Reactive nonmetal
Selenium is a chemical element; it has symbol Se and atomic number 34. It has various physical appearances, including a brick-red powder, a vitreous black solid, and a grey metallic-looking form. It seldom occurs in this elemental state or as pure ore compounds in Earth's crust. Selenium (from σελήνη 'moon') was discovered in 1817 by Jöns Jacob Berzelius, who noted the similarity of the new element to the previously discovered tellurium (named for the Earth).
Selenium is found in metal sulfide ores, where it substitutes for sulfur. Commercially, selenium is produced as a byproduct in the refining of these ores. Minerals that are pure selenide or selenate compounds are rare. The chief commercial uses for selenium today are glassmaking and pigments. Selenium is a semiconductor and is used in photocells. Applications in electronics, once important, have been mostly replaced with silicon semiconductor devices. Selenium is still used in a few types of DC power surge protectors and one type of fluorescent quantum dot.
Although trace amounts of selenium are necessary for cellular function in many animals, including humans, both elemental selenium and (especially) selenium salts are toxic in even small doses, causing selenosis. Symptoms include (in decreasing order of frequency): diarrhea, fatigue, hair loss, joint pain, nail brittleness or discoloration, nausea, headache, tingling, vomiting, and fever. …
Selenium (from Greek σελήνη, selene, meaning 'Moon') was discovered in 1817 by Jöns Jacob Berzelius and Johan Gottlieb Gahn. Both chemists owned a chemistry plant near Gripsholm, Sweden, producing sulfuric acid by the lead chamber process. Pyrite samples from the Falun Mine produced a red solid precipitate in the lead chambers, which was presumed to be an arsenic compound, so the use of pyrite to make acid was discontinued. Berzelius and Gahn, who wanted to use the pyrite, observed that the red precipitate gave off an odor like horseradish when burned. This smell was not typical of arsenic, but a similar odor was known from tellurium compounds. Hence, Berzelius's first letter to Alexander Marcet stated that this was a tellurium compound. However, the lack of tellurium compounds in the Falun Mine minerals eventually led Berzelius to reanalyze the red precipitate, and in 1818 he wrote a second letter to Marcet describing a newly found element similar to sulfur and tellurium. Because of its similarity to tellurium, named for the Earth, Berzelius named the new element after the Moon.
In 1873, Willoughby Smith found that the electrical conductivity of grey selenium was affected by light. This led to its use as a cell for sensing light. The first commercial products using selenium were developed by Werner Siemens in the mid-1870s. The selenium cell was used in the photophone developed by Alexander Graham Bell in 1879. …
Selenium forms several allotropes that interconvert with temperature changes, depending somewhat on the rate of temperature change. When prepared in chemical reactions, selenium is usually an amorphous, brick-red powder. When rapidly melted, it forms the black, vitreous form, usually sold commercially as beads. The structure of black selenium is irregular and complex and consists of polymeric rings with up to 1000 atoms per ring. Black selenium is a brittle, lustrous solid that is slightly soluble in CS2. Upon heating, it softens at 50 °C and converts to gray selenium at 180 °C; the transformation temperature is reduced by presence of halogens and amines.
The red α, β, and γ forms are produced from solutions of black selenium by varying the evaporation rate of the solvent (usually CS2). They all have a relatively low, monoclinic crystal symmetry (space group 14) and contain nearly identical puckered cyclooctaselenium (Se8) rings as in sulfur. The eight atoms of a ring are not equivalent (i.e. they are not mapped one onto another by any symmetry operation), and in fact in the γ-monoclinic form, half the rings are in one configuration (and its mirror image) and half in another. The packing is most dense in the α form. In the Se8 rings, the Se–Se distance varies depending on where the pair of atoms is in the ring, but the average is 233.5 pm, and the Se–Se–Se angle is on average 105.7°. Other selenium allotropes may contain Se6 or Se7 rings. …
Native (i.e., elemental) selenium is a rare mineral, which does not usually form good crystals, but, when it does, they are steep rhombohedra or tiny acicular (hair-like) crystals. Isolation of selenium is often complicated by the presence of other compounds and elements.
