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Hydrogen

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This article is about the chemistry of hydrogen. For the physics of atomic hydrogen,
see Hydrogen atom. For other meanings, see Hydrogen (disambiguation).

Hydrogen, H 1

Purple glow in its plasma state

Spectral lines of hydrogen

General properties

Name, symbol hydrogen, H

Appearance colorless gas

Pronunciation /hadrdn/[1]
HY-dr-jn

Hydrogen in the periodic table



H

Li

hydrogen helium

Atomic number 1
Standard atomic weight (Ar) 1.008[2] (1.007841.00811)[3]

Element category diatomic nonmetal, could be considered


metalloid

Group, block group 1, s-block

Period period 1

Electron configuration 1s1

per shell 1

Physical properties

Color colorless

Phase gas

Melting point 13.99 K (259.16 C, 434.49 F)

Boiling point 20.271 K (252.879 C, 423.182 F)

Density at stp (0 C and 0.08988 g/L


101.325 kPa)

when liquid, at m.p. 0.07 g/cm3(solid: 0.0763 gcm3)[4]

when liquid, at b.p. 0.07099 g/cm3

Triple point 13.8033 K, 7.041 kPa

Critical point 32.938 K, 1.2858 MPa

Heat of fusion (H2) 0.117 kJ/mol


Heat of vaporization (H2) 0.904 kJ/mol

Molar heat capacity (H2) 28.836 J/(molK)

vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 15 20

Atomic properties

Oxidation states 1, +1 (an amphotericoxide)

Electronegativity Pauling scale: 2.20

Ionization energies 1st: 1312.0 kJ/mol

Covalent radius 315 pm

Van der Waals radius 120 pm

Miscellanea

Crystal structure hexagonal

Speed of sound 1310 m/s (gas, 27 C)

Thermal conductivity 0.1805 W/(mK)

Magnetic ordering diamagnetic[5]

CAS Registry Number 1333-74-0

History
Discovery Henry Cavendish[6][7](1766)

Named by Antoine Lavoisier[8] (1783)

Most stable isotopes

Main article: Isotopes of hydrogen

iso NA half-life DM DE (MeV) DP


1
H 99.9885%1H is stable with 0 neutrons
2
H 0.0115%2H is stable with 1 neutron
3
H trace 12.32 y 0.01861 3He

references

Hydrogen is a chemical element with chemical symbol H and atomic number 1. With
an atomic weight of 1.00794 u, hydrogen is the lightest element on the periodic table.
Its monatomic form (H) is the most abundant chemical substance in the universe,
constituting roughly 75% of all baryonicmass.[9][note 1] Non-remnant stars are mainly
composed of hydrogen in its plasma state. The most common isotope of hydrogen,
termed protium (name rarely used, symbol 1H), has one proton and no neutrons.

The universal emergence of atomic hydrogen first occurred during the recombination
epoch. At standard temperature and pressure, hydrogen is
acolorless, odorless, tasteless, non-toxic, nonmetallic,
highly combustible diatomic gas with the molecular formula H2. Since hydrogen
readily formscovalent compounds with most non-metallic elements, most of the
hydrogen on Earth exists in molecular forms such as in the form of water or organic
compounds. Hydrogen plays a particularly important role in acidbase reactions as
many acid-base reactions involve the exchange of protons between soluble molecules.
In ionic compounds, hydrogen can take the form of a negative charge (i.e., anion)
when it is known as a hydride, or as a positively charged (i.e., cation) species denoted
by the symbol H+. The hydrogen cation is written as though composed of a bare
proton, but in reality, hydrogen cations in ionic compounds are always more complex
species than that would suggest. As the only neutral atom for which the Schrdinger
equation can be solved analytically,[10] study of the energetics and bonding of the
hydrogen atom has played a key role in the development of quantum mechanics.

Hydrogen gas was first artificially produced in the early 16th century, via the mixing
of metals with acids. In 176681, Henry Cavendish was the first to recognize that
hydrogen gas was a discrete substance,[11] and that it produces water when burned, a
property which later gave it its name: in Greek, hydrogen means "water-former".

Industrial production is mainly from the steam reforming of natural gas, and less often
from more energy-intensive hydrogen production methods like the electrolysis of
water.[12] Most hydrogen is employed near its production site, with the two largest uses
being fossil fuel processing (e.g.,hydrocracking) and ammonia production, mostly for
the fertilizer market. Hydrogen is a concern in metallurgy as it can embrittle many
metals,[13]complicating the design of pipelines and storage tanks.[14]

Contents
[hide]

1 Properties
o 1.1 Combustion
o 1.2 Electron energy levels
o 1.3 Elemental molecular forms
o 1.4 Phases
o 1.5 Compounds
1.5.1 Covalent and organic compounds
1.5.2 Hydrides
1.5.3 Protons and acids
o 1.6 Isotopes
2 History
o 2.1 Discovery and use
o 2.2 Role in quantum theory
3 Natural occurrence
4 Production
o 4.1 Metal-acid
o 4.2 Steam reforming
o 4.3 Thermochemical
o 4.4 Anaerobic corrosion
o 4.5 Geological occurrence: the serpentinization reaction
o 4.6 Formation in transformers
5 Applications
o 5.1 Consumption in processes
o 5.2 Coolant
o 5.3 Energy carrier
o 5.4 Semiconductor industry
6 Biological reactions
7 Safety and precautions
8 Notes
9 References
10 Further reading
11 External links

Properties
Combustion

The Space Shuttle Main Engine burnt hydrogen with oxygen, producing a nearly
invisible flame at full thrust.

Hydrogen gas (dihydrogen or molecular hydrogen)[15] is highly flammable and will


burn in air at a very wide range of concentrations between 4% and 75% by
volume.[16] The enthalpy of combustion for hydrogen is 286 kJ/mol:[17]

2 H2(g) + O2(g) 2 H2O(l) + 572 kJ (286 kJ/mol)[note 2]

Hydrogen gas forms explosive mixtures with air if it is 474% concentrated and with
chlorine if it is 595% concentrated. The mixtures may be ignited by spark, heat or
sunlight. The hydrogen autoignition temperature, the temperature of spontaneous
ignition in air, is 500 C (932 F).[18] Pure hydrogen-oxygen flames
emit ultraviolet light and with high oxygen mix are nearly invisible to the naked eye,
as illustrated by the faint plume of the Space Shuttle Main Engine compared to the
highly visible plume of a Space Shuttle Solid Rocket Booster. The detection of a
burning hydrogen leak may require aflame detector; such leaks can be very
dangerous. Hydrogen flames in other conditions are blue, resembling blue natural gas
flames.[19] The destruction of the Hindenburg airship was an infamous example of
hydrogen combustion; the cause is debated, but the visible orange flames were the
result of a rich mixture of hydrogen to oxygen combined with carbon compounds
from the airship skin.
H2 reacts with every oxidizing element. Hydrogen can react spontaneously and
violently at room temperature with chlorine and fluorine to form the corresponding
hydrogen halides, hydrogen chloride and hydrogen fluoride, which are also potentially
dangerous acids.[20]

Electron energy levels

Main article: Hydrogen atom

Depiction of a hydrogen atom with size of central proton shown, and the atomic
diameter shown as about twice the Bohr model radius (image not to scale)

The ground state energy level of the electron in a hydrogen atom is 13.6 eV,[21] which
is equivalent to an ultraviolet photon of roughly 91 nm wavelength.[22]

The energy levels of hydrogen can be calculated fairly accurately using the Bohr
model of the atom, which conceptualizes the electron as "orbiting" the proton in
analogy to the Earth's orbit of the Sun. However, the electromagnetic force attracts
electrons and protons to one another, while planets and celestial objects are attracted
to each other by gravity. Because of the discretization of angular
momentum postulated in early quantum mechanics by Bohr, the electron in the Bohr
model can only occupy certain allowed distances from the proton, and therefore only
certain allowed energies.[23]

A more accurate description of the hydrogen atom comes from a purely quantum
mechanical treatment that uses the Schrdinger equation, Dirac equation or even
the Feynman path integral formulationto calculate the probability density of the
electron around the proton.[24] The most complicated treatments allow for the small
effects of special relativity and vacuum polarization. In the quantum mechanical
treatment, the electron in a ground state hydrogen atom has no angular momentum at
allan illustration of how the "planetary orbit" conception of electron motion differs
from reality.
Elemental molecular forms

See also: Spin isomers of hydrogen

First tracks observed inliquid hydrogen bubble chamber at the Bevatron

There exist two different spin isomers of hydrogen diatomic molecules that differ by
the relative spin of their nuclei.[25] In the orthohydrogen form, the spins of the two
protons are parallel and form a triplet state with a molecular spin quantum number of
1 (12+12); in the parahydrogen form the spins are antiparallel and form a singlet with a
molecular spin quantum number of 0 (1212). At standard temperature and pressure,
hydrogen gas contains about 25% of the para form and 75% of the ortho form, also
known as the "normal form".[26] The equilibrium ratio of orthohydrogen to
parahydrogen depends on temperature, but because the ortho form is an excited
state and has a higher energy than the para form, it is unstable and cannot be purified.
At very low temperatures, the equilibrium state is composed almost exclusively of the
para form. The liquid and gas phase thermal properties of pure parahydrogen differ
significantly from those of the normal form because of differences in rotational heat
capacities, as discussed more fully in spin isomers of hydrogen.[27] The ortho/para
distinction also occurs in other hydrogen-containing molecules or functional groups,
such as water and methylene, but is of little significance for their thermal properties.[28]

The uncatalyzed interconversion between para and ortho H 2 increases with increasing
temperature; thus rapidly condensed H2 contains large quantities of the high-energy
ortho form that converts to the para form very slowly.[29] The ortho/para ratio in
condensed H2 is an important consideration in the preparation and storage of liquid
hydrogen: the conversion from ortho to para is exothermic and produces enough heat
to evaporate some of the hydrogen liquid, leading to loss of liquefied
material. Catalysts for the ortho-para interconversion, such as ferric oxide, activated
carbon, platinized asbestos, rare earth metals, uranium compounds, chromic oxide, or
some nickel[30] compounds, are used during hydrogen cooling.[31]
Phases

Compressed hydrogen
Liquid hydrogen
Slush hydrogen
Solid hydrogen
Metallic hydrogen

Compounds

Further information: Hydrogen compounds

Covalent and organic compounds

While H2 is not very reactive under standard conditions, it does form compounds with
most elements. Hydrogen can form compounds with elements that are
more electronegative, such as halogens (e.g., F, Cl, Br, I), or oxygen; in these
compounds hydrogen takes on a partial positive charge.[32] When bonded
to fluorine, oxygen, or nitrogen, hydrogen can participate in a form of medium-
strength noncovalent bonding with other similar molecules between their hydrogens
called hydrogen bonding, which is critical to the stability of many biological
molecules.[33][34] Hydrogen also forms compounds with less electronegative elements,
such as the metals and metalloids, in which it takes on a partial negative charge. These
compounds are often known as hydrides.[35]

Hydrogen forms a vast array of compounds with carbon called the hydrocarbons, and
an even vaster array with heteroatoms that, because of their general association with
living things, are called organic compounds.[36] The study of their properties is known
as organic chemistry[37] and their study in the context of living organisms is known
as biochemistry.[38] By some definitions, "organic" compounds are only required to
contain carbon. However, most of them also contain hydrogen, and because it is the
carbon-hydrogen bond which gives this class of compounds most of its particular
chemical characteristics, carbon-hydrogen bonds are required in some definitions of
the word "organic" in chemistry.[36] Millions of hydrocarbons are known, and they are
usually formed by complicated synthetic pathways, which seldom involve elementary
hydrogen.

Hydrides

Compounds of hydrogen are often called hydrides, a term that is used fairly loosely.
The term "hydride" suggests that the H atom has acquired a negative or anionic
character, denoted H, and is used when hydrogen forms a compound with a
more electropositive element. The existence of the hydride anion, suggested
by Gilbert N. Lewis in 1916 for group I and II salt-like hydrides, was demonstrated by
Moers in 1920 by the electrolysis of molten lithium hydride (LiH), producing
a stoichiometry quantity of hydrogen at the anode.[39] For hydrides other than group I
and II metals, the term is quite misleading, considering the low electronegativity of
hydrogen. An exception in group II hydrides is BeH
2, which is polymeric. In lithium aluminium hydride, the AlH
4 anion carries hydridic centers firmly attached to the Al(III).

Although hydrides can be formed with almost all main-group elements, the number
and combination of possible compounds varies widely; for example, there are over
100 binary borane hydrides known, but only one binary aluminium
hydride.[40] Binary indium hydride has not yet been identified, although larger
complexes exist.[41]

In inorganic chemistry, hydrides can also serve as bridging ligands that link two metal
centers in a coordination complex. This function is particularly common in group 13
elements, especially in boranes(boron hydrides) and aluminium complexes, as well as
in clustered carboranes.[42]

Protons and acids

Further information: Acidbase reaction

Oxidation of hydrogen removes its electron and gives H+, which contains no electrons
and a nucleus which is usually composed of one proton. That is why H+
is often called a proton. This species is central to discussion of acids. Under
the Bronsted-Lowry theory, acids are proton donors, while bases are proton acceptors.

A bare proton, H+
, cannot exist in solution or in ionic crystals, because of its unstoppable attraction to
other atoms or molecules with electrons. Except at the high temperatures associated
with plasmas, such protons cannot be removed from the electron clouds of atoms and
molecules, and will remain attached to them. However, the term 'proton' is sometimes
used loosely and metaphorically to refer to positively charged or cationic hydrogen
attached to other species in this fashion, and as such is denoted "H+
" without any implication that any single protons exist freely as a species.

To avoid the implication of the naked "solvated proton" in solution, acidic aqueous
solutions are sometimes considered to contain a less unlikely fictitious species, termed
the "hydronium ion" (H
3O+
). However, even in this case, such solvated hydrogen cations are more realistically
conceived as being organized into clusters that form species closer to H
9O+
4.[43] Other oxonium ions are found when water is in acidic solution with other
solvents.[44]

Although exotic on Earth, one of the most common ions in the universe is the H+
3 ion, known as protonated molecular hydrogen or the trihydrogen cation.[45]

Isotopes

Main article: Isotopes of hydrogen

Hydrogen discharge (spectrum) tube

Deuterium discharge (spectrum) tube

Protium, the most common isotope of hydrogen, has one proton and one electron.
Unique among all stable isotopes, it has no neutrons (seediproton for a discussion of
why others do not exist).

Hydrogen has three naturally occurring isotopes, denoted 1


H, 2
H and 3
H. Other, highly unstable nuclei (4
H to 7
H) have been synthesized in the laboratory but not observed in nature.[46][47]
1
H is the most common hydrogen isotope with an abundance of more than
99.98%. Because the nucleus of this isotope consists of only a single proton, it
is given the descriptive but rarely used formal name protium.[48]
2
H, the other stable hydrogen isotope, is known as deuterium and contains one
proton and one neutron in its nucleus. Essentially all deuterium in the universe
is thought to have been produced at the time of the Big Bang, and has endured
since that time. Deuterium is not radioactive, and does not represent a
significant toxicity hazard. Water enriched in molecules that include deuterium
instead of normal hydrogen is called heavy water. Deuterium and its
compounds are used as a non-radioactive label in chemical experiments and in
solvents for 1
H-NMR spectroscopy.[49] Heavy water is used as a neutron moderator and
coolant for nuclear reactors. Deuterium is also a potential fuel for
commercial nuclear fusion.[50]
3
H is known as tritium and contains one proton and two neutrons in its nucleus.
It is radioactive, decaying into helium-3 through beta decay with a half-life of
12.32 years.[42] It is so radioactive that it can be used in luminous paint, making
it useful in such things as watches. The glass prevents the small amount of
radiation from getting out.[51] Small amounts of tritium occur naturally because
of the interaction of cosmic rays with atmospheric gases; tritium has also been
released during nuclear weapons tests.[52] It is used in nuclear fusion
reactions,[53] as a tracer in isotope geochemistry,[54] and in specialized self-
powered lighting devices.[55] Tritium has also been used in chemical and
biological labeling experiments as a radiolabel.[56]

Hydrogen is the only element that has different names for its isotopes in common use
today. During the early study of radioactivity, various heavy radioactive isotopes were
given their own names, but such names are no longer used, except for deuterium and
tritium. The symbols D and T (instead of 2
H and 3
H) are sometimes used for deuterium and tritium, but the corresponding symbol for
protium, P, is already in use for phosphorus and thus is not available for protium.[57] In
its nomenclatural guidelines, the International Union of Pure and Applied
Chemistry allows any of D, T, 2
H, and 3
H to be used, although 2
H and 3
H are preferred.[58]
History
Discovery and use

Main article: Timeline of hydrogen technologies

In 1671, Robert Boyle discovered and described the reaction between iron filings and
dilute acids, which results in the production of hydrogen gas.[59][60] In 1766, Henry
Cavendish was the first to recognize hydrogen gas as a discrete substance, by naming
the gas from a metal-acid reaction "flammable air". He speculated that "flammable
air" was in fact identical to the hypothetical substance called "phlogiston"[61][62] and
further finding in 1781 that the gas produces water when burned. He is usually given
credit for its discovery as an element.[6][7] In 1783, Antoine Lavoisier gave the element
the name hydrogen (from the Greek - hydro meaning "water" and -
genes meaning "creator")[8] when he and Laplace reproduced Cavendish's
finding that water is produced when hydrogen is burned.[7]

Antoine-Laurent de Lavoisier

Lavoisier produced hydrogen for his experiments on mass conservation by reacting a


flux of steam with metallic iron through an incandescent iron tube heated in a fire.
Anaerobic oxidation of iron by the protons of water at high temperature can be
schematically represented by the set of following reactions:

Fe + H2O FeO + H2
2 Fe + 3 H2O Fe2O3 + 3 H2
3 Fe + 4 H2O Fe3O4 + 4 H2

Many metals such as zirconium undergo a similar reaction with water leading to the
production of hydrogen.
Hydrogen was liquefied for the first time by James Dewar in 1898 by
using regenerative cooling and his invention, the vacuum flask.[7] He produced solid
hydrogen the next year.[7] Deuterium was discovered in December 1931 by Harold
Urey, and tritium was prepared in 1934 by Ernest Rutherford, Mark Oliphant,
and Paul Harteck.[6] Heavy water, which consists of deuterium in the place of regular
hydrogen, was discovered by Urey's group in 1932.[7] Franois Isaac de Rivaz built the
first de Rivaz engine, an internal combustion engine powered by a mixture of
hydrogen and oxygen in 1806. Edward Daniel Clarke invented the hydrogen gas
blowpipe in 1819. The Dbereiner's lamp and limelight were invented in 1823.[7]

The first hydrogen-filled balloon was invented by Jacques Charles in


1783.[7] Hydrogen provided the lift for the first reliable form of air-travel following the
1852 invention of the first hydrogen-lifted airship by Henri Giffard.[7] German
count Ferdinand von Zeppelin promoted the idea of rigid airships lifted by hydrogen
that later were called Zeppelins; the first of which had its maiden flight in
1900.[7]Regularly scheduled flights started in 1910 and by the outbreak of World War I
in August 1914, they had carried 35,000 passengers without a serious incident.
Hydrogen-lifted airships were used as observation platforms and bombers during the
war.

The first non-stop transatlantic crossing was made by the British airship R34 in 1919.
Regular passenger service resumed in the 1920s and the discovery of helium reserves
in the United States promised increased safety, but the U.S. government refused to sell
the gas for this purpose. Therefore, H2 was used in the Hindenburg airship, which was
destroyed in a midair fire over New Jersey on 6 May 1937.[7] The incident was
broadcast live on radio and filmed. Ignition of leaking hydrogen is widely assumed to
be the cause, but later investigations pointed to the ignition of the aluminized fabric
coating by static electricity. But the damage to hydrogen's reputation as a lifting
gas was already done.

In the same year the first hydrogen-cooled turbogenerator went into service with
gaseous hydrogen as a coolant in the rotor and the stator in 1937 at Dayton, Ohio, by
the Dayton Power & Light Co.;[63]because of the thermal conductivity of hydrogen gas,
this is the most common type in its field today.

The nickel hydrogen battery was used for the first time in 1977 aboard the U.S.
Navy's Navigation technology satellite-2 (NTS-2).[64] For example, the ISS,[65] Mars
Odyssey[66] and the Mars Global Surveyor[67] are equipped with nickel-hydrogen
batteries. In the dark part of its orbit, the Hubble Space Telescope is also powered by
nickel-hydrogen batteries, which were finally replaced in May 2009,[68] more than 19
years after launch, and 13 years over their design life.[69]
Role in quantum theory

Hydrogen emission spectrum lines in the visible range. These are the four visible lines
of the Balmer series

Because of its simple atomic structure, consisting only of a proton and an electron,
the hydrogen atom, together with the spectrum of light produced from it or absorbed
by it, has been central to the development of the theory
of atomic structure.[70] Furthermore, the corresponding simplicity of the hydrogen
molecule and the corresponding cation H+
2 allowed fuller understanding of the nature of thechemical bond, which followed
shortly after the quantum mechanical treatment of the hydrogen atom had been
developed in the mid-1920s.

One of the first quantum effects to be explicitly noticed (but not understood at the
time) was a Maxwell observation involving hydrogen, half a century before
full quantum mechanical theory arrived. Maxwell observed that the specific heat
capacity of H2 unaccountably departs from that of a diatomic gas below room
temperature and begins to increasingly resemble that of a monatomic gas at cryogenic
temperatures. According to quantum theory, this behavior arises from the spacing of
the (quantized) rotational energy levels, which are particularly wide-spaced in
H2 because of its low mass. These widely spaced levels inhibit equal partition of heat
energy into rotational motion in hydrogen at low temperatures. Diatomic gases
composed of heavier atoms do not have such widely spaced levels and do not exhibit
the same effect.[71]

Antihydrogen (H) is the antimatter counterpart to hydrogen. It consists of


an antiproton with a positron. Antihydrogen is the only type of antimatter atom to
have been produced as of 2015.[72][73]

Natural occurrence
NGC 604, a giant region of ionized hydrogen in theTriangulum Galaxy

Hydrogen, as atomic H, is the most abundant chemical element in the universe,


making up 75% of normal matter by mass and over 90% by number of atoms (most of
the mass of the universe, however, is not in the form of chemical-element type matter,
but rather is postulated to occur as yet-undetected forms of mass such as dark
matter and dark energy).[74] This element is found in great abundance in stars and gas
giant planets. Molecular clouds of H2 are associated with star formation. Hydrogen
plays a vital role in powering stars through the proton-proton reaction and the CNO
cycle nuclear fusion.[75]

Throughout the universe, hydrogen is mostly found in the atomic and plasma states
whose properties are quite different from molecular hydrogen. As a plasma,
hydrogen's electron and proton are not bound together, resulting in very high electrical
conductivity and high emissivity (producing the light from the Sun and other stars).
The charged particles are highly influenced by magnetic and electric fields. For
example, in the solar wind they interact with the Earth's magnetosphere giving rise
to Birkeland currents and the aurora. Hydrogen is found in the neutral atomic state in
the interstellar medium. The large amount of neutral hydrogen found in the damped
Lyman-alpha systems is thought to dominate the cosmological baryonic density of
the Universe up to redshift z=4.[76]

Under ordinary conditions on Earth, elemental hydrogen exists as the diatomic gas,
H2. However, hydrogen gas is very rare in the Earth's atmosphere (1 ppm by volume)
because of its light weight, which enables it to escape from Earth's gravity more easily
than heavier gases. However, hydrogen is the third most abundant element on the
Earth's surface,[77] mostly in the form of chemical compounds such
as hydrocarbons and water.[42] Hydrogen gas is produced by some bacteria
and algae and is a natural component of flatus, as is methane, itself a hydrogen source
of increasing importance.[78]
A molecular form called protonated molecular hydrogen (H+
3) is found in the interstellar medium, where it is generated by ionization of molecular
hydrogen from cosmic rays. This charged ion has also been observed in the upper
atmosphere of the planet Jupiter. The ion is relatively stable in the environment of
outer space due to the low temperature and density. H+
3 is one of the most abundant ions in the Universe, and it plays a notable role in the
chemistry of the interstellar medium.[79] Neutral triatomic hydrogen H3 can only exist
in an excited form and is unstable.[80] By contrast, the positivehydrogen molecular
ion (H+
2) is a rare molecule in the universe.

Production
Main article: Hydrogen production

H
2 is produced in chemistry and biology laboratories, often as a by-product of other
reactions; in industry for the hydrogenation of unsaturated substrates; and in nature as
a means of expelling reducingequivalents in biochemical reactions.

Metal-acid

In the laboratory, H
2 is usually prepared by the reaction of dilute non-oxidizing acids on some reactive
metals such as zinc with Kipp's apparatus.

Zn + 2 H+
Zn2+
+H
2

Aluminium can also produce H


2 upon treatment with bases:

2 Al + 6 H
2O + 2 OH
2 Al(OH)
4+3H
2

The electrolysis of water is a simple method of producing hydrogen. A low voltage


current is run through the water, and gaseous oxygen forms at the anode while
gaseous hydrogen forms at the cathode. Typically the cathode is made from platinum
or another inert metal when producing hydrogen for storage. If, however, the gas is to
be burnt on site, oxygen is desirable to assist the combustion, and so both electrodes
would be made from inert metals. (Iron, for instance, would oxidize, and thus
decrease the amount of oxygen given off.) The theoretical maximum efficiency
(electricity used vs. energetic value of hydrogen produced) is in the range 8094%.[81]

2H
2O(l) 2 H
2(g) + O
2(g)

In 2007, it was discovered that an alloy of aluminium and gallium in pellet form
added to water could be used to generate hydrogen. The process also creates alumina,
but the expensive gallium, which prevents the formation of an oxide skin on the
pellets, can be re-used. This has important potential implications for a hydrogen
economy, as hydrogen can be produced on-site and does not need to be transported.[82]

Steam reforming

Hydrogen can be prepared in several different ways, but economically the most
important processes involve removal of hydrogen from hydrocarbons. Commercial
bulk hydrogen is usually produced by the steam reforming of natural gas.[83] At high
temperatures (10001400 K, 7001100 C or 13002000 F), steam (water vapor)
reacts with methane to yield carbon monoxide and H
2.

CH
4+H
2O CO + 3 H
2

This reaction is favored at low pressures but is nonetheless conducted at high


pressures (2.0 MPa, 20 atm or 600 inHg). This is because high-pressure H
2 is the most marketable product and Pressure Swing Adsorption (PSA) purification
systems work better at higher pressures. The product mixture is known as "synthesis
gas" because it is often used directly for the production of methanol and related
compounds. Hydrocarbons other than methane can be used to produce synthesis gas
with varying product ratios. One of the many complications to this highly optimized
technology is the formation of coke or carbon:
CH
4C+2H
2

Consequently, steam reforming typically employs an excess of H


2O. Additional hydrogen can be recovered from the steam by use of carbon monoxide
through the water gas shift reaction, especially with an iron oxide catalyst. This
reaction is also a common industrial source of carbon dioxide:[83]

CO + H
2O CO
2+H
2

Other important methods for H


2 production include partial oxidation of hydrocarbons:[84]

2 CH
4+O
2 2 CO + 4 H
2

and the coal reaction, which can serve as a prelude to the shift reaction above:[83]

C+H
2O CO + H
2

Hydrogen is sometimes produced and consumed in the same industrial process,


without being separated. In the Haber process for the production of ammonia,
hydrogen is generated from natural gas.[85]Electrolysis of brine to yield chlorine also
produces hydrogen as a co-product.[86]

Thermochemical

There are more than 200 thermochemical cycles which can be used for water splitting,
around a dozen of these cycles such as the iron oxide cycle, cerium(IV) oxide
cerium(III) oxide cycle, zinc zinc-oxide cycle, sulfur-iodine cycle, copper-chlorine
cycle and hybrid sulfur cycle are under research and in testing phase to produce
hydrogen and oxygen from water and heat without using electricity.[87] A number of
laboratories (including in France, Germany, Greece, Japan, and the USA) are
developing thermochemical methods to produce hydrogen from solar energy and
water.[88]
Anaerobic corrosion

Under anaerobic conditions, iron and steel alloys are slowly oxidized by the protons
of water concomitantly reduced in molecular hydrogen (H
2). The anaerobic corrosion of iron leads first to the formation of ferrous
hydroxide (green rust) and can be described by the following reaction:

Fe + 2 H
2O Fe(OH)
2+H
2

In its turn, under anaerobic conditions, the ferrous hydroxide (Fe(OH)


2 ) can be oxidized by the protons of water to form magnetite and molecular hydrogen.
This process is described by the Schikorr reaction:

3 Fe(OH)
2 Fe
3O
4+2H
2O + H
2
ferrous hydroxide magnetite + water + hydrogen

The well crystallized magnetite (Fe


3O
4) is thermodynamically more stable than the ferrous hydroxide (Fe(OH)
2 ).

This process occurs during the anaerobic corrosion of iron and steel in oxygen-
free groundwater and in reducing soils below the water table.

Geological occurrence: the serpentinization reaction

In the absence of atmospheric oxygen (O


2), in deep geological conditions prevailing far away from Earth atmosphere,
hydrogen (H
2) is produced during the process of serpentinization by the anaerobic oxidation by the
water protons (H+) of the ferrous (Fe2+) silicate present in the crystal lattice of
the fayalite (Fe
2SiO
4, the olivine iron-endmember). The corresponding reaction leading to the formation
ofmagnetite (Fe
3O
4), quartz (SiO
2) and hydrogen (H
2) is the following:

3Fe
2SiO
4+2H
2O 2 Fe
3O
4 + 3 SiO
2+3H
2
fayalite + water magnetite + quartz + hydrogen

This reaction closely resembles the Schikorr reaction observed in the anaerobic
oxidation of the ferrous hydroxide in contact with water.

Formation in transformers

From all the fault gases formed in power transformers, hydrogen is the most common
and is generated under most fault conditions; thus, formation of hydrogen is an early
indication of serious problems in the transformer's life cycle.[89]

Applications
Consumption in processes

Large quantities of H
2 are needed in the petroleum and chemical industries. The largest application of H
2 is for the processing ("upgrading") of fossil fuels, and in the production of ammonia.
The key consumers of H
2 in the petrochemical plant include hydrodealkylation, hydrodesulfurization,
and hydrocracking. H
2 has several other important uses. H
2 is used as a hydrogenating agent, particularly in increasing the level of saturation of
unsaturated fats and oils (found in items such as margarine), and in the production
of methanol. It is similarly the source of hydrogen in the manufacture ofhydrochloric
acid. H
2 is also used as a reducing agent of metallic ores.[90]
Hydrogen is highly soluble in many rare earth and transition metals[91] and is soluble in
both nanocrystalline and amorphous metals.[92] Hydrogen solubility in metals is
influenced by local distortions or impurities in the crystal lattice.[93] These properties
may be useful when hydrogen is purified by passage through hot palladium disks, but
the gas's high solubility is a metallurgical problem, contributing to
the embrittlement of many metals,[13] complicating the design of pipelines and storage
tanks.[14]

Apart from its use as a reactant, H


2 has wide applications in physics and engineering. It is used as a shielding
gas in welding methods such as atomic hydrogen welding.[94][95] H2 is used as the rotor
coolant in electrical generators at power stations, because it has the highest thermal
conductivity of any gas. Liquid H2 is used in cryogenic research,
including superconductivity studies.[96] Because H
2 is lighter than air, having a little more than 114 of the density of air, it was once
widely used as a lifting gas in balloons and airships.[97]

In more recent applications, hydrogen is used pure or mixed with nitrogen (sometimes
called forming gas) as a tracer gas for minute leak detection. Applications can be
found in the automotive, chemical, power generation, aerospace, and
telecommunications industries.[98] Hydrogen is an authorized food additive (E 949) that
allows food package leak testing among other anti-oxidizing properties.[99]

Hydrogen's rarer isotopes also each have specific applications. Deuterium (hydrogen-
2) is used in nuclear fission applications as a moderator to slow neutrons, and
in nuclear fusion reactions.[7]Deuterium compounds have applications in chemistry and
biology in studies of reaction isotope effects.[100] Tritium (hydrogen-3), produced
in nuclear reactors, is used in the production of hydrogen bombs,[101] as an isotopic
label in the biosciences,[56] and as a radiation source in luminous paints.[102]

The triple point temperature of equilibrium hydrogen is a defining fixed point on


the ITS-90 temperature scale at 13.8033 kelvins.[103]

Coolant

Main article: Hydrogen-cooled turbo generator

Hydrogen is commonly used in power stations as a coolant in generators due to a


number of favorable properties that are a direct result of its light diatomic molecules.
These include low density, lowviscosity, and the highest specific heat and thermal
conductivity of all gases.
Energy carrier

See also: Hydrogen economy and Hydrogen infrastructure

Hydrogen is not an energy resource,[104] except in the hypothetical context of


commercial nuclear fusion power plants using deuterium or tritium, a technology
presently far from development.[105] The Sun's energy comes from nuclear fusion of
hydrogen, but this process is difficult to achieve controllably on Earth.[106] Elemental
hydrogen from solar, biological, or electrical sources require more energy to make it
than is obtained by burning it, so in these cases hydrogen functions as an energy
carrier, like a battery. Hydrogen may be obtained from fossil sources (such as
methane), but these sources are unsustainable.[104]

The energy density per unit volume of both liquid hydrogen and compressed
hydrogen gas at any practicable pressure is significantly less than that of traditional
fuel sources, although the energy density per unit fuel mass is higher.[104] Nevertheless,
elemental hydrogen has been widely discussed in the context of energy, as a possible
future carrier of energy on an economy-wide scale.[107] For example,CO
2 sequestration followed by carbon capture and storage could be conducted at the
point of H
2 production from fossil fuels.[108] Hydrogen used in transportation would burn
relatively cleanly, with some NOx emissions,[109] but without carbon
emissions.[108] However, the infrastructure costs associated with full conversion to a
hydrogen economy would be substantial.[110] Fuel cells can convert hydrogen and
oxygen directly to electricity more efficiently than internal combustion engines.[111]

Semiconductor industry

Hydrogen is employed to saturate broken ("dangling") bonds of amorphous


silicon and amorphous carbon that helps stabilizing material properties.[112] It is also a
potential electron donor in various oxide materials,
including ZnO,[113][114] SnO2, CdO, MgO,[115] ZrO2, HfO2, La2O3, Y2O3, TiO2, SrTiO3, LaAl
O3, SiO2, Al2O3, ZrSiO4, HfSiO4, and SrZrO3.[116]

Biological reactions
Further information: Biohydrogen and Biological hydrogen production (Algae)

H2 is a product of some types of anaerobic metabolism and is produced by


several microorganisms, usually via reactions catalyzed by iron- or nickel-
containing enzymes called hydrogenases. These enzymes catalyze the
reversible redox reaction between H2 and its component two protons and two
electrons. Creation of hydrogen gas occurs in the transfer of reducing equivalents
produced duringpyruvate fermentation to water.[117] The natural cycle of hydrogen
production and consumption by organisms is called the hydrogen cycle.[118]

Water splitting, in which water is decomposed into its component protons, electrons,
and oxygen, occurs in the light reactions in all photosynthetic organisms. Some such
organisms, including the algaChlamydomonas reinhardtii and cyanobacteria, have
evolved a second step in the dark reactions in which protons and electrons are reduced
to form H2 gas by specialized hydrogenases in thechloroplast.[119] Efforts have been
undertaken to genetically modify cyanobacterial hydrogenases to efficiently
synthesize H2 gas even in the presence of oxygen.[120] Efforts have also been
undertaken with genetically modified alga in a bioreactor.[121]

Safety and precautions


Main article: Hydrogen safety

Hydrogen poses a number of hazards to human safety, from potential detonations and
fires when mixed with air to being an asphyxiant in its pure, oxygen-free form.[122] In
addition, liquid hydrogen is acryogen and presents dangers (such as frostbite)
associated with very cold liquids.[123] Hydrogen dissolves in many metals, and, in
addition to leaking out, may have adverse effects on them, such ashydrogen
embrittlement,[124] leading to cracks and explosions.[125] Hydrogen gas leaking into
external air may spontaneously ignite. Moreover, hydrogen fire, while being
extremely hot, is almost invisible, and thus can lead to accidental burns.[126]

Even interpreting the hydrogen data (including safety data) is confounded by a


number of phenomena. Many physical and chemical properties of hydrogen depend
on the parahydrogen/orthohydrogenratio (it often takes days or weeks at a given
temperature to reach the equilibrium ratio, for which the data is usually given).
Hydrogen detonation parameters, such as critical detonation pressure and temperature,
strongly depend on the container geometry.[122]

Notes
1. However, most of the universe's mass is not in the form of baryons or chemical elements.
See dark matter and dark energy.
2. 286 kJ/mol: energy per mole of the combustible material (molecular hydrogen)
Helium
From Wikipedia, the free encyclopedia
Jump to: navigation, search
This article is about the chemical element. For other uses, see Helium
(disambiguation).

Helium, He 2

Spectral lines of helium

General properties

Name, symbol helium, He

Appearance colorless gas, exhibiting a red-orange


glow when placed in a high-voltage
electric field

Pronunciation /hilim/
HEE-lee-m

Helium in the periodic table



He

Ne

hydrogen helium lithium


Atomic number 2

Standard atomic weight () (Ar) 4.002602(2)[1]

Element category noble gas

Group, block group 18 (noble gases), s-block

Period period 1

Electron configuration 1s2

per shell 2

Physical properties

Phase gas

Melting point 0.95 K (272.20 C, 457.96 F)


(at 2.5 MPa)

Boiling point 4.222 K (268.928 C, 452.070 F)

Density at stp(0 C and 101.325 kPa) 0.1786 g/L

when liquid, at m.p. 0.145 g/cm3

when liquid, at b.p. 0.125 g/cm3

Triple point 2.177 K, 5.043 kPa

Critical point 5.1953 K, 0.22746 MPa

Heat of fusion 0.0138 kJ/mol

Heat of vaporization 0.0829 kJ/mol


Molar heat capacity 20.78[2] J/(molK)

vapor pressure (defined by ITS-90)


P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 1.23 1.67 2.48 4.21

Atomic properties

Oxidation states 0

Electronegativity Pauling scale: no data

Ionization energies 1st: 2372.3 kJ/mol


2nd: 5250.5 kJ/mol

Covalent radius 28 pm

Van der Waals radius 140 pm

Miscellanea

Crystal structure hexagonal close-packed (hcp)

Speed of sound 972 m/s

Thermal conductivity 0.1513 W/(mK)

Magnetic ordering diamagnetic[3]

CAS Registry Number 7440-59-7

History
Naming after Helios, Greek god of the Sun

Discovery Pierre Janssen, Norman


Lockyer (1868)

First isolation William Ramsay, Per Teodor


Cleve, Abraham Langlet(1895)

Most stable isotopes

Main article: Isotopes of helium

iso NA half-life DM DE (MeV) DP


3
He0.000137%* 3He is stable with 1 neutron
4
He99.999863%* 4He is stable with 2 neutrons

* Atmospheric value, abundance may differ elsewhere

references

Helium is a chemical element with symbol He and atomic number 2. It is a colorless,


odorless, tasteless, non-toxic, inert, monatomic gas that heads thenoble gas group in
the periodic table. Its boiling and melting points are the lowest among all
the elements.

Helium is the second lightest element and is the second most abundant element in the
observable universe, being present at about 24% of the total elemental mass, which is
more than 12 times the mass of all the heavier elements combined. Its abundance is
similar to this figure in the Sun and inJupiter. This is due to the very high nuclear
binding energy (per nucleon) of helium-4 with respect to the next three elements after
helium. This helium-4 binding energy also accounts for why it is a product of
both nuclear fusion and radioactive decay. Most helium in the universe is helium-4,
and is believed to have been formed during the Big Bang. Large amounts of new
helium are being created by nuclear fusion of hydrogen in stars.

Helium is named for the Greek god of the Sun, Helios. It was first detected as an
unknown yellow spectral line signature in sunlight during a solar eclipse in 1868 by
French astronomer Jules Janssen. Janssen is jointly credited with detecting the
element along with Norman Lockyer. Jannsen observed during the solar eclipse of
1868 while Lockyer observed from Britain. Lockyer was the first to propose that the
line was due to a new element, which he named. The formal discovery of the
element was made in 1895 by two Swedish chemists, Per Teodor Cleve and Nils
Abraham Langlet, who found helium emanating from the uranium ore cleveite. In
1903, large reserves of helium were found in natural gas fields in parts of the United
States, which is by far the largest supplier of the gas today.

Liquid helium is used in cryogenics (its largest single use, absorbing about a quarter
of production), particularly in the cooling of superconducting magnets, with the main
commercial application being in MRI scanners. Helium's other industrial usesas a
pressurizing and purge gas, as a protective atmosphere for arc welding and in
processes such as growing crystals to make silicon wafersaccount for half of the gas
produced. A well-known but minor use is as a lifting gas in balloons and airships.[4] As
with any gas whose density differs from that of air, inhaling a small volume of helium
temporarily changes the timbre and quality of the human voice. In scientific research,
the behavior of the two fluid phases of helium-4 (helium I and helium II) is important
to researchers studying quantum mechanics (in particular the property
of superfluidity) and to those looking at the phenomena, such as superconductivity,
produced in matter near absolute zero.

On Earth it is relatively rare 5.2 ppm by volume in the atmosphere. Most terrestrial
helium present today is created by the natural radioactive decayof heavy radioactive
elements (thorium and uranium, although there are other examples), as the alpha
particles emitted by such decays consist of helium-4 nuclei. This radiogenic helium is
trapped with natural gas in concentrations up to 7% by volume, from which it is
extracted commercially by a low-temperature separation process called fractional
distillation. Helium is a finite resource, and once released into the atmosphere, it
readily escapes into space.[5][6][7]

Contents
[hide]

1 History
o 1.1 Scientific discoveries
o 1.2 Extraction and use
2 Characteristics
o 2.1 The helium atom
2.1.1 Helium in quantum mechanics
2.1.2 The related stability of the helium-4 nucleus and electron
shell
o 2.2 Gas and plasma phases
o 2.3 Liquid helium
2.3.1 Helium I state
2.3.2 Helium II state
3 Isotopes
4 Compounds
5 Occurrence and production
o 5.1 Natural abundance
o 5.2 Modern extraction and distribution
o 5.3 Conservation advocates
6 Applications
o 6.1 Controlled atmospheres
o 6.2 Gas tungsten arc welding
o 6.3 Minor uses
6.3.1 Industrial leak detection
6.3.2 Flight
6.3.3 Minor commercial and recreational uses
6.3.4 Scientific uses
7 Inhalation and safety
o 7.1 Effects
o 7.2 Hazards
8 Additional images
9 See also
10 References
11 Bibliography
12 External links

History
Scientific discoveries

The first evidence of helium was observed on August 18, 1868 as a bright yellow line
with a wavelength of 587.49 nanometers in the spectrum of thechromosphere of
the Sun. The line was detected by French astronomer Jules Janssen during a total solar
eclipse in Guntur, India.[8][9] This line was initially assumed to be sodium. On October
20 of the same year, English astronomer Norman Lockyer observed a yellow line in
the solar spectrum, which he named the D3 Fraunhofer line because it was near the
known D1 and D2 lines of sodium.[10] He concluded that it was caused by an element in
the Sun unknown on Earth. Lockyer and English chemist Edward Frankland named
the element with the Greek word for the Sun, (helios).[11][12]
Spectral lines of helium

In 1882, Italian physicist Luigi Palmieri detected helium on Earth, for the first time,
through its D3 spectral line, when he analyzed the lava of Mount Vesuvius.[13]

Sir William Ramsay, the discoverer of terrestrial helium

On March 26, 1895, Scottish chemist Sir William Ramsay isolated helium on Earth by
treating the mineral cleveite (a variety of uraninite with at least 10% rare earth
elements) with mineral acids. Ramsay was looking for argon but, after
separating nitrogen and oxygen from the gas liberated by sulfuric acid, he noticed a
bright yellow line that matched the D3 line observed in the spectrum of the
Sun.[10][14][15][16] These samples were identified as helium by Lockyer and British
physicist William Crookes. It was independently isolated from cleveite in the same
year by chemists Per Teodor Cleve and Abraham Langlet in Uppsala, Sweden, who
collected enough of the gas to accurately determine its atomic weight.[9][17][18] Helium
was also isolated by the American geochemist William Francis Hillebrand prior to
Ramsay's discovery when he noticed unusual spectral lines while testing a sample of
the mineral uraninite. Hillebrand, however, attributed the lines to nitrogen. His letter
of congratulations to Ramsay offers an interesting case of discovery and near-
discovery in science.[19]
In 1907, Ernest Rutherford and Thomas Royds demonstrated that alpha particles are
helium nuclei by allowing the particles to penetrate the thin glass wall of an evacuated
tube, then creating a discharge in the tube to study the spectra of the new gas inside.
In 1908, helium was first liquefied by Dutch physicist Heike Kamerlingh Onnes by
cooling the gas to less than one kelvin.[20] He tried to solidify it by further reducing the
temperature but failed because helium does not solidify at atmospheric pressure.
Onnes' student Willem Hendrik Keesom was eventually able to solidify 1 cm3 of
helium in 1926 by applying additional external pressure.[21]

In 1938, Russian physicist Pyotr Leonidovich Kapitsa discovered that helium-4 has
almost no viscosity at temperatures near absolute zero, a phenomenon now
called superfluidity.[22] This phenomenon is related to BoseEinstein condensation. In
1972, the same phenomenon was observed in helium-3, but at temperatures much
closer to absolute zero, by American physicists Douglas D. Osheroff, David M. Lee,
and Robert C. Richardson. The phenomenon in helium-3 is thought to be related to
pairing of helium-3 fermions to make bosons, in analogy to Cooper pairs of electrons
producingsuperconductivity.[23]

Extraction and use

After an oil drilling operation in 1903 in Dexter, Kansas produced a gas geyser that
would not burn, Kansas state geologist Erasmus Haworth collected samples of the
escaping gas and took them back to the University of Kansas at Lawrence where, with
the help of chemists Hamilton Cady and David McFarland, he discovered that the gas
consisted of, by volume, 72% nitrogen, 15% methane (acombustible percentage only
with sufficient oxygen), 1% hydrogen, and 12% an unidentifiable gas.[9][24] With further
analysis, Cady and McFarland discovered that 1.84% of the gas sample was
helium.[25][26] This showed that despite its overall rarity on Earth, helium was
concentrated in large quantities under the American Great Plains, available for
extraction as a byproduct of natural gas.[27]

This enabled the United States to become the world's leading supplier of helium.
Following a suggestion by Sir Richard Threlfall, the United States Navy sponsored
three small experimental helium plants during World War I. The goal was to
supply barrage balloons with the non-flammable, lighter-than-air gas. A total of
5,700 m3 (200,000 cu ft) of 92% helium was produced in the program even though
less than a cubic meter of the gas had previously been obtained.[10] Some of this gas
was used in the world's first helium-filled airship, the U.S. Navy's C-7, which flew its
maiden voyage fromHampton Roads, Virginia, to Bolling Field in Washington, D.C.,
on December 1, 1921,[28] nearly two years before the Navy's first rigid airship to be
helium-filled, the Naval Aircraft Factory-built USS Shenandoah, itself flew for the
first time in September 1923.
Although the extraction process, using low-temperature gas liquefaction, was not
developed in time to be significant during World War I, production continued. Helium
was primarily used as a lifting gasin lighter-than-air craft. This use increased demand
during World War II, as well as demands for shielded arc welding. The helium mass
spectrometer was also vital in the atomic bomb Manhattan Project.[29]

The government of the United States set up the National Helium Reserve in 1925
at Amarillo, Texas, with the goal of supplying military airships in time of war and
commercial airships in peacetime.[10]Because of the Helium Control Act (1927), which
banned the export of scarce helium on which the US then had a production monopoly,
together with the prohibitive cost of the gas, the Hindenburg, like all
German Zeppelins, was forced to use hydrogen as the lift gas. Helium use following
World War II was depressed but the reserve was expanded in the 1950s to ensure a
supply of liquid helium as a coolant to create oxygen/hydrogen rocket fuel (among
other uses) during the Space Race and Cold War. Helium use in the United States in
1965 was more than eight times the peak wartime consumption.[30]

After the "Helium Acts Amendments of 1960" (Public Law 86777), the U.S. Bureau
of Mines arranged for five private plants to recover helium from natural gas. For
this helium conservation program, the Bureau built a 425-mile (684 km) pipeline
from Bushton, Kansas, to connect those plants with the government's partially
depleted Cliffside gas field, near Amarillo, Texas. This helium-nitrogen mixture was
injected and stored in the Cliffside gas field until needed, when it then was further
purified.[31]

By 1995, a billion cubic meters of the gas had been collected and the reserve was
US$1.4 billion in debt, prompting the Congress of the United States in 1996 to phase
out the reserve.[9][32] The resulting "Helium Privatization Act of 1996"[33] (Public Law
104273) directed the United States Department of the Interior to empty the reserve,
with sales starting by 2005.[34]

Helium produced between 1930 and 1945 was about 98.3% pure (2% nitrogen), which
was adequate for airships. In 1945, a small amount of 99.9% helium was produced for
welding use. By 1949, commercial quantities of Grade A 99.95% helium were
available.[35]

For many years the United States produced over 90% of commercially usable helium
in the world, while extraction plants in Canada, Poland, Russia, and other nations
produced the remainder. In the mid-1990s, a new plant in Arzew, Algeria, producing
17 million cubic meters (600 million cubic feet) began operation, with enough
production to cover all of Europe's demand. Meanwhile, by 2000, the consumption of
helium within the U.S. had risen to above 15 million kg per year. [36] In 20042006, two
additional plants, one in Ras Laffan, Qatar, and the other in Skikda, Algeria, were
built. Algeria quickly became the second leading producer of helium.[37] Through this
time, both helium consumption and the costs of producing helium increased.[38] From
2002 to 2007 helium prices doubled.[39]

As of 2012 the United States National Helium Reserve accounted for 30 percent of the
world's helium.[40] The reserve was expected to run out of helium in 2018.[40] Despite
that a proposed bill in theUnited States Senate would allow the reserve to continue to
sell the gas. Other large reserves were in the Hugoton in Kansas, United States and
nearby gas fields of Kansas and the panhandles of Texasand Oklahoma. New helium
plants were scheduled to open in 2012 in Qatar, Russia and the United States state
of Wyoming but they were not expected to ease the shortage.[40]

In 2013, Qatar started up the world's largest helium unit.[41] 2014 was widely
acknowledged to be a year of over-supply in the helium business, following years of
renowned shortages.[42] Nasdaq reported (2015) that for Air Products, an international
corporation that sells gases for industrial use, helium volumes remain under pressure
due to feedstock supply constraints.[43]

Characteristics
The helium atom

Main article: Helium atom

The helium atom. Depicted are the nucleus (pink) and the electron cloud distribution
(black). The nucleus (upper right) in helium-4 is in reality spherically symmetric and
closely resembles the electron cloud, although for more complicated nuclei this is not
always the case.

Helium in quantum mechanics


In the perspective of quantum mechanics, helium is the second simplest atom to
model, following the hydrogen atom. Helium is composed of two electrons in atomic
orbitals surrounding a nucleus containing two protons along with some neutrons. As
in Newtonian mechanics, no system consisting of more than two particles can be
solved with an exact analytical mathematical approach (see 3-body problem) and
helium is no exception. Thus, numerical mathematical methods are required, even to
solve the system of one nucleus and two electrons. Such computational
chemistry methods have been used to create a quantum mechanical picture of helium
electron binding which is accurate to within < 2% of the correct value, in a few
computational steps.[44] In such models it is found that each electron in helium partly
screens the nucleus from the other, so that the effective nuclear charge Z which each
electron sees, is about 1.69 units, not the 2 charges of a classic "bare" helium nucleus.

The related stability of the helium-4 nucleus and electron shell

The nucleus of the helium-4 atom is identical with an alpha particle. High-energy
electron-scattering experiments show its charge to decrease exponentially from a
maximum at a central point, exactly as does the charge density of helium's
own electron cloud. This symmetry reflects similar underlying physics: the pair of
neutrons and the pair of protons in helium's nucleus obey the same quantum
mechanical rules as do helium's pair of electrons (although the nuclear particles are
subject to a different nuclear binding potential), so that all these fermions fully
occupy 1s orbitals in pairs, none of them possessing orbital angular momentum, and
each cancelling the other's intrinsic spin. Adding another of any of these particles
would require angular momentum and would release substantially less energy (in fact,
no nucleus with five nucleons is stable). This arrangement is thus energetically
extremely stable for all these particles, and this stability accounts for many crucial
facts regarding helium in nature.

For example, the stability and low energy of the electron cloud state in helium
accounts for the element's chemical inertness, and also the lack of interaction of
helium atoms with each other, producing the lowest melting and boiling points of all
the elements.

In a similar way, the particular energetic stability of the helium-4 nucleus, produced
by similar effects, accounts for the ease of helium-4 production in atomic reactions
involving both heavy-particle emission, and fusion. Some stable helium-3 is produced
in fusion reactions from hydrogen, but it is a very small fraction, compared with the
highly favorable helium-4.
Binding energy per nucleon of common isotopes. The binding energy per particle of
helium-4 is significantly larger than all nearby nuclides.

The unusual stability of the helium-4 nucleus is also important cosmologically: it


explains the fact that in the first few minutes after the Big Bang, as the "soup" of free
protons and neutrons which had initially been created in about 6:1 ratio cooled to the
point that nuclear binding was possible, almost all first compound atomic nuclei to
form were helium-4 nuclei. So tight was helium-4 binding that helium-4 production
consumed nearly all of the free neutrons in a few minutes, before they could beta-
decay, and also leaving few to form heavier atoms such as lithium, beryllium, or
boron. Helium-4 nuclear binding per nucleon is stronger than in any of these elements
(see nucleogenesis and binding energy) and thus no energetic drive was available,
once helium had been formed, to make elements 3, 4 and 5. It was barely energetically
favorable for helium to fuse into the next element with a lower energy per nucleon,
carbon. However, due to lack of intermediate elements, this process requires three
helium nuclei striking each other nearly simultaneously (see triple alpha process).
There was thus no time for significant carbon to be formed in the few minutes after
the Big Bang, before the early expanding universe cooled to the temperature and
pressure point where helium fusion to carbon was no longer possible. This left the
early universe with a very similar ratio of hydrogen/helium as is observed today (3
parts hydrogen to 1 part helium-4 by mass), with nearly all the neutrons in the
universe trapped in helium-4.

All heavier elements (including those necessary for rocky planets like the Earth, and
for carbon-based or other life) have thus been created since the Big Bang in stars
which were hot enough to fuse helium itself. All elements other than hydrogen and
helium today account for only 2% of the mass of atomic matter in the universe.
Helium-4, by contrast, makes up about 23% of the universe's ordinary matternearly
all the ordinary matter that is not hydrogen.

Gas and plasma phases


Helium discharge tube shaped like the element's atomic symbol

Helium is the second least reactive noble gas, after neon, and thus the second least
reactive of all elements.[45] It is inert and monatomic in all standard conditions.
Because of helium's relatively low molar (atomic) mass, its thermal
conductivity, specific heat, and sound speed in the gas phase are all greater than any
other gas except hydrogen. For similar reasons, and also due to the small size of
helium atoms, helium's diffusion rate through solids is three times that of air and
around 65% that of hydrogen.[10]

Helium is the least water-soluble monatomic gas,[46] and one of the least water-soluble
of any gas (CF4, SF6, and C4F8 have lower mole fraction solubilities: 0.3802, 0.4394,
and 0.2372 x2/105, respectively, versus helium's 0.70797 x2/105),[47] and helium's index
of refraction is closer to unity than that of any other gas.[48] Helium has a
negative Joule-Thomson coefficient at normal ambient temperatures, meaning it heats
up when allowed to freely expand. Only below its Joule-Thomson inversion
temperature (of about 32 to 50 K at 1 atmosphere) does it cool upon free
expansion.[10] Once precooled below this temperature, helium can be liquefied through
expansion cooling.

Most extraterrestrial helium is found in a plasma state, with properties quite different
from those of atomic helium. In a plasma, helium's electrons are not bound to its
nucleus, resulting in very high electrical conductivity, even when the gas is only
partially ionized. The charged particles are highly influenced by magnetic and electric
fields. For example, in the solar wind together with ionized hydrogen, the particles
interact with the Earth's magnetosphere giving rise to Birkeland currents and
the aurora.[49]

Liquid helium
Liquefied helium. This helium is not only liquid, but has been cooled to the point
ofsuperfluidity. The drop of liquid at the bottom of the glass represents helium
spontaneously escaping from the container over the side, to empty out of the
container. The energy to drive this process is supplied by the potential energy of the
falling helium.
Main article: Liquid helium

Unlike any other element, helium will remain liquid down to absolute zero at normal
pressures. This is a direct effect of quantum mechanics: specifically, the zero point
energy of the system is too high to allow freezing. Solid helium requires a temperature
of 11.5 K (about 272 C or 457 F) and about 25 bar (2.5 MPa) of pressure.[50] It is
often hard to distinguish solid from liquid helium since therefractive index of the two
phases are nearly the same. The solid has a sharp melting point and has
a crystalline structure, but it is highly compressible; applying pressure in a laboratory
can decrease its volume by more than 30%.[51] With a bulk modulus of about
27 MPa[52] it is ~100 times more compressible than water. Solid helium has a density
of 0.214 0.006 g/cm3 at 1.15 K and 66 atm; the projected density at 0 K and 25 bar
(2.5 MPa) is 0.187 0.009 g/cm3.[53]

Helium I state

Below its boiling point of 4.22 kelvins and above the lambda point of 2.1768 kelvins,
the isotope helium-4 exists in a normal colorless liquid state, called helium I.[10] Like
other cryogenic liquids, helium I boils when it is heated and contracts when its
temperature is lowered. Below the lambda point, however, helium does not boil, and it
expands as the temperature is lowered further.

Helium I has a gas-like index of refraction of 1.026 which makes its surface so hard to
see that floats of styrofoam are often used to show where the surface is.[10] This
colorless liquid has a very lowviscosity and a density of 0.1450.125 g/mL (between
about 0 and 4 K),[54] which is only one-fourth the value expected from classical
physics.[10] Quantum mechanics is needed to explain this property and thus both types
of liquid helium are called quantum fluids, meaning they display atomic properties on
a macroscopic scale. This may be an effect of its boiling point being so close to
absolute zero, preventing random molecular motion (thermal energy) from masking
the atomic properties.[10]
Helium II state

Main article: Superfluid helium-4

Liquid helium below its lambda point begins to exhibit very unusual characteristics, in
a state called helium II. When helium II boils, due to its high thermal conductivity it
does not bubble but rather evaporates directly from its surface. Helium-3 also has
a superfluid phase, but only at much lower temperatures; as a result, less is known
about such properties in the isotope.[10]

Unlike ordinary liquids, helium II will creep along surfaces in order to reach an equal
level; after a short while, the levels in the two containers will equalize. The Rollin
filmalso covers the interior of the larger container; if it were not sealed, the helium II
would creep out and escape.[10]

Helium II is a superfluid, a quantum mechanical state (see: macroscopic quantum


phenomena) of matter with strange properties. For example, when it flows through
capillaries as thin as 107 to 108 m it has no measurable viscosity.[9] However, when
measurements were done between two moving discs, a viscosity comparable to that of
gaseous helium was observed. Current theory explains this using thetwo-fluid
model for helium II. In this model, liquid helium below the lambda point is viewed as
containing a proportion of helium atoms in a ground state, which are superfluid and
flow with exactly zero viscosity, and a proportion of helium atoms in an excited state,
which behave more like an ordinary fluid.[55]

In the fountain effect, a chamber is constructed which is connected to a reservoir of


helium II by a sintered disc through which superfluid helium leaks easily but through
which non-superfluid helium cannot pass. If the interior of the container is heated, the
superfluid helium changes to non-superfluid helium. In order to maintain the
equilibrium fraction of superfluid helium, superfluid helium leaks through and
increases the pressure, causing liquid to fountain out of the container.[56]

The thermal conductivity of helium II is greater than that of any other known
substance, a million times that of helium I and several hundred times that
of copper.[10] This is because heat conduction occurs by an exceptional quantum
mechanism. Most materials that conduct heat well have a valence band of free
electrons which serve to transfer the heat. Helium II has no such valence band but
nevertheless conducts heat well. The flow of heat is governed by equations that are
similar to the wave equation used to characterize sound propagation in air. When heat
is introduced, it moves at 20 meters per second at 1.8 K through helium II as waves in
a phenomenon known as second sound.[10]

Helium II also exhibits a creeping effect. When a surface extends past the level of
helium II, the helium II moves along the surface, against the force of gravity.
Helium II will escape from a vessel that is not sealed by creeping along the sides until
it reaches a warmer region where it evaporates. It moves in a 30 nm-thick film
regardless of surface material. This film is called a Rollin film and is named after the
man who first characterized this trait, Bernard V. Rollin.[10][57][58] As a result of this
creeping behavior and helium II's ability to leak rapidly through tiny openings, it is
very difficult to confine liquid helium. Unless the container is carefully constructed,
the helium II will creep along the surfaces and through valves until it reaches
somewhere warmer, where it will evaporate. Waves propagating across a Rollin film
are governed by the same equation as gravity waves in shallow water, but rather than
gravity, the restoring force is the van der Waals force.[59] These waves are known
as third sound.[60]

Isotopes
Main article: Isotopes of helium

There are nine known isotopes of helium, but only helium-3 and helium-4 are stable.
In the Earth's atmosphere, there is one 3
He atom for every million 4
He atoms.[9] Unlike most elements, helium's isotopic abundance varies greatly by
origin, due to the different formation processes. The most common isotope, helium-4,
is produced on Earth by alpha decay of heavier radioactive elements; the alpha
particles that emerge are fully ionized helium-4 nuclei. Helium-4 is an unusually
stable nucleus because its nucleons are arranged into complete shells. It was also
formed in enormous quantities duringBig Bang nucleosynthesis.[61]
Helium-3 is present on Earth only in trace amounts; most of it since Earth's formation,
though some falls to Earth trapped in cosmic dust.[62] Trace amounts are also produced
by the beta decay oftritium.[63] Rocks from the Earth's crust have isotope ratios varying
by as much as a factor of ten, and these ratios can be used to investigate the origin of
rocks and the composition of the Earth'smantle.[62] 3
He is much more abundant in stars, as a product of nuclear fusion. Thus in
the interstellar medium, the proportion of 3
He to 4
He is around 100 times higher than on Earth.[64] Extraplanetary material, such as lunar
and asteroid regolith, have trace amounts of helium-3 from being bombarded by solar
winds. The Moon's surface contains helium-3 at concentrations on the order of
10 ppb, much higher than the approximately 5 ppt found in the Earth's
atmosphere.[65][66] A number of people, starting with Gerald Kulcinski in 1986,[67] have
proposed to explore the moon, mine lunar regolith and use the helium-3 for fusion.

Liquid helium-4 can be cooled to about 1 kelvin using evaporative cooling in a 1-K
pot. Similar cooling of helium-3, which has a lower boiling point, can achieve
about 0.2 kelvin in a helium-3 refrigerator. Equal mixtures of liquid 3
He and 4
He below 0.8 K separate into two immiscible phases due to their dissimilarity (they
follow different quantum statistics: helium-4 atoms are bosons while helium-3 atoms
are fermions).[10] Dilution refrigerators use this immiscibility to achieve temperatures
of a few millikelvins.

It is possible to produce exotic helium isotopes, which rapidly decay into other
substances. The shortest-lived heavy helium isotope is helium-5 with a half-
life of 7.61022 s. Helium-6 decays by emitting a beta particle and has a half-life of
0.8 second. Helium-7 also emits a beta particle as well as a gamma ray. Helium-7 and
helium-8 are created in certain nuclear reactions.[10] Helium-6 and helium-8 are known
to exhibit a nuclear halo.[10]

Compounds
See also: Noble gas compound
Structure of the helium hydride ion, HHe+

Structure of the suspected fluoroheliate anion, OHeF

Helium has a valence of zero and is chemically unreactive under all normal
conditions.[51] It is an electrical insulator unless ionized. As with the other noble gases,
helium has metastable energy levelsthat allow it to remain ionized in an electrical
discharge with a voltage below its ionization potential.[10] Helium can form
unstable compounds, known as excimers, with tungsten, iodine, fluorine, sulfur and
phosphorus when it is subjected to a glow discharge, to electron bombardment, or else
is a plasma for another reason. The molecular compounds HeNe, HgHe10, and WHe2,
and the molecular ionsHe+
2, He2+
2, HeH+
, and HeD+
have been created this way.[68] HeH+ is also stable in its ground state, but is extremely
reactiveit is the strongest Brnsted acid known, and therefore can exist only in
isolation, as it will protonate any molecule or counteranion it comes into contact with.
This technique has also allowed the production of the neutral molecule He 2, which has
a large number of band systems, and HgHe, which is apparently held together only by
polarization forces.[10]

Van der Waals compounds of helium can also be formed with cryogenic helium gas
and atoms of a substance, such as LiHe and He2.[69]

Theoretically, other true compounds may also be possible, such as helium


fluorohydride (HHeF) which would be analogous to HArF, discovered in
2000.[70] Calculations show that two new compounds containing a helium-oxygen bond
could be stable.[71] Two new molecular species, predicted using theory, CsFHeO and
N(CH3)4FHeO, are derivatives of a metastable [F HeO] anion first theorized in 2005
by a group from Taiwan. If confirmed by experiment, the only remaining element
with no known stable compounds would be neon.[72]

Helium has been put inside the hollow carbon cage molecules (the fullerenes) by
heating under high pressure. The endohedral fullerene molecules formed are stable up
to high temperatures. When chemical derivatives of these fullerenes are formed, the
helium stays inside.[73] If helium-3 is used, it can be readily observed by
helium nuclear magnetic resonance spectroscopy.[74] Many fullerenes containing
helium-3 have been reported. Although the helium atoms are not attached by covalent
or ionic bonds, these substances have distinct properties and a definite composition,
like all stoichiometric chemical compounds.

Under extremely high pressures helium can react with many elements. At
130 GPa Na2He is thermodynamically stable with a fluorite structure.[75]

Occurrence and production


Natural abundance

Although it is rare on Earth, helium is the second most abundant element in the known
Universe (after hydrogen), constituting 23% of its baryonic mass.[9] The vast majority
of helium was formed by Big Bang nucleosynthesis one to three minutes after the Big
Bang. As such, measurements of its abundance contribute to cosmological models.
In stars, it is formed by the nuclear fusion of hydrogen inproton-proton chain
reactions and the CNO cycle, part of stellar nucleosynthesis.[61]

In the Earth's atmosphere, the concentration of helium by volume is only 5.2 parts per
million.[76][77] The concentration is low and fairly constant despite the continuous
production of new helium because most helium in the Earth's atmosphere escapes into
space by several processes.[78][79][80] In the Earth's heterosphere, a part of the upper
atmosphere, helium and other lighter gases are the most abundant elements.

Most helium on Earth is a result of radioactive decay. Helium is found in large


amounts in minerals of uranium and thorium,
including cleveite, pitchblende, carnotite and monazite, because they emit alpha
particles (helium nuclei, He2+) to which electrons immediately combine as soon as the
particle is stopped by the rock. In this way an estimated 3000 metric tons of helium
are generated per year throughout the lithosphere.[81][82][83] In the Earth's crust, the
concentration of helium is 8 parts per billion. In seawater, the concentration is only 4
parts per trillion. There are also small amounts in mineral springs, volcanic gas,
and meteoric iron. Because helium is trapped in the subsurface under conditions that
also trap natural gas, the greatest natural concentrations of helium on the planet are
found in natural gas, from which most commercial helium is extracted. The
concentration varies in a broad range from a few ppm up to over 7% in a small gas
field in San Juan County, New Mexico.[84][85]

As of 2011 the world's helium reserves were estimated at 40 billion cubic meters, with
a quarter of that being in the South Pars / North Dome Gas-Condensate field owned
jointly by Qatar and Iran.[86]

Modern extraction and distribution

For large-scale use, helium is extracted by fractional distillation from natural gas,
which can contain up to 7% helium.[87] Since helium has a lower boiling point than any
other element, low temperature and high pressure are used to liquefy nearly all the
other gases (mostly nitrogen and methane). The resulting crude helium gas is purified
by successive exposures to lowering temperatures, in which almost all of the
remaining nitrogen and other gases are precipitated out of the gaseous
mixture. Activated charcoal is used as a final purification step, usually resulting in
99.995% pure Grade-A helium.[10] The principal impurity in Grade-A helium is neon.
In a final production step, most of the helium that is produced is liquefied via
a cryogenic process. This is necessary for applications requiring liquid helium and
also allows helium suppliers to reduce the cost of long distance transportation, as the
largest liquid helium containers have more than five times the capacity of the largest
gaseous helium tube trailers.[37][88]

In 2008, approximately 169 million standard cubic meters (SCM) of helium were
extracted from natural gas or withdrawn from helium reserves with approximately
78% from the United States, 10% from Algeria, and most of the remainder from
Russia, Poland and Qatar.[89] In the United States, most helium is extracted from
natural gas of the Hugoton and nearby gas fields in Kansas, Oklahoma, and the
Panhandle Field in Texas.[37][90] Much of this gas was once sent by pipeline to
the National Helium Reserve, but since 2005 this reserve is being depleted and sold
off.

Diffusion of crude natural gas through special semipermeable membranes and other
barriers is another method to recover and purify helium.[91] In 1996, the U.S.
had proven helium reserves, in such gas well complexes, of about 147 billion standard
cubic feet (4.2 billion SCM).[92] At rates of use at that time (72 million SCM per year
in the U.S.; see pie chart below) this is enough helium for about 58 years of U.S. use,
and less than this (perhaps 80% of the time) at world use rates, although factors in
saving and processing impact effective reserve numbers.

Helium must be extracted from natural gas because it is present in air at only a
fraction of that of neon, yet the demand for it is far higher. It is estimated that if all
neon production were retooled to save helium, that 0.1% of the world's helium
demands would be satisfied. Similarly, only 1% of the world's helium demands could
be satisfied by re-tooling all air distillation plants.[93] Helium can be synthesized by
bombardment of lithium or boron with high-velocity protons, but this process is a
completely uneconomic method of production.[94]

Helium is commercially available in either liquid or gaseous form. As a liquid, it can


be supplied in small insulated containers called dewars which hold up to 1,000 liters
of helium, or in large ISO containers which have nominal capacities as large as
42 m3 (around 11,000 U.S. gallons). In gaseous form, small quantities of helium are
supplied in high-pressure cylinders holding up to 8 m3 (approx. 282 standard cubic
feet), while large quantities of high-pressure gas are supplied in tube trailers which
have capacities of up to 4,860 m3 (approx. 172,000 standard cubic feet).

Conservation advocates

According to helium conservationists like Nobel laureate physicist Robert Coleman


Richardson, the free market price of helium has contributed to "wasteful" usage (e.g.
for helium balloons). Prices in the 2000s have been lowered by U.S. Congress'
decision to sell off the country's large helium stockpile by 2015.[95] According to
Richardson, the current price needs to be multiplied by 20 to eliminate the excessive
wasting of helium. In their book, the Future of helium as a natural
resource (Routledge, 2012), Nuttall, Clarke & Glowacki (2012) also proposed to
create an International Helium Agency (IHA) to build a sustainable market for this
precious commodity.[96]

Applications
The largest single use of liquid helium is to cool the superconducting magnets in
modern MRI scanners.

Estimated 2013 U.S. fractional helium use by category. Total use is 47 million cubic
meters.[97]

Cryogenics (32%)
Pressurizing and purging (18%)
Welding (13%)
Controlled atmospheres (18%)
Leak detection (4%)
Breathing mixtures (2%)
Other (13%)

While balloons are perhaps the best known use of helium, they are a minor part of all
helium use.[32] Helium is used for many purposes that require some of its unique
properties, such as its low boiling point, low density, low solubility, high thermal
conductivity, or inertness. Of the 2008 world helium total production of about 32
million kg (193 million standard cubic meters) helium per year, the largest use (about
22% of the total in 2008) is in cryogenic applications, most of which involves cooling
the superconducting magnets in medical MRI scanners.[98] Other major uses (totalling
to about 60% of use in 1996) were pressurizing and purging systems, maintenance of
controlled atmospheres, welding, and leak detection. Other uses by category were
relatively minor fractions.[99]

Controlled atmospheres

Helium is used as a protective gas in growing silicon and germanium crystals,


in titanium and zirconium production, and in gas chromatography,[51] because it is
inert. Because of its inertness, thermally and calorically perfect nature, high speed of
sound, and high value of the heat capacity ratio, it is also useful in supersonic wind
tunnels[100] and impulse facilities.[101]

Gas tungsten arc welding

Main article: gas tungsten arc welding

Helium is used as a shielding gas in arc welding processes on materials that at


welding temperatures are contaminated and weakened by air or nitrogen.[9] A number
of inert shielding gases are used in gas tungsten arc welding, but helium is used
instead of cheaper argon especially for welding materials that have higher heat
conductivity, like aluminium or copper.

Minor uses

Industrial leak detection

A dual chamber helium leak detection machine

One industrial application for helium is leak detection. Because


helium diffuses through solids three times faster than air, it is used as a tracer gas to
detect leaks in high-vacuum equipment (such as cryogenic tanks) and high-pressure
containers.[102] The tested object is placed in a chamber, which is then evacuated and
filled with helium. The helium that escapes through the leaks is detected by a sensitive
device (helium mass spectrometer), even at the leak rates as small as 109 mbarL/s
(1010 Pam3/s). The measurement procedure is normally automatic and is called
helium integral test. A simpler procedure is to fill the tested object with helium and to
manually search for leaks with a hand-held device.[103]
Helium leaks through cracks should not be confused with gas permeation through a
bulk material. While helium has documented permeation constants (thus a calculable
permeation rate) through glasses, ceramics, and synthetic materials, inert gases such
as helium will not permeate most bulk metals.[104]

Flight

Because of its low density and incombustibility, helium is the gas of choice to fill
airships such as the Goodyear blimp.

