Zinc, or spelter (which may also refer to zinc alloys), is a metallic chemical element; it has the symbol Zn and atomic number 30. It is the first element in group 12 of the periodic table. Zinc is, in some respects, chemically similar to magnesium, because its ion is of similar size and its only common oxidation state is +2Sony VPCCA3SFX/R battery. Zinc is the 24th most abundant element in the 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) Sony VPCCA3S1E battery.
Brass, which is an alloy of copper and zinc, has been used since at least the 10th century BC. Impure zinc metal was not produced in large scale until the 13th century in India, while the metal was unknown to Europe until the end of the 16th century. Alchemists burned zinc in air to form what they called “philosopher’s wool” or “white snow”Sony VPCCA3E1E battery.
The element was probably named by the alchemist Paracelsus after the German word Zinke. German chemist Andreas Sigismund Marggraf is normally given credit for 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 steel (hot-dip galvanizing) is the major application for zincSony VPCCA38EC/R battery. Other applications are in batteries 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 laboratorySony VPCCA38EC battery.
Zinc is an essential mineral of “exceptional biologic and public health importance”.[1] Zinc deficiency affects about two billion people in the developing world and is associated with many diseases.[2] In children it causes growth retardation, delayed sexual maturation, infection susceptibility, and diarrhea, contributing to the death of about 800,000 children worldwide per year. Sony VPCCA37EC/B battery 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.
Characteristics
Physical properties
Zinc, also referred to in nonscientific contexts as spelter,[3] is a bluish-white, lustrous, diamagnetic metal,[4] though most common commercial grades of the metal have a dull finish.[5] It is somewhat less dense than iron and has a hexagonal crystal structure. Sony VPCCA37EC battery
The metal is hard and brittle at most temperatures but becomes malleable between 100 and 150 °C.[4][5] Above 210 °C, the metal becomes brittle again and can be pulverized by beating.[7] Zinc is a fair conductor of electricity.[4] For a metal, zinc has relatively low melting (419.5 °C, 787.1 F) and boiling points (907 °C).[8] Its melting point is the lowest of all the transition metals aside from mercury and cadmium. Sony VPCCA36FW/W battery
Many alloys contain zinc, including brass, an alloy of zinc and copper. Other metals long known to form binary alloys with zinc are aluminium, antimony, bismuth, gold, iron, lead, mercury, silver, tin, magnesium, cobalt, nickel, tellurium and sodium.[9] While neither zinc nor zirconium are ferromagnetic, their alloy ZrZn2 exhibits ferromagnetism below 35 K. Sony VPCCA36FW/B battery
[edit]Occurrence
See also: Zinc minerals
Zinc makes up about 75 ppm (0.0075%) of the Earth’s crust, making it the 24th most abundant element. Soil contains 5–770 ppm of zinc with an average of 64 ppm. Seawater has only 30 ppb zinc and the atmosphere contains 0.1–4 µg/m3.
Sphalerite (ZnS)
The element is normally found in association with other base metals such as copper and lead in ores.[11] Zinc is a chalcophile, meaning the element has a low affinity for oxides and prefers to bond with sulfidesSony VPCCA36FH/W battery. Chalcophiles formed as the crust solidified under the reducing conditions of the early Earth’s atmosphere.[12] Sphalerite, which is a form of zinc sulfide, is the most heavily mined zinc-containing ore because its concentrate contains 60–62% zinc.[11]
Other minerals, from which zinc is extracted, include smithsonite (zinc carbonate), hemimorphite (zinc silicate), wurtzite (another zinc sulfide), and sometimes hydrozincite (basic zinc carbonate). Sony VPCCA36FG/B battery With the exception of wurtzite, all these other minerals were formed as a result of weathering processes on the primordial zinc sulfides.[12]
Identified world zinc resources total about 1.9 billion tonnes.[14] Large deposits are in Australia, Canada and the United States with the largest reserves in Iran. At the current rate of consumption, these reserves are estimated to be depleted sometime between 2027 and 2055. Sony VPCCA36FA/B battery About 346 million tonnes have been extracted throughout history to 2002, and one estimate found that about 109 million tonnes of that remains in use.[19]
Isotopes
Main article: Isotopes of zinc
Five isotopes of zinc occur in nature. 64Zn is the most abundant isotope (48.63% natural abundance).[20] This isotope has such a long half-life, at 4.3×1018 a,[21] that its radioactivity can be ignored.[22] Similarly, 70Zn (0.6%), with a half-life of 1.3×1016 a is not usually considered to be radioactive. The other isotopes found in nature are 66Zn (28%), 67Zn (4%) and 68Zn (19%)Sony VPCCA36EC/W battery.
Several dozen radioisotopes have been characterized. 65Zn, which has a half-life of 243.66 days, is the most long-lived isotope, followed by 72Zn with a half-life of 46.5 hours.[20] Zinc has 10 nuclear isomers. 69mZn has the longest half-life, 13.76 h.[20] 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 raySony VPCCA36EC battery. 61Zn has three excited states and 73Zn has two.[23] The isotopes 65Zn, 71Zn, 77Zn and 78Zn each have only one excited state.[20]
The most common decay mode of a radioisotope of zinc with a mass number lower than 66 is electron capture. The decay product resulting from electron capture is an isotope of copper.[20]
The most common decay mode of a radioisotope of zinc with mass number higher than 66 is beta decay (β–), which produces an isotope of gallium. Sony VPCCA35FW/W battery
Compounds and chemistry
Main article: Compounds of zinc
Reactivity
Zinc has an electron configuration of [Ar]3d104s2 and is a member of the group 12 of the periodic table. It is a moderately reactive metal and strong reducing agent.[24] The surface of the pure metal tarnishes quickly, eventually forming a protective passivating layer of the basic zinc carbonate, Zn5(OH)6(CO3)2, by reaction with atmospheric carbon dioxide.[25] This layer helps prevent further reaction with air and waterSony VPCCA35FW/B battery.
Zinc burns in air with a bright bluish-green flame, giving off fumes of zinc oxide.[26] Zinc reacts readily with acids, alkalis and other non-metals.[27] Extremely pure zinc reacts only slowly at room temperature with acids.[26] Strong acids, such as hydrochloric or sulfuric acid, can remove the passivating layer and subsequent reaction with water releases hydrogen gas. Sony VPCCA35FN/R battery
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.[28] This allows for the formation of four covalent bonds by accepting four electron pairs and thus obeying the octet ruleSony VPCCA35FH/D battery. The stereochemistry is therefore tetrahedral and the bonds may be described as being formed from sp3 hybrid orbitals on the zinc ion.[29] In aqueous solution an octahedral complex, [Zn(H2O)6]2+ is the predominant species.[30] The volatilization of zinc in combination with zinc chloride at temperatures above 285 °C indicates the formation of Zn2Cl2, a zinc compound with a +1 oxidation state. Sony VPCCA35FG/PI battery No compounds of zinc in oxidation states other than +1 or +2 are known.[31] Calculations indicate that a zinc compound with the oxidation state of +4 is unlikely to exist.[32]
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.[33] The ionic radii of zinc and magnesium happen to be nearly identical. Because of this some of their salts have the same crystal structureSony VPCCA35FF/P battery and in circumstances where ionic radius is a determining factor zinc and magnesium chemistries have much in common.[26] 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.[33] Complexes of zinc are mostly 4- or 6- coordinate although 5-coordinate complexes are known. Sony VPCCA35FA/PI battery
See also Clemmensen reduction.
