Abstract
Broadband dielectric spectra (1 MHz to 40 GHz) and ultrasonic attenuation spectra (300 kHz to 3 GHz) as well as frequency-dependent complex shear viscosities (6 MHz to 120 MHz) are reported for alcohols and for their mixtures with other alcohols, with alkanes, and with water. The spectra are discussed with a view to features controlling the molecular dynamics of associating liquids. Special attention is given to (i) the rotation of terminal single-hydrogen-bonded hydroxy groups of associated structures, (ii) the dominating relaxation process of the structures, involving multiply-hydrogen-bonded hydroxy groups, (iii) the alkyl chain rotational isomerization, (iv) effects of clustering in alcohol–alkane mixtures, and (v) indications of non-critical concentration fluctuations of alcohol–water mixtures. The hydrogen network fluctuations of the alcohol systems can be consistently described in terms of a wait-and-switch model of relaxation. The concentration fluctuations are well represented by a recent “unifying” theoretical model, indicating a predominant impact of hydrophobic groups in the promotion of a micro-heterogeneous structure of mixtures with water.
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Open Access This is an open access article distributed under the terms of the Creative Commons Attribution Noncommercial License (https://creativecommons.org/licenses/by-nc/2.0), which permits any noncommercial use, distribution, and reproduction in any medium, provided the original author(s) and source are credited.
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Kaatze, U. Hydrogen Network Fluctuations of Alcohols. Evidence from Ultrasonic, Dielectric, and Shear Impedance Spectrometry. Int J Thermophys 33, 653–663 (2012). https://doi.org/10.1007/s10765-011-1021-z
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DOI: https://doi.org/10.1007/s10765-011-1021-z