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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Solvent Effect on the Rate of β-Scission of the tert-Butoxyl Radical
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Solvent Effect on the Rate of β-Scission of the tert-Butoxyl Radical

机译：溶剂对叔丁氧基自由基β-断裂速率的影响

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摘要

The transient absorption spectrum of the tert-butoxyl radical in the UV region was obtained by the laser flash photolysis technique. The rate constants for β-scission and self-termination reactions of tert-butoxyl radicals were measured in five solvents; the Arrhenius parameters of the rate constant for β-scission k_β were determined. It was shown that both the solvent polarity and ability for hydrogen bonding accelerate the reaction of β-scission. The solvent effect on the rate constant of the β-scission reaction is discussed in terms of a simple Onzager-Betcher model, a point dipole model, and model of the H-bonded complex of the radical with the solvent molecule.
机译：通过激光闪光光解技术获得了紫外区叔丁氧基自由基的瞬态吸收光谱。在五种溶剂中测量了β-断裂和叔丁氧基自由基的自终止反应的速率常数。确定了β断裂k_β的速率常数的阿伦尼乌斯参数。结果表明，溶剂极性和氢键结合能力均能促进β-断裂的反应。通过简单的Onzager-Betcher模型，点偶极子模型和自由基与溶剂分子的H键结合的复合物模型，讨论了溶剂对β断裂反应速率常数的影响。

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