(1. 中南大學(xué) 化學(xué)化工學(xué)院，長(zhǎng)沙 410083；
2. 長(zhǎng)沙理工大學(xué) 化學(xué)與環(huán)境工程學(xué)院，長(zhǎng)沙 410077)
摘 要: 以SRC−100溶解反應(yīng)量熱儀恒溫系統(tǒng)、溫度傳感器和數(shù)據(jù)采集軟件，結(jié)合CHI660B電化學(xué)工作站建立了控溫精度為±0.001 K的高精度恒溫環(huán)境下電化學(xué)量熱系統(tǒng)。采用恒電流極化方法對(duì)5組不同濃度的Fe(CN)63−/Fe(CN)64−體系進(jìn)行熱電化學(xué)測(cè)試，獲得該半電池反應(yīng)電極電壓—電流—溫差—時(shí)間4維數(shù)據(jù)，根據(jù)熱電化學(xué)基本方程計(jì)算得該電對(duì)偶反應(yīng)“熱電化學(xué)表觀焓變”和絕對(duì)標(biāo)度下標(biāo)準(zhǔn)氫電極熵變分別為−80.16 kJ/mol和87.57 J/(K·mol)。
關(guān)鍵字: 熱電化學(xué)；熵變；絕對(duì)標(biāo)度；溶解反應(yīng)量熱儀
（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
