Thermodynamic analysis of chemically reacting mixtures – comparison of first and second order models

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dc.contributor.authorPekař, Miloslavcs
dc.coverage.issue35cs
dc.coverage.volume6cs
dc.date.issued2018-03-01cs
dc.description.abstractRecently, a method based on non-equilibrium continuum thermodynamics which derives thermodynamically consistent reaction rate models together with thermodynamic constraints on their parameters was analyzed using a triangular reaction scheme. The scheme was kinetically of the first order. Here, the analysis is further developed for several first and second order schemes to gain a deeper insight into the thermodynamic consistency of rate equations and relationships between chemical thermodynamic and kinetics. It is shown that the thermodynamic constraints on the so-called proper rate coefficient are usually simple sign restrictions consistent with the supposed reaction directions. Constraints on the so-called coupling rate coefficients are more complex and weaker. This means more freedom in kinetic coupling between reaction steps in a scheme, i.e., in the kinetic effects of other reactions on the rate of some reaction in a reacting system. When compared with traditional mass-action rate equations, the method allows a reduction in the number of traditional rate constants to be evaluated from data, i.e., a reduction in the dimensionality of the parameter estimation problem. This is due to identifying relationships between mass-action rate constants (relationships which also include thermodynamic equilibrium constants) which have so far been unknown.en
dc.formattextcs
dc.format.extent1-7cs
dc.format.mimetypeapplication/pdfcs
dc.identifier.citationFrontiers in Chemistry. 2018, vol. 6, issue 35, p. 1-7.en
dc.identifier.doi10.3389/fchem.2018.00035cs
dc.identifier.issn2296-2646cs
dc.identifier.orcid0000-0002-3878-0917cs
dc.identifier.other146656cs
dc.identifier.urihttp://hdl.handle.net/11012/84117
dc.language.isoencs
dc.publisherFrontierscs
dc.relation.ispartofFrontiers in Chemistrycs
dc.relation.urihttp://journal.frontiersin.org/article/10.3389/fchem.2018.00035/fullcs
dc.rightsCreative Commons Attribution 4.0 Internationalcs
dc.rights.accessopenAccesscs
dc.rights.sherpahttp://www.sherpa.ac.uk/romeo/issn/2296-2646/cs
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/cs
dc.subjectaffinityen
dc.subjectentropic inequalityen
dc.subjectindependent reactionsen
dc.subjectkineticsen
dc.subjectrate constantsen
dc.subjectrate equationsen
dc.subjectthermodynamicsen
dc.titleThermodynamic analysis of chemically reacting mixtures – comparison of first and second order modelsen
dc.type.driverarticleen
dc.type.statusPeer-revieweden
dc.type.versionpublishedVersionen
sync.item.dbidVAV-146656en
sync.item.dbtypeVAVen
sync.item.insts2025.02.03 15:38:02en
sync.item.modts2025.01.17 18:44:15en
thesis.grantorVysoké učení technické v Brně. Fakulta chemická. Centrum materiálového výzkumucs
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