Chemical reaction concentration oscillations

Only a very few experimental studies have been made for detection of mnlti-plicities of steady states to check on theoretical predictions. The studies of multiplicities and of oscillations of concentrations have similar mathematical bases. Comprehensive reviews of these topics are by Schmitz (Adv. Chem. Sen, 148, 156, ACS [1975]), Razon and Schmitz (Chem. Eng. Sci., 42, 1,005-1,047 [1987]), Morbidelli, Vamia, and Aris (in Carberry and Varma, eds.. Chemical Reaction and Reacton Engineering, Dekker, 1987, pp. 975-1,054). 

Belouzov-Zhabotinsky reaction [12, 13] This chemical reaction is a classical example of non-equilibrium thermodynamics, forming a nonlinear chemical oscillator [14]. Redox-active metal ions with more than one stable oxidation state (e.g., cerium, ruthenium) are reduced by an organic acid (e.g., malonic acid) and re-oxidized by bromate forming temporal or spatial patterns of metal ion concentration in either oxidation state. This is a self-organized structure, because the reaction is not dominated by equilibrium thermodynamic behavior. The reaction is far from equilibrium and remains so for a significant length of time. Finally,... 

A chemical reaction can be designated as oscillatory, if repeated maxima and minima in the concentration of the intermediates can occur with respect to time (temporal oscillation) or space (spatial oscillation). A chemical system at constant temperature and pressure will approach equilibrium monotonically without overshooting and coming back. In such a chemical system the concentrations of intermediate must either pass through a single maximum or minimum rapidly to reach some steady state value during the course of reaction and oscillations about a final equilibrium state will not be observed. However, if mechanism is sufficiently complex and system is far from equilibrium, repeated maxima and minima in concentrations of intermediate can occur and chemical oscillations may become possible. 

In the phase space formed by the concentrations of the chemical variables involved in the reaction, sustained oscillations correspond to the evolution towards a closed curve called a limit cycle [17]. The time taken to travel once along the closed curve represents the period of the oscillations. When a single... 

Chemical reactions with autocatalytic or thermal feedback can combine with the diffusive transport of molecules to create a striking set of spatial or temporal patterns. A reactor with permeable wall across which fresh reactants can diffuse in and products diffuse out is an open system and so can support multiple stationary states and sustained oscillations. The diffusion processes mean that the stationary-state concentrations will vary with position in the reactor, giving a profile , which may show distinct banding (Fig. 1.16). Similar patterns are also predicted in some circumstances in closed vessels if stirring ceases. Then the spatial dependence can develop spontaneously from an initially uniform state, but uniformity must always return eventually as the system approaches equilibrium. 

Despite the fact that from a principal point of view a problem of concentration oscillations could be considered as solved [4], satisfactory theoretical descriptions of experimentally well-studied particular reactions are practically absent. Due to very complicated reaction mechanism (in order to describe the Belousov-Zhabotinsky reaction even in terms of standard chemical kinetics several tens of concentration equations for intermediate products should be written down and solved numerically [4, 9, 10]) these equations contain large number of ill-defined parameters - reaction rates [10]. 

As it was mentioned in Section 2.1.1, the concentration oscillations could be simulated quite well by a set of even two ordinary differential equations of the first order but paying the price of giving up the rigid condition imposed on interpretation of mechanisms of chemical reactions namely that they are based on mono- and bimolecular stages only (remember the Hanusse theorem [19]) An example of what Smoes [7] called the heuristic-topological model is the well-known Brusselator [2], Its scheme was discussed in Section 2.1.1 see equations (2.1.33) to (2.1.35). 

In an open system such as a CSTR chemical reactions can undergo self-sustained oscillations even though all external conditions such as feed rate and concentrations are held constant. The Belousov-Zhabotinskii reaction can undergo such oscillations under isothermal conditions. As has been demonstrated both by experiments [1] and by calculations 12,3] this reaction can produce a variety of oscillation types from simple relaxation oscillations to complicated multipeaked periodic oscillations. Evidence has also been given that chaotic behavior, as opposed to periodic or quasi-periodic behavior, can take place with this reaction [4-12]. In addition, it has been shown in recent theoretical studies that chaos can occur in open chemical reactors [11,13-17]. 

