Bulk-Surface Electrothermodynamics and Applications to Electrochemistry

Entropy (Basel). 2018 Dec 6;20(12):939. doi: 10.3390/e20120939.

Abstract

We propose a modeling framework for magnetizable, polarizable, elastic, viscous, heat conducting, reactive mixtures in contact with interfaces. To this end, we first introduce bulk and surface balance equations that contain several constitutive quantities. For further modeling of the constitutive quantities, we formulate constitutive principles. They are based on an axiomatic introduction of the entropy principle and the postulation of Galilean symmetry. We apply the proposed formalism to derive constitutive relations in a rather abstract setting. For illustration of the developed procedure, we state an explicit isothermal material model for liquid electrolyte|metal electrode interfaces in terms of free energy densities in the bulk and on the surface. Finally, we give a survey of recent advancements in the understanding of electrochemical interfaces that were based on this model.

Keywords: bulk-surface electrothermodynamics; constitutive modeling; electrochemistry; entropy principle.