Thermal decomposition of energetic materials. 62. Reconciliation of the kinetics and mechanisms of TNT on the time scale from microseconds to hours

Brill, T. B.; James, K. J.

doi:10.1021/j100136a018

Cited by 57 publications

(60 citation statements)

References 9 publications

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“…Many such compounds, including 2,4,6-trinitrotoluene, are observed to produce a large amount of NO compared with NO 2 when they are heated slowly or flash heated. 37,38 When a much larger number (19) of substituents and flash heating are used, it is observed that electron-donating substituents produce much more NO than electron-withdrawing substituents. 39 It is not possible to quantitate this pattern because of the large number of possible intermolecular processes and competing secondary oxidation-reduction reactions in the condensed phase before NO appears in the gas phase.…”

Section: Discussionmentioning

confidence: 99%

Influence of the substituent on the major decomposition channels of the NO2 group inpara-substituted nitrobenzenes: a tandem mass spectrometric study

Brill

James

Chawla

et al. 1999

J. Phys. Org. Chem.

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The relative extents of loss of NO 2 and NO were determined by 70 eV electron ionization and tandem mass spectrometry using B/E linked scans to investigate metastable (unimolecular) and collision-induced dissociation processes for molecular ions formed by electron ionization of para-substituted nitrobenzene compounds. The substituents used (NO 2 , CHO, H, OCH 3 ) represent a wide range of electron donor-acceptor properties. Loss of NO 2 was favored by electron-withdrawing groups, while an electron-donor group favored loss of NO. Ion fragmentation mechanisms are consistent with the hypothesis that NO 2 to ONO (nitro to nitrite) isomerization precedes the loss of NO. Ring fragmentation (loss of CO) was observed only after all of the electron-withdrawing groups had dissociated. while the electron-donor group OCH 3 remained attached to the ring in the analogous CO elimination. These results are placed in the context of the thermolysis behavior of nitroaromatic explosives.

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Section: Discussionmentioning

confidence: 99%

Influence of the substituent on the major decomposition channels of the NO2 group inpara-substituted nitrobenzenes: a tandem mass spectrometric study

Brill

James

Chawla

et al. 1999

J. Phys. Org. Chem.

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“…Brill and James [15] and Long et al [12] suggest the presence of autocatalysis in the TNT decomposition process. Here, we apply a novel calibration methodology to modify an existing kinetic model that features autocatalysis.…”

Section: Determination Of Decomposition Kineticsmentioning

confidence: 99%

Calibration of Chemical Kinetic Models Using Simulations of Small-Scale Cookoff Experiments

Wemhoff

Becker

Burnham

2008

Heat Transfer: Volume 3

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“…For instance, at low energies, trinitrotoluene (TNT) reacts by oxidation of the methyl moiety, CH 3 , while C-NO 2 bond homolysis appears to be dominant at higher temperatures. (37) Wight and co-workers have addressed the issue of temperature control and have suggested a means to relate isothermal or non-isothermal conditions. (38,39) Our own work, to be summarized, has focused on measuring the temperature during the combustion process by monitoring the cracking pattern of a "thermometer" molecule.…”

Section: Introductionmentioning

confidence: 99%

The Mechanism and Dynamics of Explosive Combustion in Aerosol Fuels

Baer¹,

Miller²

2006

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The public reporting burden for this collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and maintaining the data needed, and completing and reviewing the collection of information. Send comments regarding this burden estimate or any other aspect of this collection of information, including suggestions for reducing the burden, to the Department of Defense, Executive Services and Communications Directorate (0704-0188). Respondents should be aware that notwithstanding any other provision of law, no person shall be subject to any penalty for failing to comply with a collection of information if it does not display a currently valid OMB control number. PLEASE DO NOT PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION Department of Chemistry REPORT NUMBERUniversity of North Carolina Chapel Hill, NC 27599-3290 SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES)AFOSR ABSTRACTThe research involves the production of high energy material particles with diameters between 1 and 5 om and the study of its subsequent combustion by rapid laser heating or photolysis. Alternatively, the high-energy ionic liquids with no vapor pressure are placed on a plate inside the vacuum and irradiated with high intensity IR radiation. In either case, the reaction products are followed by single photon vacuum UV laser ionization in a time of flight (TOF) mass spectrometer. The purpose is the elucidation of reaction mechanisms in high density or condensed phases and the development of more efficient methods of combustion. The experimental set-up includes aerosol generation tools that inject the particles at atmospheric pressure into an aerodynamic lens, which focuses the particles onto the center of a 3 mm expansion nozzle, whereupon the particles are accelerated to velocities of 200 to 300 m/s depending upon their size. The research involves the production of high energy material particles with diameters between 1 and 5 ýtm and the study of its subsequent combustion by rapid laser heating or photolysis. Alternatively, the high-energy ionic liquids with no vapor pressure are placed on a plate inside the vacuum and irradiated with high intensity IR radiation. In either case, the reaction products are followed by single photon vacuum UV laser ionization in a time of flight (TOF) mass spectrometer. The purpose is the elucidation of reaction mechanisms in high density or condensed phases and the development of more efficient methods of combustion. The experimental set-up includes aerosol generation tools that inject the particles at atmospheric pressure into an aerodynamic lens, which focuses the particles onto the center of a 3 mm expansion nozzle, whereupon the particles are accelerated to velocities of 200 to 300 m/s depending upon their size. The particles are sized by laser light scattering, ignited by a high power CO 2 laser pulse, and the products ionized by the 10.48 eV light produced by third harmonic gener...

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Thermal decomposition of energetic materials. 62. Reconciliation of the kinetics and mechanisms of TNT on the time scale from microseconds to hours

Cited by 57 publications

References 9 publications

Influence of the substituent on the major decomposition channels of the NO2 group inpara-substituted nitrobenzenes: a tandem mass spectrometric study

Influence of the substituent on the major decomposition channels of the NO2 group inpara-substituted nitrobenzenes: a tandem mass spectrometric study

Calibration of Chemical Kinetic Models Using Simulations of Small-Scale Cookoff Experiments

The Mechanism and Dynamics of Explosive Combustion in Aerosol Fuels

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