Lotka. reaction

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 ... 

Autocatalysis can cause sustained oscillations in batch systems. This idea originally met with skepticism. Some chemists believed that sustained oscillations would violate the second law of thermodynamics, but this is not true. Oscillating batch systems certainly exist, although they must have some external energy source or else the oscillations will eventually subside. An important example of an oscillating system is the circadian rhythm in animals. A simple model of a chemical oscillator, called the Lotka-Volterra reaction, has the assumed mechanism ... 

The Lotka-Volterra reaction described in Section 2.5.4 has three initial conditions—one each for grass, rabbits, and lynx—all of which must be positive. There are three rate constants assuming the supply of grass is not depleted. Use dimensionless variables to reduce the number of independent parameters to four. Pick values for these that lead to a sustained oscillation. Then, vary the parameter governing the grass supply and determine how this affects the period and amplitude of the solution. 

First model for oscillating system was proposed by Volterra for prey-predator interactions in biological systems and by Lotka for autocatalytic chemical reactions. Lotka s model can be represented as... 

The dynamics of controlled systems is an open problem that has recently attracted the attention of scientific community [13]. In fact, oscillatory behavior in chemical systems is an interesting topic (which has been typically studied in autocatalytic reactions, e.g., the Lotka system see [44] and references therein). Dynamics of controlled systems can be explained in terms of interconnections. Indeed, by analogy with control systems, autocatalytic chemical systems can be described as examples of chemical feedback [44]. 

Until the 1950s, the rare periodic phenomena known in chemistry, such as the reaction of Bray [1], represented laboratory curiosities. Some oscillatory reactions were also known in electrochemistry. The link was made between the cardiac rhythm and electrical oscillators [2]. New examples of oscillatory chemical reactions were later discovered [3, 4]. From a theoretical point of view, the first kinetic model for oscillatory reactions was analyzed by Lotka [5], while similar equations were proposed soon after by Volterra [6] to account for oscillations in predator-prey systems in ecology. The next important advance on biological oscillations came from the experimental and theoretical studies of Hodgkin and Huxley [7], which clarified the physicochemical bases of the action potential in electrically excitable cells. The theory that they developed was later applied [8] to account for sustained oscillations of the membrane potential in these cells. Remarkably, the classic study by Hodgkin and Huxley appeared in the same year as Turing s pioneering analysis of spatial patterns in chemical systems [9]. 

Lastly, non-elementary several-stage reactions are considered in Chapters 8 and 9. We start with the Lotka and Lotka-Volterra reactions as simple model systems. An existence of the undamped density oscillations is established here. The complementary reactions treated in Chapter 9 are catalytic surface oxidation of CO and NH3 formation. These reactions also reveal undamped concentration oscillations and kinetic phase transitions. Their adequate treatment need a generalization of the fluctuation-controlled theory for the discrete (lattice) systems in order to take correctly into account the geometry of both lattice and absorbed molecules. As another illustration of the formalism developed by the authors, the kinetics of reactions upon disorded surfaces is considered. 

The Lotka model is based on the following reaction chain... 

Fig. 2.5. An unstable node is obtained as a formal solution of the Lotka equations (2.1.22)—(2.1.23) with time inversion, t —> -t, and parameter pK/f32 = 2. Note that these equations cannot be associated with a set of mono- and bimolecular reactions.

More interesting aspects of stochastic problems are observed when passing to systems with unstable stationary points. Since we restrict ourselves to mono- and bimolecular reactions with a maximum of two intermediate products (freedom degrees), s — 2, only the Lotka-Volterra model by reasons discussed in Section 2.1.1 can serve as the analog of unstable systems. 

Staying within a class of mono- and bimolecular reactions, we thus can apply to them safely the technique of many-point densities developed in Chapter 5. To establish a new criterion insuring the self-organisation, we consider below the autowave processes (if any) occurring in the simplest systems -the Lotka and Lotka-Volterra models [22-24] (Section 2.1.1). It should be reminded only that standard chemical kinetics denies their ability to selforganisation either due to the absence of undamped oscillations (the Lotka model) or since these oscillations are unstable (the Lotka-Volterra model). 

To treat the stochastic Lotka and Lotka-Volterra models, we have now to extend the formalism presented in Section 2.2.2, where collective variables-numbers of particles iVA and Vg were used to describe reactions. The point is that this approach neglects local density fluctuations in small element volumes. To incorporate both these fluctuations and their correlations due to diffusive conjunction, we are in position now to reformulate these models in terms of the diffusion-controlled processes - in contrast to the rather primitive birth-death formalism used in Section 2.2.2. It permits also to demonstrate in the non-trivial way a role of diffusion in the autowave processes. The main results of this Chapter are published in [21, 25]. 

