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Peter Rieckeheer Lithium
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Transcript of Peter Rieckeheer Lithium
TOUR TO THE LITHIUM BRINE`S IN SOUTH AMERICA
E-mail [email protected]
Dedicado a mis amigos de toda la
vida y familiares.
Recuerdo del Viaje a los Salares de
Litio.
Momentos alucinantes, en un País
de imponente geografía y recursos
naturales ilimitados.
Industrial Engineer Peter Rieckeheer
The Andes Mountain Area
South America along the Pacific
7.500 Km. from Colombia to Cape Horn
Lithium
An overview
Appearance silvery white (seen here in oil)
Lithium 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 3.
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 cluster , but contact with
oxygen quickly turns it back to a dull silvery gray color. Lithium in its elemental state
is highly flammable. ~
Lithium - According to one cosmogenic theory, lithium was one of the few
elements synthesized in the Big Bang, albeit in relatively small quantities. 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 astrono-
my. 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.
Because of its high reactivity , lithium only appears naturally in the form of com-
pounds. 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 elec-
trolytically from a mixture of lithium chloride and potassium chloride. Trace amounts
of lithium are present in the oceans and in some organisms, though the element
serves no apparent vital biological function in humans. The lithium ion Li+ adminis-
tered 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 c eramics, high
strength-to-weight alloys used in aircraft, and lithium batteries. Lithium also has im-
portant 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.
Trace amounts of lithium are present in the oceans and in some organisms,
though the element serves no apparent vital biological function in humans. 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.
Physical Characteristics
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. Lithium
is 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, with3 Lithium pellets (covered in white lithium
hydroxide) which it reacts easily.
This reaction is energetic, forming hydrogen gas and lithium hydroxide in
aqueous solution. Because of its reactivity with water, lithium is usually stored
under cover of a dense hydrocarbon, often petroleum jelly; though the heavier
alkaline metals can be stored in less dense substances, such as mineral oil,
lithium is not dense enough to be fully submerged in these liquids.
Lithium possesses a low coefficient of thermal expansion and thehighest specific
heat capacity of any solid element. Lithium is superconductive below 400 °K 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 diffusion less 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.
Lithium
Chemical
In moist air, lithium meta l 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).When placed
over a flame, lithium gives 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 vapours. Lithium metal is flammable, and it is
potentially explosive when exposed to air and especially to water, though lessso
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 dificult to extingish requiring dry power fire
extinguishers , specifically class D type ( see Types of extinguishing agents ).
Lithium is the only metal which reacts with nitrogen under normal conditions.
Periodic Elements Table
Lithium compounds
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 carbona-
tes and nitrides.
Isotopes
Naturally 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 there main
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 7.58043 × 10?23 s.
7Li is one of the primordia l elements (or more properly, primordial isotopes)
produced in Big Bang nucleosynthesis . A small amount of both 6L i and 7Li are
produced in stars, but are thought to be burned as fast as it is produced. Additio-
nal 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.
Lithium isotopes fractionate substantially during a wide variety of natural proces-
ses, including mineral formation (chemical precipitation), metabolism, and ion
exchange.
Lithium ions substitute for magnesium and iron inoctahedral sites in clay mine-
rals , where 6Li is preferred to 7Li, resulting in enrichment of the light isotope
in processes of hyper filtration and rock alteration. The exotic 11 Li is known to
exhibit a nuclear halo.
History and Etymology
Petalite (LiAlSi4O10, which is lithium aluminium silicate) was first discovered in
1800 by the Brazilian chemist José Bonifacio 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 solublein water and more alkaline. Berzelius gave the alkaline material
the name "lithos", from the Greek word Litho (transliterated as lithos, meaning
"stone"), to reflect its discovery in a solid mineral, as opposed to sodium and po-
tassium, which had been discovered in plant tissues. The name of this ele-
ment 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 inflame. However, both Arfwedson and Gmelin tried and failed to isolate
the element from its salts.
