General Kinetic Rules for Chemical Reactions

However, a question arises - could similar approach be applied to chemical reactions At the first stage the general principles of the system s description in terms of the fundamental kinetic equation should be formulated, which incorporates not only macroscopic variables - particle densities, but also their fluctuational characteristics - the correlation functions. A simplified treatment of the fluctuation spectrum, done at the second stage and restricted to the joint correlation functions, leads to the closed set of non-linear integro-differential equations for the order parameter n and the set of joint functions x(r, t). To a full extent such an approach has been realized for the first time by the authors of this book starting from [28], Following an analogy with the gas-liquid systems, we would like to stress that treatment of chemical reactions do not copy that for the condensed state in statistics. The basic equations of these two theories differ considerably in their form and particular techniques used for simplified treatment of the fluctuation spectrum as a rule could not be transferred from one theory to another. 

Many important natural processes ranging from nuclear decay to uni-molecular chemical reactions are first order, or can be approximated as first order, which means that these processes depend only on the concentration to the first power of the transforming species itself. A cellular automaton model for such a system takes on an especially simple form, since rules for the movements of the ingredients are unnecessary and only transition rules for the interconverting species need to be specified. We have recently described such a general cellular automaton model for first-order kinetics and tested its ability to simulate a number of classic first-order phenomena.70... 

It is clear that these thermal criteria for stabihty are given in terms of steady-state values no transients need be calculated. Since the problem may be formulated in terms of a linear matrix, it is easily generalized to chemical reactions involving n species, in either simultaneous or sequential kinetic schemes. While probably obvious, it is worth remarking that there is very Kttle that is intuitive about the criteria of equations (6-38). One cannot rely on a guessing game for such rules. 

The effect of temperature indicates kinetic character. The other data is consistent with complete kinetic control by a preceding first order chemical reaction. A catalytic process could not be ruled out. (Continued electrolysis on a very small volume at the potential of the upper plateau, would show whether the analyte was consumed or regenerated). Either way the wave would generally not be suitable for analytical application. 

Temperature and time also affects the corrosion reaction. It is generally known that the rate of a chemical reaction increases with increasing temperature. As a rule of thumb the reaction rate doubles for every 10° increase in temperature. The kinetics of corrosion reactions can develop differently. Fig. 1-8. A constant, linear rate of reaction is observed for acidic corrosion where no protective layer is formed (curve a). Decreasing rates of corrosion are often ob-... 

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