Liquid‐phase autoxidation of organic compounds at elevated temperatures. Absolute rate constant for intermolecular hydrogen abstraction in hexadecane autoxidation at 120–190°C

Abstract

AbstractThe absolute rate constants for the intermolecular hydrogen abstraction reactions of secondary hydrogens by secondary alkylperoxy radicals in hexadecane autoxidation, k3, have been determined in the temperature range of 120–190°C using the stirred flow reactor technique. Absolute rate constants determined in this study for hexadecane are in good agreement with those determined for other hydrocarbons in liquid phase, on a per hydrogen basis, at lower temperatures. Arrhenius parameters for k3/H derived from this study are A = 108.6 M−1 s−1 and Ea = 16.0 kcal/mol. The values of these parameters provide experimental confirmation for previous estimates made from both lower temperature reactions in the liquid phase and higher temperature reactions in the gas phase. © 1994 John Wiley & Sons, Inc.