Kryolite
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Cryolite ( Na3 Al F6,
sodium hexafluoroaluminate Sodium hexafluoroaluminate is an inorganic compound with formula Na3 Al F6. This white solid, discovered in 1799 by Peder Christian Abildgaard (1740–1801), occurs naturally as the mineral cryolite and is used extensively in the industrial produc ...
) is a rare
mineral In geology and mineralogy, a mineral or mineral species is, broadly speaking, a solid substance with a fairly well-defined chemical composition and a specific crystal structure that occurs naturally in pure form.John P. Rafferty, ed. (2011): Mi ...
identified with the once-large deposit at
Ivittuut Ivittuut (formerly, Ivigtût) ( Kalaallisut: "Grassy Place") is an abandoned mining town near Cape Desolation in southwestern Greenland, in the modern Sermersooq municipality on the ruins of the former Norse Middle Settlement. Ivittuut is one ...
on the west coast of
Greenland Greenland is an autonomous territory in the Danish Realm, Kingdom of Denmark. It is by far the largest geographically of three constituent parts of the kingdom; the other two are metropolitan Denmark and the Faroe Islands. Citizens of Greenlan ...
, mined commercially until 1987. It is used in the reduction ("
smelting Smelting is a process of applying heat and a chemical reducing agent to an ore to extract a desired base metal product. It is a form of extractive metallurgy that is used to obtain many metals such as iron-making, iron, copper extraction, copper ...
") of aluminium, in pest control, and as a dye.


History

Cryolite was first described in 1798 by Danish veterinarian and physician (1740–1801), from rock samples obtained from local
Inuit Inuit (singular: Inuk) are a group of culturally and historically similar Indigenous peoples traditionally inhabiting the Arctic and Subarctic regions of North America and Russia, including Greenland, Labrador, Quebec, Nunavut, the Northwe ...
who used the mineral for washing their hides; the actual source of the ore was later discovered in 1806 by the explorer
Karl Ludwig Giesecke Carl Ludwig Giesecke FRSE (6 April 1761 in Augsburg – 5 March 1833 in Dublin) was a German actor, librettist, polar explorer and mineralogist. In his youth he was called Johann Georg Metzler; in his later career in Ireland he was Sir Charl ...
. who found the deposit at Ivigtut (old spelling) and nearby Arsuk Fjord, Southwest Greenland, where it was extracted by Øresund Chemical Industries. The name is derived from the
Greek Greek may refer to: Anything of, from, or related to Greece, a country in Southern Europe: *Greeks, an ethnic group *Greek language, a branch of the Indo-European language family **Proto-Greek language, the assumed last common ancestor of all kno ...
words (), and (). The
Pennsylvania Salt Manufacturing Company Arkema S.A. is a publicly listed, multi-national manufacturer of specialty materials, headquartered in La Défense, near Paris, France. It has three specialty materials segments (or divisions); adhesives, advanced materials and coatings. A furt ...
used large amounts of cryolite to make
caustic soda Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula . It is a white solid ionic compound consisting of sodium cations and hydroxide anions . Sodium hydroxide is a highly corrosive base and alkali t ...
and
fluorine Fluorine is a chemical element; it has Chemical symbol, symbol F and atomic number 9. It is the lightest halogen and exists at Standard temperature and pressure, standard conditions as pale yellow Diatomic molecule, diatomic gas. Fluorine is extre ...
compounds, including
hydrofluoric acid 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 (e.g. 70%) and pure HF has a boiling p ...
at its
Natrona, Pennsylvania Natrona is an unincorporated community in Harrison Township, Allegheny County, Pennsylvania. It is located in western Pennsylvania within the Pittsburgh Metropolitan Statistical Area, approximately northeast of Downtown Pittsburgh. Natrona i ...
, works, and at its integrated chemical plant in
Cornwells Heights, Pennsylvania Cornwells Heights is a census-designated place located in Bensalem Township in Bucks County, Pennsylvania, United States. The community was formerly part of Cornwells Heights-Eddington, but was split into two separate CDPs. As of the 2010 ce ...
, during the 19th and 20th centuries. It was historically used as an ore of aluminium and later in the electrolytic processing of the
aluminium Aluminium (or aluminum in North American English) is a chemical element; it has chemical symbol, symbol Al and atomic number 13. It has a density lower than that of other common metals, about one-third that of steel. Aluminium has ...
-rich oxide
ore Ore is natural rock or sediment that contains one or more valuable minerals, typically including metals, concentrated above background levels, and that is economically viable to mine and process. The grade of ore refers to the concentration ...
bauxite Bauxite () is a sedimentary rock with a relatively high aluminium content. It is the world's main source of aluminium and gallium. Bauxite consists mostly of the aluminium minerals gibbsite (), boehmite (γ-AlO(OH)), and diaspore (α-AlO(OH) ...
(itself a combination of
aluminium oxide Aluminium oxide (or aluminium(III) oxide) is a chemical compound of aluminium and oxygen with the chemical formula . It is the most commonly occurring of several Aluminium oxide (compounds), aluminium oxides, and specifically identified as alum ...
minerals such as
gibbsite Gibbsite, Al(OH)3, is one of the mineral forms of aluminium hydroxide. It is often designated as γ-Al(OH)3 (but sometimes as α-Al(OH)3). It is also sometimes called hydrargillite (or hydrargyllite). Gibbsite is an important ore of aluminium ...
,
boehmite Boehmite or böhmite is an aluminium oxide hydroxide (γ-AlO(OH)) mineral, a component of the aluminium ore bauxite. It is dimorphous with diaspore. It crystallizes in the orthorhombic dipyramidal system and is typically massive in habit. It is ...
and
diaspore Diaspore ()also called diasporite, empholite, kayserite, or tanatariteis an aluminium hydroxide oxide mineral, α-AlO(OH), crystallizing in the orthorhombic system and isomorphous with goethite. It occurs sometimes as flattened crystals, but ...
). The difficulty of separating aluminium from oxygen in the oxide ores was overcome by the use of cryolite as a
flux Flux describes any effect that appears to pass or travel (whether it actually moves or not) through a surface or substance. Flux is a concept in applied mathematics and vector calculus which has many applications in physics. For transport phe ...
to dissolve the oxide mineral(s). Pure cryolite itself melts at 1012 Â°C (1285 K), and it can dissolve the aluminium oxides sufficiently well to allow easy extraction of the aluminium by
electrolysis In chemistry and manufacturing, electrolysis is a technique that uses Direct current, direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of c ...
. Substantial energy is still needed for both heating the materials and the electrolysis, but it is much more energy-efficient than melting the oxides themselves. As natural cryolite is now too rare to be used for this purpose, synthetic sodium aluminium fluoride is produced from the common mineral
fluorite 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. The Mohs scal ...
. In 1940 before entering World War II, the United States became involved with protecting the world's largest cryolite mine in Ivittuut, Greenland from falling into Nazi Germany's control. In 1987 the main mining in Ivittuut was closed. According to economist Arindam Banerjee, exploitation of cryolite in Greenland contributed to nearly 54 billion euros to Danish economy, though this claim has been strongly disputed.


