Long-Lasting Complex Reaction Behavior in a Closed Ferroin-Bromate-Hydroxybenzenesulfonate System

Article abstract of DOI:10.1021/acs.jpca.8b07766

The bromate-phenolsulfonate reaction was found to exhibit spontaneous oscillations in a batch reactor, where the addition of small amounts of ferroin would result in nonoscillatory behavior. As the ferroin concentration was increased, the system produced very rich nonlinear behavior, including three isolated oscillatory regimes that were separated by as long as 48 h nonoscillatory period. The long-lasting nonlinear behavior may be attributed to the slow desulfonation of phenolsulfonate in an acidic solution, forming phenol-like intermediates. However, unlike the bromate-phenol oscillator, oxygen was found to greatly influence the reaction, and various complex oscillations could be observed by tuning the oxygen concentration. Mechanistic studies performed through employing ¹H NMR spectroscopy and mass spectrometry to measure intermediate species at different stages of the reaction were able to identify 1,4-benzoquinone, 2-bromo-1,4-benzoquinone, 2,6-dibromo-1,4-benzoquinone, and 2,4,6-tribromophenol as major components during the reaction.

Full text of DOI:10.1021/acs.jpca.8b07766

Article
Cite This: J. Phys. Chem. A 2018, 122, 8301−8307
pubs.acs.org/JPCA
Long-Lasting Complex Reaction Behavior in a Closed Ferroin−
Bromate−Hydroxybenzenesulfonate System
Alexander Tang, James R. Green, and Jichang Wang*
Department of Chemistry and Biochemistry, University of Windsor, Windsor, ON N9B 3P4, Canada
ABSTRACT: The bromate−phenolsulfonate reaction was
found to exhibit spontaneous oscillations in a batch reactor,
where the addition of small amounts of ferroin would result in
nonoscillatory behavior. As the ferroin concentration was
increased, the system produced very rich nonlinear behavior,
including three isolated oscillatory regimes that were separated
by as long as 48 h nonoscillatory period. The long-lasting
nonlinear behavior may be attributed to the slow desulfonation
of phenolsulfonate in an acidic solution, forming phenol-like
intermediates. However, unlike the bromate−phenol oscillator,
oxygen was found to greatly influence the reaction, and various
complex oscillations could be observed by tuning the oxygen
concentration. Mechanistic studies performed through employ-
1
ing H NMR spectroscopy and mass spectrometry to measure intermediate species at different stages of the reaction were able
to identify 1,4-benzoquinone, 2-bromo-1,4-benzoquinone, 2,6-dibromo-1,4-benzoquinone, and 2,4,6-tribromophenol as major
components during the reaction.
1
. INTRODUCTION
which involve the oxidation and bromination of an organic
substrate by acidic bromate. In the past two decades, a host of
aromatic compounds have been found to be capable of
reacting with acidic bromate to exhibit spontaneous
The study of chemical oscillators has made significant
contributions to advancing the theory of nonlinear dynamics,
which has been incorporated into a diverse array of scientific
disciplines ranging from computer science to molecular
18−21
oscillations even in the absence of metal catalysts
and
1
−5
have seen increasing use due to the lack of the formation of gas
molecules, which is a desired property when the system is
employed to explore pattern formation in reaction−diffusion
biology.
such as the flow rate in a continuous flow stirred tank reactor
CSTR), reaction temperature, reactant concentrations, etc.,
Dynamic control parameters of a chemical system
(
2
2,23
media.
The reaction of phenol with acidic bromate, for
can be conveniently manipulated, which makes the study of
chemical oscillations excellent for gaining insights into related
nonlinear behavior seen in nature. In comparison to CSTR
experiments, reactions in a closed batch reactor are much
easier to operate. Unfortunately, oscillations in a closed
chemical system are transient, lasting only from a few minutes
24,25
example, has been found to give rich nonlinear behavior,
and derivatives of phenol such as 4-aminophenol have also
been found to result in oscillatory behavior when reacting in
acidic bromate solution, although some cases require the
26−28
presence of external illumination.
The continuous supply
6
−9
of organic substrate through desulfonation of PSA makes the
to a few hours,
as opposed to the reaction dynamics in a
proposed chemical system similar to a semiopen bromate−
CSTR, which can be kept permanently at a far from a
thermodynamic equilibrium state via the continuous supply of
fresh chemicals. This transient feature severely hinders the
utilization of closed chemical systems to explore complex
24,25
aromatic compounds oscillator.
Such a dynamic property
provides opportunities of significantly prolonging the oscil-
latory window and discovering new phenomena.
1
0−13
Sulfonated aromatics are also important intermediates in the
chemical industry, and understanding their reaction kinetics
could have far-reaching impacts, far beyond nonlinear
phenomena. For example, phenolsulfonate has been used as
an antistress additive during the Ferrostan process that is the
reaction phenomena and perturbed nonlinear dynamics.
