Structural aspects in the dielectric properties of pentyl alcohols.

At temperatures between 0 and 60 °C densities, shear viscosities and dielectric spectra have been measured for isomers 1-pentanol, 2-pentanol, 3-pentanol, isopentylalcohol, and tert-pentanol, as well as for mixtures of these alcohols. The density and shear viscosity data are discussed in terms of deviations from ideal mixing behavior. The dielectric spectra are evaluated to yield the extrapolated static permittivity and the relaxation time of the principal (low-frequency) relaxation term. The former parameter is analyzed in view of dipole orientation correlations, the latter one is discussed in terms of the activation enthalpy controlling the relaxation process. A noticeable result is the effect of isomer structure on both the dipole orientation correlation and the dielectric relaxation. Especially the dielectric parameters of tert-pentanol deviate significantly from the relevant parameters of the other pentanols. Such deviations are considered in the light of models of hydrogen network structure and fluctuations.

Molecular dynamics and conformational kinetics of mono- and disaccharides in aqueous solution.

Acoustical attenuation spectra between 10 kHz and 2 GHz, complex dielectric spectra between 300 kHz and 40 GHz, and time-resolved non-equilibrium measurements are reported for aqueous solutions of various mono- and disaccharides with and without 2:1 valent salts. The spectra reveal a variety of relaxation regimes with relaxation times between 1 micros and 10 ps. In addition, the time-resolved observations enable the study of the mutarotation with relaxation times on the order of 10(3) s. Variation of the concentration and temperature as well as a careful choice of the saccharides allow a discussion of the relaxation processes in terms of a chair-chair ring inversion, two modes of pseudorotation, an exocyclic hydroxymethyl group rotation, a carbohydrate-carbohydrate association, and, in the disaccharide solutions, a rotation of the rings relative to another. Salt-containing solutions show also relaxation phenomena reflecting different steps cation-carbohydrate association and variations in the carbohydrate conformational isomerizations and associations due to interactions with cations.

Relaxation dynamics in glycerol-water mixtures: I. Glycerol-rich mixtures.

We discuss the relaxation dynamics of glycerol-water mixtures, as studied by dielectric spectroscopy in the frequency range from 1 Hz to 250 MHz and at temperatures between 173 and 323 K. The experimental results obtained for the glycerol-rich mixtures suggest that the main dielectric relaxation process, as well as the so-called high-frequency "excess wing" (EW) and dc conductivity, follow the same temperature dependence. This result indicates that all of these processes are induced by the same molecular origin. A new phenomenological function is proposed to describe the whole dielectric spectrum in the covered frequency range, and some possible mechanisms of dielectric behaviors through the dc conductivity, the main relaxation process, and the EW are discussed.

Shear viscosity relaxation of a critical binary liquid.

Two series of diffusion coefficients D are reported for the triethylamine-water binary critical mixture. One has been obtained from quasielastic light scattering measurements, the other one has been derived from broadband ultrasonic spectra, yielding the relaxation rate of order parameter fluctuations, and shear viscosity data. Using high frequency shear impedance spectrometry in the range 20-130 MHz, relaxations in the background part of the viscosity, resulting in viscoelastic mixture properties, have been found. Both series of D data agree either if a half-attenuation frequency distinctly smaller than the theoretical value Omega(1/2)=2.1 is used in the Bhattacharjee-Ferrell scaling function or if the viscosity extrapolated from the shear impedance measurements to low frequencies is applied to the Kawasaki-Ferrell relation. This extrapolated viscosity is smaller than the static shear viscosity measured with capillary viscosimeters.