This is a textbook of what is often called magnetochemistry. We take the point of view that magnetic phenomena are interesting because of what they tell us about chemical systems. Yet, we believe it is no longer tenable to write only about such subjects as distinguishing stereochemistry from the measurement of a magnetic susceptibility over a restricted temper ature region; that is, paramagnetism is so well-understood that little remains to explore which is of fundamental interest. The major purpose of this book is to direct chemists to some of the recent work of physicists, and in particular to a lengthy exposition of magnetic ordering phenomena. Chemists have long been interested in magnetic interactions in clusters, but many have shied away from long-range ordering phenomena. Now however more people are investigating magnetic behavior at temperatures in the liquid helium region, where ordering phenomena can scarcely be avoided. The emphasis is on complexes of the iron-series ions, for this is where most of the recent work, both experimental and theoretical, has been done. The discussion therefore is limited to insulating crystals; the nature of magnetism in metals and such materials as semiconductors is sufficiently different that a discussion of these substances is beyond our purposes. The book is directed more at the practical experimentalist than at the theoretician."

Electrochemical synthesis of inorganic compounds is a relatively unknown field. The successful, large industrial processes, such as chlorine-caustic production, are well known, but the large number of other compounds that have been synthesized electrochemically are much less appreciated, even by electrochemists and inorganic chemists. The last comprehensive book on this subject was published in the 1930's and no modern review or summary of the whole field is in existence. But the field is in no way dormant, as attested by the large number of publications, undiminished throughout the years, describing new syntheses and improvements of old ones. Indeed, it can be expected that practical applications of electrochemical inor ganic syntheses will increase in the future as an increasing portion of our energy will be available in electrical form. Electrochemical processes have important advantages over chemical routes: often the selectivity of the reaction can be better controlled through the use of potential control at the electrode, and the creation of environmen tally harmful waste material can be avoided more easily since one is using the purest reagent - the electron. In addition to development of new synthetic routes, many old ones, which were found to be un economical in the past, are worth reexamining in light of the recent considerable advances in cell design principles, materials of construc tion, and electrode and separator materials, together with our im proved understanding of electrode reactions and electrocatalysis. It is in the hope of accelerating this process that this bibliography is published."

This sourcebook is the detailed review of the chemistry, manufacturing processes, and uses of resorcinol and its derivatives. Citing over 1,900 references, the author clearly explains the chemical s complex development, discussing the many tests, techniques, and instruments used.

Striking a balance between the scientific and technological aspects of radiation curing, this work includes both a summary of current knowledge as well as many chapters which present the first comprehensive accounts of their subjects.

This volume documents the proceedings of the Second Symposium on Metallized Plastics: Fundamental and Applied Aspects held under the aegis of the Dielectric Science and Technology Division of the Electrochemical Society in Montreal, Canada, May 7-10, 1990. The first symposium on this topic was held in Chicago, October 10-12, 1988 and the proceedings of l which have been chronicled in a hard-bound volume l As pointed out in the Preface to the proceedings of the first symposium the metallized plastics find scores of applications ranging from very mundane to very sophisticated. Even a cursory look at the literature will convince that this field has sprouted; and there is every reason to believe that with all the research and development activities taking place, new and exciting applications of metallized plastics will emerge. The program for the second symposium was very comprehensive as it included 46 papers covering many aspects of metallized plastics. This symposium was a testimonial to the brisk research activity and keen interest in the topic of metallized plastics. The success of this symposium reinforced our earlier belief that there was a definite need to hold symposia on this topic on a regular basis. Concomitantly, the third symposium in this vein was held in Phoenix, Arizona, October 13-18, 1991 and the fourth is planned for May 16-21, 1993 in Honolulu, Hawaii. As regards the present volume, it contains a total of 35 papers covering a variety of topics ranging from very fundamental to very applied.

