MASS TRANSFER

Assoc. Prof. Dr. Emel AKYOL

2. MOLECULAR DIFFUSION IN GASES
2.1. Special Cases of the General Diffusion Equation at Steady State

5-Unequimolecular counter diffusion:

When the mass transfer rates of the two components are unequal and opposite, the process
is said to be the unequimolecular diffusion, such a process occurs in a chemical reaction.
Example: Species A in a gaseous mixture diffuses through a (3 mm) thick
film and reaches a catalyst surface where the reaction A → 3B takes place.
If the partial pressure of A in the bulk of the gas is 8.5 kN/m2 and the
diffusivity of A is 2*10-5 m2/s. Find the mole flux of A, given the pressure
and temperature of the system are 101.3 kPa and 297 K, respectively.
6. Diffusion and chemical reaction at a boundary:
Often in catalytic reactions where A and B are diffusing to and from a catalyst surface, the relation
between the fluxes NA and NB at steady state is controlled by the stoichiometry of a reaction at a
boundary. An example is gas A diffusing from the bulk gas phase to the catalyst surface, where it reacts
instantaneously and irreversibly in a heterogeneous reaction as follows:
Maxwell's Law for multicomponent mass
transfer
Considering the transfer of component A through a stationary gas consisting of
components B, C, D, ... etc, if the total partial pressure gradient can be regarded as
being made up of a series of terms each representing the contribution of the
individual component gases. The mass transfer rate can be calculated from the
previous equations using the effective diffusivity of A in the mixture (DAm).
Example: Nitrogen is diffusing under steady condition through a
mixture of 2% N2, 20% C2H6 , 30% C2H4 and 48% C4H10 at 298 K and
100 kPa. The partial pressure of nitrogen at two planes (1 mm ) apart
are 13.3 & 6.67 kPa, respectively. Calculate the rate of N2 across the
two planes. The diffusivity of N2 through C4H10 , C2H6 and C2H4 may
be taken as 9.6*10-6 m2/s , 14.8*10-6 m2/s and 16.3*10-6 m2/s,
respectively.
3.5 Diffusion Coefficient for Gases
3.5 Diffusion Coefficient for Gases
Example
Normal butanol (A) is diffusing through air (B)
at 1 atm abs. Using the Fuller et al. method,
estimate the diffusivity DAB for the following
temperatures with the experimental data:
(a) For 0 °C.
(b) For 25.9 °C.
(c) For 0 °C and 2.0 atm abs.
MOLECULAR DIFFUSION IN LIQUIDS
•Diffusion of solutes in liquids is very important in many industrial process, especially in
separation process.

•The rate of molecular diffusion in liquids is slower than in gases because the molecules are
very close together compared to gas.

•In generally, the diffusion coefficient in a gas will be greater than in a liquid but the flux in a
gas is not that much greater because the concentrations in liquids are considerably higher
than in gases.

•In diffusion in liquids an important difference from diffusion from gases is that the
diffusivities are often quite dependent on the concentration of the diffusing component
 MOLECULAR DIFFUSION IN LIQUIDS

In a binary system, containing A and B, this molar flux in the direction of z,

as given by Equation (2.6)

dyA
N A  C DAB y A (N A  N B ) (2.5)
dz
Diffusion of A Through Nondiffusing B
The most important case of diffusion in liquids is that where solute A is diffusing and solvent
B is stagnant or nondiffusing. An example is a dilute solution of propionic acid (A) in a water
(B) solution being contacted with toluene. Only the propionic acid (A) diffuses through the
water phase, to the boundary, and then into the toluene phase. The toluene- water interface
is a barrier to the diffusion of B and N B=0. Such cases often occur in industry. If Eq (3.7) is
rewritten in terms of concentrations by substituting C av=P/RT, CA1=PA1/RT and XBM=PBM/P, we
obtain the equation for liquids at steady state.

D C Av ( X A1  X A 2 )

AB
N
( z 2  z1 ) X BM
A

(5.3)

For dilute solutions XBM is close to 1.0 and C is essentially constant. Then Eq (5.3) simplifies
to

D (C A1  C A 2 )

