The oxidation process occurring on mercury electrodes in the presence of hydrogen peroxide has been analized in basic solutions by polarography and voltammetry in their linear scan and differential pulse modes. The process involves Hg(I) ion - in addition to Hg(II) ion - and hydroperoxide radicals, these last formed at trace levels. To demonstrate this radical generation radical scavengers (antioxidants), characterized with the DPPH center dot radical scavenging assay, were employed. The interaction of the radicals with the antioxidant originate the decrease in signal, but the antioxidant itself does not react with the hydrogen peroxide in the absence of Hg. In the absence of antioxidant, the process is two-electron, being the rate-determining step the second electron transfer; at high concentrations of antioxidant, the oxidation corresponds to a reversible one-electron transfer followed by a chemical reaction between the hydroperoxide radicals and the antioxidant. A reaction scheme is proposed for intermediate antioxidant concentrations. (C) 2014 The Electrochemical Society. All rights reserved.