Metal elemental selenium

Sulphur is less reactive than oxygen but still quite a reactive element and when heated it combines directly with the non-metallic elements, oxygen, hydrogen, the halogens (except iodine), carbon and phosphorus, and also with many metals to give sulphides. Selenium and tellurium are less reactive than sulphur but when heated combine directly with many metals and non-metals. 

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). 

Selenium and precious metals can be removed selectively from the chlorination Hquor by reduction with sulfur dioxide. However, conditions of acidity, temperature, and a rate of reduction must be carefliUy controlled to avoid the formation of selenium monochloride, which reacts with elemental selenium already generated to form a tar-like substance. This tar gradually hardens to form an intractable mass which must be chipped from the reactor. Under proper conditions of precipitation, a selenium/precious metals product substantially free of other impurities can be obtained. Selenium can be recovered in a pure state by vacuum distillation, leaving behind a precious metals residue. 

Since tire alkali and alkaline metals have such a high affinity for oxygen, sulphur aird selenium they are potentially useful for the removal of these iron-metallic elements from liquid metals with a lower affinity for these elements. Since the hairdling of these Group I and II elements is hazardous on the industrial scale, their production by molten salt electrolysis during metal rehning is an attractive alternative. Ward and Hoar (1961) obtained almost complete removal of sulphur, selenium and tellurium from liquid copper by the electrolysis of molten BaCla between tire metal which functioned as the cathode, and a graphite anode. 

Biological activity can be used in two ways for the bioremediation of metal-contaminated soils to immobilize the contaminants in situ or to remove them permanently from the soil matrix, depending on the properties of the reduced elements. Chromium and uranium are typical candidates for in situ immobilization processes. The bioreduction of Cr(VI) and Ur(VI) transforms highly soluble ions such as CrO and UO + to insoluble solid compounds, such as Cr(OH)3 and U02. The selenate anions SeO are also reduced to insoluble elemental selenium Se°. Bioprecipitation of heavy metals, such as Pb, Cd, and Zn, in the form of sulfides, is another in situ immobilization option that exploits the metabolic activity of sulfate-reducing bacteria without altering the valence state of metals. The removal of contaminants from the soil matrix is the most appropriate remediation strategy when bioreduction results in species that are more soluble compared to the initial oxidized element. This is the case for As(V) and Pu(IV), which are transformed to the more soluble As(III) and Pu(III) forms. This treatment option presupposes an installation for the efficient recovery and treatment of the aqueous phase containing the solubilized contaminants. 

Inorganic elements can be broadly classified as metals and nonmetals. Most metallic elements become toxic at some concentration. Nine elements (arsenic, barium, cadmium, chromium, lead, mercury, nickel, selenium, and thallium) and cyanide are defined as hazardous inorganics for the purposes of deep-well injection. 

For the preparation of secondary and tertiary selenoamides, several methods have been used reaction of lithium alkyneselenolates (obtained using metallic selenium) with amines, aromatic diselenoic acid Se-methyl esters with amines or dihalomethane with elemental selenium, NaH and amines (Scheme 83).258 266... 

An unconventional preparation of nickel diphenyldiselenophosphinate, Ni(Se2 PPh2)2, involves oxidation by elemental selenium of Ni(PPh2)2, obtained in turn by electrochemical oxidation of nickel metal in acetonitrile solutions of PhzPH.449... 

Consider the proper placement of tellurium and iodine in the periodic table, as shown in Figure 1-3. Te has the heavier atomic weight. The chemical properties of tellurium are like those of selenium because both are semi-metallic elements that form compounds like those of sulfur. Iodine resembles bromine because these elements are nonmetallic halogens that form compounds like those of chlorine. Therefore, the order in the table cannot be based solely on atomic weight. 

Toxicity Variable. The hydrides of phosphorus, arsenic, sulfur, selenium, tellurium and boron which are highly toxic, produce local irritation and destroy red blood cells. They are particularly dangerous because of their volatility and ease of entry into the body. The hydrides of the alkali metals, alkaline earths, aluminum, zirconium and titanium react with moisture to evolve hydrogen and leave behind the hydroxide of the metallic element. This hydroxide is usually caustic. See also sodium hydroxide... 

The next five chapters deal with deposition of specific groups of semiconductors. In Chapter 4, II-VI Semiconductors, all the sulphides, selenides, and (what little there is on) tellurides of cadmium (most of the chapter), zinc (a substantial part), and mercury (a small part). (Oxides are left to a later chapter.) This chapter is, understandably, a large one, due mainly to the large amount of work carried out on CdS and to a lesser extent on CdSe. Chapter 5, PbS and PbSe, provides a separate forum for PbS and PbSe, which provided much of the focus for CD in earlier years. The remaining sulphides and selenides are covered in Chapter 6, Other Sulphides and Selenides. There are many of these compounds, thus, this is a correspondingly large chapter. Chapter 7, Oxides and Other Semiconductors, is devoted mainly to oxides and some hydroxides, as well as to miscellaneous semiconductors that have only been scantily studied (elemental selenium and silver halides). These previous chapters have been limited to binary semiconductors, made up of two elements (with the exception of elemental Se). Chapter 8, Ternary Semiconductors, extends this list to semiconductors composed of three elements, whether two different metals (most of the studies) or two different chalcogens. 

The selenides may also be obtained by direct combination of the elements, either by passing selenium vapour over the heated metal in a vacuum or by heating the metal with selenium in a crucible, the reaction being started by means of a magnesium fuse.3 In the case of potassium the reaction is explosive. The compounds may also be obtained by the action of hydrogen selenide on the heated metal,4 on the heated metallic chloride or its vapour, preferably in the presence of nitrogen,5 or by reduction with hydrogen or carbon of an oxysalt such as a selenite.6 Selenides have also been prepared by electrolytic methods.7... 

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