Born and initially developed in various industrial laboratories, mainly in U.S.A. and Gennany, homogeneous phase catalytic carbon monoxide hydrogenation and alcohols and their derivatives carbonylation and homologation, have generally been considered and reviewed separately in the course of their 40 years history without concern for common aspects in the chemical transfonnations and in catalysis. Thanks to researchers of Japanese companies participating in the National C 1 Chemistry Project (1980-1987) the scientific and technical approaches in this field have been unified and applied in parallel, in the light of some common aspects of the chemical reactions and mechanisms. Now, at a moment when research seems becahned, a general presentation and discussion of the most recent topics might be an useful basis for further development of this chemistry. To delimit and simplify the discussion of the chemical aspects and the nature of the catalysts involved, the present review is limited to reactions employing homogeneous metal complexes for the direct conversion of syngas to oxygenates and to the hydrocarbonylation of these last to homologous derivatives. Since the previous practically contemporary reviews by Dombek [in Adv. Organomet. Chern. (1983)] on CO hydrogenation and by the present authors [in Asp.Homog.Catal.(Reidel Pu.l984)] on alcohol homologation fully cover the literature up to 1982, here we mainly refer to work done after 1982, and consider the cited reviews as covering the historical development of research in the 1940- 1980 period.

This book presents the third volume of a complete development of the new structural classification of minerals, which is based on the internal crystal structure, and is therefore its natural classification. Because of the large domain of the mineral kingdom, this work is divided in three volumes, in which the minerals are ordered from the structurally simple to the more complex.

Audience: This work will be of particular interest to teachers and research workers of in mineralogy, and in inorganic crystal structures in academia.

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, materials science, and engineering, with length scales ranging from Angstroms up to millimeters. The emphasis is on basic science rather than on applications. Each book focuses on a single area of current interest and brings together leading experts to give an up-to-date discussion of their work and the work of others. Each article contains enough references that the interested reader can access the relevant literature. Thanks are given to the Center for Fundamental Materials Research at Michigan State University for supporting this series. M.F. Thorpe, Series Editor E-mail: [email protected] East Lansing, Michigan, November 200 I v PREFACE The study of the atomic structure of crystalline materials began at the beginning of the twentieth century with the discovery by Max von Laue and by W.H. and W.L. Bragg that crystals diffract x-rays. At that time, even the existence of atoms was controversial.

Science and art of crystal growth represent an interdisciplinary activity based on fundamental principles of physics, chemistry and crystallography. Crystal growth has contributed over the years essentially to a widening of knowledge in its basic disciplines and has penetrated practically into all fields of experimental natural sciences. It has acted, more over, in a steadily increasing manner as a link between science and technology as can be seen best, for example, from the achievements in modern microelectronics. The aim of the course "Crystal Growth in Science and Technology" being to stress the interdisciplinary character of the subject, selected fundamental principles are reviewed in the following contributions and cross links between basic and applied aspects are illustrated. It is a very well-known fact that the intensive development of crystal growth has led to a progressive narrowing of interests in highly specialized directions which is in particular harmful to young research scientists. The organizers of the course did sincerely hope that the program would help to broaden up the horizon of the participants. It was equally their wish to contribute within the traditional spirit of the school of crystallography in Erice to the promotion of mutual understanding, personal friendship and future collaboration between all those who were present at the school.

