Gmelin Handbook of Inorganic and Organometallic Chemistry, presently comprising over 600 volumes, is the most comprehensive collection of chemical and physical data of the elements and their compounds in the world. It is Gmelin's first aim to assemble and systematically classify the research findings scattered throughout the innumerable publications of the international primary literature. This vast amount of information is classified on the basis of the chemical elements, which in itself contributes to "user friendliness". A survey of the contents of the Handbook is given in the Complete Catalog (published every second year, with supplements in between), which can, thus, be very helpful when beginning a search. Access to a specific compound becomes even easier through consultation of the Formula Index volumes. For over three years the Gmelin Formula Index (plus the Complete Catalog entries) has been available as an online database, GFI, from STN. Online searches provide for a most comfortable and fast access to the Handbook. GFI is the first constituent of the complete Gmelin database presently under development. Subscribers to the Handbook are entitled to a 50 % discount when searching GFI online.
In the first part of this volume the nitrogen-containing compounds of molybdenum are described. The Mo-N system shows that M0 N and MoN are the stable nitrides. MOlybdenum 2 metal dissolves nitrogen to some extent but only at high temperatures. To get better insight into the reactions between nitrogen and molybdenum, the solubility, diffusion, adsorption and desorption phenomena, and ion bombardment are included in the section of the Mo-N system. M0 N has a large range of homogeneity toward lower nitrogen concentrations. The black 2 hexagonal MoN has only a narrow range of homogeneity. In addition some molybdenum compounds containing nitrogen and oxygen are known. The second part contains a full description of the compounds of molybdenum with fluorine. The fluorides MoF n with n ~ 2 are metastable while those with n = 3 to 6 are stable and have been observed in the Mo-F system. Pure MoF can exist without traces of oxygen, in co nt rast 3 to earlier assumptions. MoF was unambigously prepared and characterized in 1957. Its crystal 4 structure is still unknown. MoF is often contaminated with the oxide fluoride MoOF and it is s 4 difficult to remove. Even sm all amounts affect the properties of MoF . MoF , which is liquid at s 6 room temperature and solidifies to a "plastic" crystal modification below ca. 17SC, is the most investigated of all the molybdenum fluorides.
The core of the Gmelin Index is formed by a Formula Index which includes all the definite elements, compounds, ions, and systems which are discussed or mentioned anywhere in the entire Eight Edition of the Gmelin Handbook. All volumes of the Main Series which were published before the end of 1974 are included, as well as volumes 1 through 12 of the New Supplement Series"--Introd.
Gmelin Handbook of Inorganic and Organometallic Chemistry, presently comprising over 600 volumes, is the most comprehensive collection of chemical and physical data of the elements and their compounds in the world. It is Gmelin's first aim to assemble and systematically classify the research findings scattered throughout the innumerable publications of the international primary literature. This vast amount of information is classified on the basis of the chemical elements, which in itself contributes to "user friendliness". A survey of the contents of the Handbook is given in the Complete Catalog (published every second year, with supplements in between), which can, thus, be very helpful when beginning a search. Access to a specific compound becomes even easier through consultation of the Formula Index volumes. For over three years the Gmelin Formula Index (plus the Complete Catalog entries) has been available as an online database, GFI, from STN. Online searches provide for a most comfortable and fast access to the Handbook. GFI is the first constituent of the complete Gmelin database presently under development. Subscribers to the Handbook are entitled to a 50 % discount when searching GFI online.
The present volume continues the description of the chemical reactions of eiemental tungsten started with "Tungsten" Suppl. Vol. A 7. It covers the reactions with the metallic elements from zinc to actinoids. The treatment includes phase diagrams, bulk reactions, and surface processes which again are of outstanding importance in most systems. The raader is referred to the introductory remarks on pp. X/XI. Frankfurt am Main Ernst Koch November 1987 Introductory Remarks Abbreviations In order not to overload the text, the following abbreviations are sometimes used without definitions in the present volume, in addition to the abbreviations usual in the Gmelin Handbook. a. c. alternating current AE Auger electron Auger electron spectroscopy(ic) or spectrum AES bcc body-centered cubic CPD contact potential difference counts per second cps d. c. direct current DTA differential thermoanalysis Fermi Ievel EF EI electron impact ELS electron energy loss spectroscopy or spectrum EMF, emf electromotive force fcc face-centered cubic FE field emission field electron (emission) microscope(ic) FEM FES field emission spectroscopy FIM field ion microscope(ic) F-N Fowler-Nordheim hcp hexagonal close-packed 6 L Langmuir=1·10- Torr·s LEED low energy electron diffraction monolayer ML PES photoelectron spectroscopy PSD photon-stimulated desorption RHEED reflection high energy electron diffraction room temperature RT SI secondary ion SIMS secondary ion mass spectrometry TDS thermal desorption spectroscopy(ic) or spectrum TE thermionic emission total energy distribution TED UHV ultra-high vacuum UPS ultra-violet photoelectron spectroscopy(ic) or spectrum XPS X-ray photoelectron spectroscopy(ic) or spectrum Gmelin Handbock WSuppl. Vol.
