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

Result code in 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>

Result on the web

<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>

Result language

angličtina

Original language name

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

Original language description

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.

Czech name

—

Czech description

—

Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

<a href="/en/project/LO1211" target="_blank" >LO1211: Materials Research Centre at FCH BUT- Sustainability and Development</a><br>

Continuities

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

Publication year

2016

Confidentiality

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

Name of the periodical

CHEMPHYSCHEM

ISSN

1439-4235

e-ISSN

1439-7641

Volume of the periodical

17

Issue of the periodical within the volume

20

Country of publishing house

DE - GERMANY

Number of pages

9

Pages from-to

3333-3341

UT code for WoS article

000386790600025

EID of the result in the Scopus database

2-s2.0-84991728058