2679-29-0Relevant articles and documents
FTIR and computational studies of gas-phase hydrogen atom abstraction kinetics by t-butoxy radical
Li, Shuping,Fan, Wai Yip
, p. 276 - 280 (2007/10/03)
By using Fourier-Transform Infrared (FTIR) absorption spectroscopy, rate coefficients in the range of 10-16 to 10-14 cm3 molecule-1 s-1 have been determined for the hydrogen atom abstraction reactions of several substrates including halogenated organic compounds and amines by t-butoxy radical generated from the uv photolysis of t-butyl nitrite in the gas phase. Arrhenius parameters for selected reactions have been measured in the temperature range 299-318 K. Transition states and activation barriers for such reactions have been computed with the help of Gaussian 03 software and found to match very well with the experimental values.
Reactions of Atomic Oxygen (3P) with Selected Alkanes
Miyoshi, Akira,Tsuchiya, Kentaro,Yamauchi, Noboru,Matsui, Hiroyuki
, p. 11452 - 11458 (2007/10/02)
Rate constants for the reactions of atomic oxygen (3P) with selected alkanes (C2-C6 straight chain alkanes, c-C6H12, neo-C5H12, and i-C4H10) have been determined directly by a laser photolysis-shock tube-atomic resonance absorption method at hi
Kinetics of the Reactions between CH2(3B1)-Radicals and Saturated Hydrocarbons in the Temperature Range 296 K = T = 707 K
Boehland, T.,Dobe, S.,Temps, F.,Wagner, H. Gg.
, p. 1110 - 1116 (2007/10/02)
The reaction between CH2-radicals in their ground electronic state (3B1) and n-hexane CH2() + n-C6H14 --> CH3 + C6H13 was studied in a discharge flow system with LMR detection of CH2.In the temperature regime 413 K 4 = 1E(13.22 +/- 0.20)*exp(-3380 +/- 240/T) cm3/mol s.The reaction proceeds both via direct H-atom abstraction by CH2() and via thermal excitation of CH2() to the low-lying singlet state (1A1) followed by fast consecutive reactions of CH2().The contributions due to thermal excitation and singlet reaction were evaluated for the present work as well as for a recent study of the reactions of CH2() with a series of other hydrocarbons.Corrected rate constants kT for the direct reactions of CH2() with the reactants HR = CH4 (1), C2H6 (2), C3H8 (3), n-C6H14 (4), i-C4H10 (5), and CH3CHO (6) in the temperature range 296 K 1T = 4.3E12*exp(-42 kJ mol-1/RT) cm3/mol s, k2T = 6.5E12*exp(-33.1 kJ mol-1/RT) cm3/mol s, k3T = 4.9E12*exp(-27.7 kJ mol-1/RT) cm3/mol s, k4T = 7.8E12*exp(-25.6kJ mol-1/RT) cm3/mol s, k5T = 2.5E12*exp(-22.5 kJ mol-1/RT) cm3/mol s, k6T = 1.7E12*exp(-14.7 kJ mol-1/RT) cm3/mol s.The activation energies for the reactions studied are described by an Evans Polanyi type relation.Arrhenius expressions are proposed for the rate constants of H-atom abstraction by CH2(3B1) from primary, secondary, tertiary, and aldehydic C-H bonds.The results are compared to the isoelectronic reactions of O(3P). - Keywords: Chemical Kinetics / Elementary Reactions / Radicals / Spectroscopy, Laser Magnetic Resonance