Azeotropy of alcohol–water mixtures from the viewpoint of cluster-level structures

Microheterogeneity in binary mixtures of methanol with aliphatic alcohols: ATR-IR/NIR spectroscopic, chemometrics and DFT studies

“…It is well known that alcohol-water mixtures reveal non-ideal behavior due to the presence of hydrophobic interactions disturbing the structure of liquid water. [1][2][3][4][5][6] As a result, the molecules of water and alcohol form separate clusters predominantly composed of one constituent of the mixture. This behavior is not surprising since, in contrast to the molecules of alcohol, the molecules of water do not posses the hydrophobic part.…”

Probing hydrogen-bonding in binary liquid mixtures with terahertz time-domain spectroscopy: a comparison of Debye and absorption analysis

“…Due to the importance of water in biological systems, 6 proticprotic liquid mixtures that have been studied typically include water as one of the components, and systems such as wateralcohol and water-diol mixtures have been studied extensively in the past with techniques including neutron diffraction, 7,8 NMR, [9][10][11][12][13] Raman spectroscopy, 14 infrared spectroscopy, 15,16 dielectric spectroscopy, 17 mass spectrometry 18 as well as numerical and computational studies. 19,20 In these systems, a larger than expected decrease in entropy and enthalpy upon mixing is observed and in early work this was attributed to an enhancement in the structuring of water molecules in the hydration shell of the solute molecule, where the water structure becomes more ice-like.…”

A comparison of force fields for ethanol–water mixtures

“…The local immiscibility of the components in these mixtures is often related to the highly non-trivial changes with the concentration of various properties, such as excess enthalpy, [25] speed of sound, [26,27] isothermal compressibility, [28] isentropic compressibility, [29] excess heat capacity [30 -32] and vapour -liquid equilibrium mole fraction curve. [33] The underlying structural organisation is due to the subtle compensation of the competing hydrophobic -hydrophilic interactions. Such effects are strongly dependent on the force fields, especially crosscomponent interactions.…”