Actinium

Actinium is a chemical element with the symbol Ac and atomic number 89. It was first isolated 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. Actinium gave the name to the actinide series, a group of 15 similar elements between actinium and lawrencium in the periodic table. Together with polonium, radium, and radon, actinium was one of the first non-primordial radioactive elements to be isolated.

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 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

André-Louis Debierne, 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 (in 1900) 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'' (ακτίς, ακτίνος), 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,''Actinium'', in Encyclopædia Britannica, 15th edition, 1995, p. 70 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 (although it had been proposed as early as 1892 by British chemist Henry Bassett).

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 nd¹7s² 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 actinium is generally regarded by chemists working on it as the first 5f element. 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 Ac(NO₃)₃. Except for AcPO₄, they are all similar to the corresponding lanthanum compounds. 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 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

Actinium oxide (Ac₂O₃) can be obtained by heating the hydroxide at 500 °C or the oxalate at 1100 °C, in vacuum. Its crystal lattice is isotypic with the oxides of most trivalent rare-earth metals.

Halides

Actinium trifluoride 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 700 °C in an all-platinum setup. Treating actinium trifluoride with ammonium hydroxide at 900–1000 °C yields oxyfluoride AcOF. Whereas lanthanum oxyfluoride can be easily obtained by burning lanthanum trifluoride in air at 800 °C for an hour, similar treatment of actinium trifluoride yields no AcOF and only results in melting of the initial product.Meyer, pp. 87–88

:AcF₃ + 2 NH₃ + H₂O → AcOF + 2 NH₄F

Actinium trichloride is obtained by reacting actinium hydroxide or oxalate with carbon tetrachloride vapors at temperatures above 960 °C. Similar to oxyfluoride, actinium oxychloride can be prepared by hydrolyzing actinium trichloride with ammonium hydroxide at 1000 °C. 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:
:Ac₂O₃ + 2 AlBr₃ → 2 AcBr₃ + Al₂O₃

and treating it with ammonium hydroxide at 500 °C results in the oxybromide AcOBr.

Other compounds

Actinium hydride was obtained by reduction of actinium trichloride with potassium at 300 °C, and its structure was deduced by analogy with the corresponding LaH₂ hydride. The source of hydrogen in the reaction was uncertain.

Mixing monosodium phosphate (NaH₂PO₄) with a solution of actinium in hydrochloric acid yields white-colored actinium phosphate hemihydrate (AcPO₄·0.5H₂O), and heating actinium oxalate with hydrogen sulfide vapors at 1400 °C for a few minutes results in a black actinium sulfide Ac₂S₃. It may possibly be produced by acting with a mixture of hydrogen sulfide and carbon disulfide on actinium oxide at 1000 °C.

Isotopes

Naturally occurring actinium is composed of two radioactive isotopes; (from the radioactive family of ) and (a granddaughter of ). 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-six radioisotopes have been identified, the most stable being with a half-life of 21.772 years, 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 (half-life of 69 nanoseconds) which decays through alpha decay. Actinium also has two known meta states. The most significant isotopes for chemistry are ²²⁵Ac, ²²⁷Ac, and ²²⁸Ac.

Purified comes into equilibrium with its decay products after about a half of year. It decays according to its 21.772-year half-life emitting mostly beta (98.62%) and some alpha particles (1.38%); the successive decay products are part of the actinium series. Owing to the low available amounts, low energy of its beta particles (maximum 44.8 keV) and low intensity of alpha radiation, is difficult to detect directly by its emission and it is therefore traced via its decay products.Actinium
Great Soviet Encyclopedia (in Russian) The isotopes of actinium range in atomic weight from 205  u () to 236 u ().

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 (or ²³⁹Pu) 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 (²²⁵Ac) is transiently present in the neptunium series decay chain, beginning with ²³⁷Np (or ²³³U) and ending with thallium ( ²⁰⁵Tl) and near-stable bismuth ( ²⁰⁹Bi); 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, and complete separation was never achieved. Instead, actinium is prepared, in milligram amounts, by the neutron irradiation of in a nuclear reactor.
:^_Ra + ^_n -> ^_Ra -> beta^-42.2 \ \ce] ^_Ac
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 (to about 6.0 for actinium). 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 (ITU) 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 1100 and 1300 °C. Higher temperatures resulted in evaporation of the product and lower ones lead to an incomplete transformation. Lithium was chosen among other alkali metals because its fluoride is most volatile.Hammond, C. R. ''The Elements'' in

