Hydrophobic hydration and molecular association in methanol–water mixtures studied by microwave dielectric analysis

Dielectric relaxation measurements on the methanol–water mixtures for the entire concentration range were carried out using time domain reflectometry in the frequency range from 500 MHz to 25 GHz at 20, 25, and 30 °C. The excess partial molar activation free energy, enthalpy, and entropy for methanol, ΔGMAE, ΔHMAE, and ΔSMAE, and those for water, ΔGWE, ΔHWE, and ΔSWE, were calculated from accurately measured concentration and temperature dependence of the dielectric relaxation time of the mixtures. The behavior of the excess partial molar quantities in the regions below and above X (molar fraction of methanol) ∼0.3 are quite different from each other. In a water-rich region, ΔHMAE and ΔSMAE exhibit two maxima at X∼0.045 and X∼0.12, which is clearly attributed to structural enhancement of the hydrogen bond network of water, the so-called hydrophobic hydration. Appearance of two maxima in ΔHMAE and ΔSMAE implies that water molecules surround methanol molecules in qualitatively different manners around the two points. In the concentrated region of X⩾0.3, the values of ΔHMAE and ΔSMAE become nearly zero, which means that methanol molecules in the mixtures find themselves in not a very different environment from that in pure methanol, associated and forming chainlike clusters. Water molecules seem to exothermically attach to the hydrophilic site of methanol.