• 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 >Properties and Thermal Decomposition of the Hydro-Fluoro- Peroxide CH_3OC(O)OOC(O)F
【24h】

Properties and Thermal Decomposition of the Hydro-Fluoro- Peroxide CH_3OC(O)OOC(O)F

机译：氢氟过氧化物CH_3OC（O）OOC（O）F的性质和热分解

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 thermal decomposition of methyl fluoroformyl peroxycarbonate CH_3OC(O)OOC(O)F was studied in the range of 30- 96 °C using FTIR spectroscopy to follow the course of the reaction in the presence of either N_2, O_2, or CO as bath gases. The rate constants of the homogeneous first-order process fit the Arrhenius equation kexp = (5.4 ± 0.2) × 10~(14) exp[-(27.1 ± 0.6 kcal mol~(-1)/RT)] (in units of s~(-1)). A complete mechanism of decomposition is presented. An experimental O-O bond energy of 27 ± 1 kcal mol-1 was obtained. The products observed when N_2 or O_2 are used as bath gases were CO_2, CO, HF, and CH_3OC(O)H, while in the presence of CO, CH_3OC(O)F was also observed. Transition state ab initio calculations were carried out to understand the dynamics of the decomposition. Additionally, thermodynamic properties of the atmospherically relevant CH_3OCO_2? radical were calculated. The heat of formation, ΔH°_(f 298), obtained for CH_3OCO_2? and CH_3OC(O)OOC(O)F, were 78 ± 3 kcal mol~(-1) and 191 ± 5 kcal mol~(-1), respectively.
机译：在30-96°C范围内，使用FTIR光谱研究了N_2，O_2或CO作为浴液存在时反应的过程，研究了氟代甲酸过氧碳酸甲酯CH_3OC（O）OOC（O）F的热分解气体。均匀一阶过程的速率常数符合Arrhenius方程kexp =（5.4±0.2）×10〜（14）exp [-（27.1±0.6 kcal mol〜（-1）/ RT）]（以s为单位〜（-1））。提出了完整的分解机理。获得了27±1 kcal mol-1的实验性O-O键能。将N_2或O_2用作浴液时观察到的产物为CO_2，CO，HF和CH_3OC（O）H，而在存在CO的情况下，也观察到CH_3OC（O）F。进行了过渡态从头算的计算，以了解分解的动力学。此外，与大气有关的CH_3OCO_2？的热力学性质。计算出部首。 CH_3OCO_2？的形成热ΔH°_（f 298）。 CH_3OC（O）OOC（O）F和CH_3OC（O）OOC（O）F分别为78±3 kcal mol〜（-1）和191±5 kcal mol〜（-1）。

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