Elementary Reactions in the Oxidation of Alkenes.

Article abstract of DOI:10.1002/bbpc.19830871113

The reactions of OH radicals with the isomers of butene (1-C//4H//8, cis-2-C//4H//8, trans-2-C//4H//8, iso-C//4H//8) have been studied at low pressure using an isothermal flow reactor (295-298 K, p equals 0. 9-10 Torr) and a Laval-nozzle reactor (p less than 0. 1 Torr). The hydroxyl radicals have been produced via the reactions H/D plus NO//2 or F plus H//2O/D//2O, hydroxy butyl radicals via the reactions F plus 1-C//4H//9OH, 2-C//4H//9OH, sec-C//4H//9OH, tert-C//4H//9OH. Samples were withdrawn continuously by a molecular beam sampling system and were analyzed mass spectrometrically, applying synchronous ion counting and chemical modulation techniques. The stabilization of the adduct is the main reaction channel at room temperature and around 1 Torr, abstraction reactions are negligible. The reaction mechanisms were analyzed in terms of addition/redissociation/stabilization/isomerization/decomposition, using unimolecular rate theory. The results are applied for the prediction of product formation at conditions of technical combustion processes.