Origin and occurrence of fluorine

Last updated

Fluorine is relatively rare in the universe compared to other elements of nearby atomic weight. On Earth, fluorine is essentially found only in mineral compounds because of its reactivity. The main commercial source, fluorite, is a common mineral.

Contents

In the universe

Abundance in the Solar System [1]
Atomic
number
ElementRelative
amount
6Carbon4,800
7Nitrogen1,500
8Oxygen8,800
9Fluorine1
10Neon1,400
11Sodium24
12Magnesium430

At 400 ppb, fluorine is estimated to be the 24th most common element in the universe. It is comparably rare for a light element (elements tend to be more common the lighter they are). All of the elements from atomic number 6 (carbon) to atomic number 12 (magnesium) are hundreds or thousands of times more common than fluorine except for 11 (sodium). One science writer described fluorine as a "shack amongst mansions" in terms of abundance. [2] Fluorine is so rare because it is not a product of the usual nuclear fusion processes in stars. And any created fluorine within stars is rapidly eliminated through strong nuclear fusion reactions—either with hydrogen to form oxygen and helium, or with helium to make neon and hydrogen. [2] [3] The presence of fluorine at all—outside of temporary existence in stars—is somewhat of a mystery because of the need to escape these fluorine-destroying reactions. [2] [4]

Three theoretical solutions to the mystery exist: In type II supernovae, atoms of neon could be hit by neutrinos during the explosion and converted to fluorine. In Wolf-Rayet stars (blue stars over 40 times heavier than the Sun), a strong solar wind could blow the fluorine out of the star before hydrogen or helium could destroy it. Finally, in asymptotic giant branch (a type of red giant) stars, fusion reactions occur in pulses and convection could lift fluorine out of the inner star. Only the red giant hypothesis has supporting evidence from observations, fluorine cations have been found in planetary nebulae. [2] [4]

In space, fluorine commonly combines with hydrogen to form hydrogen fluoride. (This compound has been suggested as a tracer to enable tracking reservoirs of hydrogen in the universe.) [5] In addition to HF, monatomic fluorine has been observed in the interstellar medium. [6] [7] Fluorine cations have been seen in planetary nebulae and in stars, including the Sun. [8]

On Earth

Fluorine is the thirteenth most common element in Earth's crust, comprising between 600 and 700  ppm of the crust by mass. Because of its reactivity, it is essentially only found in compounds.

Commercial sources

Three minerals exist that are industrially relevant sources of fluorine: fluorite, fluorapatite, and cryolite. [9] [10]

Major fluorine-containing minerals
Fluorite-270246.jpg Apatite Canada.jpg Ivigtut cryolite edit.jpg
FluoriteFluorapatiteCryolite

Fluorite

Fluorite (CaF2), also called fluorspar, is the main source of commercial fluorine. Fluorite is a colorful mineral associated with hydrothermal deposits. It is common and found worldwide. China supplies more than half of the world's demand and Mexico is the second-largest producer in the world.[ citation needed ]

The United States produced most of the world's fluorite in the early 20th century, but its last mine, in Illinois, shut down in 1995. Canada also exited production in the 1990s. The United Kingdom has declining fluorite mining and has been a net importer since the 1980s. [10] [11] [12] [13] [14]

Fluorapatite

Fluorapatite (Ca5(PO4)3F) is mined along with other apatites for its phosphate content and is used mostly for production of fertilizers. Most of the Earth's fluorine is bound in this mineral, but because the percentage within the mineral is low (3.5%), the fluorine is discarded as waste. Only in the United States is there significant recovery. There, the hexafluorosilicates produced as byproducts are used to supply water fluoridation. [10]

Cryolite

Cryolite (Na3AlF6) is the least abundant of the three major fluorine-containing minerals, but is a concentrated source of fluorine. It was formerly used directly in aluminium production. However, the main commercial mine, on the west coast of Greenland, closed in 1987. [10]

Minor occurrences

Several other minerals, such as the gemstone topaz, contain fluoride. Fluoride is not significant in seawater or brines, unlike the other halides, because the alkaline earth fluorides precipitate out of water. [10] Commercially insignificant quantities of organofluorines have been observed in volcanic eruptions and in geothermal springs. Their ultimate origin (from biological sources or geological formation) is unclear. [15]

The possibility of small amounts of gaseous fluorine within crystals has been debated for many years. One form of fluorite, antozonite, has a smell suggestive of fluorine when crushed. The mineral also has a dark black color, perhaps from free calcium (not bonded to fluoride). In 2012, a study reported detection of trace quantities (0.04% by weight) of diatomic fluorine in antozonite. It was suggested that radiation from small amounts of uranium within the crystals had caused the free fluorine defects. [16]

