Complex Nonlinear Behavior in the Bromate–2-Aminophenol Reaction

Article abstract of DOI:10.1002/kin.21053

The bromate–2-aminophenol reaction in a batch reactor was investigated in this research, in which both simple and sequential oscillations were observed. The occurrence of sequential oscillations were found to be very sensitive to changes of the initial concentrations, where decreasing the concentration of sulfuric acid or sodium bromate or increasing the 2-aminophenol concentration caused the two oscillation windows to coalesce. Lowering the reaction temperature from 30 to 5°C also caused the two oscillation windows to merge into one. A phase diagram in the bromate–sulfuric acid concentration plane demonstrates that sequential oscillations only occur within a narrow band of conditions. Mechanistic studies of the system through employing ¹H NMR and mass spectrometry suggest that a dibrominated ortho-benzoquinone is a major product. The oxidation of 2-aminophenol, on the other hand, can lead to the formation of pyrocatechol, which may be the substrate responsible for the second set of oscillations.

Full text of DOI:10.1002/kin.21053

Complex Nonlinear
Behavior in the
Bromate–2-Aminophenol
Reaction
ALEXANDER TANG, JEFFREY G. BELL, JAMES R. GREEN, JICHANG WANG
Department of Chemistry and Biochemistry, University of Windsor, Windsor, ON, N9B 3P4, Canada
Received 7 July 2016; revised 22 September 2016; accepted 6 October 2016
DOI 10.1002/kin.21053
Published online in Wiley Online Library (wileyonlinelibrary.com).
ABSTRACT: The bromate–2-aminophenol reaction in a batch reactor was investigated in this
research, in which both simple and sequential oscillations were observed. The occurrence of
sequential oscillations were found to be very sensitive to changes of the initial concentrations,
where decreasing the concentration of sulfuric acid or sodium bromate or increasing the 2-
aminophenol concentration caused the two oscillation windows to coalesce. Lowering the
reaction temperature from 30 to 5°C also caused the two oscillation windows to merge into
one. A phase diagram in the bromate–sulfuric acid concentration plane demonstrates that
sequential oscillations only occur within a narrow band of conditions. Mechanistic studies of
1
the system through employing H NMR and mass spectrometry suggest that a dibrominated
ortho-benzoquinone is a major product. The oxidation of 2-aminophenol, on the other hand,
can lead to the formation of pyrocatechol, which may be the substrate responsible for the
second set of oscillations. ꢀC 2016 Wiley Periodicals, Inc. Int J Chem Kinet 1–7, 2016
INTRODUCTION
catalysts such as cerium, ferroin, or ruthenium com-
plexes [15–23]. In 1978, Orb a´ n and K o¨ r o¨ s carried out
an extensive search to study the oxidation of aromatic
compounds by acidic bromate and reported that 23
phenol and aniline derivatives could produce oscilla-
tions without an addition of a metal catalyst to start
the autocatalytic cycle [24]. Their investigation led to
the establishment of a class of uncatalyzed bromate
oscillators.
Chemical oscillations and wave formation have at-
tracted a considerable amount of interest from re-
searchers working in diverse areas such as math-
ematics, engineering, physics, and biology due to
their fundamental connections in the emergence of
similar nonlinear phenomena in those areas [1–14].
Arguably, the most extensively studied oscillatory
chemical reaction is the Belousov–Zhabotinsky (BZ)
reaction, which is the oxidation of an organic sub-
strate by acidic bromate in the presence of metal
ˇ
Sev cˇ ´ı k and coworkers have discovered that using
aniline and phenol as the organic substrate the uncat-
alyzed bromate oscillator could result in the occur-
rence of sequential oscillations, in which two oscilla-
tory windows are separated by a long period of quies-
cent, nonoscillatory evolution of the reaction [25,26].
Computational investigations have illustrated that the
Correspondence to: J. R. Green; e-mail: jgreen@uwindsor.ca,
J. Wang; e-mail: jwang@uwindsor.ca.
ꢀ
2016 Wiley Periodicals, Inc.
C

2
TANG ET AL.
