Extra Exercises

for

Chemical Reactor
Analysis and Design
Fundamentals

James B. Rawlings
Department of Chemical and Biological
Engineering
University of Wisconsin
Madison, Wisconsin

D
John G. Ekerdt
Department of Chemical Engineering
The University of Texas
Austin, Texas

November 21, 2014

b Hi
No ll Publishing

Madison, Wisconsin
The extra exercises were set in Lucida using LATEX.

c 2013 by Nob Hill Publishing, LLC

Copyright

All rights reserved.

Nob Hill Publishing, LLC

Cheryl M. Rawlings, publisher
Madison, WI 53705
orders@nobhillpublishing.com
http://www.nobhillpublishing.com

The extra exercises are intended for use by students and course in-
structors.

This document has been posted electronically on the website: www.

che.wisc.edu/~jbraw/chemreacfun.
2
The Stoichiometry of Reactions

Exercise 2.16: Element balances

Consider a chemical reaction between the species P4 , Cl2 and PCl5

ν1 P4 + ν2 Cl2 )-
-* ν3 PCl5 (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 ν.

Exercise 2.17: More element balances

Consider the reaction

ν1 H3 PO4 + ν2 SrCO3 )-
-* ν3 Sr3 (PO4 )2 + ν4 CO2 + ν5 H2 O

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

(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 ν.

Exercise 2.18: A 10th grade stoichiometry problem

Consider the reaction

ν1 KClO3 + ν2 HCl )-
-* ν3 KCl + ν4 H2 O + ν5 Cl2 + ν6 ClO2

1
2 The Stoichiometry of Reactions

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

(b) How many linearly independent reactions are possible with these species?

(c) Write all possible stoichiometries for these species.

Hint: you will not obtain integer coefficients if you use standard software to find
null space of A T 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 + O2 )-
-* 2NO2

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 difficult 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−π −r
f =3+2−2−1
f =2

so I fix T and P and try to find 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
liq gas
µj = µj j = A, B, C

for three equations, and I know the condition for reaction equilibrium is
n
Y νj
K= aj
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
Y νj yC
aj = gas-phase
j
P yA yB
Y νj xC
aj = liquid-phase
j
xA xB

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

P yj = 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
yC
K=
P yA yB
P yC
=
(P yA )(P yB )
PC0 xC
=
(PA xA )(PB0 xB )
0

 0 
PC xC

=
PA0 PB xA xB
xC
K≠
xA xB

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
=1
PA0 PB
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?

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 = 1, . . . ns with velocities
vj relative to some fixed 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.
∂cj d
Z Z
(a) dΩ = cj dΩ if the volume element is well-mixed
V (t) ∂t dt V (t)

∂cj dcj
Z
(b) dΩ = VR if the volume element is well-mixed
V (t) ∂t dt

d ∂cj
Z Z Z
(c) cj dΩ = dΩ + cj (vs · n)dσ
dt V (t) V (t) ∂t S(t)

Rj

Q0 V
111
000 Q1
000
111
cj0 000
111
000
111
000
111 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 .

5
6 The Material Balance for Chemical Reactors

QA
cAf
Q
QB
VR cA
cBf cB

Figure 4.40: Organic acid and base streams fed into a CSTR.

Z
(d) cj (vj · n)dσ = −Q0 cj0 + Q1 cj if the volume element is well-mixed
S(t)

dVR
Z
(e) cj (vj ·n)dσ = −Q0 cj0 +Q1 cj +cj if the volume element is well-mixed
S(t) dt

d
Z Z Z
(f) cj dΩ = − cj (vj − vs ) · ndσ + Rj dΩ
dt V (t) S(t) V (t)

Exercise 4.24: Esterification in a CSTR

Consider the liquid-phase organic esterification 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 esterification reaction and its rate are
given by

A + B -→ ester + H2 O 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 fluid 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 flowrate Q of the effluent stream in terms of the feed
stream flowrates 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 finished. 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 7

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 specific parameter values, find the steady-state reactor concentrations
cAs , cBs

τ = 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 specific param-
eter values?

