Hexafluorosilicic acid

Last updated
Hexafluorosilicic acid
Hexafluorosilicic acid molecular structure.png
Names
Preferred IUPAC name
Hexafluorosilicic acid
Systematic IUPAC name
Dihydrogen hexafluorosilicate
Other names
Fluorosilicic acid, fluosilic acid, hydrofluorosilicic acid, silicofluoride, silicofluoric acid, oxonium hexafluorosilanediuide, oxonium hexafluoridosilicate(2−)
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.037.289 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 241-034-8
PubChem CID
RTECS number
  • VV8225000
UNII
UN number 1778
  • InChI=1S/F6Si/c1-7(2,3,4,5)6/q-2/p+2 Yes check.svgY
    Key: OHORFAFFMDIQRR-UHFFFAOYSA-P Yes check.svgY
  • InChI=1/F6Si/c1-7(2,3,4,5)6/q-2/p+2
    Key: OHORFAFFMDIQRR-SKRXCDHZAM
  • [H+].[H+].F[Si-2](F)(F)(F)(F)F
  • [H+].[H+].F[Si--](F)(F)(F)(F)F
Properties
F6H2Si
Molar mass 144.091 g·mol−1
Appearancetransparent, colorless, fuming liquid
Odor sour, pungent
Density 1.22 g/cm3 (25% soln.)
1.38 g/cm3 (35% soln.)
1.46 g/cm3 (61% soln.)
Melting point c. 19 °C (66 °F; 292 K) (60–70% solution)
< −30 °C (−22 °F; 243 K) (35% solution)
Boiling point 108.5 °C (227.3 °F; 381.6 K) (decomposes)
miscible
1.3465
Structure
Octahedral SiF62
Hazards
GHS labelling:
GHS-pictogram-acid.svg
Danger
H314
P260, P264, P280, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P310, P321, P363, P405, P501
NFPA 704 (fire diamond)
NFPA 704.svgHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
3
0
0
Flash point Non-flammable
Lethal dose or concentration (LD, LC):
430 mg/kg (oral, rat)
Safety data sheet (SDS) External MSDS
Related compounds
Other anions
Hexafluorotitanic acid
Hexafluorozirconic acid
Other cations
Ammonium hexafluorosilicate

Sodium fluorosilicate

Related compounds
Hexafluorophosphoric acid
Fluoroboric acid
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Hexafluorosilicic acid is an inorganic compound with the chemical formula H
2
SiF
6
. Aqueous solutions of hexafluorosilicic acid consist of salts of the cation and hexafluorosilicate anion. These salts and their aqueous solutions are colorless.

Contents

Hexafluorosilicic acid is produced naturally on a large scale in volcanoes. [1] [2] It is manufactured as a coproduct in the production of phosphate fertilizers. The resulting hexafluorosilicic acid is almost exclusively consumed as a precursor to aluminum trifluoride and synthetic cryolite, which are used in aluminium processing. Salts derived from hexafluorosilicic acid are called hexafluorosilicates.

Structure

Structure of (H5O2)2SiF6. The hydrogen bonding between the fluoride and protons are indicated by dashed lines. Color code: green = F, orange = Si, red = O, gray = H. (H5O2)2SiF6, ICSDcode 40388full.png
Structure of (H5O2)2SiF6. The hydrogen bonding between the fluoride and protons are indicated by dashed lines. Color code: green = F, orange = Si, red = O, gray = H.

Hexafluorosilicic acid has been crystallized as various hydrates. These include (H5O2)2SiF6, the more complicated (H5O2)2SiF6·2H2O, and (H5O2)(H7O3)SiF6·4.5H2O. In all of these salts, the octahedral hexafluorosilicate anion is hydrogen bonded to the cations. [3]

Aqueous solutions of hexafluorosilicic acid are often described as H
2
SiF
6
.

