Americium

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.<ref>Template:Cite journal</ref><ref>Template:Cite journal</ref><ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref>

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 only released to the public 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, which accumulates with time; this can cause a drift of some material properties over time, more noticeable in older samples.

History

File:Berkeley 60-inch cyclotron.jpg

The 60-inch cyclotron at the Lawrence Radiation Laboratory, University of California, Berkeley, in August 1939

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.<ref>Obituary of Dr. Leon Owen (Tom) Morgan (1919–2002), Retrieved 28 November 2010</ref> 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."<ref>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 2010</ref><ref>Template:Cite journal</ref><ref name="g1252">Greenwood, p. 1252</ref>

The new element was isolated from its oxides in a complex, multi-step process. First plutonium-239 nitrate (²³⁹PuNO₃) 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<ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref> (from Greek for all demons or hell) and delirium (from Latin for madness).<ref name="radio" /><ref>Template:Cite book</ref>

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 Template:Val years but then corrected to 432.2 years.<ref name="nubase">Template:NUBASE 1997</ref>

<math chem>\ce{^{239}_{94}Pu ->[\ce{(n,\gamma)}] ^{240}_{94}Pu ->[\ce{(n,\gamma)}] ^{241}_{94}Pu ->[\beta^-][14.35\ \ce{yr}] ^{241}_{95}Am}\ \left( \ce{->[\alpha][432.2\ \ce{yr}] ^{237}_{93}Np} \right)</math>

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.<ref name="nubase" />

<math chem>\ce{^{241}_{95}Am ->[\ce{(n,\gamma)}] ^{242}_{95}Am}\ \left(\ce{->[\beta^-][16.02\ \ce{h}] ^{242}_{96}Cm} \right)</math>

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.<ref name="radio">{{#invoke:citation/CS1|citation |CitationClass=web }}</ref> After the discovery of americium isotopes ²⁴¹Am and ²⁴²Am, their production and compounds were patented listing only Seaborg as the inventor.<ref>Seaborg, Glenn T. {{#if:3156523 |[{{#ifeq:|uspto|http://patft.uspto.gov/netacgi/nph-Parser?patentnumber=%7Chttps://patents.google.com/patent/US}}{{#iferror:{{#expr:3156523 }}|3156523}} U.S. patent {{#ifeq:Template:Replace|Template:Digits|Template:Replace|3156523}}] |{{US patent|123456|link text}}}} "Element", Filing date: 23 August 1946, Issue date: 10 November 1964</ref> 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.<ref name="AM_METALL1">Template:Cite journal</ref>

Occurrence

File:Ivy Mike - mushroom cloud.jpg

Americium was detected in the fallout from the Ivy Mike nuclear test.

The longest-lived and most common isotopes of americium, ²⁴¹Am and ²⁴³Am, have half-lives of 432.2 and 7,370 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.<ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref><ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref><ref name=ThorntonBurdette>Template:Cite journal</ref> 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.<ref name=ThorntonBurdette/>

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.<ref>Template:Cite journal</ref> 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.<ref>Template:Cite book</ref>

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.<ref name="am">Human Health Fact Sheet on Americium Template:Webarchive, Los Alamos National Laboratory, Retrieved 28 November 2010</ref>

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.<ref>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</ref> 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.<ref>Baetslé, L. Application of Partitioning/Transmutation of Radioactive Materials in Radioactive Waste Management Template:Webarchive, Nuclear Research Centre of Belgium Sck/Cen, Mol, Belgium, September 2001, Retrieved 28 November 2010</ref><ref>Fioni, Gabriele; Cribier, Michel and Marie, Frédéric Can the minor actinide, americium-241, be transmuted by thermal neutrons? Template:Webarchive, Department of Astrophysics, CEA/Saclay, Retrieved 28 November 2010</ref> The transuranic elements from americium to fermium occurred naturally in the natural nuclear fission reactor at Oklo, but no longer do so.<ref name="emsley">Template:Cite book</ref>

Americium is also one of the elements that have theoretically been detected in Przybylski's Star.<ref name=gopka08>Template:Cite journal</ref>

Synthesis and extraction

Isotope nucleosynthesis

File:Elutionskurven Tb Gd Eu und Bk Cm Am.png

Chromatographic elution curves revealing the similarity between the lanthanides Tb, Gd, and Eu and the corresponding actinides Bk, Cm, and Am

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.<ref name="g1262">Greenwood, p. 1262</ref> Nevertheless, since it was first offered for sale in 1962, its price, about Template:Convert of ²⁴¹Am, remains almost unchanged owing to the very complex separation procedure.<ref name="smoke">Smoke detectors and americium Template:Webarchive, World Nuclear Association, January 2009, Retrieved 28 November 2010</ref> 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 Template:Convert.<ref name="CRC">Hammond C. R. "The elements" in Template:RubberBible86th</ref><ref>Template:Cite book</ref>

