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{{about|the radioactive element|other meanings|Plutonium (disambiguation)}} |
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{{infobox plutonium}} |
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'''Plutonium''' ({{pronEng|pluːˈtoʊniəm}}, symbol '''Pu,''' [[atomic number]] 94) is a rare [[radioactive]], [[metal]]lic [[chemical element]]. The most significant [[isotope]] of plutonium is <sup>239</sup>Pu, with a [[half-life]] of 24,100 years; this isotope is [[fissile]] and is used in most modern [[nuclear weapon]]s. [[Plutonium-239]] can be synthesized from natural [[uranium]]. |
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The most stable isotope is <sup>244</sup>Pu, with a half-life of approximately 80 million years, long enough to be found in extremely small quantities in nature, making <sup>244</sup>Pu the most [[nucleon]]-rich <!--heaviest--> atom that naturally occurs in the [[Earth's crust]], albeit in small traces.<ref>{{Citation |
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| last =Levine |
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| first =Charles A. |
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| author-link = |
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| last2 =Glenn T. |
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| first2 =Seaborg, |
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| author2-link =Glenn T. Seaborg |
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| title =The Occurrence of Plutonium in Nature |
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| place= |
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| publisher =Radiation Laboratory, University of California |
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| year =1950 |
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| location =Berkeley, CA |
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| volume = |
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| edition = |
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| url =http://www.osti.gov/energycitations/product.biblio.jsp?osti_id=4429051 |
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| doi = |
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| id = }}</ref> |
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==Characteristics== |
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Plutonium has been called "the most complex metal" and "a physicist's dream but an engineer's nightmare"<ref>{{cite journal |title=Plutonium: An element at odds with itself |journal=Los Alamos Science |volume=26 |year=2000 |pages=16–23, on 16 |url=http://www.fas.org/sgp/othergov/doe/lanl/pubs/00818006.pdf |format=PDF |author=[[Siegfried S. Hecker]]}}</ref> for its peculiar physical and chemical properties. The element has six [[allotrope]]s normally and a seventh under pressure. The allotropes have very similar energy levels but significantly varying densities, making plutonium very sensitive to changes in temperature, pressure, or chemistry, and allowing for dramatic volume changes following phase transitions (in nuclear applications, it is usually [[alloy]]ed with a small amount of [[gallium]], which stabilizes it in the delta-phase).<ref name="HeckerPlutonium">{{cite journal |author=Siegfried S. Hecker |title=Plutonium and its alloys: from atoms to microstructure |journal=Los Alamos Science |volume=26 |year=2000 |pages=290–335 |url=http://www.fas.org/sgp/othergov/doe/lanl/pubs/00818035.pdf |format=PDF}}</ref> |
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Plutonium is silvery in pure form, but has a yellow tarnish when [[oxidation|oxidized]]. It possesses a low-symmetry structure, causing it to become progressively more brittle over time.<ref>{{cite web|title=Scientists resolve 60-year-old plutonium questions|url=http://www.llnl.gov/pao/news/news_releases/2006/NR-06-06-02.html|accessdate=2006-06-06|year=2006|author=Lawrence Livermore National Laboratory}}</ref> Because it self-irradiates, it ages both from the outside-in and the inside-out.<ref name="HeckerPlutonium" /> |
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However, self-irradiation can also lead to [[Annealing (metallurgy)|annealing]] which counteracts some of the aging effects. Overall, the precise aging properties of plutonium are very complex and poorly understood, greatly complicating efforts to predict future reliability of weapons components. |
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The heat given off by [[alpha decay|alpha particle emission]] can make plutonium warm to the touch in quantities of more than a few hundred grams, although this varies with the isotopic composition. |
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Plutonium displays five ionic [[oxidation state]]s in aqueous solution: |
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*Pu(III), as Pu<sup>3+</sup> (blue lavender) |
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*Pu(IV), as Pu<sup>4+</sup> (yellow brown) |
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*Pu(V), as PuO<sub>2</sub><sup>+</sup> (thought to be{{dubious}} pink; this ion is unstable in solution and will disproportionate into Pu<sup>4+</sup> and PuO<sub>2</sub><sup>2+</sup>; the Pu<sup>4+</sup> will then oxidize the remaining PuO<sub>2</sub><sup>+</sup> to PuO<sub>2</sub><sup>2+</sup>, being reduced in turn to Pu<sup>3+</sup>. Thus, aqueous solutions of plutonium tend over time towards a mixture of Pu<sup>3+</sup> and PuO<sub>2</sub><sup>2+</sup>.)<ref>{{cite web|title=Nuclear Criticality Safety Engineering Training Module 10 - Criticality Safety in Material Processing Operations, Part 1|url=http://ncsp.llnl.gov/ncset/Module10.pdf|format=PDF|accessdate=2006-02-15|year=2002|author=Crooks, William J.}}</ref> |
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*Pu(VI), as PuO<sub>2</sub><sup>2+</sup> (pink orange) |
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*Pu(VII), as PuO<sub>5</sub><sup>2-</sup> (dark red); the heptavalent ion is rare and prepared only under extreme oxidizing conditions. |
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The actual color shown by Pu solutions depends on both the oxidation state and the nature of the acid anion, which influences the degree of complexing of the Pu species by the acid anion.<ref>Matlack, George: A Plutonium Primer: An Introduction to Plutonium Chemistry and its Radioactivity (LA-UR-02-6594)</ref> |
