Cleavage of an aromatic ring and radical migration. (1st July 2022)

• Record Type: Journal Article
• Authors: Mebel, Alexander M.; Frenklach, Michael
• Is Part Of: Faraday discussions. Volume 238(2022)
• Page Start: 512
• Page End: 528
• Publication Date: 2022-07-01
• Subjects: Chemistry -- Periodicals; Metallurgy -- Periodicals; Electrochemistry -- Periodicals; 540
• DOI: 10.1039/d2fd00012a
• Languages: English
• ISSNs: 1359-6640

Abstract

Abstract : Reaction-rate analysis of thermal ring cleavage in sooting flames shows that it can be comparable in rate to oxyradical decomposition and that fast internal ring radical migration is comparable in frequency to reaction events of aromatic growth. Abstract : The present study undertakes a theoretical evaluation of thermal decomposition of aromatic-ring radicals. Potential energy surfaces and associated reaction rate coefficients were calculated for 1- and 2-naphthalenyl, acetanaphthylenyl, and pyrenyl radicals. Kinetic Monte-Carlo simulations were performed to examine the rates of ring cleavage in two sooting laminar premixed flames of ethylene. The simulations showed that the thermal aromatic-ring cleavage is comparable in rate to oxyradical decomposition in a heavier-sooting flame. The simulation also revealed, unexpectedly, fast internal ring radical migration, comparable in frequency to reaction events of aromatic growth.