Jc. Myland et Kb. Oldham, QUASI-REVERSIBLE LINEAR-POTENTIAL-SWEEP VOLTAMMETRY - ANALYTIC SOLUTION FOR RATIONAL-ALPHA, Analytical chemistry, 66(11), 1994, pp. 1866-1872
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.