Thermodynamics of the van der Waals Dimers of O2, N2 and the Heterodimer (N2)(O2) and Their Presence in Earth's Atmosphere.

Abstract

The dimerization thermodynamics of N2 and O2, the principal components of Earth's atmosphere, have been determined from the respective second virial coefficients of the bound and metastable dimers calculated using the method of Stogryn and Hirschfelder that utilizes the Lennard-Jones (LJ) potential to account for intermolecular interactions. In addition, the thermodynamic properties of the heterodimer (N2)(O2) have been obtained using the same approach, employing combining rules to construct the LJ potential. Thus, Keq, ΔH, and ΔS for the three dimers are reported between 80-120 K. Over this temperature range, the ranking of Keq is (N2)(O2) > (O2)(O2) > (N2)(N2). The same trend is found for the exoethalpicity of dimer formation. For example, at 100 K, the Keq values are, respectively, 0.0406(14), 0.0215(5), and 0.0181(10), and the corresponding ΔH values are -2401(5), -2344(7), and -2279(1) J/mol. The mole fraction composition of the dimers in the atmosphere was calculated for altitudes up to 20 km. These calculations show that in the troposphere and the lower stratosphere (up to 20 km), the three dimers rank fifth to seventh in abundance, between CO2 and Ne. In this region, the average mole fractions of (N2)(N2), (O2)(O2), and (N2)(O2) are calculated to be 3.4(2) × 10-4, 2.80(9) × 10-5, and 1.95(7) × 10-4, respectively.