Examine individual changes

'{{infobox bismuth}} '''Bismuth''' is a [[chemical element]] with symbol&nbsp;'''Bi''' and [[atomic number]] 83. It is a [[pentavalent]] [[post-transition metal]] and one of the [[pnictogen]]s with chemical properties resembling its lighter homologs [[arsenic]] and [[antimony]]. Elemental bismuth may occur naturally, although its [[sulfide]] and [[oxide]] form important commercial ores. The [[free element]] is 86% as dense as [[lead]]. It is a brittle metal with a silvery white color when freshly produced, but surface [[redox|oxidation]] can give it a pink tinge. Bismuth is marginally [[radioactive]], and the most naturally [[Diamagnetism|diamagnetic]] element, and has one of the lowest values of [[thermal conductivity]] among metals. Bismuth metal has been known since ancient times, although it was often confused with lead and tin, which share some physical properties. The etymology is uncertain, but possibly comes from Arabic ''bi ismid'', meaning having the properties of antimony<ref>[http://webmineral.com/data/Bismuth.shtml Bismuth]. WebMineral. Retrieved on 17 December 2011.</ref> or the German words ''weiße Masse'' or ''Wismuth'' ("white mass"), translated in the mid-sixteenth century to [[New Latin]] ''bisemutum''.<ref name=oet/> Bismuth was long considered the element with the highest atomic mass that is stable, but in 2003 it was discovered to be extremely weakly [[radioactive]]: its only [[primordial isotope]], [[bismuth-209]], decays via [[alpha decay]] with a [[half-life]] more than a [[1000000000 (number)|billion]] times the estimated [[age of the universe]].<ref>{{cite news| url=http://physicsworld.com/cws/article/news/2003/apr/23/bismuth-breaks-half-life-record-for-alpha-decay| title=Bismuth breaks half-life record for alpha decay| date=23 April 2003| publisher=Physicsworld| first=Belle| last= Dumé}}</ref><ref name=Kean>{{cite book|last=Kean|first=Sam|title=The Disappearing Spoon (and other true tales of madness, love, and the history of the world from the Periodic Table of Elements)|publisher=Back Bay Books |location=New York/Boston|year=2011|pages=158–160|isbn=978-0-316-051637}}</ref> Because of its tremendously long half-life, bismuth may still be considered stable for almost all purposes.<ref name=Kean/> Bismuth compounds account for about half the production of bismuth. They are used in cosmetics, pigments, and a few pharmaceuticals, notably [[bismuth subsalicylate]], used to treat diarrhea.<ref name="Kean"/> Bismuth's unusual propensity to expand upon freezing is responsible for some of its uses, such as in casting of printing type.<ref name="Kean"/> Bismuth has unusually low [[toxicity]] for a heavy metal.<ref name="Kean"/> As the toxicity of lead has become more apparent in recent years, there is an increasing use of bismuth alloys (presently about a third of bismuth production) as a replacement for lead. == History == [[File:Bismuth symbol by Torbern Bergman.png|thumb|upright=0.5|left|[[Alchemical symbol]] used by [[Torbern Bergman]], 1775]] The name ''bismuth'' dates from around the 1660s, and is of uncertain etymology. It is one of the first 10 metals to have been discovered. Bismuth appears in the 1660s, from obsolete [[German language|German]] ''{{lang|de|Bismuth}}'', ''{{lang|de|Wismut}}'', ''{{lang|de|Wissmuth}}'' (early 16th century); perhaps related to [[Old High German]] ''{{lang|goh|hwiz}}'' ("white").<ref name=oet>{{OEtymD|bismuth}}</ref> The [[New Latin]] ''{{lang|la|bisemutum}}'' (due to [[Georgius Agricola]], who Latinized many German mining and technical words) is from the German ''{{lang|de|Wismuth}}'', perhaps from ''{{lang|de|weiße Masse}}'', "white mass".<ref>{{cite book| url = https://books.google.com/books?id=vVhpurkfeN4C&pg=PA41| page = 41| title = Chemistry of arsenic, antimony, and bismuth| isbn = 978-0-7514-0389-3| author1 = Norman| first1 = Nicholas C.| date = 1998}}</ref> The element was confused in early times with [[tin]] and lead because of its resemblance to those elements. Bismuth has been known since ancient times, so no one person is credited with its discovery. [[Georgius Agricola|Agricola]], in [[De Natura Fossilium]] (c. 1546) states that bismuth is a distinct metal in a family of metals including tin and lead. This was based on observation of the metals and their physical properties.<ref>{{cite book| author = Agricola, Georgious| title = De Natura Fossilium| location = New York| publisher = Mineralogical Society of America| origyear= 1546 | date=1955| page = 178}}</ref><!-- https://books.google.com/books?id=9pxPAAAAcAAJ&pg=PA143 --> Miners in the age of alchemy also gave bismuth the name ''{{lang|la|tectum argenti}},'' or "silver being made," in the sense of silver still in the process of being formed within the Earth.<ref>{{cite book| url = https://books.google.com/books?id=GL5PAAAAMAAJ&pg=PT181| page = 181| chapter = Bismuth| title = American edition of the British encyclopedia: Or, Dictionary of Arts and sciences ; comprising an accurate and popular view of the present improved state of human knowledge| author1 = Nicholson| first1 = William| date = 1819}}</ref><ref name="Weeks">{{cite journal|doi = 10.1021/ed009p11|title = The discovery of the elements. II. Elements known to the alchemists|date = 1932|last1 = Weeks|first1 = Mary Elvira|authorlink1=Mary Elvira Weeks|journal = Journal of Chemical Education|volume = 9|page = 11|bibcode = 1932JChEd...9...11W}}</ref><ref>Giunta, Carmen J. [http://web.lemoyne.edu/~giunta/archems.html Glossary of Archaic Chemical Terms], [[Le Moyne College]]. See also for other terms for bismuth, including ''stannum glaciale'' (glacial tin or ice-tin).</ref> Beginning with [[Johann Heinrich Pott]] in 1738,<ref>{{cite book|url = https://books.google.com/books?id=eQVAAAAAcAAJ&pg=RA1-PA134| page=134| chapter = De Wismutho|title = Exercitationes chymicae|publisher=Berolini: Apud Johannem Andream Rüdigerum|author1 = Pott|first1 = Johann Heinrich|date = 1738}}</ref> [[Carl Wilhelm Scheele]] and [[Torbern Olof Bergman]], the distinctness of lead and bismuth became clear, and [[Claude François Geoffroy]] demonstrated in 1753 that this metal is distinct from lead and tin.<ref name="Weeks"/><ref name=CRC/><ref>{{cite journal|url = http://gallica.bnf.fr/ark:/12148/bpt6k3551g/f197.image.r=royal.langEN|title = Sur Bismuth|page = 190|date = 1753|journal = Histoire de l'Académie royale des sciences&nbsp;... avec les mémoires de mathématique & de physique&nbsp;... tirez des registres de cette Académie|author = Geoffroy}}</ref> <!-- "Artificial bismuth" was commonly used in place of the actual metal. It was made by hammering tin into thin plates, and cementing them by a mixture of white tartar, [[Potassium nitrate|saltpeter]], and [[arsenic]], stratified in a [[crucible]] over an open fire.{{Citation needed|date=May 2009}} --> Bismuth was also known to the [[Incas]] and used (along with the usual copper and tin) in a special [[Bismuth bronze|bronze alloy]] for knives.