Analysis of Quantum Yields for the Photolysis of Formaldehyde at λ > 310 nm†
Analysis of Quantum Yields for the Photolysis of Formaldehyde at λ > 310 nm†
复制标题
λ > 310 nm 处甲醛光解的量子产率分析†
DOI：
--
复制
发表时间：
2007
期刊：
影响因子：
--
通讯作者：
J. Troe
中科院分区：
文献类型：
--
作者：
J. Troe
λ > 310 nm处甲醛光解的实验量子产率结合了发生在电子基态的分子消除H2CO→H2 + CO(1)、键裂变H2CO→H + HCO(2)和分子内抽氢H2CO→H··HCO→H2 + CO(3)的绝对速率和相对速率计算。分析了量子产率与温度和压力的关系，以达到实验和模型的一致性。考虑了两个性质截然不同的波长范围：340 - 360 nm，通道1与激发态分子的碰撞失活竞争；310 - 340 nm，主要是自由基形成和分子产物之间的竞争。甲醛的光解和热解之间的密切关系，如在配套论文中分析的热解，被记录，并提供了一个内部一致的处理两个反应系统。量子产率模型和r…
Experimental quantum yields of the photolysis of formaldehyde at λ > 310 nm are combined with absolute and relative rate calculations for the molecular elimination H2CO → H2 + CO (1), the bond fission H2CO → H + HCO (2), and the intramolecular hydrogen abstraction H2CO → H ··· HCO → H2 + CO (3) taking place in the electronic ground state. Temperature and pressure dependencies of the quantum yields are analyzed with the goal to achieve consistency between experiment and modeling. Two wavelength ranges with considerably different properties are considered: 340−360 nm, where channel 1 competes with collisional deactivation of excited molecules, and 310−340 nm, which is dominated by the competition between the formation of radical and molecular products. The close relation between photolysis and pyrolysis of formaldehyde, such as analyzed for the pyrolysis in the companion paper, is documented and an internally consistent treatment of the two reaction systems is provided. The quantum yields are modeled and r...