Chemical Engineering Science. 1974, Vol. 29. pp. 967-985. Pergamon Press.

Printed in Great Britain

ON THE DYNAMIC BEHAVIOR OF CONTINUOUS

STIRRED TANK REACTORS
A. UPPAL and W. H. RAY
Department of Chemical Engineering, State University of New York at Buffalo, Buffalo, N.Y. 14214,
U.S.A.

and

A. B. POORE
Department of Mathematics, State University of New York at Buffalo, Buffalo, N.Y. 14214, U.S.A.

(Received 25 May 1973; in revised form 22 August 1973)

Abstract-The types of dynamic behavior possible for a single first order reaction carried out in a
stirred tank reactor are classified according to values of the parameters and plots in parameter space
used to define the various possibilities. Analytic criteria are developed which predict the existence and
stability character of limit cycles as a function of the system parameters. The types of dynamic be-
havior predicted are illustrated by numerical computation of the temperature and concentration trajec-
tories. Several kinds of new jump phenomena for this problem are observed and explained in terms of
the parameter space plots. The theory and analysis methods can be easily generalized to other types of
reaction systems.

1. INTRODUCTION vered these interesting phenomena [ l] and fostered

In the two decades work of Van
since the landmark
Heerdenll], there have appeared an enormous
number of papers discussing the dynamic behavior
of continuous stirred chemical reactors (CSTR).
Because of this the reader is justified in asking
“why yet another?” Our reply must be that we
think we have significant new results as well as a
sufficiently better perspective so as to allow the
previous work to be understood within a general
framework. In addition, the methods of analysis,
which we have used to obtain the results presented
here, are more powerful than previous techniques
and open the possibility for significant new results
in other lumped as well as distributed parameter
reactor systems.
The immensity of the literature treating this prob-
lem causes us to forego an exhaustive literature
survey of the subject in favor of a discussion of the
subject matter illustrated by the citation of key pap-
ers. The first recognition of multiple steady state
phenomena and stability problems in chemical
reactors seems to have been by Liljenroth[2] in
1918. However, this work lay unnoticed until 1970
when it was rediscovered by Luss [3]. Similar work
by Semenov[4], published in 1928, also was neg-
lected until rediscovered recently. In the mean-
while, Van Heerden in 1953 independently disco-
a flood of papers in the ensuing 20yr.
Bilous and Amundson [S], inspired by the work of
Van Heerden put the analysis of local stability of
the reactor steady states on a rigorous basis by the
use of the First method of Liapunov. Thus since
this paper in 1955, it has been a straightforward
matter to determine the stability properties of the
steady states. Although Bilous and Amundson did
show phase plots of concentration and temperature
trajectories in their paper [5], really extensive num-
erical calculations were only first reported in 1958
by Aris and Amundson[6]. Through the use of an
example with a variable proportional feedback con-
troller gain, Aris and Amundson[6] demonstrate
how the phase plots change as the controller gain is
increased. Through this example they show that in
addition to the presence of multiple steady states,
undamped oscillations in the form of limit cycles
can occur for some combinations of the system
parameters. They also recognized that these limit
cycles should bifurcate (originate) at the critical
value of the feedback control parameter where the
stable steady state becomes unstable. In fact, they
developed a criterion for the direction of bifurca-
tion and gave plausible arguments for the stability
of the limit cycle.
A large number of other workers have since car-

967
968 A. UPPAL et a/.

ried out numerical calculations of CSTR dynamics
(e.g. [7-331, both to illustrate the phenomena which
can occur and to analyse the performance of par-
ticular systems. A number of these papers have in-
volved the modelling of a particular reaction sys-
tem and have included experimental results show-
ing multiple steady states and limit cycle behavior
(e.g. [S, 9,27-331). Another area of interest has been
in simulating and analytically approximating the
limit cycles which arise in order to ascertain where
limit cycle operation might give improved
performance[l5-191.
Because multiple stable steady states have do-
mains of attraction which do not encompass the
whole phase space, there has been a large amount
of work applying Liapunov’s second method and
other methods to the CSTR to determine the exact
boundaries of the region of asymptotic stability
(e.g. [ 1l-141).
The problem of the existence and stability of
limit cycles has been attacked in a number of differ-
ent ways. The second Liapunov method has been
bility character of these limit cycles. An explana-
tion of a number of unusual phenomena will be
given in terms of the parameter space plots.
We believe that we have completely resolved the
problem of the various types of dynamic behavior
for the CSTR, the key being the bifurcation of
periodic orbits. The method is not new; it is, in fact,
due to Poincare [42]. Other accounts of bifurcation
of periodic orbits can be found in Minorsky[37],
Andronov [42] and Friedrichs [36]. All of these re-
ferences deal with the two dimensional problem.
The problem of bifurcation or periodic orbits from
certain steady states for higher dimensional prob-
lems (more than two equations) has been treated by
Hopf [43]. The application of this work of Hopf to
the study of dynamic behavior in higher order sys-
tems should prove to be as fruitful as our applica-
tion in the two dimensional case. Unfortunately,
this particular work of Hopf is not widely available.
2. MULTIPLICITY AND STABILITY OF THE STEADY
STATES

applied to the stability problem [ 11, 131with very li-
mited success. Luus and Lapidus[20] have used an
averaging technique to predict both the presence
and stability character of limit cycles. However,
there are gross approximations in the technique and
it is not always successful[21]. Douglas et al.
[15-191 have attempted to use a perturbation
technique to predict the form of a limit cycle, but
this approach is also uncertain[I9]. Gilles[tO] and
Hyun and Aris[26] have used a Fourier type
analysis to examine the existence and stability of
limit cycles and these seem to show moderate suc-
cess for the two examples examined.
In order to illustrate more clearly the ideas we
shall present let us consider the first order, exother-
mic, irreversible reaction A + B carried out in a
well mixed stirred tank reactor. If we allow a fresh
feed of pure A to be mixed with a perfect
undelayed) recycle stream with recycle flow rate
(1 - A)F, the material and energy balances become
V$ = AFc,, + F(1 - h)ca -Fen
E
- Vka exp
I 1
-RT CA, (1)

