First and Second-Phase Transitions of Gases at Isobaric Process; Lennard

The thermodynamic functions for Lennard–Jones (9,6) gases with a hard core that are evaluated till the third virial coefficients, are investigated at an isobaric process. Some thermodynamic functions are analytically expressed as functions of intensive variables, temperature, and pressure. Some thermodynamic quantities for carbon dioxide are calculated numerically and drawn graphically. In critical states, the heat capacity diverges to infinity at the critical point while the Gibbs free energy, volume, enthalpy, and entropy are continuous at the critical point. In the coexistence of two phases, the boiling temperatures and the enthalpy changes of vaporization are obtained by numerical calculations for 20 substances. The Gibbs free energy indicates a polygonal line; entropy, volume, and enthalpy jump from the liquid to gaseous phase at the boiling point. The heat capacity does not diverge to infinity but shows a finite discrepancy at boiling point. This suggests that a first-order phase transition at the boiling point and a second-order phase transition may occur at the critical point.