42953-38-8Relevant academic research and scientific papers
Rates of Reaction of Propyl Radicals with Molecular Oxygen
Ruiz, Rennie P.,Bayes, Kyle D.
, p. 2592 - 2595 (1984)
The rates of reaction of 1-propyl and 2-propyl radicals with O2 have been measured in the gas phase at romm temperature.The rate constants are k1(1-C3H7+O2) = (5.5 +/-0.9)E-12 cm3 molecule-1 s-1 and K2(2-C3H7+O2) = (14.1+/-2.4)E-12 cm3 molecule-1 s-1.Limited pressure studies suggest that both of these reactions are at or near their high-pressure limits at pressures of a few torr.The logarithms of these and previously measured rate constants show an excellent correlation with the ionization potential of the alkyl radical (Figure 2).Adiabatic channel model calculations have been carried out for these reactions with various long-range potential functions.It is concluded that some mixing of the charge-transfer surface (R+ + O2-) into the neutral surface (R + O2) is responsible for the correlation of log (k) with ionization potential.
Thermal Decomposition of Alkyl Peroxynitrates
Zabel, F.,Reimer, A.,Becsker, K. H.,Fink, E. H.
, p. 5500 - 5507 (2007/10/02)
The thermal decomposition of methyl peroxynitrate and ethyl peroxynitrate was studied in a temperature-controlled 420 L glass chamber at temperatures between -28 and 0 deg C and total pressures from 10 to 800 mbar (M = N2).The reactions proceed via OO-N bond fission.The unimolecular decay of the peroxynitrates was followed in situ by long-path IR absorption using a Fourier transform spectrometer.In Troe's notation, the data are represented by the following limiting low- and high-pressure first-order rate constants k0 and kinfinite and the falloff curvature parameters Fc: for R = CH3, K0/ = 9.0 x 10-5 exp(-80.6 kJ mol-1/RT) cm3 molecule-1s-1, kinfinitive = 1.1 x 1016 exp(-87.8 kJ mol-1/RT)s-1, Fc = 0.4; for R =C2H5, k0/ = 4.8 x 10-4 exp(-77.2 kJ mol-1/RT)cm3 molecule-1 s-1, kinfinitive = 8.8 x 1015 exp(-86.8 kJ mol-1/RT)s-1, Fc =0.3.Combining the present results for R = CH3 with literature data on the corresponding recombination reaction, Kc = 1.94 x 1027 exp(-10766K/T) molecule cm-3 is obtained for the equilibrium CH3OONO2 CH3OO + NO2.Some experiments were performed on the thermal decomposition of isomeric mixtures of butyl, hexyl, and octyl peroxynitrate at 253 K and in 800 mbar of N2.Atmospheric implications of the thermal stability of alkyl peroxynitrates are briefly discussed.
