Extra Exercises For Chemical Reactor Analysis and Design Fundamentals

Extra Exercises
for
Chemical Reactor
Analysis and Design
Fundamentals
James B. Rawlings
Department of Chemical Engineering
University of California, Santa Barbara
Santa Barbara, California
John G. Ekerdt
D
Department of Chemical Engineering
The University of Texas
Austin, Texas
November 29, 2020
b Hi
No ll Publishing
Santa Barbara, California

A
The extra exercises were set in Lucida using L TEX.
Copyright © 2020 by Nob Hill Publishing, LLC
All rights reserved.
Nob Hill Publishing, LLC
Cheryl M. Rawlings, publisher
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orders@nobhillpublishing.com
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The extra exercises are intended for use by students and course in-
structors.
This document has been posted electronically on the website: www.

engineering.ucsb.edu/~jbraw/chemreacfun.
2
The Stoichiometry of Reactions
Exercise 2.16: Element balances
Consider a chemical reaction between the species P , Cl 4 2 and PCl 5
1 4
P 2 Cl 2 )* 3
- - PCl 5 (2.73)
(a) Write the element matrix A for this reaction.
(b) What is the rank of A ? How many linearly independent reactions can satisfy
Reaction 2.73?
(c) Write all of the possible stoichiometries for these species using the smallest pos-
sible integers for .
Exercise 2.17: More element balances
Consider the reaction
1 3
H PO 4 2 SrCO 3 )* 3
- - Sr 3 PO 4
4 2 CO 2 5 2
H O
(b) How many linearly independent reactions are possible with these species?
(c) Write all of the possible stoichiometries for these species using the smallest pos-
sible integers for .
Exercise 2.18: A 10th grade stoichiometry problem
Consider the reaction
1 KClO 3 2 HCl - - )* 3 KCl 4 2

H O 5 Cl 2 6 ClO 2
1
2 The Stoichiometry of Reactions
(b) How many linearly independent reactions are possible with these species?
(c) Write all possible stoichiometries for these species.
AT
Hint: you will not obtain integer coef®cients if you use standard software to ®nd
null space of because the vectors of the null space are made into an or-
thonormal set. Try the Octave program nullint which gives an integer-valued
null space.
Exercise 2.19: Stoichiometry short questions
(a) What is the difference between a set of reactions that is linearly independent and
a set of reactions that is linearly dependent?
(b) For the reaction
2NO 2 )*
O - - 2NO
2
is it likely that this overall reaction would occur also as a molecular event? Why
or why not?
(c) Consider the set of reactions
A B )*
2C - - D E
)*
A - - B E
2B )*
2C - - D
1. Write out the species list and stoichiometric matrix. For ease of grading,
please keep the species in alphabetical order in the species list.
2. By inspection, what is the rank of this matrix? Explain your answer.

3
Review of Chemical Equilibrium
Exercise 3.16: Confusion over reaction equilibrium with multiple phases
A student in your class asks for your help with the following dif®cult she is having.
I have a gas/liquid two-phase system with the chemical reaction
A )*
B - - C
I assume the gas phase is an ideal-gas mixture and the liquid phase is an
ideal-liquid solution. The phase rule says that I have two free intensive vari-
ables
f n 2 r
f 3 2 2 1
f 2
so I ®x T and P and try to ®nd the phase compositions, yj , and xj j A; B; C

, .
I have 6 2 4 unknowns since the mole fractions in each phase sum to
one. I equate the chemical potentials for each component in the two phases
jliq jgas j A; B; C
for three equations, and I know the condition for reaction equilibrium is
n
Y
K aj j
j 1
for the fourth equation. But if I express the reaction equilibrium equation
for the gas phase, I get a different equation than for the liquid phase
aj PyyCy
Y j
gas-phase
j A B
Y j x
aj x xC liquid-phase
j A B
3
4 Review of Chemical Equilibrium
in which I have ignored the Poynting correction for the liquid phase because
the pressure is low. These cannot give the same solution because the phase
equilibrium relations are
Pyj Pj0 xj j A; B; C
in which Pj0 is the vapor pressure of component j at the system T . Using
the gas phase for the reaction equilibrium gives
K PyyCy
A B
PyPy C
A PyB
0 PC x C 0
0
PA xA PB xB
0
0 P C x C
PA PB xA xB
K xxxC

A B
which does not agree with the choice of using the liquid phase for the reac-
tion equilibrium. Can I conclude that the component vapor pressures must
be related by
PC0
PA0 PB
1
If not, how do I get consistent results for the equilibrium composition? Na-
ture doesn't know which phase I choose when I do my equilibrium calcula-
tion!
How do you respond to this student?
Exercise 3.17: Equilibrium, friend or foe?
The following reaction takes place at low pressure in the gas phase
A )*
B - - C
You charge a batch reactor with equal amounts of A and B and no C, run the reactor
for a long time at a given temperature and pressure, and then open it up and ®nd that
you have converted about 50 percent of the starting materials.
But you need to reach 75 percent conversion for this process to be pro®table. Your
boss asks you to troubleshoot this process and make suggestions to save the project,
which is about to be canceled. What do you tell your boss? Here are some options to
consider. Feel free to choose one or more of these, or suggest your own options. The
important point is to explain and justify your choice.

Review of Chemical Equilibrium 5
(a) Just run the reactor for a longer time. Eventually it will reach 75 percent conver-
sion, guaranteed. You just have to be patient. State what other thermochemical
data you require, if any, to justify this approach.
(b) Change the operating temperature. If you choose this option, what new tem-
perature do you select? State what other thermochemical data you require, if
any, to select the new temperature, and calculate the new temperature assuming
whatever new data you require is available in your company's thermochemical
database.
(c) Change the operating pressure. If you choose this option, what new pressure do
you select? Again state what other thermochemical data, if any, you require to
select the new pressure, and calculate the new pressure assuming whatever new
data you require is available in your company's thermochemical database.

4
The Material Balance for Chemical Reactors
Exercise 4.23: Short answers on microscopic and macroscopic balances
Consider the volume element V of total volume VR with bounding surface S and outward
normal n depicted in Figure 4.39. The volume element has one entrance and one exit
stream, and otherwise moves to contain chemical species j ; : : : ns

1 with velocities
vj relative to some ®xed laboratory coordinates. The velocity of the element's outer
bounding surface is vs . Decide whether the following statements are true or false, and
give a short explanation justifying your answer.
Z
@cj d
d Z c d
(a)
Vt @t dt Vt j if the volume element is well-mixed
Z
@cj d
dcj V
(b)
Vt @t dt R if the volume element is well-mixed
d Z c d
Z @cj d
Z c v nd
j s
(c)
dt Vt j Vt @t St
Rj
Q0 V
Q1
cj0 cj1
n
S
vs
Figure 4.39: Volume element V with one entrance stream and one exit stream. The
bounding surface is S and moves with velocity vs .
7
8 The Material Balance for Chemical Reactors
QA
cAf
Q
QB cA
VR
cBf cB
Figure 4.40: Organic acid and base streams fed into a CSTR.
Z
(d) cj vj nd Q0 cj0 Q1 cj if the volume element is well-mixed
St
Z
(e) cj vj nd Q0 cj0 Q1 cj cj dV
dt
R if the volume element is well-mixed
St
d Z c d
Z
cj vj vs nd
Z
Rj d
(f)
dt Vt j St Vt
Exercise 4.24: Esteri®cation in a CSTR
Consider the liquid-phase organic esteri®cation reaction taking place in a CSTR depicted
in Figure 4.40. Two streams, an acid stream containing no base, and a base stream
containing no acid, are fed into the CSTR. The esteri®cation reaction and its rate are
given by
A ! B - ester H O 2 r kcA cB
in which A is the organic acid and B is the organic base. The acid and base are dissolved
in an organic solvent and the acid and base feed streams have feed concentrations cAf
and cBf , respectively. You may assume that the density of the ¯uid is independent of
concentration over the concentration range of interest here. The reactor's volume is
constant during the entire operation.
(a) What are the units of k?
(b) What is the volumetric ¯owrate Q of the ef¯uent stream in terms of the feed
stream ¯owrates QA and QB ? Show your reasoning.
(c) Write out the transient material balances for components A and B. You should
have differential equations for dcA =dt dcB =dt

, when you are ®nished. What initial
conditions do you require for these two differential equations.
(d) Now consider the steady-state problem. Write the steady-state balances for the
acid and base concentrations in the reactor, cAs ; cBs .

