Chapter 3

Ideal Reactors
LEARNING OBJECTIVES
After completing this chapter, you should be able to
1. explain the differences between the three ideal reactors: batch, continuous stirred
tank, and plug flow;
2. explain how the reactant and product concentrations vary spatially in ideal batch,
ideal continuous stirred tank, and ideal plug-flow reactors;
3. derive ‘‘design equations’’ for the three ideal reactors, for both homogeneous
and heterogeneous catalytic reactions, by performing component material balances;
4. calculate reaction rates using the ‘‘design equation’’ for an ideal continuous
stirred-tank reactor;
5. simplify the most general forms of the ‘‘design equations’’ for the case of constant
mass density.
The next few chapters will illustrate how the behavior of chemical reactors can be
predicted, and how the size of reactor required for a given ‘‘job,’’ can be determined.
These calculations will make use of the principles of reaction stoichiometry and reaction
kinetics that were developed in Chapters 1 and 2.
There are many different types of reactor. One of the most important features that
differentiates one kind of reactor from another is the nature of mixing in the reactor. The
influence of mixing is easiest to understand through the material balance(s) on the reactor.
These material balances are the starting point for the discussion of reactor performance.
3.1 GENERALIZED MATERIAL BALANCE
The reaction rate r
i
is an intensive variable. It describes the rate of formation of species
‘‘i’’ at any point in a chemical reactor. However, as we learned in Chapter 2, the rate of
any reaction depends on variables such as temperature and the species concentrations. If
these variables change from point to point in the reactor, r
i
also will change from point
to point.
For the time being, to emphasize that r
i
depends on temperature and on the various
species concentrations, let’s use the nomenclature
r
i
= r
i
(T; all C
i
)
The term‘‘all C
i
’’ reminds us that the reaction rate may be influenced by the concentration of
each and every species in the system.
Consider an arbitrary volume (V) in which the temperature and the species concen-
trations vary from point to point, as shown below.
36
T
1
, all C
i,1
(Point 1)
T
2
, all C
i,2
(Point 2)
T
3
, all C
i,3
(Point 3)
The rate at which ‘‘i’’ is formed in this control volume by a chemical reaction or reactions is
designated G
i
, the generation rate of ‘‘i’’. The units of G
i
are moles/time. For a homogeneous
reaction, G
i
is related to r
i
by
Generation rate÷÷
homogeneous reaction
G
i
=
Z Z Z
V
r
i
dV
(3-1)
For a heterogeneous catalytic reaction, where r
i
has units of moles/time-weight of catalyst,
G
i
is given by
Generation rate÷÷
heterogenous catalytic
reaction
G
i
=
Z Z Z
W
r
i
dW =
Z Z Z
V
r
i
r
B
dV (3-2)
Here, r
B
is the bulk density of the catalyst (weight/volume of reactor). In Eqns. (3-1) and
(3-2), r
i
is the net rate at which ‘‘i’’ is formed by all of the reactions taking place, as given by
Eqn. (1-17).
Although they are formally correct, Eqns. (3-1) and (3-2) are not very useful in practice.
This is because the reaction rate r
i
is never known as an explicit function of position.
Therefore, the indicated integrations cannot be performed directly. The means of resolving
this apparent dilemma will become evident as we treat some specific cases.
Generalized component material balance
Consider the control volume shown below, with chemical reactions taking place that result
in the formation of species ‘‘i’’ at a rate, G
i
. Species ‘‘i’’ flows into the systemat a molar flow
rate of F
i0
(moles i/time), and flows out of the system at a molar flow rate of F
i
.
F
i0
F
i
T
1
, all C
i,1
(Point 1)
T
2
, all C
i,2
(Point 2)
T
3
, all C
i,3
(Point 3)
3.1 Generalized Material Balance 37
The molar material balance for species ‘‘i’’ for this control volume is
rate in ÷ rate out ÷ rate of generation by chemical reactions = rate of accumulation
Generalized material balance
on component ‘‘i’’
F
i0
÷ F
i
÷ G
i
=
dN
i
dt
(3-3)
Here ‘‘t’’ is the time and N
i
is the number of moles of ‘‘i’’ in the system at any time.
Now let’s consider three special cases that are of practical significance, and allow Eqn.
(3-3) to be simplified to a point that it is useful.
3.2 IDEAL BATCH REACTOR
A batch reactor is defined as a reactor in which there is no flow of mass across the system
boundaries, once the reactants have been charged. The reaction is assumed to begin at some
precise point in time, usually taken as t = 0. This time may correspond, for example, to
when a catalyst or initiator is added to the batch, or to when the last reactant is added.
As the reaction proceeds, the number of moles of each reactant decreases and the
number of moles of each product increases. Therefore, the concentrations of the species in
the reactor will change with time. The temperature of the reactor contents may also change
with time. The reaction continues until it reaches chemical equilibrium, or until the limiting
reactant is consumed completely, or until some action is taken to stop the reaction, e.g.,
cooling, removing the catalyst, adding a chemical inhibitor, etc.
Figure 3-1a Overall view of a
nominal 7000 gallon batch reactor
(in a plant of Syngenta Crop
Protection, Inc.). This reactor is used
to produce several different products.
The reactor has a jacket around it to
permit heat to be transferred into or
out of the reactor contents via a
heating or cooling fluid that
circulates through the jacket. The
hoists are used for lifting raw
materials to higher levels of the
structure. (Photo used with
permission of Syngenta Crop
Protection, Inc.)
38 Chapter 3 Ideal Reactors
Batch reactors are used extensively throughout the chemical and pharmaceutical
industries to manufacture products on a relatively small scale. Properly equipped, these
reactors are very flexible. Asingle reactor may be used to produce many different products.
Batch reactors usually are mechanically agitated to ensure that the contents are well
mixed. Agitation also increases the heat-transfer coefficient between the reactor contents
and any heat-transfer surface in the reactor. In multiphase reactors, agitation may also keep a
solid catalyst suspended, or may create surface area between two liquid phases or between a
gas phase and a liquid phase.
Very few reactions are thermally neutral (DH
R
= 0), so it frequently is necessary to
either supply heat or remove heat as the reaction proceeds. The most common means to
transfer heat is to circulate a hot or cold fluid, either through a coil that is immersed in the
reactor, or through a jacket that is attached to the wall of the reactor, or both.
For a batch reactor, F
i0
= F
i
= 0. Therefore, for a homogeneous reaction, Eqn. (3-3)
becomes
G
i
=
Z Z Z
V
r
i
dV =
dN
i
dt
(3-4)
Ideal batch reactor
Now, consider a limiting case of batch-reactor behavior. Suppose that agitation of the reactor
contents is vigorous, i.e., mixing of fluid elements in the reactor is very intense. Then the
temperature and the species concentrations will be the same at every point in the reactor, at
every point in time. A batch reactor that satisfies this condition is called an ideal batch
reactor. Many laboratory and commercial reactors can be treated as ideal batch reactors, at
least as a first approximation.
For an ideal batch reactor, r
i
is not a function of position. Therefore,
RRR
V
r
i
dV = r
i
V
and Eqn. (3-4) becomes
r
i
V =
dN
i
dt
Figure 3-1b The top of the reactor in Figure 3-1a. The view port in the left front of the picture
permits the contents of the reactor to be observed, and can be opened to permit solids to be charged to
the reactor. Amotor that drives an agitator is located in the top center of the picture, and a charging line
and valve actuator connected to a valve are on the left. (Photo used with permission of Syngenta Crop
Protection, Inc.)
3.2 Ideal Batch Reactor 39
Rearranging
Design equation÷÷
ideal batch reactor÷÷
homogeneous reaction
(moles)
1
V
dN
i
dt
= r
i
(3-5)
Equation (3-5) is referred to as the design equation for an ideal batch reactor, in
differential form. This equation is valid no matter how many reactions are taking place,
provided that Eqn. (1-17) is used to express r
i
, and provided that all of the reactions are
homogeneous.
The subject of multiple reactions is treated inChapter 7. Until then, wewill be concerned
with the behavior of one, stoichiometrically simple reaction. For that case, r
i
in Eqn. (3-5) is
just the rate equation for the formation of species ‘‘i’’ in the reaction of concern.
The variable that describes composition in Eqn. (3-5) is N
i
, the total moles of species
‘‘i’’. It sometimes is more convenient to work problems in terms of either the extent of
reaction j or the fractional conversion of a reactant, usually the limiting reactant. Extent of
reaction is very convenient for problems where more than one reaction takes place.
