Zinc

context: Zinc is a chemical element with symbol Zn and atomic number 30. It is the first element of group 12 of the periodic table. In some respects zinc is chemically similar to magnesium: its ion is of similar size and its only common oxidation state is +2. Zinc is the 24th most abundant element in Earth's crust and has five stable isotopes. The most common zinc ore is sphalerite (zinc blende), a zinc sulfide mineral. The largest mineable amounts are found in Australia, Asia, and the United States. Zinc production includes froth flotation of the ore, roasting, and final extraction using electricity (electrowinning).

context: Brass, which is an alloy of copper and zinc, has been used since at least the 10th century BC in Judea and by the 7th century BC in Ancient Greece. Zinc metal was not produced on a large scale until the 12th century in India and was unknown to Europe until the end of the 16th century. The mines of Rajasthan have given definite evidence of zinc production going back to the 6th century BC. To date, the oldest evidence of pure zinc comes from Zawar, in Rajasthan, as early as the 9th century AD when a distillation process was employed to make pure zinc. Alchemists burned zinc in air to form what they called "philosopher's wool" or "white snow".

context: The element was probably named by the alchemist Paracelsus after the German word Zinke (prong, tooth). German chemist Andreas Sigismund Marggraf is credited with discovering pure metallic zinc in 1746. Work by Luigi Galvani and Alessandro Volta uncovered the electrochemical properties of zinc by 1800. Corrosion-resistant zinc plating of iron (hot-dip galvanizing) is the major application for zinc. Other applications are in batteries, small non-structural castings, and alloys, such as brass. A variety of zinc compounds are commonly used, such as zinc carbonate and zinc gluconate (as dietary supplements), zinc chloride (in deodorants), zinc pyrithione (anti-dandruff shampoos), zinc sulfide (in luminescent paints), and zinc methyl or zinc diethyl in the organic laboratory.

context: Zinc is an essential mineral perceived by the public today as being of "exceptional biologic and public health importance", especially regarding prenatal and postnatal development. Zinc deficiency affects about two billion people in the developing world and is associated with many diseases. In children it causes growth retardation, delayed sexual maturation, infection susceptibility, and diarrhea. Enzymes with a zinc atom in the reactive center are widespread in biochemistry, such as alcohol dehydrogenase in humans. Consumption of excess zinc can cause ataxia, lethargy and copper deficiency.

context: Zinc is a bluish-white, lustrous, diamagnetic metal, though most common commercial grades of the metal have a dull finish. It is somewhat less dense than iron and has a hexagonal crystal structure, with a distorted form of hexagonal close packing, in which each atom has six nearest neighbors (at 265.9 pm) in its own plane and six others at a greater distance of 290.6 pm. The metal is hard and brittle at most temperatures but becomes malleable between 100 and 150 °C. Above 210 °C, the metal becomes brittle again and can be pulverized by beating. Zinc is a fair conductor of electricity. For a metal, zinc has relatively low melting (419.5 °C) and boiling points (907 °C). Its melting point is the lowest of all the transition metals aside from mercury and cadmium.

context: Several dozen radioisotopes have been characterized. 65Zn, which has a half-life of 243.66 days, is the most long-lived radioisotope, followed by 72Zn with a half-life of 46.5 hours. Zinc has 10 nuclear isomers. 69mZn has the longest half-life, 13.76 h. The superscript m indicates a metastable isotope. The nucleus of a metastable isotope is in an excited state and will return to the ground state by emitting a photon in the form of a gamma ray. 61Zn has three excited states and 73Zn has two. The isotopes 65Zn, 71Zn, 77Zn and 78Zn each have only one excited state.

context: The chemistry of zinc is dominated by the +2 oxidation state. When compounds in this oxidation state are formed the outer shell s electrons are lost, which yields a bare zinc ion with the electronic configuration [Ar]3d10. In aqueous solution an octahedral complex, [Zn(H
2O)6]2+ is the predominant species. The volatilization of zinc in combination with zinc chloride at temperatures above 285 °C indicates the formation of Zn
2Cl
2, a zinc compound with a +1 oxidation state. No compounds of zinc in oxidation states other than +1 or +2 are known. Calculations indicate that a zinc compound with the oxidation state of +4 is unlikely to exist.

