Fogler_ECRE_CDROM.

book Page 813 Wednesday, September 17, 2008 5:01 PM

Diffusion 12
and Reaction

Research is to see what everybody else sees, and

to think what nobody else has thought.
Albert Szent-Gyorgyi

Overview This chapter presents the principles of diffusion and reaction.

While the focus is primarily on catalyst pellets, examples illustrating these
principles are also drawn from biomaterials engineering and microelectronics.
In our discussion of catalytic reactions in Chapter 10, we assumed each
point on the interior of catalyst surface was accessible to the same concen-
tration. However, we know there are many, many situations where this equal
The concentration in accessibility will not be true. For example, when the reactants must diffuse
the internal surface inside the catalyst pellet in order to react, we know the concentration at the
of the pellet is less pore mouth must be higher than that inside the pore. Consequently, the entire
than that of the
external surface
catalytic surface is not accessible to the same concentration; therefore, the
rate of reaction throughout the pellet will vary. To account for variations in
reaction rate throughout the pellet, we introduce a parameter known as the
effectiveness factor, which is the ratio of the overall reaction rate in the pel-
let to the reaction rate at the external surface of the pellet. In this chapter we
will develop models for diffusion and reaction in two-phase systems, which
include catalyst pellets, tissue generation, and chemical vapor deposition
(CVD). The types of reactors discussed in this chapter will include packed
beds, bubbling fluidized beds, slurry reactors, trickle bed reactors, and CVD
boat reactors. After studying this chapter, you will be able to describe diffu-
sion and reaction in two- and three-phase systems, determine when internal
diffusion limits the overall rate of reaction, describe how to go about elimi-
nating this limitation, and develop models for systems in which both diffu-
sion and reaction play a role (e.g., tissue growth, CVD).

813
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814 Diffusion and Reaction Chap. 12

In a heterogeneous reaction sequence, mass transfer of reactants first takes

place from the bulk fluid to the external surface of the pellet. The reactants
then diffuse from the external surface into and through the pores within the
pellet, with reaction taking place only on the catalytic surface of the pores. A
schematic representation of this two-step diffusion process is shown in Figures
10-6 and 12-1.

Figure 12-1 Mass transfer and reaction steps for a catalyst pellet.

12.1 Diffusion and Reaction

in Spherical Catalyst Pellets
In this section we will develop the internal effectiveness factor for spherical
catalyst pellets. The development of models that treat individual pores and pel-
lets of different shapes is undertaken in the problems at the end of this chapter.
We will first look at the internal mass transfer resistance to either the products
or reactants that occurs between the external pellet surface and the interior of
the pellet. To illustrate the salient principles of this model, we consider the
irreversible isomerization
A ⎯⎯→ B
that occurs on the surface of the pore walls within the spherical pellet of radius R.

12.1.1 Effective Diffusivity

The pores in the pellet are not straight and cylindrical; rather, they are a series
of tortuous, interconnecting paths of pore bodies and pore throats with varying
cross-sectional areas. It would not be fruitful to describe diffusion within each
and every one of the tortuous pathways individually; consequently, we shall
define an effective diffusion coefficient so as to describe the average diffusion
taking place at any position r in the pellet. We shall consider only radial vari-
ations in the concentration; the radial flux WAr will be based on the total area
(voids and solid) normal to diffusion transport (i.e., 4r 2 ) rather than void area
alone. This basis for WAr is made possible by proper definition of the effective
diffusivity De .
The effective diffusivity accounts for the fact that:

1. Not all of the area normal to the direction of the flux is available (i.e.,
the area occupied by solids) for the molecules to diffuse.
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Sec. 12.1 Diffusion and Reaction in Spherical Catalyst Pellets 815

2. The paths are tortuous.

3. The pores are of varying cross-sectional areas.

An equation that relates De to either the bulk or the Knudsen diffusivity is

The effective DABφpσc

De = --------------------
- (12-1)
diffusivity τ̃
where
Actual distance a molecule travels between two points
t̃  tortuosity1 = ----------------------------------------------------------------------------------------------------------------------------------
Shortest distance between those two points
Volume of void space
φp  pellet porosity = -----------------------------------------------------------------------------
Total volume ( voids and solids )
c  Constriction factor
The constriction factor, c, accounts for the variation in the
cross-sectional area that is normal to diffusion.2 It is a function of the ratio of
maximum to minimum pore areas (Figure 12-2(a)). When the two areas, A1
and A2 , are equal, the constriction factor is unity, and when   10, the con-
striction factor is approximately 0.5.
A B

A2 A1

L
L

area A 1

(a) (b)
Figure 12-2 (a) Pore constriction; (b) pore tortuosity.

