CH 24

CHE 304
Mass Transfer
Chapter 24
Fundamentals
dV
Elemental volume containing a multicomponent mixture
For species A,
mass concentration, 𝜌𝐴 , is defined as the mass of A per unit volume
of the mixture
The total mass concentration or density,𝜌, is the total mass of the mixture
contained in the unit volume
The mass fraction, , is the mass concentration of species A divided by the
total mass density
The molecular concentration of species A, cA, is defined as the number of

moles of A present per unit volume of the mixture. By definition, one mole of
any species contains a mass equivalent to its molecular weight; the mass
concentration and molar concentration terms are related by the following
relation:
the ideal gas law

for a gaseous mixture that obeys the ideal gas law
The mole fraction for liquid or solid mixtures, xA, and for gaseous mixtures, yA, are
the molar concentrations of species A divided by the total molar density
For a gaseous mixture that obeys the ideal gas law, the mole fraction, yA, can be
written in terms of pressures
(Dalton’s law for gas mixtures)

The mass-average velocity
The mass-average velocity for a multicomponent mixture is defined in terms
of the mass densities and velocities of all components by
The molar-average velocity

The molar-average velocity for a multicomponent mixture is defined in terms
of the molar concentrations of all components by
The velocity of a particular species relative to the mass-average or molar-
average velocity is termed a diffusion velocity. We can define two different
diffusion velocities
• Species in a mixture move at different velocities vi

(where vi are relative to stationary axis)
• The diffusion relative velocity of species i

(only if conc. gradient exist)
1) relative to v: vi - v
2) relative to V: vi - V
Molecular Mass Transfer
or Molecular Diffusion/Diffusion
Fick’s Law
Molecular Mass Transfer
or Molecular Diffusion/Diffusion
The figure below shows the molecular diffusion process schematically. A

random path that the blue molecule might take in diffusing through white
molecules from right hand side to the left hand side.
Since there are greater number of blue molecules in the right hand side,
then more blue molecules will diffuse from right to left hand side. The net
diffusion of blue molecules from high to low concentration region
• Fluxes: The mass (or molar) flux of a given species is a vector
quantity denoting the amount of the particular species, in
either mass or molar units, that passes per given increment of
time through a unit area normal to the vector. The flux may be
defined with reference to coordinates that are fixed in space,
coordinates that are moving with the mass average velocity, or
coordinates that are moving with the molar-average velocity.
• Molar flux of A: (moles/time/area): JA
- general form:
- special form:
• Mass flux of A: (mass/time/area): jA
- general form:
- special form:
• Total molar Flux: NA
• Total mass Flux: nA

Fick’s Law :
The basic relation for molecular diffusion defines the molar flux relative to the
molar average velocity, JA. An empirical relation for this molar flux, first
postulated by Fick and, accordingly, often referred to as Fick’s first law, defines
the diffusion of component A in an isothermal, isobaric system:
For diffusion in only the z direction, the Fick rate equation is

An equivalent expression for jA,z, the mass flux in the z direction relative to the
mass-average velocity
Initial experimental investigations of molecular diffusion were unable to verify

Fick’s law of diffusion. This was apparently due to the fact that mass is often
transferred simultaneously by two possible means: (1) as a result of the
concentration differences as postulated by Fick and (2) by convection differences
induced by the density differences that resulted from the concentration variation.
Steffan (1872) and Maxwell (1877), using the kinetic theory of gases, proved that
the mass flux relative to a fixed coordinate was a result of two contributions: the
concentration gradient contribution and the bulk motion contribution.
For a binary system with a constant average velocity in the z direction, the molar
flux in the z direction relative to the molar-average velocity may also be
expressed by
As the component velocities, and , are velocities relative to the fixed z axis,
the Quantities and are fluxes of components A and B relative to a fixed
z coordinate;
we symbolize for components A and B relative this new type of flux that is
relative to a set of stationary axes by
This relation may be generalized and written in vector form as
It is important to note that the molar flux, NA, is a resultant of the two vector
quantities:
Either or both quantities can be a significant part of the total molar flux, NA.
Whenever ther above equation is applied to describe molar diffusion, the vector
nature of the individual fluxes, NA and NB, must be considered and then, in turn,
the direction of each of two vector quantities must be evaluated.
If species A were diffusing in a multicomponent mixture, the expression equivalent

to the above equation would be
where DAM is the diffusion coefficient of A in the mixture
The mass flux, nA, relative to a fixed spatial coordinate system, is defined for a
binary system in terms of mass density and mass fraction by
Where and
Under isothermal, isobaric conditions, this relation simplifies to
To derive the case for A through stagnant nondiffusing B, NB,Z = 0
Fick’s law of proportionality, DAB, is known as the diffusion coefficient
 JA = - DAB (dcA / dz) unit of DAB = ?
 DAB = f (T, P, composition of the system)
 (DAB)gas > (DAB)liquid > (DAB)solid
 Exp values for DAB are listed in tables J.1-J.3 (appendix)
 If exp values not available, you may use these correlations:

