Physical Sciences and Mathematics Commons^™

Peroxyl Radical Clocks, Bill Roschek, Keri A. Tallman, Christopher L. Rector, Jason G. Gillmore, Derek A. Pratt, Carlo Punta, Ned A. Porter

Faculty Publications

A series of peroxyl radical clocks has been developed and calibrated based on the competition between the unimolecular β-fragmentation (kβ) of a peroxyl radical and its bimolecular reaction with a hydrogen atom donor (kH). These clocks are based on either methyl linoleate or allylbenzene and were calibrated directly with α-tocopherol or methyl linoleate, which have well-established rate constants for reaction with peroxyl radicals (kH-tocopherol = 3.5 × 106 M-1 s-1, kH-linoleate = 62 M-1 s-1). This peroxyl radical clock methodology has been successfully applied to determine inhibition and propagation rate constants ranging from 100 to 107 M-1 s-1.