Thermodynamic and Kinetic Parameters of Cerium(IV) Complexes with Some Dicarboxylic Acids

Abstract

The thermodynamic and kinetic parameters of the cerium(IV) complexes formed in the initial stage of oxidation of dicarboxylic acids (H₂L), like pentanedioic, butanedioic, propanedioic, and ethanedioic acids, by cerium(IV) sulfate were studied by the spectrophotometric and pH-potentiometric methods with the aid of integral kinetic methods at an ionic strength I = 2 mol/L within the pH range of–0.3–1.6 in a sulfuric acid medium and at temperature of 293.15 K. The composition of these complexes, the form of organic ligand existence therein, the thermodynamic parameters of their formation, and the kinetic parameters of their intramolecular redox decomposition were determined. Linear correlations between the found thermodynamic and kinetic parameters of the examined complexes [CeOHL]⁺ were obtained. The rate equation of the redox process occurring in the systems Ce⁴⁺–H₂L was established and the corresponding reaction model was considered.