Helmholtz energy models for dipole interactions: Review and comprehensive assessment

Dipolar interactions play an important role for thermodynamic properties of many fluids and accordingly for their modeling. In molecular-based equation of state models, the effect of dipolar interactions is usually described by Helmholtz energy models. There are several Helmholtz energy models for dipolar interactions available in the literature today. In this work, eight dipole contribution models describing the dipole–dipole interactions of fluids were critically assessed by comparing their results with molecular simulation reference data of Stockmayer fluids. Therefore, the dipole contribution models were combined with an accurate Lennard-Jones (LJ) Helmholtz energy model. The following thermodynamic properties were considered in the comparison: vapor pressure, saturated densities, enthalpy of vaporization, surface tension (by using density gradient theory), critical point, second virial coefficient, and thermodynamic properties at homogeneous state points, such as the Helmholtz energy, pressure, chemical potential, internal energy, isochoric heat capacity, isobaric heat capacity, thermal expansion coefficient, isothermal compressibility, thermal pressure coefficient, speed of sound, Joule–Thomson coefficient, and Grüneisen parameter. For the evaluation of the dipole contribution models, molecular simulations for the Stockmayer fluid with the dipole moments of ${\mu }^2/4\pi {ϵ}_0\varepsilon {\sigma }^3=0.5,1,2,3,4,5$ were carried out. The results indicate, that all considered dipole models exhibit some significant weaknesses. Nevertheless, some dipole contribution models are found to provide a robust description for many properties and state ranges. Overall, the deviations of the dipole contribution models from the Stockmayer simulation data are, in most cases, an order of magnitude higher than the deviations of the LJ EOS from LJ simulation data.