Generalized corresponding states model for bulk and interfacial properties in pure fluids and fluid mixtures

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We have formulated a general approach for transforming an analytical equation of state (EOS) into the crossover form and developed a generalized cubic (GC) EOS for pure fluids, which incorporates nonanalytic scaling laws in the critical region and in the limit ρ→0 is transformed into the ideal gas equation EOS. Using the GC EOS as a reference equation, we have developed a generalized version of the corresponding states (GCS) model, which contains the critical point parameters and accentric factor as input as well as the Ginzburg number Gi. For nonionic fluids we propose a simple correlation between the Ginzburg number Gi and Zc, ω, and molecular weight Mw. In the second step, we develop on the basis of the GCS model and the density functional theory a GCS-density functional theory (DFT) crossover model for the vapor–liquid interface and surface tension. We use the GCS-DFT model for the prediction of the PVT, vapor–liquid equilibrium (VLE) and surface properties of more than 30 pure fluids. In a wide range of thermodynamic states, including the nearest vicinity of the critical point, the GCS reproduces the PVT and VLE surface and the surface tension of one-component fluids (polar and nonpolar) with high accuracy. In the critical region, the GCS-DFT predictions for the surface tension are in excellent agreement with experimental data and theoretical renormalization-group model developed earlier. Using the principle of the critical-point universality we extended the GCS-DFT model to fluid mixtures and developed a field-variable based GCS-FV model. We provide extensive comparisons of the GCS-FV model with experimental data and with the GCS-XV model formulated in terms of the conventional density variable—composition. Far from the critical point both models, GCS-FV and GCS-XV, give practically similar results, but in the critical region, the GCS-FV model yields a better representation of the VLE surface of binary mixtures than the GCS-XV model. We also show that by considering the Ginzburg number Gi as an independent CS parameter the GCS model is capable of reproducing the phase behavior of finite neutral nuclear matter.