Curium is a synthetic chemical element; it has Chemical symbol Cm and atomic number 96. This transuranic actinide element was named after eminent scientists Marie Curie 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 239Pu) with . 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 in – 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 paramagnetism 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 fluorescence 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 of curium are radioactive and have small critical mass for a nuclear chain reaction. The most stable isotope, 247Cm, has a half-life of 15.6 million years; the longest-lived curium isotopes predominantly emit alpha decay. 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 238Pu 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 and the Philae lander on comet 67P/Churyumov–Gerasimenko, to analyze the composition and structure of the surface.
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 cm2 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 (from Greek for all demons or hell) and (from Latin for madness).Krebs, Robert E. The history and use of our earth's chemical elements: a reference guide, Greenwood Publishing Group, 2006, p. 322
Curium-242 was made in July–August 1944 by bombarding 239Pu with alpha decay 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:
Another isotope 240Cm was produced in a similar reaction in March 1945:
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 (242Cm and 240Cm), its production, and its compounds was later patented listing only Seaborg as the inventor.Seaborg, G. T. "Element", Filing date: 7 February 1949, Issue date: December 1964
The 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:Greenwood, p. 1252
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.Hammond C. R. "The elements" in 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. 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 1950 by reduction of CmF3 with barium.
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 Ferrimagnetism transition at ~205 K. Curium pnictides show Ferromagnetism transitions upon cooling: 244CmN and 244CmAs at 109 K, 248CmP at 73 K and 248CmSb 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.Nave, S. E.; Huray, P. G.; Peterson, J. R. and Damien, D. A. Magnetic susceptibility of curium pnictides, Oak Ridge National Laboratory
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 (~) due to self-damage of the crystal lattice by alpha decay. This makes uncertain the true resistivity of curium (~). 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 6D7/2 and the ground state 8S7/2. Analysis of this fluorescence allows monitoring interactions between Cm(III) ions in organic and inorganic complexes.Bünzli, J.-C. G. and Choppin, G. R. Lanthanide probes in life, chemical, and earth sciences: theory and practice, Elsevier, Amsterdam, 1989
Curium ions are HSAB theory 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.Greenwood, p. 1267
247Cm |
81.90 |
57 |
0.70 |
0.000928% |
250Cm |
23.5 |
All isotopes ranging from 242Cm to 248Cm, as well as 250Cm, 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 243Cm, 245Cm and 247Cm. 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.Institut de Radioprotection et de Sûreté Nucléaire: "Evaluation of nuclear criticality safety. data and limits for actinides in transport" , p. 16 The mixed-oxide (MOX) fuel, which is to be used in power reactors, should contain little or no curium because neutron activation of 248Cm 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 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 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 245Cm, 155 grams for 243Cm and 1550 grams for 247Cm. There is significant uncertainty in these critical mass values. While it is usually on the order of 20%, the values for 242Cm and 246Cm 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. § 2 Begriffsbestimmungen (Atomic Energy Act) (in German) 245Cm and 247Cm 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 ).
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. Curium (in German) 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 245Cm, 246Cm and smaller quantities of 247Cm, 248Cm and 249Cm.
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 transuranic elements up to fermium, including curium, should have been present in the natural nuclear fission reactor at Oklo, but any quantities produced then would have long since decayed away.
Further neutron capture followed by β−-decay gives americium (241Am) which further becomes 242Cm:
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 244Cm:Morss, L. R.; Edelstein, N. M. and Fugere, J. (eds): The Chemistry of the Actinide Elements and transactinides, volume 3, Springer-Verlag, Dordrecht 2006, .
Curium-244 alpha decays to 240Pu, but it also absorbs neutrons, hence a small amount of heavier curium isotopes. Of those, 247Cm and 248Cm are popular in scientific research due to their long half-lives. But the production rate of 247Cm in thermal neutron reactors is low because it is prone to fission due to thermal neutrons. Synthesis of 250Cm by neutron capture is unlikely due to the short half-life of the intermediate 249Cm (64 min), which β− decays to the berkelium isotope 249Bk.
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 252Cf, which is available in relatively large amounts due to its long half-life (2.65 years). About 35–50 mg of 248Cm is produced thus, per year. The associated reaction produces 248Cm with isotopic purity of 97%.
Another isotope, 245Cm, can be obtained for research, from α-decay of 249Cf; the latter isotope is produced in small amounts from β−-decay of 249berkelium.
Metallic curium is obtained by Redox 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. Gmelin Handbook of Inorganic Chemistry, System No. 71, Volume 7 a, transuranics, Part B 1, pp. 67–68.
Another possibility is reduction of curium(IV) oxide using a magnesium-zinc alloy in a melt of magnesium chloride and magnesium fluoride.
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.
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 acid for curium bromide). Vapor phase hydrolysis of curium(III) chloride gives curium oxychloride:
Formation of the complexes of the type (BTP = 2,6-di(1,2,4-triazin-3-yl)pyridine), in solutions containing n-C3H7-BTP and Cm3+ 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 Cm3+ 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 . 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 Cm3+ 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 Cm3+ by bacteria and archaea, and in the laboratory both americium and curium were found to support the growth of .
A more promising use of 242Cm is for making 238Pu, a better radioisotope for thermoelectric generators such as in heart pacemakers. The alternate routes to 238Pu use the (n,γ) reaction of 237Np, or deuterium bombardment of uranium, though both reactions always produce 236Pu as an undesired by-product since the latter decays to 232U with strong gamma emission. Kronenberg, Andreas, Plutonium-Batterien (in German)
The odd-mass curium isotopes 243Cm, 245Cm, and 247Cm are all highly fissile material 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.
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. Alpha Particle X-Ray Spectrometer (APXS), Cornell University
Curium isotopes are inevitably present in spent nuclear fuel (about 20 g/tonne).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 The isotopes 245Cm–248Cm have decay times of thousands of years and must be removed to neutralize the fuel for disposal.Baetslé, L. H. Application of Partitioning/Transmutation of Radioactive Materials in Radioactive Waste Management , Nuclear Research Centre of Belgium Sck/Cen, Mol, Belgium, September 2001. 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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