高精度恒温环境电化学量热系统的建立及Fe(CN)6^3-／Fe(CN)6^4-体系的热电化学  

Establishment of electrochemistry calorimetrical system with high precision temperature-constant condition and thermo-electrochemistry of Fe(CN)_6^(3-)/Fe(CN)_6^(4-) system

作　　者：张正华[1] 方正[1] 王少芬[2] 毛英[1] 陈坤汉[2] 

机构地区：[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

出　　处：《中国有色金属学报》2008年第9期1732-1735,共4页The Chinese Journal of Nonferrous Metals

基　　金：国家自然科学基金资助项目(50374077)

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±0.001K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?80.16kJ/mol和87.57J/(K·mol)。A precision system for thermo-electrochemical measurements with controlled temperature of -4-0.001 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）6^3-/Fe（CN）6^4- 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.

关 键 词：热电化学 熵变 绝对标度 溶解反应量热仪 

分 类 号：O642.3[理学—物理化学] O646[理学—化学]