15.

Diffusion and Reaction

Research is to see what everybody else sees, and to think what nobody else has thought.

—Albert Szent-Gyorgyi

1. Diffusion and Reactions in Homogeneous Systems

For homogeneous systems, the mole balance on species A, Equation

(14-2), for one-dimensional diffusion at steady state is

For diffusion through a stagnant film at dilute

concentrations, Equation (14-9) becomes

Substituting in Equation (14-2) one obtains

Understanding and modeling diffusion with chemical

reaction is not only important for industrial catalysts
but also has many other applications. These
applications include medicine, cancer treatment
using drug laced particulates, and, as shown in the
Expanded Material on the CRE Web site
(www.umich.edu/~elements/5e/index.html), tissue engineering. In P15-15B,
we discuss the diffusion and reaction of oxygen in cartilage.

We will now discuss solid-gas catalytic reactions and diffusion limitation

in catalyst pellets.

2. Diffusion and Reactions in Spherical Catalyst Pellets

The following sections of this chapter will focus solely on the transport
and reaction in heterogeneous systems with catalyst pellets. In a
heterogeneous reaction sequence, mass transfer of reactants must first
take place from the bulk fluid to the external surface of the pellet. The
reactants then diffuse from the external surface into and through the
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pores within the pellet (CAs > CA(r)), 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, 14-1, and 15-1.

Figure 15-1 Mass transfer and reaction steps for a catalyst pellet.

In Chapter 14 we discussed external diffusion. In this section we will

discuss internal diffusion and develop the internal effectiveness factor for
spherical catalyst pellets. The development of models that treat
individual pores and pellets 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 reaction 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

that occurs on the surface of the pore walls within the spherical pellet of
radius R.

15.2.1 Effective Diffusivity

To reach the inner surface, the reactant A must diffuse from a higher
reactant concentration at the pellet external surface into and through
the pores of pellets which are at a lower concentration as shown in
Figure 15-1.

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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
interior position r in the pellet. We shall consider only radial variations in
the concentration; the radial flux WAr will be based on the total area
(voids and solid) normal to diffusion transport (i.e., 4πr2) 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.

2. The paths are tortuous.

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

An equation that relates the effective diffusivity De to either the bulk

diffusivity DAB or the Knudsen diffusivity DK is

The effective diffusivity

where

1
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1Some investigators lump the constriction factor and tortuosity into one
factor, called the tortuosity factor, and set it equal to . See C. N.
Satterfield, Mass Transfer in Heterogeneous Catalysis (Cambridge, MA: MIT
Press, 1970), pp. 33–47.

The constriction factor, σc, 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 15-2()). When the two areas,
A1 and A2, are equal, the constriction factor is unity, and when β = 10,
the constriction factor is approximately 0.5.

2SeeE. E. Petersen, Chemical Reaction Analysis (Upper Saddle River, NJ:

Prentice Hall, 1965), Chap. 3; C. N. Satterfield and T. K. Sherwood, The
Role of Diffusion in Catalysis (Reading, MA: Addison-Wesley, 1963), Chap.
1.

Figure 15-2 (a) Pore constriction; (b) pore tortuosity.

Example 15–1 Finding the Effective Diffusivity De

Using typical values of DAB, ϕ p, σc, and τ, estimate the effective

diffusivity, De.

Solution

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 First, calculate the tortuosity for the hypothetical pore of length, L
(Figure 15-2()), from the definition of .

The shortest distance

between points A and B for
the idealized pore shown in
Figure 15-2() is . The
actual distance the
molecule travels from A to
B is 2L.

Although this value is reasonable for , values for

to 10 are not uncommon. Typical values of
the constriction factor, the tortuosity, and the
pellet porosity are, respectively, σc = 0.8, , and ϕ p = 0.40.
A typical value of the gas = phase diffusivity is DAB = 10–6 m2/s.

Using these values in Equation (15-1)

therefore

De = 0.1 • 10–6 m2/s = 10–7 m2/s

Analysis: The purpose of this example was to give an understanding of

tortuosity and help the reader understand how it decreases De. We also
see that a representative value of the effective diffusivity in the porous
pellet is 10% of the gas-phase diffusivity.

15.2.2 Derivation of the Differential Equation Describing Diffusion and

Reaction in a Single Catalyst Pellet

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
+ Δr of the pellet (Figure 15-3). Note that even though A is diffusing
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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 direction of increasing r (i.e., the
outward direction). Because A is actually diffusing inward, the flux of A
will have some negative value, such as (–10 mol/m2 · s), indicating that
the flux is actually in the direction of decreasing r.

First, we will derive the concentration profile of reactant A in the pellet.

Figure 15-3 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 direction of the molar
flux shown by the arrows in
Figure 15-3.

Mole balance for diffusion and reaction inside the catalyst pellet

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where rm is some mean radius between r and r + Δr that is used to
approximate the volume ΔV of the shell, and ρc is the density of the
pellet.

The mole balance over the shell thickness Δr is

Mole balance

After dividing by (–4π Δr) and taking the limit as Δ r → 0, we obtain the
following differential equation

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 molar concentration (Section 14.2.1) and,
therefore

The flux equation

where CA is the number of moles of A per dm3 of open-pore volume (i.e.,

volume 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 (15-7) if the reactant gases are present in dilute
concentrations.

After substituting Equation (15-7) into Equation (15-6), we arrive at the

following differential equation describing diffusion with reaction in a
catalyst pellet

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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

or per unit mass of catalyst

When we study reactions on the internal surface

area of catalysts, the rate of reaction and rate
law are often based on per unit surface area

As a result, the surface area of the catalyst per unit

mass of catalyst

Sa [=] (m2/g-cat)

is an important property of the catalyst. The rate of

reaction per unit mass of catalyst, , and the
rate of reaction per unit surface area of catalyst
are related through the equation

Sa: 10 grams of catalyst may cover as much

surface area as a football field.

A typical value of Sa might be 150 m2/g of catalyst.

The rate law

As mentioned previously, at high temperatures,

the denominator of the catalytic rate law often
approaches 1 as discussed in Section 10.3.7. Consequently, for the
moment, it is reasonable to assume that the surface reaction is of nth
order in the gas-phase concentration of A within the pellet

where the units of the rate constants for –r A, , and are

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Similarly,

Substituting the rate-law equation (15-9) into Equation (15-8) gives

Differential equation and boundary conditions describing diffusion and

reaction in a catalyst pellet

Letting kn represent the terms under the bracket, differentiating the first
term and dividing through by –r2De, Equation (15-10) becomes

The boundary conditions are:

1. The concentration remains finite at the center of the pellet

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2. At the external surface of the catalyst
pellet, the concentration is CAs

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15.2.3 Writing the Diffusion with the Catalytic Reaction Equation in

Dimensionless Form

We now introduce dimensionless variables ψ and λ so that we may

arrive at a parameter that is frequently discussed in catalytic reactions,
the Thiele modulus. Let

With the transformation of

variables, the boundary
condition

becomes

and the boundary condition

becomes

We now rewrite the differential equation for

the molar flux in terms of our dimensionless
variables. Starting with

we use the chain rule to write

Then differentiate Equation (15-12) with respect to ψ and Equation (15-
13) with respect to r, and substitute the resulting expressions

into Equation (15-14) to obtain

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The flux of A in terms of the dimensionless variables, ψ and

The
λ, is flux of A in terms of the dimensionless variables, ψ and
λ, is

• The total rate of consumption of A inside the pellet, MA (mol/s)

At steady state, the net flow of species A that enters into the pellet at the external
pellet surface reacts completely within the pellet. The overall rate of reaction is
therefore equal to the total molar flow of A into the catalyst pellet. The overall rate
of reaction, MA (mol/s

• All the reactant that diffuses into the pellet is consumed (a black
hole).

