Chekcat En&ceriq Seienre. Vol. 41, No. 6, pp. 1647-1654. 1986. OW9-X09/86 S3.00 + 0.

00
Printed in Great Britain. F%zrgamoa loum.3la Ltd.

PARAMETRIC SENSITIVITY OF A CSTR

R. M. CHEMBURKAR, M. MORBIDELLI and A. VARMA+

Department of Chemical Engineering, University of Notre Dame, Notre Dame, IN 46556, U.S.A.

(Received 5 December 1985)

Abstract-It is shown that the generalizedsensitivitycriterionrecentlydeveloped in the context of thermal

explosions and tubular reactors can be easily applied in the case of a CSTR as well. An illustrativeexample
concerningsensitivityanalysisof a singlenth order irreversibleexothermicreactionin a nonadiabaticCSTR
is presented.A generaked region of parametric sensitivity is identitkd where the reactor temperature is
parametrically sensitive simultaneously to al! the input parameters. Asymptotic analysis for large heats of
reaction is performed to investigate limiting hehaviour, which leads to the classical Semenov limit in the case
of large activation energies. It is shown that parametric sensitivity can occur even when unique steady states
exist for all Damkiihler number (Da) values.Furthermore,if operatingconditions are chosen so as to avoid
completelythe possibilityof parametricsensitivityfor all Da, then the possibility of steady-state multiplicity
is automaticallyavoided.

