Thermodynamics in the limit of irreversible reactions


Тип публикации: статья из журнала

Год издания: 2013

Идентификатор DOI: 10.1016/j.physa.2012.10.009

Ключевые слова: Entropy, Free energy, Reaction network, Detailed balance, Irreversibility, Algebraic description, Classical thermodynamics, Convex hull, Enzyme reaction, Equilibrium concentration, Heterogeneous catalytic oxidation, Homogeneous combustion, Hydrogen combustion, Irreversible reactions, Kinetic equations, Limit behavior, Linear span, Lyapunov functionals, Physicochemical system, Reaction system, Relative rates, Reversible reaction, Reversible systems, Thermodynamic theory, Catalytic oxidation, Combustion, Hydrogen, Integral equations, Thermodynamics, Reaction rates

Аннотация: For many complex real physicochemical systems, the detailed mechanism includes both reversible and irreversible reactions. Such systems are typical in homogeneous combustion and heterogeneous catalytic oxidation. Most complex enzyme reactions include irreversible steps. Classical thermodynamics has no limit for irreversible reactioПоказать полностьюns, whereas kinetic equations may have such a limit. We represent systems with irreversible reactions as the limits of fully reversible systems when some of the equilibrium concentrations tend to zero. The structure of the limit reaction system crucially depends on the relative rates of this tendency to zero. We study the dynamics of the limit system and describe its limit behavior as t -> infinity. If the reversible systems obey the principle of detailed balance then the limit system with some irreversible reactions must satisfy the extended principle of detailed balance. It is formulated and proven in the form of two conditions: (i) the reversible part satisfies the principle of detailed balance and (ii) the convex hull of the stoichiometric vectors of the irreversible reactions does not intersect the linear span of the stoichiometric vectors of the reversible reactions. These conditions imply the existence of the global Lyapunov functionals and allow an algebraic description of the limit behavior. Thermodynamic theory of the irreversible limit of reversible reactions is illustrated by the analysis of hydrogen combustion. (c) 2012 Elsevier B.V. All rights reserved.

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Выпуск журнала: Vol. 392, Is. 6

Номера страниц: 1318-1335

ISSN журнала: 03784371

Место издания: AMSTERDAM



  • Gorban A.N. (Univ Leicester, Dept Math, Leicester LE1 7RH, Leics, England)
  • Mirkes E.M. (Siberian Fed Univ, Inst Space & Informat Technol, Krasnoyarsk, Russia)
  • Yablonsky G.S. (St Louis Univ, Dept Chem, Parks Coll, St Louis, MO 63103 USA)

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