Infrared chemiluminescent reactions of fluorine atoms with methanol and some deuterated analogs

Abstract

In the reactive systems F + CH 3OH, F + CH 3OD, F + CD 3OD the emission spectra were recorded from HF and/or DF in the fundamental region. Fluorine atom attack occurs at the methyl and at the hydroxyl end of the alcohols. Vibrational relaxation was suppressed and rotational relaxation took place only to a minor extent. The relative populations N υ J , which are therefore proportional to relative detailed rate constants, were used to evaluate internal branching ratios and kinetic isotope effects. For the attack of the methyl group k H/ k D = 1.2 ± 0.3 and for the attack of the hydroxyl group k H/ k D = 0.6 ± 0.2 were deduced. It is concluded that HF(DF) excitation takes place up to the thermodynamical limit in all cases. < f V > ranges between 0.41 and 0.53, < f R> between 0.02 and 0.06.