The origin and nature of chemiluminescence in the dibenzoylperoxide-dimethylaniline reaction

Article abstract of DOI:10.1002/bbpc.19981020219

It has been established that the dibenzoylperoxide (POOP)+dimethylaniIine (DMA) reaction is suitable to the slow production of free radicals at ambient temperature and in the absence of oxygen. The process is accompanied by a well measurable chemiluminescence (CL) without added sensitizer. The reaction carried out in acetonitrile is mainly ionic with the formation of radicals in between. We assume the existence of a 2:1 DMA/POOP complex as a possible source of radicals. The kinetics of CL is determined by the formation and decomposition rate of this complex. Calculated rate constant values: k_(f) = 3 × 10^-3 M^-1 s^-1 and k_(d) = 1 × 10^-3 s^-1. Based on the spectrum of the CL light and taking into consideration the analytical results we assume that the energy of CL is delivered almost totally by the cage termination product (ΔH_(r) =-385 kJ/mol) formed in excited state and this energy is transferred to the triphenylmethane dye-salt products (Malachite Green, Crystal Violet) which are the probable emitters of the CL light. Hydroperoxide is not formed in the reaction. WILEY-VCH Verlag GmbH, 1998.