In this paper we seek to do several things making V&-$= pC,,F(hT, + (1 - h)T - T)

use of the irreversible, first order, exothermic reac-
+ V(-AH)koexp{-EIRT}ca -hA(T-T,) (2)
tion as a model system. First, we analyse the mul-
tiplicity and stability properties of the CSTR as a where the last term in (2) accounts for the heat re-
function of the system parameters. We have used moved from a cooling jacket maintained at temper-
the first method of Liapunov, a local method, to ature T,. Note that A = 0 corresponds to total
obtain the stability of the steady states. To analyse recycle and A = 1 to zero recycle.
the dynamic behavior in the CSTR, we have made By defining the dimensionless variables
use of the results of Poore [34] on the direction and
stability of branches of periodic orbits which bifur-
CAf - CA V
cate from certain steady states. By following the x, =- r=g,
CAf ’
branches to their completion, we are able to show
precisely the types of dynamic behavior which can t +;, k. e-V
Da zFA= k. e-3,
occur in each region of parameter space. These
points are illustrated by numerical examples pre-
sented in the form of phase plots. Included in the x
parametric analysis is the definition of regions
where single and multiple limit cycles will occur hA hAr
- y =EIRT,
and a presentation of an exact criterion for the sta- p=Fhpc,=VpC,’
 Continuous stirred tank reactors %9

Equations (1) and (2) become

s=-x,+Da(l-x,)exp X2
___ = f,(x,, x,),
(1+x 2,,I
(3)
dxt
x=-x’+BDu(l-x,)exp

- P(XZ- X2<)= fi(X,, x2). (4)

Notice that the recycle rate, (I- A), only influences

the reactor residence time, 7, and thus the values of
Da and p. Therefore, the analysis which follows
applies directly both to systems with and without
recycle.
Multiplicity
By setting the LHS of Eqs. (3) and (4) to zero one
obtains the steady states, x,,, xzs, which satisfy
002
Da
Fig. 1. Locus of reactor steady states: (1) when there is
multiplicity, (2) no multiplicity.
is the necessary and sufficient condition for multi-
ple steady states. If we define ml and m2 to be the
values of x,, over which multiplicity may occur (cf.
Fig. 1), then these are given by

-2B[$(l+P+~)-(I++D,“Z
ml,m2=
(6)
One can combine (5) and (6) to obtain (10)
where
X 2s =
Bx,, + pxzc
*+P D,,, =B[B[++($l)(l+p)]

II. (11)
and

Da
I
=cl~~,s)exp(1 + p) - (Bx,, + Px2c)
+ (llY)(BXl, + Px2c) I .
l+fl+y,‘$+(l+B)
I[
(8) In order for ml, m2 to have real values, D,,, 2 0 must
For fixed values of B, p, y, xl0 the dependence of hold, and this produces a criterion for the existence
the steady state conversion, xls, on the Damkijhler of multiple steady states
number, Da, will have one of the possible shapes
shown in Fig. 1. Curve (1) shows the case in which 4[1+ p + (px*Jr)l’
for some values of Da, multiple steady states are (12)
B a 1+ p - (4/y)[l+ P + (PX2clY)l’
possible, while curve (2) shows the situation when
only a single steady state may exist. These curves Notice that xZr has only a small influence on the
will have the form of curve (1) only if (dDa/dx,,) < result so that a very good approximation (when the
0 for some values of x,,. Therefore the condition feed and coolant temperatures are nearly the same)
is to assume xZc = 0 giving
dDa
[($+B(l+P))Z’+[2(l+P+~)$
dX1S= B ,4(1+P)Y
y-4 . (13)
-B(l+~)]x,,+(l+~+~))

-(BxI, + &)
exp (I + p) + (llr)(Bxl, + Px~c)
When the activation energy is large, the approxima-
tion y + 00can be used to remove both the parame-
ters y and x2< from (12) to yield
‘(I- x~,)~[I + P + (l/y)(Bxl, +
(9) B 24(1+@) (14)
970 A. UPPAL et al.

4-

: (b)y-20

2t r I
IQ I.5 20 25 36 28. I .5 2.0 2.5 30 3.5
(It BETA) (ItBETA)
24. (cb=40
!

5
(I +BETA)

Fig. 2. Classification of dynamic behavior in parameter space.

as a necessary condition for multiple steady states. where

The criterion (12) is plotted in Fig. 2 as line M. Thus
for all (/3, B) values above line M in Fig. 2 multip- -af,
-- af,’
licity will occur for some values of Da (curve (1) in ax, ax2
A=
Fig. 1) and for all (p, B) values below line M in Fig. ’ af2 af2
2 m, and mz will be complex and there will be no _ax,x2
multiplicity (curve (2) in Fig. 1).
and for this case
Local stability

1
It is well known that the local stability character
of the steady states of the reactor can be deter- [l + (X&)li
A=
mined by examining the properties of Eqs. (3) and Bx,, ’
(4) linearized about the steady state.7 This set of - -(‘+~)+[l+(x2,/y)p
linearized equations can be represented by
(17)
The local stability is determined by the sign of the
(15) real part of the eigenvalues of A. These eigen-
values, A,, A?, are given by the roots of the charac-
tThe exceptional case when one or more of the eigen-
teristic equation
values of the linearized system have zero real parts must
be treated by other methods. A’-(trA)A+detA=O (18)
 Continuous stirred tank reactors 971

where the determinant of A, det A, is given by y2(1 + B)(l - xlS)(l+ x2S/Y)ztr A

f(Xl,)= B2
1 = d,+ a*&+ a0
aix1s + (23)
detA=(1-x,s)(l+-X2s/Y)~(1+P)

$+s(l+P) $5 (defined by Eq. (20)) takes on non-negative values.

K > One can easily show by Descartes Rule of Signs
+[2B(l+B+~)-B(l+,,]~,~ that the smallest root of f(x,,) is always negative,
and the other two roots, s,, sl, will be either com-
plex conjugates for B sufficiently small or sz > sI >
1 for B even smaller. Thus the values of s, and s2
will pass from complex to real at some critical value
The trace of A, tr A, can be similarly expressed as of B, say B * (cf. Fig. 3), where 0 < s, = s2 < 1. For

B2
trA=(l-x,,)(:+xl,,y)’ 1 Yz(l+P)dS

1
B +(2-t B)B* --_2B 2Bx2,B x’

B+(,+8)_2(2+P)B_2pxz,B(2+P)
Y2(l + P)’ Y r?l+P) ‘.

Yu+P)r’u
+PY

(20)

Fig. 3. Character of roots of tr A as B increases.

