By K. S. W. Sing (auth.), Alírio E. Rodrigues, M. Douglas LeVan, Daniel Tondeur (eds.)
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Extra resources for Adsorption: Science and Technology
Valenzuela, D. L. Myers, "Micropore Exclusion Theory," in preparation. 26. P. L. Myers, Adsorption Equilibrium Data Handbook, PrenticeHall, in press (1988). 27. L. Myers, O. Talu and 1. Zwiebel, AIChE J. 34, 397 (1988). M. RUTHVEN University of New Brunswick Dept. of Chemical Engineering Fredericton, NB E3B SA3 Canada 1. INTRODUCTION Statistical thermodynamics provides a useful alternative to the classical approach to the cor-elation and prediction of adsorption equilibria. In statistical thermodynamics the equilibrium properties of a system are deduced by considering the statistical behaviour of a large number of loosely coupled identical subsystems (the ensemble) which can exist with equal probability in any allowable quantum state, subject to the Boltzmann Law of energy distribution.
Whi c h i s equ1va Derivation of the Simplified Statistical Model Isotherm In the derivation of the Langmuir isotherm we were able to proceed directly from the canonical partition function but in more complex systems such as those involving interaction between molecules on adjacent sites this approach is not possible. n" (17) where" = e P / kT and:: = EFe Np / kT . If we consider M cages or cells within a zeolite lattice in which each cage can accomodate up to M guest molecules, the canonical ensemble partition function is given by: F(N,M,T) (18) where f(s) represents the partition function for a cage (or sub-system) containing s sorbate molecules and n 1 , n 2 •..
B 1] c f f' F k K 52 grand partition function defined by eqn 30 ~ chemical potential ~o standard chemical potential , , KA,K B etc. ' K"=KA 3 1/3) ~/kT A activity defined as e ~Ho enthalpy of adsorption at zero loading AU energy of adsorption at zero loading Sugscripts sand g refer to adsorbed and gaseous species. REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. L. Hill, "Introduction to Statistical Thermodynamics", Addison-Wesley, Reading, Mass (1960). V. Q. Du, J. Chem. Soc. Faraday, Trans II, 74, 367 (1978); 77, 1 (1981); 77, 17 (1981).