6594 J . Phys. Chem.

1991, 95,6594-6602

Shnple Models of Deterministic Chaos In the Belousov-Zhabotlnsky Reaction

Lisz16 Cyorgyi*.tl*and Richard J. Field*.+

Department of Chemistry, University of Montana, Missoula, Montana 59812, and Institute of Inorganic and
Analytical Chemistry, Eatuos Urcind University, P.O.B. 32, Budapest- I 12, H - 1518, Hungary
(Received: April 29, 1991)

A recently developed, chemically accurate, 11-variable model of the Belousov-Zhabotinsky reaction previously has been shown
to reproduce essentially all details of the low-flow-rate complexity and deterministic chaos observed when the reaction is
run in a continuous-flow, stirred tank reactor. However, this model is large enough that extracting the skeletal source of
the complexity in its dynamic structure was not possible. That is done here by reducing the number of variables in the model
by means of rate sensitivity analysis as well as the conventional methods of chemical kinetics, e.g., the rate-determining step,
equilibrium, and quasi-steady-state approximations. A 7-variable model retaining mass-action kinetics form is obtained first.
It is then reduced to two 4-variable models of nonpolynomial form, which may finally be reduced to a 3-variable model.
All models with four or more variables reproduce the major features of the experimentally observed chaos at low flow rates.
Agreement with experiment is less good with the 3-variable model. The 4-variable models also are able to reproduce many
features of the experimentally observed complex oscillations and chaos at high CSTR flow rates that previously has not been
possible in a chemically accurate model. The source of complexity at both high and low flow rates is found in the complex
interaction of two frequencies, one related to a negative feedback loop solely within the homogeneous kinetics of the BZ
reaction and the other related to the coupling of a feedback loop involving BrMA, a product of the reaction, with the CSTR
flow.

Introduction reproduces the vast majority of the observed low-flow-rate be-

Oscillating chemical reactions's2 are the most important ex-
amples of the presence of nonlinear dynamic laws3 in chemical
systems. They exhibit sustained oscillations in a closed system,
complex oscillations and chaos in a well-mixed, continuous-flow,
stirred tank reactor (CSTR), and traveling or stationary con-
centration waves in an unstirred medium. These reactions, though
very complex, are relatively easy to study experimentally, and often
their dynamic structure can be understood in some detail. Thus
they are used as prototypes for biological and physical systems
of similar complexity which are not as accessible to direct in-
vestigation. We are concerned here with the appearance and
modeling of temporal chaos in the Belousov4-ZhabotinskyS (BZ)
reaction.
The BZ reaction is the most investigated oscillating chemical
reaction. It is the simultaneous oxidation and bromination of an
organic compound (most often malonic acid, CH2(COOH), by
BrOy catalyzed by a metal ion catalyst (often Ce(III)/Ce(IV)).
Temporal chaos is observed when the BZ reaction is run in a
CSTR under appropriate conditions. The aperiodic oscillations
result from the internal dynamics of the system and not from
external noise. A major characteristic of this behavior is the
exponential separation of trajectories, which means that two
systems starting from arbitrarily close initial conditions will
eventually evolve away from each other. Thus long-term prediction
of the behavior of these systems is impossible, much as in the case
of weather prediction.
Experimental evidence for BZ-CSTR chaos dates back to work
by Schmitz et ale6in 1977. Several chaotic areas in the CSTR
parameter space (temperature, flow rate, feedstream concentra-
tions) have been discovered and described7-I8since then. The mmt
detailed and best documented experiments are those performed
at the University of Texas at AustinI3-l8 at low CSTR flow rates,
where most of the complexity occurs in the neighborhood of a
bifurcation between oscillations and a r e d u d steady state. There
have been several efforts to model this phenomenon.'*% Although
chaos was quickly found, the models used did not reflect new
developments'a in mechanistic understanding of the BZ reaction,
and the properties of the calculated chaos often did not agree well
with experiments. We have recently introducedz7an 1 I-variable
model of the BZ reaction with three adjustable parameters which
'To whom correspondence should be addressed.
'University of Montana.
E6tv6s LMnd University.
haviors assuming the experimental conditions and reasonable
parameter values. Although some interpretation of how the o b
served complexity arises was givenz7 in terms of two-frequency
coupling, it is difficult to analyze that large a model. Thus it is
desirable to extract those parts of the model responsible for the
observed complexity.
We show here that this 1 1-variable model can be simplified
to yield a 7-variable, mass-action model based on elementary
(1) Oscillations and Traveling Waves in Chemical Systems; Field, R. J.,
Burger, M., Eds.;Wiley-Interscience: New York. 1985.
(2) Gray, P.; Scott, S. K. Chemical Oscillations and Instabilities. Non-
linear Chemical Kinetics; Clarendon Press: Oxford, U.K.,1990.
(3) Field, R. J.; Schneider, F. W. J. Chem. Educ. 1989, 66, 195.
(4) Bclousov, B. P. In Sbornik Referatou po Radiatsionnoi Meditsine;
Medgiz: Moscow, 1958; p 145 (in Russian).
( 5 ) Zhabotinsky, A. M. Eiofnika 1964, 9, 306 (in Russian).
(6) Schmitz, R. A.; Graziani, K.R.; Hudson, J. L. J . Chem. Phys. 1977,
67,3040.
(7) Hudson, J. L.; Hart, M.; Marinko, D. J . Chem. Phys. 1979,71, 1601.
(8) Hudson, J. L.; Mankin, J. C. J. Chem. Phys. 1981, 74,6171.
(9) Roux, J. C.; Rossi, A.; Bachelart, S.; Vidal, C. Phys. Left. 1980, 77A,
391.
(IO) Pomeau, Y.;Roux, J. C.; Rossi, A,; Bachelart, S.;Vidal, C. J . Phys.
Lett. 1981, 42, L271.
(11) Argoul, F.; Arneodo, A.; Richetti, P.; Roux, J. C. J . Chem. Phys.
1987, 86, 3325.
(12) Ibison, P.; Scott, S. K. J . Chem. Soc.,Faraday Trans. 1990,86,3695.
(13) Roux, J. C.; Turner, J. S.; McCormick, W. D.; Swinney, H. L. In
Nonlinear Problems: Present and Future; Bishop, A. R., Campbell, D. K.,
Nicolaenko, B., Eds.; North-Holland: Amsterdam, 1982; p 409.
(14) Roux, J. C.; Simoyi, R. H.; Swinney, H. L. Physica D 1983,8D, 257.
(1 5 ) Coffman, K. G.; McCormick, W. D.; Noszticzius, Z.; Simoyi, R. H.;
Swinney, H. L. J. Chem. Phys. 1987,86, 119.
(16) Noszticzius, Z.; McCormick, W. D.; Swinney, H. L. J . Phys. Chem.
1987, 91, 5129.
(17) Noszticzius, Z.; McCormick, W.D.; Swinney, H. L. J . Phys. Chem.
1989, 93, 2796.
(18) Coffman, K.G. Ph.D. Thesis, University of Texas at Austin, Austin,
---.
TX. 1986.
--
(19) Richetti, P.; Roux, J. C.; Argoul, F.; Arneodo, A. J . Chem. Phys.
1987, 86, 3339.
(20) Turner, J. S.; Roux, J. C.; McCormick, W.D.; Swinney, H. L. Phys.
Lett. A 1981, 85A, 9.
(21) Ringland, J.; Turner, J. S. fhys. Lett. A 1984, IOSA, 93.
(22) Barkley, D.; Ringland, J.; Turner, J. S. J . Chem. Phys. 1987, 87,
7x13
(23) Lindberg, D.; Turner, J. S.; Barkley, D. J . Chem. Phys. 1990, 92,
3238.
(24) Ibison, P.; Scott, S.K . J. Chem. Soc., Faraday Trans. 1991,87,223.
(25) Field, R. J.; Fdrsterling. H.-D. J . Phys. Chem. 1986. 90, 5400.
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(27) Gybrgyi. L.; Rempe, S. L.: Field, R. J. J . Phys. Chem. 1991, 95, 3159.

