LITHIUM

Lithium (from Greek: lithos, "stone") is a chemical element with symbol Li and atomic number 3. It is a soft, silver-white metal belonging to the alkali metal group of chemical elements. Under standard conditions it is the lightest metal and the least dense solid element. Like all alkali metals, lithium is highly reactive and flammable. For this reason, it is typically stored in mineral oil. When cut open, lithium exhibits a metallic luster, but contact with moist air corrodesthe surface quickly to a dull silvery gray, then black tarnish. Because of its high reactivity, lithium never occurs freely in nature, and instead, only appears incompounds, which are usually ionic. Lithium occurs in a number of pegmatitic minerals, but due to its solubility as an ion is present in ocean water and is commonly obtained from brines and clays. On a commercial scale, lithium is isolated electrolytically from a mixture of lithium chloride and potassium chloride. The nuclei of lithium verge on instability, since the two stable lithium isotopes found in nature have among the lowest binding energies per nucleon of all stablenuclides. Because of its relative nuclear instability, lithium is less common in the solar system than 25 of the first 32 chemical elements even though the nuclei are very light in atomic weight. For related reasons, lithium has important links to nuclear physics. The transmutation of lithium atoms to helium in 1932 was the first fully man-made nuclear reaction, and lithium-6 deuteride serves as a fusion fuel in staged thermonuclear weapons. Lithium and its compounds have several industrial applications, including heat-resistant glass and ceramics, high strength-to-weight alloys used in aircraft,lithium batteries and lithium-ion batteries. These uses consume more than half of lithium production. Trace amounts of lithium are present in all organisms. The element serves no apparent vital biological function, since animals and plants survive in good health without it. Non-vital functions have not been + ruled out. The lithium ion Li administered as any of several lithium salts has proved to be useful as a mood-stabilizing drug in the treatment of bipolar disorder, due to neurological effects of the ion in the human body.
1 Properties

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1.1 Atomic and physical 1.2 Chemistry and compounds 1.3 Isotopes

2 Occurrence

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2.1 Astronomical 2.2 Terrestrial 2.3 Biological

3 History 4 Production 5 Uses

5.1 Ceramics and glass

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5.2 Electrical and electronics 5.3 Lubricating greases 5.4 Metallurgy

6 Precautions

6.1 Regulation

PROPERTIES Atomic and physical Like the other alkali metals, lithium has a single valence electron that is easily given up to form a cation. Because of this, it is a good conductor of heat and electricity as well as a highly reactive element, though the least reactive of the alkali metals. Lithium's low reactivity compared to other alkali metals is due to the proximity of its valence electron to its nucleus (the remaining two electrons are in lithium's 1s orbital and are much lower in energy, and therefore they do not participate in chemical bonds). Lithium metal is soft enough to be cut with a knife. When cut, it possesses a silvery-white color that quickly changes to gray due to oxidation. While it has one of the lowest melting points among all metals (180 C), it has the highest melting and boiling points of the alkali metals. Lithium has a very low density of 0.534 g/cm , comparable with that of pine wood. It is the least dense of all elements that are solids at room temperature, the next lightest solid element (potassium, at 0.862 3 g/cm ) being more than 60% denser. Furthermore, apart from helium and hydrogen, it is less dense than 3 any liquid element, being only 2/3 as dense as liquid nitrogen(0.808 g/cm ). Lithium can float on the lightest hydrocarbon oils and is one of only three metals that can float on water, the other two being sodium andpotassium. Lithium's coefficient of thermal expansion is twice that of aluminium and almost four times that of iron. It has the highest specific heat capacity of any solid element. Lithium is superconductive below 400 K at standard pressure and at higher temperatures (more than 9 K) at very high pressures (>20 GPa) At temperatures below 70 K, lithium, like sodium, undergoes diffusionless phase change transformations. At 4.2 K it has a rhombohedral crystal system (with a nine-layer repeat spacing); at higher temperatures it transforms to face-centered cubic and then body-centered cubic. At liquid-helium temperatures (4 K) the rhombohedral structure is the most prevalent. Multiple allotropic forms have been reported for lithium at high pressures. Lithium has a specific heat capacity of 3.58 kilojoules per kilogram-Kelvin, the highest of all solids. Because of this, lithium metal is often used in coolants for heat transfer applications. Chemistry and compounds Lithium reacts with water easily, but with noticeably less energy than other alkali metals do. The reaction forms hydrogen gas andlithium hydroxide in aqueous solution. Because of its reactivity with water, lithium is usually stored under cover of a hydrocarbon, often petroleum jelly. Though the heavier alkali metals can be stored in more dense substances, such as mineral oil, lithium is not dense enough to be fully submerged in these liquids. In moist air, lithium rapidly tarnishes to form a black coating of lithium hydroxide (LiOH and LiOHH2O), lithium nitride (Li3N) and lithium carbonate (Li2CO3, the result of a secondary reaction between LiOH and CO2).
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When placed over a flame, lithium compounds give off a striking crimson color, but when it burns strongly the flame becomes a brilliant silver. Lithium will ignite and burn in oxygen when exposed to water or water vapors. Lithium isflammable, and it is potentially explosive when exposed to air and especially to water, though less so than the otheralkali metals. The lithium-water reaction at normal temperatures is brisk but nonviolent, as the hydrogen produced will not ignite on its own. As with all alkali metals, lithium fires are difficult to extinguish, requiring dry powder fire extinguishers, specifically the Class D type (see Types of extinguishing agents). Lithium is the only metal which reacts with nitrogen under normal conditions. Lithium has a diagonal relationship with magnesium, an element of similar atomic and ionic radius. Chemical resemblances between the two metals include the formation of a nitride by reaction with N2, the formation of an oxide(Li2O) and peroxide (Li2O2) when burnt in O2, salts with similar solubilities, and thermal instability of the carbonatesand nitrides. The metal reacts with hydrogen gas at high temperatures to produce lithium hydride (LiH). Other known binary compounds include the halides (LiF, LiCl, LiBr, LiI), and the sulfide (Li2S), the superoxide (LiO2),carbide (Li2C2). Many other inorganic compounds are known, where lithium combines with anions to form various salts: borates, amides, carbonate, nitrate, or borohydride (LiBH 4). Multiple organolithium reagents are known where there is a direct bond between carbon and lithium atoms effectively creating a carbanion. These are extremely powerful bases and nucleophiles. In many of these organolithium compounds, the lithium ions tend to aggregate into high-symmetry clusters by themselves, which is relatively common for alkali cations. LiHe, a very weakly interacting van der Waals compound, has been detected at very low temperatures. Isotopes Naturally occurring lithium is composed of two stable isotopes, Li and Li, the latter being the more abundant (92.5% natural abundance). Both natural isotopes have anomalously low nuclear binding energy per nucleon compared to the next lighter and heavier elements, helium and beryllium, which means that alone among stable light elements, lithium can produce net energy through nuclear fission. The two lithium nuclei have lower binding energies per nucleon than any other stable nuclides other than deuterium and helium-3. As a result of this, though very light in atomic weight, lithium is less common in the solar system than 25 of the first 32 chemical elements. Seven radioisotopes have been 8 9 characterized, the most stable being Li with a half-life of 838 ms and Li with a half-life of 178 ms. All of the remaining radioactive isotopes have half-lives that are shorter than 8.6 ms. The shortest-lived isotope 4 23 of lithium is Li, which decays through proton emission and has a half-life of 7.6 10 s.
7 6 7

Li is one of the primordial elements (or, more properly, primordial nuclides) produced in Big Bang 6 7 nucleosynthesis. A small amount of both Li and Li are produced in stars, but are thought to be burned 6 7 as fast as produced. Additional small amounts of lithium of both Li and Li may be generated from solar 7 10 wind, cosmic rays hitting heavier atoms, and from early solar system Be and Be radioactive 7 decay. While lithium is created in stars during the Stellar nucleosynthesis, it is further burnt. Li can also be generated in carbon stars. Lithium isotopes fractionate substantially during a wide variety of natural processes, including mineral formation (chemical precipitation), metabolism, and ion exchange. Lithium ions substitute 6 7 for magnesium and iron in octahedral sites in clay minerals, where Li is preferred to Li, resulting in 11 enrichment of the light isotope in processes of hyperfiltration and rock alteration. The exotic Li is known

to exhibit a nuclear halo. The process known as laser isotope separation can be used to separate lithium isotopes. Nuclear weapons manufacture and other nuclear physics uses are a major source of artificial lithium 6 fractionation, with the light isotope Li being retained by industry and military stockpiles to such an extent 6 7 as to slightly but measurably change the Li to Li ratios even in natural sources, such as rivers. This has led to unusual uncertainty in the standardized atomic weight of lithium, since this quantity depends on the natural abundance ratios of these naturally-occurring stable lithium isotopes, as they are available in commercial lithium mineral sources. OCCURRENCE Astronomical According to modern cosmological theory, lithium as both of its stable isotopes lithium-6 and lithium-7 was among the 3 elementssynthesized in the Big Bang. Though the amount of lithium generated in Big Bang nucleosynthesis is dependent upon the number ofphotons per baryon, for accepted values the lithium abundance can be calculated, and there is a "cosmological lithium discrepancy" in the Universe: older stars seem to have less lithium than they should, and some younger stars have far more. The lack of lithium in older stars is apparently caused by the "mixing" of lithium into the interior of stars, where it is destroyed. Furthermore, lithium is produced in younger stars. Though it transmutes into two atoms of helium due to collision with a proton at temperatures above 2.4 million degrees Celsius (most stars easily attain this temperature in their interiors), lithium is more abundant than predicted in later-generation stars, for causes not yet completely understood. Though it was one of the three first elements (together with helium and hydrogen) to be synthesized in the Big Bang, lithium, together withberyllium and boron are markedly less abundant than other nearby elements. This is a result of the low temperature necessary to destroy lithium, and a lack of common processes to produce it. Lithium is also found in brown dwarf substellar objects and certain anomalous orange stars. Because lithium is present in cooler, less-massive brown dwarfs, but is destroyed in hotter red dwarf stars, its presence in the stars' spectra can be used in the "lithium test" to differentiate the two, as both are smaller than the Sun. Certain orange stars can also contain a high concentration of lithium. Those orange stars found to have a higher than usual concentration of lithium (such as Centaurus X-4) orbit massive objectsneutron stars or black holeswhose gravity evidently pulls heavier lithium to the surface of a hydrogen-helium star, causing more lithium to be observed. Terrestrial Although lithium is widely distributed on Earth, it does not naturally occur in elemental form due to its high reactivity. The total lithium content of seawater is very large and is estimated as 230 billion tonnes, where the element exists at a relatively constant concentration of 0.14 to 0.25 parts per million (ppm), or 25 micromolar; higher concentrations approaching 7 ppm are found near hydrothermal vents. Estimates for the Earth's crustal content range from 20 to 70 ppm by weight. In keeping with its name, lithium forms a minor part ofigneous rocks, with the largest concentrations in granites. Granitic pegmatites also provide the greatest abundance of lithium-containing minerals, with spodumene and petalite being the most commercially viable sources. Another significant mineral of lithium is lepidolite. A newer source for lithium is hectorite clay, the only active development of which is

through the Western Lithium Corporation in the United States. At 20 mg lithium per kg of Earth's crust, lithium is the 25th most abundant element. According to the Handbook of Lithium and Natural Calcium, "Lithium is a comparatively rare element, although it is found in many rocks and some brines, but always in very low concentrations. There are a fairly large number of both lithium mineral and brine deposits but only comparatively few of them are of actual or potential commercial value. Many are very small, others are too low in grade." One of the largest reserve base of lithium is in the Salar de Uyuni area of Bolivia, which has 5.4 million tonnes. US Geological Survey, estimates that in 2010 Chile had the largest reserves by far (7.5 million tonnes) and the highest annual production (8,800 tonnes). Other major suppliers include Australia, Argentina and China. In June 2010, the New York Times reported that American geologists were conducting ground surveys on dry salt lakes in western Afghanistan believing that large deposits of lithium are located there. "Pentagon officials said that their initial analysis at one location in Ghazni Province showed the potential for lithium deposits as large as those of Bolivia, which now has the world's largest known lithium reserves." These estimates are "based principally on old data, which was gathered mainly by the Soviets during their occupation of Afghanistan from 19791989" and "Stephen Peters, the head of the USGS's Afghanistan Minerals Project, said that he was unaware of USGS involvement in any new surveying for minerals in Afghanistan in the past two years. 'We are not aware of any discoveries of lithium,' he said." Biological Lithium is found in trace amount in numerous plants, plankton, and invertebrates, at concentrations of 69 to 5,760 parts per billion (ppb). In vertebrates the concentration is slightly lower, and nearly all vertebrate tissue and body fluids have been found to contain lithium ranging from 21 to 763 ppb. Marine organisms tend to bioaccumulate lithium more than terrestrial ones. It is not known whether lithium has a physiological role in any of these organisms, but nutritional studies in mammals have indicated its importance to health, leading to a suggestion that it be classed as an essential trace element with an RDA of 1 mg/day. Observational studies in Japan, reported in 2011, suggested that naturally occurring lithium in drinking water may increase human lifespan. HISTORY Petalite (LiAlSi4O10) was discovered in 1800 by the Brazilian chemist and statesman Jos Bonifcio de Andrada e Silva in a mine on the island of Ut, Sweden. However, it was not until 1817 that Johan August Arfwedson, then working in the laboratory of the chemist Jns Jakob Berzelius,detected the presence of a new element while analyzing petalite ore. This element formed compounds similar to those of sodium and potassium, though its carbonateand hydroxide were less soluble in water and more alkaline. Berzelius gave the alkaline material the name "lithion/lithina", from the Greek word o(transliterated as lithos, meaning "stone"), to reflect its discovery in a solid mineral, as opposed to potassium, which had been discovered in plant ashes, and sodium which was known partly for its high abundance in animal blood. He named the metal inside the material " lithium". Arfwedson later showed that this same element was present in the minerals spodumene and lepidolite. In 1818, Christian Gmelin was the first to observe that lithium salts give a bright red color to flame. However, both Arfwedson and Gmelin tried and failed to isolate the pure element from its salts. It was not isolated until 1821, when William Thomas Brande obtained it by electrolysis of lithium oxide, a process that had

previously been employed by the chemist SirHumphry Davy to isolate the alkali metals potassium and sodium. Brande also described some pure salts of lithium, such as the chloride, and, estimating that lithia (lithium oxide) contained about 55% metal, estimated the atomic weight of lithium to be around 9.8 g/mol (modern value ~6.94 g/mol). In 1855, larger quantities of lithium were produced through the electrolysis of lithium chloride by Robert Bunsen and Augustus Matthiessen. The discovery of this procedure henceforth led to commercial production of lithium, beginning in 1923, by the German company Metallgesellschaft AG, which performed an electrolysis of a liquid mixture of lithium chloride and potassium chloride. The production and use of lithium underwent several drastic changes in history. The first major application of lithium was in high-temperature lithium greases for aircraft engines or similar applications in World War II and shortly after. This use was supported by the fact that lithium-based soaps have a higher melting point than other alkali soaps, and are less corrosive than calcium based soaps. The small market for lithium soaps and the lubricating greases based upon them was supported by several small mining operations mostly in the United States. The demand for lithium increased dramatically during the Cold War with the production of nuclear fusion weapons. Both lithium-6 and lithium-7 produce tritium when irradiated by neutrons, and are thus useful for the production of tritium by itself, as well as a form of solid fusion fuel used inside hydrogen bombs in the form of lithium deuteride. The United States became the prime producer of lithium in the period between the late 1950s and the mid-1980s. At the end, the stockpile of lithium was roughly 42,000 tonnes of lithium hydroxide. The stockpiled lithium was depleted in lithium-6 by 75%, which was enough to affect the measured atomic weight of lithium in many standardized chemicals, and even the atomic weight of lithium in some "natural sources" of lithium ion which had been "contaminated" by lithium salts discharged from isotope separation facilities, which had found its way into ground water. Lithium was used to decrease the melting temperature of glass and to improve the melting behavior ofaluminium oxide when using the Hall-Hroult process. These two uses dominated the market until the middle of the 1990s. After the end of the nuclear arms race the demand for lithium decreased and the sale of Department of Energy stockpiles on the open market further reduced prices. But in the mid-1990s, several companies started to extract lithium from brine which proved to be a less expensive method than underground or even open-pit mining. Most of the mines closed or shifted their focus to other materials as only the ore from zoned pegmatites could be mined for a competitive price. For example, the US mines st near Kings Mountain, North Carolina closed before the turn of the 21 century. The use in lithium ion batteries increased the demand for lithium and became the dominant use in 2007. With the surge of lithium demand in batteries in the 2000s, new companies have expanded brine extraction efforts to meet the rising demand. PRODUCTION Since the end of World War II lithium production has greatly increased. The metal is separated from other elements in igneous minerals such as those above. Lithium salts are extracted from the water of mineral springs, brine pools and brine deposits. The metal is produced electrolytically from a mixture of fused o 55% lithium chloride and 45% potassium chloride at about 450 C. In 1998 it was about 95 US$ / kg (or 43 US$/pound). Worldwide identified reserves of lithium in 2008 were estimated by the US Geological Survey as 13 million tonnes. Deposits of lithium are found in South America throughout the Andes mountain

chain. Chile is the leading lithium producer, followed by Argentina. Both countries recover the lithium from brine pools. In the United States lithium is recovered from brine pools in Nevada. However, half the world's known reserves are located in Bolivia, a nation sitting along the central eastern slope of the Andes. In 2009 Bolivia was negotiating with Japanese, French, and Korean firms to begin extraction. According to the US Geological Survey, Bolivia's Uyuni Desert has 5.4 million tonnes of lithium. A newly discovered deposit in Wyoming's Rock Springs Uplift is estimated at 228,000 tons. Additional deposits in the same formation were extrapolated to be as much as 18 million tons. After an industry wide pricing reduction for lithium carbonate after the Great Financial Crisis, where major suppliers such as Sociedad Qumica y Minera(SQM) dropped pricing by 20% in light of incoming lithium resource developers and to further defend their market position, pricing in 2012 scaled up due to increased lithium demand. A 2012 Business Week article outlined the existing oligopoly in the lithium space, "SQM, controlled by billionaire Julio Ponce, is the second-largest, followed by Rockwood, which is backed by Henry Kraviss KKR & Co., and Philadelphia -based FMC." Global consumption may jump to 300,000 metric tons a year by 2020 from about 150,000 tons in 2012, as demand for lithium batteries has been growing at about 25 percent a year, outpacing the 4 percent to 5 percent overall gain in lithium A potential source is geothermal wells. Geothermal fluids carry leachates to the surface; recovery of lithium has been demonstrated in the field. As the lithium is separated by simple filtration techniques, the process and environmental costs are primarily that of the already-operating geothermal well; relative environmental impacts may thus be positive. There are differing opinions about the potential growth of lithium production. According to a 2011 study conducted at Lawrence Berkeley National Laboratory and theUniversity of California Berkeley, the currently estimated reserve base of lithium should not be a limiting factor for large-scale battery production for electric vehicles, as the study estimated that on the order of 1 billion 40 kWh Li-based batteries could be built with current reserves. Another 2011 study by researchers from theUniversity of Michigan and Ford Motor Company found that there are sufficient lithium resources to support global demand until 2100, including the lithium required for the potential widespread use of hybrid electric, plugin hybrid electric and battery electric vehicles. The study estimated global lithium reserves at 39 million tons, and total demand for lithium during the 90-year period analyzed at 1220 million tons, depending on the scenarios regarding economic growth and recycling rates. However, another study concluded that "realistically achievable lithium carbonate production will be sufficient for only a small fraction of future PHEV and EV global market requirements", that "demand from the portable electronics sector will absorb much of the planned production increases in the next decade", and that "mass production of lithium carbonate is not environmentally sound, it will cause irreparable ecological damage to ecosystems that should be protected and that LiIon propulsion is incompatible with the notion of the 'Green Car'". USES Ceramics and glass Lithium oxide is a widely used flux for processing silica, reducing the melting point and viscosity of the material and leading to glazes of improved physical properties including low coefficients for thermal expansion. Lithium oxides are a component of ovenware. Worldwide, this is the single largest use for lithium compounds. Lithium carbonate (Li2CO3) is generally used in this application: upon heating it converts to the oxide.

Electrical and electronics In the later years of the 20th century, owing to its high electrochemical potential, lithium became an important component of the electrolyte and of one of the electrodes in batteries. A typical lithium-ion battery can generate approximately 3 volts, compared with 2.1 volts for lead-acid or 1.5 volts for zinccarbon cells. Because of its low atomic mass, it also has a high charge- and power-to-weight ratio. Lithium batteries are disposable (primary) batteries with lithium or its compounds as an anode. Lithium batteries are not to be confused with lithium-ion batteries, which are high energydensity rechargeable batteries. Other rechargeable batteries include the lithium-ion polymer battery, lithium iron phosphate battery, and the nanowire battery. Lubricating greases The third most common use of lithium is in greases. Lithium hydroxide is a strong base and, when heated with a fat, produces a soap made of lithium stearate. Lithium soap has the ability to thicken oils, and it is used to manufacture all-purpose, high-temperature lubricating greases. Metallurgy When used as a flux for welding or soldering, metallic lithium promotes the fusing of metals during the process and eliminates the forming of oxides by absorbing impurities. Its fusing quality is also important as a flux for producing ceramics, enamels and glass. Alloys of the metal with aluminium, cadmium, copper andmanganese are used to make high-performance aircraft parts (see also Lithium-aluminium alloys). PRECAUTIONS Lithium is corrosive and requires special handling to avoid skin contact. Breathing lithium dust or lithium compounds (which are often alkaline) initially irritate the nose and throat, while higher exposure can cause a buildup of fluid in the lungs, leading to pulmonary edema. The metal itself is a handling hazard because of the caustic hydroxide produced when it is in contact with moisture. Lithium is safely stored in non-reactive compounds such as naphtha. Regulation Some jurisdictions limit the sale of lithium batteries, which are the most readily available source of lithium for ordinary consumers. Lithium can be used to reduce pseudoephedrine andephedrine to methamphetamine in the Birch reduction method, which employs solutions of alkali metals dissolved in anhydrous ammonia. Carriage and shipment of some kinds of lithium batteries may be prohibited aboard certain types of transportation (particularly aircraft) because of the ability of most types of lithium batteries to fully discharge very rapidly whenshort-circuited, leading to overheating and possible explosion in a process called thermal runaway. Most consumer lithium batteries have thermal overload protection built-in to prevent this type of incident, or their design inherently limits short-circuit currents. Internal shorts have been known to develop due to manufacturing defects or damage to batteries that can lead to spontaneous thermal runaway.

BERYLLIUM Beryllium is the chemical element with the symbol Be and atomic number 4. Because any beryllium synthesized in stars is short-lived, it is a relatively rare element in both the universe and in the crust of the Earth. It is a divalent element which occurs naturally only in combination with other elements in minerals. Notable gemstones which contain beryllium include beryl (aquamarine, emerald) and chrysoberyl. As a free element it is a steel-gray, strong, lightweight and brittle alkaline earth metal. Beryllium increases hardness and resistance to corrosion when alloyed with aluminium, cobalt, copper (notably beryllium copper), iron and nickel. In structural applications, high flexural rigidity, thermal stability, thermal conductivity and low density (1.85 times that of water) make beryllium a quality aerospace material for high-speed aircraft, missiles, space vehicles and communication satellites. Because of its low density and atomic mass, beryllium is relatively transparent to X-rays and other forms of ionizing radiation; therefore, it is the most common window material for X-ray equipment and in particle physics experiments. The high thermal conductivities of beryllium and beryllium oxide have led to their use in heat transport and heat sinking applications. The commercial use of beryllium presents technical challenges due to the toxicity (especially by inhalation) of beryllium-containing dusts. Beryllium is corrosive to tissue, and can cause a chronic lifethreatening allergic disease called berylliosis in some people. The element is not known to be necessary or useful for either plant or animal life.
1 Characteristics

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1.1 Physical properties 1.2 Nuclear properties 1.3 Isotopes and nucleosynthesis 1.4 Occurrence

2 Production 3 Chemical properties 4 History

4.1 Etymology

5 Applications 6 Precautions

CHARACTERISTICS

Physical properties

Beryllium is a steel gray and hard metal that is brittle at room temperature and has a close-packed hexagonal crystal structure. It has exceptional flexural rigidity (Young's modulus 287 GPa) and a reasonably high melting point. The modulus of elasticity of beryllium is approximately 50% greater than

that of steel. The combination of this modulus and a relatively low density results in an unusually fast sound conduction speed in beryllium about 12.9 km/s at ambient conditions. Other significant properties are high specific heat (1925 Jkg K ) and thermal conductivity (216 Wm K ), which make beryllium the metal with the best heat dissipation characteristics per unit weight. In combination with the relatively low coefficient of linear thermal expansion (11.410 unique stability under conditions of thermal loading.
6 1 1 1 1 1

K ), these characteristics result in a

Nuclear properties Natural beryllium, save for slight contamination by cosmogenic radioisotopes, is essentially beryllium-9, which has a nuclear spin of 3/2-. Beryllium has a large scattering cross section for high-energy neutrons, about 6 barns for energies above ~0.01 MeV. Therefore, it works as a neutron reflector and neutron moderator, effectively slowing the neutrons to the thermal energy range of below 0.03 eV, where the total cross section is at least an order of magnitude lower exact value strongly depends on the purity and size of the crystallites in the material. The single primordial beryllium isotope Be also undergoes a (n,2n) neutron reaction with neutron 8 energies over about 1.9 MeV, to produce Be, which almost immediately breaks into two alpha particles. Thus, for high-energy neutrons beryllium is a neutron multiplier, releasing more neutrons than it absorbs. This nuclear reaction is:
9 4Be + n 2(4 2He) + 2n
9

Neutrons are liberated when beryllium nuclei are struck by energetic alpha particles producing the nuclear reaction
9 4Be + 4 2He 12 6C + n , where 4 2He is an alpha particle and 12 6C is a carbon-12 nucleus.

