Liquid Structure and Hydrogen Bonding in Aqueous Hydroxylammonium Nitrate.

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.

Structural Properties of HEHN- and HAN-Based Ionic Liquid Mixtures: A Polarizable Molecular Dynamics Study.

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.

Formation and fragmentation of 2-hydroxyethylhydrazinium nitrate (HEHN) cluster ions: a combined electrospray ionization mass spectrometry, molecular dynamics and reaction potential surface study.

The 2-hydroxyethylhydrazinium nitrate ([HOCHCHNHNH]NO, HEHN) ionic liquid has the potential to power both electric and chemical thrusters and provide a wider range of specific impulse needs. To characterize its capabilities as an electrospray propellant, we report the formation of HEHN cluster ions in positive electrospray ionization (ESI) and their collision-induced dissociation. The experiment was carried out using ESI guided-ion beam mass spectrometry which mimics an electrospray thruster in terms of ion emission, injection into a vacuum and fragmentation in space.

Structures, proton transfer and dissociation of hydroxylammonium nitrate (HAN) revealed by electrospray ionization tandem mass spectrometry and molecular dynamics simulations.

Hydroxylammonium nitrate (HAN) is a potential propellant candidate for dual-mode propulsion systems that combine chemical and electrospray thrust capabilities for spacecraft applications. However, the electrospray dynamics of HAN is currently not well understood. Capitalizing on electrospray ionization guided-ion beam tandem mass spectrometry and collision-induced dissociation measurements, and augmented by extensive molecular dynamics simulations, this work characterized the structures and reaction dynamics of the species present in the electrosprays of HAN under different conditions, which mimic those possibly occurring in low earth orbit and outer space.

Thermal and Catalytic Decomposition of 2-Hydroxyethylhydrazine and 2-Hydroxyethylhydrazinium Nitrate Ionic Liquid.

To develop chemical kinetics models for the combustion of ionic liquid-based monopropellants, identification of the elementary steps in the thermal and catalytic decomposition of components such as 2-hydroxyethylhydrazinium nitrate (HEHN) is needed but is currently not well understood. The first decomposition step in protic ionic liquids such as HEHN is typically the proton transfer from the cation to the anion, resulting in the formation of 2-hydroxyethylhydrazine (HEH) and HNO. In the first part of this investigation, the high-temperature thermal decomposition of HEH is probed with flash pyrolysis (<1400 K) and vacuum ultraviolet (10.

Study of the Reaction of Hydroxylamine with Iridium Atomic and Cluster Anions ( = 1-5).

Elucidating the multifaceted processes of molecular activation and subsequent reactions gives a fundamental view into the development of iridium catalysts as they apply to fuels and propellants, for example, for spacecraft thrusters. Hydroxylamine, a component of the well-known hydroxylammonium nitrate (HAN) ionic liquid, is a safer alternative and mimics the chemistry and performance standards of hydrazine. The activation of hydroxylamine by anionic iridium clusters, Ir ( = 1-5), depicts a part of the mechanism, where two hydrogen atoms are removed, likely as H, and Ir(NOH) clusters remain.

Elucidating the differences in oxidation of high-performance α- and β- diisobutylene biofuels via Synchrotron photoionization mass spectrometry.

Biofuels are a promising ecologically viable and renewable alternative to petroleum fuels, with the potential to reduce net greenhouse gas emissions. However, biomass sourced fuels are often produced as blends of hydrocarbons and their oxygenates. Such blending complicates the implementation of these fuels in combustion applications.

Ionic Liquid Clusters Generated from Electrospray Thrusters: Cold Ion Spectroscopic Signatures of Size-Dependent Acid-Base Interactions.

We determine the intramolecular distortions at play in the 2-hydroxyethylhydrazinium nitrate (HEHN) ionic liquid (IL) propellant, which presents the interesting case that the HEH cation has multiple sites (i.e., hydroxy, primary amine, and secondary ammonium groups) available for H-bonding with the nitrate anion.

Experimental and Theoretical Investigations of the Radical-Radical Reaction: NH + NO.

The NH + NO reaction plays a key role during the early stages of hypergolic ignition between NH and NO. Here for the first time, the reaction kinetics of NH in excess NO was studied in 2.0 Torr of N and in the narrow temperature range 298-348 K in a pulsed photolysis flow-tube reactor coupled to a mass spectrometer.

Molecular Dynamics Simulations, Reaction Pathway and Mechanism Dissection, and Kinetics Modeling of the Nitric Acid Oxidation of Dicyanamide and Dicyanoborohydride Anions.

