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Books > Science & Mathematics > Chemistry > Inorganic chemistry
MICHAEL T. POPE AND ACHIM MULLER Department of Chemistry, Georgetown University, Washington, DC 20057-2222, U.S.A.; Department of Chemistry, University of Bielefeld, D-4BOO Bielefeld 1, F.R.G. Polyoxometalates, from their discovery and early development in the final decades of the 19th century to their current significance in disciplines as diverse as chemistry, mathematics, and medicine, continue to display surprisingly novel structures, unexpected reactivities and applications, and to attract increasing attention worldwide. Most of the contributors to the present volume participated in the workshop held at the Center for Interdisciplinary Research at the University of Bielefeld, July 15-17, 1992. The choice of topics illustrates some of the variety of directions and fields in which polyoxometalates can play an important role. Although many of the leading polyoxometalate research groups are represented here, we regret that time constraints, financial limitations, and in some cases difficulties of communication did not allow us to include significant and imp- tant work from other groups outside Europe and North America. In the following we briefly review the current status of the field of po- oxometalates.
This series, Mechanisms of Inorganic and Organometallic Reactions, provides an ongoing critical review of the published literature concerned with the mechanisms of reactions of inorganic and organometallic compounds. Emphasis is on reactions in solution, although solid state and gas phase studies are included where they provide mechanistic insight. The sixth volume deals with papers published during the period January 1987 through June 1988 inclusive, together with some earlier work where it is appropriate to make comparisons. Coverage spans the whole area as comprehensively as practically possible, and the cited references are chosen for their relevance to the elucidation of reaction mechanisms. The now familiar format of earlier volumes has been maintained to facilitate tracing progress in a particular topic over several volumes, but some small changes have been made. Reflecting the a'mount of mechanistic work associated with ligand reactivity, and the growing importance of this area, Chapter 12 has been renamed and enlarged to bring together informa tion on both coordination and organometallic systems involving ligand reactions. Numerical data are usually reported in the units used by the original authors, except when making comparisons and conversion to common units is necessary.
The serious study of the reaction mechanisms of transition metal com plexes began some five decades ago. Work was initiated in the United States and Great Britain; the pioneers ofthat era were, inalphabetical order, F. Basolo, R. E. Connick, 1. O. Edwards, C. S. Garner, G. P.Haight, W. C. E. Higgision, E.1. King, R. G. Pearson, H. Taube, M.1. Tobe, and R. G. Wilkins.A larger community of research scientists then entered the field, many of them stu dents ofthose just mentioned. Interest spread elsewhere as well, principally to Asia, Canada, and Europe. Before long, the results ofindividual studies were being consolidated into models, many of which traced their origins to the better-established field of mechanistic organic chemistry. For a time this sufficed, but major revisions and new assignments of mechanism became necessary for both ligand sub stitution and oxidation-reduction reactions. Mechanistic inorganic chemistry thus took on a shape of its own. This process has brought us to the present time. Interests have expanded both to include new and more complex species (e.g., metalloproteins) and a wealth of new experimental techniques that have developed mechanisms in ever-finer detail. This is the story the author tells, and in so doing he weaves in the identities of the investigators with the story he has to tell. This makes an enjoyable as well as informative reading."
Starting at the dawn of science, History of Industrial Gases traces the development of gas theory from its Aristotelian roots to its modern achievements as a global industry. Dr. Almqvist explores how environmental protection, geographical areas, and the drive for higher purity and efficiency affected development in the nineteenth and twentieth centuries, and how they will influence the future of this rapidly expanding industry. The roles of major contributing companies are also discussed to provide an informative and thought-provoking treatise valuable to anyone who studies or works in this fascinating field.
This is a book on one of the most fascinating and controversial areas in contemporary science of carbon, chemistry, and materials science. It concisely summarizes the state of the art in topical and critical reviews written by professionals in this and related fields.
