Radiolytic degradation in lanthanide/actinide separation ligands-NOPOPO: Radical kinetics and efficiencies determinations

Katy L. Swancutt; Stephen P. Mezyk; Richard D. Tillotson; Sylvie Pailloux; Manab Chakravarty; Robert T. Paine; Leigh R. Martin

doi:10.1080/07366299.2011.581051

Radiolytic degradation in lanthanide/actinide separation ligands-NOPOPO: Radical kinetics and efficiencies determinations

Katy L. Swancutt, Stephen P. Mezyk, Richard D. Tillotson, Sylvie Pailloux, Manab Chakravarty, Robert T. Paine, Leigh R. Martin

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

Abstract

Trivalent lanthanide/actinide separations from used nuclear fuel occurs in the presence radiation fields that degrades the extraction ligands and solvents. Here we have investigated the stability of a new ligand for lanthanide/actinide separation; 2,6-bis[(di(2-ethylhexyl)phosphino)methyl] pyridine N,P,P-trioxide, TEH(NOPOPO). The impact of γ-radiolysis on the distribution ratios for actinide (Am) and Lanthanide (Eu) extraction both in the presence and absence of an acidic aqueous phase by TEH(NOPOPO) was determined. Corresponding reaction rate constants for the two major radicals, hydroxyl and nitrate, were determined for TEH(NOPOPO) in the aqueous phase, with room temperature values of (3.49 ± 0.10) × 10⁹ and (1.95 ± 0.15) × 10⁸M^-1s^-1, respectively. The activation energy for this reaction was found to be 30.2 ± 4.1 kJ mol^-1. Rate constants for two analogues (2-methylphosphonic acid pyridine N,P-dioxide and 2,6-bis(methylphosphonic acid) pyridine N,P,P-trioxide) were also determined to assist in determining the major reaction pathways.

Original language	English (US)
Pages (from-to)	637-654
Number of pages	18
Journal	Solvent Extraction and Ion Exchange
Volume	29
Issue number	4
DOIs	https://doi.org/10.1080/07366299.2011.581051
State	Published - Jul 2011

Bibliographical note

Funding Information:
The kinetics measurements described here were performed at the Radiation Laboratory, University of Notre Dame, which is supported by the Office of Basic Energy Sciences, U.S. Department of Energy. Steady-state irradiations were performed at Idaho National Laboratories. Support for this work was provided by the University Nuclear Energy Research Initiative (UNERI) U.S. Department of Energy, Office of Nuclear Energy, under DOE Idaho Operations Office Contract DE-AC07-05ID14517. UNM efforts were sponsored under DOE contract DE-FC07-06ID14730.

Keywords

Actinide lanthanide separation
Radiolysis
Solvent extraction

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title = "Radiolytic degradation in lanthanide/actinide separation ligands-NOPOPO: Radical kinetics and efficiencies determinations",

abstract = "Trivalent lanthanide/actinide separations from used nuclear fuel occurs in the presence radiation fields that degrades the extraction ligands and solvents. Here we have investigated the stability of a new ligand for lanthanide/actinide separation; 2,6-bis[(di(2-ethylhexyl)phosphino)methyl] pyridine N,P,P-trioxide, TEH(NOPOPO). The impact of γ-radiolysis on the distribution ratios for actinide (Am) and Lanthanide (Eu) extraction both in the presence and absence of an acidic aqueous phase by TEH(NOPOPO) was determined. Corresponding reaction rate constants for the two major radicals, hydroxyl and nitrate, were determined for TEH(NOPOPO) in the aqueous phase, with room temperature values of (3.49 ± 0.10) × 109 and (1.95 ± 0.15) × 108M-1s-1, respectively. The activation energy for this reaction was found to be 30.2 ± 4.1 kJ mol-1. Rate constants for two analogues (2-methylphosphonic acid pyridine N,P-dioxide and 2,6-bis(methylphosphonic acid) pyridine N,P,P-trioxide) were also determined to assist in determining the major reaction pathways.",

