Reactions of O(D-1) oxygen atom with 1,1,1-trichloroethane in solid argon

Matrices formed by the cocondensation of 1,1,1-trichloroethane and ozone in argon were irradiated at 11 K with the laser line at 266 nm. The CH3CCl3 molecule was not photodecomposed at this wavelength. The product identification was made by Fourier transform infrared spectroscopy. Acetylchloride, 2,2,2-trichloroethanol and 1,1-dichloroethylene were observed in the beginning of the reaction. Trichloroethanol is the main product. It is probably formed by insertion of an O atom in a C-H bond to give an excited intermediate which may release its excess energy by relaxation in the matrix or by elimination of HOCl, leading to CH2 = CCl2. The formation of small amounts of acetylchloride is probably due to direct oxygen attack on the carbon atom. Photolysis of CH3COCl and CH2CCl2 was observed upon prolonged irradiation between 800 and 250 nm and produced ketene and chloroacetylene, respectively. Fourier transform infrared spectra of CH3COCl and CD3COCl isolated in argon matrix were also recorded in this work.