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Chemical oscillators developing mechanism

These models consider the mechanisms of formation of oscillations a mechanism involving the phase transition of planes Pt(100) (hex) (lxl) and a mechanism with the formation of surface oxides Pd(l 10). The models demonstrate the oscillations of the rate of C02 formation and the concentrations of adsorbed reactants. These oscillations are accompanied by various wave processes on the lattice that models single crystalline surfaces. The effects of the size of the model lattice and the intensity of COads diffusion on the synchronization and the form of oscillations and surface waves are studied. It was shown that it is possible to obtain a wide spectrum of chemical waves (cellular and turbulent structures and spiral and ellipsoid waves) using the lattice models developed [283], Also, the influence of the internal parameters on the shapes of surface concentration waves obtained in simulations under the limited surface diffusion intensity conditions has been studied [284], The hysteresis in oscillatory behavior has been found under step-by-step variation of oxygen partial pressure. Two different oscillatory regimes could exist at one and the same parameters of the reaction. The parameters of oscillations (amplitude, period, and the... [Pg.434]

There is an important connection. Life developed under non-equilibrium conditions. Consider first an example. Far from equilibrium, you have chemical oscillations in which millions of millions of molecules change their color simultaneously. This type of coherence is possible only if there are long-range correlations. They occur only far from equilibrium. Similarly, biomolecules, with their complex structures, would be impossible to build in equilibrium conditions. They would have a negligible probability. This is no more so in far-from-equilibrium conditions. However, the detailed mechanism by which biomolecules appeared is still a controversial problem. But surely, biomolecules are non-equilibrium structures maintained from one generation to the next by self-replication. [Pg.425]

Exit from Mil arrest of the ovulated oocyte is accomplished by fertilization with sperm, and is commonly referred to as oocyte activation . This activation is triggered by intracellular calcium oscillations induced by fertilization [17]. Due to an absence of fertihzation by sperm in SCNT embryos, reconstructed oocytes must be stimulated artificially to fuse between donor cells and oocytes, and to initiate embryo development. A variety of chemical, physical and mechanical agents have been shown to induce the activation of reconstructed oocytes, with different efficiencies. [Pg.281]

The study of nonlinear chemical dynamics begins with chemical oscillators - systems in which the concentrations of one or more species increase and decrease periodically, or nearly periodically. While descriptions of chemical oscillators can be found at least as far back as the nineteenth century (and chemical oscillation is, of course, ubiquitous in living systems), systematic study of chemical periodicity begins with two accidentally discovered systems associated with the names of Bray (2) and of Belousov and Zhabotinsky (BZ) 3,4), These initial discoveries were met with skepticism by chemists who believed that such behavior would violate the Second Law of Thermodynamics, but the development of a general theory of nonequilibrium thermodynamics (5) and of a detailed mechanism 6) for the BZ reaction brought credibility to the field by the mid-1970 s. Oscillations in the prototypical BZ reaction are shown in Figure 1. [Pg.6]

Recently there has been an increasing interest in self-oscillatory phenomena and also in formation of spatio-temporal structure, accompanied by the rapid development of theory concerning dynamics of such systems under nonlinear, nonequilibrium conditions. The discovery of model chemical reactions to produce self-oscillations and spatio-temporal structures has accelerated the studies on nonlinear dynamics in chemistry. The Belousov-Zhabotinskii(B-Z) reaction is the most famous among such types of oscillatory chemical reactions, and has been studied most frequently during the past couple of decades [1,2]. The B-Z reaction has attracted much interest from scientists with various discipline, because in this reaction, the rhythmic change between oxidation and reduction states can be easily observed in a test tube. As the reproducibility of the amplitude, period and some other experimental measures is rather high under a found condition, the mechanism of the B-Z reaction has been almost fully understood until now. The most important step in the induction of oscillations is the existence of auto-catalytic process in the reaction network. [Pg.222]

The chapter starts with a brief review of thermodynamic principles as they apply to the concept of the chemical equilibrium. That section is followed by a short review of the use of statistical thermodynamics for the numerical calculation of thermodynamic equilibrium constants in terms of the chemical potential (often designated as (i). Lastly, this statistical mechanical development is applied to the calculation of isotope effects on equilibrium constants, and then extended to treat kinetic isotope effects using the transition state model. These applications will concentrate on equilibrium constants in the ideal gas phase with the molecules considered in the rigid rotor, harmonic oscillator approximation. [Pg.77]

This chapter is devoted to numerical integration, and more specifically to the integration of rate expressions encountered in chemical kinetics. For simple cases, integration yields closed-form rate equations, while more complex reaction mechanisms can often be solved only by numerical means. Here we first use some simple reactions to develop and calibrate general numerical integration schemes that are readily applicable to a spreadsheet. We then illustrate several non-trivial applications, including catalytic reactions and the Lotka oscillator. [Pg.374]

Despite the importance of the chlorite-iodide systems in the development of nonlinear chemical dynamics in the 1980s, the Belousov-Zhabotinsky(BZ) reaction remains as the most intensively studied nonlinear chemical system, and one displaying a surprising variety of behavior. Oscillations here were discovered by Belousov (1951) but largely unnoticed until the works of Zhabotinsky (1964). Extensive description of the reaction and its behavior can be found in Tyson (1985), Murray (1993), Scott (1991), or Epstein and Pojman (1998). There are several versions of the reaction, but the most common involves the oxidation of malonic acid by bromate ions BrOj in acid medium and catalyzed by cerium, which during the reaction oscillates between the Ce3+ and the Ce4+ state. Another possibility is to use as catalyst iron (Fe2+ and Fe3+). The essentials of the mechanisms were elucidated by Field et al. (1972), and lead to the three-species model known as the Oregonator (Field and Noyes, 1974). In this... [Pg.101]


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