Rates of processes initiated by pulsed laser production of F atoms in the presence of HCl, CH4, and CF3H

Article abstract of DOI:10.1002/kin.550260804

Time-resolved vibrational chemiluminescence from HF has been recorded following the production of F atoms by the pulsed laser photolysis (λ = 266 nm) of F₂ in the presence of HCl, CH₄, and CF₃H. In the first two cases, experiments have been conducted by observing emission from HF(ν = 3) at four temperatures from 295 to 139 K. Rate constants have been determined over this range of temperature for the reactions of F atoms with HCl and CH₄ and of CH₃ radicals with F₂, and for the relaxation of HF(ν = 3) by HCl and CH₄. The reaction of F atoms with CF₃H is slower than those with HCl and CH₄ and measurements on the emission from HF(ν = 2) have been used to infer rate constants for reaction and relaxation only at 295 K.