Chemical Engineering Science 55 (2000) 991}1008

New design formulation of chemical reactors with multiple reactions:

I. basic concepts
Uzi Mann*
Department of Chemical Engineering, Texas Tech University, Lubbock, TX 79409-3121, USA
Received 3 November 1997; accepted 26 April 1999

Abstract

A new approach to formulate the design of chemical reactors with multiple reactions is presented. The new design methodology is
applicable for all reactor con"gurations, any number of chemical reactions, having any form of rate expressions. Reactor operations
are formulated in terms the smallest set of dimensionless design equations and their solutions provide dimensionless operating curves,
indicating progress of the chemical reactions, species compositions and the temperature variations without considering the reactor
size or operating time. Reactor sizing represents a `pointa on these operating curves and the required volume is readily determined for
a speci"ed feed rate and given reaction rates. The design is formulated using the least number of terms in each design equation, thus
providing the most robust set of equations for numerical solutions. The methodology also provides new design capabilities for reactor
con"gurations whose designs are not available in the literature. Part I presents the basic concepts of the new approach and illustrates
how they are applied. ( 1999 Elsevier Science Ltd. All rights reserved.

Keywords: Chemical reaction engineering; Reactor design; Simultaneous chemical reactions; Batch reactors; Flow reactors; Stoichiometry

1. Introduction f The design formulation is structured to provide in-

Despite the key role chemical reactors play in many
industrial processes, the current design formulation of
chemical reactors is limited in scope, cumbersome, and,
in many cases, results in equations that are numerically
unstable. Most design procedures in the chemical indus-
try involve two stages: (i) Generic dimensionless descrip-
tion of the operation and its features, and (ii) sizing the
equipment to meet a speci"ed production rate. However,
the current methodology to design chemical reactors
skips the "rst step, and is concerned solely with sizing the
reactor. Consequently, some characteristic features of
reactor operations are not considered in the design. Spe-
ci"cally, the current reactor design methodology has
three major de"ciencies:
f Reactor operations are described in terms of system-
specixc, extensive quantities (reactor volume, species
#ow rates, operating time, etc.) instead of intensive
quantities and dimensionless design equations (as done in
essentially all other operations in the process industries).
* Corrresponding author.
E-mail address: umann@ttu.edu (U. Mann)
formation on single `pointsa (e.g., required reactor
volume to obtain a speci"ed conversion for a given
#ow rate); little, if any, attention is given to the generic
behavior of the reactor. (It is analogous to conducting
separate sets of pressure-drop calculations for tubes of
di!erent diameters instead of using the relationship
between a dimensionless friction factor and the Reynolds
number.)
f No systematic methodology is available to design
chemical reactors with multiple reactions. The current
design methodology has been developed for chemical
reactors with single reactions and the formulation is
usually in terms of the conversion of a reactant
(Levenspiel, 1962). For reactors with multiple reac-
tions, the common approach is to write the species
balance equations for each chemical species that ap-
pears in the rate expressions and to express them in
terms of either the species concentrations or molar
#ow rates (see, for example, Fogler, 1992; Froment
& Bischo!, 1990). In many cases, this `brute-forcea
approach results in design formulations that consist of
a number of equations larger than the minimum neces-
sary to describe the operation, often leading to unsta-
ble or inaccurate numerical solutions.

0009-2509/00/$ - see front matter ( 1999 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 9 9 ) 0 0 3 6 4 - 4
992 U. Mann / Chemical Engineering Science 55 (2000) 991}1008

Nomenclature Greek letters

C concentration, mol/volume a multiplier of the mth independent reaction to ob-

km
C total concentration de"ned in Eqs. (7a) or (7b), tain the kth dependent reaction, dimensionless
0
mol/volume D change in the number of moles per unit extent of
i
E activation energy, energy/mol the ith reaction, mol
a
F molar #ow rate, mol/time q dimensionless operating time, t/t , or space time,
#3
f conversion of a reactant, dimensionless < /v t , dimensionless
R 0 #3
k reaction rate constant h dimensionless temperature, (t)/(0) or / ,
0
MW molecular mass, mass/mol dimensionless
N, N(t) number of moles in the reactor, mol
R gas constant, energy/temperature mol Subscripts
r rate of a chemical reaction, mole extent/time
volume 0 reference stream or state
(!r ) depletion rate of reactant A, mole A con- A limiting reactant
A
sumed/time volume all all reactions
(r ) formation rate of species j, mol of species j cr characteristic reaction
j
formed/time volume dep dependent reactions
s stoichiometric coe$cient, mol species/mol eq equilibrium
extent I inert
(s ) stoichiometric coe$cient of species j in the ith i the ith reaction
ji
reaction, mol j/mol extent in inlet
temperature, K ind independent reactions
t time, time j the jth species
< volume, volume k index number of dependent reactions, the kth
v volumetric #ow rate, volume/time dependent reaction
X, X(t) extent of chemical reaction, mol extent m index number of independent reactions, the mth
Xs units of extent reacted per unit time, mol ex- independent reaction
tent/time R reactor
y, y(t) mole fraction, dimensionless sp space
Z dimensionless extent, X/(N ) or Xs /(F ) , out outlet
505 0 505 0
dimensionless tot total

These de"ciencies have rami"cations beyond the design
and operation of chemical reactors. The genesis of all
procedures for system-based modeling and optimization
is the generic, dimensionless design formulations of
the operation without regard to equipment sizing.
(For example, the optimization of #ow systems is
based on the dimensionless friction factor versus
Reynolds number description of #ow in tubes.) Such
generic description is not currently available for reactor
operations, and this has prevented the development of
system-based design methodologies for integrated chem-
ical processes.
This paper describes a new general methodology to
design chemical reactors with multiple reactions that
overcomes all these de"ciencies. It brings reactor design
formulation to the same level of sophistication as formu-
lations of other process operations. The methodology
enables us to formulate the design for any reactor con"g-
uration with any number of chemical reactions with any
stoichiometry, having any form of rate expression. Reac-
tor operations are described by dimensionless variables,
and the design is formulated in terms of the smallest
number of dimensionless design equations. The solutions
of these design equations provide dimensionless opera-
ting curves of the reactor (a new concept in chemical
reaction engineering) that completely describe the
reactor operation. These dimensionless operating curves
can be readily used to derive new economic-based opti-
mization tools for reactor operations. Furthermore,
the design formulation is constructed such that each
design equation has the least number of terms, resul-
ting in the most robust set of equations for numerical
solutions.
This paper (Part I) introduces the basic concepts of the
methodology and illustrates how they are applied to
formulate the design of ideal batch, plug-#ow and con-
tinuous stirred tank reactors operated isothermally. Part
II extends the analysis to non-isothermal operations and
to other reactor con"gurations, some for which design
equations are not available in the literature.
 U. Mann / Chemical Engineering Science 55 (2000) 991}1008
2. Analysis
The reactor design methodology described herein is
based on a new approach to reactor operations * reac-
tion-based design formulation instead of the conventional
species-based formulation. The new approach is based on
basic physical principles and known stoichiometric rela-
tions but applies them in a di!erent way. It exploits certain
stoichiometric relationships that have not been applied in
the context of reactor design formulation. The new design
methodology is founded on the following tenets:
f The core of reactor operations is the chemical reac-
tions that are taking place in the reactor; the species
balance equations serve merely as the means to de-
scribe the progress of the reactions. Therefore, the
reactor design should be formulated in terms of
quantities related to chemical reactions (e.g., reaction
extents) rather than quantities related to species (con-
version, concentration, etc.). An examination of the
structure of the design equations of rate processes
indicates that "nal design equations are expressed in
terms of quantities that a!ect the operation, not the
basic quantity used in formulating them. For example,
momentum balance equation is used to describe #uid
#ow systems but the design equation is expressed in
terms of #ow-related quantities (velocity, pressure,
etc.), not momentum. Energy balance equation is used
to describe heat-transfer operations but the design
equation is expressed in terms of temperature, not
energy. By using reaction-based quantities, we de-
scribe reactor operations more accurately and obtain
more an insight into the process.
f There are two `typesa of chemical reactions * inde-
pendent and dependent reactions. All the state
variables of the reactor (species compositions, temper-
ature, etc.) are determined by a set of independent
chemical reactions. (Independent reactions represent
a smallest set of stoichiometric relationships that de-
scribes the chemical transformations taking place in
the reactor, and, in principle, we may use `reactionsa
that do not actually take place in the reactor.) On the
other hand, the species formation rates depend on all
the chemical reactions that actually take place in the
reactor, including dependent reactions. The two reac-
tion `typesa are analogous to the two types of thermo-
dynamic quantities * those dependent only on the
`statea of the system (temperature, enthalpy, etc.) and
those dependent on the path of the process (work, heat,
etc.). For reacting systems, each species balance equa-
tion consists of two distinct constituent parts; one
related to the amount of the species in the reactor (or,
for #ow reactors, species #ow rate), thus depending
only on the independent reactions, and the other re-
lated to the species formation rates, thus depending on
all the chemical reactions.
993
f Since all the state variables of the reactor are deter-
mined by the extents of the independent reactions, the
reaction extent is the most suitable reaction-based
quantity to describe reactor operations. (The extent is
a measure of `unitsa of a chemical reaction that have
been transformed.) The reluctance to use the extent
might be because it is a calculated (not-measurable)
quantity. At "rst, it seems counter productive to use
calculated quantities rather than measurable quanti-
ties, but, by doing so we simplify the design formula-
tion * formulating the design by the smallest number
of design equations. This is analogous to the use of
calculated quantities in thermodynamics (enthalpy,
free energy, etc.) to obtain simpli"ed expressions.
f The operation of a chemical reactor is, basically, a rate
process that has a characteristic time constant. By
selecting a reaction-based time constant and a conve-
nient reference state (or, for #ow reactors, a reference
stream), the design equations are readily reduced to
dimensionless form. The resulting dimensionless de-
sign equations express the reactor operation on the
time scale of the chemical reactions.
f A careful selection of the reference state (or reference
stream) that serves as a scaling factor for all the design
calculations is essential. We also de"ne a reference
reaction rate, reference heat capacity, etc. that enable
us to formulate the design in terms of dimensionless
quantities and describe the reactor operations in terms
of dimensionless operating curves. Dimensionless de-
sign equations not only provide insight into the behav-
ior of the reactor but also simplify the calculations (no
need to select appropriate time increments for numer-
ical solution).
Based on these concepts, dimensionless, reaction-based,
design equations are derived, providing the most e$cient
and robust design formulation for chemical reactors.
The derivation of design equations for chemical reac-
tors with multiple reactions involves the application of
four fundamental concepts: stoichiometry, chemical ki-
netics, species balance equation (conservation of mass),
and energy balance equation ("rst law of thermo-
dynamics). To express the design equations in terms of
reaction-related quantities, some modi"cations to the
relationships commonly used in the formulation are
required. Below we review key de"nitions and discuss
relevant relationships used in the new reactor design
methodology. We then derive the design equations for
three ideal reactor con"gurations and discuss how they
are applied to obtain dimensionless operating curves that
describe the reactor operation.
To express the amount (or #ow rate) of a chemical
species, we adopt the stoichiometric methodology based
on reaction extent, widely used in the literature (see, for
example, Aris, 1969; Hill, 1977; Reklaitis, 1983; Baerns,
Hofmann & Renken, 1992; Mann, 1999). All stoichiometric
994 U. Mann / Chemical Engineering Science 55 (2000) 991}1008