coupling of two limit cycles (i.e., simple oscillations)
may lead to the quench of the oscillatory behavior, de-
pending on the frequency and magnitude of the two
limit cycles. Working from such a theory, a chemical
oscillator consisting of two suboscillators may tem-
porally evolve into a nonoscillatory stage, where the
stoppage of oscillation is due to the subtle balance of
the two suboscillators. As a result, the phenomenon
of sequential oscillation may take place in a closed
chemical system, in which the continuous consump-
tion or buildup of chemicals ensures that properties
of suboscillators change in time. Several bromate-
based oscillators consisting of coupled autocatalytic
cycles have indeed been found to exhibit sequential
oscillations [27–36]. For example, sequential oscilla-
tions have been reported when 1,4-cyclohexanedione
EXPERIMENTAL
All reactions were carried out in a thermal-jacketed
50-mL glass beaker (ChemGlass; New Jersey, United
States). A circulating water bath (Thermo NesLab
RTE 7; Fisher Scientific; Ottawa, Canada) held the
reaction temperature constant at 25.0 ± 0.1°C un-
less stated differently. The reactions were monitored
using a Hg|Hg2SO4|K2SO4 reference electrode cou-
pled with a platinum electrode (Radiometer Analytical,
XR200 and M231 Pt-9; Villeurbanne Cedex, France).
The volume for every reaction solution was fixed
at 30.0 mL. The reaction was stirred with a mag-
netic stirring bar driven by a magnetic stirrer (Fis-
cher Isotemp; Fisher Scientific; Ottawa, Canada) to
ensure homogeneity. All measurements were recorded
through a pH/potential meter (Radiometer PHM220;
Villeurbanne Cedex, France) connected to a personal
computer through a PowerLab/4SP data logger. All
(CHD) was added to the ferroin-catalyzed BZ os-
cillator, in which the minimum 1,4-CHD required
for inducing complex oscillations depends on the
parameter of the BZ reaction [34,35]. When fer-
roin was added to bromate-hydroquinone photochem-
ical oscillators, two isolated oscillatory windows
developed [36].
In spatially extended media, the temporal occur-
rence of nonoscillatory evolution may lead to spon-
taneous breakups of existing wave activity, resulting
in the formation of spiral waves or turbulence [37].
To enrich the family of chemical oscillators exhibiting
sequential oscillations, the uncatalyzed bromate os-
cillator using 2-aminophenol (2-AP) as the aromatic
substrate has been systematically investigated here.
The Wang research group have previously studied
the reaction kinetics and wave patterns of bromate–4-
aminophenol (4-AP) oscillators [38]. Studying a sys-
tem using an ortho substituted substrate may help gain
new insights into such a system since the structures
1
H NMR studies were performed using either a Bruker
Avance 300 or 500 MHz spectrometer, and the samples
were dissolved in chloroform-d (Cambridge Isotope
Laboratories; 99.8%; Montreal, Canada) or acetone-
d6 (Cambridge Isotope Laboratories; 99.9%; Montreal,
Canada). Mass spectrometry measurements were per-
formed using a 1200-L single quadrupole MS (Varian)
through a direct insertion probe, and using a Waters
XEVO GS-XF Time-Of-Flight, with samples intro-
duced via an Atmospheric Solids Analysis probe.
Stock solutions of sodium bromate (NaBrO3;
Aldrich; 99%; Oakville, Canada), 0.06 M, and sul-
furic acid (H2SO4; Aldrich; 95%–98%; Oakville,
Canada), 6.0 M, cerium(IV) sulfate (Ce(SO4)2;
Aldrich; Oakville, Canada), 0.1 M, were prepared with
double-distilled water. 2-AP (Aldrich; 99%; Oakville,
Canada) was directly dissolved in the reaction mixture.
Bromate solution was added to the reaction mixture,
after 2-AP had dissolved completely. All chemicals
were commercial grade and were used without further
purification.
4-AP and 2-AP only vary by the location of the func-
tional groups; therefore, only the reaction rate of steps
involving 4-AP are altered, allowing for further mech-
anistic understanding of the occurrence of complex
behavior.
Different from the bromate–4-AP oscillator, the
bromate–2-AP reaction has been found to exhibit se-
quential behavior without an addition of a metal cata-
lyst. Another notable difference is that the oscillatory
behavior is not photosensitive. After extensive studies
in the concentration phase space were conducted, the
phase diagram in the bromate–sulfuric acid concentra-
tion phase space demonstrates why finding sequential
behavior in this uncatalyzed system is difficult. A pos-
sible mechanism has been suggested to explain the
emergence of sequential behavior in this uncatalyzed
bromate–2-AP system.
