LAPSE:2023.36860
Published Article
LAPSE:2023.36860
Molecular Modeling of Supercritical Processes and the Lattice—Gas Model
Yuri Konstantinovich Tovbin
November 30, 2023
The existing possibilities for modeling the kinetics of supercritical processes at the molecular level are considered from the point of view that the Second Law of thermodynamics must be fulfilled. The only approach that ensures the fulfillment of the Second Law of thermodynamics is the molecular theory based on the discrete−continuous lattice gas model. Expressions for the rates of the elementary stage on its basis give a self-consistent description of the equilibrium states of the mixtures under consideration. The common usage today of ideal kinetic models in SC processes in modeling industrial chemistry contradicts the non-ideal equation of states. The used molecular theory is the theory of absolute reaction rates for non-ideal reaction systems, which takes into account intermolecular interactions that change the effective activation energies of elementary stages. This allows the theory to describe the rates of elementary stages of chemical transformations and molecular transport at arbitrary temperatures and reagent densities in different phases. The application of this theory in a wide range of state parameters (pressure and temperature) is considered when calculating the rates of elementary bimolecular reactions and dissipative coefficients under supercritical conditions. Generalized dependencies are calculated within the framework of the law of the corresponding states for the coefficients of compressibility, shear viscosity, and thermal conductivity of pure substances, and for the coefficients of compressibility, self- and mutual diffusion, and shear viscosity of binary mixtures. The effect of density and temperature on the rates of elementary stages under supercritical conditions has been demonstrated for a reaction’s effective energies of activation, diffusion and share viscosity coefficients, and equilibrium constants of adsorption. Differences between models with effective parameters and the prospects for developing them by allowing for differences in size and contributions from the vibrational motions of components are described.
Keywords
lattice gas model, non-ideal reaction systems, supercritical conditions, theory of the absolute rate of a reaction
Suggested Citation
Tovbin YK. Molecular Modeling of Supercritical Processes and the Lattice—Gas Model. (2023). LAPSE:2023.36860
Author Affiliations
Tovbin YK: Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow 119991, Russia
Journal Name
Processes
Volume
11
Issue
9
First Page
2541
Year
2023
Publication Date
2023-08-24
Published Version
ISSN
2227-9717
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Original Submission
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PII: pr11092541, Publication Type: Journal Article
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LAPSE:2023.36860
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doi:10.3390/pr11092541
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Nov 30, 2023
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Nov 30, 2023
 
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Calvin Tsay
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