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:

<chem>^{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</chem>

The capture of two neutrons by ²³⁹Pu (a so-called (n,γ) reaction), followed by a β-decay, results in ²⁴¹Am:

<chem>^{239}_{94}Pu ->[\ce{2(n,\gamma)}] ^{241}_{94}Pu ->[\beta^-][14.35 \ \ce{yr}] ^{241}_{95}Am</chem>

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.<ref name="smoke" /> 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.<ref>BREDL Southern Anti-Plutonium Campaign, Blue Ridge Environmental Defense League, Retrieved 28 November 2010</ref>

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:<ref group=note>The "metastable" state is marked by the letter m.</ref><ref>Template:Cite journal article/200410/000020041004A0333355.php Abstract Template:Webarchive</ref>

<math chem>\begin{cases}

79\%: & \ce{^{241}_{95}Am ->[\ce{(n,\gamma)}] ^{242}_{95}Am} \\ 10\%: & \ce{^{241}_{95}Am ->[\ce{(n,\gamma)}] ^{242 m}_{95}Am} \end{cases}</math> 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:

<chem>^{239}_{94}Pu ->[\ce{4(n,\gamma)}] \ ^{243}_{94}Pu ->[\beta^-][4.956 \ \ce{h}] ^{243}_{95}Am</chem>

Metal generation

Most synthesis routines yield a mixture of different actinide isotopes in oxide forms, from which isotopes of americium can be separated. In a typical procedure, the spent reactor fuel (e.g. MOX fuel) is dissolved in nitric acid, and the bulk of uranium and plutonium is removed using a PUREX-type extraction (Plutonium–URanium EXtraction) with tributyl phosphate in a hydrocarbon. The lanthanides and 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. Americium compounds are then selectively extracted using multi-step chromatographic and centrifugation techniques<ref>Penneman, pp. 34–48</ref> with an appropriate reagent. A large amount of work has been done on the solvent extraction of americium. For example, a 2003 EU-funded project codenamed "EUROPART" studied triazines and other compounds as potential extraction agents.<ref>Template:Cite journal</ref><ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref><ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref><ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref><ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref> A bis-triazinyl bipyridine complex was proposed in 2009 as such a reagent is highly selective to americium (and curium).<ref>Template:Cite journal</ref> Separation of americium from the highly similar curium can be achieved by treating a slurry of their hydroxides in aqueous sodium bicarbonate with ozone, at elevated temperatures. Both Am and Cm are mostly present in solutions in the +3 valence state; whereas curium remains unchanged, americium oxidizes to soluble Am(IV) complexes which can be washed away.<ref>Penneman, p. 25</ref>

Metallic americium is obtained by reduction from its compounds. Americium(III) fluoride was first used for this purpose. The reaction was conducted using elemental barium as reducing agent in a water- and oxygen-free environment inside an apparatus made of tantalum and tungsten.<ref name="AM_METALL1" /><ref name = "Gmelin">Gmelin Handbook of Inorganic Chemistry, System No. 71, transuranics, Part B 1, pp. 57–67.</ref><ref name="p3">Penneman, p. 3</ref>

<math>\mathrm{2\ AmF_3\ +\ 3\ Ba\ \longrightarrow \ 2\ Am\ +\ 3\ BaF_2}</math>

An alternative is the reduction of americium dioxide by metallic lanthanum or thorium:<ref name="p3" /><ref name="AM_METALL2" />

<math>\mathrm{3\ AmO_2\ +\ 4\ La\ \longrightarrow \ 3\ Am\ +\ 2\ La_2O_3}</math>

Physical properties

File:Closest packing ABAC.png

Double-hexagonal close packing with the layer sequence ABAC in the crystal structure of α-americium (A: green, B: blue, C: red)

In the periodic table, americium is located to the right of plutonium, to the left of curium, and below the lanthanide europium, with which it shares many physical and chemical properties. Americium is a highly radioactive element. When freshly prepared, it has a silvery-white metallic lustre, but then slowly tarnishes in air. With a density of 12 g/cm³, americium is less dense than both curium (13.52 g/cm³) and plutonium (19.8 g/cm³); but has a higher density than europium (5.264 g/cm³)—mostly because of its higher atomic mass. Americium is relatively soft and easily deformable and has a significantly lower bulk modulus than the actinides before it: Th, Pa, U, Np and Pu.<ref name="pressure" /> Its melting point of 1173 °C is significantly higher than that of plutonium (639 °C) and europium (826 °C), but lower than for curium (1340 °C).<ref name="AM_METALL2">Template:Cite journal</ref><ref name="AM_METALL4" />

