Aluminium fluoride explained

Aluminium fluoride is an inorganic compound with the formula . It forms hydrates . Anhydrous and its hydrates are all colorless solids. Anhydrous is used in the production of aluminium. Several occur as minerals.

Occurrence and production

Aside from anhydrous, several hydrates are known. With the formula, these compounds include monohydrate (x = 1), two polymorphs of the trihydrate (x = 3), a hexahydrate (x = 6), and a nonahydrate (x = 9).[1]

The majority of aluminium fluoride is produced by treating alumina with hydrogen fluoride at 700 °C: Hexafluorosilicic acid may also be used make aluminium fluoride.[2]

Alternatively, it is manufactured by thermal decomposition of ammonium hexafluoroaluminate. For small scale laboratory preparations, can also be prepared by treating aluminium hydroxide or aluminium with hydrogen fluoride.

Aluminium fluoride trihydrate is found in nature as the rare mineral rosenbergite.

The anhydrous form appears as the relatively recently (as of 2020) recognized mineral óskarssonite.[3] [4] A related, exceedingly rare mineral, is zharchikhite, .[5]

Structure

According to X-ray crystallography, anhydrous adopts the rhenium trioxide motif, featuring distorted octahedra. Each fluoride is connected to two Al centers. Because of its three-dimensional polymeric structure, has a high melting point. The other trihalides of aluminium in the solid state differ, has a layer structure and and , are molecular dimers. Also they have low melting points and evaporate readily to give dimers.[6] In the gas phase aluminium fluoride exists as trigonal molecules of D3h symmetry. The Al–F bond lengths of this gaseous molecule are 163 pm.

Applications

Aluminium fluoride is an important additive for the production of aluminium by electrolysis. Together with cryolite, it lowers the melting point to below 1000 °C and increases the conductivity of the solution. It is into this molten salt that aluminium oxide is dissolved and then electrolyzed to give bulk Al metal.

Aluminium fluoride complexes are used to study the mechanistic aspects of phosphoryl transfer reactions in biology, which are of fundamental importance to cells, as phosphoric acid anhydrides such as adenosine triphosphate and guanosine triphosphate control most of the reactions involved in metabolism, growth and differentiation.[7] The observation that aluminium fluoride can bind to and activate heterotrimeric G proteins has proven to be useful for the study of G protein activation in vivo, for the elucidation of three-dimensional structures of several GTPases, and for understanding the biochemical mechanism of GTP hydrolysis, including the role of GTPase-activating proteins.[8]

Niche uses

Together with zirconium fluoride, aluminium fluoride is an ingredient for the production of fluoroaluminate glasses.

It is also used to inhibit fermentation.

Like magnesium fluoride it is used as a low-index optical thin film, particularly when far UV transparency is required. Its deposition by physical vapor deposition, particularly by evaporation, is favorable.

Safety

The reported oral animal lethal dose (LD50) of aluminium fluoride is 100 mg/kg.[9] Repeated or prolonged inhalation exposure may cause asthma, and may have effects on the bone and nervous system, resulting in bone alterations (fluorosis), and nervous system impairment.[10]

Many of the neurotoxic effects of fluoride are due to the formation of aluminium fluoride complexes, which mimic the chemical structure of a phosphate and influence the activity of ATP phosphohydrolases and phospholipase D. Only micromolar concentrations of aluminium are needed to form aluminium fluoride.[11]

Human exposure to aluminium fluoride can occur in an industrial setting, such as emissions from aluminium reduction processes,[12] or when a person ingests both a fluoride source (e.g., fluoride in drinking water or residue of fluoride-based pesticides) and an aluminium source; sources of human exposure to aluminium include drinking water, tea, food residues, infant formula, aluminium-containing antacids or medications, deodorants, cosmetics, and glassware. Fluoridation chemicals may also contain aluminium fluoride.[13] Data on the potential neurotoxic effects of chronic exposure to the aluminium species existing in water are limited.[14]

See also

External links

Notes and References

  1. The missing Hydrate AlF3·6H2O [Al(H<sub>2</sub>O)<sub>6</sub>]F3: Ionothermal Synthesis, Crystal Structure and Characterization of Aluminum Fluoride Hexahydrate. 2016. Solid State Sciences. 61. 10.1016/j.solidstatesciences.2016.09.007. Guangmei Wang. Anja-Verena Mudring. 61.
  2. Dreveton. Alain. 2012-01-01. Manufacture of Aluminium Fluoride of High Density and Anhydrous Hydrofluoric Acid from Fluosilicic Acid. Procedia Engineering. SYMPHOS 2011 - 1st International Symposium on Innovation and Technology in the Phosphate Industry. 46. Supplement C. 255–265. 10.1016/j.proeng.2012.09.471. free.
  3. Web site: Óskarssonite.
  4. Web site: List of Minerals. 21 March 2011.
  5. Web site: Zharchikhite.
  6. Book: Holleman. A. F.. Wiberg. E.. Inorganic Chemistry. Academic Press. San Diego, CA. 2001 . 0-12-352651-5. .
  7. Wittinghofer. Alfred. 1997-11-01. Signaling mechanistics: Aluminum fluoride for molecule of the year. Current Biology. 7. 11. R682–R685. 10.1016/S0960-9822(06)00355-1. 9382787. 17666164. free.
  8. Vincent. Sylvie. Brouns. Madeleine. Hart. Matthew J.. Settleman. Jeffrey. 1998-03-03. Evidence for distinct mechanisms of transition state stabilization of GTPases by fluoride. Proceedings of the National Academy of Sciences. en. 95. 5. 2210–2215. 0027-8424. 9482864. 10.1073/pnas.95.5.2210. 19296. 1998PNAS...95.2210V. free.
  9. Web site: ALUMINUM FLUORIDE, CASRN: 7784-18-1. June 24, 2005. National Library of Medicine HSDB Database. CDC.gov. October 12, 2017.
  10. Web site: ALUMINIUM FLUORIDE (ANHYDROUS) International Chemical Safety Cards (ICSC). July 22, 2015. CDC.gov National Institute for Occupational Safety and Health (NIOSH). July 17, 2017.
  11. Book: Fluoride in Drinking Water: A Scientific Review of EPA's Standards. The National Academies Press. 2006. 978-0-309-10128-8. 51–52, 219. en. 10.17226/11571.
  12. Book: TOXICOLOGICAL PROFILE FOR FLUORIDES, HYDROGEN FLUORIDE, AND FLUORINE. U.S. DEPARTMENT OF HEALTH AND HUMAN SERVICES Public Health Service Agency for Toxic Substances and Disease Registry. 2003. 211.
  13. Mullenix. Phyllis J. 2014. A new perspective on metals and other contaminants in fluoridation chemicals. International Journal of Occupational and Environmental Health. 20. 2. 157–166. 10.1179/2049396714Y.0000000062. 1077-3525. 4090869. 24999851.
  14. https://ntp.niehs.nih.gov/ntp/htdocs/chem_background/exsumpdf/aluminum_508.pdf Aluminum Compounds Review of Toxicological Literature Abridged Final Report