• 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 >Isomerization of Simple Alkoxyl Radicals: New Temperature-Dependent Rate Data and Structure Activity Relationship
【24h】

Isomerization of Simple Alkoxyl Radicals: New Temperature-Dependent Rate Data and Structure Activity Relationship

机译：简单烷氧基自由基的异构化：新的温度依赖性速率数据和结构活性关系

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

Relative-rate experiments have been carried out, at several different temperatures between 240 and 340 K, to determine the Arrhenius rate parameters for the isomerization of the 1-pentoxyl, 2-pentoxyl, and 5-methyl-2-hexoxyl radicals. Isomerization rates were measured relative to the bimolecular reaction of each alkoxyl radical (RO~·) with O2. The order of reactivity, in terms of the rate of reaction for isomerization, was 5-methyl-2-hexoxyl > 1-pentoxyl > 2-pentoxyl, reflecting the relative-strengths of tertiary, secondary, and primary C-H bonds, i.e., the nature of the bond cleaved in the isomerization process. In addition to this, the measured Arrhenius activation barriers, and reported barriers for bimolecular reactions of the methoxyl radical with several simple hydrocarbons, are shown to correlate linearly with the bond strength of the cleaving C-H bond. The A-factors obtained for the three isomerization processes also scale linearly with the number of available abstractable H atoms, with a value of 3.0 * 10~(10) s~(-1) per H atom. This value combined with the activation barrier correlation constitutes a structure activity relationship for the estimation of the kinetics of the isomerization of simple alkoxyl radicals, at temperatures pertaining to the Earth's troposphere.
机译：已经在240和340 K之间的几个不同温度下进行了相对速率实验，以确定1-戊氧基，2-戊氧基和5-甲基-2-己氧基自由基异构化的阿累尼乌斯速率参数。相对于每个烷氧基（RO〜）与O2的双分子反应测量异构化速率。就异构化反应的速度而言，反应顺序为5-甲基-2-己氧基> 1-戊氧基> 2-戊氧基，反映了叔，仲和伯CH键的相对强度，即在异构化过程中断裂的键的性质。除此之外，已显示测得的Arrhenius激活势垒，以及已报告的甲氧基与几种简单烃的双分子反应势垒，与裂解C-H键的键强度线性相关。这三个异构化过程获得的A因子也与可用的可抽象H原子数成线性比例，每个H原子的值为3.0 * 10〜（10）s〜（-1）。该值与活化势垒相关性结合，构成了一种结构活度关系，用于估算在与地球对流层有关的温度下简单烷氧基自由基的异构化动力学。

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