The thermodynamics of the van der Waals dimer and trimer formation in gaseous carbon dioxide and methane and their heterodimers with dinitrogen

• Published in: The Journal of chemical thermodynamics 2022-09, Vol.172, p.106818, Article 106818
• Main Author: Halpern, Arthur M.
• Format: Article
• Language: English
• Subjects: Carbon dioxide dimers and trimers; Equilibrium thermodynamics; Greenhouse gases; Methane dimers and trimers; Statistical thermodynamics; Van der Waals clusters
• ISSN: 0021-9614; 1096-3626
• DOI: 10.1016/j.jct.2022.106818

[Display omitted] The equilibrium thermochemical properties of the dimers and trimers of the greenhouse gases carbon dioxide and methane, as well as their heterodimers with dinitrogen, have been calculated from the CO2 and CH4 equations of state (EOSs) and statistical mechanics. The standard dimer and trimer equilibrium constants, along with the respective ΔHoandΔSo values are reported for CO2 and CH4 between 220 and 260, and 95 and 135 K, respectively, and for the heterodimers between 100 and 250 K. Statistical mechanical calculations based on experimental and computational data of the dimers provide qualitative agreement with the EOS results. The equilibrium thermochemical properties of the CH4 dimer and the CO2–N2 and CH4–N2 heterodimers are calculated using a Morse potential to represent pairwise interactions in an “atom–diatom” model that accounts for both bound and metastable rovibrational states.