The available analyses of the conditions for equilibrium in electrochemical systems do not consider the electrostatic field as a possible variable. Since there is a voltage difference between the electrodes in an electrochemical system, an electrostatic field must be present, and this field must be considered in the treatment of equilibrium because it affects the internal energy of the system. This paper presents an analysis in which the electric displacement vector is included as a possible variable. The results show that Poisson's equation is a condition of equilibrium in addition to the usual conditions of uniformity of the electrochemical potential, the pressure, and the temperature.

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