[Electronic resource]. - Electronic data (640 Kb)
. - Режим доступа: http://icm.krasn.ru/refextra.php?id=2109. - Электрон. версия печ. публикации . - Режим доступа: http://www.wkap.nl/prod/b/0-306-47401-8 : научное издание / A.N. Gorban, I.V. Karlin. - Electronic data (640 Kb) // Recent Developments in Mathematical and Experimental Physics, Volume C: Hydrodynamics and Dynamical Systems. - Dordrecht : Kluwer, 2002. - p. 19-43
Перевод заглавия: Геометрия необратимости
Аннотация: A general geometrical setting of nonequilibrium thermodynamics is developed. The approach is based on the notion of the natural projection which generalizes Ehrenfests' coarse-graining. It is demonstrated how derivations of irreversible macroscopic dynamics from the microscopic theories can be addressed through a study of stability of quasiequilibrium manifolds.
http://icm.krasn.ru/refextra.php?id=2109,
http://www.wkap.nl/prod/b/0-306-47401-8
Доп.точки доступа:
Karlin, I.V.; Карлин, Илья Вениаминович; Горбань, Александр Николаевич
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Найдено документов в текущей БД: 2
The Michaelis-Menten-Stueckelberg Theorem
[Text] : статья / A. N. Gorban, M. Shahzad // Entropy. - 2011. - Vol. 13, Iss. 5. - p. 966-1019DOI 10.3390/e13050966
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Кл.слова (ненормированные):
chemical kinetics -- Lyapunov function -- entropy -- quasiequilibrium -- detailed balance -- complex balance
Аннотация: We study chemical reactions with complex mechanisms under two assumptions: (i) intermediates are present in small amounts (this is the quasi-steady-state hypothesis or QSS) and (ii) they are in equilibrium relations with substrates (this is the quasiequilibrium hypothesis or QE). Under these assumptions, we prove the generalized mass action law together with the basic relations between kinetic factors, which are sufficient for the positivity of the entropy production but hold even without microreversibility, when the detailed balance is not applicable. Even though QE and QSS produce useful approximations by themselves, only the combination of these assumptions can render the possibility beyond the “rarefied gas” limit or the “molecular chaos” hypotheses. We do not use any a priori form of the kinetic law for the chemical reactions and describe their equilibria by thermodynamic relations. The transformations of the intermediate compounds can be described by the Markov kinetics because of their low density (low density of elementary events). This combination of assumptions was introduced by Michaelis and Menten in 1913. In 1952, Stueckelberg used the same assumptions for the gas kinetics and produced the remarkable semi-detailed balance relations between collision rates in the Boltzmann equation that are weaker than the detailed balance conditions but are still sufficient for the Boltzmann H-theorem to be valid. Our results are obtained within the Michaelis-Menten-Stueckelbeg conceptual framework.
Полный текст на сайте правообладателя
Доп.точки доступа:
Shahzad, Muhammad; Горбань, Александр Николаевич
Кл.слова (ненормированные):
chemical kinetics -- Lyapunov function -- entropy -- quasiequilibrium -- detailed balance -- complex balance
Аннотация: We study chemical reactions with complex mechanisms under two assumptions: (i) intermediates are present in small amounts (this is the quasi-steady-state hypothesis or QSS) and (ii) they are in equilibrium relations with substrates (this is the quasiequilibrium hypothesis or QE). Under these assumptions, we prove the generalized mass action law together with the basic relations between kinetic factors, which are sufficient for the positivity of the entropy production but hold even without microreversibility, when the detailed balance is not applicable. Even though QE and QSS produce useful approximations by themselves, only the combination of these assumptions can render the possibility beyond the “rarefied gas” limit or the “molecular chaos” hypotheses. We do not use any a priori form of the kinetic law for the chemical reactions and describe their equilibria by thermodynamic relations. The transformations of the intermediate compounds can be described by the Markov kinetics because of their low density (low density of elementary events). This combination of assumptions was introduced by Michaelis and Menten in 1913. In 1952, Stueckelberg used the same assumptions for the gas kinetics and produced the remarkable semi-detailed balance relations between collision rates in the Boltzmann equation that are weaker than the detailed balance conditions but are still sufficient for the Boltzmann H-theorem to be valid. Our results are obtained within the Michaelis-Menten-Stueckelbeg conceptual framework.
Полный текст на сайте правообладателя
Доп.точки доступа:
Shahzad, Muhammad; Горбань, Александр Николаевич