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Author McKee, M. L.
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ♦ ENVIRONMENTAL SCIENCES ♦ ALKANES ♦ CONFIGURATION INTERACTION ♦ CONFORMATIONAL CHANGES ♦ DECOMPOSITION ♦ PHOTOCHEMICAL REACTIONS ♦ NITRITES ♦ NITROMETHANE ♦ ENTHALPY ♦ THEORETICAL DATA ♦ THERMODYNAMICS ♦ CHEMICAL EXPLOSIVES ♦ CHEMICAL REACTIONS ♦ DATA ♦ EXPLOSIVES ♦ HYDROCARBONS ♦ INFORMATION ♦ NITRO COMPOUNDS ♦ NITROGEN COMPOUNDS ♦ NUMERICAL DATA ♦ ORGANIC COMPOUNDS ♦ ORGANIC NITROGEN COMPOUNDS ♦ OXYGEN COMPOUNDS ♦ PHYSICAL PROPERTIES ♦ THERMODYNAMIC PROPERTIES ♦ Organic Chemistry- Chemical & Physicochemical Properties- (-1987) ♦ Photochemistry ♦ Environment, Atmospheric- Basic Studies- (-1989) ♦ Combustion, Pyrolysis, & High-Temperature Chemistry
Abstract A theoretical study has been performed for the thermal rearrangements connecting nitromethane, methyl nitrite, nitrosomethanol, and aci-nitromethane by using the 6-31G* basis set to optimize geometries and introducing correlation at the MP2 level. The lowest calculated rearrangement pathways from nitromethane are to methyl nitrite (..delta..H/sup double dagger/ = 73.5 kcal/mol) and aci-nitromethane (..delta..H/sup double dagger/ = 75.0 kcal/mol). Nitrosomethanol, although predicted to be only 1.6 kcal/mol less stable, is separated by two high barriers from nitromethane. An elimination transition structure connecting methyl nitrite and formaldehyde plus nitroxyl is found to have an enthalpic barrier of 44.1 kcal/mol. Fragmentation reactions have enthalpies of reaction less than calculated barrier heights, suggesting that concerted rearrangements on the CH/sub 3/NO/sub 2/ surface in general will not be observed.
Educational Use Research
Learning Resource Type Article
Publisher Date 1986-09-17
Publisher Department Auburn Univ., AL
Publisher Place United States
Journal J. Am. Chem. Soc.
Volume Number 108
Issue Number 19
Organization Auburn Univ., AL


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