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  • 1990-1994  (2)
  • 1990  (2)
  • Kirkwood charging process  (1)
  • composition dependence  (1)
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  • 1990-1994  (2)
Year
  • 1990  (2)
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    International journal of thermophysics 11 (1990), S. 73-86 
    ISSN: 1572-9567
    Keywords: chemical potential ; Kirkwood charging process ; Lennard-Jones fluid ; scaled particle theory
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract A procedure frequently proposed in the literature for calculating chemical potentials relies on the Kirkwood charging process. Numerical problems associated with coupling large repulsive forces can be avoided by estimating the contribution to the chemical potential due to these forces with scaled particle theory. The contribution due to soft repulsive forces and attractive forces can be calculated with the Kirkwood charging process using distribution functions for a test particle obtained from integral equation theories. We have used the accurate HMSA theory of Zerah and Hansen to provide distribution functions in mixtures of Lennard-Jones molecules, and we have used the PYP theory of Lee to scale the distribution functions over the charging process. The theory provides accurate estimates of chemical potentials over a range of densities from gas-like to liquid-like when the reduced temperature kT/ɛ is greater than 2. Accurate results for excess free energy changes of mixing are also obtained at these conditions. At lower temperatures accurate results are obtained for low to moderate reduced densities (ρσ 3⩽0.5).
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    International journal of thermophysics 11 (1990), S. 373-380 
    ISSN: 1572-9567
    Keywords: composition dependence ; equation of state ; hybrid mixing rules
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract This paper discusses theoretical models for the composition dependence of equations of state and compares the quality of predictions against experimental thermodynamic property data. The mean density approximation (MDA) and the van der Waals one-fluid (VDW1) model are compared with hybrid mixing rules (HMR), in which rigorous composition dependence is used for the second and third virial coefficients and the conformai solution model is used for equation-of-state density terms beyond the third virial term. It is found that when values of unity are used for all binary and three-body unlike interaction parameters, calculated densities for methane-normal heptane mixtures have average absolute deviations of 3.54% for MDA, 4.04% for VDW1, and 2.59% for HMR. When vapor-liquid equilibrium calculations were performed for the methane-normal heptane system, average absolute deviations of calculatedK values from experimental values were 16.7% for methane and 36.4% for normal heptane using HMR, whereas when conformal solution model (CSM) mixing rules were used, the results were 34.8% for methane and 66.7% for normal heptane. When the binary interaction parameter for the characterization of interaction energies is determined, it is found to be less sensitive to state conditions in the case of HMR than either MDA or VDW1. These preliminary results suggest the potential of mixture equation-of-state methods which utilize rigorous composition dependence for the lower-order virial coefficients.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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