Fernandes Ravi X, Luther Klaus, Marowsky Gerd, Rissanen Matti P, Timonen Raimo, Troe Jürgen
†Physikalische-Technische Bundesanstalt, Bundesallee 100, D-38116 Braunschweig, Germany.
‡Institut für Physikalische Chemie, Universität Göttingen, Tammannstrasse 6, D-37077 Göttingen, Germany.
J Phys Chem A. 2015 Jul 16;119(28):7263-9. doi: 10.1021/jp511672v. Epub 2015 Feb 6.
The reaction C2H5 + O2 (+ M) → C2H5O2 (+ M) was studied at 298 K at pressures of the bath gas M = Ar between 100 and 1000 bar. The transition from the falloff curve of an energy transfer mechanism to a high pressure range with contributions from the radical complex mechanism was observed. Further experiments were done between 188 and 298 K in the bath gas M = He at pressures in the range 0.7-2.0 Torr. The available data are analyzed in terms of unimolecular rate theory. An improved analytical representation of the temperature and pressure dependence of the rate constant is given for conditions where the chemical activation process C2H5 + O2 (+ M) → C2H4 + HO2 (+ M) is only of minor importance.
