The kinetics of the gas-phase dehydrogenation of cyclopentane to cyclopentene is found to be consistent with a slow attack by a n I atom (step 4, text) on cyclopentane in the range 282-382OC. The measured rate constants fit the Xrrhenius equation, log k, = 11.95 f 0.08 -(24.9 f 0.23)/0 1 mole-l sec-
Kinetics of the reaction: 2C2H4 → C2H5 + C2H3· heat of formation of the vinyl radical
✍ Scribed by G. Ayranci; M. H. Back
- Publisher
- John Wiley and Sons
- Year
- 1983
- Tongue
- English
- Weight
- 929 KB
- Volume
- 15
- Category
- Article
- ISSN
- 0538-8066
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✦ Synopsis
The initial rates of formation of the major products in the thermal reactions of ethylene at temperatures in the neighborhood of 800 K have been measured in the presence and absence of the additives neopentane and ethane. It has been shown that in the absence of the additive the main initiation process is (1) 2CzH.4 + CzHb + CzH3 while in the presence of neopentane and ethane the following additional initiation processes occur:
From the ratios of the rates of formation of the major products in the presence and absence of the additive the ratios kN/kl and k&l were measured over the temperature range of 750-820 K. Taking values from the literature for k~ and k ~, the following value was obtained for k l :
64,200 f 2000 2.3RT log k l (L/mol. s) = 11.27 f 0.6 -Previous results using butene-1 as additive were rexamined and shown to be consistent with this measurement. From this measurement the following values were derived: AHf(CzH3) = 63.4 f 2 kcal/mol and D(C2H3-H) = 103 kcal/mol.
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The distributions of relative translational energy released during (i) loss of H, from metastable CH,CHi' ions, (ii) loss of HD from metastable CH,CDl' ions and (iii) loss of D, from metastable CD,CDl' ions ?.ere measured. The relevant parts of the potential energy surface of the reaction C,H:' + C