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A reevaluation of low temperature experimental rate data for the reactions of O atoms with methane, ethane, and neopentane
Author(s) -
Cohen N.
Publication year - 1986
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.550180107
Subject(s) - neopentane , chemistry , methane , alkane , thermodynamics , stoichiometry , reagent , reaction rate , elementary reaction , atmospheric temperature range , reaction rate constant , analytical chemistry (journal) , hydrocarbon , organic chemistry , kinetics , catalysis , molecule , physics , quantum mechanics
The experimental data for the reactions of oxygen atoms with methane, ethane, and neopentane at temperatures below ca. 600 K have been reexamined. In the case of CH 4 and C 2 H 6 reactions, detailed computer models have been assembled to test the assumptions regarding stoichiometries that were made in the original studies in order to derive elementary rate coefficients from the experimentally observed reaction rates. It was found in both cases that the measurements are especially sensitive to secondary reactions not taken into account and impurities in the reagent alkane. Because the original reports did not include sufficient experimental details, it is not now possible to correct their results quantitatively. However, it appears, qualitatively, that the values for the O + CH 4 and O + C 2 H 6 rate coefficients were overestimated by factors of approximately 2 to 3 in the 250–400 K temperature range, with the error increasing as T decreases. Although the experimental results for the O + neopentane reaction are not as sensitive to the same kinds of complications, a comparison of the low‐temperature measurements with those for the O + ethane reaction suggests that the previously recommended rate coefficients, based on the data of Herron and Huie, are probably also too high by a factor of 2 to 3.