Finding ways to prolong the oscillatory window of existing
chemical oscillators or developing new chemical oscillators that
yield long-lasting oscillations in a closed system remains an
important and challenging task.
In this research, sodium 4-hydroxybenzenesulfonate (PSA)
was selected to react with acidic bromate in a closed system, in
which the PSA is thermodynamically unstable in acidic media
and may undergo desulfonation to produce aromatic
29,30
most commonly used method for electroplating tin.
Nylon
could acquire a stain resistance if it is treated with the
condensation products of phenolsulfonate, formaldehyde, and
14
compounds that can form bromate oscillators. Arguably,
bromate-based reaction systems are the most extensively
investigated and best understood chemical oscillators,
Received: August 9, 2018
Revised: September 30, 2018
Published: October 5, 2018
15−17
©
2018 American Chemical Society
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3
1
sulfonates of dihydroxydiphenyl sulfones, and such com-
pounds have also been used to produce a resin that acts as a
purification. A Teflon cap was placed on top of the thermal-
jacketed beaker to hold the electrodes.
32
cation exchanger to catalyze esterification reactions. Sulfo-
nated aromatic compounds have also been found as
constituents of many detergents, dyes, cosmetics, and agro-
3. RESULTS AND DISCUSSION
Figure 1 presents the time series of the bromate−PSA reaction
3
3,34
−
6
−5
chemicals.
A pink dye can be produced, for example, by
with the presence of (a) 0.0, (b) 1.0 × 10 , (c) 1.0 × 10 ,
reacting hydrogen peroxide released from sucrose with
phenolsulfonate and 4-aminoantipyrine in the presence of
peroxidase enzyme, which can be used to determine the
35
relative concentration of sucrose within food samples.
As shown in the following, the bromate−PSA system was
uncovered to exhibit three isolated oscillatory regimes that
were separated by as long as 48 h of nonoscillatory evolution.
Such a result complements the earlier observation of sequential
24,25
oscillations in the bromate−phenol reaction.
mechanistic study indicates that 1,4-benzoquinone, 2-bromo-
,4-benzoquinone, 2,6-dibromo-1,4-benzoquinone, and 2,4,6-
tribromophenol are major components during the reaction.
A preliminary
1
2
. EXPERIMENTAL SECTION
All reactions were performed in a thermal-jacketed 50 mL glass
beaker (ChemGlass). A circulating water bath (Thermo
NesLab RTE 7) held the reaction temperature constant at
2
5.0 ± 0.1 °C. The reactions were monitored using a Hg|
Hg SO |K SO reference electrode coupled with a platinum
2
4
2
4
electrode (Radiometer Analytical, XR200 and M231 Pt-9).
The volume for every reaction solution was fixed at 30.0 mL.
The reaction was stirred with a magnetic stirring bar driven by
a magnetic stirrer (Fischer Isotemp) to ensure homogeneity.
All measurements were recorded through a potential meter
Figure 1. Time series of the bromate−PSA reaction performed at
−
6
different ferroin concentrations: (a) 0.0, (b) 1.0 × 10 , (c) 1.0 ×
−
5
−3
−3
−3
10 , (d) 2.4 × 10 , (e) 2.9 × 10 , and (f) 4.3 × 10 M. Other
reaction conditions were [PSA] = 0.0150 M, [H SO ] = 1.4 M, and
2
4
[
NaBrO ] = 0.040 M.
3
(
Radiometer PHM220) connected to a personal computer
through a PowerLab/4SP data logger. Mass spectrometry
measurements were performed using a Waters XEVO GS-XF
time-of-flight spectrometer with samples introduced via an
−
3
−3
−3
(d) 2.4 × 10 , (e) 2.9 × 10 , and (f) 4.3 × 10 M ferroin,
while the other conditions were held constant at [PSA] =
0.0150 M, [H SO ] = 1.4 M, and [NaBrO ] = 0.040 M. The
1
Atmospheric Solids Analysis Probe. All H NMR studies were
2
4
3
performed using a Bruker Avance 500 MHz spectrometer, and
the samples were dissolved in deuterated chloroform (Cam-
bridge Isotope Laboratories, 99.8%).
redox potential of the ferroin-free system in Figure 1a gradually
decreased within the first 3000 s, which was followed by a
group of spontaneous oscillations toward a lower potential.
Here, the autocatalytic nonlinear feedback is formed through
the oxidation of PSA intermediates by the bromine dioxide
radicals. Upon the termination of the oscillatory behavior, the
redox potential started to increase again. Notably, after the
Absorption spectra were measured with a UV−vis
spectrophotometer (Ocean Optics, 2000 USB). A quartz
cuvette (10 mm light path, HELLMA) containing 2.5 mL
sample mixture was placed in a CUV sample holder. The
cuvette was stirred with a small magnetic bar. Electrochemical
experiments were performed on a CHI 760E electrochemical
station (CHI Instruments, Bee Cave, TX). A glassy carbon
electrode with a diameter of 3.0 mm was used as the working
electrode. Platinum wire and a saturated calomel electrode
−
6
inclusion of 1.0 × 10 M ferroin, the oscillatory behavior
disappeared, where the redox potential began to increase after
the initial decrease within the first 1600 s. The inclusion of
ferroin introduced a second autocatalytic feedback through the
oxidation of ferroin by bromine dioxide radicals, which
therefore created a system consisting of two suboscillators.
