CHEMILUMINESCENCE IN HYDROCARBON OXIDATION IN SOLUTION. A QUANTITATIVE STUDY OF THE EXCITATION AND EMISSION STEPS†

Abstract
Abstract— Chemiluminescence in the visible region during liquid‐phase hydrocarbon oxidation is excited by peroxy radical disproportionation; a carbonyl compound, P, in the triplet state is the emitter. Several types of energy transfer from P to acceptors are considered. These provide valuable information (lifetimes, rate constants, emission yields) relevant to triplet state molecules. The excitation yields are estimated making use of this information, the absolute chemiluminescence intensities and the reaction rates. Electronic excitation of P, vibrational excitation of ground state P and reverse decomposition of an intermediate complex into initial peroxy radicals are considered as competing processes strongly dependent on transformation of chemical energy into vibrations.