On the nonequilibrium thermodynamics of large departures from butler-volmer behavior (2006).

Content Provider	CiteSeerX
Author	Miguel, Rodrigo De
Abstract	Large deviations from the behavior predicted by the Butler-Volmer equation of electrochemistry are accounted for using mesoscopic nonequilibrium thermodynamics. The nonequilibrium thermodynamic hypotheses are extended to include velocity space and cope with imperfect reactant transport leading to departures from Butler-Volmer behavior. This results in a modified Butler-Volmer equation in good agreement with experimental data. The distinct advantages of the method and its applicability to analyze other systems are briefly discussed. Activated processes are ubiquitous in nature and constitute a basic mechanism in the evolution of many systems. Chemical reactions, adsorption, nucleation, surface growth, elastoplasticity, and crossing of energy gaps in semiconductors are, to name a few, examples of activated processes. These processes obey a rate law often expressed as two Arrhenius terms accounting for the forward and the reverse rates, as is the case of the Butler-Volmer equation of electrochemistry.1-3 The Butler-Volmer equation describes the rate of an electrochemical reaction as a
File Format	PDF
Publisher Date	2006-01-01
Access Restriction	Open
Subject Keyword	Butler-volmer Behavior Large Departure Nonequilibrium Thermodynamics Butler-volmer Equation Rate Law Large Deviation Activated Process Good Agreement Distinct Advantage Imperfect Reactant Transport Velocity Space Basic Mechanism Electrochemical Reaction Reverse Rate Nonequilibrium Thermodynamic Hypothesis Mesoscopic Nonequilibrium Thermodynamics Chemical Reaction Surface Growth Energy Gap Arrhenius Term Many System Modified Butler-volmer Equation Experimental Data
Content Type	Text