云南民族大学学报（自然科学版）2017，Vol.26Issue(6)：443-450,8.DOI:10.3969/j.issn.1672-8513.2017.06.003
丙烯腈水解反应机理的理论研究
Theoretical study of the reaction mechanism of acrylonitrile hydrolysis
摘要
Abstract
The hydrolysis of acrylonitrile has been studied by using the density functional theory, and two reaction pathways have been designed. The geometries for the reactants, intermediates, transition states and products have been optimized at B3lyp/6-31+ +G(d,p) level. In the pathway-A, the first step involves the water molecule attacking the C atom of C— C in acrylonitrile, and the H atom of water transfers to the other C atom of C—C at the same time. In the second step, another water molecule attacks the C atom of C≡N with the H atom transfer-ring to the N atom. The next step corresponds a rotational transition state. The H atom in the hydroxyl group adja-cent to the N atom transfers to the N atom to form the final product amide in the fourth step. The free energy barrier of the first step is the highest, which is equal to 52 kcal/mol, and therefore the first step is proved to be the rate-controlling step for the pathway-A. The first step of process B is that the water molecule attacks C≡N first, and then the second water molecule attacks C—C. The following processes are similar to the pathway-A. In the path-way-B, the free energy barrier of the first step is also the highest, which is equivalent to 47kcal/mol. Conse-quently, the first step of process B is verified to be the rate-controlling step. In conclusion, the pathway-B is more favorable than the pathway-A.关键词
丙烯腈/水解/反应途径/密度泛函Key words
acrylonitrile/hydrolysis/reaction pathway/density functional theory分类
化学化工引用本文复制引用
杨翠翠,李粉吉,杨云汉,李相华,夏福婷,彭金辉,朱华..丙烯腈水解反应机理的理论研究[J].云南民族大学学报（自然科学版）,2017,26(6):443-450,8.基金项目
国家重点基础研究发展计划(973计划)(2014CB643404) （973计划）
国家自然科学基金(21567030,11447191) （21567030,11447191）
云南省科技厅应用基础研究计划青年项目(2013FD033) （2013FD033）
省部共建复杂有色金属资源清洁利用国家重点实验室2014年开放基金(CNMRCUKF1405). （CNMRCUKF1405）
