On the Relation Between Reaction Dynamics and Thermodynamics in Closed Systems

A reactive system’s slow dynamic behavior is approximated well by its evolution on manifolds of dimension lower than the dimensionality of the full composition space. This work addresses the relation between the isothermal reactive systems’ slow dynamics, described by the actual slow invariant manifolds, and notions from thermodynamics. In addition to mathematical proof, a realistic reactive system is utilized to show that other than identifying the actual equilibrium point, traditional thermodynamic potentials provide no guidance in determining a system’s actual slow invariant manifold. A comparison between several published thermodynamics-based manifolds and the actual slow invariant manifolds is presented.