Studies on A.C. Polarography. I. Theoretical Treatment

At first the rigorous and orthodox treatment of the polarographic electrolytic current due to the superposition of an alternating voltage upon a constant voltage is shown and the earlier polarographic studies, in which an alternating voltage is employed, are discussed. Next it is shown that in order to treat the a.c. polarography theoretically, we can profitably assume that the superimposed sinusoidal a.c. voltage is equivalent to the square-wave voltage of the same frequency. In a case when an a.c. voltage, is superimposed upon the usual d.c. voltage, the resulting current becomes a very complicated function of time. It can be shown, however, that the current is the algebraic sum of a.c. component and d.c. component, the latter of which is Fournier’s polarogram and the former Breyer’s polarogram. Some outstanding characteristics of both components are satisfactorily cleared up, and it demonstrated that in such a manner a rational and systematic explanation of a.c. polarography is given.