1. INTRODUCIION the classic work of Semenov (1928), several theoretical

It is well known that chemical reactors, in certain
regions of operating conditions, may exhibit a para-
metrically sensitive behaviour, i.e. small changes in
one or more of the reactor input parameters lead to
much larger changes in the output variables. This
concept was first introduced in a pioneering study by
Bilous and Amundson (1956), who investigated the
sensitivity behaviour of a pseudo-homogeneous tu-
bular reactor.
For exothermic reactions occurring in a tubular
reactor, the temperature profile along the reactor
length exhibits almost inevitably a maximum value
often referred to as a “hot spot”_ When such a reactor is
operated in the parametrically sensitive region, small
changes in the inlet or other operating conditions may
produce large increases in the hot-spot magnitude,
thus seriously affecting reactor performance or cata-
lyst activity. Therefore in practical applications, it is
usually desired to avoid such operating conditions
leading to parametric sensitivity, and it is particularly
beneficial to do so in the earlier stages of reactor
design. This necessitates the formulation of an a priori
criterion for parametric sensitivity, based upon which
any possible steady-state regime of the reactor can be
identified as either parametrically sensitive or non-
sensitive. Using such a criterion, the regions of para-
metric sensitivity in the reactor parameter space can
be identitled in an a priori fashion, i.e. without
reference to any specific reaction or reactor regime.
The practical importance of this problem has
prompted a large number of investigations, all dealing
with the case of tubular reactors, where various criteria
for parametric sensitivity have been developed.
It is worth noting at this juncture that quite similar
problems arise in the context of thermal explosion
theory, where the occurrence of parametric sensitivity
is basically identitled with ignition phenomenon. Since
-0 whom correspondenceshould be addressed.
1647
and experimental studies have been published in order
to develop and verify criteria for ignition (Zeldovich
et al., 1985). The close connection between thermal
explosion and chemical reactor theories is due to the
striking similarity between the pseudo-homogeneous
models describing the temperature history of an
explosive medium and the temperature profile along
the tubular reactor axis. This allows direct application
of any criterion, originally developed in the context of
thermal explosions, to chemical reactors and vice versa.
Earlier c1 priori criteria, which have recently been
reviewed and compared (Morbid&i and Vat-ma,
1985a), were all based on some geometric feature of the
temperature-reactor length (or time) profile. In par-
ticular, the criterion proposed by Adler and Enig
(1964), which was recommended as the most reliable
among them, defines runaway as the occurrence of a
region with a positive second-order derivative some-
where in the temperature-conversion profile, before
the hot spot.
Only recently, and in the context of thermal ex-
plosions, sensitivity criteria have been proposed based
on the rigorous concept of sensitivity (Lacey, 1983;
Boddington et al., 1983). In particular, we have pro-
posed (Morbidelli and Varma, 1985b) a generalized
sensitivity criterion based on the sensitivity of the
maximum temperature to any of the model input
parameters. It was shown that sensitivity exhibits a
sharp maximum when the heat of reaction parameter is
varied. The value of the heat of reaction parameter at
which the maximum occurs is termed the critical value,
since it separates the sensitive and nonsensitive regions
of reactor behaviour. It was also found that the same
critical value is obtained regardless of which particular
input parameter is considered in the definition of
sensitivity. Thus this criterion identifies a generalized
region of parametric sensitivity, where the reactor
becomes simultaneously sensitive to small changes of
any of the input parameters. Moreover, the sensitivity
boundaries obtained were in good agreement with
1648 R. M. CHEMBURKAR
those computed through the Adler and Enig (1964)
criterion mentioned above. This finding rigorously
supports the reliability of the latter criterion, where
sensitivity is defined without reference to any specific
model parameter-thus implicitly assuming the exist-
ence of a generalized sensitivity criterion.
In addition to its rigorous character, the great
advantage of the proposed criterion is that it can be
extended to any reactor model and to any reactor
characteristic, besides the hot-spot magnitude. This is
not true of any of the previous criteria, which are based
on some topological feature of the temperaturc-
reactor length profile, characteristic of tubular
reactors.
An example illustrating the generality of the pro-
posed criterion is given in the present work, where the
sensitivity behaviour of a single irreversible nth order
exothermic reaction in a homogeneous nonadiabatic
CSTR is examined. Even though this is the simplest of
chemical reactors, its detailed sensitivity analysis has,
to our knowledge, never been reported previously in
the literature. This may be because none of the
previous criteria can be applied in this case (in fact,
there is neither a temperature profile nor a hot spot),
and only the generalized criterion for parametric
sensitivity mentioned above can be used effectively.
Specifically this allows an a priori identification of the
regions of generalized parametric sensitivity in the
reactor parameter space.
A particularly interesting aspect of this work is that,
due to the simplicity of the model studied, both
sensitivity and steady-state multiplicity behaviour of
the reactor can be fully identified, This allows a better
understanding of the connection between these two
phenomena, often regarded as separate issues, and by
combining both these results, safe operating con-
ditions for a CSTR can be identified which avoid both
multiplicity as well as parametric sensitivity.
2. SENSITIVITY ANALYSIS
The steady-state behaviour of a single irreversible
nth order exothermic reaction occurring in a non-
Table 1. Exact analyticalformulae for various partial derivativesof F
dDa= (v- 1)
exP[Y(l-:>I
aF=D* n(1 +fi -vr-’
afi (v-1)
aF Da(l+p-vr
-=
a?
dF
--Da
an
et al.
adiabatic CSTR can be cast into the following compact
dimensionless form (Kaushus et al_, 1978):
F(v; Da, /?, y, n) = Da (1 +fl-0)”
x exp[y(l - l/v)j/(u - 1) -p-1) = 0 (1)
(u-1)-/?(l -U) =o. (2)
All the distinguishing features of the system can be
determined by investigating eq. (1) alone, since eq. (2) is
merely a linear algebraic relation between the dimen-
sionless concentration, u, and the dimensionless tem-
perature, 0.
Let us define the absolute and the normalized
sensitivities as follows:
~(0; 4) = Idv/d+(
and
S(W+) = ld(lnWd(ln#I = IW/v)s(v;#l (3)
where 6 represents any of the four model input
parameters, i.e. Da, 8, y and n. As discussed previously
in the context of thermal explosions (Morbidelli and
Varma, 1985b), normalized sensitivity is a more con-
venient quantity for sensitivity analysis since it has a
clearer physical meaning, which derives from the
normalization procedure implicit in its definition.
Hence it will be adhered to in this study. Sensitivities s
or S, readily obtained by differentiating eq. (1) with
respect to q5, can be easily written in the following
form:
s(o; 6) = 1-(+/VI (=‘lW)lW_l~~)l (4)
where the analytical expressions of all the partial
derivatives are reported in Table 1.
In Fig. 1, the steady-state value of the reactor outlet
temperature, v, is shown as a function of the heat of
reaction parameter fi, together with the corresponding
normalized sensitivity of the outlet temperature to /3,
i.e. S(v; B). The sensitivity displays a sharp maximum at
j3 = j?,, as fl is varied. At this point the outlet tempera-
ture is most sensitive to changes in /?. For j3 values
larger than fi,, the reactor is in an ignited state where
the reactor temperature has reached a much higher
-(?I -1)8”_*