Only in the past decade, has the scientific and industrial community come to realize the potential utility offered by inorganic and organometallic polymers (lOPs) for a wide variety of applications. This potential is especially important for applications requiring multifunctional polymers, e.g. for smart materials, nanotechnology, biomimetic systems (neural networks), photonics, etc; lOPs with special properties. The breadth of perfor- mance requirements for the individual areas of application is enormous as are the problems pertaining to generating low cost, high performance, processable lOPs. This book represents the third in a series of books we have edited on inorganic and organometallic polymer chemistry (1. Transfonnation of Organometallics into Common and Exotic Materials, NATO ASI Series Vol 141. 2. Inorganic and Organometallic Oligo- mers and Polymers, Kluwer publications). In this series, we have attempted to identify important trends that help to define for the reader; the potential scope of lOP science as well as the problems that must be surmounted to realize this potential. The focus of the work presented in the following chapters is primarily on the relationships between lOPs and solid state materials with special properties, e.g. conducting, magnetic, photonic and structural materials.
of Polymer Chemistry, Inc. of the American Chemical Society held its The Division 15th Biennial Polymer Symposium on the topic, "Advances in New Materials," November 17-21, 1990, at the Pier 66 Resort and Marina in Ft. Lauderdale, Florida. A three and one half day program was presented by recognized leaders in major areas of new polymeric materials. The topics of the Biennial Symposium included new high performance polymers, polymers for electronic applications, electrically conducting polymers, nonlinear optics, new polymer systems, and polymers derived from biological media. These are the subject areas of this volume of "Contemporary Topics in Polymer Science." The intent of the Symposium was to focus on recent advances in polymeric materials. The technical sessions were complemented by an initial poster session which augmented the various technical sessions. A particular highlight of the meeting was the presentation to Professor Michael Szwarc of the 1990 Division of Polymer Chemistry Award by Dr. J. L. Benham, Chairman of the T Aymer Division. During his Award address, Professor Szwarc described how he had become a polymer chemist and later developed "living polymers." Without a doubt, Professor Szwarc has made a profound contribution to the polymer field, which has yielded many new forms of living polymerization."
In the ten years since the scientific rationale for the design, synthesis and application of inorganic and organometallic polymers (IOPs) was first conceptualised, we have witnessed the first tentative exploration of IOPs as precursors to new materials, with efforts focusing on the design and synthesis of novel ceramic precursors. Developing expertise led to precursor studies combined with the characterisation of the transformation processes that occur when IOPs are converted to ceramic materials. Now at maturity, the science presented in this volume reveals the polymer precursor approach to materials synthesis together with examples of processing ceramic shapes for a range of mechanical properties, the development of sophisticated, noninvasive analytical techniques, and IOP design rationales relying on well-defined processing-property relationships. The production of multifunctional IOPs is described, providing ion conductivity, gas sensing, bioactivity, magnetic properties, etc., combined with processability. The existence of well-defined IOPs and the exquisite control that can be exerted on sol-gel systems now provide access to such a variety of mixed organic-organometallic and/or inorganic hybrid systems that their exploitation is likely to develop into an entirely new field of materials chemistry. Future exciting avenues of research are also being opened up with the advent of buckyballs, Met-Cars, dopable preceramics, rigid-rod organometallics, and molecular tinkertoys.
This book presents the proceedings of the Second International Conference on Frontiers of Polymers and Advanced Materials held in Jakarta, Indonesia during January 10-15, 1993. This conference was organized and sponsored by the Indonesian Institute of Sciences (LIPI), the State University of New York (SUNY) at Buffalo, the Agency for Assessment and Application of Technology (BPPT), and the Indonesian Polymer Association. The 244 participants represented a total of 24 countries and a wide variety of academic, industrial and government groups. The inauguration was held in the Royal Palace and was performed by President Soeharto of Indonesia. High level media coverage ensured worldwide recognition. The need for such a conference was emphasized by the fact that polymers have emerged as an important class of materials offering challenging opportunities for both fundamental research and new technological applications. There has been a tremendous growth of interest in the field of polymers, both in academia and in industry, and polymer science offers tremendous opportunities for both fundamental and applied work. This globally represented Second International Conference on Frontiers of Polymers and Advanced Materials was timely, especially given the current heightened enthusiasm for polymers and emerging novel applications.
Distinct scientific communities are usually involved in the three fields of quasi-crystals, of liquid crystals, and of systems having modulated crystalline structures. However, in recent years, there has been a growing feeling that a number of common problems were encountered in the three fields. These comprise the need to recur to "exotic" spaces for describing the type of order of the atomic or molecular configurations of these systems (Euclidian "superspaces" of dimensions greater than 3, or 4-dimensional curved spaces); the recognition that one has to deal with geometrically frustrated systems, and also the occurence of specific excitations (static or dynamic) resulting from the continuous degeneracies of the stable structures considered. In the view of discussing these problems, aNA TO-Advance Research Workshop has assembled in Preveza (Greece), in september 1989,50 experts of the three considered fields (with an equal proportion of theorists and experimentalists). 35 hours of conferences and discussions have led to a more detailed evaluation of the similarities and of the differences in the approaches implemented in the studies of the three types of systems. The papers contained in this NATO-series book provide the substance of this workshop. The reader will find three types of papers. Some very short papers giving the main ideas stated on a subject. Papers comprising 8-10 pages which stick closely to the contents of the talks presented. Longer papers providing more extensively the background and results relative to a given topic. It is worth summarizing the principal outputs of the workshop.
