Selenium
Selenium is a chemical element with the atomic number 34 and the symbol Se, classified as a nonmetal in group 16 of the periodic table, known as the chalcogens.[1][2] It exists in several allotropic forms, including gray metallic, red crystalline, and amorphous red powder, with the gray form being the most stable under standard conditions.[1][2] Chemically similar to sulfur and tellurium, selenium has an atomic mass of 78.96 and plays essential roles in biological systems at trace levels while being toxic at higher concentrations.[1][2] Discovered in 1817 by Swedish chemist Jöns Jacob Berzelius while investigating residues from a sulfuric acid factory, selenium was named after the Greek word for moon, selene, due to its resemblance to tellurium (from Latin tellus, meaning earth).[3] Berzelius identified it as a new element after noting its distinct properties, such as emitting a garlic-like odor when burned, which aided in its identification and initial isolation from industrial residues in sulfuric acid production; it is now primarily obtained from copper refinery byproducts.[4] This discovery marked an early advancement in analytical chemistry, highlighting selenium's presence in industrial processes despite its rarity in Earth's crust at about 0.05 parts per million.[2] Physically, selenium has a density of 4.81 g/cm³ for its gray allotrope, a melting point of 221°C, and a boiling point of 685°C; it is unique among nonmetals for its semiconductor properties, conducting electricity better when exposed to light, which underpins its use in photocells.[1][2] Chemically, it exhibits oxidation states of -2, +4, and +6, reacting with halogens, oxygen to form selenium dioxide, and acids like concentrated nitric acid, but it is insoluble in water.[1] Selenium occurs naturally in over 40 minerals, often associated with sulfide ores, and is commercially produced as a byproduct of copper refining, with annual global output of approximately 3,700 tonnes (as of 2024) from major producers including China, Japan, the United States, Germany, and Canada.[2][5] Selenium's applications span electronics, where it is used in photovoltaic cells, rectifiers, and photocopiers due to its photoconductive qualities; the glass industry, for decolorizing and imparting red hues; and alloys, rubber vulcanization, and pigments.[2] In agriculture, sodium selenite supplements animal feeds to prevent deficiency-related diseases.[2] Biologically, selenium is an essential trace element incorporated into selenoproteins, which function as antioxidants, support thyroid hormone metabolism, DNA synthesis, reproduction, and immune response.[6] The recommended dietary allowance for adults is 55 micrograms per day, primarily obtained from seafood, meats, grains, and Brazil nuts, with deficiency linked to conditions like Keshan disease (a cardiomyopathy) and increased oxidative stress.[6] However, excessive intake above 400 micrograms per day can cause selenosis, characterized by hair and nail brittleness, gastrointestinal distress, and a garlic-like breath odor.[6][2] Environmentally, selenium bioaccumulates in aquatic ecosystems from industrial discharges, potentially leading to reproductive issues in wildlife at elevated levels.[2]Properties
Physical properties
Selenium exists in several allotropic forms, each exhibiting distinct physical characteristics. The most stable and common allotrope is gray selenium, which appears as a metallic, lustrous solid with a crystalline structure. Other forms include red (monoclinic or amorphous), black (vitreous amorphous), and yellow (amorphous powder), with the red and yellow variants being less stable and often prepared under specific conditions.[7][1] The density of gray selenium is 4.81 g/cm³ at room temperature, while the red form has a density of 4.39 g/cm³ and the black vitreous form 4.28 g/cm³. The melting point of the gray allotrope is 221 °C, and its boiling point is 685 °C; the red form melts at a similar 221 °C, but the black form softens around 180 °C before transitioning.