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• W2035804565 abstract "The complex dielectric permittivity of methanol/water (MW), ethanol/water (EW), 1-propanol/water (1PW), and 2-propanol/water (2PW) mixtures was determined using Time Domain Reflctometry (TDR) for the entire concentration range 0≤X(mmolar fraction of alcohol)≤1.0 in 0.1–25GHz at 20°C–30°C. The dielectric relaxation mechanism of the mixtures is discussed based of the dielectric behaviors of pure water and alcohols reported by Barthel et al.[4,5] and Buchner et al.[6]. In the alcohol-rich region of ∼0.4≤X≤1.0, the spectra can be well described by the two process model, the superposition of the Cole-Cole (j=1) and the additional Debye (j=2) relaxations. We found that the relaxation amplitude for the high frequency process, Δϵ2, is kept small at the order of 2 even at maximum. The processes are validly attributed to the cooperative dynamics of the H-bond system (j=1) and a rotation of singly H-bonded alcohol monomers at the ends of chainlike cluster (j=2). The excess activation free energy, enthalpy, and entropy of the alcohol/water mixtures, ΔGE, ΔHE, and ΔSE, and their partial molar quantities, ΔGiE, ΔHiE, and ΔSiE (i=alcohol (A) and water (W)) have been calculated. Above the boundary concentration, Xb, where Xb∼0.30 (MW), 0.18 (EW), 0.14 (1PW), and 0.15 (2PW), ΔHAE and ΔSAE become nearly zero, indicating that a state of alcohol molecules in the mixtures is not very different from that in pure liquid. In the water-rich region, two maxima of ΔHAE and ΔSAE attributed to hydrophobic hydration appear at X1 and X2, where X1∼0.045 (MW), 0.08 (EW), 0.03 (1PW), and 0.03 (2PW), and X2∼0.12 (MW), 0.08 (EW), 0.06 (1PW), and 0.065 (2PW). The phenomena suggest the formation of two types of saturated hydration structure and their transition." @default.
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• W2035804565 date "2002-11-01" @default.
• W2035804565 modified "2023-10-09" @default.
• W2035804565 title "Dielectric relaxation mechanism and dynamical structures of the alcohol/water mixtures" @default.
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• W2035804565 doi "https://doi.org/10.1016/s0167-7322(02)00085-5" @default.
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