The result in Figure 1b clearly demonstrates that interactions
of two oscillators can annihilate spontaneous oscillations. In
Figure 1c, the oscillatory behavior re-emerged after the ferroin
(
SCE) were used as the counter and reference electrodes,
respectively. Prior to each experiment, the working electrode
was polished with 1 μm, 0.3 μm, and then 0.05 μm fine
alumina powder and cleaned using an ultrasonic cleaner
−
5
(
Branson 1510, USA) for 10 min in double-distilled water.
Stock solutions of analytical grade sodium bromate
concentration was increased to 1.0 × 10 M. Here, the
oscillations had a much longer induction period and lasted a
significantly longer time.
(
NaBrO , Aldrich, 99%), 0.1 M, and sulfuric acid (Aldrich,
3
9
5−98%), 6.0 M, were prepared with double-distilled water.
Phenomenologically, the reaction mixture rapidly changes
from a bright red solution to a clear blue solution upon the
addition of bromate, which indicates the formation of ferriin
from ferroin. After that, the solution gradually developed an
opaque dark green color. While no periodic color change was
apparent to the naked eye, about 1−7 oscillations in the redox
potential could be seen after an induction time of around 40
min, forming the first oscillatory window. This was then
followed by a quiescent period of ∼100 min, leading to the
2+
Ferroin (Fe(phen)3 ), 0.030 M, was prepared with FeSO ·
4
7
H O (Aldrich) and 1,10-phenanthroline (Aldrich, 98%)
2
according to a 1:3 stoichiometric relationship. The sodium
-hydroxybenzenesulfonate (Aldrich, 98+%) was directly
4
dissolved in the reaction mixture. Bromate solution was
added to the reaction mixture after sodium 4-hydroxy-
benzenesulfonate had dissolved completely. All chemicals
were commercial grade and were used without further
8
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second oscillatory window. As shown in Figure 1e, when the
ferroin concentration was close to 2.9 × 10− M, a third
oscillatory window occurred after an extremely long quiescent
period of around 40 h. The increase of ferroin concentration
also led to an increase in the number of observable oscillations
within the second and third oscillatory windows. Further
increasing ferroin concentration, however, caused the dis-
appearance of the third oscillatory window, as seen in Figure
3
1
f.
Although no visible color change could be identified by the
naked eye, with the aid of UV/vis absorption measurements,
the color changes could be monitored by following ferroin
which absorbs at a wavelength of 508 nm. Here, the reaction
began at the regular reactor until spontaneous oscillations
emerged, and then 2.0 mL of the solution was transferred to a
cuvette for the absorption measurements. The reaction
solution was stirred during the measurement. As shown in
Figure 2a, spontaneous oscillations could be observed within
Figure 3. Time series of the ferroin−bromate−PSA reaction
performed at different H SO concentrations: (a) 0.8, (b) 1.0, (c)
2
4
1.3, (d) 1.4, and (e) 1.8 M.
In Figure 4, time series conducted at different bromate
concentrations are shown, where the PSA, ferroin, and sulfuric
Figure 2. UV/vis absorption time series recorded during the (a) first,
(
[
[
b) second, and (c) third oscillatory windows. The concentrations are
PSA] = 0.0150 M, [H SO ] = 1.4 M, [NaBrO ] = 0.040 M, and
2
4
3
−
3
ferroin] = 3.0 × 10 M.
Figure 4. Time series of the ferroin-catalyzed bromate−PSA reaction
carried out at different NaBrO concentrations: (a) 0.020, (b) 0.035,
3
the first and second oscillatory windows. The amplitude of the
oscillatory behavior in the third window was very low. Results
in Figures 1a and 2a together suggest that both autocatalytic
cycles play an essential role in the occurrence of spontaneous
oscillations in the first oscillatory window. The time series in
Figure 1a illustrates that the uncatalyzed oscillator only
survives for several thousand seconds; therefore, oscillations
in the second and third oscillatory windows are likely arising
from autocatalytic reactions between ferroin−bromine dioxide
radicals. The detection of ferroin oscillations in Figure 2b,c
supports the above conclusion.
(
c) 0.040, (d) 0.045, and (e) 0.075 M. Other reaction conditions
−
3
were [PSA] = 0.0150 M, [H SO ] = 1.4 M, and [ferroin] = 3.0 × 10
M.
