THEORY OF CYCLIC VOLTAMMETRY FOR A DIMERIZATION REACTION INITIATED ELECTROCHEMICALLY

Theory of cyclic voltammetry is presented for an electrochemically initiated homogeneous dimerization reaction. The mathematical approach treats the linear partial differential equation by transformation to integral form and the nonlinear differential equation by finite difference. This approach should be of general interest, and therefore it is described in adequate detail. Results of the calculations both for planar and spherical electrodes are presented as diagnostic criteria analogous to those developed previously for a first-order reaction initiated electrolytically. Finally, a method is presented by which the dimerization rate constant can be evaluated from a single cyclic polarogram. © 1969, American Chemical Society. All rights reserved.