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Kinetics of the reactions of hydroxyl radical with aliphatic aldehydes

1985; Wiley; Volume: 17; Issue: 3 Linguagem: Inglês

10.1002/kin.550170307

1097-4601

D. H. Semmes, A. R. Ravishankara, C. A. Gump‐Perkins, P. H. Wine,

Catalytic Processes in Materials Science

Abstract Rate coefficients for OH reactions with the 2–5 carbon aliphatic aldehydes have been measured under pseudo first‐order conditions in OH. OH was generated by flash photolysis of H 2 O at wavelengths greater than 165 nm and its concentration monitored using time‐resolved resonance fluorescence spectroscopy. Two reactions were studied only at 298 K while five reactions were studied over the temperature range 250–425 K; negative activation energies were observed for all five reactions. Aldehyde reactivity toward OH is nearly independent of the identity of the hydrocarbon side chain. Our results are compared with those obtained in previous studies of OH‐aldehyde reaction kinetics and their mechanistic implications are discussed.