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{{infobox curium}} | {{infobox curium}} | ||
'''Curium''' is a ]; it has ] Cm and ] 96. This ] ] element was named after eminent scientists ] and ], both known for their research on ]. Curium was first intentionally made by the team of ], ], and ] in 1944, using the ] at ]. They bombarded the newly discovered element ] (the isotope ]) with ]s. This was then sent to the ] at ] where a tiny sample of curium was eventually separated and identified. The discovery was kept secret until after the end of ]. The news was released to the public in November 1947. Most curium is produced by bombarding ] or plutonium with ]s in ]s – one ] of spent ] contains ~20 grams of curium. | '''Curium''' is a ]; it has ] '''Cm''' and ] 96. This ] ] element was named after eminent scientists ] and ], both known for their research on ]. Curium was first intentionally made by the team of ], ], and ] in 1944, using the ] at ]. They bombarded the newly discovered element ] (the isotope ]) with ]s. This was then sent to the ] at ] where a tiny sample of curium was eventually separated and identified. The discovery was kept secret until after the end of ]. The news was released to the public in November 1947. Most curium is produced by bombarding ] or plutonium with ]s in ]s – one ] of spent ] contains ~20 grams of curium. | ||
Curium is a hard, dense, silvery metal with a high melting and boiling point for an actinide. It is ] at ], but becomes ] upon cooling, and other magnetic transitions are also seen in many curium compounds. In compounds, curium usually has ] +3 and sometimes +4; the +3 valence is predominant in solutions. Curium readily oxidizes, and its oxides are a dominant form of this element. It forms strongly ] complexes with various organic compounds |
Curium is a hard, dense, silvery metal with a high melting and boiling point for an actinide. It is ] at ], but becomes ] upon cooling, and other magnetic transitions are also seen in many curium compounds. In compounds, curium usually has ] +3 and sometimes +4; the +3 valence is predominant in solutions. Curium readily oxidizes, and its oxides are a dominant form of this element. It forms strongly ] complexes with various organic compounds. If it gets into the human body, curium accumulates in bones, lungs, and liver, where it promotes ]. | ||
All known ]s of curium are radioactive and have small ] for a ]. |
All known ]s of curium are radioactive and have small ] for a ]. The most stable isotope, <sup>247</sup>Cm, has a half-life of 15.6 million years; the longest-lived curium isotopes predominantly emit ]. ]s can use the heat from this process, but this is hindered by the rarity and high cost of curium. Curium is used in making heavier actinides and the <sup>238</sup>Pu ] for power sources in ]s and ]s for spacecraft. It served as the α-source in the ]s of several space probes, including the '']'', '']'', '']'', and '']'' ]s and the ] on ] ], to analyze the composition and structure of the surface. | ||
==History== | ==History== | ||
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The sample was prepared as follows: first ] nitrate solution was coated on a ] foil of ~0.5 cm<sup>2</sup> area, the solution was evaporated and the residue was converted into ] (PuO<sub>2</sub>) by ]. Following cyclotron irradiation of the oxide, the coating was dissolved with ] and then precipitated as the hydroxide using concentrated aqueous ]. The residue was dissolved in ], and further separation was done by ] to yield a certain isotope of curium. The separation of curium and americium was so painstaking that the Berkeley group initially called those elements '']'' (from Greek for ''all demons'' or ''hell'') and '']'' (from Latin for ''madness'').<ref name="radio" /><ref>Krebs, Robert E. , Greenwood Publishing Group, 2006, {{ISBN|0-313-33438-2}} p. 322</ref> | The sample was prepared as follows: first ] nitrate solution was coated on a ] foil of ~0.5 cm<sup>2</sup> area, the solution was evaporated and the residue was converted into ] (PuO<sub>2</sub>) by ]. Following cyclotron irradiation of the oxide, the coating was dissolved with ] and then precipitated as the hydroxide using concentrated aqueous ]. The residue was dissolved in ], and further separation was done by ] to yield a certain isotope of curium. The separation of curium and americium was so painstaking that the Berkeley group initially called those elements '']'' (from Greek for ''all demons'' or ''hell'') and '']'' (from Latin for ''madness'').<ref name="radio" /><ref>Krebs, Robert E. , Greenwood Publishing Group, 2006, {{ISBN|0-313-33438-2}} p. 322</ref> | ||
Curium-242 was made in July–August 1944 by bombarding <sup>239</sup>Pu with ] to produce curium with the release of a ]: | Curium-242 was made in July–August 1944{{Citation needed|date=October 2024}} by bombarding <sup>239</sup>Pu with ] to produce curium with the release of a ]:<ref name="E96"/> | ||
: <chem>^{239}_{94}Pu + ^{4}_{2}He -> ^{242}_{96}Cm + ^{1}_{0}n</chem> | : <chem>^{239}_{94}Pu + ^{4}_{2}He -> ^{242}_{96}Cm + ^{1}_{0}n</chem> | ||
Curium-242 was unambiguously identified by the characteristic energy of the α-particles emitted during the decay: | Curium-242 was unambiguously identified by the characteristic energy of the α-particles emitted during the decay: | ||
: <chem>^{242}_{96}Cm -> ^{238}_{94}Pu + ^{4}_{2}He</chem> | : <chem>^{242}_{96}Cm -> ^{238}_{94}Pu + ^{4}_{2}He</chem> | ||
The ] of this ] was first measured as 150 days and then corrected to 162.8 days. |
The ] of this ] was first measured as 5 months (150 days)<ref name="E96"/> and then corrected to 162.8 days.{{NUBASE2020|name}} | ||
Another isotope <sup>240</sup>Cm was produced in a similar reaction in March 1945: | Another isotope <sup>240</sup>Cm was produced in a similar reaction in March 1945: | ||
: <chem>^{239}_{94}Pu + ^{4}_{2}He -> ^{240}_{96}Cm + 3^{1}_{0}n</chem> | : <chem>^{239}_{94}Pu + ^{4}_{2}He -> ^{240}_{96}Cm + 3^{1}_{0}n</chem> | ||
The α-decay half-life of <sup>240</sup>Cm was |
The α-decay half-life of <sup>240</sup>Cm was determined as 26.8 days<ref name="E96"/> and later revised to 30.4 days.{{NUBASE2020|name}} | ||
The discovery of curium and americium in 1944 was closely related to the ], so the results were confidential and declassified only in 1945. Seaborg leaked the synthesis of the elements 95 and 96 on the U.S. radio show for children, the ], five days before the official presentation at an ] meeting on November 11, 1945, when one listener asked if any new transuranic element beside plutonium and ] had been discovered during the war.<ref name="radio">{{cite web|url = http://pubs.acs.org/cen/80th/americium.html|title = Chemical & Engineering News: It's Elemental: The Periodic Table – Americium|access-date = 2008-12-07| first = Rachel Sheremeta|last = Pepling|date = 2003}}</ref> The discovery of curium (<sup>242</sup>Cm and <sup>240</sup>Cm), its production, and its compounds was later patented listing only Seaborg as the inventor.<ref>Seaborg, G. T. {{US patent|3161462}} "Element", Filing date: 7 February 1949, Issue date: December 1964</ref> | The discovery of curium and americium in 1944 was closely related to the ], so the results were confidential and declassified only in 1945. Seaborg leaked the synthesis of the elements 95 and 96 on the U.S. radio show for children, the '']'', five days before the official presentation at an ] meeting on November 11, 1945, when one listener asked if any new transuranic element beside plutonium and ] had been discovered during the war.<ref name="radio">{{cite web|url = http://pubs.acs.org/cen/80th/americium.html|title = Chemical & Engineering News: It's Elemental: The Periodic Table – Americium|access-date = 2008-12-07| first = Rachel Sheremeta|last = Pepling|date = 2003}}</ref> The discovery of curium (<sup>242</sup>Cm and <sup>240</sup>Cm), its production, and its compounds was later patented listing only Seaborg as the inventor.<ref>Seaborg, G. T. {{US patent|3161462}} "Element", Filing date: 7 February 1949, Issue date: December 1964</ref> | ||
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The element was named after ] and her husband ], who are known for discovering ] and for their work in ]. It followed the example of ], a ] element above curium in the periodic table, which was named after the explorer of ]s ]:<ref>Greenwood, p. 1252</ref> | The element was named after ] and her husband ], who are known for discovering ] and for their work in ]. It followed the example of ], a ] element above curium in the periodic table, which was named after the explorer of ]s ]:<ref>Greenwood, p. 1252</ref> | ||
:: |
::<blockquote>As the name for the element of atomic number 96 we should like to propose "curium", with symbol Cm. The evidence indicates that element 96 contains seven 5f electrons and is thus analogous to the element gadolinium, with its seven 4f electrons in the regular rare earth series. On this basis element 96 is named after the Curies in a manner analogous to the naming of gadolinium, in which the chemist Gadolin was honored.<ref name="E96" /></blockquote> | ||
The first curium samples were barely visible, and were identified by their radioactivity. Louis Werner and ] made the first substantial sample of 30 |
The first curium samples were barely visible, and were identified by their radioactivity. Louis Werner and ] made the first substantial sample of 30 μg curium-242 hydroxide at University of California, Berkeley in 1947 by bombarding ]-241 with neutrons.<ref name="CRC">Hammond C. R. "The elements" in {{RubberBible86th}}</ref><ref>L. B. Werner, I. Perlman: "Isolation of Curium", NNES PPR (''National Nuclear Energy Series, Plutonium Project Record''), Vol. 14 B, ''The Transuranium Elements: Research Papers'', Paper No. 22.5, McGraw-Hill Book Co., Inc., New York, 1949.</ref><ref>{{cite web|url=http://www.nap.edu/readingroom.php?book=biomems&page=iperlman.html |title=National Academy of Sciences. Isadore Perlman 1915–1991 |publisher=Nap.edu |access-date=2011-03-25}}</ref> Macroscopic amounts of ] were obtained in 1950 by W. W. T. Crane, J. C. Wallmann and B. B. Cunningham. Its magnetic susceptibility was very close to that of GdF<sub>3</sub> providing the first experimental evidence for the +3 valence of curium in its compounds.<ref name="CRC" /> Curium metal was produced only in 1951 by reduction of CmF<sub>3</sub> with ].<ref name="CM_METALL">{{cite journal|first1 = J. C.|last1 = Wallmann|first2 = W. W. T.|last2 = Crane|first3 = B. B.|last3 = Cunningham|title = The Preparation and Some Properties of Curium Metal|journal = ]|date = 1951|volume =73|issue =1|pages = 493–494|doi = 10.1021/ja01145a537|hdl = 2027/mdp.39015086479790|url = https://cloudfront.escholarship.org/dist/prd/content/qt51t3d12j/qt51t3d12j.pdf}}</ref><ref>{{cite journal|author =Werner, L. B.|author2 =Perlman, I.|title =First Isolation of Curium| journal = Journal of the American Chemical Society|date = 1951| volume =73|issue =1|pages = 5215–5217|doi = 10.1021/ja01155a063|s2cid =95799539}}</ref> | ||