Beryllium also releases neutrons under bombardment by gamma rays. Thus, natural beryllium bombarded either by alphas or gammas from a suitable radioisotope is a key component of most radioisotope-powered nuclear reaction neutron sources for the laboratory production of free neutrons. As a metal, beryllium is transparent to most wavelengths of X-rays and gamma rays, making it useful for the output windows of X-ray tubes and other such apparatus. Isotopes and nucleosynthesis

Both stable and unstable isotopes of beryllium are created in stars, but these do not last long. It is believed that most of the stable beryllium in the universe was originally created in the interstellar medium when cosmic rays induced fission in heavier elements found in interstellar gas and dust. Primordial 9 beryllium contains only one stable isotope, Be, and therefore beryllium is a monoisotopic element. Radioactive cosmogenic Be is produced in the atmosphere of the Earth by the cosmic ray 10 spallationof oxygen. Be accumulates at the soil surface, where its relatively long half-life (1.36 million 10 years) permits a long residence time before decaying to boron-10. Thus, Be and its daughter products are used to examine natural soil erosion, soil formation and the development of lateritic soils, and as 10 aproxy for measurement of the variations in solar activity and the age of ice cores. The production of Be is inversely proportional to solar activity, because increased solar wind during periods of high solar 10 activity decreases the flux of galactic cosmic rays that reach the Earth. Nuclear explosions also form Be 13 by the reaction of fast neutrons with C in the carbon dioxide in air. This is one of the indicators of past 7 activity at nuclear weapon test sites. The isotope Be (half-life 53 days) is also cosmogenic, and shows an 10 atmospheric abundance linked to sunspots, much like Be.
8 10

Be has a very short half-life of about 710 s that contributes to its significant cosmological role, as elements heavier than beryllium could not have been produced by nuclear fusion in the Big Bang. This is due to the lack of sufficient time during the Big Bang's nucleosynthesis phase to produce carbon by the 4 fusion of He nuclei and the very low concentrations of available beryllium-8. The 8 12 Britishastronomer Sir Fred Hoyle first showed that the energy levels of Be and C allow carbon production by the so-called triple-alpha process in helium-fueled stars where more nucleosynthesis time is available. This process allows carbon to be produced in stars, but not in the Big Bang. Star-created carbon (the basis of carbon-based life) is thus a component in the elements in the gas and dust ejected by AGB stars and supernovae (see also Big Bang nucleosynthesis), as well as the creation of all other elements with atomic numbers larger than that of carbon. The innermost electrons of beryllium may contribute to chemical bonding. Therefore, when Be decays by electron capture, it does so by taking electrons fromatomic orbitals that may participate in bonding. This makes its decay rate dependent to a measurable degree upon its electron configuration a rare occurrence in nuclear decay. The shortest-lived known isotope of beryllium is Be which decays through neutron emission. It has a 21 6 21 half-life of 2.7 10 s. Be is also very short-lived with a half-life of 5.0 10 s. The exotic 11 14 isotopes Be and Be are known to exhibit a nuclear halo. This phenomenon can be understood as the 11 14 nuclei of Be and Be have, respectively, 1 and 4 neutrons orbiting substantially outside the classical Fermi 'waterdrop' model of the nucleus. Occurrence Beryllium has a concentration of 2 to 6 parts per million (ppm) in the Earth's crust. The Sun has a concentration of 0.1 parts per billion (ppb) of beryllium. It is most concentrated in the soils, 6 ppm, and is 9 found in 0.2 parts per trillion (ppt) of sea water. Trace amounts of Be are found in the Earth's atmosphere. In sea water, beryllium is exceedingly rare, comprising only 0.0006 ppb by weight. In stream water, however, beryllium is more abundant with 0.1 ppb by weight. Beryllium is found in over 100 minerals, but most are uncommon to rare. The more common beryllium containing minerals include: bertrandite (Be4Si2O7(OH)2), beryl (Al2Be3Si6O18), chrysoberyl (Al2BeO4)
13 7

17

and phenakite(Be2SiO4). Precious forms of beryl are aquamarine, red beryl and emerald. The green color in gem-quality forms of beryl comes from varying amounts of chromium (about 2% for emerald). The two main ores of beryllium, beryl and bertrandite, are found in Argentina, Brazil, India, Madagascar, Russia and the United States. Total world reserves of beryllium ore are greater than 400,000 tonnes. PRODUCTION The extraction of beryllium from its compounds is a difficult process due to its high affinity for oxygen at elevated temperatures, and its ability to reduce water when its oxide film is removed. The United States, China and Kazakhstan are the only three countries involved in the industrial scale extraction of beryllium. Beryllium is most-commonly extracted from beryl, which is either sintered using an extraction agent or melted into a soluble mixture. The sintering process involves mixing beryl withsodium fluorosilicate and soda at 770 C to form sodium fluoroberyllate, aluminium oxide and silicon dioxide. Beryllium hydroxide is precipitated from a solution of sodium fluoroberyllate and sodium hydroxide in water. Extraction of beryllium using the melt method involves grinding beryl into a powder and heating it to 1,650 C. The melt is quickly cooled with water and then reheated 250 to 300 C in concentrated sulfuric acid, mostly yielding beryllium sulfate and aluminium sulfate. Aqueous ammonia is then used to remove the aluminium and sulfur, leaving beryllium hydroxide. Beryllium hydroxide created using either the sinter or melt method is then converted into beryllium fluoride or beryllium chloride. To form the fluoride, aqueous ammonium hydrogen fluoride is added to beryllium hydroxide to yield a precipitate of ammonium tetrafluoroberyllate, which is heated to 1,000C to form beryllium fluoride. Heating the fluoride to 900 C with magnesium forms finely divided beryllium and additional heating to 1,300 C creates the compact metal. Heating beryllium hydroxide forms the oxide which becomes beryllium chloride when mixed with carbon and chloride. Electrolysis of molten beryllium chloride is then used to obtain the metal. CHEMICAL PROPERTIES Beryllium's chemical behavior is largely a result of its small atomic and ionic radii. It thus has very high ionization potentials and strong polarization while bonded to other atoms, which is why all of its compounds are covalent. It is more chemically similar to aluminium than its close neighbors in the periodic table due to having a similar charge-to-radius ratio. An oxide layer forms around beryllium that prevents further reactions with air unless heated above 1000 C. Once ignited, beryllium burns brilliantly forming a mixture of beryllium oxide and beryllium nitride. Beryllium dissolves readily in non-oxidizing acids, such as HCl and diluted H2SO4, but not in nitric acid or water as this forms the oxide. This behavior is similar to that of aluminium metal. Beryllium also dissolves in alkali solutions. The beryllium atom has the electronic configuration [He] 2s . The two valence electrons give beryllium a +2 oxidation state and thus the ability to form two covalent bonds; the only evidence of lower valence of beryllium is in the solubility of the metal in BeCl2. Due to the octet rule, atoms tend to seek a valence of 8 in order to resemble a noble gas. Beryllium tries to achieve a coordination number of 4 because its two covalent bonds fill half of this octet. A coordination of 4 allows beryllium compounds, such as the fluoride or chloride, to form polymers. This characteristic is employed in analytical techniques using EDTA as a ligand. EDTA preferentially 3+ forms octahedral complexes thus absorbing other cations such as Al which might interfere for 2+ example, in the solvent extraction of a complex formed between Be and acetylacetone. Beryllium(II)
2

readily forms complexes with strong donating ligands such as phosphine oxides and arsine oxides. There have been extensive studies of these complexes which show the stability of the O-Be bond. Solutions of beryllium salts, e.g. beryllium sulfate and beryllium nitrate, are acidic because of hydrolysis of 2+ the [Be(H2O)4] ion. [Be(H2O)4]
2+

+ H2O

[Be(H2O)3(OH)] + H3O

+ 3+

Other products of hydrolysis include the trimeric ion [Be3(OH)3(H2O)6] . Beryllium hydroxide, Be(OH)2, is insoluble even in acidic solutions with pH less than 6, that is at biological pH. It is amphoteric and dissolves in strongly alkaline solutions. Beryllium forms binary compounds with many non-metals. Anhydrous halides are known for F, Cl, Br and I. BeF2 has a silica-like structure with corner-shared BeF4tetrahedra. BeCl2 and BeBr2 have chain structures with edge-shared tetrahedra. All beryllium halides have a linear monomeric molecular structure in the gas phase. Beryllium difluoride, BeF2, is different than the other difluorides. In general, beryllium has a tendency to bond covalently, much more so than the other alkaline earths and its fluoride is partially covalent (although still more ionic than its other halides). BeF2 has many similarities to SiO2 (quartz) a mostly covalently bonded network solid. BeF2 has tetrahedrally coordinated metal and forms glasses (is difficult to crystallize). When crystalline, beryllium fluoride has the same room temperature crystal structure as quartz and shares many higher temperature structures also. Beryllium difluoride is very soluble in water, unlike the other alkaline earths. (Although they are strongly ionic, they do not dissolve because of the especially strong lattice energy of the fluorite structure.) However, BeF2 has much lower electrical conductivity when in solution or when molten than would be expected if it were fully ionic. The beryllium atom has the electronic configuration [He] 2s . The two valence electrons give beryllium a +2 oxidation state and thus the ability to form two covalent bonds; the only evidence of lower valence of beryllium is in the solubility of the metal in BeCl2. Due to the octet rule, atoms tend to seek a valence of 8 in order to resemble a noble gas. Beryllium tries to achieve a coordination number of 4 because its two covalent bonds fill half of this octet. A coordination of 4 allows beryllium compounds, such as the fluoride or chloride, to form polymers. This characteristic is employed in analytical techniques using EDTA as a ligand. EDTA preferentially 3+ forms octahedral complexes thus absorbing other cations such as Al which might interfere for 2+ example, in the solvent extraction of a complex formed between Be and acetylacetone. Beryllium(II) readily forms complexes with strong donating ligands such as phosphine oxides and arsine oxides. There have been extensive studies of these complexes which show the stability of the O-Be bond. Solutions of beryllium salts, e.g. beryllium sulfate and beryllium nitrate, are acidic because of hydrolysis of 2+ the [Be(H2O)4] ion. [Be(H2O)4]
2+ 2

+ H2O

[Be(H2O)3(OH)] + H3O

+ 3+

Other products of hydrolysis include the trimeric ion [Be3(OH)3(H2O)6] . Beryllium hydroxide, Be(OH)2, is insoluble even in acidic solutions with pH less than 6, that is at biological pH. It is amphoteric and dissolves in strongly alkaline solutions.

Beryllium forms binary compounds with many non-metals. Anhydrous halides are known for F, Cl, Br and I. BeF2 has a silica-like structure with corner-shared BeF4tetrahedra. BeCl2 and BeBr2 have chain structures with edge-shared tetrahedra. All beryllium halides have a linear monomeric molecular structure in the gas phase. Beryllium difluoride, BeF2, is different than the other difluorides. In general, beryllium has a tendency to bond covalently, much more so than the other alkaline earths and its fluoride is partially covalent (although still more ionic than its other halides). BeF2 has many similarities to SiO2 (quartz) a mostly covalently bonded network solid. BeF2 has tetrahedrally coordinated metal and forms glasses (is difficult to crystallize). When crystalline, beryllium fluoride has the same room temperature crystal structure as quartz and shares many higher temperature structures also. Beryllium difluoride is very soluble in water, unlike the other alkaline earths. (Although they are strongly ionic, they do not dissolve because of the especially strong lattice energy of the fluorite structure.) However, BeF2 has much lower electrical conductivity when in solution or when molten than would be expected if it were fully ionic. Beryllium oxide, BeO, is a white refractory solid, which has the wurtzite crystal structure and a thermal conductivity as high as in some metals. BeO is amphoteric. Salts of beryllium can be produced by treating Be(OH)2 with acid. Beryllium sulfide, selenide and telluride are known, all having the zincblende structure. Beryllium nitride, Be3N2 is a high-melting-point compound which is readily hydrolyzed. Beryllium azide, BeN6 is known and beryllium phosphide, Be3P2 has a similar structure to Be3N2. Basic beryllium nitrate and basic beryllium acetate have similar tetrahedral structures with four beryllium atoms coordinated to a central oxide ion. A number of beryllium borides are known, such as Be5B, Be4B, Be2B, BeB2, BeB6 and BeB12. Beryllium carbide, Be2C, is a refractory brick-red compound that reacts with water to give methane. No beryllium silicide has been identified.

HISTORY The mineral beryl, which contains beryllium, has been used at least since the Ptolemaic dynasty of Egypt. In the first century CE, Roman naturalist Pliny the Elder mentioned in his encyclopedia Natural History that beryl and emerald ("smaragdus") were similar. The Papyrus Graecus Holmiensis, written in the third or fourth century CE, contains notes on how to prepare artificial emerald and beryl. Early analyses of emeralds and beryls by Martin Heinrich Klaproth, Torbern Olof Bergman, Franz Karl Achard, and Johann Jakob Bindheim always yielded similar elements, leading to the fallacious conclusion that both substances are aluminium silicates. Mineralogist Ren Just Hay discovered that both crystals are geometrically identical, and he asked chemist Louis-Nicolas Vauquelin for a chemical analysis. In a 1798 paper read before the Institut de France, Vauquelin reported that he found a new "earth" by dissolving aluminium hydroxide from emerald and beryl in an additionalalkali. The editors of the journal Annales de Chimie et de Physique named the new earth "glucine" for the sweet taste of some of its compounds. Klaproth preferred the name "beryllina" due to fact that yttria also formed sweet salts. The name "beryllium" was first used by Whler in 1828. Friedrich Whler and Antoine Bussy independently isolated beryllium in 1828 by the chemical reaction of metallic potassium withberyllium chloride, as follows:

BeCl2 + 2 K 2 KCl + Be Using an alcohol lamp, Whler heated alternating layers of beryllium chloride and potassium in a wired-shut platinum crucible. The above reaction immediately took place and caused the crucible to become white hot. Upon cooling and washing the resulting gray-black powder he saw that it was made of fine particles with a dark metallic luster. The highly reactive potassium had been produced by theelectrolysis of its compounds, a process discovered 21 years before. The chemical method using potassium yielded only small grains of beryllium from which no ingot of metal could be cast or hammered. The direct electrolysis of a molten mixture of beryllium fluoride and sodium fluoride by Paul Lebeau in 1898 resulted in the first pure (99.5 to 99.8%) samples of beryllium. The first commercially-successful process for producing beryllium was developed in 1932 by Alfred Stock and Hans Goldschmidt. Their process involves the electrolysation of a mixture of beryllium fluorides and barium, which causes molten beryllium to collect on a water-cooled iron cathode. A sample of beryllium was bombarded with alpha rays from the decay of radium in a 1932 experiment by James Chadwick that uncovered the existence of the neutron. This same method is used in one class of radioisotope-based laboratory neutron sources that produce 30 neutrons for every million particles. Beryllium production saw a rapid increase during World War II, due to the rising demand for hard beryllium-copper alloys and phosphors for fluorescent lights. Most early fluorescent lamps used zinc orthosilicate with varying content of beryllium to emit greenish light. Small additions of magnesium tungstate improved the blue part of the spectrum to yield an acceptable white light. Halophosphate-based phosphors replaced beryllium-based phosphors after beryllium was found to be toxic. Electrolysis of a mixture of beryllium fluoride and sodium fluoride was used to isolate beryllium during the 19th century. The metal's high melting point makes this process more energy-consuming than corresponding processes used for the alkali metals. Early in the 20th century, the production of beryllium by the thermal decomposition of beryllium iodide was investigated following the success of a similar process for the production of zirconium, but this process proved to be uneconomical for volume production. Pure beryllium metal did not become readily available until 1957, even though it had been used as an alloying metal to harden and toughen copper much earlier. Beryllium could be produced by reducing beryllium compounds such as beryllium chloride with metallic potassium or sodium. Currently most beryllium is produced by reducing beryllium fluoride with purified magnesium. The price on the American market for vacuum-cast beryllium ingots was about $338 per pound ($745 per kilogram) in 2001. Between 1998 and 2008, the world's production of beryllium had decreased from 343 to about 200 tonnes, of which 176 tonnes (88%) came from the United States. Etymology Early usage of the word beryllium can be traced to many languages, including Latin Beryllus; French Bry; Greek , brullos, beryl; Prakrit veruliya; Pli veuriya, veiru or viar "to become pale", in reference to the pale semiprecious gemstone beryl. The original source is probably

the Sanskrit word vaidurya-, which is of Dravidian origin and could be derived from the name of the modern city of Belur. For about 160 years, beryllium was also known as glucinum or glucinium (with the accompanying chemical symbol "Gl",), the name coming from the Greek word for sweet: , due to the sweet taste of beryllium salts. APPLICATIONS It is estimated that most beryllium is used for military applications, so information is not readily available. PRECAUTIONS Approximately 35 micrograms of beryllium is found in the human body, but this amount is not considered harmful. Beryllium is chemically similar to magnesium and therefore can displace it from enzymes, which causes them to malfunction. Chronic berylliosis is a pulmonary and systemic granulomatous disease caused by inhalation of dust or fumes contaminated with beryllium; either large amounts over a short time or small amounts over a long time can lead to this ailment. Symptoms of the disease can take up to five years to develop; about a third of patients with it die and the survivors are left disabled. The International Agency for Research on Cancer (IARC) lists beryllium and beryllium compounds as Category 1 carcinogens. Acute beryllium disease in the form of chemical pneumonitis was first reported in Europe in 1933 and in the United States in 1943. A survey found that about 5% of workers in plants manufacturing fluorescent lamps in 1949 in the United States had beryllium-related lung diseases. Chronic berylliosis resembles sarcoidosis in many respects, and the differential diagnosis is often difficult. It killed some early workers in nuclear weapons design, such as Herbert L. Anderson. Early researchers tasted beryllium and its various compounds for sweetness in order to verify its presence. Modern diagnostic equipment no longer necessitates this highly risky procedure and no attempt should be made to ingest this highly toxic substance. Beryllium and its compounds should be handled with great care and special precautions must be taken when carrying out any activity which could result in the release of beryllium dust (lung cancer is a possible result of prolonged exposure to beryllium laden dust). Although the use of beryllium compounds in fluorescent lighting tubes was discontinued in 1949, potential for exposure to beryllium exists in the nuclear and aerospace industries and in the refining of beryllium metal and melting of beryllium-containing alloys, the manufacturing of electronic devices, and the handling of other beryllium-containing material. A successful test for beryllium in air and on surfaces has been recently developed and published as an international voluntary consensus standard ASTM D7202. The procedure uses dilute ammonium bifluoride for dissolution and fluorescence detection with beryllium bound to sulfonated hydroxybenzoquinoline, allowing up to 100 times more sensitive detection than the recommended limit for beryllium concentration in the workplace. Fluorescence increases with increasing beryllium concentration. The new procedure has been successfully tested on a variety of surfaces and is effective for the dissolution and ultratrace detection of refractory beryllium oxide and siliceous beryllium (ASTM D7458).

CARBON Carbon (from Latin: carbo "coal") is the chemical element with symbol C and atomic number 6. As a member of group 14 on the periodic table, it is nonmetallicand tetravalentmaking

four electrons available to form covalent chemical bonds. There are three naturally occurring isotopes, 12 13 14 with C and C being stable, while C is radioactive, decaying with a half-life of about 5,730 years. Carbon is one of the few elements known since antiquity. There are several allotropes of carbon of which the best known are graphite, diamond, and amorphous carbon. The physical properties of carbon vary widely with the allotropic form. For example, diamond is highly transparent, while graphite is opaque and black. Diamond is the hardest naturally-occurring material known, while graphite is soft enough to form a streak on paper (hence its name, from the Greek word "" which means "to write"). Diamond has a very lowelectrical conductivity, while graphite is a very good conductor. Under normal conditions, diamond, carbon nanotube and graphene have the highest thermal conductivities of all known materials. All carbon allotropes are solids under normal conditions with graphite being the most thermodynamically stable form. They are chemically resistant and require high temperature to react even with oxygen. The most common oxidation state of carbon in inorganic compounds is +4, while +2 is found in carbon monoxideand other transition metal carbonyl complexes. The largest sources of inorganic carbon are limestones, dolomites and carbon dioxide, but significant quantities occur in organic deposits of coal, peat, oil and methane clathrates. Carbon forms more compounds than any other element, with almost ten million pure organic compounds described to date, which in turn are a tiny fraction of such compounds that are theoretically possible under standard conditions. Carbon is the 15th most abundant element in the Earth's crust, and the fourth most abundant element in the universe by mass after hydrogen, helium, andoxygen. It is present in all known life forms, and in the human body carbon is the second most abundant element by mass (about 18.5%) after oxygen. This abundance, together with the unique diversity of organic compounds and their unusual polymer-forming ability at the temperatures commonly encountered onEarth, make this element the chemical basis of all known life.
1 Characteristics 2 Compounds

o o o

2.1 Organic compounds 2.2 Inorganic compounds 2.3 Organometallic compounds

3 History and etymology 4 Production

o o

4.1 Graphite 4.2 Diamond

5 Applications

5.1 Diamonds

6 Precautions

CHARACTERISTICS The different forms or allotropes of carbon (see below) include the hardest naturally occurring substance, diamond, and also one of the softest known substances, graphite. Moreover, it has an affinity for bonding with other smallatoms, including other carbon atoms, and is capable of forming multiple stable covalent bonds with such atoms. As a result, carbon is known to form almost ten million different compounds; the large majority of all chemical compounds. Carbon also has the highest sublimation point of all elements. At atmospheric pressure it has no melting point as its triple point is at 10.8 0.2 MPa and 4,600 300 K (~4,330 C or 7,820 F), so it sublimes at about 3,900 K. Carbon sublimes in a carbon arc which has a temperature of about 5,800 K (5,530 C; 9,980 F). Thus, irrespective of its allotropic form, carbon remains solid at higher temperatures than the highest melting point metals such astungsten or rhenium. Although thermodynamically prone to oxidation, carbon resists oxidation more effectively than elements such as iron and copper that are weaker reducing agents at room temperature. Carbon compounds form the basis of all known life on Earth, and the carbon-nitrogen cycle provides some of the energy produced by the Sun and other stars. Although it forms an extraordinary variety of compounds, most forms of carbon are comparatively unreactive under normal conditions. At standard temperature and pressure, it resists all but the strongest oxidizers. It does not react with sulfuric acid, hydrochloric acid, chlorineor any alkalis. At elevated temperatures carbon reacts with oxygen to form carbon oxides, and will reduce such metal oxides as iron oxide to the metal. Thisexothermic reaction is used in the iron and steel industry to control the carbon content of steel: Fe
3O 4

+ 4 C(s) 3 Fe(s) + 4 CO(g)

with sulfur to form carbon disulfide and with steam in the coal-gas reaction: C(s) + H2O(g) CO(g) + H2(g). Carbon combines with some metals at high temperatures to form metallic carbides, such as the iron carbide cementite in steel, and tungsten carbide, widely used as an abrasive and for making hard tips for cutting tools. As of 2009, graphene appears to be the strongest material ever tested. However, the process of separating it from graphite will require some technological development before it is economical enough to be used in industrial processes. The system of carbon allotropes spans a range of extremes:

Synthetic nanocrystalline diamond is the hardest material known.

Graphite is one of the softest materials known.

Diamond is the ultimate abrasive.

Graphite is a very good lubricant, displaying superlubricity.

Diamond is an excellent electrical insulator, and has the highest breakdown electric field of any known material.

[22]

Graphite is a conductor of electricity.

Diamond is the best known naturally occurring thermal conductor

Some forms of graphite are used for thermal insulation (i.e. firebreaks and heat shields), but some other forms are good thermal conductors.

Diamond is highly transparent.

Graphite is opaque.

Diamond crystallizes in the cubic system.

Graphite crystallizes in the hexagonal system.

Amorphous carbon is completely isotropic.

Carbon nanotubes are among the most anisotropic materials ever produced.

COMPOUNDS Organic compounds Carbon has the ability to form very long chains of interconnecting C-C bonds. This property is called catenation. Carbon-carbon bonds are strong, and stable. This property allows carbon to form an almost infinite number of compounds; in fact, there are more known carbon-containing compounds than all the compounds of the other chemical elements combined except those of hydrogen (because almost all organic compounds contain hydrogen too). The simplest form of an organic molecule is the hydrocarbona large family of organic molecules that are composed ofhydrogen atoms bonded to a chain of carbon atoms. Chain length, side chains and functional groups all affect the properties of organic molecules.

