Stability constants are fundamental to understanding the behavior of metal ions in aqueous solution. Such understanding is important in a wide variety of areas, such as metal ions in biology, biomedical applications, metal ions in the environment, extraction metallurgy, food chemistry, and metal ions in many industrial processes. In spite of this importance, it appears that many inorganic chemists have lost an appreciation for the importance of stability constants, and the thermodynamic aspects of complex formation, with attention focused over the last thirty years on newer areas, such as organometallic chemistry. This book is an attempt to show the richness of chemistry that can be revealed by stability constants, when measured as part of an overall strategy aimed at understanding the complexing properties of a particular ligand or metal ion. Thus, for example, there are numerous crystal structures of the Li+ ion with crown ethers. What do these indicate to us about the chemistry of Li+ with crown ethers? In fact, most of these crystal structures are in a sense misleading, in that the Li+ ion forms no complexes, or at best very weak complexes, with familiar crown ethers such as l2-crown-4, in any known solvent. Thus, without the stability constants, our understanding of the chemistry of a metal ion with any particular ligand must be regarded as incomplete. In this book we attempt to show how stability constants can reveal factors in ligand design which could not readily be deduced from any other physical technique.

Asphaltenes have traditionally been viewed as being extremely complex, thus very hard to characterize. In addition, certain fundamental properties of asphaltenes have pre viously been inaccessible to study by traditional macroscopic methods, further limiting understanding of asphaltenes. These limitations inhibited development of descriptions regarding the microscopic structure and solution dynamics of asphaltenes. However, a variety ofmore recent studies have implied that asphaltenes share many chemical properties with the smaller, more tractable components of crude oils. Recent measurements have indicated that asphaltene molecular weights are not as arge as previously thought, perhaps in the range of 600 to I 000 amu. In addition, new experimental methods applied to asphaltene chemical structures have been quite revealing, yielding a broad understanding. Conse quently, the ability to relate chemical structure with physical and chemical properties can be developed and extended to the understanding of important commercial properties of asphal tenes. This book treats significant new developments in the fundamentals and applications of asphaltenes. In the first section ofthe book, new experimental methods are described that characterize asphaltene structures from the molecular to colloidallength scale. The colloidal properties are understandable in terms of asphaltene chemical structures, especially with regard to the heteroatom impact on bonding. However, quantitative measurements of the of asphaltene self-association still need to be determined. In the second section of enthalpy this book, the fundamental understanding of asphaltenes is related riirectly to asphaltene utilization."

Mechanisms of Inorganic and Organometallic Reactions provides an ongoing critical review of the primary literature concerned with mechanisms of inorganic and organometallic reactions. The main focus is on reactions in solution, although solid-state and gas-phase studies are included where they provide relevant mechanistic insight. Each volume covers an eighteen-month literature period, and this, the eighth volume in the series, includes papers published during January 1990 through June 1991. Where appropriate, references to earlier reports and to specific sections in previous volumes are given. Coverage spans the whole area as comprehensively as possible in each volume, and while it is impossible to be absolutely exhaustive, every effort is made to include all of the important published work that is relevant to the elucidation of reaction mechanisms. Numerical data are reported in the units used by the original authors, and they are converted to common units only when comparisons are being made. The successful format of earlier volumes is retained to facilitate tracing progress over several years in a particular topic, and the series now permits this to be done for a twelve-year period. The introduction three volumes ago of computerized techniques to improve cross-referencing in the Index brought positive reader comments, and their use is being continued.

Mass spectrometry underwent dramatic changes during the decade of the 1980s. Fast atom bombardment (F AB) ionization, developed by Barber and coworkers, made it possible for all mass spectrometry laboratories to analyze polar, highly functionalized organic molecules, and in some cases ionic, inorganic, and organometallic compounds. The emphasis of much of this work was on molecular weight determination. Parallel with the development of ionization methods (molecular weight mass spectrometry) for polar biological molecules, the increased mass range of sector and quadrupole mass spectrometers and the development of new instruments for tandem mass spectrometry fostered a new era in structural mass spectrometry. It was during this same period that new instrument technologies, such as Fourier transform ion cyclotron resonance, radio frequency quadrupole ion trap, and new types of time-of-flight mass spectrometers, began to emerge as useful analytical instruments. In addi tion, laser methods useful for both sample ionization and activation became commonplace in almost every analytical mass spectrometry laboratory. In the last 5 years, there has been explosive growth in the area of biological mass spectrometry. Such ionization methods as electrospray and matrix-assisted laser desorption ionization (MALDI) have opened new frontiers for both molecular weight and structural mass spectrometry, with mass spectrometry being used for analysis at the picomole and even femto mole levels. In ideal cases, subfemtomole sample levels can be successfully analyzed. Sample-handling methods are now the limiting factor in analyz ing trace amounts of biological samples.