Because it is lighter than air, airships and balloons are inflated with helium for lift.
While hydrogen gas is also buoyant, helium has the advantage of being non-
flammable (in addition to being fire retardant). Another minor use is in rocketry,
where helium is used as an ullage medium to displace fuel and oxidizers in storage
tanks and to condense hydrogen and oxygen to make rocket fuel. It is also used to
purge fuel and oxidizer from ground support equipment prior to launch and to pre-
cool liquid hydrogen in space vehicles. For example, the Saturn V rocket used in
the Apollo program needed about 370,000 m3 (13 million cubic feet) of helium to
launch.[51]

Minor commercial and recreational uses

Helium as a breathing gas has no narcotic properties, so helium mixtures such


as trimix, heliox and heliair are used for deep diving to reduce the effects of
narcosis.[105][106] At depths below 150 metres (490 ft) divers breathing heliumoxygen
mixtures begin to experience tremors and a decrease in psychomotor function,
symptoms of high-pressure nervous syndrome.[107] This effect may be countered to
some extent by adding an amount of narcotic gas such as hydrogen or nitrogen to a
heliumoxygen mixture.[108] At these depths the low density of helium is found to
considerably reduce the effort of breathing.[109]

Heliumneon lasers, a type of low-powered gas laser producing a red beam, had
various practical applications which included barcode readers and laser pointers,
before they were almost universally replaced by cheaper diode lasers.[9]

For its inertness and high thermal conductivity, neutron transparency, and because it
does not form radioactive isotopes under reactor conditions, helium is used as a heat-
transfer medium in some gas-cooled nuclear reactors.[102]
Helium, mixed with a heavier gas such as xenon, is useful for thermoacoustic
refrigeration due to the resulting high heat capacity ratio and low Prandtl
number.[110] The inertness of helium has environmental advantages over conventional
refrigeration systems which contribute to ozone depletion or global warming. [111]

Helium is also used in some hard disk drives.[112]

Scientific uses

The use of helium reduces the distorting effects of temperature variations in the space
between lenses in some telescopes, due to its extremely low index of refraction.[10] This
method is especially used in solar telescopes where a vacuum tight telescope tube
would be too heavy.[113][114]

Helium is a commonly used carrier gas for gas chromatography.

The age of rocks and minerals that contain uranium and thorium can be estimated by
measuring the level of helium with a process known as helium dating.[9][10]

Helium at low temperatures is used in cryogenics, and in certain cryogenics


applications. As examples of applications, liquid helium is used to cool certain metals
to the extremely low temperatures required for superconductivity, such as
in superconducting magnets for magnetic resonance imaging. The Large Hadron
Collider at CERN uses 96 metric tons of liquid helium to maintain the temperature at
1.9 kelvin.[115]

Inhalation and safety


Effects

Neutral helium at standard conditions is non-toxic, plays no biological role and is


found in trace amounts in human blood.

Effect of helium on a
human voice
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0:00
The effect of helium on
a human voice

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The speed of sound in helium is nearly three times the speed of sound in air. Because
the fundamental frequency of a gas-filled cavity is proportional to the speed of sound
in the gas, when helium is inhaled there is a corresponding increase in the resonant
frequencies of the vocal tract.[9][116] Thefundamental frequency (sometimes called pitch)
does not change, since this is produced by direct vibration of the vocal folds, which is
unchanged.[117]However, the higher resonant frequencies cause a change in timbre,
resulting in a reedy, duck-like vocal quality. The opposite effect, lowering resonant
frequencies, can be obtained by inhaling a dense gas such as sulfur
hexafluoride or xenon.

Hazards

Inhaling helium can be dangerous if done to excess, since helium is a


simple asphyxiant and so displaces oxygen needed for normal
respiration.[9][118] Fatalities have been recorded, including a youth who suffocated in
Vancouver in 2003 and two adults who suffocated in South Florida in 2006.[119][120] In
1998, an Australian girl (her age is not known) from Victoria fell unconscious and
temporarily turned blue after inhaling the entire contents of a party
balloon.[121][122][123] Breathing pure helium continuously causes death
by asphyxiation within minutes. This fact is utilized in the design of suicide bags.

Inhaling helium directly from pressurized cylinders is extremely dangerous, as the


high flow rate can result in barotrauma, fatally rupturing lung tissue.[118][124]

Death caused by helium is rare. The first media-recorded case was that of a 15-year-
old girl from Texas who died in 1998 from helium inhalation at a friend's party; the
exact type of helium death is unidentified.[121][122][123]

In the United States only two fatalities were reported between 2000 and 2004,
including a man who died in North Carolina of barotrauma in 2002.[119][124] A youth
asphyxiated in Vancouver during 2003, and a 27-year-old man in Australia had an
embolism after breathing from a cylinder in 2000.[119] Since then two adults
asphyxiated in South Florida in 2006,[119][120][125] and there were cases in 2009 and 2010,
one a Californian youth who was found with a bag over his head, attached to a helium
tank,[126] and another teenager in Northern Ireland died of asphyxiation. [127] At Eagle
Point, Oregon a teenage girl died in 2012 from barotrauma at a party.[128][129][130][131] A girl
from Michigan died from hypoxia later in the year.[132]

On February 4, 2015 it was revealed that during the recording of their main TV show
on January 28, a 12-year-old member (name withheld) of Japanese all-girl singing
group 3B Junior suffered from air embolism, losing consciousness and falling in
a coma as a result of air bubbles blocking the flow of blood to the brain, after inhaling
huge quantities of helium as part of a game. The incident was not made public until a
week later.[133][134] The staff of TV Asahi held an emergency press conference to
communicate that the member had been taken to the hospital and is showing signs of
rehabilitation such as moving eyes and limbs, but her consciousness has not been
sufficiently recovered as of yet. Police have launched an investigation due to a neglect
of safety measures.[135][136]

The safety issues for cryogenic helium are similar to those of liquid nitrogen; its
extremely low temperatures can result in cold burns, and the liquid-to-gas expansion
ratio can cause explosions if no pressure-relief devices are installed. Containers of
helium gas at 5 to 10 K should be handled as if they contain liquid helium due to the
rapid and significant thermal expansion that occurs when helium gas at less than 10 K
is warmed to room temperature.[51]

At high pressures (more than about 20 atm or two MPa), a mixture of helium and
oxygen (heliox) can lead to high-pressure nervous syndrome, a sort of reverse-
anesthetic effect; adding a small amount of nitrogen to the mixture can alleviate the
problem.[137][138]

Additional images

3D schematic of a Helium atom

Lithium
From Wikipedia, the free encyclopedia
Jump to: navigation, search
This article is about the chemical element. For the use of lithium as a medication,
see Lithium (medication). For other uses, see Lithium (disambiguation).

Lithium, Li 3

Lithium floating in oil

Spectral lines of lithium

General properties

Name, symbol lithium, Li

Appearance silvery-white

Pronunciation /lim/
LI-thee-m

Lithium in the periodic table

H

Li

Na

helium lithium beryllium

Atomic number 3

Standard atomic weight (Ar) 6.94[1] (6.9386.997)[2]


Element category alkali metal

Group, block group 1 (alkali metals), s-block

Period period 2

Electron configuration [He] 2s1

per shell 2, 1

Physical properties

Phase solid

Melting point 453.65 K (180.50 C, 356.90 F)

Boiling point 1603 K (1330 C, 2426 F)

Density near r.t. 0.534 g/cm3

when liquid, at m.p. 0.512 g/cm3

Critical point 3220 K, 67 MPa(extrapolated)

Heat of fusion 3.00 kJ/mol

Heat of vaporization 136 kJ/mol

Molar heat capacity 24.860 J/(molK)

vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 797 885 995 1144 1337 1610

Atomic properties
Oxidation states +1 (a strongly basicoxide)

Electronegativity Pauling scale: 0.98

Ionization energies 1st: 520.2 kJ/mol


2nd: 7298.1 kJ/mol
3rd: 11815.0 kJ/mol

Atomic radius empirical: 152 pm

Covalent radius 1287 pm

Van der Waals radius 182 pm

Miscellanea

Crystal structure body-centered cubic (bcc)

Speed of soundthin rod 6000 m/s (at 20 C)

Thermal expansion 46 m/(mK) (at 25 C)

Thermal conductivity 84.8 W/(mK)

Electrical resistivity 92.8 nm (at 20 C)

Magnetic ordering paramagnetic

Young's modulus 4.9 GPa

Shear modulus 4.2 GPa

Bulk modulus 11 GPa


Mohs hardness 0.6

Brinell hardness 5 MPa

CAS Registry Number 7439-93-2

History

Discovery Johan August Arfwedson(1817)

First isolation William Thomas Brande(1821)

Most stable isotopes

Main article: Isotopes of lithium

iso NA half-life DM DE (MeV) DP


6
Li 7.5%6Li is stable with 3 neutrons
7
Li 92.5%7Li is stable with 4 neutrons

6
Li content may be as low as 3.75% in
natural samples. 7Li would therefore
have a content of up to 96.25%.

references

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 thealkali
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, it
exhibits a metallic luster, but contact with moist air corrodes the 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 in compounds, 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 oflithium 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 stable nuclides.
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.[3] 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.[4]

Lithium and its compounds have several industrial applications, including heat-
resistant glass and ceramics, lithium grease lubricants, flux additives for iron, steel
and aluminium production, lithium batteries and lithium-ion batteries. These uses
consume more than three quarters 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.

Contents
[hide]

1 Properties
o 1.1 Atomic and physical
o 1.2 Chemistry and compounds
o 1.3 Isotopes
2 Occurrence
o 2.1 Astronomical
o 2.2 Terrestrial
o 2.3 Biological
3 History
4 Production
5 Uses
o 5.1 Ceramics and glass
o 5.2 Electrical and electronics
o 5.3 Lubricating greases
o 5.4 Metallurgy
o 5.5 Other chemical and industrial uses
o 5.6 Nuclear
o 5.7 Medicine
6 Precautions
o 6.1 Regulation
7 See also
8 Notes
9 References
10 External links

Properties
Main article: Alkali metal

Atomic and physical

Lithium pellets covered in white lithium hydroxide (left) and ingots with a thin layer
of black nitride tarnish (right)

Like the other alkali metals, lithium has a single valence electron that is easily given
up to form a cation.[5] 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).[5]

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 intolithium oxide.[5] 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.[6]
Lithium has a very low density of 0.534 g/cm3, 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 g/cm3) being more than 60% denser. Furthermore,
apart from helium and hydrogen, it is less dense than any liquid element, being only
2/3 as dense as liquid nitrogen (0.808 g/cm3).[7] 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 and potassium.

Lithium floating in oil

Lithium's coefficient of thermal expansion is twice that of aluminium and almost four
times that of iron.[8] Lithium is superconductive below 400 K at standard
pressure[9] and at higher temperatures (more than 9 K) at very high pressures (>20
GPa).[10] 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.[11] Multiple allotropic forms have been
reported for lithium at high pressures.[12]

Lithium has a mass specific heat capacity of 3.58 kilojoules per kilogram-kelvin, the
highest of all solids.[13][14] Because of this, lithium metal is often used
in coolants for heat transfer applications.[13]

Chemistry and compounds

Lithium reacts with water easily, but with noticeably less energy than other alkali
metals do. The reaction forms hydrogen gas and lithium hydroxide in aqueous
solution.[5] 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.[15]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).[16]

Hexameric structure of the n-butyllithium fragment in a crystal

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.[17] Lithium 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 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 (Class D type). Lithium is the only metal which reacts
with nitrogen under normal conditions.[18][19]

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 (Li
2O) and peroxide (Li
2O
2) when burnt in O2, salts with similar solubilities, and thermal instability of
the carbonates and nitrides.[16][20] The metal reacts with hydrogen gas at high
temperatures to produce lithium hydride (LiH).[21]

Other known binary compounds include the halides (LiF, LiCl, LiBr, LiI) and
the sulfide (Li
2S), the superoxide (LiO
2), carbide (Li
2C
2). Many other inorganic compounds are known, where lithium combines
with anions to form various salts: borates, amides, carbonate, nitrate,
or borohydride (LiBH
4). Lithium aluminium hydride (LiAlH
4) is commonly used as a reducing agent in organic synthesis.

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.[22] LiHe, a very weakly
interacting van der Waals compound, has been detected at very low temperatures.[23]

Lithium has also been found to exhibit ferromagnetism in its gaseous form, under
certain conditions.[24]

Isotopes

Main article: Isotopes of lithium

Naturally occurring lithium is composed of two stable isotopes, 6Li and 7Li, the latter
being the more abundant (92.5% natural abundance).[5][15][25] 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.[26] 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.[3] 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 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 7.6 1023 s.[27]
7
Li 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.[28] 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.[29] While lithium is created in stars during stellar nucleosynthesis, it is
further burnt. 7Li can also be generated in carbon stars.[30]
Lithium isotopes fractionate substantially during a wide variety of natural
processes,[31] including mineral formation (chemical precipitation), metabolism,
and ion exchange. Lithium ions substitute formagnesium 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.[32]

Nuclear weapons manufacture and other nuclear physics uses are a major source of
artificial lithium fractionation, with the light isotope 6Li being retained by industry and
military stockpiles to such an extent as to slightly but measurably change the 6Li to 7Li
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.[33]

Occurrence

Lithium is about as common as chlorine in the Earth's upper continental crust, on a


per-atom basis.

Astronomical

Main article: Nucleosynthesis

According to modern cosmological theory, lithiumas both of its stable isotopes


lithium-6 and lithium-7was among the 3 elements synthesized in the Big
Bang.[34] Though the amount of lithium generated in Big Bang nucleosynthesis is
dependent upon the number of photons 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.[35] 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.[15]

Nova Centauri 2013 is the first in which evidence of lithium has been found.[36]

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.[37]

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.[15][38][39] 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.[15]
Terrestrial

Lithium mine production (2014) and reserves in tonnes[40]

Country Production Reserves[note 1]

Argentina 2,900 850,000

Australia 13,000 1,500,000

Brazil 400 48,000

Canada (2010) 480 180,000

Chile 12,900 7,500,000

People's Republic of China 5,000 3,500,000

Portugal 570 60,000

Zimbabwe 1,000 23,000

World total 36,000 13,500,000


See also: Lithium minerals

Although lithium is widely distributed on Earth, it does not naturally occur in


elemental form due to its high reactivity.[5] 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),[41][42] or
25 micromolar;[43] higher concentrations approaching 7 ppm are found
near hydrothermal vents.[42]

Estimates for the Earth's crustal content range from 20 to 70 ppm by weight.[16] 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.[16] Another significant mineral of lithium islepidolite.[44] A
newer source for lithium is hectorite clay, the only active development of which is
through the Western Lithium Corporation in the United States.[45] At 20 mg lithium per
kg of Earth's crust,[46] 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."[47]
One of the largest reserve bases[note 1] of lithium is in the Salar de Uyuni area of Bolivia,
which has 5.4 million tonnes. The US Geological Survey estimates that in 2010 Chile
had the largest reserves by far (7.5 million tonnes)[48] and the highest annual
production (8,800 tonnes). Other major suppliers include Australia, Argentina and
China.[40][49]

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."[50] 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."[51]

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.[42] Marine organisms tend to
bioaccumulate lithium more than terrestrial ones.[52] It is not known whether lithium
has a physiological role in any of these organisms,[42] 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.[53] Observational
studies in Japan, reported in 2011, suggested that naturally occurring lithium in
drinking water may increase human lifespan.[54]

History
Johan August Arfwedson is credited with the discovery of lithium in 1817

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.[55][56][57][58] 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.[59][60][61][62] This element formed
compounds similar to those of sodium and potassium, though
its carbonate and hydroxide were less soluble in water and more alkaline.[63] 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".[5][57][62]

Arfwedson later showed that this same element was present in the
minerals spodumene and lepidolite.[57] In 1818, Christian Gmelin was the first to
observe that lithium salts give a bright red color to flame.[64][57] However, both
Arfwedson and Gmelin tried and failed to isolate the pure element from its
salts.[57][62][65] It was not isolated until 1821, when William Thomas Brande obtained it
byelectrolysis of lithium oxide, a process that had previously been employed by the
chemist Sir Humphry Davy to isolate the alkali metals potassium and
sodium.[66][15][65][67][68] 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).[69] In 1855, larger quantities of lithium were produced through the electrolysis
of lithium chloride by Robert Bunsen and Augustus Matthiessen.[70][57] 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.[57][71][72]
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 inWorld 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.[33][73]

Lithium was used to decrease the melting temperature of glass and to improve the
melting behavior of aluminium oxide when using the Hall-Hroult process.[74][74] 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.[73] 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 21st century.

The development of lithium ion batteries increased the demand for lithium and
became the dominant use in 2007.[75] With the surge of lithium demand in batteries in
the 2000s, new companies have expanded brine extraction efforts to meet the rising
demand.[76][77]

Production
Satellite images of the Salar del Hombre Muerto, Argentina (left), and Uyuni, Bolivia
(right), salt flats are rich in lithium. The lithium-rich brine is concentrated by pumping
it into solar evaporation ponds (visible in the left image).

World production trend of lithium

Since the end of World War II lithium production has been greatly increased. The
metal is separated from other elements in igneous minerals such as those above.
Lithium salts are extracted from the water in mineral springs, brine pools and brine
deposits. The metal is produced through electrolysis from a mixture of fused
55% lithium chloride and 45% potassium chloride at about 450 C.[78] In 1998 it was
about 95 USD/kg (or 43 USD/lb).[79]

Worldwide identified reserves of lithium in 2008 were estimated by the US


Geological Survey as 13 million tonnes,[40] though it is extremely difficult to accurately
estimate the world's lithium reserves,[80] and some have predicted a Lithium Gold
Rush.[80][81] as finite reserves are depleted. 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.[13] 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.[82]According to the US Geological Survey,
Bolivia's Uyuni Desert has 5.4 million tonnes of lithium.[82][83] 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.[84]

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%[85] 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[86]

A potential source is geothermal wells. Geothermal fluids carry leachates to the


surface;[87] recovery of lithium has been demonstrated in the field.[88] 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.[89]

There are differing opinions about the potential growth of lithium production. A 2008
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'".[49]

However, according to a 2011 study conducted at Lawrence Berkeley National


Laboratory and the University 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.[90] Another 2011 study by researchers
from the University 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, plug-in 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 12
20 million tons, depending on the scenarios regarding economic growth and recycling
rates.[91]
On June 9, 2014, the Financialist publication, produced by the Credit
Suisse company, stated that demand for lithium is growing at more than 12 percent a
year; according to Credit Suisse, this rate exceeds projected availability by 25 percent.
The publication compared the 2014 lithium situation with oil, whereby "higher oil
prices spurred investment in expensive deepwater and oil sands production
techniques"; that is, the price of lithium will continue to rise until more expensive
production methods that can boost total output receive the attention of investors.[92]

Uses

Estimates of global lithium uses in 2011[93]


Ceramics and glass (29%)
Batteries (27%)
Lubricating greases (12%)
Continuous casting (5%)
Air treatment (4%)
Polymers (3%)
Primary aluminum production (2%)
Pharmaceuticals (2%)
Other (16%)

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 of thermal expansion.[94] Lithium oxides are a
component of ovenware. Worldwide, this is the single largest use for lithium
compounds.[93][clarification needed][citation needed] Lithium carbonate (Li2CO3) is generally used in this
application[clarification needed] upon heating it converts to the oxide.[95]

Electrical and electronics


In the later years of the 20th century, owing to its high electrode potential, lithium
became an important component of the electrolyte and of one of the electrodes in
batteries. Because of its low atomic mass, it has a high charge- and power-to-weight
ratio. A typical lithium-ion battery can generate approximately 3 volts per cell,
compared with 2.1 volts for lead-acid or 1.5 volts for zinc-carbon cells. Lithium-ion
batteries, which are rechargeable and have a high energy density, should not be
confused with lithium batteries, which are disposable (primary) batteries with lithium
or its compounds as theanode.[96][97] Other rechargeable batteries that use lithium
include the lithium-ion polymer battery, lithium iron phosphate battery, and
the nanowire battery.

Lubricating greases

Main article: Lithium grease

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.[13][98][99]

Metallurgy

Lithium (e.g. as lithium carbonate) is used as an additive to continuous casting mould


flux slags where it increases fluidity,[100][101] a use which accounts for 5% of global
lithium use (2011).[40] Lithium compounds are also used as additives (fluxes)
to foundry sand for iron casting to reduce veining.[102]

Lithium (as lithium fluoride) is used as an additive to aluminium smelters (Hall


Hroult process), reducing melting temperature and increasing electrical
resistance,[103] a use which accounts for 3% of production (2011).[40]

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.[citation needed] Alloys of the metal with aluminium, cadmium, copper
and manganese are used to make high-performance aircraft parts (see also Lithium-
aluminium alloys).[104]

Other chemical and industrial uses


Lithium use in flares andpyrotechnics is due to its rose-red flame.[105]

Pyrotechnics

Lithium compounds are used as pyrotechnic colorants and oxidizers in


red fireworks and flares.[13][106]

Air purification

Lithium chloride and lithium bromide are hygroscopic and are used as desiccants for
gas streams.[13] Lithium hydroxide and lithium peroxide are the salts most used in
confined areas, such as aboardspacecraft and submarines, for carbon dioxide removal
and air purification. Lithium hydroxide absorbs carbon dioxide from the air by
forming lithium carbonate, and is preferred over other alkaline hydroxides for its low
weight.

Lithium peroxide (Li2O2) in presence of moisture not only reacts with carbon dioxide
to form lithium carbonate, but also releases oxygen.[107][108] The reaction is as follows:

2 Li2O2 + 2 CO2 2 Li2CO3 + O2.

Some of the aforementioned compounds, as well as lithium perchlorate, are used


in oxygen candles that supply submarines with oxygen. These can also include small
amounts of boron, magnesium,aluminum, silicon, titanium, manganese, and iron.[109]

Optics

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 one of the
lowest refractive indexes and the farthest transmission range in the deep UV of most
common materials.[110] 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 intensity is proportional to the absorbed dose, thus allowing this
to be quantified.[111] Lithium fluoride is sometimes used in focal lenses
of telescopes.[13][112]

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.[113]

Organic and polymer chemistry

Organolithium compounds are widely used in the production of polymer and fine-
chemicals. In the polymer industry, which is the dominant consumer of these reagents,
alkyl lithium compounds arecatalysts/initiators.[114] in anionic
polymerization of unfunctionalized olefins.[115][116][117] For the production of fine
chemicals, organolithium compounds function as strong bases and as reagents for the
formation of carbon-carbon bonds. Organolithium compounds are prepared from
lithium metal and alkyl halides.[118]

Many other lithium compounds are used as reagents to prepare organic compounds.
Some popular compounds include lithium aluminium hydride (LiAlH4), lithium
triethylborohydride (LiBH(C2H5)3). n-Butyllithium (C4H9Li) and tert-
butyllithium (C4H9Li) are commonly used as extremely strong bases called superbase.

Military applications

Metallic lithium and its complex hydrides, such as Li[AlH4], are used as high-energy
additives to rocket propellants.[15] Lithium aluminum hydride can also be used by itself
as a solid fuel.[119]

The launch of a torpedo using lithium as fuel

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 heat, which is used to generate steam. The steam propels the
torpedo in a closed Rankine cycle.[120]
Lithium hydride containing lithium-6 is used in hydrogen bombs. In the bomb, it is
placed around the core of a nuclear bomb.[121]

Nuclear

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% lithium-6 from which
large amounts of lithium-6 have been produced by isotope separation for use
in nuclear weapons.[122] Lithium-7 gained interest for use in nuclear reactor coolants.[123]

Lithium deuteride was used as fuel in the Castle Bravo nuclear device.

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.[124]

Lithium fluoride, when highly enriched in the lithium-7 isotope, forms the basic
constituent of the 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. In addition, 7Li, Be, and F are among the few nuclides with
low enough thermal neutron capture cross-sections not to poison the fission reactions
inside a nuclear fission reactor.[note 2][125]

In conceptualized nuclear fusion power plants, lithium will be used to produce tritium
in magnetically confined reactors using deuterium and tritium as the fuel. Naturally
occurring tritium is extremely rare, and must be synthetically produced by
surrounding the reacting plasma with a 'blanket' containing lithium where neutrons
from the deuterium-tritium reaction in the plasma will fission the lithium to produce
more tritium:
6
Li + 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.[126][127] (Nuclear reactions and human-directed nuclear transmutation had been
accomplished as early as 1917, but by using natural radioactive bombardment
with alpha particles).

In 2013, the US Government Accountability Office said a shortage of lithium-7


critical to the operation of 65 out of 100 American nuclear reactors places their
ability to continue to provide electricity at some risk. The problem stems from the
decline of US nuclear infrastructure. The equipment needed to separate lithium-6 from
lithium-7 is mostly a cold war leftover. The US shut down most of this machinery in
1963, when it had a huge surplus of separated lithium, mostly consumed during the
twentieth century. The report said it would take five years and $10 million to $12
million to reestablish the ability to separate lithium-6 from lithium-7.[128]

Reactors that use lithium-7 heat water under high pressure and transfer heat through
heat exchangers that are prone to corrosion. The reactors use lithium to counteract the
corrosive effects of boric acid, which is added to the water to absorb excess
neutrons.[128]

Medicine

Main article: Lithium (medication)

Lithium is useful in the treatment of bipolar disorder.[129] Lithium salts may also be
helpful for related diagnoses, such as schizoaffective disorder and cyclic major
depression. The active part of these salts is the lithium ion Li+.[129] They may increase
the risk of developing Ebstein's cardiac anomaly in infants born to women who take
lithium during the first trimester of pregnancy.[130]

Lithium has also been researched as a possible treatment for cluster headaches.[131]

Precautions

NFPA 704
"fire diamond"
2
3
2
W

Fire diamond
hazard sign for
lithium metal[132]

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.[133]

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 pseudoephedrineand ephedrine to methamphetamine in the Birch
reduction method, which employs solutions of alkali metals dissolved in
anhydrous ammonia.[134][135] 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
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.[136][137]

Beryllium
From Wikipedia, the free encyclopedia
Jump to: navigation, search

Beryllium, Be 4

General properties

Name, symbol beryllium, Be

Appearance white-gray metallic

Pronunciation /brlim/
b-RIL-ee-m

Beryllium in the periodic table



Be

Mg

lithium beryllium boron

Atomic number 4

Standard atomic 9.0121831(5)[1]


weight () (Ar)

Element category alkaline earth metal


Group, block group 2 (alkaline earth metals),s-block

Period period 2

Electron configuration [He] 2s2

per shell 2, 2

Physical properties

Phase solid

Melting point 1560 K (1287 C, 2349 F)

Boiling point 3243 K (2970 C, 5378 F)

Density near r.t. 1.85 g/cm3

when liquid, at m.p. 1.690 g/cm3

Critical point 5205 K, MPa (extrapolated)

Heat of fusion 12.2 kJ/mol

Heat of vaporization 292 kJ/mol

Molar heat capacity 16.443 J/(molK)

vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 1462 1608 1791 2023 2327 2742

Atomic properties

Oxidation states +2, +1[2] (an amphotericoxide)


Electronegativity Pauling scale: 1.57

Ionization energies 1st: 899.5 kJ/mol


2nd: 1757.1 kJ/mol
3rd: 14,848.7 kJ/mol
(more)

Atomic radius empirical: 112 pm

Covalent radius 963 pm

Van der Waals radius 153 pm

Miscellanea

Crystal structure hexagonal close-packed (hcp)

Speed of soundthin rod 12,890 m/s (at r.t.)[3]

Thermal expansion 11.3 m/(mK) (at 25 C)

Thermal conductivity 200 W/(mK)

Electrical resistivity 36 nm (at 20 C)

Magnetic ordering diamagnetic

Young's modulus 287 GPa

Shear modulus 132 GPa

Bulk modulus 130 GPa


Poisson ratio 0.032

Mohs hardness 5.5

Vickers hardness 1670 MPa

Brinell hardness 5901320 MPa

CAS Registry Number 7440-41-7

History

Discovery Louis Nicolas Vauquelin(1797)

First isolation Friedrich Whler & Antoine Bussy (1828)

Most stable isotopes

Main article: Isotopes of beryllium

iso NA half-life DM DE (MeV) DP


0.862 7
Li
7
Be trace 53.12 d
0.477
9
Be 100%9Be is stable with 5 neutrons
10
Be trace 1.36106 y 0.556 10
B

references

Beryllium is a chemical element with symbol Be and atomic number 4. It is created


through stellar nucleosynthesis and is a relatively rare element in the universe. 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 improves many physical properties when added as an alloying element


to aluminium, copper (notably the alloy beryllium copper), iron andnickel.[4] Tools
made of beryllium copper alloys are strong and hard and do not create sparks when
they strike a steel surface. In structural applications, the combination of high flexural
rigidity, thermal stability, thermal conductivity and low density (1.85 times that of
water) make beryllium metal a desirable aerospace material for aircraft
components, missiles, spacecraft, and satellites.[4] 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 components of particle physics experiments.[4] The high thermal
conductivities of beryllium and beryllium oxide have led to their use in thermal
management applications.

The commercial use of beryllium requires the use of appropriate dust control
equipment and industrial controls at all times because of the toxicity of inhaled
beryllium-containing dusts that can cause a chronic life-threatening allergic disease in
some people called berylliosis.[5]

Contents
[hide]

1 Characteristics
o 1.1 Physical properties
o 1.2 Nuclear properties
o 1.3 Isotopes and nucleosynthesis
o 1.4 Occurrence
2 Production
3 Chemical properties
4 History
o 4.1 Etymology
5 Applications
o 5.1 Radiation windows
o 5.2 Mechanical applications
o 5.3 Mirrors
o 5.4 Magnetic applications
o 5.5 Nuclear applications
o 5.6 Acoustics
o 5.7 Electronic
6 Precautions
7 See also
8 Notes
9 References
10 Further reading
11 External links

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.[4] It has exceptionalstiffness (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 Jkg1K1) and thermal conductivity (216
Wm1K1), which make beryllium the metal with the best heat dissipation
characteristics per unit weight. In combination with the relatively low coefficient of
linearthermal expansion (11.4106 K1), these characteristics result in a unique
stability under conditions of thermal loading.[6]

Nuclear properties

Naturally occurring beryllium, save for slight contamination by cosmogenic


radioisotopes, is essentially beryllium-9, which has a nuclear spin of 32. Beryllium has
a large scattering cross section for high-energy neutrons, about 6 barns for energies
above approximately 10 keV. 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 9Be also undergoes a (n,2n) neutron reaction
with neutron energies over about 1.9 MeV, to produce 8Be, 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:[7]
9
4Be + n 2(4
2He) + 2n

Neutrons are liberated when beryllium nuclei are struck by energetic alpha
particles[6] 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.[7]

Beryllium also releases neutrons under bombardment by alpha 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

Main articles: Isotopes of beryllium and beryllium-10

Both stable and unstable isotopes of beryllium are created in stars, but the
radioisotopes 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.[8] Primordial beryllium
contains only one stable isotope, 9Be, and therefore beryllium is a monoisotopic
element.

Plot showing variations in solar activity, including variation in sunspot number (red)
and 10Be concentration (blue). Note that the beryllium scale is inverted, so increases on
this scale indicate lower 10Be levels

Radioactive cosmogenic 10Be is produced in the atmosphere of the Earth by the cosmic
ray spallation of oxygen.[9] 10Be accumulates at the soil surface, where its relatively
long half-life (1.36 million years) permits a long residence time before decaying
to boron-10. Thus, 10Be and its daughter products are used to examine natural soil
erosion, soil formation and the development of lateritic soils, and as a proxy for
measurement of the variations in solar activity and the age of ice cores.[10] The
production of 10Be is inversely proportional to solar activity, because increased solar
wind during periods of high solar activity decreases the flux of galactic cosmic
rays that reach the Earth.[9] Nuclear explosions also form 10Be by the reaction of fast
neutrons with 13C in the carbon dioxide in air. This is one of the indicators of past
activity at nuclear weapon test sites.[11] The isotope 7Be (half-life 53 days) is also
cosmogenic, and shows an atmospheric abundance linked to sunspots, much like 10Be.
8
Be has a very short half-life of about 71017 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.[12] This is due to the lack of sufficient time during
the Big Bang's nucleosynthesis phase to produce carbon by the fusion of 4He nuclei
and the very low concentrations of available beryllium-8. The
British astronomer Sir Fred Hoyle first showed that the energy levels of 8Be and 12C
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.[13]

The innermost electrons of beryllium may contribute to chemical bonding. Therefore,


when 7Be decays by electron capture, it does so by taking electrons from atomic
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.[14]

The shortest-lived known isotope of beryllium is 13Be which decays through neutron
emission. It has a half-life of 2.7 1021 s. 6Be is also very short-lived with a half-life
of 5.0 1021 s.[15] The exotic isotopes 11Be and 14Be are known to exhibit a nuclear
halo.[16] This phenomenon can be understood as the nuclei of 11Be and 14Be have,
respectively, 1 and 4 neutrons orbiting substantially outside the classical Fermi
'waterdrop' model of the nucleus.

Occurrence
Beryllium ore

Emerald is a naturally occurringcompound of beryllium.

The Sun has a concentration of 0.1 parts per billion (ppb) of beryllium. [17] Beryllium
has a concentration of 2 to 6 parts per million (ppm) in the Earth's crust.[18] It is most
concentrated in the soils, 6 ppm, and is found in 0.2 parts per trillion (ppt) of sea
water.[19] Trace amounts of 9Be are found in the Earth's atmosphere.[19] In sea water,
beryllium is exceedingly rare, comprising only 0.0006 ppb by weight. [20] In stream
water, however, beryllium is more abundant with 0.1 ppb by weight.[21]

Beryllium is found in over 100 minerals,[22] but most are uncommon to rare. The more
common beryllium containing minerals
include: bertrandite (Be4Si2O7(OH)2), beryl (Al2Be3Si6O18), chrysoberyl(Al2BeO4)
and phenakite (Be2SiO4). Precious forms of beryl are aquamarine, red
beryl and emerald.[6][23][24] The green color in gem-quality forms of beryl comes from
varying amounts of chromium (about 2% for emerald).[25]

The two main ores of beryllium, beryl and bertrandite, are found in Argentina, Brazil,
India, Madagascar, Russia and the United States.[25] Total world reserves of beryllium
ore are greater than 400,000 tonnes.[25]

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.[26]

Beryllium is most commonly extracted from the mineral beryl, which is


either sintered using an extraction agent or melted into a soluble mixture. The
sintering process involves mixing beryl with sodium fluorosilicate and soda at 770 C
(1,420 F) to form sodium fluoroberyllate, aluminium oxide and silicon
dioxide.[4] Beryllium hydroxide is precipitated from a solution of sodium
fluoroberyllate andsodium hydroxide in water. Extraction of beryllium using the melt
method involves grinding beryl into a powder and heating it to 1,650 C
(3,000 F).[4] The melt is quickly cooled with water and then reheated 250 to 300 C
(482 to 572 F) in concentrated sulfuric acid, mostly yielding beryllium
sulfate and aluminium sulfate.[4] 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 1,000 C (1,830 F) to form
beryllium fluoride.[4] Heating the fluoride to 900 C (1,650 F) withmagnesium forms
finely divided beryllium, and additional heating to 1,300 C (2,370 F) creates the
compact metal.[4] Heating beryllium hydroxide forms the oxide, which becomes
beryllium chloride when combined with carbon and chlorine. Electrolysis of molten
beryllium chloride is then used to obtain the metal.[4]

Chemical properties
See also: Category:Beryllium compounds.

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.[4] It is more chemically similar
to aluminium than its close neighbors in the periodic table due to having a similar
charge-to-radius ratio.[4] An oxide layer forms around beryllium that prevents further
reactions with air unless heated above 1000 C.[4][27] Once ignited, beryllium burns
brilliantly forming a mixture of beryllium oxide and beryllium nitride.[27] 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.[4] This behavior is similar to that of
aluminium metal. Beryllium also dissolves in alkali solutions.[4]
Beryllium hydrolysis as a function of pH
Water molecules attached to Be are omitted

The beryllium atom has the electronic configuration [He] 2s2. 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.[28] 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 numberof 4 because
its two covalent bonds fill half of this octet.[4] 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 forms octahedral complexes thus absorbing other cations such
as Al3+ which might interfere for example, in the solvent extraction of a complex
formed between Be2+ and acetylacetone.[29] 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.[citation
needed]

Solutions of beryllium salts, e.g. beryllium sulfate and beryllium nitrate, are acidic
because of hydrolysis of the [Be(H2O)4]2+ ion.

[Be(H2O)4]2+ + H2O [Be(H2O)3(OH)]+ + H3O+

Other products of hydrolysis include the trimeric ion [Be3(OH)3(H2O)6]3+. Beryllium


hydroxide, Be(OH)2, is insoluble even in acidic solutions with pH less than 6, that is at
biological pH. It isamphoteric 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
BeF4 tetrahedra. BeCl2 and BeBr2 have chain structures with edge-shared tetrahedra.
All beryllium halides have a linear monomeric molecular structure in the gas phase.[27]
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,[30] 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.[31][32][33][34]

Order and disorder in difluorides

The strong and stable ionic Disordered structure of beryllium


fluorite structure adopted glass (sketch, two dimensions)
bycalcium difluoride and many
other difluorides

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.[27] Beryllium sulfide, selenide and telluride are known, all having the zincblende
structure.[28]
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.[28] 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.[28] No beryllium silicide has been identified.[27]

History
The mineral beryl, which contains beryllium, has been used at least since
the Ptolemaic dynasty of Egypt.[35] In the first century CE, Roman naturalist Pliny the
Elder mentioned in his encyclopediaNatural History that beryl
and emerald ("smaragdus") were similar.[36] The Papyrus Graecus Holmiensis, written
in the third or fourth century CE, contains notes on how to prepare artificial emerald
and beryl.[36]

Louis-Nicolas Vauquelindiscovered beryllium

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.[37] Mineralogist Ren Just Hay discovered that both crystals are
geometrically identical, and he asked chemist Louis-Nicolas Vauquelin for a chemical
analysis.[35]

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
additional alkali.[38] 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.[39] Klaproth preferred the name "beryllina" due to fact that yttria also
formed sweet salts.[40][41] The name "beryllium" was first used by Whler in 1828.[42]
Friedrich Whler was one of the men who independently isolated beryllium

Friedrich Whler[43] and Antoine Bussy[44] independently isolated beryllium in 1828 by


the chemical reaction of metallic potassium with beryllium 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.[45] The highly reactive potassium had been produced by
the electrolysis 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.[45] The first commercially successful process for producing beryllium was
developed in 1932 by Alfred Stock and Hans Goldschmidt.[45] Their process involves
the electrolysis 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.[25] This same method is used in one class of radioisotope-based
laboratory neutron sources that produce 30 neutrons for every million particles.[18]

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.[46]

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.[47]

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.[25] 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.[48]

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.[49][50]

Etymology

Early precursors 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 related to the name of the modern city of Belur.[51] For about 160 years,
beryllium was also known as glucinum or glucinium (with the accompanying
chemical symbol "Gl",[52] or "G" [53]), the name coming from the Greek word for sweet:
, due to the sweet taste of beryllium salts.[54]

Applications
It is estimated that most beryllium is used for military applications, so information is
not readily available.[55]

Radiation windows
Beryllium target which "converts" a proton beam into a neutron beam

A square beryllium foil mounted in a steel case to be used as a window between a


vacuum chamber and an X-ray microscope. Beryllium is highly transparent to X-rays
owing to its low atomic number.

Because of its low atomic number and very low absorption for X-rays, the oldest and
still one of the most important applications of beryllium is in radiation windows
for X-ray tubes.[25] Extreme demands are placed on purity and cleanliness of beryllium
to avoid artifacts in the X-ray images. Thin beryllium foils are used as radiation
windows for X-ray detectors, and the extremely low absorption minimizes the heating
effects caused by high intensity, low energy X-rays typical of synchrotron radiation.
Vacuum-tight windows and beam-tubes for radiation experiments on synchrotrons are
manufactured exclusively from beryllium. In scientific setups for various X-ray
emission studies (e.g., energy-dispersive X-ray spectroscopy) the sample holder is
usually made of beryllium because its emitted X-rays have much lower energies
(~100 eV) than X-rays from most studied materials.[6]

Low atomic number also makes beryllium relatively transparent to energetic particles.
Therefore it is used to build the beam pipe around the collision region in particle
physics setups, such as all four main detector experiments at the Large Hadron
Collider (ALICE, ATLAS, CMS, LHCb),[56] the Tevatron and the SLAC. The low
density of beryllium allows collision products to reach the surrounding detectors
without significant interaction, its stiffness allows a powerful vacuum to be produced
within the pipe to minimize interaction with gases, its thermal stability allows it to
function correctly at temperatures of only a few degrees above absolute zero, and
its diamagnetic nature keeps it from interfering with the complex multipole magnet
systems used to steer and focus the particle beams.[57]

Mechanical applications

Because of its stiffness, light weight and dimensional stability over a wide
temperature range, beryllium metal is used for lightweight structural components in
the defense and aerospace industries in high-speed aircraft, guided
missiles, spacecraft, and satellites. Several liquid-fuel rockets have used rocket
nozzles made of pure beryllium.[58][59] Beryllium powder was itself studied as a rocket
fuel, but this use has never materialized.[25] A small number of bicycle frames were
built with beryllium, at "astonishing" prices.[60] From 1998 to 2000,
the McLaren Formula One team used Mercedes-Benzengines with beryllium-
aluminium-alloy pistons.[61] The use of beryllium engine components was banned
following a protest by Scuderia Ferrari.[62]

Mixing about 2.0% beryllium into copper forms an alloy called beryllium copper that
is six times stronger than copper alone.[63] Beryllium alloys are used in many
applications because of their combination of elasticity, high electrical
conductivity and thermal conductivity, high strength and hardness, nonmagnetic
properties, as well as good corrosion and fatigue resistance.[25][4] These applications
include non-sparking tools that are used near flammable gases (beryllium nickel),
in springs and membranes (beryllium nickel and beryllium iron) used in surgical
instruments and high temperature devices.[25][4] As little as 50 parts per million of
beryllium alloyed with liquid magnesium leads to a significant increase in oxidation
resistance and decrease in flammability.[4]

Beryllium Copper Adjustable Wrench

The high elastic stiffness of beryllium has led to its extensive use in precision
instrumentation, e.g. in inertial guidance systems and in the support mechanisms for
optical systems.[6] Beryllium-copper alloys were also applied as a hardening agent in
"Jason pistols", which were used to strip the paint from the hulls of ships. [64]

An earlier major application of beryllium was in brakes for military airplanes because
of its hardness, high melting point, and exceptional ability to dissipate heat.
Environmental considerations have led to substitution by other materials.[6]
To reduce costs, beryllium can be alloyed with significant amounts of aluminium,
resulting in the AlBeMet alloy (a trade name). This blend is cheaper than pure
beryllium, while still retaining many desirable properties.

Mirrors

Beryllium mirrors are of particular interest. Large-area mirrors, frequently with


a honeycomb support structure, are used, for example, in meteorological
satellites where low weight and long-term dimensional stability are critical. Smaller
beryllium mirrors are used in optical guidance systems and in fire-control systems,
e.g. in the German-made Leopard 1 and Leopard 2 main battle tanks. In these systems,
very rapid movement of the mirror is required which again dictates low mass and high
rigidity. Usually the beryllium mirror is coated with hard electroless nickel
plating which can be more easily polished to a finer optical finish than beryllium. In
some applications, though, the beryllium blank is polished without any coating. This
is particularly applicable to cryogenic operation where thermal expansion mismatch
can cause the coating to buckle.[6]

The James Webb Space Telescope[65] will have 18 hexagonal beryllium sections for its
mirrors. Because JWST will face a temperature of 33 K, the mirror is made of gold-
plated beryllium, capable of handling extreme cold better than glass. Beryllium
contracts and deforms less than glass and remains more uniform in such
temperatures.[66] For the same reason, the optics of the Spitzer Space Telescope are
entirely built of beryllium metal.[67]

Magnetic applications

Sphere Beryllium B52 -Gyrocompass

Beryllium is non-magnetic. Therefore, tools fabricated out of beryllium-based


materials are used by naval or military explosive ordnance disposal teams for work on
or near naval mines, since these mines commonly have magnetic fuzes.[68][dubious ] They
are also found in maintenance and construction materials near magnetic resonance
imaging (MRI) machines because of the high magnetic fields generated by them.[69] In
the fields of radio communications and powerful (usually military) radars, hand tools
made of beryllium are used to tune the highly
magnetic klystrons, magnetrons, traveling wave tubes, etc., that are used for
generating high levels of microwave power in the transmitters.[70]

Nuclear applications

Thin plates or foils of beryllium are sometimes used in nuclear weapon designs as the
very outer layer of the plutonium pits in the primary stages of thermonuclear bombs,
placed to surround the fissilematerial. These layers of beryllium are good "pushers"
for the implosion of the plutonium-239, and they are also good neutron reflectors, just
as they are in beryllium-moderated nuclear reactors.[71]

Beryllium is also commonly used in some neutron sources in laboratory devices in


which relatively few neutrons are needed (rather than having to use a nuclear reactor,
or a particle accelerator-poweredneutron generator). For this purpose, a target of
beryllium-9 is bombarded with energetic alpha particles from a radioisotope such
as polonium-210, radium-226, plutonium-239, or americium-241. In the nuclear
reaction that occurs, a beryllium nucleus is transmuted into carbon-12, and one free
neutron is emitted, traveling in about the same direction as the alpha particle was
heading. Such alpha decaydriven beryllium neutron sources, named "urchin" neutron
initiators, were used some in early atomic bombs.[71] Neutron sources in which
beryllium is bombarded with gamma rays from a gamma decayradioisotope, are also
used to produce laboratory neutrons.[72]

Two CANDU fuel bundles: Each about 50 cm in length and 10 cm in diameter. Notice
the small appendages on the fuel clad surfaces

Beryllium is also used in fuel fabrication for CANDU reactors. The fuel elements
have small appendages that are resistance brazed to the fuel cladding using an
induction brazing process with Be as the braze filler material. Bearing pads are brazed
on to prevent fuel bundle to pressure tube contact, and inter-element spacer pads are
brazed on to prevent element to element contact.
Beryllium is also used at the Joint European Torus nuclear-fusion research laboratory,
and it will be used in the more advanced ITER to condition the components which
face the plasma.[73] Beryllium has also been proposed as a cladding material for nuclear
fuel rods, because of its good combination of mechanical, chemical, and nuclear
properties.[6] Beryllium fluoride is one of the constituent salts of the eutectic salt
mixture FLiBe, which is used as a solvent, moderator and coolant in many
hypothetical molten salt reactor designs, including the liquid fluoride thorium
reactor (LFTR).[74]

Acoustics

The low weight and high rigidity of beryllium make it useful as a material for high-
frequency speaker drivers. Because beryllium is expensive (many times more
than titanium), hard to shape due to its brittleness, and toxic if mishandled,
beryllium tweeters are limited to high-end home,[75][76][77] pro audio, and public
address applications.[78][79] Due to the high performance of beryllium in acoustics, for
marketing purposes some products are claimed to be made of the material when they
are not.[80]

Electronic

Beryllium is a p-type dopant in III-V compound semiconductors. It is widely used in


materials such as GaAs, AlGaAs, InGaAs and InAlAs grown by molecular beam
epitaxy (MBE).[81] Cross-rolled beryllium sheet is an excellent structural support
for printed circuit boards in surface-mount technology. In critical electronic
applications, beryllium is both a structural support and heat sink. The application also
requires a coefficient of thermal expansion that is well matched to the alumina
and polyimide-glass substrates. The beryllium-beryllium oxide composite "E-
Materials" have been specially designed for these electronic applications and have the
additional advantage that the thermal expansion coefficient can be tailored to match
diverse substrate materials.[6]

Beryllium oxide is useful for many applications that require the combined properties
of an electrical insulator and an excellent heat conductor, with high strength and
hardness, and a very high melting point. Beryllium oxide is frequently used as an
insulator base plate in high-power transistors in radio frequency transmitters for
telecommunications. Beryllium oxide is also being studied for use in increasing
the thermal conductivity of uranium dioxide nuclear fuel pellets.[82] Beryllium
compounds were used in fluorescent lighting tubes, but this use was discontinued
because of the diseaseberylliosis which developed in the workers who were making
the tubes.[83]
Precautions
Main article: Beryllium poisoning

Approximately 35 micrograms of beryllium is found in the human body, but this


amount is not considered harmful.[84] Beryllium is chemically similar
to magnesium and therefore can displace it fromenzymes, which causes them to
malfunction.[84] 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.[84] The International Agency for Research on Cancer (IARC) lists
beryllium and beryllium compounds as Category 1 carcinogens.[85]

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 manufacturingfluorescent lamps in 1949 in the United States had
beryllium-related lung diseases.[86] 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.[87]

Beryllium may be found in coal slag. When the slag is formulated into an abrasive
agent for blasting paint and rust from hard surfaces, the beryllium can become
airborne and become a source of exposure.[88]

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.[4] 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.[89]

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).[90][91]

Boron
From Wikipedia, the free encyclopedia
Jump to: navigation, search
This article is about the chemical element. For other uses, see Boron
(disambiguation).
Not to be confused with borium, a tungsten carbide product.

Boron, B 5

-rhombohedral boron (most thermodynamically stable allotrope)[1]

General properties

Name, symbol boron, B

Appearance black-brown

Allotropes -, -rhombohedral, -tetragonal (and more)

Pronunciation /brn/

Boron in the periodic table




B

Al

beryllium boron carbon

Atomic number 5

Standard atomic weight (Ar) 10.81[2] (10.80610.821)[3]

Element category metalloid

Group, block group 13, p-block

Period period 2

Electron configuration [He] 2s2 2p1

per shell 2, 3

Physical properties

Phase solid

Melting point 2349 K (2076 C, 3769 F)

Boiling point 4200 K (3927 C, 7101 F)

Densitywhen liquid, at m.p. 2.08 g/cm3

Heat of fusion 50.2 kJ/mol

Heat of vaporization 508 kJ/mol

Molar heat capacity 11.087 J/(molK)


vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 2348 2562 2822 3141 3545 4072

Atomic properties

Oxidation states 3, 2, 1, 5[4][5] (a mildlyacidic oxide)

Electronegativity Pauling scale: 2.04

Ionization energies 1st: 800.6 kJ/mol


2nd: 2427.1 kJ/mol
3rd: 3659.7 kJ/mol
(more)

Atomic radius empirical: 90 pm

Covalent radius 843 pm

Van der Waals radius 192 pm

Miscellanea

Crystal structure rhombohedral

Speed of soundthin rod 16,200 m/s (at 20 C)

Thermal expansion form: 57 m/(mK) (at 25 C)[6]

Thermal conductivity 27.4 W/(mK)

Electrical resistivity ~106 m (at 20 C)


Magnetic ordering diamagnetic[7]

Mohs hardness ~9.5

CAS Registry Number 7440-42-8

History

Discovery Joseph Louis Gay-Lussac andLouis Jacques


Thnard[8](30 June 1808)

First isolation Humphry Davy[9](9 July 1808)

Most stable isotopes

Main article: Isotopes of boron

iso NA half-life DM DE (MeV) DP


10
B 19.9(7)%10B is stable with 5 neutrons[10]
11
B 80.1(7)%11B is stable with 6 neutrons[10]

10
B content may be as low as 19.1% and as high as 20.3% in natural
samples. 11B is the remainder in such cases.[11]

references

Boron is a chemical element with symbol B and atomic number 5. Because boron is
produced entirely by cosmic ray spallation and not by stellar nucleosynthesis it is a
low-abundance element in both the Solar system and the Earth's crust.[12] Boron is
concentrated on Earth by the water-solubility of its more common naturally occurring
compounds, the borate minerals. These are mined industrially as evaporites, such
as borax and kernite. The largest proven boron deposits are in Turkey, which is also
the largest producer of boron minerals.

Chemically uncombined boron, which is classed as a metalloid, is found in small


amounts in meteoroids, but is not found naturally on Earth. Industrially, very pure
boron is produced with difficulty, as boron tends to form refractory materials
containing small amounts of carbon or other elements. Several allotropes of
boron exist: amorphous boron is a brown powder, and crystalline boron is black,
extremely hard (about 9.5 on the Mohs scale), and a poor conductor at room
temperature. The primary use of elemental boron is to make boron filaments, which
are used in a similar way to carbon fibers in some high-strength materials.

Almost all boron use is as chemical compounds. About half of global consumption of
boron compounds is as additives for glass fibers in boron-containing fiberglass used
for insulation or as structural materials. The next leading use is to make
boron polymers and ceramics, that play specialized roles as high-strength lightweight
structural and refractory materials. Borosilicate glass glassware is used for its greater
strength and breakage resistance (thermal shock resistance) than ordinary soda lime
glass. Boron compounds are also used as fertilizers in agriculture, and in sodium
perborate bleaches. In minor uses, boron is an important dopant for semiconductors,
and boron-containing reagents are used as intermediates in the synthesis of organic
fine chemicals. A few boron-containing organic pharmaceuticals are used, or are in
study. Natural boron is composed of two stable isotopes, one of which (boron-10) has
a number of uses as a neutron-capturing agent.

In biology, borates have low toxicity in mammals (similar to table salt), but are more
toxic to arthropods and are used as insecticides. Boric acid is mildly antimicrobial,
and a natural boron-containing organic antibiotic is known.[13] Boron is essential to
life. Small amounts of boron compounds play a strengthening role in the cell walls of
all plants, making boron necessary in soils. Experiments indicate a role for boron as
an ultratrace element in animals, but its role in animal physiology is unknown.

Contents
[hide]

1 History
2 Preparation of elemental boron in the laboratory
3 Characteristics
o 3.1 Allotropes
o 3.2 Chemistry of the element
3.2.1 Chemical compounds
3.2.1.1 Organoboron chemistry
3.2.1.2 Compounds of B(I) and B(II)
o 3.3 Isotopes
3.3.1 Commercial isotope enrichment
3.3.2 Enriched boron (boron-10)
3.3.3 Depleted boron (boron-11)
3.3.3.1 Radiation-hardened semiconductors
3.3.3.2 Proton-boron fusion
3.3.4 NMR spectroscopy
o 3.4 Occurrence
4 Production
o 4.1 Market trend
5 Applications
o 5.1 Elemental boron fiber
o 5.2 Boronated fiberglass
o 5.3 Borosilicate glass
o 5.4 Boron carbide ceramic
o 5.5 High-hardness and abrasive compounds
o 5.6 Boron metal coatings
o 5.7 Detergent formulations and bleaching agents
o 5.8 Insecticides
o 5.9 Semiconductors
o 5.10 Magnets
o 5.11 Shielding in nuclear reactors
o 5.12 Other nonmedical uses
o 5.13 Pharmaceutical and biological applications
o 5.14 Research areas
6 Biological role
o 6.1 Analytical quantification
o 6.2 Health issues and toxicity
7 See also
8 References
9 External links

History
The word boron was coined from borax, the mineral from which it was isolated, by
analogy with carbon, which it resembles chemically. For the etymology of borax, see
that article.
Sassolite.

Borax glazes were used in China from AD 300, and some tincal (crude borax) reached
the West, where the Persian alchemist Jbir ibn Hayyn seems to mention it in AD
700. Marco Polo brought some glazes back to Italy in the 13th century. Agricola,
around 1600, reports the use of borax as a flux inmetallurgy. In 1777, boric acid was
recognized in the hot springs (soffioni) near Florence, Italy, and became known as sal
sedativum, with mainly medical uses. The rare mineral is called sassolite, which is
found at Sasso, Italy. Sasso was the main source of European borax from 1827 to
1872, at which date American sources replaced it.[14][15] Boron compounds were
relatively rarely used chemicals until the late 1800s when Francis Marion
Smith's Pacific Coast Borax Company first popularized these compounds and made
them in volume and hence cheap.[16]

Boron was not recognized as an element until it was isolated by Sir Humphry
Davy[9] and by Joseph Louis Gay-Lussac and Louis Jacques Thnard.[8] In 1808 Davy
observed that electric current sent through a solution of borates produced a brown
precipitate on one of the electrodes. In his subsequent experiments, he used potassium
to reduce boric acid instead of electrolysis. He produced enough boron to confirm a
new element and named the elementboracium.[9] Gay-Lussac and Thnard used iron to
reduce boric acid at high temperatures. By oxidizing boron with air, they showed that
boric acid is an oxidation product of boron.[8][17] Jns Jakob Berzelius identified boron
as an element in 1824.[18] Pure boron was arguably first produced by the American
chemist Ezekiel Weintraub in 1909.[19][20][21]

Preparation of elemental boron in the laboratory


The earliest routes to elemental boron involved reduction of boric oxide with metals
such as magnesium or aluminium. However the product is almost always
contaminated with metal borides. Pure boron can be prepared by reducing volatile
boron halides with hydrogen at high temperatures. Ultrapure boron for use in the
semiconductor industry is produced by the decomposition of diborane at high
temperatures and then further purified with the zone melting or Czochralski
processes.[22]

The production of boron compounds does not involve formation of elemental boron,
but exploits the convenient availability of borates.

Characteristics
Allotropes
Main article: Allotropes of boron

Boron chunks

Boron is similar to carbon in its capability to form stable covalently bonded molecular
networks. Even nominally disordered (amorphous) boron contains regular
boron icosahedra which are, however, bonded randomly to each other without long-
range order.[23][24] Crystalline boron is a very hard, black material with a high melting
point of above 2000 C. It exists in four major polymorphs: -rhombohedral and -
rhombohedral (-R and -R), and -tetragonal (-T); -tetragonal phase also exists
(-T), but is very difficult to produce without significant contamination. Whereas ,
and T[clarification needed] phases are based on B12 icosahedra, the -phase can be described as
a rocksalt-type arrangement of the icosahedra and B2 atomic pairs.[25] It can be
produced by compressing other boron phases to 1220 GPa and heating to 1500
1800 C; it remains stable after releasing the temperature and pressure. The T phase is
produced at similar pressures, but higher temperatures of 18002200 C. As to the
and phases, they might both coexist at ambient conditions with the phase being
more stable.[25][26][27] Compressing boron above 160 GPa produces a boron phase with an
as yet unknown structure, and this phase is a superconductor at temperatures 612
K.[28] Borospherene (fullerene-like B40) molecules) and borophene (proposed graphene-
like structure) have been described in 2014.

Boron phase -R -R -T
Symmetry Rhombohedral Rhombohedral Orthorhombic Tetragonal
Atoms/unit cell[25] 12 ~105 28
Density (g/cm )
3 [29][30][31][32]
2.46 2.35 2.52 2.36
Vickers hardness (GPa) [33][34]
42 45 5058
Bulk modulus (GPa) [34][35]
185 224 227
Bandgap (eV)[34][36] 2 1.6 2.1

Chemistry of the element


See also: Category:Boron compounds.

Elemental boron is rare and poorly studied because the material is extremely difficult
to prepare. Most studies on "boron" involve samples that contain small amounts of
carbon. Chemically, boron behaves more similarly to silicon than to aluminium.
Crystalline boron is chemically inert and resistant to attack by
boiling hydrofluoric or hydrochloric acid. When finely divided, it is attacked slowly
by hot concentrated hydrogen peroxide, hot concentrated nitric acid, hot sulfuric
acid or hot mixture of sulfuric and chromic acids.[20]

The rate of oxidation of boron depends upon the crystallinity, particle size, purity and
temperature. Boron does not react with air at room temperature, but at higher
temperatures it burns to form boron trioxide:[37]

4 B + 3 O2 2 B2O3

Ball-and-stick model of tetraborate anion, [B4O5(OH)4]2, as it occurs in crystalline


borax, Na2[B4O5(OH)4]8H2O. Boron atoms are pink, with bridging oxygens in red, and
four hydroxyl hydrogens in white. Note two borons are trigonally bonded sp 2with no
formal charge, while the other two borons are tetrahedrally bonded sp 3, each carrying
a formal charge of 1. The oxidation state of all borons is III. This mixture of boron
coordination numbers and formal charges is characteristic of natural boron minerals.

Boron undergoes halogenation to give trihalides, for example,

2 B + 3 Br2 2 BBr3

The trichloride in practice is usually made from the oxide.[37]

Chemical compounds
Boron (III) trifluoridestructure, showing "empty" boron p orbital in pi-type coordinate
covalent bonds

In its most familiar compounds, boron has the formal oxidation state III. These
include oxides, sulfides, nitrides, and halides.[37]

The trihalides adopt a planar trigonal structure. These compounds are Lewis acids in
that they readily form adducts with electron-pair donors, which are called Lewis
bases. For example, fluoride (F) andboron trifluoride (BF3) combined to give
the tetrafluoroborate anion, BF4. Boron trifluoride is used in the petrochemical
industry as a catalyst. The halides react with water to form boric acid.[37]

Boron is found in nature on Earth entirely as various oxides of B(III), often associated
with other elements. More than one hundred borate minerals contain boron in
oxidation state +3. These minerals resemble silicates in some respect, although boron
is often found not only in a tetrahedral coordination with oxygen, but also in a trigonal
planar configuration. Unlike silicates, the boron minerals never contain boron with
coordination number greater than four. A typical motif is exemplified by the
tetraborate anions of the common mineral borax, shown at left. The formal negative
charge of the tetrahedral borate centers is balanced by metal cations in the minerals,
such as the sodium (Na+) in borax.[37]

Main article: Boranes

Boranes are chemical compounds of boron and hydrogen, with the generic formula of
BxHy. These compounds do not occur in nature. Many of the boranes readily oxidise
on contact with air, some violently. The parent member BH3 is called borane, but it is
known only in the gaseous state, and dimerises to form diborane, B2H6. The larger
boranes all consist of boron clusters that are polyhedral, some of which exist as
isomers. For example, isomers of B20H26 are based on the fusion of two 10-atom
clusters.

The most important boranes are diborane B2H6 and two of its pyrolysis products,
pentaborane B5H9 and decaborane B10H14. A large number of anionic boron hydrides
are known, e.g. [B12H12]2.
The formal oxidation number in boranes is positive, and is based on the assumption
that hydrogen is counted as 1 as in active metal hydrides. The mean oxidation
number for the borons is then simply the ratio of hydrogen to boron in the molecule.
For example, in diborane B2H6, the boron oxidation state is +3, but in decaborane
B10H14, it is 7/5 or +1.4. In these compounds the oxidation state of boron is often not a
whole number.

Main article: Boron nitride

The boron nitrides are notable for the variety of structures that they adopt. They adopt
structures analogous to various allotropes of carbon, including graphite, diamond, and
nanotubes. In the diamond-like structure called cubic boron nitride
(tradename Borazon), boron atoms exist in the tetrahedral structure of carbons atoms
in diamond, but one in every four B-N bonds can be viewed as a coordinate covalent
bond, wherein two electrons are donated by the nitrogen atom which acts as the Lewis
base to a bond to the Lewis acidic boron(III) centre. Cubic boron nitride, among other
applications, is used as an abrasive, as it has a hardness comparable with diamond (the
two substances are able to produce scratches on each other). In the BN compound
analogue of graphite, hexagonal boron nitride (h-BN), the positively charged boron
and negatively charged nitrogen atoms in each plane lie adjacent to the oppositely
charged atom in the next plane. Consequently, graphite and h-BN have very different
properties, although both are lubricants, as these planes slip past each other easily.
However, h-BN is a relatively poor electrical and thermal conductor in the planar
directions.[38][39]
Organoboron chemistry

Main article: Organoboron chemistry

A large number of organoboron compounds are known and many are useful in organic
synthesis. Many are produced from hydroboration, which employs diborane, B2H6, a
simple borane chemical. Organoboron(III) compounds are usually tetrahedral or
trigonal planar, for example, tetraphenylborate, [B(C6H5)4] vs. triphenylborane,
B(C6H5)3. However, multiple boron atoms reacting with each other have a tendency to
form novel dodecahedral (12-sided) and icosahedral (20-sided) structures composed
completely of boron atoms, or with varying numbers of carbon heteroatoms.

Organoboron chemicals have been employed in uses as diverse as boron carbide (see
below), a complex very hard ceramic composed of boron-carbon cluster anions and
cations, to carboranes, carbon-boron cluster chemistry compounds that can be
halogenated to form reactive structures including carborane acid, a superacid. As one
example, carboranes form useful molecular moieties that add considerable amounts of
boron to other biochemicals in order to synthesize boron-containing compounds
for boron neutron capture therapy of cancer.
Compounds of B(I) and B(II)

Although these are not found on Earth naturally, boron forms a variety of stable
compounds with formal oxidation state less than three. As for many covalent
compounds, formal oxidation states are often of little meaning in boron hydrides and
metal borides. The halides also form derivatives of B(I) and B(II). BF, isoelectronic
with N2, is not isolable in condensed form, but B2F4 and B4Cl4 are well characterized.[40]

Ball-and-stick model of superconductor magnesium diboride. Boron atoms lie in


hexagonal aromatic graphite-like layers, with a charge of 1 on each boron atom.
Magnesium(II) ions lie between layers

Binary metal-boron compounds, the metal borides, contain boron in negative


oxidation states. Illustrative is magnesium diboride (MgB2). Each boron atom has a
formal 1 charge and magnesium is assigned a formal charge of 2+. In this material,
the boron centers are trigonal planar, with an extra double bond for each boron, with
the boron atoms forming sheets akin to the carbon in graphite. However, unlike the
case with hexagonal boron nitride which by comparison lacks electrons in the plane of
the covalent atoms, the delocalized electrons in the plane of magnesium diboride
allow it to conduct electricity similar to isoelectronic graphite. In addition, in 2001
this material was found to be a high-temperature superconductor.[41][42]

Certain other metal borides find specialized applications as hard materials for cutting
tools.[43] Often boron in borides has fractional oxidation states, such as 1/3 in calcium
hexaboride (CaB6).

From the structural perspective, the most distinctive chemical compounds of boron are
the hydrides. Included in this series are the cluster
compounds dodecaborate (B12H122), decaborane (B10H14), and the carboranes such as
C2B10H12. Characteristically such compounds contain boron with coordination numbers
greater than four.[37]
Isotopes

Main article: Isotopes of boron

Boron has two naturally occurring and stable isotopes, 11B (80.1%) and 10B (19.9%).
The mass difference results in a wide range of 11B values, which are defined as a
fractional difference between the11B and 10B and traditionally expressed in parts per
thousand, in natural waters ranging from 16 to +59. There are 13 known isotopes of
boron, the shortest-lived isotope is 7B which decays throughproton emission and alpha
decay. It has a half-life of 3.51022 s. Isotopic fractionation of boron is controlled by
the exchange reactions of the boron species B(OH)3 and [B(OH)4]. Boron isotopes are
also fractionated during mineral crystallization, during H2O phase changes
in hydrothermal systems, and during hydrothermal alteration of rock. The latter effect
results in preferential removal of the [10B(OH)4] ion onto clays. It results in solutions
enriched in 11B(OH)3 and therefore may be responsible for the large 11B enrichment in
seawater relative to both oceanic crust and continental crust; this difference may act as
an isotopic signature.[44] The exotic 17B exhibits a nuclear halo, i.e. its radius is
appreciably larger than that predicted by the liquid drop model.[45]

The 10B isotope is good at capturing thermal neutrons (see neutron cross
section#Typical cross sections). Natural boron is about 20% 10B and 80% 11B.
The nuclear industry enriches natural boron to nearly pure 10B. The less-valuable by-
product, depleted boron, is nearly pure 11B.

Commercial isotope enrichment

Because of its high neutron cross-section, boron-10 is often used to control fission in
nuclear reactors as a neutron-capturing substance.[46] Several industrial-scale
enrichment processes have been developed, however only the fractionated vacuum
distillation of the dimethyl ether adduct of boron trifluoride (DME-BF3) and column
chromatography of borates are being used.[47][48]

Enriched boron (boron-10)


Neutron cross section of boron (top curve is for10B and bottom curve for 11B)

Enriched boron or 10B is used in both radiation shielding and is the primary nuclide
used in neutron capture therapy of cancer. In the latter ("boron neutron capture
therapy" or BNCT), a compound containing 10B is incorporated into a pharmaceutical
which is selectively taken up by a malignant tumor and tissues near it. The patient is
then treated with a beam of low energy neutrons at a relatively low neutron radiation
dose. The neutrons, however, trigger energetic and short-range secondary alpha
particle and lithium-7 heavy ion radiation that are products of the boron +
neutron nuclear reaction, and this ion radiation additionally bombards the tumor,
especially from inside the tumor cells.[49][50][51][52]

In nuclear reactors, 10B is used for reactivity control and in emergency shutdown
systems. It can serve either function in the form of borosilicate control rods or as boric
acid. In pressurized water reactors, boric acid is added to the reactor coolant when the
plant is shut down for refueling. It is then slowly filtered out over many months
as fissile material is used up and the fuel becomes less reactive.[53]

In future manned interplanetary spacecraft, 10B has a theoretical role as structural


material (as boron fibers or BN nanotube material) which would also serve a special
role in the radiation shield. One of the difficulties in dealing with cosmic rays, which
are mostly high energy protons, is that some secondary radiation from interaction of
cosmic rays and spacecraft materials is high energy spallationneutrons. Such neutrons
can be moderated by materials high in light elements such as polyethylene, but the
moderated neutrons continue to be a radiation hazard unless actively absorbed in the
shielding. Among light elements that absorb thermal neutrons, 6Li and 10B appear as
potential spacecraft structural materials which serve both for mechanical
reinforcement and radiation protection.[54]

Depleted boron (boron-11)


Radiation-hardened semiconductors

Cosmic radiation will produce secondary neutrons if it hits spacecraft structures.


Those neutrons will be captured in 10B, if it is present in the
spacecraft's semiconductors, producing a gamma ray, analpha particle, and
a lithium ion. These resultant decay products may then irradiate nearby semiconductor
"chip" structures, causing data loss (bit flipping, or single event upset). In radiation-
hardenedsemiconductor designs, one countermeasure is to use depleted boron, which
is greatly enriched in 11B and contains almost no 10B. It is useful because 11B is largely
immune to radiation damage. Depleted boron is a byproduct of the nuclear industry.[53]
Proton-boron fusion

Main article: Proton-boron fusion

B is also a candidate as a fuel for aneutronic fusion. When struck by a proton with
11

energy of about 500 keV, it produces three alpha particles and 8.7 MeV of energy.
Most other fusion reactions involving hydrogen and helium produce penetrating
neutron radiation, which weakens reactor structures and induces long-term
radioactivity, thereby endangering operating personnel. However, the alpha
particles from 11B fusion can be turned directly into electric power, and all radiation
stops as soon as the reactor is turned off.[55]

NMR spectroscopy

Both 10B and 11B possess nuclear spin. The nuclear spin of 10B is 3 and that of 11B is 32.
These isotopes are, therefore, of use in nuclear magnetic resonance spectroscopy; and
spectrometers specially adapted to detecting the boron-11 nuclei are available
commercially. The 10B and 11B nuclei also cause splitting in the resonances of attached
nuclei.[56]

Occurrence

Main article: Borate minerals


See also: Category:Borate minerals.

A fragment of ulexite
Borax crystals

Boron is rare in the Universe and solar system due to trace formation in the Big
Bang and in stars. It is formed in minor amounts in cosmic ray
spallation nucleosynthesis and may be found uncombined in cosmic
dust and meteoroid materials. In the high oxygen environment of Earth, boron is
always found fully oxidized to borate. Boron does not appear on Earth in elemental
form.

Although boron is a relatively rare element in the Earth's crust, representing only
0.001% of the crust mass, it can be highly concentrated by the action of water, in
which many borates are soluble. It is found naturally combined in compounds such
as borax and boric acid (sometimes found in volcanic spring waters). About a
hundred borate minerals are known.

Production
Economically important sources of boron are the minerals colemanite, rasorite
(kernite), ulexite and tincal. Together these constitute 90% of mined boron-containing
ore. The largest global borax deposits known, many still untapped, are in Central and
Western Turkey, including the provinces
of Eskiehir, Ktahya and Balkesir.[57][58][59] Global proven boron mineral mining
reserves exceed one billion metric tonnes, against a yearly production of about four
million tonnes.[60]

Turkey and the United States are the largest producers of boron products. Turkey
produces about half of the global yearly demand, though Eti Mine
Works (Turkish: Eti Maden letmeleri) a Turkishstate-
owned mining and chemicals company focusing on boron products. It holds
a government monopoly on the mining of borate minerals in Turkey, which possesses
72% of the world's known deposits.[61] In 2012, it held a 47% share of production of
global borate minerals, ahead of its main competitor, Rio Tinto Group.[62]
Almost a quarter (23%) of global boron production comes from the single Rio Tinto
Borax Mine (also known as the U.S. Borax Boron
Mine) 35234.447N 1174045.412W near Boron, California.[63][64]

Market trend

The average cost of crystalline boron is $5/g.[65] Free boron is chiefly used in making
boron fibers, where it is deposited by chemical vapor deposition on a tungsten core
(see below). Boron fibers are used in lightweight composite applications, such as high
strength tapes. This use is a very small fraction of total boron use. Boron is introduced
into semiconductors as boron compounds, by ion implantation.

Estimated global consumption of boron (almost entirely as boron compounds) was


about 4 million tonnes of B2O3 in 2012. Boron mining and refining capacities are
considered to be adequate to meet expected levels of growth through the next decade.

The form in which boron is consumed has changed in recent years. The use of ores
like colemanite has declined following concerns over arsenic content. Consumers
have moved toward the use of refined borates and boric acid that have a lower
pollutant content.

Increasing demand for boric acid has led a number of producers to invest in additional
capacity. Turkey's state-owned Eti Mine Works opened a new boric acid plant with
the production capacity of 100,000 tonnes per year at Emet in 2003. Rio Tinto
Group increased the capacity of its boron plant from 260,000 tonnes per year in 2003
to 310,000 tonnes per year by May 2005, with plans to grow this to 366,000 tonnes
per year in 2006. Chinese boron producers have been unable to meet rapidly growing
demand for high quality borates. This has led to imports of sodium tetraborate (borax)
growing by a hundredfold between 2000 and 2005 and boric acid imports increasing
by 28% per year over the same period.[66][67]

The rise in global demand has been driven by high growth rates in glass
fiber, fiberglass and borosilicate glassware production. A rapid increase in the
manufacture of reinforcement-grade boron-containing fiberglass in Asia, has offset
the development of boron-free reinforcement-grade fiberglass in Europe and the USA.
The recent rises in energy prices may lead to greater use of insulation-grade
fiberglass, with consequent growth in the boron consumption. Roskill Consulting
Group forecasts that world demand for boron will grow by 3.4% per year to reach 21
million tonnes by 2010. The highest growth in demand is expected to be in Asia
where demand could rise by an average 5.7% per year.[66][68]

Applications
Nearly all boron ore extracted from the Earth is destined for refinement into boric
acid and sodium tetraborate pentahydrate. In the United States, 70% of the boron is
used for the production of glass and ceramics.[69][70] The major global industrial-scale
use of boron compounds (about 46% of end-use) is in production of glass fiber for
boron-containing insulating and structural fiberglasses, especially in Asia. Boron is
added to the glass as borax pentahydrate or boron oxide, to influence the strength or
fluxing qualities of the glass fibers.[71] Another 10% of global boron production is
for borosilicate glassas used in high strength glassware. About 15% of global boron is
used in boron ceramics, including super-hard materials discussed below. Agriculture
consumes 11% of global boron production, and bleaches and detergents about 6%.[72]

Elemental boron fiber

Boron fibers (boron filaments) are high-strength, lightweight materials that are used
chiefly for advanced aerospace structures as a component of composite materials, as
well as limited production consumer and sporting goods such as golf clubs and fishing
rods.[73][74] The fibers can be produced by chemical vapor deposition of boron on
a tungsten filament.[75][76]

Boron fibers and sub-millimeter sized crystalline boron springs are produced by laser-
assisted chemical vapor deposition. Translation of the focused laser beam allows to
produce even complex helical structures. Such structures show good mechanical
properties (elastic modulus 450 GPa, fracture strain 3.7%, fracture stress 17 GPa) and
can be applied as reinforcement of ceramics or inmicromechanical systems.[77]

Boronated fiberglass

Main article: Fiberglass

Fiberglass is a fiber reinforced polymer made of plastic reinforced by glass fibers,


commonly woven into a mat. The glass fibers used in the material are made of various
types of glass depending upon the fiberglass use. These glasses all contain silica or
silicate, with varying amounts of oxides of calcium, magnesium, and sometimes
boron. The boron is present as borosilicate, borax, or boron oxide, and is added to
increase the strength of the glass, or as a fluxing agent to decrease the melting
temperature of silica, which is too high to be easily worked in its pure form to make
glass fibers.

