The first-order phase transition of melting for molecular crystals by Frost–Kalkwarf vapor- and sublimation-pressure equations

Abstract Thermodynamic quantities in the coexistence of the liquid and the solid phases for Frost–Kalkwarf vapor- and sublimation-pressure equations are investigated at an isobaric process. Gibbs free energy changes in the gaseous and the liquid phases, Δ G GL , has been derived from the Frost–Kalkwarf vapor-pressure equation. Similarly, Gibbs free energy changes in the gaseous and the solid phases, Δ G GS , may be estimated by the Frost–Kalkwarf sublimation-pressure equations which are determined by data of sublimation pressures and temperatures for 24 substances. In coexistence between the liquid and the solid phases, Gibbs free energy changes in the liquid and the solid phases, Δ G LS , may be expressed as the difference of Δ G GL and Δ G GS . The melting temperatures and enthalpy changes of melting are evaluated by numerical calculations for 24 substances. The behaviors of H 2 O for the neighborhood at the melting and the boiling points are investigated. The Gibbs free energy indicates two polygonal lines. Entropy, volume and enthalpy jump from the solid to the liquid phase at the melting point and from the liquid to the gaseous phase at the boiling point. The heat capacity does not diverge to infinity but shows a finite discrepancy at the melting and the boiling points. This suggests that first-order phase transitions at the melting and the boiling points may occur.