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

Abstract 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: equation image 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.