0.20 0.2t 024
-6
Fig. 1. Effectof the dimensionlessheatof reaction,S, on v and
S(V; 8). Da = 0.11, y = 20, n = 1.
value which is undesirable in most cases. Thus accord-
ing to the generalized sensitivity criterion, #I, cor-
responds to the critical value for sensitivity, so that for
/I < /I, the reactor is nonsensitive, while for fl > #i, it is
parametrically sensitive.
In this situation depicted in Fig. 1, the reactor
exhibits a unique steady state for all values of /l. It is
well known that nonisothermal CSTRs may exhibit
steady-state multiplicity, leading to curves of classical
S-shape in the G-P plane under consideration. In this
case, as shown in Fig. 2, the temperature sensitivity
increases for increasing /I values and becomes infinite
at the bifurcation point /I = B*. In fact, at any bifur-
cation point aF /&I = 0, and therefore, from eq. (4),
S(v, 4) + cl, for any 4. Since sensitivity attains its
maximum value at the bifurcation point /I*, it follows,
according to the adopted sensitivity criterion, that this
point also represents the critical condition for sensi-
tivity, i.e. /I, = j?*. This agrees with the results obtained
by Barkelew (1984) about sensitivity behaviour of a
CSTR. However, in that work, no sensitivity criterion
was adopted, and the occurrence of sensitivity was
simply identified always with the occurrence of multi-
plicity_ In the present work, such a coincidence follows
rigorously from the adopted sensitivity criterion, and it
1.3 -
I
>
1.2 - -
I.1 -
8. = /3’- 0.340
IO* _ _ : . . .
0.20 0.25
Fig. 2. Effect of the dimensionlessheat of reaction, /3. on v
and S(u; B) in the multiplicity region. Da = 0.07, y = 20, n
= 1.
Parametricsensitivityof a CSTR 1649
is also evident that sensitivity is u phenomenon in-
dependent of multiplicity; in fact, it may also occur in
the region of reactor steady-state uniqueness, as
shown, for example, in Fig. 1.
It is worth pointing out that in Fig. 2 the sensitivity
values refer to a reactor steady state on the low-
temperature branch as long as this branch is available.
When the temperature jumps to the high-temperature
branch at the bifurcation point /I*, the sensitivity
exhibits a discontinuity, dropping from an infinite to a
finite value. Throughout this study we concern our-
026 028 0.30
selves mainly with the low-temperature steady state.
The case where the reactor is operating on the ignited
brzinch is of less practical interest from the viewpoint
of defining temperature runaway and parametric sensi-
tivity; nevertheless, comments about this case will be
made later in this study.
In Fig. 3 the sensitivity of the outlet temperature
with respect to various inlet parameters r$ is shown. It
appears that the critical #Ivalue, i.e. the location of the
maximum sensitivity, is the same to three significant
figures (#I, = 0.248) for any choice of 4. This clearly
shows the generalized nature of the adopted criterion
because the reactor outlet temperature becomes sensi-
tive to all the model parameters simultaneously. Thus,
the parameter range characterized by /I > fl, can be
called the generalized region of parametric sensitivity.
Thisclaim is further substantiated by the results shown
in Table 2, where the critical values of + (defined as
Da #) which maximize S(v; r#~) with respect to /I for any
choice of the input parameter 4 are reported. The
quantity + is defined to be similar to the Semenov
number in explosion theory so as to facilitate com-
parison between various reaction configurations and
to tie in general concepts later in this paper. The
reported values of critical $ (i.e. $,) in Table 2 were
obtained by computing the critical values of p(i.e. 8,)
for any chosen y and Da, then using the definition of 1/1
(i.e. +, = Dayj3,)_
Two definite trends may be noted from Table 2:
(1) For smaller Da, and a fixed y, all the /3, values
become the same. However, the difference between
the /I, values found for different choices of 4
increases as Da increases.
-4
_
^
cl_
._
m
0.30 0.35
Fig. 3. Rehaviourof sensitivitiesS(u; I$)with the dimension-
less heat of reaction. #?.Da - 0.11, y - 20, n = 1.
1650 R. M. CHEMBURKAR et al.

