On the Nonequilibrium Thermodynamics of Large Departures from Butler−Volmer Behavior | Zendy

Rodrigo de Miguel | Zendy

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On the Nonequilibrium Thermodynamics of Large Departures from Butler−Volmer Behavior

Author(s) -

Rodrigo de Miguel

Publication year - 2006

Publication title -

the journal of physical chemistry b

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 0.864

H-Index - 392

eISSN - 1520-6106

pISSN - 1520-5207

DOI - 10.1021/jp060506p

Subject(s) - non equilibrium thermodynamics , mesoscopic physics , statistical physics , thermodynamics , physics , space (punctuation) , condensed matter physics , computer science , operating system

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.

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