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Separation of Am3+ and Eu3+using hexa-n-octylnitrilo triacetamide (HONTA): complexation, extraction, luminescence, EXAFS and DFT studies

Abstract

This paper reports the solvent extraction of Am3+ and Eu3+ using N,N,N’,N’,N”,N”-hexa-n-octylnitrilotriacetamide (HONTA) as the extractant in n-dodecane. The results are in variance with those reported previously with respect to the nature of the extracted species. The solvent extraction data were entirely different than those reported previously as the extracted species conformed to 1:2 (M:L) species for both Am3+ and Eu3+ ions. The structure of the extracted complex was determined by EXAFS demonstrating that the three amidic ‘O’ atoms of HONTA complex with the Eu3+ ion. In case of Am3+ ion, the pivotal ‘N’ atom is suggested to bond to the metal ion, which may explain the significantly more favourable extraction of Am3+vis-à-vis Eu3+. The absence of H2O molecules in the inner coordination sphere of the Eu3+ - HONTA extract was confirmed by luminescence spectroscopic measurements. Complexation studies in MeOH and EtOH indicated the formation of both 1:1 and 1:2 complexes being in sharp contrast to the 1:1 complexes reported previously with Nd3+ ion. The results are explained on the basis of DFT calculations using HMNTA, the corresponding hexamethyl analogue of HONTA.

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Publication details

The article was received on 07 Sep 2017, accepted on 13 Nov 2017 and first published on 13 Nov 2017


Article type: Paper
DOI: 10.1039/C7DT03329J
Citation: Dalton Trans., 2017, Accepted Manuscript
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    Separation of Am3+ and Eu3+using hexa-n-octylnitrilo triacetamide (HONTA): complexation, extraction, luminescence, EXAFS and DFT studies

    A. Bhattacharyya, R. Egberink, P. K. Mohapatra, P. K. Verma, A. K. Yadav, S. N. Jha, D. Bhattacharyya, J. Huskens and W. Verboom, Dalton Trans., 2017, Accepted Manuscript , DOI: 10.1039/C7DT03329J

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