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452 ▶ Chapter 24 Fundamentals of Mass Transfer

where DAB is liquid-phase diffusion coefficient of A in B at infinite dilution with respect to

component A, DBA is the liquid-phasse diffusion coefficient of B in A at infinite dilution with
respect to B, and xA and xB are the mole fraction compositions of A and B, respectively.

Liquid-Phase Binary Diffusion Coefficients for Ionic Solutes The properties of

electrically conducting solutions have been studied intensively. Even so, the known
relations between electrical conductance and the liquid diffusion coefficient are valid
only for dilute solutions of salts in water.
To maintain charge neutrality, both the cation and the anion of the ionic salt must
diffuse through water as an ionic pair. The diffusion coefficient of a univalent salt in dilute
solution is given by the Nernst–Haskell equation:
2RT
DAB ˆ   (24-56a)
1=l0‡ ‡ 1=l0 …F †2
where DAB is the diffusion coefficient of the ion pair in solvent B at infinite dilution, R is the
thermodynamic gas constant …8:316 J=gmole ? K†, T is absolute temperature (K), l0‡ and l0
are the limiting (zero concentration) ionic conductances of the cation and anion, respec-
tively, in the ion pair …A ? cm2 =V ? gmole†, and F is the Faraday’s constant (96,500
C/gmole), taking note that 1 C ˆ 1 A ? s and 1 J=s ˆ 1 A ? V. Equation (24-56a) is extended
to polyvalent ions by
…1=n‡ ‡ 1=n †RT
DAB ˆ   (24-56b)
1=l0‡ ‡ 1=l0 …F †2
where n‡ and n are the valences of the cation and anion, respectively. Limiting ionic
conductances for selected ionic species8 are presented in Table 24.6.

Table 24.6 Selected limiting ionic conductances in water at 25°C, reported in units
of A
cm2/V
gmole
Cation l0‡ Anion l0
H‡ 349.8 OH 197.6
Li‡ 38.7 Cl 76.3
Na‡ 50.1 Br 78.3
K‡ 73.5 I 76.8
NH4‡ 73.4 NO3 71.4
Ag‡ 61.9 HCO3 44.5
Mg‡2 106.2 SO4 2 160
Ca‡2 119
Cu‡2 108
Zn‡2 106

Pore Diffusivity
There are many instances where molecular diffusion occurs inside the pores of porous solids.
For example, many catalysts are porous solid pellets containing catalytically active sites on the
pore walls. The porous catalyst possesses a high internal surface area to promote chemical
reactions at the catalytic surface. The separation of solutes from dilute solution by the process
of adsorption is another example. In an adsorption process, the solute sticks to a feature on the
solid surface that is attractive to the solute. Many adsorbent materials are porous to provide a
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24.2 The Diffusion Coefficient ◀ 453

high internal surface area for solute adsorption. In both examples, the molecules must diffuse
through a gas or liquid phase residing inside the pores. As the pore diameter approaches the
diameter of the diffusing molecule, the diffusing molecule can interact with the wall of the
pore. Below, we describe two types of pore diffusion: the Knudsen diffusion of gases in
cylindrical pores and the hindered diffusion of solutes in solvent-filled cylindrical pores.

Knudsen Diffusion Consider the diffusion of gas molecules through very small
capillary pores. If the pore diameter is smaller than the mean-free path of the diffusing
gas molecules and the density of the gas is low, the gas molecules will collide with the pore
walls more frequently than with each other. This process is known as Knudsen flow or
Knudsen diffusion. The gas flux is reduced by the wall collisions.
Pure molecular diffusion, pure Knudsen diffusion, and molecular diffusion in tiny
pores influenced by Knudsen diffusion within a straight cylindrical pore are compared in
Figure 24.4. The Knudsen number, Kn, given by
l mean-free path length of the diffusing species
Kn ˆ ˆ (24-57)
dpore pore diameter
is a good measure of the relative importance of Knudsen diffusion. If 0.1 < Kn < 1, then
Knudsen diffusion plays a measurable but moderate role in the overall diffusion process.
If Kn >1, then Knudsen diffusion becomes important, and if Kn > 10, then Knudsen
diffusion can dominate. At a given pore diameter, the Kn number goes up as the total system
pressure P decreases and absolute temperature T increases. In practice, Knudsen diffusion
applies only to gases because the mean-free path for molecules in the liquid state is very
small, typically near the molecular diameter of the molecule itself.