During the past few decades, much research has been reported on the formation of insoluble monomolecular films of lipids and biopolymers (synthetic polymers and proteins) on the surface of water or at the oil-water interface. This interest arises from the fact that monomolecular film studies have been found to provide much useful information on a molecular scale, information that is useful for understanding many industrial and biological phenomena in chemical, agricultural, pharmaceutical, medical, and food science applications. For instance, information obtained from lipid monolayer studies has been useful in determining the forces that are known to stabilize emulsions and biological cell membranes. The current texts on surface chemistry generally devote a single chapter to the characteristics of spread monolayers of lipids and biopolymers on liquids, and a researcher may have to review several hundred references to determine the procedures needed to investigate or analyze a particular phenomenon. Furthermore, there is an urgent need at this stage for a text that discusses the state of the art regarding the surface pheqomena exhibited by lipids and biopolymers, as they are relevant to a wide variety of surface and interfacial processes.

J.P. Dahl: Carl Johan Ballhausen (1926-2010).- J.R. Winkler and H.B. Gray: Electronic Structures of Oxo-Metal Ions.- C.D. Flint: Early Days in Kemisk Laboratorium IV and Later Studies.- J.H. Palmer: Transition Metal Corrole Coordination Chemistry. A Review Focusing on Electronic Structural Studies.- W.C. Trogler: Chemical Sensing with Semiconducting Metal Phthalocyanines.- K.M. Lancaster: Biological Outer-Sphere Coordination.- R.K. Hocking and E.I. Solomon: Ligand Field and Molecular Orbital Theories of Transition Metal X-ray Absorption Edge Transitions.- K.B. Moller and N.E. Henriksen: Time-resolved X-ray diffraction: The dynamics of the chemical bond.

Zaozao Qiu shows in this thesis that transition metals can mediate or catalyze the cycloaddition or coupling reactions of carboryne with alkynes or alkenes to afford benzocarboranes, alkenylcarboranes or dihydrobenzocarboranes. These results represent powerful strategies to assemble useful complex molecules from very simple precursors in a single operation. Carboranes have many applications in medicine. However, their unique structures make derivatization difficult and the limited efficient synthetic methods to obtain functional carborane materials have restricted applications of carboranes within a narrow scope. This work breaks a new ground in metal-carboryne chemistry and will have a significant impact on synthetic, cluster and materials chemistry.

Focusing on practical applications, the author provides a balanced introduction to the many possible technological uses of metal complexes. Coverage includes the transition metals, lanthanide and actinide complexes, metal porphyrins, and many other complexes. This volume meets the needs of students and scientists in inorganic chemistry, chemical physics, and solid-state physics.

The phenomenon of catalysis is found in many homogeneous and heterogeneous systems undergoing chemical change, where it effects the rates of approach to the equilibrium state in processes as diverse as those found in the stars, the earth's mantle, living organisms, and the various chemistries utilized by industry. The economies and the living standards of both developed and developing countries depend to varying degrees upon the efficacy of their chemical industries. Con sequently, this century has seen a wide exploration and expansion of catalytic chemistry together with an intensive investigation of specific, essential processes like those contributing to life-supporting agricultures. Prime among the latter must surely be the "fixation" of atmospheric nitrogen by catalytic hydrogenation to anhydrous ammonia, still the preferred synthetic precursor of the nitrogenous components of fertilizers. In each decade contemporary concepts and techniques have been used to further the understanding, as yet incomplete, of the catalyst, the adsorbates, the surface reactions, and the technology of large-scale operation. The contributors to the present volume review the state of the art, the science, and the technology; they reveal existing lacunae, and suggest ways forward. Around the turn of the century, Sabatier's school was extending the descriptive catalytic chemistry of hydrogenation by metals to include almost all types of multiple bond. The triple bond of dinitrogen, which continued to be more resistant than the somewhat similar bonds in carbon monoxide and ethyne, defied their efforts.

The physical properties of water and steam have been the subject of lhorough investigation for a long time. It can, on the one hand, be due to the important role of this substance in the processes that take place in nature and, on the .other hand, due to its wide industrial use. Steam is the most important working substance used in conventional and nuc lear power plants, in chemical engineering and other fields of industry. The variety of practical use of water and steam generates a need for knowing their thermodynamic, transport, electrical, and other properties over a .very wide range of temperatures and pressures. International Conferences on the Properties of Steam, which have taken place since 1929, have the aim to promote wide exchange of the results of theoretical and experimental studies into the properties of ordinary and heavy water in a11 phase states. In the course of last decade f.he investigation oC physical and chemical properties of concentrated and dilute aqueous solutions that are of interest in the first place from the point of view of power play an important part in these studies."

