The Anomalous Electroreduction of Water at the Dropping Mercury Electrode in Relatively Concentrated Salt Solutions¹

Polarographic Determination of Oxygen. Anomalous Current Encountered with Rapid-Dropping Mercury Electrode

“…If the value of 0.02 were ignored, tie values range only from 0.05 to 0.07, which may be regarded as a fair indication that some phenomenon closely related to the so-called water current (also called "maxima of the second hand") is involved here. The term, water current, may be a misnomer, as Meites' coulometric investigation ( 12) indicates that water is not reduced to produce this current; nevertheless, "water current" and "anomalous current" are used synonymously here, because the phenomenon was termed water current when first reported (15).…”

“…GELATIN AS ANOMALOUS CURRENT SUPPRESSOR Orlemann and Kolthoff (15) suggested that small amounts of gelatin (0.005 wt. %) will suppress the water current; Buckley and Taylor (2) used 0.014 wt.…”

“…ANOMALOUSCURRENT Orlemann and Kolthoff(15) proposed the following equation relating the water current (anomalous) to the capil-…”

Polarographic Theory, Instrumentation, and Methodology

“…WATER CURRENT Orlemann and Kolthoff (49,89) discovered that under certain conditions an anomalous current is observed with the dropping electrode at potentials more negative than -0.9 volt versus the saturated calomel electrode. They attributed this current to the direct combination of water molecules and electrons, H20 + e ->l/-i H2 + OH~, and presented cogent evidence in support of this conclusion.…”

Polarographic maxima revisited

“…Hydrodynamic nonuniformity duc to the flow of mercury into the drop produces "false waves" on the diffusion-current plateau; this so-called "maximum of the second kind" appears in very dilute solutions [3]; its height is very nearly proportional to the concentration of the depolarizer.…”