Exercise 4.25: PFR with changing flowrate

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 flow NA0 at temperature T0 , pressure P0 and volumetric
flowrate 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 flow N, volumetric flowrate 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 flow N expressed
solely in terms of the molar flowrate of component A NA , i.e. an expression not
involving NB and NC ?
8 The Material Balance for Chemical Reactors

(d) Assume first that the volumetric flowrate does not depend on the change in the
number of moles with reaction, nor on the temperature, i.e. Q(V ) = Q0 . Find the
reactor volume, VR , required to achieve 90% conversion of A. Call this volume VR1 .
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
flowrate 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 VR2 ? Why?

(f) Finally, assume the change in temperature is well approximated by the linear
relationship
V
T (V ) = T0 + (Tout − T0 )
VR
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 = 1.5 T0 for T in absolute temperature units

What reactor volume is required to achieve 90% conversion? Call this volume VR3 .
Find the ratio VR3 /VR2 . You can obtain a numerical value for this ratio with the
given information. Which reactor is larger, VR2 or VR3 ? 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-filled reactor of
1000 L assuming an ideal mixture. Be sure to plot the molar numbers of all components,
the reactor volume and the effluent flowrate 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 fixed and constant outlet flowrate

Q = αQf
The Material Balance for Chemical Reactors 9

A B

cA0
nB0
nA0
cB0

Figure 4.42: Species A and B in a well-mixed volume element. Continuum and molec-
ular settings.

For what range of α does the model admit a steady-state solution? Provide a
closed-form solution for the steady-state reactor volume as a function of α valid
over this range. Plot this steady-state reactor volume versus α over this range.
You may want to display this result using a semi-log plot for the y-axis.

(c) Choose α = 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 2
A + A -→ C r1 = k1 cA
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
2
r = 3kcA0
10 The Material Balance for Chemical Reactors

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 = 2cA0 , cB = 0 and the total rate is then

r = r1 + r2 + r3
2
r = k1 cA + k2 cA cB + k3 cB2
r = k(2cA0 )2 + k(2cA0 · 0) + k(0)2
2
r = 4kcA0

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
.. .. ..
... ... ..
... ... ...
.. .
. .
. .
. ................. ....
. ................
.
. ....
. .... .......
....... ..
. .
. ..... ...............
....... .......
... ...
........ ......
... ........ ....... .....
. ..
... ... .. ....
... .... ... ...
...
...
...
... + O2 -→ ... ...
... ...
....
... + 2 H2 O
... ... ... ... .....
..
...... .
. ... ...... ..............
.
....... .... ....... ... .
....... . ...
.. .... ....... .....
. ..............
....... . ....... . .......
................... .............

cyclohexanone phenol

or

k
A + O2 -→ B + 2H2 O 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.
The Material Balance for Chemical Reactors 11

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 O2 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

k
A -→ 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 modification using a second reactor
shown in Figure 4.43(b). The following parameter values are known

kVR1 /Qf = 1 kVR2 /Qf = 2

12 The Material Balance for Chemical Reactors

VR2
cA2 cA
Q2 Q2 = r Q1

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) Modified 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 find 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?
5
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.

13
14 Chemical Kinetics

species A A·X G F B D E C H2 O H2 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 effluent of
a flow reactor. Adsorbed methyl THF (A·X) is adsorbed on the catalyst and
is not present in the effluent, but is present in the reactor in nonnegligible
amount.

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) (5.163)
k−1
k2
A · X + H2 )-
-* F+ X (5.164)
k−2
k3
A · X + H2 )-
-* B+ X (5.165)
k−3
k4
G + H2 )-
-* F (fast) (5.166)
k−4
k5
H2 + F -→ C + H2 O (5.167)
k6
B )-
-* D + H2 (5.168)
k−6
k7
D -→ E + CO (5.169)
k8
H2 + B -→ C + H2 O (5.170)

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. The feed consists of A and H2 .
Typical steady-state concentrations of the gas-phase species in the effluent 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).
Chemical Kinetics 15

(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

k1 k1
cBs = cAs = cA0 e−k1 t
k2 k2

The concentration of C is always available if desired from the total species balance

cCs (t) = cA (0) + cB (0) + cC (0) − cAs (t) − cBs (t)

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 cB0 to the quasi-steady-state value for which
RB ≈ 0. Divide B’s material balance by k2 , define the fast time-scale time as
τ = k2 t, and obtain for B’s material balance

dcB 1
= k1 cA − cB =
dτ k2

We wish to find 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 (0) = cB0 Yn (0) = 0, n = 1, 2, . . .

