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Large Sample Distribution Theory

Evaporation and vapor pressure are both explained on a molecular level by the kinetic-molecular theory developed in Section 9.6 to account for the behavior of gases. The molecules in a liquid are in constant motion, but at a variety of speeds depending on the amount of kinetic energy they have. In considering a large sample, molecular kinetic energies follow a distribution curve like that... [Pg.396]

Do we expect this model to be accurate for a dynamics dictated by Tsallis statistics A jump diffusion process that randomly samples the equilibrium canonical Tsallis distribution has been shown to lead to anomalous diffusion and Levy flights in the 5/3 < q < 3 regime. [3] Due to the delocalized nature of the equilibrium distributions, we might find that the microstates of our master equation are not well defined. Even at low temperatures, it may be difficult to identify distinct microstates of the system. The same delocalization can lead to large transition probabilities for states that are not adjacent ill configuration space. This would be a violation of the assumptions of the transition state theory - that once the system crosses the transition state from the reactant microstate it will be deactivated and equilibrated in the product state. Concerted transitions between spatially far-separated states may be common. This would lead to a highly connected master equation where each state is connected to a significant fraction of all other microstates of the system. [9, 10]... [Pg.211]

The novel approach for calculation of pore size distributions, which is reported in the current study is based on recent developments in the materials science and in the theory of inhomogeneous fluids. First, an application of experimental adsorption data for well-characterized MCM-41 silicas enabled proper calibration of the pore size analysis. Second, an application of a modem theory to describe the behavior of inhomogeneous fluids in confined spaces, that is the non-local density functional theory [6], allowed the numerical calculation of model isotherms for various pore sizes. In addition, a practical numerical deconvolution method that provides a "best fit" solution representing the pore distribution of the sample was implemented [7, 8]. In this paper we describe a deconvolution method for estimating mesopore size distribution that explicitly allows for unfilled large pores, and a method for creating composite, or hybrid, models that incorporate both theoretical calculations and experimental observations. Moreover, we showed the applicability of the new approach in characterization of MCM-41 and related materials. [Pg.72]


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