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a heavy brittle diamagnetic trivalent metallic element (resembles arsenic and antimony chemically); usually recovered as a by-product from ores of other metals (同)Bi, atomic number 83

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蒼鉛(そうえん)(金属元素;化学記号はBi)

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出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2014/10/16 16:34:09」(JST)

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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. 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.^[1]^[2]

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 [Bi₆O_x(OH)_8-x]^(10-x)+ cation. There is indirect evidence that either the octahedral cation Bi₆O₄(OH)₄⁶⁺^[2] or the octahedral cation Bi₆(OH)₁₂⁶⁺^[3] is present in aqueous solution following the polymerisation of Bi(H₂O)₈³⁺, the Bi³⁺ ion present in acidic solutions.^[4] The ion Bi₆O₄(OH)₄⁶⁺ is found in the perchlorate compound Bi₆O₄(OH)₄ClO₄·7H₂O^[5] and is isoelectronic with the octahedral Sn₆O₄(OH)₄ cluster found in the hydrate of tin(II) oxide, 3SnO·H₂O.^[3] The compounds that contain this are:-

Bi₆O₄(HO)₄(NO₃)₆·H₂O^[6]^[7] (equivalent to BiONO₃·0.5 H₂O; Bi₂O₃.N₂O₅.H₂O )

Bi₆O₄(OH)₄(NO₃)₆.4H₂O^[8](equivalent to BiONO₃·H₂O; Bi₂O₃.N₂O₅.6H₂O )

[Bi₆O_4.5(OH)_3.5]₂(NO₃)₁₁ contains two different cations, [Bi₆O₄(OH)₄]⁶⁺ and [Bi₆O₅(OH)₃]⁵⁺^[9]

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.^[10]

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

Bi₂O₂(OH)NO₃ (equivalent to BiONO₃·0.5 H₂O) contains "[Bi₂O₂]²⁺ layers^[11]

Bi₅O₇NO₃ which is isostructural with β–Bi₅O₇I^[12]

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 O^2– 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.^[13]

Preparation of bismuth oxynitrates

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^[14]

At < pH 1, Bi₆O₄(OH)₄(NO₃)₆.4H₂O (BiNO₃.H₂O)is the first solid product, which when heated produced Bi₆H₂O(NO₃)O₄(OH)₄ (BiNO₃. 0.5H₂O.

Between pH 1.2 and pH 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,^[12] which is isostructural with β–Bi₅O₇I and has a layer structure.^[15] The ultimate stage of thermal decomposition of oxynitrates is bismuth(III) oxide, Bi₂O₃.

References

^ Sadler, Peter J (1991). "Chapter 1". In Sykes, A.G. ADVANCES IN INORGANIC CHEMISTRY, Volume 36. Academic Press. ISBN 0-12-023636-2.
^ ^a ^b Holleman, A. F.; Wiberg, E. (2001), Inorganic Chemistry, San Diego: Academic Press, p. 771, ISBN 0-12-352651-5
^ ^a ^b Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 0080379419.
^ 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.
^ Godfrey, S.M. et al. (1998). "Chapter 4". In Norman, N.C. Chemistry of Arsenic, Antimony and Bismuth. Blackie Academic and Professional. ISBN 0 7514 0389 X.
^ Lazarini, F. (1979). "Bismuth basic nitrate [Bi6(H2O)(NO3)O4(OH)4](NO3)5". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry 35 (2): 448–450. doi:10.1107/S0567740879003745. ISSN 0567-7408.
^ 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.
^ Lazarini, F. "Tetra-µ 3-hydroxo-tetra-µ 3-oxo-hexabismuth (III) nitrate tetrahydrate,[Bi 6 O 4 (OH) 4](NO 3) 6• 4H 2 O." Cryst. Struct. Comm 8 (1979): 69-74.
^ 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)". Dalton Transactions 41 (7): 1971. doi:10.1039/c1dt11646k. ISSN 1477-9226.
^ Lazarini, F. (1978). "The crystal structure of a bismuth basic nitrate, [Bi6O5(OH)3](NO3)5.3H2O". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry 34 (11): 3169–3173. doi:10.1107/S0567740878010419. ISSN 0567-7408.
^ Henry, Natacha, et al. "[Bi2O2] 2+ layers in Bi2O2 (OH)(NO3): synthesis and structure determination." Zeitschrift für Naturforschung. B, A journal of chemical sciences 60.3 (2005): 322-327
^ ^a ^b Kodama, Hiroshi (1994). "Synthesis of a New Compound, Bi5O7NO3, by Thermal Decomposition". Journal of Solid State Chemistry 112 (1): 27–30. doi:10.1006/jssc.1994.1259. ISSN 0022-4596.
^ 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.
^ 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.
^ Ziegler, P., M. Ströbele, and H-J. Meyer. "Crystal structure of pentabismuth heptaoxide nitrate, Bi5O7NO3." Zeitschrift für Kristallographie. New crystal structures 219.2 (2004): 91-92

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