Extended detailed balance for systems with irreversible reactions

摘要: The principle of detailed balance states that in equilibrium each elementary process is equilibrated by its reverse process. For many real physico-chemical complex systems (e.g. homogeneous combustion, heterogeneous catalytic oxidation, most enzyme reactions, etc.), mechanisms include both reversible and irreversible reactions. In this case, the cannot be applied directly. We represent reactions as limits steps obtain for with some processes. prove two consequences these mechanisms: structural condition algebraic form together extended balance. part. convex hull stoichiometric vectors has empty intersection linear span Physically, means included oriented cyclic pathways. are also when concentrations (or activities) tend to zero. Surprisingly, structure limit reaction mechanism crucially depends on relative speeds tendency