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

• Published in: The Journal of chemical physics 2004-12, Vol.121 (21), p.10715-10724
• Main Authors: Llovell, Fèlix, Pàmies, Josep C, Vega, Lourdes F
• Format: Article
• Language: English
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.1809112

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.