Temporal Self-organization Externally Controlled By Electro-chemical Constraints In B-Z Reaction System

Some experimental study has shown that chemical reaction systems can exhibit rich dynamical behaviors far from equilibrium because of interaction of each nonlinear process involved, such as chemical oscillations, multiple steady state behavior, chemical waves, chemical chaos and so on. Of which, chemical oscillations are described as periodical behaviors of the system state. As a paradigm of chemical oscillations, the B-Z reaction system has been the focus of the chemist and biochemist since 1960s. Although the theoretical and experimental investigations about this system have made great progress, few scientists has taken the systematic-dynamical analysis of electrode B-Z oscillatory reaction system.This thesis investigates the dynamical behaviors of electrode B-Z reaction system under external electrochemical constraints by means of systematic-dynamical analysis. To begin with, we review the experimental achievements and mechanistic details of B-Z reaction. The FKN mechanism and Oregonator model refined from FKN mechanism have been introduced, and values of rate constant of each reaction step are discussed as well. We also summarized the effects of nonideal properties on thermodynamic and dynamical behaviors of B-Z reaction system. Based on three-variable Oregonator model and activated complex theory of reaction rate, nonideal B-Z reaction model is proposed. Then, the establishment of rate evolutionary equations of nonideal B-Z reaction system has been introduced on the basis of Debye-Huckel activity coefficient theory. Meanwhile, we have made an elaborate retrospect of the advances in nonideal B-Z system, such as the effects of nonideality on oscillatory amplitude, oscillatory period, oscillatory parameter regimes and periodic average values of entropy production in B-Z system.In the second part, we put our emphasis on the self-organized behaviors in electrode B-Z reaction system under external constant electrode potential control. We start with considering the dynamical characters of electrode process of this kind of system from the electrochemical point of view, and the relationship between the electrode potential and the rate constant of the electrode reaction is established based on Butler-Volmer formula. For this special kind of electrochemical oscillating system, dynamical evolutionary mechanism has been proposed according to the simplified three-variable Oregonator model and electrode process dynamics. Furthermore, dynamical evolutionary equations of the research system with high dimensions have been set up. Under certain conditions, the electrode B-Z reaction system of high dimensions involving six variables is reduced to a three-variable dynamical system. Thus, the corresponding theoretical framework of the systematic-dynamical analysis has been made. Through linear stability analysis of 3-variable dynamical system, when the bulk phase is at a steady state, we calculate the electrochemical oscillatory parameter regimes beyond Hopf bifurcation in the electrode reaction phase under a fixed electrode potential. In the corresponding oscillatory regime, the electrochemical oscillations have been simulated numerically. By comparing with the non-oscillatory regime of the bulk phase, it shows that the dynamical behaviors in the bulk phase and in the electrode reaction phase have not been always synchronous.The third part of this thesis deals with temporal self-organization in electrode B-Z reaction system under external constant current constraint. Based on the dynamical model established in the second part, the dynamical evolutionary equation in the form of electrode current density is proposed. Meanwhile, we have calculated the parameter regimes of occurrence of temporal self-organization in this system under fixed current constraints according to linear stability analysis and Hanusse criterion; For the corresponding oscillatory parameter regimes, we have simulated electrochemical oscillations numerically. It turns out that limit cycle oscillations can appear in the electrode reaction s...