During the course of far-infrared investigations of inorganic and coordina tion compounds at Argonne National Laboratory in the years 1962-1966, it became apparent that no suitable book existed which correlated and dis cussed the important vibrations occurring in this region for these molecules. Early in 1967 the initial steps were taken to write such a book. Then, in 1968, an excellent text by Professor David M. Adams entitled Metal-Ligand and Related Vibrations was published. At this point serious consideration was given to discontinuing work on this book. However, upon examination of Adams' book, it became clear that the references covered only the period to 1966. This field of research is accelerating so tremendously, and the period 1966-1969 has seen so many new studies, that upon reconsideration it was decided to continue writing this text. The references in this book, particularly in the last several chapters, include many papers published in 1969. However, the proliferation of the far-infrared literature has made it impossible to present all the published material that has any bearing on the subject. Many titles do not pertain primarily to the far-infrared region as such, and some of this research has been omitted for this reason. Organometallic compounds have been neglected since the author feels that adequate reviews of that subject are available. Other studies may be missing simply because, owing to space limitations, only the more important researches could be considered. Of course, "importance" may, in this case, reflect the author's interest and prejudices."

This book contains the papers and discussions from the sympo , ium on "The Catalytic Chemistry of Nitrogen Oxides" held at the General Motors Research Laboratories on October 7-8, 1974. This symposium is the eighteenth in the annual series presented by the Research Laboratories. The topics for these symposiums have covered a broad range. Each topic was selected to be of intense current interest and of significant technical importance. There is no question that the subject of the 1974 Symposium satisfies these two criteria. The control of automotive nitrogen oxides has been perhaps the most difficult and controversial area of automotive emissions both in terms of what is necessary and in terms of what is technically feasible. This area has been a source of considerable discussion not only in the technical community but also in governments both in the U. S. and abroad. This meeting brought together scientists working in surface chemistry with engineers working on system design. It also brought together representatives of government, academia and industry. We feel that an important side benefit of the meeting was the improved understanding that was developed between these groups. Participants came from Europe and Japan as well as Canada and the United States. The technical papers spanned the range from fundamental interactions of NO on surfaces through bench scale kinetic and mechanistic studies and ended with catalytic applications. Although the emphasis was on automotive NO removal, stack gas NO x x control was also covered.

It is now some sixteen years since the author's first series of books on the analysis of organometallic compounds. Many developments in the subject have occurred since that time and a new book on the subject is now overdue. The present book aims to provide a comprehensive review of the subject. It covers not only all aspects of the analysis of organometallic compounds but also contains two additional chapters, dealing with environmental analysis and the use of chelates of metals in the determination of very low concentrations of organic metals. Whilst reviewing the literature for the present book, it was observed that whereas papers published prior to 1973 dealt almost exclusively with various forms of analysis, a high proportion of those published during the past ten years were concerned with the application of proven or newly developed methods to the determination of organometallic compounds in environmental samples such as water, air, soil, river and ocean sediments, fish life and biota samples. An increasing range of elements including mercury, lead, arsenic, tin, antimony, selenium and manganese are now being found in organically bound forms in the environment, some resulting from pollution, others formed in nature by bacterial processes. As many of these substances have appreciable implications to human and animal health and the ecosystem as a whole, it was considered that it would be timely to include a separate chapter in the book devoted entirely to this subject.

The three natural streams of present-day chemistry are Structure, Dynamics and Synthesis and all these three elements are essential for the study of materials, particularly in the solid state. The solid state provides challenging opportunities for illustrating and applying principles of chemistry to systems of academic interest and technological importance. There are several practising solid state chemists in universities and research laboratories, but the subject has not yet become part of the formal training program in chemistry. Being one of the new frontiers of chemistry, Solid State Chemistry has a tremendous future and undoubtedly demands the active involvement of many more chemists. A Winter School in Solid State Chemistry was organized at the Indian Institute of Technology, Kanpur, to promote this area and to develop curricular material. Solid State Chemistry being lighly interdisciplinary in nature, the lecturers and participants at the Winter School had widely different backgrounds and interests. It was my great desire that the lecture material from the Winter School should become available to a larger body of students, teachers and research workers interested in the solid state and hence this volume.

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.

Determining the structure of molecules is a fundamental skill that all chemists must learn. "Structural Methods in Molecular Inorganic Chemistry" is designed to help readers interpret experimental data, understand the material published in modern journals of inorganic chemistry, and make decisions about what techniques will be the most useful in solving particular structural problems.

Following a general introduction to the tools and concepts in structural chemistry, the following topics are covered in detail:

- computational chemistry- nuclear magnetic resonance spectroscopy - electron paramagnetic resonance spectroscopy - Mossbauer spectroscopy - rotational spectra and rotational structure - vibrational spectroscopy - electronic characterization techniques- diffraction methods - mass spectrometry

The final chapter presents a series of case histories, illustrating how chemists have applied a broad range of structural techniques to interpret and understand chemical systems.

