Hoffmann, Michael R. and Lim, Brian C. (1979) Kinetics and mechanism of the oxidation of sulfide by oxygen: catalysis by homogeneous metal-phthalocyanine complexes. Environmental Science and Technology, 13 (11). pp. 1406-1414. ISSN 0013-936X. http://resolver.caltech.edu/CaltechAUTHORS:20150820-144459940
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Abstract
The kinetics of the catalyzed autoxidation of hydrogen sulfide to sulfur, thiosulfate, and sulfate in aqueous solution has been investigated potentiometrically over the pH range 5-12. The catalytic effects of cobalt(II), nickel(II), and copper(I1) 4,4’,4”,4”'- tetrasulfophthalocyanine have been determined, and differences in catalytic ability have been explained in terms of relative capacity of the octahedral complexes to reversibly bind oxygen. Kinetic data have been analyzed in terms of a bisubstrate Michaelis-Menton rate law. The rate law and other data indicate that the catalyzed reaction proceeds via the formation of a tertiary-activated complex in which HS^- and O_2 reversibly bind with CoTSP^(2-). pH variations have been explained in terms of the acid dissociation of H_2S, general base catalysis, and deprotonation of pyrrole nitrogens within the phthalocyanine ring.
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| Additional Information: | © 1979 American Chemical Society. Received June 23, 1978. Accepted August 17, 1979. Funds for his research project were provided by the Graduate School and the Sommerfeld Endowment of the Department of Civil and Mineral Engineering of the University of Minnesota. This support is greatly appreciated. | |||||||||
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| Record Number: | CaltechAUTHORS:20150820-144459940 | |||||||||
| Persistent URL: | http://resolver.caltech.edu/CaltechAUTHORS:20150820-144459940 | |||||||||
| Official Citation: | Kinetics and mechanism of the oxidation of sulfide by oxygen: catalysis by homogeneous metal-phthalocyanine complexes Michael R. Hoffmann and Brian C. Lim Environmental Science & Technology 1979 13 (11), 1406-1414 DOI: 10.1021/es60159a014 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 59798 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Ruth Sustaita | |||||||||
| Deposited On: | 20 Aug 2015 23:18 | |||||||||
| Last Modified: | 20 Aug 2015 23:18 |
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