Collect. Czech. Chem. Commun. 2009, 74, 1375-1401
Published online 2009-09-18 12:36:45

Thermodynamic framework for design of reaction rate equations and schemes

Miloslav Pekař

Institute of Physical and Applied Chemistry, Faculty of Chemistry, Brno University of Technology, Purkyňova 118, 612 00 Brno, Czech Republic


It has been shown previously that rational thermodynamics provides general foundations of mass-action kinetic law from the principles of continuum, irreversible thermodynamics. Practical outcomes of this phenomenological theory are analyzed and compared with traditional kinetic approaches on the example of N2O decomposition. It is revealed that classical rate equations are only simplified forms of a polynomial approximation to a general rate function proved by the continuum thermodynamics. It is also shown that various special considerations that have been introduced formerly as additional hypothesis to satisfactorily describe experimental data are naturally included in the thermodynamic approach. The method, in addition, makes it possible to obtain more general mass-action-type rate equations that give better description of experimental data than the traditional ones. The method even reverses the classical kinetic paradigm – reaction scheme directly follows from the rate equation. Data fitting by this method also indicates connections to distinctions between processes at the molecular level and their representation by some macroscopic reaction network. The role of dependent and independent reactions in reaction kinetics and reaction schemes is clarified. A selected example demonstrates that this thermodynamic methodology may improve our design and understanding of thermodynamically and mathematically necessary and sufficient reaction schemes. The phenomenological theory thus sheds new, “thermodynamic” light on what has been and is done by generations of kineticists and gives new hints how to do it in a way consistent with non-equilibrium thermodynamics.

Keywords: Kinetics; Reaction mechanisms; Rate equations; Reaction networks; Thermodynamics.

References: 46 live references.