Polytypic crystals of semiconductors, dielectrics and magnetic materials attract an increasing attention in science and technology. On one hand, the phenomenon of polyty pism is one of the fundamental problems of solid-state physics; its solution would make it possible to elucidate- the problem of the interconnection of different structures and intraatomic forces acting in crystals. On the other hand, the polytypic difference in crystals is most strongly expressed in electro-physical properties, which makes their application promising, mainly in semiconductor electronics. Thus, the difficulties of pro ducing modulated structures in polytypic crystals can be overcome since these crystals form a class of one-dimensional natural superlattices. At present it has become clear that polytypism in crystals and compounds is the rule rather than an exception and it is determined by the conditions of their synthesis. This phenomenon seems to be rather widespread in nature and fundamental for crystal forma tion. H polytypism was recently thought to be but a specific structural feature of a few substances such as SiC, ZnS, CdI , etc. , by now this phenomenon has been discovered in 2 v an increasing range of crystalline substances, for example, in silicon, diamond, AIIIB , VI AIIB , AIBVII compounds, in ternary semiconducting compounds, metals, silicates, perovskites, mica, organic crystals. The more accurately the structural studies are per formed, the greater is the number of crystals of various substances found to exhibit the phenomenon of polytypism. Recently, excellent surveys have systematized our knowledge of polytypism.

Today large numbers of geoscientists apply thermodynamic theory to solu tions of a variety of problems in earth and planetary sciences. For most problems in chemistry, the application of thermodynamics is direct and rewarding. Geoscientists, however, deal with complex inorganic and organic substances. The complexities in the nature of mineralogical substances arise due to their involved crystal structure and multicomponental character. As a result, thermochemical solutions of many geological-planetological problems should be attempted only with a clear understanding of the crystal-chemical and thermochemical character of each mineral. The subject of physical geochemistry deals with the elucidation and application of physico-chemical principles to geosciences. Thermodynamics of mineral phases and crystalline solutions form an integral part of it. Developments in mineralogic thermody namics in recent years have been very encouraging, but do not easily reach many geoscientists interested mainly in applications. This series is to provide geoscientists and planetary scientists with current information on the develop ments in thermodynamics of mineral systems, and also provide the active researcher in this rapidly developing field with a forum through which he can popularize the important conclusions of his work. In the first several volumes, we plan to publish original contributions (with an abundant supply of back ground material for the uninitiated reader) and thoughtful reviews from a number of researchers on mineralogic thermodynamics, on the application of thermochemistry to planetary phase equilibria (including meteorites), and on kinetics of geochemical reactions."

Experiments showinga rapid and reversible change ofcolor s eem likemagic and are always fascinating. The process involved, photochromism, has a few real and many potential applications. Photochromic glasses thatdarken int he s unlight (protecting eyes from excessive light intensity) and bleach ind im lighta re today a part ofe v eryday life. Organic photochromic compounds in plastic ophthalmic lenses, more comfortable to wear, are now competing with silversalts in glasses, despite the longer lifetime oft he inorganic system. This successful commercial application has given a new impetus to research in the general field of photo chromism, which had its most recent revival in the early eighties. The storyo forganic photochromism with its ups anddowns, from the breakthroughs oft he pioneering periodi n the fifties, through the hardtimes dueto the drawbacks of photodegradation, tot he recent successes is in many ways a saga. The upsurges in this domain were marked by an increasing flow of articles in scientific journals andt he publication of several books (in 1971, 1990, and 1992) that have collectedt he important accumulatedknowledge. Over this period, a considerable number ofpatents have been issued. International meetings have accompanied this activity, the most recent being held in 1993 (ISOP 93 atLes Embiez Island, France) and in 1996 (ISOP 96 inClearwater, Florida). Remark ably, these meetings had good representation from both academia and industry. The next ISOP is planned for 1999 in Fukuoka, Japan.

In the decade since the introduction of the first commercial lithium-ion battery research and development on virtually every aspect of the chemistry and engineering of these systems has proceeded at unprecedented levels. This book is a snapshot of the state-of-the-art and where the work is going in the near future. The book is intended not only for researchers, but also for engineers and users of lithium-ion batteries which are found in virtually every type of portable electronic product.

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.

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.

