Journal of Physical Chemistry B, Vol.108, No.47, 18336-18340, 2004
Thermodynamics of electrochemical systems
A discussion of the fundamentals of thermodynamic theory describing electrochemical systems is presented. The basic relationships are deduced as properties of the electrochemical potential. The theory introduces an observable electric potential that is defined at every position within the electrochemical system as the potential of a reversible electrode placed there. To provide a good test of the formalism, five systems have been studied including equilibrium and nonequilibrium. The formalism emphasizes the advantages of the electric current density in order to characterize one of the degrees of irreversibility and the electrical equilibrium. Finally, the electrostatic potential is discussed within the framework of this theory.