Thermodynamic analysis of chemically reacting mixtures and their kinetics – example of a mixture of three isomers

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216305%3A26310%2F16%3APU120785" target="_blank" >RIV/00216305:26310/16:PU120785 - isvavai.cz</a>

Výsledek na webu

<a href="http://onlinelibrary.wiley.com/doi/10.1002/cphc.201600528/abstract" target="_blank" >http://onlinelibrary.wiley.com/doi/10.1002/cphc.201600528/abstract</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/cphc.201600528" target="_blank" >10.1002/cphc.201600528</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Thermodynamic analysis of chemically reacting mixtures and their kinetics – example of a mixture of three isomers

Popis výsledku v původním jazyce

Thermodynamics provides consequences of and restrictions on chemically reacting mixtures, particularly their kinetics, which have not been fully explored. In this paper, a comprehensive thermodynamic analysis is illustrated using a reacting mixture of three isomers. The rate equation is first derived on the basis of the results of non-equilibrium continuum thermodynamics of linear fluids, and is then subjected to the requirement of consistency with entropic inequality (the second law). This consistency test involves the correct representation of the reaction rate as a function of affinities. It is shown that entropic inequality restricts the signs or values of coefficients in the constitutive equations for reaction rates – rate constants. The use of reverse rate constants and the identification of thermodynamic and kinetic equilibrium constants are not necessary in this approach. Although the presented thermodynamic analysis works for independent reactions only, the rates of dependent reactions are not excluded from having effects on kinetics. It is shown that the rates of dependent reactions are combined from the rates of independent reactions differently than dependent reactions are combined from independent reactions. The results are compared to the classical mass action rate equations, and new restrictions on the values of the classical rate constants are derived.

Název v anglickém jazyce

Thermodynamic analysis of chemically reacting mixtures and their kinetics – example of a mixture of three isomers

Popis výsledku anglicky

Thermodynamics provides consequences of and restrictions on chemically reacting mixtures, particularly their kinetics, which have not been fully explored. In this paper, a comprehensive thermodynamic analysis is illustrated using a reacting mixture of three isomers. The rate equation is first derived on the basis of the results of non-equilibrium continuum thermodynamics of linear fluids, and is then subjected to the requirement of consistency with entropic inequality (the second law). This consistency test involves the correct representation of the reaction rate as a function of affinities. It is shown that entropic inequality restricts the signs or values of coefficients in the constitutive equations for reaction rates – rate constants. The use of reverse rate constants and the identification of thermodynamic and kinetic equilibrium constants are not necessary in this approach. Although the presented thermodynamic analysis works for independent reactions only, the rates of dependent reactions are not excluded from having effects on kinetics. It is shown that the rates of dependent reactions are combined from the rates of independent reactions differently than dependent reactions are combined from independent reactions. The results are compared to the classical mass action rate equations, and new restrictions on the values of the classical rate constants are derived.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/LO1211" target="_blank" >LO1211: Centrum materiálového výzkumu na FCH VUT v Brně - udržitelnost a rozvoj</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2016

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

CHEMPHYSCHEM

ISSN

1439-4235

e-ISSN

1439-7641

Svazek periodika

17

Číslo periodika v rámci svazku

20

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

9

Strana od-do

3333-3341

Kód UT WoS článku

000386790600025

EID výsledku v databázi Scopus

2-s2.0-84991728058