Carbon occurs in all known organic life and is the basis of organic chemistry. When united with hydrogen, it forms various hydrocarbons which are important to industry as refrigerants, lubricants, solvents, as chemical feedstock for the manufacture of plastics and petrochemicals and as fossil fuels. When combined with oxygen and hydrogen, carbon can form many groups of important biological compounds includingsugars, lignans, chitins, alcohols, fats, and aromatic esters, carotenoids and terpenes. With nitrogen it forms alkaloids, and with the addition of sulfur also it forms antibiotics, amino acids, and rubber products. With the addition of phosphorus to these other elements, it forms DNA and RNA, the chemical-code carriers of life, and adenosine triphosphate (ATP), the most important energy-transfer molecule in all living cells. Inorganic compounds Commonly carbon-containing compounds which are associated with minerals or which do not contain hydrogen or fluorine, are treated separately from classical organic compounds; however the definition is not rigid (see reference articles above). Among these are the simple oxides of carbon. The most prominent oxide is carbon dioxide (CO2). This was once the principal constituent of the paleoatmosphere, but is a minor component of the Earth's atmosphere today. Dissolved in water, it forms carbonic acid (H 2CO3), but as most compounds with multiple single-bonded oxygens on a single carbon it is unstable. Through this intermediate, though, resonance-stabilized carbonate ions are produced. Some important minerals are carbonates, notably calcite. Carbon disulfide (CS2) is similar. The other common oxide is carbon monoxide (CO). It is formed by incomplete combustion, and is a colorless, odorless gas. The molecules each contain a triple bond and are fairly polar, resulting in a tendency to bind permanently to hemoglobin molecules, displacing oxygen, which has a lower binding affinity. Cyanide (CN ), has a similar structure, but behaves much like a halide ion (pseudohalogen). For example it can form the nitridecyanogen molecule ((CN)2), similar to diatomic halides. Other uncommon oxides are carbon suboxide (C3O2), the unstable dicarbon monoxide(C2O), carbon trioxide (CO3), cyclopentanepentone (C5O5) cyclohexanehexone (C6O6), and mellitic anhydride (C12O9). With reactive metals, such as tungsten, carbon forms either carbides (C ), or acetylides (C22) to form alloys with high melting points. These anions are also associated with methane and acetylene, both very weak acids. With an electronegativity of 2.5, carbon prefers to form covalent bonds. A few carbides are covalent lattices, like carborundum (SiC), which resembles diamond. Organometallic compounds Organometallic compounds by definition contain at least one carbon-metal bond. A wide range of such 2 compounds exist; major classes include simple alkyl-metal compounds (for example, tetraethyllead), 3 alkene compounds (for example, Zeise's salt), and -allyl compounds (for example, allylpalladium chloride dimer); metallocenes containing cyclopentadienyl ligands (for example, ferrocene); and transition metal carbene complexes. Many metal carbonyls exist (for example, tetracarbonylnickel); some workers consider the carbon monoxide ligand to be purely inorganic, and not organometallic. While carbon is understood to exclusively form four bonds, an interesting compound containing an octahedral hexacoordinated carbon atom has been reported. The cation of the compound is 2+ [(Ph3PAu)6C] . This phenomenon has been attributed to the aurophilicity of the gold ligands. HISTORY AND ETYMOLOGY
4

The English name carbon comes from the Latin carbo for coal and charcoal, whence also comes the French charbon, meaning charcoal. In German, Dutch and Danish, the names for carbon are Kohlenstoff, koolstof and kulstof respectively, all literally meaning coal-substance. Carbon was discovered in prehistory and was known in the forms of soot and charcoal to the earliest human civilizations. Diamonds were known probably as early as 2500 BCE in China, while carbon in the form of charcoal was made around Roman times by the same chemistry as it is today, by heating wood in a pyramid covered withclay to exclude air. In 1722, Ren Antoine Ferchault de Raumur demonstrated that iron was transformed into steel through the absorption of some substance, now known to be carbon. In 1772, Antoine Lavoisier showed that diamonds are a form of carbon; when he burned samples of charcoal and diamond and found that neither produced any water and that both released the same amount of carbon dioxide per gram. In 1779, Carl Wilhelm Scheele showed that graphite, which had been thought of as a form of lead, was instead identical with charcoal but with a small admixture of iron, and that it gave "aerial acid" (his name for carbon dioxide) when oxidized with nitric acid. In 1786, the French scientists Claude Louis Berthollet, Gaspard Monge and C. A. Vandermonde confirmed that graphite was mostly carbon by oxidizing it in oxygen in much the same way Lavoisier had done with diamond. Some iron again was left, which the French scientists thought was necessary to the graphite structure. However, in their publication they proposed the name carbone (Latin carbonum) for the element in graphite which was given off as a gas upon burning graphite. Antoine Lavoisier then listed carbon as an element in his 1789 textbook. A new allotrope of carbon, fullerene, that was discovered in 1985 includes nanostructured forms such as buckyballs and nanotubes. Their discoverers Robert Curl,Harold Kroto and Richard Smalley received the Nobel Prize in Chemistry in 1996. The resulting renewed interest in new forms lead to the discovery of further exotic allotropes, including glassy carbon, and the realization that "amorphous carbon" is not strictly amorphous. PRODUCTION Graphite Commercially viable natural deposits of graphite occur in many parts of the world, but the most important sources economically are in China, India, Brazil and North Korea. Graphite deposits are ofmetamorphic origin, found in association with quartz, mica and feldspars in schists, gneisses and metamorphosed sandstones and limestone as lenses or veins, sometimes of a meter or more in thickness. Deposits of graphite in Borrowdale, Cumberland, England were at first of sufficient size and purity that, until the 19th century, pencils were made simply by sawing blocks of natural graphite into strips before encasing the strips in wood. Today, smaller deposits of graphite are obtained by crushing the parent rock and floating the lighter graphite out on water. There are three types of natural graphiteamorphous, flake or crystalline flake, and vein or lump. Amorphous graphite is the lowest quality and most abundant. Contrary to science, in industry "amorphous" refers to very small crystal size rather than complete lack of crystal structure. Amorphous is used for lower value graphite products and is the lowest priced graphite. Large amorphous graphite deposits are found in China, Europe, Mexico and the United States. Flake graphite is less common and of higher quality than amorphous; it occurs as separate plates that crystallized in metamorphic rock. Flake graphite can be four times the price of amorphous. Good quality flakes can be processed into expandable graphite for many uses, such as flame retardants. The foremost deposits are found in Austria, Brazil,

Canada, China, Germany and Madagascar. Vein or lump graphite is the rarest, most valuable, and highest quality type of natural graphite. It occurs in veins along intrusive contacts in solid lumps, and it is only commercially mined in Sri Lanka. According to the USGS, world production of natural graphite was 1.1 million tonnes in 2010, to which China contributed 800,000 t, India 130,000 t, Brazil 76,000 t, North Korea 30,000 t and Canada 25,000 t. No natural graphite was reported mined in the United States, but 118,000 t of synthetic graphite with an estimated value of $998 million was produced in 2009. Diamond The diamond supply chain is controlled by a limited number of powerful businesses, and is also highly concentrated in a small number of locations around the world. Only a very small fraction of the diamond ore consists of actual diamonds. The ore is crushed, during which care has to be taken in order to prevent larger diamonds from being destroyed in this process and subsequently the particles are sorted by density. Today, diamonds are located in the diamond-rich density fraction with the help of X-ray fluorescence, after which the final sorting steps are done by hand. Before the use of X-rays became commonplace, the separation was done with grease belts; diamonds have a stronger tendency to stick to grease than the other minerals in the ore. Historically diamonds were known to be found only in alluvial deposits in southern India. India led the world in diamond production from the time of their discovery in approximately the 9th century BCE to the mid-18th century AD, but the commercial potential of these sources had been exhausted by the late 18th century and at that time India was eclipsed by Brazil where the first non-Indian diamonds were found in 1725. Diamond production of primary deposits (kimberlites and lamproites) only started in the 1870s after the discovery of the Diamond fields in South Africa. Production has increased over time and now an accumulated total of 4.5 billion carats have been mined since that date. About 20% of that amount has been mined in the last 5 years alone, and during the last ten years 9 new mines have started production while 4 more are waiting to be opened soon. Most of these mines are located in Canada, Zimbabwe, Angola, and one in Russia. In the United States, diamonds have been found in Arkansas, Colorado and Montana. In 2004, a startling discovery of a microscopic diamond in the United States led to the January 2008 bulk-sampling of kimberlite pipes in a remote part of Montana. Today, most commercially viable diamond deposits are in Russia, Botswana, Australia and the Democratic Republic of Congo. In 2005, Russia produced almost one-fifth of the global diamond output, reports the British Geological Survey. Australia has the richest diamantiferous pipe with production reaching peak levels of 42 metric tons (41 long tons; 46 short tons) per year in the 1990s. There are also commercial deposits being actively mined in the Northwest Territories of Canada, Siberia (mostly in Yakutia territory; for example, Mir pipe and Udachnaya pipe), Brazil, and in Northern and Western Australia. APPLICATIONS Carbon is essential to all known living systems, and without it life as we know it could not exist (see alternative biochemistry). The major economic use of carbon other than food and wood is in the form

of hydrocarbons, most notably the fossil fuel methane gas and crude oil (petroleum). Crude oil is used by the petrochemical industry to produce, amongst other things, gasoline and kerosene, through a distillation process, in refineries. Cellulose is a natural, carbon-containing polymer produced by plants in the form of cotton, linen, and hemp. Cellulose is mainly used for maintaining structure in plants. Commercially valuable carbon polymers of animal origin include wool, cashmere and silk. Plastics are made from synthetic carbon polymers, often with oxygen and nitrogen atoms included at regular intervals in the main polymer chain. The raw materials for many of these synthetic substances come from crude oil. The uses of carbon and its compounds are extremely varied. It can form alloys with iron, of which the most common iscarbon steel. Graphite is combined with clays to form the 'lead' used in pencils used for writing and drawing. It is also used as a lubricant and a pigment, as a molding material in glass manufacture, in electrodes for dry batteries and inelectroplating and electroforming, in brushes for electric motors and as a neutron moderator in nuclear reactors. Charcoal is used as a drawing material in artwork, for grilling, and in many other uses including iron smelting. Wood, coal and oil are used as fuel for production of energy and space heating. Gem quality diamond is used in jewelry, andindustrial diamonds are used in drilling, cutting and polishing tools for machining metals and stone. Plastics are made from fossil hydrocarbons, and carbon fiber, made by pyrolysis of synthetic polyester fibers is used to reinforce plastics to form advanced, lightweight composite materials. Carbon fiber is made by pyrolysis of extruded and stretched filaments ofpolyacrylonitrile (PAN) and other organic substances. The crystallographic structure and mechanical properties of the fiber depend on the type of starting material, and on the subsequent processing. Carbon fibers made from PAN have structure resembling narrow filaments of graphite, but thermal processing may re-order the structure into a continuous rolled sheet. The result is fibers with higher specific tensile strength than steel. Carbon black is used as the black pigment in printing ink, artist's oil paint and water colours, carbon paper, automotive finishes, India ink and laser printer toner. Carbon black is also used as a filler in rubber products such as tyres and inplastic compounds. Activated charcoal is used as an absorbent and adsorbent in filter material in applications as diverse as gas masks, water purification and kitchen extractor hoods and in medicine to absorb toxins, poisons, or gases from the digestive system. Carbon is used in chemical reduction at high temperatures. Coke is used to reduce iron ore into iron. Case hardening of steel is achieved by heating finished steel components in carbon powder. Carbides of silicon,tungsten, boron and titanium, are among the hardest known materials, and are used as abrasives in cutting and grinding tools. Carbon compounds make up most of the materials used in clothing, such as natural and synthetic textiles andleather, and almost all of the interior surfaces in the built environment other than glass, stone and metal. Diamonds The diamond industry can be broadly separated into two basically distinct categories: one dealing with gem-grade diamonds and another for industrial-grade diamonds. While a large trade in both types of diamonds exists, the two markets act in dramatically different ways. A large trade in gem-grade diamonds exists. Unlike precious metals such as gold or platinum, gem diamonds do not trade as a commodity: there is a substantial mark-up in the sale of diamonds, and there is not a very active market for resale of diamonds.

The market for industrial-grade diamonds operates much differently from its gem-grade counterpart. Industrial diamonds are valued mostly for their hardness and heat conductivity, making many of the gemological characteristics of diamond, including clarity and color, mostly irrelevant. This helps explain why 80% of mined diamonds (equal to about 100 million carats or 20 tonnes annually), unsuitable for use as gemstones and known as bort, are destined for industrial use. In addition to mined diamonds, synthetic diamonds found industrial applications almost immediately after their invention in the 1950s; another 3 billion carats (600 tonnes) of synthetic diamond is produced annually for industrial use. The dominant industrial use of diamond is in cutting, drilling, grinding, and polishing. Most uses of diamonds in these technologies do not require large diamonds; in fact, most diamonds that are gem-quality except for their small size, can find an industrial use. Diamonds are embedded in drill tips or saw blades, or ground into a powder for use in grinding and polishing applications. Specialized applications include use in laboratories as containment for high pressure experiments (see diamond anvil cell), high-performance bearings, and limited use in specialized windows. With the continuing advances being made in the production of synthetic diamonds, future applications are beginning to become feasible. Garnering much excitement is the possible use of diamond as a semiconductor suitable to build microchips from, or the use of diamond as a heat sink in electronics. PRECAUTIONS Pure carbon has extremely low toxicity to humans and can be handled and even ingested safely in the form of graphite or charcoal. It is resistant to dissolution or chemical attack, even in the acidic contents of the digestive tract, for example. Consequently once it enters into the body's tissues it is likely to remain there indefinitely. Carbon blackwas probably one of the first pigments to be used for tattooing, and tzi the Iceman was found to have carbon tattoos that survived during his life and for 5200 years after his death. However, inhalation of coal dust or soot (carbon black) in large quantities can be dangerous, irritating lung tissues and causing the congestive lung diseasecoalworker's pneumoconiosis. Similarly, diamond dust used as an abrasive can do harm if ingested or inhaled. Microparticles of carbon are produced in diesel engine exhaust fumes, and may accumulate in the lungs. In these examples, the harmful effects may result from contamination of the carbon particles, with organic chemicals or heavy metals for example, rather than from the carbon itself. Carbon generally has low toxicity to almost all life on Earth; however, to some creatures it can still be toxic. For instance, carbon nanoparticles are deadly to Drosophila. Carbon may also burn vigorously and brightly in the presence of air at high temperatures, as in the Windscale fire, which was caused by sudden release of stored Wigner energy in the graphite core. Large accumulations of coal, which have remained inert for hundreds of millions of years in the absence of oxygen, may spontaneously combustwhen exposed to air, for example in coal mine waste tips. The great variety of carbon compounds include such lethal poisons as tetrodotoxin, the lectin ricin from seeds of the castor oil plant Ricinus communis, cyanide (CN ) andcarbon monoxide; and such essentials to life as glucose and protein. NITROGEN Nitrogen, symbol N, is the chemical element of atomic number 7. At room temperature, it is a gas of diatomic molecules and is colorless and odorless. Nitrogen is a common element in the universe, estimated at about seventh in total abundance in our galaxy and the Solar System. On Earth, the element is primarily found as the free element; it forms about 80% of the Earth's atmosphere. The element

nitrogen was discovered as a separable component of air, by Scottish physician Daniel Rutherford, in 1772. Many industrially important compounds, such as ammonia, nitric acid, organic nitrates (propellants and explosives), and cyanides, contain nitrogen. The extremely strong bond in elemental nitrogen dominates nitrogen chemistry, causing difficulty for both organisms and industry in converting the N2 into useful compounds, but at the same time causing release of large amounts of often useful energy when the compounds burn, explode, or decay back into nitrogen gas. Syntheticallyproduced ammonia and nitrates are key industrial fertilizers and fertilizer nitrates are key pollutants in causing the eutrophication of water systems. Outside their major uses as fertilizers and energy-stores, nitrogen compounds are versatile organics. Nitrogen is part of materials as diverse as Kevlar fabric and cyanoacrylate "super" glue. Nitrogen is a constituent of molecules in every major pharmacological drug class, including the antibiotics. Many drugs are mimics or prodrugs of natural nitrogen-containing signal molecules: for example, the organic nitrates nitroglycerin and nitroprusside control blood pressure by being metabolized to natural nitric oxide. Plant alkaloids (often defense chemicals) contain nitrogen by definition, and thus many notable nitrogencontaining drugs, such as caffeine and morphine are either alkaloids or synthetic mimics that act (as many plant alkaloids do) upon receptors of animal neurotransmitters (for example, synthetic amphetamines). Nitrogen occurs in all organisms, primarily in amino acids (and thus proteins) and also in the nucleic acids (DNA and RNA). The human body contains about 3% by weight of nitrogen, the fourth most abundant element in the body after oxygen, carbon, and hydrogen. The nitrogen cycle describes movement of the element from the air, into the biosphere and organic compounds, then back into the atmosphere.
1 History and etymology 2 Production 3 Properties 4 Occurrence 5 Compounds 6 Applications

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6.1 Nitrogen gas 6.2 Liquid nitrogen 6.3 Nitrogen compounds

7 Biological role 8 Safety

HISTORY AND ETYMOLOGY

Nitrogen is formally considered to have been discovered by Scottish physician Daniel Rutherford in 1772, who called it noxious air or fixed air. The fact that there was a component of air that does not

support combustion was clear to Rutherford. Nitrogen was also studied at about the same time by Carl Wilhelm Scheele, Henry Cavendish, and Joseph Priestley, who referred to it as burnt air or phlogisticated air. Nitrogen gas was inert enough that Antoine Lavoisierreferred to it as "mephitic air" or azote, from the Greek word (azotos) meaning "lifeless". In it, animals died and flames were extinguished. Lavoisier's name for nitrogen is used in many languages (French, Italian, Polish, Russian, Albanian, etc.) and still remains in English in the common names of many compounds, such as hydrazine and compounds of the azide ion. The English word nitrogen (1794) entered the language from the French nitrogne, coined in 1790 by French chemist Jean-Antoine Chaptal (17561832), from the Greek "nitron" (sodium carbonate) and the French gne (producing). The gas had been found in nitric acid. Chaptal's meaning was that nitrogen gas is the essential part of nitric acid, in turn formed from saltpetre (potassium nitrate), then known as nitre. This word in the more ancient world originally describedsodium salts that did not contain nitrate, and is a cognate of natron. Nitrogen compounds were well known by the Middle Ages. Alchemists knew nitric acid as aqua fortis (strong water). The mixture of nitric and hydrochloric acidswas known as aqua regia (royal water), celebrated for its ability to dissolve gold (the king of metals). The earliest military, industrial, and agricultural applications of nitrogen compounds used saltpetre (sodium nitrate or potassium nitrate), most notably in gunpowder, and later as fertilizer. In 1910, Lord Rayleigh discovered that an electrical discharge in nitrogen gas produced "active nitrogen", an allotrope considered to be monatomic. The "whirling cloud of brilliant yellow light" produced by his apparatus reacted with quicksilver to produce explosive mercury nitride. For a long time sources of nitrogen compounds were limited. Natural sources originated either from biology or deposits of nitrates produced by atmospheric reactions. Nitrogen fixation by industrial processes like the Frank-Caro process (1895-1899) and Haber-Bosch process (1908-1913) eased this shortage of nitrogen compounds, to the extent that half of global food production (see applications) now relies on synthetic nitrogen fertilizers. At the same time, use of theOstwald process (1902) to produce nitrates from industrial nitrogen fixation allowed the large-scale industrial production of nitrates which th fueled explosives in the world wars of the 20 century. PRODUCTION Nitrogen gas is an industrial gas produced by the fractional distillation of liquid air, or by mechanical means using gaseous air (i.e., pressurized reverse osmosis membrane or pressure swing adsorption). Commercial nitrogen is often a byproduct of air-processing for industrial concentration of oxygen for steelmaking and other purposes. When supplied compressed in cylinders it is often called OFN (oxygenfree nitrogen). In a chemical laboratory it is prepared by treating an aqueous solution of ammonium chloride with sodium nitrite. NH4Cl(aq) + NaNO2(aq) N2(g) + NaCl(aq) + 2 H2O (l) Small amounts of impurities NO and HNO3 are also formed in this reaction. The impurities can be removed by passing the gas through aqueous sulfuric acid containing potassium dichromate. Very pure nitrogen can be prepared by the thermal decomposition of barium azide or sodium azide.

2 NaN3 2 Na + 3 N2

PROPERTIES Nitrogen is a nonmetal, with an electronegativity of 3.04. It has five electrons in its outer shell and is, therefore, trivalent in most compounds. The triple bond in molecular nitrogen (N2) is one of the strongest. The resulting difficulty of converting N2 into other compounds, and the ease (and associated high energy release) of converting nitrogen compounds into elemental N2, have dominated the role of nitrogen in both nature and human economic activities. At atmospheric pressure, molecular nitrogen condenses (liquefies) at 77 K (195.79 C) and freezes at 63 K (210.01 C) into the beta hexagonal close-packed crystal allotropic form. Below 35.4 K (237.6 C) nitrogen assumes the cubic crystal allotropic form (called the alpha phase). Liquid nitrogen, a fluid resembling water in appearance, but with 80.8% of the density (the density of liquid nitrogen at its boiling point is 0.808 g/mL), is a common cryogen. Unstable allotropes of nitrogen consisting of more than two nitrogen atoms have been produced in the laboratory, like N3 and N4. Under extremely high pressures (1.1 million atm) and high temperatures (2000 K), as produced using a diamond anvil cell, nitrogen polymerizes into the single-bonded cubic gauche crystal structure. This structure is similar to that of diamond, and both have extremely strong covalent bonds. N4 is nicknamed "nitrogen diamond". Other (as yet unsynthesized) allotropes include hexazine (N6, benzene analog) and octaazacubane (N 8, a cubane analog). The former is predicted to be highly unstable, while the latter is predicted to be kinetically stable, for reasons of orbital symmetry. OCCURRENCE Nitrogen gas (N2) is the largest constituent of the Earth's atmosphere (78.082% by volume of dry air, 75.3% by weight in dry air). However, this high concentration does not reflect nitrogen's overall low abundance in the makeup of the Earth, from which most of the element escaped by solar evaporation, early in the planet's formation. Nitrogen is a common element in the universe, and is estimated to be approximately the seventh most abundant chemical element by mass in the universe, our galaxy and the Solar System. In these places it was originally created by fusion processes from carbon and hydrogen in supernovas. Molecular nitrogen and nitrogen compounds have been detected in interstellar space by astronomers using the Far Ultraviolet Spectroscopic Explorer. Due to the volatility of elemental nitrogen and also its common compounds with hydrogen and oxygen, nitrogen and its compounds were driven out of the planetesimals in the early Solar System by the heat of the Sun, and in the form of gases, were lost to the rocky planets of the inner Solar System. Nitrogen is therefore a relatively rare element on these inner planets, including Earth, as a whole. In this, nitrogen resembles neon, which has a similar high abundance in the universe, but is also rare in the inner Solar th System. Nitrogen is estimated at 30 of the elements in crustal abundance. There exist some relatively uncommon nitrogen minerals, such as saltpetre (potassium nitrate), Chile saltpetre (sodium nitrate) and sal ammoniac (ammonium chloride). Even these are known mainly as concentrated from evaporative

ocean beds, due to their ready solubility of most naturally-occurring nitrogen compounds in water. A similar pattern occurs with the water solubility of the uncommon light element boron. However, nitrogen and its compounds occur far more commonly as gases in the atmospheres of planets and moons that are large enough to have atmospheres. For example, molecular nitrogen is a major constituent of not only Earth's atmosphere, but also the Saturnian moon Titan's thick atmosphere. Also, due to retention by gravity at colder temperatures, nitrogen and its compounds occur in trace to appreciable amounts in planetary atmospheres of the gas giant planets. Nitrogen is present in all living organisms, in proteins, nucleic acids, and other molecules. It typically makes up around 4% of the dry weight of plant matter, and around 3% of the weight of the human body. It is a large component of animal waste (for example, guano), usually in the form of urea, uric acid, ammonium compounds, and derivatives of these nitrogenous products, which are essential nutrients for all plants that cannot fix atmospheric nitrogen. COMPOUNDS The main neutral hydride of nitrogen is ammonia (NH3), although hydrazine (N2H4) is also commonly used. Ammonia is more basic than water by 6 orders of magnitude. In solution ammonia forms theammonium ion (NH+4). Liquid ammonia (boiling point 240 K) is amphiprotic (displaying either Brnsted-Lowry acidic or basic character) and forms ammonium and the less common amide ions (NH2); both amides and nitride (N3) salts are known, but decompose in water. Singly, doubly, triply and quadruply substituted alkyl compounds of ammonia are called amines (four substitutions, to form commercially and biologically important quaternary amines, results in a positively charged nitrogen, and thus a water-soluble, or at least amphiphilic, compound). Larger chains, rings and structures of nitrogen hydrides are also known, but are generally unstable. Other classes of nitrogen anions (negatively charged ions) are the poisonous azides (N3), which are linear and isoelectronic to carbon dioxide, but which bind to important iron-containing enzymes in the body in a manner more resembling cyanide. Another molecule of the same structure is the colorless and relatively inert anesthetic gas Nitrous oxide (dinitrogen monoxide, N2O), also known as laughing gas. This is one of a variety of nitrogen oxides that form a family often abbreviated as NOx. Nitric oxide (nitrogen monoxide, NO), is a natural free radical used in signal transduction in both plants and animals, for example, in vasodilation by causing the smooth muscle of blood vessels to relax. The reddish and poisonous nitrogen dioxide NO2 contains an unpaired electron and is an important component of smog. Nitrogen molecules containing unpaired electrons show a tendency to dimerize (thus pairing the electrons), and are, in general, highly reactive. The corresponding acids are nitrous HNO2 and nitric acid HNO3, with the corresponding salts called nitrites and nitrates. The higher oxides dinitrogen trioxide N2O3, dinitrogen tetroxide N2O4 and dinitrogen pentoxide N2O5, are unstable and explosive, a consequence of the chemical stability of N2. Nearly every hypergolic rocket engine uses N2O4 as the oxidizer; their fuels, various forms of hydrazine, are also nitrogen compounds. These engines are extensively used on spacecraft such as the space shuttle and those of the Apollo Program because their propellants are liquids at room temperature and ignition occurs on contact without an ignition system, allowing many precisely controlled burns. Some launch vehicles such as the Titan II and Ariane 1 through 4 also use hypergolic fuels, although the trend is away from such engines for cost and safety reasons. N2O4 is an intermediate in the manufacture of nitric acid HNO3, one of the few acids stronger than hydronium and a fairly strong oxidizing agent.

Nitrogen is notable for the range of explosively unstable compounds that it can produce. Nitrogen triiodide NI3 is an extremely sensitive contact explosive. Nitrocellulose, produced by nitration of cellulose with nitric acid, is also known as guncotton. Nitroglycerin, made by nitration of glycerin, is the dangerously unstable explosive ingredient of dynamite. The comparatively stable, but less powerful explosivetrinitrotoluene (TNT) is the standard explosive against which the power of nuclear explosions are measured. Nitrogen can also be found in organic compounds. Common nitrogen functional groups include: amines, amides, nitro groups, imines, and enamines. The amount of nitrogen in a chemical substance can be determined by the Kjeldahl method. APPLICATIONS Nitrogen Gas Nitrogen gas has a variety of applications, including serving as an inert replacement for air where oxidation is undesirable; As a modified atmosphere, pure or mixed with carbon dioxide, to preserve the freshness of packaged or bulk foods (by delaying rancidity and other forms of oxidative damage). Pure nitrogen as food additive is labelled in the European Union with the E number E941. In ordinary incandescent light bulbs as an inexpensive alternative to argon. The production of electronic parts such as transistors, diodes, and integrated circuits. Dried and pressurized, as a dielectric gas for high-voltage equipment. The manufacturing of stainless steel. Used in some aircraft fuel systems to reduce fire hazard, (see inerting system). On top of liquid explosives as a safety measure. Filling automotive and aircraft tires due to its inertness and lack of moisture or oxidative qualities, as opposed to air. The difference in N2 content between air and pure N2 is 20%. Used as a propellant for draft wine, and as an alternative to or together with carbon dioxide for other beverages.

Nitrogen is commonly used during sample preparation procedures for chemical analysis. It is used to concentrate and reduce the volume of liquid samples. Directing a pressurized stream of nitrogen gas perpendicular to the surface of the liquid allows the solvent to evaporate while leaving the solute(s) and un-evaporated solvent behind. Nitrogen tanks are also replacing carbon dioxide as the main power source for paintball guns. Nitrogen must be kept at higher pressure than CO2, making N2 tanks heavier and more expensive. Nitrogen can be used as a replacement, or in combination with, carbon dioxide to pressurize kegs of some beers, particularly stouts and British ales, due to the smaller bubbles it produces, which makes the dispensed beer smoother and headier. A pressure-sensitive nitrogen capsule known commonly as a "widget" allows nitrogen-charged beers to be packaged in cans and bottles. Liquid Nitrogen Liquid nitrogen is a cryogenic liquid. At atmospheric pressure, it boils at 195.8 C. When insulated in proper containers such as Dewar flasks, it can be transported without much evaporative loss.

