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'''Francium''' ({{pronEng|ˈfrænsiəm}}), formerly known as '''[[caesium|eka-caesium]]''' and '''[[actinium|actinium K]]''',<ref>Actually the least unstable isotope, Fr-223</ref> is a [[chemical element]] that has the symbol '''Fr''' and [[atomic number]] 87. It has the lowest known [[electronegativity]] of all known elements, and is the [[Abundance of the chemical elements|second rarest]] naturally occurring element (after [[astatine]]). Francium is a highly [[Radioactive decay|radioactive]] metal that decays into astatine, [[radium]], and [[radon]]. As an [[alkali metal]], it has one [[valence electron]]. |
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Francium was discovered by [[Marguerite Perey]] in [[France]] (from which the element takes its name) in 1939. It was the last element discovered in [[nature]], rather than synthesized.<ref>Some synthetic elements, like [[technetium]], have later been found in nature.</ref> Outside the laboratory, francium is extremely rare, with trace amounts found in [[uranium]] and [[thorium]] ores, where the [[isotope]] francium-223 continually forms and decays. As little as 20-30 g (one ounce) exists at any given time throughout the [[Earth]]'s [[crust (geology)|crust]]; the other isotopes are entirely synthetic. The largest amount ever collected of any isotope was a cluster of 10,000 atoms (of francium-210) created as an [[Ultracold atom|ultracold]] gas at [[Stony Brook University|Stony Brook]] in 1997.<ref name="CRC2006">{{Citation |year =2006 |title = CRC Handbook of Chemistry and Physics |volume = 4 |pages = 12 |publisher = CRC |id = 0-8493-0474-1 }}</ref> |
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==Characteristics== |
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Francium is the least stable of the naturally occurring elements: its most stable isotope, francium-223, has a [[half-life]] of only 22 minutes. In contrast, [[astatine]], the second-least stable naturally occurring element, has a maximum<!--is the francium-223's 22 min half-life a maximum too?--> half-life of 8.5 hours.<ref name="andyscouse" /> All isotopes of francium decay into either astatine, radium, or radon.<ref name="andyscouse">{{cite web| last = Price| first = Andy| title = Francium| date = 2004-12-20| url = http://www.andyscouse.com/pages/francium.htm| accessdate = 2007-03-25 }}</ref> Francium is also less stable than all synthetic elements up to element [[dubnium|105]].<ref name="CRC2006" /> |
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Francium is an [[alkali metal]] whose chemical properties most resemble those of [[caesium]].<ref name="CRC2006" /> A very heavy element with a single [[valence electron]],<ref>{{cite web| last = Winter| first = Mark| title = Electron Configuration| work = Francium| publisher = The University of Sheffield| url = http://www.webelements.com/webelements/elements/text/Fr/eneg.html| accessdate = 2007-04-18 }}</ref> it has the highest [[equivalent weight]] of any element.<ref name="CRC2006" /> Similarly, francium has the lowest [[electronegativity]] of all the known elements at 0.7 on the [[Pauling scale]];<ref>{{cite book| last = Pauling| first = Linus| title = The Nature of the Chemical Bond (3rd Edn.)| authorlink = Linus Pauling| publisher = Cornell University Press| year = 1960| pages = 93 }}</ref> [[caesium]] has the second-lowest at 0.79.<ref>{{cite web| last = Winter| first = Mark| title = Electronegativies| work = Caesium| publisher = The University of Sheffield| url = http://www.webelements.com/webelements/elements/text/Cs/eneg.html| accessdate = 2007-05-09 }} Pauling places caesium and francium with the same electronegativity.</ref> Liquid francium — if such a substance were to be created — should have a [[surface tension]] of 0.05092 [[newton|N]]/[[metre|m]] at its melting point.<ref>{{cite journal| last = Kozhitov| first = L. V.| coauthors = Kol'tsov, V. B., and Kol'tsov, A. V.| title = Evaluation of the Surface Tension of Liquid Francium| journal = Inorganic Materials| volume = 39| issue = 11| pages = 1138–1141| publisher = Springer Science & Business Media B.V.| date = 2003-02-21| url = http://search.ebscohost.com/login.aspx?direct=true&db=aqh&AN=16822434&site=ehost-live| accessdate = 2007-04-14| doi = 10.1023/A:1027389223381 }}</ref> |
