1,1-Diamino-2,2-dinitroethylene: The riddles of thermal decomposition and combustion

热分解 化学 分解 等温过程 分子间力 分子 热力学 有机化学 物理
作者
Valery P. Sinditskii,Alexander A. Kushtaev,N. V. Yudin,Anton I. Levshenkov,Natalia N. Kondakova,Marina A. Alekseeva
出处
期刊:Journal of Physics and Chemistry of Solids [Elsevier BV]
卷期号:177: 111275-111275 被引量:3
标识
DOI:10.1016/j.jpcs.2023.111275
摘要

The thermal decomposition of deuterium derivatives α-FOX-7 and γ-FOX-7 have been studied using non-isothermal and isothermal kinetic methods. It was found that deuteration only affects the kinetics of the low-temperature decomposition step of α-FOX-7. A unique feature of the low-temperature stage of the decomposition of α-FOX-7 is that topochemical processes on crystal defects lead to intermolecular hydrogen transfer with the formation of its highly reactive aci-form. The decomposition of the aci-form of FOX-7 proceeds in an extremely unusual way via the molecular elimination of nitric acid and formation of nitrile N-oxide. The high-temperature decomposition stage involves the olefinic form of FOX-7 in a defect-free crystal lattice, and the decomposition is initiated by breaking the C–NO2 bond. In the gas phase, the FOX-7 molecule is also in its olefin form and exhibits high thermal stability. The combustion behavior and flame structure of α–FOX-7 and heat-treated substance (γ–FOX-7t) have been studied using a constant-pressure bomb and micro-thermocouple technique. Analysis of the thermocouple measurement data showed that the burning rate of both FOX-7 isomers is controlled by the rate of heat release in the condensed phase. This reaction is the decomposition of the substance in the melt. The higher burning rates of α-FOX-7 were due to the fact that the highly reactive aci-form of FOX-7 formed on the crystal defects remains in the melt and decomposes at the surface temperature. The break in the dependence of the burning rate on pressure observed for the α- and γ-polymorphs is associated with their complete isomerization into the internal aci-form of FOX-7 due to intramolecular hydrogen transfer. In this case, the surface temperature is determined by the vaporization of the internal aci-form of FOX-7, whose enthalpy of vaporization is higher than that of its olefin form.
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