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Selenium: The Lunar Element Unveiled

An academic exploration of the chemical element Selenium (Se), atomic number 34, delving into its multifaceted nature from allotropes to biological roles.

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Introduction

Elemental Identity

Selenium, designated by the symbol Se and atomic number 34, is a chemical element exhibiting diverse physical forms, including a brick-red powder, a vitreous black solid, and a grey metallic-like allotrope. It is seldom found in its pure elemental state or as primary ore compounds within the Earth's crust. Its discovery in 1817 by Jรถns Jacob Berzelius was prompted by its similarity to tellurium, leading to its naming after the Greek word for the Moon, 'selene'.

Occurrence and Origin

Selenium primarily occurs as a substituent within metal sulfide ores, where it replaces sulfur. Commercially, it is recovered as a byproduct during the refining of these ores. Pure selenide or selenate minerals are notably rare. Its presence in the environment, particularly in soils, can significantly influence plant life, with some species accumulating it to potentially toxic levels.

Scientific Significance

While trace amounts of selenium are vital for cellular functions in many organisms, including humans, both elemental selenium and its salts can exhibit toxicity even at low doses. Its unique semiconductor properties have historically been crucial in electronics and photocells, though silicon has largely superseded it in many applications. Its biological role as a component of essential enzymes underscores its complex nature.

Properties

Allotropes and Appearance

Selenium exists in several allotropic forms that interconvert based on temperature. Chemically prepared selenium typically appears as an amorphous, brick-red powder. When melted and rapidly cooled, it forms a black, vitreous solid. The grey, hexagonal crystalline form is the most stable and dense allotrope, characterized by helical polymeric chains. This grey form exhibits semiconductor properties and notable photoconductivity.

Physical Characteristics

Key physical properties include a melting point of 494 K (220.85 ยฐC) and a boiling point of 958 K (685 ยฐC). The density varies among its allotropes, with the grey form being the densest at 4.81 g/cmยณ. Selenium exhibits diamagnetism and possesses moderate thermal conductivity. Its mechanical properties, such as Young's modulus and hardness, are characteristic of a brittle nonmetal.

Electronic Behavior

Selenium's status as a semiconductor is central to many of its applications. Its electrical conductivity is sensitive to light (photoconductivity), a property first observed in the grey allotrope. This characteristic paved the way for its use in early photocells and light-sensing devices. The specific band structure and electron mobility contribute to its utility in photoconductive applications like X-ray detectors.

Isotopes

Natural Abundance

Selenium possesses seven naturally occurring isotopes. Five of theseโ€”74Se, 76Se, 77Se, 78Se, and 80Seโ€”are stable. Among these, 80Se is the most abundant, constituting approximately 49.6% of natural selenium. The primordial radionuclide 82Se is also naturally present, albeit in trace amounts, with an exceptionally long half-life.

Radioisotopes and Decay

Beyond the stable isotopes, selenium has numerous synthetic radioisotopes, ranging from 64Se to 95Se. The most significant radioisotope, 79Se, has a half-life measured in hundreds of thousands of years and decays via beta-minus emission. 75Se, with a half-life of approximately 119.78 days, is also notable. Isotopes lighter than the stable ones typically decay via beta-plus emission, while heavier isotopes undergo beta-minus decay.

Isotope Abundance (%) Half-life Decay Mode Product
74Se0.86Stable--
76Se9.23Stable--
77Se7.60Stable--
78Se23.7Stable--
79SeTrace3.27ร—105 yฮฒ-79Br
80Se49.8Stable--
82Se8.828.76ร—1019 y2ฮฒ-82Kr

Compounds

Oxidation States and Analogies

Selenium commonly exhibits oxidation states of -2, +2, +4, and +6. As a nonmetal, bordering on metalloid, its chemical behavior is intermediate between sulfur and tellurium, sharing similarities with arsenic. This positions it uniquely within the chalcogen group.

Oxides and Acids

Selenium forms two primary oxides: selenium dioxide (SeO2) and the less stable selenium trioxide (SeO3). Combustion of elemental selenium yields SeO2, which dissolves in water to form selenous acid (H2SeO3). Selenous acid can also be synthesized directly. Selenium trioxide decomposes readily into the dioxide and oxygen above 185 ยฐC.