The Material Balance for Chemical Reactors 9
NA0 NA ; NB ; NC
VR
T0 Tout
P0 P0
Figure 4.41: PFR with nonconstant number of moles and nonconstant temperature.
(e) Can you solve these two equations for cAs cBs
, in the general form for all values
of the parameters? Is this steady-state solution unique?
(f) Whether or not you were able to solve the equations in the general form, given the
following speci®c parameter values, ®nd the steady-state reactor concentrations
cAs ; cBs
10 min QA QB cAf 8 mol/L cBf 4 mol/L
k : 0 1 (in units of min, mol, L)
(g) What are the steady-state molar conversions of A and B for these speci®c param-
eter values?
Exercise 4.25: PFR with changing ¯owrate
Consider the gas-phase PFR depicted in Figure 4.41 in which the following reaction
takes place
A - ! B C r kcA
The feed is pure A with molar ¯ow NA0 at temperature T0 , pressure P0 and volumetric
¯owrate Q0 . The outlet of the reactor is at temperature Tout . Neglect pressure drop in
the tube P P0 . The gas may be assumed to be an ideal gas over this temperatures
range at this pressure. The rate constant may be assumed independent of temperature
over the temperature range T0 T Tout .
(a) List the ideal gas equation of state relating temperature T , pressure P and total
molar concentration c ?
(b) What is the relationship between total molar ¯ow N , volumetric ¯owrate Q , tem-
perature T , and pressure P for the ideal gas equation of state?
(c) For this reaction stoichiometry, what is the total molar molar ¯ow N expressed
solely in terms of the molar ¯owrate of component A NA , i.e. an expression not
involving NB and NC ?
(d) Assume ®rst that the volumetric ¯owrate does not depend on the change in the
number of moles with reaction, nor on the temperature, i.e. QV Q0 . Find the
reactor volume, VR , required to achieve 90% conversion of A. Call this volume VR 1 .
It should be in terms of k; R; T0 ; P0 ; NA0 and the chosen conversion (or NA at the
outlet).
(e) Assume next that the tube is isothermal, but account for the change in volumetric
¯owrate due to change in the number of moles with reaction. What reactor vol-
ume is required to achieve 90% conversion? Call this volume VR2 . Find the ratio
VR2 =VR1 . You can obtain a numerical value for this ratio with the given informa-
tion. Which reactor is larger, VR1 or VR 2 ? Why?
(f) Finally, assume the change in temperature is well approximated by the linear
relationship
TV T0 Tout T0 VV
R
Solve the problem again accounting for both the change in temperature and the
change in the number of moles with reaction. Assume the reactor temperature at
the outlet is one and a half times the temperature at the inlet
Tout : T0
1 5 for T in absolute temperature units
What reactor volume is required to achieve 90% conversion? Call this volume VR 3 .
Find the ratio VR3 =VR2 . You can obtain a numerical value for this ratio with the
given information. Which reactor is larger, VR2 or VR 3 ? Why?
(g) For this stoichiometry, conversion and temperature change, which effect has more
impact on the reactor size, changing the number of moles by reaction or changing
the temperature of the gas?
Exercise 4.26: Solving the transient nonconstant density reactor
Revisit Exercise 4.8, but solve the transient reactor starting from a water-®lled reactor of
1000 L assuming an ideal mixture. Be sure to plot the molar numbers of all components,
the reactor volume and the ef¯uent ¯owrate for each case below.
(a) First assume the reactor is operated at constant volume. Plot the solution to
the model showing the transient approach to steady state. Which set of reactor
balances from Tables 4.1 and 4.2 do you choose and why? You may want to read
Exercise 4.19 to get some ideas on what is going on with these different model
forms.
(b) Next assume the reactor has a ®xed and constant outlet ¯owrate
Q Qf
A B
cA0 nB 0
cB 0 nA0
Figure 4.42: Species A and B in a well-mixed volume element. Continuum and molec-
ular settings.
For what range of does the model admit a steady-state solution? Provide a
closed-form solution for the steady-state reactor volume as a function of valid
over this range. Plot this steady-state reactor volume versus over this range.
You may want to display this result using a semi-log plot for the y -axis.
(c) Choose : 0 987 and simulate the transient reactor behavior. Which set of
reactor balances from Tables 4.1 and 4.2 work for this situation?
Exercise 4.27: What happened to my rate?
Consider a well-mixed continuum setting in which we have positive, real-valued con-
centrations of reacting molecules of two types, A and B, as depicted in Figure 4.42.
Let the concentration of A and B molecules in the volume of interest be denoted cA0 ,
cB0 . Consider the three possible irreversible reactions between these species using the
elementary rate expressions
k1
A A - ! C r1 k1 cA2
k2
A B !
- D r2 k2 cA cB
k3
B B !
- E r3 k3 cB2
Consider also the total rate of reaction
r r1 r2 r3
(a) If the A and B species are chemically similar so the different reactions' rate con-
stants are all similar, k1 k2 k3 k , and the concentrations of A and B are
initially equal, the total rate is given by
r kcA2 0
3
But if we erase the distinctions between A and B completely and relabel the B
molecules in Figure 4.42 as A molecules, we obtain the new concentrations of A
and B as cA cA0 cB
2 , 0 and the total rate is then
r r1 r2 r3
r k1 cA2 k2 cA cB k3 cB2
r k cA0 2 k cA0 k 2
2 2 0 0
r kcA2 0
4
Why are these two total rates different and which one is correct?
(b) Repeat your analysis of the reaction rates if we reduce the length scale and con-
sider the molecular kinetic setting in which we have integer-valued nA0 nB0
,
molecules of A and B in the volume of interest.
Exercise 4.28: PFR size selection
A chemist colleague comes to you with the following reaction, kinetic data, and pro-
cessing requirements
O OH
2
O
k 2
2 H O
cyclohexanone phenol
or
A 2
O !k
- B 2H O2 r kcA cO2
in which A is cyclohexanone and B is phenol. It is required for downstream processes
that the steady-state conversion of A is 90%, and unfortunately there is no separator
available so the reactor is required to achieve the entire 90% conversion. The reactor
also needs to be operated at 0.8 bar so that if there is a leak the hydrocarbons do not
leak out of the reactor.
You have several laboratory PFRs available in stock as shown in the table below, and
need to decide which one(s) would be the best to use.

Reactor Volume
Small A 100 mL
Small B 200 mL
Medium A 1 L
Medium B 2 L
Large 50 L
Other data: T 200 C, k 1500 L/mol hr, R : 0 08314 L bar/mol K; all components
are in the gas phase at the reactor temperature and pressure.
(a) Write out the mass balances for the four components.
(b) What is Q in terms of the feed conditions and NA ?
(c) Assuming pure reactants in the feed with NAf NO2 f solve the PFR mass balance
for component A.
(d) What molar feed of A and O 2 is required to get 90% conversion in each of the
reactors given in the table.
(e) You need to produce 105 mol/yr of phenol (100 mol/yr for downstream processes
and 5 mol/yr to cover losses). What single reactor do you recommend to minimize
reactor down time?
(f) If you can use multiple reactors, what reactors do you recommend to minimize
both the number of reactors and the reactor down time? (i.e., how close can you
get to 105 mol/yr production rate using the minimal number of reactors). You
can use the same reactor type multiple times if desired.
Exercise 4.29: CSTRs and recycle
The following liquid-phase reaction
A - !k B r kcA
is taking place in the single CSTR system shown in Figure 4.43(a). You need to increase
the steady-state conversion without lowering the overall production rate. A creative
but slightly unstable colleague has proposed the modi®cation using a second reactor
shown in Figure 4.43(b). The following parameter values are known
kVR1 =Qf 1 kVR2 =Qf 2

VR2
cA2 cA
Q2 Q2 r Q 1
cAf cA cAf cA1 cA cA

Qf Qf Qf Q1 Q1 Qf
VR1 VR1
(a) (b)
Figure 4.43: (a) Original single CSTR system. (b) Modi®ed two-CSTR system with recy-
cle.
(a) Compute the steady-state exit dimensionless concentration cA =cAf for the single
CSTR. What is the steady-state conversion?
(b) Write a total mass balance at the splitting point and determine Q1 and Q2 as a
function of Qf and the recycle ratio r Q2 =Q1 .
(c) Write component A mass balances over both reactors and ®nd the concentrations
at the exits of the two CSTRs, cA =cAf and cA2 =cAf .
(d) Evaluate the steady-state overall conversion of A using the two CSTRs for recycle
ratio, r = 1 2. Which conversion is higher, the single CSTR or the two-CSTR with
recycle? Try again for r =3 4 and r = 1 4.
(e) What do you think is the best recycle ratio to use to maximize the conversion?
What are the advantages and disadvantages of your colleague's proposal to use
the second reactor? Can you suggest a better use of the second reactor?
Exercise 4.30: Selectivity of competing ®rst-order and second-order reactions
The following two reactions take place in a constant-volume batch reactor
A k!1
B - C r1 k1 cA2 cB
A k!2
B - D r2 k2 cA cB
There is a large excess of reactant B initially, and therefore we can assume that cB is ap-
proximately constant throughout the batch time. Note that, despite the stoichiometry,
the ®rst reaction is second-order in A, but the second reaction is ®rst-order in A.

