Standard rate constants of charge transfer for Nb(V)/Nb(IV) redox couple in chloride-fluoride melts: Experimental and calculation methods

被引：22

作者：

Popova, A. V. ^{[1
]}

Kremenetsky, V. G. ^{[1
]}

Solov'ev, V. V. ^{[2
]}

Chernenko, L. A. ^{[2
]}

Kremenetskaya, O. V. ^{[3
]}

Fofanov, A. D. ^{[3
]}

Kuznetsov, S. A. ^{[1
]}

机构：

[1] Russian Acad Sci, Kola Sci Ctr, Tananaev Inst Chem & Technol Rare Elements & Min, Apatity 184200, Murmansk Oblast, Russia

[2] Kondratyuk Natl Tech Univ Poltava, Poltava, Ukraine

[3] Petrozavodsk State Univ, Petrozavodsk, Russia

来源：

RUSSIAN JOURNAL OF ELECTROCHEMISTRY | 2010年 / 46卷 / 06期

基金：

俄罗斯基础研究基金会;

关键词：

melt; redox couple; niobium complexes; cyclic voltammetry; diffusion coefficients; quasireversible process; standard rate constants of charge transfer; quantum-chemical calculations; ELECTRODE; KINETICS; SINGLE;

D O I：

10.1134/S1023193510060121

中图分类号：

O646 [电化学、电解、磁化学];

学科分类号：

081704 ;

摘要：

Standard rate constants k (s) of charge transfer for Nb(V)/Nb(IV) redox couple in NaCl-KCl (the equimolar mixture) -K2NbF7, KCl-K2NbF7, and CsCl-K2NbF7 melts are determined by using cyclic voltammetry. An unconventional series of the standard rate constants is found: k (s) (KCl) < k (s) (CsCl) < k (s) (NaCl-KCl). Ab initio calculations carried out by using a PC Gamess/Firefly quantum-chemical program showed that the charge transfer activation energy can change not monotonically in the Na-K-Cs series, in compliance with the reorganization energy relationship. This leads, in its turn, to nonmonotonic change in the charge transfer rate constants.

引用

页码：671 / 679

页数：9

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