Ammonium fluorosilicate

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Ammonium fluorosilicate
Diammonium-hexafluorosilicate-unit-cell-3D-balls-A.png
Bararite & Cryptohalite.jpg
Names
IUPAC name
Ammonium hexafluorosilicate
Other names
Ammonium fluorosilicate

Ammonium fluosilicate

Ammonium silicofluoride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.037.229 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 240-968-3
PubChem CID
RTECS number
  • VV7800000
UNII
UN number 2854
  • InChI=1S/F6Si.2H3N/c1-7(2,3,4,5)6;;/h;2*1H3/q-2;;/p+2 Yes check.svgY
    Key: ITHIMUMYFVCXSL-UHFFFAOYSA-P Yes check.svgY
  • InChI=1/F6Si.2H3N/c1-7(2,3,4,5)6;;/h;2*1H3/q-2;;/p+2
    Key: ITHIMUMYFVCXSL-SKRXCDHZAK
  • F[Si-2](F)(F)(F)(F)F.[NH4+].[NH4+]
  • [NH4+].[NH4+].F[Si--](F)(F)(F)(F)F
Properties
(NH4)2[SiF6]
AppearanceWhite crystals
Density 2.0 g cm−3
Melting point 100 °C (212 °F; 373 K) (decomposes) [1]
Solubility dissolves in water and alcohol
Related compounds
Other cations
Hexafluorosilicic acid

Sodium fluorosilicate

Hazards [2] [3]
GHS labelling:
GHS-pictogram-acid.svg GHS-pictogram-skull.svg GHS-pictogram-silhouette.svg
Danger
H301, H311, H315, H319, H331, H335, H372
P260, P261, P264, P270, P271, P280, P301+P310, P302+P352, P304+P340, P305+P351+P338, P312, P314, P321, P330, P332+P313, P337+P313, P362, P403+P233, 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 hazard ACID: Acid
3
0
0
Safety data sheet (SDS) ChemicalBook MSDS
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 ?)

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. [4] It is made of white crystals, [5] which have at least three polymorphs [6] and appears in nature as rare minerals cryptohalite or bararite.

Contents

Structure

Ammonium fluorosilicate has three major polymorphs: α-(NH4)2[SiF6] form is cubic (space group Fm3m, No. 225) and corresponds to the mineral cryptohalite. The β form is trigonal (scalenohedral) and occurs in nature as mineral bararite. [7] A third (γ) form was discovered in 2001 and identified with the hexagonal 6mm symmetry. In all three configurations, the [SiF6]2− octahedra are arranged in layers. In the α form, these layers are perpendicular to [111] directions. In the β- and γ- forms, the layers are perpendicular to the c-axis. [6] (Note: trigonal symmetry is part of the hexagonal group, but not all hexagonal crystals are trigonal. [8] ) The silicon atoms of α-(NH4)2[SiF6] (alpha), have cubic close packing (CCP). The γ form has hexagonal close packing and the β-(NH4)2[SiF6] has primitive hexagonal packing. [9] In all three phases, 12 fluorine atoms neighbor the (NH4)+. [6]

Although bararite was claimed to be metastable at room temperature, [10] it does not appear one polymorph has ever turned into another. [6] Still, bararite is fragile enough that grinding it for spectroscopy will produce a little cryptohalite. [11] Even so, ammonium fluorosilicate assumes a trigonal form at pressures of 0.2 to 0.3 GPa. The reaction is irreversible. If it is not bararite, the phase is at least very closely related. [6]

The hydrogen bonding in (NH4)2[SiF6] allows this salt to change phases in ways that normal salts cannot. Interactions between cations and anions are especially important in how ammonium salts change phase. [6] (To learn more about the β-structure, see Bararite.)

Natural occurrence

This chemical makes rare appearances in nature. [12] It is found as a sublimation product of fumaroles and coal fires. As a mineral, it is either called cryptohalite or bararite, the two being two polymorphs of the compound. [7]

Chemical properties and health hazards

Ammonium fluorosilicate is noncombustible, but it will still release dangerous fumes in a fire, including hydrogen fluoride, silicon tetrafluoride, and nitrogen oxides. It will corrode aluminium. In water, ammonium fluorosilicate dissolves to form an acid solution. [5]

Inhaling dust can lead to pulmonary irritation, possibly death. Ingestion may also prove fatal. Irritation of the eyes comes from contact with the dust, as well as irritation or ulceration of the skin. [5]

Uses

Ammonium fluorosilicate finds use as a disinfectant, and it is useful in etching glass, metal casting, and electroplating. [5] It is also used to help neutralize washing machine water as laundry sour.

