Mechanism of the gas-phase decomposition of trifluoro-, trichloro-, and tribromomethanols in the presence of hydrogen halides.

Ab initio calculations at the G2 level were used in a theoretical analysis of the kinetics of the decomposition of trifluoro-, trichloro-, and tribromomethanols. The high-pressure limiting rate coefficients k(diss,∞) for the thermal dissociation of CF(3)OH, CCl(3)OH, and CBr(3)OH were calculated using the conventional transition state theory. The results of potential surface calculations show that in the presence of the hydrogen halides HX (X = F, Cl, and Br), considerably lower energy pathways are accessible for the decomposition of CF(3)OH, CCl(3)OH, and CBr(3)OH.