<ref>{{cite journal|jstor = 1692247|journal = Science|volume = 223|issue = 4636|pages = 585–586 |last1 = Gordon| first1= Robert B.|last2 = Rutledge| first2= John W.|title = Bismuth Bronze from Machu Picchu, Peru|doi = 10.1126/science.223.4636.585|pmid = 17749940|date = 1984|bibcode = 1984Sci...223..585G}}</ref> == Characteristics == [[File:Bi-crystal.jpg|thumb|left|upright|Bismuth crystal illustrating the many iridescent refraction hues of its oxide surface]] [[File:Wismut Kristall und 1cm3 Wuerfel.jpg|thumb|left|Artificially grown bismuth crystal illustrating the stairstep crystal structure, with a 1&nbsp;cm³ cube of bismuth metal]] === Physical characteristics === Bismuth is a brittle metal with a white, silver-pink hue, often with an [[Iridescence|iridescent]] [[Bismuth(III) oxide|oxide]] tarnish showing many colors from yellow to blue. The spiral, stair-stepped structure of bismuth crystals is the result of a higher growth rate around the outside edges than on the inside edges. The variations in the thickness of the oxide layer that forms on the surface of the crystal cause different wavelengths of light to interfere upon reflection, thus displaying a rainbow of colors. When [[combustion|burned]] in [[oxygen]], bismuth burns with a blue [[flame]] and [[bismuth oxide|its oxide]] forms yellow [[Vapor|fumes]].<ref name="CRC" /> Its [[toxicity]] is much lower than that of its neighbors in the [[periodic table]], such as lead, [[antimony]], and [[polonium]]. No other metal is verified to be more naturally [[Diamagnetism|diamagnetic]] than bismuth.<ref name="CRC" /><ref>[[#Kruger|Krüger]], p. 171.</ref> ([[Superdiamagnetism]] is a different physical phenomenon.) Of any metal, it has one of the lowest values of [[thermal conductivity]] (after [[manganese]], and maybe [[neptunium]] and [[plutonium]]) and the highest [[Hall effect|Hall coefficient]].<ref>{{cite journal| doi = 10.1098/rspa.1936.0126 |jstor = 96773| title = The Theory of the Galvomagnetic Effects in Bismuth| date = 1936| last1 = Jones| first1 = H.| journal = Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences| volume = 155| issue = 886| page = 653|bibcode = 1936RSPSA.155..653J}}</ref> It has a high [[Electrical resistivity and conductivity|electrical resistivity]].<ref name="CRC">{{cite book| first= C. R.|last= Hammond|page=4–1<!-- not a range --> |title = The Elements, in Handbook of Chemistry and Physics |edition = 81st| location = Boca Raton (FL, US)|publisher =CRC press| isbn = 0-8493-0485-7| date = 2004}}</ref> When deposited in sufficiently thin layers on a substrate, bismuth is a [[semiconductor]], despite being a [[post-transition metal]].<ref>{{cite journal| title = Semimetal-to-semiconductor transition in bismuth thin films|journal = Phys. Rev. B|volume =48|page =11431|date =1993|doi =10.1103/PhysRevB.48.11431|bibcode = 1993PhRvB..4811431H| issue = 15| last1 = Hoffman| first1 = C.| last2 = Meyer| first2 = J.| last3 = Bartoli| first3 = F.| last4 = Di Venere| first4 = A.| last5 = Yi| first5 = X.| last6 = Hou| first6 = C.| last7 = Wang| first7 = H.| last8 = Ketterson| first8 = J.| last9 = Wong| first9 = G.}}</ref>[[File:Bismuth sample 1B.jpg|thumb|Bismuth sample demonstrating staircase structure and iridescent properties]]Elemental bismuth is [[density|denser]] in the liquid phase than the solid, a characteristic it shares with [[germanium]], [[silicon]], [[gallium]] and [[water]].<ref name="w768">[[#Wiberg|Wiberg]], p. 768.</ref> Bismuth expands 3.32% on solidification; therefore, it was long a component of low-melting [[typesetting]] [[alloy]]s, where it compensated for the contraction of the other alloying components<ref name="CRC" /><ref>{{cite book| url =https://books.google.com/books?id=XD-dhveegRYC| page = 268| title =Modern physical science| isbn =978-0-03-007381-6| author1 =Tracy| first1 =George R.| last2 =Tropp| first2 =Harry E.| last3 =Friedl| first3 =Alfred E.| date =1974}}</ref><ref>{{cite journal| doi = 10.1039/JS8682100071| title = IX.—Freezing of water and bismuth| date = 1868| last1 = Tribe| first1 = Alfred| journal = Journal of the Chemical Society| volume = 21| page = 71}}</ref><ref>{{cite book| url =https://books.google.com/books?id=n-fiyYg3iSIC&pg=PA82|page = 82| title =The Physics of Phase Transitions| isbn =978-3-540-33390-6| author1 =Papon| first1 =Pierre| last2 =Leblond| first2 =Jacques| last3 =Meijer| first3 =Paul Herman Ernst| date =2006}}</ref> to form almost isostatic [[Lead-bismuth eutectic|bismuth-lead eutectic]] alloys. Though virtually unseen in nature, high-purity bismuth can form distinctive, colorful [[hopper crystal]]s. It is relatively nontoxic and has a low melting point just above 271&nbsp;°C, so crystals may be grown using a household stove, although the resulting crystals will tend to be lower quality than lab-grown crystals.<ref>{{cite book|url=https://books.google.com/books?id=FGaIhhZ8ivsC&pg=PA2|page=2|title=The science of crystallization: microscopic interfacial phenomena|last=Tiller| first = William A.|publisher=Cambridge University Press|date=1991|isbn=0-521-38827-9}}</ref> At ambient conditions bismuth shares the same layered structure as the metallic forms of [[arsenic]] and [[antimony]],<ref name=w767>[[#Wiberg|Wiberg]], p. 767.</ref> crystallizing in the [[Trigonal crystal system|rhombohedral lattice]]<ref>[[#Kruger|Krüger]], p. 172.</ref> ([[Pearson symbol]] hR6, [[space group]] R{{overline|3}}m No. 166), which is often classed into trigonal or hexagonal crystal systems.<ref name=str/> When compressed at room temperature, this Bi-I structure changes first to the [[monoclinic]] Bi-II at 2.55 GPa, then to the [[tetragonal]] Bi-III at 2.7 GPa, and finally to the [[body-centered cubic]] Bi-IV at 7.7 GPa. The corresponding transitions can be monitored via changes in electrical conductivity; they are rather reproducible and abrupt, and are therefore used for calibration of high-pressure equipment.<ref>{{cite book|author=Boldyreva, Elena |title=High-Pressure Crystallography: From Fundamental Phenomena to Technological Applications|url=https://books.google.com/books?id=pyN0dhHChzsC&pg=PA264|date=2010| publisher= Springer| isbn=978-90-481-9257-1|pages=264–265}}</ref><ref>{{cite book|last=Manghnani | first= Murli H.|title=Science and Technology of High Pressure: Proceedings of the International Conference on High Pressure Science and Technology (AIRAPT-17) |location=Honolulu, Hawaii |date=25–30 July 1999|volume=2|url=https://books.google.com/books?id=7OoZ9TN8ROQC&pg=PA1086|publication-date=2000|publisher=Universities Press (India) | isbn=978-81-7371-339-2|page=1086}}</ref> === Chemical characteristics === Bismuth is stable to both dry and moist air at ordinary temperatures. When red-hot, it reacts with water to make bismuth(III) oxide.<ref name=s8/> : 2 Bi + 3 H₂O → Bi₂O₃ + 3 H₂ It reacts with [[fluorine]] to make [[bismuth(V) fluoride]] at 500&nbsp;°C or [[bismuth(III) fluoride]] at lower temperatures (typically from Bi melts); with other [[halogen]]s it yields only bismuth(III) halides.