Ice Formation, Exsolution, and Multiphase Equilibria in the Methane–Ethane–Nitrogen System at Titan Surface Conditions

Titan is unique among the icy satellites in that it has a thick atmosphere, stable surficial bodies of liquid, and a precipitation system that promotes interactions between the two. Although Titan's surface conditions are typically assumed to be above the freezing point temperatures of the major constituent species of the climate system (methane, ethane, and nitrogen), conditions may be sufficiently cool across parts of Titan to allow for ice formation alongside known liquid-vapor phases. In this study, we used Raman spectroscopy, visual inspection, and the CRYOCHEM 2.0 equation of state to map the appearance of first ice and to quantify the amount of nitrogen dissolution into liquid in the methane–ethane–nitrogen system along a 1.5 bar isobaric cooling path in the temperature range 80–95 K. This was with the intent of (1) determining the effects nitrogen has on the phase behaviors of the methane–ethane binary system, and (2) establishing the temperatures and ternary mixing ratios needed for ice formation on Titan's surface. We found that ethane-rich mixtures enter a three-phase solid–liquid–vapor equilibrium and are characterized by nitrogen-rich exsolution upon freezing and ice that form at the bottom of the sample. With sufficient methane content, the mixtures cross a univariant four-phase solid–liquid–liquid–vapor boundary, which contributes to a distinct isothermal freezing point profile and ice that forms starting at the liquid–liquid interface. Our results generally agree with findings from previous studies of the methane–ethane–nitrogen system and are intended to add to our current understanding of Titan's geochemical processes.