AB
N
( z 2  z1 )
A

(5.4)
Example: An ethanol-water solution in the form of stagnant film 2.0 mm thick at 293 K is in contact at one surface
with an organic solvent in which ethanol is soluble and water is insoluble. Hence, NB= 0. At point 1 the
concentration of ethanol is 16.8 wt% and the solution density is 978.2 kg/m3. . At point 2 the concentration of
ethanol is 6.8 wt% and the solution density is 988.1 kg/m3. The diffusivity of ethanol is 0.740 x 10-9 m2/s.
Calculate the steady state flux NA
5.3 Diffusion Coefficients for Liquids
5.3.1 Experimental Determination of Diffusivities
Several different methods are used to determine the
diffusion coefficients experimentally in liquids. In one
method unsteady-state diffusion in a long capillary tube is
carried out and the diffusivity determined from
concentration profile. If the solute
A is diffusing in B, the diffusion coefficient determined is DAB.
Also, the value of diffusivity is often very dependent upon
the concentration of the diffusing solute A. Unlike gases, the
diffusivity DAB does not equal DBA for liquids.
To derive the equation, quasi-steady-state diffusion in the membrane is assumed.

𝑐−𝑐 ′
𝑁𝐴 = ε𝐷𝐴𝐵 (5.5)
𝐾1 𝛿

Where c is the concentration in the lower chamber at a time t, c’ is the concentration in the upper, and ε is
the fraction of area of the glass open to diffusion. Making the balance on solute A in the upper chamber,
where the rate in = rate out + r ate of accumulation, making a similar balance on the lower chamber, using
volume V=V ’’ , and combining and integrating the final equation is

𝑐𝑜 −𝑐𝑜′ 2εA
𝑙𝑛 𝑐−𝑐 ′ =𝐾 𝐷𝐴𝐵 𝑡 (5.6)
1 𝛿𝑉

2εA
Where 𝐾 is a cell constant that can be determined using a solute of known diffusivity, such as KCl. Tha
1 𝛿𝑉

values co and 𝑐𝑜′ are initial concentrations and c and c’ final concentrations.
Prediction of Diffusivities in Liquids
Stokes-Einstein Equation

9.96𝑥10−16 𝑇
𝐷𝐴𝐵 = 1/3
𝜇𝑉𝐴

(5.7)

Where DAB is diffusivity in m2/s, T is temperature in K, μ is viscosity of solution in Pa.s or kg/m.s, and VA is the
solute molar volume at its normal boiling point in m3/kg mol.

This equation applies very well to very large unhydrated and spherical-like solute molecules of about 1000
molecular weight or greater, or where the VA is above about 0. 500 m3/kg mol in aqueous solution.
5.3.2.2 Wilke-Chang Equation
5.3.2.2 Wilke-Chang Equation
−16 1/2 𝑇
𝐷𝐴𝐵 = 1.173𝑥10 (𝜑𝑀𝐵 )
𝜇𝐵 𝑉𝐴0.6
(5.8)
Where MB is the molecular weight of solvent B, 𝜇𝐵 is the viscosity of B in Pa.s or kg/m.s, VA is
the solute molar volume at the boiling point, and 𝜑 is an “association parameter” of the
solvent, where 𝜑 is 2.6 for water, 1.9 methanol, 1.0 benzene, 1.0 ether, 1.0 heptane, and 1.0
other unassociated solvents.
Example: Estimate the diffusivity of dilute acetic acid in water at 9.7 ° C and 25 ° C
according to Wilke-Chang and Othmer-Thakar. The experimentally found diffusivities
are given below. Calculate thepercent error.
DAB(9.7) = 0.769 x 10-5 cm2/s
DAB(25) = 1.260 x 10-5 cm2/s
μB(9.7) = 1.319 cp
μB(25) = 0.8937 cp
MB = 18 ve φ = 2.6
6.MOLECULAR DIFFUSION IN SOLIDS
This type of diffusion in solids does not depend on the actual structure of the solid.

Generally, simplified equations are used. Using the general equation (2.5) for binary
d y A CA
N A  C DAB  (N A  N B ) (2.5)
dz C

CA
The bulk flow term, ( N A  N B ) , even if present, is usually small, since XA is quite small. Hence
C
it is neglected. Also, C is assumed constant giving for diffusion in solids,
𝐷𝐴𝐵 𝑑𝐶𝐴
𝑁𝐴 = − (6.1)
𝑑𝑧
Where DAB is diffusivity in m2/s A through B and usually is assumed constant independent of
pressure for solids. Note that DABDBA in solids.
Integration of equation (6.1) for a solid slab at steady state gives
D AB
N  (C A1  C A2) (6.2)
z 2z1
A
 MOLECULAR DIFFUSION IN SOLIDS
For the case of diffusion radially through a cylinder wall of inner radius r1 and outer r2 and length L,

𝑁𝐴 𝑑𝐶𝐴
= −𝐷𝐴𝐵
2𝜋𝑟𝐿 𝑑𝑟
(6.3)

2𝜋𝐿
𝑁𝐴 = 𝐷𝐴𝐵 (𝐶𝐴1 − 𝐶𝐴2 ) 𝑟 (6.4)
ln( 2 )
𝑟1
The diffusion coefficient DAB in the solid as stated above is not dependent upon the pressure of the gas or
liquid on the outside of the solid.
The solubility of a solute gas (A) in a solid is usually expressed as S in m3 solute (at STP of 0 oC and 1 atm)
per m3 solid per atm partial pressure of A.

