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Issue 11, 2015
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Lyman α photolysis of solid nitromethane (CH3NO2) and D3-nitromethane (CD3NO2) – untangling the reaction mechanisms involved in the decomposition of model energetic materials

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Abstract

Solid nitromethane (CH3NO2) along with its isotopically labelled counterpart D3-nitromethane (CD3NO2) ices were exposed to Lyman α photons to investigate the mechanism involved in the decomposition of energetic materials in the condensed phase. The chemical processes in the ices were monitored online and in situ via infrared spectroscopy complimented by temperature programmed desorption studies utilizing highly sensitive reflectron time-of-flight mass spectrometry coupled with pulsed photoionization (ReTOF-PI) at 10.49 eV. The infrared data revealed the formation of cis-methylnitrite (CH3ONO), formaldehyde (H2CO), water (H2O), carbon monoxide (CO), and carbon dioxide (CO2). Upon sublimation of the irradiated samples, three classes of higher molecular weight products, which are uniquely formed in the condensed phase, were identified via ReTOF-PI: (i) nitroso compounds [nitrosomethane (CH3NO), nitrosoethane (C2H5NO), nitrosopropane (C3H7NO)], (ii) nitrite compounds [methylnitrite (CH3ONO), ethylnitrite (C2H5ONO), propylnitrite (C3H7ONO)], and (iii) higher molecular weight molecules [CH3NONOCH3, CH3NONO2CH3, CH3OCH2NO2, ONCH2CH2NO2]. The mechanistical information obtained in the present study suggest that the decomposition of nitromethane in the condensed phase is more complex compared to the gas phase under collision-free conditions opening up not only hitherto unobserved decomposition pathways of nitromethane (hydrogen atom loss, oxygen atom loss, retro carbene insertion), but also the blocking of several initial decomposition steps due to the ‘matrix cage effect’.

Graphical abstract: Lyman α photolysis of solid nitromethane (CH3NO2) and D3-nitromethane (CD3NO2) – untangling the reaction mechanisms involved in the decomposition of model energetic materials

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Publication details

The article was received on 09 Dec 2014, accepted on 13 Feb 2015 and first published on 16 Feb 2015


Article type: Paper
DOI: 10.1039/C4CP05759G
Phys. Chem. Chem. Phys., 2015,17, 7514-7527

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    Lyman α photolysis of solid nitromethane (CH3NO2) and D3-nitromethane (CD3NO2) – untangling the reaction mechanisms involved in the decomposition of model energetic materials

    P. Maksyutenko, L. G. Muzangwa, B. M. Jones and R. I. Kaiser, Phys. Chem. Chem. Phys., 2015, 17, 7514
    DOI: 10.1039/C4CP05759G

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