At ambient conditions, americium is present in its most stable α form which has a hexagonal crystal symmetry, and a space group P6₃/mmc with cell parameters a = 346.8 pm and c = 1124 pm, and four atoms per unit cell. The crystal consists of a double-hexagonal close packing with the layer sequence ABAC and so is isotypic with α-lanthanum and several actinides such as α-curium.<ref name="Gmelin" /><ref name = "AM_METALL4">Template:Cite journal</ref> The crystal structure of americium changes with pressure and temperature. When compressed at room temperature to 5 GPa, α-Am transforms to the β modification, which has a face-centered cubic (fcc) symmetry, space group FmTemplate:Overlinem and lattice constant a = 489 pm. This fcc structure is equivalent to the closest packing with the sequence ABC.<ref name="Gmelin" /><ref name = "AM_METALL4" /> Upon further compression to 23 GPa, americium transforms to an orthorhombic γ-Am structure similar to that of α-uranium. There are no further transitions observed up to 52 GPa, except for an appearance of a monoclinic phase at pressures between 10 and 15 GPa.<ref name="pressure">Template:Cite journal</ref> There is no consistency on the status of this phase in the literature, which also sometimes lists the α, β and γ phases as I, II and III. The β-γ transition is accompanied by a 6% decrease in the crystal volume; although theory also predicts a significant volume change for the α-β transition, it is not observed experimentally. The pressure of the α-β transition decreases with increasing temperature, and when α-americium is heated at ambient pressure, at 770 °C it changes into an fcc phase which is different from β-Am, and at 1075 °C it converts to a body-centered cubic structure. The pressure-temperature phase diagram of americium is thus rather similar to those of lanthanum, praseodymium and neodymium.<ref>Template:Cite book</ref>

As with many other actinides, self-damage of the crystal structure due to alpha-particle irradiation is intrinsic to americium. It is especially noticeable at low temperatures, where the mobility of the produced structure defects is relatively low, by broadening of X-ray diffraction peaks. This effect makes somewhat uncertain the temperature of americium and some of its properties, such as electrical resistivity.<ref>Template:Cite journal</ref> So for americium-241, the resistivity at 4.2 K increases with time from about 2 μOhm·cm to 10 μOhm·cm after 40 hours, and saturates at about 16 μOhm·cm after 140 hours. This effect is less pronounced at room temperature, due to annihilation of radiation defects; also heating to room temperature the sample which was kept for hours at low temperatures restores its resistivity. In fresh samples, the resistivity gradually increases with temperature from about 2 μOhm·cm at liquid helium to 69 μOhm·cm at room temperature; this behavior is similar to that of neptunium, uranium, thorium and protactinium, but is different from plutonium and curium which show a rapid rise up to 60 K followed by saturation. The room temperature value for americium is lower than that of neptunium, plutonium and curium, but higher than for uranium, thorium and protactinium.<ref name="res" />

Americium is paramagnetic in a wide temperature range, from that of liquid helium, to room temperature and above. This behavior is markedly different from that of its neighbor curium which exhibits antiferromagnetic transition at 52 K.<ref>Template:Cite journal</ref> The thermal expansion coefficient of americium is slightly anisotropic and amounts to Template:Val along the shorter a axis and Template:Val for the longer c hexagonal axis.<ref name = "AM_METALL4" /> The enthalpy of dissolution of americium metal in hydrochloric acid at standard conditions is Template:Val, from which the standard enthalpy change of formation (Δ_fH°) of aqueous Am³⁺ ion is Template:Val. The standard potential Am³⁺/Am⁰ is Template:Val.<ref>Template:Cite journal</ref>

Chemical properties

Americium metal readily reacts with oxygen and dissolves in aqueous acids. The most stable oxidation state for americium is +3.<ref name="p4">Penneman, p. 4</ref> The chemistry of americium(III) has many similarities to the chemistry of lanthanide(III) compounds. For example, trivalent americium forms insoluble fluoride, oxalate, iodate, hydroxide, phosphate and other salts.<ref name="p4" /> Compounds of americium in oxidation states +2, +4, +5, +6 and +7 have also been studied. This is the widest range that has been observed with actinide elements. The color of americium compounds in aqueous solution is as follows: Am³⁺ (yellow-reddish), Am⁴⁺ (yellow-reddish), Template:Chem2; (yellow), Template:Chem2 (brown) and Template:Chem2 (dark green).<ref>Americium Template:Webarchive, Das Periodensystem der Elemente für den Schulgebrauch (The periodic table of elements for schools) chemie-master.de (in German), Retrieved 28 November 2010</ref><ref name="g1265">Greenwood, p. 1265</ref> The absorption spectra have sharp peaks, due to f-f transitions' in the visible and near-infrared regions. Typically, Am(III) has absorption maxima at ca. 504 and 811 nm, Am(V) at ca. 514 and 715 nm, and Am(VI) at ca. 666 and 992 nm.<ref>Penneman, pp. 10–14</ref><ref name="amoh4" /><ref name="carbonate" /><ref name="haxav" />

Americium compounds with oxidation state +4 and higher are strong oxidizing agents, comparable in strength to the permanganate ion (Template:Chem2) in acidic solutions.<ref name = "HOWI_1956">Wiberg, p. 1956</ref> Whereas the Am⁴⁺ ions are unstable in solutions and readily convert to Am³⁺, compounds such as americium dioxide (AmO₂) and americium(IV) fluoride (AmF₄) are stable in the solid state.