Now it is easy to show that the necessary and suffi-
cient condition for the steady state to be locally
asymptotically stable is for the conditions B > B*, f(x,,) and thus tr A will be positive for s, <
x,, < s2 and the steady states will be unstable in this
det A>0 (21) region. The point where tr A = 0 defines the onset
of instability. From well known formulae for the
trA<O (22) solution of cubic equations, this occurs when
to be satisfied.? By comparing Eqs. (19) and (21)
(2a23 - ‘a;al+ 27a012+ (3a, _ (a2)*)3= 0 (24)
with Eq. (9), one can see that condition (21) will
only be violated for ml s xls s m2 i.e. for the mid-
dle of the three steady states (cf. Fig. 1). It can be
where ao, a,, a2 are the coefficients of xl, in Eq.
shown (e.g. [34,35]) that det A < 0 defines steady
(23); i.e.
states which are unstable saddle points (i.e. steady
states for which the slope of the heat removal line is
less than the slope of the heat production line [ 11).
a” = _ (2 + ml + Ph’ + 20 + PMxzcr
[ B2 B2
Thus the “slope condition”, det A>O, is satisfied
; (2+B) PXze2
for all steady states in the region of a unique steady
state (e.g. for parameters below line M in Fig. 2) (l+B) B ( >I
’
(25)
and for all steady states, xl, < ml, x,, > m2, when
a, _ Y*(l+ PI u+B2 w+ Ph
PW -___
I

there is multiplicity. B B
The second stability condition, Eq. (22), (often
called the “dynamic” stability condition) is violated _2Px2C(2+P)+2Px2c(l+P)Y+
B2 > (26)
for those values of x,, at which B(l + P)
a2 =
+Except when A has an eigenvalue with zero real part,
requiring further analysis. (27)
972 A. UPPAL
Thus Eq. (24) defines a line in the space of parame-
ters B, p, x,, y at which the onset of “dynamic”
instability begins.
The case when y -+ CCyields [34] the condition for
s,, sz real and O<sl<sz<l:
Ba3+B+2flp. (28)
The condition defined by Eqs. (24)-(28) is plotted as
line S in Fig. 2, and shows that for (/Ll,B) below line
S, roots s,, sz are complex and there is no possibil-
ity of the “dynamic” stability condition (22) being
violated. For values of (0, B) above line S, the
dynamic stability condition (22) is violated for s, <
XI, < sz.
Relative positions of m,, mz, s,, sz
It is useful in carrying out an analysis of the
dynamic behavior to define steady states where the
dynamic stability condition is violated; that is,
where s,, s2 fall in Fig. 1.
Consider the situation when s, <xi, < ml; the
steady state will be an unstable node or focus be-
cause tr A >O and det A> 0. However, as the
parameters change, s, will increase past m, to s: and
no instability will then be possible for xl, <ml.
This qualitative change in dynamic behavior can be
delineated in parameter space by determining those
parameters for which s, = ml.
Similar considerations apply for sz, although it is
easy to show that sz > m, always for this problem.
It is possible for m, < s2 < m2, in which case all
values of x,, > m2 will be stable. However as the
reactor parameters change sz may increase past m2
to s; causing the steady states in the range ml<
x,, < s; to be unstable. As the parameters change
still further, s, may increase past m2 to s’/ and s2
may increase to s’z’causing the steady states in the
range sY<x,, < s’z’to become unstable nodes or
foci. Thus it would be useful to define these
changes in dynamic behavior by finding the
parameters for which s2 = mz and s, = mz.
The line in the space of parameters B, /3, y, x2<
corresponding to s, = ml may be easily determined
by substituting m, (defined by Eq. (10)) into the
polynomial Eq. (23) whose roots are s,, s?. The re-
sulting equation contains only the system parame-
ters. Similarly, the conditions s, = m?, sz, mz, may
be found by substituting m2 into Eq. (23). The re-
sults for the special case y -+m come out quite
simply [34] as
B =(‘+fi)’
(29)
P ’
et al.
However, the more general results lead to much
more complex expressions and are presented
graphically as line SM in Fig. 2.
The influence of the parameters y, xzc on the
shape of the regions in Fig. 2 is quite interesting.
For small values of y (cf. Fig. 2a) the lines M, S,
and SM all shift to higher B, @ values, requiring
much more exothermic reactions for multiplicity
and limit cycle behavior to be observed. However,
as y increases the plots move much closer to the
ones for y +m case.
The effect of xze on the shape of those plots is
somewhat less than that of y. As a comparison of
Figs. 2(e), (b) and (f) shows, the lower the xzc value,
the more likely it is that multiplicity and limit cycles
will occur. However, this effect would not be
overly large for a physically realistic range of x2(
values. The physical implications of these results is
that more stable and less exotic operation can be
achieved by accomplishing the necessary cooling
through increasing p (the heat transfer area) rather
than by decreasing xzc (the coolant temperature).
The reader can be convinced of the truth of this
result by examining the influence of the parameters
B, x2, on the shape of the S shaped curves in Fig. 1
for a particular example.
Before proceeding to a detailed discussion of the
regimes of dynamic behavior, shown in Fig. 2, let us
analyse the nature of the periodic phenomena pos-
sible in the CSTR.
3. PERIODIC PHENOMENA
In this section we shall examine questions of the
existence and stability of periodic states of the
CSTR, e.g. limit cycles. Because this has been
treated in great detail by Poore[34], we shall only
sketch the mathematical approach and then give the
results and their implications.
Mathematical approach
To arrive at the results to follow, Poore [34] made
use of a perturbation technique developed from
Friedrichs’ Bifurcation Theorem [36] in which the
system equations (3) and (4) can be written in the
form
$=Ay+&(y./~) (30)
where y, = l/p(xi -x,,) is the deviation from the
steady state, s is a scaled time, A is the linearized
matrix about the steady state with det A > 0 and
tr A = 0, and pG(y, CL) stands for the remaining
terms in (3) and (4). When det A > 0, tr A = 0, the
 Continuous stirred tank reactors 973

system dy/dt = Ay has periodic solutions (y = 0 is
a center) and for k small one can show that (30) has
periodic solutions. We point out that the p in Eq.
(30) is on the order of magnitude of the polar vari-
able r arising when one converts (3) and (4) to an
equation in polar coordinates and applies the bifur-
cation theory as was done by Aris and
Amundson [6].
Existence and stability of periodic solutions
Since the applicability of the theory of Poincare
and Bendixson to this problem has been established
(e.g. [34]) it is clear that a periodic solution exists
around each unstable unique steady state. Thus for
the parameters in region V in Fig. 2, there will be a
limit cycle encircling an unstable steady state for
some values of the Damkiihler number. These limit
cycles will bifurcate from steady state solutions
1xIS= SI, Xzs= (Bs, + Pxz,)/(l + P)l and [xl, = sz,
xz. = (Bs, + pxzc)/(l + p)] and grow as Da changes
from the value at these bifurcation points (e.g. in
Fig. 1). For convenience in the discussion which
follows we shall refer to these bifurcation points
simply as “at s,” and “at sz”.
Now, we can make the following more genera1
statements concerning the existence and stability of
limit cycles
(i) There can be no bifurcation to periodic solu-
tions except at points s,, s2 (where the linearized
Eqs. (15) have periodic solutions) or possibly at
points m,, m2 (where one of the eigenvalues of the
linearized system vanishes).
(ii) There will be bifurcation to periodic solutions
at points s, when the parameters are in regions IV,
V, or VI in Fig. 2, and there will be bifurcation to
periodic solutions at points s2 when the parameters
are in regions III, IV, V, VI in Fig. 2.
(iii) There exist functions S@, B, 7, xzC),
&(p, B, y, xzC) which predict the direction of bifur-
cation and stability character of the periodic solu-
tions close to s, and sz. At the bifurcation point sI,
6, < 0 implies bifurcation to unstable periodic solu-
tions for values of Da to the left? of s, (cf. Fig. 16),
while S, >O predicts bifurcation to stable periodic
solutions for values of Da to the right of s, (cf. Fig.
24). For bifurcation at sz, values of S2< 0 corres-
pond to stable periodic solutions growing to the left
of sI (cf. Fig. 24), while & > 0 implies bifurcation to
unstable periodic solutions to the right of sz (cf. Fig.
7).
For the case where y +m, Poore[34] derived
expressions for 6, and &, i.e.
8, = {w,*(b, - 1) + (2b, - BsJ - (2b, - Bs,)*} (31)
62 = - {u;(bz - 1) + (2bz - BsJ - (2bz - BsJ’> (32)
where
bi=Bsi-(1+/3)
i=1,2 (33)
of = (B(si)‘- bi)bg.

