【摘要】 利用脉冲辐解技术对2-氯酚稀水溶液在多种条件下的脉冲辐解进行了详细研究。对瞬态光谱中的主要吸收作了归属,并初步考察了这些瞬态粒子的生长、衰减动力学。实验表明2-氯酚与·OH的反应符合假一级动力学,2-氯酚与·OH自由基的反应途径与pH值有关:在中性条件下·OH与2-氯酚主要生成较为稳定的羟基加成物;在酸性条件下,同时生成了羟基加成物和氢加成物,且羟基加成物可发生H⁺催化的脱H₂O反应,生成氯酚氧基;在碱性条件,2-氯酚阴离子的羟基加成物不稳定,可进一步脱HCI和OH-而生成氯代酚氧基阴离子和半醌自由基阴离子,同时2-氯酚阴离子与·OH还可直接发生电子转移,形成氯代酚氧基阴离子。更多还原

【Abstract】 The reaction between OH radicals and 2-chlorophenol in dilute aqueous solutions under different conditions wasstudied by pulse-radiolysis tecnology. The main characteristic peaks in the transient absorption spectra were attributed and thebuild-up/decay trends of several transient species were investigated. The reaction of 2-chlorophenol with·OH radicals followspseudo-first order kinetics and the reaction paths are pH dependent. Under neutral condition,·OH radicals are mainly addedto the benzyl ring to form relatively stable hexadienyl type OH-adducts. Under acidic condition, both OH-adducts and H-adducts are formed and OH-adducts can undergo H⁺ induced H₂O elimination. Under alkaline condition, chlorophenoxyl radi-cals and semiquinone radical anions can be formed through OH-addition followed by HCl/OH-elimination. In addition, 2-chlorophenoxyl radicals can also be formed through the electron transfer from 2-chlorophenol anion to ·OH.更多还原