Chemical Reaction Engineering

(Homogeneous Reactions in Ideal Reactors)

Chapter 5
Design for Multiple
Reactions

NATIONAL UNIVERSITY OF HO CHI MINH CITY

UNIVERSITY OF TECHNOLOGY
1. Multiple Reactions
For multiple reactors, both the size requirement and the distribution of reaction
products are affected by the flow within the reactor.
• The distinction between a single reaction and multiple reactions is that the
single reaction requires only one rate expression to describe its kinetic behavior
whereas multiple reactions require more than one rate expression.
• Many multiple reactions can be considered to be combinations of two
primary types: parallel reactions and series reactions.
• In this chapter, expansion effects are ignored, thus ε = 0

1.1. Qualitative Discussion About Product Distribution

Consider the decomposition of A by either one of two paths:

(5.1)

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with corresponding rate equations

(5.2a)

(5.2b)

Dividing Eq. 5.2a by Eq. 5.2b gives a measure of the relative rates of formation of
R and S. Thus

(5.3)

This ratio is expected to be as large as possible.

k1, k2, a1, and a2 are all constant for a specific system at a given temperature. Thus,
CA is the only factor in this equation which we can adjust and control.

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• If a1 > a2: the desired reaction is of higher order than the unwanted reaction.
Eq. 5.3 shows that a high reactant concentration is desirable since it increases the
R/S ratio. As a result, a batch or plug flow reactor would favor formation of
product R and would require a minimum reactor size.

• If a1 < a2: the desired reaction is of lower order than the unwanted reaction.
A low reactant concentration is needed to favor formation of R. But this would
also require large mixed flow reactor.

• If a1 = a2: the two reactions are of the same order, Eq. 5.3 becomes

(5.4)

Thus, product distribution is fixed by k1/k2 alone and is unaffected by type of

reactor used.
Product distribution can be controlled by varying k1/k2 in two ways:

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 1. Changing the temperature. If the activation energies of the two
reactions are different, k1/k2 can be varied by changing temperature.

2. Using a catalyst. One of the most important features of a catalyst is

its selectivity in depressing or accelerating specific reactions. This
may be a much more effective way of controlling product distribution
than any of the methods discussed so far.

When you have two or more reactants, combinations of high and low
reactant
concentrations can be obtained by controlling the concentration of
feed materials.

Figures 5.1 and 5.2 illustrate methods of contacting two reacting

fluids in continuous and noncontinuous operations that keep the
concentrations of these components both high, both low, or one high
and the other low. 5
 Figure 5.1 Contacting patterns for various combinations of high and low
concentration of reactants in noncontinuous operations.

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Figure 5.2 Contacting patterns for various combinations of high and low
concentration of reactants in continuous flow operations.

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 1.2. Quantitative Treatment of Product Distribution
and of Reactor Size
If rate equations are known for the individual reactions, we can quantitatively
determine product distribution and reactor-size requirements. For convenience in
evaluating product distribution we introduce two terms, φ and Φ.
Consider the composition of A:

The instantaneous fractional yield of R (φ) is defined as:

(5.5)

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overall fractional yield of R (Φ) is defined as:

For plug flow, where C, changes progressively through the reactor

For mixed flow, the composition is C,, everywhere, so cp is likewise constant

throughout the reactor,

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For a series of 1, 2, . . . , N mixed flow reactors in which the concentration of
A is CAi, C,,, . . . , C,, the overall fractional yield is obtained by summing the
fractional yields in each of the N vessels and weighting these values by the
amount of reaction occurring in each vessel

For any reactor type the exit concentration of R is

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Figure 5.3 Shaded and dashed area gives total R formed.

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EX 5.1. CONTACTING PATTERNS FOR REACTIONS IN PARALLEL

The desired liquid-phase reaction

is accompanied by the unwanted side reaction

From the standpoint of favorable product distribution, order the

contacting schemes of Fig. 5.2, from the most desirable to the least
desirable.

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 EX 5.1. CONTACTING PATTERNS FOR REACTIONS IN PARALLEL

SOLUTION
Dividing Eq. (5) by Eq. (6) gives the ratio

which is to be kept as large as possible. According to the rule for reactions in

parallel, we want to keep CA high, CB low, and since the concentration dependency
of B is more pronounced than of A, it is more important to have low CB
than high CA. The contacting schemes are therefore ordered as shown in Fig. E5.1

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Example 5. 2 Product distribution for parallel reactions

Consider the aqueous reactions

For 90% conversion of A find the concentration of R in the product stream.

Equal volumetric flow rates of the A and of B streams are fed to the reactor,
and each stream has a concentration of 20 mol/liter of reactant.
The flow in the reactor follows.
(a) Plug flow
(b) Mixed flow
(c) The best of the four plug-mixed contacting schemes of Example 5.1.

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2. Potpourri of Multiple Reactions
2.1 IRREVERSIBLE FIRST-ORDER REACTIONS IN
SERIES

proceed only in the presence of light, that they stop

the instant the light is turned off, and that for a given
intensity of radiation, the rate equations are
Figure 5.4 (8.1) Concentration-time curves if
the contents of the beaker are irradiated
uniformly.

Figure 5.5 (8.2) Concentration-

time curves for the contents of the
beaker if only a small portion of
the fluid is irradiated at any instant.
Quantitative Treatment, Plug Flow or Batch
Reactor.
Quantitative Treatment, Mixed Flow Reactor.

Figure 5.6 (8.4) Variables for reactions in series (no R or S in the feed) occurring in
a mixed flow reactor.

By the steady-state material balance we obtain for any component

input = output + disappearance by reaction

Quantitative Treatment, Mixed Flow Reactor.
For component R the material balance
2.2 FIRST-ORDER FOLLOWED BY ZERO-ORDER
REACTION
Figure 5.7 (8.7) Product distribution for the reactions
2.3 ZERO-ORDER FOLLOWED BY FIRST-ORDER
REACTION
Figure 5.8 (8.8) Product distribution for the reactions