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In both film and television shows, such as [[The Simpsons]], plutonium is often illustrated as a bright green luminous substance similar to [[Uranium glass]], or sometimes in liquid form. However, metallic plutonium normally resembles lead, and does not glow unless there is a significant amount of it decaying and emitting [[blackbody radiation]]. Even then the glow is bright orange rather than green. In powdered form it also emits light, as plutonium is naturally [[pyrophoric]] (that is, it can spontaneously ignite in air at or below room temperature). |
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==Applications== |
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The isotope <sup>239</sup>Pu is a key [[fissile]] component in [[nuclear weapon]]s, due to its ease of fissioning and availability. The [[critical mass (nuclear)|critical mass]] for an [[Nuclear weapon design#Tamper reflector|unreflected]] sphere of plutonium is 16 kg, but through the use of a [[neutron reflector|neutron-reflecting]] tamper the pit of plutonium in a fission bomb is reduced to 10 kg, which is a sphere with a diameter of 10 cm. The [[Manhattan Project]] "[[Fat Man]]" type plutonium bombs, using explosive compression of Pu to significantly higher densities than normal, were able to function with plutonium cores of only 6.2 kg.<ref>Much of the information about the plutonium in the [[Fat Man]] bomb comes from reports of the criticality accidents of [[Harry K. Daghlian, Jr.]] and [[Louis Slotin]], both of whom died after conducting experiments with plutonium bomb cores. See http://members.tripod.com/~Arnold_Dion/Daghlian/accident.html.</ref> Complete detonation may be achieved through the use of an additional neutron source (often from a small amount of fusion fuel). The [[Fat Man]] bomb had an explosive yield of 21 kilotons. (See also [[Nuclear weapon design#Enriched materials|nuclear weapon design]].) |
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The isotope [[plutonium-238]] (<sup>238</sup>Pu) has a half-life of 88 years and emits a large amount of [[thermal energy]] as it decays. Being an [[Alpha particle|alpha]] emitter, it combines high energy radiation with low penetration (thereby requiring minimal shielding). These characteristics make it well suited for electrical power generation for devices which must function without direct maintenance for timescales approximating a human lifetime. It is therefore used in [[radioisotope thermoelectric generators]] such as those powering the [[Cassini probe|Cassini]] and [[New Horizons|New Horizons (Pluto)]] space probes; earlier versions of the same technology powered the [[ALSEP]] and [[EASEP]] systems including [[seismology|seismic]] experiments on the [[Apollo program|Apollo]] [[Moon]] missions. |
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<sup>238</sup>Pu has been used successfully to power artificial heart [[Artificial pacemaker|pacemaker]]s, to reduce the risk of repeated surgery.<ref>{{cite web|url=http://www.theodoregray.com/periodictable/Elements/094/index.html |title=Theodore Gary's periodic table:Plutonium}}</ref> It has been largely replaced by [[lithium]]-based [[primary cell]]s, but as of 2003 there were somewhere between 50 and 100 plutonium-powered pacemakers still implanted and functioning in living patients.<ref>{{cite web|url=http://www.orau.org/PTP/collection/Miscellaneous/pacemaker.htm |title=Plutonium Powered Pacemaker (1974) |publisher=Orau.org |date= |accessdate=2008-09-12}}</ref> |
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==History== |
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[[Image:Seaborg Geiger Gilman Hall.jpg|thumb|left|200px|[[Glenn Seaborg]] at the Geiger Counter, 301 [[Gilman Hall]], Berkeley, California, where he discovered plutonium.]] |
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The production of plutonium and [[neptunium]] by bombarding [[uranium-238]] with neutrons was predicted in 1940 by two teams working independently: [[Edwin M. McMillan]] and [[Philip Abelson]] at [[Berkeley Radiation Laboratory]] at the [[University of California, Berkeley]]; and by [[Egon Bretscher]] and [[Norman Feather]] at the [[Cavendish Laboratory]] of the [[University of Cambridge]] for the [[Tube Alloys#Plutonium|Tube Alloys project]].{{Fact|date=February 2008}} Coincidentally both teams proposed the same names to follow on from uranium, following the sequence of the outer planets.{{Fact|date=February 2008}} |
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===First isolation=== |
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Plutonium was first produced and isolated on December 14, 1940, and chemically identified on February 23, 1941, by Dr. [[Glenn T. Seaborg]], [[Edwin McMillan|Edwin M. McMillan]], [[Joseph W. Kennedy|J. W. Kennedy]], [[Zachary M. Tatom|Z. M. Tatom]]<ref name='ACS'> {{cite web|url=http://acs.lbl.gov/Seaborg.talks/65th-anniv/14.html |title=Elements 93 and 94 |accessdate=2008-09-17 |publisher=Advanced Computing for Science Department }}</ref>, and [[Arthur Wahl|A. C. Wahl]] by [[deuteron]] bombardment of uranium in the {{convert|60|in|mm|sing=on}} cyclotron at Berkeley. The discovery was kept secret due to the [[World War II|war]]. It was named after [[Pluto]], having been discovered directly after [[neptunium]] (which itself was one higher on the periodic table than [[uranium]]), by analogy to solar system planet order as Pluto was considered to be a planet at the time (though Seaborg originally considered the name "plutium", he said that he did not think it sounded as good as "plutonium"<ref>{{cite journal |author=David L. Clark and David E. Hobart |title=Reflections on the Legacy of a Legend: Glenn T. Seaborg, 1912–1999 |journal=Los Alamos Science |volume=26 |year=2000 |pages=56–61, on 57 |url=http://www.fas.org/sgp/othergov/doe/lanl/pubs/00818011.pdf |format=PDF}}</ref>). Seaborg chose the letters "Pu" as a joke, which passed without notice into the periodic table.<ref>As one article puts it, referring to information Seaborg gave in a talk: "The obvious choice for the symbol would have been Pl, but facetiously, Seaborg suggested Pu, like the words a child would exclaim, 'Pee-yoo!' when smelling something bad. Seaborg thought that he would receive a great deal of flak over that suggestion, but the naming committee accepted the symbol without a word." {{cite journal |author=David L. Clark and David E. Hobart |title=Reflections on the Legacy of a Legend: Glenn T. Seaborg, 1912–1999 |journal=Los Alamos Science |volume=26 |year=2000 |pages=56–61, on 57 |url=http://www.fas.org/sgp/othergov/doe/lanl/pubs/00818011.pdf |format=PDF}}</ref> Originally, Seaborg and others thought about naming the element "ultinium" or "extremium" because they believed at the time that they had found the last possible [[chemical element|element]] on the [[periodic table]].<ref>[http://www.pbs.org/wgbh/pages/frontline/shows/reaction/interviews/seaborg.html Frontline interview with Seaborg]</ref> |
