Hydrogen-Atom-Induced Decomposition of Trichloroethylene at High Temperatures

Article abstract of DOI:10.1021/j100010a028

Mechanisms and rate constants for hydrogen atom attack on trichloroethylene have been determined in single-pulse shock tube experiments near 1050 K.Products from all the decomposition channels have been observed.The predominant process is the displacement of the chlorine at the least substituted site.The following rate expressions have been determined: k(H* + HClC=CCl2 -> H2C=CCl2 + Cl*) = 6 x 1E13 exp(-2439/T) cm³ mol^-1 s^-1; k(H* + HClC=CCl2 -> HClC=CClH (cis + trans) + Cl*) = 3.7 x 1E13 exp(-3946/T) cm³ mol^-1 s^-1; k(H* + HClC=CCl2 -> *HC=CCl2 or HClC=CCl* + HCl) = 3.8 x 1E14 exp(-6686/T) cm³ mol^-1 s^-1.An upper limit for the rate constant of the abstraction process H* + HClC=CCl2 -> *ClC=CCl2 + H2 is 6.5 x 1E10 cm³ mol^-1 s^-1 at 1050 K.Rate constants for chlorine attack on H2 at these temperatures are a factor of 13 smaller than those on mesitylene.The results are compared with those for hydrogen atom reactions with other unsaturated compounds.Some implications regarding the incineration of chlorinated organics will be discussed.