Table 1
Stoichiometric relations

General relationships De"nition of stoichiometric coe$cients

aA#bBPcC#dD
s "!a, s "!b, s "c, s "d, (A)
A B C D
!--
D"+ s "c#d!a!b (B)
j
j
Mathematical condition for a balanced chemical reaction
!--
+ s MW "0 (C)
j j
j
Relationship between the kth-dependent reaction and the mth independent reaction
n*/$
+ a (s ) "(s ) (D)
km j m jk
m
Closed (batch) reactors Steady #ow reactors

De"nitions Extent of the ith chemical reaction Extent per time of the ith chemical reaction
(n (t)!n ) 1 d(n )
X (t), j j0 i Xs , ji (E)
i (s ) i (s ) dt
ji ji
Dimensionless extent of the ith reaction Dimensionless extent of the ith reaction
X (t) Xs
Z (t), i Z, i (F)
i (N ) i (F )
505 0 505 0
Conversion of reactant A Conversion of reactant A
N (0)!N (t) F !F
f (t), A A f , A0 A065 (G)
A N (0) A F
A A0
n*/$ n*/$
Stoichiometric relations for reactors N (t)"N (0)# + (s ) X (t) F "F # + (s ) Xs (H)
j j jm m j j0 jm m
with multiple reactions m m

n*/$ n*/$
N (t)"N (0)# + D X (t) F "(F ) # + D Xs (I)
505 505 m m 505 505 0 m m
m m

A B A B
n*/$ n*/$
N (t)"N (0) y (0)# + (s ) Z (t) F "(F ) y # + (s ) Z (J)
j 505 j jm m j 505 0 j0 jm m
m m

A B A B
n*/$ n*/$
N (t)"N (0) 1# + D Z (t) F "(F ) 1# + D Z (K)
505 505 m m 505 505 0 m m
m m
s s
Stoichiometric relations for reactors N (t)"N (0)# j (N (t)!N (0)) F "F # j (F !F ) (L)
j j s A A j j0 s A A0
with single reactions A A

s s s s
f (t)"! A X(t)"! A Z(t) f "! A Xs "! A Z (M)
A N (0) y (0) A F y
A A A0 A0

s s
N (t)"N (0)! j N (0) f (t) F "F ! j F f (N)
j j s A A j j0 s A0 A
A A

D D
N (t)"N (0)! N (0) f (t) F "(F ) ! F f (O)
505 505 s A A 505 505 0 s A0 A
A A
 U. Mann / Chemical Engineering Science 55 (2000) 991}1008 995

de"nitions and relationships used in reactor design tion rate of species j, (r ), relates to the rate of the chemical
j
formulation are provided in Table 1. Some important reactions by
features of these relationships deserve a special attention:
n!--
(r )" + (s ) r , (2)
f Reaction extent, de"ned by (E), indicates one `unita of j ji i
the chemical reaction and is expressed in mole extent. i/1
f Each chemical reaction has a characteristic parameter where r is the rate of the ith chemical reaction, expressed
i
D, de"ned by (B), indicating the net change in the in terms of moles extent per unit time per unit volume,
and (s ) is the stoichiometric coe$cient of species j in the
number of moles per mole extent. ji
f For multiple chemical reactions, the summations in ith chemical reaction. Note that the summation in Eq. (2)
stoichiometric relations (H)}(K) are over a set of inde- is over all the chemical reactions that take place in the
pendent reactions and not all the chemical reactions reactor.
taking place. The rate of each chemical reaction varies with the
f The relationship between dependent and independent temperature and species compositions according to
reactions, (D), plays an important role in the design the reaction rate expressions that, for most instances, are
formulation. It enables us to express stoichiometric product of the reaction rate constant, k(), and a func-
coe$cients of dependent reactions in terms of stoichio- tion of species compositions. To formulate the design
metric coe$cients of the independent reactions. Index equations in terms of dimensionless quantities, we ex-
m denotes the mth-independent reaction, index k press the reaction rate constants in terms of dimension-
denotes the kth-dependent reaction and a denotes less temperature, de"ned by
km
the scalar factor relating the kth-dependent reaction to
the mth-independent reaction (a is the multiplier of h, , (3)
km
0
the mth-independent reaction to obtain the kth-inde-
pendent reaction). To determine the numerical values where is a conveniently selected reference temperature
0
of a 's, we write (D) for each species and solve the (the temperature of the reference state or stream). We also
km
resulting set of linear equations. A more detailed dis- de"ne dimensionless activation energy of a chemical
cussion of this important but rarely used stoichiomet- reaction
ric relationship is provided elsewhere (Mann, 1999).
E
f To describe the reactor operation generically, we de- c, a , (4)
R
"ne the dimensionless extent of the mth independent 0
reaction, Z , by (F) in Table 1. For batch reactors, the which is a characteristic of the reaction and the reference
m
dimensionless extent at time t, Z (t) is de"ned by temperature. Using Eqs. (3) and (4), the Arrhenius equa-
m

A B
X (t) mol tion reduces to
Z (t), m , , (1a)
m (N ) mol k(h)"k( )ec(h~1)@h, (5)
505 0 0
where (N ) is the total number of moles of a conve- where k( ) is the reaction rate constant at the reference
505 0 0
niently selected reference state (usually, the initial temperature, . The dependency of the reaction rates on
state), and X (t) is the extent of the mth-independent 0
m species compositions will be discussed later.
reaction in time t. For #ow reactors, Z is de"ned by
m Chemical reactions with the same rate expression ("rst