==Characteristics== | ==Characteristics== | ||
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===Physical=== | ===Physical=== | ||
] | ] | ||
] of the Cm(HDPA)3· |
] of the Cm(HDPA)<sub>3</sub>·H<sub>2</sub>O crystal upon ] with 420 nm light]] | ||
A synthetic, radioactive element, curium is a hard, dense metal with a silvery-white appearance and physical and chemical properties resembling ]. Its melting point of 1344 °C is significantly higher than that of the previous elements neptunium (637 °C), plutonium (639 °C) and americium (1176 °C). In comparison, gadolinium melts at 1312 °C. Curium boils at 3556 °C. With a density of 13.52 g/cm<sup>3</sup>, curium is lighter than neptunium (20.45 g/cm<sup>3</sup>) and plutonium (19.8 g/cm<sup>3</sup>), but heavier than most other metals. Of two crystalline forms of curium, α-Cm is more stable at ambient conditions. It has a hexagonal symmetry, ] P6<sub>3</sub>/mmc, lattice parameters ''a'' = 365 ] and ''c'' = 1182 pm, and four ]s per ].<ref name="Milman">{{cite journal|last1=Milman|first1=V.|title=Crystal structures of curium compounds: an ab initio study|journal=Journal of Nuclear Materials|volume=322|issue=2–3|page=165|date=2003|doi=10.1016/S0022-3115(03)00321-0|bibcode=2003JNuM..322..165M|last2=Winkler|first2=B.|last3=Pickard|first3=C. J.}}</ref> The crystal consists of double-] with the layer sequence ABAC and so is isotypic with α-lanthanum. At pressure >23 ], at room temperature, α-Cm becomes β-Cm, which has ] symmetry, space group Fm{{overline|3}}m and lattice constant ''a'' = 493 pm.<ref name = "Milman" /> On further compression to 43 GPa, curium becomes an ] γ-Cm structure similar to α-uranium, with no further transitions observed up to 52 GPa. These three curium phases are also called Cm I, II and III.<ref>Young, D. A. , University of California Press, 1991, {{ISBN|0-520-07483-1}}, p. 227</ref><ref>{{cite journal|last1=Haire|first1=R.|last2=Peterson|first2=J.|last3=Benedict|first3=U.|last4=Dufour|first4=C.|last5=Itie|first5=J.|title=X-ray diffraction of curium-248 metal under pressures of up to 52 GPa|journal=Journal of the Less Common Metals|volume=109|issue=1|page=71|date=1985|doi=10.1016/0022-5088(85)90108-0}}</ref> | A synthetic, radioactive element, curium is a hard, dense metal with a silvery-white appearance and physical and chemical properties resembling ]. Its melting point of 1344 °C is significantly higher than that of the previous elements neptunium (637 °C), plutonium (639 °C) and americium (1176 °C). In comparison, gadolinium melts at 1312 °C. Curium boils at 3556 °C. With a density of 13.52 g/cm<sup>3</sup>, curium is lighter than neptunium (20.45 g/cm<sup>3</sup>) and plutonium (19.8 g/cm<sup>3</sup>), but heavier than most other metals. Of two crystalline forms of curium, α-Cm is more stable at ambient conditions. It has a hexagonal symmetry, ] P6<sub>3</sub>/mmc, lattice parameters ''a'' = 365 ] and ''c'' = 1182 pm, and four ]s per ].<ref name="Milman">{{cite journal|last1=Milman|first1=V.|title=Crystal structures of curium compounds: an ab initio study|journal=Journal of Nuclear Materials|volume=322|issue=2–3|page=165|date=2003|doi=10.1016/S0022-3115(03)00321-0|bibcode=2003JNuM..322..165M|last2=Winkler|first2=B.|last3=Pickard|first3=C. J.}}</ref> The crystal consists of double-] with the layer sequence ABAC and so is isotypic with α-lanthanum. At pressure >23 ], at room temperature, α-Cm becomes β-Cm, which has ] symmetry, space group Fm{{overline|3}}m and lattice constant ''a'' = 493 pm.<ref name = "Milman" /> On further compression to 43 GPa, curium becomes an ] γ-Cm structure similar to α-uranium, with no further transitions observed up to 52 GPa. These three curium phases are also called Cm I, II and III.<ref>Young, D. A. , University of California Press, 1991, {{ISBN|0-520-07483-1}}, p. 227</ref><ref>{{cite journal|last1=Haire|first1=R.|last2=Peterson|first2=J.|last3=Benedict|first3=U.|last4=Dufour|first4=C.|last5=Itie|first5=J.|title=X-ray diffraction of curium-248 metal under pressures of up to 52 GPa|journal=Journal of the Less Common Metals|volume=109|issue=1|page=71|date=1985|doi=10.1016/0022-5088(85)90108-0}}</ref> | ||
Curium has peculiar magnetic properties. Its neighbor element americium shows no deviation from ] ] in the entire temperature range, but α-Cm transforms to an ] state upon cooling to 65–52 K,<ref>{{cite journal|last1=Kanellakopulos|first1=B.|title=The magnetic susceptibility of Americium and curium metal|journal=Solid State Communications|volume=17|issue=6|page=713|date=1975|doi=10.1016/0038-1098(75)90392-0|bibcode = 1975SSCom..17..713K|last2=Blaise|first2=A.|last3=Fournier|first3=J. M.|last4=Müller|first4=W. }}</ref><ref>{{cite journal|last1=Fournier|first1=J.|title=Curium: A new magnetic element|journal=Physica B+C|volume=86–88|page=30|date=1977|doi=10.1016/0378-4363(77)90214-5|bibcode = 1977PhyBC..86...30F|last2=Blaise|first2=A.|last3=Muller|first3=W.|last4=Spirlet|first4=J.-C. }}</ref> and β-Cm exhibits a ] transition at ~205 K. Curium pnictides show ] transitions upon cooling: <sup>244</sup>CmN and <sup>244</sup>CmAs at 109 K, <sup>248</sup>CmP at 73 K and <sup>248</sup>CmSb at 162 K. The lanthanide analog of curium, gadolinium, and its pnictides, also show magnetic transitions upon cooling, but the transition character is somewhat different: Gd and GdN become ferromagnetic, and GdP, GdAs and GdSb show antiferromagnetic ordering.<ref>Nave, S. E.; Huray, P. G.; Peterson, J. R. and Damien, D. A. , Oak Ridge National Laboratory</ref> | Curium has peculiar magnetic properties. Its neighbor element americium shows no deviation from ] ] in the entire temperature range, but α-Cm transforms to an ] state upon cooling to 65–52 K,<ref>{{cite journal|last1=Kanellakopulos|first1=B.|title=The magnetic susceptibility of Americium and curium metal|journal=Solid State Communications|volume=17|issue=6|page=713|date=1975|doi=10.1016/0038-1098(75)90392-0|bibcode = 1975SSCom..17..713K|last2=Blaise|first2=A.|last3=Fournier|first3=J. M.|last4=Müller|first4=W. }}</ref><ref>{{cite journal|last1=Fournier|first1=J.|title=Curium: A new magnetic element|journal=Physica B+C|volume=86–88|page=30|date=1977|doi=10.1016/0378-4363(77)90214-5|bibcode = 1977PhyBC..86...30F|last2=Blaise|first2=A.|last3=Muller|first3=W.|last4=Spirlet|first4=J.-C. }}</ref> and β-Cm exhibits a ] transition at ~205 K. Curium pnictides show ] transitions upon cooling: <sup>244</sup>CmN and <sup>244</sup>CmAs at 109 K, <sup>248</sup>CmP at 73 K and <sup>248</sup>CmSb at 162 K. The lanthanide analog of curium, gadolinium, and its pnictides, also show magnetic transitions upon cooling, but the transition character is somewhat different: Gd and GdN become ferromagnetic, and GdP, GdAs and GdSb show antiferromagnetic ordering.<ref>Nave, S. E.; Huray, P. G.; Peterson, J. R. and Damien, D. A. , Oak Ridge National Laboratory</ref> | ||
In accordance with magnetic data, electrical resistivity of curium increases with temperature – about twice between 4 and 60 K – and then is nearly constant up to room temperature. There is a significant increase in resistivity over time (~{{val|10|u= |
In accordance with magnetic data, electrical resistivity of curium increases with temperature – about twice between 4 and 60 K – and then is nearly constant up to room temperature. There is a significant increase in resistivity over time (~{{val|10|u=μΩ·cm/h}}) due to self-damage of the crystal lattice by alpha decay. This makes uncertain the true resistivity of curium (~{{val|125|u=μΩ·cm}}). Curium's resistivity is similar to that of gadolinium, and the actinides plutonium and neptunium, but significantly higher than that of americium, uranium, ] and ].<ref name="res" /> | ||
Under ultraviolet illumination, curium(III) ions show strong and stable yellow-orange ] with a maximum in the range of 590–640 nm depending on their environment.<ref name="denecke">{{cite journal|last1=Denecke|first1=Melissa A.|last2=Rossberg|first2=André|last3=Panak|first3=Petra J.|last4=Weigl|first4=Michael|last5=Schimmelpfennig|first5=Bernd|last6=Geist|first6=Andreas|title=Characterization and Comparison of Cm(III) and Eu(III) Complexed with 2,6-Di(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine Using EXAFS, TRFLS, and Quantum-Chemical Methods|journal=Inorganic Chemistry|volume=44|issue=23|date=2005|pmid=16270980|doi=10.1021/ic0511726|pages=8418–8425}}</ref> The fluorescence originates from the transitions from the first excited state <sup>6</sup>D<sub>7/2</sub> and the ground state <sup>8</sup>S<sub>7/2</sub>. Analysis of this fluorescence allows monitoring interactions between Cm(III) ions in organic and inorganic complexes.<ref name="plb">Bünzli, J.-C. G. and Choppin, G. R. ''Lanthanide probes in life, chemical, and earth sciences: theory and practice'', Elsevier, Amsterdam, 1989 {{ISBN|0-444-88199-9}}</ref> | Under ultraviolet illumination, curium(III) ions show strong and stable yellow-orange ] with a maximum in the range of 590–640 nm depending on their environment.<ref name="denecke">{{cite journal|last1=Denecke|first1=Melissa A.|last2=Rossberg|first2=André|last3=Panak|first3=Petra J.|last4=Weigl|first4=Michael|last5=Schimmelpfennig|first5=Bernd|last6=Geist|first6=Andreas|title=Characterization and Comparison of Cm(III) and Eu(III) Complexed with 2,6-Di(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine Using EXAFS, TRFLS, and Quantum-Chemical Methods|journal=Inorganic Chemistry|volume=44|issue=23|date=2005|pmid=16270980|doi=10.1021/ic0511726|pages=8418–8425}}</ref> The fluorescence originates from the transitions from the first excited state <sup>6</sup>D<sub>7/2</sub> and the ground state <sup>8</sup>S<sub>7/2</sub>. Analysis of this fluorescence allows monitoring interactions between Cm(III) ions in organic and inorganic complexes.<ref name="plb">Bünzli, J.-C. G. and Choppin, G. R. ''Lanthanide probes in life, chemical, and earth sciences: theory and practice'', Elsevier, Amsterdam, 1989 {{ISBN|0-444-88199-9}}</ref> | ||
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===Chemical=== | ===Chemical=== | ||
] | ] | ||