context: Zinc chemistry is similar to the chemistry of the late first-row transition metals nickel and copper, though it has a filled d-shell, so its compounds are diamagnetic and mostly colorless. The ionic radii of zinc and magnesium happen to be nearly identical. Because of this some of their salts have the same crystal structure and in circumstances where ionic radius is a determining factor zinc and magnesium chemistries have much in common. Otherwise there is little similarity. Zinc tends to form bonds with a greater degree of covalency and it forms much more stable complexes with N- and S- donors. Complexes of zinc are mostly 4- or 6- coordinate although 5-coordinate complexes are known.

context: Zinc(I) compounds are rare, and require bulky ligands to stabilize the low oxidation state. Most zinc(I) compounds contain formally the [Zn2]2+ core, which is analogous to the [Hg2]2+ dimeric cation present in mercury(I) compounds. The diamagnetic nature of the ion confirms its dimeric structure. The first zinc(I) compound containing the Zn—Zn bond, (η5-C5Me5)2Zn2, is also the first dimetallocene. The [Zn2]2+ ion rapidly disproportionates into zinc metal and zinc(II), and has only been obtained as a yellow glass formed by cooling a solution of metallic zinc in molten ZnCl2.

context: Binary compounds of zinc are known for most of the metalloids and all the nonmetals except the noble gases. The oxide ZnO is a white powder that is nearly insoluble in neutral aqueous solutions, but is amphoteric, dissolving in both strong basic and acidic solutions. The other chalcogenides (ZnS, ZnSe, and ZnTe) have varied applications in electronics and optics. Pnictogenides (Zn
3N
2, Zn
3P
2, Zn
3As
2 and Zn
3Sb
2), the peroxide (ZnO
2), the hydride (ZnH
2), and the carbide (ZnC
2) are also known. Of the four halides, ZnF
2 has the most ionic character, whereas the others (ZnCl
2, ZnBr
2, and ZnI
2) have relatively low melting points and are considered to have more covalent character.

context: In weak basic solutions containing Zn2+ ions, the hydroxide Zn(OH)
2 forms as a white precipitate. In stronger alkaline solutions, this hydroxide is dissolved to form zincates ([Zn(OH)4]2−). The nitrate Zn(NO3)
2, chlorate Zn(ClO3)
2, sulfate ZnSO
4, phosphate Zn
3(PO4)
2, molybdate ZnMoO
4, cyanide Zn(CN)
2, arsenite Zn(AsO2)
2, arsenate Zn(AsO4)
2·8H
2O and the chromate ZnCrO
4 (one of the few colored zinc compounds) are a few examples of other common inorganic compounds of zinc. One of the simplest examples of an organic compound of zinc is the acetate (Zn(O
2CCH3)
2).

context: The Charaka Samhita, thought to have been written between 300 and 500 AD, mentions a metal which, when oxidized, produces pushpanjan, thought to be zinc oxide. Zinc mines at Zawar, near Udaipur in India, have been active since the Mauryan period. The smelting of metallic zinc here, however, appears to have begun around the 12th century AD. One estimate is that this location produced an estimated million tonnes of metallic zinc and zinc oxide from the 12th to 16th centuries. Another estimate gives a total production of 60,000 tonnes of metallic zinc over this period. The Rasaratna Samuccaya, written in approximately the 13th century AD, mentions two types of zinc-containing ores: one used for metal extraction and another used for medicinal purposes.

