Influence of Atmospheric Carboxylic Acids on Catalytic Oxidation of Sulfur(IV)

Podkrajšek, Boštjan; Grgić, Irena; Turšič, Janja; Berčič, Gorazd

doi:10.1007/s10874-006-9018-x

Cited by 22 publications

(17 citation statements)

References 30 publications

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“…Large uncertainty exists in the reaction rates of Fe(III)‐ and Mn(II)‐catalyzed S(IV) + O 2 [ Hoffmann and Jacob , 1984; Martin and Hill , 1987a], and the reaction is thought to be inhibited by increasing ionic strength, the sulfate ion, various organics, and self‐inhibited [ Kotronarou and Sigg , 1993; Martin and Hill , 1987a, 1987b; Podkrajsek et al , 2006; Tursic et al , 2003; Zuo and Zhan , 2005]. The presence of both Fe(III) and Mn(II) enhances the reaction rate synergistically, so that the overall reaction rate is greater than the sum of the individual rates [ Berglund et al , 1993; Chughtai et al , 1993; Coichev et al , 1992; Grgic et al , 1992; Martin , 1984].…”

Section: Atmospheric Iron (Fe) and Manganese (Mn)mentioning

confidence: 99%

Transition metal‐catalyzed oxidation of atmospheric sulfur: Global implications for the sulfur budget

et al. 2009

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[1] We use observations of the oxygen-17 excess (D 17 O) of sulfate in the Arctic to quantify the sulfate source from aqueous SO 2 (S(IV)) oxidation by O 2 catalyzed by transition metals. Due to the lack of photochemically produced OH and H 2 O 2 in high latitudes during winter, combined with high anthropogenic SO 2 emissions in the Northern Hemisphere, oxidation by O 3 is predicted to dominate sulfate formation during winter in this region. However, D 17 O measurements of sulfate aerosol collected in Alert, Canada, are not consistent with O 3 as the dominant oxidant and indicate that a S(IV) oxidant with near-zero D 17 O values (O 2 ) is important during winter. We use a global chemical transport model to interpret quantitatively the Alert observations and assess the global importance of sulfate production by Fe(III)-and Mn(II)-catalyzed oxidation of S(IV) by O 2 . We scale anthropogenic and natural atmospheric metal concentrations to primary anthropogenic sulfate and dust concentrations, respectively. The solubility and oxidation state of these metals is determined by cloud liquid water content, source, and sunlight. By including metal-catalyzed S(IV) oxidation, the model is consistent with the D 17 O magnitudes in the Alert data during winter. Globally, we find that this mechanism contributes 9-17% to sulfate production. The inclusion of metal-catalyzed oxidation does not resolve model discrepancies with surface SO 2 and sulfate observations in Europe. Oxygen isotope measurements of sulfate aerosols collected near anthropogenic and dust sources of metals would help to verify the importance of this sulfur oxidation pathway.

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Section: Atmospheric Iron (Fe) and Manganese (Mn)mentioning

confidence: 99%

Transition metal‐catalyzed oxidation of atmospheric sulfur: Global implications for the sulfur budget

et al. 2009

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“…The shadow region shows the coexistent predominance area of reaction products, among which shadow area 1 is the predominance area of Mn 2+ and

S O_{6}^{2 -}

while shadow area 2 represents the dominant area of Mn 2+ and

S_{2} O_{6}^{2 -}

. As can be seen form Figure that the main possible reactions for the oxidation of aqueous SO 2 and

{HSO}_{3}^{-}

species by MnO 2 ,,, or O 2 ,, could be listed as the following overall equations:

true M n O_{2} ((), s) + S O_{2} ((), a q) = M n^{2 +} + S O_{4}^{2 -}

true M n O_{2} ((), s) + S O_{2} ((), a q) = M n^{2 +} + S_{2} O_{6}^{2 -}

true M n O_{2} ((), s) + H^{+} + H S O_{3}^{-} = M n^{2 +} H_{2} O + S O_{4}^{2 -}

true M n O_{2} ((), s) + 2 H S O_{3}^{-} + H^{+} = M n^{2 +} + H_{2} O + S_{2} O_{6}^{2 -}

true 1 / 2 O_{2} ((), a q) + ...

