Chemistry:Bismuth compounds

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See also: Category:Bismuth compounds
Bismuth(III) oxide powder

Bismuth compounds are compounds containing the element bismuth (Bi). Bismuth forms trivalent and pentavalent compounds, the trivalent ones being more common. Many of its chemical properties are similar to those of arsenic and antimony, although they are less toxic than derivatives of those lighter elements.[1]

Oxides and sulfides

At elevated temperatures, the vapors of the metal combine rapidly with oxygen, forming the yellow trioxide, Bi2O3.[2][3] When molten, at temperatures above 710 °C, this oxide corrodes any metal oxide and even platinum.[4] On reaction with a base, it forms two series of oxyanions: BiO−2, which is polymeric and forms linear chains, and BiO3−3. The anion in Li3BiO3 is a cubic octameric anion, Bi8O24−24, whereas the anion in Na3BiO3 is tetrameric.[5]

The dark red bismuth(V) oxide, Bi2O5, is unstable, liberating O2 gas upon heating.[6] The compound NaBiO3 is a strong oxidising agent.[7]

Bismuth sulfide, Bi2S3, occurs naturally in bismuth ores.[8] It is also produced by the combination of molten bismuth and sulfur.[9]

Bismuth oxychloride (BiOCl) structure (mineral bismoclite). Bismuth atoms are shown as grey, oxygen red, chlorine green.

Bismuth oxychloride (BiOCl, see figure at right) and bismuth oxynitrate (BiONO3) stoichiometrically appear as simple anionic salts of the bismuthyl(III) cation (BiO+) which commonly occurs in aqueous bismuth compounds. However, in the case of BiOCl, the salt crystal forms in a structure of alternating plates of Bi, O, and Cl atoms, with each oxygen coordinating with four bismuth atoms in the adjacent plane. This mineral compound is used as a pigment and cosmetic (see below).[10]

Bismuthine and bismuthides

Unlike the lighter pnictogens nitrogen, phosphorus, and arsenic, but similar to antimony, bismuth does not form a stable hydride. Bismuth hydride, bismuthine (BiH3), is an endothermic compound that spontaneously decomposes at room temperature. It is stable only below −60 °C.[5] Bismuthides are intermetallic compounds between bismuth and other metals.[11]

In 2014 researchers discovered that sodium bismuthide can exist as a form of matter called a “three-dimensional topological Dirac semi-metal” (3DTDS) that possess 3D Dirac fermions in bulk. It is a natural, three-dimensional counterpart to graphene with similar electron mobility and velocity. Graphene and topological insulators (such as those in 3DTDS) are both crystalline materials that are electrically insulating inside but conducting on the surface, allowing them to function as transistors and other electronic devices. While sodium bismuthide (Na3Bi) is too unstable to be used in devices without packaging, it can demonstrate potential applications of 3DTDS systems, which offer distinct efficiency and fabrication advantages over planar graphene in semiconductor and spintronics applications.[12][13]

Halides

The halides of bismuth in low oxidation states have been shown to adopt unusual structures. What was originally thought to be bismuth(I) chloride, BiCl, turns out to be a complex compound consisting of Bi5+9 cations and BiCl2−5 and Bi2Cl2−8 anions.[5][14] The Bi5+9 cation has a distorted tricapped trigonal prismatic molecular geometry and is also found in Bi10Hf3Cl18, which is prepared by reducing a mixture of hafnium(IV) chloride and bismuth chloride with elemental bismuth, having the structure [Bi+] [Bi5+9] [HfCl2−6]3.[5]:50 Other polyatomic bismuth cations are also known, such as Bi2+8, found in Bi8(AlCl4)2.[14] Bismuth also forms a low-valence bromide with the same structure as "BiCl". There is a true monoiodide, BiI, which contains chains of Bi4I4 units. BiI decomposes upon heating to the triiodide, BiI3, and elemental bismuth. A monobromide of the same structure also exists.[5] In oxidation state +3, bismuth forms trihalides with all of the halogens: BiF3, BiCl3, BiBr3, and BiI3. All of these except BiF3 are hydrolyzed by water.[5]

Bismuth(III) chloride reacts with hydrogen chloride in ether solution to produce the acid HBiCl4.[15]

The oxidation state +5 is less frequently encountered. One such compound is BiF5, a powerful oxidizing and fluorinating agent. It is also a strong fluoride acceptor, reacting with xenon tetrafluoride to form the XeF+3 cation:[15]

