STUDIES ON THE ELEMENTARY REACTIONS RELATED TO LOW-TEMPERATURE OXIDATION OF HYDROCARBONS

利用光电离质谱、激波管和激光诱导荧光技术，研究了与烃类低温氧化机理有关的几个重要基元反应。本项目研究的反应类型有：（1）O（^3P）从一系列C1-CO烷烃中直接夺取氢原子，（2）C2-CO烷基自由基的热分解和异构化过程，（3）丁基过氧自由基的热分解，以及烷氧基自由基的热分解、消耗和产生。系统地研究了C-H键的一级、二级和三级中心的位置选择性、产物的支化率和压降效应的一般速率规律。它们是第一个直接调查的检查一系列烷烃，烷基烷基过氧，烷氧基自由基的反应性。

By using photoionization mass spectrometry, shock tube, and laser induced fluorescence techniques, several important elementary reactions related to low tomperature oxidation mechanism of hydrocarbons have been investigated. The types of reactions studied in this project are ; (1) direct abstraction of hydrogen atoms by O(^3P) from a series of C1-CO alkanes, (2) thermal decomposition and isomerization processes of C2-CO alkyl radicals, (3) thermal decomposition of butylperoxi radicals, and thermal decomposition, consumption, and production of alkoxi radicals.Not only the rate constants for individual reactions, the general rate laws for the site selectivity for primary secondary and tertiary sites of C-H bond, branching fractions for the products, and the pressure fall-off effects are investigated systematically. They are the first direct investigations of examination for the reactivity of a series of alkanes, alkyl alkylperoxi, and alkoxiradicals.