Unraveling the initial steps of the ignition chemistry of the hypergolic ionic liquid 1-ethyl-3-methylimidazolium cyanoborohydride ([EMIM][CBH]) with nitric acid (HNO 3 ) exploiting chirped pulse triggered droplet merging.

The composition of the products and the mechanistic routes for the reaction of the hypergolic ionic liquid (HIL) 1-ethyl-3-methylimidazolium cyanoborohydride ([EMIM][CBH]) and nitric acid (HNO 3 ) at various concentrations from 10% to 70% were explored using a contactless single droplet merging within an ultrasonic levitation setup in an inert atmosphere of argon to reveal the initial steps that cause hypergolicity. The reactions were initiated through controlled droplet-merging manipulation triggered by a frequency chirp pulse amplitude modulation. Utilizing the high-speed optical and infrared cameras surrounding the levitation process chamber, intriguing visual images were unveiled: (i) extensive gas release and (ii) temperature rises of up to 435 K in the merged droplets. The gas development was validated qualitatively and quantitatively with Fourier Transform Infrared Spectroscopy (FTIR) indicating the major gas-phase products to be hydrogen cyanide (HCN) and nitrous oxide (N 2 O). The merged droplet was also probed by pulsed Raman spectroscopy which deciphered features for key functional groups of the reaction products and intermediates (-BH, -BH 2 , -BH 3 , -NCO); reaction kinetics revealed that the reaction was initiated by the interaction of the [CBH] - anion of the HIL with the oxidizer (HNO 3 ) through proton transfer. Computations indicate the formation of a van-der-Waals complex between the [CBH] - anion and HNO 3 initially, followed by proton transfer from the acid to the anion and subsequent extensive isomerization; these rearrangements were found to be essential for the formation of HCN and N 2 O. The exoergicity observed during the merging process provides a molar enthalpy change up to 10 kJ mol -1 to the system, which could be sufficient for a significant fraction of the reactants of about 11% to overcome the reaction barriers in the individual steps of the computationally determined minimum energy pathways.