xvii PART I PROPERTIES OF CRYSTALLINE MATERIALS The Effective U in Oxides and in Sulfides: Conceptual Phase Diagrams and their Applications . . . . . . . . . . . . . . .; . . . . . . . . . . . . . . . 1 John B. Goodenough 1. Definitions 1 2. Interatomic interactions 23 References 44 Electron Correlations in Elementary Structures. The Case of Weak Correlations: Metallic and Covalent Bondings . . . . . . . . . . . . . . . . . 45 J. Friedel Introduct i on 45 1. The H2 molecule 46 2. Other elementary diatomic molecules 52 3. Metallic aggregates 53 4. Macroscopic phases of transition metals 57 5. Aggregates and solids of tetravalent (sp) elements 64 6. Aggregates of covalent dimers 67 7. Weak distortions of metallic closepacked or covalent structures 69 Appendixes 74 References 82 Statistical Thermodynamics of Mixed Valence at Low Temperatures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85 Dieter Wohlleben 1. Introduction 85 2. The free enthalpy without mixing 86 3. The valence fluctuation temperature 89 4. 'The free enthalpy with interconfigurational mlxlng 90 5. Equation of state for the valence fluctuation n e 6. The conduction electron density of states near T=O 98 7. Application to Ce metal 101 8. Acknowledgements 104 References 104 Mixed Valency in Inorganic Chemistry . . . . . . . . . . . . . . . . . . . . 109 P. Day CONTENTS vi Important Discussion of Part I Intermedi ate Val ency (IV) Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . 111 N. F. Mott Thermal Expansion and Specific Heat of Mixed Valence Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117 R. Pott 1. Introduction 117 2. Experiments and experimental results 117 3. Discussion 120 4. Acknowledgements 122 5."

"The Exploration of Supramolecular Systems and Nanostructures by Photochemical Techniques" provides a comprehensive view of the most commonly used photochemical and photophysical techniques and their applications to the study of supramolecular systems. Optical inputs are extremely powerful in the study of nanostructures since they can be used both to read the state of the system and to provide it energy to work.
After a brief introduction to the realm of photochemistry, electronically excited state formation and the different pathways of excited state deactivation, the book focuses on the theoretical basis and the practical aspects related to the most widely used photophysical and photochemical techniques, from absorption to time-resolved emission techniques with polarized light. Each chapter illustrates an example of the application of that particular technique to the study of a supramolecular system.
"The Exploration of Supramolecular Systems and Nanostructures by Photochemical Techniques" not only discusses the latest advances of the field of supramolecular photochemistry but it also offers technical and operative details useful in the laboratory. It is therefore suitable for both the novice and the expert.

The role of chemistry in materials processing and performance, at high temperatures, is a key area in today's technology. High temperature chemistry-the combination of inorganic chemistry with high temperatures-has undergone dramatic growth within the past 50 years.
The papers in Materials Chemistry at High Temperatures highlight, in two outstanding volumes, the latest information and techniques in this fast-paced field.
Essential reading for anyone involved in this innovative technology!

This book provides an analysis of the reaction mechanisms relevant to a number of processes in which CO2 is converted into valuable products. Several different processes are considered that convert CO2 either in specialty chemicals or in bulk products or fuels. For each reaction, the mechanism is discussed and the assessed steps besides the dark sites of the reaction pathway are highlighted. From the insertion of CO2 into E-X bonds to the reduction of CO2 to CO or other C1 molecules or else to C2 or Cn molecules, the reactions are analysed in order to highlight the known and obscure reaction steps. Besides well known reaction mechanisms and energy profiles, several lesser known situations are discussed. Advancing knowledge of the latter would help to develop efficient routes for the conversion of CO2 into valuable products useful either in the chemical or in the energy industry. The content of this book is quite different from other books reporting the use of CO2. On account of its clear presentation, "Reaction Mechanisms in Carbon Dioxide Conversion" targets in particular researchers, teachers and PhD students.

