1160
DENNIS H.EVANS
Theory for a Homogeneous Reaction following a Quasireversible Electrode Reaction
by Dennis H.Evans Department of Chemistry, University of Wisconsin, Madison, Wisconsin 68706 (Received September SO, 1071) Publication costs assieted bg the National Science Foundation
Theory is developed for the electrochemical mechanism involving the irreversible homogeneous chemical reaction of the product of a quasireversible heterogeneous electron-transfer reaction at an electrode surface. A numerical method is employed to obtain theoretical current-potential curves for cyclic voltammetry. Correlations of peak potential, current function, and wave shape with dimensionless kinetic parameters are presented and discussed. Theory for cyclic voltammetry with an irreversible second-order reaction of the product of the electrode reaction is also presented. It is found that the electron-transfer reaction will be sufficiently rapid to permit use of earlier theories which assume reversible behavior if k t C ~ * @ " ~