2
4
−
3
acid concentrations were kept constant at 0.0150, 3.0 × 10 ,
and 1.4 M, respectively. Similar to that observed while
changing the ferroin or sulfuric acid concentrations, the third
oscillatory window could only be observed within a narrow
range of conditions around a bromate concentration of 0.040
M, as depicted in Figure 4c. A deviation of 0.0050 M in either
direction resulted in the disappearance of the third window.
When the bromate concentration was lowered from 0.045 M,
the number of observable oscillations in the first two oscillatory
windows began to decrease until only the initial autocatalytic
excursion could be observed, as shown in Figure 4a. Similarly,
when bromate was increased past a concentration of 0.075 M,
it resulted in all oscillatory behavior being quenched.
Figure 3 shows six time series conducted at different
concentrations of sulfuric acid: (a) 0.8, (b) 1.0, (c) 1.3, (d)
1
0
.4, and (e) 1.8 M. Other reaction conditions were [PSA] =
−
3
.0150 M, [NaBrO ] = 0.040 M, and [ferroin] = 3.0 × 10 M.
3
At a low acid concentration, there were no spontaneous
oscillations, although a very broad plateau with a high redox
potential could be seen in Figure 3a. Sequential behavior was
observed within the first 4 h of the reaction when the acid
concentration was increased above 1.0 M. Notably, within a
range of moderate acid concentration (between 1.3 and 1.5
M), a third oscillatory window also became visible. The results
presented in Figure 3 also illustrate that the increase of acid
concentration resulted in an increase in the frequency of
oscillations.
The dependence on PSA was tested and summarized in
Figure 5, where other reaction conditions were [H SO ] = 1.4
2
4
−
3
M, [NaBrO ] = 0.040 M, and [ferroin] = 3.0 × 10 M. It was
3
observed that at high concentrations of PSA (e.g., 0.0225 M in
Figure 5e) only a couple of very low frequency oscillations
could be observed. As the concentration was decreased, the
frequency and number of oscillations began to increase along
with the emergence of the two isolated oscillatory windows.
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quiescent period observed in the presence of air may be due to
the oxygen quenching the oscillatory behavior. Here, transient
complex oscillations like burst and mixed mode patterns could
be observed.
Using the same conditions as in Figure 6a, the reaction was
repeated in Figure 6b under the flow of 1:20 (v/v) mixture of
O and N , in which the long quiescent period occurred, which
2
2
led to the formation of two isolated oscillatory windows. When
pure oxygen was allowed to flow in Figure 6c, the quiescent
window became even longer, indicating the inhibitory effect of
oxygen here. Earlier studies have reported that no oxygen effect
24,25
was detected in the bromate−phenol system.
The strong
oxygen influence seen here suggests that phenol is less likely a
major product from PSA desulfonation. Such a postulation is
consistent with the UV/vis and NMR spectroscopic measure-
ments. To further confirm the oxygen influence, the reaction
was repeated under nitrogen conditions but with oxygen being
introduced at 100000 s and resulted in the immediate
quenching of oscillatory behavior as indicated by the arrow
shown in Figure 6d.
Figure 5. Time series of the ferroin-catalyzed bromate−PSA reaction
carried out at different PSA concentrations: (a) 0.0120, (b) 0.0135,
(
c) 0.0150, (d) 0.0158, and (e) 0.0225 M.
Further decrease to a concentration of 0.0150 M resulted in
the emergence of the third oscillatory window. This window
could be observed until the concentration fell below 0.0135 M,
as shown in Figure 5b.
In Figure 7 the influence of bromate concentration on
complex behavior was further explored in a nitrogen
The reaction behavior of several uncatalyzed bromate
oscillators including the bromate−phenol system has been
24,25,36−38
reported to exhibit great dependence on stirring.
Such a dependence may arise from its influences on the
extremely fast reaction steps or the influence on the diffusion
of volatile species as well as oxygen out/into the reaction
solution. It has previously been shown that oxygen can increase
the induction period as well as gradually decrease the
31,32
amplitude of the oscillatory behavior in the BZ oscillator.
To shed light on the effects of oxygen on this reaction, the
reaction solution was first purged with nitrogen gas to remove
any excess oxygen. After the addition of bromate to initiate the
reaction, a constant stream of nitrogen at a low flow rate was
applied to the space above the solution surface. Low flow rates
were used since elevated flow rates may have led to the
significant removal of the volatile species such as bromine. As
shown in Figure 6a, the second oscillatory window lasted
substantially longer when compared to the conditions run in
air. The duration of this oscillatory window was similar to the
combination of both second and third oscillatory windows of
the reaction in air (see Figure 5c). This suggests the long
Figure 7. Time series of the ferroin−bromate−PSA reaction carried
out at different NaBrO concentrations: (a) 0.036, (b) 0.040, and (c)
3
0
.044 M. Other reaction conditions were [PSA] = 0.0150 M, [H SO ]
2 4
−
3
= 1.4 M, and [ferroin] = 3.0 × 10 M. These reactions were run
under nitrogen protection.
atmosphere, where the PSA, ferroin, and sulfuric acid
−3
concentrations were kept constant at 0.0150, 3.0 × 10 , and
1
.4 M, respectively. Here, the reactor was sealed with parafilm,
while nitrogen was slowly flowed into the empty space above
the reaction solution. Clearly, increasing bromate concen-
tration from 0.036 to 0.044 M greatly prolonged the oscillation
window. Transient period-doubling and mixed mode oscil-
lations could be seen at the bromate concentrations of 0.036 M
(
Figure 7a) and 0.040 M (Figure 7b). A phenomenon of three
isolated oscillatory windows was seen at a bromate
concentration of 0.044 M, where within each oscillatory
window only simple oscillations occurred.