0022-3654/91/2095-6594$02.50/0 0 1991 American Chemical Society

Deterministic Chaos in the BZ The Journal of Physical Chemistry, Vol. 95, No. 17, 1991 6595

TABLE 1: Model A'

- -+ +
AI. HOBr + Br- + (H+} Br2 + (HzO)
rate constant
.

6.OE+8 M-' 8'

ref
46
+
+ --
A2. Br2 (H20) HOBr Br- (H+]
A3. Br- H B r 0 2 + (H+} 2HOBr
2.0 s-1
5.2E+5 M-I s-I
46
25, 26

- - -
+
A4. Br- (BrO,-} + [2H+} HOBr + HBrO, 0.01352 s-' 25, 26
A5. HOBr + HBrO, Br- + [BrO,-} + (2H+) 3.2 M-' s-I 25
A6. 2HBr02 [BrO,-} + HOBr + [H+} 3.OE+3 M-' S-I 25

A8. 2Br0; + -+ -+
A7. {BrO,-} + HBr0, + (H+} ZBrO,' + [HzO}
(H,OJ (BrO,-} HBr02 + [H+}
0.858 s-'
4.2E+7 M-l S-I
25, 26
25
A9. Ce(1II) + BrO;
+
- - (H+} HBr02 + Ce(IV)
A10. HBr0, Ce(1V) Ce(1II) + BrO,' + {H+}
1.612E+4 M-I s-'
7.OE+3 M-' s-I
25,26
25, 26

+
A12. MA HOBr -- ++
A1 1. MA + Br2 BrMA + Br- + (H')
BrMA (H,O}
40.0 M-I s-I
8.2 M-I s-I
47
48
A13. MA + Ce(IV)

- -+ MA' Ce(I1I) + {H'}

A14. BrMA + Ce(1V) Ce(1II) + Br- + [products)
0.3c M-I s-I
30.V M-I s-l
27
27

+ -
+
A15. MA' BrMA MA Br- + (products} 2.4E+4' M-I s-I 27
A16. MA'
A17. MA' + HOBr
A18. 2MA'
- +
Br2 BrMA Br'

- -+ + + Br' + (products)
MA {products}
1.5E+8 M-' s-l
1.OE+7 M-I s-l
3.OE+9 M-I c1
26,49
26, 49
27, 50
A19. Br' + MA Br- MA' [products} 1.OE+5 M-' s-I 26
= 55 M, [BrOc] = 0.1 M, [H+]
'The values [H20] = 0.26 M are included in the appropriate rate constants. The mixed-feed concentrations are
[MA]& = 0.25 M, [Ce(III)],,,f= 0.000833 M. These are exactly the experimental conditions of refs 14-18. E+n XlO". 'MA CH,(COOH),;
MA' 'CH(COOH),; BrMA = BrCH(COOH),. 'Adjustable rate constant.

reactions as well as two different 4-variable models and a still

chaotic 3-variable model resulting from further reduction of the -5.0 1
7-variable model. The 3- and 4-variable models are not of
mass-action (Le., polynomial) form.
Simplification of the 11-Variable Model
-I
-5.5

m
I

9-Variable Model. The original 11-variable model is shown in cn

-
Table I and is referred to as model A. It is effectively only a
10-variable model as [Ce(IfI)] + [Ce(IV)] is a constant. However,
-6.0

