Thermodynamic properties of Lennard-Jones chain molecules: renormalization-group corrections to a modified statistical associating fluid theory

A modified version of the statistical associating fluid theory (SAFT), the so-called soft-SAFT equation of state (EOS), has been extended by a crossover treatment to take into account the long density fluctuations encountered when the critical region is approached. The procedure, based on White's work from the renormalization group theory Fluid Phase Equilibria 75, 53 (1992); L. W. Salvino and J. A. White, J. Chem. Phys. 96, 4559 (1992)], is implemented in terms of recursion relations where the density fluctuations are successively incorporated. The crossover soft-SAFT equation provides the correct nonclassical critical exponents when approaching the critical point, and reduces to the original soft-SAFT equation far from the critical region. The accuracy of the global equation is tested by direct comparison with molecular simulation results of Lennard-Jones chains, obtaining very good agreement and clear improvements compared to the original soft-SAFT EOS. Excellent agreement with vapor-liquid equilibrium experimental data inside and outside the critical region for the n-alkane series is also obtained. We provide a set of transferable molecular parameters for this family, unique for the whole range of thermodynamic properties.