The pentavalent oxidation state of americium was first observed in 1951.<ref>Template:Cite journal</ref> In acidic aqueous solution the Template:Chem2 ion is unstable with respect to disproportionation.<ref>Template:Cite journal</ref><ref>Template:Cite journal</ref><ref name="g1275">Greenwood, p. 1275</ref> The reaction

Template:Chem2

is typical. The chemistry of Am(V) and Am(VI) is comparable to the chemistry of uranium in those oxidation states. In particular, compounds like Template:Chem2 and Template:Chem2 are comparable to uranates and the ion Template:Chem2 is comparable to the uranyl ion, Template:Chem2. Such compounds can be prepared by oxidation of Am(III) in dilute nitric acid with ammonium persulfate.<ref>Template:Cite journal</ref> Other oxidising agents that have been used include silver(I) oxide,<ref name="haxav">Template:Cite journal</ref> ozone and sodium persulfate.<ref name="carbonate">Template:Cite journal</ref>

Chemical compounds

{{#invoke:Labelled list hatnote|labelledList|Main article|Main articles|Main page|Main pages}}

Oxygen compounds

Three americium oxides are known, with the oxidation states +2 (AmO), +3 (Am₂O₃) and +4 (AmO₂). Americium(II) oxide was prepared in minute amounts and has not been characterized in detail.<ref>Template:Cite journal</ref> Americium(III) oxide is a red-brown solid with a melting point of 2205 °C.<ref name = "HOWI_1972">Wiberg, p. 1972</ref> Americium(IV) oxide is the main form of solid americium which is used in nearly all its applications. As most other actinide dioxides, it is a black solid with a cubic (fluorite) crystal structure.<ref name="g1267">Greenwood, p. 1267</ref>

The oxalate of americium(III), vacuum dried at room temperature, has the chemical formula Am₂(C₂O₄)₃·7H₂O. Upon heating in vacuum, it loses water at 240 °C and starts decomposing into AmO₂ at 300 °C, the decomposition completes at about 470 °C.<ref name="p4" /> The initial oxalate dissolves in nitric acid with the maximum solubility of 0.25 g/L.<ref name="p5">Penneman, p. 5</ref>

Halides

Halides of americium are known for the oxidation states +2, +3 and +4,<ref name="HOWI_1969">Wiberg, p. 1969</ref> where the +3 is most stable, especially in solutions.<ref name="hal1">Template:Cite journal</ref>

Oxidation state	F	Cl	Br	I
+4	Americium(IV) fluoride AmF4 pale pink
+3	Americium(III) fluoride AmF3 pink	Americium(III) chloride AmCl3 pink	Americium(III) bromide AmBr3 light yellow	Americium(III) iodide AmI3 light yellow
+2		Americium(II) chloride AmCl2 black	Americium(II) bromide AmBr2 black	Americium(II) iodide AmI2 black

Reduction of Am(III) compounds with sodium amalgam yields Am(II) salts – the black halides AmCl₂, AmBr₂ and AmI₂. They are very sensitive to oxygen and oxidize in water, releasing hydrogen and converting back to the Am(III) state. Specific lattice constants are:

• Orthorhombic AmCl₂: a = Template:Val, b = Template:Val and c = Template:Val
• Tetragonal AmBr₂: a = Template:Val and c = Template:Val.<ref>Template:Cite journal</ref> They can also be prepared by reacting metallic americium with an appropriate mercury halide HgX₂, where X = Cl, Br or I:<ref name="g1272">Greenwood, p. 1272</ref>

<chem>{Am} + \underset{mercury\ halide}{HgX2} ->[{} \atop 400 - 500 ^\circ \ce C] {AmX2} + {Hg}</chem>

Americium(III) fluoride (AmF₃) is poorly soluble and precipitates upon reaction of Am³⁺ and fluoride ions in weak acidic solutions:

<chem>Am^3+ + 3F^- -> AmF3(v)</chem>

The tetravalent americium(IV) fluoride (AmF₄) is obtained by reacting solid americium(III) fluoride with molecular fluorine:<ref name="f4">Template:Cite journal</ref><ref name="g1271">Greenwood, p. 1271</ref>