The lines 6, = 0 and 8: = 0 have been plotted in

+We shall repeatedly speak of values of Da to the left
and right of s, and So,but in actuality we mean values of Fig. 4 (for y +=). They clearly show the regions in
Da to the left and right of the value of Da corresponding parameter space for which bifurcation is to stable
to s, or sz. and unstable limit cycles. Using the results pre-

I /-%
6.51
6 1.7 1.8 19 -
16t \ I - ~ItEETAl

21 I I I I I , I
1.0 1.5 2.0 2.5 30 3.5 4.0 45
(It BETA1

Fig. 4. Classification of dynamic behavior in parameter space, y + 30.

974 A. UPPAL et al.
sented in [34], expression for 6, and & could be
derived for finite y and plotted in Fig. 2. However,
as can be seen from the work of Poore[34], the
algebra is quite laborsome, and thus will not be
carried out here.
A number of earlier workers have used various
perturbation methods to attempt to describe limit
cycle behavior in CSTR systems [6, 10, 16-22,261.
In order to put the present approach in better pers-
pective, let us briefly review some of the earlier
methods.
It was Aris and Amundson [6] who first made use
of a bifurcation theory such as can be found in
Minorsky[37]. This theory requires that one con-
vert a linearized matrix to a special canonical form
and then change over to polar coordinates. The
form of the bifurcation theory presented by
Friedrichs[36] (and applied by us to this reactor
system) is equivalent but does not require the two
above mentioned conversions. We believe that
Friedrich’s work is easier to apply but this may be
just a matter of taste. Although the bifurcation
theory is “local” in nature, we adopt the approach
that it is better to establish the existence of bifurca-
tion, direction of bifurcation, and stability of bifur-
cated periodic solutions and then analyse the
branches of the bifurcated periodic solutions num-
erically as a parameter changes (e.g. Da here).
Since the system (3) and (4) is not conservative,
there is little hope of obtaining global quantitative
information about the periodic solutions for arbit-
rary parameters without the use of these computa-
tions.
Other techniques, e.g. Fourier analysis and
averaging[lO, 19-22,261 have been used with mod-
erate success. Gilles, in 1964[10], made use of
a Fourier analysis of the periodic solution assuming
the output had a fundamental sine and cosine wave
form. By determining the wave amplitudes which
satisfied the system equations, he was able to pre-
dict the existence of single and even double limit
cycles. Although, the one example he gives showed
numerical calculation agreeing closely with the pre-
dictions, it is not clear that this technique will al-
ways be so reliable because of the special assump-
tions made about the output wave form[22]. How-
ever, by extending the analysis to the full Fourier
Series expansion as Gilles also suggests, results
similar to those presented here could be obtained.
Hyun and Aris[26] have recently applied a similar
type of analysis to a reactor with hysteresis.
A number of other workers [ 19-211 have applied
the method of averaging to a limited number of
cases. It is our feeling that an averaging method
(see for example, Hale[38]), if carefully applied,
would also be capable of predicting all the
phenomena that we have found for this problem.
4. CLASSES OF DYNAMIC BEHAVIOR
We are now able to precisely define, in terms of
the system parameters B, p, y, XZ~,the types of
dynamic behavior which may be observed in a
CSTR. We shall make use of the classifications de-
veloped by Poore [34], discuss each class, and then
illustrate our conclusions by numerical examples.
In each of the numerical examples we have solved
Eqs. (3) and (4) with y -+ m in order to produce
the concentration and temperature trajectories.
As can be seen from Fig. 2, the dependence of
the curves S, M, SM on y is slight for y >40;
thus one could expect that these phase plots for
y + m would be very close to those found for y >
40. The parameters for each case are given in Table
1.
Notice that Figs. 2, 4 are divided into 6 regions,
I-VI. We shall discuss each of these regions in turn,
but first let us refer to the caricatures in Figs. 5 and
6. Figure 5 shows a sketch of the various regions in
parameter space surrounded by typical steady state
plots of x,, vs Da for each region. The qualitative
types of phase trajectories possible for each range
of Damkiihler number, Da, are denoted by the let-
ters AB0e.J and pictorially described in Fig. 6
(though we do not explicitly distinguish between a
node or focus). While these types A-J are the total-
ity of what may occur for this system, it is of
interest to see how the portraits metamorphize
from one type to another as Da changes.
Let us now proceed to a detailed discussion of
each region in Fig. 4.
Region I
In this region below both line S and line M, s,, s2,
m ,, ml are all complex and there exists only a single
stable steady state for all values of the Damkohler
number, Da, as shown in Fig. S(a). In addition, it
can be shown]341 that this single steady state is
globally asymptotically stable and has a phase
plane of type A.
Region II
Region II is divided into 2 parts. Region Ha,
above line M and below line S, corresponds to the
case when ml and mz are real and s,, s2 are com-
plex. In region IIb, above line S and below line SM,
~~,~~,m,,m~arerealbutO<m,<s,<s~<m~<1,
so that the “dynamic” stability condition is only
violated when the “slope” condition is also viol-
 Table 1.