A B
Xs mol/time order, second order, etc.) exhibit a similar behavior with
Z , m , , (1b)
m (F ) mol/time respect to species compositions; the di!erence between
505 0 fast and slow reactions is merely the time scale over
where (F ) is the total molar #ow rate of a conve-
505 0 which the reaction takes place. To derive dimensionless
niently selected reference stream, usually the inlet design equations, we de"ne a characteristic reaction time,
stream, and Xs is the extent per time of the mth-
m indicating the time scale of the reaction (second, minute,
independent reaction from the reference stream to the etc.). For volume-based rate expressions, we de"ne the
local point. The numerical values of Z 's depend on
m characteristic time of a chemical reaction by
the selection of the reference state (or stream) and the
stoichiometry of the chemical reactions. characteristic concentration C
t " " 0, (6)
f When a single chemical reaction takes place in the #3 characteristic reaction rate r
0
reactor, the conversion of reactant A, f , is propor-
A where both, the characteristic concentration, C , and the
tional to the extent of the reaction, expressed by (M) in 0
characteristic reaction rate, r , are conveniently selected.
Table 1. 0
To de"ne a characteristic reaction time that is indepen-
To express the design equations in terms of reaction- dent of the proportion of the reactants, it is convenient to
based quantities, we have to express species formation select the total concentration of the reference state (or
rates in terms of the individual reaction rates. The forma- stream) as the characteristic concentration. For batch
996 U. Mann / Chemical Engineering Science 55 (2000) 991}1008

reactors, it is de"ned by The stoichiometric coe$cient of species j in the kth-

dependent reaction, (s ) , relates to the stoichiometric
(N ) jk
C , 505 0, (7a) coe$cients of species j in the mth independent reactions,
0 < (0)
R (s ) , by (D) in Table 1. Substituting (D) into Eq. (11), we
jm
where < (0) is the initial volume of the reactor. For #ow obtain
R
reactors, the total reference concentration is de"ned by
A B
n*/$ dZ n*/$ n$%1 n*/$
(N ) + (s ) m" + (s ) r # + + a (s ) r < (t).
(F ) 505 0 j m dt jm m km j m k R
C , 505 0, (7b) m m k m
0 v (12)
0
where v is the volumetric #ow rate of the reference
0 Since all multipliers a are constants, we can switch the
stream. For the characteristic reaction rate in Eq. (6), it is km
order of the two summations of the second term in the
convenient to select a suitably de"ned rate, depending on parentheses and obtain,
the form of the rate expression. Since, in many instances,

A B
n*/$ dZ n*/$ n*/$ n$%1
the initial (or feed) composition is a parameter of the (N ) + (s ) m" + (s ) r # + (s ) + a r < (t).
operation, we select a reference reaction rate that is 505 0 j m dt jm m jm km k R
m m m k
independent of the composition of the reference state. (13)
For chemical reactions whose rate expressions are power
Since the coe$cients and summations of all the terms are
functions of the concentrations, it is convenient to de"ne
identical, Eq. (13) reduces to,
a characteristic reaction rate as the rate, at the reference

A B
temperature, if the concentration of each species is C . dZ n$%1 < (t)
0 m" r # + a r R . (14)
Hence, if the overall order of the reaction is n dt m km k (N )
(n"a#b#c), the characteristic reaction time is k 505 0
Eq. (14) is the reaction-based, di!erential design equation
C 1
t " 0 " , (8) of an ideal batch reactor, written for the mth-independent
#3 k( )Cn k( )Cn~1 reaction. To describe the operation of an ideal batch
0 0 0 0
where k( ) is the reaction rate constant at reference reactor with multiple reactions, we have to write Eq. (14)
0 for each of the independent reactions. Note that the
temperature, . Similar characteristic reaction times are
0 reaction-based design equation is invariant of the speci"c
readily de"ned for other forms of rate expressions (Mann,
1999). species used in the derivation.
To derive the design equation of an ideal (well-mixed) To reduce the design equation of an ideal batch reactor
batch reactor with multiple chemical reactions, we write to dimensionless form, we "rst use Eq. (7a) and substitute
(N ) "C < (0) into Eq. (14). Next, we de"ne the
a balance equation for species j over the reactor, 505 0 0 R
dimensionless operating time by
dN
j"(r )< (t), (9)
dt j R q,
operating time
" .
t
(15)
characteristic reaction time t
where < (t) is the volume of the reactor at time t. To #3
R
express the species balance equation in terms of the where t is the characteristic reaction time, de"ned by
#3
chemical reactions, we di!erentiate stoichiometric rela- Eq. (6). We di!erentiate Eq. (15), dt"t dq, and substi-
#3
tion (J) in Table 1, tute it into Eq. (14) to obtain
n*/$
A BA BA B
dN
j"(N ) + (s )
dZ
m. dZ n$%1 < (q) t
505 0 j m dt m" r # + a r R #3 . (16)
dt dq m km k < (0) C
m k R 0
Substituting this on the left-hand side of Eq. (9), and Eq. (16) is the general dimensionless, reaction-based de-
using Eq. (2) to express the formation rate of species j in sign equation of an ideal batch reactor, written for the
terms of the reaction rates, we obtain mth-independent reaction.
n*/$ dZ !-- For constant-volume batch reactors, < (t)"< (0),
R R
(N ) + (s ) m"+ (s ) < (t). (10)
505 0 j m dt ji R and Eq. (16) reduces to
m i

A BA B
Note that the summation on the left-hand side of Eq. (10) dZ n$%1 t
m" r # + a r #3 . (17)
is over independent reactions only, whereas the summa- dq m km k C
k 0
tion on the right-hand side is over all reactions. We write
the right-hand side of Eq. (10) as a sum of dependent Eq. (17) is the dimensionless, reaction-based di!erential
reactions and independent reactions, design equation of a constant-volume ideal batch reactor,
written for the mth-independent reaction. For gaseous,

A B
n*/$ dZ n*/$ n$%1 variable-volume batch reactors, < (t) varies during
(N ) + (s ) m" + (s ) r # + (s ) r < (t). (11) R
505 0 j m dt jm m jk k R the operation. Assuming ideal gas behavior, the reactor
m m k
 U. Mann / Chemical Engineering Science 55 (2000) 991}1008 997

volume at time t is We use stoichiometric relation (J) in Table 1 to express

the local molar #ow rate of species j, F , in terms of the
j
A BA BA B
< (t) N (t) (t) P(0)
R " 505 . (18) extents of the independent reactions,
< (0) N (0) (0) P(t)
R 505

A B
n*/$
Using stoichiometric relation (K) in Table 1 to express F "(F ) y # + (s ) Z , (25)
j 505 0 j0 jm m
the total number of moles in terms of the extents of the m
independent chemical reactions, Eq. (18) becomes where (F ) is the total molar #ow rate of the reference
505 0
stream. Di!erentiating Eq. (25),
A BA B
< (t) n*/$ P(0)
R " 1# + D Z h , (19)
< (0) m m P(t)
R m n*/$
dF "(F ) + (s ) dZ
where h is the dimensionless temperature, de"ned by Eq. j 505 0 jm m
m
(3). Substituting Eq. (19) into Eq. (16), the dimensionless
design equation for isobaric operations is and substitute this and Eq. (2) into Eq. (24), we obtain

n*/$ dZ n!--
A BA BA B
dZ n$%1 t n*/$ (F ) + (s ) m"+ (s ) r . (26)
m" r # + a r #3 1# + D Z h . (20) 505 0 j m d< ji i
dq m mk k C m m m R i
k 0 m
Eq. (20) is the dimensionless, reaction-based, di!erential Note that here too, the summation on the left-hand side
design equation of an isobaric, gas-phase, ideal batch is over the independent reactions only, whereas the sum-
reactor, written for the mth-independent reaction. mation on the right-hand side is over all the reactions. As
For an ideal batch reactor with a single chemical in the case of the ideal batch reactor, we write the sum-
reaction, Eq. (16) reduces to mation on the right as summations over dependent
reactions and independent reactions, express the stoichio-

A BA B
dZ < (q) t metric coe$cient of species j in the kth-dependent
"r R #3 . (21) reaction, (s ) , in terms of the stoichiometric coe$cients
dq < (0) C jk
R 0 of species j in the mth independent reactions, (s ) , using
jm
For a single chemical reaction, the extent of the reaction (D) in Table 1, and then switch the order of the summa-
is proportional to the conversion of reactant A, f , given tions to obtain
A
by (M) of Table 1. We di!erentiate (M) and obtain