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Francium [[coprecipitation|coprecipitates]] with several caesium [[salt]]s, such as [[caesium perchlorate]], which results in small amounts of francium perchlorate. This coprecipitation can be used to isolate francium, by adapting the radiocaesium coprecipitation method of [[L. E. Glendenin|Glendenin]] and [[C. M. Nelson|Nelson]]. It will additionally coprecipitate with many other caesium salts, including the [[iodate]], the [[picrate]], the [[tartrate]] (also [[rubidium]] tartrate), the [[chloroplatinate]], and the [[silicotungstate]]. It also coprecipitates with [[silicotungstic acid]], and with [[perchloric acid]], without another alkali metal as a [[carrier (chemistry)|carrier]], which provides other methods of separation.<ref>{{cite journal |last= Hyde |first= E. K. |title= Radiochemical Methods for the Isolation of Element 87 (Francium) |journal= [[J. Am. Chem. Soc.]] |year= 1952 |volume= 74 |issue= 16 |pages= 4181–4184 |doi= 10.1021/ja01136a066 }}</ref><ref>E. N K. Hyde ''Radiochemistry of Francium'',Subcommittee on Radiochemistry, National Academy of Sciences-National Research Council; available from the Office of Technical Services, Dept. of Commerce, 1960.</ref> Nearly all francium salts are [[solubility|water-soluble]].<ref>A. G. Maddock. Radioactivity of the heavy elements. ''Q. Rev., Chem. Soc.'', '''1951''', ''3'', 270–314. {{doi|10.1039/QR9510500270}}</ref> |
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==Applications== |
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Due to its instability and rarity<ref>{{cite web| last = Winter| first = Mark| title = Uses| work = Francium| publisher = The University of Sheffield| url = http://www.webelements.com/webelements/elements/text/Fr/uses.html| accessdate = 2007-03-25 }}</ref><ref name="s">{{cite web| last = Bentor| first = Yinon| title = Chemical Element.com - Francium| url = http://www.chemicalelements.com/elements/fr.html| accessdate = 2007-03-25 }}</ref><ref name="nbb">{{cite book| last = Emsley| first = John| title = Nature's Building Blocks| publisher = Oxford University Press| year = 2001| location = Oxford| pages = 151–153| isbn = 0-19-850341-5 }}</ref><ref name="elemental">{{cite web| last = Gagnon| first = Steve| title = Francium| publisher = Jefferson Science Associates, LLC| url = http://education.jlab.org/itselemental/ele087.html| accessdate = 2007-04-01 }}</ref><ref name="nostrand332" /> there are no commercial applications for francium. It has been used for research purposes in the fields of [[biology]] and of [[atom|atomic structure]]. Its use as a potential diagnostic aid for various [[cancer]]s has also been explored,<ref name="andyscouse" /> but this application has been deemed impractical.<ref name="nbb" /> |
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Francium's ability to be synthesized, trapped, and cooled, along with its relatively simple [[atom|atomic structure]] have made it the subject of specialized [[spectroscopy]] experiments. These experiments have led to more specific information regarding [[energy level]]s and the [[coupling constant]]s between [[subatomic particle]]s.<ref>{{cite journal| last = Gomez| first = E| coauthors = Orozco, L A, and Sprouse, G D| title = Spectroscopy with trapped francium: advances and perspectives for weak interaction studies| journal = Rep. Prog. Phys.| volume = 69| issue = 1| pages = 79–118| date = 2005-11-07| url = http://www.iop.org/EJ/abstract/0034-4885/69/1/R02/| doi = 10.1088/0034-4885/69/1/R02| accessdate = 2007-04-11 }}</ref> Studies on the light emitted by laser-trapped francium-210 ions have provided accurate data on transitions between atomic energy levels which are fairly similar to those predicted by [[quantum mechanics|quantum theory]].<ref>{{cite news| last = Peterson| first = I| title = Creating, cooling, trapping francium atoms| pages = 294| publisher = Science News| date = 1996-05-11| url = http://search.ebscohost.com/login.aspx?direct=true&db=ulh&AN=9605167788&site=src-live| accessdate = 2007-04-11 }}</ref> |
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==History== |
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As early as 1870, chemists thought that there should be an alkali metal beyond [[caesium]], with an atomic number of 87.<ref name="andyscouse" /> It was then referred to by the provisional name ''[[Mendeleev's predicted elements|eka-caesium]]''.<ref name="chemeducator">Adloff, Jean-Pierre; Kaufman, George B. ([[2005]]-[[09-25]]). [http://chemeducator.org/sbibs/s0010005/spapers/1050387gk.htm Francium (Atomic Number 87), the Last Discovered Natural Element]. ''The Chemical Educator'' '''10''' (5). Retrieved on [[2007]]-[[03-26]].</ref> Research teams attempted to locate and isolate this missing element, and at least four false claims were made that the element had been found before an authentic discovery was made. |
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===Erroneous and incomplete discoveries=== |
