Kinetic studies on the peroxyoxalate chemiluminescence reaction: determination of the cyclization rate constant.
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.
Silva
Sandra M
SM
Instituto de Química, Universidade de São Paulo, São Paulo, S.P., Brazil.
Casallanovo
Fúlvio
F
Oyamaguchi
Karen H
KH
Ciscato
Luiz F L M
LF
Stevani
Cassius V
CV
Baader
Wilhelm J
WJ
D006861:Hydrogen Peroxide; D007700:Kinetics; D008163:Luminescent Measurements; D015394:Molecular Structure; D010070:Oxalates
D010070:Oxalates; C044622:peroxyoxalate; D006861:Hydrogen Peroxide