Like dry ice, the main use of liquid nitrogen is as a refrigerant. Among other things, it is used in the cryopreservation of blood, reproductive cells (sperm and egg), and other biological samples and materials. It is used in the clinical setting in cryotherapy to remove cysts and warts on the skin. It is used in cold traps for certain laboratory equipment and to cool infrared detectors or X-ray detectors. It has also been used to cool central processing units and other devices in computers that are overclocked, and that produce more heat than during normal operation. Nitrogen compounds Molecular nitrogen (N2) in the atmosphere is relatively non-reactive due to its strong bond, and N2 plays an inert role in the human body, being neither produced nor destroyed. In nature, nitrogen is converted into biologically (and industrially) useful compounds by lightning, and by some living organisms, notably certain bacteria(i.e., nitrogen fixing bacteriasee Biological role below). Molecular nitrogen is released into the atmosphere in the process of decay, in dead plant and animal tissues. The ability to combine, or fix, molecular nitrogen is a key feature of modern industrial chemistry. th Previously to the 20 century, access to nitrogen compounds for fertilizers and gunpowder had been through deposits of natural nitrates, such as Chilean saltpeter. However, first the Frank-Caro process for producing cyanamide, and then the Haber-Bosch process for producing ammonia from air and natural gas (developed just before the first world war) eased this shortage of nitrogen compounds, to the extent that half of global food production now relies on synthetic nitrogen fertilizers. The Ostwald process, developed a few years before the Haber process, allowed large-scale production of nitric acid and nitrate from ammonia, thus freeing large-scale industrial production of nitrate explosives and weapons propellants from the need to mine nitrate salt deposits. The organic and inorganic salts of nitric acid have been important historically as convenient stores of chemical energy for warfare and rocket fuels. Historically, such compounds included important compounds such as potassium nitrate, used in gunpowder which was often produced by biological means (bacterial fermentation) before natural mineral sources were discovered. Later, all such sources were displaced by industrial production, in the early 1900s. Ammonium nitrate has been used as both fertilizer and explosive (see ANFO). Various other nitrated organic compounds, such as nitroglycerin, trinitrotoluene, and nitrocellulose, are used as explosives and propellants for modern firearms. Nitric acid is used as an oxidizing agent in liquid fueled rockets. Hydrazine and hydrazine derivatives find use as rocket fuels and monopropellants. In most of these compounds, the basic instability and tendency to burn or explode is derived from the fact that nitrogen is present as an oxide, and not as the far more stable nitrogen molecule (N2), which is a product of the compounds' thermal decomposition. When nitrates burn or explode, the formation of the powerful triple bond in the N2 produces most of the energy of the reaction. Nitrogen is a constituent of molecules in every major drug class in pharmacology and medicine. Nitrous oxide (N2O) was discovered early in the 19th century to be a partial anesthetic, though it was not used as a surgical anesthetic until later. Called "laughing gas", it was found capable of inducing a state of social disinhibition resembling drunkenness. Other notable nitrogen-containing drugs are drugs derived from plant alkaloids, such as morphine (there exist many alkaloids known to have pharmacological effects; in some cases, they appear as natural chemical defenses of plants against predation). Drugs that contain nitrogen include all major classes of antibiotics and organic nitrate drugs

like nitroglycerin and nitroprusside that regulate blood pressure and heart action by mimicking the action of nitric oxide. BIOLOGICAL ROLE Nitrogen is an essential building block of amino and nucleic acids, essential to life on Earth. Elemental nitrogen in the atmosphere cannot be used directly by either plants or animals, and must be converted to a reduced (or 'fixed') state to be useful for higher plants and animals. Precipitation often contains substantial quantities of ammonium and nitrate, thought to result from nitrogen fixation by lightning and other atmospheric electric phenomena. This was first proposed by Liebig in 1827 and later confirmed. However, because ammonium is preferentially retained by the forest canopy relative to atmospheric nitrate, most fixed nitrogen reaches the soil surface under trees as nitrate. Soil nitrate is preferentially assimilated by tree roots relative to soil ammonium. Specific bacteria (e.g., Rhizobium trifolium) possess nitrogenase enzymes that can fix atmospheric nitrogen (see nitrogen fixation) into a form (ammonium ion) that is chemically useful to higher organisms. This process requires a large amount of energy and anoxic conditions. Such bacteria may live freely in soil (e.g., Azotobacter) but normally exist in a symbiotic relationship in the root nodules of leguminousplants (e.g. clover, Trifolium, or soybean plant, Glycine max). Nitrogen-fixing bacteria are also symbiotic with a number of unrelated plant species such as alders ( Alnus) spp., lichens, Casuarina, Myrica,liverworts, and Gunnera. As part of the symbiotic relationship, the plant converts the 'fixed' ammonium ion to nitrogen oxides and amino acids to form proteins and other molecules, (e.g., alkaloids). In return for the 'fixed' nitrogen, the plant secretes sugars to the symbiotic bacteria. Legumes maintain an anaerobic (oxygen free) environment for their nitrogen-fixing bacteria. Plants are able to assimilate nitrogen directly in the form of nitrates that may be present in soil from natural mineral deposits, artificial fertilizers, animal waste, or organic decay (as the product of bacteria, but not bacteria specifically associated with the plant). Nitrates absorbed in this fashion are converted to nitrites by the enzyme nitrate reductase, and then converted to ammonia by another enzyme called nitritereductase. Nitrogen compounds are basic building blocks in animal biology as well. Animals use nitrogencontaining amino acids from plant sources as starting materials for all nitrogen-compound animal biochemistry, including the manufacture of proteins and nucleic acids. Plant-feeding insects are dependent on nitrogen in their diet, such that varying the amount of nitrogen fertilizer applied to a plant can affect the reproduction rate of insects feeding on fertilized plants. Soluble nitrate is an important limiting factor in the growth of certain bacteria in ocean waters. In many places in the world, artificial fertilizers applied to crop-lands to increase yields result in run-off delivery of soluble nitrogen to oceans at river mouths. This process can result in eutrophication of the water, as nitrogen-driven bacterial growth depletes water oxygen to the point that all higher organisms die. Wellknown "dead zone" areas in the U.S. Gulf Coast and the Black Sea are due to this important polluting process. Many saltwater fish manufacture large amounts of trimethylamine oxide to protect them from the high osmotic effects of their environment; conversion of this compound to dimethylamine is responsible

for the early odor in unfresh saltwater fish. In animals, free radical nitric oxide (NO) (derived from an amino acid), serves as an important regulatory molecule for circulation. Nitric oxide's rapid reaction with water in animals results in production of its metabolite nitrite. Animal metabolism of nitrogen in proteins, in general, results in excretion of urea, while animal metabolism ofnucleic acids results in excretion of urea and uric acid. The characteristic odor of animal flesh decay is caused by the creation of long-chain, nitrogen-containing amines, such as putrescine and cadaverine, which are breakdown products of the amino acids ornithine and lysine, respectively, in decaying proteins. Decay of organisms and their waste products may produce small amounts of nitrate, but most decay eventually returns nitrogen content to the atmosphere, as molecular nitrogen. The circulation of nitrogen from atmosphere, to organic compounds, then back to the atmosphere, is referred to as the nitrogen cycle. SAFETY Rapid release of nitrogen gas into an enclosed space can displace oxygen, and therefore represents an asphyxiation hazard. This may happen with few warning symptoms, since the human carotid body is a relatively slow and a poor low-oxygen (hypoxia) sensing system. An example occurred shortly before the launch of the first Space Shuttle mission in 1981, when two technicians lost consciousness (and one of them died) after they walked into a space located in the Shuttle's Mobile Launcher Platform that was pressurized with pure nitrogen as a precaution against fire. The technicians would have been able to exit the room if they had experienced early symptoms from nitrogen-breathing. When inhaled at high partial pressures (more than about 4 bar, encountered at depths below about 30 m in scuba diving), nitrogen begins to act as an anesthetic agent. It can cause nitrogen narcosis, a temporary semi-anesthetized state of mental impairment similar to that caused by nitrous oxide. Nitrogen also dissolves in the bloodstream and body fats. Rapid decompression (in particular, in the case of divers ascending too quickly, or astronauts decompressing too quickly from cabin pressure to spacesuit pressure) can lead to a potentially fatal condition called decompression sickness (formerly known as caisson sickness or the bends), when nitrogen bubbles form in the bloodstream, nerves, joints, and other sensitive or vital areas. Bubbles from other "inert" gases (those gases other than carbon dioxide and oxygen) cause the same effects, so replacement of nitrogen in breathing gases may prevent nitrogen narcosis, but does not prevent decompression sickness. Direct skin contact with liquid nitrogen will cause severe frostbite (cryogenic "burns"). This may happen almost instantly on contact, or after a second or more, depending on the form of liquid nitrogen. Bulk liquid nitrogen causes less rapid freezing than a spray of nitrogen mist (such as is used to freeze certain skin growths in the practice of dermatology). The extra surface area provided by nitrogen-soaked materials is also important, with soaked clothing or cotton causing far more rapid damage than a spill of direct liquid to skin. Full "contact" between naked skin and large collected-droplets or pools of liquid nitrogen may be prevented for a second or two, by a layer of insulating gas from the Leidenfrost effect. This may give the skin a second of protection from nitrogen bulk liquid. However, liquid nitrogen applied to skin in mists, and on fabrics, bypasses this effect, and causes local frostbite immediately. Oxygen sensors are sometimes used as a safety precaution when working with liquid nitrogen to alert workers of gas spills into a confined space.

OXYGEN Oxygen is a chemical element with symbol O and atomic number 8. It is a member of the chalcogen group on the periodic table and is a highly reactivenonmetallic element and oxidizing agent that readily forms compounds (notably oxides) with most elements. By mass, oxygen is the thirdmost abundant element in the universe, after hydrogen and helium At STP, two atoms of the element bind to form dioxygen, a diatomic gas that is colorless, odorless, and tasteless; with the formula O2. Many major classes of organic molecules in living organisms, such as proteins, nucleic acids, carbohydrates, and fats, contain oxygen, as do the majorinorganic compounds that are constituents of animal shells, teeth, and bone. Most of the mass of living organisms is oxygen as it is a part of water, the major constituent of lifeforms (for example, about two-thirds of human body mass). Elemental oxygen is produced by cyanobacteria, algae and plants, and is used in cellular respiration for all complex life. Oxygen is toxic to obligately anaerobic organisms, which were the dominant form of early life on Earth until O2 began to accumulate in the atmosphere. Free elemental O2 only began to accumulate in the atmosphere about 2.5 billion years ago about a billion years after the first appearance of these organisms. Diatomic oxygen gas constitutes 20.8% of the volume of air. Oxygen is the most abundant element by mass in the Earth's crust as part of oxide compounds such as silicon dioxide, making up almost half of the crust's mass. Oxygen is an important part of the atmosphere, and is necessary to sustain most terrestrial life as it is used in respiration. However, it is too chemically reactive to remain a free element in Earth's atmosphere without being continuously replenished by the photosynthetic action of living organisms, which use the energy of sunlight to produce elemental oxygen from water. Another form (allotrope) of oxygen, ozone (O3), strongly absorbs UVB radiation and consequently the high-altitude ozone layer helps protect the biosphere from ultraviolet radiation, but is a pollutant near the surface where it is a by-product of smog. At even higher low earth orbit altitudes, atomic oxygen is a significant presence and a cause of erosion for spacecraft. Oxygen is produced industrially by fractional distillation of liquefied air, use of zeolites with pressure-cycling to concentrate oxygen from air, electrolysis of water and other means. Uses of elemental oxygen include the production of steel, plastics and textiles, brazing, welding and cutting of steels and other metals,rocket propellant, oxygen therapy and life support systems in aircraft, submarines, spaceflight and diving. Oxygen was discovered independently by Carl Wilhelm Scheele, in Uppsala, in 1773 or earlier, and Joseph Priestley in Wiltshire, in 1774, but Priestley is often given priority because his work was published first. The name oxygen was coined in 1777 by Antoine Lavoisier, whose experiments with oxygen helped to discredit the then-popular phlogiston theory of combustion and corrosion. Its name derives from the Greek roots (oxys) ("acid", literally "sharp", referring to the sour taste of acids) and (-gnos) ("producer", literally "begetter"), because at the time of naming, it was mistakenly thought that all acids required oxygen in their composition.
1 Characteristics

o o o

1.1 Structure 1.2 Allotropes 1.3 Physical properties

o o

1.4 Isotopes and stellar origin 1.5 Occurrence

2 Biological role of O2

o o o

2.1 Photosynthesis and respiration 2.2 Content in body 2.3 Build-up in the atmosphere

3 History

o o o o

3.1 Early experiments 3.2 Phlogiston theory 3.3 Discovery 3.4 Lavoisier's contribution

4 Industrial production 5 Applications

o o o o

5.1 Medical 5.2 Life support and recreational use 5.3 Industrial 5.4 Scientific

6 Compounds 7 Safety and precautions

CHARACTERISTICS Structure At standard temperature and pressure, oxygen is a colorless, odorless gas with the molecular formula O 2, in which the two oxygen atoms are chemically bonded to each other with a spin triplet electron configuration. This bond has a bond order of two, and is often simplified in description as a double bond or as a combination of one two-electron bond and two three-electron bonds. Triplet oxygen (not to be confused with ozone, O3) is the ground state of the O2 molecule. The electron configuration of the molecule has two unpaired electrons occupying two degenerate molecular orbitals. These orbitals are classified as antibonding (weakening the bond order from three to two), so the diatomic oxygen bond is weaker than the diatomic nitrogen triple bond in which all bonding molecular orbitals are filled, but some antibonding orbitals are not. In normal triplet form, O2 molecules are paramagnetic. That is, they form a magnet in the presence of a magnetic fieldbecause of the spin magnetic moments of the unpaired electrons in the molecule, and the negative exchange energy between neighboring O2 molecules. Liquid oxygen is attracted to a magnet to a sufficient extent that, in laboratory demonstrations, a bridge of liquid oxygen may be supported against its own weight between the poles of a powerful magnet.

Singlet oxygen is a name given to several higher-energy species of molecular O2 in which all the electron spins are paired. It is much more reactive towards common organic molecules than is molecular oxygen per se. In nature, singlet oxygen is commonly formed from water during photosynthesis, using the energy of sunlight. It is also produced in the troposphere by the photolysis of ozone by light of short wavelength, and by the immune system as a source of active oxygen. Carotenoids in photosynthetic organisms (and possibly also in animals) play a major role in absorbing energy from singlet oxygen and converting it to the unexcited ground state before it can cause harm to tissues. Allotropes The common allotrope of elemental oxygen on Earth is called dioxygen, O2. It has a bond length of 1 121 pm and a bond energy of 498 kJmol . This is the form that is used by complex forms of life, such as animals, in cellular respiration (see Biological role) and is the form that is a major part of the Earth's atmosphere (see Occurrence). Other aspects of O2 are covered in the remainder of this article. Trioxygen (O3) is usually known as ozone and is a very reactive allotrope of oxygen that is damaging to lung tissue. Ozone is produced in the upper atmosphere when O2 combines with atomic oxygen made by the splitting of O2 by ultraviolet (UV) radiation. Since ozone absorbs strongly in the UV region of the spectrum, the ozone layer of the upper atmosphere functions as a protective radiation shield for the planet. Near the Earth's surface, however, it is a pollutant formed as a by-product of automobile exhaust. The metastable molecule tetraoxygen (O4) was discovered in 2001, and was assumed to exist in one of the six phases of solid oxygen. It was proven in 2006 that this phase, created by pressurizing O 2 to 20 GPa, is in fact arhombohedral O8 cluster. This cluster has the potential to be a much more powerful oxidizer than either O2 or O3 and may therefore be used in rocket fuel. A metallic phase was discovered in 1990 when solid oxygen is subjected to a pressure of above 96 GPa and it was shown in 1998 that at very low temperatures, this phase becomes superconducting. Physical properties Oxygen is more soluble in water than nitrogen is. Water in equilibrium with air contains approximately 1 molecule of dissolved O2 for every 2 molecules of N2, compared to an atmospheric ratio of approximately 1 1:4. The solubility of oxygen in water is temperature-dependent, and about twice as much (14.6 mgL ) 1 dissolves at 0 C than at 20 C (7.6 mgL ). At 25 C and 1 standard atmosphere (101.3 kPa) of air, freshwater contains about 6.04 milliliters (mL) of oxygen per liter, whereas seawater contains about 4.95 mL per liter. At 5 C the solubility increases to 9.0 mL (50% more than at 25 C) per liter for water and 7.2 mL (45% more) per liter for sea water. Oxygen condenses at 90.20 K (182.95 C, 297.31 F), and freezes at 54.36 K (218.79 C, 361.82 F). Both liquid and solid O2 are clear substances with a light sky-blue color caused by absorption in the red (in contrast with the blue color of the sky, which is due to Rayleigh scattering of blue light). High-purity liquid O2 is usually obtained by the fractional distillation of liquefied air. Liquid oxygen may also be produced by condensation out of air, using liquid nitrogen as a coolant. It is a highly reactive substance and must be segregated from combustible materials. Isotopes and stellar origin Naturally occurring oxygen is composed of three stable isotopes, O, most abundant (99.762% natural abundance).
16 17

O, and O, with

18

16

O being the

Most O is synthesized at the end of the helium fusion process in massive stars but some is made in 17 the neon burning process. O is primarily made by the burning of hydrogen into helium during the CNO 18 cycle, making it a common isotope in the hydrogen burning zones of stars. Most O is produced 14 4 18 when N (made abundant from CNO burning) captures a He nucleus, making O common in the helium-rich zones of evolved, massive stars. Fourteen radioisotopes have been characterized. The most stable are O with a half-life of 14 122.24 seconds and O with a half-life of 70.606 seconds. All of the remainingradioactive isotopes have half-lives that are less than 27 s and the majority of these have half-lives that are less than 16 + 83 milliseconds. The most common decay mode of the isotopes lighter than O is decay to yield 18 nitrogen, and the most common mode for the isotopes heavier than O is beta decay to yield fluorine. Occurrence Oxygen is the most abundant chemical element by mass in the Earth's biosphere, air, sea and land. Oxygen is the third most abundant chemical element in the universe, after hydrogen and helium. About 0.9% of the Sun's mass is oxygen. Oxygen constitutes 49.2% of the Earth's crust by mass and is the major component of the world's oceans (88.8% by mass). Oxygen gas is the second most common component of the Earth's atmosphere, taking up 20.8% of its volume and 23.1% of its mass (some 15 [6][38][c] 10 tonnes). Earth is unusual among the planets of the Solar System in having such a high concentration of oxygen gas in its atmosphere: Mars (with 0.1% O2 by volume) and Venus have far lower concentrations. However, the O2 surrounding these other planets is produced solely by ultraviolet radiation impacting oxygen-containing molecules such as carbon dioxide. The unusually high concentration of oxygen gas on Earth is the result of the oxygen cycle. This biogeochemical cycle describes the movement of oxygen within and between its three main reservoirs on Earth: the atmosphere, the biosphere, and the lithosphere. The main driving factor of the oxygen cycle is photosynthesis, which is responsible for modern Earth's atmosphere. Photosynthesis releases oxygen into the atmosphere, while respiration and decay remove it from the atmosphere. In the present equilibrium, production and consumption occur at the same rate of roughly 1/2000th of the entire atmospheric oxygen per year. Free oxygen also occurs in solution in the world's water bodies. The increased solubility of O2 at lower temperatures has important implications for ocean life, as polar oceans support a much higher density of life due to their higher oxygen content. Water polluted with plant nutrients such as nitrates or phosphates may stimulate growth of algae by a process called eutrophication and the decay of these organisms and other biomaterials may reduce amounts of O2 in eutrophic water bodies. Scientists assess this aspect of water quality by measuring the water's biochemical oxygen demand, or the amount of O2 needed to restore it to a normal concentration. BIOLOGICAL ROLE OF OXYGEN Photosynthesis and respiration In nature, free oxygen is produced by the light-driven splitting of water during oxygenic photosynthesis. According to some estimates, Green algae and cyanobacteria in marine environments provide about 70% of the free oxygen produced on Earth and the rest is produced by terrestrial plants. Other estimates of the oceanic contribution to atmospheric oxygen are higher, while some estimates are lower, suggesting oceans produce ~45% of Earth's atmospheric oxygen each year.
15

16

A simplified overall formula for photosynthesis is: 6 CO2 + 6 H2O + photons C6H12O6 + 6 O2 or simply carbon dioxide + water + sunlight glucose + dioxygen Photolytic oxygen evolution occurs in the thylakoid membranes of photosynthetic organisms and requires the energy of four photons. Many steps are involved, but the result is the formation of a proton gradient across the thylakoid membrane, which is used to synthesize ATP via photophosphorylation. The O2 remaining after oxidation of the water molecule is released into the atmosphere. Molecular dioxygen, O2, is essential for cellular respiration in all aerobic organisms. Oxygen is used in mitochondria to help generate adenosine triphosphate (ATP) during oxidative phosphorylation. The reaction for aerobic respiration is essentially the reverse of photosynthesis and is simplified as: C6H12O6 + 6 O2 6 CO2 + 6 H2O + 2880 kJmol
1

In vertebrates, O2 diffuses through membranes in the lungs and into red blood cells. Hemoglobin binds O2, changing its color from bluish red to bright red (CO2 is released from another part of hemoglobin through the Bohr effect). Other animals use hemocyanin (molluscs and some arthropods) or hemerythrin (spiders andlobsters). A 3 liter of blood can dissolve 200 cm of O2. Reactive oxygen species, such as superoxide ion (O2) and hydrogen peroxide (H2O2), are dangerous by-products of oxygen use in organisms. Parts of the immune system of higher organisms, however, create peroxide, superoxide, and singlet oxygen to destroy invading microbes. Reactive oxygen species also play an important role in the hypersensitive response of plants against pathogen attack. An adult human in rest inhales 1.8 to 2.4 grams of oxygen per minute. This amounts to more than 6 billion tonnes of oxygen inhaled by humanity per year. Content in body The free oxygen partial pressure in the body of a living vertebrate organism is highest in the respiratory system, and decreases along any arterial system, peripheral tissues and venous system, respectively. Partial pressure is the pressure which oxygen would have if it alone occupied the volume. Build-up in atmosphere Free oxygen gas was almost nonexistent in Earth's atmosphere before photosynthetic archaea and bacteria evolved, probably about 3.5 billion years ago. Free oxygen first appeared in significant quantities during the Paleoproterozoic eon (between 3.0 and 2.3 billion years ago). For the first billion years, any free oxygen produced by these organisms combined with dissolved iron in the oceans to form banded iron formations. When such oxygen sinks became saturated, free oxygen began to outgas from the oceans 32.7 billion years ago, reaching 10% of its present level around 1.7 billion years ago.

