Evaluation of Derivative Properties by Various Thermodynamic Models for Polar Nonassociating Compounds

This study evaluates the performance of PC-SAFT, PCP-SAFT, SAFT-VR Mie, and SAFT-VR Mie-GV models in describing thermodynamic properties of ketones, ethers, and esters, including vapor pressure, saturation liquid density, isothermal compressibility, expansivity, heat capacities, speed of sound, and the Joule–Thomson coefficient over wide ranges of temperatures and pressures. In addition to pure-component behavior, vapor–liquid equilibria and selected derivative properties for limited polar and nonpolar binary systems are examined. SAFT-VR Mie shows a more consistent performance for second-order derivative properties. While incorporating a dipolar term aims to enhance accuracy, the impact depends on the molecular polarity and the sensitivity to dipole interactions. To gain deeper insight, the models’ performance in selected thermodynamic derivatives (∂A^res/∂V), (∂²A^res/∂V²), (∂²A^res/∂T²), and (∂²A^res/∂V∂T) is examined. Polar contributions are most significant in the second-order temperature derivative, particularly for highly polar compounds, and are more pronounced in SAFT-VR Mie-GV than in PCP-SAFT. A curated SQLite database is provided to support future model development and validation.