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. The total amount of lithium
recoverable from global reserves has been estimated at 35 million tonnes, which
includes 15 million tons of the known global lithium reserve base.In 1976 a Na-
tio nal Research Council Panel estimated lithium resources at 10.6 million tons
for the Western World. With the inclusion of Lithium mine, Salar del Hombre
Muerto, Argentina. The brine in this salar is rich in lithium, and the mine concen-
trates the brine by pumping it into solar evaporation ponds. 2009 image from
NASA’s EO-1 satellite
Applications
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 2.1volts for lead/acid or 1.5 volts for zinc cells. Because
of its low atomic mass, it also has a high charge- and power-to-weight ratio.
Lithium is also used in the pharmaceutical and fine-chemical industry in the ma-
nufacture of organolithium reagents ,which are used both as strong bases and
as reagents for the formation of carbon- carbon bonds. Organo lithiums are
also used in polymer synthesis as catalysts/initiators in anionic polymerization
of un-functionalized olefins. Lithium-6 is valued as a source material for tritium
production and as a neutron absorber in nuclear fusion. Natural lithium contains
about 7.5 percent lithium-6. Large amounts of lithium-6 have been isotopically
fractionated for use in nuclear weapons.
Medical use
Lithium salts were used during the 19th century to treat gout. Lithium salts such
as lithium carbonate (Li2CO3), lithium citrate, and lithium orotate are mood sta-
bilizers. They are used in the treatment to 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 inappro-
priate antidiuretic hormone hypersecretion (SIADH) . It was also sometimes
prescribed as a preventive treatment for migraine disease and cluster head-
aches.
The active principle in these salts is the lithium ion Li+. Although this ion has a
smaller diameter than either Na+ o r K+, in a watery environment like the cyto-
plasmic fluid, Li+ binds to the oxygen atoms of water, making it effectively larg-
er 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. Common side effects
of lithium treatment include muscle tremors, twitching, ataxia and hypothyroi-
dism. Long term use is linked to hyperparathyroidism , hypercalcemia (bone
loss) hypertension, damage of tubuli in the kidney, nephrogenic diabetes insipi-
dus (polyuria and polydipsia) and/or glomerular damage even to the point ofur-
emia, seizures and weight gain. Some of the side-effects are a result of the in-
creased elimination of potassium. There appears 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. °
Lithium Frecuent Reactions
Generic Reaction
hhhhhhhhhhhhhhhhhhhhhhhhhhhhh
Ión Lithium + Electrón === Metalic Lithium
Generic Lithium Isotopes Reaction
Cloruro de Litio + Carbonato de Sodio === Carbonato de Litio + Cloruro de Sodio
Cloruro de Potasio + Cloruro de Litio === Potasio + Litio Metálico + Cloro
Lithium Ion + Phosphoric Acid disociation ==== Lithium Phosphat + Water
Other uses
• Electrical and electronic uses:
• Lithium 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.
• Lithium 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.
• Chemical uses:
• Lithium chloride and lithium bromide are extremely hygroscopic and are
used as desiccants.
• Lithium metal is used in the preparation of organo-lithium compounds.
• General engineering:
• lithium 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).
• Optics:
• Lithium is sometimes used in focal lenses, including spectacles and the glass
for the 200-inch (5.08 m) telescope at Mt. Palomar.
The red lithium flame leads to lithium's use in flares and pyrotechnics
• The high non-linearity of lithium niobate also makes it useful in non-linear op-
tics applications.
• Lithium 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. `
• Rocketry:
• Metallic lithium and its complex hydrides, such a Li[AlH4], are used as high
energy additives to rocketpropellants.
• Lithium 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 oxigen.
• Nuclear 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 reac-
tion, 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 (highly enriched in the common isotope lithium-7) forms the ba-
sic constituent of the preferred fluoride salt mixture (LiF-BeF2) used in liquid-fluo-
ride nuclear reactors. Lithium fluoride is exceptionally chemically stable and
LiF/BeF2 mixtures have low melting points and the best neutronic. °
Lithium properties of fluoride salt combinations appropriate for reactor use. Finely
divided lithium fluoride powder has been used for thermoluminescent radiation
dosimetry (TLD): When a sample of such is exposed to radiation, it accumulates
crystal defects which, when heated, resolve via a release of bluish light whose in-
tensity is proportional to the absorbed dose, thus allowing this to be quantified
(see Eugene Tochilin, et al.).
