The Journal of Physical Chemistry A
Article
(10) Epstein, I. R., Pojman, J. A. An Introduction to Nonlinear
Chemical Dynamics: Oscillations, Waves, Patterns and Chaos; Oxford
University Press: Oxford, 1998.
(11) Oscillations and Travelling Waves in Chemical Systems; Field, R. J.,
Burger, M., Eds.; Wiley & Sons: New York, 1985.
(12) Blaha, K.; Lehnert, J.; Keane, A.; Dahms, T.; Hoevel, P.; Schoell,
E.; Hudson, J. L. Clustering in Delay-Coupled Smooth and
Relaxational Chemical Oscillators. Phys. Rev. E: Stat., Nonlinear, Soft
Matter Phys. 2013, 88, 062915.
́
(13) Pesek, O.; Schreiberova, L.; Schreiber, I. Dynamical Regimes of
a pH-Oscillator Operated in Two Mass-Coupled Flow-Through
autocatalytic cycles were effectively balanced, which was
achieved through manipulation of the individual reaction
parameters. Mixed mode oscillations were also present when
cerium(IV) was utilized. The systems’ sensitivity to illumination
was significant as removal of illumination during an oscillatory
regime completely quenched the systems’ reactivity. Analysis
1
with H NMR spectroscopy indicates that the presence of
methyl group prevents bromination during the mH2Q−
bromine reaction. However, 2-bromo-3-methyl-1,4-benzoqui-
none was detected with 1H NMR spectroscopic analysis during
the bromate−mH2Q photoreaction.
Reactors. Phys. Chem. Chem. Phys. 2011, 13, 9849−9856.
́
(14) Sagues, F.; Epstein, I. R. Nonlinear Chemical Dynamics. Dalton
Trans. 2003, 1201−1217.
ASSOCIATED CONTENT
* Supporting Information
■
(15) Rossi, F.; Lombardo, R.; Sciascia, L.; Sbriziolo, C.; Liveri, M. L.
T. Spatio-Temporal Perturbation of the Dynamics of the Ferroin
Catalyzed Belousov−Zhabotinsky Reaction in a Batch Reactor Caused
by Sodium Dodecyl Sulfate Micelles. J. Phys. Chem. B 2008, 112,
7244−7250.
S
1H NMR spectra illustrating (Figure S1) the formation of 2-
methyl-1,4-benzoquinone before oscillations begin; (Figure S2)
the formation of a product with a distinct AB coupling pattern,
of which 2-bromo-3-methyl-1,4-benzoquinone is the most
likely candidate; and (Figure S3) reaction between bromine
and mH2Q under illumination showing both the oxidation and
photoreduction products. This material is available free of
(16) Steinbock, O.; Zykov, V. S.; Muller, S. C. Control of Spiral-
̈
Wave Dynamics in Active Media by Periodic Modulation of
Excitability. Nature (London, U.K.) 1993, 366, 322−324.
̌ ́
(17) Bakes, D.; Schreiberova, L.; Schreiber, I.; Hauser, M. J. B.
Mixed-Mode Oscillations in a Homogeneous pH-Oscillatory Chemical
Reaction System. Chaos 2008, 18, 015102.
(18) Dolnik, M.; Banks, A. S.; Epstein, I. R. Oscillatory Chemical
Reaction in a CSTR with Feedback Control of Flow Rate. J. Phys.
Chem. A 1997, 101, 5148−5154.
AUTHOR INFORMATION
Corresponding Authors
Notes
■
(19) Rossi, F.; Budroni, M. A.; Marchettini, N.; Cutietta, L.; Rustici,
M.; Liveri, M. L. T. Chaotic Dynamics in an Unstirred Ferroin
Catalyzed Belousov−Zhabotinsky Reaction. Chem. Phys. Lett. 2009,
480, 322−326.
The authors declare no competing financial interest.
(20) Field, R. J., Gyorgyi, L. Chaos in Chemistry and Biochemistry;
̈
Word Scientific: Singapore, 1993.
ACKNOWLEDGMENTS
■
(21) Bell, J. G.; Green, J. R.; Wang, J. Nonlinear Dynamical Behavior
in the Photodecomposition of N-Bromo-1,4-Benzoquinone-4-Imine. J.
Phys. Chem. A 2013, 117, 4545−4550.
(22) Bell, J. G.; Wang, J. Mixed Mode and Sequential Oscillations in
the Cerium−Bromate-4-Aminophenol Photoreaction. Chaos 2013, 23,
033120.
