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Title: Nitrogen Oxides As a Chemistry Trap in Detonating Oxygen-Rich Materials

Despite decades of research, the chemical processes and states of matter that govern the behavior of energetic materials under detonation conditions are not well understood, including the molecular-level processes that determine decomposition kinetics and energy release. Oxygen content is often employed as a simple and intuitive guide to the development and practical use of explosives, but its effect on detonation chemistry remains little studied, especially for the case of oxygen overabundance. To this end, we have conducted quantum molecular dynamics (QMD) simulations of zero oxygen balance and oxygen-rich mixtures of hydrogen peroxide and nitromethane under detonation-like conditions to near-equilibrium time scales. We find excellent agreement between our extrapolated chemical equilibrium properties and those from thermochemical models for the zero oxygen balance mixture. In contrast, for the oxygen-rich mixture, we observe the formation of nitrogen oxide intermediates, particularly nitrate ions (NO 3), that effectively act as an oxygen/nitrogen “trap” by precluding the formation of the equilibrium products N 2 and CO 2. Finally, our results could have implications for the design and modeling of oxygen-rich energetics in common military and industrial use.
Authors:
 [1] ;  [1]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Publication Date:
Report Number(s):
LLNL-JRNL-648219
Journal ID: ISSN 1089-5639; 768513
Grant/Contract Number:
AC52-07NA27344
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 118; Journal Issue: 16; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Research Org:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 36 MATERIALS SCIENCE; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; detonation; liquid explosives; hydrogen peroxide; nitromethane; density functional tight binding
OSTI Identifier:
1466117

Goldman, Nir, and Bastea, Sorin. Nitrogen Oxides As a Chemistry Trap in Detonating Oxygen-Rich Materials. United States: N. p., Web. doi:10.1021/jp501455z.
Goldman, Nir, & Bastea, Sorin. Nitrogen Oxides As a Chemistry Trap in Detonating Oxygen-Rich Materials. United States. doi:10.1021/jp501455z.
Goldman, Nir, and Bastea, Sorin. 2014. "Nitrogen Oxides As a Chemistry Trap in Detonating Oxygen-Rich Materials". United States. doi:10.1021/jp501455z. https://www.osti.gov/servlets/purl/1466117.
@article{osti_1466117,
title = {Nitrogen Oxides As a Chemistry Trap in Detonating Oxygen-Rich Materials},
author = {Goldman, Nir and Bastea, Sorin},
abstractNote = {Despite decades of research, the chemical processes and states of matter that govern the behavior of energetic materials under detonation conditions are not well understood, including the molecular-level processes that determine decomposition kinetics and energy release. Oxygen content is often employed as a simple and intuitive guide to the development and practical use of explosives, but its effect on detonation chemistry remains little studied, especially for the case of oxygen overabundance. To this end, we have conducted quantum molecular dynamics (QMD) simulations of zero oxygen balance and oxygen-rich mixtures of hydrogen peroxide and nitromethane under detonation-like conditions to near-equilibrium time scales. We find excellent agreement between our extrapolated chemical equilibrium properties and those from thermochemical models for the zero oxygen balance mixture. In contrast, for the oxygen-rich mixture, we observe the formation of nitrogen oxide intermediates, particularly nitrate ions (NO3), that effectively act as an oxygen/nitrogen “trap” by precluding the formation of the equilibrium products N2 and CO2. Finally, our results could have implications for the design and modeling of oxygen-rich energetics in common military and industrial use.},
doi = {10.1021/jp501455z},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 16,
volume = 118,
place = {United States},
year = {2014},
month = {3}
}