See also

Related Research Articles

<span class="mw-page-title-main">Crystal structure</span> Ordered arrangement of atoms, ions, or molecules in a crystalline material

In crystallography, crystal structure is a description of the ordered arrangement of atoms, ions, or molecules in a crystalline material. Ordered structures occur from the intrinsic nature of the constituent particles to form symmetric patterns that repeat along the principal directions of three-dimensional space in matter.

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

The ammonium cation is a positively charged polyatomic ion with the chemical formula NH+4 or [NH4]+. It is formed by the protonation of ammonia. Ammonium is also a general name for positively charged (protonated) substituted amines and quaternary ammonium cations, where one or more hydrogen atoms are replaced by organic or other groups.

<span class="mw-page-title-main">Tridymite</span> Silica mineral, polymorph of quartz

Tridymite is a high-temperature polymorph of silica and usually occurs as minute tabular white or colorless pseudo-hexagonal crystals, or scales, in cavities in felsic volcanic rocks. Its chemical formula is SiO2. Tridymite was first described in 1868 and the type location is in Hidalgo, Mexico. The name is from the Greek tridymos for triplet as tridymite commonly occurs as twinned crystal trillings (compound crystals comprising three twinned crystal components).

<span class="mw-page-title-main">Silicon nitride</span> Compound of silicon and nitrogen

Silicon nitride is a chemical compound of the elements silicon and nitrogen. Si
3
N
4
is the most thermodynamically stable and commercially important of the silicon nitrides, and the term ″Silicon nitride″ commonly refers to this specific composition. It is a white, high-melting-point solid that is relatively chemically inert, being attacked by dilute HF and hot H
3
PO
4
. It is very hard. It has a high thermal stability with strong optical nonlinearities for all-optical applications.

In materials science, polymorphism describes the existence of a solid material in more than one form or crystal structure. Polymorphism is a form of isomerism. Any crystalline material can exhibit the phenomenon. Allotropy refers to polymorphism for chemical elements. Polymorphism is of practical relevance to pharmaceuticals, agrochemicals, pigments, dyestuffs, foods, and explosives. According to IUPAC, a polymorphic transition is "A reversible transition of a solid crystalline phase at a certain temperature and pressure to another phase of the same chemical composition with a different crystal structure." According to McCrone, polymorphs are "different in crystal structure but identical in the liquid or vapor states." Materials with two polymorphs are called dimorphic, with three polymorphs, trimorphic, etc.

<span class="mw-page-title-main">Hexafluorosilicic acid</span> Octahedric silicon compound

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.

<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.

Indium(III) sulfide (Indium sesquisulfide, Indium sulfide (2:3), Indium (3+) sulfide) is the inorganic compound with the formula In2S3.

<span class="mw-page-title-main">Nickel(II) hydroxide</span> Chemical compound

Nickel(II) hydroxide is the inorganic compound with the formula Ni(OH)2. It is a lime-green solid that dissolves with decomposition in ammonia and amines and is attacked by acids. It is electroactive, being converted to the Ni(III) oxy-hydroxide, leading to widespread applications in rechargeable batteries.

<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">Allotropes of boron</span> Materials made only out of boron

Boron can be prepared in several crystalline and amorphous forms. Well known crystalline forms are α-rhombohedral (α-R), β-rhombohedral (β-R), and β-tetragonal (β-T). In special circumstances, boron can also be synthesized in the form of its α-tetragonal (α-T) and γ-orthorhombic (γ) allotropes. Two amorphous forms, one a finely divided powder and the other a glassy solid, are also known. Although at least 14 more allotropes have been reported, these other forms are based on tenuous evidence or have not been experimentally confirmed, or are thought to represent mixed allotropes, or boron frameworks stabilized by impurities. Whereas the β-rhombohedral phase is the most stable and the others are metastable, the transformation rate is negligible at room temperature, and thus all five phases can exist at ambient conditions. Amorphous powder boron and polycrystalline β-rhombohedral boron are the most common forms. The latter allotrope is a very hard grey material, about ten percent lighter than aluminium and with a melting point (2080 °C) several hundred degrees higher than that of steel.

<span class="mw-page-title-main">Hexagonal crystal family</span> Union of crystal groups with related structures and lattices

In crystallography, the hexagonal crystal family is one of the 7 crystal families, which includes two crystal systems and two lattice systems. While commonly confused, the trigonal crystal system and the rhombohedral lattice system are not equivalent. In particular, there are crystals that have trigonal symmetry but belong to the hexagonal lattice.

