缔合水分子对H_2O_2+NH_3→H_2O+ONH_3反应机理的影响  

Effect of Inclusion of Water Molecules Associated on Mechanism of H_2O_2+ NH_3→H_2O+ONH_3

作　　者：常刚[1] 王斌举[1] 张俊[1] 夏文生[1] 万惠霖[1] 

机构地区：[1]厦门大学化学化工学院,固体表面物理化学国家重点实验室,醇醚酯清洁化工国家工程实验室,厦门361005

出　　处：《高等学校化学学报》2010年第9期1820-1826,共7页Chemical Journal of Chinese Universities

基　　金：国家"九七三"计划项目(批准号:2005CB221408;2010CB732303);福建省自然科学基金(批准号:2007J0168E0710027)资助

摘　　要：对反应H2O2+NH3→NH3O+H2O中H2O2上的O转移至NH3上所涉及的2种可能途径(即H2O2中H的迁移是否优先于O转移)及缔合水分子对反应的影响进行了量子化学计算.结果表明,两步式机理比一步式机理有利,而反应物缔合的水分子数及其排列方式对反应能垒的影响甚大.当缔合水分子数n=5时,反应活化能值达到最低,经溶剂化效应校正后反应活化能与实验值相当.溶剂化效应的大小与反应机理和反应物缔合的水分子数有关.The two possible mechanisms（ whether oxygen transfers prior to hydrogen migration） of reaction H2O2＋NH 3 →NH3O ＋ H2O with explicit inclusion of water molecules associated are investigated by means of quantum chemistry calculations. The results show that two-step mechanism（ H migration prior to O transfer） is preferred to one-step mechanism,and the reaction barrier is significantly affected by the geometric arrangement and the number of water molecules associated with reactants. When the number of water molecules associated is 5,the barrier reaches to the lowest value,which,after solvent effect correction,is comparable to the experimental results reported. The contribution from solvent effect is related to the reaction mechanisms and the number of water molecules associated.

关 键 词：缔合水 过氧化氢 氨气 反应机理 密度泛函理论 

分 类 号：O641[理学—物理化学]