Mobility Gradient of Polystyrene in Films Supported on Solid Substrates, by Yoshihisa Fujii, Hiroshi Morita, Atsushi Takahara and Keiji Tanaka Probing Properties of Polymers in Thin Films Via Dewetting, by Gunter Reiter Heterogeneous and Aging Dynamics in Single and Stacked Thin Polymer Films, by Koji Fukao, Takehide Terasawa, Kenji Nakamura, Daisuke Tahara Heterogeneous Dynamics of Polymer Thin Films as Studied by Neutron Scattering, by Rintaro Inoue and Toshiji Kanaya

The progress that has recently been made in the field and applications of thermochemistry, having as a consequence an in- crease in the interest of the subject, undoubtedly can be con- sidered highly remarkable. Traditionally, the thermochemist has provided accurate ther- mal data on chemicaZ compounds of practicaZ importance, mainly by calorimetric and by equilibrium studies. The scope has been considerably extended in recent years, following the development of microcalorimetric techniques, of flow calorimetry, of titra- tion calorimetry, and of high temperature calorimetry. The im- pact has been most noticeable in biochemical studies, in metallur- gical studies, and in organometallic and inorganic thermochemis- try. A parallel development has led to increasing output of signi- ficant thermal data on gas-phase transient species (e.g. free ra- dicals, radical ions) by kineticists, and by use of photoioniza- tion spectroscopy, mass spectroscopy and ion-cyclotron resonance spectroscopy. These species are outside the scope of traditional calorimetric study, but as more data on them become available they vastly add to the value of traditional thermochemical data and enable bond energies to be evaluated, and the inter-relation of molecular structure and bonding energy to be more closely exa- mined.

This book defines the current state-of-the-art for predicting the lifetime of plastics exposed to weather and outlines the future research needed to advance this important field of study. Coverage includes progress in developing new science and test methods to determine how materials respond to weather exposure. This book is ideal for researchers and professionals working in the field of service life prediction.

This book also:

Examines numerous consensus standards that affect commercial products allowing readers to see the future of standards related to service life prediction

Provides scientific foundation for latest commercially viable instruments

Presents groundbreaking research including the blueprint of a new test method that will significantly shorten the service life prediction process time

Covers two of the latest verified predictive models, which demonstrate realized-potential to transform the field

Emerging Mass Spectrometric Tools for Analysis of Polymers and Polymer Additives, by Nina Aminlashgari and Minna Hakkarainen. Analysis of Polymer Additives and Impurities by Liquid Chromatography/Mass Spectrometry and Capillary Electrophoresis/Mass Spectrometry, by Wolfgang Buchberger and Martin Stiftinger. Direct Insertion Probe Mass Spectrometry of Polymers, by Jale Hacaloglu Mass Spectrometric Characterization of Oligo- and Polysaccharides and Their Derivatives, by Petra Mischnick. Electrospray Ionization-Mass Spectrometry for Molecular Level Understanding of Polymer Degradation, by Minna Hakkarainen.

This monograph is devoted to different aspects associated with citric acid, inorganic citrates and their aqueous and organic solutions. It includes information about properties, occurrence and technological applications of citric acid and inorganic citrates. Phase equilibria - melting, freezing, boiling, vapour pressures, solubilities of citric acid in water, organic solvents and ternary systems are presented, correlated, and analyzed. Dynamic properties - viscosities, diffusion coefficients, electrical conductivities and surface tensions are examined. Mathematical representations of citric acid dissociation, in electrolyte solutions and in buffers are discussed. Citric acid chemistry - syntheses of citric acid, neutralization, degradation, oxidation, esterification, formation of anhydrides, amides and citrate-based siderophores is reviewed.

The chapters in this book are based upon lectures given at the NATO Advanced Study Institute on Synthetic Membranes (June 26-July 8, 1983, Alcabideche, Portugal), which provided an integrated presentation of syn thetic membrane science and technology in three broad areas. Currently available membrane formation mechanisms are reviewed, as well as the manner in which synthesis conditions can be controlled to achieve desired membrane structures. Membrane performance in a specific separa tionprocess involves complex phenomena, the understanding of which re quires a multidisciplinary approach encompassing polymer chemistry, phys ical chemistry, and chemical engineering. Progress toward a global understanding of membrane phenomena is described in chapters on the principles of membrane transport. The chapters on membrane processes and applications highlight both established and emerging membrane processes, and elucidate their myriad applications. It is our hope that this book will be an enduring, comprehensive compen dium of the state of knowledge in the field of synthetic membranes. We have been encouraged in that hope by numerous expressions of interest in the book, coming from a variety of potential users."

