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Kinetics and mechanism of the thermal gas‐phase reaction between NO 2 and trichloroethene at 303–362.2 K
Author(s) -
Czarnowski J.
Publication year - 1992
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.550240708
Subject(s) - chemistry , torr , kinetics , homogeneous , gas phase , atmospheric temperature range , phase (matter) , analytical chemistry (journal) , reaction mechanism , total pressure , infrared , thermodynamics , catalysis , chromatography , organic chemistry , optics , physics , quantum mechanics
The kinetics of the gas‐phase reaction between NO 2 and trichloroethene has been investigated in the temperature range 303–362.2 K. The pressure of NO 2 was varied betwen 5.1 and 48.7 torr and that of trichloroethene between 7.3 and 69.5 torr. The reaction was homogeneous. Two products were formed: nitrosyl chloride, ClNO, and glyoxyloxyl chloride, HC[O]C[O]Cl, which was identified by its infrared spectrum and its molecular weight determined by chromatography. The rate of consumption of the reactants was independent of the total pressure and can be represented by a second‐order reaction:\documentclass{article}\pagestyle{empty}\begin{document}$$ -d[{\rm NO}_2]/dt = - 2d[{\rm CHClCCl}_2]/dt = k[{\rm NO}_2][{\rm CHClCCl}_2] $$\end{document} The following mechanism was proposed to explain the experimental results:The following expression was obtained for k :\documentclass{article}\pagestyle{empty}\begin{document}$$ k= 2k_1 k_3/[k_2 + k_3] = 4.07 \pm 1.2 \,\times\, 10^2 \exp [-8800\, \pm\, 800\,{\rm cal\,mol}^{-1}/ RT]1\,{\rm mol}^{-1}\,{\rm s}^{-1} $$\end{document} . © John Wiley & Sons, Inc.