Case Sign of
no. (P, B) Region &, & (m,, Da,) (m,, Dad (~1, Da,) (~2, Daa) Da*

1 (0.40,U.O) III s*>o (0~1041,0~03808) (0~8958,OGMS83) (0~9192,0~000601) 0.000602

2 (3.0,22.0) III is<0 (0.2388,0.08435) (0.761 I, 0@4844) (0~9400,0~08911) 0.082
3 (3.0, 19.0) IV 6, < 0, & < 0 (0~3013,0~10307) (0.69867,0.0839) (0.2840,0.1039) (0.9264,0.15460) 0.1028
4 (3.0,16.2) IV 6, <0, 82 <O (04444,0.13223) (0.5555,0.1317) (0.3405,0.1300) (0+050,0~2467) 0.1282
5 (3.0, 14.0) V &<O,&<O (0.4059,0.1650) (0.8797,0.3365)
6 (3.0,ll.O) V S,>O,&<O (0.58017,0.2802) (0.7834,0.4195)
7 (0.74,7.06) VI 6, >0, &<O (04405,0*1318) (0.5595,0.1312) (0.6055,0.1316) (06409,0.1325)

.I - ., - I_ - ., - - .- - ., _,. .,. - . - - .,. . _ .I - - ._, ._ ._ ” ._ _

976 A. UPPAL et al.

__ STABLE s.s

Fig. 5. Typical conversion vs Da plots for the different regions in parameter space.

TYPICAL PHASE PLOTS Region III

CASE
Region III consists of all of parameter space
above the line SM and corresponds to the case
[~;s}[g;~LE] ; g y 1 % ; i ; ;
where 0<ml<s,<mz<s2<1. We shall denote
SADDLE POINT 0 0 I 0 I I I I I
the region to the left of & = 0 as region IIIa and to
K~Sl~~~El”o :, : ; “0 b b Y : the right as region IIIb. Typical plots of x,, vs Da
TOTAL INVARIANTS I 2 3 3 3 4 4 4 5 are sketched in Figs. 5(c) and (d) along with a
ABSCISSA- CMYCENTRATION OROINATE -TEMPERATURE classification of the types of phase plots possible.
To illustrate this region quantitatively we have cho-
sen two specific cases: case 1, B = 15, p = 0.4,
which falls in region IIIa where Sz > 0, and case 3,
B = 22, p = 3.0, which falls in region IIIb where
62 < 0.
Let us begin with case 1. The steady state con-
versions are plotted as a function of Damkiihler
number in Fig. 7. The limit cycles possible are plot-
ted as solid (stable) or open (unstable) dots with the
vertical distance between the dot and the steady
state equal to the maximum deviation of the oscil-
latory conversion from the corresponding steady
state value. Thus the height of the dots above the
steady state curve is an indication of the size of the
Fig. 6. Classes of phase plots possible.
limit cycle. Because & > 0, we know that bifurca-
tion at sZ must be to the right and the limit cycle
ated. Therefore in all of region II, there can be bifurcating from sz must be unstable. Unfortu-
multiple steady states (with only the middle one nately, this is all that the perturbation analysis of
being unstable) only for values of Da corresponding the last section can tell us and the remaining be-
to ml < x,, < m2. In this instance the phase plots are havior must be determined from numerical calcula-
of type E. For all other values of Da, there is a tions. The detailed behavior can best be illustrated
single stable steady state and the phase plots are of by Figs. 7 and 8. For Da =0@006017, just to the
type A. Thus, even though we have not yet proved right of s2, we see in Fig. 8 that there are 3 steady
it, we very strongly conjecture that there can be no states with the upper and lower ones stable and the
limit cycles for parameters lying in region II. upper steady state surrounded by a very thin unsta-

B= 15.0
s;
“2
8\
\ 91 -
\
Z.6. \ z90-
‘\
4-
.2-
ml -
0’
Fig. 7. Steady states and limit cycles for parameters in region Ma, B = 15.0, B = 0.4, y +oo, and
82 >O. (1) Da = 0~0006017.
Fig. 8. Phase plane trajectories, case I, Da = 0~0006017.
ble limit cycle (see blow-up in Fig. 8). This is a
phase plot of type H. Our computations show that
this limit cycle is surrounded by 2 separatrices, one
of which spirals outward to the middle steady state,
and another which passes around the other separat-
rix and goes down to the lower steady state. This
causes the CSTR trajectories from outside the limit
cycle to unwind very slowly from the unstable limit
cycle and ultimately pass very close to the middle
steady state on the way to the lower steady state.
As Da increases still further the unstable limit
cycle increases in size until it encounters the
separatrices which causes the limit cycle to disap-
pear at Da = Da * leaving only 3 steady states and a
phase plot of type E. If the value of Da is decreased
to the left of sz, the unstable limit cycle disappears,
CES Vol. 29. No. 4-F
Continuous stirred tank reactors 977
BETA=0.40
00
92 a2 --- __-_---a
__--
,A--
KX
99 m2l 4,
‘A_ Y.
--__ -.._,
--__ 98
-___ 582 59 60 Do”
--__ Da [I lo-q
---_
--__
--_
.07 .I4 21 .28 .35 42
Do[xlo-‘1
the upper steady state becomes unstable, and there
are no limit cycles. The phase trajectories for this
case are of type C. The formation and growth of a
single unstable limit cycle which disappears by en-
countering the separatrices is a very interesting
new phenomena for this problem which doesn’t
seem to have been noted in previous investigations,
Let us now consider case 2 which falls in region
IIIb. Case 2 has the same type of qualitative be-
havior as case 1 except that SZ< 0. Thus the pertur-
bation analysis predicts bifurcation to a stable
periodic solution for values of Da to the left of sZ.
As in the previous case our numerical calculations
verify these predictions. For Da to the right of sZ,
in Fig. 9, there is only one stable steady state and
the phase plots are of type A ; however, for Da to
the left of s2, a stable limit cycle forms and grows
(type I? phase plot). For values of Da between
0.0843 and 0.08911 (the value at sJ, there is only
one unstable state surrounded by a stable limit
cycle as illustrated in Fig. 10. As Da decreases
below 0.0843, the phase plots become type F, and
there are 3 steady states with the upper one being
unstable and surrounded by an enlarged stable limit
cycle, as illustrated by Fig. 11. Finally as Da is
decreased still further, past Da = Da*, the stable
limit cycle coalesces with the separatrix and disap-
pears leaving only the lower steady state as a stable
steady state. In this case the phase plots are of type
C. Finally as Da decreases further, the reactor pas-
ses from the region of multiplicity and the phase
plots become type A.
The new jump phenomena which occurs for case
2 at Da = Da* would be very striking when ob-
served experimentally; for only a slight decrease in
the Damkohler number would cause a jump from a
large amplitude oscillation, as shown in Fig. 11, to
the lower steady state. Thus it would be of interest
978 A. UPPAL et al.