(2) As y increases, the difference between the various PC

values decreases.
These results show that in the region of low heat of
reaction /I and activation energy y, the critical values
obtained from the analysis of S(u; 4) become de-
pendent on the particular choice of 4. Thus in this case
the validity of the concept of a generalized sensitivity
region is lost. The low overall energy available to the
system in these cases results in a mild nature of any
temperature-related phenomenon. This mild nature
can be evidenced by relatively low values of the
maximum S(I); 4) attained, as can be seen for the case of
large Da in Fig. 4. As Da decreases, the critical /I value
increases, and so does the value of sensitivity at
criticality. Thus for large B values, where thermal
sensitivity is a significant phenomenon, the generalized
sensitivity concept holds (see Table 2). For smaller /I
values (or larger Da values) where the concept does not
hold, the sensitivity in itself is a much less dramatic
phenomenon. In fact, for relatively large Da values,
there is no critical fi, value indicating that thermal
sensitivity no longer exists. Similar behaviour was
previously reported for tubular reactors using the
Adler and Enig criterion (Morbidelli and Varma,
1982).
From the values reported in Table 2 it may be seen
that the critical value of @, as Da + 0, approaches an
asymptotic value which depends on y. This can also be
proven analytically. For Da --* 0 (or, equivalently, for
large heats of reaction), the critical value PC can
invariably be obtained from one of the bifurcation
points of eq. (1) as long as y > 4. For n # 0 and large /i,
this bifurcation point corresponds to the smaller root
of
02 -yv+y = 0. (5)
Indicating this root by uC,the critical value of /l (i.e.
fi, = fl*) can be found by substituting v, into eq. (1).
Thus the asymptotic value of +, = Da yfi, is given by

Y (0, - 1) exp C - ~(1 - l/v31 (6)

which, in the limit of y + co, approaches e- ‘. For
n = 0, the bifurcation point is the smaller root of
eq. (5) for all values of /3_Hence, in the ease of n = 0, the
value of ti, given by eq. (6) is valid for all /I.

Fig. 4. Effect of Da on the behaviourof S(v; @ vs. 8. y = 20, n

= 1.
 Parametric sensitivityof a CSTR 1651

This conclusion agrees with classical results pre- which S(V;~), irrespective of the choice of 4, is
viously reported in the context of thermal explosion maximized with respect to any of the involved input
theory (cf. Morbidelli and Varma, 1985b), which also parameters_
apply to pseudo-homogeneous plug-how reactors. In
particular, for large values of the heat of reaction
(equivalent to fi in the CSTR case; cf. Vat-ma and Aris,
1977), it was shown that the Semenov number, defined 3. REGIONS OF PARAMETRIC SENSITIVITY FOR
as the ratio between the rate of heat production by A CSTR

