Probing the Reaction of Propargyl Radical with Molecular Oxygen by Synchrotron VUV Photoionization Mass Spectrometry.

Self-reaction of propargyl (C 3 H 3 ) radical is the main pathway to benzene, the formation of which is the rate-controlling step toward the formation of polycyclic aromatic hydrocarbons (PAHs) and soot. Oxidation of C 3 H 3 is a promising strategy to inhibit the formation of hazardous PAHs and soot. In the present study, we studied the C 3 H 3 + O 2 reaction from 650 to 1100 K in a laminar flow reactor and identified the intermediates and products by synchrotron VUV photoionization mass spectrometry. 2-Propynal, ethenone, formaldehyde, CO, CO 2 , C 2 H 2 , C 2 H 4 , and C 3 O 2 were identified. Among them, 2-propynal, ethenone, and formaldehyde provided direct evidence for the branching reaction of C 3 H 3 + O 2 → HCCCHO + OH, C 3 H 3 + O 2 → H 2 CCO + CHO, and C 3 H 3 + O 2 → H 2 CO + CHCO, respectively. Potential energy surface calculation and mechanistic analysis of the C 3 O 2 formations implied that C 3 H 3 + O 2 → CCCHO + H 2 O and C 3 H 3 + O 2 → HCCCO + H 2 O could occur, despite lacking direct observations of CCCHO and HCCCO radicals. The formation of ethenone and CO suggested the occurrence of the two CO elimination channels. We incorporated these validated reactions and the corresponding rate coefficients in the kinetic model of NUIGMech1.3, and the simulation showed obvious improvements toward the measured mole fractions of C 3 H 3 and H 2 CCO, suggesting that the new C 3 H 3 + O 2 reaction channels were crucial in the overall combustion modeling of the important intermediate propyne (C 3 H 4 ).