Hydroxylammonium Nitrate Research Articles

Study on combustion characteristics of ammonium perchlorate enhanced hydroxylamine nitrate-based electronically controlled solid propellant

Electrically controlled solid propellants (ECSPs) have attracted significant attention as a novel class of solid propellants owing to their unique electrochemical properties. In this study, a series of ECSP formulations composed of hydroxylammonium nitrate (HAN), ammonium perchlorate (AP), and polyvinyl alcohol (PVA) were prepared and experimentally investigated to understand the effect of applied voltage on their combustion characteristics, and their combustion behavior was systematically characterized. The results demonstrated that the addition of AP decreased the initial conductivity of the ECSP; however, the average combustion rate during steady-state burning increased significantly, along with a corresponding increase in the combustion temperature. This effect became more pronounced with increasing AP concentration. The dissolved AP in the system acts as an efficient charge carrier, whereas the undissolved AP enhances the combustion performance by producing oxygen through thermal decomposition. Furthermore, even under atmospheric pressure conditions, the combustion of the ECSP can be effectively controlled by adjusting the applied voltage, with combustion ceasing upon removal of the voltage. The mechanism by which AP enhances combustion was analyzed, providing new insights for the optimization of ECSP formulations.

Ignition and flow combustion characteristics of hydroxylammonium nitrate - based liquid propellant based on electric method

Hydroxylamine nitrate (HAN)-based liquid propellants are characterized by high energy content and low toxicity ionic monopropellants, offering great potential application prospects in the space engine. This paper proposes an experimental system for electric ignition and combustion of HAN-based liquid propellant. The energy for decomposition, current, and combustion image of HAN-based liquid propellant are measured under different initial voltage, propellant volume, and the initial pressures in Ar and air atmospheres. The results show that the energy for decomposition decreased with an increase in initial voltage, propellant volume, and initial pressure. An increase in the initial voltage accelerates the reaction speed of HAN-based liquid propellant, and the energy for decomposition is approximately 3 J. An increase in the propellant volume decreases the equivalent resistance in the circuit, increasing the current and enhancing the thermal effect of the propellant. The accumulation of decomposition products and heat under high pressure reduced the energy for decomposition; the energy for decomposition is less than 1.5 J for the pressurization condition. Compared with the Ar atmosphere, the energy for decomposition of HAN-based liquid propellant shows better stability in the air atmosphere. The flow combustion device of HAN-based liquid propellant for the flow state is designed. The HAN-based liquid propellant is successfully ignited for different initial voltages and flow rates. The research results provide a reference for the design of space engine for HAN-based liquid propellant based on the electric ignition method.

Enhancement effect of Mo electrodes on the ignition characteristics of HAN-based gel propellant fuel and its combustion mechanisms

Hydroxylammonium nitrate (HAN) serves as a monopropellant fuel, renowned for its low toxicity and high-performance in space propulsion systems. HAN-based gel propellant may offer additional advantages, including long-term stability and excellent throttling capabilities. To better understand the ignition performance and combustion characteristics of this gel propellant, we prepared HAN-based gel propellant, and monitored its decomposition products using thermogravimetry (TG), Fourier Transform Infrared Spectroscopy (FTIR) and mass spectrometry (MS). Electrode materials of Mo, Cu, Ti and SUS 304 were fabricated to investigated their impact on ignition performance. It was found that the Mo electrode exhibited the shortest ignition delay time (ti) compared to Cu, Ti, and SUS 304. Meanwhile, the role of surface roughness of Mo electrode on the ignition delaytime (ti) and the ignition energy (Qi) were also studied. Our results revealed that, as the voltage increased from 100 V to 200 V, the fine-surfaced Mo electrode demonstrated a lower sensitivity to changes in ti compared to the rough-surfaced electrode. Additionally, the Qi of the rough-surfaced electrode decreased from 43.5 J to 16.7 J, while the Qi of the fine-surfaced electrode decreased from 52.5 J to 17.6 J. Combining a thermocouple, the combustion wave structure of the gel propellant was divided into pre-heating zone, condensed phase, electro chemical reaction zone, microexplosion-gases mixing zone and flame zone. Finally, the combustion model of HAN-based gel propellant was inferred to explain its combustion mechanism.

