Relative rate constants of the gas-phase decomposition reactions of the s-butoxy radical

✍ Scribed by Roger M. Drew; J. Alistair Kerr; Jonathan Olive

• Publisher: John Wiley and Sons
• Year: 1985
• Tongue: English
• Weight: 432 KB
• Volume: 17
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550170205

✦ Synopsis

s-Butoxy radicals have been generated by reacting fluorine with s-butanol:

Over the temperature range 398.6 to 493.3 K the s-butoxy radical decomposes by two different pathways to yield acetaldehyde and propionaldehyde, acetaldehyde being the major product:

(1)

The ratio k , / k z was found to be temperature dependent. An Arrhenius plot of the data (398.6 to 493.3 K) yields the relative Arrhenius parameters, E , -E , = --11.2 i 0.8 kJ mol-' and (A,/A,) = 0.59 2 0.14. The ratio of rate constants k , / k , w a s shown to be independent of total pressure (80-600 torr) and of the pressure of s-butanol (2-13 torr). The kinetic results for these s-butoxy decomposition reactions are (discussed in relation to the literature data and in terms of the thermochemistry of the reactions.