Photoionization mass spectrometer studies of the collisionally stabilized product distribution in the reaction of OH radicals with selected alkenes at 298 K

Journal Article · Thu Jul 22 04:00:00 EDT 1982 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100212a030· OSTI ID:6461871

Biermann, H W; Harris, G W; Pitts, Jr, J N

The reactions of OH radicals with propene, 1-butene, and 1-pentene have been studied in a discharge flow system coupled to a photoionization mass spectrometer. At total pressures near 2 torr a collisionally stabilized OH-alkene adduct was observed in each case. For 1-butene and 1-pentene the radicals arising from abstraction of a hydrogen atom from the alkene by OH were also observed and their absolute concentrations measured under controlled conditions. Contributions of the abstraction pathway to the overall reaction were as follows: propene, < 2%; 1-butene, 20 +- 6%; 1-pentene, 13 +- 5%. These results are in excellent agreement with predictions based on linear free energy relationships using rate data for the reactions of the alkenes with O(/sup 3/P) and OH taken from the literature and/or measured in this work. Rate constants (in cm/sup 3/ molecule/sup -1/ s/sup -1/) obtained as part of this study include the following: k/sub OH+butene/ = (3.0 +- 0.4) x 10/sup -11/; k/sub OH+1-pentene/ = (2.9 +- 0.4) x 10/sup -11/, (2.87 +- 0.13) x 10/sup -11/ (50 torr of Ar); k/sub O(3P)+propene/ = (4.4 +- 0.6) x 10/sup -12/;k/sub O(3P)+1-pentene/ = (4.7 +- 0.5) x 10/sup -12/; k/sub OH+CS/sub 2// less than or equal to 5 x 10/sup -14/, at 298 K and 2 torr of He total pressure unless otherwise stated. 5 figures, 2 tables.

• Research Organization: Univ. of California, Riverside
• OSTI ID: 6461871
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 86:15; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400301 -- Organic Chemistry-- Chemical &amp; Physicochemical Properties-- (-1987)
400600* -- Radiation Chemistry
ADDUCTS
ALKENES
BUTENES
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
DATA
ELEMENTS
EXPERIMENTAL DATA
FLUIDS
GASES
HELIUM
HYDROCARBONS
HYDROXYL RADICALS
INFORMATION
KINETICS
LOW PRESSURE
MASS SPECTRA
MEDIUM TEMPERATURE
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
PENTENES
PRESSURE DEPENDENCE
PROPYLENE
RADICALS
RARE GASES
REACTION KINETICS
SPECTRA
TEMPERATURE DEPENDENCE
TIME DEPENDENCE
YIELDS