Adsorption isotherms and nucleation of methane and ethane on an analog of Titan’s photochemical aerosols

¹ GSMA, UMR CNRS 7331, Université de Reims Champagne-Ardenne, Reims, France
e-mail: pascal.rannou@univ-reims.fr
² Department of Chemistry and Biochemistry, California State University, Fullerton, CA, USA
³ Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA

Received: 25 April 2019
Accepted: 12 September 2019

Abstract

In planetary atmospheres, adsorption of volatile molecules occurs on aerosols prior to nucleation and condensation. Therefore, the way adsorption occurs affects the subsequent steps of cloud formation. In the classical theory of heterogeneous nucleation, several physical quantities are needed for gas condensing on a substrate like aerosols, such as the desorption energies of the condensing gases on the substrate and the wetting parameters of the condensed phases on the substrate. For most planetary atmospheres, the values of such quantities are poorly known. In cloud models, these values are often approximately defined from more or less similar cases or simply fixed to reproduce macroscopic observable quantities such as cloud opacities. In this work, we used the results of a laboratory experiment in which methane and ethane adsorption isotherms on tholin, an analog of photochemical aerosols, are determined. This experiment also permits determination of the critical saturation ratio of nucleation. With this information we then retrieved the desorption energies of methane and ethane, which are the quantitative functions describing the adsorption isotherms and wetting parameters of these two condensates on tholin. We find that adsorption of methane on tholin is well explained by a Langmuir isotherm and a desorption energy ΔF^o = 1.519 ± 0.0715 × 10⁻²⁰ J. Adsorption of ethane tholin can be represented by a Brunauer-Emmett-Teller isotherm of type III. The desorption energy of ethane on tholin that we retrieved is ΔF^o = 2.35 ± 0.03 × 10⁻²⁰ J. We also determine that the wetting coefficients of methane and ethane on tholin are m = 0.994 ± 0.001 and m = 0.966 ± 0.007, respectively. Although these results are obtained from experiments representative of the Titan case, they are also of general value in cases of photochemical aerosols in other planetary atmospheres.