Influence of the Second Coordination Sphere on the Electrochemical Behavior of Chromium Complexes in Chloride Melts: Experimental and Calculation Methods

被引：0
|
作者：
Stulov, Yu. V. [1 ]
Kremenetsky, V. G. [1 ]
Kuznetsov, S. A. [1 ]
机构：
[1] Russian Acad Sci, IV Tananaev Inst Chem & Technol Rare Elements & M, Kola Sci Ctr, Apatity 184209, Murmansk Region, Russia
来源：
INTERNATIONAL JOURNAL OF ELECTROCHEMICAL SCIENCE | 2013年 / 8卷 / 05期
基金：
俄罗斯基础研究基金会;
关键词：
melt; redox couple; chromium complexes; quasi-reversible process; cyclic voltammetry; standard rate constants of charge transfer; quantum-chemical calculations; CHARGE-TRANSFER; REDOX COUPLE; THERMODYNAMIC PROPERTIES; RATE CONSTANTS; MOLTEN-SALTS; SINGLE;
D O I：
暂无
中图分类号：
O646 [电化学、电解、磁化学];
学科分类号：
081704 ;
摘要：
The cyclic voltammetry method was used to determine the standard rate constants of charge transfer (k(s)) on a glassy carbon electrode for the Cr(III)/Cr(II) redox couple in the systems of NaCl-KCl-CrCl3, KCl-CrCl3, and CsCl-CrCl3 in the temperature range of 973-1173 K. It was shown that k(s) increase with increasing temperature and decreases as sodium cations are replaced by potassium and cesium cations in the second coordination sphere of chromium complexes. The calculations carried out using the Firefly quantum-chemical software by means of the DFT method showed that the values of the charge transfer activation energy change monotonously in the series of Na-K-Cs in accordance with the ratio of reorganization energies. In its turn, this leads to monotonous variation of the charge transfer rate constants.
引用
收藏
页码：7327 / 7344
页数：18
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