FTIR Study of the Kinetics and Mechanism for the Cl-Atom-Initiated Reactions of SiHCl3

Article abstract of DOI:10.1021/j100263a028

On the basis FTIR product analysis of the UV-visible (λ >= 300 nm) photolysis of Cl2-SiHCl3 mixtures in 700 torr of N2-O2, Cl atoms were shown to predominantly undergo an H-atom abstraction reaction rather than an attachement/displacement reaction with SiHCl3.The corresponding rate constant k was determined at 298 K to be 2.9 X 10E-11 cm³molecule^-1s^-1 by the competitive kinetic method with reference to the Cl + C6H6 reaction.IR absorption bands attributable to two new gaseous products, SiCl3OCl and SiCl3OH, were detected in the subsequent oxidation of the primary radical SiCl3.Kinetic and spectroscopic evidence was also obtained for the NO2-addition reaction of the oxy and peroxy radicals SiCl3O and SiCl3OO.A plausible mechanism for the formation of these products is presented.