Fluctuation–dissipation analysis of diffusion and discharge processes

A fluctuation–dissipation analysis of the noise of a microelectrode is performed. It is shown that the mass transfer step and the discharge step are fluctuationally correlated already in the first order in the constant electric current polarizing the electrode. This basic result makes necessary a certain modification of the modern macroscopic theory of electrochemical fluctuations and development of a unified theory of the reaction elementary act and electrochemical fluctuations.