in order to retain the mass-action form of the equations, we do

not use this relationship until the final stages of the simplification
process.
The reaction-rate sensitivity method developed by Turlnyi and
c o - ~ o r k e r s ~was
* * ~used
~ to analyze the chaotic behavior of the
model and to identify unimportant reaction steps. The simpli-
fication was carried out at low flow rates using the chemical
conditions specified in Table I. The matrix of log-normalized
partial derivatives of the right-hand sides of the set of differential
equations resulting from the chemical model with respect to the
rate constants (F = (8 Inf;/8 In kj) is analyzed at particular times.
It is possible by principal component analysis,30 Le., by looking
a t the eigenvalues and eigenvectors of FTF, to identify those
reactions important to the observed behavior at a particular time.
A short summary of this study follows. A more complete de-
scription of this and other sensitivity methods is given in a recent
review by T ~ r l n y i . ~ '
1. A flow rate was chosen where the system shows chaotic
behavior. It was assumed that, if a reduced system reproduces
this behavior at nearby flow rates, then the other chaotic and
complex-periodic regimes also would appear. The flow rate chosen
is kf = 3.06 X IO4 s-I.
2. SO called *redundant were identified by leaving
out one by one the consuming and then both the consuming and
producing reactions of each component in the model. A component
was considered to be "redundant" if either aperiodicity or the
complex oscillations remained after these deleticys. Only one
species, Br', was found to be redundant.
3. Appropriate time points were chosen for the principal
component analysis of a simulation that had been run long enough
for transients to decay and the strange attractor to be approached.
Figure 1 shows a 2500-s-long time series with 59 points at different
phases of the oscillations marked for principal-component analysis
of P F .
~~~ ~~
5000 5500 6000 6500 7000 7500
time /s
Figure 1. Observation points on the log [Br-] time series for reaction-
rate-sensitivity analysis of model A.
4. The eigenvectors and eigenvalues of FTF were evaluated at
each point. The eigenvectors represent reaction groups, and the
corresponding eigenvalues indicate the importance of that reaction
group at that time. Each point was analyzed separately. By
analogy to earlier work with this method,30reaction groups with
eigenvalue <0.01 were assumed to be unimportant. Reactions
within these groups were ignored. Furthermore, reactions in an
important reaction group with eigenvalue 20.01 were ignored if
their corresponding eigenvector element was less than 0.2. Re-
actions A2, A5, A6, A12, and A17 (see Table I) could be ignored
at all 59 time points and are considered to be unimportant in the
mechanism.
5 . The unimportant reactions were removed from the mech-
anism, which still showed complex oscillations. However, they
were very different from those obtained with model A because
the importance of reaction A6 at the peak of [HBr02] was ov-
erlooked. Reaction A6 was returned to the mechanism, and
complex periodic oscillations consisting of a period-doubled, 3-
large, 1-small sequence, which exist in model A at a nearby flow
rate, reappeared.
6. Principal component analysis will not fast reactions
of redundant species such as Br' to be unimportant. However,
it was shown a t stage 2 that removing them does not affect the
qualitative behavior of model A. Thus reactions A16 and A19
also are ignored. This effectively removes Br' from the mechanism
and reduces its dimension by one.
This concludes the application of rate sensitivity analysis. The
normal approximations of chemical kinetics must now be used

(28) Turinyi, T.; Birces, T.; Vajda, S. Inr. J . Chem. Kiner. 1989,21, 83.
(29) TurBnyi, T. New J . Chem. 1990, 14, 795. for further simplification. Initially we note that [CH2(COOH)2]
(30)Vajda, 5.;Valki, P.;Turhyi, T.Inr. J . Chem. Kinet. 1985, 17, 5 5 . changes very little in the CSTR. Thus its concentration is assumed
(31) TurBnyi, T. J . Marh. Chem. 1990, 5, 203. to be constant and included in the rate constants of reactions A1 1
6596 The Journal of Physical Chemistry, Vol. 95, No. 17, 1991 GyBrgyi and Field

TABLE II: Model Bb

I
I
simulation
I
-- +
~ 0

rate constant i - quasi-steady-state assumption

+
B1. HOBr + Br- (H+) Br2 (H20) 6.OE+8 M-l s-I

-
-7.0
B2. Br- + HBr02 + (H+) 2HOBr 5.2E+5 M-I s-I

-
B3. Br- + (Br03-) + (2H+) HOBr + HBr0,

-
B4. 2HBr02 (Br03-J+ HOBr + (H+)
0.01352 s-l
3.OE+3 M-I s-I
BS. (Br03-I + HBr02 + IH+I 2Br0,' + 1H20) 0.858 c1 - -8.1

-
B6. 2Br0,' + 1H201 IBr03-) + HBr02 + IH'I
h

4.2E+7 M-I s-l I

-
+
0
B7. Ce(ll1) + BrO,' + (H*) HBr02 + Ce(1V) 1.612E+4 M-l s-l 0

B9. (MA) + Br, --+

B8. HBr02 + Ce(1V) Ce(ll1) + BrO2' + (H+J 7.OE+3 M-I s-I
BrMA Br- + (H+) 40.0 [MA]
2
I
u
-8.4

-
B10. (MA) + Ce(lV) MA' + Ce(II1) + (H+) 0.3c [MA] s-l
I

m
-0
+
B11. BrMA Ce(1V) Ce(lI1) Br- + +
30.W M-I s-' -0.7

- -+ . . . -. . . . . .
(products)
+
B12. MA' BrMA (MA) + Br- + (products1 2.4E+4' M-I s-I .I
B13. 2MA' (MA) [products) 3.OE+9 M-l s-l -9.01 ' , , , , I , I , , , I
70000 70500 71000 71500 72000 72500 73000
9-variable model derived from model A. [H20] = 55 M, [Br- time /s
03-]= 0.1 M, [H+] = 0.26 M are included in the appropriate rate
constants. bMA = CH2(COOH),; MA' p 'CH(COOH),; BrMA = Rgwe 2. Comparison of simulated and estimated log [MA'] time series.
BrCH(COOH),. e Adjustable rate constant. The simulation (circles) is based on model C with k, = 3.17 X lo-' s-I,
while the approximation (solid line) is that shown in eq 2 using values
TABLE III: Model CO of the other variables taken from the simulated results.

CI. Br- + HBr0, + (H+) 2BrMA - rate constant

5.2E+5 M-Is-l
the BZ reaction (Br-, H B Q , Ce(1V)) with the addition of BrMA
are sufficient to reproduce complex oscillations and chaos. This
+
-+
C2. Br- (BrOf) (2H+) BrMA HBr0, + 0.01352 s-l

- --+
+
means that the next step in the simplification process should be
C3. 2HBr0, IBr0;l + BrMA + IH+I 3.OE+3 M-I s-l a model based on these four species derived by developing algebraic
C4. (Br03-)'+ HBr02-+ (H+) 2B&,"+ (H20) 0.858 expressions for the concentrations of Ce(III), malonyl radical
+
C5. 2BrO2* (HzO) (Br03-J HBr0, (H+) + 4.2E+7 M-l s-l

- -
C6. Ce(ll1) + BrO,' + (H') HBr0, + Ce(IV)
C7. HBr0, + Ce(lV) Ce(II1) + BrO,' + (H+)
1.612E+4 M-l s-I
7.OE+3 M-'
(MA'), and Br02'.
Cerous ion (Ce(II1)) is easily removed from model C by the

+ - +
C8. (MA) + Ce(IV) MA' + Cc(II1) + (H+I
C9. BrMA Ce(1V) Ce(l1I) Br- +
0.3' [MA] s-I
30.W M-l s-!
algebraic relationship describing the conservation of cerium atoms,
eq 1, where [Ce],,, is the mixed-feed concentration of Ce ions.

- -+ + +
(products)
+
CIO. MA' BrMA (MA) Br- (products) 2.4E+4CM-l s-I
C1 1 . 2MA' (MA) (products) 3.OE+O M-I s-I
" A 7-variable chaotic model derived from model B. [H20] = 55 M,
[BrO,-] = 0.1 M, [H+] = 0.26 M are included in the appropriate rate
constants. bMA CH,(COOH),; MA' = 'CH(COOH),; BrMA
BrCH(COOH),. CAdjustablerate constant.
and A13. This further reduces the dimension of the mechanism
by one.
The result of this first stage of simplification is the 9-variable,
13-reaction model shown in Table I1 as model B. It exhibits
chaotic behavior similar to that in model A at k f = 3.1 X lo4
s-1.
7-Variable Model. Further reduction of the model cannot be
done by removing individual reactions. It instead must be done
by looking a t relative time scales and by taking advantage of
equilibrium, rate-determining step, and steady-state approxima-