Summarizes current recycling processes, challenges, and perspectives. Offers a comprehensive review of current commercialized LIB recycling companies. Showcases an innovative closed-loop hydrometallurgical recycling process to recycle lithium cathode materials. Provides detailed modelling and economic analysis of several hydrometallurgical recycling processes. Features practical cases and data developed by the authors.

Fisheries genetics researchers will find invaluable the thirty-eight peer-reviewed contributions in this book, presented at the 20th Lowell Wakefield Fisheries Symposium "Genetics of Subpolar Fish and Invertebrates," held in May 2002 in Juneau, Alaska. Looming over concerns of lost fisheries stocks and persistent erosion of genetic variability are predictions of global warming, which may further tax genetic resources. One consequence is an increased reliance on genetic applications to many aspects of fisheries management, aquaculture, and conservation. The contributions in this book are important to modern fisheries science and genetics, and illustrate the evolution of the field over the past decade. The improved technology provides tools to address increasingly complicated problems in traditional applications and ecological and behavioral studies. The union between molecular and quantitative genetics, where many of the major questions about population structure and evolution remain unanswered, will also benefit from the new technologies.

CARGESE INSTITUfE ON DISORDER AND MIXING Convection, diffusion and reaction are the three basic mechanisms in physico-chemical hydrodynamics and chemical engineering. Both convective and diffusive processes are strongly influenced by the effect of disorder of granular matter in porous media, suspensions, fluidized beds or/and by the randomness caused in turbulent flow field. This book has been initiated by a NATO summer institute held in Cargese (Corsica, FRANCE) from June 15 th to 27 th 1987 . Its aim was to associate statistical physicists, fluid mechanicians and specialists of chemical engineering on the problems of the relation between disorder and mixing and, in this respect, this is a " premiere ." This book is made of chapters based on lectures given in the meeting. However we have paid a considerable attention to harmonize the contents and styles of chapters made by scientists trained in different communities and using different languages and techniques to describe similar problems. The Prelude by the editors of the book introduces the different points and is a biased view of some of the important and most active aspects of the subjects developed. We wish to thank all contributors and students of the institute who gave the style of the present interdisciplinary approach. We also greatly thank Elisabeth Charlaix who has shared with us the scientific and practical organisation of the institute, and Marie-France Hanseler for her technical support.

This IMA Volume in Mathematics and its Applications DYNAMICAL ISSUES IN COMBUSTION THEORY is based on the proceedings of a workshop which was an integral part of the 1989-90 IMA program on "Dynamical Systems and their Applications." The aim of this workshop was to cross-fertilize research groups working in topics of current interest in combustion dynamics and mathematical methods applicable thereto. We thank Shui-Nee Chow, Martin Golubitsky, Richard McGehee, George R. Sell, Paul Fife, Amable Liiian and Foreman Williams for organizing the meeting. We especially thank Paul Fife, Amable Liiilin and Foreman Williams for editing the proceedings. We also take this opportunity to thank those agencies whose financial support made the workshop possible: the Army Research Office, the National Science Foundation and the Office of Naval Research. Avner Friedman Willard Miller, Jr. ix PREFACE The world ofcombustion phenomena is rich in problems intriguing to the math ematical scientist. They offer challenges on several fronts: (1) modeling, which involves the elucidation of the essential features of a given phenomenon through physical insight and knowledge of experimental results, (2) devising appropriate asymptotic and computational methods, and (3) developing sound mathematical theories. Papers in the present volume, which are based on talks given at the Workshop on Dynamical Issues in Combustion Theory in November, 1989, describe how all of these challenges have been met for particular examples within a number of common combustion scenarios: reactiveshocks, low Mach number premixed reactive flow, nonpremixed phenomena, and solid propellants."

Many books cover the determination of rate constants under different experimental conditions and different chemical composition of the reaction mixture in their formal treatment of thermal kinetics. However, most textbooks are limited to simple mechanisms. In contrast, analogous treatment of photochemical reactions is limited to the publication of special reactions and investigations. Therefore, this book is aimed at providing an overall description of formal photokinetics covering a wider scope than the usual books on kinetics.

