Thermal decomposition of 1-hexene by flash pyrolysis: A study of initial decomposition mechanism |
| |
| Authors: | Xinghua Liu Wenhao Yuan Jingsong Zhang Jiuzhong Yang Zhongyue Zhou |
| |
| Institution: | 1. Key Laboratory for Power Machinery and Engineering of MOE, School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200240, P. R. China;2. Department of Chemistry, University of California, Riverside, CA 92521, U.S.A.;3. Air Pollution Research Center, University of California, Riverside, California 92521, U.S.A.;4. National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui, 230029 P R. China |
| |
| Abstract: | Thermal decomposition of 1-hexene at temperatures 295-1410 K was conducted using a flash pyrolysis micro-reactor coupled to laser-based vacuum ultraviolet photoionization time-of-flight mass spectrometer (VUV-PI-TOFMS). The decomposition mechanism of 1-hexene was developed with the help of theoretical calculation performed at the MRCI/cc-pvtz//CASSCF/6–31+G(d,p) level. The γ-scission and diradical retro-ene reactions were determined as the main initial decomposition reactions in the temperature range 990-1240 K. Two diradical retro-ene reaction channels, 1,5-diradical and 1,6-diradical reactions, were proposed in order to interpret the appearance of the C4H8 species. The 1,5-diradical retro-ene reaction involved a 1,5-diradical intermediate that subsequently decomposed via C C β-scissions to the C2, C3 and C4 products. The 1,6-diradical retro-ene reaction proceeded via a 1,6-diradical intermediate and CC β-scissions to produce the C2 and C4 species. The proposed diradical retro-ene mechanism was evidenced indirectly by the early product distribution of 1-hexene pyrolysis in a flow reactor at 1173 K determined by synchrotron radiation VUV-PI-TOFMS. It was verified in the flash pyrolysis of 1-heptene as well. |
| |
| Keywords: | |
| 本文献已被 ScienceDirect 等数据库收录！ |
|