The presence of large amounts of dissolved and free oxygen in the oceans and atmosphere may have driven most of the anaerobic organisms then living to extinction during the Great Oxygenation Event (oxygen catastrophe) about 2.4 billion years ago. However, cellular respiration using O2 enablesaerobic organisms to produce much more ATP than anaerobic organisms, helping the former to dominate Earth's biosphere. Photosynthesis and cellular respiration of O2 allowed for the evolution of eukaryotic cells and ultimately complex multicellular organisms such as plants and animals. Since the beginning of the Cambrian period 540 million years ago, O2 levels have fluctuated between 15% and 30% by volume. Towards the end of the Carboniferous period (about 300 million years ago) atmospheric O2 levels reached a maximum of 35% by volume, which may have contributed to the large size of insects and amphibians at this time. Human activities, including the burning of 7 billion tonnes of fossil fuels each year have had very little effect on the amount of free oxygen in the atmosphere. At the current rate of photosynthesis it would take about 2,000 years to regenerate the entire O2 in the present atmosphere. HISTORY Early experiments One of the first known experiments on the relationship between combustion and air was conducted by the 2nd century BCE Greek writer on mechanics, Philo of Byzantium. In his work Pneumatica, Philo observed that inverting a vessel over a burning candle and surrounding the vessel's neck with water resulted in some water rising into the neck. Philo incorrectly surmised that parts of the air in the vessel were converted into the classical element fire and thus were able to escape through pores in the glass. Many centuries laterLeonardo da Vinci built on Philo's work by observing that a portion of air is consumed during combustion and respiration. In the late 17th century, Robert Boyle proved that air is necessary for combustion. English chemist John Mayow (16411679) refined this work by showing that fire requires only a part of air that he called spiritus nitroaereus or just nitroaereus. In one experiment he found that placing either a mouse or a lit candle in a closed container over water caused the water to rise and replace one-fourteenth of the air's volume before extinguishing the subjects. From this he surmised that nitroaereus is consumed in both respiration and combustion. Mayow observed that antimony increased in weight when heated, and inferred that the nitroaereus must have combined with it. He also thought that the lungs separate nitroaereus from air and pass it into the blood and that animal heat and muscle movement result from the reaction of nitroaereus with certain substances in the body. Accounts of these and other experiments and ideas were published in 1668 in his work Tractatus duo in the tract "De respiratione". Phlogiston theory Robert Hooke, Ole Borch, Mikhail Lomonosov, and Pierre Bayen (fr) all produced oxygen in experiments in the 17th and the 18th century but none of them recognized it as a chemical element. This may have been in part due to the prevalence of the philosophy of combustion and corrosioncalled the phlogiston theory, which was then the favored explanation of those processes. Established in 1667 by the German alchemist J. J. Becher, and modified by the chemist Georg Ernst Stahl by 1731, phlogiston theory stated that all combustible materials were made of two parts. One part,

called phlogiston, was given off when the substance containing it was burned, while the dephlogisticated part was thought to be its true form, or calx. Highly combustible materials that leave little residue, such as wood or coal, were thought to be made mostly of phlogiston; whereas non-combustible substances that corrode, such as iron, contained very little. Air did not play a role in phlogiston theory, nor were any initial quantitative experiments conducted to test the idea; instead, it was based on observations of what happens when something burns, that most common objects appear to become lighter and seem to lose something in the process. The fact that a substance like wood actually gains overall weight in burning was hidden by the buoyancy of the gaseous combustion products. Indeed one of the first clues that the phlogiston theory was incorrect was that metals, too, gain weight in rusting (when they were supposedly losing phlogiston). Discovery Oxygen was first discovered by Swedish pharmacist Carl Wilhelm Scheele. He had produced oxygen gas by heating mercuric oxide and various nitrates by about 1772. Scheele called the gas "fire air" because it was the only known supporter of combustion, and wrote an account of this discovery in a manuscript he titled Treatise on Air and Fire, which he sent to his publisher in 1775. However, that document was not published until 1777. In the meantime, on August 1, 1774, an experiment conducted by the British clergyman Joseph Priestley focused sunlight on mercuric oxide (HgO) inside a glass tube, which liberated a gas he named "dephlogisticated air". He noted that candles burned brighter in the gas and that a mouse was more active and lived longer while breathing it. After breathing the gas himself, he wrote: "The feeling of it to my lungs was not sensibly different from that of common air, but I fancied that my breast felt peculiarly light and easy for some time afterwards." Priestley published his findings in 1775 in a paper titled "An Account of Further Discoveries in Air" which was included in the second volume of his book titled Experiments and Observations on Different Kinds of Air. Because he published his findings first, Priestley is usually given priority in the discovery. The noted French chemist Antoine Laurent Lavoisier later claimed to have discovered the new substance independently. However, Priestley visited Lavoisier in October 1774 and told him about his experiment and how he liberated the new gas. Scheele also posted a letter to Lavoisier on September 30, 1774 that described his own discovery of the previously unknown substance, but Lavoisier never acknowledged receiving it (a copy of the letter was found in Scheele's belongings after his death). Lavoisiers contribution What Lavoisier did indisputably do (although this was disputed at the time) was to conduct the first adequate quantitative experiments on oxidation and give the first correct explanation of how combustion works. He used these and similar experiments, all started in 1774, to discredit the phlogiston theory and to prove that the substance discovered by Priestley and Scheele was a chemical element. In one experiment, Lavoisier observed that there was no overall increase in weight when tin and air were heated in a closed container. He noted that air rushed in when he opened the container, which indicated that part of the trapped air had been consumed. He also noted that the tin had increased in weight and that increase was the same as the weight of the air that rushed back in. This and other experiments on combustion were documented in his book Sur la combustion en gnral, which was published in 1777. In that work, he proved that air is a mixture of two gases; 'vital air', which is essential to combustion and

respiration, and azote (Gk. "lifeless"), which did not support either. Azote later became nitrogen in English, although it has kept the name in French and several other European languages. Lavoisier renamed 'vital air' to oxygne in 1777 from the Greek roots (oxys) (acid, literally "sharp", from the taste of acids) and - (-gens) (producer, literally begetter), because he mistakenly believed that oxygen was a constituent of all acids. Chemists (notably Sir Humphry Davy in 1812) eventually determined that Lavoisier was wrong in this regard (it is in fact hydrogen that forms the basis for acid chemistry), but by that time it was too late; the name had taken. Oxygen entered the English language despite opposition by English scientists and the fact that the Englishman Priestley had first isolated the gas and written about it. This is partly due to a poem praising the gas titled "Oxygen" in the popular book The Botanic Garden (1791) by Erasmus Darwin, grandfather of Charles Darwin. INDUSTRIAL PRODUCTION Two major methods are employed to produce 100 million tonnes of O2 extracted from air for industrial uses annually. The most common method is to fractionally distill liquefied air into its various components, with N2 distilling as a vapor while O2 is left as a liquid. The other major method of producing O2 gas involves passing a stream of clean, dry air through one bed of a pair of identical zeolite molecular sieves, which absorbs the nitrogen and delivers a gas stream that is 90% to 93% O2. Simultaneously, nitrogen gas is released from the other nitrogen-saturated zeolite bed, by reducing the chamber operating pressure and diverting part of the oxygen gas from the producer bed through it, in the reverse direction of flow. After a set cycle time the operation of the two beds is interchanged, thereby allowing for a continuous supply of gaseous oxygen to be pumped through a pipeline. This is known as pressure swing adsorption. Oxygen gas is increasingly obtained by these noncryogenic technologies (see also the related vacuum swing adsorption). Oxygen gas can also be produced through electrolysis of water into molecular oxygen and hydrogen. DC electricity must be used: if AC is used, the gases in each limb consist of hydrogen and oxygen in the explosive ratio 2:1. Contrary to popular belief, the 2:1 ratio observed in the DC electrolysis of acidified water does not prove that the empirical formula of water is H2O unless certain assumptions are made about the molecular formulae of hydrogen and oxygen themselves. A similar method is the electrocatalytic O2 evolution from oxides and oxoacids. Chemical catalysts can be used as well, such as in chemical oxygen generators or oxygen candles that are used as part of the life-support equipment on submarines, and are still part of standard equipment on commercial airliners in case of depressurization emergencies. Another air separation technology involves forcing air to dissolve through ceramic membranes based on zirconium dioxide by either high pressure or an electric current, to produce nearly pure O2 gas. In large quantities, the price of liquid oxygen in 2001 was approximately $0.21/kg. Since the primary cost of production is the energy cost of liquefying the air, the production cost will change as energy cost varies. For reasons of economy, oxygen is often transported in bulk as a liquid in specially insulated tankers, since one litre of liquefied oxygen is equivalent to 840 liters of gaseous oxygen at atmospheric pressure and 20 C (68 F). Such tankers are used to refill bulk liquid oxygen storage containers, which stand outside hospitals and other institutions with a need for large volumes of pure oxygen gas. Liquid oxygen

is passed through heat exchangers, which convert the cryogenic liquid into gas before it enters the building. Oxygen is also stored and shipped in smaller cylinders containing the compressed gas; a form that is useful in certain portable medical applications and oxy-fuel welding and cutting. APPLICATIONS Medical Uptake of O2 from the air is the essential purpose of respiration, so oxygen supplementation is used in medicine. Treatment not only increases oxygen levels in the patient's blood, but has the secondary effect of decreasing resistance to blood flow in many types of diseased lungs, easing work load on the heart. Oxygen therapy is used to treatemphysema, pneumonia, some heart disorders (congestive heart failure), some disorders that cause increased pulmonary artery pressure, and any disease that impairs the body's ability to take up and use gaseous oxygen. Treatments are flexible enough to be used in hospitals, the patient's home, or increasingly by portable devices. Oxygen tents were once commonly used in oxygen supplementation, but have since been replaced mostly by the use of oxygen masks or nasal cannulas. Hyperbaric (high-pressure) medicine uses special oxygen chambers to increase the partial pressure of O2 around the patient and, when needed, the medical staff. Carbon monoxide poisoning, gas gangrene, and decompression sickness (the 'bends') are sometimes treated using these devices. Increased O2 concentration in the lungs helps to displace carbon monoxide from the heme group of hemoglobin. Oxygen gas is poisonous to the anaerobic bacteria that cause gas gangrene, so increasing its partial pressure helps kill them. Decompression sickness occurs in divers who decompress too quickly after a dive, resulting in bubbles of inert gas, mostly nitrogen and helium, forming in their blood. Increasing the pressure of O2 as soon as possible is part of the treatment. Oxygen is also used medically for patients who require mechanical ventilation, often at concentrations above the 21% found in ambient air. Life support and recreational use A notable application of O2 as a low-pressure breathing gas is in modern space suits, which surround their occupant's body with pressurized air. These devices use nearly pure oxygen at about one third normal pressure, resulting in a normal blood partial pressure of O2. This trade-off of higher oxygen concentration for lower pressure is needed to maintain flexible spacesuits. Scuba divers and submariners also rely on artificially delivered O2, but most often use normal pressure, and/or mixtures of oxygen and air. Pure or nearly pure O2 use in diving at higher-than-sea-level pressures is usually limited to rebreather, decompression, or emergency treatment use at relatively shallow depths (~6 meters depth, or less). Deeper diving requires significant dilution of O2 with other gases, such as nitrogen or helium, to help prevent oxygen toxicity. People who climb mountains or fly in non-pressurized fixed-wing aircraft sometimes have supplemental O2 supplies. Passengers traveling in (pressurized) commercial airplanes have an emergency supply of O2 automatically supplied to them in case of cabin depressurization. Sudden cabin pressure loss activates chemical oxygen generators above each seat, causing oxygen masks to drop. Pulling on the masks "to start the flow of oxygen" as cabin safety instructions dictate, forces iron filings into the sodium chlorate inside the canister. A steady stream of oxygen gas is then produced by the exothermic reaction.

Oxygen, as a supposed mild euphoric, has a history of recreational use in oxygen bars and in sports. Oxygen bars are establishments, found in Japan, California, and Las Vegas, Nevada since the late 1990s that offer higher than normal O2 exposure for a fee. Professional athletes, especially in American football, also sometimes go off field between plays to wear oxygen masks in order to get a "boost" in performance. The pharmacological effect is doubtful; a placebo effect is a more likely explanation. Available studies support a performance boost from enriched O2 mixtures only if they are breathed during aerobic exercise. Other recreational uses that do not involve breathing the gas include pyrotechnic applications, such as George Goble's five-second ignition of barbecue grills. Industrial Smelting of iron ore into steel consumes 55% of commercially produced oxygen. In this process, O2 is injected through a high-pressure lance into molten iron, which removes sulfur impurities and excess carbon as the respective oxides, SO2 and CO2. The reactions are exothermic, so the temperature increases to 1,700 C. Another 25% of commercially produced oxygen is used by the chemical industry. Ethylene is reacted with O2 to create ethylene oxide, which, in turn, is converted into ethylene glycol; the primary feeder material used to manufacture a host of products, including antifreeze and polyester polymers (the precursors of many plastics and fabrics). Most of the remaining 20% of commercially produced oxygen is used in medical applications, metal cutting and welding, as an oxidizer in rocket fuel, and in water treatment. Oxygen is used in oxyacetylene welding burning acetylene with O2 to produce a very hot flame. In this process, metal up to 60 cm thick is first heated with a small oxy-acetylene flame and then quickly cut by a large stream of O2. Larger rockets use liquid oxygen as their oxidizer, which is mixed and ignited with the fuel for propulsion. Scientific Paleoclimatologists measure the ratio of oxygen-18 and oxygen-16 in the shells and skeletons of marine organisms to determine what the climate was like millions of years ago (see oxygen isotope ratio cycle). Seawater molecules that contain the lighter isotope, oxygen-16, evaporate at a slightly faster rate than water molecules containing the 12% heavier oxygen-18; this disparity increases at lower temperatures. During periods of lower global temperatures, snow and rain from that evaporated water tends to be higher in oxygen-16, and the seawater left behind tends to be higher in oxygen-18. Marine organisms then incorporate more oxygen-18 into their skeletons and shells than they would in a warmer climate. Paleoclimatologists also directly measure this ratio in the water molecules of ice core samples that are up to several hundreds of thousands of years old. Planetary geologists have measured different abundances of oxygen isotopes in samples from the Earth, the Moon, Mars, and meteorites, but were long unable to obtain reference values for the isotope ratios in the Sun, believed to be the same as those of the primordial solar nebula. However, analysis of a silicon wafer exposed to the solar wind in space and returned by the crashed Genesis spacecraft has shown that the Sun has a higher proportion of oxygen-16 than does the Earth. The measurement implies that an unknown process depleted oxygen-16 from the Sun's disk of protoplanetary material prior to the coalescence of dust grains that formed the Earth.

Oxygen presents two spectrophotometric absorption bands peaking at the wavelengths 687 and 760 nm. Some remote sensing scientists have proposed using the measurement of the radiance coming from vegetation canopies in those bands to characterize plant health status from a satellite platform. This approach exploits the fact that in those bands it is possible to discriminate the vegetation's reflectance from its fluorescence, which is much weaker. The measurement is technically difficult owing to the low signal-to-noise ratio and the physical structure of vegetation; but it has been proposed as a possible method of monitoring the carbon cycle from satellites on a global scale. COMPOUNDS The oxidation state of oxygen is 2 in almost all known compounds of oxygen. The oxidation state 1 is found in a few compounds such as peroxides. Compounds containing oxygen in other oxidation states are very uncommon: 1/2 (superoxides), 1/3 (ozonides), 0 (elemental, hypofluorous acid), +1/2 (dioxygenyl), +1 (dioxygen difluoride), and +2 (oxygen difluoride). SAFETY AND PRECAUTIONS The NFPA 704 standard rates compressed oxygen gas as nonhazardous to health, nonflammable and nonreactive, but an oxidizer. Refrigerated liquid oxygen (LOX) is given a health hazard rating of 3 (for increased risk of hyperoxia from condensed vapors, and for hazards common to cryogenic liquids such as frostbite), and all other ratings are the same as the compressed gas form. FLUORINE Fluorine is the chemical element with symbol F and atomic number 9. At room temperature, the element is a pale yellow gas composed of diatomic molecules,F2. Fluorine is the lightest halogen and the most electronegative element. It requires great care in handling as it is extremely reactive and poisonous. Fluorine is the 24th most abundant element in the universe and the 13th most abundant within the Earth's crust. The main source mineral, fluorite, was first formally described in 1529. The mineral's name derives from the Latin verb fluo, meaning "flow", because fluorite was added to metal ores to lower their melting points. Suggested as a chemical element in 1811, fluorine was first isolated in 1886 by French chemist Henri Moissan. In the 1940s, the largest market for the free element, uranium enrichment, began during the Manhattan Project. Compounds of fluorine are called fluorides, and global fluorochemical sales are over US$15 billion per year. Because of the expense of refining the pure element, 99% of commercially used fluorine remains in compound form throughout its processing. About half of all mined fluorite is used directly in steel-making. The other half is converted to hydrogen fluoride, a dangerous acid which is the precursor to many fluorochemicals. About one third of created hydrogen fluoride ends up in synthetic cryolite, an inorganic material critical to aluminium refining. Even more hydrogen fluoride is used to make organic fluorides. These compounds have have very high chemical and thermal stability; their largest market segment is in refrigerant gases ("Freon"). (Even though traditional chlorofluorocarbons are now mostly prohibited, the replacement molecules still contain fluorine.) The predominant fluoropolymer is polytetrafluoroethylene (Teflon), which is used in electrical insulation and cookware. While a few plants and bacteria synthesize organofluorine poisons, fluorine has no metabolic role in mammals. The fluoride ion, when directly applied to teeth, reduces decay; for this reason, it is used in

toothpaste and water fluoridation. A significant fraction of modern pharmaceuticalssuch as atorvastatin (Lipitor) andfluoxetine (Prozac)contain fluorine.
2 History

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2.1 Early discoveries 2.2 Isolation 2.3 Later developments

3 Characteristics

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3.1 Phases 3.2 Isotopes 3.3 Electron arrangement 3.4 Chemical reactivity

4 Compounds 5 Industry and applications

6 Production of fluorine gas 8 Hazards

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8.1 Fluorine gas 8.2 Hydrofluoric acid 8.3 Fluoride ion

9 Environmental concerns

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9.1 Atmosphere 9.2 Biopersistance

HISTORY Early discoveries The word "fluorine" derives from the Latin stem of the main source mineral, fluorite. The stone was described in 1529 by Georgius Agricola, who related its use as afluxan additive that helps lower the melt temperature during smelting. Agricola, the "father of mineralogy", invented several hundred new terms in his Latin works describing 16th-century industry. For fluorite rocks (schne Flsse in the German of the time), he created the Latin noun fluors, from fluo (flow). The name for the mineral later evolved to fluorspar (still commonly used) and then to fluorite. Hydrofluoric acid was known as a glass-etching agent from the 1720s, perhaps as early as 1670. Andreas Sigismund Marggraf made the first scientific report on its preparation in 1764 when he heated fluorite with sulfuric acid; the resulting solution corroded its glass container. Swedish chemist Carl

Wilhelm Scheelerepeated this reaction in 1771, recognizing the product as an acid, which he called "fluss-spats-syran" (fluor-spar-acid). In 1810, French physicist Andr-Marie Ampre suggested that the acid was a compound of hydrogen with an unknown element, analogous to chlorine. Fluorite was then shown to be mostly composed of calcium fluoride. Sir Humphry Davy originally suggested the name fluorine, taking the root from the name of "fluoric acid" and the "-ine" suffix, similarly to other halogens. This name, with modifications, came to most European languages, although Greek, Russian, and some others (following Ampre's suggestion) use the name ftor or derivatives, from the Greek (phthorios), meaning "destructive". The New Latin name (fluorum) gave the element its current symbol, F, although the symbol Fl was used in early papers. Isolation Progress in isolating the element was slowed by the exceptional dangers of generating fluorine: several 19th-century experimenters, the "fluorine martyrs", were killed or badly hurt while working with hydrofluoric acid. Initial attempts to isolate the element were hindered by problems getting a suitable conducting liquid for electrolysis as well as by the extreme corrosiveness of hydrogen fluoride and of fluorine gas. Edmond Frmy thought that passing electric current through pure hydrofluoric acid (dry HF) might allow the element to be isolated. Previously, hydrogen fluoride was only available in a water solution. Frmy therefore devised a method for producing dry hydrogen fluoride by acidifying potassium bifluoride (KHF2). Unfortunately, pure hydrogen fluoride would not pass an electric current. French chemist Henri Moissan, formerly one of Frmy's students, continued the search. After trying many different approaches, he combined potassium bifluoride and dry hydrogen fluoride. The mixture proved to conduct electricity, making electrolysis possible. However, rapid destruction of the platinum metal in his electrochemical cells still stymied the quest. To continue, Moissan devised a strategy of cooling the reaction in a special bath to extremely low temperatures, which slowed the rate of corrosion. Moissan also constructed more corrosion-resistant equipment: containers crafted from a mixture of platinum and iridium (more chemically resistant than pure platinum) with fluorite stoppers. In 1886, Moissan crowned 74 years of effort by many chemists when he isolated elemental fluorine. Later developments In the late 1920s, chlorofluorocarbon refrigerants were tested by researchers from the Frigidaire division of General Motors. In 1930, GM formed a joint venture with DuPont, Kinetic Chemicals, to commercialize Freon-12 (CCl2F2). It proved to be a marketplace hit, rapidly replacing earlier, more toxic, refrigerants and growing the overall market for kitchen refrigerators. By 1949, DuPont had bought out the joint venture and marketed several other Freon molecules. In 1938, Teflon was discovered by accident by a recently hired Kinetic Ph.D., Roy J. Plunkett. Undertaking research on possible use of tetrafluoroethylene as a refrigerant, he encountered a mystery. Gas left in a cylinder overnight could not be released the next morning, but the weight of the container had not changed (indicating the gas had not leaked out). Cutting the cylinder open, he found white flakes of a polymer new to the world. Tests showed the substance was polytetrafluoroethylene (poly meaning many). The polymer was more resistant to corrosion and had better high temperature stability than did any other plastic. By 1941, an accelerated commercialization program was making significant quantities.

Large-scale productions of elemental fluorine began during World War II. Germany used hightemperature electrolysis to produce tons of chlorine trifluoride, a compound planned to be used as an incendiary. The Manhattan Project in the United States used even more elemental fluorine to make uranium hexafluoride for use in uranium enrichment plants. Because UF6 is corrosive in a similar manner to fluorine itself, gaseous diffusion separation plants were built with special materials. Nickel was used for the membranes; fluoropolymers such as Teflon were used for seals; and liquid fluorocarbons were used as coolants and lubricants. After the war, the nuclear weapons industry drove further development of fluorochemicals. In the 1970s, concern developed that chlorofluorocarbons were damaging the ozone layer. By 1996, almost all nations had banned CFCs, and commercial production ceased. Fluorine continued to play a role in refrigeration though: hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) were the replacement refrigerant gases. CHARACTERISTICS Phases At room temperature, fluorine is a gas of diatomic molecules. Though sometimes described as yellowgreen, pure fluorine is actually a very pale yellow. The gas has a pungent characteristic odor that is noticeable in concentrations as low as 20 ppb. Fluorine condenses to a bright yellow liquid at 188 C, which is near the condensation temperatures of oxygen and nitrogen. Fluorine solidifies at 220 C into a cubic structure called beta-fluorine. This phase is transparent and soft with significant disorder of the molecules. With further cooling to 228 C, fluorine undergoes a solid solid phase transition into a monoclinic structure called alpha-fluorine. This phase is opaque and hard with close-packed, shingled layers of molecules. The solid state phase change releases more energy than the melting point transition, and can be violent. In general, fluorine's solid state form is more similar to oxygen's than to those of the other halogens. Isotopes Fluorine is defined by its atomic number, nine, which indicates how many protons it has. One stable isotope occurs naturally: fluorine-19, which contains tenneutrons. The element is both monoisotopic (having a single stable isotope) and mononuclidic (being found on Earth in only one isotope). These attributes make it useful in uranium enrichment and in nuclear magnetic resonance. Seventeen radioisotopes have been synthesized: mass numbers 1418 and 2031. The lightest fluorine isotopes, those with mass numbers of 1416, decay viaelectron capture. Fluorine-17 and -18 undergo beta plus decay (emission of a positron). All isotopes heavier than fluorine-19 decay by beta minus mode (emission of an electron); some of these also decay by neutron emission. Fluorine-18 is the most stable radioisotope, with a half-life of 109.77 minutes before decaying to oxygen-18. Electron arrangement The neutral atom has nine electrons, one fewer than neon. The electronic configuration is 1s 2s 2p : a filled inner shell of two electrons and an unfilled outer shell containing seven (one short of being filled). The outer electrons do not shield each other much from the nucleus. They therefore experience a high effective nuclear charge of seven (nine minus two), which affects the physical properties of the atom.
2 2 5

Removal of electrons from neutral atoms is very difficult; fluorine's ionization energy (the energy required to remove an electron) is higher than that of any other element except neon and helium. Instead, fluorine exhibits a very strong preference for capturing one more electron to achieve the filled-shell electron 2 2 6 configuration of noble gas neon: 1s 2s 2p . Fluorine is the element with the highest electronegativity (a relative measure of electron attraction by atoms). Its electron affinity (the energy released by adding an electron) is higher than that of any element exceptchlorine. Fluorine atoms have a small covalent radius of around 60 picometers. This is similar to the radii of oxygen and neon, the left and right hand neighbors of the periodic table. Chemical reactivity The difluorine bond is relatively weak, with a bond energy much less than that in Cl2 or Br2 and similar to the easily cleaved oxygenoxygen bonds of peroxides. For this reason, elemental fluorine easily dissociates to react with other atoms. On the other hand, bonds to non-fluorine atoms are very strong because of atomic fluorine's electron attraction. Both the easy breaking apart of difluorine and the strong bonding to other atoms make fluorine extremely reactive. Many substances that are generally regarded as unreactivesuch as powdered steel, glass fragments, and asbestos fibersare readily consumed by cold fluorine gas. Wood and even water burn with flames when subjected to a jet of fluorine, without the need for a spark. Reactions of elemental fluorine with metals require different conditions that depend on the metal. Many such as aluminium, iron, and coppermust be powdered to overcome passivation (protective metal fluoride layers formed with initial exposure). The alkali metals, such as sodium, react explosively. The alkaline earth metals, such as calcium, react somewhat less dramatically. The noble metals (gold, platinum, etc.) react least readily, requiring pure fluorine gas at 300450 C. Fluorine reacts explosively with hydrogen in a manner similar to that of alkali metals. The other halogens react readily with fluorine gas, as does the heavy noble gas radon. The lighter noble gases xenon and krypton react directly with fluorine under special conditions. Oxygen and fluorine gases do not normally react, but they can be combined under electric discharge at low pressures and temperatures. The products can be unstable and tend to separate back into fluorine and oxygen when heated. Nitrogen, with its very strong triple bonds, requires electric discharge and very high temperatures to react with fluorine even though the end product, NF3, is quite stable. Ammonia (NH3) can react explosively with fluorine. Carbon, in graphite or diamond form, is impervious to fluorine gas at room temperature. Above 400C, graphite reacts with fluorine to make a varying-composition solid called "carbon monofluoride". At higher temperatures, gaseous fluorocarbons start to be produced; the reaction can become explosive. Carbon dioxide and carbon monoxide react with fluorine at room temperature or a little above. Organic chemicals, such as paraffins, react strongly when exposed to fluorine. Even fully halogenated organic molecules, such as normally incombustible carbon tetrachloride, can explode. The other solid nonmetals or metalloids (boron, silicon, arsenic, sulfur, germanium, phosphorus, selenium, tellurium) burn with a flame in room temperature fluorine. Hydrogen sulfide and sulfur dioxidecombine readily with fluorine; the latter reaction can be explosive. Sulfuric acid reacts much more sluggishly. COMPOUNDS