Halides and Selenides

Stable selenium halides include selenium tetrachloride (SeCl4) and selenium monochloride (Se2Cl2), analogous to their sulfur counterparts. Selenium hexafluoride (SeF6) is more reactive and toxic than sulfur hexafluoride. Selenium readily forms selenides with metals, such as zinc selenide (ZnSe) and lead selenide (PbSe), which are important semiconductors. It also forms polyselenides, characterized by chains of selenium atoms.

Organoselenium Chemistry

Selenium forms a variety of organoselenium compounds analogous to organosulfur compounds. These include selenides (R2Se), diselenides (R2Se2), and selenols (RSeH). Notably, selenocysteine and selenomethionine are biologically significant amino acids containing selenium. However, compounds like selenoketones are rarely observed due to chemical principles related to double bond stability.

History

Discovery and Naming

Discovered in 1817 by Jรถns Jacob Berzelius and Johan Gottlieb Gahn during their work with sulfuric acid production, selenium's unique properties, including a distinct odor reminiscent of tellurium compounds, led Berzelius to name it after the Moon ('selene' in Greek), reflecting its connection to tellurium (named for Earth).

Early Applications

Willoughby Smith's 1873 discovery of selenium's photoconductivity marked a significant milestone. This property enabled its use in early light-sensing devices, such as Alexander Graham Bell's photophone. Selenium rectifiers, developed in the 1930s, were important electronic components until largely replaced by silicon devices.

Biological Recognition

Selenium's biological significance emerged later. Initial observations in microorganisms in 1954 hinted at its essentiality, which was confirmed for mammalian life in 1957. Subsequent research identified selenium as a crucial component of vital enzymes like glutathione peroxidase and thioredoxin reductase, and its role in thyroid hormone metabolism was elucidated.

Occurrence

Geological Presence

Native selenium is a rare mineral, typically found in small, acicular crystals. Its isolation is often complicated by its association with other elements. Selenium is most commonly found as a trace impurity, substituting for sulfur in various metal sulfide ores. Minerals containing pure selenide or selenate are uncommon.

Biological Systems

In living organisms, selenium is incorporated into amino acids such as selenocysteine and selenomethionine, analogous to sulfur's role. Certain plants act as indicators of selenium-rich soils, accumulating the element, sometimes to levels toxic to grazing animals. Ocean water also contains significant concentrations of selenium.

Environmental Distribution

Typical background concentrations in the atmosphere, soil, and water are generally low. However, anthropogenic activities, including coal combustion and the mining and smelting of sulfide ores, contribute to environmental selenium levels. Soluble forms like selenate can leach into waterways, potentially causing pollution issues.

Production

Primary Sources

The principal source of commercial selenium is its recovery as a byproduct from the refining of sulfide ores, particularly those of copper, nickel, and lead. Electrolytic copper refining yields significant amounts of selenium from anode muds. Historically, sulfuric acid production also yielded selenium from lead chamber process residues.

Refining Processes

Industrial production typically involves extracting selenium dioxide from copper refinery residues. This is often achieved through oxidation with sodium carbonate, followed by acidification to form selenous acid. Subsequent reduction of selenous acid, commonly using sulfur dioxide, precipitates elemental selenium.

Global Output

Global selenium production is concentrated in specific countries, with Germany, Japan, Belgium, and Russia being major producers. Consumption patterns vary, with significant use in metallurgy, glass manufacturing, agriculture, and electronics. China stands out as a dominant consumer, particularly for manganese electrolysis applications.

Applications

Glass and Pigments

The largest commercial application of selenium is in glass manufacturing, where its compounds impart a red color, effectively neutralizing green tints caused by iron impurities. Selenium compounds are also used to produce vibrant red pigments.

Metallurgy and Alloys

Selenium enhances the machinability of steel and copper alloys, similar to lead and sulfur. It is also used in brass alloys (e.g., EnviroBrass) as a less toxic alternative to lead, particularly in applications related to drinking water systems.

