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Published August 1988 | public
Journal Article

Metal ion-sulfur(IV) chemistry. 3. Thermodynamics and kinetics of transient iron(III)-sulfur(IV) complexes

Abstract

Stability constants for the formation of Fe(III)-S(IV) complexes at µ = 0.4 M were determined spectroscopically. Values of K_1 = 10^(6.6) M^(-1) for Fe^(3+) + SO_3^(2-) ⇌ FeSO_3^+ and K_4 = 10^(7.3) M^(-1) for FeOH^(2+) + SO_3^(2-) ⇌ HOFeSO_3 were obtained. Raman measurements indicate that sulfite binds to the metal through oxygen. The kinetics of electron transfer between Fe(III) and S(IV) have been studied, and a mechanism is proposed. Kinetic and mechanistic aspects of the Fe(III)-catalyzed autoxidation of S(IV) are discussed in light of these results.

Additional Information

© 1988 American Chemical Society. Received for review May 1, 1987. Accepted January 6, 1988. We are indebted to Eric C. Betterton (Caltech) for his expert assistance throughout the latter stages of this work. We also acknowledge the personal support of our program officers D. Alan. Hanson (EPRI) and L. Swaby (EPA).

Additional details

Created:
August 19, 2023
Modified:
October 23, 2023