极化连续模型预测水相介质芳樟醇臭氧转化  

Linalool ozonolysis in aqueous solution with the polarizable continuum model

作　　者：弓晨[1] 张晨曦[1] 柏静[1] 赵宇阳[1] 张庆竹[1] 孙孝敏[1] 

机构地区：[1]山东大学环境研究院,济南250100

出　　处：《中国科技论文》2012年第6期418-422,共5页China Sciencepaper

基　　金：高等学校博士学科点专项科研基金资助项目(200804220046;20090131120023);国家自然科学基金资助项目(21177076;20903062;20737001);山东大学自主创新基金资助项目(2010TS064)

摘　　要：芳樟醇化学性质较活泼,易与大气中的臭氧反应形成二次有机气溶胶粒子,影响大气环境和人体健康。以芳樟醇为研究对象,研究了水相介质对芳樟醇臭氧转化的作用。在MPWB1K/6-31+G(d,p)水平上对该反应体系的反应物、中间体、过渡态及产物进行了几何构型优化和频率计算。应用极化连续模型(PCM),计算了水溶剂存在的环境下吉布斯自由能的变化。同时,得到了气相和液相中能够显示反应趋势的平衡常数。研究表明,(CH3)2C=CH—双键是臭氧的主要加成位置,芳樟醇的臭氧化过程为自发反应。Due to its high reactivity, linalool can easily react with 03 in atmosphere to generate secondary organic aerosols, which have a great impact on the atmospheric environment and human health. The effect of water on the mechanism of linalool ozonolysis has been studied using linalool as research object. The geometry optimization and harmonic vibration frequencies of the reactants, intermediates, transition states and products are calculated at the MPWB 1 K/6-3 l＋G（d,p） level as well. The polarizable continuum model （PCM） is used to calculate the change of Gibbs free energy in the aqueous solution. The equilibrium constants both in gas phase and in aqueous phase indicating the reaction trend are obtained according to the difference of Gibbs free energy. Our study shows that the addition of ozone to （CH3）2C=CH-is the main ozone addition position. The linalool ozonolysis happens spontaneously.

关 键 词：芳樟醇臭氧化 液相 吉布斯自由能 平衡常数 

分 类 号：TQ655[化学工程—精细化工]