1 R=22.0 BETA=300

Fig. 9. Steady states and limit cycles for parameters in region IIIb, B = 22.0, p = 3.0, y + ~0,& < 0.
(I) Da = 0.085, (2) Da = 0.082.

to design an experiment along the lines of the con-

*_ B=ZPO Da=0085
ditions of case 2.
BETA-30
Region IV
7- Region IV is that part of parameter space lying
between line M and line SM and to the right of their
intersection. In this region 0 < s, < ml < mz < sz<
6-
1, so that there is bifurcation to periodic solutions
at both s, and sz. Because 6, <O and S2-CO
x"
5- everywhere in region IV, then the direction of
bifurcation will always be to the left, so that there is
a growing unstable limit cycle to the left of s, and a
4- growing stable limit cycle to the left of sz. There are
two possible situations which can occur in this reg-
ion. The first, illustrated in Fig. S(e), shows bifurca-
tion of limit cycles to the left at both sI and s2.
These limit cycles grow until they encounter the
Fig. 10. Phase plane trajectories, case 2, Da = 0.085. separatices and “evaporate”. This type of behavior
may be observed in the top part of region IV, called
IVa. The second type of behavior occurs in the bot-
tom half of region IV, termed IVb. In this instance,
IO-
the limit cycles growing from s, and sz grow until
R=22.0 Do=O.ORZ they coalesce with each other and disappear. This is
RETAz3.0
R- depicted in Fig. 5(f).
The first possibility may be seen quantitatively
by considering case 3: B = 19.0, p = 3.0. For this
6- case the steady states and limit cycles are shown in
x" " Fig. 12. For values of Da to the right of sz, only one
stable steady state exists and the phase plots are of
4-
~
type A ; however, just to the left of sz, a stable limit
cycle develops around a single unstable steady
state as illustrated by Fig. 13 (type B phase planes).
e-
*u As Da decreases still further, the stable limit cycle
continues to grow and as Da enters the region of
multiplicity, the limit cycle encircles 3 unstable
00 .2 4 6 .R 1.0 steady states as shown in Fig. 14 (type G phase
XI planes). If Da is decreased further it passes to the
Fig. 11. Phase plane trajectories, case 2, Da = 0.082. left of s, and the lower steady state becomes stable
 Continuous stirred tank reactors 979

B=l9.0 EETA:3.00

Fig. 12. Steady states and limit cycles for parameters in region IVa, B = 19,0, p = 3.0, y +m, 6, < 0,
& <O. (1) Da = 0.150, (2) Da = 0.103, (3) Da = 0.10282.

and surrounded by an unstable limit cycle. This is a

type J phase plot and is illustrated in Fig. 15. How-
Et= 190 Da=0150
ever, if Da is decreased only slightly more, the un-
BETA = 3.0
7- stable limit cycle approaches both the top side of
the large stable limit cycle, and the separatrix and
both limit cycles disappear, leaving a type C phase
plot. If Da decreased further until the region of
multiplicity is left, then a type A phase plot results.
The coalescence of the two limit cycles in Fig. 15
is another type of new jump phenomena for this
problem which does not seem to have been ob-
served before. This observation seems to imply that
two limit cycles of greatly different size can
coalesce and disappear even if they come together
along only a small portion of the larger limit cycle.
The other interesting possibility, arising in Region
Fig. 13. Phase plane trajectories, case 3, Da = 0.150.
IVb, can be illustrated by case 4, B = 16.2, j3 =

12 -
,2_ B=l90 Da=010282
BETA = 30

,o_ B:l9.0 Da=0.103

IO-
BETA=3.0

8-
B-

x” -

s- x”
6-

4-

0 ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ,
0 .I .2 .3 .4 s 6 .7 .a .9 1.0
XI

Fig. 14. Phase plane trajectories, case 3, Da = 0.103. Fig. 15. Phase plane trajectories, case 3, Da = 0.10282.
980 A.
.127 147 167
187
Fig. 16. Steady states and limit cycles for parameters in region IVb, B = 16.2, p = 3.0, y +m, 6, <O,
62< 0. (1) Da = 0.20, (2) Da = 0.132, (3) Da = 0.131, (4) Da = 0.12823.
3.00. As shown in Fig. 16, there is bifurcation to an
unstable limit cycle at s, and bifurcation to a stable
limit cycle at sz just as in case 3. Thus, for values of
Da to the right of s2 there is only one stable steady
state (type A phase plot), and as Da is decreased
past sz the steady state becomes unstable and a
stable limit cycle grows up around it (type B). The
phase plane trajectory for this case is shown in Fig.
17. As Da is decreased still further, it enters the
region of multiplicity, and the growing stable limit
cycle encircles three unstable steady states. This is
a type G phase plot as shown in Fig. 18. A further
decrease in Da causes the reactor to pass out of the
region of multiplicity so that the stable limit cycle
again encircles only one unstable steady state
IO-
_ B=l62 Oa=O.ZO
BETA=30
B-
Fig. 17. Phase plane trajectories, case 4, Da = 0.20.
UPPAL et al.
247 267
207 227
Da
(again type B) as seen in Fig. 19. If Da is decreased
past s,, the steady state becomes stable and an un-
stable limit cycle grows up around it and inside the
stable limit cycle. The trajectories for this case are
type D as shown in Fig. 20. Finally, if Da is de-
creased only slightly further to Da*, the unstable
limit cycle encounters the stable one, they coalesce
and disappear leaving only a single stable steady
state (type A). This jump phenomena at Da* would
be very pronounced when observed experimentally
because the smallest decrease in Da would cause
extremely large oscillations to disappear com-
pletely. They would reappear again when Da was
increased, if the initial conditions are chosen suffi-
ciently far away from the stable steady state.
10
6=16.2 Da=0.132
Fig. 18. Phase plane trajectories, case 4, Da = 0.132.
 Continuous stirred tank reactors 981

IO
I E=lfl.Z Do=O.l31
8: 16.2

BETA = 3.0
Da = 0.12823

t BETA=3.0
8.

6.
x”

4- x”
4-

2-

2-
'0 .I 2 .3 4 .5 6 3 .E .9 I.0
XI
Fig. 19. Phase plane trajectories, case 4, Da = 0.131.
01 \ J
0 2 4 6 .8 IO
Region V Xl

The part of parameter space above line S, below
line M, and to the right of their intersection is
designated region V. In this region, ml and mZ are
complex so that only one steady state is possible.
However, s, and sz are real so that there is
“dynamic” instability for steady states in the do-
main sI <x,, < sz, and limit cycles bifurcate from s,
and s2. In region V, & < 0 holds everywhere, so that
a stable limit cycle will bifurcate to the left of sz;
however, region V is divided by the line SI = 0 with
SI < 0 in the upper part (Va where an unstable limit
cycle bifurcates to the left of s,) and 8, >O in the
lower part (Vb where a stable limit cycle bifurcates
to the right of s,.) This behavior is sketched in
Figs. 5(g) and (h). To illustrate these points more
clearly, we shall make use of two numerical
examples-case 5, B = 14.0, /3 = 3.0, which lies in
Fig. 20. Phase plane trajectories, case 4, Da = 0.12823.
region Va, and case 6, B = 11, p = 3.0, which lies in
the region Vb.
Case 5 corresponds to a case treated numerically
by Hlavacek[22]. The steady states and limit cy-
cles, shown in Fig. 21, verify the predictions of the
perturbation analysis-an unstable limit cycle
bifurcates to the left of s, and a stable limit cycle
bifurcates to the left of s2. For values of Da to the
right of sz, there is only a single stable steady state
with type A phase plot. Then as Da is decreased
past sz, the steady state becomes unstable and a
stable limit cycle grows around it. This is a type I3
phase plot as illustrated in Fig. 22. As Da is de-
creased past s,, the steady state becomes stable
again and an unstable limit cycle begins to grow in-

