Petroleum Chemistry, Vol.44, No.4, 250-255, 2004
Estimation of the O-H bond dissociation energy from kinetic data for hydroperoxides with functional groups
To determine O-H bond dissociation energies (DO-H) in hydroperoxides (RmuOOH) formed upon oxidation of ethers, esters, alcohols, ketones, and aldehydes, experimental parameters for the cooxidation of these compounds with hydrocarbons were used. The values DeltaD = D(RmuOO-H) - D(AlkylOO-H) were calculated using the method of crossing parabolas, and D(RmuOO-H) were determined for the following substituted hydroperoxides: cyclohexyl-1-hydroxy-1-hydroperoxide (362.1 kJ/mol), RPhCH(OH)OO-H (359.8 kJ/mol), ROCH(OO-H)R (367.3 kJ/mol), R2CHOC(OO-H)R-2 (358.4 kJ/mol), ROCH(OO-H)Ph (374.8 kJ/mol), 2-hydroperoxytetrahydrofuran (367.6 kJ/mol), RC(O)(OO-H) (387.1 kJ/mol), cyclohexylpercarboxylic acid (376.9 kJ/mol), R3CC(O)(OO-H) (376.9 kJ/mol), PhC(O)(OO-H) (403.9 kJ/mol), alpha-ketocyclohexylperoxide (369.8 kJ/mol), RC(O)OCH(OO-H)Ph (376.4 kJ/mol), CCl3CCl2(OO-H) (413.1 kJ/mol), and CHCl2CCl2(OO-H) (411.6 kJ/mol).