(a) Write out the component balance for species A in the reactor. How does it simplify
when noting that B is in large excess?
(b) Solve the component balance for cA t . Check that your solution satis®es the
initial condition.
(c) Draw a sketch of cA t versus t .
(d) How would you de®ne the instantaneous selectivity of product C, sC (production
of C relative to consumption of A). Explain in physical terms what this selectivity
is measuring.
(e) How would you de®ne the overall selectivity of product C, SC as a function of the
batch time, t . Explain in physical terms what this selectivity is measuring.
Are the two selectivities you have de®ned the same for this application? Why or
why not?
(f) How would you de®ne overall conversion of A for this reactor, xA ? Explain in
physical terms what this conversion is measuring.
Hint: if you need to integrate something like
Z
dx
x ax b
and, since WolframAlpha is unreachable, instead notice that you can express

x ax b b a x a x b
1 1 1 1
and you know how to integrate both terms on the right-hand side. This is called a
partial fraction expansion, and you will use it later in CBE 470.
Exercise 4.31: Optimizing selectivity and conversion
Revisit Exercise 4.30 and answer the following.
(a) Solve the problem numerically for cA t; cC t; cD t using the following parame-
ter values
cA0 1 mol/L k1 cB0 2 L/(mol hr) k2 cB0 1 hr

1
Check your analytical solution for cA t from Exam 1
(b) De®ne
sC RRC SC nnC nnC 0 xA nAn0 nA

A A0 A A0
Plot sC ; SC ; xA versus time from your numerical solution.
(c) Let's say that you have done an economic analysis of this process and decided that
you need greater than 80 percent conversion of A and greater than 50 percent yield
of C. Are these two requirements feasible? If so, what batch time do you choose
for this application?
(d) Make a plot of xA versus SC . What is the largest yield of C possible for 80 percent
or higher conversion of A? What is the largest conversion of A possible for 50
percent or higher yield of C?
Exercise 4.32: Gas-phase reaction in a PFR
The following elementary, gas-phase reaction takes place in a PFR.
2A - ! B
The reactor is fed with a mixture of of reactant A and inert diluent I at feedrates NAf
and NIfat total molar concentration cf . The feed conditions and rate constant are
cf :
0 2 mol = L NAf : 2 0 mol = min NIf =NAf 3 k : = 20 0 L mol min
The pressure and temperature are constant in the PFR, and the gas may be assumed to
behave as an ideal-gas mixture.
(a) Write a balance for the steady-state molar ¯ow of A, NA . Make sure that your
right-hand side is a function of only NA and known parameters. What is the
initial condition for this differential equation?
(b) What reactor size is required to achieve 85 percent conversion?
(c) What happens to this reactor size if you
1. Double the rate constant k ?
2. Double the feed ¯ows NAf and NIf , but keep feed concentration constant?
3. Double the feed concentration, but keep the feed ¯ows constant?
Exercise 4.33: PFR and CSTR size comparison
Even for a simple stoichiometry like
A - ! B
depending on the mechanism, we will derive a reaction rate expression in Chapter 5 as
complex as
r kcKcA 2
1A
(a) What are the units of k and K ? Draw a sketch of rcA as a function of cA . Show
what happens at both low cA concentration and high cA concentration.
(b) Draw a sketch of 1 =rcA as a function of cA . Find the minimum of 1 =rcA . Draw
this point also on your sketch.
(c) Assume we run this reaction in liquid phase in a CSTR and also in a PFR.
To achieve a conversion of A of 50 percent, and with the following parameter
values, which reactor has more volume, the CSTR or the PFR?
cAf : 1 4 mol = L K : = 2 0L mol
Justify your answer. You might ®nd your sketch of 1 =rcA in the previous part
useful.
(d) To achieve the same 50 percent conversion of A and with the following parameter
values, which reactor has more volume, the CSTR or the PFR?
cAf : 0 6 mol = L K : = 1 0L mol
Justify your answer. You might ®nd your sketch of 1 =rcA in the previous part
useful.
Exercise 4.34: Make PFR and CSTR the same size!
Let's revisit Exercise 4.33 and see if we can make the PFR and CSTR reactors the same
size.
(a) For the ®rst case with parameter values
cAf : 1 4 mol = L K : = 2 0L mol
What conversion can you choose so that the sizes of the PFR and CSTR are iden-
tical?
(b) For the second case with parameter values
cAf : 0 6 mol = L K : = 1 0L mol
what inlet feed concentration can you choose so that the sizes of the PFR and
CSTR are identical (keep the conversion at 50 percent).
(c) Why do you not need to know the reactor rate constant k in Exercise 4.33 and this
exercise?
5
Chemical Kinetics
Exercise 5.20: Hydrogenolysis of 2-methyltetrahydrofuran
Consider the reaction mechanism depicted in Figure 5.26 consisting of the following
reactions [2]
k1
A X )*
- - A X fast
k 1
k2
A
X H 2 )*
- - F X
k 2
k3
A
X H 2 )*
- - B X
k 3
k4
G H 2 )*
- - F fast
k 4
k5
H 2 F - ! C 2
H O
k6
B )*
- - D H 2
k 6
k7
D - ! E CO
k8
H 2 B - ! C 2
H O
The rates of reactions 1 and 4 are known to be fast, so these two reactions may be
assumed to be at equilibrium with respect to the other six reactions. A gas-phase CSTR
containing a platinum catalyst is used to collect data. 2

The feed consists of A and H .
Typical steady-state concentrations of the gas-phase species in the ef¯uent are listed
in the table.
(a) From the table, what species are good candidates for making the quasi-steady-
state assumption in order to simplify the reaction mechanism. Explain your
choice.
(b) Apply the QSSA to these species and the equilibrium assumption to reactions 1
and 4 and express the production rate of butane (E) in terms of reactants and
products present in large concentration in the gas phase (greater than 5 mole
percent).
19
20 Chemical Kinetics
Figure 5.26: Mechanism for hydrogenolysis of 2-methyltetrahydrofuran on platinum.
The H2 are not shown in the diagram for clarity but are listed in the mech-
anism below.
species A
A X G F B D E C 2
H O H 2 CO
mole percent 20 0 23 2 0 0 10 14 14 7 10
Table 5.9: Steady-state gas-phase mole percentages at 545 K, 1.3 bar in the ef¯uent of
a ¯ow reactor. Adsorbed methyl THF (AX) is adsorbed on the catalyst and
is not present in the ef¯uent, but is present in the reactor in nonnegligible
amount.
Chemical Kinetics 21
(c) Find the production rate of n-pentane (C) in terms of reactants and products
present in large concentration in the gas phase (greater than 5 mole percent).
Exercise 5.21: QSSA as the outer solution in a two-time-scale singular perturbation
Consider the following simple reaction mechanism taking place in a well-mixed, constant-
volume, batch reactor
k1 k2
A -! B - ! C
and assume k2 k1 so B is a low-concentration species for which we wish to examine
the QSSA.
(a) Solve A's material balance and show
cAs cA0 e k1 t
Apply the usual QSSA approach, set RB 0 and show that
cBs kk1 cAs cA0 kk1 e k1 t

2 2
The concentration of C is always available if desired from the total species balance
cCs t cA cB cC cAs t cBs t

0 0 0
These results are in agreement with Equations 5.61±5.63.
(b) The B species has two-time-scale behavior. On the fast time scale, it changes
rapidly from initial concentration cB 0 to the quasi-steady-state value for which
RB 0. Divide B's material balance by k2 , de®ne the fast time-scale time as
k2 t , and obtain for B's material balance
dcB k c c k 1
1 A B
d 2
We wish to ®nd an asymptotic solution for small . We try a series expansion in
powers of for the inner solution (fast time scale)
cBi Y0 Y1 2 Y2
The initial condition, CBi CB0 , must be valid for all , which gives for the initial
conditions of the Yn
Y0 cB0
0 Yn ; n ; ; : : :
0 0 1 2
Substitute the series expansion into B's material balance, collect like powers of
and show the following differential equations govern the Yn
0 dY0 Y
:
d 0
1 dY1 k c Y
1 A
:
d 1
n dYn Y n
n
:
d 2
(c) Solve these differential equations and show
Y0 c B 0 e
Y1 cA0 k =kk1

e e k1 =k2
1 2 1
Yn 0 n 2
Because Yn vanishes for n 2, show you obtain the exact solution for the B
concentration for all by using the ®rst two terms. Compare your result to Equa-
tion 5.59.
(d) Next we analyze B's large-time-scale behavior, also called the outer solution. Di-
vide B's material balance by k2 again but do not rescale time and obtain
dcB
dt k1 cA cB
Expand cB again in a power series of
cBo B0 B1 2 B2
Substitute the power series into the material balance and collect like powers of
to obtain the following equations
0 : B0 0
1 dB0 k c B
1 A
:
dt 1
dBn B
n n 1 n
:
dt 1
Solve these equations and show
B0 0
B1 k 1 c A
Bn kn1 cA n 2
So we see the zero-order outer solution is CB 0 0, which is appropriate for a
QSSA species, but a rather rough approximation.

