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Kinetics and mechanism of oxidation of excited state Tris-(2,2′-bipyridyl)-ruthenium (II) complex by peroxomonosulfate, peroxodisulfate, and peroxodiphosphate

✍ Scribed by Lakshmanan Venkatasubramanian; Periasamy Dharmalingam; Pichai Maruthamuthu

Publisher
John Wiley and Sons
Year
1990
Tongue
English
Weight
501 KB
Volume
22
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

Excitation of Ru(bipy)~3~^2+^ ion by visible radiation of wavelength λ = 436 nm in aqueous medium in presence of inorganic peroxides, peroxomonosulfate (PMS), peroxodisulfate (PDS), and peroxodiphosphate (PDP) was found to generate Ru(bipy)~3~^3+^. The kinetics of this photochemical oxidation of Ru(bipy)~3~^2+^ by each peroxide was followed spectrophotometrically and found to obey a total second‐order, first‐order each in [Ru(bipy)~3~^2+^] and [peroxide]. In the absence of light, thermal reaction of PMS and PDS with Ru(bipy)~3~^2+^ occurred but only when at 1.0 M [H^+^] and > 10^−2^M [peroxide]. The reaction of PMS with the complex is found to be cyclic, ie., Ru(bipy)~3~^3+^ formed oxidizes PMS itself and such a reaction was not observed in the case of PDS and PDP. The effects of pH, [peroxide], and [Ru(bipy)~3~^2+^] on the visible light induced oxidation of Ru(bipy)~3~^2+^ by these peroxides are investigated. The results are discussed with suitable reaction mechanisms.

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