Premium
Toward a comprehensive mechanism for methanol pyrolysis
Author(s) -
Norton T. S.,
Dryer F. L.
Publication year - 1990
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550220303
Subject(s) - chemistry , radical , methanol , pyrolysis , shock tube , decomposition , thermal decomposition , chain termination , atmosphere (unit) , chain reaction , reaction mechanism , kinetic energy , photochemistry , thermodynamics , organic chemistry , shock wave , catalysis , physics , radical polymerization , quantum mechanics , copolymer , polymer
A single kinetic mechanism for methanol pyrolysis is tested against multiple sets of experimental data for the first time. Data are considered from static, flow, and shock tube reactors, covering temperatures of 973 to 2000 K and pressures of 0.3 to 1 atmosphere. The model results are highly sensitive to the rates of unimolecular fuel decomposition and of various chain termination reactions that remove CH 2 OH and H radicals, as well as to experimental temperature uncertainties. The secondary fuel decomposition reaction CH 3 OH = CH 2 OH + H, which has previously been included only in mechanisms for high temperature conditions, is found to have a significant effect at low temperatures as well, through radical recombination. The reaction CH 3 O + C = CH 3 + CO 2 , rather than CH 3 OH + H = CH 3 + H 2 O, is found to be the dominant source of CH 3 at low temperatures. The reverse of CH 3 + OH = CH 2 OH + H is important to CH 3 production at high temperatures.