Figure 8 presents the cyclic voltammograms measured with a
glassy carbon electrode in two solutions containing (a) 0.0200
M PSA + 2.0 M H SO and (b) 0.0200 M PSA + 0.1 M KCl.
2
4
In the acidic solution, a new oxidation peak emerged at around
.2 V, while the anodic peak at 0.85 V also became more
1
pronounced. The qualitative and quantitative changes in the
cyclic voltammogram suggest that PSA might have decom-
posed. The UV/vis absorption method and NMR spectro-
scopic technique were deployed to examine the decomposition
products of PSA and showed there was no convincing evidence
on the formation of substantial amounts of phenol, contrary to
expectations. However, small amounts of phenol could be
Figure 6. Time series of the ferroin-catalyzed bromate−PSA reaction
carried out in the presence of different gases: (a) N , (b) 1:20 mixture
2
of O and N , (c) O , and (d) with O introduced at 100000 s. Other
2
2
2
2
reaction conditions were [PSA] = 0.0150 M, [H SO ] = 1.4 M,
2
4
−
3
[
NaBrO ], and [ferroin] = 3.0 × 10 M.
3
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Figure 8. CVs measured with a glassy carbon electrode in solutions
containing (a) 0.0200 M PSA + 2.0 M H SO and (b) 0.0200 M PSA
2
4
+
0.1 M KCl.
detected when the concentrations of PSA and H SO were
2
4
much higher. This explains why this PSA system exhibited a
24,25
very different response to oxygen.
Notably, the presence of
two well-separated anodic peaks in Figure 8 suggests that the
oxidation of PSA in acidic solution is likely occurring in two
distinct steps with very different rate constants, creating a
chemically coupled system in which the subsystems are
coupled through chemical reactions between their products
1
Figure 9. H NMR (300 MHz) spectrum of the aromatic region of
the ferroin-catalyzed bromate−PSA taken at different times: (bottom)
during the first, (middle) second, and (top) third oscillatory windows.
24,25
or intermediates.
between the two autocatalytic cycles led to the quiescent
period between the first two oscillatory windows in the form of
sequential oscillations.
To gain insight into the intermediates and final products of
1
the ferroin−bromate−PSA oscillatory reaction, H NMR
spectroscopic measurements were performed. Samples were
collected approximately halfway through each of the three
oscillatory windows and were extracted twice with diethyl
ether. After concentrating the diethyl ether solution under a
4
. CONCLUSIONS
The presence of two well-isolated anodic peaks in the cyclic
voltammogram of PSA suggests that its oxidations are likely
taking place through two stages with very different reaction
kinetics. The variation of CVs seen in Figure 8 is also indicative
on the decomposition of PSA in an acidic solution. UV/vis
absorption measurement of PSA-H SO solution at the
1
reduced pressure, H NMR samples were prepared with
1
deuterated chloroform. The H NMR throughout all three
samples showed resonances which correspond to the presence
of benzoquinone (δ = 6.80, 4H, s), 2-bromobenzoquinone (δ
=
7.32, 1H, d, J = 2.4 Hz; 6.98, 1H, d, J = 10.2 Hz; 6.84, 1H,
2
4
dd, J = 2.4, 10.2 Hz), 2,6-dibromobenzoquinone (δ = 7.34, 2H,
s), and 2,4,6-tribromophenol (δ = 7.60, 2H, s) as indicated by
the letters a−d, respectively, in Figure 9. As the reaction time
progressed from the first to the second window, the emergence
of two peaks at δ = 7.01 (2H, s) and δ = 7.41 ppm (2H, s)
could be observed, which possibly correspond to 2,3- and 2,5-
dibrominated derivatives of benzoquinone as indicated by the
letters e and f in Figure 9, respectively. The relative peak
intensity of the 2,3-dibrominated derivative continued to grow
during the third window, and due to the reaction being run for
around 50 h, the resulting spectra contained a multitude of
compounds as shown in Figure 9. The presence of these
compounds was confirmed as the mass spectrometry measure-
ments gave a series of peaks at 108, 186/188, 264/266/268,
and 320/330/332/334 m/z which correspond the benzoqui-
none, 2-bromobenzoquinone, 2,6-dibromobenzoquinone, and
wavelength of 275 nm confirms the slow decomposition of
PSA. Such a chemical property allows the ferroin−bromate−
PSA reaction to exhibit long-lasting oscillatory behavior (>2
days) in a batch reactor, making this new oscillatory system an
excellent candidate for investigating self-powered oscillating
40
gels. Notably, when only a small amount of ferroin was
introduced into the system, the system became nonoscillatory,
providing an experimental example on an earlier theoretical
prediction that the coupling of two oscillators may lead to
41
amplitude death and oscillation death.
