Abstract
Mixed correlators of 2nd order with respect to fluctuations of the electrode free charge, full charge, and potential are analyzed on the basis of classical theory of noise and fluctuations. It is shown that the mixed correlator of free and full charge fluctuations is determined by the electrochemical cell temperature and the electrical capacitance corresponding to the electrode free charge. At the same time, the mixed correlator of the electrode full charge and potential fluctuations equals the product of the Boltzmann constant and temperature. The former result corresponds to both the Gibbs fluctuation theory and the Einstein-Landau theory of the extensive quantities’ mixed correlators. The latter one corresponds to the Einstein-Landau theory for the paired mixed correlators of conjugated (extensive and intensive) quantities. The results obtained evidence that, unlike the 3rd order correlators, the ergodic hypothesis with respect to the 2nd order correlators works well even in rather complicated electrochemical systems.
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