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J Phys Chem A. 2007 Oct 25;111(42):10667-70. Epub 2007 Oct 3.

Rate constants for the reaction of cl with a series of C4 to C6 ketones using the relative rate method.

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  • 1Department of Natural Sciences, 4901 Evergreen Road, University of Michigan - Dearborn, Dearborn, Michigan 48128, USA. ewkaiser@comcast.net


Rate constants for the reaction of Cl with eight ketones were measured relative to the rate constant of propane in approximately 900 Torr of N2 at ambient temperature. Experiments were carried out in a Pyrex reactor with GC analysis of the consumption of the ketones and propane. Chlorine atoms were generated by irradiation of Cl2 in the initial mixture using a black-light-blue fluorescent lamp. The rate constants determined in these experiments (10-11 cm3 molecule-1 s-1) are: butanone (3.8 +/- 0.3); 2-pentanone (11.6 +/- 1.0); 3-pentanone (8.3 +/- 0.7); 2-hexanone (19.4 +/- 1.9); 3-hexanone (15.3 +/- 1.1); cyclopentanone (10.4 +/- 0.9); 3-methyl-2-butanone (6.2 +/- 0.5); and 4-methyl-2-pentanone (12.8 +/- 1.0). The results for 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, 3-methyl-2-butanone, and 4-methyl-2-pentanone are significantly higher (by a factor of 3 for 2-hexanone) than reported in two previous absolute rate studies. The likely explanation for this discrepancy is discussed.

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