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

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: The ratio k₁/k₂ was found to be temperature dependent. An Arrhenius plot of the data (398.6 to 493.3 K) yields the relative Arrhenius parameters, E₁ - E₂ = ?11.2 ± 0.8 kJ mol^?1 and (A₁/A₂) = 0.59 ± 0.14. The ratio of rate constants k₁/k₂ was 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.