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Chemists at the [[University of Chicago]] began to study the newly manufactured radioactive element. The [[George Herbert Jones Laboratory]] at the university was the site where, on August 18, 1942, a trace quantity of this new element was isolated and measured for the first time. This procedure enabled chemists to determine the new element's atomic weight. Room 405 of the building was named a [[National Historic Landmark]] in May 1967.<ref name="uchicago">{{cite web | title=Room 405, George Herbert Jones Laboratory | publisher=National Park Service | url=http://tps.cr.nps.gov/nhl/detail.cfm?ResourceId=735&ResourceType=Building}}</ref> |
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During the Manhattan Project, plutonium was also often referred to as simply "49":. the number 4 was for the last digit in 94 (atomic number of plutonium), and 9 was for the last digit in Pu-239, the weapon-grade fissile isotope used in nuclear bombs. |
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<ref> |
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{{Cite journal |
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| last = Hammel |
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| first = E.F. |
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| date = 2000 |
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| title = The taming of "49" — Big Science in little time. Recollections of Edward F. Hammel, pp. 2-9. In: Cooper N.G. Ed. (2000). Challenges in Plutonium Science |
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| journal = Los Alamos Science |
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| volume = 26 |
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| issue = 1 |
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| pages = 2–9 |
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| url = http://www.fas.org/sgp/othergov/doe/lanl/pubs/00818010.pdf |
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}} |
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</ref><ref> |
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{{Cite journal |
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| last = Hecker |
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| first = S.S. |
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| date = 2000 |
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| title = Plutonium: an historical overview. In: Challenges in Plutonium Science |
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| journal = Los Alamos Science |
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| volume = 26 |
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| issue = 1 |
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| pages = 1–2 |
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| url = http://www.fas.org/sgp/othergov/doe/lanl/pubs/number26.htm |
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}} |
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</ref> |
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===Production=== |
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During the [[Manhattan Project]], the first production reactor, the [[X-10 Graphite Reactor]], was built at the [[Oak Ridge, Tennessee|Oak Ridge]], [[Tennessee]] site that became [[Oak Ridge National Laboratory]]. Later, large (200MW) [[nuclear reactor|reactors]] were set up at the [[Hanford Site]] (near [[Richland, Washington]]), for the production of plutonium, which was used in the first atomic bomb used at the [[Trinity test|"Trinity" test]] in July 1945. Plutonium was also used in the "[[Fat Man]]" bomb dropped on [[Nagasaki, Nagasaki|Nagasaki, Japan]] in August 1945. The "[[Little Boy]]" bomb dropped on [[Hiroshima]] used [[uranium-235]], not plutonium. |
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Large stockpiles of "weapons-grade" plutonium were built up by both the [[Soviet Union]] and the [[United States]] during the [[Cold War]]. The U.S. reactors at [[Hanford Site|Hanford]] and the [[Savannah River Site]] in South Carolina produced 103,000 kg;<ref>{{cite web|title=Plutonium: The first 50 years: United States plutonium production, acquisition, and utilization from 1944 to 1994| publisher=U.S. Department of Energy | url=http://www.fas.org/sgp/othergov/doe/pu50yb.html#ZZ13 | date= September 1994 }} </ref> It was estimated there were another 170,000 kg of military plutonium in Russia, with 300,000 kg accumulated worldwide.<ref>{{cite web | title=Safeguarding nuclear weapons-usable materials in Russia| url=http://docs.nrdc.org/nuclear/nuc_06129701a_185.pdf | author=Thomas B. Cochran (Natural Resources Defense Council) | publisher=Proceedings of the international forum on illegal nuclear traffic | date = 1997-06-12|accessdate=2007-06-16}}</ref> Since the end of the Cold War, these stockpiles have become a focus of [[nuclear proliferation]] concerns. In 2002, the [[United States Department of Energy]] took possession of 34 metric tons of excess weapons-grade plutonium stockpiles from the [[United States Department of Defense]], and as of early 2003 was considering converting several nuclear power plants in the US from [[enriched uranium]] fuel to [[MOX fuel]] as a means of disposing of plutonium stocks. |
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[[Image:Hanford Site 1945.jpg|thumb|left|350px|Hanford Site plutonium production reactors along the [[Columbia River]] during the [[Manhattan Project]].]] |
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===Medical experimentation=== |
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During the initial years after the discovery of plutonium, when its biological and physical properties were very poorly understood, a series of [[human radiation experiments]] were performed by the U.S. government and by private organizations acting on its behalf. During and after the end of World War II, scientists working on the [[Manhattan Project]] and other nuclear weapons research projects conducted studies of the effects of plutonium on laboratory animals and human subjects. In the case of human subjects, this involved injecting solutions containing (typically) five micrograms of plutonium into hospital patients thought to be either terminally ill, or to have a life expectancy of less than ten years either due to age or chronic disease condition. These eighteen injections were made without the [[informed consent]] of those patients and were not done with the belief that the injections would heal their conditions; rather, they were used to develop diagnostic tools for determining the uptake of plutonium in the body for use in developing safety standards for people working with plutonium during the course of developing nuclear weapons.<ref>{{cite journal |journal=Los Alamos Science|title=The Human Plutonium Injection Experiments|url=http://library.lanl.gov/cgi-bin/getfile?00326640.pdf|accessdate=2006-06-06|year=1995|author=William Moss and Roger Eckhardt |volume=23 |pages=177–233 |format=PDF}}</ref> |