Fractional conversion is convenient for single-reaction problems, but can be a source of
confusion in problems that involve multiple reactions. The use of all three compositional
variables, moles (or molar flow rates), fractional conversion, and extent of reaction, will be
illustrated in this chapter, and in Chapter 4.
If ‘‘i’’ is a reactant, say A, then the number of moles of Ain the reactor at anytime can be
written in terms of the fractional conversion of A.
x
A
=
N
A0
÷ N
A
N
A0
; N
A
= N
A0
(1 ÷ x
A
)
In terms of fractional conversion, Eqn. (3-5) is
Design equation÷÷
ideal batch reactor÷÷
homogeneous reaction
(fractional conversion)
N
A0
V
dx
A
dt
= ÷r
A
(3-6)
If ‘‘A’’ is the limiting reactant, the value of x
A
that is stoichiometrically attainable will lie
between 0 and 1. However, as discussed in Chapter 1, chemical equilibrium may limit the
value of x
A
that can actually be achieved to something less than 1.
Equation (3-6) should not be applied to a product. First, N
A
will be greater than N
A0
if
‘‘A’’ is a product. Moreover, if N
A0
= 0; x
A
is infinite. However, Eqn. (3-5) can be used for
either a product or a reactant.
The design equation can also be written in terms of the extent of reaction. If only one
stoichiometrically simple reaction is taking place
j =
DN
i
n
i
=
N
i
÷ N
i0
n
i
(1-4)
Design equation÷÷
ideal batch reactor÷÷
homogeneous reaction
(extent of reaction)
n
i
V
dj
dt
= r
i
(3-7)
40 Chapter 3 Ideal Reactors
Equations (3-5)–(3-7) are alternative forms of the design equation for an ideal batch
reactor with a homogeneous reaction taking place. Despite the somewhat pretentious name,
design equations are nothing more than component material balances, i.e., molar balances
on ‘‘i’’, ‘‘A’’, etc.
The volume V in Eqns. (3-5)–(3-7) is that portion of the overall reactor volume in which
the reaction actually takes place. This is not necessarily the whole geometrical volume of
the reactor. For example, consider a reaction that takes place in a liquid that partially fills a
vessel. If no reaction takes place in the gas-filled ‘‘headspace’’ above the liquid, then Vis the
volume of liquid, not the geometrical volume of thevessel, which includes the ‘‘headspace.’’
Equations (3-5)–(3-7) apply to a homogeneous reaction. For a reaction that is catalyzed
by a solid, the design equation that is equivalent to Eqn. (3-5) is
Design equation÷÷
ideal batch reactor÷÷
heterogeneous catalytic reaction
(moles)
1
W
dN
i
dt
= r
i
(3-5a)
EXERCISE 3-1
Derive this equation.
The equivalents to Eqns. (3-6) and (3-7) for heterogeneously catalyzed reactions are givenin
Appendix 3 at the end of this chapter, and are labeled Eqns. (3-6a) and (3-7a). Be sure that
you can derive them.
Temperature variation with time
In developing Eqns. (3-5)–(3-7), we did not assume that the temperature of the reactor contents
was constant, independent of time. Only one assumption was made concerning temperature,
i.e., there are no spatial variations in the temperature at any time. An ideal batch reactor is said
to be isothermal when the temperature does not vary with time. The design equations for an
ideal batch reactor are valid for both isothermal and nonisothermal operation.
Constant volume
If Vis constant, independent of time, Eqn. (3-5) can be written in terms of concentration as
dC
i
dt
= r
i
(3-8)
where C
i
is the concentration of species i. Similarly, if V is constant, Eqn. (3-6) can be
written as
C
A0
dx
A
dt
= ÷r
A
(3-9)
where C
A0
is the initial concentration of A. Equations (3-8) and (3-9) are alternative forms of
the design equations for an ideal, constant-volume batch reactor, in differential form. The
lighter boxes around these equations indicate that they are not as general as Eqns. (3-5) and
(3-6) because they contain the assumption of constant volume.
If the volume V is constant, then the mass density of the system, r (mass/volume), must
also be constant, since the mass of material in a batch reactor does not change with time. We
could have specified that the mass density was constant instead of specifying that the reactor
volume was constant. These two statements are equivalent. However, for a batch reactor,
3.2 Ideal Batch Reactor 41
constant volume probably is easier to visualize than constant mass density. For constant-
volume (constant mass density) systems, the design equations can be written directly in
terms of concentrations, which can easily be measured. For systems where the mass density
is not constant, we must work with the most general forms of the design equations, using
moles, fractional conversion, or extent of reaction.
For a heterogeneous catalytic reaction, derivation of the constant-volume version of
Eqn. (3-5a) requires a bit of manipulation.
1
W
dN
i
dt
= r
i
(3-5a)
Dividing by the reactor volume V and multiplying by W
1
V
dN
i
dt
=
W
V

r
i
If V is constant,
Design equation÷÷
ideal batch reactor÷÷
heterogeneous catalytic reaction
(constant volume)
dC
i
dt
= C
cat
r
i
(3-8a)
Equation (3-8a) is the design equation for an ideal, constant-volume, batch reactor for a
reaction that is catalyzed by a solid catalyst. The symbol C
cat
represents the mass
concentration (mass/volume) of the catalyst. The catalyst concentration does not change
with time if V is constant.
The equivalent of Eqn. (3-9) for a heterogeneous catalytic reaction is given in Appendix
3.I at the end of this chapter and is labeled Eqn. (3-9a).
The assumption of constant volume is valid for most industrial batch reactors. The mass
density is approximately constant for a large majority of liquids, even if the temperature
changes moderately as the reaction proceeds. Therefore, the assumption of constant volume
is reasonable for batch reactions that take place in the liquid phase. Moreover, if a rigid
vessel is filled with gas, the gas volume will be constant because the dimensions of the vessel
are fixed and do not vary with time.
Variable volume
If V changes with time, Eqn. (3-5) must be written
1
V
dN
i
dt
=
1
V
d(C
i
V)
dt
=
dC
i
dt
÷
C
i
V
dV
dt
= r
i
Clearly, this equation is more complex, and harder to work with, than Eqn. (3-8).
EXERCISE 3-2
There are a few batch reactors where the assumption of constant
volume is not appropriate. Can you think of one? Hint: You
probably come within 10 ft of this reactor at least once a week,
perhaps even every day.
Integrated forms of the design equation
The design equation must be integrated in order to solve problems in reactor design and
analysis. In order to actually perform the integration, the temperature must be known as a
function of either time or composition. This is because the rate equation r
i
contains one or
more constants that depend on temperature.
42 Chapter 3 Ideal Reactors
As we shall see in Chapter 8, the energy balance determines how the reactor temper-
ature changes as the reaction proceeds. Broadly, there are three possibilities:
1. The energy balance is so complexthat the design equation and the energy balance must be
solved simultaneously. We shall leave this case for Chapter 8.
2. The reactor can be heated or cooled such that the temperature changes, but is known as a
function of time. An example of this case is treated in Chapter 4.
3. The reactor is adiabatic, or is heated or cooled so that it is isothermal. If the reactor is
isothermal, the parameters in the rate equation are constant, i.e., they do not depend on
either time or composition. In the adiabatic case, the temperature can be expressed as a
function of composition. Therefore, the parameters in the rate equation can also be
written as functions of composition. This will be illustrated in Chapter 8.
For the third case, i.e., an isothermal or adiabatic reactor, r
i
depends only on concen-
tration. If Vis constant, or can be expressed as a function of concentration, Eqn. (3-5) can be
symbolically integrated from t = 0; N
i
= N
i0
to t = t; N
i
= N
i
. The result is
Z
N
i
Ni0
1
V
dN
i
r
i
=
Z
t
0
dt = t (3-10)
When the reactor temperature varies with time in a known manner, then r
i
depends on
time as well as concentration. In such a case, Eqn. (3-5) must be used as a starting point
instead of Eqn. (3-10). This will be illustrated in the next chapter.
The integrated forms of Eqns. (3-5) through (3-9) for Case 3 above are given in
Appendix 3.I, and are labeledas Eqns. (3-10) through (3-14), respectively. Appendix 3.I also
contains the integrated forms of Eqns. (3-5a) through (3-9a) for Case 3.
