On the Thermal Fluctuations of Free Charge
in the ErshlerRandles Circuit

B. M. Grafov^z

Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia

Received October 3, 2008

Abstract—Noise method for the analyzing of thermodynamic second-order fluctuations of the electrical dou-
ble layer charge in complicated electrochemical systems is developed. The method is based on the joint appli-
cation of the Nyquist fluctuation–dissipation theorem and Laplace transform. Second-order fluctuations of the
free charge in the electrical double layer are studied under the conditions when the weak-signal faradaic imped-
ance of equilibrated electrode is determined by the diffusion impedance, alongside with the slow-discharge
resistance. It is shown that, unlike the high-order fluctuations, the level of thermodynamic second-order fluctu-
ations of the free charge does not depend on the mechanism of interaction of the thermodynamic system with
thermostat; it fully corresponds to the conceptions of the Gibbs statistical thermodynamics.

Key words: thermal fluctuations, electrical double layer, Gibbs statistical thermodynamics

DOI: 10.1134/S1023193509090092

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