𝑆𝑚3 (𝑆𝑇𝑃)/(𝑚3 𝑠𝑜𝑙𝑖𝑑.𝑎𝑡𝑚) 𝑆𝑃𝐴 𝑘𝑔 𝑚𝑜𝑙 𝐴

𝐶𝐴 = 𝑚3 𝑆𝑇𝑃
𝑃𝐴 𝑎𝑡𝑚 = (6.5)
22.414(𝑘𝑔 𝑚𝑜𝑙 𝐴) 22.414 𝑚3 𝑠𝑜𝑙𝑖𝑑
 EXAMPLE

The gas hydrogen at 17°C and 0.010 atm partial pressure is diffusing through a membrane of vulcanized neoprene
rubber 0.5 mm thick. The pressure of H2 on the other side of the 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 17°C is
0.051 m3 (at . STP of Dec and 1 atm)/m3 solid· atm and the diffusivity DAB is 1.03 X 10 -10 m 2 /sat 17°C.
 MOLECULAR DIFFUSION IN SOLIDS
. Permeability Equations for Diffusion in Solids
In many cases the experimental data for diffusion of gases in solids are not given as diffusivities
and solubilities but as permeabilities, PM, in m3 of solute gas A at STP diffusing per second per
m2 cross-sectional area through a solid 1 m thick under a pressure difference of 1 atm
pressure. This can be related to Fick’s equation (6.2) as follows
D AB
N  (C  C ) (6.2)
z 2z
A A1 A2
1

From Eq. (6.2),

𝑆𝑃 𝐴 1 𝑆𝑃 𝐴 2
𝐶𝐴1 = , 𝐶𝐴2 = (6.6)
22 .414 22 .414
Substituting eq. (6.6) into (6.2)
𝐷 𝐴𝐵 𝑆(𝑃 𝐴 1 −𝑃 𝐴 2 ) 𝑃 𝑀 (𝑃 𝐴 1 −𝑃 𝐴 2 )
𝑁𝐴 = = kg mol/s.m2 (6.7)
22.414 (𝑧 2 −𝑧 1 ) 22 .414 (𝑧 2 −𝑧 1 )

where the permeability PM is

𝑚 3 (𝑆𝑇𝑃 )
𝑃𝑀 = 𝐷𝐴𝐵 𝑆 (6.8)
𝑠.𝑚 2 𝐶.𝑆 𝑎𝑡𝑚 /𝑚

For the cgs system, the permeability is given as PM’, cc(STB)/(s.cm2 C.S. atm/cm). This is
related to PM by
𝑃𝑀 = 10−4 PM’ (6.9)
When there are several solids 1,2,3,……., in series and L1,L2,…….,represent the thickness of
each, then Eq.(6.7) becomes
𝑃 𝐴 1 −𝑃 𝐴 2 1
𝑁𝐴 = 𝐿1 𝐿 (6.10)
22 .414
𝑃𝑀1
+𝑃 2 +⋯+
𝑀2
 EXAMPLE

A polyethylene film 0.000 15 m (0.15 mm) thick is being considered for use in packaging a pharmaceutical product at
30°C. If the partial pressure of O 2 outside is 0.21 atm and inside the package it is 0.01 atm, calculate the diffusion flux
of O 2 at steady state. Use permeability data from Table. Assume that the resistances to diffusion outside the film and
inside are negligible compared to the resistance of the film.
6.2. Diffusion on Porous Solids That Depends on Structure
6.2.1 Diffusion of Liquids on Porous Solids

Fig 6. Sketch of a typical porous solid

𝜀 𝐷 𝐴𝐵 (𝐶𝐴 1 −𝐶𝐴 2 )
𝑁𝐴 = (6.11)
𝜏 (𝑧 2 −𝑧1 )
𝜀
𝐷𝐴 𝑒𝑓𝑓 = 𝐷𝐴𝐵 , m2/s (6.12)
𝜏
where 𝜀 is the open void fraction, DAB is the diffusivity of salt in water, and 𝜏 is a factor which
corrects for the path longer than (𝑧2 − 𝑧1 ). Often the terms are combined into an effective
diffusivity.
 EXAMPLE

