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Solid-Phase Thermal Decomposition of 2,4-Dinitroimidazole (2,4-DNI)

Published online by Cambridge University Press:  10 February 2011

Leanna Minier ,
Richard Behrens JR.  and
Suryanarayana Bulusu
Leanna Minier
Affiliation:
Sandia National Laboratories, Combustion Research Facility, Livermore, CA 94551
Richard Behrens JR.
Affiliation:
Sandia National Laboratories, Combustion Research Facility, Livermore, CA 94551
Suryanarayana Bulusu
Affiliation:
Energetic Materials Division, U.S. Army, ARDEC, Dover, NJ 07801-5001
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Abstract

The solid-phase thermal decomposition of the insensitive energetic aromatic heterocycle 2,4- dinitroimidazole (2,4-DNI: mp 265–274°C) is studied utilizing simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) between 200° and 247°C. The pyrolysis products have been identified using perdeuterated and N-labeled isotopomers. The products consist of low molecular-weight gases and a thermally stable solid residue. The major gaseous products are NO, CO2, CO, N2, HNCO and H2O. Minor gaseous products are HCN, C2N2, NO2, C3H4N2, C3H3N3O and NH3. The elemental formula of the residue is C2HN2O and FTIR analysis suggests that it is polyurea- and polycarbamate-like in nature. The rates of formation of the gaseous products and their respective quantities have been determined for a typical isothermal decomposition experiment at 235°C. The temporal behaviors of the gas formation rates indicate that the overall decomposition is characterized by a sequence of four events; 1) an early decomposition period induced by impurities and H2O, 2) an induction period where CO2 and NO are the primary products formed at relatively constant rates, 3) an autoacceleratory period that peaks when the sample is depleted and 4) a final period in which the residue decomposes. Arrhenius parameters for the induction period are Ea = 46.9 ± 0.7 kcal/mol and Log(A) = 16.3 ± 0.3. Decomposition pathways that are consistent with the data are presented.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 418: Symposium GG – Decomposition, Combustion, and Detonation Chemistry of Energetic Materials , 1995 , 111
Copyright
Copyright © Materials Research Society 1996

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References

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