The effect of hydrogen bonding on the diffusion of water in n-alkanes and n-alcohols measured with a novel single microdroplet method.

While the Stokes-Einstein (SE) equation predicts that the diffusion coefficient of a solute will be inversely proportional to the viscosity of the solvent, this relation is commonly known to fail for solutes, which are the same size or smaller than the solvent. Multiple researchers have reported that for small solutes, the diffusion coefficient is inversely proportional to the viscosity to a fractional power, and that solutes actually diffuse faster than SE predicts. For other solvent systems, attractive solute-solvent interactions, such as hydrogen bonding, are known to retard the diffusion of a solute. Some researchers have interpreted the slower diffusion due to hydrogen bonding as resulting from the effective diffusion of a larger complex of a solute and solvent molecules. We have developed and used a novel micropipette technique, which can form and hold a single microdroplet of water while it dissolves in a diffusion controlled environment into the solvent. This method has been used to examine the diffusion of water in both n-alkanes and n-alcohols. It was found that the polar solute water, diffusing in a solvent with which it cannot hydrogen bond, closely resembles small nonpolar solutes such as xenon and krypton diffusing in n-alkanes, with diffusion coefficients ranging from 12.5x10(-5) cm(2)/s for water in n-pentane to 1.15x10(-5) cm(2)/s for water in hexadecane. Diffusion coefficients were found to be inversely proportional to viscosity to a fractional power, and diffusion coefficients were faster than SE predicts. For water diffusing in a solvent (n-alcohols) with which it can hydrogen bond, diffusion coefficient values ranged from 1.75x10(-5) cm(2)/s in n-methanol to 0.364x10(-5) cm(2)/s in n-octanol, and diffusion was slower than an alkane of corresponding viscosity. We find no evidence for solute-solvent complex diffusion. Rather, it is possible that the small solute water may be retarded by relatively longer residence times (compared to non-H-bonding solvents) as it moves through the liquid.

U-Pb geochronology of the Santa Cruz Formation (early Miocene) at the Río Bote and Río Santa Cruz (southernmost Patagonia, Argentina): Implications for the correlation of fossil vertebrate localities

© 2016 Elsevier Ltd.The early Miocene Santa Cruz Formation (SCF) in southern Patagonia hosts the Santacrucian South American Land Mammal Age (SALMA), whose age is known mainly from exposures along the Atlantic coast. Zircon U-Pb ages were obtained from intercalated tuffs from four inland sections of the SCF: 17.36 ± 0.63 Ma for the westernmost Río Bote locality, and 17.04 ± 0.55 Ma-16.32 ± 0.62 Ma for central Río Santa Cruz localities. All ages agree with the bounding age of underlying marine units and with equivalent strata in coastal exposures. New ages and available sedimentation rates imply time spans for each section of ~18.2 to 17.36 Ma for Río Bote and 17.45-15.63 Ma for central Río Santa Cruz (Burdigalian). These estimates support the view that deposition of the SCF began at western localities ~1 Ma earlier than at eastern localities, and that the central Río Santa Cruz localities expose the youngest SCF in southern Santa Cruz Province. Associated vertebrate faunas are consistent with our geochronologic synthesis, showing older (Notohippidian) taxa in western localities and younger (Santacrucian) taxa in central localities. The Notohippidian fauna (19.0-18.0 Ma) of the western localities is synchronous with Pinturan faunas (19.0-18.0 Ma), but older than Santacrucian faunas of the Río Santa Cruz (17.2-15.6 Ma) and coastal localities (18.0-16.2 Ma). The Santacrucian faunas of the central Río Santa Cruz localities temporally overlap Colloncuran (15.7 Ma), Friasian (16.5 Ma), and eastern Santacrucian faunas.