Helium

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For other uses of this term, see Helium (disambiguation).

Helium is a colorless, odorless, tasteless chemical element. It is the most unreactive of the noble gases and therefore the least chemically-active chemical element on the periodic table. Its boiling and melting points are the lowest among the elements; except in extreme conditions, it exists only as a gas. At temperatures near absolute zero, it is a superfluid, a nearly frictionless phase of matter with unusual properties.

After hydrogen, helium is the second lightest element and the second most abundant element in the universe, which many believe was created during big bang nucleosynthesis and to a lesser extent from nuclear fusion of hydrogen in stars. On Earth, helium is primarily a product of the radioactive decay of much heavier elements, which emit helium nuclei called alpha particles; it is found in significant amounts only in natural gas, from which it is extracted at low temperatures by fractional distillation.

First detected in 1868 by French astronomer Pierre Janssen as an unknown yellow spectral line signature in the light of a solar eclipse, helium was separately identified as a new element later that year by English astronomer Norman Lockyer. Its presence in natural gas in large, useable amounts was identified in 1905. Helium is used in cryogenics, as a deep-sea breathing gas, for inflating balloons and airships, and as a protective gas for many industrial purposes, such as arc welding. Inhaling a small amount of the gas temporarily changes the quality of a person's voice; however, caution must be exercised as helium is an asphyxiant.

Notable characteristics

Gas and plasma phases

Helium is a colorless, odorless, and non-toxic gas. It is the least reactive member of group 18 (the noble gases) of the periodic table and therefore also the least reactive of all elements; it is inert and monatomic in virtually all conditions. It has a thermal conductivity that is greater than any gas except hydrogen and is specific heat is unusually high. Helium is also less water soluble than any other gas known and its diffusion rate through solids is three times that of air and around 65% that of hydrogen. Helium's index of refraction is closer to unity than 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 discharge tube shaped like the element's atomic symbol

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. Theoretically, other compounds, like helium fluorohydride (HHeF), may also be possible.

Throughout the universe, helium is found mostly in a plasma state whose properties are quite different to molecular helium. As 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 the laboratory can decrease its volume by more than 30%. With a bulk modulus on the order of 5×10⁷ Pa 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. Solid helium requires a temperature of 1–1.5 K (about −272 °C or −457 °F) and about 26 standard atmospheres (2.6 MPa) of pressure. 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.

Helium I state

Below its boiling point of 4.22 kelvins and above the lambda point of 2.1768 kelvins, the isotope helium-4 exists in a normal colorless liquid state, called helium I. Like other cryogenic liquids, helium I boils when heat is added to it. 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. 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. 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.

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.

File:Helium-II-creep.png

Helium II will "creep" along surfaces in order to find its own level - after a short while, the levels in the two containers will equalize. The Rollin film also covers the interior of the larger container; if it were not sealed, the helium II would creep out and escape.

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.

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. 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.

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.

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.

Applications

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

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.

• 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 lifting power of the alternative hydrogen.
• For 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.
• At extremely low temperatures, liquid helium is used to cool certain metals to produce superconductivity, such as in superconducting magnets used in magnetic resonance imaging. Helium at low temperatures is also used in cryogenics.
• For its inertness and high thermal conductivity, helium is used as a coolant in some nuclear reactors, such as pebble-bed reactors, and in arc welding air-sensitive metals.
• 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.
• 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 the level of helium there.
• Because helium alone is less dense than atmospheric air, it will change the timbre (not pitch ) 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 number of contaminants that may be present. These could include trace amount of other gases, in addition to aerosolized lubricating oil.
• 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.

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, 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).

On March 26 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. 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.

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.

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. With further analysis, Cady and McFarland discovered that 1.84% of the gas sample was helium. 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. 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 December 1, 1921.

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

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 early 2000s, Algeria and Qatar were added as well. Algeria quickly became the second leading producer of helium. Through this time, both helium consumption and the costs of producing helium increased.

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, largely because most helium in the Earth's atmosphere escapes into space due to its inertness and low mass. 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, 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 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.

Extraction

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

As of 2004, over one hundred and fifty million cubic metres of helium were extracted from natural gas or withdrawn from helium reserves, annually, with approximately 84% of production from the United States, 10% from Algeria, and most of the remainder from Canada, China, Poland, Qatar, and Russia. In the United States, most helium is produced in Kansas and Texas.

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.

Isotopes

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. 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. 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.

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). 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. Trace amounts are also produced by the beta decay of tritium. 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.

It is possible to produce exotic helium isotopes, which rapidly decay into other substances. The shortest-lived 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.

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 that in air. As a result, when helium is inhaled there is a corresponding increase in the resonant frequencies of the vocal tract. The higher perceived pitch is only due to a different frequency shaping of the voice, the fundamental frequency of the vocal cords remains more or less the same.

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 exception of seals) 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.

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.

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.

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 31 March 2005)
• 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, G. R. 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)

External links

General

• WebElements: Helium
• It's Elemental – Helium
• Photos and applications of Helium
• Fluidmech.net about liquid Helium-II and low temperature phase diagram

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

• Phase diagram of helium, showing lambda line
• Helium Safety regarding inhalation
• Physics in Speech with audio samples that demonstrate the unchanged voice pitch
• Article about Helium and other noble gases