• Consequently, to determine the overall rate of reaction

• Differentiating the concentration gradient, Equation (15-15),

After dividing by CAs/R2, the dimensionless form of Equation (15-11) is
written as

Then 12/77

Dimensionless form of equations describing diffusion and reaction

where

The square root of the coefficient of ψn in Equation 15-19 (i.e., ϕn) is

called the Thiele modulus (pronounced th –l ). The Thiele modulus, ϕn,
will always contain a subscript (e.g., n), which refers to the reaction
order and distinguishes this symbol from the symbol for porosity, ϕ,
used in the Ergun pressure drop equation and defined in Chapter 5,
which has no subscript. The quantity is a measure of the ratio of
“a” surface reaction rate to “a” rate of diffusion through the catalyst
pellet

Thiele modulus

When the Thiele modulus is large, internal diffusion usually limits the overall
rate of reaction; when ϕn is small, the surface reaction is usually rate-
limiting. If, for the first order reaction

A→B
Limiting conditions:

the reaction were surface reaction rate limited with respect to the
adsorption of A and desorption of B, and if A and B were weakly
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adsorbed (i.e., low surface coverage), we can write the apparent first-
order reaction rate law per unit volume of pellet as

–rA = k1CA

where k1 is the rate constant for a single catalyst pellet.

Recalling k1 = Saρck″ we could also write the rate in terms of pellet

catalytic surface area (mol/m2•s)

The units of are m3/m2 s (= m/s).

For a first-order reaction, Equation (15-19) becomes

the Thiele modulus for this first-order reaction is

where
 14/77

The boundary conditions are

15.2.4 Solution to the Differential Equation for a First-Order Reaction

Differential equation (15-22) is readily solved with the aid of the

transformation y = ψλ:

With these transformations, Equation (15-

22) reduces to

This differential equation has the following solution (see Appendix A.3):

y = A1 cosh ϕ1λ + B1 sinh ϕ1λ

In terms of ψ,
The arbitrary constants A1 and B1 can
easily be evaluated with the aid of the
boundary conditions. At λ = 0, cosh ϕ1λ
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→ 1, (1/λ) → ∞, and sinh ϕ1λ → 0. Because the second boundary condition
requires ψ to be finite at the center (i.e., λ = 0), therefore A1 must be
zero.

The constant B1 is evaluated from B.C. 1 (i.e., ψ = 1, λ = 1) and the

dimensionless concentration profile is

Concentration profile

Figure 15-4 shows the concentration profile for three different values of
the Thiele modulus, ϕ1 . Small values of the Thiele modulus indicate
surface reaction controls and a significant amount of the reactant
diffuses well into the pellet interior without reacting. As a result, the
concentration profile is very shallow, with the concentration at the
center of the pellet being close to that at the external surface. That is,
virtually the entire internal surface is accessible to the reactant
concentration CAs. Large values of the Thiele modulus indicate that the
surface reaction is rapid and that the reactant is consumed very close to
the external pellet surface and very little penetrates into the interior of
the pellet. Consequently, if the porous pellet is to be plated with a
precious metal catalyst (e.g., Pt), it should only be plated in the
immediate vicinity of the external surface when large values of ϕn
characterize the diffusion and reaction. That is, it would be a waste of
the precious metal to plate the entire pellet when internal diffusion is
limiting because the reacting gases are consumed near the outer
surface. Consequently, the reacting gases would never contact the
center portion of the pellet.
Figure 15-4 Concentration profile in a
spherical catalyst pellet.

For large values of the Thiele modulus,

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internal diffusion limits the rate of
reaction.

3. The Internal Effectiveness Factor

In Figure 15-4 we saw that the concentration varied with the pellet
radius. Consequently, for all but zero-order reactions, the rate will also
vary throughout the pellet. In order to account for this variation in rates,
we introduce the internal effectiveness factor.

1. Isothermal First-Order Catalytic Reactions

The magnitude of the effectiveness factor (ranging from 0 to 1) indicates

the relative importance of diffusion and reaction limitations. The
internal effectiveness factor is defined as

η is a measure of how far the reactant diffuses into the pellet before
reacting.

The overall rate, , is also referred to as the observed rate of reaction

[–rA (obs)]. In terms of symbols, the effectiveness factor is
To derive the effectiveness factor for a first-order reaction, it is easiest to
work in reaction rates of moles per unit time, MA, rather than in moles
per unit time per volume of catalyst (i.e., –rA)
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First, we shall consider the denominator, MAs . If the entire surface were
exposed to the concentration at the external surface of the pellet, CAs,
the rate for a first-order reaction would be

The subscript s indicates that the rate –rAs is evaluated at the conditions
(e.g., concentration, temperature) present at the external surface of the
pellet (i.e., λ = 1).

The actual rate of reaction is the rate at which the reactant diffuses into
the pellet at the outer surface; that is, all of A that diffuses into the pellet
at the outer surface reacts and no A diffuses back out. (It behaves as a
“black hole.”) We recall Equation (15-17) on page 727 for the actual rate
of reaction

The actual rate of reaction

Differentiating Equation (15-27) and then evaluating the result at λ = 1

yields

Substituting Equation (15-30) into (15-17) gives us

We now substitute Equations (15-29) and (15-31) into Equation (15-28)
to obtain an expression for the effectiveness factor
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Internal effectiveness factor for a first-order reaction in a spherical

catalyst pellet

A plot of the effectiveness factor as a function of the Thiele modulus is

shown in Figure 15-5. Figure 15-5(a) shows η as a function of the Thiele
modulus, ϕs, for a spherical catalyst pellet for reactions of zero, first, and
second order. Figure 15-5(b) corresponds to a first-order reaction
occurring in three differently shaped pellets of volume Vp and external
surface area Ap, and where the Thiele modulus for a first-order reaction,
ϕ1, is defined differently for each shape. When volume change
accompanies a reaction (i.e., ε ≠ 0), the corrections shown in Figure 15-6
apply to the effectiveness factor for a first-order reaction.
We observe that as the particle diameter becomes
very small, ϕn decreases, so that the effectiveness
factor approaches 1 and the reaction is surface
reaction-limited. On the other hand, when the 19/77

Thiele modulus ϕn is large (e.g., 30), the

internal effectiveness factor η is small (e.g.,
0.1), and the reaction is diffusion-limited within
the pellet.
Consequently, factors influencing the rate of external mass transport
such as fluid velocity will have a negligible effect on the overall reaction
rate when the reaction is either internal surface reaction rate limited or
internal diffusion limited. For large values of the Thiele modulus, the
effectiveness factor can be written as
20/77
Figure 15-5 (a) Effectiveness factor plot for nth-order kinetics on
spherical catalyst particles. [Satterfield, C. N. “Mass Transfer in
Heterogeneous Catalysis,” AIChE Journal 16(3) 509–510 (1970). With
permission of the American Institute of Chemical Engineers. Copyright 21/77 ©
1970 AIChE. All rights reserved.] (b) First-order reaction in different pellet
geometrics. [Aris, R. Introduction to the Analysis of Chemical Reactors,
1965, p. 131; reprinted by permission of Pearson Education, Upper
Saddle River, NJ.]

To express the overall rate of reaction in terms of the Thiele modulus,

we rearrange Equation (15-28) and use the rate law for a first-order
reaction in Equation (15-29)

For a first-order reaction

Combining Equations (15-33) and (15-34), the overall rate of reaction for
a first-order, internal-diffusion-limited reaction is

Note that for catalytic packed

beds the rate varies inversely
with the particle diameter of
the catalyst.

15.3.2 Effectiveness Factors

with Volume Change with
Reaction

When there is volume change, ε ≠ 0, we use a correction factor to

account for this change. The correction is obtained from a plot of the
ratio of effective factors
as a function of ε for various values of the Thiele modulus. This plot is 22/77

given in Figure 15-6.

