Problems 57

EXERCISE 3-4

Explain this result qualitatively. What is there about the oper­ Hint: Using the above figure, compare the average reaction
ation of an ideal CSTR with "normal kinetics" that causes it to rate in the PFR with the rate in the CSTR. Why are these rates
need a larger volume than an ideal PFR to achieve a specified different?
outlet conversion for a fixed F AO?

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� 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, CA, with Eqns. (3-24) and (3-37).
Plots such as those in Figures 3-5-3-7 are often referred to as "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

• Design equations are nothing more than component material the concentrations, and perhaps the temperature, do vary in the
balances. direction of flow;

• There are no spatial variations oftemperature or concentration • If (and only if) the mass density is constant, the design
in an ideal batch reactor or in an ideal continuous stirred-tank equations can be simplified and written in terms of concen­
reactor (CSTR). tration.

• There are no spatial variations oftemperature or concentration

normal to flow in an ideal plug-flow reactor (PFR). However,

PROBLEMS

Problem 3-1(Level1) Radial reactors are sometimes used in In this configuration, the feed to the reactor, a gas, is
catalytic processes where pressure drop through the reactor is an introduced through a pipe into an outer annulus. The gas dis­
important economic parameter, for example, in ammonia syn­ tributes evenly throughout the annulus, i.e., the total pressure is
thesis and in naphtha reforming to produce high-octane gasoline. essentially constant at every position in the annulus. The gas then
Top and cross-sectional views of a simplified radial cata­ flows radially inward through a uniformly packed catalyst bed, in
lytic reactor are shown below. the shape of a hollow cylinder with outer radius R0 and inner
Gas in radius Ri. 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
Retaining Reactor
screen wall total of W pounds of catalyst.
Reactant A is fed to the reactor at a molar feed rate F AO
(moles Ntime), and the average final fractional conversion ofA
in the product stream is XA.
Derive the "design equation," i.e., a relationship among FAo.
Catalyst
bed XA, and W, for a radial reactor operating at steady state.
Gas
out A more detailed design of a radial fixed-bed reactor is
Central 1
shown below.
pipe

Inlet 1 Stine, M.A., Petroleum Refining, presented at the North Carolina

pi pe State UniversityAIChE Student Chapter Meeting, November 15,
2002.
2
Levenspiel, 0., Chemical Reaction Engineering, 1st edition, John
Wiley & Sons, Inc., New York (1962).
58 Chapter 3 Ideal Reactors

Conventional radial flow reactor 1. Derive a design equation for this system by carrying out a
material balance on "A:'. Work in terms of CA, not XA or�-

Catalyst bed cover plate 2. Ultimately, we would like to determine CA 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
Scallop shield
the disappearance of A is known.

Problem 3-4 (Level 1) Plot (1/-rA) versus XA for an iso­

thermal, zero-order reaction with a rate constant of k. If the
Scallops (or outer screen) desired outlet conversion is XA= 0.50, which of the two ideal
continuous reactors requires the smaller volume, for a fixed
,......+-+--�+-H-- Catalyst bed (concentrically loaded value of FAO?
around centerpipe) What is the outlet conversion from a PFR when

�+++-- Centerpipe (punched plate V/FAo = 2/k?

wrapped with screen material)
Problem 3-5 (Level 1) Develop a graphical interpretation of
the design equation for an ideal batch reactor.
(Figure Copyright 2004 UOP LLC. All rights reserved.
Used with permission.) Problem 3-6 (Level 1) The kinetics of the catalytic reaction3

Problem 3-2 (Level 2) Rate equations of the form S02 + 2H2S --t 3S + 2H20
kCACB
-rA= 2 are being studied in an ideal CSTR. Hydrogen sulfide ( H2S ) is
(1 + KACA)
fed to the reactor at a rate of 1000 mol/h. The rate at which H2S
are required to describe the rates ofsome heterogeneous catalytic leaves the reactor is measured and found to be 115 mol/h. The
reactions. Suppose that the reaction A + B --t products occurs in feed to the reactor is a mixture of S02, H2S, and N2 in the molar
the liquid phase. Reactant B is present in substantial excess, so ratio 1/2/7.5. The total pressure and temperature in the reactor
that CB does not change appreciably as reactant A is consumed. are 1.1 atm and 250 °C, respectively. The reactor contains 3.5 kg

