Standard charge transfer rate constants for Nb(V)/Nb(IV) redox pairs in fluoride melts

Popova, A. V.; Kuznetsov, S. A.

doi:10.1134/s1023193512010132

Cited by 10 publications

(4 citation statements)

References 24 publications

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“…In turn, this leads to a nonmonotonic change in the charge transfer rate constant. At the same time in pure fluoride melts the monotonic dependence was obtained (19): k s (CsF) < k s (KF) < k s (NaF-KF).…”

Section: Introductionmentioning

confidence: 74%

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Electrochemical Behavior of Niobium Complexes in Chloride-Fluoride Melts with Addition of Alkaline Cations

2018

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The standard rate constants of charge transfer (k s) for the redox couple Nb(V)/Nb(IV) in NaCl-KCl(equimol.)-NaF(10 wt.%)-K2NbF7 (I) and NaCl-KCl(equimol.)-K2NbF7 (II) melts with addition of alkaline earth metal cations were determined. It was found that addition of alkaline earth metal cations resulted in increasing of k s to the certain ratio of Me2+/Nb(V) for the all alkaline earth metal cations due to substitution of Na+ and K+ cations by Me2+ in the second coordination sphere of niobium complexes that leads to decreasing of niobium fluoride complexes strength. Further addition brought to some decrease of the standard rate constants because the viscosity of melts increasing which brings to decrease of the diffusion coefficients. It was determined that in the melt (II) k s a little bit increased with increasing scan rate probably due to the secondary electrode process.

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Section: Introductionmentioning

confidence: 74%

“…The standard rate constants of charge transfer for the Nb(V)/Nb(IV) redox couple in the melt (II) were determined in previous our study (13,19,30).…”

Section: Ecs Transactions 86 (14) 69-80 (2018)mentioning

confidence: 99%

Electrochemical Behavior of Niobium Complexes in Chloride-Fluoride Melts with Addition of Alkaline Cations

2018

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“…However, influence of the second coordination sphere on the standard rate constants of charge transfer can not be prognosticated a priori. In (7)(8)(9)(10)(11)(12)(13)(14)(15), the method of cyclic voltammetry was used to determine the standard rate constants of charge transfer of the redox couple Nb(V)/Nb(IV) (7)(8)(9)(10)(11) and Cr(III)/Cr(II) (12)(13)(14)(15) in alkali chloride melts. The quantum-chemical calculations showed that the values of the charge transfer activation energy might indeed change nonmonotonously in the series of Na-K-Cs in accordance with the ratio of reorganization energies that leads to nonmonotonic variation of the charge transfer rate constant.…”

Section: Introductionmentioning

confidence: 99%

Influence of the Alkaline Earth Metal Cations on the Standard Rate Constants of Charge Transfer for the Redox Couple Ti(IV)/Ti(III) in Chloride-Fluoride Melts

Vetrova

Kuznetsov

2016

ECS Trans.

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The standard rate constants of charge transfer (ks ) for the redox couple Ti(IV)/Ti(III) in the (NaCl-KCl)equimol.-NaF(10 wt.%)-K2TiF6 melt were determined. It was shown, that k s increase with temperature increasing. Influence of strongly polarizing cations on the charge transfer kinetics was studied. It was determined the linear dependence of ks on ionic potential of alkaline earth metal cations and the activation energies of charge transfer were calculated.

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“…At the same time in pure fluoride melts the monotonic dependence was obtained: k s (CsF) < k s (KF) < k s (NaF-KF). 19 The purpose of the present work is to study the influence of alkaline Earth metal cations (Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ ) having high ionic potentials on the standard rate constants of charge transfer for the Nb(V)/Nb(IV) redox couple in the NaCl-KCl (equimol.) -NaF(10 wt%)-K 2 NbF 7 melt.…”

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confidence: 99%

Electrochemical Behavior of Niobium and Titanium Complexes in Chloride-Fluoride Melts with Addition of Alkaline Earth Metal Cations

Vetrova,

Popova,

Kuznetsov

2024

J. Electrochem. Soc.

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The standard rate constants of charge transfer (ks ) for the Nb(V)/Nb(IV) redox couple in the NaCl-KCl(equimol.)-NaF(10 wt.%)-K2NbF7 melt with addition of alkaline earth metal cations were determined. It was found that addition of alkaline earth metal cations resulted in increasing of ks to the certain ratio of Me2+/Nb(V) for the all alkaline earth metal cations due to substitution of Na+ and K+ cations by Me2+ in the second coordination sphere of niobium complexes that leads to decreasing of niobium fluoride complexes strength. Further addition brought to some decrease of the standard rate constants because the viscosity of melts increasing, which brings to decrease of the diffusion coefficients. The standard rate constants increase with an increase in the ionic potential and reach maximum values for the complexes with outer-sphere magnesium cations. Comparative analysis of the electrochemical behavior of Nb(V)/Nb(IV) and Ti(IV)/Ti(III) redox couples in the NaCl-KCl(equimol.)-NaF(10 wt.%) melt without and with addition of alkaline earth metal cations has been done. It was determined that mechanism of electron transfer from the cathode to niobium and titanium complexes in melts containing alkaline earth metal cations is the same and has a bridge nature.

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Standard charge transfer rate constants for Nb(V)/Nb(IV) redox pairs in fluoride melts

Cited by 10 publications

References 24 publications

Electrochemical Behavior of Niobium Complexes in Chloride-Fluoride Melts with Addition of Alkaline Cations

Electrochemical Behavior of Niobium Complexes in Chloride-Fluoride Melts with Addition of Alkaline Cations

Influence of the Alkaline Earth Metal Cations on the Standard Rate Constants of Charge Transfer for the Redox Couple Ti(IV)/Ti(III) in Chloride-Fluoride Melts

Electrochemical Behavior of Niobium and Titanium Complexes in Chloride-Fluoride Melts with Addition of Alkaline Earth Metal Cations

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