RESPONSE OF AN ECE REACTION TO A POTENTIAL LEAP

A technique is described for analyzing the chemical step of an ECE mec hanism, The current following the imposition of a large, concentration -polarizing step is semiintegrated, the semiintegral being then displa yed as a function of the logarithm of time. A wave-shaped response is predicted, during which the semiintegral doubles in magnitude (if each E reaction involves one electron). The wave may be analyzed to find v alues of the equilibrium constant K and each of the rate constants k(f ) and k(b). Such a total analysis is possible only if the pK Lies betw een -1 and +3, If pK is less than -1, k(f) alone is accessible, wherea s if pK > 3, the product k(f)K is the measurable constant.