16 Chemical Kinetics

Substitute the series expansion into B’s material balance, collect like powers of 
and show the following differential equations govern the Yn
dY0
0 : = −Y0
dτ
dY1
1 : = k1 cA − Y1
dτ
dYn
n : = −Yn n ≥ 2
dτ

(c) Solve these differential equations and show

Y0 = cB0 e−τ
k1  
Y1 = cA0 e−τ − e−k1 τ/k2
k1 /k2 − 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 first 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
 = k1 cA − cB
dt
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
dB0
1 : = k1 cA − B1
dt
dBn
n : = −Bn+1 n ≥ 1
dt
Solve these equations and show

B0 = 0
B1 = k1 cA
Bn = kn
1 cA n≥2

So we see the zero-order outer solution is CB0 = 0, which is appropriate for a

QSSA species, but a rather rough approximation.
Chemical Kinetics 17

(e) Show that the classic QSSA analysis is the first-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 first-order solutions for the following parameter values

cA0 = 1 cB0 = 1/2 k1 = 1 k2 = 10

Compare to the exact solution and the first-order outer solution (QSSA solution).

(g) Show that the infinite 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

1
  kK
− 1 2t
cAs = cA0 + cB0 e 1+K2
1 + K2
1 k1 1
  kK
− 1 2t
cBs = cA0 + cB0 e 1+K2
k−1 1 + K2 1 + K2

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  = 1/k−1 . Define
K2 = k2 /k−1 and we assume that K2 is order unity or smaller. If K2 were large, we
18 Chemical Kinetics

should have chosen  = 1/k2 as the small parameter. Collect terms of like power
of  and show
dX0 dY0
0 : = Y0 = −(1 + K2 )Y0
dτ dτ
dX1 dY1
1 : = −k1 X0 + Y1 = k1 X0 − (1 + K2 )Y1
dτ dτ
dXn dYn
n : = −k1 Xn−1 + Yn = k1 Xn−1 − (1 + K2 )Yn n≥1
dτ dτ

What are the initial conditions for the Xn and Yn variables?

(c) Solve these for the zero-order inner solution and show
1  
X0 = cA0 + cB0 1 − e−(1+K2 )τ Y0 = cB0 e−(1+K2 )τ
1 + K2

(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 (1 + K2 )B0 = 0
dA0 dB0
1 : = −k1 A0 + B1 = k1 A0 − (1 + K2 )B1
dt dt
dAn−1 dBn−1
n : = −k1 An + Bn = k1 An−1 − (1 + K2 )Bn n≥1
dt dt

(e) Solve these and show for zero order

k K
1 2t
− 1+K
A0 = A0 (0)e 2 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

lim X0 (τ) = lim A0 (t)

τ→∞ t→0
Chemical Kinetics 19

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
1
A0 (0) = cA0 + cB0
1 + K2

(f) Find also the first-order solution, B1 , and show that the QSSA solution corresponds
to the zero-order outer solution for cA and the first-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 first
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 define the fast
time scale as
t k1
τ= K1 =
k−1 k−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
= −K1 X0 + Y0 X0 (0) = cA0
dτ
dY0
= K1 X0 − Y0 Y0 (0) = cB0
dτ

(c) Solve these differential equations and show

1  
X0 = cA0 e−(1+K1 )τ + (cA0 + cB0 ) 1 − e−(1+K1 )τ
1 + K1
K1  
Y0 = cB0 e−(1+K1 )τ + (cA0 + cB0 ) 1 − e−(1+K1 )τ
1 + K1
20 Chemical Kinetics

(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 A0 − B0

and the first order terms give the two differential equations

dA0
= −K1 A0 + B1
dt
dB0
= K1 A0 − B1 − k2 B0
dt

Use the matching conditions with the fast time scale solution to derive the initial
conditions for the slow-time-scale differential equations and show

1 K1
A0 (0) = (cA0 + cB0 ) B0 (0) = (cA0 + cB0 )
1 + K1 1 + K1

(e) We now wish to eliminate the first-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
=− A0
dt 1 + K1
dB0 k2 K1
=− B0
dt 1 + K1

(f) Solve these differential equations and show the zero-order outer solution is

1 k K
− 2 1t
cAo = (cA0 + cB0 ) e 1+K1
1 + K1
K1 k K
− 2 1t
cBo = (cA0 + cB0 ) e 1+K1
1 + K1

Compare this solution to the reaction equilibrium solution of the first part. What
conclusions do you draw from this comparison?

