Abstract

In general, the electrochemical characteristics of solid/liquid or liquid/liquid interfaces are highly nonlinear, i.e., the capacitance changes markedly according to the applied voltage. In this paper, we propose a novel method for evaluating these nonlinear characteristics quantitatively. That is, a sinusoidal voltage source is applied to a test solution and the waveform of the output current is analyzed by Fourier transformation. It is shown theoretically that higher harmonic components in the Fourier transformation afford us useful information on nonlinear behavior. It is stressed that our technique is entirely different from the classical impedance method, i.e., nonlinear components of the impedance can be evaluated in our method, having been ignored previously in the classical impedance measurement. As an application of this method, we have studied the effect of taste compounds on the intensities of the higher harmonics, using an electrochemical cell containing an aqueous solution of sodium oleate. It has been found that the intensities of the higher harmonics exhibit characteristic changes upon the addition of taste compounds, the change being dependent upon the taste category. The characteristic response to taste compounds in the electrochemical nonlinearity is discussed in relation to the experimental trend of the dynamic isotherm for oleic acid at an air/water interface.

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