By L. A. Tavadyan, G. A. Martoyan
English model of: Analiz kineticheskikh modelei khimicheskikh reak'tsionnykh sistem.
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Extra info for Analysis of Kinetic Models of Chemical Reaction Systems: Value Approach
Chem. A, 115 (2011) 1556. Banks, J. Handbook of simulation: principles, methodology, advances, applications and practice. Willey Interscience, New York. 1998. Saltelli, A; Chan, K; Scott, EM. , New York, 2000. Shmidt, R; Sapunov, VN. Non-formal kinetics, Verlag Chemie, Weinheim-Dearfield Beach-Florida-Basel, 1982. Stiller, W. G. Teubner Verlagsgesellschaft, Leipzig, 1989. Helfferich, FG. 38, Comprehensive chemical kinetics, ed. G. Compton, G. Hancock. Elsevier, Amsterdam, 2001. Srivastava, R; Anderson, DF; Rawlings, JB.
The described methods are based mainly on the construction of reaction schemes with different combinations of atomic and electronic rearrangements in the elementary steps. Then a screening of steps is carried out against definite criteria, namely: restricting the molecularity of steps, the number of atoms simultaneously changing the valency, the number of atoms in a molecule with unpaired electrons, the reaction endothermy and so on. In addition, such a “deductive” procedure despite its evident usefulness is not able to bring to a base (minimum) reaction mechanism, to describe the experimental data with acceptable accuracy.
In determining the base mechanism by the value analysis the following specific features may be highlighted: 42 L. A. Tavadyan and G. A. Martoyan As mentioned above, the value contributions of species bi, and steps hj, on the basis of which the unimportant steps are identified, in our opinion, are more meaningful and comprehensive for the description of kinetic significance of these parameters, from the physicochemical, kinetic standpoint. We remind that the response of a reaction system to variation in the rates of individual steps or the accumulation of reaction species reveals the system relationship between the species and steps simultaneously, through the species concentrations and the rate constants of steps, such that their kinetic significance is determined more completely.