The thermal conductivity of argon, carbon dioxide and nitrous oxide

Abstract

The paper presents new, absolute measurements of the thermal conductivity of three gases: argon (Ar), carbon dioxide (CO 2) and nitrous oxide (N 2O). The measurements have been carried out with a transient hot-wire instrument in the temperature range 308 to 430 K and at pressures up to 11 MPa. For most of the range of thermodynamic states covered by the measurements it is estimated that the accuracy of the thermal conductivity data is one of ±0.3%. However, for carbon dioxide and nitrous oxide near their critical conditions the accuracy is degraded and the uncertainty may be as much as ±2%. The new experimental data for argon confirm the accuracy claimed for the thermal conductivity in the limit of zero-density. The thermal conductivity of the polyatomic gases in the limit of zero-density is used in conjunction with information on other transport cross-sections for the same systems, to extract a consistent set of cross-sections sensitive to the anisotropy of the intermolecular pair potential for use in the testing of proposed potential surfaces. Cross-sections for both of the available formulations of the thermal conductivity of a polyatomic gas due to Wang Chang and Uhlenbeck and Thijsse et al. are derived. For both gases it is shown that the Mason-Monchick approximation breaks down in either formulation. However, the effect of the failure on the formulation of Thijsse et al. is smaller and it is possible to represent the data with the aid of a single cross-section which has a very simple temperature dependence. The analysis also demonstrates that all available high-temperature thermal conductivity data for carbon dioxide are in substantial error. In the moderately dense gas the concept of a temperature-independent excess thermal conductivity is confirmed to a high degree of precision for carbon dioxide and argon when due allowance is made for the critical enhancement. A generalized correlation of the temperature dependence of the first density coefficient of thermal conductivity is broadly confirmed.