Bismuth oxynitrate

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Bismuth oxynitrate
BismuthOxynitrate.png
Names
IUPAC name
pentabismuth;oxygen(2-);nonahydroxide;tetranitrate
Other names
Bismuthyl nitrate
Basic bismuth nitrate
Bismuth subnitrate [USP:JAN]
Bismutum subnitricum
Magisterium bismuti
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
DrugBank
MeSH bismuth+subnitrate
PubChem CID
UNII
  • InChI=1S/5Bi.4NO3.9H2O.O/c;;;;;4*2-1(3)4;;;;;;;;;;/h;;;;;;;;;9*1H2;/q5*+3;4*-1;;;;;;;;;;-2/p-9
    Key: QGWDKKHSDXWPET-UHFFFAOYSA-E [1]
  • [N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[O-2].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[Bi+3] [1]
Properties
Bi5H9N4O22 (Basic formula) [1]
Molar mass 1461.99 g/mol [1]
Density 1.79 g/mL (H2O) [1]
Melting point Decomposes at 260 [1]
Boiling point Decomposes at 260 [1]
Insoluble [1]
Hazards
GHS labelling:
GHS-pictogram-rondflam.svg GHS-pictogram-exclam.svg
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Bismuth subnitrate monohydrate
Names
IUPAC name
oxobismuthanyl nitrate;hydrate
Identifiers
3D model (JSmol)
PubChem CID
  • InChI=1S/Bi.NO3.H2O.O/c;2-1(3)4;;/h;;1H2;/q+1;-1;;
    Key: HFJNHTDBULDRRH-UHFFFAOYSA-N
  • [N+](=O)([O-])O[Bi]=O.O
Properties
BiH2NO5 (Basic formula) [2]
Molar mass 305 g/mol [2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Bismuth oxynitrate is the name applied to a number of compounds that contain Bi3+, nitrate ions and oxide ions and which can be considered as compounds formed from Bi2O3, N2O5 and H2O. Other names for bismuth oxynitrate include bismuth subnitrate and bismuthyl nitrate. In older texts bismuth oxynitrate is often simply described as BiONO3 or basic bismuth nitrate. Bismuth oxynitrate was once called magisterium bismuti or bismutum subnitricum, and was used as a white pigment, in beauty care, and as a gentle disinfectant for internal and external use. [3] [4] It is also used to form Dragendorff's reagent, which is used as a TLC stain.

Contents

Bismuth oxynitrate is commercially available as Bi5O(OH)9(NO3)4 (CAS number: 1304-85-4 ) or as BiONO3·H2O (CAS Number: 13595-83-0 ).

Some compounds have been fully characterised with single crystal studies and found to contain the octahedral [Bi6Ox(OH)8−x](10−x)+ cation. There is indirect evidence that either the octahedral cation Bi
6O
4(OH)6+
4 [4] or the octahedral cation Bi
6(OH)6+
12 [5] is present in aqueous solution following the polymerisation of Bi(H
2O)3+
8, the Bi3+ ion present in acidic solutions. [6] The ion Bi
6O
4(OH)6+
4 is found in the perchlorate compound Bi6O4(OH)4ClO4·7H2O [7] and is isoelectronic with the octahedral Sn6O4(OH)4 cluster found in the hydrate of tin(II) oxide, 3SnO·H2O. [5] The compounds that contain this are:

Bi6O4(HO)4(NO3)6·H2O [8] [9] (equivalent to BiONO3·1/2H2O; Bi2O3·N2O5·H2O )
Bi6O4(OH)4(NO3)6·4H2O [10] (equivalent to BiONO3·H2O; Bi2O3·N2O5·6H2O )
[Bi6O4(OH)4][Bi6O5(OH)3](NO3)11, which contains two different cations, [Bi6O4(OH)4]6+ and [Bi6O5(OH)3]5+ [11]

The compound Bi6O5(OH)3(NO3)5·3H2O (equivalent to 6Bi2O3·5N2O5·9H2O) also contains the octahedral units but this time they are joined to form {[Bi6O5(OH)3]5+}2. [12]

Additionally some oxynitrates have layer structures (a common motif also found in bismuth(III) oxyhalides):

Bi2O2(OH)NO3 (equivalent to BiONO3·1/2H2O) contains "[Bi2O2]2+" layers [13]
Bi5O7NO3, which is isostructural with β-Bi5O7I [14]

