Americium is a synthetic chemical element; it has symbol Am and atomic number 95. It is radioactive and a transuranic member of the actinide series in the periodic table, located under the lanthanide element europium and was thus named after the Americas by analogy.
Americium was first produced in 1944 by the group of Glenn T. Seaborg from Berkeley, California, at the Metallurgical Laboratory of the University of Chicago, as part of the Manhattan Project. Although it is the third element in the transuranic series, it was discovered fourth, after the heavier curium. The discovery was kept secret and released to the public only in November 1945. Most americium is produced by uranium or plutonium being bombarded with neutrons in nuclear reactors – one tonne of spent nuclear fuel contains about 100 grams of americium. It is widely used in commercial ionization chamber smoke detectors, as well as in neutron sources and industrial gauges. Several unusual applications, such as nuclear batteries or fuel for space ships with nuclear propulsion, have been proposed for the isotope 242mAm, but they are as yet hindered by the scarcity and high price of this nuclear isomer.
Americium is a relatively soft radioactive metal with a silvery appearance. Its most common isotopes are 241Am and 243Am. In chemical compounds, americium usually assumes the oxidation state +3, especially in solutions. Several other oxidation states are known, ranging from +2 to +7, and can be identified by their characteristic optical absorption spectra. The crystal lattices of solid americium and its compounds contain small intrinsic radiogenic defects due to metamictization induced by self-irradiation with alpha particles. These defects accumulate with time, which can cause a drift of some material properties and is more noticeable in older samples.
History
Although americium was likely produced in previous nuclear experiments, it was first intentionally synthesized, isolated and identified in late autumn 1944, at the University of California, Berkeley, by Glenn T. Seaborg, Leon O. Morgan, Ralph A. James, and Albert Ghiorso. They used a 60-inch cyclotron at the University of California, Berkeley.Obituary of Dr. Leon Owen (Tom) Morgan (1919–2002), Retrieved 28 November 2010 The element was chemically identified at the Metallurgical Laboratory (now Argonne National Laboratory) of the University of Chicago. Following the lighter neptunium, plutonium, and heavier curium, americium was the fourth transuranium element to be discovered. At the time, the periodic table had been restructured by Seaborg to its present layout, containing the actinide row below the lanthanide one. This led to americium being located right below its twin lanthanide element europium; it was thus by analogy named after the Americas: "The name americium (after the Americas) and the symbol Am are suggested for the element on the basis of its position as the sixth member of the actinide rare-earth series, analogous to europium, Eu, of the lanthanide series."Seaborg, G. T.; James, R.A. and Morgan, L. O.: "The New Element Americium (Atomic Number 95)", THIN PPR (National Nuclear Energy Series, Plutonium Project Record), Vol 14 B The Transuranium Elements: Research Papers, Paper No. 22.1, McGraw-Hill Book Co., Inc., New York, 1949. Abstract; Full text (January 1948), Retrieved 28 November 2010Greenwood, p. 1252
The new element was isolated from its oxides in a complex, multi-step process. First plutonium-239 nitrate solution was coated on a platinum foil of about 0.5 cm2 area, the solution was evaporated and the residue was converted into plutonium dioxide (PuO2) by calcining. After cyclotron irradiation, 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. Further separation was carried out by ion exchange, yielding a certain isotope of curium. The separation of curium and americium was so painstaking that those elements were initially called by the Berkeley group as pandemonium (from Greek for all demons or hell) and delirium (from Latin for madness).
Initial experiments yielded four americium isotopes: 241Am, 242Am, 239Am and 238Am. Americium-241 was directly obtained from plutonium upon absorption of two neutrons. It decays by emission of a α-particle to 237Np; the half-life of this decay was first determined as years but then corrected to 432.2 years.
The times are half-lives
The second isotope 242Am was produced upon neutron bombardment of the already-created 241Am. Upon rapid β-decay, 242Am converts into the isotope of curium 242Cm (which had been discovered previously). The half-life of this decay was initially determined at 17 hours, which was close to the presently accepted value of 16.02 h.
The discovery of americium and curium in 1944 was closely related to the Manhattan Project; 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 Quiz Kids five days before the official presentation at an American Chemical Society meeting on 11 November 1945, when one of the listeners asked whether any new transuranium element besides plutonium and neptunium had been discovered during the war. After the discovery of americium isotopes 241Am and 242Am, their production and compounds were patented listing only Seaborg as the inventor.Seaborg, Glenn T. "Element", Filing date: 23 August 1946, Issue date: 10 November 1964 The initial americium samples weighed a few micrograms; they were barely visible and were identified by their radioactivity. The first substantial amounts of metallic americium, weighing 40–200 micrograms, were not prepared until 1951 by reduction of americium(III) fluoride with barium metal in high vacuum at 1100 °C.
Occurrence
The longest-lived and most common isotopes of americium, 241Am and 243Am, have half-lives of 432.6 and 7,350 years, respectively. Therefore, any primordial americium (americium that was present on Earth during its formation) should have decayed by now. Trace amounts of americium probably occur naturally in uranium minerals as a result of neutron capture and beta decay (238U → 239Pu → 240Pu → 241Am), though the quantities would be tiny and this has not been confirmed. Extraterrestrial long-lived 247Cm is probably also deposited on Earth and has 243Am as one of its intermediate decay products, but again this has not been confirmed.
