Helium: Difference between revisions
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For many years the United States produced over 90% of commercially usable helium in the world. Extraction plants created in [[Canada]], [[Poland]], [[Russia]], and other nations produced the remaining helium. In the mid 1990s, A new plant in Arzew, Algeria producing 600 million cubic feet (1.7{{e|7}} m<sup>3</sup>) came on stream, with enough production to cover all of Europe's demand. Subsequently, in 2004–2006 two additional plants, one in Ras Laffen, Qatar and the other in Skikda, Algeria were built, but as of early 2007, Ras Laffen is functioning at 50%, and Skikda has yet to start up. Algeria quickly became the second leading producer of helium. Through this time, both helium consumption and the costs of producing helium increased and during 2007 the major suppliers, Air Liquide, Airgas and Praxair all raised prices from 10 to 30%. |
For many years the United States produced over 90% of commercially usable helium in the world. Extraction plants created in [[Canada]], [[Poland]], [[Russia]], and other nations produced the remaining helium. In the mid 1990s, A new plant in Arzew, Algeria producing 600 million cubic feet (1.7{{e|7}} m<sup>3</sup>) came on stream, with enough production to cover all of Europe's demand. Subsequently, in 2004–2006 two additional plants, one in Ras Laffen, Qatar and the other in Skikda, Algeria were built, but as of early 2007, Ras Laffen is functioning at 50%, and Skikda has yet to start up. Algeria quickly became the second leading producer of helium. Through this time, both helium consumption and the costs of producing helium increased and during 2007 the major suppliers, Air Liquide, Airgas and Praxair all raised prices from 10 to 30%. |
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In June [[2008]], construction began in [[Darwin, Australia|Darwin]] on a plant to produce liquified helium, primarily for [[MRI]] medical scanners.<ref>{{cite web |title=Work begins on hemisphere's only helium plant|url=http://www.abc.net.au/news/stories/2008/06/03/2263645.htm}}</ref> |
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==Occurrence and production== |
==Occurrence and production== |
Revision as of 05:12, 3 June 2008
- For other uses of this term, see Helium (disambiguation).
Helium | |||||||||||||||||||||
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Pronunciation | /ˈhiːliəm/ | ||||||||||||||||||||
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) | |||||||||||||||||||||
Helium in the periodic table | |||||||||||||||||||||
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Atomic number (Z) | 2 | ||||||||||||||||||||
Group | group 18 (noble gases) | ||||||||||||||||||||
Period | period 1 | ||||||||||||||||||||
Block | s-block | ||||||||||||||||||||
Electron configuration | 1s2 | ||||||||||||||||||||
Electrons per shell | 2 | ||||||||||||||||||||
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 (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 J/(mol·K)[3] | ||||||||||||||||||||
Vapor pressure (defined by ITS-90)
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Atomic properties | |||||||||||||||||||||
Oxidation states | common: (none) 0[4] | ||||||||||||||||||||
Electronegativity | Pauling scale: no data | ||||||||||||||||||||
Ionization energies |
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Covalent radius | 28 pm | ||||||||||||||||||||
Van der Waals radius | 140 pm | ||||||||||||||||||||
Spectral lines of helium | |||||||||||||||||||||
Other properties | |||||||||||||||||||||
Natural occurrence | primordial | ||||||||||||||||||||
Crystal structure | hexagonal close-packed (hcp) | ||||||||||||||||||||
Thermal conductivity | 0.1513 W/(m⋅K) | ||||||||||||||||||||
Magnetic ordering | diamagnetic[5] | ||||||||||||||||||||
Molar magnetic susceptibility | −1.88×10−6 cm3/mol (298 K)[6] | ||||||||||||||||||||
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 | |||||||||||||||||||||
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Helium (He) is a colorless, odorless, tasteless, non-toxic, inert monatomic chemical element that heads the noble gas series in the periodic table and whose atomic number is 2. Its boiling and melting points are the lowest among the elements and it exists only as a gas except in extreme conditions. Extreme conditions are also needed to create the small handful of helium compounds, which are all unstable at standard temperature and pressure. In its most common form, helium-4, it has two neutrons in its nucleus, while a second, rarer, stable isotope called helium-3 contains just one neutron. The behavior of liquid helium-4's two fluid phases, helium I and helium II, is important to researchers studying quantum mechanics (in particular the phenomenon of superfluidity) and to those looking at the effects that temperatures near absolute zero have on matter (such as superconductivity).
