An electrochemical reaction as a branch of chemical reactions is one of the fundamental phenomena, but exact electrochemical reaction mechanisms have been unknown. We here propose a statistical thermodynamic theory for electrochemical reactions, which is vital to investigate electrochemical reactions for non-equilibrium, quasi-equilibrium, and equilibrium. The theory utilizes a postulate that electric potential, time, and space are independent and orthogonal variables in extended phase spaces. It is an internal Gibbs energy transport theory for electrochemical reactions leading to the unification of non-equilibrium and equilibrium reactions, a non-equilibrium generalization beyond quasi-equilibrium theories for migration and diffusion, and the integration of diffusion and convection mechanisms. It predicts that there are current density gaps and broken discrete symmetries at the activation potential, time, and displacement. It provides the Nernst equation, the rate equation, and the spatial cross section of electrochemical reactions. The electrochemical theory demonstrates relationships among electrochemical reactions, thermodynamics, and statistical physics.
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