Production and principal reactions

Hexafluorosilicic acid is produced commercially from fluoride-containing minerals that also contain silicates. Specifically, apatite and fluorapatite are treated with sulfuric acid to give phosphoric acid, a precursor to several water-soluble fertilizers. This is called the wet phosphoric acid process. [4] As a by-product, approximately 50 kg of hexafluorosilicic acid is produced per tonne of HF owing to reactions involving silica-containing mineral impurities. [5] :3

Some of the hydrogen fluoride (HF) produced during this process in turn reacts with silicon dioxide (SiO2) impurities, which are unavoidable constituents of the mineral feedstock, to give silicon tetrafluoride. Thus formed, the silicon tetrafluoride reacts further with HF.[ citation needed ] The net process can be described as: [6] [ page needed ]

6 HF + SiO2 → SiF2−6 + 2 H3O+

Hexafluorosilicic acid can also be produced by treating silicon tetrafluoride with hydrofluoric acid. [6]

Reactions

Hexafluorosilic acid is only stable in hydrogen fluoride or acidic aqueous solutions. In any other circumstance, it acts as a source of hydrofluoric acid. Thus, for example, hexafluorosilicic acid pure or in oleum solution evolves silicon tetrafluoride until the residual hydrogen fluoride re-establishes equilibrium: [6]

H2SiF6  2 HF(l) + SiF4(g)

In alkaline-to-neutral aqueous solutions, hexafluorosilicic acid readily hydrolyzes to fluoride anions and amorphous, hydrated silica ("SiO2"). Strong bases give fluorosilicate salts at first, but any stoichiometric excess begins hydrolysis. [6] At the concentrations usually used for water fluoridation, 99% hydrolysis occurs: [5] [7]

SiF2−
6
+ 2 H2O → 6 F + SiO2 + 4 H+

Alkali and alkaline earth salts

Neutralization of solutions of hexafluorosilicic acid with alkali metal bases produces the corresponding alkali metal fluorosilicate salts:

H2SiF6 + 2 NaOH → Na2SiF6 + 2 H2O

The resulting salt Na2SiF6 is mainly used in water fluoridation. Related ammonium and barium salts are produced similarly for other applications. At room temperature 15-30% concentrated hexafluorosilicic acid undergoes similar reactions with chlorides, hydroxides, and carbonates of alkali and alkaline earth metals. [8]

Sodium hexafluorosilicate for instance may be produced by treating sodium chloride (NaCl) by hexafluorosilicic acid: [5] :3 [9] :7

2NaCl + H2SiF627 °CNa2SiF6↓ + 2 HCl
BaCl2 + H2SiF627 °CBaSiF6↓ + 2 HCl

Heating sodium hexafluorosilicate gives silicon tetrafluoride: [9] :8

Na2SiF6>400 °CSiF4 + 2 NaF

Uses

The majority of the hexafluorosilicic acid is converted to aluminium fluoride and synthetic cryolite. These materials are central to the conversion of aluminium ore into aluminium metal. The conversion to aluminium trifluoride is described as: [6]

H2SiF6 + Al2O3 → 2 AlF3 + SiO2 + H2O

Hexafluorosilicic acid is also converted to a variety of useful hexafluorosilicate salts. The potassium salt, Potassium fluorosilicate, is used in the production of porcelains, the magnesium salt for hardened concretes and as an insecticide, and the barium salts for phosphors.

Hexafluorosilicic acid and the salts are used as wood preservation agents. [10]

Lead refining

Hexafluorosilicic acid is also used as an electrolyte in the Betts electrolytic process for refining lead.

Rust removers

Hexafluorosilicic acid (identified as hydrofluorosilicic acid on the label) along with oxalic acid are the active ingredients used in Iron Out rust-removing cleaning products, which are essentially varieties of laundry sour.

Niche applications

H2SiF6 is a specialized reagent in organic synthesis for cleaving Si–O bonds of silyl ethers. It is more reactive for this purpose than HF. It reacts faster with t-butyldimethysilyl (TBDMS) ethers than triisopropylsilyl (TIPS) ethers. [11]

Treating concrete

The application of hexafluorosilica acid to a calcium rich surface such as concrete will give that surface some resistance to acid attack. [12]

CaCO3 + H2O →  Ca2+ + 2 OH + CO2
H2SiF6 → 2 H+ + SiF2−
6
SiF2−
6
+ 2 H2O → 6 F + SiO2 + 4 H+
 Ca2+ + 2 F → CaF2

Calcium fluoride (CaF2) is an insoluble solid that is acid resistant.

