The reaction layer at microdiscs: A cornerstone for the analytical theoretical treatment of homogeneous chemical kinetics at non-uniformly accessible microelectrodes

A general definition of the linear reaction layer for electrochemical processes coupled to homogenous chemical kinetics is presented applicable to uniformly and non-uniformly accessible microelectrodes. In particular, ubiquitously-used microdisc electrodes are considered although the theoretical approach is open to any other electrode geometry. Thus, based on the suitable mathematical definition of the linear reaction layer, analytical expressions are deduced for a variety of reaction mechanisms, which enable a priori, rapid and accurate analysis of chemical kinetic effects on the system's steady state voltammetry. (C) 2016 Published by Elsevier B.V.