✦ LIBER ✦
Intramolecular conversions. V. Rational rate constants for reversible unimolecular reactions
✍ Scribed by S. H. Bauer
- Publisher
- John Wiley and Sons
- Year
- 1985
- Tongue
- English
- Weight
- 674 KB
- Volume
- 17
- Category
- Article
- ISSN
- 0538-8066
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✦ Synopsis
Abstract
The available RRKM programs which cover the full pressure range (high → low‐pressure limits) were written for nonreversible reactions. For reversible reactions the correct shapes of the fall‐off curves can be estimated by applying a correction factor to the RRKM bimolecular rate constant, which depends on a ratio of state densities at the potential maximum. It is proposed that the analysis of such systems in terms of relaxation kinetics provides a more rational treatment, free of the ambiguities associated with specifying a “transition state.”