Thermal Oxidation Reaction between NH3 and O3: Low-temperature Formation of an NH4+ -bearing Salt

Abstract

Abstract NH3 has long been predicted to be an important component of outer solar system bodies, yet detection of this compound suggests a low abundance or absence on many objects where it would be expected. Here, we demonstrate that a thermally driven oxidation reaction between ammonia (NH3) and ozone (O3) in a H2O + NH3 + O3 mixture may contribute to the low abundance of NH3 on some of these objects, as this reaction efficiently occurs at temperatures as low as 70 K. We determined the overall activation energy for this reaction to be 17 ± 2 kJ mol−1, which is consistent with other chemical systems that react at cryogenic temperatures. The loss of these two compounds coincides with the formation of NH 4 + and NO 3 − at low temperatures, both of which are observable with infrared spectroscopy. Warming our H2O + NH3 + O3 mixtures through sublimation, we find a number of higher-temperature phases, such as ammonia hemihydrate, nitric acid, and ammonium nitrate (NH4NO3). The most stable of these is NH4NO3, which remains on the substrate until temperatures near 270 K. The salt product within this sample contains near-infrared spectral features between 2.0 and 2.22 μm, which is a spectral region of interest for several outer solar system objects, including the Uranian satellites Miranda, Ariel and Umbriel, and Pluto's satellite Charon.