• 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 + 3H. Various means of doing this will be tested at the ITER reactor
being built at Cadarache, France.
• Lithium is 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 firstman-made nuclear reaction,
produced by Cockroft and Walton in 1929.
• Other uses:
• Lithium 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.
• Lithium 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.
• Lithium compounds are used in red fireworks and flares.
• The Mark 50 Torpedo Stored Chemical Energy Propulsion System (SCEPS) uses a
small tank of sulfurhexafluoride gas which is sprayed over a block of solid lithium.
The reaction generates enormous heat which isused to generate steam from
seawater. The steam propels the torpedo in a closed Rankine cycle.
Precautions
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 hydroxideproduced when it is in contact with moisture.
Lithium is safely stored in non-reactive compounds such as naphtha. °
Isotopes of lithium
Naturally occurring lithium (Li) (standard atomic mass: 6.941(2) u ) 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 ener-
gy through nuclear fission. Seven radioisotopes have been characterized, the most
stable being 8Li with a half-life of 838 ms and 9L i with a half-life of 178.3 ms. Allof
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 7.58043×10?23 s. 7Li is one of the primordial elements or, more
properly, primordial isotopes, produced in Big Bang nucleosynthesi s(a small amount
of 6Li is also produced in stars). Lithium isotopes fractionate substantially during a
wide variety of natural processes, including mineral formation (chemical precipita-
tion), metabolism, and ion exchange. Lithium ion substitutes for magnesium and
iron in octahedra l sites in clay minerals, where 6Li is preferred to 7Li, resulting
in enrichment of the light isotope in processes of hyper filtration and rock alteration.
ISOTOPES
Lithium-6 has a greate r affinity for mercury than does lithium-7. When a lithium-
mercury amalgam is in contact with a lithium hydroxide solution, lithium-6 preferen-
tially concentrates in the amalgam, and lithium-7 in the hydroxide. This is the basis of
the colex (column exchange) separation method, in which a counter-flow of amal-
gam and hydroxide passes through a cascade of stages. The lithium-6 fraction is prefe-
rentially drained by the mercury whereas the lithium-7 fraction flows preferentially
with the hydroxide. At the bottom of the column, the lithium (enriched in lithium-
6) is separated from the amalgam, the mercury is recovered and reused with fresh
feedstock. At the top, the lithium hydroxide solution is electrolyzed to liberate the
lithium-7-enriched fraction. The enrichment obtained with this method varies with
the column length and the flow speed. |
Vacuum distillation
Lithium is heated to a temperature of about 550 °C in a vacuum. Lithium atoms
evaporate from the liquid surface and are collected on a cold surface positioned a
few centimeter’s above the liquid surface. Since lithium-6 atoms have a greater
mean free path, they are collected preferentially. The theoretical separation effi-
ciency is abou t 8%. A multi-stage process may be used to obtain higher degrees of
separation. °
Isotopes of lithium
Lithium-4 contains 3 protons and one neutron. It is the shortest-lived isotope of
lithium. It decays by proton emission and has a half-life of 9.1×10?23 s. It can be
formed as an intermediate in some nuclear fusion reactions.
Lithium-6 is valued as a source material for tritium production and as a neutron
absorber in nuclear fusion. Natural lithium contains about 7.5 percent lithium-6.
Large amounts of lithium-6 have been isotopically fractionated for use in nuclear
weapons.
Lithium-7 Some of the material remaining from the production of lithium-6,
which is depleted in lithium-6 and enriched in lithium-7, is made commercially
available, and some has been released into the environment. Relative lithium-7
abundances as high as 35.4% greater than the natural value have been measured in
ground water from a carbonate aquifer underlying West Valley Creek, Pennsylvania
(USA), down-gradient from a lithium processing plant. In depleted material, the
relative 6Li abundance may be reduced by as much as 80% of its normal value,
giving the atomic mass a range from 6.94 u to more than 6.99 u. As a result, the
isotopic composition of lithium is highly variable depending on its source. An
accurate relative atomic mass cannot be given representatively for all samples.