Throughout the textbook a strong connection is made between theoretical topics and the real world of practicing chemists. Each chapter concludes with problems and discussion questions, and a supporting website contains additional advanced material.

"Structural Methods in Molecular Inorganic Chemistry" is an extensive update and sequel to the successful textbook "Structural Methods in Inorganic Chemistry" by Ebsworth, Rankin and Cradock. It is essential reading for all advanced students of chemistry, and a handy reference source for the professional chemist.

Micro Electro Mechanical Systems (MEMS) is already about a billion dollars a year industry and is growing rapidly. So far major emphasis has been placed on the fabrication processes for various devices. There are serious issues related to tribology, mechanics, surfacechemistry and materials science in the operationand manufacturingof many MEMS devices and these issues are preventing an even faster commercialization. Very little is understood about tribology and mechanical properties on micro- to nanoscales of the materials used in the construction of MEMS devices. The MEMS community needs to be exposed to the state-of-the-artoftribology and vice versa. Fundamental understanding of friction/stiction, wear and the role of surface contamination and environmental debris in micro devices is required. There are significantadhesion, friction and wear issues in manufacturing and actual use, facing the MEMS industry. Very little is understood about the tribology of bulk silicon and polysilicon films used in the construction ofthese microdevices. These issues are based on surface phenomenaand cannotbe scaled down linearly and these become increasingly important with the small size of the devices. Continuum theory breaks down in the analyses, e. g. in fluid flow of micro-scale devices. Mechanical properties ofpolysilicon and other films are not well characterized. Roughness optimization can help in tribological improvements. Monolayers of lubricants and other materials need to be developed for ultra-low friction and near zero wear. Hard coatings and ion implantation techniques hold promise.

For a long time, the properties of transition metal and rare earth compounds have fascinated chemists and physicists from a scientific view-point, and more recently also their enormous potential as new materials has been explored. Applications in different fields have already been realized or are under c- rent investigation, for example, new laser materials, IR to visible upconversion systems, compounds for photolithographic processes, systems involving pho- redox processes for solar energy conversion, new photovoltaic devices, chemical sensors, biosensors, electroluminescent devices (OLEDs) for flat panel display systems, supramolecular devices with wide-range definable photophysical properties, materials for energy harvesting, optical information and storage systems, etc. Metal complexes are also highly important in biology and me- cine. Most of the applications mentioned are directly related to the properties of the electronic ground state and the lower-lying excited states. Metal complexes with organic ligands or organometallic compounds exhibit outstanding features as compared to purely organic molecules. For instance, metal compounds can often be prepared and applied in different oxidation states. Furthermore, various types of low-lying electronic excitations can be induced by a suitable choice of ligands, for example, such as metal-centered transitions (MC, e. g. d-d* tran- tion), ligand-centered (LC, e. g. n-n*), metal-to-ligand-charge transfer (MLCT, e. g. d-7r*), intra-ligand-charge-transfer (ILCT) transitions, etc. In particular, the orbitals involved in the resulting lowest excited states determine the photoph- ical and photochemical properties and thus the specific use of the compoun

This treatise is a compendium of refereed papers based on invited talks presented at the American Chemical Society Symposium on Electrorheological (ER) Materials and Fluids. ER fluids were first investigated 50+ years ago. These fluids, which change rheology when placed in an electric field, were recognized, from the beginning, for allowing an extremely efficient interface between electrical control and mechanical devices. Critical problems, however, existed with the initial fluids, which prevented them from serious consideration for large-scale applications. While over time some of the critical problems have been solved and activity in ER technology has increased, commercial success has remained elusive. A recent Department of Energy report concluded that a primary reason for the failure to commercialize this promising technology is due to a lack in understanding the physics and chemistry of how the materials work. The goal of the symposium was to address the issue of understanding how ER materials work and how they can be used. One of the outcomes of the symposium, which we hope is conveyed in this book, is a feeling that if the mechanism of ER is to be fully understood and improved, expertise from diverse fields must be applied to the problem.

