QUASI-REVERSIBLE LINEAR-POTENTIAL-SWEEP VOLTAMMETRY - ANALYTIC SOLUTION FOR RATIONAL-ALPHA

An analytic solution is presented to the problem of predicting the sha pe of a linear-potential-sweep voltammogram for a quasireversible elec trode process under the conditions usually encountered in voltammetric experiments. It is necessary to assume that the transfer coefficient is a rational number, but in practice, this is not an important restri ction. The solution takes the form of a series of exponential function s, the coefficients of which are calculable by a simple recursion form ula. The series diverges except in the potential range corresponding t o the early stages of the experiment, but numerical methods neverthele ss permit all interesting regions of the voltammogram to be investigat ed. The exact location of the peak, as a function of cu and of the kin etic parameter k(RT/nFvD)(1/2), has been delineated. Comparison of the se results with data generated by the DigiSim software is reported.