The highly boronated glasses used in fiberglass are E-glass (named for "Electrical"
use, but now the most common fiberglass for general use). E-glass is alumino-
borosilicate glass with less than 1% w/w alkali oxides, mainly used for glass-
reinforced plastics. Other common high-boron glasses include C-glass, an alkali-lime
glass with high boron oxide content, used for glass staple fibers and insulation, and D-
glass, a borosilicate glass, named for its low Dielectric constant).[78]

Not all fiberglasses contain boron, but on a global scale, most of the fiberglass used
does contain it. Because the ubiquitous use of fiberglass in construction and
insulation, boron-containing fiberglasses consume half the global production of boron,
and are the single largest commercial boron market.

Borosilicate glass

Borosilicate glassware. Displayed are two beakers and a test tube.

Borosilicate glass, which is typically 1215% B2O3, 80% SiO2, and 2% Al2O3, has a
low coefficient of thermal expansion giving it a good resistance to thermal
shock. Schott AG's "Duran" and Owens-Corning's trademarked Pyrex are two major
brand names for this glass, used both in laboratory glassware and in
consumer cookware and bakeware, chiefly for this resistance.[79]

Boron carbide ceramic

Main article: Boron carbide


Unit cell of B4C. The green sphere andicosahedra consist of boron atoms, and black
spheres are carbon atoms.[80]

Several boron compounds are known for their extreme hardness and toughness. Boron
carbide is a ceramic material which is obtained by decomposing B2O3 with carbon in
the electric furnace:

2 B2O3 + 7 C B4C + 6 CO

Boron carbide's structure is only approximately B4C, and it shows a clear depletion of
carbon from this suggested stoichiometric ratio. This is due to its very complex
structure. The substance can be seen with empirical formula B12C3 (i.e., with
B12 dodecahedra being a motif), but with less carbon, as the suggested C3 units are
replaced with C-B-C chains, and some smaller (B6) octahedra are present as well (see
the boron carbide article for structural analysis). The repeating polymer plus semi-
crystalline structure of boron carbide gives it great structural strength per weight. It is
used in tank armor,bulletproof vests, and numerous other structural applications.

Boron carbide's ability to absorb neutrons without forming long-


lived radionuclides (especially when doped with extra boron-10) makes the material
attractive as an absorbent for neutron radiation arising in nuclear power plants.
Nuclear applications of boron carbide include shielding, control rods and shut-down
pellets. Within control rods, boron carbide is often powdered, to increase its surface
area.[81]

High-hardness and abrasive compounds

Main article: Superhard materials


Mechanical properties of BCN solids[82] and ReB2[83]

Material Diamond cubic-BC2N cubic-BC5 cubic-BN B4C ReB2

Vickers hardness (GPa) 115 76 71 62 38 22

Fracture toughness (MPa m12) 5.3 4.5 9.5 6.8 3.5

Boron carbide and cubic boron nitride powders are widely used as abrasives. Boron
nitride is a material isoelectronic to carbon. Similar to carbon, it has both hexagonal
(soft graphite-like h-BN) and cubic (hard, diamond-like c-BN) forms. h-BN is used as
a high temperature component and lubricant. c-BN, also known under commercial
name borazon,[84] is a superior abrasive. Its hardness is only slightly smaller than, but
its chemical stability is superior, to that of diamond. Heterodiamond (also called
BCN) is another diamond-like boron compound.

Boron metal coatings

Metal borides are used for coating tools through chemical vapor
deposition or physical vapor deposition. Implantation of boron ions into metals and
alloys, through ion implantation or ion beam deposition, results in a spectacular
increase in surface resistance and microhardness. Laser alloying has also been
successfully used for the same purpose. These borides are an alternative to diamond
coated tools, and their (treated) surfaces have similar properties to those of the bulk
boride.[85]

For example, rhenium diboride can be produced at ambient pressures, but is rather
expensive because of rhenium. The hardness of ReB2 exhibits
considerable anisotropy because of its hexagonal layered structure. Its value is
comparable to that of tungsten carbide, silicon carbide, titanium diboride or zirconium
diboride.[83] Similarly, AlMgB14 + TiB2 composites possess high hardness and wear
resistance and are used in either bulk form or as coatings for components exposed to
high temperatures and wear loads.[86]
Detergent formulations and bleaching agents

Borax is used in various household laundry and cleaning products,[87] including the "20
Mule Team Borax" laundry booster and "Boraxo" powdered hand soap. It is also
present in some tooth bleachingformulas.[70]

Sodium perborate serves as a source of active oxygen in many detergents, laundry


detergents, cleaning products, and laundry bleaches. However, despite its name,
"Borateem" laundry bleach no longer contains any boron compounds, using sodium
percarbonate instead as a bleaching agent.[88]

Insecticides

Boric acid is used as an insecticide, notably against ants, fleas, and cockroaches.[89]

Semiconductors

Boron is a useful dopant for such semiconductors as silicon, germanium, and silicon
carbide. Having one fewer valence electron than the host atom, it donates
a hole resulting in p-type conductivity. Traditional method of introducing boron into
semiconductors is via its atomic diffusion at high temperatures. This process uses
either solid (B2O3), liquid (BBr3), or gaseous boron sources (B2H6 or BF3). However,
after the 1970s, it was mostly replaced by ion implantation, which relies mostly on
BF3 as a boron source.[90] Boron trichloride gas is also an important chemical in
semiconductor industry, however not for doping but rather for plasma etching of
metals and their oxides.[91] Triethylborane is also injected into vapor
deposition reactors as a boron source. Examples are the plasma deposition of boron-
containing hard carbon films, silicon nitride-boron nitride films, and
for doping of diamond film with boron.[92]

Magnets

Boron is a component of neodymium magnets (Nd2Fe14B), which are among the


strongest type of permanent magnet. These magnets are found in a variety of
electromechanical and electronic devices, such as magnetic resonance imaging (MRI)
medical imaging systems, in compact and relatively small motors and actuators. As
examples, computer HDDs (hard disk drives), CD (compact disk) and DVD (digital
versatile disk) players rely on neodymium magnet motors to deliver intense rotary
power in a remarkably compact package. In mobile phones 'Neo' magnets provide the
magnetic field which allows tiny speakers to deliver appreciable audio power.[7]

Shielding in nuclear reactors


Boron shielding is used as a control for nuclear reactors, taking advantage of its high
cross-section for neutron capture.[93]

Other nonmedical uses

Launch of Apollo 15 Saturn V rocket, using triethylborane ignitor

Because of its distinctive green flame, amorphous boron is used in pyrotechnic


flares.[94]
Starch and casein-based adhesives contain sodium tetraborate decahydrate
(Na2B4O710 H2O)
Some anti-corrosion systems contain borax.[95]
Sodium borates are used as a flux for soldering silver and gold and
with ammonium chloride for welding ferrous metals.[96] They are also fire
retarding additives to plastics and rubber articles.[97]
Boric acid (also known as orthoboric acid) H3BO3 is used in the production of
textile fiberglass and flat panel displays[70][98] and in many PVAc- and PVOH-
based adhesives.
Triethylborane is a substance which ignites the JP-7 fuel of the Pratt &
Whitney J58 turbojet/ramjet engines powering the Lockheed SR-71
Blackbird.[99] It was also used to ignite the F-1 Engineson the Saturn V Rocket
utilized by NASA's Apollo and Skylab programs from 1967 until 1973.
Triethylborane is suitable for this because of its pyrophoric properties,
especially the fact that it burns with a very high temperature.[100] Triethylborane
is an industrial initiator in radical reactions, where it is effective even at low
temperatures.
Borates are used as environmentally benign wood preservatives.[101]

Pharmaceutical and biological applications

Boric acid has antiseptic, antifungal, and antiviral properties and for these reasons is
applied as a water clarifier in swimming pool water treatment.[102] Mild solutions of
boric acid have been used as eye antiseptics.
Bortezomib (Velcade). Boron appears as an active element in its first-approved
organic pharmaceutical in the novel pharmaceutical bortezomib, a new class of drug
called the proteasome inhibitors, which are active in myeloma and one form of
lymphoma (it is in currently in experimental trials against other types of lymphoma).
The boron atom in bortezomib binds the catalytic site of the 26S proteasome[103] with
high affinity and specificity.

A number of potential boronated pharmaceuticals using boron-10, have been


prepared for use in boron neutron capture therapy (BNCT).[104]
Some boron compounds show promise in treating arthritis, though none have as
yet been generally approved for the purpose.[105]

Research areas

Magnesium diboride is an important superconducting material with the transition


temperature of 39 K. MgB2 wires are produced with the powder-in-tube process and
applied in superconducting magnets.[106][107]

Amorphous boron is used as a melting point depressant in nickel-chromium braze


alloys.[108]

Hexagonal boron nitride forms atomically thin layers, which have been used to
enhance the electron mobility in graphene devices.[109][110] It also forms nanotubular
structures (BNNTs), which have with high strength, high chemical stability, and
high thermal conductivity, among its list of desirable properties.[111]

Biological role
Boron is needed by life. In 2013, a hypothesis suggested it was possible that boron
and molybdenum catalyzed the production of RNA on Mars with life being
transported to Earth via a meteorite around 3 billion years ago.[112]

There exists one known boron-containing natural antibiotic, boromycin, isolated


from streptomyces.[113][114]

Boron is an essential plant nutrient, required primarily for maintaining the integrity of
cell walls. However, high soil concentrations of > 1.0 ppm lead to marginal and tip
necrosis in leaves as well as poor overall growth performance. Levels as low as
0.8 ppm produce these same symptoms in plants that are particularly sensitive to
boron in the soil. Nearly all plants, even those somewhat tolerant of soil boron, will
show at least some symptoms of boron toxicity when soil boron content is greater than
1.8 ppm. When this content exceeds 2.0 ppm, few plants will perform well and some
may not survive. When boron levels in plant tissue exceed 200 ppm, symptoms of
boron toxicity are likely to appear.[115][116][117]

As an ultratrace element, boron is necessary for the optimal health of rats. Boron
deficiency in rats is not easy to produce, since boron is needed by rats in such small
amounts that ultrapurified foods and dust filtration of air are required. Boron
deficiency manifests in rats as poor coat or hair quality. Presumably boron is
necessary to other mammals. No deficiency syndrome in humans has been described.
Small amounts of boron occur widely in the diet, and the amounts needed in the diet
would, by extension from rodent studies, be very small. The exact physiological role
of boron in the animal kingdom is poorly understood.[118]

Boron occurs in all foods produced from plants. Since 1989 its nutritional value has
been argued. It is thought that boron plays several biochemical roles in animals,
including humans.[119] The United States Department of Agriculture conducted an
experiment in which postmenopausal women took 3 mg of boron a day. The results
showed that supplemental boron reduced excretion of calcium by 44%, and
activated estrogen and vitamin D, suggesting a possible role in the suppression
of osteoporosis. However, whether these effects were conventionally nutritional, or
medicinal, could not be determined. The U.S. National Institutes of Health states that
"Total daily boron intake in normal human diets ranges from 2.14.3 mg
boron/day."[120][121]

Congenital endothelial dystrophy type 2, a rare form of corneal dystrophy, is linked to


mutations in SLC4A11 gene that encodes a transporter reportedly regulating the
intracellular concentration of boron.[122]

Analytical quantification

For determination of boron content in food or materials the colorimetric curcumin


method is used. Boron is converted to boric acid or borates and on reaction
with curcumin in acidic solution, a red colored boron-chelate complex, rosocyanine, is
formed.[123]

Health issues and toxicity

Elemental boron, boron oxide, boric acid, borates, and many organoboron
compounds are nontoxic to humans and animals (with toxicity similar to that of table
salt). The LD50 (dose at which there is 50% mortality) for animals is about 6 g per kg
of body weight. Substances with LD50 above 2 g are considered nontoxic. The
minimum lethal dose for humans has not been established. An intake of 4 g/day of
boric acid was reported without incident, but more than this is considered toxic in
more than a few doses. Intakes of more than 0.5 grams per day for 50 days cause
minor digestive and other problems suggestive of toxicity.[124] Single medical doses of
20 g of boric acid for neutron capture therapy have been used without undue toxicity.
Fish have survived for 30 min in a saturated boric acid solution and can survive longer
in strong borax solutions.[125] Boric acid is more toxic to insects than to mammals, and
is routinely used as an insecticide.[89]

The boranes (boron hydrogen compounds) and similar gaseous compounds are quite
poisonous. As usual, it is not an element that is intrinsically poisonous, but their
toxicity depends on structure.[14][15]

The boranes are toxic as well as highly flammable and require special care when
handling. Sodium borohydride presents a fire hazard owing to its reducing nature and
the liberation of hydrogen on contact with acid. Boron halides are corrosive.[126]

Carbon
From Wikipedia, the free encyclopedia
Jump to: navigation, search
This article is about the chemical element. For other uses, see Carbon
(disambiguation).

Carbon, C 6

Graphite (left) and diamond (right), the two most well-known allotropes of
carbon

Spectral lines of carbon

General properties
Name, symbol carbon, C

Appearance graphite: black


diamond: clear

Allotropes graphite, diamond

Pronunciation /krbn/
KAR-bn

Carbon in the periodic table



C

Si

boron carbon nitrogen

Atomic number 6

Standard atomic weight (Ar) 12.011[1] (12.009612.0116)[2]

Element category polyatomic nonmetal, sometimes


considered a metalloid

Group, block group 14 (carbon group), p-block

Period period 2

Electron configuration [He] 2s2 2p2

per shell 2, 4

Physical properties

Phase solid
Sublimation point 3915 K (3642 C, 6588 F)

Density near r.t. amorphous: 1.82.1 g/cm3[3]


graphite: 2.267 g/cm3
diamond: 3.515 g/cm3

Triple point 4600 K, 10,800 kPa[4][5]

Heat of fusion graphite: 117 kJ/mol

Molar heat capacity graphite: 8.517 J/(molK)


diamond: 6.155 J/(molK)

Atomic properties

Oxidation states +4, +3,[6] +2, +1,[7] 0, 1, 2, 3, 4[8]


(a mildly acidic oxide)

Electronegativity Pauling scale: 2.55

Ionization energies 1st: 1086.5 kJ/mol


2nd: 2352.6 kJ/mol
3rd: 4620.5 kJ/mol
(more)

Covalent radius sp3: 77 pm


sp2: 73 pm
sp: 69 pm

Van der Waals radius 170 pm

Miscellanea

Crystal structure graphite: simple hexagonal


(black)

Crystal structure diamond cubic

Speed of soundthin rod diamond: 18,350 m/s (at 20 C)

Thermal expansion diamond: 0.8 m/(mK) (at 25 C)[9]

Thermal conductivity graphite: 119165 W/(mK)


diamond: 9002300 W/(mK)

Electrical resistivity graphite: 7.837 m[10]

Magnetic ordering diamagnetic[11]

Young's modulus diamond: 1050 GPa[9]

Shear modulus diamond: 478 GPa[9]

Bulk modulus diamond: 442 GPa[9]

Poisson ratio diamond: 0.1[9]

Mohs hardness graphite: 12


diamond: 10

CAS Registry Number 7440-44-0

History
Discovery Egyptians and Sumerians[12](3750 BCE)

Recognized as an element Antoine Lavoisier[13] (1789)


by

Most stable isotopes

Main article: Isotopes of carbon

iso NA half-life DM DE (MeV) DP


11
C syn 20 min+ 0.96 11
B
12
C 98.9% C is stable with 6 neutrons
12

13
C 1.1%13C is stable with 7 neutrons
14
C trace 5730 y 0.156 14
N

references

Carbon (from Latin: carbo "coal") is a chemical element with symbol C and atomic
number 6. On the Periodic table, it is the first (row 2) of six elements in column
(group) 14, which have in common the composition of their outer electron shell. It
is nonmetallic and tetravalentmaking four electrons available to
form covalent chemical bonds. There are three naturally occurring isotopes,
with 12C and 13C being stable, while 14C is radioactive, decaying with a half-life of
about 5,730 years.[14] Carbon is one of the few elements known since antiquity.[15]

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, and oxygen. It is
present in all forms of carbon-based life, and in the human body carbon is the second
most abundant element by mass (about 18.5%) after oxygen.[16] This abundance,
together with the unique diversity of organic compounds and their unusual polymer-
forming ability at the temperatures commonly encountered on Earth, make this
element the chemical basis of all known life.

The atoms of carbon can be bonded together in different ways: allotropes of carbon.
The best known are graphite, diamond, and amorphous carbon.[17] The physical
properties of carbon vary widely with the allotropic form. For example, graphite
is opaque and black, while diamond is highly transparent. Graphite is soft enough to
form a streak on paper (hence its name, from the Greek word "" which means
"to write"), while diamond is the hardest naturally-occurring material known.
Graphite is a very good conductor, while diamond has a very lowelectrical
conductivity. Under normal conditions, diamond, carbon nanotubes,
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 monoxide and other transition metalcarbonyl 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 a vast number of compounds, more than any other element,
with almost ten million compounds described to date,[18] which in turn are a tiny
fraction of such compounds that are theoretically possible under standard conditions.

Contents
[hide]

1 Characteristics
o 1.1 Allotropes
o 1.2 Occurrence
o 1.3 Isotopes
o 1.4 Formation in stars
o 1.5 Carbon cycle
2 Compounds
o 2.1 Organic compounds
o 2.2 Inorganic compounds
o 2.3 Organometallic compounds
3 History and etymology
4 Production
o 4.1 Graphite
o 4.2 Diamond
5 Applications
o 5.1 Diamonds
6 Precautions
7 Bonding to carbon
8 See also
9 References
10 External links

Characteristics
Theoretically predicted phase diagram of carbon

The different forms or allotropes of carbon (see below) include one of the softest
known substances, graphite, and also the hardest naturally occurring
substance, diamond. Moreover, it has an affinity for bonding with other small atoms,
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.[18] 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),[4][5] so it sublimes at about 3,900 K.[19][20]

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 as tungsten 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 Sunand 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, chlorine or 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.
This exothermic 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.[21] However, the
process of separating it from graphite will require some technological development
before it is economical enough to be used in industrial processes.[22]

The system of carbon allotropes spans a range of extremes:

Graphite is one of the


Synthetic nanocrystalline diamond is the hardest material known.[23]
softest materials known.
Graphite is a very
good lubricant, Diamond is the ultimate abrasive.
displaying superlubricity.[24]
Graphite is a conductor of Diamond is an excellent electrical insulator,[26] and has the highest
electricity.[25] breakdown electric field of any known material.
Some forms of graphite are
used for thermal
insulation (i.e. firebreaks
Diamond is the best known naturally occurring thermal conductor
and heat shields), but
some other forms are good
thermal conductors.
Graphite is opaque. Diamond is highly transparent.
Graphite crystallizes in
Diamond crystallizes in the cubic system.
the hexagonal system.[27]
Amorphous carbon is Carbon nanotubes are among the most anisotropic materials ever
completely isotropic. produced.

Allotropes

Main article: Allotropes of carbon

Atomic carbon is a very short-lived species and, therefore, carbon is stabilized in


various multi-atomic structures with different molecular configurations
called allotropes. The three relatively well-known allotropes of carbon are amorphous
carbon, graphite, and diamond. Once considered exotic, fullerenes are nowadays
commonly synthesized and used in research; they include buckyballs,[28][29] carbon
nanotubes,[30]carbon nanobuds[31] and nanofibers.[32][33] Several other exotic allotropes
have also been discovered, such as lonsdaleite,[34] glassy carbon,[35]carbon
nanofoam[36] and linear acetylenic carbon (carbyne).[37]

A large sample of glassy carbon.

The amorphous form is an assortment of carbon atoms in a non-crystalline, irregular,


glassy state, which is essentially graphite but not held in a crystalline macrostructure.
It is present as a powder, and is the main constituent of substances such
as charcoal, lampblack (soot) and activated carbon. At normal pressures carbon takes
the form of graphite, in which each atom is bonded trigonally to three others in a
plane composed of fused hexagonal rings, just like those in aromatic
hydrocarbons.[38] The resulting network is 2-dimensional, and the resulting flat sheets
are stacked and loosely bonded through weak van der Waals forces. This gives
graphite its softness and its cleaving properties (the sheets slip easily past one
another). Because of the delocalization of one of the outer electrons of each atom to
form a -cloud, graphite conducts electricity, but only in the plane of each covalently
bonded sheet. This results in a lower bulk electrical conductivity for carbon than for
most metals. The delocalization also accounts for the energetic stability of graphite
over diamond at room temperature.
Some allotropes of carbon: a) diamond; b)graphite; c) lonsdaleite; df) fullerenes (C60,
C540, C70); g) amorphous carbon; h) carbon nanotube.

At very high pressures carbon forms the more compact allotrope diamond, having
nearly twice the density of graphite. Here, each atom is bonded tetrahedrally to four
others, thus making a 3-dimensional network of puckered six-membered rings of
atoms. Diamond has the same cubic structure as silicon and germanium and because
of the strength of the carbon-carbon bonds, it is the hardest naturally occurring
substance in terms of resistance to scratching. Contrary to the popular belief
that "diamonds are forever", they are in fact thermodynamically unstable under
normal conditions and transform into graphite.[17] However, due to a high activation
energy barrier, the transition into graphite is so extremely slow at room temperature as
to be unnoticeable. Under some conditions, carbon crystallizes as lonsdaleite. This
form has a hexagonal crystal lattice where all atoms are covalently bonded. Therefore,
all properties of lonsdaleite are close to those of diamond.[34]

Fullerenes have a graphite-like structure, but instead of purely hexagonal packing,


they also contain pentagons (or even heptagons) of carbon atoms, which bend the
sheet into spheres, ellipses or cylinders. The properties of fullerenes (split
into buckyballs, buckytubes and nanobuds) have not yet been fully analyzed and
represent an intense area of research in nanomaterials. The
names "fullerene"and "buckyball" are given after Richard Buckminster Fuller,
popularizer of geodesic domes, which resemble the structure of fullerenes. The
buckyballs are fairly large molecules formed completely of carbon bonded trigonally,
forming spheroids (the best-known and simplest is the soccerball-shaped
C60 buckminsterfullerene).[28] Carbon nanotubes are structurally similar to buckyballs,
except that each atom is bonded trigonally in a curved sheet that forms a
hollow cylinder.[29][30] Nanobuds were first reported in 2007 and are hybrid bucky
tube/buckyball materials (buckyballs are covalently bonded to the outer wall of a
nanotube) that combine the properties of both in a single structure.[31]

Of the other discovered allotropes, carbon nanofoam is a ferromagnetic allotrope


discovered in 1997. It consists of a low-density cluster-assembly of carbon atoms
strung together in a loose three-dimensional web, in which the atoms are bonded
trigonally in six- and seven-membered rings. It is among the lightest known solids,
with a density of about 2 kg/m3.[39] Similarly, glassy carbon contains a high proportion
of closed porosity,[35] but contrary to normal graphite, the graphitic layers are not
stacked like pages in a book, but have a more random arrangement. Linear acetylenic
carbon[37] has the chemical structure[37] -(C:::C)n-. Carbon in this modification is linear
with sp orbital hybridization, and is a polymer with alternating single and triple bonds.
This type of carbyne is of considerable interest to nanotechnology as its Young's
modulus is forty times that of the hardest known material diamond.[40]

Occurrence

Graphite ore

Raw diamond crystal.


"Present day" (1990s) sea surfacedissolved inorganic carbonconcentration (from
the GLODAPclimatology)

Carbon is the fourth most abundant chemical element in the universe by mass after
hydrogen, helium, and oxygen. Carbon is abundant in the Sun, stars, comets, and in
the atmospheres of most planets.[41]Some meteorites contain microscopic diamonds
that were formed when the solar system was still a protoplanetary disk. Microscopic
diamonds may also be formed by the intense pressure and high temperature at the sites
of meteorite impacts.[42]

In 2014 NASA announced a greatly upgraded database for tracking polycyclic


aromatic hydrocarbons (PAHs) in the universe. More than 20% of the carbon in the
universe may be associated with PAHs, complex compounds of carbon and hydrogen
without oxygen.[43] These compounds figure in the PAH world hypothesis where they
are hypothesized to have a role in abiogenesis and formation of life. PAHs seem to
have been formed "a couple of billion years" after the Big Bang, are widespread
throughout the universe, and are associated with new stars and exoplanets.[41]

It has been estimated that the solid earth as a whole contains 730 ppm of carbon, with
2000 ppm in the core and 120 ppm in the combined mantle and crust.[44] Since the
mass of the earth is5.9721024 kg, this would imply 4360 million gigatonnes of
carbon. This is much more than the amounts in the oceans or atmosphere (below).

In combination with oxygen in carbon dioxide, carbon is found in the Earth's


atmosphere (approximately 810 gigatonnes of carbon) and dissolved in all water
bodies (approximately 36,000 gigatonnes of carbon). Around 1,900 gigatonnes of
carbon are present in the biosphere. Hydrocarbons (such as coal, petroleum,
and natural gas) contain carbon as well. Coal "reserves" (not "resources") amount to
around 900 gigatonnes with perhaps 18 000 Gt of resources.[45] Oil reserves are around
150 gigatonnes. Proven sources of natural gas are about 175 1012 cubic metres
(representing about 105 gigatonnes carbon), but it is estimated that there are also
about 900 1012 cubic metres of "unconventional" gas such as shale gas, representing
about 540 gigatonnes of carbon.[46] Carbon is also locked up as methane hydrates in
polar regions and under the seas. Various estimates of the amount of carbon this
represents have been made: 500 to 2500 Gt,[47] or 3000 Gt.[48] In the past, quantities of
hydrocarbons were greater. According to one source, in the period from 1751 to 2008
about 347 gigatonnes of carbon were released as carbon dioxide to the atmosphere
from burning of fossil fuels.[49] However, another source puts the amount added to the
atmosphere for the period since 1750 at 879 Gt, and the total going to the atmosphere,
sea, and land (such as peat bogs) at almost 2000 Gt.[50]

Carbon is a major component in very large masses of carbonate rock


(limestone, dolomite, marble and so on). Coal is the largest commercial source of
mineral carbon, accounting for 4,000 gigatonnes or 80% of fossil carbon fuel.[51] It is
also rich in carbon for example, anthracite contains 9298%.[52]

As for individual carbon allotropes, graphite is found in large quantities in the United
States (mostly in New York and Texas), Russia, Mexico, Greenland, and India.
Natural diamonds occur in the rockkimberlite, found in ancient volcanic "necks", or
"pipes". Most diamond deposits are in Africa, notably in South
Africa, Namibia, Botswana, the Republic of the Congo, and Sierra Leone. There are
also deposits in Arkansas, Canada, the Russian Arctic, Brazil and in Northern and
Western Australia. Diamonds are now also being recovered from the ocean floor off
the Cape of Good Hope. However, though diamonds are found naturally, about 30%
of all industrial diamonds used in the U.S. are now made synthetically.

Carbon-14 is formed in upper layers of the troposphere and the stratosphere, at


altitudes of 915 km, by a reaction that is precipitated by cosmic rays.[53] Thermal
neutrons are produced that collide with the nuclei of nitrogen-14, forming carbon-14
and a proton.

Carbon-rich asteroids are relatively preponderant in the outer parts of the asteroid
belt in our solar system. These asteroids have not yet been directly sampled by
scientists. The asteroids can be used in hypothetical space-based carbon mining,
which may be possible in the future, but is currently technologically impossible. [54]

Isotopes

Main article: Isotopes of carbon

Isotopes of carbon are atomic nuclei that contain six protons plus a number
of neutrons (varying from 2 to 16). Carbon has two stable, naturally
occurring isotopes.[14] The isotope carbon-12 (12C) forms 98.93% of the carbon on
Earth, while carbon-13 (13C) forms the remaining 1.07%.[14] The concentration of 12C is
further increased in biological materials because biochemical reactions discriminate
against 13C.[55] In 1961, the International Union of Pure and Applied
Chemistry (IUPAC) adopted the isotope carbon-12 as the basis for atomic
weights.[56] Identification of carbon in NMR experiments is done with the isotope 13C.

Carbon-14 (14C) is a naturally occurring radioisotope which occurs in trace amounts on


Earth of up to 1 part per trillion (0.0000000001%), mostly confined to the atmosphere
and superficial deposits, particularly of peat and other organic materials.[57] This
isotope decays by 0.158 MeV emission. Because of its relatively short half-life of
5730 years, 14C is virtually absent in ancient rocks, but is created in the upper
atmosphere (lower stratosphere and upper troposphere) by interaction
of nitrogen with cosmic rays.[58] The abundance of 14C in the atmosphere and in living
organisms is almost constant, but decreases predictably in their bodies after death.
This principle is used in radiocarbon dating, invented in 1949, which has been used
extensively to determine the age of carbonaceous materials with ages up to about
40,000 years.[59][60]

There are 15 known isotopes of carbon and the shortest-lived of these is 8C which
decays through proton emission and alpha decay and has a half-life of
1.98739x1021 s.[61] The exotic 19C exhibits anuclear halo, which means its radius is
appreciably larger than would be expected if the nucleus were a sphere of
constant density.[62]

Formation in stars

Main articles: Triple-alpha process and CNO cycle

Formation of the carbon atomic nucleus requires a nearly simultaneous triple collision
of alpha particles (helium nuclei) within the core of a giant or supergiant star which is
known as the triple-alpha process, as the products of further nuclear fusion reactions
of helium with hydrogen or another helium nucleus produce lithium-5 and beryllium-
8 respectively, both of which are highly unstable and decay almost instantly back into
smaller nuclei.[63] This happens in conditions of temperatures over 100 megakelvin and
helium concentration that the rapid expansion and cooling of the early universe
prohibited, and therefore no significant carbon was created during the Big Bang.
Instead, the interiors of stars in the horizontal branch transform three helium nuclei
into carbon by means of this triple-alpha process.[64] In order to be available for
formation of life as we know it, this carbon must then later be scattered into space as
dust, in supernova explosions, as part of the material which later forms second, third-
generation star systems which have planets accreted from such dust.[41][65] The Solar
System is one such third-generation star system. Another of the fusion mechanisms
powering stars is the CNO cycle, in which carbon acts as a catalyst to allow the
reaction to proceed.
Rotational transitions of various isotopic forms of carbon monoxide (for
example, 12CO, 13CO, and C18O) are detectable in the submillimeter wavelength range,
and are used in the study of newly forming stars in molecular clouds.[66]

Carbon cycle

Main article: Carbon cycle

Diagram of the carbon cycle. The black numbers indicate how much carbon is stored
in various reservoirs, in billions tonnes ("GtC" stands for gigatonnes of carbon;
figures are circa 2004). The purple numbers indicate how much carbon moves
between reservoirs each year. The sediments, as defined in this diagram, do not
include the ~70 million GtC of carbonate rock and kerogen.

Under terrestrial conditions, conversion of one element to another is very rare.


Therefore, the amount of carbon on Earth is effectively constant. Thus, processes that
use carbon must obtain it somewhere and dispose of it somewhere else. The paths that
carbon follows in the environment make up the carbon cycle. For example, plants
draw carbon dioxide out of their environment and use it to build biomass, as in carbon
respiration or the Calvin cycle, a process of carbon fixation. Some of this biomass is
eaten by animals, whereas some carbon is exhaled by animals as carbon dioxide. The
carbon cycle is considerably more complicated than this short loop; for example,
some carbon dioxide is dissolved in the oceans; dead plant or animal matter may
become petroleum or coal, which can burn with the release of carbon, should bacteria
not consume it.[67][68]

Compounds
Main article: Compounds of carbon

Organic compounds
Structural formula ofmethane, the simplest possible organic compound.

Correlation between the carbon cycle and formation of organic compounds. In plants,
carbon dioxide formed by carbon fixation can join with water
in photosynthesis (green) to form organic compounds, which can be used and further
converted by both plants and animals.

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 as well).

The simplest form of an organic molecule is the hydrocarbona large family


of organic molecules that are composed of hydrogen atoms bonded to a chain of
carbon atoms. Chain length, side chains andfunctional 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 including sugars, lignans, chitins, alcohols, fats, and
aromatic esters, carotenoids andterpenes. 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 formsDNA 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
thepaleoatmosphere, but is a minor component of the Earth's
atmosphere today.[69] Dissolved in water, it forms carbonic acid (H
2CO
3), but as most compounds with multiple single-bonded oxygens on a single carbon it
is unstable.[70] Through this intermediate, though, resonance-
stabilized carbonate ions are produced. Some important minerals are carbonates,
notably calcite. Carbon disulfide (CS
2) 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.[71][72] Cyanide (CN),
has a similar structure, but behaves much like a halide ion (pseudohalogen). For
example, it can form the nitride cyanogen molecule ((CN)2), similar to diatomic
halides. Other uncommon oxides are carbon suboxide (C
3O
2),[73] the unstable dicarbon monoxide(C2O),[74][75] carbon
trioxide (CO3),[76][77] cyclopentanepentone (C5O5)[78] cyclohexanehexone (C6O6),[78] and me
llitic anhydride (C12O9).
With reactive metals, such as tungsten, carbon forms either carbides (C4),
or acetylides (C2
2) 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,[79] carbon prefers to form covalent bonds. A few carbides are covalent lattices,
like carborundum (SiC), which resembles diamond.

Organometallic compounds

Main article: Organometallic chemistry

Organometallic compounds by definition contain at least one carbon-metal bond. A


wide range of such compounds exist; major classes include simple alkyl-metal
compounds (for example,tetraethyllead), 2-alkene compounds (for example, Zeise's
salt), and 3-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 [(Ph3PAu)6C]2+. This phenomenon has been attributed to
the aurophilicity of the gold ligands.[80]

History and etymology

Antoine Lavoisier in his youth

The English name carbon comes from the Latin carbo for coal and
charcoal,[81] whence also comes the French charbon, meaning charcoal.
In German, Dutch and Danish, the names for carbon
areKohlenstoff, 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 with clay to exclude air.[82][83]

Carl Wilhelm Scheele

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.[84] 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,[85] 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.[86] 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.[87] 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.[88]

A new allotrope of carbon, fullerene, that was discovered in


1985[89] includes nanostructured forms such as buckyballs and nanotubes.[28] Their
discoverers Robert Curl, Harold Kroto and Richard Smalley received the Nobel
Prize in Chemistry in 1996.[90] 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.[35] The developement of carbon
technology was very slow, but by the late 1960s it gave a boost.
Production
Graphite

Main article: 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.[91]

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.[91]

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.[91]

Diamond

Main article: Diamond


Diamond output in 2005

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 (see
figure).

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.[92]

Historically diamonds were known to be found only in alluvial deposits in southern


India.[93] India led the world in diamond production from the time of their discovery in
approximately the 9th century BCE[94] 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.[95]

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.[96] 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.[96]

In the United States, diamonds have been found


in Arkansas, Colorado and Montana.[97][98] In 2004, a startling discovery of a
microscopic diamond in the United States[99] led to the January 2008 bulk-sampling
of kimberlite pipes in a remote part of Montana.[100]

Today, most commercially viable diamond deposits are


in Russia, Botswana, Australia and the Democratic Republic of Congo.[101] 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.[97]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

Pencil leads for mechanical pencils are made of graphite(often mixed with a clay or
synthetic binder).

Sticks of vine and compressedcharcoal.

A cloth of woven carbon fibres


Silicon carbide single crystal

The C60 fullerene in crystalline form

Tungsten carbide milling bits

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
adistillation 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 is carbon 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 in electroplating and electroforming,
in brushes forelectric 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 qualitydiamond is used in jewelry, and industrial
diamonds are used in drilling, cutting and polishing tools for machining metals and
stone. Plastics are made from fossil hydrocarbons, and carbon fiber, made
bypyrolysis 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 higherspecific tensile strength than steel.[102]

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 inrubber products such as tyres and
in plastic compounds. Activated charcoal is used as
an absorbent and adsorbent in filter material in applications as diverse as gas
masks, water purification and kitchenextractor 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 abrasivesin cutting and grinding tools.
Carbon compounds make up most of the materials used in clothing, such as natural
and synthetic textiles and leather, 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.[103] 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.[104] 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.[105] 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.[106][107] 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 sinkin electronics.[108]

Precautions

Worker at carbon blackplant in Sunray, Texas(photo by John Vachon, 1942)


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 black was probably one of the first pigments to be used
fortattooing, and tzi the Iceman was found to have carbon tattoos that survived
during his life and for 5200 years after his death.[109] However, inhalation of coal dust
or soot (carbon black) in large quantities can be dangerous, irritating lung tissues and
causing the congestive lung disease coalworker'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.[110] 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.[111]

Carbon may also burn vigorously and brightly in the presence of air at high
temperatures. Large accumulations of coal, which have remained inert for hundreds of
millions of years in the absence of oxygen, may spontaneously combust when
exposed to air, for example in coal mine waste tips.

In nuclear applications where graphite is used as a neutron moderator, accumulation


of Wigner energy followed by a sudden, spontaneous release may occur. Annealing to
at least 250 C can release the energy safely, although in the Windscale fire the
procedure went wrong, causing other reactor materials to combust.

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)
and carbon monoxide; and such essentials to life as glucose and protein.

Nitrogen
From Wikipedia, the free encyclopedia
Jump to: navigation, search

Nitrogen, N
7
Liquid nitrogen

Spectral lines of nitrogen

General properties

Name, symbol nitrogen, N

Appearance colorless gas, liquid or solid

Pronunciation /natrdn/
NY-tr-jn

Nitrogen in the periodic table



N

P

carbon nitrogen oxygen

Atomic number 7

Standard atomic weight (Ar) 14.007[1] (14.0064314.00728)[2]


Element category diatomic nonmetal

Group, block group 15 (pnictogens), p-block

Period period 2

Electron configuration [He] 2s2 2p3

per shell 2, 5

Physical properties

Phase gas

Melting point 63.15 K (210.00 C, 346.00 F)

Boiling point 77.355 K (195.795 C,


320.431 F)

Density at stp (0 C and 101.325 kPa) 1.251 g/L

when liquid, at b.p. 0.808 g/cm3

Triple point 63.151 K, 12.52 kPa

Critical point 126.192 K, 3.3958 MPa

Heat of fusion (N2) 0.72 kJ/mol

Heat of vaporization (N2) 5.56 kJ/mol

Molar heat capacity (N2) 29.124 J/(molK)

vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 37 41 46 53 62 77
Atomic properties

Oxidation states 5, 4, 3, 2, 1, 1, 2, 3 (a
strongly acidic oxide)

Electronegativity Pauling scale: 3.04

Ionization energies 1st: 1402.3 kJ/mol


2nd: 2856 kJ/mol
3rd: 4578.1 kJ/mol
(more)

Covalent radius 711 pm

Van der Waals radius 155 pm

Miscellanea

Crystal structure hexagonal

Speed of sound 353 m/s (gas, at 27 C)

Thermal conductivity 25.83103 W/(mK)

Magnetic ordering diamagnetic

CAS Registry Number 7727-37-9

History

Discovery Daniel Rutherford (1772)

Named by Jean-Antoine Chaptal(1790)


Most stable isotopes

Main article: Isotopes of nitrogen

iso NA half-life DM DE (MeV) DP


13
N syn 9.965 min 2.220 13
C
14
N 99.634% N is stable with 7 neutrons
14

15
N 0.366%15N is stable with 8 neutrons

references

Nitrogen is a chemical element with symbol N and atomic number 7. It is the


lightest pnictogen and at room temperature, it is a transparent, odorlessdiatomic gas.
Nitrogen is a common element in the universe, estimated at about seventh in total
abundance in the Milky Way and the Solar System. On Earth, the element forms about
78% of Earth's atmosphere and as such is the most abundant uncombined element.
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 triple bond in elemental nitrogen (NN) dominates nitrogen
chemistry, causing difficulty for both organisms and industry in converting the N 2 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.
Synthetically-produced ammonia and nitrates are key industrial fertilizers and
fertilizer nitrates are keypollutants in causing the eutrophication of water systems.

Outside the major uses of nitrogen compounds as fertilizers and energy-stores,


nitrogen is a constituent of organic compounds as diverse as Kevlarfabric
and cyanoacrylate "super" glue. Nitrogen is a constituent of molecules in every major
pharmacological drug class, including antibiotics. Many drugs are mimics or prodrugs
of natural nitrogen-containing signal molecules: for example, the organic
nitrates nitroglycerin and nitroprusside controlblood pressure by being metabolized
to nitric oxide. Plant alkaloids (often defense chemicals) contain nitrogen by
definition, and thus many notable nitrogen-containing drugs, such
as caffeine and morphine are either alkaloids or synthetic mimics that act (as many
plant alkaloids do) on receptors of animal neurotransmitters (for example,
synthetic amphetamines).
Nitrogen occurs in all organisms, primarily in amino acids (and thus proteins), in
the nucleic acids (DNA and RNA) and in the energy transfer moleculeadenosine
triphosphate. The human body contains about 3% by mass 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.

Contents
[hide]

1 History and etymology


2 Production
3 Properties
o 3.1 Isotopes
o 3.2 Electromagnetic spectrum
o 3.3 Reactions
4 Occurrence
5 Compounds
6 Applications
o 6.1 Nitrogen gas
o 6.2 Liquid nitrogen
o 6.3 Nitrogen compounds
7 Biological role
8 Safety
9 See also
10 Notes
11 References
12 Bibliography
13 Further reading
14 External links

History and etymology


Nitrogen is formally considered to have been discovered by Scottish physician Daniel
Rutherford in 1772, who called it noxious air.[3][4] Though he did not recognize it as an
entirely different chemical substance, he clearly distinguished it from Joseph
Black's "fixed air", or carbon dioxide.[5] 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 thatAntoine Lavoisier referred to it as "mephitic air" or azote, from
the Greek word azotos, "lifeless".[6] In it, animals died and flames were
extinguished. This "mephitic air" consisted mostly of N2, but might also have included
more than 1% argon.

Lavoisier's name for nitrogen is used in many languages (French, Italian, Polish,
Russian, Albanian, Turkish, 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" from Greek - -genes,
"producer, begetter". 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 saltpeter (potassium nitrate), then known as niter.[7]

Nitrogen compounds were well known by the Middle Ages. Alchemists knew nitric
acid as aqua fortis (strong water). The mixture of nitric andhydrochloric acids was
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 saltpeter (sodium nitrate or potassium
nitrate), most notably in gunpowder, and later asfertilizer. In 1910, Lord
Rayleigh discovered that an electrical discharge in nitrogen gas produced "active
nitrogen", a monatomic allotrope of nitrogen. The "whirling cloud of brilliant yellow
light" produced by his apparatus reacted with quicksilver to produce
explosive mercury nitride.[8]

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 FrankCaro
process (18951899) and HaberBosch process (19081913) eased this shortage of
nitrogen compounds, to the extent that half of global food production (see
applications) now relies on synthetic nitrogen fertilizers.[9] At the same time, use of
the Ostwald process (1902) to produce nitrates from industrial nitrogen fixation
allowed the large-scale industrial production of nitrates as feedstock in the
manufacture of explosives in the World Wars of the 20th century.

Production
Further information: Air separation
Nitrogen gas is an industrial gas produced by the fractional distillation of liquid air, or
by mechanical means using gaseous air (i.e., pressurized reverseosmosis
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 (oxygen-free
nitrogen).[10]

In a chemical laboratory it is prepared by treating an aqueous solution of ammonium


chloride with sodium nitrite.[11]

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.[11] Very pure nitrogen can be prepared by the
thermal decomposition of barium azide or sodium azide.[12]

2 NaN3 2 Na + 3 N2

Properties
Nitrogen is a nonmetal, with an electronegativity of 3.04.[13] It has five electrons in
its outer shell and is, therefore, trivalent in most compounds. Thetriple bond in
molecular nitrogen (N
2) is one of the strongest. The resulting difficulty of converting N
2 into other compounds, and the ease (and associated high energy release) of
converting nitrogen compounds into elemental N
2, have dominated the role of nitrogen in both nature and human economic
activities.[citation needed]

At atmospheric pressure, molecular nitrogen condenses (liquefies) at


77 K (195.79 C) and freezes at 63 K (210.01 C)[14] 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).[15] 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.[16]

Unstable allotropes of nitrogen consisting of more than two nitrogen atoms have been
produced in the laboratory, like N
3 and N
4.[17] 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. N
4 is nicknamed "nitrogen diamond".[18]

Other (as yet unsynthesized) allotropes include hexazine (N


6, a benzene analog)[19] and octaazacubane (N
8, a cubane analog).[20] The former is predicted to be highly unstable, while the latter is
predicted to be kinetically stable, for reasons of orbital symmetry.[21]

Isotopes

See also: Isotopes of nitrogen

There are two stable isotopes of nitrogen: 14N and 15N. By far the most common is 14N
(99.634%), which is produced in the CNO cycle in stars.[22] Of the ten isotopes
produced synthetically, 13N has ahalf-life of ten minutes and the remaining isotopes
have half-lives on the order of seconds or less.[23]

Biologically mediated reactions (e.g., assimilation, nitrification, and denitrification)


strongly control nitrogen dynamics in the soil. These reactions typically result in 15N
enrichment of the substrate and depletion of the product.[24]

A small part (0.73%) of the molecular nitrogen in Earth's atmosphere is


the isotopologue 14N15N, and almost all the rest is 14N2.[25]

The radioisotope 16N is the dominant radionuclide in the coolant of pressurized water
reactors or boiling water reactors during normal operation. It is produced from 16O (in
water) via (n,p) reaction. It has a short half-life of about 7.1 s,[23] but during its decay
back to 16O produces high-energy gamma radiation (5 to 7 MeV).[23][26]

Because of this, the access to the primary coolant piping in a pressurized water reactor
must be restricted during reactor power operation. 16N is one of the main means used
to immediately detect even small leaks from the primary coolant to the secondary
steam cycle.[26]

In similar fashion, access to any of the steam cycle components in a boiling water
reactor nuclear power plant must be restricted during operation. Condensate from the
condenser is typically retained for 10 minutes to allow for decay of the 16N. This
eliminates the need to shield and restrict access to any of the feed water piping or
pumps.[citation needed]

Electromagnetic spectrum
Nitrogen discharge (spectrum) tube

Molecular nitrogen (14N2) is largely transparent to infrared and visible radiation


because it is a homonuclear molecule and, thus, has no dipole moment to couple
to electromagnetic radiation at thesewavelengths. Significant absorption occurs at
extreme ultraviolet wavelengths,[27] beginning around 100 nanometers. This is
associated with electronic transitions in the molecule to states in which charge is not
distributed evenly between nitrogen atoms. Nitrogen absorption leads to significant
absorption of ultraviolet radiation in the Earth's upper atmosphere and the
atmospheres of other planetary bodies. For similar reasons, pure molecular nitrogen
lasers typically emit light in the ultraviolet range.

Nitrogen also makes a contribution to visible air glow from the Earth's upper
atmosphere, through electron impact excitation followed by emission. This visible
blue air glow (seen in the polar aurora and in the re-entry glow of returning
spacecraft) typically results not from molecular nitrogen but rather from free nitrogen
atoms combining with oxygen to form nitric oxide (NO).

Nitrogen gas also exhibits scintillation.

Reactions

Structure of dinitrogen, N2

Structure of [Ru(NH3)5(N2)]2+
In general, nitrogen is unreactive at standard temperature and pressure. N 2 reacts
spontaneously with few reagents, being resilient to acids and bases as well as oxidants
and most reductants. When nitrogen reacts spontaneously with a reagent, the net
transformation is often called nitrogen fixation.[citation needed]

Nitrogen reacts with elemental lithium. Lithium burns in an atmosphere of N2 to


give lithium nitride:[28]

6 Li + N2 2 Li3N

Magnesium also burns in nitrogen, forming magnesium nitride.[citation needed]

3 Mg + N2 Mg3N2

N2 forms a variety of adducts with transition metals. The first example of a dinitrogen
complex is [Ru(NH3)5(N2)]2+ (see figure at right). However, it is interesting to note that
the N2 ligand was obtained by the decomposition of hydrazine, and not coordination of
free dinitrogen. Such compounds are now numerous, other examples include
IrCl(N2)(PPh3)2, W(N2)2(Ph2PCH2CH2PPh2)2, and [(5-C5Me4H)2Zr]2(2, 2,2-N2).
These complexes illustrate how N2 might bind to the metal(s) in nitrogenase and
the catalyst for the Haber process.[29] A catalytic process to reduce N2 to ammonia with
the use of a molybdenum complex in the presence of a proton source was published in
2005.[28]

The beginning point for industrial production of nitrogen compounds is the Haber
process, in which nitrogen is fixed by reacting N
2 and H
2 over an iron(II, III) oxide (Fe
3O
4) catalyst at about 500 C and 200 atmospheres pressure. Biological nitrogen fixation
in free-living cyanobacteria and in the root nodules of plants also produces ammonia
from molecular nitrogen. The reaction, which is the source of the bulk of nitrogen in
the biosphere, is catalyzed by the nitrogenase enzyme complex that contains Fe and
Mo atoms, using energy derived from hydrolysis of adenosine triphosphate (ATP)
intoadenosine diphosphate and inorganic phosphate (20.5 kJ/mol).[citation needed]

Occurrence
See also: the categories Nitrate minerals and Ammonium minerals.

Nitrogen gas (N2) is the largest constituent of Earth's atmosphere (78.082% by volume
of dry air, 75.3% by weight in dry air).[30] 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.[citation needed]

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, the Milky Way,
and the Solar System. In these places it was originally created by fusion processes
from carbon and hydrogen in supernovas.[31] Molecular nitrogen and
nitrogen compounds have been detected in interstellar space by astronomers using
the Far Ultraviolet Spectroscopic Explorer.[32]

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 System. Nitrogen is estimated at 31st element in crustal
abundance. There exist some relatively uncommon nitrogen minerals, such
as saltpeter (potassium nitrate), Chile saltpeter (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 elementboron.[citation needed]

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.[a] 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.[33]

Nitrogen is present in all known 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.[citation needed]

Compounds
See also: Category:Nitrogen compounds.
The main neutral hydride of nitrogen is ammonia (NH
3), although hydrazine (N
2H
4) 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 (NH
2); 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.[citation needed]

Other classes of nitrogen anions (negatively charged ions) are the


poisonous azides (N
3), 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, N
2O), 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 NO
2 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[clarification needed]acids
are nitrous HNO
2 and nitric acid HNO
3, with the corresponding salts called nitrites and nitrates.

The higher oxides dinitrogen trioxide N


2O
3, dinitrogen tetroxide N
2O
4 and dinitrogen pentoxide N
2O
5, are unstable and explosive, a consequence of the chemical stability of N
2. Nearly every hypergolicrocket engine uses N
2O
4 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 theApollo 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. N
2O
4 is an intermediate in the manufacture of nitric acid HNO
3, a strong acid and a fairly strong oxidizing agent.

Nitrogen is notable for the range of explosively unstable compounds that it can
produce. Nitrogen triiodide NI
3 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 explosive trinitrotoluene (TNT) is the standard
explosive against which the power of nuclear explosions are measured.[34]

Nitrogen can also be found in many 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.[citation needed]

Applications
Nitrogen gas

Nitrogen gas has a variety of applications, including serving as an inert replacement


for air where oxidation is undesirable;[35]

As a modified atmosphere, pure or mixed with carbon dioxide, to nitrogenate


and preserve the freshness of packaged or bulk foods (by delaying rancidity and
other forms of oxidative damage). Pure nitrogen as food additive is labeled in
the European Union with the E number E941.[36]
In incandescent light bulbs as an inexpensive alternative to argon.[37]
In photolithography in deep ultraviolet, nitrogenation is used to avoid the
strong oxygen absorption of UV at these wavelengths.
Dried and pressurized, as a dielectric gas for high-voltage equipment.[citation needed]
The manufacturing of stainless steel.[38]
Used in some aircraft fuel systems to reduce fire hazard, (see inerting
system).[39]
On top of liquid explosives as a safety measure.[citation needed]
Filling race cars and aircraft tires[40] due to its lower thermal expansion[citation
needed]
and lack of moisture or oxidative qualities, as opposed to air.

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.[41]

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.[42] A pressure-sensitive nitrogen capsule known commonly as a "widget"
allows nitrogen-charged beers to be packaged in cans and bottles.[43][44]

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.[45]

Nitrogen gas has become the inert gas of choice for inert gas asphyxiation, and is
under consideration as a replacement for lethal injection in Oklahoma.[46] Nitrogen is
promoted by euthanasia advocatePhilip Nitschke to end life in a "peaceful, reliable
[and] totally legal" manner.[47]

Liquid nitrogen

Air balloon submerged in liquid nitrogen


Main article: Liquid nitrogen

Liquid nitrogen is a cryogenic liquid. At atmospheric pressure, it boils at 195.8 C


(320.4 F). When insulated in proper containers such as Dewar flasks, it can be
transported without much evaporative loss.[48]
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.[49] 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.[50]

Nitrogen compounds

Molecular nitrogen (N2) in the atmosphere is relatively non-reactive due to its strong
triple bond, NN, and molecular nitrogen 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 bacteriaseeBiological 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. Previously to the 20th century, access to nitrogen compounds for fertilizers
and gunpowder had been through deposits of natural nitrates, such as
Chilean saltpeter. However, first the FrankCaro process for producing cyanamide,
and then the HaberBosch process for producing ammonia from air and natural
gas[14] (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.[35] 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[51] 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.
Table tennis ball made from nitrocellulose.

Ammonium nitrate has been used as both fertilizer[30] and explosive (see ANFO).
Various other nitrated organic compounds, such
as nitroglycerin, trinitrotoluene,[51] and nitrocellulose,[52] 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 (N 2), 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.[citation needed]

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 ofnitric oxide.[citation needed]

Biological role
See also: Nitrogen cycle and Human impacts on the nitrogen cycle

Nitrogen is an essential building block of amino and nucleic acids, essential to life on
Earth.[30]

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.[53] This was first proposed by Liebig in 1827
and later confirmed.[53] 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.[54]
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 nodulesof leguminous plants
(e.g. clover, Trifolium, or soybean plant, Glycine max) and fertilizer trees. Nitrogen-
fixing bacteria are also symbiotic with a number of unrelated plant species such as
alders (Alnus) spp., lichens, Casuarina, Myrica, liverworts, and Gunnera.[55]

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.[55] Legumes maintain an anaerobic (oxygen free) environment for
their nitrogen-fixing bacteria.[citation needed]

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 nitrite reductase.[55]

Nitrogen compounds are basic building blocks in animal biology as well. Animals use
nitrogen-containing 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.[56]

Soluble nitrate is an important limiting factor in the growth of certain bacteria in


ocean waters.[57] 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.
Well-known "dead zone" areas in the U.S. Gulf Coast and the Black Sea are due to
this important polluting process.[citation needed]

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.[58] In
animals, free radical nitric oxide (NO) (derived from an amino acid), serves as an
important regulatory molecule for circulation.[57]
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 of nucleic 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 putrescineand cadaverine,
which are breakdown products of the amino acids ornithine and lysine, respectively,
in decaying proteins.[59]

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.[55]

Safety
Rapid release of nitrogen gas into an enclosed space can displace oxygen, and
therefore presents an asphyxiation hazard. This may happen with few warning
symptoms, since the human carotid body is a relatively poor and slow low-oxygen
(hypoxia) sensing system.[60] 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 any early
symptoms from nitrogen-breathing.[citation needed]

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.[61][62]

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.[63][64] Bubbles from other "inert" gases (those gases other than
carbon dioxide and oxygen) cause the same effects, so replacement of nitrogen
in breathing gasesmay prevent nitrogen narcosis, but does not prevent decompression
sickness.[65]
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.[citation needed]

Oxygen sensors are sometimes used as a safety precaution when working with liquid
nitrogen to alert workers of gas spills into a confined space.[66]

Oxygen
From Wikipedia, the free encyclopedia
Jump to: navigation, search
This article is about the chemical element and its most stable form, O
2 or dioxygen. For other forms of this element, see Allotropes of oxygen. For other
uses, see Oxygen (disambiguation) and O2 (disambiguation).

Oxygen, O8
Liquid oxygen, boiling (oxygen is liquid below ca. 183 C (297 F), at 1
atm)

Spectral lines of oxygen

General properties

Name, symbol oxygen, O

Appearance gas: colorless


liquid: pale blue

Pronunciation /ksdn/
OK-si-jn

Oxygen in the periodic table



O

S

nitrogen oxygen fluorine

Atomic number 8

Standard atomic weight (Ar) 15.999[1] (15.9990315.99977)[2]

Element category diatomic nonmetal

Group, block group 16 (chalcogens),p-block

Period period 2

Electron configuration [He] 2s2 2p4


per shell 2, 6

Physical properties

Phase gas

Melting point 54.36 K (218.79 C, 361.82 F)

Boiling point 90.188 K (182.962 C,


297.332 F)

Density at stp (0 C and 101.325 kPa) 1.429 g/L

when liquid, at b.p. 1.141 g/cm3

Triple point 54.361 K, 0.1463 kPa

Critical point 154.581 K, 5.043 MPa

Heat of fusion (O2) 0.444 kJ/mol

Heat of vaporization (O2) 6.82 kJ/mol

Molar heat capacity (O2) 29.378 J/(molK)

vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 61 73 90

Atomic properties

Oxidation states 2, 1, 1, 2

Electronegativity Pauling scale: 3.44

Ionization energies 1st: 1313.9 kJ/mol


2nd: 3388.3 kJ/mol
3rd: 5300.5 kJ/mol
(more)

Covalent radius 662 pm

Van der Waals radius 152 pm

Miscellanea

Crystal structure cubic

Speed of sound 330 m/s (gas, at 27 C)

Thermal conductivity 26.58103 W/(mK)

Magnetic ordering paramagnetic

CAS Registry Number 7782-44-7

History

Discovery Carl Wilhelm Scheele(1772)

Named by Antoine Lavoisier (1777)

Most stable isotopes

Main article: Isotopes of oxygen

iso NA half-life DM DE (MeV) DP


16
O 99.76%16O is stable with 8 neutrons
17
O 0.039%17O is stable with 9 neutrons
18
O 0.201%18O is stable with 10 neutrons
references

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.[3] Photosynthesis releases oxygen, and respiration consumes oxygen.
Changes in phosphate[clarification needed] are related to changes in oxygen concentrations.[4]

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,[5] 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 - -genes, "producer", literally "begetter", because at the time of
naming, it was mistakenly thought that all acids required oxygen in their composition.

Contents
[hide]

1 Characteristics
o 1.1 Properties and molecular structure
o 1.2 Allotropes
o 1.3 Physical properties
o 1.4 Isotopes and stellar origin
o 1.5 Occurrence
o 1.6 Analysis
2 Biological role of O2
o 2.1 Photosynthesis and respiration
o 2.2 Living organsims
o 2.3 Build-up in the atmosphere
3 History
o 3.1 Early experiments
o 3.2 Phlogiston theory
o 3.3 Discovery
o 3.4 Lavoisier's contribution
o 3.5 Later history
4 Industrial production
5 Storage
6 Applications
o 6.1 Medical
o 6.2 Life support and recreational use
o 6.3 Industrial
7 Compounds
o 7.1 Oxides and other inorganic compounds
o 7.2 Organic compounds and biomolecules
8 Safety and precautions
o 8.1 Toxicity
o 8.2 Combustion and other hazards
9 See also
10 Notes
11 Citations
12 References
13 External links

Characteristics
By mass, oxygen is the third-most abundant element in the universe,
after hydrogen and helium.[6] At standardized conditions for temperature and pressure,
two atoms of the element bind to form dioxygen, a diatomic gas that is colorless,
odorless, and tasteless, with the formula O
2.[citation needed]

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).[citation
needed]
Elemental oxygen is produced by cyanobacteria, algaeand 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 O
2 began to accumulate in the atmosphereabout 2.5 billion years ago during the Great
Oxygenation Event, about a billion years after the first appearance of these
organisms.[7][8] Diatomic oxygen gas constitutes 20.8% of the volume of air.[9] However,
monitoring of atmospheric Oxygen levels show a global downward trend, because of
fossil-fuel burning.[10] 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.[11]
Oxygen is an important part of the atmosphere, and is necessary to sustain most
terrestrial life as it is used in respiration. 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 (O
3), 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,
sufficient atomic oxygen is present to cause erosion for spacecraft.[12]

Common usage of elemental oxygen includes the production cycle


of steel, plastics and textiles, brazing, welding and cutting of steels and
other metals,rocket propellant, in oxygen therapy and life support
systems in aircraft, submarines, spaceflight and diving.

Properties and molecular structure

Orbital diagram, after Barrett (2002),[13]showing the participating atomic orbitals from
each oxygen atom, the molecular orbitals that result from their overlap, and
the Aufbau filling of the orbitals with the 12 electrons, 6 from each O atom, beginning
from the lowest energy orbitals, and resulting in covalent double bond character from
filled orbitals (and cancelation of the contributions of the pairs of and *and and
* orbital pairs, see text).

At standard temperature and pressure, oxygen is a colorless, odorless gas with


the molecular formula O
2.
In this dioxygen, the two oxygen atoms are chemically bonded to each other. The
bond can be variously described based on level of theory, but is reasonably and
simply described as a covalent double bond that results from the filling of molecular
orbitals formed from the atomic orbitals of the individual oxygen atoms, the filling of
which results in a bond order of two. More specifically, with reference to
the molecular orbital diagram shown at the left, the double bond is the result of
sequential, low-to-high energy, or Aufbau, filling of orbitals, and the resulting:

cancellation of contributions from the 2s electrons, after sequential filling of the


low and * orbitals;
" overlap of the two [atomic] 2p orbitals that lie along the [O-O] molecular
axis and"
" overlap of... two sets [pairs] of [atomic] 2p orbitals... perpendicular to the
[O-O] molecular axis",

and then cancellation of contributions from the remaining two of the six 2p electrons
after their partial filling of the lowest and * orbitals.[13] This combination of
cancellations and and overlaps results in dioxygen's double bond character and
reactivity, and its triplet electronic ground state (see below). Note, in an early, distinct
description by Pauling in the 1960s, the bonds holding dioxygen together were
presented as a combination of a 2-electron bond and two 3-electron bonds.[14]

As noted, an electron configuration with two unpaired electrons as found in dioxygen


(see the filled * orbitals in the diagram), orbitals which are of equal energy
i.e., degenerateis a configuration termed a spin triplet state. Hence, the ground
state of the O
2 molecule is referred to as triplet oxygen.[15][a] The highest energy, partially filled
orbitals are antibonding, and so their filling weakens the bond order from three to two.

A trickle of liquid oxygen is deflected by a magnetic field, illustrating its


paramagnetic property

In the triplet form, O


2 molecules are paramagnetic. That is, they impart magnetic character to oxygen when
it is in the presence of a magnetic field, because of the spin magnetic moments of the
unpaired electrons in the molecule, and the negative exchange energy between
neighboring O
2 molecules.[clarification needed][16] 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.[17][b]

Singlet oxygen is a name given to several higher-energy species of molecular O


2 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.[18] It is also produced in the troposphere by the photolysis of ozone by light of
short wavelength,[19] and by the immune system as a source of active
oxygen.[20] Carotenoids in photosynthetic organisms (and possibly also in animals)
play a major role in absorbing energy fromsinglet oxygen and converting it to the
unexcited ground state before it can cause harm to tissues.[21]

Allotropes

Main article: Allotropes of oxygen

Ozone is a rare gas on Earth found mostly in thestratosphere.

Space-filling modelrepresentation of dioxygen (O2) molecule

The common allotrope of elemental oxygen on Earth is called dioxygen, O


2. It has a bond length of 121 pm and a bond energy of 498 kJmol1.[22] 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 O
2 are covered in the remainder of this article.
Trioxygen (O
3) is usually known as ozone and is a very reactive allotrope of oxygen that is
damaging to lung tissue.[23] Ozone is produced in the upper atmosphere when O
2 combines with atomic oxygen made by the splitting of O
2 by ultraviolet (UV) radiation.[5] 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.[5] Near the Earth's surface, it is a pollutant formed as a
by-product of automobile exhaust.[23] The metastable molecule tetraoxygen (O
4) was discovered in 2001,[24][25] 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 a rhombohedral O
8 cluster.[26] This cluster has the potential to be a much more powerful oxidizer than
either O
2 or O
3 and may therefore be used in rocket fuel.[24][25] A metallic phase was discovered in
1990 when solid oxygen is subjected to a pressure of above 96 GPa[27] and it was
shown in 1998 that at very low temperatures, this phase becomes superconducting.[28]

Physical properties

Oxygen discharge (spectrum) tube. The green color is similar to the color of
an "aurora borealis"
See also: Liquid oxygen and solid oxygen

Oxygen is more soluble in water than nitrogen is. Water in equilibrium with air
contains approximately 1 molecule of dissolved O
2 for every 2 molecules of N
2, compared to an atmospheric ratio of approximately 1:4. The solubility of oxygen in
water is temperature-dependent, and about twice as much (14.6 mgL1) dissolves at
0 C than at 20 C (7.6 mgL1).[29][30] 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.[31] 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).[32] Both liquid and solid O
2 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 O
2 is usually obtained by the fractional distillation of liquefied air.[33]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.[34]

The spectroscopy of molecular oxygen is associated with the atmospheric processes


of aurora, airglow and nightglow.[35] The absorption in the Herzberg
continuum and SchumannRunge bands in the ultraviolet produces atomic oxygen
that is important in the chemistry of the middle atmosphere.[36] Excited state singlet
molecular oxygen is responsible for red chemiluminescence in solution.[37]

Isotopes and stellar origin

Main article: Isotopes of oxygen

Late in a massive star's life, 16O concentrates in the O-shell, 17O in the H-shell and 18O
in the He-shell.

Naturally occurring oxygen is composed of three stable isotopes, 16O, 17O, and 18O,
with 16O being the most abundant (99.762% natural abundance).[38]

Most 16O is synthesized at the end of the helium fusion process in massive stars but
some is made in the neon burning process.[39] 17O is primarily made by the burning of
hydrogen into helium during theCNO cycle, making it a common isotope in the
hydrogen burning zones of stars.[39] Most 18O is produced when 14N (made abundant
from CNO burning) captures a 4He nucleus, making 18O common in the helium-rich
zones of evolved, massive stars.[39]

Fourteen radioisotopes have been characterized. The most stable are 15O with a half-
life of 122.24 seconds and 14O with a half-life of 70.606 seconds.[38] All of the
remaining radioactive isotopes have half-lives that are less than 27 s and the majority
of these have half-lives that are less than 83 milliseconds.[38] The most common decay
mode of the isotopes lighter than 16O is + decay[40][41][42] to yield nitrogen, and the most
common mode for the isotopes heavier than 18O is beta decay to yield fluorine.[38]

Occurrence

See also: Silicate minerals, Category:Oxide minerals, Stellar


population, Cosmochemistry and Astrochemistry
Ten most common elements in the Milky Way Galaxyestimated spectroscopically[43]
Z Element Mass fraction in parts per million
71 mass of oxygen
1 Hydrogen 739,000
(red bar)
23 mass of oxygen
2 Helium 240,000
(red bar)
8 Oxygen 10,400
6 Carbon 4,600
10 Neon 1,340
26 Iron 1,090
7 Nitrogen 960
14 Silicon 650
12 Magnesium 580
16 Sulfur 440

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.[6] About 0.9% of the Sun's mass is oxygen.[9] Oxygen
constitutes 49.2% of theEarth's crust by mass[11] and is the major component of the
world's oceans (88.8% by mass).[9] 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 1015 tonnes).[9][44][c] 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% O
2 by volume) and Venus have far lower concentrations. The O
2 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.

Cold water holds more dissolvedO


2.

Free oxygen also occurs in solution in the world's water bodies. The increased
solubility of O
2 at lower temperatures (see Physical properties) has important implications for ocean
life, as polar oceans support a much higher density of life due to their higher oxygen
content.[45] Water polluted with plant nutrients such as nitrates or phosphates may
stimulate growth of algae by a process calledeutrophication and the decay of these
organisms and other biomaterials may reduce amounts of O
2 in eutrophic water bodies. Scientists assess this aspect of water quality by measuring
the water'sbiochemical oxygen demand, or the amount of O
2 needed to restore it to a normal concentration.[46]

Analysis

500 million years of climate change vs18O

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.[47] 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.[47] Paleoclimatologists
also directly measure this ratio in the water molecules ofice 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. 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.[48]

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.[49] This approach exploits the
fact that in those bands it is possible to discriminate the vegetation'sreflectance 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.

Biological role of O2
Main article: Dioxygen in biological reactions

Photosynthesis and respiration


Photosynthesis splits water to liberate O
2 and fixes CO
2 into sugar in what is called a Calvin cycle.

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.[50] 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.[51]

A simplified overall formula for photosynthesis is:[52]

6 CO2 + 6 H
2O + photons C
6H
12O
6+6O
2

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.[d] Many steps are involved, but the
result is the formation of a protongradient across the thylakoid membrane, which is
used to synthesize ATP via photophosphorylation.[53] The O
2 remaining after oxidation of the water molecule is released into the atmosphere.[e]

Molecular dioxygen, O
2, 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:

C
6H
12O
6+6O
2 6 CO2 + 6 H
2O + 2880 kJmol1

In vertebrates, O
2 diffuses through membranes in the lungs and into red blood
cells. Hemoglobin binds O
2, changing its color from bluish red to bright red[23] (CO
2 is released from another part of hemoglobin through the Bohr effect). Other animals
use hemocyanin (molluscs and some arthropods)
or hemerythrin (spiders and lobsters).[44] A liter of blood can dissolve 200 cm3 of O
2.[44]

Reactive oxygen species, such as superoxide ion (O


2) and hydrogen peroxide (H
2O
2), are dangerous by-products of oxygen use in organisms.[44] Parts of the immune
system of higher organisms 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.[53]

An adult human in rest inhales 1.8 to 2.4 grams of oxygen per minute.[54] This amounts
to more than 6 billion tonnes of oxygen inhaled by humanity per year. [f]

Living organsims

Partial pressures of oxygen in the human body (PO2)


Alveolar pulmonary
Unit Arterial blood oxygen Venous blood gas
gas pressures
kPa 14.2 11[55]-13[55] 4.0[55]-5.3[55]
mmHg 107 75[56]-100[56] 30[57]-40[57]

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.[58]

Build-up in the atmosphere

Main article: Geological history of oxygen

O
2 build-up in Earth's atmosphere: 1) no O
2produced; 2) O
2 produced, but absorbed in oceans & seabed rock; 3) O
2 starts to gas out of the oceans, but is absorbed by land surfaces and formation of
ozone layer; 45) O
2 sinks filled and the gas accumulates

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).[59] 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.[59][60]

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. Cellular respiration using O
2 enables aerobic organisms to produce much more ATP, than anaerobic
organisms.[61] Cellular respiration of O
2occurs in all eukaryotes, including all complex multicellular organisms such as
plants and animals.

Since the beginning of the Cambrian period 540 million years ago, atmospheric O
2 levels have fluctuated between 15% and 30% by volume.[62] Towards the end of
the Carboniferous period (about 300 million years ago) atmospheric O
2 levels reached a maximum of 35% by volume,[62] which may have contributed to the
large size of insects and amphibians at this time.[63]

Variations of Oxygen shaped the climates of the past. When oxygen declined,
atmospheric density dropped and this in turn increased surface evaporation, and led to
precipitation increases and warmer temperatures.[64]

At the current rate of photosynthesis it would take about 2,000 years to regenerate the
entire O
2 in the present atmosphere.[65]

History
Early experiments

Philo's experiment inspired laterinvestigators.

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.[66] 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 later Leonardo da Vinci built on Philo's work by
observing that a portion of air is consumed during combustion and respiration.[67]

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.[68] 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.[69] 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.[68] 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.[68] Accounts of these and other experiments and ideas were published in 1668 in
his work Tractatus duo in the tract "De respiratione".[69]

Phlogiston theory

Main article: Phlogiston theory

Stahl helped develop and popularize the 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.[29] This may have been in part due to the prevalence of the
philosophy of combustion and corrosion called 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,[70] 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.[67]

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.[67] The fact that a substance like wood 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

Carl Wilhelm Scheele beat Priestley to the discovery but published afterwards.

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.[9][67] 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. That document was published
in 1777.[71]
Joseph Priestley is usually given priority in the discovery.

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".[9] 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."[29] 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.[67][72] Because he published his findings first, Priestley is usually
given priority in the discovery.

The French chemist Antoine Laurent Lavoisier later claimed to have discovered the
new substance independently. 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 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).[71]

Lavoisier's contribution

What Lavoisier did (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.[9] 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.
Antoine Lavoisierdiscredited the phlogiston theory.

In one experiment, Lavoisier observed that there was no overall increase in weight
when tin and air were heated in a closed container.[9] 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.[9] 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.[9]

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.[5] Chemists (such as Sir Humphry Davy in 1812)
eventually determined that Lavoisier was wrong in this regard (hydrogen 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.[71]

Later history
Robert H. Goddard and a liquid oxygen-gasolinerocket

John Dalton's original atomic hypothesis assumed that all elements were monatomic
and that the atoms in compounds would normally have the simplest atomic ratios with
respect to one another. For example, Dalton assumed that water's formula was HO,
giving the atomic mass of oxygen as 8 times that of hydrogen, instead of the modern
value of about 16.[73] In 1805, Joseph Louis Gay-Lussac andAlexander von
Humboldt showed that water is formed of two volumes of hydrogen and one volume
of oxygen; and by 1811 Amedeo Avogadro had arrived at the correct interpretation of
water's composition, based on what is now called Avogadro's law and the assumption
of diatomic elemental molecules.[74][g]

By the late 19th century scientists realized that air could be liquefied, and its
components isolated, by compressing and cooling it. Using a cascade method, Swiss
chemist and physicist Raoul Pierre Pictetevaporated liquid sulfur dioxide in order to
liquefy carbon dioxide, which in turn was evaporated to cool oxygen gas enough to
liquefy it. He sent a telegram on December 22, 1877 to the French Academy of
Sciences in Paris announcing his discovery of liquid oxygen.[75] Just two days later,
French physicist Louis Paul Cailletet announced his own method of liquefying
molecular oxygen.[75]Only a few drops of the liquid were produced in either case so no
meaningful analysis could be conducted. Oxygen was liquified in stable state for the
first time on March 29, 1883 by Polish scientists from Jagiellonian
University, Zygmunt Wrblewski and Karol Olszewski.[76]

In 1891 Scottish chemist James Dewar was able to produce enough liquid oxygen to
study.[16] The first commercially viable process for producing liquid oxygen was
independently developed in 1895 by German engineer Carl von Linde and British
engineer William Hampson. Both men lowered the temperature of air until it liquefied
and then distilled the component gases by boiling them off one at a time and capturing
them.[77] Later, in 1901, oxyacetylene welding was demonstrated for the first time by
burning a mixture of acetylene and compressed O
2. This method of welding and cutting metal later became common.[77]

In 1923 the American scientist Robert H. Goddard became the first person to develop
a rocket engine that burned liquid fuel; the engine used gasoline for fuel and liquid
oxygen as the oxidizer. Goddard successfully flew a small liquid-fueled rocket 56 m
at 97 km/h on March 16, 1926 in Auburn, Massachusetts, US.[77][78]

Industrial production

Hofmann electrolysis apparatusused in electrolysis of water.


