ABSTRACT
Hydroxylammonium nitrate (HAN) has emerged as a promising component in ionic liquid-based spacecraft propellants. However, the physicochemical and structural properties of aqueous HAN have been largely overlooked. The purpose of this study is to investigate the hydrogen bonding in aqueous HAN and understand its implications on these properties and the proton transfer mechanism as a function of concentration. Classical polarizable molecular dynamics simulations have been employed with the APPLE&P force field to analyze the geometry of individual hydrogen bonds and the overall hydrogen-bonding network in various concentrations of aqueous HAN. Radial distribution functions (RDFs) and spatial distribution functions (SDFs) indicate the structural arrangement of the species and their hydrogen bonds. Projections of water density and the orientation of its electric dipole moment near the ions provide insight into the hydrogen-bonding network. The incorporation of water into the hydrogen-bonding network at high ion concentrations occurs via interstitial accommodation around the ions immediately outside the first solvation shell. While ion pairs are observed at all concentrations considered, the frequency of Ha···On hydrogen bonds increases substantially with the ion concentration. The findings contribute to a better fundamental understanding of HAN and the precursors of reactivity, crucial to the development of "green" spacecraft propellants.
ABSTRACT
Molecular dynamics simulations of binary mixtures comprising 2-hydroxyethylhydrazinium nitrate (HEHN) and hydroxylammonium nitrate (HAN) were conducted using the polarizable APPLE&P force field to investigate fundamental properties of multimode propulsion (MMP) propellants. Calculated densities as a function of temperature were in good agreement with experiments and similar simulations. The structural properties of neat HEHN and HAN-HEHN provided insights into their inherent, protic nature. Radial distribution functions (RDFs) identified key hydrogen bonding sites located at N-H···O and O-H···O within a first solvation shell of approximately 2 Å. Angular distribution functions further affirmed the relatively strong nature of the hydrogen bonds with nearly linear directionality. The increased hydroxylammonium cation (HA+) mole fraction shows the influence of competitively strong hydrogen bonds on the overall hydrogen bond network. Dominant spatial motifs via three-dimensional distribution functions along with nearly nanosecond-long hydrogen bond lifetimes highlight the local bonding environment that may precede proton transfer reactions.
