Metal Ion Catalyzed Autoxidation Reactions: Kinetics and Mechanisms

Fábián, István; Csordás, Viktor

doi:10.1002/chin.200341281

Cited by 2 publications

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“…The sulfate ion radical (SO 4 –• ) is a very reactive species that plays a central role as an intermediate in a number of reaction systems, most notably the autoxidation of sulfur(IV) , or one-electron oxidations using the peroxomonosulfate ion. , The iodide ion is also known to catalyze the aqueous autoxidation of sulfur(IV); therefore, directly measuring the kinetics of the reaction between SO 4 –• and I – was important. It was found that the sulfate ion radical can be most favorably generated through the photolysis of a peroxodisulfate ion (S 2 O 8 2– ) initiated by a laser pulse at 266 nm In the presence I – , the following reaction takes place As a subsequent step, iodine atoms (I • ) give iodine molecule ions (I 2 –• ) with excess I – in a reversible process In the last step, I 2 –• recombines to give triiodide ions (I 3 – ) and I – Reactions and are also highly important in the aqueous photochemistry of I – . ,, The progress of reaction is primarily determined by the laser power.…”

Section: Resultsmentioning

confidence: 99%

“…Inspired by the seminal work of Alan Turing on morphogenesis (shape formation in biological systems), 21 reaction−diffusion systems have already proved very useful in interpreting chemical and biological pattern formation 22−24 as well as other nonlinear dynamic phenomena such as oscillation, chaos, or self-organizing systems up to the most recent literature studies. 25 ) is a very reactive species that plays a central role as an intermediate in a number of reaction systems, most notably the autoxidation of sulfur(IV) 31,32 or one-electron oxidations using the peroxomonosulfate ion. 33,34 The iodide ion is also known to catalyze the aqueous autoxidation of sulfur(IV); 35 therefore, directly measuring the kinetics of the reaction between SO 4 −• and I − was important.…”

Section: ■ Introductionmentioning

confidence: 99%

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Modeling Studies of Inhomogeneity Effects during Laser Flash Photolysis Experiments: A Reaction–Diffusion Approach

Dóka

Lente

2017

J. Phys. Chem. A

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This work presents a rigorous mathematical study of the effect of unavoidable inhomogeneities in laser flash photolysis experiments. There are two different kinds of inhomegenities: the first arises from diffusion, whereas the second one has geometric origins (the shapes of the excitation and detection light beams). Both of these are taken into account in our reported model, which gives rise to a set of reaction-diffusion type partial differential equations. These equations are solved by a specially developed finite volume method. As an example, the aqueous reaction between the sulfate ion radical and iodide ion is used, for which sufficiently detailed experimental data are available from an earlier publication. The results showed that diffusion itself is in general too slow to influence the kinetic curves on the usual time scales of laser flash photolysis experiments. However, the use of the absorbances measured (e.g., to calculate the molar absorption coefficients of transient species) requires very detailed mathematical consideration and full knowledge of the geometrical shapes of the excitation laser beam and the separate detection light beam. It is also noted that the usual pseudo-first-order approach to evaluating the kinetic traces can be used successfully even if the usual large excess condition is not rigorously met in the reaction cell locally.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Modeling Studies of Inhomogeneity Effects during Laser Flash Photolysis Experiments: A Reaction–Diffusion Approach

Dóka

Lente

2017

J. Phys. Chem. A

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Light-induced multistep redox reactions: The diode-array spectrophotometer as a photoreactor

Fábián

Lente

2010

Pure and Applied Chemistry

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The light source of a photometer may induce chemical reactions in photosensitive reactive systems. Diode-array spectrophotometers are particularly suitable for producing such phenomena. This paper provides an overview on how this equipment can be used as a photoreactor. The principles of various techniques to control the intensity and spectral region of the illuminating light are discussed in detail. It will be shown that the quantum yields of various photochemically induced redox reactions can be determined by exploiting specific features of diode-array spectrophotometers. Kinetic coupling between primary photochemical and secondary thermally activated reaction steps are utilized to explore intimate details of composite redox reactions. Key aspects of the method applied are demonstrated via the photoreactions of 2,6-dichloro-1,4-benzoquinone (DCQ), the photoinduced autoxidation of S(IV) and a photochemically activated redox reaction of the chlorate ion.

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Metal Ion Catalyzed Autoxidation Reactions: Kinetics and Mechanisms

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 2 publications

References 1 publication

Modeling Studies of Inhomogeneity Effects during Laser Flash Photolysis Experiments: A Reaction–Diffusion Approach

Modeling Studies of Inhomogeneity Effects during Laser Flash Photolysis Experiments: A Reaction–Diffusion Approach

Light-induced multistep redox reactions: The diode-array spectrophotometer as a photoreactor

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