See also: Air separation, Oxygen evolution and fractional distillation

Two major methods are employed to produce 100 million tonnes of O


2 extracted from air for industrial uses annually.[71] The most common method is
to fractionally distill liquefied air into its various components, with N
2 distilling as a vapor while O
2 is left as a liquid.[71]

The other major method of producing O


2 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% O
2.[71] 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 non-
cryogenic technologies (see also the related vacuum swing adsorption).[79]

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 O
2 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 O
2 gas.[46]

In large quantities, the price of liquid oxygen in 2001 was approximately


$0.21/kg.[80] Since the primary cost of production is the energy cost of liquefying the
air, the production cost will change as energy cost varies.

Storage
Oxygen storage methods include high pressure oxygen tanks, cryogenics and
chemical compounds. For reasons of economy, oxygen is often transported in bulk as
a liquid in specially insulated tankers, since one liter of liquefied oxygen is equivalent
to 840 liters of gaseous oxygen at atmospheric pressure and 20 C (68 F).[71] 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.[71]

Applications
See also: Breathing gas, Redox and Combustion

Medical

An oxygen concentrator in an emphysema patient's house


Main article: Oxygen therapy

Uptake of O
2 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
treat emphysema, 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.[81]

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.[82]

Hyperbaric (high-pressure) medicine uses special oxygen chambers to increase


the partial pressure of O
2 around the patient and, when needed, the medical staff.[83] Carbon monoxide
poisoning, gas gangrene, and decompression sickness (the 'bends') are sometimes
treated using these devices.[84] Increased O
2 concentration in the lungs helps to displace carbon monoxide from the heme group
ofhemoglobin.[85][86] Oxygen gas is poisonous to the anaerobic bacteria that cause gas
gangrene, so increasing its partial pressure helps kill them.[87][88] 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 O
2 as soon as possible is part of the treatment.[81][89][90]

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

Low pressure pure O


2 is used inspace suits.

An application of O
2 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 O
2.[91][92] 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 O


2, but most often use normal pressure, and/or mixtures of oxygen and air. Pure or
nearly pure O
2 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).[93][94] Deeper diving requires significant dilution of O
2 with other gases, such as nitrogen or helium, to help prevent oxygen toxicity.[93]

People who climb mountains or fly in non-pressurized fixed-wing aircraft sometimes


have supplemental O
2 supplies.[h] Passengers traveling in (pressurized) commercial airplanes have an
emergency supply of O
2 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.[46] A
steady stream of oxygen gas is then produced by theexothermic 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 O
2 exposure for a fee.[95] 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.[95] Available studies support a performance boost from enriched O
2 mixtures only if they are breathed during aerobic exercise.[96]

Other recreational uses that do not involve breathing the gas


include pyrotechnic applications, such as George Goble's five-second ignition
of barbecue grills.[97]

Industrial

Most commercially produced O


2is used to smelt iron into steel.

Smelting of iron ore into steel consumes 55% of commercially produced oxygen.[46] In
this process, O
2 is injected through a high-pressure lance into molten iron, which
removes sulfur impurities and excess carbon as the respective oxides, SO
2 and CO
2. The reactions are exothermic, so the temperature increases to 1,700 C.[46]

Another 25% of commercially produced oxygen is used by the chemical


industry.[46] Ethylene is reacted with O
2 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).[46]

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.[46] Oxygen is used inoxyacetylene welding burning acetylene with O
2 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 O
2.[98]

Compounds
Main article: Compounds of oxygen

Water (H
2O) is the most familiar oxygen compound.

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.[99] 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).

Oxides and other inorganic compounds

Water (H
2O) is an oxide of hydrogen and the most familiar oxygen compound. Hydrogen
atoms are covalently bonded to oxygen in a water molecule but also have an
additional attraction (about 23.3 kJmol1 per hydrogen atom) to an adjacent oxygen
atom in a separate molecule.[100] These hydrogen bonds between water molecules hold
them approximately 15% closer than what would be expected in a simple liquid with
just van der Waals forces.[101][i]

Oxides, such as iron oxide or rust, form when oxygen combines with other elements.

Due to its electronegativity, oxygen forms chemical bonds with almost all other
elements to give corresponding oxides. The surface of most metals, such
as aluminium and titanium, are oxidized in the presence of air and become coated
with a thin film of oxide that passivates the metal and slows further corrosion. Many
oxides of the transition metals are non-stoichiometric compounds, with slightly less
metal than the chemical formula would show. For example, the mineral FeO (wstite)
is written as Fe
1 xO, where x is usually around 0.05.[102]

Oxygen is present in the atmosphere in trace quantities in the form of carbon


dioxide (CO
2). The Earth's crustal rock is composed in large part of oxides of silicon (silica SiO
2, as found in granite andquartz), aluminium (aluminium oxide Al
2O
3, in bauxite and corundum), iron (iron(III) oxide Fe
2O
3, in hematite and rust), and calcium carbonate (in limestone). The rest of the Earth's
crust is also made of oxygen compounds, in particular various
complex silicates (in silicate minerals). The Earth's mantle, of much larger mass than
the crust, is largely composed of silicates of magnesium and iron.

Water-soluble silicates in the form of Na


4SiO
4, Na
2SiO
3, and Na
2Si
2O
5 are used as detergents and adhesives.[103]
Oxygen also acts as a ligand for transition metals, forming transition metal dioxygen
complexes, which feature metalO
2. This class of compounds includes
the heme proteins hemoglobin andmyoglobin.[104] An exotic and unusual reaction
occurs with PtF
6, which oxidizes oxygen to give O2+PtF6.[105]

Organic compounds and biomolecules

Acetone is an important feeder material in the chemical industry.


Oxygen
Carbon
Hydrogen

Oxygen represents more than 40% of the molecular mass of the ATPmolecule.

Among the most important classes of organic compounds that contain oxygen are
(where "R" is an organic group): alcohols (R-OH); ethers (R-O-R); ketones (R-CO-
R); aldehydes (R-CO-H); carboxylic acids (R-COOH); esters (R-COO-R); acid
anhydrides (R-CO-O-CO-R); and amides (R-C(O)-NR
2). There are many important organic solvents that contain oxygen,
including: acetone, methanol, ethanol,isopropanol, furan, THF, diethyl
ether, dioxane, ethyl acetate, DMF, DMSO, acetic acid, and formic acid. Acetone
((CH
3)
2CO) and phenol (C
6H
5OH) are used as feeder materials in the synthesis of many different substances. Other
important organic compounds that contain oxygen
are: glycerol, formaldehyde, glutaraldehyde, citric acid, acetic anhydride,
and acetamide. Epoxides are ethers in which the oxygen atom is part of a ring of three
atoms.

Oxygen reacts spontaneously with many organic compounds at or below room


temperature in a process called autoxidation.[106] Most of the organic compounds that
contain oxygen are not made by direct action of O
2. Organic compounds important in industry and commerce that are made by direct
oxidation of a precursor include ethylene oxide and peracetic acid.[103]

The element is found in almost all biomolecules that are important to (or generated
by) life. Only a few common complex biomolecules, such as squalene and
the carotenes, contain no oxygen. Of the organic compounds with biological
relevance, carbohydrates contain the largest proportion by mass of oxygen.
All fats, fatty acids, amino acids, and proteins contain oxygen (due to the presence
ofcarbonyl groups in these acids and their ester residues). Oxygen also occurs
in phosphate (PO3
4) groups in the biologically important energy-carrying molecules ATP and ADP, in
the backbone and thepurines (except adenine) and pyrimidines of RNA and DNA, and
in bones as calcium phosphate and hydroxylapatite.

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.

Toxicity

Main article: Oxygen toxicity


Main symptoms of oxygen toxicity[107]

Oxygen toxicity occurs when the lungs take in 2 12 higher than normal O
2 partial pressure, which can occur in deep scuba diving.

Oxygen gas (O
2) can be toxic at elevated partial pressures, leading to convulsions and other health
problems.[93][j][108] Oxygen toxicity usually begins to occur at partial pressures more than
50 kilopascals (kPa), equal to about 50% oxygen composition at standard pressure or
2.5 times the normal sea-level O
2 partial pressure of about 21 kPa. This is not a problem except for patients
onmechanical ventilators, since gas supplied through oxygen masks in medical
applications is typically composed of only 30%50% O
2 by volume (about 30 kPa at standard pressure).[29] (although this figure also is subject
to wide variation, depending on type of mask).
At one time, premature babies were placed in incubators containing O
2-rich air, but this practice was discontinued after some babies were blinded by the
oxygen content being too high.[29]

Breathing pure O
2 in space applications, such as in some modern space suits, or in early spacecraft such
as Apollo, causes no damage due to the low total pressures used.[91][109] In the case of
spacesuits, the O
2 partial pressure in the breathing gas is, in general, about 30 kPa (1.4 times normal),
and the resulting O
2 partial pressure in the astronaut's arterial blood is only marginally more than normal
sea-level O
2 partial pressure (for more information on this, see space suit and arterial blood gas).

Oxygen toxicity to the lungs and central nervous system can also occur in deep scuba
diving and surface supplied diving.[29][93] Prolonged breathing of an air mixture with
an O
2 partial pressure more than 60 kPa can eventually lead to permanent pulmonary
fibrosis.[110] Exposure to a O
2 partial pressures greater than 160 kPa (about 1.6 atm) may lead to convulsions
(normally fatal for divers). Acute oxygen toxicity (causing seizures, its most feared
effect for divers) can occur by breathing an air mixture with 21% O
2 at 66 m or more of depth; the same thing can occur by breathing 100% O
2 at only 6 m.[110][111][112][113]

Combustion and other hazards

The interior of the Apollo 1Command Module. Pure O


2 at higher than normal pressure and a spark led to a fire and the loss of the Apollo
1 crew.

Highly concentrated sources of oxygen promote rapid


combustion. Fire and explosion hazards exist when concentrated oxidants
and fuels are brought into close proximity; an ignition event, such as heat or a spark,
is needed to trigger combustion.[114] Oxygen is not the fuel, but the oxidant.
Combustion hazards also apply to compounds of oxygen with a high oxidative
potential, such as peroxides,chlorates, nitrates, perchlorates, and dichromates because
they can donate oxygen to a fire.

Concentrated O
2 will allow combustion to proceed rapidly and energetically. [114] Steel pipes and
storage vessels used to store and transmit both gaseous and liquid oxygen will act as a
fuel; and therefore the design and manufacture of O
2 systems requires special training to ensure that ignition sources are
minimized.[114] The fire that killed the Apollo 1 crew in a launch pad test spread so
rapidly because the capsule was pressurized with pure O
2 but at slightly more than atmospheric pressure, instead of the 13 normal pressure that
would be used in a mission.[k][116]

Liquid oxygen spills, if allowed to soak into organic matter, such


as wood, petrochemicals, and asphalt can cause these materials
to detonate unpredictably on subsequent mechanical impact.[114] As with
other cryogenic liquids, on contact with the human body it can cause frostbites to the
skin and the eyes.

See also
Geological history of oxygen
Hypoxia (environmental) for O
2 depletion in aquatic ecology
Ocean deoxygenation
Hypoxia (medical), a lack of oxygen
Limiting oxygen concentration
Oxygen compounds
Oxygen plant
Oxygen sensor

Notes
1. An orbital is a concept from quantum mechanics that models an electron as a wave-like
particle that has a spacial distribution about an atom or molecule.
2. Oxygen's paramagnetism can be used analytically in paramagnetic oxygen gas analysers that
determine the purity of gaseous oxygen. ("Company literature of Oxygen analyzers (triplet)".
Servomex. RetrievedDecember 15, 2007.)
3. Figures given are for values up to 50 miles (80 km) above the surface
4. Thylakoid membranes are part of chloroplasts in algae and plants while they simply are one of
many membrane structures in cyanobacteria. In fact, chloroplasts are thought to have evolved
from cyanobacteria that were once symbiotic partners with the progenerators of plants and algae.
5. Water oxidation is catalyzed by a manganese-containing enzyme complex known as the oxygen
evolving complex (OEC) or water-splitting complex found associated with the lumenal side of
thylakoid membranes. Manganese is an important cofactor, and calcium and chloride are also
required for the reaction to occur. (Raven 2005)
6. (1.8 grams/min/person)(60 min/h)(24 h/day)(365 days/year)(6.6 billion people)/1,000,000
g/t=6.24 billion tonnes
7. These results were mostly ignored until 1860. Part of this rejection was due to the belief that
atoms of one element would have no chemical affinity towards atoms of the same element, and
part was due to apparent exceptions to Avogadro's law that were not explained until later in terms
of dissociating molecules.
8. The reason is that increasing the proportion of oxygen in the breathing gas at low pressure acts to
augment the inspired O
2 partial pressure nearer to that found at sea-level.
9. Also, since oxygen has a higher electronegativity than hydrogen, the charge difference makes it
a polar molecule. The interactions between the different dipoles of each molecule cause a net
attraction force.
10. Since O
2's partial pressure is the fraction of O
2 times the total pressure, elevated partial pressures can occur either from high O
2 fraction in breathing gas or from high breathing gas pressure, or a combination of both.
11. No single ignition source of the fire was conclusively identified, although some evidence points
to arc from an electrical spark.[115]

Fluorine
From Wikipedia, the free encyclopedia
Jump to: navigation, search
Not to be confused with fluorene, fluorane, or fluoride.

Fluorine, F 9

Liquid fluorine at cryogenic temperatures


General properties

Name, symbol fluorine, F

Appearance gas: very pale yellow


liquid: bright yellow
solid: alpha is opaque, beta is transparent

Allotropes alpha, beta

Pronunciation /flrin/, /flrn/, /flrin/


FLOOR-een, FLOOR-in, FLOHR-een

Fluorine in the periodic table



F

Cl

oxygen fluorine neon

Atomic number 9

Standard atomic 18.998403163(6)[1]


weight () (Ar)

Element category diatomic nonmetal

Group, block group 17 (halogens), p-block

Period period 2

Electron configuration [He] 2s2 2p5[2]

per shell 2, 7
Physical properties

Phase gas

Melting point 53.48 K (219.67 C, 363.41 F)[3]

Boiling point 85.03 K (188.11 C, 306.60 F)[3]

Density at stp(0 C and 1.696 g/L[4]


101.325 kPa)

when liquid, at b.p. 1.505 g/cm3[5]

Triple point 53.48 K, 90 kPa[3]

Critical point 144.41 K, 5.1724 MPa[3]

Heat of vaporization 6.51 kJ/mol[4]

Molar heat capacity Cp: 31 J/(molK)[5](at 21.1 C)


Cv: 23 J/(molK)[5](at 21.1 C)

vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 38 44 50 58 69 85

Atomic properties

Oxidation states 1 (oxidizes oxygen)

Electronegativity Pauling scale: 3.98[2]

Ionization energies 1st: 1681 kJ/mol


2nd: 3374 kJ/mol
3rd: 6147 kJ/mol
(more)[6]
Covalent radius 64 pm[7]

Van der Waals radius 135 pm[8]

Miscellanea

Crystal structure cubic

Thermal conductivity 0.02591 W/(mK)[9]

Magnetic ordering diamagnetic(1.2104)[10][11]

CAS Registry Number 7782-41-4[2]

History

Naming after the mineral fluorite, itself named after


Latin fluo (to flow, in smelting)

Discovery Andr-Marie Ampre (1810)

First isolation Henri Moissan[2](June 26, 1886)

Named by Humphry Davy

Most stable isotopes

Main article: Isotopes of fluorine

iso NA half-life DM DE (MeV) DP


+
(96.9%) 0.634 18
O
18
F trace 109.77 min
(3.1%) 1.656 18
O
19
F 100% F is stable with 10 neutrons
19
reference[12]

references

Fluorine is a chemical element with symbol F and atomic number 9. It is the


lightest halogen and exists as a highly toxic pale yellow diatomic gas atstandard
conditions. As the most electronegative element, it is extremely reactive: almost all
other elements, including some noble gases, form compounds with fluorine.

Among the elements, fluorine ranks 24th in universal abundance and 13th in
terrestrial abundance. Fluorite, the primary mineral source of fluorine, was first
described in 1529; as it was added to metal ores to lower their melting points
for smelting, the Latin verb fluo meaning "flow" became associated with it. Proposed
as an element in 1810, fluorine proved difficult and dangerous to separate from its
compounds, and several early experimenters died or sustained injuries from their
attempts. Only in 1886 did French chemist Henri Moissan isolate elemental fluorine
using low-temperature electrolysis, a process still employed for modern production.
Industrial synthesis of fluorine gas for uranium enrichment, its largest application,
began during theManhattan Project in World War II.

Owing to the expense of refining pure fluorine, most commercial applications of the
element involve the use of its compounds, with about half of mined fluorite used
in steelmaking. The rest is converted into corrosive hydrogen fluoride en route to
various organic fluorides, or into cryolite which plays a key role in aluminium
refining. Organic fluorides have very high chemical and thermal stability; their major
uses are as refrigerants, electrical insulation and cookware, the last as PTFE (Teflon).
Pharmaceuticals such as atorvastatin and fluoxetine also contain fluorine, and
the fluoride ion inhibits dental cavities, and so finds use in toothpaste and water
fluoridation. Global fluorochemical sales amount to over US$15 billion a year.

Fluorocarbon gases are generally greenhouse gases with global-warming


potentials 100 to 20,000 times that of carbon dioxide. Organofluorine
compounds persist in the environment due to the strength of the carbonfluorine bond.
Fluorine has no known metabolic role in mammals; a few plants synthesize
organofluorine poisons which deter herbivores.

Contents
[hide]
1 Characteristics
o 1.1 Electron configuration
o 1.2 Reactivity
o 1.3 Phases
o 1.4 Isotopes
2 Occurrence
o 2.1 Universe
o 2.2 Earth
3 History
o 3.1 Early discoveries
o 3.2 Isolation
o 3.3 Later uses
4 Compounds
o 4.1 Metals
o 4.2 Hydrogen
o 4.3 Other reactive nonmetals
o 4.4 Noble gases
o 4.5 Organic compounds
5 Production
o 5.1 Industrial
o 5.2 Chemical
6 Industrial applications
o 6.1 Inorganic fluorides
o 6.2 Organic fluorides
7 Medicinal applications
o 7.1 Dental care
o 7.2 Pharmaceuticals
o 7.3 PET scanning
o 7.4 Oxygen carriers
8 Biological role
9 Toxicity
o 9.1 Hydrofluoric acid
o 9.2 Fluoride ion
10 Environmental concerns
o 10.1 Atmosphere
o 10.2 Biopersistence
11 See also
12 Notes
13 Sources
o 13.1 Citations
o 13.2 Indexed references
Characteristics
Electron configuration

Simplified structure of the fluorine atom

Fluorine atoms have nine electrons, one fewer than neon, and electron
configuration 1s22s22p5: two electrons in a filled inner shell and seven in an outer shell
requiring one more to be filled. The outer electrons are ineffective at
nuclear shielding, and experience a high effective nuclear charge of 9 2 = 7; this
affects the atom's physical properties.[2]

Fluorine's first ionization energy is third-highest among all elements, behind helium
and neon,[13] which complicates the removal of electrons from neutral fluorine atoms.
It also has a high electron affinity, second only to chlorine,[14] and tends to capture an
electron to become isoelectronic with the noble gas neon;[2] it has the
highest electronegativity of any element.[15] Fluorine atoms have a small covalent
radius of around 60 picometers, similar to those of its period neighbors oxygen and
neon.[16][17][note 1]

Reactivity

Main article: Chemical characteristics of fluorine

The bond energy of difluorine is much lower than that of either Cl


2 or Br
2 and similar to the easily cleaved peroxide bond; this, along with high
electronegativity, accounts for fluorine's easy dissociation, high reactivity and strong
bonds to non-fluorine atoms.[18][19] Conversely, bonds to other atoms are very strong
because of fluorine's high electronegativity. Unreactive substances like powdered
steel, glass fragments, and asbestos fibers react quickly with cold fluorine gas; wood
and water spontaneously combust under a fluorine jet.[4][20]

External video
Bright flames during fluorine
reactions

Fluorine reacting with caesium

Reactions of elemental fluorine with metals require varying conditions. Alkali


metals cause explosions andalkaline earth metals display vigorous activity in bulk; to
prevent passivation from the formation of metal fluoride layers most other metals such
as aluminium and iron must be powdered,[18] and noble metals require pure fluorine
gas at 300450 C (575850 F).[21] Some solid nonmetals (sulfur, phosphorus) react
vigorously in liquid air temperature fluorine.[22] Hydrogen sulfide[22] and sulfur
dioxide[23] combine readily with fluorine, the latter sometimes explosively; sulfuric
acid exhibits much less activity, requiring elevated temperatures.[24]

Hydrogen, like some of the alkali metals, reacts explosively with fluorine.[25] Carbon,
as lamp black, reacts at room temperature to yield fluoromethane. Graphite combines
with fluorine above 400 C (750 F) to produce non-stoichiometric carbon
monofluoride; higher temperatures generate gaseousfluorocarbons, sometimes with
explosions.[26] Carbon dioxide and carbon monoxide react at or just above room
temperature,[27] whereas paraffins and other organic chemicals generate strong
reactions:[28] even fully substituted haloalkanes such as carbon tetrachloride, normally
incombustible, may explode.[29] Although nitrogen trifluoride is stable, nitrogen
requires an electric discharge at elevated temperatures for reaction due to its very
strongtriple bond;[30] ammonia may react explosively.[31][32] Oxygen does not combine
with fluorine under ambient conditions, but can be made to using electric discharge at
low temperatures and pressures; the products tend to disintegrate into their constituent
elements when heated.[33][34][35] Heavier halogens[36] react readily with fluorine as does the
noble gas radon;[37] of the other noble gases only xenon and krypton react, under
special conditions.[38]

Phases

Main article: Phases of fluorine


Crystal structure of -fluorine. Spheres indicate F
2 molecules that may assume any angle. Other molecules are constrained to planes.

At room temperature, fluorine is a gas of diatomic molecules,[4] pale yellow when pure
(but sometimes described as yellow-green).[39] It has a characteristic pungent odor
detectable at 20 ppb.[40] Fluorine condenses into a bright yellow liquid at 188 C
(306 F), a transition temperature similar to those of oxygen and nitrogen.[41]

Fluorine has two solid forms, - and -fluorine. The latter crystallizes at 220 C
(364 F) and is transparent and soft, with the same disordered cubic structure of
freshly crystallized solid oxygen,[41][note 2] unlike the orthorhombic systems of other solid
halogens.[45][46] Further cooling to 228 C (378 F) induces a phase transition into
opaque and hard -fluorine, which has a monoclinicstructure with dense, angled
layers of molecules. The transition from - to -fluorine is more exothermic than the
condensation of fluorine, and can be violent.[45][46][note 3]

Isotopes

Main article: Isotopes of fluorine

Only one isotope of fluorine occurs naturally to any significant extent, the stable 19
F that has ten neutrons.[47] It has a high magnetogyric ratio[note 4] and exceptional
sensitivity to magnetic fields; because it is also the only stable isotope, it is used
in magnetic resonance imaging.[49] Seventeen radioisotopes with mass numbers from
14 to 31 have been synthesized, of which 18
F is the most stable with a half-life of 109.77 minutes. Other radioisotopes have half-
lives less than 70 seconds; most decay in less than half a second.[50] The isotopes 17
F and 18
F undergo + decay, lighter isotopes decay via electron capture, and those heavier
than 19
F undergo decay or neutron emission.[50] One metastable isomer of fluorine is
known, 18m
F, with a half-life of 234 nanoseconds.[51]

Occurrence
Main article: Origin and occurrence of fluorine

Universe

Solar System abundances[52]


Atomic Relative
Element
number amount
6 Carbon 4,800
7 Nitrogen 1,500
8 Oxygen 8,800
9 Fluorine 1
10 Neon 1,400
11 Sodium 24
12 Magnesium 430

Among the lighter elements, fluorine's abundance value of 400 ppb (parts per billion)
24th among elements in the universe is exceptional: other elements from carbon to
magnesium are twenty or more times as common.[53] This is because stellar
nucleosynthesis processes bypass fluorine, and any fluorine atoms otherwise created
have high nuclear cross sections, allowing further fusion with hydrogen or helium to
generate oxygen or neon respectively.[53][54]

Beyond this transient existence, three explanations have been proposed for the
presence of fluorine:[53][55]

during type II supernovae, bombardment of neon atoms by neutrinos could


transmute them to fluorine;
the solar wind of WolfRayet stars could blow fluorine away from any
hydrogen or helium atoms; or
fluorine is borne out on convection currents arising from fusion in asymptotic
giant branch stars.

Earth

See also: List of countries by fluorite production


Fluorine is the thirteenth most common element in Earth's crust at 600700 ppm
(parts per million) by mass.[56] Elemental fluorine in Earth's atmosphere would easily
react with atmospheric water vapor, precluding its natural occurrence;[57][58] it is found
only in combined mineral forms, of which fluorite, fluorapatite and cryolite are the
most industrially significant.[56][59] Fluorite or fluorspar (CaF
2), colorful and abundant worldwide, is fluorine's main source; China and Mexico are
the major suppliers. The U.S. led extraction in the early 20th century but ceased
mining in 1995.[59][60][61][62][63]Although fluorapatite (Ca5(PO4)3F) contains most of the
world's fluorine, its low mass fraction of 3.5% means that most of it is used as a
phosphate. In the U.S. small quantities of fluorine compounds are obtained
via fluorosilicic acid, a phosphate industry byproduct.[59] Cryolite (Na
3AlF
6), once used directly in aluminium production, is the rarest and most concentrated of
these three minerals. The main commercial mine on Greenland's west coast closed in
1987, and most cryolite is now synthesized.[59]

Major fluorine-containing minerals

Fluorite Fluorapatite Cryolite

Other minerals such as topaz contain fluorine. Fluorides, unlike other halides, are
insoluble and do not occur in commercially favorable concentrations in saline
waters.[59] Trace quantities of organofluorines of uncertain origin have been detected in
volcanic eruptions and geothermal springs.[64] The existence of gaseous fluorine in
crystals, suggested by the smell of crushed antozonite, is contentious;[65][66] a 2012 study
reported the presence of 0.04% F
2 by weight in antozonite, attributing these inclusions to radiation from the presence of
tiny amounts of uranium.[66]

History
Main article: History of fluorine

Early discoveries

Steelmaking illustration from De re metallica

In 1529, Georgius Agricola described fluorite as an additive used to lower the melting
point of metals during smelting.[67][68][note 5] He penned the Latin word fluors (fluo, flow)
for fluorite rocks. The name later evolved into fluorspar (still commonly used) and
then fluorite.[60][72][73] The composition of fluorite was later determined to be calcium
difluoride.[74]

Hydrofluoric acid was used in glass etching from 1720 onwards.[note 6] Andreas
Sigismund Marggraf first characterized it in 1764 when he heated fluorite with
sulfuric acid, and the resulting solution corroded its glass container.[76][77] Swedish
chemist Carl Wilhelm Scheele repeated the experiment in 1771, and named the acidic
product fluss-spats-syran (fluorspar acid).[77][78] In 1810, the French physicist Andr-
Marie Ampre suggested that hydrogen and an element analogous to chlorine
constituted hydrofluoric acid.[79] Sir Humphry Davy proposed that this then-unknown
substance be namedfluorine from fluoric acid and the -ine suffix of other halogens.
This word, with modifications, is used in most European languages; Greek, Russian,
and some others (following Ampre's suggestion) use the name ftor or derivatives,
from the Greek (phthorios, destructive) .[80][81] The New Latin
name fluorum gave the element its current symbol F; Fl was used in early papers.[82][note
7]

Isolation

Initial studies on fluorine were so dangerous that several 19th-century experimenters


were deemed "fluorine martyrs" after misfortunes with hydrofluoric acid.[note 8] Isolation
of elemental fluorine was hindered by the extreme corrosiveness of both it and
hydrogen fluoride, as well as the lack of a simple and suitable electrolyte.[74][83] Edmond
Frmy postulated that electrolysis of pure hydrofluoric acid to generate fluorine was
feasible and devised a method to produce anhydrous samples from
acidified potassium bifluoride; instead, he discovered that the resulting (dry) hydrogen
fluoride did not conductelectricity.[74][83][84] Frmy's former student Henri
Moissan persevered, and after much trial and error found that a mixture of potassium
bifluoride and dry hydrogen fluoride was a conductor, enabling electrolysis. To
prevent rapid corrosion of the platinum in his electrochemical cells, he cooled the
reaction to extremely low temperatures in a special bath and forged cells from a more
resistant mixture of platinum and iridium, and used fluorite stoppers.[83][85] In 1886,
after 74 years of effort by many chemists, Moissan isolated elemental fluorine.[84][86]

In 1906, two months before his death, Moissan received the Nobel Prize in
Chemistry,[87] with the following citation:[83]

[I]n recognition of the great services rendered by him in his investigation and isolation
of the element fluorine ... The whole world has admired the great experimental skill
with which you have studied that savage beast among the elements.[note 9]

1887 drawing of Moissan's apparatus

Nobel Prize photo of Moissan

Later uses

An ampoule of uranium hexafluoride or hex


The Frigidaire division of General Motors experimented with chlorofluorocarbon
refrigerants in the late 1920s, and Kinetic Chemicals was formed as a joint venture
between GM and DuPont in 1930 hoping to market Freon-12 (CCl
2F
2) as one such refrigerant. It replaced earlier and more toxic compounds, increased
demand for kitchen refrigerators, and became profitable; by 1949 DuPont had bought
out Kinetic and marketed several
other Freon compounds.[77][88][89][90] Polytetrafluoroethylene (Teflon) was serendipitously
discovered in 1938 by Roy J. Plunkett while working on refrigerants at Kinetic, and
its superlative chemical and thermal resistance lent it to accelerated commercialization
and mass production by 1941.[77][88][89]

Elemental fluorine's large-scale synthesis began during World War II. Germany used
high-temperature electrolysis to make tons of the planned incendiary chlorine
trifluoride[91] and the Manhattan Project used huge quantities to produce uranium
hexafluoride for uranium enrichment. Since UF
6 is as corrosive as fluorine, gaseous diffusion plants required special materials: nickel
for membranes, fluoropolymers for seals, and liquid fluorocarbons as coolants and
lubricants. This burgeoning nuclear industry later drove post-war fluorochemical
development.[92]

Compounds
Main article: Compounds of fluorine

Fluorine has a rich chemistry, encompassing organic and inorganic domains. It


combines with metals, nonmetals, metalloids, and most noble gases,[93] and usually
assumes an oxidation state of 1.[note 10] Fluorine's high electron affinity results in a
preference for ionic bonding; when it forms covalent bonds, these are polar, and
almost always single.[97][98][note 11]

Metals

See also: Fluoride volatility

Alkali metals form ionic and highly soluble monofluorides; these have the cubic
arrangement of sodium chloride and analogous chlorides.[99][100] Alkaline
earth difluorides possess strong ionic bonds but are insoluble[82] save for beryllium
difluoride, which also exhibits some covalent character and has a quartz-like
structure.[101] Rare earth elements and many other metals form mostly
ionictrifluorides.[102][103][104]
Covalent bonding first comes to prominence in the tetrafluorides: those of zirconium,
hafnium[105][106] and several actinides[107] are ionic with high melting points,[108][note 12] while
those of titanium,[111]vanadium,[112] and niobium are polymeric,[113] melting or
decomposing at no more than 350 C (660 F).[114] Pentafluorides continue this trend
with their linear polymers and oligomericcomplexes.[115][116][117] Thirteen
metal hexafluorides are known,[note 13] all octahedral, and are mostly volatile solids but
for liquid MoF
6 and ReF
6, and gaseous WF
6.[118][119][120] Rhenium heptafluoride, the only characterized metal heptafluoride, is a low-
melting molecular solid with pentagonal bipyramidal molecular geometry.[121] Metal
fluorides with more fluorine atoms are particularly reactive.[122]

Structural progression of metal fluorides

Rhenium
Sodium
Bismuth pentafluoride, polymeric heptafluoride,
fluoride, ionic
molecular

Hydrogen

Main articles: Hydrogen fluoride and hydrofluoric acid

Boiling points of hydrogen halides and chalcogenides, showing the unusually high
values for hydrogen fluoride and water
Hydrogen and fluorine combine to yield hydrogen fluoride, in which discrete
molecules form clusters via hydrogen bonding. Hydrogen fluoride thus behaves more
like water than hydrogen chloride.[123][124][125] It boils at a much higher temperature than
heavier hydrogen halides and unlike them is fully miscible with water.[126] Hydrogen
fluoride readily hydrates on contact with water to form aqueous hydrogen fluoride,
also known as hydrofluoric acid. Unlike the other hydrohalic acids, which are strong,
hydrofluoric acid is a weak acid (at low concentrations).[127][note 14] However, it can attack
glass, something the other acids cannot do.[129]

Other reactive nonmetals

Metalloids are included in this section

Chlorine trifluoride, whose corrosive potential ignites asbestos, concrete, sand and
other fire retardants[130]

Binary fluorides of metalloids and p-block nonmetals are generally covalent and
volatile, with varying reactivities. Period 3 and heavier nonmetals can
form hypervalent fluorides.[131]

Boron trifluoride is planar and possesses an incomplete octet. It functions as a Lewis


acid and combines with Lewis bases like ammonia to form adducts.[132] Carbon
tetrafluoride is tetrahedral and inert;[note 15] its group analogues, silicon and germanium
tetrafluoride, are also tetrahedral[133] but behave as Lewis
acids.[134][135] The pnictogens form trifluorides that increase in reactivity and basicity
with higher molecular weight, although nitrogen trifluoride resists hydrolysis and is
not basic.[136] The pentafluorides of phosphorus, arsenic, and antimony are more
reactive than their respective trifluorides, with antimony pentafluoride the strongest
neutral Lewis acid known.[115][137][138]

Chalcogens have diverse fluorides: unstable difluorides have been reported for oxygen
(the only known compound with oxygen in an oxidation state of +2), sulfur, and
selenium; tetrafluorides and hexafluorides exist for sulfur, selenium, and tellurium.
The latter are stabilized by more fluorine atoms and lighter central atoms, so sulfur
hexafluoride is especially inert.[139][140] Chlorine, bromine, and iodine can each form
mono-, tri-, and pentafluorides, but only iodine heptafluoride has been characterized
among possible interhalogen heptafluorides.[141] Many of them are powerful sources of
fluorine atoms, and chlorine trifluoride's industrial applications require precautions
similar to those applying to fluorine.[142][143]

Noble gases

Main article: Noble gas compound

These xenon tetrafluoride crystals were photographed in 1962. The compound's


synthesis, as with xenon hexafluoroplatinate, surprised many chemists.[144]

Noble gases, having complete electron shells, defied reaction with other elements
until 1962 when Neil Bartlett reported synthesis of xenon
hexafluoroplatinate;[145] xenon difluoride, tetrafluoride,hexafluoride, and multiple
oxyfluorides have been isolated since then.[146] Among other noble gases, krypton
forms a difluoride,[147] and radon and fluorine generate a solid suspected to be radon
difluoride.[148][149] Binary fluorides of lighter noble gases are exceptionally unstable:
argon and hydrogen fluoride combine under extreme conditions to give argon
fluorohydride.[38] Helium and neon have no long-lived fluorides,[150] and no neon
fluoride has ever been observed;[151] helium fluorohydride has been detected for
milliseconds at high pressures and low temperatures.[150]

Organic compounds

Main article: Organofluorine chemistry


Immiscible layers of colored water (top) and much denserperfluoroheptane (bottom)
in a beaker; a goldfish and crab cannot penetrate the boundary; quartersrest at the
bottom.

Chemical structure of Nafion, a fluoropolymer used in fuel cells and many other
applications.[152]

The carbonfluorine bond is organic chemistry's strongest,[153] and gives stability to


organofluorines.[154] It is almost non-existent in nature, but is used in artificial
compounds. Research in this area is usually driven by commercial applications;[155] the
compounds involved are diverse and reflect the complexity inherent in organic
chemistry.[88]

Discrete molecules

The substitution of hydrogen atoms in an alkane by progressively more fluorine atoms


gradually alters several properties: melting and boiling points are lowered, density
increases, solubility in hydrocarbons decreases and overall stability increases.
Perfluorocarbons,[note 16] in which all hydrogen atoms are substituted, are insoluble in
most organic solvents, reacting at ambient conditions only with sodium in liquid
ammonia.[156]

The term perfluorinated compound is used for what would otherwise be a


perfluorocarbon if not for the presence of a functional group,[157][note 17] often a carboxylic
acid. These compounds share many properties with perfluorocarbons such as stability
and hydrophobicity,[159] while the functional group augments their reactivity, enabling
them to adhere to surfaces or act as surfactants;[160]Fluorosurfactants, in particular, can
lower the surface tension of water more than their hydrocarbon-based
analogues. Fluorotelomers, which have some unfluorinated carbon atoms near the
functional group, are also regarded as perfluorinated.[159]
Polymers

Polymers exhibit the same stability increases afforded by fluorine substitution (for
hydrogen) in discrete molecules; their melting points generally increase
too.[161] Polytetrafluoroethylene (PTFE), the simplest fluoropolymer and perfluoro
analogue of polyethylene with structural unit CF
2, demonstrates this change as expected, but its very high melting point makes it
difficult to mold.[162] Various PTFE derivatives are less temperature-tolerant but easier
to mold: fluorinated ethylene propylene replaces some fluorine atoms
with trifluoromethyl groups, perfluoroalkoxy alkanes do the same
withtrifluoromethoxy groups,[162] and Nafion contains perfluoroether side chains
capped with sulfonic acid groups.[163][164] Other fluoropolymers retain some hydrogen
atoms; polyvinylidene fluoride has half the fluorine atoms of PTFE and polyvinyl
fluoride has a quarter, but both behave much like perfluorinated polymers.[165]

Production
Industrial

Industrial fluorine cells at Preston

Moissan's method is used to produce industrial quantities of fluorine, via the


electrolysis of a potassium fluoride/hydrogen fluoride mixture: hydrogen and fluoride
ions are reduced and oxidized at a steel container cathode and a carbon block anode,
under 812 volts, to generate hydrogen and fluorine gas
respectively.[61][166] Temperatures are elevated, KF2HF melting at 70 C (158 F) and
being electrolyzed at 70130 C (158266 F). KF, which acts as catalyst, is essential
since pure HF cannot be electrolyzed.[77][167][168] Fluorine can be stored in steel cylinders
that have passivated interiors, at temperatures below 200 C (392 F); otherwise
nickel can be used.[77][169] Regulator valves and pipework are made of nickel, the latter
possibly using Monel instead.[170] Frequent passivation, along with the strict exclusion
of water and greases, must be undertaken. In the laboratory, glassware may carry
fluorine gas under low pressure and anhydrous conditions; [170] some sources instead
recommend nickel-Monel-PTFE systems.[171]

Chemical

While preparing for a 1986 conference to celebrate the centennial of Moissan's


achievement, Karl O. Christe reasoned that chemical fluorine generation should be
feasible since some metal fluoride anions have no stable neutral counterparts; their
acidification potentially triggers oxidation instead. He devised a method which
evolves fluorine at high yield and atmospheric pressure:[172]

2 KMnO4 + 2 KF + 10 HF + 3 H2O2 2 K2MnF6 + 8 H2O + 3 O2


2 K2MnF6 + 4 SbF5 4 KSbF6 + 2 MnF3 + F2

Christe later commented that the reactants "had been known for more than 100 years
and even Moissan could have come up with this scheme."[173] As late as 2008, some
references still asserted that fluorine was too reactive for any chemical isolation.[174]

Industrial applications
Main article: Fluorochemical industry

Fluorite mining, which supplies most global fluorine, peaked in 1989 when 5.6
million metric tons of ore were extracted. Chlorofluorocarbon restrictions lowered this
to 3.6 million tons in 1994; production has since been increasing. Around 4.5 million
tons of ore and revenue of US$550 million were generated in 2003; later reports
estimated 2011 global fluorochemical sales at $15 billion and predicted 201618
production figures of 3.5 to 5.9 million tons, and revenue of at least $20
billion.[77][175][176][177][178] Froth flotation separates mined fluorite into two main
metallurgical grades of equal proportion: 6085% pure metspar is almost all used in
iron smelting whereas 97%+ pure acidspar is mainly converted to the key
industrial intermediate hydrogen fluoride.[61][77][179]
Clickable diagram of the fluorochemical industry according to mass flows.

SF
6 transformers at a Russian railway
See also: Industrial gas

At least 17,000 metric tons of fluorine are produced each year. It costs only $58 per
kilogram as uranium or sulfur hexafluoride, but handling challenges multiply its price
as an element, and most processes that use the latter in large amounts employ in
situ generation under vertical integration.[180]

The largest application of fluorine gas, consuming up to 7,000 metric tons annually, is
in the preparation of UF
6 for the nuclear fuel cycle. Fluorine is used to fluorinate uranium tetrafluoride, itself
formed from uranium dioxide and hydrofluoric acid.[180] Fluorine is monoisotopic, so
any mass differences between UF
6 molecules are due to the presence of 235
U or 238
U, enabling uranium enrichment via gaseous diffusion or gas centrifuge.[4][61] About
6,000 metric tons per year go into producing the inert dielectric SF
6 for high-voltage transformers and circuit breakers, eliminating the need for
hazardous polychlorinated biphenyls associated with oil-filled devices.[181] Several
fluorine compounds are used in electronics: rhenium and tungsten hexafluoride
in chemical vapor deposition,tetrafluoromethane in plasma etching[182][183][184] and
nitrogen trifluoride in cleaning equipment.[61] Fluorine is also used in the synthesis of
organic fluorides, but its reactivity often necessitates conversion first to the
gentler ClF
3, BrF
3, or IF
5, which together allow calibrated fluorination. Fluorinated pharmaceuticals use sulfur
tetrafluoride instead.[61]

Inorganic fluorides

Aluminium extraction depends critically on cryolite

As with other iron alloys, around 3 kg (6.5 lb) metspar is added to each metric ton of
steel; the fluoride ions lower its melting point and viscosity.[61][185] Alongside its role as
an additive in materials like enamels and welding rod coats, most acidspar is reacted
with sulfuric acid to form hydrofluoric acid, which is used in steel pickling, glass
etching and alkane cracking.[61] One-third of HF goes into
synthesizing cryolite and aluminium trifluoride, both fluxes in the HallHroult
process for aluminium extraction; replenishment is necessitated by their occasional
reactions with the smelting apparatus. Each metric ton of aluminium requires about
23 kg (51 lb) of flux.[61][186] Fluorosilicates consume the second largest portion,
with sodium fluorosilicate used in water fluoridation and laundry effluent treatment,
and as an intermediate en route to cryolite and silicon tetrafluoride.[187] Other important
inorganic fluorides include those of cobalt, nickel, and ammonium.[61][100][188]

Organic fluorides
Organofluorides consume over 20% of mined fluorite and over 40% of hydrofluoric
acid, with refrigerant gases dominating and fluoropolymers increasing their market
share.[61][189] Surfactants are a minor application but generate over $1 billion in annual
revenue.[190] Due to the danger from direct hydrocarbonfluorine reactions above
150 C (240 F), industrial fluorocarbon production is indirect, mostly
through halogen exchange reactions such as Swarts fluorination, in which
chlorocarbon chlorines are substituted for fluorines by hydrogen fluoride under
catalysts. Electrochemical fluorination subjects hydrocarbons to electrolysis in
hydrogen fluoride, and the Fowler process treats them with solid fluorine carriers
like cobalt trifluoride.[88][191]

Refrigerant gases

See also: Refrigerant

Halogenated refrigerants, termed Freons in informal contexts,[note 18] are identified by R-


numbers that denote the amount of fluorine, chlorine, carbon, and hydrogen
present.[61][192] Chlorofluorocarbons(CFCs) like R-11, R-12, and R-114 once dominated
organofluorines, peaking in production in the 1980s. Used for air conditioning
systems, propellants and solvents, their production was below one-tenth of this peak
by the early 2000s, after widespread international
prohibition.[61] Hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs)
were designed as replacements; their synthesis consumes more than 90% of the
fluorine in the organic industry. Important HCFCs include R-
22, chlorodifluoromethane, and R-141b. The main HFC is R-134a[61] with HFO-
1234yf coming to prominence owing to its global warming potential of less than 1%
that of HFC-134a.[193]

Polymers

Fluorosurfactant-treated fabrics are often hydrophobic


Main article: Fluoropolymer
About 180,000 metric tons of fluoropolymers were produced in 2006 and 2007,
generating over $3.5 billion revenue per year.[194] The global market was estimated at
just under $6 billion in 2011 and was predicted to grow by 6.5% per year up to
2016.[195] Fluoropolymers can only be formed by polymerizing free radicals.[161]

Polytetrafluoroethylene (PTFE), sometimes called by its DuPont name


Teflon,[196] represents 6080% by mass of the world's fluoropolymer production.[194] The
largest application is in electrical insulation since PTFE is an excellent dielectric. It is
also used in the chemical industry where corrosion resistance is needed, in coating
pipes, tubing, and gaskets. Another major use is in PFTE-coatedfiberglass cloth for
stadium roofs. The major consumer application is for non-stick cookware.[196] Jerked
PTFE film becomes expanded PTFE (ePTFE), a fine-pored membrane sometimes
referred to by the brand name Gore-Tex and used for rainwear, protective apparel,
and filters; ePTFE fibers may be made into seals and dust filters.[196] Other
fluoropolymers, including fluorinated ethylene propylene, mimic PTFE's properties
and can substitute for it; they are more moldable, but also more costly and have lower
thermal stability. Films from two different fluoropolymers replace glass in solar
cells.[196][197]

The chemically resistant (but expensive) fluorinated ionomers are used as


electrochemical cell membranes, of which the first and most prominent example
is Nafion. Developed in the 1960s, it was initially deployed as fuel cell material in
spacecraft and then replaced mercury-based chloralkali process cells. Recently, the
fuel cell application has reemerged with efforts to install proton exchange
membrane fuel cells into automobiles.[198][199][200] Fluoroelastomers such
as Viton are crosslinked fluoropolymer mixtures mainly used in O-
rings;[196] perfluorobutane (C4F10) is used as a fire-extinguishing agent.[201]

Surfactants

Main articles: Fluorinated surfactant and Durable water repellent

Fluorosurfactants are small organofluorine molecules used for repelling water and
stains. Although expensive (comparable to pharmaceuticals at $2002000 per
kilogram), they yielded over $1 billion in annual revenues by 2006; Scotchgard alone
generated over $300 million in 2000.[190][202][203] Fluorosurfactants are a minority in the
overall surfactant market, most of which is taken up by much cheaper hydrocarbon-
based products. Applications in paints are burdened by compounding costs; this use
was valued at only $100 million in 2006.[190]

Agrichemicals
About 30% of agrichemicals contain fluorine,[204] most of
them herbicides and fungicides with a few crop regulators. Fluorine substitution,
usually of a single atom or at most a trifluoromethyl group, is a robust modification
with effects analogous to fluorinated pharmaceuticals: increased biological stay time,
membrane crossing, and altering of molecular recognition.[205] Trifluralin is a
prominent example, with large-scale use in the U.S. as a weedkiller,[205][206] but it is a
suspected carcinogen and has been banned in many European countries.[207] Sodium
monofluoroacetate (1080) is a mammalian poison in which two acetic acid hydrogens
are replaced with fluorine and sodium; it disrupts cell metabolism by replacing acetate
in the citric acid cycle. First synthesized in the late 19th century, it was recognized as
an insecticide in the early 20th, and was later deployed in its current use. New
Zealand, the largest consumer of 1080, uses it to protect kiwis from the invasive
Australian common brushtail possum.[208] Europe and the U.S. have banned
1080.[209][210][note 19]

Medicinal applications
Dental care

Topical fluoride treatment in Panama


Main articles: Fluoride therapy, Water fluoridation and Water fluoridation
controversy

Population studies from the mid-20th century onwards show topical fluoride
reduces dental caries. This was first attributed to the conversion of tooth
enamel hydroxyapatite into the more durable fluorapatite, but studies on pre-
fluoridated teeth refuted this hypothesis, and current theories involve fluoride aiding
enamel growth in small caries.[211] After studies of children in areas where fluoride was
naturally present in drinking water, controlled public water supply fluoridation to fight
tooth decay[212] began in the 1940s and is now applied to water supplying 6 percent of
the global population, including two-thirds of Americans.[213][214] Reviews of the
scholarly literature in 2000 and 2007 associated water fluoridation with a significant
reduction of tooth decay in children.[215] Despite such endorsements and evidence of no
adverse effects other than mostly benign dental fluorosis,[216] opposition still exists on
ethical and safety grounds.[214][217] The benefits of fluoridation have lessened, possibly
due to other fluoride sources, but are still measurable in low-income
groups.[218] Sodium monofluorophosphate and sometimes sodium or tin(II) fluoride are
often found in fluoride toothpastes, first introduced in the U.S. in 1955 and now
ubiquitous in developed countries, alongside fluoridated mouthwashes, gels, foams,
and varnishes.[218][219]
Pharmaceuticals

Fluoxetine tablets

Twenty percent of modern pharmaceuticals contain fluorine.[220] One of these, the


cholesterol-reducer atorvastatin (Lipitor), made more revenue than any other drug
until it became generic in 2011.[221]The combination asthma prescription Seretide, a
top-ten revenue drug in the mid-2000s, contains two active ingredients, one of which
fluticasone is fluorinated.[222] Many drugs are fluorinated to delay inactivation and
lengthen dosage periods because the carbonfluorine bond is very
stable.[223] Fluorination also increases lipophilicity because the bond is more
hydrophobic than the carbonhydrogen bond, and this often helps in cell membrane
penetration and hence bioavailability.[222]

Tricyclics and other pre-1980s antidepressants had several side effects due to their
non-selective interference with neurotransmitters other than the serotonin target; the
fluorinated fluoxetine was selective and one of the first to avoid this problem. Many
current antidepressants receive this same treatment, including the selective serotonin
reuptake inhibitors: citalopram, its isomer escitalopram,
andfluvoxamine and paroxetine.[224][225] Quinolones are artificial broad-spectrum
antibiotics that are often fluorinated to enhance their effects. These
include ciprofloxacin and levofloxacin.[226][227][228][229]Fluorine also finds use in
steroids:[230] fludrocortisone is a blood pressure-raising mineralocorticoid,
and triamcinolone and dexamethasone are strong glucocorticoids.[231] The majority of
inhaledanesthetics are heavily fluorinated; the prototype halothane is much more inert
and potent than its contemporaries. Later compounds such as the
fluorinated ethers sevoflurane and desflurane are better than halothane and are almost
insoluble in blood, allowing faster waking times.[232][233]

PET scanning

Main article: Positron emission tomography


A full-body 18
F PET scan

Fluorine-18 is often found in radioactive tracers for positron emission tomography, as


its half-life of almost two hours is long enough to allow for its transport from
production facilities to imaging centers.[234] The most common tracer
is fluorodeoxyglucose[234] which, after intravenous injection, is taken up by glucose-
requiring tissues such as the brain and most malignant tumors;[235] computer-assisted
tomography can then be used for detailed imaging.[236]

Oxygen carriers

See also: Blood substitute and Liquid breathing

Liquid fluorocarbons can hold large volumes of oxygen or carbon dioxide, more so
than blood, and have attracted attention for their possible uses in artificial blood and
in liquid breathing.[237] Because fluorocarbons do not normally mix with water, they
must be mixed into emulsions (small droplets of perfluorocarbon suspended in water)
to be used as blood.[238][239] One such product, Oxycyte, has been through initial clinical
trials.[240] These substances can aid endurance athletes and are banned from sports; one
cyclist's near death in 1998 prompted an investigation into their
abuse.[241][242]Applications of pure perfluorocarbon liquid breathing (which uses pure
perfluorocarbon liquid, not a water emulsion) include assisting burn victims and
premature babies with deficient lungs. Partial and complete lung filling have been
considered, though only the former has had any significant tests in humans.[243] An
Alliance Pharmaceuticals effort reached clinical trials but was abandoned because the
results were not better than normal therapies.[244]

Biological role
Main article: Biological aspects of fluorine

The gifblaar is one of the few organofluorine-synthesizing organisms

Fluorine is not essential for humans or other mammals; small amounts may be
beneficial for bone strength, but this has not been definitively established. As there are
many environmental sources of trace fluorine, the possibility of a fluorine
deficiency could apply only to artificial diets.[245][246] Natural organofluorines have been
found in microorganisms and plants[64] but not animals.[247] The most common
is fluoroacetate, which is used as a defense against herbivores by at least 40 plants in
Africa, Australia and Brazil.[209] Other examples include terminally fluorinated fatty
acids, fluoroacetone, and 2-fluorocitrate.[247] An enzyme that binds fluorine to carbon
adenosyl-fluoride synthase was discovered in bacteria in 2002.[248]

Toxicity
Main article: Fluorine-related hazards

U.S. hazard signs for commercially transported fluorine[249]

Elemental fluorine is highly toxic to living organisms. Its effects in humans start at
concentrations lower than hydrogen cyanide's 50 ppm[250] and are similar to those of
chlorine:[251] significant irritation of the eyes and respiratory system as well as liver and
kidney damage occur above 25 ppm. Eyes and noses are seriously damaged at 100
ppm,[252] and inhalation of 1,000 ppm fluorine will cause death in minutes,[253] compared
to 270 ppm for hydrogen cyanide.[254]

Hydrofluoric acid

Hydrofluoric acid burns may not be evident for a day, after which calcium treatments
are less effective.[255]
See also: Chemical burn

Hydrofluoric acid is a contact poison with greater hazards than many strong acids like
sulfuric acid even though it is weak: it remains neutral in aqueous solution and thus
penetrates tissue faster, whether through inhalation, ingestion or the skin, and at least
nine U.S. workers died in such accidents from 1984 to 1994. It reacts with calcium
and magnesium in the blood leading to hypocalcemia and possible death
through cardiac arrhythmia.[256] Insoluble calcium fluoride formation triggers strong
pain[257] and burns larger than 160 cm2 (25 in2) can cause serious systemic toxicity.[258]

Exposure may not be evident for eight hours for 50% HF, rising to 24 hours for lower
concentrations, and a burn may initially be painless as hydrogen fluoride affects nerve
function. If skin has been exposed to HF, damage can be reduced by rinsing it under a
jet of water for 1015 minutes and removing contaminated clothing.[259] Calcium
gluconate is often applied next, providing calcium ions to bind with fluoride; skin
burns can be treated with 2.5% calcium gluconate gel or special rinsing
solutions.[260][261][262] Hydrofluoric acid absorption requires further medical treatment;
calcium gluconate may be injected or administered intravenously. Using calcium
chloride a common laboratory reagent in lieu of calcium gluconate is
contraindicated, and may lead to severe complications. Excision or amputation of
affected parts may be required.[258][263]

Fluoride ion

See also: Fluoride toxicity


Soluble fluorides are moderately toxic: 510 g sodium fluoride, or 3264 mg fluoride
ions per kilogram of body mass, represents a lethal dose for adults.[264] One-fifth of the
lethal dose can cause adverse health effects,[265] and chronic excess consumption may
lead to skeletal fluorosis, which affects millions in Asia and Africa.[265][266] Ingested
fluoride forms hydrofluoric acid in the stomach which is easily absorbed by the
intestines, where it crosses cell membranes, binds with calcium and interferes with
various enzymes, before urinary excretion. Exposure limits are determined by urine
testing of the body's ability to clear fluoride ions.[265][267]

Historically, most cases of fluoride poisoning have been caused by accidental


ingestion of insecticides containing inorganic fluorides.[268] Most current calls to poison
control centers for possible fluoride poisoning come from the ingestion of fluoride-
containing toothpaste.[265] Malfunctioning water fluoridation equipment is another
cause: one incident in Alaska affected almost 300 people and killed one
person.[269] Dangers from toothpaste are aggravated for small children, and the Centers
for Disease Control and Prevention recommends supervising children below six
brushing their teeth so that they do not swallow toothpaste.[270] One regional study
examined a year of pre-teen fluoride poisoning reports totaling 87 cases, including
one death from ingesting insecticide. Most had no symptoms, but about 30% had
stomach pains.[268] A larger study across the U.S. had similar findings: 80% of cases
involved children under six, and there were few serious cases.[271]

Environmental concerns
Atmosphere

NASA projection of stratospheric ozone over North America without the Montreal
Protocol[272]
See also: Ozone depletion and global warming

The Montreal Protocol, signed in 1987, set strict regulations on chlorofluorocarbons


(CFCs) and bromofluorocarbons due to their ozone damaging potential (ODP). The
high stability which suited them to their original applications also meant that they
were not decomposing until they reached higher altitudes, where liberated chlorine
and bromine atoms attacked ozone molecules.[273] Even with the ban, and early
indications of its efficacy, predictions warned that several generations would pass
before full recovery.[274][275] With one-tenth the ODP of CFCs,
hydrochlorofluorocarbons (HCFCs) are the current replacements,[276] and are
themselves scheduled for substitution by 20302040 by hydrofluorocarbons (HFCs)
with no chlorine and zero ODP.[277] In 2007 this date was brought forward to 2020 for
developed countries;[278] the Environmental Protection Agency had already prohibited
one HCFC's production and capped those of two others in 2003.[277] Fluorocarbon gases
are generallygreenhouse gases with global-warming potentials (GWPs) of about 100
to 10,000; sulfur hexafluoride has a value of around 20,000. [279] An outlier is HFO-
1234yf which has attracted global demand due to its GWP of 4 compared to 1,430 for
the current refrigerant standard HFC-134a.[193]

Biopersistence

Perfluorooctanesulfonic acid, a key Scotchgard component until 2000[280]


Main article: Biopersistence of fluorinated organics

Organofluorines exhibit biopersistence due to the strength of the carbonfluorine


bond. Perfluoroalkyl acids (PFAAs), which are sparingly water-soluble owing to their
acidic functional groups, are notedpersistent organic
pollutants;[281] perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA)
are most often researched.[282][283][284] PFAAs have been found in trace quantities
worldwide from polar bears to humans, with PFOS and PFOA known to reside in
breast milk and the blood of newborn babies. A 2013 review showed a slight
correlation between groundwater and soil PFAA levels and human activity; there was
no clear pattern of one chemical dominating, and higher amounts of PFOS were
correlated to higher amounts of PFOA.[282][283][285] In the body, PFAAs bind to proteins
such as serum albumin; they tend to concentrate within humans in the liver and blood
before excretion through the kidneys. Dwell time in the body varies greatly by
species, with half-lives of days in rodents, and years in humans.[282][283][286] High doses of
PFOS and PFOA cause cancer and death in newborn rodents but human studies have
not established an effect at current exposure levels.[282][283][286]

Neon
From Wikipedia, the free encyclopedia
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This article is about the noble gas. For other uses, see Neon (disambiguation).

Neon, Ne 10

Spectral lines of neon in the visible region

General properties

Name, symbol neon, Ne

Appearance colorless gas exhibiting an orange-red


glow when placed in a high voltage
electric field

Pronunciation /nin/

Neon in the periodic table

He

Ne

Ar

fluorine neon sodium

Atomic number 10
Standard atomic weight () (Ar) 20.1797(6)[1]

Element category noble gas

Group, block group 18 (noble gases), p-block

Period period 2

Electron configuration [He] 2s2 2p6

per shell 2, 8

Physical properties

Phase gas

Melting point 24.56 K (248.59 C, 415.46 F)

Boiling point 27.104 K (246.046 C, 410.883 F)

Density at stp(0 C and 0.9002 g/L


101.325 kPa)

when liquid, at b.p. 1.207 g/cm3[2]

Triple point 24.556 K, 43.37 kPa[3][4]

Critical point 44.4918 K, 2.7686 MPa[4]

Heat of fusion 0.335 kJ/mol

Heat of vaporization 1.71 kJ/mol

Molar heat capacity 20.79[5] J/(molK)

vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 12 13 15 18 21 27

Atomic properties

Oxidation states 0

Ionization energies 1st: 2080.7 kJ/mol


2nd: 3952.3 kJ/mol
3rd: 6122 kJ/mol
(more)

Covalent radius 58 pm

Van der Waals radius 154 pm

Miscellanea

Crystal structure face-centered cubic (fcc)

Speed of sound 435 m/s (gas, at 0 C)

Thermal conductivity 49.1103 W/(mK)

Magnetic ordering diamagnetic[6]

Bulk modulus 654 GPa

CAS Registry Number 7440-01-9

History

Prediction William Ramsay (1897)


Discovery and first isolation William Ramsay & Morris
Travers[7][8] (1898)

Most stable isotopes

Main article: Isotopes of neon

iso NA half-life DM DE (MeV) DP


20
Ne 90.48%20Ne is stable with 10 neutrons
21
Ne 0.27%21Ne is stable with 11 neutrons
22
Ne 9.25%22Ne is stable with 12 neutrons

references

Neon is a chemical element with symbol Ne and atomic number 10. It is in group 18
(noble gases) of the periodic table.[9] 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 were 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 Earth's 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. This led to its 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,[citation needed] presumably for this reason. It is
also lighter than air, which has further depleted it from Earth's atmosphere.

Neon gives a distinct reddish-orange glow when used in either low-voltage neon glow
lamps or in high-voltage discharge tubes or neon advertising signs.[10][11] The red
emission line from neon is also responsible for the well known red light of helium
neon lasers. Neon is used in some 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.

Contents
[hide]

1 History
2 Isotopes
3 Characteristics
4 Occurrence
5 Applications
6 Compounds
7 See also
8 References
9 External links

History

Neon gas-discharge lampsforming the symbol for neon "Ne"

Neon (Greek (non), 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, England.[12] 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.[13] 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."[14] Finally, the same team discovered xenon by the same process, in
June.

Neon's scarcity precluded its prompt application for lighting along the lines of Moore
tubes, which used nitrogen and 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.[15]

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 ofcanal 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
Main article: Isotopes of neon
The first evidence for isotopes of a stable element was provided in 1913 by
experiments on neon plasma. In the bottom right corner of J. J. Thomson's
photographic plate are the separate impact marks for the two isotopes neon-20 and
neon-22.

Neon is the second lightest inert gas. Neon has three stable isotopes: 20Ne
(90.48%), 21Ne (0.27%) and 22Ne (9.25%). 21Ne and 22Ne are partlyprimordial and
partly nucleogenic (i.e. made by nuclear reactions of other nuclides with neutrons or
other particles in the environment) and their variations in natural abundance are well
understood. In contrast, 20Ne (the chief primordial isotope made in
stellar nucleosynthesis) is not known to be nucleogenic or radiogenic (save for cluster
decay production, which is thought to produce only a small amount). The causes of
the variation of 20Ne in the Earth have thus been hotly debated.[16]

The principal nuclear reactions which generate nucleogenic neon isotopes start
from 24Mg and 25Mg, which produce 21Ne and 22Ne, respectively, after neutron
capture and immediate emission of analpha particle. The neutrons that produce the
reactions are mostly produced by secondary spallation reactions from alpha particles,
in turn derived from uranium-series decay chains. The net result yields a trend
towards lower 20Ne/22Ne and higher 21Ne/22Ne ratios observed in uranium-rich rocks
such as granites.[17] Neon-21 may also be produced in a nucleogenic reaction,
when 20Ne absorbs a neutron from various natural terrestrial neutron sources.

In addition, isotopic analysis of exposed terrestrial rocks has demonstrated


the cosmogenic (cosmic ray) production of 21Ne. 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.[18]
Similar to xenon, neon content observed in samples of volcanic gases is enriched
in 20Ne, as well as nucleogenic 21Ne, relative to 22Ne content. The neon isotopic content
of these mantle-derived samples represents a non-atmospheric source of neon.
The 20Ne-enriched components are attributed to exotic primordial rare gas components
in the Earth, possibly representing solar neon. Elevated 20Ne abundances are found
in diamonds, further suggesting a solar neon reservoir in the Earth.[19]

Characteristics

Neon discharge tube

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).[2] In most applications it is a less
expensive refrigerant than helium.[20][21]

Spectrum of neon with ultraviolet (at left) and infrared (at right) lines shown in white

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.[22]

Two quite different kinds of neon lighting are in common use. Neon glow lamps are
generally tiny, with most operating at about 100250 volts.[23] 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.[24][25] Neon
signs typically operate at much higher voltages (215 kilovolts), and the luminous
tubes are commonly meters long.[26] 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. 20Ne is created in
fusing helium and oxygen in the alpha process, which requires temperatures above
100 megakelvins and masses greater than 3 solar masses.

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.[27]

Neon's 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).[28]

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.[2]

On 17 August 2015, based on studies with the Lunar Atmosphere and Dust
Environment Explorer (LADEE) spacecraft, NASA scientists reported the detection of
neon in the exosphere of the moon.[29]

Applications
Neon signs may use neon along with other noble gases

Neon is often used in signs and produces an unmistakable bright reddish-orange light.
Although still referred to as "neon", other colors are generated with different noble
gases or by varied colors offluorescent lighting.

Neon is used in vacuum tubes, high-voltage indicators, lightning arrestors, wave meter
tubes, television tubes, and heliumneon 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.[3]

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.[2]

Sodium
From Wikipedia, the free encyclopedia
Jump to: navigation, search
This article is about the chemical element. For the commonly called "sodium"
nutrient, see salt. For the PlayStation Home game, see Sodium (PlayStation Home).
For the racehorse, see Sodium (horse).
"Natrium" redirects here. For the town in West Virginia, see Natrium, West Virginia.
Sodium, Na 11

Spectral lines of sodium

General properties

Name, symbol sodium, Na

Appearance silvery white metallic

Pronunciation /sodim/
SOH-dee-m

Sodium in the periodic table

Li

Na

K

neon sodium magnesium

Atomic number 11

Standard atomic weight () (Ar) 22.98976928(2)[1]

Element category alkali metal


Group, block group 1 (alkali metals), s-block

Period period 3

Electron configuration [Ne] 3s1

per shell 2, 8, 1

Physical properties

Phase solid

Melting point 370.944 K (97.794 C, 208.029 F)

Boiling point 1156.090 K (882.940 C, 1621.292 F)

Density near r.t. 0.968 g/cm3

when liquid, at m.p. 0.927 g/cm3

Critical point 2573 K, 35 MPa(extrapolated)

Heat of fusion 2.60 kJ/mol

Heat of vaporization 97.42 kJ/mol

Molar heat capacity 28.230 J/(molK)

vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 554 617 697 802 946 1153

Atomic properties

Oxidation states +1, 1 (a strongly basicoxide)


Electronegativity Pauling scale: 0.93

Ionization energies 1st: 495.8 kJ/mol


2nd: 4562 kJ/mol
3rd: 6910.3 kJ/mol
(more)

Atomic radius empirical: 186 pm

Covalent radius 1669 pm

Van der Waals radius 227 pm

Miscellanea

Crystal structure body-centered cubic (bcc)

Speed of soundthin rod 3200 m/s (at 20 C)

Thermal expansion 71 m/(mK) (at 25 C)

Thermal conductivity 142 W/(mK)

Electrical resistivity 47.7 nm (at 20 C)

Magnetic ordering paramagnetic[2]

Young's modulus 10 GPa

Shear modulus 3.3 GPa

Bulk modulus 6.3 GPa


Mohs hardness 0.5

Brinell hardness 0.69 MPa

CAS Registry Number 7440-23-5

History

Discovery and first isolation Humphry Davy (1807)

Most stable isotopes

Main article: Isotopes of sodium

iso NA half-life DM DE (MeV) DP


0.5454 22
Ne*
+
1.27453(2) [3] 22
Ne
22
Na trace 2.602 y 22
Ne*

1.27453(2) 22
Ne
+ 1.8200 22
Ne
23
Na 100%23Na is stable with 12 neutrons

* = excited state

references

Sodium /sodim/[4] is a chemical element with symbol Na (from New


Latin natrium) and atomic number 11. It is a soft, silver-white, highly reactivemetal.
In the Periodic table it is in column 1 (alkali metals), and shares with the other six
elements in that column that it has a single electron in its outer shell, which it readily
donates, creating a positively charged atom - a cation. Its only stable isotope is 23Na.
The free metal does not occur in nature, but instead must be prepared from its
compounds. Sodium is the sixth most abundant element in the Earth's crust, and exists
in numerous minerals such asfeldspars, sodalite and rock salt (NaCl). Many salts of
sodium are highly water-soluble: sodium ions have been leached by the action of
water from the earth's minerals over eons, so that sodium (and chlorine) are the most
common dissolved elements by weight in the oceans.
Sodium was first isolated by Humphry Davy in 1807 by the electrolysis of sodium
hydroxide. Many sodium compounds are useful, such as sodium hydroxide (lye)
for soap-making, and sodium chloride for use as a de-icing agent and a nutrient
(edible salt).

Sodium is an essential element for all animals and some plants. Sodium ions are the
major cation in the extracellular fluid (ECF), and as such are the major contributor to
the ECF osmotic pressure, and thus ECF compartment volume. Loss of only water
from the ECF compartment increases the sodium
concentration: hypernatremia. Isotonic loss of water and sodium from the ECF
compartment decreases the size of that compartment: ECF hypovolemia.

Sodium ions are pumped out of cells by Na+/K+-ATPase in exchange for potassium.
It pumps three sodium ions out of the cell for every two potassium ions pumped in,
contributing to the fact that about forty times as much potassium is inside cells
compared to outside, and about ten times as much sodium is outside cells compared to
inside. In nerve cells, a build up of electrical charge across the cell membrane allows
transmission of a nerve impulse - an action potential - when the charge is dissipated.

Contents
[hide]

1 Characteristics
o 1.1 Physical
o 1.2 Chemical
o 1.3 Isotopes
o 1.4 Occurrence
2 Compounds
o 2.1 Aqueous solutions
o 2.2 Electrides and sodides
o 2.3 Organosodium compounds
3 History
4 Commercial production
5 Applications
o 5.1 Free element
5.1.1 Heat transfer
6 Biological role
7 Precautions
8 See also
9 References
10 External links

Characteristics
Physical

Sodium at standard temperature and pressure is a soft silvery metal, that oxidizes to
grayish white unless immersed in oil or inert gas. Sodium can be readily cut with a
knife, and is a good conductor of electricity and heat. These properties change
dramatically at elevated pressures: at 1.5 Mbar, the color changes from silvery
metallic to black; at 1.9 Mbar the material becomes transparent, with a red color; and
at 3 Mbar sodium is a clear and transparent solid. All of these high-
pressure allotropes are insulators and electrides.[5]

When sodium or its compounds are introduced into a flame, they turn it
yellow,[6] 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.[7]

Chemical

Emission spectrum for sodium, showing the D line.

A positive flame test for sodium has a bright yellow color.


When freshly cut, sodium has a bright, silvery luster. If exposed to air, the surface
rapidly tarnishes, darkening at first and then forming a white coating of sodium
hydroxide and sodium carbonate.

Sodium is generally less reactive than potassium and more reactive


than lithium.[8] 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 soda (sodium hydroxide) and flammable hydrogengas. When burned
in dry air, it mainly forms sodium peroxide as well as some sodium oxide. In moist
air, sodium hydroxide results.[9] Sodium metal is highly reducing, with the reduction of
sodium ions requiring 2.71 volts.[10] Hence, the extraction of sodium metal from its
compounds (such as with sodium chloride) uses a significant amount of
energy.[9] However, potassium and lithium have even more negative potentials.[11]

Isotopes

Main article: Isotopes of sodium

20 isotopes of sodium are known, but only 23Na is stable.


Two radioactive, cosmogenic isotopes are the byproduct of cosmic ray spallation: 22Na
with ahalf-life of 2.6 years and 24Na with a half-life of 15 hours; all other isotopes
have a half-life of less than one minute.[12] Two nuclear isomers have been discovered,
the longer-lived one being 24mNa with a half-life of around 20.2 microseconds. Acute
neutron radiation, such as from a nuclear criticality accident, converts some of the
stable 23Na in human blood to 24Na; by measuring the concentration of 24Na in relation
to 23Na, the neutron radiation dosage of the victim can be calculated.[13]

Occurrence

Na is created in the carbon-burning process in stars by fusing two carbon atoms


23

together; this requires temperatures above 600 megakelvins and a star of at least three
solar masses.[14] The Earth's crust contains 2.6% sodium by weight, making it the sixth
most abundant element on Earth.[15] 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, and zeolite. 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.[16] Sodium has been detected in at least one comet;
astronomers observing Comet Hale-Bopp in 1997 observed a sodium tail, which
consisted of neutral atoms (not ions) and extended to some 50 million kilometres in
length.[17]

Compounds
See also: Category:Sodium compounds.

Structure of sodium chloride, showing octahedral coordination around Na+ and


Cl centres. This framework disintegrates upon dissolution in water and reassembles
upon evaporation.

Sodium compounds are of immense commercial importance, being particularly central


to industries producing glass, paper, soap, and textiles.[18] 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).[19] In its
compounds, sodium is usually ionically bonded to water and anions, and is viewed as
a hard Lewis acid.[20]

Two equivalent images of the chemical structure of sodium stearate, a typical soap.