(e) Show that the classic QSSA analysis is the ®rst-order outer solution.
(f) To obtain a uniform solution valid for both short and long times, we add the inner
and outer solution and subtract any common terms. Plot the uniform zeroth-order
and ®rst-order solutions for the following parameter values
cA0 1 cB 0 = 1 2 k1 1 k2 10
Compare to the exact solution and the ®rst-order outer solution (QSSA solution).
(g) Show that the in®nite order uniform solution is also the exact solution.
Exercise 5.22: QSSA and matching conditions in singular perturbation
Consider again Exercise 5.21 with a slightly more complex reaction mechanism
k1 k2
)*
A - - B - ! C
k 1
and assume that either k 1 k1 or k2 k1 (or both) so B is again a low-concentration
species for which we wish to examine the QSSA. Notice that either k 1 or k2 may be
large with respect to the other without invalidating the QSSA assumption for B. Only if
k 1 k1 k2 is the reaction equilibrium assumption also valid for this mechanism.
(a) Apply the QSSA on species B and show
k1 K2
cAs cA0 cB0 K e 1K2 t 1
2 1

k
cBs k 1K cA0 cB0 K e
1 1
k1 K2
1K2 t
1 2 1 2 1
in which K2 k2 =k 1 . Notice that these are in agreement with but more general
than Equations 5.70 and 5.71, which have assumed in addition that cB0 0.
(b) With this mechanism, both the A and B species have two-time-scale behavior, so
we use a series expansion for both cA and cB . Let the inner solution be given by
cAi X0 X1 2 X2
cBi Y0 Y1 2 Y2
in which the small parameter is the inverse of the largest rate constant in the
mechanism. In the following we assume k 1 is largest and =k 1 1. De®ne
K2 k2 =k 1 and we assume that K2 is order unity or smaller. If K2 were large, we

should have chosen =k2

1 as the small parameter. Collect terms of like power
of and show
0 dX0 Y dY0 K Y
:
d 0
d 2 0 1
1 dX1 k X Y dY1 k X K Y
:
d 1 0 1
d 1 0 2 1 1
dXn k X Y dYn k X
n 1 n 1 n 1 n 1 K2 Yn n
:
d d 1 1
What are the initial conditions for the Xn and Yn variables?
(c) Solve these for the zero-order inner solution and show

X0 cA0 cB0 K 1
1 e 1K2 Y0 cB0 e 1K2
2
1
(d) Next we construct the outer solution valid for large times. Postulate a series
expansion of the form
cAo A0 A1 2 A2
cBo B0 B1 2 B2
Substitute these into the A and B material balances and show
0 : B0 0 K2 B0
1 0
1 dA0 k A B dB0 k A K B
:
dt 1 0 1
dt 1 0 2 1 1
dAn 1 k A B dBn 1 k A
n 1 n n 1 n 1 K2 Bn n
:
dt dt 1 1
(e) Solve these and show for zero order
k1 K2
t
A0 A0 e 0
1K2 B0 0
Again we see that to zero order, the B concentration is zero after a short time.
Note also that, unlike in Exercise 5.21, we require an initial condition for the
outer solution An differential equations. We obtain the missing initial condition
by matching with the inner solution as follows
!1
lim X0 t!0 A0 t
lim
In other words, the long-time solution (steady state) on the fast-time scale is the
short-time solution (initial condition) on the slow-time scale. Using this matching
condition show
A0 cA0 cB0 K
0
1
2 1
(f) Find also the ®rst-order solution, B1 , and show that the QSSA solution corresponds
to the zero-order outer solution for cA and the ®rst-order outer solution for cB .
Exercise 5.23: Reaction equilibrium assumption as a singular perturbation
Consider again the reaction equilibrium assumption and the following reactions
k1 k2
)* ;
A - - B B -! C
k 1
in which rate constants k1 ; k 1 are much larger than the rate constants k2 , so the ®rst
reaction equilibrates quickly.
(a) Apply the method discussed in Chapter 5 to obtain differential equations for cA
and cB valid on the slow time scale. What are the correct initial conditions for
these slow-time-scale differential equations?
(b) Now consider the problem using the singular perturbation approach of Exer-
cises 5.21 and 5.22. Assume k 1 is the largest rate constant and de®ne the fast
kt K1 kk1
time scale as
1 1
Expand cA and cB on the fast time scale as
cA X0 X1 2 X2 cB Y0 Y1 2 Y2
Show the fast time-scale model for zero order is
dX0 K X Y X0 cA0
d 1 0 0 0
dY0 K X Y Y0 c B 0
d 1 0 0 0
(c) Solve these differential equations and show

X0 cA0 e 1K1 c 1K1
A0 cB 0 e
1
K1 1
1
Y0 cB0 e 1K1 cA0 cB0 K1K

1 e 1K1
1 1
(d) For the slow time scale, expand cA and cB as
cA A0 A1 2 A2 cB B0 B1 2 B2
Show the zero order terms give the single algebraic equation
0 K1 A 0 B 0
and the ®rst order terms give the two differential equations
dA0 K A B
dt 1 0 1
dB0 K A B k B
dt 1 0 1 2 0
Use the matching conditions with the fast time scale solution to derive the initial
conditions for the slow-time-scale differential equations and show
A0 cA0 cB0 K
0
1
B0 cA0 cB0 K1K
0
1 1 1 1
(e) We now wish to eliminate the ®rst-order term B1 appearing in the zero-order
differential equations. Add the two zero-order differential equations to remove
B1 1
. Use the algebraic equation and show the two zero-order differential equations
can be rewritten as
dA0 k2 K1 A
dt 1 K1 0
dB0 k2 K1 B
dt 1 K1 0
(f) Solve these differential equations and show the zero-order outer solution is
k2 K1
t
cAo cA0 cB0 K e 1
1K1
1 1
K
cBo cA0 cB0 K e
1
k2 K1
1K1 t
1 1
Compare this solution to the reaction equilibrium solution of the ®rst part. What
conclusions do you draw from this comparison?
1 Notice that this addition of the two equations to remove the unknown B1 is analogous to the step that
eliminated r2 and led to Equation 5.45 in the discussion in Chapter 5.

Exercise 5.24: Michaelis-Menten kinetics as QSSA
Consider the enzyme kinetics
k1
E S )*
- - ES
k 1
k2
ES - ! P E
in which the free enzyme E binds with substrate S to form bound substrate ES in the
®rst reaction, and the bound substrate is converted to product P and releases free en-
zyme in the second reaction. This mechanism has become known as Michaelis-Menten
kinetics [6], but it was proposed earlier by Henri [4]. If the rates of these two reactions
are such that either the free or bound enzyme is present in small concentration, the
mechanism is a candidate for model reduction with the QSSA.
Assume k1 k 1 ; k2 so E is present in small concentration. Apply the QSSA and
show that the slow-time-scale model reduces to a ®rst-order, irreversible decomposition
of S to P
S - ! P r
(a) For a well-stirred batch reactor, show the total enzyme concentration satis®es
cE t cES t cE cES 0 0
(b) Find an expression for the QSS concentration of E. What is the corresponding
concentration of ES?
(c) Show the rate expression for the reduced model's single reaction is
r kcKc
S k k2 KE0 K k k1 k E0 cE cES
0 0 (5.163)
1 S 1 2
which depends solely on the substrate concentration. The inverse of the constant
K is known as the Michaelis constant. The production rates of reactant S and
product P in the reduced model are then simply
RS r RP r
Notice we have reduced the number of reactions from two to one; we have reduced
the number of rate constants from three k1 ; k 1 ; k2 to two k; K .
(d) Plot the concentrations versus time for the full model and QSSA model for the
following values of the rate constants and initial conditions.
k1 5 k 1 k2 1 10
cE
0 1 cES 0 cS
0 0 50 cP
0 0
Exercise 5.25: Michaelis-Menten kinetics as reaction equilibrium
Consider again the enzyme kinetics given in Exercise 5.24.
k1
E S )*
- - ES
k 1
k2
ES - ! P E
Now assume the rate constants satisfy k1 ; k 1 k2 so that the ®rst reaction is at
equilibrium on the time scale of the second reaction.
(a) Find the equilibrium concentrations of E and ES
(b) Show the production rate of P is given by
RP kcKS c
e
ke k2 K1 E0 K1 k1 =k 1 (5.164)
1 1 S
in which K1 is the equilibrium constant for the ®rst reaction. Notice this form is
identical to the production rate of P given in the QSSA approach. For this reason,
these two assumptions for reducing enzyme kinetics are often mistakenly labeled
as the same approach. This second reaction equilibrium approach is sometimes
considered a special case of the QSSA [3, p.97]. That viewpoint is erroneous be-
cause neither E nor ES need to be in low concentration when assuming reaction
equilibrium, but do need to be in low concentration when assuming QSS.
It is interesting to note that in their original work in 1913, Michaelis and Menten
proposed the reaction equilibrium approximation to describe enzyme kinetics,
in which the second step is slow compared to the ®rst step [6]. Michaelis and
Menten credit Henri with proposing this mechanism to explain the experimental
observations that (i) production rate of P increases linearly with substrate at low
substrate concentration and (ii) production rate of P is independent of substrate
concentration at high substrate concentration [4].
The QSSA analysis of enzyme kinetics was introduced by Briggs and Haldane in
1925, in which the enzyme concentration is assumed small compared to the sub-
strate [1]. Since that time, the QSSA approach has become the more popular
explanation of the observed dependence of substrate in the production rate of
product RP in Equation 5.163 and Equation 5.164 [8].
Boyde provides a fascinating and detailed historical account of the contributions
of Henri, Michaelis and Menten, and Briggs and Haldane, and includes English
translations of Henri's 1901 paper in French[5] and Michaelis and Menten's 1913
paper in German [7]. Boyde concludes that Henri's pioneering contribution has
been largely overlooked in favor of Michaelis and Menten, despite Michaelis and
Menten's own explicit attribution to Henri.

