Coulometric generation of H + ions by oxidation of thiols at a platinum anode and by oxidation of mercury in acetic acid—acetic anhydride

Abstract

The coulometric generation of hydrogen ions by anodic oxidation of propane-1-thiol, butane-1-thiol, 2-mercaptopropionic acid, heptane-1-thiol, 2-mercaptoethanol, methyl and ethyl thioglycollate and p-thiocresol in acetic acid—acetic anhydride (1 + 6 v/v) is described, together with the possibility of coulometric generation of protons by mercury oxidation in the presence of p-thiocresol in the same solvent system. Current-potential curves for the solvent, indicator, titrated bases, mercury and the investigated thiols showed that in acetic acid—acetic anhydride (5 + 95, v/v), mercury and the investigated thiols are oxidized at potentials which are much more negative than those of the titrated bases and other components present in the solution. Titration of potassium hydrogenphthalate and sodium acetate with protons generated by the oxidation of thiols, and of sodium acetate, lithium acetate and pyridine with protons generated by the oxidation of mercury, demonstrated that the oxidation of both thiols and mercury proceeds quantitatively with 100% current efficiency.