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Kinetics of the reactions of hydroxyl radical with aliphatic aldehydes
Author(s) -
Semmes D. H.,
Ravishankara A. R.,
GumpPerkins C. A.,
Wine P. H.
Publication year - 1985
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550170307
Subject(s) - chemistry , flash photolysis , kinetics , aldehyde , photochemistry , reactivity (psychology) , hydroxyl radical , chemical kinetics , reaction rate constant , hydrocarbon , photodissociation , radical , organic chemistry , catalysis , medicine , physics , alternative medicine , pathology , quantum mechanics
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.