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 stable nuclides. Because of its relative 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 deuteride serves as a fusion fuel in staged thermonuclear weapons.
Trace amounts of lithium are present in the oceans and in all organisms. The element serves no apparent vital biological function, since animal and plants survive in good health without it. Nonvital 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 due to neurological effects of the ion in the human body. 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.
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 point of the alkali metals.
It is the lightest metal in the periodic table, so light that it can float on water and even on oil, and it is one of two metals that can. It has a very low density, of approximately 0.534 g/cm3, which gives sticks of the metal a similar heft to dowels of a medium density wood, such as pine. It floats on water but also reacts with it. thumb|left|150px|Lithium floating in oilIt is the least dense of all elements that are not gasses at room temperature. The next lightest element is over 60% more dense (potassium, at 0.862 g/cm3). Furthermore, aside from helium and hydrogen, it is the least dense element in a solid or liquid state, being only 2/3 as dense as liquid nitrogen (0.808 g/cm3).
Lithium's coefficient of thermal expansion is twice that of aluminum and almost four times that of iron. It has the highest specific heat capacity of any solid element. Lithium is superconductive below 400 μK 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.
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 is inflammable, and it is potentially explosive when exposed to air and especially to water, though less so than the other alkali metals. The lithium-water reaction at normal temperatures is brisk but not violent, 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 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 () and peroxide () when burnt in O2, salts with similar solubilities, and thermal instability of the carbonates and 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 (), the superoxide (), carbide (). Many other inorganic compounds are known, where lithium combines with anions to form various salts: borates, amides, carbonate, nitrate, or borohydride (). Multiple organolithium reagents are known where there is a direct bond between carbon and lithium atoms effectively creating a carbanion that 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.
7Li is one of the primordial elements (or, more properly, primordial nuclides) produced in Big Bang nucleosynthesis. A small amount of both 6Li and 7Li are produced in stars, but are thought to be burned as fast as produced. Additional small amounts of lithium of both 6Li and 7Li may be generated from solar wind, cosmic rays hitting heavier atoms, and from early solar system 7Be and 10Be radioactive decay. While lithium is created in stars during the Stellar nucleosynthesis, it is further burnt. 7Li 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 for magnesium and iron in octahedral sites in clay minerals, where 6Li is preferred to 7Li, resulting in enrichment of the light isotope in processes of hyperfiltration and rock alteration. The exotic 11Li is known to exhibit a nuclear halo. The process known as laser isotope separation can be used to separate lithium isotopes.
Though it was one of the three first elements (together with helium and hydrogen) to be synthesized in the Big Bang, lithium, together with beryllium 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 stars and certain anomalous orange stars. Because lithium is present in cooler, less-massive brown dwarf stars, 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 objects—neutron stars or black holes—whose gravity evidently pulls heavier lithium to the surface of a hydrogen-helium star, causing more lithium to be observed.
Estimates for crustal content range from 20 to 70 ppm by weight. In keeping with its name, lithium forms a minor part of igneous 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. 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. Nickel and lead have about the same abundance.
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 a few of them are of actual or potential commercial value. Many are very small, others are too low in grade."
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 2009 Chile had the largest reserves by far (7.5 million tonnes) and the highest annual production (7,400 tonnes). Other major suppliers include Australia, Argentina and China. Other estimates put Argentina's reserve base (7.52 million tonnes) above that of Chile (6 million).
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 of 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 1979–1989" 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."
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 Sir Humphry 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 became high temperature grease for aircraft engines or similar applications in World War II and shortly after. This small market 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%.
Lithium was used to decrease the melting temperature of glass and to improve the melting behavior of aluminium oxide when using the Hall-Héroult 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 near Kings Mountain, North Carolina closed before the turn of the 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 to 2000s, new companies have expanded brine extraction efforts to meet the rising demand.
There are widespread hopes of using lithium ion batteries in electric vehicles, but one 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'".
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 is 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. China may emerge as a significant producer of brine-source lithium carbonate around 2010. There is potential production of up to 55,000 tonnes per year if projects in Qinghai province and Tibet proceed.