tions. Two more components, Br2 and HOBr, can be readily
eliminated in this way because the reaction between Br- and
HOBr, (Bl), is diffusion controlled, and the bromination of
malonic acid (MA) by Br2 resulting in bromomalonic acid
(BrMA), (B9), is fast at the large [MA] used in the BZ reaction.
The steps which produce or consume Br2, (Bl) and (B9), can be
ignored by assuming that there is always enough Br- present to
convert HOBr to Br2 and replacing HOBr with BrMA in reactions
B2, B3, and B4. Two specific features of model B are also used
here. One is that (Bl) and (B9) are the major Br2 producing and
consuming steps. The other is that HOBr is consumed only in
reaction B 1.
The result of this simplification is model C shown in Table 111.
It is a 7-variable, 1 I-reaction model which shows behavior very
similar to model A at flow rates shifted slightly toward higher
values. For example, model C is periodic at kf = 3.10 X lo4 s-I
with a 2I (2 large and 1 small peak per period) pattern. It is
chaotic at k f = 3.17 X IO4 s-l and shows a periodic 3' pattern
at kf = 3.2 X IO-' s-'. Model C is the last in the series presented
here which can be treated as a mechanism of elementary reactions
following the law of mass action.
4-Variable Models. Analysis2' of the behavior of model A
suggests that the variables of the classic Oregonator model3*of
[Ce(III)] = [Ce],, - [Ce(IV)] (1)
A quasi-steadystate assumption (QSSA) can be made for [MA']
as it is a radical species present at a relatively low concentration.
The effect of the CSTR flow on the QSSA values of [MA'] and
other species present at low concentrations may be ignored com-
pared to the rapid rate of the reactions holding their concentrations
low. The QSSA value of [MA'] at kf = 3.17 X l o ' s-' calculated
from eq 2 is compared in Figure 2 with that calculated from model
C. The values of [Ce(IV)] and [BrMA] in eq 2 were obtained
[MA'lQss = {-kc1o[BrMAI + ((kclo[BrMA1)2 +
8kcskc1 I [ C e ( w 1 ) 0 ~ 5 1 / ( 4 / ~Ic) l (2)
from the simulation with model C. Agreement between the two
values of [MA'] is very good, indicating that at these flow rates
the QSSA is valid and the effect of the CSTR flow on [MA']
is indeed negligible.
There are two approximations allowing removal of Br0;. The
first is based on the results of Field and FBrsterlingZ5indicating
that reaction C 4 is usually at equilibrium under normal BZ
circumstances. Thus the rate-determining step of the sequence
+
OS(C4 + C5) + (C6 C7) is (C6) in the forward direction and
(C7) in the reverse direction. The value of [BrO,'] is estimated
by assuming that Br02' is always in equilibrium with B r O r and
HBr02, yielding eq 3, which is inserted into the rate equation in
[Br02'1 EQ = IkC4/kC5 [HBr021 (3)
terms correspending to reaction C6. It is clear, however, from
the comparison shown in Figure 3 of the values of [Br02*] cal-
culated from model C and from eq 3, that the equilibrium as-
sumption overestimates [Br02*],especially when it is very low.
The second method of approximating [BrO,'] is the QSSA
ignoring flow terms, as was done to approximate [MA']. This
results in eq 4, where [Ce(III)] is obtained from the Ce(III)/
[BrO,']qss = (-kc6[Ce(III)] + {(kc6[Ce(III)])* +
~kcs[HBrOzl(2kc4+ ~ c , ~ ~ ~ ~ ~ ~ ~ I(4)~ l o ~ S l /
(32) Field, R. J.; Noyes, R. M. J . Chem. Phys. 1974, 60,1877.
Deterministic Chaos in the BZ The Journal of Physical Chemistry, Vol. 95, No. 17, 1991 6597

TABLEIV ModclW

+
D1. Br- HBr02 (H'J + -- +
2BrMA

-.
+
D2. Br- + (Br0c-J (2H+) BrMA HBr02
D3. 2HBr02 BrMA
-
-
D4. 0.SHBr02 + (Br03-J+ (H+J HBr02 + Ce(1V)
--
DS. HBr02 + Ce(1V) 0.5HBr02
D6. Ce(1V) {MA\ +
-
+
D7. BrMA Ce(1V) Br-
D8. BrMA Br-
OChemical scheme of the two 4-variable models (depending on whether eq 3 or 4 is used for [BrO,'],) derived from model C. In this model
Br03-, H+ and MA have fixed concentrations. The differential equations for these models are given in the text. MA = CH,(COOH),; MA' 1
'CH(COOH),; BrMA = BrCH(COOH)2. [MA'], and [BrO,'],, are defined in the text. CAdjustablerate constant.

constant concentrations in the CSTR of [BrO;], [H+], and [MA]

equilibrium assumption are their mixed-feed concentrations, and since [Ce(IV)lmr= 0
~ quasi-steady-state assumption M here [Ce], = [Ce(III)]mf.
-6.4 7 Although the QSSA gives a better approximation of [BrO,']
than does the equilibrium assumption, it is worthwhile to inves-
tigate both approximations because the equilibrium assumption
-6.9 leads to significantly simpler differential equations than does the
-0" QSSA. Both 4-variable models reproduce the experimental be-
havior very well, as discussed in the Results section.
I
& -7.4
$Variable ModeL An effort was made to reduce the &variable,
0)
- chaotic model to three variables in the same way that the 3-
-7.9
variable OregonatoS2 model may be r e d ~ c e to d ~two
~ variables
~
by appropriately scaling the differential equations so as to identify
and remove a fast variable. Model , D was used in order to obtain
-8.4
the simplest possible set of differential equations, and scaled by
70000 70500 71000 71500 72000 72500 73000 using the new variables defined below.
time /s
x = [HBrO2]/X0; y = [Br-]/Yo; z = [Ce(IV)]/Zo;
Figure 3. Comparison of simulated and estimated log [BrO;] time series. Y = [BrMA]/Vo; T = t / T ,
The simulation (circles) is based on model C at kf = 3.17 X lo-* s-l, while
the approximations are those shown in eq 3 (dot-dash line) and in eq 4 where
(solid line). The values of the other variables needed in eqs 3 and 4 are
taken from the simulated results.
Xo = (kM[Ce],,,)/(lOkDl) z= 2.6 X 10" M
Ce(IV) mass balance. Figure 3 shows that there is very good
agreement between values of [BrO,'] calculated from eq 3 and YO (kDd[Ce],o,)/(4kDl) C 6.5 X IO" M
model C. This means that eq 5 is a valid relationship among
reaction rates in model C. Two 4-variable models of identical Zo = [Ce],o,/30 2.8 X M
(rC6 - rC7) 0*5(rC4- rCS) (5) Vo = (4[Br03-][H+][Ce]t,,,)/[MA]2
1.39 X M
structure thus can be obtained from the differential equations
describing the behavior of model C. The first results from the To = (kwk$4[Br0;][H+]2)-1 = 3020 s
relationship given by eq 5 along with eqs 1, 2, and 4, and the
second results from simple substitution of eqs 1, 2, and 3. Both k c 4 = kC4/([Br03-][H+]) = 33.0 M-2 s-I (10)
models are derived from the chemical mechanism in Table IV and
are referred to as model ,
D or model
,,D depending on whether (The numerical values were calculated by using the conditions
the equilibrium or the QSS assumption is used to estimate [BrO,']. in Table I.) Substitution of these definitions into eqs 6-9 leads
The differential equations of model D are as follows: to a scaled model. ,D
The fast variables were identified by substituting into q 10
d[Br-]/dt = -kD1[H+][Br-][HBrO,] - appropriate values of the rate constants and reactant concentra-
+
kD2[B a r ] [H+I2[Br-] kD7[Ce(IV)][BrMA] + tions. The two fastest variables turn out to be x and y, as ex-
kD8[MAolQSS[BrMA1+ kd[Br-lmf - [Br-l) (6) from the simple Oregonator model. A fast variable
is eliminated32-35by setting its time derivative to zero to obtain
d[HBrO,]/dr = -kDl[H+][Br-][HBr02] + an algebraic relationship between it and other variables that is
k~2[BrO3-][H+]2[Br-] - substituted into the remaining differential equations. This is
~ 0.5k~[H+I([Cel,, - [Ce(IV)I)[Br02'],t -
2 k ~ , [ H B r 0 2 ]+ essentially the QSSA. The resulting lower dimensional system
O . ~ ~ D ~ [ H B ~ O ~ ] [ C+~ (kl([HBrO2lmr
IV)] - [HBrO,]) (7) will behave similarly to the original ODE'S if the fast variable
