...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Comparative Kinetics of the 3-Buten-1-ol and 1-Butene Reactions with OH Radicals: A Density Functional Theory/RRKM Investigation
【24h】

Comparative Kinetics of the 3-Buten-1-ol and 1-Butene Reactions with OH Radicals: A Density Functional Theory/RRKM Investigation

机译：3-丁烯-1-醇和1-丁烯与OH自由基的比较动力学：密度泛函理论/ RRKM研究

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

The compared kinetics of the reactions of unsaturated alcohols and alkenes with OH radicals is a topic of great interest from both the theoretical chemistry and the atmospheric chemistry points of view. The enhanced reactivity of an unsaturated alcohol, with respect to its alkene analogue, toward OH radicals has been previously demonstrated, at 298 K, by experimental and theoretical research. In this work, a new comparative investigation of such reactions is performed for 3-buten-1-ol and 1-butene. The model assumes that the overall kinetics is governed by the first OH addition steps of the mechanism. Calculations have been performed at the DFT level, employing the BHandHLYP functional and the cc-pVDZ and aug-cc-pVDZ basis sets, and the rate coefficients have been determined on the basis of the microcanonical variational transition state theory. The rate coefficients obtained for the OH reactions with 3-buten-1-ol (k(OH)(31BO)) and 1-butene (k(OH)(1B)) at 298.15 K are lower than the experimental rate coefficient available in the literature, showing deviations of 18% and 25%, respectively. Negative temperature dependence is verified for these rate coefficients. The k(OH)(31BO)/k(OH)(1B) ratios have also been investigated as a function of the temperature, suggesting that at room temperature the unsaturated alcohol reacts with the OH radicals faster than 1-butene, by a factor of 1.2, but at higher temperatures (400-500 K), the alkene should react faster, and that the stabilization of prebarrier complexes and saddle points due to hydrogen bonds is no longer an important factor to govern the reactivity of the unsaturated alcohol toward OH radicals, with respect to the alkene analogue.
机译：从理论化学和大气化学的观点来看，比较不饱和醇和烯烃与OH基的反应动力学是一个非常感兴趣的话题。先前已通过实验和理论研究证明了不饱和醇相对于其烯烃类似物对OH自由基的反应性增强。在这项工作中，对3-丁烯-1-醇和1-丁烯进行了此类反应的新比较研究。该模型假定总体动力学受机理的第一个OH加成步骤控制。已经使用BHandHLYP函数以及cc-pVDZ和aug-cc-pVDZ基集在DFT级别上进行了计算，并且速率系数已根据微规范变分过渡状态理论进行了确定。在298.15 K时与3-丁烯-1-醇（k（OH）（31BO））和1-丁烯（k（OH）（1B））进行OH反应的速率系数低于在文献中，分别显示出18％和25％的偏差。验证了这些速率系数的负温度依赖性。还已经研究了k（OH）（31BO）/ k（OH）（1B）的比率与温度的关系，这表明在室温下，不饱和醇与OH自由基的反应要比1-丁烯快1倍。烯烃的反应速率为1.2，但在较高的温度（400-500 K）下，烯烃应反应更快，并且由于氢键导致的预阻隔配合物和鞍点的稳定不再是控制不饱和醇对OH反应性的重要因素关于烯烃类似物的自由基。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号