…”

Section: Theoretical Analysismentioning

confidence: 99%

“…(1) For aqueous SO 2 ‐MnO 2 ‐H 2 O reaction system, most studies were mainly focused on the mechanism and kinetics,,, or leaching characteristics of Mn extraction, during reaction of SO 2 with MnO 2 or the oxidation of S(IV) by MnO 2 in the absence of oxygen, which have confirmed that MnS 2 O 6 is a inevitable reaction products,, and the formation rates of

S_{2} O_{6}^{2 -}

and leaching rate of Mn are both closely related to SO 2 concentration, pH and reaction temperature ,,,,. (2) For aqueous SO 2 ‐O 2 system, SO 2 could be oxidized by dissolved O 2 , and the oxidation rate is accelerated by Mn 2+ , the concentration of which is increased with the increasing Mn extraction during pyrolusite leaching process with SO 2 . (3) For gaseous SO 2 ‐O 2 ‐MnO 2 ‐H 2 O system, mixture gas containing SO 2 and O 2 was bubbled into MnO 2 slurry, O 2 may be involved in the reaction and then influence the reaction products, which have been discussed by few published papers, but consensus results have not been reached.…”

Section: Introductionmentioning

confidence: 99%

Oxidation of SO₂ by O₂ and Its Effects on Dithionate Formation during Pyrolusite Leaching Process with Mixture Gas Containing SO₂ and O₂

Ding

et al. 2018

ChemistrySelect

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Competitive oxidations of SO2 oxidized by MnO2 and O2 are existed during pyrolusite leaching process with SO2 and O2 mixture gases. Generally, SO2 is oxidized into H2SO4 by O2, and manganese sulfate (MnSO4) and manganese dithionate (MnS2O6) are formed when oxidized by MnO2. Meanwhile, the reaction between SO2 and O2 has effect on the amount of aqueous SO2 oxidized by MnO2 and solution acidity, resulting in the variations of Mn extraction and MnS2O6 formation. In this paper, the competitive mechanism of SO2 oxidation by MnO2 and O2 was firstly discussed based on theoretical analysis of leaching process, and then concentration ratio of O2/SO2 (R) in gas flow was proposed as a determined parameter to characterize the competition, the effects of R on Mn extraction, H2SO4 generation and MnS2O6 formation. The results showed that R was the determined parameter for evaluating the oxidation effect of O2 on SO2, which had a decisive effect on H2SO4 concentration, and eventually affects MnS2O6 formation and Mn extraction under constant gas flow (10 L⋅min−1) and others experimental factor. With the increase of R, the H2SO4 concentration increased gradually but the formation of MnS2O6 sharply decreased to negligible amount when R >10, and Mn extraction increased first and then decreased significantly. The most suitable R for obtaining MnSO4 product was R=10 with 1.4 g⋅L−1 S2O62- , 96% Mn extraction and 0.07 M H2SO4.

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“…Gupta et al studied the influence of hydroxyl VOCs on the oxidation of S(IV) by oxygen and found VOCs inhibited the S(IV) oxidation. Grgic et al [36] studied the inhibition effect of acetate, oxlate, format on Fe-catalysed autoxidation of S(IV) at pH 2.8, 3.7,4.5 and found that oxlate has strong inhibiting effect on reaction rate due to the decrease amount of catalytic activity of Fe +3 due to formation of complexion with oxlate. Bostjan et al [32] studied the effect of carboxylic acid on Mn(II) catalysed oxidation of S(IV) and found that monocarboxylic acid exhibit strong inhibition and out of which acetic acid shows strong inhibition.…”

Section: Hso H Somentioning

confidence: 99%

The Inhibitive Action of Aniline on the Autoxidation of Sodium Sulfite in Acidic Medium

Sharma¹

2017

JAPLR

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The kinetics of atmospheric autoxidation of S (IV) by Ag(I) at pH 4.02-5.25 has been studied. The aqueous phase autoxidation of S (IV) is the major factor responsible for acidification of atmospheric aqueous system. The role of Aniline act as an inhibitor of Ag(I) catalysed autoxidation of S(IV) in acidic medium has been identified, and based on the observed results following rate law given and a free radical mechanism has been proposed.( )

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Influence of Atmospheric Carboxylic Acids on Catalytic Oxidation of Sulfur(IV)

Cited by 22 publications

References 30 publications

Transition metal‐catalyzed oxidation of atmospheric sulfur: Global implications for the sulfur budget

Transition metal‐catalyzed oxidation of atmospheric sulfur: Global implications for the sulfur budget

Oxidation of SO₂ by O₂ and Its Effects on Dithionate Formation during Pyrolusite Leaching Process with Mixture Gas Containing SO₂ and O₂

The Inhibitive Action of Aniline on the Autoxidation of Sodium Sulfite in Acidic Medium

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Influence of Atmospheric Carboxylic Acids on Catalytic Oxidation of Sulfur(IV)

Cited by 22 publications

References 30 publications

Transition metal‐catalyzed oxidation of atmospheric sulfur: Global implications for the sulfur budget

Transition metal‐catalyzed oxidation of atmospheric sulfur: Global implications for the sulfur budget

Oxidation of SO2 by O2 and Its Effects on Dithionate Formation during Pyrolusite Leaching Process with Mixture Gas Containing SO2 and O2

The Inhibitive Action of Aniline on the Autoxidation of Sodium Sulfite in Acidic Medium

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Oxidation of SO₂ by O₂ and Its Effects on Dithionate Formation during Pyrolusite Leaching Process with Mixture Gas Containing SO₂ and O₂