Absolute Rate Constants for Hydrocarbon Autoxidation. XXI. Activation Energies for Propagation and the Correlation of Propagation Rate Constants with Carbon–Hydrogen Bond Strengths

摘要: The rate constants, kp, for the abstraction of a hydrogen atom from wide variety organic substrates at 30° have been correlated with strengths C—H bond that are broken, D[R—H] (in units kcal/mol). Two empirical relations derived, one tertiary peroxy radicals,and secondary radicals,These equations hold extremely well hydrocarbons and reasonably containing heteroatoms. activation energies pre-exponential factors oxidation some by t-butylperoxy radicals measured relationderived. If D[t-ROO—H] is taken as 88 kcal/mol, this yields Polanyi equation,where ΔH heat reaction. These permit calculation constants chain propagation in autoxidation many also other temperatures.