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1 Central European Journal of Energetic Materials

1 2009

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Accounts of the new aspects of nitromethane initiation reactivity

Zeman S., Atalar T., Friedl Z., Ju X-H.

Central European Journal of Energetic Materials

2009

Vol. 6, nr 1

119-133

A well-known effect of amines, and also of water, on detonation characteristics of nitromethane (NM) is discussed from the point of view of the published knowledge about the study of initiation reactivity of this nitro paraffin. It is documented that bimolecular and higher interactions during the initiation of NM are impossible. The most widespread concepts of the primary steps of this initiation, i.e. formation of aci-NM anion [CH2=NO2]— by intermolecular hydrogen transfer in the neat NM submitted to shock and formation of this anion by action of an amine, have been scrutinized by the DFT B3LYP/cc-pVTZ+ method and evaluated as thermodynamically disadvantageous. Also the 1,3-intramolecular hydrogen shift in the NM molecule was characterized as a higher-barrier process. Two favorable primary mechanisms of fission in the NM initiation and development of its detonation were investigated by DFT B3LYP/cc-pVTZ+ calculations: homolysis of C–NO2 bond in the neat NM and homolysis of N–OH bond in its aci-form. The second mentioned pathway was found to be thermodynamically the most preferable mechanism of fission. Consequently, a detonation wave of NM with admixture of amine or water has a considerably reduced reaction zone length in comparison with the detonation of neat NM. The B3LYP/6-311++G(d,p) calculations of transition states revealed that an admixture of methylamine and/or water influences the conversion of nitromethane to its aci-form, and this effect is more feasible in the case of methylamine rather than water.