Cluster cation structure

The octahedral ion has 6 Bi3+ ions at the corners of an octahedron. There is no covalent bond between the Bi atoms, they are held in position by bridging O2− and OH− anions, one at the centre of each of the eight triangular faces, bridging three Bi ions. The Bi ions are essentially four coordinate and are at the apex of a flat square pyramid. An ab initio theoretical study of the hydration mechanism of Bi3+ and the structure concludes that the lone pairs on the Bi3+ ions are stereochemically active. [15]

Preparation

Bismuth oxynitrates can be prepared from bismuth(III) nitrate. For example, hydrolysis of a solution of bismuth nitrate through the addition of alkali or the reaction of the pentahydrate, BiNO3·5H2O with KOH, or the controlled thermal decomposition of the pentahydrate.

The thermal decomposition of bismuth nitrate pentahydrate proceeds through the following stages: [16]

At pH below 1.0, Bi6O4(OH)4(NO3)6·4H2O (equivalent to BiNO3·H2O) is the first solid product, which when heated produces Bi6H2O(NO3)O4(OH)4 (equivalent to BiNO3.1/2H2O).
Between pH 1.2 and 1.8, further hydrolysis occurs and Bi6O5(OH)3(NO3)5·3H2O is formed.

The final oxynitrate product of thermal dehydration is believed to be Bi5O7NO3, [14] which is isostructural with β–Bi5O7I and has a layer structure. [17] The ultimate stage of thermal decomposition of oxynitrates is bismuth(III) oxide, Bi2O3.

Related Research Articles

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

Copper(II) nitrate describes any member of the family of inorganic compounds with the formula Cu(NO3)2(H2O)x. The hydrates are blue solids. Anhydrous copper nitrate forms blue-green crystals and sublimes in a vacuum at 150-200 °C. Common hydrates are the hemipentahydrate and trihydrate.

In chemistry, water(s) of crystallization or water(s) of hydration are water molecules that are present inside crystals. Water is often incorporated in the formation of crystals from aqueous solutions. In some contexts, water of crystallization is the total mass of water in a substance at a given temperature and is mostly present in a definite (stoichiometric) ratio. Classically, "water of crystallization" refers to water that is found in the crystalline framework of a metal complex or a salt, which is not directly bonded to the metal cation.

<span class="mw-page-title-main">Iron(III) nitrate</span> Chemical compound

Iron(III) nitrate, or ferric nitrate, is the name used for a series of inorganic compounds with the formula Fe(NO3)3.(H2O)n. Most common is the nonahydrate Fe(NO3)3.(H2O)9. The hydrates are all pale colored, water-soluble paramagnetic salts.

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

Nickel nitrate is the inorganic compound Ni(NO3)2 or any hydrate thereof. In the hexahydrate, the nitrate anions are not bonded to nickel. Other hydrates have also been reported: Ni(NO3)2.9H2O, Ni(NO3)2.4H2O, and Ni(NO3)2.2H2O.

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

Bismuth chloride (or butter of bismuth) is an inorganic compound with the chemical formula BiCl3. It is a covalent compound and is the common source of the Bi3+ ion. In the gas phase and in the crystal, the species adopts a pyramidal structure, in accord with VSEPR theory.

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

Cobalt nitrate is the inorganic compound with the formula Co(NO3)2.xH2O. It is cobalt(II)'s salt. The most common form is the hexahydrate Co(NO3)2·6H2O, which is a red-brown deliquescent salt that is soluble in water and other polar solvents.

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

Bismuth oxychloride is an inorganic compound of bismuth with the formula BiOCl. It is a lustrous white solid used since antiquity, notably in ancient Egypt. Light wave interference from its plate-like structure gives a pearly iridescent light reflectivity similar to nacre. Previously, until the last decade of the twentieth century, bismuth oxochloride was known as bismuthyl chloride. It is also known as pigment pearl white.

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

Sodium bismuthate is an inorganic compound, and a strong oxidiser with chemical formula NaBiO3. It is somewhat hygroscopic, but not soluble in cold water, which can be convenient since the reagent can be easily removed after the reaction. It is one of the few water insoluble sodium salts. Commercial samples may be a mixture of bismuth(V) oxide, sodium carbonate and sodium peroxide.