The reader should be aware that either approximation may be appropriate de-
pending on the values of the rate constants and initial conditions. Although both
reduced models give the same form for the production rate of P, they are often
quite different in other respects. Finally, for some values of rate constants, in
particular k 1 k1 k2 , both the QSS assumption and the reaction equilibrium
assumption apply.
(c) Show that the slow-time-scale reduced model for the reaction equilibrium assump-
tion can be summarized by two irreversible reactions
ES - ! E S re1
!
S - P re2
with the following rate expressions
!
K 1 cE
r K c c
e1
kc
e S
ke k2 K1 E0
1 E
1 S 1 K1 c S
re2 kcKS c
e
K1 k1 =k 1
1 S
1
Notice here we have not reduced the number of reactions; we still have two re-
actions, but as before we have reduced the number of rate constants from three
( k1 ; k 1 ; k2 ) to two ( k;
e K1 ). The ®rst rate expression here depends on cS and cE
rather than only cS as in the previous QSSA reduction. Therefore the production
rates of E, ES and S depend on cE as well as cS . Only the production rate of P
( RP re2 ) loses the cE dependence.
(d) Plot the concentrations versus time for the full model and reaction equilibrium
model for the following values of the rate constants and initial conditions.
k1 : 0 5k 1 k2 : 1 0 5
cE
0 20 cES 0 cS
10 cP 0 50 0 0
Recall that you must modify the initial conditions for the slow-time-scale model
by equilibrating the ®rst reaction from these starting values.
Exercise 5.26: Highly reactive intermediates
Consider the following three elementary reactions
k1 k2 k3
A - ! B B - ! C 2B - ! D
taking place in a well-mixed batch reactor of constant volume.

(a) Write the material balances for all four species: A, B, C, and D.
(b) Assume species B is a highly reactive intermediate species. Write down the alge-
braic equation that applies in this situation.
(c) Solve this equation for intermediate B's concentration in terms of concentrations
of reactants and products A, C, and D.
(d) Remove the concentration of B from the material balances of reactants and prod-
ucts and write the reduced model for the time evolution of the concentrations of
A, C and D.
(e) For what ranges of rate constants k1 k2 k3

, , do you expect this reduced model to
agree closely with the full model?
Exercise 5.27: Catalytic reaction mechanism
You have been continuing studies on the following reaction and have noticed limitations
in the previously given rate expression
O OH
2
O
k 2
2 H O
cyclohexanone phenol
or
A 2
O !k
- C 2H O 2 r kcA cO2
Your chemist colleague does some experiments and comes up with the following mech-
anism consisting of six reactions involving two different types of catalyst sites S and S

k1
)-*
AS OS - BS 2
H OS
O O OH
k1
BS OS
-k!2 CS 2
H OS

K3
A S )*
- - AS
K
O2 2 S
)*4
- - 2 OS

K5 cyclohexanone cyclohexenone phenol
C S )*
- - CS A B C
K6
H O 2 S
)*
- -
2
H OS

We make the following assumptions
1. Reaction 2 is irreversible.
2. All adsorption/desorption reactions are in equilibrium.
3. Species BS is an intermediate and the QSSA can be used.
4. A, B, and C adsorb on surface sites S due to their large molecular sizes.
5. O 2 2
and H O adsorb on surface sites S
due to their small molecular sizes.
You have a measurement device that is calibrated to detect the total concentration
of phenyl groups in the system, both in the gas phase and on the surface. What is
the production rate of phenyl groups in the above mechanism in terms of gas-phase
concentrations cA cC cO2 cH2 O

, , , , rate/equilibrium constants ki k i Ki
, , , and total metal
sites cm cm
(for S) and

(for S )? No surface species concentration should appear in
your ®nal rate expression.
Exercise 5.28: Reduced model for catalytic CO conversion
Consider again the following mechanism for the oxidation of CO on a Pd catalyst
k1
CO S )*
- - CO ads
k 1
k2
O 2 2S )*
- - 2O ads
k 2
k3
CO ads O ads !
- CO 2 2S
(a) Express the full kinetic model for these reactions taking place in a well-mixed
batch reactor. Write balances for all six species: 2

CO, O , CO , CO 2 ads , O ads , and
S, the vacant surface sites. Solve the full model using the initial condition of an
equimolar concentration of CO and O in the gas phase and a bare catalyst surface.
Use the following parameter values (expressed in some consistent set of units)
cCO ; cO ; c CO c O ; c v c m
0 1 0 1 0
c m ; k1 k2 : ; k 1 k 2 : ; k3
1 0 01 0 05 1
Solve the resulting ODE model with Octave or MATLAB . Plot all species concentra-
tions versus time.
(b) Next increase the rate constants of the ®rst two reactions by two orders of mag-
nitude
k1 k2 ; k 1 k 2 ; k3
1 5 1
and solve the model again. Does the solution indicate that it is reasonable to
assume that the ®rst two reactions are always at equilibrium?
(c) Derive the reduced model that eliminates the ®rst two fast reactions' rate con-
stants and replaces them with the ratios
K1 k1 =k 1 ; K2 k2 =k 2
Note that your reduced model will be a mixture of differential equations and
algebraic equations. Use an implicit ODE solver to solve this model. See the com-
putational appendix for a discussion of implicit ODE solvers available in Octave
or MATLAB .
Hint: note that before solving the reduced model, you need to adjust the initial
conditions by equilibrating the two fast reactions. This step requires that you
adjust the given vector of initial concentrations to a set of equilibrium concentra-
tions, and use these equilibrated concentrations as the initial conditions for the
reduced model. We have that
ceq c T "
0
We are keeping the slow third reaction extent "3 ®xed at zero, so we have two
unknowns, "1 ; "2 . We have two constraints, the equilibrium conditions for the
fast reactions,
c CO K1 cCO c v ;0 c O K2 cO c 2v 0
Solve the reduced model using ceq as the initial condition. Does your reduced
model agree with the full model? Explain why or why not.
Exercise 5.29: Reduced model for catalytic CO conversion in a CSTR
Revisit Exercise 5.28, but this time let the reactions takes place in a constant volume
CSTR. Assume the reactor is initially charged with inert N 2 and a bare catalyst surface,
the feed is equimolar concentrations of CO and O , 2 cCOf cO2 f 1, the residence time
of the CSTR is 10. Assume that the inert N 2 feed concentration is large enough that
we may assume Q Qf without signi®cant error (even though moles are not conserved
in these reactions).
Repeat the steps of Exercise 5.28.

6
The Energy Balance for Chemical Reactors
Exercise 6.24: Mass and energy balances with multiple phases

1
Consider the process depicted in Figure 6.43 in which the reactor contents and the
streams entering and leaving the reactor consist of multiple, well-mixed phases. With-
out loss of generality, we shall consider two phases: and . Consider the state of
the reactor to be described by the following set of 2 ns

2 intensive variables and 2
extensive variables
T ; P ; m ; cj j ; : : : ns
1
T ; P ; m ; cj j ; : : : ns
1
in which m ; m are the masses of the and phases, respectively.
Let us assume the phases equilibrate with each other even though the reactor is
not assumed to be at complete chemical equilibrium. As discussed in Chapter 3, the
conditions of phase equilibrium, Equations 3.50, imply that both phases are at the
same temperature, T , and both phases are at the same pressure, P , which allows us
to describe the state of the reactor with 2 ns 2 intensive variables and 2 extensive
1 JBR would like to thank Vasilios Manousiouthakis of UCLA for helpful discussion of this and the next
two exercises.
QÇ
T P VR
cj m Q
Qf
cjf
Tf cj m Q
Figure 6.43: Reactor containing two well-mixed phases of matter.
33
34 The Energy Balance for Chemical Reactors
variables
T; P; m ; m ; cj ; cj j ; : : : ns1
Since the process in Figure 6.43 is an open system, we also have the two ef¯uent
¯owrates and the rate of heat transfer to the system
Q ; Q ; Q Ç
that need to be determined, bringing the total number of unknown variables to 2 ns 7.
We assume we have speci®ed the feed conditions, Qf ; cjf ; Tf . Let us also assume that
the the system pressure and volume are known constants and the rate of heat trans-
ferred to the system is speci®ed. So we have speci®ed two of our unknown variables
P; QÇ
which brings us back to 2 ns 5 unknowns, and we have one constraint on the total
system volume.
(a) Is the process now fully speci®ed? If so, write the 2 ns 5 equations that fully
determine the system.
(b) Let's apply this result to a simple system consisting of a single species that does
not undergo chemical reaction. An example would be a boiler fed with a pure
water stream in which liquid water and steam are the two different phase ef¯uent
streams. For this case, we have 2 ns 5 7 unknowns.
Can you write seven independent equations to specify this system? If so, write
the equations that specify the boiler system.
If not, provide a physical argument for the boiler that shows the system is under-
determined. If underdetermined, what natural additional constraint(s) would you
apply in order to fully specify the boiler system?
Exercise 6.25: Writing DAE models for systems with multiple phases
(a) Describe the system of Exercise 6.24 with a set of DAEs of the form
dx f x; y
dt
g x ; y
0
in which x are the differential states and y are the algebraic states. Be sure that
f and g are functions of only x y

, , and other, known variables. Assume you
have access to complete thermochemical data, which means you can evaluate any
intensive thermodynamic variable of a phase given the set T; P; cj of that phase.
(b) Identify the variables that comprise x and y .