In 1868, the French astronomer Pierre Janssen first detected helium as an unknown yellow spectral line signature in light from a solar eclipse. Since then large reserves of helium have been found in the natural gas fields of the United States, which is by far the largest supplier of the gas. It is used in cryogenics, in deep-sea breathing systems, to cool superconducting magnets, in helium dating, for inflating balloons, for providing lift in airships and as a protective gas for many industrial uses (such as arc welding and growing silicon wafers). A much less serious use is to temporarily change the timbre and quality of one's voice by inhaling a small volume of the gas (for dangers see Biological effects section below).
Helium is the second most abundant and second lightest element in the known universe and is one of the elements believed to have been created in the Big Bang. In the modern universe almost all new helium is created as a result of the nuclear fusion of hydrogen in stars. On Earth helium is rare, and almost all of that which exists was created by the radioactive decay of much heavier elements (alpha particles are helium nuclei). After its creation, part of it was trapped with natural gas in concentrations up to 7% by volume, from which it is extracted commercially by fractional distillation. Large reserves of helium have been found in the natural gas fields of the United States (the largest supplier) but helium is known in gas reserves of a few other countries.
Notable characteristics
Gas and plasma phases
Helium is the least reactive member of the noble gas elements, and thus also the least reactive of all elements; it is inert and monatomic in virtually all conditions. Due to helium's relatively low molar (atomic) mass, in the gas phase its thermal conductivity, specific heat, and sound conduction velocity are all greater than for 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.[8]
Helium is less water soluble than any other gas known[9] and helium's index of refraction is closer to unity than that of any other gas[citation needed]. 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 40 K at 1 atmosphere) does it cool upon free expansion. Once precooled below this temperature, helium can be liquefied through expansion cooling.
Throughout the universe, helium is found mostly in a plasma state whose properties are quite different from atomic helium. In a plasma, helium's electrons and protons are not bound together, 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, they interact with the Earth's magnetosphere giving rise to Birkeland currents and the aurora.
Solid and liquid phases
Helium solidifies only under great pressure. The resulting colorless, almost invisible solid is highly compressible; applying pressure in a laboratory can decrease its volume by more than 30%.[10] With a bulk modulus on the order of 5×107 Pa[11] it is 50 times more compressible than water. Unlike any other element, helium will fail to solidify and remain a 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 1–1.5 K (about −272 °C or −457 °F) and about 25 bar (2.5 MPa) of pressure.[12] It is often hard to distinguish solid from liquid helium since the refractive index of the two phases are nearly the same. The solid has a sharp melting point and has a crystalline structure.
Solid helium has a density of 0.214 ±0.006 g/ml (1.15 K, 66 atm) with a mean isothermal compressibility of the solid at 1.15 K between the solidus and 66 atm of 0.0031 ±0.0008/atm. Also, no difference in density was noted between 1.8 K and 1.5 K. This data projects that T=0 solid helium under 25 bar of pressure (the minimum required to freeze helium) has a density of 0.187 ±0.009 g/ml.[13]
Helium I state
Below its boiling point of 4.22 kelvin and above the lambda point of 2.1768 kelvin, the isotope helium-4 exists in a normal colorless liquid state, called helium I. Like other cryogenic liquids, helium I boils when it is heated. It also contracts when its temperature is lowered until it reaches the lambda point, when it stops boiling and suddenly expands. The rate of expansion decreases below the lambda point until about 1 K is reached; at which point expansion completely stops and helium I starts to contract again.
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.[14] This colorless liquid has a very low viscosity and a density one-eighth that of water, which is only one-fourth the value expected from classical physics.[14] 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 could be explained as an effect of its boiling point being so close to absolute zero, preventing random molecular motion (heat) from masking the atomic properties.[14]
Helium II state
Liquid helium below its lambda point begins to exhibit very unusual characteristics, in a state called helium II. Boiling of helium II is not possible due to its high thermal conductivity; heat input instead causes evaporation of the liquid directly to gas. The isotope 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 helium-3.
