Beyond onsager–casimir relations: shared dependence of phenomenological coefficients on state variables

Phenomenological coefficients in linear nonequilibrium thermodynamics have been considered to be independent, apart from restrictions due to the Onsager–Casimir reciprocal relations and the requirement to have non-negative entropy production. Recently, it has been shown that functional constraints b...

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Main Authors: Klika, V, Krause, A
Format: Journal article
Language:English
Published: American Chemical Society 2018
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author Klika, V
Krause, A
author_facet Klika, V
Krause, A
author_sort Klika, V
collection OXFORD
description Phenomenological coefficients in linear nonequilibrium thermodynamics have been considered to be independent, apart from restrictions due to the Onsager–Casimir reciprocal relations and the requirement to have non-negative entropy production. Recently, it has been shown that functional constraints between these coefficients may hold, restricting their dependence on state variables, especially in the case of coupled phenomena. Here we demonstrate that such restrictions require only mild assumptions on the system of interest and are, in fact, much more constraining than previously reported. Such constraints vastly reduce the set of plausible models for constitutive relations and allow for simpler experimental determinations of dependencies in coupled systems. These results may also clarify inconsistencies in the literature regarding constitutive models used that do not obey these thermodynamic constraints.
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spelling oxford-uuid:bfd4735b-46ec-4e26-ae04-8357f0c4c39f2022-03-27T05:50:19ZBeyond onsager–casimir relations: shared dependence of phenomenological coefficients on state variablesJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:bfd4735b-46ec-4e26-ae04-8357f0c4c39fEnglishSymplectic Elements at OxfordAmerican Chemical Society2018Klika, VKrause, APhenomenological coefficients in linear nonequilibrium thermodynamics have been considered to be independent, apart from restrictions due to the Onsager–Casimir reciprocal relations and the requirement to have non-negative entropy production. Recently, it has been shown that functional constraints between these coefficients may hold, restricting their dependence on state variables, especially in the case of coupled phenomena. Here we demonstrate that such restrictions require only mild assumptions on the system of interest and are, in fact, much more constraining than previously reported. Such constraints vastly reduce the set of plausible models for constitutive relations and allow for simpler experimental determinations of dependencies in coupled systems. These results may also clarify inconsistencies in the literature regarding constitutive models used that do not obey these thermodynamic constraints.
spellingShingle Klika, V
Krause, A
Beyond onsager–casimir relations: shared dependence of phenomenological coefficients on state variables
title Beyond onsager–casimir relations: shared dependence of phenomenological coefficients on state variables
title_full Beyond onsager–casimir relations: shared dependence of phenomenological coefficients on state variables
title_fullStr Beyond onsager–casimir relations: shared dependence of phenomenological coefficients on state variables
title_full_unstemmed Beyond onsager–casimir relations: shared dependence of phenomenological coefficients on state variables
title_short Beyond onsager–casimir relations: shared dependence of phenomenological coefficients on state variables
title_sort beyond onsager casimir relations shared dependence of phenomenological coefficients on state variables
work_keys_str_mv AT klikav beyondonsagercasimirrelationsshareddependenceofphenomenologicalcoefficientsonstatevariables
AT krausea beyondonsagercasimirrelationsshareddependenceofphenomenologicalcoefficientsonstatevariables