The Energy Balance for Chemical Reactors 35
Notice that neither the heat of reaction nor the heat of phase change are required in
the energy balance when one has complete thermochemical data available. These two
enthalpy changes are only useful for simplifying the required thermochemical data.
When full thermochemical data are available on the other hand, using heats of reaction
and phase change merely complicates the energy balance, and their use should there-
fore be avoided. Experience indicates that always using heat of reaction and heat of
phase change can be a dif®cult habit for chemical engineers to break. It seems new
training on how to express energy balances would be useful given the current wide
availability of computer-based thermochemical databases.
Exercise 6.26: Using thermochemical databases that contain reference states
Many thermochemical databases provide energies relative to some internal reference
state. Say a given database has de®ned a particular reference pressure, temperature,
composition and phase of matter, which determines all intensive thermochemical prop-
erties. Denote the speci®c internal energy and enthalpy of the reference state by
Uref Href
Ã Ã
which are related by
Uref Href Pref

Ã Ã
ref
Consider these common material and energy balances for a two-phase system
dnj Q c Q c Q c X r r j ; : : : ; n
f jf j j ij i i s
dt i
1
dU P dVR Q H Q H Q H Q
dt dt f f f Ã Ã Ã Ç
Now de®ne the following shifted internal energies and enthalpies
Ue U Uref
Ã Ã Ue U Uref
Ã Ã He H Href
Ã Ã He H Href
Ã Ã
Calling the thermochemical database functions returns these shifted quantities. De®ne
the shifted total internal energy by
Ue m U Uref m U Uref
Ã Ã Ã Ã
m U m U m m Uref
Ã Ã Ã
Ue U mUref Ã
in which m m m is the total mass of the system.

(a) We would like to use a new energy balance expressed in terms of these shifted
variables. Is the following shifted energy balance correct?
dUe P dVR Q He Q He Q He Q
dt dt f f f Ç (6.95)
If so, provide a derivation. If not, derive a correct form.
(b) Consider a second approach in which the same reference energy, Ã Eref is subtracted
from all energies (both the internal energy and enthalpy)
Ue U Eref
Ã Ã Ue U Eref He H Eref
Ã Ã Ã Ã He H Eref
Ã Ã
Ue U mEref Ã
Is the shifted energy balance, Equation 6.95, correct with these de®ned quantities? If
so, provide a derivation. If not, derive a correct form.
Exercise 6.27: Equal time for internal energy
In deriving the energy balances in Chapter 6, we often found enthalpy rather than inter-
nal energy to be the more convenient energy function. For situations in which internal
energy is more convenient, provide derivations for the following useful relations

@U TV PV
(a)
T
@P T;nj
(b)
!
@U H j TV j
@nj T;V;nkj T
Exercise 6.28: Nonisothermal plug-¯ow reactor
The reaction
A )*
B - - C D
is carried out adiabatically in a series of tubular reactors with interstage cooling as
shown in Figure 6.44. The feed is equimolar in A and B and enters each reactor at 27 C.

The heat removed between the reactors is :
87 5 kcal/min.
(a) What is the outlet temperature of the ®rst reactor?
(b) What is the conversion of A at the outlet of the ®rst reactor?
(c) Is the ®rst reactor close to equilibrium at the exit?

T0
27 C T0 27 C

NA0 NB0 10 mol/min
Q Ç :
87 5 kcal/min
Figure 6.44: Tubular Reactors with Interstage Cooling.
State any assumptions that you make while solving the problem.
Data:
HR 30 kcal/mol
Cp 25 cal/mol K
K
at 50 C :
5 0 10
5
NA0 NB0
, 10 mol/min
Q
Ç :
87 5 kcal/min
R :
1 987 cal/mol K
Exercise 6.29: A colleague's batch reactor energy balance
A colleague presents you with the following derivation of the energy balance for a
constant-volume batch reactor.
You know, the people writing our textbooks sure make things complicated. I
found a much simpler energy balance for the constant-volume batch reactor.
Here's how it goes. Because you cannot do work on a closed system at
constant volume, the total energy balance is simply
dU Q
dt
Ç (6.96)
For a single-phase system, internal energy UT; V; nj changes due to changes
in T V
, and nj by
!
dU @U dT @U dV X @U dnj
@T V;nj @V T;nj j @nj T;V;nkj
(6.97)
The de®nitions of constant volume heat capacity and partial molar internal
energy are

CV @U@T V;nj (6.98)
!
@U
U j @n (6.99)
j T;V;nkj
Since the reactor volume is constant, dV 0, and forming the time derivative
of the internal energy from Equation 6.97 reduces to
dU C dT X U dnj
V
dt dt j j dt (6.100)
From the de®nition of enthalpy ( H U PV ), we know that
H j U j PV j (6.101)
in which Hj is the partial molar enthalpy and Vj is the partial molar volume.
The material balance for the batch reactor is
dnj R V X r V ; j ; : : : ; ns
j R ij i R
dt i
1 (6.102)
in which ri is the reaction rate per reactor volume and ij is the stoichio-
metric coef®cient for species j in reaction i. We can de®ne the change in
enthalpy and change in volume for reaction i by
ns
X ns
X
HRi ij H j VRi ij V j (6.103)
j 1 j 1
I put the material balance and these de®nitions in Equation 6.100 and I obtain
CV dT
X
dt HRi P VRi ri VR Q Ç (6.104)
Notice that my result doesn't agree with Equation 6.66 in our text!
CV dT HRi T VRi ri VR Q
X
dt
Ç
i T
What's going on here?
Answer the following questions yes or no and provide a short justi®cation.
(a) Is Equation 6.96 correct for the constant-volume batch reactor given the other
assumptions?
(b) Is Equation 6.97 correct for this situation?
(c) Do Equations 6.98 and 6.99 agree with the usual de®nitions of constant-volume
heat capacity and partial molar internal energy?
(d) Is Equation 6.100 a correct rearrangement of the previous equations?

(e) Is Equation 6.101 valid also for partial molar properties?
(f) Is Equation 6.102 a correct statement of the material balance for the batch reactor?
(g) Does Equation 6.103 agree with the usual de®nitions of enthalpy change and vol-
ume change upon reaction?
(h) Is Equation 6.104 a correct rearrangement of the previous equations?
(i) Provide a short discussion of the apparent energy balance contradiction.
If your answers to all questions above were yes, do you think the two energy
balances are equivalent? If so, how would you show this equivalence?
If your answers to some of the questions above were no, how would you repair
your colleague's derivation?
Exercise 6.30: Dynamic plug-¯ow reactor energy balance
Start with the plug-¯ow energy balance of Section 6.5, rewritten here,
@ U @ QH q
@t @V
Ã Ã Ç
(a) Derive the dynamic energy balance in the variables T; P; cj for a single-phase sys-
tem.
2
(b) Does your dynamic energy balance reduce at steady state to Equation 6.50? Dis-
cuss why or why not.
Exercise 6.31: Solving the autothermal plug-¯ow reactor with collocation
Revisit the ammonia synthesis in an autothermal plug-¯ow reactor described in Exam-
ple 6.6.
(a) Solve the resulting boundary-value problem for the parameters given in Table 6.6
with collocation and compare your three steady-state pro®les to the results given
in Figures 6.39 and 6.40. Be sure to note that the ¯owrate should be Qf
: 3
0 05713 m /s in Table 6.6, and that the the middle steady-state pro®le (B) in
Figures 6.39 and 6.40 is shifted somewhat from the correct answer. See the er-
rata posted on www.engineering.ucsb.edu/~jbraw/chemreacfun for the cor-
rect pro®les.
2 The following is one form the answer can take.
CP @T T @P Q C @T @P
T @V
X
HRi ri q
@t
Ã
@t P @V Ã 1 Ç
i
(b) What initial guesses for the collocation equations did you use to converge to the
three steady-state pro®les?
(c) Vary the number of collocation points and demonstrate convergence for the upper
steady-state solution. How many collocation points are required for a reasonably
accurate solution?
(d) Describe the advantages and disadvantages of the shooting method versus collo-
cation for solving this boundary-value problem.
Exercise 6.32: Finite-sized PFRs and interstage cooling
Reconsider Example 6.4. The reaction
k1
)*
A - - B
k 1
takes place in two adiabatic PFRs with interstage cooling as depicted in Figure 6.33. In
Example 6.4 the PFRs were assumed to be long and the reaction reached equilibrium at
the exit of both reactors. We determined the heat duty to be
Q
Ç ;
200 000 BTU/hr
to reach the conversion xA : 0 7 at the exit of the second reactor.
Here we consider two ®nite-sized reactors, each with volume
Vt : 2 22 ft
3
The forward rate constant and activation energy are given by
k1 :
3 47 s
1 at T Tf Ea =R 9000
R
(a) Solve for the NA and T pro®les in both reactors. Plot NA and T versus reactor
volume for both reactors. Compute the conversion at the exit of each reactor
and compare to the answers given in Figure 6.34. You should see that the overall
conversion has dropped to xA2 : 0 653 due to the ®nite-sized reactors.
(b) Next let's see if we can achieve xA2 : 0 7 by changing the heat duty. Vary Q
Ç
between ;
125 000 and ;
250 000 BTU/hr, and make a plot of xA2 Q
versus Ç over
this range. Can you reach xA2 : 0 7 by changing the heat duty? If so, what value
Q
of Ç do you use? If not, why not?
Exercise 6.33: Maximum rate of heat release in series reaction
Consider the elementary reactions in series
k1 k2
A - ! B B -! C
starting with no B or C. It was shown previously that for an isothermal, constant volume
cB cA0 k k1 k e
batch reactor
c A c A0 e k1 t k1 t e k2 t
2 1
We wish to maintain an isothermal reactor, but the reactions are quite exothermic.
To size the heat exchange equipment appropriately, we must know how much heat to
remove over time, as this quantity varies considerably.
Q
(a) Give an expression for Ç , the heat removed by the heat exchanger. You may use
the parameters VR cA0 HR1 HR2 k1