Once the integrations of the design equations have been performed, the time required
to reach a concentration C
A
, or a fractional conversion x
A
, or an extent of reaction j can be
calculated. Conversely, the value of C
A
; x
A
, or j that results for a specified reaction time can
also be calculated. Chapter 4 illustrates the solution of some batch-reactor problems where the
reactor is isothermal, or where the temperature is knownas a function of time. The simultaneous
solution of the design equation and the energy balance is considered in Chapter 8.
3.3 CONTINUOUS REACTORS
When the demand for a single chemical product reaches a high level, in the region of tens of
million pounds per year, there generally will be an economic incentive to manufacture the
product continuously, using a reactor that is dedicated to that product. The reactor may
operate at steady state for a year or more, with planned shutdowns only for regular
maintenance, catalyst changes, etc.
Almost all of the reactors in a petroleum refinery operate continuously because of the
tremendous annual production rates of the various fuels, lubricants, and chemical inter-
mediates that are manufactured in a refinery. Many well-known polymers such as poly-
ethylene and polystyrene are also produced in continuous reactors, as are many large-
volume chemicals such as styrene, ethylene, ammonia, and methanol.
Figure 3-3 is a simplified flowsheet showing some of the auxiliary equipment that may be
associated with a continuous reactor. In this example, the feed stream is heated to the desired
inlet temperature, first in a feed/product heat exchanger and then in a fired heater. The stream
leavingthe reactor contains the product(s), the unconvertedreactants, andanyinert components.
3.3 Continuous Reactors 43
This streamis cooled in the feed/product heat exchanger and then is cooled further to condense
some of its components. The gas and liquid phases are separated. The liquid phase is sent to a
separations section (fractionation unit), where the product is recovered. A purge is taken from
the gas that leaves the separator, in part to prevent buildup of impurities in the recycle loop. The
remainder of the gas is recycled.
Most of the unconverted reactants from a continuous reactor will be recycled back into
the feed stream, unless the fractional conversion of the reactants is very high. Some of the
product and/or inert components also may be recycled, to aid in control of the reactor
temperature, for example.
Continuous reactors normally operate at steady state. The flowrate and composition of
the feed stream do not vary with time, and the reactor operating conditions do not vary with
time. We will assume steady state in developing the design equations for the two ideal
Figure 3-2 A continuous reactor,
with associated equipment, for the
catalytic isomerization of heavy
normal paraffins, containing about 35
carbon atoms, to branched paraffins.
The catalyst is comprised of platinum
on an acidic zeolite that has relatively
large pores. The reaction produces
lubricants that have a high viscosity at
high temperatures, but retain the
characteristics of a liquid at low
temperatures. Without the
isomerization reaction, the lubricant
would become ‘‘waxy’’ and would not
flow at low temperatures. This unit is
located at the ExxonMobil refinery in
Fawley, UK. (Photo, ExxonMobil
2003 Summary Annual Report.)
44 Chapter 3 Ideal Reactors
continuous reactors, the ideal continuous stirred-tank reactor (CSTR), and the ideal plug-
flow reactor (PFR).
3.3.1 Ideal Continuous Stirred-Tank Reactor (CSTR)
Like the ideal batch reactor, the ideal CSTR is characterized by intense mixing. The
temperature and the various concentrations are the same at every point in the reactor. The
feed stream entering the reactor is mixed instantaneously into the contents of the reactor,
immediately destroying the identity of the feed. Since the composition and the temperature
are the same everywhere in the CSTR, it follows that the effluent stream must have exactly
the same composition and temperature as the contents of the reactor.
Feed
Composition and
temperature are the
same everywhere in
the reactor
Composition and
temperature are the
same in the effluent as
in the reactor
Effluent
Charge heater
Reactor
Combined
feed-reactor
effluent exchanger
Effluent condenser
Separator liquid
to fractionation
Separator
Net
separator
gas
Recycle
compressor
Charge
Figure 3-3 A typical flow scheme for
the reactor section of a continuous plant.
1
Several items of heat exchange
equipment, a recycle compressor, and a
phase separator are required to support
the steady-state operation of the reactor.
(Figure Copyright 2004 UOP LLC. All
rights reserved. Used with permission.)
1
Stine, M. A., Petroleum Refining, presented at the North Carolina State University AIChE Student Chapter
Meeting, November 15, 2002.
3.3 Continuous Reactors 45
On a small scale, e.g., a laboratory reactor, mechanical agitation is usually required to
achieve the necessary high intensity of mixing. On a commercial scale, the required mixing
sometimes can be obtained by introducing the feed streaminto the reactor at a high velocity,
such that the resulting turbulence produces intense mixing. A bed of catalyst powder that is
fluidized by an incoming gas or liquid stream, i.e., a fluidized-bed reactor, might be treated
as a CSTR, at least as a first approximation. Another reactor configuration that can
approximate a CSTR is a slurry bubble column reactor, in which a gas feed stream is
sparged through a suspension of catalyst powder in a liquid. Slurry bubble column reactors
are used in some versions of the Fischer–Tropsch process for converting synthesis gas, a
mixture of H
2
and CO, into liquid fuels.
The continuous stirred-tank reactor is also known as a continuous backmix, backmixed,
or mixed flow reactor. In addition to the catalytic reactors mentioned in the preceding
paragraph, the reactors that are used for certain continuous polymerizations, e.g., the
polymerization of styrene monomer to polystyrene, closely approximate CSTRs.
Because of the intense mixing in a CSTR, temperature and concentration are the same
at every point in the reactor. Therefore, as with the ideal batch reactor, r
i
does not depend on
position. For a homogeneous reaction, Eqns. (3-1) and (3-3) simplify to
F
i0
÷ F
i
÷ r
i
V =
dN
i
dt
(3-15)
Equation (3-15) describes the unsteady-state behavior of a CSTR. This is the equation that
must be solved to explore strategies for starting up the reactor, or shutting it down, or
switching from one set of operating conditions to another.
At steady state, the concentrations and the temperature of the CSTR do not vary with
time. The exact temperature of operation is determined by the energy balance, as we shall
see in Chapter 8. At steady state, the right-hand side of Eqn. (3-15) is zero.
F
i0
÷ F
i
÷ r
i
V = 0
Design equation÷÷
ideal CSTR÷÷
homogeneous reaction
(molar flowrates)
V =
F
i0
÷ F
i
÷r
i
(3-16)
Equation (3-16) is the designequation for an ideal CSTR. It can be applied to a reactor where
more than one reaction is taking place, if Eqn. (1-17) is used to express r
i
.
For a single reaction, it frequently is convenient to write Eqn. (3-16) in terms of either
extent of reaction or fractional conversion of a reactant. If ‘‘i’’ is a reactant, say A,
F
A
= F
A0
(1 ÷ x
A
)
and Eqn. (3-16) becomes
Design equation÷÷
ideal CSTR÷÷
homogeneous reaction
(molar flowrates)
V
F
A0
=
x
A
÷r
A
(3-17)
Alternatively, if only one, stoichiometrically simple reaction is taking place,
j =
F
i
÷ F
i0
n
i
46 Chapter 3 Ideal Reactors
and Eqn. (3-16) becomes
Design equation÷÷
ideal CSTR÷÷
homogeneous reaction
(extent of reaction)
V =
n
i
j
r
i
(3-18)
Equations (3-16)–(3-18) are equivalent forms of the design equation for an ideal CSTR.
In these equations, ÷r
A
(or r
i
) is always evaluated at the exit conditions of the reactor, i.e., at
the temperature and concentrations that exist in the effluent stream, and therefore in the
whole reactor volume. Once again, the design equation is simply a molar component
material balance.
For a heterogeneous catalytic reaction, the equivalent form of Eqn. (3-16) is
Design equation÷÷
ideal CSTR÷÷
heterogeneous catalytic reaction
(molar flowrates)
W =
F
i0
÷ F
i
÷r
i
(3-16a)
EXERCISE 3-3
Derive this equation.
Appendix 3.II gives the forms of the design equation for a heterogeneous catalytic
reaction that are equivalent to Eqns. (3-17) and (3-18). These equations are labeled Eqns.
(3-17a) and (3-18a).
Space time and space velocity
The molar feed rate, F
A0
, is the product of the inlet concentration C
A0
and the inlet
volumetric flow rate y
0
, i.e.,
F
A0
= y
0
C
A0
(3-19)
For a homogeneous reaction, the space time at inlet conditions t
0
is defined as
t
0
=V=y
0
(3-20)
This definition of space time applies to any continuous reactor, whether it is a CSTR or not.
