Nitrogen Oxides As a Chemistry Trap in Detonating Oxygen-Rich Materials
Abstract
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.
- Authors:
-
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1466117
- Report Number(s):
- LLNL-JRNL-648219
Journal ID: ISSN 1089-5639; 768513
- Grant/Contract Number:
- AC52-07NA27344
- Resource 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
- 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
Citation Formats
Goldman, Nir, and Bastea, Sorin. Nitrogen Oxides As a Chemistry Trap in Detonating Oxygen-Rich Materials. United States: N. p., 2014.
Web. doi:10.1021/jp501455z.
Goldman, Nir, & Bastea, Sorin. Nitrogen Oxides As a Chemistry Trap in Detonating Oxygen-Rich Materials. United States. https://doi.org/10.1021/jp501455z
Goldman, Nir, and Bastea, Sorin. Mon .
"Nitrogen Oxides As a Chemistry Trap in Detonating Oxygen-Rich Materials". United States. https://doi.org/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 = {Mon Mar 31 00:00:00 EDT 2014},
month = {Mon Mar 31 00:00:00 EDT 2014}
}
Web of Science
Works referenced in this record:
The heat and products of detonation in a calorimeter of CNO, HNO, CHNF, CHNO, CHNOF, and CHNOSi explosives
journal, August 1974
- Ornellas, D. L.
- Combustion and Flame, Vol. 23, Issue 1
Nitrogen-Rich Heterocycles as Reactivity Retardants in Shocked Insensitive Explosives
journal, April 2009
- Manaa, M. Riad; Reed, Evan J.; Fried, Laurence E.
- Journal of the American Chemical Society, Vol. 131, Issue 15
Aggregation kinetics of detonation nanocarbon
journal, May 2012
- Bastea, Sorin
- Applied Physics Letters, Vol. 100, Issue 21
Some aspects of detonation. Part 2.—Detonation velocity as a function of oxygen balance and heat of formation
journal, January 1958
- Martin, A. R.; Yallop, H. J.
- Trans. Faraday Soc., Vol. 54, Issue 0
The relationship of Impact Sensitivity with Structure of Organic High Explosives. II. Polynitroaromatic explosives
journal, April 1979
- Kamlet, M. J.; Adolph, H. G.
- Propellants, Explosives, Pyrotechnics, Vol. 4, Issue 2
Tris(triazolo)benzene and Its Derivatives: High-Density Energetic Materials
journal, September 2012
- Thottempudi, Venugopal; Forohor, Farhad; Parrish, Damon A.
- Angewandte Chemie International Edition, Vol. 51, Issue 39
The Stability of Detonation.
journal, August 1949
- Eyring, Henry; Powell, Richard E.; Duffy, George H.
- Chemical Reviews, Vol. 45, Issue 1
Diameter Effect Curve and Detonation Front Curvature Measurements for ANFO
conference, January 2002
- Catanach, R. A.
- Shock Compression of Condensed Matter - 2001: 12th APS Topical Conference, AIP Conference Proceedings
Advances in science and technology of modern energetic materials: An overview
journal, March 2008
- Badgujar, D. M.; Talawar, M. B.; Asthana, S. N.
- Journal of Hazardous Materials, Vol. 151, Issue 2-3
Synthesis of glycine-containing complexes in impacts of comets on early Earth
journal, September 2010
- Goldman, Nir; Reed, Evan J.; Fried, Laurence E.
- Nature Chemistry, Vol. 2, Issue 11
Prebiotic Chemistry within a Simple Impacting Icy Mixture
journal, May 2013
- Goldman, Nir; Tamblyn, Isaac
- The Journal of Physical Chemistry A, Vol. 117, Issue 24
Construction of tight-binding-like potentials on the basis of density-functional theory: Application to carbon
journal, May 1995
- Porezag, D.; Frauenheim, Th.; Köhler, Th.
- Physical Review B, Vol. 51, Issue 19
Self-consistent-charge density-functional tight-binding method for simulations of complex materials properties
journal, September 1998
- Elstner, M.; Porezag, D.; Jungnickel, G.
- Physical Review B, Vol. 58, Issue 11, p. 7260-7268
Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965
- Kohn, W.; Sham, L. J.
- Physical Review, Vol. 140, Issue 4A, p. A1133-A1138
First principles simulation of a superionic phase of hydrogen fluoride (HF) at high pressures and temperatures
journal, July 2006
- Goldman, Nir; Fried, Laurence E.
