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Title: Metal ion-sulfur(IV) chemistry. 2. Kinetic studies of the redox chemistry of copper(II)-sulfur(IV) complexes

Abstract

The redox chemistry of Cu(II)-S(IV) complexes is examined, and the rate of reduction of Cu(II) is determined. The reduction of Cu(II) is shown to proceed via Cu/sup II//sub 2/SO/sub 3//sup 2 +/ and Cu/sup II//sub 2/CO/sub 3/OH/sup +/ intermediates. Copper(I), SO/sub 4//sup 2 -/, and a mixed-valence compound, Cu/sup II/SO/sub 3/Cu/sub 2//sup I/SO/sub 3/ x 2H/sub 2/O, are determined to be the principal products. The rate law is consistent with consecutive first-order reactions. Results are interpreted in terms of the initial formation of an inner-sphere complex, which is followed by a rate-limiting electron-transfer step. These results are discussed in light of previously accepted mechanisms for the trace metal catalysis of the autoxidation of SO/sub 3//sup 2 -/.

Authors:
;
Publication Date:
Research Org.:
California Institute of Technology, Pasadena (USA)
OSTI Identifier:
6774025
Resource Type:
Journal Article
Journal Name:
Environ. Sci. Technol.; (United States)
Additional Journal Information:
Journal Volume: 22:8
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COPPER; REDOX REACTIONS; SULFUR; COMPLEXES; ELECTRON TRANSFER; CHEMICAL REACTIONS; ELEMENTS; METALS; NONMETALS; TRANSITION ELEMENTS; 400201* - Chemical & Physicochemical Properties

Citation Formats

Conklin, M H, and Hoffmann, M R. Metal ion-sulfur(IV) chemistry. 2. Kinetic studies of the redox chemistry of copper(II)-sulfur(IV) complexes. United States: N. p., 1988. Web. doi:10.1021/es00173a005.
Conklin, M H, & Hoffmann, M R. Metal ion-sulfur(IV) chemistry. 2. Kinetic studies of the redox chemistry of copper(II)-sulfur(IV) complexes. United States. https://doi.org/10.1021/es00173a005
Conklin, M H, and Hoffmann, M R. 1988. "Metal ion-sulfur(IV) chemistry. 2. Kinetic studies of the redox chemistry of copper(II)-sulfur(IV) complexes". United States. https://doi.org/10.1021/es00173a005.
@article{osti_6774025,
title = {Metal ion-sulfur(IV) chemistry. 2. Kinetic studies of the redox chemistry of copper(II)-sulfur(IV) complexes},
author = {Conklin, M H and Hoffmann, M R},
abstractNote = {The redox chemistry of Cu(II)-S(IV) complexes is examined, and the rate of reduction of Cu(II) is determined. The reduction of Cu(II) is shown to proceed via Cu/sup II//sub 2/SO/sub 3//sup 2 +/ and Cu/sup II//sub 2/CO/sub 3/OH/sup +/ intermediates. Copper(I), SO/sub 4//sup 2 -/, and a mixed-valence compound, Cu/sup II/SO/sub 3/Cu/sub 2//sup I/SO/sub 3/ x 2H/sub 2/O, are determined to be the principal products. The rate law is consistent with consecutive first-order reactions. Results are interpreted in terms of the initial formation of an inner-sphere complex, which is followed by a rate-limiting electron-transfer step. These results are discussed in light of previously accepted mechanisms for the trace metal catalysis of the autoxidation of SO/sub 3//sup 2 -/.},
doi = {10.1021/es00173a005},
url = {https://www.osti.gov/biblio/6774025}, journal = {Environ. Sci. Technol.; (United States)},
number = ,
volume = 22:8,
place = {United States},
year = {Mon Aug 01 00:00:00 EDT 1988},
month = {Mon Aug 01 00:00:00 EDT 1988}
}