context: The name of the metal was probably first documented by Paracelsus, a Swiss-born German alchemist, who referred to the metal as "zincum" or "zinken" in his book Liber Mineralium II, in the 16th century. The word is probably derived from the German zinke, and supposedly meant "tooth-like, pointed or jagged" (metallic zinc crystals have a needle-like appearance). Zink could also imply "tin-like" because of its relation to German zinn meaning tin. Yet another possibility is that the word is derived from the Persian word سنگ seng meaning stone. The metal was also called Indian tin, tutanego, calamine, and spinter.

context: William Champion's brother, John, patented a process in 1758 for calcining zinc sulfide into an oxide usable in the retort process. Prior to this, only calamine could be used to produce zinc. In 1798, Johann Christian Ruberg improved on the smelting process by building the first horizontal retort smelter. Jean-Jacques Daniel Dony built a different kind of horizontal zinc smelter in Belgium, which processed even more zinc. Italian doctor Luigi Galvani discovered in 1780 that connecting the spinal cord of a freshly dissected frog to an iron rail attached by a brass hook caused the frog's leg to twitch. He incorrectly thought he had discovered an ability of nerves and muscles to create electricity and called the effect "animal electricity". The galvanic cell and the process of galvanization were both named for Luigi Galvani and these discoveries paved the way for electrical batteries, galvanization and cathodic protection.

context: Zinc metal is produced using extractive metallurgy. After grinding the ore, froth flotation, which selectively separates minerals from gangue by taking advantage of differences in their hydrophobicity, is used to get an ore concentrate. This concentrate consists of about 50% zinc with the rest being sulfur (32%), iron (13%), and SiO
2 (5%). The composition of this is normally zinc sulfide (80% to 85%), iron sulfide (7.0% to 12%), lead sulfide (3.0% to 5.0%) silica (2.5% to 3.5%), and cadmium sulfide (0.35% to 0.41%).

context: The production for sulfidic zinc ores produces large amounts of sulfur dioxide and cadmium vapor. Smelter slag and other residues of process also contain significant amounts of heavy metals. About 1.1 million tonnes of metallic zinc and 130 thousand tonnes of lead were mined and smelted in the Belgian towns of La Calamine and Plombières between 1806 and 1882. The dumps of the past mining operations leach significant amounts of zinc and cadmium, and, as a result, the sediments of the Geul River contain significant amounts of heavy metals. About two thousand years ago emissions of zinc from mining and smelting totaled 10 thousand tonnes a year. After increasing 10-fold from 1850, zinc emissions peaked at 3.4 million tonnes per year in the 1980s and declined to 2.7 million tonnes in the 1990s, although a 2005 study of the Arctic troposphere found that the concentrations there did not reflect the decline. Anthropogenic and natural emissions occur at a ratio of 20 to 1.

context: Zinc is more reactive than iron or steel and thus will attract almost all local oxidation until it completely corrodes away. A protective surface layer of oxide and carbonate (Zn
5(OH)
6(CO
3)
2) forms as the zinc corrodes. This protection lasts even after the zinc layer is scratched but degrades through time as the zinc corrodes away. The zinc is applied electrochemically or as molten zinc by hot-dip galvanizing or spraying. Galvanization is used on chain-link fencing, guard rails, suspension bridges, lightposts, metal roofs, heat exchangers, and car bodies.

context: The relative reactivity of zinc and its ability to attract oxidation to itself makes it an efficient sacrificial anode in cathodic protection (CP). For example, cathodic protection of a buried pipeline can be achieved by connecting anodes made from zinc to the pipe. Zinc acts as the anode (negative terminus) by slowly corroding away as it passes electric current to the steel pipeline.[note 2] Zinc is also used to cathodically protect metals that are exposed to sea water from corrosion. A zinc disc attached to a ship's iron rudder will slowly corrode, whereas the rudder stays unattacked. Other similar uses include a plug of zinc attached to a propeller or the metal protective guard for the keel of the ship.

