Dissipations and polarizations in irreversible electrode processes: A unite formalism of stochastic thermodynamics of both concentration polarizationand activation polarization

A generalized stochastic model of the irreversible electrode processes is p roposed. By means of it the dissipation and the fluctuation around nonequil ibrium steady states of the electrode chemical reaction systems is analyzed . It is shown that the polarizations, in spite of the concentration polariz ation or the electrochemical polarization, originate from the nontrivial di ssipations together with the non-Poissonian fluctuations in irreversible el ectrode processes. Furthermore a dissipation-fluctuation formula of electro de polarization is deduced explicitly. This formula is a dominant nonequili brium thermodynamic equality, useful for the theoretic analysis of the pola rization in irreversible electrode processes when the validity of the class ical equilibrium thermodynamics breaks down. It turns out that the well-kno wn Nernst formula followed by concentration polarization and the famous Taf el equation valid for electrochemical polarization are only the macroscopic approximations of two special limit cases in the formalism presented in th is paper. If the fluctuation departs from the Gaussian a revision will be i nevitable. (C) 1999 American Institute of Physics. [S0021-9606(99)70609-4].