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The episode is now considered to be a serious breach of medical ethics and of the [[Hippocratic Oath]], and has been sharply criticised as failing "both the test of our national values and the test of humanity."<ref>{{cite web|publisher=Bulletin of the Atomic Scientists|title=Injected! (Review of Eileen Welsome's ''The Plutonium Files'')|url=http://www.thebulletin.org/article.php?art_ofn=nd99longworthf|accessdate=2006-06-06|year=1999|author=R.C. Longworth}}</ref> More sympathetic commentators have noted that while it was definitely a breach in trust and ethics, "the effects of the plutonium injections were not as damaging to the subjects as the early news stories painted, nor were they so inconsequential as many scientists, then and now, believe."<ref>{{cite journal |author=Michael S. Yesley |title='Ethical Harm' and the Plutonium Injection Experiments |journal=Los Alamos Science |volume=23 |year=1995 |pages=280–283, on 283 |url=http://www.fas.org/sgp/othergov/doe/lanl/pubs/00326649.pdf |format=PDF}}</ref> |
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==Occurrence== |
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While almost all plutonium is manufactured synthetically, extremely tiny trace amounts are found naturally in [[uranium]] ores. These come about by a process of [[neutron capture]] by <sup>238</sup>U nuclei, initially forming <sup>239</sup>U; two subsequent [[beta decay]]s then form <sup>239</sup>Pu (with a <sup>239</sup>[[Neptunium|Np]] intermediary), which has a half-life of 24,110 years. This is also the process used to manufacture <sup>239</sup>Pu in [[nuclear reactor]]s. Some traces of <sup>244</sup>Pu remain{{Fact|date=January 2008}} from the birth of the solar system from the waste of supernovae, because its half-life of 80 million years is fairly long. |
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A relatively high concentration of plutonium was discovered at the [[natural nuclear fission reactor]] in [[Oklo]], [[Gabon]] in 1972. |
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===Manufacture===<!-- This section is linked from [[Radioactive waste]] --> |
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====Pu-240, Pu-241 and Pu-242==== |
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The activation [[Cross section (physics)|cross section]] for <sup>239</sup>Pu is 270 [[Barn (unit)|barns]], while the fission cross section is 747 barns for thermal neutrons. The higher plutonium isotopes are created when the uranium fuel is used for a long time. It is the case that for high burnup used fuel that the concentrations of the higher plutonium isotopes will be higher than the low burnup fuel which is reprocessed to obtain bomb grade plutonium. |
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{| class="wikitable" |
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|+ The formation of <sup>240</sup>Pu, <sup>241</sup>Pu and <sup>242</sup>Pu from <sup>238</sup>U |
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!rowspan="2"| Isotope !!colspan="2"|[[Thermal neutron]]<br>[[Cross section (physics)|cross section]] !!rowspan="2"| [[decay mode]] !! rowspan="2"|[[halflife]] |
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|- |
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! Capture !! Fission |
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|- |
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| [[uranium-238|<sup>238</sup>U]] || 2.7 || || α || 4.47 x 10<sup>9</sup> years |
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|- |
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| [[uranium-239|<sup>239</sup>U]] || || || β || 23 minutes |
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|- |
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| [[neptunium-239|<sup>239</sup>Np]] || || || β || 2.36 days |
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|- |
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| [[plutonium-239|<sup>239</sup>Pu]] || 270 || || α || 24,110 years |
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|- |
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| [[plutonium-240|<sup>240</sup>Pu]] || 289 || || α || 6,564 years |
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|- |
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| [[plutonium-241|<sup>241</sup>Pu]] || 362 || || β || 14.35 years |
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|- |
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| [[plutonium-242|<sup>242</sup>Pu]] || 18.8 || || α || 373,300 years |
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|} |
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====Pu-239==== |
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{{Main|Plutonium-239}} |
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Plutonium-239 is one of the three [[fissile]] materials used for the production of [[nuclear weapon]]s and in some [[nuclear reactor]]s as a source of energy. The other fissile materials are [[uranium-235]] and [[uranium-233]]. Plutonium-239 is virtually nonexistent in nature. It is made by bombarding [[uranium-238]] with neutrons in a nuclear reactor. Uranium-238 is present in quantity in most reactor fuel; hence plutonium-239 is continuously made in these reactors. Since plutonium-239 can itself be split by [[neutron]]s to release energy, plutonium-239 provides a portion of the energy generation in a nuclear reactor. |
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[[Image:Plutonium ring.jpg|right|300px|thumb|A ring of weapons-grade electrorefined plutonium, with 99.96% purity. This 5.3 kg ring is enough plutonium for use in an efficient nuclear weapon.]] |
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{| class="wikitable" |
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|+ The formation of <sup>239</sup>Pu from <sup>238</sup>U |
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! Element !! Isotope !! [[Thermal neutron]]<br>[[Cross section (physics)|cross section]] !! [[decay mode]] !! [[halflife]] |
