Polonium: did it kill Alexander Litvinenko?

Polonium metal structurePolonium metal structureIt is suggested that poisoning by polonium-210 may have caused the death of Alexander Litvinenko, said to be a former Russian spy, in November 2006. Following his death at the end of November 2006, traces of polonium were found at several places he had visited before becoming ill. Before his death it was thought that thallium, or even radiothallium, might have been the cause of his illness. At the time of writing it is not clear who killed him, but not surprisingly the Russians deny it. Polonium-210 decays through the emission of α-particles and these emissions are noramlly easy to stop, but they are very dangerous if the polonium is inside the body.

Polonium is radioactive and present only in extremely low abundances in the environment. It is quite metallic in nature despite its location beneath oxygen in the periodic table. It is made in very small quantities through a nuclear reaction of bismuth. Neutron irradiation of 209bismuth (atomic number 83) gives 210polonium (atomic number 84).

209Bi + 1n → 210Po + e-

Polonium-210, 210Po, transmutes into the lead isotope 206Pb by the emission of an α-particle. The half life for this process is just over 138 days meaning that after 138 days one-half of the original 210Po has disappeared and after 2 times 138 days 3/4 has gone.

21084Po → 20682Pb + 42He

The short half life of polonium-210 and the heat generated with the above radioactive decay means that polonium metal generates considerable heat (141 W), meaning that the metal and its compounds self-heat. This is a useful property and polonium can be used as a small heat source (if expensive!). It can be used in space satellites for this purpose and is especially desirable as there are no moving parts. It was also used in the lunar rovers to keep internal parts warm during the frigid lunar nights.

Polonium metal is unique in that it is the only element whose structure (known as the α-form) is a simple cubic array of atoms in which each atom is surrounded by six other polonium atoms. On gentle warming to 36°C, this converts into a second form known as the β-form.

Polonium dioxidePolonium dioxidePolonium dissolves in acids to form pink hydrated Po(II), presumably as[Po(OH2)6]2+. This seems to oxidize to yellow Po(IV) species perhaps as a consequence of oxidizing agents produced through the α-particle induced decay of water. The polonium(II) oxide PoO is known but this oxidizes easily to the Po(IV) oxide PoO2.

Polonium dichloridePolonium dichlorideThe Po(II) halides PoX2 (X = Cl, Br, I) are known (the chloride and bromide are particularly well characterised) while all the Po(IV) halides PoX4 (X = F, Cl, Br, I) are known.

There are few crystallographically characterised polonium compounds largely because not many researchers work with polonium and the difficulties associated with characterising such radioactive compounds. The 14-electron polonium(IV) anion [PoI6]2– is strictly octahedral meaning the lone pair is sterochemically inactive.

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Copyright 1993-2011 Mark Winter [The University of Sheffield and WebElements Ltd, UK]. All rights reserved.