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Russian chemist [[D. K. Dobroserdov]] was the first scientist to claim to have found eka-caesium, or francium. In 1925, he observed weak radioactivity in a sample of [[potassium]], another alkali metal, and concluded that eka-caesium was contaminating the sample.<ref name="fontani">{{cite conference| first = Marco| last = Fontani| title = The Twilight of the Naturally-Occurring Elements: Moldavium (Ml), Sequanium (Sq) and Dor (Do)| booktitle = International Conference on the History of Chemistry| pages = 1–8| date = 2005-09-10| location = Lisbon| url = http://5ichc-portugal.ulusofona.pt/uploads/PaperLong-MarcoFontani.doc| archiveurl = http://web.archive.org/web/20060224090117/http://5ichc-portugal.ulusofona.pt/uploads/PaperLong-MarcoFontani.doc| archivedate=2006-02-24| accessdate = 2007-04-08 }}</ref> He then published a thesis on his predictions of the properties of eka-caesium, in which he named the element ''russium'' after his home country.<ref name="vanderkroft">{{cite web| last = Van der Krogt| first = Peter| title = Francium| work = Elementymology & Elements Multidict| date = 2006-01-10| url = http://www.vanderkroft.net/elements/elem/fr.html| accessdate = 2007-04-08 }}</ref> Shortly thereafter, Dobroserdov began to focus on his teaching career at the Polytechnic Institute of Odessa, and he did not pursue the element further.<ref name="fontani"/> |
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The following year, [[England|English]] chemists [[Gerald J. F. Druce]] and [[Frederick H. Loring]] analyzed [[X-ray]] photographs of [[manganese(II) sulfate]].<ref name="vanderkroft"/> They observed spectral lines which they presumed to be of eka-caesium. They announced their discovery of element 87 and proposed the name ''alkalinium'', as it would be the heaviest alkali metal.<ref name="fontani"/> |
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In 1930, [[Fred Allison]] of the [[Alabama Polytechnic Institute]] claimed to have discovered element 87 when analyzing [[pollucite]] and [[lepidolite]] using his [[magneto-optic effect|magneto-optical]] machine. Allison requested that it be named ''virginium'' after his home state of [[Virginia]], along with the symbols Vi and Vm<!--along with them how? and proposed the symbols Vi and Vm?-->.<ref name="vanderkroft"/><ref>{{cite news| title = Alabamine & Virginium| publisher = TIME| date = 1932-02-15| url = http://www.time.com/time/magazine/article/0,9171,743159,00.html| accessdate = 2007-04-01 }}</ref> In 1934, however, H.G. MacPherson of [[University of California, Berkeley|UC Berkeley]] disproved the effectiveness of Allison's device and the validity of this false discovery.<ref>{{cite journal| last = MacPherson| first = H. G.| title = An Investigation of the Magneto-Optic Method of Chemical Analysis| journal = Physical Review| volume = 47| issue = 4| pages = 310–315| publisher = American Physical Society| date = 1934-12-21| url = http://prola.aps.org/abstract/PR/v47/i4/p310_1| doi = 10.1103/PhysRev.47.310| accessdate = 2007-04-08 }}</ref> |
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In 1936, Romanian chemist [[Horia Hulubei]] and his French colleague [[Yvette Cauchois]] also analyzed pollucite, this time using their high-resolution X-ray apparatus.<ref name="fontani"/> They observed several weak emission lines, which they presumed to be those of element 87. Hulubei and Cauchois reported their discovery and proposed the name ''moldavium'', along with the symbol Ml, after [[Moldavia]], the Romanian province where they conducted their work.<ref name="vanderkroft"/> In 1937, Hulubei's work was criticized by American physicist [[F. H. Hirsh Jr.]], who rejected Hulubei's research methods. Hirsh was certain that eka-caesium would not be found in nature, and that Hulubei had instead observed [[mercury (element)|mercury]] or [[bismuth]] X-ray lines. Hulubei, however, insisted that his X-ray apparatus and methods were too accurate to make such a mistake. Because of this, [[Jean Baptiste Perrin]], [[Nobel Prize]] winner and Hulubei's mentor, endorsed moldavium as the true eka-caesium over [[Marguerite Perey]]'s recently discovered francium. Perey, however, continuously criticized Hulubei's work until she was credited as the sole discoverer of element 87.<ref name="fontani"/> |
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===Perey's analysis=== |
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Eka-caesium was discovered in 1939 by [[Marguerite Perey]] of the [[Curie Institute (Paris)|Curie Institute]] in [[Paris, France]] when she purified a sample of [[actinium]]-227 which had been reported to have a decay energy of 220 keV. However, Perey noticed decay particles with an energy level below 80 keV. Perey thought this decay activity might have been caused by a previously unidentified decay product, one which was separated during purification, but emerged again out of the pure actinium-227. Various tests eliminated the possibility of the unknown element being [[thorium]], radium, [[lead]], bismuth, or [[thallium]]. The new product exhibited chemical properties of an alkali metal (such as coprecipitating with caesium salts), which led Perey to believe that it was element 87, caused by the [[alpha decay]] of actinium-227.<ref name="chemeducator" /> Perey then attempted to determine the proportion of [[beta decay]] to alpha decay in actinium-227. Her first test put the alpha branching at 0.6%, a figure which she later revised to 1%.<ref name="mcgraw" /> |