Pure Knudsen Knudsen + molecular Pure molecular

diffusion diffusion diffusion
Pore wall Pore wall Pore wall
A A A
dpore B
B

Figure 24.4 Influence of Knudsen and molecular diffusion on the effective diffusion within a
straight pore.

The diffusion coefficient for Knudsen diffusion is obtained from the self-diffusion
coefficient derived from the kinetic theory of gases:
rffiffiffiffiffiffiffiffiffiffiffiffi
lu l 8kNT
DAA* ˆ ˆ
3 3 pM A
For Knudsen diffusion, we replace path length l with pore diameter dpore, as species A is
now more likely to collide with the pore wall as opposed to another molecule. In this
instance, the Knudsen diffusivity for diffusing species A, DKA, is
rffiffiffiffiffiffiffiffiffiffiffiffiffiffi
d pore dpore 8 kN T
DKA ˆ uˆ (24-58a)
3 3 pM A
Or, since k and N are physical constants, equation (24-58a) is also given by
rffiffiffiffiffiffiffi
T
DKA ˆ 4850 dpore (24-58b)
MA
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454 ▶ Chapter 24 Fundamentals of Mass Transfer

The simplified equation (24-58b) requires that dpore has units of cm, MA has units of
g/gmole, and temperature T has units of K. The Knudsen diffusivity, DKA, is dependent on
the pore diameter, species A molecular weight, and temperature.
We can make two comparisons of DKA to the binary gas-phase diffusivity, DAB. First,
DKA is not a function of absolute pressure P, or the presence of species B in the binary gas
mixture. Second, the temperature dependence for the Knudsen diffusivity is T1/2, vs. T3/2 for
the binary gas-phase diffusivity.
Generally, the Knudsen diffusion process is significant only at low pressure and small
pore diameter. However, there are instances where both Knudsen diffusion and molecular
diffusion can be important. If we consider that Knudsen diffusion and molecular diffusion
compete with one another by a “resistances in series” approach, then it can be shown that the
effective diffusion coefficient of species A in a gaseous binary mixture of A and B within the
pore is determined by
1 1 ayA 1
ˆ ‡ (24-59)
DAe DAB DKA
with
NB
aˆ1‡
NA
For cases where a ˆ 0 …N A ˆ N B †, or where yA is close to zero—e.g., for a dilute mixture
of A in carrier gas B—equation (24-59) reduces to
1 1 1
ˆ ‡ (24-60)
DAe DAB DKA
In general, DAe ≠ DBe .
The above relationships for the effective diffusion coefficient are based on diffusion
within straight, cylindrical pores aligned in a parallel array. However, in most porous
materials, pores of various diameters are twisted and interconnected with one another, and
the path for diffusion of the gas molecule within the pores is “tortuous,” as shown in
Figure 24.5. For these materials, if an average pore diameter is assumed, a reasonable
approximation for the effective diffusion coefficient in random pores is

D0Ae ˆ e2 DAe (24-61)

where e is the volume void fraction of the porous volume within the porous material, which
is defined as
the volume occupied by pores within the porous solid
eˆ
total volume of porous solid …solid ‡ pores†

Random porous material

A B

Figure 24.5 Diffusion in random porous materials.

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24.2 The Diffusion Coefficient ◀ 455

The void fraction (e) is usually experimentally determined for a specific material. In cases
of large pore diameters or high pressure where Knudsen diffusion is not important, equation
(24-61) reduces to

D0Ae ˆ e2 DAB
The e2 term accounts for the available cross-sectional area for flux of the fluid mixture
through the porous solid, as species A and B can only enter the porous material
from the surrounding bulk fluid through the available flux area defined by the pore
openings.

