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On the kinetics and mechanism of oxidation of aquated sulfur dioxide by ozone

Hoffmann, Michael R. (1986) On the kinetics and mechanism of oxidation of aquated sulfur dioxide by ozone. Atmospheric Environment, 20 (6). pp. 1145-1154. ISSN 0004-6981. http://resolver.caltech.edu/CaltechAUTHORS:20150818-100953585

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Abstract

Kinetic data obtained from a number of different investigators on the reaction of S(IV) with ozone in aqueous solution have been analyzed in terms of a single self-consistent rate expression. The rate expression that most appropriately fits all kinetic observations treated in this study is: −d[S(IV)]/dt = (k_0α_0 + k_1α_1 + k_2α_2)[S(IV)][O_3] where α_0, α_1, and α_2 denote the fraction of S(IV) in the form of SO_2·H_2O, HSO^−_3 and SO^(2−)_3, respectively. This kinetic expression is similar in form to the empirical rate laws reported by Erickson et al. (1977, Atmospheric Environment 11, 813–817) and Hoigne et al. (1985, Water Res. 19, 993–1004). The recommended values for k_0, k_1 and k_2 are (2.4 ± 1.1) × 10^4 M^(−1) s^(−1), (3.7 ± 0.7) × 10^5 M^(−1) s^(−1), and (1.5 ± 0.6) × 10^9 M^(−1) s^(−1), respectively. The activation energies that are recommended for k_1 and k_2 are taken from Erickson et al. (1977) as 46.0 kJ mol^(−1) and 43.9 kJ mol^(−1), respectively. The reaction proceeds via three independent pathways that involve a nucleophilic attack on ozone by SO^(2−)_3, HO-SO−_2, and SO_2·H_2O. Rate laws and kinetic data of five investigators are compared for an open cloud water system with a liquid water content of 0.2 g m^(−3).


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1016/0004-6981(86)90147-2DOIArticle
http://www.sciencedirect.com/science/article/pii/0004698186901472PublisherArticle
ORCID:
AuthorORCID
Hoffmann, Michael R.0000-0002-0432-6564
Additional Information:© 1986 Elsevier. First received 21 March 1985 and in final form 5 November 1985. Special thanks are extended to Dr Jack G. Calvert of the National Center for Atmospheric Research for providing the support, space, time and encouragement to write this paper, and to Dr Marcia Dodge, U.S. EPA Project Officer, for providing financial support through lnteragency Agreement DW 930237. This work was performed while the author was a Visiting Scientist at NCAR.
Funders:
Funding AgencyGrant Number
Environmental Protection Agency (EPA)DW930237
Record Number:CaltechAUTHORS:20150818-100953585
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20150818-100953585
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:59687
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:19 Aug 2015 22:12
Last Modified:19 Aug 2015 22:12

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