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Liquid‐phase autoxidation of organic compounds at elevated temperatures. Absolute rate constant for intermolecular hydrogen abstraction in hexadecane autoxidation at 120–190°C
Author(s) -
Jensen R. K.,
Korcek S.,
Zinbo M.
Publication year - 1994
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550260608
Subject(s) - autoxidation , chemistry , arrhenius equation , intermolecular force , hydrogen atom abstraction , reaction rate constant , atmospheric temperature range , hydrogen , hexadecane , radical , thermodynamics , phase (matter) , photochemistry , organic chemistry , activation energy , kinetics , molecule , physics , quantum mechanics
The absolute rate constants for the intermolecular hydrogen abstraction reactions of secondary hydrogens by secondary alkylperoxy radicals in hexadecane autoxidation, k 3 , 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 k 3 /H derived from this study are A = 10 8.6 M −1 s −1 and E a = 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.