Rate constants for the bimolecular self‐reaction of tertbutyl radicals in nalkane solvents
Rate constants for the bimolecular self‐reaction of tertbutyl radicals in nalkane solvents
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正烷烃溶剂中叔丁基自由基双分子自反应的速率常数
DOI：
10.1002/kin.550080303
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发表时间：
1976
影响因子：
1.5
通讯作者：
H. Fischer
中科院分区：
文献类型：
--
作者：
H. Schuh;H. Fischer
速率常数的叔丁基自由基在六个正构烷烃的自反应的动力学电子自旋共振光谱和产品形成的速度作为温度的函数。它们被很好地描述了Smoluchowski-Stokes-Einstein处理，包括微摩擦和自旋统计因子的影响，表明完全扩散控制。发现歧化与组合产物的比率取决于温度和溶剂。这是暂时归因于重新定向的影响，在遇到对。
Rate constants for the self-reaction of tertbutyl radicals in six nalkanes are determined as functions of temperature by kinetic electron-spin resonance spectroscopy and from rates of product formation. They are well described by a Smoluchowski–Stokes–Einstein treatment including effects of microfriction and spin statistical factors, indicating complete diffusion control. The ratio of disproportionation to combination products is found to depend on temperature and solvent. This is tentatively ascribed to reorientational effects in the encounter pairs.