The reaction between phenyl radical and phenylacetylene is a prototype for the reactions of aryl radicals and alkynyl peri‑condensed aromatic hydrocarbons (PCAHs), which may help explain the dimerization of PCAHs by covalent bond with acetylene assistance. In this work, we have experimentally and theoretically investigated reaction kinetics of phenyl radical and phenylacetylene. Gas chromatography-mass spectrometry (GC–MS) is applied to separate and identify molecular structures of reaction products in a jet-stirred reactor (JSR). Diphenylacetylene is observed as the major product of this reaction, which shows dominant concentration near 1000 K. Formation of phenanthrene increases with temperature, while 9-methylene-fluorene is a minor product, and 2-ethynyl-biphenyl is negligible. The potential energy surface and rate coefficients of phenyl and phenylacetylene reaction are calculated by quantum chemistry and transition state theory. 1,2-Diphenylvinyl is the only resonance-stabilized radical (RSR) among the adducts formed via all six possible addition reaction channels. Its formation reaction channel has a much lower energy barrier and deeper potential well and, therefore, it wins the competition in the reaction of phenyl and phenylacetylene at combustion-relevant intermediate temperatures.
|Original language||English (US)|
|Journal||Combustion and Flame|
|State||Published - Feb 1 2022|
Bibliographical noteKAUST Repository Item: Exported on 2022-02-09
Acknowledgements: This research was funded by the Office of Sponsored Research at King Abdullah University of Science and Technology (KAUST), Hefei Science Center CAS (2020HSC-KPRD001 and 2021HSC-UE005), and State Key Laboratory of Engines in Tianjin University (Grant No. K2021–15). Quantum calculations in this study were supported by the KAUST Supercomputing Laboratory.