A B
dZ 1 n$%1
dZ y (0) df m" r #+ a r . (27)
"! A A, (22) d< (F ) m km k
dt s dt R 505 0 k
A
Eq. (27) is the reaction-based, di!erential design equation
where y (0)"N (0)/(N ) is the mole fraction of reac- for steady #ow reactors, written for the mth-independent
A A 505 0
tant A in the reference state. Using Eq. (2), the depletion reaction. To describe the operation of the reactor with
rate of reactant A, (!r ), relates to the reaction rate by multiple reactions, we have to write Eq. (27) for each of
A
(!r )"!s r, and from Eq. (15), dt"t dq. Substitu- the independent reactions.
A A #3
ting these into Eq. (21), we obtain To reduce design equation (27) to a dimensionless
form, we "rst use Eq. (7b) and substitute (F ) "v C
N (0) 505 0 0 0
dt" A df . (23) into Eq. (27). Next, we de"ne the dimensionless reactor
(!r )< (t) A
A R space time,
This is the conventional di!erential design equation of an
reactor space time <
ideal batch reactor with a single chemical reaction, ex- q, " R , (28)
characteristic reaction time v t
pressed in terms of the conversion of reactant A. 0 #3
To derive the design equation for steady #ow reactors
where < is the reactor volume, v is the volumetric #ow
with multiple chemical reactions, we consider a dif- R 0
rate of the reference stream and t is the characteristic
ferential #ow reactor, d< , with a single inlet and a #3
R reaction time de"ned by Eq. (6). Di!erentiating Eq. (28),
single outlet. We write a species balance equation for
d< "v t dq and substituting it in Eq. (27), the design
species j, over the reactor, R 0 #3
equation becomes

A BA B
dZ n$%1 t
m" r # + a r #3 . (29)
dq m km k C
k 0
Eq. (29) is the dimensionless, reaction-based di!erential
dF "(r ) d< . (24) design equation of steady #ow reactors, written for the
j j R
998 U. Mann / Chemical Engineering Science 55 (2000) 991}1008

mth-independent reaction. It is also the di!erential design
equation of plug-#ow reactors.
For steady #ow reactors with a single chemical reac-
tion, Eq. (29) reduces to
This is the conventional design equation of a CSTR with
a single chemical reaction, expressed in terms of the
conversion of reactant A.
To understand the structure of the dimensionless,
reaction-based design equations, recall the de"nition

A B
dZ t of the characteristic reaction time, de"ned by Eq. (6),
"r #3 . (30) t "C /r . It follows that the scaling factor is
dq C #3 0 0
0 (t /C )"1/r , where r is the reference rate of a selected
#3 0 0 0
For a single chemical reaction, the extent of the reaction chemical reaction. Substituting this relation into Eq. (29),
is proportional to the conversion of reactant A, f , given the dimensionless design equation of a plug-#ow reactor
A becomes
by (M) in Table 1. We di!erentiate (M) and obtain

AB AB
y dZ r n$%1 r
dZ"! A0 df , (31) m" m # + a k . (35)
s A dq r km r
A 0 k 0
where y "F /(F ) is the mole fraction of reactant The physical meaning of Eq. (35) is that the dimension-
A0 A0 505 0
A in the reference stream. Using Eq. (2), the depletion rate less, reaction-based design equations are expressed in
of reactant A, (!r ), relates to the reaction rate by terms of relative reaction rates (r /r )'s and (r /r )'s. They
A m 0 k 0
(!r )"!s r, and from Eq. (28), d< "v t dq. Sub- provide the dimensionless extents of the independent
A A R 0 #3
stituting these into Eq. (30), we obtain reactions as functions of the dimensionless space time (or
dimensionless operating time) where the latter is de"ned
F on a basis of the reference reaction rate.
d< " A0 df . (32)
R (!r ) A
A
This is the conventional di!erential design equation of
3. Application
a plug-#ow reactor with a single chemical reaction, ex-
pressed in terms of the conversion of reactant A.
The dimensionless, reaction-based, design equations
For steady, continuous stirred-tank reactors (CSTRs),
(16), (29) and (34) are written for the mth-independent
the reaction rates are uniform throughout the reactor
reaction and, as indicated, to design a chemical reactor
volume (independent of q) and are the rates at the outlet
with multiple reactions we have to write them for each
conditions, r and r . We separate the variables and
.065 ,065 independent chemical reaction. Since we can select di!er-
integrate Eq. (29) to obtain
ent sets of independent reactions, the question is what is
the most appropriate set of independent reactions for the

A BA B
n$%1 t
Z !Z " r # + a r q #3 , (33) design formulation. Since the design equations include
.065 .*/ .065 km ,065 C
k 0 the rates of all chemical reactions that take place in the
reactor but are expressed in terms of extents of indepen-
where Z and Z are, respectively, the dimensionless
.*/ .065 dent reactions, by selecting a set of independent reactions
extents of the mth-independent reaction between the ref- among these reactions, we minimize the number of terms
erence stream and the reactor inlet and outlet. Eq. (33) is in each design equation. Hence, we adopt the following
the dimensionless, reaction-based, design equation of heuristic rule:
a CSTR, written for the mth-independent reaction. select a set of independent reactions among the chemical
For a CSTR with a single chemical reaction, Eq. (33) reactions whose rate expressions are provided.
reduces to The heuristic rule may be stated di!erently:
do not select a set of independent reactions that includes

A B
t
Z !Z "r q #3 . (34) a chemical reaction whose rate expression is not provided.
065 */ 065 C By adopting this heuristic rule, we formulate the design
0
in terms of the least number of rate expressions in the
We use (M) of Table 1 to express the dimensionless extent design equations; hence by the most robust set of alge-
in terms of the conversion of reactant A, and Eq. (2) to braic or di!erential equations for numerical solutions.
express the rate of depletion of reactant A, (!r ), in Reaction-based design equations (16), (29) and (34) are
A
terms of the reaction rate, (!r )"!s r. Substituting not expressed in useful forms. To solve them, we have to
A A
these into Eq. (31) and using Eq. (28), we obtain express the rates of the chemical reactions in terms of the
dimensionless extents of the independent reactions. Since
< f !f the reaction rates depend on the temperature and species
R " A065 A*/.
F (!r ) concentrations, we have to derive relationships between
A0 A 065
 U. Mann / Chemical Engineering Science 55 (2000) 991}1008 999

the species concentrations and the extents of the indepen- Eq. (19) and the concentration of species j for isobaric
dent reactions. operations is
For steady #ow reactors, the local concentration of
species j is C "F /v, where F and v are the local molar y (0)#+n*/$(s ) Z (t)
j j j C (t)"C j m jm m , (43)
#ow rate of species j and volumetric #ow rate, respec- j 0 (1#+n*/$ D Z (t))h
tively. To express the local molar #ow rate of species m m m
j in terms of the dimensionless extents, we use stoichio- We can now substitute the concentration relations into
metric relation (J) in Table 1, the rate expressions and the latter into the design equa-
tions. For ideal batch and plug-#ow reactors, the design

A B
F (F ) n*/$
C " j" 505 0 y # + (s ) Z , (36) formulation results in a set of non-linear, "rst-order,
j v v j0 jm m di!erential equations of the form
m
For liquid-phase reactions, the volumetric #ow rate is dZ 1
m "G (q, Z , Z ,2, Z , h),
assumed constant, v+v , and Eq. (36) reduces to
0 dq 1 m1 m2 n*/$
dm
q"G (q, Z , Z ,2, Z , h),
A B
n*/$ (44)
C "C y # + (s ) Z , (37) dq 2 m1 m2 n*/$
j 0 j0 jm m .
m
F
where C is the concentration of the reference stream,
0 dZ */$
de"ned by Eq. (7b). For gas-phase reactions, assuming n "G (q, Z , Z ,2, Z , h)
ideal gas behavior, the local volumetric #ow rate is dq n*/$ m1 m2 n*/$

A BA BA B
F P We have here a set of n equations with n #1 depen-
v"v 505

0 . (38) */$ */$
0 (F ) P dent variables. The additional equation is derived from
505 0 0 the energy balance equation (see Part II) and reduces to
Using stoichiometric relation (K) in Table 1, Eq. (38) the form
becomes
dh
"G */$ (q, Z 1, Z 2,2, Z */$, h). (45)