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|- |
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! [[uranium|U]] |
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| 238 || 2.7 || α || 4.47 x 10<sup>9</sup> years |
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|- |
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! [[uranium|U]] |
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| 239 || - || β || 23 minutes |
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|- |
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! [[neptunium|Np]] |
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| 239 || - || β || 2.36 days |
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|- |
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! [[plutonium|Pu]] |
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| 239 || - || α || 24,110 years |
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|} |
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====Pu-238==== |
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{{Main|Plutonium-238}} |
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There are small amounts of Pu-238 in the plutonium of usual plutonium-producing reactors. However, isotopic separation would be quite expensive compared to another method: when a U-235 atom captures a neutron, it is converted to an excited state of U-236. Some of the excited U-236 nuclei undergo fission, but some decay to the ground state of U-236 by emitting gamma radiation. Further neutron capture creates U-237 which has a half-life of 7 days and thus quickly decays to [[Neptunium|Np]]-237. Since nearly all neptunium is produced in this way or consists of isotopes which decay quickly, one gets nearly pure Np-237 by chemical separation of neptunium. After this chemical separation, Np-237 is again irradiated by reactor neutrons to be converted to Np-238 which decays to Pu-238 with a half-life of 2 days. |
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{| class="wikitable" |
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|+ The formation of <sup>238</sup>Pu from <sup>235</sup>U |
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! Element !! Isotope !! [[Thermal neutron]]<br>[[Cross section (physics)|cross section]] !! [[decay mode]] !! [[halflife]] |
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|- |
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! [[uranium|U]] |
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| 235 || 99 || α || 703,800,000 years |
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|- |
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! [[uranium|U]] |
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| 236 || 5.3 || α || 23,420,000 years |
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|- |
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! [[uranium|U]] |
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| 237 || - || β || 6.75 days |
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|- |
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! [[neptunium|Np]] |
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| 237 || 165 (capture) || α || 2,144,000 years |
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|- |
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! [[neptunium|Np]] |
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| 238 || - || β || 2.11 days |
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|- |
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! [[plutonium|Pu]] |
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| 238 || - || α || 87.7 years |
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|} |
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==Compounds== |
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[[Image:Plutonium in solution.jpg|thumb|right|370px|Image showing colors of various oxidation states of Pu in solution on the left and colors of only one Pu oxidation state (IV) on the right in solutions containing different anions.]] |
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Plutonium reacts readily with [[oxygen]], forming PuO and [[Plutonium dioxide|PuO<sub>2</sub>]], as well as intermediate oxides. It reacts with the [[halogen]]s, giving rise to compounds such as PuX<sub>3</sub> where X can be F, Cl, Br or I; [[Plutonium fluoride|PuF<sub>4</sub>]] and PuF<sub>6</sub> are also seen. The following oxyhalides are observed: PuOCl, PuOBr and PuOI. It will react with [[carbon]] to form PuC, [[nitrogen]] to form [[Plutonium nitride|PuN]] and [[silicon]] to form PuSi<sub>2</sub>. |
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Plutonium like other actinides readily forms a dioxide plutonyl core (PuO<sub>2</sub>). In the environment, this plutonyl core readily complexes with carbonate as well as other oxygen moieties (OH<sup>-</sup>, NO<sub>2</sub><sup>-</sup>, NO<sub>3</sub><sup>-</sup>, and SO<sub>4</sub><sup>-2</sup>) to form charged complexes which can be readily mobile with low affinities to soil. |
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*PuO<sub>2</sub>(CO<sub>3</sub>)<sub>1</sub><sup>-2</sup> |
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*PuO<sub>2</sub>(CO<sub>3</sub>)<sub>2</sub><sup>-4</sup> |
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*PuO<sub>2</sub>(CO<sub>3</sub>)<sub>3</sub><sup>-6</sup> |
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PuO<sub>2</sub> formed from neutralizing highly acidic nitric acid solutions tends to form polymeric PuO<sub>2</sub> which is resistant to complexation. Plutonium also readily shifts valences between the +3, +4, +5 and +6 states. It is common for some fraction of plutonium in solution to exist in all of these states in equilibrium. |
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==Allotropes== |
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{{main|Allotropes of plutonium}} |
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[[Image:Pu-phases.png|frame|A diagram of the allotropes of plutonium at ambient pressure]] |
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Even at ambient pressure, plutonium occurs in a variety of [[allotrope]]s. These allotropes differ widely in crystal structure and density; the α and δ allotropes differ in density by more than 25% at constant pressure. |
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The presence of these many allotropes makes machining plutonium very difficult, as it changes state very readily. The reasons for the complicated phase diagram are not entirely understood; recent research has focused on constructing accurate computer models of the [[phase transition]]s.{{inote|Ambient pressure phase diagram of plutonium}} |
