Abstract
Fast changes in the kinetic characteristics occur at the beginning of the transition processes of nonlinear chemical reactions, which are often not observed during nonstationary experiments. These periods of fast relaxations may carry important information about the mechanisms of complex reactions. The evolution of the period of fast relaxations of typical chemical reactions as they move away from equilibrium is studied in this paper. A three-level classification of the forms of nonequilibrium kinetic dependences with respect to the level of informativity is introduced. Nonmonotonic curves with bends (ravines, hills) have the maximum informativity, monotonic curves with bends (waves) have the average informativity, and monotonic curves without bends (descents, ascents) have the minimum informativity. The criterion of existence of the period of fast relaxations, during which the informative forms of the kinetic curves (ravines, hills, waves) exist, is formulated. It is shown that the states of false equilibrium can be observed during their study in which kinetic curves seem to be constant far from the equilibrium. The obtained results may be useful in the reconstruction of the mechanisms of chemical reactions.
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REFERENCES
A. A. Andronov, A. A. Vitt, and S. E. Khaikin, Theory of Oscillations (Nauka, Moscow, 1981) [in Russian].
V. V. Vol’ter and I. E. Sal’nikov, Stability of Operations of Chemical Reactors (Khimiya, Moscow, 1981) [in Russian].
G. Nicolis and I. Prigogine, Self-Organization in Non-Equilibrium Systems (Wiley, New York, 1977).
S. L. Kiperman, Fundamentals of Chemical Kinetics in Heterogeneous Catalysis (Khimiya, Moscow, 1979) [in Russian].
G. S. Yablonskii, V. I. Bykov, and V. I. Elokhin, The Kinetics of Model Reactions of Heterogeneous Catalysis (Nauka, Novosibirsk, 1984) [in Russian].
A. N. Gorban’, Bypassing Equilibrium (Equations of Chemical Kinetics and their Thermodynamical Analysis) (Nauka, Novosibirsk, 1984) [in Russian].
V. I. Bykov and S. B. Tsybenova, Nonlinear Models of Chemical Kinetics (KRASAND, Moscow, 2011) [in Russian].
V. I. Bykov, Simulation of Critical Phenomena in Chemical Kinetics (URSS, Moscow, 2014) [in Russian].
V. I. Bykov, S. B. Tsybenova, and G. S. Yablonsky, Chemical Complexity via Simple Models (De Gruyter, Berlin, New York, 2018).
Ya. B. Zel’dovich, Selected Works, Chemical Physics and Hydrodynamics (Nauka, Moscow, 1984), p. 43 [in Russian].
N. I. Kol’tsov, B. V. Alekseev, and V. Kh. Fedotov, Dokl. Akad. Nauk SSSR 317, 147 (1991).
N. I. Kol’tsov, V. Kh. Fedotov, and B. V. Alekseev, Dokl. Akad. Nauk SSSR 318, 1179 (1991).
N. I. Kol’tsov, V. Kh. Fedotov, and B. V. Alekseev, Direct and Inverse Problems in Chemical Kinetics (Nauka, Novosibirsk, 1993), p. 175 [in Russian].
N. I. Kol’tsov, B. V. Alekseev, I. V. Kozhevnikov, and V. Kh. Fedotov, Russ. J. Phys. Chem. A 71, 671 (1997).
V. Kh. Fedotov, N. I. Kol’tsov, and B. V. Alekseev, Zh. Fiz. Khim. 61, 1399 (1987).
D. Constales, G. S. Yablonsky, and G. B. Marin, Comput. Math. Appl. 65, 1614 (2013).
G. S. Yablonsky, Theor. Found. Chem. Eng. 48, 608 (2014).
D. Branco-Pinto, G. Yablonsky, G. Marin, and D. Constales, Entropy 17, 6783 (2015).
A. N. Gorban’, V. I. Bykov, and G. S. Yablonskii, Essays on Chemical Relaxation (Nauka, Novosibirsk, 1986) [in Russian].
B. V. Alekseev, V. Kh. Fedotov, N. I. Kol’tsov, and S. L. Kiperman, Khim. Fiz. 1, 776 (1982).
V. Kh. Fedotov, N. I. Kol’tsov, and S. L. Kiperman, Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol. 28 (12), 38 (1985).
N. I. Kol’tsov, V. Kh. Fedotov, B. V. Alekseev, and S. L. Kiperman, Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol. 30 (5), 57 (1987).
N. I. Kol’tsov and V. Kh. Fedotov, Surf. Sci. 206, 518 (1988).
N. I. Kol’tsov, V. Kh. Fedotov, and B. V. Alekseev, Mathematical Methods in Chemical Kinetics (Nauka, Novosibirsk, 1990) [in Russian].
V. Kh. Fedotov and N. I. Kol’tsov, Russ. J. Phys. Chem. B 8, 309 (2014).
N. I. Kol’tsov and B. V. Alekseev, Soobshch. Kinet. Katal. 24, 309 (1984).
V. Kh. Fedotov and N. I. Kol’tsov, Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol. 57 (2), 63 (2014).
V. L. Bodneva, G. K. Ivanov, and B. R. Shub, Khim. Fiz. 23 (6), 24 (2004).
V. F. Kharlamov and F. V. Kharlamov, Russ. J. Phys. Chem. B 2, 53 (2008).
A. S. Moskalenko and S. Ya. Umanskii, Russ. J. Phys. Chem. B 6, 140 (2012).
D. A. Meshkov, V. A. Ivanov, S. K. Nechaev, and V. A. Avetisov, Russ. J. Phys. Chem. B 8, 518 (2014).
G. M. Grigoryan and T. L. Tkachenko, Russ. J. Phys. Chem. B 11, 20 (2017).
G. Korn and T. Korn, Mathematical Handbook for Scientists and Engineers (Nauka, Moscow, 1978; McGraw-Hill, New York, 1961).
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The author thanks V.Kh. Fedotov for the useful discussions of the results of this study.
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Translated by E. Boltukhina
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Kol’tsov, N.I. Kinetic Characteristic Features of the Fast Relaxations of Chemical Reactions. Russ. J. Phys. Chem. B 14, 765–772 (2020). https://doi.org/10.1134/S1990793120050061
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DOI: https://doi.org/10.1134/S1990793120050061