Lead-based paint has become a national issue and will continue to be a hi- priority focus ofnational, state, and local agencies until there is no lead-based paint in the United States. Lead-based paint has become a tremendous health hazard for people and animals. Lead-based paint has been in widespread use throughout Europe and the United States. Lead has been known to be a health hazard since the time ofPliny the Elder (A. D. 23-79), but it was deemed that the advantages of lead in paint outweighed the health hazards. There has been a change in outlook, and in 1973 the U. S. Congress banned all lead paint from residential structures. A voluminous number of law suits have been initiated since, and continue to be litigated with the purpose of determining the parties responsible for the lead poisoning of children and others and to exact the indemnities. Lead-based paint is still authorized for use on bridges and nonresidential structures, and thousands of city, state, military, and federal government housing projects still contain lead-based paint. This paint must be removed if these dwellings are to be safe living quarters, especially for children. Aba- ment techniques continue to be evaluated; some have been used successfully. Lead-based paint abatement will continue into the next century, and it is hoped that this comprehensive volume will serve as a guide for those seriously interested in this important subject.

aiThis book starts with depiction of the phosphorus role in life creation and evolution. Then it outlines in which vital processes different phosphates participate in life of all flora and fauna, from DNA molecules till body tissues. Crucial function of phosphates was noticed long ago, but only in XIX century discovery of mineral fertilizers made it possible to sustain the needs of growing global population, thus initiating a green revolution. Though, for many decades after it, the complexity of interactions fertilizer-soil-plant roots was underrated, causing massive damages, such as soil destruction and eutrophication of waters. Still, mining of exhausting natural phosphate reserves continued worldwide. Lessons of what happened in XIX century due to scarcity of phosphates were ignored. In the meantime, production of phosphates reached its peak few years ago. Immediate implementation of phosphate recycling technologies from municipal wastes can help avoid imminent global disaster.ai

I. G OLOGY OF CALCIUM CARBO ATE 1 by Jacques Geyssant 1. Features and characteristics of calcium carbonate 2 1. 1 Calcium carbonate - a special compound 2 1. 2 The crystal forms of calcium carbonate - mineralogy 9 2. The limestones - development and classification 15 2. 1 Sedimentation 16 2. 2 Diagenesis - from sediment to rock 23 2. 3 Classification of the limestones 24 2. 4 Metamorphism - from limestone to marble 26 2. 5 Carbonatites - extraordinary limestones 29 3. Limestone deposits 31 3. 1 Recognition of limestones 31 3. 2 Distribution on the Earth's surface 33 3. 3 Limestone deposits in the geological ages 36 3. 4 CaC0 cycle 42 3 3. 5 Industrially exploitable CaC0 deposits 3 44 53 II. TH C LT RAt HI TORY F LIME TONE by Johannes Rohleder 1. The history of chalk 55 2. Marble and limestone 69 2. 1 Quarrying stones 70 2. 2 Transport, organisation and trade 80 2. 3 The uses 97 137 III. CALCI M CARBOl\ATE - A MODER RESOURCE 1. The beginnings: Calcium carbonate in glazing putty and rubber 138 by Johannes Rohleder 1. 1 A chalk industry is born 139 1. 2 Rubber and glazing putty 142 1. 3 From chalk to calcium carbonate 156 2. Calcium carbonate - pigment and filler 160 by Eberhard Huwald 2. 1 Properties and effects of a filler 164 2. 2 Chalk, limestone, marble, pec - common features and differences 165 2. 2.

Metal-Oxygen Clusters is the first book, providing an overview of the surface chemistry and catalytic properties of heteropoly oxometalates. After a brief look at the early knowledge of heteropoly oxometalates, the book discusses the synthesis, characterization, structure, bulk properties and stability of these materials. The remainder and the largest portion of the book explores the properties of these solids as catalysts in acid-catalyzed and oxidation processes in supported or unsupported forms. The book provides an up-to-date review of the methods for synthesizing heteropoly oxometalates of Keggin structure, techniques from spectroscopic through electrochemical to elemental analysis for their characterization and the current information on their structure, bulk properties and their stabilities at high temperatures and under acid and alkaline conditions. The book discusses the materials employed as supports for the title solid and the results of the examination of the supported materials. Methods for the identification of the nature and source of the two catalytic functions, the acidic and oxidative properties, of the heteropoly oxometalates are reviewed and discussed. The use of both the supported and unsupported heteropoly oxometalates as catalysts in acidity-requisite processes ranging from methanol conversion to hydrocarbons to ring-expansion and contraction processes and in oxidation processes from methane cyclohexane are described and related to the aforementioned properties.

