Hydrogen-atom abstraction from alkanes by OH. 6. Cyclopentane and cyclohexane

Journal Article · Thu Feb 26 04:00:00 EST 1987 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100289a037· OSTI ID:6868691

Droege, A T; Tully, F P

Absolute rate coefficients for the reactions of the hydroxyl radical with cyclopentane-h/sub 10/ (k/sub 1/), cyclopentane-d/sub 10/ (k/sub 2/), cyclohexane-h/sub 12/ (k/sub 3/), and cyclohexane-d/sub 12/ (k/sub 4/) were determined by the laser photolysis/laser-induced fluorescence technique. Kinetic data were obtained at a pressure of 400 torr of helium over the temperature ranges 295-491 (k/sub 1/), 295-602 (k/sub 2/), 292-491 (k/sub 3/), and 292-603 K (k/sub 4/). Rate-coefficient results are fitted to the modified-Arrhenius expressions k/sub 1/ (T) = 6.04 x 10/sup -16/T/sup 1.52/ exp(+220 cal mol/sup -1//RT) cm/sup 3/ molecule/sup -1/ s/sup -1/, k/sub 2/(T) = 4.50 x 10/sup -15/T/sup 1.21/ exp (-511 cal mol/sup -1//RT) cm/sup 3/ molecule/sup -1/ s/sup -1/, k/sub 3/(T) = 1.09 x 10/sup -15/T/sup 1.47/ exp(+249 cal mol/sup -1//RT) cm/sup 3/ molecule/sup -1/ s/sup -1/, and k/sub 3/(T) = 3.48 x 10/sup -16/T/sup 1.62/ exp(-112 cal mol/sup -1//RT) cm/sup 3/ molecule/sup -1/ s/sup -1/. Rate coefficients for abstraction of hydrogen atoms from methylene sites are determined and compared with their previous measurements on other alkanes. The kinetic isotope effect for abstraction of H and D atoms from cyclopentane and cyclohexane is characterized, and it is found to be very similar to that measured for H- and D-atom transfer to OH from the secondary sites in propane and n-butane.

• Research Organization: Sandia National Labs., Livermore, CA
• OSTI ID: 6868691
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 91:5; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
ALKANES
ARRHENIUS EQUATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CYCLOALKANES
CYCLOHEXANE
DATA
DECOMPOSITION
DEUTERIUM
EQUATIONS
EXPERIMENTAL DATA
FLUORESCENCE
HIGH TEMPERATURE
HYDROCARBONS
HYDROGEN ISOTOPES
HYDROGEN TRANSFER
HYDROXYL RADICALS
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LASERS
LIGHT NUCLEI
LOW PRESSURE
LUMINESCENCE
MEDIUM TEMPERATURE
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
PENTANE
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADICALS
REACTION KINETICS
STABLE ISOTOPES