Compounds
Zinc acetate
Zinc chloride
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.[26] The other chalcogenides (ZnS, ZnSe, and ZnTe) have varied applications in electronics and optics. Sony VPCCA2Z0E battery Pnictogenides (Zn3N2, Zn3P2, Zn3As2 and Zn3Sb2), the peroxide (ZnO2), the hydride (ZnH2), and the carbide (ZnC2) are also known.[38] Of the four halides, ZnF2 has the most ionic character, whereas the others (ZnCl2, ZnBr2, and ZnI2) have relatively low melting points and are considered to have more covalent character.[39]
In weak basic solutions containing Zn2+ ions, the hydroxide Zn(OH)2 forms as a white precipitate. In stronger alkaline solutionsSony VPCCA2SFX/R battery, this hydroxide is dissolved to form zincates ([Zn(OH)4]2−).[26] The nitrate Zn(NO3)2, chlorate Zn(ClO3)2, sulfate ZnSO4, phosphate Zn3(PO4)2, molybdate ZnMoO4, cyanide Zn(CN)2, arsenite Zn(AsO2)2, arsenate Zn(AsO4)2·8H2O and the chromate ZnCrO4 (one of the few colored zinc compounds) are a few examples of other common inorganic compounds of zinc.[40][41] One of the simplest examples of an organic compound of zinc is the acetate (Zn(O2CCH3)2) Sony VPCCA2S1E battery.
Organozinc compounds are those that contain zinc–carbon covalent bonds. Diethylzinc ((C2H5)2Zn) is a reagent in synthetic chemistry. It was first reported in 1848 from the reaction of zinc and ethyl iodide, and was the first compound known to contain a metal–carbon sigma bond.[42] Decamethyldizincocene contains a strong zinc–zinc bond at room temperature. Sony VPCCA2S0E battery
History
Ancient use
Late Roman brass bucket – the Hemmoorer Eimer from Warstade, Germany, second to third century AD
Various isolated examples of the use of impure zinc in ancient times have been discovered. A possibly prehistoric statuette containing 87.5% zinc was found in a Dacian archaeological site in Transylvania (modern Romania).[44] Ornaments made of alloys that contain 80–90% zinc with lead, iron, antimonySony VPCCA2AJ battery, and other metals making up the remainder, have been found that are 2500 years old.[11] The Berne zinc tablet is a votive plaque dating to Roman Gaul made of an alloy that is mostly zinc.[45] Also, some ancient writings appear to mention zinc. The Greek historian Strabo, in a passage taken from an earlier writer of the 4th century BC, mentions “drops of false silver”, which when mixed with copper make brass. This may refer to small quantities of zinc by-product of smelting sulfide oresSony VPCCA1S3C/CN1 battery.[46] The Charaka Samhita, thought to have been written in 500 BC or before, mentions a metal which, when oxidized, produces pushpanjan, thought to be zinc oxide.[47]
Zinc ores were used to make the zinc–copper alloy brass many centuries prior to the discovery of zinc as a separate element. Palestinian brass from the 14th to 10th centuries BC contains 23% zinc.[48] The Book of Genesis, written between the 10th and 5th centuries BC,[49] mentions (in the King James translation) Sony VPCCA1S2C/CN1 battery Tubal-cain as an “instructor of every artificer in brass and iron” (Genesis 4:22), but since the word nechosheth, translated as “brass”, also means “copper”, the significance of this is not clear. Knowledge of how to produce brass spread to Ancient Greece by the 7th century BC but few varieties were made.[50]
The manufacture of brass was known to the Romans by about 30 BC.[51] They made brass by heating powdered calamine (zinc silicate or carbonate) Sony VPCCA1S1E/W battery, charcoal and copper together in a crucible.[51] The resulting calamine brass was then either cast or hammered into shape and was used in weaponry.[52] Some coins struck by Romans in the Christian era are made of what is probably calamine brass.[53] In the West, impure zinc was known from antiquity to exist in the remnants in melting ovens, but it was usually discarded, as it was thought to be worthless. Sony VPCCA1S1E/P battery
Zinc mines at Zawar, near Udaipur in India, have been active since the Mauryan period in the late 1st millennium BC. The smelting of metallic zinc here however appears to have begun around the 12th century AD.[55][56] One estimate is that this location produced an estimated million tonnes of metallic zinc and zinc oxide from the 12th to 16th centuries.[13] Another estimate gives a total production of 60,000 tonnes of metallic zinc over this periodSony VPCCA1S1E/G battery.[55] The Rasaratna Samuccaya, written in approximately the 14th century AD, mentions two types of zinc-containing ores; one used for metal extraction and another used for medicinal purposes.[56]
[edit]Early studies and naming
Zinc was distinctly recognized as a metal under the designation of Fasada in the medical Lexicon ascribed to the Hindu king Madanapala and written about the year 1374.[57] Smelting and extraction of impure zinc by reducing calamine with wool and other organic substances was accomplished in the 13th century in India. Sony VPCCA1S1E/D battery The Chinese did not learn of the technique until the 17th century.
Various alchemical symbols attributed to the element zinc
Alchemists burned zinc metal in air and collected the resulting zinc oxide on a condenser. Some alchemists called this zinc oxide lana philosophica, Latin for “philosopher’s wool”, because it collected in wooly tufts while others thought it looked like white snow and named it nix album. Sony VPCCA1S1E/B battery
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.[58][60] 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). Sony VPCCA1S1E battery Zink could also imply “tin-like” because of its relation to German zinn meaning tin.[62] Yet another possibility is that the word is derived from the Persian word سنگ seng meaning stone.[63] The metal was also called Indian tin, tutanego, calamine, and spinter.[11]
German metallurgist Andreas Libavius received a quantity of what he called “calay” of Malabar from a cargo ship captured from the Portuguese in 1596.[64] Libavius described the properties of the sample, which may have been zinc. Zinc was regularly imported to Europe from the Orient in the 17th and early 18th centuries,[58] but was at times very expensive. Sony VPCCA1S1C/CN1 battery
Isolation of the pure element
Andreas Sigismund Marggraf is given credit for first isolating pure zinc
The isolation of metallic zinc in the West may have been achieved independently by several people. Postlewayt’s Universal Dictionary, a contemporary source giving technological information in Europe, did not mention zinc before 1751 but the element was studied before thenSony VPCCA1C5E battery.
Flemish metallurgist P.M. de Respour reported that he extracted metallic zinc from zinc oxide in 1668.[13] By the turn of the century, Étienne François Geoffroy described how zinc oxide condenses as yellow crystals on bars of iron placed above zinc ore being smelted.[13] In Britain, John Lane is said to have carried out experiments to smelt zinc, probably at Landore, prior to his bankruptcy in 1726. Sony VPCCA1AHJ battery
In 1738, William Champion patented in Great Britain a process to extract zinc from calamine in a vertical retort style smelter.[67] His technology was somewhat similar to that used at Zawar zinc mines in Rajasthan but there is no evidence that he visited the Orient.[68] Champion’s process was used through 1851. Sony VPCCA1AGJ battery
German chemist Andreas Marggraf normally gets credit for discovering pure metallic zinc even though Swedish chemist Anton von Swab distilled zinc from calamine four years before.[58] In his 1746 experiment, Marggraf heated a mixture of calamine and charcoal in a closed vessel without copper to obtain a metal.[54] This procedure became commercially practical by 1752. Sony VPCCA1AFJ battery
Later work
Galvanization was named after Luigi Galvani.