A BA B
n*/$ P dq n `1 m m n
v"v 1# + D Z h 0 , (39)
0 m m P
m We solve these equations for Z 1,2, Z */$, h as functions
m n
where h is the dimensionless temperature de"ned by of q, subject to the initial condition that at q"0, the
Eq. (3). Substituting Eq. (39) into Eq. (36), for isobaric, dimensionless extents and the dimensionless temperature
gas-phase reactions, the concentration of species j is are speci"ed. For isothermal operations, Eq. (45) reduces
to dh/dq"0; hence, only the design equations should be
y #+n*/$(s ) Z solved. For steady ideal stirred-tank reactors, the design
C "C j0 m jm m, (40)
j 0 (1#+n*/$ D Z )h formulation reduces to a set of non-linear, homogeneous,
m m m algebraic equations of the form
For ideal batch reactors, the concentration of species
j in the reactor at operating time t is C (t)"N (t)/< (t). G (q, Z 1, Z 2,2, Z */$, h)"0,
j j R 1 m m n
To express the moles of species j in the reactor at time t in G (q, Z 1, Z 2,2, Z */$, h)"0,
terms of the reaction extents, we use stoichiometric rela- 2 m m n (46)
tion (J) in Table 1, hence, F
G */$(q, Z 1, Z 2,2, Z */$, h)"0
n m m n
A B
N (0) n*/$
C (t)" 505 y (0)# + (s ) Z (t) , (41)
j < (t) j jm m and the energy balance equation reduces to the form
R m
For constant-volume batch reactors, < (t)"< (0), and G */$ (q, Z 1, Z 2,2, Z */$, h)"0. (47)
R R n `1 m m n
Eq. (41) reduces to
We solve these equations for Z 1,2, Z */$, h for di!erent
m n
A B
n*/$ values of q.
C (t)"C y (0)# + (s ) Z (t) , (42)
j 0 j jm m Table 2 provides the dimensionless design equations of
m the three ideal reactor con"gurations as well as key
where C is the concentration of the reference state, de"nitions and relationships for species concentrations.
0
de"ned by Eq. (7a). For gaseous, variable-volume batch Usually, the design equations are solved numerically,
reactors, and assuming ideal-gas behavior, we use but, for simple cases, we can obtain analytical solutions.
1000 U. Mann / Chemical Engineering Science 55 (2000) 991}1008

Table 2
Dimensionless design equations for ideal reactors with multiple chemical reactions

Batch reactor Plug-#ow reactor CSTR

Design equation For constant-volume reactor General design equation General design equation
for the mth independent

A BA B A BA B A BA B
dZ n$%1 t dZ n$%1 t n$%1 t
reaction m" r # + a r #3 m" r # + a r #3 Z !Z " r # + a r q #3
dq m km k C dq m km k C .065 .*/ m km k C
k 0 k 0 k 0

For variable-volume, isobaric, gas reactor

A BA BA B
dZ n$%1 t n*/$
m" r # + a r #3 1# + D Z h
dq m mk k C m m
k 0 m
Species concentrations Concentration in constant-volume reactor Concentration for liquid-phase reactions

A B A B
n*/$ n*/$
C (q)"C y (0)#+ (s ) Z (q) C "C y #+ (s ) Z
j 0 j jm m j 0 j0 jm m
m m
Concentration in variable-volume Concentration for gas-phase reactions
gaseous reactor
y (0)#+n*/$(s ) Z (t) y #+n*/$(s ) Z
C (q)" C j m jm m C "C j0 m jm m
j 0 (1#+n*/$D Z (q))h j 0 (1#+n*/$D Z )h
m m m m m m
De"nitions Dimensionless operating time Dimensionless space time
t t <
q, q, 41" R
t t v t
#3 #3 0 #3
Dimensionless extent Dimensionless extent
X (q) Xs
Z (q), m Z , m
m (N ) m (F )
505 0 505 0
Reference concentration Reference concentration
(N ) (F )
C , 505 0 C , 505 0
0 < (0) 0 v
R 0
Reference species composition Reference species composition
N (0) F
y (0), j y , j0
j (N ) j0 (F )
505 0 505 0

Note that the structures of the dimensionless design
equations (16), (29) and (34) are convenient for numerical
solutions, since we can solve them numerically without
substituting the rate expressions explicitly. The species
concentrations and the reaction rates of the chemical
reactions can be calculated separately (in subroutines)
and then their numerical values used to solve the design
equations.
4. Results
The solutions of the design equations and the energy
balance equation (Z 's and h as functions of q) describe
m
the generic reactor operation and provide complete in-
formation on the reactor operation without considering
its size. The plots of Z 's versus q are the dimensionless
m
reaction operating curves, indicating the progress of
the independent chemical reactions at each stage of the
reactor operation. Since di!erent sets of independent
reactions can be used in the formulation, the reaction
operating curves do not have any physical signi"cance,
per se. However, they are very useful in calculating the
species operating curves as well as a tool in optimization
of the reactor operations. Note that, in principle, the
values of the extents of an independent reaction may
be negative. This occurs when a reaction proceeds in the
opposite direction of the chemical reaction selected as an
 U. Mann / Chemical Engineering Science 55 (2000) 991}1008
independent reaction (see Example 2 below) or due de-
pendent reactions (see Example 1 below). Once Z 's as
m
functions of s are known, we use stoichiometric relation
(J) in Table 1 to calculate F /(F ) (or N (q)/(N ) ) as
j 505 0 j 505 0
a function of q for each species * the dimensionless
species molar #ow rates (or contents). The plots of
F /(F ) versus q are the dimensionless species opera-
j 505 0
ting curves of the reactor, indicating the species com-
positions at each stage of the reactor operation. They
are very useful in determining operating conditions
required to maximize the production of a desirable prod-
uct or to minimize the production of undesirable prod-
ucts. The plot of h versus q is the dimensionless
temperature operating curve of the chemical reactor,
indicating the temperature at each stage of the reactor
operation.
Sizing of chemical reactors (or, for batch reactors,
determining the operating time) is reduced to selecting
a point (given value of q) on the dimensionless operating
curves. Once q is known, we can readily determine the
reactor volume (or operating time), using Eq. (28) or
Eq. (15), the given value of the characteristic reaction time
and the speci"ed #ow rate of the reference stream. This is
analogous to calculating a pipe diameter in a #ow system
when the Reynolds number is known and the #uid prop-
erties are speci"ed.
The procedure for designing chemical reactors with
multiple reactions goes as follows:
1. Identify all the chemical reactions taking place in the
reactor and de"ne the stoichiometric coe$cients of
each species in each reaction.
2. Determine the number of independent chemical
reactions.
3. Select a set of independent reactions among the reac-
tions whose rate expressions are given.
4. For each dependent reaction, determine its a multi-
km
pliers with each of the independent reactions using
(D) in Table 1.
5. Select a reference state (or stream) and determine
, C , (N ) or (F ) , and the reference species
0 0 505 0 505 0
compositions, y (0)'s or y 's.
j j0
6. Write the appropriate design equation for each inde-
pendent chemical reaction.
7. Select a leading (or desirable) reaction and determine
the characteristic reaction time, t .
#3
8. Express the reaction rates in terms of the dimension-
less extents of the independent reactions, Z 's, and
m at the reactor exit.
the dimensionless temperature, h, using the appropri-
ate concentration expression.
9. Solve the design equations for Z 's and h as functions
m 1
of the dimensionless space time (or operating time), q,
and obtain the dimensionless reaction and temper-
ature operating curves.
10. Calculate the dimensionless species operating curves,
using stoichiometric relation (J) in Table 1.
1001
11. Determine the reactor volume or operating time
from the desirable of speci"ed value of q.
The two examples below illustrate the new reactor
design formulation and how it is applied. Note that
the conventional (species-based) design formulation of
Example 1 involves six design equations with a total of 15
terms whereas here we formulate the design in terms of
three design equations with a total of "ve terms. The
conventional formulation of Example 2 involves four
design equations with a total of 16 terms whereas here we
formulate the design in terms of three design equations
with a total of six terms. The robustness of the new design
formulation can be readily illustrated by taking the rate
constants of Reactions 3}6 in Example 2 to be six orders
of magnitude higher than the given values. The reaction-
based formulation provides accurate solution, whereas
the species-based formulation does not. Example 2
also illustrates that the new methodology is general,
independent of the inlet composition, and that it is not
necessary to know a priori the direction of the chemical
reactions.
Example 1
We want to compare the operation of an isothermal
plug-#ow reactor to that of a CSTR with the following
gaseous chemical reactions:
4NH #5O P4NO#6H O, r "k C 3C2 2,
3 2 2 1 1 NH O
4NH #3O P2N #6H O, r "k C 3C 2,
3 2 2 2 2 2 NH O
2NO#O P2NO , r "k C 2C2 ,
2 2 3 3 O NO
4NH #6NOP5N #6H O, r "k C2@33C .
3 2 2 4 4 NH NO
The desired product is NO. A stream consisting of
50% NH and 50% O (mol%) at 609 K and 2 atm is fed
3 2
into the reactor at a rate of 24 l/min. Based on the data
below,
(a) derive the design equations and plot the operating
curves of the plug-#ow reactor,
(b) determine the volume of the plug-#ow reactor for
optimal production of NO; what is the #ow rate of
each species at the reactor exit,
(c) derive the design equations and plot the operating
curves of the CSTR, and
(d) determine the volume of the CSTR for optimal pro-
duction of NO; what is the #ow rate of each species
Data: At 609 K k "20 l2 mol~2 min~1, k "0.08
2
l mol~1 min~1, k "40 l2 mol~2 min~1, k "0.0547
3 4
l2@3 mol~2@3 min~1.
Solution: First, we determine the number of indepen-
dent reactions and select a set. We construct a matrix of
1002 U. Mann / Chemical Engineering Science 55 (2000) 991}1008