(23) Berenstein, I.; Yang, L.; Dolnik, M.; Zhabotinsky, A. M.;
Epstein, I. R. Dynamic Mechanism of Photochemical Induction of
Turing Superlattices in the Chlorine Dioxide−Iodine−Malonic Acid
Reaction−Diffusion System. J. Phys. Chem. A 2005, 109, 5382−5387.
(24) Harati, M.; Amiralaei, S.; Green, J. R.; Wang, J. Nonlinear
Instabilities in the Light-Mediated Bromate-4-Aminophenol Reaction.
J. Photochem. Photobiol., A 2008, 198, 92−97.
(25) Li, J.; Wang, J. Complex Dynamical Behavior in the Highly
Photosensitive Cerium−Bromate−1,4-Benzoquinone Reaction. J. Phys.
Chem. A 2012, 116, 8130−8137.
(26) Zhao, B.; Wang, J. Chemical Oscillations During the
Photoreduction of 1,4-Benzoquinone in Acidic Bromate Solution. J.
Photochem. Photobiol., A 2007, 192, 204−210.
(27) Zhao, B.; Wang, J. Photo-Mediated Bromate−1,4-Benzoquinone
Reaction: A Novel Photochemical Oscillator. Chem. Phys. Lett. 2006,
430, 41−44.
(28) Amemiya, T.; Wang, J. Design of Photo-Controlled Chemical
Oscillators. Acta Phys.-Chim. Sin. 2010, 26, 99−109.
The researchers thank the Natural Sciences and Engineering
Research Council of Canada (NSERC) and Canada Founda-
tion for Innovation (CFI) for financial support.
REFERENCES
■
(1) Szalai, I.; Koros, E. The 1,4-Cyclohexanedione−Bromate−Acid
̈
̈
Oscillatory System. 3. Detailed Mechanism. J. Phys. Chem. A 1998,
102, 6892−6897.
(2) Gorner, H. Photoprocesses of p-Benzoquinones in Aqueous
Solution. J. Phys. Chem. A 2003, 107, 11587−11595.
(3) Li, N.; Wang, J. Ferroin-Induced Complex Oscillations in the
Bromate−Hydroquinone Photochemical Reaction. J. Phys. Chem. A
2009, 113, 6297−6300.
(4) Amemiya, T.; Wang, J. A Chemical Oscillator Based on the
Photoreduction of 2-Methyl-1,4-benzoquinone. J. Phys. Chem. A 2010,
114, 13347−13352.
(5) Field, R. J.; Koros, E.; Noyes, R. M. Oscillations in Chemical
̈
̈
Systems. II. Thorough Analysis of Temporal Oscillation in the
Bromate−Cerium−Malonic Acid System. J. Am. Chem. Soc. 1972, 94,
8649−8664.
(6) 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.
(7) Luengviriya, C.; Luengviriya, J.; Sutthiopad, M.; Porjai, P.;
(29) Johnson, B. R.; Scott, S. K.; Thompson, B. W. Modelling
Complex Transient Oscillations for the BZ Reaction in a Batch
Reactor. Chaos 1997, 7, 350−358.
Tomapatanaget, B.; Muller, S. C. Excitability of the Ferroin-Catalyzed
̈
Belousov-Zhabotinsky Reaction with Pyrogallol. Chem. Phys. Lett.
2013, 561, 170−174.
(30) Gragnani, A. Qualitative Analysis of the Belousov−Zhabotinskii
Reaction in a Batch Reactor. Int. J. Bifurcation Chaos Appl. Sci. Eng.
2006, 16, 579−588.
́ ́
(8) Bansagi, T.; Leda, M.; Toiya, M.; Zhabotinsky, A. M.; Epstein, I.
R. High-Frequency Oscillations in the Belousov−Zhabotinsky
Reaction. J. Phys. Chem. A 2009, 113, 5644−5648.
(31) Wang, J.; Soerensen, P. G.; Hynne, F. Transient Period
Doublings, Torus Oscillations, and Chaos in a Closed Chemical
System. J. Phys. Chem. 1994, 98, 725−727.
(9) Koros, E.; Orban, M.; Habon, I. Chemical Oscillations during the
̈
̈
Uncatalyzed Reaction of Aromatic Compounds with Bromate. 3.
Effect of One-Electron Redox Couples on Uncatalyzed Bromate
Oscillators. J. Phys. Chem. 1980, 84, 559−560.
(32) Ruoff, P.; Noyes, R. M. An Amplified Oregonator Model
Simulating Alternative Excitabilities, Transitions in Types of
E
dx.doi.org/10.1021/jp505378r | J. Phys. Chem. A XXXX, XXX, XXX−XXX