Selenium selenides

Sulfation Roasting. Acid roasting technology (Fig. 2) rehes on differences in the volatiUty of the tetravalent oxides of selenium and tellurium at roasting temperatures of 500—600°C to selectively volatilise selenium from slimes. Acid roasting uses sulfuric acid as the oxidant for the conversion of selenium/selenides and tellurium/teUurides to their respective tetravalent oxides. Typical oxidation reactions are as foUow ... 

Iron and Selenium—Selenides—Selenites—Selenates—Double Selenates. 

Se Se (general) Se, monoselenium >Se, selanediyl = Se, selanylidene selenoxo selenium selenide (general) Se -, selanidyl, selenide( l—) Se2-, selanediide, selenide(2—) selenide selenido (general) Se -, selanidyl, selenido( l—) Se2-, selanediido, selenido(2—)... 

Various benzoselenophenes 106 were successfully prepared using the Sni reaction at selenium. Selenides 104, readily prepared from the corresponding epoxides, react under standard radical conditions by homolytic substitution at selenium to the heterocycles 105. Water elimination finally provides the benzoselenophenes 106 in high yields (Equation 13.17) [165, 166]. In analogy, Te-containing heterocycles can also be prepared [166, 167]. 

A range of oxides, phosphates, carbonates and elemental nanoparticles can be produced. Of special interest to nanotechnologists are the enzymatically controlled redox changes that result in biomineral formation which are linked to microbial respiration such as dissimilatory metal reduction. This latter process has been shown, for instance, to produce Ag(0) nanoparticles 5-40 pm in size ° (Fig. 2), selenium/selenide/telluride nanospheres and rods (Figs. 3 and 4), Au(0), Pd(0) " as well as Tc(IV) and U(IV) (see also for recent reviews). 

Selenium and tellurium react similarly, forming selenides and selenates(IV), and tellurides and tellurates(IV) respectively. Like the sulphide ion, S , the ions Se and Te form polyanions but to a much lesser extent. 

Hydrogen selenide (selenium hydride), HjSe, and hydrogen telluride (tellurium hydride), HjTe... 

These closely resemble the corresponding sulphides. The alkali metal selenides and tellurides are colourless solids, and are powerful reducing agents in aqueous solution, being oxidised by air to the elements selenium and tellurium respeetively (cf. the reducing power of the hydrides). 

Elemental selenium has been said to be practically nontoxic and is considered to be an essential trace element however, hydrogen selenide and other selenium compounds are extremely toxic, and resemble arsenic in their physiological reactions. 

Hydrogen selenide in a concentration of 1.5 ppm is intolerable to man. Selenium occurs in some solid in amounts sufficient to produce serious effects on animals feeding on plants, such as locoweed, grown in such soils. Exposure to selenium compounds (as Se) in air should not exceed 0.2 mg/m3 (8-hour time-weighted average - 40-hour week). 

Selenium heterocycles receive far less mention in the literature than do such homologs as oxazole, thiazole, or imidazole. In fact, preparative methods of selenium heterocycles are much more limited than for the other series, mainly because of manipulatory difficulties arising from the toxicity of selenium (hydrogen selenide is even more toxic) that can produce severe damage to the skin, lungs, kidneys, and eyes. Another source of difficulty is the reactivity of the heterocycle itself, which can easily undergo fission, depending on the reaction medium and the nature of the substituents. 

Selenium is an essential element and is beneficial at low concentrations, serving as an antioxidant. Lack of selenium affects thyroid function, and selenium deficiencies have been linked to Keshan Disease (34). Selenium at high levels, however, is toxic. Hydrogen selenide (which is used in semiconductor manufacturing) is extremely toxic, affecting the mucous membranes and respiratory system. However, the toxicity of most organ oselenium compounds used as donor compounds for organic semiconductors is not weU studied. 

Selenium occurs in the slimes as intermetallic compounds such as copper silver selenide [12040-91 -4], CuAgSe disilver selenide [1302-09-6], Ag2Se and Cu2 Se [20405-64-5], where x < 1. The primary purpose of slimes treatment is the recovery of the precious metals gold, silver, platinum, palladium, and rhodium. The recovery of selenium is a secondary concern. Because of the complexity and variabiUty of slimes composition throughout the world, a number of processes have been developed to recover both the precious metals and selenium. More recently, the emphasis has switched to the development of processes which result in early recovery of the higher value precious metals. Selenium and tellurium are released in the later stages. Processes in use at the primary copper refineries are described in detail elsewhere (25—44). 

Wet chlorination is performed by sparging slimes slurried either in water or hydrochloric acid using chlorine gas, or other oxidants such as sodium chlorate or hydrogen peroxide which Hberate chlorine from hydrochloric acid, at about 100°C. Under these conditions, selenium and selenides rapidly oxidize and dissolve. 

Inorganic Compounds. Inorganic selenium compounds are similar to those of sulfur and tellurium. The most important inorganic compounds are the selenides, haUdes, oxides, and oxyacids. Selenium oxidation states are —2, 0, +1, +2, +4, and +6. Detailed descriptions of the compounds, techniques, and methods of preparation, and references to original work are available (1—3,5,6—10, 51—54). Some important physical properties of inorganic selenium compounds are Hsted in Table 3. 

Selenides. Selenium forms compounds with most elements. Biaary compounds of selenium with 58 metals and 8 nonmetals, and alloys with three other elements have been described (55). Most of the selenides can be prepared by a direct reaction. This reaction varies from very vigorous with alkah metals to sluggish and requiring high temperature with hydrogen. 

Bina Selenides. Most biaary selenides are formed by beating selenium ia the presence of the element, reduction of selenites or selenates with carbon or hydrogen, and double decomposition of heavy-metal salts ia aqueous solution or suspension with a soluble selenide salt, eg, Na2Se or (NH 2S [66455-76-3]. Atmospheric oxygen oxidizes the selenides more rapidly than the corresponding sulfides and more slowly than the teUurides. Selenides of the alkah, alkaline-earth metals, and lanthanum elements are water soluble and readily hydrolyzed. Heavy-metal selenides are iasoluble ia water. Polyselenides form when selenium reacts with alkah metals dissolved ia hquid ammonia. Metal (M) hydrogen selenides of the M HSe type are known. Some heavy-metal selenides show important and useful electric, photoelectric, photo-optical, and semiconductor properties. Ferroselenium and nickel selenide are made by sintering a mixture of selenium and metal powder. 

Organ oselenium compounds, such as phosphine selenides, are being evaluated in solvent extraction systems for silver and gold (63). Also, potential pharmaceuticals containing selenium have been prepared (64). 

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