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Intramolecular hydrogen isotope effect in the pyrolysis of diethyl carbonate-1,1,1,2,2-d5

✍ Scribed by William E. Farneth; Thomas L. Beck

Publisher: John Wiley and Sons
Year: 1983
Tongue: English
Weight: 332 KB
Volume: 15
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550150506

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✦ Synopsis

The thermal unimolecular decomposition of diethyl carbonate-1,1,1,2,2-d5 has been examined in the high-pressure-limiting region. The observed chemistry is consistent with a simple, competitive two-channel model:

The intramolecular isotope effect k H / k D has been determined, and the relative Arrhenius parameters for the two channels are given by k H l k D = (0.80 f 0.18) exp [(1140 f 260) cal/mol/RT] over the temperature range of 540-620 K. These Arrhenius parameters predict an isotope effect k ~/ k ~ = 5.4 at 300 K.

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