KINETICS AND MECHANISM OF THE REACTION OF CH3 AND CH3O WITH CLO AND OCLO AT 298 K

A discharge-flow system equipped with a laser-induced fluorescence cell to detect the methoxyl radical and a quadrupole mass spectrometer to detect bath the chlorine monoxide and chlorine dioxide radicals has been used to measure the rate constants for the reactions CH3 + ClO --> procuts (1) CH3O + ClO --> products (2) CH3 + OClO --> products (3) CH3O + OClO --> products (4) at T = 298 K and P = 1-3 Torr. The observed products of these reactions are CH3O for reaction (1), HOCl for reaction (2), and CH3O and ClO for reaction (3). For reaction (4), CH3OCl is a possible product. The rate constants derived for reactions (1)-(4) are: k(1) = (1.3 +/- 0.4) x 10-(10) cm(3) molecule(-1) s(-1); k(2) = (1.3 +/- 0.3) x 10(-11) cm(3) molecule(-1) s(-1); k(3) = (1.6 +/- 0.3) x 10(-11) cm(3) molecule(-1) s(-1); k(4) = (1.5 +/- 0.5) x 10-(12) cm(3) molecule(-1) s(-1). The likely mechanisms for reactions (1)-(4) are briefly discussed.