Infrared multiphoton generation of radicals: A new technique for obtaining absolute rate constants. Application to reactions of CF3

The infrared multiphoton dissociation of CF3I is used as a convenient source of CF3 radicals under very low pressure conditions. Measurement of thermal absolute rate constants at 298 K for the reactions CF3+Br2→CF3Br+Br, CF3+ClNO→CF3Cl+NO, CF3+O3→CF3O+O2, and CF3+NO2→CF3O+NO yield (7.8±1.3) ×108, (3.5±0.5) ×108, (5.6±0.8) ×108, and (1.6±0.3) ×109 M−1 s−1, respectively. This new technique shows great promise for production of other free radicals of interest and measurement of thermal absolute rate constants over a wide temperature range.

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