The 14th International Conference on

Miniaturized Systems for Chemistry and Life Sciences

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Astatine





 

Astatine

Astatine is a radioactive chemical element with the symbol At and atomic number 85. It is the rarest naturally occurring element in the Earth's crust, occurring only as the decay product of various heavier elements. All of astatine's isotopes are short-lived; the most stable is astatine-210, with a half-life of 8.1 hours. A sample of the pure element has never been assembled, because any macroscopic specimen would be immediately vaporized by the heat of its own radioactivity.

The bulk properties of astatine are not known with any certainty. Many of them have been estimated based on the element's position on the periodic table as a heavier analog of iodine, and a member of the halogens (the group of elements including fluorine, chlorine, bromine, and iodine). Astatine is likely to have a dark or lustrous appearance and may be a semiconductor or possibly a metal; it probably has a higher melting point than that of iodine. Chemically, several anionic species of astatine are known and most of its compounds resemble those of iodine. It also shows some metallic behavior, including being able to form a stable monatomic cation in aqueous solution (unlike the lighter halogens).

Astatine is an extremely radioactive element; all its isotopes have short half-lives of 8.1 hours or less, decaying into other astatine isotopes, bismuth, polonium or radon. Most of its isotopes are very unstable with half-lives of one second or less. Of the first 101 elements in the periodic table, only francium is less stable, and all the astatine isotopes more stable than francium are in any case synthetic and do not occur in nature.

The bulk properties of astatine are not known with any certainty. Research is limited by its short half-life, which prevents the creation of weighable quantities. A visible piece of astatine would immediately vaporize itself because of the heat generated by its intense radioactivity. It remains to be seen if, with sufficient cooling, a macroscopic quantity of astatine could be deposited as a thin film. Astatine is usually classified as either a nonmetal or a metalloid; metal formation has also been predicted.

Astatine has an electronegativity of 2.2 on the revised Pauling scale - lower than that of iodine (2.66) and the same as hydrogen. In hydrogen astatide (HAt) the negative charge is predicted to be on the hydrogen atom, implying that this compound could be referred to as astatine hydride according to certain nomenclatures. That would be consistent with the electronegativity of astatine on the Allred¥Rochow scale (1.9) being less than that of hydrogen (2.2). However, official IUPAC stoichiometric nomenclature is based on an idealized convention of determining the relative electronegativities of the elements by the mere virtue of their position within the periodic table. According to this convention, astatine is handled as though it is more electronegative than hydrogen, irrespective of its true electronegativity. The electron affinity of astatine is predicted to be reduced by one-third because of spin-orbit interactions.

Only a few compounds with metals have been reported, in the form of astatides of sodium, palladium, silver, thallium, and lead. Some characteristic properties of silver and sodium astatide, and the other hypothetical alkali and alkaline earth astatides, have been estimated by extrapolation from other metal halides.

The first claimed discovery of eka-iodine was made by Fred Allison and his associates at the Alabama Polytechnic Institute (now Auburn University) in 1931. The discoverers named element 85 "alabamine", and assigned it the symbol Ab, designations that were used for a few years. In 1934, H. G. MacPherson of University of California, Berkeley disproved Allison's method and the validity of his discovery. There was another claim in 1937, by the chemist Rajendralal De. Working in Dacca in British India (now Dhaka in Bangladesh), he chose the name "dakin" for element 85, which he claimed to have isolated as the thorium series equivalent of radium F (polonium-210) in the radium series. The properties he reported for dakin do not correspond to those of astatine; moreover, astatine is not found in the thorium series, and the true identity of dakin is not known.

In 1940, the Swiss chemist Walter Minder announced the discovery of element 85 as the beta decay product of radium A (polonium-218), choosing the name "helvetium" (from Helvetia, the Latin name of Switzerland). Karlik and Bernert were unsuccessful in reproducing his experiments, and subsequently attributed Minder's results to contamination of his radon stream (radon-222 is the parent isotope of polonium-218). In 1942, Minder, in collaboration with the English scientist Alice Leigh-Smith, announced the discovery of another isotope of element 85, presumed to be the product of thorium A (polonium-216) beta decay. They named this substance "anglo-helvetium", but Karlik and Bernert were again unable to reproduce these results.

Astatine's alpha decay energies follow the same trend as for other heavy elements. Lighter astatine isotopes have quite high energies of alpha decay, which become lower as the nuclei become heavier. Astatine-211 has a significantly higher energy than the previous isotope, because it has a nucleus with 126 neutrons, and 126 is a magic number corresponding to a filled neutron shell. Despite having a similar half-life to the previous isotope (8.1 hours for astatine-210 and 7.2 hours for astatine-211), the alpha decay probability is much higher for the latter: 41.81% against only 0.18%. The two following isotopes release even more energy, with astatine-213 releasing the most energy. For this reason, it is the shortest-lived astatine isotope. Even though heavier astatine isotopes release less energy, no long-lived astatine isotope exists, because of the increasing role of beta decay (electron emission). This decay mode is especially important for astatine; as early as 1950 it was postulated that all isotopes of the element undergo beta decay, though nuclear mass measurements reveal that 215At is in fact beta-stable, as it has the lowest mass of all isobars with A = 215. A beta decay mode has been found for all other astatine isotopes except for astatine-213, astatine-214, and astatine-216m. Astatine-210 and lighter isotopes exhibit beta plus decay (positron emission), astatine-216 and heavier isotopes exhibit beta (minus) decay, and astatine-212 decays via both modes, while astatine-211 undergoes electron capture.

The most important isotope is astatine-211, the only one in commercial use. To produce the bismuth target, the metal is sputtered onto a gold, copper, or aluminium surface at 50 to 100 milligrams per square centimeter. Bismuth oxide can be used instead; this is forcibly fused with a copper plate. The target is kept under a chemically neutral nitrogen atmosphere, and is cooled with water to prevent premature astatine vaporization. In a particle accelerator, such as a cyclotron, alpha particles are collided with the bismuth. Even though only one bismuth isotope is used (bismuth-209), the reaction may occur in three possible ways, producing astatine-209, astatine-210, or astatine-211. In order to eliminate undesired nuclides, the maximum energy of the particle accelerator is set to a value (optimally 29.17 MeV) above that for the reaction producing astatine-211 (to produce the desired isotope) and below the one producing astatine-210 (to avoid producing other astatine isotopes).







 

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