甲基乙基替代Criegee中间体与SO2的双分子反应
Meijun Zou1, Tianlin Liu1, Michael F Vansco2
1Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, United States.
The journal of physical chemistry. A
|October 23, 2023
概括
甲基乙基替代克里吉中间体 (MECI) 与二氧化硫 (SO2) 反应的速度比缺乏共振稳定性的类似化合物要快. 这项研究揭示了结构和共振如何影响大气化学中的Criegee中间反应性.
科学领域:
- 大气化学 大气化学
- 化学动力学 化学动力学
- 有机化学 有机化学
背景情况:
- 克里基中间体是大气氧化过程中的关键物种.
- 了解它们的反应性对于大气建模至关重要.
- 甲基乙基替代的Criegee中间体 (MECI) 由于缺乏共振稳定,提供了对结构反应关系的洞察.
研究的目的:
- 在实验和理论上研究MECI与二氧化硫 (SO2) 的双分子反应.
- 阐明Criegee中间结构和共振稳定对反应动力学的影响.
- 为了比较MECI与其他Criegee中间体,如甲基乙烯基氧化物 (MVK-氧化物) 的反应性.
主要方法:
- 复合光电离子质谱法用于测量MECI + SO2反应的速率系数.
- 高层次的理论计算探索了最小能量路径和反应动态.
- 修改后的阿雷尼乌斯方程用于syn和anti MECI符合的温度依赖的速率系数.
主要成果:
- 对MECI + SO2的实验速率系数被确定为 (1.3 ± 0.3) × 10^-10 cm^3 s^-1 在298 K和10 Torr.
- 硫三氧化物 (SO3) 被确定为反应的产物.
- 理论计算为同步和反MECI符合者提供了温度依赖的速率系数,显示了与298K的实验数据相符的合理一致.
结论:
- MECI与SO2的反应明显快于MVK氧化物与SO2的反应.
- 这种差异凸显了共振稳定对Criegee中间反应性的重大影响.
- 这些发现有助于更好地了解涉及Criegee中间体的大气氧化机制.
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