Electronics and Energy

Historically vital for photocells, light meters, and early solar cells, selenium's photoconductive properties remain relevant in modern X-ray detectors. While silicon has largely replaced it in solar cells, research continues into selenium-based tandem cells. Selenium rectifiers still find niche use in surge protection.

Emerging Technologies

Lithium-selenium batteries have been explored for energy storage applications. Furthermore, cadmium selenide (CdSe) is utilized in the production of quantum dots, highlighting selenium's role in advanced materials science.

Biological Role

Essential Micronutrient

Selenium is an essential trace element for animal life, functioning as a critical cofactor for antioxidant enzymes such as glutathione peroxidases and thioredoxin reductases. These enzymes play vital roles in cellular redox balance and protection against oxidative damage.

Thyroid Function

In conjunction with iodine, selenium is integral to thyroid health. It serves as a cofactor for deiodinase enzymes, which regulate the activation and inactivation of thyroid hormones. Selenium deficiency, particularly when combined with other stressors, is being investigated for its potential link to thyroid disorders like Hashimoto's disease.

Nutritional Sources

Dietary selenium is obtained from sources like meat, nuts (especially Brazil nuts, which are exceptionally rich), cereals, and mushrooms. The Recommended Dietary Allowance (RDA) for adults is 55 micrograms per day. Selenium is available in various supplement forms, including multivitamins.

Toxicity

Selenosis and Symptoms

Ingestion of excessive selenium, particularly from highly bioavailable forms like selenates and selenites, can lead to selenosis. Symptoms range from garlic breath, gastrointestinal issues, hair loss, and nail changes to neurological damage and, in severe cases, liver cirrhosis or pulmonary edema. The Tolerable Upper Intake Level is established at 400 micrograms per day.

Hazard Classification

Under the Globally Harmonized System (GHS), elemental selenium is classified as toxic if swallowed or inhaled (H301+H331), suspected of damaging fertility or the unborn child (H361), and causing damage to organs through prolonged or repeated exposure (H372). It may also cause long-lasting harmful effects to aquatic life (H413).

Occupational Exposure

Occupational Safety and Health Administration (OSHA) has set permissible exposure limits for selenium in the workplace. Prolonged exposure to airborne selenium dust or fumes requires careful monitoring and control measures to prevent adverse health effects.

Pollution

Sources of Contamination

Selenium pollution can arise from agricultural runoff, particularly in arid regions where soluble selenium compounds leach into waterways. Industrial processes, including coal combustion, mining, smelting, and crude oil processing, also contribute to environmental selenium levels.

Aquatic Ecosystem Impacts

Elevated selenium concentrations in aquatic environments can be detrimental, causing developmental abnormalities and mortality in fish and waterbirds. Bioaccumulation occurs along the food chain, leading to significantly higher concentrations in organisms than in the surrounding water. Certain thresholds are considered highly hazardous to aquatic life.

Health Implications

While fish consumption is generally beneficial, high selenium levels in fish can pose risks. Selenium poisoning can lead to physiological changes in fish, including respiratory impairment and reproductive issues. The interaction between selenium and methylmercury can amplify toxicity in aquatic species.

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References

References

  1.  http://weppi.gtk.fi/publ/foregsatlas/text/Se.pdf
  2.  R. Baselt, Disposition of Toxic Drugs and Chemicals in Man, 8th edition, Biomedical Publications, Foster City, CA, 2008, pp. 1416รขย€ย“1420.
A full list of references for this article are available at the Selenium Wikipedia page

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Important Notice

This document was generated by an AI model and is intended for educational and informational purposes only. The content is derived from publicly available data and has been refined for clarity and academic tone, suitable for higher education students. While efforts have been made to ensure accuracy based on the provided source material, completeness and current applicability cannot be guaranteed.

This is not professional advice. The information presented here does not constitute chemical, medical, or safety consultation. Users should consult official documentation and qualified professionals for any specific applications or concerns related to selenium, including its handling, toxicity, and biological interactions. Reliance on the information provided herein is solely at the user's own risk.

The creators of this page are not liable for any errors, omissions, or consequences arising from the use of this information.