A new statistical mechanical model for fluids model for fluids : [part i] an equation of state based on the hole theory on the hole theory

Abstract EN

The core principle of this model is to consider free space as an essential, explicit thermodynamic component of the fluid system.

The Hole Theory formulates this principle into statistical mechanical terms.

The model uses a modified Simha function with a liner combination of volumes rather than free lengths.

Here, the critical parameters are reproduced and the Van der Waals equation is obtained as an approximation.

Intermolecular attractions are regarded as weak, short-range contact bonds with chemical nature.

The bond energy is defined and determined in the close-packed fluid state (CPF) where the reference molecule is trapped inside a cage of its neighbors.

A suitable analytical function approximating the Lenard-Jones Devonshire cell potential is employed and the constants of this function are determinable from experimental vapor pressure data.

Non-random distribution is treated by the newly developed coordination state theory (CST).

The CST is also expressed in terms of the non-random factors.

It is general but reduces to the quasi-chemical theory for the 01 and the 1, 2-systems.

The local composition assumptions proved, on the light of the CST, invalid for describing non-randomness.