ABSTRACT
This chapter develops the theoretical basis for understanding the relationships between current i(t) and radiant intensity I(t), the analytical variables in any quantitative study of electrogenerated chemiluminescence (ECL). Because the observed CL intensity results from the reaction of species generated electrochemically at a solution/electrode interface, this development begins with an understanding of the mass transfer and mass transport of solution species to an electrochemical interface to generate the precursors to ECL. Only then is it possible to address the ECL phenomenon as these precursors undergo subsequent mass transfer and transport from the electrochemical interface to react in a spatial reaction zone within the diffusion layer. Ultimately, the observed CL intensity depends upon the rate at which these precursors react within this reaction zone to produce excited state species and the rate at which these species go on to produce photons. Each of these processes may influence the observed current as well as being the rate-determining step for the observed CL intensity.