Citations

  1. Cameron, A. G. W. (1973). "Abundance of the elements in the Solar System" (PDF). Space Science Reviews. 15 (1): 121–146. Bibcode:1973SSRv...15..121C. doi:10.1007/BF00172440. S2CID   120201972. Archived from the original (PDF) on 2011-10-21.
  2. 1 2 3 4 Croswell, Ken (2003). "Fluorine: An element–ary mystery". Sky and Telescope. Retrieved 3 May 2011.
  3. Handbook of Isotopes in the Cosmos: Hydrogen to Gallium; Donald Clayton; pages 101-104
  4. 1 2 Renda, A.; Fenner, Y.; Gibson, B.K.; Karakas, A.I.; et al. (2004). "On the origin of fluorine in the Milky Way" (PDF). Monthly Notices of the Royal Astronomical Society . 354 (2): 575–580. arXiv: astro-ph/0410580 . Bibcode:2004MNRAS.354..575R. doi: 10.1111/j.1365-2966.2004.08215.x . S2CID   12330666.
  5. Neufeld, David; Bergin, Edwin; Gerin, Maryvonne (2010). "Tracing the Milky Way's hidden reservoirs of gas". European Space Agency.
  6. Snow, T. P. Jr.; York, D. G. (1981). "The detection of interstellar fluorine in the line of sight toward Delta Scorpii". Astrophysical Journal. 247: L39. Bibcode:1981ApJ...247L..39S. doi: 10.1086/183585 .
  7. Snow, Theodore, P.; Destree, Joshua D.; Jensen, Adam G. (2007). "The abundance of interstellar fluorine and its implications". The Astrophysical Journal. 655 (1): 285–298. arXiv: astro-ph/0611066 . Bibcode:2007ApJ...655..285S. doi:10.1086/510187. S2CID   15700217.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  8. Zhang, Y.; Liu, X.-W. (2005). "Fluorine abundances in planetary nebulae". The Astrophysical Journal. 631 (1): L61–L63. arXiv: astro-ph/0508339 . Bibcode:2005ApJ...631L..61Z. doi:10.1086/497113. S2CID   18619904.
  9. Jaccaud et al. 2005, p. 4.
  10. 1 2 3 4 5 Greenwood & Earnshaw 1998, p. 795.
  11. Villalba, Gara; Ayres, Robert U.; Schroder, Hans (2008). "Accounting for fluorine: production, use, and loss". Journal of Industrial Ecology. 11: 85–101. doi:10.1162/jiec.2007.1075. S2CID   153740615.
  12. Kelly, T.D. "Historical fluorspar statistics" (PDF). United States Geological Service. Retrieved 25 January 2012.
  13. Lusty, P. A. J.; Brown, T. J.; Ward, J; Bloomfeld, S. (2008). "The need for indigenous fluorspar production in England". British Geological Survey. Retrieved 25 January 2012.
  14. Norwood, Charles J.; Fohs, Julius F. (1907). "Fluorspar and its Occurrence". Kentucky geological survey Bulletin 9: Fluorspar deposits of Kentucky. Globe Printing Company. p. 52.
  15. Gribble, Gordon W. (2002). "Naturally occurring organofluorines". Organofluorines. The Handbook of Environmental Chemistry. Vol. 3N. pp. 121–136. doi:10.1007/10721878_5. ISBN   3-540-42064-9.
  16. Schmedt, Jörn; Mangst, Martin; Kraus, Florian (2012). "Elementares Fluor F2 in der Natur – In-situ-Nachweis und Quantifizierung durch NMR-Spektroskopie". Angewandte Chemie (in German). 124 (31): 7968–7971. Bibcode:2012AngCh.124.7968S. doi:10.1002/ange.201203515.

Indexed references

Related Research Articles

<span class="mw-page-title-main">Halogen</span> Group of chemical elements

The halogens are a group in the periodic table consisting of six chemically related elements: fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and the radioactive elements astatine (At) and tennessine (Ts), though some authors would exclude tennessine as its chemistry is unknown and is theoretically expected to be more like that of gallium. In the modern IUPAC nomenclature, this group is known as group 17.

<span class="mw-page-title-main">Noble gas</span> Group of low-reactive, gaseous chemical elements

The noble gases are the naturally occurring members of group 18 of the periodic table: helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and radon (Rn). Under standard conditions, these elements are odorless, colorless, monatomic gases with very low chemical reactivity and cryogenic boiling points.

<span class="mw-page-title-main">Planetary nebula</span> Type of emission nebula created by dying red giants

A planetary nebula is a type of emission nebula consisting of an expanding, glowing shell of ionized gas ejected from red giant stars late in their lives.