Tuning combustion and energy in hydroxylammonium nitrate (HAN)-based electrically controlled solid propellant

Solid propellants have been widely applied due to its high energy, rapid reaction, easy storage and convenient equipment. However, the further development of solid propellants has been hindered by the challenges associated with controlling their combustion process. In this research, we presented an electrically controlled solid propellant (ECSP), and its burning rate could be continuously adjusted with voltage. We investigated thermal decomposition behavior and gaseous products of ECSP using thermogravimetry–differential scanning calorimetry-mass spectrometry (TG-DSC-MS). The solid products were analyzed through energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). Based on the thermal decomposition behavior, gaseous products, and solid products, it was found that the thermal decomposition process could be divided into two stages: decomposition of ammonium nitrate (AN) and interactions between hydroxylamine nitrate (HAN) and other substances. The electrochemical impedance spectroscopy (EIS) experiments revealed that the electrical conductivity of ECSP increased with the pressure. Significantly, the peak combustion pressure of propellant increased by the rise of voltage from 3.17 MPa (150 V) to 5 MPa (250 V) in closed bomb. In addition, electricity reinforced the burning rate and powder force of propellant. Additionally, the electricity simultaneously affects electric and thermal decomposition processes. Electricity is used to control the burning rate and the total energy produced by propellant combustion. The characteristics of controllable energy has the potential to achieve controllable range of weapons, providing a new direction for development of smart weapons.

Laser-induced fluorescence detection of nitroxyl (HNO) formed from the thermal decomposition of hydroxylammonium nitrate vapor

The decomposition of the ionic liquid hydroxylammonium nitrate (HAN) produces gas phase products which have utility in spacecraft propulsion systems. Among the various gas phase species generated from HAN decomposition is the nitroxyl (HNO) radical, a highly reactive molecule with implications in both chemical and electric propulsion applications. The work described here used a laser-induced fluorescence platform to directly detect the relative density of the HNO radical formed by passing HAN vapor through heated porous disks of varying composition. The use of heated porous 316-stainless steel and aluminum disks showed significant HNO density production and is attributed to a surface hydrogen abstraction mechanism. There was also evidence of surface modification to the metal disks which resulted in a shift in the HNO density temperature profiles. The results reported demonstrate that use of a heated porous material can easily generate a molecular vapor at moderate temperatures for combustion and electric propulsion applications.

On the formation of ammonia from the thermal decomposition of hydroxylammonium nitrate vapor

The ionic liquid hydroxylammonium nitrate (HAN) is a promising propellant for various types of spacecraft propulsion systems. With respect to combustion and plasma-based electric propulsion, the thermal decomposition of HAN into gas phase species provides a convenient feed gas supply. While the decomposition of HAN in the liquid phase has been extensively studied, little is known about the decomposition chemistry of HAN vapor interacting with heated surfaces. The ability to decompose HAN vapor on a reactive surface could provide a means to control the feed gas composition and enhance the performance of spacecraft propulsion systems.In this initial qualitative study, HAN was vaporized and thermally decomposed using porous 316-stainless-steel and quartz disks under vacuum conditions. Decomposition products with low vapor pressures would condense on an in-line quartz tube which was subsequently collected and analyzed with Raman spectroscopy, NMR spectroscopy, and FT-IR spectroscopy. At temperatures above 440 K the 316-stainless-steel system produced significant quantities of ammonia which reacted with vaporized nitric acid to form ammonium nitrate. Temperatures below 440 K yielded partial HAN decomposition which resulted in a binary mixture of HAN and ammonium nitrate. The degree to which HAN was consumed was determined by analysis of the 1008 cm−1N-OH asymmetric Raman band of HAN and the 1049 cm−1 symmetric stretching Raman band of the nitrate ion, NO3−. The quartz system yielded significantly different results with no ammonium nitrate detected at temperatures above 440 K. Reformed HAN was the primary product detected at lower temperatures. The difference in reported measurements and visual observations highlights the distinct differences in HAN vapor decomposition chemistry from the two materials examined.