Curium ion in solution almost always has a +3 ], the most stable oxidation state for curium.<ref>Penneman, p. 24</ref> A +4 oxidation state is seen mainly in a few solid phases, such as CmO<sub>2</sub> and CmF<sub>4</sub>.<ref>{{cite journal|last1=Keenan|first1=Thomas K.|title=First Observation of Aqueous Tetravalent Curium|journal=Journal of the American Chemical Society|volume=83|issue=17|page=3719|date=1961|doi=10.1021/ja01478a039}}</ref><ref name = "asprey" /> Aqueous curium(IV) is only known in the presence of strong oxidizers such as ], and is easily reduced to curium(III) by ] and even by water itself.<ref name="Lumetta" /> Chemical behavior of curium is different from the actinides thorium and uranium, and is similar to americium and many ]s. In aqueous solution, the Cm<sup>3+</sup> ion is colorless to pale green;<ref name="g1265">Greenwood, p. 1265</ref> Cm<sup>4+</sup> ion is pale yellow.<ref name="HOWI_1956">Holleman, p. 1956</ref> The optical absorption of Cm<sup>3+</sup> ion contains three sharp peaks at 375.4, 381.2 and 396.5 |
Curium ion in solution almost always has a +3 ], the most stable oxidation state for curium.<ref>Penneman, p. 24</ref> A +4 oxidation state is seen mainly in a few solid phases, such as CmO<sub>2</sub> and CmF<sub>4</sub>.<ref>{{cite journal|last1=Keenan|first1=Thomas K.|title=First Observation of Aqueous Tetravalent Curium|journal=Journal of the American Chemical Society|volume=83|issue=17|page=3719|date=1961|doi=10.1021/ja01478a039}}</ref><ref name = "asprey" /> Aqueous curium(IV) is only known in the presence of strong oxidizers such as ], and is easily reduced to curium(III) by ] and even by water itself.<ref name="Lumetta" /> Chemical behavior of curium is different from the actinides thorium and uranium, and is similar to americium and many ]s. In aqueous solution, the Cm<sup>3+</sup> ion is colorless to pale green;<ref name="g1265">Greenwood, p. 1265</ref> Cm<sup>4+</sup> ion is pale yellow.<ref name="HOWI_1956">Holleman, p. 1956</ref> The optical absorption of Cm<sup>3+</sup> ion contains three sharp peaks at 375.4, 381.2 and 396.5 nm and their strength can be directly converted into the concentration of the ions.<ref>Penneman, pp. 25–26</ref> The +6 oxidation state has only been reported once in solution in 1978, as the curyl ion ({{chem|CmO|2|2+}}): this was prepared from ] of ] in the americium(V) ion {{chem|242|AmO|2|+}}.<ref name="CmO3" /> Failure to get Cm(VI) from oxidation of Cm(III) and Cm(IV) may be due to the high Cm<sup>4+</sup>/Cm<sup>3+</sup> ] and the instability of Cm(V).<ref name="Lumetta">{{cite book|first1 = Lumetta|last1 = Gregg J.|first2 = Major C.|last2 = Thompson|first3 = Robert A.|last3 = Penneman|first4 = P. Gary|last4 = Eller|contribution = Curium|title = The Chemistry of the Actinide and Transactinide Elements|editor1-first = Lester R.|editor1-last = Morss|editor2-first = Norman M.|editor2-last = Edelstein|editor3-first = Jean|editor3-last = Fuger|edition = 3rd|date = 2006|volume = 3|publisher = Springer|location = Dordrecht, the Netherlands|pages = 1397–1443|url = http://radchem.nevada.edu/classes/rdch710/files/neptunium.pdf|doi = 10.1007/1-4020-3598-5_9|isbn = 978-1-4020-3555-5|access-date = 2013-10-18|archive-date = 2018-01-17|archive-url = https://web.archive.org/web/20180117190715/http://radchem.nevada.edu/classes/rdch710/files/neptunium.pdf|url-status = dead}}</ref> | ||
Curium ions are ] and thus form most stable complexes with hard bases.<ref>{{cite journal|last1=Jensen|first1=Mark P.|last2=Bond|first2=Andrew H.|title=Comparison of Covalency in the Complexes of Trivalent Actinide and Lanthanide Cations|journal=Journal of the American Chemical Society|volume=124|issue=33|date=2002|pmid=12175247|doi=10.1021/ja0178620|pages=9870–9877|url=https://figshare.com/articles/Comparison_of_Covalency_in_the_Complexes_of_Trivalent_Actinide_and_Lanthanide_Cations/3640428}}</ref> The bonding is mostly ionic, with a small covalent component.<ref>{{cite journal|last1=Seaborg |first1=Glenn T. |title=Overview of the Actinide and Lanthanide (the ''f'') Elements|journal=Radiochimica Acta|date=1993|volume=61|issue=3–4 |pages=115–122|doi=10.1524/ract.1993.61.34.115 |s2cid=99634366 }}</ref> Curium in its complexes commonly exhibits a 9-fold coordination environment, with a ].<ref>Greenwood, p. 1267</ref> | Curium ions are ] and thus form most stable complexes with hard bases.<ref>{{cite journal|last1=Jensen|first1=Mark P.|last2=Bond|first2=Andrew H.|title=Comparison of Covalency in the Complexes of Trivalent Actinide and Lanthanide Cations|journal=Journal of the American Chemical Society|volume=124|issue=33|date=2002|pmid=12175247|doi=10.1021/ja0178620|pages=9870–9877|url=https://figshare.com/articles/Comparison_of_Covalency_in_the_Complexes_of_Trivalent_Actinide_and_Lanthanide_Cations/3640428}}</ref> The bonding is mostly ionic, with a small covalent component.<ref>{{cite journal|last1=Seaborg |first1=Glenn T. |title=Overview of the Actinide and Lanthanide (the ''f'') Elements|journal=Radiochimica Acta|date=1993|volume=61|issue=3–4 |pages=115–122|doi=10.1524/ract.1993.61.34.115 |s2cid=99634366 }}</ref> Curium in its complexes commonly exhibits a 9-fold coordination environment, with a ].<ref>Greenwood, p. 1267</ref> | ||
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===Isotopes=== | ===Isotopes=== | ||
{{see also|Isotopes of curium}} | {{see also|Isotopes of curium}} | ||
About 19 ]s and 7 ]s, <sup>233</sup>Cm to <sup>251</sup>Cm, are known; none are ]. The longest half-lives are 15.6 million years (<sup>247</sup>Cm) and 348,000 years (<sup>248</sup>Cm). Other long-lived ones are <sup>245</sup>Cm (8500 years), <sup>250</sup>Cm (8300 years) and <sup>246</sup>Cm (4760 years). Curium-250 is unusual: it mostly (~86%) decays by ]. The most commonly used isotopes are <sup>242</sup>Cm and <sup>244</sup>Cm with the half-lives 162.8 days and 18. |
About 19 ]s and 7 ]s, <sup>233</sup>Cm to <sup>251</sup>Cm, are known; none are ]. The longest half-lives are 15.6 million years (<sup>247</sup>Cm) and 348,000 years (<sup>248</sup>Cm). Other long-lived ones are <sup>245</sup>Cm (8500 years), <sup>250</sup>Cm (8300 years) and <sup>246</sup>Cm (4760 years). Curium-250 is unusual: it mostly (~86%) decays by ]. The most commonly used isotopes are <sup>242</sup>Cm and <sup>244</sup>Cm with the half-lives 162.8 days and 18.11 years, respectively.{{NUBASE2020|name}} | ||
<div style="float:right; margin:0.5em; font-size:85%;"> | <div style="float:right; margin:0.5em; font-size:85%;"> | ||
{| class="wikitable" | {| class="wikitable" | ||
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</div> | </div> | ||
All isotopes <sup>242</sup>Cm |
All isotopes ranging from <sup>242</sup>Cm to <sup>248</sup>Cm, as well as <sup>250</sup>Cm, undergo a self-sustaining ] and thus in principle can be a ] in a reactor. As in most transuranic elements, ] cross section is especially high for the odd-mass curium isotopes <sup>243</sup>Cm, <sup>245</sup>Cm and <sup>247</sup>Cm. These can be used in ]s, whereas a mixture of curium isotopes is only suitable for ] since the even-mass isotopes are not fissile in a thermal reactor and accumulate as burn-up increases.<ref name="irsn">Institut de Radioprotection et de Sûreté Nucléaire: {{webarchive |url=https://web.archive.org/web/20110519171204/http://ec.europa.eu/energy/nuclear/transport/doc/irsn_sect03_146.pdf |date=May 19, 2011 }}, p. 16</ref> The mixed-oxide (MOX) fuel, which is to be used in power reactors, should contain little or no curium because ] of <sup>248</sup>Cm will create ]. Californium is a strong ] emitter, and would pollute the back end of the fuel cycle and increase the dose to reactor personnel. Hence, if ]s are to be used as fuel in a thermal neutron reactor, the curium should be excluded from the fuel or placed in special fuel rods where it is the only actinide present.<ref>{{cite book|author=National Research Council (U.S.). Committee on Separations Technology and Transmutation Systems|title=Nuclear wastes: technologies for separations and transmutation|url=https://books.google.com/books?id=iRI7Cx2D4e4C&pg=PA231|access-date=19 April 2011|date=1996|publisher=National Academies Press|isbn=978-0-309-05226-9|pages=231–}}</ref> | ||
] | ] | ||
The adjacent table lists the ]es for curium isotopes for a sphere, without moderator or reflector. With a metal reflector (30 cm of steel), the critical masses of the odd isotopes are about 3–4 kg. When using water (thickness ~20–30 cm) as the reflector, the critical mass can be as small as 59 |
The adjacent table lists the ]es for curium isotopes for a sphere, without moderator or reflector. With a metal reflector (30 cm of steel), the critical masses of the odd isotopes are about 3–4 kg. When using water (thickness ~20–30 cm) as the reflector, the critical mass can be as small as 59 grams for <sup>245</sup>Cm, 155 grams for <sup>243</sup>Cm and 1550 grams for <sup>247</sup>Cm. There is significant uncertainty in these critical mass values. While it is usually on the order of 20%, the values for <sup>242</sup>Cm and <sup>246</sup>Cm were listed as large as 371 kg and 70.1 kg, respectively, by some research groups.<ref name="irsn" /><ref>{{cite journal|author=Okundo, H.|author2=Kawasaki, H.|name-list-style=amp |title=Critical and Subcritical Mass Calculations of Curium-243 to −247 Based on JENDL-3.2 for Revision of ANSI/ANS-8.15|journal=Journal of Nuclear Science and Technology|date=2002|volume=39|pages=1072–1085|doi=10.3327/jnst.39.1072|issue=10|doi-access=free}}</ref> | ||
Curium is not currently used as nuclear fuel due to its low availability and high price.<ref> (in German)</ref> <sup>245</sup>Cm and <sup>247</sup>Cm have very small critical mass and so could be used in ]s, but none are known to have been made. Curium-243 is not suitable for such, due to its short half-life and strong α emission, which would cause excessive heat.<ref>{{cite book|author1=Jukka Lehto|author2=Xiaolin Hou|title=Chemistry and Analysis of Radionuclides: Laboratory Techniques and Methodology|url=https://books.google.com/books?id=v2iRJaO3SMIC&pg=PA303|access-date=19 April 2011|date=2 February 2011|publisher=Wiley-VCH|isbn=978-3-527-32658-7|pages=303–}}</ref> Curium-247 would be highly suitable due to its long half-life, which is 647 times longer than ] (used in many existing ]s). | Curium is not currently used as nuclear fuel due to its low availability and high price.<ref> (in German)</ref> <sup>245</sup>Cm and <sup>247</sup>Cm have very small critical mass and so could be used in ]s, but none are known to have been made. Curium-243 is not suitable for such, due to its short half-life and strong α emission, which would cause excessive heat.<ref>{{cite book|author1=Jukka Lehto|author2=Xiaolin Hou|title=Chemistry and Analysis of Radionuclides: Laboratory Techniques and Methodology|url=https://books.google.com/books?id=v2iRJaO3SMIC&pg=PA303|access-date=19 April 2011|date=2 February 2011|publisher=Wiley-VCH|isbn=978-3-527-32658-7|pages=303–}}</ref> Curium-247 would be highly suitable due to its long half-life, which is 647 times longer than ] (used in many existing ]s). | ||
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===Occurrence=== | ===Occurrence=== | ||