Helium II is a superfluid, a quantum-mechanical state of matter with strange properties. For example, when it flows through even capillaries of 10−7 to 10−8 m width it has no measurable viscosity. However, when measurements were done between two moving discs, a viscosity comparable to that of gaseous helium was observed. Current theory explains this using the two-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.[15]
Helium II also exhibits a creeping effect. When a surface extends past the level of helium II, the helium II moves along the surface, seemingly 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.[16][17] 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.[18] These waves are known as third sound.
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.[19]
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. This is because heat conduction occurs by an exceptional quantum-mechanical 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. So when heat is introduced, it will move at 20 meters per second at 1.8 K through helium II as waves in a phenomenon called second sound.[16]
Applications
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. Helium is commercially available in either liquid or gaseous form. As a liquid, it can be supplied in small containers called dewars which hold up to 1,000 liters of helium, or in large ISO containers which have nominal capacities as large as 11,000 gallons (41,637 liters). In gaseous form, small quantities of helium are supplied in high pressure cylinders holding up to 300 standard cubic feet, while large quantities of high pressure gas are supplied in tube trailers which have capacities of up to 180,000 standard cubic feet.
- Because it is lighter than air, airships and balloons are inflated with helium for lift. In airships, helium is preferred over hydrogen because it is not flammable and has 92.64% of the buoyancy (or lifting power) of the alternative hydrogen (see calculation.)
- For its low solubility in water, the major part of human blood, mixtures of helium with oxygen and nitrogen (trimix), with oxygen only (heliox), with common air (heliair), and with hydrogen and oxygen (hydreliox), are used in deep-sea breathing systems to reduce the high-pressure risk of nitrogen narcosis.
- 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 tonnes of liquid helium to maintain the temperature at 1.9 Kelvin.[20] Helium at low temperatures is also used in cryogenics.
- 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 coolant in some nuclear reactors, such as pebble-bed reactors.
- Helium is used as a shielding gas in arc welding processes on materials that are contaminated easily by air. It is especially useful in overhead welding, because it is lighter than air and thus floats, whereas other shielding gases sink.
- Because it is inert, helium is used as a protective gas in growing silicon and germanium crystals, in titanium and zirconium production, in gas chromatography, and as an atmosphere for protecting historical documents. This property also makes it useful in supersonic wind tunnels.
- In rocketry, 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 booster used in the Apollo program needed about 13 million cubic feet (370,000 m³) of helium to launch.[10]
- The gain medium of the helium-neon laser is a mixture of helium and neon.
- Because it diffuses through solids at a rate three times that of air, helium is used as a tracer gas to detect leaks in high-vacuum equipment and high-pressure containers, as well as in other applications with less stringent requirements such as heat exchangers, valves, gas panels, etc.
- Because of its extremely low index of refraction, the use of helium reduces the distorting effects of temperature variations in the space between lenses in some telescopes.
- The age of rocks and minerals that contain uranium and thorium, radioactive elements that emit helium nuclei called alpha particles, can be discovered by measuring the level of helium with a process known as helium dating.
- The high thermal conductivity and sound velocity of helium is also desirable in thermoacoustic refrigeration. The inertness of helium adds to the environmental advantage of this technology over conventional refrigeration systems which may contribute to ozone depleting and global warming effects.
- Because helium alone is less dense than atmospheric air, it will change the timbre (not pitch[21]) of a person's voice when inhaled. However, inhaling it from a typical commercial source, such as that used to fill balloons, can be dangerous due to the risk of asphyxiation from lack of oxygen, and the number of contaminants that may be present. These could include trace amounts of other gases, in addition to aerosolized lubricating oil.