Natural salts

Some rare minerals, encountered either within volcanic or coal-fire fumaroles, are salts of the hexafluorosilicic acid. Examples include ammonium hexafluorosilicate that naturally occurs as two polymorphs: cryptohalite and bararite. [13] [14] [15]

Safety

Hexafluorosilicic acid can release hydrogen fluoride (HF) when evaporated, so it has similar risks. Inhalation of the vapors may cause lung edema. Like hydrogen fluoride, it attacks glass and stoneware. [16] The LD50 value of hexafluorosilicic acid is 430 mg/kg. [5]

See also

Related Research Articles

Fluoride is an inorganic, monatomic anion of fluorine, with the chemical formula F
, whose salts are typically white or colorless. Fluoride salts typically have distinctive bitter tastes, and are odorless. Its salts and minerals are important chemical reagents and industrial chemicals, mainly used in the production of hydrogen fluoride for fluorocarbons. Fluoride is classified as a weak base since it only partially associates in solution, but concentrated fluoride is corrosive and can attack the skin.

<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. 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.

<span class="mw-page-title-main">Sodium fluoride</span> Ionic compound (NaF)

Sodium fluoride (NaF) is an inorganic compound with the formula NaF. It is a colorless or white solid that is readily soluble in water. It is used in trace amounts in the fluoridation of drinking water to prevent tooth decay, and in toothpastes and topical pharmaceuticals for the same purpose. In 2021, it was the 291st most commonly prescribed medication in the United States, with more than 600,000 prescriptions. It is also used in metallurgy and in medical imaging.

<span class="mw-page-title-main">Monocalcium phosphate</span> Chemical compound

Monocalcium phosphate is an inorganic compound with the chemical formula Ca(H2PO4)2 ("AMCP" or "CMP-A" for anhydrous monocalcium phosphate). It is commonly found as the monohydrate ("MCP" or "MCP-M"), Ca(H2PO4)2·H2O. Both salts are colourless solids. They are used mainly as superphosphate fertilizers and are also popular leavening agents.

<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 an aqueous solution termed 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, e.g. 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, much higher than other hydrogen halides.

<span class="mw-page-title-main">Ammonium bifluoride</span> Chemical compound

Ammonium bifluoride is the inorganic compound with the formula [NH4][HF2] or [NH4]F·HF. It is produced from ammonia and hydrogen fluoride. This colourless salt is a glass-etchant and an intermediate in a once-contemplated route to hydrofluoric acid.

<span class="mw-page-title-main">Silicon tetrafluoride</span> Chemical compound

Silicon tetrafluoride or tetrafluorosilane is a chemical compound with the formula SiF4. This colorless gas is notable for having a narrow liquid range: its boiling point is only 4 °C above its melting point. It was first prepared in 1771 by Carl Wilhelm Scheele by dissolving silica in hydrofluoric acid., later synthesized by John Davy in 1812. It is a tetrahedral molecule and is corrosive.

<span class="mw-page-title-main">Zirconium tetrafluoride</span> Chemical compound

Zirconium(IV) fluoride describes members of a family inorganic compounds with the formula (ZrF4(H2O)x. All are colorless, diamagnetic solids. Anhydrous Zirconium(IV) fluoride' is a component of ZBLAN fluoride glass.

The chemical element nitrogen is one of the most abundant elements in the universe and can form many compounds. It can take several oxidation states; but the most common oxidation states are -3 and +3. Nitrogen can form nitride and nitrate ions. It also forms a part of nitric acid and nitrate salts. Nitrogen compounds also have an important role in organic chemistry, as nitrogen is part of proteins, amino acids and adenosine triphosphate.

