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

作　　者：QI Bin CHAO YuTao CHEN ZhongMing 

机构地区：[1]School of Chemistry and Material Sciences,Shaanxi Normal University,Xi’an 710062,China [2]State Key Laboratory of Environmental Simulation and Pollution Control,Peking University,Beijing 100871,China

出　　处：《Science China Chemistry》2007年第3期425-431,共7页中国科学（化学英文版）

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

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.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 (k3) of reaction CH2O2+H2O→HMHP (R3) determined by fitting model calculations to ex-perimental data range from (1.6―6.0)×10?17 cm3·molecule?1·s?1. Moreover, a theoretical study of reac-tion (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 reac-tion coordinates, the classic transitional state theory (TST) derived k3 (kTST), canonical variational tran-sition state theory (CVT) derived k3 (kCVT), and the corrected kCVT with small-curvature tunneling (kCVT/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-1·s-1, respectively, generally in agreement with those fitted by the model.

关 键 词：ETHANE OZONE rate constant HMHP density functional theory 

分 类 号：O621.2[理学—有机化学]