Kinetics of aqueous phase reactions of the SO sub 4 sup minus radical with potential importance in cloud chemistry

Journal Article · Fri Jan 20 04:00:00 EST 1989 · Journal of Geophysical Research; (United States)

DOI:https://doi.org/10.1029/JD094iD01p01085· OSTI ID:5383443

Wine, P H; Tang, Y; Thorn, R P; Wells, J R; Davis, D D ^[1]

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1. Georgia Inst. of Tech., Atlanta (USA)

A laser flash photolysis/long path absorption technique has been employed to study at 298 K the kinetics of aqueous phase reactions of the SO{sub 4}{sup {minus}} radical with a number of species commonly found in cloud water. Much lower radical concentrations were employed than in all previous direct studies of SO{sub 4}{sup {minus}} reaction kinetics. In the zero ionic strength limit, rate coefficients for SO{sub 4}{sup {minus}} reaction with the anions HSO{sub 3}{sup {minus}}, Cl{sup {minus}}, NO{sub 2}{sup {minus}}, HCOO{sup {minus}}, and CH{sub 3}COO{sup {minus}} are found to be 7.5 {times} 10{sup 8}, 2.6 {times} 10{sup 8}, 9.8 {times} 10{sup 8}, 1.1 {times} 10{sup 8}, and 3.7 {times} 10{sup 6} M{sup {minus}1}s{sup {minus}1}, respectively. Rate coefficients for SO{sub 4}{sup {minus}} reactions with the neutral species H{sub 2}O{sub 2}, CH{sub 3}OH, HCOOH, and CH{sub 3}COOH are found to be 1.2 {times} 10{sup 7}, 8.8 {times} 10{sup 6}, 4.6 {times} 10{sup 5}, and 1.4 {times} 10{sup 4} M{sup {minus}1}s{sup {minus}1}, respectively. For many of the reactions studied, agreement with previously reported rate data is poor. Of particular importance for cloud chemistry is the fact that the SO{sub 4}{sup {minus}} + HSO{sub 3}{sup {minus}} reaction proceeds more slowly than previously believed, while the SO{sub 4}{sup {minus}} + Cl{sup {minus}} reaction is somewhat faster than previously thought. Incorporation of these results into cloud chemistry models should reduce the calculated efficiency of free radical chain reactions as an oxidation mechanism for S IV.

• OSTI ID: 5383443
• Journal Information: Journal of Geophysical Research; (United States), Journal Name: Journal of Geophysical Research; (United States) Vol. 94:D1; ISSN 0148-0227; ISSN JGREA
• Country of Publication: United States
• Language: English

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ABSORPTION
ACETIC ACID
ACID RAIN
ALCOHOLS
AQUEOUS SOLUTIONS
ATMOSPHERIC CHEMISTRY
ATMOSPHERIC PRECIPITATIONS
CARBOXYLIC ACIDS
CHEMICAL REACTION KINETICS
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CHEMISTRY
CHLORINE
CLOUDS
DECOMPOSITION
DISPERSIONS
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ELEMENTS
FLASH HEATING
FORMIC ACID
HALOGENS
HEATING
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HYDROXY COMPOUNDS
IONIC CONDUCTIVITY
KINETICS
MATHEMATICAL MODELS
METHANOL
MIXTURES
MONOCARBOXYLIC ACIDS
NITRITES
NITROGEN COMPOUNDS
NONMETALS
ORGANIC ACIDS
ORGANIC COMPOUNDS
OXYGEN COMPOUNDS
PEROXIDES
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
PHYSICAL PROPERTIES
RADICALS
RAIN
REACTION KINETICS
SOLUTIONS
SULFATES
SULFUR COMPOUNDS