ABSTRACT
The interiors of reverse micelles formed using nonionic surfactants to sequester water droplets in a nonpolar environment have been investigated using the decavanadate molecule as a probe. Chemical shifts and line widths of the three characteristic signals in the 51V NMR spectrum of decavanadate, corresponding to vanadium atoms in equatorial peripheral, equatorial interior, and axial locations, measure the local proton concentration and characteristics of the reverse micellar interior near the decavandate probe. All samples investigated indicate deprotonation of the vanadate probe in the reverse micelle environment. However, the relative mobility of the decavanadate molecule depends on the reverse micellar components. Specifically, the 51V NMR signals of the decavandate in reverse micelles formed using only the Igepal CO-520 surfactant display sharp signals indicating that the decavandate molecule tumbles relatively freely while reverse micelles formed from a mixture of Igepal CO-610 and -430 present a more viscous environment for the decavanadate molecule; the nature of the interior of the nonionic reverse water pool varies significantly depending on the specific Igepal. The 51V NMR spectra also indicate that the interior core water pool of the reverse micelles is less acidic than the bulk aqueous solution from which the samples were created. Together, these data provide a description that allows for a comparison of the water pools in these different nonionic reverse micelles.
ABSTRACT
The translational and rotational motions of water and dimethyl sulfoxide, [DMSO, (CH(3))(2)SO] have been investigated using quasi-elastic neutron scattering. Water-DMSO mixtures at five DMSO mole fractions, chi(DMSO), ranging from 0 to 0.75, were measured. Hydrogen-deuterium substitution was used to extract independently the water proton dynamics (d-DMSO-H(2)O), the DMSO methyl proton dynamics (h-DMSO-D(2)O) and to obtain background corrections (d-DMSO-D(2)O). The translational diffusion of water slows down significantly compared to bulk water at all chi(DMSO)>0. The rotational time constant for water exhibits a maximum at chi(DMSO)=0.33 that corresponds to the observed maximum of the viscosity of the mixture. Data for DMSO can be analyzed in terms of a relatively slow tumbling of the molecule about its center-of-mass in conjunction with random translational diffusion. The rotational time constant for this motion exhibits some dependence on chi(DMSO), while the translational diffusion constant shows no clear variation for chi(DMSO)>0. The results presented reinforce the idea that due to the stronger associative nature of DMSO, DMSO-water aggregates are formed over the whole composition range, disturbing the tetrahedral natural arrangement of the water molecules. As a consequence adding DMSO to water causes a drastic slowing down of the dynamics of the water molecule, and vice versa.