Silicon compounds are compounds containing the element silicon (Si). As a carbon group element, silicon often forms compounds in the +4 oxidation state, though many unusual compounds have been discovered that differ from expectations based on its valence electrons, including the silicides and some silanes. Metal silicides, silicon halides, and similar inorganic compounds can be prepared by directly reacting elemental silicon or silicon dioxide with stable metals or with halogens. Silanes, compounds of silicon and hydrogen, are often used as strong reducing agents, and can be prepared from aluminum–silicon alloys and hydrochloric acid.

<span class="mw-page-title-main">Fluoroboric acid</span> Chemical compound

Fluoroboric acid or tetrafluoroboric acid is an inorganic compound with the simplified chemical formula H+[BF4]. Unlike other strong acids like H2SO4 or HClO4, the pure tetrafluoroboric acid does not exist. The term "fluoroboric acid" refers to a range of chemical compounds, depending on the solvent. The H+ in the simplified formula of fluoroboric acid represents the solvated proton. The solvent can be any suitable Lewis base. For instance, if the solvent is water, fluoroboric acid can be represented by the formula [H3O]+[BF4], although more realistically, several water molecules solvate the proton: [H(H2O)n]+[BF4]. The ethyl ether solvate is also commercially available, where the fluoroboric acid can be represented by the formula [H( 2O)n]+[BF4], where n is most likely 2.

<span class="mw-page-title-main">Manganese(IV) fluoride</span> Chemical compound

Manganese tetrafluoride, MnF4, is the highest fluoride of manganese. It is a powerful oxidizing agent and is used as a means of purifying elemental fluorine.

<span class="mw-page-title-main">Sodium fluorosilicate</span> Chemical compound

Sodium fluorosilicate is a compound with the chemical formula Na2[SiF6]. Unlike other sodium salts, it has a low solubility in water.

<span class="mw-page-title-main">Bararite</span> Halide mineral

Bararite is a natural form of ammonium fluorosilicate (also known as hexafluorosilicate or fluosilicate). It has chemical formula (NH4)2SiF6 and trigonal crystal structure. This mineral was once classified as part of cryptohalite. Bararite is named after the place where it was first described, Barari, India. It is found at the fumaroles of volcanoes (Vesuvius, Italy), over burning coal seams (Barari, India), and in burning piles of anthracite (Pennsylvania, U.S.). It is a sublimation product that forms with cryptohalite, sal ammoniac, and native sulfur.

Ammonium fluorosilicate (also known as ammonium hexafluorosilicate, ammonium fluosilicate or ammonium silicofluoride) has the formula (NH4)2SiF6. It is a toxic chemical, like all salts of fluorosilicic acid. It is made of white crystals, which have at least three polymorphs and appears in nature as rare minerals cryptohalite or bararite.

<span class="mw-page-title-main">Germanium tetrafluoride</span> Chemical compound

Germanium tetrafluoride (GeF4) is a chemical compound of germanium and fluorine. It is a colorless gas.

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">Aluminium compounds</span>

Aluminium (British and IUPAC spellings) or aluminum (North American spelling) combines characteristics of pre- and post-transition metals. Since it has few available electrons for metallic bonding, like its heavier group 13 congeners, it has the characteristic physical properties of a post-transition metal, with longer-than-expected interatomic distances. Furthermore, as Al3+ is a small and highly charged cation, it is strongly polarizing and aluminium compounds tend towards covalency; this behaviour is similar to that of beryllium (Be2+), an example of a diagonal relationship. However, unlike all other post-transition metals, the underlying core under aluminium's valence shell is that of the preceding noble gas, whereas for gallium and indium it is that of the preceding noble gas plus a filled d-subshell, and for thallium and nihonium it is that of the preceding noble gas plus filled d- and f-subshells. Hence, aluminium does not suffer the effects of incomplete shielding of valence electrons by inner electrons from the nucleus that its heavier congeners do. Aluminium's electropositive behavior, high affinity for oxygen, and highly negative standard electrode potential are all more similar to those of scandium, yttrium, lanthanum, and actinium, which have ds2 configurations of three valence electrons outside a noble gas core: aluminium is the most electropositive metal in its group. Aluminium also bears minor similarities to the metalloid boron in the same group; AlX3 compounds are valence isoelectronic to BX3 compounds (they have the same valence electronic structure), and both behave as Lewis acids and readily form adducts. Additionally, one of the main motifs of boron chemistry is regular icosahedral structures, and aluminium forms an important part of many icosahedral quasicrystal alloys, including the Al–Zn–Mg class.

