Evaluation of different equations of state and free-volume approaches for unified modeling of diffusion and thermodiffusion coefficients

This article is a development and testing of the previously suggested theoretical approach for simultaneous thermodynamic modeling of diffusion and thermodiffusion coefficients. The new theoretical framework allows for the calculation of transport properties with the aid of the concepts of penetration distances and emission functions, which are fully determined from thermodynamic equations that relate functions of state variables, that is, equations of state (EoS). Four underlying EoS were tested in this work, 3 different cubic EoS and PC-SAFT, with the aim of investigating the effect of the thermodynamic model on the description of experimental data. We also investigated the impact of different approaches to estimating the free volume, which is an essential part of the model. The results indicate that the application of the effective co-volume provides a superior representation of the diffusion and thermodiffusion coefficients, which should be included in the parameterization procedure for the selection of the unified model parameters. We evaluated the use of infinite dilution diffusion coefficient data and molecular dynamics simulation to validate model parameters, and discussed the possible ways to improve the model, including predicting diffusion data as a function of temperature.