15

(3) Diffusion

In this section we will consider applications of the mass transfer equations for the case in
which there is no bulk flow of the material induced by mechanical action. In other words, we will
consider motion of the material due to diffusion only. The section is organized as follows: first,
we will consider examples of steady-state, one-dimensional diffusion in the absence of chemical
reactions; second, we will analyze steady-state diffusion problems with chemical reactions; and,
finally, we will analyze transient diffusion problems.
The problems to be solved here will correspond to binary systems or multicomponent systems
in which the species whose transport is being studied (A) is present at dilute conditions (xA«1).
The approach to a specific problem will depend on whether the mixture is dilute in A or not:
(1) For dilute systems, equation (69) applies. Note that taking v=0 is really an approximation,
since A will be diffusing and hence there will be motion in the material. However, bulk motion
will be negligible due to the low concentrations of A. In terms of the representation of the molar
flux of A (equation 31), we can see that, since xA«1, we can state that

N A ≈ J *A (70)

and the components of the molar flux of A can be directly found from Fick's law (equations in
pages 13 and 14 for various coordinate systems). In this case, a diffusion problem is analogous to
a heat conduction problem, with concentration replacing temperature and molar flux of A
replacing conductive heat flux.
(2) For concentrated systems (binary: A and B), the continuity equation in terms of the molar
flux (equation 60) must be used, along with the general form of the flux equation (equation 61).
For these problems, information will be needed on both components (i.e. if solving for
concentration profiles and flux of A, we will need to have information on the flux of B).

One-dimensional, steady-state diffusion

(1) Steady diffusion through an annular membrane.
Solid membranes through which components of a mixture can diffuse are used often as
separation devices. Separation will occur if the diffusion rates of the various components through
the membrane are different. In this example, we will consider the diffusion of a species (A)
through an annular solid membrane made of a species B that separates two fluids with different
concentrations of A (Figure 4). The conditions and assumptions for this application are:
- Steady state.
- No chemical reactions in the membrane, RA=0.
- Species A is dilute in the membrane (xA«1).
- Symmetry in both z and θ directions allows us to state that the concentration will depend
only on radial direction: cA=cA(r) in the membrane.
- Within the membrane, c and DAB are uniform.
- The fluid inside the cylinder is the same as outside the cylinder, and the concentration of A
in the fluid is uniform (cA1 and cA2 are uniform in the fluid phases).
- At the fluid/solid interface, the principle of local equilibrium implies that the concentration
of A in the membrane is at equilibrium with the concentration of A in the liquid. We will assume
that the equilibrium relation is linear, so that equilibrium is represented by the equation

c Am = Kc Af (71)
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where cAm is the concentration of A in the membrane that would be at equilibrium with a
concentration of A in the fluid cAf, and K is a constant. An equilibrium equation like equation
(71) is called a linear partitioning (it is identical to Henry's law for a gas/liquid system), and K is
called the partition coefficient.

Figure 4. A long annular membrane of thickness R2-R1 separates two fluids with different
concentration of A.

With all the conditions listed above, the diffusion equation in cylindrical coordinates (page
14) simplifies to

d ⎛ dc A ⎞
⎜r ⎟=0 (72)
dr ⎝ dr ⎠

Integrating this equation twice leads to the solution

c A = a1 ln r + a 2 (73)

where a1 and a2 are integration constants. To determine these two constants, we will use the
boundary conditions that are a result of the equilibrium condition (71):

cA=KcA1, r=R1 (74)

cA=KcA2, r=R2 (75)

using these two conditions to find the integration constants yields the concentration profile:

ln(r / R1 )
c A = Kc A1 − K (c A1 − c A 2 ) (76)
ln(R 2 / R1 )

The molar flux of A is given by

dc A
N Ar = −D AB (77)
dr
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which yields

D ABK (c A1 − c A 2 )
N Ar = (78)
r ln(R 2 / R1 )

The solution presented here is mathematically equivalent to the solution for heat conduction in a
cylindrical wall (page II-14). Note that the fact that the molar flux of A is inversely proportional
to r is due to the increase in area with r. At any radial position, we can calculate the molar flow
rate of A in the radial direction by

WAr = 2πrLN Ar (79)

where L is the length of the cylinder. This yields

(c A1 − c A 2 )
WAr = 2πLD ABK (80)
ln(R 2 / R1 )

which is independent of r because of mass conservation.

The solution found assumes that mass transfer within the fluids is fast enough that
concentrations within them are uniform (cA1 and cA2). If this is not the case and mass transfer in
the fluids occurs by convection, the concentration of A at the fluid/membrane interface will be
different from the bulk concentration in the fluid. The concentration profile in this case is
illustrated in Figure 5 for cA1>cA2. The fact that the concentrations of A at the fluid/membrane
interfaces (cAi1 and cAi2) are at equilibrium with those in the membrane leads to a discontinuity of
the concentration at the interface. This is the only difference between the mathematical analysis
of this problem and that of heat conduction where the temperature is a continuous function of
position, even across phase boundaries.
For the case shown in Figure 5, the application of equation (80) yields

(c Ai1 − c Ai2 )
WAr = 2πLD ABK (81)
ln(R 2 / R1 )

To find the interfacial concentrations, we represent the fluxes at the interfaces using convective
mass transfer coefficients,

N Ar r = R = k c1 (c A1 − c Ai1 ) (82)
1

N Ar r = R = k c2 (c Ai2 − c A 2 ) (83)
2

From these, we can find the molar flow rate of A, which is the same everywhere:

WAr = 2πR 1Lk c1 (c A1 − c Ai1 ) (84)

WAr = 2πR 2 Lk c 2 (c Ai 2 − c A 2 ) (85)

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Figure 5. Shape of the concentration profiles when there is transport by convection in the
fluids.

In typical applications, equations (81), (84) and (85) conform a system of three equations
with three unknowns (WAr, cAi1 and cAi2). The usual way used to solve this system is to divide the
equations by the factor that multiplies the concentration difference and add them all up to
eliminate the interfacial concentrations (see pages II-16 and II-17 for a similar procedure). The
result is

2πL(c A1 − c A 2 )
WAr = (86)
1 ln(R 2 / R1 ) 1
+ +
R1k c1 D AB K R 2 k c2

Each terms in the denominator of this equation can be interpreted as a mass transfer resistance,
using an analysis similar to that applied to heat transfer problems.