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Catalysis of the autoxidation of aquated sulfur dioxide by homogeneous metal-phthalocyanine complexes

Boyce, Scott D. and Hoffmann, Michael R. and Hong, P. Andrew and Moberly, Lorraine M. (1983) Catalysis of the autoxidation of aquated sulfur dioxide by homogeneous metal-phthalocyanine complexes. Environmental Science and Technology, 17 (10). pp. 602-611. ISSN 0013-936X. doi:10.1021/es00116a008. https://resolver.caltech.edu/CaltechAUTHORS:20150820-073728749

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Abstract

The autoxidation of sulfur dioxide to sulfate in aqueous solution has been examined over the pH range 4-13 in the presence of water-soluble transition metal-4,4’,4”,4”‘-tetrasulfophthaloc anine com lexes, MTSP (where M = Fe^(II), Mn^(II),Co^(II), Ni^(II), Cu^(II), and V^(IV). Experimental rate data have been analyzed in terms of a Michaelis-Menten kinetic expression derived from a bisubstrate kinetic model. The rate law and spectroscopic measurements indicate that the reaction proceeds via the formation of an activated complex in which O_2 and two molecules of SO_3^(2-) are reversibly bonded to the catalytic center. Relative reactivity is determined by the ability of the central metal atom to reversibly bind molecular oxygen. Analysis of the spectroscopic data suggests that photaassisted catalysis arises from the absorption of light by a ternary activated complex.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/es00116a008DOIArticle
http://pubs.acs.org/doi/abs/10.1021/es00116a008PublisherArticle
ORCID:
AuthorORCID
Hoffmann, Michael R.0000-0001-6495-1946
Additional Information:© 1983 American Chemical Society. Received for review December 21,1982. Accepted May 23,1983. Financial support for this research was provided by the U.S. Environmental Protection Agency under Contract R808086-01.
Funders:
Funding AgencyGrant Number
Environmental Protection Agency (EPA)R808086-01
Issue or Number:10
DOI:10.1021/es00116a008
Record Number:CaltechAUTHORS:20150820-073728749
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150820-073728749
Official Citation:Catalysis of the autoxidation of aquated sulfur dioxide by homogeneous metal-phthalocyanine complexes Scott D. Boyce, Michael R. Hoffman, P. Andrew. Hong, and Lorraine M. Moberly Environmental Science & Technology 1983 17 (10), 602-611 DOI: 10.1021/es00116a008
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:59780
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:20 Aug 2015 21:44
Last Modified:10 Nov 2021 22:25

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