For a homogeneous reaction, space time has the dimension of time. It is related to the
average time that the fluid spends in the reactor, although it is not necessarily exactly equal
to the average time. However, the space time and the average residence time behave in a
similar manner. If the reactor volume V increases and the volumetric flow rate y
0
stays
constant, both the space time and the average residence time increase. Conversely, if the
volumetric flowrate y
0
increases and the reactor volume stays constant, both the space time
and the average residence time decrease.
Space time influences reaction behavior in a continuous reactor in the same way that
real time influences reaction behavior in a batch reactor. In a batch reactor, if the time that the
reactants spend in the reactor increases, the fractional conversion and the extent of reaction
will increase, and the concentrations of the reactants will decrease. The same is true for
space time and a continuous reactor. If a continuous reactor is at steady state, the conversion
and the extent of reaction will increase, and the reactant concentrations will decrease, when
the space time is increased.
3.3 Continuous Reactors 47
Using Eqns. (3-19) and (3-20), Eqn. (3-17) can be written as
Design equation÷÷
ideal CSTR÷÷
homogeneous reaction
(in terms of space time)
t
0
=
C
A0
x
A
÷r
A
(3-21)
The concept of space time is also applicable to heterogeneously catalyzed reactions. In
this case, t
0
is defined by
t
0
=W=y
0
(3-22)
Here, the units of t
0
are (wt. catalyst-time/volume of fluid). With this definition, Eqn. (3-21)
applies to both homogeneous reactions and reactions catalyzed by solids.
The inverse of space time is known as space velocity. Space velocity is designated in
various ways, e.g., SV, GHSV(gas hourly space velocity), and WHSV(weight hourly space
velocity). ‘‘Space velocity’’ is commonly used in the field of heterogeneous catalysis, and
there can be considerable ambiguity in the definitions that appear in the literature. For
example, GHSV may be defined as the volumetric flowrate of gas entering the catalyst
divided by the weight of catalyst. In this case, the units of space velocity are (volume of fluid/
time-wt. catalyst). The volumetric flowrate may correspond to inlet conditions or to STP.
However, it is not uncommon to find space velocity defined as the volumetric flowrate of gas
divided by the volume of catalyst bed, or by the volume of catalyst particles. With either of
these definitions, the units of space time are inverse time, even though the reaction is
catalytic.
When the term ‘‘space velocity’’ is encountered in the literature, it is important to
pay very careful attention to how this parameter is defined! Analysis of the units may
help.
This book will emphasize the use of space time, since it is analogous to real time in a
batch reactor. Space velocity can be a bit counterintuitive. Conversion increases as space
time increases, but conversion decreases as space velocity increases.
Constant fluid density
If the mass density (mass/volume) of the fluid flowing through the reactor is constant, i.e., if
it is the same in the feed, in the effluent, and at every point in the reactor, then the subscript
‘‘0’’ can be dropped from both t and y. In this case Eqn. (3-21) can be written as
t =
C
A0
x
A
÷r
A
(3-23)
When the fluid density is constant, then t(=V=y) is the average residence time that the
fluid spends in the reactor. This is true for the CSTR, and for any other continuous reactor
operating at steady state.
If (and only if ) the fluid density is constant,
x
A
=
F
A0
÷ F
A
F
A0
=
yC
A0
÷ yC
A
yC
A0
=
C
A0
÷ C
A
C
A0
48 Chapter 3 Ideal Reactors
so that Eqn. (3-23) becomes
t =
C
A0
÷ C
A
÷r
A
(3-24)
Equations (3-23) and (3-24) are design equations for an ideal CSTR with a constant-
density fluid. The lighter box around these equations indicates that they are not as
general as Eqn. (3-21), which is not restricted to a constant-density fluid. Equations
(3-23) and (3-24) apply to both homogeneous and heterogeneously catalyzed reactions,
provided that t is calculated from the appropriate equation, either Eqn. (3-20) or Eqn.
(3-22).
Calculating the reaction rate
The various forms of the design equation for an ideal CSTR (Eqns. (3-16) through (3-18),
(3-21), (3-23), and (3-24)) can be used to calculate a numerical value of the rate of reaction,
if all of the other parameters in the equation are known. The following example illustrates
this use of the CSTR design equation.
EXAMPLE 3-1
Calculation of Rate
of Disappearance
of Thiophene
The catalytic hydrogenolysis of thiophene was carried out in a reactor that behaved as an ideal CSTR.
The reactor contained 8.16 g of ‘‘cobalt molybdate’’ catalyst. In one experiment, the feed rate of
thiophene to the reactor was 6:53 × 10
÷5
mol/min. The fractional conversion of thiophene in the
reactor effluent was measured and found to be 0.71. Calculate the value of the rate of disappearance
of thiophene for this experiment.
APPROACH Equation (3-16a) is the most fundamental form of the design equation for a heterogeneous catalytic
reaction in an ideal CSTR.
W =
F
i0
÷ F
i
÷r
i
(3-16a)
Using the subscript ‘‘T’’ for thiophene and rearranging,
÷r
T
=
F
T0
÷ F
T
W
From the definition of fractional conversion, F
T0
÷ F
T
= F
T0
x
T
. Therefore, all of the param-
eters on the right-hand side of the above equation are known and ÷r
T
can be calculated.
SOLUTION
÷r
T
=
F
T0
x
T
W
=
6:53 × 10
÷5
(mol/min) × 0:71
8:16(g)
= 0:57 × 10
÷5
(mol/min-g)
3.3.2 Ideal Continuous Plug-Flow Reactor (PFR)
The plug-flow reactor is the third and last of the so-called ‘‘ideal’’ reactors. It is frequently
represented as a tubular reactor, as shown below.
3.3 Continuous Reactors 49
z
Little “plugs” of fluid flow single file
through reactor:
• no mixing in direction of flow, i.e.,
one fluid element cannot pass or mix
with another;
• no temperature or concentration
variations normal to flow.
F
i0
F
i
The ideal plug-flow reactor has two defining characteristics:
1. There is no mixing in the direction of flow. Therefore, the concentrations of the
reactants decrease in the direction of flow, from the reactor inlet to the reactor outlet. In
addition, the temperature may vary in the direction of flow, depending on the magnitude of
the heat of reaction, and on what, if any, heat transfer takes place through the walls of the
reactor. Because of the variation of concentration, and possibly temperature, the reaction
rate, r
i
, varies in the direction of flow;
2. There is no variation of temperature or concentration normal to the direction of flow.
For a tubular reactor, this means that there is no radial or angular variation of temperature or
of any species concentration at a given axial position z. As a consequence, the reaction rate r
i
does not vary normal to the direction of flow, at any cross section in the direction of flow.
The plug-flowreactor may be thought of as a series of miniature batch reactors that flow
through the reactor in single file. Each miniature batch reactor maintains its integrity as it
flows from the reactor inlet to the outlet. There is no exchange of mass or energy between
adjacent ‘‘plugs’’ of fluid.
In order for a real reactor to approximate this ideal condition, the fluid velocity cannot
vary normal to the direction of flow. For a tubular reactor, this requires a flat velocity profile
in the radial and angular directions, as illustrated below.
50 Chapter 3 Ideal Reactors
For flow through a tube, this flat velocity profile is approached when the flow is highly
turbulent, i.e., at high Reynolds numbers.
Let’s analyze the behavior of an ideal plug-flowreactor. We might be tempted to choose
the whole reactor as a control volume as we did with the ideal batch reactor and the ideal
CSTR and apply Eqn. (3-3),
F
i0
÷ F
i
÷ G
i
=
dN
i
dt
(3-3)
Assuming a homogeneous reaction, setting the right-hand side equal to 0 to reflect steady
state, and substituting Eqn. (3-1),
F
i0
÷ F
i
÷
Z Z Z
V
r
i
dV = 0 (3-25)
For a PFR, the reaction rate varies with position in the direction of flow. Therefore, r
i
is a
function of V and the above integral cannot be evaluated directly.
We can solve this problem in two ways, the easy way and the hard way.
3.3.2.1 The Easy Way—Choose a Different Control Volume
Let’s choose a different control volume over which towrite the component material balance.
More specifically, let’s choose the control volume such that r
i
does not depend on V.