William Champion’s brother, John, patented a process in 1758 for calcining zinc sulfide into an oxide usable in the retort process.[11] 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.[70] Jean-Jacques Daniel Dony built a different kind of horizontal zinc smelter in Belgium, which processed even more zincSony VPCCA190 battery.[58] 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.[71] He incorrectly thought he had discovered an ability of nerves and muscles to create electricity and called the effect “animal electricity”.[72] 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 protectionSony VPCCA18EC/D battery.[72]
Galvani’s friend, Alessandro Volta, continued researching this effect and invented the Voltaic pile in 1800.[71] The basic unit of Volta’s pile was a simplified galvanic cell, which is made of a plate of copper and a plate of zinc connected to each other externally and separated by an electrolyte. These were stacked in series to make the Voltaic cell, which in turn produced electricity by directing electrons from the zinc to the copper and allowing the zinc to corrodeSony VPCCA18EC battery.[71]
The non-magnetic character of zinc and its lack of color in solution delayed discovery of its importance to biochemistry and nutrition.[73] This changed in 1940 when carbonic anhydrase, an enzyme that scrubs carbon dioxide from blood, was shown to have zinc in its active site.[73] The digestive enzyme carboxypeptidase became the second known zinc-containing enzyme in 1955. Sony VPCCA17FX/G battery
Production
Mining and processing
Zinc is the fourth most common metal in use, trailing only iron, aluminium, and copper with an annual production of about 12 million tonnes.[14] The world’s largest zinc producer is Nyrstar, a merger of the Australian OZ Minerals and the Belgian Umicore.[75] About 70% of the world’s zinc originates from mining, while the remaining 30% comes from recycling secondary zincSony VPCCA17FX/D battery.[76] Commercially pure zinc is known as Special High Grade, often abbreviated SHG, and is 99.995% pure.[77]
Worldwide, 95% of the zinc is mined from sulfidic ore deposits, in which sphalerite ZnS is nearly always mixed with the sulfides of copper, lead and iron.[78] There are zinc mines throughout the world, with the main mining areas being China, Australia and Peru. China produced 29% of the global zinc output in 2010. Sony VPCCA17EC/W battery
Zinc metal is produced using extractive metallurgy.[79] 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.[79] A final concentration of zinc of about 50% is reached by this process with the remainder of the concentrate being sulfur (32%), iron (13%), and SiO2 (5%).Sony VPCCA17EC battery
Roasting converts the zinc sulfide concentrate produced during processing to zinc oxide:[78]
2 ZnS + 3 O2 → 2 ZnO + 2 SO2
The sulfur dioxide is used for the production of sulfuric acid, which is necessary for the leaching process. If deposits of zinc carbonate, zinc silicate or zinc spinel, like the Skorpion Deposit in Namibia are used for zinc production the roasting can be omitted.
For further processing two basic methods are used: pyrometallurgy or electrowinning. Pyrometallurgy processing reduces zinc oxide with carbon or carbon monoxide at 950 °C (1,740 °F) into the metal, which is distilled as zinc vapor.Sony VPCCA16FW/W battery The zinc vapor is collected in a condenser.[78] The below set of equations demonstrate this process:[78]
2 ZnO + C → 2 Zn + CO2
ZnO + CO → Zn + CO2
Electrowinning processing leaches zinc from the ore concentrate by sulfuric acid:[82]
ZnO + H2SO4 → ZnSO4 + H2O
After this step electrolysis is used to produce zinc metal.[78]
2 ZnSO4 + 2 H2O → 2 Zn + 2 H2SO4 + O2
The sulfuric acid regenerated is recycled to the leaching step.
[edit]Environmental impact
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. Sony VPCCA16FH/B battery 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.[83] 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 1990sSony VPCCA16FG/W battery, 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.[84]
Levels of zinc in rivers flowing through industrial or mining areas can be as high as 20 ppm.[85] Effective sewage treatment greatly reduces this; treatment along the Rhine, for example, has decreased zinc levels to 50 ppb.[85] Concentrations of zinc as low as 2 ppm adversely affects the amount of oxygen that fish can carry in their blood. Sony VPCCA16FG/B battery
Historically responsible for high heavy metal levels in the Derwent River,[87] the zinc works at Lutana is the largest exporter in Tasmania, generating 2.5% of the state’s GDP, and producing over 250 thousand tonnes of zinc per year.[88]
Soils contaminated with zinc through the mining of zinc-containing ores, refining, or where zinc-containing sludge is used as fertilizer, can contain several grams of zinc per kilogram of dry soilSony VPCCA16EC/P battery. 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. Zinc levels of 2000 ppm to 180,000 ppm (18%) have been recorded in some soil samples.[85]
Applications
Major applications of zinc include (numbers are given for the US)[89]
Galvanizing (55%)
Alloys (21%)
Brass and bronze (16%)
Miscellaneous (8%)
Anti-corrosion and batteries
Hot-dip handrail galvanized crystalline surface
The metal is most commonly used as an anti-corrosion agent.[90] Galvanization, which is the coating of iron or steel to protect the metals against corrosion, is the most familiar form of using zinc in this way. In 2009 in the United States, 55% or 893 thousand tonnes of the zinc metal was used for galvanization. Sony VPCCA16EC battery
Zinc is more reactive than iron or steel and thus will attract almost all local oxidation until it completely corrodes away.[91] A protective surface layer of oxide and carbonate (Zn5(OH)6(CO3)2) forms as the zinc corrodes.[92] This protection lasts even after the zinc layer is scratched but degrades through time as the zinc corrodes away. Sony VPCCA15FX/W batteryThe 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.[10]
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. Sony VPCCA15FW/W battery Zinc acts as the anode (negative terminus) by slowly corroding away as it passes electric current to the steel pipeline.[92][note 2] Zinc is also used to cathodically protect metals that are exposed to sea water from corrosion.[93] A zinc disc attached to a ship’s iron rudder will slowly corrode while the rudder stays unattacked.[91] Other similar uses include a plug of zinc attached to a propeller or the metal protective guard for the keel of the shipSony VPCCA15FW/P battery.
With a standard electrode potential (SEP) of −0.76 volts, zinc is used as an anode material for batteries. (More reactive lithium (SEP −3.04 V) is used for anodes in lithium batteries ). Powdered zinc is used in this way in alkaline batteries and sheets of zinc metal form the cases for and act as anodes in zinc–carbon batteries.[94][95] Zinc is used as the anode or fuel of the zinc-air battery/fuel cellSony VPCCA15FW/D battery.
Alloys
A widely used alloy which contains zinc is brass, in which copper is alloyed with anywhere from 3% to 45% zinc, depending upon the type of brass.[92] Brass is generally more ductile and stronger than copper and has superior corrosion resistance.[92] These properties make it useful in communication equipment, hardware, musical instruments, and water valves. Sony VPCCA15FW/B battery
Cast brass microstructure at magnification 400x
Other widely used alloys that contain zinc include nickel silver, typewriter metal, soft and aluminium solder, and commercial bronze.[4] Zinc is also used in contemporary pipe organs as a substitute for the traditional lead/tin alloy in pipes.[99] Alloys of 85–88% zinc, 4–10% copper, and 2–8% aluminium find limited use in certain types of machine bearingsSony VPCCA15FH/W battery. Zinc is the primary metal used in making American one cent coins since 1982.[100] 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.[101]
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.[4] These alloys are marketed under the name ZamakSony VPCCA15FH/P battery.[102] 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. Sony VPCCA15FH/L batteryThis superplasticity of the alloy allows it to be molded using die casts made of ceramics and cement.[4]
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.[105] 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. Sony VPCCA15FH/G batteryUnalloyed zinc is too brittle for these kinds of manufacturing processes.[106]
As a dense, inexpensive, easily-worked material, zinc is used as a lead replacement. In the wake of lead concerns, zinc appears in lab weights,[107] tire weights, and flywheels.[108]
Cadmium zinc telluride (CZT) is a semiconductive alloy that can be divided into an array of small sensing devicesSony VPCCA15FH/B battery. These devices are similar to an integrated circuit and can detect the energy of incoming gamma ray photons.[109] When placed behind an absorbing mask, the CZT sensor array can also be used to determine the direction of the rays.[109]
Other industrial uses
Zinc oxide is used as a white pigment in paints.
