Helium

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From Wikipedia, the free encyclopedia

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This article is about the chemical element. For other uses, see Helium (disambiguation).

"2He" redirects here. For the isotope of helium with two nucleons (2He), see Helium-2.

Helium, 2He

Helium

Pronunciation /ˈhiːliəm/ (HEE-lee-əm)

Appearance colorless gas, exhibiting a gray,

cloudy glow (or reddish-orange if
 an especially high voltage is used)
when placed in an electric field

Standard atomic weight Ar°(He)

 4.002602±0.000002[1]

 4.0026±0.0001 (abridged)[2]

Helium in the periodic table

H
yd
ro
ge
n

LitBe
hi ryl
u liu
mm

SoM
di ag
u ne
m si
u
m

P Ca Sc Tit
ot lci an ani
as u di u
si m u m
u m
m

R St Y Zir
u ro ttr co
bi n iu niu
di ti mm
u u
mm
 C Ba La C Pr N Pr SaE G Te DyH ErTh Y Lu Ha
aeri nt e as eo o m ur ad rb sp ol bi uli tt te fni
si u hari eo dy m ar o oli iu ro mi u u er tiuu
u m n u dy mi et iu pi ni m si u m m bi m m
m u mmi u hi m u u u m u
m u mu mm m m
m m

Fr Ra AcT Pr Ur N Pl A C B Ca Ei F M N La Ru
a di ti h ot an ep ut m ur er lif ns eren o wr th
nc u ni o ac iu tu o er iu keor teim de b en erf
iu m u ri tinim ni ni ici m li ni ni iu lev el ci or
m muu u u u u u u m iu iu u diu
mm m mm mm m m mm m

hydrogen ← helium → lithium

Atomic 2
number (Z)

Group group 18 (noble gases)

Period period 1

Block s-block

Electron 1s2
configuration

Electrons per 2
shell

Physical properties

Phase at STP gas

Boiling point 4.222 K (−268.928 °C, −452.070 °F)

Density (at STP) 0.1786 g/L

when liquid 0.125 g/cm3
(at b.p.)

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 0.0829 kJ/mol

vaporization

Molar heat 20.78 J/(mol·K)[3]

capacity

Vapor pressure (defined by ITS-90)

P (Pa) 1 10 100 1k 10 k 100 k

at T (K) 1.23 1.67 2.48 4.21

Atomic properties

Oxidation states common: (none)

0[4]

Electronegativit Pauling scale: no data

y

Ionization  1st: 2372.3 kJ/mol

energies
 2nd: 5250.5 kJ/mol

Covalent radius 28 pm

Van der Waals 140 pm

radius

Spectral lines of
helium

Other properties
Natural primordial
occurrence

Crystal hexagonal close-packed (hcp)

structure

Thermal 0.1513 W/(m⋅K)

conductivity

Magnetic diamagnetic[5]
ordering

Molar magnetic −1.88×10−6 cm3/mol (298 K)[6]

susceptibility

Speed of sound 972 m/s

CAS Number 7440-59-7

History

Naming after Helios, Greek god of the Sun

Discovery Norman Lockyer (1868)

First isolation William Ramsay, Per Teodor

Cleve, Abraham Langlet (1895)

Isotopes of helium

 v

 e

Main isotopes[7] Decay

abundance half-life (t1/2) mode product

3
He 0.0002% stable

4
He 99.9998% stable

Category: Helium
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Helium (from Greek: ἥλιος, romanized: helios, lit. 'sun') is a chemical element; it
has symbol He and atomic number 2. It is a colorless, odorless, non-
toxic, inert, monatomic gas and the first in the noble gas group in the periodic table.
[a]
Its boiling point is the lowest among all the elements, and it does not have a melting
point at standard pressures. It is the second-lightest and second most abundant element in
the observable universe, after hydrogen. It is 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 in both the Sun and Jupiter, because of 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. The most common isotope of helium in the universe is helium-
4, the vast majority of which was formed during the Big Bang. Large amounts of new helium
are created by nuclear fusion of hydrogen in stars.

Helium was first detected as an unknown, yellow spectral line signature in sunlight during
a solar eclipse in 1868 by Georges Rayet,[15] Captain C. T. Haig,[16] Norman R. Pogson,[17] and
Lieutenant John Herschel,[18] and was subsequently confirmed by French astronomer Jules
Janssen.[19] Janssen is often jointly credited with detecting the element, along with Norman
Lockyer. Janssen recorded the helium spectral line during the solar eclipse of 1868, while
Lockyer observed it from Britain. However, only Lockyer proposed that the line was due to a
new element, which he named after the Sun. The formal discovery of the element was made
in 1895 by chemists Sir William Ramsay, Per Teodor Cleve, and Nils Abraham Langlet, who
found helium emanating from the uranium ore cleveite, which is now not regarded as a
separate mineral species, but as a variety of uraninite.[20][21] In 1903, large reserves of helium
were found in natural gas fields in parts of the United States, by far the largest supplier of
the gas today.

