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

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The hydrolysis of hydroxamic acid complexants in the presence of non-oxidizing metal ions 1: Ferric ions. / Andrieux, Fabrice Pierre Louis; Boxall, C.; Taylor, R. J.
In: Journal of Solution Chemistry, Vol. 36, No. 10, 10.2007, p. 1201-1217.

Research output: Contribution to Journal/MagazineJournal articlepeer-review

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Andrieux FPL, Boxall C, Taylor RJ. The hydrolysis of hydroxamic acid complexants in the presence of non-oxidizing metal ions 1: Ferric ions. Journal of Solution Chemistry. 2007 Oct;36(10):1201-1217. doi: 10.1007/s10953-007-9183-9

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@article{1792a6f06a7d4a1b8ddb7073e3835237,
title = "The hydrolysis of hydroxamic acid complexants in the presence of non-oxidizing metal ions 1: Ferric ions.",
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.",
keywords = "acetohydroxamic acid, ferric ions, complexation, speciation, hydrolysis, kinetics, NUCLEAR-FUEL, BENZOHYDROXAMIC ACID, ORGANIC EXTRACTANTS, IRRADIATED FUELS, HYDROXYLAMINE, SEPARATION, REDUCTION, BEHAVIOUR, KINETICS, POWER",
author = "Andrieux, {Fabrice Pierre Louis} and C. Boxall and Taylor, {R. J.}",
note = "The original publication is available at www.springerlink.com",
year = "2007",
month = oct,
doi = "10.1007/s10953-007-9183-9",
language = "English",
volume = "36",
pages = "1201--1217",
journal = "Journal of Solution Chemistry",
issn = "0095-9782",
publisher = "Springer New York",
number = "10",

}

RIS

TY - JOUR

T1 - The hydrolysis of hydroxamic acid complexants in the presence of non-oxidizing metal ions 1: Ferric ions.

AU - Andrieux, Fabrice Pierre Louis

AU - Boxall, C.

AU - Taylor, R. J.

N1 - The original publication is available at www.springerlink.com

PY - 2007/10

Y1 - 2007/10

N2 - 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.

AB - 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.

KW - acetohydroxamic acid

KW - ferric ions

KW - complexation

KW - speciation

KW - hydrolysis

KW - kinetics

KW - NUCLEAR-FUEL

KW - BENZOHYDROXAMIC ACID

KW - ORGANIC EXTRACTANTS

KW - IRRADIATED FUELS

KW - HYDROXYLAMINE

KW - SEPARATION

KW - REDUCTION

KW - BEHAVIOUR

KW - KINETICS

KW - POWER

U2 - 10.1007/s10953-007-9183-9

DO - 10.1007/s10953-007-9183-9

M3 - Journal article

VL - 36

SP - 1201

EP - 1217

JO - Journal of Solution Chemistry

JF - Journal of Solution Chemistry

SN - 0095-9782

IS - 10

ER -