"Nanotechnology" is now very well known as one of the most important key technologies in science and industry. In the field of material science and engineering, nanoparticles should be unit materials, as well as atoms and molecules, to build ceramics, devices, catalysts, and machines, and the "nanoparticle technology" is thus attracting. This novel technology includes various methodologies for nanoparticles: preparation, surface-modification via chemical and/or physical treatments, immobilization and arrangement on supports or substrates, to achieve high performance for luminescence properties in light emitting devices, and high efficiency for catalytic and photocatalytic reactions in chemical synthesis, chemical decomposition, and artificial photosynthesis, etc. It should be needless to say that the preparation of nanoparticles, having precisely controlled particle size, size distribution, chemical composition, and surface properties, is essentially important to realize "true nanoparticle technology". This book, written by Dr. Dibyendu Ganguli and Dr. Munia Ganguli, deals with the preparation methodologies for inorganic nanoparticles using macro- and microemulsions as "microreactor". There are several differences between these two emulsions, in addition to water droplet size: thermodynamic stability, and fusion-redispersion dynamics of the droplets. The properties of the nanoparticles prepared in these emulsion systems are seriously influenced and controlled by the selection of dynamic and static conditions.
Alexander L. Reznichenko and Kai C. Hultzsch: Catalytic -Bond Metathesis Zhichao Zhang, Dongmei Cui, Baoli Wang, Bo Liu, Yi Yang: Polymerization of 1,3-Conjugated Dienes with Lanthanide Precursors Frank T. Edelmann: Homogeneous Catalysis using Lanthanide Amidinates and Guanidinates Tianshu Li, Jelena Jenter, Peter W. Roesky: Rare Earth Metal Post-metallocene Catalysts with Chelating Amido Ligands
Microcluster Physics provides a lucid account of the fundamental physics of all types of microclusters, outlining the dynamics and static properties of this new phase of matter intermediate between a solid and a molecule. Since originally published in 1991, the field of microclusters has experienced surprising developments, which are reviewed in this new edition: The determination of atomic structure, spontaneous alloying, super-shell, fission, fragmentation, evaporation, magnetism, fullerenes, nanotubes, atomic structure of large silicon clusters, superfluidity of a He cluster, water clusters in liquid, electron correlation and optimizsation of the geometry, and scattering.
Maximum Entropy (ME) techniques have found widespread applicability in the reconstruction of incomplete or noisy data. These techniques have been applied in many areas of data analysis including imaging, spectroscopy, and scattering [Gull and Skilling, 1984]. The techniques have proven particularly useful in astronomy [Narayan and Nityanada, 1984]. In many of these applications the goal of the reconstruction is the detection of point objects against a noisy background. In this work we investigate the applicability of ME techniques to data sets which have strong components which are periodic in space or time. The specific interest in our laboratory is High Resolution Electron Micrographs of beam sensitive materials. However, ME techniques are of general interest for all types of data. These data mayor may not have a spatial or temporal character. Figure 1 shows an HREM image of the rigid-rod polymer poly(paraphenylene benzobisoxazole) (PBZO). The 0.55 nm spacings in the image correspond to the lateral close-packing between the extended polymer molecules. Near the center of this crystallite there is evidence for an edge dislocation. In HREM images both the frequency and position of the infonnation is important for a proper interpretation. Therefore, it is necessary to consider how image processing affects the fidelity of this information in both real and Fourier space.
A humoristic view of the physics of soft matter, which nevertheless has a ring of truth to it, is that it is an ill-defined subject which deals with ill-condensed matter by ill-defined methods. Although, since the Nobel prize was awarded to Pierre-Gilles de Gennes, this subject can be no longer shrugged-away as "sludge physics" by the physics community, it is still not viewed universally as "main stream" physics. While, at first glance, this may be considered as another example of inertia, a case of the "establishment" against the "newcomer", the roots of this prejudice are much deeper and can be traced back to Roger Bacon's conception about the objectivity of science. All of us would agree with the weaker form of this idea which simply says that the final results of our work should be phrased in an observer-independent way and be communicable to anybody who made the effort to learn this language. There exists, however, a stronger form of this idea according to which the above criteria of "objectivity" and "communicability" apply also to the process of scientific inquiry. The fact that major progress in the physics of soft matter was made in apparent violation of this approach, by applying intuition to problems which appeared to defy rigorous analysis, may explain why many physicists feel somewhat ill-at-ease with this subject.
