The first evidence of helium was observed on August 18, 1868, as a bright yellow line with a wavelength of 587.49 nanometers in the spectrum of the chromosphere of the Sun. The line was detected by French astronomer Jules Janssen during a total solar eclipse in Guntur, India. This line was initially assumed to be sodium. On October 20 of the same year, English astronomer Norman Lockyer observed a yellow line in the solar spectrum, which he named the D3 because it was near the known D1 and D2 Fraunhofer line lines of sodium. He concluded that it was caused by an element in the Sun unknown on Earth. Lockyer and English chemist Edward Frankland named the element with the Greek word for the Sun, ἥλιος (helios).
In 1881, Italian physicist Luigi Palmieri detected helium on Earth for the first time through its D3 spectral line, when he analyzed a material that had been sublimated during a recent eruption of Mount Vesuvius.
The cleveite sample from which Ramsay first purified helium.
On March 26, 1895, Scottish chemist Sir William Ramsay isolated helium on Earth by treating the mineral cleveite (a variety of uraninite with at least 10% rare earth elements) with mineral acids. Ramsay was looking for argon but, after separating nitrogen and oxygen from the gas liberated by sulfuric acid, he noticed a bright yellow line that matched the D3 line observed in the spectrum of the Sun. These samples were identified as helium by Lockyer and British physicist William Crookes. It was independently isolated from cleveite in the same year by chemists Per Teodor Cleve and Abraham Langlet in Uppsala, Sweden, who collected enough of the gas to accurately determine its atomic weight. 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.
In 1907, Ernest Rutherford and Thomas Royds demonstrated that alpha particles are helium nuclei by allowing the particles to penetrate the thin glass wall of an evacuated tube, then creating a discharge in the tube to study the spectrum of the new gas inside. 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 solidify at atmospheric pressure. Onnes' student Willem Hendrik Keesom was eventually able to solidify 1 cm3 of helium in 1926 by applying additional external pressure.
In 1913, Niels Bohr published his "trilogy" on atomic structure that included a reconsideration of the Pickering–Fowler series as central evidence in support of his model of the atom. This series is named for Edward Charles Pickering, who in 1896 published observations of previously unknown lines in the spectrum of the star ζ Puppis (these are now known to occur with Wolf–Rayet and other hot stars). Pickering attributed the observation (lines at 4551, 5411, and 10123 Å) to a new form of hydrogen with half-integer transition levels. In 1912, Alfred Fowler managed to produce similar lines from a hydrogen-helium mixture, and supported Pickering's conclusion as to their origin. Bohr's model does not allow for half-integer transitions (nor does quantum mechanics) and Bohr concluded that Pickering and Fowler were wrong, and instead assigned these spectral lines to ionised helium, He+. Fowler was initially skeptical but was ultimately convinced that Bohr was correct, and by 1915 "spectroscopists had transferred [the Pickering–Fowler series] definitively [from hydrogen] to helium." Bohr's theoretical work on the Pickering series had demonstrated the need for "a re-examination of problems that seemed already to have been solved within classical theories" and provided important confirmation for his atomic theory.
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. 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 use
After an oil drilling operation in 1903 in Dexter, Kansas, produced a gas geyser that would not burn, Kansas state geologist Erasmus Haworth collected samples of the escaping gas and took them back to the University of Kansas at Lawrence where, with the help of chemists Hamilton Cady and David McFarland, he discovered that the gas consisted of, by volume, 72% nitrogen, 15% methane (a combustible percentage only with sufficient oxygen), 1% hydrogen, and 12% an unidentifiable gas. With further analysis, Cady and McFarland discovered that 1.84% of the gas sample was helium. This showed that despite its overall rarity on Earth, helium was concentrated in large quantities under the American Great Plains, available for extraction as a byproduct of natural gas.
This enabled the United States to become the world's leading supplier of helium. Following a suggestion by Sir Richard Threlfall, the United States Navy sponsored three small experimental helium plants during World War I. The goal was to supply barrage balloons with the non-flammable, lighter-than-air gas. A total of 5,700 m3 (200,000 cu ft) of 92% helium was produced in the program even though less than a cubic meter of the gas had previously been obtained. 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, nearly two years before the Navy's first rigid helium-filled airship, the Naval Aircraft Factory-built USS Shenandoah, flew in September 1923.
Although the extraction process, using low-temperature gas liquefaction, was not developed in time to be significant during World War I, production continued. Helium was primarily used as a lifting gas in lighter-than-air craft. During World War II, the demand increased for helium for lifting gas and for shielded arc welding. The helium mass spectrometer was also vital in the atomic bomb Manhattan Project.
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. Because of the Helium Act of 1925, which banned the export of scarce helium on which the US then had a production monopoly, together with the prohibitive cost of the gas, the Hindenburg, like all German Zeppelins, was forced to use hydrogen as the lift gas. The helium market after World War II was depressed but the reserve was expanded in the 1950s to ensure a supply of liquid helium as a coolant to create oxygen/hydrogen rocket fuel (among other uses) during the Space Race and Cold War. Helium use in the United States in 1965 was more than eight times the peak wartime consumption.
After the "Helium Acts Amendments of 1960" (Public Law 86–777), the U.S. Bureau of Mines arranged for five private plants to recover helium from natural gas. For this helium conservation program, the Bureau built a 425-mile (684 km) pipeline from Bushton, Kansas, to connect those plants with the government's partially depleted Cliffside gas field near Amarillo, Texas. This helium-nitrogen mixture was injected and stored in the Cliffside gas field until needed, at which time it was further purified.
By 1995, a billion cubic meters of the gas had been collected and the reserve was US$1.4 billion in debt, prompting the Congress of the United States in 1996 to phase out the reserve. The resulting Helium Privatization Act of 1996 (Public Law 104–273) directed the United States Department of the Interior to empty the reserve, with sales starting by 2005.
Helium produced between 1930 and 1945 was about 98.3% pure (2% nitrogen), which was adequate for airships. In 1945, a small amount of 99.9% helium was produced for welding use. By 1949, commercial quantities of Grade A 99.95% helium were available.
For many years, the United States produced more than 90% of commercially usable helium in the world, while extraction plants in Canada, Poland, Russia, and other nations produced the remainder. In the mid-1990s, a new plant in Arzew, Algeria, producing 17 million cubic meters (600 million cubic feet) began operation, with enough production to cover all of Europe's demand. Meanwhile, by 2000, the consumption of helium within the U.S. had risen to more than 15 million kg per year. In 2004–2006, additional plants in Ras Laffan, Qatar, and Skikda, Algeria were built. Algeria quickly became the second leading producer of helium. Through this time, both helium consumption and the costs of producing helium increased. From 2002 to 2007 helium prices doubled.
As of 2012, the United States National Helium Reserve accounted for 30 percent of the world's helium. The reserve was expected to run out of helium in 2018. Despite that, a proposed bill in the United States Senate would allow the reserve to continue to sell the gas. Other large reserves were in the Hugoton in Kansas, United States, and nearby gas fields of Kansas and the panhandles of Texas and Oklahoma. New helium plants were scheduled to open in 2012 in Qatar, Russia, and the US state of Wyoming, but they were not expected to ease the shortage.
In 2013, Qatar started up the world's largest helium unit, although the 2017 Qatar diplomatic crisis severely affected helium production there. 2014 was widely acknowledged to be a year of over-supply in the helium business, following years of renowned shortages. Nasdaq reported (2015) that for Air Products, an international corporation that sells gases for industrial use, helium volumes remain under economic pressure due to feedstock supply constraints.