Insights on the origin of the Debye process in monoalcohols from dielectric spectroscopy under extreme pressure conditions.
The dielectric spectra of most simple liquids are characterized by two relaxation processes: (i) the alpha-process, an intense, broad non-Debye relaxation with a non-Arrhenius temperature dependence and (ii) a beta process, evident mainly below the glass transition and having nearly Arrhenius temperature behavior. However, the dielectric spectra of monoalcohols show three processes: two that resemble those of normal liquids and a third very intense Debye peak at lower frequencies, which is non-Arrhenius. Interestingly, this third process is not observed with other techniques such as light scattering and mechanical spectroscopy. There is a disagreement in the literature concerning the nature of this third relaxation. We investigated 2-ethyl-1-hexanol under high pressures (up to approximately 1.4 GPa) over a broad range of temperatures. The Debye process, which is the slowest, is strongly affected by pressure. At higher pressures the relaxation times and intensities of the two non-Arrhenius relaxations become more nearly equal. In light of these results, we propose a modified interpretation of the relaxation processes and their underlying structures in monoalcohols.
Fragiadakis
D
D
Chemistry Division, Naval Research Laboratory, Washington, DC 20375-5342, USA.
Roland
C M
CM
Casalini
R
R
D000441:Hexanols / Q000737:chemistry*; D011312:Pressure; D013696:Temperature
D000441:Hexanols; C034017:2-ethylhexanol