Different from the bromate−phenol oscillator, in which
oxygen was reported to have no effect on its oscillatory
25
phenomena, oxygen was found to have strong inhibitory
effects in the ferroin−bromate−PSA system. Oscillations that
occurred within the earlier or near the end of the reaction were
not quenched by oxygen. On the other hand, spontaneous
oscillations were completely quenched by oxygen during the
intermediate stage of the reaction, which led to the
development of a very long nonoscillatory region and three
isolated oscillatory regimes. The observed inhibitory influence
of oxygen is likely through its interactions with organic
substrate radicals such as 1,4-semiquinone, which would
otherwise undergo autocatalytic reactions with bromine
dioxide radicals. It is similar to the BZ reaction, in which
oxygen influence has been attributed to the interactions
2
,4,6-tribromophenol, respectively.
A plausible reaction pathway demonstrating the formation of
benzoquinone and bromobenzoquinones is proposed as the
following: the starting material PSA undergoes oxidation and
bromination reactions in the presence of acidic bromate.
Because of the presence of the sulfonate group in the para-
position, the phenol-like reagents may also participate in
oxidation reactions in the ortho-position in ways similar to that
2
4,39
reported earlier.
With the presence of ferroin, a second
42−45
autocatalytic cycle was introduced through a reaction between
ferroin and bromine dioxide radicals. The competition
between oxygen and malonyl radicals.
Benzoquinone and
several brominated benzoquinones have been detected with
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NMR spectroscopy and mass spectrometry as major
components during the reaction. Indeed, benzoquinone,
monobromobenzoquinone, and tribromobenzoquinone could
be found in a sample that was prepared at 10 min after the start
of the reaction.
(16) Vanag, V. K.; Epstein, I. R. Pattern Formation in a Tunable
Medium : The Belousov-Zhabotinsky Reaction in an Aerosol OT
Microemulsion. Phys. Rev. Lett. 2001, 87, 1−4.
(17) Koros, E.; Varga, M.; Gyorgyi, L. Thorough Study of Bromide
̈ ̈
́
Control in Bromate Oscillators. 1. The Effect of Bromo-Complex-
Forming Metal Ions. J. Phys. Chem. 1984, 88, 4116−4121.
(18) Tang, A.; Bell, J. G.; Green, J. R.; Wang, J. Complex Nonlinear
AUTHOR INFORMATION
Corresponding Author
(J.W.) E-mail jwang@uwindsor.ca; fax 1-519-973-7089.
■
*
Behavior in the Bromate-2-Aminophenol Reaction. Int. J. Chem. Kinet.
2017, 49, 21−27.
(19) Bell, J. G.; Wang, J. Mixed Mode and Sequential Oscillations in
the Cerium-Bromate-4-Aminophenol Photoreaction. Chaos 2013, 23,
33120.
20) Amemiya, T.; Ohmori, T.; Yamaguchi, T. An Oregonator-Class
ORCID
0
Jichang Wang: 0000-0001-8647-6496
Notes
The authors declare no competing financial interest.
(
2
+
Model for Photoinduced Behavior in the Ru (Bpy)
Belousov-Zhabotinsky Reaction. J. Phys. Chem. A 2000, 104, 336−
44.
21) Vanag, V. K.; Zhabotinsky, A. M.; Epstein, I. R. Oscillatory
-Catalyzed
3
3
(
ACKNOWLEDGMENTS
This research is supported by Natural Sciences and Engineer-
ing Research Council of Canada (NSERC).
■
Clusters in the Periodically Illuminated, Spatially Extended Belousov-
Zhabotinsky Reaction. Phys. Rev. Lett. 2001, 86, 552−555.
(22) Manz, N.; Steinbock, O. Dynamics of Excitation Pulses with
Attractive Interaction: Kinematic Analysis and Chemical Wave
Experiments. Phys. Rev. E 2004, 70, 1−7.
REFERENCES
■
(23) Manz, N.; Mueller, S. C.; Steinbock, O. Anomalous Dispersion
(
1) Jaeger, H.; Haas, H. Harnessing Nonlinearity: Predicting Chaotic
Systems and Saving Energy in Wireless Communication. Science 2004,
of Chemical Waves in a Homogeneously Catalyzed Reaction System.
J. Phys. Chem. A 2000, 104, 5895−5897.
3
(
04, 78−80.
2) Peyrard, M. Nonlinear Dynamics and Statistical Physics of DNA.