History
Scientific discoveries
Evidence of helium was first detected on August 18, 1868 as a bright yellow line with a wavelength of 587.49 nanometres in the spectrum of the chromosphere of the Sun, by French astronomer Pierre Janssen during a total solar eclipse in Guntur, India. 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 line, for it was near the known D1 and D2 lines of sodium,[22] and concluded that it was caused by an element in the Sun unknown on Earth. He and English chemist Edward Frankland named the element with the Greek word for the Sun, ἥλιος (helios)[23]
On 26 March 1895 British chemist 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, noticed a bright-yellow line that matched the D3 line observed in the spectrum of the Sun.[24][25][26][27][24] These samples were identified as helium by Lockyer and British physicist William Crookes. It was independently isolated from cleveite 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.[28] 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.[29]
In 1907, Ernest Rutherford and Thomas Royds demonstrated that alpha particles are helium nuclei, by allowing them to penetrate the thin glass wall of a 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. He tried to solidify it by further reducing the temperature but failed, because helium does not have a triple point temperature where the solid, liquid, and gas phases are at equilibrium. It was first solidified in 1926 by his student Willem Hendrik Keesom by subjecting helium to 25 atmospheres of pressure.
In 1938, Russian physicist Pyotr Leonidovich Kapitsa discovered that helium-4 (a boson) has almost no viscosity at temperatures near absolute zero, a phenomenon now called superfluidity. 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.
Extraction and uses
After an oil drilling operation in 1903 in Dexter, Kansas, U.S. 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 contained, by volume, 72% nitrogen, 15% methane—insufficient to make the gas combustible, 1% hydrogen, and 12% of an unidentifiable gas.[30] With further analysis, Cady and McFarland discovered that 1.84% of the gas sample was helium.[31] Far from being a rare element, helium was present in vast quantities under the American Great Plains, available for extraction from natural gas.
This put the United States in an excellent position 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 production plants during World War I. The goal was to supply barrage balloons with the non-flammable lifting gas. A total of 200 thousand cubic feet (5,700 m3) of 92% helium was produced in the program even though only a few cubic feet (less than 100 liters) of the gas had previously been obtained.[24] 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 from Hampton Roads, Virginia to Bolling Field in Washington, D.C. on 1 December 1921.[32]
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. This use increased demand during World War II, as well as demands for shielded arc welding. Helium was also vital in the atomic bomb Manhattan Project.
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. Due to a US military embargo against Germany that restricted helium supplies, the Hindenburg 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.
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, when it then was further purified.
By 1995, a billion cubic metres 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.[30][33] The resulting "Helium Privatization Act of 1996"[34] (Public Law 104–273) directed the United States Department of the Interior to start liquidating the reserve by 2005.[35]
Helium produced before 1945 was about 98% 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 99.995% helium were available.
For many years the United States produced over 90% of commercially usable helium in the world. Extraction plants created in Canada, Poland, Russia, and other nations produced the remaining helium. In the mid 1990s, A new plant in Arzew, Algeria producing 600 million cubic feet (1.7×107 m3) came on stream, with enough production to cover all of Europe's demand. Subsequently, in 2004–2006 two additional plants, one in Ras Laffen, Qatar and the other in Skikda, Algeria were built, but as of early 2007, Ras Laffen is functioning at 50%, and Skikda has yet to start up. Algeria quickly became the second leading producer of helium. Through this time, both helium consumption and the costs of producing helium increased and during 2007 the major suppliers, Air Liquide, Airgas and Praxair all raised prices from 10 to 30%.
In June 2008, construction began in Darwin on a plant to produce liquified helium, primarily for MRI medical scanners.[36]
Occurrence and production
Natural abundance
Helium is the second most abundant element in the known Universe after hydrogen and constitutes 23% of the elemental mass of the universe. It is concentrated in stars, where it is formed from hydrogen by the nuclear fusion of the proton-proton chain reaction and CNO cycle. According to the Big Bang model of the early development of the universe, the vast majority of helium was formed during Big Bang nucleosynthesis, from one to three minutes after the Big Bang. As such, measurements of its abundance contribute to cosmological models.
In the Earth's atmosphere, the concentration of helium by volume is only 5.2 parts per million.[37] 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.[38][39] In the Earth's heterosphere, a part of the upper atmosphere, helium and other lighter gases are the most abundant elements.
Nearly all helium on Earth is a result of radioactive decay. The decay product is primarily found in minerals of uranium and thorium, including cleveites, pitchblende, carnotite and monazite, because they emit alpha particles, which consist of helium nuclei (He2+) to which electrons readily combine. In this way an estimated 3.4 litres of helium per year are generated per cubic kilometer of the Earth's crust. 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. The greatest concentrations on the planet are in natural gas, from which most commercial helium is derived.
