Kinetics of the Homogeneous Gas Phase Hydrolysis of CCl3COCl,CCl2HCOCl,CH2CICOCl and COCl2

The homogeneous gas phase hydrolysis kinetics of the above compounds has been investigated in the 470° to 620°K temperature range. The following biomolecular rate constants were obtained: k(CCl₃COCl) = 2.54 × 10⁶ exp (?18,350 ± 1750)/RT, k(CClH₂COCl) = 1.14 × 10⁸ exp (?22,630 ± 780)/RT, and fr(COCl₂) = 9192 exp (?14,200 ± 2100)/RT liter mole^?1 sec^?1. Experimental difficulties prevented data being obtained for CHCl₂COCl. The half lives of these species with respect to homogeneous gas phase hydrolysis in the atmosphere have been estimated and it is concluded that this is not an efficient conversion process. Heterogeneous hydrolysis by water droplets may be a more efficient atmospheric scavenging process for these compounds.