Chemical Activation Study of the Unimolecular Reactions of CD3CD2CHCl2and CHCl2CHCl2with Analysis of the 1,1-HCl Elimination Pathway.
Chemically activated C2D5CHCl2molecules were generated with 88 kcal mol-1of vibrational energy by the recombination of C2D5and CHCl2radicals in a room temperature bath gas. The competing 2,1-DCl and 1,1-HCl unimolecular reactions were identified by the observation of the CD3CD═CHCl and CD3CD═CDCl products. The initial CD3CD2C-Cl carbene product from 1,1-HCl elimination rearranges to CD3CD═CDCl under the conditions of the experiments. The experimental rate constants were 2.7 × 107and 0.47 × 107s-1for 2,1-DCl and 1,1-HCl elimination reactions, respectively, which corresponds to branching fractions of 0.84 and 0.16. The experimental rate constants were compared to calculated statistical rate constants to assign threshold energies of 54 and ≈66 kcal mol-1for the 1,2-DCl and 1,1-HCl reactions, respectively. The statistical rate constants were obtained from models developed from electronic-structure calculations for the molecule and its transition states. The rate constant (5.3 × 107s-1) for the unimolecular decomposition of CHCl2CHCl2molecules formed with 82 kcal mol-1of vibrational energy by the recombination of CHCl2radicals also is reported. On the basis of the magnitude of the calculated rate constant, 1,1-HCl elimination must contribute less than 15% to the reaction; 1,2-HCl elimination is the major reaction and the threshold energy is 59 kcal mol-1. Calculations also were done to analyze previously published rate constants for chemically activated CD2ClCHCl2molecules with 86 kcal mol-1of energy to obtain a better overall description of the nature of the 1,1-HCl pathway for 1,1-dichloroalkanes. The interplay of the threshold energies for the 2,1-HCl and 1,1-HCl reactions and the available energy determines the product branching fractions for individual molecules. The unusual nature of the transition state for 1,1-HCl elimination is discussed.
Department of Chemistry, University of North Carolina-Asheville , One University Heights, Asheville, North Carolina 28804-8511, United States.
Allie C
AC
Larkin
Department of Chemistry, University of North Carolina-Asheville , One University Heights, Asheville, North Carolina 28804-8511, United States.
Matthew J
MJ
Nestler
Department of Chemistry, University of North Carolina-Asheville , One University Heights, Asheville, North Carolina 28804-8511, United States.
Caleb A
CA
Smith
Department of Chemistry, University of North Carolina-Asheville , One University Heights, Asheville, North Carolina 28804-8511, United States.
George L
GL
Heard
Department of Chemistry, Kansas State University , Manhattan, Kansas 66506, United States.
D W
DW
Setser
Department of Chemistry, University of North Carolina-Asheville , One University Heights, Asheville, North Carolina 28804-8511, United States.
Bert E
BE
Holmes