Extremum and optimization methods to evaluate the electrochemical Peltier heat are proposed based on the energy balance equations derived in part I. Using these methods the Peltier heat and other characteristic thermal constants of an electrode system can be obtained after only one potential step perturbation. The value of Pi(ox) for [Fe(CN)(6)](3-)/[Fe(CN)(6)](4-) (0.1 mol dm(-3) on Pt) is determined as -41.48 +/- 2.39 kJ mol(-1) and good agreement is observed between the values derived using the two methods and two types of heat-sensor electrode.