The overall rate constants for H-abstraction (k_H) from CH₃CHClCH₃ and D-abstraction (k_D) from CD₃CDClCD₃ by chlorine atoms in the temperature range 298–528.5 K were determined and are described by the expressions: k_H = (3.52 ± 0.21) × 10^–11 exp(−184 ± 19/T) cm³ molecule^–1 s^–1 and k_D = (1.91 ± 0.16) × 10^–11 exp(−185 ± 31/T) cm³ molecule^–1 s^–1 respectively. The results of the experiment show that the value of the kinetic isotope effect (k_H/k_D) for the overall rate constants is temperature independent and is equal to 1.85 ± 0.17. A theoretical examination of these reaction mechanisms revealed some unusual properties, such as negative values of the activation energy for the H-abstraction reaction from the secondary carbon atom. Moreover, it was proved that in the radical process of H-abstraction from the primary carbon atom of 2-chloropropane the created R–Cl···Cl complex is the most stable structure responsible for the value of the activation energy of this transformation.

中文翻译：

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氯原子与CH ₃ CHClCH ₃和CD ₃ CDClCD ₃反应的动力学和机理的实验和理论研究

整体速率常数H-抽象（ķ _ħ从CH）₃ CHClCH ₃和d-抽象（ķ _d）从CD ₃ CDClCD ₃的温度范围内298-528.5 K内由氯原子被确定，由表达式描述：k _H =（3.52±0.21）×10 ^–11 exp（-184±19 / T）cm ³分子^–1 s ^–1和k _D =（1.91±0.16）×10 ^–11 exp（-185±31 / T）cm ³分子^–1 s ^–1分别。实验结果表明，总速率常数的动力学同位素效应值（k _H / k _D）与温度无关，等于1.85±0.17。对这些反应机理的理论研究揭示了一些不寻常的性质，例如来自仲碳原子的H吸收反应的活化能为负值。此外，已经证明，在从2-氯丙烷的伯碳原子中吸氢的自由基过程中，生成的R–Cl···Cl络合物是最稳定的结构，是该转变的活化能值。