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Kinetic study and modeling of the hetero‐homo‐geneous pyrolysis and oxidation of isobutane around 800 K. Part III. Pyrolysis‐oxidation in unpacked and in pbO‐coated packed Pyrex reactors
Author(s) -
Zils R.,
Perrin D.,
Martin R.
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)30:9<657::aid-kin7>3.0.co;2-r
Subject(s) - isobutane , chemistry , pyrolysis , radical , oxygen , batch reactor , atmospheric temperature range , chemical engineering , organic chemistry , thermodynamics , catalysis , physics , engineering
Isobutane pyrolysis has been studied in the presence of oxygen at about 773 K in unpacked and in PbO‐coated packed Pyrex reactors. The reaction is shown to be accelerated by oxygen in reactors of low surface‐to‐volume ratio and strongly inhibited in packed PbO‐coated reactors. These oxygen effects are explained in terms of interaction between two radical chain systems, one of pyrolysis, the other of oxidation. Oxygen introduces additional chain initiations and a degenerate chain branching step due to H 2 O 2 while oxygenated radicals are efficiently removed at the reactor wall. All experimental results have been modeled and many rate constants of elementary steps were evaluated. The collision efficiency of HO 2. radicals on a PbO‐coated Pyrex surface has been determined in the temperature range of this study. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 657–671, 1998