reaction and heat removal from the system (i.e. +
= Day/3 in the CSTR case), approaches a finite value
given precisely by eq. (6). Moreover, for y + co, this
value approaches the classical Semenov limit e- ‘. This
is a rather interesting finding, which, in view of the
different nature of the chemically reacting system
examined, indicates the intrinsic nature of the sensi-
tivity concept.
Up to this point, S(v; 4) has been maximized with
respect to /3 only, in the process of finding 8,. We now
examine the results when the maximization is done
with respect to some other parameter. In Table 3, half
of the values are reproduced from Table 2 [where
S(U; 4) was maximized with respect to /I], while the
others are obtained by maximizing S(u; 4) with respect
to Da. Again the same conclusion as before is reached;
i.e. despite the discrepancies at large Da, the sensitivity
criterion becomes general as Da is decreased. This
reaRlrms the generalized character of the obtained
sensitivity region, since it is bounded by a curve on
After establishing the concept of a generalized
region of parametric sensitivity for the case of a CSTR,
these regions are mapped by examining the behaviour
of S(v; Du) with respect to /YIfor various values of y (for
a first-order reaction, i.e. n = 1) and for different
reaction orders (for y = 20) in Fig. 5(a) and (b),
respectively. Each curve in these figures represents the
critical conditions for parametric sensitivity. Thus
values of the operating parameters lying above the
curves indicate parametric sensitivity, while nonsensi-
tive safe operation is obtained below the curves. These
figures indicate that sensitivity is more likely as either
the activation energy y increases or the reaction order n
decreases.
The asymptotic behaviour in the limit of small Da,
which is not clearly seen in Fig. 5, is illustrated in Fig. 6
obtained by transforming Fig. 5 from the &Da plane
to the $-Da plane. Figure 6 confirms attainment of the
limits given by eq. (6) for various y values, and the
Semenov limit +, = e-i as y becomes large.

Table 3. Critical values of 1,4= DONS; n = 1, y = 2Ot

The critical value found by maximizing S(q 4)

with respect to fi with respect to Da

d
DU Da B Y n Da B Y ”
l_
0.01 0.3992 0.3992 0.3992 0.3992 0.3992 0.3992 0.3992 0.3992
0.05 0.4488 0.4488 0.4488 0.4488 0.4488 0.4488 0.4488 0.4488

0.11 0.5454 0.5454 0.5454 0.5454 0.5452 0.5452 0.5458 0.5452

0.14 0.6076 0.6121 0.6129 0.6140 0603 1 0.6075 0.6106 0.6cr97
0.17 0.6640 0.68 10 0.6824 0.6851 0.6481 0.6638 0.6610 0.6698
0.20 0.7144 0.7504 0.7428 0.7504 0.6826 0.7159 0.7002 0.7254
0.30 0.8688 1.0332 0.9552 0.9618 0.7411 0.8709 0.7687 0.8824
0.40 0.9992 $ 1.1728 1.1752 0.7365 1.0091 0.7682 1.0040

+For entries above the solid line. the rector exhibits steady-state multiplicity; below the solid line, the steady
state is unique.
tThe curve S(Y; j?) does not exhibit any maximum in this case.

