Photooxidation of C5-C7 Cycloalkanes in the NO-H2O-Air System

Article abstract of DOI:10.1021/j150618a028

Photooxidation of C5-C7 cycloalkane-NO-H2O-air systems was investigated.Reaction products were analyzed by FID gas chromatography (GC), GC/Ms, and FT IR.Cycloalkanone and cycloalkyl nitrate were observed to form as undergraded products.Among the C5-C7 cycloalkanes, the ratios of cycloalkyl nitrate produced to cycloalkane consumed were nearly equal (0.05-0.1), while marked variations were observed in the ratios of cycloalkanone produced to cycloalkane consumed (0.0016, 0.23, and 0.031 for C5, C6, and C7 cycloalkanes, respectively).These differences were explained by the ring rupture of cycloalkane ring, assuming that the extent of the ring rupture process depends on the strain energy of the cycloalkane ring.Cycloalkanone and cycloalkyl nitrate were minor product except for cyclohexanone, which amounted 20-30percent of cyclohexane consumed.Formaldehyde was observed as a ring rupture product (3-9percent of cycloalkane consumed).Major products were unidentified carbonyls produced by ring cleavage reactions.These carbonyls amounted to about 45percent of cycloalkane consumed.Formation of carbonyls and formaldehyde could be explained by the ring cleavage decomposition of the vibrationally hot cycloalkyloxy radicals.