Kinetics of chemically activated ethane
作者:
F. B. Growcock,
W. L. Hase,
J. W. Simons,
期刊:
International Journal of Chemical Kinetics
(WILEY Available online 1973)
卷期:
Volume 5,
issue 1
页码: 77-92
ISSN:0538-8066
年代: 1973
DOI:10.1002/kin.550050108
出版商: John Wiley&Sons, Inc.
数据来源: WILEY
摘要:
AbstractChemically activated ethane, with an excitation energy of 114.9 ± 2 kcal/mole, was formed by reaction with methane of excited singlet methylene radicals produced by the 4358 Å photolysis of diazomethane. A decomposition rate constant of (4.6 ± 1.2) × 109sec−1was 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 forE0= 85.8 kcal/mole,E* = 114.9 kcal/mole, andkE= 4.6 × 101 sec−1, a thermalA‐factor at 600°K of 1016.6±0.2sec−1, in approximate agreement with the more recent experimental values. Combining 2 kcal/mole uncertainties inE0andE* with the uncertainty in our rate constant yields anA‐factor range of 1016.6±0.7sec−1. It is emphasized that this large uncertainty in theA‐factor results from an improbable combination of uncertainty limits for the various parameters. These decomposition results predict, via absolute rate theory (withE0(recombination) = 0) and statistical thermodynamic equilibrium constants, methyl radical recombination rates at 25°C of between 4.4 × 108to 3.1 × 109l.‐mole−1‐sec−1, which are 60 to 8 times lower, respectively, than the apparently quite reliable experimental value. A value ofE0(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 andE0(recombination) = 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 alka
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