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Kinetic studies on the chemiluminescent decomposition of an isolated intermediate in the peroxyoxalate reaction
Author(s) -
Stevani Cassius V.,
Baader Wilhelm J.
Publication year - 1997
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/(sici)1099-1395(199708)10:8<593::aid-poc926>3.0.co;2-h
Subject(s) - chemistry , peroxyoxalate , chemiluminescence , photochemistry , reactive intermediate , potassium hydroxide , reaction rate constant , imidazole , potassium periodate , catalysis , organic chemistry , kinetics , physics , quantum mechanics
The peroxyoxalate system undergoes one of the most efficient chemiluminescence reactions and is the only one considered to involve an intermolecular chemically initiated electron exchange luminescence mechanism, with proven high efficiency. Several reactive intermediates have been proposed, which, upon interaction with a fluorescent activator, lead to excited‐state generation. The synthesis and spectral characterization of 4‐chlorophenyl O,O ‐hydrogen monoperoxyoxalate ( 1 ), a compound analogous to one of the proposed reactive intermediates, was recently reported. Here the results of a kinetic study on the chemiluminescent decomposition of this peracid 1 , catalyzed by oxygen bases (potassium hydroxide, potassium tert ‐butoxide and potassium p ‐chlorophenolate) or nitrogen bases [pyridine, imidazole and 1,8‐bis(dimethylamino)naphthalene] are presented. Based on the dependence of the observed rate constants on the base concentration, kinetic schemes are proposed for the catalyzed decomposition of 1 and rate constants are assigned to specific reaction steps. The results obtained with the nitrogen bases give further support in favor of 1,2‐dioxetane dione as the reactive intermediate in the peroxyoxalate reaction. © 1997 John Wiley & Sons, Ltd.