Selenium occurs naturally in a number of inorganic forms, including selenide, selenate, and selenite, but these minerals are rare. The common mineral selenite is not a selenium mineral, and contains no selenite ion, but is rather a type of gypsum (calcium sulfate hydrate) named like selenium for the moon well before the discovery of selenium. Selenium is most commonly found as an impurity, replacing a small part of the sulfur in sulfide ores of many metals.
In living systems, selenium is found in the amino acids selenomethionine, selenocysteine, and methylselenocysteine. In these compounds, selenium plays a role analogous to that of sulfur. Another naturally occurring organoselenium compound is dimethyl selenide.
Certain soils are selenium-rich, and selenium can be bioconcentrated by some plants. In soils, selenium most often occurs in soluble forms such as selenate (analogous to sulfate), which are leached into rivers very easily by runoff. Ocean water contains significant amounts of selenium.
Typical background concentrations of selenium do not exceed 1 ng/m3 in the atmosphere; 1 mg/kg in soil and vegetation and 0.5 μg/L in freshwater and seawater, 0.05 - 0.09 mg/kg average crustal abundance. …
During the electrowinning of manganese, the addition of selenium dioxide decreases the power necessary to operate the electrolysis cells. China is the largest consumer of selenium dioxide for this purpose. For every tonne of manganese, an average 2 kg selenium oxide is used.
The largest commercial use of selenium, accounting for about 50% of consumption, is for the production of glass. Selenium compounds confer a red color to glass. This color cancels out the green or yellow tints that arise from iron impurities typical for most glass. For this purpose, various selenite and selenate salts are added. For other applications, a red color may be desired, produced by mixtures of CdSe and CdS.
Selenium is used with bismuth in brasses to replace more toxic lead. The regulation of lead in drinking water applications such as in the US with the Safe Drinking Water Act of 1974, made a reduction of lead in brass necessary. The new brass is marketed under the name EnviroBrass. Like lead and sulfur, selenium improves the machinability of steel at concentrations around 0.15%. Selenium produces the same machinability improvement in copper alloys.
The lithium–selenium (Li–Se) battery was considered for energy storage in the family of lithium batteries in the 2010s.
Selenium was used as the photoabsorbing layer in the first solid-state solar cell, which was demonstrated by the English physicist William Grylls Adams and his student Richard Evans Day in 1876. …
Selenium has seven naturally occurring isotopes. Five of these, 74Se, 76Se, 77Se, 78Se, 80Se, are stable, with 80Se being the most abundant (49.6% natural abundance). Also naturally occurring is the long-lived primordial radionuclide 82Se, with a half-life of 8.76×1019 years. The non-primordial radioisotope 79Se also occurs in minute quantities in uranium ores as a product of nuclear fission. Selenium also has numerous unstable synthetic isotopes ranging from 64Se to 95Se; the most stable are 75Se with a half-life of 119.78 days and 72Se with a half-life of 8.4 days. Isotopes lighter than the stable isotopes primarily undergo beta plus decay to isotopes of arsenic, and isotopes heavier than the stable isotopes undergo beta minus decay to isotopes of bromine, with some minor neutron emission branches in the heaviest known isotopes.
Although it is toxic in large doses, selenium is an essential micronutrient for animals. In plants, it occurs as a bystander mineral, sometimes in toxic proportions in forage (some plants may accumulate selenium as a defense against being eaten by animals, but other plants, such as locoweed, require selenium, and their growth indicates the presence of selenium in soil). The selenium content in the human body is believed to be in the range of 13–20 mg.
Selenium is a component of the unusual amino acids selenocysteine and selenomethionine. In humans, selenium is a trace element nutrient that functions as cofactor for reduction of antioxidant enzymes, such as glutathione peroxidases and certain forms of thioredoxin reductase found in animals and some plants (this enzyme occurs in all living organisms, but not all forms of it in plants require selenium).
The glutathione peroxidase family of enzymes (GSH-Px) catalyze reactions that remove reactive oxygen species such as hydrogen peroxide and organic hydroperoxides.
The thyroid gland and every cell that uses thyroid hormone also use selenium, which is a cofactor for the three of the four known types of thyroid hormone deiodinases, which activate and then deactivate various thyroid hormones and their metabolites; the iodothyronine deiodinases are the subfamily of deiodinase enzymes that use selenium as the otherwise rare amino acid selenocysteine. …