Time-resolved laser fluorescence spectroscopy and extended X-ray absorption spectroscopy investigations of-the N-3(-) complexation of Eu(III), Cm(III), and Am(III) in an ionic liquid: Differences and similarities

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Output type: Journal article

Author list: Stumpf S, Billard I, Gaillard C, Panak PJ, Dardenne K

Publisher: American Chemical Society

Publication year: 2008

Journal: Inorganic Chemistry (0020-1669)

Volume number: 47

Issue number: 11

Start page: 4618

End page: 4626

Number of pages: 9

ISSN: 0020-1669

eISSN: 1520-510X

Languages: English-Great Britain (EN-GB)

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Open access status: closed

Abstract

The complexation of the lanthanide Eu(III) and the actinides Cm(III) and Am(III) by N-3(-) was investigated by application of time-resolved laser fluorescence spectroscopy (TRLFS) and X-ray absorption spectroscopy (XAFS) in the ionic liquid solution Of C(4)mimTf(2)N (1-butyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide). TRLFS, measurements show that the interaction of azide with Eu(CF3SO3)(3) and Eu(ClO4)(3) results in both dynamic luminescence quenching by collisional encounters of N-3(-) with Eu(III) and static luminescence quenching by inner-sphere complexation of Eu(III) by N-3(-). Hereby, the complexation of Eu-triflate by azide starts at a lower N-3(-) concentration as compared to the perchlorate salt. The authors ascribe this phenomenon to a stronger bonding Of ClO4- toward the metal ion than triflate, as well as to a stronger electrostatic repulsion of N-3(-) by the perchlorate ligand. In both actinide samples (Cm(ClO4)(3), Am(ClO4)(3)), the complexation with azide exhibits a clear kinetic hindrance. Nevertheless, mixed actinide-perchlorate-azide complexes are formed after several days in C(4)mimTf(2)N. The different reaction kinetics for the Ln- and An-complexation by azide may provide the opportunity for an effective separation of lanthanides from actinides in the nuclear fuel cycle by the use of N-based extractants in ionic liquid solution.

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