Direct dynamics simulations of HNO with dicyanamide anion DCA (, N(CN)) and dicyanoborohydride anion DCBH (, BH(CN)) were performed at the B3LYP/6-31+G(d) level of theory in an attempt to elucidate the primary and secondary reactions in the two reaction systems. Guided by trajectory results, reaction coordinates and potential energy diagrams were mapped out for the oxidation of DCA and DCBH by one and two HNO molecules, respectively, in the gas-phase and in the condensed-phase ionic liquids using the B3LYP/6-311++G(d,p) method. The oxidation of DCA by HNO is initiated by proton transfer.

Molecular Dynamics Simulations and Product Vibrational Spectral Analysis for the Reactions of NO with 1-Ethyl-3-methylimidazolium Dicyanamide (EMIMDCA), 1-Butyl-3-methylimidazolium Dicyanamide (BMIMDCA), and 1-Allyl-3-methylimidazolium Dicyanamide (AMIMDCA).

Direct dynamics trajectory simulations were carried out for the NO oxidation of 1-ethyl-3-methylimidazolium dicyanamide (EMIMDCA), which were aimed at probing the nature of the primary and secondary reactions in the system. Guided by trajectory results, reaction coordinates and potential energy diagrams were mapped out for NO with EMIMDCA, as well as with its analogues 1-butyl-3-methylimidazolium dicyanamide (BMIMDCA) and 1-allyl-3-methylimidazolium dicyanamide (AMIMDCA). Reactions of the dialkylimidazolium-dicyanamide (DCA) ionic liquids (ILs) are all initiated by proton transfer and/or alkyl abstraction between 1,3-dialkylimidazolium cations and DCA anion, of which two exoergic pathways are particularly relevant to their oxidation activities.

Kinetics of Methylamine Radical Thermal Decomposition and H-Abstraction from Monomethylhydrazine by H-Atom.

Methylamine radicals (CHNH) and amino radicals (NH) are major products in the early pyrolysis/ignition of monomethylhydrazine (CHNHNH). kinetics of thermal decomposition of CHNH radicals was analyzed by RRKM master equation simulations. It was found that β-scission of the methyl H-atom from CHNH radicals is predominant and fast enough to induce subsequent H-abstraction reactions in CHNHNH to trigger ignition.

Thermal Decomposition and Hypergolic Reaction of a Dicyanoborohydride Ionic Liquid.

In this study, in situ infrared spectroscopy techniques and thermogravimetric analysis coupled with mass spectrometry (TGA-MS) are employed to characterize the reactivity of the ionic liquid, 1-butyl-3-methylimidazolium dicyanoborohydride (BMIMDCBH), in comparison to the well-characterized 1-butyl-3-methylimidazolium dicyanamide (BMIMDCA) ionic liquid. TGA measurements determined the enthalpy of vaporization (Δ) to be 112.7 ± 12.

Computational Study of the Reaction of 1-Methyl-4-amino-1,2,4-triazolium Dicyanamide with NO: From Reaction Dynamics to Potential Surfaces, Kinetics and Spectroscopy.

Direct dynamics trajectories were calculated at the B3LYP/6-31G(d) level of theory in an attempt to understand the reaction of 1-methyl-4-amino-1,2,4-triazolium dicyanamide (MATDCA) with NO. The trajectories revealed an extensive intra-ion-pair proton transfer in MATDCA. The reaction pathways of the ensuing HDCA (i.

Ignition Delay Reduction with Sodium Addition to Imidazolium-Based Dicyanamide Ionic Liquid.

A range of ionic liquids (ILs) have been synthesized and modeled to better understand the role of the cation in the ignition of hypergolic ionic liquids. Vogelhuber et al. have shown by density functional theory methods that the addition of sodium cations to an ionic liquid promotes ignition with white fuming nitric acid (WFNA) by lowering energy barriers.

Spectroscopic Investigation of the Primary Reaction Intermediates in the Oxidation of Levitated Droplets of Energetic Ionic Liquids.

The production of the next generation of hypergolic, ionic-liquid-based fuels requires an understanding of the reaction mechanisms between the ionic liquid and oxidizer. We probed reactions between a levitated droplet of 1-methyl-4-amino-1,2,4-triazolium dicyanamide ([MAT][DCA]), with and without hydrogen-capped boron nanoparticles, and the nitrogen dioxide (NO) oxidizer. The apparatus exploits an ultrasonic levitator enclosed within a pressure-compatible process chamber equipped with complementary Raman, ultraviolet-visible, and Fourier-transform infrared (FTIR) spectroscopic probes.