A sintered solid of silica 2.0 mm thick is porous with a void fraction ε of 0.30 and a tortuosity r of 4.0. The pores are filled
with water at 298 K. At one face the concentration of KCI is held at 0.1 0 g mol/liter, and fresh water flows rapidly by the
other face. Neglecting any other resistances but that in the porous solid, calculate the diffusion of KCl at steady state.
6.2.2 Diffusion of Gases on Porous Solids
If the voids shown in Figure 6 are filled with gases, then a somewhat similar situation exists. If
the pores are very large so that diffusion occurs only by Fickian-type diffusion, then Eq.(6.11)
becomes, for gases,
𝜀𝐷𝐴𝐵 (𝐶𝐴 1 −𝐶𝐴 2 ) 𝜀𝐷𝐴𝐵 (𝑃𝐴 1 −𝑃𝐴 2 )
𝑁𝐴 = = (6.13)
𝜏 (𝑧2 −𝑧1 ) 𝜏𝑅𝑇 (𝑧2 −𝑧1 )
7.DIFFUSION OF GASES IN POROUS
SOLIDS AND CAPILLARIES
In previous section diffusion in porous solids that depends on structure was discussed
for liquids and for gases. For gases it was assumed that the pores were very large and
Fickian-type diffusion occured. However, often the pores are small in diameter and
the mechanism of diffusion is basically changed.
Diffusion of gases in small pores occurs often in heterogeneous catalysis where gases
diffuse through very small pores to react on the surface of the catalyst. In freeze
drying of foods such as turkey meat, gaseous H 2 0 diffuses through very fine pores of
the porous structure.
7.DIFFUSION OF GASES IN POROUS
SOLIDS AND CAPILLARIES
Since the pores or capillaries of porous solids are often small, the diffusion of gases may depend upon the
diameter of the pores. We first define a mean free path λ; which is the average distance a gas molecule travels
before it collides with another gas molecule.
7.DIFFUSION OF GASES IN POROUS
SOLIDS AND CAPILLARIES

Figure 7.1
 Knudsen Diffusion of Gases

Knudsen Diffusion of Gases d t In Fig. 7.1 (a) a gas molecule A at partial pressure PA1 at
the entrance to a capillary is diffusing through the capillary having a diameter of d m.
The total pressure P is constant throughout. The mean free path ), is large compared
to the diameter d. As a result, the molecule collides with the wall and molecule-wall
collisions are important. This type is called Knudsen diffusion.
EXAMPLE

A H2(A)-C2H6(B) gas mixture is diffusing in a pore of a nickel catalyst used for

hydrogenation at 1.01325 x 105 Pa pressure and 373 K. The pore radius is 60 A
(angstrom). Calculate the Knudsen diffusivity DKA of H2 .
 Molecular Diffusion of Gases
As shown in Fig. 7.1 (b )when the mean free path λ is small compared to the pore diameter d or where
NKn ≤1/100, molecule-molecule collisions predominate and molecule-wall collisions are few. Ordinary
molecular or Fickian diffusion holds and Fick's law predicts the diffusion to within about 10%. The error
diminishes as NKn gets smaller since the diffusion approaches more closely the Fickian type.
 Transition-Region Diffusion of Gases
As shown in Fig. 7.1c, when the mean free path λ and pore diameter are intermediate in size between the two limits
given for Knudsen and molecular diffusion, transition-type diffusion occurs where molecule-molecule and molecule-
wall collisions are important in diffusion.
 Flux Ratios for Diffusion of Gases in Capillaries
1. Diffusion in open system. If diffusion in porous solids or channels with no chemical reaction is occurring where the
total pressure P remains constant, then for an open binary counterdiffusing system, the ratio of NA/NB is constant in
all of the three diffusion regimes

2. Diffllsion ill closed system. When molecular diffusion is occurring in a closed system shown in Fig. 7.2 at
constant total pressure P, equimolar counterdiffusion occurs.
EXAMPLE

A gas mixture at a total pressure of 0.10 atm abs and 298 K is composed of N2 (A) and He (B). The mixture is diffusing
through an open capillary 0.010 m long having a diameter of 5 x 10 -6 m. The mole fraction of N2 at one end is
XA1 =0.8 and at the other end is XA2 = 0.2. The molecular diffusivity DAB is 6.98 x 10 -5 m2/s at 1 atm, which is an
average value by several investigators. Calculate the flux NA at steady state