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Perey named the new isotope ''actinium-K'' (now referred to as francium-223)<ref name="chemeducator" /> and in 1946, she proposed the name ''catium'' for her newly discovered element, as she believed it to be the most [[electronegativity|electropositive]] [[cation]] of the elements. [[Irène Joliot-Curie]], one of Perey's supervisors, opposed the name due to its connotation of ''cat'' rather than ''cation''.<ref name="chemeducator"/> Perey then suggested ''francium'', after France. This name was officially adopted by the [[International Union of Pure and Applied Chemistry]] in 1949,<ref name="andyscouse" /> becoming the second element after [[gallium]] to be named after France. It was assigned the symbol Fa, but this abbreviation was revised to the current Fr shortly thereafter.<ref name="hackh">{{Citation| last = Grant| first = Julius| contribution = Francium| year = 1969| title = Hackh's Chemical Dictionary| pages = 279–280| publisher = McGraw-Hill }}</ref> Francium was the last element discovered in nature, rather than synthesized, following [[rhenium]] in 1925.<ref name="chemeducator" /> Further research into francium's structure was carried out by, among others, [[Sylvain Lieberman]] and his team at [[CERN]] in the 1970s and 1980s.<ref>{{cite web |
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| title = History |
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| work = Francium |
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| publisher = [[State University of New York at Stony Brook|SUNY Stony Brook]] Physics & Astronomy |
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| date = 2007-02-20 |
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| url = http://fr.physics.sunysb.edu/francium_news/history.HTM |
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| accessdate = 2007-03-26 }}</ref> |
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==Occurrence== |
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===Natural=== |
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Francium-223 is the result of the alpha decay of actinium-227 and can be found in trace amounts in [[uranium]] and [[thorium]] [[mineral]]s.<ref name="CRC2006" /> In a given sample of uranium, there is estimated to be only one francium atom for every 1×10<sup>18</sup> uranium atoms.<ref name="nbb" /> It is also calculated that there is at most 30 [[Gram|g]] of francium in the [[Crust (geology)|earth's crust]] at any time.<ref>{{cite web |
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| last = Winter |
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| first = Mark |
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| title = Geological information |
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| work = Francium |
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| publisher = The University of Sheffield |
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| url = http://www.webelements.com/webelements/elements/text/Fr/geol.html |
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| accessdate = 2007-03-26 }}</ref> This makes it the second [[Abundance of the chemical elements|rarest element]] in the crust after [[astatine]].<ref name="andyscouse" /><ref name="nbb" /> |
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===Synthesized=== |
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[[Image:franciumtrap.PNG|thumb|upright|In the MOT, a magnetic field is created by the copper solenoids. Neutral francium atoms enter the glass bulb from the left and are trapped by lasers.<ref name="sbtrapping" />]] |
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Francium can be synthesized in the nuclear reaction <sup>197</sup>Au + <sup>18</sup>O → <sup>210</sup>Fr + 5n. This process, developed by [[State University of New York at Stony Brook|Stony Brook]] Physics, yields francium isotopes with masses of 209, 210, and 211,<ref name="sbproduction">{{cite web| title = Production of Francium| work = Francium| publisher = [[State University of New York at Stony Brook|SUNY Stony Brook]] Physics & Astronomy| date = 2007-02-20| url = http://fr.physics.sunysb.edu/francium_news/production.HTM| accessdate = 2007-03-26 }}</ref> which are then isolated by the [[Magneto-optic effect|magneto-optic trap]] (MOT).<ref name="sbtrapping">{{cite web| title = Cooling and Trapping| work = Francium| publisher = [[State University of New York at Stony Brook|SUNY Stony Brook]] Physics & Astronomy| date = 2007-02-20| url = http://fr.physics.sunysb.edu/francium_news/trapping.HTM| accessdate = 2007-05-01 }}</ref> Other synthesis methods include bombarding radium with neutrons, and bombarding thorium with protons, [[deuterium|deuterons]], or [[helium]] [[ion]]s.<ref name="mcgraw">{{Citation| contribution = Francium| year = 2002| title = [[McGraw-Hill Encyclopedia of Science & Technology]]| volume = 7| pages = 493–494| publisher = McGraw-Hill Professional| isbn = 0-07-913665-6 }}</ref> Francium has not yet, [[as of 2008]], been synthesized in amounts large enough to weigh.<ref name="CRC2006" /><ref name="andyscouse" /><ref name="nbb" /><ref name="losalamos">{{cite web| title = Francium| publisher = [http://www.lanl.gov/ Los Alamos National Laboratory] Chemistry Division| date = 2003-12-15| url = http://periodic.lanl.gov/elements/87.html| accessdate = 2007-03-29 }}</ref> |
