Modeling of Strong Electrolytes with ePPC-SAFT up to High Temperatures

作者：Rozmus Justyna; de Hemptinne Jean Charles^*; Galindo Amparo; Dufal Simon; Mougin Pascal

来源：Industrial & Engineering Chemistry Research, 2013, 52(29): 9979-9994.

DOI：10.1021/ie303527j

An extension of the PPC-SAFT equation of state to treat strong electrolyte aqueous solutions is presented. It is capable of describing the behavior of such systems up to 473 K with a good precision and without requiring temperature-dependent model parameters. Long-range Coulombic interactions are taken into account using the mean spherical approximation (MSA) for a primitive model of the electrolyte solution, and the effect of solvation is described using short-range ion water interactions mediated through association sites. Pairing between anions and cations is also treated through site site interactions. A Born term is added to describe the change of dielectric constant resulting from solvation. A single ion-specific, temperature-independent model parameters are used, for 20 alkali-halide aqueous solutions. The Pauling ionic diameters are used for all terms (hard sphere, MSA, and Born). The dispersion energy of the ions is considered negligible. In the resulting ePPC-SAFT model, only the water ion association energy is considered as an adjustable parameter. The results show coherent energy density behavior with respect to ionic size. The approach allows the calculation of the mean ionic activity coefficient, density, or vapor pressure of the aqueous solutions over a wide range of temperatures and molalities (298-573 K and 0-6 m). Moreover, salting out of carbon dioxide and methane in saline water can also be predicted accurately. A discussion of the changes in ion hydration at different salinity is also presented taking advantage of the model proposed that explicitly includes ion water site site interactions.

• 出版日期2013-7-24