Abstract
The electrochemical Peltier effect is the heat effect observed at an electrode interphase when a reversible electrode reaction proceeds. The values of the molar Peltier heat Π for Cu(0)/Cu(II) and Ag(0)/Ag(I) systems are determined by combining controlled current electrolysis and thermometry in aqueous perchlorate solution. The values of Π for Ag(0)/0.02 M AgClO 4, 1 M HClO 4 and Cu(0)/0.02 M Cu(ClO 4) 2, 1 M HClO 4 are determined as −28 and 12 kJ mol −1 respectively. The dependence of Π upon the solution composition is theoretically calculated by using ionic entropy and ionic entropy of transport, and is compared with experimental results. The influence of electrochemically inactive supporting ions on Π is ascribed to the ionic heat of transport, and is of the order of several kJ mol −1. The values of the ionic heat of transport for copper aquo ion and ammonium ion are evaluated.
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