has a relaxation time much faster than the characteristic time
d[Ce(IV)l/dr = kD4[H+l([Cel,o, - [Ce(IV)I)[BrO,'l,t - of the overall reaction. The mathematical theorem on which this
k~s[HBfl21[ce(rv)l - k ~ d M A l [ C e ( W l- assumption is based is due to T i k h ~ n o v . ~It~ is
. ~clear
~ from eqs
k ~ d C e ( W l [ B r M A l+ kd[Ce(IV)l,r - [Ce(IV)l) (8) 6-9 that x (scaled [HBr02]) cannot be easily eliminated because
d[BrMAl /dt = 2kD1[H+l[Br-] [HBr021 + kD2[Br03-] x
[H+12[Br-l + k ~ ~ [ H B r 0 -2 ]k~~ t [ c e ( I V )[BrMA]
] - (33) Tyson, J. In Nonlinear Phenomena in Chemical Ktnetics; Vidal, C.,
~ D ~ [ M A ' ] ~ [ B ~+M kd[BrMAImf
A] - [BrMA]) (9) Pacault, A., Eds.;Springer-Verlag: Berlin, 1981; p 222.
(34) Tyson, J. J . Phys. Chem. 1982,86, 3006.
The subscript mf refers to the mixed-feed concentration of that (35) Heineken. F. G.; Tsuchiya, H. M.; Ark, R. Math. Biacd. 1967, I ,
95.
component, which is assumed to be zero for variable species in (36) Tikhonov. A. N. Mar. Sb. 1952,31, 575.
model D. [Br02']crr is either [BrO,'IEQ or [BrO2'Iw. The (37) Vasil'eva, A. B. Russ. Math. Surveys 1963, 18, 13.
6598 The Journal of Physical Chemistry, Vol. 95, No. 17, 1991 Gy6rgyi and Field
-4.80 -4.80 7
...I.,.,.,l.ll.;l..,:,.,1p.1q,...,., I....,.. :a
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flow rate /E-' flow rate /s-'

Figure 4. A bifurcation diagram obtained from simulations based on Figure 5. Bifurcation diagrams obtained in simulations with model,D
model DW at flow rates <2.0 X 104s-l. The log [Ce(IV)J values are at flow rates higher than 2.0 X IO4 s-l. The log [Ce(IV)] values are
intersectionsof the trajectory with the Poincar€ plane perpendicular to intersections of the trajectory with the same Poincart plane as in Figure
the [Br-] axis and containing the point: ([Br-] = 2.12540 X IOd M, 4. Results are shown when gradually increasing (A) or decreasing (B)
[ H B Q ] = 1.22126 X lo-' M,[Ce(IV)] = 2.80401 X IO4 M,[BrMA] the CSTR flow rate. Differences between parts A and B suggest bista-
= 1.205 64 X IO-' M) when [Br-] is increasing. Results are shown when bility in that region. Periodic behavior is indicated when only few in-
gradually increasing (A) or decreasing (B) the CSTR flow rate. Dif- tersections are visible at a particular k~ while many intersections indicate
ferences between parts A and B suggest bistability in that region. Per- chaos.
iodic behavior is indicated when only few intersections are visible at a
particular kl, while many intersections indicate chaos. The system is in its reduced steady state for the lowest flow
rates used. A supercritical Hopf bifurcation giving rise to
a fourth-order equation has to be solved. On the other hand, dy/d.r small-amplitude, sinusoidal oscillations is encountered initially
is linear in y; thus yQss = flx,y,v) is easily calculated: upon increasing the flow rate. These oscillations evolve to mix-
ed-mode (large and small oscillations) behavior at kf = (1.37 f
YqSS = {(kD7ZOVO/YO)Zv + (kC10VO)/(4kCllYO) 0.01) X lo4 s-l. There is bistability in this region between
(4kcioVo)v + ( ( ~ c I o V O+) (~~~ ~ C I I ~ D ~ [ M A+I Z ~ ) ~mixed-mode
) ~ ~ ~ ) ~and sinusoidal oscillations, just as in model A, and
(kr[Br-lmr)/Yo)~/((k~2[BrO,-l[H+l2) + ( ~ D [H+Ixo)x
I + krl in the experimentsn3* There are more than 10 small oscillations
(11) between two large excursions in the mixed-mode patterns. Model
A shows similar behavior, while experimentally'* there are only
Model ,E is obtained by substituting y q into ~ the
~ scaled dx/d.r about 5. Periodic and chaotic windows with a decreasing ratio
dz/dr and dv/dr equations of model D,. It is a 3-variable model of small to large oscillations are encountered as the flow rate is
of the BZ reaction derived from the chaotic model A. increased further. Figure 5 shows that at kf values between 2.3
X lo" and 2.8 X lo" PI there are several bistable regions between
Results two periodicities of the same large/small ratio, but one having
Model B and model C were not studied in any detail as the twice the number of peaks as the other (e.g., 24 vs 12). This
4-variable models reproduce the experimental behavior very well. phenomenon also was seen in model A.
In the following we discuss model DW, model DE,, and finally The high-flow-rate end of the complexity also is very similar
model EE . to that of model A. The periodic windows contain limit cycles
Model 8- Low Flow Rates. The phenomena exhibited by with more than one large-amplitude oscillation per period as the
model DQ, at low CSTR flow rates were studied first. The flow rate is increased from the 1' periodic window. There are
chemical conditions used were the same as those of the Texas chaotic regimes between the periodic windows. Three of the
experiments:Ic1* [Br0<Inf = 0.1 M, [H+],,,, = 0.26 M, [MAImr strange attractors in this region are shown in Figure 6, along with
= 0.25 M, [Ce(lII)],,,r = O.OOO833 M. Model D, behaves like their corresponding return maps39created from the log [Ce(IV)]
model AZ7and the experimental system in essentially every respect. PoincarE plane crossings in Figures 4 and 5. The maps are very
Figures 4 and 5 show the bifurcation structure of model DqSSas similar to those obtained in the Texas experiments using purified
the log [Ce(IV)] values (ordinate) when the trajectory crosses MAI5 and almost identical with those resulting from model A.
a threedimensional hyperplane (Poincarg plane) for different flow Some of the limit cycles in the major periodic windows lose their
rates (abscissa). Typically, 250-300 crossings are recorded at stability via a cascade of period-doubling bifurcations. We did
a particular flow rate. Periodic behavior is indicated by the not attempt to investigate in detail the transitions from periodicity
appearance of a small number of points at a particular flow rate, to chaos. One difference between model DW and model A is
and chaotic behavior is indicated by the appearance of a large that in the 4-variable model a periodic window with a 5' limit cycle
number of points. High log [Ce(IV)] crossings result from appears which was not seen in the simulations with the 1 1-variable
large-amplitude excursions, while crossings at low log [Ce( IV)] model. At the high-flow-rate end of this complexity regular, lo
values result from small-amplitude oscillations. Parts A and B
of Figures 4 and 5 were recorded by gradually increasing and (38) Noszticzius, 2. Personal communication.
decreasing the flow rate, respectively, in order to determine (39) We use the term "map" locwely here and elsewhere since we do not
whether bistability exists in the model. require these curves to be single valued.
Deterministic Chaos in the BZ The Journal of Physical Chemistry, Vol. 95, No. 17, 1991 6599
A kl=l . 6 3 ~ - 3 S-’
kl=2.96s-4 s-’
-5.00 7 A
-k -5.35

-5.85
I

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k,=3.130-4 s-l

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. . . . ..
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. . . . .
7NO
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-LU -3.33 -5.11 -LW 4 9 ? -4.00 -6.54

time /s loo[c.(lv)l I
-7.04l , I . a . , . I . ,
5.5E4 5.6E4 5.714 5.8E4 5.9E4 6.OE4
t i m e /s
kl=3.24a-4 a-’
E Figure 7. Simulations based on model D ~ s at
s high CSTR flow rates for
-5.00 7
-4.M I [BrO3-lmf= 0.1 14 M, [H+Id = 0.38 M, [MAId = 0.3 M, [Ce(III)]d
= 0.001 M. (A) Periodic behavior at kf = 1.63 X IO” s-l. (B) Chaotic
behavior at kf = 1.76 X IO” s-l.

occur between two large ones. The characterization of these

