Cryolite | |
---|---|
General | |
Category | Halide mineral |
Formula (repeating unit) | Na3AlF6 |
IMA symbol | Crl [1] |
Strunz classification | 3.CB.15 |
Dana classification | 11.6.1.1 |
Crystal system | Monoclinic |
Crystal class | Prismatic (2/m) (same H-M symbol) |
Space group | P21/n |
Unit cell | a = 7.7564(3) Å, b = 5.5959(2) Å, c = 5.4024(2) Å; β = 90.18°; Z = 2 |
Identification | |
Formula mass | 209.9 g mol−1 |
Color | Colorless to white, also brownish, reddish and rarely black |
Crystal habit | Usually massive, coarsely granular. The rare crystals are equant and pseudocubic |
Twinning | Very common, often repeated or polysynthetic with simultaneous occurrence of several twin laws |
Cleavage | None observed |
Fracture | Uneven |
Tenacity | Brittle |
Mohs scale hardness | 2.5 to 3 |
Luster | Vitreous to greasy, pearly on {001} |
Streak | White |
Diaphaneity | Transparent to translucent |
Specific gravity | 2.95 to 3.0. |
Optical properties | Biaxial (+) |
Refractive index | nα = 1.3385–1.339, nβ = 1.3389–1.339, nγ = 1.3396–1.34 |
Birefringence | δ = 0.001 |
2V angle | 43° |
Dispersion | r < v |
Melting point | 1012 °C |
Solubility | Soluble in AlCl3 solution, soluble in H2SO4 with the evolution of HF, which is poisonous. Insoluble in water. [2] |
Other characteristics | Weakly thermoluminescent. Small clear fragments become nearly invisible when placed in water, since its refractive index is close to that of water. May fluoresce intense yellow under SWUV, with yellow phosphorescence, and pale yellow phosphorescence under LWUV. Not radioactive. |
References | [3] [4] [5] [6] [7] |
Cryolite (Na 3 Al F 6, sodium hexafluoroaluminate) is an uncommon mineral identified with the once-large deposit at Ivittuut on the west coast of Greenland, mined commercially until 1987. [8]
It is used in the reduction ("smelting") of aluminium, in pest control, and as a dye.
Cryolite was first described in 1798 by Danish veterinarian and physician Peder Christian Abildgaard (1740–1801); [9] [10] it was obtained from a deposit of it in Ivigtut (old spelling) and nearby Arsuk Fjord, Southwest Greenland. [11] The name is derived from the Greek language words κρύος (cryos) = frost, and λίθος (lithos) = stone. [12] The Pennsylvania Salt Manufacturing Company used large amounts of cryolite to make caustic soda and fluorine compounds, including hydrofluoric acid at its Natrona, Pennsylvania, works, and at its integrated chemical plant in Cornwells Heights, Pennsylvania, during the 19th and 20th centuries.[ citation needed ]
It was historically used as an ore of aluminium and later in the electrolytic processing of the aluminium-rich oxide ore bauxite (itself a combination of aluminium oxide minerals such as gibbsite, boehmite and diaspore). The difficulty of separating aluminium from oxygen in the oxide ores was overcome by the use of cryolite as a flux to dissolve the oxide mineral(s). Pure cryolite itself melts at 1012 °C (1285 K), and it can dissolve the aluminium oxides sufficiently well to allow easy extraction of the aluminium by electrolysis. 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.[ citation needed ]
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. [13]
Besides Ivittuut, on the west coast of Greenland where cryolite was once found in commercial quantities, small deposits of cryolite have also been reported in some areas of Spain, at the foot of Pikes Peak in Colorado, Francon Quarry near Montreal in Quebec, Canada and also in Miask, Russia. [14] [15]
Molten cryolite is used as a solvent for aluminium oxide (Al2O3) in the Hall–Héroult process, used in the refining of aluminium. It decreases the melting point of aluminium oxide from 2000–2500 °C to 900–1000 °C, and increases its conductivity [16] thus making the extraction of aluminium more economical. [17]
Cryolite is used as an insecticide and a pesticide. [18] It is also used to give fireworks a yellow color. [19]
Cryolite occurs as glassy, colorless, white-reddish to gray-black prismatic monoclinic crystals. It has a Mohs hardness of 2.5 to 3 and a specific gravity of about 2.95 to 3.0. It is translucent to transparent with a very low refractive index of about 1.34, which is very close to that of water; thus if immersed in water, cryolite becomes essentially invisible. [7]
Aluminium is a chemical element; it has symbol Al and atomic number 13. Aluminium has a density lower than that of other common metals, about one-third that of steel. It has a great affinity towards oxygen, forming a protective layer of oxide on the surface when exposed to air. Aluminium visually resembles silver, both in its color and in its great ability to reflect light. It is soft, nonmagnetic, and ductile. It has one stable isotope, 27Al, which is highly abundant, making aluminium the twelfth-most common element in the universe. The radioactivity of 26Al, a more unstable isotope, leads to it being used in radiometric dating.
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 and diaspore, mixed with the two iron oxides goethite and haematite, the aluminium clay mineral kaolinite and small amounts of anatase and ilmenite . Bauxite appears dull in luster and is reddish-brown, white, or tan.
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.
Titanium is a chemical element; it has symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resistant to corrosion in sea water, aqua regia, and chlorine.
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.
Aluminium oxide (or aluminium(III) oxide) is a chemical compound of aluminium and oxygen with the chemical formula Al2O3. It is the most commonly occurring of several aluminium oxides, and specifically identified as aluminium oxide. It is commonly called alumina and may also be called aloxide, aloxite, or alundum in various forms and applications. It occurs naturally in its crystalline polymorphic phase α-Al2O3 as the mineral corundum, varieties of which form the precious gemstones ruby and sapphire. Al2O3 is used to produce aluminium metal, as an abrasive owing to its hardness, and as a refractory material owing to its high melting point.
