Kinetic and Thermodynamic Stability of Cerium (IV) Complexes with a Series of Aliphatic Organic Compounds

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

Series: Chemistry Research and Applications
BISAC: SCI013050

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Edited by I Leslie Rubin, Robert J Geller, Abby Mutic, Benjamin A Gitterman, Nathan Mutic, Wayne Garfinkel, Claire D Coles, Kurt Martinuzzi, and Joav Merrick

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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)

Preface

Chapter 1. Introduction

Chapter 2. Methods for Investigation of Thermodynamic and Kinetic Stability of Cerium(IV) Complexes

Chapter 3. Investigating Stability of Cerium(IV) Complexes with Some
Aliphatic Organic Compounds

Chapter 4. A Comparative Study of the Investigated Systems

Index

"...This book is of undoubted scientific and methodological interest. The principal audience for the book are researchers in the field of coordination and physical chemistry, university faculty, undergraduate and graduate students." READ MORE... - Dr. Larisa N. Kurina, Academician of the Russian Academy of Natural History, Professor at Tomsk State University

"Investigation of the thermodynamic and kinetic aspects in formation and redox decompo-sition of the complexes with cations in anomalous oxidation states (OSs) is of considerable importance in relation to the problem of stabilizing the unstable OSs of elements. This prob-lem has recently become particular significance due to the accumulation of information on unusual OSs and the development of a number of topical issues in materials science." READ MORE... - Dr. Boris V. Spitsyn, Leading Researcher at the A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Institution of the Russian Academy of Sciences

"The book of Dr. Olga Voskresenskaya, a well-know expert in the field of coordination chemistry, is devoted to kinetic and thermodynamic aspects associated with the formation and redox decomposition of cerium(IV) complexes with various organic ligands. Cerium(IV) solutions, being a strong oxidation and complexation reagents, are widely applied in many analytical procedures. By theuse of redox and complexation reactions, they are extensively employed in determination of diverse inorganic and organic compounds." READ MORE... - Professor Emeritus Alexander Apelblat , Chemical Engineering Department, Ben Gurion University of the Negev

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