-5.50’
2500
. . . . .
5000
. , . . ,
7500
. . , .
10000
I periodic states thus is not always simple.
time / I There are periodic states of various complexity in this region,
and aperiodicity was not encountered with our rather crude
Figure 6. Chaotic behavior found in simulations based on model D ~ s s flow-rate grid until kf = 1.76 X lo-’ s-l, where the chaotic time
at low CSTR flow rates. (A) log [ B f ] time series at kf = 2.96 X IO4 series shown in Figure 7b was obtained. More chaos is seen as
s-I. (B) A return map constructed by plotting consecutive values of log the flow rate is increased. The time spent in the vicinity of the
[Ce(lV)] from Figure 5 against one another at kf= 2.96 X lo-* s-l. (C) oxidized state also increases with increasing flow rate until at 1.98
log [Br-] time series at kf = 3.13 X lo4 s-l. (D) log [Ce(IV)] return X s-I small-amplitude, sinusoidal oscillations around the
map at kf= 3.13 X lo-* PI. (E) log [Br-] time series at kf = 3.24 X IO4 oxidized steady state appear, as seen experimentally. At kf = 2.0
8. (F) log [Ce(lV)] return map at kf = 3.24 X 104s-l.
X s-I the system reaches the oxidized steady state. The gross
type oscillations are reached via a cascade of reverse period- characteristics of this behavior are the same as observed exper-
doubling bifurcations, as seen in model A and experimentally. imentally.
Higb Fbw Rates. There is some controversy concerning whether Model + Low Flow Rates. The chemical conditions of the
low-flow-rate study agreed with those used with model D, and
the aperiodicity observed at high CSTR flow rates is indeed
deterministicchaos. This complexity occurs around the oxidized, in experiments. The low-flow-rate complexity appears at some-
low Br- state rather than around the reduced, high Br- steady state what higher flow rates with model DEQ than with either model
as at low flow rates. Miinster and Schneider” concluded that A or experimentally. This shift occurs because the equilibrium
the high-flow-rate aperiodicity in their experiments was due to approximation for [BrO,’] leads to a 0.5-order autocatalysis in
the noisedriven wandering of the system between two attracting HBr02, which is probably weaker than in the real system. This
limit cycles. On the other hand, many authorsHJ1J2have claimed shifts the reduced steady state and the complexity associated with
to see high-flow-rate chaos for different feedstream concentrations. it to higher flow rates. While the flow rate region in which
We have pointed out2’ that model A should be able to simulate complexity appears is not reproduced very well by model DE,,
high-flow-rate complexity, but we did not try to do it. We do so the phenomena observed are very similar to the experimental. In
here with model D, for high CSTR flow rates and for CSTR fact, model D, seems to match the qualitative features of the
feedstream concentrations intermediate to two used experimentally, experiments better than does model D,. Figure 8 shows the
that used by Hudson and Mankid to find high-flow-rate aper- bifurcation diagrams resulting from flow-rate scans in both di-
iodicity that appears to be a mixture of neighboring periodic states rections designed to reveal hysteresis in model D,. The system
and that used by Miinster and Schneider.“ These concentrations is in its reduced steady state at the lowest flow rates used.
are [MA],f = 0.3 M, [Ce(III)ld = 0.001 M (these two were the Small-amplitude, sinusoidal oscillations develop initially as the
same in both experiments), [Br03-lmf= 0.144 M, and [H+Imf= flow rate is increased followed by the sudden appearance of
0.38 M (these two mixed-feed concentrations were different in mixed-mode oscillations. Comparison of Figure 8, A and B, reveals
the two experiments). Model DqS is indeed chaotic at certain a narrow region of bistability between these two oscillatory be-
high flow rates. Regular oscillations appear at kf = 1.0 X lo-’ haviors. There are at most 5-7 small-amplitude oscillations be-
s-I (lo), 1.5 X s-l (l’), and 1.65 X s-l (12). There are tween two large-amplitude excursions at the low-flow-rate end
a number of other periodic states between the 1’ and the l 2 limit of the mixed mode behavior. This is a better fit to experiment
cycles. The small oscillations are close to the oxidized state, than model Dw provides. There are chaotic regions between the
following an oxidative excursion rather than being close to the mixed-mode limit cycles. This simulated periodi-haotic sequence
reduced state after a reduced excursion as in the low-flow-rate also matches experimentlcIs better than when model DQss is used.
complexity. Figure 7a shows the periodic state at kf = 1.63 X The last major periodic window as the flow rate is increased is
lo-) s-I and illustrates that at high flow rates it is not always a 2l limit cycle, which is followed by a narrow chaotic regime and
possible to unambiguously decide how many small oscillations a cascade of reverse period-doubling bifurcations leading to the
~~
canonical l o periodic behavior. Two chaotic time series from
(40)Monster, A.; Schneider, F. W. J . Phys. Chem. 1991, 95, 2130. windows between 1’ and lo periodicities and their corresponding
Schneider. F.W. Personal communication. return maps are shown in Figure 9. These return maps, in
6600 The Journal of Physical Chemistry, Vol. 95, No. 17, 1991 Gyorgyi and Field
-4.77 -
: 0
$ -4.81 .
t
u
$ -4.81 -
0

d -
-z5
h
-4.89

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-J-
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0
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5.3E4 5.4E4 5.5E4

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-
.
$
-4.77

-4.81 -
t
8
5 -4.85 .
0
8
f
-
-z -4.89
/
Y
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/..‘
-: B tlme /s

-4.97’ ,
a-
. . , 1
Figure 10. Simulations based on model Dw at high flow rates with
[BrO3-Imr= 0.114 M, [H+]& = 0.38 M,[MA]& = 0.3 M, [Ce(III)]d
I I I 1 I

5.1 5E-4 5.46E-4 5.77E-4 6.088-4 6.39E-4 6.70E-4

= 0.001 M. (A) Periodic behavior at kf = 1.96 X lo-’ s-l. (B) Deter-
flow rate /a’ ministic chaos at kf = 2.08 X IO-’ s-l.
Figure 8. Bifurcation diagrams obtained in simulations based on model
D, at low flow rates. The log [Ce(IV)] values on the ordinate are
intersections of the trajectories with the Poincari plane perpendicular to
the [Br-] axis and containing the point ([Br-] = 2.8260 X IO* M,
o’22 1
0.21
[HBr02] = 2.8420 X lW5 M,[Ce(IV)] = 1.1405 X lo-’ M, [BrMA] -0n
= 1.271 54 X IO-’ M)when [Br-] is increasing. Results are shown when t 0.20
gradually increasing (A) or decreasing (B) the flow rate. Differences 8
between (A) and (B) suggest bistability in that region. Periodic behavior 0

is indicated when only few intersections are visible at a particular kf, :

f
0.1 9
while many intersections indicate chaos.
--
2
E

0.1 8
k,=S.l 8.-4 a-’
U
I

0.1 7
-4.11 ’,. 4.5E-4 5.OE-4 5.5E-4 6.OE-4 6.5E-4 7.OE-4 7.5E-4

flow rate /s-‘

Figure 11. Bifurcation diagram obtained in simulations with model E

at low CSTR flow rates. The log [Ce(IV)] values are intersections 3
the trajectory with the Poincari plane perpendicular to the x -
-6.2JJ . . . . I . . . . I . . . . + -4.0 I
-4.9) -4.90 -4.17 -4.14 -4.11 -470 ([HBrO,]/X,J axis and containing the point ( x = 0.18, z = 0.20, u =
0 2500 5WO 7500
llmo /a IoglCe(tV)I I 1.589) when x is decreasing for gradually increasing flow rate (kf).
Periodic behavior is indicated when only a few intersections are visible
at a particular kf, while many intersections indicate deterministic chaos.
