performed the: .
2.3 Lithium compounds
3 History and etymology
6.1 Medical use
6.2 Other uses
(pronounced /ˈlɪθiəm/, LITH-ee-əm) is a
soft, silver-white metal that belongs to the alkali metal group of chemical
elements. It is represented by the symbol Li, and it has the atomic number
three. Under standard conditions it is the lightest metal and the least dense
solid element. Like all alkali metals, lithium is highly reactive, corroding
quickly in moist air to form a black tarnish. For this reason, lithium metal is
typically stored under the cover of petroleum. When cut open, lithium exhibits
a metallic luster, but contact with oxygen quickly turns it back to a dull
silvery gray color. Lithium in its elemental state is highly flammable.
theory, lithium was one of the few elements synthesized in the Big Bang. Since
its current estimated abundance in the universe is vastly less than that
predicted by physical theories, the processes by which new lithium is created
and destroyed, and the true value of its abundance, continue to be active
matters of study in astronomy. The nuclei of lithium are relatively
fragile: the two stable lithium isotopes found in nature have lower binding
energies per nucleon than any other stable compound nuclides, save deuterium,
and helium-3 (3He). Though very light in atomic weight, lithium is less
common in the solar system than 25 of the first 32 chemical elements.
Due to its
high reactivity it only appears naturally in the form of compounds. Lithium
occurs in a number of pegmatitic minerals, but is also commonly obtained from
brines and clays. On a commercial scale, lithium metal is isolated
electrolytically from a mixture of lithium chloride and potassium chloride.
of lithium are present in the oceans and in some organisms, though the element
serves no apparent vital biological function in humans, though 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, and lithium batteries. Lithium also has important links to
nuclear physics. The transmutation of lithium atoms to tritium was the first
man-made form of a nuclear fusion reaction, and lithium deuteride serves as a
fusion fuel in staged thermonuclear weapons.
Silvery white (seen here in oil)
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 both heat and
electricity and highly reactive, though it is the least reactive of the alkali
metals due to the proximity of its valence electron to its nucleus.
soft enough to be cut with a knife, and it is the lightest of the metals of the
periodic table. When cut, it possesses a silvery-white color that quickly
changes to gray due to oxidation. It also has a low density (approximately
0.534 g/cm3) and thus will float on water, with which it reacts easily. This
reaction is energetic, forming hydrogen gas and lithium hydroxide in aqueous
solution. Due to its reactivity with water, lithium is usually stored in
mineral oil or kerosene.
possesses a low coefficient of thermal expansion and 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 kelvin) at very
high pressures (over 200,000 atmospheres) At cryogenic temperatures,
lithium, like sodium, undergoes diffusionless phase change transformations. At
4.2K 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.
Lithium pellets (covered in white lithium hydroxide)
In moist air,
lithium metal rapidly tarnishes to form a black coating of lithium hydroxide
(LiOH and LiOH·H2O), lithium nitride (Li3N) and lithium carbonate (Li2CO3, the
result of a secondary reaction between LiOH and CO2).
over a flame, lithium gives off a striking crimson color, but when it burns
strongly the flame becomes a brilliant white. Lithium will ignite and burn in
oxygen when exposed to water or water vapours.
is flammable, 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, though
the hydrogen produced can ignite. 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 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 when burnt in O2, salts
with similar solubilities, and thermal instability of the carbonates and
occurring lithium is composed of two stable isotopes, 6Li and 7Li, 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.
Seven radioisotopes have been characterized, the most stable being 8Li with a
half-life of 838 ms and 9Li with a half-life of 178.3 ms. All of the remaining
radioactive isotopes have half-lives that are shorter than 8.6 ms. The
shortest-lived isotope of lithium is 4Li, which decays through proton emission
and has a half-life of 7.58043x10−23 s.
7Li is one of
the primordial elements (or, more properly, primordial isotopes) 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 it is produced. Additional
small amounts of lithium of both 6Li and 7Li may be generated from solar wind,
cosmic rays, and early solar system 7Be and 10Be radioactive decay. 7Li can
also be generated in carbon stars.
