Reactions of oxygenated radicals in the gas phase. Part 8. Reactions of alkoxyl radicals with aldehydes and ketones

Abstract

Rate data for the abstraction reactions between t-butoxyl radicals and formaldehyde, acetaldehyde, acetone, and [²H₆]acetone were determined between 399 and 434 K. The alkoxyl radicals were generated by thermolysis of di-t-butyl peroxide. Data are obtained for the rate of reactions (6) and (13)—(16)(numbered in the text). The Bu^tO˙+ HCHO → Bu^tOH +˙CHO (6) Bu^tO˙+ CH₃CHO → Bu^tOH +˙CH₂CHO (13) Bu^tO˙+ CH₃CHO → Bu^tOH + CH₃ĊO (14) Bu^tO˙+ CH₃COCH₃→ Bu^tOH +˙CH₂COCH₃(15) Bu^tO˙+ CD₃COCD₃→ Bu^tOD +˙CD₂COCD₃(16) experimentally determined activation energies of several of these reactions are compared with those that may be calculated by a semi-empirical method.