Synthesis of Hydroxylammonium Nitrate and Its Decomposition over Metal Oxide/Honeycomb Catalysts

The objectives of this study were to prepare a high-purity hydroxylammonium nitrate (HAN) solution and evaluate the performance of various types of metal oxide/honeycomb catalysts during the catalytic decomposition of the HAN solution. Hydroxylammonium nitrate was prepared via a neutralization reaction of hydroxylamine and nitric acid. FT-IR was used to analyze the chemical composition, chemical structure, and functional groups of the HAN. The aqueous HAN solution obtained from pH 7.06 showed the highest concentration of HAN of 60% and a density of 1.39 g/mL. The concentration of HAN solution that could be obtained when the solvent was evaporated to the maximum level could not exceed 80%. In this study, catalysts were prepared using a honeycomb structure made of cordierite (5SiO2-2MgO-2Al2O3) as a support, with Mn, Co, Cu, Pt, or Ir impregnated as active metals. The pore structure of the metal oxide/honeycomb catalysts did not significantly depend on the type of metal loaded. The Cu/honeycomb catalyst showed the strongest effect of lowering the decomposition onset temperature in the decomposition of the HAN solution likely due to the intrinsic activity of the Cu metal being superior to that of the other metals. It was confirmed that the effect of the catalyst on the decomposition mechanism of the aqueous HAN solution was negligible. Through a repetitive cycle of HAN decomposition, it was confirmed that the Cu/honeycomb catalyst could be recovered and reused as a catalyst for the decomposition of an aqueous HAN solution.

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. 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.

Experimental studies on effects of electrode material and voltage on electrolytic decomposition of Hydroxylammonium nitrate solution

Hydroxylammonium nitrate (HAN)-based propellants have been attracting attention as future low-toxicity liquid propellants owing to their ionic properties. HAN-based propellants are primarily decomposed via catalytic reactions. However, this method has several drawbacks, such as catalyst preheating and deactivation. Therefore, in this study, the electrical characteristics of the electrolysis process of a HAN solution, as well as the by-product gases and reaction residues were analyzed considering the electrode material and applied voltage as the controlling variables. SUS (a designation of stainless steel) electrodes have higher durability than Cu electrodes; however, their decomposition proceeds more slowly because of the suppression of the initial reaction at low voltages. This study confirmed that this suppression could be significantly addressed at a high voltage of 400 V. The investigated electrolytic decomposition mechanism of the HAN solution was validated by analyzing the gases generated during the electrolysis and residue after the reaction, using Fourier-transform infrared spectroscopy. This study has important implications for the development of volume-limited propulsion systems, such as micro-thrusters.

COMBUSTION CHARACTERISTICS OF HYDROXYLAMMONIUM NITRATE - WATER GELS

Linear burn rates of 80 wt.% hydroxylammonium nitrate (HAN) gels were characterized between 0.1 and 3.1 MPa. The burn rate of a HAN aqueous solution is relatively slow when the boiling temperature of the water content is lower than the decomposition temperature of HAN at lower pressures. However, the burn rate abruptly surges when the pressure exceeds a threshold value, at which the boiling temperature is higher than the decomposition temperature. As a result, additional fuels and stabilizers had to be added in HAN-based liquid monopropellants to improve the burning characteristics. Fumed silica adsorbs water in a HAN aqueous solution through the formation of hydrogen bonds between the silica particles and water molecules and is effective on stabilizing the burn rate in the high pressure range. Hydrophilic fumed silica (CAB-O-SIL M5) was added to 80 wt.% HAN aqueous solutions to produce the HAN gel. Burn rate behavior of the gelled HAN solution was experimentally studied via strand burner tests at pressures between 0.1-3.1 MPa, which is the operating pressure range relevant to space thrusters, using a pressure chamber with observation windows. It was found that gelation of HAN aqueous solutions using fumed silica effectively eliminated the burn rate jump between 1.1-1.6 MPa that typically occurs in HAN aqueous solutions.