Nonlinearity 2004, 17, R1−R40.
3) Wong, W. W.; Tsai, T. Y.; Liao, J. C. Single-Cell Zeroth-Order
̌
24) Adamcíkova, L.; Farbulova, Z.; Sevcík, P. Dynamic Behavior
̌ ́ ́ ̌
(
During the Oxidation of Phenol with Bromate in a Closed Reactor.
New J. Chem. 2001, 25, 487−490.
(
̌
25) Adamcíkova, L.; Farbulova, Z.; Sevcík, P.; Kawczynski, A. L.
̌ ́ ́ ̌
(
Protein Degradation Enhances the Robustness of Synthetic Oscillator.
Mol. Syst. Biol. 2007, 3, 130.
Sequential Oscillations in the Uncatalyzed Bromate Oscillator and
Their Simple Qualitative Model. J. Phys. Chem. A 2003, 107, 508−
(4) Fiorillo, C. D.; Tobler, P. N.; Schultz, W. Evidence That the
5
(
11.
Delay-Period Activity of Dopamine Neurons Corresponds to Reward
Uncertainty Rather Than Backpropagating TD Errors. Behav. Brain
Funct. 2005, 1, 7.
26) Orban, M.; Koros, E. Chemical Oscillations During the
́
̋
̈
Uncatalyzed Reaction of Aromatic Compounds with Bromate. 1.
Search for Chemical Oscillators. J. Phys. Chem. 1978, 82, 1672−1674.
(
5) Phillips, J. D. Sources of Nonlinearity and Complexity in
Geomorphic Systems. Prog. Phys. Geogr. 2003, 27, 1−23.
6) Field, R. J.; Koros, E.; Noyes, R. M. Oscillations in Chemical
(27) Harati, M.; Amiralaei, S.; Green, J.; Wang, J. Chemical
Oscillations in the 4-Aminophenol − Bromate Photoreaction. Chem.
(
̈
̈
Phys. Lett. 2007, 439, 337−341.
Systems. II. Thorough Analysis of Temporal Oscillations in the
(28) Li, N.; Wang, J. Ferroin-Induced Complex Oscillations in the
Bromate-Cerium-Malonic Acid System. J. Am. Chem. Soc. 1972, 94,
Bromate−Hydroquinone Photochemical Reaction. J. Phys. Chem. A
009, 113, 6297−6300.
29) Morimitsu, M.; Tamura, H.; Matsunaga, M.; Otogawa, R.
Polarization Behaviour and Lifetime of IrO -Ta O -SnO /Ti Anodes
8
(
649−8664.
2
(
7) Noszticzius, Z.; Stirling, P.; Wittmann, M. Measurement of
Bromine Removal Rate in the Oscillatory BZ Reaction of Oxalic Acid.
Transition From Limit Cycle Oscillations to Excitability via Saddle-
Node Infinite Period Bifurcation. J. Phys. Chem. 1985, 89, 4914−
2
2
5
2
in p-Phenolsulfonic Acid Solutions for Tin Plating. J. Appl.
Electrochem. 2000, 30, 511−514.
4
(
921.
(30) Bengoa, L. N.; Tuckart, W. R.; Zabala, N.; Prieto, G.; Egli, W.
8) Noszticzius, Z.; Bodiss, J. A Heterogeneous Chemical Oscillator.
́
A. Tin Coatings Electrodeposited from Sulfonic Acid-Based Electro-
lytes: Tribological Behavior. J. Mater. Eng. Perform. 2015, 24, 2274−
The Belousov-Zhabotinskii-Type Reaction of Oxalic Acid. J. Am.
Chem. Soc. 1979, 101, 3177−3182.
(
2
281.
9) Marchettini, N.; Budroni, A.; Rossi, F.; Masia, M.; Liveri, M. L.
(
31) Cooke, T. F.; Weigmann, H.-D. Stain Blockers for Nylon
Fibres. Rev. Prog. Color. Relat. Top. 1990, 20, 10−18.
32) Minakawa, M.; Baek, H.; Yamada, Y. M. A.; Han, J. W.;
T. Role of the Reagents Consumption in the Chaotic Dynamics of the
Belousov−Zhabotinsky Oscillator in Closed Unstirred Reactors. Phys.
Chem. Chem. Phys. 2010, 12, 11062−11069.
(
(10) Maselko, J.; Swinney, H. L. Complex Periodic Oscillations and
Uozumi, Y. Direct Dehydrative Esterification of Alcohols and
Carboxylic Acids with a Macroporous Polymeric Acid Catalyst. Org.
Lett. 2013, 15, 5798−5801.
(33) Du, X.; Lu, Y.; Li, L.; Wang, J.; Yang, Z. Synthesis and Unusual
Properties of Novel Alkylbenzene Sulfonate Gemini Surfactants.
Colloids Surf., A 2006, 290, 132−137.
Farey Arithmetic in the Belousov − Zhabotinskii Reaction. J. Chem.