context: Other widely used alloys that contain zinc include nickel silver, typewriter metal, soft and aluminium solder, and commercial bronze. Zinc is also used in contemporary pipe organs as a substitute for the traditional lead/tin alloy in pipes. Alloys of 85–88% zinc, 4–10% copper, and 2–8% aluminium find limited use in certain types of machine bearings. Zinc is the primary metal used in making American one cent coins since 1982. The zinc core is coated with a thin layer of copper to give the impression of a copper coin. In 1994, 33,200 tonnes (36,600 short tons) of zinc were used to produce 13.6 billion pennies in the United States.

context: Alloys of primarily zinc with small amounts of copper, aluminium, and magnesium are useful in die casting as well as spin casting, especially in the automotive, electrical, and hardware industries. These alloys are marketed under the name Zamak. An example of this is zinc aluminium. The low melting point together with the low viscosity of the alloy makes the production of small and intricate shapes possible. The low working temperature leads to rapid cooling of the cast products and therefore fast assembly is possible. Another alloy, marketed under the brand name Prestal, contains 78% zinc and 22% aluminium and is reported to be nearly as strong as steel but as malleable as plastic. This superplasticity of the alloy allows it to be molded using die casts made of ceramics and cement.

context: Similar alloys with the addition of a small amount of lead can be cold-rolled into sheets. An alloy of 96% zinc and 4% aluminium is used to make stamping dies for low production run applications for which ferrous metal dies would be too expensive. In building facades, roofs or other applications in which zinc is used as sheet metal and for methods such as deep drawing, roll forming or bending, zinc alloys with titanium and copper are used. Unalloyed zinc is too brittle for these kinds of manufacturing processes.

context: Roughly one quarter of all zinc output in the United States (2009), is consumed in the form of zinc compounds; a variety of which are used industrially. Zinc oxide is widely used as a white pigment in paints, and as a catalyst in the manufacture of rubber. It is also used as a heat disperser for the rubber and acts to protect its polymers from ultraviolet radiation (the same UV protection is conferred to plastics containing zinc oxide). The semiconductor properties of zinc oxide make it useful in varistors and photocopying products. The zinc zinc-oxide cycle is a two step thermochemical process based on zinc and zinc oxide for hydrogen production.

context: Zinc chloride is often added to lumber as a fire retardant and can be used as a wood preservative. It is also used to make other chemicals. Zinc methyl (Zn(CH3)
2) is used in a number of organic syntheses. Zinc sulfide (ZnS) is used in luminescent pigments such as on the hands of clocks, X-ray and television screens, and luminous paints. Crystals of ZnS are used in lasers that operate in the mid-infrared part of the spectrum. Zinc sulfate is a chemical in dyes and pigments. Zinc pyrithione is used in antifouling paints.

context: 64Zn, the most abundant isotope of zinc, is very susceptible to neutron activation, being transmuted into the highly radioactive 65Zn, which has a half-life of 244 days and produces intense gamma radiation. Because of this, Zinc Oxide used in nuclear reactors as an anti-corrosion agent is depleted of 64Zn before use, this is called depleted zinc oxide. For the same reason, zinc has been proposed as a salting material for nuclear weapons (cobalt is another, better-known salting material). A jacket of isotopically enriched 64Zn would be irradiated by the intense high-energy neutron flux from an exploding thermonuclear weapon, forming a large amount of 65Zn significantly increasing the radioactivity of the weapon's fallout. Such a weapon is not known to have ever been built, tested, or used. 65Zn is also used as a tracer to study how alloys that contain zinc wear out, or the path and the role of zinc in organisms.

context: Zinc is included in most single tablet over-the-counter daily vitamin and mineral supplements. Preparations include zinc oxide, zinc acetate, and zinc gluconate. It is believed to possess antioxidant properties, which may protect against accelerated aging of the skin and muscles of the body; studies differ as to its effectiveness. Zinc also helps speed up the healing process after an injury. It is also suspected of being beneficial to the body's immune system. Indeed, zinc deficiency may have effects on virtually all parts of the human immune system.

