Medium effects 345 from difference

According to Owen s definitions, the AG term in 2.11.11 is related to the total medium effect, AG to the primary medium effect and the logarithmic term is the secondary medium effect. It is evident therefore that the primary medium effect (or simply the medium effect) reflects differences in ion-solvent interactions, and the secondary medium effect (or salt effect or concentration effect ) reflects differences in ion-ion interactions and solvation effects the former quantity is, of course, independent of concentration whereas the latter quantity, which is usually several orders of magnitude smaller, is defined for a constant (finite) concentration. The standard free energy of transfer is defined for the transfer of 1 mole of substance from water to the organic solvent, i.e. 

By combining this with eqns. 3.4.4 and 3.4.5 we obtain a relation that enables us to find the medium effect from the difference in pKa values... 

A micelle-bound substrate will experience a reaction environment different from bulk water, leading to a kinetic medium effect. Hence, micelles are able to catalyse or inhibit organic reactions. Research on micellar catalysis has focused on the kinetics of the organic reactions involved. An overview of the multitude of transformations that have been studied in micellar media is beyond the scope of this chapter. Instead, the reader is referred to an extensive set of review articles and monographs" ... 

Yasui et al. [29] have used solution of wave equation based on finite element method for characterization of the acoustic field distribution. A unique feature of the work is that it also considers contribution of the vibrations occurring due to the reactor wall and have evaluated the effect of different types of the reactor walls or in other words the effect of material of construction of the sonochemical reactor. The work has also contributed to the understanding of the dependence of the attenuation coefficient due to the liquid medium on the contribution of the vibrations from the wall. It has been shown that as the attenuation coefficient increases, the influence of the acoustic emission from the vibrating wall becomes smaller and for very low values of the attenuation coefficient, the acoustic field in the reactor is very complex due to the strong acoustic emission from the wall. 

Extensions of BCS beyond the oral IR area has also been suggested, for example to apply BCS in the extended-release area. However, this will provide a major challenge since the release from different formulations will interact in different ways with in vitro test conditions and the physiological milieu in the gastrointestinal tract. For example, the plasma concentration-time profile differed for two felodipine ER tablets for which very similar in vitro profiles had been obtained, despite the fact that both tablets were of the hydrophilic matrix type based on cellulose derivates [70], This misleading result in vitro was due to interactions between the gel strength of the matrix and components in the dissolution test medium of no in vivo relevance. The situation for ER formulations would be further complicated by the need to predict potential food effects on the drug release in vivo. 

It is easy to understand the lower reactivity of non-ionic nucleophiles in micelles as compared with water. Micelles have a lower polarity than water and reactions of non-ionic nucleophiles are typically inhibited by solvents of low polarity. Thus, micelles behave as a submicroscopic solvent which has less ability than water, or a polar organic solvent, to interact with a polar transition state. Micellar medium effects on reaction rate, like kinetic solvent effects, depend on differences in free energy between initial and transition states, and a favorable distribution of reactants from water into a micellar pseudophase means that reactants have a lower free energy in micelles than in water. This factor, of itself, will inhibit reaction, but it may be offset by favorable interactions with the transition state and, for bimolecular reactions, by the concentration of reactants into the small volume of the micellar pseudophase. 

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