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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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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.

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Author notes

  1. I. May

    Present address: Inorganic, Isotope and Actinide Chemistry, (C-IIAC), Los Alamos National Laboratory, Mail Stop J-514, Los Alamos, NM, 87545, USA

Authors and Affiliations

  1. Centre for Materials Science, University of Central Lancashire, Preston, PR1 2HE, UK

    F. P. L. Andrieux & C. Boxall

  2. Centre for Radiochemistry Research, University of Manchester, Oxford Rd, Manchester, M13 9PL, UK

    I. May

  3. Nexia Solutions Ltd, British Technology Centre, Sellafield, Seascale, Cumbria, CA20 1PG, UK

    R. J. Taylor

Authors
  1. F. P. L. Andrieux
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  2. C. Boxall
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  3. I. May
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  4. R. J. Taylor
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Correspondence to C. Boxall.

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Andrieux, F.P.L., Boxall, C., May, I. et al. The Hydrolysis of Hydroxamic Acid Complexants in the Presence of Non-Oxidizing Metal Ions 2: Neptunium (IV) Ions. J Solution Chem 37, 215–232 (2008). https://doi.org/10.1007/s10953-007-9225-3

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  • DOI: https://doi.org/10.1007/s10953-007-9225-3

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