Fluorine's common oxidation state is 1. Because of its attraction for electrons, fluorine forms many ionic compounds. Covalent bonds involving fluorine are polar and almost always, within molecules, are single bonds. Fluorine has a rich chemistry including compounds formed with hydrogen, metals, main group nonmetals, and even noble gases, as well as a diverse set of organic compounds. INDUSTRY AND APPLICATIONS The main source of fluorine, fluorite mining, was a growing industry through 1989 when it reached a high of 5.6 million metric tons per year. Environmental restrictions on a main end market (chlorofluorocarbons) led to reduced production, down to 3.6 million tons in 1994. Since then production has steady risen. In 2003, it was estimated at 4.5 million tons and a corresponding revenue of $550 million. A 2012 market research report estimated that production would hit about 5.9 million tons by 2017. Mined fluorite is concentrated by flotation separation into two main grades, with about equal production of each. Metspar (6085% purity) is used almost exclusively for iron smelting. Acidspar (97%+ purity) is primarily converted to hydrogen fluoride, which is the primary chemical intermediate for the industry. A market survey estimated 2011 global fluorochemical sales at $15 billion. It predicted 5% growth to 2018, when the market would exceed $20 billion. A different report said that, in 2016, global fluorochemical production would be almost $20 billion with a volume of 3.5 million metric tons per year PRODUCTION OF FLUORINE GAS Modern industrial production of elemental fluorine uses Moissan's process of electrolyzing potassium fluoride/hydrogen fluoride mixtures but with an apparatus made of different materials. The steel container + acts as the cathode, attracting H ions and releasing hydrogen gas. A carbon block (similar to that used in aluminium production) acts as the anode, attracting F ions and releasing fluorine gas. The voltage is 8 12 volts. Commercial temperatures are now higher than what Moissan used. A mixture with the approximate composition KF2HF melts at 70 C (158 F) and is electrolyzed at 70130 C. Because HF alone cannot be electrolyzed, the presence of some KF is critical even though it is not consumed in the cell. Pure fluorine gas may be stored in steel cylinders, where the inside surface is passivated, as long as the temperature is kept below 200 C. Above that temperature, nickel is required. Regulator valves are made of nickel. Fluorine piping is generally made of nickel or Monel (nickel-copper alloy). Care must be taken to passivate all surfaces frequently and to exclude any water or greases. In the laboratory, fluorine gas may be used in glass tubing provided the pressure is low and moisture is excluded, but some sources recommend systems made of nickel, Monel, and PTFE. HAZARDS Fluorine gas Elemental fluorine is highly toxic. Above a concentration of 25 ppm, it causes significant irritation while attacking the eyes, airways and lungs and affecting the liver and kidneys. At a concentration of 100 ppm, human eyes and noses are seriously damaged. Hydrofluoric acid Hydrofluoric acid, the water solution of hydrogen fluoride, is a contact poison. Even though it is chemically only a weak acid, it is far more dangerous than the conventional strong mineral acids, such as nitric acid,

sulfuric acid, or hydrochloric acid. Owing to its lesser chemical dissociation in water (remaining a neutral molecule), hydrogen fluoride penetrates tissue more quickly than typical acids. Poisoning can occur readily through the skin or eyes or when inhaled or swallowed. From 1984 to 1994, at least nine U.S. workers died from accidents with HF. Once in the blood, hydrogen fluoride reacts with calcium and magnesium, resulting in electrolyte imbalance (potentially hypocalcemia). The consequent effect on the heart (cardiac arrhythmia) may be fatal. Formation of insoluble calcium fluoride also causes strong pain. Burns with areas larger than 2 160 cm , about the size of a man's hand, can cause serious systemic toxicity. Symptoms of exposure to hydrofluoric acid may not be immediately evident, with 8-hour delay for 50% HF and up to 24 hours for lower concentrations. Hydrogen fluoride interferes with nerve function, meaning that burns may not initially be painful. If the burn has been initially noticed, then HF should be washed off with a forceful stream of water for ten to fifteen minutes to prevent its further penetration into the body. Clothing used by the person burned may also present a danger. Hydrofluoric acid exposure is often treated with calcium gluconate, a source of 2+ Ca that binds with the fluoride ions. Skin burns can be treated with a water wash and 2.5% calcium gluconate gel or special rinsing solutions. Because HF is absorbed, further medical treatment is necessary. Calcium gluconate may be injected or administered intravenously. Use of calcium chloride is contraindicated and may lead to severe complications. Sometimes surgical excision of tissue or amputation is required. Fluoride ion Soluble fluorides are moderately toxic. For sodium fluoride, the lethal dose for adults is 5 10 g, which is equivalent to 3264 mg of elemental fluoride per kilogram of body weight. The dose that may lead to adverse health effects is about one fifth the lethal dose. Chronic excess fluoride consumption can lead to skeletal fluorosis, a disease of the bones that affects millions in Asia and Africa. The fluoride ion is readily absorbed by the stomach and intestines. Ingested fluoride forms hydrofluoric acid in the stomach. In this form, fluoride crosses cell membranes and then binds with calcium and interferes with various enzymes. Fluoride is excreted through urine. Fluoride exposure limits are based on urine testing, which has determined the human body's capacity for ridding itself of fluoride. Historically, most cases of fluoride poisoning have been caused by accidental ingestion of insecticides containing inorganic fluoride. Most current calls to poison control centers for possible fluoride poisoning come from the ingestion of fluoride-containing toothpaste. Malfunction of water fluoridation equipment has occurred several times, including an Alaskan incident that sickened nearly 300 people and killed one. Dangers from toothpaste are more serious for small childrenthe U.S. CDC recommends children under 6 years of age be supervised when brushing their teeth so they don't swallow toothpaste. One regional study examined a year of fluoride poisoning reports for pre-teens. Amongst 87 cases, there was one fatality (from insecticide). The other 86 were all from dental fluoride. Most had no symptoms, but about 30% had stomach pains, with symptoms more likely when more fluoride was consumed. A larger study of American fluoride poisoning reports showed similar findings. 80% of the reports were related to children under 6. Few were serious, although several hundred cases were treated at health facilities yearly. ENVIRONMENTAL CONCERNS

Atmosphere Because they deplete the ozone layer, chlorofluorocarbons (CFCs) and bromofluorocarbons (BFCs) have been strictly regulated via a series of international agreements called the Montreal Protocol. It is the chlorine and bromine from these molecules that cause harm, not the fluorine. Because of the inherent stability of these fully halogenated molecules (which makes them so nonflammable and useful), they are able to attain the upper reaches of the atmosphere before decomposing. At high altitudes, they release chlorine and bromine atoms which attack ozone molecules. Predictions are that generations will be required, even after the CFC ban, for these molecules to leave the atmosphere and for the ozone layer to fully recover. Early indications are that the CFC ban is working: ozone depletion has stopped, and recovery has started. Hydrochlorofluorocarbons (HCFCs) are current replacements for CFCs, with about one tenth the ozone damaging potential (ODP). They were themselves originally scheduled for elimination by 2030 in developed nations and 2040 in undeveloped with replacement by hydrofluorocarbons (HFCs) which have no chlorine and thus zero ODP. In 2003, the U.S. Environmental Protection Agency prohibited production of one HCFC and capped the production of the two others. In 2007, a new treaty was signed by almost all nations to move HCFC phaseout up to 2020. Fluorocarbon gases of all sorts (CFCs, HFCs, etc.) are greenhouse gases about 4,000 to 10,000 times as potent as carbon dioxide. Sulfur hexafluoride exhibits an even stronger effect, about 20,000 times the global warming potential of carbon dioxide. Biopersistance Because of the strength of the carbonfluorine bond, organofluorines endure in the environment. Perfluoroalkyl acids (PFAAs) have attracted particular attention as persistent global contaminants. These compounds can enter the environment from their direct uses in waterproofing treatments and firefighting foams or indirectly from leaks from fluoropolymer production plants (where they are intermediates). Because of the acid group, PFAAs are water soluble in low concentrations. While there are other PFAAs, the lion's share of environmental research has been done on the two most wellknown:perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). The U.S. Environmental Protection Agency classifies these materials as "emerging contaminants" based on the growing but still incomplete understanding of their environmental impact. Trace quantities of PFAAs have been detected worldwide, from polar bears in the Arctic to the global human population. Both PFOS and PFOA has been detected in breast milk and the blood of newborns. A 2013 review showed widely varying amounts of PFOS and PFOA in different soils and groundwater, with no clear pattern of one chemical dominating. PFAA concentration was generally higher in areas with more human populations or industrial activity, and areas with more PFOS generally also had more PFOA. Human populations also showed different concentrations of the two chemicals; for example one study showed more PFOS than PFOA in Germans, while another study showed the reverse for Americans. PFAAs may be starting to decrease in the biosphere: one study indicated that PFOS levels in wildlife in Minnesota were going down, presumably because of ceased production of the chemical by 3M. In the body, PFAAs bind to proteins such as serum albumin. Their tissue distribution in humans is unknown, but studies in rats suggest it is present mostly in the liver, kidney, and blood. They are not metabolized by the body but are excreted by the kidneys. Dwell time in the body varies greatly by species. Rodents have half-lives of days, while in humans they remain for years. Many animals show sex

differences in the ability to rid the body of PFAAs, but without a clear pattern. It varies by the animal if half lives are longer for males or females. The potential health impact of PFAAs is unclear. Unlike chlorinated hydrocarbons, PFAAs are not lipophilic (stored in fat), nor genotoxic (damaging genes). Both PFOA and PFOS in high doses cause cancer and the death of newborns in rodents. However, studies on humans have not been able to prove an impact at current exposures. Bottlenose dolphins have some of the highest PFOS concentrations of any wildlife studied; one study suggests an impact on their immune systems. The biochemical causes of toxicity are also unclear and may differ by molecule, health effect, and even animal. Significant research has been done looking at PPAR-alpha (a protein that interacts with PFAAs and is commonly implicated in contaminant-caused rodent cancers. Less fluorinated chemicals (not perfluorinated compounds) are also detectable in the environment. Because biological systems do not metabolize fluorinated molecules easily, fluorinated pharmaceuticals (often antibiotics and antidepressants) are among the major fluorinated organics found in treated city sewage and wastewater. Fluorine-containing agrichemicals are measurable in farmland runoff and nearby rivers. NEON Neon is a chemical element with symbol Ne and atomic number 10. It is in group 18 (noble gases) of the periodic table. Neon is a colorless, odorless, inert monatomic gas under standard conditions, with about two-thirds the density of air. It was discovered (along with krypton and xenon) in 1898 as one of the three residual rare inert elements remaining in dry air, after nitrogen, oxygen, argon and carbon dioxide are removed. Neon was the second of these three rare gases to be discovered, and was immediately recognized as a new element from its bright red emission spectrum. The name neon is derived from the Greek word , neuter singular form of [neos], meaning new. Neon is chemically inert and forms no uncharged chemical compounds. During cosmic nucleogenesis of the elements, large amounts of neon are built up from the alpha-capture fusion process in stars. Although neon is a very common element in the universe and solar system (it is fifth in cosmic abundance after hydrogen, helium, oxygen and carbon), it is very rare on Earth. It composes about 18.2 ppm of air by volume (this is about the same as the molecular or mole fraction), and a smaller fraction in the crust. The reason for neon's relative scarcity on Earth and the inner (terrestrial) planets, is that neon forms no compounds to fix it to solids, and is highly volatile, therefore escaping from the planetesimals under the warmth of the newly ignited Sun in the early Solar System. Even the atmosphere of Jupiter is somewhat depleted of neon, presumably for this reason. Neon gives a distinct reddish-orange glow when used in either low-voltage neon glow lamps or in highvoltage discharge tubes or neon advertising signs. The red emission line from neon is also responsible for the well known red light of helium-neon lasers. Neon is used in a few plasma tube and refrigerant applications but has few other commercial uses. It is commercially extracted by the fractional distillation of liquid air. It is considerably more expensive than helium, since air is its only source.
1 History 2 Isotopes 3 Characteristics

4 Occurrence 5 Applications 6 Compounds

HISTORY Neon (Greek (neon), neuter singular form of meaning "new"), was discovered in 1898 by the British chemists Sir William Ramsay (18521916) and Morris W. Travers (18721961) in London. Neon was discovered when Ramsay chilled a sample of air until it became a liquid, then warmed the liquid and captured the gases as they boiled off. The gases nitrogen, oxygen, and argon had been identified, but the remaining gases were isolated in roughly their order of abundance, in a six-week period beginning at the end of May 1898. First to be identified was krypton. The next, after krypton had been removed, was a gas which gave a brilliant red light under spectroscopic discharge. This gas, identified in June, was named neon, the Greek analogue of "novum," (new), the name Ramsay's son suggested. The characteristic brilliant red-orange color that is emitted by gaseous neon when excited electrically was noted immediately; Travers later wrote, "the blaze of crimson light from the tube told its own story and was a sight to dwell upon and never forget." Finally, the same team discovered xenon by the same process, in July. Neon's scarcity precluded its prompt application for lighting along the lines of Moore tubes, which used nitrogenand which were commercialized in the early 1900s. After 1902, Georges Claude's company, Air Liquide, was producing industrial quantities of neon as a byproduct of his air liquefaction business. In December 1910 Claude demonstrated modern neon lighting based on a sealed tube of neon. Claude tried briefly to get neon tubes to be used for indoor lighting, due to their intensity, but failed, as homeowners rejected neon light sources due to their color. Finally in 1912, Claude's associate began selling neon discharge tubes as advertising signs, where they were instantly more successful as eye catchers. They were introduced to the U.S. in 1923, when two large neon signs were bought by a Los Angeles Packard car dealership. The glow and arresting red color made neon advertising completely different from the competition. Neon played a role in the basic understanding of the nature of atoms in 1913, when J. J. Thomson, as part of his exploration into the composition of canal rays, channeled streams of neon ions through a magnetic and an electric field and measured their deflection by placing a photographic plate in their path. Thomson observed two separate patches of light on the photographic plate (see image), which suggested two different parabolas of deflection. Thomson eventually concluded that some of the atoms in the neon gas were of higher mass than the rest. Though not understood at the time by Thomson, this was the first discovery of isotopes of stable atoms. It was made by using a crude version of an instrument we now term as a mass spectrometer. ISOTOPES Neon is the second lightest inert gas. Neon has three stable isotopes: Ne (90.48%), Ne (0.27%) 22 21 22 and Ne (9.25%). Ne and Ne are partly primordial and partly nucleogenic (i.e., made by nuclear reactions of other nuclides with neutrons or other particles in the environment) and their variations 20 in natural abundance are well understood. In contrast, Ne (the chief primordial isotope made in stellar nucleosynthesis) is not known to be nucleogenic or radiogenic (save forcluster decay production,
20 21

which is thought to produce only a small amount). The causes of the variation of thus been hotly debated.

20

Ne in theEarth have
24 25

The principal nuclear reactions which generate nucleogenic neon isotopes start from Mg and Mg, 21 22 which produce Ne and Ne, respectively, after neutron capture and immediate emission of an alpha particle. The neutrons that produce the reactions are mostly produced by secondary spallation reactions from alpha particles, in turn derived from uranium-seriesdecay chains. The net result yields a trend 20 22 21 22 towards lower Ne/ Ne and higher Ne/ Ne ratios observed in uranium-rich rocks such 20 as granites. Neon-21 may also be produced in a nucleogenic reaction, when Ne absorbs a neutron from various natural terrestrial neutron sources. In addition, isotopic analysis of exposed terrestrial rocks has demonstrated the cosmogenic (cosmic ray) 21 production of Ne. This isotope is generated by spallation reactions on magnesium, sodium, silicon, and aluminium. By analyzing all three isotopes, the cosmogenic component can be resolved from magmatic neon and nucleogenic neon. This suggests that neon will be a useful tool in determining cosmic exposure ages of surface rocks and meteorites. Similar to xenon, neon content observed in samples of volcanic gases is enriched in Ne, as well as 21 22 nucleogenic Ne, relative to Ne content. The neon isotopic content of these mantle-derived samples 20 represents a non-atmospheric source of neon. The Ne-enriched components are attributed to exotic 20 primordial rare gas components in the Earth, possibly representing solar neon. Elevated Ne abundances are found in diamonds, further suggesting a solar neon reservoir in the Earth. CHARACTERISTICS Neon is the second-lightest noble gas, after helium. It glows reddish-orange in a vacuum discharge tube. Also, neon has the narrowest liquid range of any element: from 24.55 K to 27.05 K (248.45 C to 245.95 C, or 415.21 F to 410.71 F). It has over 40 times the refrigerating capacity of liquid helium and three times that of liquid hydrogen (on a per unit volume basis). In most applications it is a less expensive refrigerant than helium. Neon plasma has the most intense light discharge at normal voltages and currents of all the noble gases. The average color of this light to the human eye is red-orange due to many lines in this range; it also contains a strong green line which is hidden, unless the visual components are dispersed by a spectroscope. Two quite different kinds of neon lighting are in common use. Neon glow lamps are generally tiny, with most operating at about 100250 volts. They have been widely used as power-on indicators and in circuit-testing equipment, but light-emitting diodes (LEDs) now dominate in such applications. These simple neon devices were the forerunners of plasma displays and plasma television screens. Neon signs typically operate at much higher voltages (215 kilovolts), and the luminous tubes are commonly meters long. The glass tubing is often formed into shapes and letters for signage as well as architectural and artistic applications. OCCURRENCE Stable isotopes of neon are produced in stars. Ne is created in fusing helium and oxygen in the alpha process, which requires temperatures above 100 megakelvins and masses greater than 3 solar masses.
20 20

Neon is abundant on a universal scale; it is the fifth most abundant chemical element in the universe by mass, after hydrogen, helium, oxygen, and carbon (see chemical element). Its relative rarity on Earth, like that of helium, is due to its relative lightness, high vapor pressure at very low temperatures, and chemical inertness, all properties which tend to keep it from being trapped in the condensing gas and dust clouds which resulted in the formation of smaller and warmer solid planets like Earth. Neon is monatomic, making it lighter than the molecules of diatomic nitrogen and oxygen which form the bulk of Earth's atmosphere; a balloon filled with neon will rise in air, albeit more slowly than a helium balloon. Mass abundance in the universe is about 1 part in 750 and in the Sun and presumably in the proto-solar system nebula, about 1 part in 600. The Galileo spacecraft atmospheric entry probe found that even in the upper atmosphere of Jupiter, the abundance of neon is reduced (depleted) by about a factor of 10, to a level of 1 part in 6,000 by mass. This may indicate that even the ice-planetesimals which brought neon into Jupiter from the outer solar system, formed in a region which was too warm for them to have kept their neon (abundances of heavier inert gases on Jupiter are several times that found in the Sun). Neon is rare on Earth, found in the Earth's atmosphere at 1 part in 55,000, or 18.2 ppm by volume (this is about the same as the molecule or mole fraction), or 1 part in 79,000 of air by mass. It comprises a smaller fraction in the crust. It is industrially produced by cryogenic fractional distillation of liquefied air. APPLICATIONS Neon is often used in signs and produces an unmistakable bright reddish-orange light. Although still referred to as "neon", all other colors are generated with the other noble gases or by many colors of fluorescent lighting. Neon is used in vacuum tubes, high-voltage indicators, lightning arrestors, wave meter tubes, television tubes, and helium-neon lasers. Liquefied neon is commercially used as a cryogenic refrigerant in applications not requiring the lower temperature range attainable with more extreme liquid helium refrigeration. Both neon gas and liquid neon are relatively expensive for small quantities, the price of liquid neon can be more than 55 times that of liquid helium. The driver for neon's expense is the rarity of neon, which unlike helium, can only be obtained from air. The triple point temperature of neon (24.5561 K) is a defining fixed point in the International Temperature Scale of 1990. COMPOUNDS Neon is the first p-block noble gas. Neon is generally considered to be inert. No true neutral compounds + + + + of neon are known. However, the ions Ne , (NeAr) , (NeH) , and (HeNe ) have been observed from optical and mass spectrometric studies, and there are some unverified reports of an unstable hydrate. SODIUM Sodium is a chemical element with the symbol Na (from Latin: natrium) and atomic number 11. It is a 23 soft, silver-white, highly reactive metal and is a member of the alkali metals; its only stable isotope is Na. The free metal does not occur in nature, but instead must be prepared from its compounds; it was first isolated by Humphry Davy in 1807 by the electrolysis of sodium hydroxide. Sodium is the sixth most abundant element in the Earth's crust, and exists in numerous minerals such

as feldspars, sodalite and rock salt. Many salts of sodium are highly water-soluble, and their sodium has been leached by the action of water so that chloride and sodium (NaCl) are the most common dissolved elements by weight in the Earth's bodies of oceanic water. Many sodium compounds are useful, such as sodium hydroxide (lye) for soap-making, and sodium chloride for use as a deicing agent and a nutrient (edible salt). Sodium is an essential element for all animals and some plants. In animals, sodium ions are used against potassium ions to build up charges on cell membranes, allowing transmission of nerve impulses when the charge is dissipated. The consequent need of animals for sodium causes it to be classified as a dietary inorganic macro-mineral.
1 Characteristics

o o o o

1.1 Physical 1.2 Chemical 1.3 Isotopes 1.4 Occurrence

2 Compounds 3 History 4 Commercial production

5 Applications 6 Biological role 7 Precautions

CHARACTERISTICS

Physical

Sodium at standard temperature and pressure is a soft metal that can be readily cut with a knife and is a good conductor of electricity. Freshly exposed, sodium has a bright, silvery luster that rapidly tarnishes, forming a white coating of sodium hydroxide and sodium carbonate. These properties change at elevated pressures: at 1.5 Mbar, the color changes to black, then to red transparent at 1.9 Mbar, and finally clear transparent at 3 Mbar. All of these allotropes are insulators and electrides. When sodium or its compounds are introduced into a flame, they turn it yellow, because the excited 3s electrons of sodium emit a photon when they fall from 3p to 3s; the wavelength of this photon corresponds to the D line at 589.3 nm. Spin-orbit interactions involving the electron in the 3p orbital split the D line into two; hyperfine structures involving both orbitals cause many more lines.
Chemical

Sodium is generally less reactive than potassium and more reactive than lithium. Like all the alkali metals, it reacts exothermically with water, to the point that sufficiently large pieces melt to a sphere and may explode; this reaction produces caustic sodium hydroxide and flammable hydrogen gas. When burned in dry air, it mainly forms sodium peroxide as well as some sodium oxide. In moist air, sodium hydroxide results. Sodium metal is highly reducing, with the reduction of sodium ions requiring 2.71 volts. Hence, the extraction of sodium metal from its compounds (such as with sodium chloride) uses a significant amount of energy. However, potassium and lithium have even more negative potentials. Isotopes 20 isotopes of sodium are known, but only byproduct of cosmic ray spallation:
24m 22 23

Na is stable. Two radioactive, cosmogenic isotopes are the

24

Na with a half-life of 2.6 years and

Na with a half-life of 15 hours;

all other isotopes have a half-life of less than one minute. Two nuclear isomers have been discovered, the longer-lived one being Na with a half-life of around 20.2 microseconds. Acute neutron radiation, such
23 24

as from a nuclear criticality accident, converts some of the stable measuring the concentration of calculated.
Occurrence
23 24

Na in human blood to

Na; by

Na in relation to

23

Na, the neutron radiation dosage of the victim can be

Na is created in the carbon-burning process in stars by fusing two carbon atoms together; this requires

temperatures above 600 megakelvins and a star of at least three solar masses. The Earth's crust contains 2.6% sodium by weight, making it the sixth most abundant element on Earth. Because of its high reactivity, it is never found as a pure element. It is found in many different minerals, some very soluble, such as halite and natron, others much less soluble such as amphibole, andzeolite. The insolubility of certain sodium minerals such as cryolite and feldspar arises from their polymeric anions, which in the case of feldspar is a polysilicate. In the interstellar medium, sodium is identified by the D spectral line; though it has a high vaporization temperature, its abundance allowed it to be detected by Mariner 10 in Mercury's atmosphere.

COMPOUNDS Sodium compounds are of immense commercial importance, being particularly central to industries producing glass,paper, soap, and textiles. The sodium compounds that are the most important include table salt (NaCl), soda ash(Na2CO3), baking soda (NaHCO3), caustic soda (NaOH), sodium nitrate (NaNO3), di- and tri-sodium phosphates,sodium thiosulfate (Na2S2O35H2O), and borax (Na2B4O710H2O). In its compounds, sodium is usually ionically bonded to water and anions, and is viewed as a hard Lewis acid.

Most soaps are sodium salts of fatty acids. Sodium soaps are harder (higher melting) soaps than potassium soaps. Sodium chloride is extensively used for anti-icing and de-icing and as a preservative; sodium bicarbonateis mainly used for cooking. Along with potassium, many important medicines have sodium added to improve theirbioavailability; although in most cases potassium is the better ion, sodium is selected for its lower price and atomic weight. Sodium hydride is used as a base for various reactions (such as the aldol reaction) in organic chemistry, and as a reducing agent in inorganic chemistry. HISTORY Salt has been an important commodity in human activities, as shown by the English word salary, which derives from salarium, the wafers of salt sometimes given to Roman soldiers along with their other wages. In medieval Europe, a compound of sodium with the Latin name of sodanum was used as a headacheremedy. The name sodium is thought to originate from the Arabic suda (), meaning headache, as the headache-alleviating properties of sodium carbonate or soda were well known in early times. The chemical abbreviation for sodium was first published by Jns Jakob Berzelius in his system of atomic symbols, and is a contraction of the element's new Latin name natrium, which refers to the Egyptian natron, a natural mineral salt primarily made of hydrated sodium carbonate. Natron historically had several important industrial and household uses, later eclipsed by other sodium compounds. Although sodium, sometimes called soda, had long been recognised in compounds, the metal itself was not isolated until 1807 by Sir Humphry Davy through the electrolysis of sodium hydroxide. COMMERCIAL PRODUCTION Enjoying rather specialized applications, only about 100,000 tonnes of metallic sodium are produced annually. Metallic sodium was first produced commercially in 1855 by carbothermal reduction of sodium carbonate at 1100 C, in what is known as the Deville process: Na2CO3 + 2 C 2 Na + 3 CO A related process based on the reduction of sodium hydroxide was developed in 1886. Sodium is now produced commercially through the electrolysis of molten sodium chloride, based on a process patented in 1924. This is done in a Downs cell in which the NaCl is mixed with calcium chloride to lower the melting point below 700 C. As calcium is less electropositive than sodium, no calcium will be deposited at the cathode. This method is less expensive than the previous Castner processof electrolyzing sodium hydroxide. Reagent-grade sodium in tonne quantities sold for about US$3.30/kg in 2009; lower purity metal sells for considerably less. The market for sodium is volatile due to the difficulty in its storage and shipping; it must be stored under a dry inert gas atmosphere or anhydrous mineral oil to prevent the formation of a surface layer of sodium oxide or sodium superoxide. These oxides can react violently in the presence of organic materials. Smaller quantities of sodium cost far more, in the range of US$165/kg; the high cost is partially due to the expense of shipping hazardous material. APPLICATIONS Though metallic sodium has some important uses, the major applications of sodium use it in its many compounds; millions of tons of the chloride, hydroxide, and carbonate are produced annually. BIOLOGICAL ROLE

In humans, sodium is an essential nutrient that regulates blood volume, blood pressure, osmotic equilibrium and pH; the minimum physiological requirement for sodium is 500 milligrams per day. Sodium chloride is the principal source of sodium in the diet, and is used as seasoning and preservative, such as for pickling and jerky; most of it comes from processed foods. The DRI for sodium is 2.3 grams per day, but on average people in the United States consume 3.4 grams per day, the minimum amount that promotes hypertension; this in turn causes 7.6 million premature deaths worldwide. The renin-angiotensin system regulates the amount of fluids and sodium in the body. Reduction of blood pressure and sodium concentration in the kidney result in the production of renin, which in turn produces aldosterone and angiotensin, retaining sodium in the urine. Because of the increase in sodium concentration, the production of renin decreases, and the sodium concentration returns to normal. Sodium is also important in neuron function and osmoregulation between cells and the extracellular fluid, + + their distribution mediated in all animals by Na /K -ATPase; hence, sodium is the most prominent cation in extracellular fluid. In C4 plants, sodium is a micronutrient that aids in metabolism, specifically in regeneration of phosphoenolpyruvate and synthesis of chlorophyll. In others, it substitutes for potassium in several roles, such as maintaining turgor pressure and aiding in the opening and closing of stomata. Excess sodium in the soil limits the uptake of water due to decreased water potential, which may result in wilting; similar concentrations in the cytoplasm can lead to enzyme inhibition, which in turn causes necrosis and chlorosis. To avoid these problems, plants developed mechanisms that limit sodium uptake by roots, store them in cell vacuoles, and control them over long distances; excess sodium may also be stored in old plant tissue, limiting the damage to new growth. PRECAUTIONS Care is required in handling elemental sodium, as it generates flammable hydrogen and caustic sodium hydroxide upon contact with water; powdered sodium may spontaneously explode in the presence of oxygen. Excess sodium can be safely removed by hydrolysis in a ventilated cabinet; this is typically done by sequential treatment with isopropanol, ethanol and water. Isopropanol reacts very slowly, generating the corresponding alkoxide and hydrogen. Fire extinguishers based on water accelerate sodium fires; those based on carbon dioxide and bromochlorodifluoromethane lose their effectiveness when they dissipate. An effective extinguishing agent is Met-L-X, which comprises approximately 5% Saran in sodium chloride together with flow agents; it is most commonly hand-applied with a scoop. Other materials include Lith+, which has graphite powder and an organophosphate flame retardant, and dry sand. MAGNESIUM Magnesium is a chemical element with the symbol Mg and atomic number 12. Its common oxidation number is +2. It is an alkaline earth metal and the eighth most abundant element in the Earth's crust and ninth in the known universe as a whole. Magnesium is the fourth most common element in the Earth as a whole (behind iron, oxygen and silicon), making up 13% of the planet's mass and a large fraction of the planet's mantle. The relative abundance of magnesium is related to the fact that it easily builds up in supernova stars from a sequential addition of three helium nuclei to carbon (which in turn is made from three helium nuclei). Due to magnesium ion's high solubility in water, it is the third most abundant element dissolved in seawater. Magnesium is produced in stars larger than 3 solar masses by fusing helium and neon in the alpha process at temperatures above 600 megakelvins.

