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利用脉冲电子束辐解水产生· OH自由基、· H及水合电子 (e- aq) ,研究了这些活性粒子在多种条件下与水相中 2 -氯酚的微观反应机理 ,对其瞬态光谱中的主要吸收峰做了归属 ,并初步考察了这些瞬态物种的生长、衰减等行为 .研究表明 ,· OH自由基与 2 -氯酚在碱性条件下可直接反应生成邻氯代酚氧自由基 ,速率常数为 1 .0× 1 0 9L· mol- 1 · s- 1 ,也有部分· OH自由基与 2 -氯酚反应先生成 OH-加合物 ,再进一步消除水分子生成邻氯代酚氧基 ;在酸性条件下要经过 OH-加合物 .· H则与 2 -氯酚反应生成 H-加合物 ;e- aq可直接从 2 -氯酚分子夺氯 ,在近中性和碱性环境中 ,该反应的速率常数分别为 1 .2 5× 1 0 9L· mol- 1 ·s- 1 和 6.3×1 0 8L·mol- 1· s- 1 .
The mechanism of microscopic reaction between 2-chlorophenol and 2-chlorophenol in aqueous solution was studied under various conditions by using pulsed electron beam to generate · OH free radical, · H and hydrated electron (e-aq) The main absorption peaks in the spectra were assigned and the growth, decay and other behaviors of these transient species were investigated preliminarily.The results showed that · OH radical reacted directly with 2 - chlorophenol under alkaline conditions to form o - chlorinated Phenolic oxygen free radicals, the rate constant of 1.0 × 109L · mol-1 · s-1, but also some · OH radical reaction with 2-chlorophenol into OH-adduct, and then further eliminate the water molecules O-chlorophenoxy, O-adduct under acidic conditions H Reacts with 2-chlorophenol to form H-adduct E-aq can take chlorine directly from 2- Nearly neutral and alkaline environments, the rate constants of this reaction are respectively 1.25 × 109L · mol-1 · s-1 and 6.3 × 108L · mol-1 · s-1.