Kinetics of Catalytic Oxidation of Sulfite in Diluted Aqueous Solutions

Opletal, M.; Novotný, Petr; Rejl, F.J.; Moucha, T.; Kordač, M.

doi:10.1002/ceat.201500064

Cited by 4 publications

(4 citation statements)

References 20 publications

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“…Reactions to form radical species are as follows (similar reactions can also be written for HSO 3 − ): − This reaction sequence is a known important in-cloud sulfate formation pathway. − …”

Section: Introductionmentioning

confidence: 99%

Formation of Organosulfur Compounds through Transition Metal Ion-Catalyzed Aqueous Phase Reactions

Huang

Cochran

Coddens

et al. 2018

Environ. Sci. Technol. Lett.

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Organosulfur compounds, particularly organosulfates, are considered as important tracers of secondary organic aerosol formation. However, the mechanistic pathways for the formation of these compounds in the atmosphere are still not well understood. In this study, we show for the first time that C 2 −C 4 organosulfur compounds, as well as their oligomers, can form in the aqueous phase from reactions of unsaturated carbonyl compounds, i.e., methacrolein (MACR) and methyl vinyl ketone (MVK), with the bisulfite anion (HSO 3 − ) in the presence of Fe 3+ . The mechanism for product formation in the presence of Fe 3+ involves sulfite and sulfate ion radicals. As shown here, the formation of specific organosulfur compounds depends on the concentrations of MVK and MACR and the solution pH. Our findings provide new insights into pathways for forming organosulfur compounds in the atmosphere and the role that transition metal ions, such as Fe 3+ , play in catalyzing these reactions.

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Section: Introductionmentioning

confidence: 99%

Formation of Organosulfur Compounds through Transition Metal Ion-Catalyzed Aqueous Phase Reactions

Huang

Cochran

Coddens

et al. 2018

Environ. Sci. Technol. Lett.

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“…For instance, oxygen scavenging by sulfite compounds is an important task to inhibit corrosion in industrial water circuits. In chemical engineering and mass transfer studies the cobalt‐catalysed reaction of sulfite to sulfate has been intensively investigated [Scheme , (1)] , , , . Mostly, oxygen and its consumption is indicated by ruthenium complexes and their fluorescence abilities as mentioned above by LIF.…”

Section: Systems With O2mentioning

confidence: 99%

Reaction Systems for Bubbly Flows

et al. 2018

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Reactive bubbly flows are at the heart of multiphase flows which are a major topic in chemical engineering since many bulk chemicals are produced in bubbly flows. However, the factors determining product yield and selectivity are often subject of complicated mass transfer effects. Herein, we describe the latest developments in the detection of mass transfer [a] is holding a permanent position in the Herres-Pawlis group at RWTH Aachen University for advanced spectroscopy, density functional calculations and X-ray crystallography. He studied Chemistry at the University of Paderborn and finished his PhD thesis at TU Dortmund in 2011 on the coordination chemistry of late transition metals for catalysis and bioinorganic chemistry. Then, he moved to LMU Munich and turned to the theoretical description of N-donor transition metal systems with focus on copper-dioxygen chemistry. In 2013, he was awarded with the Römer-Postdoc Prize.

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“…For example, it has been established that some organic acids, such as oxalic acid and formic acid, have a strong inhibition effect on iron-catalyzed S(IV) oxidation due to the complexation of organic ligands with iron. 4−6 The catalytic oxidation of S(IV) is a free-radical chain reaction, 3,7,8 where sulfoxy radicals, that is, SO 3 − , SO 4 − , and SO 5 − radicals, are the major intermediates. Therefore, besides complexation with TMI, organic compounds can also react with sulfoxy radicals, resulting in the decrease of sulfoxy radical concentration and subsequently altering the rate of catalytic S(IV) oxidation as well as the conversion of S(IV).…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, recent studies have shown that this reaction can also be influenced by other reactions, in particular, in the presence of organic compounds. For example, it has been established that some organic acids, such as oxalic acid and formic acid, have a strong inhibition effect on iron-catalyzed S(IV) oxidation due to the complexation of organic ligands with iron. − The catalytic oxidation of S(IV) is a free-radical chain reaction, ,, where sulfoxy radicals, that is, SO 3 – , SO 4 – , and SO 5 – radicals, are the major intermediates. Therefore, besides complexation with TMI, organic compounds can also react with sulfoxy radicals, resulting in the decrease of sulfoxy radical concentration and subsequently altering the rate of catalytic S(IV) oxidation as well as the conversion of S(IV). − The three main pathways for these reactions in aqueous phase are summarized in reactions – (using SO 4 – radical as an example): , Specifically, the ·SO 4 – radical can react with saturated organic compounds through hydrogen abstraction (R1), transfer of an electron from an aromatic compound (R2), and undergo addition reactions with organic compounds containing carbon–carbon double bonds (R3).…”

Section: Introductionmentioning

confidence: 99%

Influence of Glyoxal on the Catalytic Oxidation of S(IV) in Acidic Aqueous Media

Coddens

Huang

Wong

et al. 2018

ACS Earth Space Chem.

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The role of glyoxal in S(IV) oxidation in acidic aqueous solutions catalyzed by iron in the form of aqueous Fe3+ ions and solid iron oxide was investigated under different experimental conditions. It is found that the rate of Fe3+(aqueous (aq)) ion-catalyzed S(IV) oxidation decreases in the presence of glyoxal. The results of mass spectral analysis and infrared spectra suggest that the trapping of SO4 – radicals, as well as the formation of glyoxal–S(IV) adducts, are responsible for this inhibition effect. Interestingly, although sulfur oxidation is kinetically inhibited in the presence of glyoxal, S(IV) in the form of sulfite is over time completely converted to sulfate. Additionally, the inhibition effects of glyoxal can also be observed in the reaction of S(IV) catalyzed by iron oxide particles, albeit less than that catalyzed by dissolved Fe3+(aq). The observed inhibition effect for the iron oxide particles is proposed to be attributed to competitive surface adsorption on the iron oxide particle surface. Overall, these findings suggest that the effects of glyoxal on the catalytic oxidation of S(IV) are highly dependent on the mechanism, form of iron (dissolved vs solid), and the ambient conditions including pH and concentration.

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Kinetics of Catalytic Oxidation of Sulfite in Diluted Aqueous Solutions

Cited by 4 publications

References 20 publications

Formation of Organosulfur Compounds through Transition Metal Ion-Catalyzed Aqueous Phase Reactions

Formation of Organosulfur Compounds through Transition Metal Ion-Catalyzed Aqueous Phase Reactions

Reaction Systems for Bubbly Flows

Influence of Glyoxal on the Catalytic Oxidation of S(IV) in Acidic Aqueous Media

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