stoichiometric coe$cients for the given reactions. and obtain a "2.5. We write (D) of Table 1 for NH ,
42 3
a (!4)#a (!4)#a (0)"!4 (e)
NH O NO H O N NO 41 42 43
3 2 2 2 2
Reaction 1 !4 !5 4 6 0 0 and obtain a "!1.5. Hence,
41
Reaction 2 !4 !3 0 6 2 0 . (a)
Reaction 4"!1.5 Reaction 1#2.5 Reaction 2.
Reaction 3 0 !1 !2 0 0 2
Reaction 4 !4 0 !6 6 5 0 (a) To design a plug-#ow reactor, we write the dimen-
sionless design equation of plug-#ow reactors, (29), for
each of the independent chemical reactions,
Performing Gaussian elimination, matrix (a) reduces to

A B
dZ t
1"(r !1.5r ) #3 , (f )
NH O NO H O N NO ds 1 4 C
3 2 2 2 2 0
!4 !5 4 6 0 0

A B
dZ t
0 1 !2 0 1 0 . (b) 2"(r #2.5r ) #3 , (g)
dq 2 4 C
0
0 0 !4 0 1 2

A B
dZ t
0 0 0 0 0 0 3"r #3 . (h)
dq 3 C
0
Since there are three non-zero rows in reduced matrix (b), We select the inlet stream as the reference stream and,
there are three independent reactions. The non-zero rows using stoichiometric relation (J) of Table 1, express the
in matrix (b) represent a set of independent reactions, molar #ow rate of each species at any point in the reactor
in terms of Z , Z , and Z ,
1 2 3
4NH #5O P4NO#6H O,
3 2 2 F 3"(F ) (y 3 !4Z !4Z ), (i)
2NOPO #N , NH 505 0 NH 0 1 2
2 2
4NOPN #2NO . F 2"(F ) (y 2 !5Z !3Z !Z ), ( j)
2 2 O 505 0 O 0 1 2 3
F "(F ) (y #4Z !2Z ), (k)
However, applying the heuristic rule of selecting a set of NO 505 0 NO0 1 3
independent reactions whose rate expressions are known, F 2 "(F ) (y 2 #6Z #6Z ), (l)
we select a set of three independent reactions from the HO 505 0 H O0 1 2
given chemical reactions. Reactions 1}3, represent such F 2"(F ) (y 2 #2Z ), (m)
N 505 0 N 0 2
a set, hence, m"1, 2, 3, k"4, and we express the design
equations in terms of Z , Z and Z . The stoichiometric F 2"(F ) (y 2 #2Z ), (n)
1 2 3 NO 505 0 NO 0 3
coe$cients of the independent reactions are
Using (K) of Table 1, the total molar #ow rate at any
point in the reactor is
(s 3) "!4, (s 2) "!5, (s ) "4,
NH 1 O 1 NO 1
(s 2 ) "6, (s 2) "0, (s 2) "0, D "1, F "(F ) (1#Z #Z !Z ).
505 505 0 1 2 3
(o)
HO1 N 1 NO 1 1
(s 3) "!4, (s 2) "!3, (s ) "0,
NH 2 O 2 NO 2 For gas-phase reactions, we express the species concen-
(s 2 ) "6, (s 2) "2, (s 2) "0, D "1, trations by Eq. (40), and the rates of the four chemical
HO2 N 2 NO 2 2
(s 3) "0, (s 2) "!1, (s ) "!2, reactions, expressed in terms of dimensionless extents,
NH 3 O 3 NO 3 are
(s 2 ) "0, (s 2) "0, (s 2) "2, D "!1.
HO3 N 3 NO 3 3
r "
1
To determine the multipliers a 's of the dependent reac-
km
A BA B
y !4Z !4Z y 2 !5Z !3Z !Z 2
tion (Reaction 4) and the three independent reactions, we k C3 NH30 1 2 O0 1 2 3 ,
write (D) of Table 1 for NO , 1 0 1#Z #Z !Z 1#Z #Z !Z
2 1 2 3 1 2 3
(p)
a (0)#a (0)#a (2)"0 (c)
41 42 43 r "
2
and obtain a "0. We write (D) of Table 1 for N ,
A BA B
y !4Z !4Z y 2 !5Z !3Z !Z
43 2 k C2 NH30 1 2 O0 1 2 3 ,
2 0 1#Z #Z !Z 1#Z #Z !Z
1 2 3 1 2 3
a (0)#a (2)#a (0)"5, (d) (q)
41 42 43
 U. Mann / Chemical Engineering Science 55 (2000) 991}1008 1003

r "
3

A BA B
y 2 !5Z !3Z !Z y #4Z !2Z 2
k C3 O0 1 2 3 NO0 1 3 ,
3 0 1#Z #Z !Z 1#Z #Z !Z
1 2 3 1 2 3
(r)
r "
4

A B A B
y !4Z !4Z 2@3 y #4Z !2Z
k C5@3 NH30 1 2 NO0 1 3 ,
4 0 1#Z #Z !Z 1#Z #Z !Z
1 2 3 1 2 3
(s)
We select Reaction 1, the leading reaction, as the refer- Fig. 1. Reaction operating curves of plug-#ow reactor for Example 1.
ence reaction and, using Eq. (8), the characteristic reac-
tion time is
C 1
t " 0 " . (t)
#3 k C3 k C2
1 0 1 0
Substituting Eqs. (p)}(s) and Eq. (t) into Eqs. (f ), (g) and
(h), the design equations reduce to
dZ (y !4Z !4Z )(y 2 !5Z !3Z !Z )2
1" NH30 1 2 O0 1 2 3
dq (1#Z #Z !Z )3
1 2 3

A B
k (y 3 !4Z !4Z )2@3(y #4Z !2Z )
!1.5 4 NH 0 1 2 NO0 1 3,
k C4@3 (1#Z #Z !Z )5@3
1 0 1 2 3
(u)
dZ
2" Fig. 2. Species operating curves of plug-#ow reactor for Example 1.
dq

A B
k (y 3 !4Z !4Z )(y 2 !5Z !3Z !Z )
2 NH 0 1 2 O0 1 2 3 Using Eq. (t), the numerical value of the characteristic
k C (1#Z #Z !Z )2
1 0 1 2 3 reaction time constant is

A B
k (y 3 !4Z !4Z )2@3(y #4Z !2Z )
#2.5 4 NH 0 1 2 NO0 1 3 , 1 1
k C4@3 (1#Z #Z !Z )5@3 t " " "31.25 min.
1 0 1 2 3 #3 k C2 (20)(0.04)2
(v) 1 0
The parameters of the dimensionless design equations
dZ
3" are
dq