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.

The book discusses the present strategies towards antioxidant capacity evaluation including optical, chromatography, electrochemical methods as well as photoelectrochemical technique, where the advantages, limitations and different applications are analyzed and compared. Subsequently, the corresponding analysis instruments are introduced and interpreted combining with their technical characteristics, scope and performance indicators.

Besides its obvious destructive potential, military R&D also serves to protect human lives, equipment and facilities against the effects of weapons. Concepts have therefore been developed that improve safety of stationary and mobile facilities against pressure waves, thermal radiation and fire. Effective, fast fire extinguishing equipment has been designed for tank compartments and motors. Closed buildings are demolished and landmines are removed with gas and dust explosions. Stringent safety requirements have been developed for the production of ammunition and explosives. Military and related industries have accumulated a vast knowledge and sophisticated experience that are very valuable in a variety of civil applications. The knowledge is based on theoretical and experimental research work, the origin of which sometimes dates back many centuries. It has often been classified and therefore has remained unknown to the civilian population, until now.

Light scattering is a very powerful method to characterize the structure of polymers and nanoparticles in solution. Recent technical developments have strongly enhanced the possible applications of this technique, overcoming previous limitations like sample turbidity or insufficient experimental time scales. However, despite their importance, these new developments have not yet been presented in a comprehensive form. In addition, and maybe even more important to the broad audience, there lacks a simple-to-read textbook for students and non-experts interested in the basic principles and fundamental techniques of light scattering. As part of the Springer Laboratory series, this book tries not only to provide such a simple-to-read and illustrative textbook about the seemingly very complicated topic of light scattering from polymers and nanoparticles in dilute solution, but also intends to cover some of the newest technical developments in experimental light scattering.

The current state of the art of several aspects of minerals and petroleum is presented in this volume. It documents the proceedings of the Internationl symposium on Particle Technology and Surface Phenomena in Minerals and Petroleum sponsored by the Fine Particle Society (FPS). This meeting was held in San Diego, California, August 21-25, 1990. The symposium upon which this volume is based was organized in five sessions emphasizing various basic and applied aspects of research on minerals and petroleum technology. Major topics discussed involve surface phenomena in minerals, mineral flotation, characterization of aspaltenes, theoretical aspects of reservoir simulation, porosity, permeability, residual water saturation, hydrocarbon and gas potential in north slope Alaska, polymer/alkaline flooding, surfactant flooding and foam flooding for enhanced oil recovery. This edition includes eighteen selected papers presented in the symposium. These papers are divided in four broad categories: (1) Asphaltene Aggregation and Characterization, (2) Theoretical Aspects and Reservoir Characterization, (3) Colloidal Dispersions in Minerals/Petroleum, and (4) Surface Phenomena and Petroleum Recovery. Several mineral and oil recovery processes using various chemicals with special reference to surface phenomena and particle technology are described in these sections.

Keeping up with the advances in modern heterocyclic chemistry is essential for many of our colleagues in academia and industry. It is the aim of this series on "Stereoselective Heterocyclic Synthesis" to assist the chemical community in this respect by presenting a selection of exciting recent developments. As it was for the first two volumes (1997), the stereoselective synthesis of - or with the aid of - heterocycles is the common motif for all the chapters in this third volume. I am very glad that again leading researchers in this area have contrib- ed highly stimulating accounts with up-to-date coverage. "Stereoselective Heterocyclic Synthesis 111" features chapters on "Stereoselective Intramolecular J,3-Dipolar Cycloadditions" by I. N. N. Nambothiiri and A. Hassner giving an in depth survey of the generation and synthetic application of valuable 1,3-dipoles,"4-Acetoxy- and 4-Cyano-12-dioxanes in Synthesis" by C. J. Sinz and S. D. Rychnovsky presenting a comprehensive summary of the utility of the versatile title compounds in natural products synthesis,"The Synthetic Potential of Three-Membered Ring Aza-Heterocycles" by B. Zwanenburg and l? ten Holte highlighting the fascinating chemistry of aziridine and azirine carboxylic esters, and '(Synthesis of Medium-Sized Ring Lactams" by U. Nubbemeyer discussing a wide range of modern strategies for the stereoselective preparation of these important heterocycles. I wish to express my thanks to all contributors for their dedicated effort and to Mrs. Kollmar-Thoni, Springer-Verlag, for her continuous support. Dresden, March 2001 Peter Metz Contents Stereoselective Intramolecular 1. 3. Dipolar Cycloadditions I. N. N. Namboothiri. A . Hassner . . . . . . . . . . . . . . . . . . . . . . .

