Cathodic reduction of acids in dimethylformamide on platinum

A linear correlation was shown to exist between the acidity and the cyclic voltammetric half-potential of the reduction of acids in DMF for carboxylic and N-acids in the pKa range of 6–16. Chlorophenols are reduced at slightly lower potentials giving a separate parallel line. Applying the obtained equation and employing the same method to literature data in DMSO, the pKa values for conjugate aids of DMF and DMSO can be calculated, showing DMSO·H+ to be more acidic (pKa = 2.9) than DMF·H+ (pKa = 5.7). The analysis of cyclovoltammetric data demonstrated that a CE mechanism operates in the reduction of strong acids, including the conjugate acid of DMF. Weaker acids are reduced by direct discharge or a mixed mechanism.