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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Unimolecular Reactions of CH2BrCH2Br, CH2BrCH2Cl, and CH2BrCD2Cl: Identification of the Cl-Br Interchange Reaction
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Unimolecular Reactions of CH2BrCH2Br, CH2BrCH2Cl, and CH2BrCD2Cl: Identification of the Cl-Br Interchange Reaction

机译：CH2BrCH2Br，CH2BrCH2Cl和CH2BrCD2Cl的单分子反应：Cl-Br交换反应的鉴定

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摘要

The recombination reactions of CH2Br and CH2Cl radicals have been used to generate vibrationally excited CH2BrCH2Br and CH2BrCH2Cl molecules with 91 kcal mol-1 of energy in a room-temperature bath gas. The experimental unimolecular rate constants for elimination of HBr and HCl were compared to calculated statistical rate constants to assign threshold energies of 58 kcal mol-1 for HBr elimination from C2H4Br2 and 58 and 60 kcal mol-1, respectively, for HBr and HCl elimination from C2H4BrCl. The Br-Cl interchange reaction was demonstrated and characterized by studying the CH2BrCD2Cl system generated by the recombination of CH2Br and CD2Cl radicals. The interchange reaction was identified from the elimination of HBr and DCl from CH2ClCD2Br. The interchange reaction rate is much faster than the rates of either DBr or HCl elimination from CH2BrCD2Cl, and a threshold energy of =43 kcal mol-1 was assigned to the interchange reaction. The statistical rate constants were calculated from models of the transition states that were obtained from densityfunctional theory using the B3PW91 method with the 6-31G(d,p) basis set. The model for HBr elimination was tested versus published thermal and chemical activation data for C2H5Br. A comparison of Br-Cl interchange with the Cl-F and Br-F interchange reactions in 1,2-haloalkanes is presented.
机译：CH2Br和CH2Cl自由基的重组反应已用于在室温浴气体中产生能量为91 kcal mol-1的振动激发的CH2BrCH2Br和CH2BrCH2Cl分子。将用于消除HBr和HCl的实验单分子速率常数与计算出的统计速率常数进行比较，以分别为从C2H4Br2中消除HBr和58和60 kcal mol-1阈值能量分别指定从C2H4Br2中消除HBr和58 kcal mol-1中消除HBr和HCl。 C2H4BrCl。通过研究由CH2Br和CD2Cl自由基重组产生的CH2BrCD2Cl体系，证明并表征了Br-Cl交换反应。通过从CH 2 ClCD 2 Br中消除HBr和DC1来鉴定交换反应。交换反应速率比从CH2BrCD2Cl中除去DBr或HCl的速率快得多，并且将交换能量指定为= 43 kcal mol-1的阈值能量。统计速率常数是从过渡态模型中计算出来的，这些模型是使用B3PW91方法从密度泛函理论中获得的，该模型具有6-31G（d，p）基集。测试了消除HBr的模型与已发布的C2H5Br的热和化学活化数据之间的关系。给出了在1，2-卤代烷烃中Br-Cl交换与Cl-F和Br-F交换反应的比较。

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