In other words, K(t) is afunctional of the joint correlation function of similar particles. In this respect, a set of equations (8.2.12) and (8.2.13) is similar to the stochastic treatment of the Lotka-Volterra model (equations (2.2.68) and (2.2.69)) considered in Section 2.3.1 using the similar time-dependent reaction rate (2.2.67). 

These two kinds of dynamics - for particle correlations and concentrations -become coupled through the reaction rate. The functionals J[Z] in (8.2.15) to (8.2.17) were defined in Chapter 5 (5.1.36) to (5.1.38) for different space dimensions d = 1,2,3. They emerge in those terms of (8.2.9) to (8.2.11) which are affected by the superposition approximation. It should be stressed that in the case of the Lotka-Volterra model it is the only approximation used for deriving the equations of the basic model. 

Fig. 8.4. The reaction rate in the Lotka-Volterra model. Parameters k = 0.5, d = 2.

The Lotka-Volterra model [23, 24] considered in the preceding Section 8.2 involves two autocatalytic reaction stages. Their importance in the self-organized chemical systems was demonstrated more than once [2], In this... 

Section we show that presence of two such intermediate stages is more than enough for the self-organization manifestation. Lotka [22] was the first to demonstrate theoretically that the concentration oscillations could be in principle described in terms of a simplest kinetic scheme based on the law of mass action [4], Its scheme given by (2.1.21) is similar to that of the Lotka-Volterra model, equation (2.1.27). The only difference is the mechanism of creation of particles A unlike the reproduction by division, E + A - 2A, due to the autocatalysis, a simpler reproduction law E —> A with a constant birth rate of A s holds here. Note that analogous mechanism was studied by us above for the A + B — B and A + B — 0 reactions (Chapter 7). 

Due to a similarity of reaction stages in the Lotka and Lotka-Volterra models the equations for the pop and pop remain the same as in Section 8.2. Other kinetic equations are slightly simplified, a number and multiplicity of integrals are reduced. 

Here the first term arises from the diffusive approach of reactants A into trapping spheres around B s it is nothing but the standard expression (8.2.14). The second term arises due to the direct production of particles A inside the reaction spheres (the forbidden for A s fraction of the system s volume). Unlike the Lotka-Volterra model, the reaction rate is defined by an approximate expression (due to use of the Kirkwood superposition approximation), therefore first equations (8.3.9) and (8.3.10) of a set are also approximate. 

This statement comes from analytical and topological studies [4], Unlike the Lotka-Volterra model where due to the dependence of the reaction rate K(t) on concentrations NA and NB, the nature of the critical point varied, in the Lotka model the concentration motion is always decaying. Autowave regimes in the Lotka model can arise under quite rigid conditions. It is easy to show that not any time dependence of K(t) emerging due to the correlation motion is able to lead to the principally new results. For example, the reaction rate of the A + B -> 0 reaction considered in Chapter 6 was also time dependent, K(t) oc t1 d/4 but its monotonous change accompanied by a strong decay in the concentration motion has resulted only in a monotonous variation of the quasi-steady solutions of (8.3.20) and (8.3.21) jVa(t) (3/K(t) and N, (t) p/f3 = const. 

In a system with strong damping of the concentration motion the concentration oscillations are constrained they follow oscillations in the correlation motion. As compared to the Lotka-Volterra model, where the concentration motion defines essentially the autowave phenomena, in the Lotka model it is less important being the result of the correlation motion. This is why when plotting the results obtained, we focus our main attention on the correlation motion in particular, we discuss in detail oscillations in the reaction rate K(t). 

Statement 1) a stable stationary solution of a complete set of equations of the Lotka model holds. At long t the reaction rate K(t) strives for the stationary value. Time development of concentrations obeys standard chemical kinetics, Section 2.1.1. 

For example, the standard synergetic approach [52-54] denies the possibility of any self-organization in a system with with two intermediate products if only the mono- and bimolecular reaction stages occur [49] it is known as the Hanusse, Tyson and Light theorem. We will question this conclusion, which in fact comes from the qualitative theory of non-linear differential equations where coefficients (reaction rates) are considered as constant values and show that these simplest reactions turn out to be complex enough to serve as a basic models for future studies of non-equilibrium processes, similar to the famous Ising model in statistical physics. Different kinds of auto-wave processes in the Lotka and Lotka-Volterra models which serve as the two simplest examples of chemical reactions will be analyzed in detail. We demonstrate the universal character of cooperative phenomena in the bimolecular reactions under study and show that it is reaction itself which produces all these effects. 

The impressive application of IET/MET to the study of Lotka-Volterra autocatalytic oscillatory reactions [203]... 

Lotka-Volterra reaction scheme A + X— 2X X y — 2Y Y— Z structurally unstable oscillation... 

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