Group contribution methodology based on the statistical associating fluid theory for heteronuclear molecules formed from Mie segments

Abstract

A group contribution method for associating chain molecules based on the statistical associating fluid theory (SAFT-) The Journal of Chemical Physics 127, 234903 (2007) (2013)] is formulated within the framework of a group contribution approach (SAFT-γ Mie). Molecules are represented as comprising distinct functional (chemical) groups based on a fused heteronuclear molecular model, where the interactions between segments are described with the Mie (generalized Lennard-Jonesium) potential of variable attractive and repulsive range. A key feature of the new theory is the accurate description of the monomeric group-group interactions by application of a high-temperature perturbation expansion up to third order. The capabilities of the SAFT-γ Mie approach are exemplified by studying the thermodynamic properties of two chemical families, the n-alkanes and the n-alkyl esters, by developing parameters for the methyl, methylene, and carboxylate functional groups (CH 3 , CH 2 , and COO). The approach is shown to describe accurately the fluid-phase behavior of the compounds considered with absolute average deviations of 1.20% and 0.42% for the vapor pressure and saturated liquid density, respectively, which represents a clear improvement over other existing SAFT-based group contribution approaches. The use of Mie potentials to describe the group-group interaction is shown to allow accurate simultaneous descriptions of the fluid-phase behavior and second-order thermodynamic derivative properties of the pure fluids based on a single set of group parameters. Furthermore, the application of the perturbation expansion to third order for the description of the reference monomeric fluid improves the predictions of the theory for the fluid-phase behavior of pure components in the near-critical region. The predictive capabilities of the approach stem from its formulation within a group-contribution formalism: predictions of the fluid-phase behavior and thermodynamic derivative properties of compounds not included in the development of group parameters are demonstrated. The performance of the theory is also critically assessed with predictions of the fluid-phase behavior (vapor-liquid and liquid-liquid equilibria) and excess thermodynamic properties of a variety of binary mixtures, including polymer solutions, where very good agreement with the experimental data is seen, without the need for adjustable mixture parameters.

High-pressure densities and interfacial tensions of binary systems containing carbon dioxide+n-alkanes: (n-Dodecane, n-tridecane, n-tetradecane)

“…The reader is referred to reviews on the topic for further discussions [71,72,73,74,75,76]. Here we employ the SAFT version proposed by Lafitte et al [69], the basis of the third-generation SAFT-γ group contribution EoS [77]. Briefly, this SAFT version is a particular case of the generic SAFT methodology for potentials of variable range for molecules conformed of segments interacting through the Mie potential, u Mie , which can be represented by:…”

Fluid–fluid coexistence in an athermal colloid–polymer mixture: thermodynamic perturbation theory and continuum molecular-dynamics simulation

“…Very accurate versions of the statistical associating fluid theory (SAFT), which incorporate Wertheim's TPT1 treatment of chains [59], have been developed recently for molecules formed from segments interacting through the Mie potential (SAFT-VR and SAFT-γ Mie) [95,96]. The analytical SAFT-γ Mie equation of state can be employed to develop coarse-grained force fields for use in large-scale molecular simulation of a variety of systems [97][98][99][100][101] including surfactants [102,103], long chain molecules and polymeric systems [104].…”

A feasibility-based algorithm for Computer Aided Molecular and Process Design of solvent-based separation systems

“…The spent solvent is regenerated in an adiabatic flash drum at 1 bar. The property prediction model employed is the Statistical Associating Fluid Theory -γ Mie equation of state (Papaioannou et al, 2014). More details on the process and molecular models may be found in Burger et al (2015).…”