Source locations

Besides
Ivittuut Ivittuut (formerly, Ivigtût) ( Kalaallisut: "Grassy Place") is an abandoned mining town near Cape Desolation in southwestern Greenland, in the modern Sermersooq municipality on the ruins of the former Norse Middle Settlement. Ivittuut is one ...
, on the west coast of
Greenland Greenland is an autonomous territory in the Danish Realm, Kingdom of Denmark. It is by far the largest geographically of three constituent parts of the kingdom; the other two are metropolitan Denmark and the Faroe Islands. Citizens of Greenlan ...
where cryolite was once found in commercial quantities, small deposits of cryolite have also been reported in some areas of
Spain Spain, or the Kingdom of Spain, is a country in Southern Europe, Southern and Western Europe with territories in North Africa. Featuring the Punta de Tarifa, southernmost point of continental Europe, it is the largest country in Southern Eur ...
, at the foot of
Pikes Peak Pikes Peak is the List of mountain ranges of Colorado#Mountain ranges, highest summit of the southern Front Range of the Rocky Mountains in North America. The Ultra-prominent peak, ultra-prominent fourteener is located in Pike National Forest, ...
in
Colorado Colorado is a U.S. state, state in the Western United States. It is one of the Mountain states, sharing the Four Corners region with Arizona, New Mexico, and Utah. It is also bordered by Wyoming to the north, Nebraska to the northeast, Kansas ...
, Francon Quarry near
Montreal Montreal is the List of towns in Quebec, largest city in the Provinces and territories of Canada, province of Quebec, the List of the largest municipalities in Canada by population, second-largest in Canada, and the List of North American cit ...
in
Quebec Quebec is Canada's List of Canadian provinces and territories by area, largest province by area. Located in Central Canada, the province shares borders with the provinces of Ontario to the west, Newfoundland and Labrador to the northeast, ...
,
Canada Canada is a country in North America. Its Provinces and territories of Canada, ten provinces and three territories extend from the Atlantic Ocean to the Pacific Ocean and northward into the Arctic Ocean, making it the world's List of coun ...
and also in Miask,
Russia Russia, or the Russian Federation, is a country spanning Eastern Europe and North Asia. It is the list of countries and dependencies by area, largest country in the world, and extends across Time in Russia, eleven time zones, sharing Borders ...
.


