Experimental and Calculation Methods of Studying the Effect of Second Coordination Sphere on Standard Rate Constants of Charge Transfer for Cr(III)/Cr(II) Redox Couple in Chloride Melts

被引：8

作者：

Stulov, Yu V. ^{[1
]}

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

Kremenetskaya, O. V. ^{[2
]}

Fofanov, A. D. ^{[2
]}

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

机构：

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

[2] Petrozavodsk State Univ, Petrozavodsk, Russia

来源：

RUSSIAN JOURNAL OF ELECTROCHEMISTRY | 2011年 / 47卷 / 08期

基金：

俄罗斯基础研究基金会;

关键词：

melt; redox couple; chromium complexes; diffusion coefficients; quasireversible process; cyclic voltammetry; standard rate constants of charge transfer; quantum-chemical calculations; ELECTRODE PROCESSES; MOLTEN-SALTS; REDUCTION/OXIDATION; COMPLEXES; CHROMIUM; CR(II); SINGLE;

D O I：

10.1134/S1023193511080143

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) grows at an increase in the 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 PC GAMESS/Firefly quantum-chemical software by means of the DFT technique 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

页码：948 / 958

页数：11

共 14 条

[1] Experimental and calculation methods of studying the effect of second coordination sphere on standard rate constants of charge transfer for Cr(III)/Cr(II) redox couple in chloride melts
Yu. V. Stulov
V. G. Kremenetsky
O. V. Kremenetskaya
A. D. Fofanov
S. A. Kuznetsov
Russian Journal of Electrochemistry, 2011, 47 : 948 - 958
[2] Effect of the Second Coordination Sphere on the Standard Rate Constants of Charge Transfer for the Cr(III)/Cr(II) Redox Couple in Chloride Melts
Stulov, Yu. V.
Kremenetsky, V. G.
Kuznetsov, S. A.
MOLTEN SALTS AND IONIC LIQUIDS 18, 2012, 50 (11): : 135 - 152
[3] Unusual effect of the second coordination sphere on the standard charge transfer rate constants for the Nb(V)/Nb(IV) redox couple in chloride—Fluoride melts
S. A. Kuznetsov
V. G. Kremenetskii
A. V. Popova
O. V. Kremenetskaya
V. T. Kalinnikov
Doklady Physical Chemistry, 2009, 428 : 209 - 212
[4] Unusual effect of the second coordination sphere on the standard charge transfer rate constants for the Nb(V)/Nb(IV) redox couple in chloride-Fluoride melts
Kuznetsov, S. A.
Kremenetskii, V. G.
Popova, A. V.
Kremenetskaya, O. V.
Kalinnikov, V. T.
DOKLADY PHYSICAL CHEMISTRY, 2009, 428 : 209 - 212
[5] Standard rate constants of charge transfer for Nb(V)/Nb(IV) redox couple in chloride-fluoride melts: Experimental and calculation methods
A. V. Popova
V. G. Kremenetsky
V. V. Solov’ev
L. A. Chernenko
O. V. Kremenetskaya
A. D. Fofanov
S. A. Kuznetsov
Russian Journal of Electrochemistry, 2010, 46 : 671 - 679
[6] Standard rate constants of charge transfer for Nb(V)/Nb(IV) redox couple in chloride-fluoride melts: Experimental and calculation methods
Popova, A. V.
Kremenetsky, V. G.
Solov'ev, V. V.
Chernenko, L. A.
Kremenetskaya, O. V.
Fofanov, A. D.
Kuznetsov, S. A.
RUSSIAN JOURNAL OF ELECTROCHEMISTRY, 2010, 46 (06) : 671 - 679
[7] The Effect of the Second Coordination Sphere on Electrochemistry of Niobium Complexes in Alkali Halide Melts II. Standard Rate Constants of Charge Transfer for the Nb(V)/Nb(IV) Redox Couple
Popova, A. V.
Kuznetsov, S. A.
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2016, 163 (02) : H53 - H58
[8] Unusual influence of the temperature on the standard rate constants of charge transfer for the Eu(III)/Eu(II) redox couple in chloride-bromide melts
Kuznetsov, Sergey A.
Gaune-Escard, Marcelle
ZEITSCHRIFT FUR NATURFORSCHUNG SECTION A-A JOURNAL OF PHYSICAL SCIENCES, 2007, 62 (7-8): : 445 - 451
[9] Standard Rate Constants of the Charge Transfer in the Cr(III)/Cr(II) Redox Couple in NaCl-KCl-CrCl3 and NaCl-KCl-K3CrF6 Salt Melts
Stulov Y.V.
Kuznetsov S.A.
Russian Metallurgy (Metally), 2011, 2011 (2) : 158 - 163
[10] 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, D. A.
Kuznetsov, S. A.
MOLTEN SALTS AND IONIC LIQUIDS 20, 2016, 75 (15): : 363 - 371

← 1 2 →