RESULTS AND DISCUSSION
Figure 1 shows five time series of the bromate–2-AP
reaction conducted at different concentrations of 2-AP:
(a) 0.0128 M, (b) 0.0112 M, (c) 0.0096 M, (d) 0.0064
M, and (e) 0.0032 M. In Fig. 1a, simple transient oscil-
lations with a decreasing frequency were seen after a
long induction time (ca. 4000 s). Phenomenologically,
after mixing all reactants together the reaction solution
slowly changes from a bright orange to a dark brown
color; this corresponds to the long induction time that is
International Journal of Chemical Kinetics DOI 10.1002/kin.21053

COMPLEX NONLINEAR BEHAVIOR IN THE BROMATE–2-AMINOPHENOL REACTION
3
Figure 1 Time series of the bromate–2-AP reaction carried
out at different 2-AP concentrations: (a) 0.0128 M, (b) 0.0112
M, (c) 0.0096 M, (d) 0.0064 M, and (e) 0.0032 M. Other
reaction conditions were [H2SO4] = 1.3 M and [NaBrO3] =
Figure 2 Time series of the bromate–2-AP reaction carried
out at different H2SO4 concentrations: (a) 1.4 M, (b) 1.3 M,
0
.03 M.
(c) 1.2 M, and (d) 0.6 M. Other reaction conditions were
[
2-AP] = 0.008 M and [NaBrO3] = 0.03 M.
observed. This is then followed by a rapid color change
to a bright yellow-orange solution as indicated by a
sharp spike in the redox potential. Spontaneous oscilla-
tions in the bromate–2-AP system has been reported by
Orb a´ n and K o¨ r o¨ s in 1978; however, only simple oscil-
lations were observed. [24] Once the concentration of
the excursion would occur almost instantaneously af-
ter mixing all reactants together as 2-AP concentration
was decreased to 0.0016 M.
2
-AP reaches above 0.0208 M, the oscillatory behavior
Figure 2 shows time series illustrating the effect of
changing the concentration of sulfuric acid on the os-
cillatory behavior. Other conditions are kept constant
at [2-AP] = 0.008 M and [NaBrO3] = 0.03 M. At the
sulfuric acid concentration of 1.4 M, Fig. 2a shows
that several oscillations took place about 2500 s af-
ter the start of the reaction. When the sulfuric acid
concentration was increased to 1.7 M, only a single
clock reaction could be observed. The second set of
oscillations emerge in Fig. 2b as a result of decreas-
ing sulfuric acid concentration to 1.3 M. When the acid
concentration was decreased further, the nonoscillatory
period slowly decreases until there was an overlap of
the two sets leading to a single set of oscillations seen in
Fig. 2c. Under the conditions employed in this figure,
sequential behavior was observed to occur in the range
of 1.2 M to 1.3 M H2SO4. At an acid concentration
of 0.6 M, the initial excursion was less sudden and no
oscillatory behavior could be observed.
disappears. As the 2-AP concentration was decreased
to 0.0112 M in Fig. 1b, there was a noticeable change
in the oscillatory behavior at about 6000 s after the
start of the reaction, signaling the possible occurrence
of complex oscillations. Upon further lowering 2-AP
concentration to 0.0096 M in Fig. 1c, a period of quies-
cent nonoscillatory evolution became visible, forming
two isolated oscillation windows. The frequency of os-
cillations in the first window was much higher than
that in the second oscillation window. When the con-
centration of 2-AP was decreased from the sequential
oscillation conditions, the second set of oscillations
rapidly disappear as depicted in Figs. 1d and 1e. This
would indicate that the concentration of the interme-
diates that start the second oscillatory regime was too
low to induce an oscillatory cycle. The decrease of 2-
AP concentration also resulted in the decrease in the
number of oscillations until only one clock reaction
is present at 0.0048 M 2-AP. The induction time of
the potential excursion also continues to decrease, and
Figure 3 presents five time series conducted at dif-
ferent bromate concentrations, while the 2-AP and
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4
TANG ET AL.
Figure 4 Phase diagram of the bromate–2-AP reaction in
the bromate–sulfuricacid concentration plane. 2-APwas kept
at a constant concentration of 0.008 M. ◦ Indicates the con-
ditions under which the system exhibits simple oscillation, ꢀ
indicates sequential behavior, ꢁ indicates a single peak be-
havior, and × indicates the boundary at which no oscillatory
behavior occurs.
lations since it produces the bromine dioxide radicals
for the autocatalytic steps.
Figure 4 presents a phase diagram in the bromate–
sulfuric acid concentration phase plane while the con-
centration of 2-AP was kept constant at a concentration
of 0.008 M. The circles represent conditions at which
simple oscillations have been found, and the crosses
represent the boundary at which no oscillatory behav-
ior was observed. One can see that oscillatory behavior
can occur over broad concentrations of bromate and
sulfuric acid. However, sequential behavior can only
be observed within a very narrow band of conditions
as depicted by the triangles. Small increases in the con-
centrations of sulfuric acid or bromate would result in
rapid disappearance of the second set of oscillations. A
decrease in concentration results in the overlap of the
two sets, making it impossible to see two individual
sets of oscillations. This phase diagram also contains
no upper boundaries in either the sulfuric acid or the
bromate plane, meaning that oscillatory behavior will
continue to be observed at high levels of bromate and
sulfuric acid. However, only a single clock reaction
can be observed at those conditions as depicted by
the squares, while the induction period continues to
decrease until it approaches zero.