Lithium-7 finds a use as a constituent of the solvent lithium fluoride in liquid-
fluoride nuclear reactors. Indeed, the large neutron absorption cross-section of
lithium-6 (941 barns, thermal) versus the small neutron absorption cross-section of
lithium-7 (0.045 barns, thermal) make strict isotopic separation of lithium a requi-
rement for fluoride reactor use. Lithium-7 hydroxide is used for alkalizing of the
coolant in pressurized water reactors.
Dilithium
Miscellany
Dilithium, Li2, is a diatomic molecule comprising two lithium atoms covalently
bonded together. Li2 is known in the gas phase. It has a bond orderof 1, an
internuclear separation of 267.3 pm and a bond energy of 101 kJ/mol.
Higher numbers of covalently bonded lithium atoms exist, albeit in small Quan -
tities. It has been observed, for example, that 1% of lithium in the vapor phase
(by mass) is in the form of dilithium. Clusters of lithium atoms also exist; the
most common arrangement is Li6.
Lithia water
Lithia water is mineral water containing lithium salts. Lithia water can occur
naturally in spring form. One example can be found in Ashland, Oregon's Lithia
Park. The water is pumped to a fountain where hundreds of people come to
drink it for its supposed positive psychological effects.
Bottled Brands
• Londonderry Lithia
• Lithia Springs Water
Lithium battery
Lithium batteries are disposable (primary) batteries that have lithium metal
or lithium compounds as an anode. Depending on the design and chemical
compounds used, lithium cells can produce voltages from 1.5V to about 3.7 V,
over twice the voltage of an ordinary zinc-carbon battery or alkaline cell.Lithium
batteries are widely used in products such as portable consumer electronic devi-
ces.
Description CR2032 lithium button cell battery
The term "lithium battery" refers to a family of different chemistries, comprising
many types of cathodes and electrolytes. One type of lithium cell having a large
energy density is the lithium-thionyl chloride cell. In this cell, a liquid mixture
of thionyl chloride (SOCl2) and lithium tetrachloroaluminate (LiAlCl4) acts as the
cathode and electrolyte respectively. A porous carbon material serves as a ca-
thode current collector which receives electrons from the external circuit.
However, lithium-thionyl chloride batteries are generally not sold to the con-
sumer market, and find more use in commercial / industrial applications, or
are installed into devices where no consumer replacement is performed. Li-
thiumthionyl chloride batteries are well suited to extremely low-current appli-
cations where long life is necessary, e.g. wireless alarm systems. The most
common type of lithium cell used in consumer applications uses metallic lithium
as anode and manganese dioxide as cathode, with a salt of lithium dissolved in
an organic solvent.
The liquid organic electrolyte is usually a solution of an ion-forming inorganic lithium
compound in a mixture of a high-permittivity solvent (eg. Propylene carbonate) and a
low-viscosity solvent (eg. dimethoxyethane).
Applications
Lithium batteries find application in many long-life, critical devices, such as artificial
pacemakers and other implantable electronic medical devices. These devices use
specialized lithium-iodide batteries designed to last 15 or more years. But for other,
less critical, applications such as in toys, the lithium battery may actually outlast the
toy.In such cases, an expensive lithium battery is not cost-efficient. Lithium batte-
ries can be used in place of ordinary alkaline cells in many devices, such as clocks
and cameras. Although they are more costly, lithium cells will provide much longer
life, thereby minimizing battery replacement. However, attention must be given to
the higher voltage developed by the lithium cells before using them as a drop-in
replacement in devices that normally use ordinary cells. °
Lithium battery
Small lithium batteries are very commonly used in small, portable electronic devices
such as PDAs, watches, thermometers, and calculators, as backup batteries in com-
puters and communication equipment, and in remote car locks. They are available
in many shapes and sizes, with a common variety being the 3 volt "coin" type
manganese variety, typically 20 mm in diameter and 1.6–4 mm thick. The heavy
electrica demands of many of these devices make lithium batteries a particularly
attractive option. In particular, lithium batteries can easily support the brief, heavy
current demands of devices such as digital cameras, and they maintain a higher
voltage for a longer period than alkaline cells.
Some other lithium batteries use a platinum-iridium alloy instead of more usual
compounds. These batteries are generally not preferred, as their cost is high and
they tend to be fragile.
