The electrochemical Peltier heat of the standard hydrogen electrode reaction

A method for measuring the electrochemical Peltier heat (EPH) of a single electrode reaction has been developed and an absolute scale is suggested to obtain EPH of the standard hydrogen electrode. The scale is based on ϕ0* = 0 and ΔS0* = 0 for any electrode reaction at zero Kelvin, in accord with the third law of thermodynamics. The relationships between entropy, enthalpy and free energy changes on this scale and on the conventional scale are derived. Calorimetric experiments were made on the Fe(CN)63−/Fe(CN)64− system at five different concentrations at 298.15 K, and EPH for the standard hydrogen electrode reaction is obtained. EPHs and the entropy change on the absolute scale for the studied redox are linearly related to concentration of electrolyte. The reversible electric work is almost concentration independent in the range of concentration studied.