A B AB A B
k k k
2 "0.1, 3 "2, 4 "0.2.
AB
k (y 2 !5Z !3Z !Z )(y #4Z !2Z )2
3 O0 1 2 3 NO0 1 3 . k C k k C4@3
k (1#Z #Z !Z )3 1 0 1 1 0
1 1 2 3
(w) We substitute these values into Eqs. (u)}(w), and solve
them numerically for Z , Z , and Z , subject to the initial
For the given feed, y 3 "0.5, y 2 "0.5, y " 1 2 3
NH 0 O0 NO0 conditions that at q"0, Z "Z "Z "0, using
y 2 "y 2 "y 2 "0 and the reference concentra- 1 2 3
H O0 N0 NO 0 a mathematical software such as Mathcad, Matlab, HiQ,
tion is etc. Based on the solutions of Z , Z , and Z , we use Eqs.
1 2 3
P (2 atm) (i)}(o) to calculate the dimensionless species molar #ow
C "
0 R
" rates as functions of q. Fig. 1 shows the reaction opera-
(0.08205 l atm/mol K)(609 K)
0 ting curves and Fig. 2 shows the species operating curves
"0.04 mol/l. of the plug-#ow reactor.
(b) From Fig. 2 (or the table of calculated data), opti-
The total molar #ow rate of the reference stream is mal production of NO is achieved at q"0.96 and at that
time Z "0.0295, Z "0.0296 and Z "0.0043. Substi-
(F ) "v C "(24 l/min)(0.04 mol/l)
505 0 0 0 1 2 3
tuting these values into Eqs. (i)}(o), the molar #ow rates
"0.961 mol/min. of the species in the outlet stream are: F 3 "
NH 065
1004 U. Mann / Chemical Engineering Science 55 (2000) 991}1008

0.254, F 2 "0.249, F "0.105, F 2 "0.340, Example 2

O 065 NO065 H O065
F 2 "0.0568, F 2 "0.0082 and (F ) "1.013 The following reversible chemical reactions represent
N 065 NO 065 505 065
mol/min. Using the de"nition of the dimensionless space gas-phase cracking of hydrocarbons:
time, Eqs. (28) and (p), the required reactor volume is
A 2B r "k C , r "k C2,
1 1 A 2 2 B
< "qv t "(0.96) (24 l/min) (31.25 min)"720 l. A#B C r "k C C , r "k C ,
R 0 #3 3 3 A B 4 4 C
(c) To design the CSTR, we write the dimensionless A#C D r "k C C , r "k C .
5 5 A C 6 6 D
design equation of CSTRs, (34), for each of the indepen-
Species B is the desired product. We want to design an
dent reactions,
isothermal, isobaric tubular reactor (PFR) to be operated

A B
t at 4893C and 5 atm. A stream of pure A is fed into the
Z !Z "(r !1.5r )q #3 , (x) reactor at a rate of 1 mol/s. Based on the data below,
1065 1*/ 1065 4065 C
0
(a) derive the design equations and plot the operating
A B
t
Z !Z "(r #2.5r )q #3 , (y) curves of the independent reactions,
2065 2*/ 2065 4065 C
0 (b) plot the species operating curves,

A B
t (c) determine the volume of the reactor needed for opti-
Z !Z "r q #3 . (z) mal production of B; what is the production rate of
3065 3*/ 3065 C
0 each species, and
Since the inlet stream is also the reference stream, (d) determine the mole fractions of the species at equilib-
Z "Z "Z "0. Substituting Eqs. (p)}(t) and the rium (q"R).
1*/ 2*/ 3*/
reference compositions into Eqs. (x)}(z), the design equa- (e) Repeat parts a, b, and d for a feed stream that
tions reduce to consists only of species D.

A B
(0.5!4Z !4Z )(0.5!5Z !3Z !Z )2
Z ! 1065 2065 1065 2065 3065 q
1065 (1#Z #Z !Z )3
1065 2065 3065

A BA B
k (0.5!4Z !4Z )2@3(4Z !2Z )
#1.5 4 1065 2065 1065 3065 q"0, (aa)
k C4@3 (1#Z #Z !Z )5@3
1 0 1065 2065 3065

A BA B
k (0.5!4Z !4Z )(0.5!5Z !3Z !Z )
Z ! 2 1065 2065 1065 2065 3065 q
2065 k C (1#Z #Z !Z )2
1 0 1065 2065 3065

A BA B
k (0.5!4Z !4Z )2@3(4Z !2Z )
!2.5 4 1065 2065 1065 3065 q"0, (bb)
k C4@3 (1#Z #Z !Z )5@3
1 0 1065 2065 3065

A BA B
k (0.5!5Z !3Z !Z )(4Z !2Z )2
Z ! 3 1065 2065 3065 1065 3065 q"0. (cc)
3065 k (1#Z #Z !Z )3
1 1065 2065 3065

We solve these equations numerically for di!erent values Data: At 4893C, k "2 min~1, k "20 l mol~1 min~1,
1 2
of q using a mathematical software. Based on the solu- k "50 l mol~1 min~1, k "0.8 min~1, k "125 l mol~1
3 4 5
tions, we use (i)}(o) to calculate the dimensionless molar min~1 and k "2 min~1.
6
#ow rates of the individual species as a function of q. Solution: First, we determine the number of indepen-
Fig. 3 shows the reaction operating curves and Fig. 4 dent reactions and select a set of independent reactions.
shows the species operating curves of the CSTR. We represent the given chemical reactions by the follow-
(d) From Fig. 4 (or the table of calculated data), opti- ing six reactions:
mal production of NO is achieved at q"1.04 and at that
Reaction 1: AP2B,
time Z "0.0198, Z "0.0261 and Z "0.00312. Sub-
1 2 3 Reaction 2: 2BPA,
stituting these values into Eqs. (e)}(i), the molar #ow
rates of the species in the outlet stream are: Reaction 3: A#BPC,
F 3 "0.304, F 2 "0.307, F "0.0701, F 2
NH 065 O 065 NO065 H O065 Reaction 4: CPA#B,
"0.265, F 2 "0.0501, F 2 "0.0060 and (F )
N 065 NO 065 505 065 Reaction 5: A#CPD,
"1.002 mol/min. Using the de"nition of the dimension-
less space time, Eqs. (28) and (p), the required reactor Reaction 6: DPA#C.
volume is
We can construct the matrix of stoichiometric coe$-
< "qv t "(1.04) (24 l/min) (31.25 min)"780 l. cients and reduce it to a diagonal form to determine the
R 0 #3
 U. Mann / Chemical Engineering Science 55 (2000) 991}1008 1005

are

a "!1, a "0, a "0,

21 23 25
a "0, a "!1, a "0, (a)
41 43 45
a "0, a "0, a "!1.
61 63 65
(a) We write the dimensionless design equation of
plug-#ow reactors, (29), for each of the independent reac-
tions,

A B
dZ t
1"(r !r ) #3 , (b)
dq 1 2 C
0

A B
Fig. 3. Reaction operating curves of CSTR for Example 1. dZ t
3"(r !r ) #3 , (c)
dq 3 4 C
0

A B
dZ t
5"(r !r ) #3 . (d)
dq 5 6 C
0
We select the inlet stream as the reference stream and,
using stoichiometric relation (J) of Table 1, we express the
molar #ow rate of each species at any point in the reactor
in terms of Z , Z , and Z ,
1 3 5
F "(F ) (y !Z !Z !Z ), (e)
A 505 0 A0 1 3 5
F "(F ) (y #2Z !Z ), (f )
B 505 0 B0 1 3
F "(F ) (y #Z !Z ), (g)
C 505 0 C0 3 5
F "(F ) (y #Z ). (h)
D 505 0 D0 5
Fig. 4. Species operating curves of CSTR for Example 1.
Using (K) of Table 1, the total molar #ow rate at any
point in the reactor is

F "(F ) (1#Z !Z !Z ). (i)

505 505 0 1 3 5
number of independent reactions. However, in this case
we have three reversible reactions, and since each of the For gas-phase reactions, we express the species concen-
three forward reactions has a species that does not ap- trations by Eq. (40), and the rates of the six chemical
pear in the other two, we have three independent reac- reactions are
tions and three dependent reactions. We select the three
y !Z !Z !Z
forward reactions as the set of independent reactions. r "k C A0 1 3 5, (j)
Hence, the indices of the independent reactions are 1 1 0 1#Z !Z !Z
1 3 5
m"1, 3, 5, and we describe the reactor operation in