Applications

Owing to its scarcity, high price and radioactivity, ²²⁷Ac currently has no significant industrial use, but ²²⁵Ac is currently being studied for use in cancer treatments such as targeted alpha therapies.
²²⁷Ac is highly radioactive and was therefore studied for use as an active element of radioisotope thermoelectric generators, for example in spacecraft. The oxide of ²²⁷Ac pressed with beryllium is also an efficient neutron source with the activity exceeding that of the standard americium-beryllium and radium-beryllium pairs.Russell, Alan M. and Lee, Kok Loong (2005
''Structure-property relations in nonferrous metals''
Wiley. , pp. 470–471 In all those applications, ²²⁷Ac (a beta source) is merely a progenitor which generates alpha-emitting isotopes upon its decay. Beryllium captures alpha particles and emits neutrons owing to its large cross-section for the (α,n) nuclear reaction:

: ^_Be + ^_He -> ^_C + ^_n + \gamma

The ²²⁷AcBe neutron sources can be applied in a neutron probe – a standard device for measuring the quantity of water present in soil, as well as moisture/density for quality control in highway construction. Such probes are also used in well logging applications, in neutron radiography, tomography and other radiochemical investigations.

²²⁵Ac is applied in medicine to produce in a reusable generator or can be used alone as an agent for radiation therapy, in particular targeted alpha therapy (TAT). This isotope has a half-life of 10 days, making it much more suitable for radiation therapy than ²¹³Bi (half-life 46 minutes). Additionally, ²²⁵Ac decays to nontoxic ²⁰⁹Bi rather than stable but toxic lead, which is the final product in the decay chains of several other candidate isotopes, namely ²²⁷Th, ²²⁸Th, and ²³⁰U. Not only ²²⁵Ac itself, but also its daughters, emit alpha particles which kill cancer cells in the body. The major difficulty with application of ²²⁵Ac was that intravenous injection of simple actinium complexes resulted in their accumulation in the bones and liver for a period of tens of years. As a result, after the cancer cells were quickly killed by alpha particles from ²²⁵Ac, the radiation from the actinium and its daughters might induce new mutations. To solve this problem, ²²⁵Ac was bound to a chelating agent, such as citrate, ethylenediaminetetraacetic acid (EDTA) or diethylene triamine pentaacetic acid (DTPA). This reduced actinium accumulation in the bones, but the excretion from the body remained slow. Much better results were obtained with such chelating agents as HEHA () or DOTA () coupled to trastuzumab, a monoclonal antibody that interferes with the HER2/neu receptor. The latter delivery combination was tested on mice and proved to be effective against leukemia, lymphoma, breast, ovarian, neuroblastoma and prostate cancers.

The medium half-life of ²²⁷Ac (21.77 years) makes it very convenient radioactive isotope in modeling the slow vertical mixing of oceanic waters. The associated processes cannot be studied with the required accuracy by direct measurements of current velocities (of the order 50 meters per year). However, evaluation of the concentration depth-profiles for different isotopes allows estimating the mixing rates. The physics behind this method is as follows: oceanic waters contain homogeneously dispersed ²³⁵U. Its decay product, ²³¹Pa, gradually precipitates to the bottom, so that its concentration first increases with depth and then stays nearly constant. ²³¹Pa decays to ²²⁷Ac; however, the concentration of the latter isotope does not follow the ²³¹Pa depth profile, but instead increases toward the sea bottom. This occurs because of the mixing processes which raise some additional ²²⁷Ac from the sea bottom. Thus analysis of both ²³¹Pa and ²²⁷Ac depth profiles allows researchers to model the mixing behavior.

There are theoretical predictions that AcH_x hydrides (in this case with very high pressure) are a candidate for a near room-temperature superconductor as they have T_c significantly higher than H3S, possibly near 250 K.

Precautions

²²⁷Ac is highly radioactive and experiments with it are carried out in a specially designed laboratory equipped with a tight glove box. When actinium trichloride is administered intravenously to rats, about 33% of actinium is deposited into the bones and 50% into the liver. Its toxicity is comparable to, but slightly lower than that of americium and plutonium. For trace quantities, fume hoods with good aeration suffice; for gram amounts, hot cells with shielding from the intense gamma radiation emitted by ²²⁷Ac are necessary.

See also

* Actinium series

Notes

References

Bibliography

* Meyer, Gerd and Morss, Lester R. (1991
''Synthesis of lanthanide and actinide compounds''
Springer.

External links

at ''The Periodic Table of Videos'' (University of Nottingham)

NLM Hazardous Substances Databank – Actinium, Radioactive

Actinium
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Chemical elements
Chemical elements with face-centered cubic structure
Actinides