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."

These two volumes together comprise forty papers coming from the most outstanding contributions to the third European Quantum Systems in Chemistry and Physics Workshop held in Granada, Spain (1997). These books cover a very broad spectrum of scientific research work from quantum-mechanical many-body methods to important applications and computational developments, and from atoms and molecules to condensed matter. The first volume is subtitled Basic Problems and Model Systems, and includes the following topics: density matrices and density functionals, electron correlation effects, relativistic formulations, valence theory, and nuclear motions. The second volume is subtitled Advanced Problems and Complex Systems and covers the following topics: response theory, condensed matter, reactive collisions and chemical reactions, and computational chemistry and physics.

According to R.H. Crabtree, Metal Dihydrogen and sigma-Bond Complexes is described as the definitive account of twentieth-century work in the area of sigma complexation'. It covers not only Kubas' discovery of dihydrogen coordination and the study of its structure and general properties but also discusses both the theoretical beliefs and experimental results of bonding and activation of dihydrogen on metal centers and the coordination and activation of C-H, B-H, X-H, and X-Y bonds, giving an overview of one of the hottest areas in chemistry'.

With the resurgence of nuclear power around the world, and the increasingly important role of hydrogen as a clean energy carrier, the utilization of nuclear energy for large-scale hydrogen production will have a key role in a sustainable energy future. Co-generation of both electricity and hydrogen from nuclear plants will become increasingly attractive. It enables load leveling together with renewable energy and storage of electricity in the form of hydrogen, when electricity prices and demand are lowest at off-peak hours of nuclear plants, such as overnight.

"Hydrogen Production from Nuclear Energy "provides an overview of the latest developments and methods of nuclear based hydrogen production, including electrolysis and thermochemical cycles. Particular focus is given to thermochemical water splitting by the copper-chlorine and sulphur-based cycles. Cycle configurations, equipment design, modeling and implementation issues are presented and discussed. The book provides the reader with an overview of the key enabling technologies towards the design and industrialization of hydrogen plants that are co-located and linked with nuclear plants in the future.

The book includes illustrations of technology developments, tables that summarize key features and results, overviews of recent advances and new methods of nuclear hydrogen production. The latest results from leading authorities in the fields will be presented, including efficiencies, costs, equipment design, and modeling.

"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.

This long-awaited and thoroughly updated version of the classic text (Plenum Press, 1970) explains the subject of electrochemistry in clear, straightforward language for undergraduates and mature scientists who want to understand solutions. Like its predecessor, the new text presents the electrochemistry of solutions at the molecular level. The Second Edition takes full advantage of the advances in microscopy, computing power, and industrial applications in the quarter century since the publication of the First Edition. Such new techniques include scanning-tunneling microscopy, which enables us to see atoms on electrodes; and new computers capable of molecular dynamics calculations that are used in arriving at experimental values. A description of the electrochemical stage - the high field region near the interface - is the topic of Chapter 6 and involves a complete rewrite of the corresponding chapter in the First Edition, particularly the various happenings which occur with organic molecules which approach surfaces in solution. The chapter on electrode kinetics retains material describing the Butler-Volmer equation from the First Edition, but then turns to many new areas, including electrochemical theories of potential-dependent gas catalysis. Chapter 8 is a new one devoted to explaining how electrochemists deal with the fast-changing nature of the electrode surface. Quantum Mechanics as the basis to electrode kinetics is given an entirely new look - up to and including considerations of bond-breaking reactions.

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 breadth of scientific and technological interests in the general topic of photochemistry is truly enormous and includes, for example, such diverse areas as microelectronics, atmospheric chemistry, organic synthesis, non-conventional photoimaging, photosynthesis, solar energy conversion, polymer technologies, and spectroscopy. This Specialist Periodical Report on Photochemistry aims to provide an annual review of photo-induced processes that have relevance to the above wide-ranging academic and commercial disciplines, and interests in chemistry, physics, biology and technology. In order to provide easy access to this vast and varied literature, each volume of Photochemistry comprises sections concerned with photophysical processes in condensed phases, organic aspects which are sub-divided by chromophore type, polymer photochemistry, and photochemical aspects of solar energy conversion. Volume 34 covers literature published from July 2001 to June 2002. Specialist Periodical Reports provide systematic and detailed review coverage in major areas of chemical research. Compiled by teams of leading authorities in the relevant subject areas, the series creates a unique service for the active research chemist, with regular, in-depth accounts of progress in particular fields of chemistry. Subject coverage within different volumes of a given title is similar and publication is on an annual or biennial basis.

