TY - JOUR
T1 - Solvent Extraction and Fluorescence Spectroscopic Investigation of the Selective Am(III) Complexation with TS-BTPhen
AU - Kaufholz, Peter
AU - Modolo, Giuseppe
AU - Wilden, Andreas
AU - Sadowski, Fabian
AU - Bosbach, Dirk
AU - Wagner, Christoph
AU - Geist, Andreas
AU - Panak, Petra
AU - Lewis, Frank
AU - Harwood, Laurence
PY - 2016/2
Y1 - 2016/2
N2 - An americium(III) selective separation procedure was developed based on the coextraction of trivalent actinides (An(III)) and lanthanides (Ln(III)) by TODGA (N,N,N′,N′-tetraoctyl-diglycolamide), followed by Am(III) selective stripping using the hydrophilic complexing agent TS-BTPhen (3,3′,3ʺ,3ʺ′-[3-(1,10-phenanthroline-2,9-diyl)-1,2,4-triazine-5,5,6,6-tetrayl]tetrabenzenesulfonic acid). Distribution ratios were found at an acidity of 0.65 mol L−1 nitric acid that allowed for the separation of Am(III) from Cm(III) (DCm > 1; DAm <1), giving a separation factor between curium and americium of SFCm/Am = 3.6 within the stripping step. Furthermore, Am(III) was readily separated from the lanthanides with the lowest selectivity for the Ln(III)/Am(III) separation being lanthanum with a separation factor of SFLa/Am = 20. The influence of the TS-BTPhen concentration on Am(III) distribution ratios was studied, giving a slope (logD vs. log[TS-BTPhen]) of approximately −1 for the stripping of Am(III) with TS-BTPhen from the TODGA-based organic phase. Time-resolved laser fluorescence spectroscopy (TRLFS) measurements of curium(III) were used to analyze the speciation of Cm(III)-TS-BTPhen complexes. Both 1:1 and 1:2 complexes were identified in single-phase experiments. The formation of the 1:1 complex was suppressed in 0.5 mol L−1 nitric acid but it was significantly present in HClO4 at pH 3. Conditional stability constants of the complex species were calculated from the TRLFS experiments.
AB - An americium(III) selective separation procedure was developed based on the coextraction of trivalent actinides (An(III)) and lanthanides (Ln(III)) by TODGA (N,N,N′,N′-tetraoctyl-diglycolamide), followed by Am(III) selective stripping using the hydrophilic complexing agent TS-BTPhen (3,3′,3ʺ,3ʺ′-[3-(1,10-phenanthroline-2,9-diyl)-1,2,4-triazine-5,5,6,6-tetrayl]tetrabenzenesulfonic acid). Distribution ratios were found at an acidity of 0.65 mol L−1 nitric acid that allowed for the separation of Am(III) from Cm(III) (DCm > 1; DAm <1), giving a separation factor between curium and americium of SFCm/Am = 3.6 within the stripping step. Furthermore, Am(III) was readily separated from the lanthanides with the lowest selectivity for the Ln(III)/Am(III) separation being lanthanum with a separation factor of SFLa/Am = 20. The influence of the TS-BTPhen concentration on Am(III) distribution ratios was studied, giving a slope (logD vs. log[TS-BTPhen]) of approximately −1 for the stripping of Am(III) with TS-BTPhen from the TODGA-based organic phase. Time-resolved laser fluorescence spectroscopy (TRLFS) measurements of curium(III) were used to analyze the speciation of Cm(III)-TS-BTPhen complexes. Both 1:1 and 1:2 complexes were identified in single-phase experiments. The formation of the 1:1 complex was suppressed in 0.5 mol L−1 nitric acid but it was significantly present in HClO4 at pH 3. Conditional stability constants of the complex species were calculated from the TRLFS experiments.
KW - Am(III) separation
KW - TODGA
KW - selective stripping
KW - curium
KW - americium
KW - lanthanides
KW - partitioning
KW - TS-BTPhen
KW - americium–curium separation
U2 - 10.1080/07366299.2016.1151308
DO - 10.1080/07366299.2016.1151308
M3 - Article
SN - 0736-6299
VL - 34
SP - 126
EP - 140
JO - Solvent Extraction and Ion Exchange
JF - Solvent Extraction and Ion Exchange
IS - 2
ER -