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Acetohydroxamatoiron(III) Complexes: Thermodynamics of Formation and Temperature Dependent Speciation

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Abstract

Studies of the thermodynamics of formation of the acetohydroxamatoiron(III) complexes were carried out in acidic media at temperatures ranging from 293 to 323 K. Through the isolation of the unique UV–visible spectra of all three complexes, it was possible to determine their formation constants and deduce enthalpies and entropies of formation as well as their molar absorptivities. The enthalpies of formation of the mono-, bis- and trisacetohydroxamatoiron(III) complexes were found to be −56.4, −17.09 and +19.74 kJ⋅mol−1, respectively. Following the determination of the enthalpy and entropy of formation of these complexes, speciation diagrams were calculated for the complexes at temperatures ranging from 293 to 323 K.

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References

  1. Muri, E.M.F., Nieto, M.J., Sindelar, R.D., Williamson, J.S.: Hydroxamic acids as pharmacological agents. Current Med. Chem. 9, 1631–1653 (2002)

    CAS  Google Scholar 

  2. Desaraju, P., Winston, A.: Synthesis and iron complexation studies of bis-hydroxamic acids. J. Coord. Chem. 14, 241–248 (1986)

    Article  CAS  Google Scholar 

  3. Carrott, M.J., Fox, O.D., Maher, C.J., Mason, C., Taylor, R.J., Sinkov, S.I., Choppin, G.R.: Solvent extraction behaviour of plutonium(IV) ions in the presence of simple hydroxamic acids. Solv. Extr. Ion Exch. 25, 723–746 (2007)

    Article  CAS  Google Scholar 

  4. Ghosh, K.K.: Kinetic and mechanistic aspects of acid catalysed hydrolysis of hydroxamic acids. Indian J. Chem. 36B, 1089–1102 (1997)

    CAS  Google Scholar 

  5. Vernon, F.: Chelating ion exchangers. The synthesis and use of poly(hydroxamic acid) resins. Pure Appl. Chem. 54, 2151–2158 (1982)

    Article  CAS  Google Scholar 

  6. Raymond, K.N., Freeman, G.E., Kappel, M.J.: Actinide-specific complexing agents: Their structural and solution chemistry. Inorg. Chim. Acta 84, 193–204 (1984)

    Article  Google Scholar 

  7. Renshaw, J.C., Robson, G.D., Trinci, A.P.J., Wiebe, M.G., Livens, F.R., Collinson, D., Taylor, R.J.: Fungal siderophores: Structures, functions and applications. Mycol. Res. 106, 1123–1142 (2002)

    Article  CAS  Google Scholar 

  8. Monzyk, B., Crumbliss, A.L.: 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) complexes. J. Am. Chem. Soc. 101, 6203–6213 (1979)

    Article  CAS  Google Scholar 

  9. John, S.G., Ruggiero, C.E., Hersman, L.E., Tung, C.-S., Neu, M.P.: Siderophore mediated plutonium accumulation by microbacterium flavescens (JG-9). Environ. Sci. Technol. 35, 2942–2948 (2001)

    Article  CAS  Google Scholar 

  10. Birkett, J.E., Carrott, M.J., Fox, O.D., Jones, C.J., Maher, C.J., Roube, C.V., Taylor, R.J., Woodhead, D.A.: Recent developments in the Purex process for nuclear fuel reprocessing: Complexant based stripping for uranium–plutonium separation. Chimia 59, 898–904 (2005)

    Article  CAS  Google Scholar 

  11. Andrieux, F.P.L., Boxall, C., Taylor, R.J.: The hydrolysis of hydroxamic acid complexants in the presence of non-oxidising metal ions 1: Ferric ions. J. Solution Chem. 36, 1201–1217 (2007)

    Article  CAS  Google Scholar 

  12. Andrieux, F.P.L., Boxall, C., Mason, C., Taylor, R.J.: The hydrolysis of hydroxamic acid complexants in the presence of non-oxidising metal ions 2: Neptunium(IV) ions. J. Solution Chem. 37, 215–232 (2008)

    Article  CAS  Google Scholar 

  13. Carrott, M.J., Fox, O.D., LeGurun, G., Jones, C.J., Mason, C., Taylor, R.J., Andrieux, F.P.L., Boxall, C.: Oxidation-reduction reactions of simple hydroxamic acids and plutonium(IV) ions in nitric acid. Radiochim. Acta 96, 333–344 (2008)

    Article  CAS  Google Scholar 

  14. Roos, Y.H.: Phase transitions and transformations in food systems. In: Heldmann, D.R., Lund, D.B. (eds.) Handbook of Food Engineering, 2nd edn, p. 328. CRC, Boca Raton (2006)

    Google Scholar 

  15. Schwarzenbach, G., Schwarzenbach, K., Hydroxamatkomplexe, I: Die Stabilität der Eisen(III)-Komplexe einfacher Hydroxamsäuren und des Ferrioxamins B. Helv. Chim. Acta 46, 1390–1400 (1963)

    Article  CAS  Google Scholar 

  16. Cornell, R.M., Schwertmann, U.: The Iron Oxides, p. 175. VCH, New York (1996)

    Google Scholar 

  17. Heusler, K.E., Lorenz, W.J.: In: Bard, A.J., Parsons, R., Jordan, J. (eds.) Standard Potentials in Aqueous Solution, p. 391. Dekker, New York (1985)

    Google Scholar 

  18. Sapieszko, R.S., Patel, R.C., Matijevic, E.: Ferric hydrous oxide sols. 2. Thermodynamics of aqueous hydroxo and sulfato ferric complexes. J. Phys. Chem. 81, 1061–1068 (1977)

    Article  CAS  Google Scholar 

  19. Farkas, E., Kozma, E., Pethő, M., Herlihy, K.M., Micera, G.: Equilibrium studies on copper(II)- and iron(III)-monohydroxamates. Polyhedron. 17, 3331–3342 (1998)

    Article  CAS  Google Scholar 

  20. Arif-Kazmi, S., McArdle, J.V.: Kinetics of formation of bis- and tris(acetohydroxamato)Fe(III). J. Inorg. Nucl. Chem. 43, 3031–3034 (1981)

    Article  Google Scholar 

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Authors and Affiliations

  1. John Tyndall Institute for Nuclear Research, University of Central Lancashire, Preston, PR1 2HE, UK

    Fabrice P. L. Andrieux & Colin Boxall

  2. National Nuclear Laboratory, Central Laboratory, Sellafield, Seascale, Cumbria, CA20 1PG, UK

    Robin J. Taylor

Authors
  1. Fabrice P. L. Andrieux
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  2. Colin Boxall
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  3. Robin J. Taylor
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Correspondence to Fabrice P. L. Andrieux.

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Andrieux, F.P.L., Boxall, C. & Taylor, R.J. Acetohydroxamatoiron(III) Complexes: Thermodynamics of Formation and Temperature Dependent Speciation. J Solution Chem 37, 1511–1527 (2008). https://doi.org/10.1007/s10953-008-9327-6

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  • DOI: https://doi.org/10.1007/s10953-008-9327-6

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