Pulse radiolysis study of the reaction of OH radicals with methanesulfonate and hydroxymethanesulfonate
Journal Article
·
· Journal of Physical Chemistry
- Univ. of California, Irvine, CA (United States)
- Univ. of Notre Dame, IN (United States)
Pulse radiolysis studies of the reaction kinetics of methanesulfonate and hydroxymethanesulfonate with hydroxyl radicals were conducted by relative rate methods. The rate constant for the reduction of CH{sub 3}SO{sub 3}{sup {minus}} with OH{sup {sm_bullet}} was determined as 1.24 ({plus_minus} 0.07) {times} 10{sup 7} M{sup {minus}1}s{sup {minus}1} at an ionic strength of 0.2 M, with thiocyanate as the reference solute. For the same ionic strength conditions, the rate constant for the attack of OH{sup {sm_bullet}} with CH{sub 2}(OH)SO{sub 3}{sup {minus}}, k = 2.65 ({plus_minus} 0.12) {times} 10{sup 8} M{sup {minus}1} s{sup {minus}1}, was more than an order of magnitude greater than the rate constant for methanesulfonate. Previous estimates of the rate constants for the methanesulfonate reaction varied by approximately 2 orders of magnitude; our results are in best agreement with the slowest value. Our rate constant for hydroxymethanesulfonate was also significantly smaller than two previously reported values. Both reactions are independent of pH over the pH range studied (3.8-6.5) and are nearly independent of ionic strength. These results imply that the oxidation of methanesulfonate by OH{sup {sm_bullet}} is too slow to be significant in typical remote cloud droplets, but may be important in aerosols. The reaction of OH{sup {sm_bullet}} with hydroxymethanesulfonate would be significant in atmospheric droplets when hydroxyl radical concentrations are at least 10{sup {minus}12} M. 29 refs., 2 figs., 2 tabs.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 437073
- Journal Information:
- Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 8 Vol. 96; ISSN JPCHAX; ISSN 0022-3654
- Country of Publication:
- United States
- Language:
- English
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