Abstract
Abstract The reaction of oxygen atoms with (CD3)2CHCl in a fast flow system was studied with a photoionization mass spectrometer. The (CD3)2\dotCCl radical formed by the initial hydrogen abstraction at the 2-position was detected directly. (CD3)2CHCl+O(3P)→(CD3)2\dotCCl+OH (1) The rate data for Reaction 1 were fitted by an Arrhenius expression: k1=(3.5−0.9+1.2)×10−11exp[(−4973±278 cal mol−1)/RT] cm3 molecule−1 s−1 (399–628 K). Among the products formed in the subsequent reaction of (CD3)2\dotCCl radicals with atomic oxygen, CD3CCl=CD2 (31%) produced by the deuterium abstraction and (CD3)2CO (24%) by the oxygen addition were observed. Competition experiments show that (CD3)2\dotCCl radicals react (0.0079±0.0010) times as fast with O2 as with O(3P). In the presence of an excess of O2, CD3CCl=CD2 was observed in decreased yield (3.5%) and (CD3)2CO increased to 56%.
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