Theoretical kinetics study of the reactions CHClBr + HBr ⇄ CH2ClBr + Br, CCl2Br + HBr ⇄ CHCl2Br + Br and CClBr2 + HBr ⇄ CHClBr2 + Br

Abstract The kinetics of CHClBr + HBr ⇄ CH 2 ClBr + Br (1, -1) , CCl 2 Br + HBr ⇄ CHCl 2 Br + Br (2, -2) and CClBr 2  + HBr ⇄ CHClBr 2  + Br (3, -3) reactions at 293–787 K has been studied by using the canonical transition state theory with molecular information provided by different quantum chemical methods. The obtained rate constants (in cm 3 molecule −1 s −1 ) are k 1  = 5.24 × 10 −13 exp[−1.47 kcal mol −1 /RT], k −1  = 2.70 × 10 −11 exp[−10.21 kcal mol −1 /RT], k 2  = 4.18 × 10 −13 exp[−2.49 kcal mol −1 /RT], k −2  = 6.96 × 10 −12 exp[−7.36 kcal mol −1 /RT], k 3  = 3.29 × 10 −13 exp[−2.20 kcal mol −1 /RT], and k −3  = 8.45 × 10 −13 exp[−7.10 kcal mol −1 /RT]. Rate constants for (2, -2) and (3, -3) are here reported for the first time.