A study of the spectra and reactivity of oxysulphur-radical anions involved in the chain oxidation of S(IV): A pulse and γ-radiolysis study

Buxton, George V.; McGowan, S.; Salmon, G. Arthur; Williams, J. E.; Wood, Nicholas D.

doi:10.1016/1352-2310(95)00473-4

Cited by 115 publications

(62 citation statements)

References 19 publications

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“…These rates have been reported in a number of publications, including Neta et al (1977), and Buxton et al (1988Buxton et al ( , 1996Buxton et al ( , 1999. However, given the complexity of these systems, it is mathematically cumbersome to develop precise analytical models tracking specific reactive species.…”

Section: Fundamental Reaction Kinetics and Modeling Approachesmentioning

confidence: 93%

“…These include the superoxide anion (O 2 Á À ) and the perhydroxyl radical (HO 2 Á ), which are also common in hydrogen peroxide systems (De Laat and Gallard, 1999) (see Chapter 2). There are other sulfur-based radicals that have been noted to be important in free radical reactions with sulfite and peroxymonosulfate reaction systems, including SO 5 Á À and SO 3 Á À radicals (Buxton et al, 1996;Anipsitakis and Dionysiou, 2003), but their occurrence or importance in persulfate-based ISCO systems is not yet known.…”

Section: Free Radical Oxidationmentioning

confidence: 99%

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Fundamentals of ISCO Using Persulfate

Petri

Watts

Tsitonaki³

et al. 2010

SERDP/ESTCP Environmental Remediation Technology

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ScopeChemistry and use of persulfate for in situ chemical oxidation of subsurface contaminants, including free radical and other reaction mechanisms, catalysts, subsurface transport, and contaminant treatability. Key ConceptsPersulfate reaction chemistry is complex. Persulfate can react through direct electron transfer or free radical reactions. Electron transfer reactions are relatively slow and selective. Upon activation, the free radicals generated have nonspecific reactivity that allows for the degradation of a wide range of organic contaminants. The radicals that are presently understood to play a major role in reactions are the sulfate radical and the hydroxyl radical. However, there is emerging evidence that the superoxide anion and the perhydroxyl radical also may be important. Persulfate activation may be achieved by heat, chelated or non-chelated transition metals (especially iron), hydrogen peroxide, and alkaline pH conditions. The efficiency, effectiveness, and reaction products may vary between contaminants, activation methods, and the porous media to be treated. Carbonate, bicarbonate, or chloride ions can act as free radical scavengers and reduce reaction efficiency and effectiveness. The kinetics of reaction between persulfate and target compounds is complex. To simplify, pseudo first-order kinetics are often assumed. However, these usually require laboratory estimation because extrapolating between systems is difficult. The interaction of aquifer solids and persulfate is not well understood; persulfate does react with aquifer solids resulting in oxidant consumption, but the rate and magnitude of this process are not well characterized. Persistence varies from days to months, depending on conditions. The impact of persulfate on metal mobility is not well understood. Conceivably, persulfate could impact metal concentrations in groundwater through modification of pH, oxidation of metals, injection of activation amendments, and other mechanisms.

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Section: Fundamental Reaction Kinetics and Modeling Approachesmentioning

confidence: 93%

Section: Free Radical Oxidationmentioning

confidence: 99%

Fundamentals of ISCO Using Persulfate

Petri

Watts

Tsitonaki³

et al. 2010

SERDP/ESTCP Environmental Remediation Technology

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“…f Averaged in CAPRAM. g 5.5×10 6 Herrmann et al (1995), ∼ 2.2×10 8 Buxton et al (1996). h Waygood and McElroy (1992).…”

Section: Chemical Mechanism and Simulation Of Experimentsmentioning

confidence: 99%

“…k Rudziński (2004). l 1.7×10 9 Buxton et al (1996). 4.1 Group 1 -auto-oxidation of Mn II in presence of sulphite or bisulphite ions (Fig. 7) Chemical-kinetic modeling of our experiments required some mechanism for the initial oxidation of Mn II to Mn III in the presence of sulphite or bisulphite ions.…”

Section: Chemical Mechanism and Simulation Of Experimentsmentioning

confidence: 99%

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Reactions of isoprene and sulphoxy radical-anions – a possible source of atmospheric organosulphites and organosulphates

2009

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Abstract. Transformation of isoprene coupled with autooxidation of S IV in aqueous solutions was studied experimentally and by chemical-kinetic modelling over a broad range of solution acidities (pH=3-9) to complement the research on aqueous-phase and heterogeneous transformation of isoprene reported recently by many laboratories. Isoprene significantly slowed down the auto-oxidation in acidic and basic solutions, and accelerated it slightly in neutral solutions. Simultaneously, production of sulphate ions and formation of solution acidity were significantly reduced. Formation of sulphite and sulphate derivatives of isoprene -sulphurous acid mono-(2-methyl-4-oxo-but-2-enyl) ester (m/z=163), sulphurous acid mono-(4-hydroxy-2-methyl-but-2-enyl) ester (m/z=165), sulphuric acid mono-(2-methyl-4-oxo-but-2-enyl) ester (m/z=179), sulphuric acid mono-(4-hydroxy-2-methyl-but-2-enyl) ester (m/z=181), and possible structural isomers of these species -was indicated by electrospray ionisation mass spectrometric analysis of postreaction mixtures. The experimental results were explained by changes in a subtle quantitative balance of three superimposed processes whose rates depended in different manner on the acidity of reacting solutions -the scavenging of sulphoxy radical-anions by isoprene, the formation of sulphoxy radical-anions during further reactions of isoprene radicals, and the auto-oxidation of S IV itself. A chemical mechanism based on this idea was explored numerically to show good agreement with experimental data. In basic and neutral solutions, the model overestimated the consumption of isoprene, probably because reactions of primary sulphite and sulphate derivatives of isoprene with sulphoxy radical-anions were not included. Interaction of isoprene Correspondence to: K. J. Rudziński (kjrudz@ichf.edu.pl) with sulphur(IV) species and oxygen can possibly result in formation of new organosulphate and organosulphite components of atmospheric aerosols and waters, and influence the distribution of reactive sulphur and oxygen species in isoprene-emitting organisms exposed to S IV pollutants.

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Chlorine Oxide Radicals ClOx (x=1-4) Studied by Matrix Isolation Spectroscopy

2002

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Ethylen ist das kleinste Reifungshormon der Pflanzen. In der Zuschrift auf berichten T. M. Swager et al. über ein Gemisch aus einwandigen Kohlenstoffnanoröhren und einem Kupfer(I)‐Komplex als chemoresistive Funktionseinheit für den hoch empfindlichen und selektiven Nachweis von Ethylen im Sub‐ppm‐Bereich. Mit diesem Sensor ließen sich die Reifungsstadien verschiedener Früchte ermitteln.

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A study of the spectra and reactivity of oxysulphur-radical anions involved in the chain oxidation of S(IV): A pulse and γ-radiolysis study

Cited by 115 publications

References 19 publications

Fundamentals of ISCO Using Persulfate

Fundamentals of ISCO Using Persulfate

Reactions of isoprene and sulphoxy radical-anions – a possible source of atmospheric organosulphites and organosulphates

Chlorine Oxide Radicals ClOx (x=1-4) Studied by Matrix Isolation Spectroscopy

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