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Chapter 3 Problem Statements
Chapter 3 Problem Statements
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.
• 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.
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
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�-
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
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.
3. How do you explain the behavior of the reaction when air was Wo (water concentration in feed)= l .Omol/l
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
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
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
= =
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 =
-- = 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)
=
t (3-13)
fdCi
C;
= Ccatt (3-13a)
ri -
ri
C;o C;o
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:
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
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 )
Concentration of reactant A, CA
Note 1:
For the PFR equivalent of Case 3 (p. 43). See the discussion on p. 53.