Kinetic study of the hexacyanoferrate (III) oxidation of dihydroxyfumaric acid in acid

The kinetics of the hexacyanoferrate (III) oxidation of dihydroxyfumaric acid to hexacyanoferrate (11) and diketosuccinic acid was looked into within the 0.04 to 5.3 M HCl acidity range under different temperatures, ionic strengths, and solvent permittivity conditions. The kinetic effect of alkali metal ions, transition metal impurities, and substrate concentrations have also been analyzed. The observed inhibition effect brought about by addition of the reaction product, hexacyanoferrate (II), is a sign of a complex mechanism. The rate constants remained essentially unchanged up to 1 M HCl, diminished between 1.0 and 3.0 M HCl, and rose above 3.0 M HCl. Depending on the medium acidity, three mechanisms can be put forward, which involve different kinetically active forms. At low acidity, the rate-determining step involves a radical cation and both the neutral and the anion substrate forms are equally reactive (k(1) = k(2) = 2.18 +/- 0.05 M-1 s(-1), k(-1) = 0.2 +/- 0.03). When the medium acidity is boosted, the rate-determining step involves the neutral dihydroxyfumaric acid and two hexacyanoferrate (111) forms. In the intermediate region the rate constant diminished with rising [H+] (k(1)' = 0.141 +/- 0.01 and k(2)' = 6.80 +/- 0.05). Specific catalytic effect by binding of alkali metal ions to oxidant has not been observed. In all instances it was assessed that the substrate decomposition is slow compared to the redox reaction.