All parameter values are those inherited from model D except kM = 1.0
M-1 s-I

complex limit cycles are seen in this region, e.g., lo at kf = 1.80

X lo-’ s-I, 1’ at kf = 1.95 X lO-’s-I, and l2 at kf = 2.0 X 10”
s-l. A more complicated periodicity of this region, at kf = 1.96
X lo-’ s-l, is shown in Figure 10A. The ratio of small to large
oscillations increases as the flow rate increases. We found the
-6.23’ . . , .
, . . . . . . . , -4.14 I I
first chaotic time series at kf = 2.08 X lo-’ s-I and is shown in
0 2500
tlma /s
5WO 7MO -4.14 -4.11 -4.12 4 1 0 -4.79 -471 Figure 10B. As with model ,,D the flow-rate grid of the sim-
log[ce(IV)l ulations is too coarse to exclude the existence of robust chaotic
I

Figure 9. Chaotic behavior in simulations based on model Dw at low
flow rates. (A) log [ B r ] time series at kf= 6.18 X l p s-l. (B) A return
map constructed by plotting consecutive values of log [Ce(IV)] from
Figure 8 against one another at kf = 6.18 X l p s-l. (C) log [Br-] time
series at kf= 6.35 X ip s-l. (D) log [Ce(IV)] return map at kf= 6.35
x 10-4 s-1.
particular the one in Figure 9D,show striking similarity to ex-
periment .‘I
High Flow Rates. The same feedstream concentrations were
used to test the high-flow-rate behavior of model as were used
for model,,D and the results obtained were similar. Many
(41) See Fig. 5.3.b p 107 in ref 18.
regions at lower flow rates. The length of time spent near the
oxidized state increases as the flow rate is increased, and a
transition to small-amplitude, sinusoidal oscillations occurs between
kf = 2.15 X lo-’ and 2.17X lo-’ s-I. The system is already at
the oxidized steady state at kf= 2.20 X lo-’cl. The gross features
of this sequence agree with both model,D and experiments.
Model.,E The same chemical conditions were used as for
the low-flow-rate studies of model D. Model ,E did not exhibit
complexity for the parameter values inherited from model D.
However, changing kM, an adjustable parameter?’ from 0.3 to
1.O M-’ s-’ resulted in complex periodic and chaotic behavior. No
attempt was made to determine the value of kM giving the best
quantitative agreement with experiment. Figure 1 1 shows the
bifurcation diagram for model ,E obtained with increasing flow
Deterministic Chaos in the BZ
0.2015
P.ZW7
0.05' . . . , , . . 11.11
. . . 0.1 999
11.0 11.2 11.4 11.6 120
tlmm
0.21 91
0.2071
0.35
0.1931
0.25
0.1 831
0.1 5
0.05'
11.0
. ,
11.2
. .
11.4
. ,
11.6
. .
11.1
. 7
120
0.1711
0.171 1 0.1 831 0.1 951 0.2071 0.2191
tima
Figure 12. Chaotic behavior found in simulations based on model EEQ
at low flow rates. (A) z time series at k, 5 4.89 X 10-4 PI. (B) A return
map constructed by plotting consecutive values of z from Figure 11
against one another at kl= 4.89 X lCr's-I. (C) z time series at kf = 5.31
X lCr' s-l. (D) z return map at kf = 5.31 X lO-'s-I. All parameter
values are those inherited from model D except kw = 1 .O M-' s-l.
rate. Essentially identical results were obtained when the flow
rate was decreased. No complexity was observed at very low flow
rates, e.g., kf= 2 X 10-4 s-l. The amplitude increases as the flow
rate is increased, and a cascade of period-doubling bifurcation
above kf = 4.5 X 10-4 s-l results in chaos. There is a wide chaotic
window before l 6 periodicity is reached by way of a reverse pe-
riod-doubling bifurcation. There is another chaotic window as
the flow rate is increased further, which is followed by several
complex periodicities with decreasing number of small peaks per
period. Time series and return maps from these two chaotic
windows are shown in Figure 12. No chaos was observed at flow
rates above where the l 5 limit cycle appears. Slight differences
between the bifurcation diagrams obtained with flow rate scans
of opposite direction suggest that bistability may exist between
consecutive windows of complex periodicities in this region. There
is a simple limit cycle at the highest flow rates shown in Figure
11, which is quickly followed by an oxidized steady state. The
width of the window for these regular oscillations is rather narrow,
=2 X lod s-l. It is possible to increase the width of this region
by decreasing kclo. The addition of one small cycle per period
('period adding")'2 as a bifurcation parameter is changed mon-
otonically is characteristic of a family of cusp-shaped, one-di-
mensional return maps related to a saddle-node bifurcation.
Although our results suggest that the dynamia of model E, could
be analyzed in terms of such a map, we did not attempt to verify
this.
Model E , does not satisfactorily reproduce the experimental
sequence of periodic and chaotic windows with the parameters
used here. Nevertheless, it is a kariable, chaotic model derived
from a good model of the BZ-CSTR chaos, and it is possible that
another parametrization would result in a better fit to experiment.
Furthermore, the chaos and the complex periodicities observed
in these simulations result from the same chemical mechanism,
i.e. [BrMA], ( u ) moving around a bifurcation point by the balance
between its chemical production and its removal by the flow, as
those in the larger models and most probably in the real system.
Discussion
A chemical, two-frequency-couplingexplanation of the com-
plexity in low-flow-rate BZ-CSTR experiments was given when
we introduced model A. It was based mostly on numerical ex-
periments and chemical intuition. The key reaction steps necessary
(42) Kawczynski, A. L.; Misiurewicz, M.Z. Phys. Chem. (Leipzig), in
press.
The Journal of Physical Chemistry, Vol. 95, No. 17, 1991 6601
I
b CBrO 2
1.
(, Ef-
0.6
\
%
\.
0.1999 0.2007 0.2Do 0.2013 0,2031
21
k,=5.31 0-4 s-'
Figure 13. Schematic representation of the chemical mechanism of
r model D. Boxes represent chemical reactions and solid lines represent
the intermediates of the model. Numbers represent the stoichiometry of
a given reaction if other than 1. Dashed lines indicate components of
constant concentration. Only the dominant consuming and producing
reactions of the intermediates are shown. Light shading marks proceases
active during the oxidized (low [Br-1, high [HBrO,]) state, heavy shading
marks the process (D2)active during the reduced (high [Br-], low
zt [HBr02))state of the system. No shading indicates that the CSTR flow
is always an active process.
for the simulation of this complexity have been identified here,
and the two four-variable models derived allow this mechanistic
analysis to be made more concrete. Some review of BZ chemistry
is needed to do this.
Figure 13 shows the most important processes of the 4-variable
models and their dominant interactions via chemical species. The
r ~ ~ if the processes within the dashed box
simple O r e g ~ n a t o results
are replaced by one step:
Ce(1V) -$Br- (05)
The Oregonator oscillations are easily rationalized. When it is
in its oxidized, low [Br-1, high [HBr02] state, the autocatalytic
reaction between Br03- and HBr02 (D4) produces Ce(1V).
Bromide ion is produced in (05)after a delay while Ce(1V)
accumulates. Note that reaction D1 is a switch process. When
[Br-] gets sufficiently large, it depletes HBr02 via (Dl), thus
stopping the HBr02 autocatalysis and production of Ce(1V). This
allows [Br-] to grow until Ce(IV) is depleted by (05).Bromide
ion then is slowly removed by B r O r in (D2). Step D4 switches
on again when [Br-] reaches a low enough level, allowing (Dl)
to remove the remaining Br-, completing the cycle.
The simple Oregonator contains only one feedback loop (cycle)
and does not show complex oscillations or chaos. However, there
