A GENERALIZED ENTROPY PRODUCTION ANALYSIS FOR REDUCTION OF CHEMICAL MECHANISMS INVOLVING IRREVERSIBLE REACTIONS

The paper introduces a generalized formulation of the entropy production analysis proposed for the reduction of detailed chemical reaction mechanisms [1] using more general expressions for the entropy generated by chemical reactions. The formulation is extended for the cases where the principle of detailed balance is not valid, namely in the case of irreversible reactions or when the reverse rate constants are not computed considering the thermodynamic equi- librium constants. The new formulation is compared to the original using a mechanism for n-butane consisting exclusively of reversible reactions, and then applied for the construction of skeletal mechanisms for n-dodecane starting from a detailed mechanism formed predom- inantly by irreversible reactions. The skeletal schemes are found to accurately capture the ignition delay times over an extended range of pressure, initial temperature and equivalence ratio.