Methyl-and tert-butyl-substituted hydroquinones and semiquinone radicals: Bond strength estimates, enthalpy of formation, and the rate constants of their reactions with peroxy radicals

Abstract

The strength of the O-H bonds (D) in hydroquinone (HQH) and its alkyl derivatives has been estimated by the intersecting parabolas method using rate constants known for the reactions of these compounds with the styrene peroxy radical. For unsubstituted HQH, D = 352.6 kJ/mol; for substituted HQH derivatives, D = 349.9 (Me), 346.9 (2,5-Me2), 343.0 (Me3), 347.6 (CMe3), and 340.2 (2,5-(CMe3)2) kJ/mol. The enthalpies of formation of these HQH derivatives have been calculated. The O-H bond strengths in the semiquinone radicals (HQ.) resulting from the above HQH derivatives have been calculated using a thermochemical equation to be $$D_{HQ^. } $$ = 236.7, 237.4, 239.8, 244.7, 240.1, and 247.5 kJ/mol, respectively. Rate constants have been determined for the reactions of the hydroquinones with tertiary and secondary peroxy radicals and HOO. at 323 K. The rate constants of the reactions between HOO. and benzoquinones and the relative reactivities of the HQ. radicals in their reactions with ROO. have been estimated.