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

The demand for selective organic reactions is growing more acute everyday. Indeed, greater product selectivity has an important impact on energy and resource utilization, in terms of reduced process energy requirements for product separation and purification, in terms of low-value by-products, and in terms of environmental acceptance and compatibility. Moreover, more and more chemicals, especially pharmaceuticals, have to be sold in an optically active form. The search for selectivity constitutes a tremendous challenge for the chemists. In the last two decades, homogeneous transition metal based catalysis has emerged as one of the most promising tools for obtaining selectivity. In connection with developments in this area, this book contains updated and expanded versions of most of the lectures presented at a Cornett course held in Trieste (Italy) in 1989 and sponsored by the European Community. A primary aim is to cultivate a deeper understanding of the parameters that govern the selectivities and stimulate a wider utilization of transition metal based catalysis in organic synthesis. All aspects of selectivity, chemo-, regio-, stereo- and enantioselectivity are considered and illustrated by applications in various fields or organic synthesis. The impact of catalysis in oxydation, reduction, carbonylation reactions, carbene chemistry, in Ni and Pd promoted dimerizations, oligomerizations as well as fonctionalisations is stressed, quite often with special emphasis laid on reaction mechanisms. In this aspect, the last chapter examplifies the interest of high pressure NMR and IR when investigating the nature of reaction intermediates in homogeneous reactions.

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.

This volume contains the papers presented at the Sixth International Ion Exchange Conference organised by the SCI and held at Churchill College, Cambridge, UK, in July 1992. As on previous occasions, most recently in 1988, the organising committee did not engage plenary speakers but decided to solicit state-of-the-art contributions from the ion exchange community. This book contains the refereed papers presented at the meeting, whether in poster or oral form. Extra papers were presented at the meeting as posters because they were not available in time for refereeing purposes. The subject matter of the meeting and therefore the contents of the book is subdivided into seven separate topic areas as follows: resin developments; water treatment; fundamentals; biotechnology, food and pharmaceuticals; environmental and pollution control; membranes, inorganic materials and nuclear; and hydrometallurgy. The coverage of the meeting is similar to 1988 although there are fewer subdivisions on this occasion. The more restricted coverage this time reflects the smaller number of papers offered by authors. This is probably due to the world wide industrial recession which has affected commercial development and exploitation of the technology and restricts the ability of practitioners and academics to contribute to and attend international meetings. Nevertheless, the advances in biotechnology, growing concern about the environment and the. need for novel separation processes have provided sufficient impetus to stimulate a sufficient number of workers in the field.

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."

The Computational Biomechanics for Medicine titles provide an opportunity for specialists in computational biomechanics to present their latest methodologies and advancements. This volume comprises eighteen of the newest approaches and applications of computational biomechanics, from researchers in Australia, New Zealand, USA, UK, Switzerland, Scotland, France and Russia. Some of the interesting topics discussed are: tailored computational models; traumatic brain injury; soft-tissue mechanics; medical image analysis; and clinically-relevant simulations. One of the greatest challenges facing the computational engineering community is to extend the success of computational mechanics to fields outside traditional engineering, in particular to biology, the biomedical sciences, and medicine. We hope the research presented within this book series will contribute to overcoming this grand challenge.

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.

Recognized experts present incisive analysis of both fundamental and applied problems in this continuation of a highly acclaimed series. Topics discussed include: A review of the literature on the potential-of-zero charge by Trasatti and Lust. A thorough review and discussion of nonequilibrium fluctuations in corrosion processes. A wide-ranging discussion of conducting polymers, electrochemistry, and biomimicking processes. Microwave (photo)electrochemistry, from its origins to today's research opportunities, including its relation to electrochemistry. New fluorine cell design, from model development through preliminary engineering modeling, laboratory tests, and pilot plant tests. A comprehensive account of the major and rapidly developing field of the electrochemistry of electronically conducting polymers and their applications. These authoritative studies will be invaluable for researchers in engineering, electrochemistry, analytical chemistry, materials science, physical chemistry, and corrosion science.

"Electrochemical Impedance Spectroscopy in PEM Fuel Cells" discusses one of the most powerful and useful diagnostic tools for various aspects of the study of fuel cells: electrochemical impedance spectroscopy (EIS). This comprehensive reference on EIS fundamentals and applications in fuel cells contains information about basic principles, measurements, and fuel cell applications of the EIS technique. Many illustrated examples are provided to ensure maximum clarity and observability of the spectra. "Electrochemical Impedance Spectroscopy in PEM Fuel Cells" will enable readers to explore the frontiers of EIS technology in PEM fuel cell research and other electrochemical systems. As well as being a useful text for electrochemists, it can also help researchers who are unfamiliar with EIS to learn the technique quickly and to use it correctly in their fuel cell research. Managers or entrepreneurs may also find this book a useful guide to accessing the challenges and opportunities in fuel cell technology.

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.