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Lecture Notes on the Estimation of Binary Diffusivities

The lecture notes provide an overview of estimating binary diffusivities in gases and liquids, highlighting the dependence on temperature and pressure, as well as specific equations for non-polar molecular pairs. Key equations include the Hirschfelder, Bird, Spotz equation for gas phase diffusivity and the Wilke-Chang correlation for liquid phase diffusivity at infinite dilution. Recent remarks emphasize methods for estimating diffusion coefficients in multicomponent mixtures, referencing a 2019 review by Taylor and Duss.

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4 views

Lecture Notes on the Estimation of Binary Diffusivities

The lecture notes provide an overview of estimating binary diffusivities in gases and liquids, highlighting the dependence on temperature and pressure, as well as specific equations for non-polar molecular pairs. Key equations include the Hirschfelder, Bird, Spotz equation for gas phase diffusivity and the Wilke-Chang correlation for liquid phase diffusivity at infinite dilution. Recent remarks emphasize methods for estimating diffusion coefficients in multicomponent mixtures, referencing a 2019 review by Taylor and Duss.

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abbasmuhammad20022
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© © All Rights Reserved
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Lecture Notes on the Estimation of Binary Diffusivities

Updated April 2020

R. Shankar Subramanian
Department of Chemical and Biomolecular Engineering
Clarkson University

Information from Section 24.2 of the textbook by Welty et al.

Binary diffusivity in gases

Temperature and Pressure dependence


Gas phase diffusivities are approximately proportional to T 1.75 / P , where T is the
absolute temperature, and P is the absolute pressure. The inverse dependence on
pressure holds up to about 25 atmospheres. If an experimental value of the
diffusivity is available at a given temperature and pressure, the diffusivity at some
other temperature and pressure can be estimated from the above dependence.
Binary diffusivities in the gas phase are relatively insensitive to composition. This
is not the case in liquids.

Hirschfelder, Bird, Spotz equation


Equation (24-33) on page 443 for pairs A-B of non-polar molecules:
1/2
 1 1 
3/2
0.001858 T  +
 M A M B 
DAB =
P σ AB
2
ΩD

DAB : Binary gas phase diffusivity of A in B in cm 2 / s .


T: Absolute temperature in Kelvin
P: Absolute pressure in atmospheres
M A , M B : Molecular weights of A and B, respectively
σ AB : Lennard-Jones collision diameter in Angstroms
ΩD : Collision integral for molecular diffusion.

1
If σ AB is not known for a given binary system composed of a non-polar molecular
pair, construct it using

1
σ AB
= (σ A + σ B ) Equation (24-39), page 444
2

Individual values of σ A are given in Table K-2 in Appendix K of the textbook.

Values of the collision integral for molecular diffusion are given in Table K-1 in
Appendix K as a function of a dimensionless temperature kT / ε AB . Table K-2 in the
same Appendix lists values of ε / k for several molecules. For a binary system
composed of a non-polar molecular pair, construct ε AB / k using

ε AB  εA  εB 
=   
k  k  k 

which is the same result as Equation (24-40): ε AB = ε Aε B

Fuller-Schettler-Giddings Equation

The Fuller-Schettler-Giddings Equation (Equation (24-42) on page 445) can be


used for estimating binary diffusivities when the Lennard-Jones parameters are not
available for one or both species in a nonpolar binary gas mixture.

1/2
−3  1 1 
M + M 
1.75
10 T
DAB =  A B 

P ( ∑ v ) A + ( ∑ v ) B 
1/3 1/3 2

 

DAB : Binary gas phase diffusivity of A in B in cm 2 / s .


T: Absolute temperature in Kelvin
P: Absolute pressure in atmospheres
M A , M B : Molecular weights of A and B, respectively
(∑ v) , (∑ v)
A B
: molecular volumes in cm3 / g − mol

Obtain the molecular volumes from Table 24.3 on page 445.

