A Theoretical Kinetic Study on Concerted Elimination Reaction Class of Peroxyl-hydroperoxyl-alkyl Radicals (•OOQOOH) in Normal-alkyl Cyclohexanes

• Published in: Molecules (Basel, Switzerland) Switzerland), 2023-09, Vol.28 (18), p.6612
• Main Authors: Yao, Xiaoxia, Zhang, Jilong, Zhu, Yifei
• Format: Article
• Language: English
• Subjects: Aircraft; Aviation; Carbon; Combustion; concerted elimination reaction; Hydrocarbons; Hydrogen bonds; kinetic parameters; Outdoor air quality; Oxidation; peroxyl-hydroperoxyl alkyl radicals; reaction rate rules; Superoxide
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules28186612

The concerted elimination reaction class of peroxyl-hydroperoxyl alkyl radicals (•OOQOOH) plays a crucial role in the low-temperature combustion of normal-alkyl cyclohexanes. The generation of the relatively unreactive HO2 radicals in this reaction is one of the factors leading to the negative temperature coefficient (NTC) behavior, which hinders the low-temperature oxidation of normal-alkyl cyclohexanes. In this study, 44 reactions are selected and divided into 4 different subclasses according to the nature of the carbon atom where the H atom is eliminated and the reaction center position. Utilizing the CBS-QB3 method, we compute the energy barriers for the concerted elimination reactions of peroxyl-hydroperoxyl alkyl radicals. Following this, we assess both the high-pressure limit and pressure-dependent rate constants for all reactions by applying TST and RRKM/ME theory. These calculations allow for the development of rate rules, which come to fruition through an averaging process involving the rate constants of representative reactions within each subclass. Our work provides accurate rate constants and rate rules for this reaction class, which can aid in constructing more accurate combustion mechanisms for normal-alkyl cyclohexanes.