This volume chronicles the proceedings of the Third Symposium on Particles on Surfaces : Detection, Adhesion and Removal held as a part of the 21st Annual Meeting of the Fine Particle Society in San Diego , California, August 21 - 25 , 1990 . The first two symposia i n t h i s series were held in 1986 and 1988 , respectively, and have been properly l documented ,2. Li ke its antecedent s the Third symposium was very well received, and the continuing success of these symposia reinforced our earlier belief that regular symposia on the topic of particles on surfaces were very much needed. Concomitantly, the fourth symposium in this series is planned in Las Vegas , July 13-17 , 199 2 . l As pointed out in the Preface to the earlier two volumes ,2, the topic of particles on surfaces is of tremendous interest and concern in a wide spectrum of technological areas . The objectives of the Third symposium were es s ent i a l ly the same as those of the earlier two and our intent her e was to provide an update on the research and development activities in the world of particles on surfaces . Apropos , there has been a deliberate attempt every time to s eek out new people to present their research results and we have been very succes s f ul in this mission.

This book is an introduction to the dynamics of reaction-diffusion systems, with a focus on fronts and stationary spatial patterns. Emphasis is on systems that are non-standard in the sense that either the transport is not simply classical diffusion (Brownian motion) or the system is not homogeneous. A important feature is the derivation of the basic phenomenological equations from the mesoscopic system properties. Topics addressed include transport with inertia, described by persistent random walks and hyperbolic reaction-transport equations and transport by anomalous diffusion, in particular subdiffusion, where the mean square displacement grows sublinearly with time. In particular reaction-diffusion systems are studied where the medium is in turn either spatially inhomogeneous, compositionally heterogeneous or spatially discrete. Applications span a vast range of interdisciplinary fields and the systems considered can be as different as human or animal groups migrating under external influences, population ecology and evolution, complex chemical reactions, or networks of biological cells. Several chapters treat these applications in detail.

This book highlights recent advances in and diverse techniques for exploring the plasma membrane's structure and function. It starts with two chapters reviewing the history of membrane research and listing recent advances regarding membrane structure, such as the semi-mosaic model for red blood cell membranes and the protein layer-lipid-protein island model for nucleated tissue cell membranes. It subsequently focuses on the localization and interactions of membrane components, dynamic processes of membrane transport and transmembrane signal transduction. Classic and cutting-edge techniques (e.g. high-resolution atomic force microscopy and super-resolution fluorescence microscopy) used in biophysics and chemistry are presented in a very comprehensive manner, making them useful and accessible to both researchers in the field and novices studying cell membranes. This book provides readers a deeper understanding of the plasma membrane's organization at the single molecule level and opens a new way to reveal the relationship between the membrane's structure and functions, making it essential reading for researchers in various fields.

The rapidly-developing field of confined polymers is reviewed in this volume. Special emphasis is given to polymer aspects of this interdisciplinary problem. Taken together, the contributions offer ample evidence of how the field of polymer science continues to evolve with the passage of time. The topics revolve around the tendency of surfaces to impede chain relaxation and to stimulate new sorts of chain organization. These have been implicated in a variety of spectacular phenomena. Here is a listing of authors and affiliations: K. Binder (Johannes Gutenberg-Universit t Mainz, Germany); P.-G. de Gennes (College de France, France); E.P. Giannelis, R. Krishnamoorti, and E. Manias (Cornell University and University of Houston, USA); G.S. Grest (Exxon Research and Engineering Co., USA); L. Leger, E. Raphael, and H. Hervet (College de France, France); S.-Q. Wang (Case Western Reserve University, USA).