From the above discussion, it should be clear that the new control volume must be
differential in the direction of flow, since r
i
varies in this direction. However, the control volume
can span the whole cross section of the reactor, normal to flow, since there are no temperature or
concentrationgradients normal toflow. Therefore, r
i
will beconstant over anysuchcross section.
For a tubular reactor, the control volume is a slice through the reactor perpendicular to
the axis (z direction), with a differential thickness dz, as shown below.
dz
F
i
+ dF
i
F
i
z = z
The inlet face of the control volume is located at an axial position, z. The molar flowrate
of ‘‘i’’ into the element is F
i
and the molar flow rate of ‘‘i’’ leaving the element is F
i
÷ dF
i
.
For this element, the steady-state material balance on ‘‘i’’ is
F
i
÷ (F
i
÷ dF
i
) ÷ r
i
dV = 0
Design equation÷÷
ideal PFR÷÷
homogeneous reaction
(molar flowrate)
dV =
dF
i
r
i
(3-26)
3.3 Continuous Reactors 51
Equation (3-26) is the design equation for an ideal PFR, in differential form. This equation
applies to a PFR where more than one reaction is taking place, provided that r
i
is expressed
using Eqn. (1-17).
For a single reaction, it may be convenient to write Eqn. (3-26) in terms of either
extent of reaction or fractional conversion. If ‘‘i’’ is a reactant, say A, the molar flow rates
may be written in terms of the fractional conversion x
A
, i.e., F
A
= F
A0
(1 ÷ x
A
), and
dF
A
= ÷F
A0
dx
A
. With these transformations, Eqn. (3-26) becomes
Design equation÷÷
ideal PFR÷÷
homogeneous reaction
(fractional conversion)
dV
F
A0
=
dx
A
÷r
A
(3-27)
If only one, stoichiometrically simple reaction takes place,
j =
F
i
÷ F
i0
n
i
; dF
i
= n
i
dj
Design equation÷÷
ideal PFR÷÷
homogeneous reaction
(extent of reaction)
dV =
n
i
dj
r
i
(3-28)
Equations (3-26)–(3-28) are various forms of the design equation for a homogeneous
reaction in an ideal, plug-flowreactor, in differential form. The equivalents of Eqns. (3-26)–
(3-28) for a heterogeneous catalytic reaction are given in Appendix 3.IIIAas Eqns. (3-26a),
(3-27a), and (3-28a). Be sure that you can derive them.
Temperature variation with position
In developing Eqns. (3-26)–(3-28), we assumed that the temperature was constant in any
cross section normal to the direction of flow. We did not assume that the temperature was
constant in the direction of flow. For a PFR, the reactor is said to be isothermal if the
temperature does not vary with position in the direction of flow, e.g., with axial position in
a tubular reactor. On the other hand, for nonisothermal operation, the temperature will
vary with axial position. Consequently, the rate constant and perhaps other parameters in
the rate equation such as an equilibrium constant will also vary with axial position. The
design equations for an ideal PFR are valid for both isothermal and nonisothermal
operation.
Space time and space velocity
As notedinthediscussionof theideal CSTR, thespace time at inlet conditions, t
0
, is definedby
t
0
=
V
y
0
(3-20)
Using Eqn. (3-20), Eqn. (3-27) can be written in terms of C
A0
and t
0
as
dt
0
= C
A0
dx
A
(÷r
A
)
(3-29)
52 Chapter 3 Ideal Reactors
This equation is also valid for a heterogeneous catalytic reaction, if Eqn. (3-22) is used to
define t
0
.
The concept of ‘‘space velocity,’’ discussed in connection with the ideal CSTR, also
applies to ideal PFRs.
Constant density
If the mass density of the flowing fluid is the same at every position in the reactor, the
subscript ‘‘0’’ can be dropped fromt and y. As noted in the discussion of the ideal CSTR, for
the case of constant density, t(=V=y) is the average residence time of the fluid in the reactor.
This is true for any continuous reactor operating at steady state. However, for the ideal PFR, t
has an even more exact meaning. Not only is t the average residence time of the fluid in the
reactor, it is also the exact residence time that each and every fluid element spends in the
reactor. For an ideal PFR, there is no mixing in the direction of flow, i.e., adjacent fluid
elements cannot mix with or pass each other. Therefore, every element of fluid must spend
exactly the same time in the reactor. That time is t, when the mass density is constant.
For the case of constant density, Eqn. (3-29) becomes
dt = C
A0
dx
A
(÷r
A
)
(3-30)
For constant density, x
A
= (C
A0
÷ C
A
)=C
A0
and dx
A
= ÷dC
A
=C
A0
, so that Eqn. (3-30) can
be written as
dt =
÷dC
A
(÷r
A
)
(3-31)
Equations (3-30) and (3-31) are also valid for a PFR with a heterogeneous catalytic
reaction taking place, provided that Eqn. (3-22) is used to define t.
Integrated forms of the design equation
As with the batch reactor, the design equations in differential form for the PFR must be
integrated to solve engineering problems. The same three possibilities that were discussed
for the batch reactor also exist here, except that the variable of time for the batch reactor is
replaced by position in the direction of flowfor the ideal PFR. For Case 3, where the reactor
is either isothermal or adiabatic, Eqns. (3-26) and (3-27) can be integrated symbolically to
give
V =
Z
Fi
F
i0
dF
i
r
i
(3-32)
V
F
A0
=
Z
x
A
0
dx
A
÷r
A
(3-33)
The initial conditions for these integrations are V = 0, F
i
= F
i0
, x
A
= 0.
Appendix 3.III contains the equivalents of these equations for different variables (e.g., j
and t), for heterogeneous catalytic reactions, and for the constant-density case. The
numbering of the equations in Appendix 3.IIIA continues from Eqn. (3-33) above.
3.3 Continuous Reactors 53
3.3.2.2 The Hard Way—Do the Triple Integration
Let’s return to Eqn. (3-25) and again focus on a tubular reactor, with flow in the axial
direction.
F
i0
÷ F
i
÷
Z Z Z
V
r
i
dV = 0 (3-25)
The triple integral may be written in terms of three coordinates z (axial position), u (angular
position), and R (radial position).
F
i0
÷ F
i
÷
Z
2p
0
Z
R0
0
Z
L
0
r
i
du RdRdz = 0 (3-38)
In this equation, R
0
is the inside radius of the tube and L is its length. Since there are no
temperature or concentration gradients normal to the direction of flow, r
i
does not depend on
either u or R. Since
R
2p
0
R
R
0
0
du RdR = A, where A is the cross-sectional area of the tube
(A = pR
2
0
), Equation (3-38) may be written as
F
i0
÷ F
i
÷ A
Z
L
0
r
i
dz = 0
Differentiating this equation with respect to z gives dF
i
=dz = Ar
i
, which can be rearranged
to
Adz = dV =
dF
i
r
i
(3-26)
Equation (3-26) has been recaptured. Therefore, all of the equations derived from it can be
obtained via the triple integration in Eqn. (3-38).
3.4 GRAPHICAL INTERPRETATION OF THE DESIGN EQUATIONS
Figure 3-4 is a plot of (1= ÷ r
A
), the inverse of the rate of disappearance of Reactant A,
versus the fractional conversion of reactant A (x
A
). The shape of the curve in Figure 3-4 is
based on the assumption that ÷r
A
decreases as x
A
increases. In this case, (1=÷r
A
) will
increase as x
A
increases. We will refer to this situation as ‘‘normal kinetics.’’
1/(–r
A
)
Fractional conversion (x
A
)
Figure 3-4 Inverse of reaction rate (rate
of disappearance of reactant A) versus
fractional conversion of A.
54 Chapter 3 Ideal Reactors
‘‘Normal kinetics’’ will be observed in a number of situations, e.g., if the reactor is
isothermal and the concentration-dependent term in the rate equation obeys Generalization III
fromChapter 2. Recall that GeneralizationIII statedthat theconcentration-dependent termF(all
C
i
) decreases as the concentrations of the reactants decrease, i.e., as the reactants are consumed.
In the discussion of graphs of
À
1=÷r
A
Á
versus x
A
, the term‘‘isothermal’’ will be used to
mean that the temperature does not change as x
A
changes. This definition is consistent with
the definitions, given previously, for isothermal ideal batch reactors and isothermal ideal
plug-flow reactors. However, this definition of ‘‘isothermal’’ is more general and can apply
to a CSTR or to a series of reactors.