<chem>2AmF3 + F2 -> 2AmF4</chem>

Another known form of solid tetravalent americium fluoride is KAmF₅.<ref name="f4" /><ref name="p6">Penneman, p. 6</ref> Tetravalent americium has also been observed in the aqueous phase. For this purpose, black Am(OH)₄ was dissolved in 15-M NH₄F with the americium concentration of 0.01 M. The resulting reddish solution had a characteristic optical absorption spectrum which is similar to that of AmF₄ but differed from other oxidation states of americium. Heating the Am(IV) solution to 90 °C did not result in its disproportionation or reduction, however a slow reduction was observed to Am(III) and assigned to self-irradiation of americium by alpha particles.<ref name="amoh4">Template:Cite journal</ref>

Most americium(III) halides form hexagonal crystals with slight variation of the color and exact structure between the halogens. So, chloride (AmCl₃) is reddish and has a structure isotypic to uranium(III) chloride (space group P6₃/m) and the melting point of 715 °C.<ref name="HOWI_1969" /> The fluoride is isotypic to LaF₃ (space group P6₃/mmc) and the iodide to BiI₃ (space group RTemplate:Overline). The bromide is an exception with the orthorhombic PuBr₃-type structure and space group Cmcm.<ref name="hal1" /> Crystals of americium(III) chloride hexahydrate (AmCl₃·6H₂O) can be prepared by dissolving americium dioxide in hydrochloric acid and evaporating the liquid. Those crystals are hygroscopic and have yellow-reddish color and a monoclinic crystal structure.<ref>Template:Cite journal</ref>

Oxyhalides of americium in the form Am^VIO₂X₂, Am^VO₂X, Am^IVOX₂ and Am^IIIOX can be obtained by reacting the corresponding americium halide with oxygen or Sb₂O₃, and AmOCl can also be produced by vapor phase hydrolysis:<ref name="g1272" />

AmCl₃ + H₂O -> AmOCl + 2HCl

Chalcogenides and pnictides

The known chalcogenides of americium include the sulfide AmS₂,<ref name="AM_S_SE">Template:Cite journal</ref> selenides AmSe₂ and Am₃Se₄,<ref name = "AM_S_SE " /><ref name="AM_METALLIDE">Template:Cite journal</ref> and tellurides Am₂Te₃ and AmTe₂.<ref>Template:Cite journal</ref> The pnictides of americium (²⁴³Am) of the AmX type are known for the elements phosphorus, arsenic,<ref>Template:Cite journal</ref> antimony and bismuth. They crystallize in the rock-salt lattice.<ref name="AM_METALLIDE" />

Silicides and borides

Americium monosilicide (AmSi) and "disilicide" (nominally AmSi_x with: 1.87 < x < 2.0) were obtained by reduction of americium(III) fluoride with elementary silicon in vacuum at 1050 °C (AmSi) and 1150−1200 °C (AmSi_x). AmSi is a black solid isomorphic with LaSi, it has an orthorhombic crystal symmetry. AmSi_x has a bright silvery lustre and a tetragonal crystal lattice (space group I4₁/amd), it is isomorphic with PuSi₂ and ThSi₂.<ref>Template:Cite journal</ref> Borides of americium include AmB₄ and AmB₆. The tetraboride can be obtained by heating an oxide or halide of americium with magnesium diboride in vacuum or inert atmosphere.<ref>Lupinetti, A. J. et al. {{#if:6830738 |[{{#ifeq:|uspto|http://patft.uspto.gov/netacgi/nph-Parser?patentnumber=%7Chttps://patents.google.com/patent/US}}{{#iferror:{{#expr:6830738 }}|6830738}} U.S. patent {{#ifeq:Template:Replace|Template:Digits|Template:Replace|6830738}}] |{{US patent|123456|link text}}}} "Low-temperature synthesis of actinide tetraborides by solid-state metathesis reactions", Filed 4 Apr 2002, Issued 14 December 2004</ref><ref>Template:Cite journal</ref>

Organoamericium compounds

File:Uranocene-3D-balls.png

Predicted structure of amerocene [(η⁸-C₈H₈)₂Am]

Analogous to uranocene, americium is predicted to form the organometallic compound amerocene with two cyclooctatetraene ligands, with the chemical formula (η⁸-C₈H₈)₂Am.<ref>Template:Cite book</ref> A cyclopentadienyl complex is also known that is likely to be stoichiometrically AmCp₃.<ref>Template:Cite book</ref><ref>Template:Cite journal</ref>

Formation of the complexes of the type Am(n-C₃H₇-BTP)₃, where BTP stands for 2,6-di(1,2,4-triazin-3-yl)pyridine, in solutions containing n-C₃H₇-BTP and Am³⁺ ions has been confirmed by EXAFS. Some of these BTP-type complexes selectively interact with americium and therefore are useful in its selective separation from lanthanides and another actinides.<ref>Template:Cite journal</ref>