Most soaps are sodium salts of fatty acids. Sodium soaps are harder (higher melting)
soaps than potassium soaps.[19] Sodium chloride is extensively used for anti-
icing and de-icing and as a preservative;sodium bicarbonate is mainly used for
cooking. Along with potassium, many important medicines have sodium added to
improve their bioavailability; although in most cases potassium is the better ion,
sodium is selected for its lower price and atomic weight.[21]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.[22]
Aqueous solutions

Sodium tends to form water-soluble compounds, such


as halides, sulfates, nitrates, carboxylates and carbonates. The main aqueous species
are the aquo complexes [Na(H2O)n]+, where n = 46.[23] The high affinity of sodium
for oxygen-based ligands is the basis of crown ethers; macrolide antibiotics, which
interfere with Na+ transport in the infecting organism, are functionally related and
more complex.[citation needed]

Direct precipitation of sodium salts from aqueous solutions is rare, because sodium
salts typically have a high affinity for water; an exception is sodium
bismuthate (NaBiO3).[24] Because of this, sodium salts are usually isolated as solids by
evaporation or by precipitation with an organic solvent, such as ethanol; for example,
only 0.35 g/L of sodium chloride will dissolve in ethanol. [25] Crown ethers, like15-
crown-5, may be used as a phase-transfer catalyst.[26]

Sodium content in bulk may be determined by treating with a large excess of uranyl
zinc acetate; the hexahydrate (UO2)2ZnNa(CH3CO2)6H2O precipitates and can be
weighed. Caesium and rubidium do not interfere with this reaction, but potassium and
lithium do.[27] Lower concentrations of sodium may be determined by atomic
absorption spectrophotometry[28] or by potentiometry using ion-selective electrodes.[29]

Electrides and sodides

Like the other alkali metals, sodium dissolves in ammonia and some amines to give
deeply colored solutions; evaporation of these solutions leaves a shiny film of metallic
sodium. The solutions contain the coordination complex (Na(NH3)6)+, whose positive
charge is counterbalanced by electrons as anions; cryptands permit the isolation of
these complexes as crystalline solids. Cryptands, like crown ethers and
other ionophores, have a high affinity for the sodium ion; derivatives of
the alkalide Na are obtainable[30] by the addition of cryptands to solutions of sodium in
ammonia viadisproportionation.[31]

Organosodium compounds
The structure of the complex of sodium (Na+, shown in yellow) and the
antibiotic monensin-A.

Many organosodium compounds have been prepared. Because of the high polarity of
the C-Na bonds, they behave like sources of carbanions (salts with organic anions).
Some well known derivatives include sodium cyclopentadienide (NaC5H5) and trityl
sodium ((C6H5)3CNa).[32]

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 headache remedy. 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.[33] The chemical abbreviation for sodium was first published by Jns Jakob
Berzelius in his system of atomic symbols,[34] and is a contraction of the element's New
Latin name natrium, which refers to the Egyptian natron,[33] 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.[35][36]

Sodium imparts an intense yellow color to flames. As early as


1860, Kirchhoff and Bunsen noted the high sensitivity of a sodium flame test, and
stated in Annalen der Physik und Chemie:[37]

In a corner of our 60 m3 room farthest away from the apparatus, we exploded 3 mg.
of sodium chlorate with milk sugar while observing the nonluminous flame before
the slit. After a while, it glowed a bright yellow and showed a strong sodium line
that disappeared only after 10 minutes. From the weight of the sodium salt and the
volume of air in the room, we easily calculate that one part by weight of air could
not contain more than 1/20 millionth weight of sodium.
Commercial production
Enjoying rather specialized applications, only about 100,000 tonnes of metallic
sodium are produced annually.[18] Metallic sodium was first produced commercially in
1855 by carbothermal reduction ofsodium carbonate at 1100 C,[citation needed] in what is
known as the Deville process:[38][39][40]

Na2CO3 + 2 C 2 Na + 3 CO

A related process based on the reduction of sodium hydroxide was developed in


1886.[38]

Sodium is now produced commercially through the electrolysis of molten sodium


chloride, based on a process patented in 1924.[41][42] This is done in a Downs cell in
which the NaCl is mixed withcalcium 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 previousCastner process of
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.[citation needed] 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.[43]

Applications
Though metallic sodium has some important uses, the major applications of sodium
use is in its many compounds; millions of tons of the chloride, hydroxide,
and carbonate are produced annually.
Free element

Metallic sodium is mainly used for the production of sodium borohydride, sodium
azide, indigo, and triphenylphosphine. Previous uses were for the making
of tetraethyllead and titanium metal; because applications for these chemicals were
discontinued, the production of sodium declined after 1970.[18] Sodium is also used as
an alloying metal, an anti-scaling agent,[44] and as a reducing agent for metals when
other materials are ineffective. Note the free element is not used as a scaling agent,
ions in the water are exchanged for sodium ions. Sodium vapor lamps are often used
for street lighting in cities and give colours ranging from yellow-orange to peach as
the pressure increases.[45] By itself or with potassium, sodium is a desiccant; it gives an
intense blue colouration with benzophenone when the desiccate is dry.[46] In organic
synthesis, sodium is used in various reactions such as the Birch reduction, and
the sodium fusion test is conducted to qualitatively analyse compounds.[47] Lasers
emitting light at the D line, utilising sodium, are used to create artificial laser guide
stars that assist in the adaptive optics for land-based visible light telescopes.[citation needed]

Heat transfer

NaK phase diagram, showing the melting point of sodium as a function of potassium
concentration. NaK with 77% potassium is eutectic and has the lowest melting point
of the NaK alloys at 12.6 C.[48]

Liquid sodium is used as a heat transfer fluid in some fast reactors,[49] due to its high
thermal conductivity and low neutron absorption cross section, which is required to
achieve a high neutron flux; the high boiling point allows the reactor to operate at
ambient pressure. Drawbacks of using sodium include its opacity, which hinders
visual maintenance, and its explosive properties. Radioactive sodium-24may be
formed by neutron activation during operation, posing a slight radiation hazard; the
radioactivity stops within a few days after removal from the reactor. If a reactor needs
to be frequently shut down, NaK is used; due to it being liquid at room temperature,
cooling pipes do not freeze. In this case, the pyrophoricity of potassium means extra
precautions against leaks need to be taken. Another heat transfer application is in
high-performance internal combustion engines with poppet valves, where valve stems
partially filled with sodium are used as a heat pipe to cool the valves.

Biological role
Main article: Sodium in biology

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.[50]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.[51] The UL for sodium is 2.3 grams per
day,[52] the threshold which could lead to hypertension when exceeded,[53] but on
average people in the United States consume 3.4 grams per day.[54] Hypertension
causes 7.6 million premature deaths worldwide each year.[55] (Note that salt contains
about 39.3% sodium[56]the rest being chlorine and other trace chemicals; thus the UL
of 2.3g sodium would be about 5.9g, or 2.7ml of saltabout half a US teaspoon[57])

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.[58] 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;[59] hence, sodium is
the most prominent cation in extracellular fluid.[60]

Unusually low or high sodium levels in humans are recognized in medicine


as hyponatremia and hypernatremia. These conditions may be caused by genetic
factors, physical factors associated with ageing or illnesses involving vomiting or
diarrhea.[61]

In C4 plants, sodium is a micronutrient that aids in metabolism, specifically in


regeneration of phosphoenolpyruvate and synthesis of chlorophyll.[62] In others, it
substitutes for potassium in several roles, such as maintaining turgor pressure and
aiding in the opening and closing of stomata.[63] 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.[64] To avoid these problems, plants developed mechanisms that
limit sodium uptake by roots, store them in cell vacuoles, and control them over long
distances;[65] excess sodium may also be stored in old plant tissue, limiting the damage
to new growth.

Precautions

NFPA 704
"fire diamond"

1
3
2
W

The fire diamond


hazard sign for
sodium metal[66]

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 an oxidizer.[citation needed] 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.[67] 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
From Wikipedia, the free encyclopedia
Jump to: navigation, search
Magnesium (Mg) is not to be confused with manganese (Mn).

Magnesium, Mg 12

Spectral lines of magnesium

General properties

Name, symbol magnesium, Mg

Appearance shiny grey solid

Pronunciation /mnizim/
mag-NEE-zee-m

Magnesium in the periodic table

Be

Mg

Ca

sodium magnesium aluminium

Atomic number 12
Standard atomic weight (Ar) 24.305[1] (24.30424.307)[2]

Element category alkaline earth metal

Group, block group 2 (alkaline earth metals),s-block

Period period 3

Electron configuration [Ne] 3s2

per shell 2, 8, 2

Physical properties

Phase solid

Melting point 923 K (650 C, 1202 F)

Boiling point 1363 K (1091 C, 1994 F)

Density near r.t. 1.738 g/cm3

when liquid, at m.p. 1.584 g/cm3

Heat of fusion 8.48 kJ/mol

Heat of vaporization 128 kJ/mol

Molar heat capacity 24.869 J/(molK)

vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 701 773 861 971 1132 1361

Atomic properties
Oxidation states +2, +1[3] (a strongly basicoxide)

Electronegativity Pauling scale: 1.31

Ionization energies 1st: 737.7 kJ/mol


2nd: 1450.7 kJ/mol
3rd: 7732.7 kJ/mol
(more)

Atomic radius empirical: 160 pm

Covalent radius 1417 pm

Van der Waals radius 173 pm

Miscellanea

Crystal structure hexagonal close-packed (hcp)

Speed of soundthin rod 4940 m/s (at r.t.) (annealed)

Thermal expansion 24.8 m/(mK) (at 25 C)

Thermal conductivity 156 W/(mK)

Electrical resistivity 43.9 nm (at 20 C)

Magnetic ordering paramagnetic

Young's modulus 45 GPa

Shear modulus 17 GPa


Bulk modulus 45 GPa

Poisson ratio 0.290

Mohs hardness 12.5

Brinell hardness 44260 MPa

CAS Registry Number 7439-95-4

History

Naming after Magnesia, Greece

Discovery Joseph Black (1755)

First isolation Humphry Davy (1808)

Most stable isotopes

Main article: Isotopes of magnesium

iso NA half-life DM DE (MeV) DP


24
Mg 78.99%24Mg is stable with 12 neutrons
25
Mg 10.00%25Mg is stable with 13 neutrons
26
Mg 11.01%26Mg is stable with 14 neutrons

references

Magnesium is a chemical element with symbol Mg and atomic number 12. It is a


shiny gray solid which bears a close physical resemblance to the other five elements
in the second column (Group 2, or alkaline earth metals) of the periodic table: they
each have the same electron configuration in their outer electron shell producing a
similar crystal structure.

Magnesium is the ninth most abundant element in the universe.[4][5] It is synthesized in


large, aging stars from the sequential addition of three helium nuclei to
a carbon nucleus. When such a star explodes as a supernova, much of its magnesium
is expelled into the interstellar medium, where it can be recycled into new star
systems. Consequently, magnesium is the eighth most abundant element in the Earth's
crust[6] and the fourth most common element in the Earth
(below iron, oxygen and silicon), making up 13% of the planet's mass and a large
fraction of the planet's mantle. It is the third most abundant element dissolved in
seawater, after sodium and chlorine.[7]

Magnesium only occurs naturally in combination with other elements, where it


invariably has a +2 oxidation state. The free element (metal) can be produced
artificially, and is highly reactive (though once produced, it is coated in a thin layer of
oxide, which partly inhibits this reactivity seepassivation). The free metal burns
with a characteristic brilliant-white light, making it a useful ingredient in flares. The
metal is now obtained mainly byelectrolysis of magnesium salts obtained from brine.
In commerce, 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, this alloy is prized for its properties of lightness combined
with strength.

Magnesium is the eleventh most abundant element by mass in the human body.
Its ions are essential to all cells. They interact with polyphosphatecompounds such
as ATP, DNA, and RNA. Hundreds of enzymes require magnesium ions to function.
Magnesium compounds are used medicinally as common laxatives, antacids (e.g.,
milk of magnesia), and to stabilize abnormal nerve excitation or blood vessel spasm
such as in eclampsia. Magnesium ions are sour to the taste, and in low concentrations
they help impart a natural tartness to fresh mineral waters. Magnesium is the metallic
ion at the center of chlorophyll, and is a common additive to fertilizers.[8]

Contents
[hide]

1 Characteristics
o 1.1 Physical properties
o 1.2 Chemical properties
1.2.1 Flammability
1.2.2 Source of light
o 1.3 Occurrence
2 Forms
o 2.1 Alloy
2.1.1 Corrosion
2.1.2 High-temperature creep and flammability
o 2.2 Compounds
o 2.3 Isotopes
3 Production
4 History
5 Uses as a metal
o 5.1 Aircraft
o 5.2 Automotive
o 5.3 Electronics
o 5.4 Other
o 5.5 Safety precautions
6 Uses in compounds
7 Biological roles
o 7.1 Mechanism of action
o 7.2 Dietary sources, recommended intake, and supplementation
o 7.3 Metabolism
o 7.4 Detection in serum and plasma
o 7.5 Deficiency
o 7.6 Therapy
o 7.7 Overdose
o 7.8 Function in plants
8 See also
9 Notes
10 References
11 External links

Characteristics
Physical properties

Elemental magnesium is a gray-white lightweight metal, two-thirds the density of


aluminium. It tarnishes slightly when exposed to air, although, unlike the other 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.
Magnesium has both the lowest melting and the lowest boiling points of any of the
alkali earth metals, at 923 K (1,202 F) and 1,363 K (1,994 F), respectively.[9]

Magnesium reacts with water at room temperature, though it reacts much more slowly
than the similar earth alkali metal 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 amagnesium-based engine.

Magnesium also reacts exothermically with most acids, such as hydrochloric


acid (HCl). This reaction with HCl produces the chloride of the metal and releases
hydrogen gas (just as when HCl reacts with aluminium, zinc, and many other metals).

Chemical properties

Flammability

Magnesium is a highly flammable metal, especially when powdered or shaved into


thin strips; (it is, however, difficult to ignite in mass or bulk). Flame temperatures of
magnesium and magnesium alloys can reach 3,100 C (3,370 K; 5,610 F),[10] although
flame height above the burning metal is usually less than 300 mm (12 in).[11] 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 thefirebombing of cities in World War II, the only
practical civil defense being to smother a burning flare under dry sand to exclude the
atmosphere. Magnesium may also be used as an ignition source for thermite, a
mixture of aluminium and iron oxide powder that is otherwise difficult to ignite.

Source of light

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 flashbulbs. Magnesium powder is used in the manufacture
of fireworks and marine flares where a brilliant white light is required.

Occurrence

See also: Category:Magnesium minerals.

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.[6] 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 hydroxideprecipitate.

MgCl
2 + Ca(OH)
2 Mg(OH)
2 + CaCl
2

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 MgCl
2+2H
2O

From magnesium chloride, electrolysis produces magnesium.

Forms
Alloy

As of 2013, magnesium alloy consumption was less than one 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.[12]

Corrosion

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.[12] Reducing the quantity of these
metals improves corrosion resistance. Sufficient manganeseovercomes the corrosive
effects of iron. This requires precise control over composition, increasing
costs.[12] 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.[12][13]

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.[12]

Compounds

Magnesium forms a variety of industrially and biologically important compounds,


including magnesium carbonate, magnesium chloride, magnesium citrate, magnesium
hydroxide (milk of magnesia),magnesium oxide, magnesium sulfate, and magnesium
sulfate heptahydrate (Epsom salts).

Isotopes

Main article: Isotopes of magnesium

Magnesium has three stable isotopes: 24


Mg, 25
Mg and 26
Mg. All are present in significant amounts (see table of isotopes above). About 79%
of Mg is 24
Mg. The isotope 28
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
Mg has found application in isotopic geology, similar to that of aluminium. 26
Mg is a radiogenic daughter product of 26
Al, which has a half-life of 717,000 years. Large enrichments of stable 26
Mg have been observed in the Ca-Al-rich inclusions of some carbonaceous
chondrite meteorites. The anomalous abundance of 26
Mg is attributed to the decay of its parent 26
Al in the inclusions. Therefore, the meteorite must have formed in the solar
nebula before the 26
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 26
Mg/24
Mg against an Al/Mg ratio. In an isochron dating plot, the Al/Mg ratio plotted is27
Al/24
Mg. The slope of the isochron has no age significance, but indicates the initial 26
Al/27
Al ratio in the sample at the time when the systems were separated from a common
reservoir.

Production
2011 production
Country
(tonnes)[14]
China 661,000
U.S. [note 1]
63,500
Russia 37,000
Israel 30,000
Kazakhstan 21,000
Brazil 16,000
Ukraine 2,000
Serbia 1,500
Total 832,000

Magnesium sheets and ingots

China is the dominant supplier of magnesium, with approximately 80% of the world
market share. China is almost completely reliant on the silicothermic Pidgeon
process (the reduction of the oxide at high temperatures with silicon, often provided
by a ferrosilicon alloy in which the iron is but a spectator in the reactions) to obtain
the metal.[15] The process can also be carried out with carbon at approx 2300 C:

2MgO
(s) + Si
(s) + 2CaO
(s) 2Mg
(g) + Ca
2SiO
4(s)
MgO
(s) + C
(s) Mg
(g) + CO
(g)

In the United States, magnesium is obtained principally with the Dow process,
by electrolysis of fused magnesium chloride from brine and sea water. A saline
solution containing Mg2+
ions is first treated with lime (calcium oxide) and the precipitated magnesium
hydroxide is collected:

Mg2+
(aq) + CaO
(s) + H
2O Ca2+
(aq) + Mg(OH)
2(s)

The hydroxide is then converted to a partial hydrate of magnesium chloride by


treating the hydroxide with hydrochloric acid and heating of the product:

Mg(OH)
2(s) + 2 HCl MgCl
2(aq) + 2H
2O
(l)

The salt is then electrolyzed in the molten state. At the cathode, the Mg2+
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
Cl
2 (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 Yttria-
stabilized zirconia (YSZ). The anode is a liquid metal. At the YSZ/liquid metal
anode O2
is oxidized. 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.[16] It has been reported that this method provides a 40% reduction
in cost per pound over the electrolytic reduction method.[17] 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.[18]

History
The name magnesium originates from the Greek word for a district
in Thessaly called Magnesia.[19] 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
47H
2O.

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.[20] Antoine
Bussy prepared it in coherent form in 1831. Davy's first suggestion for a name was
magnium,[20] but the name magnesium is now used.
Uses as a metal

An unusual application of magnesium as an illuminationsource while wakeskating in


1931

Magnesium is the third-most-commonly-used structural metal, following iron and


aluminium. It has been called the lightest useful metal by The Periodic Table of
Videos.[21]

The main applications of magnesium are, in order: component of aluminium alloys,


in die-casting (alloyed with zinc),[22] to remove sulfur in the production of iron and
steel, and the production oftitanium in the Kroll process.[23]

Historically, magnesium was one of the main aerospace construction metals and was
used for German military aircraft as early as World War I and extensively for German
aircraft in World War II.

The Germans coined the name "Elektron" for magnesium alloy. The term is still used
today. The application of magnesium in the commercial aerospace industry was
generally restricted to engine-related components, due either to perceived hazards
with magnesium parts in the event of fire or to corrosion. Currently, the use of
magnesium alloys in aerospace is increasing, mostly driven by the increasing
importance of fuel economy and the need to reduce weight.[24] The development and
testing of new magnesium alloys continues, notably Elektron 21, which has
successfully undergone extensive aerospace testing for suitability in engine and
internal and airframe components.[25] The European Community runs three R&D
magnesium projects in the Aerospace priority of Six Framework Program.

Aircraft

Wright Aeronautical used a magnesium crankcase in the WWII-era Wright


Duplex Cyclone aviation engine. This presented a serious problem for the
earliest examples of the Boeing B-29 heavy bomber, as engine fires in flight
could ignite the engine crankcases, literally "torching" the wing spar apart.[26][27]

Automotive

Mg alloy motorcycle engine blocks

Mercedes-Benz used the alloy Elektron in the body of an early


model Mercedes-Benz 300 SLR; these cars ran (with successes) at Le Mans,
the Mille Miglia, and other world-class race events in 1955.
Porsche used magnesium alloy frames in the 917/053 that won Le Mans in
1971, and continues to use magnesium alloys for its engine blocks due to the
weight advantage.
Volkswagen Group has used magnesium in its engine components for many
years.[citation needed]
Mitsubishi Motors also uses magnesium for its paddle shifters.
BMW used magnesium alloy engine blocks in the 2006 325i and 330i models,
including an aluminium alloy insert for the cylinder walls and cooling jackets
surrounded by a high-temperature magnesium alloy AJ62A.
Chevrolet used the magnesium alloy AE44 in the 2006 Corvette Z06.

Both AJ62A and AE44 are recent developments in high-temperature low-


creep magnesium alloys. The general strategy for such alloys is to
form intermetallic precipitates at the grain boundaries, for example by
adding mischmetal or calcium.[28] New alloy development and lower costs that make
magnesium competitive with aluminium will increase the number of automotive
applications.

Electronics

Because of low weight and good mechanical and electrical properties, magnesium is
widely used for manufacturing of mobile phones, laptop and tablet computers,
cameras, and other electronic components.
Products made of magnesium: firestarter and shavings, sharpener, magnesium ribbon

Other

Magnesium, being readily available and relatively nontoxic, has a variety of uses:

Magnesium is flammable, burning at a temperature of approximately 3,100 C


(3,370 K; 5,610 F),[10] and the autoignition temperature of magnesium ribbon is
approximately 473 C (746 K; 883 F).[29] It produces intense, bright, white light
when it burns. Magnesium's high combustion temperature makes it a useful
tool for starting emergency fires. Other uses include flashphotography,
flares, pyrotechnics, and fireworks sparklers. Magnesium is also often used to
ignite thermite or other materials that require a high ignition temperature.

Magnesium firestarter (in left hand), used with a pocket knifeand flint to create
sparks that ignite the shavings

In the form of turnings or ribbons, to prepare Grignard reagents, which are


useful in organic synthesis.
As an additive agent in conventional propellants and the production of nodular
graphite in cast iron.
As a reducing agent to separate uranium and other metals from their salts.
As a sacrificial (galvanic) anode to protect boats, underground tanks, pipelines,
buried structures, and water heaters.
Alloyed with zinc to produce the zinc sheet used in photoengraving plates in
the printing industry, dry-cell battery walls, and roofing.[22]
As a metal, this element's principal use is as an alloying additive to aluminium
with these aluminium-magnesium alloys being used mainly for beverage cans,
sports equipment such as golf clubs, fishing reels, and archery bows and
arrows.
Specialty, high-grade car wheels of magnesium alloy are called "mag wheels",
although the term is often more broadly misapplied to include aluminium
wheels. Many car and aircraft manufacturers have made engine and body parts
from magnesium.

Safety precautions

The combusting magnesium-bodied Honda RA302 at the1968 French Grand Prix,


after the crash that killed driver Jo Schlesser.

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.[30]

Magnesium is capable of reducing water to highly flammable hydrogen gas:[31]

Mg (s) + 2 H
2O (l) Mg(OH)
2 (s) + H
2 (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 + CO
2 2 MgO + C (s)

hence, carbon dioxide fire extinguishers are also ineffective for extinguishing
magnesium fires.[32]

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.

Uses in compounds
Magnesium compounds, primarily magnesium oxide (MgO), are used as
a refractory material in furnace linings for producing iron, steel, nonferrous
metals, glass, and cement. Magnesium oxide and other magnesium compounds are
also used in the agricultural, chemical, and construction industries. Magnesium oxide
from calcination is used as an electrical insulator in fire-resistant cables.[33]

Magnesium reacted with an alkyl halide gives a Grignard reagent, which is a very
useful tool for preparing alcohols.

Magnesium salts are frequently included in various foods, fertilizers (magnesium is a


component of chlorophyll), and culture media.

Magnesium sulfite is used in the manufacture of paper (sulfite process).

Magnesium phosphate is used to fireproof wood used in construction.

Magnesium hexafluorosilicate is used in mothproofing of textiles.

In the form of turnings or ribbons, Mg is useful in purification of solvents, for


example the preparation of super-dry ethanol.

Biological roles
Main article: Magnesium in biology

Mechanism of action

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.[34]

Dietary sources, recommended intake, and supplementation

Examples of food sources of magnesium

Spices, nuts, cereals, cocoa and vegetables are rich sources of magnesium.[35] Green
leafy vegetables such as spinach are also rich in magnesium since they contain
chlorophyll.

The UK recommended daily values for magnesium is 300 mg for men and 270 mg for
women.[36] 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.[37]

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, is
the least bioavailable.[38][39]

Metabolism

An adult has 2226 grams of magnesium,[40] with 60% in the skeleton, 39%
intracellular (20% in skeletal muscle), and 1% extracellular.[41] Serum levels are
typically 0.71.0 mmol/L or 1.82.4 mEq/L. Serum magnesium levels may be normal
even when intracellular magnesium is deficient. The mechanisms for maintaining the
magnesium level in the serum are varying gastrointestinal absorption and renal
excretion. Intracellular magnesium is correlated with intracellular potassium.
Increased magnesium lowers calcium[42] and can either prevent hypercalcemia or cause
hypocalcemia depending on the initial level.[42] Low and high protein intake inhibit
magnesium absorption, as does the amount of phosphate, phytate, and fat in the gut.
Excess dietary magnesium is excreted in feces, urine, and sweat.[37] Magnesium status
may be assessed via serum and erythrocyte magnesium concentrations coupled with
urinary and fecal magnesium content, but intravenous magnesium loading tests are
more accurate and practical.[43] A retention of 20% or more of the injected amount
indicates deficiency.[44] No biomarker has been established for magnesium.[45]

Detection in serum and plasma

Magnesium concentrations in plasma or serum may be measured to monitor for


efficacy and safety in those receiving the drug therapeutically, to confirm the
diagnosis in potential poisoning victims or to assist in the forensic investigation in a
case of fatal overdosage. The newborn children of mothers having received parenteral
magnesium sulfate during labor may exhibit toxicity with normal serum magnesium
levels.[46]

Deficiency

Magnesium deficiency (hypomagnesemia) is common: it is found in 2.515% of the


general population.[47] The primary cause of deficiency is decreased dietary intake:
only 32% of people in the United States meet the recommended daily
allowance.[48] Other causes are increased renal or gastrointestinal loss, an increased
intracellular shift, and proton-pump inhibitor antacid therapy. Most are asymptomatic,
but symptoms referable to neuromuscular, cardiovascular, and metabolic dysfunction
may occur.[47] Alcoholism is often associated with magnesium deficiency. Chronically
low serum magnesium levels are associated with metabolic syndrome, diabetes
mellitus type 2, fasciculation, and hypertension.[49]

Therapy

Intravenous magnesium is recommended by the ACC/AHA/ESC 2006


Guidelines for Management of Patients With Ventricular Arrhythmias and the
Prevention of Sudden Cardiac Death for patients with
ventricular arrhythmia associated with torsades de pointes who present
with long QT syndrome; and for the treatment of patients with digoxin induced
arrhythmias.[50]
Magnesium is the drug of choice in the management of pre-
eclampsia and eclampsia.[51][52]
Hypomagnesemia, including that caused by alcoholism, is reversible by oral or
parenteral magnesium administration depending on the degree of deficiency.[53]
There is limited evidence that magnesium supplementation may play a role in
the prevention and treatment of migraine.[54]
Oral magnesium may be therapeutic for restless leg syndrome.[55]

Sorted by type of magnesium salt, other therapeutic applications include:

Magnesium sulfate, as the heptahydrate called Epsom salts, is used as bath


salts, as a laxative, and as a highly soluble fertilizer.[56]
Magnesium hydroxide, suspended in water, is used in milk of
magnesia antacids and laxatives.
Magnesium chloride, oxide, gluconate, malate, orotate, glycinate and citrate are
all used as oral magnesium supplements.
Magnesium borate, magnesium salicylate, and magnesium sulfate are used
as antiseptics.
Magnesium bromide is used as a mild sedative (this action is due to
the bromide, not the magnesium).
Magnesium stearate is a
slightly flammable white powder with lubricating properties.
In pharmaceutical technology, it is used in the manufacturing of numerous
kinds of tablets to prevent the tablets from sticking to the equipment during the
tablet compression process (i.e., when the tablet's substance is pressed into
tablet form).
Magnesium carbonate powder is used by athletes such
as gymnasts, weightlifters, and climbers to eliminate moisture and improving
the grip on a gymnastic apparatus, lifting bar, and climbing rocks.
Magnesium L-threonate is used as a dietary magnesium supplement

Overdose

Overdose from dietary sources alone is unlikely because excess magnesium in the
blood is promptly filtered by the kidneys.[47] Overdose with magnesium tablets is
possible in the presence of impaired renal function. There is a single case report
of hypermagnesemia in a woman with normal renal function using high doses of
magnesium salts for catharsis.[57] The most common symptoms of overdose are nausea,
vomiting and diarrhea; other symptoms include hypotension, confusion, slowed heart
and respiratory rate, deficiencies of other minerals, coma, cardiac arrhythmia, and
death from cardiac arrest.[42]

Function in plants
Plants require magnesium to synthesize chlorophyll, essential for photosynthesis.
Magnesium in the center of the porphyrin ring in chlorophyll functions in a manner
similar to the iron in the center of the porphyrin ring in heme. Magnesium
deficiency in plants causes late-season yellowing between leaf veins, especially in
older leaves, and can be corrected by applying to the soil either Epsom salts (which is
rapidly leached), or crushed dolomitic limestone.

Aluminium
From Wikipedia, the free encyclopedia
Jump to: navigation, search
This article is about the metallic element. For other uses, see Aluminium
(disambiguation).

Aluminium, Al 13

Spectral lines of aluminium

General properties

Name, symbol aluminium, Al

Appearance silvery gray metallic

Pronunciation UK i /ljmnim/
AL-ew-MIN-ee-m
US i /ljumnm/
-LEW-mi-nm

Alternative name aluminum (US)

Aluminium in the periodic table

B

Al

Ga

magnesium aluminium silicon

Atomic number 13

Standard atomic weight () (Ar) 26.9815385(7)[1]

Element category post-transition metal, sometimes


considered ametalloid

Group, block group 13, p-block

Period period 3

Electron configuration [Ne] 3s2 3p1

per shell 2, 8, 3

Physical properties

Phase solid

Melting point 933.47 K (660.32 C, 1220.58 F)

Boiling point 2743 K (2470 C, 4478 F)


Density near r.t. 2.70 g/cm3

when liquid, at m.p. 2.375 g/cm3

Heat of fusion 10.71 kJ/mol

Heat of vaporization 284 kJ/mol

Molar heat capacity 24.20 J/(molK)

vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 1482 1632 1817 2054 2364 2790

Atomic properties

Oxidation states 3, 2,[2] 1[3] (an amphotericoxide)

Electronegativity Pauling scale: 1.61

Ionization energies 1st: 577.5 kJ/mol


2nd: 1816.7 kJ/mol
3rd: 2744.8 kJ/mol
(more)

Atomic radius empirical: 143 pm

Covalent radius 1214 pm

Van der Waals radius 184 pm

Miscellanea

Crystal structure face-centered cubic (fcc)


Speed of soundthin rod (rolled) 5000 m/s (at r.t.)

Thermal expansion 23.1 m/(mK) (at 25 C)

Thermal conductivity 237 W/(mK)

Electrical resistivity 28.2 nm (at 20 C)

Magnetic ordering paramagnetic[4]

Young's modulus 70 GPa

Shear modulus 26 GPa

Bulk modulus 76 GPa

Poisson ratio 0.35

Mohs hardness 2.75

Vickers hardness 160350 MPa

Brinell hardness 160550 MPa

CAS Registry Number 7429-90-5

History

Prediction Antoine Lavoisier[5] (1787)

First isolation Hans Christian rsted[6](1825)


Named by Humphry Davy[5] (1807)

Most stable isotopes

Main article: Isotopes of aluminium

iso NA half-life DM DE (MeV) DP


+ 1.17 26
Mg
26
Al trace 7.17105 y 26
Mg
1.8086
27
Al 100%27Al is stable with 14 neutrons

references

Aluminium (or aluminum; see spelling differences) is a chemical element in


the boron group with symbol Al and atomic number 13. It is a silvery-white, soft,
nonmagnetic, ductile metal. Aluminium is the third most abundant
element (after oxygen and silicon) in the Earth's crust, and the most abundant
metal there. It makes up about 8% by weight of the crust, though it is less common in
the mantle below. 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.[7]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, no known form of life uses


aluminium salts metabolically. In keeping with its pervasiveness, aluminium is well
tolerated by plants and animals.[8] Owing to their prevalence, potential beneficial (or
otherwise) biological roles of aluminium compounds are of continuing interest.

Contents
[hide]

1 Characteristics
o 1.1 Physical
o 1.2 Chemical
o 1.3 Isotopes
o 1.4 Natural occurrence
2 Production and refinement
o 2.1 Recycling
3 Compounds
o 3.1 Oxidation state +3
3.1.1 Halides
3.1.2 Oxide and hydroxides
3.1.3 Carbide, nitride, and related materials
o 3.2 Organoaluminium compounds and related hydrides
o 3.3 Oxidation states +1 and +2
3.3.1 Aluminium(I)
3.3.2 Aluminium(II)
o 3.4 Analysis
4 Applications
o 4.1 General use
o 4.2 Aluminium compounds
4.2.1 Alumina
4.2.2 Sulfates
4.2.3 Chlorides
4.2.4 Niche compounds
o 4.3 Aluminium alloys in structural applications
5 History
o 5.1 Hall-Heroult process: availability of cheap aluminium metal
6 Etymology
7 Biology
8 Health concerns
o 8.1 Alzheimer's disease
o 8.2 Occupational safety
9 Effect on plants
10 Biodegradation
11 See also
12 References
13 External links

Characteristics
"Red mud" storage facility inStade, Germany. The aluminium industry generates
about 70 million tons of this waste annually.

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, whilealuminium alloys have yield strengths ranging from 200 MPa to 600
MPa.[9] Aluminium has about one-third the density and stiffness of steel. It is
easilymachined, cast, drawn and extruded.

Aluminium atoms are arranged in a face-centered cubic (fcc) structure. Aluminium


has a stacking-fault energy of approximately 200 mJ/m2.[10]

Aluminium is a good thermal and electrical conductor, having 59% the conductivity
of copper, both thermal and electrical, while having only 30% ofcopper's density.
Aluminium is capable of being a superconductor, with a superconducting critical
temperature of 1.2 kelvin and a critical magnetic field of about
100 gauss (10 milliteslas).[11]

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
further oxidation.[12] The strongest aluminium alloys are less corrosion resistant due
to galvanic reactions with alloyed copper.[9] This corrosion resistance is also often
greatly reduced by aqueous salts, particularly in the presence of dissimilar metals.

In highly acidic solutions aluminium reacts with water to form hydrogen, and in
highly alkaline ones to form aluminates protective passivation under these
conditions is negligible. Also, chlorides such as common sodium chloride are well-
known sources of corrosion of aluminium and are among the chief reasons that
household plumbing is never made from this metal.[13]

However, owing to its resistance to corrosion generally, 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) bysilver, gold, and copper.[14]

Aluminium is oxidized by water at temperatures below 280 C to


produce hydrogen, aluminium hydroxide and heat:

2 Al + 6 H2O 2 Al(OH)3 + 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.[15]

Isotopes

Main article: Isotopes of aluminium

Aluminium has many known isotopes, whose mass numbers range from 21 to 42;
however, only 27Al (stable isotope) and 26Al (radioactive isotope,t12 = 7.2105 y) occur
naturally. 27Al has a natural abundance above 99.9%. 26Al is produced from argon in
the atmosphere by spallation caused bycosmic-ray protons. Aluminium isotopes have
found practical application in dating marine sediments, manganese nodules, glacial
ice, quartz in rockexposures, and meteorites. The ratio of 26Al to 10Be has been used to
study the role of transport, deposition, sediment storage, burial times, and erosion on
105 to 106 year time scales.[16] Cosmogenic 26Al was first applied in studies of
the Moon and meteorites. Meteoroid fragments, after departure from their parent
bodies, are exposed to intense cosmic-ray bombardment during their travel through
space, causing substantial 26Al production. After falling to Earth, atmospheric
shielding drastically reduces 26Al production, and its decay can then be used to
determine the meteorite's terrestrial age. Meteorite research has also shown that 26Al
was relatively abundant at the time of formation of our planetary system. Most
meteorite scientists believe that the energy released by the decay of 26Al was
responsible for the melting and differentiation of some asteroids after their formation
4.55 billion years ago.[17]

Natural occurrence
See also: List of countries by bauxite production

Stable aluminium is created when hydrogen fuses with magnesium, either in large
stars or in supernovae.[18] It is estimated to be the 14th most common element in the
Universe, by mass-fraction.[19] However, among the elements that have odd atomic
numbers, aluminium is the third most abundant by mass fraction, after hydrogen and
nitrogen.[20]

In the Earth's crust, aluminium is the most abundant (8.3% by mass) metallic element
and the third most abundant of all elements (after oxygen and silicon).[21] The Earth's
crust has a higher prevalence of aluminum than the rest of the planet, due to
aluminium silicates in the crust. In the Earths mantle, which is only 2% aluminium by
mass, these aluminium silicate minerals are largely replaced by silicaand magnesium
oxides. Overall, the Earth is about 1.4% aluminium by mass (eighth in abundance by
mass). In the Earth as a whole, aluminium gains in abundance as compared with the
Solar system and Universe, due to Earth's loss of a number of elements which are
common in the universe, but which are volatiles at the Earth's distance from the Sun
(hydrogen, helium, neon, nitrogen, carbon as hydrocarbon).

Because of its strong affinity to oxygen, aluminum 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.[22] Native aluminium has been reported in cold seeps in
the northeastern continental slope of the South China Sea and Chen et
al. (2011)[23] have proposed a theory of its origin as resulting by reduction from
tetrahydroxoaluminate Al(OH)4 to metallic aluminium by bacteria.[23]

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 orebauxite (AlOx(OH)32x). Bauxite occurs as
a weathering product of low iron and silica bedrock in tropical climatic
conditions.[24] Large deposits of bauxite occur in
Australia, Brazil, Guinea and Jamaicaand the primary mining areas for the ore are
in Australia, Brazil, China, India, Guinea, Indonesia, Jamaica, Russia and Suriname.

Production and refinement


See also: Category:Aluminium minerals and List of countries by aluminium
production

Bauxite, a major aluminium ore. The red-brown color is due to the presence
of iron minerals.

Bauxite is converted to aluminium oxide (Al2O3) via the Bayer


process.[8] Relevant chemical equations are:

Al2O3 + 2 NaOH 2 NaAlO2 + H2O


2 H2O + NaAlO2 Al(OH)3 + NaOH

The intermediate sodium aluminate, given the simplified formula NaAlO 2, is soluble
in strongly alkaline water, and the other components of the ore are not. Depending on
the quality of the bauxite ore, twice as much waste ("red mud") as alumina is
generated.

The conversion of alumina to aluminium metal is achieved by the Hall-Hroult


process. In this energy-intensive process, a solution of alumina in a molten (950 and
980 C (1,740 and 1,800 F)) mixture of cryolite (Na3AlF6) with calcium
fluoride is electrolyzed to give the metal:

Al3+ + 3 e Al

At the anode, oxygen is formed:

2 O2 O2 + 4 e

The aluminium metal then sinks to the bottom of the solution and is tapped off,
usually cast into large blocks called aluminium billets for further processing. To some
extent, the carbon anode is consumed by subsequent reaction with oxygen to form
carbon dioxide. The anodes in a reduction cell must therefore be replaced regularly,
since they are consumed in the process. The cathodes do erode, mainly due to
electrochemical processes and metal movement. After five to ten years, depending on
the current used in the electrolysis, a cell must be rebuilt because of cathode wear.
World production trend of aluminium

Aluminium electrolysis with the Hall-Hroult process consumes a lot of energy. The
worldwide average specific energy consumption is approximately 150.5 kilowatt-
hours per kilogram of aluminium produced (52 to 56 MJ/kg). The most modern
smelters achieve approximately 12.8 kWh/kg (46.1 MJ/kg). (Compare this to the heat
of reaction, 31 MJ/kg, and the Gibbs free energy of reaction, 29 MJ/kg.) Reduction
line currents for older technologies are typically 100 to 200 kiloamperes; state-of-the-
art smelters operate at about 350 kA. Trials have been reported with 500 kA cells.[citation
needed]

The Hall-Heroult process produces aluminium with a purity of above 99%. Further
purification can be done by the Hoopes process. The process involves the electrolysis
of molten aluminium with a sodium, barium and aluminium fluoride electrolyte. The
resulting aluminium has a purity of 99.99%.[8][25]

Electric power represents about 20% to 40% of the cost of producing aluminium,
depending on the location of the smelter. Aluminium production consumes roughly
5% of electricity generated in the U.S.[26] Aluminium producers tend to locate smelters
in places where electric power is both plentiful and inexpensivesuch as the United
Arab Emirates with its large natural gas supplies,[27] andIceland[28] and Norway[29] with
energy generated from renewable sources. The world's largest smelters of alumina are
located in the People's Republic of China, Russia and the provinces
of Quebec andBritish Columbia in Canada.[26][30][31]

Aluminium spot price 19872012


In 2005, the People's Republic of China was the top producer of aluminium with
almost a one-fifth world share, followed by Russia, Canada, and the US, reports
the British Geological Survey.

Over the last 50 years, Australia has become the world's top producer of bauxite ore
and a major producer and exporter of alumina (before being overtaken by China in
2007).[30][32] Australia produced 77 million tonnes of bauxite in 2013.[33] The Australian
deposits have some refining problems, some being high in silica, but have the
advantage of being shallow and relatively easy to mine.[34]

Recycling

Aluminium recycling code


Main article: Aluminium recycling

Aluminium is theoretically 100% recyclable without any loss of its natural qualities.
According to the International Resource Panel's Metal Stocks in Society report, the
global per capita stock of aluminium in use in society (i.e. in cars, buildings,
electronics etc.) is 80 kg (180 lb). Much of this is in more-developed countries (350
500 kg (7701,100 lb) per capita) rather than less-developed countries (35 kg (77 lb)
per capita). Knowing the per capita stocks and their approximate lifespans is
important for planning recycling.

Recovery of the metal via recycling has become an important use of the aluminium
industry. Recycling was a low-profile activity until the late 1960s, when the growing
use of aluminium beverage cansbrought it to the public awareness.

Recycling involves melting the scrap, a process that requires only 5% of the energy
used to produce aluminium from ore, though a significant part (up to 15% of the input
material) is lost as dross (ash-like oxide).[35] An aluminium stack melter produces
significantly less dross, with values reported below 1%.[36] The dross can undergo a
further process to extract aluminium.

In Europe aluminium experiences high rates of recycling, ranging from 42% of


beverage cans, 85% of construction materials and 95% of transport vehicles.[37]
Recycled aluminium is known as secondary aluminium, but maintains the same
physical properties as primary aluminium. Secondary aluminium is produced in a
wide range of formats and is employed in 80% of alloy injections. Another important
use is for extrusion.

White dross from primary aluminium production and from secondary recycling
operations still contains useful quantities of aluminium that can be extracted
industrially.[38] The process produces aluminium billets, together with a highly
complex waste material. This waste is difficult to manage. It reacts with water,
releasing a mixture of gases (including, among others, hydrogen, acetylene,
andammonia), which spontaneously ignites on contact with air;[39] contact with damp
air results in the release of copious quantities of ammonia gas. Despite these
difficulties, the waste has found use as a filler in asphalt and concrete.[40]

Compounds
See also: Category:Aluminium compounds.

Oxidation state +3

The vast majority of compounds, including all Al-containing minerals and all
commercially significant aluminium compounds, feature aluminium in the oxidation
state 3+. The coordination number of such compounds varies, but generally Al3+ is six-
coordinate or tetracoordinate. Almost all compounds of aluminium(III) are
colorless.[21]

Halides

All four trihalides are well known. Unlike the structures of the three heavier
trihalides, aluminium fluoride (AlF3) features six-coordinate Al. The octahedral
coordination environment for AlF3 is related to the compactness of fluoride ion, six of
which can fit around the small Al3+ center. AlF3 sublimes (with cracking) at 1,291 C
(2,356 F). With heavier halides, the coordination numbers are lower. The other
trihalides are dimeric or polymeric with tetrahedral Al centers. These materials are
prepared by treating aluminium metal with the halogen, although other methods exist.
Acidification of the oxides or hydroxides affords hydrates. In aqueous solution, the
halides often form mixtures, generally containing six-coordinate Al centers, which are
feature both halide and aquo ligands. When aluminium and fluoride are together in
aqueous solution, they readily form complex ions such as [AlF(H
2O)
5]2+
, AlF
3(H
2O)
3, and [AlF
6]3
. In the case of chloride, polyaluminium clusters are formed such as
[Al13O4(OH)24(H2O)12]7+.

Oxide and hydroxides

Aluminium forms one stable oxide, known by its mineral


name corundum. Sapphire and ruby are impure corundum contaminated with trace
amounts of other metals. The two oxide-hydroxides, AlO(OH),
are boehmite and diaspore. There are three trihydroxides: bayerite, gibbsite,
and nordstrandite, which differ in their crystalline structure (polymorphs). Most are
produced from ores by a variety of wet processes using acid and base. Heating the
hydroxides leads to formation of corundum. These materials are of central importance
to the production of aluminium and are themselves extremely useful.

Carbide, nitride, and related materials

Aluminium carbide (Al4C3) is made by heating a mixture of the elements above


1,000 C (1,832 F). The pale yellow crystals consist of tetrahedral aluminium
centers. It reacts with water or dilute acids to give methane. The acetylide, Al2(C2)3, is
made by passing acetylene over heated aluminium.

Aluminium nitride (AlN) is the only nitride known for aluminium. Unlike the oxides
it features tetrahedral Al centers. It can be made from the elements at 800 C
(1,472 F). It is air-stable material with a usefully high thermal
conductivity. Aluminium phosphide (AlP) is made similarly, and hydrolyses to
give phosphine:

AlP + 3 H2O Al(OH)3 + PH3

Organoaluminium compounds and related hydrides

Main article: Organoaluminium compound


Structure of trimethylaluminium, a compound that features five-coordinate carbon.

A variety of compounds of empirical formula AlR3 and AlR1.5Cl1.5 exist.[41] These


species usually feature tetrahedral Al centers, e.g. "trimethylaluminium" has the
formula Al2(CH3)6 (see figure). With large organic groups, triorganoaluminium exist as
three-coordinate monomers, such as triisobutylaluminium. Such compounds are
widely used in industrial chemistry, despite the fact that they are often
highly pyrophoric. Few analogues exist between organoaluminium and organoboron
compounds except for large organic groups.

The important aluminium hydride is lithium aluminium hydride (LiAlH4), which is


used in as a reducing agent in organic chemistry. It can be produced from lithium
hydride and aluminium trichloride:

4 LiH + AlCl3 LiAlH4 + 3 LiCl

Several useful derivatives of LiAlH4 are known, e.g. sodium bis(2-


methoxyethoxy)dihydridoaluminate. The simplest hydride, aluminium hydride or
alane, remains a laboratory curiosity. It is a polymer with the formula (AlH3)n, in
contrast to the corresponding boron hydride with the formula (BH 3)2.

Oxidation states +1 and +2

Although the great majority of aluminium compounds feature Al3+ centers, compounds
with lower oxidation states are known and sometime of significance as precursors to
the Al3+ species.

Aluminium(I)

AlF, AlCl and AlBr exist in the gaseous phase when the trihalide is heated with
aluminium. The composition AlI is unstable at room temperature with respect to the
triiodide:[42]

3 AlI AlI3 + 2 Al
A stable derivative of aluminium monoiodide is the cyclic adduct formed
with triethylamine, Al4I4(NEt3)4. Also of theoretical interest but only of fleeting
existence are Al2O and Al2S. Al2O is made by heating the normal oxide, Al2O3, with
silicon at 1,800 C (3,272 F) in a vacuum.[42] Such materials
quickly disproportionates to the starting materials.

Aluminium(II)

Very simple Al(II) compounds are invoked or observed in the reactions of Al metal
with oxidants. For example, aluminium monoxide, AlO, has been detected in the gas
phase after explosion[43] and in stellar absorption spectra.[44] More thoroughly
investigated are compounds of the formula R4Al2 which contain an Al-Al bond and
where R is a large organic ligand.[45]

Analysis

The presence of aluminium can be detected in qualitative analysis using aluminon.

Applications

Etched surface from a high purity (99.9998%) aluminium bar, size 5537 mm

General use

Aluminium is the most widely used non-ferrous metal.[46] Global production of


aluminium in 2005 was 31.9 million tonnes. It exceeded that of any other metal
except iron (837.5 million tonnes).[47]Forecast for 2012 is 4245 million tonnes, driven
by rising Chinese output.[48]

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.[49] 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.[50]
Household aluminium foil

Aluminium-bodied Austin "A40 Sports" (c. 1951)

Aluminium slabs being transported from a smelter

Some of the many uses for aluminium metal are in:

Transportation (automobiles, aircraft, trucks, railway cars, marine


vessels, bicycles, spacecraft, etc.) as sheet, tube, castings, etc.
Packaging (cans, foil, frame of etc.)
Construction (windows, doors, siding, building wire, etc.).[51]
A wide range of household items, from cooking utensils to baseball bats,
watches.[52]
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, and also in wires/cabling.
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 reacts with hydrochloric acid or with sodium hydroxide to produce
hydrogen gas.
Aluminium is used to make food containers, because of its resistance to
corrosion.
Aluminium with magnesium [alloy] is used to make body of aircraft.
Aluminium with other metals, used to make railway tracks.[citation needed]
Aluminium is used to make cooking utensils, because it is resistant to
corrosion, and light-weight.
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.[53][54]
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 distinctive 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. Aluminum-based
alloys abruptly increase their strength characteristics with small additions of
scandium, as well as zirconium and hafnium.[55] A thin layer of aluminium can be
deposited onto a flat surface by physical vapor deposition or (very
infrequently) chemical vapor deposition or other chemical means[which?] to form optical
coatings and mirrors.

Aluminium compounds

Because aluminium is abundant and most of its derivatives exhibit low toxicity, the
compounds of aluminium enjoy wide and sometimes large-scale applications.

Alumina

Main article: Aluminium oxide


Aluminium oxide (Al2O3) and the associated oxy-hydroxides and trihydroxides are
produced or extracted from minerals on a large scale. The great majority of this
material is converted to metallic aluminium. In 2013 about 10% of the domestic
shipments in the United States were used for other applications.[56] A major use is as an
absorbent. For example, alumina removes water from hydrocarbons, which enables
subsequent processes that are poisoned by moisture. Aluminium oxides are common
catalysts for industrial processes, e.g. the Claus process for converting hydrogen
sulfideto sulfur in refineries and for the alkylation of amines. Many industrial
catalysts are "supported", meaning generally that an expensive catalyst
(e.g., platinum) is dispersed over a high surface area material such as alumina. Being a
very hard material (Mohs hardness 9), alumina is widely used as an abrasive and the
production of applications that exploit its inertness, e.g., in high pressure
sodiumlamps.

Sulfates

Several sulfates of aluminium find applications. Aluminium sulfate (Al2(SO4)3(H2O)18)


is produced on the annual scale of several billions of kilograms. About half of the
production is consumed inwater treatment. The next major application is in the
manufacture of paper. It is also used as a mordant, in fire extinguishers, as a food
additive (E number E173), in fireproofing, and in leather tanning. Aluminium
ammonium sulfate, which is also called ammonium alum, (NH4)Al(SO4)212H2O, is
used as a mordant and in leather tanning.[8] Aluminium potassium sulfate
([Al(K)](SO4)2)(H2O)12 is used similarly. The consumption of both alums is declining.

Chlorides

Aluminium chloride (AlCl3) is used in petroleum refining and in the production of


synthetic rubber and polymers. Although it has a similar name, aluminium
chlorohydrate has fewer and very different applications, e.g. as a hardening agent and
an antiperspirant. It is an intermediate in the production of aluminium metal.

Niche compounds

Given the scale of aluminium compounds, a small scale application could still involve
thousands of tonnes. One of the many compounds used at this intermediate level
include aluminium acetate, a saltused in solution as an astringent. Aluminium
borate (Al2O3B2O3) is used in the production of glass and ceramics. Aluminium
fluorosilicate (Al2(SiF6)3) is used in the production of synthetic gemstones, glass and
ceramic. Aluminium phosphate (AlPO4) is used in the manufacture: of glass and
ceramic, pulp and paper products, cosmetics, paints and varnishes and in making
dental cement. Aluminium hydroxide (Al(OH)3) is used as an antacid, as a mordant,
in water purification, in the manufacture of glass and ceramic and in the
waterproofing of fabrics. Lithium aluminium hydride is a powerful reducing agent
used in organic chemistry. Organoaluminiums are used as Lewis acids and
cocatalysts. For example, methylaluminoxane is a cocatalyst for Ziegler-
Natta olefin polymerization to producevinyl polymers such as polyethene.

Aluminium alloys in structural applications

Main article: Aluminium alloy

Aluminium foam

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

The statue of the Anteros inPiccadilly Circus, London, was made in 1893 and is one
of the first statues cast in aluminium.

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 alumalumine. In 1808, Humphry Davy identified
the existence of a metal base of alum, which he at first termed alumium and
later aluminum (see etymology section, below).

The metal was first produced in 1825 in an impure form by Danish physicist and
chemist Hans Christian rsted. He reacted anhydrous aluminium
chloride with potassium amalgam, yielding a lump of metal looking similar to
tin.[57] 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.[57] Whler is generally credited with isolating
aluminium (Latin alumen, alum). Further, Pierre Berthier discovered aluminium in
bauxite ore. Henri Etienne Sainte-Claire Deville improved Whler's method in 1846.
As described in his 1859 book, aluminium trichloride could be reduced by sodium,
which was more convenient and less expensive than potassium used by Whler.[58] In
the mid-1880s, aluminium metal was exceedingly difficult to produce, which made
pure aluminium more valuable than gold.[59] So celebrated was the metal that bars of
aluminium were exhibited at the Exposition Universelle of 1855.[60] Napoleon III of
France is reputed to have held a banquet where the most honored guests were given
aluminium utensils, while the others made do with gold.[61][62]

Aluminium was selected as the material to use for the 100 ounces (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 (in 1884 about $1 for 10 hours of labor;
today, a construction worker in the US working on such a project might earn $25$35
per hour and therefore around $300 in an equivalent single 10-hour day).[63] The
capstone, which was set in place on 6 December 1884 in an elaborate dedication
ceremony, was the largest single piece of aluminium cast at the time.[63]

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.[64][65][66]

Hall-Heroult process: availability of cheap aluminium metal

Charles Martin Hall of Ohio in the U.S. and Paul Hroult of France independently
developed the Hall-Hroult electrolytic process that facilitated large-scale production
of metallic aluminium. This process remains in use today.[67] In 1888, with the
financial backing of Alfred E. Hunt, the Pittsburgh Reduction Company started; today
it is 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.[68]
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.[69]

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.

Aluminium wire was once widely used for domestic electrical wiring. Owing to
corrosion-induced failures, a number of fires resulted.

Etymology
Two variants of the metal's name are in current
use, aluminium (pronunciation: /ljmnim/) and aluminum (/lumnm/)besides
the obsolete alumium. The International Union of Pure and Applied
Chemistry (IUPAC) adopted aluminium as the standard international name for the
element in 1990 but, three years later, recognized aluminum as an acceptable variant.
Hence their periodic table includes both.[70] IUPAC internal publications use either
spelling in nearly the same number.[71]

Most countries use the spelling aluminium. In the United States and Canada, the
spelling aluminum predominates.[21][72] The Canadian Oxford
Dictionary prefers aluminum, whereas the AustralianMacquarie
Dictionary prefers aluminium. In 1926, the American Chemical Society officially
decided to use aluminum in its publications; American dictionaries typically label the
spelling aluminium as "chiefly British".[73][74]

The various names all derive from its status as a base of alum. It is borrowed from Old
French; its ultimate source, alumen, in turn is a Latin word that literally means "bitter
salt".[75]

The earliest citation given in the Oxford English Dictionary for any word used as a
name for this element is alumium, which British chemist and inventor Humphry
Davy employed in 1808 for the metal he was trying to isolate electrolytically from the
mineral alumina. The citation is from the journal Philosophical Transactions of the
Royal Society of London: "Had I been so fortunate as to have obtained more certain
evidences on this subject, and to have procured the metallic substances I was in search
of, I should have proposed for them the names of silicium, alumium, zirconium, and
glucium."[76][77]

Davy settled on aluminum by the time he published his 1812 book Chemical
Philosophy: "This substance appears to contain a peculiar metal, but as yet Aluminum
has not been obtained in a perfectly free state, though alloys of it with other metalline
substances have been procured sufficiently distinct to indicate the probable nature of
alumina."[78] But the same year, an anonymous contributor to theQuarterly Review, a
British political-literary journal, in a review of Davy's book, objected
to aluminum and proposed the name aluminium, "for so we shall take the liberty of
writing the word, in preference to aluminum, which has a less classical sound."[79]

The -ium suffix conformed to the precedent set in other newly discovered elements of
the time: potassium, sodium, magnesium, calcium, and strontium (all of which Davy
isolated himself). Nevertheless,-um spellings for elements were not unknown at the
time, as for example platinum, known to Europeans since the 16th
century, molybdenum, discovered in 1778, and tantalum, discovered in 1802. The -
um suffix is consistent with the universal spelling alumina for the oxide (as opposed to
aluminia), as lanthana is the oxide of lanthanum, and magnesia, ceria, and thoria are
the oxides of magnesium,cerium, and thorium respectively.

The aluminum spelling is used in the Webster's Dictionary of 1828. In his advertising
handbill for his new electrolytic method of producing the metal in 1892, Charles
Martin Hall used the -um spelling, despite his constant use of the -ium spelling in all
the patents[67] he filed between 1886 and 1903. Hall's domination of production of the
metal ensured that aluminum became the standard English spelling in North America.

Biology
Schematic of Al absorption by human skin.[80]

There are five major Al forms absorbed by human body: the free solvated trivalent
cation (Al3+(aq)); low-molecular-weight, neutral, soluble complexes (LMW-Al0(aq)); high-
molecular-weight, neutral, soluble complexes (HMW-Al0(aq)); low-molecular-weight,
charged, soluble complexes (LMW-Al(L)n+/(aq)); nano and micro-particulates (Al(L)n(s)).
They are transported across cell membranes or cell epi-/endothelia through five major
routes: (1) paracellular; (2) transcellular; (3) active transport; (4) channels; (5)
adsorptive or receptor-mediated endocytosis.[80]

Despite its widespread occurrence in nature, aluminium has no known function in


biology. Aluminium salts are remarkably nontoxic, aluminium sulfate having
an LD50 of 6207 mg/kg (oral, mouse), which corresponds to 500 grams for an 80 kg
(180 lb) person.[8] 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.
Health concerns
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 is associated with altered function of the bloodbrain barrier.[81] 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 antiperspirants and 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 amounts greater than 40 mg/day per kg of body
mass.[82] 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,[83] and maltol has been shown to increase the accumulation of aluminium in
nervous and osseous tissue.[84] Furthermore, aluminium increases estrogen-related gene
expression in human breast cancer cells cultured in the laboratory.[85] The estrogen-like
effects of these salts have led to their classification as a metalloestrogen.

The effects of aluminium in antiperspirants have been examined over the course of
decades with little evidence of skin irritation.[8] Nonetheless, its occurrence in
antiperspirants, dyes (such as aluminiumlake), and food additives has caused
concern.[86] Although there is little evidence that normal exposure to aluminium
presents a risk to healthy adults,[87] some studies point to risks associated with
increased exposure to the metal.[86] Aluminium in food may be absorbed more than
aluminium from water.[88] It is classified as a non-carcinogen by the US Department of
Health and Human Services.[82]

In case of suspected sudden intake of a large amount of aluminium, deferoxamine


mesylate may be given to help eliminate it from the body by chelation.[89]

Alzheimer's disease

Aluminium has controversially been implicated as a factor in Alzheimer's


disease.[90] 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.[91]

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.[92]Nevertheless, some studies, such as those on the PAQUID
cohort,[93] cite aluminium exposure as a risk factor for Alzheimer's disease. Some brain
plaques have been found to contain increased levels of the metal.[94] Research in this
area has been inconclusive; aluminium accumulation may be a consequence of the
disease rather than a causal agent.[95][96] A new study, dated Feb 5 2015, links the brain
translocation of alum particles to a Trojan horse mechanism, that obeys to CCL2,
signaling the major inflammatory monocyte chemoattractant.[97]

Occupational safety

Aluminium exposure can occur through inhalation, skin contact, and eye contact.
Exposure can cause irritation of the affected area or organ. Exposure to powdered
aluminium or aluminium welding fumes can cause pulmonary fibrosis. The United
States Occupational Safety and Health Administration (OSHA) has set a permissible
exposure limit of 15 mg/m3 time weighted average (TWA) for total exposure and
5 mg/m3 TWA for respiratory exposure. The US National Institute for Occupational
Safety and Health (NIOSH) recommended exposure limit is the same for respiratory
exposure but is 10 mg/m3 for total exposure, and 5 mg/m3 for fumes and powder. Fine
aluminium powder can ignite or explode, posing another workplace hazard.[98][99]

Effect on plants
Aluminium is primary among the factors that reduce plant growth on acid soils.
Although it is generally harmless to plant growth in pH-neutral soils, the
concentration in acid soils of toxic Al3+ cationsincreases and disturbs root growth and
function.[100][101][102][103]

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.[104] This concept of
"corrected lime potential"[105] 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"[106] of soils.[107]

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.[108] This is not the case in all
plants.

Biodegradation
A Spanish scientific report from 2001 claimed that the fungus Geotrichum
candidum consumes the aluminium in compact discs.[109][110] However, other reports on
it always refer back to the 2001 Spanish report and there is no supporting original
research since that report. Better documented, the bacterium Pseudomonas
aeruginosa and the fungus Cladosporium resinae are commonly detected in aircraft
fuel tanks using kerosene-based fuels (not AV gas), and can degrade aluminium in
cultures.[111] However, this is not a matter of the bacteria or fungi directly attacking or
consuming the aluminium, but rather a result of the microbes' waste having a
corrosive nature.[112]

Silicon
From Wikipedia, the free encyclopedia
Jump to: navigation, search
This article is about the chemical element. For other uses, see Silicon
(disambiguation).
Not to be confused with the silicon-containing synthetic polymer silicone.
"Element 14" redirects here. For other uses, see Element 14 (disambiguation).

Silicon, Si 14

Spectral lines of silicon

General properties
Name, symbol silicon, Si

Appearance crystalline, reflective with bluish-tinged faces

Pronunciation /slkn/ or /slkn/


SIL--kn or SIL--kon

Silicon in the periodic table

C

Si

Ge

aluminium silicon phosphorus

Atomic number 14

Standard atomic weight (Ar) 28.085[1] (28.08428.086)[2]

Element category metalloid

Group, block group 14 (carbon group), p-block

Period period 3

Electron configuration [Ne] 3s2 3p2

per shell 2, 8, 4

Physical properties

Phase solid

Melting point 1687 K (1414 C, 2577 F)

Boiling point 3538 K (3265 C, 5909 F)


Density near r.t. 2.3290 g/cm3

when liquid, at m.p. 2.57 g/cm3

Heat of fusion 50.21 kJ/mol

Heat of vaporization 383 kJ/mol

Molar heat capacity 19.789 J/(molK)

vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 1908 2102 2339 2636 3021 3537

Atomic properties

Oxidation states 4, 3, 2, 1[3] 1, 2, 3, 4


(anamphoteric oxide)

Electronegativity Pauling scale: 1.90

Ionization energies 1st: 786.5 kJ/mol


2nd: 1577.1 kJ/mol
3rd: 3231.6 kJ/mol
(more)

Atomic radius empirical: 111 pm

Covalent radius 111 pm

Van der Waals radius 210 pm

Miscellanea

Crystal structure diamond cubic


Speed of soundthin rod 8433 m/s (at 20 C)

Thermal expansion 2.6 m/(mK) (at 25 C)

Thermal conductivity 149 W/(mK)

Electrical resistivity 2.3103 m (at 20 C)[4]

Band gap 1.12 eV (at 300 K)


Magnetic ordering diamagnetic[5]
Young's modulus 130188 GPa[6]
Shear modulus 5180 GPa[6]
Bulk modulus 97.6 GPa[6]
Poisson ratio 0.0640.28[6]
Mohs hardness 7
CAS Registry Number 7440-21-3

History
Naming after Latin 'silex' or 'silicis', meaning flint
Prediction Antoine Lavoisier (1787)
Discovery and first isolation Jns Jacob Berzelius[7][8](1823)
Named by Thomas Thomson (1817)

Most stable isotopes

Main article: Isotopes of silicon


iso NA half-life DM DE (MeV) DP
28
Si 92.23%28Si is stable with 14 neutrons
29
Si 4.67%29Si is stable with 15 neutrons
30
Si 3.1%30Si is stable with 16 neutrons
32
Si trace 153 y 13.020 32
P

references
Silicon is a chemical element with symbol Si and atomic number 14. It is
a tetravalent metalloid, 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
in dusts, sands, planetoids, and planets as various forms of silicon dioxide (silica)
or silicates. Over 90% of the Earth's crust is composed ofsilicate minerals, making
silicon the second most abundant element in the Earth's crust (about 28% by mass)
after oxygen.[9]

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. Silicate goes into Portland
cement for mortar and stucco, and when combined with silica sand andgravel, to
make concrete. Silicates are also in whiteware ceramics such as porcelain, and in
traditional quartz-based soda-lime glass and many other specialty glasses. More
modern silicon compounds such as silicon carbide form abrasives and high-strength
ceramics. Silicon is the basis of the widely used synthetic 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, aluminium-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.[10] However, various sea sponges as well as microorganisms
like diatoms and radiolaria secrete skeletal structures made of silica. Silica is often
deposited in plant tissues, such as in the bark and wood of Chrysobalanaceae and the
silica cells and silicified trichomes of Cannabis sativa, horsetails and many grasses.[11]

Contents
[hide]
1 Characteristics
o 1.1 Physical
o 1.2 Chemical
o 1.3 Isotopes
2 History
3 Occurrence
4 Production
o 4.1 Alloys
o 4.2 Metallurgical grade
o 4.3 Polysilicon
4.3.1 Siemens process and alternatives
o 4.4 Electronic grade
4.4.1 Early purification techniques
5 Compounds
6 Applications
o 6.1 Compounds
o 6.2 Alloys
o 6.3 Electronics
7 Biological role
8 See also
9 References
10 Bibliography
11 External links

Characteristics
Physical

Silicon crystallizes in a diamond cubic crystal structure


Further information: Monocrystalline silicon

Silicon is a solid at room temperature, with relatively high melting and boiling points
of 1414 and 3265 C, respectively. Like water, it has a greaterdensity in a liquid state
than in a solid state, and so, like water but unlike most substances, it does not contract
when it freezes, but expands. With a relatively high thermal conductivity of 149
Wm1K1, silicon conducts heat well.

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 ).[12]

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 3psubshell 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 the piezoresistive effect.[13]

Chemical

Silicon powder

Silicon is a metalloid, readily either donating or sharing its four outer electrons and it
typically forms four bonds. Like carbon, its four bonding electrons give it
opportunities to combine with many other elements or compounds to form a wide
range of compounds. 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 hyper-reactive combinations of nitric acid and hydrofluoric acid) have no
known effect on it.

Isotopes

Main article: isotopes of silicon


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).[14] Out of these, only silicon-29 is of use in NMR and EPR
spectroscopy.[15] Twenty radioisotopes 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.[14] 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.[14] Silicon does not have any known nuclear isomers.[14]

The isotopes of silicon range in mass number from 22 to 44.[14] 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.[14] 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.[14]

History
Attention was first drawn to silica as the possible oxide of a fundamental chemical
element by Antoine Lavoisier, in 1787.[16] After an attempt to isolate silicon in 1808,
Sir Humphry Davy proposed the name "silicium" for silicon, from the
Latin silex, silicis for flint, and adding the "-ium" ending because he believed it was a
metal.[17] In 1811, Gay-Lussac and Thnard are thought to have prepared
impure amorphous 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.[18] Silicon was given its present name in 1817 by Scottish
chemistThomas Thomson. He retained part of Davy's name but added "-on" because
he believed that silicon was a nonmetal similar to boron and carbon.[19] 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.[20] As a result, he is usually given credit
for the element's discovery.[21][22]

Silicon in its more common crystalline form was not prepared until 31 years later,
by Deville.[23][24] By electrolyzing impure sodium-aluminium chloride containing
approximately 10% silicon, he was able to obtain a slightly impure allotrope of silicon
in 1854.[25] 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, bears the element's name since it is the base for a number of
computer technology-related industries. 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 Slopes in Salt Lake City,
Utah, Silicon Saxony in Germany, Silicon Valley in India, Silicon Border in Mexicali,
Mexico, Silicon Fen inCambridge, England, Silicon Roundabout in London, Silicon
Glen in Scotland, and Silicon Gorge in Bristol, England.

Occurrence

Quartz crystal cluster from Tibet. The naturally occurring mineral is a network solid
with the formula SiO2.
See also: Silicate minerals

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. [26] Silicon
is usually found in the form of complex silicate minerals, and less often as silicon
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


metalsaccount 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 readily combine chemically, forming network solids of silicon and
oxygen in compounds of very low volatility. Since oxygen and silicon were the most
common non-gaseous and non-metallic elements in the debris from supernova 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 (aluminium,
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 metallic iron and
nickel sank to the planet's core, leaving a thick mantle between core and crust,
consisting mostly of magnesium and iron silicates. These are thought to be
mostly silicate perovskites, followed in abundance by the magnesium/iron
oxideferropericlase.[27]

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. In the crust, silica occurs
in minerals consisting of very pure silicon dioxide in different crystalline
forms, quartz, agate amethyst, rock crystal, chalcedony, flint, jasper, and opal. 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 glass obsidian. 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.

Production
Alloys

Ferrosilicon alloy

Ferrosilicon, an iron-silicon alloy that contains varying ratios of elemental silicon and
iron, accounts for about 80% of the world's production of elemental silicon, with
China, the leading supplier of elemental silicon, providing 4.6 million tonnes (or 2/3
of the world output) of silicon, most of which is in the form of ferrosilicon. It is
followed by Russia (610,000 t), Norway (330,000 t), Brazil (240,000 t) and the United
States (170,000 t).[28] Ferrosilicon is primarily used by the steel industry (see below).
Aluminium-silicon alloys (called silumin alloys) are heavily used in the aluminium
alloy casting industry, where silicon is the single most important additive to
aluminium to improve its casting properties. Since cast aluminium is widely used in
the automobile industry, this use of silicon is thus the single largest industrial use
(about 55% of the total) of "metallurgical grade" pure silicon (as this purified silicon
is added to pure aluminium, whereas ferrosilicon is never purified before being added
to steel).[29]

Metallurgical grade

Elemental silicon not alloyed with significant quantities of other elements, and usually
> 95%, is often referred to loosely as silicon metal. It makes up about 20% of the
world total elemental silicon production, with less than 1 to 2% of total elemental
silicon (510% of metallurgical grade silicon) ever purified to higher grades for use in
electronics. Metallurgical grade silicon is commercially prepared by the reaction of
high-purity silica with wood, charcoal, and coal in an electric arc furnace using
carbon electrodes. At temperatures over 1,900 C (3,450 F), the carbon in the
aforementioned materials and the silicon undergo the chemical reaction SiO2 + 2 C
Si + 2 CO. Liquid silicon collects in the bottom of the furnace, which is then drained
and cooled. The silicon produced in this manner is called metallurgical grade
silicon and is at least 98% pure. Using this method, silicon carbide (SiC) may also
form from an excess of carbon in one or both of the following ways: SiO 2 + C SiO
+ CO or SiO + 2 C SiC + CO. However, provided the concentration of SiO2 is kept
high, the silicon carbide can be eliminated by the chemical reaction 2 SiC + SiO2 3
Si + 2 CO.

As noted above, metallurgical grade silicon "metal" has its primary use in the
aluminium casting industry to make aluminium-silicon alloy parts. The remainder
(about 45%) is used by the chemical industry, where it is primarily employed to
make fumed silica, with the rest used in production of other fine chemicals such
as silanes and some types of silicones.[30]

As of September 2008, metallurgical grade silicon costs about US$1.45 per pound
($3.20/kg),[31] up from $0.77 per pound ($1.70/kg) in 2005.[32]

A polycrystalline siliconrod made by the Siemens process


Polysilicon

Main article: Polycrystalline silicon

Today's purification processes involve the conversion of silicon into volatile liquids,
such as trichlorosilane (HSiCl3) and silicon tetrachloride (SiCl4) or into the
gaseous silane (SiH4). These compounds are then separated by a distillation and
transformed into high-purity silicon, either by a redox reaction or by chemical
decomposition at high temperatures.

In the late 1950s, the American chemical company DuPont patented a method for the
production of 99.99% pure silicon, using the metal zinc as a reductant to transform
redistilled silicon tetrachloride into high-purity silicon by a vapor phase reaction at
900 C. This technique, however, was plagued with practical problems, as the
byproduct zinc chloride (ZnCl2) solidified and clogged lines, and was eventually
abandoned in favor of more sophisticated processes.[33]

Schematic diagram of the traditional Siemens and theFluidized bed


reactor purification process.

Siemens process and alternatives

The best known technique is the so-called Siemens process. This technique does not
require a reductant such as zinc, as it grows high-purity silicon crystallites directly on
the surface of (pre-existing) pure silicon seed rods by a chemical decomposition that
takes place when the gasous trichlorosilane is blown over the rod's surface at 1150 C.
A common name for this type of technique is chemical vapor deposition (CVD) and
produces high-purity polycrystalline silicon, also known as polysilicon. While the
conventional Siemens process produces electronic grade polysilicon at typically 9N
11N purities, that is, it contains impurity levels of less than one part per billion (ppb),
the modified Siemens process is a dedicated process-route for the production of solar
grade silicon (SoG-Si) with purities of 6N (99.9999%) and less energy demand.[34][35][36]
A more recent alternative for the production of polysilicon is the fluidized bed
reactor (FBR) manufacturing technology. Compared to the traditional Siemens
process, FBR features a number of advantages that lead to cheaper polysilicon
demanded by the fast-growing photovoltaic industry. Contrary to Siemens' batch
process, FBR runs continuously, wasting fewer resources and requires less setup and
downtime. It uses about 10 percent of the electricity consumed by a conventional rod
reactor in the established Siemens process, as it does not waste energy by placing
heated gas and silicon in contact with cold surfaces. In the FBR, silane (SiH4) is
injected into the reactor from below and forms a fluidized bed together with the
silicon seed particles that are fed from above. The gaseous silane then decomposes
and deposits silicon on the seed particles. When the particles have grown to larger
granules, they eventually sink to the bottom of the reactor where they are continuously
withdrawn from the process.

The FBR manufacturing technology outputs polysilicon at 6N to 9N, a purity still


higher than the 5N to 6N of upgraded metallurgical silicon (UMG-Si), a third
technology used by the photovoltaic industry, that dispenses altogether with chemical
purification, using metallurgical techniques instead. Currently most silicon for the
photovoltaic market is produced by the Siemens process and only about 10 percent by
the FBR technology, while UMG-Si accounts for about 2 percent. By 2020, however,
IHS Technology predicts that market shares for FBR technology and UMG-Si will
grow to 16.7 and 5.4 percent, respectively.[37]

The company REC is one of the leading producers of silane and polysilicon using
FBR technology. The three-step chemical reaction involves (last step occurs inside the
FB-reactor): (1.) 3 SiCl4 + Si + 2 H2 4 HSiCl3, followed by (2.) 4 HSiCl3
3 SiCl4 + SiH4, and (3.) SiH4 Si + 2 H2.[38] Other precursors such
as tribromosilane had been used by other companies as well.