]'' nuclear test.]] | ]'' nuclear test.]] | ||
The longest-lived isotope, <sup>247</sup>Cm, has half-life 15.6 |
The longest-lived isotope, <sup>247</sup>Cm, has half-life 15.6 million years; so any ] curium, that is, present on Earth when it formed, should have decayed by now. Its past presence as an ] is detectable as an excess of its primordial, long-lived daughter <sup>235</sup>U.<ref>{{cite news |url=https://phys.org/news/2016-03-cosmochemists-evidence-unstable-heavy-element.html |title=Cosmochemists find evidence for unstable heavy element at solar system formation |date=2016 |publisher=University of Chicago |website=phys.org |access-date=6 June 2022}}</ref> Traces of <sup>242</sup>Cm may occur naturally in uranium minerals due to neutron capture and beta decay (<sup>238</sup>U → <sup>239</sup>Pu → <sup>240</sup>Pu → <sup>241</sup>Am → <sup>242</sup>Cm), though the quantities would be tiny and this has not been confirmed: even with "extremely generous" estimates for neutron absorption possibilities, the quantity of <sup>242</sup>Cm present in 1 × 10<sup>8</sup> kg of 18% uranium pitchblende would not even be one atom.<ref name=ThorntonBurdette/><ref>{{Cite web|url=https://www.livescience.com/39915-facts-about-curium.html|title=Facts About Curium|last=Earth|first=Live Science Staff 2013-09-24T21:44:13Z Planet|website=livescience.com|date=24 September 2013|language=en|access-date=2019-08-10}}</ref><ref>{{Cite web|url=http://www.rsc.org/periodic-table/element/96/curium|title=Curium - Element information, properties and uses {{!}} Periodic Table|website=www.rsc.org|access-date=2019-08-10}}</ref> Traces of <sup>247</sup>Cm are also probably brought to Earth in ]s, but this also has not been confirmed.<ref name=ThorntonBurdette>{{cite journal |last1=Thornton |first1=Brett F. |last2=Burdette |first2=Shawn C. |date=2019 |title=Neutron stardust and the elements of Earth |url=https://www.nature.com/articles/s41557-018-0190-9 |journal=Nature Chemistry |volume=11 |issue=1 |pages=4–10 |doi=10.1038/s41557-018-0190-9 |pmid=30552435 |bibcode=2019NatCh..11....4T |s2cid=54632815 |access-date=19 February 2022}}</ref> There is also the possibility of <sup>244</sup>Cm being produced as the ] daughter of natural <sup>244</sup>Pu.<ref name=ThorntonBurdette/><ref name="Tretyak2002">{{Cite journal | ||
|last1=Tretyak |first1=V.I. | |||
|last2=Zdesenko |first2=Yu.G. | |||
|year=2002 | |||
|title=Tables of Double Beta Decay Data — An Update | |||
|journal=] |volume=80 |issue=1 |pages=83–116 | |||
|doi=10.1006/adnd.2001.0873 | |||
|bibcode=2002ADNDT..80...83T }}</ref> | |||
Curium is made artificially in small amounts for research purposes. It also occurs as one of the waste products in ].<ref>{{cite journal |vauthors = Chaplin J, Warwick P, Cundy A, Bochud F, Froidevaux P |title=Novel DGT Configurations for the Assessment of Bioavailable Plutonium, Americium, and Uranium in Marine and Freshwater Environments |journal=Analytical Chemistry |date=25 August 2021 |volume=93 |issue=35 |pages=11937–11945 |doi=10.1021/acs.analchem.1c01342 |pmid=34432435 |s2cid=237307309 |doi-access=free }}</ref><ref>{{cite journal |vauthors = Chaplin J, Christl M, Straub M, Bochud F, Froidevaux P |title=Passive Sampling Tool for Actinides in Spent Nuclear Fuel Pools |journal=ACS Omega |date=2 June 2022 |volume=7 |issue=23 |pages=20053−20058 |doi=10.1021/acsomega.2c01884 |pmid=35722008 |pmc=9202248 |hdl=20.500.11850/554631 |url=https://doi.org/10.1021/acsomega.2c01884}}</ref> Curium is present in nature in some areas used for ].<ref name="lenntech"> (in German)</ref> Analysis of the debris at the test site of the ]' first ], ] |
Curium is made artificially in small amounts for research purposes. It also occurs as one of the waste products in ].<ref>{{cite journal |vauthors = Chaplin J, Warwick P, Cundy A, Bochud F, Froidevaux P |title=Novel DGT Configurations for the Assessment of Bioavailable Plutonium, Americium, and Uranium in Marine and Freshwater Environments |journal=Analytical Chemistry |date=25 August 2021 |volume=93 |issue=35 |pages=11937–11945 |doi=10.1021/acs.analchem.1c01342 |pmid=34432435 |s2cid=237307309 |doi-access=free }}</ref><ref>{{cite journal |vauthors = Chaplin J, Christl M, Straub M, Bochud F, Froidevaux P |title=Passive Sampling Tool for Actinides in Spent Nuclear Fuel Pools |journal=ACS Omega |date=2 June 2022 |volume=7 |issue=23 |pages=20053−20058 |doi=10.1021/acsomega.2c01884 |pmid=35722008 |pmc=9202248 |hdl=20.500.11850/554631 |url=https://doi.org/10.1021/acsomega.2c01884}}</ref> Curium is present in nature in some areas used for ].<ref name="lenntech"> (in German)</ref> Analysis of the debris at the test site of the ]' first ], ] (1 November 1952, ]), besides ], ], ] and ] also revealed isotopes of berkelium, californium and curium, in particular <sup>245</sup>Cm, <sup>246</sup>Cm and smaller quantities of <sup>247</sup>Cm, <sup>248</sup>Cm and <sup>249</sup>Cm.<ref>{{cite journal|last1=Fields|first1=P. R.|last2=Studier|first2=M. H.|last3=Diamond|first3=H.|last4=Mech|first4=J. F.|last5=Inghram|first5=M. G.|last6=Pyle|first6=G. L.|last7=Stevens|first7=C. M.|last8=Fried|first8=S.|last9=Manning|first9=W. M.|last10=Ghiorso|first10=A.|last11=Thompson|first11=S. G.|last12=Higgins|first12=G. H.|last13=Seaborg|first13=Glenn T.|display-authors=3|title=Transplutonium Elements in Thermonuclear Test Debris|date=1956|journal=Physical Review|volume=102|issue=1|pages=180–182|doi=10.1103/PhysRev.102.180|bibcode=1956PhRv..102..180F}}</ref> | ||
Atmospheric curium compounds are poorly soluble in common solvents and mostly adhere to soil particles. Soil analysis revealed about 4,000 times higher concentration of curium at the sandy soil particles than in water present in the soil pores. An even higher ratio of about 18,000 was measured in ] soils.<ref name="LA2" /> | Atmospheric curium compounds are poorly soluble in common solvents and mostly adhere to soil particles. Soil analysis revealed about 4,000 times higher concentration of curium at the sandy soil particles than in water present in the soil pores. An even higher ratio of about 18,000 was measured in ] soils.<ref name="LA2" /> | ||
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===Metal preparation=== | ===Metal preparation=== | ||
] ] curves revealing the similarity between Tb, Gd, Eu lanthanides and corresponding Bk, Cm, Am actinides |
] ] curves revealing the similarity between Tb, Gd, Eu lanthanides and corresponding Bk, Cm, Am actinides]] | ||
Most synthesis routines yield a mix of actinide isotopes as ]s, from which a given isotope of curium needs to be separated. An example procedure could be to dissolve spent reactor fuel (e.g. ]) in ], and remove the bulk of the uranium and plutonium using a ] ('''P'''lutonium – '''UR'''anium '''EX'''traction) type extraction with ] in a hydrocarbon. The lanthanides and the remaining actinides are then separated from the aqueous residue (]) by a diamide-based extraction to give, after stripping, a mixture of trivalent actinides and lanthanides. A curium compound is then selectively extracted using multi-step ] and centrifugation techniques with an appropriate reagent.<ref>Penneman, pp. 34–48</ref> ] complex has been recently proposed as such reagent which is highly selective to curium.<ref>{{cite journal|author = Magnusson D|author2 = Christiansen B|author3 = Foreman MRS|author4 = Geist A|author5 = Glatz JP|author6 = Malmbeck R|author7 = Modolo G|author8 = Serrano-Purroy D|author9 = Sorel C|name-list-style = amp|journal = Solvent Extraction and Ion Exchange|date = 2009|volume = 27|issue = 2|page = 97|doi = 10.1080/07366290802672204|title = Demonstration of a SANEX Process in Centrifugal Contactors using the CyMe4-BTBP Molecule on a Genuine Fuel Solution|title-link = centrifugal extractor|s2cid = 94720457}}</ref> Separation of curium from the very chemically similar americium can also be done by treating a slurry of their hydroxides in aqueous ] with ] at elevated temperature. Both americium and curium are present in solutions mostly in the +3 valence state; americium oxidizes to soluble Am(IV) complexes, but curium stays unchanged and so can be isolated by repeated centrifugation.<ref>Penneman, p. 25</ref> | Most synthesis routines yield a mix of actinide isotopes as ]s, from which a given isotope of curium needs to be separated. An example procedure could be to dissolve spent reactor fuel (e.g. ]) in ], and remove the bulk of the uranium and plutonium using a ] ('''P'''lutonium – '''UR'''anium '''EX'''traction) type extraction with ] in a hydrocarbon. The lanthanides and the remaining actinides are then separated from the aqueous residue (]) by a diamide-based extraction to give, after stripping, a mixture of trivalent actinides and lanthanides. A curium compound is then selectively extracted using multi-step ] and centrifugation techniques with an appropriate reagent.<ref>Penneman, pp. 34–48</ref> ] complex has been recently proposed as such reagent which is highly selective to curium.<ref>{{cite journal|author = Magnusson D|author2 = Christiansen B|author3 = Foreman MRS|author4 = Geist A|author5 = Glatz JP|author6 = Malmbeck R|author7 = Modolo G|author8 = Serrano-Purroy D|author9 = Sorel C|name-list-style = amp|journal = Solvent Extraction and Ion Exchange|date = 2009|volume = 27|issue = 2|page = 97|doi = 10.1080/07366290802672204|title = Demonstration of a SANEX Process in Centrifugal Contactors using the CyMe4-BTBP Molecule on a Genuine Fuel Solution|title-link = centrifugal extractor|s2cid = 94720457}}</ref> Separation of curium from the very chemically similar americium can also be done by treating a slurry of their hydroxides in aqueous ] with ] at elevated temperature. Both americium and curium are present in solutions mostly in the +3 valence state; americium oxidizes to soluble Am(IV) complexes, but curium stays unchanged and so can be isolated by repeated centrifugation.<ref>Penneman, p. 25</ref> | ||
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==Compounds and reactions== | ==Compounds and reactions== | ||
{{ |
{{Main|Curium compounds}} | ||
===Oxides=== | ===Oxides=== | ||
Curium readily reacts with oxygen forming mostly Cm<sub>2</sub>O<sub>3</sub> and CmO<sub>2</sub> oxides,<ref name="lenntech" /> but the divalent oxide CmO is also known.<ref name="HOWI_1972">Holleman, p. 1972</ref> Black CmO<sub>2</sub> can be obtained by burning curium ] ({{chem|Cm|2|(C|2|O|4|)|3}}), nitrate ({{chem|Cm|(N|O|3|)|3}}), or hydroxide in pure oxygen.<ref name="asprey" /><ref name="g1268">Greenwood, p. 1268</ref> Upon heating to 600–650 °C in vacuum (about 0.01 |
