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Mechanistic Studies on the Peroxyoxalate Chemiluminescence Using Sodium Salicylate as Base Catalyst

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Author(s):
Souza, Glalci A. ; Lang, Andre P. ; Baader, Wilhelm J.
Total Authors: 3
Document type: Journal article
Source: Photochemistry and Photobiology; v. 93, n. 6, p. 7-pg., 2017-11-01.
Abstract

Mechanistic studies on the peroxyoxalate chemiluminescence are often conducted with imidazole as base and nucleophilic catalyst. However, it is also known that this compound, at high concentrations, leads to a drastic reduction in the chemiluminescence quantum yields, apparently due to the destruction of the high-energy intermediate. Consequently, the search for new catalysts for this transformation is of importance for mechanistic studies as well as analytical application. Therefore, we report here a study on the mechanism of the peroxyoxalate reaction with sodium salicylate as base catalyst, which has already been utilized in this reaction; however, no detailed mechanistic investigation is known. In this work, a kinetic study on the sodium salicylate-catalyzed reaction of bis(2,4,6-trichlorophenyl) oxalate with hydrogen peroxide using 9,10-diphenylanthracene as activator is reported, where observed rate constants, singlet quantum yields and activation parameters are determined in different reaction conditions, leading to the formulation of a general mechanistic reaction scheme. (AU)

FAPESP's process: 14/22136-4 - Use of green solvents and their mixtures for optimizing chemical processes
Grantee:Omar Abou El Seoud
Support Opportunities: Research Projects - Thematic Grants