Kinetics of radical reactions involved in the gas-phase thermal decomposition of nitrobenzene

Scanning Tunneling and Atomic Force Microscopy Evidence for Covalent and Noncovalent Interactions between Aryl Films and Highly Ordered Pyrolytic Graphite

“…We attribute these changes to a thermal decomposition process that generates film-based radicals. Decomposition of nitrobenzene in the gas phase at 450 °C is reported to proceed via homolytic cleavage of the N−C bond to yield phenyl radicals, 38 whereas Toupin and Beĺanger's study of the thermal stability of NP films grafted to carbon powder suggested that heating generates film-based phenoxy and phenyl radicals. 37 Hence, we propose that during heating of NP films on HOPG, decomposition of NP groups is accompanied by radical coupling between neighboring aryl groups, giving a more rigid film structure and increasing its resistance to disruption by the STM tip.…”

Predicting the Initial Thermal Decomposition Path of Nitrobenzene Caused by Mode Vibration at Moderate-Low Temperatures: Temperature-Dependent Anti-Stokes Raman Spectra Experiments and First-Principals Calculations

“…8 One of the previous common mechanisms of the initial thermal decomposition of nitrobenzene is the homolytic cleavage of the C-NO 2 bond. 11 The later theoretical research 12 for the kinetics of nitrobenzene shows that the decomposition way was different at different temperatures: the C-NO 2 cleavage is dominant above 850 K, while the O-NO break via the nitro-nitrite isomerization becomes competitive at about 500 K. Besides, under high pressure (from 5 to 20 Torr), a radical reaction also was proposed at early stages of nitrobenzene thermal decomposition 13 at low temperature (723 K) through the study of a minimum kinetic mechanism. Recent report 17 showed that the thermal dissociation of nitrobenzene was dominated by roamingmediated isomerization to phenyl nitrite, which subsequently decomposed to give C 6 H 5 O + NO.…”

“…The energetic materials have accidental explosion hazards when subjected to external heat or shock stimulation, resulting in significant damage in applications fields of military and industry. However, the detailed triggered mechanisms are still unknown, which hinders its safe storage, usage, and further development. − Nitrobenzene, as one of the prototypical molecules employed in studies of the combustion and decomposition of energetic materials, − has received some experimental and theoretical investigations in the thermal decomposition − and photodissociation − mechanism. Early studies of nitrobenzene have proposed three major photodissociation channels, producing C 6 H 5 + NO 2 , C 6 H 5 O + NO, and C 6 H 5 NO + O, respectively. , However, the thermal decomposition is different from the photodissociation.…”