Electrochemistry of CeCl3 in Molten LiCl-KCl Eutectic

作     者：ZHANG Meng HAN Wei ZHANG Milin LI Yunna ZHU Fengyan XUE Yun 

作者机构：Fundamental Science on Nuclear Safety and Simulation Technology Laboratory Key Laboratory of Superlight Materials and Surface Technology Ministry of Education Harbin Engineering University Harbin 150001 P. R. China 

出 版 物：《Chemical Research in Chinese Universities》 (高等学校化学研究（英文版）)

年 卷 期：2014年第30卷第3期

页      面：489-494页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 080502[工学-材料学] 0805[工学-材料科学与工程（可授工学、理学学位）] 0703[理学-化学] 

基　　金：Supported by the High Technology Research and Development Program of China(No.2011AA03A409)  the National Natural Science Foundation of China(Nos.51104050  91326113  21271054  21173060)  the China Postdoctoral Science Foundation(No.20110491029)  the Heilongjiang Postdoctoral Fund  China(No.LBH-Z10208)  the Heilongjiang Educational Commission Foundation  China(No.12513045)  the Fundamental Research Funds for the Central Universities  China(No.HEUCF141502)  the Project of the Scientific Technology Bureau of Harbin  China(No.2012RFQXS 102) and the Basic Research Foundation of Harbin Engineering University  China(No.HEUFT08031) 

主　　题：LiCl-KCl eutectic melt CeCl3 Standard rate constant Standard apparent potential Activity coefficient 

摘      要：The electrochemical properties of CeCl3, dissolved in LiCI-KCI eutectic melt, were investigated by electrochemical techniques, such as cyclic voltammetry and square wave voltammetry on Mo electrode. It was shown that Ce（Ⅲ） is reduced to Ce（0） based on a three-step mechanism. In a temperature range of 833-923 K, the diffusion coefficient of Ce（Ⅲ） is lgDceoH）=-2.49-1704/T determined by means of the Berzins-Delahay equation with two different expressions under reversible and irreversible conditions. The apparent standard potential of a Ce（Ⅲ）/Ce（0） redox system is ECE^3＋0^＊/Ce^0 =3.551＋0.0006132T（K） vs. Cl2/Cl^-. Some thermochemical properties of CeCl3 solutions were also derived from the electrochemical measurements, such as the enthalpy, entropy, Gibbs free energies and the activity coefficients of Ce（Ⅲ）. The Gibbs free energy of a dilute solution of CeCl3 in this system was determined to be △G^0CeCl3/（kJ·mol^-1）=-1027.9＋0.178T（K） And the activity coefficients, γCeCl3 , range between （7.78-9.14）×10^-3. Furthermore, the standard rate constant of kinetic reaction was calculated to be （4.94-9.72）× 10^-3 cmZ/s and the reaction was regarded as a quasi-reversible reaction under the present experimental conditions at 833 K.