Thermochemistry of explosives

Rogers, R. N.

doi:10.1016/0040-6031(75)80016-5

Cited by 142 publications

(56 citation statements)

References 10 publications

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“…(12) and (13) and the 2-NT data for equation (11). Of the three reactions in the gas phase, equation (12) has the fastest rate up to 950"C. At this temperature equation (11) becomes the fastest reaction. A similar analysis of the relative rates of decomposition channels can be made of 1,3,5-trinitrobenzene versus 2 4,6-trinitroaniline.…”

Section: C-no 2 Homolysismentioning

confidence: 92%

“…However, a discrepancy exists concerning the relative importance of equations (11) and (12). Equation (12) In both the laser pulse and the shock tube, the temperature of the reactant is stepped in several Asec to the 800 -10009C range.…”

Section: C-no 2 Homolysismentioning

confidence: 99%

“…2,4,6-Trinitroaniline is known to decompose by two branches shown in equation (14) to the furazan and furoxan derivatives. These cyclized products are equivalent to equation (12) for nitrotoluene. Two gas phase rate constant measurements are available (References 53,84) for equation (14) giving k -108 exp(-38500/RT) sec" 1 and k = 1011 exp(-41800/RT) sec" 1 .…”

Section: C-no 2 Homolysismentioning

confidence: 99%

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Kinetics and mechanisms of thermal decomposition of nitroaromatic explosives

Brill¹,

James²

1993

Chem. Rev.

390

337

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Section: C-no 2 Homolysismentioning

confidence: 92%

Section: C-no 2 Homolysismentioning

confidence: 99%

Section: C-no 2 Homolysismentioning

confidence: 99%

See 1 more Smart Citation

Kinetics and mechanisms of thermal decomposition of nitroaromatic explosives

Brill¹,

James²

1993

Chem. Rev.

390

337

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“…The kinetic parameters of the model were fitted to reproduce the ODTX in experiments. Rogers et al 6,7 estimated the kinetic parameters from calorimetry experiments near the melting temperature of PETN. Our ReaxFF RMD yields reaction rates for temperatures of 1200-1800 K, while most of the experimental data were obtained at temperatures below B500 K, requiring extrapolation of the measured rates to much higher temperatures.…”

Section: Molecular and Crystal Structures Of Si-petnmentioning

confidence: 99%

“…The explosive properties of pentaerythritol tetranitrate (PETN, C-(CH 2 -O-NO 2 ) 4 ) have been studied thoroughly both experimentally [1][2][3][4][5][6][7][8][9] and theoretically. [10][11][12][13][14][15][16] It has good detonation velocity and pressure, slightly below those of RDX (cyclotrimethylene trinitramine) but well above TNT (trinitrotoluene), 17 making it extensively used in blasting cap fillings, detonation cords, demolition devices, industrial explosives, etc.…”

Section: Introductionmentioning

confidence: 99%

ReaxFF reactive molecular dynamics on silicon pentaerythritol tetranitrate crystal validates the mechanism for the colossal sensitivity

Zhou

Liu

Goddard

et al. 2014

Phys. Chem. Chem. Phys.

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Recently quantum mechanical (QM) calculations on a single Si-PETN (silicon-pentaerythritol tetranitrate) molecule were used to explain its colossal sensitivity observed experimentally in terms of a unique Liu carbon-silyl nitro-ester rearrangement (R 3 Si-CH 2 -O-R 2 -R 3 Si-O-CH 2 -R 2 ). In this paper we expanded the study of Si-PETN from a single molecule to a bulk system by extending the ReaxFF reactive force field to describe similar Si-C-H-O-N systems with parameters optimized to reproduce QM results. The reaction mechanisms and kinetics of thermal decomposition of solid Si-PETN were investigated using ReaxFF reactive molecular dynamics (ReaxFF-RMD) simulations at various temperatures to explore the origin of the high sensitivity. We find that at lower temperatures, the decomposition of Si-PETN is initiated by the Liu carbon-silyl nitro-ester rearrangement forming Si-O bonds which is not observed in PETN. As the reaction proceeds, the exothermicity of Si-O bond formation promotes the onset of NO 2 formation from N-OC bond cleavage which does not occur in PETN. At higher temperatures PETN starts to react by the usual mechanisms of NO 2 dissociation and HONO elimination; however, Si-PETN remains far more reactive. These results validate the predictions from QM that the significantly increased sensitivity of Si-PETN arises from a unimolecular process involving the unusual Liu rearrangement but not from multi-molecular collisions. It is the very low energy barrier and the high exothermicity of the Si-O bond formation providing energy early in the decomposition process that is responsible.

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Electrostatic Discharge Ignition of Energetic Materials

Skinner

Olson

Block-Bolten

1998

Propellants, Explosives, Pyrotechnics

110

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Electrostatic discharge (ESD) ignition of explosives, pyrotechnics, or propellants is often considered to be mainly dependent upon various physical characteristics of the energetic material. This work shows that ESD ignition of secondary explosives tested in powdered form is primarily dependent upon the chemical characteristics of the energetic material (i.e., the decomposition rate kinetics of the materials). We propose that ignition occurs when a spark raises the temperature of the explosive particles to the point where thermal runaway occurs. ESD sensitivities of a diverse series of explosives were measured using a traveling needle test apparatus with the powders slightly con®ned by Mylar tape to prevent formation and ignition of a dust cloud.Using global thermal decomposition rate coef®cient expressions, two parameters were calculated for each explosive: (1) the critical temperatures according to the Frank-Kamenetskii formula for 20 mm particles of each explosive and (2) the temperatures at which the rate coef®cient equaled 10 3 s À1 . These two sets of data were correlated with the observed ESD sensitivities for 50 percent probability of ignition, E 50 . Excellent correlations resulted, indicating that for ESD ignition under these conditions the spark discharge is primarily a thermal source.

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Thermochemistry of explosives

Cited by 142 publications

References 10 publications

Kinetics and mechanisms of thermal decomposition of nitroaromatic explosives

Kinetics and mechanisms of thermal decomposition of nitroaromatic explosives

ReaxFF reactive molecular dynamics on silicon pentaerythritol tetranitrate crystal validates the mechanism for the colossal sensitivity

Electrostatic Discharge Ignition of Energetic Materials

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