A thermodynamic framework for the thermal conductivity of dense fluids

Abstract

A thermodynamic framework that predicts the thermal conductivity $\lambda$ of simple fluids beyond the dilute-gas limit is introduced. By generalizing the transition-rate approach of particles on a lattice to conserved quantities in continuous space, an expression for the ratio $\lambda/\lambda_{\rm id}$ is derived, where $\lambda_{\rm id}$ is the dilute-gas value; the ratio depends solely on equilibrium thermodynamic properties and is therefore directly computable from any equation of state. The resulting formula quantitatively reproduces simulation data for hard spheres throughout almost the entire fluid range, and captures the behavior of Lennard-Jones fluids in the supercritical region where thermodynamic fluctuations remain moderate. Comparison with experimental data for argon, reported by other authors, also shows good agreement. These results provide evidence that transport coefficients of dense fluids can be expressed as their dilute-gas values multiplied by a universal function of equilibrium thermodynamic properties.