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An approach to the investigation of the thermodynamic and kinetic stability of variable-valence metal complexes has been developed. Concepts of the generalised inverse problems of quantitative instrumental analysis and the complex formation equilibria are introduced. The procedure for this investigation is regarded as a sequential procedure for solving these two inverse problems. The classical methods for investigating the complex formations in solution are analysed in terms of these in-verse problems. Their generalisations are given to determine together with the formation constants also redox-decomposition rate constants of variable-valence metal complexes and the rate law of numerous redox processes, for which the rate-determining step is the decay of an intermediate complex, are presented. Classification is discussed and their implementation on the examples of the study of the complexation and in-tramolecular redox decomposition of cerium(IV) hydroxo complexes with some dicarboxylic, oxycarboxylic acids and aliphatic polyatomic alcohols in dependence on acidity (pH 0.73.4) of a sulphate medium at the ionic strength I=2 and temperatures of 10.043.0℃C by UV-Vis spectroscopy and pH measurements. The region of existence, composition, ligand speciation, stability constants of the complexes [CeOH(H-xR)n]3-nx, rate constants, and activation energies of the intramolecular redox decomposition were determined for these complexes on the sulphate background. The rate law of the redox process occurring in the studied systems on the basis of the calculated constants and set of all the chemical and algebraic equations describing the equilibria in systems is derived, and the quantitative model of this process is created. 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 was found on the sulphate background. Discussed also are the computational aspects of solving the regarded generalised problems. This book is well-suited for researchers in the chemistry of co-ordination compounds, physical chemistry, and biochemistry, as well as faculty and advanced students.
Cerium is the most abundant of the rare earth elements, making up about 0.0046% of the Earth's crust by weight. It is found in a number of minerals, the most important being monazite and bastnasite. Commercial applications of cerium include catalysts, additives to fuel to reduce emissions and to glass and enamels to change their colour. In this book, the authors study the molecular structure, technological applications and health effects of cerium. Topics include the synthetic and structural features of ceriopolyoxotungstates; cerium-based corrosion inhibitors; tetravalent cerium chemistry; comparative toxicity of cerium and other rare earth elements (REEs) in plant and invertebrate test systems; cerium-based catalysts for the selective catalytic reduction of NOx with NH3; cerium oxide and its reduction in composite materials under hydrogen containing atmosphere; cerium as fertiliser for soils in Russia; and the structure and reactivity of cerium IV complexes with aliphatic organic compounds.
Most syntheses in the chemical research laboratory fail and usually require several attempts before proceeding satisfactorily. Failed syntheses are not only discouraging and frustrating, but also cost a lot of time and money. Many failures may, however, be avoided by understanding the structure-reactivity relationship of organic compounds. This textbook highlights the competing processes and limitations of the most important reactions used in organic synthesis. By allowing chemists to quickly recognize potential problems this book will help to improve their efficiency and success-rate. A must for every graduate student but also for every chemist in industry and academia. Contents: 1 Organic Synthesis: General Remarks 2 Stereoelectronic Effects and Reactivity 3 The Stability of Organic Compounds 4 Aliphatic Nucleophilic Substitutions: Problematic Electrophiles 5 The Alkylation of Carbanions 6 The Alkylation of Heteroatoms 7 The Acylation of Heteroatoms 8 Palladium-Catalyzed C-C Bond Formation 9 Cyclizations 10 Monofunctionalization of Symmetric Difunctional Substrates
Chemical Kinetics and Reaction Dynamics brings together the major facts and theories relating to the rates with which chemical reactions occur from both the macroscopic and microscopic point of view. This book helps the reader achieve a thorough understanding of the principles of chemical kinetics and includes: Detailed stereochemical discussions of reaction steps Classical theory based calculations of state-to-state rate constants A collection of matters on kinetics of various special reactions such as micellar catalysis, phase transfer catalysis, inhibition processes, oscillatory reactions, solid-state reactions, and polymerization reactions at a single source. The growth of the chemical industry greatly depends on the application of chemical kinetics, catalysts and catalytic processes. This volume is therefore an invaluable resource for all academics, industrial researchers and students interested in kinetics, molecular reaction dynamics, and the mechanisms of chemical reactions.