The free element (metal) is not found naturally on Earth, as it is highly reactive (though once produced, it is coated in a thin layer of oxide (see passivation), which partly masks this reactivity). The free metal burns with a characteristic brilliant white light, making it a useful ingredient in flares. The metal is now mainly obtained by electrolysis of magnesium salts obtained from brine. Commercially, the chief use for the metal is as an alloying agent to make aluminium-magnesium alloys, sometimes called magnalium or magnelium. Since magnesium is less dense than aluminium, these alloys are prized for their relative lightness and strength. In human biology, magnesium is the eleventh most abundant element by mass in the human body. Its ions are essential to all living cells, where they play a major role in manipulating important biological polyphosphate compounds like ATP, DNA, and RNA. Hundreds of enzymes thus require magnesium ions to function. Magnesium compounds are used medicinally as common laxatives, antacids (e.g., milk of magnesia), and in a number of situations where stabilization of abnormal nerve excitation and blood vessel spasm is required (e.g., to treat eclampsia). Magnesium ions are sour to the taste, and in low concentrations they help to impart a natural tartness to fresh mineral waters. In vegetation, magnesium is the metallic ion at the center of chlorophyll, and is thus a common additive to fertilizers.
1 Characteristics

o o

1.1 Properties 1.2 Occurrence

2 Forms

o o o

2.1 Alloy 2.2 Compounds 2.3 Isotopes

3 Production

4 History 6 Biological roles 7 Safety precautions for magnesium metal

CHARACTERISTICS

Properties

Elemental magnesium is a rather strong, silvery-white, light-weight metal (two thirds the density of aluminium). It tarnishes slightly when exposed to air, although unlike the alkali metals, an oxygen-free environment is unnecessary for storage because magnesium is protected by a thin layer of oxide that is fairly impermeable and difficult to remove. Like its lower periodic table group neighbor calcium, magnesium reacts with water at room temperature, though it reacts much more slowly than calcium.

When submerged in water, hydrogen bubbles almost unnoticeably begin to form on the surface of the metalthough if powdered, it reacts much more rapidly. The reaction occurs faster with higher temperatures (see precautions). Magnesium's ability to react with water can be harnessed to produce energy and run a magnesium-based engine. Magnesium also reacts exothermically with most acids, such as hydrochloric acid (HCl). As with aluminium, zinc and many other metals, the reaction with hydrochloric acid produces the chloride of the metal and releases hydrogen gas. Magnesium is a highly flammable metal, but while it is easy to ignite when powdered or shaved into thin strips, it is difficult to ignite in mass or bulk. Once ignited, it is difficult to extinguish, being able to burn in nitrogen (forming magnesium nitride), carbon dioxide (forming magnesium oxide and carbon) and water (forming magnesium oxide and hydrogen). This property was used in incendiary weapons used in the firebombing of cities in World War II, the only practical civil defense being to smother a burning flare under dry sand to exclude the atmosphere. On burning in air, magnesium produces a brilliant white light that includes strong ultraviolet. Thus magnesium powder (flash powder) was used as a source of illumination in the early days of photography. Later, magnesium ribbon was used in electrically ignited flash bulbs. Magnesium powder is used in the manufacture of fireworks and marine flares where a brilliant white light is required. Flame temperatures of magnesium and magnesium alloys can reach 3,100 C (3,370 K; 5,610 F), although flame height above the burning metal is usually less than 300 mm (12 in). Magnesium may be used as an ignition source for thermite, a mixture of aluminium and iron oxide powder that is otherwise difficult to ignite. Those properties are due to magnesium's high specific heat, the fourth highest specific heat among the metals. Magnesium compounds are typically white crystals. Most are soluble in water, providing the sour-tasting 2+ magnesium ion Mg . Small amounts of dissolved magnesium ion contribute to the tartness and taste of natural waters. Magnesium ion in large amounts is an ionic laxative, and magnesium sulfate (common name: Epsom salt) is sometimes used for this purpose. So-called "milk of magnesia" is a water suspension of one of the few insoluble magnesium compounds,magnesium hydroxide. The undissolved particles give rise to its appearance and name. Milk of magnesia is a mild base commonly used as an antacid, which has some laxative side effect.
Occurrence

Magnesium is the eighth most abundant element in the Earth's crust by mass and tied in seventh place with iron in terms of molarity. It is found in large deposits of magnesite, dolomite, and other minerals, and in mineral waters, where magnesium ion is soluble. Although magnesium is found in over 60 minerals, only dolomite, magnesite, brucite, carnallite, talc, and olivine are of commercial importance. The Mg2+ cation is the second most abundant cation in seawater (occurring at about 12% of the mass of sodium there), which makes seawater and sea-salt an attractive commercial source of Mg. To extract the magnesium, calcium hydroxide is added to seawater to form magnesium hydroxide precipitate. MgCl2 + Ca(OH)2 Mg(OH)2 + CaCl2 Magnesium hydroxide (brucite) is insoluble in water so it can be filtered out, and reacted with hydrochloric acid to obtain concentrated magnesium chloride. Mg(OH)2 + 2 HCl MgCl2 + 2 H2O

From magnesium chloride, electrolysis produces magnesium.

FORMS

Alloy

As of 2013 magnesium alloy consumption is less than a million tons per year, compared with 50 million tons of aluminum alloys. Its use has been historically limited by its tendency to corrode, high-temperature creep and flammability. Research and development eliminated magnesium's tendency toward high-temperature creep by inclusion of scandium and gadolinium. Flammability was greatly reduced by introducing a small amount of calcium into the mix. The presence of iron, nickel, copper and cobalt strongly activates corrosion. This is due to their low solid solubility limits (above a very small percentage they precipitate out as intermetallic compounds) and because they behave as active cathodic sites that reduce water and cause the loss of magnesium. Reducing the quantity of these metals improves corrosion resistance. Sufficient manganese overcomes the corrosive effects of iron. This requires precise control over composition, increasing costs. Adding a cathodic poison captures atomic hydrogen within the structure of a metal. This prevents the formation of free hydrogen gas which is required for corrosive chemical processes. The addition of about one-third of a percent of arsenic reduces its corrosion rate in a salt solution by a factor of nearly ten.
Compounds

Magnesium forms a variety of industrially and biologically important compounds, including magnesium oxide, various salts and others. Isotopes Magnesium has three stable isotopes: Mg, Mg and Mg. All are present in significant amounts (see 24 28 table of isotopes above). About 79% of Mg is Mg. The isotope Mg is radioactive and in the 1950s to 1970s was made commercially by several nuclear power plants for use in scientific experiments. This isotope has a relatively short half-life (21 hours) and so its use was limited by shipping times.
26 24 25 26

Mg has found application in isotopic geology, similar to that of aluminium. Mg is a radiogenic daughter 26 26 product of Al, which has a half-life of 717,000 years. Large enrichments of stable Mg have been observed in the Ca-Al-rich inclusions of some carbonaceous chondrite meteorites. The anomalous 26 26 abundance of Mg is attributed to the decay of its parent Al in the inclusions. Therefore, the meteorite 26 must have formed in the solar nebula before the Al had decayed. Hence, these fragments are among the oldest objects in the solar system and have preserved information about its early history. It is conventional to plot Mg/ Mg against an Al/Mg ratio. In an isochron dating plot, the Al/Mg ratio 27 24 26 27 plotted is Al/ Mg. The slope of the isochron has no age significance, but indicates the initial Al/ Al ratio in the sample at the time when the systems were separated from a common reservoir.
26 24

26

PRODUCTION

China is the dominant supplier of magnesium, with approximately 80% of the world market share. China is almost completely reliant on the silicothermicPidgeon process (the reduction of the oxide at high temperatures with silicon) to obtain the metal. In the United States, magnesium is principally obtained by electrolysis of fused magnesium chloride from brines, wells, and sea water. At the cathode, theMg2+ ion is reduced by two electrons to magnesium metal: Mg2+ + 2 e Mg At the anode, each pair of Cl ions is oxidized to chlorine gas, releasing two electrons to complete the circuit: 2 Cl Cl2 (g) + 2 e A new process, solid oxide membrane technology, involves the electrolytic reduction of MgO. At the cathode Mg2+ ion is reduced by two electrons to magnesium metal. The electrolyte is Yttriastabilized zirconia(YSZ). The anode is a liquid metal. At the YSZ/liquid metal anode O2 is reduced. A layer of graphite borders the liquid metal anode, and at this interface carbon and oxygen react to form carbon monoxide. When silver is used as the liquid metal anode, there is no reductant carbon or hydrogen needed, and only oxygen gas is evolved at the anode. It has been reported that this method provides a 40% reduction in cost per pound over the electrolytic reduction method. This method is more environmentally sound than others because there is much less carbon dioxide emitted. The United States has traditionally been the major world supplier of this metal, supplying 45% of world production even as recently as 1995. Today, the US market share is at 7%, with a single domestic producer left, US Magnesium, a Renco Group company in Utah born from now-defunct Magcorp.
HISTORY

The name magnesium originates from the Greek word for a district in Thessaly called Magnesia. It is related to magnetite and manganese, which also originated from this area, and required differentiation as separate substances. See manganese for this history. In 1618, a farmer at Epsom in England attempted to give his cows water from a well there. The cows refused to drink because of the water's bitter taste, but the farmer noticed that the water seemed to heal scratches and rashes. The substance became known as Epsom salts and its fame spread. It was eventually recognized as hydrated magnesium sulfate, MgSO 47H2O. The metal itself was first produced by Sir Humphry Davy in England in 1808. He used electrolysis on a mixture of magnesia and mercuric oxide. Antoine Bussyprepared it in coherent form in 1831. Davy's first suggestion for a name was magnium, but the name magnesium is now used. BIOLOGICAL ROLES Because of the important interaction between phosphate and magnesium ions, magnesium ions are essential to the basic nucleic acid chemistry of life, and thus are essential to all cells of all known living

organisms. Over 300 enzymes require the presence of magnesium ions for their catalytic action, including all enzymes utilizing or synthesizing ATP, or those that use other nucleotides to synthesize DNAand RNA. ATP exists in cells normally as a chelate of ATP and a magnesium ion. Plants have an additional use for magnesium in that chlorophylls are magnesiumcentered porphyrins. Magnesium deficiency in plants causes late-season yellowing between leaf veins, especially in older leaves, and can be corrected by applying Epsom salts (which is rapidly leached), or else crushed dolomitic limestone to the soil. Magnesium is a vital component of a healthy human diet. Human magnesium deficiency (including conditions that show few overt symptoms) is relatively rare although only 32% of people in the United States meet the RDA-DRI; low levels of magnesium in the body has been associated with the development of a number of human illnesses such as asthma, diabetes, and osteoporosis. Taken in the proper amount magnesium plays a role in preventing both stroke and heart attack. The symptoms of people with fibromyalgia, migraines, and girls going through their premenstrual syndrome are less severe and magnesium can shorten the length of the migraine symptoms. Adult human bodies contain about 24 grams of magnesium, with 60% in the skeleton, 39% intracellular (20% in skeletal muscle), and 1% extracellular. Serum levels are typically 0.71.0 mmol/L or 1.82.4 mEq/L. Serum magnesium levels may appear normal even in cases of underlying intracellular deficiency, although no known mechanism maintains a homeostatic level in the blood other than renal excretion of high blood levels. Intracellular magnesium is correlated with intracellular potassium. Magnesium is absorbed in the gastrointestinal tract, with more absorbed when status is lower. Magnesium competes with calcium in the human body, in this way it actually keeps calcium in check. However, this can cause a calcium deficiency if calcium levels are already low. Low and high protein intake inhibit magnesium absorption, and other factors such as phosphate, phytate, and fat affect absorption. Absorbed dietary magnesium is largely excreted through the urine, although most magnesium "administered orally" is excreted through the feces. Magnesium status may be assessed roughly through serum and erythrocyte Mg concentrations and urinary and fecal excretion, but intravenous magnesium loading tests are likely the most accurate and practical in most people. In these tests, magnesium is injected intravenously; a retention of 20% or more indicates deficiency. Other nutrient deficiencies are identified throughbiomarkers, but none are established for magnesium. The UK recommended daily values for magnesium is 300 mg for men and 270 mg for women. Spices, nuts, cereals, coffee, cocoa, tea, and vegetables are rich sources of magnesium. Green leafy vegetables such as spinach are also rich in magnesium as they contain chlorophyll. Observations of reduced dietary magnesium intake in modern Western countries compared to earlier generations may be related to food refining and modern fertilizers that contain no magnesium. Numerous pharmaceutical preparations of magnesium, as well as magnesium dietary supplements are available. Magnesium oxide, one of the most common forms in magnesium dietary supplements because it has high magnesium content per weight, has been reported the least bioavailable. Magnesium citrate has been reported as more bioavailable than oxide or amino-acid chelate (glycinate) forms. Excess magnesium in the blood is freely filtered at the kidneys, and for this reason it is difficult to overdose on magnesium from dietary sources alone. With supplements, overdose is possible, however, particularly in people with poor renal function; occasionally, with use of high cathartic doses of

magnesium salts, severe hypermagnesemia has been reported to occur even without renal dysfunction. Alcoholism can produce a magnesium deficiency, which is easily reversed by oral or parenteral administration, depending on the degree of deficiency. SAFETY PRECAUTIONS FOR MAGNESIUM METAL Magnesium metal and its alloys are explosive hazards; they are highly flammable in their pure form when molten or in powder or ribbon form. Burning or molten magnesium metal reacts violently with water. When working with powdered magnesium, safety glasses with welding eye protection are employed, because the bright white light produced by burning magnesium contains ultraviolet light that can permanently damage the retinas of the eyes. Magnesium is capable of reducing water to highly flammable hydrogen gas: Mg (s) + 2 H2O (l) Mg(OH)2 (s) + H2 (g) As a result, water cannot extinguish magnesium fires. The hydrogen gas produced only intensifies the fire. Dry sand is an effective smothering agent, but only on relatively level and flat surfaces. Magnesium also reacts with carbon dioxide to form magnesium oxide and carbon: 2 Mg (s) + CO2 2 MgO (s) + C (s) hence, carbon dioxide fire extinguishers cannot be used for extinguishing magnesium fires either. Burning magnesium is usually quenched by using a Class D dry chemical fire extinguisher, or by covering the fire with sand or magnesium foundry flux to remove its air source.

.ALUMINUM Aluminium (or aluminum) is a chemical element in the boron group with symbol Al and atomic number 13. It is a silvery white, soft, ductile metal. Aluminium is the third most abundant element (after oxygen and silicon), and the most abundant metal, in the Earth's crust. It makes up about 8% by weight of the Earth's solid surface. Aluminium metal is so chemically reactive that native specimens are rare and limited to extreme reducing environments. Instead, it is found combined in over 270 different minerals. The chief ore of aluminium is bauxite. Aluminium is remarkable for the metal's low density and for its ability to resist corrosion due to the phenomenon of passivation. Structural components made from aluminium and its alloys are vital to the aerospace industry and are important in other areas of transportation and structural materials. The most useful compounds of aluminium, at least on a weight basis, are the oxides and sulfates. Despite its prevalence in the environment, aluminium salts are not known to be used by any form of life. In keeping with its pervasiveness, aluminium is well tolerated by plants and animals. Owing to their prevalence, potential beneficial (or otherwise) biological roles of aluminium compounds are of continuing interest.
1 Characteristics

o o o o

1.1 Physical 1.2 Chemical 1.3 Isotopes 1.4 Natural occurrence

4 Applications

o o

4.1 General use 4.2 Aluminium compounds

4.2.1 Alumina 4.2.2 Sulfates 4.2.3 Chlorides 4.2.4 Niche compounds

4.3 Aluminium alloys in structural applications

5 History 7 Health concerns 8 Effect on plants

CHARACTERISTICS

Physical

Aluminium is a relatively soft, durable, lightweight, ductile and malleable metal with appearance ranging from silvery to dull gray, depending on the surface roughness. It is nonmagnetic and does not easily ignite. A fresh film of aluminium serves as a good reflector (approximately 92%) of visible light and an excellent reflector (as much as 98%) of medium and far infrared radiation. The yield strength of pure aluminium is 711 MPa, while aluminium alloys have yield strengths ranging from 200 MPa to 600 MPa. Aluminium has about one-third the density and stiffness of steel. It is easily machined, cast, drawn and extruded. Aluminium atoms are arranged in a face-centered cubic (fcc) structure. Aluminium has a stacking-fault 2 energy of approximately 200 mJ/m . Aluminium is a good thermal and electrical conductor, having 59% the conductivity of copper, both thermal and electrical, while having only 30% of copper's density. Aluminium is capable of being a superconductor, with a superconducting critical temperature of 1.2 Kelvinand a critical magnetic field of about 100 gauss (10 milliteslas).
Chemical

Corrosion resistance can be excellent due to a thin surface layer of aluminium oxide that forms when the metal is exposed to air, effectively preventing furtheroxidation. The strongest aluminium alloys are less

corrosion resistant due to galvanic reactions with alloyed copper. This corrosion resistance is also often greatly reduced by aqueous salts, particularly in the presence of dissimilar metals. Owing to its resistance to corrosion, aluminium is one of the few metals that retain silvery reflectance in finely powdered form, making it an important component of silver-colored paints. Aluminium mirror finish has the highest reflectance of any metal in the 200400 nm (UV) and the 3,00010,000 nm (far IR) regions; in the 400700 nm visible range it is slightly outperformed by tin and silver and in the 7003000 (near IR) by silver, gold, and copper. Aluminium is oxidized by water to produce hydrogen and heat: 2 Al + 3 H2O Al2O3 + 3 H2 This conversion is of interest for the production of hydrogen. Challenges include circumventing the formed oxide layer which inhibits the reaction and the expenses associated with the storage of energy by regeneration of the Al metal.
Isotopes
27

Aluminium has many known isotopes, whose mass numbers range from 21 to 42; however, only (stable isotope) and
26

Al

Al (radioactive isotope, t1/2 = 7.210 y) occur naturally.

26

27

Al has a natural

abundance above 99.9%.

Al is produced from argon in the atmosphere by spallation caused by cosmic26 10

rayprotons. Aluminium isotopes have found practical application in dating marine sediments, manganese nodules, glacial ice, quartz in rock exposures, andmeteorites. The ratio of
26

Al to

Be has been used to

5 6

study the role of transport, deposition, sediment storage, burial times, and erosion on 10 to 10 year time scales. Cosmogenic Al was first applied in studies of the Moon and meteorites. Meteoroid fragments,
26

after departure from their parent bodies, are exposed to intense cosmic-ray bombardment during their travel through space, causing substantial drastically reduces
26

Al production. After falling to Earth, atmospheric shielding

26

Al production, and its decay can then be used to determine the meteorite's terrestrial Al was relatively abundant at the time of formation of our
26

age. Meteorite research has also shown that

planetary system. Most meteorite scientists believe that the energy released by the decay of

Al was

responsible for the melting and differentiation of some asteroids after their formation 4.55 billion years ago. Natural occurrence Stable aluminium is created when hydrogen fuses with magnesium either in large stars or in supernovae. In the Earth's crust, aluminium is the most abundant (8.3% by weight) metallic element and the third most abundant of all elements (after oxygen and silicon). Because of its strong affinity to oxygen, it is almost never found in the elemental state; instead it is found in oxides or silicates. Feldspars, the most common group of minerals in the Earth's crust, are aluminosilicates. Native aluminium metal can only be found as a minor phase in low oxygen fugacity environments, such as the interiors of certain volcanoes. Native aluminium has been reported in cold seeps in the northeastern continental slope of the South China

Sea and Chen et al. (2011) have proposed a theory of its origin as resulting by reduction from tetrahydroxoaluminate Al(OH)4 to metallic aluminium by bacteria. It also occurs in the minerals beryl, cryolite, garnet, spinel and turquoise. Impurities in Al2O3, such as chromium or iron yield the gemstones ruby and sapphire, respectively. Although aluminium is an extremely common and widespread element, the common aluminium minerals are not economic sources of the metal. Almost all metallic aluminium is produced from the ore bauxite (AlOx(OH)32x). Bauxite occurs as a weathering product of low iron and silica bedrock in tropical climatic conditions. Large deposits of bauxite occur in Australia, Brazil, Guinea and Jamaica and the primary mining areas for the ore are in Australia, Brazil, China,India, Guinea, Indonesia, Jamaica, Russia and Suriname. APPLICATIONS General use Aluminium is the most widely used non-ferrous metal. Global production of aluminium in 2005 was 31.9 million tonnes. It exceeded that of any other metal except iron (837.5 million tonnes). Forecast for 2012 is 4245 million tonnes, driven by rising Chinese output. Aluminium is almost always alloyed, which markedly improves its mechanical properties, especially when tempered. For example, the common aluminium foils and beverage cans are alloys of 92% to 99% aluminium. The main alloying agents are copper, zinc, magnesium, manganese, and silicon (e.g., duralumin) and the levels of these other metals are in the range of a few percent by weight. Some of the many uses for aluminium metal are in: Transportation (automobiles, aircraft, trucks, railway cars, marine vessels, bicycles, etc.) as sheet, tube, castings, etc. Packaging (cans, foil, frame of etc.) Construction (windows, doors, siding, building wire, etc.). A wide range of household items, from cooking utensils to baseball bats, watches. Street lighting poles, sailing ship masts, walking poles, etc. Outer shells of consumer electronics, also cases for equipment e.g. photographic equipment, MacBook Pro's casing Electrical transmission lines for power distribution MKM steel and Alnico magnets Super purity aluminium (SPA, 99.980% to 99.999% Al), used in electronics and CDs. Heat sinks for electronic appliances such as transistors and CPUs. Substrate material of metal-core copper clad laminates used in high brightness LED lighting. Powdered aluminium is used in paint, and in pyrotechnics such as solid rocket fuels and thermite. Aluminium can be reacted with hydrochloric acid or with sodium hydroxide to produce hydrogen gas. A variety of countries, including France, Italy, Poland, Finland, Romania, Israel, and the former Yugoslavia, have issued coins struck in aluminium or aluminium-copper alloys.

Some guitar models sport aluminium diamond plates on the surface of the instruments, usually either chrome or black. Kramer Guitars and Travis Bean are both known for having produced guitars with necks made of aluminium, which gives the instrument a very distinct sound.

Aluminium is usually alloyed it is used as pure metal only when corrosion resistance and/or workability is more important than strength or hardness. A thin layer of aluminium can be deposited onto a flat surface by physical vapour deposition or (very infrequently) chemical vapour deposition or other chemical means to formoptical coatings and mirrors. Aluminum compounds Because aluminium is abundant and most of its derivatives exhibit low toxicity, the compounds of aluminium enjoy wide and sometimes large-scale applications. Aluminum alloys in structural applications Aluminium alloys with a wide range of properties are used in engineering structures. Alloy systems are classified by a number system (ANSI) or by names indicating their main alloying constituents (DIN and ISO). The strength and durability of aluminium alloys vary widely, not only as a result of the components of the specific alloy, but also as a result of heat treatments and manufacturing processes. A lack of knowledge of these aspects has from time to time led to improperly designed structures and gained aluminium a bad reputation. One important structural limitation of aluminium alloys is their fatigue strength. Unlike steels, aluminium alloys have no well-defined fatigue limit, meaning that fatigue failure eventually occurs, under even very small cyclic loadings. This implies that engineers must assess these loads and design for a fixed life rather than an infinite life. Another important property of aluminium alloys is their sensitivity to heat. Workshop procedures involving heating are complicated by the fact that aluminium, unlike steel, melts without first glowing red. Forming operations where a blow torch is used therefore require some expertise, since no visual signs reveal how close the material is to melting. Aluminium alloys, like all structural alloys, also are subject to internal stresses following heating operations such as welding and casting. The problem with aluminium alloys in this regard is their low melting point, which make them more susceptible to distortions from thermally induced stress relief. Controlled stress relief can be done during manufacturing by heat-treating the parts in an oven, followed by gradual coolingin effect annealing the stresses. The low melting point of aluminium alloys has not precluded their use in rocketry; even for use in constructing combustion chambers where gases can reach 3500 K. The Agena upper stage engine used a regeneratively cooled aluminium design for some parts of the nozzle, including the thermally critical throat region. Another alloy of some value is aluminium bronze (Cu-Al alloy). HISTORY Ancient Greeks and Romans used aluminium salts as dyeing mordants and as astringents for dressing wounds; alum is still used as a styptic. In 1761, Guyton de Morveau suggested calling the base alum alumine. In 1808, Humphry Davy identified the existence of a metal base of alum, which he at first termed alumium and later aluminum.

