Polarography of some sulphur-containing compounds : Part XII. Anodic waves of monoalkyldithiocarbamates and their reactions with heavy metals

Monoalkyldithiocarbamates give two anodic polarographic waves, corresponding to a one-electron and a two-electron process. A reaction scheme is proposed. The unusual behaviour observed during controlled-potential electrolysis in sodiumhydroxide media is interpreted as a chemical reaction of the primary electrolysis product; the species formed gives a wave similar to the original compound. Different adsorption phenomena are probably caused by varying orientation of the mercury compound on the electrode surface. The adsorbed layer formed in sodium hydroxide solution is so close-packed that it prevents hydroxyl ions from penetrating and thus giving an anodic wave. For analytical purposes, 0.1 M sodium hydroxide is the most suitable supporting electrolyte; linear calibration graphs can be obtained over the range 5 · 10^-5–1 · 10^-3M.