Safety issues and regulation. The computer industry's drive to increase battery
capacity can test the limits of sensitive components such as the membrane sepa-
rator, a polyethylene or poly-propylene film that is only 20-25 µm thick. The
energy density of lithium Batteries has more than doubled since they were
introduced in 1991. When the battery is made to contain more material, the
separator can undergo stress.
Lithium batteries can provide extremely high currents and can discharge very
rapidly when short-circuited. Although this is useful in applications where high
currents are required, a too-rapid discharge of a lithium battery can result in
overheating of the battery, rupture, and even explosion. Lithium-thionyl chloride
batteries are particularly susceptible to this type of discharge. Consumer batteries
usually incorporate overcurrent or thermal protection or vents in order to prevent
explosion.
Air travel. Because of the above risks, shipping and carriage of lithium batteries is
restricted in some situations, particularly transport of lithium batteries by air. The
United States Transportation Security Administration announced restrictions
effective January 1, 2008 on lithium batteries in checked and carry-on luggage.
The rules forbid lithium batteries not installed in a device from checked luggage
and restrict them in carry-on luggage by total lithium content.
Lithium batteries and methamphetamine labs. Unused lithium batteries provide a
convenient source of lithium metal for use as reducing agent in methamphetamine
labs. Some jurisdictions have passed laws to restrict lithium battery sales or asked
businesses to make voluntary restrictions in an attempt to help curb the creation of
illegal meth labs. For example a newspaper
article from January 2004 reports that Wal-Mart stores limit the sale of disposable
lithium batteries to three packages in Missour and four packages in other states.
However, the heavy demand for lithium batteries for use in modern, current hun-
gry devices such as digital cameras conflicts with such restrictions. Via internet
retailers, such restrictions can usually be bypassed with little effort.
Lithium pharmacology
Lithium pharmacology refers to use of the lithium ion, Li+, as a drug. A number of
chemical salts of lithium are used medically as a mood stabilizing drug, prima-rily in
the treatment of bipolar disorder, where they have a role in the treat-ment of
depression and particularly of mania, both acutely and in the long term. As a mood
stabilizer, lithium is probably more effective in preventing mania than depression,
and may reduce the risk of suicide. In depression alone (unipolar disorder) lithium
can be used to augment other antidepressants. Lithium carbonate (Li2CO3), sold
under several trade names, is the most commonly prescribed, while the citrate
salt lithium citrate Lithium citrate (Li3C6H5O7), the sulfate salt lithium sulfate
(Li2SO4), lithium aspartate and the orotate salt lithium orotate are alternatives.
Upon ingestion, lithium becomes widely distributed in the central nervous system
and interacts with a number of neurotransmitters and receptors, decreasing nore-
pinephrine release and increa-sing serotonin synthesis.
History
Against the background of nineteenth century theories linking excess uric acid to
a range of disorders, including depressive and manic disorders, Carl Lange in
Denmark and William Alexander Hammond in New York used lithium to treat
mania from the 1870s onwards. However, by the turn of the century, the use of
lithium in this way died out and was seemingly forgotten. This was also due to
the reluctance of the pharmaceutical industry to invest in a drug that could not be
patented. The use of lithium salts to treat mania was rediscovered by the Austra-
lian psychiatrist John Cade in 1949.Cade was injecting rodents with urine extracts
taken from schizophrenic patients, in an attempt to isolate a metabolic compound
which might be causing mental symptoms. Since uric acid in gout was known
to be psychoactive (adenosine receptors on neurons are stimulated by it; caffeine
blocks them), Cade needed soluble urate for a control. He used lithium urate,
already known to be the most soluble urate compound, and observed that
this caused the rodents to be tranquilized. Cade traced the effect to the lithium
ion itself. Soon, Cade proposed lithium salts as tranquilizers, and soon succeeded
in controlling mania in chronically hospitalized patients with them. This was one
of the first successful applications of a drug to treat mental illness, and it opened
the door for the development of medicines for other mental problems in the
next decades. The rest of the world was slow to adopt this treatment, largely
because of deaths which resulted from even relatively minor overdosing, and
from deaths reported from use of lithium chloride as a substitute for table salt.
Largely through the research and other efforts of Denmark's Mogens Schou
in Europe, and Samuel Gershon in the U.S., this resis-tance was slowly overcome.
