Ideal kinetic model equilibrium approximations

A qualified question is then whether or not the multicomponent models are really worthwhile in reactor simulations, considering the accuracy reflected by the flow, kinetics and equilibrium model parts involved. For the present multiphase flow simulations, the accuracy reflected by the flow part of the model is still limited so an extended binary approach like the Wilke model sufEce in many practical cases. This is most likely the case for most single phase simulations as well. However, for diffusion dominated problems multicomponent diffusion of concentrated ideal gases, i.e., for the cases where we cannot confidently designate one of the species as a solvent, the accuracy of the diffusive fluxes may be significantly improved using the Maxwell-Stefan approach compared to the approximate binary Fickian fluxes. The Wilke model might still be an option and is frequently used for catalyst pellet analysis. 

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. 

The representation of the kinetic operators in the form (6.1.13)-(6.1.16), (6.1.18) does not reduce essentially the general nature of the kinetic equation (6.1.11) because the non-ideality of the media can be (up to the certain degree of approximation) taken into account in expressions for the trmisition probabilities. The latter can be determined by the methods of equilibrium and non-equilibrium thermodynamics, with the help of dynamical models for elementsiry processes, and via empirical formulae. 

This model, as wets discussed in Chap.6, gives one an opportunity to describe the kinetics of non-ideal gas media in static and fluctuating surface field. Therefore, when approximating the kinetic operators (6.2.4), (6.2.5) one can use the results of quasiparticle method for non-ideal media kinetics (Dubrovskiy and Bogdanov 1979b), theory of liquids (Croxton 1974), theory of Brownian motion (Akhiezer and Peletminskiy 1977), theory of phase transitions, models of equilibrium properties of such systems (Jaycock and Parfitt 1981) with further application of methods of statistical thermodynamics of irreversible processes (Kreuzer and Payne 1988b) and experimental data on pair correlation function (Flood 1967). 

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