Helium

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Helium (He) is a colorless, odorless, tasteless, non-toxic, nearly 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. It has a second, rare, stable isotope which is called helium-3. 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).

Helium is the second most abundant and second lightest element in the universe and was one of the elements 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 it is created by the radioactive decay of much heavier elements (alpha particles are helium nuclei). After its creation, part of it is trapped with natural gas in concentrations up to 7% by volume. It is extracted from the natural gas by a low temperature separation process called fractional distillation.

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 (see precautions section below).

[edit] Notable characteristics

[edit] 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 (molecular) mass, in the gas phase it has a thermal conductivity, specific heat, and sound conduction velocity that are all greater than any gas, except hydrogen. For similar reasons, and also due to the small size of its molecules, helium's diffusion rate through solids is three times that of air and around 65% that of hydrogen.^[1]

Helium is less water soluble than any other gas known, and helium's index of refraction is closer to unity than that of any other gas. 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.

Helium is chemically unreactive under all normal conditions due to its valence of zero. 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⁺, He₂⁺⁺, 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.^[1] Theoretically, other compounds, like helium fluorohydride (HHeF), may also be possible.

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. 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.

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.

[edit] Solid and liquid phases

Main article: Liquid helium

Helium solidifies only under great pressure. The resulting colorless, almost invisible solid is highly compressible; applying pressure in the laboratory can decrease its volume by more than 30%.^[2] With a bulk modulus on the order of 5×10⁷ Pa^[3] 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.^[4] 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.^[5]

[edit] 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.^[6] This colorless liquid has a very low viscosity and a density 1/8th that of water, which is only 1/4th the value expected from classical physics.^[6] 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 is probably due to its boiling point being so close to absolute zero, which prevents random molecular motion (heat) from masking the atomic properties.^[6]

[edit] 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.^[7]

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.^[8][9] 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.^[10] 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.^[11]

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.^[8]

[edit] 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. Pressurized helium is commercially available in large quantities, although it can be very difficult to obtain in times of helium shortages.^[12]

As a lighter than air gas, 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 lifting power of the alternative hydrogen.

Due to its low solubility in water, the major part of human blood, air 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, decompression sickness, and oxygen toxicity.

Liquid helium can be used as a cryogenic material, and is used to cool certain metals to produce superconductivity, such as in superconducting magnets use in magnetic resonance imaging and NMR spectroscopy.

Due to its inertness, 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. It is also 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.^[2]

Apart from its inertness, helium has high thermal conductivity, neutron transparency, and does not form radioactive isotopes under reactor conditions, so it is used as a coolant in some nuclear reactors, such as pebble-bed reactors. 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.

Other applications include:

• 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 to detect leaks in high-vacuum equipment and high-pressure containers.
• 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.
• Because helium alone is less dense than atmospheric air, it will change the timbre (not pitch^[13]) 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 suffocation 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.

[edit] History

[edit] 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,^[14] 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)^[15]

On 26 March 1895 British chemist William Ramsay isolated helium on Earth by treating the mineral cleveite 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.^{[16][17][18][19] [16]} 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.^[20] 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.^[21]

In 1907, Ernest Rutherford and Thomas Royds demonstrated that an alpha particle is a helium nucleus. 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 has almost no viscosity at temperatures near absolute zero, a phenomenon now called superfluidity. In 1972, the same phenomenon was observed in helium-3 by American physicists Douglas D. Osheroff, David M. Lee, and Robert C. Richardson.

[edit] History of extraction and use

After an oil drilling operation in 1903 in Dexter, Kansas, USA 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.^[22] With further analysis, Cady and McFarland discovered that 1.84% of the gas sample was helium.^[23] 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 200,000 cubic feet (5700 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.^[16] 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.^[24]

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 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.^[22][25] The resulting "Helium Privatization Act of 1996"^[26] (Public Law 104–273) directed the United States Department of the Interior to start liquidating the reserve by 2005.^[27]

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.

[edit] Occurrence and production

[edit] 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.

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, monazite and beryl, 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 atmosphere, the concentration of helium by volume is only 5.2 parts per million.^[28] 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.^[29][30]

In the Earth's heterosphere, a part of the upper atmosphere, helium and other lighter gases are the most abundant elements.

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.

[edit] Modern extraction

For large-scale use, helium is extracted by fractional distillation from natural gas, which contains up to 7% helium.^[31] 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.^[32] The principal impurity in Grade-A helium is neon.

Diffusion of crude natural gas through special semi-permeable 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.

In 2006, approximately 170 million cubic meters of helium were extracted from natural gas or withdrawn from helium reserves, with approximately 79% from the United States, 13% from Algeria, and most of the remainder from Qatar, Russia, Poland, Canada, and China. In recent years, worldwide extraction of helium has been increasing by about 10 million cubic meters per year. In the United States, most helium is extracted in Kansas and Texas.^[33]

[edit] Isotopes

Main article: Isotopes of helium

Although there are eight known isotopes of helium, 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.^[34] However, helium is unusual in that its isotopic abundance varies greatly depending on its origin. In the interstellar medium, the proportion of He-3 is around a hundred times higher.^[35] Rocks from the Earth's crust have isotope ratios varying by as much as a factor of ten; this is used in geology to study the origin of such rocks.

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.

Evaporative cooling of liquid helium-4, in a so-called 1-K pot, cools the liquid to about 1 degree kelvin. In a helium-3 refrigerator, similar cooling of helium-3, which has a lower boiling point, reaches a temperature of about 0.2 kelvin. Equal mixtures of liquid helium-3 and helium-4 below 0.8 K will 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).^[36] Dilution refrigerators take advantage of the immiscibility of these two isotopes to achieve temperatures of a few millikelvins. There is only a trace amount of helium-3 on Earth, primarily present since the formation of the Earth, although some falls to Earth trapped in cosmic dust.^[37] Trace amounts are also produced by the beta decay of tritium.^[38] In stars, however, helium-3 is more abundant, a product of nuclear fusion. Extraplanetary material, such as lunar and asteroid regolith, have trace amounts of helium-3 from being bombarded by solar winds.

The different formation processes of the two stable isotopes of helium produce the differing isotope abundances. These differing isotope abundances can be used to investigate the origin of rocks and the composition of the Earth's mantle.^[37]

It is possible to produce exotic helium isotopes, which rapidly decay into other substances. The shortest-lived helium isotope is helium-5 with a half-life of 7.6×10⁻²² second. 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 hyperfragments that are created in certain nuclear reactions.^[39]

The exotics helium-6 and helium-8 are known to exhibit a nuclear halo.

[edit] Precautions

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 greater than 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.^[20] (The opposite effect, lowering frequencies, can be obtained by inhaling sulfur hexafluoride.)

Although the vocal effect of inhaling helium may be amusing, it can be dangerous if done to excess since helium is a simple asphyxiant, thus it displaces oxygen needed for normal respiration. Death by asphyxiation will result within minutes if pure helium is breathed continuously. In mammals (with the notable exceptions of 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..^[40]

Neutral helium at standard conditions is non-toxic, plays no biological role and is found in trace amounts in human blood. At high pressures, a mixture of helium and oxygen (heliox) can lead to high pressure nervous syndrome; however, increasing the proportion of nitrogen can alleviate the problem.^[41]

Containers of helium gas at 5 to 10 K should be handled as if they have liquid helium inside due to the rapid and significant thermal expansion that occurs when helium gas at less than 10 K is warmed to room temperature.^[2]