The world's helium supply may be in danger, according to Washington University in St. Louis chemist Lee Sobotka. The largest reserve is in Texas and would run out in eight years if consumed at the current pace.[40] Helium is non-renewable and irreplaceable by conventional methods. In total, there is currently 25,000 million m³ of helium in reserve bases of various countries.[41]
Modern extraction
For large-scale use, helium is extracted by fractional distillation from natural gas, which contains up to 7% helium.[42] 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.[43] 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.
In 2005, approximately 160 million m³ of helium were extracted from natural gas or withdrawn from helium reserves, with approximately 83% from the United States, 11% from Algeria, and most of the remainder from Russia and Poland. In the United States, most helium is extracted from natural gas in Kansas and Texas.
Diffusion of crude natural gas through special semipermeable membranes and other barriers is another method to recover and purify helium. Helium can be synthesized by bombardment of lithium or boron with high-velocity protons, but this is not an economically viable method of production.
Isotopes
There are eight known isotopes of helium, but only helium-3 and helium-4 are stable. In the Earth's atmosphere, there is one He-3 atom for every million He-4 atoms.[44] 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 during Big Bang nucleosynthesis.
Helium-3 is present on Earth only in trace amounts, most of it since Earth's formation thought some falls to Earth trapped in cosmic dust.[45] Trace amounts are also produced by the beta decay of tritium.[46] 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's mantle.[45] He-3 is much more abundant in stars, as a product of nuclear fusion. Thus in the interstellar medium, the proportion of He-3 is around 100 times higher than on Earth.[47] 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 0.01 ppm.[48][49] A number of people, starting with Gerald Kulcinski in 1986,[50] 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 He-3 and He-4 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).[51] 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 7.6×10−22 seconds. Helium-6 decays by emitting a beta particle and has a half life of 0.8 seconds. Helium-7 also emits a beta particle as well as a gamma ray. Helium-7 and helium-8 are hyperfragments that are created in certain nuclear reactions.[52] Helium-6 and helium-8 are known to exhibit a nuclear halo. Helium-2 (two protons, no neutrons) is a radioisotope that decays by proton emission into protium (hydrogen), with a half-life of 3x10−27 second.[51]
Biological effects
The voice of a person who has inhaled helium temporarily sounds high-pitched. This is because 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.[28] (The opposite effect, lowering frequencies, can be obtained by inhaling sulfur hexafluoride)
Inhaling helium can be dangerous if done to excess, since helium is a simple asphyxiant and so displaces oxygen needed for normal respiration. Breathing pure helium continuously causes death by asphyxiation within minutes. In most mammals (except seals and many burrowing animals) the breathing reflex is triggered by excess of carbon dioxide rather than lack of oxygen, so asphyxiation by helium progresses without the victim experiencing air hunger. Inhaling helium directly from pressurized cylinders is extremely dangerous, as the high flow rate can result in barotrauma, fatally rupturing lung tissue.[53]
Neutral helium at standard conditions is non-toxic, plays no biological role and is found in trace amounts in human blood. 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.[54]
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.[10]
Compounds
Helium is chemically unreactive under all normal conditions due to its valence of zero.[55] It is an electrical insulator unless ionized. As with the other noble gases, helium has metastable energy levels that allow it to remain ionized in an electrical discharge with a voltage below its ionization potential. Helium can form unstable compounds with tungsten, iodine, fluorine, sulfur and phosphorus when it is subjected to an electric glow discharge, through electron bombardment or is otherwise a plasma. HeNe, HgHe10, WHe2 and the molecular ions He2+, He22+, HeH+, and HeD+ have been created this way. This technique has also allowed the production of the neutral molecule He2, which has a large number of band systems, and HgHe, which is apparently only held together by polarization forces.[8] Theoretically, other compounds may also be possible, such as helium fluorohydride (HHeF) which would be analogous to HArF, discovered in 2000.