1 Notice that this addition of the two equations to remove the unknown B is analogous to the step that
1
eliminated r2 and led to Equation 5.45 in the discussion in Chapter 5.
Chemical Kinetics 21

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
first 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 first-order, irreversible decomposition
of S to P

S -→ P r

(a) For a well-stirred batch reactor, show the total enzyme concentration satisfies

cE (t) + cES (t) = cE (0) + cES (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
kcS k1
r = k = k2 KE0 K= E0 = cE (0) + cES (0) (5.171)
1 + KcS k−1 + k2
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 = 1 k2 = 10
cE (0) = 1 cES (0) = 0 cS (0) = 50 cP (0) = 0
22 Chemical Kinetics

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 first 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

kc
e S
RP = k
e = k2 K1 E0 K1 = k1 /k−1 (5.172)
1 + K1 cS

in which K1 is the equilibrium constant for the first 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 first 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 5.171 and Equation 5.172 [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.
Chemical Kinetics 23

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

!
K1 cE kc
  e S
re1 = k
e = k 2 K1 E 0
1 + K1 (cE + cS ) 1 + K1 c S
kc
e S
re2 = K1 = k1 /k−1
1 + K1 c S

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 first 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 = 0.5 k−1 = 1 k2 = 0.5

cE (0) = 20 cES (0) = 10 cS (0) = 50 cP (0) = 0

Recall that you must modify the initial conditions for the slow-time-scale model
by equilibrating the first 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.

24 Chemical Kinetics

(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
... ... ...
... ... ..
......... ...
.. . . ..
....
..... ............
.
. .
...
...... ..............
...
...... ....... .....
. ....... .......
.... ....... .... ....... .......
........ .... ........ ...... ....
.... .... .... ... .....
... ... ... ... ...
... ...
...
+ O2 -→ ... ... ...
...
+ 2 H2 O
... ... ....
.... ..... ... . .....
....... . ...... ...
....... .
.. .
. ..... . ....... .
. ....................
. .
....... ... ....... .. .
....... ..................
....... ............. .........
.......

cyclohexanone phenol
or
k
A + O2 -→ C + 2H2 O 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 + H2 OS∗
k−1 O O OH
∗ k2
.... .... ..
BS + OS -→ CS + H2 OS∗ .. ....
.
.
..........
.... ............
.
.. . ..
.
.
..........
.... ............
. .
. ....
..
......
.
..... .....................
.... ...... .... ...... ....
....... ... ....... .......
. ............
K3 .... ... .... ... ..... ... ...
...
...
... ... ... .... .... ... ... ...
A+ S )-
-* AS ....
...... .
...
. ....
......
... ...
. ... ...
........ ...
...
.
....... .
...
. .... ....... .
...
. ..... ....... ........................
.
....... ......... ....... ......... ..............
K4 .... .... ..
O2 + 2 S∗ )-
-* 2 OS∗
cyclohexanone cyclohexenone phenol
K5 A B C
C+ S )-
-* CS
K6
H2 O + S∗ )-
-* H2 OS∗
Chemical Kinetics 25

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. O2 and H2 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 (for S) and cm∗ (for S∗ )? No surface species concentration should appear in
your final rate expression.
6
The Energy Balance for Chemical Reactors

Exercise 6.24: Mass and energy balances with multiple phases1

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: α and β. Consider the state of
the reactor to be described by the following set of 2(ns + 2) intensive variables and 2
extensive variables

T α , P α , mα , cjα j = 1, . . . ns
β
T β , P β , mβ , cj j = 1, . . . ns

in which mα , mβ are the masses of the α and β 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
1 JBR would like to thank Vasilios Manousiouthakis of UCLA for helpful discussion of this and the next

two exercises.