For example, if the Thiele modulus were 10 for the gas-phase reaction
A
→ 2B with (ε = 1) then the effectiveness factor with volume change would
be η′ = 0.8η .

How can the rate of reaction be increased?

15.3.3 Internal Diffusion Limited Reactions Other Than First Order

To increase the reaction rate, , for internal diffusion limited

reactions, we can (1) decrease the radius R (make pellets smaller); (2)
increase the temperature; (3) increase the concentration; and (4)
increase the internal surface area. For reactions of order n, we have
from Equation (15-20)
 23/77

Figure 15-6 Effectiveness factor ratios for first-order kinetics on spherical

catalyst pellets for various values of the Thiele modulus of a sphere, ϕs,
as a function of volume change. [From V. W. Weekman and R.
L. Goring, “Influence of Volume Change on Gas-Phase Reactions in
Porous Catalysts.” J. Catal., 4(2), 260 (1965).]

Correction for volume change with reaction (i.e., ε ≠ 0)

For large values of the Thiele modulus, the effectiveness factor is

Consequently, for reaction orders greater than 1, the effectiveness

factor decreases with increasing concentration at the external pellet
surface.

15.3.4 Weisz–Prater Criterion for Internal Diffusion Limitations

The Weisz–Prater criterion uses measured values of the rate of

reaction,
 (obs), to determine if internal diffusion is limiting the reaction. This
criterion can be developed intuitively for a first-order reaction by first
rearranging Equation (15-32) in the form
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The left-hand side is the Weisz–Prater parameter:

Showing where the Weisz–Prater comes from

Substituting for

in Equation (15-59) we obtain

Are there any internal diffusion limitations indicated from the Weisz–
Prater criterion?

All the terms in Equation (15-39) are either measured or known.

Consequently, we can calculate CWP to learn if there are any diffusion
limitations.

If
No diffusion limitations

there are no diffusion limitations and consequently no concentration 25/77

gradient exists within the pellet.

However, if

Severe diffusion limitations

internal diffusion limits the reaction severely. Ouch!

Example 15–2 Estimating the Thiele Modulus and Effectiveness Factor

The first-order reaction

was carried out over two different-sized pellets. The

pellets were contained in a spinning basket reactor that
was operated at sufficiently high rotation speeds that external mass
transfer resistance was negligible. The results of two experimental runs
made under identical conditions are given in Table E15-2.1.

(a) Estimate the Thiele modulus and effectiveness factor for each pellet.

(b)How small should the pellets be made to virtually eliminate all

internal diffusion resistance, e.g., η = 0.95?

These two experiments yield an enormous amount of

information.

Solution

(a) Combining Equations (15-36) and (15-39), we obtain

Letting the subscripts 1 and 2 refer to runs 1 and 2, we apply Equation
(E15-2.1) to runs 1 and 2 and then take the ratio to obtain

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The terms ρc, De, and CAs cancel because the runs were carried out
under identical conditions. The Thiele modulus is

Taking the ratio of the Thiele moduli for runs 1 and 2, we obtain

or

Substituting for ϕ11 in Equation (E15-2.2) above and evaluating and

R for runs 1 and 2 gives us

We now have one equation and one unknown. Solving Equation (E15-
2.7) we find that
The corresponding effectiveness
factors are

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Given two experimental points, one can predict the particle size where
internal mass transfer does not limit the rate of reaction.

(b) Next we calculate the particle radius needed to virtually eliminate

internal diffusion control (say, η = 0.95)

The solution to Equation (E15-2.8) yields ϕ 13 = 0.9

A particle size of 0.55 mm is

necessary to virtually
eliminate diffusion control
(i.e., η = 0.95).

Analysis: This example is important because it shows us how, with only

two measurements and some assumptions, we can determine internal
diffusion limitations for the two pellet sizes, and predict the pellet size
necessary to completely eliminate internal diffusion.

15.4 Falsified Kinetics

There are circumstances under which the measured reaction order and
activation energy are not the true values. Consider the case in which we
obtain reaction-rate data in a differential reactor at two different
temperatures, T1 and T2, where precautions are taken to virtually
eliminate external mass transfer resistance (i.e., CAs = CAb). From these
data, we construct a log-log plot of the measured rate of reaction
as a function of the gas-phase concentration, CAs (Figure 15-7). The slope
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of this plot is the apparent reaction order n’ and the measured rate law
takes the form

You may not be measuring what you think you are.

Measured rate:

Measured rate with apparent reaction order n’

Figure 15-7 Determining the

apparent reaction order (–rA =
ρb ( )).

We will now proceed to relate

this measured reaction order n’
to the true reaction order n.
Using the definition of the
effectiveness factor, noting that
the actual rate, , is the
product of η and the rate of
reaction evaluated at the
external surface, , i.e.,

Actual rate:

For large values of the Thiele modulus, ϕn, where internal mass is
limiting, we can use Equation (15-38) to substitute into Equation ( 15-41)
to obtain
Simplifying
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We equate the true reaction rate, Equation (15-42), to the measured

reaction rate, Equation (15-40), to get

The functional dependence of the reaction rate on concentration must

be the same for both the measured rate and the theoretically predicted
rate

therefore the measured apparent reaction order n’

(nApparent) is related to the true reaction order n (nTrue)
by

The true and the apparent reaction order

In addition to an apparent reaction order, there is also an apparent

activation energy, EApp . This value is the activation energy we would
calculate using the experimental data from the slope of a plot of ln (
) as a function of (1/T) at a fixed concentration of A. Substituting for the
measured and true specific reaction rates in terms of the activation
energy gives
into Equation (15-43), we find
that

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Taking the natural log of both sides gives us

where ET is the true activation energy.

As with the dependence rate on concentration, the temperature

dependence must be the same for the analytical rate. Comparing the
temperature-dependent terms on the right- and left-hand sides of
Equation (15-45), we see that the true activation energy is equal to twice
the apparent activation energy.

The true activation energy

This measurement of the apparent reaction order and activation energy

results primarily when internal diffusion limitations are present and is
referred to as disguised or falsified kinetics. Serious consequences could
occur if the laboratory data were taken in the disguised regime and the
reactor were operated in a different regime. For example, what if the
particle size were reduced so that internal diffusion limitations became
negligible? The higher activation energy, ET, would cause the reaction to
be much more temperature sensitive, and there is the possibility for
runaway reaction conditions causing an explosion to occur.
Important industrial consequence of falsified kinetic runaway reactions.
Safety considerations!

15.5 Overall Effectiveness Factor 31/77

For first-order reactions, we can use an overall effectiveness factor to

help us analyze diffusion, flow, and reaction in packed beds. We now
consider a situation where external and internal resistance to mass
transfer to and within the pellet are of the same order of magnitude (
Figure 15-8). At steady state, the transport of the reactant(s) from the
bulk fluid to the external surface of the catalyst is equal to the net rate
of reaction of the reactant within and on the pellet.

Figure 15-8 Mass transfer and reaction steps.

Here, both internal and external diffusion are important.

The molar rate of mass transfer from the bulk fluid to the external
surface is

where ac is the external surface area per unit reactor volume (cf.
Chapter 14) and ΔV is the volume.

This molar rate of mass transfer to the surface, MA, is equal to the net
(total) rate of reaction on and within the pellet
 32/77

See nomenclature note in Example 15-4.

Recall that ρc is the density of catalyst pellet, kg per

volume of pellet and ρB is the bulk density of catalyst,
kg-cat per reactor volume.

We now combine the above equations, to obtain total molar flow into all
the catalyst in volume ΔV

Combining Equations (15-47) and (15-48), and canceling the volume ΔV,
we see the flux to the pellet surface, WAzac, is equal to the rate of
consumption of A in and on the catalyst.

