Anomalous Excess Heat Capacities of Ethanol + Alkane Mixtures

A thermodynamic study at atmospheric pressure on the ethanol+n-dodecane and ethanol+n-tridecane binary systems near their liquid–liquid critical points has been carried out. To this end, densities and speeds of sound were determined in the temperature range from 288.15 to 308.15 K, whereas differential scanning calorimetry was used to obtain isobaric heat capacities per unit volume from 288.15 to 303.15K as well as liquid–liquid equilibrium curves. All these results for the mentioned properties were obtained over the complete composition range. They were used to obtain molar volumes, isentropic compressibilities, isobaric thermal expansivities, isothermal compressibilities, isochoric heat capacities, and the excess quantities of all these properties. An untypical behavior of the excess heat capacities at the lowest measuring temperatures resulting from the critical behavior of the isobaric heat capacity is observed. No clear anomalies for the excess volumetric properties are detected.