1. The value of-rA goes through a maximum as CA is increased. of catalyst.

At what value of CA does this maximum occur? What is the rate of disappearance of H2S? What are the
corresponding concentrations of H2S, S02, S, and H20?
2. The concentration of A in the feed to a continuous reactor is
CAo = 1.5/KA. The concentration of A in the effluent is Problem 3-7 (Level 2) The homogeneous decomposition of

0.50/KA. Make a sketch of (1/-rA) versus CA that covers the free-radical polymerization initiator diethyl peroxydicarbon­

this range of concentration. One ideal continuous reactor will ate (DEPDC) has been studied in supercritical carbon dioxide

be used to carry out this reaction. Should it be a CSTR or using an ideal, continuous, stirred-tank reactor (CSTR).4 The

PFR? Explain your answer. concentration of DEPDC in the feed to the CSTR was
0.30 mmol. Because of this very low concentration, constant
3. Would your answer to Part b be different if the inlet concen­
fluid density can be assumed. At 70 °C and a space time of
tration was CAo= 1.5/KA and the outlet concentration was
10 min, the fractional conversion ofDEPDC was 0.21. At 70 °C
CA= 1.0/KA? Explain your answer.
and a space time of 30 min, the fractional conversion ofDEPDC
was 0.44.
Problem 3-3 (Level 2) In an ideal, semi-batch reactor, some of
The rate equation for DEPDC decomposition is believed to
the reactants are charged initially. The remainder ofthe reactants
have the form
are fed, either continuously or in "slugs," over time. The
-rnEPDC = k[DEPDcr
contents of the reactor are mixed vigorously, so that the re are
no spatial gradients of temperature or concentration in the 1. What is the value of n, and what is the value of k, at 70 °C?
reactor at any time.
2. The activation energy of the decomposition reaction is
Consider the single liquid-phase reaction
132 kJ/mol. What is the value of the rate constant k at 85 °C?
A + B --t products
3 This reaction is the catalytic portion of the well-known Claus
which takes place in an ideal, semi-batch reactor. The initial
process for converting H2S in waste gas streams into elemental sulfur.
volume ofliquid in the reactor is Vo and the initial concentrations
4Adapted from Charpentier, P. A., DeSimone, J. M., and Roberts,
of A and B in this liquid are CAo and CBo respectively. Liquid
G. W. Decomposition of polymerization initiators in supercritical
is fed continuously to the reactor at a volumetric flow rate v.
COz: a novel approach to reaction kinetics in a CSTR, Chem. Eng.
The concentrations of A and B in this feed are CAf and C Bf·
Sci., 55, 5341-5349 (2000).
respectively.
 Problems 59

Problem 3-8 (Level 1) An early study of the dehydrogenation Calculate -TT (the rate of disappearance of thiophene) and
5
of ethylbenzene to styrene contains the following comments the partial pressures of thiophene, hydrogen, hydrogen sulfide,
concerning the behavior of a palladium-black catalyst: butenes (total), and butane in the effluent. You may assume that
"A fair yield (of styrene) was obtained at 400 °C. A 12-g the ideal gas laws are valid.
sample of catalyst produced no greater yield than the 8-g sample. Problem 3-10 (Level 2) The hydrolysis of esters, i.e.,
By passing air with the ethylbenzene vapor, the dehydrogenation
occurred at even lower temperatures and water was produced." 0 0

II
�
The Pd-black catalyst was contained in a quartz tube and the + R'OH
flow rate of ethylbenzene through the tube was 5 cc (liquid) per
R"" R' R/�OH
hour for all experiments. The measured styrene yields (moles
styrene formed/mole ethylbenzene fed) were about 0.2 with both
(E) 0/11) (A)
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 frequently is catalyzed by acids. As the above hydrolysis
benzene, and assume that the dehydrogenation of ethylbenzene is reaction proceeds, more acid is produced and the concentration
stoichiometrically simple. Also assume that the reaction took of catalyst increases. This phenomenon, known as "autocatal­
place at 1 atm total pressure. In answering the questions below, ysis," is captured by the rate equation
assume that the experimental reactor was an ideal PFR.

