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Kinetic studies on the peroxyoxalate chemiluminescence reaction: determination of the cyclization rate constant
Sandra M Silva1, Fúlvio Casallanovo, Karen H Oyamaguchi
1Instituto de Química, Universidade de São Paulo, São Paulo, S.P., Brazil.
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.
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