ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Hydrogen abstration from H2S by CF3 radicals, generated by the photolysis of both CF3COCF3 and CF3I, has been studied in the temperature range 314-434 K. The rate constant, based on the value of 1013.36 cm3/mol · s for the recombination of CF3 radicals, is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log }\,k_2 \, = \,\left( {12.20\, \pm \,0.05} \right)\, - \,{{\left( {19,220\, \pm \,360} \right)} \mathord{\left/ {\vphantom {{\left( {19,220\, \pm \,360} \right)} {19.145T}}} \right. \kern-\nulldelimiterspace} {19.145T}} $$\end{document} with CF3COCF3 as the radical source, and \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log }\,k_2 \, = \,\left( {12.00\, \pm \,0.07} \right)\, - \,{{\left( {18,270\, \pm \,470} \right)} \mathord{\left/ {\vphantom {{\left( {18,270\, \pm \,470} \right)} {19.145T}}} \right. \kern-\nulldelimiterspace} {19.145T}} $$\end{document} with CF3I as the radical source, where k2 is in cm3/mol · s and E is in J/mol. These results resolve a previously existing controversy concerning the values of the rate constants for this reaction. They show that CF3 radicals are less reactive than CH3 radicals in attacking H2S, and this behavior indicates that polar effects play a significant role in the hydrogen transfer reactions of CF3 radicals.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550160404
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