Scientists who have had the opportunity of being associated with Professor Egon T. Degens, to whom this Festschrift is devoted, have been influenced by his ideas on subjects as varied as: extraterrestrial organic matter, origin of life, evolution of organisms, isotope biogeochemistry down to more imminent ones such as the carbon cycle and its implications on climate. This variety is also reflected in the papers in the present volume contributed by colleagues who have known Egon or have worked with him. Egon Theodor Degens was born on April 16, 1928 at Inden, Germany and had his education in Bonn and Wiirzburg. After a stint at the Pennsylvania State University he returned to Wiirzburg to help set up one of the first organic geochemistry laboratories in the world. This laboratory was the breeding ground for some of the eminent organic geochemists at work today. Later, he joined the California Institute of Technology and began his work on stable carbon isotopes, and later on biogeochemical compounds in natural waters. From California he moved on to the east coast, which led to yet another productive phase at the Woods Hole Oceanographic Institution. He was instrumental in the pioneering work carried out by the Woods Hole scientists in the Black Sea which is the largest anoxic basin in the world, and in the Red Sea where the first hydrothermal ore deposits on the seafloor were discovered.

Nitrogen dioxide (N0 ) is notorious for its complex visible spectrum and has 2 frustrated many chemists and physicists. Despite their intense investigations the molecule still resists complete analysis of its spectrum. Because of the high density of lines, it is apparent that high-resolution measurements are essential to a thorough understanding of the spectrum. The major part of this book consists of an atlas, described in Chap. 2, of the absorption spectrum and the Stark modulation spectrum of N0 mea 2 sured using a cw dye laser. The narrow spectral width as well as the wide scan range of the dye laser made it possible to record the spectra contin uously over a wide range with Doppler-limited resolution. In the spectral range 16751-17885 em-I, about 13300 peaks have been observed in the absorption spectrum and their wave numbers, calibrated against Ar lines, are listed in the tables. The Stark modulation spectrum also shown provides useful information about the energy level structures complementary to that obtained from the absorption spectrum."

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'.

The field of Physical Chemistry has developed through the application of theories and concepts developed by physicists to properties or processes of interest to chemists. Physicists, being principally concerned with the basic ideas, have generally restricted their attention to the simplest systems to which the concepts applied, and the task of applying the techniques and theories to the myriad substances and processes that comprise chemistry has been that of the physical chemists. The field of Solid State Chemistry has developed with a major impetus from the synthetic chemists who prepared unusual, novel materials with the principal guid ing ideas growing out of an understanding of crystal structure and crystal structure relationships. The novel materials that pour forth from this chemical cornucopia cry out for further characterization and interpretation. The major techniques for the characterization and interpretation of crystalline solids have been developed in the fields of Solid State Physics and Crystallography. Thus, the need arose for expanding the realm of Physical Chemistry from its traditional concern with molecules and their properties and reactions to include the physics and chemistry of crystalline solids. This book deals with the applications of crystallography, group theory and thermodynamics to problems dealing with non molecular crystalline solids."

1. A.-R. Grimmer, Berlin, FRG; B. Bl}mich, Aachen, FRG: Introduction to Solid-State NMR 2. F. Laupretre, Paris, France: High-Resolution 13C NMRInvestigations of Local Dynamics in Bulk Polymers at Temperatures Below andAbove the Glass-Transition Temperature 3. D. Raftery, Philadelphia, PA;B.F. Chmelka, Santa Barbara, CA: Xenon NMR Spectroscopy 4. G. Fleischer, Leipzig, FRG; F. Fujara, Mainz, FRG: NMR as a Generalized Incoherent Scattering Experiment 5. P. Bl}mler, B. Bl}mich, Mainz, FRG: NMR Imaging of Solids

Assembling a program in bioinorganic chemistry that is scientifi cally relevant, well defined, and self-consistent is not an easy task. In this attempt we decided to consider zinc enzymes, copper oxidases, cytochromes and cytochrome oxidase. The choice is in part due to the great attention that the current specialized literature devotes to these topics, which are now debated among chemists, biochemists, biophysicists, etc .. We believe that hydration reactions, hydrolytic and oxidative processes have much in common from the point of view of the reaction mechanisms, the comprehension of which represents a frontier of science. For these reasons these topics have been the subject of the NATO-ASI held at San Miniato, Pisa, Italy, from May 28 to June 8, 1982. We hope we can transfer here the main conclusions of what (we believe) was a very stimulating scientific meeting. We would like to thank the local saving bank, Cassa di Risparmio di San Miniato, for helping in many ways. The financial contribution from the European Research Office of the US Army, and from the Bruker Spectrospin s.r.l., Italy, is also acknowledged. The National Science Foundation of the United States has provided a travel grant to one of the participants from the U.S.A. We are grateful to the NATO Scientific Affairs Division which provided a grant to finance this Institute."