0.5 0.5
a b

E L!!sd
ynlo Il.1 y = 20
0.4 0.4

” -3
0.3 0.3

1;
0.2

0.1
50
20

100
‘i 0.2

0.1
2
I

0 0.5

0 0. I 0
0.2 0.3 0.4 0.5 0.1 0.2 0.3 0.4 0.5
- Da - Da

Fig. 5. Effect of (a) dimensionless activation energy y and (b) reaction order non the parametrically sensitive
region in the B-Da plane.
1652 R. M. CHEMBURKAR
Fig. 6. Effect of (a) dimensionless activation energy y and (b) reaction order n on the parametrically sensitive
region in the $-Da plane.
4. COMPARISON OF THE REGIONS OF PARAMETRIC
SENSITIVITY AND STEADY-STATE MULTIPLICITY
‘The multiplicity analysis of a CSTR, wherein an nth
order exothermic reaction occurs, has been the subject
of numerous earlier studies. It is well known that for
y > 4, for every reaction order n, there exists a region in
the &Da plane where multiple solutions are possible
for eq. (1).
Figure 7 represents typical behaviour in the /l--Ba
plane for lixed values of y and n, where the region of
parametric sensitivity lies above the solid curve, and
the multiplicity region exists between the dashed and
the solid curves. For an existing unique nonsensitive
steady state on the low-temperature branch, any
change in the operating variables is considered safe as
long as these changes are restricted to the para-
metrically insensitive region, e.g. the excursion P,Q1 in
Fig. 7. The same holds for excursion PaQI, but during
this excursion the multiplicity region is encountered.
This type of excursion results when /l is increased from
a value less than fi* to a value lying between ~3. and /I*,
keeping Da constant as in Fig. 2. Thus it is evident from
Fig. 2 that local sensitivity of the low-temperature
steady state does not exhibit a maximum, and hence
the excursion is safe from a local sensitivity point of
view. However, the existing steady state is no longer
O’O-
Fig. 7. Regions of multiplicity and parametric sensitivity in
the /?-Da plane. The region of parametric sensitivity lies above
the solid curve. The region of multiplicity is enclosed by the
dashed and the solid curves.
et a!.
globally stable; any large perturbation in the operating
conditions (or the transients during start-up or shut-
down) can be detrimental-thus global sensitivity is
affected. In fact, using this reasoning, Bilous and
Amundson (1955) restricted themselves to multiplicity
considerations while studying the sensitivity of
CSTRs. In the case of excursions like PBQa and P4Q4,
the sensitivity exhibits a maximum when the boundary
of parametric sensitivity region is crossed, i.e. when the
excursion cuts across the solid curve in Fig. 7.
Consider now the case where the reactor is being
operated in the ignited state; i.e. on the high-
temperature branch of Fig. 2, when Da K Da=_ in Fig.
7. The boundary of the parametric sensitivity region in
this case will be different from that found earlier by
analysing the sensitivity of the low-temperature steady
state. It is self-explanatory from Fig. 2 that sensitivity
will now become infinite at /3 = /I,_ Hence in this case,
as the solid curve in Fig. 7 (loci of /?*) is crossed from
the top, the region of multiplicity is entered which will
affect global sensitivity; however, local sensitivity will
not be affected. In fact, local sensitivity is not affected
as long as the operating conditions remain above the
dashed curve in Fig. 7 (loci of fl*).
In practical situations, the volumetric flow rate q is
the variable which can be subjected to change most
readily. Thus it is of significant interest to know a priori
whether for a given set of physicochemical par-
ameters, any multiplicity or parametric sensitivity is
encountered for any value of the flow rate q. In order to
conduct this analysis, it is necessary to cast the physico-
chemical parameters into dimensionless quantities
which are independent of the flow rate q_ Recently,
multiplicity analysis from this point of view was
reported by Balakotaiah and Luss (198 1). This involves
defining two new variables, a = 6/Da and B = yfl(l
+ a), which are completely independent of q for the
case of T, = T,. Since now only the Damkiihler
number involves q, the results obtained about multi-
plicity/sensitivity for some q can equivalently be said
for some Da.
Balakotaiah and Luss (1981) used singularity theory
to identify regions of all different types of multiplicities
for some Da in the a-8 plane. These results for the case
of T, = Tr are shown in Fig. 8. In Fig. 9, the a-B plane
is shown divided into the region of multiplicity for
some Da, and the region where no multiplicity is
 Parametric sensitivity of a CSTR
4 some Da values, then parametric sensitivity also exists
