Light-induced nonequilibrium phase transition between quasistationary states of the Briggs-Rauscher reaction under batch conditions

Vanag, Vladimir K.; Алфимов, М. В.

doi:10.1021/j100111a027

Cited by 26 publications

(45 citation statements)

References 6 publications

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“…It was supposed that IMA (or diiodomalonic acid) could act as a source of iodine in the Briggs-Rauscher reaction. [16][17][18][19] On the basis of the results reported here, similar role of IMA in the present oscillatory reaction is anticipated. A kinetic study of the light-induced decomposition of iodide-free IMA solution to tartronic acid, iodine, and iodide ion can shed light on the details of the mechanism of this photosensitive oscillator as well as that of the Briggs-Rauscher reaction.…”

Section: Discussionsupporting

confidence: 86%

Light-Induced State Transitions in the Oscillatory ClO2--Cl--Iodomalonic Acid System in a Semibatch Reactor

Rábai

Hanazaki

1994

J. Phys. Chem.

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The dynamical behavior of the oscillatory ClOz--Cl--iodomalonic acid reaction in a semibatch reactor has been found to be extremely sensitive to the UV light, while the light above 420 nm does not affect the kinetics. Continuous illumination increases the amplitude and the period. Oscillations are completely extinguished beyond a critical light power. Light-induced transitions from nonoscillatory to oscillatory state and bursting-like responses upon periodic perturbations with 370 nm light have been found. The lightaccelerated formation of a reactive iodine species from iodomalonic acid and its subsequent reaction with the chlorite ion is responsible for the light sensitivity of the dynamical behavior.

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Section: Discussionsupporting

confidence: 86%

Light-Induced State Transitions in the Oscillatory ClO2--Cl--Iodomalonic Acid System in a Semibatch Reactor

Rábai

Hanazaki

1994

J. Phys. Chem.

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“…It is reasonably concluded that I 2 formation at the end of reaction (state II) must proceed through iodomalonic acid decomposition mediated by I • formation. This decomposition (i.e., transition I → II) is energetically demanding and may be facilitated by light . Besides a very puzzling stochasticity, the interesting question is why this transition occurs at all, at the end of oscillatory evolution, taking into account that no new chemicals are added into the system.…”

Section: Discussionmentioning

confidence: 99%

“…This decomposition (i.e., transition I → II) is energetically demanding and may be facilitated by light. 39 Besides a very puzzling stochasticity, the interesting question is why this transition occurs at all, at the end of oscillatory evolution, taking into account that no new chemicals are added into the system. According to the mentioned Occam's razor-attitude, the simplest explanation may be nucleation-coupled chemical reactions.…”

Section: ■ Discussionmentioning

confidence: 99%

Is Iodine Oxidation with Hydrogen Peroxide Coupled with Nucleation Processes?

2019

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An intriguing step of the Bray−Liebhafsky oscillatory reaction, that is, iodine oxidation with hydrogen peroxide, was examined. This process is characterized by enormous stochasticity of reaction induction times in the presence of mild mixing. In the present investigations, it was found that even in the presence of mixing, stochasticity is seriously reduced with simple glass powder addition. Using transparent glass, standard deviations changed from 184.9 to 10.6 min for 19 °C, and from 128.2 to 1.9 min for 27 °C. Repeating experiments with amber glass further confirmed those results as standard deviations changed from the mentioned ones to 8.7 min for 19 °C and to 2.5 min for 27 °C. Inert glass particles enhanced heterogeneous nucleation of oxygen formed in chemical reactions. Together with the previous analysis of the involved kinetic barrier of the whole reaction, it is an additional strong evidence of a possible energetic coupling between nucleation of glass cavities and chemical reactions. Such processes are usually neglected and may considerably change the investigations of the reaction mechanisms in other complex systems. Reaction was followed by the potentiometric method at 19 and 27 °C. The adjusted stopped-flow titration method was used in order to confirm the high degree of iodine to iodate conversion in the presence of nucleation centers.

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“…These radicals have been known to exist in aqueous solutions. It should be noted that in a study on the Briggs-Rauscher reaction, Vanag and Alfimov [16] arrived at a conclusion that reaction ( M l ) was not sensitive to light when they tested it in the presence of excess malonic acid. They considered that in addition to 12, only di-iodomalonic acid could be held responsible for the observed photoresponses of the Briggs-Rauscher system.…”

Section: Mechanismmentioning

confidence: 99%

Photo‐induced disproportionation of iodomalonic acid

Rábai

Hanazaki

1995

Int J of Chemical Kinetics

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The stoichiometry, equilibrium, and kinetics of the photo-induced disproportionation of iodomalonic acid to I-, 12, and tartronic acid have been studied by means of spectrophotometry and iodide selective electrode at 20.0 2 0.2"C, pH 2.0-4.0. At pH > 2.9, only Iand HOCH(COOHI2 are detected as major products and the reaction reaches 100% conversion. At pH < 2.9, 12 and malonic acid are also formed and the reaction stops at a conversion rate less than 100%. Both UV (band with a peak at 360 nm) and visible light (480 nm) have been found to be effective. Two primary photochemical processes are identified: (MU ICH(COOH)2 + hv I' + 'CH(C0OH)z (M2) While both reactions are sensitive to UV light, only (M2) can be affected by visible light. (Ml) and (M2) are considered to initiate a chain reaction sequence in which I' radicals oxidize iodomalonic acid, Dual effects of reaction products on the reaction rate have been observed: while iodine increases the efficiency of visible light and accelerates the reaction, malonic acid inhibits the photo-decomposition by mediating the recombination of I' radicals to 12. 0 1995 John Wiley & Sons, Inc. I2 + hv = 21. of the iodination of MA [91 and methylmalonic acid [lo] have already been carried out

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Light-induced nonequilibrium phase transition between quasistationary states of the Briggs-Rauscher reaction under batch conditions

Cited by 26 publications

References 6 publications

Light-Induced State Transitions in the Oscillatory ClO2--Cl--Iodomalonic Acid System in a Semibatch Reactor

Light-Induced State Transitions in the Oscillatory ClO2--Cl--Iodomalonic Acid System in a Semibatch Reactor

Is Iodine Oxidation with Hydrogen Peroxide Coupled with Nucleation Processes?

Photo‐induced disproportionation of iodomalonic acid

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