keywords = "Actinide lanthanide separation, Radiolysis, Solvent extraction",

author = "Swancutt, {Katy L.} and Mezyk, {Stephen P.} and Tillotson, {Richard D.} and Sylvie Pailloux and Manab Chakravarty and Paine, {Robert T.} and Martin, {Leigh R.}",

note = "Funding Information: The kinetics measurements described here were performed at the Radiation Laboratory, University of Notre Dame, which is supported by the Office of Basic Energy Sciences, U.S. Department of Energy. Steady-state irradiations were performed at Idaho National Laboratories. Support for this work was provided by the University Nuclear Energy Research Initiative (UNERI) U.S. Department of Energy, Office of Nuclear Energy, under DOE Idaho Operations Office Contract DE-AC07-05ID14517. UNM efforts were sponsored under DOE contract DE-FC07-06ID14730.",

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AU - Swancutt, Katy L.

AU - Mezyk, Stephen P.

AU - Tillotson, Richard D.

AU - Pailloux, Sylvie

AU - Chakravarty, Manab

AU - Paine, Robert T.

AU - Martin, Leigh R.

N1 - Funding Information: The kinetics measurements described here were performed at the Radiation Laboratory, University of Notre Dame, which is supported by the Office of Basic Energy Sciences, U.S. Department of Energy. Steady-state irradiations were performed at Idaho National Laboratories. Support for this work was provided by the University Nuclear Energy Research Initiative (UNERI) U.S. Department of Energy, Office of Nuclear Energy, under DOE Idaho Operations Office Contract DE-AC07-05ID14517. UNM efforts were sponsored under DOE contract DE-FC07-06ID14730.

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N2 - Trivalent lanthanide/actinide separations from used nuclear fuel occurs in the presence radiation fields that degrades the extraction ligands and solvents. Here we have investigated the stability of a new ligand for lanthanide/actinide separation; 2,6-bis[(di(2-ethylhexyl)phosphino)methyl] pyridine N,P,P-trioxide, TEH(NOPOPO). The impact of γ-radiolysis on the distribution ratios for actinide (Am) and Lanthanide (Eu) extraction both in the presence and absence of an acidic aqueous phase by TEH(NOPOPO) was determined. Corresponding reaction rate constants for the two major radicals, hydroxyl and nitrate, were determined for TEH(NOPOPO) in the aqueous phase, with room temperature values of (3.49 ± 0.10) × 109 and (1.95 ± 0.15) × 108M-1s-1, respectively. The activation energy for this reaction was found to be 30.2 ± 4.1 kJ mol-1. Rate constants for two analogues (2-methylphosphonic acid pyridine N,P-dioxide and 2,6-bis(methylphosphonic acid) pyridine N,P,P-trioxide) were also determined to assist in determining the major reaction pathways.

AB - Trivalent lanthanide/actinide separations from used nuclear fuel occurs in the presence radiation fields that degrades the extraction ligands and solvents. Here we have investigated the stability of a new ligand for lanthanide/actinide separation; 2,6-bis[(di(2-ethylhexyl)phosphino)methyl] pyridine N,P,P-trioxide, TEH(NOPOPO). The impact of γ-radiolysis on the distribution ratios for actinide (Am) and Lanthanide (Eu) extraction both in the presence and absence of an acidic aqueous phase by TEH(NOPOPO) was determined. Corresponding reaction rate constants for the two major radicals, hydroxyl and nitrate, were determined for TEH(NOPOPO) in the aqueous phase, with room temperature values of (3.49 ± 0.10) × 109 and (1.95 ± 0.15) × 108M-1s-1, respectively. The activation energy for this reaction was found to be 30.2 ± 4.1 kJ mol-1. Rate constants for two analogues (2-methylphosphonic acid pyridine N,P-dioxide and 2,6-bis(methylphosphonic acid) pyridine N,P,P-trioxide) were also determined to assist in determining the major reaction pathways.

KW - Actinide lanthanide separation

KW - Radiolysis

KW - Solvent extraction

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Radiolytic degradation in lanthanide/actinide separation ligands-NOPOPO: Radical kinetics and efficiencies determinations

Abstract

Bibliographical note

Keywords

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