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Kinetics of chemically activated ethane

โœ Scribed by F. B. Growcock; W. L. Hase; J. W. Simons


Publisher
John Wiley and Sons
Year
1973
Tongue
English
Weight
835 KB
Volume
5
Category
Article
ISSN
0538-8066

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โœฆ Synopsis


Chemically activated ethane, with an excitation energy of 114.9 f 2 kcal/mole, was forme; by reaction with methane of excited singlet methylene radicals produced by the 4358 A photolysis of diazomethane. A decomposition rate constant of (4.6 =k 1.2) X l o 9 sec-' was measured for the chemically activated ethane. This result agrees, via RRKM theory, with most other chemically activated ethane data, and the result predicts, via RRKM and absolute rate theory for Eo = 85.8 kcal/mole, E* = 114.9 kcal/niole, and k E = 4.6X 10' sec-I, a thermal A-factor at 600ยฐK of 1016.6io * sec-I, in approximate agreement with the more recent experimental values. Combining 2 kcal/mole uncertainties in Eo and E * with the uncertainty in our rate constant yields an A-factor range of lox6 6i0.7 sec-'. It is emphasized that this large uncertainty in the A-factor results from an improbable combination of uncertainty limits for the various parameters. These decomposition results predict, via absolute rate theory (with &(recombination) = 0) and statistical thermodynamic equilibrium constants, methyl radical recombination rates at 25ยฐC of between 4.4X l o 8 to 3.1 X 109 l.-rnole-'-sec-', which are 60 to 8 times lower, respectively, than the apparently quite reliable experimental value. A value of &(recombination) greater than zero offers no improvement, and a value less than zero would be quite unusual. Activated complexes consistent with the experimental recombination rate and Eo(recombinati0n) = 0 greatly overestimate the experimental chemical activation and high pressure thermal decomposition rate data. Absolute rate theory as it is applied here in a straightforward way has failed in this case, or a significant amount of internally consistent data are in serious error. Some corrections to our previous calculations for higher alkanes are discussed in Appendix 11.


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