Studies of electroreduction of nitropentane and nitrohexane on mercury electrodes in the presence of adsorbed aliphatic alcohols

Abstract

AbstractElectroreduction of 1‐nitropentane and 1‐nitrohexane was studied on mercury electrodes in aqueous solutions, together with the inhibitors: n‐pentanol, n‐hexanol and n‐heptanol. The electrode behavior of these species was not found to be influenced by inhibitors at concentrations lower than 10 mM and 2 mM for n‐pentanol and n‐hexanol, respectively, because adsorption of nitrocompounds is stronger than that of alcohols. For high alcohol concentrations, when a total surface coverage by inhibitor molecules is almost achieved, the reaction of nitroalkanes is inhibited. Steric factors evaluated using the dependence of rate constant on inhibitor concentration were used in the determination of the orientation of reactant molecule on the electrode. For alcohol concentrations near saturation, the rate constant becomes independent of inhibitor concentration. In this case a reaction of nitroalkanes dissolved in the surface organic phase was postulated.