Example 5
A dilute mixture of carbon dioxide (CO2) in ethylene (C2H4) gas is diffusing within a random porous material with void fraction
of 0.45 at a total system pressure of 2.0 atm and temperature of 350 K. Estimate the effective diffusion coefficient of CO2 and
ethylene within the porous material if the mean pore diameter is 0.20 mm.
Let species A represent CO2 with molecular weight of 44 g/mole, and species B represent C2H4 with a molecular weight of
28 g/mole. From Example 3, the gas-phase binary molecular diffusion coefficient, DAB, is 0.077 cm2/s at 2.0 atm total system
pressure and 350 K absolute temperature. Given that the diffusion process is within a mesoporous material, which has
pore diameters less than 1:0 mm …1:0 mm ˆ 1:0  10 6 m†, Knudsen diffusion may contribute to the molecular mass-transfer
process. The Knudsen diffusion coefficient for CO2 is estimated by equation (24-58b), with dpore ˆ 2.0  10 5 cm and MA ˆ
44 g/gmole:
rffiffiffiffiffiffiffi rffiffiffiffiffiffiffiffi
T 350
DKA ˆ 4850 d pore ˆ 4850 …2:0  10 5 † ˆ 0:274 cm2 =s
MA 44
Consequently, from equation (24-60), for CO2 diluted in ethylene, effective diffusion coefficient of species A in a dilute gas
mixture within the pore is
  
DAB DKA 0:077 cm2 =s 0:274 cm2 =s
DAe ˆ ˆ ˆ 0:060 cm2 =s
DAB ‡ DKA …0:077 cm2 =s† ‡ …0:274 cm2 =s†
We note that DAe < DAB , showing the effect of Knudsen diffusion. To this point, the mean-free path and Knudsen number for
CO2 inside the pore are
 
16 erg 1 N m
1:38  10 …350 K †
kT K 107 erg
l ˆ pffiffiffi 2 ˆ  2  
2ps A P pffiffiffi 1m 101;300 N=m2
2p 0:3996 nm 9 2:0 atm
10 nm atm

ˆ 3:36  10 8
m ˆ 0:0336 mm
and
l 0:0336 mm
Kn ˆ ˆ ˆ 0:17
d pore 0:200 mm
From this analysis, Knudsen diffusion plays only a moderate role at the conditions of the process even though the pore diameter is
only 0.2 mm. Finally, the effective diffusion coefficient for CO2, as corrected for the void fraction within the random porous
material, is

D0Ae ˆ e2 DAe ˆ …0:45†2 …0:060 cm2 =s† ˆ 0:012 cm2 =s

The effect of total system pressure on the ratio DAe/DAB is shown in Figure 24.6. At high total system pressures, the effective
diffusion coefficient (DAe) approaches the molecular diffusion coefficient, DAB. At low total system pressures, Knudsen diffusion
becomes important.
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456 ▶ Chapter 24 Fundamentals of Mass Transfer

1.0

0.8

DAe / DAB
0.6

0.4

0.2 Figure 24.6 Effect of total system

pressure on the ratio of the effective
0.0 diffusion coefficient to the binary gas-
0 2 4 6 8 10 phase molecular diffusion coefficient,
Total system pressure, P (atm) Example 5.

Hindered Solute Diffusion in Solvent-Filled Pores Consider the diffusion of a

solute molecule (species A) through a tiny capillary pore filled with liquid solvent (species
B), as shown in Figure 24.7. As the molecular diameter of the solute approaches the diameter
of the pore, the diffusive transport of the solute through the solvent is hindered by the
presence of the pore and the pore wall. General models for diffusion coefficients describing
the “hindered diffusion” of solutes in solvent-filled pores assume the form of
DAe
ˆ F 1 …j†F 2 …j† (24-62)
DoAB

Pore wall

ds
dpore
Solute Solvent

Cross section

ds
𝜑=
ds dpore

dpore Figure 24.7 Diffusion of solute in solvent-filled pore.

The molecular diffusion coefficient of solute A in the solvent B at infinite dilution, DoAB , is
reduced by two correction factors, F 1 …j†, and F 2 …j†, both of which are theoretically
bounded by 0 and 1. Furthermore, both correction factors are functions of the reduced pore
diameter j
ds solute molecular diameter
jˆ ˆ (24-63)
dpore pore diameter
If j > 1, then the solute is too large to enter the pore. This phenomenon is known as solute
exclusion, and it is used to separate large biomolecules such as proteins from dilute
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24.2 The Diffusion Coefficient ◀ 457

aqueous mixtures containing solutes of much smaller diameter. As j approaches 1, both

F 1 …j† and F 2 …j† decrease asymptotically toward zero, so at j ˆ 1, the effective diffusion
coefficient is zero.
The correction factor F 1 …j†, the stearic partition coefficient, is based on simple
geometric arguments for stearic exclusion:
 2
flux area available to solute p dpore d s
F 1 …j † ˆ ˆ ˆ …1 j†2 (24-64)
total flux area pd 2pore

and holds for 0 £ F 1 …j† £ 1:0.