1. In view of the design equation for an ideal PFR in which a

Here ko is the rate constant in the absence of the organic acid that
heterogeneously catalyzed reaction takes place, how would
is produced by the reaction.
you expect the yield of styrene to have changed when the
To illustrate the behavior of autocatalytic reactions, let's
amount of catalyst was increased from 8 to 12 g?
arbitrarily assumed the following values:
2. How do you explain the fact that the yield of styrene did not
change when the catalyst weight was increased from 8 to 12 g? E0 (ester concentration in feed)= 1.0 mol/l

3. How do you explain the behavior of the reaction when air was Wo (water concentration in feed)= l .Omol/l

added to the feed? Ao (acid concentration in feed)= 0

Problem 3-9 (Level 1) The hydrogenolysis of thiophene The concentration of the alcohol (R'OH) in the feed also is
(C4H4S) has been studied at 235-265 °C over a cobalt-molyb­ zero. The rate constants are
date catalyst, using a CSTR containing 8.16 g of catalyst. The
ko= 0.01 l/mol-h
stoichiometry of the system can be represented by
ki = 0.20 12/mol2-h
C4H4S + 3H2 --t C4Hs + H2S Reaction 1 In answering the following questions, assume that the

C4Hs + H2 --t C4H10 Reaction 2 reaction takes place in the liquid phase.

All species are gaseous at reaction conditions. 1. Calculate values of -rE at fractional conversions of ester
The feed to the CSTR consisted of a mixture of thiophene, (xE) = 0, 0.10, 0.20, 0.30, 0.40, 0.50, 0.60, and 0.70.
hydrogen, and hydrogen sulfide. The mole fractions of butene
2. Plot 1/ - 7E versus XE.
(C4H8), butane (C4H10), and hydrogen sulfide in the reactor
effluent were measured. The mole fractions of hydrogen and 3. What kind of continuous reactor system would you use if a

thiophene were not measured. final ester conversion of 0.60 were desired, and if the reaction

The data from one particular experimental run are given were to take place isothermally. Choose the reactor or

below: combination of reactors that has the smallest volume. Justify

your answer.
Total pressure in reactor= 832 mmHg

Feed rate Problem 3-11 As pointed out in Chapter 2, kinetics are not
4 always "normal" (e.g., see Figure 2-3). Consider a liquid-phase
Thiophene= 0.653 x 1 0- g·mol/min
4 reaction that obeys the rate equation: -rA= kCA.1 , over some
Hydrogen= 4.933 x 10- g·mol/min
range of concentration. Suppose this reaction was to be carried out
Hydrogen sulfide= 0
in a continuous, isothermal reactor, with feed and outlet concen­
Mole fractions in effluent
trations within the range where the rate equation is valid.
H2S = 0.0719
1. Make a sketch of (1/-rA) versus CA for the range of
Butenes (total)= 0.0178
concentration where the rate equation is valid.
Butane= 0.0541
2. What kind of continuous reactor (or system of continuous
5Taylor, H. S. and McKinney, P. V., Adsorption and activation of carbon reactors) would you use for this job, in order to minimize the
monoxide at palladium surfaces, J. Am. Chem. Soc., 53, 3604 (1931). volume required? Explain your answer.
60 Chapter 3 Ideal Reactors

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.

I. Ideal batch reactor

A. General-differential form Design equation

Homogeneous Heterogeneous
Variable reaction catalytic reaction

Moles of species "i", Ni _!_dNi rI· (3-5)

1dNi =
ri (3-Sa)
Vdt
=

W dt
NAoclxA NAoclxA
Fractional conversion of reactant A, XA -rA t -rA
Vdt
(3-6) (3-6a)
W d
= =

Vi� Vid�
Extent of reaction, � ri (3-7) ri (3-7a)
Vdt Wdt
= =

B. Constant volume-differential Homogeneous Heterogeneous

form reaction catalytic reaction

dCi dCi
Concentration of species "i", Ci dt =
ri (3-8) dt =
Ccat(ri) (3-8a)

dxA dxA
Fractional conversion of reactant A, XA CAodt -rA (3-9) CAo t Ccat(-rA) (3-9a)
=
d =

C. General-integrated form (see Homogeneous Heterogeneous

Note 1) reaction catalytic reaction

Moles of species "i", Ni

f
N;
ldNi
--
= t (3-10)
j
N;
_1_ dNi = t (3-lOa)
V ri W ri
N;o N;o

Fractional conversion of reactant A, XA NAo

f 1 dxA
- -- = t (3-1 1)
NAo
-
j clxA
XA

-- = t (3-l l a)
V(-rA) W (-rA)
0

f �
1 d� Vi
�
�
Extent of reaction, � Vi
0
--

Vri
=
t (3-12) -

W l ri
0
-
=
t (3-12a)

D. Constant volume-integrated form Homogeneous Heterogeneous

(see Note 1) reaction catalytic reaction

Concentration of species "i", Ci

fdCi
C;

=
t (3-13)
fdCi
C;

= Ccatt (3-13a)
ri -
ri
C;o C;o

Fractional conversion of reactant A, XA

Note 1: For Case 3 (p. 43).