‘‘Normal kinetics’’ will also be observed if Generalization III applies and the reaction
temperature decreases as x
A
increases. The temperature will decrease as x
A
increases, for
example, when an endothermic reaction is carried out in an adiabatic reactor.
The shape of the (÷1=r
A
) versus x
A
curve is not always ‘‘normal.’’ This curve can be
very different if the reaction is exothermic and the reactor is adiabatic, or if the rate equation
does not obey Generalization III.
Now, let’s reexamine one form of the design equation for an ideal CSTR:
V
F
A0
=
x
A
÷r
A
(3-17)
In order to discriminate between the variable x
A
and the outlet conversion from the CSTR,
let’s call the latter x
A,e
(‘‘e’’ for ‘‘effluent’’), and write the design equation as
V
F
A0
=
x
A;e
÷r
A
(x
A;e
)
This equation tells us that (V=F
A0
) for an ideal CSTR is the product of the fractional
conversion of A in the reactor outlet stream (x
A,e
) and the inverse of the reaction rate,
evaluated at the outlet conditions [1=÷r
A
(x
A;e
)[. This product is shown graphically in
Figure 3-5. The length of the shaded area is equal to x
A,e
, and the height is equal to
1=÷r
A
(x
A;e
). The area is equal to V=F
A0
, according to the above equation.
Now, let’s examine the comparable design equation for an ideal PFR:
V
F
A0
=
Z
xA;e
0
dx
A
÷r
A
(3-33)
Area = V/F
A0
x
A,e
1/(–r
A
)
1/[–r
A
(x
A,e
)]
Fractional conversion (x
A
)
Figure 3-5 Graphical representation of the design equation for an ideal CSTR.
3.4 Graphical Interpretation of the Design Equations 55
This equation tells us that (V=F
A0
) for an ideal PFR is the area under the curve of (1=÷r
A
)
versus x
A
, between the inlet fractional conversion (x
A
= 0) and the outlet fractional
conversion (x
A,e
). This area is shown graphically in Figure 3-6.
Now we can compare the volumes (or weights of catalyst) required to achieve a
specified conversion in each of the two ideal, continuous reactors. Suppose we have an ideal
CSTRand an ideal PFR. The same reaction is being carried out in both reactors. The PFRis
isothermal and operates at the same temperature as the CSTR. The molar feed rate of
Reactant A to both reactors is F
A0
. If the kinetics are ‘‘normal,’’ which reactor will require
the smaller volume to produce a specified conversion, x
A,e
, in the effluent stream?
Figure 3-7 shows the graphical answer to this question. For a given F
A0
, the required
volume for an ideal CSTRis proportional to the entire shaded area (both types of shading). The
required volume for an ideal PFR is proportional to the area under the curve. Clearly, the
required volume for the PFRis substantially less than the required volume for the ideal CSTR.
Area = V/F
A0
x
A,e
1/(–r
A
)
Fractional conversion (x
A
)
Figure 3-6 Graphical representation of the design equation for an ideal PFR.
1/(–r
A
)
Fractional conversion (x
A
)
x
A,e
1/[–r
A
(x
A,e
)]
Figure 3-7 Comparison of the volumes required to achieve a given conversion in an ideal PFR
and an ideal CSTR, for a given feed rate, F
A0
. The required volume for a PFRis proportional to the area
under the curve. The required volume for a CSTRis proportional to the area of the rectangle (the sum
of the two cross-hatched areas).
56 Chapter 3 Ideal Reactors
EXERCISE 3-4
Explain this result qualitatively. What is there about the oper-
ation of an ideal CSTR with ‘‘normal kinetics’’ that causes it to
need a larger volume than an ideal PFR to achieve a specified
outlet conversion for a fixed F
A0
?
Hint: Using the above figure, compare the average reaction
rate in the PFR with the rate in the CSTR. Why are these rates
different?
The graphical interpretation of the design equations for the two ideal continuous
reactors has been illustrated using fractional conversion to measure the progress of the
reaction. The analysis could have been carried out using the extent of reaction j with Eqns.
(3-18) and (3-34). Moreover, for a constant-density system, the analysis could have been
carried out using the concentration of Reactant A, C
A
, with Eqns. (3-24) and (3-37).
Plots suchas those inFigures 3-5–3-7are oftenreferredtoas ‘‘Levenspiel’’ plots. Octave
Levenspiel, a pioneering figure in the field of chemical reaction engineering, popularized the
use of this type of plot as a pedagogical tool more that 40 years ago.
2
‘‘Levenspiel plots’’ will
recur in Chapter 4, as a means of analyzing the behavior of ‘‘systems’’ of ideal reactors.
SUMMARY OF IMPORTANT CONCEPTS
v
Design equations are nothing more than component material
balances.
v
There are no spatial variations of temperature or concentration
in an ideal batch reactor or in an ideal continuous stirred-tank
reactor (CSTR).
v
There are no spatial variations of temperature or concentration
normal to flow in an ideal plug-flow reactor (PFR). However,
the concentrations, and perhaps the temperature, do vary in the
direction of flow;
v
If (and only if ) the mass density is constant, the design
equations can be simplified and written in terms of concen-
tration.
PROBLEMS
Problem 3-1 (Level 1) Radial reactors are sometimes used in
catalytic processes where pressure drop through the reactor is an
important economic parameter, for example, in ammonia syn-
thesis and in naphtha reforming to produce high-octane gasoline.
Top and cross-sectional views of a simplified radial cata-
lytic reactor are shown below.
In this configuration, the feed to the reactor, a gas, is
introduced through a pipe into an outer annulus. The gas dis-
tributes evenly throughout the annulus, i.e., the total pressure is
essentially constant at every position in the annulus. The gas then
flows radially inward through a uniformly packed catalyst bed, in
the shape of a hollow cylinder with outer radius R
o
and inner
radius R
i
. The total pressure is essentially constant along the
length of the central pipe. There is no fluid mixing in the radial
direction. There are no temperature or concentration gradients in
the vertical or angular directions. The catalyst bed contains a
total of W pounds of catalyst.
Reactant A is fed to the reactor at a molar feed rate F
A0
(moles A/time), and the average final fractional conversion of A
in the product stream is x
A
.
Derive the ‘‘design equation,’’ i.e., a relationship among F
A0
,
x
A
, and W, for a radial reactor operating at steady state.
A more detailed design of a radial fixed-bed reactor is
shown below.
1
Gas in
Reactor
wall
Reactor
wall
Central
pipe
Retaining
screen
Gas
out
Catalyst
bed
Inlet
pipe
Annulus
1
Stine, M. A., Petroleum Refining, presented at the North Carolina
State University AIChE Student Chapter Meeting, November 15,
2002.
2
Levenspiel, O., Chemical Reaction Engineering, 1st edition, John
Wiley & Sons, Inc., New York (1962).
Problems 57
Conventional radial flow reactor
Catalyst bed cover plate
Scallop shield
Centerpipe shroud
Scallops (or outer screen)
Catalyst bed (concentrically loaded
around centerpipe)
Centerpipe (punched plate
wrapped with screen material)
(Figure Copyright 2004 UOP LLC. All rights reserved.
Used with permission.)
Problem 3-2 (Level 2) Rate equations of the form
÷r
A
=
kC
A
C
B
(1 ÷ K
A
C
A
)
2
are requiredto describe the rates of some heterogeneous catalytic
reactions. Suppose that the reaction A ÷ B!products occurs in
the liquid phase. Reactant B is present in substantial excess, so
that C
B
does not change appreciably as reactant A is consumed.
1. Thevalue of ÷r
A
goes through a maximumas C
A
is increased.
At what value of C
A
does this maximum occur?
2. The concentration of A in the feed to a continuous reactor is
C
A0
= 1:5=K
A
. The concentration of A in the effluent is
0:50=K
A
. Make a sketch of (1=÷r
A
) versus C
A
that covers
this range of concentration. One ideal continuous reactor will
be used to carry out this reaction. Should it be a CSTR or
PFR? Explain your answer.
3. Would your answer to Part b be different if the inlet concen-
tration was C
A0
= 1:5=K
A
and the outlet concentration was
C
A
= 1:0=K
A
? Explain your answer.
Problem3-3 (Level 2) In an ideal, semi-batch reactor, some of
the reactants are charged initially. The remainder of the reactants
are fed, either continuously or in ‘‘slugs,’’ over time. The
contents of the reactor are mixed vigorously, so that there are
no spatial gradients of temperature or concentration in the
reactor at any time.
