Oxidation of S(IV) in Atmospheric Water by Photooxidants and Iron in the Presence of Copper

Sedlak, David L.; Hoigne, Juerg.

doi:10.1021/es00060a021

Cited by 57 publications

(37 citation statements)

References 21 publications

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“…[28][29][30][31][32][33][34][35][36][37][38][39][40][41] The Cu(II)-S(IV) system was proposed by Conklin …”

Section: Redox Chemistry Of Cu(ii)-s(iv) Complexesmentioning

confidence: 99%

Isomorphic series of double sulfites of the Cu2SO3.MSO3.2H2O (M = Cu, Fe, Mn, and Cd) Type: a review

Silva¹,

Andrade²

2004

J. Braz. Chem. Soc.

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Embora o primeiro sulfito duplo de valência mista, Cu 2 SO 3 .CuSO 3 .2H 2 O, tenha sido preparado no início do século XIX por M. Chevreul, o interesse por compostos dessa natureza ressurgiu só depois da metade do século XX com a determinação da estrutura cristalina deste composto e a caracterização de seu espectro de absorção na região do infravermelho. Nos últimos anos, os estudos referentes a este tema têm se intensificado, especialmente após a descoberta da possibilidade de substituição isomórfica do Cu(II) no sal de Chevreul por diversos cátions com o mesmo estado de oxidação, gerando uma série de compostos cujas propriedades são fortemente dependentes da natureza do cátion M(II). Devido às suas propriedades interessantes, esses sistemas de valência mista podem ser usados como modelos para identificar intermediários em processos de corrosão atmosférica, bem como para avaliar o papel de metais de transição como catalisadores de autooxidação de S(IV) na conversão do SO 2 na atmosfera.Although the first mixed valence double sulfite, Cu 2 SO 3 .CuSO 3 .2H 2 O, was prepared in the early 19 th century by M. Chevreul, interest in this type of compound was only rekindled in the mid-1960s, when the crystalline structure of Chevreul's salt was determined and its infrared spectrum characterized. Studies of this type of compound have been intensified in recent years, especially after the discovery that the isomorphic Cu(II) in Chrevreul's salt could be replaced by a divalent metal ion, forming an isomorphic series whose properties are strongly dependent on the nature of the M(II) cation. Because of their interesting properties, these mixed valence systems can be used as models to identify intermediates in atmospheric corrosion processes, and to evaluate the role of transition metals as catalysts of S(IV) autoxidation in the conversion of SO 2 in the atmosphere.

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“…[28][29][30][31][32][33][34][35][36][37][38][39][40][41] The Cu(II)-S(IV) system was proposed by Conklin …”

Section: Redox Chemistry Of Cu(ii)-s(iv) Complexesmentioning

confidence: 99%

Isomorphic series of double sulfites of the Cu2SO3.MSO3.2H2O (M = Cu, Fe, Mn, and Cd) Type: a review

Silva¹,

Andrade²

2004

J. Braz. Chem. Soc.

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“…[4,5] Peroxoiron complexes have also been shown to catalyze the polymerization of styrene and organic substrates. [6,7] The formation of a peroxoiron complex in the decomposition of hydrogen peroxide by Fe III in aqueous solution is relevant in the chemistry of natural waters and atmospheric water droplets, [8][9][10] and the presence of a peroxo complex in -with hydrogen peroxide by using a stopped-flow technique. [2] The rate law for the formation of the complex was found to be d [ [1] and in our study were conducted using a total Fe III concentration of Յ1 × 10 -3 .…”

