RATE CONSTANTS AND THE LIMITING DIFFUSION FLUX FOR REACTIONS ON MICROELECTRODES

We present a new theory for rates of diffusion-controlled reactions on small electrodes in binary electrolytes. The theory reproduces the re sults of conventional theory for macroelectrodes and for microelectrod es with small electrode-ion interaction (as would apply for macroelect rodes) as compared to ion-ion interactions while allowing extension be yond this traditional macroelectrode regime. It predicts a new depende nce of the limiting current on the parameters of the electrode and of the environment when the electrode-ion interaction is large.