交流电化学热法测定电极反应熵变①董良俊庄继华江志裕＊（复旦大学化学系上海２００４３３）电极反应的熵变是电极过程的重要物理化学参数之一．测定电极反应的熵变不仅有助于分析电极反应，而且由于熵变与电极反应时的温度变化密切相关，对于一些实际体系，如化学电源、...
An ac electrochemical thermal method was developed for measuring the entropy change of the electrochemical reaction. When an ac current i 0 cos ωt passed through an electrode in the solution, the heat produced at the surface consisted of several parts. The part varied with frequency ω was caused by the entropy change of the electrochemical reaction, so called the Peltier heat. It could be measured by using a pyroelectric PVDF film detector with a lock in amplifier. This method presents the advantage to inhibit the influence of the polarization heat and Joule heat. The entropy changes of electrochemical reactions in the Fe 2+ /Fe 3+ and Cu/Cu 2+ systems were measured by this method, and some mechanisms were discussed.
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