Curium readily reacts with oxygen forming mostly Cm<sub>2</sub>O<sub>3</sub> and CmO<sub>2</sub> oxides,<ref name="lenntech" /> but the divalent oxide CmO is also known.<ref name="HOWI_1972">Holleman, p. 1972</ref> Black CmO<sub>2</sub> can be obtained by burning curium ] ({{chem|Cm|2|(C|2|O|4|)|3}}), nitrate ({{chem|Cm|(N|O|3|)|3}}), or hydroxide in pure oxygen.<ref name="asprey" /><ref name="g1268">Greenwood, p. 1268</ref> Upon heating to 600–650 °C in vacuum (about 0.01 ]), it transforms into the whitish Cm<sub>2</sub>O<sub>3</sub>:<ref name="asprey">{{cite journal|last1=Asprey|first1=L. B.|title=Evidence for Quadrivalent Curium: X-Ray Data on Curium Oxides1|last2=Ellinger|first2=F. H.|last3=Fried|first3=S.|last4=Zachariasen|first4=W. H.|journal=Journal of the American Chemical Society|volume=77|issue=6|page=1707|date=1955|doi=10.1021/ja01611a108}}</ref><ref>{{cite journal|last1=Noe|first1=M.|title=Self-radiation effects on the lattice parameter of 244CmO2|journal=Inorganic and Nuclear Chemistry Letters|volume=7|issue=5|page=421|date=1971|doi=10.1016/0020-1650(71)80177-0|last2=Fuger|first2=J.}}</ref> | ||
: <chem>4CmO2 -> 2Cm2O3 + O2</chem>. | : <chem>4CmO2 -> 2Cm2O3 + O2</chem>. | ||
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Also, a number of ternary oxides of the type M(II)CmO<sub>3</sub> are known, where M stands for a divalent metal, such as barium.<ref>{{cite journal|last1=Fuger|first1=J.|last2=Haire|first2=R.|last3=Peterson|first3=J.|title=Molar enthalpies of formation of BaCmO3 and BaCfO3|journal=Journal of Alloys and Compounds|volume=200|issue=1–2|page=181|date=1993|doi=10.1016/0925-8388(93)90491-5|url=https://zenodo.org/record/1258637}}</ref> | Also, a number of ternary oxides of the type M(II)CmO<sub>3</sub> are known, where M stands for a divalent metal, such as barium.<ref>{{cite journal|last1=Fuger|first1=J.|last2=Haire|first2=R.|last3=Peterson|first3=J.|title=Molar enthalpies of formation of BaCmO3 and BaCfO3|journal=Journal of Alloys and Compounds|volume=200|issue=1–2|page=181|date=1993|doi=10.1016/0925-8388(93)90491-5|url=https://zenodo.org/record/1258637}}</ref> | ||
Thermal oxidation of trace quantities of curium hydride (CmH<sub>2–3</sub>) has been reported to give a volatile form of CmO<sub>2</sub> and the volatile trioxide CmO<sub>3</sub>, one of two known examples of the very rare +6 state for curium.<ref name="CmO3" /> Another observed species was reported to behave similar to a supposed plutonium tetroxide and was tentatively characterized as CmO<sub>4</sub>, with curium in the extremely rare +8 state;<ref name="CmO4">{{cite journal |last1=Domanov |first1=V. P. |date=January 2013 |title=Possibility of generation of octavalent curium in the gas phase in the form of volatile tetraoxide CmO<sub>4</sub> |journal=Radiochemistry |volume=55 |issue=1 |pages=46–51 |doi=10.1134/S1066362213010098 |s2cid=98076989 }}</ref> but new experiments seem to indicate that CmO<sub>4</sub> does not exist, and have cast doubt on the existence of PuO<sub>4</sub> as well.<ref>{{cite journal|last1=Zaitsevskii|first1=Andréi|last2=Schwarz|first2=W. H. Eugen|date=April 2014|title=Structures and stability of AnO4 isomers, An = Pu, Am, and Cm: a relativistic density functional study.|journal=Physical Chemistry Chemical Physics|volume=2014|issue=16|pages=8997–9001|bibcode=2014PCCP...16.8997Z|doi=10.1039/c4cp00235k|pmid=24695756}}<!--|access-date=March 8, 2015--></ref> | Thermal oxidation of trace quantities of curium hydride (CmH<sub>2–3</sub>) has been reported to give a volatile form of CmO<sub>2</sub> and the volatile trioxide CmO<sub>3</sub>, one of two known examples of the very rare +6 state for curium.<ref name="CmO3" /> Another observed species was reported to behave similar to a supposed plutonium tetroxide and was tentatively characterized as CmO<sub>4</sub>, with curium in the extremely rare +8 state;<ref name="CmO4">{{cite journal |last1=Domanov |first1=V. P. |date=January 2013 |title=Possibility of generation of octavalent curium in the gas phase in the form of volatile tetraoxide CmO<sub>4</sub> |journal=Radiochemistry |volume=55 |issue=1 |pages=46–51 |doi=10.1134/S1066362213010098 |bibcode=2013Radch..55...46D |s2cid=98076989 }}</ref> but new experiments seem to indicate that CmO<sub>4</sub> does not exist, and have cast doubt on the existence of PuO<sub>4</sub> as well.<ref>{{cite journal|last1=Zaitsevskii|first1=Andréi|last2=Schwarz|first2=W. H. Eugen|date=April 2014|title=Structures and stability of AnO4 isomers, An = Pu, Am, and Cm: a relativistic density functional study.|journal=Physical Chemistry Chemical Physics|volume=2014|issue=16|pages=8997–9001|bibcode=2014PCCP...16.8997Z|doi=10.1039/c4cp00235k|pmid=24695756}}<!--|access-date=March 8, 2015--></ref> | ||
===Halides=== | ===Halides=== | ||
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A series of ternary fluorides are known of the form A<sub>7</sub>Cm<sub>6</sub>F<sub>31</sub> (A = ]).<ref>{{cite journal|last1=Keenan|first1=T.|title=Lattice constants of K7Cm6F31 trends in the 1:1 and 7:6 alkali metal-actinide(IV) series|journal=Inorganic and Nuclear Chemistry Letters|volume=3|issue=10|page=391|date=1967|doi=10.1016/0020-1650(67)80092-8}}</ref> | A series of ternary fluorides are known of the form A<sub>7</sub>Cm<sub>6</sub>F<sub>31</sub> (A = ]).<ref>{{cite journal|last1=Keenan|first1=T.|title=Lattice constants of K7Cm6F31 trends in the 1:1 and 7:6 alkali metal-actinide(IV) series|journal=Inorganic and Nuclear Chemistry Letters|volume=3|issue=10|page=391|date=1967|doi=10.1016/0020-1650(67)80092-8}}</ref> | ||
The colorless ] (CmCl<sub>3</sub>) is made by reacting ] (Cm(OH)<sub>3</sub>) with anhydrous ] gas. It can be further turned into other halides such as curium(III) bromide (colorless to light green) and ] (colorless), by reacting it with the ] salt of the corresponding halide at temperatures of ~400–450°C:<ref>{{cite journal|title=Crystal Structures of the Trifluorides, Trichlorides, Tribromides, and Triiodides of Americium and Curium|last1=Asprey|first1=L. B.|last2=Keenan|first2=T. K.|last3=Kruse|first3=F. H.|journal=Inorganic Chemistry|volume=4|issue=7|page=985|date=1965|doi=10.1021/ic50029a013|s2cid=96551460 |url=https://digital.library.unt.edu/ark:/67531/metadc1035960/}}</ref> | The colorless ] (CmCl<sub>3</sub>) is made by reacting ] (Cm(OH)<sub>3</sub>) with anhydrous ] gas. It can be further turned into other halides such as curium(III) bromide (colorless to light green) and ] (colorless), by reacting it with the ] salt of the corresponding halide at temperatures of ~400–450 °C:<ref>{{cite journal|title=Crystal Structures of the Trifluorides, Trichlorides, Tribromides, and Triiodides of Americium and Curium|last1=Asprey|first1=L. B.|last2=Keenan|first2=T. K.|last3=Kruse|first3=F. H.|journal=Inorganic Chemistry|volume=4|issue=7|page=985|date=1965|doi=10.1021/ic50029a013|s2cid=96551460 |url=https://digital.library.unt.edu/ark:/67531/metadc1035960/}}</ref> | ||
: <math>\mathrm{CmCl_3\ +\ 3\ NH_4I\ \longrightarrow \ CmI_3\ +\ 3\ NH_4Cl}</math> | : <math>\mathrm{CmCl_3\ +\ 3\ NH_4I\ \longrightarrow \ CmI_3\ +\ 3\ NH_4Cl}</math> | ||
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Formation of the complexes of the type {{chem|Cm|(|n-C|3|H|7|-BTP)|3}} (BTP = 2,6-di(1,2,4-triazin-3-yl)pyridine), in solutions containing n-C<sub>3</sub>H<sub>7</sub>-BTP and Cm<sup>3+</sup> ions has been confirmed by ]. Some of these BTP-type complexes selectively interact with curium and thus are useful for separating it from lanthanides and another actinides.<ref name="denecke" /><ref>{{cite journal|last1=Girnt|first1=Denise|last2=Roesky|first2=Peter W.|last3=Geist|first3=Andreas|last4=Ruff|first4=Christian M.|last5=Panak|first5=Petra J.|last6=Denecke|first6=Melissa A.|s2cid=978265|title=6-(3,5-Dimethyl-1H-pyrazol-1-yl)-2,2′-bipyridine as Ligand for Actinide(III)/Lanthanide(III) Separation|journal=Inorganic Chemistry|volume=49|issue=20|date=2010|pmid=20849125|doi=10.1021/ic101309j|pages=9627–9635}}</ref> Dissolved Cm<sup>3+</sup> ions bind with many organic compounds, such as ],<ref name="pl1">{{cite journal|last1=Glorius|first1=M.|last2=Moll|first2=H.|last3=Bernhard|first3=G.|title=Complexation of curium(III) with hydroxamic acids investigated by time-resolved laser-induced fluorescence spectroscopy|journal=Polyhedron|volume=27|issue=9–10|page=2113|date=2008|doi=10.1016/j.poly.2008.04.002}}</ref> ],<ref name="pl2">{{cite journal|last1=Heller|first1=Anne|last2=Barkleit|first2=Astrid|last3=Bernhard|first3=Gert|last4=Ackermann|first4=Jörg-Uwe|title=Complexation study of europium(III) and curium(III) with urea in aqueous solution investigated by time-resolved laser-induced fluorescence spectroscopy|journal=Inorganica Chimica Acta|volume=362|issue=4|page=1215|date=2009|doi=10.1016/j.ica.2008.06.016}}</ref> ]<ref name="pl3">{{cite journal|last1=Moll|first1=Henry|last2=Johnsson|first2=Anna|last3=Schäfer|first3=Mathias|last4=Pedersen|first4=Karsten|last5=Budzikiewicz|first5=Herbert|last6=Bernhard|first6=Gert|title=Curium(III) complexation with pyoverdins secreted by a groundwater strain of Pseudomonas fluorescens|journal=BioMetals|volume=21|issue=2|date=2007|pmid=17653625|doi=10.1007/s10534-007-9111-x|pages=219–228|s2cid=24565144}}</ref> and ].<ref name="pl4">{{cite journal|last1=Moll|first1=Henry|last2=Geipel|first2=Gerhard|last3=Bernhard|first3=Gert|title=Complexation of curium(III) by adenosine 5′-triphosphate (ATP): A time-resolved laser-induced fluorescence spectroscopy (TRLFS) study|journal=Inorganica Chimica Acta|volume=358|issue=7|page=2275|date=2005|doi=10.1016/j.ica.2004.12.055}}</ref> Many of these compounds are related to biological activity of various ]s. The resulting complexes show strong yellow-orange emission under UV light excitation, which is convenient not only for their detection, but also for studying interactions between the Cm<sup>3+</sup> ion and the ligands via changes in the half-life (of the order ~0.1 ms) and spectrum of the fluorescence.<ref name="plb" /><ref name="pl1" /><ref name="pl2" /><ref name="pl3" /><ref name="pl4" /> | Formation of the complexes of the type {{chem|Cm|(|n-C|3|H|7|-BTP)|3}} (BTP = 2,6-di(1,2,4-triazin-3-yl)pyridine), in solutions containing n-C<sub>3</sub>H<sub>7</sub>-BTP and Cm<sup>3+</sup> ions has been confirmed by ]. Some of these BTP-type complexes selectively interact with curium and thus are useful for separating it from lanthanides and another actinides.<ref name="denecke" /><ref>{{cite journal|last1=Girnt|first1=Denise|last2=Roesky|first2=Peter W.|last3=Geist|first3=Andreas|last4=Ruff|first4=Christian M.|last5=Panak|first5=Petra J.|last6=Denecke|first6=Melissa A.|s2cid=978265|title=6-(3,5-Dimethyl-1H-pyrazol-1-yl)-2,2′-bipyridine as Ligand for Actinide(III)/Lanthanide(III) Separation|journal=Inorganic Chemistry|volume=49|issue=20|date=2010|pmid=20849125|doi=10.1021/ic101309j|pages=9627–9635}}</ref> Dissolved Cm<sup>3+</sup> ions bind with many organic compounds, such as ],<ref name="pl1">{{cite journal|last1=Glorius|first1=M.|last2=Moll|first2=H.