Temperature dependence of differential capacitance in the electric double layer.Symmetric valency 1:1 electrolytes

The differential capacitance of an electric double layer formed by an aqueous solution of KNO3 on a glassy carbon electrode is measured by impedance analysis at constant frequency. Results are obtained at electrolyte concentrations of 0.1 mol/dm(3), 0.5 mol/dm(3), and 1.0 mol/dm(3), and at a series of temperatures, viz., 288 K, 298 K, 308 K, 318 K, and 328 K. The differential capacitance envelopes reveal a rich, complex pattern of maxima, minima, and local minima, whose magnitude and position change with a change in solution concentration. At the two lower concentrations, the temperature dependence of the capacitance, for example, at zero electrode potential, shows an alternating positive-negative behavior, while at the highest concentration of 1.0 mol/dm(3), the slope of the differential capacitance-electrode potential curve is always positive. The experimental results are supplemented by a numerical grand canonical Monte Carlo simulation study of a restricted primitive model double layer but with an off-center cationic charge achieved by displacing the charge center from the ion sphere center toward its surface. The simulations, performed at the electrolyte concentration of 1.0 mol/dm(3) and constant cation charge center displacement, and at varying electrode potentials and temperatures, show, in general, a negative temperature dependence of the differential capacitance. However, this temperature dependence can also be positive for a negative electrode charge and for a sufficiently large gradient of the cation charge center displacement with temperature. This feature is seen to be associated with an increase in the entropy of formation of the double layer.