Section: Introductionmentioning

confidence: 99%

Mössbauer Investigation of Peroxo Species in the Iron(III)–EDTA–H₂O₂ System

et al. 2005

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The reaction of a diiron(III)–EDTA complex with H2O2 in alkaline medium is studied by Mössbauer spectroscopy in conjunction with the rapid‐freeze/quench technique in order to identify possible intermediate species during the formation and decomposition of the purple (EDTA)FeIII(η2‐O2)3– complex ion. Starting from the six‐coordinate [FeIIIEDTA]– species at acidic pH, it is demonstrated that mononuclear complexes formed at a pH of about 1 are convert into the diiron(III)–EDTA complex [(EDTA)FeIII‐O‐FeIII(EDTA)]4– upon raising the pH to around 10.4. H2O2 reacts with the diiron(III) complex to give peroxide/hydroperoxide related adducts. Initially, the reaction tears apart the dimers to form a peroxo adduct, namely the seven‐coordinate mononuclear [(EDTA)FeIII(η2‐O2)]3–, which is stable only at very high pH. The decomposition of this peroxo adduct gives two new species, which are reported for the first time. The Mössbauer parameters of these species suggest a six‐coordinate μ‐peroxodiiron(III) complex [(EDTA)FeIII‐(OO)‐FeIII(EDTA)]4– and a seven‐coordinate μ‐hydroxo‐μ‐peroxodiiron(III) complex [(EDTA)FeIII‐(OO)(OH)‐FeIII(EDTA)]5–. A badly resolved, extremely broad component is observed in the Mössbauer spectra during the conversion of the monomer to dimeric peroxo species, which may be attributed to the short‐lived [(EDTA)FeIII‐OO]3– or [(EDTA)FeIII‐OOH]2– intermediate species. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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“…They are known to be powerful reagents for a variety of metal species such as Cu(II) and Fe(III), 22,23 and the effect of these reactions on metal-redox chemistry has been studied extensively. 24 Photoreduction of Hg(II) would eventually yield elemental Hg(0), which is much more volatile than the ionic Hg(I) or Hg(II). Volatility will enhance the partitioning of mercury to the gas phase and therefore affect its deposition to the ground.…”

Section: Introductionmentioning

confidence: 99%

Aqueous Photochemistry of Mercury with Organic Acids

Pehkonen

Lin

1998

Journal of the Air & Waste Management Association

109

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To understand the dynamic chemical changes of mercury taking place in atmospheric water, a more detailed knowledge of the reactions of mercury with organic acids must be obtained. The rate of the above chemical reactions with different Hg(II) species is especially essential for understanding the dominant pathway of mercury transformation in the atmosphere. The objective of this research is to study the rate of photochemical reactions of dissolved divalent mercury with organic acids such as oxalate, acetate, and formate, which are abundant in atmospheric water. Laboratory photochemical experiments with simulated sunlight were conducted to assess the role of homogeneous photochemistry in changing the redox states of mercury in atmospheric water. It is observed that Hg(II) is readily reduced by hydroperoxyl radicals produced by the photolysis of oxalate. The second-order rate constant for the Hg(II)-hydroperoxyl radical reaction was found to be 1.7 × 10 4 M -1 s -1 when no chloride is present and 1

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Oxidation of S(IV) in Atmospheric Water by Photooxidants and Iron in the Presence of Copper

Cited by 57 publications

References 21 publications

Isomorphic series of double sulfites of the Cu2SO3.MSO3.2H2O (M = Cu, Fe, Mn, and Cd) Type: a review

Isomorphic series of double sulfites of the Cu2SO3.MSO3.2H2O (M = Cu, Fe, Mn, and Cd) Type: a review

Mössbauer Investigation of Peroxo Species in the Iron(III)–EDTA–H₂O₂ System

Aqueous Photochemistry of Mercury with Organic Acids

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Oxidation of S(IV) in Atmospheric Water by Photooxidants and Iron in the Presence of Copper

Cited by 57 publications

References 21 publications

Isomorphic series of double sulfites of the Cu2SO3.MSO3.2H2O (M = Cu, Fe, Mn, and Cd) Type: a review

Isomorphic series of double sulfites of the Cu2SO3.MSO3.2H2O (M = Cu, Fe, Mn, and Cd) Type: a review

Mössbauer Investigation of Peroxo Species in the Iron(III)–EDTA–H2O2 System

Aqueous Photochemistry of Mercury with Organic Acids

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Product

Resources

About

Mössbauer Investigation of Peroxo Species in the Iron(III)–EDTA–H₂O₂ System