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.
Homogeneous catalysis plays an important role both in the laboratory and in the industry. Successful applications in industry involve new polymerisation processes with complexes of zirconium and related metals, new carbonylation processes employing palladium and rhodium, ring opening polymerisations, and new enantioselective isomerisation catalysts as in the preparation of menthol. Also in the synthesis of organic compounds in the laboratory highly selective homogeneous catalysts represent an irreplaceable part of the toolbox of the synthetic chemist. Examples of such reactions are cross-coupling (Ni, Pd), nucleophilic substitution of allylpalladium complexes, Heck reactions (Pd), asymmetric epoxidation, Wacker type reactions (Pd), asymmetric hydrogenations (Rh, Ru), reactions of chromium complexes, enantioselective reactions with Lewis acids, reactions with the McMurry reagent, etc. There is hardly any multistep organic synthesis that does not involve one of these metal catalysed reactions. Most of these catalysts have been developed by empiricism. The metal catalysed processes consist of a series of elementary steps which often have been studied in isolation in organometallic chemistry. The knowl- edge of such elementary steps - effect ofligands, anions, coordination number, valence states - has greatly contributed to the development of improved cata- lysts for the reactions mentioned above. In addition to the empirical approach theoretical methods have given support and guidance to the development of improved processes. Often the key steps of a cycle escape from a direct ob- servation and then theoretical contributions are even more wanted.
This book presents mathematical models that arise in current photographic science. The book contains seventeen chapters, each dealing with one area of photographic science, and a final chapter containing exercises. Each chapter, except the two introductory chapters, begin with general background information at a level understandable by graduate and undergraduate students. It then proceeds to develop a mathematical model, using mathematical tools such as ordinary differential equations, partial differential equations, and stochastic processes. Next, some mathematical results are mentioned, often providing a partial solution to problems raised by the model. Finally, most chapters include open problems. The last chapter of the book contains "Modeling and Applied Mathematics" exercises based on the material presented in the earlier chapters. These exercises are intended primarily for graduate students and advanced undergraduates.
We are proud to celebrate the 50th anniversary of the calixarenes. In 1944, Zinke and Ziegler proposed a cyclotetrameric structure for an oligomer extracted from the condensation product mixture obtained by reacting p-tert-butyl phenol with formaldehyde in the presence of sodium hydroxide. Fifty years on, calixarenes are the basis of many different areas of chemical research, with development occurring at an increasing pace over the past decade in particular. The present volume does not provide an overview of all these developments, but is rather a celebration of some of the highlights. This presentation of the intricate mosaic of diversity that characterizes calixarene chemistry will stimulate further developments in this fascinating field.
The creation of molecular materials that have desired electrical conductance and magnetic properties demands the precise arrangement of molecules in the solid state. Such controlled arrangement has been achieved very elegantly by supramolecular chemists, especially those practising crystal engineering. This book, which presents articles by foremost experts in crystal engineering, molecular conductors and magnetic magnetism, reveals the results of an interdisciplinary union that may well have a profound influence on the future of materials science. Theoretical studies reveal potential areas of interest for those investigating molecular conductors and magnets, as well as materials that exhibit both properties. A unique survey of the state of the art appealing to all those doing research in supramolecular chemistry and materials science.
* Much progress has been made in the last 8 years in understanding the theory and practice of silane coupling agents. A major advance in this direction was the measurement of true equilibrium constants for the hydroly sis and formation of siloxane bonds. Equilibrium constants for bond reten tion are so favorable that a silane coupling agent on silica has a thousandfold advantage for bond retention in the presence of water over an alkoxysilane bond formed from hydroxy-functional polymers and silica. In practice, the bonds of certain epoxies to silane-primed glass resist debonding by water about a thousand times as long as the epoxy bond to unprimed glass. Oxane bonds of silane coupling agents to metal oxides seem to follow the same mechanism of equilibrium hydrolysis and rebonding, although equilibrium constants have not been measured for individual metal-oxygen silicon bonds. This suggests, however, that methods of improving bond retention to glass will also improve the water resistance of bonds to metals. of standard coupling agents with a hydrophobic silane or one Modification with extra siloxane cross-linking have improved the water resistance of bonds to glass and metals another hundredfold over that obtained with single coupling agents."
