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Oxidation of aqueous sulfur dioxide by peroxymonosulfate

Betterton, Eric A. and Hoffmann, Michael R. (1988) Oxidation of aqueous sulfur dioxide by peroxymonosulfate. Journal of Physical Chemistry, 92 (21). pp. 5962-5965. ISSN 0022-3654 . http://resolver.caltech.edu/CaltechAUTHORS:20150814-140635289

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Abstract

Recent model calculations suggest that peroxymonosulfate may constitute a significant fraction of the total sulfur budget in remote tropospheric water droplets such as cloud, fog, and rain. However, little is known about the oxidation of dissolved SO_2 by peroxymonosulfate (HSO_5^-). We have found in aqueous solution that the rate of S(IV) oxidation is comparable to the rate of oxidation of S(IV) by hydrogen peroxide and that HSO_4^- is the only detectable oxidation product. We propose a mechanism in which the rate-determining step involves the acid-catalyzed decomposition of a peroxide-bisulfite intermediate to disulfate ion, S2_7O^(2-), and ultimately to sulfuric acid. The rate equation for this mechanism is -d[HSO_3^-]/dr = k_1(k_2/k_(-1))K_(a1){H^+}[HSO_5^-][S(IV+)]/(1 + (k_2/k_(-1){H^+})(k_(al) + {H+))), where k_1 = 1.21 x 10^6 M^(-1) s^(-1), k_2/k_(-1) = 5.9 M^(-1), k_1k_2/k^(-1) = 7.14 x 10^6 M^(-2) s^(-1), K_(a1) = 2.64 x 10^(-2) M at 5 ºC, and µ = 0.2 M. The activation parameters are ΔH_(k1) = 25.74 ± 0.77 kJ mol^(-1) and ΔS_(k1)^*= -88.1 ± 2.7 J mol^(-1) K^(-1).


Item Type:Article
Related URLs:
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http://dx.doi.org/10.1021/j100332a025DOIArticle
http://pubs.acs.org/doi/abs/10.1021/j100332a025PublisherArticle
ORCID:
AuthorORCID
Hoffmann, Michael R.0000-0002-0432-6564
Alternate Title:Oxidation of Aqueous SO_2 by Peroxymonosulfate
Additional Information:© 1988 American Chemical Society. Received: January 4, 1988.
Record Number:CaltechAUTHORS:20150814-140635289
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20150814-140635289
Official Citation:Oxidation of aqueous sulfur dioxide by peroxymonosulfate Eric A. Betterton and Michael R. Hoffmann The Journal of Physical Chemistry 1988 92 (21), 5962-5965 DOI: 10.1021/j100332a025
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:59547
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:17 Aug 2015 16:34
Last Modified:17 Aug 2015 16:34

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