Prediction of High‐Pressure Phase Equilibria using Cubic EOS: What Can Be Learned?

Modern semi‐empirical cubic EOSs are usually attached by complex functionalities, such as Huron‐Vidal (HV)‐type mixing rules. Although this practice improves the flexibility of the models, it also complicates consideration of an overall picture of phase behavior. As a result, G E ‐based equations are usually adjusted to the experimental data by way of a local fit. The latter approach tends to ignore that different regions of the thermodynamic phase space are closely inter‐related. The present study demonstrates that the contribution of (HV)‐type mixing rules to predicting high‐pressure phase equilibria can be quite modest and that in addition they may generate non‐realistic phase diagrams.