Q̇

T P VR

α cjα mα Qα
Qf

cjf
β
Tf β cj mβ Qβ

Figure 6.43: Reactor containing two well-mixed phases of matter.

27
28 The Energy Balance for Chemical Reactors

to describe the state of the reactor with 2ns + 2 intensive variables and 2 extensive
variables
β
T , P , mα , mβ , cjα , cj j = 1, . . . ns

Since the process in Figure 6.43 is an open system, we also have the two effluent
flowrates and the rate of heat transfer to the system

Qα , Qβ , Q̇

that need to be determined, bringing the total number of unknown variables to 2ns + 7.
We assume we have specified 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 specified. So we have specified two of our unknown variables

P , Q̇

which brings us back to 2ns + 5 unknowns, and we have one constraint on the total
system volume.

(a) Is the process now fully specified? If so, write the 2ns + 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 effluent
streams. For this case, we have 2ns + 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
0 = g(x, y)

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.
The Energy Balance for Chemical Reactors 29

(b) Identify the variables that comprise x and y.

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 difficult 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 defined a particular reference pressure, temperature,
composition and phase of matter, which determines all intensive thermochemical prop-
erties. Denote the specific internal energy and enthalpy of the reference state by

Ûref Ĥref

which are related by

Pref
Ûref = Ĥref +
ρref
Consider these common material and energy balances for a two-phase system

dnj β
X 
β

= Qf cjf − Qα cjα − Qβ cj + νij riα + ri j = 1, . . . , ns
dt i
dU dVR
+P = Qf ρf Ĥf − Qα ρ α Ĥ α − Qβ ρ β Ĥ β + Q̇
dt dt
Now define the following shifted internal energies and enthalpies
α β α β
e = Û α − Ûref
U e = Û β − Ûref
U e = Ĥ α − Ĥref
H e = Ĥ β − Ĥref
H

Calling the thermochemical database functions returns these shifted quantities. Define
the shifted total internal energy by

e = mα (Û α − Ûref ) + mβ (Û β − Ûref )

U
= mα Û α + mβ Û β − (mα + mβ )Ûref
U
e = U − mÛref

in which m = mα + mβ is the total mass of the system.

30 The Energy Balance for Chemical Reactors

(a) We would like to use a new energy balance expressed in terms of these shifted
variables. Is the following shifted energy balance correct?

dU dVR α β
e f − Qα ρ α H
e − Qβ ρ β H
e
+P = Qf ρf H e + Q̇ (6.95)
dt dt
If so, provide a derivation. If not, derive a correct form.

(b) Consider a second approach in which the same reference energy, Êref is subtracted
from all energies (both the internal energy and enthalpy)
α β α β
e = Û α − Êref
U e = Û β − Êref
U e = Ĥ α − Êref
H e = Ĥ β − Êref
H
U
e = U − mÊref

Is the shifted energy balance, Equation 6.95, correct with these defined 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

(a)
∂U
 
= −αT V + P V κT
∂P T ,nj

(b) !
∂U α
= Hj − TVj
∂nj T ,V ,nk≠j
κT

Exercise 6.28: Nonisothermal plug-flow 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 first reactor?

(b) What is the conversion of A at the outlet of the first reactor?

(c) Is the first reactor close to equilibrium at the exit?

The Energy Balance for Chemical Reactors 31

T0 = 27◦ C T0 = 27◦ C

NA0 = NB0 = 10 mol/min

Q̇ = −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 × 105
NA0 , NB0 10 mol/min
Q̇ −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
= Q̇ (6.96)
dt
For a single-phase system, internal energy U (T , V , nj ) changes due to changes
in T , V and nj by
!
∂U ∂U X ∂U
   
dU = dT + dV + dnj (6.97)
∂T V ,nj ∂V T ,nj j
∂nj T ,V ,nk≠j

The definitions of constant volume heat capacity and partial molar internal
energy are

∂U
 
CV = (6.98)
∂T V ,nj
!
∂U
Uj = (6.99)
∂nj T ,V ,nk≠j
32 The Energy Balance for Chemical Reactors

