Actinium

Actinium is a chemical element; it has symbol Ac and atomic number 89. It was discovered by Friedrich Oskar Giesel in 1902, who gave it the name emanium; the element got its name by being wrongly identified with a substance André-Louis Debierne found in 1899 and called actinium. The actinide series, a set of 15 elements between actinium and lawrencium in the periodic table, is named after actinium. Together with polonium, radium, and radon, actinium was one of the first non-primordial radioactive elements to be discovered.
A soft, silvery-white radioactive metal, actinium reacts rapidly with oxygen and moisture in air, forming a white coating of actinium oxide that prevents further oxidation. As with most lanthanides and many actinides, actinium assumes oxidation state +3 in nearly all its chemical compounds. Actinium is found only in traces in uranium and thorium ores as the isotope ²²⁷Ac, which decays with a half-life of 21.772 years, predominantly emitting beta and sometimes alpha particles, and ²²⁸Ac, which is beta active with a half-life of 6.15 hours. One tonne of natural uranium in ore contains about 0.2 milligrams of actinium-227, and one tonne of thorium contains about 5 nanograms of actinium-228. The close similarity of physical and chemical properties of actinium and lanthanum makes the separation of actinium from the ore impractical. Instead, the element is prepared, in milligram amounts, by the neutron irradiation of in a nuclear reactor. Owing to its scarcity, high price, and radioactivity, actinium has no significant industrial use. Its current applications include a neutron source and an agent for radiation therapy.

History

, a French chemist, announced the discovery of a new element in 1899. He separated it from pitchblende residues left by Marie and Pierre Curie after they had extracted radium. In 1899, Debierne described the substance as similar to titanium and as similar to thorium. Friedrich Oskar Giesel found in 1902 a substance similar to lanthanum and called it "emanium" in 1904. After a comparison of the substances' half-lives determined by Debierne, Harriet Brooks in 1904, and Otto Hahn and Otto Sackur in 1905, Debierne's chosen name for the new element was retained because it had seniority, despite the contradicting chemical properties he claimed for the element at different times.
Articles published in the 1970s and later suggest that Debierne's results published in 1904 conflict with those reported in 1899 and 1900. Furthermore, the now-known chemistry of actinium precludes its presence as anything other than a minor constituent of Debierne's 1899 and 1900 results; in fact, the chemical properties he reported make it likely that he had, instead, accidentally identified protactinium, which would not be discovered for another fourteen years, only to have it disappear due to its hydrolysis and adsorption onto his laboratory equipment. This has led some authors to advocate that Giesel alone should be credited with the discovery. A less confrontational vision of scientific discovery is proposed by Adloff. He suggests that hindsight criticism of the early publications should be mitigated by the then nascent state of radiochemistry: highlighting the prudence of Debierne's claims in the original papers, he notes that nobody can contend that Debierne's substance did not contain actinium. Debierne, who is now considered by the vast majority of historians as the discoverer, lost interest in the element and left the topic. Giesel, on the other hand, can rightfully be credited with the first preparation of radiochemically pure actinium and with the identification of its atomic number 89.
The name actinium originates from the Ancient Greek aktis, aktinos, meaning beam or ray. Its symbol Ac is also used in abbreviations of other compounds that have nothing to do with actinium, such as acetyl, acetate and sometimes acetaldehyde.

Properties

Actinium is a soft, silvery-white, radioactive, metallic element. Its estimated shear modulus is similar to that of lead. Owing to its strong radioactivity, actinium glows in the dark with a pale blue light, which originates from the surrounding air ionized by the emitted energetic particles. Actinium has similar chemical properties to lanthanum and other lanthanides, and therefore these elements are difficult to separate when extracting from uranium ores. Solvent extraction and ion chromatography are commonly used for the separation.
The first element of the actinides, actinium, gave the set its name, much as lanthanum had done for the lanthanides. The actinides are much more diverse than the lanthanides and therefore it was not until 1945 that the most significant change to Dmitri Mendeleev's periodic table since the recognition of the lanthanides, the introduction of the actinides, was generally accepted after Glenn T. Seaborg's research on the transuranium elements.
Actinium reacts rapidly with oxygen and moisture in air, forming a white coating of actinium oxide that impedes further oxidation. As with most lanthanides and actinides, actinium exists in the oxidation state +3, and the Ac³⁺ ions are colorless in solutions. The oxidation state +3 originates from the 6d¹7s² electronic configuration of actinium, with three valence electrons that are easily donated to give the stable closed-shell structure of the noble gas radon. Although the 5f orbitals are unoccupied in an actinium atom, it can be used as a valence orbital in actinium complexes and hence it is generally considered the first 5f element by authors working on it. Ac³⁺ is the largest of all known tripositive ions and its first coordination sphere contains approximately 10.9 ± 0.5 water molecules.

Chemical compounds

Due to actinium's intense radioactivity, only a limited number of actinium compounds are known. These include: AcF₃, AcCl₃, AcBr₃, AcOF, AcOCl, AcOBr, Ac₂S₃, Ac₂O₃, AcPO₄ and Ac₃. They all contain actinium in the oxidation state +3. In particular, the lattice constants of the analogous lanthanum and actinium compounds differ by only a few percent.
Here a, b and c are lattice constants, No is the space group number, and Z is the number of formula units per unit cell. Density was not measured directly but calculated from the lattice parameters.

Oxides

can be obtained by heating the hydroxide at or the oxalate at, in vacuum. Its crystal lattice is isotypic with the oxides of most trivalent rare-earth metals.

