Mechanisms and products of the reactions of NO3 with cycloalkenes |
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| Authors: | Ingvar Wängberg |
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| Institution: | (1) Department of Inorganic Chemistry, University of Göteborg and Chalmers University of Technology, S-412 96 Göteborg, Sweden |
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| Abstract: | The NO3 radical initiated oxidation of cyclopentene, cyclohexene and 1-methyl-cyclohexene has been studied. The products formed in an N2O5-NO2-N2-O2-cycloalkene-static reactor system, at 0.1 MPa and 296 K, were investigated using long path FTIR. The principal products were aldehydes formed via a ring opening process. The reactions also resulted in significant yields of three types of ring retaining nitrooxy-substituted compounds. The average yields of alkyl nitrates from, e.g., reactions with cycloalkene were 25.1% 2-oxo-cyclohexyl nitrate, 22.8% 2-hydroxy-cyclohexyl nitrate and 4.0% 1,2-cyclohexyl dinitrate. The mechanisms involved resembles those proposed for acyclic alkenes. In absence of NO,  -oxo and -hydroxy-cycloalkyl nitrates are formed via self reactions of -nitrooxy substituted cycloalkyl peroxy radicals. Estimated branching ratios for the reactants leading to ring retaining products in the presence and in the absence of NO are given and the possible relevance of these reactions for cycloalkenes under tropospheric conditions is discussed. |
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| Keywords: | NO3 radical cycloalkene gas-phase FTIR mechanism study cycloalkyl nitrates |
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