context: Although not yet tested as a therapy in humans, a growing body of evidence indicates that zinc may preferentially kill prostate cancer cells. Because zinc naturally homes to the prostate and because the prostate is accessible with relatively non-invasive procedures, its potential as a chemotherapeutic agent in this type of cancer has shown promise. However, other studies have demonstrated that chronic use of zinc supplements in excess of the recommended dosage may actually increase the chance of developing prostate cancer, also likely due to the natural buildup of this heavy metal in the prostate.

context: There are many important organozinc compounds. Organozinc chemistry is the science of organozinc compounds describing their physical properties, synthesis and reactions. Among important applications is the Frankland-Duppa Reaction in which an oxalate ester(ROCOCOOR) reacts with an alkyl halide R'X, zinc and hydrochloric acid to the α-hydroxycarboxylic esters RR'COHCOOR, the Reformatskii reaction which converts α-halo-esters and aldehydes to β-hydroxy-esters, the Simmons–Smith reaction in which the carbenoid (iodomethyl)zinc iodide reacts with alkene(or alkyne) and converts them to cyclopropane, the Addition reaction of organozinc compounds to carbonyl compounds. The Barbier reaction (1899) is the zinc equivalent of the magnesium Grignard reaction and is better of the two. In presence of just about any water the formation of the organomagnesium halide will fail, whereas the Barbier reaction can even take place in water. On the downside organozincs are much less nucleophilic than Grignards, are expensive and difficult to handle. Commercially available diorganozinc compounds are dimethylzinc, diethylzinc and diphenylzinc. In one study the active organozinc compound is obtained from much cheaper organobromine precursors:

context: Zinc serves a purely structural role in zinc fingers, twists and clusters. Zinc fingers form parts of some transcription factors, which are proteins that recognize DNA base sequences during the replication and transcription of DNA. Each of the nine or ten Zn2+ ions in a zinc finger helps maintain the finger's structure by coordinately binding to four amino acids in the transcription factor. The transcription factor wraps around the DNA helix and uses its fingers to accurately bind to the DNA sequence.

context: Other sources include fortified food and dietary supplements, which come in various forms. A 1998 review concluded that zinc oxide, one of the most common supplements in the United States, and zinc carbonate are nearly insoluble and poorly absorbed in the body. This review cited studies which found low plasma zinc concentrations after zinc oxide and zinc carbonate were consumed compared with those seen after consumption of zinc acetate and sulfate salts. However, harmful excessive supplementation is a problem among the relatively affluent, and should probably not exceed 20 mg/day in healthy people, although the U.S. National Research Council set a Tolerable Upper Intake of 40 mg/day.

context: For fortification, however, a 2003 review recommended zinc oxide in cereals as cheap, stable, and as easily absorbed as more expensive forms. A 2005 study found that various compounds of zinc, including oxide and sulfate, did not show statistically significant differences in absorption when added as fortificants to maize tortillas. A 1987 study found that zinc picolinate was better absorbed than zinc gluconate or zinc citrate. However, a study published in 2008 determined that zinc glycinate is the best absorbed of the four dietary supplement types available.

context: Symptoms of mild zinc deficiency are diverse. Clinical outcomes include depressed growth, diarrhea, impotence and delayed sexual maturation, alopecia, eye and skin lesions, impaired appetite, altered cognition, impaired host defense properties, defects in carbohydrate utilization, and reproductive teratogenesis. Mild zinc deficiency depresses immunity, although excessive zinc does also. Animals with a diet deficient in zinc require twice as much food in order to attain the same weight gain as animals given sufficient zinc.

context: Despite some concerns, western vegetarians and vegans have not been found to suffer from overt zinc deficiencies any more than meat-eaters. Major plant sources of zinc include cooked dried beans, sea vegetables, fortified cereals, soyfoods, nuts, peas, and seeds. However, phytates in many whole-grains and fiber in many foods may interfere with zinc absorption and marginal zinc intake has poorly understood effects. The zinc chelator phytate, found in seeds and cereal bran, can contribute to zinc malabsorption. There is some evidence to suggest that more than the US RDA (15 mg) of zinc daily may be needed in those whose diet is high in phytates, such as some vegetarians. These considerations must be balanced against the fact that there is a paucity of adequate zinc biomarkers, and the most widely used indicator, plasma zinc, has poor sensitivity and specificity. Diagnosing zinc deficiency is a persistent challenge.