- The Journal of Chemical Physics, Vol. 125, Issue 4
X-ray scattering intensities of water at extreme pressure and temperature
journal, April 2007
- Goldman, Nir; Fried, Laurence E.
- The Journal of Chemical Physics, Vol. 126, Issue 13
Ab initio simulation of the equation of state and kinetics of shocked water
journal, March 2009
- Goldman, Nir; Reed, Evan J.; Kuo, I. -F. William
- The Journal of Chemical Physics, Vol. 130, Issue 12
Quantum mechanical corrections to simulated shock Hugoniot temperatures
journal, November 2009
- Goldman, Nir; Reed, Evan J.; Fried, Laurence E.
- The Journal of Chemical Physics, Vol. 131, Issue 20
A transient semimetallic layer in detonating nitromethane
journal, December 2007
- Reed, Evan J.; Riad Manaa, M.; Fried, Laurence E.
- Nature Physics, Vol. 4, Issue 1
Electronic structure of solid nitromethane: Effects of high pressure and molecular vacancies
journal, July 2002
- Margetis, Dionisios; Kaxiras, Efthimios; Elstner, Marcus
- The Journal of Chemical Physics, Vol. 117, Issue 2
Comparison of ReaxFF, DFTB, and DFT for Phenolic Pyrolysis. 1. Molecular Dynamics Simulations
journal, October 2013
- Qi, Tingting; Bauschlicher, Charles W.; Lawson, John W.
- The Journal of Physical Chemistry A, Vol. 117, Issue 44
Comparison of ReaxFF, DFTB, and DFT for Phenolic Pyrolysis. 2. Elementary Reaction Paths
journal, October 2013
- Bauschlicher, Charles W.; Qi, Tingting; Reed, Evan J.
- The Journal of Physical Chemistry A, Vol. 117, Issue 44
Ultrafast Shock Initiation of Exothermic Chemistry in Hydrogen Peroxide
journal, October 2013
- Armstrong, Michael R.; Zaug, Joseph M.; Goldman, Nir
- The Journal of Physical Chemistry A, Vol. 117, Issue 49
Chemical Equilibrium Detonation
book, September 2011
- Bastea, Sorin; Fried, Laurence E.
- Shock Waves Science and Technology Library, Vol. 6
Exp6-polar thermodynamics of dense supercritical water
journal, May 2008
- Bastea, Sorin; Fried, Laurence E.
- The Journal of Chemical Physics, Vol. 128, Issue 17
Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995
- Plimpton, Steve
- Journal of Computational Physics, Vol. 117, Issue 1
DFTB+, a Sparse Matrix-Based Implementation of the DFTB Method †
journal, July 2007
- Aradi, B.; Hourahine, B.; Frauenheim, Th.
- The Journal of Physical Chemistry A, Vol. 111, Issue 26
Extended Lagrangian Born–Oppenheimer molecular dynamics with dissipation
journal, June 2009
- Niklasson, Anders M. N.; Steneteg, Peter; Odell, Anders
- The Journal of Chemical Physics, Vol. 130, Issue 21
Thermal Properties of the Inhomogeneous Electron Gas
journal, March 1965
- Mermin, N. David
- Physical Review, Vol. 137, Issue 5A
A molecular dynamics method for simulations in the canonical ensemble
journal, June 1984
- Nosé, Shūichi
- Molecular Physics, Vol. 52, Issue 2
Canonical dynamics: Equilibrium phase-space distributions
journal, March 1985
- Hoover, William G.
- Physical Review A, Vol. 31, Issue 3
A Method for Tractable Dynamical Studies of Single and Double Shock Compression
journal, June 2003
- Reed, Evan J.; Fried, Laurence E.; Joannopoulos, J. D.
- Physical Review Letters, Vol. 90, Issue 23
Ultrafast transformation of graphite to diamond: An ab initio study of graphite under shock compression
journal, May 2008
- Mundy, Christopher J.; Curioni, Alessandro; Goldman, Nir
- The Journal of Chemical Physics, Vol. 128, Issue 18
Analysis of simulation technique for steady shock waves in materials with analytical equations of state
journal, November 2006
- Reed, Evan J.; Fried, Laurence E.; Henshaw, William D.