 Eq. (24-33): “Hirschfelder eq”
 Assumptions:
- for non-polar, non-reacting molecules
- for binary mixture
- P: up to 25 atm
Variables:
T (K)
P (atm)
σAB (Ǻ): collision diamter (L-J parameter): from table K.2
ΩD: collision integral = f (k T /εAB)
Appendix Table K.1 lists VD as a function of k T /εAB, k is the
Boltzmann constant, which is 1:38 1016 ergs/K, and εAB is the
energy of molecular interaction for the binary system A and B.
DAB (cm2/s)
Effect of P and T:
For a binary system composed of nonpolar molecular pairs, the Lennard–Jones

parameters of the pure component may be combined empirically by the
following relations:
Example 2
From Appendix Table K.2, the

values are obtained
Equation (24-41) will be used to correct for the differences in temperature
Equation (24-33) was developed for dilute gases consisting of nonpolar, spherical
monatomic molecules. However, this equation gives good results for most
nonpolar, binary gas systems over a wide range of temperatures.
Other empirical equations have been proposed9 for estimating the diffusion
coefficient for nonpolar, binary gas systems at low pressures. The empirical
correlation recommended by Fuller, Schettler, and Giddings permits the evaluation
of the diffusivity when reliable Lennard–Jones parameters
Fuller correlation
Example 3
Brokaw11 has suggested a method for estimating diffusion coefficient for
binary gas mixtures containing polar compounds. The Hirschfelder equation ()
is still used; however, the collision integral is evaluated by
Where,
with each component’s evaluated by
and
with each component’s characteristic length evaluated by
Mass transfer in gas mixtures of several components can be described by
theoretical equations involving the diffusion coefficients for the various binary pairs
involved in the mixture.
Hirschfelder, Curtiss, and Bird present an expression in its most general form.
Wilke has simplified the theory and has shown that a close approximation to the
correct form is given by the relation
Example 4
Solution
Liquid mass diffusivity:
 Eq. (24-52): “Wilke & Chang eq”
 Assumptions:
- nonelectrolytes
- very dilute solutions
 Variables:
- T (K)
- μB (cp)
- ΦB : association parameter for solvent B
- VA (cm3/mol) : molecular volume of solute
- DAB (cm2/s)
An equation that has been developed from the hydrodynamical theory is the
Stokes–Einstein equation
Where,
DAB is the diffusivity of A in dilute solution in B
k is the Boltzmann constant,
T is the absolute temperature,
r is the solute particle radius
𝜇𝐵 is the solvent viscosity.
Wilke and Chang have proposed the following correlation for nonelectrolytes
in an infinitely dilute solution
Where,
DAB is the mass diffusivity of A diffusing through liquid solvent B, in cm2/s;
𝜇𝐵 is the viscosity of the solution, in centipoises;
T is absolute temperature, in K;
MB is the molecular weight of the solvent;
VA is the molal volume of solute at normal boiling point, in cm3/g mol;
𝜑𝐵 is the ‘‘association’’ parameter for solvent B.
Example 5
Solutions
Scheibel21 has proposed that the Wilke–Chang relation be modified to
eliminate the association factor, 𝜑𝐵 , yielding
Pore Diffusivity
diffusion of gases or liquids into the pores of the solid

Practical examples:
mass transfer in porous catalysts
mass transfer in porous adsorbents
mass transfer in porous membranes
Knudsen diffusion:
important if:
gas mixture fill the pores of the solid object
the size of the pores is less than the mean free path
of the diffusing gas molecule
density of the gas is low.
Generally, the Knudsen process is significant only at low pressure and small
pore diameter. However, there are instances where both Knudsen diffusion
and molecular diffusion (DAB) can be important. If we consider that Knudsen
diffusion and molecular diffusion compete with one another by a ‘‘resistances
in series’’ approach, then the effective diffusivity of species A in a binary
mixture of A and B, DAe, is determined by
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.’’
For these materials, if an average pore diameter is assumed, a reasonable

approximation for the effective diffusion coefficient in random pores is
Example 6 Knudsen diffusion:
Convective Mass Transfer
 Mass transfer between a moving fluid and a surface,

or between two immiscible moving fluids.
 It depends both on the transport properties and on the dynamic

characteristics of the moving fluid.
 - Forced convection: due to external source (e.g. pump)

- natural (free) convection: due to density difference
 NA = kc ∆cA
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CHE 304

Elemental volume containing a multicomponent mixture

The molecular concentration of species A, cA, is defined as the number of

the ideal gas law

(Dalton’s law for gas mixtures)

The molar-average velocity

• Species in a mixture move at different velocities vi

• The diffusion relative velocity of species i

The figure below shows the molecular diffusion process schematically. A

• Total mass Flux: nA

For diffusion in only the z direction, the Fick rate equation is

Initial experimental investigations of molecular diffusion were unable to verify

This relation may be generalized and written in vector form as

If species A were diffusing in a multicomponent mixture, the expression equivalent

where DAM is the diffusion coefficient of A in the mixture

 JA = - DAB (dcA / dz) unit of DAB = ?

 DAB = f (T, P, composition of the system)

 (DAB)gas > (DAB)liquid > (DAB)solid

 Exp values for DAB are listed in tables J.1-J.3 (appendix)

 If exp values not available, you may use these correlations:

For a binary system composed of nonpolar molecular pairs, the Lennard–Jones

From Appendix Table K.2, the

with each component’s evaluated by

diffusion of gases or liquids into the pores of the solid

For these materials, if an average pore diameter is assumed, a reasonable

 Mass transfer between a moving fluid and a surface,

 It depends both on the transport properties and on the dynamic

 - Forced convection: due to external source (e.g. pump)

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