Vapor pressures and thermophysical properties of selected hexenols and recommended vapor pressure for hexan-1-ol

• Thermodynamic properties of hexenols and hexan-1-ol were studied.
• New vapor pressure data were determined using the static method.
• New liquid phase heat capacities were determined.
• Ideal-gas thermodynamic properties were calculated.
• Recommended vapor pressure equations were developed.

A thermodynamic study of selected unsaturated alcohols, cis-hex-3-en-1-ol, trans-hex-2-en-1-ol, and hex-1-en-3-ol, together with hexan-1-ol, is presented in this work. The vapor pressure measurements were performed using the static method over the environmentally important temperature range from 238 to 308 K. Liquid heat capacities were measured by Tian–Calvet calorimetry in the temperature interval from 258 to 355 K and were extended by controlled extrapolation by differential scanning calorimetry (DSC) toward the normal boiling point temperatures. The phase behavior was investigated by DSC from 183 K. The thermodynamic properties in the ideal-gas state were calculated by combining statistical thermodynamics and density functional theory (DFT) calculations. Scaling factors were evaluated based on measured Raman and IR spectra. Calculated ideal-gas heat capacities and experimental data on vapor pressures, condensed phase heat capacities, and vaporization enthalpies were treated simultaneously to obtain a consistent thermodynamic description.