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In weapons applications, plutonium is often [[alloy]]ed with another metal (e.g., delta phase with a small percentage of [[gallium]]) to increase phase stability and thereby enhance workability and ease of handling. Interestingly, in fission weapons, the explosive [[shock wave]]s used to compress a plutonium core will also cause a transition from the usual delta phase plutonium to the denser alpha phase, significantly helping to achieve [[supercriticality]]. |
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==Isotopes== |
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{{main|Isotopes of plutonium}} |
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Twenty-one plutonium [[radioisotope]]s have been characterized. The most stable are Pu-244, with a [[half-life]] of 80.8 million years, Pu-242, with a half-life of 373,300 years, and Pu-239, with a half-life of 24,110 years. Because of its comparatively large half-life, minute amounts of Pu-244 can be found in nature,<ref>D.C . Hoffman, F. O. Lawrence, J. L. Mewheter, F. M. Rourke: ''Detection of Plutonium-244 in Nature.'' In: ''Nature'', Nr. 34, 1971, pp. 132–134</ref> All of the remaining [[radioactive]] isotopes have half-lives that are less than 7,000 years. This element also has eight [[meta state]]s, though none are very stable (all have half-lives less than one second). |
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The isotopes of plutonium range in [[atomic weight]] from 228.0387 [[atomic mass unit|u]] (Pu-228) to 247.074 u (Pu-247). The primary [[decay mode]]s before the most stable isotope, Pu-244, are [[spontaneous fission]] and [[alpha emission]]; the primary mode after is [[beta emission]]. The primary [[decay product]]s before Pu-244 are uranium and neptunium isotopes (neglecting the wide range of daughter nuclei created by fission processes), and the primary products after are [[americium]] isotopes. |
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[[Image:Plutonium pellet.jpg|right|thumb|250px|A pellet of plutonium-238, glowing due to [[blackbody radiation]], used for [[radioisotope thermoelectric generator]]s.]] |
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Key isotopes for applications are Pu-239, which is suitable for use in nuclear weapons and nuclear reactors, and Pu-238, which is suitable for use in [[radioisotope thermoelectric generators]]; see above for more details. The isotope Pu-240 undergoes spontaneous fission very readily, and is produced when Pu-239 is exposed to neutrons. The presence of Pu-240 in a material limits its nuclear bomb potential since it emits neutrons randomly, increasing the difficulty of initiating accurately the [[chain reaction]] at the desired instant and thus reducing the bomb's reliability and power. Plutonium consisting of more than about 90% Pu-239 is called '''[[weapons-grade]] plutonium'''; plutonium obtained from commercial reactors generally contains at least 20% Pu-240 and is called '''reactor-grade plutonium'''. |
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Pu-240, while of little importance by itself, plays a crucial role as a contaminant in plutonium used in nuclear weapons. It spontaneously fissions at a high rate, and a 1% impurity in Pu-239 will lead to unacceptably early initiation of a fission chain reaction in gun-type atomic weapons (e.g. the proposed [[Thin Man nuclear bomb|Thin Man]] bomb), blowing the weapon apart before much of its material can fission. Pu-240 contamination is the reason plutonium weapons must use an implosion design. A theoretical 100% pure Pu-239 weapon could be constructed as a gun-type device, but achieving this level of purity is prohibitively difficult. Pu-240 contamination has proven a mixed blessing to weapons designers. While it created delays and headaches during the Manhattan Project because of the need to develop implosion technology, those very same difficulties are currently a barrier to nuclear proliferation. Implosion devices are also inherently more efficient and less prone toward accidental detonation than are gun-type weapons. |
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==Precautions== |
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===Toxicity=== |
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[[Image:Plutonium pyrophoricity.jpg|thumb|right|350px|[[incandescence|Glowing]] hot bits of plutonium in a box, which have been set alight due to plutonium's [[pyrophoric]] nature. The "glow" is due to heat produced by a spontaneous chemical reaction with oxygen and has nothing to do with radioactivity.]] |
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Isotopes and compounds of plutonium are toxic due to its radioactivity<ref name="ATSDR">U.S. Department of Health and Human Services, Agency for Toxic Substances and Disease Registry (ATSDR), [http://www.atsdr.cdc.gov/toxprofiles/tp143.html Toxicological Profile for Plutonium], Draft for Public Comment, September 2007 (accessed May 22, 2008)</ref> While plutonium is sometimes described in media reports as "the most toxic substance known to man", from the standpoint of actual chemical or radiological [[toxicity]] this is incorrect.<ref>Bernard L. Cohen in ''Nuclear Engergy;'' Karl Otto Ott and Bernard I. Spinrad, eds. (New York: Plenum Press, 1985), pp. 355-365</ref><ref name="world-nuclear">[http://www.world-nuclear.org/info/inf15.html Plutonium], World Nuclear Association, April 2008 (website accessed May/22/2008)</ref> When taken in by mouth, plutonium is less poisonous than if inhaled, since it is not absorbed into the body efficiently when ingested. The U.S. Department of Energy estimates the increase in lifetime cancer risk for inhaled plutonium as 3×10<sup>−8</sup> pCi<sup>−1</sup>.<ref> {{cite web| url= http://consolidationeis.doe.gov/PDFs/PlutoniumANLFactSheetOct2001.pdf| title=ANL human health fact sheet--plutonium| publisher=Argonne National Laboratory| date=October 2001| accessdate=2007-06-16}}</ref> (this means that inhaling 1 μCi, or about 2.5 μg of reactor-grade plutonium is estimated to increase one's lifetime risk of developing cancer as a result of the exposure to 3%). When plutonium is absorbed into the body, it is excreted very slowly, with a [[biological half-life]] of 200 years.<ref>{{cite web|title=Radiological control technical training DOE-HDBK-1122-99 | publisher=U.S. Department of Energy| url=http://hss.energy.gov/NuclearSafety/techstds/standard/hdbk1122-04/part9of9.pdf }}</ref> From a purely chemical standpoint, it is about as poisonous as [[lead]] and other [[heavy metals]]. {{Fact|date=June 2007}} Plutonium has a metallic taste.<ref>{{cite book |