is an additional negative feedback loop in model D created by the
introduction of the additional variable, [BrMA], which acts as
a bifurcation parameter for the Oregonator-core (reactions outside
of the dashed box + 05)of the model and which is removed from
the system primarily by the CSTR flow. The [BrMA] may act
as a bifurcation parameter because BrMA is a product of the
overall reaction so that its concentration is usually high and hardly
changes during oscillations. Furthermore, it is the sole source of
Br-, the inhibitor of (Dl). Oscillations occur only if [BrMA] is
in a certain range. The rate of Br- production is so high when
[BrMA] is above a critical value that the system approaches a
reduced steady state. So little Br- is produced when [BrMA] is
below another critical value that the system remains in an oxidized
steady state. These critical points correspond to Hopf bifurcations
in the simple Oregonator, and the additional negative feedback
manifests itself when [BrMA] oscillates across them.
Its concentration oscillates because BrMA is produced at
different rates during different phases of the oscillations. It is
synthesized very rapidly in (DI) when the system is in its oxidized
(low Br-, high HBr02) state and very slowly yhen it is in its
reduced (high Br-, low HBrOJ state. At low flow rates when
[BrMA] is high, a few pulses of oxidation may push it above the
critical [BrMA] where (Dl) is inhibited and no further oxidative
pulses can occur. In terms of the diagram in Figure 13, this means
that a product of (Dl) switches (Dl) off. This is a negative
feedback, which the CSTR flow makes the source of a second
frequency. The rate of BrMA synthesis is very slow in this reduced
6602 The Journal of Physical Chemistry, Vol. 95, No. 17, 1991
state, and if the flow rate is in the region of complexity, it washes
BrMA out of the reactor fast enough for [BrMA] to fall back
below its critical value where oscillation and its relatively rapid
synthesis begin again. Thus the second frequency is related to
cycling of [BrMA] around its critical value and is determined by
two independent rates, that of synthesis of BrMA by the Ore-
gonator core and that at which the flow washes it out of the CSTR.
It is the independence of the flow time scale from that of the
Oregonator core that keeps the [BrMA] frequency from always
entraining with the Oregonator core frequency. At high flow rates,
when its concentration is low, BrMA may be washed out of the
CSTR so rapidly even during oscillations that it falls below the
lower critical value, causing the Oregonator core to be attracted
to the oxidized steady state. The synthesis of BrMA in this state
is so rapid that its concentration may again exceed the critical
[BrMA] and oscillations restart. This also is a negative feedback
in that a flow-driven decrease in [BrMA] causes passage of the
system into a state that causes [BrMA] to increase, counteracting
the original effect. The flow again plays a crucial role in de-
termining the frequency generated by this feedback loop as it
affects both the time needed for [BrMA] to fall below its critical
value and the time needed to bring it back into the oscillatory
regime.
The complexity at both high and low CSTR flow rates is caused
by the interaction of the frequency generated by the Oregonator
core with the frequency generated by the interplay of the second
negative feedback loop and the flow.
The same mechanism creates the complex oscillations in sim-
ulations based on model EEQ However, choosing B f to be the
fast variable effectively removes the reduced state of the relaxation
oscillations. The length of the reduced excursion in the real system
is determined by the time scale on which Br- is removed by its
slow reaction with B Q - . Eliminating Br- from the mechanism
by the QSSA thus is not a very good approximation in the high
[Br-] state. Nevertheless, model E, does simulate low-flow-rate
chaos and is the mathematically most tractable of all chaotic
models of the BZ reaction.
Conclusion
The two 4-variable models introduced here simulate with great
accuracy the periodic-haotic sequence found in BZ-CSTR ex-
periments at low flow rates, and they also show complex per-
iodicities and chaos at high flow rates. A 3-variable model is
presented which exhibits complex periodicities and chaos at low
CSTR flow rates. These models, though simple, are capable of
simulating a wide variety of experimental phenomena in a CSTR.
Since they include BrMA as a variable, they are also expected
to show an induction period in closed system, a feature missing
from previous simple mechanisms. They also use up-to-date
chemistry of this system. We suggest that they should be con-
sidered as viable alternatives to other simple BZ models, e.g., the
Oregonator and SNB43models.
Our results demonstrate that it is possible to obtain chaotic
behavior at both high and low CSTR flow rates using simple
(43) Showalter, K.; Noyes, R. M.; Bar-Eli, K. J . Chem. Phys. 1978,69,
2514.
Gyorgyi and Field
chemical models of the BZ reaction. Both experiments and sim-
ulations now convincingly support the existence of chemical chaos
in BZ-CSTR experiments at low flow rates. The situation at high
CSTR flow rates is not completely resolved yet, although we show
here that it is possible to numerically simulate chaos at high CSTR
flow rates. This suggests that at least some of the aperiodicity
found in these experiments may indeed be deterministic chaos
resulting from the homogeneous kinetics of the Belousov-Zha-
botinsky reaction.
Numerical Aspects
The numerical integrator L S O D E ~was used on a VAX 8600
or a 25-MHz "386" PC with a Weitek 3167 coprocessor. The
relative error tolerance used was between lo-' and lo4 and the
absolute error tolerance was between l@13 and 1@l5. The absolute
error tolerance was for the scaled model E. There was no
dependence of observed behavior on the error tolerances. All
integrations were carried out for at least 70000 s, and up to
15OOOO s at the lowest flow rates used, before data collection in
order to avoid transients. The end point of the preceding calcu-
lation was used to start the next when searching flow-rate space,
as is done experimentally. Poincart sections were calculated by
using a slight modification of the algorithm of Parker and C h ~ a . 4 ~
The accuracy of the plane intersection in time was usually f 5
X lo4 s for model D and f 5 X lo4 dimensionless time units for
model.,E
The simulated phenomena were classified on the basis of visual
examination of the time series, the log [BrMA] vs log [Br"] phase
portrait, and Poincart sections constructed as described in the
legend for Figures 4, 5 , 8, and 10. These methods, especially the
last, are very efficient for distinguishing transients from complex
periodic behavior. Although we recognize the importance of other
methods, e.g., calculating the correlation dimension or the spec-
trum of Lyapunov characteristic exponents of experimental data,
in the case of noise-free, simulated data, the above-mentioned
graphical procedures are fast and reliable.
Acknowledgment. This work was supported by the National
Science Foundation under Grant CHE-8822886. We thank
Tamils Turgnyi of the Central Research Institute of the Hungarian
Academy of Sciences, the members of the Center for Nonlinear
Dynamics in Austin TX, in particular Zoltin Noszticzius, for
valuable discussions and the University of Montana Computing
and Information Services for computing time and technical
support.
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