- Physical Review E, Vol. 74, Issue 5
Catalytic behaviour of dense hot water
journal, March 2009
- Wu, Christine J.; Fried, Laurence E.; Yang, Lin H.
- Nature Chemistry, Vol. 1, Issue 1
Extending the Density Functional Tight Binding Method to Carbon Under Extreme Conditions
journal, November 2011
- Goldman, Nir; Fried, Laurence E.
- The Journal of Physical Chemistry C, Vol. 116, Issue 3
Determination of a Density Functional Tight Binding Model with an Extended Basis Set and Three-Body Repulsion for Carbon Under Extreme Pressures and Temperatures
journal, April 2013
- Goldman, Nir; Goverapet Srinivasan, Sriram; Hamel, Sebastien
- The Journal of Physical Chemistry C, Vol. 117, Issue 15
Simulations of Shocked Methane Including Self-Consistent Semiclassical Quantum Nuclear Effects
journal, October 2012
- Qi, Tingting; Reed, Evan J.
- The Journal of Physical Chemistry A, Vol. 116, Issue 42
Electron-Ion Coupling in Shocked Energetic Materials
journal, November 2011
- Reed, Evan J.
- The Journal of Physical Chemistry C, Vol. 116, Issue 3
Phase Diagram and Electrical Conductivity of High Energy-Density Water from Density Functional Theory
journal, July 2006
- Mattsson, Thomas R.; Desjarlais, Michael P.
- Physical Review Letters, Vol. 97, Issue 1
Anomalous sound propagation and slow kinetics in dynamically compressed amorphous carbon
journal, January 2010
- Reed, Evan J.; Maiti, Amitesh; Fried, Laurence E.
- Physical Review E, Vol. 81, Issue 1
Ultrafast Detonation of Hydrazoic Acid ( )
journal, July 2012
- Reed, Evan J.; Rodriguez, Alejandro W.; Manaa, M. Riad
- Physical Review Letters, Vol. 109, Issue 3
Bonding in the Superionic Phase of Water
journal, May 2005
- Goldman, Nir; Fried, Laurence E.; Kuo, I-Feng W.
- Physical Review Letters, Vol. 94, Issue 21
Modeling of nitrogen oxides formation and destruction in combustion systems
journal, August 2000
- Hill, S. C.; Douglas Smoot, L.
- Progress in Energy and Combustion Science, Vol. 26, Issue 4-6
Formation of nitric oxide dimers on MgO-supported gold particles
journal, December 2012
- Fuente, Silvia A.; Fortunato, Leandro F.; Domancich, Nicolás
- Surface Science, Vol. 606, Issue 23-24
Very Low Temperature Surface Reaction: N2O Formation from NO Dimers at 70 to 90 K on Ag{111}
journal, May 1995
- Brown, W. A.; Gardner, P.; King, D. A.
- The Journal of Physical Chemistry, Vol. 99, Issue 18
A statistical mechanical theory of chemically reacting multiphase mixtures: Application to the detonation properties of PETN
journal, August 1984
- Ree, Francis H.
- The Journal of Chemical Physics, Vol. 81, Issue 3
Thermodynamics and diffusion in size-symmetric and asymmetric dense electrolytes
journal, August 2011
- Bastea, Sorin
- The Journal of Chemical Physics, Vol. 135, Issue 8
Decomposition of HMX at Extreme Conditions: A Molecular Dynamics Simulation
journal, August 2002
- Manaa, M. Riad; Fried, Laurence E.; Melius, Carl F.
- The Journal of Physical Chemistry A, Vol. 106, Issue 39
Thermal decomposition of energetic materials 58. Chemistry of ammonium nitrate and ammonium dinitramide near the burning surface temperature
journal, January 1993
- Brill, T. B.; Brush, P. J.; Patil, D. G.
- Combustion and Flame, Vol. 92, Issue 1-2, p. 178-186
Works referencing / citing this record:
Reactive flow modeling of the polymer bonded explosive LX-17 double shock experiments
journal, September 2018
- Rehagen, Thomas J.; Vitello, Peter; Bastea, Sorin
- Journal of Applied Physics, Vol. 124, Issue 12
First-Principles Monte Carlo Simulations of Reaction Equilibria in Compressed Vapors
journal, April 2016
- Fetisov, Evgenii O.; Kuo, I-Feng William; Knight, Chris
- ACS Central Science, Vol. 2, Issue 6