Rates of processes initiated by pulsed laser production of F atoms in the presence of HCl, CH 4 , and CF 3 H

Time‐resolved vibrational chemiluminescence from HF has been recorded following the production of F atoms by the pulsed laser photolysis (λ = 266 nm) of F 2 in the presence of HCl, CH 4 , and CF 3 H. 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 CH 4 and of CH 3 radicals with F 2 , and for the relaxation of HF(ν = 3) by HCl and CH 4 . The reaction of F atoms with CF 3 H is slower than those with HCl and CH 4 and measurements on the emission from HF(ν = 2) have been used to infer rate constants for reaction and relaxation only at 295 K. © 1994 John Wiley & Sons, Inc.