The application of lithium for manic illness was approved by the United States
Food and Drug Administration in 1970.
In 2009, Japanese researchers at Oita University reported that low levels of
naturally-occuring lithium in drinking water supplies reduced suicide rates. A
previous report found similar data in the American state of Texas .In response,
psychiatrist Peter Kramer raised the hypothetical possibility of adding lithium
to drinking water.Bioethicist Jacob Appel lent moral support to the possibility
shortly thereafter, arguing that "One person's right to drink lithium-free water
is no greater than another's right to drink lithium-enhanced water.
Lithium pharmacology Use in 7up. As with cocaine in Coca-Cola,
lithium was widely marketed as one of a number of patent medicine products
popular in the late-19th and early-20th centuries, and was later to evolve into
a refreshment beverage. 7 Up was created by Charles Leiper Grigg who
launched his St. Louis-based company The Howdy Corporation in 1920. Grigg
came up with the formula for a lemon-lime soft drink in 1929. The product,
originally named "Bib-Label Lithiated Lemon-Lime Soda", was launched two
weeks before the Wall Street Crash of 1929.] It contained lithium citrate,
amood-stabilizing drug. It was one of a number of patent medicine products
popular in the late-19th and early-20th centuries; they made claims similar to
today's health foods. Specifically it was marketed as a hangover cure. The pro-
duct's name was soon changed to 7 Up. According to Professor Gary Yu (UCSB)
and researchers for the once popular "Uncle John's Bathroom Reader" the
name is derived from the atomic mass of Lithium, 7, which was originally one
of the key ingredients of the drink (as lithium citrate). Lithium citrate was re-
moved from 7 Up's formula in 1950.
Treatment
Lithium treatment is used to treat mania in bipolar disorder. Initially, lithium is
often used in conjunction with antipsychotic drugs as it can take up to a month
for lithium to have an effect. Lithium is also used as prophylaxis for depression
and mania in bipolar disorder. It is sometimes used for other psychiatric disor-
ders such as cycloid psychosis and major depressive disorder. Non – psychiatric
uses are limited, however its use in the prophylaxis of some headaches related
to cluster headaches (trigeminal autonomic cephalgias) particularly hypnic
headache is well established. More recently, Lithium has shown promising
results in a human trial in the neurodegenerative disease amyotrophic lateral
sclerosis. It is sometimes used as an "augmenting" agent, to increase the bene-
fits of standard drugs used for unipolar depression. Lithium treatment was
previously considered to be unsuitable for children, however more recent stu-
dies show its effectiveness for treatment of early-onset bipolar disorder in chil-
dren as young as eight. The required dosage (15–20 mg per kg of body weight)
is slightly less than the toxic level, requiring blood levels of lithium to be moni-
tored closely during treatment.
In order to prescribe the correct dosage, the patient's entire medical history, both
physical and psychological, is sometimes taken into consideration. Those who use
lithium should receive regular serum level tests and should monitor thyroid and
kidney function for abnormalities. As it interferes with the regulation of sodium
and water levels in the body, lithium can cause dehydration. Dehydration, which is
compounded by heat, can result in increasing lithium levels. High doses of halope-
ridol, fluphenazine, or flupenthixol may be hazardous when used with lithium; ire-
versible toxic encephalopathy has been reported. Lithium salts have a narrow
therapeutic/toxic ratio and should therefore not be prescribed unless facilities for-
monitoring plasma concentrations are available. Patients should be carefully selec-
ted. Doses are adjusted to achieve plasma concentrations of 0.6 to 1.2 mmol
Li+/litre (lower end of the range for maintenance therapy and elderly patients,
higher end for pediatric patients) on samples taken 12 hours after the preceding
dose. Over dosage, usually with plasma concentrations over 1.5 mmol Li+/liter,
may be fatal and toxic effects include tremor, ataxia, dysarthria, nystagmus, renal
impairment, and convulsions. If these potentially hazardous signs occur, treat-
ment should be stopped, plasma lithium concentrations redetermined, and steps
taken to reverse lithium toxicity. The most common side effects end up being an
overall dazed feeling and a fine hand tremor. These side effects are generally
present during the length of the treatment but can sometimes disappear in
certain patients. Other common side effects such as nausea and headache, can
be generally remedied by a higher intake of water. Lithium unbalances electro-
lytes; to counteract this, increased water intake is suggested.
