Oxidation of a Levitated Droplet of 1-Allyl-3-methylimidazolium Dicyanamide by Nitrogen Dioxide.

Understanding the reaction mechanisms of ionic liquids and their oxidizers is necessary to develop the next generation of hypergolic, ionic-liquid-based fuels. We studied reactions between a levitated droplet of 1-allyl-3-methylimidazolium dicyanamide ([AMIM][DCA]), with and without hydrogen-capped boron nanoparticles, and nitrogen dioxide (NO2 ). The reactions were monitored with Fourier-transform infrared (FTIR) and Raman spectroscopy. The emergence of new structures in the FTIR and Raman spectra is consistent with the formation of functional groups including organic nitrites (RONO), nitroamines (R1 R2 NNO2 ), and carbonitrates (R1 R2 C=NO2 - ). Possible reaction mechanisms based on these new functional groups are discussed. The reaction rates were deduced at various temperatures by heating the levitated droplets with a carbon dioxide laser. We thereby determined an overall activation energy of 38.5 ± 2.3 kJ mol-1 for the oxidation of [AMIM][DCA] for the first time.