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Kinetics and mechanism of the thermal chlorination of chloroform in the gas phase
Author(s) -
Huybrechts G.,
Hubin Y.,
Van Mele B.
Publication year - 2000
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 - 10.1002/1097-4601(2000)32:8<466::aid-kin3>3.0.co;2-4
Subject(s) - chemistry , torr , dissociation (chemistry) , chloroform , quartz , kinetics , gas phase , pyrolysis , elementary reaction , analytical chemistry (journal) , thermodynamics , organic chemistry , physics , paleontology , quantum mechanics , biology
The gas‐phase thermal chlorination of CHCl 3 has been studied up to high conversions by photometry and gas chromatography in a conditioned static quartz reaction vessel between 573 and 635 K. The initial pressures of both CHCl 3 and Cl 2 ranged from about 10–100 Torr, and the initial total pressure was varied between about 30–190 Torr. The reaction is rather complex because the produced CCl 4 is not stable. The rate of consumption of Cl 2 therefore increases in the course of time. This acceleration is explained quantitatively in terms of a radical mechanism and its kinetic and thermodynamic parameters. This reaction model is based on a known model for the pyrolysis of CCl 4 to which only one reaction couple involving CHCl 3 has been added. Analyses of the rates of the homogeneous elementary steps show that the primary source of Cl atoms is the second‐order dissociation of Cl 2 , which is rapidly superseded by a secondary source, the first‐order dissociation of the CCl 4 primary product. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 466–472, 2000