Temperature Dependence of the Reaction of Chlorine Atoms with CH3OH and CH3CHO.

Abstract

Rate constants of the reactions Cl + CH3OH → CH2OH + HCl ( k1) and Cl + CH3CHO → CH3C(O) + HCl ( k3) were measured at 100 Torr over the temperature range 230.3-297.1 K. Radical chemistry was initiated by pulsed laser photolysis of Cl2 in mixtures of CH3OH and CH3CHO in a flow reactor. Heterodyne near-IR wavelength modulation spectroscopy was used to directly detect HO2 produced from the subsequent reaction of CH2OH with O2 in real time to determine the rate of reaction of Cl with CH3OH. The rate of Cl + CH3CHO was measured relative to that of the Cl + CH3OH reaction. Secondary chemistry, including that of the adducts HO2·CH3OH and HO2·CH3CHO, was taken into account. The Arrhenius expressions were found to be k1( T) = 5.02-1.5+1.8 × 10-11 exp[(20 ± 88)/ T] cm3 molecule-1 s-1 and k3( T) = 6.38-2.0+2.4 × 10-11 exp[(56 ± 90)/ T] cm3 molecule-1 s-1 (2σ uncertainties). The average values of the rate constants over this temperature range were k1 = (5.45 ± 0.37) × 10-11 cm3 molecule-1 s-1 and k3 = (8.00 ± 1.27) × 10-11 cm3 molecule-1 s-1 (2σ uncertainties), consistent with current literature values.