A B
y #2Z !Z 2
terms of their dimensionless extents, Z , Z , and Z . The r "k C2 B0 1 3 , (k)
1 3 5 2 2 0 1#Z !Z !Z
indices of the dependent reactions are k"2, 4, 6. The 1 3 5
stoichiometric coe$cients of the three independent reac-
(y !Z !Z !Z )(y #2Z !Z )
tions are r "k C2 A0 1 3 5 B0 1 3 , (l)
3 3 0 (1#Z !Z !Z )2
1 3 5
y #Z !Z
s 1"!1, s 1"2, s 1"0, s 1"0, D "1, r "k C C0 3 5 , (m)
A B C D 1 4 4 0 1#Z !Z !Z
s 3"!1, s 3"!1, s 3"1, s 3"0, D "!1, 1 3 5
A B C D 3
s 5"!1, s 5"0, s 5"!1, s 5"1, D "!1, (y !Z !Z !Z )(y #Z !Z )
A0 1 3 5 C0 3 5 ,
A B C D 5 r "k C2
5 5 0
(n)
(1#Z !Z !Z )2
1 3 5
We use (D) of Table 1 to determine the a multi- y #Z
D0 5
km r "k C
6 6 0 1#Z !Z !Z
. (o)
pliers for each of the dependent reactions. The values
1 3 5
1006 U. Mann / Chemical Engineering Science 55 (2000) 991}1008

We select Reaction 1, the leading reaction, as the refer-

ence reaction and use Eq. (8) to determine the character-
istic reaction time,

C 1
t " 0 " "0.5 min. (p)
#3 k C k
1 0 1
Substituting Eqs. (j)}(o) and Eq. (p) into Eqs. (b), (c) and
(d), the three design equations reduce to

dZ y !Z !Z !Z
1" A0 1 3 5
dq 1#Z !Z !Z
1 3 5

A BA B
k C y #2Z !Z 2 Fig. 5. Reaction operating curves for Example 2 * feed of species A.
! 2 0 B0 1 3 , (q)
k 1#Z !Z !Z
1 1 3 5

A B
dZ k C (y !Z !Z !Z )(y #2Z !Z )
3" 3 0 A0 1 3 5 B0 1 3
dq k (1#Z !Z !Z )2
1 1 3 5

AB
k y #Z !Z
! 4 C0 3 5 , (r)
k 1#Z !Z !Z
1 1 3 5

A B
dZ k C (y !Z !Z !Z )(y #Z !Z )
5" 5 0 A0 1 3 5 C0 3 5
dq k (1#Z !Z !Z )2
1 1 3 5

AB
k y #Z
! 6 D0 5 . (s)
k 1#Z !Z !Z
1 1 3 5
Fig. 6. Species operating curves for Example 2 * feed of species A.
For the given feed, y "1, y "y "y "0, and in
A0 B0 C0 D0
this case
(c) From Fig. 6 (or the table of calculated data), max-
P (5 atm) imum production rate of species B is achieved at q"0.8
C " "
0 R (0.08205 l atm/mol K) (762 K) and at that time Z "0.3641, Z "0.2369 and Z "
0 1 3 5
0.0940. Using the de"nition of the dimensionless space
"0.08 mol/l,
time Eqs. (28) and (p), the needed reactor volume is
(F ) (1 mol/s)
A B
v " 505 0" "12.5 l/s. qv (0.8) (12.5 l/s) 60 s
0 C (0.08 mol/l) < " 0" "300 l.
0 R k (2 min~1) 1 min
1
The parameters of the dimensionless design equations Substituting the values of Z , Z and Z into Eqs. (i)}(o),
are 1 3 5
the molar #ow rates of the species in the outlet stream
are: F "0.3049, F "0.4913, F "0.1429, F "
A B A B AB
k C
2 0 "0.8,
k C
3 0 "2,
k
4 "0.4, A065 B065 C065 D065
0.0940, and (F ) "1.033 mol/s.
k k k 505 065
1 1 1 (d) To determine the equilibrium composition, we cal-
culate the extents of the independent reactions at equilib-
A B AB
k C k
5 0 "5, 6 "1. rium by equating Eqs. (q), (r) and (s) to zero. We obtain
k k
1 1 a set of non-linear algebraic equations whose solution is
We substitute these values into Eqs. (q), (r) and (s), and
Z "0.3587, Z "0.3786, and Z "0.1518.
solve them numerically for Z , Z , and Z , subject to the 1%2 3%2 5%2
1 3 5
initial conditions that at q"0, Z "Z "Z "0. They Substituting these values into Eqs. (e)}(i), the dimension-
1 3 5
can be solved by a mathematical software. Fig. 5 shows less species molar #ow rates at equilibrium are
the solutions of the design equations * the reaction
operating curves of the reactor. F F F
A%2 "0.1109, B%2 "0.3388, C%2 "0.2268,
(b) Based on the solutions of Z , Z , and Z , we use (F ) (F ) (F )
1 3 5 505 0 505 0 505 0
Eqs. (e)}(i) to calculate the dimensionless species molar
#ow rates as a function of q. Fig. 6 shows the species F
D%2 "0.1518,
(F )
505 %2"0.8283.
operating curves of the reactor. (F ) (F )
505 0 505 0
 U. Mann / Chemical Engineering Science 55 (2000) 991}1008 1007

The corresponding molar fractions at equilibrium are

y "0.1339, y "0.4090, y "0.2738 and y "
A%2 B%2 C%2 D%2
0.1833.
Note that the equilibrium dimensionless species molar
#ow rates here are di!erent from those in part (c) because
the basis of the calculation is di!erent, but, the equilib-
rium composition (mole fractions) is the same.

5. Conclusions

The cornerstone of the new design formulation is the

Fig. 7. Reaction operating curves for Example 2 * feed of species D. recognition that reactor design equations should be ex-
pressed in terms of reaction-based quantities rather than
species-based quantities. By identifying the role that in-
dependent and dependent chemical reactions play in
reactor design formulations and applying stoichiometric
relations that are rarely used, we derived a new, general,
design methodology for chemical reactors with multiple
reactions. Combining these with a reaction-based char-
acteristic time constant and careful selecting a reference
state (or stream), the design equations are readily reduced
to dimensionless forms.
The main features of the new design methodology are:
f A unixed, general methodology to analyze and design
chemical reactors with multiple reactions (reactors
with single reactions are merely simple, special cases).
Fig. 8. Species operating curves for Example 2 } feed of species D. It is applicable to all reactor con"gurations, any com-
plex stoichiometry, and all forms of reaction rate
expressions.
The corresponding species mole fractions at equilibrium f Reactor operations are described in terms of generic
are: y "0.1339, y "0.4090, y "0.2738 and y dimensionless design equations that generate dimen-
A%2 B%2 C%2 D%2
"0.1833. sionless operating curves (a new concept in chemical
(e) When the feed stream consists of species D, we reaction engineering). These curves provide complete
carry out the design in the same way as we did in parts information on the progress of the chemical reactions,
a and b. The only di!erence is that now y " the formation (or depletion) of the species, and changes
A0
y "y "0 and y "1. We substitute these values in temperature. Speci"c cases (designs) are `pointsa
B0 C0 D0
into Eqs. (q), (r) and (s), and solve them numerically. on these curves (similar to the way a `pointa on
Fig. 7 shows the reaction operating curves for this case. dimensionless friction factor versus Reynolds number
Note that the extents of independent reactions 3 and charts is used to determine pressure-drop in a given
5 are negative, since the reverse reactions (Reactions tube).
4 and 6) take place. For these solutions of Z , Z , and Z ,
1 3 5 f Reactor operations are described in terms of the most
we use Eqs. (e)}(i) to calculate the species operating robust set of design equations (smallest number of
curves, shown in Fig. 8. design equations and the least number of terms in
To determine the equilibrium composition, we equate each). Since, in many instances, the design equations
Eqs. (q), (r) and (s) to zero and obtain a set of non-linear are sti! di!erential equations, the new formulation is
algebraic equations whose solutions are Z "0.3968, not merely a matter of mathematical elegance, but it
1%2
Z "!0.0535 and Z "!0.6205. enables us to obtain accurate numerical solutions.
3%2 5%2
Substituting these values into Eqs. (i)}(o), we obtain f New design capabilities for reactor con"gurations
whose design equations are not currently available in
F F F the literature ("lling reactor, plug-#ow reactor with
A%2 "0.277, B%2 "0.847, C%2 "0.567,
(F ) (F ) (F ) distributed feed, etc., discussed in Part II).
505 0 505 0 505 0
f A framework for developing new economic-based op-
F F timization tools for chemical reactor operations as
D%2 "0.3795 and 505%2 "2.071.
(F ) (F ) well as for integrated chemical processes.
505 0 505 0
1008 U. Mann / Chemical Engineering Science 55 (2000) 991}1008
Acknowledgements
Financial support for this work was provided by Texas
Tech University's Center for Energy Research and by
Tekton Technology, Inc. Mr. Sandeep Lal proof-read the
manuscript and provided helpful suggestions.
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