INFRARED MATRIX-ISOLATION STUDY OF THE REACTION BETWEEN TRICHLOROMETHANE AND OXYGEN-ATOMS

The reactions Of CHCl3 With both excited and ground state oxygen atoms have been investigated in argon matrices at 12 K by Fourier transform IR spectroscopy. Ozone was employed as photolytic oxygen atoms source. Products were identified by using O-18(3) precursor and deuterium substitution in the CH bond. Two major pathways are observed for the CHCl3+O(1D) reaction and lead, respectively, to complexed phosgene and formylchloride as primary products. With O(3P) the second pathway is forbidden. No evidence is obtained for the formation of an intermediate species. Appearance of CO...HCl complexes is attributed to a secondary photolysis decomposition of primary products. A change in the primary products distribution is observed with CDCl3 and confirmed by relative kinetic studies of the products growth.