For most catalysts, the internal surface area

is much greater than the external surface
area (i.e., ), in which case we
have

Comparing units on the r.h.s. and l.h.s. of Equation

(15-49), we find
where is the overall rate of
reaction within and on the pellet per
unit surface area, is the rate of
reaction per mass of catalyst 33/77

and –rA is the overall rate per volume of reactor, i.e.,

then

with the corresponding units for each term in Equation (15-49) shown
below.

The relationship for the rate of

mass transport to the external
catalyst surface is

Again, comparing units on the l.h.s. and r.h.s.

where kc is the external mass transfer coefficient (m/s). Because internal

diffusion resistance is also significant, not all of the interior surface of
the pellet is accessible to the concentration at the external surface of the
pellet, CAs . We have already learned that the effectiveness factor is a
measure of this surface accessibility [see Equation (15-41)]:
 34/77

Assuming that the surface reaction is first order with respect to A, we

can utilize the internal effectiveness factor to write

Recall that

We need to eliminate the surface concentration from

any equation involving the rate of reaction or rate of
mass transfer, because CAs cannot be measured by
standard techniques. To accomplish this elimination, we use Equations (
15-49), (15-50), and (15-51) in order to equate the mass transfer rate of
A to the pellet surface, –WArac, to the rate of consumption of A within the
pellet, ηk1CAs

WAr ac = ηk1CAs

Then substitute for WAr ac using Equation (15-50)

Solving for CAs, we obtain

Concentration at the pellet surface as a function of bulk gas

concentration

Substituting for CAs in Equation (15-51) gives

In discussing the surface accessibility, we defined the internal
effectiveness factor η with respect to the concentration at the external
surface of the pellet, CAs, as
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We now define an overall effectiveness factor that is based on the bulk

concentration

Two different effectiveness factors

Dividing the numerator and denominator of Equation (15-54) by kc ac,

we obtain the net rate of reaction, –rA, in terms of the bulk fluid
concentration, which is a measurable quantity:

The actual rate of reaction is related to the reaction rate evaluated at the
bulk concentration of A. Consequently, the overall rate of reaction in
terms of the bulk concentration CAb is

where
Overall effectiveness factor for a first-order reaction

Note that the rates of reaction based on surface and bulk

concentrations are related by
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where

The actual rate can be expressed in terms of the rate per

unit volume, –rA, the rate per unit mass, , and the
rate per unit surface area, , which are related by
the equation

Recall that is given in terms of the catalyst

surface area (m3/m2 · s), is given in terms
of catalyst mass (m3/g-cat · s), and k1 is given
in terms of reactor volume (1/s)

We saw in Chapter 14 that as the velocity of the

fluid increases, the external mass transfer
coefficient kc increases (cf. 14-49). Consequently,
for large flow rates resulting in large values of the external mass transfer
coefficient kc, we can neglect the ratio in the denominator

High flow rates of fluid

and the overall effectiveness factor approaches the internal

effectiveness factor

15.6 Estimation of Diffusion- and Reaction-Limited Regimes

In many instances it is of interest to obtain “quick and dirty” estimates to
learn which is the rate-limiting step in a heterogeneous reaction.

Dial soap 37/77

15.6.1 Mears Criterion for External Diffusion Limitations

The Mears criterion, like the Weisz–Prater criterion, uses the measured
rate of reaction, , (kmol/kg-cat · s) to learn if external mass transfer
from the bulk gas phase to the catalyst surface can be neglected.6 Mears
proposed that when the Mears number is

6
D. E. Mears, Ind. Eng. Chem. Process Des. Dev., 10, 541 (1971). Other
interphase transport-limiting criteria can be found in AIChE Symp. Ser.
143 (S. W. Weller, ed.), 70 (1974).

Is external diffusion limiting?

Here, we measure (obs), CAb, ρb, R and n, and then calculate kc to

determine MR, where

Mears proposed that when

MR < 0.15
external mass transfer effects can be neglected and no concentration
gradient exists between the bulk gas and external surface of the catalyst
pellet. This proposal by Mears was endorsed unanimously by the
Jofostan legislature. The mass transfer coefficient can be calculated from
38/77

the appropriate correlation, such as that of Thoenes–Kramers, for the

flow conditions through the bed.

Mears also proposed that the bulk fluid temperature, T, will be virtually
the same as the temperature at the external surface of the pellet when

T b ≅ Ts

and the other symbols are as in Equation (15-62).

15.7 Mass Transfer and Reaction in a Packed Bed

We now consider the same isomerization taking place in a packed bed of

catalyst pellets rather than on one single pellet (see Figure 15-9). The
concentration CAb is the bulk gas-phase concentration of A at any point
along the length of the bed.

Figure 15-9 Packed-bed reactor.

We shall perform a balance on species A over the volume element, ΔV,
neglecting any radial variations in concentration and assuming that the
bed is operated at steady state. The following symbols will be used in
developing our model: 39/77

A mole balance on ΔV, the volume element (A c Δz), yields

Mole Balance

Dividing by Ac Δz and taking the limit as Δz 0 yields

Combining Equation (14-5) and (14-7), we get

Also, writing the bulk flow term in

the form

BAz = yAb (WAz + WBz) = yAb cU =

UCAb

Equation (15-64) can be written in

the form
Now we will see how to use η and Ω to calculate conversion in a packed
bed.

The term DAB (d2CAb/dz2) is used to represent either diffusion and/or 40/77

dispersion in the axial direction. Consequently, we shall use the symbol

Da for the dispersion coefficient to represent either or both of these
cases. We will come back to this form of the diffusion equation when we
discuss dispersion in Chapter 18. The overall reaction rate, –rA , is a
function of the reactant concentration within the catalyst. This overall
rate can be related to the rate of reaction of A that would exist if the
entire surface were exposed to the bulk concentration CAb through the
overall effectiveness factor Ω

For the first-order reaction considered here

Substituting this equation for –rA into Equation (15-65), we form the
differential equation describing diffusion with a first-order reaction in a
catalyst bed

Flow and first-order reaction in a packed bed

As an example, we shall solve this equation for the case in which the
flow rate through the bed is very large and the axial diffusion can be
neglected. Young and Finlayson have shown that axial dispersion can be
neglected when7

7
L. C. Young and B. A. Finlayson, Ind. Eng. Chem. Fund., 12, 412.

Criterion for neglecting axial dispersion/diffusion

where U0 is the superficial velocity, dp the particle diameter, and Da is 41/77

the effective axial dispersion coefficient. In Chapter 18 we will consider

solutions to the complete form of Equation (15-67).

Neglecting axial dispersion with respect to forced axial convection

Equation (15-67) can be arranged in the form

With the aid of the boundary condition at the entrance of the reactor

at z = 0
CAb = CAb0

Equation (15-69) can be integrated to give

Conversion in a packed-bed reactor

The conversion at the reactor’s exit, z = L, is

Example 15–3 Reducing Nitrous Oxides in a Plant’s Effluent 42/77

In Section 7.1.4 we saw that Nitric Oxide (NO) plays an important role in
smog formation and there are great incentives for reducing its
concentration in the atmosphere. It is proposed to reduce the
concentration of NO in an effluent stream from a plant by passing it
through a packed bed of spherical, porous carbonaceous solid pellets. A
2% NO and 98% air mixture flows at a rate of 1 × 10–6 m3/s (0.001 dm3/s)
through a 2-in.-ID tube packed with porous solid pellets at a
temperature of 1173 K and a pressure of 101.3 kPa. The reaction

Green chemical reaction engineering

is first order in NO; that is,

and occurs primarily in the pores inside the pellet,

where

From those values of and we find

k1 = ρbk ′ = (1.4 × 10 g / m3)(2.34 × 10–7m3 / g / s) = 0.328s–1

This example is long and detailed. Don’t fall asleep, as
you need to know every detail of how to carry out these 43/77

1.Calculate the Weisz–Prater parameter, CWP. Is internal

mass transfer limiting?

