RESUMO
Micelles formed in water from tetramethyl-, tetraethyl-, tetrapropyl- and tetrabutylammonium dodecyl sulfate (TMADS, TEADS, TPADS, and TBADS, respectively) are characterized as reaction media. All of the results are identical in the presence or absence of added salt, provided micelles of the same aggregation number, N, are compared. The microviscosity (eta) deduced from the rotational motion of the nitroxide group of a spin probe increases modestly as a function of N in TMADS and TEADS, decreases slightly in TPADS, and decreases slightly before increasing in TBADS. The activation energy for the viscosity is remarkably similar in all of the tetraalkylammonium dodecyl sulfate (TAADS) micelles and is similar to that in ethanol/water mixtures as well as other anionic and cationic micelles. The volume fraction occupied by water in the polar shell, H(t), decreases with N in TMADS, TEADS, and TPADS at 10, 25, and 45 degrees C whereas it decreases, goes through a minimum, and then increases in TBADS. H(t) also decreases with the size of the counterion. The bimolecular collision rate as deduced from fluorescence quenching of pyrene by dodecylpyridinium chloride conforms well to a hydrodynamic description, varying linearly with T/eta, where T is the absolute temperature and passing through the origin. Quenching probablities of 0.53, 0.51, 0.45, 0.39 for TMADS, TEADS, TPADS, and TBADS, respectively, are rationalized in terms of small shifts of the diffusion zones outside of the Stern layer by an average of 16% of the Stern layer thickness.