BiF5 + XeF4 → XeF+3BiF−6

Aqueous species

In aqueous solution, the Bi3+ ion is solvated to form the aqua ion Bi(H2O)3+8 in strongly acidic conditions.[16] At pH > 0 polynuclear species exist, the most important of which is believed to be the octahedral complex [Bi6O4(OH)4]6+.[17]

Applications

Bismuth vanadate, a yellow pigment
  • Bismuth is included in BSCCO (bismuth strontium calcium copper oxide) which is a group of similar superconducting compounds discovered in 1988 that exhibit the highest superconducting transition temperatures.[18]
  • Bismuth subnitrate is a component of glazes that produces an iridescence and is used as a pigment in paint.
  • Bismuth telluride is a semiconductor and an excellent thermoelectric material.[10][19] Bi2Te3 diodes are used in mobile refrigerators, CPU coolers, and as detectors in infrared spectrophotometers.[10]
  • Bismuth oxide, in its delta form, is a solid electrolyte for oxygen. This form normally breaks down below a high-temperature threshold, but can be electrodeposited well below this temperature in a highly alkaline solution.
  • Bismuth germanate is a scintillator, widely used in X-ray and gamma ray detectors.
  • Bismuth vanadate is an opaque yellow pigment used by some artists' oil, acrylic, and watercolor paint companies, primarily as a replacement for the more toxic cadmium sulfide yellows in the greenish-yellow (lemon) to orange-toned yellow range. It performs practically identically to the cadmium pigments, such as in terms of resistance to degradation from UV exposure, opacity, tinting strength, and lack of reactivity when mixed with other pigments. The most commonly-used variety by artists' paint makers is lemon in color. In addition to being a replacement for several cadmium yellows, it also serves as a non-toxic visual replacement for the older chromate pigments made with zinc, lead, and strontium. If a green pigment and barium sulfate (for increased transparency) are added it can also serve as a replacement for barium chromate, which possesses a more greenish cast than the others. In comparison with lead chromates, it does not blacken due to hydrogen sulfide in the air (a process accelerated by UV exposure) and possesses a particularly brighter color than them, especially the lemon, which is the most translucent, dull, and fastest to blacken due to the higher percentage of lead sulfate required to produce that shade. It is also used, on a limited basis due to its cost, as a vehicle paint pigment.[20][21]
  • A catalyst for making acrylic fibers.[22]
  • As an electrocatalyst in the conversion of CO2 to CO.[23]
  • Ingredient in lubricating greases.[24]
  • In crackling microstars (dragon's eggs) in pyrotechnics, as the oxide, subcarbonate or subnitrate.[25][26]
  • As catalyst for the fluorination of arylboronic pinacol esters through a Bi(III)/Bi(V) catalytic cycle, mimicking transition metals in electrophilic fluorination.[27]