2.Calculate the Mears parameter, MR, for external

diffusion limited. Is external mass transfer limiting?

3.Calculate the weight of solid porous catalyst necessary to reduce the

NO concentration of 0.004%, which is below the Environmental
Protection Agency’s limit.

Additional information:

At 1173 K, the fluid properties are

The properties of the

catalyst and bed are
 44/77

Also see the Web site www.rowan.edu/greenengineering

Solution

It is desired to reduce the NO concentration from 2.0% to 0.004%.

Neglecting any volume change at these low concentrations gives us

where A represents NO.

The variation of NO down the length of

the reactor is given by Equation (15-69).
Replacing k1 by

Multiplying the denominator on the right and left hand sides of Equation
(15-69) by the cross-sectional area, Ac, and realizing that the weight of
the catalyst up to a point z in the bed is

W = p b Ac z

the variation of NO concentration with solids is

(Mole balance) + (Rate law) + (Overall effectiveness factor)

Because NO is present in dilute concentrations (i.e., yA0 ),

we shall take e and set AcU = υ0 . We integrate Equation (E15-3.1)
using the boundary condition that when W = 0, then CAb = CAb0
where 45/77

Rearranging, we have

4. Calculating the internal effectiveness factor for spherical pellets in which

a first-order reaction is occurring, we obtained

As a first approximation, we shall neglect any changes in the pellet size

resulting from the reactions of NO with the porous carbon. The Thiele
modulus for this system is8

where

Substituting in Equation (E15-3.4)

 46/77

Because ϕ1 is large

1. Calculate CWP

2. To calculate the external mass transfer coefficient, the Thoenes–Kramers

correlation is used. From Chapter 14 we recall

For a 2-in.-ID pipe, Ac = 2.03 × 10–3 m2 . The superficial velocity is

Procedure
Calculatem
Re’
Sc 47/77

Then
Sh’
Then
kc

3.
Calcul
ating
the
extern
al
4. Evaluating the overall effectiveness factor. Substituting into Equation
area
per
(15-58), we have
unit
reacto
r
volum
e, we
obtai
n

In this example we see that both the external and internal resistances to
mass transfer are significant.

5. Calculate the Mears criterion, MR, to see if mass transfer limits the
reaction.
 48/77

MR (i.e., 0.97 > 0.15) and diffusion limits the reaction.

6. Calculating the weight of solid necessary to achieve 99.8% conversion.

Substituting into Equation (E15-3.3), we obtain

7. The reactor length is

This catalyst weight and

corresponding reactor length
are rather small and as such we
could easily increase the feed
rate to the reactor.

Analysis: One of the purposes of this example was to show how to carry
out detailed calculations of the diffusion and reaction rate in order to
size (i.e., calculate V or W) a reactor for a specified conversion, when
both external and internal diffusion resistances affect the rate of
reaction. These calculations are tedious and detailed, and it was my
feeling that we should show and know all the intermediate calculations,
e.g., ac, η and Ω, so that the reader will have a better understanding of
how to make such calculations in the future.
15.8 Determination of Limiting Situations from Reaction-Rate Data

For external mass transfer-limited reactions in packed beds, the rate of

reaction per unit mass of catalyst at a point in the bed is 49/77

Variation of reaction rate with system variables

The correlation for the mass transfer coefficient, Equation (14-66),

shows that kc is directly proportional to the square root of the velocity
and inversely proportional to the square root of the particle diameter

We recall from Equation

(E15-3.5), ac = 6(1 – ϕ)/dp,
that the variation of
external surface area with
catalyst particle size is

We now combine Equations (15-72), (15-73), and (15-74) to obtain

Consequently, for external mass transfer–limited reactions, the rate

proportional to the velocity to the one-half power is inversely
proportional to the particle diameter to the three-halves power.

From Equation (14-72), we see that for gas-phase external mass

transfer– limited reactions, the rate increases approximately linearly
with temperature.

Many heterogeneous reactions are diffusion limited.

When internal diffusion limits the rate of reaction, we observe from
Equation (15-42) that the rate of reaction varies inversely with particle
diameter, is independent of velocity, and exhibits an exponential
temperature dependence that is not as strong as that for surface- 50/77

reaction-controlling reactions. For surface-reaction-limited reactions, the

rate is independent of particle size and is a strong function of
temperature (exponential). Table 15-1 summarizes the dependence of
the rate of reaction on the velocity through the bed, particle diameter,
and temperature for the three types of limitations that we have been
discussing.

TABLE 15-1 LIMITING CONDITIONS

Very Important Table

The exponential temperature dependence for internal diffusion

limitations is usually not as strong a function of temperature as is the
dependence for surface reaction limitations (cf. Section 15.4). If we
would calculate an activation energy between 8 and 24 kJ/mol, chances
are that the reaction would be strongly diffusion-limited. An activation
energy of 200 kJ/mol, however, suggests that the reaction is reaction
rate–limited.

15.9 Multiphase Reactors in the Professional Reference Shelf

Multiphase reactors are reactors in which two or more phases are

necessary to carry out the reaction. The majority of multiphase reactors
involve gas and liquid phases that contact a solid. In the case of the
slurry and trickle bed reactors, the reaction between the gas and the
liquid takes place on a solid catalyst surface (see Table 15-2). However, in
some reactors the liquid phase is an inert medium for the gas to contact
the solid catalyst. The latter situation arises when a large heat sink is 51/77
required for highly exothermic reactions. In many cases, the catalyst life
is extended by these milder operating conditions.

I. Slurry reactor

A. Hydrogenation

1. of fatty acids over a supported nickel catalyst

2. of 2-butyne-1,4-diol over a Pd-CaCO3 catalyst

3. of glucose over a Raney nickel catalyst

B. Oxidation

4. of C2 H4 in an inert liquid over a PdCl2-carbon catalyst

5. of SO2 in inert water over an activated carbon catalyst

C. Hydroformation

of CO with high-molecular-weight olefins on either a cobalt or ruthenium

complex bound to polymers

D. Ethynylation

Reaction of acetylene with formaldehyde over a CaCl2-supported catalyst

II. Trickle bed reactors

A. Hydrodesulfurization

Removal of sulfur compounds from crude oil by 52/77

reaction with hydrogen on Co-Mo on alumina

B. Hydrogenation

1. of aniline over a Ni-clay catalyst

2.of 2-butyne-1,4-diol over a supported Cu-Ni

catalyst

3.of benzene, a-CH3 styrene, and

crotonaldehyde

4. of aromatics in napthenic lube

oil distillate

C. Hydrodenitrogenation

1. of lube oil distillate

2. of cracked light furnace oil

D. Oxidation

3. of cumene over activated

carbon

4. of SO2 over carbon

Source: Satterfield, C. N. AIChE Journal., 21, 209

(1975); P. A. Ramachandran and R. V. Chaudhari,
Chem. Eng., 87(24), 74 (1980); R. V. Chaudhari and
P. A. Ramachandran, AIChE Journal., 26, 177
(1980). With permission of the American Institute
of Chemical Engineers. Copyright © 1980 AIChE.
All rights reserved.
The multiphase reactors discussed in this edition of the book are the
slurry reactor, fluidized bed, and the trickle bed reactor. The trickle bed
reactor, which has reaction and transport steps similar to the slurry
reactor, is discussed in the first edition of this book and on the CRE Web 53/77

site along with the bubbling fluidized bed. In slurry reactors, the catalyst
is suspended in the liquid, and gas is bubbled through the liquid. A
slurry reactor may be operated in either a semibatch or continuous
mode.

15.9.1 Slurry Reactors

A complete description of the slurry reactor and the transport and

reaction steps are given on the CRE Web site, along with the design
equations and a number of examples. Methods to determine which of
the transport and reaction steps are rate limiting are included. See
Professional Reference Shelf R15.1.

