Flash photolysis-resonance fluorescence kinetic study of the reactions hydroxyl + molecular hydrogen .fwdarw. water + atomic hydrogen and hydroxyl + methane .fwdarw. water + methyl from 298 to 1020 K
Flash photolysis-resonance fluorescence kinetic study of the reactions hydroxyl + molecular hydrogen .fwdarw. water + atomic hydrogen and hydroxyl + methane .fwdarw. water + methyl from 298 to 1020 K
复制标题
羟基分子氢反应的闪光光解-共振荧光动力学研究.fwdarw。
DOI：
10.1021/j100460a031
复制
发表时间：
1980
期刊：
影响因子：
--
通讯作者：
A. Ravishankara
中科院分区：
文献类型：
--
作者：
F. P. Tully;A. Ravishankara
自由基分子反应的绝对速率常数的实验测量历来是根据温度制度划分的。在低温（T; S500 K），近年来，为满足大气化学模拟的输入需求，各种技术得到了发展和应用。一般来说，这些技术允许调整实验条件，使得许多特定自由基-分子反应的绝对速率常数测量可以在竞争反应过程的干扰很小和/或可量化的情况下进行。在高温（Ts 1000 K）下，给定反应的动力学分离已被证明是更难以实现的。火焰温度下的实验通常包括仅利用最终产物分析的研究，以及涉及许多相互作用化学非常复杂的自由基（稳定分子）物质的详细浓度映射与时间（距离）的研究。序列的反应方案与参数化的绝对rateconstant值被用来迭代地重现测得的浓度分布（产品收率）。通常，提取的速率常数依赖于模型，与其他不充分表征的反应的速率常数成比例，或者仅在所获得的原始数据的宽范围内敏感。高温动力学测量的解释清晰度已被观察到平行的实验控制水平。在介于这些不同区域之间的温度（500-1000 K），对自由基-分子反应速率常数的研究相对较少。两个反应（方程式1和2）已经得到了
Experimental measurements of absolute rate constants for radical-moleculereactions have historically been divided according to temperature regime. At low tempera-ture (T; S 500 K) a variety of techniques1 have been de-veloped and utilized inrecent years in response to the input demands of atmospheric chemical modeling. Gen-erally speakingthese techniques permit the adjustment of experimental conditions such that the absolute rate-constant measurements for many specific radical-molecule reactions may be made with little, and/or quantifiable, interference from competing reaction processes. At high temperature (Ts 1000 K) kinetic isolation of a given reaction has proved to be much more difficult to achieve. Experiments at flame temperatures typically range from studies utilizing end-product analysis alone to investigations involving detailed concentration mapping vs. time (distance) of a number of radical (stable molecule) species whose interactive chemistry is very complex. Sequences of reaction schemes with parameterized absolute rateconstant values are used to iteratively reproduce the measured concentration profiles (product yields). Fre-quently the extracted rateconstants are model dependent, ratioed to those of other insufficiently characterized re-actions, or sensitive within only broad limits on the ob-tained raw data. The interpretive clarity of high-temperature kinetic measurements has been observed to parallel the level of experimental control. At temperatures intermediate between these separated regimes, 500-1000 K, relatively few investigations of rad-ical-molecule reaction rate constantshave been undertaken. Two reactions (eq 1 and 2) which have recieved