Comprehensive Chemical Kinetics – serie

The whole of Volume 22 is devoted to the kinetics and mechanisms of the decomposition and interaction of inorganic solids, extended to include metal carboxylates. After an introductory chapter on the characteristic features of reactions in the solid phase, experimental methods of investigation of solid reactions and the measurement of reaction rates are reviewed in Chapter 2 and the theory of solid state kinetics in Chapter 3. The reactions of single substances, loosely grouped on the basis of a common anion since it is this constituent which most frequently undergoes breakdown, are discussed in Chapter 4, the sequence being effectively that of increasing anion complexity. Chapter 5 covers reactions between solids, and includes catalytic processes where one solid component remains unchanged, double compound formation and rate processes involving the interactions of more than three crystalline phases. The final chapter summarises the general conclusions drawn in the text of Chapter 2-5.

This book addresses primarily the engineer in industrial process development, the research chemist in academia and industry, and the graduate student intending to become a reaction engineer. In industry, competitive pressures put a premium on scale-up by large factors to cut development time. To be safe, such development should be based on "fundamental" kinetics that reflect the elementary steps of which the reaction consists. The book forges fundamental kinetics into a practical tool by presenting new, effective methods for elucidation of mechanisms and reduction of complexity without unacceptable sacrifice in accuracy: fewer equations (lesser computational load), fewer coefficients (fewer experiment to determine them). For network elucidation, new rules relating network configurations to observable kinetic behaviour allow incorrect networks to be ruled out by whole classes instead of one by one. For modelling, general equations and algorithms are given from which equations for specific networks can be recovered by simple substitutions.

The procedures are illustrated with examples of industrial reactions including, among others, paraffin oxidation, ethoxylation, hydroformylation, hydrocyanation, shape-selective catalysis, ethane pyrolysis, styrene polymerization, and ethene oligomerization. Many of the rate equations have not been published before.

The expanded edition of the 2001 title, Kinetics of Homogeneous Multistep Reactions includes new chapters on heterogeneous catalysis and periodic and chaotic re-actions; new sections on adsorption, statistical methods, and lumping; and other new detail.

The generally accepted definitions of acids and bases together with the generalized definition for the solvent system introduced by the author for the description of both molecular and ionic solvents are discussed. The oxobasicity index introduced as a measure of relative oxoacidic properties of ionic melts (pIL) and methods of its determination are presented. Moreover, the oxoacidity scales of ionic melts based on alkali metal halides at different temperatures are constructed. The sequential addition method (SAM), proposed by the author to investigate the effect of oxide particle size on oxide solubilities is presented.

This book is meant for specialists developing theoretical and applied aspects of molten salt chemistry, acid-base theories and solubility phenomena. It will also be useful for those chemists who wish to extend their knowledge of physical and solution chemistry.

Unimolecular Kinetics: Part 2: Collisional Energy Transfer and the Master Equation, Volume�43 in Elsevier's Comprehensive Molecular Kinetics series, addresses collision energy transfer and the effects it has on gas phase reactions, particularly at low gas density. Such systems include combustion, industrial gas phase processes and atmospheric/environmental processes. The book also discusses The Master Equation to give a good overview of the mechanics underpinning unimolecular kinetics. This new volume will be of interest to researchers investigating gas phase processes which involve unimolecular reactions and the related intermolecular reactions.

This volume attempts to provide a concise treatment of both thermo- and photochemical reactions by means of generalised differential equations, their set-up in matrix notation, and their solution by a formalism using numerical integration. At a first glance this approach might be surprising. However, apart from the argument that the didactics of thermal reactions are easier to handle than those of kinetics, the book provides additional reasons in support of this approach. Therefore, the formalism derived allows the evaluation of photochemical reactions, which are superimposed thermal reactions taking into account that the amount of light absorbed varies during the reaction. Because of this, any approximation, either by using total absorbance or negligible absorbance, will cause considerable errors even for simple reactions. The approach chosen to transform the axis of the radiation time into a new variable that includes the photokinetic factor proves that formal kinetics can be applied to thermal and photochemical reactions as well, and even allows the handling of solutions that cannot be homogenised or solid samples in which the concentration varies locally. By using this approach to introduce partial photochemical quantum yields even complex mechanisms can be determined quantitatively.

A large number of examples for different mechanisms and an introduction to many spectroscopic and chromatographic methods suitable for photokinetic analyses are provided to enable the reader to carry out a step-by-step evaluation of his own measurements. To reduce the number of formula in some chapters an appendix has been included which contains a detailed description of the calculus of some essential examples. For the convenience of the reader the following has been included:

. A large number of examples describing the use of formula

. A detailed description of the procedure for applying photokinetics to complex consecutive photoreactions

. An Internet address where the reader can find a tutorial for this procedure:http://www.barolo.ipc.uni-tuebingen.de/tele/photokin/

. A simple macro to help in programming his own evaluation procedure.