<ref name=w770>[[#Wiberg|Wiberg]], pp. 769–770.</ref><ref name=g559>[[#Greenwood|Greenwood]], pp. 559–561.</ref><ref name=k185/> The trihalides are corrosive and easily react with moisture, forming [[oxyhalides]] with the formula BiOX.<ref name=s9>[[#Suzuki|Suzuki]], p. 9.</ref> : 2 Bi + 3 X₂ → 2 BiX₃ (X = F, Cl, Br, I) Bismuth dissolves in concentrated [[sulfuric acid]] to make [[bismuth(III) sulfate]] and [[sulfur dioxide]].<ref name=s8>[[#Suzuki|Suzuki]], p. 8.</ref> : 6 H₂SO₄ + 2 Bi → 6 H₂O + Bi₂(SO₄)₃ + 3 SO₂ It reacts with [[nitric acid]] to make [[bismuth(III) nitrate]]. : Bi + 6 HNO₃ → 3 H₂O + 3 NO₂ + Bi(NO₃)₃ It also dissolves in [[hydrochloric acid]], but only with oxygen present.<ref name=s8/> : 4 Bi + 3 O₂ + 12 HCl → 4 BiCl₃ + 6 H₂O It is used as a [[Transmetalation|transmetalating]] agent in the synthesis of alkaline-earth metal complexes: : 3 Ba + 2 BiPh₃ → 3 BaPh₂ + 2 Bi === Isotopes === {{main|Isotopes of bismuth}} The only primordial [[isotope]] of bismuth, [[bismuth-209]], was traditionally regarded as the heaviest stable isotope, but it had long been suspected<ref>{{cite journal|doi = 10.1007/BF02824346|title = Alpha-activity of209Bi|date = 1972|last1 = Carvalho|first1 = H. G.|last2 = Penna|first2 = M.|journal = Lettere al Nuovo Cimento|volume = 3|issue = 18|page = 720}}</ref> to be unstable on theoretical grounds. This was finally demonstrated in 2003, when researchers at the Institut d'Astrophysique Spatiale in [[Orsay]], France, measured the [[Alpha decay|alpha emission]] [[half-life]] of {{SimpleNuclide2|Bismuth|209|link=yes}} to be {{val|1.9|e=19|u=years}},<ref>{{cite journal|last = Marcillac|first = Pierre de| author2 = Noël Coron| author3 = Gérard Dambier| author4 = Jacques Leblanc| author5 = Jean-Pierre Moalic| last-author-amp = yes|date=2003|title = Experimental detection of α-particles from the radioactive decay of natural bismuth|journal = Nature|volume = 422|pages = 876–878|pmid=12712201|doi = 10.1038/nature01541|issue = 6934| bibcode= 2003Natur.422..876D}}</ref> over a [[1000000000 (number)|billion]] times longer than the current estimated [[age of the universe]].<ref name=Kean /> Owing to its extraordinarily long half-life, for all presently known medical and industrial applications, bismuth can be treated as if it is stable and nonradioactive. The radioactivity is of academic interest because bismuth is one of a few elements whose radioactivity was suspected and theoretically predicted before being detected in the laboratory.<ref name=Kean /> Bismuth has the longest known alpha decay half-life, although [[Isotopes of tellurium|tellurium-128]] has a [[double beta decay]] half-life of over {{val|2.2|e=24|u=years}}.<ref name="NUBASE">{{cite journal| first = Audi| last = Georges|title = The NUBASE Evaluation of Nuclear and Decay Properties| journal = Nuclear Physics A| volume = 729| pages = 3–128| publisher = Atomic Mass Data Center| date = 2003| doi=10.1016/j.nuclphysa.2003.11.001| bibcode= 2003NuPhA.729....3A| last2 = Bersillon| first2 = O.| last3 = Blachot| first3 = J.| last4 = Wapstra| first4 = A. H.}}</ref> Bismuth's extremely long half life means that less than one billionth of the bismuth present at the formation of the planet Earth would have decayed into thallium since then. Several isotopes of bismuth with short half-lives occur within the radioactive disintegration chains of [[actinium]], [[radium]], and [[thorium]], and more have been synthesized experimentally. Bismuth-213 is also found on the decay chain of [[uranium-233]].<ref>{{cite book |url=https://books.google.com/books?id=ZAHJkrJlwbYC&pg=PA78|page =78 |title=Modern Nuclear Chemistry |isbn=978-0-471-11532-8 |last1= Loveland |first1=Walter D. |last2=Morrissey |first2=David J. |last3=Seaborg |first3=Glenn T. |date=2006}}</ref> Commercially, the radioactive isotope bismuth-213 can be produced by bombarding [[radium]] with [[bremsstrahlung]] photons from a [[linear particle accelerator]]. In 1997, an antibody conjugate with bismuth-213, which has a 45-minute half-life and decays with the emission of an alpha particle, was used to treat patients with leukemia. This isotope has also been tried in cancer treatment, for example, in the targeted alpha therapy (TAT) program.<ref>{{cite journal|doi=10.1016/S0360-3016(01)01585-1| title=Advancements in cancer therapy with alpha-emitters: a review|date=2001| last1=Imam|first1=S.| journal=International Journal of Radiation Oncology Biology Physics|volume=51|page=271}}</ref><ref>{{cite book |url=https://books.google.com/books?id=Y6haWM6lFkYC&pg=PT520|page =520 |title=Issues in Cancer Epidemiology and Research |date= 2011 |isbn=978-1-4649-6352-0 |last= Acton | first= Ashton}}</ref> == Chemical compounds == {{category see also|Bismuth compounds}} 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. === Oxides and sulfides === At elevated temperatures, the vapors of the metal combine rapidly with oxygen, forming the yellow trioxide, [[Bismuth(III) oxide|{{chem|Bi|2|O|3}}]].<ref name="w768"/><ref name=g553>[[#Greenwood|Greenwood]], p. 553.</ref> When molten, at temperatures above 710&nbsp;°C, this oxide corrodes any metal oxide, and even platinum.<ref name=k185>[[#Kruger|Krüger]], p. 185</ref> On reaction with base, it forms two series of [[oxyanion]]s: {{chem|BiO|2|-}}, which is polymeric and forms linear chains, and {{chem|BiO|3|3-}}. The anion in {{chem|Li|3|BiO|3}} is actually a cubic octameric anion, {{chem|Bi|8|O|24|24-}}, whereas the anion in {{chem|Na|3|BiO|3}} is tetrameric.<ref name="norman1" /> The dark red bismuth(V) oxide, {{chem|Bi|2|O|5}}, is unstable, liberating [[oxygen|{{chem|O|2}}]] gas upon heating.<ref>{{cite book | title = Concise encyclopedia chemistry | first1 = Thomas|last1 = Scott | first2 = Mary|last2 = Eagleson | publisher = Walter de Gruyter | date = 1994 | isbn = 3-11-011451-8 | page = 136 }}</ref> The compound [[sodium bismuthate|NaBiO₃]] is a strong oxidising agent.<ref name=g578>[[#Greenwood|Greenwood]], p. 578.</ref> Bismuth sulfide, [[Bismuth(III) sulfide|{{chem|Bi|2|S|3}}]], occurs naturally in bismuth ores.<ref>{{cite book|title=An Introduction to the Study of Chemistry|url=https://books.google.com/books?id=lGjTyw9gYfYC&pg=PA363|publisher=Forgotten Books|isbn=978-1-4400-5235-4|page=363}}</ref> It is also produced by the combination of molten bismuth and sulfur.<ref name="g559"/> [[File:MatlockiteStructure.png|thumb|Bismuth oxychloride (BiOCl) structure (mineral [[bismoclite]]). Bismuth atoms 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).<ref name=k184/> === Bismuthine and bismuthides === Unlike the lighter [[pnictogen]]s nitrogen, phosphorus, and arsenic, but similar to [[antimony]], bismuth does not form a stable [[hydride]]. Bismuth hydride, [[bismuthine]] ({{chem|BiH|3}}), is an [[endothermic]] compound that spontaneously decomposes at room temperature. It is stable only below −60&nbsp;°C.