Uses

Molten cryolite is used as a solvent for
aluminium oxide Aluminium oxide (or aluminium(III) oxide) is a chemical compound of aluminium and oxygen with the chemical formula . It is the most commonly occurring of several Aluminium oxide (compounds), aluminium oxides, and specifically identified as alum ...
(Al2O3) in the
Hall–Héroult process The Hall–Héroult process is the major industrial process for smelting aluminium. It involves dissolving aluminium oxide (alumina) (obtained most often from bauxite, aluminium's chief ore, through the Bayer process) in molten cryolite and e ...
, used in the refining of
aluminium Aluminium (or aluminum in North American English) is a chemical element; it has chemical symbol, symbol Al and atomic number 13. It has a density lower than that of other common metals, about one-third that of steel. Aluminium has ...
. It decreases the melting point of aluminium oxide from 2000–2500 Â°C to 900–1000 Â°C, and increases its conductivity thus making the extraction of aluminium more economical. Cryolite is used as an
insecticide Insecticides are pesticides used to kill insects. They include ovicides and larvicides used against insect eggs and larvae, respectively. The major use of insecticides is in agriculture, but they are also used in home and garden settings, i ...
and a
pesticide Pesticides are substances that are used to control pests. They include herbicides, insecticides, nematicides, fungicides, and many others (see table). The most common of these are herbicides, which account for approximately 50% of all p ...
. It is also used to give
firework Fireworks are Explosive, low explosive Pyrotechnics, pyrotechnic devices used for aesthetic and entertainment purposes. They are most commonly used in fireworks displays (also called a fireworks show or pyrotechnics), combining a large numbe ...
s a yellow color. It is used in glass manufacturing as a "powerful opaliser."


Physical properties

Cryolite occurs as glassy, colorless, white-reddish to gray-black prismatic
monoclinic In crystallography, the monoclinic crystal system is one of the seven crystal systems. A crystal system is described by three Vector (geometric), vectors. In the monoclinic system, the crystal is described by vectors of unequal lengths, as in t ...
crystals. It has a
Mohs hardness The Mohs scale ( ) of mineral hardness is a qualitative ordinal scale, from 1 to 10, characterizing scratch resistance of mineral In geology and mineralogy, a mineral or mineral species is, broadly speaking, a solid substance with a fair ...
of 2.5 to 3 and a
specific gravity Relative density, also called specific gravity, is a dimensionless quantity defined as the ratio of the density (mass of a unit volume) of a substance to the density of a given reference material. Specific gravity for solids and liquids is nea ...
of about 2.95 to 3.0. It is translucent to transparent with a very low
refractive index In optics, the refractive index (or refraction index) of an optical medium is the ratio of the apparent speed of light in the air or vacuum to the speed in the medium. The refractive index determines how much the path of light is bent, or refrac ...
of about 1.34, which is very close to that of
water Water is an inorganic compound with the chemical formula . It is a transparent, tasteless, odorless, and Color of water, nearly colorless chemical substance. It is the main constituent of Earth's hydrosphere and the fluids of all known liv ...
; thus if immersed in water, cryolite becomes essentially invisible.


References


''Phase transitions and volumetric properties of cryolite, Na3AlF6: Differential thermal analysis to 100 MPa;'' American Mineralogist; January 2006; v. 91; no. 1; p. 97-103
{{Authority control Aluminium minerals History of Greenland Natural history of Greenland Pyrotechnic colorants Sodium minerals Monoclinic minerals Minerals in space group 14 Fluorine minerals Inorganic insecticides Pesticides