title: Thermal reactivity of some nitro- and nitroso-compounds derived from 1,3,5,7-tetraazabicyclo[3.3.1]nonane at contamination by ammonium nitrate.
abstract: Thermal reactivity of 3,7-dinitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane (DPT), 3,7-dinitroso-1,3,5,7-tetraazabicyclo[3.3.1]nonane (DNPT), 1,3,5-trinitroso-1,3,5-triazinane (TMTA or R-salt), 1,3,5-trinitro-1,3,5-triazinane (hexogen or RDX), 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetrazocane (DADN), alpha-modification of the 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (octogen or HMX) and of their mixtures with 2wt.% of ammonium nitrate (AN) has been examined by means of non-isothermal differential thermal analysis. The resulting data were analyzed according to the Kissinger method. The reactivity was expressed as the E(a)R(-1) slopes of the Kissinger relationship. A relatively high reactivity has been found with mixtures of DPT and DNPT with AN. Electronic charges q(N) at nitrogen atoms in molecules of the compounds studied were calculated by means of ab initio DFT B3LYP/6-31G** method. The relationships were confirmed between the slopes E(a)R(-1) and the q(N) values for the nitrogen atoms primarily undergoing reaction. On the basis of these relationships it is stated that the destabilizing effect of AN is due to acidolytic attack of nitric acid (resulting from dissociation of ammonium nitrate) at the nitrogen atoms with the most negative q(N) values in the molecules of the compounds studied.
authors.affiliation: Department of Theory and Technology of Explosives (DTTX), University of Pardubice CZ-532 10 Pardubice, Czech Republic. svatopluk.zeman@upce.cz
authors.forename: Svatopluk
authors.initials: S
authors.lastname: Zeman
authors.forename: Yuanjie
authors.initials: Y
authors.lastname: Shu
authors.forename: Zdenek
authors.initials: Z
authors.lastname: Friedl
authors.forename: Jirí
authors.initials: J
authors.lastname: Vágenknecht
mesh_terms: D000473:Alkanes / Q000737:chemistry*; D001643:Bridged Bicyclo Compounds / Q000737:chemistry*; D004055:Differential Thermal Analysis; D009566:Nitrates / Q000737:chemistry*; D009574:Nitro Compounds / Q000737:chemistry*; D009603:Nitroso Compounds / Q000737:chemistry*; D013696:Temperature; D013816:Thermodynamics
chemical_list: D000473:Alkanes; D001643:Bridged Bicyclo Compounds; D009566:Nitrates; D009574:Nitro Compounds; D009603:Nitroso Compounds; C006568:ammonium nitrate; C017573:nonane