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. doi:10.1021/es00082a005. 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 | |||||||||
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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 | |||||||||
DOI: | 10.1021/es00082a005 | |||||||||
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: | 10 Nov 2021 22:21 |
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