8=140 BETA=300
IO

Fig. 21. Steady states and limit cycles for parameters in region Va, I3 = 14.0, p = 3.0, y +=, S, (0,
& < 0. (1) Da = 0.166, (2) Da = 0.162.
982 A. UPPAL et al.

B=llO Da=0320
BETA=30
8~140 Do=O.l66
BETA=3 0

3-

x”
Z-

I-

O
0 L .6 .6 3
XI
.8
I
.9 1.0

Fig. 25. Phase plane trajectories, case 6, Da = 0.320.

side the stable limit cycle. This situation is type D

and is illustrated in Fig. 23. If Da is decreased only
Fig. 22. Phase plane trajectories, case 5, Da = 0.166.
slightly more, the unstable limit cycle grows up and
coalesces with the stable one and they both disap-
pear, leaving only a stable steady state with type A
phase plot.
Case 6, (B = 11.0, p = 3.0) in the lower part of
6=14.0 Da=0 162
BETA=3.0
region V illustrates the sitaution when a stable limit
t cycles bifurcate to the right of s, (cf. Fig. 24). For
8
values of Da to the right of sz and to the left of sI
there is only one stable steady state and a type A
6 phase plot, while for Da values between points s,
2 and sz, the steady state is unstable and surrounded
by a stable limit cycle. This is illustrated in Fig. 25.
4

Region VI
There is one remaining region in parameter space
2
which is so small that it is blown up in Fig. 4 in
order for it to be seen more clearly. This region lies
0
above lines M and S and below line SM, so that
0 .I .2 .3 4 .5 .6 .7 .6 .9 1.0
XI
0 < m, < m2 < s, < sz < 1. Also the region lies en-
tirely to the right of & = 0 and below SI = 0 so that
Fig. 23. Phase plane trajectories, case 5, Da = 0.162. 6, > 0 and & < 0 everywhere in region VI. There-

B=llO BETA = 3.00

IO-

Fig. 24. Steady states and limit cycles for parameters in Region Vb, B = 11.O, p = 3.0, y + m, 8, > 0,
82 < 0. (1) Da = 0.320
 Continuous stirred tank reactors 983

8=7.06 BETA=074

;il,cil-:--_i
1.30 131 I 32 1.33 1.34 I 35 I 36 1.37 I 38 1.39 1.40
Do [i IO-‘]

Fig. 26. Steady states and limit cycles for parameters in region VI, B = 7.06, p = 0.74, y +m, 6, > 0,
& < 0. (1) Da = 0.1322, (2) Da = 0.1317.

fore limit cycles will form only in the region s, < stable steady state is possible (type A). As Da is
x,, < s2 and they will be stable. This situation is decreased past s2, the steady state becomes unsta-
shown in Fig. 5(i) and can be quantitatively illus- ble and a limit cycle grows around it as illustrated in
trated by case 7, B = 7.06, /3 = 0.74, shown in Fig. Fig. 27 (type B). If Da is decreased still further, it
26. For values of Da to the right of sz, only a single enters the region of multiplicity, and then the lower
steady state is stable and the upper (unstable)
steady state is surrounded by a small stable limit

I
B=706 Da= 1322 cycle (type F). This is illustrated in Fig. 28. Finally
BETA = 74
as Da is decreased past s,, the limit cycle disap-
3
pears and the upper steady state becomes stable,
leaving a type E phase plot. Further decreases in
Da cause the system to move out of the region of
multiplicity and have a type A phase plot.

5. DISCUSSION OF OTHER PHENOMENA

Having classified and illustrated the phenomena
we know are possible for this system, let us discuss
OOh, 5 6 7 6 9
I
10
a number of other phenomena, some of which were
Xl suggested by earlier workers.
Fig. 27. Phase plane to trajectories, case 7, Da = 0.1322.
Pseudo limit cycles
A number of previous papers [ 11, 151 have
suggested the existence of pseudo limit cycles
which might be stable from the inside and unstable
from without or vice versa. We note that this does
Bc7.06 Do= ,317
indeed occur for exactly one value of the Dam-

--y’:-“:
BETA= .74 ”

kijhler number (i.e. when the stable and unstable

limit cycles coalesce) for each value of /3 and B
in that part of region V where 8, < 0 and also in
2 2 parts of region IV. However, we find it difficult to
t believe that this singular case is observed often and
suggest that there might be a number of other plaus-
ible explanations for these numerical observations.
For example, two limit cycles (one stable, the other
unstable) quite close together would appear numer-

OO L .b .5
Xl
5
6
.7
ically to be a pseudo limit cycle. Also, the existence
of a stable limit cycle quite close to the separatrix,
as in Fig. I I, would appear under computation as a
Fig. 28. Phase plane trajectories, case 7, Da = 0.1317. pseudo limit cycle. Therefore it would seem best to
984 A. UPPAL et al.