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==Isotopes== |
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{{main|Isotopes of francium}} |
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There are 34 known isotopes of francium ranging in [[atomic mass]] from 199 to 232.<ref name="CRC2006">{{Citation |year = 2006 |title = CRC Handbook of Chemistry and Physics |editor-last = Lide |editor-first = David R. |volume = 11 |pages = 180–181 |publisher = CRC |id = 0-8493-0487-3 }}</ref> Francium has seven [[metastability|metastable]] [[nuclear isomer]]s.<ref name="CRC2006" /> Francium-223 and francium-221 are the only isotopes that occur in nature, though the former is far more common.<ref name="nostrand679">{{Citation |contribution = Francium |year = 2005| title = Van Nostrand's Encyclopedia of Chemistry| editor-last = Considine| editor-first = Glenn D.| pages = 679| place= New York| publisher = Wylie-Interscience| isbn = 0-471-61525-0 }}</ref> |
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Francium-223 is the most stable isotope with a half-life of 21.8 minutes,<ref name="CRC2006" /> and it is highly unlikely that an isotope of francium with a longer half-life will ever be discovered or synthesized.<ref name="mcgraw" /> Francium-223 is the fifth product of the [[actinium]] decay series as the daughter isotope of actinium-227.<ref name="nostrand332">{{Citation |contribution = Chemical Elements |year = 2005| title = Van Nostrand's Encyclopedia of Chemistry| editor-last = Considine| editor-first = Glenn D.| pages = 332| place= New York| publisher = Wylie-Interscience| isbn = 0-471-61525-0 }}</ref> Francium-223 then decays into radium-223 by [[beta decay]] (1149 keV [[decay energy]]), with a minor (0.006%) [[alpha decay]] path to astatine-219 (5.4 MeV decay energy).<ref>{{cite web |author=National Nuclear Data Center |year=1990 |title=Table of Isotopes decay data |url=http://ie.lbl.gov/toi/nuclide.asp?iZA=870223 |publisher=[[Brookhaven National Laboratory]] |accessdate=2007-04-04}}.</ref> |
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Francium-221 has a half-life of 4.8 minutes.<ref name="CRC2006" /> It is the ninth product of the [[neptunium]] decay series as a daughter isotope of actinium-225.<ref name="nostrand332" /> Francium-221 then decays into astatine-217 by alpha decay (6.457 MeV decay energy).<ref name="CRC2006" /> |
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The least stable [[ground state]] isotope is francium-215, with a half-life of 0.12 μs. (9.54 MeV alpha decay to astatine-211):<ref name="CRC2006" /> Its [[metastable isomer]], francium-215m, is less stable still, with a half-life of only 3.5 ns.<ref name="NNDClist">{{cite web |author=National Nuclear Data Center |year=2003 |title=Fr Isotopes |url=http://ie.lbl.gov/education/parent/Fr_iso.htm |publisher=[[Brookhaven National Laboratory]] |accessdate=2007-04-04}}.</ref> |
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==See also== |
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{{alkalimetals}} |
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==Notes== |
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{{reflist|2}} |
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==External links== |
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{{Commons|Francium}} |
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{{wiktionary|francium}} |
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*[http://www.webelements.com/webelements/elements/text/Fr/index.html WebElements.com - Francium] |
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*[http://periodic.lanl.gov/elements/87.html Los Alamos National Laboratory - Francium] |
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*[http://fr.physics.sunysb.edu/francium_news/frconten.htm Stony Brook University Physics Dept.] |
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{{featured article}} |
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{{Compact periodic table}} |
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[[Category:Alkali metals]] |
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[[Category:Chemical elements]] |
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[[Category:Francium]] |
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