Bismuth oxynitrate


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.

Bismuth oxynitrate
IUPAC name
Other names
Basic bismuth nitrate
Bismuth subnitrate [USP:JAN]
  • 1304-85-4 checkY
3D model (JSmol)
  • Interactive image
  • CHEBI:31293 checkY
  • 65321938 checkY
  • DB13209 checkY
MeSH bismuth+subnitrate
  • 73415757
  • H19J064BA5 checkY
  • InChI=1S/5Bi.4NO3.9H2O.O/c;;;;;4*2-1(3)4;;;;;;;;;;/h;;;;;;;;;9*1H2;/q5*+3;4*-1;;;;;;;;;;-2/p-9
  • [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]
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]
GHS labelling:
GHS03: Oxidizing GHS07: Exclamation mark
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references
Bismuth subnitrate monohydrate
IUPAC name
oxobismuthanyl nitrate;hydrate
  • 13595-83-0 checkY
3D model (JSmol)
  • Interactive image
  • 129842132
  • InChI=1S/Bi.NO3.H2O.O/c;2-1(3)4;;/h;;1H2;/q+1;-1;;
  • [N+](=O)([O-])O[Bi]=O.O
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).
Infobox references

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
[4] or the octahedral cation Bi
[5] is present in aqueous solution following the polymerisation of Bi(H
, the Bi3+ ion present in acidic solutions.[6] The ion Bi
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 edit

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 edit

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.

References edit

  1. ^ a b c d e f g h PubChem. "Bismuth subnitrate". Retrieved 2020-11-11.
  2. ^ a b PubChem. "Bismuth subnitrate monohydrate". 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. ^ a b 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. ^ a b 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. ^ a b 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.