Abstract
The thermal decomposition of trinitropyrazole (I) and its ammonium salt proceeds with a very strong self-acceleration, caused mainly by the catalytic action of the condensed products. The first-order rate constant for the initial stage k 1 describes the decomposition to a depth of conversion of 0.5% and is characterized by the following kinetic parameters E (kJ/mol) and log(A, s−1): 131.8 and 9.60 for the liquid phase and 116.0 and 8.57 for the solid state. The rate constant k 1 is smaller if the reaction occurs in nonpolar solvents and if I is methylated at position 1. All these data are interpreted in the framework of a mechanism according to which the reaction involves the oxidation by a nitro group of a neighboring carbon atom and proceeds through a highly polar cyclic transition state. Evaluation of the thermal stability of I is conducted using the method of a reference series composed of well-known regular HEs, which for the first time was implemented in terms of k 1. In the temperature range 20–80°C, the stability of trinitropyrazole is close to that of nitroglycerin. Trinitropyrazole ammonium salt is severalfold more stable than trinitropyrazole itself.
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Original Russian Text © V.V. Dubikhin, G.M. Nazin, V.G. Prokudin, Z.G. Aliev, I.L. Dalinger, S.A. Shevelev, 2015, published in Khimicheskaya Fizika, 2015, Vol. 34, No. 3, pp. 28–34.
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Dubikhin, V.V., Nazin, G.M., Prokudin, V.G. et al. Thermal stability of 3,4,5-trinitropyrazole and its ammonium salt. Russ. J. Phys. Chem. B 9, 211–217 (2015). https://doi.org/10.1134/S1990793115020037
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DOI: https://doi.org/10.1134/S1990793115020037