Second Law of Thermodynamics, Gibbs’ Thermodynamics, and Relaxation Times of Thermodynamic Parameters

Tovbin, Yu. K.

doi:10.1134/s0036024421020266

Cited by 8 publications

(3 citation statements)

References 36 publications

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“…Clausius' formulation of the second law of thermodynamics contained a way to consider the transfer of nonmechanical energy in the first law of thermodynamics. This formulation is rather complex to understand because it simultaneously contains both the process of development toward equilibrium in a closed system and the limiting equilibrium state [25,111,112]. The mathematical formulation of the combined equation of thermodynamics is dU ≤ TdS − PdV, where U is the internal energy, P is pressure, and V is the volume of the system; the sign of the equality corresponds to the equilibrium.…”

Section: The Second Law Of Thermodynamics and Connection Between Mode...mentioning

confidence: 99%

“…Dividing the second law of thermodynamics into two parts [112][113][114], Gibbs omitted the requirements, contained in bases of thermodynamics, about a self-consistence description of reaction rates and an equilibrium condition [115]. The existing law of mass action [21,34] was highlighted, although it is not valid in non-ideal systems that comprise the majority of real processes.…”

Section: The Second Law Of Thermodynamics and Connection Between Mode...mentioning

confidence: 99%

“…To calculate the change in entropy during the transition processes between different initial and final states, it is necessary to know the state of the system at two points (the equal sign refers to reversible processes). The transition between initial and final states is described by kinetic equations, which determine their key importance in modeling any technological processes [112].…”

Section: Kinetic Equationsmentioning

confidence: 99%

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Molecular Modeling of Supercritical Processes and the Lattice—Gas Model

Tovbin

2023

Processes

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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.

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Section: The Second Law Of Thermodynamics and Connection Between Mode...mentioning

confidence: 99%