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Time-Resolved Laser Fluorescence Spectroscopy Study of the Coordination Chemistry of a Hydrophilic CHON [1,2,3-Triazol-4-yl]pyridine Ligand with Cm(III) and Eu(III)

Christoph WagnerKarlsruher Institut für Technologie (KIT), Institut für Nukleare Entsorgung (INE), P.O. Box 3640, 76021 Karlsruhe, GermanyEros MossiniPolitecnico di Milano, Department of Energy, Nuclear Engineering Division, Piazza Leonardo da Vinci 32, 20133 Milano, ItalyElena MacerataPolitecnico di Milano, Department of Energy, Nuclear Engineering Division, Piazza Leonardo da Vinci 32, 20133 Milano, ItalyMario MarianiPolitecnico di Milano, Department of Energy, Nuclear Engineering Division, Piazza Leonardo da Vinci 32, 20133 Milano, ItalyArturo ArduiniUniversità di Parma, Dipartimento di Scienze Chimiche, della Vita e della Sostenibilità Ambientale, Area delle Scienze 17/a, 43124 Parma, ItalyAlessandro CasnatiUniversità di Parma, Dipartimento di Scienze Chimiche, della Vita e della Sostenibilità Ambientale, Area delle Scienze 17/a, 43124 Parma, ItalyAndreas GeistKarlsruher Institut für Technologie (KIT), Institut für Nukleare Entsorgung (INE), P.O. Box 3640, 76021 Karlsruhe, GermanyPetra J. PanakKarlsruher Institut für Technologie (KIT), Institut für Nukleare Entsorgung (INE), P.O. Box 3640, 76021 Karlsruhe, Germany
2017en
ABI

Abstract

The complexation of Cm(III) and Eu(III) with the novel i-SANEX complexing agent 2,6-bis[1-(propan-1-ol)-1,2,3-triazol-4-yl]pyridine (PTD) was studied by time-resolved laser fluorescence spectroscopy (TRLFS). The formation of 1:3, 1:2, and 1:1 metal/ligand complexes was identified upon increasing PTD concentration in 10–3 mol/L HClO4 and in 0.44 mol/L HNO3 solutions. For all these complexes, stability constants were determined at different acid concentrations. Though under the extraction conditions proposed for an An/Ln separation process, that is, for 0.08 mol/L PTD in 0.44 mol/L HNO3, 1:3 complexes represent the major species, a significant fraction of 1:2 complexes was found. This is caused by ligand protonation, and results in lower Eu(III)/Am(III) separation factors compared to SO3–Ph–BTP, until now considered the i-SANEX reference ligand. Focused extraction studies performed at lower proton concentration, where the 1:3 complex is formed exclusively, confirm this assumption.

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