Solid-State NMR is a branch of Nuclear Magnetic Resonance which is presently experiencing a phase of strongly increasing popularity. The most striking evidence is the large number of contributions from Solid-State Resonance at NMR meetings, approaching that ofliquid state resonance. Important progress can be observed in the areas of methodological developments and applications to organic and inorganic matter. One volume devoted to more or less one of each of these areas has been published in the preceding three issues. This volume can be considered an addendum to this series. Selected methods and applications of Solid-State NMR are featured in three chapters. The first one treats the recoupling of dipolar interactions in solids, which are averaged by fast sample rotation. Following an introduction to effective Hamiltonians and Floquet theory, different types of experiment such as rotary resonance, dipolar chemical shift correlation spectroscopy, rotational resonance and multipulse recoupling are treated in the powerful Floquet formalism. In the second chapter, the different approaches to line narrowing of quadrupolar nuclei are reviewed in a. consistent formulation of double resonance (DaR) and dynamic angle spinning (DAS). Practical aspects of probe design are considered as well as advanced 2D experiments, sensitivity enhancement techniques, and spinning sideband manipulations. The use of such techniques dramatically increases the number of nuclei which can be probed in high resolution NMR spectroscopy. The final chapter describes new experimental approaches and results of structural studies of noncrystalline solids."

"Modern Crystallography IV" is devoted to a systematic and up- to-date description of fundamental physical properties of solid and liquid crystals. These include elastic and mechanical, dielectric and ferroelectric, magnetic and optical properties, transport phenomena and spectroscopy. An important feature of the treatment is its use of the crystallographic approach, an introduction to which is given in the opening chapter of the book. The topics are treated at a level understandable to students who have two years of university physics. Researchers and engineers working on practical applications should also find the book useful, as should specialists in other fields who wish to broaden their knowledge of crystallography and materials science. The book is written by a group of leading scientists from the Institute of Crystallography of the USSR Academy of Sciences.

This book contains the proceedings of the international workshop on Many-Atom Interactions in Solids, which was held June 5-9, 1989, in Pajulahti, Finland. The purpose of the workshop was to bring together physicists, chemists and materials scientists working in the field of interatomic interactions and their applications in computer simulations of condensed matter. The workshop attracted a good fraction of the active groups in the field, and created lively discussion and interchange of ideas. The contributions in this volume have been grouped by the editors into review type articles and more specific applications to different topics. The order of the articles does not follow the order of the presentations in the workshop. The editors wish to express their gratitude first of all to all the workshop par ticipants for creating an enjoyable and fruitful workshop and to the contributors for their efforts in putting together these proceedings. We hope that this volume will be a useful resource for practitioners in and newcomers to this exciting field. We would like to thank Jens N!l1rskov for his help in planning the scientific pro gramme and Eija Jarvinen for taking care of most of the practical arrangements of the workshop. The workshop was made possible by financial support from the Finnish Ministry of Education, the Research Institute for Theoretical Physics (Helsinki), NORDITA (Copenhagen), and Helsinki University of Technology.