endeavor to explain pseudo limit cycles through NOMENCLATURE

careful checking of known phenomena before in- aoraI, a2 parameters, see Eq. (23)
volving a new hypothesis. A heat transfer area
B dimensionless adiabatic temperature rise
((-AH)c,,/pC,Tf)(EIRTf)
Multiple stable limit cycles concentration
Although no one seems to have found them ex- d specific heat
perimentally or computationally, it is conceivable activation energy
that more than one stable limit cycle might exist for fbZ functions given by Eqs. (3) and (4)
some reactor systems just as multiple steady states F volumetric feed rate
exist. However, we have seen no indication of such h heat transfer coefficient
phenomena for this particular reactor system. AH heat of reaction
ko reaction rate constant for 1st order reac-
tion A +B
6. CONCLUSIONS ml, m2 roots of Eq. (9)
In this paper we have examined the dynamic be- R universal gas constant
havior of the well stirred tank reactor in which a SI, s2 roots of Eq. (23)
first order exothermic reaction is carried out. For t dimensionless time t ‘FA / V
this system we have classified, in parameter space, t’ time
the types of dynamic behavior to be expected. T temperature
Some of the more important conclusions reached V reactor volume
are. XI conversion (caf - cn)/cA,
(1) For those system parameters which violate XZ dimensionless temperature NT-
the “dynamic” stability condition and for which the T)/Trl(E/RT)
“slope” condition is satisfied, limit cycles will al- Da Damkiihler number, Da = (k. em’v/FA)
ways be found for some values of the Damkiihler P dimensionless heat transfer coefficient
number. hAr/ VpC,
(2) The stability character of these limit cycles dimensionless activation energy E/RT,
for Damkiihler numbers close to the bifurcation 6,; parameters, see Eqs. (30) and (31)
point can be determined by an algebraic criterion. A coefficient of recirculation
(3) Limit cycles are seen to disappear by three P density
mechanisms (i) shrinking into a critical point, (ii) 7 residence time in the reactor
coalescence of a stable and unstable limit cycle,
and (iii) interference of a limit cycle with a separat-
Subscripts
rix (period of oscillation becomes infinite).
A species A
It should be stressed that the methods of classifi-
c cooling medium
cation and analysis used here may be readily ex-
tended to more complex systems such as those hav- f feed state
ing other reaction rate expressions, multiple reac-
s steady state
tions, etc. It would seem that this approach could
be useful, for example, in designing experiments
REFERENCES
for the observation of limit cycles, analysing other
[II VAN HEERDEN
C., Ind. Engng Chem. 1953 45
reactor systems, and examining other periodic
1242.
phenomena such as found in biological PI LILJENROTH F. G., Chem. metall. Engng 1918 19
systems [39,40]. We again point out the value of the 287.
approach of Hopf [43] for these problems. A [31 LUSS D., Private communication.
number of such extensions will be treated in forth- [41 SEMENOV N. N., 2. Phys. 1928 48 571.
coming publications. PI BILOUS 0. and AMUNDSON N. R., A.1.Ch.E. JI
1955 1513.
161ARIS R. and AMUNDSON N. R., Chem. Engng Sci.
1958 7 121 132 148.
Acknowledgements-We would like to thank Professor R. [71 GILLES E. D. and HOFMANN H., Chem. Engng
Aris for suggesting Figs. 2, 5 and 6 as a means of com- Sci. 1961 15 328.
pactly summarizing our results. We are also indebted to PI HOFMANN H., Remarks to paper by F. J. Kylstra,
the SUNYAB Computing Center for providing computer Proceedings 3rd European Reaction Engineering
time. Symposium, p. 283, 1964.
 Continuous stirred tank reactors
[91 HOFMANN H., Grundlagen der Chemische Prozes-
sregelung, P. 89. Oldenbourg 1964.
[lo] GILLEsc D., ibid. p. 111:
[ll] WARDEN R. B., ARIS R. and AMUNDSON N. R.,
Chem. Engng Sci. 1964 19 149 173.
[12] BERGER J. S. and PERLMUTTER D. D., Chem.
Engng Sci. 1965 20 147.
[131 GUREL 0. and LAPIDUS L., CEP Symposium Ser.
1965 61 78.
[14] PERLMUTTER D. D., Stability of Chemical Reac-
tors. Prentice-Hall, New York 1972.
[15] DOUGLAS .I. M. and RIPPIN D. W. T., Chem.
Engng Sci. 1966 21 305.
[16] DOUGLAS J. M. and GAITONDE N. Y., lnd.
Engng Chem. Fund. 1967 6 265.
[I71 GAITONDE N. Y. and DOUGLAS J. M.. Paoer 34f.
Cleveland A.1.Ch.E. meeting May 1%9.’ _ _ _ tial Equations. Gordon & Breach 1965.
1181 DORAWALA T. G. and DOUGLAS J. M.,
A.Z.CH.E. JI 1971 17 974.
[I91 HEBERLING P. V., GAITONDE N. Y. and DOUG-
LAS J. M., ibid. p. 1506.
ml LUUS R. and LAPIDUS L., Chem. Engng Sci. 1966
21 159.
VII LUUS R. and LAPIDUS L., A.1.Ch.E. JI 1972 18
1060.
La HLAVACEK V., KUBICEK M. and JELINEK J.,
Chem. Engng Sci. 1970 25 1441.
1231 SCHMITZ R. A. and AMUNDSON N. R., Chem.
Engng Sci. 1963 18 265, 391, 415, 447.
~241 HLAVACEK V., KUBICEK M. and VISNAK K.,
Chem. Engng Sci. 1972 27 719.
~251 FURUSAWA T. and NISHIMURA H., J. them.
Engng Japan I%8 1 180
P61 HYUN J. C. and ARIS R., Chem. Engng Sci. 1972 27
1341, 1361.
985
1271 FURUSAWA T., NISHIMURA H. and MIYAUCKI
T., J. Chem. engng Japan 1%9 2 95.
1281 GILLES E. D., Chei. engng Tech. 1%8 40 469.
~291 HAFKE C. and GILLES E. D.. Mess. Steuem Ren.
1968 11 204.
[301 VEJTASA S. A. and SCHMITZ R. A., A.1.Ch.E. JI
1960 16 410.
1311 RAMIRIZ W. F. and TURNER B. A., A.1.Ch.E. JI
1969 15 853.
[321 BUSH S. F., Proc. R. Sot. 1969 A309 1.
r331 HORAK J., JIRACEK F. AND KRAUSOVA L.,
Chem. Engng Sci. 1971 26 1.
[341 POORE A. B.. Archs ration. Mech. In mess.
r351 GAVALAS G., Nonlinear Digerentiai Equations of
Chemically Reaction Systems. Springer, Berlin 1%8.
1361 FRIEDRICHS K. O., Advanced Ordinary Difleren-
[371 MINORSKY N., Nonlinear Oscillations. Von Nos-
trand, Princeton, N.J. 1962.
1381 Hale J., Orindary Diflerential Equations. Wiley 1%9.
1391 HIGGINS J., Ind. Engng Chem. 59, I%7 No. 5,18.
1401 FEINBERG M. and HORN F. J. M., Paper pre-
sented at New York A.1.Ch.E. meeting, Dec. 1972.
[411 ANDRONOV A. A., GORDON I. I., LEON-
TOVICH E. A. and MAIER A. G., Theory of Bifur-
cations of Dynamic Systems on a Plane. Israel Prog-
ram for Scientific Translations, Jerusalem 1971.
~421 POINCARE H., Sur I’tquilibre d’une mass fluide
animte d’une mouvement de rotation, Acta math.
1885 7 259.
[431 HOPF E., Abzweigung einer periodischen Liisung
eines Differentialsystems. Aus den Berichten der
Mathematisch-Phvsikalischen Klasse der Sachsis-
then Akademie de; Wissenshaften zn Leipzig XCIV,
l-22 1942.