Rate coefficient for the reaction of CCl3 radicals with ozone

Abstract

AbstractThe rate coefficient for the reaction of CCl3 radicals with ozone has been measured at 303 ± 2 K. The CCl3 radicals were generated by the pulsed laser photolysis of carbon tetrachloride at 193 nm. The time profile of CCl3 concentration was monitored with a photoionization mass spectrometer. Addition of the O3–O2 mixture to this system caused a decay of the CCl3 concentration because of the reactions of CCl3 + O3 → products (5) and CCl3 + O2 → products (4). The decay of signals from the CCl3 radical was measured in the presence and absence of ozone. In the absence of ozone, the O3–O2 mixture was passed through a heated quartz tube to convert the ozone to molecular oxygen. Since the rate coefficient for the reaction of CCl3 + O2 could be determined separately, the absolute rate coefficient for reaction (5) was obtained from the competition among these reactions. The rate coefficient determined for reaction (5) was (8.6 ± 0.5) × 10−13 cm3 molecule−1 s−1 and was also found to be independent of the total pressure (253–880 Pa of N2). This result shows that the reaction of CCl3 with O3 cannot compete with its reaction with O2 in the ozone layer. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 310–316, 2003