Roughly one quarter of all zinc output, in the United States (2009), is consumed in the form of zinc compounds;[89] 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 rubberSony VPCCA15FG/W battery. 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).[10] The semiconductor properties of zinc oxide make it useful in varistors and photocopying products.[110] The zinc zinc-oxide cycle is a two step thermochemical process based on zinc and zinc oxide for hydrogen production. Sony VPCCA15FG/R battery
Zinc chloride is often added to lumber as a fire retardant[112] and can be used as a wood preservative.[113] It is also used to make other chemicals.[112] Zinc methyl (Zn(CH3)2) is used in a number of organic syntheses.[114] 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 spectrumSony VPCCA15FG/P battery. Zinc sulfate is a chemical in dyes and pigments.[112] Zinc pyrithione is used in antifouling paints.[117]
Zinc powder is sometimes used as a propellant in model rockets.[118] When a compressed mixture of 70% zinc and 30% sulfur powder is ignited there is a violent chemical reaction.[118] This produces zinc sulfide, together with large amounts of hot gas, heat, and light.[118] Zinc sheet metal is used to make zinc bars. Sony VPCCA15FG/G battery
Zinc has been proposed as a salting material for nuclear weapons (cobalt is another, better-known salting material).[120] A jacket of isotopically enriched 64Zn, irradiated by the intense high-energy neutron flux from an exploding thermonuclear weapon, would transmute into the radioactive isotope 65Zn with a half-life of 244 days and produce massive gamma radiation, significantly increasing the radioactivity of the weapon’s fallout for several days. Sony VPCCA15FG/D battery Such a weapon is not known to have ever been built, tested, or used.[120] 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.
Zinc dithiocarbamate complexes are used as agricultural fungicides; these include Zineb, Metiram, Propineb and Ziram.[122] Zinc naphthenate is used as wood preservative.[123] Zinc, in the form of ZDDP, is also used as an anti-wear additive for metal parts in engine oil. Sony VPCCA15FG/B battery
Dietary supplement
GNC zinc 50 mg tablets (AU)
Zinc is included in most single tablet over-the-counter daily vitamin and mineral supplements.[125] Preparations include zinc oxide, zinc acetate, and zinc gluconate.[125] 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.[126] Zinc also helps speed up the healing process after an injury. Sony VPCCA15FG battery
The efficacy of zinc compounds when used to reduce the duration or severity of cold symptoms is controversial. A 2011 systematic review concludes that supplementation yields a mild decrease in duration and severity of cold symptoms.[128]
Zinc gluconate is one compound used for the delivery of zinc as a dietary supplement.
Zinc preparations can protect against sunburn in the summer and windburn in the winter.[51] Applied thinly to a baby’s diaper area (perineum) with each diaper change, it can protect against diaper rash. Sony VPCCA15FF/W battery
The Age-Related Eye Disease Study determined that zinc can be part of an effective treatment for age-related macular degeneration.[129] Zinc supplementation is an effective treatment for acrodermatitis enteropathica, a genetic disorder affecting zinc absorption that was previously fatal to babies born with it. Sony VPCCA15FF/P battery
Zinc lactate is used in toothpaste to prevent halitosis.[130] Zinc pyrithione is widely applied in shampoos because of its anti-dandruff function. Zinc ions are effective antimicrobial agents even at low concentrations.[132] Gastroenteritis is strongly attenuated by ingestion of zinc, and this effect could be due to direct antimicrobial action of the zinc ions in the gastrointestinal tractSony VPCCA15FF/L battery, or to the absorption of the zinc and re-release from immune cells (all granulocytes secrete zinc), or both. In 2011, researchers at John Jay College of Criminal Justice reported that dietary zinc supplements can mask the presence of drugs in urine. Similar claims have been made in web forums on that topic.[135]
Although not yet tested as a therapy in humans, a growing body of evidence indicates that zinc may preferentially kill prostate cancer cellsSony VPCCA15FF/G battery. 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.[136] 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. Sony VPCCA15FF/B battery
Use in organic chemistry
There are many important organozinc compounds. Organozinc chemistry is the science of organozinc compounds describing their physical properties, synthesis and reactions.[138][139][140][141] 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, Sony VPCCA15FA/W battery 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) which is the zinc equivalent of the magnesium Grignard reaction and is better of the twoSony VPCCA15FA/P battery. 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[143][144] the active organozinc compound is obtained from much cheaper organobromine precursorsSony VPCCA15FA/L battery:
The Negishi coupling is also an important reaction for the formation of new carbon carbon bonds between unsaturated carbon atoms in alkenes, arenes and alkynes. The catalysts are nickel and palladium. A key step in the catalytic cycle is a transmetalation in which a zinc halide exchanges its organic substituent for another halogen with the palladium (nickel) metal centerSony VPCCA15FA/G battery. The Fukuyama coupling is another coupling reaction but this one with a thioester as reactant forming a ketone.
[edit]Biological role
Zinc is an essential trace element, necessary for plants,[84] animals,[145] and microorganisms.[146] Zinc is found in nearly 100 specific enzymes[147] (other sources say 300), serves as structural ions in transcription factors and is stored and transferred in metallothioneins.[148] It is “typically the second most abundant transition metal in organisms” after iron and it is the only metal which appears in all enzyme classes. Sony VPCCA15FA/B battery
In proteins, Zn ions are often coordinated to the amino acid side chains of aspartic acid, glutamic acid, cysteine and histidine.[149] The theoretical and computational description of this zinc binding in proteins (as well as that of other transition metals) is difficult.[149]
There are 2–4 grams of zinc[150] distributed throughout the human body. Most zinc is in the brain, muscle, bones, kidney, and liverSony VAIO VPCF135Z1E/B battery, with the highest concentrations in the prostate and parts of the eye.[151] Semen is particularly rich in zinc, which is a key factor in prostate gland function and reproductive organ growth.[152]
In humans, zinc plays “ubiquitous biological roles”.[1] It interacts with “a wide range of organic ligands”,[1] and has roles in the metabolism of RNA and DNA, signal transduction, and gene expression. It also regulates apoptosisSony VAIO VPCF137HG/BI battery. A 2006 study estimated that about 10% of human proteins (2800) potentially bind zinc, in addition to hundreds which transport and traffic zinc; a similar in silico study in the plant Arabidopsis thaliana found 2367 zinc-related proteins.[84]
In the brain, zinc is stored in specific synaptic vesicles by glutamatergic neurons[153] and can “modulate brain excitability”.[1] It plays a key role in synaptic plasticity and so in learning. Sony VAIO VPCF136FG/BI battery However it has been called “the brain’s dark horse”[153] since it also can be a neurotoxin, suggesting zinc homeostasis plays a critical role in normal functioning of the brain and central nervous system.
Enzymes
Ribbon diagram of human carbonic anhydrase II, with zinc atom visible in the center
Zinc fingers help read DNA sequences.