15.9.2 Trickle Bed Reactors

The CRE Web site includes all the material on trickle bed reactors from
the first edition of this book. A comprehensive example problem for
trickle bed reactor design is included. See Professional Reference Shelf
R15.2.

15.10 Fluidized Bed Reactors

The Kunii-Levenspiel model for fluidization is given on the CRE Web site
along with a comprehensive example problem. The rate-limiting
transport steps are also discussed. See Professional Reference Shelf R15.3.
 54/77

15.11 Chemical Vapor Deposition (CVD)

Chemical vapor deposition in boat reactors is discussed and modeled.

The equations and parameters that affect wafer thickness and shape are
derived and analyzed. This material is taken directly from the second
edition of this book. See Professional Reference Shelf R15.4.

Summary

1. The concentration profile for a first-order reaction occurring in a

spherical catalyst pellet is

where ϕ1 is the Thiele modulus. For a first-order reaction

2. The effectiveness factors are

 55/77

3. For large values of the Thiele modulus for an nth order reaction

4. For internal diffusion control, the true reaction order is related to the
measured reaction order by

The true and apparent activation energies are related by

5. A. The Weisz–Prater Parameter

The Weisz–Prater criterion dictates that

56/77

B. The Mears Criterion for Neglecting External Diffusion and Heat

Transfer

There will be no external diffusion limitations if

And there will be no temperature gradients if

CRE Web Site Materials

• Extended Material on the Web Site

1. Web Example 15-1 Application of Diffusion and Reaction to Tissue

Engineering (also see P15-15B)

From Prof. Kristi Anseth, University of Colorado.

Figure WE15-1.1 Damaged cartilage. (Newsweek, September 3, 2001.)
Photo of “damaged cartilage” originally appeared in “21 Million
Americans Suffer from Arthritis,” by Jerry Adler.
57/77
2.15.3.3 Effectiveness Factor for Nonisothermal First-Order Catalytic
Reactions

3. Problem 15-12C Diffusion and Reaction in Spherical Catalyst

Pellets

4. Additional Homework Problems

• Learning Resources

1. Summary Notes

2. Solved Problems

•Professional Reference Shelf

R15.1. Slurry Reactors

A. Description of the Use of Slurry Reactors

Example R15-1 Industrial Slurry Reactor

B. Reaction and Transport Steps in a Slurry Reactor

C. Determining the Rate-Limiting Step

1.Effect of Loading, Particle Size, and Gas

Adsorption
58/77

2. Effect of Shear

Example R15-2 Determining the

Controlling Resistance

D. Slurry Reactor Design

Example R15-3 Slurry Reactor Design

R15.2. Trickle Bed Reactors

A. Fundamentals

B. Limiting Situations
C. Evaluating the Transport Coefficients

59/77

R15.3. Fluidized Bed Reactors

A. Descriptive Behavior of the Kunii-Levenspiel Bubbling Bed Model

B. Mechanics of Fluidized Beds

Example R15-4 Maximum Solids Hold-Up

C. Mass Transfer in Fluidized Beds

D. Reaction in a Fluidized Bed

E. Solution to the Balance Equations for a First-Order Reaction

Example R15-5 Catalytic Oxidation of
Ammonia

F. Limiting Situations
60/77

Example R15-6 Calculation of the

Resistances

Example R15-7 Effect of Particle Size

on Catalyst Weight for a Slow
Reaction

Example R15-8 Effect of Catalyst

Weight for a Rapid Reaction

R15.4. Chemical Vapor Deposition

Reactors

A. Chemical Reaction Engineering in Microelectronic Processing

B. Fundamentals of CVD

C.Effectiveness Factors for Boat Reactors

Example R15-9 Diffusion Between Wafers

Example R15-10 CVD Boat Reactor

 61/77

Questions and Problems

The subscript to each of the problem numbers indicates the level of

difficulty: A, least difficult; D, most difficult.

Questions

Q15-1C Make up an original problem using the concepts presented in

Section (your instructor will specify the section). Extra credit
will be given if you obtain and use real data from the literature. (See
Problem P5-1A for the guidelines.)

Q15-2 Suppose someone had used the false kinetics (i.e., wrong E, wrong
n)? Would the catalyst weight be overdesigned or underdesigned? What
are other positive or negative effects that occur?

Problems

P15-1B

(a) Example 15-1. Effective Diffusivity. Make a sketch of a diffusion path

for which the tortuosity is 5. How would your effective gas-phase
diffusivity change if the absolute pressure were tripled and the
temperature were increased by 50%?
(b) Example 15-2. If possible, determine the percent of the total
resistance for (1) internal diffusion and (2) for reaction rate for each of
the three particles studied. Apply the Weisz-Prater criteria to a particle
0.005 m in diameter. 62/77

(c) Example 15-3. Overall Effectiveness Factor. (1) Calculate the percent of
the total resistance for the resistance of external diffusion, internal
diffusion, and surface reaction. Qualitatively, how would each of your
percentages change (2) If the temperature were increased significantly?
(3) If the gas velocity were tripled? (4) If the particle size were decreased
by a factor of 2? How would the reactor length change in each case? (5)
What length would be required to achieve 99.99% conversion of the
pollutant NO?

What if...

(d)you applied the Mears and Weisz–Prater criteria to Examples 15-4

and 15-3? What would you find? What would you learn if
kcal/mol, h = 100 Btu/h · ft2 · °F, and E = 20 kcal/mol?

(e)your internal surface area decreased with time because of sintering

(see Section 10.7). Describe how your effectiveness factor would change
and the rate of reaction change with time if kd = 0.01 h–1 and η = 0.01 at t
= 0? Explain, being as quantitative as possible when you can.

(f)you were to assume that the resistance to gas absorption in the CRE
Web site Professional Reference Shelf R15.1 was the same as in
Professional Reference Shelf R15.3 and that the liquid-phase reactor
volume in Professional Reference Shelf R15.3 was 50% of the total? Could
you determine the limiting resistance? If so, what is it? What other things
could you calculate in Professional Reference Shelf R15.1 (e.g., selectivity,
conversion, molar flow rates in and out)? Hint: Some of the other
reactions that occur include
(g)the temperature in the CRE Web site
Example R15.2 were increased? How would
the relative resistances in the slurry reactor
change? 63/77

(h)you were asked for all the things that could go wrong in the
operation of a slurry reactor? What would you say?

P15-2B Concept problem: The catalytic reaction

takes place within a fixed bed containing spherical porous

catalyst X22. Figure P15-2B shows the overall rates of
reaction at a point in the reactor as a function of temperature for
various entering total molar flow rates, FT0 .

(i) Is the reaction limited by external diffusion?

(j)If your answer to part (a) was “yes,” under what conditions of those
shown (i.e., T, FT0) is the reaction limited by external diffusion?

(k) Is the reaction “reaction-rate-limited”?

(l)If your answer to part (c) was “yes,” under what conditions of those
shown (i.e., T, FT0) is the reaction limited by the rate of the surface
reactions?

(m)Is the reaction limited by internal diffusion?

(n)If your answer to part (e) was “yes,” under what conditions of those
shown (i.e., T, FT0) is the reaction limited by the rate of internal diffusion?

(o)For a flow rate of 10 g mol/h, determine (if possible) the overall

effectiveness factor, Ω, at 360 K.

(p)Estimate (if possible) the internal effectiveness factor, η, at 367 K.

(Ans.: η = 0.86)

(i) If the concentration at the external catalyst surface is 0.01

mol/dm3,
calculate (if possible) the concentration at r = R/2 inside the porous
catalyst at 367 K. (Assume a first-order reaction.)

64/77

Figure P15-2B Reaction rates in a catalyst bed.

