title: Calculation of the thermal conductivity of low-density CH4-N2 gas mixtures using an improved kinetic theory approach.
abstract: The thermal conductivity of low-density CH4-N2 gas mixtures has been calculated by means of the classical trajectory method using state-of-the-art intermolecular potential energy surfaces for the CH4-CH4, N2-N2, and CH4-N2 interactions. Results are reported in the temperature range from 70 K to 1200 K. Since the thermal conductivity is influenced by the vibrational degrees of freedom of the molecules, which are not included in the rigid-rotor classical trajectory computations, a new correction scheme to account for vibrational degrees of freedom in a dilute gas mixture is presented. The calculations show that the vibrational contribution at the highest temperature studied amounts to 46% of the total thermal conductivity of an equimolar mixture compared to 13% for pure nitrogen and 58% for pure methane. The agreement with the available experimental thermal conductivity data at room temperature is good, within ±1.4%, whereas at higher temperatures, larger deviations up to 4.5% are observed, which can be tentatively attributed to deteriorating performance of the measuring technique employed. Results are also reported for the magnitude and temperature dependence of the rotational collision number, Z(rot), for CH4 relaxing in collisions with N2 and for N2 relaxing in collisions with CH4. Both collision numbers increase with temperature, with the former being consistently about twice the value of the latter.
authors.affiliation: Institut für Chemie, Universität Rostock, 18059 Rostock, Germany.
authors.forename: Robert
authors.initials: R
authors.lastname: Hellmann
authors.affiliation: Institut für Chemie, Universität Rostock, 18059 Rostock, Germany.
authors.forename: Eckard
authors.initials: E
authors.lastname: Bich
authors.affiliation: Department of Earth Science and Engineering, Imperial College London, London SW7 2AZ, United Kingdom.
authors.forename: Velisa
authors.initials: V
authors.lastname: Vesovic