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.
3. History and etymology
(LiAlSi4O10, which is lithium aluminium silicate) was first discovered in 1800
by the Brazilian chemist José Bonifácio de Andrade e Silva, who
discovered this mineral in a mine on the island of Utö,
Sweden. However, it was not until 1817 that Johan August Arfwedson,
then working in the laboratory of the chemist Jöns 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 carbonate and hydroxide were less soluble in water and
more alkaline. Berzelius gave the alkaline material the name
"lithos", from the Greek word λιθoς
(transliterated as lithos, meaning "stone"), to reflect its discovery
in a solid mineral, as opposed to sodium and potassium, which had been
discovered in plant tissues. The name of this element was later standardized as
"lithium". Arfwedson later showed that this same element
was present in the minerals spodumene and lepidolite. In 1818, Christian
Gmelin was the first man to observe that lithium salts give a bright red color
in flame. However, both Arfwedson and Gmelin tried and failed to isolate
the element from its salts. This element, lithium, was not isolated
until 1821, when William Thomas Brande isolated the element by performing
electrolysis on lithium oxide, a process that had previously 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 he performed an estimate of its atomic weight. 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 metal, beginning in 1923 by
the German company Metallgesellschaft AG, which performed an electrolysis of a
liquid mixture of lithium chloride and potassium chloride.
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 when in the beginning of the
cold war the need for the production of nuclear fusion weapons arose and the
dominant fusion material tritium had to be made by irradiating lithium-6. 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 tons of
lithium hydroxide. The stockpiled lithium was depleted in lithium-6 by 75%
used to decrease the melting temperature of glass and to improve the melting
behavior of aluminium chloride when using the Hall-Héroult
process. These two uses dominated the market until the middle of the
1990's. 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. Then, in the mid 1990's several companies started to extract
lithium from brine; this method proved to be less expensive 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. New
companies have expanded brine extraction efforts to meet the rising demand.
theory, the stable isotopes 6Li and 7Li were created in the Big Bang, but the
amounts are unclear. Lithium is a fusion fuel in main sequence stars. Because
of the method by which elements are built up by fusion in stars, there is a
general trend in the cosmos that the lighter elements are more common. However,
lithium (element number 3) is tied with krypton as the 32nd/33rd most abundant
element in the cosmos (see Cosmochemical Periodic Table of the Elements in the
Solar System), being less common than any element between carbon (element 6)
and scandium (element 21). It is not until atomic number 36 (krypton) and
beyond that chemical elements are found to be universally less common in the
cosmos than lithium. The reasons have to do with the failure of any good
mechanisms to synthesize lithium in the fusion reactions between nuclides in
supernovae. Due to the absence of any quasi-stable nuclide with five nucleons,
nuclei of lithium-5 produced from helium and a proton has no time to fuse with
a second proton or neutron to form a six nucleon isotope which might decay to
lithium-6, even under extreme conditions of bombardment. Also, the product of
helium-helium fusion (berylium-8) is immediately unstable toward disintegration
to helium again, and is thus not available for formation of lithium. Some
lithium-7 is formed in the pp III branch of the proton-proton chain in main
sequence and red giant stars, but it is normally consumed by lithium burning as
fast as it is formed. This leaves new formation of the stable isotopes lithium
6 and 7 to rare cosmic ray spallation on carbon or other elements in cosmic
dust. Meanwhile, existing Li-6 and Li-7 is destroyed in many nuclear reactions
in supernovae and by lithium burning in main sequence stars, resulting in net
removal of lithium from the cosmos. In turn the destruction of lithium isotopes
is due to their very low energy of binding per nucleon with regard to all other
nuclides save deuterium (also destroyed in stars) and helium-3. This low
energy of binding encourages breakup of lithium in favor of more tightly-bound
nuclides under thermonuclear reaction conditions.
widely distributed on Earth but does not naturally occur in elemental form due
to its high reactivity. 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.