Additional information:

P15-3B Concept problem: The reaction

is carried out in a differential packed-bed reactor at
different temperatures, flow rates, and particle sizes. The
results shown in Figure P15-3B were obtained.
65/77

Figure P15-3B Reaction rates in a catalyst bed.

(a)What regions (i.e., conditions dp, T, FT0) are external mass transfer–
limited?

(b) What regions are reaction rate–limited?

(c) What region is internal-diffusion-controlled?

(d)What is the internal effectiveness factor at T = 400 K and dp = 0.8 cm?

(Ans.: η = 0.625) 66/77

P15-4A Concept problem: Curves A, B, and C in Figure P15-4A show the

variations in reaction rate for three different reactions catalyzed by solid
catalyst pellets. What can you say about each reaction?

Figure P15-4A Temperature

dependence of three reactions.

P15-5B A first-order heterogeneous

irreversible reaction is taking place
within a spherical catalyst pellet that
is plated with platinum throughout
the pellet (see Figure 15-3). The
reactant concentration halfway
between the external surface and the center of the pellet (i.e., r = R/2) is
equal to one-tenth the concentration of the pellet’s external surface. The
concentration at the external surface is 0.001 g mol/dm3, the diameter
(2R) is 2 × 10 –3 cm, and the diffusion coefficient is 0.1 cm2/s.

(e) What is the concentration of reactant at a distance of 3

× 10–4 cm in from the external pellet surface? (Ans.: CA =
2.36 × 10–4 mol/dm3.)

(b)To what diameter should the pellet be reduced if the effectiveness

factor is to be 0.8? (Ans.: dp = 6.8 × 10–4 cm. Critique this answer!)

(c)If the catalyst support were not yet plated with platinum, how would
you suggest that the catalyst support be plated after it had been
reduced by grinding?
P15-6B The swimming rate of a small organism [J. Theoret. Biol., 26, 11
(1970)] is related to the energy released by the hydrolysis of adenosine
triphosphate (ATP) to adenosine diphosphate (ADP). The rate of
hydrolysis is equal to the rate of diffusion of ATP from the midpiece to 67/77
the tail (see Figure P15-6B). The diffusion coefficient of ATP in the
midpiece and tail is 3.6 × 10–6 cm2/s. ADP is converted to ATP in the
midsection, where its concentration is 4.36 × 10–5 mol/cm3. The cross-
sectional area of the tail is 3 × 10–10 cm2.

Figure P15-6B Swimming of an organism.

(a) Derive an equation for diffusion and reaction in the tail.

(b) Derive an equation for the effectiveness factor in the tail.

(c)Taking the reaction in the tail to be of zero order, calculate the length
of the tail. The rate of reaction in the tail is 23 × 10–18 mol/s.

(d)Compare your answer with the average tail length of 41 μm. What
are possible sources of error?

P15-7B A first-order, heterogeneous, irreversible reaction is taking place

within a catalyst pore that is plated with platinum entirely along the
length of the pore (Figure P15-7B). The reactant concentration at the
plane of symmetry (i.e., equal distance from the pore mouth) of the pore
is equal to one-tenth the concentration at the pore mouth. The
concentration at the pore mouth is 0.001 mol/dm3, the pore length (2L)
is 2 × 10–3 cm, and the diffusion coefficient is 0.1 cm2/s.

(e) Derive an equation for the effectiveness factor.

(f) What is the concentration of reactant at L/2?

Figure P15-7B Single catalyst pore.

(c)To what length should the pore

length be reduced if the 68/77

effectiveness factor is to be 0.8?

(d) If the catalyst support were not

yet plated with platinum, how would you suggest the catalyst support be
plated after the pore length, L, had been reduced by grinding?

P15-8A A first-order reaction is taking place inside a porous catalyst.

Assume dilute concentrations and neglect any variations in the axial (x)
direction.

(e)Derive an equation for both the internal and overall effectiveness

factors for the rectangular porous slab shown in Figure P15-8A.

(f)Repeat part (a) for a cylindrical catalyst pellet where the reactants
diffuse inward in the radial direction. (C-level problem, i.e., P15-8C(b).)

Figure P15-8A Flow over

porous catalyst slab.

P15-9B The irreversible

reaction

is taking place in the

same
porous catalyst slab shown in Figure P15-8A. The reaction
is zero order in A.

(a) Show that the concentration profile using the

symmetry B.C. is
where 69/77

(b)For a Thiele modulus of 1.0, at what point in the slab is the

concentration zero? For ϕ0 = 4?

(c)What is the concentration you calculate at z = 0.1 L and ϕ0 = 10 using

Equation (P15-9.1)? What do you conclude about using this equation?

(d)Plot the dimensionless concentration profile ψ = CA/CAs as a function

of λ = z/L for ϕ 0 = 0.5, 1, 5, and 10. Hint: there are regions where the
concentration is zero. Show that λC = (1 – 1/ϕ0) is the start of this region
where the gradient and concentration are both zero. [L. K. Jang, R. L.
York, J. Chin, and L. R. Hile, Inst. Chem. Engr., 34, 319 (2003).]

Show that for λC ≤ λ > 1.

(e)The effectiveness factor can be

written as

where zC (λC) is the point at which both the concentration gradients and
flux go to zero, and Ac is the cross-sectional area of the slab. Show for a
zero-order reaction that

(f) Make a sketch for η versus ϕ 0 similar to the one shown in Figure 15-5.

(g) Repeat parts (a) to (f) for a spherical catalyst pellet.

(h) What do you believe to be the point of this problem?

P15-10C The second-order decomposition reaction

is carried out in a tubular reactor packed with 70/77

catalyst pellets 0.4 cm in diameter. The reaction is

internal-diffusion-limited. Pure A enters the reactor at a superficial
velocity of 3 m/s, a temperature of 250°C, and a pressure of 500 kPa.
Experiments carried out on smaller pellets where surface reaction is
limiting yielded a specific reaction rate of 0.05 m6/mol · g-cat · s.
Calculate the length of bed necessary to achieve 80% conversion.
Critique the numerical answer. (Ans.: L = 2.8 x 10–5 m)

Additional information:

P15-11C Derive the concentration profile and effectiveness factor for

cylindrical pellets 0.2 cm in diameter and 1.5 cm in length. Neglect
diffusion through the ends of the pellet.

(a)Assume that the reaction is a first-order isomerization. Hint: Look for a

Bessel function.

(b) Rework Problem P15-10C for these pellets.

P15-12B Extension of Problem P15-7B. The elementary isomerization

reaction

is taking place on the walls of a cylindrical catalyst pore

(see Figure P15-7B.) In one run, a catalyst poison P
entered the reactor together with the reactant A. To estimate the effect
of poisoning, we assume that the poison renders the catalyst pore walls
near the pore mouth ineffective up to a distance z1, so that no reaction
takes place on the walls in this entry region.
(a) Show that before poisoning of the pore occurred, the effectiveness
factor was given by

where
71/77

(b) Derive an expression for the concentration profile and also for the
molar flux of A in the ineffective region, 0 < z < z1, in terms of z1, DAB, CA1,
and CAs . Without solving any further differential equations, obtain the
new effectiveness factor η’ for the poisoned pore.

P15-13B Falsified Kinetics. The irreversible gas-phase dimerization

is carried out at 8.2 atm in a stirred contained-solids

reactor to which only pure A is fed. There are 40 g of
catalyst in each of the four spinning baskets. The following runs were
carried out at 227°C:

The following experiment was carried out at 237°C:

(a) What are the apparent reaction

order and the apparent activation
energy?
(b)Determine the true reaction order, specific reaction rate, and
activation energy.

(c) Calculate the Thiele modulus and effectiveness factor.

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(d)What pellet diameter should be used to make the catalyst more

effective?

