Two sides of thermal stability of energetic liquid: Vaporization and decomposition of 3-methylfuroxan

Two sides of thermal stability of energetic liquid: Vaporization and decomposition of 3-methylfuroxan Full article

Journal

Journal of Molecular Liquids
ISSN: 0167-7322 , E-ISSN: 1873-3166

Output data

Year: 2022, Volume: 348, Article number : 118059, Pages count : DOI: 10.1016/j.molliq.2021.118059

Authors

Muravyev Nikita V. ¹ , Melnikov Igor N ¹ , Chaplygin Daniil A. ² , Fershtat Leonid L. ² , Monogarov Konstantin A. ¹

Affiliations

1	N.N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, 4 Kosygina Str., 119991, Moscow, Russia
2	N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Ave., 119991 Moscow, Russia

Analysis of thermal behavior of liquids is often accompanied by vaporization. In an extreme case, the calorimetric (DSC) experiment reveals the only endothermic evaporation instead of the more valuable thermal decomposition. 3-Methylfuroxan (MMF) is an energetic monosubstituted 1,2,5-oxadiazole N-oxide that shows the above behavior. We investigate the sample mass and confinement effects and show that the pressure DSC allows observing thermal decomposition of target compound at 2.0 MPa. Advanced model-fitting kinetic analysis reveals two global stages, the first of which is a competition between the noncatalytic reaction and autocatalytic one, whereas the second global stage is a second-order reaction. Analysis of MMF thermolysis in solution in dibutyl phthalate shows the activation energy for noncatalytic reaction to be 145.4 ± 1.7 kJ mol−1. To resolve the gas decomposition products in experiments at 0.1 MPa pressure, where the evaporation is abundant, a gas chromatography–mass spectrometry coupled with thermal analyzer was used. Among the gases that are consistent with a furoxan ring rupture by Csingle bondC and Nsingle bondO bonds (HNCO, CH3CN), we detect CH3COCN that retains Csingle bondC bond. The formation of geminal cyanonitro compound in the course of thermolysis is proposed to explain the composition of the gas reaction products. Overall, with the range of thermal analysis tools (DSC, PDSC, GC–MS/TGA, thermokinetic modeling) we performed a detailed analysis of thermal transformations of unexplored simple monosubstituted furoxan. The applied methodological approaches could be transferred to other molecular liquids.

Muravyev N.V. , Melnikov I.N. , Chaplygin D.A. , Fershtat L.L. , Monogarov K.A.
Two sides of thermal stability of energetic liquid: Vaporization and decomposition of 3-methylfuroxan
Journal of Molecular Liquids. 2022. V.348. 118059 . DOI: 10.1016/j.molliq.2021.118059 WOS Scopus OpenAlex

Web of science:	WOS:000754539500015
Scopus:	2-s2.0-85119417783
OpenAlex:	W3213594186

DB	Citing
OpenAlex	11
Scopus	9
Web of science	10