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

This volume contains a series of papers originally presented at the Symposium on Polymer Gels organized and sponsored by the Research Group on Polymer Gels, The Society of Polymer Science of Japan and co-sponsored by the Science and Technology Agency (ST A) and MIT , Japan. The Symposium took place at Tsukuba Science City on 18th and 19th September, 1989. Recognized experts in their fields were invited to speak and there was a strong attendance from government, academic and industrial research centers. The purpose of the Symposium was to review the state of the art and to present and discuss recent progress in the understanding of the behavioral properties of polymer gels and their application to biomedical, environmental and robotic fields. Most of the papers and related discussions concentrated on the swelling behavior of hydrogels and chemomechanical systems, both artificial and naturally occurring, in which external stimuli of a physical or chemical nature control energy transformation or signal transduction. The recent great interest in chemomechanical systems based on polymer gels has stimulated considerable effort towards the development of new sensors and actuators, controllable membrane separation processes, and delivery systems in which the functions of sensing, processing and actuation are all built into the polymeric network device. Artificial chemomechanical systems, through the use of environmentally sensitive polymer gels, are emerging as interesting materials for mimicking basic processes previously only confined to the biological world, and commercially viable applications are also foreseen in the not-too-distant future

The main objective of this book is to systematically describe the basic principles of the most widely used techniques for the analysis of physical, structural, and compositional properties of solids with a spatial resolution of approxi mately 1 ~m or less. Many books and reviews on a wide variety of microanalysis techniques have appeared in recent years, and the purpose of this book is not to replace them. Rather, the motivation for combining the descriptions of various mi croanalysis techniques in one comprehensive volume is the need for a reference source to help identify microanalysis techniques, and their capabilities, for obtaining particular information on solid-state materials. In principle, there are several possible ways to group the various micro analysis techniques. They can be distinguished by the means of excitation, or the emitted species, or whether they are surface or bulk-sensitive techniques, or on the basis of the information obtained. We have chosen to group them according to the means of excitation. Thus, the major parts of the book are: Electron Beam Techniques, Ion Beam Techniques, Photon Beam Techniques, Acoustic Wave Excitation, and Tunneling of Electrons and Scanning Probe Microscopies. We hope that this book will be useful to students (final year undergrad uates and graduates) and researchers, such as physicists, material scientists, electrical engineers, and chemists, working in a wide variety of fields in solid state sciences.

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.

When we see a jumbo jet at the airport, we sometimes wonder how such a huge, heavy plane can fly high in the sky. To the extent that we think in a static way, it is certainly not understandable. In such a manner, dynamics yields behavior quite different from statics. When we want to prepare an iron nitride, for example, one of the most orthodox ways is to put iron in a nitrogen atmosphere under pressures higher than the dissociation pressure of the iron nitride at temperatures sufficiently high to let the nitrogen penetrate into the bulk iron. This is the way thermodynamics tells us to proceed, which requires an elaborate, expensive high-pressure apparatus, sophisticated techniques, and great efforts. However, if we flow ammonia over the iron, even under low pressures, we can easily prepare the nitride-provided the hydrogen pressure is sufficiently low. Since the nitrogen desorption rate is the determining step of the ammonia decomposition on the iron surface, the virtual pressure of nitrogen at the surface can reach an extremely high level (as is generally accepted) because, in such a dynamic system, the driving force of the ammonia decomposition reaction pushes the nitrogen into the bulk iron to form the nitride. Thus, dynamics is an approach considerably different from statics.

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.

Boron has all the best tunes. That may well be the first impression of the Group 13 elements. The chemical literature fosters the impression not only in the primary journals, but also in asteady outflowofbooks focussing more or less closely on boron and its compounds. The same preoccupation with boron is apparent in the coverage received by the Group 13 elements in the comprehensive and regularly updated volume of the Gmelin Handbook. Yet such an imbalance cannot be explained by any inherent lack ofvariety, interest or consequence in the 'heavier elements. Aluminium is the most abundant metal in the earth's crust; in the industrialised world the metal is second only to iron in its usage, and its compounds can justifiably be said to touch our lives daily - to the potential detriment of those and other lives, some would argue. From being chemical curios, gallium and indium have now gained considerably prominence as sources of compound semiconductors like gallium arsenide and indium antimonide. Nor is there any want ofincident in the chemistriesofthe heavier Group 13 elements. In their redox, coordination and structural properties, there is to be found music indeed, notable not always for its harmony but invariably for its richness and variety. Thisbook seeks to redress the balance with a definitive, wide-rangingand up-to-date review of the chemistry of the Group 13 metals aluminium, gallium, indium and thallium.

