Differential Equations of Mass Transfer

THE DIFFERENTIAL EQUATION FOR MASS TRANSFER

Consider the control volume, x y z, through which a mixture including
component A is flowing, as shown in Figure 25.1. The control-volume
expression for the conservation of mass is:

If we consider the conservation of a given species A, this relation should also

include a term that accounts for the production or disappearance of A by
chemical reaction within the volume. The general relation for a mass balance
of species A for our control volume may be stated as:

The individual terms will be evaluated for constituent A, and a discussion of

their meanings will be given below. The net rate of mass efflux from the
control volume may be evaluated by considering the mass transferred across
control surfaces. For example, the mass of A transferred across the area y
z at x will be AvAx y z|x, or in terms of the flux vector, nA= AvA, it would
be nA,x y z|x. The net rate of mass efflux of constituent A will be
If A is produced within the control volume by a chemical reaction at a rate rA,
where rA has the units (mass of A produced) / (volume) (time), the rate of
production of A is:

rA x y z
Substituting each term in equation (25-1), we obtain:

Equation (25-4) is the equation of continuity for component A. As nA,x; nA,y;

and nA,z are the rectangular components of the mass flux vector, nA, equation
(25-4) may be written
 A similar equation of continuity may be developed for a second
constituent B in the same manner. The differential equations are

where rB is the rate at which B will be produced within the control volume by
a chemical reaction. Adding equations (25-5) and (25-7), we obtain

For a binary mixture of A and B, we have

nA + nB = AvA + BvB = v
A + B = 
and
rA = - r B

by the law of conservation of mass. Substituting these relations into (25-8),

we obtain

We could follow the same development in terms of molar units. If RA

represents the rate of molar production of A per unit volume, and RB
represents the rate of molar production of B per unit volume, the molar-
equivalent equations are
SPECIAL FORMS OF THE DIFFERENTIAL MASS-TRANSFER
EQUATION
Special forms of the equation of continuity applicable to commonly
encountered situations follow. In order to use the equations for evaluating the
concentration profiles, we replace the fluxes, nA and NA, by the appropriate
expressions developed in Chapter 24. These expressions are
Either equation (25-15) or (25-16) may be used to describe concentration
profiles within a diffusing system. Both equations are completely general;
however, they are relatively unwieldy. These equations can be simplified by
making restrictive assumptions. Important forms of the equation of continuity,
with their qualifying assumptions, include:
(i) If the density, , and the diffusion coefficient, DAB can be assumed
constant, equation (25-15) becomes

Dividing each term by the molecular weight of A and rearranging, we obtain

(ii) If there is no production term, RA = 0, and if the density and diffusion

coefficient are assumed constant, equation (25-17) reduces to
(iii) In a situation in which there is no fluid motion, v = 0, no production term,
RA = 0, and no variation in the diffusivity or density, equation (25-18) reduces
to

Equation (25-20) is commonly referred to as Fick’s second “law” of diffusion.

The assumption of no fluid motion restricts its applicability to diffusion in
solids, or stationary liquids, and for binary systems of gases or liquids, where
NA is equal in magnitude, but acting in the opposite direction to N; that is, the
case of equimolar counter diffusion. Equation (25-20) is analogous to
Fourier’s second ‘‘law’’ of heat conduction
COMMONLY ENCOUNTERED BOUNDARY CONDITIONS
The initial condition in mass transfer processes is the concentration of the
diffusing species at the start of the time interval of interest expressed in either
mass or molar concentration units. The concentration may be simply equal to
a constant, for example

Four types of boundary conditions are commonly encountered in mass

transfer.
(1) The concentration of the transferring species A at a boundary surface
is specified. Surface concentration can assume a variety of units, for
example, molar concentration cAs, mass concentration As, gas mole
fraction yAs, liquid mole fraction xAs, etc. When the boundary surface
is defined by a pure component in one phase and a mixture in the
second phase, then the concentration of transferring species A in the
mixture at the interface is usually at thermodynamic saturation
conditions. Specifically, for a gas mixture in contact with a pure
volatile liquid A or pure volatile solid A, the partial pressure of species
A in the gas at the surface is saturation vapor pressure, PA, so that pAs
= PA. For a liquid mixture in contact with a pure solid A, the
concentration of species A in the liquid at the surface is the
For a contacting gas and liquid where transferring species A is present in both
phases, there are two ways to specify the concentration at the gas–liquid
interface. First, if both of the species in the liquid phase are volatile, then the
boundary condition at the gas–liquid surface is defined for an ideal liquid
mixture by Raoult’s law

where xA is the mole fraction in the liquid, PA is the vapor pressure of species
A evaluated at the temperature of the liquid, and PAs is the partial pressure of
species A in the gas. The partial pressure of species A at the interface is related
to surface mole fraction yAs by Dalton’s law

Second, for solutions where species A is only weakly soluble in the liquid,
Henry’s law may be used to relate the mole fraction of A in the liquid to the
partial pressure of A in the gas

where coefficient H is known as Henry’s constant. Values of H in pressure

units for selected gaseous solutes dissolved in aqueous solution are listed in
Table 25.1. A similar equation may also be used to determine the boundary
conditions at a gas–solid interface

where cA; solid is the molar concentration of A within the solid at the interface
in units of kg mol/m3 and pA is the partial pressure of gas phase species A over
the solid in units of Pa. The partition coefficient S, also known as the solubility
constant, has units of kg mol/m3Pa. Values of S for several gas–solid pairs
reported by Barrer1 are listed in Table 25.2.
(2) A reacting surface boundary is specified. There are three common
situations, all dealing with heterogeneous surface reactions. First, the flux of
one species may be related to the flux of another species by chemical reaction
stoichiometry. For example, consider the generic chemical reaction at the
boundary surface A + 2B  3C, where reactants A and B diffuse to the
surface, and product C diffuses away from the surface. The fluxes for A and
B move in the opposite direction to the flux for C. Consequently, the flux NA
is related to the flux of the other species by NB = +2NA or NC =-3 NA. Second,
a finite rate of chemical reaction might exist at the surface, which in turn sets
the flux at the surface. For example, if component A is consumed by a first-
order on a surface at z = 0, and the positive z direction is opposite to the
direction of flux of A along z, then

where ks is a surface reaction rate constant with units of m/s. Third, the
reaction may be so rapid that cAs = 0 if species A is the limiting reagent in the
chemical reaction.
(3) The flux of the transferring species is zero at a boundary or at a centerline
of symmetry. This situation can arise at an impermeable boundary, or at the
centerline of symmetry of the control volume, where the net flux is equal to
zero. In either case, for a one-dimensional flux along z

where the impermeable boundary or the centerline of symmetry is located at

z = 0.
(4) The convective mass transfer flux at the boundary surface is specified.
When a fluid flows over the boundary, the flux can be defined by convection.
For example, at some surface located at z = 0, the convective mass transfer
flux across the fluid boundary layer is
where cA∞ is the bulk concentration of A the flowing fluid, cAs is the surface
concentration of A at z = 0 and kc is the convection mass-transfer coefficient
defined in Section 24.3.

Solve examples 1, 2, and 3