Zinc is an efficient Lewis acid, making it a useful catalytic agent in hydroxylation and other enzymatic reactions. Sony VAIO VPCF135FG/B battery The metal also has a flexible coordination geometry, which allows proteins using it to rapidly shift conformations to perform biological reactions.[155] Two examples of zinc-containing enzymes are carbonic anhydrase and carboxypeptidase, which are vital to the processes of carbon dioxide (CO2) regulation and digestion of proteins, respectively. Sony VAIO VPCF127HG/BI battery
In vertebrate blood, carbonic anhydrase converts CO2 into bicarbonate and the same enzyme transforms the bicarbonate back into CO2 for exhalation through the lungs.[157] Without this enzyme, this conversion would occur about one million times slower[158] at the normal blood pH of 7 or would require a pH of 10 or more.[159] The non-related β-carbonic anhydrase is required in plants for leaf formationSony VAIO VPCF11Z1E battery, the synthesis of indole acetic acid (auxin) and alcoholic fermentation.[160]
Carboxypeptidase cleaves peptide linkages during digestion of proteins. A coordinate covalent bond is formed between the terminal peptide and a C=O group attached to zinc, which gives the carbon a positive charge. This helps to create a hydrophobic pocket on the enzyme near the zinc, which attracts the non-polar part of the protein being digested. Sony VAIO VPCF11S1E battery
Other proteins
Zinc serves a purely structural role in zinc fingers, twists and clusters.[161] 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. Sony VAIO VPCF11M1E/H batteryThe transcription factor wraps around the DNA helix and uses its fingers to accurately bind to the DNA sequence.
In blood plasma, zinc is bound to and transported by albumin (60%, low-affinity) and transferrin (10%).[150] Since transferrin also transports iron, excessive iron reduces zinc absorption, and vice-versa. A similar reaction occurs with copper.[162] The concentration of zinc in blood plasma stays relatively constant regardless of zinc intake. Sony VAIO VPCF11M1E battery Cells in the salivary gland, prostate, immune system and intestine use zinc signaling as one way to communicate with other cells.[164]
Zinc may be held in metallothionein reserves within microorganisms or in the intestines or liver of animals.[165] Metallothionein in intestinal cells is capable of adjusting absorption of zinc by 15–40%. However, inadequate or excessive zinc intake can be harmful; excess zinc particularly impairs copper absorption because metallothionein absorbs both metals. Sony VAIO VPCF11JFX/B battery
Dietary intake
Foods & spices containing zinc
In the U.S., the Recommended Dietary Allowance (RDA) is 8 mg/day for women and 11 mg/day for men.[168] Median intake in the U.S. around 2000 was 9 mg/day for women and 14 mg/day in men.[169] Oysters, lobster [170] and red meats, especially beef, lamb and liver have some of the highest concentrations of zinc in food. Sony VAIO VPCF119FJ battery
The concentration of zinc in plants varies based on levels of the element in soil. When there is adequate zinc in the soil, the food plants that contain the most zinc are wheat (germ and bran) and various seeds (sesame, poppy, alfalfa, celery, mustard).[171] Zinc is also found in beans, nuts, almonds, whole grains, pumpkin seeds, sunflower seeds and blackcurrant. Sony VAIO VPCF119FC/BI battery
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.[173] This review cited studies which found low plasma zinc concentrations after zinc oxide andSony VAIO VPCF119FC battery zinc carbonate were consumed compared with those seen after consumption of zinc acetate and sulfate salts.[173] However, harmful excessive supplementation is a problem among the relatively affluent, and should probably not exceed 20 mg/day in healthy people,[174] although the U.S. National Research Council set a Tolerable Upper Intake of 40 mg/day. Sony VAIO VPCF117HG/BI battery
For fortification, however, a 2003 review recommended zinc oxide in cereals as cheap, stable, and as easily absorbed as more expensive forms.[176] 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.[177] A 1987 study found that zinc picolinate was better absorbed than zinc gluconate or zinc citrate. Sony VAIO VPCF116FG/BI batteryHowever, a study published in 2008 determined that zinc glycinate is the best absorbed of the four dietary supplement types available.[179]
[edit]Deficiency
Main article: Zinc deficiency
Zinc deficiency is usually due to insufficient dietary intake, but can be associated with malabsorption, acrodermatitis enteropathica, chronic liver disease, chronic renal disease, sickle cell disease, diabetes, malignancy, and other chronic illnesses. Sony VAIO VPCF115FG/B battery Symptoms of mild zinc deficiency are diverse.[169] 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.[163] Mild zinc deficiency depresses immunity,[180] although excessive zinc does alsoSony VAIO VPCF21ZHJ battery.[150] 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.[115]
Groups at risk for zinc deficiency include the elderly, and those with renal insufficiency. The zinc chelator phytate, found in seeds and cereal bran, can contribute to zinc malabsorption.[2]
Despite some concerns,[181] western vegetarians and vegans have not been found to suffer from overt zinc deficiencies any more than meat-eatersSony VAIO VPCF21Z1E/BI battery.[182] Major plant sources of zinc include cooked dried beans, sea vegetables, fortified cereals, soyfoods, nuts, peas, and seeds.[181] However, phytates in many whole-grains and fiber in many foods may interfere with zinc absorption and marginal zinc intake has poorly understood effects. 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. Sony VAIO VPCF21AHJ battery 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.[183] Diagnosing zinc deficiency is a persistent challenge.[1]
Nearly two billion people in the developing world are deficient in zinc.[2] In children it causes an increase in infection and diarrhea, contributing to the death of about 800,000 children worldwide per year. Sony VAIO VPCF21AGJ batteryThe World Health Organization advocates zinc supplementation for severe malnutrition and diarrhea.[184] Zinc supplements help prevent disease and reduce mortality, especially among children with low birth weight or stunted growth.[184] However, zinc supplements should not be administered alone, since many in the developing world have several deficiencies, and zinc interacts with other micronutrients. Sony VAIO VPCF21AFJ battery
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. Sony VAIO VPCF219FJ/BI battery 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, limestone, manure, sewage sludge, and particles from galvanized surfaces. Excess zinc is toxic to plants, although zinc toxicity is far less widespread. Sony VAIO VPCF217HG/BI battery
Precautions
Main article: Zinc toxicity
Toxicity
Although zinc is an essential requirement for good health, excess zinc can be harmful. Excessive absorption of zinc suppresses copper and iron absorption.[167] The free zinc ion in solution is highly toxic to plants, invertebrates, and even vertebrate fish.[186] The Free Ion Activity Model is well-established in the literature, and shows that just micromolar amounts of the free ion kills some organismsSony VAIO VPCF217HG battery. A recent example showed 6 micromolar killing 93% of all Daphnia in water.[187]
The free zinc ion is a powerful Lewis acid up to the point of being corrosive. Stomach acid contains hydrochloric acid, in which metallic zinc dissolves readily to give corrosive zinc chloride. Swallowing a post-1982 American one cent piece (97.5% zinc) can cause damage to the stomach lining due to the high solubility of the zinc ion in the acidic stomach. Sony VAIO VPCF14ZHJ battery
There is evidence of induced copper deficiency at low intakes of 100–300 mg Zn/day; a recent trial had higher hospitalizations for urinary complications compared to placebo among elderly men taking 80 mg/day.[189] The USDA RDA is 11 and 8 mg Zn/day for men and women, respectively.[168] Even lower levels, closer to the RDASony VAIO VPCF14AHJ battery, may interfere with the utilization of copper and iron or adversely affect cholesterol.[167] 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.[85] 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. Sony VAIO VPCF14AGJ battery Zinc is a common ingredient of denture cream which may contain between 17 and 38mg of zinc per gram. There have been cases of disability or even death due to excessive use of these products.[190]
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 infectionsSony VAIO VPCF14AFJ battery.[191] 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 itSony VAIO VPCF149FJ/BI battery.[192] 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.[193]
[edit]Poisoning
In 1982, the United States 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 fatalSony VAIO VPCF148FJ/B battery. One reported case of chronic ingestion of 425 pennies (over 1 kg of zinc) resulted in death due to gastrointestinal bacterial and fungal sepsis, while another patient, who ingested 12 grams of zinc, only showed lethargy and ataxia (gross lack of coordination of muscle movements).[194] Several other cases have been reported of humans suffering zinc intoxication by the ingestion of zinc coins. Sony VAIO VPCF13ZHJ battery
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.[197] Zinc is highly toxic in parrots and poisoning can often be fatal. Sony VAIO VPCF13Z0E/B batteryThe consumption of fruit juices stored in galvanized cans has resulted in mass parrot poisonings with zinc.[51]
Gallium ( /ˈɡæliəm/ gal-ee-əm) is a chemical element that has the symbol Ga and atomic number 31. Elemental gallium does not occur in nature, but as the gallium(III) compounds in trace amounts in bauxite and zinc ores. A soft silvery metallic poor metalSony VAIO VPCF13M8E/B battery, elemental gallium is a brittle solid at low temperatures. As it liquefies at temperature slightly above room temperature, it will melt in the hand. Its melting point is used as a temperature reference point. The alloy Galinstan (68.5% Ga, 21.5% In, 10% Sn) has an even lower melting point of −19 °C (−2 °F). From its discovery in 1875 until the semiconductor era, gallium was used primarily as an agent to make low-melting alloysSony VAIO VPCF13AHJ battery.
