通过控制溶液中的热反应中的能量分离来控制选择性
Hiroaki Kurouchi1, Ivonne L Andujar-De Sanctis1, Daniel A Singleton1
1Department of Chemistry, Texas A&M University , P.O. Box 30012, College Station, Texas 77842, United States.
Journal of the American Chemical Society
|October 22, 2016
概括
使用动态同位素效应来评估基分裂的统计速率理论. 具有较大的替代剂的基质中的非统计能量分布导致同位素效应低于理论预测.
科学领域:
- 化学运动学
- 物理化学
- 反应动态
背景情况:
- 动态同位素效应 (KIE) 是反应机制的敏感探测器.
- 统计速率理论,如RRKM理论,假设分子内的能量随机化.
- 这些理论对于激素反应,特别是α-裂变的适用性,需要仔细研究.
研究的目的:
- 评估用于预测alkoxy基α裂变中的KIEs的统计率理论的有效性.
- 研究替代物大小对能量分布和KIE的影响.
- 确定在哪些条件下进行非统计学分离.
主要方法:
- 实验KIE与统计速率理论的预测进行比较.
- 替代剂大小的系统变化
- 分析激素所传递的能量及其分布.
主要成果:
- 裂变行为 (统计与非统计) 取决于裂变屏障和内基能量.
- 大型基替代剂增加振动能量,但导致非统计分布.
- 这种非统计式的能量分布导致KIEs低于纯统计模型预测的值.
结论:
- 统计速率理论并不普遍适用于基α裂变.
- 替代效应在确定反应的统计性质方面起着至关重要的作用.
- 一个半统计局部RRKM模型可以在特定条件下近似观察到KIE.
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