<ref name="norman1">{{cite book | title = Chemistry of arsenic, antimony, and bismuth | first1 = S. M. |last1 =Godfrey | first2 = C. A. |last2 =McAuliffe | first3 = A. G. |last3 =Mackie | first4 = R. G. |last4 =Pritchard | editor = Nicholas C. Norman | publisher = Springer | date = 1998 | isbn = 0-7514-0389-X | pages = 67–84 }}</ref> Bismuthides are [[intermetallic]] compounds between bismuth and other metals. 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 fermion]]s in bulk. It is a natural, three-dimensional counterpart to [[graphene]] with similar [[electron mobility]] and velocity. Graphene and [[topological insulator]]s (such as those in 3DTDS) are both crystalline materials that are electrically insulating inside but conducting on the surface, allowing them to function as [[transistor]]s and other electronic devices. While sodium bismuthide ({{chem|Na|3|Bi}}) 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. <ref name=k1401>{{cite journal|url=http://www.kurzweilai.net/3d-counterpart-to-graphene-discovered |title=3D counterpart to graphene discovered [UPDATE]|date=20 January 2014|publisher=KurzweilAI |accessdate=28 January 2014}}</ref><ref>{{Cite journal | last1 = Liu | first1 = Z. K. | last2 = Zhou | first2 = B. | last3 = Zhang | first3 = Y. | last4 = Wang | first4 = Z. J. | last5 = Weng | first5 = H. M. | last6 = Prabhakaran | first6 = D. | last7 = Mo | first7 = S. K. | last8 = Shen | first8 = Z. X. | last9 = Fang | first9 = Z. | last10 = Dai | first10 = X. | last11 = Hussain | first11 = Z. | last12 = Chen | first12 = Y. L. | title = Discovery of a Three-Dimensional Topological Dirac Semimetal, Na₃Bi | doi = 10.1126/science.1245085 | journal = Science | year = 2014 |arxiv=1310.0391| pmid = 24436183| url=http://sciencepubs.org/content/343/6173/864.full.pdf | volume=343 | issue = 6173 | pages=864–7|bibcode = 2014Sci...343..864L }}</ref> === Halides === The [[halide]]s 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 Bi{{su|b=9|p=5+}} cations and BiCl{{su|b=5|p=2−}} and Bi{{su|b=2}}Cl{{su|b=8|p=2−}} anions.<ref name="norman1" /><ref name="gillespie1">{{cite book | title = Advances in Inorganic Chemistry and Radiochemistry | first1 = R. J. |last1 = Gillespie | first2 = J. |last2 = Passmore | editor = Emeléus, H. J. | editor2 = Sharp A. G. | publisher = Academic Press | date = 1975 | isbn = 0-12-023617-6 | pages = 77–78 }}</ref> The Bi{{su|b=9|p=5+}} cation has a distorted tricapped [[trigonal prism]]atic molecular geometry, and is also found in {{chem|Bi|10|Hf|3|Cl|18}}, which is prepared by reducing a mixture of [[hafnium(IV) chloride]] and [[bismuth chloride]] with elemental bismuth, having the structure {{chem|[Bi|+|] [Bi|9|5+|] [HfCl|6|2-|]|3}}.<ref name="norman1"/>{{rp|50}} Other polyatomic bismuth cations are also known, such as Bi{{su|b=8|p=2+}}, found in {{chem|Bi|8|(AlCl|4|)|2}}.<ref name="gillespie1" /> Bismuth also forms a low-valence bromide with the same structure as "BiCl". There is a ''true'' monoiodide, BiI, which contains chains of {{chem|Bi|4|I|4}} units. BiI decomposes upon heating to the triiodide, [[Bismuth(III) iodide|{{chem|BiI|3}}]], and elemental bismuth. A monobromide of the same structure also exists.<ref name="norman1" /> In oxidation state +3, bismuth forms trihalides with all of the halogens: [[bismuth trifluoride|{{chem|BiF|3}}]], [[bismuth(III) chloride|{{chem|BiCl|3}}]], [[bismuth tribromide|{{chem|BiBr|3}}]], and [[bismuth(III) iodide|{{chem|BiI|3}}]]. All of these except {{chem|BiF|3}} are [[hydrolyze]]d by water.<ref name="norman1" /> [[Bismuth(III) chloride]] reacts with [[hydrogen chloride]] in [[ether]] solution to produce the acid {{chem|HBiCl|4}}.<ref name=s8/> The oxidation state +5 is less frequently encountered. One such compound is [[bismuth pentafluoride|{{chem|BiF|5}}]], a powerful oxidizing and fluorinating agent. It is also a strong fluoride acceptor, reacting with [[xenon tetrafluoride]] to form the {{chem|XeF|3|+}} cation:<ref name=s8/> : {{chem|BiF|5}} + {{chem|XeF|4}} → {{chem|XeF|3|+|BiF|6|-}} === Aqueous species === In [[aqueous]] solution, the Bi{{su|p=3+}} ion is solvated to form the aqua ion {{chem|Bi(H|2|O)|8|3+}} in strongly acidic conditions.<ref name="Persson2010">{{cite journal|last1=Persson|first1=Ingmar|title=Hydrated metal ions in aqueous solution: How regular are their structures?|journal=Pure and Applied Chemistry|volume=82|issue=10|date=2010|pages=1901–1917|doi=10.1351/PAC-CON-09-10-22}}</ref> At pH > 0 polynuclear species exist, the most important of which is believed to be the octahedral complex [{{chem|Bi|6|O|4|(OH)|4}}]{{su|p=6+}}.<ref name="NäslundPersson2000">{{cite journal|last1=Näslund|first1=Jan|last2=Persson|first2=Ingmar|last3=Sandström|first3=Magnus|title=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|journal=Inorganic Chemistry|volume=39|issue=18|date=2000|pages=4012–4021|doi=10.1021/ic000022m}}</ref> == Occurrence and production == {{See also|List of countries by bismuth production}} [[File:Bismite.jpg|thumb|left|upright|[[Bismite]] mineral]] <!-- Deleted image removed: [[File:Bismuth (mined)2.PNG|thumb|upright=1.3|Bismuth output in 2005]] --> In the Earth's crust, bismuth is about [[Abundances of the elements (data page)|twice as abundant as gold]]. The most important [[ore]]s of bismuth are [[bismuthinite]] and [[bismite]].<ref name=CRC/> Native bismuth is known from Australia, Bolivia, and China.<ref name="arizona1">{{cite book|editor=Anthony, John W.|editor2=Bideaux, Richard A.|editor3=Bladh, Kenneth W.|editor4=Nichols, Monte C. |title=Handbook of Mineralogy |publisher=Mineralogical Society of America |place=Chantilly, VA, US |volume=I (Elements, Sulfides, Sulfosalts) |url=http://rruff.geo.arizona.edu/doclib/hom/bismuth.pdf |format=PDF |chapter=Bismuth |accessdate=5 December 2011 |isbn=0-9622097-0-8}}</ref><ref>[[#Kruger|Krüger]], pp. 172–173.</ref> According to the [[United States Geological Survey]], the world mining production of bismuth in 2014 was 13,600 tonnes, with the major contributions from China (7,600 tonnes), Vietnam (4,950 tonnes) and Mexico (948 tonnes).<ref name=usgs2016>{{cite web|url=http://minerals.usgs.gov/minerals/pubs/commodity/bismuth/mcs-2016-bismu.pdf|title=2016 USGS Minerals Yearbook: Bismuth|format = PDF| accessdate =1 July 2016|publisher = United States Geological Survey|last=Anderson|first= Schuyler C.}}</ref> The refinery production in 2010 was 16,000 tonnes, of which China produced 13,000, Mexico 850 and Belgium 800 tonnes.<ref name=usgs2010>{{cite web|url=http://minerals.usgs.gov/minerals/pubs/commodity/bismuth/myb1-2010-bismu.pdf|title=2010 USGS Minerals Yearbook: Bismuth|format = PDF| accessdate =9 September 2010|publisher = United States Geological Survey|last=Carlin|first= James F., Jr.}}</ref> The difference reflects bismuth's status as a byproduct of extraction of other metals such as lead, copper, tin, molybdenum and tungsten.<ref>[[#Kruger|Krüger]], p. 173.</ref> World bismuth production from refineries is a more complete and reliable statistic.