19884-77-6Relevant articles and documents
Thermal Decomposition of Alkyl Peroxynitrates
Zabel, F.,Reimer, A.,Becsker, K. H.,Fink, E. H.
, p. 5500 - 5507 (1989)
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.
Diphenol radical cations and semiquinone radicals as direct products of the free electron transfer from catechol, resorcinol and hydroquinone to parent solvent radical cations
Brede, Ortwin,Kapoor, Sudhir,Mukherjee, Tulsi,Hermann, Ralf,Naumov, Sergej
, p. 5096 - 5104 (2007/10/03)
In the pulse radiolysis of solutions of catechol, resorcinol and hydroquinone in n-butylchloride, dihydroxybenzene radical cations (40%) as well as semiquinone radicals (60%) are observed as direct synchronously formed products of the electron transfer from the solvent parent ions to the solute. This is explained in terms of free electron transfer succeeding in nearly every encounter of the reactants, which in the case of the studied dihydroxybenzenes involves femtosecond molecular dynamics effects. The rotation of the C-OH bond causes cycling of the molecule through transient conformations also exhibiting different electron distributions. From the more chemical point of view, the diphenol radical cations represent the first and till now unknown intermediates of oxidative semiquinone radical formation.
The Nucleophilicity of Superoxide towards Different Alkyl Halides Estimated from Kinetic Measurements
Daasbjerg, Kim,Lund, Henning
, p. 597 - 604 (2007/10/02)
Values of the rate constant ksub are measured for the substitution reaction between superoxide O2 anion-radical and the alkyl halides butyl chloride, 2-butyl chloride, benzyl chloride, ethyl bromide, butyl bromide, 2-butyl bromide, neopentyl bromide, benzyl bromide, (1-bromo-2,2-dimethylpropyl)benzene and 1-iodoadamantane.These rate constants are compared with the expected rate constant kET for the electron transfer reaction between the same alkyl halides and an aromatic anion radical A anion-radical with the same standard oxidation potential as O2 anion-radical.The ksub/kET ratios show that the mechanism of the substitution reaction amy shift from SN2-like to ET-like on changes in the steric hindrance and the acceptor ability of the alkyl halide.The influence on ksub/kET of the difference in self-exchange reorganization energy λ(0) between O2 anion-radical/O2 and A anion-radical/A is discussed.
