Rare sulfides

Selenium is found in a few rare minerals such as crooksite and clausthalite. In years past it has been obtained from flue dusts remaining from processing copper sulfide ores, but the anode metal from electrolytic copper refineries now provide the source of most of the world s selenium. Selenium is recovered by roasting the muds with soda or sulfuric acid, or by smelting them with soda and niter. 

The blue-emitting component of most television screens and computer terminals is another sulfide, ZnS Ag,Al. Although rare-earth activated blue-emitting phosphors ZnS Tm " and Sr (P0 2d-Eu (30) have also been evaluated for this appHcation, the search for a good blue phosphor that does not saturate at high current densities and maintains weU continues. 

SoHd lubricants ate added to help control high friction characteristics in high speed or heavy-duty appHcations where high temperatures are generated. Molybdenum disulfide [1317-33-5] M0S2, may be used alone or in a complex compound formed by grinding with fine natural graphite, and zinc sulfide [1314-98-3] ZnS. Other compounds include calcium fluoride, cryoHte [15096-52-3] Na AlF, rare-earth oxides, and metal sulfides, eg, iron, antimony, or zinc (see LUBRICATION AND LUBRICANTS). 

Metal sulfides can be prepared in the laboratory or on an industrial scale by a number of reactions pure products are rarely obtained without considerable refinement and nonstoichiometric phases abound (p. 679). The more important preparative routes include ... 

Ruthenium and osmium are generally found in the metallic state along with the other platinum metals and the coinage metals. The major source of the platinum metals are the nickel-copper sulfide ores found in South Africa and Sudbury (Canada), and in the river sands of the Urals in Russia. They are rare elements, ruthenium particularly so, their estimated abundances in the earth s crustal rocks being but O.OOOl (Ru) and 0.005 (Os) ppm. However, as in Group 7, there is a marked contrast between the abundances of the two heavier elements and that of the first. 

The inverse electron-demand Diels-Alder reaction is also accelerated by Lewis acids, but the successful application of chiral Lewis acids to this kind of Diels-Alder reaction is very rare. Marko and coworkers applied Kobayashi s catalyst system (Yb(OTf)3-BINOL-amine) to the Diels-Alder reaction of 3-methoxycarbonyl-2-py-rone with vinyl ether or sulfide [58] (Scheme 1.72, Table 1.29). A bulky ether or... 

In each of the composition diagrams in Fig. 14.2, the numbers represent a series of reactions run at a defined composition and temperature. These are isometric sulfur slices through three-dimensional K/P/RE/S quaternary phase diagrams. As just one example of what we have studied. Table 14.1 identifies the compositions at each point and the resulting phase(s). We have rigorously studied how phase formation is dependent upon the compositions of reactions for the rare-earth elements Y, Eu, and La and we have also discovered key structural relationships between the rare-earth elements, indicating a significant dependence on rare-earth and alkali-metal size for sulfides and selenides. 

We have developed a systematic study of quaternary chalco-gallates, indates (trielates) and chalco-silicates, and germinates (tetrelates) of the rare-earth metals. We have demonstrated that a series of new compounds could be formed in these families of materials [1, 3, 9, 10, 14, 81, 82]. There have been reports in the literature of a few examples of these types of materials, but there is sufficient evidence to support the fact that this area is wide open for exploring the likelihood for new rare-earth metal-based materials [83-90]. Our studies have focused on the gallium, indium, germanium and sihcon sulfides, selenides, and teUurides. 

Nearly all transition metals are oxidized readily, so most ores are compounds in which the metals have positive oxidation numbers. Examples include oxides (Ti02, mtile Fc2 O3, hematite C112 O, cuprite), sulfides (ZnS, sphalerite M0S2, molybdenite), phosphates (CeP04, monazite YPO4, xenotime both found mixed with other rare earth metal phosphates), and carbonates (FeC03, siderite). Other minerals contain oxoanions (MnW04, wolframite) and even more complex stmctures such as camotite, K2 (002)2 ( 4)2 2 O ... 

Mercuric sulfide (HgS) is dimorphic. The more common form, cinnabar (red a-form), has a distorted RS, trigonal structure which is unique among the monosulfides, for the crystal is built of helical chains in which Hg has two nearest neighbors at 2.36 A, two more at 3.10 A, and two at 3.30 A. Bulk a-HgS is a large-gap semiconductor (2.1 eV), transparent in the red and near IR bands. The rare, black mineral metacinnabarite is the 3-HgS polymorph with a ZB structure, in which Hg forms tetrahedral bonds. Upon heating, 3-HgS is converted to the stable a-form. The ZB structure of HgS is stabilized under a few percent admixture of transition metals, which replace Hg ions in the lattice. 

Rare earth sulfides, selenides, and tellurides show semiconducting properties and have potential for application in thermoelectric generation. Thin film chalcogenides of various rare earths have been prepared by multisource evaporator systems [233]. 

Heavy Rare Earth Element). Therefore, it is considered that negative Ce and positive Eu anomalies in hydrothermally altered volcanic rocks, Kuroko ores, and ferruginous chert and LREE enrichment in the Kuroko ores have been caused by hydrothermal alteration and precipitations of minerals from hydrothermal solution responsible for sulfides-sulfate (barite) mineralization. 

Adularia is abundant in Au-Ag deposits, where it is commonly found with Au-Ag minerals only rarely does it occur in Pb-Zn and Cu deposits. Albite is very rare and is reported only from the Nebazawa Au-Ag deposits. Barite is a common gangue constituent in Pb-Zn-Mn deposits, especially those in the southwestern part of Hokkaido and the northern part of Honshu, where it is usually a late-stage mineral coexisting with carbonate and quartz but rarely with sulfide minerals. Other rare gangue minerals include fluorite, apatite, gypsum, bementite, rutile, and sphene, but they have not been studied. 

Bence, A.E. (1983) Volcanogenic massive sulfides rtx k/water interactions in ba.saltic systems and their effects on the distribution of the rare earth elements and selected first. series transition elements (abst.). 4th International Symposium on Water-Rock interaction, Mi.sasa, Japan, 48. 

Graf, J.L. Jr. (1977) Rare earth element as hydrothermal tracers during the formation of massive sulfide deposits in volcanic rocks. Econ. Geoi, 72, 527-548. 

Whitford, D.J., Korsch, M.J., Orritt, PM. and Craven, S.J. (1988) Rare-earth element mobility around the volcanogenic polymetallic massive sulfide deposit at Que River, Tasmania, Australia. Chem. Geol, 8, 105-112,... 

---