Flash photolysis resonance fluorescence investigation of the gas-phase reactions of OH radicals with a series of aliphatic ketones over the temperature range 240-440 K

Journal Article · Thu Sep 10 00:00:00 EDT 1987 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100303a033· OSTI ID:5889836

Wallington, T J; Kurylo, M J

Absolute rate constants have been determined for the gas-phase reactions of OH radicals with a series of aliphatic ketones by the flash photolysis resonance fluorescence measurement technique. Experiments were performed over the temperature range 240-440 K at total pressures (using Ar diluent gas) between 25 and 50 Torr. The rate constant data for acetone (k/sub 1/), 2-butanone (k/sub 2/), and 3-pentanone (k/sub 3/) were used to derive the Arrhenius expressions k/sub 1/ = (1.7 +/- 0.4) x 10/sup -12/ exp(-(600 +/- 75)/T) cm/sup 3/ molecule/sup -1/ s/sup -1/, k/sub 2/ = (2.3 +/- 1.1) x 10/sup -12/ exp(-170 +/- 120)/T) cm/sup 3/ molecule/sup -1/ s/sup -1/, and k/sub 3/ = (2.8 +/- 0.3) x 10/sup -12/ exp(10 +/- 35)/T) cm/sup 3/ molecule/sup -1/ s/sup -1/. At 296 K, the measured rate constants (in units of 10/sup -13/ cm/sup 3/ molecule/sup -1/ s/sup -1/) were k/sub 1/ = 2.16 +/- 0.16, k/sub 2/ = 11.5 +/- 1.0, and k/sub 3/ = 27.4 +/- 1.3. Room temperature rate constants for the reaction of OH radicals with a number of other 2-ketones were also determined. These were (in the above units) 3,3-dimethyl-2-butanone (12.1 +/- 0.5), 2-pentanone (40.0 +/- 2.9), 2-hexanone (66.4 +/- 5.6), 2-heptanone (86.7 +/- 8.4reverse arrow, 2-octanone (110 +/- 9), 2-nonanone (122 +/- 13), and 2-decanone (132 +/- 12). The error limits represent 2 standard deviations (from the least-squares analysis); the authors estimate that an additional 5% uncertainty should be added to account for possible systematic error in the measurements. These results are discussed in terms of reactivity trends for C-H bonds located in the ..cap alpha.., ..beta.., and ..gamma.. positions with respect to the carbonyl group.

• Research Organization: National Bureau of Standards, Gaithersburg, MD
• OSTI ID: 5889836
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 91:19; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
500100 -- Environment
Atmospheric-- Basic Studies-- (-1989)
54 ENVIRONMENTAL SCIENCES
ABSORPTION
ACETONE
ARRHENIUS EQUATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
EQUATIONS
EXPERIMENTAL DATA
FLUORESCENCE
HYDROXYL RADICALS
INFORMATION
KETONES
KINETICS
LUMINESCENCE
NUMERICAL DATA
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADICALS
REACTION KINETICS
RESONANCE ABSORPTION