Non-equilibrium thermodynamics of closed-system reactions

Stoichiometric chemical reactions in a closed isothermal system are studied in terms of classical and statistical thermodynamics. It is demonstrated that the affinity decay rate in such a system is independent of reaction mechanism. On this basis a general thermodynamic description of the reactions is provided, valid for reactions with diverse mechanisms. In contrast to earlier approaches dealing only with systems close to equilibrium, the present formalism is applicable to systems arbitrarily far from equilibrium. The agreement between computation and experiment is distinctly better than in calculations based on absolute rate theory.