Statistics
Scientific paper
Oct 1969
adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=1969phrv..186..210g&link_type=abstract
Physical Review, vol. 186, Issue 1, pp. 210-225
Statistics
77
Scientific paper
The thermodynamic properties of nonideal or interacting gases are studied using a thermodynamically consistent method which derives a state function for the gas from a separable Hamiltonian for the many-body system. The state function - the Helmholtz free energy - is a sum of translational, configurational, and internal components, and the statistical equilibrium state is calculated on a computer by minimizing the free energy in composition space at a given volume and temperature. A series of free-energy models is constructed to investigate the effects of various interactions. The effects on the equilibrium state of including Fermi-Dirac statistics in the translational free energy is shown to be small, while Coulomb and excluded-volume configurational terms produce large thermodynamic effects. The most important interaction effect, the modification of the internal partition function, is studied using a free-atom model and a confined-atom model which introduces volume- and temperature-dependent energy eigenvalues and partition-function sum terminations. The free-energy minimization method is shown to be a versatile and efficient tool for studying interacting gases, and provides quantitative estimates of the limits of validity of the various interaction models.
Graboske Harold C.
Harwood D. J.
Rogers Forrest J.
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