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Relationships have been developed for the saturated-liquid density and the compressibility factor of saturated vapors by an extension of Pitzer's acentric factor approach. The fourth parameter for polar fluids defined previously by the authors in terms of the vapor pressure was utilized. For the saturated-liquid density and the critical compressibility factor quadratic terms were necessary to accurately represent the data for a wide range of normal and polar fluids including large polar molecules. Comparisons for substances not used in the development of the relationships indicate that good results can be obtained for polar fluids by the method of this study.Halm and Stiel (13) have extended Pitzer's acentric factor approach to the calculation of the vapor pressure and entropy of vaporization of polar fluids. A fourth parameter was defined in terms of the vapor pressure and shown to be applicable for other thermodynamic properties. In the present study this approach has been used to develop relationships for the calculation of the saturated-liquid and vapor densities of polar fluids.For saturated polar fluids, the functional dependence of the compressibility factor on temperature and molecular properties is( PO a E p2 po3 1 Equation (1) corresponds to the use of an intermolecular potential iunction containing four characteristic parameters, such as the superposition of the Kihara spherical core potential with a term accounting for dipole-dipole interactions, where po is the shortest distance between molecular cores at the potential minimum, r is the distance between molecular centers, a is the radius of the core, and g(e) represents the angular dependence of the dipole-dipole interaction. Only little theoretical progress has been made in the use of an intermolecular potential of this type for the calculation of the thermodynamic properties of polar fluids. O'Connell and Prausnitz ( 2 3 ) have obtained an expression for the second-virial coefficient of polar gases for spherical cores.Halm and Stiel (13) defined the reduced vapor pressure of a polar fluid as logPR= (logPR)(o) + O(bgPR)(l) +x(logPR)(2) ( 3 )where o is Pitzer's acentric factor ( 2 5 ) . At TR = 0.7, log PRto) = -1.00, log P,(l) = -1.00, and the polar correction log P R t z ) = 0 for TR 2 0.7, so that o .has the same definition as for a normal fluid, and the values of (log PR)(O) and (log P,)(l) are the same as tabulated by Pitzer, et al. for T R = 0.56 to 1.00. Log P R (~) was also defined to be 1.00 at TR = 0.6 so that the fourth
Relationships have been developed for the saturated-liquid density and the compressibility factor of saturated vapors by an extension of Pitzer's acentric factor approach. The fourth parameter for polar fluids defined previously by the authors in terms of the vapor pressure was utilized. For the saturated-liquid density and the critical compressibility factor quadratic terms were necessary to accurately represent the data for a wide range of normal and polar fluids including large polar molecules. Comparisons for substances not used in the development of the relationships indicate that good results can be obtained for polar fluids by the method of this study.Halm and Stiel (13) have extended Pitzer's acentric factor approach to the calculation of the vapor pressure and entropy of vaporization of polar fluids. A fourth parameter was defined in terms of the vapor pressure and shown to be applicable for other thermodynamic properties. In the present study this approach has been used to develop relationships for the calculation of the saturated-liquid and vapor densities of polar fluids.For saturated polar fluids, the functional dependence of the compressibility factor on temperature and molecular properties is( PO a E p2 po3 1 Equation (1) corresponds to the use of an intermolecular potential iunction containing four characteristic parameters, such as the superposition of the Kihara spherical core potential with a term accounting for dipole-dipole interactions, where po is the shortest distance between molecular cores at the potential minimum, r is the distance between molecular centers, a is the radius of the core, and g(e) represents the angular dependence of the dipole-dipole interaction. Only little theoretical progress has been made in the use of an intermolecular potential of this type for the calculation of the thermodynamic properties of polar fluids. O'Connell and Prausnitz ( 2 3 ) have obtained an expression for the second-virial coefficient of polar gases for spherical cores.Halm and Stiel (13) defined the reduced vapor pressure of a polar fluid as logPR= (logPR)(o) + O(bgPR)(l) +x(logPR)(2) ( 3 )where o is Pitzer's acentric factor ( 2 5 ) . At TR = 0.7, log PRto) = -1.00, log P,(l) = -1.00, and the polar correction log P R t z ) = 0 for TR 2 0.7, so that o .has the same definition as for a normal fluid, and the values of (log PR)(O) and (log P,)(l) are the same as tabulated by Pitzer, et al. for T R = 0.56 to 1.00. Log P R (~) was also defined to be 1.00 at TR = 0.6 so that the fourth
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