·Cl引发萘的大气氧化机制及动力学
Atmospheric Oxidation Mechanism and Kinetics of Naphthalene Initiated by Chlorine Radicals (·Cl)
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摘要: 氯自由基（·Cl）内陆来源的新发现增强了其对转化大气有机污染物的贡献，因此，需要更深入地研究·Cl引发有机污染物的转化机制和动力学。萘（Nap）是一种重要的化学品，也是城市大气浓度最高的多环芳烃，前人针对羟基自由基（·OH）引发Nap的大气氧化开展了研究。然而，目前对于·Cl引发Nap的大气氧化机制还不清楚。本研究通过量子化学计算（ωB97XD/6-311++G（3df，2pd）//ωB97XD/6-31+G（d，p））和动力学模拟相结合的方法研究了·Cl引发Nap的大气氧化机制与动力学，发现·Cl主要加成到Nap分子的C5位置，形成加成中间体·C10H8Cl（R1）。随后，O2加成到R1的C2和C6位置生成过氧自由基（RO2·）R1-2OO-s/a和R1-6OO-s/a（s/a=syn/anti，syn表示O2加成方向和·Cl加成方向相同，anti表示O2加成方向和·Cl加成方向相反）。这4种RO2·的环化、氢迁移和氯迁移反应均很难（能垒>20 kcal·mol-1）发生。因此，在低NO浓度条件下，RO2·主要和HO2·反应生成氢过氧化合物（QOOH）和烷氧自由基（RO·）R1-2O-s/a和R1-6O-s/a；在高NO浓度条件下，RO2·将主要与NO反应生成RO·（R1-2O-s/a和R1-6O-s/a）和有机硝酸酯（C10H8ClNO3）。生成的RO·进一步通过单分子环化反应生成双环产物R1-21O-s/a和R1-61O-s/a。重要的是，生成的有机氢过氧化合物和有机硝酸酯的水生毒性比其母体化合物Nap更强，表明·Cl引发Nap反应增加了Nap释放的环境风险。揭示的机制对理解大气Nap化学及Nap释放导致的环境风险具有重要意义。Abstract: The new findings of chlorine radicals (·Cl) in mid-continental areas increase the importance of ·Cl in transforming atmospheric organic pollutants. Hence, more research should be performed on the atmospheric transformation of organic pollutants initiated by ·Cl. Naphthalene (Nap) is one type of chemicals and the most abundant polycyclic aromatic hydrocarbons in the urban atmosphere. Atmospheric oxidation of Nap initiated by hydroxyl radicals (·OH) have been studied previously. However, the mechanism of ·Cl initiated reaction of Nap is not fully understood. Herein, ·Cl initiated reactions of Nap were investigated by a quantum chemical method (ωB97XD/6-311++G(3df,2pd)//ωB97XD/6-31+G(d,p)) and kinetics modeling. Results show that ·Cl addition to the C5-position of Nap, forming radicals ·C10H8Cl(R1), is the dominant reaction pathway. Subsequently, O2 is mainly added to the C2 and C6 positions of R1 to form peroxy radicals (RO2·) R1-2OO-s/a and R1-6OO-s/a depending on the attacking direction of O2 (s/a=syn/anti, syn and anti correspond to the O2 additions from the same and opposite sites of the direction of ·Cl addition). In the atmosphere, the isomerization reactions (including cyclization, H-transfer, and Cl-transfer) of the four RO2· proceed very slowly due to the high reaction energy barriers (> 20 kcal·mol-1). Therefore, the formed four RO2· will mainly react with HO2· to form hydroperoxide (QOOH) and alkoxy radicals (RO·) under the condition of low NO concentration, or react with NO to form organonitrates (C10H8ClNO3) and RO· (R1-2O-s/a, R1-6O-s/a) under the condition of high NO concentration. The formed RO· will finally undergo ring-closure reactions forming bi-cyclic intermediates (R1-21O-s/a, R1-61O-s/a). More importantly, the predicted toxicity of the formed organonitrates and hydroperoxide is much higher than that of Nap, indicating the ·Cl initiated transformation of Nap increases the environmental risk caused by Nap emission. The revealed mechanism is of great significance for understanding atmospheric chemistry and environmental risk assessment of Nap.
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Key words:
- naphthalene /
- chlorine radicals /
- quantum chemistry /
- transformation mechanism /
- kinetics
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