Existing americium is concentrated in the areas used for the atmospheric nuclear weapons tests conducted between 1945 and 1980, as well as at the sites of nuclear incidents, such as the Chernobyl disaster. For example, the analysis of the debris at the testing site of the first U.S. hydrogen bomb, Ivy Mike, (1 November 1952, Enewetak Atoll), revealed high concentrations of various actinides including americium; but due to military secrecy, this result was not published until later, in 1956. Trinitite, the glassy residue left on the desert floor near Alamogordo, New Mexico, after the plutonium-based Trinity nuclear bomb test on 16 July 1945, contains traces of americium-241. Elevated levels of americium were also detected at the crash site of a US Boeing B-52 bomber aircraft, which carried four hydrogen bombs, in 1968 in Greenland.
In other regions, the average radioactivity of surface soil due to residual americium is only about 0.01 picocuries per gram (0.37 mBq/g). Atmospheric americium compounds are poorly soluble in common solvents and mostly adhere to soil particles. Soil analysis revealed about 1,900 times higher concentration of americium inside sandy soil particles than in the water present in the soil pores; an even higher ratio was measured in loam soils.Human Health Fact Sheet on Americium , Los Alamos National Laboratory, Retrieved 28 November 2010
Americium is produced mostly artificially in small quantities, for research purposes. A tonne of spent nuclear fuel contains about 100 grams of various americium isotopes, mostly 241Am and 243Am.Hoffmann, Klaus 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 Their prolonged radioactivity is undesirable for the disposal, and therefore americium, together with other long-lived actinides, must be neutralized. The associated procedure may involve several steps, where americium is first separated and then converted by neutron bombardment in special reactors to short-lived nuclides. This procedure is well known as nuclear transmutation, but it is still being developed for americium.Baetslé, L. Application of Partitioning/Transmutation of Radioactive Materials in Radioactive Waste Management , Nuclear Research Centre of Belgium Sck/Cen, Mol, Belgium, September 2001, Retrieved 28 November 2010Fioni, Gabriele; Cribier, Michel and Marie, Frédéric Can the minor actinide, americium-241, be transmuted by thermal neutrons? , Department of Astrophysics, CEA/Saclay, Retrieved 28 November 2010
The transuranic elements up to fermium, including americium, should have been present in the natural nuclear fission reactor at Oklo, but any quantities produced then would have long since decayed away.
Synthesis and extraction
Isotope nucleosynthesis
Americium has been produced in small quantities in nuclear reactors for decades, and kilograms of its 241Am and 243Am isotopes have been accumulated by now.Greenwood, p. 1262 Nevertheless, since it was first offered for sale in 1962, its price, about of 241Am, remains almost unchanged owing to the very complex separation procedure.Smoke detectors and americium , World Nuclear Association, January 2009, Retrieved 28 November 2010 The heavier isotope 243Am is produced in much smaller amounts; it is thus more difficult to separate, resulting in a higher cost of the order .Hammond C. R. "The elements" in
Americium is not synthesized directly from uranium – the most common reactor material – but from the plutonium isotope 239Pu. The latter needs to be produced first, according to the following nuclear process:
^{238}_{92}U ->[\ce{(n,\gamma)}] ^{239}_{92}U ->[\beta^-][23.5 \ \ce{min}] ^{239}_{93}Np ->[\beta^-][2.3565 \ \ce{d}] ^{239}_{94}Pu
The capture of two neutrons by 239Pu (a so-called (n,γ) reaction), followed by a β-decay, results in 241Am:
^{239}_{94}Pu ->[\ce{2(n,\gamma)}] ^{241}_{94}Pu ->[\beta^-][14.35 \ \ce{yr}] ^{241}_{95}Am
The plutonium present in spent nuclear fuel contains about 12% of 241Pu. Because it beta-decays to 241Am, 241Pu can be extracted and may be used to generate further 241Am. However, this process is rather slow: half of the original amount of 241Pu decays to 241Am after about 15 years, and the 241Am amount reaches a maximum after 70 years.BREDL Southern Anti-Plutonium Campaign, Blue Ridge Environmental Defense League, Retrieved 28 November 2010
The obtained 241Am can be used for generating heavier americium isotopes by further neutron capture inside a nuclear reactor. In a light water reactor (LWR), 79% of 241Am converts to 242Am and 10% to its nuclear isomer 242mAm:The "m" denotes that it is a metastable state. article/200410/000020041004A0333355.php Abstract
Americium-242 has a half-life of only 16 hours, which makes its further conversion to 243Am extremely inefficient. The latter isotope is produced instead in a process where 239Pu captures four neutrons under high neutron flux:
^{239}_{94}Pu ->[\ce{4(n,\gamma)}] \ ^{243}_{94}Pu ->[\beta^-][4.956 \ \ce{h}] ^{243}_{95}Am
Metal generation