Halides

can be produced either in solution or in solid reaction. The former reaction is carried out at room temperature, by adding hydrofluoric acid to a solution containing actinium ions. In the latter method, actinium metal is treated with hydrogen fluoride vapors at in an all-platinum setup. Treating actinium trifluoride with ammonium hydroxide at yields oxyfluoride AcOF. Whereas lanthanum oxyfluoride can be easily obtained by burning lanthanum trifluoride in air at for an hour, similar treatment of actinium trifluoride yields no AcOF and only results in melting of the initial product.
Actinium trichloride is obtained by reacting actinium hydroxide or oxalate with carbon tetrachloride vapors at temperatures above. Similarly to the oxyfluoride, actinium oxychloride can be prepared by hydrolyzing actinium trichloride with ammonium hydroxide at. However, in contrast to the oxyfluoride, the oxychloride could well be synthesized by igniting a solution of actinium trichloride in hydrochloric acid with ammonia.
Reaction of aluminium bromide and actinium oxide yields actinium tribromide:
and treating it with ammonium hydroxide at results in the oxybromide AcOBr.

Other compounds

was obtained by reduction of actinium trichloride with potassium at, and its structure was deduced by analogy with the corresponding LaH₂ hydride. The source of hydrogen in the reaction was uncertain.
Mixing monosodium phosphate with a solution of actinium in hydrochloric acid yields white-colored actinium phosphate hemihydrate, and heating actinium oxalate with hydrogen sulfide vapors at for a few minutes results in a black actinium sulfide Ac₂S₃. It may be produced by acting with a mixture of hydrogen sulfide and carbon disulfide on actinium oxide at.

Isotopes

Naturally occurring actinium is principally composed of two radioactive isotopes; and . decays mainly as a beta emitter with a very small energy, but in 1.38% of cases it emits an alpha particle, so it can readily be identified through alpha spectrometry. Thirty-three radioisotopes have been identified, the most stable being with a half-life of 21.772 years, actinium-225| with a half-life of 10.0 days and with a half-life of 29.37 hours. All remaining radioactive isotopes have half-lives that are less than 10 hours, and the majority of them have half-lives shorter than one minute. The shortest-lived known isotope of actinium is which decays through alpha decay. Actinium also has two known meta states. The most significant isotopes for chemistry are,, and.
Purified comes into equilibrium with its decay products after about a half-year. It decays according to its 21.772-year half-life, emitting mostly beta and some alpha particles ; the successive decay products are part of the actinium series. Owing to the low available amounts, low energy of its beta particles and low intensity of alpha radiation, is difficult to detect directly by its emission, and it is therefore traced via its decay products. The isotopes of actinium range in atomic weight from to .

Occurrence and synthesis

Actinium is found only in traces in uranium ores – one tonne of uranium in ore contains about 0.2 milligrams of ²²⁷Ac – and in thorium ores, which contain about 5 nanograms of ²²⁸Ac per one tonne of thorium. The actinium isotope ²²⁷Ac is a transient member of the uranium-actinium series decay chain, which begins with the parent isotope ²³⁵U and ends with the stable lead isotope ²⁰⁷Pb. The isotope ²²⁸Ac is a transient member of the thorium series decay chain, which begins with the parent isotope ²³²Th and ends with the stable lead isotope ²⁰⁸Pb. Another actinium isotope is transiently present in the neptunium series decay chain, beginning with ²³⁷Np and ending with thallium and near-stable bismuth ; even though all primordial ²³⁷Np has decayed away, it is continuously produced by neutron knock-out reactions on natural ²³⁸U.
The low natural concentration and the close similarity of physical and chemical properties to those of lanthanum and other lanthanides, which are always abundant in actinium-bearing ores, render separation of actinium from the ore impractical. The most concentrated actinium sample prepared from raw material consisted of 7 micrograms of ²²⁷Ac in less than 0.1 milligrams of La₂O₃, and complete separation was never achieved. Instead, actinium is prepared, in milligram amounts, by the neutron irradiation of in a nuclear reactor.
The reaction yield is about 2% of the radium weight. ²²⁷Ac can further capture neutrons resulting in small amounts of ²²⁸Ac. After the synthesis, actinium is separated from radium and from the products of decay and nuclear fusion, such as thorium, polonium, lead, and bismuth. The extraction can be performed with thenoyltrifluoroacetone-benzene solution from an aqueous solution of the radiation products, and the selectivity to a certain element is achieved by adjusting the pH. An alternative procedure is anion exchange with an appropriate resin in nitric acid, which can result in a separation factor of 1,000,000 for radium and actinium vs. thorium in a two-stage process. Actinium can then be separated from radium, with a ratio of about 100, using a low cross-linking cation exchange resin and nitric acid as eluant.
²²⁵Ac was first produced artificially at the Institute for Transuranium Elements in Germany using a cyclotron and at St George Hospital in Sydney using a linac in 2000. This rare isotope has potential applications in radiation therapy and is most efficiently produced by bombarding a radium-226 target with 20–30 MeV deuterium ions. This reaction also yields ²²⁶Ac which however decays with a half-life of 29 hours and thus does not contaminate ²²⁵Ac.
Actinium metal has been prepared by the reduction of actinium fluoride with lithium vapor in vacuum at a temperature between. Higher temperatures resulted in evaporation of the product, and lower temperatures led to an incomplete transformation. Lithium was chosen among other alkali metals because its fluoride is the most volatile.