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Kinetics and mechanism of the oxidation of aqueous hydrogen sulfide by peroxymonosulfate

Betterton, Eric A. and Hoffmann, Michael R. (1990) Kinetics and mechanism of the oxidation of aqueous hydrogen sulfide by peroxymonosulfate. Environmental Science and Technology, 24 (12). pp. 1819-1824. ISSN 0013-936X. https://resolver.caltech.edu/CaltechAUTHORS:20150813-105953302

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Abstract

The stoichiometry and mechanism of the oxidation of aqueous S(-II) by HSO_5^-, is similar to the oxidation of S(-II) by H_2O_2, but the rate of oxidation by HSO_5^-; is 3-4 orders of magnitude faster than the corresponding reaction with H_2O_2. A two-term rate law of the following form is found to be valid for the pH range of 2.0-6.3: -d[S(-II)]/dt = k_1[H_2S][HSO_5^-] + k_2K_(a1)[H_2S][HSO_5^-]/[H^+], where k_1 = 1.98 X 10^1 M^(-1) s^(-1),k2 = 1.22 X 10^4 M^(-1) s^(-1), and K_(al) = [H^+][HS^-]/[H_2S] = 2.84 X 10^(-8) M at 4.9 °C, µ = 0.2 M, and [S(-II)] = [H_2S] + [HS^-] + [S^(2-). At high pH and high [HSO_5^-]/[S(-II)] ratios SO_4^(2-) and H^+ formation are favored, whereas at low pH and low [HSO_5^-]/[S(-II)] ratios elemental sulfur (S_8) is favored as the principal reaction product. Peroxymonosulfate is a monosubstituted derivative of hydrogen peroxide that is thermodynamically more powerful as an oxidant than H_2O_2 and kinetically more reactive. These properties make HSO_5^- a potentially important oxidant in natural systems such as remote tropospheric clouds and also a viable alternative to H_2O_2 for the control of malodorous sulfur compounds and for the control of sulfide-induced corrosion in concrete sewers.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/es00082a005DOIArticle
http://pubs.acs.org/doi/abs/10.1021/es00082a005PublisherArticle
ORCID:
AuthorORCID
Hoffmann, Michael R.0000-0002-0432-6564
Additional Information:© 1990 American Chemical Society. Received for review January 30, 1990. Revised manuscript received June 1, 1990. Accepted June 11, 1990.
Issue or Number:12
Record Number:CaltechAUTHORS:20150813-105953302
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150813-105953302
Official Citation:Kinetics and mechanism of the oxidation of aqueous hydrogen sulfide by peroxymonosulfate Eric A. Betterton and Michael R. Hoffmann Environmental Science & Technology 1990 24 (12), 1819-1824 DOI: 10.1021/es00082a005
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:59485
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:14 Aug 2015 15:46
Last Modified:03 Oct 2019 08:47

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