Helium has been put inside the hollow carbon cage molecules (the fullerenes) by heating under high pressure of the gas. The neutral molecules formed are stable up to high temperatures. When chemical derivatives of these fullerenes are formed, the helium stays inside. If helium-3 is used, it can be readily observed by helium NMR spectroscopy. Many fullerenes containing helium-3 have been reported. Although the helium atoms are not attached by covalent or ionic bonds, these substances fit the definition of compounds in the Handbook of Chemistry and Physics. They are the first stable neutral helium compounds to be formed.
References
- Prose
- The Elements: Third Edition, by John Emsley (New York; Oxford University Press; 1998; pages 94–95) ISBN 0-19-855818-X
- United States Geological Survey (usgs.gov): Mineral Information for Helium (PDF) (viewed 5 January 2007)
- The thermosphere: a part of the heterosphere, by J. Vercheval (viewed 1 April 2005)
- Isotopic Composition and Abundance of Interstellar Neutral Helium Based on Direct Measurements, Zastenker G.N. et al., [1], published in Astrophysics, April 2002, vol. 45, no. 2, pp. 131–142(12)
- Dynamic and thermodynamic properties of solid helium in the reduced all-neighbours approximation of the self-consistent phonon theory, C. Malinowska-Adamska, P. Sŀoma, J. Tomaszewski, physica status solidi (b), Volume 240, Issue 1 , Pages 55–67; Published Online: 19 September 2003
- The Two Fluid Model of Superfluid Helium, S. Yuan, (viewed 4 April 2005)
- Rollin Film Rates in Liquid Helium, Henry A. Fairbank and C. T. Lane, Phys. Rev. 76, 1209–1211 (1949), from the online archive
- Introduction to Liquid Helium, at the NASA Goddard Space Flight Center (viewed 4 April 2005)
- Tests of vacuum VS helium in a solar telescope, Engvold, O.; Dunn, R. B.; Smartt, R. N.; Livingston, W. C.. Applied Optics, vol. 22, 1 January 1983, p. 10–12
- Bureau of Mines (1967). Minerals yearbook mineral fuels Year 1965, Volume II (1967). U. S. Government Printing Office.
- Helium: Fundamental models, Don L. Anderson, Gillian Foulger & Anders Meibom (viewed 5 April 2005)
- High Pressure Nervous Syndrome, Diving Medicine Online (viewed 5 April 2005)
- Table
- Nuclides and Isotopes Fourteenth Edition: Chart of the Nuclides, General Electric Company, 1989
- WebElements.com and EnvironmentalChemistry.com per the guidelines at Wikipedia's WikiProject Elements (viewed 10 October 2002)
Notes
- ^ "Standard Atomic Weights: Helium". CIAAW. 1983.
- ^ Prohaska, Thomas; Irrgeher, Johanna; Benefield, Jacqueline; Böhlke, John K.; Chesson, Lesley A.; Coplen, Tyler B.; Ding, Tiping; Dunn, Philip J. H.; Gröning, Manfred; Holden, Norman E.; Meijer, Harro A. J. (2022-05-04). "Standard atomic weights of the elements 2021 (IUPAC Technical Report)". Pure and Applied Chemistry. doi:10.1515/pac-2019-0603. ISSN 1365-3075.
- ^ Shuen-Chen Hwang, Robert D. Lein, Daniel A. Morgan (2005). "Noble Gases". Kirk Othmer Encyclopedia of Chemical Technology. Wiley. pp. 343–383. doi:10.1002/0471238961.0701190508230114.a01.
- ^ Disodium helide, (Na+)2He(e-)2, has been synthesized at high pressure, see Dong, Xiao; Oganov, Artem R.; Goncharov, Alexander F.; Stavrou, Elissaios; Lobanov, Sergey; Saleh, Gabriele; Qian, Guang-Rui; Zhu, Qiang; Gatti, Carlo; Deringer, Volker L.; Dronskowski, Richard; Zhou, Xiang-Feng; Prakapenka, Vitali B.; Konôpková, Zuzana; Popov, Ivan A.; Boldyrev, Alexander I.; Wang, Hui-Tian (6 February 2017). "A stable compound of helium and sodium at high pressure". Nature Chemistry. 9 (5): 440–445. arXiv:1309.3827. Bibcode:2017NatCh...9..440D. doi:10.1038/nchem.2716. PMID 28430195. S2CID 20459726.
