Photodissociation dynamics of dinitrite at 355 nm: initiation of a reactive pathway

Abstract

Dinitrites are effective nitrosating reagents in preparative chemistry and their decomposition products are involved in the atmospheric reaction of volatile organic compounds with nitrogen oxides (NO). In this work, photodissociation dynamics of five alkyl dinitrites were investigated by detecting the LIF spectra of the dissociation products and theoretical calculations. The results showed that the C-C bond connecting the two nitrosooxy (-ONO) functional groups was the weakest bond in vicinal dinitrites and aldehydes were the dissociation products. For dinitrites with two ONO groups separated by a CH group, vinoxy and 1-methylvinoxy radicals were detected as the fragments via photodissociation, indicating a different mechanism compared to thermal decomposition. This observation demonstrated that a new reactive pathway could be initiated by photolysis of dinitrites.

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

“…The former usually does not give rise to a substantial number of ions in the reaction system. 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.…”

“…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.…”

“…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. The former usually does not give rise to a substantial number of ions in the reaction system . One of the previous common mechanisms of the initial thermal decomposition of nitrobenzene is the homolytic cleavage of the C-NO 2 bond .…”

HOx and NOx production in oxidation flow reactors via photolysis of isopropyl nitrite, isopropyl nitrite-d7, and 1,3-propyl dinitrite at λ = 254, 350, and 369 nm

“…In this case, it is possible that higher NO 2 production during 1,3-Pr(ONO) 2 photolysis and/or production of more reactive intermediates (e.g. malonaldehyde) offset any benefit gained from faster OH production via photolysis of both -ONO groups or more efficient photolysis of one -ONO group (Wang and Zu, 2016).…”