<span class="mw-page-title-main">Fluorite</span> Mineral form of calcium fluoride

Fluorite (also called fluorspar) is the mineral form of calcium fluoride, CaF2. It belongs to the halide minerals. It crystallizes in isometric cubic habit, although octahedral and more complex isometric forms are not uncommon.

<span class="mw-page-title-main">Nucleosynthesis</span> Process that creates new atomic nuclei from pre-existing nucleons, primarily protons and neutrons

Nucleosynthesis is the process that creates new atomic nuclei from pre-existing nucleons and nuclei. According to current theories, the first nuclei were formed a few minutes after the Big Bang, through nuclear reactions in a process called Big Bang nucleosynthesis. After about 20 minutes, the universe had expanded and cooled to a point at which these high-energy collisions among nucleons ended, so only the fastest and simplest reactions occurred, leaving our universe containing hydrogen and helium. The rest is traces of other elements such as lithium and the hydrogen isotope deuterium. Nucleosynthesis in stars and their explosions later produced the variety of elements and isotopes that we have today, in a process called cosmic chemical evolution. The amounts of total mass in elements heavier than hydrogen and helium remains small, so that the universe still has approximately the same composition.

<span class="mw-page-title-main">Apatite</span> Mineral group, calcium phosphate

Apatite is a group of phosphate minerals, usually hydroxyapatite, fluorapatite and chlorapatite, with high concentrations of OH, F and Cl ion, respectively, in the crystal. The formula of the admixture of the three most common endmembers is written as Ca10(PO4)6(OH,F,Cl)2, and the crystal unit cell formulae of the individual minerals are written as Ca10(PO4)6(OH)2, Ca10(PO4)6F2 and Ca10(PO4)6Cl2.

<span class="mw-page-title-main">H II region</span> Large, low-density interstellar cloud of partially ionized gas

An H II region or HII region is a region of interstellar atomic hydrogen that is ionized. It is typically in a molecular cloud of partially ionized gas in which star formation has recently taken place, with a size ranging from one to hundreds of light years, and density from a few to about a million particles per cubic centimetre. The Orion Nebula, now known to be an H II region, was observed in 1610 by Nicolas-Claude Fabri de Peiresc by telescope, the first such object discovered.

<span class="mw-page-title-main">Cat's Eye Nebula</span> Planetary nebula in the constellation Draco

The Cat's Eye Nebula is a planetary nebula in the northern constellation of Draco, discovered by William Herschel on February 15, 1786. It was the first planetary nebula whose spectrum was investigated by the English amateur astronomer William Huggins, demonstrating that planetary nebulae were gaseous and not stellar in nature. Structurally, the object has had high-resolution images by the Hubble Space Telescope revealing knots, jets, bubbles and complex arcs, being illuminated by the central hot planetary nebula nucleus (PNN). It is a well-studied object that has been observed from radio to X-ray wavelengths. At the centre of the Cat's Eye Nebula is a dying Wolf Rayet star, the sort of which can be seen in the Webb Telescope's image of WR 124. The Cat's Eye Nebula's central star shines at magnitude +11.4. Hubble Space Telescope images show a sort of dart board pattern of concentric rings emanating outwards from the centre.

<span class="mw-page-title-main">Hydrofluoric acid</span> Solution of hydrogen fluoride in water

Hydrofluoric acid is a solution of hydrogen fluoride (HF) in water. Solutions of HF are colorless, acidic and highly corrosive. A common concentration is 49% (48-52%) but there are also stronger solutions and pure HF has a boiling point near room temperature. It is used to make most fluorine-containing compounds; examples include the commonly used pharmaceutical antidepressant medication fluoxetine (Prozac) and the material PTFE (Teflon). Elemental fluorine is produced from it. It is commonly used to etch glass and silicon wafers.

The abundance of the chemical elements is a measure of the occurrences of the chemical elements relative to all other elements in a given environment. Abundance is measured in one of three ways: by mass fraction, by mole fraction, or by volume fraction. Volume fraction is a common abundance measure in mixed gases such as planetary atmospheres, and is similar in value to molecular mole fraction for gas mixtures at relatively low densities and pressures, and ideal gas mixtures. Most abundance values in this article are given as mass fractions.

Calcium fluoride is the inorganic compound of the elements calcium and fluorine with the formula CaF2. It is a white solid that is practically insoluble in water. It occurs as the mineral fluorite (also called fluorspar), which is often deeply coloured owing to impurities.

