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Kinetics and mechanisms of OH‐initiated oxidation of small unsaturated alcohols
Author(s) -
Takahashi Kenshi,
Hurley Michael D.,
Wallington Timothy J.
Publication year - 2010
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.20475
Subject(s) - chemistry , glycolaldehyde , radical , acetone , allyl alcohol , yield (engineering) , alcohol , kinetics , torr , molar ratio , double bond , medicinal chemistry , photochemistry , organic chemistry , catalysis , materials science , physics , quantum mechanics , metallurgy , thermodynamics
Smog chamber relative rate techniques were used to measure rate coefficients of (5.00 ± 0.54) × 10 −11 , (5.87 ± 0.63) × 10 −11 , and (6.49 ± 0.82) × 10 −11 cm 3 molecule −1 s −1 in 700 Torr air at 296 ± 1 K for reactions of OH radicals with allyl alcohol, 1‐buten‐3‐ol, and 2‐methyl‐3‐buten‐2‐ol, respectively; the quoted uncertainties encompass the extremes of determinations using two different reference compounds. The OH‐initiated oxidation of allyl alcohol in the presence of NO x gives glycolaldehyde in a molar yield of 0.85 ± 0.08; the quoted uncertainty is two standard deviations. Oxidation of 2‐methyl‐3‐buten‐2‐ol gives acetone and glycolaldehyde in molar yields of 0.66 ± 0.06 and 0.56 ± 0.05, respectively. The reaction of OH radicals with allyl alcohol, 1‐buten‐3‐ol, and 2‐methyl‐3‐buten‐2‐ol proceeds predominately via addition to the >CCH 2 double bond with most of the addition occurring to the terminal carbon. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 151–158, 2010

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