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| last =Welsome |
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| first =Eileen |
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| authorlink = |
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| coauthors = |
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| title =The Plutonium Files: America's Secret Medical Experiments in the Cold War |
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| publisher =Random House |
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| date =2000 |
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| location =New York |
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| pages = p. 17 |
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| url = |
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| doi = |
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| id = ISBN 0-385-31954-1}} |
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</ref> |
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Plutonium may be extremely dangerous when handled incorrectly. The [[alpha particle|alpha]] radiation it emits does not penetrate the skin, but can irradiate internal organs when plutonium is inhaled or ingested. Particularly at risk is the [[skeleton]], where it is likely to be absorbed by the bone surface, and the [[liver]], where it will likely collect and become concentrated. Extremely fine particles of plutonium (on the order of micrograms) can cause [[lung cancer]] if inhaled.{{Fact|date=July 2007}} |
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Other substances including [[ricin]], [[tetrodotoxin]], [[botulinum]] toxin, and [[tetanus]] toxin are fatal in doses of (sometimes far) under one milligram, and others (the [[nerve agent]]s, the [[amanita]] toxin) are in the range of a few milligrams. As such, plutonium is not unusual in terms of toxicity, even by inhalation. In addition, those substances are fatal in hours to days, whereas plutonium (and other cancer-causing radioactives) give an increased chance of illness decades in the future. Considerably larger amounts may cause acute [[radiation poisoning]] and death if ingested or inhaled; however, so far, no human is known to have immediately died because of inhaling or ingesting plutonium and many people have measurable amounts of plutonium in their bodies.<ref name="world-nuclear"/> |
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===Disposal difficulties=== |
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In contrast to naturally occurring radioisotopes such as [[radium]] or [[Carbon-14|C-14]], plutonium was manufactured, concentrated, and isolated in large amounts (hundreds of metric tons) during the [[Cold War]] for weapons production. These stockpiles, whether or not in weapons form, pose a significant problem because, unlike chemical or biological agents, no chemical process can destroy them. One proposal to dispose of surplus weapons-grade plutonium is to mix it with highly radioactive isotopes (e.g., spent reactor fuel) to deter handling by potential thieves or terrorists. Another is to mix it with uranium and use it to fuel nuclear power reactors (the ''mixed oxide'' or [[MOX]] approach). This would not only fission (and thereby destroy) much of the Pu-239, but also transmute a significant fraction of the remainder into Pu-240 and heavier isotopes that would make the resulting mixture useless for nuclear weapons.<ref>{{cite web|url=http://www.nap.edu/books/0309050421/html/index.html|author=National Academy of Sciences, Committee on International Security and Arms Control|title=Management and Disposition of Excess Weapons Plutonium|year=1994}}</ref> |
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===Criticality potential=== |
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Toxicity issues aside, care must be taken to avoid the accumulation of amounts of plutonium which approach [[Critical mass (nuclear)|critical mass]], particularly because plutonium's critical mass is only a third of that of uranium-235's. Despite not being confined by external pressure as is required for a nuclear weapon, it will nevertheless heat itself and break whatever confining environment it is in. Shape is relevant; compact shapes such as spheres are to be avoided. Plutonium in solution is more likely to form a critical mass than the solid form (due to moderation by the hydrogen in water). A weapon-scale nuclear explosion cannot occur accidentally, since it requires a greatly supercritical mass in order to explode rather than simply melt or fragment. However, a marginally critical mass will cause a lethal dose of radiation and has in fact done so in the past on several occasions. |
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[[Criticality accident]]s have occurred in the past, some of them with lethal consequences. Careless handling of tungsten carbide bricks around a 6.2 kg plutonium sphere resulted in a lethal dose of radiation at [[Los Alamos National Laboratory|Los Alamos]] on August 21, 1945, when scientist [[Harry K. Daghlian, Jr.]] received a dose estimated to be 510 [[Roentgen equivalent man|rems]] (5.1 [[Sievert|Sv]]) and died four weeks later. Nine months later, another Los Alamos scientist, [[Louis Slotin]], died from a similar accident involving a beryllium reflector and the same plutonium core (the so-called "[[demon core]]") that had previously claimed the life of Daghlian. These incidents were fictionalized in the 1989 film ''[[Fat Man and Little Boy]]''. In 1958, during a process of purifying plutonium at Los Alamos, a critical mass was formed in a mixing vessel, which resulted in the death of a crane operator. Other accidents of this sort have occurred in the [[Soviet Union]], [[Japan]], and many other countries. (See [[List of nuclear accidents]].) The 1986 [[Chernobyl accident]] caused a [[Plutonium in the environment|minor release of plutonium.]]{{Fact|date=July 2007}} |
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===Flammability=== |