Potassium fluorosilicate is a chemical compound with the chemical formula K2[SiF6].

References

  1. Palache, C., Berman, H., and Frondel, C. (1951) Dana’s System of Mineralogy, Volume II: Halides, Nitrates, Borates, Carbonates, Sulfates, Phosphates, Arsenates, Tungstates, Molybdates, etc. John Wiley and Sons, Inc., New York, 7th edition.
  2. Anthony, J.W., Bideaux, R.A., Bladh, K.W., and Nichols, M.C. (1997) Handbook of Mineralogy, Volume III: Halides, Hydroxides, Oxides. Mineral Data Publishing, Tucson.
  3. 1 2 Mootz, D.; Oellers, E.-J. (1988). "The Crystalline Hydrates of Hexafluorosilicic Acid: A Combined Phase-Analytical and Structural Study". Zeitschrift für anorganische und allgemeine Chemie. 559: 27–39. doi:10.1002/zaac.19885590103.
  4. USGS. Fluorspar.
  5. 1 2 3 4 "Sodium Hexafluorosilicate [CASRN 16893-85-9] and Fluorosilicic Acid [CASRN 16961-83-4] Review of Toxicological Literature" (PDF). National Toxicology Program (U.S.). Archived (PDF) from the original on 22 October 2012. Retrieved 13 July 2017.
  6. 1 2 3 4 5 Aigueperse, J.; Mollard, P.; Devilliers, D.; Chemla, M.; Faron, R.; Romano, R.; Cuer, J. P. "Fluorine Compounds, Inorganic". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a11_307. ISBN   978-3527306732.
  7. Finney, William F.; Wilson, Erin; Callender, Andrew; Morris, Michael D.; Beck, Larry W. (2006). "Reexamination of Hexafluorosilicate Hydrolysis by 19F NMR and pH Measurement". Environ. Sci. Technol. 40 (8): 2572–2577. Bibcode:2006EnST...40.2572F. doi:10.1021/es052295s. PMID   16683594.
  8. Hoffman CJ, Gutowsky HS, Schumb WC, Breck DW (1953). Silicon Tetrafluoride. Inorganic Syntheses. Vol. 4. pp. 147–8. doi:10.1002/9780470132357.ch47.
  9. 1 2 UsGranted A345458,Keith, C. Hansen&L. Yaws, Carl,"Patent Silicon tetrafluoride generation",published January 3, 1982,issued 1982
  10. Carsten Mai, Holger Militz (2004). "Modification of wood with silicon compounds. inorganic silicon compounds and sol-gel systems: a review". Wood Science and Technology. 37 (5): 339. doi:10.1007/s00226-003-0205-5. S2CID   9672269.
  11. Pilcher, A. S.; DeShong, P. (2001). "Fluorosilicic Acid". Encyclopedia of Reagents for Organic Synthesis. John Wiley & Sons. doi:10.1002/047084289X.rf013. ISBN   0471936235.
  12. Properties of Concrete by A M Neville
  13. "Cryptohalite".
  14. "Bararite".
  15. Kruszewski, Łukasz; Fabiańska, Monika J.; Segit, Tomasz; Kusy, Danuta; Motyliński, Rafał; Ciesielczuk, Justyna; Deput, Ewa (2020). "Carbon‑nitrogen compounds, alcohols, mercaptans, monoterpenes, acetates, aldehydes, ketones, SF6, PH3, and other fire gases in coal-mining waste heaps of Upper Silesian Coal Basin (Poland) – a re-investigation by means of in situ FTIR external database approach". Science of the Total Environment. 698: 134274. Bibcode:2020ScTEn.698m4274K. doi:10.1016/j.scitotenv.2019.134274. PMID   31509784. S2CID   202563638.
  16. "Fluorosilicic Acid – International Chemical Safety Cards". NIOSH. Retrieved 2015-03-10.