Lithium toxicity is compounded by sodium depletion. Concurrent use of diuretics
that inhibit the uptake of sodium by the distal tubule (e.g. thiazides) is hazardous
and should be avoided. In mild cases withdrawal of lithium and administration of
generous amounts of sodium and fluid will reverse the toxicity. Plasma concen-
trations in excess of 2.5 mmol Li+/litre are usually associated with serious toxi-
city requiring emergency treatment. When toxic concentrations are reached
there may be a delay of 1 or 2 days before maximum toxicity occurs. In long term
use, therapeutic concentrations of lithium have been thought to cause histological
and functional changes in the kidney. The significance of such changes is not clear
but is of sufficient concern to discourage long-term use of lithium unless it is
definitely indicated. Doctors may change a bipolar patient's medication from
lithium to another mood stabilizing drug, such as Depakot (divalproex sodium), if
problems with the kidneys arise. An important potentiall consequence of long-
term lithium usage is the development of renal diabetes insipidus (inability to
concentrate urine). Patients should therefore be maintained on lithium treat-
ment after 3–5 years only if, on assessment, benefit persists. Conventional and
sustained-release tablets are available . Preparations vary widely in bioavaila-
bility, and a change in the formulation used requires the same precautions as initia-
tion of treatment. There are few reasons to prefer any one simple salt of lithium;
the carbonate has been the more widely used, but the citrate is also available.
Lithium may be used as a treatment of seborrhoeic der-matitis.
Mechanism of action
Unlike other psychoactive drugs, Li+ typically produces no obvious psychotropic
effects (such as euphoria) in normal individuals at therapeutic concentrations.
The precise mechanism of action of Li+ as a mood-stabilizing agent is currently
unknown. It is possible that Li+ produces its effects by interacting with the transport
of monovalent or divalent cations in neurons. However, because it is a poor subs-
trate at the sodium pump, it cannot maintain a membrane potential and only sus-
tains a small gradient across biological membranes. Li+ is similar enough to Na+ in
that under experimental conditions, Li+ can replace Na+ for production of a single
action potential in neurons. Recent research suggests three different mechanisms
which may act together to deliver the mood-stabilizing effect of this ion. The exci-
tatory neurotransmitter glutamate could be involved in the effect of Lithium as
other mood stabilizers such as valproate and lamotrigine exert influence over glu-
tamate, suggesting a possible biological explanation for mania. The other mecha-
nisms by which lithium might help to regulate mood include the alteration of gene
expression. An unrelated proposed mechanism of action put forth at the Uni-
versity of Pennsylvania in 1996 posits that lithium ion deactivates the GSK-3B
enzyme. The regulation of GSK-3B by lithium may affect the circadian clock and re-
cent research (Feb 2006) seems to support this conclusion. When GSK-3B is activa-
ted, the protein Bmal1 is unable to reset the "master clock" inside the brain; as a
result, the body's natural cycle is disrupted. When the cycle is disrupted, the rou-
tine schedules of many functions (metabolism, sleep, body temperature) are dis-
turbed Lithium may thus restore normal brain function after it is disrupted in some
people. The complete mechanism related to mood in this mechanism is not hypo-
thesized. Another mechanism proposed in 2007 is that lithium may interact with
nitric oxide (NO) signaling pathway in the central nervous system which plays a
crucial role in the neural plasticity. Ghasemiet al. (2008, 2009) have shown that the
NO system could be involved in the antidepressant effect of lithium in the Porsolt
forced swimming test in mice. It was also reported that NMDA receptors blockage
augments antidepressant-like effects of lithium in the mouse forced swimming test
indicating the possible involvement of NMDA receptor/NO signaling in the action
of lithium in this animal model of learned helplessness. Lithium treatment has
been found to inhibit the enzyme inositol monophosphatase leading to higher
levels of inositol triphosphate. This effect was enhanced further with an inositol
triphosphate reuptake inhibitor. Inositol disruptions have been linked to memory
impairment and depression.
END