<ref name="Oje"/><ref>{{cite journal |doi = 10.1016/0891-3919(57)90180-8 |title = The preparation of bismuth for use in a liquid-metal fuelled reactor |date = 1957 |last1 = Horsley |first1 = G. W. |journal = Journal of Nuclear Energy (1954) |volume = 6 |page = 41}}</ref><ref>{{cite journal |doi = 10.1134/S0020168511020166 |title = Pb distribution in multistep bismuth refining products |date = 2011 |last1 = Shevtsov |first1 = Yu. V. |last2 = Beizel’ |first2 = N. F. |journal = Inorganic Materials |volume = 47 |issue = 2 |page = 139}}</ref><!-- patent US 2955931 --> Bismuth travels in crude lead bullion (which can contain up to 10% bismuth) through several stages of refining, until it is removed by the [[Kroll-Betterton process]] which separates the impurities as slag, or the electrolytic [[Betts process]]. Bismuth will behave similarly with another of its major metals, copper.<ref name="Oje">{{cite journal |doi = 10.1007/BF03222821 |title = Bismuth—Production, properties, and applications |date = 1992 |last1 = Ojebuoboh |first1 = Funsho K. |journal = JOM |volume = 44 |issue = 4 |pages = 46–49|bibcode = 1992JOM....44d..46O}}</ref> The raw bismuth metal from both processes contains still considerable amounts of other metals, foremost lead. By reacting the molten mixture with chlorine gas the metals are converted to their chlorides while bismuth remains unchanged. Impurities can also be removed by various other methods for example with fluxes and treatments yielding high-purity bismuth metal (over 99% Bi). === Price === [[File:BiPrice.png|thumb|upright=1.3|World mine production and annual averages of bismuth price (New York, not adjusted for inflation).<ref name=usgs/>]] The price for pure bismuth metal has been relatively stable through most of the 20th century, except for a spike in the 1970s. Bismuth has always been produced mainly as a byproduct of lead refining, and thus the price usually reflected the cost of recovery and the balance between production and demand.<ref name=usgs/> Demand for bismuth was small prior to World War II and was pharmaceutical – bismuth compounds were used to treat such conditions as digestive disorders, [[sexually transmitted infection]]s and burns. Minor amounts of bismuth metal were consumed in fusible alloys for [[fire sprinkler]] systems and [[Fuse (electrical)|fuse wire]]. During World War II bismuth was considered a [[strategic material]], used for solders, fusible alloys, medications and atomic research. To stabilize the market, the producers set the price at $1.25 per pound (2.75 $/kg) during the war and at $2.25 per pound (4.96 $/kg) from 1950 until 1964.<ref name=usgs/> In the early 1970s, the price rose rapidly as a result of increasing demand for bismuth as a metallurgical additive to aluminium, iron and steel. This was followed by a decline owing to increased world production, stabilized consumption, and the recessions of 1980 and 1981–82. In 1984, the price began to climb as consumption increased worldwide, especially in the United States and Japan. In the early 1990s, research began on the evaluation of bismuth as a nontoxic replacement for lead in ceramic glazes, fishing sinkers, food-processing equipment, free-machining [[brass]]es for plumbing applications, lubricating greases, and shot for [[waterfowl hunting]].<ref name=s14>[[#Suzuki|Suzuki]], p. 14.</ref> Growth in these areas remained slow during the middle 1990s, in spite of the backing of lead replacement by the US Government, but intensified around 2005. This resulted in a rapid and continuing increase in price.<ref name=usgs>[http://minerals.usgs.gov/minerals/pubs/commodity/bismuth/ Bismuth Statistics and Information]. see "Metal Prices in the United States through 1998" for a price summary and "Historical Statistics for Mineral and Material Commodities in the United States" for production. USGS.</ref> === Recycling === Most bismuth is produced as a byproduct of other metal-extraction processes including the smelting of lead, and also of tungsten and copper. Its [[sustainability]] is dependent on increased recycling, which is problematic. It was once believed that bismuth could be practically recycled from the soldered joints in electronic equipment. Recent efficiencies in solder application in electronics mean there is substantially less solder deposited, and thus less to recycle. While recovering the silver from silver-bearing solder may remain economic, recovering bismuth is substantially less so.<ref>{{cite web|url = http://leadfree.ipc.org/files/RoHS_15.pdf|author = Warburg, N|publisher = University of Stuttgart|title = IKP, Department of Life-Cycle Engineering|accessdate = 5 May 2009|deadurl = yes|archiveurl = https://web.archive.org/web/20090225155540/http://leadfree.ipc.org/files/RoHS_15.pdf|archivedate = 25 February 2009|df = dmy-all}}</ref> Next in recycling feasibility would be sizeable catalysts with a fair bismuth content, such as bismuth phosphomolybdate.{{citation needed|date=March 2018}}, bismuth used in galvanizing, and as a free-machining metallurgical additive.{{citation needed|date=March 2018}} Bismuth in uses where it is dispersed most widely include certain stomach medicines ([[bismuth subsalicylate]]), paints ([[bismuth vanadate]]), [[pearlescent]] cosmetics ([[bismuth oxychloride]]), and bismuth-containing bullets. Recycling bismuth from these uses is impractical. == Applications == Bismuth has few commercial applications, and those applications that use it generally require small quantities relative to other raw materials. In the United States, for example, 884 tonnes of bismuth were consumed in 2010, of which 63% went into chemicals (including pharmaceuticals, pigments, and cosmetics); 26% into metallurgical additives for casting and galvanizing;<ref>{{cite journal|doi = 10.1016/j.matlet.2006.06.029|title = The effect of bismuth on the structure of zinc hot-dip galvanized coatings|date = 2007|last1 = Pistofidis|first1 = N.|last2 = Vourlias|first2 = G.|last3 = Konidaris|first3 = S.|last4 = Pavlidou|first4 = El.|last5 = Stergiou|first5 = A.|last6 = Stergioudis|first6 = G.|journal = Materials Letters|volume = 61|issue = 4–5|page = 994}}</ref> 7% into bismuth alloys, solders and ammunition; and 4% into research and other uses.<ref name=usgs2010/> Some manufacturers use bismuth as a substitute in equipment for potable water systems such as valves to meet "lead-free" mandates in the U.S. (began in 2014). This is a fairly large application since it covers all residential and commercial building construction. In the early 1990s, researchers began to evaluate bismuth as a nontoxic replacement for lead in various applications. === Medicines === Bismuth is an ingredient in some pharmaceuticals,<ref name=Kean /> although the use of some of these substances is declining.<ref name=k184/> * [[Bismuth subsalicylate]] is used as an [[diarrhea|antidiarrheal]];<ref name=Kean /> it is the [[active ingredient]] in such "Pink Bismuth" preparations as [[Pepto-Bismol]], as well as the 2004 reformulation of [[Kaopectate]]. It is also used to treat some other gastro-intestinal diseases and [[cadmium poisoning]].