Example 12–1 Finding the Tortuosity

Calculate the tortuosity for the hypothetical pore of length, L (Figure 12-2(b)), from
the definition of t̃ .

1 Some investigators lump constriction and tortuosity into one factor, called the tortuos-
ity factor, and set it equal to t̃ ⁄ σc . C. N. Satterfield, Mass Transfer in Heterogeneous
Catalysis (Cambridge, Mass.: MIT Press, 1970), pp. 33–47, has an excellent discus-
sion on this point.
2 See E. E. Petersen, Chemical Reaction Analysis (Upper Saddle River, N.J.: Prentice

Hall, 1965), Chap. 3; C. N. Satterfield and T. K. Sherwood, The Role of Diffusion in

Catalysis (Reading, Mass.: Addison-Wesley, 1963), Chap. 1.
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816 Diffusion and Reaction Chap. 12

Solution
Actual distance molecule travels from A to B
t̃ = ------------------------------------------------------------------------------------------------------------
Shortest distance between A and B
The shortest distance between points A and B is 2 L . The actual distance the mol-
ecule travels from A to B is 2L.
2L
t̃ = ---------- = 2 = 1.414
2L
Although this value is reasonable for t̃ , values for t̃  6 to 10 are not unknown.
Typical values of the constriction factor, the tortuosity, and the pellet porosity are,
respectively, c  0.8, t̃  3.0, and φp  0.40.

12.1.2 Derivation of the Differential Equation

Describing Diffusion and Reaction

We now perform a steady-state mole balance on species A as it enters, leaves,

and reacts in a spherical shell of inner radius r and outer radius r  r of the
pellet (Figure 12-3). Note that even though A is diffusing inward toward the
center of the pellet, the convention of our shell balance dictates that the flux be
in the direction of increasing r. We choose the flux of A to be positive in the
First we will derive direction of increasing r (i.e., the outward direction). Because A is actually
the concentration
profile of reactant diffusing inward, the flux of A will have some negative value, such as
A in the pellet. 10 mol/m2 s, indicating that the flux is actually in the direction of decreas-
ing r.

CAs

r + Δr
r

Figure 12-3 Shell balance on a catalyst pellet.

We now proceed to perform our shell balance on A. The area that appears
in the balance equation is the total area (voids and solids) normal to the direc-
tion of the molar flux:
Rate of A in at r  WAr Area  WAr
4r 2  r (12-2)
Rate of A out at (r  r)  WAr Area  WAr
4r 2  rr (12-3)
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Sec. 12.1 Diffusion and Reaction in Spherical Catalyst Pellets 817

Rate of
generation
Rate of reaction Mass catalyst
of A within a  --------------------------------------- × -------------------------------- × Volume of shell
Mass of catalyst Volume
shell of thickness
Δr
 rA′ × ρc × 2
4 π rm Δ r
(12-4)
Mole balance for where rm is some mean radius between r and r  r that is used to approxi-
diffusion and
reaction inside the
mate the volume V of the shell and ρc is the density of the pellet.
catalyst pellet The mole balance over the shell thickness r is
Mole balance (In at r)  (Out at r + Δr)  (Generation within Δr)  0
(12-5)
( WAr × 4πr2 r )  ( WA r × 4 π r r  Δ r ) 
2 ( rA′ ρc × 4πrm2 Δr ) 0
After dividing by (4 r) and taking the limit as r → 0, we obtain
the following differential equation:
2
d( WArr ) 2
- – r′Aρcr = 0
-------------------- (12-6)
dr
Because 1 mol of A reacts under conditions of constant temperature and
pressure to form 1 mol of B, we have Equal Molar Counter Diffusion (EMCD)
at constant total concentration (Section 11.2.1A), and, therefore,
dy dC
The flux equation WAr = –cDe --------A = –De ---------A- (12-7)
dr dr
where CA is the number of moles of A per dm3 of open pore volume (i.e., vol-
ume of gas) as opposed to (mol/vol of gas and solids). In systems where we
do not have EMCD in catalyst pores, it may still be possible to use Equation
(12-7) if the reactant gases are present in dilute concentrations.
After substituting Equation (12-7) into Equation (12-6), we arrive at the
following differential equation describing diffusion with reaction in a catalyst
pellet:
2
d[ –De( dCA/dr )r ] 2
------------------------------------------- – r ρcr′A = 0 (12-8)
dr
We now need to incorporate the rate law. In the past we have based the
rate of reaction in terms of either per unit volume,
3
–rA[ = ](mol/dm ⋅ s)
or per unit mass of catalyst,
–r′A [ = ](mol/g cat ⋅ s)