To the biochemist, water is, of course, the only solvent worthy of consideration, because natural macromolecules exhibit their remarkable conformational properties only in aqueous media. Probably because of these remarkable properties, biochemists do not tend to regard proteins, nucleotides and polysaccharides as polymers in the way that real polymer scientists regard methyl methacrylate and polyethylene. The laws of polymer statistics hardly apply to native biopolymers. Between these two powerful camps, lies the No-man's land of water soluble synthetic polymers: here, we must also include natural polymers which have been chemically modified. The scientific literature of these compounds is characterized by a large number of patents, which is usually a sign of little basic understanding, of 'know-how' rather than of 'know-why'. Many of the physical properties of such aqueous solutions are intriguing: the polymer may be completely miscible with water, and yet water is a 'poor' solvent, in terms of polymer parlance. ~kiny of the polymers form thermorever sible gels on heating or cooling. The phenomena of exothermic mixing and salting-in are common features of such systems: neither can be fully explained by the available theories. Finally, the eccentric behaviour of polyelectrolytes is well documented. Despite the lack of a sound physico-chemical foundation there is a general awareness of the importance of water soluble vinyl, acrylic, polyether, starch and cellulose derivatives, as witnessed again by ~he vast patent literature.

The field of transition metal catalysis has experienced incredible growth during the past decade. The reasons for this are obvious when one considers the world's energy problems and the need for new and less energy demanding syntheses of important chemicals. Heterogeneous catalysis has played a major industrial role; however, such reactions are generally not selective and are exceedingly difficult to study. Homogeneous catalysis suffers from on-site engineering difficulties; however, such reactions usually provide the desired selectivity. For example, Monsanto's synthesis of optically-active amino acids employs a chiral homogeneous rhodium diphosphine catalyst. Industrial uses of homogeneous catalyst systems are increasing. It is not by accident that many homogeneous catalysts contain tertiary phosphine ligands. These ligands possess the correct steric and electronic properties that are necessary for catalytic reactivity and selectivity. This point will be emphasized throughout the book. Thus the stage is set for a comprehensive be treatment of the many ways in which phosphine catalyst systems can designed, synthesized, and studied."

In this reference, the author thoroughly reviews the current state of condensed phosphate chemistry. A unique feature of this volume is an examination of the recent developments in X-ray structural techniques, reporting on fundamental results obtained through their use. Enhanced by comprehensive tables reporting crystal data, chapters identify and characterize more than 2,000 compounds. Additional features include a concise survey of the historical development of condensed phosphate chemistry; the presently accepted classification system; a review of each family of condensed phosphates and much more.

The purpose of this volume is to present the latest planetary studies of an international body of scientists concerned with the physical and chemical aspects of terrestrial planets. In recent years planetary science has developed in leaps and bounds. This is a result of the application of a broad range of scientific disciplines, particularly physical and chemical, to an understanding of the information received from manned and unmanned space exploration. The first five chapters expound on many of the past and recent observations in an attempt to develop meaningful physical-chemical models of planetary formation and evolution. For any discussion of the chemical processes in the solar nebula, it is important to understand the boundary conditions of the physical variables. In Chapter 1, Saf ranov and Vitjazev have laid down explicitly all the physical constraints and the problems of time-dependence of nebular evolutionary processes. Planetary scientists and students will find in this chapter a collection of astrophysical parameters on the transfer of angular momentum, formation of the disk and the gas envelope, nebular turbulence, physical mixing of particles of various origins and growth of planetesimals. The authors conclude their work with important information on ev olution of terrestrial planets. Although symbols are defined in the text of the article, readers who are not familiar with the many symbols and abbreviations in astrophysical literature will find it useful to consult the Appendix for explanations."

As nanomaterials and their end products occupy the pinnacle position of consumer markets, it becomes vital to analyze their generation processes. One of the green chemistry principles underlines the need for unusual energy sources to generate them. Utilizing the extreme energy from the collapse of cavitation bubbles, generated by either ultrasound or hydrodynamic forces, for the generation of nanomaterials is a merit to consider in this "Green Chemical Processing Era." A wide range of nanomaterials have been developed in the past decade using cavitation or coupling cavitation with other techniques such as microwave, photochemistry, and electrochemistry, resulting in nanomaterials with unique morphologies, reduced size, narrow size distribution, and innumerous advantages. While a few currently available books deal with the fundamental aspects of cavitation and sonochemistry, this book is devoted specifically to the technologically important nanomaterials obtained by cavitation.