[7][1] Gray selenium adopts a hexagonal crystal structure, consisting of helical chains of selenium atoms arranged in a trigonal lattice, which contributes to its metallic appearance and relative stability. In contrast, the red allotrope features a monoclinic structure, and the black form is amorphous without long-range order.[7][1] As a p-type semiconductor, gray selenium exhibits notable electrical conductivity that can increase by up to 1000 times upon exposure to light, a property known as photoconductivity. This behavior arises from its band gap of approximately 2 eV, allowing photoexcitation of electrons. Other allotropes, such as red and amorphous forms, are generally insulators.[7] Elemental selenium is insoluble in water and ethanol but dissolves in carbon disulfide (solubility of about 2 mg/100 mL) and concentrated sulfuric acid. It also shows solubility in concentrated nitric acid and certain organic solvents like ether.[7][1] The allotropes of selenium display varying stabilities, with the gray hexagonal form being thermodynamically the most stable at standard conditions. The red monoclinic and amorphous forms are metastable and undergo transitions to the gray phase upon heating: the vitreous black form converts around 180 °C, and the alpha red form above 120 °C. These transitions highlight the tendency toward the denser, more ordered hexagonal structure.[7][1]Chemical properties
Selenium is a chemical element with atomic number 34, positioned in group 16 of the periodic table, known as the chalcogens, and in period 4.[8][9] Its electron configuration is [Ar] 3d¹⁰ 4s² 4p⁴, which contributes to its semiconductor properties and variable valence.[8] The most common oxidation states of selenium are -2, +4, and +6, reflecting its ability to gain or lose electrons in various chemical environments.[8]/Descriptive_Chemistry/Elements_Organized_by_Group/Group_16:The_Oxygen_Family/Z034_Chemistry_of_Selenium(Z34)) As a nonmetal, selenium predominantly forms covalent bonds due to its moderate electronegativity of 2.55 on the Pauling scale, which is lower than that of oxygen (3.44) and slightly lower than sulfur (2.58).[10] This electronegativity influences its reactivity, making it less polar in bonds compared to oxygen but similar to sulfur in many respects. Selenium reacts with hydrogen to produce hydrogen selenide (H₂Se), a toxic, flammable gas, and with halogens such as chlorine or bromine to form tetrahalides like SeCl₄ or SeBr₄./Descriptive_Chemistry/Elements_Organized_by_Group/Group_16:The_Oxygen_Family/Z034_Chemistry_of_Selenium(Z34))[11] At elevated temperatures, selenium oxidizes in air to yield selenium dioxide (SeO₂), demonstrating its susceptibility to oxidation under thermal conditions.[11] Selenium exhibits amphoteric behavior, capable of acting as either an acid or a base depending on the reaction conditions, which is evident in the properties of its oxides./Descriptive_Chemistry/Elements_Organized_by_Group/Group_16:The_Oxygen_Family/Z034_Chemistry_of_Selenium(Z34)) It forms selenous acid (H₂SeO₃) upon reaction with water, a weaker acid than sulfuric acid, and selenic acid (H₂SeO₄), which is a strong, oxidizing acid analogous to sulfuric acid.[8][12] In redox chemistry, the standard reduction potential for the Se/Se²⁻ couple is approximately -0.92 V, indicating a lower tendency for selenium to form the selenide ion compared to sulfur (E° ≈ -0.48 V for S/S²⁻), which underscores selenium's greater stability in higher oxidation states. The reactivity of selenium is also influenced by its allotropes; for instance, the amorphous red form, often produced in reduction reactions, is more reactive than the stable gray hexagonal allotrope due to its disordered structure and higher surface area.[13]Isotopes
Selenium has six stable isotopes: ^{74}Se, ^{76}Se, ^{77}Se, ^{78}Se, ^{80}Se, and ^{82}Se. These occur in nature with the following approximate abundances: ^{74}Se at 0.89%, ^{76}Se at 9.37%, ^{77}Se at 7.63%, ^{78}Se at 23.77%, ^{80}Se at 49.61%, and ^{82}Se at 8.73%.[14]| Isotope | Mass Number | Natural Abundance (%) |
|---|---|---|
| ^{74}Se | 74 | 0.89 |
| ^{76}Se | 76 | 9.37 |
| ^{77}Se | 77 | 7.63 |
| ^{78}Se | 78 | 23.77 |
| ^{80}Se | 80 | 49.61 |
| ^{82}Se | 82 | 8.73 |