The electrochemical Peltier heats of Fe(CN)63−/Fe(CN)64− system at 295.15 K

A specially designed thermo-electrochemical calorimeter was applied to measure the electrochemical Peltier heats (EPH) of Fe(CN) 6 3−/4− system at 295.15 K. The curves of the electrode potential changes and temperature changes against time for Fe(CN) 6 3−/4− couple with five groups of different concentrations were obtained under the condition of various constant-current polarizations. The EPH values for the considered electrode reaction are determined to be −41.31, −42.73, −44.28, −45.87, and −46.65 kJ mol−1 at the respective concentrations of 0.125, 0.175, 0.225, 0.275, and 0.300 mol dm−3; and the EPH and the apparent enthalpy change corresponding to the infinite dilution to be −37.42 and −84.10 kJ mol−1 at 295.15 K, respectively.