[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
Труды сотрудников ИВМ СО РАН
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Найдено документов в текущей БД: 2
Extended Detailed Balance for Systems with Irreversible Reactions
[Text] : статья / A. N. Gorban, G. S. Yablonskii // Chemical Engineering Science. - 2011. - Vol. 66, Iss. 21. - p. 5388-5399DOI 10.1016/j.ces.2011.07.054
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Кл.слова (ненормированные):
Reaction network -- Detailed balance -- Microreversibility -- Pathway -- Irreversibility -- Kinetics
Аннотация: The principle of detailed balance states that in equilibrium each elementary process is equilibrated by its reverse process. For many real physico-chemical complex systems (e.g. homogeneous combustion, heterogeneous catalytic oxidation, most enzyme reactions, etc.), detailed mechanisms include both reversible and irreversible reactions. In this case, the principle of detailed balance cannot be applied directly. We represent irreversible reactions as limits of reversible steps and obtain the principle of detailed balance for complex mechanisms with some irreversible elementary processes. We prove two consequences of the detailed balance for these mechanisms: the structural condition and the algebraic condition that form together the extended form of detailed balance. The algebraic condition is the principle of detailed balance for the reversible part. The structural condition is the convex hull of the stoichiometric vectors of the irreversible reactions has empty intersection with the linear span of the stoichiometric vectors of the reversible reactions. Physically, this means that the irreversible reactions cannot be included in oriented cyclic pathways. The systems with the extended form of detailed balance are also the limits of the reversible systems with detailed balance when some of the equilibrium concentrations (or activities) tend to zero. Surprisingly, the structure of the limit reaction mechanism crucially depends on the relative speeds of this tendency to zero.
Полный текст на сайте правообладателя
Доп.точки доступа:
Yablonskii, G.S.; Горбань, Александр Николаевич
Кл.слова (ненормированные):
Reaction network -- Detailed balance -- Microreversibility -- Pathway -- Irreversibility -- Kinetics
Аннотация: The principle of detailed balance states that in equilibrium each elementary process is equilibrated by its reverse process. For many real physico-chemical complex systems (e.g. homogeneous combustion, heterogeneous catalytic oxidation, most enzyme reactions, etc.), detailed mechanisms include both reversible and irreversible reactions. In this case, the principle of detailed balance cannot be applied directly. We represent irreversible reactions as limits of reversible steps and obtain the principle of detailed balance for complex mechanisms with some irreversible elementary processes. We prove two consequences of the detailed balance for these mechanisms: the structural condition and the algebraic condition that form together the extended form of detailed balance. The algebraic condition is the principle of detailed balance for the reversible part. The structural condition is the convex hull of the stoichiometric vectors of the irreversible reactions has empty intersection with the linear span of the stoichiometric vectors of the reversible reactions. Physically, this means that the irreversible reactions cannot be included in oriented cyclic pathways. The systems with the extended form of detailed balance are also the limits of the reversible systems with detailed balance when some of the equilibrium concentrations (or activities) tend to zero. Surprisingly, the structure of the limit reaction mechanism crucially depends on the relative speeds of this tendency to zero.
Полный текст на сайте правообладателя
Доп.точки доступа:
Yablonskii, G.S.; Горбань, Александр Николаевич