Electronic grade
Monocrystalline siliconingot grown by theCzochralski process
Main article: Monocrystalline silicon

The use of silicon in semiconductor devices demands a much greater purity than
afforded by metallurgical grade silicon. Very pure silicon (>99.9%) can be extracted
directly from solid silica or other silicon compounds by molten salt
electrolysis.[39][40] This method, known as early as 1854[41] (see also FFC Cambridge
process), has the potential to directly produce solar-grade silicon without anycarbon
dioxide emission at much lower energy consumption.

Solar grade silicon cannot be used for microelectronics. To properly control the
quantum mechanical properties, the purity of the silicon must be very high. Bulk
silicon wafers used at the beginning of the integrated circuit making process must first
be refined to a purity of 99.9999999% often referred to as "9N" for "9 nines", a
process which requires repeated applications of refining technology.

The majority of silicon crystals grown for device production are produced by
the Czochralski process, (Cz-Si) It was the cheapest method available. However,
single crystals grown by the Czochralski process contain impurities because
the crucible containing the melt often dissolves. Historically, a number of methods
have been used to produce ultra-high-purity silicon.
Early purification techniques

Early silicon purification techniques were based on the fact that if silicon is melted
and re-solidified, the last parts of the mass to solidify contain most of the impurities.
The earliest method of silicon purification, first described in 1919 and used on a
limited basis to make radar components during World War II, involved crushing
metallurgical grade silicon and then partially dissolving the silicon powder in an acid.
When crushed, the silicon cracked so that the weaker impurity-rich regions were on
the outside of the resulting grains of silicon. As a result, the impurity-rich silicon was
the first to be dissolved when treated with acid, leaving behind a more pure product.

In zone melting, also called zone refining, the first silicon purification method to be
widely used industrially, rods of metallurgical grade silicon are heated to melt at one
end. Then, the heater is slowly moved down the length of the rod, keeping a small
length of the rod molten as the silicon cools and re-solidifies behind it. Since most
impurities tend to remain in the molten region rather than re-solidify, when the
process is complete, most of the impurities in the rod will have been moved into the
end that was the last to be melted. This end is then cut off and discarded, and the
process repeated if a still higher purity is desired.[42]

Compounds
See also: Category:Silicon compounds.

PDMS a silicone compound

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.[43]
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.[44] There is a range of catenated silicon hydrides that form a
homologous series of compounds, Si
nH
2n+2 where n = 28 (analogous to thealkanes). These are all readily hydrolyzed
and are thermally unstable, particularly the heavier members.[45][46]
Disilenes contain a silicon-silicon double bond (analogous to the alkenes) and
are generally highly reactive requiring large substituent groups to stabilize
them.[47] A disilyne 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.[48]
Tetrahalides, SiX4, are formed with all the halogens.[49] Silicon tetrachloride, for
example, reacts with water, unlike its carbon analogue, carbon
tetrachloride.[50] 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, (SiF
2)
n.[46]
Silicon dioxide (silica) is a high melting solid with a number of crystal forms;
the most familiar of which is the mineral quartz. In crystalline quartz each
silicon atom is surrounded by four oxygen atoms that bridge to other silicon
atoms to form a three dimensional lattice (see below for the vitreous or glass
form of pure silica). [50] Silica is soluble in water at high temperatures forming a
range of compounds called monosilicic acid, Si(OH)4.[51]
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.[51]
Silica can be fused directly into glass form, as so-called fused quartz, which
contains no crystalline structure. With oxides of other elements, the high
temperature reaction of silicon dioxide can give a wide range of mixed glasses
and glass-like network solids with various properties.[52] 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).[53]
Silicon forms a nitride, Si3N4 which is a ceramic.[54] Silatranes, a group of
tricyclic compounds containing five-coordinate silicon, may have physiological
properties.[55]
Many transition metal complexes containing a metal-silicon bond are now
known, which include complexes containing SiH
nX
3n ligands, SiX3 ligands, and Si(OR)3 ligands.[55]
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 and elastomers.[56]
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 centralchirality exists. Long chain polymers
containing a silicon backbone are known, such as polydimethysilylene (SiMe
2)
n.[57] Polycarbosilane, [(SiMe
2)
2CH
2]
n with a backbone containing a repeating -Si-Si-C unit, is a precursor in the
production of silicon carbide fibers.[57]

Applications
Compounds

Building materials. 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, which are
compounds of silicon and oxygen, often with metallic ions when negatively charged
silicate anions require cations to balance the charge. 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). Silicates are used in making Portland
cement (made mostly of calcium silicates) which is used in building mortar and
modern 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. [58]

Ceramics and glass. Silica is used to make fire brick, a type of ceramic. Silicate
minerals are also in whiteware ceramics, an important class of products usually
containing various types of fired clayminerals (natural aluminium phyllosilicates). An
example is porcelain which is based on the silicate mineral kaolinite.
Traditional glass (silica-based soda-lime glass) also functions in many of the same
ways, and is also used for windows and containers. In addition, specialty silica
based glass fibers are used for optical fiber, as well as to produce fiberglass for
structural support and glass wool for thermal insulation.

Artificial silicon compounds. Very occasional elemental silicon is found in nature,


and also naturally-occurring compounds of silicon and carbon (silicon carbide) or
nitrogen (silicon nitride) are found in stardust samples or meteorites in presolar grains,
but the oxidizing conditions of the inner planets of the solar system make planetary
silicon compounds found there mostly silicates and silica. Free silicon, or compounds
of silicon in which the element is covalently attached to hydrogen, boron, or elements
other than oxygen, are mostly artificially produced. They are described below.

Silicon compounds of more modern origin function as high-technology abrasives and


new high-strength ceramics based upon silicon carbide. Silicon is a component of
some 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 silicon-oxygen 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 temperaturegreases and waxes, and caulking compounds. Silicone is also
sometimes used in breast implants, contact
lenses, explosives and pyrotechnics.[59] Silly Putty was originally made by adding boric
acid tosilicone oil.[60]

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 grossly impure, it accounts for 80% of the world's use of
free silicon. Silicon is an important constituent of electrical steel, modifying
its resistivity and ferromagnetic properties.

The properties of silicon can be used to modify alloys with metals other than iron.
"Metallurgical grade" silicon is silicon of 9599% purity. About 55% of the world
consumption of metallurgical purity silicon goes for production of aluminium-silicon
alloys (silumin alloys) for aluminium part casts, mainly for use in the automotive
industry. Silicon's importance in aluminium casting is that a significantly high amount
(12%) of silicon in aluminium 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 aluminium.[29][30]

Electronics

Main article: Semiconductor device fabrication

Silicon wafer with mirror finish

Most elemental silicon produced remains as ferrosilicon alloy, and 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.[30] 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 photovoltaic applications. 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 dopedwith 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 for transistors, solar cells, semiconductor
detectors and other semiconductor devices, which are used in the computer industry
and other technical applications. For example, in silicon 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.[61]

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.[30]

Biological role
Silica skeletons of radiolaria in false color.

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.[62][63][64] The possible
biological potential of silicon as bioavailable orthosilicic acid and the potential
beneficial effects on human health has been reviewed.[65]

Silicon is needed for synthesis of elastin and collagen;[not in citation given] the aorta contains the
highest quantity of elastin and silicon.[66] 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)."[67][68] Silicon has been shown in university
and field studies to improve plant cell wall strength and structural integrity,[69] improve
drought and frost resistance, decrease lodging potential and boost the plant's natural
pest and disease fighting systems.[70] 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.[69]

Phosphorus
From Wikipedia, the free encyclopedia
Jump to: navigation, search
This article is about the chemical element. For other uses, see Phosphorus
(disambiguation).

Phosphorus, P 15

waxy white (yellow cut), red (granules centre left, chunk centre right), and
violet phosphorus

General properties

Name, symbol phosphorus, P

Appearance colourless, waxy white, yellow, scarlet,


red, violet, black

Pronunciation /fsfrs/
FOS-fr-s

Phosphorus in the periodic table

N

P

As

silicon phosphorus sulfur

Atomic number 15

Standard atomic weight () (Ar) 30.973761998(5)[1]

Element category polyatomic nonmetal, sometimes


considered ametalloid

Group, block group 15 (pnictogens), p-block

Period period 3

Electron configuration [Ne] 3s2 3p3

per shell 2, 8, 5

Physical properties
Phase solid

Density near r.t. white: 1.823 gcm3


red: 2.22.34 gcm3
violet: 2.36 gcm3
black: 2.69 g/cm3

Heat of fusion white: 0.66 kJ/mol

Heat of vapourisation white: 51.9 kJ/mol

Molar heat capacity white: 23.824 J/(molK)

vapour pressure (white)


P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 279 307 342 388 453 549

vapour pressure (red, b.p. 431 C)


P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 455 489 529 576 635 704

Atomic properties

Oxidation states 5, 4, 3, 2,[2] 1,[3] 1, 2, 3 (a


mildly acidic oxide)

Electronegativity Pauling scale: 2.19

Ionisation energies 1st: 1011.8 kJ/mol


2nd: 1907 kJ/mol
3rd: 2914.1 kJ/mol
(more)

Covalent radius 1073 pm

Van der Waals radius 180 pm


Miscellanea

Crystal structure body-centered cubic (bcc)

Thermal conductivity white: 0.236 W/(mK)


black: 12.1 W/(mK)

Magnetic ordering white, red, violet, black:diamagnetic[4]

Bulk modulus white: 5 GPa


red: 11 GPa

CAS Registry Number white: 12185-10-3


red: 7723-14-0

History

Discovery Hennig Brand (1669)

Recognized as an element by Antoine Lavoisier[5] (1777)

Most stable isotopes

Main article: Isotopes of phosphorus

iso NA half-life DM DE (MeV) DP


31
P 100%31P is stable with 16 neutrons
32
P syn 14.28 d 1.709 32
S
33
P syn 25.3 d
0.249 33
S

references

Phosphorus is a chemical element with symbol P and atomic number 15. As an


element, phosphorus exists in two major formswhite phosphorus andred
phosphorusbut due to its high reactivity, phosphorus is never found as a free
element on Earth. Instead phosphorus-containing minerals are almost always present
in their maximally oxidised state, as inorganic phosphate rocks.

The first form of elemental phosphorus to be produced (white phosphorus, in 1669)


emits a faint glow upon exposure to oxygen hence its name given from Greek
mythology, meaning "light-bearer" (Latin Lucifer), referring to the
"Morning Star", the planet Venus (or Mercury). The term "phosphorescence",
meaning glow after illumination, originally derives from this property of phosphorus,
although this word has since been used for a different physical process that produces a
glow. The glow of phosphorus itself originates from oxidation of the white (but not
red) phosphorus a process now termed chemiluminescence. Together with nitrogen,
arsenic, and antimony, phosphorus is classified as a pnictogen.

Phosphorus is essential for life. Phosphates (compounds containing the phosphate ion,
PO43) are a component of DNA, RNA, ATP, and also thephospholipids, which form
all cell membranes. Demonstrating the link between phosphorus and life, elemental
phosphorus was first isolated from human urine, and bone ash was an important early
phosphate source. Phosphate minerals are fossils.[clarification needed] Low phosphate levels are
an important limit to growth in some aquatic systems. In a commercial sense, the vast
majority of phosphorus compounds are consumed as fertilisers. Phosphate is needed
to replace the phosphorus that plants remove from the soil, and its annual demand is
rising nearly twice as fast as the growth of the human population.[6] Other applications
include the role of organophosphorus compounds in detergents, pesticides, and nerve
agents.[7] Of all the pnictogens, phosphorus is the most abundant in the Earth's crust,
composing 9.9102% of said crust.[8]

Contents
[hide]

1 Characteristics
o 1.1 Physical
1.1.1 White phosphorus and related molecular forms
1.1.2 Red phosphorus
1.1.3 Violet phosphorus
1.1.4 Black phosphorus
o 1.2 Isotopes
2 Occurrence
o 2.1 Minerals (phosphate rock)
o 2.2 Urine
o 2.3 Other organic sources
3 Production
o 3.1 Elemental phosphorus
4 Compounds
o 4.1 Oxoacids of phosphorus
o 4.2 Phosphorus(V) compounds
4.2.1 Oxides
o 4.3 Nitrides
o 4.4 Sulfides
o 4.5 Phosphorus(III) compounds
o 4.6 Organophosphorus compounds
o 4.7 Phosphorus(I) and phosphorus(II) compounds
o 4.8 Phosphines
o 4.9 Phosphides
5 Spelling and etymology
6 History and discovery
o 6.1 Glow
7 Applications
o 7.1 Fertiliser
o 7.2 Organophosphorus compounds
o 7.3 Metallurgical aspects
o 7.4 Matches
o 7.5 Water softening
o 7.6 Niche applications
8 Biological role
o 8.1 Bone and teeth enamel
o 8.2 Phosphorus deficiency
o 8.3 Food sources
9 Precautions
o 9.1 US DEA List I status
10 See also
11 Notes
12 References
o 12.1 Sources
13 External links

Characteristics
Main article: Allotropes of phosphorus

Physical
P4 molecule

Phosphorus exists as several forms (allotropes) that exhibit strikingly different


properties.[9] The two most common allotropes are white phosphorusand red
phosphorus. Another form, scarlet phosphorus, is obtained by allowing a solution of
white phosphorus in carbon disulfide to evaporate insunlight. Black phosphorus is
obtained by heating white phosphorus under high pressures (about 12,000 standard
atmospheres or 1.2 gigapascals). In appearance, properties, and structure, it
resembles graphite, being black and flaky, a conductor of electricity, and has puckered
sheets of linked atoms. Another allotrope is diphosphorus; it contains a
phosphorus dimer as a structural unit and is highly reactive.[10]

White phosphorus and related molecular forms

White phosphorus

White phosphorus exposed to air glows in the darkness

The most important form of elemental phosphorus from the perspective of


applications and the chemical literature is white phosphorus, often abbreviated as WP.
It consists of tetrahedral P
4 molecules, in which each atom is bound to the other three atoms by a single bond.
This P
4 tetrahedron is also present in liquid and gaseous phosphorus up to the temperature of
800 C (1,470 F) when it starts decomposing to P
2 molecules.[11] Solid white exists in two forms. At low-temperatures, the form is
stable. At high-temperatures the form is predominant. These forms differ in terms of
the relative orientations of the constituent P4 tetrahedra.

White phosphorus is the least stable, the most reactive, the most volatile, the
least dense, and the most toxic of the allotropes. White phosphorus gradually changes
to red phosphorus. This transformation is accelerated by light and heat, and samples
of white phosphorus almost always contain some red phosphorus and accordingly
appear yellow. For this reason, white phosphorus that is aged or otherwise impure
(e.g. weapons-grade not lab-grade WP) is also called yellow phosphorus. White
phosphorus glows in the dark (when exposed to oxygen) with a very faint tinge of
green and blue, is highlyflammable and pyrophoric (self-igniting) upon contact with
air and is toxic (causing severe liver damage on ingestion). Owing to its
pyrophoricity, white phosphorus is used as an additive in napalm. The odour of
combustion of this form has a characteristic garlic smell, and samples are commonly
coated with white "(di)phosphorus pentoxide", which consists of P
4O
10 tetrahedra with oxygen inserted between the phosphorus atoms and at their vertices.
White phosphorus is insoluble in water but soluble in carbon disulfide.[12]

Thermolysis (cracking) of P4 at 1100 kelvin) gives diphosphorus, P2. This species is


not stable as a solid or liquid. The dimeric unit contains a triple bond and is analogous
to N2. It can also be generated as a transient intermediate in solution by thermolysis of
organophosphorus precursor reagents.[13] At still higher temperatures, P2 dissociates
into atomic P.

Although the term phosphorescence is derived from phosphorus, the reaction that
gives phosphorus its glow is properly called chemiluminescence (glowing due to a
cold chemical reaction), not phosphorescence (re-emitting light that previously fell
onto a substance and excited it).

Red phosphorus

Crystal structure of red phosphorus


Red Phosphorus

Red phosphorus is polymeric in structure. It can be viewed as a derivative of


P4 wherein one P-P bond is broken, and one additional bond is formed with the
neighbouring tetrahedron resulting in a chain-like structure. Red phosphorus may be
formed by heating white phosphorus to 250 C (482 F) or by exposing white
phosphorus to sunlight.[14] Phosphorus after this treatment is amorphous. Upon further
heating, this material crystallises. In this sense, red phosphorus is not an allotrope, but
rather an intermediate phase between the white and violet phosphorus, and most of its
properties have a range of values. For example, freshly prepared, bright red
phosphorus is highly reactive and ignites at about 300 C (572 F),[15] though it is still
more stable than white phosphorus, which ignites at about 30 C (86 F).[16] After
prolonged heating or storage, the color darkens (see infobox images); the resulting
product is more stable and does not spontaneously ignite in air.[17]

Violet phosphorus

Violet phosphorus is a form of phosphorus that can be produced by day-long


annealing of red phosphorus above 550 C. In 1865, Hittorf discovered that when
phosphorus was recrystallized from moltenlead, a red/purple form is obtained.
Therefore, this form is sometimes known as "Hittorf's phosphorus" (or violet or -
metallic phosphorus).[10]

Black phosphorus

Crystal structure of black phosphorus


Black phosphorus is the least reactive allotrope and the thermodynamically stable
form below 550 C (1,022 F). It is also known as -metallic phosphorus and has a
structure somewhat resembling that of graphite.[18][19] High pressures are usually
required to produce black phosphorus, but it can also be produced at ambient
conditions using metal salts as catalysts.[20]

Properties of some allotropes of phosphorus[9][10]


Form white() white() violet black
Symmetry Body-centred cubic Triclinic Monoclinic Orthorhombic
Pearson symbol aP24 mP84 oS8
Space group I43m P1 No.2 P2/c No.13 Cmca No.64
Density (g/cm3) 1.828 1.88 2.36 2.69
Bandgap (eV) 2.1 1.5 0.34
Refractive index 1.8244 2.6 2.4

Isotopes

Main article: Isotopes of phosphorus

Twenty-three isotopes of phosphorus are known,[21] including all possibilities from 24


P up to 46
P. Only 31
P is stable and is therefore present at 100% abundance. The half-integer nuclear
spin and high abundance of 31P make phosphorus-31 NMR spectroscopy a very useful
analytical tool in studies of phosphorus-containing samples.

Two radioactive isotopes of phosphorus have half lives suitable for biological
scientific experiments. These are:

32
P, a beta-emitter (1.71 MeV) with a half-life of 14.3 days, which is used
routinely in life-science laboratories, primarily to produce radiolabeled DNA
and RNA probes, e.g. for use in Northern blots or Southern blots. Because the
high energy beta particles produced penetrate skin and corneas, and because
any 32
P ingested, inhaled, or absorbed is readily incorporated into bone and nucleic
acids, Occupational Safety and Health Administration in the United States, and
similar institutions in other developed countries require that a lab coat,
disposable gloves and safety glasses or goggles be worn when working with 32
P, and that working directly over an open container be avoided in order to
protect the eyes. Monitoring personal, clothing, and surface contamination is
also required. In addition, due to the high energy of the beta
particles, shielding this radiation with the normally used dense materials
(e.g. lead), gives rise to secondary emission of X-
rays viaBremsstrahlung (braking radiation). Therefore, shielding must be
accomplished with low density materials, e.g. Plexiglas (Lucite), other plastics,
water, or (when transparency is not required), even wood.[22]
33
P, a beta-emitter (0.25 MeV) with a half-life of 25.4 days. It is used in life-
science laboratories in applications in which lower energy beta emissions are
advantageous such as DNA sequencing.

Occurrence
See also: Category:Phosphate minerals.

Minerals (phosphate rock)

Mining of phosphate rock inNauru in the Pacific Ocean

Phosphorus is not found free in nature, but it is widely distributed in many minerals,
mainly phosphates. Inorganic phosphate rock, which is partially made of apatite (an
impure tri-calcium phosphatemineral), is today the chief commercial source of this
element. According to the US Geological Survey (USGS), about 50 percent of the
global phosphorus reserves are in the Arab nations.[23] Large deposits of apatite are
located in China, Russia, Morocco,[6] Florida, Idaho, Tennessee, Utah, and
elsewhere.[24] Albright and Wilson in the UK and their Niagara Falls plant, for
instance, were using phosphate rock in the 1890s and 1900s from Tennessee, Florida,
and the les du Conntable (guano island sources of phosphate); by 1950 they were
using phosphate rock mainly from Tennessee and North Africa.[25] In the early 1990s
Albright and Wilson's purified wet phosphoric acid business was being adversely
affected by phosphate rock sales by China and the entry of their long-standing
Moroccan phosphate suppliers into the purified wet phosphoric acid business.[26]
Guano mining in the Central Chincha Islands, ca. 1860.

In 2012, the USGS estimated 71 billion tons of world reserves, where reserve figures
refer to the amount assumed recoverable at current market prices; 0.19 billion tons
were mined in 2011.[27] Critical to contemporary agriculture, its annual demand is
rising nearly twice as fast as the growth of the human population.[6]

Recent reports suggest that production of phosphorus may have peaked, leading to the
possibility of global shortages by 2040.[28] In 2007, at the rate of consumption, the
supply of phosphorus was estimated to run out in 345 years.[29] However, some
scientists now believe that a "peak phosphorus" will occur in 30 years and that "At
current rates, reserves will be depleted in the next 50 to 100 years."[30] Cofounder
of Boston-based investment firm and environmental foundation Jeremy
Grantham wrote in Nature in November 2012, that consumption of the element "must
be drastically reduced in the next 20-40 years or we will begin to
starve."[6][31] According to N.N. Greenwood and A. Earnshaw, authors of the
textbook, Chemistry of the Elements, however, phosphorus comprises about 0.1% by
mass of the average rock, and consequently the Earth's supply is vast, although
dilute.[12]

Urine

Main article: Reuse of excreta

Urine contains most (94% according to Wolgast[32]) of the NPK nutrients excreted by
the human body. The more general limitations to using urine as fertilizer depend
mainly on the potential for buildup of excess nitrogen (due to the high ratio of that
macronutrient),[33] and inorganic salts such as sodium chloride, which are also part of
the wastes excreted by the renal system. The degree to which these factors impact the
effectiveness depends on the term of use, salinity tolerance of the plant, soil
composition, addition of other fertilizing compounds, and quantity of rainfall or other
irrigation.
Urine typically contributes 70% of the nitrogen and more than half the phosphorus
and potassium found in urban waste water flows, while making up less than 1% of the
overall volume. Thus far, source separation, or urine diversion and on-site treatment
has been implemented in South Africa, China, and Sweden among other countries
with the Bill and Melinda Gates Foundation provided some of the funding
implementations.[34]

"Urine management" is a relatively new way to view closing the cycle of agricultural
nutrient flows and reducing sewage treatment costs and ecological consequences such
as eutrophication resulting from the influx of nutrient rich effluent into aquatic or
marine ecosystems.[35] Proponents of urine as a natural source of agricultural fertilizer
claim the risks to be negligible or acceptable.[36]

Other organic sources

Historically-important but limited commercial sources were organic, such as bone ash
and (in the latter 19th century) guano.

Production
Main article: Phosphoric acid

The majority of phosphorus-containing compounds are produced for use as fertilisers.


For this purpose, phosphate-containing minerals are converted to phosphoric acid.
Two distinct routes are employed, the main one being treatment of phosphate minerals
with sulfuric acid. The other process utilises white phosphorus, which may be
produced by reaction and distillation from very low grade phosphate sources. The
white phosphorus is then oxidised to phosphoric acid and subsequently neutralised
with base to give phosphate salts. Phosphoric acid obtained via white phosphorus is
relatively pure and is the main source of phosphates used in detergents and other non-
fertiliser applications.

Elemental phosphorus

Presently, about 1,000,000 short tons (910,000 t) of elemental phosphorus is produced


annually. Calcium phosphate (phosphate rock), mostly mined in Florida and North
Africa, can be heated to 1,2001,500 C with sand, which is mostly SiO
2, and coke (impure carbon) to produce vaporized P
4. The product is subsequently condensed into a white powder under water to prevent
oxidation by air. Even under water, white phosphorus is slowly converted to the more
stable red phosphorus allotrope. The chemical equation for this process when starting
with fluoroapatite, a common phosphate mineral, is:
4 Ca5(PO4)3F + 18 SiO2 + 30 C 3 P4 + 30 CO + 18 CaSiO3 + 2 CaF2

Side products from this production include ferrophosphorus, a crude form of Fe2P,
resulting from iron impurities in the mineral precursors. The silicate slag is a useful
construction material. The fluoride is sometimes recovered for use in water
fluoridation. More problematic is a "mud" containing significant amounts of white
phosphorus. Production of white phosphorus is conducted in large facilities in part
because it is energy intensive. The white phosphorus is transported in molten form.
Some major accidents have occurred during transportation, train derailments
at Brownston, Nebraska andMiamisburg, Ohio led to large fires. The worst incident in
recent times was an environmental one in 1968 when the sea became contaminated
due to spillages and/or inadequately treated sewage from a white phosphorus plant
at Placentia Bay, Newfoundland.[37]

Another process by which elemental phosphorus is extracted includes applying at high


temperatures (1500 C):[38]

2 Ca3(PO4)2 + 6 SiO2 + 10 C 6 CaSiO3 + 10 CO + P4

Historically, before technology allowed mineral-based extractions, white phosphorus


was isolated on an industrial scale from bone ash.[39] In this scheme the tricalcium
phosphate in bone ash is converted to monocalcium phosphate with sulfuric acid:

Ca3(PO4)2 + 2 H2SO4 Ca(H2PO4)2 + 2 CaSO4

Monocalcium phosphate is then dehydrated to the corresponding metaphosphate:

Ca(H2PO4)2 Ca(PO3)2 + 2 H2O

Calcium metaphosphate yields, when ignited to a white heat with charcoal, two-thirds
of its weight of white phosphorus while one-third of the phosphorus remains in the
residue as calcium orthophosphate:

3 Ca(PO3)2 + 10 C Ca3(PO4)2 + 10 CO + P4

Compounds
See also: Category:Phosphorus compounds.

Oxoacids of phosphorus
Phosphorous oxoacids are extensive, often commercially important, and sometimes
structurally complicated. They all have acidic protons bound to oxygen atoms, some
have nonacidic protons that are bonded directly to phosphorus and some contain
phosphorus - phosphorus bonds.[12] Although many oxoacids of phosphorus are
formed, only nine are important, and three of them, hypophosphorous
acid, phosphorous acid, and phosphoric acid, are particularly important ones.

Oxidation state Formula Name Acidic protons Compounds


+1 HH2PO2 hypophosphorous acid 1 acid, salts
+3 H2HPO3 phosphorous acid 2 acid, salts
+3 HPO2 metaphosphorous acid 1 salts
+3 H3PO3 (ortho)phosphorous acid 3 acid, salts
+4 H4P2O6 hypophosphoric acid 4 acid, salts
+5 (HPO3)n metaphosphoric acids n salts (n=3,4,6)
+5 H(HPO3)nOH polyphosphoric acids n+2 acids, salts (n=1-6)
+5 H5P3O10 tripolyphosphoric acid 3 salts
+5 H4P2O7 pyrophosphoric acid 4 acid, salts
+5 H3PO4 (ortho)phosphoric acid 3 acid, salts

Phosphorus(V) compounds

Oxides

The most prevalent compounds of phosphorus are derivatives of phosphate (PO 43), a
tetrahedral anion.[40] Phosphate is the conjugate base of phosphoric acid, which is
produced on a massive scale for use in fertilisers. Being triprotic, phosphoric acid
converts stepwise to three conjugate bases:

H3PO4 + H2O H3O+ + H2PO4 Ka1= 7.25103


H2PO4 + H2O H3O+ + HPO42 Ka2= 6.31108
HPO42 + H2O H3O+ + PO43 Ka3= 3.981013

Phosphate exhibits the tendency to form chains and rings with P-O-P bonds. Many
polyphosphates are known, including ATP. Polyphosphates arise by dehydration of
hydrogen phosphates such as HPO42 and H2PO4. For example, the industrially
important trisodium triphosphate (also known as sodium tripolyphosphate, STPP) is
produced industrially on a megatonne scale via this condensation reaction:

2 Na2[(HO)PO3] + Na[(HO)2PO2] Na5[O3P-O-P(O)2-O-PO3] + 2 H2O


Phosphorus pentoxide (P4O10) is the acid anhydride of phosphoric acid, but several
intermediates are known between the two. This waxy white solid reacts vigorously
with water.

The tetrahedral structure of P4O10and P4S10.

With metal cations, phosphate forms a variety of salts. These solids are polymeric,
featuring P-O-M linkages. When the metal cation has a charge of 2+ or 3+, the salts
are generally insoluble, hence they exist as common minerals. Many phosphate salts
are derived from hydrogen phosphate (HPO42).

PCl5 and PF5 are common compounds. PF5 is a colourless gas and the molecules
have trigonal bypramidal geometry. PCl5 is a colourless solid which has an ionic
formulation of PCl4+ PCl6, but adopts the trigonal bypramidal geometry when molten
or in the vapour phase.[12] PBr5 is an unstable solid formulated as PBr4+Brand PI5 is not
known.[12] The pentachloride and pentafluoride are Lewis acids. With fluoride,
PF5 forms PF6, an anion that is isoelectronic with SF6. The most important oxyhalide
is phosphorus oxychloride, (POCl3), which is approximately tetrahedral.

Before extensive computer calculations were feasible, it was proposed that bonding in
phosphorus(V) compounds involved d orbitals. It is now accepted that the bonding
can be better explained bymolecular orbital theory and involves only s- and p-orbitals
on phosphorus.[41]

Nitrides

The PN molecule is considered unstable, but is a product of crystalline Phosphorus


nitride decomposition at 1100 K. Similarly, H2PN is considered unstable, and
phosphorus nitride halogens like F2PN, Cl2PN, Br2PN, and I2PN oligomerize into
cyclic Polyphosphazenes. For example, compounds of the formula (PNCl2)n exist
mainly as rings such as the trimer hexachlorophosphazene. The phosphazenes arise by
treatment of phosphorus pentachloride with ammonium chloride: PCl 5 + NH4Cl
1/n (NPCl2)n + 4 HCl The chloride groups can be replaced by alkoxide (RO) to give
rise to a family of polymers with potentially useful properties.[42]

Sulfides

Main article: phosphorus sulfide

Phosphorus forms a wide range of sulfides, where phosphorus can be P(V), P(III) or
other oxidation states. Most famous is the three-fold symmetric P4S3 used in strike-
anywhere matches. P4S10 and P4O10 have analogous structures.[43]

Phosphorus(III) compounds

All four symmetrical trihalides are well known: gaseous PF3, the yellowish
liquids PCl3 and PBr3, and the solid PI3. These materials are moisture sensitive,
hydrolysing to give phosphorous acid. The trichloride, a common reagent, is produced
by chlorination of white phosphorus:

P4 + 6 Cl2 4 PCl3

The trifluoride is produced from the trichloride by halide exchange. PF3 is toxic
because it binds to haemoglobin.

Phosphorus(III) oxide, P4O6 (also called tetraphosphorus hexoxide) is the anhydride of


P(OH)3, the minor tautomer of phosphorous acid. The structure of P4O6 is like that of
P4O10 less the terminal oxide groups.

Mixed oxyhalides and oxyhydrides of phosphorus(III) are almost unknown.

Organophosphorus compounds

Main article: organophosphorus compounds

Compounds with P-C and P-O-C bonds are often classified as organophosphorus
compounds. They are widely used commercially. The PCl3 serves as a source of P3+ in
routes to organophosphorus(III) compounds. For example, it is the precursor
to triphenylphosphine:

PCl3 + 6 Na + 3 C6H5Cl P(C6H5)3 + 6 NaCl

Treatment of phosphorus trihalides with alcohols and phenols gives phosphites,


e.g. triphenylphosphite:
PCl3 + 3 C6H5OH P(OC6H5)3 + 3 HCl

Similar reactions occur for phosphorus oxychloride, affording triphenylphosphate:

OPCl3 + 3 C6H5OH OP(OC6H5)3 + 3 HCl

Phosphorus(I) and phosphorus(II) compounds

These compounds generally feature P-P bonds.[12] Examples include catenated


derivatives of phosphine and organophosphines. Compounds containing P=P double
bonds have also been observed, although they are rare.

A stable diphosphene, a derivative of phosphorus(I).

Phosphines

Phosphine (PH3) and its organic derivatives (PR3) are structural analogues with
ammonia (NH3) but the bond angles at phosphorus are closer to 90 for phosphine and
its organic derivatives. It is an ill-smelling, toxic compound. Phosphorus has an
oxidation number of -3 in phosphine. Phosphine is produced by hydrolysis of calcium
phosphide, Ca3P2. Unlike ammonia, phosphine is oxidised by air. Phosphine is also far
less basic than ammonia. Other phophines are known which contain chains of up to
nine phosphorus atoms and have the formula PnHn+2.[12] The highly flammable
gas diphosphine(P2H4) is an analogue of hydrazine.

Phosphides

Phosphides arise by reaction of metals with red phosphorus. The alkali metals (group
1) and alkaline earth metals can form ionic compounds containing the phosphide ion,
P3. These compounds react with water to form phosphine. Other phosphides, for
example Na3P7, are known for these reactive metals. With the transition metals as well
as the monophosphides there are metal rich phosphides, which are generally hard
refractory compounds with a metallic lustre, and phosphorus rich phosphides which
are less stable and include semiconductors.[44] Schreibersite is a naturally occurring
metal rich phosphide found in meteorites. The structures of the metal rich and
phosphorus rich phosphides can be structurally complex.

Spelling and etymology


The name Phosphorus in Ancient Greece was the name for the planet Venus and is
derived from the Greek words ( = light, = carry), which roughly translates
as light-bringer or light carrier.[14](In Greek mythology and tradition, Augerinus
( = morning star, still in use today), Hesperus or Hesperinus ( or
or = evening star, still in use today) and Eosphorus
( = dawnbearer, not in use for the planet after Christianity) are close
homologues, and also associated with Phosphorus-the-planet).

According to the Oxford English Dictionary, the correct spelling of the element
is phosphorus. The word phosphorous is the adjectival form of the P3+ valence: so,
just as sulfur forms sulfurous and sulfuric compounds, phosphorus forms
phosphorous compounds (e.g., phosphorous acid) and P5+ valence
phosphoric compounds (e.g., phosphoric acids and phosphates).

History and discovery


Phosphorus was the 13th element to be discovered. For this reason, and also due to its
use in explosives, poisons and nerve agents, it is sometimes referred to as "the Devil's
element".[45] It was the first element to be discovered that was not known since ancient
times.[46] The discovery of phosphorus is credited to the German alchemist Hennig
Brand in 1669, although other chemists might have discovered phosphorus around the
same time.[47] Brand experimented with urine, which contains considerable quantities
of dissolved phosphates from normal metabolism.[14] Working in Hamburg, Brand
attempted to create the fabled philosopher's stone through the distillation of
some salts by evaporating urine, and in the process produced a white material that
glowed in the dark and burned brilliantly. It was named phosphorus
mirabilis ("miraculous bearer of light").[48] His process originally involved letting urine
stand for days until it gave off a terrible smell. Then he boiled it down to a paste,
heated this paste to a high temperature, and led the vapours through water, where he
hoped they would condense to gold. Instead, he obtained a white, waxy substance that
glowed in the dark. Brand had discovered phosphorus. We now know that Brand
produced ammonium sodium hydrogen phosphate, (NH
4)NaHPO
4. While the quantities were essentially correct (it took about 1,100 litres [290 US gal]
of urine to make about 60 g of phosphorus), it was unnecessary to allow the urine to
rot. Later scientists discovered that fresh urine yielded the same amount of
phosphorus.

Robert Boyle

Brand at first tried to keep the method secret,[49] but later sold the recipe for 200 thalers
to D Krafft from Dresden,[14] who could now make it as well, and toured much of
Europe with it, including England, where he met with Robert Boyle. The secret that it
was made from urine leaked out and first Johann Kunckel (16301703) in Sweden
(1678) and later Boyle in London (1680) also managed to make phosphorus, possibly
with the aid of his assistant, Ambrose Godfrey-Hanckwitz, who later made a business
of the manufacture of phosphorus. Boyle states that Krafft gave him no information as
to the preparation of phosphorus other than that it was derived from "somewhat that
belonged to the body of man". This gave Boyle a valuable clue, so that he, too,
managed to make phosphorus, and published the method of its manufacture.[14] Later
he improved Brand's process by using sand in the reaction (still using urine as base
material),

4 NaPO
3 + 2 SiO
2 + 10 C 2 Na
2SiO
3 + 10 CO + P
4

Robert Boyle was the first to use phosphorus to ignite sulfur-tipped wooden splints,
forerunners of our modern matches, in 1680.

In 1769 Johan Gottlieb Gahn and Carl Wilhelm Scheele showed that calcium
phosphate (Ca
3(PO
4)
2) is found in bones, and they obtained elemental phosphorus from bone ash. Antoine
Lavoisierrecognized phosphorus as an element in 1777.[50] Bone ash was the major
source of phosphorus until the 1840s. The method started by roasting bones, then
employed the use of clay retorts encased in a very hot brick furnace to distill out the
highly toxic elemental phosphorus product.[51] Alternately, precipitated phosphates
could be made from ground-up bones that had been de-greased and treated with strong
acids. White phosphorus could be then be made by heating the precipitated
phosphates, mixed with ground coal or charcoal in an iron pot, and distilling off
phosphorus vapour in a retort.[52]Carbon monoxide and other flammable gases
produced during the reduction process were burnt off in a flare stack.

In the 1840s, world phosphate production turned to the mining of tropical island
deposits formed from bird and bat guano (see also Guano Islands Act). These became
an important source of phosphates for fertilizer in the latter half of the 19th century.

Phosphate rock, a mineral containing calcium phosphate, was first used in 1850 to
make phosphorus, and following the introduction of the electric arc furnace in 1890,
elemental phosphorus production switched from the bone-ash heating, to electric arc
production from phosphate rock. After the depletion of world guano sources about the
same time, mineral phosphates became the major source of phosphate fertilizer
production. Phosphate rock production greatly increased after World War II, and
remains the primary global source of phosphorus and phosphorus chemicals today.
See the article onpeak phosphorus for more information on the history and present
state of phosphate mining. Phosphate rock remains a feedstock in the fertilizer
industry, where it is treated with sulfuric acid to produce various "superphosphate"
fertilizer products.

White phosphorus was first made commercially in the 19th century for
the match industry. This used bone ash for a phosphate source, as described above.
The bone-ash process became obsolete when thesubmerged-arc furnace for
phosphorus production was introduced to reduce phosphate rock.[53][54] The electric
furnace method allowed production to increase to the point where phosphorus could
be used in weapons of war.[55][56] In World War I it was used in incendiaries, smoke
screens and tracer bullets.[56] A special incendiary bullet was developed to shoot
at hydrogen-filled Zeppelins over Britain (hydrogen being
highly flammable).[56] During World War II, Molotov cocktails made of phosphorus
dissolved in petrol were distributed in Britain to specially selected civilians within the
British resistance operation, for defence; and phosphorus incendiary bombs were used
in war on a large scale. Burning phosphorus is difficult to extinguish and if it splashes
onto human skin it has horrific effects.[12]

Early matches used white phosphorus in their composition, which was dangerous due
to its toxicity. Murders, suicides and accidental poisonings resulted from its use. (An
apocryphal tale tells of a woman attempting to murder her husband with white
phosphorus in his food, which was detected by the stew's giving off luminous
steam).[55] In addition, exposure to the vapours gave match workers a
severe necrosis of the bones of the jaw, the infamous "phossy jaw". When a safe
process for manufacturing red phosphorus was discovered, with its far lower
flammability and toxicity, laws were enacted, under the Berne Convention (1906),
requiring its adoption as a safer alternative for match manufacture.[57] The toxicity of
white phosphorus led to discontinuation of its use in matches.[58] The Allies used
phosphorus incendiary bombs in World War II to destroy Hamburg, the place where
the "miraculous bearer of light" was first discovered.[48]

Glow

It was known from early times that the green glow emanating from white phosphorus
would persist for a time in a stoppered jar, but then cease. Robert Boyle in the 1680s
ascribed it to "debilitation" of the air; in fact, it is oxygen being consumed. By the
18th century, it was known that in pure oxygen, phosphorus does not glow at
all;[59] there is only a range of partial pressure at which it does. Heat can be applied to
drive the reaction at higher pressures.[60]

In 1974, the glow was explained by R. J. van Zee and A. U. Khan.[55][61] A reaction with
oxygen takes place at the surface of the solid (or liquid) phosphorus, forming the
short-lived molecules HPO andP
2O
2 that both emit visible light. The reaction is slow and only very little of the
intermediates are required to produce the luminescence, hence the extended time the
glow continues in a stoppered jar.

Since that time, phosphors and phosphorescence were used loosely to describe
substances that shine in the dark without burning. Although the term phosphorescence
was originally coined as a term by analogy with the glow from oxidation of elemental
phosphorus, it is now reserved for another fundamentally different processre-
emission of light after illumination.

Applications
Fertiliser

Main article: Fertiliser

The dominant application of phosphorus is in fertilisers, which provides phosphate as


required for all life and is often a limiting nutrient for crops. Phosphorus, being an
essential plant nutrient, finds its major use as a constituent
of fertilisers for agriculture and farm production in the form of concentrated
phosphoric acids, which can consist of 70% to 75% P2O5. Global demand for
fertilisers led to large increase in phosphate (PO43) production in the second half of
the 20th century. Due to the essential nature of phosphorus to living organisms, the
low solubility of natural phosphorus-containing compounds, and the slow natural
cycle of phosphorus, the agricultural industry relies on fertilisers that contain
phosphate. A major form of these fertilisers is superphosphate of lime, a mixture of
two salts, calcium dihydrogen phosphate Ca(H2PO4)2 and calcium sulfate dihydrate
CaSO42H2O, produced by the reaction of sulfuric acid and water with calcium
phosphate.

So large is the need to process phosphate minerals with sulfuric acid to obtain
fertiliser, that this use is the major global industrial use for important industrial
chemical sulfuric acid (the production of which, in turn, is the largest industrial use of
the element sulfur).

Widely used compounds Use


Ca(H2PO4)2H2O Baking powder and fertilizers
CaHPO42H2O Animal food additive, toothpowder
H3PO4 Manufacture of phosphate fertilizers
PCl3 Manufacture of POCl3 and pesticides
POCl3 Manufacture of plasticizer
P4S10 Manufacturing of additives and pesticides
Na5P3O10 Detergents

Organophosphorus compounds

White phosphorus is widely used to make organophosphorus compounds, through the


intermediates phosphorus chlorides and two phosphorus sulfides, phosphorus
pentasulfide, and phosphorus sesquisulfide.[62] Organophosphorus compounds have
many applications, including in plasticizers, flame retardants, pesticides, extraction
agents, and water treatment.[12]

Metallurgical aspects

Phosphorus is also an important component in steel production, in the making


of phosphor bronze, and in many other related products. Phosphorus is added to
metallic copper during its smelting process to react with oxygen present as an
impurity in copper and to produce phosphorus-containing copper (CuOFP) alloys with
a higher hydrogen embrittlement resistance than normal copper.
Matches

Match striking surface made of a mixture of red phosphorus, glue and ground glass.
The glass powder is used to increase the friction.
Main article: Match

Phosphorus-contained matches were first produced in the 1830s and contained a


mixture of white phosphorus, an oxygen-releasing compound (potassium
chlorate, lead dioxide or some nitrate) and a binder in their heads. They were rather
sensitive to storage conditions, toxic and unsafe, as they could be lit by striking on
any rough surface. Therefore, their production was gradually banned between 1872
and 1925 in different countries.[63] The international Berne Convention, adopted in
1906, prohibited the use of white phosphorus in matches. As a consequence, the
'strike-anywhere' matches were gradually replaced by 'safety matches' where white
phosphorus was replaced by phosphorus sesquisulfide (P4S3), sulfur or antimony
sulfide. Such matches are hard to ignite on an arbitrary surface and require a special
strip. The strip contains red phosphorus which heats up upon striking, reacts with the
oxygen-releasing compound in the head and ignites the flammable material of the
head.[15][62]

Water softening

Sodium tripolyphosphate made from phosphoric acid is used in laundry detergents in


some countries, but banned for this use in others.[17] It is useful for softening water to
enhance the performance of the detergents and to prevent pipe/boiler tube corrosion.

Niche applications

Phosphates are utilized in the making of special glasses that are used
for sodium lamps.[17]
Bone-ash, calcium phosphate, is used in the production of fine china.[17]
Phosphoric acid made from elemental phosphorus is used in food applications
such as some soft drinks. The acid is also a starting point to make food grade
phosphates.[62] These include mono-calcium phosphate that is employed
in baking powder and sodium tripolyphosphate and other sodium
phosphates.[62] Among other uses these are used to improve the characteristics of
processed meat and cheese. Others are used in toothpaste.[62]
White phosphorus, called "WP" (slang term "Willie Peter") is used
in military applications as incendiary bombs, for smoke-screening as smoke
pots and smoke bombs, and in tracer ammunition. It is also a part of an obsolete
M34 White Phosphorus US hand grenade. This multipurpose grenade was
mostly used for signalling, smoke screens and inflammation; it could also cause
severe burns and had a psychological impact on the enemy.[64][65] Military uses of
white phosphorus are constrained by international law[66]
In trace amounts, phosphorus is used as a dopant for n-type semiconductors.
32
P and 33P are used as radioactive tracers in biochemical laboratories.
Phosphate is a strong complexing agent for the hexavalent uranyl (UO22+)
species and this is the reason why apatite and other natural phosphates can
often be very rich in uranium.
Tributylphosphate is an organophosphate soluble in kerosene and used to
extract uranium in the Purex process applied in the reprocessing of spent
nuclear fuel.

Biological role
Inorganic phosphorus in the form of the phosphate PO3
4 is required for all known forms of life,[67] playing a major role in biological molecules
such as DNA and RNA where it forms part of the structural framework of these
molecules. Living cells also use phosphate to transport cellular energy in the form
of adenosine triphosphate (ATP). Nearly every cellular process that uses energy
obtains it in the form of ATP. ATP is also important for phosphorylation, a key
regulatory event in cells. Phospholipids are the main structural components of all
cellular membranes. Calcium phosphate salts assist in stiffening bones.[12]

Living cells are defined by a membrane that separates it from its surroundings.
Biological membranes are made from a phospholipid matrix and proteins, typically in
the form of a bilayer. Phospholipids are derived from glycerol, such that two of the
glycerol hydroxyl (OH) protons have been replaced with fatty acids as an ester, and
the third hydroxyl proton has been replaced with phosphate bonded to another
alcohol.[68]

An average adult human contains about 0.7 kg of phosphorus, about 8590% of which
is present in bones and teeth in the form of apatite, and the remainder in soft tissues
and extracellular fluids (~1%). The phosphorus content increases from about 0.5
weight% in infancy to 0.651.1 weight% in adults. Average phosphorus concentration
in the blood is about 0.4 g/L, about 70% of that is organic and 30% inorganic
phosphates.[69] A well-fed adult in the industrialized world consumes and excretes
about 13 grams of phosphorus per day, with consumption in the form of inorganic
phosphate and phosphorus-containing biomolecules such as nucleic acids and
phospholipids; and excretion almost exclusively in the form of phosphate ions such
as H
2PO
4 and HPO2
4. Only about 0.1% of body phosphate circulates in the blood, and this amount reflects
the amount of phosphate available to soft tissue cells.

Bone and teeth enamel

The main component of bone is hydroxyapatite as well as amorphous forms of


calcium phosphate, possibly including carbonate. Hydroxyapatite is the main
component of tooth enamel. Water fluoridation enhances the resistance of teeth to
decay by the partial conversion of this mineral to the still harder material called
fluoroapatite:[12]

Ca
5(PO
4)
3OH + F
Ca
5(PO
4)
3F + OH

Phosphorus deficiency

In medicine, low-phosphate syndromes are caused by malnutrition, by failure to


absorb phosphate, and by metabolic syndromes that draw phosphate from the blood
(such as re-feeding after malnutrition) or pass too much of it into the urine. All are
characterized by hypophosphatemia, which is a condition of low levels of soluble
phosphate levels in the blood serum, and therefore inside cells. Symptoms of
hypophosphatemia include muscle and neurological dysfunction, and disruption of
muscle and blood cells due to lack of ATP. Too much phosphate can lead to diarrhoea
and calcification (hardening) of organs and soft tissue, and can interfere with the
body's ability to use iron, calcium, magnesium, and zinc.[70]
Phosphorus is an essential macromineral for plants, which is studied extensively
in edaphology in order to understand plant uptake from soil systems.
In ecological terms, phosphorus is often a limiting factor in many environments; i.e.
the availability of phosphorus governs the rate of growth of many organisms.
In ecosystems an excess of phosphorus can be problematic, especially in aquatic
systems, resulting in eutrophication which sometimes lead to algal blooms.

Food sources

The main food sources for phosphorus are foods containing protein, although proteins
do not contain phosphorus. For example, milk, meat, and soya typically also have
phosphorus. As a rule, if one holds a meal plan providing sufficient amount of protein
and calcium then the amount of phosphorus is also likely sufficient.[71]

Precautions
Organic compounds of phosphorus form a wide class of materials, many are required
for life, but some are extremely toxic. Fluorophosphate esters are among the most
potent neurotoxins known. A wide range of organophosphorus compounds are used
for their toxicity to certain organisms
as pesticides (herbicides, insecticides, fungicides, etc.) and weaponised as nerve
agents. Most inorganic phosphates are relatively nontoxic and essential nutrients.[12]

The white phosphorus allotrope presents a significant hazard because it ignites in air
and produces phosphoric acid residue. Chronic white phosphorus poisoning leads to
necrosis of the jaw called "phossy jaw". Ingestion of white phosphorus may cause a
medical condition known as "Smoking Stool Syndrome".[72]

Phosphorus explosion

Upon exposure to elemental phosphorus, in the past it was suggested to wash the
affected area with 2% copper sulfate solution to form harmless compounds that can be
washed away. According to the recent US Navy's Treatment of Chemical Agent
Casualties and Conventional Military Chemical Injuries: FM8-285: Part 2
Conventional Military Chemical Injuries, "Cupric (copper(II)) sulfate has been used
by U.S. personnel in the past and is still being used by some nations. However, copper
sulfate is toxic and its use will be discontinued. Copper sulfate may produce kidney
and cerebral toxicity as well as intravascular hemolysis."[73]

The manual suggests instead "a bicarbonate solution to neutralize phosphoric acid,
which will then allow removal of visible white phosphorus. Particles often can be
located by their emission of smoke when air strikes them, or by their phosphorescence
in the dark. In dark surroundings, fragments are seen as luminescent spots.
Promptly debride the burn if the patient's condition will permit removal of bits of WP
(white phosphorus) that might be absorbed later and possibly produce systemic
poisoning. DO NOT apply oily-based ointments until it is certain that all WP has been
removed. Following complete removal of the particles, treat the lesions as thermal
burns."[note 1] As white phosphorus readily mixes with oils, any oily substances or
ointments are not recommended until the area is thoroughly cleaned and all white
phosphorus removed.

Sulfur
From Wikipedia, the free encyclopedia
Jump to: navigation, search
This article is about the chemical element. For other uses, see Sulfur
(disambiguation).

Sulfur, S 16

Spectral lines of sulfur

General properties
Name, symbol sulfur, S

Appearance lemon yellow sintered microcrystals

Pronunciation /slfr/
SUL-fr

Sulfur in the periodic table

O

S

Se

phosphorus sulfur chlorine

Atomic number 16

Standard atomic weight (Ar) 32.06[1] (32.05932.076)[2]

Element category polyatomic nonmetal

Group, block group 16 (chalcogens), p-block

Period period 3

Electron configuration [Ne] 3s2 3p4

per shell 2, 8, 6

Physical properties

Phase solid

Melting point 388.36 K (115.21 C, 239.38 F)

Boiling point 717.8 K (444.6 C, 832.3 F)


Density near r.t. alpha: 2.07 g/cm3
beta: 1.96 g/cm3
gamma: 1.92 g/cm3

when liquid, at m.p. 1.819 g/cm3

Critical point 1314 K, 20.7 MPa

Heat of fusion mono: 1.727 kJ/mol

Heat of vaporization mono: 45 kJ/mol

Molar heat capacity 22.75 J/(molK)

vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 375 408 449 508 591 717

Atomic properties

Oxidation states 6, 5, 4, 3, 2, 1, 1, 2
(a strongly acidic oxide)

Electronegativity Pauling scale: 2.58

Ionization energies 1st: 999.6 kJ/mol


2nd: 2252 kJ/mol
3rd: 3357 kJ/mol
(more)

Covalent radius 1053 pm

Van der Waals radius 180 pm

Miscellanea
Crystal structure orthorhombic

Thermal conductivity 0.205 W/(mK) (amorphous)

Electrical resistivity 21015 m (at 20 C) (amorphous)

Magnetic ordering diamagnetic[3]

Bulk modulus 7.7 GPa

Mohs hardness 2.0

CAS Registry Number 7704-34-9

History

Discovery Chinese[4] (before 2000 BCE)

Recognized as anelement by Antoine Lavoisier (1777)

Most stable isotopes

Main article: Isotopes of sulfur

iso NA half-life DM DE (MeV) DP


32
S 95.02%32S is stable with 16 neutrons
33
S 0.75%33S is stable with 17 neutrons
34
S 4.21%34S is stable with 18 neutrons
35
S syn 87.32 d 0.167 35
Cl
36
S 0.02% S is stable with 20 neutrons
36

references
Sulfur or sulphur (see spelling differences) is a chemical element with
symbol S and atomic number 16. It is an abundant, multivalent non-metal.
Under normal conditions, sulfur atoms form cyclic octatomic molecules with
chemical formula S8. Elemental sulfur is a bright yellow crystalline solid when at
room temperature. Chemically, sulfur can react as either an oxidant or a reducing
agent. It oxidizes most metals and several nonmetals, including carbon, which leads to
its negative charge in most organosulfur compounds, but it reduces several strong
oxidants, such as oxygen andfluorine.

Sulfur occurs naturally as the pure element (native sulfur) and as sulfide and sulfate
minerals. Elemental sulfur crystals are commonly sought after by mineral collectors
for their distinct, brightly colored polyhedron shapes. Being abundant in native form,
sulfur was known in ancient times, mentioned for its uses in ancient India, ancient
Greece, China and Egypt. Fumes from burning sulfur were used as fumigants, and
sulfur-containing medicinal mixtures were used as balms and antiparasitics. Sulfur is
referred to in the Bible as brimstone (burn stone) in English, with this name still used
in several nonscientific tomes.[5] It was needed to make the best quality of black
gunpowder. In 1777, Antoine Lavoisier helped convince the scientific community that
sulfur was a basic element rather than a compound.

Elemental sulfur was once extracted from salt domes where it sometimes occurs in
nearly pure form, but this method has been obsolete since the late 20th century.
Today, almost all elemental sulfur is produced as a byproduct of removing sulfur-
containing contaminants from natural gas and petroleum. The element's largest
commercial use (after mostly being converted to sulfuric acid) is to produce sulfate
and phosphate fertilizers, because of the relatively high requirement of plants for
sulfur and phosphorus. Sulfuric acid is also a primary industrial chemical outside
fertilizer manufacture. Other well-known uses for the element are
in matches, insecticides and fungicides. Many sulfur compounds are odoriferous, and
the smell of odorized natural gas, skunk scent, grapefruit, and garlic is due to sulfur
compounds. Hydrogen sulfide produced by living organisms imparts the characteristic
odor to rotting eggs and other biological processes.

Sulfur is an essential element for all life, and is widely used in biochemical processes.
In metabolic reactions, sulfur compounds serve as both fuels (electron donors) and
respiratory (oxygen-alternative) materials (electron acceptors). Sulfur in organic form
is present in the vitamins biotin andthiamine, the latter being named for the Greek
word for sulfur. Sulfur is an important part of many enzymes and in antioxidant
molecules likeglutathione and thioredoxin. Organically bonded sulfur is a component
of all proteins, as the amino acids cysteine and methionine. Disulfide bonds are
largely responsible for the mechanical strength and insolubility of the protein keratin,
found in outer skin, hair, and feathers, and the element contributes to their pungent
odor when burned.

Contents
[hide]

1 Spelling and etymology


2 Characteristics
o 2.1 Physical properties
o 2.2 Chemical properties
o 2.3 Allotropes
o 2.4 Isotopes
o 2.5 Natural occurrence
3 Production
4 Compounds
o 4.1 Sulfur polycations
o 4.2 Sulfides
o 4.3 Oxides, oxoacids and oxoanions
o 4.4 Halides and oxyhalides
o 4.5 Pnictides
o 4.6 Metal sulfides
o 4.7 Organic compounds
5 History
o 5.1 Antiquity
o 5.2 Modern times
6 Applications
o 6.1 Sulfuric acid
o 6.2 Other large-scale sulfur chemicals
o 6.3 Fertilizer
o 6.4 Fine chemicals
o 6.5 Fungicide and pesticide
o 6.6 Bactericide in winemaking and food preservation
o 6.7 Pharmaceutical use
7 Biological role
o 7.1 Protein and organic cofactors
o 7.2 Metalloproteins and inorganic cofactors
o 7.3 Sulfur metabolism and the sulfur cycle
8 Precautions
9 See also
10 References
11 External links

Spelling and etymology


Sulfur is historically a Latin word. The original Latin spelling was sulpur, but this
was Hellenized to sulphur; the form sulfur appears toward the end of the Classical
period. (The true Greek word for sulfur, , is the source of the international
chemical prefix thio-.) In 12th-century Anglo-French, it was sulfre; in the 14th
century the Latin ph was restored, for sulphre; and by the 15th century the full Latin
spelling was restored, for sulfur, sulphur. The parallel f~ph spellings continued in
Britain until the 19th century, when the word was standardized
as sulphur.[6] Sulfur was the form chosen in the United States, whereas Canada uses
both. However, the IUPAC adopted the spelling sulfur in 1990, as did the
Nomenclature Committee of the Royal Society of Chemistry in 1992, restoring the
spelling sulfur to Britain.[7] The Oxford Dictionaries note that "in chemistry ... the -f-
spelling is now the standard form in all related words in the field in both British and
US contexts."[8]

The late Latin form also continues in the Romance languages: French soufre,
Italian zolfo (from solfo), Spanish azufre (from aufre, from earlier ufre),
Portuguese enxofre (from xofre). The Spanish and Portuguese forms are prefixed with
the Arabic article, despite not being Arabic words.[6] The root has been traced back to
reconstructed proto-Indo-European *swpl (genitive *sulpls), a nominal derivative
of *swelp 'to burn', a lineage also preserved in the Germanic languages, where it is
found for example as modern German Schwefel, Dutch zwavel, and Swedish svavel,
and as Old English swefl.[9]

Characteristics
When burned, sulfur melts to a blood-red liquid and emits a blue flame that is best
observed in the dark.

Physical properties

Sulfur forms polyatomic molecules with different chemical formulas, with the best-
known allotrope being octasulfur, cyclo-S8. The point group of cyclo-S8 is D4d and its
dipole moment is 0 D.[10] Octasulfur is a soft, bright-yellow solid with only a faint
odor, similar to that of matches.[11] It melts at 115.21 C (239.38 F), boils at 444.6 C
(832.3 F) and sublimes easily.[5] At 95.2 C (203.4 F), below its melting temperature,
cyclo-octasulfur changes from -octasulfur to the -polymorph.[12] The structure of the
S8 ring is virtually unchanged by this phase change, which affects the intermolecular
interactions. Between its melting and boiling temperatures, octasulfur changes its
allotrope again, turning from -octasulfur to -sulfur, again accompanied by a lower
density but increasedviscosity due to the formation of polymers.[12] At even higher
temperatures, however, the viscosity decreases as depolymerization occurs. Molten
sulfur assumes a dark red color above 200 C (392 F). The density of sulfur is about
2 gcm3, depending on the allotrope; all of its stable allotropes are excellent electrical
insulators.

Chemical properties

Sulfur burns with a blue flame concomitant with formation of sulfur dioxide, notable
for its peculiar suffocating odor. Sulfur is insoluble in water but soluble in carbon
disulfide and, to a lesser extent, in other nonpolar organic solvents, such
as benzene and toluene. The first and the second ionization energies of sulfur are
999.6 and 2252 kJmol1, respectively. Despite such figures, the +2 oxidation state is
rare, with +4 and +6 being more common. The fourth and sixth ionization energies are
4556 and 8495.8 kJmol1, the magnitude of the figures caused by electron transfer
between orbitals; these states are only stable with strong oxidants as fluorine, oxygen,
and chlorine.

Allotropes

The structure of the cyclooctasulfur molecule, S8.


Main article: Allotropes of sulfur

Sulfur forms over 30 solid allotropes, more than any other element.[13] Besides S8,
several other rings are known.[14] Removing one atom from the crown gives S7, which
is more deeply yellow than S8.HPLC analysis of "elemental sulfur" reveals an
equilibrium mixture of mainly S8, but with S7 and small amounts of S6.[15] Larger rings
have been prepared, including S12 and S18.[16][17]

Amorphous or "plastic" sulfur is produced by rapid cooling of molten sulfurfor


example, by pouring it into cold water. X-ray crystallography studies show that the
amorphous form may have a helicalstructure with eight atoms per turn. The long
coiled polymeric molecules make the brownish substance elastic, and in bulk this
form has the feel of crude rubber. This form is metastable at room temperature and
gradually reverts to crystalline molecular allotrope, which is no longer elastic. This
process happens within a matter of hours to days, but can be rapidly catalyzed.

Isotopes

Main article: Isotopes of sulfur

Sulfur has 25 known isotopes, four of which are stable: 32S (95.02%), 33S (0.75%), 34S
(4.21%), and 36S (0.02%). Other than 35S, with a half-life of 87 days and formed
in cosmic ray spallation of 40Ar, the radioactive isotopes of sulfur have half-lives less
than 3 hours.

When sulfide minerals are precipitated, isotopic equilibration among solids and liquid
may cause small differences in the S-34 values of co-genetic minerals. The
differences between minerals can be used to estimate the temperature of equilibration.
The C-13 and S-34 of coexisting carbonate minerals and sulfides can be used to
determine the pH and oxygen fugacity of the ore-bearing fluid during ore formation.

In most forest ecosystems, sulfate is derived mostly from the atmosphere; weathering
of ore minerals and evaporites contribute some sulfur. Sulfur with a distinctive
isotopic composition has been used to identify pollution sources, and enriched sulfur
has been added as a tracer in hydrologic studies. Differences in the natural
abundances can be used in systems where there is sufficient variation in the 34S of
ecosystem components. Rocky Mountain lakes thought to be dominated by
atmospheric sources of sulfate have been found to have different 34S values from
lakes believed to be dominated by watershed sources of sulfate.

Natural occurrence

Most of the yellow and orange hues of Io are due to elemental sulfur and sulfur
compounds, produced by active volcanoes.

Native sulfur crystals


A man carrying sulfur blocks from Kawah Ijen, a volcano in East Java, Indonesia,
2009

S is created inside massive stars, at a depth where the temperature exceeds


32

2.5109 K, by the fusion of one nucleus of silicon plus one nucleus of helium.[18] As
this is part of the alpha process that produces elements in abundance, sulfur is the 10th
most common element in the universe.

Sulfur, usually as sulfide, is present in many types of meteorites. Ordinary chondrites


contain on average 2.1% sulfur, and carbonaceous chondrites may contain as much as
6.6%. It is normally present astroilite (FeS), but there are exceptions, with
carbonaceous chondrites containing free sulfur, sulfates and other sulfur
compounds.[19] The distinctive colors of Jupiter's volcanic moon Io are attributed to
various forms of molten, solid and gaseous sulfur.[20]

Sulfur could be found in fumarolessuch as this one in Vulcano, Italy

On Earth, elemental sulfur can be found near hot springs and volcanic regions in
many parts of the world, especially along the Pacific Ring of Fire; such volcanic
deposits are currently mined inIndonesia, Chile, and Japan. Such deposits are
polycrystalline, with the largest documented single crystal measuring
221611 cm.[21] Historically, Sicily was a large source of sulfur in the Industrial
Revolution.[22]

Native sulfur is synthesised by anaerobic bacteria acting on sulfate minerals such


as gypsum in salt domes.[23][24] Significant deposits in salt domes occur along the coast
of the Gulf of Mexico, and inevaporites in eastern Europe and western Asia. Native
sulfur may be produced by geological processes alone. Fossil-based sulfur deposits
from salt domes have until recently been the basis for commercial production in
the United States, Russia, Turkmenistan, and Ukraine.[25] Currently, commercial
production is still carried out in the Osiek mine in Poland. Such sources are now of
secondary commercial importance, and most are no longer worked.
Common naturally occurring sulfur compounds include the sulfide minerals, such
as pyrite (iron sulfide), cinnabar (mercury sulfide), galena (lead
sulfide), sphalerite (zinc sulfide) and stibnite (antimony sulfide); and the sulfates, such
as gypsum (calcium sulfate), alunite (potassium aluminium sulfate),
and barite (barium sulfate). On Earth, just as upon Jupiter's moon Io, elemental sulfur
occurs naturally in volcanic emissions, including emissions from hydrothermal vents.

Production
Sulfur may be found by itself and historically was usually obtained in this way, while
pyrite has been a source of sulfur via sulfuric acid.[disputed ][26] In volcanic regions in Sicily,
in ancient times, it was found on the surface of the Earth, and the "Sicilian
process" was used: sulfur deposits were piled and stacked in brick kilns built on
sloping hillsides, with airspaces between them. Then, some sulfur was pulverized,
spread over the stacked ore and ignited, causing the free sulfur to melt down the hills.
Eventually the surface-borne deposits played out, and miners excavated veins that
ultimately dotted the Sicilian landscape with labyrinthine mines. Mining was
unmechanized and labor-intensive, with pickmen freeing the ore from the rock, and
mine-boys or carusi carrying baskets of ore to the surface, often through a mile or
more of tunnels. Once the ore was at the surface, it was reduced and extracted in
smelting ovens. The conditions in Sicilian sulfur mines were horrific,
prompting Booker T. Washington to write "I am not prepared just now to say to what
extent I believe in a physical hell in the next world, but a sulphur mine in Sicily is
about the nearest thing to hell that I expect to see in this life.".[27]

Today's sulfur production is as a side product of other industrial processes such as oil
refining; in these processes, sulfur often occurs as undesired or detrimental
compounds that are extracted and converted to elemental sulfur. As a mineral, native
sulfur under salt domes is thought to be a fossil mineral resource, produced by the
action of ancient bacteria on sulfate deposits. It was removed from such salt-dome
mines mainly by the Frasch process.[25] In this method, superheated water was pumped
into a native sulfur deposit to melt the sulfur, and then compressed air returned the
99.5% pure melted product to the surface. Throughout the 20th century this procedure
produced elemental sulfur that required no further purification. However, due to a
limited number of such sulfur deposits and the high cost of working them, this process
for mining sulfur has not been employed in a major way anywhere in the world since
2002.[28][29]
Sulfur recovered from hydrocarbons in Alberta, stockpiled for shipment in North
Vancouver, B.C.

Today, sulfur is produced from petroleum, natural gas, and related fossil resources,
from which it is obtained mainly as hydrogen sulfide. Organosulfur compounds,
undesirable impurities in petroleum, may be upgraded by subjecting them
to hydrodesulfurization, which cleaves the CS bonds:[28][29]

R-S-R + 2 H2 2 RH + H2S

The resulting hydrogen sulfide from this process, and also as it occurs in natural gas,
is converted into elemental sulfur by the Claus process. This process entails oxidation
of some hydrogen sulfide to sulfur dioxide and then the comproportionation of the
two:[28][29]

3 O2 + 2 H2S 2 SO2 + 2 H2O


SO2 + 2 H2S 3 S + 2 H2O

Production and price (US market) of elemental sulfur

Owing to the high sulfur content of the Athabasca Oil Sands, stockpiles of elemental
sulfur from this process now exist throughout Alberta, Canada.[30] Another way of
storing sulfur is as a binder for concrete, the resulting product having many desirable
properties (see sulfur concrete).[31] Sulfur is still mined from surface deposits in poorer
nations with volcanos, such as Indonesia, and worker conditions have not improved
much since Booker T. Washington's days.[32]

The world production of sulfur in 2011 amounted to 69 million tonnes (Mt), with
more than 15 countries contributing more than 1 Mt each. Countries producing more
than 5 Mt are China (9.6), US (8.8), Canada (7.1) and Russia (7.1).[33] While the
production has been slowly increasing from 1900 to 2010, the price was much less
stable, especially in the 1980s and around 2010.[34]

Compounds
See also: Category:Sulfur compounds.

Common oxidation states of sulfur range from 2 to +6. Sulfur forms stable
compounds with all elements except the noble gases.

Sulfur polycations

Sulfur polycations, S82+, S42+ and S192+ are produced when sulfur is reacted with mild
oxidising agents in a strongly acidic solution.[35] The colored solutions produced by
dissolving sulfur in oleum were first reported as early as 1804 by C.F Bucholz, but the
cause of the color and the structure of the polycations involved was only determined
in the late 1960s. S82+ is deep blue, S42+ is yellow and S192+ is red.[12]

Sulfides

Treatment of sulfur with hydrogen gives hydrogen sulfide. When dissolved in water,
hydrogen sulfide is mildly acidic:[5]

H2S HS + H+

Hydrogen sulfide gas and the hydrosulfide anion are extremely toxic to mammals, due
to their inhibition of the oxygen-carrying capacity of hemoglobin and
certain cytochromes in a manner analogous tocyanide and azide (see below,
under precautions).

Reduction of elemental sulfur gives polysulfides, which consist of chains of sulfur


atoms terminated with S centers:

2 Na + S8 Na2S8

This reaction highlights arguably the single most distinctive property of sulfur: its
ability to catenate (bind to itself by formation of chains). Protonation of these
polysulfide anions gives the polysulfanes, H2Sx where x = 2, 3, and 4.[36] Ultimately
reduction of sulfur gives sulfide salts:

16 Na + S8 8 Na2S
The interconversion of these species is exploited in the sodium-sulfur battery.
The radical anion S3 gives the blue color of the mineral lapis lazuli.

Lapis lazuli owes its blue color to a trisulfur radical anion (S


3)

Oxides, oxoacids and oxoanions

The principal sulfur oxides are obtained by burning sulfur:

S + O2 SO2
2 SO2 + O2 2 SO3

Other oxides are known, sulfur-rich oxides e.g. sulfur monoxide and disulfur mono-
and dioxides and higher oxides containing peroxo groups.

Sulfur forms a number of sulfur oxoacids, some of which cannot be isolated and are
only known through their salts. Sulfur dioxide and sulfites (SO2
3) are related to the unstable sulfurous acid (H2SO3).Sulfur trioxide and sulfates (SO2
4) are related to sulfuric acid. Sulfuric acid and SO3 combine to give oleum, a solution
of pyrosulfuric acid (H2S2O7) in sulfuric acid.

Peroxydisulfuric acid
The sulfate anion, SO2
4

Thiosulfate salts (S
2O2
3), sometimes referred as "hyposulfites", used in photographic fixing (HYPO) and as
reducing agents, feature sulfur in two oxidation states. Sodium dithionite (Na
2S
2O
4), contains the more highly reducing dithionite anion (S
2O2
4).

Halides and oxyhalides

The two main sulfur fluorides are sulfur hexafluoride, a dense gas used as an insulator
gas in high voltage transformers and a nonreactive and nontoxic propellant, and sulfur
tetrafluoride, a rarely used organic reagent that is highly toxic.[37] Sulfur
dichloride and disulfur dichloride are important industrial chemicals. Sulfuryl
chloride and chlorosulfuric acid are derivatives of sulfuric acid; thionyl
chloride (SOCl2) is a common reagent in organic synthesis.[38]

Pnictides

An important SN compound is the cage tetrasulfur tetranitride (S4N4). Heating this


compound gives polymeric sulfur nitride ((SN)x), which has metallic properties even
though it does not contain anymetal atoms. Thiocyanates contain the SCN group.
Oxidation of thiocyanate gives thiocyanogen, (SCN)2 with the connectivity NCS-
SCN. Phosphorus sulfides are numerous, the most important commercially being the
cages P4S10 and P4S3.[39][40]

Metal sulfides
Main article: Sulfide mineral

The principal ores of copper, zinc, nickel, cobalt, molybdenum, and other metals are
sulfides. These materials tend to be dark-colored semiconductors that are not readily
attacked by water or even many acids. They are formed, both geochemically and in
the laboratory, by the reaction of hydrogen sulfide with metal salts. The
mineral galena (PbS) was the first demonstrated semiconductor and found a use as a
signal rectifier in the cat's whiskers of early crystal radios. The iron sulfide
called pyrite, the so-called "fool's gold," has the formula FeS2.[41] The upgrading of
these ores, usually by roasting, is costly and environmentally hazardous. Sulfur
corrodes many metals via the process called tarnishing.

Organic compounds

Main article: Organosulfur compounds

Illustrative organosulfur compounds

Allicin, the active ingredient in garlic

(R)-cysteine, an amino acid containing a thiol group

Methionine, an amino acid containing a thioether

Diphenyl disulfide, a representative disulfide


Perfluorooctanesulfonic acid, a controversial surfactant

Dibenzothiophene, a component of crude oil

Penicillin

Some of the main classes of sulfur-containing organic compounds include the


following:[42]

Thiols or mercaptans (as they are mercury capturers as chelators) are the sulfur
analogs of alcohols; treatment of thiols with base gives thiolate ions.
Thioethers are the sulfur analogs of ethers.
Sulfonium ions have three groups attached to a cationic sulfur
center. Dimethylsulfoniopropionate (DMSP) is one such compound, important
in the marine organic sulfur cycle.
Sulfoxides and sulfones are thioethers with one and two oxygen atoms attached
to the sulfur atom, respectively. The simplest sulfoxide, dimethyl sulfoxide, is a
common solvent; a common sulfone is sulfolane.
Sulfonic acids are used in many detergents.

Compounds with carbonsulfur multiple bonds are uncommon with the notable
exception of carbon disulfide, a volatile colorless liquid that is structurally similar to
carbon dioxide. It is used as a reagent to make the polymer rayon and many
organosulfur compounds. Unlike carbon monoxide, carbon monosulfide is only stable
as a dilute gas, as in the interstellar medium.[43]

Organosulfur compounds are responsible for some of the unpleasant odors of


decaying organic matter. They are used in the odoration of natural gas and cause the
odor of garlic and skunk spray. Not all organic sulfur compounds smell unpleasant at
all concentrations: the sulfur-containing monoterpenoid grapefruit mercaptan in small
concentrations is responsible for the characteristic scent of grapefruit, but has a
generic thiol odor at larger concentrations. Sulfur mustard, a potent vesicant,
was used in World War I as a disabling agent.[44]

Sulfur-sulfur bonds are a structural component to stiffen rubber, in a way similar to


the biological role of disulfide bridges to rigidify proteins (see biological below). In
the most common type of industrial "curing" or hardening and strengthening of
natural rubber, elemental sulfur is heated with the rubber to the point that chemical
reactions form disulfide bridges between isoprene units of the polymer. This process,
patented in 1843, allowed rubber to become a major industrial product, especially
automobile tires. Because of the heat and sulfur, the process was named vulcanization,
after the Roman god of the forge and volcanism.