Worldwide reserves of lithium are estimated to be 23 million tonnes. Using the battery efficiency figure of 400 g of lithium per kWh, this gives a total maximum lithium battery capacity of 52 billion kWh which, assuming it is used exclusively for car batteries, is enough for approximately 2 billion cars with a 24 kWh battery (like a Nissan Leaf ).
Metallic lithium and its complex hydrides, such a Li[AlH4], are used as high energy additives to rocket propellants.
Lithium hydroxide and lithium peroxide are the salts most used in confined areas, such as aboard spacecraft and submarines, for carbon dioxide removal and air purification. Lithium hydroxide absorbs carbon dioxide from the air by reacting with it to form lithium carbonate, and is preferred over other alkaline hydroxides for its low weight. Lithium peroxide (Li2O2) in presence of moisture not only absorbs carbon dioxide to form lithium carbonate, but also releases oxygen. For example: :2 Li2O2 + 2 CO2 → 2 Li2CO3 + O2.
The high non-linearity of lithium niobate also makes it useful in non-linear optics applications. It is used extensively in telecommunication products such as mobile phones and optical modulators, for such components as resonant crystals. Lithium applications are used in more than 60% of mobile phones.
The Mark 50 Torpedo stored chemical energy propulsion system (SCEPS) uses a small tank of sulfur hexafluoride gas which is sprayed over a block of solid lithium. The reaction generates enormous heat which is used to generate steam from seawater. The steam propels the torpedo in a closed Rankine cycle.
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 and manganese are used to make high-performance aircraft parts (see also Lithium-aluminium alloys). Lithium compounds are also used as pyrotechnic colorants and oxidizers in red fireworks and flares.
Lithium metal is also used in the pharmaceutical and fine-chemical industry in the manufacture of organolithium reagents, which are used both as strong bases and as reagents for the formation of carbon-carbon bonds. Organolithium compounds are also used in polymer synthesis as catalysts/initiators in anionic polymerization of unfunctionalized olefins. Lithium is used in the preparation of organolithium compounds, which are in turn very reactive and are the basis of many synthetic applications.
Lithium deuteride was the fusion fuel of choice in early versions of the hydrogen bomb. When bombarded by neutrons, both 6Li and 7Li produce tritium—this reaction, which was not fully understood when hydrogen bombs were first tested, was responsible for the runaway yield of the Castle Bravo nuclear test. Tritium fuses with deuterium in a fusion reaction that is relatively easy to achieve. Although details remain secret, lithium-6 deuteride still apparently plays a role in modern nuclear weapons, as a fusion material.
Lithium fluoride as highly enriched in the lithium-7 isotope forms the basic constituent of the fluoride salt mixture LiF-BeF2 that used in liquid-fluoride nuclear reactors. Lithium fluoride is exceptionally chemically stable and LiF-BeF2 mixtures have low melting points. In addition, 7Li, Be, and F are among the few nuclides with low enough thermal neutron capture cross-sections to not poison the fission reactions inside a nuclear fission reactor.
In conceptualized nuclear fusion power plants, lithium will be used to produce tritium in magnetically confined reactors using deuterium and tritium as the fuel. Tritium does not occur naturally and will be produced by surrounding the reacting plasma with a 'blanket' containing lithium where neutrons from the deuterium-tritium reaction in the plasma will react with the lithium to produce more tritium: :6Li + n → 4He + 3T.
Lithium is also used as a source for alpha particles, or helium nuclei. When 7Li is bombarded by accelerated protons 8Be is formed, which undergoes fission to form two alpha particles. This feat, called "splitting the atom" at the time, was the first fully man-made nuclear reaction. It was produced by Cockroft and Walton in 1932. (Nuclear reactions and human-directed nuclear transmutation had been accomplished as early as 1917, but by using natural radioactive bombardment with alpha particles).
There have been suggestions of increased risk of developing Ebstein's cardiac anomaly in infants born to women taking lithium during the first trimester of pregnancy.
Category:Alkali metals Category:Chemical elements Category:Reducing agents
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