The correction factor F 2 …j†, the hydrodynamic hindrance factor, is based on the
complicated hydrodynamic calculations involving the hindered Brownian motion of the
solute within the solvent-filled pore. Equations for F 2 …j†, assuming diffusion of a rigid
spherical solute in a straight cylindrical pore, have been developed. The analytical models
are generally asymptotic solutions over a limited range of j, and ignore electrostatic or other
energetic solute-solvent-pore wall interactions, polydispersity of solute diameters, and
noncircular pore cross sections. The most common equation, developed by Renkin,20
is reasonable for the range 0 < j < 0:6:

F 2 …j † ˆ 1 2:104j ‡ 2:09j3 0:95j5 (24-65)

The effect of reduced pore diameter on the effective diffusion coefficient is presented in
Figure 24.8.

1.0

0.8
DAe / DAB

0.6

0.4

0.2
Figure 24.8 Effect of reduced pore
0.0 diameter on the effective diffusion
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
coefficient, using the Renkin equation for
Reduced pore diameter, 𝜑 = ds / dpore
the hydrodynamic hindrance factor.

Example 6
It is desired to separate a mixture of two industrial enzymes, lysozyme and catalase, in a dilute, aqueous solution by a gel filtration
membrane. A mesoporous membrane with cylindrical pores of 30 nm diameter is available (Figure 24.9). The following
separation factor (a) for the process is proposed:
DAe
aˆ
DBe

20
E. M. Renkin, J. Gen. Physiol., 38, 225 (1954).
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458 ▶ Chapter 24 Fundamentals of Mass Transfer

ds,B = 10 nm Bulk solvent

ds,A = 4 nm

Nanoporous
membrane
material

Figure 24.9 Hindered

diffusion of enzyme
molecules in liquid water-
dpore = 30 nm filled nanopores.

Determine the separation factor for this process. The properties of each enzyme as reported by Tanford21 are given below.

Lysozyme (species A) Catalase (species B)

MA ˆ 14,100 g/gmole MB ˆ 250,000 g/gmole
ds,A ˆ 4.12 nm ds,B ˆ 10.44 nm
DoA H2 O ˆ 1:04  10 6 cm2 =s DoB H2 O ˆ 4:10  10 7 cm2 =s

The transport of large enzyme molecules through pores filled with liquid water represents a hindered diffusion process. The
reduced pore diameters for lysozyme and catalase are
ds;A 4:12 nm ds;B 10:44 nm
jA ˆ ˆ ˆ 0:137 and jB ˆ ˆ ˆ 0:348
d pore 30:0 nm d pore 30:0 nm
For lysozyme, F 1 …jA †, by equation (24-64), and F 2 …jA †, by the Renkin equation (24-65), are

F 1 …j A † ˆ …1 jA †2 ˆ …1 0:137†2 ˆ 0:744
F 2 …j A † ˆ 1 2:104jA ‡ 2:09j3A 0:95j5A
ˆ 1 2:104…0:137† ‡ 2:090…0:137†3 0:95…0:137†5 ˆ 0:716
The effective diffusivity of lysozyme in the pore, DAe , is estimated by equation (24-62)

cm2 cm2
DAe ˆ DA H2 O F 1 …jA †F 2 …jA † ˆ 1:04  10 6
…0:744†…0:716† ˆ 5:54  10 7
s s
Likewise, for catalase F 1 …jB † ˆ 0:425; F 2 …jB † ˆ 0:351, and DBe ˆ 6:12  10 8
cm2 =s. Finally, the separation factor is

DAe 5:54  10 7
cm2 =s
aˆ ˆ ˆ 9:06
DBe 6:12  10 8
cm2 =s
It is interesting to compare the value above with a0 , the ratio of molecular diffusivities at infinite dilution:

DA 1:04  10 6 cm2 =s
a0 ˆ
H2 O
ˆ ˆ 1:75
DB H2 O 4:1  10 7 cm2 =s
The small pore diameter enhances the value for a, because the diffusion of the large catalase molecule is significantly hindered
inside the pore relative to the smaller lysozyme molecule.

21
C. Tanford, Physical Chemistry of Macromolecules, John Wiley & Sons, New York, 1961.