Kinetics and mechanism of the oxidation of sulfite by trans-[Ru(tmc)O2]2+ (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)22_Publication in policy or professional journal

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Original languageEnglish
Pages (from-to)313-315
Journal / PublicationJournal of the Chemical Society - Dalton Transactions
Issue number3
Publication statusPublished - 7 Feb 1997

Abstract

The kinetics of the oxidation of SO3 2- by trans-[Ru(tmc)O2]2+ (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) has been studied in aqueous solution at 25.0°C. The reaction has the following stoichiometry: trans-[RuVI(tmc)O2]2+ + SO3 2- + H2O → trans-[RuIV(tmc)O(OH2)]2+ + SO4 2-. Sulfite and sulfur-containing products were analysed by ion chromatography. No S2O6 2- could be detected. The rate law is -d[RuVI]/dt = k/{1 + ([H+]/K)}[RuVI][SIV] with k = (7.0 ± 1.4) × 104 dm3 mol-1 s-1 and K= (3.4 ± 1.0) × 10-7 mol dm-3 at I = 1.0 mol dm-3. The value of k is more than two orders of magnitude greater than predicted by Marcus theory, and an inner-sphere mechanism involving the intermediate [O=RuVI=O-SO3] is proposed. This may decompose by one- or two-electron pathways.

Citation Format(s)

Kinetics and mechanism of the oxidation of sulfite by trans-[Ru(tmc)O2]2+ (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane). / Lau, Tai-Chu; Chow, Kwok-Ho; Lau, Kent W. C.; Tsang, Wenny Y. K.

In: Journal of the Chemical Society - Dalton Transactions, No. 3, 07.02.1997, p. 313-315.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)22_Publication in policy or professional journal