Structural Isomerization and Molecular Motions of Liquid<i>n</i>-Alkanes. Ultrasonic and High-Frequency Shear Viscosity Relaxation

Between 20 and 120 MHz, the complex shear viscosity of n-tetradecane, n-pentadecane, n-hexadecane, and a n-eicosane/n-tetradecane mixture has been measured using a shear impedance spectrometer. The data are compared to ultrasonic absorption spectra of the liquids as measured between 1 MHz and 2 GHz. Relaxational behavior has been found. The extrapolated high-frequency shear viscosity ηs(∞) is distinctly smaller than the static shear viscosity ηs(0). The shear viscosity relaxation time is discussed in light of literature data of the orientational correlation time from depolarized Rayleigh scattering and also of the collision time as resulting from dielectric spectrometry. The assumption appears to be likely that the shear viscosity relaxation is due to rotational isomerizations of the chain molecules. A damped torsional oscillator model has been used to evaluate the spectra. The reasonable number of three carbon atoms per oscillator unit results. The activation energies and enthalpies are derived from measurements at different temperatures.

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