C14H10 polycyclic aromatic hydrocarbon formation by acetylene addition to naphthalenyl radicals observed?

Physical Chemistry Chemical Physics Pub Date: 2021-06-15 DOI: 10.1039/D1CP01565F

Abstract

The formation of polycyclic aromatic hydrocarbons (PAHs) during combustion has a substantial impact on environmental pollution and public health. The hydrogen-abstraction-acetylene-addition (HACA) mechanism is expected to be a significant source of larger PAHs containing more than two rings. In this study, the reactions of 1-naphthalenyl and 2-naphthalenyl radicals with acetylene (C2H2) are investigated using VUV photoionization time-of-flight mass spectrometry at 500 to 800 K, 15 to 50 torr, and reaction times up to 10 ms. Our experimental conditions allow us to probe the Bittner–Howard and modified Frenklach HACA routes, but not routes that require multiple radicals to drive the chemistry. The kinetic measurements are compared to a temperature-dependent kinetic model constructed using quantum chemistry calculations and accounting for chemical-activation and fall-off effects. We measure significant quantities of C14H10 (likely phenanthrene and anthracene), as well as 2-ethynylnaphthalene (C12H8), from the reaction of the 2-naphthalenyl radical with C2H2; these results are consistent with the predictions of the kinetic model and the HACA mechanism, but contradict a previous experimental study that indicated no C14H10 formation in the 2-naphthalenyl + C2H2 reaction. In the 1-naphthalenyl radical + C2H2 reaction system, the primary product measured is C12H8, consistent with the predicted formation of acenaphthylene via HACA. The present work provides direct experimental evidence that single-radical HACA can be an important mechanism for the formation of PAHs larger than naphthalene, validating a common assumption in combustion models.

Graphical abstract: C14H10 polycyclic aromatic hydrocarbon formation by acetylene addition to naphthalenyl radicals observed
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