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. 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.

Enhancing risk/safety management of HAN-based liquid propellant as a green space propulsion fuel: A study of its hazardous characteristics

The knowledge of hazard classification of hydroxylammonium nitrate (HAN)-based liquid propellant is an essential subject in prevention of safe and transportation accidents. To improve hazard classification of the propellant, various tests were conducted on both material sample and packaged sample. Differential scanning calorimeter was utilized to study thermal decomposition parameters, resulting in the determination of high values for both thermal decomposition and explosion temperatures. Koenen and EIDS gap tests were used to evaluate the heat response under high confinement and the sensitivity of shock, respectively. The results indicated that the propellant was insensitive to shock wave, with a limiting diameter of 3.0 mm. The external fire test was conducted to elucidate the explosion characteristics of the packaged propellant. Pictorial information and temperature data were recorded using high-speed camera and infrared imager. The results revealed that a mass explosion occurred during the fire process. The combination of the perforated witness screen, long-range metallic projections and high-value heat flux led to the classification of the packaged HAN-based liquid propellant as Class 1.1 C, more stringent than the traditional Class 1.3 C. The study is expected to offer valuable insights for the safety of development, preservation, and conveyance of HAN-based liquid propellant.

Experimental and simulation studies on the influencing factors of mechanical stimulation threshold of HAN-based liquid propellant

ABSTRACT This paper presents a comprehensive analysis of the effects of water content and ambient temperature on the mechanical stimulation threshold of hydroxylammonium nitrate (HAN) based liquid propellant. Based on the stability analysis of slow cook-off test for HAN-based liquid propellant, the mechanical sensitivity of the liquid propellant with different water content was evaluated at different ambient temperatures in detailed. Differential scanning calorimetry was employed to investigate the influence of water content on the stability, demonstrating a significant dependence on water content. Additionally, the impact sensitivity of liquid propellant, which is strongly influenced by the variation of initiating bond length with the ambient temperature, was investigated using large scale atomic/molecular massively parallel simulator (LAMMPS), highlighting a notable correlation between the impact sensitivity and ambient temperature. The findings of this research contribute towards understanding the hazard level associated with HAN-based liquid propellant, providing crucial guidance for its formulation design, practical application and safety management.

Experimental Study on the Catalytic Ignition Characteristics of a Dual-Mode Ionic Liquid Propellant in Model Thrusters

An experimental study was carried out on the ignition characteristics of the HAN/(Emim)(EtSO4) (hydroxylammonium nitrate and 1-ethyl-3-methyl-imidazolium ethyl sulfate) dual-mode ionic liquid monopropellant in chemical propulsion mode in model thrusters. Firstly, a model thruster with a detachable convergent nozzle was designed and fabricated. Secondly, catalytic ignition experiments at different flow rates were carried out in atmosphere and in high chamber pressure environment, respectively, using a model thruster, with and without the convergent nozzle. During the catalytic ignition process, measurement methods such as thermocouple, pressure sensor, and flue gas analyzer were employed to obtain the temperature at different depths of the catalytic bed, the pressure of the combustion chamber, and the concentration variations of gaseous products CO, CO2, CH4, SO2, NO, and NO2. Then the three characteristic stages of water evaporation, HAN decomposition, and (Emim)(EtSO4) combustion were analyzed at the initiation time, and the reaction characteristics in the process of the catalytic ignition were analyzed. In addition, the composition and concentration of the combustion products at equilibrium were theoretically calculated. The effects of temperature and pressure on the concentrations of five main gaseous products were studied. Finally, the exhaust gas of the three groups of catalytic ignition experiments under different pressure environments was separately collected and measured with gas chromatography (GC) when the experiments approached equilibrium, the result of which roughly agrees with the theoretical calculations. These results are of great significance for exploring the chemical propulsion of the dual-mode ionic liquid propellant and understanding its physical catalytic combustion mechanisms.

