A new non-extensive equation of state for the fluid phases of argon including the metastable states, from the melting line to 2300 K and 50 GPa

TL;DR

This paper introduces a new non-extensive equation of state for argon that accurately models its thermodynamic behavior across a wide range of temperatures and pressures, including metastable states.

Contribution

The work derives a novel equation of state from measured CV and P data, explicitly incorporating metastable states and extending validity to high pressures and temperatures.

Findings

Valid for temperatures up to 2300 K and pressures up to 50 GPa.

Predicts a maximum in the isochoric heat capacity along isochors.

Provides an approximate Tait-Tammann equation for the liquid phase.

Abstract

A new equation of state for argon has been developed in view to extend the range of validity of the equation of state previously proposed by Tegeler et al. (Ref. 4) and to obtain a better physical description of the experimental thermodynamic data for the whole fluid region (single-phase, metastable and saturation states). As proposed by Tegeler et al., this equation is also based on a functional form of the residual part of the reduced Helmholtz free energy. However in this work, the fundamental equation for the Helmholtz free energy has been derived from the measured quantities CV(rho,T) and P(rho,T). The empirical description of the isochoric heat capacity CV(rho,T) is based on an original empirical description containing explicitly the metastable states. The thermodynamic properties (internal energy, entropy, free energy) are then obtained by combining integration of CV(rho,T). The arbitrary functions introduced by the integration process have been deduced from a comparison between calculated and experimental pressure P(rho,T) data. The new formulation is valid for the whole fluid region from the melting line to 2300 K and for pressures up to 50 GPa. It also predicts existence of a maximum of the isochoric heat capacity CV along isochors as experimentally observed in several other fluids. For many applications, an approximate form of the equation of state for the liquid phase may be sufficient. A Tait-Tammann equation is therefore proposed between the triple point temperature and 148 K.