Figure 3 Time series of the bromate–2-AP reaction car-
ried out at different NaBrO3 concentrations: (a) 0.042 M,
(
b) 0.033 M, (c) 0.030 M, (d) 0.024 M, and (e) 0.012 M. Other
reaction conditions were [2-AP] = 0.008 M and [H2SO4] =
.3 M.
1
H2SO4 concentrations were kept constant at 0.008 M
and 1.3 M, respectively. At NaBrO3 concentration of
0.042 M, an excursion of redox potential took place
at about 1000 s after the start of the reaction, fol-
lowed by a few spontaneous oscillations (see Fig. 3a).
The number of oscillations increased as the bromate
concentration was decreased in Fig. 3b. As shown in
Fig. 3c, sequential behavior could be observed at a
bromate concentration near 0.030 M. Similar to de-
creasing the concentration of sulfuric acid, decreas-
ing the bromate concentration resulted in a decrease
in the nonoscillatory period until the two sets begin to
merge. This disappearance occurs at a concentration of
0.024 M bromate in Fig. 3d. Notably, the remaining
oscillatory behavior did not occur right after the ex-
cursion of the redox potential and their frequency re-
sembles those of the second oscillation window seen
in Fig. 1c or 2b. This leads us to suggest that the first
oscillatory window was disfavored at the low bromate
concentration. At 0.012 M NaBrO3, no oscillatory be-
havior can be observed, as depicted in Fig. 3e. Overall,
sequential behavior is only observed within a narrow
range of bromate concentration around 0.03 M, con-
firming the importance of bromate in both sets of oscil-
Figure 5 illustrates the temperature dependence of
the reaction behavior in the bromate–2-AP system. As
to be expected, increasing the temperature results in
an increase in the rate of reactions, leading to the in-
crease of the oscillation frequency in both oscillatory
windows. Sequential behavior was observed at temper-
atures above 25°C as shown in Figs. 5a and 5b. Please
note that the x axis had to be changed to fit all the
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COMPLEX NONLINEAR BEHAVIOR IN THE BROMATE–2-AMINOPHENOL REACTION
5
tory behavior is also not photosensitive, as opposed to
what was seen in the 4-AP (para substituted benzene)
system. To understand those differences, in particular
the occurrence of sequential oscillations in this uncat-
1
alyzed system, H NMR and mass spectrometry anal-
yses were conducted at different stages throughout the
reaction: (1) when the reaction was at about 10 min af-
ter mixing all reagents together while the reaction was
still in its induction period, (2) a sample was obtained
at about 50 min reaction time when the system was
oscillating, and (3) a sample was obtained at around
180 min, when the oscillatory window had ended. In
all three cases, the reaction solution was extracted by
diethyl ether solvent and then analyzed using NMR
and mass spectrometry.
1
The H NMR and mass spectra for each sample
contained many peaks which made it very difficult
to identify all the compounds. However, a dominant
intermediate giving resonances at δ 7.02 and 6.96
(
2H, ABq, J = 10.5 Hz), which is indicative of the
presence of a dibrominated ortho-benzoquinone can
be seen at a reaction time of around 180 min (af-
ter sequential oscillations occur) as shown in Fig. 6.
A series of peaks at 264/266/268 m/z in the mass
spectrum also suggested the presence of this dibromi-
nated species, which is most likely 3,4-dibromo ortho-
Figure 5 A time series of the bromate–2-AP reaction
carried out at different temperatures: (a) 30°C, (b) 25°C,
(
c) 20°C, (d) 15°C, and (e) 5°C. Other reaction conditions
were [2-AP] = 0.008 M, [H2SO4] = 1.24 M, and [NaBrO3]
0.03 M.
1
benzoquinone. H NMR spectroscopy of the precipi-
=
tate in acetone-d6 revealed multiple resonances in the
δ 6.3–7.6 and 9.0–9.1 regions, whereas peaks with
high m/z in the mass spectrum suggest multiple 2-
AP/quinone/catechol oligomers. The high-resolution
mass spectrum of the precipitate also contained a se-
ries of peaks at 264/266 and 342/344/346 m/z, which
indicated the presence of a dibrominated and tribromi-
nated C11 species, specifically with C11H6BrNO2 and
data in one figure, highlighting the significant influ-
ence of reaction temperature. As depicted in the figure,
the majority of the reactions were out of the oscilla-
tory window within a 5 h time span, but a temperature
drop to 15°C caused the oscillatory period to last 7 h.
