A general method for ensuring the self-consistent assignment of thermodynamic parameters in simulations of electrochemical-chemical systems is described. An essential part of the method is the identification of thermodynamically superfluous reactions (TSRs) which are defined as reactions in which the value of K(m) or E(m)o is a function of one or more previously specified values of K(m) or E(m)o for other reactions. A TSR can be removed from the system without altering the final equilibrium distribution of concentrations. However, a TSR can modify the time-dependent behavior of the system significantly. By identifying a TSR, assignment of an athermodynamic value for its equilibrium constant or formal potential can be precluded. The value of the equilibrium constant K(m) or formal potential E(m)o associated with any given TSR can be computed. This approach, which is designed to function in a cyclic voltammetric simulator which can generate and solve the requisite kinetic equations for any user-specified mechanism, is also generally applicable to any chemical or electrochemical simulation.