Olga Voskresenskaya
Joint Institute for Nuclear Research, Dubna, Moscow region, Russia

Series: Chemistry Research and Applications
BISAC: SCI013050

This book presents generalizations of the classical thermodynamic methods for investigating the complex formation and also the kinetic analogues of these methods to determine together with formation constants also redox-decomposition rate constants of complexes with cations in an unstable oxidation state, as well as the rate law of numerous redox processes for which the rate-controlling step is the decay of such intermediate complexes. A classification of these generalized thermodynamic and kinetic methods is performed. Their implementation is discussed on examples of studying the complexation and intramolecular redox decomposition of cerium(IV) complexes with a series of aliphatic organic compounds.

Generalized methods are applied to the study of cerium(IV) complexes with three groups of organic ligands: dicarboxylic, oxycarboxylic acids, and polyatomic alcohols. The region of existence, composition, ligand speciation, stability constants, rate constants, and activation energies of intracomplex redox decomposition are determined for the complexes [CeOH(H-xR)n]3-nx in a sulfate medium. The rate law occurring in the systems redox processes and corresponding mechanism are established on the basis of calculated parameters and the set of all equations describing the establishment and violation of equilibria in the investigated systems. The existence of positive correlation between thermodynamic and kinetic stability of the complexes [CeOHH-xR]3-x with x = 2 and its absence for x > 2 are found on the sulfate background. Some computational aspects of simultaneous determining the stability constants and redox-decompositions rate constants for variable-valence metal complexes in solutions also are discussed.

This book is intended for researchers in the chemistry of coordination compounds and physical chemistry, as well as faculty and advanced students. (Imprint: Nova)