Liquid helium is used in cryogenics (its largest single use, consuming about a quarter of
production), and in the cooling of superconducting magnets, with its main commercial
application in MRI scanners. Helium's other industrial uses—as a pressurizing and purge gas,
as a protective atmosphere for arc welding, and in processes such as growing crystals to
make silicon wafers—account for half of the gas produced. A small but well-known use is as
a lifting gas in balloons and airships.[22] 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 decay of 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 as great as 7% by volume, from which it is extracted commercially by a low-
temperature separation process called fractional distillation. Terrestrial helium is a non-
renewable resource because once released into the atmosphere, it promptly escapes into
space. Its supply is thought to be rapidly diminishing.[23][24] However, some studies suggest
that helium produced deep in the Earth by radioactive decay can collect in natural gas
reserves in larger-than-expected quantities,[25] in some cases having been released by
volcanic activity.[26]

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 the chromosphere of the Sun. The
line was detected by French astronomer Jules Janssen during a total solar eclipse in Guntur,
India.[27][28] 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 because it was near the known D1 and D2 Fraunhofer lines of sodium.[29][30] He
concluded that it was caused by an element in the Sun unknown on Earth. Lockyer named
the element with the Greek word for the Sun, ἥλιος (helios).[31][32] It is sometimes said that
English chemist Edward Frankland was also involved in the naming, but this is unlikely as he
doubted the existence of this new element. The ending "-ium" is unusual, as it normally
applies only to metallic elements; probably Lockyer, being an astronomer, was unaware of
the chemical conventions.[33]

Spectral lines of helium

In 1881, Italian physicist Luigi Palmieri detected helium on Earth for the first time through its
D3 spectral line, when he analyzed a material that had been sublimated during a recent
eruption of Mount Vesuvius.[34]
 Sir William Ramsay, the discoverer of terrestrial helium

The cleveite sample from which Ramsay first purified helium[35]

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.[30][36][37][38] These samples were identified as helium by
Lockyer and British physicist William Crookes.[39][40] 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.[41][42][28]
[43]
Helium was also isolated by 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.[44] His letter of
congratulations to Ramsay offers an interesting case of discovery, and near-discovery, in
science.[45]

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 spectrum of the new gas inside. [46] In
1908, helium was first liquefied by Dutch physicist Heike Kamerlingh Onnes by cooling the
gas to less than 5 K (−268.15 °C; −450.67 °F).[47][48] 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.[49][50]

In 1913, Niels Bohr published his "trilogy"[51][52] on atomic structure that included a
reconsideration of the Pickering–Fowler series as central evidence in support of his model of
the atom.[53][54] This series is named for Edward Charles Pickering, who in 1896 published
observations of previously unknown lines in the spectrum of the star ζ Puppis[55] (these are
now known to occur with Wolf–Rayet and other hot stars).[56] Pickering attributed the
observation (lines at 4551, 5411, and 10123 Å) to a new form of hydrogen with half-integer
transition levels.[57][58] In 1912, Alfred Fowler[59] managed to produce similar lines from a
hydrogen-helium mixture, and supported Pickering's conclusion as to their origin. [60] Bohr's
model does not allow for half-integer transitions (nor does quantum mechanics) and Bohr
concluded that Pickering and Fowler were wrong, and instead assigned these spectral lines
to ionised helium, He+.[61] Fowler was initially skeptical[62] but was ultimately
convinced[63] that Bohr was correct,[51] and by 1915 "spectroscopists had transferred [the
Pickering–Fowler series] definitively [from hydrogen] to helium."[54][64] Bohr's theoretical
work on the Pickering series had demonstrated the need for "a re-examination of problems
that seemed already to have been solved within classical theories" and provided important
confirmation for his atomic theory.[54]

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.
[65]
This phenomenon is related to Bose–Einstein 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 producing superconductivity.[66]

In 1961, Vignos and Fairbank reported the existence of a different phase of solid helium-4,
designated the gamma-phase. It exists for a narrow range of pressure between 1.45 and
1.78 K.[67]

Extraction and use

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discuss the issue on the talk page, or create a new section, as
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 Historical marker, denoting a massive helium find
near Dexter, Kansas

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 (a combustible percentage only with sufficient oxygen),
1% hydrogen, and 12% an unidentifiable gas.[28][68] With further analysis, Cady and McFarland
discovered that 1.84% of the gas sample was helium.[69][70] 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.[71]

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.[30] Some of this gas was used in the world's first helium-filled
airship, the U.S. Navy's C-class blimp C-7, which flew its maiden voyage from Hampton
Roads, Virginia, to Bolling Field in Washington, D.C., on December 1, 1921,[72] nearly two
years before the Navy's first rigid helium-filled airship, the Naval Aircraft Factory-
built USS Shenandoah, flew 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 gas in lighter-than-air craft. During World War II, the demand increased for
helium for lifting gas and for shielded arc welding. The helium mass spectrometer was also
vital in the atomic bomb Manhattan Project.[73]