This volume is the first of two which cover mononuclear iron compounds with ligands bonded by six C atoms (denoted by 6L ligands). Prominent and well documented examples are complexes with n-bonded arenes, but complexes with n6-bonded cyclooctatetraene and with n5 -n1, n4 -n2, or n3 - n3-bonded ligands are also known. The first volume deals with compounds with one 6L ligand and additional ligands bonded only by heteroatoms or by one to four C atoms (1L to 4L ligands), including carbaborane ligands. From the great number of 6LFe5L compounds, mostly monocations, those included contain C6H6 or monosubstituted benzenes as 6L ligand. These organoiron complexes are important intermediates in synthesis of substituted cyclohexadienes or benzenes and other organic compounds. The reducing properties of neutral 6LFe5L compounds are used in stoichiometric and catalytic reactions. The literature closing date is 1990. The volume contains empirical formula and ligand formula indexes.
Volume Organoiron Compounds B 14 systematically covers the literature through the end of 1986 and includes most references from 1987 and some from 1988. The volume continues Series B (volumes B 1 to B 13 already published) on mononuclear organoiron compounds. Series A (volumes A 1 to A 8 already published) is devoted to the ferrocenes and Series C (volumes C 1 to C 5 and C 7 already published) treats organoiron compounds with two or more Fe atoms in the molecule. The present volume completes the description of C5H5Fe(CO)2R compounds. The volume is completed by a formula and ligand index covering both volumes B 13 and B 14.
The Gmelin Formula Index and its First Supplement covered those volumes of the Eighth Edition of the Gmelin Handbook which had been issued up to the end of 1979. The present Second Supplement updates the Index by inclusion of the volumes which appeared up to the end of 1987. With this Second Supplement all compounds described in the Gmelin Handbook of Inorganic Chemistry in the period between 1924 and 1987 can be located. The basic structure of the Formula Index remains the same as in the previous editions. Computer techniques were employed in the preparation and print of the Second Supple ment. The data acquisition, sorting, and further data handling were performed with the aid of a series of computer programs developed by staff members of the former" Online Group" of the Gmelin Institute, now at Chemplex GmbH, and by the printer" Universitiits druckerei H. StOrtz AG, WOrzburg". Whereas the Handbook itself will continue to appear in printed form, the present Second Supplement of the Index is intended to be the last one issued in print. The cumulated contents of the Index and its Supplements are contained in the Gmelin Formula Index (GFI) database which is available to the scientific community via STN. This database will be updated annually to include the published Handbook volumes.
The present volume Uranium C12 covers the binary and polynary carbides of uranium, including ternary carbides with nonmetals like the carbide oxides and carbide nitrides U(C,O) and U(C,N). The binary carbide UC and especially the mixed carbide (UO.80PUO.20)C are of special importance due to their potential as the fuel for advanced .. Fast Breeder Reactors" because of properties such as the short doubling time, the high fissionable material density, and the good thermal conductivity. On the other hand, the dicarbide UC is of interest for .. High 2 Temperature Reactors", especially in the form of the mixed carbide (U . Th . )C . For O80 o20 2 the first time, India used mixed uranium-plutonium carbide (U . PU .)C as the fuel for its O3 O7 own newly developed 15 MW Fast Breeder Reactor at Kalpakkam, south of Madras. el Because of the technological importance of the uranium carbides a lot of data were published only in reports. In most cases, it was the aim of these less-scientifically based studies to promote the carbide fuel development on an economical basis. The lack of analyti cal data on the purity of the samples, missing characterization of the present phases, etc., hQINever, does not allow the discussion of the results of such references in this handbook. Therefore, only reliable publications were cited. For the technical fabrication of uranium carbides and their irradiation behavior, see Volumes A3 and A4 of this Handbook.
