【摘要】 利用激光闪光光解技术研究了在355 nm激光作用下甲苯与亚硝酸的交叉反应机理,考察了反应瞬态物种的生长和衰减行为,对产物进行了GC-MS分析.结果表明,HNO₂在355 nm的紫外光照下产生的OH自由基和甲苯有两种反应途径,其一是加成反应,甲苯与OH自由基反应生成CH₃C₆H₅-OH加合物,反应速率常数为（4.1±0.4）×10⁹L·mol^-1·s^-1,该反应途径在对流层大气中占主导地位;其二是发生在侧链甲基上的提氢反应,反应生成苄基自由基.有氧条件下,CH₃C₆H₅-OH可与O₂反应,氧化为CH₃C₆H₅-OHO₂,反应速率常数为（6.8±0.2）×10⁸L·mol^-1·s^-1.更多还原

【Abstract】 Reaction mechanism of aqueous solution of toluene with nitrous acid in the presence of O₂ and absence of O₂ were studied by laser flash photolysis. The main characteristic peaks in these transient absorbance spectra were assigned and the build-up/decay processes of several transient species were investigated. Results illustrated ·OH was produced in aqueous solution of nitrous acid exposed to 355 nm laser beam. There are two possible pathways of the reaction between ·OH and toluene. The first is radical adduct formation,especially the addition of ·OH to aromatic ring. The bimolecular rate constant was measured to be（ 4.1±0.4） ×109L·mol^-1·s^-1,and it was considered as a dominated way of the reaction between ·OH and toluene in troposphere system. In addition,·OH could also abstract a hydrogen atom from side chain methyl group to form benzyl radicals. The transient product CH₃C₆H₅-OH reacted with O₂ to form CH₃C₆H₅-OHO₂ with a rate constant of（ 6.8±0.2） ×10⁸L·mol^-1·s^-1. The photo products were analyzed by GC/MS and the possible reaction pathways were discussed.更多还原