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Alternative reference system in the thermodynamics of solid elastic electrodes
Authors:B M Grafov  G Paasch
Institution:(1) A.N. Frumkin Institute of Electrochemistry RAS, 31 Leninskii prospekt, Moscow, 119071, Russia;(2) Leibniz Institute for Solid State and Materials Research IFW Dresden, PF 270016, 01171 Dresden, Germany
Abstract:Basic quantities in the thermodynamics of the solid elastic electrode are the surface tension tensor g mn and the work needed for the formation of the surface (interface) γ. It is scarcely mentioned explicitly anywhere that these intensive (specific) quantities are related to the surface of the elastically deformed electrode. On the other hand, in the thermodynamics of the volume elasticity, the free energy density of the deformed solid is related to the volume of the undeformed solid. In this paper, we introduce equivalently the undeformed surface of the solid elastic electrode as reference for both the surface tension tensor and the work of formation of the surface. Generalizing the analysis of two model systems, we deduce the corresponding alternative form of the Shuttleworth equation, where the two quantities appear as generalized force and generalized potential, and discuss consequences for the formulation of the differential of the surface excess of the internal energy.Dedicated to the memory of W. Schwabe
Keywords:Solid electrode  Surface thermodynamics  Shuttelworth equation
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