 Appendix 3 Summary of Design Equations 61

II. Ideal continuous stirred-tank reactor (CSTR)

A. General-in terms of V or W Homogeneous Heterogeneous

reaction catalytic reaction

Fi - Fi
V = i O - Fi
F
Molar flow rate of species "i", Fi (3-16) W= O (3-16a)
-ri -ri
W X
Fractional conversion of reactant A, XA �=� (3-17) -= A -- (3-17a)
FAo (-rA) FAo (-rA)
V� Vj�
Extent of reaction, � V= i (3-18) W= - (3-18a)
Tj ri
B. General-in terms of To Homogeneous Heterogeneous
(see Note 1) reaction catalytic reaction

C oX C oX
Fractional conversion of reactant A, XA ro = A A (3-21) ro = A A (3-21)
-rA -rA
C. Constant density-in terms of T Homogeneous Heterogeneous
(see Note 2) reaction catalytic reaction

CAoXA _ CAoXA _
Fractional conversion of reactant A, XA r= (3 23) r= (3 23)
-rA -rA
C C o- CA
Concentration of reactant A, CA r = CAo- A (3-24) r= A (3-24)
-rA -rA

Note 1:

For a homogeneous reaction, To= V/vo= VCAo/FAo·

For a heterogeneous reaction, To= W/vo= WCAo/FAo·
Note 2:
For a homogeneous reaction, T = V/v = VCAo/FAo·
For a heterogeneous reaction, T = W/v = WCAo/FAo·

III. Ideal continuous plug-flow reactor (PFR)

A. General-differential form-in Homogeneous Heterogeneous

terms of V or W reaction catalytic reaction

dFi dF·
Molar flow rate of species "i", Fi dV = (3-26) dW = -1 (3-2 6a)
Tj Tj

dV dxA _ dW dxA
Fractional conversion of reactant A, XA = (3 27) = (3-27a)
FAo -rA FAo -rA
Vid� Vid�
Extent of reaction, � dV = (3-28) dW = (3-28a)
Tj ri
B. General-differential form-in Homogeneous Heterogeneous
terms of To (see Note 1) reaction catalytic reaction

dxA dxA
Fractional conversion of reactant A, XA dro = CAo- - (3-29) dro = CAo- - (3-29)
(-rA) (
-rA )
C. Constant density-differential Homogeneous Heterogeneous catalytic
form in terms of T (see Note 2) reaction reaction

dxA (3-30)
dxA (3-30)
Fractional conversion of reactant A, XA dr = CAo- - dr = CAo- -

(-rA) (-rA)
-dCA d
- CA
Concentration of reactant A, CA dr = (3-31) dr = (3-31)
(-rA) (-rA)
62 Chapter 3 Ideal Reactors

D. General-integrated form (see Homogeneous Heterogeneous

Note 3) reaction catalytic reaction
!Fi dFi
!Fi dF·
Molar flow rate of species "i", Fi V= - (3-32) W= _I (3-32a)
Ti Tj

Fractional conversion of reactant A, XA �= fXA dxA

(3-33)
W
=
fXA dxA
(3-33a)
-r -r
-

FAo FAo
--

( A) ( A)
0 0

Extent of reaction, � V=
f V;�
�

(3-34) W=
f V;�
�

(3-34a)
Tj Tj
0 0
XA XA
dxA dxA
Fractional conversion of reactant A,
XA-
ro (see Note 1)
in terms of
ro = CAo
J 0
-r
( A)
(3-35) ro = CAo
J
0
-r
( A)
(3-35 )

E. Integrated form-constant Homogeneous Heterogeneous

density-in terms of r (see Note 2 reaction catalytic reaction
and 3)
Fractional conversion of reactant A, XA

Concentration of reactant A, CA

Note 1:

For a homogeneous reaction, <o = V/vo = VCAo/FAo·

For a heterogeneous reaction,<o = W/vo = WCAo/FAo·
Note 2:

For a homogeneous reaction,<= V/v = VCAo/FAo·

For a heterogeneous reaction,<= W/v = WCAo/FAo·
Note 3:

For the PFR equivalent of Case 3 (p. 43). See the discussion on p. 53.