The commercial availability and decreasing cost of polyhedral oligomeric silsesquioxanes in recent years has opened up the field to everybody who wishes to apply these unique properties in their own technologies. This is the first book to provide a comprehensive overview of these applications, and covers the synthesis, characterization and history of polyhedral oligomeric silsesquioxanes, their use as metallasilsesquioxane catalysts, their effect upon polymer properties and plastics performance, and their use in superhydrophobic nanocomposites, and electronics, energy, space and biomedical applications.

"Applications of Polyhedral Oligomeric Silsesquioxanes" is a valuable reference for those working across a range of disciplines, including chemists, materials scientists, polymer physicists, plastics engineers, surface scientists, and anybody with a commercial or academic interest in plastics, composite materials, space materials, dental materials, tissue engineering, drug delivery, lithography, fuel cells, batteries, lubricants, or liquid crystal, LED, sensor, photovoltaic or biomedical devices.

The aim of this compilation has been to provide a comprehensive, non-criti cal source of information concerning organometallic compounds. The scope is limited to the compounds containing at least one carbon-metal bond. The in formation includes methods of preparation, properties, chemical reactions, and applications. The First Edition comprised the literature from 1937 to 1958. The Second Edition is completely revised and extended through 1964. The literature prior to 1937 was thoroughly covered by E. Krause and A. von Grosse in I~ie Chemie der meta11-organischen Verbindungen, " Verlag von Gebrueder Borntraeger, Berlin, 1937. Our work consists of three volumes. Volume I contains derivatives of the transition metals of Groups III through VIII of the Periodic Table. Volume II contains derivatives of germanium, tin, and lead. Volume III contains derivatives of arsenic, antimony, and bismuth. The compilation is based on searches through Chemical Abstracts. The col lection of references for 1964 was completed before the Subject Indexes to Volumes 60 and 61 of the Abstracts were available; thus some omissions in the coverage of that year are possible. We have attempted to make the coverage of the literature complete in order that the compilation may have best utility to the chemist, chemical engineer, patent attorney, and editor. In the interest of brevity, certain numerical data are omitted, but references to the original literature are given. Yield data are rounded to two significant figures. Wherever possible, tables have been used. The entries in the Bibliography section include references to Chemical Abstracts.

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'.

In the short time since the first nitroxyl radical was obtained in 1959, a new branch of chemical science has arisen and taken shape-the chemistry of stable nitroxyl radicals. The present book was written by E. G. Rozantsev, one of the pioneers in this field and a prominent specialist on stable radicals at the Division of Chemical and Biological Processes of the Institute of Chemical Physics, Academy of Sciences of the USSR. His numerous papers have contributed greatly to the present situation, wherein nitroxyl radicals have acquired unusually wide popularity, including the fields of biology, medicine, chemis try, physics, biophysics, and instrument construction. A clear illustration of the astonishingly vigorous development of this new field of chemistry can be given by the enormous flow of information on the synthesis and use of nitroxyl radicals. There is no doubt that this monograph, which in part generalizes the results of many workers studying these radicals, will be received with interest by specialists working in this field. The author has not attempted to give an exhaustive account of the material. His aim is to introduce the reader to this new field and to show the wide possibilities for using radicals in scientific experiment. The voluminous bibliography, including many papers by the author himself which may not be well enough known to the American reader, will undoubtedly contribute to the usefulness of the monograph."

Environmental Chemistry is a relatively young science. Interest in this subject, however, is growing very rapidly and, although no agreement has been reached as yet about the exact content and limits of this interdisciplinary subject, there appears to be increasing interest in seeing environmental topics which are based on chemistry embodied in this subject. One of the first objectives of Environ mental Chemistry must be the study of the environment and of natural chemical processes which occur in the environment. A major purpose of this series on Environmental Chemistry, therefore, is to present a reasonably uniform view of various aspects of the chemistry of the environment and chemical reactions occuring in the environment. The industrial activities of man have given a new dimension to Environ mental Chemistry. We have now synthesized and described over five million chemical compounds and chemical industry produces about one hundred and fifty million tons of synthetic chemicals annually. We ship billions of tons of oil per year and through mining operations and other geophysical modifications, large quantities of inorganic and organic materials are released from their natural deposits. Cities and metropolitan areas of up to 15 million inhabitants produce large quantities ofwaste in relatively small and confined areas. Much of the chemical products and was te products of modern society are released into the environment either during production, storage, transport, use or ultimate disposal. These released materials participate in natural cycles and reactions and frequently lead to interference and disturbance of natural systems."