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The Hydrolysis of Hydroxamic Acid Complexants in the Presence of Non-oxidizing Metal Ions 3: Ferric Ions at Elevated Temperatures

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Abstract

The hydrolysis of acetohydroxamic acid (AHA) was investigated both in the absence and presence of ferric ions at the range of temperatures (293–333 K). The data were then analyzed using a previously published mathematical model to determine the Arrhenius factor (A) and activation energy (E a) of the hydrolysis reactions of free AHA and AHA bound to iron in the form of the monoacetohydroxamatoiron(III) complex. The Arrhenius factor and activation energy were found to be 4.24 × 109 dm3·mol−1·s−1 and 80.1 kJ·mol−1 respectively for the hydrolysis of free AHA in solution and 2.44 × 1011 dm3·mol−1·s−1 and 89.6 kJ·mol−1 respectively for the hydrolysis of iron-bound AHA, suggesting a difference in the mechanism for the hydrolysis of the free and complexed ligand. This was further investigated using quantum mechanical calculations.

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Acknowledgments

The authors wish to thank the National Nuclear Laboratory and the Nuclear Decommissioning Authority (NDA) for financial support. CB is supported by the Lloyd’s Register Foundation (LRF), a UK Registered charity and sole shareholder of Lloyd’s Register Group Ltd, which invests in science, engineering and technology for public benefit worldwide.

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Correspondence to Fabrice P. L. Andrieux.

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Andrieux, F.P.L., Boxall, C., Steele, H.M. et al. The Hydrolysis of Hydroxamic Acid Complexants in the Presence of Non-oxidizing Metal Ions 3: Ferric Ions at Elevated Temperatures. J Solution Chem 43, 608–622 (2014). https://doi.org/10.1007/s10953-014-0142-y

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  • DOI: https://doi.org/10.1007/s10953-014-0142-y

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