Some autocatalytic chemical reactions such as the Brusselator and the Belousov-Zhabotinsky reaction schemes can produce temporal oscillations in a stirred homogeneous solution. In the presence of even a small initial concentration inhomogeneity, autocatalytic processes can couple with diffusion to produce organized systems in time and space. 

For a chemical reaction system, the characteristics of the periodic solutions are uniquely determined by the kinetic constants as well as by the concentrations of the reactants and final products. Starting from the neighborhood of steady state as an initial condition, the system asymptotically attains a closed orbit or limit cycle. Therefore, for long times, the concentrations sustain periodic undamped oscillations. The characteristics of these oscillations are independent of the initial conditions, and the system always approaches the same asymptotic trajectory. Generally, the further a system is in the unstable region, the faster it approaches the limit cycle. 

Autocatalysis is a distinctive phenomenon while in ordinary catalysis the catalyst re-appears from the reaction apparently untouched, additional amounts of catalyst are actively produced in an autocatalytic cycle. As atoms are not interconverted during chemical reactions, this requires (all) the (elementary or otherwise essential) components of autocatalysts to be extracted from some external reservoir. After all this matter was extracted, some share of it is not introduced in and released as a product but rather retained, thereafter supporting and speeding up the reaction(s) steadily as amounts and possibly also concentrations of autocatalysts increase. At first glance, such a system may appear doomed to undergo runaway dynamics ( explosion ), but, apart from the limited speeds and rates of autocatalyst resupply from the environment there are also other mechanisms which usually limit kinetics even though non-linear behavior (bistability, oscillations) may not be precluded ... 

H. Qian, S. Saffarian, E.L. Elson, Concentration fluctuations in a mesoscopic oscillating chemical reaction system. Proc. Natl. Acad. Sci. USA 99(16), 10376-10381 (2002)... 

The majority of chemical reactions exhibit a monotonic time course, but it is not unusual for concentrations of intermediates in a series of coupled reactions, such as the concentration of B in the sequence A —> B —> C, to rise and fall. Less often, but still in quite a number of well-documented cases, concentrations go up and down more than once, and reactions that exhibit this behavior are called oscillatory. Typically, such oscillations will eventually die out once some or all of the starting material has been consumed. However, some reactions can be kept to oscillate indefinitely by keeping their initial concentrations constant, i.e., by replenishing any reagent lost. 

The Belousov-Zhabotinskii (BZ) reaction has been selected as an example illustrating diverse dynamical states observable in chemical systems. The BZ reagent is very convenient both for experimental and theoretical investigations, since the BZ reaction has many dynamical states of interest, which will be described below. In the BZ reaction one may observe the steady state, the time periodic state (concentration oscillations), the spatially periodic state, the stationary state (dissipative structures), the time and spatially periodic state (propagating chemical waves) and turbulent states (chaotic oscillations, stochastic spatial structures, stochastic chemical waves). 

It should be emphasized that there have been exceptions to this attitude. In 1910 and 1920 Lotka published his theory of chemical reactions in which the oscillations of reagent concentrations could appear. An essential feature of the Lotka models was nonlinearity. In mathematics and physics a trend has long persisted to examine linear systems and phenomena and to replace non-linear models by (approximate) linear models. The trend, originating from insufficient mathematical means, has turned into specific philosophy. The non-linear Lotka models thus constituted a deviation from a canon. Hence, general arguments of thermodynamic nature, lack of interest in non-linear models and commonness of observations of a monotonic attainment of the equilibrium in chemical reactions were the reasons for skepticism and disbelief which the results of Belousov have met with. 

Fig. 92. Concentration oscillations in the Belousov-Zhabotinskii reaction. Reprinted with permission from R.J. Field, E. Kotos and R.M. Noyes, Journal of American Chemical Society, 94 (1972), 8649.

The first theoretical model of a chemical reaction providing for oscillations in concentrations of reagents was the Lotka model from 1910. A mechanism of the hypothetical Lotka reaction has the following form ... 

Investigations of the chemical reactions, in which concentration oscillations, formation of non-homogeneous complex structures from homogeneous solution and the occurrence of chaotic dynamics have been observed, seem to be particularly promising. The question concerning the nature of couplings between chemical reactions is considered to be crucial in our anxiety to understand life. 

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