(1. 中南大学 化学化工学院，长沙 410083；
2. 长沙理工大学 化学与环境工程学院，长沙 410077)
摘 要: 以SRC−100溶解反应量热仪恒温系统、温度传感器和数据采集软件，结合CHI660B电化学工作站建立了控温精度为±0.001 K的高精度恒温环境下电化学量热系统。采用恒电流极化方法对5组不同浓度的Fe(CN)63−/Fe(CN)64−体系进行热电化学测试，获得该半电池反应电极电压—电流—温差—时间4维数据，根据热电化学基本方程计算得该电对偶反应“热电化学表观焓变”和绝对标度下标准氢电极熵变分别为−80.16 kJ/mol和87.57 J/(K·mol)。
关键字: 热电化学；熵变；绝对标度；溶解反应量热仪
（1. School of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China;
2. College of Chemistry and Environmental Engineering, Changsha University of Science and Technology, Changsha 410083, China）
Abstract:A precision system for thermo-electrochemical measurements with controlled temperature of ±0.001 K was set up based on the SRC−100 solution reaction isoperibol calorimeter and an electrochemical workstation. The data of electric potential and temperature difference against time for equal molar Fe(CN)63−/Fe(CN)64− couple with 5 sets of different concentrations at 298.15 K were obtained under the condition of various constant-current polarizations. According to the basic equation for thermo-electrochemistry (TEC), the thermo-electrochemical apparent enthalpy change for the studied couple and the entropy change for the standard electrode reaction on the absolute scale are determined as −80.16 kJ/mol and 87.57 J/(K·mol), respectively, being close to those in literatures.
Key words: thermo-electrochemistry; entropy change; absolute scale; solution-reaction isoperibol calorimeter
