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

摘要

The kinetics of CHClBr + HBr reversible arrow CH2ClBr + Br (1, -1), CCl2Br + HBr reversible arrow CHCl2Br + Br (2, -2) and CClBr2 + HBr reversible arrow CHClBr2 + 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 x 10(-13) exp[-1.47 kcal mol(-1)/RT], k(-1) = 2.70 x 10(-11) exp [-10.21 kcal mol(-1)/RT], k(2) = 4.18 x 10(-13) exp[-2.49 kcal mol(-1)/RT], k(-2) = 6.96 x 10(-12) exp[-7.36 kcal mol(-1)/RT], k(3) = 3.29 x 10(-13) exp[-2.20 kcal mol(-1)/RT], and k(-3) = 8.45 x 10(-13) exp[-7.10 kcal mol(-1)/RT]. Rate constants for (2, -2) and (3, -3) are here reported for the first time. (C) 2018 Elsevier B.V. All rights reserved.