水相中喹啉的辐解机理研究

Pulse radiolysis mechanism study of quinoline in dilute solutions

利用纳秒级脉冲辐解技术对多种条件下喹啉水溶液的氧化还原机理进行了研究,并对瞬态粒子的主要吸收峰作了归属。探讨了喹啉在羟基、氢自由基、水合电子作用下所产生的瞬态粒子的生成、衰减行为。研究表明,·OH与喹啉在碱性条件下反应生成OH-加合物,速率常数为5.5×109L/mol?s?;在酸性条件下喹11啉先与氢离子反应生成喹啉阳离子,再与羟基发生加成反应,反应速率常数为7.9×109L/mol?s?;在中性条11件下和在碱性条件下反应相似,反应速率常数为7.2×109L/mol?s?;喹啉与水合电子反应生成的喹啉阴离子11自由基,其反应速率常数为7.05×109L/mol?s?;喹啉还可以与氢自由基的发生亲电加成反应。

Pulse radiolysis of aqueous quinoline in dilute solutions under different conditions was studied. The main characteristic peaks in the transient absorption spectra were attributed and the build?up/decay trends of several transient species were investigated. Under alkaline conditions, interactions between OH radicals and quinoline molecules yield OH?adducts with a rate constant of 5.5×109 L/mol ?1s? . Under acidic conditions, quinoline 1 molecules react with H+ radicals to form quinoline cations, which react with OH radicals to yield quinoline cation OH?adducts with a rate constant of 7.90×109 L/mol ?1 ?1 s . The reaction mechanism of OH in alkaline conditions and in neutral conditions are the same, the rate constant in neutral condition is 7.15×109 L/mol ?1 ?1 s . The reaction of H with quinoline produces H–adduct. In neutral solutions, eaq react with quinoline and produce quinoline anion with a ? rate constant of 7.05×109 L/mol ?1 ?1 s .