Abstract
The rate of decomposition of 2-pentoxy radical to acetaldehyde and n-propyl radical has been studied in the presence of NO in competition with nitrite formation at and above 200 kPa pressure over the temperature range of 363-413 K. The rate coefficient for the decomposition is given as log(kla/s−1) = (14.2 ± 0.4) - (13.8 ± 0.8) kcal mol−1/RT ln 10. Isomerization of 2-pentoxy radical by 1,5-hydrogen shift has been investigated in the range 279–385 K in competition with the decomposition in a static system, with methyl radicals present in high concentration to ensure trapping of the isomerized free radicals. The rate coefficient for isomerization is given as log(k3/s−1) = (11.1 ± 0.7) - (9.5 ± 1.1) kcal mol−1/RT ln 10. The implications of the results for atmospheric chemistry are discussed.
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