Ilmenite is a titanium-iron oxide mineral with the idealized formula FeTiO
3. It is a weakly magnetic black or steel-gray solid. Ilmenite is the most important ore of titanium and the main source of titanium dioxide, which is used in paints, printing inks, fabrics, plastics, paper, sunscreen, food and cosmetics.
The Hall–Héroult process is the major industrial process for smelting aluminium. It involves dissolving aluminium oxide (alumina) in molten cryolite and electrolyzing the molten salt bath, typically in a purpose-built cell. The Hall–Héroult process applied at industrial scale happens at 940–980 °C and produces 99.5–99.8% pure aluminium. Recycling aluminum requires no electrolysis, thus it is not treated in this way.
The mineral bastnäsite (or bastnaesite) is one of a family of three carbonate-fluoride minerals, which includes bastnäsite-(Ce) with a formula of (Ce, La)CO3F, bastnäsite-(La) with a formula of (La, Ce)CO3F, and bastnäsite-(Y) with a formula of (Y, Ce)CO3F. Some of the bastnäsites contain OH− instead of F− and receive the name of hydroxylbastnasite. Most bastnäsite is bastnäsite-(Ce), and cerium is by far the most common of the rare earths in this class of minerals. Bastnäsite and the phosphate mineral monazite are the two largest sources of cerium and other rare-earth elements.
Group 4 is the second group of transition metals in the periodic table. It contains the four elements titanium (Ti), zirconium (Zr), hafnium (Hf), and rutherfordium (Rf). The group is also called the titanium group or titanium family after its lightest member.
Industrial processes are procedures involving chemical, physical, electrical, or mechanical steps to aid in the manufacturing of an item or items, usually carried out on a very large scale. Industrial processes are the key components of heavy industry.
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.
Hexafluorosilicic acid is an inorganic compound with the chemical formula H
2SiF
6. Aqueous solutions of hexafluorosilicic acid consist of salts of the cation and hexafluorosilicate anion. These salts and their aqueous solutions are colorless.
Aluminium fluoride is an inorganic compound with the formula AlF3. It forms hydrates AlF3·xH2O. Anhydrous AlF3 and its hydrates are all colorless solids. Anhydrous AlF3 is used in the production of aluminium. Several occur as minerals.
Sodium hexafluoroaluminate is an inorganic compound with formula Na3AlF6. 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 production of aluminium. The compound is the sodium (Na+) salt of the hexafluoroaluminate (AlF63−) ion.
Aluminium smelting is the process of extracting aluminium from its oxide, alumina, generally by the Hall-Héroult process. Alumina is extracted from the ore bauxite by means of the Bayer process at an alumina refinery.
Carl Ludwig Giesecke FRSE 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 Charles Lewis Giesecke. He is falsely accused of being the librettist of his friend Mozart’s The Magic Flute.
Spent Potlining (SPL) is a waste material generated in the primary aluminium smelting industry. Spent Potlining is also known as Spent Potliner and Spent Cell Liner.
Red mud, now more frequently termed bauxite residue, is an industrial waste generated during the processing of bauxite into alumina using the Bayer process. It is composed of various oxide compounds, including the iron oxides which give its red colour. Over 97% of the alumina produced globally is through the Bayer process; for every tonne (2,200 lb) of alumina produced, approximately 1 to 1.5 tonnes of red mud are also produced; the global average is 1.23. Annual production of alumina in 2023 was over 142 million tonnes resulting in the generation of approximately 170 million tonnes of red mud.
Aluminium metal is very rare in native form, and the process to refine it from ores is complex, so for most of human history it was unknown. However, the compound alum has been known since the 5th century BCE and was used extensively by the ancients for dyeing. During the Middle Ages, its use for dyeing made it a commodity of international commerce. Renaissance scientists believed that alum was a salt of a new earth; during the Age of Enlightenment, it was established that this earth, alumina, was an oxide of a new metal. Discovery of this metal was announced in 1825 by Danish physicist Hans Christian Ørsted, whose work was extended by German chemist Friedrich Wöhler.
In der ordentlichen Versammlung der königl. Gesellschaft der Wissenschaften am 1. Februar dieses Jahres stattete Hr. Prof. Abildgaard einen Bericht über die Norwegischen Titanerze und über die von ihm mit denselben angestellten Analysen ab. Zugleich theilte er auch eine Nachricht von einer vor wenigen Jahren aus Grönland nach Dänemark gebrachten besonders weißen spathartigen Miner mit. Einer damit angestellten Untersuchung zu folge bestand sie aus Thonerde und Flußspathsäure. Eine Verbindung, von welcher noch kein ähnliches Beyspiel im Mineralreich vorgekommen ist. Sie hat den Namen Chryolit erhalten, weil sie vor dem Löthrohre wie gefrorne Salzlauge schmilzt.(At the ordinary session of the [Danish] Royal Society of Science on February 1st of this year, Prof. Abildgaard presented a report about Norwegian titanium ores and about the analysis of them undertaken by him. He also communicated a notice of an especially white, spar-like mineral that was brought several years ago from Greenland to Denmark. According to an investigation performed on it, it consists of alumina and hydrofluoric acid. A compound of which no similar example in the mineral realm has yet been found. It received the name "cryolite" because under a blowpipe, it melts like frozen brine.)
[From p. 312] Han har kaldt denne grönlandske Steen Kryolith eller Iissteen formedelst dens Udseende, og fordi den smelter saa meget let for Blæsröret.(He has named this Greenlandic stone cryolite or ice stone on account of its appearance, and because it melts so easily under a blowpipe.)