When the temperature was further decreased to 5°C,
no oscillatory behavior could be observed until the
+
C11H5Br2NO2 (as the M + H ions), along with tri-
and tetrabrominated C11 species.
15 h mark. An overall decrease in the number of sim-
Ce(IV) was reacted with a solution of 2-AP to de-
termine the direct oxidation product of 2-AP as shown
in Fig. 7. Ce(IV) was used as the oxidizing agent as
ple oscillations were also observed as the temperature
was decreased.
−
opposed to BrO3 to prevent unwanted bromination of
1
the aromatic sites. The resulting H NMR spectra cor-
MECHANISTIC CHARACTERIZATION
responded to the production of a significant amount of
ꢁ
ꢁ
pyrocatechol (δ 6.82 and 6.88, 4H, AA BB ). Scheme 1
presents a proposed mechanism for the production of
pyrocatechol from 2-AP, where 2-AP is initially oxi-
dized to produce an ortho-benzoquinone imine. This
is then followed by a hydrolysis reaction to produce
ortho-benzoquinone [39]. Finally, ortho-benzoquinone
is reduced by residual 2-AP resulting in pyrocatechol.
Owing to the formation of pyrocatechol, this
bromate–2-AP reaction may actually consist of two su-
boscillators, with the second one being the result from
the formation of pyrocatechol from 2-AP oxidation.
Similar to the bromate–4-AP reaction, precipitate was
found to form in the 2-AP system after mixing the re-
actants together. To test whether the precipitate would
affect the oscillatory behavior, the reaction was filtered
during the oscillatory period. If the oscillatory behavior
was a result of the precipitate, the oscillations would
disappear after the reaction was filtered. However, the
resulting behavior did not change which would indi-
cate that the presence of precipitate does not affect the
oscillatory behavior. Meanwhile, the observed oscilla-
International Journal of Chemical Kinetics DOI 10.1002/kin.21053

6
TANG ET AL.
Figure 6 1H NMR (300 MHz) spectrum of the aromatic
region of the bromate–2-AP reaction taken at 180 min when
the oscillatory window had ended at the conditions [2-AP] =
0
.008 M, [H2SO4] = 1.24 M, and [NaBrO3] = 0.03 M using
a CDCl3 solvent.
There have been earlier reports on chemical oscilla-
tors being formed through the uncatalyzed oxidation
of pyrocatechol by acidic bromate. [40–42] Competi-
tions between the two suboscillators may lead to the
occurrence of a long quiescent period in the middle
of an oscillatory process, resulting in the behavior of
sequential oscillations. We have examined this hypoth-
esis by perturbing the system with 1/10 of 2-AP used in
the system, and the first oscillatory window was indeed
quenched.
Figure 7 1H NMR spectrum of the direct oxidation product
-AP using Ce(IV) as an oxidant. Initial reaction conditions
2
were [2-AP] = 0.008 M with excess Ce(IV) using CDCl3 sol-
vent.
CONCLUSIONS
This study demonstrated that the uncatalyzed bromate–
2-AP reaction in a batch reactor could exhibit se-
quential oscillations. The development of a quiescent,
nonoscillatory evolution is likely the result of interac-
tions between two suboscillators, in which the second
suboscillator is being formed through acidic bromate
Scheme 1 Proposed dominant pathway.
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COMPLEX NONLINEAR BEHAVIOR IN THE BROMATE–2-AMINOPHENOL REACTION
7
and the oxidation products of 2-AP. Preliminary mech-
anistic studies suggest that pyrocatechol could be the
substance. Since this newly formed organic substrate,
presumably pyrocatechol, is also subjected to the con-
tinuous consumption through reactions with acidic bro-
mate, whether this intermediate substance can be built
up in the system (i.e., its formation from 2-AP over-
whelms its subsequent consumption) will be critical
in the development of the second suboscillator as well
as its competition with the bromate–2-AP oscillator. A
decrease in the induction period of the potential excur-
sion would cause the rapid disappearance of the second
set, whereas an increase would result in the overlap of
the two sets. This may indicate that the accumulation
of the intermediate pyrocatechol needs to reach a cer-
tain level prior to the excursion to exhibit sequential
behavior.
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International Journal of Chemical Kinetics DOI 10.1002/kin.21053