Biological aspects

Americium is an artificial element of recent origin, and thus does not have a biological requirement.<ref>Toeniskoetter, Steve; Dommer, Jennifer and Dodge, Tony The Biochemical Periodic Tables – Americium, University of Minnesota, Retrieved 28 November 2010</ref><ref>Template:Cite journal</ref> It is harmful to life. It has been proposed to use bacteria for removal of americium and other heavy metals from rivers and streams. Thus, Enterobacteriaceae of the genus Citrobacter precipitate americium ions from aqueous solutions, binding them into a metal-phosphate complex at their cell walls.<ref>Template:Cite journal</ref> Several studies have been reported on the biosorption and bioaccumulation of americium by bacteria<ref>Template:Cite journal</ref><ref>Template:Cite journal</ref> and fungi.<ref>Template:Cite journal</ref> In the laboratory, both americium and curium were found to support the growth of methylotrophs.<ref>Template:Cite journal</ref>

Fission

The isotope ^242mAm (half-life 141 years) has the largest cross sections for absorption of thermal neutrons (5,700 barns),<ref name = "Karlsruhe">Pfennig, G.; Klewe-Nebenius, H and Seelmann Eggebert, W. (Eds.): Karlsruhe nuclide, 7 Edition 2006.</ref> that results in a small critical mass for a sustained nuclear chain reaction. The critical mass for a bare ^242mAm sphere is about 9–14 kg (the uncertainty results from insufficient knowledge of its material properties). It can be lowered to 3–5 kg with a metal reflector and should become even smaller with a water reflector.<ref>Template:Cite journal Abstract Template:Webarchive</ref> Such small critical mass is favorable for portable nuclear weapons, but those based on ^242mAm are not known yet, probably because of its scarcity and high price. The critical masses of the two readily available isotopes, ²⁴¹Am and ²⁴³Am, are relatively high – 57.6 to 75.6 kg for ²⁴¹Am and 209 kg for ²⁴³Am.<ref name="irsn">Institut de Radioprotection et de Sûreté Nucléaire, "Evaluation of nuclear criticality safety data and limits for actinides in transport", p. 16.</ref> Scarcity and high price yet hinder application of americium as a nuclear fuel in nuclear reactors.<ref>Template:Cite journal</ref>

There are proposals of very compact 10-kW high-flux reactors using as little as 20 grams of ^242mAm. Such low-power reactors would be relatively safe to use as neutron sources for radiation therapy in hospitals.<ref>Template:Cite journal</ref>

Isotopes

Template:See also About 18 isotopes and 11 nuclear isomers are known for americium, having mass numbers 229, 230, and 232 through 247.<ref name="NUBASE2020"/> There are two long-lived alpha-emitters; ²⁴³Am has a half-life of 7,370 years and is the most stable isotope, and ²⁴¹Am has a half-life of 432.2 years. The most stable nuclear isomer is ^242m1Am; it has a long half-life of 141 years. The half-lives of other isotopes and isomers range from 0.64 microseconds for ^245m1Am to 50.8 hours for ²⁴⁰Am. As with most other actinides, the isotopes of americium with odd number of neutrons have relatively high rate of nuclear fission and low critical mass.<ref name = "nubase" />

Americium-241 decays to ²³⁷Np emitting alpha particles of 5 different energies, mostly at 5.486 MeV (85.2%) and 5.443 MeV (12.8%). Because many of the resulting states are metastable, they also emit gamma rays with the discrete energies between 26.3 and 158.5 keV.<ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref>

Americium-242 is a short-lived isotope with a half-life of 16.02 h.<ref name="nubase" /> It mostly (82.7%) converts by β-decay to ²⁴²Cm, but also by electron capture to ²⁴²Pu (17.3%). Both ²⁴²Cm and ²⁴²Pu transform via nearly the same decay chain through ²³⁸Pu down to ²³⁴U.

Nearly all (99.541%) of ^242m1Am decays by internal conversion to ²⁴²Am and the remaining 0.459% by α-decay to ²³⁸Np. The latter subsequently decays to ²³⁸Pu and then to ²³⁴U.<ref name="nubase" />

Americium-243 transforms by α-emission into ²³⁹Np, which converts by β-decay to ²³⁹Pu, and the ²³⁹Pu changes into ²³⁵U by emitting an α-particle.

Applications

Ionization-type smoke detector

{{#invoke:Labelled list hatnote|labelledList|Main article|Main articles|Main page|Main pages}}

Americium is used in the most common type of household smoke detector, which uses ²⁴¹Am in the form of americium dioxide as its source of ionizing radiation.<ref>Template:Citation</ref> This isotope is preferred over ²²⁶Ra because it emits 5 times more alpha particles and relatively little harmful gamma radiation.