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." At 20 mg lithium per kg of Earth's crust , lithium is the
25th most abundant element. Nickel and lead have the about the same abundance.
reserve base of lithium is in the Salar de Uyuni area of Bolivia, which has 5.4 million tons. According to the US Geological Survey, the production and
reserves of lithium in metric tons are as follows:
the USGS data in the table, other estimates put Chile's reserve base at
7,520,000 metric tons of lithium, and Argentina's at 6,000,000 metric tons. Seawater contains an estimated 230
billion tons of lithium, though at a low concentration of 0.1 to 0.2 ppm.
Lithium is about as common as chlorine in the Earth's upper continental crust,
on a per-atom basis.
Since the end
of World War II lithium metal 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
The metal is
produced electrolytically from a mixture of fused lithium and potassium
chloride. In 1998 it was about US$ 43 per pound ($95 per kg).
lithium are found in South America throughout the Andes mountain chain. Chile is the leading lithium metal producer, followed by Argentina. Both countries recover the
lithium from brine pools. In the United States lithium is recovered from brine
pools in Nevada. Nearly 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 even Korean firms to begin
extraction. According to the US Geological Survey, Bolivia's Uyuni Desert
has 5.4 million tons of lithium, which can be used to make batteries for hybrid
and electric vehicles.
China may emerge as a
significant producer of brine-source lithium carbonate around 2010. There is
potential production of up to 55,000 tons per year if projects in Qinghai province and Tibet proceed.
amount of lithium recoverable from global reserves has been estimated at 35
million tonnes, which includes 15 million tons of the known global lithium
In 1976 a National Research Council Panel estimated lithium resources at 10.6 million tons for the
Western World. With the inclusion of Russian and Chinese resources as well
as new discoveries in Australia, Serbia, Argentina and the United States, the
total had nearly tripled by 2008.
Lithium mine, Salar del Hombre Muerto, Argentina. The brine in this salar is
rich in lithium, and the mine concentrates the brine by pumping it into solar
evaporation ponds. 2009 image from NASA’s EO-1 satellite.
Salar de Uyuni, Bolivia.
Because of its
specific heat capacity, the highest of all solids, lithium is often used in
heat transfer applications.
In the latter
years of the 20th century lithium became important as an anode material. Used
in lithium-ion batteries because of its high electrochemical potential, a
typical cell can generate approximately 3 volts, compared with 1.5 volts for
lead/acid or zinc cells. Because of its low atomic mass, it also has a high charge-
and power-to-weight ratio.
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. Organolithiums are also used in
polymer synthesis as catalysts/initiators in anionic polymerisation of
were used during the 19th century to treat gout. Lithium salts such as lithium
carbonate (Li2CO3), lithium citrate, and lithium orotate are mood stabilizers.
They are used in the treatment of bipolar disorder since, unlike most other
mood altering drugs, they counteract both mania and depression. Lithium can
also be used to augment antidepressants. Because of Lithium's nephrogenic
diabetes insipidus effects, it can be used to help treat the syndrome of
inappropriate antidiuretic hormone hypersecretion (SIADH). It was also
sometimes prescribed as a preventive treatment for migraine disease and cluster
principle in these salts is the lithium ion Li+. Although this ion has a
smaller diameter than either Na+ or K+, in a watery environment like the
cytoplasmic fluid, Li+ binds to the hydrogen atoms of water, making it effectively
larger than either Na+ or K+ ions. How Li+ works in the central nervous system
is still a matter of debate. Li+ elevates brain levels of tryptophan, 5-HT
(serotonin), and 5-HIAA (a serotonin metabolite). Serotonin is related to mood
stability. Li+ also reduces catecholamine activity in the brain (associated
with brain activation and mania), by enhancing reuptake and reducing release.