Janus-type hypergolic fuels for hybrid systems using hydrogen peroxide and hydroxylammonium nitrate-based oxidizers

Development of fully green hybrid propulsion systems, in which both the oxidizer and the fuel are environmentally benign, while having a desirable performance under in-space conditions, is a formidable challenge. Herein, we present new air-stable solid propellants capable of exhibiting hypergolic ignitions with commercially available H2O2 (70 %) and its low-freezing formulation containing hydroxylammonium nitrate (HAN). A top performing Janus-type fuel 15 showed remarkable ignition delay time of 4 ms with HAN-H2O2 formulation, even at −40 ℃. The Janus-type design approach allowed modulation of the ignition delay times by varying the carbon chain-length, the type of the used transition metals and the molecular structure of the resulted solid fuels. Studies of HAN and related salts formulations with H2O2 allowed us to get an insight into the reasons of the stability of HAN-H2O2 formulations. UV–vis and EPR monitoring of selected fuels reactions with oxidizers, as well as surface wettability measurements, provided a valuable information related to the better understanding of the hypergolic reaction mechanisms, which should contribute to the design of the next generation of green hypergolic propulsion systems. We also successfully tested fuel 15 in a custom-made small-scale static hybrid motor system, injecting H2O2 in a sequence of pulse or in continuous flow modes.

Ignition of an ionic liquid dual-mode monopropellant using a microwave plasma torch

The blend of hydroxylammonium nitrate (HAN) and imidazole-based ionic liquid has shown good feasibility in chemical and electric dual-mode green space propulsion. As conventional catalyst-driven ignition faces challenges arising from long preheat delay and catalyst failure, this work designs a novel ignition actuator using a microwave plasma torch. The precise tuning of the ¼-λ resonant cavity and improvement in the quality factor (QF) of the microwave igniter make the device efficient and thus allow the propellant to be ignited at a power of approximately 100 W. In the present reduced test rig, the maximum fuel flow rate corresponds to 0.1 N chemical thrusters, and the plasma-assisted ignition is mainly attributed to thermal and kinetic effects. The temperature of the actuator and the plasma torch is investigated by infrared thermometry and spectral fitting of excited molecule nitrogen, respectively. First, the hot electrode tube helps evaporate water molecules and accelerate the liquid jet through rapid gas expansion. Then, the ionic liquid quickly decomposes to small species when the flow reaches the torch with a nitrogen vibrational temperature above 4000 K and rotational temperature above 2000 K. Meanwhile, the nonequilibrium plasma-excited species enhance the combustion of gaseous intermediates by direct impact dissociation, where the OH radical profile is visualized using the planar laser-induced fluorescence technique. In addition, the copper atoms released by plasma erosion are expected to exhibit a significant catalytic effect on ionic liquid decomposition, which is a critical step in controlling the overall reaction rate. It is also noted that such mild erosion does not affect the multi-start operations during the firing test that lasts for at least 30 min.

Experimental Studies on Parametric Effects and Reaction Mechanisms in Electrolytic Decomposition and Ignition of HAN Solutions.

