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The kinetics of the gas-phase decomposition of the 2-methyl-2-butoxyl and 2-methyl-2-pentoxyl radicals

Johnson, D., Carr, S. and Cox, R.A. (2005) The kinetics of the gas-phase decomposition of the 2-methyl-2-butoxyl and 2-methyl-2-pentoxyl radicals. Physical Chemistry Chemical Physics, 7 (10). pp. 2182-2190. ISSN 1463-9076

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Official URL: http://pubs.rsc.org/en/Journals/JournalIssues/CP

Abstract/Summary

The kinetics of the title reactions have been studied by relative-rate methods as a function of temperature. Relative-rate coefficients for the two decomposition channels of 2-methyl-2-butoxyl have been measured at five different temperatures between 283 and 345 K and the observed temperature dependence is consistent with the results of some previous experimental studies. The kinetics of the two decomposition channels of 2-methyl-2-pentoxyl have also been investigated, as a function of temperature, relative to the estimated rate of isomerisation of this radical. Room-temperature rate coefficient data for the two decomposition channels of both 2-methyl-2-pentoxyl and 2-methyl-2-butxoyl (after combining the relative rate coefficient for this latter with a value for the rate coefficient of the major channel, extrapolated from the data presented by Batt et al., Int. J. Chem. Kinet., 1978, 10, 931) are shown to be consistent with a non-linear kinetic correlation, for alkoxyl radical decomposition rate data, previously presented by this laboratory (Johnson et al., Atmos. Environ., 2004, 38, 1755-1765).

Item Type:Article
Refereed:Yes
Divisions:Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:11367
Uncontrolled Keywords:THERMAL UNIMOLECULAR DECOMPOSITION, I-PROPOXY RADICALS, ALKOXY RADICALS, RATE CONSTANTS, ALKYL NITRITES, ATMOSPHERIC CHEMISTRY, 3-PENTOXY RADICALS, 2-BUTOXY RADICALS, ORGANIC-COMPOUNDS, PHOTO-OXIDATION

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