Carbon Dioxide Chemistry on Titan's Surface

The surfaces of the moons of the outer Solar System are usually considered too cold (30-100 K) for significant chemistry to occur without the input of energy from exogenic sources (such as charged particles or VUV irradiation). In particular, Titan's thick atmosphere prevents significant amounts of high energy radiation from reaching the surface, limiting opportunities for surface chemical reactivity. Recently, we have identified carbamation, the reaction of carbon dioxide with primary amines to form carbamic acids, as a reaction that could occur thermally on Titan's surface. Amines should be present on Titan's surface, formed by photochemical reactions of N2 and CH4 in the upper atmosphere, and amine-containing molecules have been detected as a component of laboratory tholins made in terrestrial laboratories. There is some spectral evidence that CO2 is present on the surface, and CO2 has been definitively identified in the atmosphere. We use a combination of micro-Raman spectroscopy and UHV FTIR spectroscopy to examine the reaction products and kinetics of the carbamation reaction for a variety of primary amines. The reaction occurs readily at Titan surface temperatures (94 K), and leads to both carbamic acids and ammonium carbamate salts. Our kinetic data can be used to estimate the lifetime of CO2 on Titan's surface, and thus constrain the age of possible CO2-bearing cryovolcanic deposits.