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

Manganese(II) nitrate refers to the inorganic compounds with formula Mn(NO3)2·(H2O)n. These compounds are nitrate salts containing varying amounts of water. A common derivative is the tetrahydrate, Mn(NO3)2·4H2O, but mono- and hexahydrates are also known as well as the anhydrous compound. Some of these compounds are useful precursors to the oxides of manganese. Typical of a manganese(II) compound, it is a paramagnetic pale pink solid.

<span class="mw-page-title-main">Bismuth(III) nitrate</span> Chemical compound

Bismuth(III) nitrate is a salt composed of bismuth in its cationic +3 oxidation state and nitrate anions. The most common solid form is the pentahydrate. It is used in the synthesis of other bismuth compounds. It is available commercially. It is the only nitrate salt formed by a group 15 element, indicative of bismuth's metallic nature.

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

Cerium nitrate refers to a family of nitrates of cerium in the +3 or +4 oxidation state. Often these compounds contain water, hydroxide, or hydronium ions in addition to cerium and nitrate. Double nitrates of cerium also exist.

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

Zirconium nitrate is a volatile anhydrous transition metal nitrate salt of zirconium with formula Zr(NO3)4. It has alternate names of zirconium tetranitrate, or zirconium(IV) nitrate.

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

Thorium(IV) nitrate is a chemical compound, a salt of thorium and nitric acid with the formula Th(NO3)4. A white solid in its anhydrous form, it can form tetra- and pentahydrates. As a salt of thorium it is weakly radioactive.

<span class="mw-page-title-main">Neodymium nitrate</span> Inorganic chemical compound

Neodymium nitrate is a chemical compound with the formula Nd(NO3)3. It is typically encountered as the hexahydrate, Nd(NO3)3·6H2O, which is more accurately formulated as [Nd(NO3)3(H2O)4].2H2O to reflect the crystal structure. It decomposes to NdONO3 at elevated temperature. This water-soluble salt finds use in fabrication of perovskite (CaTiO3) based solid oxide fuel cells, synthesis of Nd3+ doped vanadium pentoxide (V2O5) nanostructure for potential usage in supercapacitors and as a catalyst for Friedlander synthesis of surface modified quinolones for application in medicinal chemistry.

Indium(III) nitrate is a nitrate salt of indium which forms various hydrates. Only the pentahydrate has been crystallographically verified. Other hydrates are also reported in literature, such as the trihydrate.

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

Nitratoauric acid, hydrogen tetranitratoaurate, or simply called gold(III) nitrate is a crystalline gold compound that forms the trihydrate, HAu(NO3)4·3H2O or more correctly H5O2Au(NO3)4·H2O. This compound is an intermediate in the process of extracting gold. In older literature it is also known as aurinitric acid.

The nitrate selenites are mixed anion compounds containing distinct nitrate (NO3−)and selenite (SO32−) groups. The compounds are colourless unless coloured by cations.

<span class="mw-page-title-main">Ytterbium(III) nitrate</span> Chemical compound

Ytterbium(III) nitrate is an inorganic compound, a salt of ytterbium and nitric acid with the chemical formula Yb(NO3)3. The compound forms colorless crystals, dissolves in water, and also forms crystalline hydrates.

<span class="mw-page-title-main">Transition metal nitrate complex</span> Compound of nitrate ligands

A transition metal nitrate complex is a coordination compound containing one or more nitrate ligands. Such complexes are common starting reagents for the preparation of other compounds.

<span class="mw-page-title-main">Bismuthyl (ion)</span> Chemical compound

Bismuthyl — inorganic oxygen-containing singly charged ion with the chemical formula BiO+, is an oxycation of bismuth in the +3 oxidation state. Most often it is formed during the hydrolysis of trivalent bismuth salts, primarily nitrate, chloride and other halides. In chemical compounds, bismuthyl plays the role of a monovalent cation.

