Chemical and Biomolecular Engineering Research and Publications



Demirel 0000-0002-8183-0991

Date of this Version



Industrial Engineering and Chemistry Research (1995) 34(3): 921–927

doi: 10.1021/ie00042a027


Copyright © 2006, American Chemical Society. Used by permission


Hydroorganic mixtures are industrial solvents that can serve as media to solubilize either water in hydrocarbon or a hydrophobic substance in water. In many cases the solubilizing capability is obtained via a homogeneous complex aqueous mixtures containing an alcohol. Since excess heat capacity CPE, is very sensitive to structural changes in mixtures, concentration and temperature dependence of CPE have been calculated by using the UNIQUAC model for the mixtures methanol(l)-water(%, ethanol(l)-water(2), and l-propanol(l)-water(2). The temperature-dependent parameters of the model estimated directly from CPE data at more than one different isotherm are used in the calculations. The overall deviations between the calculated and experimental data points change in the range 6.52-10.15%, which indicates the satisfactory representation of CPE data by the model for engineering calculations. The temperature range of experimental data for the mixtures is 288.15and 308.15K. Surfaces of reduced, apparent and partial molar excess heat capacities are also derived. The concentration and temperature dependencies of these functions suggest the existence of transitions of microstructure in the water-rich region, qualitatively similar to micellization. The surface of these thermodynamic functions facilitates a better understanding of thermodynamic properties and association of alcohol-water mixtures over a whole or certain concentration and temperature range. Such thermodynamic surfaces may be represented satisfactorily by the UNIQUAC model at low pressures.