Metallated sulfides

In view of the synthetic applications, among carbanions stabilized by only one divalent sulfur atom, allylic thiocarbanions proved to be particularly valuable, as shown with Biellmann coupling of allylic groups, applied to an elegant synthesis of squalene from farnesyl bromide [301]. In this synthesis, the retention of the allylic double bond position and stereochemistry in both the metallation-alkylation and the desulfurization steps are noteworthy. However, the results are not always as clear-cut, and 

We owe to Corey and Seebach [302] an efficient procedure for the generation of phenylthiomethyllithium (PhSCH2Li), opening the way for practical applications. They found that this reagent was produced in about a 97% yield through reaction of equimolar amounts of n-butyllithium, DABCO and thioanisole in THF at 0°C for 45 min. 

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Iodine monochloride Aluminum foil, organic matter, metal sulfides, phosphorus, potassium, rubber, sodium... 

Metals treatments Metal sulfides Metal surface cleaners Metal surface treatment Metal surface treatments... 

Arsenic is another element with different bioavailabiUty in its different redox states. Arsenic is not known to be an essential nutrient for eukaryotes, but arsenate (As(V)) and arsenite (As(III)) are toxic, with the latter being rather more so, at least to mammals. Nevertheless, some microorganisms grow at the expense of reducing arsenate to arsenite (81), while others are able to reduce these species to more reduced forms. In this case it is known that the element can be immobilized as an insoluble polymetallic sulfide by sulfate reducing bacteria, presumably adventitiously due to the production of hydrogen sulfide (82). Indeed many contaminant metal and metalloid ions can be immobilized as metal sulfides by sulfate reducing bacteria. 

Direct splitting requires temperatures above 977°C. Yields of around 30% at 1127°C are possible by equiUbrium. The use of catalysts to promote the reaction can lower the temperature to around the 327—727°C range. A number of transition metal sulfides and disulfides are being studied as potential catalysts (185). Thermal decomposition of H2S at 1130°C over a Pt—Co catalyst with about 25% H2 recovery has been studied. 

A more economical route appears to be the iadirect route, usiag a two-step reactioa sequeace via a sulfuri2atioa and desulfuri2ation of a metal sulfide. Decomposition usiag the mixed oxidatioa-state Ni2S2 has beea proposed ... 

Roasting ofSulRdes. Most nonferrous metals occur in nature mainly as sulfides. These cannot be easily reduced directly to the metal. Burning metallic sulfides in air transforms them into oxides or sulfates which are more easily reduced. The sulfur is released as sulfur dioxide, as shown by the foHowing typical reaction for a divalent metal, M ... 

This reaction is strongly exothermic and proceeds spontaneously from left to right for most common metallic sulfides under normal roasting conditions, ie, in air, because P q + Pq = - 20 kPa (0.2 atm) at temperatures ranging from 650 to 1000°C. The physical chemistry of the roasting process is more complex than indicated by equation 3 alone. Sulfur trioxide is also formed,... 

The red tetrathiomolybdate ion appears to be a principal participant in the biological Cu—Mo antagonism and is reactive toward other transition-metal ions to produce a wide variety of heteronuclear transition-metal sulfide complexes and clusters (13,14). For example, tetrathiomolybdate serves as a bidentate ligand for Co, forming Co(MoSTetrathiomolybdates and their mixed metal complexes are of interest as catalyst precursors for the hydrotreating of petroleum (qv) (15) and the hydroHquefaction of coal (see Coal conversion processes) (16). The intermediate forms MoOS Mo02S 2> MoO S have also been prepared (17). 

Deposits. Selenium forms natural compounds with 16 other elements. It is a main constituent of 39 mineral species and a minor component of 37 others, chiefly sulfides. The minerals are finely disseminated and do not form a selenium ore. Because there are no deposits that can be worked for selenium recovery alone, there are no mine reserves. Nevertheless, the 1995 world reserves, chiefly in nonferrous metals sulfide deposits, are ca 70,000 metric tons and total resources are ca 130,000 t (24). The principal resources of the world are in the base metal sulfide deposits that are mined primarily for copper, zinc, nickel, and silver, and to a lesser extent, lead and mercury, where selenium recovery is secondary. 

