Selenium, elemental

The procedure for the selection of data for selenium has been the following  

A complete set of thermodynamic data for the polymorphs of solid selenium, the liquid, and the gas molecules Se (g), = 1 to 8, was derived in the review by Mills [74MIL]. This work has been a valuable source of information, but several important later studies have appeared. A compilation of data for the equilibrium between liquid selenium and saturated selenium vapour was made by Rao [82RAO]. The work was mainly based on the contribution by Rau [74RAU] and the selection of data sources was limited. 

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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. 

It is apparent from these equations that significant quantities of sulfur dioxide are generated. For selenium, the reaction shown for oxidation of elemental selenium reverses itself at the lower temperatures employed for water scmbbing, thus regenerating sulfuric acid. The tellurium dioxide remains in the sulfated slimes. 

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. 

Comprehensive accounts of the various gravimetric, polarographic, spectrophotometric, and neutron activation analytical methods have been pubHshed (1,2,5,17,19,65—67). Sampling and analysis of biological materials and organic compounds is treated in References 60 and 68. Many analytical methods depend on the conversion of selenium in the sample to selenous acid, H2Se02, and reduction to elemental selenium when a gravimetric deterrnination is desired. 

A number of substances, such as the most commonly used sulfur dioxide, can reduce selenous acid solution to an elemental selenium precipitate. This precipitation separates the selenium from most elements and serves as a basis for gravimetry. In a solution containing both selenous and teUurous acids, the selenium may be quantitatively separated from the latter by performing the reduction in a solution which is 8 to 9.5 W with respect to hydrochloric acid. When selenic acid may also be present, the addition of hydroxylamine hydrochloride is recommended along with the sulfur dioxide. A simple method for the separation and deterrnination of selenium(IV) and molybdenum(VI) in mixtures, based on selective precipitation with potassium thiocarbonate, has been developed (69). 

A widely used procedure for determining trace amounts of selenium involves separating selenium from solution by reduction to elemental selenium using tellurium (as a carrier) and hypophosphorous acid as reductant. The precipitated selenium, together with the carrier, are collected by filtration and the filtered soflds examined directly in the wavelength-dispersive x-ray fluorescence spectrometer (70). Numerous spectrophotometric and other methods have been pubHshed for the deterruination of trace amounts of selenium (71—88). 

Contact with elemental selenium does not injure the skin. Selenium dioxide, however, upon contact with water, sweat, or tears, forms selenous acid, a severe skin irritant. Selenium oxyhaHdes are extremely vesicant and cause bums when in contact with human skin (91,92). Hydrogen selenide affects the mucous membranes of the upper respiratory tract and the eyes (93). 

The fumes from the roaster are passed through a train of water-spray scmbbers and an electrostatic precipitator. In the scmbber, selenium dioxide [7446-08-4] reacts with sulfur dioxide (eq. 37) to produce elemental selenium, which is purified to provide a commercial product. 

Sulfur diamides (diaminosulfanes) are obtained by the action of sulfur chlorides with an aliphatic secondary amine (Eq. 10.10). ° The monoselanes Se(NR2)2 (R = Me, Et) have also been prepared. Polyselanes Scx(NR2)2 (x = 2 - 4, NR2 = morpholinyl x = 4, NR2 = piperidinyl) are formed in the reaction of elemental selenium with the boiling amine in the presence of Pb304. ... 

In the various editions of his textbook, and in the publications dealing specifically with his predictions, Mendeleev repeatedly gives the example of calculating the atomic weight of the element selenium, a value that was known at the time and which could thus be used to test the reliability of his method. 

FIGURE 15.13 Two of the Croup 16/VI elements selenium, which is a nonmelal, on the left and tellurium, a metalloid, on the right. 

Selenic acid, H2Se04, is a strong acid (/fai 2) and the solubility of its salts parallels that of the corresponding sulfates. It is formed by the oxidation of selenous acid or elemental selenium with strong oxidizing agents in the presence of water. Telluric acid, H2Te04, or tellurates are obtained by oxidation of tellurides,... 

Elemental sulfur dissolves in boiling aqueous sodium sulfite solutions with the formation of sodium thiosulfate (Na2S203). The reaction proceeds quantitatively if sulfur and excess sodium sulfite are boiled for some time in weakly alkaline solutions. In the cold, however, practically no reaction occurs. Alternatively, thiosulfate can be produced quantitatively in solution phase by using organic solvents to first dissolve sulfur and then accomplish the reaction with aqueous sulfite. In a parallel reaction, elemental selenium dissolves in alkaline sulfite solution to produce selenosulfate, SeSO ... 

The value of this method lies in the fact that formation of elemental selenium is unlikely to occur since the high-valency species such as Se(IV) that could oxidize the selenide ions are absent from solution. The SeSO and SOj ions (or their protonated forms) do not oxidize Se , while any free Se that may be formed would redissolve in sulfite giving selenosulfate again, since the latter is prepared by dissolving Se in excess sulfite. 

Although the sulfur-gold bond has been most investigated, the Group 16 elements selenium and tellurium have also attracted attention and are discussed in detail here (polonium has not received attention due to its radioactivity). 

When a compound that can form several modifications crystallizes, first a modification may form that is thermodynamically unstable under the given conditions afterwards it converts to the more stable form (Ostwald step rule). Selenium is an example when elemental selenium forms by a chemical reaction in solution, it precipitates in a red modification that consists of Se8 molecules this then converts slowly into the stable, gray form that consists of polymeric chain molecules. Potassium nitrate is another example at room temperature J3-KN03 is stable, but above 128 °C a-KNOs is stable. From an aqueous solution at room temperature a-KN03 crystallizes first, then, after a short while or when triggered by the slightest mechanical stress, it transforms to )3-KN03. 

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. 

Many selenium compounds can be reduced to produce elemental selenium when exposed to organic matter in subsurface environment. 

The formation of silaneselone 57 was evidenced by the trapping reaction with mesitonitrile oxide leading to the corresponding cycloadduct 58 and was also supported by the observation of a remarkably downfield 29Si chemical shift (8Si = 174) indicative of the Si=Se double bond of 57. Although this direct selenation of silylene 55 with an equimolar amount of selenium was not reproducible, the use of excess amount of elemental selenium resulted in the formation of a new cyclic diselenide, diselenasilirane 59, as a stable compound (8Si = -44 and... 

Fig. 3.7 Jons Jacob Berzelius (1779-1848), professor of chemistry in Stockholm and discoverer of the elements selenium, silicon, thorium and zirconium. He introduced the modem chemical symbols and also the term organic chemistry . From the book Berzelius, Europaresendren by C. G. Bernhard with kind permission of the Royal Swedish Academy of Sciences...

Losi M.E., Frankenberger W.T. Microbial oxidation and solubilization of precipitated elemental selenium in soil. J Environ Qual 1998 27 836-843. 

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