is 0.007 m³ STP of 0 ̊ C & 1
atm and the diffusivity of DAB is 5 * 10 ^-10 m ²/s at
70 ̊C. Calculate the steady state flux of CO2.

14
 1/23/2019

• CO2, 1 = S * p CO2
22.414 m³
• CO2, 2 = 0
• l = 200 micron = 2 * 10 ^ -4 m ( 1 micron = 1 * 10 ^ -6)

1 kPa = 0.0098 atm

10 kPa = 10 * 0.0098
= 0.98 atm

• CO2, 1 = 0.007 * 0.98 ( p CO2 in atm)

22.414 m³
= 3.123 * 10 ^ -5
• N CO2 = DAB (CA1 – CA2)
l
N CO 2 = 5 * 10 ^ -10 * (3.123 * 10 ^ -5 – 0)
2 * 10 ^ -4
= 7.81 * 10 ^ -11 kmol CO 2 / m²s

• Example:

(Steady-state diffusion of a gas through a solid wall):

Hydrogen gas at 25°C and 1 atm pressure is diffusing
through an unglazed neoprene rubber wall 12.5 mm
thick. The solubility of hydrogen in the rubber has been
estimated to be 0.053 cm3 (at STP) per cubic centimetre.
The diffusivity of hydrogen through the rubber wall is
1.8 * 10-6 cm2/s.
Estimate the rate of diffusion of hydrogen per square
metre of the wall.

15
 1/23/2019

• Concentration of hydrogen at the inner side of the rubber wall is

CA1 = = 2.37 # 10-3 kmol/m3.

Assuming the resistance to diffusion of hydrogen at the outside surface

of the wall is negligible, the concentration of hydrogen at the outer
surface of the wall is CA2 = 0.

Given: DA = 1.8 * 10 ^ -6 cm2/s = 1.8 * 10 ^ -10 m2/s.

Thickness of the rubber wall, z = 12.5 mm = 1.25 * 10 ^-2 m

NA = D CA1 – CA2/ z
Substituting the values,
NA = D CA1 – CA2/ z
= 3.41 * 10-11 kmol/m2s
= 3.41 * 10-8 mol/m2s
The rate of diffusion of hydrogen per square metre =
3.41 * 2 * 10-8
= 6.82 * 10-8 kg/m2s

Knudsen Diffusion: (Diffusion in porous solids)

• Diffusion of gas molecules in capillaries
• The collision of gas molecules with the pore wall due
to more mean free path than pore diameter is known as
Knudsen Diffusion.

Example
• A long pore with a narrow diameter(2-50 nm) because
molecules frequently collide with the pore wall.

16
 1/23/2019

Rate of Knudsen diffusion now depends on the :

• Molecular velocity
• Diameter of the passage
• Partial pressure gradient / concentration gradient

Example:
transport of particles in the catalyst containing fine
pores

Surface diffusion:

• Transport of adsorbed molecules on the surface in the

presence of concentration gradient
• Molecules adsorbed on the surface remain anchored to the
active sites
• If the active sites remain vacant an adsorbed molecule tends
to migrate to an adjacent empty site if it has sufficient
energy to jump
• This shifting of molecules in surface diffusion is known as
hopping mechanism
• Flux = - Ds dCs/ dz
• Cs = Surface concentration of the adsorbed molecules in
kmol/m²
• Ds = Surface diffusion coefficient in m² /s

17
 1/23/2019

• Expression for Knudsen diffusivity:

DK = (2/3) rp vT
Where ,
rp = radius of the passage or capillary
vT = (8RT/πM) ^ 0.5 average velocities of the molecules
by virtue of their thermal energy
T= temperature in K
M = Molecular weight

• Estimate the Knudsen Diffusivity of ethylene within a

100 A pore of a catalyst at 600 K

• T = 100 A = 10 -6 cm
• M= 28
• R= 82.1 cm³ atm/ K gmol

• 1 atm = 1.013 * 10 ^ 6 g cm/s2

cm2
Dk = 2/3 rp (8 RT/π M) ^ 0.5
Dk = 0.045 cm2/s

18