Oxidation of uranium(IV) by vanadium(V) in perchlorate media

Ekstrom, A.

doi:10.1021/ic50170a024

Cited by 4 publications

(2 citation statements)

References 23 publications

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“…It has been demonstrated that the oxidation of uranium(IV) by multiequivalent oxidants such as MnO 4 – as an oxyanion and VO 2 + as an oxycation occurred by successive one-electron transfer mechanism in a sequence with the formation of ion-pairs, but the oxidation of U IV by oxyanion chromate, CrO 4 2– , was proceeding by a simultaneous two-electron changes in a single step. The transfer of one and/or two oxygen atoms from the oxidant to form single or doubly bridged transition states between the reactants was postulated in those redox reactions.…”

Section: Introductionmentioning

confidence: 99%

A Mechanistic Approach to the Kinetics of Oxidation of Uranium(IV) by Hexachloroplatinate(IV) in Aqueous Perchlorate Solutions. Evidence of the Formation of a Binuclear Intermediate Complex

Hassan

2011

J. Phys. Chem. A

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The kinetics of hexachloroplatinate(IV) oxidation of uranium(IV) ion in aqueous perchloric acid solutions at a constant ionic strength of 1.0 mol dm(-3) has been investigated using the stopped-flow and conventional spectrophotometric techniques. The oxidation reaction was found to proceed through two distinct stages. The initial stage was found to be relatively fast corresponding to the formation of [(H(2)O)(n)U(IV)·Cl(6)Pt(IV)](2+) binuclear intermediate complex (with the rate constant k(1) = 1.75 × 10(4) dm(3) mol(-1)s(-1), k(-1) = 6.8 s(-1), and the formation constant K = 2.6 × 10(3) dm(3) mol(-1) at [H(+)] = 1.0 mol dm(-3) and 25 °C for binuclear formation). This stage was followed by a much slower stage corresponding to the transfer of two electrons from U(IV) to Pt(IV) in the rate-determining step (with the rate constant k = 5.32 × 10(-5) s(-1) at [H(+)] = 1.0 mol dm(-3) and 25 °C). The reaction stoichiometry was found to depend on the molar ratio of the reactants concentration. The experimental results indicated the decrease of the observed first-order rate constants with increasing the [H(+)] for the decomposition of the binuclear intermediate complex through the slow-second stage, whereas no change was observed with respect to the rate of formation of the binuclear complex at the initial rapid part. A tentative reaction mechanism consistent with the kinetic results is discussed.

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Section: Introductionmentioning

confidence: 99%

A Mechanistic Approach to the Kinetics of Oxidation of Uranium(IV) by Hexachloroplatinate(IV) in Aqueous Perchlorate Solutions. Evidence of the Formation of a Binuclear Intermediate Complex

Hassan

2011

J. Phys. Chem. A

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“…".~' A doubly bridged transition state undergoing a simultaneous transfer of two oxygen atoms was suggested for the reactions UIV-HCr04-2 1 and U'v-V02+ . 22 Therefore, an analogous transition state seems plausible. The configuration dub simulates the structures of both Uv and Uv' and has frequently been postulated in actinide reactions.…”

Section: Discussionmentioning

confidence: 99%

Kinetics of oxidation of uranium(IV) by permanganate ion in aqueous perchlorate media

Hassan¹,

Mouśa²,

El-Shatovry³

1988

J. Chem. Soc., Dalton Trans.

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The kinetics of oxidation of uranium(iv) b y permanganate ion in 1 .O rnol dm-3 perchloric acid solution has been investigated using a stopped-flow spectrophotometer. The reaction was found to be second order overall and first order in the concentrations of both reactants. The catalytic effect of the perchlorates of Hg2+, Cu2+, and Fe3+ on the reaction rate has been investigated. The activation parameters were evaluated and found to be ASs = 30.52 f 1.22 J K-' mot-',

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ChemInform Abstract: OXIDATION OF URANIUM(IV) BY VANADIUM(V) IN PERCHLORATE MEDIA

Ekstrom¹

1977

Chemischer Informationsdienst

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Oxidation of uranium(IV) by vanadium(V) in perchlorate media

Cited by 4 publications

References 23 publications

A Mechanistic Approach to the Kinetics of Oxidation of Uranium(IV) by Hexachloroplatinate(IV) in Aqueous Perchlorate Solutions. Evidence of the Formation of a Binuclear Intermediate Complex

A Mechanistic Approach to the Kinetics of Oxidation of Uranium(IV) by Hexachloroplatinate(IV) in Aqueous Perchlorate Solutions. Evidence of the Formation of a Binuclear Intermediate Complex

Kinetics of oxidation of uranium(IV) by permanganate ion in aqueous perchlorate media

ChemInform Abstract: OXIDATION OF URANIUM(IV) BY VANADIUM(V) IN PERCHLORATE MEDIA

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