Today, almost all gallium is used for microelectronics. Gallium arsenide, the primary use of gallium, is used in microwave circuitry and infrared applications. Gallium nitride and indium gallium nitride, minority semiconductor uses, produce blue and violet light-emitting diodes (LEDs) and diode lasersSony VAIO VPCF13AGJ battery.
Gallium has no known role in biology. Because gallium(III) and ferric salts behave similarly in biological systems, gallium ions often mimic iron ions in medical applications. Gallium-containing pharmaceuticals and radiopharmaceuticals have been developed.
Properties
Elemental gallium is not found in nature, but it is easily obtained by smeltingSony VAIO VPCF13AFJ battery. Very pure gallium metal has a brilliant silvery color and its solid metal fractures conchoidally like glass. Gallium metal expands by 3.1% when it solidifies, and therefore storage in either glass or metal containers is avoided, due to the possibility of container rupture with freezing. Gallium shares the higher-density liquid state with only a few materials like silicon, germanium, bismuth, antimony, plutonium and waterSony VAIO VPCF138FJ/BI battery.
Gallium attacks most other metals by diffusing into their metal lattice. Gallium, for example, diffuses into the grain boundaries of Al/Zn alloys[1] or steel,[2] making them very brittle. Also, gallium metal easily alloys with many metals, and was used in small quantities as a plutonium-gallium alloy in the plutonium cores of the first and third nuclear bombs, to help stabilize the plutonium crystal structure. Sony VAIO VPCF138FJ/B battery
The melting point of 302.9146 K (29.7646 °C, 85.5763 °F) is near room temperature. Gallium’s melting point (mp) is one of the formal temperature reference points in the International Temperature Scale of 1990 (ITS-90) established by BIPM. The triple point of gallium of 302.9166 K (29.7666 °C, 85.5799 °F), is being used by NIST in preference to gallium’s melting point. Sony VAIO VPCF138FC/BI battery
Gallium metal melts in one’s hand. This metal has a strong tendency to supercool below its melting point/freezing point. Seeding with a crystal helps to initiate freezing. Gallium is one of the metals (with caesium, rubidium, mercury and likely francium) which are liquid at or near normal room temperature, and can therefore be used in metal-in-glass high-temperature thermometersSony VAIO VPCF135FG battery. It is also notable for having one of the largest liquid ranges for a metal, and (unlike mercury) for having a low vapor pressure at high temperatures. Unlike mercury, liquid gallium metal wets glass and skin, making it mechanically more difficult to handle (even though it is substantially less toxic and requires far fewer precautions). For this reason as well as the metal contamination and freezing-expansion problemsSony VAIO VPCF12AHJ battery, samples of gallium metal are usually supplied in polyethylene packets within other containers.
Crystallization of gallium from the melt
Gallium does not crystallize in any of the simple crystal structures. The stable phase under normal conditions is orthorhombic with 8 atoms in the conventional unit cell. Each atom has only one nearest neighbor (at a distance of 244 pm) and six other neighbors within additional 39 pm. Many stable and metastable phases are found as function of temperature and pressureSony VAIO VPCF12AGJ battery.
The bonding between the nearest neighbors is found to be of covalent character, hence Ga2 dimers are seen as the fundamental building blocks of the crystal. This explains the drop of the melting point compared to its neighbour elements aluminium and indium.
[edit]Chemical properties
High-purity gallium is dissolved slowly by mineral acids.
History
In 1871, existence of gallium was first predicted by Russian chemist Dmitri Mendeleev, who named it “eka-aluminium” on the basis of its position in his periodic tableSony VAIO VPCF12AFJ battery. He also predicted several properties of the element, which correspond closely to real gallium properties, such as density, melting point, oxide character and bonding in chloride.[8]
Gallium was discovered spectroscopically by Paul Emile Lecoq de Boisbaudran in 1875 by its characteristic spectrum (two violet lines) in an examination of a sphalerite sample.[9] Later that year, Lecoq obtained the free metal by electrolysis of its hydroxide in potassium hydroxide solutionSony VAIO VPCF129FJ/BI battery. He named the element “gallia”, from Latin Gallia meaning gaul, after his native land of France. It was later claimed that, in one of those multilingual puns so beloved of men of science in the 19th century, he had also named gallium after himself, as his name, “Le coq”, is the French for “the rooster”, and the Latin for “rooster” is “gallus”; however, in an 1877 article Lecoq denied this supposition.[10] (Cf. the naming of the J/ψ meson and the dwarf planet Pluto.) Sony VAIO VPCF128FJ/B battery
From its discovery in 1875 up to the era of semiconductors, its primary uses were in high-temperature thermometric applications and in preparation of metal alloys with unusual properties of stability, or ease of melting; some being liquid at room temperature or below. The development of gallium arsenide as a direct band gap semiconductor in the 1960′s ushered in the most important stage in the applications of galliumSony VAIO VPCF127FJ/W battery.
[edit]Occurrence
Gallium does not exist in free form in nature, and the few high-gallium minerals such as gallite (CuGaS2) are too rare to serve as a primary source of the element or its compounds. Its abundance in the Earth’s crust is approximately 16.9 ppm.[11] Gallium is found and extracted as a trace component in bauxite and to a small extent from sphaleriteSony VAIO VPCF11ZHJ battery. The amount extracted from coal, diaspore and germanite in which gallium is also present is negligible. The United States Geological Survey (USGS) estimates gallium reserves to exceed 1 million tonnes, based on 50 ppm by weight concentration in known reserves of bauxite and zinc ores.[12][13] Some flue dusts from burning coal have been shown to contain small quantities of gallium, typically less than 1% by weightSony VAIO VPCF11AHJ battery.
[edit]Production
99.9999% (6N) Gallium sealed in vacuum ampoule.
