Thermal decomposition of alkenes: role of allylic C-C bond cleavage

Abstract

Thermal decomposition of alkenes is critical in many chemical processes. In the alkene moiety, allylic CC bonds are significantly weaker than alkylic and vinylic CC bonds. To address literature discrepancies in the rate of allylic CC bond cleavage, the current work investigates the thermal decomposition of two prototype molecules, namely 1-hexene (k1) and 4-methyl-1-pentene (k2). The formation of product allyl radicals is tracked using a highly sensitive UV laser diagnostic to determine the rate coefficients of k1 and k2 over 1178–1359 K in a shock tube. Both reactions exhibit a positive Arrhenius temperature dependence, with the decomposition of 4-methyl-1-pentene occurring 1.5–3 times faster than that of 1-hexene. Values of k1 adopted in literature models vary by an order of magnitude.By integrating our previous measurements of 1-butene and 1-pentene decomposition (Zhou et al., 2024), this work establishes a comprehensive set of rate rules that encompasses the decomposition of allylic-primary (P), allylic-secondary (S21 and S22), and allylic-tertiary (T) CC bonds. At 1200 K, the decomposition of a tertiary allylic CC bond (kT) occurs 42 times faster than that of the primary CC bond (kP). Notably, our established rate rules caution against commonly adopted analogies between the rate coefficients of the thermal decomposition of 1-butene and 1-pentene, as kS21 proceeds 3–7 times faster than kP.The implementation of these rate rules in various kinetic models of alkenes and biofuels greatly enhances the accuracy of their predictions. This work thus contributes to a deeper understanding of the mechanisms underlying soot formation during from the combustion of unsaturated fuels.