Thermodynamic properties of glycerol: Experimental and theoretical study

• Vapor pressures of glycerol were measured by static and transpiration method.
• Vaporization enthalpies were derived and compared with the literature.
• Vapor pressures were evaluated and reliable approximating equation was developed.
• Thermodynamic functions of formation derived for the liquid and gas phase.
• Strength of hydrogen bonding in the gas and in the liquid phase was discussed.

Vapor pressures of highly pure glycerol were measured by the static and the transpiration methods in a broad temperature range. The standard molar enthalpy of vaporization of glycerol was derived from the vapor pressure temperature dependencies. Thermodynamic data on glycerol available in the literature were collected, evaluated, and combined with own experimental results. We recommend the set of vaporization and formation enthalpies for glycerol at 298.15 K (in kJ mol−1): ΔfHm° (g) = −(578.8 ± 0.6), ΔfHm° (l) = −(669.3 ± 0.5), and ΔlgHm° = (90.5 ± 0.3) as the reliable benchmark properties for further thermochemical calculations. Quantum-chemical calculations of the gas phase molar enthalpy of formation of glycerol have been performed using the G4 method and results were in agreement with the recommended experimental data. The standard molar entropy of formation and the standard molar Gibbs function of formation of glycerol were estimated.