<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.

Isostructural chemical compounds have similar chemical structures. "Isomorphous" when used in the relation to crystal structures is not synonymous: in addition to the same atomic connectivity that characterises isostructural compounds, isomorphous substances crystallise in the same space group and have the same unit cell dimensions. The IUCR definition used by crystallographers is:

Two crystals are said to be isostructural, if they have the same structure, but not necessarily the same cell dimensions nor the same chemical composition, and with a 'comparable' variability in the atomic coordinates to that of the cell dimensions and chemical composition. For instance, calcite CaCO3, sodium nitrate NaNO3 and iron borate FeBO3 are isostructural. One also speaks of isostructural series, or of isostructural polymorphs or isostructural phase transitions. The term isotypic is synonymous with isostructural.

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

Ammonium carbamate is a chemical compound with the formula [NH4][H2NCO2] consisting of ammonium cation NH+4 and carbamate anion NH2COO. It is a white solid that is extremely soluble in water, less so in alcohol. Ammonium carbamate can be formed by the reaction of ammonia NH3 with carbon dioxide CO2, and will slowly decompose to those gases at ordinary temperatures and pressures. It is an intermediate in the industrial synthesis of urea (NH2)2CO, an important fertilizer.

<span class="mw-page-title-main">Iron–hydrogen alloy</span>

Iron–hydrogen alloy, also known as iron hydride, is an alloy of iron and hydrogen and other elements. Because of its lability when removed from a hydrogen atmosphere, it has no uses as a structural material.

<span class="mw-page-title-main">Triphosphorus pentanitride</span> Chemical compound

Triphosphorus pentanitride is an inorganic compound with the chemical formula P3N5. Containing only phosphorus and nitrogen, this material is classified as a binary nitride. While it has been investigated for various applications this has not led to any significant industrial uses. It is a white solid, although samples often appear colored owing to impurities.

<span class="mw-page-title-main">Solid nitrogen</span> Solid form of the 7th element

Solid nitrogen is a number of solid forms of the element nitrogen, first observed in 1884. Solid nitrogen is mainly the subject of academic research, but low-temperature, low-pressure solid nitrogen is a substantial component of bodies in the outer Solar System and high-temperature, high-pressure solid nitrogen is a powerful explosive, with higher energy density than any other non-nuclear material.

<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. ammonium silicofluoride
  2. "Ammonium Hexafluorosilicate". PubChem. National Institute of Health. Retrieved October 12, 2017.
  3. "SAFETY DATA SHEET Ammonium hexafluorosilicate, 99.999%". Fisher Scientific. Archived from the original on 2017-10-16. Retrieved October 15, 2017.
  4. Wiberg, E., Wiberg, N., and Holleman, A. F. (2001) Inorganic chemistry. Academic Press, San Diego.
  5. 1 2 3 4 Ammonium fuorosilicate, CAMEO Chemicals, NOAA
  6. 1 2 3 4 5 6 Boldyreva, E. V.; Shakhtshneider, T. P.; Sowa, H.; Ahsbas, H. (2007). "Effect of hydrostatic pressure up to 6 GPa on the crystal structures of ammonium and sodium hexafluorosilicates, (NH4)2[SiF6] and Na2[SiF6]; a phase transition in (NH4)2[SiF6] at 0.2–0.3 GPa". Zeitschrift für Kristallographie. 222: 23–29. doi:10.1524/zkri.2007.222.1.23. S2CID   97174719.
  7. 1 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.
  8. Klein, C. and Dutrow, B. (2008) The 23rd Edition of the Manual of Mineral Science. John Wiley & Sons, Hoboken, NJ.
  9. To learn about the primitive hexagonal structure, see Primitive hexagonal packing Archived 2009-05-26 at the Wayback Machine .
  10. Schlemper, Elmer O. (1966). "Structure of Cubic Ammonium Fluosilicate: Neutron-Diffraction and Neutron-Inelastic-Scattering Studies". The Journal of Chemical Physics. 44 (6): 2499–2505. Bibcode:1966JChPh..44.2499S. doi:10.1063/1.1727071.
  11. Oxton, I. A., Knop, O., and Falk, M. (1975) "Infrared Spectra of the Ammonium Ion in Crystals". II. The Ammonium Ion in Trigonal Environments, with a Consideration of Hydrogen Bonding. Canadian Journal of Chemistry, 53, 3394–3400.
  12. Barnes, J. and Lapham, D. (1971) "Rare Minerals Found in Pennsylvania". Pennsylvania Geology, 2, 5, 6–8.