A Contribution to the Theory of Pulse Polarography. I. Theory of Current-Potential Curves

A general theory of pulse polarographic current-potential curves is developed for a simple electrode reaction proceeding at the expanding plane electrode. It is shown that when the ratio of the sampling time to the pre-electrolysis time is smaller than 1/30, this condition being satisfied in usual pulse polarographic practice, the equation of current-potential curves can be greatly simplified. The theory developed is applied to the three modes of pulse polarography nowadays practically employed, i.e., normal pulse, scan-reversal pulse and differential pulse polarography. For each mode, the dependence of current-potential curves on the kinetic parameters of electrode reaction as well as on the experimental variables is discussed.