Kinetic investigation of sulfur(IV) oxidation by peroxo compounds R-OOH in aqueous solution

Drexler, Chad I.; Elias, Horst; Fecher, B.; Wannowius, Klaus J.

doi:10.1007/bf00321521

Cited by 44 publications

(32 citation statements)

References 26 publications

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“…It is known that the rate of reaction for both preservatives with hydrogen peroxide is characterized by a strong pH dependence. In the pH range 2-6, lower pH values increase the rate of reaction for SO 2 (Drexler et al 1991), while the oxidation rate of GSH by hydrogen peroxide increases with increasing pH (Finley et al 1981). However, taking into account the low amount of GSH used in this experiment and the high O 2 :GSH molar reaction ratio, it seems that the more relevant effect produced by GSH is due to other reactions than to its reaction with H 2 O 2 , likely due to its capability of reacting rapidly with quinones (Nikolantonaki and Waterhouse 2012) and other organic compounds such as catechin, hydroxycinnamic acids, and carbonyls involved in wine oxidation (Bouzanquet et al 2012, Sonni et al 2011b).…”

Section: Resultsmentioning

confidence: 99%

Sulfur Dioxide and Glutathione Alter the Outcome of Microoxygenation

Gambuti

Han

Peterson

et al. 2015

Am. J. Enol. Vitic.

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Section: Resultsmentioning

confidence: 99%

Sulfur Dioxide and Glutathione Alter the Outcome of Microoxygenation

Gambuti

Han

Peterson

et al. 2015

Am. J. Enol. Vitic.

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“…This constant has only been measured once by Amels et al [1996] study, which is part of the PhD work of Götz [1996] and this value can be a source of potential error. Despite the lack of data on the reaction constant of reaction (A69), the reactivity of peroxo compounds R‐OOH toward the sulfur(IV) has been investigated in details by Drexler et al [1991]. In this study, looking at the reactivity of hydrogen peroxide (R = H), peroxonitrous acid (R = NO) and peroxoacetic acid (R = Ac), a general relationship for the rates of oxidation of sulfur(IV) by peroxo compounds following a three‐term rates law was established including available data for reactivity of peroxomonosulfuric acid (R = SO 3 − ) and methyl hydroperoxide (R = CH 3 ).…”

Section: Resultsmentioning

confidence: 99%

Modeling study of strong acids formation and partitioning in a polluted cloud during wintertime

Leriche¹

2003

J. Geophys. Res.

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[1] A multiphase chemistry model coupled with a quasi-spectral microphysical model has been applied to measurements from the European Cloud Ice Mountain Experiment campaign to quantify the formation of the strong acids nitrate and sulfate and to evaluate the role of microphysical processes in redistributing reactive species among the different phases (gas versus cloud and/or rain). Significant formation of nitrate and sulfate are found to be due to the reaction of pernitric acid with the sulfite ion. Moreover, pernitric acid, because of its equilibrium in the gas phase and its high solubility, is always available both in cloud water and in rainwater via mass transfer from the gas phase. The sulfite ion comes from the mass transfer from the gas phase of sulfur dioxide in cloud water. When rain formation begins, it is efficiently transferred to the rainwater by collision/ coalescence processes. This leads to an enhancement in strong acid production when microphysics is activated in the model. Modeled results have been compared with experimental data in an effort to retrieve a behavior law related to the partitioning between the gas and aqueous phases of the cloud. In particular, when collision/coalescence processes are considered, an improvement in retrieving the partitioning of soluble species and especially nitrate is observed. A higher production in sulfate could help interpret the discrepancy of global model calculations with observed sulfate concentrations in Europe in wintertime.

