Thermodynamic or density scaling of the thermal conductivity of liquids.

Abstract

Thermodynamic or density scaling is applied to thermal conductivity (λ) data from the literature for the model Lennard-Jones (12-6) fluid; the noble gases neon to xenon; nitrogen, ethene, and carbon dioxide as examples of linear molecules; the quasi-spherical molecules methane and carbon tetrachloride; the flexible chain molecules n-hexane and n-octane; the planar toluene and m-xylene; the cyclic methylcyclohexane; the polar R132a and chlorobenzene; and ammonia and methanol as H-bonded fluids. Only data expressed as Rosenfeld reduced properties could be scaled successfully. Two different methods were used to obtain the scaling parameter γ, one based on polynomial fits to the group (TVγ) and the other based on the Avramov equation. The two methods agree well, except for λ of CCl4. γ for the thermal conductivity is similar to those for the viscosity and self-diffusion coefficient for the smaller molecules. It is significantly larger for the Lennard-Jones fluid, possibly due to a different dependence on packing fraction, and much larger for polyatomic molecules where heat transfer through internal modes may have an additional effect. Methanol and ammonia, where energy can be transmitted through intermolecular hydrogen bonding, could not be scaled. This work is intended as a practical attempt to examine thermodynamic scaling of the thermal conductivity of real fluids. The divergence of the scaling parameters for different properties is unexpected, suggesting that refinement of theory is required to rationalize this result. For the Lennard-Jones fluid, the Ohtori-Iishi version of the Stokes-Einstein-Sutherland relation applies at high densities in the liquid and supercritical region.