|last3=Bernhard|first3=G.|title=Complexation of curium(III) with hydroxamic acids investigated by time-resolved laser-induced fluorescence spectroscopy|journal=Polyhedron|volume=27|issue=9–10|page=2113|date=2008|doi=10.1016/j.poly.2008.04.002}}</ref> ],<ref name="pl2">{{cite journal|last1=Heller|first1=Anne|last2=Barkleit|first2=Astrid|last3=Bernhard|first3=Gert|last4=Ackermann|first4=Jörg-Uwe|title=Complexation study of europium(III) and curium(III) with urea in aqueous solution investigated by time-resolved laser-induced fluorescence spectroscopy|journal=Inorganica Chimica Acta|volume=362|issue=4|page=1215|date=2009|doi=10.1016/j.ica.2008.06.016}}</ref> ]<ref name="pl3">{{cite journal|last1=Moll|first1=Henry|last2=Johnsson|first2=Anna|last3=Schäfer|first3=Mathias|last4=Pedersen|first4=Karsten|last5=Budzikiewicz|first5=Herbert|last6=Bernhard|first6=Gert|title=Curium(III) complexation with pyoverdins secreted by a groundwater strain of Pseudomonas fluorescens|journal=BioMetals|volume=21|issue=2|date=2007|pmid=17653625|doi=10.1007/s10534-007-9111-x|pages=219–228|s2cid=24565144}}</ref> and ].<ref name="pl4">{{cite journal|last1=Moll|first1=Henry|last2=Geipel|first2=Gerhard|last3=Bernhard|first3=Gert|title=Complexation of curium(III) by adenosine 5′-triphosphate (ATP): A time-resolved laser-induced fluorescence spectroscopy (TRLFS) study|journal=Inorganica Chimica Acta|volume=358|issue=7|page=2275|date=2005|doi=10.1016/j.ica.2004.12.055}}</ref> Many of these compounds are related to biological activity of various ]s. The resulting complexes show strong yellow-orange emission under UV light excitation, which is convenient not only for their detection, but also for studying interactions between the Cm<sup>3+</sup> ion and the ligands via changes in the half-life (of the order ~0.1 ms) and spectrum of the fluorescence.<ref name="plb" /><ref name="pl1" /><ref name="pl2" /><ref name="pl3" /><ref name="pl4" /> | ||
There are a few reports on ] of Cm<sup>3+</sup> by ] and ],<ref>{{cite journal|doi=10.1021/es0301166|last1=Moll|first1=H.|last2=Stumpf|first2=T.|last3=Merroun|first3=M.|last4=Rossberg|first4=A.|last5=Selenska-Pobell|first5=S.|last6=Bernhard|first6=G.|title=Time-resolved laser fluorescence spectroscopy study on the interaction of curium(III) with Desulfovibrio äspöensis DSM 10631T|journal=Environmental Science & Technology|volume=38|issue=5|pages=1455–1459|date=2004|pmid=15046347|bibcode = 2004EnST...38.1455M }}</ref><ref>{{cite journal|author=Ozaki, T.|display-authors=etal|url=http://sciencelinks.jp/j-east/article/200305/000020030503A0110480.php|archive-url=https://web.archive.org/web/20090225195752/http://sciencelinks.jp/j-east/article/200305/000020030503A0110480.php|url-status=dead|archive-date=2009-02-25|title=Association of Eu(III) and Cm(III) with Bacillus subtilis and Halobacterium salinarium|journal=Journal of Nuclear Science and Technology|date=2002|volume=Suppl. 3|pages=950–953|doi=10.1080/00223131.2002.10875626|bibcode=2002JNST...39S.950O |s2cid=98319565}}</ref> and in the laboratory both americium and curium were found to support the growth of ]s.<ref>{{cite journal |last1=Remick |first1=Kaleigh |last2=Helmann |first2=John D. |title=The Elements of Life: A Biocentric Tour of the Periodic Table |journal=Advances in Microbial Physiology |publisher=PubMed Central |date=30 January 2023 |volume=82 |pages=1–127 |doi=10.1016/bs.ampbs.2022.11.001 |pmid=36948652 |pmc=10727122 |isbn=978-0-443-19334-7}}</ref> | |||
==Applications== | ==Applications== | ||
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==Safety== | ==Safety== | ||
Due to its radioactivity, curium and its compounds must be handled in appropriate labs under special arrangements. While curium itself mostly emits α-particles which are absorbed by thin layers of common materials, some of its decay products emit significant fractions of beta and gamma rays, which require a more elaborate protection.<ref name="lenntech" /> If consumed, curium is excreted within a few days and only 0.05% is absorbed in the blood. From there, ~45% goes to the ], 45% to the bones, and the remaining 10% is excreted. In bone, curium accumulates on the inside of the interfaces to the ] and does not significantly redistribute with time; its radiation destroys bone marrow and thus stops ] creation. The ] of curium is about 20 years in the liver and 50 years in the bones.<ref name="lenntech" /><ref name="LA2" /> Curium is absorbed in the body much more strongly via inhalation, and the allowed total dose of <sup>244</sup>Cm in soluble form is 0.3 |
Due to its radioactivity, curium and its compounds must be handled in appropriate labs under special arrangements. While curium itself mostly emits α-particles which are absorbed by thin layers of common materials, some of its decay products emit significant fractions of beta and gamma rays, which require a more elaborate protection.<ref name="lenntech" /> If consumed, curium is excreted within a few days and only 0.05% is absorbed in the blood. From there, ~45% goes to the ], 45% to the bones, and the remaining 10% is excreted. In bone, curium accumulates on the inside of the interfaces to the ] and does not significantly redistribute with time; its radiation destroys bone marrow and thus stops ] creation. The ] of curium is about 20 years in the liver and 50 years in the bones.<ref name="lenntech" /><ref name="LA2" /> Curium is absorbed in the body much more strongly via inhalation, and the allowed total dose of <sup>244</sup>Cm in soluble form is 0.3 μ].<ref name="CRC" /> Intravenous injection of <sup>242</sup>Cm- and <sup>244</sup>Cm-containing solutions to rats increased the incidence of ], and inhalation promoted ] and ].<ref name="lenntech" /> | ||
Curium isotopes are inevitably present in spent nuclear fuel (about 20 g/tonne).<ref>Hoffmann, K. ''Kann man Gold machen? Gauner, Gaukler und Gelehrte. Aus der Geschichte der chemischen Elemente'' (Can you make gold? Crooks, clowns and scholars. From the history of the chemical elements), Urania-Verlag, Leipzig, Jena, Berlin 1979, no ISBN, p. 233</ref> The isotopes <sup>245</sup>Cm–<sup>248</sup>Cm have decay times of thousands of years and must be removed to neutralize the fuel for disposal.<ref>Baetslé, L. H. {{Webarchive|url=https://web.archive.org/web/20050426092418/http://www.ictp.trieste.it/~pub_off/lectures/lns012/Baetsle.pdf |date=2005-04-26 }}, Nuclear Research Centre of Belgium Sck/Cen, Mol, Belgium, September 2001.</ref> Such a procedure involves several steps, where curium is first separated and then converted by neutron bombardment in special reactors to short-lived nuclides. This procedure, ], while well documented for other elements, is still being developed for curium.<ref name="denecke" /> | Curium isotopes are inevitably present in spent nuclear fuel (about 20 g/tonne).<ref>Hoffmann, K. ''Kann man Gold machen? Gauner, Gaukler und Gelehrte. Aus der Geschichte der chemischen Elemente'' (Can you make gold? Crooks, clowns and scholars. From the history of the chemical elements), Urania-Verlag, Leipzig, Jena, Berlin 1979, no ISBN, p. 233</ref> The isotopes <sup>245</sup>Cm–<sup>248</sup>Cm have decay times of thousands of years and must be removed to neutralize the fuel for disposal.<ref>Baetslé, L. H. {{Webarchive|url=https://web.archive.org/web/20050426092418/http://www.ictp.trieste.it/~pub_off/lectures/lns012/Baetsle.pdf |date=2005-04-26 }}, Nuclear Research Centre of Belgium Sck/Cen, Mol, Belgium, September 2001.</ref> Such a procedure involves several steps, where curium is first separated and then converted by neutron bombardment in special reactors to short-lived nuclides. This procedure, ], while well documented for other elements, is still being developed for curium.<ref name="denecke" /> | ||
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==External links== | ==External links== | ||
{{Commons |
{{Commons}} | ||
{{wiktionary|curium}} | {{wiktionary|curium}} | ||
* at '']'' (University of Nottingham) | * at '']'' (University of Nottingham) | ||
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{{Curium compounds}} | {{Curium compounds}} | ||
{{Nuclear Technology}} | {{Nuclear Technology}} | ||
⚫ | {{Marie & Pierre Curie}} | ||
{{Authority control}} | {{Authority control}} | ||
⚫ | {{Marie & Pierre Curie}} | ||
] | ] |
Latest revision as of 09:33, 25 November 2024
Not to be confused with cerium. This article is about the chemical element. For the ancient city located in Cyprus, see Kourion.Chemical element with atomic number 96 (Cm)
Curium is a synthetic chemical element; it has symbol Cm and atomic number 96. This transuranic actinide element was named after eminent scientists Marie and Pierre Curie, both known for their research on radioactivity. Curium was first intentionally made by the team of Glenn T. Seaborg, Ralph A. James, and Albert Ghiorso in 1944, using the cyclotron at Berkeley. They bombarded the newly discovered element plutonium (the isotope Pu) with alpha particles. This was then sent to the Metallurgical Laboratory at University of Chicago where a tiny sample of curium was eventually separated and identified. The discovery was kept secret until after the end of World War II. The news was released to the public in November 1947. Most curium is produced by bombarding uranium or plutonium with neutrons in nuclear reactors – one tonne of spent nuclear fuel contains ~20 grams of curium.
Curium is a hard, dense, silvery metal with a high melting and boiling point for an actinide. It is paramagnetic at ambient conditions, but becomes antiferromagnetic upon cooling, and other magnetic transitions are also seen in many curium compounds. In compounds, curium usually has valence +3 and sometimes +4; the +3 valence is predominant in solutions. Curium readily oxidizes, and its oxides are a dominant form of this element. It forms strongly fluorescent complexes with various organic compounds. If it gets into the human body, curium accumulates in bones, lungs, and liver, where it promotes cancer.
All known isotopes of curium are radioactive and have small critical mass for a nuclear chain reaction. The most stable isotope, Cm, has a half-life of 15.6 million years; the longest-lived curium isotopes predominantly emit alpha particles. Radioisotope thermoelectric generators can use the heat from this process, but this is hindered by the rarity and high cost of curium. Curium is used in making heavier actinides and the Pu radionuclide for power sources in artificial cardiac pacemakers and RTGs for spacecraft. It served as the α-source in the alpha particle X-ray spectrometers of several space probes, including the Sojourner, Spirit, Opportunity, and Curiosity Mars rovers and the Philae lander on comet 67P/Churyumov–Gerasimenko, to analyze the composition and structure of the surface.
