Scavenging of SO4− radical anions by mono- and dicarboxylic acids in the Mn(II)-catalyzed S(IV) oxidation in aqueous solution

The rate constants for reactions of the SO4− radical anion with some low molecular weight monocarboxylic acids (MCAs) and dicarboxylic acids (DCAs) and their anions using the laser flash photolysis-long path laser absorption (LFP-LPLA) technique were determined. The present study contains the first measured rate constants for SO4− reactions with glycolic, lactic, malic and malonic acid. The rate constants are found to be in the range from 105 to 107 M−1 s−1, with the lower values found for acids and higher values for their respective anions. In addition, the rate constants for scavenging of SO4− by all investigated organics in the Mn(II)-catalyzed S(IV) autoxidation at pH 4.5 and T=25 °C were determined by means of the reversed rate method. The comparison between these rate constants and the rate constants obtained by direct measurements confirms the proposed inhibiting mechanism for the Mn(II)-catalyzed S(IV) autoxidation in the presence of monocarboxylic acids. In the case of formic acid, which causes the highest inhibition, this mechanism can explain the second part of kinetic traces (i.e. after the induction period). Surprisingly, although dicarboxylic acids are reactive toward SO4− they do not contribute to the inhibition of S(IV) oxidation (especially malic and malonic acids).