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A computational modeling study of the low‐temperature pyrolysis of n ‐alkanes; mechanisms of propane, n ‐butane, and n ‐pentane pyrolyses
Author(s) -
Allara D. L.,
Edelson D.
Publication year - 1975
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.550070402
Subject(s) - propane , butane , chemistry , pentane , alkane , pyrolysis , a priori and a posteriori , radical , thermodynamics , organic chemistry , hydrocarbon , physics , catalysis , philosophy , epistemology
The mechanisms of the pyrolyses of the n ‐alkanes C 3 H 8 , n ‐C 4 H 10 , and n ‐C 5 H 12 at temperatures between 390 and 560°C have been studied by the construction and evaluation of sets of several hundred reactions. Rate parameter values were assigned using literature data and calculated estimates. Time‐dependent numerical solutions were computed for the experimental conditions of several rate and product studies reported in the literature. The comparisons of these a priori computations with experiment show excellent agreement for propane and agreement for butane and pentane within the estimated error limits of the assigned rate parameters. These results demonstrate that the general “state of knowledge” of the mechanism of alkane pyrolysis, namely, the reactions and their rate parameters, is such that reasonable a priori predictions of experimental results can be made. Discussions of the major stepwise processes in the pyrolyses are presented, and the importance of allyl radicals in termination is demonstrated.