History
Though curium had likely been produced in previous nuclear experiments as well as the natural nuclear fission reactor at Oklo, Gabon, it was first intentionally synthesized, isolated and identified in 1944, at University of California, Berkeley, by Glenn T. Seaborg, Ralph A. James, and Albert Ghiorso. In their experiments, they used a 60-inch (150 cm) cyclotron.
Curium was chemically identified at the Metallurgical Laboratory (now Argonne National Laboratory), University of Chicago. It was the third transuranium element to be discovered even though it is the fourth in the series – the lighter element americium was still unknown.
The sample was prepared as follows: first plutonium nitrate solution was coated on a platinum foil of ~0.5 cm area, the solution was evaporated and the residue was converted into plutonium(IV) oxide (PuO2) by annealing. Following cyclotron irradiation of the oxide, the coating was dissolved with nitric acid and then precipitated as the hydroxide using concentrated aqueous ammonia solution. The residue was dissolved in perchloric acid, and further separation was done by ion exchange to yield a certain isotope of curium. The separation of curium and americium was so painstaking that the Berkeley group initially called those elements pandemonium (from Greek for all demons or hell) and delirium (from Latin for madness).
Curium-242 was made in July–August 1944 by bombarding Pu with α-particles to produce curium with the release of a neutron:
Curium-242 was unambiguously identified by the characteristic energy of the α-particles emitted during the decay:
The half-life of this alpha decay was first measured as 5 months (150 days) and then corrected to 162.8 days.
Another isotope Cm was produced in a similar reaction in March 1945:
The α-decay half-life of Cm was determined as 26.8 days and later revised to 30.4 days.
The discovery of curium and americium in 1944 was closely related to the Manhattan Project, so the results were confidential and declassified only in 1945. Seaborg leaked the synthesis of the elements 95 and 96 on the U.S. radio show for children, the Quiz Kids, five days before the official presentation at an American Chemical Society meeting on November 11, 1945, when one listener asked if any new transuranic element beside plutonium and neptunium had been discovered during the war. The discovery of curium (Cm and Cm), its production, and its compounds was later patented listing only Seaborg as the inventor.
Marie and Pierre CurieThe element was named after Marie Curie and her husband Pierre Curie, who are known for discovering radium and for their work in radioactivity. It followed the example of gadolinium, a lanthanide element above curium in the periodic table, which was named after the explorer of rare-earth elements Johan Gadolin:
As the name for the element of atomic number 96 we should like to propose "curium", with symbol Cm. The evidence indicates that element 96 contains seven 5f electrons and is thus analogous to the element gadolinium, with its seven 4f electrons in the regular rare earth series. On this basis element 96 is named after the Curies in a manner analogous to the naming of gadolinium, in which the chemist Gadolin was honored.
The first curium samples were barely visible, and were identified by their radioactivity. Louis Werner and Isadore Perlman made the first substantial sample of 30 μg curium-242 hydroxide at University of California, Berkeley in 1947 by bombarding americium-241 with neutrons. Macroscopic amounts of curium(III) fluoride were obtained in 1950 by W. W. T. Crane, J. C. Wallmann and B. B. Cunningham. Its magnetic susceptibility was very close to that of GdF3 providing the first experimental evidence for the +3 valence of curium in its compounds. Curium metal was produced only in 1951 by reduction of CmF3 with barium.
Characteristics
Physical
A synthetic, radioactive element, curium is a hard, dense metal with a silvery-white appearance and physical and chemical properties resembling gadolinium. Its melting point of 1344 °C is significantly higher than that of the previous elements neptunium (637 °C), plutonium (639 °C) and americium (1176 °C). In comparison, gadolinium melts at 1312 °C. Curium boils at 3556 °C. With a density of 13.52 g/cm, curium is lighter than neptunium (20.45 g/cm) and plutonium (19.8 g/cm), but heavier than most other metals. Of two crystalline forms of curium, α-Cm is more stable at ambient conditions. It has a hexagonal symmetry, space group P63/mmc, lattice parameters a = 365 pm and c = 1182 pm, and four formula units per unit cell. The crystal consists of double-hexagonal close packing with the layer sequence ABAC and so is isotypic with α-lanthanum. At pressure >23 GPa, at room temperature, α-Cm becomes β-Cm, which has face-centered cubic symmetry, space group Fm3m and lattice constant a = 493 pm. On further compression to 43 GPa, curium becomes an orthorhombic γ-Cm structure similar to α-uranium, with no further transitions observed up to 52 GPa. These three curium phases are also called Cm I, II and III.
Curium has peculiar magnetic properties. Its neighbor element americium shows no deviation from Curie-Weiss paramagnetism in the entire temperature range, but α-Cm transforms to an antiferromagnetic state upon cooling to 65–52 K, and β-Cm exhibits a ferrimagnetic transition at ~205 K. Curium pnictides show ferromagnetic transitions upon cooling: CmN and CmAs at 109 K, CmP at 73 K and CmSb at 162 K. The lanthanide analog of curium, gadolinium, and its pnictides, also show magnetic transitions upon cooling, but the transition character is somewhat different: Gd and GdN become ferromagnetic, and GdP, GdAs and GdSb show antiferromagnetic ordering.
In accordance with magnetic data, electrical resistivity of curium increases with temperature – about twice between 4 and 60 K – and then is nearly constant up to room temperature. There is a significant increase in resistivity over time (~10 μΩ·cm/h) due to self-damage of the crystal lattice by alpha decay. This makes uncertain the true resistivity of curium (~125 μΩ·cm). Curium's resistivity is similar to that of gadolinium, and the actinides plutonium and neptunium, but significantly higher than that of americium, uranium, polonium and thorium.
Under ultraviolet illumination, curium(III) ions show strong and stable yellow-orange fluorescence with a maximum in the range of 590–640 nm depending on their environment. The fluorescence originates from the transitions from the first excited state D7/2 and the ground state S7/2. Analysis of this fluorescence allows monitoring interactions between Cm(III) ions in organic and inorganic complexes.
Chemical
Curium ion in solution almost always has a +3 oxidation state, the most stable oxidation state for curium. A +4 oxidation state is seen mainly in a few solid phases, such as CmO2 and CmF4. Aqueous curium(IV) is only known in the presence of strong oxidizers such as potassium persulfate, and is easily reduced to curium(III) by radiolysis and even by water itself. Chemical behavior of curium is different from the actinides thorium and uranium, and is similar to americium and many lanthanides. In aqueous solution, the Cm ion is colorless to pale green; Cm ion is pale yellow. The optical absorption of Cm ion contains three sharp peaks at 375.4, 381.2 and 396.5 nm and their strength can be directly converted into the concentration of the ions. The +6 oxidation state has only been reported once in solution in 1978, as the curyl ion (CmO
2): this was prepared from beta decay of americium-242 in the americium(V) ion
AmO
2. Failure to get Cm(VI) from oxidation of Cm(III) and Cm(IV) may be due to the high Cm/Cm ionization potential and the instability of Cm(V).
Curium ions are hard Lewis acids and thus form most stable complexes with hard bases. The bonding is mostly ionic, with a small covalent component. Curium in its complexes commonly exhibits a 9-fold coordination environment, with a tricapped trigonal prismatic molecular geometry.
Isotopes
See also: Isotopes of curiumAbout 19 radioisotopes and 7 nuclear isomers, Cm to Cm, are known; none are stable. The longest half-lives are 15.6 million years (Cm) and 348,000 years (Cm). Other long-lived ones are Cm (8500 years), Cm (8300 years) and Cm (4760 years). Curium-250 is unusual: it mostly (~86%) decays by spontaneous fission. The most commonly used isotopes are Cm and Cm with the half-lives 162.8 days and 18.11 years, respectively.
Thermal neutron cross sections (barns) | ||||||
---|---|---|---|---|---|---|
Cm | Cm | Cm | Cm | Cm | Cm | |
Fission | 5 | 617 | 1.04 | 2145 | 0.14 | 81.90 |
Capture | 16 | 130 | 15.20 | 369 | 1.22 | 57 |
C/F ratio | 3.20 | 0.21 | 14.62 | 0.17 | 8.71 | 0.70 |
LEU spent nuclear fuel 20 years after 53 MWd/kg burnup | ||||||
3 common isotopes | 51 | 3700 | 390 | |||
Fast-neutron reactor MOX fuel (avg 5 samples, burnup 66–120 GWd/t) | ||||||
Total curium 3.09×10% | 27.64% | 70.16% | 2.166% | 0.0376% | 0.000928% |
Isotope | Cm | Cm | Cm | Cm | Cm | Cm | Cm | Cm |
Critical mass, kg | 25 | 7.5 | 33 | 6.8 | 39 | 7 | 40.4 | 23.5 |
All isotopes ranging from Cm to Cm, as well as Cm, undergo a self-sustaining nuclear chain reaction and thus in principle can be a nuclear fuel in a reactor. As in most transuranic elements, nuclear fission cross section is especially high for the odd-mass curium isotopes Cm, Cm and Cm. These can be used in thermal-neutron reactors, whereas a mixture of curium isotopes is only suitable for fast breeder reactors since the even-mass isotopes are not fissile in a thermal reactor and accumulate as burn-up increases. The mixed-oxide (MOX) fuel, which is to be used in power reactors, should contain little or no curium because neutron activation of Cm will create californium. Californium is a strong neutron emitter, and would pollute the back end of the fuel cycle and increase the dose to reactor personnel. Hence, if minor actinides are to be used as fuel in a thermal neutron reactor, the curium should be excluded from the fuel or placed in special fuel rods where it is the only actinide present.
The adjacent table lists the critical masses for curium isotopes for a sphere, without moderator or reflector. With a metal reflector (30 cm of steel), the critical masses of the odd isotopes are about 3–4 kg. When using water (thickness ~20–30 cm) as the reflector, the critical mass can be as small as 59 grams for Cm, 155 grams for Cm and 1550 grams for Cm. There is significant uncertainty in these critical mass values. While it is usually on the order of 20%, the values for Cm and Cm were listed as large as 371 kg and 70.1 kg, respectively, by some research groups.
Curium is not currently used as nuclear fuel due to its low availability and high price. Cm and Cm have very small critical mass and so could be used in tactical nuclear weapons, but none are known to have been made. Curium-243 is not suitable for such, due to its short half-life and strong α emission, which would cause excessive heat. Curium-247 would be highly suitable due to its long half-life, which is 647 times longer than plutonium-239 (used in many existing nuclear weapons).
Occurrence
The longest-lived isotope, Cm, has half-life 15.6 million years; so any primordial curium, that is, present on Earth when it formed, should have decayed by now. Its past presence as an extinct radionuclide is detectable as an excess of its primordial, long-lived daughter U. Traces of Cm may occur naturally in uranium minerals due to neutron capture and beta decay (U → Pu → Pu → Am → Cm), though the quantities would be tiny and this has not been confirmed: even with "extremely generous" estimates for neutron absorption possibilities, the quantity of Cm present in 1 × 10 kg of 18% uranium pitchblende would not even be one atom. Traces of Cm are also probably brought to Earth in cosmic rays, but this also has not been confirmed. There is also the possibility of Cm being produced as the double beta decay daughter of natural Pu.
Curium is made artificially in small amounts for research purposes. It also occurs as one of the waste products in spent nuclear fuel. Curium is present in nature in some areas used for nuclear weapons testing. Analysis of the debris at the test site of the United States' first thermonuclear weapon, Ivy Mike (1 November 1952, Enewetak Atoll), besides einsteinium, fermium, plutonium and americium also revealed isotopes of berkelium, californium and curium, in particular Cm, Cm and smaller quantities of Cm, Cm and Cm.
Atmospheric curium compounds are poorly soluble in common solvents and mostly adhere to soil particles. Soil analysis revealed about 4,000 times higher concentration of curium at the sandy soil particles than in water present in the soil pores. An even higher ratio of about 18,000 was measured in loam soils.
The transuranium elements from americium to fermium, including curium, occurred naturally in the natural nuclear fission reactor at Oklo, but no longer do so.
