Thermodynamic Analysis of Chemically Reacting Mixtures-Comparison of First and Second Order Models

被引:4
作者
Pekar, Miloslav [1 ,2 ]
机构
[1] Brno Univ Technol, Inst Phys & Appl Chem, Fac Chem, Brno, Czech Republic
[2] Brno Univ Technol, Mat Res Ctr, Fac Chem, Brno, Czech Republic
来源
FRONTIERS IN CHEMISTRY | 2018年 / 6卷
关键词
affinity; entropic inequality; independent reactions; kinetics; rate constants; rate equations; thermodynamics; KINETICS; SYSTEMS;
D O I
10.3389/fchem.2018.00035
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Recently, a method based on non-equilibrium continuum thermodynamics which derives thermodynamically consistent reaction rate models together with thermodynamic constraints on their parameters was analyzed using a triangular reaction scheme. The scheme was kinetically of the first order. Here, the analysis is further developed for several first and second order schemes to gain a deeper insight into the thermodynamic consistency of rate equations and relationships between chemical thermodynamic and kinetics. It is shown that the thermodynamic constraints on the so-called proper rate coefficient are usually simple sign restrictions consistent with the supposed reaction directions. Constraints on the so-called coupling rate coefficients are more complex and weaker. This means more freedom in kinetic coupling between reaction steps in a scheme, i.e., in the kinetic effects of other reactions on the rate of some reaction in a reacting system. When compared with traditional mass-action rate equations, the method allows a reduction in the number of traditional rate constants to be evaluated from data, i.e., a reduction in the dimensionality of the parameter estimation problem. This is due to identifying relationships between mass-action rate constants (relationships which also include thermodynamic equilibrium constants) which have so far been unknown.
引用
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页数:7
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共 22 条
[1]   One-dimensional slow invariant manifolds for spatially homogenous reactive systems [J].
Al-Khateeb, Ashraf N. ;
Powers, Joseph M. ;
Paolucci, Samuel ;
Sommese, Andrew J. ;
Diller, Jeffrey A. ;
Hauenstein, Jonathan D. ;
Mengers, Joshua D. .
JOURNAL OF CHEMICAL PHYSICS, 2009, 131 (02)
[2]   A Thermodynamic Approach to Kinetics of Reactions [J].
Arato, Elisabetta ;
Morro, Angelo .
ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE-INTERNATIONAL JOURNAL OF RESEARCH IN PHYSICAL CHEMISTRY & CHEMICAL PHYSICS, 2014, 228 (08) :793-815
[3]   Mesoscopic non-equilibrium thermodynamics of non-isothermal reaction-diffusion [J].
Bedeaux, D. ;
Pagonabarraga, I. ;
Ortiz de Zarate, J. M. ;
Sengers, J. V. ;
Kjelstrup, S. .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2010, 12 (39) :12780-12793
[4]   Continuum thermodynamics of chemically reacting fluid mixtures [J].
Bothe, Dieter ;
Dreyer, Wolfgang .
ACTA MECHANICA, 2015, 226 (06) :1757-1805
[5]   ON STOICHIOMETRY OF CHEMICALLY REACTING MATERIALS [J].
BOWEN, RM .
ARCHIVE FOR RATIONAL MECHANICS AND ANALYSIS, 1968, 29 (02) :114-&
[6]   MACROSCOPIC AND MICROSCOPIC RESTRICTIONS ON CHEMICAL-KINETICS [J].
BOYD, RK .
CHEMICAL REVIEWS, 1977, 77 (01) :93-119
[7]   Thermodynamic Constraints in Kinetic Modeling: Thermodynamic-Kinetic Modeling in Comparison to Other Approaches [J].
Ederer, M. ;
Gilles, E. D. .
ENGINEERING IN LIFE SCIENCES, 2008, 8 (05) :467-476
[8]   Integrated stoichiometric, thermodynamic and kinetic modelling of steady state metabolism [J].
Fleming, R. M. T. ;
Thiele, I. ;
Provan, G. ;
Nasheuer, H. P. .
JOURNAL OF THEORETICAL BIOLOGY, 2010, 264 (03) :683-692
[9]   Nonequilibrium thermodynamic formalism of nonlinear chemical reaction systems with Waage-Guldberg's law of mass action [J].
Ge, Hao ;
Qian, Hong .
CHEMICAL PHYSICS, 2016, 472 :241-248
[10]   Non-equilibrium thermodynamics analysis of transcriptional regulation kinetics [J].
Hernandez-Lemus, Enrique ;
Tovar, Hugo ;
Mejia, Carmen .
JOURNAL OF NON-EQUILIBRIUM THERMODYNAMICS, 2014, 39 (04) :205-218