丁二酸脱水制备丁二酸酐的微观反应机理研究TheoreticalStudyon.PDFVIP

2005 年第 63 卷 化 学 学 报 Vol. 63, 2005 第 16 期, 1545～1550 ACTA CHIMICA SINICA No. 16, 1545～1550 ·研究简报· 丁二酸脱水制备丁二酸酐的微观反应机理研究 李来才*,a 查 东 a 田安民 b (a 四川师范大学化学学院 成都 610066) (b 四川大学化学学院 成都 610064) 摘要 丁二酸脱水法是工业生产丁二酸酐的方法之一. 用量子化学密度泛函理论(DFT)对该反应的微观机理进行了详 细研究, 得到了该反应的微观过程. 根据计算和分析可知: 丁二酸脱水制备丁二酸酐的微观反应途径为 IM1→TS1→ IM2→TS2→IM3→TS3→P ＋H O, 在反应过程中 IM3 为氢键复合物, 整个反应的速控步为 IM3→TS3→P ＋H O, 其所 2 2 需活化能为 167.17 kJ/mol. 关键词 丁二酸酐; 丁二酸; 反应机理; 密度泛函理论 Theoretical Study on the Microcosmic Mechanism of Succinic Acid Dehydration to Produce Succinic Anhydride LI, Lai-Cai*,a ZHA, Donga TIAN, An-Minb a ( Department of Chemistry, Sichuan Normal University, Chengdu 610066) b ( Department of Chemistry, Sichuan University, Chengdu 610064) Abstract Succinic acid dehydration is one of industrial methods to produce succinic anhydride. In this work, density functional theory has been performed to study the microcosmic reaction mechanism of succinic acid dehydration. According to the calculational and analytic results, the microcosmic reaction process is IM1→ TS1→IM2→TS2→IM3→TS3→P ＋H2O. Especially, IM3 is a hydrogen-bond compound. The controlling step of the whole reaction is IM3→TS3→P ＋H2O, with its activation energy of 167.17 kJ/mol. Keywords succinic anhydride; succinic acid; reaction mechanism; density functional theory 丁二酸酐是涂料、染料、医药的原料,