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The hydrolysis of hydroxamic acid complexants in the presence of non-oxidizing metal ions 1: Ferric ions.

By Fabrice Pierre Louis Andrieux, C. Boxall and R. J. Taylor

Abstract

Hydroxamic acids (XHAs) are organic compounds with affinities for cations such as Fe3+, Np4+ and Pu4+ and have been identified as useful reagents in nuclear fuel reprocessing. Acid catalyzed hydrolysis of free XHAs is well known and may impact negatively on reprocessing applications. The hydrolysis of metal-bound XHAs within metal ion-XHA complexes is less understood. With the aid of speciation diagrams, we have modelled UV-visible spectrophotometric kinetic studies of the acid-catalyzed hydrolysis of acetohydroxamic acid (AHA) bound to the model ion Fe(III). These studies have yielded the following information for the hydrolysis of AHA in the Fe(AHA)2+ complex at 293 K: (i) the order with respect to [H+] during the rate determining step, m=0.97, is the same as for the free ligand, indicating a similarity of mechanisms; and (ii) the kinetic rate parameter, k 1=1.02×10−4 dm3⋅mol−1⋅s−1, is greater than that for the free ligand, k 0=1.84×10−5 dm3⋅mol−1⋅s−1 for pH>−0.5, a result that is consistent with a Hammett analysis of the system

Year: 2007
OAI identifier: oai:eprints.lancs.ac.uk:26511
Provided by: Lancaster E-Prints

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Citations

  1. (1976). A Kinetic Study of the Reaction of Plutonium(IV) with Hydroxylamine.
  2. (2000). A preliminary study of the reduction of Np(VI) by formohydroxamic acid using stopped-flow near-infrared spectrophotometry.
  3. (1986). A.: Synthesis and Iron Complexation Studies of BisHydroxamic Acids.
  4. (2006). Advanced Separation Technologies for Processing Spent Nuclear Fuel and the Potential Benefits to a Geologic Repository. In: Separations for the Nuclear Fuel Cycle
  5. (2001). Critical Stability Constants, doi
  6. (2007). G.R.: Solvent Extraction Behaviour of Plutonium Ions in the Presence of Simple Hydroxamic Acids, Solvent Extraction and Ion Exchange, to be submitted doi
  7. (1981). J.V.: Kinetics of Formation of Bis- doi
  8. (1997). Kinetic and Mechanistic Aspects of Acid Catalysed Hydrolysis of Hydroxamic Acids. Indian J.Chem. 36B, doi
  9. (1979). Mechanism of Ligand Substitution on High-Spin Iron(III) by Hydroxamic Acid Chelators. Thermodynamic and Kinetic Studies on the Formation and Dissociation of a Series of Monohydroxamatoiron (III) doi
  10. (1987). On the Rate Maxima Observed in the Acid Hydrolysis of Some Alkylhydroxamic Acids. doi
  11. (2006). R.J.: Advanced PUREX flowsheets for future Np and Pu fuel cycle demands. In: Separations for the Nuclear Fuel Cycle
  12. (2006). R.J.: Advanced PUREX flowsheets for future Np and Pu fuel cycle demands. In: Separations for the Nuclear Fuel Cycle in the 21 st Century;
  13. (2007). R.J.: The Hydrolysis of Hydroxamic Acid Complexants in the Presence of Non-Oxidising Metal Ions 2: Neptunium (IV) Ions. J.Solution Chem., doi
  14. (2005). Recent Developments in the Purex Process for Nuclear Fuel Reprocessing: Complexant Based Stripping for Uranium - Plutonium Separation.
  15. (1996). Reprocessing Irradiated Fuel. In:
  16. (1965). The Complexing Power of Hydroxamic Acids and its Effects on Behaviour of Organic Extractants in the Reprocessing of Irradiated Fuels I.
  17. (1966). The Complexing Power of Hydroxamic Acids and its Effects on Behaviour of Organic Extractants in the Reprocessing of Irradiated Fuels II.
  18. (1996). The Iron Oxides, doi
  19. (1982). The Role of Hydroxamic Acids in the Retention of Fission Products in TBP Diluents. A Quantitative Study in a Model System. doi
  20. (1998). Y.S.: The Applications of Formo- and Aceto- Hydroxamic Acids

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