Curium, and other non-primordial actinides, have also been suspected to exist in the spectrum of Przybylski's Star.
Synthesis
Isotope preparation
Curium is made in small amounts in nuclear reactors, and by now only kilograms of Cm and Cm have been accumulated, and grams or even milligrams for heavier isotopes. Hence the high price of curium, which has been quoted at 160–185 USD per milligram, with a more recent estimate at US$2,000/g for Cm and US$170/g for Cm. In nuclear reactors, curium is formed from U in a series of nuclear reactions. In the first chain, U captures a neutron and converts into U, which via β decay transforms into Np and Pu.
(the times are half-lives). | (1) |
Further neutron capture followed by β-decay gives americium (Am) which further becomes Cm:
. | (2) |
For research purposes, curium is obtained by irradiating not uranium but plutonium, which is available in large amounts from spent nuclear fuel. A much higher neutron flux is used for the irradiation that results in a different reaction chain and formation of Cm:
(3) |
Curium-244 alpha decays to Pu, but it also absorbs neutrons, hence a small amount of heavier curium isotopes. Of those, Cm and Cm are popular in scientific research due to their long half-lives. But the production rate of Cm in thermal neutron reactors is low because it is prone to fission due to thermal neutrons. Synthesis of Cm by neutron capture is unlikely due to the short half-life of the intermediate Cm (64 min), which β decays to the berkelium isotope Bk.
(4) |
The above cascade of (n,γ) reactions gives a mix of different curium isotopes. Their post-synthesis separation is cumbersome, so a selective synthesis is desired. Curium-248 is favored for research purposes due to its long half-life. The most efficient way to prepare this isotope is by α-decay of the californium isotope Cf, which is available in relatively large amounts due to its long half-life (2.65 years). About 35–50 mg of Cm is produced thus, per year. The associated reaction produces Cm with isotopic purity of 97%.
(5) |
Another isotope, Cm, can be obtained for research, from α-decay of Cf; the latter isotope is produced in small amounts from β-decay of Bk.
(6) |
Metal preparation
Most synthesis routines yield a mix of actinide isotopes as oxides, from which a given isotope of curium needs to be separated. An example procedure could be to dissolve spent reactor fuel (e.g. MOX fuel) in nitric acid, and remove the bulk of the uranium and plutonium using a PUREX (Plutonium – URanium EXtraction) type extraction with tributyl phosphate in a hydrocarbon. The lanthanides and the remaining actinides are then separated from the aqueous residue (raffinate) by a diamide-based extraction to give, after stripping, a mixture of trivalent actinides and lanthanides. A curium compound is then selectively extracted using multi-step chromatographic and centrifugation techniques with an appropriate reagent. Bis-triazinyl bipyridine complex has been recently proposed as such reagent which is highly selective to curium. Separation of curium from the very chemically similar americium can also be done by treating a slurry of their hydroxides in aqueous sodium bicarbonate with ozone at elevated temperature. Both americium and curium are present in solutions mostly in the +3 valence state; americium oxidizes to soluble Am(IV) complexes, but curium stays unchanged and so can be isolated by repeated centrifugation.
Metallic curium is obtained by reduction of its compounds. Initially, curium(III) fluoride was used for this purpose. The reaction was done in an environment free of water and oxygen, in an apparatus made of tantalum and tungsten, using elemental barium or lithium as reducing agents.
Another possibility is reduction of curium(IV) oxide using a magnesium-zinc alloy in a melt of magnesium chloride and magnesium fluoride.
Compounds and reactions
Main article: Curium compoundsOxides
Curium readily reacts with oxygen forming mostly Cm2O3 and CmO2 oxides, but the divalent oxide CmO is also known. Black CmO2 can be obtained by burning curium oxalate (Cm
2(C
2O
4)
3), nitrate (Cm(NO
3)
3), or hydroxide in pure oxygen. Upon heating to 600–650 °C in vacuum (about 0.01 Pa), it transforms into the whitish Cm2O3:
- .
Or, Cm2O3 can be obtained by reducing CmO2 with molecular hydrogen:
Also, a number of ternary oxides of the type M(II)CmO3 are known, where M stands for a divalent metal, such as barium.
Thermal oxidation of trace quantities of curium hydride (CmH2–3) has been reported to give a volatile form of CmO2 and the volatile trioxide CmO3, one of two known examples of the very rare +6 state for curium. Another observed species was reported to behave similar to a supposed plutonium tetroxide and was tentatively characterized as CmO4, with curium in the extremely rare +8 state; but new experiments seem to indicate that CmO4 does not exist, and have cast doubt on the existence of PuO4 as well.
Halides
The colorless curium(III) fluoride (CmF3) can be made by adding fluoride ions into curium(III)-containing solutions. The brown tetravalent curium(IV) fluoride (CmF4) on the other hand is only obtained by reacting curium(III) fluoride with molecular fluorine:
A series of ternary fluorides are known of the form A7Cm6F31 (A = alkali metal).
The colorless curium(III) chloride (CmCl3) is made by reacting curium hydroxide (Cm(OH)3) with anhydrous hydrogen chloride gas. It can be further turned into other halides such as curium(III) bromide (colorless to light green) and curium(III) iodide (colorless), by reacting it with the ammonia salt of the corresponding halide at temperatures of ~400–450 °C:
Or, one can heat curium oxide to ~600°C with the corresponding acid (such as hydrobromic for curium bromide). Vapor phase hydrolysis of curium(III) chloride gives curium oxychloride:
Chalcogenides and pnictides
Sulfides, selenides and tellurides of curium have been obtained by treating curium with gaseous sulfur, selenium or tellurium in vacuum at elevated temperature. Curium pnictides of the type CmX are known for nitrogen, phosphorus, arsenic and antimony. They can be prepared by reacting either curium(III) hydride (CmH3) or metallic curium with these elements at elevated temperature.
Organocurium compounds and biological aspects
Organometallic complexes analogous to uranocene are known also for other actinides, such as thorium, protactinium, neptunium, plutonium and americium. Molecular orbital theory predicts a stable "curocene" complex (η-C8H8)2Cm, but it has not been reported experimentally yet.
Formation of the complexes of the type Cm(n-C
3H
7-BTP)
3 (BTP = 2,6-di(1,2,4-triazin-3-yl)pyridine), in solutions containing n-C3H7-BTP and Cm ions has been confirmed by EXAFS. Some of these BTP-type complexes selectively interact with curium and thus are useful for separating it from lanthanides and another actinides. Dissolved Cm ions bind with many organic compounds, such as hydroxamic acid, urea, fluorescein and adenosine triphosphate. Many of these compounds are related to biological activity of various microorganisms. The resulting complexes show strong yellow-orange emission under UV light excitation, which is convenient not only for their detection, but also for studying interactions between the Cm ion and the ligands via changes in the half-life (of the order ~0.1 ms) and spectrum of the fluorescence.
There are a few reports on biosorption of Cm by bacteria and archaea, and in the laboratory both americium and curium were found to support the growth of methylotrophs.
Applications
Radionuclides
Curium is one of the most radioactive isolable elements. Its two most common isotopes Cm and Cm are strong alpha emitters (energy 6 MeV); they have fairly short half-lives, 162.8 days and 18.1 years, and give as much as 120 W/g and 3 W/g of heat, respectively. Therefore, curium can be used in its common oxide form in radioisotope thermoelectric generators like those in spacecraft. This application has been studied for the Cm isotope, while Cm was abandoned due to its prohibitive price, around 2000 USD/g. Cm with a ~30-year half-life and good energy yield of ~1.6 W/g could be a suitable fuel, but it gives significant amounts of harmful gamma and beta rays from radioactive decay products. As an α-emitter, Cm needs much less radiation shielding, but it has a high spontaneous fission rate, and thus a lot of neutron and gamma radiation. Compared to a competing thermoelectric generator isotope such as Pu, Cm emits 500 times more neutrons, and its higher gamma emission requires a shield that is 20 times thicker—2 inches (51 mm) of lead for a 1 kW source, compared to 0.1 inches (2.5 mm) for Pu. Therefore, this use of curium is currently considered impractical.
A more promising use of Cm is for making Pu, a better radioisotope for thermoelectric generators such as in heart pacemakers. The alternate routes to Pu use the (n,γ) reaction of Np, or deuteron bombardment of uranium, though both reactions always produce Pu as an undesired by-product since the latter decays to U with strong gamma emission. Curium is a common starting material for making higher transuranic and superheavy elements. Thus, bombarding Cm with neon (Ne), magnesium (Mg), or calcium (Ca) yields isotopes of seaborgium (Sg), hassium (Hs and Hs), and livermorium (Lv, Lv, and possibly Lv). Californium was discovered when a microgram-sized target of curium-242 was irradiated with 35 MeV alpha particles using the 60-inch (150 cm) cyclotron at Berkeley:
96Cm
+
2He
→
98Cf
+
0n
Only about 5,000 atoms of californium were produced in this experiment.
The odd-mass curium isotopes Cm, Cm, and Cm are all highly fissile and can release additional energy in a thermal spectrum nuclear reactor. All curium isotopes are fissionable in fast-neutron reactors. This is one of the motives for minor actinide separation and transmutation in the nuclear fuel cycle, helping to reduce the long-term radiotoxicity of used, or spent nuclear fuel.
X-ray spectrometer
The most practical application of Cm—though rather limited in total volume—is as α-particle source in alpha particle X-ray spectrometers (APXS). These instruments were installed on the Sojourner, Mars, Mars 96, Mars Exploration Rovers and Philae comet lander, as well as the Mars Science Laboratory to analyze the composition and structure of the rocks on the surface of planet Mars. APXS was also used in the Surveyor 5–7 moon probes but with a Cm source.
An elaborate APXS setup has a sensor head containing six curium sources with a total decay rate of several tens of millicuries (roughly one gigabecquerel). The sources are collimated on a sample, and the energy spectra of the alpha particles and protons scattered from the sample are analyzed (proton analysis is done only in some spectrometers). These spectra contain quantitative information on all major elements in the sample except for hydrogen, helium and lithium.
Safety
Due to its radioactivity, curium and its compounds must be handled in appropriate labs under special arrangements. While curium itself mostly emits α-particles which are absorbed by thin layers of common materials, some of its decay products emit significant fractions of beta and gamma rays, which require a more elaborate protection. If consumed, curium is excreted within a few days and only 0.05% is absorbed in the blood. From there, ~45% goes to the liver, 45% to the bones, and the remaining 10% is excreted. In bone, curium accumulates on the inside of the interfaces to the bone marrow and does not significantly redistribute with time; its radiation destroys bone marrow and thus stops red blood cell creation. The biological half-life of curium is about 20 years in the liver and 50 years in the bones. Curium is absorbed in the body much more strongly via inhalation, and the allowed total dose of Cm in soluble form is 0.3 μCi. Intravenous injection of Cm- and Cm-containing solutions to rats increased the incidence of bone tumor, and inhalation promoted lung and liver cancer.
Curium isotopes are inevitably present in spent nuclear fuel (about 20 g/tonne). The isotopes Cm–Cm have decay times of thousands of years and must be removed to neutralize the fuel for disposal. Such a procedure involves several steps, where curium is first separated and then converted by neutron bombardment in special reactors to short-lived nuclides. This procedure, nuclear transmutation, while well documented for other elements, is still being developed for curium.
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{{cite web}}
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Bibliography
- Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
- Holleman, Arnold F. and Wiberg, Nils Lehrbuch der Anorganischen Chemie, 102 Edition, de Gruyter, Berlin 2007, ISBN 978-3-11-017770-1.
- Penneman, R. A. and Keenan T. K. The radiochemistry of americium and curium, University of California, Los Alamos, California, 1960
External links
- Curium at The Periodic Table of Videos (University of Nottingham)
- NLM Hazardous Substances Databank – Curium, Radioactive
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