See also

References

  1. ↑ Kean, Sam (2011). The Disappearing Spoon (and other true tales of madness, love, and the history of the world from the Periodic Table of Elements). New York/Boston: Back Bay Books. pp. 158–160. ISBN 978-0-316-051637. 
  2. ↑ Wiberg, p. 768.
  3. ↑ Greenwood, p. 553.
  4. ↑ Krüger, p. 185
  5. ↑ 5.0 5.1 5.2 5.3 5.4 5.5 Godfrey, S. M.; McAuliffe, C. A.; Mackie, A. G.; Pritchard, R. G. (1998). Nicholas C. Norman. ed. Chemistry of arsenic, antimony, and bismuth. Springer. pp. 67–84. ISBN 978-0-7514-0389-3. 
  6. ↑ Scott, Thomas; Eagleson, Mary (1994). Concise encyclopedia chemistry. Walter de Gruyter. p. 136. ISBN 978-3-11-011451-5. https://archive.org/details/conciseencyclope00eagl. 
  7. ↑ Greenwood, p. 578.
  8. ↑ An Introduction to the Study of Chemistry. Forgotten Books. p. 363. ISBN 978-1-4400-5235-4. https://books.google.com/books?id=lGjTyw9gYfYC&pg=PA363. 
  9. ↑ Greenwood, pp. 559–561.
  10. ↑ 10.0 10.1 10.2 Krüger, p. 184.
  11. ↑ "bismuthide". https://www.yourdictionary.com/bismuthide. Retrieved 2020-04-07. 
  12. ↑ "3D counterpart to graphene discovered [UPDATE"]. KurzweilAI. 20 January 2014. https://www.kurzweilai.net/3d-counterpart-to-graphene-discovered. 
  13. ↑ Liu, Z. K.; Zhou, B.; Zhang, Y.; Wang, Z. J.; Weng, H. M.; Prabhakaran, D.; Mo, S. K.; Shen, Z. X. et al. (2014). "Discovery of a Three-Dimensional Topological Dirac Semimetal, Na3Bi". Science 343 (6173): 864–7. doi:10.1126/science.1245085. PMID 24436183. Bibcode: 2014Sci...343..864L. 
  14. ↑ 14.0 14.1 Gillespie, R. J.; Passmore, J. (1975). Emeléus, H. J.. ed. Advances in Inorganic Chemistry and Radiochemistry. Academic Press. pp. 77–78. ISBN 978-0-12-023617-6. https://archive.org/details/isbn_0120236176. 
  15. ↑ 15.0 15.1 Suzuki, p. 8.
  16. ↑ 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. 
  17. ↑ Näslund, Jan; Persson, Ingmar; Sandström, Magnus (2000). "Solvation of the Bismuth(III) Ion by Water, Dimethyl Sulfoxide, N,N'-Dimethylpropyleneurea, and N,N-Dimethylthioformamide. An EXAFS, Large-Angle X-ray Scattering, and Crystallographic Structural Study". Inorganic Chemistry 39 (18): 4012–4021. doi:10.1021/ic000022m. PMID 11198855. 
  18. ↑ "BSCCO". National High Magnetic Field Laboratory. http://www.magnet.fsu.edu/magnettechnology/research/asc/research/bscco.html. 
  19. ↑ Tritt, Terry M. (2000). Recent trends in thermoelectric materials research. Academic Press. p. 12. ISBN 978-0-12-752178-7. https://books.google.com/books?id=jO3nzAbzAWYC&pg=PA12. 
  20. ↑ Tücks, Andreas; Beck, Horst P. (2007). "The photochromic effect of bismuth vanadate pigments: Investigations on the photochromic mechanism". Dyes and Pigments 72 (2): 163. doi:10.1016/j.dyepig.2005.08.027. 
  21. ↑ Müller, Albrecht (2003). "Yellow pigments". Coloring of plastics: Fundamentals, colorants, preparations. Hanser Verlag. pp. 91–93. ISBN 978-1-56990-352-0. https://books.google.com/books?id=WZV_hX9u0yIC&pg=PA92. 
  22. ↑ Hammond, C. R. (2004). The Elements, in Handbook of Chemistry and Physics (81st ed.). Boca Raton (FL, US): CRC press. pp. 4–1. ISBN 978-0-8493-0485-9. https://archive.org/details/crchandbookofche81lide/page/4. 
  23. ↑ DiMeglio, John L.; Rosenthal, Joel (2013). "Selective conversion of CO2 to CO with high efficiency using an bismuth-based electrocatalyst". Journal of the American Chemical Society 135 (24): 8798–8801. doi:10.1021/ja4033549. PMID 23735115. 
  24. ↑ Mortier, Roy M.; Fox, Malcolm F.; Orszulik, Stefan T. (2010). Chemistry and Technology of Lubricants. Springer. p. 430. ISBN 978-1-4020-8661-8. Bibcode: 2010ctl..book.....M. https://books.google.com/books?id=YTa5TsL0KnIC&pg=PA430. 
  25. ↑ Croteau, Gerry; Dills, Russell; Beaudreau, Marc; Davis, Mac (2010). "Emission factors and exposures from ground-level pyrotechnics". Atmospheric Environment 44 (27): 3295. doi:10.1016/j.atmosenv.2010.05.048. Bibcode: 2010AtmEn..44.3295C. 
  26. ↑ Ledgard, Jared (2006). The Preparatory Manual of Black Powder and Pyrotechnics. Lulu. pp. 207, 319, 370, 518, search. ISBN 978-1-4116-8574-1. https://books.google.com/books?id=370UwG8CuNwC&pg=PA518. 
  27. ↑ Planas, Oriol; Wang, Feng; Leutzsch, Markus; Cornella, Josep (2020). "Fluorination of arylboronic esters enabled by bismuth redox catalysis". Science 367 (6475): 313–317. doi:10.1126/science.aaz2258. PMID 31949081. Bibcode: 2020Sci...367..313P. 



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