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“…at an ionic strength of 0.5 M, 1.0 M, and 2.0 M (NaC104), respectively, with a stopped-flow equipment described earlier [2]. The details of the experimental procedure were described [2]. The pH (-0.3 to 13) was adjusted with buffers based on HClO4, CICH,COOH, HCOOH, CH,COOH, H2P07, HTRIS+ and NaOH.…”

Section: Methodsmentioning

confidence: 99%

“…The pKa of the species H3O; as derived from the kinetic data, is found to be pKRl = 1.5-2.0. -In the pH range 6-8, the rate is given by (2) (pKs2 = pKa(HSO;)).…”

Section: Referencesmentioning

confidence: 99%

“…Mechanistically, the reaction of the HSOT-ion with H202 is initiated by fast formation of HOOSO, (= anion of peroxosulfurous acid). The internal redox reaction occurs through an intramolecular, general-acid catalyzed rearrangement of the intermediate HOOSO, [2]. According to (6) (ko = buffer-corrected k2), the pH-profile lgko = f(pH) is linear in the pH range 2 -6 (slope = -l), the contribution of kHoH [H20] being negligible.…”

Section: Introductionmentioning

confidence: 99%

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Kinetics and Mechanism of Sulfur(IV) Oxidation by Hydrogen Peroxide in Aqueous Phase: The Non‐Linear Parts of the pH‐Profile

Drexler

Elias

Fecher

et al. 1992

Ber Bunsenges Phys Chem

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Similar results were observed when Mn(I1) is added to the Fe(I1) system, the effect being most significant in the presence of some initially added Fe(II1). A series of typical results for the sulfite induced autoxidation of Fe(I1) as a function of Mn(I1) concentration are reported in Fig. 6. In this case the Mn(I1) effect seems to exhibit a square dependence on its concentration. Although the details of this synergistic effect are not well understood at present, the observed Mn(I1) dependence may suggest the participation of dimeric species. Again the reaction of Fe(II1) with Mn(I1) t o produce Fe(I1) and Mn(II1) can initiate the overall sulfite induced autoxidation of Fe(I1). ConclusionsThe work described in this report has resolved important aspects of the autoxidation of metal ions that is needed in order to complete the catalytic cycle for metal catalyzed autoxidation reactions of S(IV) oxides. The remarkable finding that sulfite can induce such oxidation processes and the resulting redox cycling of the metal ions may be of significance in accounting for the importance of such reactions in atmospheric oxidation processes. The relative concentration ratio of oxygen (or another oxidant such as H202 or 0,) and sulfite determines the oxidation state and the catalytic activity of the investigated metal ions. This concentration ratio will vary under atmospheric conditions depending on the oxygen and sulfite levels present, and as such have a dynamic effect on the overall autoxidation chemistry.The authors gratefully acknowledge financial support from the Deutsche Forschungsgemeinschaft, Bundesministerium fur Forschung und Technologie, and Commission of the European Communities. a) On leave from the Stopped-flow spectrophotometry was used to study the oxidation of S(IV) by H202 at 285 K and 298 K, respectively, in the pH range -0.3 to 13 in buffered aqueous solution under pseudo-first-order conditions (I = 0.5, 1.0 and 2.0 M NaC104, respectively). The reaction of HSOT with H202 is subject to generalacid catalysis whereas that of the s@,ion is not. The dependence of the experimental first-order rate constant on the concentration of the excess partner [H202] was studied in detail. -In the pH range -0.3 to 6 the rate is given by Eq. (1) (KRl and Ksl: acid dissociation constants of H302+ and SO2, respectively; [HI = proton activity).

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Kinetic investigation of sulfur(IV) oxidation by peroxo compounds R-OOH in aqueous solution

Cited by 44 publications

References 26 publications

Sulfur Dioxide and Glutathione Alter the Outcome of Microoxygenation

Sulfur Dioxide and Glutathione Alter the Outcome of Microoxygenation

Modeling study of strong acids formation and partitioning in a polluted cloud during wintertime

Kinetics and Mechanism of Sulfur(IV) Oxidation by Hydrogen Peroxide in Aqueous Phase: The Non‐Linear Parts of the pH‐Profile

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