Computational Kinetic Study on the Intramolecular H-Migration of Hydroperoxyalkylperoxy Radicals (•OOQOOH) in Normal-Alkyl Cyclohexanes
Xiaoxia Yao, Juanqin Li, Zerong Li
TL;DR
This study calculates accurate reaction rates for hydrogen migration in hydroperoxyalkylperoxy radicals in cyclohexane fuels, improving combustion predictions.
Contribution
New high-pressure rate constants and subclass-based rate rules for H-migration in normal-alkyl cyclohexanes are derived.
Findings
Rate constants for 110 H-migration reactions were calculated and grouped into 15 subclasses.
Updated mechanisms for ethyl and n-propyl cyclohexane show better agreement with experimental combustion data.
Disparities were found between current mechanisms and the newly calculated rate constants for cyclohexanes.
Abstract
Hydroperoxyalkylperoxy radicals (•OOQOOH) are important intermediates in the low-temperature oxidation chemistry of conventional fuels. In these species, a hydrogen atom may migrate from a non-adjacent carbon to the peroxy group, forming a dihydroperoxyalkyl radical (•P(OOH)2). This research delves into the theoretical kinetics of a set of 110 H-migration reactions in normal-alkyl cyclohexanes, calculating high-pressure limit rate constants for these reactions. The reactions are further classified into 15 subclasses based on distinctions in the reaction center and its environment, with rate rules derived by averaging the rate constants within each subclass. A comparison of our calculated rate constants for specific H-migration reactions of •OOQOOH with existing mechanisms and similar reactions in non-cyclic alkanes reveals significant disparities, emphasizing the necessity for precise…
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Taxonomy
TopicsCatalysis and Oxidation Reactions · Catalytic Processes in Materials Science · Free Radicals and Antioxidants