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

Journal Article · Fri Jan 20 00:00:00 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), Vol. 94:D1; ISSN 0148-0227
• Country of Publication: United States
• Language: English

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54 ENVIRONMENTAL SCIENCES
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540120* - Environment
Atmospheric- Chemicals Monitoring & Transport- (1990-)
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