History
Antiquity

Pharmaceutical container for sulfur from the first half of the 20th century. From
the Museo del Objeto del Objeto collection

Being abundantly available in native form, sulfur was known in ancient times and is
referred to in the Torah (Genesis). English translations of the Bible commonly
referred to burning sulfur as "brimstone", giving rise to the term "fire-and-
brimstone" sermons, in which listeners are reminded of the fate of eternal
damnation that await the unbelieving and unrepentant. It is from this part of the Bible
that Hell is implied to "smell of sulfur" (likely due to its association with volcanic
activity). According to the Ebers Papyrus, a sulfur ointment was used in
ancient Egypt to treat granular eyelids. Sulfur was used for fumigation in
preclassical Greece;[45] this is mentioned in the Odyssey.[46] Pliny the Elder discusses
sulfur in book 35 of his Natural History, saying that its best-known source is the
island of Melos. He mentions its use for fumigation, medicine, and bleaching cloth.[47]

A natural form of sulfur known as shiliuhuang was known in China since the 6th
century BC and found in Hanzhong.[48] By the 3rd century, the Chinese discovered that
sulfur could be extracted frompyrite.[48] Chinese Daoists were interested in sulfur's
flammability and its reactivity with certain metals, yet its earliest practical uses were
found in traditional Chinese medicine.[48] A Song dynastymilitary treatise of 1044 AD
described different formulas for Chinese black powder, which is a mixture
of potassium nitrate (KNO
3), charcoal, and sulfur.

Indian alchemists, practitioners of "the science of mercury" (sanskrit rasastra,


), wrote extensively about the use of sulfur in alchemical operations
with mercury, from the eighth century AD onwards.[49] In the rasastra tradition,
sulfur is called "the smelly" (sanskrit gandhaka, ).

Early European alchemists gave sulfur its own alchemical symbol, a triangle at the top
of a cross. In traditional skin treatment before the modern era of scientific medicine,
elemental sulfur was used, mainly in creams, to alleviate conditions such
as scabies, ringworm, psoriasis, eczema, and acne. The mechanism of action is
unknownthough elemental sulfur does oxidize slowly to sulfurous acid, which in
turn (through the action of sulfite) acts as a mild reducing and antibacterial
agent.[50][51][52]

Modern times

Sicilian kiln used to obtain sulfur from volcanic rock.

In 1777, Antoine Lavoisier helped convince the scientific community that sulfur was
an element, not a compound. Sulfur deposits in Sicily were the dominant supply
source for over half a century. Approximately 2000 tons per year of sulfur were
imported into Marseilles, France for the production of sulfuric acid via the Leblanc
process by the late 18th century. In industrializing Britain, with the repeal of tariffs on
salt in 1824, demand for sulfur from Sicily surged upward. The increasing British
control and exploitation of the mining, refining and transportation of the sulfur,
coupled with the failure of this lucrative export to transform Sicily's backward and
impoverished economy led to the 'Sulfur Crisis' of 1840, when King Ferdinand II gave
a monopoly of the sulfur industry to a French firm, violating an earlier 1816 trade
agreement with Britain. A peaceful negotiated solution was eventually mediated by
France.[53][54]

In 1867, sulfur was discovered in underground deposits in Louisiana and Texas. The
highly successful Frasch process was developed to extract this resource.[55]

In the late 18th century, furniture makers used molten sulfur to produce
decorative inlays in their craft. Because of the sulfur dioxide produced during the
process of melting sulfur, the craft of sulfur inlays was soon abandoned. Molten sulfur
is sometimes still used for setting steel bolts into drilled concrete holes where high
shock resistance is desired for floor-mounted equipment attachment points. Pure
powdered sulfur was used as a medicinal tonic and laxative.[25] With the advent of
the contact process, the majority of sulfur today is used to make sulfuric acid for a
wide range of uses, particularly fertilizer.[56]

Applications
Sulfuric acid

Elemental sulfur is mainly used as a precursor to other chemicals. Approximately


85% (1989) is converted to sulfuric acid (H2SO4):

2 S + 3 O2 + 2 H2O 2 H2SO4

Sulfuric acid production in 2000

Because of its importance, sulfuric acid was considered an excellent indicator of a


country's industrial well-being.[57] For example, with 32.5 million tonnes in 2010, the
United States produces more sulfuric acid every year than any other inorganic
industrial chemical.[34] The principal use for the acid is the extraction of phosphate ores
for the production of fertilizer manufacturing. Other applications of sulfuric acid
include oil refining, wastewater processing, and mineral extraction.[25]

Other large-scale sulfur chemicals


Sulfur reacts directly with methane to give carbon disulfide, which is used to
manufacture cellophane and rayon.[25] One of the direct uses of sulfur is
in vulcanization of rubber, where polysulfide chains crosslink organic
polymers. Sulfites are heavily used to bleach paper and as preservatives in dried fruit.
Many surfactants and detergents, e.g. sodium lauryl sulfate, are produced are sulfate
derivatives.Calcium sulfate, gypsum, (CaSO42H2O) is mined on the scale of 100
million tons each year for use in Portland cement and fertilizers.

When silver-based photography was widespread, sodium and


ammonium thiosulfate were widely used as "fixing agents." Sulfur is a component
of gunpowder.

Fertilizer

Sulfur is increasingly used as a component of fertilizers. The most important form of


sulfur for fertilizer is the mineral calcium sulfate. Elemental sulfur
is hydrophobic (that is, it is not soluble in water) and, therefore, cannot be directly
utilized by plants. Over time, soil bacteria can convert it to soluble derivatives, which
can then be utilized by plants. Sulfur improves the use efficiency of other essential
plant nutrients, particularly nitrogen and phosphorus.[58] Biologically produced sulfur
particles are naturally hydrophilic due to a biopolymer coating. This sulfur is,
therefore, easier to disperse over the land (via spraying as a diluted slurry), and results
in a faster release.

Plant requirements for sulfur are equal to or exceed those for phosphorus. It is one of
the major nutrients essential for plant growth, root nodule formation of legumes and
plants protection mechanisms. Sulfur deficiency has become widespread in many
countries in Europe.[59][60][61] Because atmospheric inputs of sulfur continue to decrease,
the deficit in the sulfur input/output is likely to increase, unless sulfur fertilizers are
used.

Fine chemicals

A molecular model of the pesticide malathion.


Organosulfur compounds are used in pharmaceuticals, dyestuffs, and agrochemicals.
Many drugs contain sulfur, early examples being antibacterial sulfonamides, known
as sulfa drugs. Sulfur is a part of many bacterial defense molecules. Most -
lactam antibiotics, including the penicillins, cephalosporins and monolactams contain
sulfur.[42]

Magnesium sulfate, known as Epsom salts when in hydrated crystal form, can be used
as a laxative, a bath additive, an exfoliant, magnesium supplement for plants, or
(when in dehydrated form) as adesiccant.

Fungicide and pesticide

Sulfur candle originally sold for home fumigation

Elemental sulfur is one of the oldest fungicides and pesticides. "Dusting sulfur,"
elemental sulfur in powdered form, is a common fungicide for grapes, strawberry,
many vegetables and several other crops. It has a good efficacy against a wide range
of powdery mildew diseases as well as black spot. In organic production, sulfur is the
most important fungicide. It is the only fungicide used inorganically farmed apple
production against the main disease apple scab under colder conditions. Biosulfur
(biologically produced elemental sulfur with hydrophilic characteristics) can be used
well for these applications.

Standard-formulation dusting sulfur is applied to crops with a sulfur duster or from a


dusting plane. Wettable sulfur is the commercial name for dusting sulfur formulated
with additional ingredients to make it water miscible.[62][63] It has similar applications
and is used as a fungicide against mildew and other mold-related problems with plants
and soil.
Elemental sulfur powder is used as an "organic" (i.e. "green") insecticide (actually
an acaricide) against ticks and mites. A common method of use is to dust clothing or
limbs with sulfur powder.

Diluted solutions of lime sulfur (made by combining calcium hydroxide with


elemental sulfur in water), are used as a dip for pets to destroy ringworm
(fungus), mange and other dermatoses and parasites. Sulfur candles consist of almost
pure sulfur in blocks or pellets that are burned to fumigate structures. It is no longer
used in the home due to the toxicity of the products of combustion.

Bactericide in winemaking and food preservation

Small amounts of sulfur dioxide gas addition (or equivalent potassium


metabisulfite addition) to fermented wine to produce traces of sulfurous
acid (produced when SO2 reacts with water) and its sulfitesalts in the mixture, has
been called "the most powerful tool in winemaking."[64] After the yeast-fermentation
stage in winemaking, sulfites absorb oxygen and inhibit aerobic bacterial growth that
otherwise would turn ethanol into acetic acid, souring the wine. Without this
preservative step, indefinite refrigeration of the product before consumption is usually
required. Similar methods go back into antiquity but modern historical mentions of
the practice go to the fifteenth century. The practice is used by large industrial wine
producers and small organic wine producers alike.

Sulfur dioxide and various sulfites have been used for their antioxidant antibacterial
preservative properties in many other parts of the food industry also. The practice has
declined since reports of an allergy-like reaction of some persons to sulfites in foods.

Pharmaceutical use

Sulfur is used in pharmaceutical skin preparations for the treatment of acne and other
conditions. it acts as a keratolytic agent and also kills bacteria, fungi, scabies mites
and other parasites.[65]Precipitated sulfur and colloidal sulfur are used, in form
of lotions, creams, powders, soaps, and bath additives, for the treatment of acne
vulgaris, acne rosacea, and seborrhoeic dermatitis.[66]

Biological role
Protein and organic cofactors

Sulfur is an essential component of all living cells. It is the seventh or eighth most
abundant element in the human body by weight, being about as common
as potassium, and a little more common than sodium or chlorine. A 70 kg (150 lb)
human body contains about 140 grams of sulfur.

In plants and animals, the amino acids cysteine and methionine contain most of the
sulfur. The element is thus present in all polypeptides, proteins, and enzymes that
contain these amino acids. In humans, methionine is an essential amino acid that must
be ingested. However, save for the vitamins biotin and thiamine, cysteine and all
sulfur-containing compounds in the human body can be synthesized from methionine.
The enzyme sulfite oxidase is needed for the metabolism of methionine and cysteine
in humans and animals.

Disulfide bonds (S-S bonds) formed between cysteine residues in peptide chains are
very important in protein assembly and structure. These covalent bonds between
peptide chains confer extra toughness and rigidity.[67] For example, the high strength of
feathers and hair is in part due to their high content of S-S bonds and their high
content of cysteine and sulfur. Eggs are high in sulfur because large amounts of the
element are necessary for feather formation, and the characteristic odor of rotting eggs
is due to hydrogen sulfide. The high disulfide bond content of hair and feathers
contributes to their indigestibility and to their characteristic disagreeable odor when
burned.

Homocysteine and taurine are other sulfur-containing acids that are similar in
structure, but not coded by DNA, and are not part of the primary structure of proteins.
Many important cellular enzymes use prosthetic groups ending with -SH moieties to
handle reactions involving acyl-containing biochemicals: two common examples from
basic metabolism are coenzyme A and alpha-lipoic acid.[67] Two of the 13 classical
vitamins, biotin and thiamine contain sulfur, with the latter being named for its sulfur
content. Sulfur plays an important part, as a carrier of reducing hydrogen and its
electrons, for cellular repair of oxidation. Reduced glutathione, a sulfur-containing
tripeptide, is a reducing agent through its sulfhydryl (-SH) moiety derived
from cysteine. The thioredoxins, a class of small protein essential to all known life,
using neighboring pairs of reduced cysteines to act as general protein reducing agents,
to similar effect.

Methanogenesis, the route to most of the world's methane, is a multistep biochemical


transformation of carbon dioxide. This conversion requires several organosulfur
cofactors. These include coenzyme M, CH3SCH2CH2SO3, the immediate precursor
to methane.[68]

Metalloproteins and inorganic cofactors


Inorganic sulfur forms a part of iron-sulfur clusters as well as many copper, nickel,
and iron proteins. Most pervasive are the ferrodoxins, which serve as electron shuttles
in cells. In bacteria, the important nitrogenase enzymes contains an Fe-Mo-S cluster,
is a catalyst that performs the important function of nitrogen fixation, converting
atmospheric nitrogen to ammonia that can be used by microorganisms and plants to
make proteins, DNA, RNA, alkaloids, and the other organic nitrogen compounds
necessary for life.[69]

Sulfur metabolism and the sulfur cycle

Main articles: Sulfur metabolism and Sulfur cycle

The sulfur cycle was the first of the biogeochemical cycles to be discovered. In the
1880s, while studying Beggiatoa (a bacterium living in a sulfur rich
environment), Sergei Winogradsky found that it oxidized hydrogen sulfide (H2S) as an
energy source, forming intracellular sulfur droplets. Winogradsky referred to this form
of metabolism as inorgoxidation (oxidation of inorganic compounds). He continued to
study it together with Selman Waksman until the 1950s.

Sulfur oxidizers can use as energy sources reduced sulfur compounds, including
hydrogen sulfide, elemental sulfur, sulfite, thiosulfate, and various polythionates
(e.g., tetrathionate).[70] They depend on enzymes such as sulfur oxygenase and sulfite
oxidase to oxidize sulfur to sulfate. Some lithotrophs can even use the energy
contained in sulfur compounds to produce sugars, a process known aschemosynthesis.
Some bacteria and archaea use hydrogen sulfide in place of water as the electron
donor in chemosynthesis, a process similar to photosynthesis that produces sugars and
utilizes oxygen as the electron acceptor. The photosynthetic green sulfur
bacteria and purple sulfur bacteria and some lithotrophs use elemental oxygen to carry
out such oxidization of hydrogen sulfide to produce elemental sulfur (S 0), oxidation
state = 0. Primitive bacteria that live around deep ocean volcanic vents oxidize
hydrogen sulfide in this way with oxygen; see giant tube worm for an example of
large organisms that use hydrogen sulfide (via bacteria) as food to be oxidized.

The so-called sulfate-reducing bacteria, by contrast, "breathe sulfate" instead of


oxygen. They use organic compounds or molecular hydrogen as the energy source.
They use sulfur as the electron acceptor, and reduce various oxidized sulfur
compounds back into sulfide, often into hydrogen sulfide. They can grow on a number
of other partially oxidized sulfur compounds (e.g. thiosulfates, thionates, polysulfides,
sulfites). The hydrogen sulfide produced by these bacteria is responsible for some of
the smell of intestinal gases (flatus) and decomposition products.

Sulfur is absorbed by plants via the roots from soil as the sulfate and transported as a
phosphate ester. Sulfate is reduced to sulfide via sulfite before it is incorporated
into cysteine and other organosulfur compounds.[71]

SO42 SO32 H2S cysteine methionine

Precautions

Effect of acid rain on a forest, Jizera Mountains, Czech Republic

Elemental sulfur is non-toxic, as generally are the soluble sulfate salts, such as Epsom
salts. Soluble sulfate salts are poorly absorbed and laxative. However, when injected
parenterally, they are freely filtered by the kidneys and eliminated with very little
toxicity in multi-gram amounts.

When sulfur burns in air, it produces sulfur dioxide. In water, this gas produces
sulfurous acid and sulfites, which are antioxidants that inhibit growth of aerobic
bacteria and allow its use as a food additive in small amounts. However, at high
concentrations these acids harm the lungs, eyes or other tissues. In organisms without
lungs such as insects or plants, it otherwise prevents respiration in high
concentrations. Sulfur trioxide (made by catalysis from sulfur dioxide) and sulfuric
acid are similarly highly corrosive, due to the strong acids that form on contact with
water.

The burning of coal and/or petroleum by industry and power plants generates sulfur
dioxide (SO2), which reacts with atmospheric water and oxygen to produce sulfuric
acid (H2SO4) and sulfurous acid(H2SO3). These acids are components of acid rain,
which lower the pH of soil and freshwater bodies, sometimes resulting in substantial
damage to the environment and chemical weathering of statues and structures. Fuel
standards increasingly require that fuel producers extract sulfur from fossil fuels to
prevent acid rain formation. This extracted and refined sulfur represents a large
portion of sulfur production. In coal-fired power plants, flue gases are sometimes
purified. More modern power plants that use synthesis gas extract the sulfur before
they burn the gas.

Hydrogen sulfide is as toxic as hydrogen cyanide, and kills by the same mechanism
(inhibition of the respiratory enzyme cytochrome oxidase),[72] though hydrogen sulfide
is less likely to cause surprise poisonings from small inhaled amounts, because of its
disagreeable warning odor. However, hydrogen sulfide quickly deadens the sense of
smell-so a victim may breathe increasing quantities and be unaware of its presence
until severe symptoms occur, which can quickly lead to death.
Dissolved sulfide and hydrosulfide salts are also toxic by the same mechanism.

Chlorine
From Wikipedia, the free encyclopedia
Jump to: navigation, search
This article is about the chemical element. For the bleach, see Sodium hypochlorite.
For the film, see Chlorine (film).
"Cl" and "Cl2" redirect here. For other uses, see CL and CL2.

Chlorine, Cl 17

A glass container filled with chlorine gas

Emission line spectra; 400700 nm

General properties

Name, symbol chlorine, Cl


Appearance pale yellow-green gas

Pronunciation /klrin/ or /klrn/


KLOHR-een or KLOHR-n

Chlorine in the periodic table

F

Cl

Br

sulfur chlorine argon

Atomic number 17

Standard atomic weight (Ar) 35.45[1] (35.44635.457)[2]

Element category diatomic nonmetal

Group, block group 17 (halogens), p-block

Period period 3

Electron configuration [Ne] 3s2 3p5

per shell 2, 8, 7

Physical properties

Phase gas

Melting point 171.6 K (101.5 C, 150.7 F)

Boiling point 239.11 K (34.04 C, 29.27 F)

Density at stp (0 C and 101.325 kPa) 3.2 g/L


when liquid, at b.p. 1.5625 g/cm3[3]

Critical point 416.9 K, 7.991 MPa

Heat of fusion (Cl2) 6.406 kJ/mol

Heat of vaporization (Cl2) 20.41 kJ/mol

Molar heat capacity (Cl2)


33.949 J/(molK)

vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 128 139 153 170 197 239

Atomic properties

Oxidation states 7, 6, 5, 4, 3, 2, 1, 1 (a
strongly acidic oxide)

Electronegativity Pauling scale: 3.16

Ionization energies 1st: 1251.2 kJ/mol


2nd: 2298 kJ/mol
3rd: 3822 kJ/mol
(more)

Covalent radius 1024 pm

Van der Waals radius 175 pm

Miscellanea

Crystal structure orthorhombic


Speed of sound 206 m/s (gas, at 0 C)

Thermal conductivity 8.9103 W/(mK)

Electrical resistivity >10 m (at 20 C)


Magnetic ordering diamagnetic[4]
CAS Registry Number 7782-50-5

History
Discovery and first isolation Carl Wilhelm Scheele(1774)
Recognized as anelement by Humphry Davy (1808)

Most stable isotopes

Main article: Isotopes of chlorine


iso NA half-life DM DE (MeV) DP
35
Cl 75.77%35Cl is stable with 18 neutrons
0.709 36
Ar
36
Cl trace 3.01105 y
36
S
37
Cl 24.23% Cl is stable with 20 neutrons
37

references

Chlorine is a chemical element with symbol Cl and atomic number 17. Chlorine is in
the halogen group (17) and is the second lightest halogen following fluorine. The
element is a yellow-green gas under standard conditions, where it forms diatomic
molecules. Chlorine has the highest electron affinity and the third
highest electronegativity of all the reactive elements. For this reason, chlorine is a
strong oxidizing agent. Free chlorine is rare on Earth, and is usually a result of direct
or indirect oxidation by oxygen.

The most common compound of chlorine, sodium chloride (common salt), has been
known since ancient times. Around 1630, chlorine gas was first synthesized in a
chemical reaction, but not recognized as a fundamentally important substance.
Characterization of chlorine gas was made in 1774 byCarl Wilhelm Scheele, who
supposed it to be an oxide of a new element. In 1809, chemists suggested that the gas
might be a pure element, and this was confirmed by Sir Humphry Davy in 1810, who
named it from Ancient Greek: (khlros) "pale green".

Nearly all chlorine in the Earth's crust occurs as chloride in various ionic compounds,
including table salt. It is the second most abundant halogen and 21st most abundant
chemical element in Earth's crust. Elemental chlorine is commercially produced
from brine by electrolysis. The high oxidizing potential of elemental chlorine led
commercially to free chlorine's bleaching and disinfectant uses, as well as its many
uses of an essential reagent in the chemical industry. Chlorine is used in the
manufacture of a wide range of consumer products, about two-thirds of them organic
chemicals such aspolyvinyl chloride, as well as many intermediates for production
of plastics and other end products which do not contain the element. As a common
disinfectant, elemental chlorine and chlorine-generating compounds are used more
directly in swimming pools to keep them clean and sanitary.

In the form of chloride ions, chlorine is necessary to all known species of life. Other
types of chlorine compounds are rare in living organisms, and artificially produced
chlorinated organics range from inert to toxic. In the upper atmosphere, chlorine-
containing organic molecules such aschlorofluorocarbons have been implicated
in ozone depletion. Small quantities of elemental chlorine are generated by oxidation
of chloride tohypochlorite in neutrophils, as part of the immune response against
bacteria. Elemental chlorine at high concentrations is extremely dangerous
andpoisonous for all living organisms, and was used in World War I as the first
gaseous chemical warfare agent.

Contents
[hide]

1 Characteristics
o 1.1 Physical characteristics of chlorine and its compounds
o 1.2 Chemical characteristics
1.2.1 Hydrolysis of free chlorine or disproportionation in water
1.2.2 Chemistry and compounds
1.2.2.1 Chlorides
1.2.2.2 Chlorine oxides
1.2.2.3 Interhalogen compounds
1.2.2.4 Organochlorine compounds
o 1.3 Occurrence
o 1.4 Isotopes
2 History
3 Production
o 3.1 Laboratory methods
4 Applications
o 4.1 Production of industrial and consumer products
o 4.2 Public sanitation, disinfection, and antisepsis
4.2.1 Combating putrefaction
4.2.2 Against infection and contagion
4.2.3 Semmelweis and experiments with antisepsis
4.2.4 Public sanitation
o 4.3 Use as a weapon
4.3.1 World War I
4.3.2 Iraq War
4.3.3 Syrian Civil War
4.3.4 Islamic State of Iraq and the Levant (ISIL/ISIS)
5 Health effects of the free element and hazards
o 5.1 Chlorine induced cracking in structural materials
o 5.2 Chlorine-iron fire
6 Organochlorine compounds as pollutants
7 See also
8 References
9 Bibliography
10 External links

Characteristics
Physical characteristics of chlorine and its compounds

Chlorine, liquefied under a pressure of 7.4 bar at room temperature, displayed in a


quartz ampule embedded in acrylic glass.
At standard temperature and pressure, two chlorine atoms form the diatomic
molecule Cl2.[5] This is a yellow-green gas that has a distinctive strong odor, familiar to
most from common household bleach.[6] The bonding between the two atoms is
relatively weak (only 242.580 0.004 kJ/mol), which makes the Cl2 molecule highly
reactive. The boiling point at standard pressure is around 34 C, but it can be
liquefied at room temperature with pressures above 740 kPa (107 psi).[7]

Although elemental chlorine is yellow-green, the chloride ion, in common with


other halide ions, has no color in either minerals or solutions (example, table salt).
Similarly, (again as with other halogens) chlorine atoms impart no color to organic
chlorides when they replace hydrogen atoms in colorless organic compounds, such
as tetrachloromethane. The melting point and density of these compounds is increased
by substitution of hydrogen in place of chlorine. Compounds of chlorine with other
halogens, however, as well as many chlorine oxides, are visibly colored.

Chemical characteristics

Along with fluorine, bromine, iodine, and astatine, chlorine is a member of


the halogen series that forms the group 17 (formerly VII, VIIA, or VIIB) of the
periodic table. Chlorine forms compounds with almost all of the elements to give
compounds that are usually called chlorides. Chlorine gas reacts with most organic
compounds, and will even sluggishly support the combustion of hydrocarbons.[8]

Hydrolysis of free chlorine or disproportionation in water

At 25 C and atmospheric pressure, one liter of water dissolves 3.26 g or 1.125 L of


gaseous chlorine.[9] Solutions of chlorine in water contain chlorine (Cl2), hydrochloric
acid, and hypochlorous acid:

Cl2 + H2O HCl + HClO

This conversion to the right is called disproportionation, because the ingredient


chlorine both increases and decreases in formal oxidation state. The solubility of
chlorine in water is increased if the water contains dissolved alkali hydroxide, and in
this way, chlorine bleach is produced.[10]

Cl2 + 2 OH ClO + Cl + H2O

Chlorine gas only exists in a neutral or acidic solution.

Chemistry and compounds

See also: Category:Chlorine compounds.


Chlorine exists in all odd numbered oxidation states from 1 to +7, as well as the
elemental state of zero and four in chlorine dioxide (see table below, and also
structures in chlorite).[11] Chlorine typically has a 1 oxidation state in compounds,
except for compounds containing fluorine, oxygen and nitrogen, all of which are even
more electronegative than chlorine. Progressing through the states, hydrochloric acid
can be oxidized using manganese dioxide, or hydrogen chloride gas oxidized
catalytically by air to form elemental chlorine gas.[12]

Oxidation
Name Formula Characteristic compounds
state
1 chlorides Cl ionic chlorides, organic chlorides, hydrochloric acid
0 chlorine Cl2 elemental chlorine
sodium hypochlorite, calcium hypochlorite, dichlorine
+1 hypochlorites ClO
monoxide
+3 chlorites ClO sodium chlorite
2

+4 chlorine(IV) ClO chlorine dioxide


2
ClO potassium chlorate, chloric acid, dichloryl trisulfate
+5 chloryl, chlorates 3 ClO+
[ClO2]2[S3O10].
2
dichlorine hexoxide (gas). In liquid or solid
disproportionates to mix of +5 and +7 oxidation states, as
Cl ionic chloryl perchlorate [ClO
+6 chlorine(VI) 2O 2] +
6 [ClO
4]

ClO perchloric acid, perchlorate salts such as magnesium


+7 perchlorates
4 perchlorate, dichlorine heptoxide

Chlorides

Main article: Chloride

Chlorine combines with almost all elements to give chlorides. Compounds


with oxygen, nitrogen, xenon, and krypton are known, but do not form by direct
reaction of the elements.[13] Chloride is one of the most common anions in
nature. Hydrogen chloride and its aqueous solution, hydrochloric acid, are produced
on megaton scale annually both as valued intermediates but sometimes as undesirable
pollutants.
Chlorine oxides
Chlorine forms a variety of oxides, as seen above: chlorine dioxide (ClO2), dichlorine
monoxide (Cl2O), dichlorine hexoxide (Cl2O6), dichlorine heptoxide (Cl2O7). The
anionic derivatives of these same oxides are also well known including chlorate (ClO
3), chlorite (ClO
2), hypochlorite (ClO), and perchlorate (ClO
4). The acid derivatives of these anions are hypochlorous acid (HOCl), chloric
acid(HClO3) and perchloric acid (HClO4). The chloroxy cation chloryl (ClO2+) is
known and has the same structure as chlorite but with a positive charge and chlorine
in the +5 oxidation state.[14] The compound "chlorine trioxide" does not occur, but
rather in gas form is found as the dimeric dichlorine hexoxide (Cl2O6) with a +6
oxidation state. This compound in liquid or solid form disproportionates to a mixture
of +5 and +7 oxidation states, occurring as the ionic compound chloryl
perchlorate, [ClO
2]+
[ClO
4]
.[15]

In hot concentrated alkali solution hypochlorite disproportionates:

2 ClO Cl + ClO
2
ClO + ClO
2 Cl + ClO
3

Sodium chlorate and potassium chlorate can be crystallized from solutions formed by
the above reactions. If their crystals are heated to a high temperature, they undergo a
further, final disproportionation:

4 ClO
3 Cl + 3 ClO
4

This same progression from chloride to perchlorate can be accomplished


by electrolysis. The anode reaction progression is:[16]

Electrode
Reaction
potential
Cl + 2 OH ClO + H2O + 2 e +0.89 volts

ClO + 2 OH ClO
+0.67 volts
2 + H2O + 2 e
ClO
2 + 2 OH ClO +0.33 volts
3 + H2O + 2 e
ClO
3 + 2 OH ClO +0.35 volts
4 + H2O + 2 e

Each step is accompanied at the cathode by

2 H2O + 2 e 2 OH + H2 (0.83 volts)


Interhalogen compounds

Chlorine oxidizes bromide and iodide salts to bromine and iodine, respectively.
However, it cannot oxidize fluoride salts to fluorine. It makes a variety
of interhalogen compounds, such as the chlorine fluorides, chlorine
monofluoride (ClF), chlorine trifluoride (ClF
3), chlorine pentafluoride (ClF
5). Chlorides of bromine and iodine are also known.[17]

Organochlorine compounds

Main article: Organochloride

Chlorine is used extensively in organic chemistry in substitution and addition


reactions. Chlorine often imparts many desired properties to an organic compound, in
part owing to its electronegativity.

Like the other halides, chlorine undergoes electrophilic addition reactions, the most
notable one being the chlorination of alkenes and aromatic compounds with a Lewis
acid catalyst. Organic chlorine compounds tend to be less reactive in nucleophilic
substitution reactions than the corresponding bromine or iodine derivatives, but they
tend to be cheaper. They may be activated for reaction by substituting with
a tosylate group, or by the use of a catalytic amount of sodium iodide.[citation needed]

Occurrence

See also: Category:Halide minerals.

Essentially no chlorine was created in the Big Bang. Chlorine in the universe is
created and distributed through the interstellar medium from creation in supernovae,
via the r-process.[18] This chlorine provides the supply found in the Solar System.
In meteorites and on Earth, chlorine is found primarily as the chloride ion which
occurs in minerals. In the Earth's crust, chlorine is present at average concentrations of
about 126 parts per million,[19]predominantly in such minerals as halite (sodium
chloride), sylvite (potassium chloride), and carnallite (potassium magnesium chloride
hexahydrate).

Chloride is a component of the salt that is deposited in the earth or dissolved in


the oceans about 1.9% of the mass of seawater is chloride ions. Even higher
concentrations of chloride are found in theDead Sea and in
underground brine deposits. Most chloride salts are soluble in water, thus, chloride-
containing minerals are usually only found in abundance in dry climates or deep
underground.

Over 2000 naturally occurring organic chlorine compounds are known.[20]

Isotopes

Main article: Isotopes of chlorine

Chlorine has a wide range of isotopes. The two stable isotopes are 35Cl (75.77%)
and 37Cl (24.23%).[21] Together they give chlorine an atomic weight of 35.4527 g/mol.
The half-integer value for chlorine's weight caused some confusion in the early days
of chemistry, when it had been postulated that atoms were composed of even units of
hydrogen (see Proust's law), and the existence of chemicalisotopes was unsuspected.[22]

Trace amounts of radioactive 36Cl exist in the environment, in a ratio of about


7x1013 to 1 with stable isotopes. 36Cl is produced in the atmosphere
by spallation of 36Ar by interactions with cosmic rayprotons. In the subsurface
environment, 36Cl is generated primarily as a result of neutron capture by 35Cl or muon
capture by 40Ca. 36Cl decays to 36S and to 36Ar, with a combined half-life of 308,000
years. The half-life of this isotope makes it suitable for geologic dating in the range of
60,000 to 1 million years. Additionally, large amounts of 36Cl were produced by
irradiation of seawater during atmospheric detonations of nuclear weapons between
1952 and 1958. The residence time of 36Cl in the atmosphere is about 1 week. Thus, as
an event marker of 1950s water in soil and groundwater, 36Cl is also useful for dating
waters less than 50 years before the present. 36Cl has seen use in other areas of the
geological sciences, including dating ice and sediments.[21]

History
The most common compound of chlorine, sodium chloride, has been known since
ancient times; archaeologists have found evidence that rock salt was used as early as
3000 BC and brine as early as 6000 BC.[23] Around 1630, chlorine was recognized as a
gas by the Flemish chemist and physician Jan Baptist van Helmont.[24]

Carl Wilhelm Scheele

Elemental chlorine was first prepared and studied in 1774 by Swedish chemist Carl
Wilhelm Scheele, and, therefore, he is credited for its discovery.[25] He called it
"dephlogisticated muriatic acid air" since it is a gas (then called "airs") and it came
from hydrochloric acid (then known as "muriatic acid").[25] However, he failed to
establish chlorine as an element, mistakenly thinking that it was the oxideobtained
from the hydrochloric acid (see phlogiston theory).[25] He named the new element
within this oxide as muriaticum.[25] Regardless of what he thought, Scheele did isolate
chlorine by reactingMnO2 (as the mineral pyrolusite) with HCl:[24]

4 HCl + MnO2 MnCl2 + 2 H2O + Cl2

Scheele observed several of the properties of chlorine: the bleaching effect on litmus,
the deadly effect on insects, the yellow green color, and the smell similar to aqua
regia.[26]

At the time, common chemical theory was: any acid is a compound that contains
oxygen (still sounding in the German and Dutch names
of oxygen: sauerstoff or zuurstof, both translating into English asacid substance), so a
number of chemists, including Claude Berthollet, suggested that
Scheele's dephlogisticated muriatic acid air must be a combination of oxygen and the
yet undiscovered element,muriaticum.[27][28][29]

In 1809, Joseph Louis Gay-Lussac and Louis-Jacques Thnard tried to


decompose dephlogisticated muriatic acid air by reacting it with charcoal to release
the free element muriaticum (and carbon dioxide).[25] They did not succeed and
published a report in which they considered the possibility that dephlogisticated
muriatic acid air is an element, but were not convinced.[30]
In 1810, Sir Humphry Davy tried the same experiment again, and concluded that it is
an element, and not a compound.[25] He named this new element as chlorine, from the
Greek word (chlros), meaning green-yellow.[31] The name "halogen",
meaning "salt producer", was originally used for chlorine in 1811 by Johann Salomo
Christoph Schweigger. However, this term was later used as a generic term to
describe all the elements in the chlorine family (fluorine, bromine, iodine), after a
suggestion by Jns Jakob Berzelius in 1842.[32][33] In 1823, Michael Faraday liquefied
chlorine for the first time,[34][35] and demonstrated that what was then known as "solid
chlorine" had a structure of chlorine hydrate (Cl2H2O).[24]

Chlorine gas was first used by French chemist Claude Berthollet to bleach textiles in
1785.[36][37] Modern bleaches resulted from further work by Berthollet, who first
produced sodium hypochlorite in 1789 in his laboratory in the town of Javel (now part
of Paris, France), by passing chlorine gas through a solution of sodium carbonate. The
resulting liquid, known as "Eau de Javel" ("Javel water"), was a weak solution
of sodium hypochlorite. However, this process was not very efficient, and alternative
production methods were sought. Scottish chemist and industrialist Charles
Tennant first produced a solution of calcium hypochlorite ("chlorinated lime"), then
solid calcium hypochlorite (bleaching powder).[36] These compounds produced low
levels of elemental chlorine, and could be more efficiently transported than sodium
hypochlorite, which remained as dilute solutions because when purified to eliminate
water, it became a dangerously powerful and unstable oxidizer. Near the end of the
nineteenth century, E. S. Smith patented a method of sodium hypochlorite production
involving electrolysis of brine to produce sodium hydroxide and chlorine gas, which
then mixed to form sodium hypochlorite.[38] This is known as the chloralkali process,
first introduced on an industrial scale in 1892, and now the source of essentially all
modern elemental chlorine and sodium hydroxide production (a related low-
temperature electrolysis reaction, the Hooker process, is now responsible for bleach
and sodium hypochlorite production).

Elemental chlorine solutions dissolved in chemically basic water (sodium and calcium
hypochlorite) were first used as anti-putrification agents and disinfectants in the
1820s, in France, long before the establishment of the germ theory of disease. This
work is mainly due to Antoine-Germain Labarraque, who adapted Berthollet's "Javel
water" bleach and other chlorine preparations for the purpose (for a more complete
history, see below). Elemental chlorine has since served a continuous function in
topical antisepsis (wound irrigation solutions and the like) as well as public sanitation
(especially of swimming and drinking water).

In 1826, silver chloride was used to produce photographic images for the first
time.[39] Chloroform was first used as an anesthetic in 1847.[39]
Polyvinyl chloride (PVC) was invented in 1912, initially without a purpose.[39]

Chlorine gas was first introduced as a weapon on April 22, 1915, at Ypres by
the German Army,[40][41] and the results of this weapon were disastrous because gas
masks had not been mass distributed and were tricky to get on quickly.

Production

Liquid chlorine analysis


Main articles: Chlorine production and Chloralkali process

In industry, elemental chlorine is usually produced by the electrolysis of sodium


chloride dissolved in water. This method, the chloralkali process industrialized in
1892, now provides essentially all industrial chlorine gas.[42] Along with chlorine, the
method yields hydrogen gas and sodium hydroxide (with sodium hydroxide actually
being the most crucial of the three industrial products produced by the process). The
process proceeds according to the following chemical equation:[12]

2 NaCl + 2 H2O Cl2 + H2 + 2 NaOH

The electrolysis of chloride solutions all proceed according to the following


equations:

Cathode: 2 H+(aq) + 2 e H2(g)


Anode: 2 Cl(aq) Cl2(g) + 2 e

Overall process: 2 NaCl (or KCl) + 2 H2O Cl2 + H2 + 2 NaOH (or KOH)

In diaphragm cell electrolysis, an asbestos (or polymer-fiber) diaphragm separates a


cathode and an anode, preventing the chlorine forming at the anode from re-mixing
with the sodium hydroxide and the hydrogen formed at the cathode.[43] The salt
solution (brine) is continuously fed to the anode compartment and flows through the
diaphragm to the cathode compartment, where the caustic alkali is produced and the
brine is partially depleted. Diaphragm methods produce dilute and slightly impure
alkali but they are not burdened with the problem of preventing mercury discharge
into the environment and they are more energy efficient. Membrane cell electrolysis
employ permeable membrane as an ion exchanger. Saturated sodium (or potassium)
chloride solution is passed through the anode compartment, leaving at a
lower concentration.[44] This method is more efficient than the diaphragm cell and
produces very pure sodium (or potassium) hydroxide at about 32% concentration, but
requires very pure brine.

Membrane cell process for chloralkali production

Laboratory methods

Small amounts of chlorine gas can be made in the laboratory by combining


hydrochloric acid and manganese dioxide. Alternatively a strong acid such as sulfuric
acid or hydrochloric acid reacts withsodium hypochlorite solution to release chlorine
gas but reacts with sodium chlorate to produce chlorine gas and chlorine dioxide gas
as well. In the home, accidents occur when hypochlorite bleach solutions are
combined with certain acidic drain-cleaners.
Applications
Production of industrial and consumer products

Principal applications of chlorine are in the production of a wide range of industrial


and consumer products.[45][46] For example, it is used in making plastics, solvents for dry
cleaning and metal degreasing, textiles, agrochemicals and pharmaceuticals,
insecticides, dyestuffs, household cleaning products, etc.

Many important industrial products are produced via organochlorine intermediates.


Examples
include polycarbonates, polyurethanes, silicones, polytetrafluoroethylene, carboxymet
hyl cellulose, andpropylene oxide. Like the other halogens, chlorine participates
in free-radical substitution reactions with hydrogen-containing organic compounds.
When applied to organic substrates, reaction is oftenbut not invariablynon-
regioselective, and, hence, may result in a mixture of isomeric products. It is often
difficult to control the degree of substitution as well, so multiple substitutions are
common. If the different reaction products are easily separated, e.g., by distillation,
substitutive free-radical chlorination (in some cases accompanied by concurrent
thermal dehydrochlorination) may be a useful synthetic route. Industrial examples of
this are the production of methyl chloride, methylene chloride, chloroform,
and carbon tetrachloride from methane, allyl chloride from propylene,
andtrichloroethylene, and tetrachloroethylene from 1,2-dichloroethane.

Quantitatively, about 63% and 18% of all elemental chlorine produced is used in the
manufacture of organic and inorganic chlorine compounds, respectively. [42] About
15,000 chlorine compounds are being used commercially.[26] The remaining 19% is
used for bleaches and disinfection products.[42] The most significant of organic
compounds in terms of production volume are 1,2-dichloroethane andvinyl chloride,
intermediates in the production of PVC. Other particularly important organochlorines
are methyl chloride, methylene chloride, chloroform, vinylidene
chloride, trichloroethylene,perchloroethylene, allyl
chloride, epichlorohydrin, chlorobenzene, dichlorobenzenes, and trichlorobenzenes.
The major inorganic compounds include HCl, Cl2O, HOCl, NaClO3, chlorinated
isocyanurates, AlCl3, SiCl4, SnCl4, PCl3, PCl5, POCl3, AsCl3, SbCl3, SbCl5, BiCl3, S2Cl2,
SCl2, SOCI2, ClF3, ICl, ICl3, TiCl3, TiCl4, MoCl5, FeCl3, ZnCl2, etc.[42][47]

Pulp bleaching was done often with elemental chlorine in the past. However, this
tends to produce organochlorine pollution, and today environmental laws make it
prohibitive. Chlorine is used either inchlorine dioxide and sodium hypochlorite stages
in elemental chlorine free (ECF) bleaching, or not at all (total chlorine free or TCF
bleaching).

Public sanitation, disinfection, and antisepsis

Main articles: Water chlorination, Bleach and Antoine Labarraque

Combating putrefaction

Antoine-Germain Labarraque

In France (as elsewhere) there was a need to process animal guts in order to make
musical instrument strings, Goldbeater's skin and other products. This was carried out
in "gut factories" (boyauderies) as an odiferous and unhealthy business. In or about
1820, the Socit d'encouragement pour l'industrie nationale offered a prize for the
discovery of a method, chemical or mechanical, that could be used to separate the
peritoneal membrane of animal intestines without causing putrefaction. [48][49] It was won
by Antoine-Germain Labarraque, a 44-year-old French chemist and pharmacist who
had discovered that Berthollet's chlorinated bleaching solutions ("Eau de Javel") not
only destroyed the smell of putrefaction of animal tissue decomposition, but also
retarded the decomposition process itself.[49][50]

Labarraque's research resulted in chlorides and hypochlorites of lime (calcium


hypochlorite) and of sodium (sodium hypochlorite) being employed not only in
the boyauderies but also for the routine disinfection and deodorisation
of latrines, sewers, markets, abattoirs, anatomical theatres and morgues.[51] They were
also used, with success, in hospitals, lazarets, prisons, infirmaries (both on land and at
sea), magnaneries, stables, cattle-sheds, etc.; and for exhumations,[52] embalming,
during outbreaks of epidemic illness, fever, blackleg in cattle, etc.[48]
Against infection and contagion

Labarraque's chlorinated lime and soda solutions have been advocated since 1828 to
prevent infection (called "contagious infection", and presumed to be transmitted by
"miasmas") and also to treatputrefaction of existing wounds, including septic
wounds.[53] In this 1828 work, Labarraque recommended for the doctor to breathe
chlorine, wash his hands with chlorinated lime, and even sprinkle chlorinated lime
about the patient's bed, in cases of "contagious infection". In 1828, it was well known
that some infections were contagious, even though the agency of the microbe was not
to be realized or discovered for more than half a century.

During the Paris cholera outbreak of 1832, large quantities of so-called chloride of
lime were used to disinfect the capital. This was not simply modern calcium chloride,
but contained chlorine gas dissolved in lime-water (dilute calcium hydroxide) to
form calcium hypochlorite (chlorinated lime). Labarraque's discovery helped to
remove the terrible stench of decay from hospitals and dissecting rooms, and, by
doing so, effectively deodorised the Latin Quarter of Paris.[54] These "putrid miasmas"
were thought by many to be responsible for the spread of "contagion" and "infection"
both words used before the germ theory of infection. The use of chloride of lime
was based on destruction of odors and "putrid matter". One source has claimed that
chloride of lime was used by Dr. John Snow to disinfect water from the cholera-
contaminated well feeding the Broad Street pump in 1854 London.[55] Three reputable
sources that described the famous Broad Street pump cholera epidemic do not
mention Snow performing any disinfection of water from that well.[56][57][58] Instead, one
reference makes it clear that chloride of lime was used to disinfect the offal and filth
in the streets surrounding the Broad Street pumpa common practice in mid-
nineteenth century England.[56]:296

Semmelweis and experiments with antisepsis


Ignaz Semmelweis

Perhaps the most famous application of Labarraque's chlorine and chemical


base solutions was in 1847, when Ignaz Semmelweis used (first) chlorine-water
(simply chlorine dissolved in pure water), then cheaper chlorinated lime solutions, to
deodorize the hands of Austrian doctors, which Semmelweis noticed still carried the
stench of decomposition from the dissection rooms to the patient examination rooms.
Semmelweis, still long before the germ theory of disease, had theorized that
"cadaveric particles" were somehow transmitting decay from fresh medical cadavers
to living patients, and he used the well-known "Labarraque's solutions" as the only
known method to remove the smell of decay and tissue decomposition (which he
found that soap did not). The solutions proved to be far more effective germicide
antiseptics than soap (Semmelweis was also aware of their greater efficacy, but not
the reason), and this resulted in Semmelweis's (later) celebrated success in stopping
the transmission ofchildbed fever ("puerperal fever") in the maternity wards of Vienna
General Hospital in Austria in 1847.[59]

Much later, during World War I in 1916, a standardized and diluted modification of
Labarraque's solution, containing hypochlorite (0.5%) and boric acid as an acidic
stabilizer, was developed by Henry Drysdale Dakin (who gave full credit to
Labarraque's prior work in this area). Called Dakin's solution, the method of wound
irrigation with chlorinated solutions allowed antiseptic treatment of a wide variety of
open wounds, long before the modern antibiotic era. A modified version of this
solution continues to be employed in wound irrigation in the modern era, where it
remains effective against multiply antibiotic resistant bacteria (see Century
Pharmaceuticals).
Public sanitation

By 1918, the US Department of Treasury called for all drinking water to be


disinfected with chlorine. Chlorine is presently an important chemical for water
purification (such as in water treatment plants), in disinfectants, and in bleach.
Chlorine in water is more than three times as effective as a disinfectant
against Escherichia coli than an equivalent concentration of bromine, and is more
than six times more effective than an equivalent concentration of iodine.[60]

Chlorine is usually used (in the form of hypochlorous acid) to kill bacteria and other
microbes in drinking water supplies and public swimming pools. In most private
swimming pools, chlorine itself is not used, but rather sodium hypochlorite, formed
from chlorine and sodium hydroxide, or solid tablets of chlorinated isocyanurates. The
drawback of using chlorine in swimming pools is that the chlorine reacts with the
proteins in human hair and skin (see Hypochlorous acid). Once the chlorine reacts
with the hair and skin, it becomes chemically bonded. Even small water supplies are
now routinely chlorinated.[8]

It is often impractical to store and use poisonous chlorine gas for water treatment, so
alternative methods of adding chlorine are used. These include hypochlorite solutions,
which gradually release chlorine into the water, and compounds like sodium dichloro-
s-triazinetrione (dihydrate or anhydrous), sometimes referred to as "dichlor",
and trichloro-s-triazinetrione, sometimes referred to as "trichlor". These compounds
are stable while solid and may be used in powdered, granular, or tablet form. When
added in small amounts to pool water or industrial water systems, the chlorine atoms
hydrolyze from the rest of the molecule forming hypochlorous acid (HOCl), which
acts as a general biocide, killing germs, micro-organisms, algae, and so on.[61][62]

Use as a weapon

World War I

Main article: Chemical weapons in World War I

Chlorine gas, also known as bertholite, was first used as a weapon in World War I by
Germany on April 22, 1915 in the Second Battle of Ypres.[63] As described by the
soldiers it had a distinctive smell of a mixture between pepper and pineapple. It also
tasted metallic and stung the back of the throat and chest. Chlorine can react with
water in the mucosa of the lungs to form hydrochloric acid, an irritant that can be
lethal. The damage done by chlorine gas can be prevented by the activated
charcoal commonly found in gas masks, or other filtration methods, which makes the
overall chance of death by chlorine gas much lower than those of other chemical
weapons. It was pioneered by a German scientist later to be a Nobel laureate, Fritz
Haber of the Kaiser Wilhelm Institute in Berlin, in collaboration with the German
chemical conglomerate IG Farben, who developed methods for discharging chlorine
gas against an entrenched enemy. It is alleged that Haber's role in the use of chlorine
as a deadly weapon drove his wife, Clara Immerwahr, to suicide.[64] After its first use,
chlorine was utilized by both sides as a chemical weapon, but it was soon replaced by
the more deadly phosgene and mustard gas.[65] Theodore Gray wrote in his book The
Elements: A Visual Exploration of Every Atom in the Universe "Chlorine was used as
a poison gas during the grueling trench-warfare phase. Soldiers would position a line
of gas cylinders at the front lines, wait for the wind to shift towards the enemy, then
open the valves and run like hell. This practice---sometimes overseen personally by
Fritz Haber, a man whose positive contributions to humanity are listed under nitrogen
(7)--- was slowly phased out as experience showed that roughly equal numbers of
soldiers on both sides died regardless of who set off the gas."[66]

Iraq War

Main article: 2007 chlorine bombings in Iraq

Chlorine gas has also been used by insurgents against the local population and
coalition forces in the Iraq War in the form of chlorine bombs. On March 17, 2007,
for example, three chlorine-filled trucks were detonated in the Anbar province killing
two and sickening over 350.[67] Other chlorine bomb attacks resulted in higher death
tolls, with more than 30 deaths on two separate occasions.[68] Most of the deaths were
caused by the force of the explosions rather than the effects of chlorine, since the toxic
gas is readily dispersed and diluted in the atmosphere by the blast. The Iraqi
authorities have tightened security for elemental chlorine, which is essential for
providing safe drinking water to the population.

Syrian Civil War

There have been allegations of chlorine gas attacks during the Syrian Civil War such
as the 2014 Kafr Zita chemical attack.

Islamic State of Iraq and the Levant (ISIL/ISIS)

See also: Islamic_State_of_Iraq_and_the_Levant Use_of_chemical_weapons

On October 24, 2014 it was reported that the Islamic State of Iraq and the Levant had
used chlorine gas in the town of Duluiyah, Iraq.[69]
Laboratory analysis of clothing and soil samples confirmed the use of chlorine gas
against Kurdish Peshmerga Forces in a vehicle-borne improvised explosive device
attack on January 23, 2015 at the Highway 47 Kiske Junction near Mosul. [70]

Health effects of the free element and hazards

NFPA 704
"fire diamond"

0
3
0
OX

[71]

Chlorine is a toxic gas that irritates the respiratory system. Because it is denser than
air, it tends to accumulate at the bottom of poorly ventilated spaces. Chlorine gas is a
strong oxidizer, which may react with flammable materials.[72]

Chlorine is detectable with measuring devices in concentrations of as low as 0.2 parts


per million (ppm), and by smell at 3 ppm. Coughing and vomiting may occur at 30
ppm and lung damage at 60 ppm. About 1000 ppm can be fatal after a few deep
breaths of the gas.[26] Breathing lower concentrations can aggravate the respiratory
system, and exposure to the gas can irritate the eyes.[73] The toxicity of chlorine comes
from its oxidizing power. When chlorine is inhaled at concentrations above 30 ppm, it
begins to react with water and cells, which change it into hydrochloric acid (HCl)
and hypochlorous acid (HClO).

When used at specified levels for water disinfection, the reaction of chlorine with
water is not a major concern for human health. Other materials present in the water
may generate disinfection by-products that are associated with negative effects on
human health.[74][75]
Chlorine induced cracking in structural materials

Chlorine "attack" on an acetal resin plumbing joint.

The element is widely used for purifying water owing to its powerful oxidizing
properties, especially potable water supplies and water used in swimming pools.
Several catastrophic collapses of swimming pool ceilings have occurred owing to
chlorine induced stress corrosion cracking of stainless steel rods used to suspend
them.[76] Some polymers are also sensitive to attack, including acetal
resin and polybutene. Both materials were used in hot and cold water domestic
supplies, and stress corrosion cracking caused widespread failures in the USA in the
1980s and 1990s. The picture on the right shows a fractured acetal joint in a water
supply system. The cracks started at injection molding defects in the joint and slowly
grew until finally triggered. The fracture surface shows iron and calcium salts that
were deposited in the leaking joint from the water supply before failure.[77]

Chlorine-iron fire

The element iron can combine with chlorine at high temperatures in a strong
exothermic reaction, creating a chlorine-iron fire.[78][79] Chlorine-iron fires are a risk in
chemical process plants, where much of the pipework used to carry chlorine gas is
made of steel.[78][79]

Organochlorine compounds as pollutants


Some organochlorine compounds are serious pollutants. These are produced either as
by-products or end products of industrial processes which are persistent in the
environment, such as certain chlorinated pesticides and chlorofluorocarbons. Chlorine
is added both to pesticides and pharmaceuticals to make the molecules more resistant
to enzymatic degradation by bacteria, insects, and mammals, but this property also has
the effect of prolonging the residence time of these compounds when they enter the
environment. In this respect chlorinated organics have some resemblance to
fluorinated organics.
Argon
From Wikipedia, the free encyclopedia
Jump to: navigation, search
This article is about the chemical element. For other uses, see Argon
(disambiguation).
Not to be confused with Argonne (disambiguation).

Argon, Ar 18

Spectral lines of argon

General properties

Name, symbol argon, Ar

Appearance colorless gas exhibiting a lilac/violet


glow when placed in a high voltage
electric field

Pronunciation /rn/
AR-gon

Argon in the periodic table

Ne

Ar

Kr
chlorine argon potassium

Atomic number 18

Standard atomic weight () (Ar) 39.948(1)[1]

Element category noble gas

Group, block group 18 (noble gases), p-block

Period period 3

Electron configuration [Ne] 3s2 3p6

per shell 2, 8, 8

Physical properties

Phase gas

Melting point 83.81 K (189.34 C, 308.81 F)

Boiling point 87.302 K (185.848 C, 302.526 F)

Density at stp(0 C and 1.784 g/L


101.325 kPa)

when liquid, at b.p. 1.3954 g/cm3

Triple point 83.8058 K, 68.89 kPa[2]

Critical point 150.687 K, 4.863 MPa[2]

Heat of fusion 1.18 kJ/mol

Heat of vaporization 6.53 kJ/mol


Molar heat capacity 20.85[3] J/(molK)

vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 47 53 61 71 87

Atomic properties

Oxidation states 0

Electronegativity Pauling scale: no data

Ionization energies 1st: 1520.6 kJ/mol


2nd: 2665.8 kJ/mol
3rd: 3931 kJ/mol
(more)

Covalent radius 10610 pm

Van der Waals radius 188 pm

Miscellanea

Crystal structure face-centered cubic (fcc)

Speed of sound 323 m/s (gas, at 27 C)

Thermal conductivity 17.72103 W/(mK)

Magnetic ordering diamagnetic[4]


CAS Registry Number 7440371

History
Discovery and first isolation Lord Rayleigh and William
Ramsay (1894)

Most stable isotopes

Main article: Isotopes of argon


iso NA half-life DM DE (MeV) DP
36
Ar 0.337% (++) 0.4335 36S
37
Ar syn 35 d 0.813 37
Cl
38
Ar 0.063% Ar is stable with 20 neutrons
38

39
Ar trace 269 y 0.565 39
K
40
Ar 99.600% Ar is stable with 22 neutrons
40

41
Ar syn 109.34 min 2.49 41
K
42
Ar syn 32.9 y
0.600 42
K
Decay modes in parentheses are predicted, but have not yet been observed

references

Argon is a chemical element with symbol Ar and atomic number 18. It is in group 18
of the periodic table and is a noble gas.[5] Argon is the third most common gas in
the Earth's atmosphere, at 0.93% (9,300 ppm), making it approximately 23.7 times as
abundant as the next most common atmospheric gas, carbon dioxide (390 ppm), and
more than 500 times as abundant as the next most common noble gas, neon (18 ppm).
Nearly all of this argon isradiogenic argon-40 derived from the decay of potassium-
40 in the Earth's crust. In the universe, argon-36 is by far the most common
argon isotope, being the preferred argon isotope produced by
stellar nucleosynthesis in supernovas. In addition, argon is the most prevalent of the
noble gases in Earth's crust, with the element composing 0.00015% of this crust.[6]

The name "argon" is derived from the Greek word , neuter singular form
of meaning "lazy" or "inactive", as a reference to the fact that the element
undergoes almost no chemical reactions. The complete octet (eight electrons) in the
outer atomic shell makes argon stable and resistant to bonding with other elements.
Its triple point temperature of 83.8058 K is a defining fixed point in the International
Temperature Scale of 1990.

Argon is produced industrially by the fractional distillation of liquid air. Argon is


mostly used as an inert shielding gas in welding and other high-temperature industrial
processes where ordinarily non-reactive substances become reactive; for example, an
argon atmosphere is used in graphite electric furnaces to prevent the graphite from
burning. Argon gas also has uses in incandescent and fluorescent lighting, and other
types of gas discharge tubes. Argon makes a distinctive blue-green gas laser. Argon is
also used in fluorescent glow starters.
Contents
[hide]

1 Characteristics
2 History
3 Occurrence
4 Isotopes
5 Compounds
6 Production
o 6.1 Industrial
o 6.2 In radioactive decays
7 Applications
o 7.1 Industrial processes
o 7.2 Scientific research
o 7.3 Preservative
o 7.4 Laboratory equipment
o 7.5 Medical use
o 7.6 Lighting
o 7.7 Miscellaneous uses
8 Safety
9 See also
10 References
11 Further reading
12 External links

Characteristics

A small piece of rapidly melting solid argon.

Argon has approximately the same solubility in water as oxygen, and is 2.5 times
more soluble in water than nitrogen. Argon is colorless, odorless, nonflammable and
nontoxic as a solid, liquid, and gas.[7] Argon is chemically inert under most conditions
and forms no confirmed stable compounds at room temperature.
Although argon is a noble gas, it has been found to have the capability of forming
some compounds. For example, the creation of argon fluorohydride(HArF), a
compound of argon with fluorine and hydrogen which is stable below 17 K, was
reported by researchers at the University of Helsinki in 2000.[8][9] Although the neutral
ground-state chemical compounds of argon are presently limited to HArF, argon can
form clathrates with water when atoms of it are trapped in a lattice of the water
molecules.[10] Argon-containing ions and excited state complexes, such as ArH+
and ArF, respectively, are known to exist. Theoretical calculations have predicted
several argon compounds that should be stable,[11] but for which no synthesis routes are
currently known.

History

Lord Rayleigh's method for the isolation of argon, based on an experiment ofHenry
Cavendish's. The gases are contained in a test-tube (A) standing over a large quantity
of weakalkali (B), and the current is conveyed in wires insulated by U-shaped glass
tubes (CC) passing through the liquid and round the mouth of the test-tube. The inner
platinum ends (DD) of the wire receive a current from a battery of fiveGrove cells and
aRuhmkorff coil of medium size.

Argon (, neuter singular form of , Greek meaning "inactive", in reference


to its chemical inactivity)[12][13] was suspected to be present in air by Henry
Cavendish in 1785 but was not isolated until 1894 by Lord Rayleigh and Sir William
Ramsay at University College London in an experiment in which they removed all of
the oxygen, carbon dioxide, water and nitrogen from a sample of clean air.[14][15][16] They
had determined that nitrogen produced from chemical compounds was one-half
percent lighter than nitrogen from the atmosphere. The difference seemed
insignificant, but it was important enough to attract their attention for many months.
They concluded that there was another gas in the air mixed in with the
nitrogen.[17] Argon was also encountered in 1882 through independent research of H. F.
Newall and W. N. Hartley. Each observed new lines in the color spectrum of air but
were unable to identify the element responsible for the lines. Argon became the first
member of the noble gases to be discovered. The symbol for argon is now "Ar", but
up until 1957 it was "A".[18]

Occurrence
Argon constitutes 0.934% by volume and 1.288% by mass of the Earth's
atmosphere,[19] and air is the primary raw material used by industry to produce purified
argon products. Argon is isolated from air by fractionation, most commonly
by cryogenic fractional distillation, a process that also produces
purified nitrogen, oxygen, neon, krypton and xenon.[20] The Earth's crust and seawater
contain 1.2 ppm and 0.45 ppm of argon, respectively.[21]

Isotopes
Main article: Isotopes of argon

The main isotopes of argon found on Earth are 40


Ar (99.6%), 36
Ar (0.34%), and 38
Ar (0.06%). Naturally occurring 40
K, with a half-life of 1.25109 years, decays to stable 40
Ar (11.2%) by electron capture or positron emission, and also to stable 40
Ca (88.8%) via beta decay. These properties and ratios are used to determine the age
of rocks by the method of K-Ar dating.[21][22]

In the Earth's atmosphere, 39


Ar is made by cosmic ray activity, primarily with 40
Ar. In the subsurface environment, it is also produced through neutron capture by 39
K or alpha emission by calcium. 37
Aris created from the neutron spallation of 40
Ca as a result of subsurface nuclear explosions. It has a half-life of 35 days.[22]
Argon is notable in that its isotopic composition varies greatly between different
locations in the Solar System. Where the major source of argon is the decay of 40
K in rocks, 40
Ar will be the dominant isotope, as it is on Earth. Argon produced directly by stellar
nucleosynthesis, in contrast, is dominated by the alpha process nuclide, 36
Ar. Correspondingly, solar argon contains 84.6% 36
Ar based on solar wind measurements,[23] and the ratio of the three
isotopes 36Ar : 38Ar : 40Ar in the atmospheres of the outer planets is measured to be
8400 : 1600 : 1.[24] This contrasts with the abundance of primordial 36
Ar in Earth's atmosphere: only 31.5 ppmv (= 9340 ppmv 0.337%), comparable to
that of neon (18.18 ppmv); and with measurements by interplanetary probes.

The Martian atmosphere contains 1.6% of 40


Ar and 5 ppm of 36
Ar. The Mariner probe fly-by of the planet Mercury in 1973 found that Mercury has a
very thin atmosphere with 70% argon, believed to result from releases of the gas as a
decay product from radioactive materials on the planet. In 2005, the Huygens probe
discovered the presence of exclusively 40
Ar on Titan, the largest moon ofSaturn.[21][25]

The predominance of radiogenic 40


Ar is responsible for the standard atomic weight of terrestrial argon being greater than
that of the next element, potassium, which was puzzling at the time when argon was
discovered. Mendeleev had placed the elements in his periodic table in order of
atomic weight, but the inertness of argon suggested a placement before the
reactive alkali metal. Henry Moseley later solved this problem by showing that the
periodic table is actually arranged in order of atomic number. (See History of the
periodic table).

Compounds
See also: Van der Waals molecule

Space-filling model ofargon fluorohydride.


Argon's complete octet of electrons indicates full s and p subshells. This full outer
energy level makes argon very stable and extremely resistant to bonding with other
elements. Before 1962, argon and the other noble gases were considered to be
chemically inert and unable to form compounds; however, compounds of the heavier
noble gases have since been synthesized. In August 2000, the first argon compound
was formed by researchers at the University of Helsinki. By shining ultraviolet light
onto frozen argon containing a small amount of hydrogen fluoride with caesium
iodide,[26] argon fluorohydride (HArF) was formed.[9][27] It is stable up to
40 kelvin (233 C). The metastable ArCF2+
2 dication, which is valence isoelectronic with carbonyl fluoride, was observed in
2010.[28] Argon-36, in the form of argon hydride ions, has been detected in cosmic
dust associated with the Crab Nebula supernova; this was the first noble-gas
molecule detected in outer space.[29][30]

Production
Industrial

Argon is produced industrially by the fractional distillation of liquid air in


a cryogenic air separation unit; a process that separates liquid nitrogen, which boils at
77.3 K, from argon, which boils at 87.3 K, and liquid oxygen, which boils at 90.2 K.
About 700,000 tonnes of argon are produced worldwide every year.[21][31]

In radioactive decays
40
Ar, the most abundant isotope of argon, is produced by the decay of 40K with a half-
life of 1.25109 years by electron capture or positron emission. Because of this, it is
used in potassium-argon datingto determine the age of rocks.

Applications
Cylinders containing argon gas for use in extinguishing fire without damaging server
equipment

There are several different reasons argon is used in particular applications:

An inert gas is needed. In particular, argon is the cheapest alternative


when nitrogen is not sufficiently inert.
Low thermal conductivity is required.
The electronic properties (ionization and/or the emission spectrum) are
necessary.

Other noble gases would probably work as well in most of these applications, but
argon is by far the cheapest. Argon is inexpensive since it occurs naturally in air, and
is readily obtained as a byproduct of cryogenic air separation in the production
of liquid oxygen and liquid nitrogen: the primary constituents of air are used on a
large industrial scale. The other noble gases (except helium) are produced this way as
well, but argon is the most plentiful by far. The bulk of argon applications arise
simply because it is inert and relatively cheap.

Industrial processes

Argon is used in some high-temperature industrial processes, where ordinarily non-


reactive substances become reactive. For example, an argon atmosphere is used in
graphite electric furnaces to prevent the graphite from burning.

For some of these processes, the presence of nitrogen or oxygen gases might cause
defects within the material. Argon is used in various types of arc welding such as gas
metal arc welding and gas tungsten arc welding, as well as in the processing
of titanium and other reactive elements. An argon atmosphere is also used for growing
crystals of silicon and germanium.

See also: shielding gas

Argon is used in the poultry industry to asphyxiate birds, either for mass culling
following disease outbreaks, or as a means of slaughter more humane than the electric
bath. Argon's relatively high density causes it to remain close to the ground during
gassing. Its non-reactive nature makes it suitable in a food product, and since it
replaces oxygen within the dead bird, argon also enhances shelf life.[citation needed][32]

Argon is sometimes used for extinguishing fires where damage to equipment is to be


avoided.

Scientific research

Liquid argon is used as the target for neutrino experiments and direct dark
matter searches. The interaction of a hypothetical WIMP particle with the argon
nucleus produces scintillation light that is detected by photomultiplier tubes. Two-
phase detectors also use argon gas to detect the ionized electrons produced during the
WIMP-nucleus scattering. As with most other liquefied noble gases, argon has a high
scintillation lightyield (~ 51 photons/keV[33]), is transparent to its own scintillation
light, and is relatively easy to purify. Compared to xenon, argon is cheaper and has a
distinct scintillation time profile which allows the separation of electronic recoils from
nuclear recoils. On the other hand, its intrinsic beta-ray background is larger due to 39
Ar contamination, unless one uses underground argon sources which has much less 39
Ar contamination. Most of the argon in the Earths atmosphere was produced by
electron capture of long-lived 40
K (40
K + e 40
Ar + ) present in natural potassium within the earth. The 39
Ar activity in the atmosphere is maintained by cosmogenic production through 40
Ar(n,2n)39
Ar and similar reactions. The half-life of 39
Ar is only 269 yr. As a result, the underground Ar, shielded by rock and water, has
much less 39
Ar contamination.[34] Dark matter detectors currently operating with liquid argon
include DarkSide, WArP, ArDM, microCLEAN and DEAP-I. Neutrino experiments
include Icarus and MicroBooNE both of which use high purity liquid argon in a time
projection chamber for fine grained three-dimensional imaging of neutrino
interactions.
Preservative

A sample of caesium is packed under argon to avoid reactions with air

Argon is used to displace oxygen- and moisture-containing air in packaging material


to extend the shelf-lives of the contents (argon has the European food additive
code of E938). Aerial oxidation, hydrolysis, and other chemical reactions which
degrade the products are retarded or prevented entirely. Bottles of high-purity
chemicals and certain pharmaceutical products are available in sealed bottles or
ampoules packed in argon.

In winemaking, argon is used in a variety of activities to provide a barrier against


oxygen at the liquid's surface, which can spoil wine by fueling both microbial
metabolism (such as with acetic acid bacteria) and standard redox chemistry.

Argon is also available in aerosol-type cans, which may be used to preserve


compounds such as varnish, polyurethane, paint, etc. for storage after opening.[35]

Since 2002, the American National Archives stores important national documents
such as the Declaration of Independence and the Constitution within argon-filled
cases to retard their degradation. Using argon reduces gas leakage, compared with the
helium used in the preceding five decades.[36]

Laboratory equipment
Gloveboxes are often filled with argon, which recirculates over scrubbers to maintain
an oxygen-,nitrogen-, and moisture-free atmosphere
See also: Air-free technique

Argon may be used as the inert gas within Schlenk lines and gloveboxes. The use of
argon over comparatively less expensive nitrogen is preferred where nitrogen may
react with the experimental reagents or apparatus.

Argon may be used as the carrier gas in gas chromatography and in electrospray
ionization mass spectrometry; it is the gas of choice for the plasma used
in ICP spectroscopy. Argon is preferred for the sputter coating of specimens
for scanning electron microscopy. Argon gas is also commonly used for sputter
deposition of thin films as in microelectronics and for wafer cleaning in
microfabrication.

Medical use

Cryosurgery procedures such as cryoablation use liquefied argon to destroy tissue


such as cancer cells. In surgery it is used in a procedure called "argon enhanced
coagulation" which is a form of argonplasma beam electrosurgery. The procedure
carries a risk of producing gas embolism in the patient and has resulted in the death of
one person via this type of accident.[37]

Blue argon lasers are used in surgery to weld arteries, destroy tumors, and to correct
eye defects.[21]

Argon has also been used experimentally to replace nitrogen in the breathing or
decompression mix known as Argox, to speed the elimination of dissolved nitrogen
from the blood.[38]

Lighting

Argon gas-discharge lampforming the symbol for argon "Ar".


Incandescent lights are filled with argon, to preserve the filaments at high temperature
from oxidation. It is used for the specific way it ionizes and emits light, such as
in plasma globes and calorimetry in experimental particle physics. Gas-discharge
lamps filled with pure argon provide lilac/violet light, filled with argon and some
mercury blue light. Argon is also used for the creation of blue and green laser light.

Miscellaneous uses

Argon is used for thermal insulation in energy efficient windows.[39] Argon is also used
in technical scuba diving to inflate a dry suit, because it is inert and has low thermal
conductivity.[40] Argon is being used as a propellant in the development of the Variable
Specific Impulse Magnetoplasma Rocket (VASIMR). Compressed argon gas is
allowed to expand, to cool the seeker heads of the AIM-9 Sidewinder missile, and
other missiles that use cooled thermal seeker heads. The gas is stored at high
pressure.[41]

Argon-39, with a half-life of 269 years, has been used for a number of applications,
primarily ice core and ground water dating. Also, potassium-argon dating is used in
dating igneous rocks.[21]

Argon has been used by athletes as a doping agent to simulate hypoxic conditions. On
August 31, 2014 the World Anti Doping Agency (WADA) added argon and xenon to
the list of prohibited substances and methods, although at this time there is no reliable
test for abuse.[42]

Safety
Although argon is non-toxic, it is 38% denser than air and is therefore considered a
dangerous asphyxiant in closed areas. It is also difficult to detect because it is
colorless, odorless, and tasteless. A 1994 incident in which a man
was asphyxiated after entering an argon-filled section of oil pipe under construction
in Alaska highlights the dangers of argon tank leakage in confined spaces, and
emphasizes the need for proper use, storage and handling.[43]

Potassium
From Wikipedia, the free encyclopedia
Jump to: navigation, search

Potassium, K
19
Potassium pearls under paraffin oil. The large pearl measures 0.5 cm.

Spectral lines of potassium

General properties

Name, symbol potassium, K

Appearance silvery gray

Pronunciation /ptsim/
po-TAS-ee-m

Potassium in the periodic table

Na

K

Rb

argon potassium calcium

Atomic number 19

Standard atomic weight () (Ar) 39.0983(1)[1]

Element category alkali metal


Group, block group 1 (alkali metals),s-block

Period period 4

Electron configuration [Ar] 4s1

per shell 2, 8, 8, 1

Physical properties

Phase solid

Melting point 336.7 K (63.5 C, 146.3 F)

Boiling point 1032 K (759 C, 1398 F)

Density near r.t. 0.862 g/cm3

when liquid, at m.p. 0.828 g/cm3

Critical point 2223 K, 16 MPa[2]

Heat of fusion 2.33 kJ/mol

Heat of vaporization 76.9 kJ/mol

Molar heat capacity 29.6 J/(molK)

Atomic properties

Oxidation states +1, 1 (a strongly basicoxide)

Electronegativity Pauling scale: 0.82

Ionization energies 1st: 418.8 kJ/mol


2nd: 3052 kJ/mol
3rd: 4420 kJ/mol
(more)

Atomic radius empirical: 227 pm

Covalent radius 20312 pm

Van der Waals radius 275 pm

Miscellanea

Crystal structure body-centered cubic(bcc)

Speed of soundthin rod 2000 m/s (at 20 C)

Thermal expansion 83.3 m/(mK) (at 25 C)

Thermal conductivity 102.5 W/(mK)

Electrical resistivity 72 nm (at 20 C)

Magnetic ordering paramagnetic[3]

Young's modulus 3.53 GPa

Shear modulus 1.3 GPa

Bulk modulus 3.1 GPa

Mohs hardness 0.4

Brinell hardness 0.363 MPa


CAS Registry Number 7440-09-7

History

Discovery and first isolation Humphry Davy (1807)

Most stable isotopes

Main article: Isotopes of potassium

iso NA half-life DM DE (MeV) DP


39
K 93.26% K is stable with 20 neutrons
39

1.311 40
Ca
40
K 0.012% 1.248(3)10 y 1.505
9 40
Ar
+ 1.505 40
Ar
41
K 6.73% K is stable with 22 neutrons
41

references

Potassium is a chemical element with symbol K (derived from Neo-Latin kalium)


and atomic number 19. It was first isolated from potash, the ashes of plants, from
which its name is derived. In the Periodic table, potassium is one of seven elements in
column (group) 1 (alkali metals): they all have a single electron in their outer electron
shell, which they readily give up to create an atom with a positive charge - a cation,
and combine with anions to form salts. Potassium in nature occurs only in ionic salts.
Elemental potassium is a soft silvery-white alkali metal that oxidizes rapidly in air and
reacts vigorously with water, generating sufficient heat to ignite hydrogen emitted in
the reaction and burning with a lilac flame. It is found dissolved in sea water (which is
0.04% potassium by weight[4][5]), and is part of many minerals. Naturally occurring
potassium is composed of three isotopes, one of which, 40
K, is radioactive. Traces of 40
K are found in all potassium, and it is the most common radioisotope in the human
body.