The metal was first produced in 1825 in an impure form by Danish physicist and chemist Hans Christian rsted. He reacted anhydrous aluminium chloride withpotassium amalgam, yielding a lump of metal looking similar to tin. Friedrich Whler was aware of these experiments and cited them, but after redoing the experiments of rsted he concluded that this metal was pure potassium. He conducted a similar experiment in 1827 by mixing anhydrous aluminium chloride with potassium and yielded aluminium. Whler is generally credited with isolating aluminium (Latin alumen, alum). Further, Pierre Berthier discovered aluminium in bauxite ore and successfully extracted it. Frenchman Henri Etienne Sainte-Claire Deville improved Whler's method in 1846, and described his improvements in a book in 1859, chief among these being the substitution of sodium for the considerably more expensive potassium. Deville likely also conceived the idea of the electrolysis of aluminium oxide dissolved in cryolite; Charles Martin Hall and Paul Hroult might have developed the more practical process after Deville. Prior to commercial electrical generation in the early 1880s, and the Hall-Hroult process in the mid 1880s, aluminium was exceedingly difficult to extract from its various ores. This made pure aluminium more valuable than gold. Bars of aluminium were exhibited at the Exposition Universelle of 1855. Napoleon III of France is reputed to have given a banquet where the most honoured guests were given aluminium utensils, while the others made do with gold. Aluminium was selected as the material to be used for the 100 ounce (2.8 kg) capstone of the Washington Monument in 1884, a time when one ounce (30 grams) cost the daily wage of a common worker on the project. The capstone, which was set in place on December 6, 1884, in an elaborate dedication ceremony, was the largest single piece of aluminium cast at the time, when aluminium was as expensive as silver. The Cowles companies supplied aluminium alloy in quantity in the United States and England using smelters like the furnace of Carl Wilhelm Siemens by 1886. Charles Martin Hall of Ohio in the U.S. and Paul Hroult of France independently developed the Hall-Hroult electrolytic process that made extracting aluminium from minerals cheaper and is now the principal method used worldwide. Hall's process, in 1888 with the financial backing of Alfred E. Hunt, started the Pittsburgh Reduction Company today known as Alcoa. Hroult's process was in production by 1889 in Switzerland at Aluminium Industrie, now Alcan, and at British Aluminium, now Luxfer Group and Alcoa, by 1896 in Scotland. By 1895, the metal was being used as a building material as far away as Sydney, Australia in the dome of the Chief Secretary's Building. With the explosive expansion of the airplane industry during World War I (1914-1917), major governments demanded large shipments of aluminium for light, strong airframes. They often subsidized factories and the necessary electrical supply systems. Many navies have used an aluminium superstructure for their vessels; the 1975 fire aboard USS Belknap that gutted her aluminium superstructure, as well as observation of battle damage to British ships during the Falklands War, led to many navies switching to all steel superstructures. The Arleigh Burke class was the first such U.S. ship, being constructed entirely of steel. Aluminium wire was once widely used for domestic electrical wiring. Owing to corrosion-induced failures, a number of fires resulted. HEALTH CONCERNS

Despite its natural abundance, aluminium has no known function in biology. It is remarkably nontoxic, aluminium sulfate having an LD50 of 6207 mg/kg (oral, mouse), which corresponds to 500 grams for a 80 kg person. The extremely low acute toxicity notwithstanding, the health effects of aluminium are of interest in view of the widespread occurrence of the element in the environment and in commerce. Some toxicity can be traced to deposition in bone and the central nervous system, which is particularly increased in patients with reduced renal function. Because aluminium competes with calcium for absorption, increased amounts of dietary aluminium may contribute to the reduced skeletal mineralization (osteopenia) observed in preterm infants and infants with growth retardation. In very high doses, aluminium can cause neurotoxicity, and is associated with altered function of the bloodbrain barrier. A small percentage of people are allergic to aluminium and experience contact dermatitis, digestive disorders, vomiting or other symptoms upon contact or ingestion of products containing aluminium, such as deodorants or antacids. In those without allergies, aluminium is not as toxic as heavy metals, but there is evidence of some toxicity if it is consumed in excessive amounts. Although the use of aluminium cookware has not been shown to lead to aluminium toxicity in general, excessive consumption of antacids containing aluminium compounds and excessive use of aluminium-containing antiperspirants provide more significant exposure levels. Studies have shown that consumption of acidic foods or liquids with aluminium significantly increases aluminium absorption, and maltol has been shown to increase the accumulation of aluminium in nervous and osseus tissue. Furthermore, aluminium increases estrogen-related gene expression in human breast cancer cells cultured in the laboratory. The estrogen-like effects of these salts have led to their classification as a metalloestrogen. The effects of aluminium in antiperspirants has been examined over the course of decades with little evidence of skin irritation. Nonetheless, its occurrence in antiperspirants, dyes (such as aluminium lake), and food additives is controversial in some quarters. Although there is little evidence that normal exposure to aluminium presents a risk to healthy adults, some studies point to risks associated with increased exposure to the metal. Aluminium in food may be absorbed more than aluminium from water. Some researchers have expressed concerns that the aluminium in antiperspirants may increase the risk of breast cancer, and aluminium has controversially been implicated as a factor in Alzheimer's disease. The Camelford water pollution incident involved a number of people consuming aluminium sulfate. Investigations of the long-term health effects are still ongoing, but elevated brain aluminium concentrations have been found in post-mortem examinations of victims, and further research to determine if there is a link with cerebral amyloid angiopathy has been commissioned. According to the Alzheimer's Society, the medical and scientific opinion is that studies have not convincingly demonstrated a causal relationship between aluminium and Alzheimer's disease. Nevertheless, some studies, such as those on the PAQUID cohort, cite aluminium exposure as a risk factor for Alzheimer's disease. Some brain plaques have been found to contain increased levels of the metal.Research in this area has been inconclusive; aluminium accumulation may be a consequence of the disease rather than a causal agent. In any event, if there is any toxicity of aluminium, it must be via a very specific mechanism, since total human exposure to the element in the form of naturally occurring clay in soil and dust is enormously large over a lifetime. Scientific consensus does not yet exist about whether aluminium exposure could directly increase the risk of Alzheimer's disease. EFFECT ON PLANTS

Aluminium is primary among the factors that reduce plant growth on acid soils. Although it is generally 3+ harmless to plant growth in pH-neutral soils, the concentration in acid soils of toxic Al cationsincreases and disturbs root growth and function. Most acid soils are saturated with aluminium rather than hydrogen ions. The acidity of the soil is therefore a result of hydrolysis of aluminium compounds. This concept of "corrected lime potential" to define the degree of base saturation in soils became the basis for procedures now used in soil testing laboratories to determine the "lime requirement" of soils. Wheat's adaptation to allow aluminium tolerance is such that the aluminium induces a release of organic compounds that bind to the harmful aluminium cations. Sorghum is believed to have the same tolerance mechanism. The first gene for aluminium tolerance has been identified in wheat. It was shown that sorghum's aluminium tolerance is controlled by a single gene, as for wheat. This is not the case in all plants. SILICON Silicon, a tetravalent metalloid, is a chemical element with the symbol Si and atomic number 14. It is less reactive than its chemical analog carbon, thenonmetal directly above it in the periodic table, but more reactive than germanium, the metalloid directly below it in the table. Controversy about silicon's character dates to its discovery; it was first prepared and characterized in pure form in 1823. In 1808, it was given the name silicium (from Latin: silex, hard stone or flint), with an -ium word-ending to suggest a metal, a name which the element retains in several non-English languages. However, its final English name, first suggested in 1817, reflects the more physically similar elements carbon and boron. Silicon is the eighth most common element in the universe by mass, but very rarely occurs as the pure free element in nature. It is most widely distributed industs, sands, planetoids, and planets as various forms of silicon dioxide (silica) or silicates. Over 90% of the Earth's crust is composed of silicate minerals, making silicon the second most abundant element in the Earth's crust (about 28% by mass) after oxygen. Most silicon is used commercially without being separated, and indeed often with little processing of compounds from nature. These include direct industrial building-use of clays, silica sand and stone. Silica is used in ceramic brick. Silicate goes into Portland cement for mortar and stucco, and when combined with silica sand and gravel, to make concrete. Silicates are also in whiteware ceramics such as porcelain, and in traditional quartz-based soda-lime glass. More modern silicon compounds such as silicon carbide form abrasives and high-strength ceramics. Silicon is the basis of the ubiquitous synthetic siliconbased polymers called silicones. Elemental silicon also has a large impact on the modern world economy. Although most free silicon is used in the steel refining, aluminum-casting, and fine chemical industries (often to make fumed silica), the relatively small portion of very highly purified silicon that is used in semiconductor electronics (< 10%) is perhaps even more critical. Because of wide use of silicon in integrated circuits, the basis of most computers, a great deal of modern technology depends on it. Silicon is an essential element in biology, although only tiny traces of it appear to be required by animals. However, various sea sponges as well as microorganisms like diatoms need silicon in order to have structure. It is much more important to the metabolism of plants, particularly many grasses.
1 Characteristics

o o
o o

1.1 Physical 1.2 Chemical

1.3 Isotopes 1.4 Occurrence

3 Compounds 4 History 5 Applications

o o o

5.1 Compounds 5.2 Alloys 5.3 Electronics

6 Biological role

CHARACTERISTICS

Physical

Silicon is a solid at room temperature, with relatively high melting and boiling points of 1414 and 3265 degrees Celsius respectively. It has a greater density in a liquid state than a solid state. It does not contract when it freezes like most substances, but expands, similar to how ice is less dense than water. 1 1 With a relatively high thermal conductivity of 149 Wm K , silicon conducts heat well and as a result is not often used to insulate hot objects. In its crystalline form, pure silicon has a gray color and a metallic luster. Like germanium, silicon is rather strong, very brittle, and prone to chipping. Silicon, like carbon and germanium, crystallizes in a diamond cubic crystal structure, with a lattice spacing of 0.5430710 nm (5.430710 ). The outer electron orbital of silicon, like that of carbon, has four valence electrons. The 1s, 2s, 2p and 3s subshells are completely filled while the 3p subshell contains two electrons out of a possible six. Silicon is a semiconductor. It has a negative temperature coefficient of resistance, since the number of free charge carriers increases with temperature. The electrical resistance of single crystal silicon significantly changes under the application of mechanical stress due to thepiezoresistive effect.
Chemical

Silicon is a metalloid, readily either donating or sharing its four outer electrons, allowing for many forms of chemical bonding. Like carbon, it typically forms four bonds. Unlike carbon, it can accept additional electrons and form five or six bonds in a sometimes more labile silicate form. Tetra-valent silicon is relatively inert, but still reacts with halogens and dilute alkalis, but most acids (except for some hyperreactive combinations of nitric acid and hydrofluoric acid) have no known effect on it. However, having

four bonding electrons gives it, like carbon, many opportunities to combine with other elements or compounds under the right circumstances. Isotopes Naturally occurring silicon is composed of three stable isotopes, silicon-28, silicon-29, and silicon-30, with silicon-28 being the most abundant (92% natural abundance). Out of these, only silicon-29 is of use in NMR and EPR spectroscopy. Twentyradioisotopes have been characterized, with the most stable being silicon-32 with a half-life of 170 years, and silicon-31 with a half-life of 157.3 minutes. All of the remaining radioactive isotopes have half-lives that are less than seven seconds, and the majority of these have half-lives that are less than one tenth of a second. Silicon does not have any known nuclear isomers. The isotopes of silicon range in mass number from 22 to 44. The most common decay mode of six isotopes with mass numbers lower than the most abundant stable isotope, silicon-28, is +, primarily forming aluminium isotopes (13 protons) as decay products. The most common decay mode(s) for 16 isotopes with mass numbers higher than silicon-28 is , primarily forming phosphorus isotopes (15 protons) as decay products.
Occurrence

Measured by mass, silicon makes up 27.7% of the Earth's crust and is the second most abundant element in the crust, with only oxygen having a greater abundance. Silicon is usually found in the form of complex silicate minerals, and less often assilicon dioxide (silica, a major component of common sand). Pure silicon crystals are very rarely found in nature. The silicate mineralsvarious minerals containing silicon, oxygen and reactive metals account for 90% of the mass of the Earth's crust. This is due to the fact that at the high temperatures characteristic of the formation of the inner solar system, silicon and oxygen have a great affinity for each other, forming networks of silicon and oxygen in chemical compounds of very low volatility. Since oxygen and silicon were the most common non-gaseous and non-metallic elements in the debris fromsupernova dust which formed the protoplanetary disk in the formation and evolution of the Solar System, they formed many complex silicates which accreted into larger rocky planetesimals that formed the terrestrial planets. Here, the reduced silicate mineral matrix entrapped the metals reactive enough to be oxidized (aluminum, calcium, sodium, potassium and magnesium). After loss of volatile gases, as well as carbon and sulfur via reaction with hydrogen, this silicate mixture of elements formed most of the Earth's crust. These silicates were of relatively low density with respect to iron, nickel, and other metals non-reactive to oxygen and thus a residuum of uncombined iron and nickel sank to the planet's core, leaving a thick mantle consisting mostly of magnesium and iron silicates. These are thought to be mostly silicate perovskites, followed in abundance by the magnesium/iron oxide ferropericlase. Examples of silicate minerals in the crust include those in the pyroxene, amphibole, mica, and feldspar groups. These minerals occur in clay and various types of rock such as granite and sandstone. Silica occurs in minerals consisting of very pure silicon dioxide in different crystalline forms, quartz, agate amethyst, rock crystal, chalcedony, flint, jasper, andopal. The crystals have the

empirical formula of silicon dioxide, but do not consist of separate silicon dioxide molecules in the manner of solid carbon dioxide. Rather, silica is structurally a network-solid consisting of silicon and oxygen in three-dimensional crystals, like diamond. Less pure silica forms the natural glassobsidian. Biogenic silica occurs in the structure of diatoms, radiolaria and siliceous sponges. Silicon is also a principal component of many meteorites, and is a component of tektites, a silicate mineral of possibly lunar origin, or (if Earth-derived) which has been subjected to unusual temperatures and pressures, possibly from meteorite strike.
COMPOUNDS

Silicon forms binary compounds called silicides with many metallic elements whose properties range from reactive compounds, e.g. magnesium silicide, Mg2Si through high melting refractory compounds such as molybdenum disilicide, MoSi2. Silicon carbide, SiC (carborundum) is a hard, high melting solid and a well known abrasive. It may also be sintered into a type of high-strength ceramic used in armor. Silane, SiH4, is a pyrophoric gas with a similar tetrahedral structure to methane, CH4. When pure, it does not react with pure water or dilute acids; however, even small amounts of alkali impurities from the laboratory glass can result in a rapid hydrolysis. There is a range of catenated silicon hydrides that form a homologous series of compounds, SinH2n+2 where n = 28 (analogous to the alkanes). These are all readily hydrolyzed and are thermally unstable, particularly the heavier members. Disilenes contain a silicon-silicon double bond (analogous to the alkenes) and are generally highly reactive requiring large substituent groups to stabilize them. Adisilyne with a silicon-silicon triple bond was first isolated in 2004; although as the compound is non-linear, the bonding is dissimilar to that in alkynes. Tetrahalides, SiX4, are formed with all the halogens. Silicon tetrachloride, for example, reacts with water, unlike its carbon analogue, carbon tetrachloride. Silicon dihalides are formed by the high temperature reaction of tetrahalides and silicon; with a structure analogous to a carbene they are reactive compounds. Silicon difluoride condenses to form a polymeric compound, (SiF2)n. Silicon dioxide is a high melting solid with a number of crystal forms; the most familiar of which is the mineral quartz. In quartz each silicon atom is surrounded by four oxygen atoms that bridge to other silicon atoms to form a three dimensional lattice. Silica is soluble in water at high temperatures forming a range of compounds called monosilicic acid, Si(OH)4. Under the right conditions monosilicic acid readily polymerizes to form more complex silicic acids, ranging from the simplest condensate, disilicic acid (H6Si2O7) to linear, ribbon, layer and lattice structures which form the basis of the many silicate minerals and are called polysilicic acids {Six(OH)42x}n. With oxides of other elements the high temperature reaction of silicon dioxide can give a wide range of glasses with various properties. Examples include soda lime glass, borosilicate glass and lead crystal glass. Silicon sulfide, SiS2, is a polymeric solid (unlike its carbon analogue the liquid CS2). Silicon forms a nitride, Si3N4 which is a ceramic. Silatranes, a group of tricyclic compounds containing five-coordinate silicon, may have physiological properties.

Many transition metal complexes containing a metal-silicon bond are now known, which include complexes containing SiHnX3n ligands, SiX3 ligands, and Si(OR)3 ligands. Silicones are large group of polymeric compounds with an (Si-O-Si) backbone. An example is the silicone oil PDMS (polydimethylsiloxane). These polymers can be crosslinked to produce resins andelastomers. Many organosilicon compounds are known which contain a silicon-carbon single bond. Many of these are based on a central tetrahedral silicon atom, and some are optically active when central chiralityexists. Long chain polymers containing a silicon backbone are known, such as polydimethysilylene (SiMe2)n. Polycarbosilane, [(SiMe2)2CH2]n with a backbone containing a repeating -Si-Si-C unit, is a precursor in the production of silicon carbide fibers.

HISTORY

Attention was first drawn to silica as the possible oxide of a fundamental chemical element by Antoine Lavoisier, in 1787. After an attempt to isolate silicon in 1808, Sir Humphry Davy proposed the name "silicium" for silicon, from the Latin silex, silicis for flint, flints, and adding the "-ium" ending because he believed it was a metal. In 1811, Gay-Lussac and Thnard are thought to have prepared impureamorphous silicon, through the heating of recently isolated potassium metal with silicon tetrafluoride, but they did not purify and characterize the product, nor identify it as a new element. Silicon was given its present name in 1817 by Scottish chemist Thomas Thomson. He retained part of Davy's name but added "-on" because he believed that silicon was a nonmetal similar to boron and carbon. In 1823,Berzelius prepared amorphous silicon using approximately the same method as Gay-Lussac (potassium metal and potassium fluorosilicate), but purifying the product to a brown powder by repeatedly washing it. As a result he is usually given credit for the element's discovery. Silicon in its more common crystalline form was not prepared until 31 years later, by Deville. By electrolyzing impure sodium-aluminum chloride containing approximately 10% silicon, he was able to obtain a slightly impure allotrope of silicon in 1854. Later, more cost-effective methods have been developed to isolate silicon in several allotrope forms, the most recent being silicene. Because silicon is an important element in semiconductors and high-technology devices, many places in the world bear its name. For example, Silicon Valley in California, since it is the base for a number of technology-related industries, bears the name silicon. Other geographic locations with connections to the industry have since been named after silicon as well. Examples include Silicon Forest in Oregon,Silicon Hills in Austin, Texas, Silicon Saxony in Germany, Silicon Valley in India, Silicon Border in Mexicali, Mexico, Silicon Fen in Cambridge, England, Silicon Roundabout in London, Silicon Glen inScotland, and Silicon Gorge in Bristol, England.
APPLICATIONS

Compounds

Most silicon is used industrially without being separated into the element, and indeed often with comparatively little processing from natural occurrence. Over 90% of the Earth's crust is composed of silicate minerals. Many of these have direct commercial uses, such as clays, silica sand and most kinds of building stone. Thus, the vast majority of uses for silicon are as structural compounds, either as the

silicate minerals or silica (crude silicon dioxide). For example, silica is an important part of ceramic brick. Silicates are used in making Portland cement which is used in building mortar and stucco, but more importantly combined with silica sand, and gravel (usually containing silicate minerals like granite), to make the concrete that is the basis of most of the very largest industrial building projects of the modern world. Silicate minerals are also in whiteware ceramics, an important class of products usually containing various types of fired clay (natural aluminum silicate). An example is porcelain which is based on silicate mineral kaolinite. Ceramics include art objects, and domestic, industrial and building products. Traditional quartz-based soda-lime glass also functions in many of the same roles. More modern silicon compounds also function as high-technology abrasives and new high-strength ceramics based upon (silicon carbide), and in superalloys. Alternating silicon-oxygen chains with hydrogen attached to the remaining silicon bonds form the ubiquitous silicon-based polymeric materials known as silicones. These compounds containing siliconoxygen and occasionally silicon-carbon bonds have the capability to act as bonding intermediates between glass and organic compounds, and to form polymers with useful properties such as impermeability to water, flexibility and resistance to chemical attack. Silicones are often used in waterproofing treatments, molding compounds, mold-release agents, mechanical seals, high temperature greases and waxes, andcaulking compounds. Silicone is also sometimes used in breast implants, contact lenses, explosives and pyrotechnics. Silly Putty was originally made by adding boric acid to silicone oil.
Alloys

Elemental silicon is added to molten cast iron as ferrosilicon or silicocalcium alloys to improve performance in casting thin sections and to prevent the formation of cementite where exposed to outside air. The presence of elemental silicon in molten iron acts as a sink for oxygen, so that the steel carbon content, which must be kept within narrow limits for each type of steel, can be more closely controlled. Ferrosilicon production and use is a monitor of the steel industry, and although this form of elemental silicon is impure, it accounts for 80% of the world's use of free silicon. The properties of silicon itself can be used to modify alloys. Silicon's importance in aluminum casting is that a significantly high amount (12%) of silicon in aluminum forms a eutectic mixture which solidifies with very little thermal contraction. This greatly reduces tearing and cracks formed from stress as casting alloys cool to solidity. Silicon also significantly improves the hardness and thus wear-resistance of aluminum. Silicon is an important constituent of electrical steel, modifying its resistivity and ferromagnetic properties. Metallurgical grade silicon is silicon of 9599% purity. About 55% of the world consumption of metallurgical purity silicon goes for production of aluminum-silicon alloys for aluminum part casts, mainly for use in the automotive industry. The reason for the high silicon use in these alloys is noted above. Much of the rest of metallurgical-grade silicon is used by the chemical industry for production of the important industrial product fumed silica. The remainder is used in production of other fine chemicals such as silanes and some types of silicones.
Electronics

Since most elemental silicon produced remains as ferrosilicon alloy, only a relatively small amount (20%) of the elemental silicon produced is refined to metallurgical grade purity (a total of 1.31.5 million metric tons/year). The fraction of silicon metal which is further refined to semiconductor purity is estimated at only 15% of the world production of metallurgical grade silicon. However, the economic importance of this small very high-purity fraction (especially the ~ 5% which is processed to monocrystalline silicon for use in integrated circuits) is disproportionately large. Pure monocrystalline silicon is used to produce silicon wafers used in the semiconductor industry, in electronics and in some high-cost and high-efficiency photovoltaicapplications. In terms of charge conduction, pure silicon is an intrinsic semiconductor which means that unlike metals it conducts electron holes and electrons that may be released from atoms within the crystal by heat, and thus increase silicon's electrical conductivity with higher temperatures. Pure silicon has too low a conductivity (i.e., too high a resistivity) to be used as a circuit element in electronics. In practice, pure silicon is doped with small concentrations of certain other elements, a process that greatly increases its conductivity and adjusts its electrical response by controlling the number and charge (positive or negative) of activated carriers. Such control is necessary fortransistors, solar cells, semiconductor detectors and other semiconductor devices, which are used in the computer industry and other technical applications. For example, insilicon photonics, silicon can be used as a continuous wave Raman laser medium to produce coherent light, though it is ineffective as an everyday light source. In common integrated circuits, a wafer of monocrystalline silicon serves as a mechanical support for the circuits, which are created by doping, and insulated from each other by thin layers of silicon oxide, an insulator that is easily produced by exposing the element to oxygen under the proper conditions. Silicon has become the most popular material to build both high power semiconductors and integrated circuits. The reason is that silicon is the semiconductor that can withstand the highest temperatures and electrical powers without becoming dysfunctional due to avalanche breakdown (a process in which an electron avalanche is created by a chain reaction process whereby heat produces free electrons and holes, which in turn produce more current which produces more heat). In addition, the insulating oxide of silicon is not soluble in water, which gives it an advantage over germanium (an element with similar properties which can also be used in semiconductor devices) in certain type of fabrication techniques. Monocrystalline silicon is expensive to produce, and is usually only justified in production of integrated circuits, where tiny crystal imperfections can interfere with tiny circuit paths. For other uses, other types of pure silicon which do not exist as single crystals may be employed. These include hydrogenated amorphous silicon and upgraded metallurgical-grade silicon (UMG-Si) which are used in the production of low-cost, large-area electronics in applications such as liquid crystal displays, and of large-area, low-cost, thin-film solar cells. Such semiconductor grades of silicon which are either slightly less pure than those used in integrated circuits, or which are produced in polycrystalline rather than monocrystalline form, make up roughly similar amount of silicon as are produced for the monocrystalline silicon semiconductor industry, or 75,000 to 150,000 metric tons per year. However, production of such materials is growing more quickly than silicon for the integrated circuit market. By 2013 polycrystalline silicon production, used mostly in solar cells, is projected to reach 200,000 metric tons per year, while monocrystalline semiconductor silicon production (used in computer microchips) remains below 50,000 tons/year.
BIOLOGICAL ROLE

Although silicon is readily available in the form of silicates, very few organisms have a use for it. Diatoms, radiolaria and siliceous sponges use biogenic silica as a structural material to construct skeletons. In more advanced plants, the silica phytoliths (opal phytoliths) are rigid microscopic bodies occurring in the cell; some plants, for example rice, need silicon for their growth. Although silicon was proposed to be an ultra trace nutrient, its exact function in the biology of animals is still under discussion. Higher organisms are only known to use it in very limited occasions in the form of silicic acid and soluble silicates. Silicon is known to be needed for synthesis of elastin and collagen; the aorta contains the highest quantity of elastin and silicon. Silicon is currently under consideration for elevation to the status of a "plant beneficial substance by the Association of American Plant Food Control Officials (AAPFCO)." Silicon has been shown in university and field studies to improve plant cell wall strength and structural integrity, improve drought and frost resistance, decrease lodging potential and boost the plant's natural pest and disease fighting systems. Silicon has also been shown to improve plant vigor and physiology by improving root mass and density, and increasing above ground plant biomass and crop yields. Hypothetical silicon-based lifeforms are the subject of silicon biochemistry, by analogy with carbon-based lifeforms. Silicon, being below carbon in the periodic table, is thought to have similar enough properties that would make silicon-based life possible, but much different from life as we know it.