(e)Calculate the rate of reaction on a rotating disk made of the catalytic

material when the gas-phase reactant concentration is 0.01 g mol/L and
the temperature is 227°C. The disk is flat, nonporous, and 5 cm in
diameter.

Additional information:

P15-14B Derive Equation (15-39). Hint: Multiply both sides of Equation

(15-25) for nth order reaction; that is,

by 2dy/dλ, rearrange to get

and solve using the boundary conditions dy/dλ = 0 at λ =

0.

P15-15B Applications of Diffusion and Reaction to Tissue

Engineering. The equations describing diffusion
and reaction in porous catalysts also can be used to derive rates of
tissue growth and have been studied by Professor Kristi Anseth and her
students at the University of Colorado. One important area of tissue
growth is in cartilage tissue in joints such as the knee. Over 200,000
patients per year receive knee joint replacements. Alternative strategies
include the growth of cartilage to repair the damaged knee.
One approach is to deliver cartilage-forming cells in a hydrogel to the
damaged area such as the one shown in Figure WP15-1.1 on the CRE
Web site.
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Here, the patient’s own cells are obtained from a biopsy and embedded
in a hydrogel, which is a cross-linked polymer network that is swollen in
water. In order for the cells to survive and grow new tissue, many
properties of the gel must be tuned to allow diffusion of important
species in and out (e.g., nutrients in and cell-secreted extracellular
molecules such as collagen out). Because there is no blood flow through
the cartilage, oxygen transport to the cartilage cells is primarily by
diffusion. Consequently, the design must be such that the gel can
maintain the necessary rates of diffusion of nutrients (e.g., O2) into the
hydrogel. These rates of exchange in the gel depend on the geometry
and the thickness of the gel. To illustrate the application of chemical
reaction engineering principles to tissue engineering, we will examine
the diffusion and consumption of one of the nutrients, oxygen.

Figure P15-15B Schematic of cartilage cell system.

Our examination of diffusion and reaction in catalyst pellets showed that

in many cases the reactant concentration near the center of the particle
was virtually zero. If this condition were to occur in a hydrogel, the cells
at the center would die. Consequently, the gel thickness needs to be
designed to allow rapid transport of oxygen.

Let’s consider the simple gel geometry shown in Figure P15-15B. We 74/77
want to find the gel thickness at which the minimum oxygen
consumption rate is 10–13 mol/cell/h .

The cell density in the gel is 1010 cells/dm3, the bulk

concentration of oxygen CA0 (z = 0) is 2 x 10–4
mol/dm3, and the diffusivity, DAB, is 10–5 cm2/s.

(a) Show that the dimensionless form of

concentration and length, ψ =
CA/CA0, and λ = z/L, differential mole balance on O2
gives

(b)Show the dimensionless O2 concentration

profile in the gel is

where

(c)Solve the gel thickness when the

concentration at z = 0 and CA = 0.1
mmole/dm3.

(d)How would your answers change if the reaction

kinetics were (1) first order in the O2 concentration
with k1 = 10–2 h–1?

(e)Carry out a quasi-steady-state analysis using Equation (E15-1.19)

along with the overall balance

to predict the O2 flux and collagen build-up as a

function of time.

(f) Sketch ψ versus λ at different times.

(g) Sketch λc as a function of time. Hint: V = AcL. Assume α = 10 and the
stoichiometric coefficient for oxygen to collagen, υc, is 0.05 mass fraction
of cell/mol O2. Ac = 2 cm2.
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Journal Critique Problems

P15C-1 Use the Weisz–Prater criterion to determine if the reaction

discussed in AIChE J., 10, 568 (1964) is diffusion-rate-limited.

P15C-2 Use the references given in Ind. Eng. Chem. Prod. Res. Dev., 14,
226 (1975) to define the iodine value, saponification number, acid
number, and experimental setup. Use the slurry reactor analysis to
evaluate the effects of mass transfer and determine if there are any
mass transfer limitations.

Supplementary Reading

1. There are a number of books that discuss internal diffusion in catalyst

pellets; however, one of the first books that should be consulted on this
and other topics on heterogeneous catalysis is

LAPIDUS, L., AND N. R. AMUNDSON, Chemical Reactor Theory: A Review , Upper

Saddle River, N.J.: Prentice Hall, 1977.

In addition, see

ARIS, R., Elementary Chemical Reactor Analysis. Upper Saddle River, NJ:
Prentice Hall, 1989, Chap. 6. Old, but one should find the references
listed at the end of this reading particularly useful.

FOGLER, JOSEPH J., AKA JOFO, A Chemical Reaction Engineers Guide to the
Country of Jofostan. To be self published, hopefully by 2020.
LUSS, D., “Diffusion—Reaction Interactions in Catalyst Pellets,” p. 239 in
Chemical Reaction and Reactor Engineering. New York: Marcel Dekker,
1987.
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The effects of mass transfer on reactor performance are also discussed
in

COLLINS, FRANK C., AND GEORGE E. KIMBALL, “Diffusion Controlled Reaction

Rates,” Journal of Colloid Science, Vol. 4, Issue 4, August 1949, Pages 425-
437.

SATTERFIELD, C. N., Heterogeneous Catalysis in Industrial Practice, 2nd ed.

New York: McGraw-Hill, 1991.

2. Diffusion with homogeneous reaction is discussed in

ASTARITA, G., and R. OCONE, Special Topics in Transport Phenomena. New

York: Elsevier, 2002.

Gas-liquid reactor design is also discussed in

BUTT, JOHN B., Reaction Kinetics and Reactor Design, 2nd ed. Boca Raton,
FL: CRC Press, 2000.

SHAH, Y. T., Gas–Liquid–Solid Reactor Design. New York: McGraw-Hill,

1979.

3. Modeling of CVD reactors is discussed in

DOBKIN, DANIEL, AND M. K. ZUKRAW, Principles of Chemical Vapor Deposition.

The Netherlands: Kluwer Academic Publishers, 2003.

HESS, D. W., K. F. JENSEN, and T. J. ANDERSON, “Chemical Vapor Deposition:

A Chemical Engineering Perspective,” Rev. Chem. Eng., 3, 97, 1985.

4. Multiphase reactors are discussed in

RAMACHANDRAN, P. A., and R. V. CHAUDHARI, Three-Phase Catalytic Reactors.

New York: Gordon and Breach, 1983.
RODRIGUES, A. E., J. M. COLO, and N. H. SWEED, eds., Multiphase Reactors,
Vol. 1: Fundamentals. Alphen aan den Rijn, The Netherlands: Sitjhoff and
Noordhoff, 1981.
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RODRIGUES, A. E., J. M. COLO, and N. H. SWEED, eds., Multiphase Reactors,
Vol. 2: Design Methods. Alphen aan den Rijn, The Netherlands: Sitjhoff
and Noordhoff, 1981.

SHAH, Y. T., B. G. KELKAR, S. P. GODBOLE, and W. D. DECKWER, “Design

Parameters Estimations for Bubble Column Reactors” (journal
review),
AIChE J., 28, 353 (1982).

The following Advances in Chemistry Series volume discusses a number of

multiphase reactors:

FOGLER, H. S., ed., Chemical Reactors, ACS Symp. Ser. 168. Washington,
DC: American Chemical Society, 1981, pp. 3–255.

5. Fluidization

KUNII, DAIZO, AND OCTAVE LEVENSPIEL, Fluidization Engineering, 2nd ed.

(Butterworths Series in Chemical Engineering Deposition). Stoneham,
MA: Butterworth-Heinemann, 1991.

In addition to Kunii and Levenspiel’s book, many correlations can be

found in

DAVIDSON, J. F., R. CLIFF, and D. HARRISON, Fluidization, 2nd ed. Orlando:

Academic Press, 1985.

YATES, J. G., Fundamentals of Fluidized-Bed Chemical Processes, 3rd ed.

London: Butterworth, 1983.