<ref name=Kean /> The mechanism of action of this substance is still not well documented, although an [[oligodynamic effect]] (toxic effect of small doses of heavy metal ions on microbes) may be involved in at least some cases. [[Salicylic acid]] from [[hydrolysis]] of the compound is antimicrobial for toxogenic ''E. coli,'' an important pathogen in [[traveler's diarrhea]].<ref>{{cite journal|author=Sox TE|author2= Olson CA|title=Binding and killing of bacteria by bismuth subsalicylate|journal =Antimicrob Agents Chemother|date= 1989|volume=33|issue=12|pages=2075–82|pmid=2694949|pmc=172824|doi=10.1128/AAC.33.12.2075}}</ref> * a combination of [[bismuth subsalicylate]] and [[bismuth subcitrate]] is used to treat the bacteria causing [[peptic ulcer]]s. * [[Bibrocathol]] is an organic bismuth-containing compound used to treat eye infections. * [[Bismuth subgallate]], the [[active ingredient]] in Devrom, is used as an internal deodorant to treat malodor from [[flatulence]] and [[feces]]. * Bismuth compounds (including [[sodium bismuth tartrate]]) were formerly used to treat syphilis<ref>{{cite journal|author=Parnell, R. J. G. |title=Bismuth in the Treatment of Syphilis|journal=Journal of the Royal Society of Medicine|date=1924|volume=17|pages=19–26|pmc=2201253|issue=War section|pmid=19984212}}</ref><ref>{{cite patent|country=USA|number=1540117|title=Manufacture of bismuth tartrates|inventor=Giemsa, Gustav }}</ref> * "Milk of bismuth" (an aqueous solution of [[bismuth hydroxide]] and [[bismuth subcarbonate]]) was marketed as an alimentary cure-all in the early 20th century * [[Bismuth subnitrate]] (Bi₅O(OH)₉(NO₃)₄) and [[bismuth subcarbonate]] (Bi₂O₂(CO₃)) are also used in medicine.<ref name=CRC/> === Cosmetics and pigments === [[Bismuth oxychloride]] (BiOCl) is sometimes used in cosmetics, as a pigment in paint for eye shadows, hair sprays and nail polishes.<ref name=Kean /><ref name=k184/><ref name="Effp">{{cite journal|doi = 10.1016/j.porgcoat.2005.07.003|title = Effect pigments—past, present and future|date = 2005|last1 = Maile|first1 = Frank J.|last2 = Pfaff|first2 = Gerhard|last3 = Reynders|first3 = Peter|journal = Progress in Organic Coatings|volume = 54|issue = 3|page = 150}}</ref><ref name="Paff">{{cite book|url = https://books.google.com/books?id=Q1Pc0aY-vg4C&pg=PA36| page = 36|title = Special effect pigments: Technical basics and applications|isbn = 978-3-86630-905-0|author1 = Pfaff|first1 = Gerhard|date = 2008|publisher=Vincentz Network GmbH}}</ref> This compound is found as the mineral bismoclite and in crystal form contains layers of atoms (see figure above) that refract light chromatically, resulting in an [[iridescent]] appearance similar to [[nacre]] of pearl. It was used as a cosmetic in [[ancient Egypt]] and in many places since. ''Bismuth white'' (also "Spanish white") can refer to either bismuth oxychloride or [[bismuth oxynitrate]] (BiONO₃), when used as a white pigment. Bismuth vanadate is used as a light-stable non-reactive paint pigment (particularly for artists' paints), often as a replacement for the more toxic cadmium sulfide yellow and orange-yellow pigments. The most common variety in artists' paints is a lemon yellow, visually indistinguishable from its cadmium-containing alternative. === Metal and alloys === Bismuth is used in metal alloys with other metals such as iron, to create alloys to go into automatic sprinkler systems for fires. It was also used to make [[bismuth bronze]] which was used in the Bronze Age. ==== Lead replacement ==== The density difference between lead (11.32&nbsp;g/cm³) and bismuth (9.78&nbsp;g/cm³) is small enough that for many [[ballistics]] and weighting applications, bismuth can substitute for [[lead]]. For example, it can replace lead as a dense material in [[fishing sinker]]s. It has been used as a replacement for lead in [[Shot (pellet)|shot]], bullets and [[less-lethal]] [[riot gun]] ammunition. The Netherlands, Denmark, England, Wales, the US, and many other countries now prohibit the use of lead shot for the hunting of wetland birds, as many birds are prone to [[lead poisoning]] owing to mistaken ingestion of lead (instead of small stones and grit) to aid digestion, or even prohibit the use of lead for all hunting, such as in the Netherlands. Bismuth-tin alloy shot is one alternative that provides similar ballistic performance to lead. (Another less expensive but also more poorly performing alternative is "steel" shot, which is actually soft iron.) Bismuth's lack of [[malleability]] does, however, make it unsuitable for use in expanding hunting bullets.{{Citation needed|reason=Reliable source needed for the whole paragraph|date=January 2015}} Bismuth, as a dense element of high atomic weight, is used in bismuth-impregnated [[latex shield]]s to shield from X-ray in medical examinations, such as [[X-ray computed tomography|CTs]], mostly as it is considered non-toxic.<ref>{{cite journal|author=Hopper KD|author2=King SH|author3=Lobell ME|author4=TenHave TR|author5=Weaver JS|title= The breast: inplane x-ray protection during diagnostic thoracic CT—shielding with bismuth radioprotective garments|pmid=9393547|date=1997|volume=205|issue=3|pages=853–8|journal=Radiology|doi=10.1148/radiology.205.3.9393547}}</ref> The [[European Union]]'s [[Restriction of Hazardous Substances Directive]] (RoHS) for reduction of lead has broadened bismuth's use in electronics as a component of low-melting point solders, as a replacement for traditional tin-lead solders.<ref name=usgs2010/> Its low toxicity will be especially important for solders to be used in food processing equipment and copper water pipes, although it can also be used in other applications including those in the automobile industry, in the EU for example.<ref name=lohse>{{cite web|first1 = Joachim |last1 = Lohse|first2 = Stéphanie |last2 = Zangl|first3=Rita|last3=Groß|first4=Carl-Otto|last4=Gensch|first5=Otmar|last5=Deubzer|url = http://ec.europa.eu/environment/waste/pdf/description_layout.pdf|format = PDF| accessdate =11 September 2009|title = Adaptation to Scientific and Technical Progress of Annex II Directive 2000/53/EC|publisher=European Commission|date=September 2007}}</ref> Bismuth has been evaluated as a replacement for lead in free-machining [[brass]]es for [[plumbing]] applications,<ref>{{cite journal|doi = 10.1016/j.matchar.2006.02.005|title = Compositional distributions in classical and lead-free brasses|date = 2006|last1 = La Fontaine|first1 = A.|last2 = Keast|first2 = V. J.|journal = Materials Characterization|volume = 57|issue = 4–5|page = 424}}</ref> although it does not equal the performance of leaded steels.<ref name=lohse/> ==== Other metal uses and specialty alloys ==== <!-- *The high diamagnetic susceptibility of bismuth is used for [[Magnetic levitation|diamagnetic levitation]].<ref>{{cite web|url=http://www.instructables.com/id/Magnetic-Levitation-Sculpture/ |title=Magnetic Levitation Sculpture |publisher=Instructables.com |date=30 August 2011 |accessdate=14 April 2012}}</ref> --><!