ABSTRACT
This work consists of the adaptation of a non-additive hard sphere theory inspired by Malakhov and Volkov [Polym. Sci., Ser. A 49(6), 745-756 (2007)] to a square-well chain. Using the thermodynamic perturbation theory, an additional term is proposed that describes the effect of perturbing the chain of square well spheres by a non-additive parameter. In order to validate this development, NPT Monte Carlo simulations of thermodynamic and structural properties of the non-additive square well for a pure chain and a binary mixture of chains are performed. Good agreements are observed between the compressibility factors originating from the theory and those from molecular simulations.
ABSTRACT
In this work, we propose a new methodology to determine association scheme and association parameters (energy and volume) of a SAFT-type EoS for hydrogen-bonding molecules. This paper focuses on 1-alkanol molecules, but the new methodology can also be applied for any other associating system. The idea is to use molecular simulation technique to determine independently monomer and free hydrogen fractions from which the association scheme can be deduced. The 3B scheme thus appeared to be the most appropriate for 1-alkanols. Once the association scheme is defined, the association strength can be back-calculated from molecular simulation results and used as an independent property for the equation of state parameters regression, in addition of the classical phase properties such as vapor pressure and liquid molar volume. A new set of parameters for 1-alkanol for the PPC-SAFT equation of state has been proposed following this methodology. Results are found in good agreement with experimental data for both phase properties and free hydrogen-bonding sites. Hence, this new methodology makes it possible to optimize parameters allowing an accurate reproduction of pure compounds data and yielding physically significant values for associating energy and associating volume.
