Model for diffusion‐limited electrochemiluminescence

An approximate analytic expression is derived, based on a novel model for the reactive–diffusive processes in a electrochemiluminescence (ecl) experiment. The physical system treated is one in which ecl is produced by stepping the voltage of a planar electrode to the diffusion‐limited reduction value for an emitter species in the presence of a bulk oxidant precursor (9,10‐DPA with benzoyl peroxide). The unknown rate constants are determined by a least‐squares curve‐fitting computer code. The model, though crude, provides an excellent fit to the ecl intensity versus time data, including the rise portion of the curve.