m for some Da values; however, the converse is not true.
II
iy
I
c
F
CI
E
I Da, parametric sensitivity may occur for some Da.
P Ip
Fig. 8. Identification of different types of multiplicity pat-
terns in the a-B plane (not to scale). (I) Unique steady state;
(ID isola; (III) mushroom: (IV) S pattern; (V) S+isola
20 I I I I
‘/
-e
Fig. 9. Comparison between the region of multiplicity and
the region of parametric sensitivity. Multiplicity exists for
some Da below curve a, while parametric sensitivity exists for
some Da below curve b. y = 100, T, = T,, n = 1.
possible for any Da by curve a Curve a is formed by the
hysteresis (S pattern) line for J!3< B, and the isola curve
for B > 3 (see Fig. 8); hence above curve a lies the
region where multiplicity is not possible for any Da,
while multiplicity occurs for some Da below curve a.
Curve b in Fig. 9 is obtained using the following
procedure. Every point on the solid curve in Fig. 7, say
(Da,, #?J, represents the critical conditions for para-
metric sensitivity. Each of these critical points is
translated into a critical line in the a-B plane by
varying S and computing a, = a/Da, and B, = ~$3,(1
+a). Each such line divides the a-B plane for that
choice of /I, and Da, into two parts; below the line lies
the region of parametric sensitivity, while nonsensitive
operations occur above the line. Repeating this pro-
cedure for many such critical points (Da,, fi,) gives rise
to many such lines, and curve b is tangential to all these
lines. Thus parametric sensitivity cannot occur for any
Da above curve b, while it is possible for some Da
below curve b.
Figure 9 shows that the region of multiplicity for
some Da, is a subset of the region of parametric
sensitivity for some Da. Thus if multiplicity exists for
1653
The same conclusion can also be reached from Fig. 7,
where for j3 > fl,, both multiplicity and parametric
sensitivity occur for some Da values; however, for
#3 -z flFUsP
although multiplicity is not possible for any
5. CONCLUDING REMARKS
In this study, the region of parametric sensitivity for
a CSTR has been identified. It is shown that a
generalized region of parametric sensitivity can be
defined, which is independent of the input parameter
chosen for defining the sensitivity. These findings are in
complete agreement with results previously obtained
in the case of thermal explosions and pseudo-
homogeneous tubular reactors (Morbidelli and
Varma, 1985b). Specifically, also for these reacting
systems, using the same sensitivity criterion, the exist-
ence of a generalized sensitivity region was proven. The
I
similarity among these systems is not only qualitative
but also quantitative. In the limit of large heat of
reaction parameter, the so-called Semenov number I&,
representing the ratio between the rate of heat produc-
tion and cooling, approaches the same asymptotic
value. Thus, using dimensionless parameters having
equivalent physical meaning (cf. Varma and Aris,
1977), the CSTR and the plug-flow reactor exhibit the
same sensitivity region, at least in the limit of large heat
of reaction_ This finding supports the intrinsic nature
of the adopted sensitivity criterion, which brings
together seemingly different chemically reacting
systems.
Another important conclusion of this work con-
cerns the comparison between the regions of par-
ametric sensitivity and steady-state multiplicity. This
leads to an identification of the range of operating
variables that will yield unique nonsensitive steady
states, required for safe operations. The results ob-
tained by analysing the a-B plane for the regions in
which steady-state multiplicity or parametric sensi-
tivity is observed for some Da show that the former is
always completely enveloped by the latter. In practical
applications, since it is usually not desirable to operate
in the sensitive region, it follows that certainly the
situations where the reactor exhibits multiplicity
would not be approached. Therefore, with respect to
practical applications, it is of primary importance to
establish the boundary of the sensitivity region. Once
this is avoided, multiplicity is automatically avoided.
This conclusion is also more general than what is
shown in this work for a homogeneous CSTR. In
particular, Morbidelli and Varma (1986a, b) have
examined a heterogeneous plug-flow reactor for both
sensitivity and multiplicity behaviour and reached
similar results. With respect to reactor design, this
finding stresses the need for sensitivity analysis, which
would automatically account for any possible steady-
state multiplicity as well.
1654 R. M. CHEMBURKAR etal.