Although this is a handbook for policy and regulation, the major part of it is filled with data on the three heavy metals that served as examples: mercury, cadmium and lead. Their stocks, productions, prices, trade flows, uses and applications, recovery and recycling, as well as their (eco)toxicological characteristics have been collected and presented to their fullest extent. In addition, they are thoroughly analysed for consistency, future developments and trends and, of course, their consequences for sustainable development and future policy and regulation. The second part, on policy and regulation, begins with an extensive and fundamental consideration on the characteristics of a sustainable heavy metals policy, whereby innovative policy tools are developed. In many aspects, these considerations are also valid for other metals and even non-metallic persistent substances. Addressing the European Union in particular, its policy-making structure and practice are critically analysed, in order to develop feasible and viable guidelines for long-, medium- and short-term EU policy measures. The results of this exercise are then applied to the three heavy metals. In each of these three chapters, all existing EU measures are presented in detail and confronted with better practices elsewhere, resulting in many suggestions and recommendations for the future. In the last chapter, the main conclusions and recommendations are carefully summarised. Together with a very extended table of contents, this makes the book easily accessible, in spite of its volume. This Handbook is a must for policy-makers and administrators at all levels, as well as for their counterparts in a wide variety of industries. In addition, it is well-suited for environmental science courses at academic or higher professional level.
Although, carbon is only one of one hundred plus elements, the polymer science lit erature consists primarily of studies on carbon based polymers. In part, this reflects the varied feedstock sources and in part, the type of bonds and bond forming reactions avail able to form organic polymers that are not available to the inorganic and organometallic chemist. However, recent intense interest in polymers with novel optical, electronic or magnetic properties or polymers that can serve as precursors to ceramic, semiconductor, metallic or superconductor materials has served as a driver for the development of novel synthetic routes and characterization techniques that have launched many new inorganic and organometallic oligomers and polymer systems. The following chapters represent an effort to provide an overview of several new and continuing areas of development in inorganic and organometallic polymer science. This book represents the second in a series of books we have edited on inorganic and organometallic polymer chemistry (1. Transformation of Organo-metallics into Common and Exotic Materials, NATO ASI Series Vol 141. 3. Inorganic and Organometallic Polymers with Special Properties, NATO ASI Series in press). In this series, we attempt to develop, for the reader, an understanding of the breadth, depth and potential of inorganic and organometallic polymer science."
The book presents the method of thermodynamic Green Functions applied to the problems of electrochemistry. The basic theorems and their derivations are found at the didactic level which requires, however, a knowledge of the principles of quantum mechanics and statistical physics. The book is mainly based on the results of papers published during the last fifteen years by its authors and their coworkers from the Department of Theoretical Chemistry and the Department of Solid State Physics of the University ofL6di (poland) within the context of the results reported in literature. Although the Green Functions Method has become very popular in solid state physics, there are almost no applications of this technique to electrochemistry. The only papers where the Green Functions Method is applied to the molten salts and liquid mercury theory are the precursory works published by Professor S. G. Davison and his coworkers from the Waterloo University (Canada) in the early eighties. We hope that the present book can fill this gap in the electrochemical literature.
Over the past twenty five years the Commission on Equilibrium Data of the Analytical Division of the International Union of Pure and Applied Chemistry has been sponsoring a noncritical compilation of metal complex formation constants and related equilibrium constants. This work was extensive in scope and resulted in publication of two large volumes of Stability Constants by the Chemical Society (London). The first volume, edited by L. G. Sillen (for inorganic ligands) and by A. E. Martell (for organic ligands), was published in 1964 and covered the literature through 1962. The second volume, subtitled Supplement No. 1, edited by L. G. Sillen and E. Hogfeldt (for inorganic ligands), and A. E. Martell and R. M. Smith (for organic ligands), was published in 1971 and covered the literature up to 1969. These two large compilations attempted to cover all papers in the field related to metal complex equilibria (heats, entropies, and free energies). Most recently a noncritical compilation of organic ligands by D. D. Perrin (Pergamon Press) extended coverage of the literature through 1973 and a similar volume for inorganic ligands by E. Hogfeldt covered through 1974. Since it was the policy of the Commission during that period to avoid decisions concerning the quality and reliability of the published work, th~ compilation would frequently contain from ten to twenty values for a single equilibrium constant. |
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