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Modelling compressible electrolytes with phase transition

2014, Dreyer, Wolfgang, Giesselmann, Jan, Kraus, Christiane

A novel thermodynamically consistent diffuse interface model is derived for compressible electrolytes with phase transitions. The fluid mixtures may consist of N constituents with the phases liquid and vapor, where both phases may coexist. In addition, all constituents may consist of polarizable and magnetizable matter. Our introduced thermodynamically consistent diffuse interface model may be regarded as a generalized model of Allen-Cahn/Navier-Stokes/Poisson type for multi-component flows with phase transitions and electrochemical reactions. For the introduced diffuse interface model, we investigate physically admissible sharp interface limits by matched asymptotic techniques. We consider two scaling regimes, i.e. a non-coupled and a coupled regime, where the coupling takes place between the smallness parameter in the Poisson equation and the width of the interface. We recover in the sharp interface limit a generalized Allen-Cahn/Euler/Poisson system for mixtures with electrochemical reactions in the bulk phases equipped with admissible interfacial conditions. The interfacial conditions satisfy, for instance, a generalized Gibbs-Thomson law and a dynamic Young-Laplace law.

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Galilean Bulk-Surface Electrothermodynamics and Applications to Electrochemistry

2023, Müller, Rüdiger, Landstorfer, Manuel

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 (Formula presented.), which is divided into (Formula presented.) and (Formula presented.) by a possibly moving singular surface S, where a charged reacting mixture of a viscous medium can be present on each geometrical entity (Formula presented.). 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.