Study of the electrochemical oxidation of Am with lacunary heteropolyanions and silver nitrate

Electrochemical oxidation of Am(III) with certain lacunary heteropolyanions (LHPA α2-P2W17O6110- or αSiW11O398-) and silver nitrate is an efficient way to prepare Am(VI). This document presents bibliographic data and an experimental study of the process. Thus, it has been established that Am(IV) is an intermediate species in the reaction and occurs in 1:1 (AmtIVLHPA) or 1:2 (Am IV(LHAP)2) complexes with the relevant LHPA. These 1:1 complexes of Am(IV) have been identified and isolated in this work whereas 1:2 complexes were known from previous studies. The reactivity of these complexes in oxidation shows that 1:1 complexes of Am(IV) are oxidised much more quickly than 1:2 complexes. Apparent stability constants of Am(III) and Am(IV) complexes with the relevant LHPA have been measured for a 1 M nitric acid medium. Thermodynamic data of the reaction are then assessed: redox potentials of Am pairs are computed for a 1 M nitric acid medium containing various amount of LHPA ligands. Those results show that the role of LHPA is to stabilize the intermediate species Am(IV) by lowering the Am(IV)/Am(III) pair potential of about 1 Volt. Nevertheless, if this stabilisation is too strong (i.e. of tungsto-silicate), the oxidation of Am(IV) requires high anodic potential (more than 2 V/ENH). Then, the faradic yield of the oxidation of americium is poor because of water oxidation. This study has also shown that the main role of silver is to catalyze the electrochemical oxidation of AmIV(LHPA)X complexes. Indeed, these oxidations without silver are extremely slow. An oxygen tracer experiment has been performed during the oxidation of Am(III) in Am(VI). It has been shown that the oxygen atoms of Am(VI) (AMO22+) come from water molecules of the solvent and not from the complexing oxygen atoms of the ligands. (author)