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The hydrolysis of hydroxamic acid complexants in the presence of non-oxidizing metal ions 2: Neptunium (IV) ions.

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The hydrolysis of hydroxamic acid complexants in the presence of non-oxidizing metal ions 2: Neptunium (IV) ions. / Andrieux, Fabrice Pierre Louis; Boxall, C.; May, I. et al.

In: Journal of Solution Chemistry, Vol. 37, No. 2, 02.2008, p. 215-232.

Research output: Contribution to Journal/MagazineJournal articlepeer-review

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Andrieux FPL, Boxall C, May I, Taylor RJ. The hydrolysis of hydroxamic acid complexants in the presence of non-oxidizing metal ions 2: Neptunium (IV) ions. Journal of Solution Chemistry. 2008 Feb;37(2):215-232. doi: 10.1007/s10953-007-9225-3

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@article{2daeac8f38f944a4ade6882547a5a603,
title = "The hydrolysis of hydroxamic acid complexants in the presence of non-oxidizing metal ions 2: Neptunium (IV) ions.",
abstract = "Hydroxamic acids are salt free, organic compounds with affinities for cations such as Fe3+, Np4+ and Pu4+, and have been identified as suitable reagents for the control of Pu and Np in advanced nuclear fuel reprocessing. The results of a UV-visible, near-IR spectrophotometric study of the 1:1 and 2:1 complexes formed between formo- and aceto-hydroxamic acids (FHA, AHA) and Np(IV) ions are interpreted using speciation diagrams for the identification of the species present at different pH and ligand to metal ratios. A kinetic model that describes the instability of the complex due to hydrolysis of the hydroxamate moiety, previously developed for the Fe(III)-AHA complexes (Andrieux et al. in J. Solution Chem. 36:1201-1217, [2007]), is tested here against experimental Np(IV)-FHA data. Consequently, the complexation constant for formation of the 1:1 Np(IV)-FHA complex in nitric acid is estimated at K-1=2715 and indications are that complexation protects the ligand against hydrolysis at 0.1 > pH >-0.1.",
keywords = "formohydroxamic acid, acetohydroxamic acid, advanced Purex, neptunium, complexation, speciation, hydrolysis, kinetics, NUCLEAR-FUEL, NITRIC-ACID, FLOWSHEETS, SEPARATION, REDUCTION",
author = "Andrieux, {Fabrice Pierre Louis} and C. Boxall and I. May and Taylor, {R. J.}",
note = "The original publication is available at www.springerlink.com",
year = "2008",
month = feb,
doi = "10.1007/s10953-007-9225-3",
language = "English",
volume = "37",
pages = "215--232",
journal = "Journal of Solution Chemistry",
issn = "0095-9782",
publisher = "Springer New York",
number = "2",

}

RIS

TY - JOUR

T1 - The hydrolysis of hydroxamic acid complexants in the presence of non-oxidizing metal ions 2: Neptunium (IV) ions.

AU - Andrieux, Fabrice Pierre Louis

AU - Boxall, C.

AU - May, I.

AU - Taylor, R. J.

N1 - The original publication is available at www.springerlink.com

PY - 2008/2

Y1 - 2008/2

N2 - Hydroxamic acids are salt free, organic compounds with affinities for cations such as Fe3+, Np4+ and Pu4+, and have been identified as suitable reagents for the control of Pu and Np in advanced nuclear fuel reprocessing. The results of a UV-visible, near-IR spectrophotometric study of the 1:1 and 2:1 complexes formed between formo- and aceto-hydroxamic acids (FHA, AHA) and Np(IV) ions are interpreted using speciation diagrams for the identification of the species present at different pH and ligand to metal ratios. A kinetic model that describes the instability of the complex due to hydrolysis of the hydroxamate moiety, previously developed for the Fe(III)-AHA complexes (Andrieux et al. in J. Solution Chem. 36:1201-1217, [2007]), is tested here against experimental Np(IV)-FHA data. Consequently, the complexation constant for formation of the 1:1 Np(IV)-FHA complex in nitric acid is estimated at K-1=2715 and indications are that complexation protects the ligand against hydrolysis at 0.1 > pH >-0.1.

AB - Hydroxamic acids are salt free, organic compounds with affinities for cations such as Fe3+, Np4+ and Pu4+, and have been identified as suitable reagents for the control of Pu and Np in advanced nuclear fuel reprocessing. The results of a UV-visible, near-IR spectrophotometric study of the 1:1 and 2:1 complexes formed between formo- and aceto-hydroxamic acids (FHA, AHA) and Np(IV) ions are interpreted using speciation diagrams for the identification of the species present at different pH and ligand to metal ratios. A kinetic model that describes the instability of the complex due to hydrolysis of the hydroxamate moiety, previously developed for the Fe(III)-AHA complexes (Andrieux et al. in J. Solution Chem. 36:1201-1217, [2007]), is tested here against experimental Np(IV)-FHA data. Consequently, the complexation constant for formation of the 1:1 Np(IV)-FHA complex in nitric acid is estimated at K-1=2715 and indications are that complexation protects the ligand against hydrolysis at 0.1 > pH >-0.1.

KW - formohydroxamic acid

KW - acetohydroxamic acid

KW - advanced Purex

KW - neptunium

KW - complexation

KW - speciation

KW - hydrolysis

KW - kinetics

KW - NUCLEAR-FUEL

KW - NITRIC-ACID

KW - FLOWSHEETS

KW - SEPARATION

KW - REDUCTION

U2 - 10.1007/s10953-007-9225-3

DO - 10.1007/s10953-007-9225-3

M3 - Journal article

VL - 37

SP - 215

EP - 232

JO - Journal of Solution Chemistry

JF - Journal of Solution Chemistry

SN - 0095-9782

IS - 2

ER -