Equilibrium chemical kinetics

L.S. Polak, Non-Equilibrium Chemical Kinetics and its Applications (Nauka, Moscow, 1979). 

A.N. Gorban , Round the Equilibrium. Chemical Kinetics Equations and their Thermodynamic Analysis, Nauka, Novosibirsk, 1984 (in Russian). 

Several basic principles tliat engineers and scientists employ in performing design calculations and predicting Uie performance of plant equipment includes Uiemiochemistry. chemical reaction equilibrium, chemical kinetics, Uie ideal gas law, partial pressure, pliase equilibrium, and Uie Reynolds Number. 

The coefficient of viscosity r plays the same role in the Kramers model as the cross section a in the theory of Curtiss and Prigogine and the transition probabilities W, in the Zwolinski-Eyring treatment. Neither its value nor analytical form can be determined from our present knowledge of intermolecular forces. Itisinterest-5. g to see how this factor enters into all the theories and models of. microscopic nonequilibrium chemical kinetics. Its absence from equilibrium chemical kinetics is, of course, due to the fact that the properties of the equilibrium state are independent of the manner of its establishment. 

The first passage time given by Eq. VII.28 is that of equilibrium chemical kinetics since it corresponds to the expression for z (t) (Eq, VII. 18) which in the limit as JV oo would be the Boltzmann distribution. Substitution of Eqs. VII.29ato VII.29d and VII. 12 into Eq. VII.28 yields... 

First, we consider the one-temperature model for the non-equilibrium chemical kinetics in thermally equilibrium gas flows or deviating weakly from thermal equilibrium state. Then, the models for vibrational-chemical coupling in gas flows are derived from the kinetic theory taking into account state-to-state and multi-temperature vibrational distributions. 

We consider strong non-equilibrium chemical kinetics in a flow under the following conditions for relaxation times... 

Euler) approximation, the governing equations describe non-equilibrium chemical kinetics in a thermally equilibrium inviscid non-conducting gas mixture ... 

In this Chapter, the theoretical models for non-equilibrium chemical kinetics in multi-component reacting gas flows are proposed on the basis of three approaches of the kinetic theory. In the frame of the one-temperature approximation the chemical kinetics in thermal equilibrium flows or deviating weakly from thermal equilibrium is studied. The coupling of chemical kinetics and fluid dynamics equations is considered in the Euler and Navier-Stokes approximations. Chemical kinetics in vibrationaUy non-equilibrium flows is considered on the basis of the state-to-state and multi-temperature approaches. Different models for vibrational-chemical coupling in the flows of multi-component mixtures are derived. The influence of non-equilibrium distributions on reaction rates in the flows behind shock waves and in nozzle expansion is demonstrated. 

The vibrational relaxation of molecules is an important process in non-equilibrium chemical kinetics. Out of the many different relaxation phenomena the simplest one involves diatomic molecules for which there is no complicated intramolecular energy transfer. If the degree of vibrational excitation is not too high, the most important processes correspond to one-quantum transitions. This results in considerable simplification of relaxation kinetics which simplifies even further under the condition of a constant translational temperature T. 

Strictly speaking, the chemical potential is only defined as a time-independent quantity for a system at equilibrium. Chemical kinetics belongs to the discipline of irreversible, nonequilibrium thermodynamics. Whereas thermodynamics of reversible processes has a solid foundation, this is not the case for the thermodynamics of irreversible prcx esses. At present, the latter is one of the frontier areas of chemical research. We will highlight these developments where relevant to chemical kinetics and catalysis. 

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