THE REACTION OF OXYGEN ATOMS WITH CARBON TETRACHLORIDE

Abstract

The homogeneous reaction between O atoms and CCl4 was studied in a flow system under conditions of complete consumption of atoms, in the presence and in the absence of molecular oxygen. The only products of the reaction are Cl2, CO, CO2, and COCl2. No compounds containing more than one carbon atom were detected. The dependence of the products on CCl4 concentration suggests that the primary reactions are[Formula: see text]which are too slow to consume all the atoms. Carbon dioxide is produced by secondary reactions which are fast enough to consume all the atoms, the most important of which is[Formula: see text]However, the dependence of the ratio (CO2 + COCl2/CO on CCl4 concentration in the presence of O2 indicates other reactions also produce CO2. The rapid disappearance of O atoms in the systems containing O2 suggests a chain mechanism in which Cl2 is mainly converted to the atomic form. Carbon dioxide can then be produced by the sequence[Formula: see text]The rate constant for the primary process was found to be independent of O, O2, and CCl4 concentration and could be represented by the equation[Formula: see text]