- ^ Magnetic susceptibility of the elements and inorganic compounds, in Handbook of Chemistry and Physics 81st edition, CRC press.
- ^ Weast, Robert (1984). CRC, Handbook of Chemistry and Physics. Boca Raton, Florida: Chemical Rubber Company Publishing. pp. E110. ISBN 0-8493-0464-4.
- ^ Kondev, F. G.; Wang, M.; Huang, W. J.; Naimi, S.; Audi, G. (2021). "The NUBASE2020 evaluation of nuclear properties" (PDF). Chinese Physics C. 45 (3): 030001. doi:10.1088/1674-1137/abddae.
- ^ a b The Encyclopedia of the Chemical Elements, edited by Cifford A. Hampel, "Helium" entry by L. W. Brandt (New York; Reinhold Book Corporation; 1968; page 261) Library of Congress Catalog Card Number: 68-29938
- ^ Helium (He) and water
- ^ a b c Los Alamos National Laboratory (LANL.gov): Periodic Table, "Helium" (viewed 10 October 2002 and 25 March 2005)
- ^ C. Malinowska-Adamska, P. Soma, J. Tomaszewski. "Dynamic and thermodynamic properties of solid helium in the reduced all-neighbours approximation of the self-consistent phonon theory". physica status solidi (b). 240 (1): 55–67. doi:10.1002/pssb.200301871.
{{cite journal}}
: CS1 maint: multiple names: authors list (link) - ^ Solid Helium, Dept. of Physics, at the University of Alberta
- ^ Structure of Solid Helium by Neutron Diffraction, D. G. Henshaw, Physical Review Letters 109, Pg. 328 – 330 (Issue 2 – January 1958)
- ^ a b c The Encyclopedia of the Chemical Elements, page 262
- ^ Yuan, Sidney. The Two Fluid Model of Superfluid Helium (He II, Superfluidity). Yutiopian.com. Retrieved on 5 January 2007.
- ^ a b The Encyclopedia of the Chemical Elements, page 263
- ^ "Rollin Film Rates in Liquid Helium". Physical Review. 76 (8): 1209–1211. October 1949. doi:10.1103/PhysRev.76.1209.
{{cite journal}}
: Unknown parameter|authors=
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ignored (help)CS1 maint: date and year (link) - ^ Ellis, Fred M. Third sounds. Wesleyan Quantum Fluids Laboratory. Retrieved on 2007-11-08.
- ^ Warner, Brent. "Introduction to Liquid Helium". NASA. Archived from the original on 2005-09-01. Retrieved 2007-01-05.
- ^ LHC Guide booklet "CERN - LHC: Facts and Figures". CERN. Retrieved 2008-04-30.
{{cite web}}
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value (help) - ^ Physics in speech, phys.unsw.edu.au. Retrieved on 5 January 2007.
- ^ The Encyclopedia of the Chemical Elements, page 256
- ^ Oxford English Dictionary (1989), s.v. "helium". Retrieved on December 16, 2006, from Oxford English Dictionary Online. Also, from quotation there: Thomson, W. (1872). Rep. Brit. Assoc. xcix: "Frankland and Lockyer find the yellow prominences to give a very decided bright line not far from D, but hitherto not identified with any terrestrial flame. It seems to indicate a new substance, which they propose to call Helium."
- ^ a b c The Encyclopedia of the Chemical Elements, page 257
- ^ William Ramsay (1895). "On a Gas Showing the Spectrum of Helium, the Reputed Cause of D3 , One of the Lines in the Coronal Spectrum. Preliminary Note". Proceedings of the Royal Society of London. 58: 65–67.
- ^ William Ramsay (1895). "Helium, a Gaseous Constituent of Certain Minerals. Part I". Proceedings of the Royal Society of London. 58: 80–89.
- ^ William Ramsay (1895). "Helium, a Gaseous Constituent of Certain Minerals. Part II--". Proceedings of the Royal Society of London. 59: 325–330.
