THE TEMPERATURE-DEPENDENCE OF THE ELECTROREDUCTION RATE OF THE PERSULFATE ANION IN THE PRESENCE OF A CONDENSED LAYER OF 1-HYDROXYADAMANTANE

The temperature dependence of the electroreduction rate of the S2O82- anion is studied at the electrode covered with a condensed adsorption layer of 1-hydroxyadamantane (1-AdOH). The electroreduction rate in th e region of relatively low temperatures is found to be almost independ ent of the temperature and the nature of the supporting-electrolyte ca tion. Assuming that the width of the potential barrier for electron tr ansfer increases by a thickness of an adsorbed molecule of 1-AdOH, the barrier height is estimated. Modeling calculations of the electrode p rocess rate are performed for various lengths of the tunneling path of electron and different temperatures. The characteristic features of t he S2O82- electroreduction are believed to be intrinsic to the electro de processes at low temperatures, provided the activation energy is lo w and the potential barrier is sufficiently wide.