Large Intermediates in Hydrazine Decomposition: A Theoretical Study of the N3H5 and N4H6 Potential Energy Surfaces

Dana, Alon Grinberg; Moore, Kevin B.; Jasper, Ahren W.; Green, William

doi:10.1021/acs.jpca.9b02217

Cited by 14 publications

(11 citation statements)

References 64 publications

(124 reference statements)

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“…Early works suggested N 2 H 4 decomposes either to a N 2 H 3 + H or NH 2 + NH 2 radical, with subsequent reactions involving the produced radicals producing NH 3 , H 2 , and N 2 . − Later, additional kinetics involving interactions with an active N 2 H 2 radical were added. − These studies and others were incorporated by Konnov and De Ruyck into a comprehensive mechanism which included NNH, H, and N radical interactions for the first time . More recently, N 3 H 5 and N 4 H 6 intermediates were suggested to participate in N 2 H 4 reaction pathways . Interactions between hydrazine and ammonia mechanisms are reciprocal since N 2 H 4 decomposition produces NH 3 and since NH 3 -derived NH 2 may recombine to produce N 2 H 4 .…”

Section: Nitrogen-based Fuel Oxidation and Decomposition Mechanismsmentioning

confidence: 99%

Progress and Prospective of Nitrogen-Based Alternative Fuels

et al. 2020

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Alternative fuels are essential to enable the transition to a sustainable and environmentally friendly energy supply. Synthetic fuels derived from renewable energies can act as energy storage media, thus mitigating the effects of fossil fuels on environment and health. Their economic viability, environmental impact, and compatibility with current infrastructure and technologies are fuel and power source specific. Nitrogen-based fuels pose one possible synthetic fuel pathway. In this review, we discuss the progress and current research on utilization of nitrogen-based fuels in power applications, covering the complete fuel cycle. We cover the production, distribution, and storage of nitrogen-based fuels. We assess much of the existing literature on the reactions involved in the ammonia to nitrogen atom pathway in nitrogen-based fuel combustion. Furthermore, we discuss nitrogen-based fuel applications ranging from combustion engines to gas turbines, as well as their exploitation by suggested end-uses. Thereby, we evaluate the potential opportunities and challenges of expanding the role of nitrogen-based molecules in the energy sector, outlining their use as energy carriers in relevant fields.

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Section: Nitrogen-based Fuel Oxidation and Decomposition Mechanismsmentioning

confidence: 99%

Progress and Prospective of Nitrogen-Based Alternative Fuels

et al. 2020

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“…detected it in the gas phase. See Richard and Ball, and Dana et al for computation studies of triazane.…”

Section: Results and Discussionmentioning

confidence: 99%

“…Kim et al 264 and Heo et al 265 also isolated triazane N 3 H 5 in its complexes with Ag + , whereas Forstel et al 266 detected it in the gas phase. See Richard and Ball, 267 and Dana et al 268 for computation studies of triazane.…”

Section: Isotactic Polyazane (Nh)mentioning

confidence: 99%

Helical Organic and Inorganic Polymers

et al. 2023

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Despite being a staple of synthetic plastics and biomolecules, helical polymers are scarcely studied with Gaussianbasis-set ab initio electron-correlated methods on an equal footing with molecules. This article introduces an ab initio second-order many-body Green's function [MBGF(2)] method with nondiagonal, frequency-dependent Dyson self-energy for infinite helical polymers using screw-axis-symmetry-adapted Gaussianspherical-harmonics basis functions. Together with the Gaussianbasis-set density-functional theory for energies, analytical atomic forces, translational-period force, and helical-angle force, it can compute correlated energy, quasiparticle energy bands, structures, and vibrational frequencies of an infinite helical polymer, which smoothly converge at the corresponding oligomer results. These methods can handle incommensurable structures, which have an infinite translational period and are hard to characterize by any other method, just as efficiently as commensurable structures. We apply them to polyethylene (2/1 helix), polyacetylene (Peierls' system) and polytetrafluoroethylene (13/6 helix) to establish the quantitative accuracy of MBGF(2)/cc-pVDZ in simulating their (angle-resolved) ultraviolet photoelectron spectra and of B3LYP/cc-pVDZ or 6-31G** in reproducing their structures, infrared and Raman band positions, phonon dispersions, and (coherent and incoherent) inelastic neutron scattering spectra. We then predict the same properties for infinitely catenated chains of nitrogen or oxygen and discuss their possible metastable existence under ambient conditions. They include planar zigzag polyazene (N 2 ) x (Peierls' system), 11/3-helical isotactic polyazane (NH) x , 9/4-helical isotactic polyfluoroazane (NF) x , and 7/2-helical polyoxane (O) x as potential high-energy-density materials.

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“…The present model does not consider the large complex formation and doubly protonated species such as H 2 NO 3 + in the thermal decomposition of N 2 H 4 . Green and co-workers investigated and established the mechanism for the reactions in the gas phase using transition state theory-based theoretical kinetics. Lang and Bohn found that the formation of the reactive H 2 NO 3 + can accelerate the decomposition of ammonium dinitramide (NH 4 N(NO 2 ) 2 ) based on the DFT calculations.…”

Section: Results and Discussionmentioning

confidence: 99%

Detailed Kinetic Model for the Thermal Decomposition of Hydrazine Nitrate in Nitric Acid Solution Based on Quantum Chemistry Calculations Combined with the Polarizable Continuum Model

2022

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The decomposition mechanism of hydrazine nitrate in nitric acid solutions was investigated using quantum chemistry calculations combined with the polarizable continuum model at the CBS-QB3//ωB97X-D/SMD level of theory. These calculations provided a detailed kinetic model incorporating rate coefficients and thermodynamic data. Rate coefficients were determined using traditional transition state theory, while diffusion-limited reactions were modeled based on the Einstein–Stokes equations. The resulting model comprised the kinetics for 108 reactions and thermodynamic data for 58 species. This model was validated by comparing simulations of the variations in chemical species during the decomposition process to experimental data acquired under isothermal conditions at 100 °C. The model was found to accurately reproduce the concentration changes of N2H4, HN3, and NH3 and also explained the reaction mechanism. The thermal decomposition was found to proceed via two parallel paths: N2H4 + HNO3 → H2O + HONO + N2H2 and N2H4 + HONO → HN3 + 2H2O. Following these reactions, a portion of the HN3 decomposes to produce NH3 through a multistep process. A sensitivity analysis showed that the rate of decomposition is greatly affected by the pH of the solution.

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Large Intermediates in Hydrazine Decomposition: A Theoretical Study of the N₃H₅ and N₄H₆ Potential Energy Surfaces

Cited by 14 publications

References 64 publications

Progress and Prospective of Nitrogen-Based Alternative Fuels

Progress and Prospective of Nitrogen-Based Alternative Fuels

Helical Organic and Inorganic Polymers

Detailed Kinetic Model for the Thermal Decomposition of Hydrazine Nitrate in Nitric Acid Solution Based on Quantum Chemistry Calculations Combined with the Polarizable Continuum Model

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