<span class="mw-page-title-main">Asymptotic giant branch</span> Stars powered by fusion of hydrogen and helium in shell with an inactive core of carbon and oxygen

The asymptotic giant branch (AGB) is a region of the Hertzsprung–Russell diagram populated by evolved cool luminous stars. This is a period of stellar evolution undertaken by all low- to intermediate-mass stars (about 0.5 to 8 solar masses) late in their lives.

<span class="mw-page-title-main">Metallicity</span> Relative abundance of heavy elements in a star or other astronomical object

In astronomy, metallicity is the abundance of elements present in an object that are heavier than hydrogen and helium. Most of the normal currently detectable matter in the universe is either hydrogen or helium, and astronomers use the word "metals" as convenient shorthand for "all elements except hydrogen and helium". This word-use is distinct from the conventional chemical or physical definition of a metal as an electrically conducting solid. Stars and nebulae with relatively high abundances of heavier elements are called "metal-rich" when discussing metallicity, even though many of those elements are called nonmetals in chemistry.

<span class="mw-page-title-main">Hydrogen fluoride</span> Chemical compound

Hydrogen fluoride (fluorane) is an inorganic compound with chemical formula HF. It is a very poisonous, colorless gas or liquid that dissolves in water to yield hydrofluoric acid. It is the principal industrial source of fluorine, often in the form of hydrofluoric acid, and is an important feedstock in the preparation of many important compounds including pharmaceuticals and polymers such as polytetrafluoroethylene (PTFE). HF is also widely used in the petrochemical industry as a component of superacids. Due to strong and extensive hydrogen bonding, it boils at near room temperature, which is much higher of a temperature than other hydrogen halides.

Organofluorine chemistry describes the chemistry of organofluorine compounds, organic compounds that contain a carbon–fluorine bond. Organofluorine compounds find diverse applications ranging from oil and water repellents to pharmaceuticals, refrigerants, and reagents in catalysis. In addition to these applications, some organofluorine compounds are pollutants because of their contributions to ozone depletion, global warming, bioaccumulation, and toxicity. The area of organofluorine chemistry often requires special techniques associated with the handling of fluorinating agents.

<span class="mw-page-title-main">Fluorine</span> Chemical element with atomic number 9 (F)

Fluorine is a chemical element; it has symbol F and atomic number 9. It is the lightest halogen and exists at standard conditions as pale yellow diatomic gas. Fluorine is extremely reactive as it reacts with all other elements except for the light inert gases. It is highly toxic.

Fluorine forms a great variety of chemical compounds, within which it always adopts an oxidation state of −1. With other atoms, fluorine forms either polar covalent bonds or ionic bonds. Most frequently, covalent bonds involving fluorine atoms are single bonds, although at least two examples of a higher order bond exist. Fluoride may act as a bridging ligand between two metals in some complex molecules. Molecules containing fluorine may also exhibit hydrogen bonding. Fluorine's chemistry includes inorganic compounds formed with hydrogen, metals, nonmetals, and even noble gases; as well as a diverse set of organic compounds. For many elements the highest known oxidation state can be achieved in a fluoride. For some elements this is achieved exclusively in a fluoride, for others exclusively in an oxide; and for still others the highest oxidation states of oxides and fluorides are always equal.

<span class="mw-page-title-main">Fluorochemical industry</span> Industry dealing with chemicals from fluorine

The global market for chemicals from fluorine was about US$16 billion per year as of 2006. The industry was predicted to reach 2.6 million metric tons per year by 2015. The largest market is the United States. Western Europe is the second largest. Asia Pacific is the fastest growing region of production. China in particular has experienced significant growth as a fluorochemical market and is becoming a producer of them as well. Fluorite mining was estimated in 2003 to be a $550 million industry, extracting 4.5 million tons per year.

<span class="mw-page-title-main">History of fluorine</span> History of the chemical element fluorine

Fluorine is a relatively new element in human applications. In ancient times, only minor uses of fluorine-containing minerals existed. The industrial use of fluorite, fluorine's source mineral, was first described by early scientist Georgius Agricola in the 16th century, in the context of smelting. The name "fluorite" derives from Agricola's invented Latin terminology. In the late 18th century, hydrofluoric acid was discovered. By the early 19th century, it was recognized that fluorine was a bound element within compounds, similar to chlorine. Fluorite was determined to be calcium fluoride.

<span class="mw-page-title-main">Fluorine cycle</span> Biogeochemical cycle

The fluorine cycle is the series of biogeochemical processes through which fluorine moves through the lithosphere, hydrosphere, atmosphere, and biosphere. Fluorine originates from the Earth’s crust, and its cycling between various sources and sinks is modulated by a variety of natural and anthropogenic processes.