Theory of excluded volume equation of state: higher approximations and new generation of equations of state for entire density range.
A novel theory of an equation of state based on excluded volume and formulated in two preceding papers for gases and gaseous mixtures is extended to the entire density range by considering higher (beginning from the third) approximations of the theory. The algorithm of constructing higher approximations is elaborated. Equations of state are deduced using the requirement of maximum simplicity and contain a single free parameter to be chosen by reason of convenience or simplicity or to be used as a fitting parameter with respect to the computer simulation database. In this way, precise equations of state are derived for the hard-sphere fluid in the entire density range. On the side, the theory reproduces most known earlier equations of state for hard spheres and determines their place in the hierarchy of approximations. Equations of state for van der Waals fluids are also presented, and their critical parameters are estimated.
Rusanov
Anatoly I
AI
Mendeleev Center, St. Petersburg State University, St. Petersburg 199034, Russia.