-- Hardly a significant application --><!-- *Diamagnetic levitation with bismuth uses blocks of this metal as a shield to provide the levitation of very strong small magnets (typically neodymium, iron, boron compositions). The system must be very well adjusted including many times the action of external strong magnets. Practical examples of experiments can be found in the Internet under the clue "Bismuth Magnetic Levitation" --> Many bismuth [[alloy]]s have low [[melting point]]s and are found in specialty applications such as [[solder]]s. Many automatic sprinklers, electric fuses, and safety devices in fire detection and suppression systems contain the eutectic In19.1-Cd5.3-Pb22.6-Sn8.3-Bi44.7 alloy that melts at {{convert|47|C}}<ref name=CRC/> This is a convenient temperature since it is unlikely to be exceeded in normal living conditions. Low-melting alloys, such as Bi-Cd-Pb-Sn alloy which melts at 70&nbsp;°C, are also used in automotive and aviation industries. Before deforming a thin-walled metal part, it is filled with a melt or covered with a thin layer of the alloy to reduce the chance of breaking. Then the alloy is removed by submerging the part in boiling water.<ref name=k183>[[#Kruger|Krüger]], p. 183.</ref> Bismuth is used to make [[free-machining steel]]s and free-machining aluminium alloys for precision machining properties. It has similar effect to lead and improves the chip breaking during machining. The shrinking on solidification in lead and the expansion of bismuth compensate each other and therefore lead and bismuth are often used in similar quantities.<ref>{{cite book|url = https://books.google.com/books?id=Wl1azjcJblIC&pg=PA239|page = 239|title = Steels: Metallurgy and applications|isbn = 978-0-7506-3757-2|author1 = Llewellyn|first1 = D. T.|last2 = Hudd|first2 = Roger C.|date = 1998|publisher=Butterworth-Heinemann}}</ref><ref>{{cite book|url =https://books.google.com/books?id=Lskj5k3PSIcC&pg=PA41| page = 41|title =Aluminum and Aluminum Alloys|isbn =978-0-87170-496-2|author1 =Davis & Associates|last-author-amp =yes|first1 =J. R.|last2 =Handbook Committee|first2 =ASM International|date =1993}}</ref> Similarly, alloys containing comparable parts of bismuth and lead exhibit a very small change (on the order 0.01%) upon melting, solidification or aging. Such alloys are used in high-precision casting, e.g. in dentistry, to create models and molds.<ref name=k183/> Bismuth is also used as an alloying agent in production of malleable irons and as a [[thermocouple]] material.<ref name=CRC/><ref name=usgs2010/> Bismuth is also used in aluminium-silicon cast alloys in order to refine silicon morphology. However, it indicated a poisoning effect on modification of strontium (Sr).<ref>{{cite journal|last=Farahany|first=Saeed|author2=A. Ourdjini|author3=M.H. Idris|author4=L.T. Thai|title=Poisoning effect of bismuth on modification behavior of strontium in LM25 alloy|journal=Journal of Bulletin of Materials Science|date=2011|volume=34|issue=6|pages=1223–1231|doi=10.1007/s12034-011-0239-5}}</ref><ref>{{cite journal|last=Farahany|first=Saeed|author2=A. Ourdjini|author3=M. H. Idris|author4=L.T. Thai|title=Effect of bismuth on the microstructure of unmodified and Sr-modified Al-7%Si-0.4Mg alloy|journal=Journal of Transactions of Nonferrous Metals Society of China|date=2011|volume=21|issue=7|pages=1455–1464|doi=10.1016/S1003-6326(11)60881-9}}</ref> Some bismuth alloys, such as Bi35-Pb37-Sn25, are combined with non-sticking materials such as [[mica]], glass and [[Vitreous enamel|enamels]] because they easily wet them allowing to make joints to other parts. Addition of bismuth to caesium enhances the quantum yield of caesium cathodes.<ref name=k184>[[#Kruger|Krüger]], p. 184.</ref> [[Sintering]] of bismuth and manganese powders at 300&nbsp;°C produces a permanent magnet and [[magnetostrictive]] material, which is used in ultrasonic generators and receivers working in the 10–100&nbsp;kHz range and in magnetic memory devices.<ref name=s15>[[#Suzuki|Suzuki]], p. 15.</ref> === Other uses as compounds === [[File:Bismuthvanadat.jpg|thumb|right| 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.<ref>{{cite web|accessdate =19 January 2010|publisher = National High Magnetic Field Laboratory|title = BSCCO| url = http://www.magnet.fsu.edu/magnettechnology/research/asc/research/bscco.html}}</ref><!-- 9780199565917Oxford University Press, 2009Laszlo Solymar, Donald WalshElectrical Properties of Materials https://books.google.com/books?id=AiWyp0NQW6UC&pg=PA389 --> * [[Bismuth subnitrate]] is a component of [[ceramic glaze|glazes]] that produces an [[iridescence]] and is used as a pigment in paint. * [[Bismuth telluride]] is a semiconductor and an excellent [[thermoelectric effect|thermoelectric]] material.<ref name=k184/><ref>{{cite book |url = https://books.google.com/books?id=jO3nzAbzAWYC&pg=PA12|page = 12 |title = Recent trends in thermoelectric materials research |isbn = 978-0-12-752178-7 |author1 = Tritt |first1 = Terry M. |date = 2000|publisher=Academic Press}}</ref> Bi₂Te₃ diodes are used in mobile refrigerators, [[CPU]] coolers, and as detectors in [[infrared]] spectrophotometers.<ref name=k184/> * [[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 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 an vehicle paint pigment.<ref>{{cite journal|doi = 10.1016/j.dyepig.2005.08.027|title = The photochromic effect of bismuth vanadate pigments: Investigations on the photochromic mechanism|date = 2007|last1 = Tücks|first1 = Andreas|last2 = Beck|first2 = Horst P.|journal = Dyes and Pigments|volume = 72|issue = 2|page = 163}}</ref><ref>{{cite book|url = https://books.google.com/books?id=WZV_hX9u0yIC&pg=PA92|chapter = Yellow pigments|pages = 91–93|title = Coloring of plastics: Fundamentals, colorants, preparations|isbn = 978-1-56990-352-0|author = Müller, Albrecht|publisher=Hanser Verlag|date = 2003}}</ref> * A catalyst for making acrylic fibers.<ref name=CRC/> * As an [[electrocatalyst]] in the conversion of CO₂ to CO.<ref>{{Cite journal|title=Selective conversion of CO2 to CO with high efficiency using an bismuth-based electrocatalyst|author=DiMeglio, John L.|author2=Rosenthal, Joel |date=2013 |journal=Journal of the American Chemical Society|volume=135 |issue=24 |pages=8798–8801|doi=10.1021/ja4033549|pmid=23735115|pmc=3725765}}</ref> * Ingredient in [[lubrication|lubricating]] [[grease (lubricant)|greases]].<ref>{{cite book |url =https://books.google.com/books?id=YTa5TsL0KnIC&pg=PA430|page = 430 |title =Chemistry and Technology of Lubricants |isbn =978-1-4020-8661-8 |author1 =Mortier |first1 =Roy M. |last2 =Fox |first2 =Malcolm F. |last3 =Orszulik |first3 =Stefan T. |date =2010|publisher=Springer}}</ref> * In crackling microstars ([[dragon's eggs]]) in [[pyrotechnics]], as the [[Bismuth(III) oxide|oxide]], [[Bismuth subcarbonate|subcarbonate]] or subnitrate.