, , , , , and k2 .
(b) At what time is the maximum heat generated in the reactor? Do not assume
numerical values for the parameters. Obtain the general result.
(c) Consider next the following parameter values.
VR 1000 L cA0 3 mol= L
HR1 150 kcal =

mol HR2 100 kcal = mol k1 1 min
1 k2 2 min
1
How much heat should the heat exchanger be able to remove? When does the
maximum occur? If you were not able to answer part (b) analytically, estimate the
maximum heat removal rate and time of the maximum for the parameter values
given.
(d) After the reaction has gone for 3 min, how many moles of A have reacted? Moles
of B? How much total energy has the heat exchanger removed?
Exercise 6.34: Managing the heat in a CSTR
The exothermic liquid-phase reaction
A !kB - C
takes place in a CSTR equipped with a heat exchanger. The feed consists of A and B
dissolved in an inert solvent. An inhibitor is stripped from the feed just before addition
to the reactor.
(a) You plan to start up the CSTR with a solvent ®lled reactor at the feed temperature.
Simulate the reactor behavior ( cA t; cB t; Tt ) for six hours after start up.
(b) Simulate the reactor again for the following situation. After running for one hour,
the coolant pump fails for 2 1/2 hours (the reactor runs adiabatically), and then
the pump is restored. Simulate the response of the reactor for the six-hour start
up period. Does the system return to the steady state observed in part (a)? Explain
why or why not.
(c) Calculate the adiabatic temperature rise for the feed. Start the reactor ®lled with
solvent with initial temperature equal to the feed temperature plus the adiabatic
temperature rise of the feed. Simulate for six hours. Compare the steady state
achieved with the results in (a) and (b).
The reaction parameters are listed in the following table in which kT km e E1=T 1=Tm
and U A= C
Ã V .
p R
Parameter Value Units
km 5 10
4 min
1
Tm 298 K
E 8000 K
HR 3 5
10 kJ =
kmol
1000 kg = 3
m
CP
Ã 4 0 : kJ =
kg K
:
0 015 min
1
Ta 298 K
Tf 298 K
cAf 3 0 : kmol = m
3
cBf 2 0 : kmol = m
3
30 min
7
Fixed-Bed Catalytic Reactors
Exercise 7.22: Changing catalyst and temperature
The production rate of a heterogeneously catalyzed, ®rst-order reaction in a 0.75-cm
diameter spherical pellet is RAp :

3 25 10
5 mol/cm
3 s when the catalyst is exposed
to pure, gaseous A at a pressure of 1 atm and a temperature of 525 K. This reaction's
activation energy is Ea ; 18 600 cal/mol. Further, the effective diffusivity of A in the
pellet is DA : 2
0 009 cm /s at 525 K and that diffusion is in the regime of Knudsen
¯ow. The bulk ¯uid and the external surface concentrations can be assumed the same.
Find the production rate if the catalyst is changed to a cylindrical pellet that is 0.5 cm
in diameter and 1.0 cm in length, and the temperature is increased to 600 K.
Exercise 7.23: Diffusion, external mass transfer, and reaction rates
The following second order liquid-phase catalytic reaction is conducted in an isothermal
®xed-bed reactor:
A - ! B r kcA2
The intrinsic rate constant is 16 L = mol s. The feed is 0 8 L : = s of a solution of A with
the concentration of A at 4 mol = L. Spherical catalyst pellets of radius 0 12 cm are used :

to pack the reactor. The catalyst has a pellet density of 0 88 g : = 3
cm , and the reactor
bed density is 0 5 g : = 3
cm . The effective diffusivity of A inside the catalyst pellet is
:
3 14 10
3 cm2 =
s. You wish to achieve 99.9% conversion of A.
(a) First neglect both diffusional resistance and mass transfer resistance. What is the
mass of catalyst required to achieve the desired conversion?
(b) Next consider diffusional resistance but neglect mass transfer resistance. What
are the Thiele modulus and effectiveness factor at the entrance of the reactor?
What are the Thiele modulus and effectiveness factor at the exit of the reactor?
Given these two effectiveness factors, compute an upper bound and a lower bound
on the mass of catalyst required to achieve the desired conversion.
(c) Next consider both diffusional resistance and mass transfer resistance. Assume
that we have estimated the mass transfer coef®cient to be km : =

0 35 cm s. Find
43
44 Fixed-Bed Catalytic Reactors
the effectiveness factor at the entrance of the reactor. Find the effectiveness factor
at the exit of the reactor.
Given these two effectiveness factors, compute an upper bound and a lower bound
on the mass of catalyst required to achieve the desired conversion.
(d) Compare your answers to parts (a)±(c). Discuss whether diffusion and/or mass
transfer limitations are important in this packed bed reactor.

8
Mixing in Chemical Reactors
Exercise 8.16: PFRs, CSTRs, and mixing
Consider the following irreversible, liquid-phase reaction with 1/2-order kinetics
A - ! ; B r kcA1=2
Assume this reaction takes place in the the PFR in Figure 8.44, which is operating at
steady state with residence time and feed A concentration cAf . The total overall
reaction rate is r1 , which is the moles of A converted per time in the entire reactor
volume, divided by the volume of the reactor. At time zero, we turn on a stirrer and
perfectly mix the reactor contents. Immediately upon mixing the reactor achieves an
overall reaction rate r2 . Also consider the steady-state overall reaction rate achieved at
long times by the mixed reactor, r3 .
(a) Rank order the three overall reaction rates, r1 r2

, and r3 . Justify your answer.
(b) Calculate the exact values of r1 r2

, , and r3 for the following parameters: k
1 (mol/L)
1=2 (1/hr); 1 hr; cAf 1 mol/L.
Exercise 8.17: Dispersed PFR
You have been continuing studies on aromatization of cyclohexanone to phenol, when
your chemistry colleague comes to you with a catalytic breakthrough. By using a ho-
mogeneous catalyst the reaction can now tolerate various substituents on the cyclohex-
anone ring
PFR
steady state: r1 stirrer started: r2 steady state: r3
Figure 8.44: Reactor in three conditions: PRF at steady state, just after a perfect stirrer
is started, and stirred reactor at steady state. The overall reaction rates
are: r1 , r2 and r3 , respectively.
45
46 Mixing in Chemical Reactors
OH O
R5 R1 R5 R1
O2 2
2 H O
R4 R2 R4 R2
R3 R3
This new reaction has a downside though. The substituted cyclohexanones and
phenols can no longer tolerate high temperatures and must remain in the liquid phase,
but the O 2 is still in the gas phase. These new issues now need to be understood.
Assume the reaction rate is given by r kcA when excess O 2 is present. To provide
the required O 2 the reaction takes place in an isothermal, isobaric tubular membrane
reactor inside a large cylinder with a continuous supply of O 2 as shown in the following
schematic.
Liquid in Liquid out
2
O supply
The following parameter values are known.
VR ; Qf
66 mL = 3 mL min ; cAf : = ; cA VR :
0 1 mol L 0 01 mol =;
L
T ; P80 C 3 MPa ; R : 3 =

8 314 MPa cm mol K
(a) Ideal PFR. What is the residence time for this reactor? Solve the steady-state PFR
material balance. Given the steady-state outlet concentration of A is cA VR

:
0 01 mol =L, what is the value of the rate constant k ?
(b) Nonideal ¯ow. To perform an RTD step test on the reactor, two inert solvents
are used, toluene and cyclohexane. The reactor (PFR) begins with toluene ¯owing
through at steady state. At time t 0 a valve is turned introducing the cyclohex-
ane ¯ow and cutting off the toluene ¯ow. The measured RTD is shown in Figures
8.45 and 8.46.
What is the mean residence time for the reactor?
(c) Dispersion number. From Figure 8.47, which is similar to Figure 8.10 in the
text, and the experimental data shown in Figures 8.45 and 8.46, estimate the
dimensionless dispersion number, D , describing this reactor.