context: Nearly two billion people in the developing world are deficient in zinc. In children it causes an increase in infection and diarrhea, contributing to the death of about 800,000 children worldwide per year. The World Health Organization advocates zinc supplementation for severe malnutrition and diarrhea. Zinc supplements help prevent disease and reduce mortality, especially among children with low birth weight or stunted growth. However, zinc supplements should not be administered alone, because many in the developing world have several deficiencies, and zinc interacts with other micronutrients.

context: Zinc deficiency is crop plants' most common micronutrient deficiency; it is particularly common in high-pH soils. Zinc-deficient soil is cultivated in the cropland of about half of Turkey and India, a third of China, and most of Western Australia, and substantial responses to zinc fertilization have been reported in these areas. Plants that grow in soils that are zinc-deficient are more susceptible to disease. Zinc is primarily added to the soil through the weathering of rocks, but humans have added zinc through fossil fuel combustion, mine waste, phosphate fertilizers, pesticide (zinc phosphide), limestone, manure, sewage sludge, and particles from galvanized surfaces. Excess zinc is toxic to plants, although zinc toxicity is far less widespread.

context: There is evidence of induced copper deficiency in those taking 100–300 mg of zinc daily. A 2007 trial observed that elderly men taking 80 mg daily were hospitalized for urinary complications more often than those taking a placebo. The USDA RDA is 11 and 8 mg Zn/day for men and women, respectively. Levels of 100–300 mg may interfere with the utilization of copper and iron or adversely affect cholesterol. Levels of zinc in excess of 500 ppm in soil interfere with the ability of plants to absorb other essential metals, such as iron and manganese. There is also a condition called the zinc shakes or "zinc chills" that can be induced by the inhalation of freshly formed zinc oxide formed during the welding of galvanized materials. Zinc is a common ingredient of denture cream which may contain between 17 and 38 mg of zinc per gram. There have been claims of disability, and even death, due to excessive use of these products.

context: The U.S. Food and Drug Administration (FDA) has stated that zinc damages nerve receptors in the nose, which can cause anosmia. Reports of anosmia were also observed in the 1930s when zinc preparations were used in a failed attempt to prevent polio infections. On June 16, 2009, the FDA said that consumers should stop using zinc-based intranasal cold products and ordered their removal from store shelves. The FDA said the loss of smell can be life-threatening because people with impaired smell cannot detect leaking gas or smoke and cannot tell if food has spoiled before they eat it. Recent research suggests that the topical antimicrobial zinc pyrithione is a potent heat shock response inducer that may impair genomic integrity with induction of PARP-dependent energy crisis in cultured human keratinocytes and melanocytes.

context: In 1982, the US Mint began minting pennies coated in copper but made primarily of zinc. With the new zinc pennies, there is the potential for zinc toxicosis, which can be fatal. One reported case of chronic ingestion of 425 pennies (over 1 kg of zinc) resulted in death due to gastrointestinal bacterial and fungal sepsis, whereas another patient, who ingested 12 grams of zinc, only showed lethargy and ataxia (gross lack of coordination of muscle movements). Several other cases have been reported of humans suffering zinc intoxication by the ingestion of zinc coins.

context: Pennies and other small coins are sometimes ingested by dogs, resulting in the need for medical treatment to remove the foreign body. The zinc content of some coins can cause zinc toxicity, which is commonly fatal in dogs, where it causes a severe hemolytic anemia, and also liver or kidney damage; vomiting and diarrhea are possible symptoms. Zinc is highly toxic in parrots and poisoning can often be fatal. The consumption of fruit juices stored in galvanized cans has resulted in mass parrot poisonings with zinc.