The amount of americium in a typical new smoke detector is 1 microcurie (37 kBq) or 0.29 microgram. This amount declines slowly as the americium decays into neptunium-237, a different transuranic element with a much longer half-life (about 2.14 million years). With its half-life of 432.2 years, the americium in a smoke detector includes about 3% neptunium after 19 years, and about 5% after 32 years. The radiation passes through an ionization chamber, an air-filled space between two electrodes, and permits a small, constant current between the electrodes. Any smoke that enters the chamber absorbs the alpha particles, which reduces the ionization and affects this current, triggering the alarm. Compared to the alternative optical smoke detector, the ionization smoke detector is cheaper and can detect particles which are too small to produce significant light scattering; however, it is more prone to false alarms.<ref>Residential Smoke Alarm Performance, Thomas Cleary. Building and Fire Research Laboratory, National Institute of Standards and Technology; UL Smoke and Fire Dynamics Seminar. November 2007</ref><ref name="NIST">Bukowski, R. W. et al. (2007) Performance of Home Smoke Alarms Analysis of the Response of Several Available Technologies in Residential Fire Settings Template:Webarchive, NIST Technical Note 1455-1</ref><ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref><ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref>

Radionuclide

As ²⁴¹Am has a roughly similar half-life to ²³⁸Pu (432.2 years vs. 87 years), it has been proposed as an active element of radioisotope thermoelectric generators, for example in spacecraft.<ref name="RTG">Basic elements of static RTGs Template:Webarchive, G.L. Kulcinski, NEEP 602 Course Notes (Spring 2000), Nuclear Power in Space, University of Wisconsin Fusion Technology Institute (see last page)</ref> Although americium produces less heat and electricity – the power yield is 114.7 mW/g for ²⁴¹Am and 6.31 mW/g for ²⁴³Am<ref name="res" /> (cf. 390 mW/g for ²³⁸Pu)<ref name="RTG" /> – and its radiation poses more threat to humans owing to neutron emission, the European Space Agency is considering using americium for its space probes.<ref>Space agencies tackle waning plutonium stockpiles, Spaceflight now, 9 July 2010</ref>

Another proposed space-related application of americium is a fuel for space ships with nuclear propulsion. It relies on the very high rate of nuclear fission of ^242mAm, which can be maintained even in a micrometer-thick foil. Small thickness avoids the problem of self-absorption of emitted radiation. This problem is pertinent to uranium or plutonium rods, in which only surface layers provide alpha-particles.<ref name="rocket">{{#invoke:citation/CS1|citation |CitationClass=web }}</ref><ref>Template:Cite conference</ref> The fission products of ^242mAm can either directly propel the spaceship or they can heat a thrusting gas. They can also transfer their energy to a fluid and generate electricity through a magnetohydrodynamic generator.<ref name="mprice">Template:Cite journal</ref>

One more proposal which utilizes the high nuclear fission rate of ^242mAm is a nuclear battery. Its design relies not on the energy of the emitted by americium alpha particles, but on their charge, that is the americium acts as the self-sustaining "cathode". A single 3.2 kg ^242mAm charge of such battery could provide about 140 kW of power over a period of 80 days.<ref>Genuth, Iddo Americium Power Source Template:Webarchive, The Future of Things, 3 October 2006, Retrieved 28 November 2010</ref> Even with all the potential benefits, the current applications of ^242mAm are as yet hindered by the scarcity and high price of this particular nuclear isomer.<ref name="mprice" />

In 2019, researchers at the UK National Nuclear Laboratory and the University of Leicester demonstrated the use of heat generated by americium to illuminate a small light bulb. This technology could lead to systems to power missions with durations up to 400 years into interstellar space, where solar panels do not function.<ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref><ref>Template:Cite magazine</ref>

Neutron source

The oxide of ²⁴¹Am pressed with beryllium is an efficient neutron source. Here americium acts as the alpha source, and beryllium produces neutrons owing to its large cross-section for the (α,n) nuclear reaction:

<chem>^{241}_{95}Am -> ^{237}_{93}Np + ^{4}_{2}He + \gamma</chem>

<chem>^{9}_{4}Be + ^{4}_{2}He -> ^{12}_{6}C + ^{1}_{0}n + \gamma</chem>

The most widespread use of ²⁴¹AmBe neutron sources is a neutron probe – a device used to measure the quantity of water present in soil, as well as moisture/density for quality control in highway construction. ²⁴¹Am neutron sources are also used in well logging applications, as well as in neutron radiography, tomography and other radiochemical investigations.<ref name="Binder" />

Production of other elements

Americium is a starting material for the production of other transuranic elements and transactinides – for example, 82.7% of ²⁴²Am decays to ²⁴²Cm and 17.3% to ²⁴²Pu. In the nuclear reactor, ²⁴²Am is also up-converted by neutron capture to ²⁴³Am and ²⁴⁴Am, which transforms by β-decay to ²⁴⁴Cm:

<chem>^{243}_{95}Am ->[\ce{(n,\gamma)}] ^{244}_{95}Am ->[\beta^-][10.1 \ \ce{h}] ^{244}_{96}Cm</chem>

Irradiation of ²⁴¹Am by ¹²C or ²²Ne ions yields the isotopes ²⁴⁷Es (einsteinium) or ²⁶⁰Db (dubnium), respectively.<ref name="Binder">Template:Cite book</ref> Furthermore, the element berkelium (²⁴³Bk isotope) had been first intentionally produced and identified by bombarding ²⁴¹Am with alpha particles, in 1949, by the same Berkeley group, using the same 60-inch cyclotron. Similarly, nobelium was produced at the Joint Institute for Nuclear Research, Dubna, Russia, in 1965 in several reactions, one of which included irradiation of ²⁴³Am with ¹⁵N ions. Besides, one of the synthesis reactions for lawrencium, discovered by scientists at Berkeley and Dubna, included bombardment of ²⁴³Am with ¹⁸O.<ref name="g1252" />

Spectrometer

Americium-241 has been used as a portable source of both gamma rays and alpha particles for a number of medical and industrial uses. The 59.5409 keV gamma ray emissions from ²⁴¹Am in such sources can be used for indirect analysis of materials in radiography and X-ray fluorescence spectroscopy, as well as for quality control in fixed nuclear density gauges and nuclear densometers. For example, the element has been employed to gauge glass thickness to help create flat glass.<ref name="g1262" /> Americium-241 is also suitable for calibration of gamma-ray spectrometers in the low-energy range, since its spectrum consists of nearly a single peak and negligible Compton continuum (at least three orders of magnitude lower intensity).<ref>Nuclear Data Viewer 2.4 Template:Webarchive, NNDC</ref> Americium-241 gamma rays were also used to provide passive diagnosis of thyroid function. This medical application is however obsolete.

Health concerns

As a highly radioactive element, americium and its compounds must be handled only in an appropriate laboratory under special arrangements. Although most americium isotopes predominantly emit alpha particles which can be blocked by thin layers of common materials, many of the daughter products emit gamma-rays and neutrons which have a long penetration depth.<ref>Public Health Statement for Americium Section 1.5., Agency for Toxic Substances and Disease Registry, April 2004, Retrieved 28 November 2010</ref>

If consumed, most of the americium is excreted within a few days, with only 0.05% absorbed in the blood, of which roughly 45% goes to the liver and 45% to the bones, and the remaining 10% is excreted. The uptake to the liver depends on the individual and increases with age. In the bones, americium is first deposited over cortical and trabecular surfaces and slowly redistributes over the bone with time. The biological half-life of ²⁴¹Am is 50 years in the bones and 20 years in the liver, whereas in the gonads (testicles and ovaries) it remains permanently; in all these organs, americium promotes formation of cancer cells as a result of its radioactivity.<ref name="am" /><ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref><ref>Frisch, Franz Crystal Clear, 100 x energy, Bibliographisches Institut AG, Mannheim 1977, Template:ISBN, p. 184</ref>

Americium often enters landfills from discarded smoke detectors. The rules associated with the disposal of smoke detectors are relaxed in most jurisdictions. In 1994, 17-year-old David Hahn extracted the americium from about 100 smoke detectors in an attempt to build a breeder nuclear reactor.<ref name="Silverstein2005">Ken Silverstein, The Radioactive Boy Scout: When a teenager attempts to build a breeder reactor. Harper's Magazine, November 1998</ref><ref>Template:Cite news</ref><ref>Template:Cite news</ref><ref>Template:Cite news</ref> There have been a few cases of exposure to americium, the worst case being that of chemical operations technician Harold McCluskey, who at the age of 64 was exposed to 500 times the occupational standard for americium-241 as a result of an explosion in his lab. McCluskey died at the age of 75 of unrelated pre-existing disease.<ref name="tristateherald">Template:Cite news</ref><ref>Template:Cite news</ref>

See also

• Actinides in the environment
• Category:Americium compounds

Bibliography

• Template:Greenwood&Earnshaw2nd
• Penneman, R. A. and Keenan T. K. The radiochemistry of americium and curium, University of California, Los Alamos, California, 1960
• Template:Cite book

Further reading

• Nuclides and Isotopes – 14th Edition, GE Nuclear Energy, 1989.
• {{#invoke:citation/CS1|citation

|CitationClass=web }}

• Template:Cite book

External links

• Americium at The Periodic Table of Videos (University of Nottingham)
• ATSDR – Public Health Statement: Americium
• World Nuclear Association – Smoke Detectors and Americium