<ref>{{cite journal|doi = 10.1016/j.atmosenv.2010.05.048|title = Emission factors and exposures from ground-level pyrotechnics|date = 2010|last1 = Croteau|first1 = Gerry|last2 = Dills|first2 = Russell|last3 = Beaudreau|first3 = Marc|last4 = Davis|first4 = Mac|journal = Atmospheric Environment|volume = 44|issue = 27|page = 3295|bibcode = 2010AtmEn..44.3295C }}</ref><ref>{{cite book|url = https://books.google.com/books?id=370UwG8CuNwC&pg=PA518|title = The Preparatory Manual of Black Powder and Pyrotechnics|isbn = 978-1-4116-8574-1|author1 = Ledgard|first1 = Jared|date = 2006|publisher=Lulu|pages=207, 319, 370, 518, search}}</ref> == Toxicology and ecotoxicology == :''See also [[bismuthia]], a rare dermatological condition that results from the prolonged use of bismuth.'' Scientific literature indicates that some of the compounds of bismuth are less toxic to humans via ingestion compared to other heavy metals (lead, arsenic, antimony, etc.)<ref name=Kean /> presumably due to the comparatively low solubility of bismuth salts.<ref name=":0" /> Its biological half-life for whole-body retention is reported to be 5 days but it can remain in the kidney for years in people treated with bismuth compounds.<ref name=Fowler>{{cite book |url = https://books.google.com/books?id=nKulgztuzL8C&pg=PA433| pages = 433 ff.|chapter=Bismuth|title = Handbook on the toxicology of metals|publisher=Academic Press |isbn = 978-0-12-369413-3 |author = Fowler, B.A. |author2 = Sexton M.J. |last-author-amp = yes |editor=Nordberg, Gunnar |date= 2007}}</ref> Bismuth poisoning can occur and has according to some reports been common in relatively recent times.<ref name=":0">{{Cite journal|last=DiPalma|first=Joseph R.|year=2001|title=Bismuth Toxicity, Often Mild, Can Result in Severe Poisonings|url=http://journals.lww.com/em-news/Fulltext/2001/04000/Bismuth_Toxicity,_Often_Mild,_Can_Result_in_Severe.12.aspx|journal=Emergency Medicine News|volume=23 |issue=3|pages=16|via=|doi=10.1097/00132981-200104000-00012}}</ref><ref name="Lenntech">[http://www.lenntech.com/periodic/elements/bi.htm Data on Bismuth's health and environmental effects]. Lenntech.com. Retrieved on 17 December 2011.</ref> As with lead, bismuth poisoning can result in the formation of a black deposit on the [[gingiva]], known as a [[bismuth line]].<ref name="biline">[http://medical-dictionary.thefreedictionary.com/bismuth+line "Bismuth line"] in ''TheFreeDictionary's Medical dictionary''. Farlex, Inc.</ref><ref>{{cite journal|doi = 10.1111/j.1365-2133.1973.tb01932.x|title = Drug induced changes in pigmentation|date = 1973|last1 = Levantine|first1 = Ashley|last2 = Almeyda|first2 = John|journal = British Journal of Dermatology|volume = 89|pages = 105–12|pmid = 4132858|issue = 1}}</ref><ref>[[#Kruger|Krüger]], pp. 187–188.</ref> Poisoning may be treated with [[dimercaprol]]; however, evidence for benefit is unclear.<ref name=WHO2008>{{cite book|title=WHO Model Formulary 2008|date=2009|publisher=World Health Organization|isbn=9789241547659|page=62|url=http://apps.who.int/medicinedocs/documents/s16879e/s16879e.pdf|accessdate= 8 December 2016}}</ref><ref name=AHFS2016>{{cite web|title=Dimercaprol|url=https://www.drugs.com/monograph/dimercaprol.html|publisher=The American Society of Health-System Pharmacists|accessdate= 8 December 2016}}</ref> Bismuth's environmental impacts are not well known; it may be less likely to bioaccumulate than some other heavy metals, and this is an area of active research.<ref>{{Cite journal|last=Boriova et al.|first=|year=2015|title=Bismuth(III) Volatilization and Immobilization by Filamentous Fungus Aspergillus clavatus During Aerobic Incubation|url=https://link.springer.com/article/10.1007/s00244-014-0096-5|journal=Archives of Environmental Contamination and Toxicology|volume=68 |issue=2|pages=405–411|via=|doi=10.1007/s00244-014-0096-5}}</ref><ref>{{Cite journal|last=Boriova et al.|first=|year=2013|title=Bioaccumulation and biosorption of bismuth Bi (III) by filamentous fungus Aspergillus clavatus|url=http://www.iaea.org/inis/collection/NCLCollectionStore/_Public/44/078/44078300.pdf|journal=Student Scientific Conference PriF UK 2013. Proceedings of reviewed contributions|volume=|pages=|via=https://inis.iaea.org/search/search.aspx?orig_q=RN:44078325}}</ref> == Bioremediation == The fungus ''[[Marasmius oreades]]'' can be used for the [[biological remediation]] of bismuth in polluted soils.<ref>{{cite journal|url=http://www.wseas.us/e-library/conferences/2010/Corfu/EDUCATION/EDUCATION-04.pdf|title=The Mycoremediation of Metals Polluted Soils Using Wild Growing Species of Mushrooms|journal=Engineering Education|author1=Carmen Cristina Elekes|author2=Gabriela busuioc|access-date=28 January 2014|archive-url=https://web.archive.org/web/20160303231241/http://www.wseas.us/e-library/conferences/2010/Corfu/EDUCATION/EDUCATION-04.pdf|archive-date=3 March 2016|dead-url=yes|df=dmy-all}}</ref> == See also == {{Wikipedia books|Bismuth}} * [[Lead-bismuth eutectic]] * [[List of countries by bismuth production]] * [[:Category:Bismuth minerals|Bismuth minerals]] * [[Patterns in nature]] == References == {{Reflist|30em}} == Bibliography == {{Source-attribution| Brown, R. D., Jr. "Annual Average Bismuth Price", USGS (1998)}} * {{cite book|ref=Greenwood|author=Greenwood, N. N.|author2=Earnshaw, A.|last-author-amp=yes |date=1997|title=Chemistry of the Elements|edition=2nd|place= Oxford|publisher= Butterworth-Heinemann|isbn=0-7506-3365-4}} * {{cite book|ref=Kruger|author=Krüger, Joachim|author2=Winkler, Peter|author3=Lüderitz, Eberhard|author4=Lück, Manfred|author5=Wolf, Hans Uwe|chapter=Bismuth, Bismuth Alloys, and Bismuth Compounds|title=Ullmann's Encyclopedia of Industrial Chemistry|date= 2003|publisher= Wiley-VCH, Weinheim|pages=171–189 |doi=10.1002/14356007.a04_171}} * {{cite book|ref=Suzuki|author=Suzuki, Hitomi |title=Organobismuth Chemistry|url=https://books.google.com/books?id=qODswAbaBmsC&pg=PA8|date=2001|publisher=Elsevier|isbn=978-0-444-20528-5|pages=1–20}} * {{cite book|ref=Wiberg | title = Inorganic chemistry | last1= Wiberg | first1=Egon| last2= Holleman | first2=A. F. |last3= Wiberg | first3=Nils | publisher = Academic Press | date = 2001 | isbn = 0-12-352651-5 }} == External links == {{Commons|Bismuth}} {{wiktionary|bismuth}} * [[:File:Bismuth-501g.jpg|Laboratory growth of large crystals of Bismuth]] by Jan Kihle Crystal Pulling Laboratories, Norway * [http://www.periodicvideos.com/videos/083.htm Bismuth] at ''[[The Periodic Table of Videos]]'' (University of Nottingham) * [http://physicsworld.com/cws/article/news/2003/apr/23/bismuth-breaks-half-life-record-for-alpha-decay Bismuth breaks half-life record for alpha decay] * [http://www.amazingrust.com/Experiments/how_to/Bismuth_Crystals.html Bismuth Crystals – Instructions & Pictures] {{clear}} {{Compact periodic table}} {{Bismuth compounds}} {{Use dmy dates|date=January 2015}} {{Good article}} {{Authority control}} [[Category:Bismuth| ]] [[Category:Chemical elements]] [[Category:Post-transition metals]] [[Category:Pnictogens]] [[Category:Trigonal minerals]] [[Category:Alchemical substances]] [[Category:Native element minerals]]'