Title: Time-Resolved Laser Fluorescence Spectroscopy and Extended X-Ray Absorption Spectroscopy Investigations of the N3- Complexation of Eu(III), Cm(III), and Am(III) in an Ionic Liquid: Differences and Similarities
Citation: INORGANIC CHEMISTRY vol. 47 no. 11 p. 4618-4626
Publication Year: 2008
JRC N°: JRC47069
ISSN: 0020-1669
URI: http://pubs.acs.org/cgi-bin/abstract.cgi/inocaj/2008/47/i11/abs/ic7023567.html
DOI: 10.1021/ic7023567
Type: Articles in periodicals and books
Abstract: The complexation of the lanthanide Eu(III) and the actinides Cm(III) and Am(III) by N3- was investigated by application of time-resolved laser fluorescence spectroscopy (TRLFS) and X-ray absorption spectroscopy (XAFS) in the ionic liquid solution of C4mimTf2N (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 N3- with Eu(III) and static luminescence quenching by inner-sphere complexation of Eu(III) by N3-. Hereby, the complexation of Eu-triflate by azide starts at a lower N3- 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 N3- 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 C4mimTf2N. 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.
JRC Directorate:Nuclear Safety and Security

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