Since the reactor volume is constant, dV = 0, and forming the time derivative
of the internal energy from Equation 6.97 reduces to

dU dT X dnj
= CV + Uj (6.100)
dt dt j
dt

From the definition of enthalpy (H = U + P V ), we know that

Hj = U j + P V j (6.101)

in which H j is the partial molar enthalpy and V j is the partial molar volume.
The material balance for the batch reactor is
dnj X
= Rj VR = νij ri VR , j = 1, . . . , ns (6.102)
dt i

in which ri is the reaction rate per reactor volume and νij is the stoichio-
metric coefficient for species j in reaction i. We can define the change in
enthalpy and change in volume for reaction i by
ns
X ns
X
∆HRi = νij H j ∆VRi = νij V j (6.103)
j=1 j=1

I put the material balance and these definitions in Equation 6.100 and I obtain

dT X
CV = − (∆HRi − P ∆VRi ) ri VR + Q̇ (6.104)
dt i

Notice that my result doesn’t agree with Equation 6.66 in our text!

dT X α

CV =− ∆HRi − T ∆VRi ri VR + Q̇
dt i
κT

What’s going on here?

Answer the following questions yes or no and provide a short justification.

(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 definitions of constant-volume
heat capacity and partial molar internal energy?

(d) Is Equation 6.100 a correct rearrangement of the previous equations?

The Energy Balance for Chemical Reactors 33

(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 definitions 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-flow reactor energy balance

Start with the plug-flow energy balance of Section 6.5, rewritten here,

∂ ∂
(ρ Û ) = − (Qρ Ĥ) + q̇
∂t ∂V

(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-flow reactor with collocation

Revisit the ammonia synthesis in an autothermal plug-flow 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 profiles to the results given
in Figures 6.39 and 6.40. Be sure to note that the flowrate should be Qf =
0.05713 m3 /s in Table 6.6, and that the the middle steady-state profile (B) in
Figures 6.39 and 6.40 is shifted somewhat from the correct answer. See the errata
posted on www.che.wisc.edu/~jbraw/chemreacfun for the correct profiles.
2 The following is one form the answer can take.
 ∂T ∂P ∂cj ∂T ∂P
 X   X
ρ ĈP − αP + (P κT − αT ) − PVj = −Q ρ ĈP + (1 − αT ) − ∆HRi ri + q̇
∂t ∂t ∂t ∂V ∂V
j i
34 The Energy Balance for Chemical Reactors

(b) What initial guesses for the collocation equations did you use to converge to the
three steady-state profiles?

(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

Q̇ = −200, 000 BTU/hr

to reach the conversion xA = 0.7 at the exit of the second reactor.

Here we consider two finite-sized reactors, each with volume

Vt = 2.22 ft3

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 profiles 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 finite-sized reactors.

(b) Next let’s see if we can achieve xA2 = 0.7 by changing the heat duty. Vary Q̇
between −125, 000 and −250, 000 BTU/hr, and make a plot of xA2 versus Q̇ over
this range. Can you reach xA2 = 0.7 by changing the heat duty? If so, what value
of Q̇ do you use? If not, why not?
The Energy Balance for Chemical Reactors 35

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
batch reactor
k1
cA = cA0 e−k1 t e−k1 t − e−k2 t


cB = cA0
k2 − k1
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.

(a) Give an expression for Q̇, 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
k
A + B -→ 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 filled reactor at the feed temperature.
Simulate the reactor behavior (cA (t), cB (t), T (t)) for six hours after start up.
36 The Energy Balance for Chemical Reactors

(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 filled 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 k(T ) = km e−E(1/T −1/Tm )
and α = (U ◦ A)/(ρ Ĉp VR ).

