Thermal Decomposition of Nitromethane and Reaction between CH3 and NO2

The Journal of Physical Chemistry. a
Akira Matsugi, Hiroumi Shiina

Abstract

The thermal decomposition of gaseous nitromethane and the subsequent bimolecular reaction between CH3 and NO2 have been experimentally studied using time-resolved cavity-enhanced absorption spectroscopy behind reflected shock waves in the temperature range 1336-1827 K and at a pressure of 100 kPa. Temporal evolution of NO2 was observed following the pyrolysis of nitromethane (diluted to 80-140 ppm in argon) by monitoring the absorption around 400 nm. The primary objectives of the current work were to evaluate the rate constant for the CH3 + NO2 reaction (k2) and to examine the contribution of the roaming isomerization pathway in nitromethane decomposition. The resultant rate constant can be expressed as k2 = (9.3 ± 1.8) × 10-10(T/K)-0.5 cm3 molecule-1 s-1, which is in reasonable agreement with available literature data. The decomposition of nitromethane was found to predominantly proceed with the C-N bond fission process with the branching fraction of 0.97 ± 0.06. Therefore, the upper limit of the branching fraction for the roaming pathway was evaluated to be 0.09.

References

Jun 28, 2008·Accounts of Chemical Research·Arthur G Suits
Nov 8, 2008·Physical Chemistry Chemical Physics : PCCP·Jeng-Da Chai, Martin Head-Gordon
Dec 19, 2009·The Journal of Physical Chemistry. a·R SivaramakrishnanS J Klippenstein
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Mar 19, 2016·The Journal of Physical Chemistry. a·Akira MatsugiKazuo Takahashi
Apr 26, 2017·The Journal of Physical Chemistry. a·James P A LockhartRobert S Tranter

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Citations

Feb 12, 2021·The Journal of Physical Chemistry. a·Jason FordTodd J Martínez
Apr 2, 2020·The Journal of Physical Chemistry. a·Romain PerriotShawn D McGrane
Jan 10, 2020·The Journal of Physical Chemistry. a·Akira Matsugi

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