Mixing in Chemical Reactors 47
(d) Dispersed PFR model. What differential equations would you use to model the
dispersed PFR? Include all required boundary conditions. Make sure that all pa-
rameters appearing in your model are known.
How would you solve this model? Describe what you would do; you do not need
to actually solve it. Do you need any additional information to solve the problem?
If so, what?
(e) Engineering intuition. Would you expect the outlet A concentration to be higher,
lower, or the same as the ideal PFR case? Assume both cases have the same mean
residence times, ¯ow rates, rate constants, temperatures, pressures, etc. and base
your argument on only the nonideal ¯ow and dispersion. Justify your answer.
48 Mixing in Chemical Reactors
0.9
0.8
0.7
0.6
0.5
xc
0.4
0.3
0.2
0.1
-0.1
0 500 1000 1500 2000 2500 3000
time (s)
Figure 8.45: Mole fraction of cyclohexane in the ef¯uent versus time after step change
at t 0.
0.9
0.8
0.7
0.6
0.5
xc
0.4
0.3
0.2
0.1
-0.1
1200 1300 1400 1500 1600 1700 1800
time (s)
Figure 8.46: Mole fraction of cyclohexane in the ef¯uent versus time after step change
at t 0; expanded time scale.

Mixing in Chemical Reactors 49
:
0 9
:
0 8
:
0 7
:
0 6
P :
0 5
:
0 4
:
0 3
:
0 2 D :
0 0001
D :
0 0005
:
0 1 D :
0 001
D :
0 005
0
:
0 8 :
0 85 :
0 9 :
0 95 1 :
1 05 :
1 1 :
1 15 :
1 2
=
Figure 8.47: P versus = for dispersed plug ¯ow with different dispersion number
D.
9
Parameter Estimation for Reactor Models
Exercise 9.16: Least squares estimation and estimating measurement variance from
data
Consider the following reaction mechanism
H O2 )*C0 - - CO 2 H 2 (9.59)
H O2 )* H - - H 2 OH (9.60)
with reaction rates and production rates given by
2 3
RH
6 R H2
6 7
" # 7
6 7
r rr1 R 66 RROH
6 7
7
7
2 6 H2 O 7
6 7
4 RCO 5
RCO2
We have replicate measurements of the six species production rates. We wish to es-
timate the two reaction rates. Twenty replicate measurements are given on the class
website in the Exams folder. I also list the actual variance of the measurement error,
Qac . Download the ®le confestvar_measurements.dat and load these into Octave
using the load command; you should obtain two matrices, Qac and Rmeas. Perform the
following analysis.
(a) Assume we do not know Qac (the usual case) so we assume the measurement
error variance is an identity matrix, QI . Find the least-squares estimate of r

for each of the 20 measurements. Calculate the mean over the 20 estimates. Plot
all 20 estimates, and the 95% con®dence interval with center located at the mean
estimate.
Notice you should use Qac to compute the con®dence interval, not QI . We
want to analyze how the estimates are actually distributed, not how they would
be distributed if QI . Ask me if this point is not clear.
(b) Next calculate the covariance matrix for the twenty measurement samples. Call
this matrix Qest . Print out this matrix.
51
52 Parameter Estimation for Reactor Models
(c) Next using Q Qest , reestimate the values of r using weighted least squares. Plot
all twenty estimates and the 95% con®dence intervals with center located at the
mean estimate. How different are the mean estimates using QI and Q Qest ?
(d) Finally, using zero as the center, plot the 95% con®dence intervals for estimates
using Q I Q Qest
, , and Q Qac . How do these ellipses compare in size? Do
you obtain tighter con®dence interval (smaller variance) when you use Qest instead
of I in the least-squares estimate? How does the con®dence interval using Qest
compare to the one using Qac ? Why?
Bibliography
[1] G. E. Briggs and J. B. S. Haldane. A note on the kinetics of enzyme action. Biochem. J., 19:
338±339, 1925.
[2] U. Gennari, R. Kramer, and H. Gruber. Hydrogenolysis of methyltetrahydrofurane on plat-
inum. Applied Catalysis, 11:341±351, 1984.
[3] G. G. Hammes. Thermodynamics and Kinetics for the Biological Sciences. Wiley-Interscience,
New York, 2000.
[4] M. V. Henri. ThÂ

eorie gÂ
enÂ
erale de l'action de quelques diastases. Comptes Rendu, 135:916±
919, 1901.
[5] M. V. Henri. General theory of the action of certain enzymes. In T. R. C. Boyde, editor,
Foundation Stones of Biochemistry. Voile et Aviron, Hong Kong, 1980. English translation.
[6] L. Michaelis and M. L. Menten. Die Kinetik der Invertinwirkung. Biochem. Z., 49:333±369,
1913.
[7] L. Michaelis and M. L. Menten. The kinetics of invertin action. In T. R. C. Boyde, editor,
Foundation Stones of Biochemistry. Voile et Aviron, Hong Kong, 1980. English translation.
[8] D. L. Nelson and M. M. Cox. Lehninger Principles of Biochemistry. Worth Publishers, New
York, third edition, 2000.
53

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Exercise 2.16: Element balances

Consider a chemical reaction between the species P , Cl 4 2 and PCl 5

(a) Write the element matrix A for this reaction.

sible integers for  .

Exercise 2.17: More element balances

Consider the reaction

(a) Write the element matrix A for this reaction.

sible integers for  .

Exercise 2.18: A 10th grade stoichiometry problem

Consider the reaction

1 KClO 3  2 HCl - - )* 3 KCl  4 2

(a) Write the element matrix A for this reaction.

(c) Write all possible stoichiometries for these species.

Exercise 2.19: Stoichiometry short questions

a set of reactions that is linearly dependent?

(b) For the reaction

(c) Consider the set of reactions

please keep the species in alphabetical order in the species list.

2. By inspection, what is the rank of this matrix? Explain your answer.

Exercise 3.16: Confusion over reaction equilibrium with multiple phases

I have a gas/liquid two-phase system with the chemical reaction

so I ®x T and P and try to ®nd the phase compositions, yj , and xj j  A; B; C

I have 6 2  4 unknowns since the mole fractions in each phase sum to

equilibrium relations are

the gas phase for the reaction equilibrium gives

ture doesn't know which phase I choose when I do my equilibrium calcula-

How do you respond to this student?

Exercise 3.17: Equilibrium, friend or foe?

you have converted about 50 percent of the starting materials.

important point is to explain and justify your choice.

data you require, if any, to justify this approach.

whatever new data you require is available in your company's thermochemical

data you require is available in your company's thermochemical database.

Exercise 4.23: Short answers on microscopic and macroscopic balances

stream, and otherwise moves to contain chemical species j  ; : : : ns

give a short explanation justifying your answer.

bounding surface is S and moves with velocity vs .

Exercise 4.24: Esteri®cation in a CSTR

constant during the entire operation.

(a) What are the units of k?

stream ¯owrates QA and QB ? Show your reasoning.

have differential equations for dcA =dt dcB =dt

conditions do you require for these two differential equations.

acid and base concentrations in the reactor, cAs ; cBs .

of the parameters? Is this steady-state solution unique?

following speci®c parameter values, ®nd the steady-state reactor concentrations

k : 0 1 (in units of min, mol, L)

Exercise 4.25: PFR with changing ¯owrate

over the temperature range T0  T  Tout .

perature T , and pressure P for the ideal gas equation of state?

sible integers for .

sible integers for .

1 KClO 3 2 HCl - - )* 3 KCl 4 2

so I ®x T and P and try to ®nd the phase compositions, yj , and xj j A; B; C

I have 6 2 4 unknowns since the mole fractions in each phase sum to

stream, and otherwise moves to contain chemical species j ; : : : ns

k : 0 1 (in units of min, mol, L)

over the temperature range T0 T Tout .

stants are all similar, k1 k2 k3 k , and the concentrations of A and B are

kVR1 =Qf 1 kVR2 =Qf 2

function of Qf and the recycle ratio r Q2 =Q1 .

recycle? Try again for r =3 4 and r = 1 4.

(c) Draw a sketch of cA t versus t .

cA0 1 mol/L k1 cB0 2 L/(mol hr) k2 cB0 1 hr

Check your analytical solution for cA t from Exam 1

sC RRC SC nnC nnC 0 xA nAn0 nA

cAf : 1 4 mol = L K : = 2 0L mol

cAf : 0 6 mol = L K : = 1 0L mol

cAf : 1 4 mol = L K : = 2 0L mol