Insight into the gas–liquid transition from the Berthelot model

Abstract

We extend the parametric method developed for the van der Waals model by Lekner [Am. J. Phys. 50(2), 161–163 (1982)] to other equations of state, particularly the Berthelot model, thereby making the testing of these equations of state much faster and simpler. We systematically investigate important properties of first-order phase transitions in the Berthelot model. Thermodynamic properties near the critical point are discussed and the predictions of the Berthelot and van der Waals models are compared with experimental data. The Berthelot equation affords an improved fit to the density–temperature coexistence curve for many substances when compared to the van der Waals equation. A failure of the Berthelot model is its prediction of latent heat and heat capacities that are convex functions at lower temperatures. We also examine two modifications of the Berthelot equation of state that, like the van der Waals model, are also solvable by the parameter method. These, which we call the cPF and dPF models, reduce to the van der Waals and Berthelot models in different limits of their parameters. They give improved fits to the experimental data away from the critical point but involve an additional fitting parameter.