DETERMINATION OF HETEROGENEOUS RATE CONSTANTS BY DOUBLE-STEP POTENTIOSTATIC METHOD

The theory of a new technique for the measurement of electrochemical rate constants is developed. It is shown that the double-step potentiostatic methods, hitherto applied only in the study of homogeneous kinetics, may be extended to the study of heterogeneous rate constants. The boundary value problem for this system has been solved analytically for the case of a plane electrode, and the solution has been extended to the case of the dropping mercury electrode. Algebraic and tabulated functions are presented relating the current or charge measured to the kinetic parameters governing the charge transfer processes occurring in either step. © 1969.