This series of books, which is published at the rate of about one per year, addresses fundamental problems in materials science. The contents cover a broad range of topics from small clusters of atoms to engineering materials and involve chemistry, physics, and engineering, with length scales ranging from Angstromsup to millimeters. The emphasis is on basic science rather than on applications. Each book focuses on a single area ofcurrent interest and brings together leading experts to give an up-to-date discussion of their work and the work ofothers. Each article contains enough references that the interested reader can accesstherelevant literature. Thanks aregiven to the Center forFundamental Materials Research atMichigan State University forsupportingthis series. M.F. Thorpe, Series Editor E-mail: [email protected] EastLansing, Michigan, September, 1995 PREFACE This book records selected papers given at an interdisciplinary Symposium on Access in Nanoporous Materials held in Lansing, Michigan, on June 7-9, 1995. Broad interest in the synthesis of ordered materials with pore sizes in the 1.0-10 nm range was clearly manifested in the 64 invited and contributed papers presented by workers in the formal fields of chemistry, physics, and engineering. The intent of the symposium was to bring together a small number ofleading researchers within complementary disciplines to share in the diversity of approaches to nanoporous materials synthesis and characterization."

Environmental pollution is one of the main problems to confront humanity, with the heavy metals occupying a leading role among the most pernicious pollutants. The metals cause cancer and other sicknesses. Their cytotoxic, mutagenic and carcinogenic potentials are not fully understood, and any thorough investigation demands the combined efforts of scientists drawn from many different disciplines. But the effects of heavy metals are not all negative: some, like cis-DDP, and some ruthenium and tin complexes, have antitumour activity. The idea underlying the present work is therefore to present a multidisciplinary perspective on heavy metals in the environment, affording a better understanding of their action on human organisms and health, aiming to make them less polluting and more environmentally friendly.

The intrinsic properties of a solid, i. e. , the properties that result from its specific structure, can be largely modified by crystallographic and chem ical defects. The formation of these defects is governed by the heat and mass transfer conditions which prevail on and near a crystal-nutrient in terface during crystallization. Hence, both the growth of highly perfect crystals and the preparation of samples having predetermined defect-induced (extrinsic) properties require a thorough understanding of the reaction and transport mechanisms that govern crystallization from vapors, solutions and melts. Crystal growth, as a science, is therefore mostly concerned with the chemistry and physics of heat and mass transport in these fluid-solid phase transitions. Solid-solid transitions are, at this time, not widely employed for high quality single-crystal production. Transport concepts are largely built upon equilibrium considerations, i. e. , on thermodynamic and phase equilibrium concepts. Hence to supply a "workable" foundation for the succeeding discussions, this text begins in Chapter 2 with a concise treatment of thermodynamics which emphasizes applications to mate rials preparation. After working through this chapter, the reader should feel at ease with often (particularly among physicists) unfamiliar entities such as chemical potentials, fugacities, activities. etc. Special sections on ther mochemical calculations (and their pitfalls) and compilations of thermochemi cal data conclude the second chapter. Crystal growth can be called. in a wide sense, the science and technology of controlling phase transitions that lead to (single crystalline) solids.

Radiationless transitions comprise an important class of physical phenomena occurring in the excited states of molecules. They affect the lifetimes of the ex cited states and govern primary photochemical and photophysical processes. Much effort has been devoted to the understanding of radiationless transi tions. Still, owing to recent advances, the field continues to attract attention. The demand for a book on the theory of these processes naturally arises in at tempting to comprehend a large body of literature, as the famous review article by K. F. Freed and the book by R. Englman do not encompass some issues of current interest. Our intent is to highlight the underlying physical principles and methods in such a way that the book both in its content and its presentation is instruc tive for a wide audience. The basic ideas are treated in simple mathematical terms intelligible to ex perimentalists and to readers unfamiliar with the field. Complicated theoret ical methods are always expounded from first principles, so that a knowledge of quantum mechanics and mathematics at the graduate-student level will enable the reader to easily follow the derivations. Experts will find efficient methods of calculating the transition rates, as well as new applications of quasiclassical methods and fresh treatments of standard problems. Details of measurements are not discussed, and experimental data are only invoked to illustrate the theory."