In this study, the reliability of the Peng–Robinson–Stryjek–Vera (PRSV) cubic equation of state to estimate the second and third virial coefficients and the Joule–Thomson inversion curves for the binary mixtures of benzene with 2-propanol, 2-butanol, and 2-pentanol was demonstrated. Besides, the mutual diffusion coefficients for the binary mixtures in the whole composition range were determined. Obtained results indicate that the considered mixtures show a positive deviation from Raoult’s Law. The results were analyzed to gain information to understand the structure of liquid influencing the diffusion phenomenon. The interplay between kinetic and thermodynamic contributions on the mutual diffusion coefficients was discussed. It has been shown that the structural changes and intermolecular interactions between benzene and 2-alkanol, which changes with the alcohol chain length, have a significant impact on the diffusion process. The investigation has shown that increasing in the alcohol chain length reinforces the strength of intermolecular forces
