ChemInform Abstract: Mechanisms of the Gas‐Phase Decomposition of C‐Nitro Compounds Inferred from Quantum Chemical Calculations

Храпковский, Г. М.; Шамов, А. Г.; Николаева, Е. В.; Чачков, Д. В.

doi:10.1002/chin.201015274

Cited by 7 publications

(13 citation statements)

References 1 publication

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“…Quantum calculations as well as experimental data show that the most probable channel of the decomposition of FOX-7 and its carbocyclic homologues is channel 1, the limiting stage of which is hydrogen transfer to a carbon atom. This conclusion agrees well with the previous experimental and theoretical data on the thermal stability of these compounds [15][16][17][18][19][20].…”

Section: Discussionsupporting

confidence: 93%

“…The reactions that FOX-7 molecules can enter into have been systematized in 2 reviews [17,18], the second of which concluded that during the decomposition of aminonitroethylenes, the most likely channel of gas-phase decomposition is the formation of substituted oxazetes (such as VI, Figure 2) at the limiting stage. Along with this, based on the results of molecular dynamics and quantum calculations, it was shown [19,20] that NO 2 elimination reactions, as well as intra-and inter-molecular hydrogen transfer, could play an important role in the thermal stability of FOX-7.…”

Section: Figure 2 New Reaction Paths Of Fox-7 Decompositionmentioning

confidence: 99%

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On the Mechanism of Thermal Decomposition of 1,1-Diamino-2,2-dinitroethene (FOX-7) and its Cyclic Derivatives

Krisyuk¹,

Захаров²,

Чуканов³

2020

Cent. Eur. J. Energ. Mater.

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Section: Discussionsupporting

confidence: 93%

Section: Figure 2 New Reaction Paths Of Fox-7 Decompositionmentioning

confidence: 99%

On the Mechanism of Thermal Decomposition of 1,1-Diamino-2,2-dinitroethene (FOX-7) and its Cyclic Derivatives

Krisyuk¹,

Захаров²,

Чуканов³

2020

Cent. Eur. J. Energ. Mater.

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“…This stepwise reaction was found to be highly exothermic with the heat release of 34.9 kcal/mol. The decomposition mechanism through a formation of the 1,2-oxazete 2-oxide structure, initially proposed for high-temperature pyrolysis of β-nitrostyrenes, has been recently reported for nitroalkenes and DADNE …”

Section: Resultsmentioning

confidence: 93%

Searching for Low-Sensitivity Cast-Melt High-Energy-Density Materials: Synthesis, Characterization, and Decomposition Kinetics of 3,4-Bis(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole-2-oxide

et al. 2015

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The most comprehensive approach to analyze and characterize energetic materials is suggested and applied to enable rational, rigorous design of novel materials and targeted improvements of existing materials to achieve desired properties. We report synthesis, characterization of the structure and sensitivity, and modeling of thermal and electronic stability of the energetic, heterocyclic compound, 3,4-bis(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole-2-oxide (BNFF). The proposed novel, relatively simple synthesis of BNFF in excellent yields allows for an efficient scale up. Performing careful characterization indicates that these materials offer an unusual combination of properties and exhibit a relatively high energy density, high and controllable stability against decomposition, low melting temperature, and low sensitivity to initiation of detonation. First-principles calculations of activation barriers and reaction rate constants reveal the decomposition scenarios that govern the thermal stability and chemical behavior of BNFF, which appreciably differ from conventional nitro compounds. Details of the electronic structure and calculated electronic properties suggest that BNFF is an excellent candidate energetic material on its own and an attractive ingredient of modern energetic formulations to improve their stability and enable highly controllable chemical decomposition.

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“…Nitroethylene (CH 2 CHNO 2 ) as the simplest member of the nitro-olefin series was usually considered to be a useful surrogate for understanding the behavior of nitro groups in the insensitive high energetic material 1,1-diamino-2,2-dinitroethylene (DADNE). Due to the fact that the experimental interpretations of decomposition processes of energetic materials are very complicated, quantum chemical calculations have been performed by Gindulytėet al, 1 Shamov et al, 2 and Khrapkovskii et al 3 to investigate the unimolecular decomposition mechanism of nitroethylene. Four distinct thermally initiated gas-phase decomposition pathways have been identified: direct C−NO 2 bond fission (R1), nitro to nitrite rearrangement with subsequent O−NO bond fission to yield CH 2 CHO and NO (R2), which is a result of the weak O−NO bond, HONO elimination reaction with formation of acetylene (R3), and 1,3-H shift with generation of CH 2 CN(O)OH (R4).…”

Section: ■ Introductionmentioning

confidence: 99%

Investigation on the Thermal Dissociation of Vinyl Nitrite with a Saddle Point Involved

Guan

Lou

et al. 2019

ACS Omega

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Hybrid and double-hybrid density functionals are employed to explore the O–NO bond dissociation mechanism of vinyl nitrite (CH2=CHONO) into vinoxy (CH2=CHO) and nitric monoxide (NO). In contrast to previous investigations, which point out that the O–NO bond dissociation of vinyl nitrite is barrierless, our computational results clearly reveal that a kinetic barrier (first-order saddle point) in the O–NO bond dissociation is involved. Furthermore, a radical–radical adduct is recommended to be present on the dissociation path. The activation and reaction enthalpies at 298.15 K for the vinyl nitrite dissociation are calculated to be 91 and 75 kJ mol–1 at the M062X/MG3S level, respectively, and the calculated reaction enthalpy compares very well with the experimental result of 76.58 kJ mol–1. The M062X/MG3S reaction energetics, gradient, Hessian, and geometries are used to estimate vinyl nitrite dissociation rates based on the multistructural canonical variational transition-state theory including contributions from hindered rotations and multidimensional small-curvature tunneling at temperatures from 200 to 3000 K, and the rate constant results are fitted to the four-parameter Arrhenius expression of 4.2 × 109 (T/300)4.3 exp[−87.5(T – 32.6)/(T2 + 32.62)] s–1.

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ChemInform Abstract: Mechanisms of the Gas‐Phase Decomposition of C‐Nitro Compounds Inferred from Quantum Chemical Calculations

Cited by 7 publications

References 1 publication

On the Mechanism of Thermal Decomposition of 1,1-Diamino-2,2-dinitroethene (FOX-7) and its Cyclic Derivatives

On the Mechanism of Thermal Decomposition of 1,1-Diamino-2,2-dinitroethene (FOX-7) and its Cyclic Derivatives

Searching for Low-Sensitivity Cast-Melt High-Energy-Density Materials: Synthesis, Characterization, and Decomposition Kinetics of 3,4-Bis(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole-2-oxide

Investigation on the Thermal Dissociation of Vinyl Nitrite with a Saddle Point Involved

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