Phenomenological derivation of the mass action law of homogeneous chemical kinetics

Samohýl, Ivan; Malijevský, Alexandr

doi:10.1135/cccc19762131

Cited by 12 publications

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“…Samohýl and Malijevský [32] proved, using phenomenological non-equilibrium (rational) thermodynamics, that in a reacting mixture of linear fluids, reaction rates are functions of temperature and concentration only, r = f(T, c 1 , c 2 ,…, c n ). This is a general statement of what the mass-action law says specifically.…”

Section: Introductionmentioning

confidence: 99%

Macroscopic derivation of the kinetic mass-action law

Pekař

2009

Reac Kinet Mech Cat

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Using several reaction examples with experimentally determined rate equations, traditional mass-action rate equations are shown to be simplified forms of polynomial approximation to a general rate function derived by non-equilibrium thermodynamics for a mixture of fluids with linear transport properties. The mass-action kinetic law is thus proved also on the macroscopic level and limited to this type of fluids.

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Section: Introductionmentioning

confidence: 99%

Macroscopic derivation of the kinetic mass-action law

Pekař

2009

Reac Kinet Mech Cat

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“…There is no indication for other cases while the function   also out of it and the final simplified approximating polynomial, called thermodynamic polynomial, follows and represents rate equation of mass action type. More details on this method can be found elsewhere (Samohýl & Malijevský, 1976;Pekař, 2009Pekař, , 2010. Here it is illustrated on two examples relevant for this article.…”

Section:   mentioning

confidence: 99%

“…But it clearly states assumptions and models, i. e. scope of its potential application. The first assumption, besides standard balances and entropic inequality (see, e.g., Samohýl, 1982Samohýl, , 1987, or model is the mixture of linear fluids in which the functional form of reaction rates was proved: Samohýl & Malijevský, 1976;Samohýl, 1982Samohýl, , 1987. Only independent reaction rates are sufficient that can be easily obtained from component rates, cf.…”

Section: Solution Offered By Rational Thermodynamicsmentioning

confidence: 99%

“…Let us now trace one relatively simple non-equilibrium approach to description of chemically reacting systems and its results regarding the chemical potential. Samohýl has developed rational thermodynamic approach for chemically reacting fluids with linear transport properties (henceforth called briefly linear fluids) and these fluids seem to include many (non-electrolyte) systems encountered in chemistry (Samohýl & Malijevský, 1976;Samohýl, 1982Samohýl, , 1987. This is a continuum mechanics based approach working with densities of quantities and specific quantities (considered locally, in other words, as fields but this is not crucial for the present text) therefore it primarily uses densities of components (more precisely, the density of component mass) instead of their molar concentrations or fractions that are common in chemistry.…”

Section:   mentioning

confidence: 99%

“…, is approximated by a polynomial of suitable degree (Samohýl & Malijevský, 1976;Samohýl, 1982Samohýl, , 1987. Equilibrium constant is defined for each independent reaction as follows:…”

Section: Solution Offered By Rational Thermodynamicsmentioning

confidence: 99%

See 2 more Smart Citations

Thermodynamics and Reaction Rates

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Thermodynamic Analysis of Chemically Reacting Mixtures and Their Kinetics: Example of a Mixture of Three Isomers

Pekař

2016

ChemPhysChem

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Thermodynamics provides consequences of and restrictions on chemically reacting mixtures, particularly their kinetics, which have not been fully explored. Herein, a comprehensive thermodynamic analysis is illustrated for a reacting mixture of three isomers. The rate equation is first derived on the basis of the results of nonequilibrium 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 only for independent reactions, 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.

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Phenomenological derivation of the mass action law of homogeneous chemical kinetics

Cited by 12 publications

References 0 publications

Macroscopic derivation of the kinetic mass-action law

Macroscopic derivation of the kinetic mass-action law

Thermodynamics and Reaction Rates

Thermodynamic Analysis of Chemically Reacting Mixtures and Their Kinetics: Example of a Mixture of Three Isomers

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