Parameter Value Units

km 5 × 10−4 min−1
Tm 298 K
E 8000 K
∆HR −3 × 105 kJ/kmol
ρ 1000 kg/m3
ĈP 4.0 kJ/kg · K
α 0.015 min−1
Ta 298 K
Tf 298 K
cAf 3.0 kmol/m3
cBf 2.0 kmol/m3
τ 30 min
7
Fixed-Bed Catalytic Reactors

Exercise 7.22: Changing catalyst and temperature

The production rate of a heterogeneously catalyzed, first-order reaction in a 0.75-cm
diameter spherical pellet is RAp = −3.25×10−5 mol/cm3 ·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 = 0.009 cm2 /s at 525 K and that diffusion is in the regime of Knudsen
flow. The bulk fluid 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
fixed-bed reactor:

2
A -→ B r = kcA

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/cm3 , and the reactor
bed density is 0.5 g/cm3 . 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 coefficient to be km = 0.35 cm/s. Find

37
38 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

1/2
A -→ B, r = kcA

Assume this reaction takes place in the the PFR in Figure 8.44, which is operating at
steady state with residence time τ 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); τ = 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-

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.

39
40 Mixing in Chemical Reactors

mogeneous catalyst the reaction can now tolerate various substituents on the cyclohex-
anone ring

O OH
... ... ...
... ... ..
... ... ...
.
...
. ..................
. .
..
. .. . .
.... ............
.
R5 .......... ............ . .......
....... .......... R1 R5 .......... ............ ......................... ......... R1
.
............ .......... ............ ....... .............
. . .. ..
.... ..... .... . ...
... ... .... .... ...
....
..
...
...
+ O2 -→ .... ....
.. ..
...
... + 2 H2 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
O2 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 O2 is present. To provide
the required O2 the reaction takes place in an isothermal, isobaric tubular membrane
reactor inside a large cylinder with a continuous supply of O2 as shown in the following
schematic.

Liquid in Liquid out

O2 supply

The following parameter values are known.

VR = 66 mL, Qf = 3 mL/min, cAf = 0.1 mol/L, cA (VR ) = 0.01 mol/L,

T = 80 C, P = 3 MPa, R = 8.314 (MPa · cm3 )/(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 flow. To perform an RTD step test on the reactor, two inert solvents
are used, toluene and cyclohexane. The reactor (PFR) begins with toluene flowing
through at steady state. At time t = 0 a valve is turned introducing the cyclohex-
ane flow and cutting off the toluene flow. The measured RTD is shown in Figures
8.45 and 8.46.
What is the mean residence time for the reactor?
Mixing in Chemical Reactors 41

(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.

(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, flow rates, rate constants, temperatures, pressures, etc. and base
your argument on only the nonideal flow and dispersion. Justify your answer.
 42 Mixing in Chemical Reactors

1
0.9
0.8
0.7
0.6
0.5
xc
0.4
0.3
0.2
0.1
0
-0.1
0 500 1000 1500 2000 2500 3000
time (s)

Figure 8.45: Mole fraction of cyclohexane in the effluent versus time after step change
at t = 0.

1
0.9
0.8
0.7
0.6
0.5
xc
0.4
0.3
0.2
0.1
0
-0.1
1200 1300 1400 1500 1600 1700 1800
time (s)

Figure 8.46: Mole fraction of cyclohexane in the effluent versus time after step change
at t = 0; expanded time scale.
Mixing in Chemical Reactors 43

0.9

0.8

0.7

0.6

P (θ) 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
θ/τ

Figure 8.47: P (θ) versus θ/τ for dispersed plug flow 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

H2 O + C0 )-
-* CO2 + H2 (9.59)
H2 O + H )-
-* H2 + OH (9.60)

with reaction rates and production rates given by

 
RH
RH2
 
" #  
r1 ROH
 
 
r = R= 
r2 
 RH2 O 

RCO
 
 
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 file 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, Q = I. 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% confidence interval with center located at the mean
estimate.
Notice you should use Qac to compute the confidence interval, not Q = I. We
want to analyze how the estimates are actually distributed, not how they would
be distributed if Q = I. 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.

45
46 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% confidence intervals with center located at the
mean estimate. How different are the mean estimates using Q = I and Q = Qest ?

(d) Finally, using zero as the center, plot the 95% confidence intervals for estimates
using Q = I, Q = Qest , and Q = Qac . How do these ellipses compare in size? Do
you obtain tighter confidence interval (smaller variance) when you use Qest instead
of I in the least-squares estimate? How does the confidence 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. Théorie générale 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.
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47