Rate constants and kinetic isotope effects for methoxy radical reacting with NO₂ and O₂

Absolute rate constants k2 were determined using laser flash photolysis/laser-induced fluorescence under the same conditions. The analogous experiments were carried out for the reactions of the perdeuterated methoxy radical (CD3O·).

Absolute rate constants k2 were in excellent agreement with the recommendations of the JPL Data Evaluation panel. The combined data (i.e., k1/k2 and k2) allow the determination of k1 as 1.3-0.5+0.9 × 10–14 exp[-(663 ± 144)/T] cm3 s-1, corresponding to 1.4 × 10-15 cm3 s-1 at 298 K. The rate constant at 298 K is in excellent agreement with previous work, but the observed temperature dependence is less than was previously reported.