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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Unimolecular rate constants for HX or DX elimination (X = F, Cl) from chemically activated CF3CH2CH2Cl, C2H5CH2Cl, and C2D5CH2Cl: Threshold energies for HF and HCl elimination
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Unimolecular rate constants for HX or DX elimination (X = F, Cl) from chemically activated CF3CH2CH2Cl, C2H5CH2Cl, and C2D5CH2Cl: Threshold energies for HF and HCl elimination

机译：化学活化的CF3CH2CH2Cl，C2H5CH2Cl和C2D5CH2Cl消除HX或DX的单分子速率常数（X = F，Cl）：消除HF和HCl的阈值能量

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Vibrationally activated CF3CH2CH2Cl Molecules were prepared with 94 kcal mol(-1) of vibrational energy by the combination of CF3CH2 and CH2Cl radicals and with 101 kcal mol(-1) of energy by the combination of CF3 and CH2CH2Cl radicals at room temperature. The unimolecular rate constants for elimination of HCl from CF3CH2CH2Cl were 1.2 x 10(7) and 0.24 x 10(7) s(-1) with 101 and 94 kcal mol(-1), respectively. The product branching ratio, k(HCl)/k(HF), was 80 +/- 25. Activated CH3CH2CH2Cl and CD3CD2CH2Cl molecules with 90 kcal mol(-1) of energy were prepared by recombination Of C2H5 (or C2D5) radicals with CH2Cl radicals. The unimolecular rate constant for HCl elimination was 8.7 x 10(7) s(-1), and the kinetic isotope effect was 4.0. Unified transition-state models obtained from density-functional theory calculations, with treatment of torsions as hindered internal rotors for the molecules and the transition states, were employed in the calculation of the RRKM rate constants for CF3CH2CH2Cl and CH3CH2CH2Cl. Fitting the calculated rate constants from RRKM theory to the experimental values provided threshold energies, E-0, of 58 and 71 kcal mol(-1) for the elimination of HCl or HF, respectively, from CF3CH2CH2Cl and 54 kcal mol(-1) for HCl elimination from CH3CH2CH2Cl. Using the hindered-rotor model, threshold energies for HF elimination also were reassigned from previously published chemical activation data for CF3CH2CH3, CF3CH2CF3, CH3CH2CH2F, CH3CHFCH3, and CH3CF2CH3. In an appendix, the method used to assign threshold energies was tested and verified using the combined thermal and chemical activation data for C2H5Cl, C2H5F, and CH3CF3.
机译：在室温下，振动能量为94 kcal mol（-1）的分子是通过CF3CH2和CH2Cl自由基的组合制备的，振动能量为101 kcal mol（-1）的分子是通过CF3和CH2CH2Cl自由基的组合制备的。从CF3CH2CH2Cl去除HCl的单分子速率常数分别为101 x 94 kcal mol（-1）为1.2 x 10（7）和0.24 x 10（7）s（-1）。产物支化比k（HCl）/ k（HF）为80 +/-25。通过将C2H5（或C2D5）自由基与CH2Cl重组，制备了具有90 kcal mol（-1）能量的CH3CH2CH2Cl和CD3CD2CH2Cl分子。部首。消除HCl的单分子速率常数为8.7 x 10（7）s（-1），动力学同位素效应为4.0。从密度泛函理论计算获得的统一过渡态模型中，使用扭力作为分子和过渡态的受阻内转子，用于计算CF3CH2CH2Cl和CH3CH2CH2Cl的RRKM速率常数。将根据RRKM理论计算出的速率常数与实验值进行拟合可提供分别从CF3CH2CH2Cl和54 kcal mol（-1）消除HCl或HF的阈值能量E-0，分别为58和71 kcal mol（-1）。用于从CH3CH2CH2Cl中除去HCl。使用受阻转子模型，还从先前发布的CF3CH2CH3，CF3CH2CF3，CH3CH2CH2F，CH3CHFCH3和CH3CF2CH3的化学活化数据中重新分配了消除HF的阈值能量。在附录中，使用C2H5Cl，C2H5F和CH3CF3的热和化学活化数据的组合对用于分配阈值能量的方法进行了测试和验证。

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