- ^ a b Emsley, Nature's Building Blocks, 177
- ^ Pat Munday (1999). Biographical entry for W.F. Hillebrand (1853–1925), geochemist and US Bureau of Standards administrator in American National Biography, ed. John A. Garraty and Mark C. Carnes, 24 vols. (Oxford University Press: 1999): v. 10, pp. 808–9; v. 11, pp. 227-8.
- ^ a b Emsley, Nature's Building Blocks, 179
- ^ American Chemical Society (2004). "The Discovery of Helium in Natural Gas". Retrieved 2006-05-17.
- ^ Eugene M. Emme, comp., ed. (1961). "Aeronautics and Astronautics Chronology, 1920–1924". Aeronautics and Astronautics: An American Chronology of Science and Technology in the Exploration of Space, 1915–1960. Washington, DC: NASA. pp. 11–19.
{{cite book}}
:|access-date=
requires|url=
(help); External link in
(help); Unknown parameter|chapterurl=
|chapterurl=
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suggested) (help) - ^ Guide to the Elements: Revised Edition, by Albert Stwertka (New York; Oxford University Press; 1998; page 24) ISBN 0-19-512708-0
- ^ "Helium Privatization Act of 1996". Retrieved 2007-01-05.
- ^ Executive Summary, nap.edu. Retrieved on 5 January 2007.
- ^ "Work begins on hemisphere's only helium plant".
- ^ "The Atmosphere: Introduction". JetStream - Online School for Weather. National Weather Service.
- ^ Lie-Svendsen, Ø.; Rees, M. H. (1996). "Helium escape from the terrestrial atmosphere: The ion outflow mechanism". Journal of Geophysical Research. 101 (A2): 2435–2444. doi:10.1029/95JA02208.
{{cite journal}}
: CS1 maint: multiple names: authors list (link) - ^ Strobel, Nick (2007). "Nick Strobel's Astronomy Notes". Retrieved 2007-09-25.
{{cite web}}
:|chapter=
ignored (help) - ^ Helium supplies endangered, threatening science and technology
- ^ U.S. Geological Survey, Mineral Commodity Summaries, January 2004
- ^ WebElements Periodic Table: Professional Edition: Helium: key information
- ^ The Encyclopedia of the Chemical Elements, page 258
- ^ Emsley, John. Nature's Building Blocks: An A-Z Guide to the Elements. Oxford: Oxford University Press, 2001. Page 178. ISBN 0-19-850340-7
- ^ a b Helium Fundamentals
- ^ Periodic Table of Elements: Li - Lithium (EnvironmentalChemistry.com)
- ^ "Isotopic Composition and Abundance of Interstellar Neutral Helium Based on Direct Measurements". Astrophysics. 45 (2): 131–142. April 2002. Retrieved 2007-01-05.
{{cite journal}}
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- ^ E. N. Slyuta and A. M. Abdrakhimov, and E. M. Galimov (2007). "The estimation of helium-3 probable reserves in lunar regolith" (PDF). Lunar and Planetary Science XXXVIII.
- ^ Eric R. Hedman (January 16, 2006). "A fascinating hour with [[Gerald Kulcinski]]". The Space Review.
{{cite news}}
: URL–wikilink conflict (help) - ^ a b The Encyclopedia of the Chemical Elements, page 264
- ^ The Encyclopedia of the Chemical Elements, page 260
- ^ Stay Out of That Balloon! The dangers of helium inhalation, Slate.com. Retrieved on 18 September 2007.
- ^ HPNS, scuba-doc.com. Retrieved on 5 January 2007.
- ^ "Helium - Valency". Retrieved 14 May.
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See also
- Abiogenic petroleum origin
- Helium-3 propulsion
- Leidenfrost effect
- Superfluid
- Tracer-gas leak testing method
External links
- General
- US Government' Bureau of Land Management: Sources, Refinement, and Shortage. With some History of Helium.
- WebElements: Helium
- It's Elemental – Helium
- More detail
- Helium at the Helsinki University of Technology; includes pressure-temperature phase diagrams for helium-3 and helium-4
- Lancaster University, Ultra Low Temperature Physics - includes a summary of some low temperature techniques
- Miscellaneous
- Physics in Speech with audio samples that demonstrate the unchanged voice pitch
- Article about helium and other noble gases
- Ebyte article on helium scarcity and potential effects on NMR and MRI communities