Phys. 1986, 85, 6430−6441.
(11) Strizhak, P. E.; Kawczynski, A. L. Regularities in Complex
Transient Oscillations in the Belousov-Zhabotinsky Reaction in a
Batch Reactor. J. Phys. Chem. 1995, 99, 10830−10833.
(12) Pelle, K.; Wittmann, M.; Noszticzius, Z.; Lombardo, R.;
(34) Turcanu, A.; Bechtold, T. Dyes and Pigments PH Dependent
Redox Behaviour of Alizarin Red S (1,2-Dihydroxy-9,10-Anthraqui-
none-3-Sulfonate) - Cyclic Voltammetry in Presence of Dispersed Vat
Dye. Dyes Pigm. 2011, 91, 324−331.
Sbriziolo, C.; Liveri, M. L. T. Perturbation of the Oscillatory BZ
Reaction with Methanol and Ethylene Glycol : Experiments and
Model Calculations. J. Phys. Chem. A 2003, 107, 2039−2047.
(13) Zeyer, K. P.; Schneider, F. W. Periodicity and Chaos in
(35) Alcazar, A.; Jurado, J.; Martin, M.; Pablos, A.; Gonzalez, A.
Enzymatic-Spectrophotometric Determination of Sucrose in Coffee
Beans. Talanta 2005, 67, 760−766.
Chemiluminescence: The Ruthenium-Catalyzed Belousov-Zhabotin-
sky Reaction. J. Phys. Chem. A 1998, 102, 9702−9709.
(14) Ralph, C. H.; Murel, M. B. o-Bromophenol. Org. Synth. 1934,
(36) Orban, M.; Kurin-Csorgei, K.; Zhabotinsky, A. M.; Epstein, I.
́
̈
1
(
4, 14−16.
15) Kadar
Waves in Sub-Excitable Media. Nature 1998, 391, 770−772.
R. New Indicators for Visualizing Pattern Formation in Uncatalyzed
Bromate Oscillatory Systems. J. Am. Chem. Soc. 1998, 120, 1146−
1150.
́ ́
, S.; Wang, J.; Showalter, K. Noise-Supported Travelling
8
306
DOI: 10.1021/acs.jpca.8b07766
J. Phys. Chem. A 2018, 122, 8301−8307

The Journal of Physical Chemistry A
Article
(
37) Zhao, B.; Wang, J. Stirring-Controlled Bifurcations in the 1,4-
Cyclohexanedione - Bromate Reaction. J. Phys. Chem. A 2005, 109,
647−3651.
38) Li, J.; Wang, J. Complex Kinetics and Significant Influences of
3
(
Bromine Removal in Ferroin−Bromate−Metol Reaction. Phys. Chem.
Chem. Phys. 2011, 13, 15539−15545.
(39) Gyorgyi, L.; Varga, M.; Koros, E.; Field, R. J.; Ruoff, P.
̈ ̈ ̈
Simulations of the Iodide Ion Perturbed Uncatalyzed Belousov-
Zhabotinskii Oscillator with 1-Hydroxy-4-(2-(Methylamino)Propyl)-
Benzene. J. Phys. Chem. 1989, 93, 2836−2842.
(40) Ren, L.; She, W.; Gao, Q.; Pan, C.; Ji, C.; Epstein, I. R.
Retrograde and Direct Wave Locomotion in a Photosensitive Self-
Oscillating Gel. Angew. Chem., Int. Ed. 2016, 55, 14301−14305.
(41) Kamal, N. K.; Sharma, P. R.; Shrimali, M. D. Oscillation
Suppression in Indirectly Coupled Limit Cycle Oscillators. Phys. Rev.
E 2015, 92, 022928.
(
42) Bar-Eli, K.; Haddad, S. Effect of Oxygen on the Belousov-
Zhabotinskii Oscillating Reaction. J. Phys. Chem. 1979, 83, 2952−
958.
43) Wang, J.; Hynne, F.; Sørensen, P. G.; Nielsen, K. Oxygen
2
(
Influence on Complex Oscillations in a Closed Belousov -
Zhabotinsky Reaction. J. Phys. Chem. 1996, 100, 17593−17598.
(44) Steinbock, O.; Hamik, C. T.; Steinbock, B. Oxygen Inhibition
of Oscillations in the Belousov-Zhabotinsky Reaction. J. Phys. Chem. A
000, 104, 6411−6415.
45) Neumann, B.; Mueller, S. C.; Hauser, M. J. B.; Steinbock, O.;
2
(
Simoyi, R. H.; Dalal, N. S. Identification and Kinetic Study of the
Peroxymalonyl Radical in the Aerobic Oxidation of Malonic Acid by
Cerium(IV). J. Am. Chem. Soc. 1995, 117, 6372−6373.
8
307
DOI: 10.1021/acs.jpca.8b07766
J. Phys. Chem. A 2018, 122, 8301−8307