An Experimental and Theoretical Study of Pyrrole Pyrolysis with Tunable Synchrotron VUV Photoionization and Molecular-Beam Mass Spectrometry

被引:37
作者
Hong, Xin [1 ]
Zhang, Lidong [1 ]
Zhang, Taichang [1 ]
Qi, Fei [1 ]
机构
[1] Univ Sci & Technol China, Natl Synchrotron Radiat Lab, Hefei 230029, Anhui, Peoples R China
关键词
PULSE SHOCK-TUBE; AB-INITIO; ELEVATED-TEMPERATURES; HYDROGEN-CYANIDE; ISOMERIZATION; DECOMPOSITION; IONIZATION; KINETICS; ENERGY; PHENYLNITRENE;
D O I
10.1021/jp9002966
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The Pyrolysis of pyrrole (6.46% pyrrole in argon) has been performed with the tunable synchrotron vacuum ultraviolet (VUV) photoionization and molecular-beam mass spectrometry (MBMS) technique. The experiment was carried out over the temperature range of 1260-1710 K at a pressure of 267 Pa. About 30 intermediates have been identified by near-threshold measurements of photoionization mass spectra, and the corresponding mole fractions versus temperatures have been obtained. Moreover, the isomers of some pyrolysis products have been identified by the measurement of photoionization efficiency spectrum. The major products are H-2, C2H2, HCN, C3H4 (propyne), and C2H3N (acetonitrile). Meanwhile, some new intermediates, such as C4H4N (cyanoallyl radical) and C2H2N (cyanomethyl radical), have been determined. The major pyrolysis channels have been provided with the high-level ab initio G3B3 calculation and are well consistent with the experimental observation. The formation pathway of HCN via the cyclic carbene tautomer has been proved to be the lowest formation pathway, which is in accordance with previous theoretical work. The potential pathways of the early formed C4H4N species together with their subsequent consumption to C2H2N and C2H2 have been discussed in detail. Also, the formation pathways of the major products of C2H3N and C2H2 have been investigated as well.
引用
收藏
页码:5397 / 5405
页数:9
相关论文
共 45 条
[21]   Analysis of flame structure by molecular-beam mass spectrometry using electron-impact and synchrotron-photon ionization [J].
Ph. R. Westmoreland ;
M. E. Law ;
T. A. Cool ;
J. Wang ;
A. McIlroy ;
C. A. Taatjes ;
N. Hansen .
Combustion, Explosion and Shock Waves, 2006, 42 :672-677
[22]   Analysis of flame structure by molecular-beam mass spectrometry using electron-impact and synchrotron-photon ionization [J].
Westmoreland, Ph. R. ;
Law, M. E. ;
Cool, T. A. ;
Wang, J. ;
McIlroy, A. ;
Taatjes, C. A. ;
Hansen, N. .
COMBUSTION EXPLOSION AND SHOCK WAVES, 2006, 42 (06) :672-677
[23]   Online Analysis of Volatile Products from Bituminous Coal Pyrolysis with Synchrotron Vacuum Ultraviolet Photoionization Mass Spectrometry [J].
Jia, Liangyuan ;
Weng, Junjie ;
Wang, Yu ;
Sun, Shaobo ;
Zhou, Zhouyue ;
Qi, Fei .
ENERGY & FUELS, 2013, 27 (02) :694-701
[24]   Catalytic pyrolysis of xylan over alkali metal salts as revealed by synchrotron vacuum ultraviolet photoionization mass spectrometry [J].
Li, Yamin ;
Wang, Jinglan ;
Chen, Xiamin ;
Cheng, Zhanjun ;
Xu, Minggao ;
Yang, Jiuzhong ;
Jia, Liangyuan ;
Pan, Yang .
JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS, 2018, 135 :94-100
[25]   Terpene speciation: Analytical insights into the oxidation and pyrolysis of limonene and 1,8-cineole via molecular-beam mass spectrometry [J].
Bierkandt, Thomas ;
Gaiser, Nina ;
Bachmann, Jasmin ;
Osswald, Patrick ;
Koehler, Markus .
COMBUSTION AND FLAME, 2025, 272
[26]   Mechanistic Study of Thermal Decomposition of Hexamethyldisilane by Flash Pyrolysis Vacuum Ultraviolet Photoionization Time-of-Flight Mass Spectrometry and Density Functional Theory [J].
Liu, Xinghua ;
Zhang, Jingsong ;
Vazquez, Alexis ;
Wang, Daxi ;
Li, Shuyuan .
JOURNAL OF PHYSICAL CHEMISTRY A, 2019, 123 (49) :10520-10528
[27]   Online study on the co-pyrolysis of coal and corn with vacuum ultraviolet photoionization mass spectrometry [J].
Weng, Jun-Jie ;
Liu, Yue-Xi ;
Zhu, Ya-Nan ;
Pan, Yang ;
Tian, Zhen-Yu .
BIORESOURCE TECHNOLOGY, 2017, 244 :125-131
[28]   Comprehensive study of the low-temperature oxidation chemistry by synchrotron photoionization mass spectrometry and gas chromatography [J].
Xu, Qiang ;
Liu, Bingzhi ;
Chen, Weiye ;
Yu, Tongpo ;
Zhang, Zunhua ;
Zhang, Cheng ;
Wei, Lixia ;
Wang, Zhandong .
COMBUSTION AND FLAME, 2022, 236
[29]   Pyrolysis study on cattle manure: From conventional analytical method to online study of pyrolysis photoionization time-of-flight mass spectrometry [J].
He, Sirong ;
Cao, Congcong ;
Wang, Jinglan ;
Yang, Jiuzhong ;
Cheng, Zhanjun ;
Yan, Beibei ;
Pan, Yang ;
Chen, Guanyi .
JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS, 2020, 151
[30]   Cellulose pyrolysis under NH3 atmosphere for levoglucosan and pyrrole: An experimental and theoretical study [J].
Chen, Wei ;
Shi, Xiaolei ;
Tao, Xuan ;
Guo, Wenjuan ;
Wang, Yurou ;
Deng, Shijing ;
Gong, Meng ;
Chen, Yingquan ;
Yang, Haiping .
FUEL, 2024, 361