REACTION OF CH3O2 WITH SO2

Mixtures of Cl2, CH4, and O2 were flash photolyzed at room temperature and pressures of ∽60–760 Torr to produce CH3O2. The CH3O2 radicals decay by the second‐order process (Formula Presented.) with k6 = (3.7 ± 0.3) × 10−13 cm3/sec in good agreement with other studies. This value ignores any removal by secondary radicals produced as a result of reaction (6), and therefore the true value might be as much as 30% lower. The value is independent of total pressure or the presence of H2O vapor. With SO2 also present, the CH3O2 decay becomes pseudo first order at sufficiently high SO2 pressure which indicates the reaction (Formula Presented.) The value of (8.2 ± 0.5) × 10−15 cm3/sec at about 1 atm total pressure (mostly CH4) was found for CH3O2 removal by SO2, in good agreement with another recent measurement. This value can be equated with k1, unless the products rapidly remove another CH3O2 radical, in which case k1 would be a factor of 2 smaller. Copyright © 1979 John Wiley & Sons, Inc.