Mechanism and kinetics of the production of hydroxymethyl hydroperoxide in ethene/ozone/water gas-phase system

作     者：QI Bin CHAO YuTao CHEN ZhongMing 

作者机构：School of Chemistry and Material SciencesShaanxi Normal UniversityXi’an 710062China State Key Laboratory of Environmental Simulation and Pollution ControlPeking UniversityBeijing 100871China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2007年第50卷第3期

页      面：425-431页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：Supported by the National Natural Science Foundation of China (Grant No. 20107001) 

主　　题：ethane ozone rate constant HMHP density functional theory 

摘      要：The mechanism and kinetics of the production of hydroxymethyl hydroperoxide (HMHP) in ethene/ozone/water gas-phase system were investigated at room temperature (298±2 K) and atmospheric pressure (1×105 Pa). The reactants were monitored in situ by long path FTIR spectroscopy. Peroxides were measured by an HPLC post-column fluorescence technique after sampling with a cold trap. The rate constants (k 3) of reaction CH2O2+H2O→HMHP (R3) determined by fitting model calculations to experimental data range from (1.6?6.0)×10?17 cm3·molecule?1·s?1. Moreover, a theoretical study of reaction (R3) was performed using density functional theory at QCISD(T)/6-311+(2d,2p)//B3LYP/6-311+G(2d,2p) level of theory. Based on the calculation of the reaction potential energy surface and intrinsic reaction coordinates, the classic transitional state theory (TST) derived k 3 (k TST), canonical variational transition state theory (CVT) derived k 3 (k CVT), and the corrected k CVT with small-curvature tunneling (k CVT/SCT) were calculated using Polyrate Version 8.02 program to be 2.47×10?17, 2.47×10?17 and 5.22×10?17 cm3·molecule?·s?1, respectively, generally in agreement with those fitted by the model.