Chapter 17

Heterogeneous
Reactions-Introduction

The second half of this book treats the kinetics and design of chemical reactors
for heterogeneous systems of various kinds, each chapter considering a different
system (see Chapter 1 for discussions of heterogeneous and homogeneous sys-
tems). For these systems there are two complicating factors that must be ac-
counted for beyond what is normally considered in homogeneous systems. First,
we have the complication of the rate expression, and second the complication
of the contacting patterns for two-phase systems. Let us briefly discuss these
in turn.

The Complications of the Rate Equation. Since more than one phase is present,
the movement of material from phase to phase must be considered in the rate
equation. Thus the rate expression in general will incorporate mass transfer
terms in addition to the usual chemical kinetics term. These mass transfer terms
are different in type and numbers in the different kinds of heterogeneous systems;
hence, no single rate expression has general application. Here are some sim-
ple examples.

THE BURNING OF A CARBON PARTICLE IN AIR

Tell how many rate steps are involved. The kinetics is given by

C + O,+CO,

and ignore the possible formation of CO.

From Fig. E17.1 we see that two steps in series are involved-mass transfer of
oxygen to the surface followed by reaction at the surface of the particle.
369
370 Chapter 17 Heterogeneous Reactions-Introduction

J'
r,sJ;,.

' 3 2
-
Model

Burning carbon particle

Gas film

Fig. E17.1

AEROBIC FERMENTATION

w many rate steps are involved when air bubbles through a tank of liquid

product material.

From Fig. E17.2 we see that there are up to seven possible resistance steps, only
one involving the reaction. How many you choose to consider depends on you
and on the situation.

To get an overall rate expression, write the individual rate steps on the same
basis (unit surface of burning particle, unit volume of fermenter, unit volume of
cells, etc.).

1 dNA - mol A reacted

-TA=
V dt volume of reactor fluid. time
 Chapter 17 Heterogeneous Reactions-Introduction 371

1 dNA - mol A reacted

-ri= W dt mass of solid. time

1d N A - mol A reacted
-rL= S dt interfacial surface. time

Now put all the mass transfer and reaction steps into the same rate form and
then combine. Thus

mol A reacted -
- (-rA)v = ( - r i ) W = (-rL)S
time

and if the steps are in series, as in Examples 17.1 and 17.2

roverall = r1 = r2 = r3

If they are in parallel

Consider steps in series. In general, if all the steps are linear in concentration,
then it is easy to combine them. However, if any of the steps are nonlinear, then
you will get a messy overall expression. Therefore, you may try to bypass this
nonlinear step in one of various ways. Approximating the r, versus C, curve by
a first-order expression is probably the most useful procedure.
Another point: in combining rates we normally do not know the concentration
of materials at intermediate conditions, so these are the concentrations that we
eliminate in combining rates. Example 17.3 shows this.
 372 Chapter 17 Heterogeneous Reactions-Introduction

0 VERALL RATE FOR A LINEAR PROCESS

Dilute A diffuses through a stagnant liquid film onto a plane surface consisting
of B, reacts there to produce R which diffuses back into the mainstream. Develop
the overall rate expression for the L/S reaction

A(1) + B(s) -+ R(1)

which takes place on this flat surface, see Fig. E17.3.

Figure E17.3.

SOLUTION

I By diffusion, the flux of A to the surface is

Reaction is first order with respect to A, so based on unit surface

At steady state the flow rate to the surface is equal to the reaction rate at the
surface (steps in series). So

and from Eqs. (i) and (ii)

 Chapter 17 Heterogeneous Reactions-Introduction 373

from which

(iii)

Replacing Eq. (iii) into either Eq. (i) or Eq. (ii) then eliminates C, which cannot
be measured, giving

Comment This result shows that llk, and llk" are additive resistances. It so
happens that the addition of resistances to obtain on overall resistance is permissi-
ble only when the rate is a linear function of the driving force and when the
processes occur in series.

OVERALL RATE FOR A NONLINEAR PROCESS

Repeat Example 17.3 with just one change: let the reaction step be second order
with respect to A, or

1 SOLUTION
Combining the reaction steps to eliminate C, as was done in Example 17.3, is
now not so simple, and gives

Contacting Patterns for Two-Phase Systems

There are many ways that two phases can be contacted, and for each the design
equation will be unique. Design equations for these ideal flow patterns may
be developed without too much difficulty. However, when real flow deviates
considerably from these, we can do one of two things: we may develop models
to mirror actual flow closely, or we may calculate performance with ideal patterns
which "bracket" actual flow. Fortunately, most real reactors for heterogeneous
systems can be satisfactorily approximated by one of the five ideal flow patterns
of Fig. 17.1. Notable exceptions are the reactions which take place in fluidized
beds. There special models must be developed.
374 Chapter 17 Heterogeneous Reactions-Introduction

Plug Alplug B Plug Alplug B Plug Alplug B

countercurrent cocurrent crosscurrent

Micro-micro

Reaction in either
A or B phase

Reaction in either

Plug Almixed B Mixed Alrnixed B

(two cases) (two cases)

Figure 17.1. Ideal contacting patterns for two flowing fluids.

Final Thoughts on Flow Modeling

In reactor design and scale-up, it is essential to select a flow model which reason-
ably represents our setup. Too often we put too little thought here, carelessly
picking a nonrepresentative model and then doing computer calculations to the
nth degree of accuracy. And then we are surprised when design and scale-up do
not agree with our predictions. A simple reasonable model is much better than
a precise and detailed model which does not represent the contacting. Often the
choice of a good flow model and the knowledge of how the flow pattern changes
with scale-up spells the difference between success and failure.
The preceding thoughts guide us in our approach to heterogeneous reaction,
which we will consider in the rest of the book.

PROBLEMS

17.1. Gaseous reactant A diffuses through a gas film and reacts on the surface
of a solid according to a reversible first-order rate,

where CA, is the concentration of A in equilibrium with the solid surface.

Develop an expression for the rate of reaction of A accounting for both
the mass transfer and reaction steps.
 Problems 375
17.2. Example 17.4 gives the final rate expression for film mass transfer followed
by a second-order rate expression for reaction on a plane surface. Please
derive this expression and show that it is correct.

17.3. In slurry reactors, pure reactant gas is bubbled through liquid containing
suspended catalyst particles. Let us view these kinetics in terms of the film
theory, as shown in Fig. P17.3. Thus, to reach the surface of the solid, the

Typical liquid-

Figure P17.3

reactant which enters the liquid must diffuse through the liquid film into
the main body of liquid, and then through the film surrounding the catalyst
particle. At the surface of the particle, reactant yields product according
to first-order kinetics. Derive an expression for the rate of reaction in terms
of these resistances.