Criteria for chemical equilibrium with application to methane steam reforming

A literature survey reveals significant inaccuracy of the prediction of equilibrium models. A thermodynamic analysis is presented to show that the equilibrium calculations rest on a critical assumption of reversible heat exchange between a reactive system and its surrounding. Indeed, a correct application of the energy conservation and entropy balance equation leads to a modified Gibbs function. Minimization of the modified Gibbs function happens to be identical to maximization of the total entropy generation. The actual chemical equilibrium is shown through a methane steam reforming, as an illustrative example, to be correctly predicted by kinetic modeling. The state of chemical equilibrium does not necessarily correspond to maximum entropy generation. Once a chemical equilibrium has been established, both the total entropy generation and the modified Gibbs function remain unaltered and independent of time.