The Hydrolysis of Hydroxamic Acid Complexants in the Presence of Non-Oxidizing Metal Ions 2: Neptunium (IV) Ions

被引:0
作者
F. P. L. Andrieux
C. Boxall
I. May
R. J. Taylor
机构
[1] University of Central Lancashire,Centre for Materials Science
[2] University of Manchester,Centre for Radiochemistry Research
[3] British Technology Centre,Nexia Solutions Ltd
[4] Sellafield,Inorganic, Isotope and Actinide Chemistry, (C
[5] Los Alamos National Laboratory,IIAC)
来源
Journal of Solution Chemistry | 2008年 / 37卷
关键词
Formohydroxamic acid; Acetohydroxamic acid; Advanced Purex; Neptunium; Complexation; Speciation; Hydrolysis; Kinetics;
D O I
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中图分类号
学科分类号
摘要
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 K1=2715 and indications are that complexation protects the ligand against hydrolysis at 0.1>pH>−0.1.
引用
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页码:215 / 232
页数:17
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