Oxidation Kinetics and Thermodynamics of Resonance-Stabilized Radicals: The Pent-1-en-3-yl + O-2 Reaction

Dontgen Malte; Pekkanen Timo T.; Joshi Satya P.; Timonen Raimo S.; Eskola Arkke J.

首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Oxidation Kinetics and Thermodynamics of Resonance-Stabilized Radicals: The Pent-1-en-3-yl + O-2 Reaction

【24h】

Oxidation Kinetics and Thermodynamics of Resonance-Stabilized Radicals: The Pent-1-en-3-yl + O-2 Reaction

机译：共振稳定基团的氧化动力学和热力学：PET-1-EN-3-YL + O-2反应

获取原文

获取原文并翻译 | 示例

掌桥外文数据库（机构版） >>

开具论文收录证明 >>

文献代查 >>

页面导航

摘要
著录项
相似文献
相关主题

摘要

The kinetics and thermochemistry of the pent-1-en-3-yl radical reaction with molecular oxygen (CH2CHCHCH2CH3 + O-2) has been studied by both experimental and computational methods. The bimolecular rate coefficient of the reaction was measured as a function of temperature (198-370 K) and pressure (0.2-4.5 Torr) using laser photolysis-photoionization mass-spectrometry. Quantum chemical calculations were used to explore the potential energy surface of the reaction, after which Rice-Ramsperger-Kassel-Marcus theory/master equation simulations were performed to investigate the reaction. The experimental data were used to adjust key parameters, such as well depths, in the master equation model within methodological uncertainties. The master equation simulations suggest that the formation rates of the two potential RO2 adducts are equal and that the reaction to QOOH is slower than for saturated hydrocarbons. The initial addition reaction, CH2CHCHCH2CH3 + O-2, is found to be barrierless when accounting for multireference effects. This is in agreement with the current experimental data, as well as with past experimental data for the allyl + O-2 reaction. Finally, we conducted numerical simulations of the pent-1-en-3-yl + O-2 reaction system and observed significant amounts of penta-1,3-diene being formed under engine-relevant conditions.

机译：通过实验和计算方法研究了与分子氧（CH2CHCHCH2CH3 + O-2）的PET-1-ZH-3-YL自由基反应的动力学和热化学。使用激光光解 - 光相质量 - 光谱法测量反应的双分子率系数作为温度（198-370k）和压力（0.2-4.5托）的函数。量子化学计算用于探索反应的潜在能量表面，之后进行稻米二枪康狼 - 马库斯理论/母型方程模拟以研究反应。实验数据用于调整在方法的不确定因素中的主方程模型中的关键参数，例如深度深度。主级方程模拟表明，两个潜在的RO2加合物的形成速率相等，并且对QOOH的反应比饱和烃的反应慢。初始添加反应CH2CHCHCH2CH3 + O-2被发现在考虑多次引导效应时是障碍。这与目前的实验数据一致，以及烯丙基+ O-2反应的过去的实验数据。最后，我们进行了PET-1-ZH-3-YL + O-2反应体系的数值模拟，并观察到在发动机相关条件下形成的大量五环 - 1,3-二烯。

著录项

来源
《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2019年第37期|共14页
作者
Dontgen Malte; Pekkanen Timo T.; Joshi Satya P.; Timonen Raimo S.; Eskola Arkke J.;
展开▼
作者单位

Univ Helsinki Dept Chem POB 55 AI Virtasen Aukio 1 FI-00014 Helsinki Finland;

Univ Helsinki Dept Chem POB 55 AI Virtasen Aukio 1 FI-00014 Helsinki Finland;

Univ Helsinki Dept Chem POB 55 AI Virtasen Aukio 1 FI-00014 Helsinki Finland;

Univ Helsinki Dept Chem POB 55 AI Virtasen Aukio 1 FI-00014 Helsinki Finland;

Univ Helsinki Dept Chem POB 55 AI Virtasen Aukio 1 FI-00014 Helsinki Finland;

展开▼
收录信息
原文格式 PDF
正文语种 eng
中图分类物理化学（理论化学）、化学物理学;
关键词

相似文献

外文文献
中文文献
专利

1. Oxidation Kinetics and Thermodynamics of Resonance-Stabilized Radicals: The Pent-1-en-3-yl + O-2 Reaction [J] . Dontgen Malte, Pekkanen Timo T., Joshi Satya P., The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2019,第37期

机译：共振稳定基团的氧化动力学和热力学：PET-1-EN-3-YL + O-2反应
2. Atmospheric chemistry of propionaldehyde: Kinetics and mechanisms of reactions with OH radicals and Cl atoms, UV spectrum, and self-reaction kinetics of CH3CH2C(O)O-2 radicals at 298 K [J] . Le Crane JP, Villenave E, Hurley MD, The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2005,第51期

机译：丙醛的大气化学：与OH自由基和Cl原子，UV光谱以及298 K时CH3CH2C（O）O-2自由基的自反应动力学的动力学和反应机理
3. Kinetics of the Methyl-Vinyl Radical + O-2 Reactions Associated with Propene Oxidation [J] . Joshi Satya P., Pekkanen Timo T., Timonen Raimo S., The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2019,第5期

机译：与丙烯氧化相关的甲基乙烯基自由基+ O-2反应的动力学
4. Thermochemical properties, Δ_fH°(298), S°(298), and C_P°(T), for n-butyl and n-pentyl hydroperoxides, the alkyl and peroxy radicals, transition states and kinetics for intramolecular hydrogen shift reactions to the peroxy radicals [C] . Li Zhu, Christopher J. Pope, Lisa M. Kardos, Technical Meeting of Western States Section of the Combustion Institute . 2011

机译：热化学性质，Δ_fh°（298），s°（298）和c_p°（t），用于正丁基和正戊基氢过氧化物，烷基和过氧基团，过渡态和用于分子内氢转移反应的过氧化物的动力学激进
5. Section I. Thermodynamic properties of hydrocarbon radicals, peroxy hydrocarbon and peroxy chlorohydrocarbon molecules and radicals. Section II. Kinetics and reaction mechanisms for: (1) chloroform pyrolysis and oxidation; (2) benzene and toluene oxidation under atmospheric conditions. [D] . Lay, Tsan-Horng. 1995

机译：第一节：烃基，过氧烃和过氧氯烃分子和基团的热力学性质。第二节。动力学和反应机理为：（1）氯仿热解和氧化；（2）在大气条件下苯和甲苯的氧化。
6. Thermodynamic and kinetic considerations for the reaction of semiquinone radicals to form superoxide and hydrogen peroxide [O] . Yang Song, Garry R. Buettner -1

机译：用于形成超氧化物和过氧化氢的半醌基团反应的热力学和动力学考虑
7. Oxidation Kinetics and Thermodynamics of Resonance-Stabilized Radicals: The Pent-1-en-3-yl + O2 Reaction [O] . -1

机译：共振稳定基团的氧化动力学和热力学：PET-1-ZH-YL + O 2反应
8. Photochemistry of the Gaseous Hydrogen Peroxide-Carbon Monoxide System:Rate Constants for Hydroxyl Radical Reactions by Competitive Kinetics. [R] . volman,david h. gorse,robert a. 1974

机译：气态过氧化氢 - 一氧化碳体系的光化学：竞争动力学的羟基自由基反应速率常数。

Oxidation Kinetics and Thermodynamics of Resonance-Stabilized Radicals: The Pent-1-en-3-yl + O-2 Reaction

摘要

著录项

相似文献

相关主题

期刊订阅