Gallium is a byproduct of the production of aluminium and zinc. Whereas the sphalerite for zinc production is the minor source. most gallium is extracted from the crude aluminium hydroxide solution of the Bayer process for producing alumina and aluminium. A mercury cell electrolysis and hydrolysis of the amalgam with sodium hydroxide leads to sodium gallateSony VAIO VPCF11AGJ battery. Electrolysis then gives gallium metal. For semiconductor use, further purification is carried out using zone melting, or else single crystal extraction from a melt (Czochralski process). Purities of 99.9999% are routinely achieved and commercially widely available.[18]
An exact number for the worldwide production is not available, but it is estimated that in 2007 the production of gallium was 184 tonnes with less than 100 tonnes from mining and the rest from scrap recyclingSony VAIO VPCF11AFJ battery.[12] In 1986, the production was estimated at 40 tons, according to a separate source.[19]
[edit]Applications
The semiconductor applications dominate the commercial use of gallium, accounting for 98% of applications. The next major application is for gadolinium gallium garnets. [19]
Semiconductors
Gallium-based blue LEDs
Because of this application, extremely high-purity (99.9999+%) gallium is commercially availability. Gallium arsenide (GaAs) and gallium nitride (GaN) used in electronic components represented about 98% of the gallium consumption in the United States in 2007Sony VAIO VPCF118FJ battery. About 66% of semiconductor gallium is used in the U.S. in integrated circuits (mostly gallium arsenide), such as the manufacture of ultra-high speed logic chips and MESFETs for low-noise microwave preamplifiers in cell phones. About 20% is used in optoelectronics.[12] Worldwide, gallium arsenide makes up 95% of the annual global gallium consumptionSony VAIO VPCF117FJ battery.[18]
Gallium arsenide is used in optoelectronics in a variety of infrared applications. Aluminium gallium arsenide (AlGaAs) is used in high-powered infrared laser diodes. As a component of the semiconductors indium gallium nitride and gallium nitride, gallium is used to produce blue and violet optoelectronic devices, mostly laser diodes and light-emitting diodesSony VAIO VGN-CS33H battery. For example, gallium nitride 405 nm diode lasers are used as a violet light source for higher-density compact disc data storage, in the Blu-ray Disc standard.[20]
Multijunction photovoltaic cells, developed for satellite power applications, are made by molecular beam epitaxy or metalorganic vapour phase epitaxy of thin films of gallium arsenide, indium gallium phosphide or indium gallium arsenide.The Mars Exploration Rovers and several satellites use triple junction gallium arsenide on germanium cellsSony VAIO VGN-CS33H/Z battery.[21] Gallium is also a component in photovoltaic compounds (such as copper indium gallium selenium sulfide or Cu(In,Ga)(Se,S)2) for use in solar panels as a cost-efficient alternative to crystalline silicon.[22]
[edit]Galinstan and other alloys
Gallium readily alloys with most metals, and has been used as a component in low-melting alloys. A nearly eutectic alloy of gallium, indium, and tin is a room temperature liquid which is available in medical thermometers. This alloy, with the trade-name Galinstan (with the “-stan” referring to the tin), has a low freezing point of −19 °C (−2.2 °F) Sony VAIO VGN-CS33H/B battery.[23] It has been suggested that this family of alloys could also be used to cool computer chips in place of water.[24] Gallium alloys have been evaluated as substitutes for mercury dental amalgams, but these materials have yet to see wide acceptance.
Because gallium wets glass or porcelain, gallium can be used to create brilliant mirrors. When the wetting action of gallium-alloys is not desired (as in Galinstan glass thermometers), the glass must be protected with a transparent layer of gallium(III) oxideSony VAIO VGN-CS31Z/Q battery.[25]
The plutonium used in nuclear weapon pits is machined by alloying with gallium to stabilize its δ phase.[26]
Gallium added in quantities up to 2% in common solders can aid wetting and flow characteristics.
Alloys of Al and Ga have been evaluated for hydrogen production.[27]
It is used as alloying element in the magnetic shape memory alloy Ni-Mn-Ga.
[edit]Biomedical applications
Although gallium has no known role in biology, it mimics iron(III), the gallium ion localizes to and interacts with many processes in the body in which iron(III) is manipulatedSony VAIO VGN-CS31S/W battery. As these processes include inflammation, which is a marker for many disease states, several gallium salts are used, or are in development, as both pharmaceuticals and radiopharmaceuticals in medicine. When gallium ions are mistakenly taken up by bacteria such as Pseudomonas, the bacteria’s ability to respire is interfered with and the bacteria die. The mechanism behind this is that iron is redox active, which allows for the transfer of electrons during respiration, but gallium is redox inactive. Sony VAIO VGN-CS31S/V battery
Gallium nitrate (brand name Ganite) has been used as an intravenous pharmaceutical to treat hypercalcemia associated with tumor metastasis to bones. Gallium is thought to interfere with osteoclast function. It may be effective when other treatments for maligancy-associated hypercalcemia are not. Sony VAIO VGN-CS31S/T battery
Gallium maltolate, an orally absorbable form of gallium(III) ion, is in clinical and preclinical trials as a potential treatment for a number of types of cancer, infectious disease, and inflammatory disease.[31]
A complex amine-phenol Ga(III) compound MR045 was found to be selectively toxic to parasites that have developed resistance to chloroquine, a common drug against malaria. Both the Ga(III) complex and chloroquine act by inhibiting crystallization of hemozoin, a disposal product formed from the digestion of blood by the parasitesSony VAIO VGN-CS31S/R battery.
Radiogallium salts
Gallium-67 salts such as gallium citrate and gallium nitrate are used as radiopharmaceutical agents in a nuclear medicine imaging procedure commonly referred to as a gallium scan. The form or salt of gallium is unimportant. For these applications, the radioactive isotope 67Ga is used. The body handles Ga3+ in many ways as though it were iron, and thus it is bound Sony VAIO VGN-CS31S/P battery (and concentrates) in areas of inflammation, such as infection, and also areas of rapid cell division. This allows such sites to be imaged by nuclear scan techniques. This use has largely been replaced by fluorodeoxyglucose (FDG) for positron emission tomography, “PET” scan and indium-111 labelled leukocyte scans. However, the localization of gallium in the body has some properties which make it unique in some circumstances from competing modalities using other radioisotopesSony VAIO VGN-CS28 battery.
Gallium-68, a positron emitter with a half life of 68 min., is now used as a diagnostic radionuclide in PET-CT when linked to pharmaceutical preparations such as DOTATOC, a somatostatin analogue used for neuroendocrine tumors investigation, and DOTA-TATE, a newer one, used for neuroendocrine metastasis and lung neuroendocrine cancer, such as certain types of microcytomaSony VAIO VGN-CS28/Q battery. Galium-68′s preparation as a pharmaceutical is chemical and the radionuclide is extracted by elution from germanium-68, a synthetic radioisotope of germanium, in gallium-68 generators.
Other uses
Magnesium gallate containing impurities (such as Mn2+), is beginning to be used in ultraviolet-activated phosphor powder.
Neutrino detection. Possibly the largest amount of pure gallium ever collected in a single spot is the Gallium-Germanium Neutrino Telescope used by the SAGE experiment at the Baksan Neutrino Observatory in RussiaSony VAIO VGN-CS27 battery. This detector contains 55–57 tonnes of liquid gallium.[34] Another experiment was the GALLEX neutrino detector operated in the early 1990s in an Italian mountain tunnel. The detector contained 12.2 tons of watered gallium-71. Solar neutrinos caused a few atoms of Ga-71 to become radioactive Ge-71, which were detected. The solar neutrino flux deduced was found to have a deficit of 40% from theorySony VAIO VGN-CS27/W battery. This was not explained until better solar neutrino detectors and theories were constructed (see SNO).[35]
As a liquid metal ion source for a focused ion beam.