Pb, respectively (7). Por E, the formulas are (—) AgOH and (-----------) Ag2S. Curves for metal sulfides are based on experimental data Hsted in Reference 8. 

Sulfur constitutes about 0.052 wt % of the earth s cmst. The forms in which it is ordinarily found include elemental or native sulfur in unconsohdated volcanic rocks, in anhydrite over salt-dome stmctures, and in bedded anhydrite or gypsum evaporate basin formations combined sulfur in metal sulfide ores and mineral sulfates hydrogen sulfide in natural gas organic sulfur compounds in petroleum and tar sands and a combination of both pyritic and organic sulfur compounds in coal (qv). 

Occurrence. The metal sulfides, which are scattered throughout most of the world, have been an important source of elemental sulfur. The potential for recovery from metal sulfides exists, although these sources are less attractive economically and technologicaky than other sources of sulfur. Nevertheless sulfide ores are an important source of sulfur in other forms, such as sulfur dioxide and sulfuric acid. 

Some of the most important metal sulfides are pyrite [1309-36-0] EeS2 chalcopyrite [1308-56-1J, CuEeS2 pyrrhotite [1310-50-5] Ee sphalerite [12169-28-7] ZnS galena [12179-39-4] PbS arsenopyrite [1303-18-0] 2 pentlandite [53809-86-2] (Fe,Ni)2Sg. Sulfide deposits often occur in... 

Pyrite is the most abundant of the metal sulfides. Eor many years, until the Erasch process was developed, pyrite was the main source of sulfur and, for much of the first half of the twentieth century, comprised over 50% of world sulfur production. Pyrite reserves are distributed throughout the world and known deposits have been mined in about 30 countries. Possibly the largest pyrite reserves in the world are located in southern Spain, Portugal, and the CIS. Large deposits are also in Canada, Cypms, Einland, Italy, Japan, Norway, South Africa, Sweden, Turkey, the United States, and Yugoslavia. However, the three main regional producers of pyrites continue to be Western Europe Eastern Europe, including the CIS and China. 

Hydrometallurgical Processes. Recovery of sulfur in the processing of nonferrous metal sulfides has been in the form of SO2 and/or H2SO4 when smelter (pyrometallurgical) operations are employed. However, there have been accounts of processes, mainly hydrometallurgical, in which sulfur is recovered in the elemental form (see Metallurgy, extractive). 

The H2S sulfanes are the subject of several reviews (129,133). Except for hydrogen sulfide these have no practical utiUty. Sodium tetrasulfide [12034-39-8] is available commercially as a 40 wt % aqueous solution and is used to dehair hides in taimeries, as an ore flotation agent, in the preparation of sulfur dyes (qv), and for metal sulfide finishes (see Leather Mineral recovery and processing). 

This reaction is cataly2ed by silica, bauxite, and various metal sulfides. The usual catalyst is activated alumina, which also cataly2es the reduction by methane (228). Molybdenum compounds on alumina are especially effective catalysts for the hydrogen sulfide reaction (229). 

With hot metals, sulfur dioxide usually forms both metal sulfides as well as metal oxides. In aqueous solution, sulfur dioxide is reduced by certain metals or by borohydrides to dithionites. 

In general, plants using SO2 gas derived from metallic sulfides, spent acids, or gypsum anhydrite purify the gas stream before drying it by cold, ie, wet, gas purification. Various equipment combinations including humidification towers, reverse jet scmbbers, packed gas cooling towers, impingement tray columns and electrostatic precipitators are used to clean the gas. 

Like selenium, tellurium minerals, although widely disseminated, do not form ore bodies. Hence, there are no deposits that can be mined for tellurium alone, and there are no formally stated reserves. Large resources however, are present in the base-metal sulfide deposits mined for copper, nickel, gold, silver, and lead, where the recovery of tellurium, like that of selenium, is incidental. 

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