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A comprehensive mechanism for methanol oxidation
Author(s) -
Held Timothy J.,
Dryer Frederick L.
Publication year - 1998
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/(sici)1097-4601(1998)30:11<805::aid-kin4>3.0.co;2-z
Subject(s) - chemistry , mechanism (biology) , methanol , biochemical engineering , combinatorial chemistry , organic chemistry , epistemology , philosophy , engineering
A comprehensive detailed chemical kinetic mechanism for methanol oxidation has been developed and validated against multiple experimental data sets. The data are from static‐reactor, flow‐reactor, shock‐tube, and laminar‐flame experiments, and cover conditions of temperature from 633–2050 K, pressure from 0.26–20 atm, and equivalence ratio from 0.05–2.6. Methanol oxidation is found to be highly sensitive to the kinetics of the hydroperoxyl radical through a chain‐branching reaction sequence involving hydrogen peroxide at low temperatures, and a chain‐terminating path at high temperatures. The sensitivity persists at unusually high temperatures due to the fast reaction of CH 2 OH+O 2 =CH 2 O+HO 2 compared to CH 2 OH+M=CH 2 O+H+M. The branching ratio of CH 3 OH+OH=CH 2 OH/CH 3 O+H 2 O was found to be a more important parameter under the higher temperature conditions, due to the rate‐controlling nature of the branching reaction of the H‐atom formed through CH 3 O thermal decomposition. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 805–830, 1998