Grela, M. A. and Amorebieta, V. T. and Colussi, A. J. (1992) High-temperature oxidation of methyl radicals in open systems. Journal of Physical Chemistry, 96 (17). pp. 7013-7018. ISSN 0022-3654. doi:10.1021/j100196a031. https://resolver.caltech.edu/CaltechAUTHORS:20150623-154806290
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Abstract
Rates of CH_3 oxidation by O_2 in a continuous flow, low-pressure reactor were determined by molecular beam mass spectrometry between 982 and 1395 K. F = {([CH_3]_0/[CH_3])- 1}, a measure of the extent of reaction, increases with [O_2] above threshold values [O_2]_c , and exhibits a complex dependence on [CH_3]_0; [O_2]_c values decrease with temperature. These findings are quantitatively accounted for by a gas-phase branched-chain mechanism with carrier losses at the reactor walls. Numerical simulations were performed by using two adjustable parameters. Adoption of recent data for k_2 (CH_3 + O_2 → CH_3O + O) led to〈γ〉= 8 x 10^(-4) for the combined probability of radical recombination on silica in this range and to k_2 (CH_3 + O_2 → CH_2O + OH) values that are in agreement with updated estimates and new shock tube results. An exploratory analysis of the nonlinearities dated with this process provides clues for the rational control of selectivity in the oxidative dimerization of methane.
| Item Type: | Article | |||||||||
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| Additional Information: | © 1992 American Chemical Society. (Received: February 18, 1992; In Final Form: May 12, 1992) This study was financially supported by CONICET of Argentina. | |||||||||
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| Issue or Number: | 17 | |||||||||
| DOI: | 10.1021/j100196a031 | |||||||||
| Record Number: | CaltechAUTHORS:20150623-154806290 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20150623-154806290 | |||||||||
| Official Citation: | High-temperature oxidation of methyl radicals in open systems M. A. Grela, V. T. Amorebieta, and A. J. Colussi The Journal of Physical Chemistry 1992 96 (17), 7013-7018 DOI: 10.1021/j100196a031 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 58515 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | George Porter | |||||||||
| Deposited On: | 26 Jun 2015 14:46 | |||||||||
| Last Modified: | 10 Nov 2021 22:06 |
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