Potassium is chemically very similar to sodium, which is also in column 1 of the


Periodic table, and is in row 3, adjacent to potassium in row 4. They both have a
similar ionization energy, which allows for each atom to give up its sole outer
electron. The fact that they are different elements, each combining with the
same anions to make similar salts, was suspected in 1702,[6] and was proven in 1807
using electrolysis.
Most industrial applications of potassium exploit the high solubility in water of
potassium compounds, such as potassium soaps. Heavy crop production rapidly
depletes soils of potassium, and this depletion is prevented and remedied with
agricultural fertilizers containing potassium, which account for 95% of global
potassium chemical production.[7]

Potassium ions are necessary for the function of all living cells. Potassium ion shifts
across nerve cell membranes are necessary for normal nerve transmission: potassium
depletion or excess can result in numerous abnormalities, including an abnormal heart
rhythm and various electrocardiographic (ECG) abnormalities. Fresh fruits and
vegetables are good dietary sources of potassium. The body responds to the influx of
dietary potassium, which raises serum potassium levels, with a shift of potassium
from outside to inside cells, and an increase in potassium excretion by the kidney.

Contents
[hide]

1 Properties
o 1.1 Physical
o 1.2 Chemical
1.2.1 Compounds
o 1.3 Isotopes
2 Cosmic formation and distribution
3 Etymology
4 Potash
5 The metal
6 Geology
7 Commercial production
8 Biological role
o 8.1 Biochemical function
o 8.2 Homeostasis
8.2.1 Plasma levels
8.2.2 Control mechanisms
8.2.3 Renal filtration, reabsorption, and excretion
o 8.3 In diet
8.3.1 Detection by taste buds
8.3.2 Adequate intake
8.3.3 Optimal intake
8.3.4 Deficient intake
8.3.5 Supplementation
9 Applications
o 9.1 Fertilizer
o 9.2 Food
o 9.3 Industrial
9.3.1 Niche uses
9.3.2 Laboratory uses
10 Precautions
11 See also
12 References
13 Bibliography
14 External links

Properties
Physical

The flame test of potassium.

Potassium is the second least dense metal after lithium. It is a soft solid that has a
low melting point and can easily be cut with a knife. Freshly cut potassium is silvery
in appearance, but it begins to tarnish toward gray immediately after being exposed to
air.[8] In a flame test, potassium and its compounds emit a lilac color with a peak
emission wavelength of 766.5 nanometers[9]

Chemical

Potassium atoms have 19 electrons, which is one more than the extremely stable
configuration of the noble gas argon. Because of this and its low firstionization
energy of 418.8 kJ/mol, the potassium atom is thus much more likely to lose the
"extra" electron, acquiring a positive charge, than to gain one and acquire a negative
charge; (however, such negatively charged alkalide ions (K
) are known.[10][11]) This process requires so little energy that potassium is readily
oxidized by atmospheric oxygen. In contrast, the second ionization energy is very
high (3052 kJ/mol), because removal of two electrons breaks the stable noble gas
electronic configuration (the configuration of the inert argon).[11] Potassium therefore
does not readily form compounds with the oxidation state of +2 or higher. [10]

Potassium is an extremely active metal, which reacts violently with oxygen and water
in air. With oxygen it forms potassium peroxide, and with water potassium
forms potassium hydroxide. The reaction of potassium with water is dangerous
because of its violent exothermic character and the production of hydrogen gas.
Hydrogen reacts again with atmospheric oxygen, producing water, which reacts with
the remaining potassium. This reaction requires only traces of water; because of this,
potassium and its liquid alloy with sodium NaK are potent desiccants that can
be used to dry solvents prior to distillation.[12]

Because of the sensitivity of potassium to water and air, reactions with other elements
are possible only in inert atmosphere, such as argon gas using air-free techniques.
Potassium does not react with most hydrocarbons such as mineral oil or kerosene.[13] It
readily dissolves in liquid ammonia, up to 480 g per 1000 g of ammonia at 0 C.
Depending on the concentration, the ammonia solutions are blue to yellow, and their
electrical conductivity is similar to that of liquid metals. In a pure solution, potassium
slowly reacts with ammonia to form KNH
2, but this reaction is accelerated by minute amounts of transition metal
salts.[14] Because it can reduce the salts to the metal, potassium is often used as the
reductant in the preparation of finely divided metals from their salts by the Rieke
method.[15] For example, the preparation of Rieke magnesium employs potassium as
the reductant:

MgCl
2 + 2 K Mg + 2 KCl

Compounds
Structure of solid potassium superoxide (KO
2}.

The only common oxidation state for potassium is +1. Potassium metal is a
powerful reducing agent that is easily oxidized to the monopositive cation, K+
. Once oxidized, it is very stable and difficult to reduce back to the metal.[10]

Potassium hydroxide reacts readily with carbon dioxide to produce potassium


carbonate, and is used to remove traces of the gas from air. In general, potassium
compounds have excellent water solubility, owing to the high hydration energy of
the K+
ion. The potassium ion is colorless in water and is very difficult to precipitate;
possible precipitation methods include reactions with sodium
tetraphenylborate, hexachloroplatinic acid, and sodium cobaltinitrite.[13]

Potassium oxidizes faster than most metals and forms oxides with oxygen-oxygen
bonds, as do all alkali metals except lithium. Three species are formed during the
reaction: potassium oxide, potassium peroxide, and potassium superoxide,[16] which
contain three different oxygen-based ions: oxide (O2
), peroxide (O2
2), and superoxide (O
2). The last two species, especially the superoxide, are rare and are formed only in
reaction with very electropositive metals; these species contain oxygen-oxygen
bonds.[14] All potassium-oxygen binary compounds are known to react with water
violently, formingpotassium hydroxide. This compound is a very strong alkali, and
1.21 kg of it can dissolve in as little as a liter of water.[17][18]

Potassium compounds are typically highly ionic and thus most of them are soluble in
water. The main species in water are the aquated complexes [K(H
2O)
n]+
where n = 6 and 7.[19] Some of the few poorly soluble potassium salts
include potassium tetraphenylborate, potassium hexachloroplatinate, and potassium
cobaltinitrite.[13]

Isotopes

Main article: Isotopes of potassium

There are 24 known isotopes of potassium, three of which occur naturally: 39


K (93.3%), 40
K (0.0117%), and 41
K (6.7%). Naturally occurring 40
K has a half-life of 1.250109 years. It decays to stable 40
Ar by electron capture or positron emission (11.2%) or to stable 40
Ca by beta decay (88.8%).[20] The decay of 40
K to 40
Ar enables a commonly used method for dating rocks. The conventional K-Ar dating
method depends on the assumption that the rocks contained no argon at the time of
formation and that all the subsequent radiogenic argon (i.e., 40
Ar) was quantitatively retained. Minerals are dated by measurement of the
concentration of potassium and the amount of radiogenic 40
Ar that has accumulated. The minerals that are best suited for dating
include biotite, muscovite, metamorphichornblende, and volcanic feldspar; whole
rock samples from volcanic flows and shallow instrusives can also be dated if they are
unaltered.[20][21] Outside of dating, potassium isotopes have been used astracers in
studies of weathering and for nutrient cycling studies because potassium is
a macronutrient required for life.[22]
40
K occurs in natural potassium (and thus in some commercial salt substitutes) in
sufficient quantity that large bags of those substitutes can be used as a radioactive
source for classroom demonstrations. 40
K is the radioisotope with the largest abundance in the body. In healthy animals and
people, 40
K represents the largest source of radioactivity, greater even than 14
C. In a human body of 70 kg mass, about 4,400 nuclei of 40
K decay per second.[23] The activity of natural potassium is 31 Bq/g.[24]

Cosmic formation and distribution


Potassium in feldspar

Potassium is formed in supernovas by nucleosynthesis from lighter atoms. Potassium


is principally created in Type II supernovas via the explosive oxygen-burning
process.[25] 40
K is also formed in s-process nucleosynthesis and the neon burning process.[citation needed]

Potassium makes up about 2.6% of the weight of the earth's crust and is the seventh
most abundant element in the crust.[26] It is the 17th most abundant element by weight
in the earth, and 20th most abundant element in the solar system. The potassium
concentration in seawater is 0.39 g/L[4] (0.039 wt/v%), about one-quarter the
concentration of sodium.[27][28]

Etymology
Neither elemental potassium nor potassium salts (as separate entities from other salts)
were known in Roman times, and the Latin name of the element, kalium, is
not Classical Latin but rather neo-Latin.Kalium was taken from the word "alkali",
which in turn came from Arabic: al-qalyah "plant ashes." The similar-sounding
English term alkali is from this same root, whereas the word for potassium in Modern
Standard Arabic is btsym. The English name for the
element potassium comes from the word "potash",[29] and refers to the method by
which potassium was obtained placing in apot the ash of burnt wood or tree leaves,
adding water, heating, and evaporating the solution.

Potash
Potash is primarily a mixture of potassium salts because plants have little or no
sodium content, and the rest of a plant's major mineral content consists of calcium
salts of relatively low solubility in water. While potash has been used since ancient
times, it was not understood for most of its history to be a fundamentally different
substance from sodium mineral salts. Georg Ernst Stahl obtained experimental
evidence that led him to suggest the fundamental difference of sodium and potassium
salts in 1702,[6] and Henri Louis Duhamel du Monceau was able to prove this
difference in 1736.[30] The exact chemical composition of potassium and sodium
compounds, and the status as chemical element of potassium and sodium, was not
known then, and thus Antoine Lavoisier did not include the alkali in his list of
chemical elements in 1789.[31][32]For a long time the only significant applications for
potash were the production of glass, bleach, soap and gunpowder as potassium
nitrate.[33] Potassium soaps from animal fats and vegetable oils were especially prized,
as they tended to be more water-soluble and of softer texture, and were known as
soft soaps.[7] The discovery by Justus Liebig in 1840 that potassium is a necessary
element for plants and that most types of soil lack potassium[34] caused a steep rise in
demand for potassium salts. Wood-ash from fir trees was initially used as a potassium
salt source for fertilizer, but, with the discovery in 1868 of mineral deposits
containing potassium chloride near Stafurt, Germany, the production of potassium-
containing fertilizers began at an industrial scale.[35][36][37] Other potash deposits were
discovered, and by the 1960s Canada became the dominant producer.[38][39]

The metal

Humphry Davy

Potassium metal was first isolated in 1807 in England by Sir Humphry Davy, who
derived it from caustic potash (KOH, potassium hydroxide) by the use of electrolysis
of the molten KOH with the newly discovered voltaic pile. Potassium was the first
metal that was isolated by electrolysis.[40] Later in the same year, Davy reported
extraction of the metal sodium from a mineral derivative (caustic soda, NaOH, or lye)
rather than a plant salt, by a similar technique, demonstrating that the elements, and
thus the salts, are different.[31][32][41][42] Although the production of potassium and sodium
metal should have shown that both are elements, it took some time before this view
was universally accepted.[32]

Geology
Elemental potassium does not occur in nature because of its high reactivity. It reacts
violently with water (see section Precautions below)[13] and also reacts with
oxygen. Orthoclase (potassium feldspar) is a common rock-forming
mineral. Granite for example contains 5% potassium, which is well above the average
in the Earth's crust. Sylvite (KCl), carnallite (KClMgCl
26(H
2O)), kainite(MgSO
4KCl3H
2O) and langbeinite (MgSO
4K
2SO
4) are the minerals found in large evaporite deposits worldwide. The deposits often
show layers starting with the least soluble at the bottom and the most soluble on
top.[28] Deposits of niter (potassium nitrate) are formed by decomposition of organic
material in contact with atmosphere, mostly in caves; because of the good water
solubility of niter the formation of larger deposits requires special environmental
conditions.[43]

Commercial production

Sylvite from New Mexico

Potassium salts such as carnallite, langbeinite, polyhalite, and sylvite form extensive
deposits in ancient lake bottoms and seabeds,[27] making extraction of potassium salts
in these environments commercially viable. The principal source of potassium
potash is mined in Canada, Russia, Belarus, Germany, Israel, United States, Jordan,
and other places around the world.[44][45][46] The first mined deposits were located near
Stafurt, Germany, but the deposits span from Great Britain over Germany into
Poland. They are located in the Zechstein and were deposited in the Middle to
LatePermian. The largest deposits ever found lie 1,000 meters (3,300 feet) below the
surface of the Canadian province of Saskatchewan. The deposits are located in the Elk
Point Group produced in theMiddle Devonian. Saskatchewan, where several large
mines have operated since the 1960s, pioneered the use of freezing of wet sands (the
Blairmore formation) in order to drive mine shafts through them. The main potash
mining company in Saskatchewan is the Potash Corporation of Saskatchewan.[47] The
water of the Dead Sea is used by Israel and Jordan as a source for potash, while the
concentration in normal oceans is too low for commercial production at current
prices.[45][46]

Monte Kali, a potash mining andbeneficiation waste heap in Hesse, Germany,


consisting mostly ofsodium chloride.

Several methods are applied to separate the potassium salts from the present sodium
and magnesium compounds. The most-used method is to precipitate some compounds
relying on the solubility difference of the salts at different temperatures. Electrostatic
separation of the ground salt mixture is also used in some mines. The resulting sodium
and magnesium waste is either stored underground or piled up in slag heaps. Most of
the mined potassium minerals end up as potassium chloride after processing. The
mineral industry refers to potassium chloride either as potash, muriate of potash, or
simply MOP.[28]

Pure potassium metal can be isolated by electrolysis of its hydroxide in a process that
has changed little since Davy. Although the electrolysis process was developed and
used in industrial scale in the 1920s the thermal method by reacting sodium
with potassium chloride in a chemical equilibrium reaction became the dominant
method in the 1950s. The production of sodium potassium alloys is possible by
changing the reaction time and the amount of sodium used in the reaction. The
Griesheimer process employing the reaction of potassium fluoride with calcium
carbide was also used to produce potassium.[28][48]

Na + KCl NaCl + K (Thermal method)


2 KF + CaC
2 2 K + CaF
2 + 2 C (Griesheimer process)
Reagent-grade potassium metal cost about $10.00/pound ($22/kg) in 2010 when
purchased in tonne quantities. Lower purity metal is considerably cheaper. The market
is volatile due to the difficulty of the long-term storage of the metal. It must be stored
under a dry inert gas atmosphere or anhydrous mineral oil to prevent the formation of
a surface layer of potassium superoxide. This superoxide is a pressure-
sensitive explosive that will detonate when scratched. The resulting explosion will
usually start a fire that is difficult to extinguish.[49][50]

Biological role
Main article: Potassium in biology

Potassium is the eighth or ninth most common element by mass (0.2%) in the human
body, so that a 60 kg adult contains a total of about 120 g of
potassium.[51] The body has about as much potassium as sulfur and chlorine, and only
calcium and phosphorus are more abundant.[52]

Biochemical function

Potassium levels influence multiple physiological processes, including[53][54][55]

resting cellular-membrane potential and the propagation of action potentials in


neuronal, muscular, and cardiac tissue. Due to their electrostatic and chemical
properties, K+
ions are larger than Na+
ions, and ion channels and pumps in cell membranes can distinguish between
the two types of ions, actively pumping or passively allowing one of the two
ions to pass, while blocking the other.[56]
hormone secretion and action
vascular tone
systemic blood pressure control
gastrointestinal motility
acidbase homeostasis
glucose and insulin metabolism
mineralocorticoid action
renal concentrating ability
fluid and electrolyte balance

Homeostasis

Potassium homeostasis denotes the maintenance of the total body potassium content,
plasma potassium level, and the ratio of the intracellular to extracellular potassium
concentrations within narrow limits, in the face of pulsatile intake (meals), obligatory
renal excretion, and shifts between intracellular and extracellular compartments.

Plasma levels

The plasma potassium is normally kept at 3.5 to 5.0 millimoles (mmol), [or
milliequivalents (mEq]) per liter by multiple mechanisms. Levels outside this range
are associated with an increased rate of death of any cause;[57] and some cardiac,
kidney,[58] and lung diseases progress more rapidly if serum potassium levels are not
maintained with the normal range.

An average meal of 40-50 mmol presents the body with more potassium than is
present in all plasma (20-25 mmol). However, this surge causes the plasma potassium
to rise at most only 10% because of prompt and efficient clearance by both renal and
extra-renal mechanisms.[59]

Hypokalemia, a deficiency of potassium in the plasma, can be fatal if severe.


Common causes are increased gastrintestinal loss (vomiting, diarrhea), and increased
renal loss (diuresis).[60] Deficiency symptoms include muscle weakness, paralytic ileus,
ECG abnormalities, decreased reflex response; and in severe cases, respiratory
paralysis, alkalosis and cardiac arrhythmia.[61]

Control mechanisms

There are four basic mechanisms which maintain tight control of the plasma
potassium: they have various names and various classifications. The four are 1) a
reactive negative-feedback system, 2) a reactive feed-forward system, 3) a predictive
or circadian system, and 4) an internal or cell membrane transport system. The first
three are sometimes referred to collectively as the "external potassium homeostasis
system"; the first two as the "reactive potassium homeostasis system".

The reactive negative-feedback system refers to the system which induces renal
secretion of potassium in response to a rise in the plasma potassium (potassium
ingestion, shift out of cells, or intravenous infusion.)
The reactive feed-forward system refers to an incompletely understood system
which induces renal potassium secretion in response to potassium ingestion
prior to any rise in the plasma potassium. This is probably initiated by gut cell
potassium receptors which detect ingested potassium and
trigger vagal afferent signals to the pituitary gland.
The predictive or circadian system increases renal secretion of potassium
during mealtime hours (e.g. daytime for humans, nighttime for rodents)
independent of the presence, amount, or absence of potassium ingestion. It is
mediated by a circadian oscillator in the suprachiasmatic nucleus of the brain
(central clock), which entrains the kidney (peripheral clock) to secrete
potassium in this rhythmic circadian fashion.

The action of the sodium-potassium pump is an example of primary active


transport. The two carrier proteins embedded in the cell membrane on the left
are using ATP to move sodium out of the cell against the concentration
gradient; The two proteins on the right are using secondary active transport to
move potassium into the cell: this process results in reconstitution of ATP.

The internal or cell membrane transport system shifts potassium in and out of
all cells across their cell membrane using two mechanisms. One is active and
pumps sodium out of, and potassium into, the cell. The other is passive and
allows potassium to leak out of the cell. Potassium and sodium cations
influence fluid distribution between intracellular and extracellular
compartments viaosmotic forces. The movement of potassium and sodium
between these compartments is mediated by the Na+/K+-
ATPase pump.[62] This ion pump uses ATP to pump three sodium ions out of the
cell and two potassium ions into the cell, thus creating an electrochemical
gradient over the cell membrane. In addition, the highly selective potassium ion
channels (which are tetramers) are crucial for hyperpolarization, for example
inside neurons, after an action potential is fired. The most recently discovered
potassium ion channel is KirBac3.1, which makes a total of five potassium ion
channels (KcsA, KirBac1.1, KirBac3.1, KvAP, and MthK) with a determined
structure.[63] All five are from prokaryotic species.

Renal filtration, reabsorption, and excretion

Renal handling of potassium is closely connected to sodium handling. Potassium is


the major cation (positive ion) inside animal cells [150 mmol/L, (4.8 g)], while
sodium is the major cation of extracellular fluid [150 mmol/L, (3.345 g)]. In the
kidneys, plasma is filtered through the glomeruli and into the renal tubules in
enormous amounts, about 180 liters per day.[64] Normally each day about 600 g of
sodium and 33 g of potassium are filtered, while 110 g of sodium and the 14 g of
potassium are reabsorbed in the tubules; the remainder is excreted.

Sodium is reabsorbed to maintain extracellular volume, osmotic pressure, and serum


sodium concentration within narrow limits; potassium is reabsorbed to maintain serum
potassium concentration within narrow limits.[65] Sodium pumps in the renal tubules
operate to reabsorb sodium. Potassium must sometimes be conserved also, but, as the
amount of potassium in the blood plasma is very small and the pool of potassium in
the cells is about thirty times as large, the situation is not so critical for potassium.
Since potassium is moved passively[66][67] in counter flow to sodium in response to an
apparent (but not actual) Donnan equilibrium,[68] the urine can never sink below the
concentration of potassium in serum except sometimes by actively excreting water at
the end of the processing. Potassium is secreted twice and reabsorbed three times
before the urine reaches the collecting tubules.[69] At that point, it usually has about the
same potassium concentration as plasma. At the end of the processing, potassium is
secreted one more time if the serum levels are too high.

With no potassium intake, there is an obligatory excretion of about 200 mg per day,
until in about a week the serum potassium declines to a mildly deficient level of 3.0
3.5 mmol/L.[70] It continues to fall to create a severe deficiency in the plasma and
eventually death.[71]

The potassium moves passively through pores in the cell membrane. When ions move
through pumps there is a gate in the pumps on either side of the cell membrane and
only one gate can be open at once. As a result, approximately 100 ions are forced
through per second. Pores have only one gate, and there only one kind of ion can
stream through, at 10 million to 100 million ions per second.[72] The pores require
calcium in order to open[73] although it is thought that the calcium works in reverse by
blocking at least one of the pores.[74] Carbonyl groups inside the pore on the amino
acids mimic the water hydration that takes place in water solution[75] by the nature of
the electrostatic charges on four carbonyl groups inside the pore.[76]

In diet

Detection by taste buds

Potassium can be detected by taste because it triggers three of the five types of taste
sensations, according to concentration. Dilute solutions of potassium ions taste sweet,
allowing moderate concentrations in milk and juices, while higher concentrations
become increasingly bitter/alkaline, and finally also salty to the taste. The combined
bitterness and saltiness of high-potassium solutions makes high-dose potassium
supplementation by liquid drinks a palatability challenge.[77][78]

Adequate intake

Adequate potassium intake is achieved by eating a variety of foods. Potassium is


present in all fruits, vegetables, meat and fish. Foods with high potassium
concentrations include yam, parsley, driedapricots, dried milk, chocolate,
all nuts (especially almonds and pistachios), potatoes, bamboo
shoots, bananas, avocados, coconut water, soybeans, and bran.[79] Dried apricots have
the highest concentration of potassium per calorie of any food. Many processed foods
contain no potassium.

Optimal intake

Epidemiological studies indicate that diets high in potassium can reduce the risk
of hypertension and possibly stroke (by a mechanism independent of blood pressure).
The 2004 guidelines of the Institute of Medicine specify a Dietary Reference
Intake (DRI]) of 4,700 mg of potassium (100 mEq); most Americans consume only
half that amount per day.[80][81] Likewise, in the European Union, in particular
in Germany and Italy, insufficient potassium intake is somewhat common.[82] A meta-
analysis concluded that a 1640 mg increase in the daily intake of potassium was
associated with a 21% lower risk of stroke.[83]

Deficient intake

Diets low in potassium can lead to hypertension[84] and hypokalemia.

Supplementation

Supplements of potassium are most widely used in conjunction with diuretics that
block reabsorption of sodium and water upstream from the distal
tubule (thiazides and loop diuretics), because this promotes increased distal tubular
potassium secretion, with resultant increased potassium excretion. A variety of
prescription and over-the counter supplements are available. Potassium chloride may
be dissolved in water, but the salty/bitter taste make liquid supplements
unpalatable.[77] Typical doses range from 10 mmol (400 mg), to 20 mmol (800 mg).
Potassium is also also available in tablets or capsules, which are formulated to allow
potassium to leach slowly out of a matrix, since very high concentrations of potassium
ion which occur adjacent to a solid tablet cause injury to the gastric or intestinal
mucosa. For this reason, non-prescription potassium pills are limited by law in the US
to a maximum of 99 mg of potassium.

Since the kidneys are the site of potassium excretion, individuals with impaired
kidney function are at risk for hyperkalemia if dietary potassium and supplements are
not restricted. The more severe the impairment, the more severe is the restriction
necessary to avoid hyperkalemia.

Applications
Fertilizer

Potassium sulfate/magnesium sulfate fertilizer

Potassium ions are an essential component of plant nutrition and are found in
most soil types.[7] They are used as a fertilizer in agriculture, horticulture,
and hydroponic culture in the form of chloride(KCl), sulfate (K
2SO
4), or nitrate (KNO
3). Agricultural fertilizers consume 95% of global potassium chemical production, and
about 90% of this potassium is supplied as KCl.[7] The potassium content of most
plants range from 0.5% to 2% of the harvested weight of crops, conventionally
expressed as amount of K
2O. Modern high-yield agriculture depends upon fertilizers to replace the potassium
lost at harvest. Most agricultural fertilizers contain potassium chloride, while
potassium sulfate is used for chloride-sensitive crops or crops needing higher sulfur
content. The sulfate is produced mostly by decomposition of the complex
minerals kainite (MgSO
4KCl3H
2O) and langbeinite (MgSO
4K
2SO
4).
Only a very few fertilizers contain potassium nitrate.[85] In 2005, about 93% of
world potassium production was consumed by the fertilizer industry.[46]

Food

The potassium cation is a nutrient necessary for human life and health. Potassium
chloride and bicarbonate are used by those seeking to
control hypertension.[86] The USDA lists tomato paste, orange juice, beet greens, white
beans, potatoes, bananas and many other dietary sources of potassium, ranked in
descending order according to potassium content.[87]

Potassium sodium tartrate (KNaC


4H
4O
6, Rochelle salt) is the main constituent of baking powder; it is also used in
the silvering of mirrors. Potassium bromate (KBrO
3) is a strong oxidizer (E924), used to improve dough strength and rise
height. Potassium bisulfite (KHSO
3) is used as a food preservative, for example in wine and beer-making (but not in
meats). It is also used to bleach textiles and straw, and in the tanning of leathers.[88][89]

Industrial

Major potassium chemicals are potassium hydroxide, potassium carbonate, potassium


sulfate, and potassium chloride. Megatons of these compounds are produced
annually.[90]

Potassium hydroxide KOH is a strong base, which is used in industry to neutralize


strong and weak acids, to control pH and to manufacture potassium salts. It is also
used to saponify fats and oils, in industrial cleaners, and in hydrolysis reactions, for
example of esters.[91][92]

Potassium nitrate (KNO


3) or saltpeter is obtained from natural sources such as guano and evaporites or
manufactured via the Haber process; it is the oxidant in gunpowder (black powder)
and an important agricultural fertilizer. Potassium cyanide (KCN) is used industrially
to dissolve copper and precious metals, in particular silver and gold, by
forming complexes. Its applications include gold mining, electroplating,
and electroforming of these metals; it is also used in organic synthesis to
make nitriles. Potassium carbonate (K
2CO
3 or potash) is used in the manufacture of glass, soap, color TV tubes, fluorescent
lamps, textile dyes and pigments.[93] Potassium permanganate (KMnO
4) is an oxidizing, bleaching and purification substance and is used for production
of saccharin. Potassium chlorate (KClO
3) is added to matches and explosives. Potassium bromide (KBr) was formerly used as
a sedative and in photography.[7]

Potassium chromate (K
2CrO
4) is used in inks, dyes, stains (bright yellowish-red color);
in explosives and fireworks; in the tanning of leather, in fly paper and safety
matches,[94] but all these uses are due to the properties of chromate ion containment
rather than potassium ions.

Niche uses

There are thousands of uses of various potassium compounds. One example


is potassium superoxide, KO
2, an orange solid that acts as a portable source of oxygen and a carbon dioxide
absorber. It is widely used in respiration systems in mines, submarines and spacecraft
as it takes less volume than the gaseous oxygen.[95][96]

4 KO
2 + 2 CO2 2 K
2CO
3+3O
2

Another example is potassium cobaltinitrite, K


3[Co(NO
2)
6] which is used as artist's pigment under the name of Aureolin or Cobalt Yellow.[97]

Laboratory uses

An alloy of sodium and potassium, NaK is a liquid used as a heat-transfer medium


and a desiccant for producing dry and air-free solvents. It can also be used in reactive
distillation.[98] The ternary alloy of 12% Na, 47% K and 41% Cs has the lowest melting
point of 78 C of any metallic compound.[8]

Metallic potassium is used in several types of magnetometers.[99]


Precautions

A reaction of potassium metal with water. Hydrogen is liberated that burns with a
pink or lilac flame, the flame color owing to burning potassium vapor. Strongly
alkaline potassium hydroxide is formed in solution.

Potassium metal reacts very violently with water producing potassium


hydroxide (KOH) and hydrogen gas.

2 K (s) + 2 H2O (l) 2 KOH (aq) + H


2 (g)

This reaction is exothermic and releases enough heat to ignite the resulting hydrogen.
It in turn may explode in the presence of oxygen. Potassium hydroxide is a
strong alkali that causes skin burns. Finely divided potassium will ignite in air at room
temperature. The bulk metal will ignite in air if heated. Because its density is 0.89
g/cm3, burning potassium floats in water that exposes it to atmospheric oxygen. Many
common fire extinguishing agents, including water, either are ineffective or make a
potassium fire worse. Nitrogen, argon, sodium chloride (table salt), sodium
carbonate (soda ash), and silicon dioxide (sand) are effective if they are dry.
Some Class D dry powder extinguishers designed for metal fires are also effective.
These agents deprive the fire of oxygen and cool the potassium metal.[100]

Potassium reacts violently with halogens and will detonate in the presence of bromine.
It also reacts explosively with sulfuric acid. During combustion potassium forms
peroxides and superoxides. These peroxides may react violently with organic
compounds such as oils. Both peroxides and superoxides may react explosively with
metallic potassium.[101]

Because potassium reacts with water vapor present in the air, it is usually stored under
anhydrous mineral oil or kerosene. Unlike lithium and sodium, however, potassium
should not be stored under oil for longer than 6 months, unless in an inert (oxygen
free) atmosphere, or under vacuum. After prolonged storage in air dangerous shock-
sensitive peroxides can form on the metal and under the lid of the container, and can
detonate upon opening.[102]

Because of the highly reactive nature of potassium metal, it must be handled with
great care, with full skin and eye protection and preferably an explosion-resistant
barrier between the user and the metal. Ingestion of large amounts of potassium
compounds can lead to hyperkalemia strongly influencing the cardiovascular
system.[103][104] Potassium chloride is used in the United States for executions vialethal
injection.[103]

Calcium
From Wikipedia, the free encyclopedia
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This article is about the metallic element. For the place, see Calcium, New York.

Calcium, Ca 20

Spectral lines of calcium

General properties

Name, symbol calcium, Ca

Appearance dull gray, silver

Pronunciation /klsim/
KAL-see-m
Calcium in the periodic table

Mg

Ca

Sr

potassium calcium scandium

Atomic number 20

Standard atomic weight () (Ar) 40.078(4)[1]

Element category alkaline earth metal

Group, block group 2 (alkaline earth metals),s-block

Period period 4

Electron configuration [Ar] 4s2

per shell 2, 8, 8, 2

Physical properties

Phase solid

Melting point 1115 K (842 C, 1548 F)

Boiling point 1757 K (1484 C, 2703 F)

Density near r.t. 1.55 g/cm3

when liquid, at m.p. 1.378 g/cm3

Heat of fusion 8.54 kJ/mol


Heat of vaporization 154.7 kJ/mol

Molar heat capacity 25.929 J/(molK)

vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 864 956 1071 1227 1443 1755

Atomic properties

Oxidation states +2, +1, 1[2] (a strongly basicoxide)

Electronegativity Pauling scale: 1.00

Ionization energies 1st: 589.8 kJ/mol


2nd: 1145.4 kJ/mol
3rd: 4912.4 kJ/mol
(more)

Atomic radius empirical: 197 pm

Covalent radius 17610 pm

Van der Waals radius 231 pm

Miscellanea

Crystal structure face-centered cubic (fcc)

Speed of soundthin rod 3810 m/s (at 20 C)

Thermal expansion 22.3 m/(mK) (at 25 C)


Thermal conductivity 201 W/(mK)

Electrical resistivity 33.6 nm (at 20 C)

Magnetic ordering diamagnetic

Young's modulus 20 GPa

Shear modulus 7.4 GPa

Bulk modulus 17 GPa

Poisson ratio 0.31

Mohs hardness 1.75

Brinell hardness 170416 MPa

CAS Registry Number 7440-70-2

History

Discovery and first isolation Humphry Davy (1808)

Most stable isotopes

Main article: Isotopes of calcium

iso NA half-life DM DE (MeV) DP


40
Ca 96.941% >5.91021 y(++) 0.194 40
Ar
41
Ca trace 1.0310 y
5
41
K
42
Ca 0.647%42Ca is stable with 22 neutrons
43
Ca 0.135%43Ca is stable with 23 neutrons
44
Ca 2.086%44Ca is stable with 24 neutrons
45
Ca syn 162.7 d 0.258 45
Sc
46
Ca 0.004% >8.810 y( ) 0.988
22 46
Ti

0.694, 1.99 47
Sc
47
Ca syn 4.536 d
1.297
4.274 48
Ti
48
Ca 0.187% 4.31019 y
( ) 0.0058 48
Sc

Decay modes in parentheses are predicted, but have not yet been observed

references

Calcium is a chemical element with symbol Ca and atomic number 20. Calcium is a
soft gray alkaline earth metal, fifth-most-abundant element by massin
the Earth's crust. The ion Ca2+ is also the fifth-most-abundant
dissolved ion in seawater by both molarity and mass,
after sodium, chloride,magnesium, and sulfate.[3] Free calcium metal is too reactive to
occur in nature. Calcium is produced in the explosions at the end of the life of massive
stars

Calcium is essential for living organisms, in particular in cell physiology, where


movement of the calcium ion into and out of the cytoplasm functions as a signal for
many cellular processes. As a major material used in mineralization
of bone, teeth and shells, calcium is the most abundant metal by mass in
many animals.

Contents
[hide]

1 Notable characteristics
o 1.1 H and K lines
2 Compounds
3 Isotopes
o 3.1 Isotope fractionation
4 Geochemical cycling
5 History
6 Occurrence
7 Applications
o 7.1 Calcium compounds
8 Nutrition
o 8.1 Dietary supplements
o 8.2 Bone health
o 8.3 Cardiovascular impact
o 8.4 Cancer
9 Hazards and toxicity
10 See also
11 References
12 Further reading
13 External links

Notable characteristics

Flame test. Brick-red color originates from calcium.

In chemical terms, calcium is reactive and soft for a metal; though harder than lead, it
can be cut with a knife with difficulty. It is a silvery metallic element that must be
extracted by electrolysis from a fused salt like calcium chloride.[4] Once produced, it
rapidly forms a gray-white coating of calcium oxide and calcium nitride for reacting
with the oxygen and nitrogen in the air when exposed to it. In bulk form (typically as
chips or "turnings"), the metal is somewhat difficult to ignite, more so even than
magnesium chips; but, when lit, the metal burns in air with a brilliant high-intensity
orange-red light. Calcium metal reacts with water, generating hydrogen gas at a rate
rapid enough to be noticeable, but not fast enough at room temperature to generate
much heat, making it useful for generating hydrogen.[5] In powdered form, however,
the reaction with water is extremely rapid, as the increased surface area of the powder
accelerates the reaction with the water. Part of the reason for the slowness of the
calciumwater reaction is a result of the metal being partly protected by insoluble
white calcium hydroxide; in water solutions of acids, where this salt is soluble,
calcium reacts vigorously.

With a density of 1.54 g/cm3,[6] calcium is the lightest of the alkaline earth metals;
magnesium (specific gravity 1.74) and beryllium (1.84) are denser though lighter in
atomic mass. From strontium onward, the alkali earth metals become denser with
increasing atomic mass.

Calcium has two allotropes.[7]

Calcium has a higher electrical resistivity than copper or aluminium, yet weight-for-
weight, due to its much lower density, it is a better conductor than either. Its use as
such in terrestrial applications is usually limited by its high reactivity with air;
however, it has potential for use as wiring in off-world applications.[8]

Calcium salts are colorless from any contribution of the calcium, and ionic solutions
of calcium (Ca2+) are colorless as well. As with magnesium salts and other alkaline
earth metal salts, calcium salts are often quite soluble in water. Notable exceptions
include calcium hydroxide, calcium sulfate(unusual for sulfate salts), calcium
carbonate and tricalcium phosphate. With the exception of calcium sulfate, even the
insoluble calcium salts listed are in general more soluble than the transition
metal counterparts. When in solution, the calcium ion varies remarkably to the human
taste, being reported as mildly salty, sour, "mineral-like" or even "soothing." It is
apparent that many animals can taste, or develop a taste, for calcium, and use this
sense to detect the mineral in salt licks or other sources.[9] In human nutrition, soluble
calcium salts may be added to tart juices without much effect to the average palate.

Calcium is the fifth-most-abundant element by mass in the human body, where it is an


important cellular ionic messenger with many functions. Calcium also serves as a
structural element in bone. It is the relatively high-atomic-number calcium in the
skeleton that causes bone to be radio-opaque. Of the human body's solid components
after drying and burning of organics (as for example, after cremation), about a third of
the total "mineral" mass remaining is the approximately one kilogram of calcium that
composes the average skeleton (the remainder being mostly phosphorus and oxygen).

H and K lines
Visible spectra of many stars, including the Sun, exhibit strong absorption lines of
singly ionized calcium. Prominent among these are the H-line at 3968.5 and the K
line at 3933.7 of singly ionized calcium, or Ca II. When observing the Sun, or stars
with low temperatures, the prominence of the H and K lines in the visible spectra can
be an indication of strong magnetic activity in the chromosphere. Measurement of
periodic variations of these active regions can also be used to deduce the rotation
periods of these stars.[10]

Compounds
See also: Category:Calcium compounds.

Calcium, combined with phosphate, forming hydroxylapatite, is the mineral portion of


human and animal bones and teeth. The mineral portion of somecorals can also be
transformed into hydroxylapatite.

Calcium forms a family of ionic compounds known as lime; they are all alkaline white
powders (at STP). Calcium carbonate (CaCO3) is one of the common compounds of
calcium and occurs naturally as limestone and chalk. When heated at high temperature
(above 825 C), it forms calcium oxide(CaO), also known as quicklime. When added
to water (H2O), quicklime vigorously reacts (hence its name) to form calcium
hydroxide (Ca(OH)2). Also known as slaked lime, this substance is an inexpensive
base material used throughout the chemical industry. When mixed with sand, it
hardens into amortar and is turned into plaster by carbon dioxide uptake. Mixed with
other compounds, lime forms an important part of Portland cement.

When water percolates through limestone or other soluble carbonate-containing rocks,


it partially dissolves the rock and causes cave formation with their
characteristic stalactites and stalagmites, and also forms hard water. Other important
calcium compounds are calcium nitrate, calcium sulfide,calcium chloride, calcium
carbide, calcium cyanamide and calcium hypochlorite.

A few calcium compounds where calcium is in the oxidation state +1 have also been
investigated recently.[2] Charlotte Froese Fischer predicted that a Ca ion would be
stable; this ion was discovered experimentally in 1987.[11]

Isotopes
Main article: Isotopes of calcium
Calcium has five stable isotopes (40Ca, 42Ca, 43Ca, 44Ca and 46Ca), plus one more isotope
(48Ca) that has such a long half-life that for all practical purposes it can also be
considered stable. The 20% range in relative mass among naturally occurring calcium
isotopes is greater than for any other element except hydrogen and helium. Calcium
also has a cosmogenic isotope, radioactive 41Ca, which has a half-life of 103,000
years. Unlike cosmogenic isotopes that are produced in the atmosphere, 41Ca is
produced by neutron activation of 40Ca. Most of its production is in the upper metre or
so of the soil column, where the cosmogenic neutron flux is still sufficiently
strong. 41Ca has received much attention in stellar studies because it decays to 41K, a
critical indicator of solar-system anomalies.

Ninety-seven percent of naturally occurring calcium is in the form of 40Ca. 40Ca is one
of the daughter products of 40K decay, along with 40Ar. While KAr dating has been
used extensively in thegeological sciences, the prevalence of 40Ca in nature has
impeded its use in dating. Techniques using mass spectrometry and a double spike
isotope dilution have been used for K-Ca age dating.

The most abundant isotope, 40Ca, has a nucleus of 20 protons and 20 neutrons. This is
the heaviest stable isotope of any element that has equal numbers of protons and
neutrons. In supernova explosions, calcium is formed from the reaction of carbon with
various numbers of alpha particles (helium nuclei), until the most common calcium
isotope (containing 10 helium nuclei) has been synthesized.[citation needed]

Isotope fractionation

As with the isotopes of other elements, a variety of processes fractionate, or alter the
relative abundance of, calcium isotopes.[12] The best studied of these processes is the
mass-dependent fractionation of calcium isotopes that accompanies the precipitation
of calcium minerals, such as calcite, aragonite and apatite, from solution. Isotopically
light calcium is preferentially incorporated into minerals, leaving the solution from
which the mineral precipitated enriched in isotopically heavy calcium. At room
temperature the magnitude of this fractionation is roughly 0.25 (0.025%) per atomic
mass unit (AMU). Mass-dependent differences in calcium isotope composition
conventionally are expressed the ratio of two isotopes (usually 44Ca/40Ca) in a sample
compared to the same ratio in a standard reference material. 44Ca/40Ca varies by about
1% among common earth materials.[13]

Calcium isotope fractionation during mineral formation has led to several applications
of calcium isotopes. In particular, the 1997 observation by Skulan and DePaolo[14] that
calcium minerals are isotopically lighter than the solutions from which the minerals
precipitate is the basis of analogous applications in medicine and in
paleooceanography. In animals with skeletons mineralized with calcium the calcium
isotopic composition of soft tissues reflects the relative rate of formation and
dissolution of skeletal mineral. In humans changes in the calcium isotopic
composition of urine have been shown to be related to changes in bone mineral
balance. When the rate of bone formation exceeds the rate of bone resorption, soft
tissue 44Ca/40Ca rises. Soft tissue 44Ca/40Ca falls when bone resorption exceeds bone
formation. Because of this relationship, calcium isotopic measurements of urine or
blood may be useful in the early detection of metabolic bone diseases
like osteoporosis.[15]

A similar system exists in the ocean, where seawater 44Ca/40Ca tends to rise when the
rate of removal of Ca2+ from seawater by mineral precipitation exceeds the input of
new calcium into the ocean, and fall when calcium input exceeds mineral
precipitation. It follows that rising 44Ca/40Ca corresponds to falling seawater
Ca2+ concentration, and falling 44Ca/40Ca corresponds to rising seawater
Ca2+concentration. In 1997 Skulan and DePaolo presented the first evidence of change
in seawater 44Ca/40Ca over geologic time, along with a theoretical explanation of these
changes. More recent papers have confirmed this observation, demonstrating that
seawater Ca2+ concentration is not constant, and that the ocean probably never is in
steady state with respect to its calcium input and output.[16][17]This has important
climatological implications, as the marine calcium cycle is closely tied to the carbon
cycle (see below).

Geochemical cycling
Calcium provides an important link between tectonics, climate and the carbon cycle.
In the simplest terms, uplift of mountains exposes Ca-bearing rocks to chemical
weathering and releases Ca2+ into surface water. This Ca2+ eventually is transported to
the ocean where it reacts with dissolved CO2 to form limestone. Some of this
limestone settles to the sea floor where it is incorporated into new rocks. Dissolved
CO2, along with carbonate and bicarbonate ions, are referred to as dissolved inorganic
carbon (DIC).

Travertine terraces Pamukkale, Turkey


The actual reaction is more complicated and involves the bicarbonate ion (HCO3) that
forms when CO2 reacts with water at seawater pH:

Ca2+
+ 2HCO
3 CaCO
3 (limestone) + CO
2+H
2O

Note that at ocean pH most of the CO2 produced in this reaction is immediately
converted back into HCO
3. The reaction results in a net transport of one molecule of CO 2 from the
ocean/atmosphere into the lithosphere.[18]

The result is that each Ca2+ ion released by chemical weathering ultimately removes
one CO2 molecule from the surficial system (atmosphere, ocean, soils and living
organisms), storing it in carbonate rocks where it is likely to stay for hundreds of
millions of years. The weathering of calcium from rocks thus scrubs CO 2 from the
ocean and atmosphere, exerting a strong long-term effect on climate.[19]Analogous
cycles involving magnesium, and to a much smaller extent strontium and barium,
have the same effect.

As the weathering of limestone (CaCO3) liberates equimolar amounts of Ca2+ and CO2,
it has no net effect on the CO2 content of the atmosphere and ocean. The weathering
of silicate rocks like granite, on the other hand, is a net CO2 sink because it produces
abundant Ca2+ but very little CO2.

History
'Ain Ghazal figure

Lime as building material was used since prehistoric times going as far back as 7000
to 14000 BC.[20] Significant statues made from lime plaster date back into the 7
millennia BC were found in 'Ain Ghazal.[21] The first dated lime kiln dates back to
2500 BC and was found in Khafajah mesopotamia.[22][23] Calcium
(from Latin calx, genitive calcis, meaning "lime")[24] was known as early as the first
century when the Ancient Romans prepared lime as calcium oxide. Literature dating
back to 975 AD notes that plaster of paris (calcium sulfate), is useful for setting
broken bones. It was not isolated until 1808 in England when Sir Humphry
Davy electrolyzed a mixture of lime and mercuric oxide.[25] Calcium metal was not
available in large scale until the beginning of the 20th century.

Occurrence
See also: Category:Calcium minerals.

Calcium is not naturally found in its elemental state. Calcium occurs most commonly
in sedimentary rocks in the minerals calcite, dolomite and gypsum. It also occurs
in igneous and metamorphic rockschiefly in the silicate
minerals: plagioclases, amphiboles, pyroxenes and garnets.

Applications
Calcium is used[26]

as a reducing agent in the extraction of other metals, such


as uranium, zirconium, and thorium.
as a deoxidizer, desulfurizer, or decarbonizer for various ferrous and
nonferrous alloys.
as an alloying agent used in the production
of aluminium, beryllium, copper, lead, and magnesium alloys.
in the making of cements and mortars to be used in construction.
in the making of cheese, where calcium ions influence the activity of rennin in
bringing about the coagulation of milk.

Calcium compounds

See also: Category:Calcium compounds.

Calcium carbonate (CaCO3) is used in manufacturing cement and


mortar, lime, limestone (usually used in the steel industry) and aids in
production in the glass industry. It also has chemical and optical uses as
mineral specimens in toothpastes, for example.
Calcium hydroxide solution (Ca(OH)2) (also known as limewater) is used to
detect the presence of carbon dioxide by being bubbled through a solution. It
turns cloudy where CO2 is present.
Calcium arsenate (Ca3(AsO4)2) is used in insecticides.
Calcium carbide (CaC2) is used to make acetylene gas (for use in
acetylene torches for welding) and in the manufacturing of plastics.
Calcium chloride (CaCl2) is used in ice removal and dust control on dirt roads,
in conditioner for concrete, as an additive in canned tomatoes, and to provide
body for automobile tires.
Calcium citrate (Ca3(C6H5O7)2) is used as a food preservative.
Calcium cyclamate (Ca(C6H11NHSO3)2) is used as a sweetening agent in several
countries. In the United States it is no longer permitted for use because of
suspected cancer-causing properties.[27]
Calcium gluconate (Ca(C6H11O7)2) is used as a food additive and
in vitamin pills.
Calcium hypochlorite (Ca(OCl)2) is used as a swimming pool disinfectant, as
a bleaching agent, as an ingredient in deodorant, and
in algaecide and fungicide.
Calcium permanganate (Ca(MnO4)2) is used in liquid rocket
propellant, textile production, as a water sterilizing agent and in dental
procedures.
Calcium phosphate (Ca3(PO4)2) is used as a supplement
for animal feed, fertilizer, in commercial production
for dough and yeast products, in the manufacture of glass, and in dental
products.
Calcium phosphide (Ca3P2) is used
in fireworks, rodenticide, torpedoes and flares.
Calcium stearate (Ca(C18H35O2)2) is used in the manufacture
of wax crayons, cements, certain kinds of plastics and cosmetics, as a food
additive, in the production of water resistant materials and in the production
of paints.
Calcium sulfate (CaSO42H2O) is used as common blackboard chalk, as well as,
in its hemihydrate form better known as Plaster of Paris.
Calcium tungstate (CaWO4) is used in luminous paints, fluorescent lights and
in X-ray studies.
Hydroxylapatite (Ca5(PO4)3(OH), but is usually written Ca10(PO4)6(OH)2) makes
up seventy percent of bone. Also carbonated-calcium deficient hydroxylapatite
is the main mineral of whichdental enamel and dentin are comprised.
Nutrition
Main articles: Calcium in biology, Calcium metabolism and Disorders of calcium
metabolism
Recommended adequate intake by the IOM for calcium:[28][29]
Age Calcium (mg/day)
06 months 200
712 months 260
13 years 700
48 years 1000
918 years 1300
1950 years 1000
5170 years (male) 1000
5170 years (female) 1200
71+ years 1200

Calcium is an important component of a healthy diet and a mineral necessary for life.
The National Osteoporosis Foundation says, "Calcium plays an important role in
building stronger, denser bones early in life and keeping bones strong and healthy
later in life." Approximately 99 percent of the body's calcium is stored in the bones
and teeth.[30] The rest of the calcium in the body has other important uses, such as
some exocytosis, especially neurotransmitter release, and muscle contraction. In
the electrical conduction system of the heart, calcium replaces sodium as the mineral
that depolarizes the cell, proliferating the action potential. In cardiac muscle, sodium
influx commences an action potential, but during potassium efflux, the cardiac
myocyte experiences calcium influx, prolonging the action potential and creating a
plateau phase of dynamic equilibrium. Long-term calcium deficiency can lead
to rickets and poor blood clotting and in case of a menopausal woman, it can lead
to osteoporosis, in which the bone deteriorates and there is an increased risk of
fractures. While a lifelong deficit can affect bone and tooth formation, over-retention
can cause hypercalcemia (elevated levels of calcium in the blood), impaired kidney
function and decreased absorption of other minerals.[31][32] Several sources suggest a
correlation between high calcium intake (2000 mg per day, or twice the
U.S. recommended daily allowance, equivalent to six or more glasses of milk per day)
and prostate cancer.[33] High calcium intakes or high calcium absorption were
previously thought to contribute to the development of kidney stones. However, a
high calcium intake has been associated with a lower risk for kidney stones in more
recent research.[34][35][36]Vitamin D is needed to absorb calcium.
Dairy products, such as milk and cheese, are a well-known source of calcium. Some
individuals are allergic to dairy products and even more people, in particular those of
non Indo-European descent, are lactose-intolerant, leaving them unable to consume
non-fermented dairy products in quantities larger than about half a liter per serving.
Others, such as vegans, avoid dairy products for ethical and health reasons.

Many good vegetable sources of calcium exist, including seaweeds such


as kelp, wakame and hijiki; nuts and seeds like almonds, hazelnuts, sesame,
and pistachio; blackstrap molasses; beans (especiallysoy
beans); figs; quinoa; okra; rutabaga; broccoli; dandelion leaves; and kale. In addition,
several foods and drinks, such as orange juice, soy milk, tofu, breakfast cereals, and
breads are often fortifiedwith calcium.[37]

Numerous vegetables, notably spinach, chard and rhubarb have a high calcium
content, but they may also contain varying amounts of oxalic acid that binds calcium
and reduces its absorption. The same problem may to a degree affect the absorption of
calcium from amaranth, collard greens, and chicory greens. This process may also be
related to the generation of calcium oxalate.

An overlooked source of calcium is eggshell, which can be ground into a powder and
mixed into food or a glass of water.[38][39][40]

The calcium content of most foods can be found in the USDA National Nutrient
Database.[41]

Dietary supplements

500 milligram calcium supplements made from calcium carbonate

Calcium supplements are used to prevent and to treat calcium deficiencies. Office of
Dietary Supplements (National Institutes of Health) recommends that no more than
600 mg of supplement should be taken at a time because the percent of calcium
absorbed decreases as the amount of calcium in the supplement increases.[28] It is
therefore recommended to spread doses throughout the day.[42]Recommended daily
calcium intake for adults ranges from 1000 to 1300 mg.[42] Calcium supplements may
have side effects such as bloating and constipation in some people. It is suggested that
taking the supplements with food may aid in nullifying these side effects.[42]

Vitamin D is added to some calcium supplements. Proper vitamin D status is


important because vitamin D is converted to a hormone in the body, which then
induces the synthesis of intestinal proteins responsible for calcium absorption.[43]

The absorption of calcium from most food and commonly used dietary
supplements is very similar.[44] This is contrary to what many calcium
supplement manufacturers claim in their promotional materials.
Milk is an excellent source of dietary calcium for those whose bodies tolerate it
because it has a high concentration of calcium and the calcium in milk is
excellently absorbed.[44]
Soymilk and other vegetable milks are usually sold with calcium added so that
their calcium concentration is as high as in milk.
Also different kind of juices boosted with calcium are widely available.
Calcium carbonate is the most common and least expensive calcium
supplement. It should be taken with food, and depends on low pH levels
(acidic) for proper absorption in the intestine.[45] Some studies suggests that the
absorption of calcium from calcium carbonate is similar to the absorption of
calcium from milk.[46][47]
Antacids frequently contain calcium carbonate, and are a commonly used,
inexpensive calcium supplement.
Coral calcium is a salt of calcium derived from fossilized coral reefs. Coral
calcium is composed of calcium carbonate and trace minerals.
Calcium citrate can be taken without food and is the supplement of choice for
individuals with achlorhydria or who are taking histamine-2 blockers or proton-
pump inhibitors.[48] Calcium citrate is about 21% elemental calcium. 1000 mg
will provide 210 mg of calcium. It is more expensive than calcium carbonate
and more of it must be taken to get the same amount of calcium.
Calcium phosphate costs more than calcium carbonate, but less than calcium
citrate. Microcrystalline Hydroxyapatite (MH) is one of several forms of
calcium phosphate used as a dietary supplement. Hydroxyapatite is about 40%
calcium.
Calcium lactate has similar absorption as calcium carbonate,[49] but is more
expensive. Calcium lactate and calcium gluconate are less concentrated forms
of calcium and are not practical oral supplements.[48]

Bone health

Calcium supplementation is generally not necessary for maintaining bone mineral


density, and carries risks and costs that outweigh any benefits.[50]
Cardiovascular impact

A study investigating the effects of personal calcium supplement use on


cardiovascular risk in the Womens Health Initiative Calcium/Vitamin D
Supplementation Study (WHI CaD Study) found a modestly increased risk of
cardiovascular events, particularly myocardial infarction in postmenopausal women.
A broad recommendation of calcium/vitamin D supplements is therefore not
warranted.[51]In contrast, the authors of a 2013 literature review concluded that the
benefits of calcium supplementation, such as on bone health, appear to outweigh any
risk calcium supplementation may theoretically pose to the cardiovascular health.[52]

Cancer

Overall, there is no strong evidence calcium supplementation helps prevent cancer in


people: some studies suggest it might decrease the risk, but others suggest it might
increase the risk. The National Cancer Institute, part of the National Institutes of
Health, does not recommend the use of calcium supplements to prevent any type of
cancer, due to the lack of evidence supporting its use for this purpose.[53]

There is weak evidence calcium supplementation might have a preventative effect


against developing colorectal adenomatous polyps, but the evidence is insufficient to
recommend such supplementation as a beneficial practice.[54]

Hazards and toxicity


Compared with other metals, the calcium ion and most calcium compounds have low
toxicity. This is not surprising given the very high natural abundance of calcium
compounds in the environment and in organisms. Calcium poses few serious
environmental problems, with kidney stones the most common side-effect in clinical
studies. Acute calcium poisoning is rare, and difficult to achieve unless calcium
compounds are administered intravenously. For example, the oral median lethal
dose (LD50) for rats for calcium carbonate and calcium chloride are 6.45[55] and
1.4 g/kg,[56] respectively.

Calcium metal is hazardous because of its sometimes-violent reactions with water and
acids. Calcium metal is found in some drain cleaners, where it functions to generate
heat and calcium hydroxide thatsaponifies the fats and liquefies the proteins (e.g.,
hair) that block drains. When swallowed calcium metal has the same effect on the
mouth, esophagus and stomach, and can be fatal.[57]

Excessive consumption of calcium carbonate antacids/dietary supplements (such as


Tums) over a period of weeks or months can cause milk-alkali syndrome, with
symptoms ranging from hypercalcemiato potentially fatal renal failure. What
constitutes excessive consumption is not well known and, it is presumed, varies a
great deal from person to person. Persons consuming more than 10 grams/day of
CaCO3 (=4 g Ca) are at risk of developing milk-alkali syndrome,[58] but the condition
has been reported in at least one person consuming only 2.5 grams/day of CaCO3 (=1
g Ca), an amount usually considered moderate and safe.[59]

Oral calcium supplements diminish the absorption of thyroxine when taken within
four to six hours of each other.[60] Thus, people taking both calcium and thyroxine run
the risk of inadequate thyroid hormone replacement and thence hypothyroidism if
they take them simultaneously or near-simultaneously.[61][unreliable medical source?]

Excessive[vague] calcium supplementation can be detrimental to cardiovascular health,


especially in men.[62][63]

Scandium
From Wikipedia, the free encyclopedia
Jump to: navigation, search
Not to be confused with Scandinavium.
"Element 21" redirects here. For the golf company, see Element 21 (company).

Scandium, Sc 21

General properties

Name, symbol scandium, Sc

Appearance silvery white

Pronunciation /skndim/
SKAN-dee-m
Scandium in the periodic table



Sc

Y

calcium scandium titanium

Atomic number 21

Standard atomic weight () (Ar) 44.955908(5)[1]

Element category transition metal

Group, block group 3, d-block

Period period 4

Electron configuration [Ar] 3d1 4s2

per shell 2, 8, 9, 2

Physical properties

Phase solid

Melting point 1814 K (1541 C, 2806 F)

Boiling point 3109 K (2836 C, 5136 F)

Density near r.t. 2.985 g/cm3

when liquid, at m.p. 2.80 g/cm3

Heat of fusion 14.1 kJ/mol


Heat of vaporization 332.7 kJ/mol

Molar heat capacity 25.52 J/(molK)

vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 1645 1804 (2006) (2266) (2613) (3101)

Atomic properties

Oxidation states 3, 2,[2] 1[3] (anamphoteric oxide)

Electronegativity Pauling scale: 1.36

Ionization energies 1st: 633.1 kJ/mol


2nd: 1235.0 kJ/mol
3rd: 2388.6 kJ/mol
(more)

Atomic radius empirical: 162 pm

Covalent radius 1707 pm

Van der Waals radius 211 pm

Miscellanea

Crystal structure hexagonal close-packed(hcp)

Thermal expansion , poly: 10.2 m/(mK) (at r.t.)

Thermal conductivity 15.8 W/(mK)

Electrical resistivity , poly: 562 nm (at r.t., calculated)


Magnetic ordering paramagnetic

Young's modulus 74.4 GPa

Shear modulus 29.1 GPa

Bulk modulus 56.6 GPa

Poisson ratio 0.279

Brinell hardness 7361200 MPa

CAS Registry Number 7440-20-2

History

Naming after Scandinavia

Prediction Dmitri Mendeleev (1871)

Discovery and first isolation Lars Fredrik Nilson(1879)

Most stable isotopes

Main article: Isotopes of scandium

iso NA half-life DM DE (MeV) DP


IT 0.2709 44
Sc
44m2
Sc syn 58.61 h 1.0, 1.1, 1.1 Sc
44

44
Ca
45
Sc 100% Sc is stable with 24 neutrons
45

0.3569 46
Ti
46
Sc syn 83.79 d
0.889, 1.120
0.44, 0.60 47
Ti
47
Sc syn 3.3492 d
0.159

0.661 48
Ti
48
Sc syn 43.67 h
0.9, 1.3, 1.0
references

Scandium is a chemical element with symbol Sc and atomic number 21. A silvery-
white metallic d-block element, it has historically been sometimes classified as a rare
earth element, together with yttrium and the lanthanoids. It was discovered in 1879 by
spectral analysis of the minerals euxenite andgadolinite from Scandinavia.

Scandium is present in most of the deposits of rare earth and uranium compounds, but
it is extracted from these ores in only a few mines worldwide. Because of the low
availability and the difficulties in the preparation of metallic scandium, which was
first done in 1937, it took until the 1970s before applications for scandium were
developed. The positive effects of scandium on aluminium alloys were discovered in
the 1970s, and its use in such alloys remains its only major application. The global
trade of the pure metal is around fifty kilograms per year on average.[4]

The properties of scandium compounds are intermediate between those


of aluminium and yttrium. A diagonal relationship exists between the behavior
of magnesium and scandium, just as there is between beryllium and aluminium. In the
chemical compounds of the elements in group 3, the predominantoxidation state is +3.

Contents
[hide]

1 Properties
o 1.1 Chemical characteristics of the element
o 1.2 Isotopes
o 1.3 Occurrence
2 Production
3 Compounds
o 3.1 Oxides and hydroxides
o 3.2 Halides and pseudohalides
o 3.3 Organic derivatives
o 3.4 Uncommon oxidation states
4 History
5 Applications
6 Health and safety
7 See also
8 References
9 Further reading
10 External links

Properties
Chemical characteristics of the element

Scandium is a soft metal with a silvery appearance. It develops a slightly yellowish or


pinkish cast when oxidized by air. It is susceptible to weathering and dissolves slowly
in most dilute acids. It does not react with a 1:1 mixture of nitric acid (HNO3) and
48% hydrofluoric acid (HF), possibly due to the formation of an impermeable passive
layer. Scandium turnings ignite in air with a brilliant yellow flame to
form scandium(III) oxide.[5]

Isotopes

Main article: Isotopes of scandium

Scandium exists naturally exclusively as the isotope 45Sc, which has a nuclear spin of
7/2. Thirteen radioisotopes have been characterized with the most stable being 46Sc
with a half-life of 83.8 days, 47Sc with a half-life of 3.35 days,the positron
emitter 44Sc with a half-live of 4 h, and 48Sc with a half-life of 43.7 hours. All of the
remaining radioactive isotopes have half-lives that are less than 4 hours, and the
majority of these have half-lives that are less than 2 minutes. This element also has
five meta states with the most stable being 44mSc (t1/2 = 58.6 h).[6]

The isotopes of scandium range from 36Sc to 60Sc. The primary decay mode at masses
lower than the only stable isotope, 45Sc, is electron capture, and the primary mode at
masses above it is beta emission. The primary decay products at atomic weights
below 45Sc are calcium isotopes and the primary products from higher atomic weights
are titanium isotopes.[6]

Occurrence

In terms of Earth's crust, scandium is not particularly rare. Estimates vary from 18 to
25 ppm, which is comparable to the abundance of cobalt (2030 ppm). Scandium is
only the 50th most common element on Earth (35th most abundant in the crust), but it
is the 23rd most common element in theSun.[7] However, scandium is distributed
sparsely and occurs in trace amounts in many minerals.[8] Rare minerals from
Scandinavia[9] andMadagascar[10] such as thortveitite, euxenite, and gadolinite are the
only known concentrated sources of this element. Thortveitite can contain up to 45%
of scandium in the form of scandium(III) oxide.[9]
The stable form of scandium is created in supernovas via the r-process.[11]

Production
World production of scandium is in the order of 2 tonnes per year in the form
of scandium oxide. The primary production is 400 kg while the rest is from stockpiles
that Russia generated during the Cold War. In 2003, only three mines produced
scandium: the uranium and iron mines in Zhovti Vodyin Ukraine, the rare earth mines
in Bayan Obo, China, and the apatite mines in the Kola peninsula, Russia. In each
case scandium is a byproduct from the extraction of other elements[12] and is sold as
scandium oxide.

The production of metallic scandium is in the order of 10 kg per year.[12][13] The oxide is
converted to scandium fluoride and reduced with metalliccalcium.

Madagascar and Iveland-Evje region in Norway have the only deposits of minerals
with high scandium content, thortveitite (Sc,Y)2(Si2O7) andkolbeckite ScPO42H2O, but
these are not being exploited.[13]

The absence of reliable, secure, stable and long term production has limited
commercial applications of scandium. Despite this low level of use, scandium offers
significant benefits. Particularly promising is the strengthening of aluminium alloys
with as little as 0.5% scandium. Scandium-stabilized zirconia enjoys a growing
market demand for use as a high efficiency electrolyte in solid oxide fuel cells.

Compounds
See also: the categories Scandium compounds and Scandium minerals.

The chemistry is almost completely dominated by the trivalent ion, Sc3+. The radii of
M3+ ions in the table below indicate that in terms of chemical properties, scandium
ions are more similar to those of yttrium than to those of aluminium. In part because
of this similarity, scandium is often classified as a lanthanide-like element.

Ionic radii (pm)


Al Sc Y La Lu
53.5 74.5 90.0 103.2 86.1

Oxides and hydroxides

The oxide Sc2O3 and the hydroxide Sc(OH)3 are amphoteric:[14]


Sc(OH)3 + 3 OH Sc(OH)3
6
Sc(OH)3 + 3 H+ + 3 H2O [Sc(H2O)6]3+

The - and - forms of scandium oxide hydroxide (ScO(OH)), are isostructural with
their aluminium oxide hydroxide counterparts.[15] Solutions of Sc3+in water are acidic
because of hydrolysis.

Halides and pseudohalides

The halides ScX3 (X = Cl, Br, I) are very soluble in water, but ScF3 is insoluble. In all
four halides the scandium is 6-coordinated. The halides are Lewis acids; for
example, ScF3 dissolves in a solution containing excess fluoride ion to form [ScF6]3.
The coordination number 6 is typical of Sc(III). In the larger Y3+ and
La3+ ions, coordination numbers of 8 and 9 are common. Scandium(III) triflate is
sometimes used as a Lewis acid catalyst in organic chemistry.

Organic derivatives

Main article: Organoscandium chemistry

Scandium forms a series of organometallic compounds with cyclopentadienyl ligands


(Cp), similar to the behavior of the lanthanides. One example is the chlorine-bridged
dimer, [ScCp2Cl]2 and related derivatives of pentamethylcyclopentadienyl ligands.[16]

Uncommon oxidation states

Compounds that feature scandium in the oxidation state other than +3 are rare but well
characterized. The blue-black compound CsScCl3 is one of the simplest. This material
adopts a sheet-like structure that exhibits extensive bonding between the scandium(II)
centers.[17] Scandium hydride is not well understood, although it appears not to be
a saline hydride of Sc(II).[2] As is observed for most elements, a diatomic scandium
hydride has been observed spectroscopically at high temperatures in the gas
phase.[3] Scandium borides and carbides are non-stoichiometric, as is typical for
neighboring elements.[18]

Lower oxidation states (+2, +1, 0) have also been observed in organoscandium
compounds.[19][20][21][22]

History
Dmitri Mendeleev, who is referred to as the father of the periodic table, predicted the
existence of an element ekaboron, with an atomic mass between 40 and 48 in
1869. Lars Fredrik Nilson and his teamdetected this element in the
minerals euxenite and gadolinite. Nilson prepared 2 grams of scandium oxide of high
purity.[23][24] He named the element scandium, from the Latin Scandia meaning
"Scandinavia". Nilson was apparently unaware of Mendeleev's prediction, but Per
Teodor Cleve recognized the correspondence and notified Mendeleev.[25]

Metallic scandium was produced for the first time in 1937 by electrolysis of
a eutectic mixture of potassium, lithium, and scandium chlorides, at 700
800 C.[26] The first pound of 99% pure scandium metal was produced in 1960. The use
for aluminium alloys began in 1971, following a US patent.[27] Aluminium-scandium
alloys were also developed in the USSR.[28]

Laser crystals of gadolinium-scandium-gallium garnet (GSGG) were used in strategic


defense applications developed in the Strategic Defense Initiative (SDI) in the 1980s
and the 1990s.[29][30]

Applications

Parts of the MiG-29 are made from Al-Sc alloy.[31]

The addition of scandium to aluminium limits the excessive grain growth that occurs
in the heat-affected zone of welded aluminium components. This has two beneficial
effects: the precipitated Al3Sc forms smaller crystals than are found in
other aluminium alloys,[31] and the volume of precipitate-free zones that normally exist
at the grain boundaries of age-hardening aluminium alloys is reduced.[31]Both of these
effects increase the usefulness of the alloy.[why?] However, titanium alloys, which are
similar in lightness and strength, are cheaper and much more widely used.[32]

An alloy called Al20Li20Mg10Sc20Ti30 has been shown to be as strong as titanium, light as


aluminium, and hard as ceramic.[33]

The main application of scandium by weight is in aluminium-scandium alloys for


minor aerospace industry components. These alloys contain between 0.1% and 0.5%
of scandium. They were used in the Russian military aircraft, specifically the MiG-
21 and MiG-29.[31]

Some items of sports equipment, which rely on high performance materials, have been
made with scandium-aluminium alloys, including baseball
bats,[34] and bicycle[35] frames and components.Lacrosse sticks are also made with
scandium. The American firearm manufacturing company Smith & Wesson produces
revolvers with frames composed of scandium alloy and cylinders of titanium or
carbon steel.[36][37]

Dentists use erbium, chromium: yttrium-scandium-gallium garnet (Er,Cr:YSGG)


lasers for cavity preparation and in endodontics.[38]

The first scandium-based metal halide lamps were patented by General Electric and
initially made in North America, although they are now produced in all major
industrialized countries. Approximately 20 kg (as Sc2O3) of scandium is used annually
in the United States to make high-intensity discharge lamps.[39] Scandium iodide, along
with sodium iodide, when added to a modified form of mercury-vapor lamp, produces
a form of metal halide lamp. This lamp is a white light source with high color
rendering index that sufficiently resembles sunlight to allow good color-reproduction
with TVcameras.[40] About 80 kg of scandium is used in metal halide lamps/light bulbs
globally per year.

The radioactive isotope 46Sc is used in oil refineries as a tracing agent.[39] Scandium
triflate is a catalytic Lewis acid used in organic chemistry.[41]

Health and safety


Elemental scandium is considered non-toxic and little animal testing of scandium
compounds has been done.[42] The median lethal dose (LD50) levels for scandium(III)
chloride for rats have been determined as 4 mg/kg for intraperitoneal and 755 mg/kg
for oral administration.[43] In the light of these results compounds of scandium should
be handled as compounds of moderate toxicity.

Titanium
From Wikipedia, the free encyclopedia
Jump to: navigation, search
This article is about the chemical element. For other uses, see Titanium
(disambiguation).
Titanium, Ti 22

General properties

Name, symbol titanium, Ti

Appearance silvery grey-white metallic

Pronunciation /tatenim/
ty-TAY-nee-m

Titanium in the periodic table



Ti

Zr

scandium titanium vanadium

Atomic number 22

Standard atomic weight () (Ar) 47.867(1)[1]

Element category transition metal

Group, block group 4, d-block

Period period 4
Electron configuration [Ar] 3d2 4s2

per shell 2, 8, 10, 2

Physical properties

Phase solid

Melting point 1941 K (1668 C, 3034 F)

Boiling point 3560 K (3287 C, 5949 F)

Density near r.t. 4.506 g/cm3

when liquid, at m.p. 4.11 g/cm3

Heat of fusion 14.15 kJ/mol

Heat of vaporization 425 kJ/mol

Molar heat capacity 25.060 J/(molK)

vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 1982 2171 (2403) 2692 3064 3558

Atomic properties

Oxidation states 4, 3, 2, 1[2] (anamphoteric oxide)

Electronegativity Pauling scale: 1.54

Ionization energies 1st: 658.8 kJ/mol


2nd: 1309.8 kJ/mol
3rd: 2652.5 kJ/mol
(more)
Atomic radius empirical: 147 pm

Covalent radius 1608 pm

Miscellanea

Crystal structure hexagonal close-packed(hcp)

Speed of soundthin rod 5090 m/s (at r.t.)

Thermal expansion 8.6 m/(mK) (at 25 C)

Thermal conductivity 21.9 W/(mK)

Electrical resistivity 420 nm (at 20 C)

Magnetic ordering paramagnetic

Young's modulus 116 GPa

Shear modulus 44 GPa

Bulk modulus 110 GPa

Poisson ratio 0.32

Mohs hardness 6.0

Vickers hardness 8303420 MPa

Brinell hardness 7162770 MPa

CAS Registry Number 7440-32-6


History

Discovery William Gregor (1791)

First isolation Jns Jakob Berzelius(1825)

Named by Martin Heinrich Klaproth(1795)

Most stable isotopes

Main article: Isotopes of titanium

iso NA half-life DM DE (MeV) DP


44
Sc
44
Ti syn 63 y
0.07D, 0.08D
46
Ti 8.0%46Ti is stable with 24 neutrons
47
Ti 7.3%47Ti is stable with 25 neutrons
48
Ti 73.8%48Ti is stable with 26 neutrons
49
Ti 5.5%49Ti is stable with 27 neutrons
50
Ti 5.4%50Ti is stable with 28 neutrons

references

Titanium is a chemical element with symbol Ti and atomic number 22. It is a


lustrous transition metal with a silver color, low density and high strength. It is highly
resistant to corrosion in sea water, aqua regia and chlorine.

Titanium was discovered in Cornwall, Great Britain, by William Gregor in 1791 and
named by Martin Heinrich Klaproth for the Titans of Greek mythology. The element
occurs within a number of mineral deposits, principally rutile and ilmenite, which are
widely distributed in the Earth's crust andlithosphere, and it is found in almost all
living things, rocks, water bodies, and soils.[3] The metal is extracted from its principal
mineral ores via theKroll process[4] or the Hunter process. Its most common
compound, titanium dioxide, is a popular photocatalyst and is used in the manufacture
of white pigments.[5] Other compounds include titanium tetrachloride (TiCl4), a
component of smoke screens and catalysts; and titanium trichloride (TiCl3), which is
used as a catalyst in the production of polypropylene.[3]

Titanium can be alloyed with iron, aluminium, vanadium, and molybdenum, among
other elements, to produce strong, lightweight alloys for aerospace (jet
engines, missiles, and spacecraft), military, industrial process (chemicals and petro-
chemicals, desalination plants, pulp, and paper), automotive, agri-food,
medical prostheses, orthopedic implants, dental and endodontic instruments and
files, dental implants, sporting goods, jewelry, mobile phones, and other
applications.[3]

The two most useful properties of the metal are corrosion resistance and the highest
strength-to-density ratio of any metallic element.[6] In its unalloyed condition, titanium
is as strong as some steels, but less dense.[7] There are two allotropic forms[8] and five
naturally occurring isotopes of this element,46Ti through 50Ti, with 48Ti being the
most abundant (73.8%).[9] Although they have the same number of valence
electrons and are in the same group in the periodic table, titanium
and zirconium differ in many chemical and physical properties.

Contents
[hide]

1 Characteristics
o 1.1 Physical properties
o 1.2 Chemical properties
o 1.3 Occurrence
o 1.4 Isotopes
2 Compounds
o 2.1 Oxides, sulfides, and alkoxides
o 2.2 Nitrides, carbides
o 2.3 Halides
o 2.4 Organometallic complexes
3 History
4 Production and fabrication
5 Applications
o 5.1 Pigments, additives and coatings
o 5.2 Aerospace and marine
o 5.3 Industr