In a classic prank by scientists, who fashion gallium spoons and serve tea to unsuspecting guests. The spoons melt in the hot tea.[36]
As an additive in glide wax for skiis, and other low friction surface materials. US 5069803, Sugimura, Kentaro; Shoji Hasimoto & Takayuki Ono, “Use of a synthetic resin composition containing gallium particles in the glide surfacing material of skis and other applications”, issued 1995Sony VAIO VGN-CS27/R battery
Chemistry
See also Category: Gallium compounds
Gallium is found primarily in the +3 oxidation state. The +1 oxidation is also attested in some compounds, although they tend to disproportionate into elemental gallium and gallium(III) compounds. What are sometimes referred to as gallium(II) compounds are actually mixed-oxidation state compounds containing both gallium(I) and gallium(III). Sony VAIO VGN-CS27/P battery
[edit]Chalcogen compounds
At room temperature, gallium metal is unreactive towards air and water due to the formation of a passive, protective oxide layer. At higher temperatures, however, it reacts with oxygen in the air to form gallium(III) oxide, Ga2O3.[37] Reducing Ga2O3 with elemental gallium in vacuum at 500 °C to 700 °C yields the dark brown gallium(I) oxide, Ga2O.Sony VAIO VGN-CS27/C battery:285 Ga2O is a very strong reducing agent, capable of reducing H2SO4 to H2S.[38]:207 It disproportionates at 800 °C back to gallium and Ga2O3.[39]
Gallium sulfide, Ga2S3, has 3 possible crystal modifications.[39]:104 It can be made by the reaction of gallium with hydrogen sulfide (H2S) at 950 °C.[38]:162 Alternatively, Ga(OH)3 can also be used at 747 °C: Sony VAIO VGN-CS26T/W battery
2 Ga(OH)3 + 3 H2S → Ga2S3 + 6 H2O
Reacting a mixture of alkali metal carbonates and Ga2O3 with H2S leads to the formation of thiogallates containing the [Ga2S4]2− anion. Strong acids decompose these salts, releasing H2S in the process.[39]:104–105 The mercury salt, HgGa2S4, can be used as a phosphor.[41]
Gallium also forms sulfides in lower oxidation states, such as gallium(II) sulfide and the green gallium(I) sulfide, the latter of which is produced from the former by heating to 1000 °C under a stream of nitrogen. Sony VAIO VGN-CS26T/V battery
The other binary chalcogenides, Ga2Se3 and Ga2Te3, have zincblende structure. They are all semiconductors, but are easily hydrolysed, limiting their usefulness.[39]:104
[edit]Aqueous chemistry
Strong acids dissolve gallium, forming gallium(III) salts such as Ga2(SO4)3 and Ga(NO3)3. Aqueous solutions of gallium(III) salts contain the hydrated gallium ion, [Ga(H2O)6]3+.[42]:1033 Gallium(III) hydroxide, Ga(OH)3Sony VAIO VGN-CS26T/T battery, may be precipitated from gallium(III) solutions by adding ammonia. Dehydrating Ga(OH)3 at 100 °C produces gallium oxide hydroxide, GaO(OH).[38]:140–141
Alkaline hydroxide solutions dissolve gallium, forming gallate salts containing the Ga(OH)−
4 anion.[37][42]:1033[43] Gallium hydroxide, which is amphoteric, also dissolves in alkali to form gallate salts.[38]:141 Although earlier work suggested Ga(OH)3−
6 as another possible gallate anion,[44] this species was not found in later work. Sony VAIO VGN-CS26T/R battery
[edit]Pnictogen compounds
Gallium reacts with ammonia at 1050 °C to form gallium nitride, GaN. Gallium also forms binary compounds with phosphorus, arsenic, and antimony: gallium phosphide (GaP), gallium arsenide (GaAs), and gallium antimonide (GaSb). These compounds have the same structure as ZnS, and have important semiconducting properties. GaP, GaAs, and GaSb can be synthesized by the direct reaction of gallium with elemental phosphorus, arsenic, or antimony. Sony VAIO VGN-CS26T/Q battery They exhibit higher electrical conductivity than GaN.[39]:101 GaP can also be synthesized by the reaction of Ga2O with phosphorus at low temperatures.[45]
Gallium also forms ternary nitrides; for example:[39]:99
Li3Ga + N2 → Li3GaN2
Similar compounds with phosphorus and antimony also exist: Li3GaP2 and Li3GaAs2. These compounds are easily hydrolyzed by dilute acids and water.[39]:101
[edit]Halides
See also: Gallium halides
Gallium(III) oxide reacts with fluorinating agents such as HF or F2 to form gallium(III) fluoride, GaF3. It is an ionic compound strongly insoluble in waterSony VAIO VGN-CS26T/P battery. However, it does dissolve in hydrofluoric acid, in which it forms an adduct with water, GaF3·3H2O. Attempting to dehydrate this adduct instead forms GaF2OH·nH2O. The adduct reacts with ammonia to form GaF3·3NH3, which can then be heated to form anhydrous GaF3.[38]:128–129
Gallium trichloride is formed by the reaction of gallium metal with chlorine gasSony VAIO VGN-CS26T/C battery.[37] Unlike the trifluoride, gallium(III) chloride exists as dimeric molecules, Ga2Cl6, with a melting point of 78 °C. This is also the case for the bromide and iodide, Ga2Br6 and Ga2I6.[38]:133
Like the other group 13 trihalides, gallium(III) halides are Lewis acids, reacting as halide acceptors with alkali metal halides to form salts containing GaX−
4 anions, where X is a halogen. They also react with alkyl halides to form carbocations and GaX−
4. Sony VAIO VGN-CS25H battery
When heated to a high temperature, gallium(III) halides react with elemental gallium to form the respective gallium(I) halides. For example, GaCl3 reacts with Ga to form GaCl:
2 Ga + GaCl3 3 GaCl (g)
At lower temperatures, the equilibrium shifts toward the left and GaCl disproportionates back to elemental gallium and GaCl3. GaCl can also be made by the reaction of Ga with HCl at 950 °C; it can then be condensed as red solid. Sony VAIO VGN-CS25H/W battery
Gallium(I) compounds can be stabilized by forming adducts with Lewis acids. For example:
GaCl + AlCl3 → Ga+[AlCl4]−
The so-called “gallium(II) halides”, GaX2, are actually adducts of gallium(I) halides with the respective gallium(III) halides, having the structure Ga+[GaX4]−. For example:
GaCl + GaCl3 → Ga+[GaCl4]−
Hydrogen compounds
Like aluminium, gallium also forms a hydride, GaH3, known as gallane, which may be obtained by the reaction of lithium gallanate (LiGaH4) with gallium(III) chloride at −30 °C: Sony VAIO VGN-CS25H/R battery
3 LiGaH4 + GaCl3 → 3 LiCl + 4 GaH3
In the presence of dimethyl ether as solvent, GaH3 polymerizes to (GaH3)n. If no solvent is used, the dimer Ga2H6 (digallane) is formed as a gas. Its structure is similar to diborane, having two hydrogen atoms bridging the two gallium centers, unlike α-AlH3 in which aluminium has a coordination number of 6.
Gallane is unstable above −10 °C, decomposing to elemental gallium and hydrogen. Sony VAIO VGN-CS25H/Q battery
Precautions
The Ga(III) ion of soluble gallium salts tends to form the insoluble hydroxide when injected in large amounts, and in animals precipitation of this has resulted in renal toxicity. In lower doses, soluble gallium is tolerated well, and does not accumulate as a poison.
While metallic gallium is not considered toxic, the data are inconclusive. Some sources suggest that it may cause dermatitis from prolonged exposure; other tests have not caused a positive reactionSony VAIO VGN-CS25H/P battery. Like most metals, finely divided gallium loses its luster and powdered gallium appears gray. Thus, when gallium is handled with bare hands, the extremely fine dispersion of liquid gallium droplets, which results from wetting skin with the metal, may appear as a gray skin stain.