title: Pyrolysis of methyl tert-butyl ether (MTBE). 2. Theoretical study of decomposition pathways.
abstract: The thermal decomposition pathways of MTBE have been investigated using the G3B3 method. On the basis of the experimental observation and theoretical calculation, the pyrolysis channels are provided, especially for primary pyrolysis reactions. The primary decomposition pathways include formation of methanol and isobutene, CH4 elimination, H2 elimination and C-H, C-C, C-O bond cleavage reactions. Among them, the formation channel of methanol and isobutene is the lowest energy pathway, which is in accordance with experimental observation. Furthermore, the secondary pyrolysis pathways have been calculated as well, including decomposition of tert-butyl radical, isobutene, methanol and acetone. The radicals play an important role in the formation of pyrolysis products, for example, tert-butyl radical and allyl radical are major precursors for the formation of allene and propyne. Although some isomers (isobutene and 1-butene, allene and propyne, acetone and propanal) are identified in our experiment, these isomerization reaction pathways occur merely at the high temperature due to their high activation energies. The theoretical calculation can explain the experimental results reported in part 1 and shed further light on the thermal decomposition pathways.
authors.affiliation: National Synchrotron Radiation Laboratory, University of Science and Technology of China,Hefei, Anhui 230029, PR China.
authors.forename: Taichang
authors.initials: T
authors.lastname: Zhang
authors.forename: Lidong
authors.initials: L
authors.lastname: Zhang
authors.forename: Jing
authors.initials: J
authors.lastname: Wang
authors.forename: Tao
authors.initials: T
authors.lastname: Yuan
authors.forename: Xin
authors.initials: X
authors.lastname: Hong
authors.forename: Fei
authors.initials: F
authors.lastname: Qi
mesh_terms: D000096:Acetone / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry; D003198:Computer Simulation; D005609:Free Radicals / Q000737:chemistry; D006358:Hot Temperature; D006859:Hydrogen / Q000737:chemistry; D008697:Methane / Q000737:chemistry; D000432:Methanol / Q000737:chemistry; D008738:Methyl Ethers / Q000737:chemistry*; D008956:Models, Chemical; D010084:Oxidation-Reduction; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D005609:Free Radicals; D008738:Methyl Ethers; D000096:Acetone; C043243:methyl tert-butyl ether; D006859:Hydrogen; D008697:Methane; C008176:isobutylene; D000432:Methanol