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.[30] Because of the Helium Act of 1925, which banned the export of
scarce helium on which the US then had a production monopoly, together with the
prohibitive cost of the gas, German Zeppelins were forced to use hydrogen as lifting gas,
which would gain infamy in the Hindenburg disaster. The helium market after 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.[74]

After the Helium Acts Amendments of 1960 (Public Law 86–777), 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, at which time it was further purified.[75]

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 discontinue
the reserve.[28][76] The resulting Helium Privatization Act of 1996[77] (Public Law 104–273)
directed the United States Department of the Interior to empty the reserve, with sales
starting by 2005.[78]

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. [79]

For many years, the United States produced more than 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
metres (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 more than 15 million kg per year.[80] In 2004–2006, additional plants in Ras Laffan, Qatar,
and Skikda, Algeria were built. Algeria quickly became the second leading producer of
helium.[81] Through this time, both helium consumption and the costs of producing helium
increased.[82] From 2002 to 2007 helium prices doubled.[83]

As of 2012, the United States National Helium Reserve accounted for 30 percent of the
world's helium.[84] The reserve was expected to run out of helium in 2018.[84] Despite that, a
proposed bill in the United 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 Texas and Oklahoma. New helium plants were scheduled to
open in 2012 in Qatar, Russia, and the US state of Wyoming, but they were not expected to
ease the shortage.[84]

In 2013, Qatar started up the world's largest helium unit,[85] although the 2017 Qatar
diplomatic crisis severely affected helium production there.[86] 2014 was widely
acknowledged to be a year of over-supply in the helium business, following years of
renowned shortages.[87] Nasdaq reported (2015) that for Air Products, an international
corporation that sells gases for industrial use, helium volumes remain under economic
pressure due to feedstock supply constraints.[88]
Characteristics

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.

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 and (usually) two neutrons. As in
Newtonian mechanics, no system that consists 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.[89] Such models show that each
electron in helium partly screens the nucleus from the other, so that the effective nuclear
charge Zeff which each electron sees is about 1.69 units, not the 2 charges of a classic "bare"
helium nucleus.

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. This arrangement is thus
energetically extremely stable for all these particles and has astrophysical implications.
[90]
Namely, adding another particle – proton, neutron, or alpha particle – would consume
rather than release energy; all systems with mass number 5, as well as beryllium-
8 (comprising two alpha particles), are unbound.[91]

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 that involve either heavy-
particle emission or fusion. Some stable helium-3 (two protons and one neutron) is
produced in fusion reactions from hydrogen, though its estimated abundance in the universe
is about 10−5 relative to helium-4.[92]

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.
Owing to the relatively tight binding of helium-4 nuclei, its production consumed nearly all
of the free neutrons in a few minutes, before they could beta-decay, and thus few neutrons
were available 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, once helium had been formed, no
energetic drive was available to make elements 3, 4 and 5.[93] It is barely energetically
favorable for helium to fuse into the next element with a lower energy per nucleon, carbon.
However, due to the short lifetime of the intermediate beryllium-8, this process requires
three helium nuclei striking each other nearly simultaneously (see triple-alpha process).
[91]
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,
comprises about 24% of the mass of the universe's ordinary matter—nearly all the ordinary
matter that is not hydrogen.[92][94]

Gas and plasma phases

Helium discharge tube shaped into 'He', the element's symbol.

Helium is the second least reactive noble gas after neon, and thus the second least reactive
of all elements.[95] It is chemically 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
these reasons and the small size of helium monatomic molecules, helium diffuses through
solids at a rate three times that of air and around 65% that of hydrogen.[30]

Helium is the least water-soluble monatomic gas,[96] 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
x2/10−5, respectively, versus helium's 0.70797 x2/10−5),[97] and helium's index of refraction is
closer to unity than that of any other gas.[98] 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.[30] Once precooled below this temperature,
helium can be liquefied through expansion cooling.

Most extraterrestrial helium is plasma in stars, 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.[99]

Liquid phase

Main article: Liquid helium

 Phase diagram of helium-4. (Atmospheric

pressure is about 0.1 MPa) Liquefied helium. This helium is

not only liquid, but has been cooled to the point of superfluidity. 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.

Helium liquifies when cooled below 4.2 K at atmospheric pressure. Unlike any other
element, however, helium remains liquid down to a temperature of absolute zero. This is a
direct effect of quantum mechanics: specifically, the zero point energy of the system is too
high to allow freezing. Pressures above about 25 atmospheres are required to freeze it.
There are two liquid phases: Helium I is a conventional liquid, and Helium II, which occurs at
a lower temperature, is a superfluid.