Abstract
The Cl‐atom‐initiated oxidation of two esters, ethyl formate [HC(O)OCH~2~CH~3~] and ethyl acetate [CH~3~C(O)OCH~2~CH~3~], has been studied at pressures close to 1 atm as a function of temperature (249–325 K) and O~2~ partial pressure (50–700 Torr), using an environmental chamber technique. In both cases, Cl‐atom attack at the CH~2~ group is most important, leading in part to the formation of radicals of the type RC(O)OCH(O^•^)CH~3~ [R = H, CH~3~]. The atmospheric fate of these radicals involves competition between reaction with O~2~ to produce an anhydride compound, RC(O)OC(O)CH~3~, and the so‐called α‐ester rearrangement that produces an organic acid, RC(O)OH, and an acetyl radical, CH~3~C(O). For both species studied, the α‐ester rearrangement is found to dominate in air at 1 atm and 298 K. Barriers to the rearrangement of 7.7 ± 1.5 and 8.4 ± 1.5 kcal/mole are estimated for CH~3~C(O)OCH(O^•^)CH~3~ and HC(O)OCH(O^•^)CH~3~, respectively, leading to increased occurrence of the O~2~ reaction at reduced temperature. The data are combined with those obtained from similar studies of other simple esters to provide a correlation between the rate of occurrence of the α‐ester rearrangement and the structure of the reacting radical. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 397–413, 2010