Consider the single liquid-phase reaction
A ÷ B!products
which takes place in an ideal, semi-batch reactor. The initial
volume of liquid in the reactor is V
0
and the initial concentrations
of A and B in this liquid are C
A0
and C
B0
respectively. Liquid
is fed continuously to the reactor at a volumetric flow rate y.
The concentrations of A and B in this feed are C
Af
and C
Bf
,
respectively.
1. Derive a design equation for this system by carrying out a
material balance on ‘‘A’’. Work in terms of C
A
, not x
A
or j.
2. Ultimately, we would like to determine C
A
as a function of
time. Under what conditions is the design equation that you
derived sufficient to do this? Assume that the rate equation for
the disappearance of A is known.
Problem 3-4 (Level 1) Plot (1=÷r
A
) versus x
A
for an iso-
thermal, zero-order reaction with a rate constant of k. If the
desired outlet conversion is x
A
= 0:50, which of the two ideal
continuous reactors requires the smaller volume, for a fixed
value of F
A0
?
What is the outlet conversion from a PFR when
V=F
A0
= 2=k?
Problem 3-5 (Level 1) Develop a graphical interpretation of
the design equation for an ideal batch reactor.
Problem 3-6 (Level 1) The kinetics of the catalytic reaction
3
SO
2
÷ 2H
2
S!3S ÷ 2H
2
O
are being studied in an ideal CSTR. Hydrogen sulfide (H
2
S) is
fed to the reactor at a rate of 1000 mol/h. The rate at which H
2
S
leaves the reactor is measured and found to be 115 mol/h. The
feed to the reactor is a mixture of SO
2
; H
2
S, and N
2
in the molar
ratio 1/2/7.5. The total pressure and temperature in the reactor
are 1.1 atmand 250 8C, respectively. The reactor contains 3.5 kg
of catalyst.
What is the rate of disappearance of H
2
S? What are the
corresponding concentrations of H
2
S; SO
2
, S, and H
2
O?
Problem 3-7 (Level 2) The homogeneous decomposition of
the free-radical polymerization initiator diethyl peroxydicarbon-
ate (DEPDC) has been studied in supercritical carbon dioxide
using an ideal, continuous, stirred-tank reactor (CSTR).
4
The
concentration of DEPDC in the feed to the CSTR was
0.30 mmol. Because of this very low concentration, constant
fluid density can be assumed. At 70 8C and a space time of
10 min, the fractional conversion of DEPDC was 0.21. At 70 8C
and a space time of 30 min, the fractional conversion of DEPDC
was 0.44.
The rate equation for DEPDC decomposition is believed to
have the form
÷r
DEPDC
= k[DEPDC[
n
1. What is the value of n, and what is the value of k, at 70 8C?
2. The activation energy of the decomposition reaction is
132 kJ/mol. What is the value of the rate constant k at 85 8C?
3
This reaction is the catalytic portion of the well-known Claus
process for converting H
2
S in waste gas streams into elemental sulfur.
4
Adapted from Charpentier, P. A., DeSimone, J. M., and Roberts,
G. W. Decomposition of polymerization initiators in supercritical
CO
2
: a novel approach to reaction kinetics in a CSTR, Chem. Eng.
Sci., 55, 5341–5349 (2000).
58 Chapter 3 Ideal Reactors
Problem3-8 (Level 1) An early study of the dehydrogenation
of ethylbenzene to styrene
5
contains the following comments
concerning the behavior of a palladium-black catalyst:
‘‘A fair yield (of styrene) was obtained at 400 8C. A 12-g
sample of catalyst produced no greater yield than the 8-g sample.
By passing air with the ethylbenzene vapor, the dehydrogenation
occurred at even lower temperatures and water was produced.’’
The Pd-black catalyst was contained in a quartz tube and the
flow rate of ethylbenzene through the tube was 5 cc (liquid) per
hour for all experiments. The measured styrene yields (moles
styrene formed/mole ethylbenzene fed) were about 0.2 with both
8 and 12 g of catalyst. For the purposes of this problem, assume
that ‘‘yield’’ of styrene is the same as the conversion of ethyl-
benzene, andassume that the dehydrogenation of ethylbenzene is
stoichiometrically simple. Also assume that the reaction took
place at 1 atm total pressure. In answering the questions below,
assume that the experimental reactor was an ideal PFR.
1. In view of the design equation for an ideal PFR in which a
heterogeneously catalyzed reaction takes place, how would
you expect the yield of styrene to have changed when the
amount of catalyst was increased from 8 to 12 g?
2. How do you explain the fact that the yield of styrene did not
change when the catalyst weight was increased from8 to 12 g?
3. Howdo you explain the behavior of the reaction when air was
added to the feed?
Problem 3-9 (Level 1) The hydrogenolysis of thiophene
(C
4
H
4
S) has been studied at 235–265 8C over a cobalt–molyb-
date catalyst, using a CSTR containing 8.16 g of catalyst. The
stoichiometry of the system can be represented by
C
4
H
4
S ÷ 3H
2
!C
4
H
8
÷ H
2
S Reaction 1
C
4
H
8
÷ H
2
!C
4
H
10
Reaction 2
All species are gaseous at reaction conditions.
The feed to the CSTR consisted of a mixture of thiophene,
hydrogen, and hydrogen sulfide. The mole fractions of butene
(C
4
H
8
), butane (C
4
H
10
), and hydrogen sulfide in the reactor
effluent were measured. The mole fractions of hydrogen and
thiophene were not measured.
The data from one particular experimental run are given
below:
Total pressure in reactor = 832 mmHg
Feed rate
Thiophene = 0:653 × 10
÷4
gmol/min
Hydrogen = 4:933 × 10
÷4
gmol/min
Hydrogen sulfide = 0
Mole fractions in effluent
H
2
S = 0:0719
Butenes (total) = 0:0178
Butane = 0:0541
Calculate ÷r
T
(the rate of disappearance of thiophene) and
the partial pressures of thiophene, hydrogen, hydrogen sulfide,
butenes (total), and butane in the effluent. You may assume that
the ideal gas laws are valid.
Problem 3-10 (Level 2) The hydrolysis of esters, i.e.,
C
O
OR'
(E) (W) (A)
+ H
2
O + R'OH
R
C
O
OH R
frequently is catalyzed by acids. As the above hydrolysis
reaction proceeds, more acid is produced and the concentration
of catalyst increases. This phenomenon, known as ‘‘autocatal-
ysis,’’ is captured by the rate equation
÷r
E
= (k
0
÷ k
1
[A[)[E[[H
2
O[
Here k
0
is the rate constant in the absence of the organic acid that
is produced by the reaction.
To illustrate the behavior of autocatalytic reactions, let’s
arbitrarily assumed the following values:
E
0
(ester concentration in feed) = 1:0 mol/l
W
0
(water concentration in feed) = 1:0 mol/l
A
0
(acid concentration in feed) = 0
The concentration of the alcohol (R
0
OH) in the feed also is
zero. The rate constants are
k
0
= 0:01 l/mol-h
k
1
= 0:20 l
2
/mol
2
-h
In answering the following questions, assume that the
reaction takes place in the liquid phase.
1. Calculate values of ÷r
E
at fractional conversions of ester
(x
E
) = 0; 0:10; 0:20; 0:30; 0:40; 0:50; 0:60; and 0:70:
2. Plot 1=÷r
E
versus x
E
.
3. What kind of continuous reactor system would you use if a
final ester conversion of 0.60 were desired, and if the reaction
were to take place isothermally. Choose the reactor or
combination of reactors that has the smallest volume. Justify
your answer.
Problem 3-11 As pointed out in Chapter 2, kinetics are not
always ‘‘normal’’ (e.g., see Figure 2-3). Consider a liquid-phase
reaction that obeys the rate equation: ÷r
A
= kC
÷1
A
, over some
range of concentration. Suppose this reaction was to be carried out
in a continuous, isothermal reactor, with feed and outlet concen-
trations within the range where the rate equation is valid.
1. Make a sketch of (1=÷r
A
) versus C
A
for the range of
concentration where the rate equation is valid.
2. What kind of continuous reactor (or system of continuous
reactors) would you use for this job, in order to minimize the
volume required? Explain your answer.