Acknowledgement-One of us (A.V.) acknowledges with fond f feed condition

memory and great pleasure the period of his graduate studies * lower bifurcation point
under direction of the “Chief”.

Superscript
NOTATION * higher bifurcation point
a area of heat transfer
B YS(l +a)
B notation used in Figs 8 and 9 REFERENCES
C reactant concentration Adler, J. and Enig, J. W., 1964, The critical conditions in
specific heat thermal explosion theory with reactant consumption.
CP Comb. Flame 8,97-103.
Da Damkijhler number, V CT- ’ k( T,)/q
Balakotaiah, V. and Luss. D., 1981, Analysis of the multi-
E activation energy plicity patterns of a CSTR. Chem. Engw Commun. 13,
F (u; Da, 111-132.
B, Y. n) function defined by eq. (1) Barkelew, C. H., 1984, Stability of adiabatic reactors. Am.
rate constant as a function of tempera- Chem. Sot. Symp. Ser. 237, 337-359.
k(T)
Bilous, 0. and Amundson, N. R., 1955, Chemical reactor
ture, T
stability and sensitivity. A.I.Ch.E. J. 1, 513-521.
reaction order Bilous, 0. and Amundson. N. R, 1956, Chemical reactor
volumetric flow rate stabilityand sensitivity-II. Effect of parameterson sensi-
universal gas constant tivity of empty tubular reactors.A.I.Ch.E. J. 2, 117-126.
sensitivity of u with respect to 4 Boddington, T., Gray, P., Kordylewski, W. and Scott, S. K.,
1983, Thermal explosions with extensive reactant con-
normalized sensitivity of t, with respect sumption: a new criterion for criticality. Proc. R. Sot. A390,
to 4 13-30.
temperature of the CSTR Kaushus, W., Demont, J. and Hartmann, K., 1978, On the
coolant temperature steady states of continuous stirred tank reactors. Chem
Engng Sci. 33, 1283-1285.
mean temperature, (T,+ ST,)/(l + 6)
Lacey, A. A.. 1983, Critical behavior for homogeneous
dimensionless concentration, C/C, reacting systems with large activation energy. Int. J. En#ng
overall heat-transfer coefficient Sci. 23, 501-515.
dimensionless temperature, T/T, Morbidelli, M. and Varma, A., 1982, Parametric sensitivity
and runaway in tubular reactors. A.I.CLE. J. 28,705-713.
volume of the CSTR
Morbidelli, M. and Varma, A., 1985a, On parametric sensi-
tivity and runaway criteria of pseudohomogeneous tubular
Greek letters reactors. Chem. Engng Sci. 40, 2165-2168.
a S/Da Morbidelli, M. and Varma, k. 1985b. A generalized criterion
notation used in Figs 8 and 9 for parametric sensitivity: application to thermal explosion
z
theory. Proc. R. Sot.
B dimensionless heat of reaction, Morbidelli, M. and Varma, A., 1986a, Parametric sensitivity
(- AH) G/PC, T,(l + 6) in fixed-bed reactors: the role of interparticle transfer
6 Ua/PqcP resistances. A.I.Ch.E. J. 32, 297-306.
AH heat of reaction Morbidelli, M. and Varma, A., 1986b, Parametric sensitivity
an input parameter and runaway in catalytic reactors. Accepted for presen-
4 tation at ISCRE 9, Philadelphia, 18-21 May.
Y dimensionless activation energy, E/RT, Semenov, N. N., 1928, Zur theorie des verbrennungs-
P density prozesses. 2. Pbys. 48, 571-582.
# DayS Varma, A. and Aris, R., 1977, in Chemical Reactor Theory. A
Review (Edited by Lapidus, L. and Amundson, N. R.),
Chap. 2, pp. 79-155. Prentice-Hall, Englewood Cliffs, NJ.
Subscripts
Zeldovich, Ya. B.. Barenblatt, G. I., Librovich, V. B. and
C critical value Makhvjladze, G. M., 1985, The Mathematical Theory of
cusp cusp point Combustion and Explosions. Plenum Press, New York.