References

  1. 1 2 3 4 5 6 7 8 PubChem. "Bismuth subnitrate". pubchem.ncbi.nlm.nih.gov. Retrieved 2020-11-11.
  2. 1 2 PubChem. "Bismuth subnitrate monohydrate". pubchem.ncbi.nlm.nih.gov. Retrieved 2020-11-23.
  3. ↑ Sadler, Peter J (1991). Sykes, A.G. (ed.). Advances in Inorganic Chemistry. Vol. 36. Academic Press. ch. 1. ISBN   0-12-023636-2.
  4. 1 2 Holleman, Arnold Frederik; Wiberg, Egon (2001), Wiberg, Nils (ed.), Inorganic Chemistry, translated by Eagleson, Mary; Brewer, William, San Diego/Berlin: Academic Press/De Gruyter, p. 771, ISBN   0-12-352651-5
  5. 1 2 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN   978-0-08-037941-8.
  6. ↑ Persson, Ingmar (2010). "Hydrated metal ions in aqueous solution: How regular are their structures?". Pure and Applied Chemistry. 82 (10): 1901–1917. doi: 10.1351/PAC-CON-09-10-22 . ISSN   0033-4545.
  7. ↑ Godfrey, S.M.; et al. (1998). "Chapter 4". In Norman, N.C. (ed.). Chemistry of Arsenic, Antimony and Bismuth. Blackie Academic and Professional. ISBN   0-7514-0389-X.
  8. ↑ Lazarini, F. (1979). "Bismuth basic nitrate [Bi6(H2O)(NO3)O4(OH)4](NO3)5". Acta Crystallographica Section B. 35 (2): 448–450. doi:10.1107/S0567740879003745. ISSN   0567-7408.
  9. ↑ Sundvall, Bengt; Elgsaeter, Arnljot; Oftedal, Gunnhild; Strand, Knut A.; Hoyer, Eberhard; Spiridonov, V. P.; Strand, T. G. (1979). "Crystal and Molecular Structure of Tetraoxotetrahydroxobismuth(III) Nitrate Monohydrate, Bi6O4(HO)4(NO3)6.H2O". Acta Chemica Scandinavica. 33a: 219–224. doi: 10.3891/acta.chem.scand.33a-0219 . ISSN   0904-213X.
  10. ↑ Lazarini, F. (1979). "Tetra-μ3-hydroxo-tetra-μ3-oxo-hexabismuth (III) nitrate tetrahydrate, [Bi6O4(OH)4](NO3)6·4H2O". Crystal Structure Communications. 8: 69–74.
  11. ↑ Nørlund Christensen, Axel; Lebech, Bente (2012). "Investigation of the crystal structure of a basic bismuth(III) nitrate with the composition [Bi6O4(OH)4]0.54(1)[Bi6O5(OH)3]0.46(1)(NO3)5.54(1)" (PDF). Dalton Transactions . 41 (7): 1971–1980. doi:10.1039/c1dt11646k. ISSN   1477-9226. PMID   22180862. S2CID   205791388.
  12. ↑ Lazarini, F. (1978). "The crystal structure of a bismuth basic nitrate, [Bi6O5(OH)3](NO3)5·3H2O". Acta Crystallographica Section B . 34 (11): 3169–3173. doi:10.1107/S0567740878010419. ISSN   0567-7408.
  13. ↑ Henry, Natacha; et al. (2005). "[Bi2O2]2+ layers in Bi2O2(OH)(NO3): synthesis and structure determination". Zeitschrift für Naturforschung B. 60 (3): 322–327. doi: 10.1515/znb-2005-0315 . S2CID   197047627.
  14. 1 2 Kodama, Hiroshi (1994). "Synthesis of a New Compound, Bi5O7NO3, by Thermal Decomposition". Journal of Solid State Chemistry . 112 (1): 27–30. Bibcode:1994JSSCh.112...27K. doi:10.1006/jssc.1994.1259. ISSN   0022-4596.
  15. ↑ Pye, C C; Gunasekara, C M; Rudolph, W W (2007). "An ab initio investigation of bismuth hydration". Canadian Journal of Chemistry . 85 (11): 945–950. doi:10.1139/v07-108. ISSN   0008-4042.
  16. ↑ Lazarini, F. (1981). "Thermal dehydration of some basic bismuth nitrates". Thermochimica Acta. 46 (1): 53–55. doi:10.1016/0040-6031(81)85076-9. ISSN   0040-6031.
  17. ↑ Ziegler, P.; Ströbele, M.; Meyer, H.-J. (2004). "Crystal structure of pentabismuth heptaoxide nitrate, Bi5O7NO3". Zeitschrift für Kristallographie: New Crystal Structures. 219 (2): 91–92. doi: 10.1524/ncrs.2004.219.2.91 . S2CID   201123614.
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