Thermodynamic properties of water in the water-poor region of binary water + alcohol mixtures

Abstract

In our previous thermodynamic studies, we suggested that alcohol molecules in water-poor water + alcohol mixtures exist as alcohol clusters in a form similar to the pure alcohols. Here, we use calorimetry and densitometry to investigate how H2O interacts with alcohol clusters in water-poor binary aqueous mixtures of 12 different alcohols. The composition dependence of the measured excess partial molar enthalpy and volume of water (HEW and VEW), along with entropy data calculated from HEW and literature data for excess chemical potentials, showed that in water-poor solutions of small alcohols such as methanol, ethanol, and 1-propanol, mutual water–water interactions are endothermic, but entropically favorable. Conversely, in long-chain solvents such as 1-octanol and 1-decanol, the interaction is exothermic and entropically unfavorable. We suggest that these observations reflect water–alcohol hydrogen bonding in short-chain solvents and water clustering with more hydrogen bonding than in pure water or "dewetting" in mixtures of the longer alcohols, respectively. The composition dependence of HEW was also used to locate anomalies that specify the boundary between the mixing schemes characterizing the intermediate and the water-poor regions of alcohol + water mixtures.Key words: aqueous alkane-mono-ols, excess partial molar enthalpy, entropy and volume, mixing schemes.