Chemical and Biomolecular Engineering Research and Publications


Excess Heat Capacity Surfaces for Water-Alkanol Mixtures by the UNIQUAC Model

Dr Y. Demirel, University of Nebraska-Lincoln

Document Type Article

The authors of this article are Dr.Yasar Demirel & Dr.Halime O.Paksoy .This article was originally published in the journal of "Industrial Engineering & chemistry research ” [DOI: 10.1021/ie000429027] © Copyright (2006) American Chemical Society. This article may be downloaded for personal use only. Any other use of this article requires prior permission of the author and the American Chemical Society. Further details about the following article can be found at American Chemical Society,Ing.Eng.Chem. Res 1995,34,921-927..


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 is very sensitive to structural changes in mixtures, concentration and temperature dependence of excess heat capacity 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 excess heat capacity 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 excess heat capacity 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.