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Dithiocarbamic acids have been investigated with regards to their monobasic or dibasic characteristics using three methods of analysis. The variation of the summit potentials for oxidation of dithiocarbamic acids at a dropping mercury electrode in ac polarography enables the determination of acid dissociation constants for the sulfur protonation. This factor, and the rate profiles as a function of pH for the decomposition of several dithiocarbamic acids, is used to interpret the unusual acid-base titration curves of dithiocarbamates. It is concluded that dithiocarbamic acids are monobasic. An explanation is given of the difference in the acid-base properties of dithiocarbamates