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Functional constraints on phenomenological coefficients

Author(s): Klika, Václav; Pavelka, Michal; Benziger, Jay B.

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Abstract: Thermodynamic fluxes (diffusion fluxes, heat flux, etc.) are often proportional to thermodynamic forces (gradients of chemical potentials, temperature, etc.) via the matrix of phenomenological coefficients. Onsager’s relations imply that the matrix is symmetric, which reduces the number of unknown coefficients is reduced. In this article we demonstrate that for a class of nonequilibrium thermodynamic models in addition to Onsager’s relations the phenomenological coefficients must share the same functional dependence on the local thermodynamic state variables. Thermodynamic models and experimental data should be validated through consistency with the functional constraint. We present examples of coupled heat and mass transport (thermodiffusion) and coupled charge and mass transport (electro-osmotic drag). Additionally, these newly identified constraints further reduce the number of experiments needed to describe the phenomenological coefficient.
Publication Date: Feb-2017
Electronic Publication Date: 21-Feb-2017
Citation: Klika, Václav, Pavelka, Michal, Benziger, Jay B. (2017). Functional constraints on phenomenological coefficients. Physical Review E, 95 (2), 10.1103/PhysRevE.95.022125
DOI: doi:10.1103/PhysRevE.95.022125
ISSN: 2470-0045
EISSN: 2470-0053
Type of Material: Journal Article
Journal/Proceeding Title: Physical Review E
Version: Final published version. Article is made available in OAR by the publisher's permission or policy.

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