title: Kinetic studies on the peroxyoxalate chemiluminescence reaction: determination of the cyclization rate constant.
abstract: Although more currently utilized as analytical tool because of its high sensitivity and good reproducibility, the mechanism of the peroxyoxalate system, a chemiluminescence reaction with quantum yields only comparable to bioluminescence systems, has been extensively studied. The light emission mechanism can be divided in the pathway before chemiexcitation, which contains the rate-limiting steps, and the fast and kinetically non-observable chemiexcitation step. In this work, we obtain information on the mechanism of the slow pathways, attribute values to several rate constants prior to chemiexcitation and suggest a mechanistic scheme that could help optimization of conditions when the peroxyoxalate reaction is used as analytical tool.
authors.affiliation: Instituto de Química, Universidade de São Paulo, São Paulo, S.P., Brazil.
authors.forename: Sandra M
authors.initials: SM
authors.lastname: Silva
authors.forename: Fúlvio
authors.initials: F
authors.lastname: Casallanovo
authors.forename: Karen H
authors.initials: KH
authors.lastname: Oyamaguchi
authors.forename: Luiz F L M
authors.initials: LF
authors.lastname: Ciscato
authors.forename: Cassius V
authors.initials: CV
authors.lastname: Stevani
authors.forename: Wilhelm J
authors.initials: WJ
authors.lastname: Baader
mesh_terms: D006861:Hydrogen Peroxide; D007700:Kinetics; D008163:Luminescent Measurements; D015394:Molecular Structure; D010070:Oxalates
chemical_list: D010070:Oxalates; C044622:peroxyoxalate; D006861:Hydrogen Peroxide