Chemiluminescence from reactions of bis(pentachlorophenyl)oxalate, hydrogen peroxide and fluorescent compounds. Kinetics and mechanism

Abstract

The chemiluminescence arising from the reaction between bis(pentachlorophenyl)oxalate (PCPO) and hydrogen peroxide in the presence of the fluor 9,10-diphenylanthracene (DPA) has been examined in detail. The effects of varying reactant, base catalyst and fluor concentrations on chemiluminescence decay rates and quantum yields have been investigated and a mechanism which accounts for the kinetics of the reaction has been proposed. The rate-determining step is a reaction between PCPO and the hydroperoxide anion (OOH^–) and does not involve the fluorescent activator. The lifetime of the reactive intermediate formed in the rate-determining step is short (5 × 10^–7 s) and consistent with the proposed mechanism.