A fascinating aspect of many of the selenium- and tellurium-containing compounds described in this volume is that they are built up from octahedral Mo6 clusters which are surrounded by eight other atoms X in the form of a cube: Mo6X8. The Mo atoms occupy the centers of the faces of the X8 cube. The interesting variety in the substiution of the X positions can be encountered throughout the whole volume. The X atoms can be of a single element as in Mo6Te8, but can also be statistically occupied by two elements, e.g., in Mo6(Te,S)8, or even by more elements as in Mo6(Te,Se)8-yIy. In addition, there are channels with vacant positions between the Mo6X8 clusters in the diagonal direction of the X8 cube. These vacant positions offer more possibilities for the fantasy of the chemist.
This volume 8 is the fourth in a series dealing with organomolybdenum compounds. An Empirical Formula Index and a Ligand Formula Index provide ready access to the compounds covered. Volume 5 describes mononuclear organomolybdenum compounds with isocyanide, 3 4 carbene, carbyne, alkynyl, alkene, alkyne, L, and L ligands with and without additional CO groups. Volume 6 starts the description of mononuclear organomolybdenum compounds with 5 one L Ligand, a Ligand bonded to molybdenum by five carbon atoms. The compounds contain either zero or one CO group bonded to the molybdenum atom. Volume 7 continues the 5 description of L-molybdenum compounds containing two CO groups, but no additional nl 5 ligands. This volume describes L-molybdenum compounds with two CO groups and additional 1 4 L to L ligands. Following the nomenclature used in this series of organomolybdenum com pounds, nl is an organic Ligand bonded by n C atoms to molybdenum, and mo is an electron 2 donor Ligand with m donor electrons. Thus 0 denotes a Ligand such as PR . 3 Many of the data, particular those in tables, are given in an abbreviated form without units; for explanations see p. X. Additional information, if necessary, is given before the individual table. Frankfurt am Main Manfred Winter November 1992 Wolfgang Petz X Remarks on Abbreviations and Dimensions Many compounds in this volume are presented in tables in which numerous abbreviations are used, the dimensions are omitted for the sake of conciseness. This necessitates the following clarifications.
The volume comprises an updated and critical description of the binary and ternary thorium carbides. These compounds are of technological interest because of their possible use as fertile materials in advanced nuclear power reactors. The fuel for the Thermal Breeder consists of a ThC-UC solid solution and that for the Thorium High Temperature Reactor of coated ThC2-UC2 particles. The binary Th-C system and ternary carbides were intensively investigated worldwide for nearly 20 years. Because of general discussions on the use of nuclear technology, interest in advanced nuclear reactors declined in recent years. Nevertheless, the research activity in the solid state science of binary and ternary thorium carbides increased and the Th-C system became one of the best known binary systems. At high temperatures there exists a series of solid solutions ranging from Th metal to the hypostoichiometric cubic ThC1.96' including the monocarbide ThC. A body-centered cubic Th2C3 of the Pu2C3 structure type only exists at pressures above 30 kbar. The Th carbides are refractory compounds with high melting points, e.g., 2500° C for the composition ThC0.97. Ternary carbides are either stoichiometric compounds, like ThAl4C4, ThAlC2, and Th4Al2C5 in the Th-Al-C system, or they form solid solutions with more or less broad ranges of composition. On the other hand, ThC is immiscible with group IV and V transition metal carbides because of its large unit cell. The normally metastable Th2C3 can be stabilized by forming solid solutions like (Th, La)2C3 with other sesquicarbides. Some ternary phases are superconductors with transition temperatures as high as 17 K.
The current volume on the metallurgy of iron covers ingot casting, mold casting, and the powder metallurgy of steel. The expert authors reviewed an enormous amount of published information in these areas while adding their own extensive, not yet published practical experience. Discussions on the quality of ingots and semifinished products, on the detailed steps of various powder-metallurgical processes, and on special material and product properties extend the scope of Gmelin-Durrer series. The material presented in this volume is of interest to metallurgists in the steel industry, research institutes, and universities. The wide scope, moreover, makes this volume an invaluable source also for practitioners associated with supplying industries, engineering firms, and contractors.
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