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Metallic plutonium is also a fire hazard, especially if the material is finely divided. It reacts chemically with oxygen and water, which may result in an accumulation of [[plutonium hydride]], a [[pyrophoric]] substance; that is, a material that will ignite in air at room temperature. Plutonium expands considerably in size as it oxidizes and thus may break its container. The radioactivity of the burning material is an additional hazard. Magnesium-oxide sand is the most effective material for extinguishing a plutonium fire. It cools the burning material, acting as a [[heat sink]], and also blocks off oxygen. There was a major plutonium-initiated fire at the [[Rocky Flats Plant]] near [[Boulder, Colorado|Boulder]], [[Colorado]] in 1969.<ref>David Albright and Kevin O'Neill (1999). ''[http://www.isis-online.org/publications/usfacilities/Rfpbrf.html The Lessons of Nuclear Secrecy at Rocky Flats]''. ISIS Issue Brief.</ref> To avoid these problems, special precautions are necessary to store or handle plutonium in any form; generally a dry [[inert]] atmosphere is required.<ref>[http://www.hss.energy.gov/NuclearSafety/techstds/standard/hdbk1081/hbk1081d.html#ZZ281 Primer on Spontaneous Heating and Pyrophoricity - Pyrophoric Metals - Plutonium], Department of Energy Handbook DOE-HDBK-1081-94, December 1994. U.S. Department of Energy, Washington, D.C.</ref> |
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==See also== |
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*[[Nuclear engineering]] |
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*[[Nuclear fuel cycle]] |
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*[[Nuclear physics]] |
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*[[Nuclear reactor]] |
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*[[Plutonium in the environment]] |
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==References== |
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{{reflist|2}} |
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==External links== |
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{{Commons|Plutonium}} |
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{{wiktionary|plutonium}} |
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* [http://www.llnl.gov/csts/publications/sutcliffe/ "A Perspective on the Dangers of Plutonium" by Lawrence Livermore National Laboratory] [no longer online, but still available from the [http://web.archive.org/web/20060929015050/http://www.llnl.gov/csts/publications/sutcliffe/ Internet Archive] ] |
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* [http://www.ccnr.org/index_plute.html Collection of articles on plutonium at the Canadian Coalition for Nuclear Responsibility] |
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* [http://russp.org/BLC-3.html The Myth of Plutonium Toxicity] |
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* [http://www.lanl.gov/worldview/news/releases/archive/00-099.shtml Criticality Accidents Report Issued] |
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* [http://www.globalsecurity.org/wmd/library/report/crs/97-564.htm Nuclear Weapons: Disposal Options for Surplus Weapons-Usable Plutonium] |
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* [http://www-cms.llnl.gov/s-t/pu-phase_diagram.html Unraveling the Phase Diagram of Plutonium **Dead Link**] |
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* [http://www.ieer.org/fctsheet/pu-props.html Physical, Nuclear, and Chemical, Properties of Plutonium] from IEER |
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*[http://periodic.lanl.gov/elements/94.html Los Alamos National Laboratory — Plutonium] |
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* [http://education.jlab.org/itselemental/ele094.html It's Elemental — Plutonium] |
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* [http://consolidationeis.doe.gov/PDFs/PlutoniumANLFactSheetOct2001.pdf DOE Plutonium fact sheet (PDF)] |
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* ''[http://www.discover.com/issues/nov-05/features/end-of-plutonium/ End of the Plutonium Age]'', D. Samuels, Discover Magazine, vol. 26, no. 11 (November, 2005). |
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* [http://www.webelements.com/webelements/elements/text/Pu/index.html WebElements.com — Plutonium] |
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* [http://environmentalchemistry.com/yogi/periodic/Pu.html EnvironmentalChemistry.com — Plutonium] (JavaScript required) |
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* [http://www.fas.org/nuke/intro/nuke/plutonium.htm Federation of American Scientists — Plutonium production] |
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* [http://nuclearweaponarchive.org/Library/Plutonium/ nuclearweaponarchive.org — Plutonium Manufacture and Fabrication] |
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* ''[http://www.edpsciences.org/journal/index.cfm?v_url=epl/full/2001/16/6673/6673.html Ambient pressure phase diagram of plutonium — A unified theory for α-Pu and δ-Pu]'', P. Söderlind, Europhys. Lett., 55 (4), p. 525 (2001). |
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* [http://www.nuclearfiles.org/menu/key-issues/nuclear-energy/issues/world-plutonium-inventories-ong.htm Nuclear Files.org] Information regarding world plutonium inventories |
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* [http://www.fas.org/sgp/othergov/doe/lanl/pubs/number26.htm "Challenges in Plutonium Science"] — Special issue of ''Los Alamos Science'' from 2000 dedicated to scientific work on plutonium. |
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*[http://toxnet.nlm.nih.gov/cgi-bin/sis/search/r?dbs+hsdb:@term+@na+@rel+plutonium,+radioactive NLM Hazardous Substances Databank – Plutonium, Radioactive] |
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*[http://www.americanscientist.org/BookReviewTypeDetail/assetid/55118#55199 Plutonium: A History of the World's Most Dangerous Element] |
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* [http://alsos.wlu.edu/qsearch.aspx?browse=science/Plutonium Annotated bibliography on plutonium from the Alsos Digital Library.] |
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{{Nuclear Technology}} |
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{{compact periodic table}} |
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[[Category:Actinides]] |
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[[Category:Chemical elements]] |
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[[Category:Nuclear materials]] |
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[[Category:Plutonium|*]] |
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[[Category:Carcinogens]] |
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[[Category:Element toxicology]] |
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[[Category:Synthetic elements]] |
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Revision as of 15:21, 17 October 2008
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