Therapeutically useful amounts of lithium (~ 0.6 to 1.2 mmol/l) are only
slightly lower than toxic amounts (>1.5 mmol/l), so the blood levels of
lithium must be carefully monitored during treatment to avoid toxicity.
effects of lithium treatment include muscle tremors, twitching, ataxia and
hypothyroidism. Long term use is linked to hyperparathyroidism,
hypercalcemia (bone loss), hypertension, kidney damage, nephrogenic diabetes
insipidus (polyuria and polydipsia), seizures and weight gain. Some of
the side-effects are a result of the increased elimination of potassium.
to be an increased risk of Ebstein (cardiac) Anomaly in infants born to women
taking lithium during the first trimester of pregnancy.
According to a
study in 2009 at Oita University in Japan and published in the British Journal
of Psychiatry, communities whose water contained larger amounts of lithium had
significantly lower suicide rates but did not address whether
lithium in drinking water causes the negative side effects associated with
higher doses of the element.
batteries are disposable (primary) batteries with lithium metal or lithium
compounds as an anode. Lithium batteries are not to be confused with
lithium-ion batteries, which are high energy-density rechargeable batteries.
Other rechargeable batteries include the Lithium-ion polymer battery, Lithium
iron phosphate battery, and the Nanowire battery. New technologies are
constantly being announced.
niobate 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.
chloride and lithium bromide are extremely hygroscopic and are used as
is used in the preparation of organo-lithium compounds.
stearate is a common all-purpose, high-temperature lubricant.
When used as a
flux for welding or soldering, lithium promotes the fusing of metals during 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).
sometimes used in focal lenses, including spectacles and the glass for the
200-inch (5.08 m) telescope at Mt. Palomar.
non-linearity of lithium niobate also makes it useful in non-linear optics
fluoride, artificially grown as crystal, is clear and transparent and often
used in specialist optics for IR, UV and VUV (vacuum UV) applications. It has
the lowest refractive index and the farthest transmission range in the deep UV
of all common materials.
lithium and its complex hydrides, such a Li[AlH4], are used as high energy
additives to rocket propellants.
peroxide, lithium nitrate, lithium chlorate and lithium perchlorate are used as
oxidizers in rocket propellants, and also in oxygen candles that supply
submarines and space capsules with oxygen.
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.
fluoride (highly enriched in the common isotope lithium-7) forms the basic
constituent of the preferred fluoride salt mixture (LiF-BeF2) used in
liquid-fluoride nuclear reactors. Lithium fluoride is exceptionally chemically
stable and LiF/BeF2 mixtures have low melting points and the best neutronic
properties of fluoride salt combinations appropriate for reactor
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 + 3H. Various means of doing this will be
tested at the ITER reactor being built at Cadarache, France.
used as a source for alpha particles, or helium nuclei. When 7Li is bombarded
by accelerated protons 8Be is formed, which undergoes spontaneous fission to
form two alpha particles. This was the first man-made nuclear reaction,
produced by Cockroft and Walton in 1929.
hydroxide (LiOH) is an important compound of lithium obtained from lithium
carbonate (Li2CO3). It is a strong base, and when heated with a fat it produces
a lithium soap. Lithium soap has the ability to thicken oils, and it is used to
manufacture lubricating greases.
hydroxide and lithium peroxide are used in confined areas, such as aboard
spacecraft and submarines, for 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.
compounds are used in red fireworks and flares.
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.
Figure. 5. The
red lithium flame leads to lithium's use in flares and pyrotechnics
Due to its
alkaline tarnish, lithium metal 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.
Lithium ingots with a thin layer of black oxide tarnish
jurisdictions limit the sale of lithium batteries, which are the most readily
available source of lithium metal for ordinary consumers. Lithium can be used
to reduce pseudoephedrine and ephedrine to methamphetamine in the Birch
reduction method, which employs solutions of alkali metals dissolved in
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 when
short-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.
individual representative of the periodic table of chemical elements Dmitry
Ivanovich Mendeleyev, the element has unique chemical and physical properties
Element is of
great economic importance and plays a major role in world culture
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