𝔖 Bobbio Scriptorium
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Energy transfer in unimolecular reactions at high temperatures

✍ Scribed by J. A. Barnard; T. K. Parrott

Publisher
John Wiley and Sons
Year
1977
Tongue
English
Weight
588 KB
Volume
9
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

The application of modern theories of energy transfer to unimolecular reactions taking place at very high temperatures is discussed. It is shown that the efficiency of energy transfer for both reactant–reactant and reactant–inert diluent collisions may be substantially smaller than the values determined experimentally at lower temperatures. Consequently at high temperatures unimolecular falloff effects, particularly in some shock‐tube measurements, may be greater than has been believed hitherto.

The application of these calculations to the unimolecular reactions of cyclopropane, cyclobutane, and cyclohexene at temperatures around 1300°K is discussed, and it is shown that under shock‐tube conditions the apparent first‐order rate coefficient may be at least ten times less than the high‐pressure limiting value.

📜 SIMILAR VOLUMES

Measurements of collisional energy trans
Measurements of collisional energy transfer in unimolecular processes
✍ Robert G. Gilbert 📂 Article 📅 1983 🏛 Elsevier Science 🌐 English ⚖ 388 KB

It is shown that the optimal means of tabulating collisional energy transfer parameters in gas-phase uni-and ter-molecular reactions is as the average downward energy transfer, rather than the total energy transferred or the collision efficiency.