Catalytic Decomposition of Hydroxylammonium Nitrate Ionic Liquid: Enhancement of NO Formation.

Hydroxylammonium nitrate (HAN) is a promising candidate to replace highly toxic hydrazine in monopropellant thruster space applications. The reactivity of HAN aerosols on heated copper and iridium targets was investigated using tunable vacuum ultraviolet photoionization time-of-flight aerosol mass spectrometry. The reaction products were identified by their mass-to-charge ratios and their ionization energies.

Flow-Tube Investigations of Hypergolic Reactions of a Dicyanamide Ionic Liquid Via Tunable Vacuum Ultraviolet Aerosol Mass Spectrometry.

The unusually high heats of vaporization of room-temperature ionic liquids (RTILs) complicate the utilization of thermal evaporation to study ionic liquid reactivity. Although effusion of RTILs into a reaction flow-tube or mass spectrometer is possible, competition between vaporization and thermal decomposition of the RTIL can greatly increase the complexity of the observed reaction products. In order to investigate the reaction kinetics of a hypergolic RTIL, 1-butyl-3-methylimidazolium dicyanamide (BMIMDCA) was aerosolized and reacted with gaseous nitric acid, and the products were monitored via tunable vacuum ultraviolet photoionization time-of-flight mass spectrometry at the Chemical Dynamics Beamline 9.

Ab initio kinetics and thermal decomposition mechanism of mononitrobiuret and 1,5-dinitrobiuret.

Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory.

Binding of alkenes and ionic liquids to B-H-functionalized boron nanoparticles: creation of particles with controlled dispersibility and minimal surface oxidation.

The interaction of B-H-functionalized boron nanoparticles with alkenes and nitrogen-rich ionic liquids (ILs) is investigated by a combination of X-ray photoelectron spectroscopy, FTIR spectroscopy, dynamic light scattering, thermogravimetric analysis, and helium ion microscopy. Surface B-H bonds are shown to react with terminal alkenes to produce alkyl-functionalized boron particles. The interaction of nitrogen-rich ILs with the particles appears, instead, to be dominated by boron-nitrogen bonding, even for an ILs with terminal alkene functionality.

Thermal decomposition mechanisms of alkylimidazolium ionic liquids with cyano-functionalized anions.

Because of the unusually high heats of vaporization of room-temperature ionic liquids (RTILs), volatilization of RTILs through thermal decomposition and vaporization of the decomposition products can be significant. Upon heating of cyano-functionalized anionic RTILs in vacuum, their gaseous products were detected experimentally via tunable vacuum ultraviolet photoionization mass spectrometry performed at the Chemical Dynamics Beamline 9.0.

Dynamics simulations and statistical modeling of thermal decomposition of 1-ethyl-3-methylimidazolium dicyanamide and 1-ethyl-2,3-dimethylimidazolium dicyanamide.

Quasi-classical, direct dynamics trajectories were calculated at the B3LYP/6-31G* level of theory, in an attempt to understand decomposition mechanisms of 1-ethyl-3-methylimidazolium dicyanamide (EMIM(+)DCA(-)) and 1-ethyl-2,3-dimethylimidazolium dicyanamide (EMMIM(+)DCA(-)). The trajectories showed many dissociation paths for these two ionic liquids. Using trajectory results as a guide, structures of transition states and products that might be important for decomposition of these two compounds were determined using density functional theory calculations.

Helium nanodroplet isolation and infrared spectroscopy of the isolated ion-pair 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide.

The ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide was vaporized at 420 K, and the ion-pair constituents were entrained in a beam of liquid He nanodroplets and cooled to 0.4 K. The vapor pressure was optimized such that each He droplet picked up a single ion-pair from the gas phase.

Thermal decomposition mechanism of 1-ethyl-3-methylimidazolium bromide ionic liquid.

In order to better understand the volatilization process for ionic liquids, the vapor evolved from heating the ionic liquid 1-ethyl-3-methylimidazolium bromide (EMIM(+)Br(-)) was analyzed via tunable vacuum ultraviolet photoionization time-of-flight mass spectrometry (VUV-PI-TOFMS) and thermogravimetric analysis mass spectrometry (TGA-MS). For this ionic liquid, the experimental results indicate that vaporization takes place via the evolution of alkyl bromides and alkylimidazoles, presumably through alkyl abstraction via an S(N)2 type mechanism, and that vaporization of intact ion pairs or the formation of carbenes is negligible. Activation enthalpies for the formation of the methyl and ethyl bromides were evaluated experimentally, ΔH(‡)(CH(3)Br) = 116.