''A must for anyone interested in metal-containing polymers and all its aspects.'' ---American Scientist ''Nicely organized...well-written....An excellent shapshot of the current state of this field.'' ---MRS Bulletin, July 1998

This volume represents an edited selection of papers presented at the International symposium on the geology of tin deposits held in Nanning City in October 1984. It documents a great advance in our knowledge of tin deposits, particularly of the People's Republic of China. Details are presented in English for the first time on the major tin-polymetallic sulphide deposits of Dachang and Gejiu, which bear similarities to the deposits of Tasmania, but are little known to the geological community outside of China. The publication of this volume was sponsored by the United Nations ESCAP Regional Mineral Resources Development Centre (RMRDC), now a Regional Mineral Resources Development Project (RMRDP) within ESCAP. The Centre had previously published a report on the Symposium in Nanning City and the following field trip to the Dachang tin-polymetallic sulphide deposit of Guangxi, entitled "Report on the International Symposium on the Geology of Tin Deposits: Nanning and Dachang, China, 27 October - 8 November 1984." It is my privilege to acknowledge the help provided by Dr. J. F. McDivitt and Dr. H. W. Gebert, co-ordinator of ESCAP-RMRDC.

In the last two decades low-dimensional (low-d) physics has matured into a major branch of science. Quite generally we may define a system with restricted dimensionality d as an object that is infinite only in one or two spatial directions (d = 1 and 2). Such a definition comprises isolated single chains or layers, but also fibres and thin layers (films) of varying but finite thickness. Clearly, a multitude of physical phenomena, notably in solid state physics, fall into these categories. As examples, we may mention: * Magnetic chains or layers (thin-film technology). * Metallic films (homogeneous or heterogeneous, crystalline, amorphous or microcristalline, etc.). * I-d or 2-d conductors and superconductors. * Intercalated systems. * 2-d electron gases (electrons on helium, semiconductor interfaces). * Surface layer problems (2-d melting of monolayers of noble gases on a substrate, surface problems in general). * Superfluid films of ~He or 'He. * Polymer physics. * Organic and inorganic chain conductors, superionic conductors. * I-d or 2-d molecular crystals and liquid crystals. * I-d or 2-d ferro- and antiferro electrics.

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.

It is now IS years since the first patents in polymer supported metal complex catalysts were taken out. In the early days ion-exchange resins were used to support ionic metal complexes. Soon covalent links were developed, and after an initially slow start there was a period of explosive growth in the mid to late 1970s during which virtually every homogeneous metal complex catalyst ever reported was also studied bound to a support. Both polymers and inorganic oxides were studied as supports, although the great preponderance of workers studied polymeric supports, and of these polystyrene was by far the commonest used. This period served to show that by very careful design polymer-supported metal complex catalysts could have specific advantages over homogeneous metal complex catalysts. However the subject was a complicated one. Merely immobilising a successful metal complex catalyst to a functionalised support rarely yielded other than an inferior version of the catalyst. Amongst the many discouraging results of the 1970s, there were more than enough results that were sufficiently encouraging to demonstrate that, by careful design, supported metal complex catalysts could be prepared in which both the metal complex and the support combined together to produce an active catalyst which, due to the combination of support and complex, had advantages of activity, selectivity and specificity not found in homogeneous catalysts. Thus a new generation of catalysts was being developed.

The primary literature on organometallic chemistry has undergone phenomenal growth. The number of papers published from 1951 to 1976 is about equal to all prior literature. Together with this intense activity there has developed a complexity in the literature. Thus, specialized texts and teaching texts, a review journal, an advanced series, and a research journal have all appeared during this period. The present series also reflects this growth and recognizes that many categories of organometallic compounds now have numerous representatives in the literature. The purpose of Organometallic Reactions and Syntheses is to provide complete chapters on selected categories of organometallic compounds, describing the methods by which they have been synthesized and the reactions they undergo. The emphasis is on the experimental aspects, although struc tures of compounds and mechanisms of reactions are discussed briefly and referenced. Tables of all of the compounds prepared in the category under consideration and detailed directions for specific types make these chapters particularly helpful to the preparative chemist. While the specific directions have not been referenced in the same way. as are those in Organic Syntheses and Inorganic Syntheses, the personal experiences of the authors often lend special merit to the procedures and enable the reader to avoid many of the pitfalls frequently encountered in selecting an experimental procedure from the literature."