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Books > Science & Mathematics > Chemistry > Inorganic chemistry > General
This book introduces the concept of crystallographic non- rigidity and asymmetry of the transition elements as central atoms organometallic compounds. This intrinsic behavior of central atoms in condensed matter is quantified by applying statistical approach. Averaging of extrinsic factors in crystal structures is tested by using variance analysis. Introductionof the above mentioned concept and applications of variance analysis as an approximation for considering factors influencing properties of central atomin the crystal is original and new.
Nearly three years have passed since the publication of the original Russian edition, in which time there have appeared various papers on recent research on the transuranium elements, of which the most notable concern the production of element 105 at Dubna and Berkeley. There has also been much fresh information on elements 104 (kurchatovium) and 103 (lawrencium). Our knowledge of shell effects in the fission barrier has been extended. Hopes of finding relatively stable superheavy elements have stimulated searches for such elements in nature as well as rapid development in heavy ion acceleration. We may see some very considerable discoveries in the next few years. The new results vary in reliability, and so it is not surprising that some papers on the properties of the heaviest elements have given rise to vigorous debates, whose value lies in the way they ad vance the subject. We have not attempted to give an exhaustive survey of recent papers and have merely added brief sections to reflect what we con sider to be the most important points from these. So far, the United states and the USSR have made the most considerable contributions to the synthesis, study, and use of the transuranium elements, so it is especially welcome to us that this book, first published in our country, should now appear in the USA in an English translation.
The ever-increasing importance of chemical reactions at high and superhigh temperatures in crystalline, amorphous, and semicrystalline SOlids, as well as the reactions of these solids with gases, prompted the authors of this book to examine critically the literature available in this field and to present a general review of the subject. In this monograph we discuss those chemical and physicochemical points which we consider to be most important for solving a series of problems in the preparation and use of new inorganic materials. We hope that this book will be of interest to the many specialists working on inorganic materials. N. A. Toropov PREFACE Modem technology demands ever more materials with high mechanical strength, heat and chemical re sistance, fire resistance, special electrical properties, particular behavior toward active radiations, etc. The search for such materials requires the study of various chemical compounds, metallic alloys, and other fused in organic systems, especially oxide systems. Materials based on oxides begin to assume increasing importance in many fields of the new technology. In this connection the investigation of oxides and systems consisting of two and more oxides is expanding greatly.
During the last decade there has been a renewed interest in under standing from a fundamental point of view the gasification of carbon. Basi cally there are two major issues in controlling the reactivity of carbon: i) reduction of the gasification rate of carbon materials in hostile environment ii) increase of the gasification rate in order to utilize carbonaceous compounds more effectively. Although these two objectives look somewhat contradictory, they are part of the general topics of understanding gasification reactivity of carbon. Refractory applications of carbon in furnace linings, seals and vanes, as well as the use of carbon-carbon or carbon-ceramic composites in struc tures able to withstand corrosion at high temperature require a better understanding of the fundamentals involved in carbon-oxidizing gas (02' CO, H 0) reactions. Furthermore a great interest of aluminium producers 2 2 is 10 extending the lifetime of carbon electrodes in alumina electrolysis which primarily depends on reducing their consumption rates by air or carbon dioxide. Proper control of gasification reactions is also of prime importance in manufacturing carbonaceous adsorbents like granular activated carbon clothes of high adsorption characteristics. The balance between increase of porosity and decrease in mechanical strength during activation is critical for developing new porous types of carbon materials in particular for carbon clothes and this can only be achieved by a careful control of the gasification reaction."
Within the last few years, iron research has yielded exciting new insights into the under standing of normal iron homeostasis. However, normal iron physiology offers little protec tion from the toxic effects of pathological iron accumulation, because nature did not equip us with effective mechanisms of iron excretion. Excess iron may be effectively removed by phlebotomy in hereditary hemochromatosis, but this method cannot be applied to chronic anemias associated with iron overload. In these diseases, iron chelating therapy is the only method available for preventing early death caused mainly by myocardial and hepatic iron toxicity. Iron chelating therapy has changed the quality of life and life expectancy of thalassemic patients. However, the high cost and rigorous requirements of deferoxamine therapy, and the significant toxicity of deferiprone underline the need for the continued development of new and improved orally effective iron chelators. Such development, and the evolution of improved strategies of iron chelating therapy require better understanding of the pathophysiology of iron toxicity and the mechanism of action of iron chelating drugs. The timeliness of the present volume is underlined by several significant develop ments in recent years. New insights have been gained into the molecular basis of aberrant iron handling in hereditary disorders and the pathophysiology of iron overload (Chapters 1-5)."
The activation of dioxygen by metal ions has both synthetic potential and biological relevance. Dioxygen is the cleanest oxidant for use in emission-free technologies to minimize pollution of the environment. The book gives a survey of those catalyst systems based on metal complexes which have been discovered and studied in the last decade. They activate molecular oxygen and effect the oxidation of various organic compounds under mild conditions. Much of the recent progress is due to a search for biomimetic catalysts that would duplicate the action of metalloenzymes. Mechanistic aspects are emphasized throughout the book. An introductonary chapter reviews the chemistry of transition metal dioxygen complexes, which are usually the active intermediates in the catalytic reactions discussed. Separate chapters are devoted to oxidation of saturated, unsaturated and aromatic hydrocarbons, phenols, catechols, oxo-compounds, phosphorus, sulfur and nitrogen compounds.
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.
In common with the editor of the first edition, my own personal involvement with tin chemistry began when I had the privilege of studying for a PhD degree under the supervision of Professor Alwyn G. Davies FRS at University College London (UCL) almost exactly 30 years ago. Then, following 21 years' service with the International Tin Research Institute, it was a great pleasure for me when the wheel turned full circle and, in 1994, Alwyn - now an Emeritus Professor - asked me to return to UCL as an Honorary Research Fellow in the Chemistry Department. One of my first tasks was when I received an invitation from Blackie A&P to edit the second edition of the Chemistry of Tin, which I was delighted to accept, since it enabled me to continued my life-long interest in tin chemistry and to maintain contact with my former friends and colleagues, many of whom have contributed to this book.
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.
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."
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.
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."
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.
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.
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.
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
* 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."
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.
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.
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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