Galilean Bulk-Surface Electrothermodynamics and Applications to Electrochemistry

Entropy (Basel). 2023 Feb 25;25(3):416. doi: 10.3390/e25030416.

Abstract

In this work, the balance equations of non-equilibrium thermodynamics are coupled to Galilean limit systems of the Maxwell equations, i.e., either to (i) the quasi-electrostatic limit or (ii) the quasi-magnetostatic limit. We explicitly consider a volume Ω, which is divided into Ω+ and Ω- by a possibly moving singular surface S, where a charged reacting mixture of a viscous medium can be present on each geometrical entity (Ω+,S,Ω-). By the restriction to the Galilean limits of the Maxwell equations, we achieve that only subsystems of equations for matter and electromagnetic fields are coupled that share identical transformation properties with respect to observer transformations. Moreover, the application of an entropy principle becomes more straightforward and finally helps estimate the limitations of the more general approach based the full set of Maxwell equations. Constitutive relations are provided based on an entropy principle, and particular care is taken in the analysis of the stress tensor and the momentum balance in the general case of non-constant scalar susceptibility. Finally, we summarise the application of the derived model framework to an electrochemical system with surface reactions.

Keywords: asymptotic analysis; bulk-surface systems; constitutive modelling; electrothermodynamics; entropy principle.