Silver(I) and Copper(II) Catalysis for Oxidation of Histidine by Cerium(IV) in Acid Medium: A Comparative Kinetic Study

The catalytic effect of silver(I) and copper(II) ions on the oxidation of histidine by cerium(IV) in aqueous sulfuric acid solutions was studied spectrophotometrically at a constant ionic strength of 3.0 mol dm^?3 and at 25°C. In both uncatalyzed and metal ions‐catalyzed paths, the reactions exhibited first‐order kinetics with respect to Ce(IV)] and catalyst], and fractional first‐order dependences with respect to His] and H⁺]. The oxidation rates increased as the ionic strength and dielectric constant of the reactions media increased. The catalytic efficiency of Ag(I) was higher than that of Cu(II). Plausible mechanistic schemes for both uncatalyzed and catalyzed reactions were proposed, and the rate laws associated with the suggested mechanisms were derived. In both cases, the final oxidation products of histidine were identified as 2‐imidazole acetaldehyde, ammonium ion, and carbon dioxide. The activation parameters associated with the second‐order rate constants were evaluated.