Fundamental Studies on the Current-Voltage Curve in Polarography. II

In this paper authors have derived the equations of the polarographic current-voltage curve from the standpoint of chemical kinetics, assuming that the net electrode process is activation-controlled. The results obtained are summarized as follows: (1) Half-wave potential is the constant of the substance concerned, and is independent of its activity. (2) The potential where the current is equal to zero is only defined by the activities of the oxidant and the reductant in the body of the solution. (3) The inflection point of the cathodic or anodic wave agrees with its half-wave potential. (4) The relation between log(I⁄Id–I) and V of the cathodic or anodic wave is a straight line. The values of ΔF1, ΔF2 and a possible to be caluclated from the experimental date. (6) The theoretical curve is essentially the same as the experimental curve of the irreversible type.