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PEKAŘ, M.
Original Title
Thermodynamic analysis of chemically reacting mixtures – comparison of first and second order models
Type
journal article in Web of Science
Language
English
Original Abstract
Recently, 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.
Keywords
affinity; entropic inequality; independent reactions; kinetics; rate constants; rate equations; thermodynamics
Authors
Released
1. 3. 2018
Publisher
Frontiers
ISBN
2296-2646
Periodical
Frontiers in Chemistry
Year of study
6
Number
35
State
Swiss Confederation
Pages from
1
Pages to
7
Pages count
URL
http://journal.frontiersin.org/article/10.3389/fchem.2018.00035/full
Full text in the Digital Library
http://hdl.handle.net/11012/84117
BibTex
@article{BUT146656, author="Miloslav {Pekař}", title="Thermodynamic analysis of chemically reacting mixtures – comparison of first and second order models", journal="Frontiers in Chemistry", year="2018", volume="6", number="35", pages="1--7", doi="10.3389/fchem.2018.00035", issn="2296-2646", url="http://journal.frontiersin.org/article/10.3389/fchem.2018.00035/full" }