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THETHERMODYNAMICSOFLINEARFLUIDSANDFLUIDMIXTURES
REACTION KINETICS AND MECHANISMS
Section 4.9 of our book shows kinetic consequences of the thermodynamic method described in the book. Among them there is a possibility to design reaction schemes (networks, mechanisms) on the thermodynamic basis and related mathematics. More details and examples can be found in papers:
- PEKAŘ M. Thermodynamic framework for design of reaction rate equations and schemes. Collect. Czech. Chem. Commun., 2009, vol. 74, no. 9, p. 1375–1401. ISSN 0010-0765. See here.
- PEKAŘ M. Macroscopic derivation of the kinetic mass-action law. Reac. Kinet. Mech. Cat., 2010, vol. 99, no. 1, p. 29-35. ISSN 1878-5190.
Comment – THE DRIVING FORCE
Science magazine brought in December 2013 a perspective on enzyme kinetics in which also the “thermodynamic driving force for chemical reactions” was discussed. However, the approach presented there is not free of problems. Comments including the more correct “driving force”, based on the approach described in our book, can be found here.
THERMODYNAMICS & KINETICS
Paper on proper thermodynamic analysis of reaction kinetics based on the methodology of our book was published in October 2016: PEKAŘ, M. Thermodynamic analysis of chemically reacting mixtures and their kinetics – example of a mixture of three isomers. ChemPhysChem, 2016, vol. 17, no. 20, p. 3333-3341.
An extension appeared as open access article: PEKAŘ, M. Thermodynamic Analysis of Chemically Reacting Mixtures—Comparison of First and Second Order Models. Frontiers in Chemistry, 2018, vol. 6, article 35.
Autocatalytic reactions possess a specific stoichiometry. Apparently their kinetics is unsuitable for the stoichiometry-based analysis presented in our book (sections 4.2 and 4.9). An open access paper shows that the thermodynamic polynomial works also in autocatalysis cases (PEKAŘ, M. Non-Equilibrium Thermodynamics View on Kinetics of Autocatalytic Reactions—Two Illustrative Examples. MOLECULES, 2021, vol. 26, no. 3, article 585).
A related note on (generally desirable) using rates in kinetic studies was posted on Qeios platform.Its substantially extended version was posted on the same platform.