The green propellant hydroxylammonium nitrate (HAN) is a good alternative to the conventional propellants in space propulsion applications because of its low toxicity and high energy density. Electrolytic decomposition and ignition of HAN solution, an ionic liquid, is a promising approach. In this work, comprehensive experimental studies were conducted to examine effects of different electrolytic voltages, electrode surface areas, and HAN concentrations on the decomposition process. In the test cases, an optimum electrolytic voltage appears to exist, which leads to the fastest decomposition process. As the voltage increases, a larger electrode surface area on the anode side should be used to overcome an anodic inhibition phenomenon and accelerate the electrolytic process. A high concentration of HAN solution is preferred for its decomposition and ignition. Results also reveal that the electrolytic process of a HAN solution could eventually trigger thermal decomposition reactions, raising the maximum temperature to around 550 K at the final stage. A detailed chemical reaction mechanism was proposed, based on the experimental data and FTIR spectra analyses. Results obtained herein would provide fundamental understandings on the complex electrochemical and physical processes and should be helpful for future applications of the electrolytic decomposition and ignition technology.

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. While being ionic in nature, the HAN monomer, however, adopts a stable covalent structure HONH2·HNO3 in the gas phase. Spontaneous proton transfer between the HONH2 and HNO3 moieties within the HAN monomer can be induced in the presence of a NO3-, a water ligand or a second HAN monomer within 3-5 Å or a H+ within 8 Å, regardless of their collision impact parameters. These facts imply that HAN proton transfer is trigged by a charge and/or a dipole of the collision partner without the need of chemical interaction or physical contact. Moreover, the addition of NO3- to HAN leads to the formation of a stable -O3N·HONH3+·NO3- anion in negative electrosprays. In contrast, when a proton approaches the HONH2·HNO3 structure, dissociative reactions occur that lead to the H2O, NO2 and HONH2 fragments (and their cations) but not intact HAN species in positive electrosprays.

COMPARATIVE STUDY OF THE THERMAL DECOMPOSITION OF HYDROXYLAMMONIUM NITRATE GREEN ENERGETIC COMPOUND: COMBINATION BETWEEN EXPERIMENTAL AND DFT CALCULATION

COMPARATIVE STUDY OF THE THERMAL DECOMPOSITION OF HYDROXYLAMMONIUM NITRATE GREEN ENERGETIC COMPOUND: COMBINATION BETWEEN EXPERIMENTAL AND DFT CALCULATION

Effect of Metal Sequestrants on the Decomposition of Hydroxylammonium Nitrate

Hydroxylammonium nitrate (HAN) is an energetic salt used in flight-proven green monopropellants such as ASCENT (formerly AF-M315E), flown in NASA’s 2019 Green Propellant Infusion Mission, and SHP163, flown in JAXA’s Rapid Innovative Satellite Technology Demonstration-1. The decomposition of HAN is catalyzed by metals commonly found in storage tanks, a factor limiting its use. This work investigates the ability of metal-sequestering chelating agents to inhibit the decomposition of HAN. Isothermal and dynamic thermogravimetric analysis (TGA) were used to find isothermal decomposition rates, decomposition onset temperatures, and first-order Arrhenius reaction rate parameters. In the present research, 2,2′-bipyridine (Bipy), triethanolamine (TEA), and ethylenediaminetetraacetic acid (EDTA) were studied as 0.05, 0.1, 0.5, 1, and 5% by weight additives in 90% aqueous HAN. An isothermal decomposition rate of 0.137%/h at 348 K was observed for HAN. The addition of 1% Bipy and 1% TEA reduced the isothermal decomposition rate by 20.4% to 0.109%/h, and by 3.65% to 0.132%/h, respectively, showing that Bipy can inhibit decomposition. The addition of 1% EDTA increased the isothermal decomposition rate by 12.4% to 0.154%/h. Bipy was found to increase the decomposition onset temperature from 454.8 K to 461.8 K, while the results for TEA and EDTA were inconclusive. First order reaction rates calculated by the Ozawa-Flynn-Wall method were found to be insufficient to capture the effects of the tested additives. Bipy was found to inhibit the decomposition of HAN, while TEA and EDTA produced little or negative effect, a result believed to be due to poor metal complex stability at low pH and high acidity, respectively. Spectrophotometry, used for colorimetric analysis of Bipy+iron complexes, showed that Bipy forms chelate complexes with trace iron impurities when added to HAN solutions.