Ion-Molecule Reactions in Unsaturated Hydrocarbons: Allene, Propyne, Diacetylene, and Vinylacetylene

Abstract

Ion-molecule reactions in allene, propyne, diacetylene, and vinylacetylene (1-buten-3-yne) have been studied at near-thermal energies by the technique of ion cyclotron resonance mass spectrometry. Rate coefficients and branching ratios are reported for the reactions of C_3H^+_n (n = 1-4) with allene and propyne and for the reactions of C_4H^+_n (n = 0-5) with diacetylene and vinylacetylene. Branching ratios are also given for the reactions of C_4H^+_n, C_5H_n, and C_6H^+_n with propyne and for reactions of C_6H^+_n with diacetylene and vinylacetylene. More than 90% of the reactive channels lead to product ions having a larger carbon skeleton than the reactant ion. Evidence for ions with the same m/e ratio having differing reactivities was obtained for C_3H^+_3, C_6H^+_7, and C_7H^+_7. Ion reaction sequences in allene and propyne were followed at higher pressures (l0^(-4) torr) to investigate secondary, tertiary, and higher order processes.