The behaviour of the lead dioxide electrode. Part 2.—The irreversible discharge of the lead accumulator

Abstract

It is shown that the evidence that has at various times been advanced against the double sulphation theory of the working of the lead accumulator is invalid. From a study of the behaviour of the lead dioxide electrode, under various conditions of discharge, it is concluded that the reaction mechanism remains the same as for the reversible electrode. The consequence of this proof of the identity of mechanism is that no detailed mechanism for the electrode processes is acceptable unless it conforms with the thermodynamical requirement that it contains no spontaneous non-electrochemical stage.

Anodization of Lead and Lead Alloys in Sulfuric Acid

“…When reanodized in H~SO~ flPbO~ was the solid product. Therefore, formation of aPbO~ may be considered an irreversible electrode process when it occurs in the positive plate of the lead acid cell, and it is necessary to differentiate between studies of reversible systems such as reported by Beck, Lind, and Wynne-Jones (18) and of irreversible systems such as grid corrosion.…”

The Discharge Mechanism of Certain Oxide Electrodes

“…The minimum in the discharge curve.--It has been noticed previously (24,1) that in the discharge of fl-PbO2 and ~/-MnO~ electrodes in acid electrolytes the electrode potential passes through a minimum before the attainment of a steady state. In the present investigation minima were found in the discharges of fl-PbO~ in all electrolytes, TI~O~ (m alkaline electrolyte) and blue TiO~, and were not observed for normal TiO2 and a-PbO~.…”

The Discharge Properties of a-PbO[sub 2] in Dilute H[sub 2]SO[sub 4] Electrolyte

“…The discharge properties and discharge mechanism of fl-PbO_~ in H2SO, electrolyte have been studied in considerable detail (1)(2)(3). There is disagreement as to the mechanism (1-3), but the experimental characteristics of the discharge, such as reduction overpotentials, shape of the potential-time discharge curves, etc., are well known (1,3).…”