2
Predictions can be made for polar-non-polar pairs or for polar-polar pairs, but we
won’t be able to discuss them here. See pages 446-447 in the book for information
about one approach called Brokaw’s method.

Diffusion coefficient of species 1 in a mixture of n species

If we know binary diffusivities D1−2 , D1−3 ,  , D1−n , for species 1 in a mixture of n


species, the diffusivity of species 1 in the mixture can be approximated using
Equation (24-49) on page 448.

1 y2′ y′ y′
= + 3 + + n
D1− mixture D1− 2 D1−3 D1− n

yn′ is the mole fraction of component n in the gas mixture evaluated on a


component-1-free basis, that is

y2 y2
=y2′ =
y2 + y3 +  + yn 1 − y1

3
Binary diffusivity in liquids

In liquids, it is possible to estimate the diffusivity of a non-electrolyte solute in


dilute solution (in principle, at infinite dilution) using the Wilke-Chang correlation,
given as Equation (24-52) on page 449 of the textbook.

T 7.4 ×10 ( Φ B M B )
−8 1/2

DAB =
µB VA0.6
DAB : Binary diffusivity of A at infinite dilution in B cm 2 / s .
T: Absolute temperature in Kelvin
µ B : Viscosity of solvent B in cp (this means centipoise)
M B : Molecular weight of solvent B
Φ B : Association parameter of solvent B
VA : Molal volume of solute A at normal boiling point in cm3 / g − mol
Use Tables 24.4 and 24.5 on pages 449-450 to estimate atomic and molal volumes
at the normal boiling point. The association parameter for common solvents can
be found in a table that appears below Table 24.5 on page 450.

A simpler result that gives nearly the same prediction is the correlation of Hayduk
and Laudie, which is to be used for evaluating the diffusion coefficients of non-
electrolytes in water in dilute solution (in principle, at infinite dilution). It is given
as Equation (24-53) on page 450 in the book.

DAB 13.26 ×10−5 ( µ B ) (VA )


−1.14 −0.589
=

The notation is the same as that used in the Wilke-Chang correlation, and the
diffusivity of A at infinite dilution in B is obtained in cm 2 / s .

Note that the above estimates for a solute at infinite dilution. In practice, they can
be used as adequate approximations so long as the solution is reasonably dilute;
however, unlike binary gas phase diffusivities, liquid phase diffusivities depend
strongly on concentration. In pages 451-452 in Chapter 24 of the textbook, the
authors briefly mention a common method used to obtain binary diffusivities in
non-dilute solutions.

4
Remarks added in April 2020

In a recent review article on separation column efficiency, Taylor and Duss (2019)
discuss a general approach for estimating the diffusion coefficient of a key species
in a multicomponent mixture in both gas phase mixtures and liquid mixtures. For
example, when using the equations proposed by Hirschfelder, Bird, and Spotz or
Fuller,-Schechter-Giddings for gas phase diffusion coefficients, if A is the key
species in the mixture, we lump all the other species into B, and obtain M B from

n
xi
MB = ∑ x ′M
i = 1≠ A
i i where xi′ =
1 − xA

In the summation, the case i = A is omitted, and the result for xi′ is used only for
i ≠ A . A similar weighted result is used for the “molecular volume” of B, if needed
in the correlation.
n
VB = ∑ x ′V
i = 1≠ A
i i

These ideas also can be extended to the liquid phase in the correlations of Wilke-
Chang or Hayduk and Laudie. Wherever information for species B is needed, a
weighted average on an A-free basis obtained in the above manner is substituted.
The viscosity of the solvent B is estimated using any method applicable to
mixtures, but on an A-free basis.

For more details, please consult the article by Taylor and Duss (2019).

References

R. Taylor and M. Duss, Industrial and Engineering Chemistry Research, 58,


16877-16893 (2019).

J. Welty, C.E. Wicks, G.L. Rorrer, and R.E. Wilson, Fundamentals of Momentum,
Heat, and Mass Transfer, 5th edition, Wiley, Hoboken, NJ (2007).

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