Abstract: This report presents general expressions for isothermal chemical reaction kinetics under zero-field and resonant microwave-field (MWF) conditions by applying irreversible thermodynamics and assuming the Onsager phenomenological coefficient as a function of concentration of the reacting matter along the reaction coordinate. For isothermal reactions under zero-field conditions, the global steady-state reaction rate is predicted to be proportional to the product of a negative exponential function of activation energy and a non-linear function of affinity. Conversely, for isothermal reactions under MWF conditions, the highly enhanced reaction rate, relatively independent of its affinity, is dominantly governed by the negative exponential function of a reduced activation energy, attributed to the enormous MWF-produced molar free energy (chemical potential) input to the total chemical potential of the reactant.
The irreversible-thermodynamics-derived reaction-rate expressions proposed in this report are consistent with the traditional chemical kinetic theories based on the law of mass action. In addition, the rationale accordingly developed may also be applied to comprehend and describe the kinetic behavior of most solid-state chemical reactions, such as oxide-reduction processes, occurring under zero-field and MWF conditions reported in the MS&T community.
Author: Boon Wong
Keywords: Resonant microwave-field (MWF), Irreversible thermodynamics, Total chemical potential, Affinity (driving force), Reaction coordinate (path), Chemical reaction kinetics (rate)