5
Taylor, H. S. and McKinney, P. V., Adsorption and activation of carbon
monoxide at palladium surfaces, J. Am. Chem. Soc., 53, 3604 (1931).
Problems 59
I. Ideal batch reactor
A. General—differential form Design equation
Variable
Homogeneous
reaction
Heterogeneous
catalytic reaction
Moles of species ‘‘i’’, N
i
1
V
dN
i
dt
= r
i
(3-5)
1
W
dN
i
dt
= r
i
(3-5a)
Fractional conversion of reactant A, x
A
N
A0
V
dx
A
dt
= ÷r
A
(3-6)
N
A0
W
dx
A
dt
= ÷r
A
(3-6a)
Extent of reaction, j
n
i
V
dj
dt
= r
i
(3-7)
n
i
W
dj
dt
= r
i
(3-7a)
B. Constant volume—differential
form
Homogeneous
reaction
Heterogeneous
catalytic reaction
Concentration of species ‘‘i’’, C
i
dC
i
dt
= r
i
(3-8)
dC
i
dt
= C
cat
(r
i
) (3-8a)
Fractional conversion of reactant A, x
A
C
A0
dx
A
dt
= ÷r
A
(3-9) C
A0
dx
A
dt
= C
cat
(÷r
A
) (3-9a)
C. General—integrated form (see
Note 1)
Homogeneous
reaction
Heterogeneous
catalytic reaction
Moles of species ‘‘i’’, N
i
Z
N
i
N
i0
1
V
dN
i
r
i
= t (3-10)
1
W
Z
N
i
N
i0
dN
i
r
i
= t (3-10a)
Fractional conversion of reactant A, x
A
N
A0
Z
1
V
dx
A
(÷r
A
)
= t (3-11)
N
A0
W
Z
x
A
0
dx
A
(÷r
A
)
= t (3-11a)
Extent of reaction, j n
i
Z
j
0
1
V
dj
r
i
= t (3-12)
n
i
W
Z
j
0
dj
r
i
= t (3-12a)
D. Constant volume—integrated form
(see Note 1)
Homogeneous
reaction
Heterogeneous
catalytic reaction
Concentration of species ‘‘i’’, C
i
Z
C
i
C
i0
dC
i
r
i
= t (3-13)
Z
C
i
C
i0
dC
i
r
i
= C
cat
t (3-13a)
Fractional conversion of reactant A, x
A
C
A0
Z
x
A
0
dx
A
(÷r
A
)
= t (3-14) C
A0
Z
x
A
0
dx
A
(÷r
A
)
= C
cat
t (3-14a)
Note 1: For Case 3 (p. 43).
3.5 APPENDIX 3 SUMMARY OF DESIGN EQUATIONS
Warning: Careless use of the equations in this appendix can be damaging to per-
fomance. In extreme cases, improper use of these materials can be academically fatal.
Always carry out a careful analysis of the problem being solved before using this
appendix.
When in doubt, first carefully choose the type of reactor for which calculations are to be
performed. Then decide whether the reaction is homogeneous or heterogeneous. Finally,
begin with the most general form of the appropriate design equation and make any
simplifications that are warranted.
60 Chapter 3 Ideal Reactors
II. Ideal continuous stirred-tank reactor (CSTR)
A. General—in terms of V or W Homogeneous
reaction
Heterogeneous
catalytic reaction
Molar flow rate of species ‘‘i’’, F
i
V =
F
i0
÷ F
i
÷r
i
(3-16) W =
F
i0
÷ F
i
÷r
i
(3-16a)
Fractional conversion of reactant A, x
A
V
F
A0
=
x
A
(÷r
A
)
(3-17)
W
F
A0
=
x
A
(÷r
A
)
(3-17a)
Extent of reaction, j V =
n
i
j
r
i
(3-18) W =
n
i
j
r
i
(3-18a)
B. General—in terms of t
0
(see Note 1)
Homogeneous
reaction
Heterogeneous
catalytic reaction
Fractional conversion of reactant A, x
A
t
0
=
C
A0
x
A
÷r
A
(3-21) t
0
=
C
A0
x
A
÷r
A
(3-21)
C. Constant density—in terms of t
(see Note 2)
Homogeneous
reaction
Heterogeneous
catalytic reaction
Fractional conversion of reactant A, x
A
t =
C
A0
x
A
÷r
A
(3-23) t =
C
A0
x
A
÷r
A
(3-23)
Concentration of reactant A, C
A
t =
C
A0
÷ C
A
÷r
A
(3-24) t =
C
A0
÷ C
A
÷r
A
(3-24)
Note 1:
For a homogeneous reaction, t
0
= V=y
0
= VC
A0
=F
A0
.
For a heterogeneous reaction, t
0
= W=y
0
= WC
A0
=F
A0
.
Note 2:
For a homogeneous reaction, t = V=y = VC
A0
=F
A0
.
For a heterogeneous reaction, t = W=y = WC
A0
=F
A0
.
III. Ideal continuous plug-flow reactor (PFR)
A. General—differential form—in
terms of V or W
Homogeneous
reaction
Heterogeneous
catalytic reaction
Molar flow rate of species ‘‘i’’, F
i
dV =
dF
i
r
i
(3-26) dW =
dF
i
r
i
(3-26a)
Fractional conversion of reactant A, x
A
dV
F
A0
=
dx
A
÷r
A
(3-27)
dW
F
A0
=
dx
A
÷r
A
(3-27a)
Extent of reaction, j dV =
n
i
dj
r
i
(3-28) dW =
n
i
dj
r
i
(3-28a)
B. General—differential form–in
terms of t
0
(see Note 1)
Homogeneous
reaction
Heterogeneous
catalytic reaction
Fractional conversion of reactant A, x
A
dt
0
= C
A0
dx
A
(÷r
A
)
(3-29) dt
0
= C
A0
dx
A
(÷r
A
)
(3-29)
C. Constant density—differential
form in terms of t (see Note 2)
Homogeneous
reaction
Heterogeneous catalytic
reaction
Fractional conversion of reactant A, x
A
dt = C
A0
dx
A
(÷r
A
)
(3-30) dt = C
A0
dx
A
(÷r
A
)
(3-30)
Concentration of reactant A, C
A
dt =
÷dC
A
(÷r
A
)
(3-31) dt =
÷dC
A
(÷r
A
)
(3-31)
Appendix 3 Summary of Design Equations 61
D. General—integrated form (see
Note 3)
Homogeneous
reaction
Heterogeneous
catalytic reaction
Molar flow rate of species ‘‘i’’, F
i
V =
Z
F
i
F
i0
dF
i
r
i
(3-32) W =
Z
F
i
F
i0
dF
i
r
i
(3-32a)
Fractional conversion of reactant A, x
A
V
F
A0
=
Z
x
A
0
dx
A
(÷r
A
)
(3-33)
W
F
A0
=
Z
x
A
0
dx
A
(÷r
A
)
(3-33a)
Extent of reaction, j V =
Z
j
0
n
i
dj
r
i
(3-34) W =
Z
j
0
n
i
dj
r
i
(3-34a)
Fractional conversion of reactant A,
x
A
—in terms of t
0
(see Note 1)
t
0
= C
A0
Z
x
A
0
dx
A
(÷r
A
)
(3-35) t
0
= C
A0
Z
x
A
0
dx
A
(÷r
A
)
(3-35)
E. Integrated form—constant
density—in terms of t (see Note 2
and 3)
Homogeneous
reaction
Heterogeneous
catalytic reaction
Fractional conversion of reactant A, x
A
t = C
A0
Z
x
A
0
dx
A
(÷r
A
)
(3-36) t = C
A0
Z
x
A
0
dx
A
(÷r
A
)
(3-36)
Concentration of reactant A, C
A
t = ÷
Z
C
A
C
A0
dC
A
(÷r
A
)
(3-37) t = ÷
Z
C
A
C
A0
dC
A
(÷r
A
)
(3-37)
Note 1:
For a homogeneous reaction, t
0
= V=y
0
= VC
A0
=F
A0
.
For a heterogeneous reaction, t
0
= W=y
0
= WC
A0
=F
A0
.
Note 2:
For a homogeneous reaction, t = V=y = VC
A0
=F
A0
.
For a heterogeneous reaction, t = W=y = WC
A0
=F
A0
.
Note 3:
For the PFR equivalent of Case 3 (p. 43). See the discussion on p. 53.
62 Chapter 3 Ideal Reactors

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