The Intermediate in the Reaction between Vanadium(II) and Vanadium(IV)

Newton, T. W.; Baker, F. B.

doi:10.1021/ic50014a028

Cited by 61 publications

(18 citation statements)

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“…vanadium (III) (Newton and Baker, 1964). This and other examples of dissociation between metal and complexing ligand, oxidative reactions of metal and ligand, and degradation of protein show that the correct nature of the vanadium (Webb, 1939).…”

Section: Discussionmentioning

confidence: 67%

THE BLOOD OF ASCIDIA NIGRA: BLOOD CELL FREQUENCY DISTRIBUTION, MORPHOLOGY, AND THE DISTRIBUTION AND VALENCE OF VANADIUM IN LIVING BLOOD CELLS

Kustin

Levine

McLeod

et al. 1976

The Biological Bulletin

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Section: Discussionmentioning

confidence: 67%

THE BLOOD OF ASCIDIA NIGRA: BLOOD CELL FREQUENCY DISTRIBUTION, MORPHOLOGY, AND THE DISTRIBUTION AND VALENCE OF VANADIUM IN LIVING BLOOD CELLS

Kustin

Levine

McLeod

et al. 1976

The Biological Bulletin

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“…One possible mechanism is that two adsorbed vanadium intermediates form a dimer on the carbon surface to facilitate two-electron transfer, after which the dimer desorbs/dissociates (no dimers were detected in bulk solution by UV−vis, as mentioned above). Another possible mechanism involves formation of V 4+ as a reaction intermediate, which reacts with V 2+ , undergoing a comproportionation reaction observed in a previous study in perchlorate solutions 58 to give V 3+ , facilitating an overall twoelectron transfer. A similar mechanism as that shown in Scheme 1b may occur in HBr, but additional tests are needed and will be the focus of future work.…”

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confidence: 99%

V²⁺/V³⁺ Redox Kinetics on Glassy Carbon in Acidic Electrolytes for Vanadium Redox Flow Batteries

et al. 2019

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Vanadium redox flow batteries are a promising technology for energy storage, yet the mechanism of the kinetically limiting V 2+ /V 3+ redox reaction remains poorly understood. Here, we elucidate the impact of anion complexation on V 2+ /V 3+ kinetics on a glassy carbon electrode in three common electrolytes: hydrochloric acid, sulfuric acid, and mixed HCl/H 2 SO 4 . The V 2+ /V 3+ kinetics are ∼2.5 times faster in HCl and have lower apparent activation energies than those in H 2 SO 4 or HCl/H 2 SO 4 . We also identify the presence of [V(H 2 O) 4 Cl 2 ] + species in HCl by UV−vis spectroscopy. We confirm that the V 2+ /V 3+ reaction proceeds via an adsorbed intermediate and propose a bridging mechanism through adsorbed *Cl (in HCl) and *OH (in H 2 SO 4 or HCl/H 2 SO 4 ). A bridging mechanism through *Cl is supported by even faster redox kinetics in HBr than in HCl, possibly due to the higher polarizability of *Br. By measuring the exchange current densities using steady-state current measurements and impedance spectroscopy, we show that the overall reaction is a two-electron process in HCl as opposed to a one-electron process in H 2 SO 4 and HCl/H 2 SO 4 .

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“…This observation is significant because the reaction of O2 with V +3 is slow; further, it is extremely unlikely that any O2-formed by le-reduction of 02 would show a marked preference for reaction with V +8 over V +2, particularly because the latter is present in great abundance. The conclusions based on product identification are, of course, possible only because the reaction of V +2 with V O +~ is not extremely rapid (40). The analysis described depends on correcting for the contribution to the immediate stoichiometry made by the reaction of the peroxide which it is assumed is formed in the rate-determining step.…”

Section: I Ii Tillmentioning

confidence: 99%

Mechanisms of Oxidation with Oxygen

Taube

1965

The Journal of General Physiology

139

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Several topics are dealt with in discussing the reactions of molecular oxygen, but a common goal is pursued in each: to try to understand the reactions in terms of the fundamental properties of the oxygen molecule, and of the other reactants. The paper first describes the electronic structure of oxygen and of two low-lying electronically excited states. Concern with the low-lying electronically excited states is no longer the sole property of spectroscopists; recently, evidence has been presented for the participation of such activated molecules in chemical reactions. The chemistry of oxygen is dominated by the fact that the molecule in the ground state has two unpaired electrons, whereas the products of oxidation in many important reactions have zero spin. In its reactions with transition metal ions the restrictions imposed by the spin state of the oxygen molecule are easily circumvented. A number of reactions of oxygen with metal ions have been studied in considerable detail; conclusions on basic aspects of the reaction mechanism are outlined. Among the most interesting reactions of oxygen are those in which it is reversibly absorbed by reducing agents. Reversible absorption to form a peroxide in the bound state is possible; some of the conditions which must be fulfilled by a reducing system to qualify as storing oxygen in this way are reasonably well understood and are here enunciated. Little has been done on the formation of oxygen from water; some factors involved in this process are discussed.

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The Intermediate in the Reaction between Vanadium(II) and Vanadium(IV)

Cited by 61 publications

References 0 publications

THE BLOOD OF ASCIDIA NIGRA: BLOOD CELL FREQUENCY DISTRIBUTION, MORPHOLOGY, AND THE DISTRIBUTION AND VALENCE OF VANADIUM IN LIVING BLOOD CELLS

THE BLOOD OF ASCIDIA NIGRA: BLOOD CELL FREQUENCY DISTRIBUTION, MORPHOLOGY, AND THE DISTRIBUTION AND VALENCE OF VANADIUM IN LIVING BLOOD CELLS

V²⁺/V³⁺ Redox Kinetics on Glassy Carbon in Acidic Electrolytes for Vanadium Redox Flow Batteries

Mechanisms of Oxidation with Oxygen

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The Intermediate in the Reaction between Vanadium(II) and Vanadium(IV)

Cited by 61 publications

References 0 publications

THE BLOOD OF ASCIDIA NIGRA: BLOOD CELL FREQUENCY DISTRIBUTION, MORPHOLOGY, AND THE DISTRIBUTION AND VALENCE OF VANADIUM IN LIVING BLOOD CELLS

THE BLOOD OF ASCIDIA NIGRA: BLOOD CELL FREQUENCY DISTRIBUTION, MORPHOLOGY, AND THE DISTRIBUTION AND VALENCE OF VANADIUM IN LIVING BLOOD CELLS

V2+/V3+ Redox Kinetics on Glassy Carbon in Acidic Electrolytes for Vanadium Redox Flow Batteries

Mechanisms of Oxidation with Oxygen

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V²⁺/V³⁺ Redox Kinetics on Glassy Carbon in Acidic Electrolytes for Vanadium Redox Flow Batteries